Arrhenius Theory Svante Arrhenius (Swedish) 1880s Acid - a substance that produces H+(aq)in solution Base - a substance that

produces OH(aq) in solution

Brnsted-Lowry Theory Johannes Brnsted (Danish) Thomas Lowry (English) 1923 Acid - a substance that donates protons (H+) Base - a substance that accepts protons (H+)

Proton Transfer Reaction H3O+(aq) + NH3(aq) 6 H2O(l) + NH4+(aq)

In general terms, all acid-base reactions fit the general pattern HA acid + B A base + HB+

Conjugate Acid-Base Pairs L When an acid, HA, loses a proton it becomes its conjugate base, A, a species capable of accepting a proton in the reverse reaction. HA acid L + A conjugate base H+

When a base, B, gains a proton, it becomes its conjugate acid, BH+, a species capable of donating a proton in the reverse reaction. B + base H+ HB+ conjugate acid

Acid-Base Reactions L We can analyze Brnsted-Lowry type proton transfer reactions in terms of conjugate acid-base pairs. The generic reaction between HA and B can be viewed as HA A + H+ H+ + B HB+ HA + B A + HB+ acid1 base2 base1 acid2 Species with the same subscripts are conjugate acid-base pairs.

Acid Hydrolysis and the Role of Solvent Water L When any Brnsted-Lowry acid HA is placed in water it undergoes hydrolysis to produce hydronium ion, H3O+, and the conjugate base, A, according to the equilibrium: HA acid1 + H2O base2 A + H3O+ base1 acid2

The acid HA transfers a proton to H2O, acting as a base, thereby forming the conjugates A and H3O+, respectively. The position of this equilibrium indicates the strength of the acid. HCl + H2O acid1 base2 Cl + H3O+ base1 acid2 Ka >> 1

Equilibrium lies right. Y HCl is a strong acid. HOAc + H2O acid1 base2 OAc + H3O+ base1 acid2 Ka = 1.8 105

Equilibrium lies left. Y HOAc is a weak acid.

Base Hydrolysis and the Role of Solvent Water L Hydrolysis of a base also involves water as an active participant, functioning as an acid. B + H2O base1 acid2 HB+ + OH acid1 base2

H2O acts as the acid, transferring a proton to B, thereby forming the conjugates OH and HB+, respectively. The position of this equilibrium indicates the strength of the base. + H2O O2 base1 acid2 OH + OH acid1 base2 Kb >> 1

Equilibrium lies right. Y O2 is a strong base. NH3 + H2O base1 acid2 NH4+ + OH acid1 base2 Kb = 1.8 105

Equilibrium lies left. Y NH3 is a weak base.

Strongest Acid and Base L In Brnsted-Lowry theory, the strongest acid and strongest base that can exist in a protonic solvent is defined by the solvent<s autoprotolysis reaction. 2 H2O(l) H3O+ strongest acid 2NH3(l) NH4+ strongest acid OH strongest base + NH2 strongest base + Kw = 1.0 1014 at 25 oC K = 1.9 x 1033 at 50oC

Any stronger molecular acid or base is leveled to the strength of the strongest acid or base for the solvent. Any molecular acid or base that is completely dissociated in its solvent is a strong acid or base that has been leveled. Any acid or base that is only partially dissociated in its solvent is a weak acid or base and is not leveled. HCl + H2O H3O+ + Cl Ka >> 1 HF + H2O H3O+ + F Ka = 6.8 104 leveled not leveled

An ionic compound whose anion is the strongest base of the solvent is not leveled, but merely dissociated. NaOH Na+ + OH strong base solution but not leveling

Brnsted-Lowry Theory of NH3(l) L In NH3(l), any substance that reacts with NH3(l) to produce NH4+ in solution is an acid. HClO4 + NH3(l) NH4+ + ClO4 HOAc + NH3(l) NH4+ + OAc NH2CONH2 + NH3(l) NH4+ + NH2CONH strong acid strong acid weak acid

! HClO4 and HOAc are leveled to the strength of NH4+ in NH3(l). ! NH2CONH2 is not leveled. L In NH3(l), any substance that reacts with NH3(l) to produce NH2 in solution is a base. Na3N + 2 NH3 3 Na+ + 3 NH2 ! N3 is leveled to the strength of NH2 in NH3(l) L Any ionic salt that contains NH4+ or NH2 is an acid or base in NH3(l). acid solution in NH3(l) NH4Cl NH4+ + Cl NaNH2 Na+ + NH2 base solution in NH3(l) ! Dissociation of these ionic salts in NH3(l) is not leveling. strong base

Acid Strength in Non-aqueous Solvents ! In water, the well-known strong acids are equally strong, because they are completely dissociated (leveled): HClO4 = HCl = H2SO4 = HNO3 ! Differences in acid strength can be discerned in non-aqueous media. ! In glacial acetic acid, HOAc(l), these acids are not completely dissociated, being weaker than H2OAc+: 2 HOAc H2OAc+ + OAc K = 3.5 1015

! In HOAc(l) the acid strengths are in the following order: HClO4 > HCl > H2SO4 > HNO3

Solvent System Concept ! The solvent system concept of acid-base character can be applied to aprotic solvents that have significant autodissociation. L In the solvent system concept, an acid is a substance that produces the cationic species of the autodissociation, and the base is a substance that produces the anionic species of the autodissociation.

