Basic Principles of Forensic Chemistry

JaVed I. Khan • Thomas J. Kennedy

Donnell R. Christian, Jr.

Basic Principles
of Forensic Chemistry
JaVed I. Khan Donnell R. Christian, Jr.
U.S. Crime Laboratory Criminalist.us
California Department of Justice Professional Business Solutions
Riverside, CA, USA Chesterfield, VA, USA
[email protected] [email protected]

Thomas J. Kennedy
Department of Chemistry
Victor Valley Community College
Victorville, CA, USA
[email protected]

ISBN 978-1-934115-06-0 e-ISBN 978-1-59745-437-7

DOI 10.1007/978-1-59745-437-7
Springer New York Dordrecht Heidelberg London

Library of Congress Control Number: 2011937225

© Springer Science+Business Media, LLC 2012

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This book is dedicated to the students and teachers in the field
of forensic sciences.
JaVed I. Khan

To my family: Tammy, Breanna, McKenna, and Holden. This work is

dedicated to each of you for the sacrifices you have made. Thank you
for enduring the long hours, you are my inspiration, and I love you all
very much!!
For my mother, Nancy, and my sister, Susan. Thank you for your love,
guidance, and support for so many years. It is the foundation that drives me
to be a better man. I love you.
Thomas J. Kennedy

To my parents and my wife Stephanie.

Donnell R. Christian, Jr.
Foreword

Forensic chemistry was once the foundation of the crime laboratory. The modern forensic
laboratory seems to be drifting away from its traditional roots, with the introduction of DNA
evidence and the plethora of forensic shows on television. Emphasis in biology has replaced
chemistry with serological and biological examinations. Degrees in forensic science have been
created to address the demand created by the CSI culture. However, forensic chemistry remains
the backbone of the modern forensic laboratory.
I was once asked how I would council a person seeking a degree in forensic science. I reflected
on the words of my mentor, my own personal experience with a degree in criminalistics, and the
employment prospects for new graduates with a degree in forensic science as I formulated my
response. I responded that I would advise them against seeking a degree in forensic science.
Unfortunately, that was not the response the selection committee wanted to hear.
This may seem an odd opening for a book foreword. However, the issues that factored into
my response have been incorporated into this text.
My mentor believed that he was not a science teacher. He would teach me how to apply the
science I knew to the analysis of physical evidence. He was not going to waste his time teaching
me things I should have learned in college. He was a brilliant man and could teach anyone to
do the analysis, given enough time. He knew that it requires a scientist to understand how the
analysis functions. He wanted to develop an examiner’s mind to be able to solve a problem, not
train a technician to push buttons.
A background in science is essential to work as a forensic examiner. The minimum require-
ment for most entry-level forensic laboratory positions is a degree in a hard or physical science.
It was not until recently that forensic science was added to the list of accepted degrees. Additionally,
a demonstrable minimum number of credit hours in chemistry and physics is required as part
of the applicant’s course work. These requirements are in place to ensure that an entry-level
person had a basic understanding of science to build a forensic scientist from.
Finally, my degree is in criminalistics. In the early 1980s, no one knew what a criminalist
or a forensic scientist was. Because a degree in chemistry was a requirement, every job appli-
cation had a letter from the Chemistry Department Chairman stating that I had the equivalent
course work to an ACS-certified degree in chemistry. This was in addition to a copy of my college
transcripts.
This rambling story does relate to Basic Principles of Forensic Chemistry. It has to do with
the way the book is organized. Basic Principles of Forensic Chemistry is designed to develop
the student’s understanding of forensic chemistry in a sequential manner. Basic chemistry
principles are established. Generic examination techniques are presented followed by specific
applications. Each section builds on the information developed in the previous sections.
The focus of Basic Principles of Forensic Chemistry is on the analysis of controlled substances,
specifically drugs of abuse. However, it provides all of the conceptual information used in any
forensic chemistry section of a modern forensic laboratory. The science and the examination
techniques discussed are as applicable to the analysis of drugs as they are to trace evidence.

