The

MCAT
Chemistry Book
A Comprehensive Review of
General Chemistry and Organic Chemistry
for the Medical College Admission Test

Ajikumar Aryangat

* M C A T i s a r e g i s t e r e d trademark o f the A s s o c i a t i o n o f A m e r i c a n Medical C o l l e g e s

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Copyright 02006 by Nova Press

Previous editions: 2001, 1998
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ISBN 1-889057-37-1

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To my parents, Vasu and Nalini Aryangat, for their guidance and encouragement
for the pursuit of educational excellence.
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CONTENTS
INTRODUCTION

Part I General Chemistry

CHAPTER 1: MATTER ....................................................................5
A . INTRODUCTION ................................................................................5
B. ATOMS ................................................................................................... 5
Elements ...................................................................................................... 5
Compounds.................................................................................................. 5
Mixtures ....................................................................................................... 6
C . DALTON'S ATOMIC THEORY ......................................................... 6
Ramifications of Dalton's Theory ........................................................... 7
D . THE GENERAL STRUCTURE O F THE ATOM .............................. 7
E . ELECTRONS ......................................................................................... 8
Charge of Electrons ..................................................................................... 8
F . PROTONS .............................................................................................. 9
G . NEUTRONS ..................................................................................... 9
H . ATOMIC NUMBER AND MASS NUMBER ......................................9
I . ATOMIC WEIGHT .............................................................................. 10
J . MOLECULES ........................................................................................10
Molecular Weight ...................................................................................... 10
..
Emplrlcal Formula ..................................................................................... 11
K . THE CONCEPT O F MOLE ............................................................... 12
L. COMPOSITION BY PERCENTAGE ................................................ 13
Predicting Formulas from Percentage Compositions ............................... 14
M . DENSITY ............................................................................................. 16
Chapter 1 PRACTICE QUESTIONS....................................................... 17

CHAPTER 2: CHEMICAL REACTIONS .............................. 21

A . INTRODUCTION ..............................................................................21
B. CHEMICAL REACTIONS ................................................................. 21
C . TYPES OF CHEMICAL REACTIONS .............................................21
. .
Comblnat~onReaction ...............................................................................22
Combustion Reaction ................................................................................22
Decomposition Reaction ...........................................................................22
Displacement Reaction (single-replacementreaction) ............................... 22
Metathesis Reaction (double-replacement reaction) .................................. 23
D . BALANCING SIMPLE EQUATIONS ..............................................23
E. OXIDATION NUMBER ..................................................................... 24
F . OXIDATION-REDUCTION REACTIONS ..................................... 27
Balancing Oxidation-Reduction Reactions ................................................ 28
G . CALCULATIONS INVOLVING CHEMICAL REACTIONS ........ 31
H . THE CONCEPT OF LIMITING REAGENT ................................... 32
I. PERCENT YIELD ................................................................................ 33
CHAPTER 2 PRACTICE QUESTIONS...............................................35

CHAPTER 3: ELECTRONIC STRUCTURE ........................ 39

A. INTRODUCTION .............................................................................. 39
B. ATOMIC STRUCTURE......................................................................39
Electromagnetic Waves .............................................................................. 39
The Wave Nature ...................................................................................... 39
The Particle Nature and Quantum Theory ............................................... 40
Photoelectric Effect .................................................................................... 41
Key Observations on Photoelectric Effect .................................................42
. .
Atomic Emission Spectra ...........................................................................42
Bohr's Model of Hydrogen Atom ............................................................. 43
C. QUANTUM NUMBERS.....................................................................44
D . ELECTRONIC CONFIGURATION ................................................47
Hund's Rule ...............................................................................................49
CHAPTER 3 PRACTICE QUESTIONS ................................................ 50

CHAPTER 4: PERIODIC TABLE .............................................. 53

A. INTRODUCTION ..............................................................................53
B. T H E PERIODIC TABLE ..................................................................... 53
Group IA ...................................................................................................53
Group IIA ..................................................................................................54
Group IIIA................................................................................................. 54
Group IVA .................................................................................................54
Group VA ..................................................................................................55
Group VIA ................................................................................................. 55
Group VIIA ...............................................................................................55
Group VIIIA .............................................................................................. 55
C . PERIODIC TRENDS .ONE BY ONE ........................................ 55
Atomic Size ................................................................................................ 56
Ionic Radius ............................................................................................... 56
Ionization Energy (IE) ............................................................................... 57
..
Electron Affinity ........................................................................................ 57
. .
Electronegatlvity ........................................................................................ 57
CHAPTER 4 PRACTICE QUESTIONS ...............................................58
CHAPTER 5: CHEMICAL BONDING ..................................61
A . INTRODUCTION ............................................................................. 61
What are Chemical Bonds? ........................................................................ 61
B. IONIC BOND ..................................................................................... 61
Formation of the Ionic Bond in NaF .........................................................62
C . COVALENT BOND ........................................................................... 63
Covalent Bond Formation ........................................................................63
D . COORDINATE COVALENT BOND .............................................64
E . POLAR AND NONPOLAR COVALENT BONDS ........................ 65
F . THE LEWIS ELECTRON-DOT FORMULAS ..................................66
Writing Lewis Formulas ............................................................................ 66
G . RESONANCE ..................................................................................... 68
H . FORMAL CHARGE ........................................................................... 68
I . BOND LENGTH A N D BOND ENERGY .........................................70
J . MOLECULAR GEOMETRY ...............................................................70
Valence Shell Electron Pair Repulsion Theory .........................................71
CHAPTER 5 PRACTICE QUESTIONS ...............................................74

CHAPTER 6: GASES .......................................................................77

A . INTRODUCTION ..............................................................................77
B. GASES .AN OVERVIEW ...................................................................77
Standard Temperature and Pressure ..........................................................77
Molar Volume ............................................................................................78
C . GAS LAWS ...........................................................................................79
Boyle's Law ................................................................................................ 79
Charles' Law .............................................................................................. 80
Combined Gas Law ................................................................................... 81
The Ideal Gas Law .................................................................................... 81
D . KINETIC THEORY OF GASES ...................................................... 82
Some Aspects Related to Kinetic Theory .................................................. 82
E . PARTIAL PRESSURE AND MOLE FRACTION ............................. 83
Dalton's Law of Partial Pressures ............................................................ 84
F . GRAHAM'S LAW ................................................................................ 85
CHAPTER 6 PRACTICE QUESTIONS............................................... 87
CHAPTER 7 : LIQUIDS. SOLIDS.
AND PHASE TRANSITIONS ............................................. 91
A. INTRODUCTION .............................................................................. 91
B. THE LIQUID STATE ..........................................................................91
C . INTERMOLECULAR FORCES ........................................................ 92
Hydrogen .Bonding ......................................
. . 92
Dipole-Dipole Interactions ....................................................................... 93
London Forces ........................................................................................... 93
D . THE SOLID STATE............................................................................ 94
Ionic Solid .................................................................................................. 94
Metallic Solid ............................................................................................. 94
Molecular Solid .......................................................................................... 95
Network Solid............................................................................................95
E. PHASE TRANSITIONS ......................................................................95
Types of Phase Transitions ....................................................................96
F . HEAT TRANSFER ..............................................................................97
G. PHASE DIAGRAMS ...........................................................................98
H . COLLIGATIVE PROPERTIES ......................................................... 101
Vapor-pressure Lowering .......................................................................1 0 1
Boiling-point Elevation ..................:.....................................i ...........:........102
Freezing-point Depression ........................................................................103
Osmotic Pressure ......................................................................................104
CHAPTER 7 PRACTICE QUESTIONS .............................................. 106

CHAPTER 8: CHEMISTRY OF SOLUTIONS ...................109

A . INTRODUCTION .............................................................................109
B. THE CONCEPT OF SOLUBILITY ..................................................109
..
The Reasons for Solubility........................................................................110
Ionic Solutions ..........................................................................................110
C . MOLARITY ........................................................................................110
D . MOLALITY ........................................................................................110
E. NORMALITY ..................................................................................... 111
F. THE SOLUBILITY PRODUCT CONSTANT ................................. 112
Ion Product ...............................................................................................
114
G. COMMON-ION EFFECT ................................................................. 114
H. ELECTROLYTES .............................................................................. 116
CHAPTER 8 PRACTICE QUESTIONS .............................................. 118
CHAPTER 9: ACID-BASE EQUILIBRIUM .........................121
A . INTRODUCTION ............................................................................. 121
B. DEFINITIONS OF ACIDS AND BASES .......................................... 121
..
The Arrhenius Definition ......................................................................... 121
The Bronsted-Lowry Definition ............................................................... 121
C . THE LEWIS THEORY .......................................................................122
D . IONIZATION OF WATER .............................................................. 122
E . THE CONCEPT OF pH ...................................................................123
F . STRONG ACIDS AND BASES .......................................................... 124
G. WEAK ACIDS AND BASES .............................................................. 125
Acid-ionization Constant (Ka).................................................................. 125
. .
Percentage Ionization ................................................................................ 126
Base-ionization Constant (Kb) .................................................................. 127
H . DISSOCIATION OF POLYPROTIC ACIDS ..................................128
I: DIFFERENTIATING ACIDIC AND BASIC SALTS ........................129
J . BUFFERS ............................................................................................. -130
K.TITRATION CURVES OF ACIDS AND BASES .............................131
Indicators .................................................................................................. 131
Titration of a Strong Acid with a Strong Base ..........................................133
Titration of a Weak Acid with a Strong Base ........................................... 134
Titration of a Weak Base with a Strong Acid ........................................... 135
CHAPTER 9 PRACTICE QUESTIONS ..............................................136

CHAPTER 10: THERMODYNAMICS ...................................139

A . INTRODUCTION ............................................................................. 139
What is Thermodynamics? .......................................................................139
B. THE FIRST LAW O F THERMODYNAMICS ................................. 139
Basic Aspects of Thermodynamics ...........................................................140
C . ENDOTHERMIC AND EXOTHERMIC REACTIONS ................140
D . LAW OF HEAT SUMMATION ....................................................... 140
E. THE SECOND LAW OF THERMODYNAMICS ...........................142
F . THE THIRD LAW OF THERMODYNAMICS ...............................143
G . FREE ENERGY ..................................................................................144
How Can We Predict Spontaneity? ..........................................................144
H. TEMPERATURE .SOME BASICS ...................................................145
CHAPTER 10 PRACTICE QUESTIONS ..............................................146
CHAPTER 11: EQUILIBRIUM A N D KINETICS .............147
A . INTRODUCTION ............................................................................. 147
B . RATE OF REACTION ....................................................................... 147
Rate Law ...................................................................................................
148
C . TRANSITION STATE ....................................................................... 150
D . TEMPERATURE DEPENDANCE O F RATE ................................152
E . A BRIEF LOOK AT CATALYSTS .................................................... 152
F . CHEMICAL EQUILIBRIUM ............................................................. 153
. . .
The Equilibrium Constant ........................................................................ 153
G. FACTORS T H A T AFFECT
THE EQUILIBRIUM O F REACTIONS ........................................... 154
Effect of Temperature ..............................................................................154
Effect of Pressure ......................................................................................
155
CHAPTER 11 PRACTICE QUESTIONS ............................................. 156

CHAPTER 12: ELECTROCHEMISTRY ................................159

A . INTRODUCTION ............................................................................. 159
B. ELECTROLYTIC CELL ..................................................................... 159
C . FARADAY'S LAW ............................................................................. 161
D . GALVANIC CELL ............................................................................. 161
E . STANDARD ELECTRO.DE POTENTIALS ....................................163
Finding the emf of a Cell ..........................................................................
165
F . THE FREE ENERGY-EMF RELATION ..........................................166
CHAPTER 12 PRACTICE QUESTIONS ............................................ 168

CHAPTER 13: RADIOACTIVITY ...........................................171

A . INTRODUCTION ............................................................................. 171
B. STABILITY O F NUCLEUS ................................................................ 171
C . RADIOACTIVE DECAY ..................................................................171
D . HALF-LIFE ........................................................................................-172
CHAPTER 13 PRACTICE QUESTIONS.......................................... 174
 Part I1 Organic Chemistry
CHAPTER 14: GENERAL CONCEPTS .................................179
A . INTRODUCTION ............................................................................. 179
B. THE CARBON ATOM ...................................................................... 179
C . BONDING .......................................................................................... 180
D . HYBRIDIZATION OF ORBITALS ..................................................180
. . . ....................................................................................... 180
sp Hybridization
. .
sp2 Hybridization ....................................................................................... 181
sp Hybridization .......................................................................................182
E. RESONANCE ..................................................................................... 182
F . FUNCTIONAL GROUPS .................................................................. 183
CHAPTER 14 PRACTICE QUESTIONS ............................................184

CHAPTER 15: ALKANES ............................................................ 187

A . INTRODUCTION ............................................................................. 187
B. ALKANES ........................................................................................... 187
C . PROPERTIES O F ALKANES............................................................188
D . STRAIGHT CHAIN AND BRANCHED ALKANES .....................188
E. ALKYL GROUPS................................................................................ 189
F . THE IUPAC NAMING OF ALKANES ........................................... 189
G. CYCLOALKANES .............................................................................190
H . REACTIONS O F ALKANES ............................................................191
Combustion ............................................................................................. 191
Halogenation ...........................................................................................-191
I . MECHANISM O F FREE RADICAL SUBSTITUTION
OF ALKANES .................................................................................... 192
J . REACTIVITY O F ALKANES.............................................................193
Primary, Secondary, and Tertiary Carbons .............................................. 193
K. CONFORMATION AND STABILITY OF ALKANES.................. 194
Conformations ..........................................................................................194
L. CONFORMATION AND STABILITY OF CYCLOALKANES ....196
Conformations of Cyclohexane ................................................................196
CHAPTER 15 PRACTICE QUESTIONS ............................................201

CHAPTER 16: ALKENES ...........................................................205

A . INTRODUCTION .............................................................................205
B. NAMING O F ALKENES ...................................................................205
C . STRUCTURAL INTEGRITY AND ISOMERISM OF ALKENES .206
Isomerism ..................................................................................................
206
The E-Z System of Naming Alkenes ........................................................206

vii
D . GENERAL PROPERTIES O F ALKENES ........................................ 207
E . SYNTHESIS OF ALKENES ...............................................................207
From Alkanes ...........................................................................................208
From Alcohols ..........................................................................................208
From Alkyl Halides by Dehydrohalogenation ........................................208
From Vicinal Dibromides by Dehalogenation ........................................209
F . REACTIONS OF ALKENES ............................................................. 210
Hydrogenation ........................................................................................ -210
Alkenes with Hydrogen Halides ..............................................................210
Anti-Markovnikov Addition ....................................................................212
Alkenes with Halogens ............................................................................-214
Alkenes with Halogens in Aqueous Medium ...........................................215
. .
Epoxidatlon .............................................................................................. -216
Ozonolysis ................................................................................................ 216
Hydroxylation using Osmium Tetroxide ................................................. 217
Acid Catalyzed Reaction ........................................................................... 218
Hydroboration-Oxidation ....................................................................... 218
Oxymercuration-Demercuration ............................................................ -219
The Diels-Alder Reaction .........................................................................221
CHAPTER 16 PRACTICE QUESTIONS ............................................ 222

CHAPTER 17: ALKYNES ........................................................... -227

A . INTRODUCTION ............................................................................. 227
B. NAMING O F ALKYNES ................................................................... 227
C . SYNTHESIS O F ALKYNES ...............................................................228
Acetylene Synthesis by Adding H z0 to CaC, (calcium carbide) .............. 228
From Dihalogenoalkanes .......................................................................... 228
From Acetylene ........................................................................................ 228
D . REACTIONS O F ALKYNES ............................................................ 229
Hydrogenation ..........................................................................................229
Acid-Catalyzed Hydration ........................................................................229
Alkynes with Hydrogen Halides ..............................................................230
Alkynes with Halogens .............................................................................230
Ozonolysis ................................................................................................231
Reaction Involving the Acidic Hydrogen in an Alkyne ...........................231
Acetylide with Aldehydes and Ketones .....................;..............................232
CHAPTER 17 PRACTICE QUESTIONS ............................................. 233

viii
CHAPTER 18: AROMATIC COMPOUNDS ......................237
A . INTRODUCTION .............................................................................237
B. BENZENE ...........................................................................................238
Structure of Benzene .................................................................................238
C . DERIVATIVES O F BENZENE .........................................................239
D . PROPERTIES OF AROMATIC COMPOUNDS ............................240
E . CONCEPT OF AROMATICITY ......................................................240
F. REACTIONS OF AROMATIC COMPOUNDS ..............................243
Benzene Stability ......................................................................................243
Electrophilic Substitution Reactions ........................................................243
Nitration ..................................................................................................244
Friedel-Crafts Reactions ............................................................................245
Halogenation .............................................................................................249
Sulfonation ..............................................................................................-249
G. DIRECTIVE EFFECTS OF SUBSTITUENTS .................................249
. .
Activating Groups..................................................................................... 250
Deactivating Groups ................................................................................. 252
CHAPTER 18 PRACTICE QUESTIONS ............................................256

CHAPTER 19: STEREOCHEMISTRY ....................................261

A . INTRODUCTION ..............................................................................261
B. STEREOISOMERS.............................................................................. 262
Enantiomers .............................................................................................. 262
Diastereomers ........................................................................................... 263
C . OPTICAL ACTIVITY ...................................................................... 263
Some Generalizations Regarding Optical Activity ...................................263
Properties of Enantiomers and Diastereomers ......................................... 264
D . CONFIGURATIONS ........................................................................ 264
Chirality and Achirality ........................................................................... 264
Absolute Configuration ............................................................................ 266
R-SSystem of Representation .................................................................. 266
CHAPTER 19 PRACTICE QUESTIONS ............................................. 270

CHAPTER 20: ALKYL HALIDES ............................................. 273

A . INTRODUCTION .............................................................................273
B. NAMING OF ALKYL HALIDES ...................................................... 273
C . PROPERTIES OF ALKYL HALIDES ............................................... 273
D . SYNTHESIS OF ALKYL HALIDES ................................................. 274
From Alcohols ..........................................................................................274
From Alkanes ...................... ...................................................................274
;

From Alkenes ...........................................................................................275

E. REACTIONS OF ALKYL HALIDES ................................................ 275
Nucleophilic Substitution Reactions ........................................................275
The S. 2 Reaction ......................................................................................275
The Mechanism of SN2Reaction ...............................................................276
The S, 1 Reaction ...................................................................................... 278
The Mechanism of SN1Reaction ...............................................................278
. .
Elimlnatlon reactions ................................................................................280
The E2 reaction ......................................................................................... 280
The E l Reaction ....................................................................................... 281
Substitution versus Elimination ................................................................ 281
CHAPTER 20 PRACTICE QUESTIONS .............................................283

CHAPTER 21: ALCOHOLS ........................................................ 285

A. INTRODUCTION ............................................................................. 285
B. PROPERTIES OF ALCOHOLS ......................................................... 285
Boiling Point ............................................................................................. 285
Solubility in H, 0 ...................................................................................... 286
Acidity of Alcohols ................................................................................... 286
C . SYNTHESIS OF ALCOHOLS ........................................................... 287
Acid-Catalyzed Reaction ........................................................................... 287
Hydroboration-Oxidation ........................................................................ 287
Oxymercuration-Demercuration ............................................................. 288
From E~oxides.......................................................................................... 288
D . REACTIONS OF ALCOHOLS ......................................................... 288
Formation of Alkoxides ............................................................................ 288
Formation of Alkyl Halides ...................................................................... 289
Oxidation of Alcohols .............................................................................. 289
Acid-Catalyzed Dehydration ....................................................................290
Mechanism of Acid-Catalyzed Dehydration of Alcohols .........................290
Rearrangement .An Example ...................................................................291
CHAPTER 21 PRACTICE QUESTIONS .............................................293

CHAPTER 22: ALDEHYDES AND KETONES ................. 297

A . INTRODUCTION .............................................................................297
B. SOME ALDEHYDES AND KETONES ............................................ 298
C . PROPERTIES OF ALDEHYDES AND KETONES ........................298
D . SYNTHESIS O F ALDEHYDES AND KETONES...........................298
From Alcohols ..........................................................................................298
From Alkenes by Ozonolysis ...................................................................299
E . NUCLEOPHILIC ADDITION T O THE CARBONYL GROUP...299
F . REACTIONS O F ALDEHYDES AND KETONES .........................300
Formation of Carboxylic Acids ................................................................ 300
With Grignard Reagents ...........................................................................300
G. ALDOL ADDITION AND CONDENSATION REACTIONS .....301
H . REDUCTION REACTIONS OF
ALDEHYDES A N D KETONES .....................................................303
Conversion to Alcohols .......................................................................... 303
Conversion to Hydrocarbons ...................................................................303
I. FORMATION O F ACETALS ............................................................-304
CHAPTER 22 PRACTICE QUESTIONS............................................305

CHAPTER 23: CARBOXYLIC ACIDS ..................................309

A . INTRODUCTION ............................................................................. 309
B. PROPERTIES O F CARBOXYLIC ACIDS...................................... 309
C . SYNTHESIS OF CARBOXYLIC ACIDS .......................................... 310
. .
By Oxidation.............................................................................................310
From Grignard Reagents ............................................'..............................311
From Alkyl Halides via Nitriles ...............................................................311
D . REACTIONS O F CARBOXYLIC ACIDS ....................................... 312
Esterification .............................................................................................
312
De~arbox~lation ......................................................................................312
CHAPTER 23 PRACTICE QUESTIONS ............................................. 313

CHAPTER 24: ACID DERIVATIVES .....................................317

A . INTRODUCTION ............................................................................. 317
B. ACID CHLORIDES ............................................................................ 318
Reactions of Acid chlorides ...................................................................... 319
C . ACID ANHYDRIDES ........................................................................319
Reaction Involving Acid Anhydrides .......................................................320
D . AMIDES ..............................................................................................321
Hydrolysis of Amides ............................................................................... 321
E. ESTERS ................................................................................................321
Synthesis of Esters..................................................................................... 321
F . Reactions of Esters ................................................................................ 322
Reduction .................................................................................................
322
Esters with Grignard Reagents.................................................................. 322
Saponification ..........................................................................................-322
CHAPTER 24 PRACTICE QUESTIONS............................................. 324
CHAPTER 25: ETHERS ............................................................... 327
A. INTRODUCTION ............................................................................. 327
B. PROPERTIES OF ETHERS ............................................................... 327
C. PREPARATION OF ETHERS ..........................................................327
D . CLEAVAGE OF ETHERS BY ACID ................................................ 328
E. THE BASICITY OF ETHERS ............................................................ 328
F. EPOXIDES .......................................................................................... -328
Some Reactions of Epoxides .....................................................................329
CHAPTER 25 PRACTICE QUESTIONS .............................................331

CHAPTER 26: PHENOLS ............................................................ 333

A. INTRODUCTION ............................................................................. 333
B. PROPERTIES OF PHENOLS ............................................................ 334
C . EFFECTS O F SUBSTITUENTS O N THE ACIDITY
OF PHENOLS .................................................................................... 334
D . REACTIONS OF PHENOLS ............................................................ 335
Formation of Quinones ............................................................................ 335
E. ELECTROPHILIC AROMATIC SUBSTITUTION REACTIONS335
CHAPTER 26 PRACTICE QUESTIONS .............................................. 337

CHAPTER 27: AMINES .............;.................................................. 339

A. INTRODUCTION ............................................................................. 339
B. STRUCTURE OF AMINES ...............................................................339
C . PROPERTIES OF AMINES ...............................................................339
D . PREPARATION OF AMINES ..........................................................340
Alkylation Method ................................................................................... 340
E. REACTIONS OF AMINES ................................................................ 341
Formation of Amides ................................................................................341
F. BASICITY OF AMINES .....................................................................341
CHAPTER 27 PRACTICE QUESTIONS .............................................342

CHAPTER 28: AMINO ACIDS AND PROTEINS ...........347

A. INTRODUCTION .............................................................................347
B. AMINO ACIDS ...................................................................................347
Peptide Bond .............................................................................................348
C . PEPTIDES ...........................................................................................349
D . ALPHA AND BETA AMINO ACIDS ..............................................349
E . DIPOLAR NATURE OF AMINO ACIDS .......................................349
F. CLASSIFICATION OF AMINO ACIDS...........................................350
G. PROPERTIES OF AMINO ACIDS ...................................................353
H . PROTEINS .........................................................................................354

xii
Primary Structure of Proteins ................................................................... 354
Secondary Structure of Proteins ............................................................... 356
Tertiary Structure of Proteins................................................................... 356
Quaternary Structure of Proteins .............................................................356
I. DENATURATION OF PROTEINS ................................................ 358
CHAPTER 28 PRACTICE QUESTIONS .............................................359

CHAPTER 29: CARBOHYDRATES ....................................... 363

A. INTRODUCTION .............................................................................363
B. MONOSACCHARIDES ..................................................................... 363
C . CONFIGURATIONS OF MONOSACCHARIDES ........................365
D . CYCLIC STRUCTURE O F HEXOSES ............................................ 366
Glucose .................................................................................................... -366
Fructose ..................................................................................................... 367
E . OXIDATION OF MONOSACCHARIDES .....................................368
F . DISACCHARIDES .............................................................................. 369
G . POLYSACCHARIDES ....................................................................... 371
Starch ........................................................................................................ 371
. ................................................................................................... 371
Glycogen
.
Cellulose................................................................................................... -371
CHAPTER 29 PRACTICE QUESTIONS ........................................... 373

CHAPTER 30: LIPIDS ................................................................... 377

A . INTRODUCTION ............................................................................. 377
B. FATTY ACIDS .................................................................................... 377
C . TRIACYLGLY CEROLS ................................................................... -378
D . STEROIDS ..........................................................................................379
CHAPTER 30 PRACTICE QUESTIONS .............................................382

CHAPTER 31: PHOSPHORIC ACID CHEMISTRY........383

A . INTRODUCTION .............................................................................383
B. DISSOCIATION OF PHOSPHORIC ACID ....................................383
C . ESTERS AND ANHYDRIDES ..........................................................384
D . BIOLOGICAL SIGNIFICANCE OF PHOSPHORIC ACID ..........385
CHAPTER 31 PRACTICE QUESTIONS ..............................................387

xiii
CHAPTER 32: SEPARATION. PURIFICATION.
A N D STRUCTURAL ANALYSIS OF
ORGANIC COMPOUNDS .........................................................389
A . INTRODUCTION ............................................................................. 389
B. EXTRACTION .................................................................................-389
C. CRYSTALLIZATION ....................................................................... 389
Qualities of the Solvent Used for Crystallization .....................................389
D . DISTILLATION .................................................................................390
E. CHROMATOGRAPHY..................................................................... 390
Thin-layer Chromatography (TLC) .........................................................390
Gas-liquid Chromatography (GLC) .........................................................391
F . INFRARED (IR) SPECTROSCOPY .................................................. 392
Vibrational Modes ...................................................................................393
G . NUCLEAR MAGNETIC RESONANCE (NMR)
SPECTROSCOPY ............................................................................. 397
The Basics of Proton NMR ...................................................................... 397
Spin-Spin Coupling ..................................................................................398
CHAPTER 32 PRACTICE QUESTIONS .............................................. 402

SOLUTIONS .......................................................................................405

APPENDIX ..........................................................................................453

xiv
 Introduction

INTRODUCTION
The science portion of the Medical College Admission Test (MCAT)
consists of questions which test the basic concepts in general chemistry, organic
chemistry, physics, and biology. The concepts are tested with respect to
application, problem solving, and analytical thinking. These skills, which are
measured by the test, are considered essential in the study of medicine. Most of
the questions asked are based on passages. There will be independent questions
as well. On the MCAT, the general chemistry questions appear as a part of the
physical sciences section, and the organic chemistry questions as a part of the
biological sciences section.

The MCAT Chemistry Book provides all the key concepts in general
chemistry and organic chemistry that are required for the MCAT. The topic
reviews in this book have been written with respect to their relevance to the
MCAT.

The MCAT tests your ability to understand new concepts based on

undergraduate science courses. Sometimes the passages contain topics and data
that you have not seen before. Nevertheless, you do not need advanced courses
in chemistry to be successful in the MCAT. All you need is to understand the
basic concepts in chemistry. You should be familiar with the common equations
and constants that are used in the undergraduate level of studies. For example,
simple formulas such as the density-mass equation, or the gas equations may
not be given to you in the passages or independent questions. Such simple
equations should be memorized. More importantly, you should know how to
use the equations in both numerical and conceptual situations. Advanced
equations will be provided to you in the passages, if necessary. A periodic table
will be provided for both physical and biological science sections of the test.
The MCAT Chemistry Book

When studying this book, you should not focus just on facts. You should
grasp the reasoning behind the facts and think conceptually about the various
ideas in chemistry. The following guidelines will help you maximize your e E -
ciency in reviewing this book.

A Few Guidelines for the Efficient Study of this Book

1) Read the review sections actively.

2) Take side notes as you review the material.
3) Give special attention to the topics that you have forgotten from your under-
graduate courses.
4) Plan ahead and give yourself sufficient time for reviewing and studying.
5) Avoid cramming.
6) Create a schedule of study that fits into your daily agenda.
7) Study the examples that are provided, thoroughly and analytically, to under-
stand the concepts discussed.
8) After reviewing each chapter, answer practice questions.
9) After answering the questions, refer to the answers and explanations for the
practice questions provided at the end of the book.

Good Luck!
GENERAL CHEMISTRY
This page intentionally left blank
Chapter 1 Matter

Matter

A. INTRODUCTION

A firm grasp of the basic ideas of division of matter is important for the
understanding of physical sciences. These basic ideas presented here are not
only used in chemistry and physics, but in many diverse fields such as medicine,
engineering, astronomy, geology, and so on. In this chapter, we will discuss
ideas about atoms and molecules, and related aspects such as moles, Avogadro
number, percentage composition, atomic mass, atomic weight, and subatomic
particles.

B. ATOMS

Atoms are the basic units of elements and compounds. In normal chemical
reactions, atoms retain their identity. In this section, we will present a quick
review of some of the basic terms and concepts such as elements, compounds,
and mixtures.

Elements

An element is defined as matter which is made of only one type of atom.

Elements are the basic building blocks of more complex matter. Some examples
of elements include hydrogen (H), helium (He), potassium (K), carbon (C), and
mercury (Hg).

Compounds

A compound is matter formed by the combination of two or more ele-

ments in fixed ratios. Let's consider an example. Hydrogen peroxide (H202)is a
compound composed of two elements, hydrogen and oxygen, in a fixed ratio.
The MCAT Chemistry Book

Mixtures

A combination of different elements, or a combination of elements and

compounds, or a combination of different compounds is called a mixture. For
example, an aqueous solution of potassium hydroxide (KOH + H,O). In this
example, the two components are potassium hydroxide and water.

Though these definitions illustrate basic ideas, you need to understand

them fully; otherwise it will be almost impossible to decipher higher concepts
that are based on these simple ideas. The MCAT tests your understanding of
basic concepts by incorporating simple ideas into passages. So in order to succeed
on the test, you need to thoroughly understand the basics.

1 MATTER L

PURE SUBSTANCES Phys~calchanges

'
.
, Chemical changes
I
,
,

C. DALTON'S ATOMIC THEORY

In 1803, John Dalton proposed the atomic theory of matter. The main
postulates of his atomic theory can be summarized as follows:

1) Matter is composed of indivisible particles - atoms.

2) An element is composed of only one kind of atom. These atoms in a particu-
lar element have the same properties such as mass, size, or even shape.
3) A compound is composed of two or more elements combined in fixed ratios
or proportions.
4) In a chemical reaction, the atoms in the reactants recombine, resulting in
products which represent the combination of atoms present in the reactants.
In the process, atoms are neither created, nor destroyed. So a chemical reac-
tion is essentially a rearrangement of atoms.
Chapter 1 Matter

Ramifications of Dalton's Theory

The atomic theory put forward by Dalton is consistent with the law of
conservation of mass. As the fourth postulate says, chemical reaction is just a
rearrangement of atoms, and thus the total mass remains constant during a chemi-
cal reaction.

The postulates also account for the law of definite proportions. Com-
pounds are made of elements in fixed or definite proportions. Since the atoms
have fixed mass, compounds should have elements in a fixed ratio with respect
to mass. Finally, these postulates predict what is known as the law of multiple
proportions. According to this law, if two elements form two or more different
compounds, the ratio of the mass of one element of these compounds to a fixed
mass of the other element is a simple whole number.

D. THE GENERAL STRUCTURE OF THE ATOM

During the early twentieth century, scientists discovered that atoms can
be divided into more basic particles. Their findings made it clear that atoms
contain a central portion called the nucleus. The nucleus contains protons and
neutrons. Protons are positively charged, and neutrons are neutral. Whirling
about the nucleus are particles called electrons .which are negatively charged.
The electrons are relatively small in mass. Take a look at Table 1-1 for a size
comparison.

Table 1-1

RELATIVE
PARTICLE ChXRGE CHARGE MASS (kd
(Coulombs)

Neutron 0 0 1.675 x

Proton +1 .6 x 10-l9 +1 1.673 x

Electron -1.6 x 10-19 -1 9.11 x

The MCAT Chemistry Book

E. ELECTRONS

As mentioned above, the late nineteenth century scientists conducted

several experiments, and found that atoms are divisible. They conducted
experiments with gas discharge tubes.

GAS DISCHARGE TUBE,

SHOWING CATHODE RAYS ORIGINATING
FROM THE CATHODE

HIGH VOLTAGE
SOURCE

To a vaccum pump

Figure 1-1 Gas discharge tube

A gas discharge tube is shown in Figure 1-1. The gas discharge tube is
an evacuated glass tube and has two electrodes, a cathode (negative electrode)
and an anode (positive electrode). The electrodes are connected to a high volt-
age source. Inside the tube, an electric discharge occurs between the electrodes.
The discharge or 'rays' originate from the cathode and move toward the anode,
and hence are called cathode rays. Using luminescent techniques, the cathode
rays are made visible and it was found that these rays are deflected away from
negatively charged plates. The scientist J. J. Thompson concluded that the cath-
ode ray consists of negatively charged particles (electrons).

Charge of Electrons

R. A. Millikan conducted the famous oil drop experiments and came to

several conclusions: The charge of an electron is -1.602 x 10-l9
C. From the charge-
to-mass ratio, the mass of an electron was also calculated.

-Charge
- - - 1 . 7 6 ~1o8 Coulombs 1 gram
Mass
Chapter 1 Matter

-1.6 x lo-''
mass = = 9 . 1 1 ~ 1 0 - ~=' ~9 . 1 1 ~ 1 0 - ~ ' k g
- 1.76 x 10'
F. PROTONS

Protons are positively charged nuclear particles. The charge of a proton

is (positive electronic charge) +1.6 x 10-l9C. The net positive charge of the
nucleus is due to the presence of the protons. A proton is about 1800 times more
massive than an electron.

G. NEUTRONS

Neutrons have mass comparable to that of protons, but neutrons are

devoid of any electric charge. We will talk more about neutrons and their where-
abouts when we study radioactivity.

Now a natural question is whether electrons, protons, and neutrons are

the most fundamental particles. The answer is no. These fundamental particles
are made of more fbndamental particles called quarks. But, we don't have to go
that far for the MCAT. Just be aware that such sub-fundamental particles exist,
fundamental particles being electrons, protons, and neutrons.

H. ATOMIC NUMBER AND MASS NUMBER

The atomic number denotes the number of protons in an atom's nucleus.

The mass number denotes the total number of protons and neutrons. Protons
and neutrons are often called nucleons. By convention, the atomic number is
usually written to the left of the elemental notation, and the mass number to the
left above the elemental notation as represented by the example below. The
element shown is aluminum.

27
Al
e mass number

atomic number dl
3

Some atoms have the same atomic number, but different mass numbers.
This means different number of neutrons. Such atoms are called isotopes.
The MCAT Chemistry Book

I. ATOMIC WEIGHT

The atomic weight of an element is the average weight of all the isoto-
pic masses of the element, calculated on the basis of their relative abundance in
nature. The atomic weights are set on a "carbon-12" scale. This is the standard
weight scale that is used worldwide to express atomic weights. Exploring this
further, we can say that 12 atomic mass units ( m u ) make up the mass of one
atom of 'i C isotope. In other words, one arnu is equal to 1/12 the mass of one
carbon-12 atom. We can also say that the atomic weight of carbon- 12 is 12 m u .
Even though it is popular to use the term atomic weight, atomic mass is a more
appropriate term since we are really talking about the mass rather than the weight.

J. MOLECULES

A molecule is a set or group of atoms which are chemically bonded. It

can be represented by a molecular formula. A molecular formula represents the
different kinds of atoms that are present in a molecule, along with the actual
ratio of its atomic combination in forming that molecule.
ooo*o

/ \ Water molecule
H H

A molecule of H,O (water) contains two hydrogen atoms bonded to one atom
of oxygen.

NaOH Sodium Hydroxide

A molecule of sodium hydroxide contains one sodium atom, one oxygen atom,
and one hydrogen atom. The point is that molecular formula represents the mol-
ecules and the actual ratio of the atoms present in them.

Molecular Weight

Molecular weight represents the sum of the atomic weights of all the
atoms in that molecule. Molecular weight is also known as formula weight.
Chapter 1 Matter

Example 1-1

Calculate the molecular weight of sulfuric acid (H2S0,).

2 hydrogens 2x1 = 2
1 sulfur 1 x 32 = 32
4 oxygens 4 x 16=@
98 glmol

Example,1- 2

Calculate the molecular weight of carbon dioxide (CO,).

1 carbon 1 x 12 = 12
2 oxygens 2x16=2
44 glmol

Empirical Formula

Empirical formula of a molecule represents the simplest ratio of the

atoms present in the molecule. For example, acetylene has the molecular for-
mula C H . The empirical formula of acetylene is CH. In essence, empirical
?
formula gives the simplest ratio of atoms in a molecule.

Problem 1-1

Write the empirical formula of the following molecules.

Answers:

Notice that sometimes the empirical formula is the same as the molecular for-
mula as in the case of water (H20).
The MCAT Chemistry Book

K. THE CONCEPT OF MOLE

The quantity of a given substance that contains as many units or mol-

ecules as the number of atoms in 12 grams of carbon-12 is called a mole. For
example, one mole of glucose contains the same number of glucose molecules
as in 12 grams of carbon-12. The mass of one mole of a substance is called its
molar mass. The number of atoms in 12 grams of carbon-12 is represented by
the Avogadro number (6.023 x loz3).So one mole of any substance contains
Avogadro number of units in them.

To understand this concept thoroughly, try different possible scenarios

where the Avogadro number can be used. Here are some. One mole of hydrogen
atoms contains Avogadro number of hydrogen atoms. One mole of hydrogen
molecules contains Avogadro number of hydrogen molecules. A mole of water
contains 6.023 x 1023water molecules. These are all different ways of express-
ing the same concept.

The molar mass of a substance is equal to the molecular weight of that

substance. The molecular weight (formula weight) of water is 18 m u . Since
this is the molar mass, we can express it as 18 grarnslmol.

Example 1-3

Calculate the mass of one molecule of sodium hydroxide (NaOH).

Ans: We know that the formula weight of sodium hydroxide is 40 glmol.

Sodium 23
Oxygen 16
Hydrogen - 1
40 glmol

We also know that one mole of NaOH contains Avogadro number of molecules.
So the mass of the NaOH molecule can be found by the following method:

Mass of one molecule of sodium hydroxide

Chapter 1 Matter

Example 1-4

Calculate the number of moles in 109.5 grams of hydrogen chloride.

Ans: Just like the last example, we have to find the molar mass of the molecule.
The molar mass is 35.5 + 1 = 36.5 glmol.

1 mol HCl
Number of moles = 109.5 g HC1 x = 3 moles of HC1
36.5 g HC1

So, 109.5 grams of HC1 correspond to 3 moles of HC1.

You should be able to do these types of conversions back and forth, from grams
to moles and moles to grams.

Try the next problem to see whether you have mastered the idea.

Problem 1-2

Calculate the number of grams in 8 moles of sulfur dioxide.

Ans: If your answer is close to 5 12.8 g, you solved the problem correctly.

L. COMPOSITION BY PERCENTAGE

The MCAT often contains percentage composition problems. Percent-

age composition is the percentage contribution (by weight) of each element to
the total mass. Let's explore this idea by looking at some examples.
The MCAT Chemistry Book

Example 1-5

Calcium carbonate (CaCO,), commonly known as limestone is used in the prepa-

ration of a variety of compounds. Calculate the percentage composition of each
element in calcium carbonate.

Solution:

# of atoms molar weight of the atoms total mass of the element

per molecule per mol

1 Calcium 1 x 40.1 g 40.1 g

1 Carbon 1 x 12.0 g 12.0 g
3 Oxygen 3 x 16.0 g 48.0 g
100.1 g

The percentage composition of each element can be found as follows:

40.1
% of calcium = -x 100 = 40.1% calcium
100.1

12 ,
% of carbon = -x 100 = 12% carbon
100.1

48
%of oxygen = -x 100 = 47.9% oxygen
100.1

Predicting Formulas from Percentage Compositions

You should be able to predict the formula of a compound on the basis of

a given data of percentage compositions. Study the next example to understand
how it is done.

Example 1-6

A carbon compound contains 27.27% carbon and 72.73% oxygen by mass. Pre-
dict the simplest ratio or formula of the compound.

Solution:

The best way to approach this problem is to consider that we have 100 grams of
this compound. Logically it should contain 27.27 grams of carbon and 72.73
Chapter 1 Matter

grams of oxygen. With that in mind, we can calculate the number of moles of
each element or atom. After that we can obtain the simple ratio.

Step 1
27.27
# of moles of carbon atoms = -- 2.2725 moles of carbon atoms
12

72.73
# of moles of oxygen atoms = -- 4.546 moles of oxygen atoms
16
Step 2

Divide every number of moles with the smallest number of moles that you got
in Step 1. Here the smaller one is 2.2725. So divide the number of moles of
carbon atoms and the number of moles of oxygen atoms by 2.2725. That will
give you the simplest ratio between them.
2.2725
Carbon: --
2.2725 -
4.546
Oxygen: -
2.2725

Since the ratio of carbon to oxygen is 1:2, the compound is CO,.

Example 1-7

Calculate the mass of sulfur in 150 grams of H,SO,.

Solution:

The easiest way to calculate this is to find the percentage composition of sulfur.
Then, use that percentage to find the mass of sulfur in the given amount of
substance.

Step 1
32.1
% of sulfur = -x 100, roughly 33%
98
Step 2

The mass of sulfur present in 150 grams of sulfuric acid is

The MCAT Chemistry Book

M. DENSITY

Density is defined as the mass per unit volume.

Density =
volume

This property can be used to identify a compound or an element, since

the density of a pure substance is a constant. Since density relates mass and
volume, it can be used to find the volume occupied by a given mass, or if the
volume is known, we can find the mass.

Density of water is 1.0 glml.

Let's explore some calculations involving density. You'll see that these
calculations have tremendous laboratory significance.

Example 1-8

The density of carbon tetrachloride is about 1.6 glml at 20C. Calculate the
volume occupied by 320 g of CC1,.

Solution:
mass
Densitv = -
volume
mass - 320 g
Volume = = 200 ml
density 1.6 g 1 ml

So, 320 grams of carbon tetrachloride will occupy a volume of 200 ml.

Example 1-9

A 20 ml sample of mercury has a mass of 271 g. Calculate the density of mercury.

Solution:
mass ---
271 g
Density = - - 13.55 g / ml
volume 20 ml
This question tests your knowledge of a basic equation. Though the equation is
simple, you should be able to manipulate this equation so that you can connect
this piece of information with other facts and formulas that are given in your
test question or passage.
Chapter 1 Matter

CHAPTER 1 PRACTICE QUESTIONS 4. Which of the following is true regarding a

typical atom?
1. A student preparing a solution for an
experiment measured the weight of the A. Neutrons and electrons have the same
sample solute to be used. If she is supposed mass.
to use 2 moles of calcium hydroxide, she B. The mass of neutrons is much less than
must use: that of electrons.
C. Neutrons and protons together make the
A. 57.1 grams. nucleus electrically neutral.
B. 74.1 grams. D. Protons are more massive than elec-
C. 114.2 grams. trons.
D. 148.2 grams.

5. The empirical formula of butane is:

2. Which of the following best represents the
total number of atoms present in a sample A. CH,
of oxygen gas weighing 56 g? B. C,H,
0
A. 6.0 x lo2' ions D. CH,
B. 10.5 x 1O25ons
C. 12.0 x ions
D. 2 1 x 1023ions 6. The mass of one mol of a substance is
numerically equal to:

3. Experiments conducted with gas discharge A. mass number.

tubes during the late 19"' century resulted B. Avogadro number.
in many important conclusions in atomic C. molecular weight.
chemistry. Among those, one of the most D. 22.4.
important was the discovery of rays known
as cathode rays. Cathode rays when passed
near negative plates will most likely:

A. bend toward the negative plate.

B. bend away from the negative plate.
C. will not bend, because they are uncharged.
D. will not bend, because they are high
energy radiations.
The MCAT Chemistry Book

7. If m represents the number of moles of a 10. A student researcher analyzing the identity
substance, M represents the molar mass of of the by-product of a reaction found that
the substance, and d represents the density the compound contained 63.6% nitrogen
of the substance, which of the following and 36.4% oxygen. What is the most likely
expressions equals to the volume of the formula of this compound?
sample substance?
A. NO
B. NO,
C. N,O
D. N;O,

Questions 11-14 are based on the following

passage.

Passage 1

The following reactions were conducted in a

lab for studies related to reaction kinetics. Con-
8. The mass of oxygen in 96 grams of sulfur sider the reactions shown below:
dioxide is closest to:
Reaction 1
CH4 + 202 ------t C02 + 2H20

9. Choose the best value that corresponds to

2C2H6 + 702 -
Reaction 2
4Co2 + 6H20

the percentage composition of chlorine in

carbon tetrachloride? 11. Reaction 2 is best described by which of
the following?
A. 92%
B. 90% A. A metathesis reaction
C. 86% B. A combustion reaction
D. None of the above C. An endothermic reaction
D. A decomposition reaction
Chapter 1 Matter

12. In Reaction 2, if 54 g of water was formed,

how much ethane and oxygen must have
reacted?

A. 30 g of ethane and 224 g of oxygen

B. 60 g of ethane and 224 g of oxygen
C. 30 g of ethane and 112 g of oxygen
D. 60 g of ethane and 112 g of oxygen

13. Which of the following is the actual formula

of dextrose, if the empirical proportion is
1:2:1, where the proportion number 2 is that
of hydrogen. Dextrose has a molecular
weight of 180 g/mol? (Dextrose molecule
is composed of carbon, hydrogen, and
oxygen)

A. CHO

14. Which of the following equals the number

of hydrogen atoms in 40 grams of methane?
This page intentionally left blank
Chapter 2 Chemical Reactions

Chemical Reactions

A. INTRODUCTION

Chemical reaction is a process at the molecular or ionic level by which

one or more types of substances are transformed into one or more new types of
substances by different modes of combination. In this chapter, we will explore
the different types of chemical reactions including oxidation-reduction reac-
tions. We will also learn how to balance equations.

B. CHEMICAL REACTIONS

A chemical reaction can be represented by a chemical equation. In a

chemical equation representing an irreversible reaction, the substances that react
(reactants) are written on the left side, while the resulting substances (products)
are written on the right side of an arrow.

In the reaction shown above, two molecules of hydrogen react with one
molecule of oxygen, forming two molecules of water. Balancing of equations
will be covered a little later in this chapter.

C. TYPES OF CHEMICAL REACTIONS

There are five types of chemical reactions.

1) Combination reaction
2) Combustion reaction
3) Decomposition reaction
4) Displacement reaction or single-replacement reaction
5) Metathesis reaction or double-replacement reaction
The MCAT Chemistry Book

Combination Reaction

A reaction involving the formation of a compound from two or more

substances is called a combination reaction.

-
Some representative combination reactions

2Na (s) + C12 (g) 2 NaCl (s)

S02 (g) + H2 (0 * H2S03 (aq)

Combustion Reaction

A combustion reaction involves the reaction of substances with oxy-

gen, and it is usually accompanied by the release of large amounts of heat. Com-
bustion reactions are thus highly exothermic.

-
Some representative combustion reactions

c (s) + 0 2 (g) co2(g)

Decomposition Reaction

A decomposition reaction is a process in which one compound decom-

poses or splits to form two or more simpler compounds and/or elements.

CaC03 (s) -
A representative decomposition reaction

CaO (s) + C02 (g)

Displacement Reaction (single-replacement reaction)

In a single-replacement reaction, an element reacts with a compound,

and results in the displacement of an element or group from the compound. An
example of a single-replacement reaction is shown.
Chapter 2 Chemical Reactions

-
A single-replacement reaction

Zn ( s ) + CuC12 (aq) ZnC12 (aq) + Cu (s)

In this reaction, Zn substitues for Cu.

Metathesis Reaction (double-replacement reaction)

A metathesis (double-replacement)reaction involves the exchange of

two groups or two ions among the reactants. Remember that in a single-replace-
ment reaction, there is only one group or ion being switched. A metathesis reac-
tion can often result in an insoluble product from soluble reactants, and the
insoluble compound formed is called a precipitate.
A metathesis reaction

(a9) + NaCl (a9) - AgCl (s) + NaNO, (aq)

Note that this reaction involves the formation of a precipitate of AgC1.

With respect to the types of reactions, your objective should be to understand

the basis behind the categorization.

D. BALANCING SIMPLE EQUATIONS

A chemical equation is said to be balanced if all the atoms present in the

reactants appear in the same numbers among the products. Here is an example.

Example 2-1

Balance the following equation.

Solution:

Start by balancing the oxygen atoms. There are two oxygen atoms on the reac-
tant side and three oxygen atoms on the product side. To balance this, put 3 as
the coefficient of oxygen on the reactant side. When we write '3 O,,' that means
we have 6 oxygen atoms on the reactant side. To make the same number of
oxygen atoms on the product side, let's put 2 as the coefficient of Fe,O,. Now
the oxygen atoms seem to be balanced.
T h e MCAT Chemistry Book

Let's take a look at Fe. Since the coefficient of Fe,O, is 2, we have 4 atoms of Fe
on the product side. We can balance this by writing 4 as the coefficient of Fe on
the reactant side. So the balanced equation is as follows:

Problem 2-1

Balance the following equations:

(a)

(b)

(c)
Cu +

Fe203

H2S04
+
AgN03

+
CO

NaOH
--
----t Ag

Fe

Na2S04
+
+
CU(NO~)~

C02

+ H20

(d) Ba(OH)2 + HC1- BaC12 + H20

Answers:

(a) Cu + 2 AgN03 -- 2Ag + Cu(N03)2

(b)

(c)

(d)
Fe203

H2S04

Ba(OH),
+ 3 CO
+ 2 NaOH -
+ 2 HC1 -BaC12
2 Fe

Na2S04
+ 3 C02
+ 2 H20
+ 2 H20

E. OXIDATION NUMBER

Electrons are exchanged during oxidation-reduction reactions. The

behavior of atoms or ions in terms of the number of electrons transferred is
expressed as the oxidation state (oxidation number). We can define oxidation
number as the charge of an atom or ion, based on a set of standard rules. If the
given species is an ion containing a single atom, then its oxidation state is its
charge itself. Let's analyze this by looking at a few examples.

In NaC1, the oxidation state of sodium is +1 and the oxidation state of

chlorine is -1. Generally, the elements at the top right comer of the periodic
table are assigned negative oxidation numbers. Some of the elements on the
right side of the periodic table can have positive or negative oxidation numbers
depending upon the atom to which the given element is bonded to. The ele-
ments in the middle and the left portions of the periodic table have almost
exclusively positive oxidation numbers.
Chapter 2 Chemical Reactions

Table 1-1

General guidelines for assigning oxidation numbers

1. The elemental natural state oxidation number of any atom is zero. For
example, the oxidation number of oxygen atom in 0, is zero.
2. The sum of the oxidation numbers of the atoms in a compound should be
zero.
3. The sum of the oxidation numbers of the atoms in an ionic species (a spe-
cies with a net charge) should equal the net charge of the ionic species.
4. The oxidation number of a given ion containing a single atom is its charge
itself.

Oxidation numbers of some common elements

1 . The common oxidation number of Group IA metals is + l . E.g., lithium,

sodium, potassium.
2. The common oxidation number of Group IIA metals is 1-2. E.g., beryllium,
magnesium, calcium.
3. The common oxidation number of Group IIIA is +3. E.g., aluminum, boron.
4. The common oxidation number of Group IVA is +4. +2 is also seen in some
compounds such as CO.
5. The common oxidation numbers of Group V A are +5 and -3.
6. The common oxidation number of Group VIA is -2.
7. The common oxidation number of Group VIIA is -1.
8. The common oxidation number of H is +1. In some metal hydrides, hydrogen
shows an oxidation number of -1.

The above list of common oxidation numbers is not comprehensive.Nevertheless,

it gives you a basic and essential picture about assigning oxidation numbers in
common compounds and ionic species. Most elements can have multiple
oxidation states, depending on the element or ionic species they are bonded to.
You have to always follow the general guidelines in Table 1- 1, and check whether
the items listed are satisfied.

Now that we have learned the theory of assigning oxidation numbers, let's do an
example to see how it works.
The MCAT Chemistry Book

Example 2-2

What is the oxidation number of sulfur in sulfuric acid?

Solution:

Sulfuric acid is H,SO,. The oxidation number of hydrogen is +l. But we have
two hydrogens which add up to a charge of +2. Since the total charge of this
molecule should be zero, we can say that the charge of sulfate ion is -2. We also
know that the oxidation number of oxygen is -2. But there are four oxygens in
a sulfate ion. So the charge adds to -8. Now let's solve this algebraically.

Oxidation number of sulfur

- Oxidation number of oxygen
ONoXy~""

So the oxidation number of sulfur in sulfuric acid is +6.

Problem 2-2

Calculate the oxidation state of the element indicated in each of the following
problems.

(a) What is the oxidation state of hydrogen in MgH,?

(b) What is the oxidation state of chlorine in C10,-?
(c) What is the oxidation state of oxygen in Na,O,?
(d) What is the oxidation state of nitrogen in NH,?
(e) What is the oxidation state of oxygen in O,?
(f) What is the oxidation state of bromine in HBrO,?
(g) What is the oxidation state of manganese in KMnO,?

Answers:
Chapter 2 Chemical Reactions

F. OXIDATION-REDUCTION REACTIONS

Oxidation-reduction (redox) reactions involve the transfer of electrons

from one compound or species to another. In this section, we will discuss oxida-
tion-reduction reactions and learn how to balance them.

Oxidation is the prooess by which an atom or species loses its electrons.

In reduction, an atom or species gains electrons. Let's first consider oxidation Mnemonic:
LEO the lion says GER
and reduction separately.
-Losing Electrons Oxidation
-Gaining _ElectronsRedzrction
Consider the conversion of iron from its neutral elemental state to its ionic form.

Notice that in the process iron lost electrons. The process is oxidation.

Consider another example. An example involving the conversion of bromine to

its ionic form.

Notice that in the process bromine gained electrons. The process is reduction.

Now let's go one step forward. Consider the next reaction.

This reaction is a typical example of an oxidation-reduction reaction. The

oxidation number of iron on the reactant side is 0. The oxidation number of bro-
mine on the reactant side is also 0. What are the oxidation numbers of iron and
bromine in FeBr,? Well, we know that bromine has an oxidation number of -1.
So the oxidation number of iron in FeBr, is +3. Thus iron is oxidized and bromine
is reduced. The species that gets oxidized is called the reducing agent. The spe-
cies that gets reduced is called the oxidizing agent. In this reaction, evidently iron
acts as the reducing agent, and bromine acts as the oxidizing agent.

Oxidation results in an increase in the oxidation number: In the process of

oxidation, electrons are lost.

Reduction results in a decrease in the oxidation number: In the process, electrons

are gained.
The MCAT Chemistry Book

Balancing Oxidation-Reduction Reactions

Balancing of an oxidation-reduction reaction is a little more complex

than balancing a simple reaction. The main rule that you have to follow when
balancing oxidation-reduction reactions is that the absolute value of the increase
in oxidation number of all the atoms that are oxidized should equal the absolute
value of the decrease in oxidation number of all the atoms that are reduced.
Balancing oxidation-reduction reaction is sometimes time-consuming and quite
often frustrating. We will look at two methods of balancing oxidation-reduction
reactions.

Method A

1. Write the unbalanced equation.

2. Find the oxidation numbers of the atoms that undergo change in oxidation
states and write on top of each atom the corresponding oxidation number.
3. By this process, we will be able to see which atoms are getting oxidized and
reduced.
4. Compare and indicate the change in oxidation numbers from the reactant
side and the product side, and write down the change in the oxidation
numbers.
5. Make the necessary changes by writing coefficients that will equalize the
changes in the oxidation numbers. In other words, the net decrease in the
oxidation numbers should equal the net increase in the oxidation numbers.
Add water if necessary.
6. Do a final check on whether all the atoms and charges balance out.

Method B

1. Write the unbalanced equation.

2. Separate the two half-reactions,write them out, and balance any of the atoms.
From this point onward, we balance the reactions separately. Do the obvious
or the simple balancing by inspection if possible.
3. Balance the oxygen atoms by adding water on the appropriate side of the
half-reaction.
4. Balance the hydrogen atoms by adding H' on the appropriate side of the
half-reaction.
5. Add sufficient number of electrons so that the charges are balanced.
6. Once the half-reactions are balanced, combine the half-reactions and cancel
out any common terms that appear on both sides of the equation to get the
refined and balanced oxidation-reduction equation.
Chapter 2 Chemical Reactions

Example 2-3

Zn NO; -
Balance the following oxidation-reduction reaction.

+ zn2+ + N 2 0
The MCAT Chemistry Book

Before we combine the equations, the electrons need to be balanced out.

So multiplying the balanced half-reaction # (I) by 4, we get

Combining the two half reactions

Chapter 2 Chemical Reactions

G. CALCULATIONS INVOLVING CHEMICAL REACTIONS

In this section, we will look at some chemical equations and find what
we can do with the information represented in a chemical equation. The equa-
tion shown below represents the reaction of methane and oxygen to form carbon
dioxide and water.

From this balanced equation we can infer many things. Let's consider a few.

1) One molecule of methane reacts with 2 molecules of oxygen to form 1 mol-

ecule of carbon dioxide and 2 molecules of water.
2) We can also say that 1 mole of methane reacts with 2 moles of oxygen to
form 1 mole of carbon dioxide and 2 moles of water.
3) Since one mole contains Avogadro number of molecules, we can say that
6.023 x lo2' molecules of methane reacts with 1.2046 x (=2 x 6.023 x
1023)molecules of oxygen to form 6.023 x 1023molecules of carbon dioxide
and 1.2046 x 1024molecules of water.
4) We can confidently say that 16 g of methane reacts with 64 g of oxygen to
form 44 g of carbon dioxide and 36 g of water.

Example 2-4

Calculate the number of moles of water produced when 5.25 moles of methane
undergo the reaction depicted below. (Assume there is plenty of oxygen for the

-
reaction)

CH, + 2 0, CO2 + 2 H2.0

Solution:

From the equation, it is clear that for every mole of methane, 2 moles of water
are formed. So without any elaborate calculations, you should be able to come
up with the correct answer. It is very much like a ratio problem. Since there are
5.25 moles of methane, 10.5 moles of water will be formed.

Number of moles of water formed = 5.25 x 2 = 10.5 moles

The MCAT Chemistry Book

Example 2-5

110 g of CO, were formed as a result of the reaction shown below. How many
grams of oxygen must have reacted to form that much carbon dioxide?

Solution:

According to the equation, 2 moles of oxygen result in 1 mole of carbon diox-

ide. For example, if 2 moles of carbon dioxide were formed, 4 moles of oxygen
must have reacted. Here, the amount of carbon dioxide formed is given in terms
of grams. So the first step is to convert the grams to moles.
110 g
Moles of carbon dioxide = = 2.5 moles
44 g / mol

Hence, 5 moles of oxygen must have reacted to form 2.5 moles of carbon diox-
ide. But the question asks for this quantity in grams. So the final step is to
convert moles to grams.

The amount of required oxygen = 5 moles x -32 g - 160 g

1 mol

H. THE CONCEPT OF LIMITING REAGENT

So far we have been considering reactions in which all the reactants

exist in adequate quantities. In this section, we will consider what happens when
the amount of one of the reactants available is less than the amount required to
complete the reaction. When such a condition exists, we call that reactant or
reagent the limiting reagent.

We will further explore this scenario through the following examples.

Example 2-6

A reaction mixture contains 60.75 g magnesium and 146 g hydrogen chloride.

Predict the limiting reagent if the reaction occurs as shown below.
Chapter 2 Chemical Reactions

Solution:

First, we have to convert the grams of the substances to moles. Then make the
comparison to see which one is the limiting reagent. By now, you should be
comfortable with the conversion of moles to grams and vice versa. The number
of moles of magnesium present is 2.5 moles. According to the equation, 1 mole
of magnesium reacts with 2 moles of hydrogen chloride. For magnesium to
completely react, there should be at least 5 moles of hydrogen chloride present.
If you calculate the number of moles of hydrogen chloride present, you will get
4 moles. This amount of hydrogen chloride is not enough to completely react
with the amount of magnesium present. So the limiting reagent is hydrogen
chloride.

I. PERCENT YIELD

If we know the chemical equation and the amounts of reactants, we can

calculate the theoretical yield of that reaction. But in reality, the yield depends
on many other factors also. Most of the time in synthesis reactions, even in your
own lab experiments, you probably noticed that the actual yield is lower than
the theoretical yield. The percent yield denotes the amount of actual yield in
terms of the theoretical yield. The formula to find the percent yield is given
below:
actual yield of the product
Percent yield = X 100%
theoretical yield of the product

Example 2-7

A student conducted the above reaction in a lab as a part of her research assign-
ment. She used 138 g of sodium nitrite, with excess of hydrogen chloride. What
is the percent yield of HNO,, if the actual yield of HNO, was 61.1 g?

Solution:

First, you should find the number of moles of NaNO,. Since she used 138 g, the
number of moles of NaNO, is 2 (Mol.wt of NaNO, is 69 glmol). Since the ratio
of formation of HNO, is 1:1 with respect to NaNO,, theoretically 2 moles of
HNO, should be formed. Two moles of HNO, correspond to 94 g. But actually,
only 6 1.1 g of HNO, was formed. Now it is just a matter of plug and chug in the
percent yield formula.
The MCAT Chemistry Book

6 1.1 grams
The percentage yield of HNO, = x 100% =65%
94 grams
In this experiment, the actual yield was not high (i.e., only 65% of the theoreti-
cally predicted yield) as expected.

Example 2-8

Match the following reactions with the appropriate type of reaction

1. 2KC103- 2 KC1 + 3 0 2 A. Combination reaction

2. 2KC1 + C1,-2KC1

3. HNO

Solution:
3
+ NaOH - NaNO
3
+ H,O
B. Double-replacement reaction

C. Decomposition reaction

2KCl0,- 2 KC1 + 3 0 2 C. Decomposition reaction

2KC1 + C1, -2KC1 A. Combination reaction

HNO + NaOH +N ~ N O+ H,O B. Double-replacement reaction

3 3
Chapter 2 Chemical Reactions

CHAPTER 2 PRACTICE QUESTIONS 4. How many grams of sodium chloride are

required to synthesize 73 grams of hydrogen
chloride, if the reaction involves sodium

-
chloride and sulfuric acid?
1. The reaction shown here can be best clas-
sified as a: NaCl + H2SO4 Na2S04+ HC1

A. combustion reaction. A. 58.5 grams

B. combination reaction. B. 117 grams
C. single-replacement reaction. C. 175.5 grams
D. double-replacement reaction. D. 234 grams

2. All the following reactant-combinations are 5. In some reactions, you will often encounter
neutralization reactions, EXCEPT: ions in aqueous solutions which are not
actually involved in the reaction. Such ions
are best termed:
A. HN02 + NaOH
A. cations.
B. KOH + HC1
' B. anions.
C. ~ 1 ' + 30H C. salt-bridge ions.
D. spectator ions.
D. H3P04 + NaOH

6. Some substances can act as a base or an acid.

Such substances are called:
3. An unbalanced equation is shown below.
What is the coefficient of aluminum
A. aliphatic substances.
hydroxide in the final balanced equation?
B. amphibasic substances.
C. lyophilic substances.
D. amphoteric substances.

7. Predict the coefficient of iron in the bal-

anced equation for a reaction in which iron
reacts with oxygen to form Fe,O,.
The MCAT Chemistry Book

8. The number of molecules are the same in

which of the following pairs? 2 Al(OH)3 (s) ---t A1203(s) + product x
A. 32 grams of 0, and 32 grams of SO, Experiment 3
B. 49 grams of NO, and 40 grams of
NaOH
C. 20 grams of HF and 36 grams of H,O Fe2Q3(s) + 3 C 0 ( g ) --t 2 Fe (s) + 3 C 0 2 (g)
heat
D. 60 grams of C,H, and 156 grams of
C6H6
9. What is the most likely identity of product x?
Questions 9-15 are based on the following
passage. A. aluminum
B. water
Passage 1 C. hydrogen
D. oxygen
Information regarding the amounts of
substances that actually react to form the
products are of extreme help. Analyzing 10. In Experiment 3, which of the following is
reactions and having the balanced equations the limiting reagent?
help chemists to determine the correct and
optimum proportions of reactants to be used. A. Fe,O, because there is only 1 mole of it
There are various other factors besides the B. CO because of its gas phase
amount of reactants, which determine the C. Fe because of its insufficiency
efficiency of reactions. D. Cannot be determined without more
data
Experiment 1

11. Based on the given information, which

o f the following are true regarding
Student 1 used 40.5 g of aluminum and 80 g Experiment 1?
of Fe,03 for Reaction I. A second student
conducted the same reaction with a different I. The second student had the highest yield
amount for one of the reactants. The second for aluminum oxide.
student used 40.5 g of aluminum, and 90 grams 11. The third student had a higher yield for
of FeiO,. A third student also conducted the same aluminum oxide than the first student.
reaction with 54 g of aluminum and the same 111. The first and the third students had the
amount of Fe,O, used by the first student. same yield for aluminum oxide.

Experiment 2 A. I only
B. I and 11 only
Reaction 11involved the production of A1203 C. I and I11 only
from aluminum hydroxide This was done by D. I1 and I11 only
heating aluminum hydroxide.
Chapter 2 Chemical Reactions

12. Which of the following changes will fur-

ther increase the overall yield for the reac-
tions conducted in the Experiment l ?

A. Increasing the amount of aluminum

used by Student 1
B. Increasing the amount of aluminum
used by Student 2
C. Increasing the amount of Fe,O, used by
Student 2
D. None of the above

13. Roughly 80 g of Fe,03 was present in

Experiment 3, and upon completion of the
reaction, it was measured that 22 g of CO,
was formed. If this is true, how much CO
must have reacted before reaching
completion of the reaction?

A. 14 grams
B. 28 grams
C. 56 grams
D. 84 grams

14. In the previous question, which of the

reactants acts as the limiting reagent?

A. Fe,O,
B. CO
C. CO,
D. Cannot be determined

15. If 0.1 mol of CO was reacted with excess

of Fe,03, how many molecules of carbon
dioxide will be produced?

A. 6.0 x molecules
B. 6.0 x 1022molecules
C. 3.0 x 1023 molecules
D. 18.0 x molecules
This page intentionally left blank
Chapter 3 Electronic Structure

Electronic Structure

A. INTRODUCTION

In this chapter, we will discuss the electronic arrangement of atoms. We

will also talk about quantum numbers, orbitals, various rules pertaining to elec-
tron-filling, and electronic configuration.

B. ATOMIC STRUCTURE

The first ideas about electronic arrangement in atoms were primarily

figured out from atomic emission spectra. In various experiments, atoms were
made to be thermally or electrically excited, and this resulted in different kinds
of bands or lines on photographic plates. Our understanding of atomic structure
is based on these types of experiments. All elements have their characteristic
line spectra with which they can be analyzed and identified.

Electromagnetic Waves

Before we discuss the atomic structure, we will touch on the topic of

electromagnetic radiation to have a better analytical understanding of the key
ideas. All electromagnetic radiations travel with a constant speed of 3 x los mls.
The electromagnetic spectrum ranges from radiowaves to gamma rays.

The Wave Nature

Light has wave nature. It has electric and magnetic fields which are per-
pendicular to each other, and can travel through space. No medium is required.
Because of its wave character, we can define light in terms of frequency and
wave length. The distance between two adjacent crests or troughs, or any two
adjacent identical points on a wave is called wave length (A). Frequency (f) is
The MCAT Chemistry Book

the number of wavelengths passing through a point in unit time. Wavelength

and frequency are related by the relation given below. Frequency is usually ex-
pressed in llsecond (s-'), which is otherwise known as hertz (Hz).

I t wavelength

Velocity = frequency x wavelength

c = f?L

The Particle Nature and Quantum Theory

Light has particle nature. These particles or forms (packages) of energy

are called quanta. A more modern term for such as particle of light is photon.
The energy of a photon can be expressed in terms of the following formula.

Energy = h f,

where h is the Planck's constant, and f is the frequency.

Planck's constant = 6.63 x J.s

According to Heisenberg's Uncertainty Principle, we cannot determine

both the momentum and the position of subatomic particles simultaneously. This
is because we are using other particles (electromagneticparticles-like photons) of
comparable energy to detect these subatomic particles, and by the time these other
particles find the subatomic particles (say electrons), they are also disturbing the
pathway of these electrons. In essence, the' study of something extremely small
and fast (about the magnitude of electrons) cannot be done without interference of
its natural course or position.
Cha ter3 Electronic Structure

Photoelectric Effect

The photoelectric effect can be defined as the ejection of electrons from

a metal surface when light rays strike on it. The ejected electrons are often called
"photoelectrons." The ejection of electrons occurs only if the incident light has
a certain minimum or thresholdfiequency. The required threshold frequency is
a characteristic specific to each metal. Experimentally, it has been found that
the photoelectrons emitted with maximum energy do not have the full energy
equivalent supplied by the incident photon. This is because energy is required to
break loose the electrons from the surface of the metal. The energy required for
this is called the "work function," which is characteristic of each metal. The
photoelectrons can be accelerated to a positively charged plate, creating a flow
of charges along a wire-photocurrent. The current can be measured by an am-
meter connected to the wire.

Light-sensitive
metal plate Positive plate
\
'\

I
Ammeter

The maximum kinetic energy (Kmax)

of a photoelectron is given by the following
equation:
Kmax = ?4mvmax2
= hf - 9

In this equation, m is the mass of an electron, vrnax is the maximum velocity of

the electrons, h is the Planck's constant, f is the frequency of the incident light,
p(pronouncedphi) is the "work hnction" of the metal. The entity hf represents
the energy of the incident photon.
The MCAT Chemistry Book

Key Observations on Photoelectric Effect

1) The photoelectric effect exemplifies the particle nature of light.

2) Based on conservation of energy, no photoelectron can have energy more
than that of an incident photon.
3) The energy of the photoelectrons is always less than that of the incident
photons, because some energy (work function) is required to break the elec-
trons loose.
4) The maximum energy of the photoelectrons is independent of the intensity
of the incident light.
5) Electrons are not ejected no matter how high the intensity of the incident
light is, unless the incident light has the energy corresponding to the thresh-
old frequency characteristic of a particular metal.

Atomic Emission Spectra

When we pass white light through a prism, dispersion of the light occurs
resulting in continuous spectrum of wavelengths. Another type of spectrum results
when heated gas emits light. Thls results in a line spectrum. Line spectrum contains
only certain specific wavelengths of light. The wavelengths in the visible spectrum
of hydrogen is given by the following formula:

where h is the wavelength of the light, R (Rydberg constant) = 2.18 x 10-Is J,

h (Planck's constant) = 6.63 x J.s, c (speed of light) = 3.0 x l O h I s , and
n is some whole number that is greater than 2 which corresponds to the orbit-
number from which the electron is making the transition. For example, if the
transition of an electron is from orbit-number 4 to 2, the n value is 4.
Chapter 3 Electronic Structure

Bohr's Model of Hydrogen Atom

Niel Bohr's explanation of the hydrogen spectrum was a major break-

through toward the understanding of atomic structure. The following are the
postulates:

1) In each hydrogen atom, the electron revolves around the nucleus in one of
the several stable orbits.
2) Each orbit has a definite radius and thus has a definite energy associated
with it.
3) An electron in an orbit closest to the nucleus has the lowest energy, and if
the electron is in the lowest orbit the atom is said to be in its ground state.
4) The electron in an atom may absorb discrete amounts of energy and move to
another orbit with higher energy, and this state is called the excited state.
5) An electron in an excited atom can go back to a lower energy level and this
process will result in the release of excess energy as light.
6) The amount of energy released or absorbed is equal to the difference between
the energies of the initial and final orbits.

Based on Bohr's theory, light energy is emitted when an electron in a

higher energy level (EitiaI)jumps to a lower energy level(Efina,). Based on the law
of conservation of energy, the sum of energies of the emitted photon (hA and the
electron's final energy(Efina,)
should be equal to the electron's initial energy(Ejnltla,).
This can be represented mathematically as follows:

Transitions of the electron in the hydrogen atom result in different spectral lines.
The MCAT Chemistry Book

I
W
%

m
L
b,
s
Lyman serles (ultraviolet rays)

The energy of the 'emitted photon hf =

where n,,,, and n m , ,are the principal quantum numbers of final and initial
energy levels, and R is the Rydberg constant(2.18 x 10-Is J). The figure given
below shows the transitions that can result in the Lyman (ultraviolet region),
Balmer (visible region), and Paschen series (infrared region) for nfinal values
I, 2, and 3 respectively.

A photon is emitted when an electron in an atom jumps from a higher to a

lower energy level. The energy of the emittedphoton is equal to the difference
in energy between the two energy levels.

C. QUANTUM NUMBERS

All electrons present in an atom have specific addresses or attributes by

which each electron can be referred to. The four quantum numbers are the ones
with which we can describe each and every electron that is present in an atom.
One of the quantum numbers describes the shape or the most probable area
around the nucleus where we can find the particular electrons of interest. This
wave function of an electron is called an orbital.
Chapter 3 Electronic Structure

Principal quantum number (n). The principal quantum number denotes the
energy level of electrons. The larger the principal quantum number is, the larger
the energy. The smaller the principal quantum number is, the lower the energy.
The shells are often named K, L, M, N, . . ., which correspond to the principal
quantum numbers 1, 2, 3,4, . . ., respectively.

The orbital size depends on n. This means that the larger the n value, the larger
the orbital. Orbitals with the same n belong to the same shell.

Angular momentum quantum number (0. Angular momentum quantum num-

ber (azimuthal quantum number) denotes the shape of the orbital. The values
range from 0 to n - 1, where n stands for the principal quantum number. If an
electron has a principal quantum number of 4, the values of angular momentum
quantum numbers are 0, 1,2, and 3. The angular momentum quantum numbers
correspond to different subshells. An angular momentum quantum number 0
corresponds to s subshell, 1 top subshell, 2 to d subshell, 3 tof subshell, and so on.
For instance, 3d denotes a subshell with quantum numbers n = 3 and I = 2.

s orbital

2 p, orbital 2 p, orbital 2 p, orbital

The MCAT Chemistry Book

Magnetic quantum number (m,).Magnetic quantum numbers define the

different spatial orientations of the orbitals. The values range from -1 to +I. For
example, let's say the value of 1 is 1. So the magnetic quantum numbers will be
-1, 0, and +l. The I value corresponds to p sublevel and the three magnetic
quantum numbers correspond to the three atomic orbitals in the p subshell.

Spin quantum number (mS). Spin quantum number has to do with the spin
orientations of an electron. The two possible spins are denoted by the spin quan-
tum numbers + !h and - !h .

/
7

Spatial orientation of d orbitals b

Chapter 3 Electronic Structure

D. ELECTRONIC CONFIGURATION

We talked about quantum numbers and atomic orbitals. In this section,

we will focus our attention mainly on writing the electronic configuration of
atoms and the rules associated with it. First, let's talk about the ground state
electronic configuration. The ground state configuration means the electronic
configuration at the lowest energy state.

There are certain rules that should be applied to the filling of orbitals. In
order to do that properly, we need to know the Aufbau principle. According to
the Aufbau principle, the filling order of electrons obeys a general pattern in
which the electrons try to occupy the orbitals in such a way as to minimize the
total energy; that is, they occupy the lowest energy orbitals first and then step-
by-step go to the next available higher energy levels successively. Of course,
there are some exceptions to these generalizations. Some students find it hard to
remember the order of filling. The diagram given below may help you. So take
a close look. Filling order can be depicted as follows:

This is an easy way to remember the general order of electron-filling in the

subshells. The order of filling is Is, 2s, 2p, 3s, 3p, 4s, 4p, 5s, . . ., and so on.
The MCAT Chemistry Book

An s orbital is spherical in shape. All p orbitals have dumbbell shape

with two lobes aligned along an axis (see page 47). All d orbitals have slightly
complex shapes (see page 48) and are beyond the scope of our discussion. Each
orbital can accomodate a maximum of two electrons. Hence, an s subshell, (only
one orbital) can accomodate a maximum of two electrons. Similarly, p (three
orbitals), d (five orbitals), andf (seven orbitals) subshells can have maximum of
six, ten, and fourteen electrons, respectively.
Table 3-1 Some possible combinations of quantum numbers for atomic orbitals
Angular Maximum
Principal
momentum Magnetic quantum Number Of
quantum number of
quantum number (m,) Orbitals
electrons
number (") number (4
1 0 0 1s 1 2

2 0 0 2s 1 2

2 1 -1,0,+1 2P 3 6

3 0 0 3s 1 2

3 1 -1,0,+1 3P 3 6

3 2 -2,-1,0,+1,+2 3d 5 10

4 0 0 4s 1 2

4 1 -1,0,+1 4P 3 6

4 2 -2,-1,0,+1,+2 4d 5 10

4 3 -3,-2,-1,0,+1,+2,+3 4f 7 14

Example 3-1

Write the electronic configuration of lithium.

Solution: From the periodic table, we can get the atomic number of lithium.
The lithium atom has 3 electrons. As we know, 1s subshell is the first one to be
filled. The s orbital can hold a maximum of 2 electrons. We have one electron
remaining. It will occupy the 2s subshell which is the next energy level. So the
third electron will occupy the 2s subshell. Hence, the configuration of lithium is
1 s22s1.

Example 3-2

Write the electronic configuration of oxygen in its ground state form.

Solution: The oxygen atom contains 8 electrons. The first 2 electrons will go to
the 1s level. The next 2 electrons will occupy the 2s level. We have 4 electrons
Chapter 3 Electronic Structure

remaining. What is the next subshell according to the filling order? It is 2p. The
p subshell can hold a maximum of 6 electrons in its orbitals. So the remaining 4
electrons will occupy the 2p level. Hence, the configurationof oxygen is 12 22 2p4.

Murad's Rule

We have learned the order of filling the subshells. Now let's take a closer
look at the filling of electrons in an orbital level. Each orbital can be occupied
by a maximum of 2 electrons, and these electrons will have opposite spins as
dictated by the spin quantum number. Hund's rule describes the way the elec-
trons fill'up the orbitals. According to the Hund's rule, each electron starts fill-
ing up each orbital of a given subshell. After all the orbitals in a given subshell
have been filled singly (half-filled), then the electrons start pairing. Let's look at
some examples.

Example 3-3

Write the electronic configuration of sulfur and also show the filling of elec-
trons with orbital notation.

Solution: Sulfur atom has 16 electrons. The electronic configuration is written

as ls22s2 2p6 3s2 3p4.To see the significance of the Hund's rule, look at the 3p
subshell. In the 3p subshell, we have 3 orbitals.

3p subshell of sulfur
11 denotes paired electrons

1 denotes unpaired electrons

Note that the electrons first occupy singly in the orbitals. Altogether there are 4
electrons in the 3p subshell. Instead of filling the orbitals in pairs, the first 3
electrons start filling the three orbitals singly, and then the remaining electron
occupies the orbital with the other electron as paired electrons. (See the orbital
notation of 3p subshell shown above.) If this were not the case, you would have
seen two electron-paired orbitals followed by an empty orbital.

Another idea we want to touch on concerns paramagnetic and diamagnetic sub-

stances. Substances that have unpaired electrons are called paramagnetic.
Substances that have only paired electrons are called diamagnetic.
The MCAT Chemistry Book

CHAPTER 3 PRACTICE QUESTIONS 5. Consider this statement: No two electrons

of an atom can have the same sets of four
1. Which of the following shows the correct quantum numbers. This is known as the:
order of filling of subshells?
A. Heisenberg's Uncertainty Principle.
B. Hund's Rule.
C. Pauli Exclusion Principle.
D. Aufbau Principle.

6. Which of the following is true with respect

2. Which of the following represents the outer to subshells?
most shell configuration of an inert gas?
A. The 4p subshell has higher energy than
the 5s subshell.
B. The 3p subshell can have a maximum
of 3 electrons.
C. The 5d subshell has higher energy than
the 6s subshell.
D. The 4f subshell has higher energy than
3. The electronic configuration shown below the 5d subshell.
is that of the element:

[Kr] 5s24d l o 5p2 7. Which of the following is NOT isoelec-

tronic with any of the noble gases?
A. Sb.
B. Rb.
C. In.
D. Sn.

4. The maximum number of electrons that can

occupy the energy levels is calculated using 8. Which of the following is NOT a possible
a formula, where n represents the number set of quantum number values for the
corresponding to the energy level. The nitrogen atom, in the order of principal
formula is: quantum number, azimuthal quantum
number, magnetic quantum number, and
spin quantum number?
Chapter 3 Electronic Structure

9. The electronic configuration [Ar] 3d l o 4s2

4p2 is that of:

A. Ge.
B. Zn.
C. Se.
D. Ar.

10. The electronic configuration of a given

element has a 4d subshell. This CANNOT
be the electronic configuration of:

A. 0s.
B. Cu.
C. Ag.
D. Ra.
Chapter 4 Periodic Table

Periodic Table

A. INTRODUCTION

The periodic table is a systematic representation of elements in a par-

ticular order. From the periodic table, we can gather a tremendous amount of
information about the characteristics of an element. In this chapter, we will look
at the trends and other important aspects of the periodic table.

The properties of elements are periodic functions of their atomic numbers.

B. THE PERIODIC TABLE

The vertical columns of elements represented in the periodic table are

called groups, and the horizontal rows are called periods. There are seven periods
in the periodic table. The groups are usually designated by roman numerals
followed by the letter A or B as shown in the periodic table.

The groups IA through VIIA are called the representative elements. These
elements have either s or p orbital valence electrons. The last group in the peri-
odic table is the noble gas group otherwise known as the zero group. The groups
ranging from IB through VIII are called transition metals, and finally the metals
from lanthanum through hafnium and metals from actinium onward are called
the inner transition metals.

We will discuss some of these groups.

Group IA

The Group IA contains hydrogen, lithium, sodium, potassium, rubidium,

cesium, and francium. The Group IA elements are also known as alkali metals,
with the exception of hydrogen which is not a metal. Alkali metals are very reactive.
The MCAT Chemistry Book

-
All of them react with water to form alkaline solutions.

2 Na ( s ) + 2 H20 HZ ( g ) + 2 NaOH (aq)

The reactivity of alkali metals to water increases from top to bottom of

the periodic table. For example, potassium reacts much more rapidly than lithium.
They can also form oxides (For example, lithium can form oxides such as Li,O.)
and a variety of other compounds, since they are highly reactive. Alkali metals
are good electrical and thermal conductors. All of them have one valence elec-
tron in their outer most shell, which is in the s orbital in the ground state. The
Group IA elements usually exhibit an oxidation state of +l . They have a valence
shell configuration of ns'.

Group IIA

The Group IIA elements are called alkaline earth metals. The alkaline earth
metals consist of beryllium, magnesium, calcium, strontium, barium, and radium.
Their oxides are basic. They have a valence shell configurationof ns2,and exhibit an
oxidation state of +2. These elements are not as reactive as alkali metals.

Metallic character decreases from left to right along a period, and incrcci~es
from top to bottom of a group.

Group IIIA

The Group IIIA elements consist of boron, aluminum, gallium, indium,

and thallium. They have a valence shell configuration of ns2np'. They usually
have oxidation states of +l and +3.

Group IVA

The Group IVA is the carbon family. Carbon is the most versatile ele-
ment, and thus it has its own separate subject. Yes, you guessed right - organic
chemistry. Carbon can exist in many different forms by itself such as graphite
and diamond. These forms of carbon are very contrasting in the sense that graphite
is relatively soft whereas diamond is very hard. The Group IVA elements have a
valence shell configuration of ns2np2.

The carbon family consists of carbon, silicon, germanium, tin, and lead.
All these form oxides which look like CO, (e.g., SiO,, PbO,). They also form
monoxides. As medical enthusiasts, you probably have heard of carbon monox-
ide, and its harmful effects. CO is a colorless and odorless gas, and it has even
higher affinity for hemoglobin than oxygen in the red blood cells.
Chapter 4 Periodic Table

Group VA

The Group VA is the nitrogen family. The group consists of nitrogen,

phosphorus, arsenic, antimony, and bismuth. Nitrogen is a diatomic, colorless,
and odorless gas, and is not a very reactive element. The Group VA elements
have a valence shell configuration of ns2np3.

Group VIA

The Group VIA elements are oxygen, sulfur, selenium, tellurium, and
polonium. They have a valence shell configuration of m2np4.Oxygen (0,)is a
diatomic gas, and it also exists in an allotropic form called ozone (0,). Sulfur
forms acidic oxides (e.g., SO,, SO,).

Group VIIA

The Group VIIA is more commonly known as the halogen family of

elements. They are fluorine, chlorine, bromine, iodine, and astatine. They have
an outer configuration of m2np5.Halogens are highly reactive nonmetals, and
form diatomic molecules. Halogens form hydrogen halides which are very acidic.
These hydrogen halides can dissolve in water to form aqueous acids (e.g., HC1).

Fluorine yellow gas

Chlorine greenish-yellow gas
Bromine reddish brown liauid
Iodine - dark colored solid

Group VIIIA

The elements of the Group VIIIA, otherwise known as noble gases are
extremely unreactive. They are found as non-combined forms in nature. Because
of this, they are called inert gases. They have an outer configuration of ns2np6.

C. PERIODIC TRENDS - ONE BY ONE

In this section, we will discuss the periodic properties and trends. It is

very important from the MCAT point of view to understand the trends of the
periodic table.
The MCAT Chemistry Book

Atomic Size

As mentioned earlier, the periodic table is very versatile. The periodic

table can give you the relative atomic sizes of atoms, and elemental ions. The
two trends regarding the atomic radii are given below.

1 . From left to right along aperiod, the atomic radius decreases, as the atomic
number increases.
2. Along a group from top to bottom, the atomic radius increases.

One reason for such a trend is attributed to the principal quantum number.
As the principal quantum number increases, the size of the orbital increases.
Another reason for this trend is attributed to the nuclear shielding by the electron
cloud that is between the nucleus and the outermost shells, thereby decreasing
the influence of the effective nuclear charge.

Problem 4-1

Arrange the following elements in terms of increasing atomic radius:

Mg, K, C1, Ba

A) C1, Mg, K, Cs
B) C1, K, Mg, Cs
C) Cs, K, Mg, C1
D) Mg, K, C1, Ba

The answer is choice A. Mg and C1 are in the same period (Period 3). But C1 is
in Group VIIA and Mg is in Group IIA. So Mg is larger than C1. The next is K
which is in period 4, and thus bigger than both Mg and C1. Finally, Cs which is
in period 6 has the largest atomic radius. So in the increasing order of atomic
size is: Cl<Mg<K<Cs.

Ionic Radius

Often you will get questions on arranging ions and atoms according to
their sizes. Some of the trends that you should keep in mind regarding ionic
radii are listed below:

1. Negatively charged ions have bigger ionic radii than the corresponding
neutral atoms.
2. Positively charged ions have smaller ionic radii than the corresponding
neutral atoms.
 Chapter 4 Periodic Table

Ionization Energy (IE)

Ionization energy is the minimum amount of energy required to remove

an electron from an atom. The amount of energy required to remove the first
electron is called the first ionization energy (IE,). The second ionization energy
(IE,) refers to the amount of energy required to remove the second electron. The
second ionization energy is always greater than the first ionization energy, since
it is more difficult to remove a second electron from an already positive ion,
compared to the removal from an electrically neutral atom. The third ionization

!jflq
lonlzation energy
energy is greater than the second ionization energy, and so on. increases

First IE < Second IE < Third IE < Fourth IE < Fifth IE < Sixth IE < . . . .o I
3g
.-
The general trend of ionization energy is summarized as follows: -
-

1 . Generally, along a periodfiom left to right, the ionization energy increases

with increasing atomic number.
2 . The ionization energy decreases fiom top to bottom along a group as the
atomic size increases.
Electron affinity
Electron Affinity increases

Electron affinity is the change in amount (energy either released or

absorbed) of energy for the process of adding an electron to an atom (neutral) in
its gaseous state, resulting in an ion of -1 charge. The general trend of electron
affinity is given below:

The electron aflnity increases or in other words, the negativeness of the elec-
tron afJinity increasesfrom left to right along a period.

Electronegativity Electronegawity
Increases
The relative tendency of an atom to attract the bonding electrons to itself %
is called electronegativity.The popularly used electronegativity scale is based
on a system called Pauling's scale, according to which fluorine (the most %g
ii
TABLE

electronegative element) has an electronegativity value of 4.0. Nonmetals are

the most electronegative elements. The general trend of the electronegativity is
as follows:

1 . Generally, the electronegativity increasesfiom left to right along a period.

2. The electronegativity decreases down a groupfiom top to bottom.
.
The MCAT Chemistry Book

CHAPTER 4 PRACTICE QUESTIONS 5. Which of the following is NOT diatomic?

1. Sulfur belongs to the classification of ele- A. Oxygen

ments called the: B. Nitrogen
C. Neon
A. inner transition elements. D. Chlorine
B. representative elements.
C. transition elements.
D. alkali metals. 6. Choose the atom that has the biggest atomic
radius.

2. Which of the following is an alkaline earth

metal?

7. Which of the following represents the

correct arrangement of atoms according to
their atomic radii?
3. Which of the following elements has the
lowest electronegativity?

8. Choose the true statement regarding the

periodic trends.
4. Which of the following belongs to the f
block in the periodic table? A. Along a period from left to right, atomic
radius increases.
B. Along a period from left to right, ion-
ization energy decreases.
C. Electronegativity of elements increases
from right to left along a period.
D. None of the above.
Chapter 4 Periodic Table

9. Which of the following is the most acidic?

A. HF
B. HBr
C. HC1
D. HI

10. The outer electronic configuration ns2np2

belongs to which of the following groups?
This page intentionally left blank
Chapter 5 Chemical Bonding

Chemical Bonding

A. INTRODUCTION

MCAT students are expected to know the electronic structures of atoms

and apply this knowledge to the formation of bonds and other related aspects.
This chapter is devoted to the review of chemical bonding and related aspects
such as ionic character and polarity.

What are Chemical Bonds?

Chemical bonds are strong attractive forces that enable atoms or groups
of atoms to hold together. The two major categories of chemical bonds are ionic
and covalent bonds. In this chapter, we will discuss ionic bonds, covalent bonds,
and other atomic and molecular interactions.

B. IONIC BOND

The major force behind the formation of an ionic bond is the electro-
static attractive force that exists between negative and positive ions. It is formed
by the transfer of one or more electrons from one atom to another. The atom that
donates the electrons becomes positive (cation), and the counterpart atom that
receives those electrons becomes negative (anion). The attractive force between
two oppositely charged ions or species holds the atoms together in an ionic
bond.

In an ionic compound, any ion can attract not only the pairing ion or
group, but it can also attract neighboring oppositely charged ions, resulting in
strong ionic solids.
The MCAT Chemistry Book

Now let us take a look at an example to understand this better. The sodium
fluoride (NaF) molecule is a result of ionic bond formation between sodium and
fluoride ions. Together with this, you should also try to understand Lewis dot
structures. Lewis structure will be discussed in detail later in this chapter.

Lewis Electron-Dot Formulas: Lewis electron-dotformulas are diagrammatic

representations of the atoms involved and their valence electrons. The valence
electrons are usually represented as dots around the elemental symbol.

Formation of the Ionic Bond in NaF

-

THE ELECTRONIC CONFIGURATION OF SODIUM AND FLUORINE

Na - 1 2. ~2 26 ~1 2 ~ 3 ~

F - l s22 s22 p5
In the formation of the ionic bond, the sodium atom loses the electron
from its 3s subshell, thereby becoming Na'.

On the other hand, the fluorine atom takes the electron that is being lost from
the sodium atom to form a (F-) fluoride ion.
- -
F + e -F
These resulting ions are oppositely charged and therefore have electrostatic
attractive forces between them, resulting in the formation of the ionic bond.

The attractive energy in an ionic bond can be expressed in terms of Coulombic

energy, according to Coulomb's law. Imagine this by considering that the ions
are spherical and are separated by particular distances. The attractive energy can
be expressed as follows:

kq,q,
Energy, E = r

Here, k (= 9x lo9 J.m/C2)is a constant, q, and q, are the charges, and r is the
distance between the nuclei of the two ionic entities involved in the bonding.
Chapter 5 Chemical Bonding

C. COVALENT BOND

A covalent bond is formed as a result of the sharing of a pair of electrons

between atoms. Covalent bonds result when the difference in electronegativities
between the bonding atoms is very small. Though the intramolecular bonds of
covalent compounds are significant, the intermolecular forces are relatively weak.
Because of this, covalent compounds have relatively lower boiling and melting
points when compared to ionic compounds.

Covalent Bond Formation

)
Internuclear distance I
Figure 5-1

In this section, we will look at the covalent bond formation in the hydro-
gen molecule (H,). The hydrogen molecule is diatomic. The hydrogen atom has
an electronic configuration of 1s" The formation can be expressed in terms of
Lewis formula as follows:

He + OH * H:H or H-H
The MCAT Chemistry Book

After the bond is formed, the electrons are shared by both hydrogen
atoms, as expected in a covalent bond. This 1s overlap makes the configuration
of hydrogen atom the same as that of helium (ls2). Another aspect that you
should understand is that the total potential energy (see Figure 5-1) of the
hydrogen molecule is lower than that of the hydrogen atoms in their separate
forms. The potential energy diagram of hydrogen molecule formation should
make this clear.

Figure 5-2

The distribution of bonded electrons in the HBr molecule is shown above

(Figure 5-2). In this bond formation, hydrogen shares its electron with bromine,
whereas bromine gives the one electron that is needed for hydrogen to complete
its shell. Bromine atom has 7 electrons in its outermost shell, and it requires 1
more to complete its octet. Octet is the state in which an atom has 8 electrons in
its outennost shell. Now, since hydrogen has 2 electrons, and bromine has eight
electrons in its valence shell, they are both satisfied in terms of their stability,
the stability being facilitated by the formation of the covalent bond.

D. COORDINATE COVALENT BOND

In coordinate covalent bonds, the same aspect of the sharing of elec-

trons exists, just as in simple covalent bonds, but the difference is that both
shared electrons are supplied by the same atom.

Coordinate covalent bond isformed when the two electrons that are shared in the
formation of the bond are donated by one group or atom involved in the bond.
Chapter 5 Chemical Bonding

An example of coordinate covalent bond is seen in the formation of ammonium

ion (NH,').

Proton Ammonia Ammonium ion

Ammonium ion can also be represented as

E. POLAR AND NONPOLAR COVALENT BONDS

When two atoms combine, just like in the formation of a hydrogen mol-
ecule, the atoms are one and the same and they have the same electronegativity.
But, if the two atoms that are combined via covalent bond are different, then
there is unequal sharing of electrons due to the electronegativity difference be-
tween those atoms. Such a bond is called a polar covalent bond. The former
case (H, molecule) is an example of a nonpolar covalent compound. In the HBr
molecule, the bonding electrons will be more attracted to the more electronega-
tive of the two atoms, namely bromine. So the bonding electrons are likely to
spend more time closer to the more electronegative atom or group. Hence, this
bond is polar.
-
8' s
H-Br
The delta' (6') indicates the partial positive charge of the hydrogen atom,
and delta-(6-) indicates the partial negative charge of the bromine atom. Small
and equal charges being separated by a small distance constitute a dipole. The
polarity is quantitatively represented in terms of dipole moment, which is the
charge times the distance between the charges. Now that you know dipole
moment, let's learn how to represent this.
s+ g
H-Br Here the net dipole moment is as indicated by the arrow.
The MCAT Chemistry Book

When there are more than two dipoles, the net effect is the vector sum of
all individual dipoles in the molecule. For example, in carbon dioxide (CO,) the
net dipole moment is as shown below.

o=c=o
C------t

Since the dipoles are equal and opposite, the vectors of the dipoles cancel out.

F. THE LEWIS ELECTRON-DOT FORMULAS

Lewis Electron-Dot Formulas: Lewis electron-dotformulas are diagrammatic

representations of the atoms involved and their valence electrons. The valence
electrons are usually represented as dots around the elemental symbol. It is a
two-dimensional way of representing the structural formula, showing the bond-
ing electrons and the lone electrons that are in the valence shells.

Writing Lewis Formulas

The objective of this section is to become comfortable with writing Lewis struc-
tural formulas. We can only predict the Lewis structures of simple molecules.
Other complex structures require complicated analysis and predictions based
on experimental data.

1. First, determine the main structural make up of the molecule, such as guessing
which atom will be the central atom of the molecule. The central atom of the
molecule is usually the atom with the lowest electronegativity.
2. Next, determine the total number of valence (outermost) electrons.
3. Draw the basic skeletal structure of the molecule or ion.
4. Next, determine the distribution of those valence electrons so as to com-
plete the octet of the atoms that are around or bonded to the central atom.
5. The remaining electrons are to be distributed in pairs around the central
atom.
6. Sometimes you might find that the central atom is not reaching the octet
level even at this point. The most likely reason is that there might be a need
of a double bond or a triple bond.

Let's go through an example. Before looking at the solution of the

example shown below, determine the Lewis structure on your own.
Chapter 5 Chemical Bonding

Example 5-1

Write the Lewis dot formula of carbonate ion (CO,)?-.

Solution:

Since carbon is the least electronegative, it is the most likely atom to be in the
center. With this information, we can draw the carbonate ion as indicated below.

Next, calculate the number of valence electrons. Carbon has 4 electrons, whereas
oxygen has 6 electrons each, and do not forget the net charge of -2, which
accounts for two more electrons. This tallies to a total of 24 electrons. We can
set up all these valence electrons around individual atoms in the structure drawn
so far, as shown below:

Now that we have set all the valence electrons, we are done, right? No!
Watch out for the carbon. The octet of carbon is not satisfied, and thus carbon
will not be very stable with its valency at this point. Since there are no more
electrons to spare, we have to move one of the pairs of electrons from an oxygen
atom, which results in 1 double bond and 2 single bonds. The completed Lewis
structure of the carbonate ion should look as follows:
The MCAT Chemistry Book

G. RESONANCE

Resonance is an important concept in chemistry. Though we represent

definite Lewis structures of molecules, in actuality the electrons are not local-
ized. They are shared and delocalized by atoms in such a way as to be in the
most stable electron distribution. This is called resonance.
Acetate ion

The actual form of these resonance structures is an average of all the

possible resonance forms of the group or molecule.

H. FORMAL CHARGE

The concept of formal charge is based on the assumption that the

electrons involved in the bonds are equally shared between the involved atoms.
As you have already seen, this is not exactly the case. But for simplicity and
from an analytical point of view, we assume that the electrons are equally
distributed.

Formal charge of the atoms is the charge of those atoms in a formula, under the
assumption that the electrons in the bonds are equally distributed between the
atoms that contain the bond.
J

Formal - Group number Number of

charge
-
of the atom of interest - Number of bonds - unshared electrons

There are different ways to find formal charges. One way is mentioned here.
You can either choose to do it this way, or whichever way you are comfortable
with.
Chapter 5 Chemical Bonding

Example 5-2

Find the formal charges of all the atoms in thionyl chloride (SOCl,).

Solution:

The Lewis structure of thionyl chloride is written below:

Using the formal charge formula, it is just a matter of plugging in the numbers.
Both oxygen and sulfur belong to Group VI. Chlorine belongs to Group VII.
Sulfur has 3 bonds and 2 unshared electrons. Oxygen has 1 bond and 6 unshared
electrons. Chlorine has 1 bond and 6 unshared electrons.

Formal - Group number Number of

of the atom of interest - Number of bonds -
- unshared electrons
charge

The formal charge of sulfur = 6 - 3 - 2 = +1

The formal charge of oxygen = 6 - 1 - 6 = -1
The formal charge of chlorine = 7 - 1 - 6 = 0

Notice that the net charge of the molecule is zero, as expected, since it is a
molecule and not an ion.

Problem 5-1

Which of the following represents the formal charge of sulfur in sulfuric acid
(H2S04)?

Solution:

If you draw the structure, you'll see that sulfur is the central atom, and has 2
single bonds to the 2 oxygen atoms, and 2 single bonds to the OH groups. The
answer is +2.
The MCAT Chemistry Book

I. BOND LENGTH AND BOND ENERGY

Bond length is the distance between the nuclei of the atoms that are
bonded together. Bond energy is the amount of energy required to pull the
atoms involved in the bond away from each other. Bond order is the number of
bonds (covalent) that exist between the two bonded atoms. The bond length and
bond order are inversely proportional. Hence, as the bond order increases, the
bond length decreases and the bond energy increases.

As the bond order Bond energy

increases increases

Bond length
decreases

Problem 5-2

Which of the following will have the highest bond energy?

A) A carbon-carbon single bond

B) A carbon-carbon double bond
C) A carbon-carbon triple bond
D) A carbon-hydrogen bond

Solution:

The bond order of a triple bond is 3. Carbon-carbon single bond and carbon-
hydrogen bond have bond orders of 1. This eliminates choices A and D. The
bond order of carbon-carbon double bond is 2. The one with the highest bond
order will have the highest bond energy. So the answer is choice C.

J. MOLECULAR GEOMETRY

In this section, we will study the valence shell electron pair repulsion
theory and the basis for predicting the shapes of some structures.
Chapter 5 Chemical Bonding

Valence Shell Electron Pair Repulsion Theory

Valence shell electron pair repulsion theory (VSEPR) can be used to

predict the shapes of molecules. According to this theory, the geometry of a
molecule is such that the valence-electron pairs of the central atom are kept
farthest apart to minimize the electron repulsions. Again, you have to view mol-
ecules in terms of Lewis structure so that the shape of the molecules can be
predicted with the VSEPR theory.

Molecular geometry of a molecule is the directional orientation of the bonded

pairs around the central atom, excluding the unshared electron pairs.

Let's look at the practical significance of this theory through some examples.

Example 5-3

Predict the molecular geometry of the CO, molecule.

Solution:

Carbon, obviously the central atom, has four electrons in its valence shell. In
order to complete the octet, carbon requires four more electrons or two pairs of
electrons. Oxygen atom has six electrons in its valence shell. In order to com-
plete its octet, each oxygen atom requires two electrons or one pair of electrons.
The Lewis structure of CO, should look like the figure shown below. Note that
the valence electrons of the carbon atom are denoted by asterisks (*) and that of
the oxygen are denoted by dots.

The molecule keeps this linear shape, so that the electrons are placed far apart as
predicted by the VSEPR theory. Also notice that the carbon-oxygen bonds are
double bonds. Hence the CO, molecule is linear in shape.

Example 5-4

Predict the shape of the BeF, molecule.

Solution:

Beryllium has two electrons in its outer most shell. In this case, there is an
exception to the octet rule, because in the formation of the molecule, only two
The MCAT Chemistry Book

pairs (four electrons) are present in the valence shell of beryllium. Each fluorine
atom requires one electron to attain the complete octet. Take a look at the structure
shown below. Again for clarity, beryllium electrons are denoted by asterisks and
fluorine electrons are denoted by dots.

Example 5-5

predict the shape of the water (H,O) molecule.

Solution:

When dealing with bond formation with the possibility of existence of lone
pairs, we have to take that into consideration. You will see that in this example.
The oxygen atom has six valence electrons, and the hydrogen atom has one
valence electron. So in the structural formation, there are two lone pairs in the
central oxygen atom. How do you think this will change the shape of the mol-
ecule? Well, because of the lone pairs, the molecule will be bent, rather than
linear. The structure is shown below.

Angular, or bent shape of the

water molecule

Problem 5-3

Predict the geometry of the following molecules.

Chapter 5 Chemical Bonding

Answers:

A) linear
B) trigonal pyramidal
C) tetrahedral
D) trigonal planar
E) tetrahedral

Table 5-1
SOME COMMON GEOMETRIES AND THEIR CHARACTERISTICS

BONDING ELECTRON LONE PAIRS GEOMETRY

PAIRS

2 NONE LINEAR

3 NONE TRIGONAL PLANAR

2 1 BENT

4 NONE TETRAHEDRAL

3 1 TRIGONAL PYRAMIDAL

5 NONE TRIGONAL BIPYRAMIDAL

4 1 SEESAW SHAPED

3 2 T-SHAPED

6 NONE OCTAHEDRAL
The MCAT Chemistry Book

CHAPTER 5 PRACTICE QUESTIONS I. Ammonia (NH,) can bond with boron

trifluoride (BF,). For the bond formation,
1. Which of the following best represents the the electrons are most likely supplied by:
Lewis structure of SO,-*?
A. nitrogen.
B. boron.
C. both boron and nitrogen because the
bond formed is covalent.
D. hydrogen.

5. Which of the following has the highest

dipole moment?

A. HF
B. CC1,
C. HBr
D. CO,

6 . The molecular geometry of BCl, is:

A. linear.
B. trigonal planar.
C. tetrahedral.
D. trigonal bipyramidal.

2. Which of the following has a net dipole 7. CC1, molecule is:

moment of zero?
A. trigonal planar.
A. H,O B. linear.
B. HC1 C. octahedral.
C. CO D. tetrahedral.
D. CH,

8. Which of the following best describes the

3. The bond between nitrogen and oxygen in geometry of nitrate (NO,-)?
NO, is most likely:
A. Trigonal planar
A. an ionic bond. B. Trigonal bipyramidal
B. a covalent bond. C. Tetrahedral
C. a hydrogen bond. D. Angular
D. a dipole-dipole interaction.
Chapter 5 Chemical Bonding

9. What is the molecular geometry of SF,?

A. Hexagonal
Compound A
B. Tetrahedral
C. Octahedral
D. Trigonal planar

10. CH, and SiF, are examples of tetrahedral

geometry. Which of the following are true
regarding these two molecules?
Compound B
I. The carbon-hydrogen bonds are dipoles
11. The silicon-fluorine bonds are dipoles
111. Methane is nonpolar
n! SiF, has zero dipole moment

A. I & 11 only
B. I1 only
C. 11 & I11 only
D. I, 11, I11 & IV

11. Which of the following types of bonds has

the least electronegativity difference
between the bonding atoms?

A. Ionic bond
B. Polar covalent bond
C. Nonpolar covalent bond
D. Cannot be predicted without the actual
electronegativity data. 13. Choose the answer which best denotes the
electronic orientation (electronic geometry)
of the water molecule.
12. Which of the following choices represents
the vectors of bond dipoles of the indicated A. Angular
(indicated by the arrows) bonds of the com- B. Bent
pounds A & B, respectively? C. Trigonal planar
D. Tetrahedral
This page intentionally left blank
Chapter 6 Gases

Gases

A. INTRODUCTION

In this chapter, we will review the essential aspects of gases, and the
terms that are commonly associated with them. This chapter will also discuss
the various laws such as Charles' law, Boyle's law, and ideal gas law. Finally,
the kinetic law of gases will be explored.

B. GASES - AN OVERVIEW

Gases are unique when compared to liquids and solids. Gases can be
compressed into smaller volumes, and they can be mixed extensively. They have
relatively very low densities. Ideally, a gas exerts pressure on all sides of the
container it occupies in a uniform manner. These are some of the properties of
gases. Let's explore these ideas in detail.

Standard Temperature and Pressure

It is very important to understand the general aspects of gas pressure, its

measurements, and calibrations. Pressure is force exerted over unit area. The
unit of pressure is pascal (Pa) which is equivalent to kg/(m.s2).In chemistry, we
usually use a mercury-based barometer to measure the pressure. The unit is
millimeter of mercury (mmHg). This is the same as the unit ton. Another unit
commonly used to denote pressure is atmosphere (atm). You should be able to
convert these units back and forth as required.

1 atm = 760 mmHg = 760 torr

1 atm = 1.01 x lo5Pa

The MCAT Chemistry Book

Gases can be compressed or expanded by adjusting the temperature and

other conditions that prevail. In order to standardize the quantities of gases mea-
sured and conveyed, arbitrary reference conditions called standard temperature
and pressure (STP) have been chosen and internationally accepted. The specific
values of temperature and pressure at STP are 0" C (273 K) and 1 atm (760
mmHg).

STANDARD TEMPERATUFUZ AND PRESSURE (STP)

Temperature - O0 C or 273 K
Pressure 1 atm or 760 mmHg

You should know what STP is, because in many questions and passages,
the actual temperature and pressure situations will not be explicit. Rather, they
will say, for example, that the reaction was undertaken at standard temperature
and pressure. This means, you have to automatically know that they are talking
about the temperatures corresponding to STP reference conditions, which you
already know.

Molar Volume

Ideally, one mole of gas at STP occupies a volume of 22.4 L. This is

known as molar volume. We should bear in mind the fact that this is under
standard conditions. Do the example below on your own, before you look at the
solution.

Example 6-1

Calculate the number of moles of oxygen at STP present in a volume of 78.75 L.

Solution:

One mole of gas occupies a volume of 22.4 L. To get the number of moles, you
have to divide 78.75 L by 22.4 Llmol.
1 mol of 0 ,
Number of moles of oxygen = 78.75 L x = 3.5 moles
22.4 L
Chapter 6 Gases

C. GAS LAWS

Gases behave ideally under reasonably high temperatures and low

pressures. The gas laws are helpful in quantitatively relating pressure, volume,
temperature, and molar units.

Boyle's Law

According to Boyle's law, the volume of a fixed amount of gas is inversely

proportional to the pressure, provided that the temperature is kept constant. A
simple and good example with biological significance is the way we take air
into our lungs. The way we breathe can be summarized as follows. As the
respiratory centers signal, during inspiration the diaphragm contracts resulting
in an increase in the thoracic volume, which in turn translates into an increase in
the lung volume. This increase in lung volume results in a decrease in pressure.
This decrease in pressure inside the lung results in the rushing of air into the
lung from the outside - inspiration. The exact opposite conditions result in
expiration. The point is that at constant temperature, the volume of a gaseous
sample is inversely proportional to its pressure.

Volume o~
Pressure

This can be represented mathematically as shown below:

1
BOYLE'S LAW V K - or PV = k (Constant)
P

Example 6-2

200 ml of a gas is present in a cylinder at a pressure of 760 torr. If the gas is

compressed by using a piston to a pressure of 950 torr, calculate the final vol-
ume occupied by the gas. (Assume the temperature to be constant)

Solution:

This problem specifically tests your knowledge of Boyle's law. We know that
PV is a constant, provided that the temperature is kept constant. Since the tem-
perature is constant, we can readily apply Boyle's law. We can equate the initial
and final stages of the system. PIand V , represent the initial pressure and vol-
ume respectively. P2 and V2represent, the final pressure and volume respectively.
The MCAT Chemistry Book

Now it is just a matter of solving for V, Cfinal volume).

760 torr
& = V, = 200 o
ml ( 9 5 0 ton) = 160 rnl

Charles' Law

In 1787, Jacques Charles showed that gas expands to occupy a larger

volume as the temperature increases. Volume can be plotted against the tem-
perature as shown below:

Temperature (OC )
i
Figure 6-1

When the temperature is increased, the volume increases. Charles found

that the volume of a gas is directly proportional to its absolute temperature,
provided that the pressure is kept constant. So the volume and temperature have
a linear relationship as represented by the graph. Charles's law can be math-
ematically expressed as follows:
Chapter 6 Gases

Volume K Temperature
V X T

V = kT or
v
- = k (constant),
T
where k represents the proportionality constant.

The volume-temperature graph shows that at zero volume, the correspond-

ing temperature value is -273.15" C. This means that at -273.15O C, the volume
occupied by the gas is zero. This temperature is unique, and scientists so far have
not been able to devise a way to lower the temperature to -273.15O C.

Combined Gas Law

The gas laws (Charles' and Boyle's law) can be combined to form the
combined gas law. The resulting law can be represented mathematically as shown
below:

COMBINED GAS LAW = P2V2 =

k (constant)
? T2
This relationship can be used to do a variety of calculations involving
gases, since it relates pressure, volume, and temperature.

The Ideal Gas Law

This is an extension of the combined gas law. In the combined gas law,
we saw the relationship between pressure, volume, and temperature. The ideal
gas law can be expressed mathematically as follows:

THE IDBU GAS LAW PV = n RT

P - pressure
V - volume
n - number of moles
R - molar gas constant
T - temperature
 The MCAT Chemistry Book

Here, R (molar gas constant) has values 0.082 L.atm/(K.mol), or 8.3 1 J/(K.mol),
and of course the difference in values is due to the fact that the gas constant is
expressed here in two different units.

D. KINETIC THEORY OF GASES

The kinetic theory of gases can be explored in terms of the following

assumptions. The theory tries to answer the questions regarding the various
properties of gases. It also gives the relationship between the kinetic energy of

R]
the molecules and the absolute temperature. The important points in kinetic
theory of gases are listed below:

1. A gas consists of small particles (sizes are considered relatively negligible)

known as molecules, which are separated widely apart and thus the gas con-
tainer is mostly empty.
2. The molecules are in a state of continuous random motion, and colliding
0 , against each other and also against the sides of the container, and further-
more the collisions are elastic.
Ideal gas molecules
travel randomly in 3. These collisions result in the pressure of the gas.
straight lines at differ- 4. The molecules are expected to travel in straight lines at different speeds in
ent speeds. all directions.
5. The forces (attractive or repulsive) between the molecules are negligible.
6. The average kinetic energy of the molecules is proportional to the temperature.

Some Aspects Related to Kinetic Theory

The main aspect of kinetic theory is that the molecules in a gas are in a
state of continuous random motion. The speed of molecules depends on the
temperature, and can have a range of values. Maxwell's distribution curve is
perfect to analyze this fact. In the Maxwell's distribution curve, the relative
number of molecules are plotted against the molecular speed on the x-axis. Take
a look at the curve in Figure 6-2.

Note that the speed corresponding to the maximum number of molecules

is called the most probable speed. This is always smaller than the average
speed, which is in turn smaller than the root-mean-square speed (rms speed).

The formula for root-mean-square speed is given below:

Root-mean-square speed = jy
Here, R is the gas constant, T is the absolute temperature, and M is the molar
mass of the gas.
Chapter 6 Gases

I000 2000 3000 4000 5000

Molecular speed
(mls)
MAXWELL'S DISTRIBUTION CURVE
Figure 6-2

E. PARTIAL PRESSURE AND MOLE FRACTION

Let's consider a container which has different gases in it. According to

the Dalton's law of partial pressures, the partial pressures of the gases present in
a gaseous mixture can be added to get the net total pressure of the mixture. But,
what is partial pressure? Partial pressure is the pressure exerted by a particular
gas in a mixture of gases. Now that you know what partial pressure is, take a
look at the boxed information which summarizes the whole idea of Dalton's
law of partial pressures.
The MCAT Chemistry Book

Dalton's Law of Partial Pressures

Plola,= P A + PB + PC + PD + . . . (at constant volume &temperature)

P,, - Total pressure

PA,P,, PC,P,, . . . represent the partial pressures ofgases A, B, C, D, andso on.

Another concept you have to understand is mole fraction. The mole frac-
tion of a gas is the fraction or ratio of moles of that particular gas against the
total number of moles of gases present in the mixture. Mole fraction is defined
as follows:

Number of moles of gas A - - n~

Mole fraction =
Total number of moles of gases in the mixture n,,,,,

Example 6-3

A 1 liter flask contains 0.4 mol of helium and 1.2 moles of hydrogen gas. Find
the mole fractions and partial pressures of both gases, if the total pressure of the
mixture is 790 mmHg.

Solution:

The total number of moles of gases present in the container is 0.4 + 1.2 = 1.6 moles

0.4
The mole fraction of helium = - = 0.25
1.6

1.2
The mole fraction of hydrogen =- = 0.75
1.6

Notice that the sum of the mole fractions is always one. If it is not, you probably
made an error somewhere in your calculation. Here,

Next, we have to find the partial pressures of the gases. We know that the partial
pressures of the gases should add up to get the total pressure of the gases. Now
that we know the total pressure and the mole fractions, we can calculate the
partial pressures of helium and hydrogen.
Chapter 6 Gases

Partial pressure of gas A = mole fraction of gas A x total pressure

Partial pressure of helium = 0.25 x 790 mmHg = 197.5 mmHg

Partial pressure of hydrogen = 0.75 x 790 mmHg = 592.5 rnrnHg

F. GRAHAM'S LAW

Diffusion of gases can be described as the process by which a gas spreads

to occupy the available and accessible space, thereby creating a uniform pressure
throughout the space the gas occupies. A gas having a higher partial pressure
will travel or diffuse toward regions of gases having a lower partial pressure,
until an equilibrium is reached. To analyze the diffusion of gases, it is much
simpler to think in terms of effusion. The difference between diffusion and
effusion is that diffusion is the movement of gas through the entire volume of
the container, whereas effision is the movement of gas through a tiny hole of
the container.

Figure 6-3
The figure depicts the effusion of gas molecules through a small hole in the container.

According to Graham's law of effusion, the effusion rate of a gas is

inversely related to the square root of the molecular weight of the gas. This is
true provided that we have the same pressure and temperature conditions.
Graham's law can be expressed as shown below:
Graham's law of effusion

1
Effusion rate of gas molecules a
/, molecular weight

Graham's law can also be applied to diffusion.

The MCAT Chemistry Book

Example 6-4

Calculate the ratio of efision of the gases oxygen and hydrogen. Assume that
the two gases are in the same container having a tiny hole in it.

Solution:

First, we have to consider the fact that according to Graham's law, the rate of
effusion is inversely proportional to the square of molecular weight of the gas,
which is effused. This can be represented as follows. Keep in mind that both
gases are diatomic.
Rate of e f s i o n of H = - 4
- - = 4
Rate of effusion of 0 , 1

So the ratio of the rates of efision of hydrogen and oxygen is 4 : 1.

We should think about the implications of this ratio. This means that the hydro-
gen molecules will effuse four times faster than the oxygen molecules.
Chapter 6 Gases

CHAPTER 6 PRACTICE QUESTIONS 4. A hypothetical reaction R occurs only at

elevated pressures. It was noted that the
1. Consider the reaction between nitric oxide optimum pressure required for the reaction
and oxygen to form nitrogen dioxide. If 4 was 1330 mmHg. This value is roughly
liters of nitrogen dioxide were formed, how equal to: (1 atm = 101.3 kPa)
many liters of nitric oxide and oxygen must
have reacted? A. 1.3 x Pa.
B. 1.8 x lo5 Pa.
C. 1.35 x 10' Pa.
D. 1.8 x 10, Pa.

5. -27O C is the same as:

2. At a particular temperature and pressure, 1

mol of gas M occupies 45 liters. If the den-
sity of gas M at the same temperature and
pressure is 1.8 g/L, the molecular weight
of gas M is:

A. 25 glmol. 6. The volume occupied by 11.5 g of carbon

B. 8 1 glmol. dioxide at STP is approximately equal to:
C. 40.5 glmol.
D. 4 glmol.

3. A certain gas behaves ideally at STP. If the

density of the gas is 1.4 g/L, what is the
most likely identity of this gas? (The gas is
diatomic.)
Questions 7-13 are based on the following
A. SO, passage.
B. N,
C. 0, Passage 1
D. F,
The behavior of gases can be predicted
to a large extent on the basis of various laws.
Gases are expressed mainly in terms of
pressure, volume, and temperature. Many gases
obey the ideal gas laws and those gases are
called ideal gases. If we are not doing precision
experiments, we can normally ignore the slight
deviations that occur under normal conditions.
Nevertheless, we cannot completely ignore the
deviation factors.
The MCAT Chemistry Book

According to Boyle's law, the pressure Table 1

is inversely proportional to the volume at a con-
stant temperature. Charles' law states that the
volume is directly proportional to the tempera-
ture at a constant pressure. Combining these
laws and Avogadro's law gives the combined
gas law.

PV = nRT
(The ideal gas law)

Not all gases behave ideally. There are

often deviations from the ideal behavior. At low
temperatures, gases often behave differently
apart from what is described by kinetic-
molecular theory of gases. Considering these
correction factors,. the modified gas equation 9.390 0.09 1
Propane
is:

7. Under which of the following conditions

will gases behave most ideally?
The correction constants or Vander Waal con-
stants, a and by of gases are experimentally A. Low temperature and high pressure
found. The Van der Waal constants of some B. High temperature and low pressure
gases are given in Table 1. C. Low temperature and low pressure
D. Gas behavior does not depend on
temperature and pressure if the gas is
an ideal gas, and such a gas will behave
ideally regardless of the conditions
Chapter 6 Gases

8. What is the unit of universal gas constant R? 11. What is the most likely Van der Waal con-
stant correction factor of bromine?
mol. K
A. -
L. atm
atm
B. -
mol. K
L. atm
C. -
mol. K 12. Equal volumes of gases will contain the
L. atm same number of molecules at the same tem-
D. - perature and pressure. This prediction is
mol.
directly based on:

9. A group of general chemistry students were A. Charles law.

assigned to conduct gas experiments. The B. Boyle's law.
vessel that contained the gases had a small C. kinetic-molecular theory.
hole in it. The gases used in the experiments D. Avogadro's law.
were SO, and 0,.What is the rate of leakage
of SO, to 0, through the hole?
13. Based on kinetic-molecular theory, which
of the following are true?

I. At a given temperature, all gases have

the same average kinetic energy.
11. At a given temperature, different gases
have different average velocities.
10. If the Vander Waal constant a is found to 111. The average kinetic energy is propor-
be zero for gas A, what are true regarding tional to the absolute temperature.
this gas?
A. I only
I. Gas A does not behave ideally. B. I1 only
11. Gas A behaves ideally. C . I & I11 only
111. Gas A is Xenon. D. I, I1 & I11

A. I only
B. I1 only
C. I1 & I11 only
D. I11 only
This page intentionally left blank
Chapter 7 Liquids, Solids, and Phase Transitions

Liquids, Solids,
and Phase Transitions

A. INTRODUCTION

In this chapter, we will explore the other two important phases of matter;
liquids and solids. From your own experience, you probably have noticed that it
is easier to handle liquids and solids than to handle gases. Gases have negligible
intermolecular interactions and attractive forces. But this is not the case with
either liquids or solids. They both have much stronger intermolecular forces
than gases. These forces make substances exist as liquids and solids. As we go
along, we will explore the ideas such as hydrogen bonding, London dispersion
forces, and dipole interactions.

In addition to just knowing these phases, you will have to know the
different theories and their implications, and how to work with some of the
formulas involved. We will review the different kinds of molecular interactions
that dictate the phase characteristics of molecules. The phase diagram that is
discussed in this chapter is also important from the MCAT point of view.

B. THE LIQUID STATE

Liquids are considered to be relatively incompressible. Unlike gas mol-

ecules, liquid molecules are tightly packed. Liquids have a fixed volume, whereas
gases do not. Liquids do not have a definite shape. The properties of liquids can
be attributed to the presence of various types of intermolecular forces.
The MCAT Chemistry Book

C. INTERMOLECULAR FORCES

Intermolecular forces are weak attractive forces that contribute to many

of the physical properties exhibited by liquids. From the MCAT point of view,
you have to be familiar with the main three types of attractive forces:

1) Hydrogen bonding
2) Dipole-dipole interactions
3) London forces

Hydrogen Bonding

Hydrogen bonding is an intermolecular attractive force that exists

between a hydrogen atom covalently bonded to an electronegative atom (fluorine,
oxygen, nitrogen), and another electronegativeatom (fluorine, chlorine, nitrogen)
in the neighboring molecule. Hydrogen bonding in water is shown below:

Figure 7-1 Hydrogen bonding in water

As you can see in Figure 7-1, the hydrogen which is covalently bonded
to the electronegative atom (in this case it is oxygen), can undergo hydrogen
bonding with an electronegative atom (the oxygen of another water molecule)
present in the neighboring molecule.
Chapter 7 Liquids, Solids, and Phase Transitions

Dipole-Dipole Interactions

Polar molecules have negative and positive polarity. This is because of

the difference in electronegativities of the bonded atoms in such molecules.
This polarity results in the formation of attractive forces among molecules. Such
interactions are called dipole-dipole interactions. Consequently, the positive
end of one molecule is attracted to the negative end of another. Figure 7-2 illus-
trates the dipole-dipole interactions between hydrogen chloride molecules.

Dipole-dipole attractive
(represented by wavy lines)

Figure 7-2 Dipole-dipole interaction between HCI molecules

London Forces

London forces are weak attractive forces that exist between instantaneous
dipoles. What is an instantaneous dipole? In order to understand this, let us talk
about atoms. Atoms have a central positively charged nucleus surrounded by
electrons. These electrons are constantly moving and the electronic cloud may
not be always perfectly distributed. In other words, the electrons at any given
moment may be distributed more on one side and less on the other, creating an
instantaneous dipole. The side which has more electrons at any moment will
have a slight negative charge, whereas the side which is electron deficient will
have a slight positive charge. The polarity that results from such charge
The MCAT Chemistry Book

separations in a molecule can induce polarity in other molecules when they are
close enough to the instantaneous dipole molecule. For this reason, London
forces are often called instantaneous dipole-induced dipole interactions. London
forces are more pronounced in bigger molecules, because they are more
polarizable.

Let us talk about the importance of these ideas. It is more likely that a
polar molecule will exist as a liquid or solid than a nonpolar molecule. Why is it
so? It is because of the intermolecular interactions that are possible among polar
molecules.

D. THE SOLID STATE

A solid has a well-defined shape. Because of the tight packing of the

molecules, solids can be considered almost incompressible. There are four types
of solids:

1) Ionic solid
2) Metallic solid
3) Molecular solid
4) Network solid

Ionic Solid

An ionic solid consists of cations and anions which are held together by
the electrostatic attraction between them. These attractive forces are very strong
and thus ionic solids have high melting points. Sodium chloride (NaCl), and cesium
chloride (CsC1) are examples of ionic solids.