vii
viii Foreword

Specific reagents may change or sample preparation techniques may be modified, but the concepts
are interchangeable.
Part I lays the scientific foundation that the examiner needs to understand the science of
analysis. The information in Part I reviews basic principles of chemistry beginning with atomic
structure and expanding through molecules and into organic chemistry. The section is intended
to be a review of chemistry basics, not a replacement for formal class work.
Part II discusses the tools used by all examiners in the forensic chemistry section. Chapters
5 and 6 establish the terminology and paperwork flow common to all forensic chemistry sec-
tions. The following chapters discuss analytical techniques. Each chapter begins with generic
theory and follows it with drug-analysis applications. Chapters 7 through 9 discuss the use of
nonspecific tests and sample preparation techniques that are used as part of the screening pro-
cess. Each section presents the basis for the examinations followed by sections of practical
application. Chapters 10 and 11 address the instrumentation frequently used by drug chemists
to confirm the identity of the controlled substance indicated by the screening process. The fol-
lowing Chaps. 8 and 9 are theoretical discussions on practical application. Additionally, the
strengths and weaknesses of each instrument are addressed.
Part III deals with the job at hand, specifically the different types of controlled substances
encountered by forensic drug chemists. This section divides the controlled substances into
generic categories based on structural similarities. Each chapter addresses the drugs most fre-
quently encountered in the group under discussion. In turn, a brief history of topic drugs is
provided along with pharmacological information and the analytical techniques used to iden-
tify them.
Part IV concentrates on the most challenging portion of a forensic drug chemist’s job, clan-
destine laboratory operations. These operations force the forensic chemist out of the clinical
analytical mindset. This type of analysis requires the chemist to utilize his knowledge of chem-
istry (Part I), combine it with analytical tools (Part II), and understand drugs of abuse (Part III).
These examinations allow the drug chemist to use all the tools in his toolbox, along with
deductive reasoning, to objectively examine and evaluate the data from evidence obtained from
suspected clandestine drug labs.
As you can see, Basic Principles of Forensic Chemistry is a process. A foundation of chemi-
cal knowledge supports an analytical scheme. The tools from the analytical toolbox are used
to initially identify a generic class of drug followed by a specific compound identification.
Finally, the chemist’s complete knowledge base and power of deductive reasoning are used to
bring calm from the chaos of the evidence obtained from clandestine lab operations.
Basic Principles of Forensic Chemistry will not turn the reader into a forensic chemist.
However, it will provide the fundamental knowledge required to begin a very rewarding journey.
Good luck on your journey.

Chesterfield, VA Donnell R. Christian, Jr.

Preface

I have not reinvented the wheel on forensic chemistry in this book. This book is merely an
effort to consolidate previously developed, yet scattered, forensic chemistry-related informa-
tion under one umbrella. I used all reliable resources that my predecessors and contemporary
experts in the field of forensic chemistry have developed. For this reason, I consider myself an
editor rather than an author of this book. The material presented is very basic and is not intended
or recommended for legislative use.
Primarily, this book is a milestone textbook toward teaching forensic chemistry at colleges
and universities. Second, it is the first major, consolidated resource book for forensic laborato-
ries throughout the country and overseas to train newly hired staff in controlled substance
examination. I have developed a parallel laboratory manual with the book. The laboratory
manual has 17 experiments that are exclusively designed to provide initial training to students
and trainees of forensic chemistry. I also have developed an instructional PowerPoint presenta-
tion to assist instructors when teaching this course. This presentation is available to instructors
at no extra cost.
Unlike many other chemistry books, most of the questions at the end of each chapter in this
book pertain to court testimony. The answers to these questions affect many lives positively or
negatively. For this reason, I wanted the students of forensic chemistry to learn to answer court
testimony-related questions.
This book has room for improvement. I would like your suggestions, complaints, compli-
ments, or concerns about the book. Please do not hesitate to drop me a line with suggestions
for improvements to the future editions of this book.

Illustrations

I have used many original illustrations in this book.

I owe a special thanks to my forensic community at large for providing me hundreds of
valuable original photos and illustrations for this book. If I ever requested one photo, I was
given ten photos to choose from. Thank you once again.
In addition, GCMS and FTIR instrument manufacturers such as Varian Instruments, Avatar
(Nicolet) Instruments, HP Instruments, and Agilent Instruments have generously permitted the
use of photos of their instruments for this book. Thank you all.

ix
x Preface

I also used some photos from the public domain (citizen information centers) of US
DOJ-DEA and other (forensic-related public domains) websites. Thank you for posting
valuable photos on your websites for educational purposes. Microgram also permitted me to
use illustrations.
I am thankful to all of you for permitting the use your material for this book. This book
would not be in its current form without your generous contributions.
I always respected the copyrights and have avoided the use of any copyrighted material
without permission in this book.