Metallic Solid

A metallic solid consists of positive atomic cores surrounded by elec-

trons. Almost all metals are solids at room temperature. The free electrons in
metallic solids account for their superior electrical conductivity (e.g., iron, gold,
silver).
Chapter 7 Liquids, Solids, and Phase Transitions

Molecular Solid

A molecular solid consists of atoms or molecules held together by

intermolecular attractive forces. In molecular solids, the attractive forces include
hydrogen bonds and dipole-dipole forces (e.g., Ice [H,O (s)]).

Network Solid

Figure 7-3 Structure of diamond

In a network solid, the atoms are held together by large networks of
covalent bonds. A perfect example is diamond. Because of such an intricate
network (see Figure 7-3) of covalent bonding through the entire crystal, the
diamond crystal itself can be considered as one big molecule. Each and every
carbon in a diamond is covalently linked to four other carbon atoms. For these
reasons, network solids have very high melting points. Other examples of net-
work solids include graphite and asbestos.

E. PHASE TRANSITIONS

Phase transition or change of state refers to the change of a substance's

phase from one state to another. In this section, we will talk about the different
phase changes, the associated terminology, and the key ideas related to all these.
The MCAT Chemistry Book

Types of Phase Transitions

There are different types of phase transitions. From the MCAT point of
view, you should have a good grasp of phase transitions. Let's look at the basic
terminology.

The conversion of a solid to a liquid is called melting.

The temperature at which a substance changes fiom solid state to its liquid
state is called its melting point.

SOLID melting + LlQUlD

(endothermic)

LlQUlD freezing + SOLID

(exothermic)

LlQUlD vaporization GAS

(endothermic)

GAS condensation + LlQUlD

(exothermic)

SOLID sublimation GAS

(endothermic)

deposition
GAS w SOLID
(exothermic)

The conversion of a liquid to a solid is called freezing.

The temperature at which a substance changespom liquid state to its solid

state is called itsfreezing point.

The conversion of a liquid to a gas is called vaporization.

The temperature at which a substance changespom liquid state to its gas state
is called its boilingpoint.

The conversion of a gas to a liquid is called condensation.

The direct conversion of a solid to a gas is called sublimation.

Chapter 7 Liquids, Solids, and Phase Transitions

F. HEAT T.RANSFER

In order to increase the temperature of a substance, we have to supply

heat. The heat that should be supplied to increase the temperature varies from
one substance to another. So scientists have come up with a way to define this -
the specific heat. The specific heat (J/g.CO)of a substance is the amount of heat
that should be added to one gram of that substance to raise its temperature by
one degree Celsius. The Heat capacity of a given sample substance is the amount
of heat that is required to increase the temperature by one degree Celsius. Heat
capacity, specific heat, and temperature are related according to the following
relations:

q = C ( t , - t l ) = C At,

where q is the heat required,

C is the heat capacity, and
A t is the change in temperature.

q = m CSPA t,

where q is the heat required,

m is the mass of the substance in grams,
Clpis the specific heat, and
A t is the change in temperature.

Let's now talk about the temperature change when heat is added to a
substance - the changes in temperature that occur during the change of a sub-
stance from its solid state to gaseous state or vice versa. It is easier to understand
this fiom the Figure 7-4.

Let's say we are adding heat to a substance which is in its solid state. As
the heat increases, the temperature increases until the melting point is attained.
Then the temperature will not rise until the substance has melted. Keep in mind
that the process of melting requires energy. As more heat is supplied, the
temperature again starts increasing until the boiling point has been reached.
Then again the temperature will not rise during the process of boiling or
vaporization, because the energy that is supplied is used for the process of
vaporization. After vaporization is completed, as more heat is supplied, the
temperature again starts increasing.
The MCAT Chemistry Book

, Boil~ng

2rri C
Condensing
1
a4
0.

b I
Melting
Freezing
I

Heat I >

Figure 7-4
Some related terms:

Heat of fusion of a solid substance is the quantity of heat required to melt one
gram of that substance at its melting point. The usual unit used is Jlg.

Heat of vaporization of a liquid substance is the quantity of heat required to

vaporize one gram of that substance at its boiling point. The unit used is Jlg.

Heat of condensation of a substance is the quantity of heat that should be

removed to condense one gram of that substance at its condensation point. The
unit used is Jlg.

Heat of crystallization of a substance is the quantity of heat that should be

removed to crystallize one gram of that substance at its freezing point. The unit
used is Jlg.

G. PHASE DIAGRAMS

A phase diagram is a graphical representation of phase transitions under

different pressures and temperatures. By analyzing the phase diagram of a
Chapter 7 Liquids, Solids, and Phase Transitions

substance, we can predict the state of that substance at a given temperature and
pressure. For the MCAT, you should be familiar with the phase diagram and
what exactly it represents, and also be able to predict some of the related trends
from a given phase diagram.

In a phase diagram, there are three sections representing the solid, the
liquid, and the gas phases. The phase diagram of a substance enables us to
determine the phase of that substance at a given temperature and pressure. The
phase diagram is actually plotted using experimentally determined values at
different temperatures and pressures. Let's take a look at the phase diagram
(Figure 7-5) of water.

point-Temperature & Pressure at

I which three phases coexist in equilibrium)

--

Temperature (K)

Figure 7-5 Phase diagram of water (diagram not drawn to scale)

As you can see in the phase diagram of water shown above, there are
three regions in the graph representing solid, liquid, and gas phases. The seg-
ment BC divides the solid and the liquid phases of water. This segment represents
the equilibrium region between the solid and the liquid phases. Because water is
The MCAT Chemistry Book

denser than ice, the segment BC is slightly slanting toward the left. For most
phase diagrams (Figure 7-6), the segment BC will be slightly slanting toward
the right (positive slope), since the liquid phase is usually less dense than the
solid phase.

The segment BD divides the liquid and the gas phases in the graph. It
also denotes the vapor pressures at different temperatures. The intersecting point
of the curves represented by point B is called the triple point. This point repre-
sents the temperature and pressure at which the three phases of a substance are
in equilibrium. How many triple points are likely to exist for a substance? The
answer is one. There is only one pair of temperature-pressure combination for a
substance at which the three states will be in equilibrium. Figure 7-6 shows a
phase diagram representing the majority of other compounds that we see in
nature.

Temperature (K)

Figure 7-6 Phase diagram of most substances (diagram not drawn to scale)
(Notice the positive slope of segment BC, unlike that of water which has a negative slope)
Chapter 7 Liquids, Solids, and Phase Transitions

Substances in their gas phase can usually be liquefied by increasing the

pressure. But it reaches a point where this conversion is not possible. The tem-
perature above which liquid phase cannot be achieved regardless of the applied
pressure is called the critical temperature. The vapor pressure at the critical
temperature is called the critical pressure.

H. COLLIGATIVE PROPERTIES

Colligative properties are properties that depend only on the number

(concentration) of solute particles present in a solution. These properties do not
depend on the identity of the solute. As an example let's talk about two aqueous
solutions; one containing glucose and the other containing urea. As far as the
colligative properties are concerned, the two solutions are not different as long
as the number of glucose and urea particles are the same. In other words, if the
concentration of the given samples of urea and glucose are the same, the colli-
gative properties of both solutions will be the same.

The colligative properties that you have to be familiar with for the MCAT are:

1) vapor-pressure lowering
2) boiling-point elevation
3) freezing-point depression
4) osmotic pressure generating

A simple solution is a mixture of a solute and a solvent.

SOLUTE + SOLVENT = SOLUTION

Vapor-pressure Lowering

When a solvent contains impurities (solutes), there will be a reduction

in its vapor pressure. This means the vapor pressure shown by a solvent when it
is pure is lowered by the addition of solutes. The change in vapor pressure is
proportional to the quantity of the dissolved solute. Raoult's law explains this
relationship.
The MCAT Chemistry Book

According to Raoult's law, the mole fraction of the solvent times the
vapor pressure of the pure solvent is numerically equal to the vapor pressure of
the solution. This is mathematically represented as shown below:

PA = XA X PA

Here, PA is the vapor pressure of the solution (impure solvent),

X,is the mole fraction of the solvent, and

PAis the vapor pressure of the pure solvent.

Example 7-1

Calculate the mole fractions of sodium chloride and water in a solution contain-
ing 11.7 g of sodium chloride and 9 g of water.

Solution:

In this solution, we have 11.7 grams of NaCl and 9 grams of H,O. First; you
have to find the number of moles of NaCl and H,O.

11.7 g
Number of moles of NaCl = = 0.2 mol
58.5 g / rnol

9g = 0.5 rnol
Number of moles of H,O =
18 g / rnol

The total number of moles in the solution = 0.2 + 0.5 = 0.7 mol

0.2 rnol
Mol fraction of sodium chloride = 0.3
0.7 rnol

0.5 rnol
Mol fraction of water = = 0.7
0.7 rnol

Boiling-point Elevation

The boiling point of a liquid is defined as the temperature at which its

vapor pressure equals the prevailing pressure. The prevailing pressure is normally
Chapter 7 Liquids, Solids, and Phase Transitions

the atmospheric pressure, provided that the container in which the liquid is present
is kept open while boiling. When a nonvolatile solute is added to a pure solvent,
the boiling point increases. The increase is proportional to the number of moles
of the solute added to the solvent. The relationship is mathematically represented
as shown below:

ATb = i Kb Cn,

Here, ATb is the boiling-point elevation,

i is the ionization factor,

Kb is the boiling-point elevation constant, and

Cmis the molal concentration of the solution.

Example 7-2

Calculate the boiling point of 0.2 m aqueous solution of glucose. (K, of water is
0.5 12OClm.)

Solution:

The formula for finding the boiling-point elevation is:

AT, = i K, Cm

In this problem, we have all the necessary values to find the boiling-point
elevation. Here, the ionization factor is 1, since glucose doesn't ionize. Let's
substitute the values into the formula.

AT, = K,Cm =0.512Clmx 0.2m *O.lC

The boiling point of 0.2 m solution of glucose is 100 + 0.1 = 100.lC

Freezing-point Depression

The solute concentration affects the freezing point of a solvent. The fieez-
ing point of a pure solvent is decreased when solutes are added to it. Just like the
boiling-point elevation, freezing-point depression is proportional to the molal
concentration. The relationship is shown:
The MCAT Chemistry Book

AT, = i K, Cm

Here, AT, is the freezing-point depression,

i is the ionization factor,

K, is the freezing-point depression constant, and

Cmis the molal concentration of the solution.

Example 7-3

Calculate the freezing point of 2 m aqueous solution of glucose. (K, of water is

1.86"Clm)

Solution:

The formula for finding the freezing-point depression is:

AT, = iKiCm

In this problem, we have.al1 the necessary values to find the freezing-point

depression. The ionization factor is 1.

So the freezing point of 2 m solution of glucose is 0.0 - 3.7 = - 3.7"C

Osmotic Pressure

Osmotic pressure is also a colligative property. Before we talk about

osmotic pressure let's turn our attention to the process of osmosis. Consider two
solutions that are made out of the same solvent with different concentrations of
solute separated by a semipermeable membrane. The solvent will flow through
the semipermeable membrane fiom the solution of lower concentration to the
solution of higher concentration. Thus, osmosis is defined as the flow of sol-
vent through a semipermeable membrane .resulting in the equilibrium of con-
centrations on both sides of the semipermeable membrane.

We will explore the process of osmosis with an experiment. A dilute

solution of sodium chloride is taken in a funnel. The mouth of the funnel is
covered by a semipermeable membrane. The funnel is then placed upside down
into a beaker which is filled with pure distilled water. The set up is done accord-
ing to the diagram shown (Figure 7-7):
Chapter 7 Liquids, Solids, and Phase Transitions

solution

membrane - Water

Figure 7-7 Osmosis experiment

The arrow indicates the direction of flow of the solvent (H,O).

Water will flow into the funnel through the semipermeable membrane,
and the liquid level of the funnel will gradually increase. The osmotic pressure
is the pressure required or applied to the solution to stop the flow of the solvent,
or in other words, to stop the process of osmosis. The osmotic pressure and
concentration are related by the following equation:

Osmotic pressure, 7~ = MR T

Here, M is the molar concentration of the solute,

R is the gas constant, and
T is the absolute temperature.
The MCAT Chemistry Book

CHAPTER 7 PRACTICE QUESTIONS Questions 5-10 are based on the following

passage.
1. The phase change that involves the conver-
sion of a gas to a solid is called: Passage 1

A. sublimation. A phase diagram illustrates the physi-

B. condensation. cal state of a substance with respect to the
C. freezing. temperature and the pressure of the surround-
D. deposition. ings. The points plotted to draw the phase
diagram are derived experimentally, and are
usually plotted with temperature on the x-axis
2. Which of the following processes accom- and pressure on the y-axis. A typical phase dia-
panies a release of heat? gram is shown below in Figure-l .

A. Vaporization
B. Condensation
C. Sublimation
D. Melting

3. Potassium fluoride is:

A. a covalent solid.
B. a metallic solid.
C. a network solid.
D. an ionic solid.

4. Which of the following is the strongest type

of force that is present in an ionic bonding? Temperature

A. London forces
B. Covalent forces Figure 1
C. Electrostatic forces
D. Hydrogen bonding forces
Chapter 7 Liquids, Solids, and Phase Transitions

5. Which of the following represents the 6. The phase diagram given in the passage
correct phase diagram of water? CANNOT be that of:

A. CO,
B. H,O
c. co
D. 0,

From the phase diagram given in the

passage, predict the likely phase change if
the following changes happen. Consider
point A as the current phase of substance
M. What is the most likely effect on
substance M, if the pressure was decreased
without changing the temperature of the
system?

A. Gas to liquid
B. Liquid to gas
C. Liquid to solid
D. Solid to liquid

8. The point marked 'X' in the phase diagram

given in the passage is called:

A. the critical point.

B. the maximum point.
C. the triple point.
D. the critical pressure point.

9. The critical temperature of a substance is

best defined as:

A. the temperature below which a gas can-

not be liquefied.
B. the temperature above which a liquid
cannot be vaporized.
C. the temperature above which a sub-
stance exists only as gas.
D. the temperature which is essential for a
substance to obey ideal gas laws.
The MCAT Chemistry Book

10. The segment XZ in the phase diagram given

in the passage represents the equilibrium
between:

A. gas and liquid.

B. liquid and solid.
C. solid and gas.
D. gas and plasma.
Chapter 8 Chemistry of Solutions

Chemistry of Solutions

A. INTRODUCTION

When we think of solutions, we normally think of a solution formed by

dissolving a solid (e.g., sugar) in a liquid (e.g., water). In reality, any combina-
tion of the three states can be considered a solution. In fact, air is a solution
which is a mixture of various gases. Carbonated water (soda) is a mixture of a
gas (CO,) dissolved in a liquid (H,O). Even alloys such as gold-silver alloys are
solutions containing two solids. A true solution is a solution which has only one
solvent with one or more solutes. In this chapter, we will be limiting our discus-
sion mostly to water based solutions because of their versatility and importance
to life sciences. We will discuss various aspects such as solubility of compounds,
and precipitation reactions.

B. THE CONCEPT OF SOLUBILITY

Solubility of a substance is defined as the amount of the substance that

will dissolve in a particular solvent. Let's consider an example in which sucrose
is added to water. When we add sucrose and' stir, it dissolves in the water. Let's
say we keep on adding more and more sucrose to the solution. Since more and
more sucrose is dissolving, the solution is not saturated or it is called an
unsaturated solution.

It reaches a point where additional amount of sucrose will not dissolve

in that solution. At that point the solution is said to be saturated. We have yet
another category in this tradition of categorizing solutions. In some cases, cer-
tain solutes become more soluble if the solution is heated. Such solutions are
called supersaturated solutions. If we carefully and slowly cool down a super-
saturated solution without disturbing its contents, normally we will still have a
supersaturated solution. At this stage, even the slightest addition of the solute
will result in crystallization. .
The MCAT Chemistry Book

The Reasons for Solubility

One basic rule that you have to keep in mind is "like dissolves like."
This means that substances which have similar polarity dissolve one another.
We know that water is a polar substance. Since oil is nonpolar, water and oil
cannot mix. Solubility helps in maintaining the lowest energy possible when the
solute and the solvent are mixed together.

Ionic Solutions

Ionic compounds have very peculiar solubility trends. Some are highly
soluble, whereas some others have very little solubility. The solubility of ionic
compounds can be explained in terms of the interactions between the ions and
the water molecules. Let's take sodium chloride as an example. Sodium chloride
has a solubility of 360 g per liter or 36 g per 100 ml at room temperature.

Since water is a polar molecule, when we add sodium chloride to water,

the water molecules will orient themselves according to the surrounding ions.
Here we have sodium @a+) and chloride (Cl-) ions. So the slightly negative
pole (the negative pole is due to the electronegativity of the oxygen atom) of the
water molecules will align toward the sodium ions, and the other pole will ori-
ent toward the chloride ions. This attraction is otherwise called hydration. Besides
hydration, there is another force called lattice energy of the crystal lattice. The
greater the lattice energy of an ionic solid is, the lesser its solubility.

C. MOLARITY

When we are working with solutions, it is better to have a concentration

measure in terms of the volume. Molarity is defined as the number of moles of
the solute per liter of solution.

moles of solute - - -mol

Molarity =
liter of solution L

D. MOLALITY

The molality of a solution is defined as the number of moles of the

solute per kilogram of solvent.

moles of solute
Molality =
kilograms of solvent
Chapter 8 Chemistry of Solutions

Molarity is usually denoted by the letter M, and molality is denoted by

the letter m.

Example 8-1

Calculate the molarity of a solution that contains 18.65 g of KC1 in 3 liters of

solution.

Solution:

We have 18.65 grams of KC1, and the total volume of the solution is 3 liters.
First, find the number of moles of KC1 present. The number of moles of KC1 is
0.25 mol, which can be calculated from the formula weight and the grams of
solute.

moles of solute
Molarity =
liters of solution

- 0.25 mol = 0.08 M

3L
E.NORMALITY

The normality (N) of a solution is the number of equivalents of solute

per liter of solution. The equivalent is usually defined in terms of a chemical
reaction. For acid-base reactions, an equivalent is the amount of substance that
will react or form 1 mole of hydrogen (H') or hydroxide (OH-) ions. For redox
(oxidation-reduction) reactions, an equivalent is the amount of substance that
will react or form 1 mole of electrons.

number of equivalents
Normality =
1 liter of solution

Normality is a multiple of molarity. The following equation relates normality

and molarity.

For acids, the number of H+ available from a formula unit of the acid gives the
number of equivalents (n). For example, 1 M H2S04solution is a 2 N solution,
because each molecule of H,S04 can give two H'. For bases, the number of OH-
available from a formula unit of the base gives the number of equivalents. For
example, a 2 M Ca(OH), solution is a 4 N solution.
The MCAT Chemistry Book

F. THE SOLUBILITY PRODUCT CONSTANT

Let's say we are adding silver chloride (AgC1) into a liter of water. We
can express the equilibrium as follows:

AgCl (s) ---

H20
- &+ (a91 + 61 (a91
The solubility product (Ksp)is defined as the equilibrium constant for
the solubility equilibrium of ionic compounds. The solubility product of AgCl
is expressed as:

The solubility product constant is equal to the product of the concentrations of

the ions in a saturated solution, each concentration raised to a power equal to its
coefficient (number of moles of individual ions formed per mole of the com-
pound) in the balanced equation.Take a look at the solubility product equation
of calcium fluoride (CaF,).

H2O -
CaF2 0 ) - - ca2' (aq) + 2 F (aq)

It is imperative that you understand these ideas involving the solubility

product constant.Let's look at another example. One mole of aluminum hydrox-
ide [Al(OH),] gives one mole of aluminum ions and three moles of hydroxide
ions in solution.
Al(OH), (s) 4 ~ 1 ~ + (+a ~
3 OH-(aq)
)

From the balanced equation, we can see that the coefficient of A13+is 1 and that
of OH- is 3. So, the solubility constant (Ksp) expression for AI(OH), is given
by:
Ksp = [A13+][OH-l3
The solubility product depends on the temperature, and at a given temperature it
is constant for a particular ionic compound. Molar-solubility is defined as the
number of moles of solute dissolved in one liter of its saturated solution. Using
the molar solubility of a compound, the solubility product of that compound can
be determined or vice versa.
 Chapter 8 Chemistry of Solutions

Example 8r2

Calculate the molar solubility of silver chloride (AgCl). The solubility product
KSp)of AgCl is 1.8 x 10-lo.

Solution:

AgCl(s) -
H20
- ~ g ( a+ d + ~i(aq)

Let x be the molar solubility of AgC1. So we can write:

Initial 0 0

Equilibrium x M xM

Ksp = [Ag'] [CL ] = (x) (x) = (x)' = 1.8 x lo-"

So the molar solubility of AgC1, x = 1.8 10- 10 = 1.34 10- M

Example 8-3

If 'x' represents the molar solubility of Al(OH),, find the expression for the
solubility product of Al(OH), in terms of x. What is the molar solubility of
Al(OH),, if the solubility product constant is 2 x 10-33?

Solution:

Al(OH), (s) M3+(aq) + 3 OK(aq)

Intial Concentration 0 0

1 Equilibrium concentration x 3x I
The solubility product expression is, Ksp= [A13+][OH-l3 = [x] [3xI3 = 27x4

Ksp= 27x4 = 2 x
The MCAT Chemistry Book

The solubility, = d s =-d = 2.9 x 1o - moll

~ L
You can approximate numbers to find the correct answer among the choices in
the MCAT. In this example, to take the 4th root of 7.4 x first we can
rewrite this as 74 x 1O-36.The 4th root of 8 1 is 3. Since 74 is less than 8 1, we can
approximate the 4th root of 74 close to 2.8 or 2.9. If you had trouble realizing
that, think of the 4th root of 16 which is 2. Again, the best approximation for the
4th root of 74 is a number below and close to 3. The 4th root of 10-36is 1O-9.
Such approximation-techniques can save time during the test.

Ion Product

Ion product is the product of the concentrations of the ions from the
compound (solute) in a solution, each concentration raised to a power equal to
its coefficient in the balanced equation. In other words, the expression for the
ion product is the same as that of Ksp.In a saturated solution, the ion product is
equal to Ksp.If the ion product is greater than Ksp,the solution is supersaturated
and can undergo precipitation. If the ion product is less than Ksp,the solution is
unsaturated. Thus, by comparing the ion product of a compound against its Ksp,
we can predict whether or not precipitation is likely to occur.

Unsaturated No precipitate is
Ion product < Ksp
solution formed
Saturated No precipitate is
Ion product = KSp
solution formed
Supersaturated Precipitation can
Ion product > KSp
solution occur

G . COMMON-ION EFFECT

When a salt is added to a solution containing either the same cation or

anion, there will be changes in the solubility because of what is commonly known
as common-ion effect. This is so because the solubility of the salt added is
affected by the common ions which are already present in the solution. Consider
a solution of sodium fluoride (NaF). We are adding magnesium fluoride (MgF,)
to this solution. Notice that there is a common ion in sodium fluoride and
magnesium fluoride, namely fluoride. You will see that the solubility of
magnesium fluoride will be less than expected. To be more precise, the solubility
of magnesium fluoride will be less than that of its solubility in pure water. Why
is it so? Well the answer is simple; common-ion effect. The phenomenon can
be best explained in terrns of Le Chatelier's principle. Consider the dissociation
of magnesium and sodium fluorides.
H20
~ g is)~ - 2 - ~ ++
M ~ (aq) 2F (aq) equation 1

NaF (s) -
H2O
- ~ a (aq)
' + F -(aq) equation 2

Magnesium fluoride is not a very soluble salt. It is a mildly soluble salt, whereas
sodium fluoride is a highly soluble salt. Because of the higher solubility of sodium
fluoride, there will be a lot of fluoride ions in the solution. This increased fluoride
ion concentration in the solution will drive the equilibrium of Equation 1 to the
left. Thus the solubility of magnesium fluoride will be highly diminished because
of the fluoride ions already present in the solution.

Table 8-1 Some general trends regarding solubilities (in water) of common ionic compounds

SOLUBLE IONIC COMPOUNDS

All salts of alkali metals (e.g., sodium, potassium), and ammonium ion are
soluble.
All nitrates, acetates, chlorates, and perchlorates are soluble.
All halides (chlorides, bromides, and iodides) are soluble. Exceptions include
lead(ll), mercury (I), and silver halides.
All sulfates are soluble. Exceptions include calcium, strontium, barium, and
lead(ll) sulfates.
INSOLUBLE IONIC COMPOUNDS

All carbonates and phosphates are insoluble except those of ammonium ion and
alkali metals.
All hydroxides are insoluble except those of calcium, strontium, barium, and
alkali metals.
All sulfides are insoluble except those of alkali metals and ammonium ion.
The MCAT Chemistry Book

H. ELECTROLYTES

Pure distilled water is not a good conductor of electricity. If KC1 is added

to it, the resulting aqueous KC1 solution becomes a good conductor of electric-
ity. Such a substance that dissolves in water to give a solution that can conduct
electricity is called an electrolyte. The free ions that are present in an electro-
lytic solution enable the flow of electric current. Most ionic substances are good
electrolytes because they dissolve in water as ions. A substance that exists al-
most completely as ions in a solution is called a strong electrolyte. Hydrochloric
acid is a strong electrolyte because when HC1 is dissolved in water, it com-
pletely exists as H,O+ and C1- ions by reacting with water (H,O).

Some substances (solutes) form aqueous solutions that weakly conduct

electricity. Such substances are called weak electrolytes. This weak conduction
of electricity is mainly because weak electrolytes only dissociate partially in
solution. In other words, only a small fraction of the solute exists as ions, result-
ing in a solution that conducts electricity very weakly. Acetic acid (CH,COOH)
and ammonia (NH,) are examples of weak electrolytes.

A substance that can dissolve in water but results in a poorly conducting

solution is called a nonelectrolyte. Glucose (C,H!,O,) is a nonelectroly~e.A
nonelectrolyte is not charged in solution because it dissolves as molecules in
water rather than ions, and thus cannot conduct electricity.
Table 8-2

SOME COMMON POLYATOMIC IONS

Acetate (C2H30; ) Nitrate (NO; )

Ammonium (NH: ) Nitrite (NO; )

Bicarbonate (HCO~-) Oxalate ( ~ ~ )0 ;

Bisulfate (HSO; ) Perchlorate ( ~ 1 0 4)

Bisulfite (HSO~-) Permanganate ( ~ n 0 4)

Carbonate (~0:- ) Peroxide (0; )

Chlorite ( ~ 1 0 2) Phosphate (PO:-)

Chromate ( c ~ o2-~) Sulfate (so3- )

Cyanide (CN 3 Sulfide (s2- )

Dichromate ( C r 2 0 T )
-
Dihydrogen phosphate (H,PO; ) Thiosulfate ( ~ ~ ) 0 , ~

Hydroxide (OH- ) Oxide (0:)

Hypochlorite ( ~ 1 0 )-
The MCAT Chemistry Book

CHAPTER 8 PRACTICE QUESTIONS 5. How many grams of NaCl are required to

prepare 250 ml of 0.35 MNaCl solution?
1. Equivalents of solute per liter of solution
is:

A. molality.
B. molarity.
C. normality.
D. none of the above.
Questions 6-10 are based on the following
passage.
2. The concentration of a given solution of
glucose (C6H,,06)is 270 g per liter of solu- Passage 1
tion. What is the molarity of this solution?
The concentration of solutions are gen-
erally expressed in terms of molarity, molality,
normality, and weight percent. The formation
of the solutions itself has many ramifications.
The solubility of solutes differ considerably
from one other. Some of the factors that can
influencethe solubility include temperature and
3. You are presented with a 2.5 M solution of pressure. Solubility depends on other factors
hydrochloric acid. If the total volume of the as well. Given below in Figure-1 is a graph
solution is 1.25 L, how many grams of HCl which depicts solubility differences of some
is present in this solution? solutes.

4. You are asked to prepare 30 ml of a 2 M

solution of HNO, fiom a stock solution of
10 M solution of HNO,. How much of the
stock solution is required to make this 30
ml of 2 M HNO, solution?

Temperature
Figure-1
 Chapter 8 Chemistry of Solutions

Quite often, the freezing and boiling A solution was made by using 3 15 g of glu-
point changes that are brought about by the dis- cose in 750 g of water. What is the boiling
solved solutes can be predicted reasonably. But point of this solution?
this is not always the case.

The predictions and calculations are

done for freezing point depression (ATJ based
on the following formula:

AT, = K, m,
Two experiments were conducted for
where m is the molality and K, is the freezing analyzing the solubility properties and their
point depression constant. (Kf = 1.86 "Clm) effects on colligative properties. In
Experiment I, a 1.0 m solution of KBr was
For boiling point elevation (AT,), the calcula- analyzed and in Experiment 11, a 2.3 m
tions are based on the following formula: solution of KBr was analyzed. The
experimental values of freezing and boiling
AT, = K, m, points were slightly different from the
expected values based on the theoretical
where m is the molality and K, is the boiling calculations discussed in the passage.
point elevation constant. (Kb = 0.512 "Clm) Which of the following is most likely
correct regarding the two experiments?

6. The graph in the passage shows the solu- A. The experimental values of the solution
bilities of some compounds (salts). Which in Experiment I was more different fiom
of the following is most likely true regard- the theoretical calculations than the
ing the Compounds A, B, C and D? solution in Experiment 11.
B. The experimental values of the solution
A. The solubility process of Compound B in Experiment I1 was more different
is exothermic, and those of Compounds from the theoretical calculations than
A, C and D are endothermic. the solution in Experiment I.
B. The solubility process of Compound B C. Both experiments have the same extent
is endothermic, and those of Com- of differences from the theoretical
pounds A, C and D are exothermic. predictions.
C. The solubility processes of Compounds D. The discrepancy noted in the experi-
A, ByC and D are exothermic. ments is absolutely a result o f
D. The solubility processes of Compounds instrumental error, because the differ-
A, B, C and D are endothermic. ences in Experiments I & I1 cannot
change colligative properties.
The MCAT Chemistry Book

9. If the amount of glucose used in Question

7 is doubled, while the same 750 g of water
was used, what must have happened to the
boiling point of the solution?

A. It doubled.
B. It quadrupled.
C. It decreased slightly.
D. It increased slightly.

10. Which of the following statements is true

regarding solutions?

A. As the concentration of a solution

increases, the vapor pressure increases.
B. As the concentration of a solution
decreases, the vapor pressure decreases.
C. As the concentration of a solution
increases, the vapor pressure decreases.
D. None of the above
Chapter 9 Acid-Base Equilibrium

Acid-Base Equilibrium

A. INTRODUCTION

In this chapter, we will explore different aspects involving acids and

bases. We will start with the definitions, followed by ionization reactions,
including various key concepts involving strong acids, strong bases, weak acids,
weak bases, and buffers. Finally, we will discuss some of the important titration
reactions.

B. DEFINITIONS OF ACIDS AND BASES

The Arrhenius Definition

According to Arrhenius, an acid is a substance that increases H+ ions in

an aqueous solution. A base is a substance that increases OH- ions in an aque-
ous solution. The Arhhenius definitions explain the reactions involving acids
that contain acidic hydrogens, and bases that contain basic hydroxyl groups
(e.g., metal hydroxides). But the definitions are not able to explain the behavior
of acids and bases of other types, such as in nonaqueous solutions.

The Bronsted-Lowry Definition

During the early twentieth century, scientists J.N. Bronsted and T.M.
Lowry put forth their theories. According to them, an acid is a proton donor,
and a base is a proton acceptor.

Consider the ionization reaction of hydrogen iodide. Since hydrogen

iodide is a strong acid, it completely dissociates. In this ionization reaction, note
that the water molecule acts as the base.
 The MCAT Chemistry Book

-
-
H' (aq) + H 2 0 ( I ) H,O+

1
- - - - - -- - - -

Hl (aq) + H 2 0 ( I ) H,O+ + l<aq) Overall reaction

THIS REACTION IS AN EXAMPLE THAT FITS THE BRONSTED- LOWRY DEFINITION

In this ionization reaction, obviously HI is the acid. HI transfers or donates
its proton to water. Thus, water is the base in this reaction because it accepts the
proton. The conjugate base of HI is I-.

C. THE LEWIS THEORY

The scientist G.N. Lewis put forward a more elaborate theory regarding
acids and bases. According to him, a Lewis acid is a species that can accept a
pair of electrons from another species. He defined Lewis base as any species
that can donate a pair of electrons to another species. For a thorough under-
standing of this concept, let's look at a typical Lewis acid-base reaction. The
reaction between ammonia (NH,) and boron trichloride (BC1,) is shown:

- .. ..
Lewis acid-electron pair
acceptor :B H
0.

:C1 H
0. 0
. 0. 0. 0.
:c1 :B + :N:H :C1 :B:N:H
Lewis base-electron pair '0 0. 0. 00

donor :C1
** H tC1 H
0.

Lewis acid Lewis base

In this reaction, the electron acceptor is boron trichloride (Lewis acid)

and the electron donor is ammonia (Lewis base). The new bond that is formed
between the acid and the base is a coordinate covalent bond.

D. IONIZATION OF WATER

Usually pure water is considered to be a nonelectrolyte. Nevertheless, it

actually can conduct small amounts of electricity. This is because of the self-
ionization of water. Since the species that act as the acid and the base are one
and the same, we can describe it as follows:
Chapter 9 Acid-Base Equilibrium

A proton is grabbed from one water molecule, and is accepted by another water
molecule. The resulting products are hydronium and hydroxide ions.

The equilibrium expression (K,) is written as:

K, = [ H,O+] [ OH-] = 1.0 x 10-l4at 2.5" C

K,, is more correctly called the ion-product constant for water, which is actually
the equilibrium value of the ion product.

E. THE CONCEPT OF pH

In order to describe the acidity of a solution, scientists have devised the

pH scale. The pH is defined as the negative log of the hydrogen-ion concentration.

Example 9 -1

What is the pH of a solution having a 1x 10-2M hydrogen-ion concentration?

Solution:

The formula for pH is pH = - log [ H+1. Substituting in this formula,

pH = -log(lx = 2

The pH of this solution is 2.

We can also find pH if we know the hydroxide-ion concentration.

pOH = - log [OH-]

Since pH + pOH = 14, if we know the pOH, the pH can be easily calculated or
vice versa.
The MCAT Chemistry Book

Example 9-2

Find the pH of solution X, if it has a hydroxide-ion concentration of 1x 10- M.

Solution:

Since the hydroxide-ion concentration is 1x 10- M, the pOH is 8. Since we

know that pH + pOH is 14,

The pH value of solution X is 6.

E STRONG ACIDS AND BASES

Strong acids such as HNO,, HC1, and HI dissociate almost completely.

If we were asked to predict the direction of such a dissociation reaction, we
should say that the direction of reaction favors the dissociation of the acid. The
dissociation of HI is shown below:

HI (aq) + H 2 0 (1) H,O* (aq) +

Since there is complete dissociation for every mole of HI present, equal

number of hydronium ions are formed. You may be wondering whether protons
can be supplied by the water molecules that are present. Usually this supply is
negligible (the self-ionization of water is extremely low) compared to the con-
centration of the strong acid present. But this may not be always the case. Think
about an instance when the proton contribution of water is significant in an
acidic solution such as that of hydrogen iodide. When you have a strong acid
solution which is very dilute, water does contribute protons significantly com-
pared to that of the strong acid present.

Now let's consider a strong base such as potassium hydroxide. Let's say
the solution is 1 x 10-3M. Since KOH is a strong base, it dissociates completely.
So we can confidently say that the concentration of hydroxide-ion formed is
also 1 x lo-, M. Just like the strong acid, we can ignore the possibility of
hydroxide-ion formation from water, since the self-ionization of water is
negligible. Since the OH- concentration is 1 x the pOH is 3. From this, we
can say that the pH of this solution is close to 11, since pH + pOH = 14.

A pH value below 7 is acidic, a pH value above 7 is basic, and a pH value 7 is

neutral.
Chapter 9 Acid-Base Equilibrium

Table 9-1

SOME EXAMPLES OF STRONG ACIDS

acid
H P S H P++ CI-
base

Sulfuric acid H2S04 HCI +

Nitric acid HN03 acid base
Hydrochloric acid HC1
In this reaction, HCl
Hydrobromic acid HBr
(acid)reacts toform CI -
Hydroiodic acid HI
(base). HCI and C1 c a n
Perchloric acid HClO,
be inter-convertedby the
Chloric acid HC10,
gain or loss of one
proton. Such a pair is
SOME EXAMPLES OF STRONG BASES
called a conjugate acid-
base pair. Here, C1 - is
Lithium hydroxide LiOH
the conjugate base of
Sodium hydroxide NaOH
HCI, and HCI is the
Potassium hydroxide KOH
conjugate acid of Cl -.
Cesium hydroxide CsOH
Calcium hydroxide Ca(OH),
Strontium hydroxide Sr(OH),
Barium hydroxide Ba(OH),

G . WEAK ACIDS AND BASES

Weak acids and bases cannot dissociate completely. They undergo the
same type of dissociation as that of strong acids and bases, but the extent of
dissociation is very little compared to strong acid or strong base dissociations.

Acid-ionization Constant (Ka)

A typical way to represent the dissociation of a weak acid is shown below:

HA ( a d
weak acid
+ H20 (1) - - H30 (aq) + A-

In this reaction, the protons from the weak acid are transferred to the water
molecules. The acid-ionization constant (KO)of this reaction is shown below:

[ H ~ O +I [ A-I
Acid-ionization constant, K, =
[HA1

We encounter weak acids every day. An example is carbonated water that

contains dissolved carbon dioxide, and is called carbonic acid. Fruits like lemons
and oranges contain citric acid which is also a weak acid. The list goes on and on.
The MCAT Chemistry Book

Percentage Ionization

Percentage ionization is the percentage expression of the degree of ion-

ization. What is the degree of ionization of a weak acid? Degree of ionization is
the fractional amount of the weak acid that gets ionized.

Example 9-3

Find the degree of ionization of 0.1 M solution of acetic acid (CH,COOH). Also
find the pH of the solution.
(The acid-ionization constant of acetic acid is 1.8 x 10-5)

Solution:

-
CH3COOH (aq) - ~ + ( a ~ ) + CH3COO(oq)

We will logically dissect the events that lead to the dissociation. At first we do
not have any H+and CH,COO- ions. Let's say we have a unit volume (a liter) of
acetic acid and x M (mol/L) of it was ionized. We can represent the equation as
follows:

CH3COOH (aq) , - ~'(aq) + C H ~ C O(aq)

O
Initial 0.1 M -0 -0
At equilibrium (0.1 - x) M x M xM

With the concentrations at equilibrium we can substitute the concentrations in

the acid-ionization constant expression.

[ H*] [ CH3COO- ]
Acid-ionization constant, K, =
[ CH3COOH ]
Chapter 9 Acid-Base Equilibrium

Even though this has to be solved using a quadratic equation, we can skip that
elaborate process by making some chemically acceptable assumptions. Since
the acid-ionization constant is very small, we can assume the same with the
value of x. So the expression changes as follows. For the MCAT, you won't be
given problems that require extensive calculations. The problems will test mostly
concepts, and when calculations are involved the numbers will usually be man-
ageable ones.

(XI * ( x ) ~-
becomes - - 1.8 X 1 0 - ~
(0.1 - x) 0.1

Solving for x you will get roughly 1.34 x 10' = 0.001 34 M.

Degree of ionization = 0.00134 = 0.0134

0.1

The question also asks for pH of the solution.

pH = - log [ H+]

The hydrogen ion concentration is 0.00134 M. By substituting in the pH for-

mula you should get the following result.

The pH of the solution is 2.87.

Base-ionization Constant (K,)

Just like the acid-ionization constant, there is also the base-ionization

constant. Consider the ionization of ammonia in water.

For the above reaction, we can write the base-ionization constant (K,) for the
above reaction as follows:

Base-ionization constant, Kb =
The MCAT Chemistry Book

H. DISSOCIATION OF POLYPROTIC ACIDS

Some acids have two or more protons that can be released upon disso-
ciation. Such acids are called polyprotic acids. For example, phosphoric acid
(H3P04)can lose up to three protons in aqueous solution.

-
Sulfuric acid is a polyprotic acid that can lose two protons in solution. The first
ionization is complete because sulfuric acid is a strong acid.
H2SO4(aq) ~ ' ( a ~+) HS0,-(aq) Dissociation constant, Kal= very large

The second proton comes off as depicted by the next equation. In this case,
an equilibrium exists because hydrogen sulfate ion (HS04-) is not as strong
as H,SO,.
HS04- ( a d - -
~ ' ( a q ) + s0:-(aq) Dissociation constant, Ka2= 1.2 xl o - ~

It is clear from this example that the second dissociation constant is always
lower than the first dissociation constant. Thus, it is easier to remove a proton
from an uncharged species (H,S04) than from a charged species (HS0,-).

Based on the Bronsted-Lowry definition of acids and bases, an acid is a proton

donor and base is a proton acceptor. A species (charged or uncharged) that can
gain or lose a proton is called arnphoteric or arnphiprotic species. For example,
(bicarbonate ion) HC03- can donate a proton acting as an acid. The same spe-
cies can accept a proton acting as a base. Hence, amphoteric species can act as
an acid or a base depending on the surrounding conditions.

under basic conditions, HC03- can act as a Bronsted-acid

I >
- ~'(aq) + C O ~ ~ - ( ~ )

under acidic conditions, HC03- can act as a Bronsted-base

Chapter 9 Acid-Base Equilibrium

I. DIFFEWNTIATING ACIDIC AND BASIC SALTS

Salt solutions can be acidic, neutral, or basic. Let's consider a salt solu-
tion of NaF. NaF dissolves in water to form sodium and fluoride ions.

While the sodium ion is not reactive to water, the fluoride ion is reactive to
water (fluoride is the conjugate base of a weak acid, HF). The fluoride ion can
act as a base by accepting a proton from H 2 0 by the process of hydrolysis. The
reaction is shown below.
H20(1) + F-(aq) a HF(aq) + OH-(aq)
The increased presence of hydroxide ions (notice the formation of hydroxide
ions as one of products of the hydrolysis reaction) makes the solution basic.
This strategy can be used to predict whether a salt solution is acidic, basic, or
neutral.

1. A salt of a strong base and a strong acid gives a neutral aqueous solution.
Eg: NaCl is a salt of a strong acid (HC1) and a strong base (NaOH).
2. A salt of a weak acid and a strong base gives a basic aqueous solution.
Eg: NaCN is a salt of a weak acid (HCN) and a strong base (NaOH).
3. A salt of a weak base and a strong acid gives an acidic aqueous solution.
Eg: Zn(NO), is salt of a weak base (Zn(OH),) and a strong acid (HNO,).
The MCAT Chemistry Book

J. BUFFERS

A solution which resists changes in pH when small amounts of acid or

base are added to it is called a buffer solution. A buffer solution is usually a
mixture of a weak acid and its conjugate base or a weak base and its conjugate
acid. A buffer solution contains equilibrium amounts of acid and base species.
Consider a buffer solution containing equal molar amounts of a weak acid
(H,CO,) and its conjugate base (HC0,-).

If a strong acid is added to this buffer solution, the H' concentration

increases and they react with the base (HCO;) thereby decreasing the H'con-
centration and maintaining the initial pH. On the other hand, if a strong base is
added, the OH- ions supplied by it will react with the H+ so that more of H,CO,
will dissociate thereby restoring the initial pH. In this case, when a strong acid is
added, the equilibrium shifts to the left. When a strong base is added, the equi-
librium shifts to the right. In both cases, the pH or the hydrogen ion concentra-
tion is maintained. This does not mean that a buffer solution can maintain a
constant pH no matter how much acid or base is added. In other words, buffers
do not have unlimited capacity to resist pH-change. The buffer capacity of a
buffer depends on the nature of the buffer and the amount of acid and conjugate
base present in the solution. The buffering capacity (the amount of acid or base
the buffer can resist) of a buffer can be increased by increasing the concentra-
tion of the acid-conjugate pair. The Henderson-Hasselbalch equation can be
used to relate the pH of a buffer and the concentrations of base and acid.

[conjugate base]
For a weak acid-conjugate base buffer, pH = pK, + log
[weak acid]
In a weak acid buffer solution, when the concentrations of the weak acid and its
conjugate base are equal the pH of the solution is equal to the pKa of the weak
acid.
[conjugate acid]
For a weak base-conjugate acid buffer, pOH = pK, + log [weak base]
In a weak base buffer solution, when the concentrations of the weak base and its
conjugate acid are equal the pOH of the solution is equal to the pKb of the weak
base.
Chapter 9 Acid-Base Equilibrium

K. TITRATION CURVES OF ACIDS AND BASES

Acid-base titrations are reactions by which we can determine the amount

of acid or base present in a solution. This is done by reacting the solution with a
base or acid (of known concentration), and by measuring the volume of the known
acid or base used up in the process. The reaction data is usually plotted with the
volume of the substance (concentration known) in the x-axis, and the pH of the
solution in the y-axis. The graph is called a titration curve.

Take a look at the first titration plot (Figure 9- 1) given. You will see a
steep region in the plot. The center of this steep region is called the equivalence
point. The equivalence point denotes the point at which equivalent amounts of
acid and base have reacted. To know the equivalence point, we usually add an
indicator which will change its color close to the equivalence point. We can use
the following relation to equate the amount of acid or base present in a solution
against the volume of acid or base added whose concentration is known.

N,V,= N,V,

where N, is the normality of the unknown acid or base,

N, is the normality of the known base or acid,
V, is the volume of unknown acid or base, and
V, is the volume of the known base or acid.

Indicators

An indicator is usually used to detect the equivalence point in an acid-

base reaction or titration. The most common indicators used are weak organic
acids or bases that change color in response to a change from acidic to basic
medium or vice versa. The pH at which the color change occurs is characteristic
of each indicator. For an acid-base reaction, the indicator is chosen based on the
pH at which the equivalence point is expected to occur. Consider the hypotheti-
cal dissociation reaction of an indicator represented by HIn.
HIn -' H+ + In-
yellow blue
color color

Let's consider a scenario in which the indicator is in an acidic solution.

Acidic solution means there is excess H+.So the equilibrium will shift to the left
(LeChatelier's principle), and the predominant species will be HIn making the indi-
cator show yellow color. On the other hand, in a basic solution, the equilibrium will
The MCAT Chemistry Book

shift favoring the forward reaction and the predominant species will be In-(blue
color). Because HIn (acid form) and In have different colors, this can indicate
the equivalence point of acid-base reactions. You might be thinking that the
dissociation of the indicator used itself might change or affect the pH of the
tested solution. But this is negligible because only a tiny amount of the indicator
is needed to show a visible color change.

Table 9-2
Some Common Indicators
Chapter 9 Acid-Base Equilibrium

Titration of a Strong Acid with a Strong Base

Consider the titration reaction involving HC1 against NaOH. Let's say
that we have 50 ml of a 0.1 M solution of HC1, titrated with 0.1 M solution of
NaOH. As we add NaOH into the solution of HC1, initially the pH increase will
not be very drastic. The pH increases slowly. When certain amount of NaOH is
added, the change in pH becomes more drastic and the plot becomes very steep,
as indicated in the plot (Figure 9-1). At this steep region, the equivalence point
is reached. Can you guess the pH at the equivalence point? If you guessed 7, you
are right. At the equivalence point of this titration you have a salt which is
neutral, and hence the pH is 7.

pH of
the
solution

Volume of NaOH added in mL

'==3
Figure 9-1
The MCAT Chemistry Book

Titration of a Weak Acid with a Strong Base

The curve of a weak acid-strong base titration is different from that of

the plot we learned for the strong acid-strong base titration. Unlike the previous
curve, this plot will have a region which has buffering properties. Besides that,
the equivalence point will be above the pH value 7. The general shape of the
curve is shown in Figure 9-2.

14 --

12 --

10 --

pHof
the
'--
6 --
solution

Volume of base added

i
Figure 9-2
Chapter 9 Acid-Base Equilibrium

Titration of a Weak Base with a Strong Acid

The trend seen in the weak base-strong acid titration curve is somewhat
similar to that of the weak acid-strong base curve. At first, as we add the acid,
the pH slowly decreases. Then the decrease in pH becomes drastic, as you can
see in Figure 9-3.

pHof 7 - -
the 6--
solution Equivalence point

4 --

2 --

-
Volume of acid added

Figure 9-3
The MCAT Chemistry Book

CHAPTER 9 PRACTICE QUESTIONS [conjugate acid]

C. logK, + log [OH-]= log
[base]
1. If the pH of a solution is 2.5, what is the
concentration of H30+in that solution?
D. None of the above are valid.

5. Which of the following species has the

highest pKa value?

A. H,PO,-
2. NaCl solution is most likely: B. H3P04 -
C. HP0,2
A. acidic. D. All the above species have almost the
B. basic. same pKa values, since they all have the
C. neutral. same type of phosphate anionic
D. cannot be predicted. counterpart.

3. Which of the following is NOT a polyprotic Questions 6-10 are based on the following
acid? passage.

A. H2S0, Passage 1
B. H2P04-
C. H,As04 Strong acids and bases ionize
D. None of the above completely in aqueous solutions. Weak acids
and bases ionize only partially in aqueous
solutions. An acid-base reaction is shown
4. Based on the equation, below. A titration was done by adding a base
[conjugate acid] to a known concentration and fixed volume of
pOH = pK, + log [base]
an acid. The reaction follows:
Reaction 1
which of the following is NOT valid?
HC104 (aq) + NaOH (aq) -NaC1O4 (aq) + H 2 0 (I)
[conjugate acid]
A. logK, = log [OH-]+ log
[basel The dissociation of a weak acid can be repre-
sented as:

logK, = log [OH-]- log [basel

B.
[conjugate acid:
Chapter 9 Acid-Base Equilibrium

Chemists often use Henderson-Hasselbach 7. The titration curve of the acid-base reac-
equation to calculate the pH of solutions con- tion (Reaction 1) is best represented by:
taining a weak acid of known pKa, provided
that the other concentrations are known. A.
Henderson-Hasselbach equation is:

pH = pKa [A-
+ log - I
[HA]

This equation is also used to calculate the buff-

ering capability of solutions. It is roughly esti-
mated that a given buffer is most likely to be NaOH
effective at pH levels between (pKa + 1) and
B.
(pKa - 1).

6. The net ionic equation of Reaction 1 is:

0
- pH
H' (aq) + OH (aq)

-
A. + H20 (I)

B. Nai (aq) + C I (aq)

~ NaClO, (aq)

-
C- H' (aq) + ~10;(aq) + ~a'(aq) + ~ ~ ( a q )
Na+ (aq) + ~10; (aq) + H20 (1)
D. Perchloric acid is a weak acid and cannot
NaOH @

ionize completely, so that net ionic equation

cannot be written.

NaOH 0
The MCAT Chemistry Book

8. What are the base-to-acid ratios correspond-

ing to the lower and upper limits of pH val-
ues which make the best buffer?

A. lOand 1
B. lOOand 1
C. 0.01 and 10
D. 0.1 and 10

9. What is the pH of a 3.2 x M solution

of HCl?

10. The pH at which the base and the acid con-

centrations equal in a buffer system is called
the:

A. equivalence point.
B. pKa.
C. neutralization point.
D. non-buffering zone.
Chapter 10 Thermodynamics

Thermodynamics

A. INTRODUCTION

In this chapter, the review will mainly focus on the laws of thennody-
namics and their implications. The discussion includes concepts such as enthalpy,
entropy, specific heat, heat capacity, Gibbs free energy, spontaneity of reactions,
and related aspects. We have many ideas to discuss. So buckle up!

What is Thermodynamics?

In our busy modern life, we often forget about the fundamental aspects
of today's life that make it so unique. Everyday we use machines and gadgets,
big and small, which depend on some type of energy. We harvest the available
energy and use it in many ways. But how is this done? We use natural energy
sources such as coal, petroleum products, and nuclear energy. The question is,
what are the fundamental principles regarding the harvesting of energy from
these sources? It is by chemical reactions that we make use of the hidden energy
available from these sources. What we learn from thermodynamics is the
dynamics of energy (heat) transfer during chemical changes. In this chapter, we
will review the various aspects of thermodynamics and the related principles.

B. THE FIRST LAW OF THERMODYNAMICS

According to the first law of thermodynamics, energy is neither cre-

ated nor destroyed, which also implies that the total energy present in the whole
universe is constant. Based on this law, we can say that the energy is just taken
from one form and converted to another form. This is exactly what we are doing
when we are burning fuels such as gasoline to get sufficient energy to run the
internal combustion engine, or when we are using nuclear reactions to turn the
turbines of a nuclear power plant,to make electricity.
The MCAT Chemistry Book

Basic Aspects of Thermodynamics

First, let's talk about internal energy. Internal energy of a substance is

the total energy present in the particular quantity of that substance. For a chemical
reaction or a physical change of reactants, the change in internal energy (A E ) of
the reactants is expressed as follows:

Change in internal energy,

A E = Final internal energy (E,,,,) - Initial internal energy (Einitia,)

AE= Q +W
Here, Q represents the heat and W represents the work done.

Based on the above equation, these conventions are followed:

When heat is absorbed by a system, heat (Q)is positive.

When heat is given off by a system, heat (Q)is negative.
When work is done on a system, work (W) is positive.
When work is done by a system, work (W) is negative.

C. ENDOTHERMIC AND EXOTHERMIC REACTIONS

The change in heat for chemical reactions at constant pressure is called

enthalpy change, denoted by AH. The change in enthalpy (AH) of a reaction is
represented as shown below:

* = Hpro~ucts H reactants

If the reaction is endothermic, the change in enthalpy is positive. In an

endothermic reaction, the enthalpy of the reactants is less than the enthalpy of
the products. So the reaction is accomplished by supplying energy to the reaction.
On the other hand, the change in enthalpy is negative if the reaction is exothermic.
Energy is released in this case. Also it is worth remembering that in an exothermic
reaction, the enthalpy of the reactants is greater than the enthalpy of the products.
Hence, if we have the enthalpy data, we can predict whether the reaction is
endothermic or exothermic.

D. LAW OF HEAT SUMMATION

According to the law of heat summation put forth by Henri Hess, we

can find the total enthalpy of a reaction by adding the enthalpy changes of the
 Chapter 10 Thermodynamics

individual steps in a reaction. It doesn't really matter if the reaction occurs in

many steps or in one step. As long as the enthalpy values that we sum up are
correct, we will get the overall enthalpy change.

Law of heat summation: The total enthalpy of a reaction can be derived by

adding the enthalpy changes of the individual steps in the reaction.

Example 10-1

Calculate the AH of the reaction between HC1 and fluorine, forming HF and

2 HC1 (g) -
chlorine. The enthalpies of the related reactions are also given.
+ F2 2 HF (1) + C12 (g)

(Reaction 1) HC1 (g) + 114 O2 (g) - 11 2 H 2 0 (1) + 112 C12 (g) -37.1 kJ/mol

(Reaction 2) 2 HF (1) - H2 (g) + F2 (g) +I200 kJ/mol

(Reaction 3)

Solution:

AH

2HCl(g) + 1/202(g) - H2O (1) c12 (g) - 74.2 kJ/mol

-
+

- 1200 kJ/mol

-
H2 (g) + F2 (g) 2 HF (1)

H20 (1) H2 (g) + 11 2 0 2 (g) + 285.8 kJ/mol

Overall reaction:
2 HC1 (g) -
+ F2 2 HF ( I ) + C12 (g) - 988.4 kJ1mol

The individual reactions that are given have to be reversed if necessary, so that
the sum of the sub-reactions will add up to the overall equation. Reaction 1
should be multiplied by 2. The second and third reactions should be reversed.
This applies to the corresponding enthalpy values as well. That means, if the
reaction is reversed the sign of the corresponding change in enthalpy should
also be reversed. The enthalpy of the overall reaction is -988.4 kJ/mol.
The MCAT Chemistry Book

E. THE SECOND LAW OF THERMODYNAMICS

We learned how to predict the mode of a reaction in terms of whether

the reaction will be endothermic or exothermic. In this section, we will explore
the dynamics and the factors that influence the spontaneity of reactions. For
that, we have to be familiar with the term "entropy."

Entropy (S) is the measure of how disordered a system is. The entropy
is dependent on the prevailing conditions such as pressure and temperature.
From the MCAT point view, the values of entropy and related aspects that you
will be dealing with are at standard state. The standard state refers to 1 atm
and 25" C.

Entropy of a system is the measure of disorder or randomness of the system.

Let's talk more about entropy. The higher the disorder is, the greater the
entropy of that system. In terms of the phases of matter, think about which phases
will have a higher entropy. We can generalize that the gas phase of a substance
has higher entropy than its liquid phase, and the liquid phase has higher entropy
than its corresponding solid phase. Thus, as the temperature increases the entropy
increases. The change in entropy (AS) is equal to the final entropy minus the
initial entropy.

According to the second law of thermodynamics, there is an overall

natural tendency toward disorder. You have to understand that we are talking
about the overall entropy. Do not confuse this with the fact that we sometimes
look at individual systems or reactions and categorize them as having either
. increasing entropy or decreasing entropy. But the overall entropy of all the events
together is increasing.

Example 10-2

Solution:
co2 (4 -
Predict whether the entropy is increasing or decreasing for the following change.

co2 (g)

The question asks whether the entropy of the system is increasing or decreasing
for the above written equation. Your response should be that there is an increase
in entropy. Why? As we discussed, the change in phase is the key aspect to
watch here. Carbon dioxide is changing from its solid form to gaseous form.
Hence, the randomness of the system is increasing. So the entropy is increasing.
Chapter 10 Thermodynamics

Example 19-3

Predict whether the entropy of the system is increasing as the reaction given
below goes to completion.

Solution:

The reaction shown above is the combustion reaction of acetylene. This reaction
is made use of in welding, commonly called the "acetylene torch." Tremendous
amount of heat is liberated as a result of this reaction and is used for welding
purposes. As you can see from the equation, the number of moles of the reactants
is greater than the number of moles of the products. Thus, as the reaction proceeds,
there is a decrease in the number of moles of gas. If you predicted a decrease in
entropy, your answer is correct.

F. THE THIRD LAW OF THERMODYNAMICS

) Temperature (K)

Figure 10-1 Entropy versus temperature

The MCAT Chemistry Book

Let's state the third law of thermodynamics. The law states that pure
and perfect crystalline substances have an entropy of zero at 0 Kelvin. What
does that mean? It means that a pure crystalline substance will have perfect
order at absolute zero temperature. An increase in temperature will destroy this
zero entropy. By looking at the graph (Figure 10-l), it is clear that an increase in
temperature increases the entropy.

G. FREE ENERGY

Free energy denoted by the letter G is a thermodynamic quantity, with

which we can predict the spontaneity of a reaction. The change in free energy
(AG) is related to the changes in enthalpy and entropy, and temperature as indi-
cated by the equation:

AG = AH - TAS

Here, AG represents the change in free energy, AH represents the change in

enthalpy, AS represents the change in entropy, and T represents the temperature.

How Can We Predict Spontaneity?

On the basis of free energy change we can predict the spontaneity of a

reaction. You should be able to manipulate the above mentioned equation, and
once you have found the free energy change, you can do the prediction using the
following guidelines.

If AG is positive, the reaction generally is nonspontaneous. If AG is nega-

tive, then the reaction is generally spontaneous. The changes in free energy and
spontaneity depend on the change in enthalpy as well as the change in entropy.
Besides these two important factors, the temperature at which the reaction takes
place also plays a major role in dictating the spontaneity of reactions. Take a
look at Table 10-1.

Table 10-1

AG AH AS
Spontaneous at all
temperatures
- +
Spontaneous at low - -
temperatures

Spontaneous at high
temperatures + +
Nonspontaneous at all
temperatures + -
Chapter 10 Thermodynamics

H. TEMPERATURE - SOME BASICS

We use the term temperature quite a lot in Chemistry, but how can we
define it? Students often get conhsed with the terms temperature and heat. Even
though temperature and heat are related, they are not the same. Let us consider
two objects that are at different temperatures; a hot object and a cold object.
Let's say we kept them in close proximity for some time. The heat passes from
the hot object to the cold one, until they reach equilibrium. So it is the heat
(energy) that passes from the hot object to the cold one resulting in a change in
temperature.

The common scales used to denote temperature are the Celsius scale
and the Kelvin scale (K). The SI unit of temperature is actually kelvin (K). The
Celsius and the Kelvin scales can be easily converted back and forth, and are
related by the following simple relations:

The other temperature scale that we are more familiar with is the Fahr-
enheit scale. Temperature denoted in degree Celsius can be converted to degree
Fahrenheit using the following relation:

You are expected to know these conversions at this level of study in college.
So know them!
The MCAT Chemistry Book

CHAPTER 10 PRACTICE QUESTIONS C . Entropy is not affected since the change

does not constitute an actual reaction,
1. Bomb calorimeter is a device used to but only a change in physical state of
determine the energy changes associated H,O.
with reactions. The calorimeter measures D. Randomness is decreased.
the heat absorbed or evolved during a
reaction. Which of the following is true with
respect to bomb calorimeter? 3. If the change in free energy of a reaction is
zero at constant temperature and pressure,
A. The measurements are done at constant what is true regarding such a system?
volume.
B. The measurements are not done at con- A. The reaction is spontaneous.
stant volume, because we cannot keep B. The reaction is nonspontaneous.
the volume constant. C. The reaction is at its equilibrium state.
C. Theoretically work is done during the D. Cannot be predicted.
reaction in a bomb calorimeter.
D. None of the above.
4. Mercury sulfide can be converted to mer-
cury by heating while exposed to air. What
2. Consider the figure shown below in which is probably true about this reaction?
ice is melted to form water. Which of the
following is true regarding this conversion?

A. The reaction is nonspontaneous.

B. The reaction is endothermic.
C. 0, acts as the catalyst.
D. None of the above can be ascertained
without further data.

5. All the following are FALSE regarding

entropy, EXCEPT:

A. the entropy of pure substance at 0 K

u WATER

A. Entropy is decreased.
temperature is greater than 1.
B. the entropy of pure substance at 0 K
temperature is between 0 & 1.
C. the entropy of pure substance at 0 K
temperature is 0.
D. the entropy of pure substance at 0 K
temperature is a negative number.

B. Entropy is increased.
Chapter 11 Equilibrium and Kinetics

Equilibrium and Kinetics

A. INTRODUCTION

Different chemical reactions occur at different rates. Some reactions

occur very fast, whereas some others take years and years to complete. A better
understanding of chemical kinetics (the study of reaction rates) and equilibrium
enables chemists to optimize the production of desirable products. This explo-
ration of chemical kinetics has increased the understanding of biochemical
pathways and other pharmaceutical endeavors. We will also discuss catalysts
and their effects on reactions.

B. RATE OF REACTION

The rate of a reaction depends on many factors such as the concentration

of reactants, the temperature at the time of the reaction, the states of reactants,
and catalysts. The rate of a reaction is defined as the change of reactant or
product concentration in unit time. If we were to define the rate of a reaction in
terms of the reactants, we should define the rate as the rate of disappearance of
reactants. If we were to define the rate in terms of the products formed, we
should define it as the rate of appearance of products.