Riverside, CA JaVed I. Khan

Acknowledgments

Many selfless and silent individuals are behind a successful individual. Although I do not
consider myself so successful, I do consider myself fortunate to be surrounded by the many
silent, selfless, giving, and encouraging individuals of the forensic community.
I owe a special thanks to the forensic community at large for their support and assistance
from various angles. Your contributions have made this book very valuable and resourceful.
California Department of Justice (CA-DOJ)–Division of Law Enforcement (DLE)–Bureau
of Forensic Service (BFS) has invested and contributed in my professional growth and devel-
opment for many years. Thank you.
Joseph Rynearson and John DeHaan of the BFS are my role models. Both are the authors
of well-read books in the field of forensic science. My mentor, the late Alfred Moses, was also
a very inspiring soul.
I thank the entire BFS staff for their support. Bureau chief Lance Gima and assistant chiefs
Gill Spriggs and Eva Steinberger deserve my special thanks. My laboratory director, Gary
Asbury, placed various encouraging posters all around the laboratory for me. My supervisor,
Kristen Rager, provided me with unreserved support. Assistant laboratory directors Tom
Nasser, Elisa Mayo, Steven Secofsky, Glen Owens, and Caroline Kim supported me as well. I
thank Jerry Massetti of the California Criminalistic Institute (CCI) for his support and Waheed
Jawadi of the CCI library for dispatching requested material in a timely manner. I thank my
retired administrators Arthur Young, Mike White, Cecil Hider, and the late Jan Bashinsky.
I thank my colleagues Hillary Bantrup, Anatoly Zolatoryov, Chantalle Clement, Brian
Reinarz, Jennifer Dernoncourt, Bronwyn Weis, Gina Williams, and Larry Joiner for permitting
the use of their photos in this book, and Bertha Castro, Cosette Larsen, Christina Ramirez,
Alicia Lomas-Gross, David Wu, Marla Richardson, Michele Merritt, Rich Takanaga, Marianne
Stam, Paul Sham, Lourdes Peterson, Phil Palez, Jim Hall, Kim Kreuz, Lynn Melgoza, Donna
Merrill, John Bowden, Trina Duke-Robinson, Greg Crew, Frank Shagoya, Martin Romero,
Tom Abercrombie, Terry Fickies, Tory Johnson, Bill Matty, and Theresa Anderson at Riverside
Crime Laboratory for support and assistance. I learned much from all of my past and current
colleagues.
I thank my college colleagues Richard Collins, Lori Kildal, Camille Kraft, Richard Rowley,
Pat Gummo, Angela Seavey, Richard LeGarra, E. Ozolin, Brianna Aliabdi, John Schuler,
Nancy Politano, Jeff Splesky, Shelly Aguilar, and Randy Lim for support and assistance.
I thank my co-authors T.J. Kennedy and D.R. Christian who helped me improve the overall
outcome of this book. We made an awesome team. Thank you for believing in me.
My parents would be proud of my efforts if they were alive. But I feel their prayers are with
me forever.

xi
xii Acknowledgments

Best of all, my family members deserve the utmost credit and thanks. Knowing my life’s
goals and ambitions, they never demanded any time from me. They, instead, created a calm
home environment so I could work on the computer for hours without any disturbance or dis-
traction. Thank you Fatima, Ahmed, and Sadia for unconditional support and love. Yes, I love
you too.
JaVed I. Khan

My appreciation and respect to JaVed Khan for his leadership on this project. I would also like
to thank those individuals who took time to contribute to this project.
Thomas J. Kennedy

I would like to thank Mr. Khan and Mr. Kennedy for the opportunity to participate in this project.
I would also like to thank the people who researched the source documents used to reference
this work.
Donnell R. Christian, Jr.
About the Authors

Mr. Khan holds a master of science degree in biochemistry

from the University of California, Riverside, a master of science
degree in biochemistry from the University of Agriculture,
Faisalabad, Pakistan, and a bachelor of science in chemistry/
biology from B.Z. University, Multan, Pakistan. He has more
than 17 years of experience in the field of forensic sciences at
the California State Department of Justice in the Riverside
Crime Laboratory. He is an accomplished forensic scientist
whose expertise expands in various fields, including forensic
chemistry, forensic biology, and forensic toxicology. He has
authored a number of publications on related topics.
JaVed I. Khan Mr. Khan responded to hundreds of clandestine laboratory
operations as a clandestine laboratory field expert. He exam-
ined the evidence from thousands of clandestine laboratory operations. Mr. Khan testified in
various courts as a clandestine laboratory analyses expert witness. Mr. Khan is a recognized
expert witness in other fields of forensics and has appeared more than 300 times in federal,
state, and local county courts in this capacity.
Mr. Khan has more than 12 years of teaching experience as a part-time college instructor of
forensic chemistry and biology. He has developed curriculum of forensic chemistry, forensic
biology, and forensic toxicology courses for Mt. San Jacinto College in Riverside, California.
He is a dedicated professional whose insight and tireless efforts provided the driving force for
this project.

Mr. Kennedy holds a bachelor of science degree in

chemistry from the University of Rochester,
Rochester, NY and a master of science degree in
chemistry from California State Polytechnic
University, Pomona, CA. Mr. Kennedy is a former
police officer and has been teaching chemistry at
Victor Valley College since 1994. He has been chair-
man of the Department of Chemistry for the past
eight years. Mr. Kennedy is a passionate teacher
focused on student success.