For further exploration of this concept, let's look at a hypothetical reac-

tion. In the hypothetical representative reaction shown below, the small letters
denote the coefficients of the corresponding capital letter reactants or products.
In this reaction, A and B are reactants, and a and b their coefficients respec-
tively. X and Y are the products, and x and y their coefficients respectively.
The MCAT Chemistry Book

For this reaction, we can represent the rate in terms of the disappearance of each
reactant or appearance of each product. The numerators are the concentrations
of either the reactant or the product, and At represents the elapsed time.
A [A1
Rate = --
At
We can also represent it in terms of reactant B. That looks the same as the rate in
terms of concentration of A. In order to express it in terms of B's concentration,
substitute the numerator with the concentration of B. The minus sign conven-
tion indicates that the rate is expressed in terms of the rate of disappearance
(decreasing concentration) of the reactants.
A [Bl
Rate = --
At
Also shown below are the representations of the rate in terms of the products:
A [XI A M
Rate = - Rate = -
At At

Rate Law

Rate law is an expression that we can find experimentally, which relates

the concentration of reactants and the rate of a reaction. Let's consider the same
hypothetical equation:

For this reaction, we can write the rate as follows:

Rate = k [A]" [B]"

Here, k is the rate constant,

m and n are the corresponding exponential values, and
[A] and [B] are the concentrations of reactants A and B.

Note that the rate constant and the exponents of a reaction are found
experimentally. For questions related to finding the actual rate expression of a
reaction, you will be given the relevant experimental data. We will look at some
examples to familiarize ourselves with this concept.

We mentioned the exponent values (for this reaction, we represented

them as m and n) in the rate law. Those exponents represent the order with
respect to a particular reactant, or by adding all the exponents, you will get
overall order of the reaction. For our hypothetical reaction, the reaction order
Chapter 11 Equilibrium and Kinetics

with respect to reactant A is m. The order with respect to reactant B is n. The

overall order of the reaction is m+n. That is one way to determine the order of a
reaction. Chemists categorize them as first order, second order, etc. You may
have heard of zero order. In some reactions, even if a reactant appears in the
balanced equation of a reaction, it may not appear in the experimentally found
rate expression. The reason for this is that the particular reactant that does not
appear in the rate expression has an exponent of 0. So the order with respect to
that reactant is zero.

Example 11-1

From the given experimental data, determine the rate law of the hypothetical
reaction indicated below:

InitiaI Initial Initial Rate

Experiment concentration concentration of product
of P of Q formation

1 0.20 M 0.20 M 0.012 Mimin

2 0.20 M 0.40 M 0.048 Wmin

3 0.40 M 0.40 M 0.096 Mimin

Solution:

The rate of the reaction will have the general look as shown. Assume that the
rate law of the reaction is:

Rate = k [ P 1" [ Q 1".

The plan is to find out the actual values of m and n from the given data. Let's do
it step by step.

Look at the given experimental data. If we compare Experiments 1 and 2, we

can see that the concentration of Q is doubled in Experiment 2. But the concen-
tration of P is kept constant. With these changes, we see the quadrupling of the
The MCAT Chemistry Book

rate. That means the exponent of Q is 2. At this point we can rewrite the rate law
as follows:

Rate = k [ P 1"' [ Q ]*

Now compare Experiments 2 and 3. Here the concentration of Q is kept constant,

but the concentration of P is doubled. The rate is doubling because of this change.
So the exponent of P is 1. We can now write the completed rate law of the
reaction.
Rate = k [ P ] [ Q l2

C. TRANSITION STATE

From our earlier discussions, we know that exothermic reactions release

energy and endothermic reactions consume energy. Here, we will plot the
potential energy diagrams of exothermic and endothermic reactions. Before we
do that, we will discuss the concept of transition state. Consider the hypothetical
reaction shown below:
A + B * X + Y + heat energy
Can you say what type of reaction this is? It is an exothermic reaction.
For reactions to proceed, there should be breaking of bonds and formation of
bonds. For many reactions, the stability barrier that originally made the reactant
molecules stable should be overcome. This is achieved by the formation of an
energy-state that has higher energy than the reactants and the products. This
high-energy state is often referred as transition state. These transition states
have a relatively short life span, and once this highly unstable transition state is
formed, it quickly disintegrates to form the products. For a reaction to reach this
transition energy level, a certain amount of energy is required. This energy is
called the activation energy or the energy of activation.

In the diagram (Figure 11-I), the activation energy depicted in both Figures (a)
and (b) are for the forward reactions.
Chapter 11 Equilibrium and Kinetics

Transition
Fig. (a) state

Exothermic reaction
Potential
energy

Progress of reaction
_______)

Transition
state
Fig. (b)
4

Endothermic reaction

Potential
energy
7
1 Energy absorbed

Progress of reaction
A
Figure 11-1
The MCAT Chemistry Book

D. TEMPERATURE DEPENDANCE OF RATE

The rate of a reaction depends on the prevailing temperature. Hence, the

rate law is dependent on the temperature at which the reaction takes place. The
reactants must attain a high energy form (transition state) in order for the reac-
tion to occur. For this, the activated reactive species must collide (with feasible
orientation) with each other with a minimum kinetic energy which is greater
than that of the reactants. This kinetic energy depends on the temperature of the
system in which the reaction takes place. At a particular temperature, some of
the reactants will attain the activation energy to undergo the reaction. If we
increase the temperature, more reactant molecules will attain this energy. More
reactants attaining the required energy level means more reaction is taking place.

A mathematical relationship was introduced by Arrhenius. The expres-

sion relating the rate constant and the energy of activation is:

k = A e- E, /RT
,

where k is the rate constant of the reaction,

Eo is the activation energy,
R is the gas constant (8.3 1 J/mol.K), and
T is the temperature.

There is no need to memorize this equation, but you should understand how to
work with the equation conceptually.

E. A BRIEF LOOK AT CATALYSTS

We all have heard of catalysts. In lay terms we know that catalysts speed
up reactions. But the question is how do they accomplish this? Consider the
formal definition of a catalyst.

A catalyst is a chemical substance that can increase the rate of a reaction. Even
ifthe catalyst is involved in the reaction, by the end of the reaction you will get
the catalyst intact. In other words, the catalyst retains its identity. Ifa substance
changes its identity and does not have the original nature after the reaction has
occurred, it is not a catalyst, but a reactant.

As we said earlier, the activation energy is the minimum energy required

by the reactants to reach the transition state. A catalyst lowers the activation
energy of a reaction. Thus it provides a lower energy pathway for the reaction to
occur. So the transition state bump in the potential energy diagram (see Figure
11-2) is lowered in a catalyzed reaction, compared to the corresponding
uncatalyzed reaction.
Chapter 11 Equilibrium and Kinetics

Transition state
(uncatalvzed)

Progress of reactlon

Catalysts are often classified on the basis of the phases (solid, liquid,
and gas) in which they exist during a chemical reaction. If a catalyst exists in the
same phase as the reactants of a reaction, then it is called a homogeneous cata-
lyst. If a catalyst's phase is different from that of the reactants of a reaction, then
it is called a heterogeneous catalyst.

F. CHEMICAL EQUILIBRIUM

Many reactions are reversible. Reversible reactions are reactions in

which there are both forward and backward reactions. Consider an experiment
in which two reactants have been mixed. At first, the reaction proceeds with
considerable rate in the forward direction (forward reaction favored). Before
the reaction goes on to completion, the backward reaction takes place. Then
again the forward reaction takes place, followed by the backward reaction and
so on. These uneven back-and-forth directional changes take place until the
reaction mixture reaches the equilibrium. At the equilibrium, the rate will be the
same for both forward and backward reactions.

The Equilibrium Constant

We already talked about the rate of a reaction and its general expression.
For reactions involving simple one-step mechanisms, we can easily write the
rates of forward and backward reactions. Examine a one-step hypothetical reac-
tion represented by the equation (balanced) given below:
aA + bB * cC+dD
The equilibrium constant of a reversible reaction is equal to the ratio
of the product of the concentrations of the products raised to their corresponding
The MCAT Chemistry Book

coefficients, to the product of the concentrations of the reactants raised to their

corresponding coefficients. Keep in mind that the coefficients are taken from
the balanced equation. To further clarify this concept, take a look at the
mathematical expression for equilibrium constant (K,) shown below:

The best way to find out the equilibrium constant of a particular reaction
at a given condition is to do it experimentally. Equilibrium constant depends on
temperature, and hence it differs with change in temperature. You should also
ask yourself this question. Does the initial concentration of the reactants dictate
the equilibrium constant? The answer is no.

We can also explore the meaning of equilibrium constant in terms of

forward and backward reactions. A small value (less than one) for the equilibrium
constant indicates that the forward reaction is not favored. A value greater than
one for the equilibrium constant indicates that the forward reaction is favored.

G. FACTORS THAT AFFECT THE EQUILIBRIUM OF REACTIONS

The equilibrium of a reaction is affected by factors such as changes in

concentration, pressure, and temperature. The likely resulting changes in equi-
librium can be predicted on the basis of Le Chatelier's principle which can be
stated as follows:

lf we change the conditions factors such as the ones mentioned above) of a

reaction system in equilibrium, the system will shift in such a way as to reduce
the imbalance caused by the stress. This is Le Chatelier 's principle.

Based on this principle, we will look at some of the factors that affect the equi-
librium of reactions.

Effect of Temperature

What is your first instinct when you think of a reaction scenario in which
the temperature is changed? It is true that the reaction rate will change. We
might even think that the reaction rates of all reactions invariably increase. This
is not true. Even though many reactions speed up with the increase in tempera-
ture, that is not always the case. Consider the reaction given below:

N2 ( g ) + 3H2(g) - 2 NH3 ( g ) + heat

Chapter 11 Equilibrium and Kinetics

The reaction between nitrogen and hydrogen to give ammonia is an exo-

thermic reaction. The reaction produces heat energy during the forward reac-
tion. For this reaction at equilibrium, if we increase the temperature, it will only
facilitate the backward reaction. Now we will consider another reaction.

C (s) + H 2 0 (g) + heat , - co (g) + H2(g)

For this reaction, we are supplying heat. So what kind of reaction is it? It
is an endothermic reaction. If we subject this reaction in equilibrium to an increase
in temperature, the forward reaction will be favored. We can generalize our
observations as follows:

An increase in temperature favors endothermic reactions. An increase in

temperature decreases the reaction rate, if the reaction is exothermic.

Effect of Pressure

The effects of pressure are significant in reactions involving gases. Think

about what happens when we increase the pressure of a reaction in equilibrium.
When the pressure is increased, the equilibrium no longer exists. Consider the
reaction given below.

The direction of reactions can be predicted based on Le Chatelier's principle.

For the above reaction, if the pressure is increased the forward reaction is favored.
Why is the forward reaction favored? The reason is that the forward reaction
will result in less moles of gas, thereby decreasing the strain caused by the
increased pressure. This influence of pressure will not affect the reaction if the
total number of moles of reactants and the total number of moles of products are
equal. The influence of pressure is not seen with reactants or products which are
either in their solid or liquid state because they are almost non-compressible.
The MCAT Chemistry Book

CHAPTER 11 PRACTICE QUESTIONS / 3. Which of the following factors will affect

/ the rate of a reaction?
1. Choose the correct equilibrium expression
for the following reaction. A. The concentration of reactants
B. Temperature
N2 (d+ 3 H2 (g)a 2 NH3 (g) C. The state of reactants
D. All the above

4. Figure 1 represents the potential energy dia-

gram of a reaction. Pick the true statement
regarding this reaction.

2. Based on the given data, what is the rate

law of the following hypothetical reaction?

Time (reaction coordinate)

A. The reaction requires no activation

energy, since it is spontaneous.
B. There is a net absorption of energy by
the reaction.
C. Reactants have lower energy than that
of the products.
D. None of the above.
A. Rate = k [ Y ]
B. Rate=k[X][Y]
C. Rate = k [ X ]* [ Y ]
D. Rate = k [ X ] [ Y l2
Chapter 11 Equilibrium and Kinetics

5. Which of the following is true regarding 6. If the reverse reaction of Reaction 1 is

catalysts? endothermic, what is the sign of AH of the
reaction in which HI is on the product side?
A. Catalysts can change the rate of a
reaction. A. Positive
B. Catalysts increase the activation energy. B. Negative
C. Catalysts are often consumed complete- C. Neither positive nor negative, because
ly by the reactants. the reaction is reversible
D. All the above. D. Cannot be predicted, because more data
is required regarding the individual
enthalpy values
Questions 6-13 are based on the following
passage.
7. Which of the following is most likely to
Passage P occur, if we take away H, from the reaction
mixture in Reaction 1?
A t this point of advancements in
science, chemists have a good understanding A. The reaction will proceed to the right.
of the kinetics of reactions. They can predict B. The reaction will suddenly reach
the effects of changes in pH, temperature, and equilibrium.
concentration in chemical reactions. C. The reaction will proceed to the left.
D. No apparent effect will be observed.
Experiment 1
In a cylinder, there is a reaction mix-
ture of hydrogen and iodine. The hydrogen and 8. If the pressure applied to Reaction 1 is
the iodine react to form hydrogen iodide. decreased, what is the most likely effect?

H2 (g) + 12 ( g ) 'T-- 2HI (g) (Reaction 1 A. The equilibrium will shift toward the
left.
The industrial production of ammonia B. The equilibrium will shift toward the
is done by a process called Haber process. The right.
reaction occurs as shown below, and is usually C. There will be n o effect on the
done in the presence of an iron catalyst. equilibrium.
D. The volume of the system will decrease.
N2 (g) + 3H,(g) 2NH3 (g) (~eaction2
AH = -92kJ
The MCAT Chemistry Book

9. A student researcher conducted experi- 11. If 70 g of nitrogen is reacted with hydro-

ments on the effects of changes in the gen, how many grams of ammonia will be
conditions on reactions. The student did the produced ? (The weight of hydrogen used
experiments with Reaction 2, by increas- =lo g)
ing the pressure on the cylinder where the
reaction mixture was present. Which of the
following are completely true regarding the
experiment?

I. The reaction will shift toward the right,

because there are more moles on the
product side. 12. In Reaction 2 for the production of arnmo-
11. The reaction will shift toward the left, nia from nitrogen and hydrogen, what is
because there are more moles on the most likely to be true about entropy?
reactant side.
1II.The reaction will have increased pro- A. Entropy increases and is positive
duction of ammonia, because there are B. Entropy decreases and is negative
more moles on the reactant side. C. Entropy increases and is negative
D. Entropy increases and is positive
A. I only
B. I1 only
C. 111only 13. In the Haber process for the production of
D. I1 & I11 ammonia, what can you say about the spon-
taneity of the reaction with the available
information in the passage?
10. Which of the following best explains the
theory behind the predictions of the effects A. The reaction is definitely spontaneous.
of increasing the concentrations of reactants B. The reaction is definitely nonspontaneous.
or products in a reaction system? C. The reaction is endothermic, and defi-
nitely spontaneous.
A. Dalton's law D. Cannot be predicted accurately without
B. Markovnikov's principle further data.
C. De Broglie principle
D. Le Chatelier's principle
Chapter 12 Electrochemistry

Electrochemistry

A. INTRODUCTION

Electrochemistry is the study of chemical reactions that result in the

production of electric current, and chemical reactions that occur when subjected
to electric current. Electrochemical applications are part of everybody's day-to-
day life. Energy storing batteries that we use for TV remotes, flashlights, auto-
mobiles are a few examples. Electroplating is another achievement among many
others. In this chapter, our discussion will revolve around two types of electro-
chemical cells - the electrolytic cell and the galvanic cell.

B. ELECTROLYTIC CELL

In an electrolytic cell, electric current drives the chemical reaction. The

chemical reaction involved in an electrolytic cell is nonspontaneous. Electric
current is used to drive the reaction. This process is called electrolysis and hence
the name, electrolytic cell. The reaction involves the transfer of electrons and
thus it is a redox reaction. For further understanding of the functioning of an
electrolytic cell, we will look at an example of an electrolytic cell involving the
electrolysis of molten sodium chloride. Molten sodium chloride is a good con-
ductor of electricity. The melting point of NaCl is around 800" C.

The cell contains molten sodium chloride into which two electrodes are
immersed, as shown in Figure L2-1. One electrode is connected to the positive
terminal of the battery, and the other is connected to the negative terminal of the
battery. The electrode that is c~nnectedto the positive terminal of the battery is
the anode. The other electrode is the cathode. Reduction occurs at the cathode,
and oxidation occurs at the anode. When the current starts flowing the reaction
starts, as described below:
The MCAT Chemistry Book

- +

Battery

Chlorine gas
evolves at the
anode

Cathode Anode

molten sodium
chloride

\
Sodium metal
deposits at the cathode

Figure 12-1 Electrolytic cell set up showing the electrolysis of molten NaCI

As the reaction proceeds, the sodium ions (Na') are reduced to sodium
(Na) at the cathode, and the sodium metal is deposited at the cathode. On the
other hand, the chloride (Cl-) ions are oxidized at the anode forming chlorine

~171) -
gas (Cl,). The half-reactions and the overall reaction are represented below:
1
r ~ 1 2(g) + e
-
Anode
N;(I>

N;(Q +
+ e-

CI- -
-----) Na (1)
Na (1) ,
+ 1 c12 (g)
Cathode

Overall reaction
Chapter 12 Electrochemistry

C . FARADAY'S LAW

According to Faraday's law, the amount of substance that undergoes

oxidation-reduction reaction at the electrodes is directly proportional to the
amount of electric current that the reaction is subjected to. Faraday constant is
equal to the charge of one mol of electrons, and is numerically equal to 96500
coulombs. You probably remember 'coulombs' from your physics undergradu-
ate courses. The unit coulomb is related to the unit ampere (SIunit of current).

amperes x seconds = coulombs

current x time = charge

D. GALVANIC CELL

Galvanic cell is also known as voltaic cell. The major difference between
an electrolytic cell and a galvanic cell is that the reaction in a galvanic cell is
spontaneous, and the reaction produces electric current. The batteries that we
use in TV remotes and flash lights are galvanic cells. Galvanic cells convert the
stored chemical energy into electrical energy for usage.

A galvanic cell has two half-cells. Each half-cell consists of a metal

electrode immersed in a solution containing the same ions. The two half-cells
are connected by a wire as shown in Figure 12-2. As we mentioned earlier, the
galvanic cell produces electric current. Thus the voltage developed can be
measured by setting a voltmeter along the connecting wire, as seen in the figure.

Here, we will look at a cell setup which uses zinc and copper as the
electrodes. In addition to the electrodes, the two containers which hold the
appropriate solutions and the connecting wire, there is a salt bridge which
connects the two solutions. The salt bridge is usually dipped into the solutions
of the two half-cells. It contains a gel in which an electrolyte is present. The
electrolyte present in the salt bridge will neutralize the buildup of ionic charge
in the cells; a buildup which will otherwise slow down and stop the reaction
from proceeding.
The MCAT Chemistry Book

Figure 12-2 Galvanic cell

In the zinc half-cell, a zinc electrode is immersed in zinc sulfate solution.

In the copper half-cell, a copper electrode is immersed in copper sulfate solution.
The two electrodes are connected by a wire through which there will be flow of
electrons resulting from the reaction. The half-reactions are shown below:

Zn (s) -
- Zn 2i (aq) + (Oxidation half-reaction)

b~,
-
CL?' (aq) + cu (s) (Reduction half-reaction)

cu2+(aq) + Zn (s) Cu (s) + Zn 2t (aq) (Overall reaction)

The process of oxidation occurs at the anode and the process of reduc-
tion occurs at the cathode. So the first half-reaction (oxidation half-reaction)
occurs at the anode, and second half-reaction (reduction half-reaction) occurs at
the cathode. The overall reaction can be obtained by adding the two half reac-
tions. Here, the zinc electrode is the anode, and the copper electrode is the cathode.
In a galvanic cell, the anode is the negative electrode and the cathode is the
positive electrode. As far as electron flow is concerned, the flow is always from
the anode to the cathode.
Chapter 12 Electrochemistry

Let's take a look at Figure 12-2 again. Notice the irregular edges of the
electrodes. Why is that so? The reason is simple. As the reaction proceeds, zinc
is stripped away from the zinc electrode, and thus it becomes thinner and thin-
ner until the reaction stops (when it is at equilibrium). On the other hand, the
copper electrode becomes thicker and thicker due to the deposition of metal
copper on the copper electrode.

The half-reactions are often represented by the notation shown below.

By convention, the oxidation reaction is written on the left of the symbol denot-
ing the salt bridge, and the reduction reaction is written on the right side of the
salt bridge symbol.

Anode half-reaction Cathode half-reaction

I
Zn zn2+ 1 cu2+ 1 cu
1 denotes salt bridge

Note: See Table 12-2 at the end of this chapter for electrolytic versus galvanic cell
comparison.

E. STANDARD ELECTRODE POTENTIALS

Before we discuss standard electrode potential, we will talk about elec-

tromotive force (emf). The electromotive force of a cell is the potential difference
between the two electrodes. This can be measured using a voltmeter. The max-
imum voltage of a cell can be calculated using experimentallydetermined values
called standard electrode potentials. By convention, the standard electrode
potentials are usually represented in terms of reduction half-reactions for 1 molar
solute concentration. The standard electrode potential values are set under ideal
and standard-state conditions (1atm pressure and 25C temperature). From the
MCAT point of view, you can assume that the conditions are standard, unless
stated otherwise. Table 12-1 shows a list of standard electrode potentials (in
aqueous solution) at 25OC.

The standard electrode potential at the above mentioned standard state

conditions is denoted by E O.For the MCAT, the values of the standard electrode
(reduction) potentials will be given to you if you are required to solve such a
question. Do not try to memorize those values. The standard electrode potentials
are based on an arbitration with reference to standard hydrogen electrode. The
standard hydrogen electrode potential is considered to be 0 volt.
 The MCAT Chemistry Book

Table 12-1 Some Standard Electrode (Reduction) Potentials

-
....................
~ i ++ Li -3.04 I
TOP TO BOTTOM
K+ + f K -2.93 Oxidizing Strength Increases

A13' + 3 6 -*A1 j -1.66

zn2+ + 2 e in -0.76
cr3+ + 3

-
Cr -0.74 a

Fe2++ 2 ~ - Fe -0.41 j
cd2+ 2 e ~d k0.40
j Ni2+ + 2 +j ~ i -0.23
I
I pb2+ + 2 e F ~b -0.13
I REFERENCE STANDARD 2H+ + 2C- I
--
Hs 0.00
I

cu!+ + 2 e--+ cu - +0.34

j + 2e 2 I - 10.54
j ~ e ' ++ 3 e Fe +0.77
H ~ +~2 e-+ ~g +o.~o
I--- - + e-- ~g +0.80
Br2 + 2;- 2 B r t-1.07
C12 + 2 c- 2 C1 +1.36
. .#
- 0
'
A U ~ ++ 3 e- AU +1.50
F2 + 2 e - 2 F +2.87
Chapter 12 Electrochemistry

Finding the emf of a Cell

The emf of a cell can be calculated from the standard electrode potentials
of the half-reactions. In order to find the emf, we have to look at the two half-
reactions involved in the reaction. Then, set up the two half-reactions so that
when they are added we will get the net reaction. Once we have set the equations
properly and assigned the prpper potentials to those half-reactions, we can add
the standard electrode potentials. A common mistake that students make is that
they forget the fact that the standard electrode potentials are given in terms of
reduction reactions. Redox reactions involve both oxidation and reduction. If
one half-reaction is reduction, the other should be oxidation. So we must be
careful about the signs of the half-reaction potentials, before we add the two
half-reaction potentials to get the emf value. Do the next example.

Example 12-1

-
Calculate the emf of the cell, based on the following net reaction.

c?' (aq) + Zn (s) Cu (s) + Zn 21 (aq)

Standard Electrode Potentials of the half-cells
Half-reaction

Zn 2t (aq)
cu2+(aq)
+ 2 e-
+ 2 e-
-
- Zn ( s )
cu (s)
EO (volts)

-0.76

0.34

Solution:

First, we have to write the half-reactions as indicated below.

cu2' (aq)
Zn (s)
+ 2e
-
- Zn 2t (aq)
cu (s)
+ 2 e (Oxidation half-reaction)

(Reduction half-reaction)

From Table 12-1, we can take the standard electrode potential values. The cell
containing the copper electrode has a standard potential value of 0.34 V. For the
other half-cell, the reaction is oxidation. Since the value given in the table is in
terms of reduction half-reactions, we have to reverse the sign of the standard
The MCAT Chemistry Book

electrode potential given. The correct value for the oxidation half-cell is N.76V
instead of -0.76 V. Now, you can add the two values to get the emf of the whole
setup.

emf = 0.34 + 0.76 = 1.10 V

The answer is 1.10 V.

Table 12-2 Electrolytic cell & Galvanic cell - A comparison

ELECTROLYTIC
CELL

aontaneity? Nonspontaneous 9ontaneous

Qfhode Negative electrode Fbative electrode

Anode bative electrode Negative electrode

Oxidation Anode Anode

I
Mudjon Cathode Cathode

Ehegy dynamics Bedrical to chemical Chemical to electrical

E THE FREE ENERGY-EMF RELATION

The change in free energy (AG) is the maximum amount of energy that
is available to do useful work. In an electrochemical cell, this free energy is
equal to electrical work which is equal to the product of the number electrons,
the Faraday constant, and the electrochemical cell's emf.

In this equation, n is the number of equivalents of electrons transferred in the

reaction, F is the Faraday constant (96,500 coulombs), and Pee,, (cell's emf). From
this equation, we can deduce that if the emf is positive, the corresponding change
in fiee energy (AG) will be negative. In other words, if the emf is positive the
reaction is most likely to be spontaneous. On the other hand, if the emf of a cell is
negative, the AG will be positive indicating a nonspontaneous reaction.
Example 12-2

Calculate the standard free energy change at 25OC for the redox reaction in
Example 12-1. (Faraday constant = 96,500 coulombs)

Solution:
cu2' (aq) + Zn (s) - Cu (s) + Zn 2+ (aq)
From the previous example, we know that the emf of this reaction is 1.10 V. The
formula for AG in terms of the potential difference is:
coulombs x volts =joules
AG = - n FEOcell

Here, the number of electrons transferred is 2. This number is obtained by exam-

ining the balanced equation and evaluating the change in oxidation numbers. For
example, copper ions with +2 oxidation state changed to copper (solid) with an
oxidation state of 0. In other words, each half-reaction involves two electrons.

AG= - n FEace,,=- 2 x 96500 C x 1.10 V = -2.12 x lo5 Joules

Notice that the change in free energy is negative and this indicates that the reac-
tion is likely to be spontaneous.
The MCAT Chemistry Book

CHAPTER 12 PRACTICE QUESTIONS 4. In an electrolytic cell, 5 A of current passes

for about 3.5 minutes. The amount of elec-
1. Given below i s the standard electrode tric charge equals:
potential (EO) o f the following redox
reaction. Predict the most feasible event, if A. 17.5 coulombs.
the reaction occurred spontaneously. I B. 85.7 coulombs.
C. 1050 coulombs.
zn2' ( s ) + Sn ( s ) Zn (s) + sn2+ D. 96500 x 5 x 3.5 coulombs.

Questions 5-10 are based on the following

A. Zn2+was reduced. passage.
B. Sn was oxidized.
C. Zn lost electrons. Passage 1
D. Ether was used as the solvent medium.

2. In an electrochemical cell, the redox reac-

tion involved the change of oxidation state
I Table 1 I
of chromium from +2 to +3. This half-reac-
tion most likely must have occured at the:

A. anode, because it is oxidation.

B. anode, because it is reduction.
C. cathode, because it is oxidation.
D. cathode, because it is reduction.

3. The standard potential EOis related to equi-

librium constant K by the following
relation:

In a reaction occurring at standard state

conditions, if the concentrations of the prod-
ucts are greater than that of the reactants at
equilibrium, which of the following is true?

A. K is negative.
B. Eo is negative.
C. The reaction is nonspontaneous.
D. None of the above
 By comparing standard reduction 9. Which of the following species has the
potentials, we can compare the reduction and highest oxidation potential?
oxidation powers of elements or ionic species.
Some standard reduction potential values are
given in Table 1.

5. Which of the following processes is most

likely to be a spontaneous process?

A. Oxidation of copper 10. The process of corrosion is a redox reac-

B. Reduction of chlorine tion. Consider the rusting of the body panel
C. Oxidation of fluoride ion of automobiles. Certain parts of the object
D. Reduction of zinc ion that are undergoing corrosion act as if they
were half cells. For the corrosion of iron,
iron is changed to Fe2+ions. Which of the
6. What is the overall cell potential for a cell following best represents the area where this
which is formed with Ni/Ni2+and Ag/Ag+ change occurs?
half-cells?
A. Cathode
B. Anode
C. Both anode and cathode
D. Cannot be predicted without more data

7. In a galvanic cell, usually a salt bridge is

used. What is the most likely purpose of
this?

A. To conduct electricity
B. To prevent corrosion
C. To regulate electricity
D. To maintain neutrality in the half-cells

8. Which of the following will act as an oxi-

dizing agent the most?
This page intentionally left blank
Chapter 13 Radioactivity

Radioactivity

A. INTRODUCTION

This is the last chapter in Part I of the general chemistry review. In this
chapter, we will discuss the different aspects of radioactivity. Radioactivity is a
nuclear phenomenon. It results from natural nuclear instability or externally
induced nuclear instability. We will limit our discussion of nuclear chemistry to
the basic aspects of radioactivity involving radioactive emissions such as alpha
emission, beta emission, gamma rays, positron emission, and electron capture.
We will also review other ideas such as the half-lives of radioactive substances
and the mass-energy equation.

B. STABILITY OF NUCLEUS

The nucleus is not involved in normal chemical reactions. In radioactivity,

it is the nucleus that is undergoes the changes. Nuclear forces are extremely
strong forces that hold the nuclear particles together. These forces make the
nucleus very stable. Remember that the protons are positively charged and can
exert repulsive forces among themselves. It has been found out that there are
certain predictable behavioral patterns in elements as the atomic number
increases. As the atomic number increases, the neutron-to-proton ratio increases
and as more and more protons are present in the nucleus, the stabilizing forces
are not sufficient to keep the nucleus stable. Thus the stability of the nucleus
decreases as the neutron-to-proton ratio increases.

C. RADIOACTIVE DECAY

Atoms with unstable nuclei can undergo radioactive decay to become

atoms which are more stable than their parent atoms. In the process, different
types of particles are emitted. We will discuss some of the important ones that
you have to know from the MCAT point of view.
The MCAT Chemistry Book

Alpha emission: Alpha emission (a)is a low-penetrating emission. It is actually

helium nucleus and is often represented as % He. An example of radioactive decay
of radium226 is given below:

As you can see, the resulting atom has both mass number and atomic
number changed. The atomic number decreases by 2, and the mass number
decreases by 4.

Beta emission: Beta particles (P-) are emissions having medium level penetra-
tion. They are fast traveling electrons. As a result of beta emission, the resulting
atom will have an increase in the atomic number by 1. There is no change in the
mass number. In the process, there is also a proton formation from the neutron
inside the nucleus, along with the electron formation. In the following example,
thorium-234 decays to protactinium-234 by emitting a beta particle.

Positron emission: Positron emission (p+) is the positive counterpart of an

electron emission. A positron has the exact mass of an electron, but has a positive
charge. During this event, a proton is converted to a neutron and a positron. The
product of a positron decay will have an atomic number less than that of the
decayed atom by one unit. There is no change in mass number.

Electron capture: As a result of electron capture, a proton is converted into a

neutron. The electron is usually captured from the innermost shell of the atom.
The atomic number of the product will be one less than that of the original atom.
There is no change in mass number.

Gamma emission: Gamma (y) emissions or gamma rays, as they are commonly
referred to, are highly penetrating and dangerous emissions. They are high
frequency electromagnetic rays. Gamma rays travel at the speed of light. The
resulting product atom has the same atomic and mass numbers as those of the
parent atom from which the gamma rays are emitted. Gamma rays have no charge.

D. HALF-LIFE

All radioactive elements do not decay at the same pace. They have
drastically different rates of decay. The radioactive decay time is expressed in
terms of half-life period. The half-life of a radioactive substance is the time
required for the decay of half the substance present in a sample of that substance.
Chapter 13 Radioactivity

Regardless of the amount of a particular radioactive substance we have, it takes

the same time (half-life) to complete the decay of half the number of nuclei in
that sample.
7

The half-life of a radioactive substance is the time required for the complete
decay of exactly halfthe amount of that substance.

Example 13-1

Calculate the amount of time (in years) it takes for the decay of 75% of a given
sample of carbon-14. Carbon-14 has a half-life of approximately 5700 years.

Solution:

After the first 5700 years of decay, 50% of the original sample is left. After 5700
more years, 50% of that sample will have decayed, which means that there is
now 25% of the original intact sample. This is the amount of time that the question
is asking for. To be clear about our analysis, let's rephrase what we have said.
We have 25% of the original sample left at this point. Thus the decay of 75% of
the original sample is complete. So the answer is 5700 x 2 = 11400 years.
Table 13-1 Summary of changes in the parent nucleus due to
different decay modes.
M = mass number of the parent nucleus undergoing decay.
Z = atomic number of the parent nucleus undergoing decay.
MASS NUMBER OF ATOMIC NUMBER OF
TYPE OF DECAY THE DAUGHTER THE DAUGHTER
NUCLEUS NUCLEUS

Alpha decay M-4 2-2

Beta- decay M Z +1

Beta+decay
M Z-1
(Positron)

Electron capture M Z-1

Gamma decay M Z
The MCAT Chemistry Book

CHAPTER 13 PRACTICE QUESTIONS 5. Substance X has a radioactive half-life of

12 years. How much time must have
1. Radium 226 can undergo radioactive decay elapsed if only 9 grams is left from an origi-
to form Radon 222. Which of the following nal sample of 150 grams?
is the most likely type of particle that is
emitted? A. 12 years
B. 24 years
A. Beta particle C. 36 years
B. Alpha particle D. 48 years
C. Gamma particle
D. Positron particle
Questions 6-11 are based on the following
passage.
2. Consider the radioactive-decay equation
given below. What is the most likely iden- Passage 1
tity of X?
In nuclear reactions, significant changes
occur in the composition of the nuclei of the
atoms involved. These reactions usually release
tremendous amounts of energy. One of the rea-
A. Alpha particle
sons for the nuclear changes can be attributed
B. Beta particle
to the stability of the nucleus.
C. Positron particle
D. Neutron
The formation of nucleus from the sub-
atomic particles - neutrons and protons, results
in the release of energy. The mass of these indi-
3. Which of the following emissions travels
at the speed of light? vidual particles in the nucleus is greater than that
of the actual nucleus that is formed. This loss of
mass is due to the change of mass into energy.
A. Gamma ray
The energy-mass relation can be represented in
B. Beta particle
terms of the equation:
C. Alpha particle
D. Antineutrino

where m represents the mass, and c represents

4. Which of the following has the highest pen-
the speed of light (3x lo8mls).
etrating power?
If the nucleus of an atom is not stable,
A. Alpha particles
it can get transformed into another nucleus. A
B. Beta particles
plot of the number of neutrons versus the
C. Gamma rays
number of protons is often used to assess the
D. All the above have the same penetrat-
stability trends of elements. If the number of
ing power
protons and neutrons are equal, the nucleus is
Chapter 13 Radioactivity

considered. to be reasonably stable. As the 6. A sample of 226Radisintegrates to 3% of

atomic number increases, the trend changes. its original quantity. How many half-lives
have this sample passed?
Isotopes of elements having atomic numbers
above x83 are unstable atoms. These unstable A. two
atoms can undergo disintegrations. The half- B. three
lives of some radioactive elements are shown C. four
in Table 1. D. five

7. 234Thundergoes radioactive decay. If the

thorium nucleus emitted a P-particle during
its decay, what is the identity of the element
that is formed?

TABLE 1
atom
Carbon 14
Uranium 238
-
number of protons

half-life
5.73 x 10 years
4.47 x 10' years
8. All the following are true regarding radio-
active rays, EXCEPT:

A. a-particles are positively charged.

B. P-particles are negatively charged.
C. y rays are electromagnetic rays and can
be deflected by an electric field.
D. There are radioactive emissions in
which the mass number is not affected.
Radon 222 3.82 days
Radium 226 1.6 x l o 3 years
Krypton 89 3.2 minutes
The MCAT Chemistry Book

9. Which of the following is true regarding

radioactivity?

A. As the atomic number increases, even-

tually the neutron-proton ratio values
become 2 1.
B. As the atomic number increases, even-
tually the neutron-proton ratio values
become 2 1.
C. As the atomic number increases, even-
tually the proton-neutron ratio values
become 2 1.
D. None of the above

10. When a helium nucleus is formed, there is

always some degree of loss of mass. If the
loss of mass equals 3.1 x lo-* kg during
the formation of one mol of it, what is the
binding energy?

11. The most probable set of particles that were

given off during the series of nuclear
changes from 232Thto 224Raare:

A. two alpha particles and one beta

particle.
B. one alpha particle and two beta particle.
C. one alpha particle and three beta
particles.
D. two alpha particles and two beta
particles.
ORGANIC CHEMISTRY
This page intentionally left blank
Chapter 14 General Concepts

General Concepts

A. INTRODUCTION

Organic Chemistry is the study of carbon compounds. Carbon can form

a wide array of compounds, because of its size and ability to form covalent
bonds with other carbon atoms. In addition, carbon can form bonds with many
other elements. This property of carbon increases the facility of forming
multitudes of different compounds. The particular electronegativity of carbon
also plays a key role in its versatility. In this chapter, we will review some of the
fundamental aspects of carbon atom and the main types of hybridizations
involving carbon compounds.

B. THE CARBON ATOM

Electrons are found in regions around the nucleus in an atom. and those
regions are called orbitals. The orbitals can be defined and differentiated by
size, shape, and orientation. Valence electrons are electrons that are found in
the outermost shell. The carbon atom has four valence electrons. These valence
electrons are involved in chemical reactions and bonding.

The electronic configuration:

Electronic 1s'2s22p2
configuration
The MCAT Chemistry Book

C. BONDING

Ionic bond - Ionic bond is formed between an electropositive and electronega-

tive atom (ion), or generally we can define it as an attractive force between a
positive and a negative ion (e.g., KC1).

Covalent bond - Covalent bond is formed by the sharing of a pair of electrons

between two atoms. Carbon compounds generally contain covalent bonds.

For a more detailed discussion of this topic see the general chemistry section of
this book - Chapter 5.

D. HYBRIDIZATION OF ORBITALS

The six electrons of a carbon atom are distributed in the orbitals as follows:

Electronic configuration - ls22s22p2

Ground state carbon atom '

sp3Hybridization

The carbon atoms of alkanes (e.g., methane, ethane) are sp3hybridized.

In order to form the four bonds in methane, a carbon atom needs four half-filled
orbitals. In order to have more fkee half-filled orbitals, the carbon atoms undergo
hybridization.

H-C-H
I METHANE

I
H
Chapter 14 General Concepts

sp3 hybrid state of carbon atom

The hybridization results in one half-filled 2s orbital, and three half-filled 2p

orbitals (a total of four half-filled orbitals). These unpaired electrons form the
sp3 hybridized carbon, which can form the four covalent bonds in the methane
molecule. The four sp3hybrids are directed to the corners of a tetrahedron with
bond angles of 109S0.

sp2Hybridization

In carbon-carbon double bonds, the carbons undergo another type of

hybridization called the sp2hybridization. In this hybridization, only one 2s, and

oi
two 2p orbitals are involved. The C=C contains a sigma (o)bond and a pi (n)
bond. The pi bond is formed by the unhybridized 2p orbital overlap. The three
equal hybrids lie in an xy-plane with bond angles of 120.

Ethylene

sp2 hybrid state of carbon atom

1-3.

One 2s and two 2p orbitals

The MCAT Chemistry Book

sp Hybridization

Yet another hybridization called the sp hybridization exists in carbon-

carbon triple bonds. An sp hybridized carbon atom is bonded only to two other
atoms. In this type of hybridization, one 2s orbital and one 2p orbital are involved.
A carbon-carbon triple bond contains one sigma bond and two pi bonds.
>

HC=CH Acetylene
1 J
sp hybrid state of carbon atom

One 2s and one 2p orbitals

E. RESONANCE

Resonance is an important aspect in Organic chemistry. Though we rep-

resent definite Lewis structures of molecules, in reality the electrons are not
localized. They are shared and delocalized by the atoms in a molecule to have
the most stable electron distribution. This is called resonance. Resonance pro-
motes stability.

a Acetate ion
Chapter 14 General Concepts

E FUNCTIONAL GROUPS

IMPORTANT FUNCTIONAL GROUPS

R-C-X R-C-0-C-R
Acid halide Acid anhydride Alcohol

R-C-H
Aldehyde Alkane Alkene

"p-pq R COH
Carboxylic cid
R- C-OR
Ester
Ether

RC-R Thiol
Ketone
The MCAT Chemistry Book

CHAPTER 14 PRACTICE QUESTIONS 5. How many electrons are actually involved

in the carbon-carbon bond of acetylene?
1. The carbon indicated by the arrour has
which of the following hybridizations?

6. Which of the following best represents the

A. sp hybridization hydrogen-carbon-hydrogen bond angles in
B. sp2 hybridization methane?
C. sp3 hybridization
D. sp3d hybridization

2. In acetylene, h.ow many sigma bonds are

present between the two carbons?

A. One
B. Two
C. Three
D. Four

3. The triple bond of 2-propyne contains:

A. one sigma bond and one pi bond.

B. one sigma bond and two pi bonds.
C. two sigma bonds and one pi bond.
D. three sigma bonds.

4. Which of the following represents the

arrangement of the sp3 hybrid orbitals in
methane?

A. Planar
B. Tetragonal planar
C. Tetrahedral
D. Bipyramidal
Chapter 14 General Concepts

7. Which of the following bonds indicated by

the arrows has the shortest bond length?

Figure for 0 - 7
N/

8. The carbon-hydrogen bond in propane can

be best described as:

A. an ionic bond.
B. a covalent bond.
C. a hydrogen bond.
D. a dipole-dipole bond.
This page intentionally left blank
Chapter 15 Alkanes

Alkanes

A. INTRODUCTION

Hydrocarbons are compounds containing only carbon and hydrogen.

They are classified into aliphatic and aromatic hydrocarbons. Aliphatic
hydrocarbons can be divided into three major groups - alkanes, alkenes, and
alkynes. Alkanes come under saturated hydrocarbons, because they have carbon-
carbon single bonds. Alkenes and alkynes are unsaturated hydrocarbons, since
they have carbon-carbon double and triple bonds, respectively.

B. ALKANES

Alkanes have the general molecular formula CnHZni2. Hence, if we know

the number of carbons present in an alkane, we can calculate the number of
hydrogens in it or vice versa. Methane is the first member of the alkane family.
It has a molecular formula of CH,. Natural gases which are found in petroleum
deposits contain gases such as methane, ethane, and propane. They are the first
three members of the alkane family.

ALKANES WITH 1-12 CARBON ATOMS

Methane CH4 Heptane c7H16

Ethane CZH~ Octane csH18

Propane C3Hs Nonane C9H2o

Butane C~HIO Decane C 10H22

Pentane Cd12 Undecane C11H24

Hexane C~HIA Dodecane C 12H26

*
The MCAT Chemistry Book

Methane is a colorless, odorless gas. Ethane, propane, and butane are

also gases, with butane having the highest boiling point among these. What
kind of trend can we see from these observations? As the number of carbons
and hydrogens increases, the boiling point increases. Each carbon in an alkane
is sp3hybridized.

C. PROPERTIES OF ALKANES

At room temperature, the first four members of the alkane family are
gases. The straight chain alkanes from pentane and up are liquids, and octadecane
(18 carbons) and up in the alkane family are solids. As the number of carbons
increases, the boiling point increases. Branched alkanes have lesser boiling points
than their unbranched or less branched isomeric counterparts. The reason for
this is that the unbranched molecules have more intermolecular interactions
than the branched ones.

D. STRAIGHT CHAIN AND BRANCHED ALKANES

Butane (C,H,,) and the other alkanes above it can exhibit constitutional
isomerism. If the alkane is unbranched and has a straight chain, it is called
n-alkane. For example, the straight chain pentane is called n-Pentane.

Constitutional (structural) isomers are isomers with the same molecular for-
mula, but are different in terms of the order in which the atoms are connected.

Butane has two possible isomers: n-Butane and Isobutane

n-Butane Isobutane
H
CH3CH2CH2CH3
Chapter 15 Alkanes

Pentane has three isomers: n-Pentane, Isopentane, and neopentane

n-Pentane Isopentane Neopentane

The best way to find the number of possible isomers is by drawing out the
structures sequencially and systematically, starting from the straight chain com-
pound. There is no simple general formula to calculate the number of possible
isomers of an alkane.

E. ALKYL GROUPS

Alkyl groups are groups which lack one hydrogen atom compared to its
parent alkane. For example, methyl group is CH, , which lacks one hydrogen
atom with respect to its parent alkane, methane (CH,). Similarly, ethyl group
(C,H,--) lacks one hydrogen atom compared to ethane (C2H6).

Some common alkyl groups

P ~ O P Y(n-propyl)
~ isopropyl butyl isobutyl

sec-butyl

F. THE IUPAC NAMING OF ALKANES

Main rules and strategies for the IUPAC naming of alkanes

1. Write out the expanded structural formula, if it is not given in the expanded form.
2. Find the longest carbon chain and then identify the alkyl or other substitu-
ents that are connected to this long chain.
3. The numbering of carbons should start from the specific end of the long
chain, so that the numbers assigned for the substituents are the lowest.
The MCAT Chemistry Book

2-methyl hexane

4-ethyl-2-methyl heptane

2,2-dimethyl-4-ethyl heptane

G. CYCLOALKANES

Cycloalkanes are cyclic compounds with ring structures. The general

molecular formula of a cycloalkane is CnHln.

Cyclopropane
H 2 C C H 2
Chapter 15 Alkanes

H2

"1%'
HC
c'
C
,H. cyc~opentane

H2

H2

0 H2r rH2
/C\

Cyclohexane
H2C-CH2
OR
CH2

H. REACTIONS OF ALKANES

Combustion

Hydrocarbons undergo combustion reactions in the presence of oxygen

to form carbondioxide and water as products. Combustion reactions are very
exothermic giving out energy, as they burn in the presence of oxygen.

Sample reaction 15-1

CH, + 20, -----+ CO, + 2 H 2 0 AHO = - 890 kJ

Halogenation

The halogenation reaction can be generalized as follows:

In this substitution reaction, the halogen (fluorine, chlorine, bromine, iodine)

substitutes one hydrogen atom in the alkane, forming hydrogen halide and alkyl
halide as the products. The reactivity of halogens in the halogenation reactions
is as follows:
-

Fluorine > Chlorine > Bromine > Iodine

Fluorine is the most reactive among halogens in halogenation reactions, and

iodine is the least reactive.
The MCAT Chemistry Book

I. MECHANISM OF FREE RADICAL SUBSTITUTION OF ALKANES

Halogenation reactions occur via a mechanism called free radical sub-

stitution. There are three main steps in the free radical mechanism. They are:

(1) initiation
(2) propagation
(3) termination.

The overall reaction of chlorination of methane.

CH, + C1, ----+ CH,Cl + HCl

(1) Initiation

This step involves the dissociation of the halogen molecule (e.g., chlo-
rine molecule) into two chlorine atoms. Even though the total reaction is
exothermic, initially energy should be supplied for the reaction to proceed.

0. 0.

:CI
0. : Cl: 0. 2
Chlorine 2 Chlorine
molecule atoms

(2) Propagation steps

During the propagation step, the hydrogen atom is abstracted from meth-
ane by a chlorine atom. This is followed by the reaction between the methyl
radical and the chlorine molecule.

:CI. + CH3:H
0.

Chlorine atom Methane

)-
..
HZCI: + .CH 3
2 Chlorine Methyl
atoms radical
Chapter 15 Alkanes

:CI:Clt
*. **
+ C H3*
Chlorine Methyl
----;1 *CI: + CH3tClt
l

Chlorine atom
Methyl
-
chloride
molecule radical

(3) Termination

The termination steps involve the combination of the radicals.

.CH
3
+ CH*
3
, HC-CH
3 3

J. REACTIVITY OF ALKANES

Primary, Secondary, and Tertiary Carbons

A carbon which is attached directly to only one other carbon is called a

primary (lo)carbon. If it is attached directly to two other carbons, it is a second-
ary (2O) carbon. A carbon is called a tertiary (39 carbon, if it is directly attached
to three other carbons.
The MCAT Chemistry Book

primary carbon

/C\
HZ n
tertiary

CH

I
iary carbon

/CH3

/""\
secondary
carbon

Though alkanes are not so reactive, they can undergo some reactions by
forming intermediates. These intermediates can be alkyl radicals, carbocations,
or carbanions. Alkyl radicals are intermediates of free radical reactions.
Carbocations (carbonium ions) are species with a positive charge on one of the
carbon atoms. A carbanion has a negative charge on one of its carbon atoms.
Some major trends are given below:

CarbocationIAlkyl radical stability

3' > 2' > lo > methyl

CarbocationIAkyl radical reactivity

1
3' < 2' < lo < methyl

F a r b a n i o n stability

3' < 2' < lo< methyl

Carbanion reactivity

K. CONFORMATION AND STABILITY O F ALKANES

Conformations

Alkanes can have different conformations. By analyzing the structure of

ethane, we can define certain aspects regarding its conformations. Conforma-
tions are different arrangements of the atoms in a molecule, as a result of rotation
around a single bond.
Chapter 15 Alkanes

Figure 15-1 STAGGERED CONFORMATlON

SAWHORSE REPRESENTATION NEWMAN PROJECTION

In staggered conformation, the torsional angle is 60. In eclipsed com-

formation, each carbon-hydrogen bond is aligned with the carbon-hydrogen
bond of the next carbon.

Figure 15-2 ECLIPSED CONFORMATION

SAWHORSE REPRESENTATION NEWMAN PROJECTlON

In eclipsed conformations, the torsional angle is 0". In staggered

conformations, the torsional angles can either be 60" (gauche) or 180" (anti).
The anti conformation is more stable than the gauche conformation. We should
also consider the fact that in this analysis of staggered conformation, the ethane
molecule looks the same in the Newman projections, whether it is gauche or
anti. Reason: There are no substituents other than just hydrogens. To denote the
positional significance, the hydrogens are indicated in bold in the diagrams shown
in Figure 15-4.
The MCAT Chemistry Book

Eclipsed

ANGLE OF TORSION
IS o0
Figure 15-3

Gauche Anti

ANGLE OF TORSION ANGLE OF TORSION

IS 60'
Figure 15-4 IS 180'

L. CONFORMATION AND STABILITY OF CYCLOALKANES

According to Baeyer strain theory, the stability of a cycloalkane is based

on how close its angles are to 109S0.The closer the angle is to 109S0,the more
stable the cycloalkane. Deviation from this angle can cause angle strain. An
increase in the angle strain means a decrease in the stability of the molecule.

Conformations of Cyclohexane

Cyclohexane has a non-planar structure that makes it almost free from

ring strain. The most important conformations that it can have include chair
conformation and boat conformation. The chair conformation is more stable
than the boat conformation. The boat conformation can sometimes be more
stable than it usually is, by a slight rotation in the C-C bonds and is called the
twist boat conformat'ion.Nevertheless, the chair conformation is the most stable
cyclohexane form.
Chapter 15 Alkanes

a chair form
- <-d half-chair

boat twist-boat

Figure 15-5
Relative energy levels of the conformations of cyclohexane

A conformation having
a lower energy implies
higher relative stability.

I chair
chair form

Based on the energy diagram of cyclohexane, the following inference can be made regarding the stability
of the conformations:
chair conformation >twist boat conformation > boat conformation > half-chair conformation

increasing stability
The MCAT Chemistry Book

In the chair form of cyclohexane, there are two different kinds of carbon-hydro-
gen bonds. Of the twelve carbon hydrogen bonds in a cyclohexane, six bonds
are pointed up or down and are called axial bonds. The remaining six carbon-
hydrogen bonds are pointed at an angle out of the ring and are called equatorial
bonds. Each carbon atom in the ring is attached to one hydrogen atom by an
axial bond, and to the other hydrogen atom by an equatorial bond.

(a) axial position

(e) equatorial position

';I axial

equatorial

When ring flipping occurs between conformers, equatorial groups become axial,
and axial groups become equatorial.

Experimental analysis has confirmed that among the two chair confor-
mations of methylcyclohexane, 95% of the molecules have their methyl group
in the equatorial position. In other words, the methyl group being in the equa-
torial position is more stable than methyl group in the axial position. The
lower stability of the axial position can be attributed to the fact that there is an
increased steric hindrance because of the proximity of the axial methyl group
to the axial hydrogens that are attached to carbon atoms 3 and 5. This interac-
tion called 1,3-diaxial interaction results in steric strain. This accounts for the
increased relative stability of the conformation when the methyl group is in
the equatorial position.
 Chapter 15 Alkanes

axial
1,3-diaxial interactions

H
(more stable) equatorial

CH3
down
cis- l,2-dimethylcyclohexane I

down
trans-l,2-dimethylcyclohexane
The MCAT Chemistry Book

Example 15-1

The cis-geometric isomer of 1,3-dimethylcyclohexane is more stable than its

trans-isomer. Why?

Solution:

To understand why the cis-isomer is more stable, let's draw the possible chair
forms of 1,3-dimethylcyclohexane.

(more stable)

3c:*!:t --
H H

cis- 1,3-dimethylcyclohexane

CH,(~)

trans- 1,3-dimethylcyclohexane

When the two methyl substituents are in 1,3 positions, the cis-isomer can have
both substituents in equatorial position. In the trans-isomer, one methyl group
must always be axial.
Chapter 15 Alkanes

CHAPTER 15 PRACTICE QUESTIONS 4. Choose the correct name of the following

compound from the choices given below.
1. A student is assigned to identi@an unknown
compound in an organic chemistry class. She
is sure that the compound contains only car-
bon and hydrogen atoms. In addition, the
unknown compound is a saturated hydrocar-
bon. If there are fourteen hydrogens in a
molecule of this unknown compound, and it
does not have a ring structure, what is the most
likely number of carbons in this compound?

A. 2-propyl-5-methyl heptane
B. 3-methyl-6-propyl heptane
C. 3,6-dimethyl nonane
2. Which of the following represents the gen-
D. 4,7-dimethyl nonane
eral formula of an alkane?

5. In the combustion reaction of butane, how

many moles of carbon dioxide are formed,
if one mole of butane undergoes complete
combustion in a controlled environment in
the presence of excess oxygen?
3. n-Butane and isobutane are best described
A. one
as:
B. two
C. four
A. stereoisomers.
D. eight
B. anomers.
C. diastereomers.
D. constitutional isomers.
The MCAT Chemistry Book

6. Which of the following represents secondary

carbons?

10. Which of the following alkanes has the

highest boiling point?

A. I & I1 only
B. I & I11 only
C. I1 & IV only
D. I, 11, I11 & IV

7. Carbonium ions have:

A. a positive charge.
B. a negative charge.
C. no charge.
D. either a positive or a negative charge.

8. The gauche conformation is a form of:

A. eclipsed conformation.
B. anti-conformation.
C. staggered conformation.
D. none of the above conformations.

9. In cycloalkanes which of the following

bond angles will have the least angle strain?
Chapter 15 Alkanes

Questions 11-15 are based on the following 13. Alkenes can undergo free radical substitu-
passage. tion reactions with halogens. Which of the
following best represents a chain propaga-
Passage 1 tion step during the free radical chlorina-

-
tion of methane?
Hydrocarbons are compounds com-
posed of carbon and hydrogen atoms. Alkanes A. Cl, 2 :&
are hydrocarbons. As the number of carbons la

increases in straight-chain alkanes: there is a

steady gradation of properties which can be
easily compared and predicted. The properties
of branched alkanes vary considerably imd are C. 'CH3 + CI, -+CH3Cl +;
: 0. l
hard to predict because of other intervening
forces that come into play. The boiling points
of a few alkanes are given below:

14. What is the most likely boiling point of 2,3-

dimethylbutane?

15. The total number of possible structural iso-

mers of heptane is:
11. Which o f the following intermolecular A. three.
forces a r e important with respect to B. seven.
alkanes? C. nine.
D. twelve.
A. Hydrogen bonding
B. Dipole-dipole electrostatic forces
C. Ionic forces
D. Van der Waals forces

12. The melting point of butane is close to:

This page intentionally left blank
Chapter 16 Alkenes

Al kenes

A. INTRODUCTION

Alkenes are hydrocarbon compounds that contain carbon-carbon dou-

ble bonds. The first member of the alkene family is ethene (ethylene), similar to
ethane of the alkane family in terms of the basic name, though the ending is -ene
rather than -ane. The general molecular formula of alkenes is CnHZn.

B. NAMING OF ALKENES

Ethene (Ethylene) CH2=CH,

Propene (Propylene) CH2=CH-CH,

From the third member (butene) of the alkene family onward, there is a
need to specify the location of the double bond to recognize the correct structure
denoted by the name. When naming alkenes, the numbering should begin from
the carbon chain end which gives the double bond position the lowest number.

Watch the numbering of carbons in the following examples.

 The MCAT Chemistry Book

C. STRUCTURAL INTEGRITY AND ISOMERISM OF ALKENES

The carbon atoms which contain the double bonds in alkenes are sp2
hybridized. Each carbon-carbon double bond is made of one sigma and one pi
bond.

Isomerism

Any compound with a carbon-carbon double bond can exhibit cis-trans

isomerism, provided that the carbons involved in the double bond do not have
two of the same groups or atoms attached to each of them. 2-Butene is the
simplest alkene that can have cis-trans isomerism. Trans isomers are generally
More substituted more stable than their cis counterparts. Alkyl groups are mildly electron-donat-
alkenes are usually
ing toward the double bond. This can lead to polarity. For instance, cis-2-butene
more stable than
less subslituted has a net dipole moment as shown in the diagram given below. On the other
alkenes. hand, in trans-2-butene the net dipole is zero since the dipole moments cancel
out (the vector sum of the dipole moments is zero).
cis-isomer trans-isomer

f
net dipole= yes net dipole= no

Both cis and trans-2-butene have van der Waals attractive forces. But, only the
cis-isomer can have dipole-dipole interactions because it has a net dipole mo-
ment. Hence, cis-2-butene has a higher boiling point than trans-2-butene.

The E-Z System of Naming Alkenes

Sometimes we are not able to categorize alkenes into trans and cis iso-
mers. The following example will reveal why that is the case.
Chapter 16 Alkenes

For compounds such as the ones shown above, we have to prioritize the
substituents, and that is the only way to name and identify these compounds. A
new system was proposed by scientists, which categorizes these compounds
under E (entgegen), and Z (zusamnten) configurations. E configuration
describes opposite, whereas Z configuration describes same side. Study the
following examples to get familiarized with this system of naming alkenes. In
order to recognize which substituent is higher or lower, you have to compare
their atomic numbers. That means an atom with a higher atomic number takes
precedence over an atom with a lower atomic number.

Fig. a Fig. b

E- configuration Z- configuration

One key aspect to remember is that when we compare which substituent

is higher or lower, we should compare the substitutions in the same carbon. In
the above example, it is easy to see that on the left substitution, obviously bro-
mine is higher (higher in the atomic number sense) than hydrogen. On the right
side, chlorine is higher (atomic number: 17) than carbon (atomic number:6). So
the compound shown in Fig. (a) has an E configuration, and the one shown in
Fig.(b) has a Z configuration.

D. GENERAL PROPERTIES OF ALKENES

Just like alkanes, the melting and boiling points of alkenes increase with
an increase in the number of carbons (increase in chain length). Carbon-carbon
double bonds are shorter than carbon-carbon single bonds. Alkenes are insoluble
in water, but are soluble in nonpolar solvents such as hexane, and ethers.

E. SYNTHESIS OF ALKENES

We can synthesize alkenes by processes such as dehydrogenation of

alkanes, dehydrohalogenation of alkyl halides, and dehydration of alcohols.
 The MCAT Chemistry Book

From Alkanes

An alkene can be synthesized by the process of dehydrogenation (removal

of hydrogen atoms), by heating an alkane up to about 700-750.

Sample reaction 16-1

Ethane Ethylene Hydrogen

From Alcohols

When alcohols undergo dehydration reactions, alkenes are generated.

There is a chance of rearrangement of the carbocation intermediates to form
more stable carbocation intermediates, whenever possible, resulting in the for-
mation of more than one type of alkenes. The mechanisms of such rearrangements
are discussed in Chapter 21.

The order of
Sample reaction 16-2

CH,CH,OH -H,SO,, heat

CH,=CH, + H20
The only product in the above reaction is ethylene, since there is no
carbocation stability: rearrangement. This is because the intermediate formed in this reaction is a
30 > 20 > 10 primary carbocation, and rearrangement cannot produce a more stable carbocation
since there are only two carbons in the cation intermediate formed from ethanol.

From Alkyl Halides by Dehydrohalogenation

Alkenes can be synthesized by reacting the corresponding alkyl halides with a

suitable strong base that can abstract a proton from one of the carbon atoms,
while the leaving group attached to the adjacent carbon leaves. The general
mechanism is shown below.
 Chapter 16 Alkenes

According to Zaitsev's rule, the major alkene product is the one that is the most
highly substituted. Consider the following example involving 2-bromobutane
with potassium hydroxide.

Sample reaction 16-3

minor product(20%)
C H ~ C H ~ C H = C H ~monosubstituted alkene
H2 H
H 3 C C C C H 3 -* +
I
Br
KOH
CH3CH=CHCH3 disubstituted alkene
major product(80%)

If bulky bases are used, the least substituted alkene may predominate as the
product. In the next example, the base used is tert-butoxide ion. Since it is a
bulky base it will preferentially abstract the less hindered hydrogen, leading to
the formation of the least substituted alkene-the Hofmann product.

Sample reaction 16-4

H
\
H2 CH3
NaOC(CH3)3
H 3 C C C C H 3 -+
H3C/C=C
+
\ CH3
Zaitseb product (minor)

I
Br
HC(CH3h CH3CH2,
,C=C /H
Hoffman product (major)
\
H3C H

From Vicinal Dibromides by Dehalogenation

Vicinal dibromides have two bromines on adjacent carbon atoms. Vici-

nal dibromides can be converted to alkenes by reduction with zinc or iodide ion.
A sample reaction is given below.

Sample Reaction 16-5

I Br
Alkene
Vicinal dibromide
The MCAT Chemistry Book

E REACTIONS OF ALKENES

Hydrogenation

In hydrogenation reactions, H, is added to the unsaturated (carbon-car-

bon double or triple bonds) bonds. he resulting product of hydrogenation of a
pure alkene is an alkane.

Usually, catalysts like platinum, palladium, or nickel are used for these types of
hydrogenation reactions. Hydrogenation reactions are exothermic. Thus heat is
generated as result of hydrogenation and is called heat of hydrogenation.

The greater the substitution of the carbon-carbon double bond is, the lesser the
heat of hydrogenation, and higher the stability of the alkene.

Alkenes with Hydrogen Halides

Alkenes undergo electrophilic addition reactions with hydrogen halides,

to form alkyl halides.

Sample reaction 16-6

CH,=CH2
Ethylene
+ HX -
Hydrogen halide
CH,-CH,X
Ethyl halide

In the process, the hydrogen halide attacks the double bond in the alk-
ene, and the pi electrons in the double bond are transferred to the electrophile,

-
resulting in a carbocation intermediate. This is followed by the formation of the
alkyl halide.

CH,=CH, + HX CH,-CH,X
Ethylene Hydrogen halide Ethyl halide
Chapter 16 Alkenes

-
Alkene Hydrogen halide Carbocation Chloride ion

+
c-
i + cf
i'I
1-
(2) C-C-

I I I
Carbocation Chloride ion Alkyl halide

If the alkene used is not symmetrical, the possibility of different prod-

ucts from hydrogen halide addition is an issue. In such cases, the hydrogen from
the hydrogen halide adds to the double-bonded carbon that already has the greater
number of hydrogens. This is Markovnikov's rule. Based on this rule, we can
predict the major product in such reactions. Consider the following reaction
involving 2-methyl-2-butene with hydrogen bromide.

2-methyl-2-butene
(an unsymmetrical alkene)

more stable

the hydrogen from the hydrogen - H3C-C-C-H

CH3 CH3

I I
3 A\
halide can add here resulting in a
tertiary carbocation
Br CH3 CH3
less stable
CH3 CH3 I
H 3 C C P C H
I
the hydrogen fiom the hydrogen I I I I
secondary carbocation
+
halide can add here resulting in a H

not observed
3 C
I
H
C

BF
C
'
H
Br H

Markovnikov product
(major product)
The MCAT Chemistry Book

An example of a Markovnikov addition is shown below. Watch where the

hydrogen and the bromine are added.

Sample reaction 16-7

Markovnikov addition of hydrogen and bromine

- RI HBr I I
--r / H-C- C-Br

A
R*
Alkene

Sample reaction 16-8

H goes to the double-bonded

carbon that has the greatest
number of hydrogens
Anti-Markovnikov Addition

Hydrogen bromide in the presence of peroxides can add to an unsymmetrical

alkene resulting in anti-Markovnikov products. The change in trend can be ex-
plained based on the mechanistic difference of HBr addition in the presence of
peroxides. Peroxides can easily form free radicals, since the oxygen-oxygen
bond in peroxides is weak. This type of addition is not seen with HC1 or HI. The
mechanism of HBr addition to an alkene in the presence of a peroxide is shown
below.
Chapter 16 Alkenes

ROOR -
Formation of Br radical

2 RO

RO- + - heat

HBr ROH + Br-

Addition of Br radical to alkene (formation of alkyl radical)

+ Br- - 7"' iH3-3' radical ( more stable)

H3C-CC-H
iH3iH3
H 3 C - C C H

I I
H Br
HBr anti-Markovnikov product

H3C-C-C-H
I
Br 2' radical ( less stable)

Notice that when the bromine radical adds to the double-bonded carbon that
contains the most number of hydrogens, the resulting alkyl radical is more stable
(here, tertiary radical is formed). Remember that free radical stability parallels
carbocation stability. A tertiary radical is more stable than a secondary radical
which is more stable than a primary radical.
The MCAT Chemistry Book

Alkenes with Halogens

We will consider the reaction of ethylene with chlorine.

Sample reaction 16-9

The overall reaction:

The mechanism of the reaction:

This is an example of electrophilic addition of C1, to an alkene. The mechanism of

this reaction involves the following steps. In the first step, the ethylene reacts with
chlorine to form the cyclic ethylene chloroniurn ion (intermediate) and chloride ion.
Note that in this cyclic intermediate, the chlorine has a positive charge. This step is
followed by the nucleophilic attack by chloride ion on the chloronium ion. The
reaction is enhanced by electron-donating substituents such as alkyl groups on the
carbon-carbon double bond, since such groups can firher stabilize the formation of
the transition state which results in the formation of the chloroniurn ion. Halogen
addition is usually an anti addition process.

Halogen addition is usually an anti addition process. See the next reaction that
exemplifies this aspect.

Sample reaction 16-10

-
:Br : trans- l,2-Dibromocyclopentane
cyclopentene

H H Br
bromonium
Ion
Chapter 16 Alkenes

Alkenes with Halogens in Aqueous Medium

When a halogen is reacted with an alkene in the presence of water, an

organic product called halohydrin is formed by the addition of a halogen atom
and a hydroxyl group to the double bond. The reaction proceeds by the attack of
halogen resulting in a halonium ion. Once the halonium ion is formed, the nu-
cleophile (water) will attack the halonium ion resulting in a halohydrin. The
reaction follows an anti addition pattern. If the alkene is unsymmetrical, the
nucleophilic attack of water will be on the most highly substituted carbon.

Sample reaction 16-11

CH,=CH,
Ethylene
+ C1, + H 2 0
Chlorine
- HOCH,CH2C1 + HC1
Halohydrin Hydrogen
chloride

Chloronium ion
(halonium ion)
H

H
\
/'='\
7

H
3
c1-
- H - C C H
CI
I
H
CH3
I

H H
H H
Nuclenph~l~c
attack
by water

C1 CH3

HCI + H C
I C -
I H

H :o-H
~alohgrin

Sample reaction 16-12

cyclopentene

anti addition product

The MCAT Chemistry Book

Epoxidation

Sample reaction 16-13

(Peroxyacid)

II
RC-OOH
0
II
CH2=CH2 + RC-OH
Ethylene
0
iH2 Carboxylic acid

Epoxide
Alkenes react with peroxy acids to form epoxides and carboxylic acids as products.

Ozonolysis

Alkenes react with 0, (Ozone) to form ozonides, which on hydrolysis

with water form aldehydes or ketones or both, depending on the type of the
reacting alkene. This is illustrated by the sample reactions.

Sample reaction 16-14

AN ALDEHYDE

Sample reaction 16-15

A KETONE AN ALDEHYDE
Chapter 16 Alkenes

Hydroxylation using Osmium Tetroxide

Sample reaction 16-16

o,, /p

\
/c=c\
/ + Os04
Osmium
tetroxide
- -I
0'

/c-c\
0s
0
'
I
--I II
H202
OH OH
I
C-C- + 0sO4

Cyclic osmate Glycol(diol)

Osmium tetroxide can undergo reaction with alkenes to form a cyclic

osmate, which in the presence of hydrogen peroxide results in a glycol (diol).
Hydrogen peroxide oxidizes the osmium back to osmium tetroxide, while hydro-
lyzing the cyclic osmate to glycol. The predominant product is a syn addition
product.
The MCAT Chemistry Book

Acid Catalyzed Reaction

Sample reaction 16-17

CH;
H3C\
C
/CH3 H2S04/H 2 0
*
I
HO-C-CH2CH3
/C= \
H3C H I
CH3
(major product)
Alkenes react with aqueous acidic solutions to form alcohols. The reac-
tion intermediate is a carbocation. There is possibility of rearrangement of the
intermediates. The major product can be predicted using Markovnikov's rule.

Hydroboration-Oxidation

sample reaction 16-18

CH3CH2CH2CH=CH2 CH3CH2CH2CH2CH20H
2. Hz02, NaOH
(major product)
Oxidation followed by hydroboration of alkenes results in alcohols. This
reaction takes place in an anti-Markovnikov fashion. Notice that the hydrogen
atom, instead of attaching to the carbon contained in the double bond with the
highest number of hydrogen substituents, attaches to the carbon with the least
number of hydrogen substituents.

Diborane (B,H,), a dimer of borane (BH,), is usually used complexed

together with tetrahydrofuran (THF) since diborane by itself is a toxic, and
flammable gas. Borane entity actually adds to one of the double-bonded car-
bons resulting in an alkylborane. BH, is a strong electrophile and adds to the
least highly substituted double-bonded carbon. This preference makes sense
because in the transition state, the electron deprived boron pulls electrons
from the pi cloud resulting in a partial positive charge to the other carbon
atom. This partial positive charge is better stabilized on the more highly sub-
stituted carbon. Hydrogen peroxide under basic conditions oxidizes the
alkylborane to an alcohol. In effect, the addition in hydroboration-oxidation is
anti-Markovnikov.
Chapter 16

Sample reaction 16-19

CHI

CH3
\
/C=C\
/H

H
-* $1
H,C-C-C-H
CH2
----

H- - - -BH2
-
H202MaOH
H20
H3C-C-C-H
I I
H OH
H-BH2
6-
anti-Markovni kov product
(major product)

The addition of hydrogen and boron is simultaneous, and they must add to the
same side of the double bond. Hence, this addition reaction involves syn addi-
tion or same-side addition. Study the next reaction.

Sample reaction 16-20

transition state

v
syn addition
Oxymercuration-Demercuration

Sample reaction 16-21

Alkenes can be converted into alcohols by oxymercuration-demercura-

tion. The addition of H and OH is in accordance with the Markovnikov's rule.
There is no rearrangement of the intermediates in this process.
The MCAT Chemistry Book

In the oxymercuration process, the electrophilic addition of the mercu-

ric species occurs resulting in a mercurinium ion which is a three-membered
ring. This is followed by the nucleophilic attack of water and as the proton
leaves, an organomercuric alcohol (addition product) is formed. The next step,
demercuration, occurs when sodium borohydride (NaBH,) substitutes the mer-
curic acetate substituent with hydrogen. If an alkene is unsymmetric,
Oxymercuration-demercuration results in Markovnikov addition. The addition
of mercuric species and water follows an anti (opposite side) addition pattern.
This reaction has good yield, since there is no possibility of rearrangement un-
like acid-catalyzed hydration of alkenes.

~2.~
Sample reaction 16-22

(mercuric acetate)

R
CH3
- H
0
II
Hg(0CCH3)2 CHI

Hg
H
- ~ ..
H
H

cH~
3 - 4%
N 2
Hg(OAc)
0
(94~)
mercurlnium ion - H+

2
1
_
Hg(OCCH3)2 is represented as Hg(OAc)*

HG- .. NaBH4 " .- 6

0
0 H
6 %c Q 5
5
CH~ H cH; Hg(0Ac)
I -methyl- 1-cyclopentanol organomercuric alcohol
Chapter 16 Alkenes

The Diels-Alder Reaction

The Diels-Alder reaction is an addition reaction involving an alkene and

a diene. Let's look at a representative Diels-Alder reaction involving 1,3-buta-
diene and an alkene (dienophile means diene-lover). The reaction involves a
cyclic transition state. The product is usually a cyclic addition product. Study
the representative reaction given below. Pay close attention to how the new
bonds are formed in relation to the reactants.

H H
RI
R2
1,3-Butadiene Alkene The Cyclic Cycloaddition
(dienophile) transition product
state
Notice that the substituents in the alkene remain the same way in the product. In
other words, cis substituents remain cis in the cycloaddition product. Hence, the
Diels-Alder reaction is stereospecific.

Sample reaction 16-23

)-y + - Product
Diene Maleic anhydride
(dienophile)

Diels-Alder product
The MCAT Chemistry Book

CHAPTER 16 PFUCTICE QUESTIONS A student researcher calculated the num-

ber of moles of hydrogen used per mol for
1. All the following are possible products of the hydrogenation of an unsaturated (only
the acid-catalyzed dehydration reaction of double bonds) aliphatic non-cyclic hydro-
the compound shown below, EXCEPT: carbon compound. If the number of moles
of hydrogen used for the complete hydro-
genation of each mol of the hydrocarbon is
eight, how many double bonds were there
in the con~poundthat was hydrogenated?

A. two
B. four
C. eight
D. sixteen
Chapter 16 Alkenes

3. Choose the product of the following

reaction.

D. none of the above

5. Which ofthe following is the major product

of the hydroboration-oxidationof 1-butene?
and
0
II
H 3 C C O H
0

D*
II
H3C-C-CH3 and

6. Which of the following compounds has the

highest heat of hydrogenation?
4. Which of the following is the most likely
product of the reaction indicated below? 1 A. ethylene
/ B. propene
The MCAT Chemistry Book

7. The major product that results in a reaction 111) There is no intermediate involved.
involving 1-propene with hydrogen bro- IV) Methyl shifts can occur in the interme-
mide, in the presence of peroxides is: diates.
V) Hydride shift can occur in the interme-
diates.

A. I, IV & V only
B. 11, IV & V only
C . I11 only
D. I1 & V only
8. Which of the following is true regarding a
reaction of cis-2-pentene with KMnO,? Questions 11-15 are based on the following
passage.
A. A trans diol will be formed.
B. A cis diol will be formed. Passage 1
C. The reagent is not strong enough to
oxidize cis-2-pentene. The following synthesis reactions involving
D. The double bond will be broken, and is alkenes were done in a lab.
followed by a ring closure or ring
formation. Reaction 1

9. In the acid catalyzed dehydration reaction

of an alcohol, which of the following
aspects listed can definitely be true? Reaction 2

A. There can be no rearrangement of the

intermediate, regardless of the alcohol
involved.
B. There can be rearrangement involved,
resulting in less stable intermediates
from more stable intermediates. (isolated) 5(
C . If possible, the major product is the [CH3C=0 ] + CH20
most substituted product because of its
higher stability.
D. None of the above.
Product A
10. In the acid-catalyzed dehydration of
alcohols to alkenes, which of the following
are true?

I) A carbanion intermediate is involved.

11) A carbocation intermediate is involved.
Chapter 16 Alkenes

Reaction 3 11. Which of the following can be the oxida-

tion product of an alkene?

A. CH,CH,CHO
B. HOCH,CH,OH
C. CH,CH,CH,COOH
D. All the above

12. Ethylene oxide in the presence of H,O can

be converted to ethylene glycol by bxida-
tion. In the process, the ring in ethylene
oxide is attacked by water. Which of the
following best describes the role of water?

A. Electrophile
Reaction 4 B. Nucleophile
C. Merely a solvent
D. No active part in the reaction other ~ h a n
being a spectator molecule

13. In Reaction 2, what is the identit! of

H2
Lindlar Product A?
catalyst
A. Acetic acid
7 B. Carbon dioxide
Product X C. Methane
D. None of the above

14. Products X and Y in Reaction 4 are best

described as:
Nai NH3 (0
A. mirror images.
v B. tautomers.
C. anomers.
Product Y
D. geometrical isomers.
The MCAT Chemistry Book

15. What is the correct name of the compound

shown below?
Chapter 17 Alkynes

Al kynes

A. INTRODUCTION

Alkynes are hydrocarbons that contain carbon-carbon triple bonds. The

general formula of alkynes is CnHzn
- 2.

HCSCH Acetylene

In acetylene, the carbon is sp hybridized. The triple bond is composed

of one sigma bond, and two pi bonds. The bond angle is 180". We should also
realize that the sigma bonds are formed by sp hybrid orbitals, and the pi bonds
are formed by the p orbitals.

If the triple bond in an alkyne is at the end of a carbon chain, it is called a

terminal alkyne. If the triple bond is not at the end of a carbon chain, it is called
an internal alkyne.
HCCCH2CH2CH3 H3CH2CH2CCCCH2CH3
A terminal alkyne An internal alkyne

B. NAMING OF ALKYNES

The naming of alkynes is similar to that of alkenes.

sp hybridized

Ethyne (Acetylene) Propyne 3-methyl- 1-hexyne

The MCAT Chemistry Book

C. SYNTHESIS OF ALKYNES

Acetylene Synthesis by Adding H,O to CaC, (calcium carbide)

Sample reaction 17-1

CaO
Calcium
- -
C (Carbon)
heat
CaC2
Calcium carbide
H20
HCeCH

Acetylene
+ Ca(OH)?

Calcium Hydroxide
Oxide

From Dihalogenoalkanes

Sample reaction 17-2

A representative reaction is given below:

R 1 - C C R Z * R,-C==C-R2

H
I BrI KOH, C2H20H
Alkyne
A dibromoalkane
From Acetylene

Higher alkynes can be synthesized from acetylene by reacting with NaNH,

followed by treatment with the appropriate alkyl halide.Termina1 alkynes can be
deprotonated using strong bases such as sodium amide. Hydroxides or alkoxides

r
are not strong enough to deprotonate an acetylenic hydrogen.
Acetylenic hydrogen(acidic proton)

H 3 C H 2 C H 2 C C EC H
A terminal alkyne

Sample reaction 17-3

Acetylene Sodium amide Sodium acetylide ~rn&nia

Chapter 17 Alkynes

D. REACTIONS OF ALKYNES

Hydrogenation

In the presence of catalysts such as palladium, platinum, or nickel, alkynes

can be hydrogenated to the corresponding alkanes.

Sample reaction 17-4

1-Pentyne Pentane
Alkynes can be hydrogenated to alkenes by using specific catalysts such
as Lindlar palladium. This reaction is stereoselective resulting in syn addition.

Sample reaction 17-5

-
HZ/Lindlar
Palladium
CH3CeCCH2CH3 H3C\
/"=\
C/CH2CH3

An alkyne can be hydrogenated to a trans-alkene by hydrogenating the

alkyne with sodium in liquid ammonia.

Sample reaction 17-6

Na / Liquid NH3
CH3C CCH2CH3 t "\ C/CH2CH3
/C=
2-Pentyne CH3
trans-2-Pentene
Acid-Catalyzed Hydration

Alkynes can undergo acid-catalyzed hydration reactions. The product is

an enol, which is an unstable intermediate, and is immediately converted to a
ketone. The formation of en01 is based on Markovnikov addition (hydration).

Alkyne En01 Ketone

The MCAT Chemistry Book

Sample reaction 17-7

Alkynes *ith Hydrogen Halides

Alkynes can undergo reactions with hydrogen halides. The reaction

follows Markovnikov's addition of hydrogen and halogen to the triple bond.
When two moles of hydrogen halide gets added to an alkyne, the reaction
follows the same Markovnikov's pattern resulting in a geminal dihalide (two
halogen atoms attached to the same carbon atom). Study the reactions given
below.

Sample reaction 17-8

Br

HC CCH2CH2CH3
HBr I
H2C=CCH,CH2CH3
1-Pentyne 2-Bromo- 1-pentene

2'2-dibromopropane
Alkynes with Halogens (A geminal dihalide)

Alkynes can undergo reactions with halogens forming di- and tetra-haloge-
nated products.

Sample reaction 17-9

Chapter 17 Alkynes

Ozonolysis

Alkynes can undergo ozonolysis. The products formed are carboxylic acids.

Sample reaction 17-10

In this reaction, the products formed are butanoic acid and acetic acid. If a ter-
minal alkyne is used, the products are carbon dioxide and a carboxylic acid. See
the example given below.

Reaction Involving the Acidic Hydrogen in an Alkyne

The acidic hydrogen present in terminal alkynes can undergo reactions

with Grignard reagents. A sample reaction is shown.

Sample reaction 17-11

Alkyl magnesium halide

(Grignard reagent)

The acidic hydrogen

The MCAT Chemistry Book

Acetylide with Aldehydes and Ketones

Acetylides are strong bases and are good nucleophiles. So they can add to the
carbonyl groups in aldehydes and ketones. The alkoxide ion that is formed dur-
ing the reaction can be protonated to an alcohol by treating it with aqueous
dilute acid.

-
R C C H - NaNH2
(sodurn amide)
Acetylide ion

R C E C :
-
(Nudeophile)
\
YC\
R4*
)I
H
Aldehyde
Chapter 17 Alkynes

CHAPTER 17 PRACTICE QUESTIONS

4. The compound shown above is treated with

hydrogen in the presence of Lindlar catalyst.
The major product is:

A. pentanol.
B. cis-2-pentene.
C. pentane.
D. trans-2-pentene.
1. In the compound shown above, which of
the indicated bonds (arrows) have the short-
est carbon-carbon bond? 5. 1-Butyne is treated with aqueous sulfuric
acid in the presence of mercuric oxide as
the catalyst. The major product is:

2. If bottle A contains cis-2-butene, bottle B

contains 1-propyne, and bottle C contains
butane, identifl the bottle that contains the 6. Which of the following choices represents
compound with carbon-carbon bonds of the the product of ozonolysis of 3-Hexyne?
highest bond energy.
A. Propanone
A. Bottle A B. Propanal
B. Bottle B C. Hexanoic acid
C. Bottle C D. Propanoic acid
D. They all have equal bond dissociation
energies.
7. Double dehydrohalogenation of an alkyl
vicinal dihalide can directly result in:
3. Which of following compounds has the
lowest pKa value? A. a carboxylic acid.
B. an alkyne.
A. Ethane C. an alcohol.
B. Ethene D. an ester.
C. Acetylene
D. None of the above listed compounds are
strong acids, and hence they do not have
pKa values
The MCAT Chemistry Book

-
8. The process by which an alkyne can be
directly converted into an alkane is called: Reaction 1
ZaC, + 2 H 2 0 HC=CW t Ca (OH)?
A. dehydrohalogenation.
B. dehydration.
Reaction 2
C. hydrolysis.
D. hydrogenation.

9. If liquid ammonia in the presence of sodium

is added to an alkyne, the major product is:
I
CH3CH-CHCH,
I - KOH
A CH3CeCCH3

A. a trans-alkene. 41so consider the following reactions.

B. a cis-alkene.
C. an aldehyde. Reaction 3
D. a carboxylic acid.

10. Which of the following is true regarding

H3CCECH - HBr
Br
I
H,cc=CH~

alkynes? Reaction 4 Br
A. Alkynes have generally higher boiling
points than corresponding alkanes.
B. Alkynes have sp hybridized carbons. Quinoline
C . Acetylene (an alkyne) can form salts
called acetylides when exposed to Quinoline is a heterocyclic amine.
strong bases.
D. Ali the above are true.
11. The hybrid orbital that characterizes and
differentiates alkynes from other simple
Questions 11-16 are based on the following hydrocarbons like alkanes and alkenes, is
passage. that alkynes have hybrid orbitals which
have:
Passage 1
A. 75%p character and 25% s character.
Alkynes are hydrocarbons with carbon- B. 6 6 % character
~ and 33% s character.
carbon triple bonds in them. The simplest C. 50% p character and 50% s character.
alkyne can be prepared by the process shown D. none of the above.
in Reaction 1.
Chapter 17 Alkynes

12. Reaction 3 is best described as: 15. Which of the following is the most likely
structure of quinoline?
A. a substitution reaction.
B. an addition reaction.
C. an elimination reaction.
D. a dehydrogenation reaction.

13. Which of the following sequences best

describes a way to synthesize 1-hexyne
from acetylene?

A. 1. NaNH2/liq. ammonia
2. n-propyl bromide
B. 1. NaNH2/liq. ammonia
2. tert-butyl bromide
C. 1. n-Propyl bromide
2. NaNH2/liq. ammonia
D. 1. NaNH2/liq. ammonia
2. n-butyl bromide

14. Lindlar's catalyst is often used for the

reduction of alkynes to alkenes. The catalyst
consists of palladium which is deposited in
a finely divided state of barium sulfate, which
is subsequently treated with a heterocyclic
amine called quinoline. Which of the
following is the most likely function of
quinoline?

A. To speed up the reaction so that the

alkyne is completely converted to its
most reduced form of hydrocarbon
B. To slow down the reaction, because the
function of a catalyst is to slow down
the reaction
C. To moderate the catalytic activity to
facilitate a restrictive reduction
D. It acts as an oxidizing agent so that the
alkyne is reduced.
The MCAT Chemistry Book

16. Predict the major product of the reaction

shown below:

H3CH2CCeCCH3 - K

Liquid NH,

A. H3CH2CC=CCH2K
Chapter 18 Aromatic Compounds

Aromatic Compounds

A. INTRODUCTION

Aromatic compounds are compounds which have benzene rings in them.

Aromatic hydrocarbons are also called arenes. Some compounds have struc-
tures which look like fused benzene rings. Such compounds are called
polycyclic aromatic compounds.

Benzene Toluene

Polycyclic aromatic hydrocarbons

Naphthalene Anthracene
The MCAT Chemistry Book

R. BENZENE

Structure of Benzene

The formula of benzene is C6H6.The ring structure has alternate double

and single bonds as shown in the diagrams below. According to the latest theories,
benzene is in resonance between the two structural entities as shown below.
Benzene has a structure that is a hybridized form of these two structures.

The hybridized structure is usually represented as shown below:

Figure 18-1
Chapter 18 Aromatic Compounds

The six carbons in the benzene ring have a planar arrangement of a reg-
ular hexagon. The carbons are located at the vertices of the hexagon. The
carbon-carbon bonds have the same length, and each bond angle is 120". The
hybridization is sp2.The sigma bonds are formed by the sp2hybridized orbitals.
However, the unhybridized 2p orbitals in each carbon overlap to form a cyclic ~nbenzene, there are
pi system around the ring. The delocalization of these electrons creates the pi six pi electrons in
system in aromatic compounds. The electron cloud of the pi system occupies *he ring with Over-
the regions above and belowthe ring as depicted in Figure 18-1. lapping p orbitals.

C. DERIVATIVES OF BENZENE

Many derivatives of benzene are substituted derivative compounds. Some

examples of such compounds are shown below:

SOME MONOSUBSTITUTED AROMATIC COMPOUNDS

Toluene Chlorobenzene Nitrobenzene Aniline

COOH CHO

Phenol Benzoic acid Benzaldehyde

- 1 Benzyl group
Styrene
The MCAT Chemistry Book

b\ t
(3)
"\(2)

With respect to the substituent (the methyl group)

arrow (1) indicates the ortho position,
arrow (2) indicates the meta position,
arrow (3) indicates the para position.

(Xylene is the general name of a dimethyl-substituted benzene)

D. PROPERTIES OF AROMATIC COMPOUNDS

Aromatic hydrocarbons are nonpolar, and are insoluble in water. They

commonly undergo reactions like aromatic electrophilic substitution reac-
tions and reduction reactions.

E. CONCEPT OF AROMATICITY

Aromaticity of compounds is based on certain rules. According to Huckel's

rule, the number of pi electrons present should be a number denoted by the
formula 4n + 2, where n is 0, 1,2,3, . . .. Hence, for compounds to be consid-
ered aromatic the number of pi electrons should be 2 , 6 , 10, . . .. In addition,
Chapter 18 Aromatic Compounds

the structure should also have a cyclic pi system to be aromatic. Atoms in the
ring must have unhybridizedp orbitals. These unhybridizedp orbitals must over-
lap resulting in a cyclic pi system. For this type of overlap, the structure must
have planar (or nearly planar) configuration.In other words, the atoms related or
involved in the pi bond should be in the same plane.

Test whether you can recognize the aromaticity of the structures in the examples
that follow:

Tips for testing aromaticity

Step 1 - Count the number of pi electrons.

Step 2 - See whether there is a cyclic p orbital overlap.

Predict the aromaticity of the compounds given below:

Compound 1

Number of pi electrons - 6
Cyclic overlap o f p orbitals - Yes
Aromatic - Yes

Compound 2

Number of pi electrons - 4
Cyclic overlap o f p orbitals - No
Aromatic - No
The MCAT Chemistry Book

Compound 3

Cyclopentadienyl anion
Number of pi electrons - 6
Cyclic overlap o f p orbitals - Yes
Aromatic - Yes

Some examples of heterocyclic aromatic compounds

0
ON
Pyridine

The nonbonded electron pair is in an sp2 orbital which is perpendicular

sp2
to the pi system and thus not part of the pi system. Since it has six
pi electrons in a planar confirmation, it is aromatic.

sp2
(Tk py-le

O H The nonbonded electrons occupy the unhybridized p orbital and thus

are part of the cyclic pi system. With a total of six pi electrons,
p y ~ o l eis aromatic.

0 0
There are two lone pairs of electrons on the oxygen atom in Furan.
sp2
One of the lone pairs occupies the sp2hybrid orbital, while the other
pair occupies the unhybridizedp orbital and forms the overlap with
the pi electrons of the carbon atoms to form a continuous ring of
six electrons. Hence, furan is aromatic.
 Chapter 18 Aromatic Compounds

E REACTIONS OF AROMATIC COMPOUNDS

Benzene Stability

Benzene, unlike alkenes, will not react with halogens to form addition products.

Br2
-
+ No addition product

This exemplifies the extra stability of the double bonds present in the benzene
ring. However, benzene can undergo substitution reactions with halogens in the
presence of a Lewis acid catalyst. The Lewis acid enhances the electrophilic
nature of the halogen, thus enabling the reaction to proceed.

+ HBr

Electrophilic Substitution Reactions

One of the most characteristic reactions of benzene is the electrophilic

substitution reaction, in which a hydrogen is replaced by an electrophile. In
such reactions, the benzene acts as the nucleophile.

ELECTROPHILIC AROMATIC SUBSTITUTION REACTION

Benzene Electrophilic reagent Substitution products

The MCAT Chemistry Book

In a typical aromatic substitution reaction, the electrophile (means elec-

tron loving) accepts the electron pair from the pi system of benzene, resulting in a
carbocation. This cation of benzene is called the cyclohexadienyl cation. Then,
the cyclohexadienyl cation loses a proton forming the substitution product.

MECHANISM OF ELECTROPHILIC AROMATIC SUBSTITUTION

Benzene

slow
w

d-
H E----Z Cyclohexadienyl
cation
Electrophile

. Electrophilic substitution
product

Nitration

Benzene can be nitrated by reacting with nitric acid (HNO,). This is

usually done in the presence of sulfuric acid (H,SO,).

Sample reaction 18-1

Benzene Nitrobenzene
In this reaction, nitroniurn ion (NO,' ) acts as the electrophile.
Chapter 18 Aromatic Compounds

Friedel-Crafts Reactions

In Friedel-Crafts reactions, benzene is reacted with acyl or alkyl chlo-

rides, in the presence of metal halides as catalysts. The metal halides act as
Lewis acids in these reactions. The two types of Friedel-Crafts reactions are
alkylation and acylation.

(1) Alkylation

In Friedel-Crafts alkylation, benzene is reacted with alkyl chlorides in the

presence of metal halides (AlCl,, AlBr,) as catalysts. The-catalyst serves as
Lewis acid and increases the electrophilicity of the alkyl halide. Alkylation is
important for the synthesis of alkyl substituted derivatives of benzene. But there
is a possibility of rearrangement of the intermediatesresulting in undesired prod-
ucts. For example, if primary halides are used in alkylation, they can rearrange
to form secondary or tertiary carbocations which are more stable intermediates.
This can result in multiple products.

Sample reaction 18-2

Benzene Ethyl chloride Ethylbenzene Hydrogen

chloride
The MCAT Chemistry Book

The Mechanism of Alkylation Rearrangement

primary

0 CH3
I
+ CH3CHCH;Cl ~ 1
carbocation (less stable)

YH3
~ C H1 ~ C ~H C H

J
6 ~-CI-

1
- 6-AICI,
-

I
CH3CCH3
+
hydride shift resulting
in a more stable carbocation
CH3 -tertiary carbocation

6-
C1- -A1C13
0
0' 1
..
C"I-AICI~
:

CH3
I

I OH
1
;l--Alc13
/
CH2CHCH3

CFH3 I
'ICH)
CH3
CH3
I
H2CHCH3
+ HCI + AIC13
Chapter 18 Aromatic Compounds

(2) Acylation

In Friedel-Crafts acylation reactions, benzene is reacted with acyl

chlorides or acid anhydrides in the presence of metal halides (Lewis acids). The
importance of acylation is that there is no rearrangement, unlike alkylation where
there is a possibility of rearrangement of the cation intermediates.

The acyl halide forms a complex with the Lewis acid (AlCl,), followed by the
leaving of the halogen along with the Lewis acid. The resulting ion, called acylium
ion, is resonance stabilized and is strongly electrophilic. This ion reacts with
benzene to form an acylbenzene.

'0% +;i
II Ill
CH3CH2-cH CH3CH2-c
(The acylium ion is resonance stabilized)

0 + AICI~
:0'
II
C-CH2CH3

og-c~~o + HCI
\-
+ salts
The MCAT Chemistry Book

Sample reaction 18-3

0

Benzene Acyl chloride Acyl benzene Hydrogen chloride

Acyl products that are formed can be reduced by reactions such as

Clemmenson or Wolf-Kishner reductions.

0 Clemrnenson reduction
II
0 c c H 2 c H 2 c H 2Znc (Hg)/
H 3 HCI * ~ ~ ~ 2 ~ ~

0
Wolf-Kishner reduction
c- CH~CH,

Sample reaction 18-4

NH2-NH2/KOH

-
ethylene glycoL
heat 0'cH2
0
I
ICCH2CH2COOH
+ HCI
AICI3
Benzene Acid anhydride
Chapter 18 Aromatic Compounds

Halogenation

Sample reaction 18-5

Benzene can be halogenated in the presence of Fe. In this reaction, the

iron(II1) bromide acts as the catalyst, which is formed from the iron and the
bromine. The bromine-iron(II1)bromide complex that is formed acts as the elec-
trophile which attacks the benzene.

Sulfonation

Benzene can be sulfonated by heating with sulfuric acid.

Sample reaction 18-6

H,SO, / heat w H
30s'J( +
H20

Benzene Benzenesulfonic acid

G. DIRECTIVE EFFECTS OF SUBSTITUENTS

Consider the reaction of benzene with an electrophile (E).

Notice that the positive charge is spread only on secondary carbons, and thus all
resonance structures are equally stable.
The MCAT Chemistry Book

In aromatic substitution reactions, the groups already present in the

benzene ring can significantly influence the place of electrophilic attack of
the incoming substituent. In other words, the substitution is influenced by the
groups that are already present in the benzene ring. There are two types of
substituents (groups) - activators and deactivators. The groups that are
activators cause the ring to be increasingly reactive than benzene. The groups
that are deactivators cause the ring to be decreasingly reactive than benzene.

Activating Groups

As mentioned above, the activators increase the reactivity of the ring

than that of benzene. The substitution primarily occurs in the ortho and para
positions of the ring relative to the activating group. For this reason, activators
are also called ortholpara directors. Let us analyze this with an example. In
the following reaction, phenol is nitrated. Notice that phenol contains a hydroxyl
group (-OH) which is an ortholpara activator. So the substitution occurs at ortho
and para positions with respect to the -OH group.

Sample reaction 18-7

Phenol Ortho-Nitrophenol Para-Nitrophenol

Chapter 18 Aromatic Compounds

Now let's us consider an electrophilic attack on toluene.

Ortho attack o n toluene

H
__t u u
+
+ /
most Because the attack
favorable on the ortho or para
attack results in
more stable cation
Para attack o n toluene . intermediates, those
intermediates are
formed faster and
thus the resulting
products,fiom those
intermediates are
t h e predominant
products.
H E H E H E
H
most favorable

Meta attack o n toluene

By observing the resonance forms of the cation intermediates, it is clear

that ortho and para attacks are favored. This is because ortho and para attacks
have the possibility of spreading or sharing the positive charge by a tertiary
carbon. Notice that when the attack is at the meta position, the positive charge is
only shared by secondary carbons. A positive charge is better stabilized when it
is on a tertiary carbon than on a secondary carbon. The methyl substituent is
electron-donating and activates the benzene ring toward electrophilic attack,
and the activation is more towards the ortho and para positions than the meta
positions. In other words, alkyl groups are electron-donating substituents that
are ortho-para directing by donating the electron density and thereby induc-
tively stabilizes the intermediate.
The MCAT Chemistry Book

Alkyl groups are electron-donating substituents, but it might seem

counterintuitive to think that groups like -OH (hydroxyl) and -0CH3 (methoxy)
are also ortho/para activators since oxygen is highly electronegative atom. This
is because the oxygen atom that is bonded to the ring carbon has lone electrons
or nonbonding electrons. As a result, the positive charge on the carbon atom in
the intermediates formed from ortho and para attacks is stabilized through reso-
nance. In other words, such groups can also donate electron density because of
the presence of nonbonded electrons.

Para
attack

Deactivating Groups

Deactivators make the ring less reactive than benzene. There are two
types of deactivators - ortholpara and meta deactivators.

1) Ortholpara deactivators

Some deactivators direct the incoming substituents primarily to the ortho

and para positions. Halogens (Fluorine, Chlorine, Bromine, Iodine) are ortho/
para deactivators.They are electron withdrawing substituents through inductive
effect. Furthermore, they have nonbonded electrons that can donate electron
density by resonance. Because of the high electronegativity of halogens, they
pull the electron density away from the ring, making the ring less susceptible to
electrophilic substitution (deactivating property). Halogen substituents have
nonbonded electrons which can be donated to a positively charged carbon in the
intermediates resulting from ortho and para attacks. Hence, halogens are ortho,
para-directing, and deactivating substituents.
Chapter 18 Aromatic Compounds

Ortho
attack

Para
attack

2) Meta deactivators

The meta deactivating groups direct the incoming substituents to the meta
position. These groups are strongly electron-withdrawing groups. Consider the
following example.

Major product
(meta substitution)

The substituent acyl group has a highly polarized carbon-oxygen double bond.

The positively charged carbon withdraws electron density from the benzene
ring inductively. This accounts for the deactivation (less reactivity than ben-
zene) of the ring toward electrophilic substitution.
The MCAT Chemistry Book

Ortho
attack
6
-
6
- 6
-
!

-- unstable
H

(adjacent positve charges)

Para
attack

unstable

Meta
attack

Both ortho and para attacks result in an intermediate that has adjacent
positively charged (polarized) atoms, making it a highly unstable (higher energy)
form. On the other hand, meta substitution doesn't result in an intermediate with
positively charged atoms adjacent to each other. Thus, meta substitution results in
the most stable (lower energy) intermediates. This accounts for the predominance
of meta substitution products if acyl or similar groups are present in the ring.
Chapter 18 Aromatic Compounds

Table 18-1 Some Common Directors

ORTHO, PARA DIRECTORS

Activating Deactivating
-OH Halogens (-X)
-OR
-NH2
-R
-Ar
-NHR
-NR2

0
II
-0CR
T h e MCAT Chemistry Book

CHAPTER 18 PRACTICE QUESTIONS 2. The carbons in the benzene ring are:

1. Which of the following compounds is com- A. sp hybridized.

monly known as xylene? B. sp2'hybridized.
C. sp' hybridized.
D. not hybridized.

3. All the following are monosubstituted aro-

matic compounds, EXCEPT:

A. phenol.
B. benzoic acid.
C. xylene.
D. toluene.

4. A compound can be aromatic, only if it has

a certain number of pi electrons in its ring.
All the following numbers can be attributed
to the number of pi electrons and aromati-
city, EXCEPT:

A. two.
B. four.
C. six.
D. ten.

5. For the reaction involving benzene and

nitric acid in the presence of sulfuric acid,
which of the following is true?

A. The nitronium ion acts as the electrophile.

B. The reaction is an example of nucleo-
philic hydrogenation.
C. The reaction is an example of electro-
philic addition reaction.
D. None of the above
Chapter 18 Aromatic Compounds

6. What is. the name of the reaction shown 8. The group -NO, can be best described as:
below?
A. an ortholpara activator.
B. a meta activator.
C. an orthoipara deactivator.
D. a meta deactivator.

A. Clemmenson reaction 9. Halogens can be best described as:

B. Williamson synthesis
C. Raman synthesis A. orthoipara activators.
D. Friedel-Crafts reaction B. meta activators.
C. ortholpara deactivators.
D. meta deactivators.

10. If the compound shown below was reacted

with nitric acid in the presence of sulfuric
acid, which of the following is the major
product?

CHO

A. A para substituted product

7. The reaction shown is commonly known B. A meta substituted product
as: C. An ortho substituted product
D. No net reaction occurs
A. Clernrnenson reduction.
B. Wolff-Kishner reaction.
C. Benedicts reaction.
D. Zaitsev reaction.
The MCAT Chemistry Book

Questions 11-16 are based on the following

passage.

Passage 1

The earliest predictions about the struc-

ture of benzene could not completely explain
some of its properties. Later it was found that
benzene has a cyclic structure which is com-
monly represented as follows:

Compound A + Compound B + Compound C

(major product)

11. Which of the following is true regarding

Reaction 1 described in the passage?
These two structures are resonance
structures of benzene. Benzene is also com- A. It is a Friedel-Crafts acylation reaction.
monly represented as shown below: B. It is a reaction which results in a single
product.
C . AlC1, acts as a Lewis base.
D. Rearrangement is possible.

12. Alkoxy group is best described as:

A series of reactions were conducted using ben-
zene and other aromatic compounds.
A. an ortho, para-director, and an activating
group.
Reaction 1
B. an ortho, para-director, and a deactivat-
ing group.
In Reaction 1, benzene was reacted with n-pro-
C . a meta-director, and an activating group.
pyl chloride in the presence of AlC1,.
D. a meta-director, and a deactivating
group.
Reaction 2

Nitrobenzene was reacted with nitric acid and

sulfuric acid. The reaction occurred as follows:
Chapter 18 Aromatic Compounds

13. If phenol is reacted with bromine, the major 14. The reaction shown here is:
product formed is:

a:> Br2
w
Carbon disulfide

A.
B.
an electrophilic substitution reaction.
an electrophilic addition reaction.
C. a reduction-addition reaction.
D. an electrophilic elimination reaction.

15. The inscribed circle in the benzene ring rep-

resents:

A. the carbon chain in the cyclic ring.

B. the sigma-system of electrons.
C. the pi-system of electrons.
D. the eight pi-electrons in the cyclic
system.

16. All the following are FALSE about Reac-

tion 2, EXCEPT that:

A. Compound A is a meta product.

B. the major product is a 1,2 substituted
product.
C. the major product is a para substituted
product.
Br D. Compound C is a 1,3 substituted product.
OBr
This page intentionally left blank
Chapter 19 Stereochemistry

Stereochemistry

A. INTRODUCTION

Stereochemistry is the study of the three-dimensional structures of com-

pounds. In this chapter, we will discuss the various concepts in stereochemistry
starting with some simple terms such as isomers. What are isomers? Isomers
are compounds with the same molecular formula, but with different arrange-
ments of atoms. Stereochemistry takes us further into the intricacies of isomerism
in terms of three-dimensional perspectives. Furthermore, stereochemistry helps
us understand the differences in activities of molecules that are structurally rather
close. In many compounds, the slightest changes in the three-dimensional form
of molecules make them active or inactive. This concept is especially important
in many biologically significant molecules. Stereochemistry has taken us deep
into the secrets of many naturally occurring molecules in our body.

Constitutional isomers have the same molecular formula but different

arrangements. Look at the examples shown in Figure 19-1. They are constitu-
tional isomers.

Figure 19-1
The MCAT Chemistry Book

B. STEREOISOMERS

Isomers with atoms having the same order of bonding, but different spatial
arrangements are called stereoisomers. Stereoisomers which are non-
superimposable mirror images are called enantiomers. Diastereomers are
stereoisomers that are not mirror images.

Achiral Chiral
carbon carbon
In glycine, the carbon indicated by the arrow is achiral because the carbon has two
hydrogen (two of the same substituents) attached to it. That is not the case in alanine,
and thus the carbon indicated by the arrow is chiral.

Figure 19-2

A carbon which is sp3hybridized (tetrahedral structure) with four differ-

ent substituents is called a chiral carbon. If the carbon doesn't have four different
substituents or say at least the carbon has two of the same substituents, then it is
an achiral carbon.

Enantiomers

Enantiomers are compounds with same molecular formula and are

nonsuperimposable mirror images. Look at the example shown in Figure 19-3.

Figure 19-3
Chapter 19 Stereochemistry

Diastereomers

Diastereomers have the same molecular formula, but they do not have a
mirror-image relationship to each other. Study the examples in Figure 19-4.

H Diastereomers OH

H$ H CH20HOH
* HT CH20HOH

mannose glucose
Figure 19-4

C. OPTICAL ACTIVITY

The molecular structure and the geometry of a compound dictate many

of its properties. The structural integrity of certain molecules makes them capa-
ble of rotating the plane of polarized light. In order to make use of this
phenomenon, we must have a source of plane polarized light. When light waves
are passed through polarizing materials, the electric field vector of the processed
light oscillates in one plane. This is plane polarized light.

To examine the chiral properties, experimenters pass plane polarized

light through solutions of chiral compounds. The rotation of light is noted with
a detector. If the rotation perceived by an observer looking through the solution
toward the source of light is clockwise, positive (+) sign is used to denote the
optical activity. For counterclockwise rotation, negative (-) sign is used to denote
the optical activity. The positive rotation is often referred as d (dextrorotatory)
and negative rotation as 1 (levorotatory).

Some Generalizations Regarding Optical Activity

Consider two solutions - A and B. Solution A contains a pure enanti-

omer, and solution B contains the enantiomer of the compound in solution A.
Let's say that solution A exhibited positive rotation.

Since the solution A containing a pure enantiomer exhibits positive rotatory

properties, its enantiomer will have negative rotatory properties. What can we
conclude about these compounds? Well, we can be certain that both compounds
present in the solutions A and B are chiral, since they exhibit optical activity.
The MCAT Chemistry Book

The specific rotation [ a ] of a compound at a given wavelength is denoted by

a
[al=,,
where a is the observed rotation,
c is the concentration in g/ml,
and 1 is the length (in decimeters) of the polarimeter tube (the
optically active solution is taken in the polarimeter tube for the
analysis) that is used.

Properties of Enantiomers and Diastereomers

Enantiomers have identical physical properties. So they cannot be distin-

guished based on their melting points, boiling points, and densities. But enanti-
omers do differ in terms of optical activity. Enantiomers rotate plane polarized
light with the same magnitude, but in opposite directions. Because enantiomers
have identical physical properties, separation of enantiomers using conventional
methods such as simple distillation and recrystallization is not possible. Enanti-
omers react the same way with achiral molecules, but react differently with chiral
molecules. This difference in reactivity of enantiomers toward chiral molecules is
utilized in separating enantiomers. The process is called resolution. The enantio-
meric mixture is reacted with a chiral molecule to form a pair of diastereomers.
Because diastereomers have different physical properties, they can easily be sepa-
rated. Diastereomers usually have different solubilities. Followed by the separa-
tion of the diastereomers that are fonned, the original reaction is reversed to get
the original enantiomer corresponding to the diastereomer.

D. CONFIGURATIONS

Chirality and Achirality

Figure 19-5

If a molecule does not have a plane of symmetry, it is chiral. A chiral

molecule is not superimposable on its mirror image. The structures represented
in Figure 19-5 are mirror images. These mirror images are non-superimposable.
The molecules depicted in Figure 19-5 are chiral.
Chapter 19 Stereochemistry

Figure 19-6

We will now consider Figure 19-6. The mirror images of the molecule depicted
are superimposable. Hence it is an achiral molecule. Notice that two of the atoms
attached to the central carbon atom are the same, namely the hydrogen atoms.

Achirality can also be recognized by looking at the molecular structure.

When we are analyzing the structure of a molecule, we should look and deter-
mine whether there is any plane of symmetry in the molecule. Plane of symmetry
reflects achirality.
The figure given below shows a stereoisomer of tartaric acid. Notice that this
compound has two chiral (stereogenic) centers. But, there is a plane of symrne-
try and thus the molecule itself is achiral and optically inactive. Such com-
pounds that contain one or more stereogenic centers, but are achiral, are called
meso compounds. Hence, having a stereogenic center or chiral carbon does not
always lead to chirality of the entire molecule.

- - - Plane of Symmetry
HO

H
meso-tartaric acid
The MCAT Chemistry Book

Absolute Configuration

In three-dimen- Fischer projection Three-dimensional form

sional repre-
sentation, the
solid wedges
represent bonds
that are point-
ing towards
you. Figure 19-7
The dashed
wedges repre-
sent bonds that
In Fischer projection, the horizontal lines represent bonds that are toward you,
are pointing
awayfvom you. and the vertical lines represent bonds that are pointing away from you.

Absolute configuration is the arrangement of substituents around the

stereogenic center of a chiral molecule. The Fischer projection and the absolute
configuration of the amino acid alanine is shown in Figure 19-7.

R-S System of Representation

The R-S system of representation is a convenient and essential way of

looking at molecules. The R-S convention is done by prioritizing the substituents
that are bonded to the chiral carbon.

The following rules will familiarize you with the R-S naming of compounds.

1. The orientation of the molecule should be in such a way that the lowest
priority group is pointing away from you.

First, prioritize each group that is bonded to the chiral carbon. The priority
is based on atomic number. Higher the atomic number of the atom (in the
group) that is connected to the chiral carbon, higher the priority of that group.
For example, if the four groups connected to a chiral carbon are CH,, H,
OH, and Br, then the bromine atom (atomic number 35) has the highest
priority. This is followed by the oxygen atom (atomic number 8) of the hy-
droxyl group, then the carbon atom of the methyl group, followed by the
hydrogen atom (atomic number 1). It is important to realize that the priority
is determined by the atomic number of the atom that is directly connected to
the chiral atom.

3. If two groups that are attached to a chiral carbon are isotopes (same atomic
number, different mass numbers), the heavier isotope takes precedence.
Chapter 19 Stereochemistry

4. If two groups have the same atom connected to a chiral carbon, then the next
atom along the chain determines the priority. If that too fails (if it is the same
atom), then go to the next atom to determine which group has higher prior-
ity. For example, -CH,F has a lower priority than -CH,I. If the groups con-
tain unsaturations such as double or triple bonds, consider that the atoms on
both ends are duplicated depending on the number of bonds.

-C E C-H implies C - C
I
-I H

5. After prioritizing, draw an arrow starting from the first priority group to the
third priority group through the second priority group. This is illustrated in
the example given below.
6. If the arrow points in the clockwise direction, the configuration of that chiral
carbon is R. If the arrow points in the counterclockwise direction, the con-
figuration of that chiral carbon is S.

Notice that the lowest priority group S

(H) is pointing away from you.
The MCAT Chemistry Book

If the given orientation of a molecule shows the lowest priority group pointing
toward the viewer, the orientation should be changed so that the lowest priority
group points away from the viewer. In Fischer projection, if the lowest priority
group is attached to a vertical bond (the one that points up or down), the mol-
ecule should be viewed from another angle so that the lowest priority group
points away from the viewer. This can be achieved by doing 2 two-group switches
or interchanges. If only 1 two-group interchange is done, the opposite configu-
ration results. See the example given below.
1 two-group interchange
0 results in the opposite confuguration @ counterclockwise

OHo+-cH3@ HO.+CH&H3 a ?H3CH2p,$ S configuration

BCH3
Notice that the lowest priority group
CH3

2 two-group interchanges
(-CH3) is NOT pointing away from you. restore the original confuguration
Example 19-1

Find the absolute configuration of the molecule shown below in terms of R-S
notation.

Solution:

First, we have to think about the order of priority of the substituents. The order
is as follows:
OH > CH,CH, > CH, > H
We can simplify the structure by looking at the three substituents that determine
the configuration. Let's redraw them as shown below:

Since the direction of priority is clockwise, the configuration is R.

Chapter 19 Stereochemistry

Some sample conversions to Fischer projection

CHO
I -CI30 CHO
I
HO : H

""7"
-

--
-
CH3 CH3

Fischer prqjection
viewing angleldirection

Example 19-2

Draw the L configuration of the compound shown in Example 19-1

Solution:

For L configuration, the direction of priority should be counterclockwise. So the

structure can be best represented as follows:

Counterclockwise

CH2CH3
The MCAT Chemistry Book

CHAPTER 19 PRACTICE QUESTIONS 2. What is the best term that can be used to
express the relationship between the two
1. What is the best term that can be used to structures shown below?
express the relationship between the two
structures shown below?
CHO

COOH H-C-OH
I
C-H H-C-OH

HO-C-H
I H-C-OH
I
H-C-OH
I I
I
COOH CHO

COOH I
H-C-OH
I I
H-C-OH
I HO-C-

I
H

HO-C-H
I H-C-OH
I
I
A. Diastereomers
A. Diastereomers B. Enantiomers
B. Enantiomers C. Identical con~pounds
C. Mesocompounds D. None of the above
D. Anomers
Chapter 19 Stereochemistry

3. The structure shown below is that of 2,3,4- c. COOH

trihydroxy glutaric acid. Choose the correct
enantiomer of this compound. H-C-OH
I
H-C-OH
I
COOH

I HO-C-H
I
I
D. COOH
H-c-OH
I H-C-OH
I
COOH
H-C-OH
I
HO-C-H
A. COOH

HO-C-H
I COOH
I
HO-C-H
I 4. All are equivalent structures or representations
of the compound given below, EXCEPT:
I
COOH

B. COOH
I
H-C-OH

H-C-OH
I
I

D. All the above are equivalent

structural representations.
The MCAT Chemistry Book

5. What is the name of Compound X? Saw horse representation of a compound is

given below. Which of the following is true
F
about this structure?

Compound X

A. The compound has an eclipsed confor-

mation.
6. Which of the following are true? B. The compound has a staggered confor-
mation.
I. Diastereomers are stereoisomers. C. The compound has a cis-configuration.
11. All stereoisomers are enantiomers. D. None of the above
III.Al1 enantiomers are stereoisomers.

A. I & I1 only
B. I & 111 only
C. I1 & I11 only
D. I, 11, & I11
Chapter 20 Alkyl Halides

Al kyl Halides

A. INTRODUCTION

Alkyl halides are organic compounds with the general formula RX, where
R denotes the alkyl group and X denotes the halogen.

B. NAMING OF ALKYL HALIDES

l o alkyl halide 1 alkyl halide 2' alkyl halide 3' alkyl halide

We can classify alkyl halides as primary (lo), secondary (2O), and tertiary (3O)
alkyl halides. The general formulas for these are as follows:

Primary alkyl halide RCH,X

Secondary alkyl halide %CHX

Tertiary alkyl halide R3CX

C. PROPERTIES OF ALKYL HALIDES

Alkyl halides have large dipole moments since the carbon-halogen bond
is polar. They also have reasonably high boiling points because of the polarity
and the high molecular weights.
The MCAT Chemistry Book

Alkyl halides are generally insoluble in water. Density of alkyl halides increases
as the atomic weight of the halogen present increases. The heavier the halogen
is, the higher the density.
- - --

3 Increasing order of density

D. SYNTHESIS OF ALKYL HALIDES

From Alcohols
< RC1 < RBr < RI

Alkyl halides can be prepared from alcohols. The following examples

show some representative reactions. The conversion of an alcohol to an alkyl
halide is an example of a nucleophilic substitution reaction.

-
Sample reaction 20-1
HC1
CH3CH20H CH3CH2C1
Ethyl Alcohol Ethyl chloride

Sample reaction 20-2

From Alkanes

Alkyl halides can be synthesized from alkanes. In this reaction, one of

the alkane's hydrogen atoms is substituted with a halogen atom. The reaction
occurs by free radical mechanism.

Sample reaction 20-3

Cl2 RC1 + HC1

RH
Alkane Alkyl halide
Chapter 20 Alkyl Halides

From Alkenes

Alkyl halides can be prepared from alkenes.

Sample reaction 20-4

CH2=CH2
Ethylene
+ HX -
Hydrogen halide
CH,-CH2X
Ethyl halide

Sample reaction 20-5

Markovnikov addition of hydrogen and bromine

Alkene

E. REACTIONS OF ALKYL HALIDES

Nucleophilic Substitution Reactions

In this section, we will discuss the two major substitution reactions -

S,1 and SN2reactions. In nucleophilic substitution reactions involving alkyl
halides as the substrate, a Lewis base (nucleophile) substitutes the halogen present
in the alkyl halide. We will discuss nucleophilic reactions in which alkyl halides
react with nucleophiles. A general representation can be done as follows:

RX -
(Alkyl halide)

NU-
(Substitution
product)

RNu + X
-

(Nucleophile)

The S,2 Reaction

S,2 stands for bimolecular nucleophilic substitution reaction. Consider

CH,I + NaOH -
the reaction between methyl iodide and sodium hydroxide.
CH,OH +
This reaction follows SN2mechanism. Experimentally, it has been confirmed
NaI

that the rate of this reaction depends on both the alkyl halide and the nucleophile
(OH-) involved. The reaction rate is written as follows:
Rate = k [CH,I] [OH- ]
The MCAT Chemistry Book

The Mechanism of S,2 Reaction

We will look at the mechanism involved in the reaction between methyl

iodide and sodium hydroxide. The S,2 reaction proceeds via a five-coordinate
transition state. This transition state has weak (the weak bonds are indicated by
the dotted lines in the mechanism) carbon-iodine and carbon-oxygen bonds.
Even though these two are weak bonds, the other three bonds involving the
central carbon atom are complete bonds. As the leaving group detaches, there is
an inversion of configuration (in chiral molecules) at the carbon where the leaving
group was attached.

H
Methanol

Figure 20-1 The mechanism of S,2 reaction

In S,2 reactions, the nucleophilic attack occurs opposite (backside attack)

to the side where the leaving group is present. This type of nucleophilic approach
is thermodynamically favored since the backside attack minimizes 'the
electrostatic repulsions between the nucleophile and the leaving group involved.
If substituents (especially bulky ones) are present on the carbon where the
nucleophilic attack occurs, this can hinder the S,2 process. Hence, primary alkyl
halides are the most reactive among alkyl halides with respect to S,2 reactions.

S,2 reactivity: Methyl > Primary > Secondary > Tertiary

Chapter 20 Alkyl Halides

CH3CH2 CH2CH3
(9 -2-chlorobutane transition
state
(R) -2-butanol -.-
CI:

1 inversion of configuration

As mentioned earlier, the nucleophile and its concentration can influence

the rate of S,2 reactions. So the rate is different for different nucleophiles. Nu-
cleophilicity or the strength of a nucleophile depends on how efficiently it can
make the leaving group leave from the alkyl halide or whatever the substrate is.
Some generalizations can be made regarding nucleophiles. Along a period (in the
periodic table), as basicity decreases, nucleophilicity decreases (e.g., F- < RO- <
R,N- < R,C-). However, a strong base does not always imply a good nucleophile.
For example, the order of basicity of halide ions is F- > C1- > B r > I-. But the
order of nucleophilicity in solution follows the opposite trend. The important as-
pect that we should note is that this trend-reversal is seen when polar protic solvents
are used. Polar protic solvents (e.g. water, alcohol) have protons that can hydro-
gen bond to negatively charged nucleophiles. Hence, the size of a nucleophile
plays a big part in terms of such a scenario. The smaller the nucleophile (anion),
the more strongly it is solvated by a protic solvent. Thus, more energy is required
to overcome this wrapping effect of the solvent molecules on the nucleophile, and
that can reduce the nucleophilicity of the nucleophile. Fluoride ions, that are much
smaller than iodide ions, are strongly solvated. This explains why iodide, even
though less basic than fluoride ions, acts as stronger nucleophiles in protic envi-
ronment. In aprotic solvents, this trend is reversed, and so does when a reaction is
conducted in gas phase without a solvent.

Nucleophilicity can also be compared among species having the same

nucleophilic atom. A negatively charged conjugate base of a neutral species (con-
jugate acid) is more nucleophilic than its corresponding neutral species. For
example, HO- is a better nucleophile than H20.

A leaving group plays an important role in both substitution and

elimination reactions. A good leaving group has a weak, polarized carbon-leaving
group (C-X) bond. It should be stable on its own once it leaves the substrate,
regardless of whether it stays as an ion or a neutral species. Sometimes solvation
helps a leaving group to achieve this. Halides are good leaving groups. The
order of leaving group ability is F < C1< Br < I. In general, less basic the species
is, the better the leaving group. Other good leaving groups include mesylate and
tosylate.
The MCAT Chemistry Book

Common nucleophiles (in polar protic solvents)

II Good nnucleophilei 1
- .. - - .. - ..
I ..
:S-H
0.

: :
-
(CH,CH~)~;H :C E N
..
0-H :O-CH3
I

-
"
C
Increasing nucleophilicity
I I
Moderate nucleophiles
.... -
:Br: :NH3 1
-.:- 0
CH3C-$:
.. -

I Increasing nucleophilicity

: Increasing nucleophilicity

The S,1 Reaction

SNlstands for u~irnolecularnucleophilic substitutionreaction. Let's con-

-
sider a typical S,1 reaction.

H20
(CH3)3C1 (CH3)3COH + HI
tert-Butyl iodide tert-Butyl alcohol

The rates of S,1 reactions depend only on the substrate (alkyl halide) concentra-
tion. The nucleophile does not influence the reaction rate of a typical SN1 reaction.
The reaction rate is represented as follows:

Rate = k [ (CH,),CI ]

The Mechanism of S,1 Reaction

In this two-step reaction, the alkyl halide splits to form a carbocation
intermediate and a halide ion. During the second step, the cation reacts with the
nucleophile to form the final product. Since the carbocation formed is planar,
the nucleophile can attack the electrophilic carbon fiom either side. Thus an S,1
reaction results in racemization.
Chapter 20 Alkyl Halides

Nucleophilic attack
from the top I YCH3

S configuration
Nucleophilic attack
from the bottom

OCH,
R configuration

Figure 20-2 The mechanism of S,1 reaction

S,1 reactivity: Methyl < Primary < Secondary < Tertiary

SN2reaction is favored when the alkyl halide involved is a primary or a

secondary alkyl halide. S,1 reaction is favored when the alkyl halide involved is a
tertiary or a secondary alkyl halide. In many cases, it is hard to predict the mode of
reaction with secondary alkyl halides -it can either be SN1or SN2,depending on
certain other aspects such as the solvent used. The SN1reaction being favored by
tertiary halides is understandable, because of the carbocation intermediate that is
formed during the SN1process.

Polar solvents increase the rate of both types of substitution reactions.

Polar solvents which have high dielectric constants can stabilize the transition
state and this is highly useful in S,1 reactions. In SN2reactions, the solvent
effects are slightly different. Here what matters is whether the solvent is aprotic.
Protic polar solvents such as water and carboxylic acids can undergo hydrogen
bonding which in turn can interact with the nucleophile. This can decrease the
rate of SN2reactions. So it is better to use aprotic polar solvents when we are
dealing with S,2 reactions. Dimethyl sulfoxide (DMSO) is a polar aprotic solvent.
The MCAT Chemistry Book

Quite often nucleophilic reactions compete with elimination reactions. Next,

we will review elimination reactions.

Elimination reactions

There are two types of elimination reactions in general - E l and E2

reactions. We will first consider an E2 reaction.

The E2 reaction

The E2 reaction mechanism can generally be represented as shown. In

the mechanistic representation shown, B stands for the base and X stands for the
halogen.

Alkyl halide
I I
Transition State
B:
Base B - - - - H- ---C-C-

"
I I
- - -X
I
Figure 20-3 The mechanism of E2 reaction

The steps involved in an E2 reaction are the breaking of the carbon-

hydrogen bond, the carbon double bond formation, and the breaking away of
the carbon-halogen bond.

The rate of the E2 reaction is: Rate = k [ RX ] [ base ]

So the reaction rate depends on both the substrate (RX) and'the base involved.

In an elimination reaction, the major product formed is the most stable alkene.
Usually, the most stable alkene is the most substituted alkene. The increased sta-
bility of more highly substituted alkenes can be attributed to electronic effect.
Chapter 20 Alkyl Halides

The E l Reaction

Study the mechanism of El reaction.

Step 1

Methanol TH3 ..-

u
Carbocation

Step 2

Figure 20-4 The mechanism of E l reaction

In step (I), the alkyl halide forms (slow step) the carbocation and the halide ion.
In step (2), the base abstracts the proton to form the product (alkene).

E l reactivity:Methyl < Primary < Secondary < Tertiary

(Slowest) (Fastest)
Substitution versus Elimination

Reaction mechanisms are influenced by many factors. Different

combination of factors result in different outcomes. Even though this is the
case, let's boil down some of the factors that we can rely on for reasonably
judging the outcome of reactions. We will consider some conditions that favor
substitution over elimination, and vice versa. The two key factors that we look
for are the type of substrate that is undergoing the reaction, and the extent of
nucleophilicity or basicity of the anion involved in the reaction.