Thomas J. Kennedy

xiii
xiv About the Authors

Donnell R. Christian is a PhD candidate at the University of

South Africa, holds a Masters in Criminal Justice from American
Military University and Bachelor’s degrees in Chemistry and
Police Administration from Northern Arizona University. He is
the author of Forensic Investigation of Clandestine Laboratories
(2003). His companion book, Field Guide to Clandestine
Laboratory Identification and Investigation (2004), provides a
ready reference for police, fire, and emergency responders who
potentially encounter clandestine labs in their daily activities. Mr.
Christian has published articles on the analysis, and the clandes-
tine manufacture and analysis, of controlled substances and has
Donnell R. Christian developed training programs for investigators, laboratory exam-
iners, and attorneys involved in the investigation, examination,
and prosecution of clandestine labs. He also authored a chapter concerning the analysis of
controlled substances in Forensic Science, An Introduction to Scientific and Investigative
Techniques (2002, 2005, 2009) and the forensic chemistry section in The Forensic Laboratory
Handbook, Procedures and Practices (2005, 2011).
Mr. Christian is the director of Forensic Programs at Professional Business Solutions, Inc.,
and is the former Forensic Science Development Coordinator for the United States Department
of Justice’s International Criminal Investigative Training Assistance Program (ICITAP). With
ICITAP, he has assisted in establishing forensic science programs in the developing democra-
cies of Armenia, Azerbaijan, Bosnia, Bulgaria, Georgia, Haiti, Kazakhstan, Kyrgyzstan,
Senegal, Turkmenistan, and Uzbekistan. Mr. Christian served as president and chairman of the
Board of Directors for the Southwestern Association of Forensic Scientists (SWAFS).
Additionally, he spent 15 years with the Arizona Department of Public Safety Crime Laboratory
specializing in forensic chemistry and trace analysis, with emphasis in the clandestine manu-
facture of controlled substances (i.e., drugs and explosives). He has responded to hundreds of
clandestine lab scenes, examined thousands of exhibits, and provided untold hours of
testimony.
Contents

Part I Introduction to Forensic Chemistry

1 Introduction .............................................................................................................. 3
1.1 Forensic Chemistry ......................................................................................... 3
1.2 Scientific Investigation .................................................................................... 4
1.3 Forensic Investigation ..................................................................................... 4
1.4 Properties of Matter ........................................................................................ 5
1.5 Physical Properties .......................................................................................... 5
1.6 Chemical Properties ........................................................................................ 6
1.7 Questions......................................................................................................... 7
2 Atomic Structure ...................................................................................................... 9
2.1 Introduction ..................................................................................................... 9
2.2 Periodic Table ................................................................................................. 9
2.3 Atomic Structure ............................................................................................. 10
2.4 Subatomic Particles ......................................................................................... 11
2.5 The Arrangement of Electrons in an Atom ..................................................... 12
2.6 Electron Configurations .................................................................................. 13
2.7 Periodic Trends: Understanding the Periodic Table........................................ 17
2.8 Isotopes ........................................................................................................... 18
2.9 Radioactivity ................................................................................................... 18
2.10 Types of Radioactive Decay............................................................................ 19
2.11 Nuclear Radiation: Forensic Applications ...................................................... 19
2.12 The Mole and Molar Mass .............................................................................. 20
2.13 Elements of Forensic Interest.......................................................................... 20
2.14 Questions......................................................................................................... 20
Suggested Reading ..................................................................................................... 21
3 Molecules .................................................................................................................. 23
3.1 Introduction ....................................................................................................... 23
3.2 Chemical Bonding ............................................................................................ 23
3.2.1 Ionic Bonds ......................................................................................... 23
3.2.2 Covalent Bonds ................................................................................... 24
3.2.3 Polar Bonds ......................................................................................... 25
3.2.4 Hydrogen Bonding .............................................................................. 26
3.2.5 Multiple Bonds.................................................................................... 26
3.3 Predicting Bond Types ...................................................................................... 27
3.3.1 Nonpolar Covalent Bonds ................................................................... 27
3.3.2 Polar Covalent Bonds .......................................................................... 27

xv
xvi Contents

3.3.3 Hydrogen Bonds ................................................................................. 27

3.3.4 Ionic Bonds ......................................................................................... 27
3.4 Molar Mass ....................................................................................................... 27
3.5 Molarity............................................................................................................. 28
3.6 Chemical Reactions .......................................................................................... 28
3.7 Questions........................................................................................................... 29
4 Organic Chemistry................................................................................................... 31
4.1 Introduction ..................................................................................................... 31
4.2 Classification of Organic Compounds: Functional Groups ............................ 31
4.2.1 Alkanes ............................................................................................. 32
4.2.2 Alkenes ............................................................................................. 37
4.2.3 Alkynes ............................................................................................. 39
4.2.4 Aromatic Compounds ....................................................................... 40
4.2.5 Alcohols ............................................................................................ 41
4.2.6 Ketones ............................................................................................. 44
4.2.7 Aldehydes ......................................................................................... 46
4.2.8 Carboxylic Acids .............................................................................. 47
4.2.9 Esters................................................................................................. 49
4.2.10 Nitro Compounds.............................................................................. 50
4.2.11 Amines .............................................................................................. 51
4.3 Methyl Group (–CH3) ..................................................................................... 54
4.4 Compounds Containing Multiple Functional Groups ..................................... 54
4.5 Chirality .......................................................................................................... 55
4.6 Questions......................................................................................................... 56
Suggested Reading ..................................................................................................... 57

Part II Tools of Forensic Chemistry

5 Forensic Language .................................................................................................. 61