1) Higher temperatures usually favor elimination over substitution.To be more

precise, we can say that elimination is more favored than substitution reactions
if the reaction occurs at a high temperature. The latter is more accurate because
The MCAT Chemistry Book

both types of reactions are favored by an increase in temperature, but

elimination is more favored.
2) Strong bases guide or dictate elimination over substitution in most cases. In
general, E2 type of elimination is favored under such conditions.
3) If there is less hindrance or less bulky substituents at the carbon where the
leaving group is present, substitution (S,2) is favored over elimination (E2).
Remember that in S,2 reactions, the transition intermediate is a species in
which both the leaving group and the incoming nucleophile are attached to
the carbon, where the substitution is taking place.
4) Alkyl halides (tertiary), because of their bulky substituents, mostly prefer
elimination rather than substitution provided that a strong base is present.
Mild bases can make substitution to predominate even in tertiary alkyl halides.
Can you think of a reason why tertiary alkyl halides prefer to undergo
elimination? The reason is steric hindrance to the nucleophilic approach.

Note: We have been discussing a number of reactions, both substitution and

elimination in terms of alkyl halides. This surely doesn't mean that only alkyl
halides undergo these types of reactions.
Nucleophilic Substitution in Alkyl Halides - S,1 vs S,2 Comparison

Table 20-1

SN1 SN1
Unimolecular Bimolecular
Mdecularity
(First order) (Second order)

Rate Rate = k [RX] Rate = k [RX] [Nu]

Stereochemical Inversion of
Racemization
aspect configuration

Yes; Carbocation No; No carbocation

Rearrangement?
formation formation

Rate independent of Rate dependent on

Rate dependency
nucleophile nucleophile

Solvent effect Best: Polar protic Best: Polar aprotic

Reactivity RX<R,X<R,X R,X<R,X<RX

Reactrvw Of a'kyi RF<<RCI<RBr<RI RF<<RCI<RBr<RI

halkles
Chapter 20 Alkyl Halides

CHAPTER 20 PRACTICE QUESTIONS 1. Which of the following is true regarding

alkyl halides?

A. Alkyl halides have relatively very low

boiling points, because of its polarity.
1. The compound shown above can be best B. Alkyl fluorides have lower densities
described as a: than those of comparable alkyl bro-
mides.
A. primary alkyl halide. C. Alkyl halides are completely soluble in
B. secondary alkyl halide. water.
C. tertiary alkyl halide. D. None of the above
D. primary alkenyl halide.

Questions 5-9 are based on the following

2. Pick out the compound with the highest passage.
boiling point.
Passage 1
A. 1-Chloroethane
B. 1,l -Dichloroethane Alkyl halides undergo substitution
C. 1,1,1-Trichloroethane reactions and a variety of other reactions as
D. Cannot be predicted well. The type of reaction that occurs depends
on a variety of factors. The structural integrity
of the alkyl group to which the halogen is
3. Alcohols can react with hydrogen halides attached plays an important role in determining
t o form alkyl halides. Which of the the type of product that is likely to result. A
following alcohols is the most reactive reaction involving t-butyl bromide is given
toward hydrogen halides? below:
Ethyl alcohol1
H20
(CH,),CBr Products
The MCAT Chemistry Book

5. Which of the following best represents the 7. Consider the reaction given in the passage.
increasing rate of bimolecular substitution Which of the following compound is
reaction for the following alkyl halides? produced as a result of that particular
reaction?

CH3CH2Br = Compound A
..................................
CH3Er = Compound B
---------------------------------.
(CH313CBr = Compound C
..................................
(CH3)2CHBr = Compound D

D. All the above are possible products.

8. Which of the following is characteristic of

6. Which of the following is true regarding a typical SN2reaction?
substitution reactions?
A. Rate = k [alkyl halide]
A. Tertiary alkyl halides always undergo B. Inversion of configuration
substitution by SN2mechanism. C. Carbocation intermediate
B. Only alkyl halides can undergo substi- D. Unimolecular mechanism
tution reaction by S,2 mechanism.
C. S,2 reactions involve the formation of
a carbocation intermediate. 9. Which of the following is the most reac-
D. None of the above tive by substitution mechanism?

A. CH,I
B. CH,F
C. CH,C1
D. All are equally reactive.
Chapter 21 Alcohols

Alcohols

A. INTRODUCTION

Alcohols have the general form.ula ROH.

Some common examples of alcohols:

CH30H CH3CH20H CH3CH2CH20H

methyl alcohol ethyl alcohol n-propyl alcohol

isopropyl alcohol isobutyl alcohol sec-butyl alcohol tert-butyl alcohol

B. PROPERTIES OF ALCOHOLS

Boiling Point

One of the most important properties of alcohols is their ability to form

hydrogen bonds. Since alcohols can form hydrogen bonds, they have very high
boiling points. Consider the following comparative analysis to clarify this idea.

The boiling point of ethane (C,H,) is - 88.7 O C.

The boiling point of propane (C:,H,) is - 42.2 O C.

The boiling point of ethanol (C,H,OH) is 78 O C.

The MCAT Chemistry Book

Note the drastic difference in their boiling points.

By the above comparison, it is clear that some extra forces (here mainly H bonds)
are working to increase the boiling points of alcohols.

Hydrogen bonds in alcohols (the arrows point to some of the hydrogen bonds)
Figure 21-1

Solubility in H,O

Low-molecular weight alcohols are soluble in water. The hydrogen bond

formation plays a key role in the solubility of alcohols in water. In other words,
hydrogen bonds enhance the solubility of alcohols in H,O. As the number of
carbons increases, the solubility of alcohols decreases as they become more and
more similar to hydrocarbons with longer and longer nonpolar hydrocarbon
chains.

Acidity of Alcohols

Alcohols are weakly acidic. In fact, they are weaker in acidity than water.
Alcohols have Ka values around 10 - I 7 .

Alcohols give off the acidic hydrogen to form alkoxide ions. Alkoxide
ion is the conjugate base of alcohols and they are strong bases.

R-OH
Alcohol
- OH-
R-0
-

Alkoxide ion
+ H20
Water

Among alcohols, primary alcohols are the most acidic, and tertiary alcohols are
the least acidic.
Chapter 21 Alcohols

3 alcohols < 2' alcohols < 1 alcohols

C. SYNTHESIS OF ALCOHOLS

Acid-Catalyzed Reaction

Sample reaction 21-1

H3C\
/C-
-C p
\
H 3 H2S04/H 2 0 TH3
HO-C-CH2CH3
H3C H 1
CH3
(major product)
Alkenes react with aqueous acidic solutions to form alcohols. The reac-
tion intermediate is a carbocation.Hence, there is a possibility of rearrangement
of the intermediates in such acid-catalyzed reactions. The reaction follows the
Markovnikov's rule. Keep in mind that a tertiary carbocation is more stable
than a secondary carbocation, which in turn is more stable than a primary
carbocation.

Hydroboration-Oxidation

Sample reaction 21-2

1. B2H6
CH3CH2CH2CH=CH2 * CH3CH2CH2CH2CH20H
2. Hz02, NaOH
(major product)

Oxidation followed by hydroboration of alkene results in alcohols. The

reaction occurs in an anti-Markovnikov fashion. Notice that hydrogen, instead
of attaching to the carbon with the highest number of hydrogens, attaches to the
carbon with the least number of hydrogens.
The MCAT Chemistry Book

Oxymercuration-Demercuration

Sample reaction 21-3

Alkenes can be converted to alcohols by oxymercuration-demercura-

tion. The addition of H and OH is in accordance with the Markovnikov's rule.
There is no rearrangement in this reaction.

From Epoxides

Preparation of an alcohol from an epoxide is shown below. The epoxide

(ethylene oxide) ring opens when the nucleophile attacks the carbon-oxygen
bond. Note the fact that the nucleophilic carbon is supplied by the Grignard
reagent (methyl magnesium bromide).

Sample reaction 21-4

Methyl magnesium bromide
CH3MgBr
CH3CH2CH20H
Diethyl ether
Propanol
Ethylene H,O'
oxide

Alcohols can also be produced from aldehydes and ketones via Grignard reagents.
Other methods to synthesize alcohols include the reduction of aldehydes and
ketones. These reactions will be discussed in Chapter 22.

D. REACTIONS OF ALCOHOLS

Formation of Alkoxides

Alcohols when treated with Group I metals like sodium and potassium
result in alkoxides.

Sample reaction 21-5

2 Na
2 CH30H ------------t 2 CH30Na + 2 H2
Methanol Sodium methoxide
Chapter 21 Alcohols

Formation.of Alkyl Halides

Sample reaction 21-6

2-butanol 2-iodo butane

Sample reaction 21-7

Oxidation of Alcohols

Primary alcohols can be oxidized to aldehydes by reagents like pyridinium

dichromate (PDC), and pyridinium chlorochromate (PCC).

Sample reaction 21-8

CH3CH2CH2CH20H
PCC
t CH3CH2CH2CH
II
Butanol Butanal (aldehyde)

Secondary alcohols can also be oxidized. The product is a ketone.

Sample reaction 21-9

- PDC

Since tertiary alcohols do not have a hydrogen atom in the carbon carrying the
hydroxyl group, they cannot be easily oxidized.
The MCAT Chemistry Book

Strong oxidizing agents can oxidize alcohols to carboxylic acids. We

can use potassium permanganate or chromic acid to do this conversion.

Sample reaction 21-10

Primary alcohol Carboxylic acid

Primary alcohol 1 oxidization ) Aldehyde 7)

Carboxylic acid

Secondary alcohol 7
oxidization )
Ketone

Acid-Catalyzed Dehydration

Alcohols undergo acid-catalyzed dehydration reactions to form alkenes.

The reaction is accomplished by the formation of a carbocation intermediate.
Thus there is the possibility of rearrangement in the process. First, we will take
a look at the mechanisnl of this reaction.

Mechanism of Acid-Catalyzed Dehydration of Alcohols

Sample reaction 21-11

(CH3)3COH * (H3C)2C=CH2
H,O+ 1 heat

The alcohol is protonated.

Chapter 21 Alcohols

The formation of carbocation.

Step (2)

The formation of double bond.

Rearrangement - An Example

Organic chemists have conducted experiments to understand the forma-

tion of multiple products in acid-catalyzed reactions such as that of
3,3-dimethyl-2-butanol. Let's consider the acid-catalyzed dehydration reaction
of 3,3-dimethyl-2-butanol and explore the possibility of rearrangement.
The MCAT Chemistry Book

(secondary carbocation)
H
H3C-F-C-CH3
TH3 H YH3
I T H2C=C-C-CH3 I (minor product)

1
CH3 H+ CH3

(Rearrangement - a methyl shift results

in a Inore stable carbocation)

(tertiary carbocation)
H
H3C-C-$-CH3
I
TH3
-7- (cH~)H,c-
rH3
c=CH~

CH3 H+

(major product)

Figure 21-2
The major product fonned in this reaction is 2,3-Dimethyl-1-butene. Notice
(Figure 2 1-2) the rearrangement that occurs in this reaction. The rearrangement
results in a more stable carbocation (A tertiary carbocation is more stable than a
secondary carbocation).
Chapter 21 Alcohols

CHAPTER 21 PRACTICE QUESTIONS

1. The higher boiling points exhibited by

alcohols with respect to comparable alkanes
and ethers are primarily due to:

A. ionic bonds. An organic chemist synthesized and isolated

B. covalent bonds. the above represented compound. If this
C. hydrogen bonds. compound undergoes oxymercuration-
D. none of the above. demercuration reaction, the major product
is most likely:

2. The conjugate base of alcohols are gener-

ally called:

A. alkyl ions.
B. alcoholic ions.
C. alkoxide ions.
D. vinyl ions.

3. Which of the following is a possible way

of making alcohols?

A. Hydroboration-oxidation of alkenes
B. Acid catalyzed hydration of alkenes
C. Oxymercuration-demercuration of
alkenes
D. All the above
The MCAT Chemistry Book

8. The major product of the following

reaction is:
Compound A CH3CH2CH2CH20H
Ethyl magnesium bromide
OH (Diethyl ether)
I Ck7CH2 ~~6
Compound B CH3CHCH3 0

Compound C H 3 C C O H
YH3 A.
B.
C.
a four-carbon ketone.
a four-carbon halohydrin.
a two-carbon aldehyde.
I
CH3 D. a four-carbon alcohol.

Compound D CH3CH2CH2CH3 9. Identify Compound B from the sequence

of reactions.
Table X (Question 5)

5. From Table X, the most acidic compound is:

A. Compound A
B. Compound B Compound A /
C. Compound C /'
D. Compound D ( Pyridinium dichromate
I
Compound I3
6. Direct oxidation of which of the following
can result in a carboxylic acid?
A. Propanol
A. Secondary alcohol B. Propanal
B. Tertiary alcohol C. Acetone
C. Primary alcohol D. Formaldehyde
D. All the above

7. Choose the correct product formed as a

result of the reduction of a ketone.

A. A primary alcohol
B. A secondary alcohol
C. A tertiary alcohol
D. None of the above
Chapter 21 Alcohols

12. Which of the following is the most acidic?

A. (CH,),COH
B. NH,
C. (CH,),CHOH
10. Reduction of the organic compound shown D. CH,OH
above results in:

A. a ketone. 13. In Reaction 1, predict the identity of the

B. a primary alcohol. other product, if any.
C. a carboxylic acid.
D. an ester. A. H,O
B. 0,
Questions 11-15 are based on the following C. H,
passage. D. No other products are produced.

Passage 1
14. Which of the following is the most reac-
Alcohols are of tremendous use for the tive alcohol toward sodium?
synthesis of a wide variety of organic
compounds. They also have some very unique
properties. Alcohols are in fact slightly weaker
acids than water, and have pKa values between
16 and 18.
An alcohol can loose its acidic hydro-
gen to form an alkoxide ion.
Reaction 1

2 CH3CH20H - 2 Na
2 NaOCH2CH3

11. The alcohol shown below is:

A. cis-2-ethylcyclohexano1.
B. cis-2-ethylcycloctanol.
C. cis- 1-ethyl-2-hydroxycyclopentcule.
D. trans-2-ethylcyclohexanol.
The MCAT Chemistry Book

15. Which of the following can be used to make

propanol directly by oxidation?

D. None of the above

Chapter 22 Aldehydes and Ketones

Aldehydes and Ketones

A. INTRODUCTION

Aldehydes and ketones are compounds containing the acyl group. The
carbonyl group present in them is polar because of the electronegativityof oxygen.
It is noteworthy to mention that the carbonyl group in aldehydes and ketones are
very reactive.

II
FORMULA

0
KETONE
FORMULA

ACYL GROUP CARBONYL GROUP

The partial negative charge on the oxygen is because of its higher electronegativity
compared to carbon. This gives the carbonyl carbon a partial positive charge.
The MCAT Chemistry Book

B. SOME ALDEHYDES AND KETONES

Methanal Ethanal Butanal

(formaldehyde) (acetaldehyde) (butanaldehyde)

-
cH3
Acetone 2-pentanone 3-methyl-2-pentanone

C. PROPERTIES OF ALDEHYDES AND KETONES

The carbonyl group present in aldehydes and ketones make them polar
in nature. Both aldehydes and ketones have higher boiling points than comparable
hydrocarbons. Aldehydes and ketones do not form hydrogen bonds themselves.
Hence, they have lower boiling and melting points compared to alcohols with
comparable molecular weights. Finally, aldehydes and ketones have higher
solubility in water than hydrocarbons, but less solubility than alcohols. Even
though aldehydes and ketones cannot undergo hydrogen bonding themselves,
they can undergo hydrogen bonding with water molecules.

D. SYNTHESIS OF ALDEHYDES AND KETONES

From Alcohols

Aldehydes can be prepared by the oxidation of primary alcohols.

Oxidizing zgents such as pyridinium chlorochromate (PCC) or pyridinium
dichromate (PDC) can be used for such conversions.

Sample reaction 22-1

CH3CH2CH2CH20H
PCC
w CH3CH2CH2CH
1
Butanol Butanal (an aldehyde)
Chapter 22 Aldehydes and Ketones

Oxidation of secondary alcohols results in ketones.

Sample reaction 22-2

A secondary alcohol A ketone

From Alkenes by Ozonolysis

Aldehydes and ketones can be prepared by the ozonolysis of alkenes.

Sample reaction 22-3

AN ALDEHYDE

Sample reaction 22-4

H3C\ /CH3 H3C\ H3C\

1. o3

H3C
/"=C\ H 2. H20/ Z n
t
/c=o +
H3C H/C=o
A KETONE AN ALDEHYDE

E. NUCLEOPHILIC ADDITION TO THE CARBONYL GROUP

The carbon of the carbonyl group is an electrophile. Thus it is susceptible

to nucleophilic attack. During most addition reactions of alkenes, it is an
electrophile that attacks the pi system. But in an addition reaction involving a
carbonyl group, we see that the attack on the carbonyl carbon is made by a
nucleophile. Think about why this is the case? One reason for this is the polar
nature (due to electronegativity,of the oxygen atom) of the carbonyl group.
Furthermore, the resonance capability of the carbonyl group also enhances this
type of reactive property. A generalized nucleophilic attack is shown below in
Figure 22-1.
The MCAT Chemistry Book

..
c i' Nucleophile

..
NU-

Electrophile

Figure 22-1

F. REACTIONS OF ALDEHYDES AND KETONES

Formation of Carboxylic Acids

Aldehydes can be oxidized to carboxylic acids using oxidizing agents

such as potassium permanganate or potassium dichromate.

Sample reaction 22-5

KMn04
RCHO RCOOH

-
Sample reaction 22-6
0
II II
CH3CH2-C-H CH3CH2-C-OH
Na2Cr207
1 dil. H2S04
Aldehydes selectively react in a solution of silver-ammonia complex called

-
Tollen's reagent. A sample reaction is given below.

Sample reaction 22-7

CH3CH-C-H
B + 3 OH-
+ 2 Ag(~H3ht -)
B
+ 4 NHl + 2 H 2 0 + 2 Ag*
CH~CH-C-0-
I I silver
CH3 CH3
Tollens reagent

With Grignard Reagents

Aldehydes and ketones react with Grignard reagents to form alcohols.

Grignard reagents are organornetallic compounds. These reagents can be prepared from organic halides
by reacting with magnesium.

Mg + RMgBr
RBr
Mg + CH3MgBr
CH3Br
Chapter 22 Aldehydes and Ketones

Formaldehyde reacts with Grignard reagents to form primary alcohols.

Sample reaction 22-8

Formaldehyde Ethyl alcohol

Other aldehydes react with Grignard reagents to form secondary alcohols.

Sample reaction 22-9

0 H
II CH3MgBr
*H I
3 C C O H
/C\H H+
H3C I
CH3
Aldehyde 2-Propanol
Ketones give tertiary alcohols.

Sample reaction 22-10

0
II CH3MgBr
*H TH3
3 C C O H
H3C /'\CH3 H+ I
CH3
Ketone Tertiary alcohol
G. ALDOL ADDITION AND CONDENSATION REACTIONS

In aldol addition reactions, a carbon-carbon bond is formed between the

carbonyl carbon of one aldehyde molecule and the a-carbon of another aldehyde
molecule. The product is.a P-hydroxy aldehyde. After the nucleophilic addition
of the enolate ion to the carbonyl group, removal of water of the P-hydroxy
aldehyde can occur resulting in an a$-unsaturated aldehyde. Study Sample
reactions 22-1 1 and 22- 12.
The MCAT Chemistry Book

Sample reaction 22-11

Propanal 0
The enolate adds to this carbonyl carbon (P-hydroxyaldehyde)
2-Methyl-3-hydroxypentanal
(Aldol addition product)

The new carbon-carbon bond

This a- carbon loses one proton

to the base and forms the enolate ion

Sample reaction 22-12

The addition product upon heating will undergo elimination (dehydration) to

form the a$-unsaturated aldehyde.

a,P-Unsaturated aldehyde
(aldol condensation product)
Chapter 22 Aldehydes and Ketones

H. REDUCTION REACTIONS OF ALDEHYDES AND KETONES

Conversion to Alcohols

Aldehydes and ketones can be reduced to alcohols using reducing agents

such as lithium aluminum hydride (LiAlH,), and sodium borohydride (NaBH,).

Sample reaction 22-13

Sodium bwohydride
(NaBH,) c a n reduce
a l d e h y d e s and ke-
t o n e s w h e n reacted
in' a q u e o u s or alco-
hol solutions. Car-
boxylic acids and es-
Acetaldehyde Ethyl alcohol ters are not reactive
t o sodium borohy-
dride reduction.
Sample reaction 22-14 Lithium aluminum
h y d r i d e (LiAIH,), a
more powerful reduc-
ing agent, can reduce

CH,CR
11 , NaBH4
t Secondary alcohol
a l d e h y d e s , ketones,
esters, and carbo.uy-
lic acids.
Ketone H20

Conversion to Hydrocarbons

The carbonyl groups of aldehydes and ketones can be converted to

methylene groups by Clemmenson and Wolf-Kishner reduction reactions.

Sample reaction 22-15

0
II (Wolff-Kishner reduction)
H3CC-
II H2NNH2,KOH H2
CH3 ) H,C-C- CH3
heat

Zinc(Hg) / HC1
* (-\)?-CH3
(Clemmensen reduction)
The MCAT Chemistry Book

I. FORMATION OF ACETALS

Aldehydes can undergo reactions with alcohols under acidic conditions.

The product of this nucleophilic addition reaction is called hemiacetal.
Hemiacetal is formed by the nucleophilic addition of alcohol to the carbonyl
carbon. Hemiacetal can react with one more mole of alcohol to form an acetal.

Hemiacetal

Aldehyde

R-C-H
I + H2O
I
OR'

Acetal
FORMATION OF CYCLIC STRUCTURE OF GLUCOSE

6
CHIOH
In monosaccharides (e.g., glucose,
/ fructose), the cyclic ring structure is
formed by the intramolecular reaction
between the carbonyl and the hydroxyl
groups within the same molecule.
Glucose (an aldohexose) forms a cyclic
hemiacetal b y the intramolecular
reaction between the aldehyde group of
carbon 1 and the hydroxyl group of
carbon 5.
OH

p-D-Gluwp~rano~ a-DGlumpymwc
Chapter 22 Aldehydes and Ketones

CHAPTER 22 PRACTICE QUESTIONS 4. Predict the aldol addition product of the

structure shown below:
1. Propanal is treated with ethyl magnesium
halide (with diethyl ether & H,O+).Which
of the following is true regarding this
reaction?

A. A five-carbon ether is the major product.

B. A five-carbon secondary alcohol is the A.
major product.
C. A five-carbon ketone is the major CHO
product.
D. None of the above are true.

2. The structure shown below represents:

C.
CHO
A. a ketal.
B. a hemiacetal.
C. an acetal.
D. a hemiketal.

3. The Baeyer-Villiger reaction is a very use-

ful synthesis reaction. An example is the 5. Which of the following carbons indicated
reaction of acetone with peroxyacetic acid by arrows has the most acidic protons?
to give an ester and a carboxylic acid. This
reaction can be generalized as:

A. a reduction reaction.
B. an oxidation reaction.
C. a hydrolysis reaction.
D. an isomerization reaction.

A. a
B. b
C. c
D. No acidic protons are present, since
ketones cannot be acidic.
305
The MCAT Chemistry Book

6. The structure represented below can be 8. Which of the following is the conjugate
most appropriately called an: base of a ketone?

'CH~
A. alkenyl ion.
B. acyl ion.
C. alkoxide cation.
D. enolate ion.

7. Predict the aldol condensation product

(major product) of the following compound.

9. A student is trying to prove the identity of

a compound that she synthesized. She
knows that the compound is a methyl
ketone. Which of the following qualitative
tests can be used to prove the identity of
the synthesized compound as a methyl
ketone?

A. Ignition test
B. Potassium permanganate test
C. Beilstein test
I D. Iodoform test
I
Chapter 22 Aldehydes and Ketones

10. Chromic acid test can be used for the identi- (excess) CH30H
fication of: CH3CH2CH0 * CH3CH2CH(OCH3)2
HC1
A. aldehydes and ketones.
B. aldehydes only. Experiment 3
C. ketones only.
D. carboxylic acids only.

Questions 11-16 are based on the following

passage.
Experiment 3 involved merely the analysis of
Passage 1 a conversion. Students were asked to discuss a
method to accomplish this synthesis reaction.
Students of an organic chemistry class
conducted several experiments with aldehydes Experiment 4
and ketones. Some of the reactions are sum-
marized below:

Experiment 1

Acetophenone was reacted with Reagent A. The

product was ethyl benzene.

Compound Y

Experiment 2

Propanal underwent acid-catalyzed reaction

with alcohol.
The MCAT Chemistry Book

11. Which of the following best represents the C. Reaction is possible, if the reactant is
general name of the product formed in treated with an appropriate Grignard
Experiment 2? reagent followed by hydrolysis.
D. Reaction is not possible, because alde-
A. Hemiacetal hyde carbonyls are nucleophilic and are
B. Acetal thus unreactive.
C. Ketal
D. Hemiacetal
15. Which of the following is not an organo-
metallic compound?
12. The conversion presented in Experiment 1
is:

A. an oxidation reaction.
B. a reduction reaction.
C. a dehydrohalogenation reaction.
D. a dehydrogenation reaction.

13. Which of the following Grignard reagents

will serve the purpose for the reaction in
Experiment 4?

16. In our body, toxic chemicals are metabo-

lized in the liver. One such process involves
the production of acetaldehyde from etha-
nol. This conversion is best described as:

Ethanol - alcohol
- Acetaldehyde
dehydrogenase

A. a dehydrogenation reaction.
B. a hydrogenation reaction.
14. In Experiment 3, which of the following is C. an oxidation reaction.
a possible scenario? D. a reduction reaction.
A. Reaction is possible, because propanal
can be directly oxidized to form the
product indicated.
B. Reaction is not possible, because you
cannot convert an aldehyde to a second-
ary alcohol.
Chapter 23 Carboxylic Acids

Carboxylic Acids

A. INTRODUCTION

Carboxylic acids are compounds with the general formula RCOOH.

II Carboxyl group

0
II
HCOH
Formic acid Acetic acid
(Methanoic acid) (Ethanoic acid)

Propanoic acid Benzoic acid

B. PROPERTIES OF CARBOXYLIC ACIDS

It is clear from the name that carboxylic acids are acidic. The hydrogen
of the carboxyl group (-COOH) is acidic. The strength of these acids can be
explained in terms of the relative stabilities of their conjugate bases. Weaker the
conjugate base is, the stronger the acid. Keep in mind the fact that carboxylic
acids are weak acids.

Acetic acid Acetate ion

The K, of acetic acid is to the order of
The MCAT Chemistry Book

The acidity of a carboxylic acid is influenced by its substituents. Sub-

stituents which are very electronegative, especially when they are attached to
the a-carbon, increase the acidity of carboxylic acids. As the number of elec-
tronegative substituents increases, so does the acidity. This increase in acidity is
because of the increased stability of the carboxylate ion formed, as a result of
the presence of the electronegative substituent. This effect is due to what is
known as inductive effect. Because of the electron withdrawing effect of the
substituent, the charge is dispersed and the ion (carboxylate ion) is stabilized.
Study the following gradation of increasing acidity to reinforce the point just
made.
INCREASING ACIDITY

Carboxylic acids can undergo extensive hydrogen,bonding. So they have

higher boiling points than alkanes or even alcohols. Carboxylate ions are reso-
nance stabilized (Figure 23-11. The negative charge in the carboxylate anion is
shared by both the oxygens.

Figure 23-1

C. SYNTHESIS OF CARBOXYLIC ACIDS

By Oxidation

Carboxylic acids can be prepared by the oxidation of primary alcohols,

and aldehydes. An oxidizing agent such as KMnO, can accomplish these
conversions.

Sample reaction 23-1

Chapter 23 Carboxylic Acids

From Grignard Reagents

Another way to synthesize carboxylic acids is to react Grignard reagents

with C02. The Grignard reagent acts as a nucleophile toward the carbon diox-
ide. In an acidic medium the carboxylate entity formed is converted to carboxy-
lic acid. Grignard reagents can be prepared by reacting alkyl halides with mag-
nesium.

Sample reaction 23-2

R C O

Carboxylic acid
From Alkyl Halides via Nitriles

Primary or secondary alkyl halides can be converted into nitriles (alkyl

cyanide) by nucleophilic substitution. The nitriles formed can in turn be con-
verted to carboxylic acids by hydrolysis.

Sample reaction 23-3

NaCN
CH3CH2C1 t CH3CH2CN + NaCl

-
tCENt Cyanide ion

The cyanide ion is negatively charged and the negatively charged carbon atom
has nucleophilic character. The reaction usually occurs via S,2 mechanism. The
nitrile formed can be hydrolyzed to a carboxylic acid.

H20, H'
CH3CH2CEN t CH3CH2COOH
heat
The MCAT Chemistry Book

D. REACTIONS OF CARBOXYLIC ACIDS

Esterification

Carboxylic acids and alcohols can react in the presence of an acid cata-
lyst. The products formed are ester and water.

Sample reaction 23-4

H2S04
RCOOH + R'QH w RCOOR' + H20
Carboxylic acid Alcohol Ester Water

Decarboxylation

In a decarboxylation reaction, the carboxylic acid loses carbon dioxide.

The process usually requires heat to progress.

Sample reaction 23-4

Heat
HOOCCH,COOH * co2 + CH3COOH
Malonic acid Carbon dioxide Acetic acid
Chapter 23 Carboxylic Acids

CHAPTER 23 PRACTICE QUESTIONS 3. Predict the identity of Compound X from

the following reaction.
1. An alkyl magnesium halide is reacted with
carbon dioxide under very low pH (acidic
conditions). Which of the following are true
regarding this reaction?

I) Carbon dioxide acts as the nucleophile in

this reaction
11) Carboxylic acid is one of the products
111) Grignard reagent acts as the nucleophile

A. I only
B. I1 only
C. I & I11 Compound X
D. I1 & I11
A. Butyl methanoate
B. Butanaldehyde
2. Predict the major product (Compound B) C. Methyl butanoate
from the series of reactions shown below. D. Butanol

4. Which of the following has the highest boil-

ing point?

A. Pentanoic acid
B. Pentanol
C. Pentane
D. Pentanone
Compound A

I H2S04I H 2 0
Heat

Compound B

A. A four carbon carboxylic acid

B. A four carbon alkene
C. A five carbon carboxylic acid
D. A five carbon aldehyde
The MCAT Chemistry Book

5. Which of the following is true regarding 7. The product of the following reaction is:
the acidity of Compounds A & B?

H3C H C \ 0 H
Compound A
COOH - LiAlH4
H2O

P A. toluene.
H3C ' O' H B.
C.
benzene.
benzophenone.
Compound B
D. benzyl alcohol.
A. Compound B is more acidic, because
ethoxide is resonance stabilized.
B. Compound A is less acidic, because 8. The general formula indicated below is that
acetate is resonance stabilized. of:
C. Compound B is less acidic, because RCOOH
ethoxide is resonance stabilized.
D. Compound A is more acidic, because A. an alkane.
acetate is resonance stabilized. B. an aldehyde.
C. an ester.
6. Predict the most acidic compound from the D. a carboxylic acid.
choices below?
0
9. Which of the following compounds has the
highest boiling point?

A. Propanal
B. Propanoic acid
C. Propanone
D. Propane
Chapter 23 Carboxylic Acids

10. The name of the structure shown is: Questions 11-16 are based on the following
passage.

Passage

The sequence of reactions shown below were

done in a lab.

A. benzaldehyde.
B.
C.
D.
benzoic acid.
phenyl ethanoic acid.
heptanoic acid. 1 Reaction 1

1 Reaction 2

I Reaction 3

1 Reaction 4
 The MCAT Chemistry Book

Some of the reactions were done to synthesize 14. Formaldehyde can be converted to formic
compounds that were used to conduct other acid. What is the correct hybridization of
reactions. The experiments were also used to the carbon atom in the formic acid?
analyze the efficiency of these reactions.

11. All the statements given below are true,

EXCEPT:

A. CH3COOH can undergo hydrogen

bonding.
B. The melting point of carboxylic acids 15. Which of the following compounds has the
are higher than that of comparable highest pKa value?
alcohols.
C. The carbonyl group in carboxylic acids
are more electrophilic than that of
ketones.
D. In carboxylic acids, resonance is
possible.

16. From the following compounds, choose the

12. Which of the following is true about the compound that is the most acidic?
conversion involved in Reaction 2?

A. The conversion is an oxidation reaction,

and can be accomplished by using
LiAlH,.
B. The conversion is a reduction reaction,
and can be accomplished by using
LiAlH,.
C. The conversion is an oxidation reaction,
and can be accomplished by using
KMnO,.
D. The conversion is a reduction reaction,
and can be accomplished by using
KMnO,.

13. If the product of Reaction 2 were converted

to an ester, which of the following reagents
should be used for this conversion to be
done most easily?

A. NaBH4/H20
B. Alcohol/HCl
C. Thionyl chlorideheat
3 16 D. EtherIHCl
Chapter 24 Acid Derivatives

Acid Derivatives

A. INTRODUCTION

Acid chlorides, anhydrides, amides, esters, and ketoacids are some

examples of acid derivatives. An acid derivative has an acyl group which is
attached to a hnctional group. If the functional group attached to the acyl group
is a hydroxyl group, then it is a carboxylic acid.

Acid derivative

The acyl group is circled.

R-C-C1
0
II Acid chloride (Acyl chloride)

I
The MCAT Chemistry Book

0
11
R C N H 2
Arnide

0
II
RC-OR
Ester

R C e N Nitrile

Nitrile is also considered as a carboxylic acid derivative, even though it has no

acyl group.

An acid derivative can be converted to the corresponding carboxylic acid by

hydrolysis.

0 0

R-C-X
II H20
R-C-OH
II + HX
Acid derivative Carboxylic acid

This hydrolysis reaction occurs by nucleophilic substitution.

Increasing rate of hydrolysis

I
Arnide < Ester < Acid anhydride < Acid chloride

B. ACID CHLORIDES

An acid chloride can be prepared by using thionyl chloride and the

corresponding carboxylic acid.
Chapter 24 Acid Derivatives

Sample reaction 24-1

Propanoic acid Propanoyl chloride

Reactions of Acid chlorides

Acid chlorides form arnides when reacted with amines or ammonia.

Sample reaction 24-2

Acid chloride hide

Acid chlorides react with alcohols to form esters.

Sample reaction 24-3

0
II
H 2 C H 3 C C C 1
Acid chloride
Alcohol
CH30H
- H2CH3CCOCH3
0
II
Ester
+ HC1

C. ACID ANHYDRIDES

Acid anhydrides have important commercial uses. One of the acid anhy-
drides of such importance is acetic anhydride.

Acetic anhydride
Acetic anhydride can be synthesized by reacting a compound called ketene with
acetic acid.
The MCAT Chemistry Book

Sample reaction 24-4

Acetic acid 0 0

Ketene Acetic anhydride

Cyclic anhydrides such as succinic anhydride, maleic anhydride, and
glutaric anhydride can be prepared by heating the corresponding dicarboxylic
acids. The reaction results in intramolecular dehydration and ring formation.
Study the following example.

Sample reaction 24-5

Succinic anhydride
H2O

Reaction Involving Acid Anhydrides

Acid anhydrides react with alcohols to form esters and carboxylic acids.
A general equation representing this type of reaction is shown in the next sample
reaction.

Sample reaction 24-6

Acid anhydride Ester Carboxylic acid

Chapter 24 Acid Derivatives

D. AMIDES

Arnides can be synthesized from acid chlorides by reacting with ammonia.

Sample reaction 24-7

Acid chloride Amide

Hydrolysis of Amides

In the hydrolysis reaction of an arnide in the presence of acids or bases,

the products formed are carboxylic acid and amine. This is a nucleophilic acyl
substitution reaction.

E. ESTERS
0
II
RC-OR

Esters are compounds having the general structure formula shown above.
They have moderate dipole moments, resulting in intermolecular attractive forces.
For this reason, they have higher boiling points than the corresponding
hydrocarbons of comparable weights. But compared to alcohols, esters have
lower boiling points, since they cannot form hydrogen bonds among themselves
(Reason: No hydroxyl group). Esters can have hydrogen bonds with other
hydroxyl containing compounds such as water and carboxylic acids.

Synthesis of Esters

Esters can be synthesized by reacting carboxylic acids with alcohols, in

the presence of acid catalysts.

Sample reaction 24-8

RCOOH + R'OH w RCOOR' + H2O

Carboxylic acid Alcohol Ester Water
The MCAT Chemistry Book

F. REACTIONS OF ESTERS

Reduction

Esters can be converted to alcohols by reacting with reducing agents

such as lithium aluminum hydride.

Sample reaction 24-9

0 LiA1H4/ H 2 0 0
II II
CH3COCH2CH3 * CH3CH,0H + CH3COH
Ethyl acetate Ethyl alcohol Acetic acid

Esters with Grignard Reagents

Esters can react with Grignard reagents (two equivalents) to form tertiary
alcohols. See the following example.

Sample reaction 24-10

CH,
Saponification

The hydrolysis of esters in the presence of bases is called saponification.

Sample reaction 24-11

Ester Carboxylate salt

Chapter 24 Acid Derivatives

H-C-OH
I
H-C-OH
I Glycerol

H-C-OH
I
H
I
Fats are carboxylic acid esters of glycerol. When these esters are hydro-
lyzed, carboxylic acids with long hydrocarbon chains called fatty acids are
formed, along with the parent alcohol (glycerol).

..
H-C-0- C-R

Fat (triacyl glycerol)

The MCAT Chemistry Book

CHAPTER 24 PRACTICE QUESTIONS 3. The reaction of an ester with Grignard

reagent (excess) in the presence of an
1. Which of the following most readily aqueous acid results in:
undergoes hydrolysis among the acid
derivatives given below? A. a primary alcohol.
B. a secondary alcohol.
C. a tertiary alcohol.
D. no reaction at all, because esters are not
reactive with Grignard reagents.

4. Name the following compound.

A. Methyl propanoate
B. Ethyl butanoate'
C. Propionic anhydride
D. Propyl ethanone

2. Which ofthe following is the major product

of the reaction of an acid chloride with an
alcohol?

A. An ester
B. An aldehyde
C. A ketone
D. An alkane
Chapter 24 Acid Derivatives

5. Predict the product of the reaction shown

below.

A. Ortho-methylbenzyl acetate
B. Para-methyl benzoic acid
C. Para-methylbenzyl acetate
D. Para-methylethylbenzoate

6. The most likely product of an acyl chloride

reaction with ammonia is:

A. a carboxylic acid.
B. anamide.
C. an anhydride.
D. an azide.

7. All the following reactions can be used for

the preparation of carboxylic acids,
EXCEPT:

A. ester hydrolysis.
B. nitrile hydrolysis.
C. by the reaction of Grignard reagent with
carbon dioxide.
D. by the reduction of aldehydes.
This page intentionally left blank
Chapter 25 Ethers

Ethers

A. INTRODUCTION

Ethers are compounds with the general formula ROR' (e.g.,CF$qoCyCHJ.

B. PROPERTIES OF ETHERS

Ethers are polar molecules. Compared to alcohols, ethers have very low
boiling points mainly because they cannot form hydrogen bonds (intermolecular).
The boiling points of ethers are close to alkanes of comparable weights. Ethers
are not very reactive.

C. PREPARATION OF ETHERS

Simple ethers can be prepared by acid-catalyzed intermolecular dehy-

dration of alcohols.

Sample reaction 25-1

H2S04
2 C2H50H *
heat C2H50C2H5

An ether can also be prepared by the nucleophilic substitution of an

alkyl halide by an alkoxide. The reaction is an example of S,2 reaction. The
reaction is called Williamson ether synthesis (Sample reaction 25-2).
The MCAT Chemistry Book

Sample reaction 25-2

Sodium propoxide Propyl ethyl ether

A primary alkyl halide

It is best to use primary alkyl halides in this type of reaction. Other halides most
likely undergo elimination rather than substitution reaction.
D. CLEAVAGE OF ETHERS BY ACID

Ethers are cleaved when reacted with hydrogen halides to form alkyl
halides and water. A sample reaction is shown:

Sample reaction 25-3

2 HI
CH3CH20CH3 - CH31 + CH3CH21 + H20
heat

E. THE BASICITY OF ETHERS

Ethers are weakly basic. The basicity is due to the presence of the unshared
electrons that are present on the oxygen atom of ethers.

R - O R
....

F. EPOXIDES

Epoxides are three-membered cyclic ethers. Epoxides can be synthesized by the

oxidation of corresponding alkenes with peroxy acid.

Ethylene Peroxy benzoic acid Ethylene oxide Benzoic acid

Chapter 25 Ethers

Some Reactions of Epoxides

Epoxides can undergo acid or base-catalyzed ring-opening reactions. If the ep-

oxide used in the reaction is symmetric, the product will be the same under both
conditions. But the products will be different, if the epoxide is unsymmetric.

Under Acid-Catalyzed Conditions

H3C-f:CH2
H
- -
CH30H, H+
H3Cw?CH2

.. 1 CH~-~-H

- rH3$1"
r H
More stable (lower transition state energy)

+
HCPCH2 + CH30H2 H C C H 2
I
:G-CH3 P:Q-CH3
I
/
H

Under acidic conditions, the nucleophilic attack is directed to the proto-

nated epoxide. The nucleophile adds to the more highly substituted carbon in
the epoxide ring. This is because in the protonated epoxide, the positive charge
is shared by the ring-carbon atoms attached to the oxygen. The positive charge
is more stabilized when it is on the more highly substituted carbon (stronger
electrophile), and thus the attack of the nucleophile is preferentially on the more
substituted carbon under acidic conditions.
The MCAT Chemistry Book

Under Basic Conditions

In a base-catalyzed ring opening of an epoxide, the nucleophilic attack

is on the less substituted (less hindered) carbon atom in the epoxide ring. The
mechanism is shown below.
Chapter 25 Ethers

CHAPTER 25 PRACTICE QUESTIONS 4. Which of the following is true regarding

ethers?
1. All the reactions described below CANNOT
prepare ethers, EXCEPT: I. Ethers are not very reactive.
11. Ethers are extremely reactive.
A. Williamson synthesis. 1II.Ethers are flammable.
B. dehydrogenation of alkenes. IV. Ethers have higher boiling points than
C. decarboxylation of carboxylic acids. alcohols.
D. Clemmenson reaction.
A. I & III only
B. I1 & 111 only
2. In terms of boiling point, ethers most C. 11,111, an IV only
resemble which of the following types of D. I & IV only
compounds?

A. alcohols 5. The reaction sequence shown in the passage

B. water is most likely to be effective if the reaction
C. carboxylic acids runs by S,2 mechanism. Which of the
D. alkanes following is the best suited alkyl halide to
conduct this reaction most efficiently?

3. Which of the following regarding ethers is

true?

A. They are polar.

B. They are relatively less reactive.
C. They can b e used as solvents in
reactions.
D. All the above

Questions 4-8 are based on the following

passage.

Passage 1

Consider the following synthesis reaction.

Reaction 1
CH3CH2CH20Na+ RC1
CH3CH2CH20R + ~
- a ~ i

where R represents an alkyl group.

The MCAT Chemistry Book

6. All the following alkyl halides can undergo 8. Which of the following is not an ether?
elimination by the reaction represented in
Experiment 1, EXCEPT:

H3C, ,CH3
C-C,
C* H \/ H
0

7. Predict the major product (Compound M)

of the following reaction.

CH,OCH, -conc.HBr
Compound M

A. CH,Br
B. CH30Br
C. CH30BrCH,
D. No reaction occurs.
Chapter 26 Phenols

Phenols

A. INTRODUCTION

Phenol is a compound which has a hydroxyl group attached to a benzene

ring. Although phenols have similar properties like alcohols (one aspect of
similarity is that both phenols and general alcohols have the hydroxyl group),
phenols are unique because of their aromatic ring.

Phenol 6

@..
Salicylic acid
COOH'

OH
(0-hydroxybenzoic acid) Resorcinol
Ilydroquinone
(1 ,CBenzenediol) ( I ,3-Benzenediol)
The MCAT Chemistry Book

B. PROPERTIES OF PHENOLS

Hydrogen bonding is significant in phenols, because of the presence of

the hydroxyl group. Phenols can form hydrogen bonds with other phenol
molecules and water. Hence the boiling and melting points are relatively high
for phenols. Phenols are acidic. In terms of acidity, phenols are in between
carboxylic acids and alcohols.

I Increas~ng acidity

ALCOHOLS < PHENOLS < CARBOXYLIC ACIDS

Phenol Phenoxide anion

It is important to analyze the fact that the phenoxide ion's negative charge
is stabilized by the delocalization of the electrons into the benzene ring. This is
one of the reasons for phenols' increased acidity compared to alcohols. In alkoxide
ions negative charge is localized in the oxygen atom (not delocalized).

C. EFFECTS OF SUBSTITUENTS ON THE ACIDITY OF PHENOLS

When a phenol has a strongly electron-withdrawing substituent group,

the acidity of the phenol is increased. The reason for this increase is the electron-
withdrawing group's ability to delocalize the negative charge, more than the
phenoxide ion itself.
Increasing acidity
I

NO2
The effect of substituents on the acidity of phenol

On the contrary, electron-donating substituents decrease the acidity of phenols.

Chapter 26 Phenols

D. REACTIONS OF PHENOLS

Formation of Quinones

Oxidation of phenols results in compounds called quinones. They are

conjugated, and they contain two carbonyl groups (dicarbonyl). See the example
below:

Sample reaction 26-1

OH OXIDATION The quinone compound

E. ELECTROPHILIC AROMATIC SUBSTITUTION REACTIONS

Certain compounds (electrophilic) can react with phenols (nucleophilic).

The nucleophilic activity can be either in the aromatic ring or the oxygen in the
hydroxyl group. Examples of electrophilic aromatic substitution include nitration,
halogenation, Friedel-Craftsreactions (alkylationand acylation), and sulfonation.
The halogenation example shown below is a polysubstitution reaction involving
bromine. The polysubstitution usually occurs when polar solvents are used.

Sample reaction 26-2

Phenol

2,4,6-Tribromophenol
(Polysubstitutionproduct)
The MCAT Chemistry Book

Monobromination can be achieved by using nonpolar solvents.

Sample reaction 26-3

Phenol

p-Bromophenol
(major product)
Chapter 26 Phenols

CHAPTER 26 PRACTICE QUESTIONS 3. Which of the following compounds can

have significant amounts of intramolecular
1. The product of the reaction sequence shown hydrogen bonding?
below is:
A. ortho-nitrophenol
B. para-nitrophenol
C. phenol
D. para-hydroxy benzaldehyde

Compound A

/- H20
[ NaOH,
heat

Compound B

A. meta cresol.
B. phenol.
C. toluene.
D. styrene.

2. The reaction of phenol with Br2 1 H 2 0 can

lead to all the following products in
relatively significant quantities, EXCEPT:

A. ortho-Bromophenol.
B. meta-Bromophenol.
C. 2,4,6-Tribromophenol.
D. all the above are formed in significant
amounts.
This page intentionally left blank
Chapter 27 Amines

Amines

A. INTRODUCTION

Amines are derivatives of ammonia. The alkyl derivatives of ammonia

are called alkyl amines, and the aryl (aromatic) derivatives of ammonia are
called aryl amines. These nitrogen-containing compounds are unique for their
basicity.

Ammonia
NH3

.
e ee ee

RNH2 R2NH R3N

Primary amine Secondary amine Tertiary arnine

R= alkyl or aryl group

B. STRUCTURE OF AMINES

The carbon to which the nitrogen is attached in an alkyl m i n e is sp3

hybridized, and in aryl amines it is sp2hybridized. The nitrogen in the amines is
sp3hybridized. As you have probably noticed, the nitrogen present in an amine
has an unshared electron pair. In alkyl amines, the substituents attached to the
nitrogen atom are arranged in a pyramidal manner around the nitrogen. In aryl
amines, this pyramidal mode is more flat compared to alkyl amines. Moreover,
the unshared pair of electrons in aryl amines has the advantage of delocalization
into the pi electrons in the aromatic ring.

C. PROPERTIES OF AMINES

Amines are somewhat polar. But the polarity is not as high as that of
alcohols. As Figure 27-1 indicates, the arnines have intermediate boiling points.
The MCAT Chemistry Book

Keep in mind that we are comparing the boiling points of arnines with comparable
alkanes and alcohols. Among amines only primary and secondary amines can
form hydrogen bonds. Lower amines are soluble in water.
Increasing boiling point

Alkanes < Amines < Alcohols

Figure 27-1

D. PREPARATION OF AMINES

Alkylation Method

Arnines can be prepared by the alkylation of ammonia. In this array of

reactions (Figure 27-2), the amines nucleophilically attack the alkyl halides. As
shown below, the first reaction yields a primary amine. Primary amines yield
secondary arnines which in turn yield tertiary arnines, and tertiary amines yield
quaternary ammonium salts.

Primary Secondary
amine amine

-2Y+ R,NH
AkJl
halide HX HX

K
HX
R3N
Tertiary
amine

Quaternary
ammonium salt R,N+X-
1 A
Figure 27-2
Chapter 27 Amines

E. REACTIONS OF AMINES

Formation of Amides

Amines can react with acid chlorides to form amides. A representative

reaction (Sample reaction 27- 1) is shown. The reaction proceeds by nucleophilic
addition to the carbonyl group by the amine.

Sample reaction 27-1

Amine Acid chloride -HC1 Amide

0 Amine OH 0
II
RCCI + R'NH* - - R-C-~1 I II
R-C-NHR'
I
Acyl Amide
chloride
The tetrahedral intermediate

F. BASICITY OF AMINES

Amines are weakly basic compounds. Alkyl amines are more basic than
ammonia, and aryl arnines are less basic than ammonia.

aryl arnines < ammonia < alkyl amines

The MCAT Chemistry Book

CHAPTER 27 PRACTICE QUESTIONS 3. All the following are nitrogen-containing

compounds, EXCEPT:
1. Arrange the following compounds in the
increasing order of boiling points? A. aniline.
B. quaternary ammonium salt.
Compound A CH3CH2CH2COOH C. oxime.
D. ester.
Compound B CH3CH2CH2CH3

Compound C CH3CH2CH2CH20H

Compound D

A. A<B<C<D
B. B<D<C<A
CH3CH2CH2CH2NH3
Reaction 1

1
CH3CH2CH2CH2NH2

C. B<C<D<A
D. B<D<A<C 4. The conversion involved in Reaction 1 can
be best characterized as:

2. Which of the following compounds has the A. oxidation.

highest basicity? B. dehydrogenation.
C. isomerization.
D. reduction.
Chapter 27 Amines

Questions 5-10 are based on the following I There are a wide variety of naturally
passage. 1 occurring amines. Amines include caffeine,
morphine, cocaine, quinine, and amphetamines,
Passage 1 just to name a few. Amines are also biologically
important. Some of the biologically important
Amines range from simple structures to amines include thiamine, adrenaline, acetyl
very complex structures. Some simple arnines choline, and riboflavin.
and their K, values are given below.
Gamma-arninobutyrate is an m i n e and
a neurotransmitter. It has mainly an inhibitory
Kb of conjugate bases

n function and is extensively found as a

neurotransmitter in the Purkinje cells of the
central nervous system.
The MCAT Chemistry Book

I (Compound P)
CH2
I

I
coo-

LGD k
+H~NCH~CH~CH~COO-
Compound Q
Compound A

to other cycles

Compound B
NADH + H+

I
(Compound N) C H ~

I
coo-
Compound P - L-Glutamate
Compound Q - Y-Aminobutyrate
Chapter 27 Amines

5. Which of the following is the most acidic? 10. y-Aminobutyrate can be best described as a:

A. primary arnine.
B. secondary arnine.
C. tertiary amine.
D. peptide.

6. All the following can undergo hydrogen

bonding themselves, EXCEPT:

A. aniline.
B. triethylamine.
C. ammonia.
D. methylamine.

7. The conjugate acid of which of the follow-

ing is the most acidic?

A. Methylamine.
B. Ammonia.
C. tert-Butylamine.
D. Aniline.

8. The conversion of glutarnate to aminobu-

tyrate is best described as:

A. a neutralization reaction.
B. a decarboxylation reaction.
C. a dearnination reaction.
D. an amination reaction.

9. The conversion of Compound M to

Compound N is done by the process of:

A. oxidation.
B. transamination.
C. inversion of configuration.
D. reduction.
This page intentionally left blank
Chapter 28 Amino Acids and Proteins

Amino Acids and Proteins

A. INTRODUCTION

Proteins are polymers of amino acids. Proteins are extremely important

since they have a wide range of biological significance. They serve as nutrients,
enzymes, cellular products of genes by translation (reflects the hereditary
information), building material of muscles and other biologically important
structures.

B. AMINO ACIDS

Amino acids are the monomeric units of proteins. The general structure
of an amino acid is as follows:

a
carboxyl group

R
I

amino group

In the above diagram representing an amino acid, the characteristic amino and
carboxyl groups are indicated by the arrows. Amino acids combine with other
amino acids to form peptides.
 The MCAT Chemistry Book

Peptide Bond
mmoom
An amido linkage formed between two amino acids is called peptide
11
C I? /
bond. Figure 28-1 shows the peptide bond between the amino acids, alanine
and serine.
/ ';
The peptide bond

Figure 28-1
The peptide bond is
resonance stabilized.

Peptide linkage

Based on stereochemical analysis, it has been proved that in a typical

peptide linkage such as shown in the figure, the atoms indicated in
bold-type occupy the same plane

Figure 28-2
Chapter 28 Amino Acids and Proteins

C. PEPTIDES

Dipeptide - contains two amino acids.

Tripeptide - contains three amino acids.
Tetrapeptide - contains four amino acids.
Pentapeptide - contains five amino acids.

Polypeptides - contain many amino acids.

Proteins - contain fifty or more amino acids.
(classifications slightly vary)

D. ALPHA AND BETA AMINO ACIDS

Amino acids can be classified as a , P, y, and so on. If the amino group is

attached to the carbon next to the carboxylic carbon, the amino acid is an a-amino
acid. If it is attached to carbon next to the a-carbon, the amino acid is a p-amino
acid.

I
'N H3- CH- C O ~a-amino acid
a

I
'N H~CH~CH-~06
p-amino acid
P a

E. DIPOLAR NATURE OF AMINO ACIDS

Amino acids possess a dipolar nature. They are amphoteric, since they
have both acidic and basic functional groups. Dipolar ions are often referred as
mitterions. In certain pH ranges, the amino acids exist predominantly as
zwitterions, with a net charge of zero.
The MCAT Chemistry Book

PREDOMINANT AMINO ACID SPECIES

AT ISOELECTRIC POINT (ZWITTERIONIC)

PREDOMINANT AMINO ACID SPECIES PREDOMINANT AMINO ACID SPECIES

AT VERY ACIDIC ENVIRONMENT AT VERY BASIC ENVIRONMENT
[acidic pH] [alkaline pH]

F. CLASSIFICATION OF AMINO ACIDS

On the basis of the R groups present in the amino acids, they can be
classified into various groups. There are about 20 important amino acids that
are found in proteins.
Chapter 28 Amino Acids and Proteins

HYDROPHOBIC AMINO ACIDS

1. Nonpolar amino acids with aliphatic R groups

I
Glycine Alanine CH3 Valine

Leucine Isoleucine Proline

2. Nonpolar amino acids with aromatic R groups

OH
Phenylalanine Tryptophan Tyrosine
The MCAT Chemistry Book

HYDROPHILIC AMINO ACIDS

1. Polar amino acids

0 0 0

+
H 3 N C H C O H
II +
H3NpCH-C-OH
II +
H 3 N C H C O H
II
I I I
PH2
OH
CH-OH
I
CH3
rH2
SH

Serine Threonine Cysteine

0
+
H 3 N C H C O H
+
H 3 N C H C O H
+
H 3 N C H - C O H
II
I I I
PH2 PH2 TH2
c o
TH2
c o
TH2
S OH
I
NH2
I
CH3
Glutarnine Methionine Asparagine

2.Acidic amino acids

Aspartate I
c o
I
Chapter 28 Amino Acids and Proteins

HYDROPHILIC AMINO ACIDS

3. Basic amino acids

C N H
I
Lysine Arginine Histidine

G. PROPERTIES OF AMINO ACIDS

Amino acids have ionizable groups. Each ionizable group has its own
pKa value, which is the pH at which half of that particular ionizable group is in
the dissociated state and the other half in the undissociated state. For the MCAT
you should be familiar with the concept of isoelectric point. Isoelectric point of
an amino acid is the pH at which the net charge of the amino acid is zero. Amino
acids can sometimes act as acids or bases. This nature (property) of amino acids
is called amphoteric property.
The MCAT Chemistry Book

..
H 3 N C H C 0

I
H
s a \ \
Acting as (proton acceptor)
an acid
(proton donor)

H+ + H2N-CH-C-0
i - +
H3NPCH-COH
i
I I
Figure 28-3

The amino acid shown in the above example is glycine. The amphoteric species
is shown on top (bold faced).

H. PROTEINS

The structure of proteins can be classified into primary, secondary, tertiary,

and quaternary structures, according to the level of complexity of the proteins.

Primary Structure of Proteins

The simple sequence of amino acids in a protein is called the primary

structure of the protein. These sequences of amino acid chains can bend, fold,
and bond to form more complex structures of proteins, which can be described
in terms of secondary, tertiary, and quaternary structures. Figure 28-4 shows a
tetrapeptide with amino acids: alanine, lysine, glycine, and phenylalanine.
Chapter 28 Amino Acids and Proteins

+
NH3- alanine-lysine-glycine-phenyalanin? COO-

N-terminal end v'

+

I I
I u PU,

Figure 28-4

peptide bonds
A peptide chain has an amino acid with the free (without a peptide bond)
amino group on one end (the N-terminal end), and an amino acid with free
(without a peptide bond) carboxylic group on the other end (the C-terminal
end).

the peptide bond

Figure 28-5

The nitrogen and carbon atoms (indicated

by arrows) are sp2 hybridized
 The MCAT Chemistry Book

Secondary Structure of Proteins

The two main types of secondary structural arrangements are the a-helix
and the P-pleated sheet. Generally, these conformations generate the secondary
structure of proteins.

The a-helical structure or conformation is one of most important aspects

of the secondary structure of proteins. This conformation of peptide chain has
Disulfide bond formatiom interactions within its chains by hydrogen bonding. A simple arrangement can
be described as a helical structure in which the long polypeptide chain is wound
Cysteine around the long axis. The side chains (R groups) of the amino acids extend out
H~N-CH-C-OH of the helical backbone. Figure 28-6 shows right- and left-handed a-helical
I structures.
r"'
SH 2. P-Pleated sheet

I" These represent the sheetlike arrangement of the polypeptide chains.

The hydrogen bonds we found between the adjacent polypeptide chains. The
i"'
Cyste~ne
polypeptide chains involved in the pleated sheet structure can be either parallel
or antiparallel. Hydrogen bonds stabilize the P-pleated sheet (see Figure 28-7).
H2N-CH-f-0H 0
Tertiary Structure of Proteins
I

H2N-CH-COH
I oxla-

fi
II
The tertiary structure of proteins is the three dimensional arrangement
of the polypeptide chain. Tertiary structure depicts the way in which the secondary
structure folds to form the three dimensional form. Different kinds of bonds or
interactions are responsible for the maintenance of the tertiary structure. They
include hydrophobic forces, hydrogen bonds, disulfide bonds, salt bridges, and
Van der Waal forces.
I
Disulfide bonds: These are bonds formed by two cysteines.
I t H,O

Hydrophobic bonding: Hydrophobic bonding or forces are weak interactions

CH2
I between hydrophobic side chains of the hydrophobic amino acids in a protein.

I
H 2 N C H - C O H
Quaternary Structure of Proteins

Cystme II
o Some proteins can be complex, when they contain multiple subunits of
polypeptide structural entities. The way in which three-dimensional subunits
interact to form the complete hnctional protein is called the quaternary structure
of a protein. This level of hierarchy is possible only if the protein has multiple
units. An example is hemoglobin.
Chapter 28 Amino Acids and Proteins

-eft handed helix Right handed helix

Figure 28-6

Figure 28-7
n-terminal

C-terminal
C-terminal

n-terminal

Pleated sheet (antiparallei)

The MCAT Chemistry Book

I. DENATURATION OF PROTEINS

Proteins can be denatured in many ways. A common example that we all

have seen is the denaturation of egg albumin when we cook them. In this case,
the denaturing agent is the temperature. Most biologically significant proteins
are extremely heat sensitive. An increase in temperature can disrupt hydrogen
bonds as well as hydrophobic interactions in proteins. This is one reason why
we cannot survive in extreme (hot or cold) temperatures because at extreme
temperatures, the proteins and other sensitive chemicals in our body denature
and cease to function. Besides temperature changes, pH changes can also affect
proteins. Other denaturing agents include detergents, oxidizing agents, reducing
agents, UV light, and pressure.

Generally, protein denaturation includes the complete or partial unfolding

of the polypeptide chain, cleavage of disulfide linkages, and breakage of
noncovalent interactions. Denaturation is sometimes reversible. The reversing
process is called renaturation.
Chapter 28 Amino Acids and Proteins

CHAPTER 28 PRACTICE QUESTIONS 5. Amino acids can be bonded to each other

covalently by means of:
1. Which of the following is a basic amino
acid? A. hydrogen bonds.
B. dipole-dipole interactions.
A. Valine C. phosphodiester linkages.
B. Tryptophan D. peptide linkages.
C. Arginine
D. Threonine
6. Proteins are made of:

2. All the following amino acids are optically A. monosaccharides.

active, EXCEPT: B. sugars.
C. lipids.
A. Valine D. amino acids.
B. Proline
C. Glutamic acid
D, Glycine 7. Which of the following will certainly NOT
affect the structure of a protein?

3. At a particular pH, the amino acid glutamic A. Proteases

acid has a net charge of zero. When this pH B. Strong bases
is achieved, it is said to be at glutamic C. Strong acids
acid's: D. All the above can have some effect on
the structure of proteins.
A. isobaric point.
B. isomeric point.
C. isotonic point . 8. Which amino acid is responsible for the
D. isoelectric point. formation of disulfide bonds?

A. lysine
4. Which of following groups are not present B. phenylalanine
in any of the common amino acids? C. tryptophan
D. cysteine
A. Amino group
B. Carbonyl group
C. Aldehyde group
D. All the above groups are present.
The MCAT Chemistry Book

Questions 9-14 are based on the following

passage.

Passage 1

Amino acids play an essential role in

I -COO* I NH; I Side
chain
I

the physiological processes in our body. They

are the main building blocks of the principal Arginine 2.2 9.0 12.5
structures in our body. Amino acids themselves
or in combination with carbohydrates, lipids, Cysteine 2.0 10.3 8.2
etc., form an intricate system of physiologically
Glutamate 2.2 9.7 4.3
important structures and functional domains
without which life as we know it cannot exist. Glycine 2.3 9.6

From a biological point of view with Serine

respect to life forms, only 20 amino acids are Threonine
important, even though many more are found
in nature. Most amino acids are optically active. Trylstophan 2.8 9.4
With the functional groups and their chemical
behavior, we can predict certain properties of Tyrosine 2.2 9.1 10.1
amino acids such as ionization properties.
Amino acids join together to form peptides.
Lysine I 2.2 9.0 10.5
Table-1 shows the pKa values of some amino
acids.

OH
Aspartic acid
Chapter 28 Amino Acids and Proteins

9. Which of the following are true regarding 12. In our body, some amino acids are changed
amino acids? into metabolic intermediates which can
enter metabolic cycles. One such example
I. Amino acids have carboxyl group. is given below. The example shows the
11. Amino acids have high melting points. conversion of serine into pyruvate which
11I.Some amino acids can have a net posi- can be converted to acetyl CoA and enter
tive charge. the Krebs cycle. Compound Y can be best
IV. Some amino acids can have a net nega- described as:
tive charge.

A. I, I11 & IV only

Compound X
B. I, I1 & I11 only
C. I, I11 & IV only
D. I, 11, I11 & IV

10. Which of the following represents the pH

at which there is no net movement of the
amino acid when subjected to an electric
field?
H,C- C- COO-
A. pH at pKa 11
NH
Compound Y
B. pH at pKb
C. pH at isoelectric point
D. There is no such pH for amino acids
because some amino acids are acidic,
some are basic, and some are neutral.
H,C- C- COO
11. Which of the following represents a peptide 11
0
Compound Z
bond?

Acetyl CoA

A. an amide.
B. an imine.
C. a phenol.
D. an imidazol.
The MCAT Chemistry Book

13. Which of the following amino acids will 14. All the following are NOT basic amino
migrate toward the positive electrode when acids, EXCEPT:
subjected to an electric field at a pH of 7.0?
A. Glutamate.
B. Aspartate.
C. Alanine.
D. Lysine.

I Glutamic acid

A. Alanine
B. Arginine
C . Lysine
D. Glutamic acid
Chapter 29 Carbohydrates

Carbohydrates

A. INTRODUCTIQN

Carbohydrates, commonly known as sugars, are the most abundant group

of biomolecules in nature. Our daily regimen of foods includes different forms
of carbohydrates. Potatoes, rice, bread, pasta are carbohydrate-rich sources of
food. There are different types of carbohydrates. The simplest units are called
monosaccharides. A disaccharide contains two monosaccharides. A polysac-
charide contains many monosaccharide subunits.

B. MONOSACCHARIDES

Based on the number of carbons, monosaccharides can be called trioses

(three carbons), tetroses (four carbons), pentoses (five carbons), hexoses (six
carbons), heptoses (seven carbons), octoses (eight carbons), and so on.

Monosaccharides contain many hydroxyl groups and a carbonyl group.

If a monosaccharide contains an aldehyde group, it is called an aldose sugar. If
a monosaccharide contains an keto group, it is called an ketose sugar.

HO-C-H

H H-C-OH
I
H-C-OH
I
" T O
CH20H
H I
CH20H
Glucose Fructose
(an aldohexose) (a ketohexose)
Figure 29-1 Glucose is an aldose sugar. Fructose is a ketose sugar.
The MCAT Chemistry Book

CHO

Glyceraldehyde
I

CHO CHO

CH20H
:+:. CH20H
Erythrose Threose

CHO CHO CHO CHO

;H
+!-

CH20H
;$H

CH20H
; ;H
$

CH20H
:$: CH20H
OH

Ribose Arabinose Xylose Lyxose

CHO CHO

3
CHO
I
H

H OH

H
CH20H
OH
CH20H CH20H CH20H

i
Allose Altrose Glucose Mannose

:$
OH H H

T
OH OH H H
HO OH
H HO H H HO H

H H H H
H
$ CH20H
OH CH20H
OH CH20H
OH
CH20H
Gulose ldose Galactose Talose

Figure 29-2 D-aldose sugars

Chapter 29 Carbohydrates

C. CONFIGURATIONS OF MONOSACCHARIDES

Monosaccharides have chiral centers and thus exhibit optical activity.

Let's explore the structure of glyceraldehyde. In the three-dimensional
representation, the dotted wedges indicate the bonds that extent backwards from
the chiral carbon (away from you or into the plane of the page); and the solid
wedges indicate the bonds that are pro-jectedtoward you (out of the plane of the
page). In stereochemistry, Fischer projection is an important way to represent
the spatial orientation of molecules. In Fischer projection representation, the
bonds that are pointed backward (away from you or into the page) are indicated
by vertical lines, and the bonds that extend toward you (out of the page) are
represented by horizontal lines. For a more detailed approach, refer to Chapter
19 (Stereochemistry).

CHO
I
H-c-OH I
- I H-C-OH
I

D glyceraldehyde

L glyceraldehyde

Figure 29-3

By convention, the carbonyl group is always drawn on top. With that as

the standard, we can describe the structure of D-glyceraldehyde as follows:

D-glyceraldehyde has a hydroxyl group represented on the right side of

the chiral carbon. L-Glyceraldehyde has a hydroxyl group represented on the
left side of the chiral carbon. To determine whether a sugar structure shown is L
or D, we have to locate the chiral carbon that is farthest from the carbonyl group,
and see whether the hydroxyl group is on the right or on the left of the chiral
carbon.
The MCAT Chemistry Book

D. CYCLIC STRUCTURE OF HEXOSES

Glucose

Glucose is a six-carbon aldohexose. The straight chain hexose structures

can become cyclic. When aldehydes and ketones undergo reactions with alcohols,
hemiacetals or hemiketals are formed. In aldohexoses, the cyclic structure is
formed when the hydroxyl group in the fifth carbon reacts (nucleophilic addition)
with the carbonyl carbon of the aldehyde group. The product formed is a
hemiacetal. The cyclization is represented in Figure 29-4.

A few facts worth remembering

1) The six-membered (hemiacetal) ring formed is called the pyranose ring.

2) The oxygen in the ring is from the hydroxyl group involved in the ring closure.
3) The carbon which is denoted as "carbon one" in the cyclic structure is the
carbonyl carbon of the straight chain (the aldehyde group).
4) Notice that the cyclic structure can go either way in the sense that the resulting
cyclic structure can either be an a- or a p-anomer.
5) The carbon number 'one' shown in the cyclic structure is called the anomeric
carbon.
6 ) In aqueous solutions, the a- and p-anomers can interconvert, and the process
is termed mutarotation.
Chapter 29 Carbohydrates

H - C O H
I
\
HO-C-H
1
H-C-OH
3 I
A l

Figure 29-4 The formation of cyclic structures of glucose

Fructose

Fructose is a ketohexose sugar. The cyclic structure formed is called a

hemiketal, and the five membered ring that is formed is called furanose ring.
The straight chain structure and the cyclic structures of fructose are shown in
Figure 29-5.
The MCAT Chemistry Book

P-D-~ructofuranose a-D-Fructofuranose

CYCLIC STRUCTURES OF FRUCTOSE

Figure 29-5

Epimers are any two isomeric sugars which differ in their configurations
only at one of the chiral carbon atoms. Glucose and mannose are epimers. Glucose
and galactose are also epimers.

E. OXIDATION OF MONOSACCHARIDES

Monosaccharides can be oxidized. Benedict's reagent (oxidizing agent)

can accomplish this by reacting with the aldehyde group of the open-chain form.
Thus aldose and ketose sugars are reducing sugars. In fact, all monosaccharides
are reducing sugars. Some disaccharides can be oxidized by Benedict's reagent.
Chapter 29 Carbohydrates

BENEDICT'S TEST FOR REDUCING SUGARS

[red precipitate]

RCHO + 2cu2+ - OH
-
RCOOH +
Copper(1) oxide
Cu20 + H20

I OXIDATION

Benedict's reagent is reduced in the process to cuprous oxide.

F. DISACCHARIDES

Disaccharides are sugar units containing two monosaccharides linked

by a covalent bond called glycosidic bond. Maltose, sucrose, and lactose are
examples of disaccharides. Maltose is formed by the linkage of two glucose
molecules by a glycosidic bond. Sucrose is a combination of glucose and fructose.
Lactose is composed of glucose and galactose. The hydrolysis of disaccharides
gives their corresponding monosaccharide subunits.

Maltose \ t glucose + glucose

Sucrose \ t glucose + fructose

Lactose glucose + galactose

HYDROLYSIS OF DISACCHARIDES
The MCAT Chemistry Book

Figure 29-6 The structure of maltose

Figure 29-7 The structure of sucrose

7H20H

H HO
Figure 29-8 The structure of lactose
Chapter 29 Carbohydrates

G. POLYSACCHARIDES

Polysaccharides are polymers of monosaccharides. Starch, glycogen,

and cellulose are examples of polysaccharides. Polysaccharides can be homo-
geneous in terms of its fundamental unit (monosaccharide). If more than one
type of monosaccharide is present in a polysaccharide, then it is called a het-
eropolysaccharide.

Starch

Starch is composed of two types of polymer structures derived from

a-glucose - a linear polymer form called amylose, and a branched polymer
form called amylopectin. Figure 29-9 shows the two types of glucose polymers
involved in the formation of starch. The amylose has a(l+4) linkages of
glucose subunits, and the amylopectin has a(1+6) and a(1+4) linkages.

Glycogen

Glycogen is a polysaccharide found in most animals as a storage medium

of carbohydrate. It is stored mainly in the skeletal muscles and the liver. We can
say that starch is to plants as glycogen is to animals. In other words, the animal
carbohydrate storage medium is glycogen, and the plant carbohydrate storage
medium is starch. The structure of glycogen is mostly like that of the amylopectin
structures found in starch, only with more branching.

Cellulose

Cellulose is a polysaccharide found in plants. But unlike starch and gly-

cogen, the monosaccharide units that build up the cellulose are P-glucose units.
Also the polysaccharide chains found in the cellulose structure are unbranched.
In addition, the linkages in cellulose units are P-linkages instead of a-linkages.
This type of P-linkage is the reason why humans cannot digest cellulose. To be
more precise, the enzymes that we have do not work on such linkages. Some
herbivores such as cattle have cellulose digesting bacteria in their stomachs
which digest the foods containing cellulose. Once the bacterial enzymes break
the cellulose structures into simple sugars, then the animal can use them for its
metabolic needs.
 The MCAT Chemistry Book

Long chans

CH20H

'0

H OH H OH n OH

Long chams

Figure 29-9 The glucose polymers that are involved in the formation of starch
Chapter 29 Carbohydrates

CHAPTER 29 PRACTICE QUESTIONS 4. Which of the following is NOT a

disaccharide?
1. All the following are monosaccharides,
EXCEPT: A. Maltose
B. Sucrose
A. galactose C. Glycogen
B. glucose D. Lactose
C. ribose
D. maltose
5. The structure shown below is that of a
monosaccharide. How many optical
2. What is the name of the structure drawn isomers are possible for this structure?
below?
CHO

3. A lab technician making a fresh sugar

solution noticed that the optical activity of
the sugar solution changed after the solution
had been standing for several hours. This
change in optical activity is best explained
by the phenomenon called:

A. Tyndall effect.
B. Brownian movement.
C. optical anomaly.
D. mutarotation.
 The MCAT Chemistry Book

Questions 6-11 are based on the following 6 . All the following are monosaccharides,
passage. EXCEPT:

Passage 1 A. sucrose.
The structures of some monosaccharides B. fructose.
are drawn below. C. glucose.
CHO D. galactose.

7. The structure given below is:

; ; * :H

H OH

H OH

CH20H CH20H
Altrose Glucose

CHO CHO

CH,OH CH~OH
Mannose Allose
A. glucose.
B. ribose.
C. fructose.
D. maltose.

374
H *
HO

HO

H
CH~OH
Gulose

CHO

CH20H
Galactose
OH
* CH~OH
Idose

CHO

CH20H
Talose
H

OH
Chapter 29 Carbohydrates

8. Which of the following statements are true 10. The structure of a disaccharide is shown
regarding the two structures (Compounds I below. The bond indicated by the arrow is
& 11) drawn below? called:

Compound I

A. a glycosidic linkage.
B. a peptide linkage.
H H C. a glucose linkage.
Compound I1 D. an ester linkage.

Statement (1) - Compound I is glucose. 11. The two stereogenic structures shown
Statement (2) - Compound I1 is glucose. below are best related by the term:
Statement (3) - Compound I1 is fructose.
Statement (4) - Compound I1 is fructose.

A. Statements 1 & 2
B. Statements 2 & 3
C. Statements 3 & 4
D. Statements 2 & 3

9. Glucose and mannose are:

y/g- "\YH
A. anomers.
OH C
C
-
T/Y H
B. epimers. I I
C. enantiomers.
D, non superimposable mirror images.
A. enantiomers.
B. resonance structures.
C. anomers.
D. mesomers.
This page intentionally left blank
Chapter 30 Lipids

Lipids

A. INTRODUCTION

Lipids are a group of compounds which are hydrophobic, and have

nonpolar groups predominantly. They can also contain polar groups. Lipids are
important to living beings. Fats, a form of lipid, are used to store energy in
organisms. Lipids are found in a wide variety of capacities; as hormones, as part
of membranes, and as cofactors. Lipids are water insoluble. This makes them
different and unique for their roles as biomolecules. Examples of lipids include
waxes, steroids, and prostaglandins.

B. FATTY ACIDS

Fatty acids are carboxylic acids with long hydrocarbon chains. If the
hydrocarbon chain in a fatty acid is saturated (no carbon-carbon double bonds),
then it is called a saturated fatty acid. If there are (one or more) carbon-carbon
double bonds in the hydrocarbon chain of a fatty acid, then it is called an
unsaturated fatty acid. As the length of the hydrocarbon chain increases, the
lipid solubility of fatty acids increases, and the water solubility decreases. Fats
and oils are derivatives of fatty acids.
Table 30-1

Saturated Fatty Acids

CH3(CH2)12COOH Myristic acid

CH3(CH2)14COOH Palmitic acid

CH3(CH2)16COOH Stearic acid

L
The MCAT Chemistry Book

Table 30-2
r

Unsaturated Fatty Acids

H3C(H2C),HC=CH(CH2),COOH Oleic acid

H3C(H2C),HC=CHCH2CH=CH(CH2),C0OH Linoleic acid

H3CH2CHC=CHCH2CH=CHCH2CH=CH(CH2)7COOH Linolenic acid

L

C. TRIACYLGLYCEROLS

Triacylglycerols are esters of fatty acids. Fats or triglycerides are

triacylglycerols. In a triacylglycerol, a glycerol molecule is linked with three
fatty acids by ester linkages. The structure of glycerol is shown below:

GLYCEROL

The fatty acids that are present in fats are mostly straight-chain fatty
acids (saturated and unsaturated), with even number of carbon atoms. According
to the number of fatty acids esterifying the glycerol's hydroxyl groups, the
glyceride formed could be a monoglyceride, a diglyceride or a triglyceride.
Glycerides with long chain fatty acids are insoluble in water.

TRIACYLGLYCEROL

1 1 FATTY ACID 1

FATTY AClD 3

Figure 30-1
Chapter 30 Lipids

A diagrammatic representation of a triglyceride (triacylglycerol) is shown

in Figure 30-1. In the figure, the vertical bar represents glycerol and the hori-
zontal bars represent the fatty acids. The fatty acids (1, 2, & 3) present in a
triacylglycerol molecule can be the same three fatty acids, or can be different
fatty acids.

Fats can be solid or liquid. This physical property is a direct effect of the
fatty acid substituents that are present in them. When fats are in their liquid state
they are commonly called oils. Broadly we can generalize that solid fats mainly
contain saturated fatty acids, and liquid fats mainly contain unsaturated fatty
acids. We should not confuse this generalization with the fact that the naturally
occurring fats and oils contain many different types of fatty acids, both saturated
and unsaturated. The physical properties of fats are mostly a function of the
fatty acids that are present in them. For example, human stored fat contains
predominantly oleic acid (a saturated fatty acid) which constitutes about 47 %
of the total fatty acid content. It also contains palmitic acid, linoleic acid, stearic
acid, myristic acid, and other fatty acids in decreasing amounts respectively.

D. STEROIDS

A steroid has a drastically different structure from that of fats. Steroids

are lipids having a particular fused-ring structure; a ring structure which has
three six-carbon rings and a five-carbon ring. All steroids have this basic unit in
their structures. Steroids include a wide variety of molecules, including
cholesterol and its derivatives such as steroid hormones, and have tremendous
biological significance. The steroid hormones include adrenocorticoidhormones
and sex hormones.

The fused ring of steroids

The MCAT Chemistry Book

Adrenocorticoid hormones

Cortisone

Aldosterone
Chapter 30 Lipids

Sex hormones

Testosterone Estradiol

Notice that all these compounds have the fused-ring structure that we
mentioned earlier. In fact, cholesterol acts as the starting material for the synthe-
sis of steroid hormones. The steroid hormones play a very important role in the
proper development and functioning of our body. The structures given above
are just for reference and understanding the general structural integrity of ste-
roids. You don't have to memorize them.
The MCAT Chemistry Book

CHAPTER 30 PRACTICE QUESTIONS

1. If 1 mol of triglyceride is subjected to

complete hydrolysis by using a lipase
enzyme, the products formed are:

A. 3 moles of glycerol and 1 mol of fatty

acid.
B. 1 mol of glycerol and 3 moles of fatty
acid.
C. 1 mol of glycerol and 1 mol of fatty acid.
D. 2 moles of cholesterol.

2. Which of the following is not a steroid?

A. Vitamin D
B. Testosterone
C. Estradiol
D. All the above are steroids.
Chapter 31 Phosphoric Acid Chemistry

Phosphoric Acid Chemistry

A. INTRODUCTION

Phosphoric acid is H,PO,. It is an important molecule with respect to

its part in a wide variety of biomolecules in our body such as adenosine triphos-
phate (ATP), deoxyribonucleic acid (DNA), and ribonucleic acid (RNA).

II Phosphoric acid
Hoi-oH OH
B. DISSOCIATION OF PHOSPHORIC ACID

Phosphoric acid is a triprotic acid. That means it has three pKa values.
The MCAT Chemistry Book

C. ESTERS AND ANHYDRIDES

Phosphoric acid can form esters with alcohols. It can form monoesters,
diesters, and triesters. A general representation of the formation of phosphoesters
is given below. R represents the alkyl group.

ROH

n Phosphoric acid

RO-P-OH
II
a Monoester

Figure 31-1
i Triester

Besides esters, phosphoric acid forms anhydrides such as phosphoric anhydrides

by reacting with themselves. One such combination is shown in Figure 3 1-2.

1
10
-
0

HO- P 0-H
I

I Pyrophorphoric acid ) HO-P-0-:-OH

I /'
High energy P-0-P linkage
Figure 31-2
Chapter 31 Phosphoric Acid Chemistry

These anhydrides are biologically useful since the - P a p - link-

ages found in them are high energy linkages, and are used by the body to store
energy. When energy is required, the linkage is hydrolyzed to give off the stored
energy which is in turn used for the metabolic processes in the body.

D. BIOLOGICAL SIGNIFICANCE OF PHOSPHORIC ACID

We cannot completely fathom the importance of phosphoric acid in

biological processes. It is a part of our genetic make up in the sense that
phosphoric acid is a part of the deoxyribonucleic acid (DNA) and the ribonucleic
acid (RNA). The deoxyribose sugars in the DNA are connected using phosphoric
acid entities by forming linkages called phosphodiester bonds. These
phosphodiester bonds connect the 3' hydroxyl group of one sugar to the 5'
hydroxyl group of the next sugar forming the back bone of the nucleic acids.
See Figure 3 1-3.
9

0-

Phosphodiester
bond

Phosphate groups

Figure 31-3 Part of a DNA backbone showing the phosphodiester bonds. The deoxyribose
sugars are linked by the phosphate groups (indicated by the circles).
The MCAT Chemistry Book

At normal biological pH range (7.35-7.45), the phosphate esters usually

show a double negative charge. This property of the phosphate esters makes
them generally water soluble, and thus perfect for the physiological environ-
ment in our body.

Another noteworthy biomolecule that contains the phosphate groups is

the ATP (adenosine triphosphate). The ATP molecules act as one of the major
energy currencies of living beings. It is a triphosphate ester. The formation of
ATP from AMP (adenosine monophosphate) is shown in Figure 31-4.

Figure 31-4 The formation of ATP from AMP

AMP
(Adenosine monphosphate)

ii
<TJ N

I
0-

ATP
(Adenosine triphosphate)
Chapter 31 Phosphoric Acid Chemistry

CHAPTER 31 PRACTICE QUESTIONS Reaction 1 depicts the conversion of phospho-

en01 pyruvate to pyruvate.
Questions 1-7 are based on the following
passage. Phosphate is a part of many high-energy
compounds in biological systems. Examples
Passage 1 include ATP (adenosine triphosphate)) and GTP
(guanosine triphosphate).
Phosphoric acid is an integral part of some of
the most important biomolecules in our body.

Reaction 1
0

The structure of ATP OH OH

ATP - H20
ADP + Pi

1. The bond indicated by the arrow is a:

Compound X

A. phosphate ketone bond.

B. phosphate anhydride bond.
C. phosphate ester bond.
D. N-glycosidic bond.

Compound Y
The MCAT Chemistry Book

2. Reaction 1 can be best described as a: 5. The phosphate anhydride bonds present in

the ATP molecules are high-energy bonds.
A. reduction reaction. Which of the following is true regarding
B. dehydration reaction. the hydrolysis of these bonds?
C. dehydrohalogenation reaction.
D. hydrolysis reaction. A. The products of hydrolysis have less
energy than that of the reactants.
B. The products of hydrolysis have the
3. The interconversion of Compounds X and same energy as that of the reactants.
Y is called: C. The reactants of hydrolysis have less
energy than that of the products.
A. resolution. D. None of the above
B. tautomerism.
C. Tyndall effect.
D. Brownian movement. 6. Choose the correct change in free energy
in the following conversion. (The products
have higher free energy than the reactants)
4. The bond indicated by the arrow is a:
Adenosine + Phosphate -+ AMP

7. Phosphoric acid is a:

A. phosphate ketone bond. A. monoprotic acid.

B. phosphate anhydride bond. B. diprotic acid.
C. phosphate ester bond. C. triprotic acid.
D. N-glycosidic bond. D. strong acid.
Chapter 32 Separation, Purification, and Structural Analysis of Organic Compounds

Separation, Purification, and

Structural Analysis of
Organic Compounds
A. INTRODUCTION

For the MCAT, we should be familiar with the basic features of separa-
tion and purification of organic compounds. In this chapter, we will review some
of the techniques that are commonly used by organic chemists.

B. EXTRACTION

Simple extraction involves the mixing of the organic solution with water
in a separating funnel. Thorough mixing of the two phases (organic and aqueous)
is done, and then the mixture is allowed to settle for sometime until the two
phases separate. Then the lower layer can be poured into another flask. This
procedure can separate water soluble impurities such as inorganic salts, low
molecular weight carboxylic acids, and alcohols. Similarly, extraction can be
done with dilute aqueous acids to remove organic bases, and with dilute aqueous
bases to remove organic acids.

C. CRYSTALLIZATION

Organic compounds (solids) can be purified by a method called

crystallization. Crystallization works by dissolving the material to be purified
in a solvent (under hot conditions), followed by slow cooling of the solution. If
the impurities are also solublejust like the substance we are purifying, obviously
the purification will not be that effective. After the crystallizationby slow cooling
is completed, the crystals are collected by vacuum filtration. Then the crystals
are dried.

Qualities of the Solvent Used for Crystallization

(i) The compound that is purified should be soluble in the selected solvent,
only at high temperatures. At low temperatures, the compound should be
insoluble.
The MCAT Chemistry Book

(ii) The solvent used should have a relatively low boiling point. The boiling
point of the selected solvent should not be higher than the melting point of
the compound to be purified.

Solubility depends on the polarities of the solute and the solvent. According to
the principle "like dissolves like," if the solute is polar, the solvent required
should be polar too. 011 the other hand, ifthe solute is nonpolar, a nonpolar
solvent should be used.

Some of the solvents commonly used for crystallization include acetone,

chloroform, methanol, benzene, diethyl ether, carbon tetrachloride, and water.

D. DISTILLATION

Distillation is a technique that can be employed if the compounds to be

separated have reasonably different boiling points. Distillation involves boiling
ofthe mixture to vaporize it. This is followed by condensation to get the distillate.
The distillates are eventually collected in the order of their condensation. There
are different types of distillations.

Simple distillation is used to separate compounds, which have boiling points

that sufficiently differ (difference of about >50C).

Vacuum distillation is used for the separation of compounds that have very
high boiling points.

Fractional distillation is used for the separation of compounds that have very
close boiling points.

E. CHROMATOGRAPHY

Chromatography is a popular and widely used method of purification.

Chromatography is based on the differences in the adsorption and the solubil-
ity of the compounds to be separated. It involves two phases - a stationary
phase and a moving (mobile) phase. The moving phase actually carries the com-
pounds along the stationary phase. Depending on the interactions between the
compounds and the stationary phase, the compounds get held up or slowed down
by the stationary phase.

Thin-layer Chromatography (TLC)

Thin-layer chromatography is used for the separation of small quanti-

ties of the desired compound, especially for qualitative analysis. It is a widely
Chapter 32 Separation, Purification, and Structural Analysis of Organic Compounds

used technique. In TLC, the liquid (mobile) phase is allowed to run along a
layer of adsorbent. This thin layer of adsorbent (usually alumina or silica gel) is
usually coated on a plate. After the sample (mixture dissolved in a solvent) is
put onto the plate (usually a spot of sample is placed at the bottom of the plate),
the plate is held vertical with a small amount of the solvent just touching the
bottom of the plate. Due to capillary action, the solvent will ascend up the plate.

The sample will be separated between the various phases. The separa-
tion occurs as a result of differences in the rate of mobilities of the individual
components of the sample. This is because of the difference in the affinities of
the solute with respect to the two phases. As a rule of thumb, the higher the
polarity of the compound (component) is, the lesser the rate of upward
mobility of that compound. This generalization is based on the fact that the
stationary phase used is highly polar. Polar substances bind strongly to the sta-
tionary phase. Also, the moving phase generally used is less polar with respect
to the adsorbent. The separated and migrated components will appear as a series
of spots on the plate. If the components are colorless, certain reagents are used
to make the spots visible. Choosing the correct solvent is extremely important,
and is best achieved by experience. Sometimes the best choice of solvent can be
attained only by trial and error.

Rf value is the ratio of the distance traveled by a compound

to the distance traveled by the solvent.

Using known Rf values of compounds under the same conditions, we

can make sure that the desired compound is present in the mixture and can be
separated. Rfvalue is a constant (under specific conditions) for a given compound,
and if the TLC is done exactly under the same conditions specified, we can be
reasonably sure about the identity of the compound. Keep in mind that it is
always safe to make sure of the identity of a compound with other qualitative
analysis as well.

In addition to the function of identifying compounds, TLC is also used

to monitor the progression of reactions, and to test the authenticity or the effec-
tiveness of other separation techniques.

Gas-liquid Chromatography (GLC)

As the name implies, a gas phase (moving phase) and a liquid phase
(stationary phase) are involved in gas-liquid chromatography. Gas-liquid
chromatography is usually employed for the separation of volatile compounds.
The device used for this is called a gas chromatograph. Usually a syringe is used
to inject the sample into the device, and the sample injected is readily turned
The MCAT Chemistry Book

into vapor form. This vaporized form of the sample is carried along the flow of
an inert gas. The sample is passed through a column containing the adsorbent
(liquid-stationary phase). The column is the site where the separation of the
components occurs. The separated samples as they emerge from the column are
detected using a detection device.

The maintenance of the correct temperature of the column is extremely

important for an efficient separation of the components. The choice of the sta-
tionary liquid phase is also important, and so is the maintenance of an optimum
rate of flow of the sample through the column. The latter can be maintained by
controlling the flow of the carrier gas. This technique is highly sensitive. Hence,
it can be used to detect compounds even if very little of the compound is present
(as low as in the order of micrograms).

Technological developments in the field of identification of compounds

using infia red and NMR techniques have revolutionized the ease with which
we can analyze and identify even the most complex structures in organic chem-
istry. For the MCAT, we should be familiar with the techniques and the basic
principles that are used in this field.

F. INFRARED (IR) SPECTROSCOPY

Infrared spectroscopy is a widely used tool to identify and analyze

compounds. As you know, the infrared radiation is part of the electromagnetic
spectrum. The IR has wavelengths between those of the visible light and the
microwaves. From the analytical point of view, only a portion of the entire infiared
range is actually useful for the spectroscopic analysis.

In order to analyze organic compounds, certain properties at the molecular

level are put to use in the infiared spectroscopy. In this technique, the infrared
light is passed through organic compound.samp1es. By doing this, some of the
frequencies are absorbed by the sample and the other frequencies simply pass
through. The percentage absorbance or transmittance is plotted against the
frequency or, to be more precise, the wave number. The wave number (cm-') is
the reciprocal of wavelength expressed in centimeters. The plot can be used to
analyze the structure of a compound by identifling the peaks that are characteristic
to the groups present in the compound.

For example, the carbonyl group (>C=O) shows absorbance close to

1700 cm-' in the IR spectrum. The peaks around this value indicate the presence
of carbonyl group in the compound that is analyzed. By knowing the IR values,
we can predict the structure of a compound. Our discussion from the MCAT
point of view will be limited to some of the common and important IR peaks.
Chapter 32 Separation, Purification, and Structural Analysis of Organic Compounds

Other very complex IR diagrams can only be interpreted by skilled and

experienced professionals.

Vibrational Modes

Chemical bonds have characteristic natural frequencies with which they

vibrate (bending and stretching) in certain specific energy levels. The special
range of frequencies used in IR spectrometry is within the range of the natural
vibrational frequencies of the bonds in organic compounds. By looking at the
peaks, we can tell whether a particular functional group is present or absent in
the compound that we are analyzing. The bonds present in the molecules of the
sample vibrate when they absorb characteristic frequencies.

Molecules are always in a state of vibration. The bonds present in mol-

ecules have their own unique stretching and bending modes. Let's consider a
hypothetical molecule A which has n atoms per molecule. Then, theoretically
molecule A will have 3n - 6 modes of vibration. But this does not mean that the
vibrational modes strictly follow this rule. Some of the vibrational modes have
frequencies that do not coincide with the frequencies of the IR that we use. We
will consider the vibrational modes of the methylene group.

STRETCHING VIBRATIONS

Figure 32- 1
The stretching vibrational modes of methylene group. The two drawings show stretching
vibrations -symmetric (on the left) and asymmetric on the right.
The MCAT Chemistry Book

BENDING VIBRATIONS

0
.. , .

Figure 32-2
The bending vibrational modes of methylene group
The top two diagrams from the left are scissoring and rocking modes. The bottom two
diagrams show wagging and twisting modes.

Besides the fundamental vibrational frequencies, overtones and combination

tones can appear in the IR spectrum. For example, the overtone of a carbonyl
group can appear close to 3400cm-I (the carbonyl peak is close to 1700 cm-I).
Combination frequencies are peaks that appear when two frequencies intermingle,
resulting in two weak frequencies.
Chapter 32 Separation, Purification, and Structural Analysis of Organic Compounds

Table 32-1

SOME IR ABSORBANCES
1I I
1 TYPE OF BOND

I1) -OH
-OH
(Alcohol)
(Carboxylic acid)
3200-3600
2500-3300
I -Aromatic ring
I -CH (Aromatic)
-CH (sp3) 2850-3000
=CH (sp2) 3000-3 100
Z C H (sp) -3300
Aldehyde -2720, -2820
-CZN 22 10-2260
Ethers -1000, -1300
I Amines -NH I 3300-3500
I -C=O (Carbonyl) I -1715 (1640-1750)

- - - - - --

- C= 0 (Aldehyde) -1715 (1660-1740)

- C=O (Amide) -1690 (1630-1690)
-C=O (Ester) -1735 (1 735-1750)
- C=O (Acid) -1 7 10 (1700- 1730)
-C=O (Acid) -1710 (1700-1730)
\ /
/
C= C, (Alkene) 1620-1680
The MCAT Chemistry Book

Example 32-1

Analyze the IR diagram shown below.

The given IR spectrum is that of phenol. Look at some of the important peaks
that are present in this IR spectrum of phenol.

Analysis:

1) The peak 1 around 3400 cm-' represents the peak caused by the -OH group.
2) The peak 2 at 3050 cm-' represents the aromatic -CH.
3) The peak 3 denotes the benzene ring stretch.
Chapter 32 Separation, Purification, and Structural Analysis of Organic Compounds

Problem 32-1

5
4000 3500 3000 2500
1
PEAK 2
2000 1800
I
1600 1400
. I!
1200
. I

1000
I .
800
I
.

600
( I
400
.
200
1
In the IR spectrum shown above, identify the most likely peak which represents
the carbonyl group.

Solution:

The carbonyl peak is roughly around 1700 cm-I. So Peak 2 indicated in the IR
diagram is the correct answer.

G. NUCLEAR MAGNETIC RESONANCE (NMR) SPECTROSCOPY

Nuclear magnetic resonance spectroscopy (NMR) is a type of analysis

with which we can identify the positions of certain atoms in a compound. Only
those atoms which possess nuclear spinning properties can exhibit NMR
behavior. NMR spectroscopy is based on the magnetic properties exhibited by
the nuclei of certain atoms. We will limit our discussion to the resonance
spectroscopy (proton NMR) involving the nuclei of hydrogen atoms. With proton
NMR, we can find or recognize the characteristic groups in the unknown
compound, to which the specific protons are attached. In addition, we can also
identi@ the number of different types of equivalent protons in a compound that
we are analyzing.

The Basics of Proton NMR

The nucleus of an atom has an electric charge. Nuclear spin properties

lead to nuclear magnetic moments. When hydrogen nuclei are exposed to a
magnetic field, the nuclei will align themselves in coherence with the applied
The MCAT Chemistry Book

magnetic field as if they were tiny magnets. The alignment can be either along
or opposite to the direction of the applied magnetic field. Among these two
orientations, the one with the lower energy occurs when the alignment is along
the direction of the field compared to the other orientation.

When sufficient energy (in the form of radio-frequency of the

electromagnetic spectrum) is applied, the nuclei that are aligned along the
magnetic field can reverse their orientation to align opposite to that of the applied
magnetic field. The extent to which the nucleus is shielded from the magnetic
field dictates the amount of energy required to change the orientation to a higher
energy level. Based on this principle, we have to understand that depending on
the extent of shielding they will absorb different frequencies. The energy that is
absorbed is monitored and is recorded in the form of NMR spectrum. Thus
protons in different regions of a molecule have different shifts (chemical shifts).

For the standard applied magnetic field, the absorption of frequencies

differ only in terms of a few parts per million (ppm). In NMR spectroscopy, the
relative standard molecule used is tetramethyl silane (TMS), and thus chemical
shift (6) is measured in ppm relative to the proton signal of TMS. Note that all
the protons of TMS are equivalent, and thus have the same frequency of absorp-
tion, and it is considered to have a standard arbitrary value of "0 ppm" - the
reference standard.

TH3
H3C-Si-CH3
ICH3
The reference compound used - Tetra-methyl silane

Spin-Spin Coupling

Spin-spin coupling results from the possibility of the coupling of the

neighboring protons. Signals often appear as groups of peaks as a result of spin-
spin coupling. This results in what is called signal multiplicity. The number of
peaks in a signal is dictated by the following means. Consider this hypothetical
situation. Let's say there are N, equivalent protons in set 1, and N, equivalent
protons in the adjacent carbon (set 2). (Note: Equivalent protons do not split
themselves.) If this is the case, signal 1 will have (N, + 1) peaks, and signal 2
will have (N, + 1) peaks. The intensities of a split pattern are symmetrical (bilat-
erally symmetrical). The relative intensities of the peaks in a signal follow a
pattern. A singlet has only one peak. There is no splitting in singlets. So there is
Chapter 32 Separation, Purification, and Structural Analysis of Organic Compounds

no relative ratio to compare with. A doublet has a 1 : 1 proportion of relative

intensities. A triplet has 1 : 2 : 1 proportion of relative intensities. A quartet has
1 : 3 : 3 : 1 proportion of relative intensities, and so on.

The different types of equivalent protons reflect the total number of

signals. In the NMR spectrum of a compound, the levels of intensities of the
signals denote the proportion of equivalent protons present in the compound.
For example, the intensity of a signal resulting from six equivalent protons will
be greater than the intensity of a signal resulting from two equivalent protons.
The intensity is equivalent to the areas under the signals, and is proportional to
the number of protons creating that particular signal.

i NUMBER OF PROTONS ATTACHED El

ADJACENT CARBONIS, WHICH ARE 1
RESPONSIBLE FOR THE SPLITTING
-. -- I
SINGLET 1 0

I
I
DOUBLET 1 1
1 1 1
TRIPLET 1 2 1 2

QUARTET 1 3 3 1 3
I I

PENTET 1 4 6 4 1 4

SEXTET 1 5 10 10 5 1 5
,
1 SEPTET 1 6 15 20 15 6
I
Figure 32-3 Relative intensities of the peaks
The MCAT Chemistry Book

Proton Chemical Shifts

Table 32-2

Type of Proton
*
Chemical shift, 6 (ppm) ,
R-CH3 (Primary) 0.9

R2-CH2(Secondary) 1.3
R,-CH (Tertiary) 1.5

-HC=CH (Vinyl) 4.5 - 6

-C r CH (Acetylenic) 2-3

Ar-H (Aromatic) 6 - 8.5

Ar-CH (Benzylic) 2-3

C=CHCH3(Allylic) 1.6

-CHX (Halides) 2 - 4.5

-CHOH (Alcohol) 3.4 - 4

-CHOR (Ether) 3.4 - 4

-CHCOOH (Carboxylic) 2 - 2.6
-CHCOOR (Ester) 2 - 2.2
RCH=O (Aldehyde) 9 - 10

-CHOH (Hydroxyl) 1 - 5.6

-Ar-OH (Phenolic hydroxyl) 4-12

-CHCOOH (Carboxylic acid) 10 - 12

R-NH2 (Amino) 1-5

*Approximate values with respect to TMS

Chapter 32 Separation, Purification, and Structural Analysis of Organic Compounds

Chemical shift ( 6 ) ppm

Figure 32-4 The NMR spectrum of methyl propionate

Look at the NMR spectrum of methyl propionate given in Figure 32-4.

CH3-0-
11
C-
H2
C- CH3 Methyl propionate

In the NMR spectrum, the signal at 0 ppm represents tetra methyl silane
(standard). There are three distinct signals (sets of peaks). Altogether, there are
8 peaks -a set of three just after 1 ppm, a set of four just after 2 ppm, and a
single peak around 3.5 ppm, totaling eight peaks. The set X is a triplet. The set
Y is a quartet, and the set Z is a singlet. Sometimes it is hard to recognize the
peaks distinctly because of interference between the nuclei, especially when
there are multiple number of peaks.

In methyl propionate, there are three different types of protons denoted

by X, Y, and Z. In the NMR spectrum, the set X is represented by the triplet in
the NMR spectrum, the set Y is denoted by the quartet, and the set Z is denoted
by the singlet.
The MCAT Chemistry Book

CHAPTER 32 PRACTICE QUESTIONS )henylhydrazine. The compound tested for the

:onfirmation was propanone. The product
1. All the following are true regarding the ormed as a result of this test involving pro-
process of crjrstallization, EXCEPT: lanone is shown below.

A. The solvent used should easily dissolve

the compound when cold.
B. Minimum amount of solvent should be
used.
C. Crystallization process is generally used
when there aren't many impurities in the
material purified. Experiment 3
D. Hexane is a good solvent that can be
used to purify hydrocarbons. [nExperiment 3, three compounds were tested.
rhese three compounds were treated with
:oncentrated hydrochloric acid in the presence
2. Distillation is a very widely used technique of zinc chloride (ZnCl,). Compound A was
for purifying compounds. Which of the ethyl alcohol, Compound B was tert-butyl
following processes is involved? alcohol, and Compound C was 2-propanol. The
reactions were based on unimolecular
A. Vaporization is involved. substitution mechanism.
B. Boiling is involved.
C. Condensation is involved. Experiment 4
D. All the above
In Experiment 4, the chemists synthesized the
Questions 3-8 are based on the following following compound.
passage.

Passage 1

A set of qualitative experiments were

conducted in an organic chemistry lab.

Experiment 1

Chemist 1 treated cyclohexene with 1% aq.

KMnO,. One of the products was a cis-glycol.

Experiment 2

Chemist 2 conducted qualitative tests for some

carbonyl compounds. Aldehydes and ketone:
gave a positive test for the reagent 2,4-dinitro.
Chapter 32 Separation, Purification, and Structural Analysis of Organic Compounds

3. Based on Experiment 3, choose the true 7. How many sets of peaks (signals) are
statement from the following choices. expected for the Compound B?

A. Compound A had the fastest reaction

rate among the compounds tested.
B. Compound B had the slowest reaction
rate among the compounds tested.
C . Compound C did not undergo the
reaction.
D. Compound A did not undergo the 8. Which of the following are true for the com-
reaction. pound synthesized in Experiment 4?

I. The compound is insoluble in H,O.

4. In Experiment 2, which of the following IR 11. The compound is soluble in 5% aqueous
peaks must have disappeared after the treat- solution of NaOH.
ment of the compound with the reagent? 1II.The compound is an aromatic com-
pound.
A. A broad IR band at 3400 cm-I IV. The compound is a strong base.
B. A peak at 1700 cm-I
C. A peak at 800 cm-I A. I & I1 only
D. All the above peaks will be present for B. I & I11 only
the product formed as a result of the C. I1 & IV only
reaction with the reagent. D. I1 & I11 only

5. Which of the following best describes the

process involved in Experiment 1?

A. Reduction
B. Esterification
C. Oxidation
D. Dehydrohalogenation

6. Which of the following is true regarding

Compounds A , B and C?

A. They all have carboxyl groups.

B. They all have double bonds.
C. They all have IR peaks close to 3400 cm-I.
D. They all have the same reaction rate in
terms of substitution reactions.
This page intentionally left blank
SOLUTIONS
This page intentionally left blank
 Solutions

Chapter 1 Solutions

1. The answer is D. This question tests your understanding of the concept of mole. The student is
preparing a solution using calcium hydroxide. The formula of calcium hydroxide is Ca(OH),. The
formula weight of calcium hydroxide is 74.1 gramslmol. Here, the student added two moles of it.
So the answer is 74.1 x 2 = 148.2 g.

2. The answer is D. The sample weighs 56 g. The formula weight of 0, is 32 glmol. So the number of
moles of oxygen present is roughly 1.75. Remember that 1 mol contains Avogadro number of
particles. Since 1.75 moles of oxygen is present, there are 1.75 x 6.0 x 10" molecules of oxygen.
Are we done at this point? No! The question asks for the total number of atoms present in the
sample. Since each oxygen molecule is composed of two oxygen atoms, the total number of atoms
present in this sample equals 2 x 1.75 x 6.0 x 1023= 21 x

3. The answer is B. Gas discharge tubes are vacuum tubes with electrodes connected to very high
voltages. Cathode rays are emitted from the cathode of the tube. A cathode ray consists of a beam
of electrons. Since electrons are negatively charged, cathode rays will bend away from a nega-
tively charged plate.

4. The answer is D. This question asks for a true statement from the choices. Let's look at each of
those choices. Choice A is incorrect, because neutrons and electrons do not have the same mass.
Choice B claims that the mass of a neutron is less than that of an electron. That is not true either.
Protons are positive and neutrons are neutral. They cannot together make the nucleus neutral. In
fact, the nucleus is positively charged, not electrically neutral. So Choice C is wrong. The last
choice makes perfect sense. A proton is more massive than an electron.

5. The answer is B. The actual formula of butane is C,H,,. But the question is not about butane's
actual formula. The question asks for the empirical formula of butane. Empirical formula is the
most simplified ratio of the actual formula. So the correct answer is C,H,.

6 . The answer is C. Let's look at the question carefully. If you did not get the right answer, carefully
think about it again. The question is simply testing your understanding of a definition. The mass
of a substance in one mole of it is numerically equal to its molecular weight.

7. The answer is A. Density is equal to mass per volume. Further more, the mass is equal to the
product of number moles and molar mass. Equating these two equations we can get the answer.
Using the letter notations given in the question, the expression of volume is given by Choice A.

8. The answer is D. The formula of sulfur dioxide is SO,. The formula weight of SO, is 64 gimol. This
sample of SO, contains 1.5 moles of it. If we calculate the percentage mass of the oxygen, we can
see that the oxygen's mass contribution is 50% in SO,. So regardless of the amount of SO, present,
half of its mass is due to the presence of oxygen and the other half is due to the presence of sulfur.
Here we have 96 g of SO,. Now, one half of 96 g gives 48 g.
The MCAT Chemistry Book

9. The answer is A. The formula of carbon tetrachloride is CC1,. The formula weight of CCl, is 154
glmol. The percentage composition of C1 can be calculated as follows:
mass of chlorine 142
% chlorine = x 100% = - x 100% x 92%
mass of CCl, 154

10. The answer is C. In the question, the percentage compositions of nitrogen and oxygen are given.
With that information, we have to find the formula of that compound. Just as discussed in our
review, assume that we have 100 grams of this compound. If there are 100 grams, logically it
should contain 63.6 grams of nitrogen and 36.4 grams of oxygen.

Step 1
63.6
# of moles of nitrogen = -= 4.5 moles of nitrogen
14
36.4
# of moles of oxygen = -= 2.275 moles of oxygen
16
Step 2

Divide every number of moles with the smallest number of moles calculated in Step 1. Here the
smaller one is 2.275. Divide both mole numbers by 2.275. This will give you the simplest ratio
between them.
4.5 2.275
Nitrogen -= 2 Oxygen -
2.275 2.275 =

Since the ratio of nitrogen to oxygen is 2: 1, the compound is N,O.

11. The answer is B. Reaction 2 is a typical example of a combustion reaction.

12. The answer is C.

2C2H, + 702 -
Reaction 2
4CO2 + 6H20

According to Reaction 2, two moles of ethane will react with 7 moles of oxygen to form 4 moles
of carbon dioxide and 6 moles of water. In the question, it is given that 54 g of water was formed.
This corresponds to 3 moles of water. From the equation, we can say that 1 mol of ethane must
have reacted to form 3 moles of water. We can also say that 3.5 moles of oxygen must have reacted
in the formation of 3 moles of water. The last step is the conversion of moles to grams. The
corresponding quantities in grams are 30 g of ethane and 112 g of oxygen.

13. The answer is B. From the question, we can say that the empirical formula of dextrose is CH,O.
The molecular weight of dextrose is also given. Let's first calculate the weight of the empirical
 Solutions

formula. Maybe the empirical formula represents the actual formula. The weight of the empirical
formula is 30 glmol. But the question says it is 180 glmol. In this case, the molecular formula is
not the same as the empirical formula. By dividing the actual weight by the empirical weight, we
will get the coefficient with which we have to multiply the empirical formula to get the actual
formula. The coefficient is 180130 = 6. So the molecular formula is C6H,,06.Have you heard of
glucose? Well, dextrose is the same thing. If you knew that, you could have picked the answer
right away. But more importantly, it is the process that you have to learn from this question.

14. The answer is C. The formula of methane is CH,. The molecular weight is 16 glmol. We have 40
g of methane. That means we have 2.5 moles of methane. So the number of hydrogen atoms can
be calculated.

6.0 x x 2.5 moles x 4 hydrogen atomslmol = 6.0 x atoms

Chapter 2 Solutions

1. The answer is D. This question tests your understanding of the general classification of reactions.
The reaction is clearly not a combustion reaction. Combustion reactions occur in the presence of
oxygen and involve release of heat. There is no indication of that in the given reaction. You might
be tempted to select Choice C since the given reaction is a replacement reaction, but double-
replacement reaction best describes the given reaction. In the reaction, the iodine is replaced with
the chlorine, and the chlorine is replaced with the iodine.

2. The answer is C. Choices A, B, and D are all acid-base reactions, which are neutralization reac-
tions. Choice C is actually the formation of a base (AlOH,), and it is not a neutralization reaction.

3. The answer is B. Let's start balancing the equation from the sulfate point of view. You have 3
sulfate groups in aluminum sulfate. It has to come from the sulfuric acid. So the coefficient is 3 for
the sulfuric acid. Since there are 2 alurninums in aluminum sulfate, we can assign a coefficient of
2 to the aluminum hydroxide. The rest of the hydrogens and oxygens can be balanced with water.

The balanced equation should look like this:

4. The answer is B. First, we have to check whether the given reaction is balanced. Without the
balanced equation, the calculations will be incorrect. As a matter of fact, the given reaction is not

-
balanced. The balanced equation is this:

2 NaCl + H2SO4 Na2S04+ 2 HCI

Now we can work out our magic calculations. The question specifies the grams of HC1 syn-
thesized. The 73 grams converted to moles should give 2 moles. According to the equation, 2
moles of NaCl are required to synthesize two moles of HC1. All you have to do now is to convert
moles to grams. The correct value is 117 grams of NaC1.
409
The MCAT Chemistry Book

5. The answer is D. This is a straightforward definition-type question. The ions that are present in
the solution sometimes do not actually participate in the reaction. By writing the complete ionic
equation of such a reaction, we can see that the spectator ions on both sides of the equation are in
the same state or form. We can cancel them out and get the net equation of the reaction. Spectator
ions are not usually depicted in the net ionic equation.

6. The answer is D. This is also a definition-type question. Amphoteric substances can exhibit both
acidic and basic properties depending on the environment that they are subjected to.

4 Fe + 3 O2 -
7. The answer is D. The reaction mentioned in this question is the rusting of iron. The balanced
reaction should look like this:
2 Fe203

8. The answer is D. The question tests your understanding of the concept of mole. In Choice A, we
have 32 g of 0, which corresponds to 1 mol of oxygen, and 32 g of SO, which corresponds to half
a mol. Choice A is not correct. In Choice Bywe have 49 g of NO, which corresponds to a little
more than 1 mol, and 40 g of NaOH which corresponds to 1 mol. So this may be our answer.
Choice C is not 'correct, because we have 20 g of HF which is 1 mol, and 36 g of water which is 2
moles. So Choice C is incorrect. Choice D has 60 g of C2H, which is 2 moles, and 156 g of C6H6
is also 2 moles. So D is a better choice than B.

9. The answer is B. To answer this question, you have to use your intuition. The reaction occurs by
means of the heat supplied to the aluminum hydroxide, and it is a dehydration reaction. So the
most plausible answer is water.

10. The answer is D. The reactant coefficients in a balanced equation cannot be used to determine the
identity of the limiting reagent. Without comparing the amounts of reactants that are actually
present, we cannot determine the identity of the limiting reagent. CO being a gas has nothing to do
with being the limiting reagent for the given reaction. Choice C is not logical, because it is a
product. The best answer is that we cannot determine the identity of the limiting reagent, if any,
without any data regarding the amount of reactants used.

11. The answer is C. Look at the items one by one. Item I says that the second student had the highest
yield of products. In Experiment 1, the first student used 40.5 g of A1 and 80 g of Fe203.This
translates to 1.5 moles of A1 and roughly 0.5 moles of Fe203.Here Fe203is the limiting reagent.
What was the second student doing? Well, the second student increased the amount of Fe20, used,
keeping the same amount of Al. Since Fe203is the limiting reagent, an increase of Fe203will
increase the product yield. So the second student must have had more yield than the first student.
The first and the third students have the same yield for aluminum oxide, because the amount of
limiting reagent present is the same in both cases. So items I and I1 are true.

12. The answer is C. By increasing the amount of aluminum used by the first student, there will not be
an increase in the yield because Fe,O, is the limiting reagent. Hence, Choice A is not correct. The
same reasoning rules out Choice B. Increasing the amount of Fe,03 by the second student will
 Solutions

increase the yield further, because we actually have unreacted A1 left according to the amounts
used in the experiment. Hence, if we further increase the amount of Fe,03 used, it will increase the
yield until the A1 runs out. Choice D is wrong.

13. The answer is A. In the question, we are given that 80 g of Fe,03 is used in the reaction mixture.
How much of this actually reacted is another story. That is to be found out from the yield data. The
amount of CO, produced is 22 g. Based on the balanced equation, we can infer that for every 3
moles of CO reacted, 3 moles of CO, are produced. So CO and CO, have a 1:1 ratio. If 22 g or 0.5
moles of CO, is produced, 0.5 moles of CO must have reacted.

14. The answer is B. Based on the question, we can say that about 0.5 mol of Fe,03 and 0.5 mol CO
was present in the reacting mixture. Since the Fe,03 to CO reacting ratio is 1:3, CO will com-
pletely react, and there will be some leftover unreacted Fe203after the reaction is complete. So the
limiting reagent is CO.

15. The answer is B. This question tests your understanding of the mole concept. Since we have excess
amounts of Fe 0 ,we do not have to worry about it. But, what you should consider is that the amount
?
of CO present dictates the reaction. One mol of CO, contains Avogadro number (6.02 x lo?" of
molecules. The reaction results in 0.1 mol of CO,. So 0.1 mol of CO, contains 6.02 x molecules.

Chapter 3 Solutions

1. The answer is A. The correct order of filling from 3s onward is 3s, 3p, 4s, 3d, and 4p. For the
MCAT, you must know the order of filling of subshells.

2. The answer is D. Inert gases (noble gases) have the completed outermost s andp subshells. He-
lium is an exception to this.

3. The answer is D. The atomic number of Kr (krypton) is 36. After the representation of Kr, how
many electrons do we have? There are 14 more electrons. That adds up to an atomic number of 50.
The atomic number 50 corresponds to the element Sn.

4. The correct answer is B. This is a straightforward question. The maximum number of electrons
that can occupy the principal energy level is calculated using the formula 2n2.

5. The answer is C. The statement "no two electrons of an atom can have the same set of four
quantum numbers" is Pauli exclusion principle.

6. The answer is C. The only correct statement in the set of choices is "the 5d subshell has higher
energy than the 6s subshell." All other choices are wrong.

7. The answer is D. The question asks us to pick the species that is not isoelectronic (same number
of electrons) with the noble gases. In order to solve this problem, you have to find the number of
electrons present in them, and if it matches with the number of electrons in any of the noble gases,
you can eliminate that choice. All the ions match with one or the other noble gas in terms of the
number of electrons, except Mg'.
41 1
The MCAT Chemistry Book

8. The answer is D. The nitrogen atom has a total of 7 electrons. The principal quantum number
could be 1 or 2. With that alone, we cannot rule out any of the choices. The next quantum number
given is the azimuthal quantum number, also known as the angular momentum quantum number.
The angular momentum quantum number can have values from 0 to n - I , where n represents the
principal quantum number. Since 2 denotes the maximum n value, we cannot rule out any of the
choices yet. Look at the next quantum number, which is the magnetic quantum number. The
magnetic quantum number can have values from - 1 to $1, where 1 represents angular momentum
quantum number. So the magnetic quantum number cannot be +2 for nitrogen.

9. The answer is A. This question tests your ability to recognize a given electronic configuration.
The fastest way to approach this type of question is to look at the root element given. The atomic
number of argon is 18. We can count 14 more electrons in the given configuration to get a total of
32 electrons. The atomic number 32 is that of germanium (Ge).

10. The answer is B. Osmium, silver, and radium can have the 4d subshell. Copper belongs to the 4th
period and therefore cannot have a 4d subshell. All the other elements listed belong to the periods
5, 6 and 7.

Chapter 4 Solutions

1. The answer is B. Sulfur belongs to Group VIA (the representative elements). The inner transition
elements are the group of elements that are in the two rows below the main section of the periodic
table. The transition elements range from IB through VIIB including the collective group of ele-
ments under Group VIII (not the zero group). Choices A and B are ruled out. Sulfur is not classi-
fied as a metal. This rules out Choice D.

2. The answer is C. The Group IA metals are collectively called the alkaline metals. The Group IIA
metals are the alkaline earth metals. Among the choices, only strontium belongs to this group.

3. The answer is D. Electronegativity increases from left to right along the rows. For this question
let's rephrase this trend. Electronegativity decreases from right to left along the columns, and
from top to bottom.

4. The answer is B. The f block contains the inner-transition elements. The only element that is
listed among the choices that is an inner-transition element is uranium.

5. The answer is C. This question can be answered on the basis of trivial knowledge. Oxygen, nitro-
gen, and chlorine are diatomic gases. Neon is a noble gas (zero group element) which is stable on
its own.

6. The answer is D. This question tests your knowledge of a periodic trend. Here, the trend of atomic
radius is asked. Along a period as the atomic number increases, the atomic radius decreases.
Down a group, the atomic radius increases.
 Solutions

7. The answer is A. This question is similar to the previous one. It is again just a matter of comparing
the size of the atoms according to the periodic trend of the atomic radius.

8. The answer is D. All the trends listed as choices are wrong. Along a period from left to right, the
atomic radius decreases. So Choice A is incorrect. Along a period from left to right, the ionization
energy increases. This rules out Choice B. The electronegativity of elements decreases from right
to left along a period. Since Choice C contradicts this, it is incorrect.

9. The answer is D. HF is a weak acid and all the other choices are strong acids. This rules out
Choice A. Among the other choices, HI is the strongest acid because it can give off the protons
more easily than any of the other acids listed. The order of acidity is HI > HBr > HCl.

10. The answer is B. The given configuration is that of Group IVA (carbon family).

Chapter 5 Solutions

1. The answer is A. The central atom of the structure is sulfur. So draw the skeletal (structural)
framework. In this structure, sulfur doesn't have the octet. So the next move is to introduce a
double bond.

(framework) -I The actual structure is: -

2. The answer is D. Let us look at the choices one by one. The water molecule is a bent molecule. So
there is good reason to believe that it has a net nonzero dipole moment. In HC1, the hydrogen-
chlorine bond is a polar bond, and thus there is clearly a separation of charge. This means it has a
dipole moment. Oxygen is more electronegative than carbon. This creates a charge separation in
the CO molecule. Thus the oxygen has a partial negative charge. So CO is a good candidate,
having a net nonzero dipole moment. The CH, molecule has a tetrahedral structure and the small
individual dipoles cancel out. So the net dipole of methane is zero.

3. The answer is B. The electronegativity difference between the nitrogen and the oxygen in NO, is
not enough to cause an ionic interaction. Hence, it is not an ionic bond. The correct answer is
covalent bond, because the bond is formed by the sharing of electrons between the nitrogen and
the oxygen.

4. The answer is A. Ammonia (NH,) and boron trifluoride (BF,) can undergo a special type of cova-
lent bonding - coordinate covalent bond. Even though this is a covalent bond, the electrons for the
bond formation are supplied by one of the partners involved in the bonding. Boron has only three
electrons in its outermost shell and they are already involved in the formation of the BF, molecule
itself. There are no more electrons available from boron. But that is not the case with the nitrogen
atom in NH,. Two lone electrons are available from the nitrogen in NH, which make this bond
formation possible.
The MCAT Chemistry Book

5. The answer is A. To answer this question, we have to use our intuition. We do not have any
specific data on any of the compounds listed as choices. But we can do an intelligent elimination.
Choices B and D have the same zero dipole moment. Now it is just a matter of deciding which one
of the remaining choices (A and C) is the answer. The electronegativity of fluorine is higher than
that of bromine. So HF has the highest dipole moment.

6. The answer is B. BC1, can be drawn as shown below. The geometry is trigonal planar.

7. The answer is D. If you draw the electron-dot structure of the CC1, molecule, you can see that
there are four electron pairs around the central carbon atom. All these electrons form four carbon-
chlorine bonds which make the molecular geometry - tetrahedral.

8. The answer is A. The Lewis structure of the nitrate ion is shown. By analyzing the Lewis struc-

:
..
ture, the best prediction is that the nitrate ion is trigonal planar.
0:
-

9. The answer is C.

10. The answer is D. All the statements (I, 11,111, and IV) are correct. Let's see why this is the case. All
the individual bonds in both compounds are dipoles. This makes items I and I1 correct. The ques-
tion says that both molecules are tetrahedral. Hence, these individual bond dipoles cancel out to
give a net zero dipole.

11. The answer is C. An ionic bond is formed mainly when there is a noticeable electronegativity
difference between the atoms. Usually ionic bonds have the highest electronegativity difference.
Choice A is incorrect. Covalently bonded atoms have lesser electronegativity difference. Among
Choices B and C, nonpolar covalent bonds obviously have the least electronegativity difference.
So our answer is C. Choice D is not true in this case. We do not need any more data to predict this
general trend.

12. The answer is C. For Compound A, we should compare the atoms involved in the bond in ques-
tion. Chlorine is more electronegative than boron. This rules out Choices B and D. For Compound
B, the bond dipole should be directed toward the carbon atom. This rules out Choices A and D. So
the only choice which has not been ruled out is C.
 Solutions

13. The answer is D. This question is a bit tricky. Many students will quickly select angular as the
answer. But you have to be careful. The question is not asking for the molecular geometry of
water. It is actually asking for the electronic orientation or electronic geometry of water which is
tetrahedral. The four electron pairs (two bonded pairs and two lone pairs) of the water molecule
result in a tetrahedral geometry. Moreover, Choices A and B are essentially the same. If one is not
correct, the other cannot be correct either.

Chapter 6 Solutions

1. The answer is C. First, we should write the balanced equation. Without the balanced equation
there is a good chance we might choose the incorrect answer.

According to the balanced equation, 2 liters of NO react with 1 liter of 0, to give 2 liters of NO,.
According to the question, 4 liters of NO, were formed. By taking proportionality, we can say that
4 liters of NO and 2 liters of 0, must have reacted so far.

2. The answer is B. Density is mass per unit volume. Since we know the density and the volume, we
can find the weight of the gas. Since this represents 1 mol of the gas, that itself is its molecular
weight.

Molecular weight of the gas 1.8

g
x 45 - -
L
= - - 81 g l m o l
L mol
3. The answer is C. One mol of an ideal gas occupies 22.5 L at STP. From the density-volume-mass
relationship, we can find the mass of 1 mol of this gas. We know both the density and the volume
of the gas.
Weight of the gas = 1.4 x 22.5
This molecular weight is closest to that of oxygen.
xol = 3 1.5 gOl
4. The answer is B. The objective of this question is to convert the given pressure value (in mmHg)
to Pascal units. In order to do this, we should first convert the given value into atmospheres. Since
one atm equals 760 rnrnHg, 1330 mmHg equals 1.75 atm. The conversion of atmospheres to
Pascal units is given in the question. The conversion is:
1.75atm=1.75atm x 101.3 kPa = 1 . 8 ~ 1 kPa
0 ~ = l . 8 x l o 5 Pa
5. The answer is B. This is a simple conversion problem that every MCAT student should know and
do without any reference. This conversion should come automatically

6. The answer is A. The given quantity of CO, corresponds to 0.26 mol. This quantity of CO, will
occupy 0.26 x 22.5 = 5.9 L. If you still don't understand this type of calculation, review the
chapter again.
The MCAT Chemistry Book

7. The answer is B. Gases best behave the most ideally under conditions such as high temperature
and low pressure. Choice D is wrong. The passage makes the behavior of gases very clear: They
depend on the prevailing temperature and pressure.

8. The answer is C. By rearranging the ideal gas equation, we can find the correct unit of the gas
constant.

9. The answer is A. The question is asking for effusion rates of SO, and 0,. The rate of effusion of a
molecule is inversely proportional to the square root of its molecular weight. The problem should
be solved as follows:
Rate of SO, effusion Mol.wt o f 0 ,
Rate of 0, effusion ~ o lwt. of SO,
10. The answer is A. A value of zero alone will not ensure ideal behavior. So gas A does not behave
ideally. Hence item I is correct. Item I1 contradicts what we just said. We cannot say whether gas
A is xenon. So item I11 is not a valid statement.