5.1 Defining Drugs ................................................................................................ 61
5.2 Origin of Drugs (Narcotics) ............................................................................ 61
5.2.1 Natural Drugs ...................................................................................... 61
5.2.2 Synthetic Drugs ................................................................................... 61
5.2.3 Psychotropic Drugs (Mind Altering) .................................................. 61
5.3 Dependence and Addiction ............................................................................. 62
5.3.1 Physical Dependence .......................................................................... 62
5.3.2 Psychological Dependence ................................................................. 62
5.4 Drug Abuse ..................................................................................................... 63
5.5 Hazards of Drug Abuse ................................................................................... 63
5.6 Structural Relationships .................................................................................. 64
5.6.1 Analogs ............................................................................................... 64
5.6.2 Designer Drugs ................................................................................... 64
5.6.3 Isomers ................................................................................................ 65
5.7 Controlled Substance Statutes......................................................................... 66
5.7.1 Controlled Substances Act .................................................................. 66
5.7.2 Controlled Substances Laws ............................................................... 66
5.7.3 Controlled Substance: Charges and Offenses ..................................... 67
5.8 Controlled Substance Submission to Crime Laboratories .............................. 67
5.9 Drug Cases in Crime Laboratories .................................................................. 68
5.10 Examination of Controlled Substances ........................................................... 69
5.11 Usable Quantity .............................................................................................. 69
5.12 Court Testimony.............................................................................................. 69
5.13 Qualifications and Education .......................................................................... 69
5.14 Questions......................................................................................................... 70
Suggested Reading ..................................................................................................... 70
Contents xvii

6 Forensic Documentation .......................................................................................... 71

6.1 Introduction ..................................................................................................... 71
6.2 Chain of Custody ............................................................................................ 71
6.3 Case Notes ...................................................................................................... 72
6.3.1 Types ................................................................................................... 72
6.3.2 Purpose ................................................................................................ 74
6.3.3 Content ................................................................................................ 74
6.3.4 Format ................................................................................................. 75
6.3.5 Dissemination...................................................................................... 75
6.4 Case Report ..................................................................................................... 75
6.4.1 Purpose ................................................................................................ 75
6.4.2 Format and Content ............................................................................. 75
6.5 Examples ......................................................................................................... 76
6.5.1 Example One ....................................................................................... 76
6.5.2 Example Two ...................................................................................... 76
6.6 Questions......................................................................................................... 76
Suggested Reading ..................................................................................................... 77
7 Chemical Screening.................................................................................................. 79
7.1 Introduction ..................................................................................................... 79
7.2 Chemistry of Color Formation ........................................................................ 79
7.3 Limitations of Chemical Color Tests .............................................................. 81
7.4 Chemical Color-Test Methods ........................................................................ 81
7.5 Documentation ................................................................................................ 82
7.6 Chemical Color Tests ...................................................................................... 82
7.6.1 Chen’s Test........................................................................................ 82
7.6.2 Dille–Koppanyi’s Test ...................................................................... 83
7.6.3 Mecke’s Test ..................................................................................... 83
7.6.4 Marquis’ Test .................................................................................... 84
7.6.5 Nitric Acid Test................................................................................. 85
7.6.6 Primary Amine Test .......................................................................... 86
7.6.7 Secondary Amine Test ...................................................................... 86
7.6.8 Tertiary Amine Test .......................................................................... 86
7.6.9 Van-Urk’s Test .................................................................................. 86
7.6.10 Duquenois–Levine Test .................................................................... 87
7.6.11 Froehde’s Test ................................................................................... 87
7.6.12 Janovsky Test .................................................................................... 87
7.6.13 Weber Test ........................................................................................ 88
7.7 Summary of Chemical Color Tests ................................................................. 88
7.8 Questions......................................................................................................... 90
Suggested Reading ..................................................................................................... 90
8 Microcrystal Techniques ......................................................................................... 91
8.1 Introduction ....................................................................................................... 91
8.2 Advantages of Microcrystal Techniques ........................................................... 91
8.3 Disadvantages of Microcrystal Techniques ...................................................... 92
8.4 Documentation .................................................................................................. 92
8.5 Microcrystal Test Techniques ........................................................................... 94
8.5.1 Aqueous Test Technique ..................................................................... 94
8.5.2 Volatility Test Technique..................................................................... 95
8.5.3 Acid and Anionic Test Technique ....................................................... 95
8.6 Aqueous Test Reagents ..................................................................................... 95
8.6.1 Gold Chloride Test .............................................................................. 95
8.6.2 Gold Chloride in Phosphoric Acid Test .............................................. 95
8.6.3 Platinum Chloride Test........................................................................ 96
xviii Contents

8.6.4 Mercuric Iodide Test ........................................................................... 96

8.6.5 Mercuric Chloride Test ....................................................................... 96
8.6.6 Potassium Permanganate Test ............................................................. 96
8.6.7 Sodium Acetate Test ........................................................................... 96
8.7 Critical Considerations.................................................................................... 96
8.8 Questions......................................................................................................... 97
Suggested Reading ..................................................................................................... 97
9 Chemical Extractions and Sample Preparation .................................................... 99
9.1 Introduction ..................................................................................................... 99
9.2 Techniques ...................................................................................................... 99
9.2.1 Solid–Liquid Extraction ...................................................................... 99
9.2.2 Liquid–Liquid Extraction .................................................................... 100
9.2.3 Acid–Base Extraction .......................................................................... 101
9.2.4 Neutral Compound Extraction ............................................................. 102
9.3 Sample Preparation ......................................................................................... 103
9.4 Gas Chromatography/Gas Chromatography Mass Spectrometry ................... 103
9.5 Dry-Extraction Gas-Chromatography Modification ....................................... 104
9.6 Acid–Base-Extraction Gas-Chromatography Modification ............................ 104
9.7 Infrared Spectroscopy ..................................................................................... 104
9.8 Acid–Base-Extraction Infrared-Modification-I .............................................. 105
9.9 Acid–Base-Extraction Infrared-Modification-II ............................................. 105
9.10 Methanol Extraction........................................................................................ 105
9.11 Questions......................................................................................................... 106
Selected Reading........................................................................................................ 106
10 Chromatography and Mass Spectrometry ............................................................ 107
10.1 Introduction ..................................................................................................... 107
10.2 Chromatographic Techniques ......................................................................... 107
10.2.1 Paper Chromatography ...................................................................... 107
10.2.2 Thin-Layer Chromatography ............................................................. 109
10.2.3 Column Chromatography .................................................................. 110
10.2.4 Ion-Exchange Chromatography......................................................... 110
10.2.5 High-Performance Liquid Chromatography...................................... 111
10.2.6 Gas Chromatography ......................................................................... 112
10.2.7 Chromatography: Limitations ........................................................... 115
10.2.8 Interpretation of GC Chromatograms ................................................ 115
10.3 Mass Spectrometry.......................................................................................... 116
10.3.1 Ionization ........................................................................................... 117
10.3.2 Electron Impact ................................................................................. 117
10.3.3 Chemical Ionization........................................................................... 118
10.3.4 Mass Spectral Fragmentation ............................................................ 118
10.3.5 Mass Analyzers (Filters).................................................................... 119
10.3.6 Quadrupole Mass Analyzers.............................................................. 119
10.3.7 Magnetic Sector Mass Analyzers ...................................................... 123
10.3.8 Ion Trap Mass Analyzers ................................................................... 123
10.4 Advantages of Gas Chromatography Mass Spectrometry .............................. 124
10.5 Disadvantages of Gas Chromatography Mass Spectrometry .......................... 124
10.6 Questions......................................................................................................... 125
Suggested Reading ..................................................................................................... 125
11 Infrared Spectroscopy ............................................................................................. 127
11.1 Introduction ..................................................................................................... 127
11.2 Theory of Infrared Spectroscopy .................................................................... 127
11.3 Infrared Spectrum ........................................................................................... 129
Contents xix

11.4 Instrumentation ............................................................................................. 129

11.4.1 Dispersive Infrared Spectrometer.................................................... 129
11.4.2 Spectrometer Components .............................................................. 129
11.4.3 Spectrometer Design ....................................................................... 131
11.4.4 Limitations of Dispersive Infrared .................................................. 132
11.5 Fourier Transform Infrared Spectrometer ...................................................... 132
11.5.1 Spectrometer Components .............................................................. 133
11.5.2 Spectrometer Design ....................................................................... 133
11.5.3 Advantages of Fourier Transform Infrared Spectrometers ............. 134
11.5.4 Fourier Transform Infrared Sample Preparation Techniques .......... 134
11.6 Sampling Techniques .................................................................................... 136
11.6.1 Nujol Mull ....................................................................................... 136
11.6.2 Cast Film A ..................................................................................... 136
11.6.3 Cast Film B ..................................................................................... 136
11.6.4 Pellets .............................................................................................. 136
11.6.5 Synthetic Membrane Sample Cards ................................................ 137
11.7 Reflectance .................................................................................................... 137
11.8 Fourier Transform Infrared Spectroscopy ..................................................... 137
11.9 Advantages of Fourier Transform Infrared Spectroscopy............................. 137
11.10 Disadvantages of Fourier Transform Infrared Spectroscopy ........................ 137
11.11 Instrument Selection for Forensic Identification........................................... 137
11.12 Inorganic Analysis ........................................................................................ 138
11.13 Organic Analysis ........................................................................................... 139
11.14 Questions....................................................................................................... 141
Suggested Reading ..................................................................................................... 141

Part III Examination of Drugs/Narcotics

12 Cannabis ................................................................................................................... 145