11. The answer is D. The clues to answer this question have to be taken from the given data. What can
we infer from the data given about halogens? The correction factor of fluorine is 1.170 L2.atm/mo12.
The correction factor of chlorine is 6.340 L2.atm/mo12.By analyzing the trend, we can deduce that
bromine must have a correction factor that is higher than that of chlorine. The only value that is
higher than that of chlorine is 9.80 L2.atm/mo12.Hence, the best choice is D. If you were looking at
the values of b, you probably did not notice the units represented in the answers. All units correspond
to that of constant a and not of b.

12. The answer is D.

13. The answer is D. According to the kinetic-molecular theory, all the items are true.

Chapter 7 Solutions

1. The answer is D. The conversion of a gas to a solid is called deposition. Sublimation is the conver-
sion of a solid to a gas. Condensation is the conversion of a gas to a liquid. Freezing is the conver-
sion of a liquid to a solid.

2. The answer is B. Vaporization, sublimation, and melting require heat (consume heat). The only
process listed which releases heat is condensation.

3. The answer is D. Potassium fluoride is an ionic compound. See the chapter for descriptions of all
types of solids.

4. The answer is C. In order to answer this question we have to think in terms of ionic bonding. What
enables the formation of an ionic bond in the first place? The electronegativity differences between
the bonded atoms make ionic bonds possible. It is in fact the electrostatic forces that hold the
atoms involved in an ionic bond.
 Solutions

5. The answer is B. To answer this question, we need to recall some basic aspects regarding phase
diagrams. Just by knowing those, we can eliminate some of the choices right away. In Choices A
and D, the phases are wrongly labeled. The phases are correctly labeled only in Choices B and C.
This rules out Choices A and D. Water has some anomalous properties. Such properties make
water unique. In fact, the solid-liquid segment in the phase diagram of water has a negative slope.

6 . The answer is B. See the explanation for Question 5.

7. The answer is B. The question describes a phase change scenario based on the diagram given in
the passage. Substance M will be a liquid at point A. If the pressure is decreased, the most likely
phase change will be from liquid (the phase before the change) to gas.

8. The answer is C. This is a definition-type question. The point indicated by the X mark is called
"triple point." At the triple point of a substance, the three phases coexist at equilibrium. Below
this point, the solid to gas conversion or vice versa is direct without the intermediate liquid phase.

9. The answer is C. The critical temperature is defined to be the temperature above which a gas
cannot be changed into a liquid. The choice that best reflects this idea is C.

10. The answer is A. In the phase diagram given in the passage, locate the segment XZ. This segment
separates the liquid and the gas phases.

Chapter 8 Solutions

1. The answer is C. Normality of a solution is the number of equivalents of solute per liter of solution.

2. The answer is A.
270 g
The number of moles of glucose = = 1.5 moles
180 g o 1

moles of solute - 1.5 moles

Molarity = - = 1.5 M.
liters of solution 1 liter
3. The answer is D. First, we should calculate the molar mass of HCl which is 36.5 glmol. We have
a 2.5 molar solution of HC1. That means every liter of the solution will have 2.5 moles of HC1.
Here we have 1.25 L of the solution, and a total of 3.125 moles of HC1. That comes closest to
3.125 x 36.5 = 114 g.

4. The answer is B. We can equate the diluted solution with the stock solution as follows:
(Molarity of solution made x Volume of solution made) is equal to (Molarity of the stock solution
x Volume of the stock solution required). With this in mind, let's plug in the values that we know.

2 M x 30 ml = 10 M x Volume of the stock solution required

 The MCAT Chemistry Book

We need not convert the milliliters into liters for this problem, because the molar units will cancel out.
2 M x 30ml
Volume of stock solution required = = 6ml
10 M

5. The answer is C. The quickest way to solve this problem is to calculate how many moles of NaCl
are present in this solution. Then convert the number of moles to grams of NaC1. The correct
answer is 5.1 g.

6. The answer is D. All the solubilities shown in the graph are endothermic. In fact most compounds
(solids) dissolve endothermically. The graph shows that as the temperature increases, the solubil-
ity of the salts increases. In other words, as the temperature increases, more and more of the salt
present is dissociated into ions. This is exactly how an endothermic process works.

7. The answer is D. The first step in answering this question is to find the molality of the solution.
Then plug that number into the boiling-point-change equation given in the passage.
1 mol C,H,,O,
Molality of the glucose solution = 315 g C,H,,O, x = 2.33 m
0.750 kg H 2 0 180 g C,H,,O,
AT, = K, m = (0.512O C/m)(2.33 m) = 1.2O C.

The answer is 100' C + 1.2' C = 101.2' C.

8. The answer is B. The observed changes in colligative properties are less than what was theoreti-
cally predicted. This is because the ionization of salts in water is not as complete as we expect.
Some of the oppositely charged ions stick together and function as a unit. So the number of
particles (units) is lower than what we expect. As the concentration increases, the possibility of
the oppositely charged ions sticking together is greater than that in dilute solutions.

9. The answer is D. This question is a bit tricky. You may have selected Choice A. But you have to
understand what exactly is asked in the question. The question is not asking about the change in
boiling point (AT). Instead, it asks what happens to the boiling point. It will not double; it will
only increase slightly.

10. The answer is C. Choice C is the only true statement given. Looking closely at Choices A and B,
you should realize that they represent the same relationship. Since you cannot have two correct
answers, this rules out Choices A and B. Thus, such logical elimination-techniquescan be used to
solve many MCAT problems and save valuable time.

Chapter 9 Solutions

1. The answer is B. This question tests your understanding of the concept of pH. You also have to
use some mathematical skill to answer this question, since you are not allowed to use a calculator.

pH = - log [H']
418
 Solutions

To get the hydrogen ion (hydronium or H30+)concentration, we have to take the antilog. If the pH
were 2, the molar concentration would have been If the pH were 3, the molar concentration
would have been Since the pH is 2.5, the best choice is 3 . 2 ~ 1 0 - ~ .

2. The answer is C. NaCl is a salt. Think about its source. NaCl is a salt of sodium hydroxide and
hydrogen chloride. NaOH is a strong base and HC1 is a strong acid. A salt solution of a strong acid
and a strong base is neutral.

3. The answer is D. An acid which can furnish more than one proton per molecule of the acid is
called a "polyprotic acid." Choices A, B and C are all polyprotic acids. So the reasonable choice
is 'none of the above.' Note that the question asked for an acid which is NOT a polyprotic acid.
You should make a habit of underlining or circling key words in the question, especially when the
question stem contains words such as "not, except, increasing, decreasing."

4. The answer is C. To answer this question, you have to manipulate the given equation.

The given equation is:

[conjugate acid]
pOH = pK, + 1% [base]

pOH = - log [OH-]

[conjugate acid]
- log [OH-] = - log [I$] + log [base]
[conjugate acid]
log [K,] = log [OH-] + 1% [base]

[base]
log fKbI = log [OH-] - log [conjugate acid]
5. The answer is C.

The choices are phosphoric acid and its dissociation products (see above). In a polyprotic acid,
such as H,PO,, almost invariably the first dissociation will be of the highest degree. So the highest
The MCAT Chemistry Book

pKa is for HPO,'. This is Choice C. For a comparison, the Ka values are given below. But as you
know, we do not need them to answer this question.

H3P04 Ka, = 7.5 x ~ O - ~

H,PO,- Ka, = 6.2 x ~ O - ~
HP0,2- Ka, = 3.6 x10-"

6. The answer is A. The question asks for the net ionic equation of the given acid-base equation. The
given reaction is a strong acid-strong base reaction.

7. The answer is A. For this question, we are looking for a strong acid-strong base curve. Why? Well,
the answer is simple. In Reaction 1, we have a strong monoprotic acid (HC10,) reacting against a
strong base (NaOH). The only curve that satisfies this criterion is given in Choice A.

8. The answer is D. In this question, we are asked to analyze the upper and lower limit ratios of base-to-
acid at the best buffering pH. How can we answer this question? Well, there are some clues in the
passage. According to the passage, the effective pH range of a buffer system is between pKa - 1 and
pKa + 1. What other relevant information do we have in the passage? The passage also gives us an
equation with which we can relate the pH and the pKa.

pH =, pKa + log [A-

- I
[HA]
In order to have a pH value of pKa - 1, the second half of the equation with the log should be
negative 1. For this the base-acid ratio should be 0.1;log 0.1 = -1. For the other criterion pKa + I , the
log value should be +l. For this, the ratio should be 10.

9. The answer is B. This is a straight forward question. The question asks for the pH of a solution of -
HC1. HC1 is a strong acid, and strong acids completely ionize. So we don't have to worry about
partial ionization such as in weak acids.
pH = log[^ +]=3.2 x 10- = 3.5
10. The answer is B. This is actually one way of defining pKa value. At the pKa value, the acid-base
ratio is 1. So the best answer is Choice B. In addition, it is near the pKa value that the solution will
have its best buffering capacity. So Choice D wrong.

Chapter 10 Solutions

1. The answer is A. "Bomb calorimeter" is a device used to determine the energy changes that are
associated with reactions by measuring the amount of heat generated or absorbed by a reaction at
constant volume. The changes (measurements) are made at constant temperature and constant
volume. There is nothing true about Choice B. Keeping the volume constant is not an impossible
task! This rules out Choice B. Choice C is wrong, since there is no change in volume, and theo-
retically there is no work done.
 Solutions

2. The answer is B. The figure shows the conversion of ice (s) to water (I). The process is melting.
What happens when a solid is converted to its liquid form? There will be an increase in randomness.
This rules out Choice D. Choice C doesn't make any sense. Since the randomness is increased, the
entropy is increased.

3. The answer is C. The change in free energy (AG) is related to enthalpy and entropy by the follow-
ing equation:
AG = AH - T AS
In this question, the change in free energy is zero. This means that there is no net transfer of free
energy. This in turn means that the forward and backward reactions are both favorable and thus
the reacting system is in equilibrium.

4. The answer is D. This question tests your knowledge and ability to make reasonable judgements
based on a limited amount of information. We are given only an equation and a description of that
equation. Without further data on this reaction, we cannot be sure whether the reaction is exother-
mic or endothermic. We cannot say whether the reaction is spontaneous or nonspontaneous with-
out pertinent data. Choice C is untrue.

5. The answer is C. According to the third law of thermodynamics, the entropy of a pure, crystalline
substance at 0 K is zero.

Chapter 11 Solutions

1. The answer is D. The equilibrium constant is the equilibrium molar concentrations of the products
raised to their corresponding coefficients, divided by concentrations of the reactants raised to
their corresponding coefficients. The coefficients can be taken directly from the balanced equa-
tion of the reaction.
N2 (g)+ 3 H2 (g) =2 NH3 (g)
The equilibrium expression is:

2. The answer is C. From the given equation, we can write the general form of the rate as:

Rate = k [XIm[Y]"

Our next step is to find m and n using the given information. Examining the first and the second
experiments shows that the concentration of X is kept constant, but the concentration of Y is
doubled. When the concentration of Y is doubled, the rate also is doubled. So the order (n) with
respect to Y is 1. Now compare experiments 2 and 3. In experiments 2 and 3, the concentration of
Y is kept constant, but the concentration of X is doubled. This time, the rate is quadrupled. Hence,
the order (m) with respect to X should be 2. So the correct expression is Rate = k [ X ]* [ Y 1.
The MCAT Chemistry Book

3. The answer is D. This question tests your basic understanding of the factors that affect the rate of
reactions. All the listed factors can influence the rate of reactions.

4. The answer is D. This is the potential energy diagram of a reaction. For the MCAT, you should be
familiar with diagrams of this type. Since the direction of the reaction-coordinate is indicated in
the diagram, we can predict the potential energy level of the reactants and the products. The bump
in the graph represents the activation energy of the reaction. So Choice A doesn't make any sense.
According to Choice B, there is a net absorption of energy. But in contrast to this statement, there
is a net release of energy. This prediction is based on the fact that the energy level of the products
is below that of the reactants. This makes Choice C wrong. That leaves us with Choice D. In fact
the diagram is that of an exothermic reaction.

5. The answer is A. Catalysts can change the rate of reactions, by decreasing the activation energy.
Catalysts are not consumed by the reactants. If a substance is consumed in the process, it cannot
be a catalyst.

6 . The answer is B. According to the question, the reverse reaction of Reaction 1 is endothermic.
This means the forward reaction is exothermic. For exothermic reactions, the AH is negative.

7. The answer is C. In the experiment, the hydrogen is removed. Such a change in concentration will
upset the equilibrium. We have to approach this problem in terms of LeChatelier's principle.
Changes in the c~ncentrationsof reactants or products of this reaction will turn the system into a
non-equilibrium state. The result will be an adjustment of the reaction mode to restore the system
to equilibrium. So if we take H, away, the backward reaction will be favored for restoring the
equilibrium.

8. The answer is C. The pressure is decreased in the system. Such a decrease in pressure will not
change the reaction mode. Let's take a look at the reacting system.

(Reaction 1)

Both sides of the equation have equal number of moles - two on the reactant side and two on the
product side. So the pressure change will not affect the reaction in this case.

9. The answer is C.

N2(g) + 3H,(g) 2NH3 (g) (Reaction 2)

In Reaction 2, a pressure change will affect the reaction. Here, the pressure is increased and that
will increase the forward reaction. In other words, the reaction shifts to the right. Item I says that
the reaction shifts to the right. But for the wrong reason. According to the equation, we have more
moles on the reactant side. So item I is not hlly correct. Item I1 is also ruled out because the
reaction shifts to the right. Item I11 makes perfect sense.
 Solutions

10. The answer is D.

11. The answer is B. There are 2.5 moles (70 g) of nitrogen. The amount of H, used should also be
taken into account. According to the question, 10 g of hydrogen was used, which is equivalent to
5 moles. So the hydrogen acts as the limiting reagent. By the reaction of 5 moles of hydrogen with
excess of nitrogen, the number of moles of ammonia produced should equal 1013 moles. Now, it
is a matter of converting moles to grams.
10 17g NH,
- moles x = 57 grams
3 1 mol NH,
12. The answer is B. Entropy is a thermodynamic quantity which measures the randomness in a sys-
tem. An increase in randomness means an increase in the entropy. In general, gas phase has a
higher entropy than liquid phase, and liquid phase has a higher entropy than solid phase. But in
this reaction, all the components are in their gas phases, and the reactant side has more of them.
The production of ammonia causes the entropy to decrease because there is less randomness than
before the reaction began.

13. The answer is D. We cannot predict the spontaneity of the reaction accurately based on the infor-
mation given in the passage. The only fact that we know regarding the reaction is that it has a AH
value of -92 kJ. Based on that alone, it is not possible to predict the spontaneity accuratel>.

Chapter 12 Solutions

1. The answer is C. A redox equation is represented in the question. The electrode potential of'the
reaction is also given. The question also says that the reaction occurred spontaneously. For the
given direction of the reaction, the electrode potential is negative. So the reaction must have taken
place in the opposite direction of what is given in the question and thus had a positive potential. A
net positive potential means a negative free energy change. A negative free energy change denotes
spontaneity. We can rewrite the equation:
~n (s) + sn2+ + zn2' (s) + Sn (s)
EO = + 0.62 V
Now we have a positive voltage, where the zinc is oxidized and a tin ion is reduced. Oxidation of zinc
means it is losing electrons. Recall that oxidation is losing electrons, and reduction is gaining electrons.

2. The answer is A. In the half-reaction, chromium is going from a +2 oxidation state to a +3 oxida-
tion state. This is oxidation. Oxidation involves the losing of electrons. You can also predict this
by simply examining the increase in oxidation number (+2 to +3), which is a result of oxidation.
Oxidation occurs at the anode, whereas reduction occurs at the cathode.

3. The answer is D. Based on the given information in the question, we can say that E" is directly
related to K. The question also says that the product concentrations are greater than the reactant
concentrations. So we can say that the equilibrium constant value is greater than 1. We can rule out
Choice A, because there is no such thing as a negative concentration. So K cannot be negative
 The MCAT Chemistry Book

anyway. Since we know that K is greater than 1, the natural logarithm of K will be positive. So from
the equation, we can say that E" cannot be negative, which rules out Choice B. Hence, the EOvalue
should be positive. The change in free energy, AG = - n F EO.From this equation, we can predict
that if the overall potential (EO)is positive, the change in free energy (AG) is negative. A negative
AG means that the reaction is spontaneous.

4. The answer is C. Ampere is defined as the total amount of charge that flows per second.
Coulombs
Ampere =
seconds
The charge in coulombs = 5 A x 3.5 min. x 60 s/ 1 min. = 1050 coulombs.

5. The answer is B. For a reaction to be spontaneous, the electrode potential should be positive.
Oxidation of copper has a negative electrode potential. That rules out Choice A. Oxidation of
fluoride ion and reduction of zinc ion have negative electrode potentials, which rules out Choices
C and D respectively. The reduction of chlorine represented below has a positive potential which
indicates spontaneity.
C12 + 2 e + 2 C1 EO (V) = +1.36

6. The answer is D. The two half-reactions can be written as shown below:

Now, it is just a matter of adding the individual potentials to get the overall potential. A word of
caution: when you add the individual half-electrode potentials, make sure that the appropriate
sign has been assigned to them.

7. The answer is D. Even though a salt bridge allows an electrical connection between the two half-
cells in a galvanic cell, the function of a salt bridge is not to conduct electricity. So Choice A is
ruled out. Choice B makes no sense. The salt bridge does not control the voltage. The function of
a salt bridge is to maintain electrical neutrality in the half-cells so that excess buildup of charge
will not occur in the half-cells. If excess charge builds up in the half-cells, the reaction will slow
down and quickly die out.

8. The answer is C. The question asks for the best oxidizing agent. An oxidizing agent gets reduced
in the process. So the oxidizing agent (species) should be able to accept electrons with ease. The
most positive reduction potential is that of chlorine (Cl,); which makes chlorine the best oxidizing
agent among the choices.
Cl2+2i-2cl- '1.36
9. The answer is B. The question asks for the species that has the highest oxidation potential. Oxida-
tion is losing electrons. Thus all the half reactions should be considered in the oxidation sense.
Since the table gives you reduction half-reactions, you have to reverse all the equations, and when
you reverse the equations the sign of the potentials should also be reversed. The most positive
424 value is that of the oxidation of potassium.
 Solutions

10. The answer is B. The process described in the question is Fe changing to Fe2+,which is oxidation.
Oxidation occurs at the anode and reduction occurs at the cathode.

Chapter 13 Solutions

1. The answer is B. We are asked to evaluate the radioactive change. The equation should look like
this:

Notice that the atomic and mass numbers decreased by 2 and 4 units, respectively. The helium
nucleus shown in the equation is an alpha particle.

2. The answer is C. In the given radioactive decay, sodium is converted to neon. Notice that the
atomic number decreased by one, but the mass number remained the same. The most likely par-
ticle that is emitted is a positron. A positron is a positively charged electron. The equation is
shown below:
, , N a + f i ~ e+ ye' + y
22

A gamma particle is also emitted, but that information is not needed to answer this question.

3. The answer is A. This question tests your knowledge of common radioactive emissions. The only
emission listed that is a high-energy electromagnetic radiation is the gamma ray. Electromagnetic
rays travel at the speed of light. The only emission that travels close to the speed of light are beta
particles. But the best choice is gamma ray. So the answer is A. In addition to the greater speed,
gamma rays have the highest penetrating power.

4. The answer is C. See the explanation for Question 3.

5. The answer is D. This question tests your knowledge of the concept of half-life. Half-life is de-
fined as the amount of time for a radioactive substance to decay to half its initial quantity. Since
the half-life of substance X is 12 years, it takes twelve years for substance X to decay to half its
initial quantity. We have 9 grams of substance X present. The amount of substance X that was
originally present is 150 grams. So it must have undergone radioactive decay for at least four half-
lives. Write the decay mode, starting from the original amount present.

Each arrow indicates one half-life, for a total of four half-lives. Since one half-life is 12 years, the
total time elapsed is 12 x 4 = 48 years. The exact answer is a little above 48 years. But the
approximation is correct since the choices are far apart and no values higher than 48 are given. 425
The MCAT Chemistry Book

6. The answer is D. Half-life is the amount of time required for a radioactive substance to disinte-
grate to half its initial quantity. The sample described in the question has disintegrated to 3% of its
original quantity. The disintegration can be analyzed as follows:

This means, at least 5 half-lives must have elapsed.

7. The answer is A. A beta particle is an electron. By the emission of a P-particle, the nucleus must
have changed into protactinium (Pa) which has atomic number 91. Remember that a P emission
decreases the atomic number by one.

8. The answer is C. Since alpha particles are positively charged and beta particles are negatively
charged, Choices A and B are true. Gamma rays are not deflected because they have no charge.
Choice D is also true.

9. The answer is B. According to the figure given in the passage, as the number of protons increases
the neutron-proton ratio increases and becomes greater than or equal to one. (Clue: Look at the
slope)

10. The answer is D. The mass loss can be equated with the binding energy. In essence, mass loss can
be calculated using the equation E = mc2.

Energy = (3.1x ~ x loi2kg. mls2 = 2.8 x 1012J.

kg)( 3 x 1O8 m / ~ =) 2.8

11. The answer is D.

232
,,Th + ??? + 2ii~a
The question tests your ability to evaluate radioactive emissions by analyzing a given radioactive
emission reaction. Notice that the atomic number decreased by 2 and the mass number decreased
by 8. If two alpha particles were emitted, that would decrease the mass number to 224, because an
alpha particle is a helium nucleus (4, He ). It would also decrease the atomic number by 4. But
apparently that is not the case here. The atomic number decrease by only 2. This can be accounted
for if two P-particles were also emitted.

Chapter 14 Solutions

1. The answer is B. The carbon indicated by the arrow is an sp2 hybridized carbon atom. Notice that
the indicated carbon has a double bond and two single bonds. The double bond connects this
carbon to the end-carbon. A hydrogen atom and the 3rdcarbon are attached to this carbon via
single bonds.

2. The answer is A. Acetylene is the first member of the alkyne group. The carbon-carbon bond is a
triple bond which contains only one sigma bond.
 Solutions

3. The answer is B. The triple bond of 2-propyne (an alkyne) contains one sigma bond and two pi
bonds.

4. The answer is C. The sp3hybrid orbitals such as those seen in alkanes have a tetrahedral orienta-
tion.

5. The answer is D. This question also tests your basic knowledge of hybridization in carbon com-
pounds. A triple bond means three bonds. Since there are three bonds, six electrons are involved
in the bond.

6. The answer is B. Methane has a tetrahedral geometry. So the hydrogen-carbon-hydrogen bond

angle is closest to 109.5".

7. The answer is C. The triple bond is the shortest among the bonds indicated by the arrows. The
only triple bond-bearing compound given is Choice C.

8. The answer is B. The carbon-hydrogen bond is a single covalent bond.

Chapter 15 Solutions

1. The answer is B.

To answer this question, we can use the following clues from the question:
i) The compound is composed of only carbon and hydrogen atoms.
ii) It is a saturated hydrocarbon.
iii) It does not have a ring structure.
So the compound is an alkane. Alkanes have the general formula C,H,,+,. NOWthis becomes a
simple algebra problem. Since there are 14 hydrogens, 2n+2 = 14.

2. The answer is A.

3. The answer is D. Constitution isomers are compounds with the same molecular formula, but
differ in the order with which the atoms are bonded. This definition matches the relationship
between n-butane and isobutane.

4. The answer is C. First, we have to number the carbon chain to get the longest possible chain in the
structure. The numbering should be done in such a way that the branches will have the smallest
substituent number. The numbering is done as follows:
The MCAT Chemistry Book

There are 9 carbons in the parent chain. So the parent chain is clear and the complete name ends
with "nonane." This rules out Choices A and B. There are 2 methyl groups on carbons 3 and 6. So
the compound is 3,6-dimethyl nonane.

5. The answer is C. Butane contains 4 carbon atoms and if one mole of butane is completely com-
busted, at least 4 moles of carbon dioxide will be formed provided that there is enough oxygen.

6. The answer is B. A secondary carbon atom should be attached to two other carbon atoms. The
carbon atoms indicated by arrows I and I11 are secondary carbon atoms.

7. The answer is A. A carbonium ion is the same as a carbocation. A carbocation is a positively

charged species.

8. The answer is C. Gauche conformation is a form of staggered conformation. The conformation is

Gauche if the relative separation of two substituents on adjacent atoms is 60". The Newrnan rep-
resentation of a Gauche conformation is shown:
Gauche

9. The answer is B. The angle closest to 109.5' is 110'. That is the most likely bond angle, having the
least angle strain.

10. The answer is A. All the given choices are alkanes. Item I is an unbranched alkane. Items 11,111, IV
have increasing degrees of branching. Branching decreases the area of contact and thereby de-
creases the intermolecular interactions. So the unbranched alkane has the highest boiling point.
Keep in mind that without actually measuring the properties, we can only compare compounds of
comparable weights and number of carbons with reasonable accuracy.

11. The answer is D. The question asks for the type of force that is important with respect to alkanes.
Alkanes cannot undergo hydrogen bonding. So Choice A is out. Choice B is generally not impor-
tant in alkanes. Since there are no ionic bonds in an alkane, Choice C is wrong. The correct choice
is Van der Waals forces.

12. The answer is D. To answer this question you have to do some intuitive thinking based on the
information given in the passage. Butane is a four-carbon alkane with the formula C,H,,. It is a
bigger molecule than propane, but a smaller molecule than pentane. So the boiling point of butane
should be between propane and pentane. We are talking in terms of the relative boiling points. But
the question asks for the melting point. So let's translate this idea in terms of melting point.
Obviously, the melting point of a substance should be below its boiling point. So the answer
 Solutions

cannot be either 37.5"C or 55.1C. This rules out Choices A and B. Choice C is not a sensible
answer because butane is a gas at 25C.

13. The answer is C. Choice A is an initiation step. Choice B is a chain termination step. Choice D is also
a chain termination step. The only choice which represents a chain propagation step is Choice C.

14. The answer is A. This question tests your knowledge of intermolecular forces and other interactions
that give rise to some of the chemical and physical properties of compounds. Let's take a look at
the compound 2,3-dimethylbutane. We do not have a clue about the precise properties of the
compound asked in this question. But what we do know is the boiling point of one of its relatives.
In the table given in the passage, we are told that the boiling point of 3-methylpentane is 63.3" C.
If we compare these two compounds, we see that they have the same number of carbons and
hydrogens - both are six-carbon alkanes. If the boiling point of 3-methylpentane is 63.3" C, then
2,3-dimethylbutane will have a boiling point lower than that. The only choice with a lower value
is Choice A.

15. The answer is C. The only way to answer this question is to draw the possible isomers by trial and
error. There is no choice other than drawing out the possible structures, starting from the straight
chain form of heptane.

Chapter 16 Solutions

1. The answer is B. Acid-catalyzed dehydration of the alcohol shown will result in a mixture of
alkenes. All the given choices are alkenes. But Choice B is different, because it has 8 carbons. The
parent alcohol has only 7 carbons. So Choice B is not possible as one of the products. All the other
compounds given are possible products because of the rearrangement involved in this type of
reaction.

2. The answer is C. The question asks for the number of double bonds present in the unsaturated
alkene that undergoes complete hydrogenation. Each double bond to be converted to a saturated
bond requires 2 hydrogen atoms. If 8 moles'of hydrogen (hydrogen is diatomic) is used per mole
of the compound, the compound should have 8 double bonds.

3. The answer is D. Ozonolysis is a two-step reaction sequence in which carbonyl groups are gener-
ated. The double bonded carbon atoms become the carbon of the carbonyl groups that are created.

4. The answer is B. In this reaction, 2-butene is reacted with peroxyacetic acid. This reagent converts
the alkene into an epoxide, which is a compound that has a three-sided ring with an oxygen atom
in the ring.

5. The answer is C. This reaction (hydroboration-oxidation) involves the conversion of 1-butene

into an alcohol by hydration. The hydration follows anti-Markovnikov's rule. There is no
rearrangement in this reaction. .'
 The MCAT Chemistry Book

6 . The answer is A. The heat of hydrogenation decreases as there are more and more substituents in
the alkene group. Among the choices, the least amount of substitution is for ethylene.

7. The answer is A. The reaction between 1-propene and HBr in the presence of peroxides results in
the addition of HBr into the alkene group. The addition follows anti-Markovnikov's rule. The
reaction is shown below:

8. The answer is B.

9. The answer is C. Since acid-catalyzed dehydration sequence may involve rearrangement depending
on the alcohol involved, Choice A is wrong. Choice B is only partially correct. Even though it is
true that there can be rearrangement, the process of rearrangement results in more stable
intermediates rather than less stable intermediates. The major product is the most substituted
product, because the most substituted product translates to higher stability.

10. The answer is B. Rearrangement is possible in acid-catalyzed dehydration of alcohols. The inter-
mediate is a carbocation, not a carbanion. This eliminates statements I and 111. Depending on the
type of alcohol, the rearrangement may involve either methyl shift or hydride shift.

11. The answer is D. All the compounds listed in the choices can be synthesized by the oxidation of
alkenes.

12. The answer is B.

13. The answer is B.

14. The answer is D.

CH3CECCH3
, 3 (0
H3C\
H/c=' /H

\
CH3

H2 H3C\ ,CH3
* /c=C
Lindlar \
catalyst H H
These two products are cis-trans isomers and are commonly called geometric isomers.
430
 Solutions

15. The answer is B.

LOW H3C H LOW
\ /

HIGH B; NO, HIGH

The given structure has Z-configuration. Recall that the priorities are based on the atomic number
of the atom bonded to the double bonded carbon.

Chapter 17 Solutions

' 1. The answer is B. The shortest bond here is the triple bond.

2. The answer is B.

Bottle A - cis-2-Butene
Bottle B - 1-Propyne
Bottle C - Butene

Compare the carbon-carbon bonds that distinguish these compounds. cis-2-Butene is an alkene
which has a carbon-carbon double bond. 1-Butyne is an alkyne and has a carbon-carbon triple
bond and butane has carbon-carbon single bonds. The triple bonded carbon-carbon bonds have
the highest bond dissociation energy. Bottle B contains 1-propyne.

3. The answer is C. Of the given choices, acetylene is the most acidic and has the lowest pKa value.

4. The answer is B. Lindlar catalyst is a combination catalyst which does selective or restrictive
hydrogenation of alkynes to alkenes. Furthermore, the product is a cis-alkene.

5. The answer is C. When 1-butyne is treated with sulfuric acid in the presence of mercuric oxide as
catalyst, hydration occurs. The hydration follows Markovnikov's rule and forms a ketone. The
reaction is given below:

Mercuric
oxide 2-Butanone

6. The answer is D. When 3-hexyne undergoes ozonolysis, propanoic acid is formed.

 The MCAT Chemistry Book

7. The answer is B.

The general structure of a vicinal dihalide:

The double dehydrohalogenation (two dehydrohalogenations or eliminations) of vicinal dihalide

results in an alkyne.

8. The answer is D. There is nothing there to dehydrate or dehydrohalogenate in an alkyne. This

eliminates Choices A and B. Hydrolysis will not help the direct conversion of an alkyne to alkane.
A simple hydrogenation is the best way to accomplish this conversion.

9. The answer is A. The liquid ammonia-sodium combination can be used to convert an alkyne to a
trans-alkene. In essence, this reaction involves the restrictive hydrogenation of an alkyne to an
alkene (trans-product).

10. The answer is D. Alkynes have higher boiling points than corresponding alkanes. So Choice A is
true. Alkynes have sp hybridized carbons. So Choice B is true. Choice C is also true, since a
terminal alkyne like acetylene can form acetylide ions when exposed to strong bases.
-
H C c :~ (Acetylide ion)

11. The answer is C. Alkynes are characterized by hybrid orbitals called sp orbitals. In the sp orbitals,
there is 50% s character and 5 0 % character.
~

12. The answer is B.

Reaction 3

H3CCECH - HBr
Br
I
H,cc=CH;!
Alkynes, just like alkenes, can undergo addition reactions. Reaction 2 is a typical example of an
addition reaction.

13. The answer is D.

HCECH - - NaNH,

Liq.NH,
+
H C E C Na
- n-butyl
bromide
HCsC(CH2)3CH3

14. The answer is C. Oxidizing agents oxidize other compounds; they do not reduce! This rules out
Choice D. Choice B does not make any sense either. The alkyne is not being reduced to an alkane,
but is being reduced to an alkene. This is not the most reduced form. Choice A is incorrect. The
function of quinoline is to moderate the activity of the catalyst so that the double bonded alkenes
that are formed will not undergo further reduction to form alkanes. Moreover, quinoline is not the
432 actual catalyst.
 Solutions

15. The answer is D. According to the passage, quinoline is a heterocyclic arnine.

16. The answer is D. The product of this catalytic conversion reaction is a trans-alkene. The combina-
tion of reagents (group I metal with liquid ammonia) used is unique in the sense that the product
formed is a trans-product. The intermediate involved in this reaction, called the alkenyl radical,
readily forms the resulting trans-product.

Chapter 18 Solutions

1. The answer is B. Dimethylated benzenes are called xylenes.

2. The answer is B.

The carbons in the benzene ring are sp2hybridized.

3. The answer is C. See explanation for Question 1.

Phenol Benzoic acid Toluene

The MCAT Chemistry Book

4. The answer is B. For a compound to be aromatic, it should have 4n+2 number of pi electrons. So
the numbers satisfying the 4n+2 condition are 2 , 6 , 10, 14, . . .. Four is not in this series and that
is the answer.

5. The answer is A. This reaction is an electrophilic aromatic substitution reaction. The product
formed is nitrobenzene. In the reaction, nitronium ion acts as the electrophile which attacks the
benzene to form the cyclohexadienyl intermediate, followed by the elimination of the proton to
form nitrobenzene. The reaction mechanism follows:
+
0=N=O
N=O
Cyclohexadienyl ion

6. The answer is D. This reaction is best described as a Friedel-Crafts alkylation reaction.

7. The answer is A. This reaction is commonly called the Clemmenson reaction.

8. The answer is D. The nitro group (-NO,) is a strongly electron withdrawing group, and thus a meta
deactivating group. So it favors meta substitutions the most.

9. The answer is C. The regioselectivity of halogens favor ortho/para positions. Halogens are elec-
tron withdrawing entities that are ortholpara directing and also deactivating groups.

10. The answer is B. The -CHO group present in the ring is best described as a meta-directing group.
So the most likely position of substitution is the meta position.

11. The answer is D. This reaction is a Friedel-Crafts alkylation reaction. This rules out Choice A. In
an alkylation reaction, there is a possibility of rearrangement. The primary alkyl halide (n-propyl
chloride) can form secondary carbocations by rearrangement. To avoid this type of rearrangement,
chemists often use Friedel-Crafts acylation reactions which do not involve rearrangement. The
carbonyl group in the acylation product can be easily reduced to get the desired hydrocarbon.

12. The answer is A. An alkoxy group can be represented as -OR, where R stands for an alkyl group.
It is an ortholpara-directing group and also a good activating group.
 Solutions

13. The answer is C. The substituent -OH is an ortholpara activator. The resulting product is a bro-
mine substitution product. The only choice that fits the reasoning is C.

14. The answer is A. The reaction shown is neither an addition reaction, nor an elimination reaction.
So the Choices B, C, and D can be ruled out. This is a typical electrophilic substitution reaction.

15. The answer is C. The inscribed circle stands for the pi-system of electrons present in the benzene
ring. Let's be more precise: The circle represents the 6 pi electrons of the benzene ring. Choice D
states "8 pi-electrons" which is wrong.

16. The answer is D. To answer this question, we have to think about the substituent; the nitro group.
The nitro group is a meta deactivating group. So the substitution predominantly results in a meta-
product (1,3 substituted). According to the passage, compound C is the major product. .

Chapter 19 Solutions

1. The answer is B. Enantiomers are non-superimposable mirror images. These compounds are
enantiomers.

2. The answer is A. The two compounds are stereoisomers. To be precise, they are diastereomers.
Diastereomers are not mirror images. Hence, the two compounds given are not mirror images.

3. The answer is D. Since the enantiomer is what is asked for, the answer can be ascertained by
visualizing the mirror image,

4. The answer is C. The given representation is called Fischer projection. The Fischer projection is a
2-dimensional way of representing stiuctures. To manipulate the Fischer projection, we should
think in terms of 3-D. This can be done by interchanging two pairs of substituents at a time. If only
 The MCAT Chemistry Book

one pair is interchanged, we will not get the equivalent structure. Let's say we interchanged only
one pair. This will result in its enantiomer. Such an example is Choice C which is the only non-
equivalent structure.

5. The answer is D. The given structure is an ethane derivative, not a methane derivative. This rules
out Choices A and B. In the Fischer projection, the horizontal lines represent the bonds extending
out of the plane of the paper toward you. The vertical lines represent the bonds pointing into the
plane of the paper (away from you). With this in mind, we can start the switching of groups as
follows:

The switching is done so that the lowest ranking substituent (here, it is H) points away (into the
plane of paper). The numbering or priority is based on decreasing atomic number. That means the
substituent atom with the highest atomic number gets number 1, the next highest gets number 2,
and so on. Since the order is clockwise, the configuration is R.

6 . The answer is B. Only statements I and I1 are true. All enantiomers are stereoisomers, but not all
stereoisomers are enantiomers. Diastereomers are also stereoisomers.

7. The answer is B.

Chapter 20 Solutions

1. The answer is B.

This is straightforward question, involving an important idea. The halogen is attached to a sec-
ondary carbon atom and hence it is a secondary alkyl halide.

2. The answer is C. In general, as the number of carbons increases, the boiling point increases. But in
this question, all the given choices are derivatives of the same alkane. In other words, they all have
the same number of carbon atoms. The compound I-chloroethane is monochlorinated, the
compound I, 1-dichloroethane is dichlorinated, and the compound 1,1,3-trichloroethane is
trichlorinated. As the number of C1 atoms increases, the attractive forces also increase, which
means the boiling point increases.

3. The answer is D. The reactivity-trend of alcohols with hydrogen halides:

436 Tertiary alcohol > Secondary alcohol > Primary alcohol

 Solutions

4. The answer is B. The generalization in Choice A is not correct. Alkyl halides are generally in-
soluble in water. Choice C is wrong. The only reasonable choice is B.

5. The answer is C. The question asks for the order of reactivity of bimolecular substitution reac-
tions. The general order of reactivity is:

Methyl halide > Primary halide > Secondary halide > Tertiary halide.

6. The answer is D. Choice A is not true because tertiary halides usually undergo substitution by S, 1
mechanism. Choice B doesn't make any sense at all. Choice C is not correct, because SN2mechanism
generally does not involve a carbocation intermediate, whereas SN1mechanism does involve a
carbocation intermediate. Hence, by elimination the answer is D.

7. The answer is D. For this reaction, Choices A, B, and C are possible products. Besides substitu-
tion, elimination is also possible, resulting in three products.

C2H50H
(CH3)CBr I(cH~)~c+I CH3CH20C(CH3)3
carbocation
intermediate

8. The answer is B. The inversion of configuration (at the stereogenic carbon involved in the substi-
tution) is a characteristic of SN2reactions.

9. The answer is A. Among alkyl halides, alkyl fluorides have the lowest nucleophilic substitution
rate. The fastest are alkyl iodides, followed by alkyl bromides and alkyl chlorides.

Chapter 21 Solutions

1. The answer is C. One of the most important properties of alcohols is their ability to undergo
hydrogen bonding. The higher boiling points exhibited by alcohols when compared to similar
alkanes and ethers are caused by the ability of alcohols to undergo hydrogen bonding.

2. The answer is C.

3. The answer is D. All the listed processes are possible ways of making alcohols.

4. The answer is B. The oxymercuration-demercurationreaction converts an alkene to an alcohol.

The hydration follows Markovnikov's rule and thus the hydrogen adds to the carbon atom with
greater number of hydrogens. 437
The MCAT Chemistry Book

5. The answer is A. Alcohols are much more acidic than alkanes. Among alcohols, primary alcohols
are the most acidic ones. Compound A is a primary alcohol. Compound B is a secondary alcohol
and Compound C is a tertiary alcohol.

6. The answer is C. Primary alcohols can be converted (oxidized) directly to carboxylic acids. Oxi-
dation of secondary alcohols results in ketones. In some rare cases, secondary alcohols can be
converted into carboxylic acids using very strong oxidizing agents, but generally that is not the
case. Tertiary alcohols cannot be oxidized. So the best choice is C.

7. The answer is B. Reduction of a ketone usually results in a secondary alcohol.

8. The answer is D. When ethyl magnesium bromide is reacted with ethylene oxide, the carbon chain
extends by two more carbons. The product is an alcohol with four carbon atoms.
Ethyl magnesium bromide
(Diethyl ether)
C H 2CH2 CH~CH~CH~CH~OH
\/
0
~~d
9. The answer is B.

CH3CH2CH20H (Compound A)

Pyridinium dichromate

CH3CH2CH0
(Compound B)

Reaction I sequence results in the alcohol shown above (Compound A). The alcohol formed is
oxidized by pyridinium dichromate. The product formed is an aldehyde (propanal).

10. The answer is B. The given organic compound is an aldehyde. The reduction of an aldehyde
results in a primary alcohol.
 Solutions

11. The answer is A. The numbering of carbon in the ring should be done as follows:

The substituents are cis to each other.

12. The answer is D. Primary alcohols are more acidic than secondary alcohols, and secondary alcohols
are more acidic than tertiary alcohols. Ammonia is much weaker than any other compound in the
remaining choices. In fact NH, has a pKa of roughly 36. All the alcohols listed have pKa values
ranging from 16 through 18.

13. The answer is C. The complete reaction is shown below:

14. The answer is A. Primary alcohols are the most reactive alcohols toward metals. Methanol is a
primary alcohol. The other choices are tertiary and secondary alcohols.

15. The answer is D. The question asks for a compound which can be directly converted to propanol
by oxidation. If an aldehyde is oxidized, it is converted to a carboxylic acid. Oxidation of com-
pounds in Choices B and C cannot produce an alcohol directly by oxidation.

Chapter 22 Solutions

1. The answer is B. Aldehydes can undergo nucleophilic addition reaction with Grignard reagents.
The major product here is 3-pentanol which is a five carbon alcohol.

CH3CH2MgBrl~ ,b
CH3CH2CH0 CH3CH2CHOHCH2CH3
(ether)

2. The answer is B.
OH
I
CH3CH2CHOCH2CH3
The product formed as a result of nucleophilic addition reaction between an alcohol and an alde-
hyde is called a hemiacetal. The given structure is a hemiacetal.

3. The answer is B. The reaction described in the question is an oxidation reaction.

The MCAT Chemistry Book

4. The choice is A. The reaction can be written as follows:

5. The answer is B. The carbonyl group can act as an electron-withdrawing group. This greatly
increases the acidity of a carbonyl compound. Proximity to the carbonyl group is of very great
influence in the case of acidity. In essence, carbonyl groups increase the acidity of protons that are
connected to the adjacent carbon atoms. The closest protons influenced by the carbonyl group are
indicated by the arrows a and b. Among these positions, the protons indicated by b are more acidic
because they are influenced by the carbonyl groups from both sides.

6. The answer is D.

(En01 form) OH
I / 0-
CH3CH=C CH3CH=C,
C
' H, (Enolate ion) CH3

7. The correct answer is D.

2 AH NaOH/H2z
heat
H
 Solutions

8. The answer is C.

9. The answer is D. Iodoforrn test is used to identify methyl ketones. Methyl ketones give a positive
iodoform test which is indicated by a yellow precipitate.

10. The answer is B. Chromic acid test is a qualitative test that can be used to confirm whether a given
unknown compound is an aldehyde or not. Even though aldehydes give a positive response to this
test, ketones do not. A sample reaction is shown below:
(orange color)
H2Cr207/ H2SO4
CH3CH0 * CH3COOH + Cr2(S04)3
(green precipitate)
A green precipitate confirms a positive test.

11. The answer is B. The product that is formed in Experiment 2 is an acetal. When one mol of the
given compound reacts with two moles of the alcohol, the product formed is an acetal. A simple
acetal does not have the -OH group, whereas a hemiacetal has the -OH group.

12. The answer is B. This question tests your ability to judge the type of reaction presented. The
conversion is a reduction reaction.

13. The answer is D.

The compound shown in Experiment 4 can be converted to an alcohol by the addition of Grignard
reagents. The proper Grignard reagent that should be used for this conversion can be found by
comparing the reactant and the desired product.

14. The answer is C. In the experiment, 3-propanal is converted to 2-butanol. Direct oxidation is not
an option because there aren't enough carbons in propanal to form an alcohol with four carbons.
So Choice A is ruled out. Choice B is not completely true. With appropriate steps, the reaction is
possible. One of the best ways to accomplish the reaction is to first treat the reactant with the
appropriate Grignard reagent. Since Grignard reagents are nucleophilic, they can add to the carbonyl
group. This extends the carbon chain. The product formed can be then hydrolyzed to form the
alcohol.
44 1
 The MCAT Chemistry Book

OMgBr

15. The answer is D. By definition, an organometallic compound should have a bond between a
carbon atom and a metal atom. The only compound listed here which does not satisfy the definition
is Choice D.

16. The answer is C. The conversion is an oxidation reaction.

Chapter 23 Solutions

1. The answer is D. Alkyl magnesium halide or Grignard reagent can react with carbon dioxide to
form carboxylic salts. The description of the reaction mentioned in the question also says that the

- -
reaction occured in acidic conditions. Under acidic conditions, the salt is converted to a carboxy-
lic acid. So statement I1 is true. Furthermore, alkyl magnesium halide (Grignard reagent) acts as
the nucleophile in the reaction. So statement I11 is true.

2. The answer is C. The first step results in n-butyl cyanide (Compound A). n-Butyl cyanide on
hydrolysis produces pentanoic acid.

C1
-
NaCN
H20
',/"-'
(Conlpound A)
-
CN H2SO4/H20
Heat
(Compound B)
COOH

3. The answer is C. Butanoic acid reacts with methanol in the presence of an acid catalyst to form
methyl butanoate.

4. The answer is A. Alkanes and ketones have lower boiling points compared to carboxylic acids
and alcohols. This aspect rules out Choices C and D. Comparing Choices A and B, we can say that
carboxylic acid is a better choice since it can undergo extensive hydrogen bonding. In essence,
carboxylic acids have higher boiling points than comparable alcohols.

5. The answer is D. Compound A is more acidic because it is a carboxylic acid. In general, carboxy-
lic acids are more acidic than alcohols.

6. The answer is D. Substituents, especially electronegative ones, increase the acidity of carboxylic
acids. Choice D has more substituents of this type than the other choices. S O the carboxylic acid
represented in Choice D is the most acidic.

7. The answer is D. LiAlH, is a very good reducing agent. The product is benzyl alcohol.

8. The answer is D.
442
 Solutions

9. The answer is B.

10. The answer is B.

11. The answer is C. Choice A is true. Carboxylic acids can undergo hydrogen bonding. Choice B is
also true and so is Choice D. Choice C is not true. In fact, the hydroxyl group makes its carbonyl
group less electrophilic. In a ketone there is no hydroxyl group and that makes its carbonyl group
more electrophilic than that of a carboxylic acid.

12. The answer is C. The conversion is an oxidation reaction. This rules out Choices B and D. LiAlH,
is a reducing agent. So Choice A is wrong. KMnO, is a good oxidizing agent which can accom-
plish this conversion.

13. The answer is B.

14. The answer is D.

Formic acid is HCOOH.

H-C-OH
II ..
sp2 hybridization

15. The answer is C. The question asks for the compound that has the highest pKa value. Highest pKa
value means the weakest acid. The inductive effects become less and less pronounced as the
electronegative substituents are farther away from the carboxylic group.

16. The answer is C. NaOCH, is basic. Carboxylic acids are much more acidic than alkynes. Choices
B and D are ruled out. It is a tough call between Choices A and C. The carboxylic group of acetic
acid is attached to an alkyl group. The carboxylic group of benzoic acid is attached to an aryl
group. The sp2carbons in the benzoic acid ring are more electron withdrawing than the sp" carbon
in the acetic acid. This makes benzoic acid more acidic than acetic acid.

Chapter 24 Solutions

1. The answer is B. Among the acid derivatives, the acyl chloride is the least stable and the most
reactive compound toward hydrolysis.

2. The answer is A.
 The MCAT Chemistry Book

3. The answer is C. Esters can react with Grignard reagents to form tertiary alcohols. The intermedi-
ary compound formed is a ketone which reacts with the second Grignard reagent molecule to form
the tertiary alcohol. A representative reaction is shown below:

4. The answer is B.

5. The answer is C.

6. The answer is B.

Amide
7. The answer is D. Choices A, B, and C describe possible ways of preparing carboxylic acids.
Oxidation of an aldehyde can result in a carboxylic acid.

Chapter 25 Solutions

1. The answer is A.

2. The answer is D. Alcohols, water, and carboxylic acids can undergo intermolecular hydrogen
bonding. Ethers cannot undergo intermolecular hydrogen bonding. Alkanes cannot form intermo-
lecular hydrogen bonding either. So the best conclusion is that ethers have boiling points similar
to that of alkanes.

3. The answer is D. Ethers are polar. Hence, Choice A is true. Ethers are relatively less reactive and
are widely used as solvents. Hence, Choices B and C are true.

4. The answer is A. It is true that ethers are not very reactive. Hence, statement I is true and statement
I1 is false. Ethers are flammable. Hence, statement 111 is true. Ethers have very low boiling points
compared to that of alcohols. Hence, statement IV is false.

5. The answer is A. The reaction given in the passage is called Williamson ether synthesis. By
looking at the reaction we cannot answer this question.But a clue is given in the question. According
444
 Solutions

to the question the reaction is most effective if it undergoes by SN2mechanism. Now we have
something to hang on to. Since the reaction is mostly effective when undergoing by SN2mechanism,
the alkyl halide most appropriately used must be a primary alkyl halide. The only primary halide
among the choices is methyl chloride.

6 . The answer is D. In the Williamson ether synthesis, if the alkyl halide is either tertiary or secondary,
there is a good chance that elimination reaction can prevail. However, this is not desired in this
reaction. In fact, the compounds given in Choices A, B, and C can undergo elimination reaction.
Only the compound in Choice D is exempt from undergoing elimination.

7. The answer is A. Ethers are usually not so reactive, but they will react with concentrated acids.
This is exactly the type of reaction given in the question. Methyl bromide is the product formed,
and the reaction is a nucleophilic substitution reaction.

8. The answer is B. All the compounds given are ethers except in Choice B. Choice B is an ester.

Chapter 26 Solutions

1. The answer is B.

NaOH, H30 Reaction 2

Reaction 1 results in bromobenzene (Compound A). In Reaction 2, the bromobenzene formed is

hydrolyzed to phenol.

2. The answer is B. Phenol has the hydroxyl group which is an ortholpara activator. So the substitu-
tions are more likely to be in the ortho and para positions of the ring.

3. The answer is A.
The MCAT Chemistry Book

As you can see in the diagram, the intramolecular hydrogen bonding is most pronounced in ortho-
nitrophenol because of the proximity of the.-NO, group to the hydroxyl group.

Chapter 27 Solutions

1. The answer is B. The lowest boiling point is likely to be exhibited by Compound B which is an
alkane. The highest boiling point is attributed to Compound A which can undergo extensive inter-
molecular hydrogen bonding, followed by the alcohol, and trailed by Compound D.

2. The answer is D. In general, aryl amines are less basic than ammonia. Alkyl amines are more
basic than ammonia. Among alkyl arnines, secondary amines are generally more basic than pri-
mary amines.

3. The answer is D.

4. The answer is D. This is a straightforward question. The given reaction is a reduction reaction.

5. The answer is D. In general, alcohols (comparable) are more acidic than amines. In the choices,
the only alcohol given is ethanol.

6. The answer is B. Tertiary arnines cannot have hydrogen bonds themselves, because they have no
nitrogen-hydrogen bond connections unlike the other compounds listed.
 Solutions

7. The answer is D. From the values in Table 1, we can compare the basicity of the compounds. It
appears that the weakest base is the conjugate base of aniline, which also makes it the most acidic.

8. The answer is B. The conversion that is asked for in the question is accompanied by the loss of
carbon dioxide (CO,). This is a typical example of a decarboxylation reaction.
coo
I

I
p
CH2
LGD
+H~NCH~CH~CH~CO~

(Gamma aminobutyrate)
I

9. The answer is D. The conversion is best described as a reduction reaction.

(Compound M) I I (Compound N)
CH2
I
I NADH+ H+ NAD+ I
coo- coo-

10. The answer is A.

Chapter 28 Solutions

1. The answer is C.

2. The answer is D. All amino acids are optically active except glycine. Glycine has a simple structure
and is achiral.

The structure of glycine.

H' \
Achiral

3. The answer is D. At a certain pH (unique for each amino acid), the net charge of an amino acid
equals zero. When this pH is achieved, it is said to be at the.amino acid's isoelectric point. At the
The MCAT Chemistry Book

isoelectric pH of an amino acid, the net movement of that particular amino acid will be zero when
the amino acid is subjected to an electric field.

4. The answer is C. The general structure of an amino acid is shown below:

5. The answer is D.

6. The answer is D.

7. The answer is D. Proteases are enzymes that can affect the structural integrity of proteins. Strong
bases and acids can also affect the structural mode of proteins.

8. The answer is D.

9. The answer is D. All amino acids have at least one carboxyl group. Hence, statement I is true.
Amino acids have high melting points since they can have multiple charges. This results in strong
ionic interactions and hence much energy is required to break the ionic interactions between them.
Thus it is hard to break the crystal lattice, and they have high boiling points. Hence, statement I1 is
true. Depending on the pH and the particular amino acid's nature, amino acids can have either a
net positive charge, a net negative charge, or a net zero charge. Hence, statements I11 and IV are
true.

10. The answer is C. See the explanation for Question 3.

11. The answer is C. Peptide bond is a co~~alent

bond which connects amino acids in the formation of
a peptide or the primary structure of a protein. The peptide link is formed between the amino
group of one amino acid and the carboxyl group of the adjacent amino acid.

12. The answer is B.

13. The answer is D. From the table, we can assess the behavior of amino acids by comparing the pKa
values of the amino acids. At pH 7 only glutamate will have a net negative charge.

14. The answer is D.

Chapter 29 Solutions

1. The answer is D. Galactose, glucose, and ribose are monosaccharides. Maltose is a disaccharide
made of glucose units.
 Solutions

2. The answer is B. We can rule out Choices A and C, because the given sugar is not a D-sugar.
Ribose is a.5-carbon sugar. So Choice D is also ruled out.

3. The answer is D. The synthesis of sugar probably resulted in mostly one form of the sugar. According
to the question, there was a change in optical activity. This is due to a phenomenon called
mutarotation. The sugar solution that was made mutarotated to form its corresponding anomer,
which changed the observed optical activity. The mutarotation will continue until an equilibrium
is established.

4. The answer is C. Glycogen is the only non-disaccharide listed. All the other molecules are disac-
charide~.In animals, carbohydrates are stored mainly in the form of glycogen. It is mostly stored
in the liver and the skeletal muscles.

5. The answer is B.
CHO

There are two chiral carbons in the given structure. So the number of possible optical isomers is 2? = 4.

6. The answer is A. Fructose, glucose, and galactose are monosaccharides. The only choice that is
not a monosaccharide is sucrose. Sucrose is a disaccharide formed by glucose and fructose.
The MCAT Chemistry Book

7. The correct answer C. The given structure is not glucose. Ribose is a five-carbon sugar. The given
structure is a six-carbon sugar. Maltose is a disaccharide. Further, the given structure is a ketose
sugar, and the only ketohexose sugar listed is fructose.

8. The answer is A.
Compound I H ?H Compound I1
H
HOH,C o ~ o v ~

H OH

Statements 1 and 2 are true. Both given structures are glucose; one is in the furanose ring form,
and the other is in the pyranose ring form. The five-membered ring of glucose is called
glucofuranose. The six-membered ring of glucose is called glucopyranose.

9. The answer is B. Glucose and mannose are not anomers, nor are they are mirror images. So
Choices A and C are ruled out. Choice D is not true. In fact, they are epimers. Epimers are iso-
meric sugars that differ in their configurations only at one of their stereogenic centers.

10. The answer is A. Disaccharides are formed by the combination or bonding of two monosaccha-
rides by a linkage called the glycosidic linkage.

11. The answer is C. Anomers differ only in stereogenicity at the anomeric carbon. The structures of
a-D-glucose and P-D-glucose are drawn below. They are anomers.

I I

-:/7 7/2- "\YH

T\yH C
OH
I
,/IH
O\T
1-1

C
I
C\yHCI
OH y/?
C
I
H
 Solutions

Chapter 30 Solutions

1. The answer is B. Triglycerides are triesters of glycerol. A triglyceride can be represented as follows:

(fatty acid)

H2C-OH

Triglyceride (Glycerol)
(general structure)

As a result of hydrolysis, each mole of a triglyceride can give 1 mol of glycerol and 3 moles of fatty
acids.

2. The answer is D.

Chapter 31 Solutions

1. The answer is B. The indicated bond is best described as a phosphate anhydride bond.

2. The answer is D. The given reaction is a hydrolysis reaction.

3. The answer is B. The interconversion between the compounds X and Y is a typical example of
tautomerism. Compound X is the en01 form of pyruvate. Compound Y is the keto form of pyru-
vate. The interconversion of such forms is called tautomerism.

4. The answer is D. The bond indicated by the arrow is an example of N-glycosidic bond.

5. The answer is A. According to the passage, the hydrolysis of ATP has a negative change in free
energy (AG). So it is sensible to say that the products have less energy than that of the reactants.

6. The answer is C. ATP is a higher energy-currencythan AMP. So the hydrolysis of AMP will have
a AG that is less negative than -31 kJ/mol (given in the passage). Moreover, the conversion
represented in the question is the formation of AMP rather than the hydrolysis of AMP. This
eliminates Choices B and D. According to the clue given in the question, the products have higher
free energy than the reactants. This can give only a positive A G.

7. The answer is C.
The MCAT Chemistry Book

Chapter 32 Solutions

1. The answer is A.

2. The answer is D.

3. The answer is D. According to the passage, the reactions in Experiment 3 are based on unimolecular
substitution mechanism. Based on this information, we can say that compound B has the fastest
reaction rate. The second fastest is Compound C. These observations rule out Choices A, B, and
C. Compound A is a primary alcohol and is not likely to undergo S,1 reaction.

4. The answer is B. According to the passage, propanone is reacted with the reagent to form a prod-
uct that lacks the carbonyl group. Note that the compound propanone is a ketone and contains a
carbonyl group. But after the reaction, the carbonyl group is not present in the product formed. So
the peak that disappeared is the carbonyl peak.

5. The answer is C. The conversion results in the formation of a glycol (an alcohol). Such a conver-
sion is best described as an oxidation reaction.

6. The answer is C. The compounds A, B and C are alcohols. They do not have carboxyl groups.
They have different reaction rates in terms of substitution reactions. Since they are alcohols, they
all will exhibit broad IR peaks around 3400 cm-'.

7. The answer is A.

The compound B is tert-butyl alcohol.

Even though there are three methyl groups, all the methyl groups are equivalent and so are their
protons. So the methyl protons give rise to one peak. The hydroxylic proton will give rise to
another peak, totaling two sets of NMR peaks.

8. The answer is B. Since the compound is insoluble in water, statement I is true. Since the com-
pound is insoluble in 5% aqueous sodium hydroxide, statement I1 is false. Since the compound is
an aromatic compound, statement I11 is true. The compound is not a strong base. Hence, statement
IV is false.
APPENDIX
This page intentionally left blank
 Appendix

Table-1 Common Physical Constants

Avogadro's number (NA) = 6.02 x Imol

Electronic charge (e) = 1.60 x lo-19C
Electron's mass (me) = 9.1 1 x kg
Neutron's mass (m,) = 1.675 x lop2?kg
Proton's mass (m,) = 1.673 x 1o - ~ ?kg
Faraday constant (F) = 96500 Clmol
Molar gas constant (R) = 0.082 L . atm/K . mol) = 8.31 J/(K . mol)
Standard Temperature & Pressure, STP + 273K & latm
Standard State (temperature & pressure) + 298K (25 O C ) & latm
Ideal molar gas volume at STP = 22.4 Llmol
Planck's constant (h) = 6.63 x J .s
Speed of light in vacuum (C) = 3.0 x 108m/s
Rydberg constant for H atom (RH) = 2.18 x 10-Is J
The MCAT Chemistry Book

Table3 Conversion Factors

t

1 arnu = 1.66 x 1o - kg ~ ~
l c a l = 4.184J
1J = l k g . m2/ s2
1 atm = 760 rnrnHg = 760 torr = 1.01325 x 1o5 Pa
1Pa = 1 k g / ( m . s ) 2 = 1 ~ l m 2
OC = 519 (OF - 32)
OF = 915 OC + 32
K =O C + 273
IL =1dm3=10-3rn3
 Appendix

Table3 SI prefixes
(most important ones are starred)

1012 tera (T)

lo9 giga (G)*
lo6 mega (M)*
lo3 kilo (k)*
lo2 hecto (h)
10' deka(da)
lo-' deci (d)*
1o - ~ centi (c)*
1o - ~ milli (m)*
10-6 micro (p)*
lo-' nano (n)*
pic0 (p)
The MCAT Chemistry Book

Table-4
Some Common Groups

0
CH3- methyl II
CH3-C- acetyl

CH3CH2- ethyl
H2C=C-CH2- ally1
H
CH3CH2CH2- prOpyl
H2C=c- vinyl
H

0
CH3 \
/CH- isopmpyl

CH3 phenyl

CH3CH2CH2CH2-

CH3 \
CH- CH~-
n-but~l

isobutyl
0 cH2- e'n'.

0
CH3

CH3CH2CH2-
CH3
I see-butyl \ /
1- benzoyl

CH3
C H ~ -CH-
I tert-butyl (t-butyl)
I
CH3
 Appendix

Table-5 Some Common Functional Groups

Name General Formula Example

alkane R- H CH3CH2CM3(butane)

alkene R C F CHR' CH3CH=CHCH3 (2-butene)

alkyne

Arene Ar-H H G H (benzene)

H H
alkyl halide R- X
I CH3CH2CH2Br(butyl bromide)
1 alcohol R- O H
I CH3CH2CH20H (propanol)

1 thiol R- S H CH3CH2SH (ethanethiol)

1 ether I R- 0-R' CH3CH20CH2CH3 (diethyl ether)

0 0
II II
aldehyde R-C-H CH?CH7CH7-C-H (butanal)
--

0 0
II II
ketone R-C-R' CH3- C- CH2CH3 (2-butanone)
0 0
II II (acetic acid
carboxylic acid R-C-OH CH3-C-0H or ethanoic acid))

ester
::
CH3- C- OCH2CH3 (ethyl acetate)

0
II
H~C-C-NH~ (ethanamide)

0 0 0
II II II
anhydride R-C-0-C-R' CH3-C-0- C- CH3 (acetic anhydride)

I acyl halide

amine
R
R-C-X

R-NH2
CH3-C-
0
II
Cl (ethanoyl chloride)

H ~ C - N H (methylamine)
~

R - C N
- CH3-C=
-N (ethanenitrile or
acetonitrile)
NOTES