12.1 Introduction ..................................................................................................... 145
12.2 History............................................................................................................. 145
12.3 Packaging for Forensic Examination .............................................................. 147
12.4 Forms of Cannabis .......................................................................................... 147
12.5 Psychoactive Ingredient .................................................................................. 147
12.6 Forensic Identification of Marijuana ............................................................... 149
12.6.1 Botanical Identification ..................................................................... 149
12.6.2 Macroscopic Properties ..................................................................... 149
12.6.3 Microscopic Identification ................................................................. 151
12.6.4 Chemical Identification (Duquenois–Levine Test) ............................ 151
12.6.5 Thin-Layer Chromatography ............................................................. 153
12.6.6 Gas Chromatography Mass Spectrometry ......................................... 154
12.7 Documentation ................................................................................................ 154
12.8 Questions......................................................................................................... 156
Suggested Reading ..................................................................................................... 156
13 Phenethylamines ...................................................................................................... 157
13.1 Introduction ..................................................................................................... 157
13.2 Methyl Derivatives .......................................................................................... 157
13.2.1 Amphetamine .................................................................................... 158
13.2.2 Methamphetamine ............................................................................. 159
13.2.3 Phentermine ....................................................................................... 161
13.3 Hydroxyl Derivatives ...................................................................................... 162
13.3.1 Phenylpropanolamine ........................................................................ 162
13.3.2 Ephedrine/Pseudoephedrine .............................................................. 163
13.3.3 Ephedra Plant: Introduction and History ........................................... 164
xx Contents

13.4 Ketone Derivatives .......................................................................................... 164

13.4.1 Cathinone ........................................................................................... 164
13.4.2 Methcathinone ................................................................................... 165
13.4.3 Khat ................................................................................................... 165
13.5 Methylenedioxy Derivatives ........................................................................... 166
13.5.1 3,4-Methylenedioxyamphetamine ..................................................... 167
13.5.2 3,4-Methylenedioxymethamphetamine ............................................. 167
13.6 Methoxy Derivatives ....................................................................................... 168
13.6.1 Mescaline ........................................................................................... 168
13.7 Analytical Methods ......................................................................................... 170
13.7.1 Visual Inspection ............................................................................... 170
13.7.2 Chemical Screening ........................................................................... 170
13.7.3 Microcrystal Tests.............................................................................. 170
13.7.4 Extraction Techniques ....................................................................... 171
13.7.5 Extraction of Mescaline from Peyote ................................................ 172
13.7.6 Confirmatory Examination ................................................................ 172
13.8 Questions......................................................................................................... 175
Suggested Reading ..................................................................................................... 175
14 Tertiary Amines........................................................................................................ 177
14.1 Introduction ..................................................................................................... 177
14.2 Natural Tertiary Amines .................................................................................. 177
14.2.1 Cocaine .............................................................................................. 177
14.2.2 Opiates ............................................................................................... 179
14.3 Synthetic Tertiary Amines............................................................................... 182
14.3.1 Phenylcyclohexylpiperidine .............................................................. 182
14.4 Analytical Methods ......................................................................................... 183
14.4.1 Visual Inspections .............................................................................. 183
14.4.2 Chemical Screening of Tertiary Amines ........................................... 183
14.4.3 Confirmatory Examination ................................................................ 185
14.5 Questions ......................................................................................................... 190
Suggested Reading ..................................................................................................... 190
15 Tryptamines .............................................................................................................. 191
15.1 Introduction ..................................................................................................... 191
15.2 Natural Tryptamines ....................................................................................... 192
15.2.1 Psilocin and Psilocybin (Psychoactive Mushrooms) ......................... 192
15.2.2 Bufotenin ........................................................................................... 193
15.2.3 Methoxy Derivatives.......................................................................... 195
15.3 Synthetic Tryptamines .................................................................................... 197
15.4 Analytical Methods ......................................................................................... 197
15.4.1 Visual Identification........................................................................... 197
15.4.2 Chemical Screening Tests.................................................................. 198
15.4.3 Extraction of Psilocin and Psilocybin from Mushrooms ................... 199
15.4.4 Thin-Layer Chromatography ............................................................. 199
15.4.5 Gas-Chromatography Mass Spectrometry......................................... 199
15.5 Questions......................................................................................................... 205
Suggested Reading ..................................................................................................... 206
16 Anabolic Steroids ..................................................................................................... 207
16.1 Introduction and History ................................................................................. 207
16.2 Naturally Occurring Steroid Hormones .......................................................... 208
16.3 Anabolic Steroids ............................................................................................ 210
16.3.1 General Structure ............................................................................... 210
16.3.2 Physical and Psychological Effects ................................................... 211
Contents xxi

16.3.3 Methods of Administration................................................................ 211

16.3.4 Nomenclature of Anabolic Steroids .................................................. 211
16.3.5 Frequently Encountered Steroids ...................................................... 212
16.4 Analytical Methods ......................................................................................... 213
16.4.1 Visual Inspections .............................................................................. 213
16.4.2 Gas Chromatography Mass Spectrometry ......................................... 213
16.4.3 Mass Spectra of Commonly Encountered Steroids ........................... 214
16.5 Questions......................................................................................................... 222
Suggested Reading ..................................................................................................... 222
17 Miscellaneous Controlled Substances .................................................................... 223
17.1 Introduction ..................................................................................................... 223
17.2 Barbiturates ..................................................................................................... 223
17.3 Fentanyl........................................................................................................... 225
17.4 Gamma-Hydroxybutyric Acid: g-Hydroxybutyric Acid ................................. 226
17.5 Ketamine ......................................................................................................... 227
17.6 Lysergic Acid Diethylamide ........................................................................... 228
17.7 Analytical Methods ......................................................................................... 229
17.7.1 Visual Identification........................................................................... 229
17.7.2 Chemical Screening Tests.................................................................. 230
17.7.3 Gas-Chromatography Mass Spectrometry......................................... 230
17.8 Questions......................................................................................................... 237
Suggested Reading ..................................................................................................... 237

Part IV Clandestine Laboratory Operations

18 Clandestine Operations: Synthetic Methods, Hazards, and Safety ............... 241

18.1 Introduction ..................................................................................................... 241
18.2 Clandestine Operations ................................................................................... 241
18.2.1 Synthesis of Cocaine ......................................................................... 241
18.2.2 Synthesis of Fentanyl......................................................................... 242
18.2.3 Synthesis of g-Hydroxybutyric Acid ................................................. 242
18.2.4 Synthesis of Heroin ........................................................................... 244
18.2.5 Synthesis of Lysergic Acid Diethylamide ......................................... 245
18.2.6 Synthesis of 3,4-Methylenedioxymethamphetamine ........................ 246
18.2.7 Synthesis of Methcathinone .............................................................. 247
18.2.8 Synthesis of Phencyclidine ................................................................ 248
18.2.9 Synthesis of N,N-Dimethyltryptamine .............................................. 248
18.3 Synthesis of Methamphetamine: The Clandestine Operation of Choice ........ 249
18.3.1 Cold Method ...................................................................................... 249
18.3.2 Hot Method ........................................................................................ 251
18.4 Potential Hazards Associated with Clandestine Operations ........................... 253
18.5 Safety Considerations ..................................................................................... 253
18.6 Role of the Forensic Chemist at Clandestine Lab Sites .................................. 253
18.6.1 Advisory ............................................................................................ 254
18.6.2 Evidence Collection........................................................................... 254
18.7 Questions......................................................................................................... 254
Suggested Reading ..................................................................................................... 254
19 Evidence Identification and Collection .................................................................. 257
19.1 Clandestine Operations: A Forensic Analogy................................................. 257
19.2 Signs of Clandestine Operations ..................................................................... 257
19.3 Identification of Related Evidence .................................................................. 258
19.4 Solutions Frequently Encountered at Clandestine Sites ................................. 260
xxii Contents

19.5 Clandestine Production of Methamphetamine ................................................ 261

19.5.1 Extraction of Pseudoephedrine from Cold Tablets (Step I) ............... 261
19.5.2 Manufacturing of Methamphetamine (Step II).................................. 262
19.5.3 Processing of Methamphetamine (Step III) ....................................... 263
19.5.4 Icing of Methamphetamine (Step IV)................................................ 263
19.6 Collection of Evidence.................................................................................... 263
19.7 Collection of Washes ...................................................................................... 266
19.8 Questions......................................................................................................... 267
Suggested Reading ..................................................................................................... 267
20 Examination of Clandestine Evidence ................................................................... 269
20.1 Introduction ..................................................................................................... 269
20.2 Examination of Evidence to Prove Extraction (Step I) .................................. 269
20.2.1 Evidence Type ................................................................................... 269
20.2.2 Examination ....................................................................................... 270
20.3 Examination of Evidence to Prove Manufacturing
of Methamphetamine (Step II) .......................................................... 270
20.3.1 Evidence Type ................................................................................... 270
20.3.2 Examination ....................................................................................... 271
20.3.3 Confirmatory Examination ................................................................ 274
20.4 Examination of Evidence to Prove Processing
of Methamphetamine (Step III) ...................................................................... 274
20.4.1 Evidence Type ................................................................................... 274
20.4.2 Examination of Biphasic Solutions ................................................... 275
20.5 Examination of Evidence to Prove Icing (Step IV) ........................................ 275
20.6 Examination of Stains ..................................................................................... 277
20.7 Examination of Washes................................................................................... 278
20.8 Determining Methods of Methamphetamine Production ............................... 279
20.9 Questions......................................................................................................... 282
Suggested Reading ..................................................................................................... 282

Laboratory Manual ......................................................................................................... 283

Experiment # 2 ........................................................................................................... 286
Experiment # 3 ........................................................................................................... 288
Experiment # 4 ........................................................................................................... 290
Experiment # 5 ........................................................................................................... 292
Experiment # 6 ........................................................................................................... 298
Experiment # 7 ........................................................................................................... 300
Experiment # 8 ........................................................................................................... 304
Experiment # 9 ........................................................................................................... 310
Experiment # 10 ......................................................................................................... 312
Experiment # 11 ......................................................................................................... 314
Experiment # 12 ......................................................................................................... 316
Experiment # 13 ......................................................................................................... 320
Experiment # 14 ......................................................................................................... 323
Experiment # 15 ......................................................................................................... 325
Experiment # 16 ......................................................................................................... 328
Experiment # 17 ......................................................................................................... 332
Experiment # 18 ......................................................................................................... 335
Experiment # 19 ......................................................................................................... 338
Experiment # 20 ......................................................................................................... 341

Index .................................................................................................................................. 345