Example: Solvent system BrF3(l), m.p. = 9 oC, b.p. = 126 oC 2 BrF3 Acidic solution: SbF5 in BrF3 SbF5 + BrF3 SbF6 + BrF2+ Basic solution: F in BrF3 BrF3 + F BrF4 L Solvent system concept and the corollary leveling effect cannot be applied to non-dissociating solvents. ! For example, strengths of acids in hydrocarbon solvents depend mainly on the reactivities of the solute species, and little on the solvent itself. BrF2+ + acid BrF4 base

Lewis Acid-Base Theory G. N. Lewis - 1923 Lewis acid - an electron-pair acceptor Lewis base - an electron-pair donor T T T Lewis acids are electrophiles. Lewis bases are nucleophiles. The product of a Lewis acid-base reaction is often called an adduct.

Comparison of Theories T Acids and bases in Arrhenius and Brnsted-Lowry theories are also acids and bases in Lewis theory:
hydronium ion H O H H + + N H ammonia H H O H water H + H N H adduct ammonium ion H H +

e-pair acceptor e-pair donor = acid = electrophile = base = nucleophile

Some acid-base reactions in Lewis theory are not seen as such by the other theories: :NH3 + BF3 base acid 6 H3N:BF3 adduct

Examples of Lewis Acid-Base Reactions Co3+ acid SbF5 acid + 6 H2O 6 [Co(H2O)6]3+ base adduct + F base 6 [SbF6] adduct

CO2 + OH 6 HCO3 acid base adduct

Frontier Orbital Concept L The frontier orbital concept sees Lewis acid-base interactions in terms of the base donating an electron pair from its highest occupied molecular orbital (HOMO) into the acid's lowest unoccupied molecular orbital (LUMO).

BF3

F3B:NH3 *

NH3

LUMO HOMO D3h (a2")

C3v (a1)

HOMO-LUMO Model of NH4+ Formation

L L

In frontier orbital terms, a Lewis base has an electron pair in a HOMO of suitable symmetry to interact with the LUMO of the acid. The more similar the energies of the HOMO and LUMO the stronger the interaction will be.

Hydrogen Bonding ! Hydrogen bonding can be understood in terms of frontier orbital concepts. ! For a very strong hydrogen bond, such as in FHF, the LUMO of the acid species (HF) has comparable energy to the HOMO of the base species (F), resulting in a complex with a lower overall energy.

Variations in B@@@HA Interactions B HOMO << HA LUMO

HOMO HOMO B--HA

HA

! Bonding MO of B@@@HA only slightly more stable than HA HOMO ! Non-bonding n MO of B@@@HA much higher than B HOMO L B@@@HA energy higher (less stable) than separate B and HA energies, so no interaction. (Example: CH4 + H2O)

Variations in B@@@HA Interactions B HOMO . HA LUMO

HOMO

B--HA

HA

! Bonding MO of B@@@HA much more stable than HA HOMO ! Non-bonding n MO of B@@@HA much more stable than B HOMO L B@@@HA energy lower (more stable) than separate B and HA energies, so strong interaction. (Example: FHF)

Variations in B@@@HA Interactions B HOMO << HA HOMO B LUMO << HA LUMO

HOMO HOMO

BH+

A-

HA

! Extreme mismatch of B HOMO and HA LUMO with B HOMO < HA HOMO, so no MO formation L Proton transfer from HA to B favored (e.g., NH3 + HCl NH4+ + Cl)

Visible and UV Absorption Spectra of I2(g) and I2(soln) in Donor Solvents

UV/Vis of I2(g)

! The characteristic purple color of I2(g) is due to absorption at ~500 nm, due to promotion of electrons from the 4g* MO (HOMO) to the 9u* MO (LUMO).

Visible and UV Absorption of I2 in Donor Solvents ! Donor solvents form adducts with I2 through interaction of the solvents HOMO and iodines LUMO (9u*), causing the adduct LUMO to rise and shifting the absorption to higher energy (blue shift). N Donor-acceptor transition is g* u*. N Charge transfer (CT) band results from adduct u u* promotions.

Non-donor Solvents ! Non-donor or weak donor solvents do not have effective HOMOLUMO interactions, so visible absorption is similar to that of I2(g). N Solutions in hexane and benzene have purple color similar to I2(g)

Strong Donor Solvents ! Strong donors have effective LUMO-HOMO interactions between I2 (acid) and the solvent (base). N This causes greater energy separation between the adduct HOMO and LUMO, shifting the donor-acceptor visible absorption to higher energy (blue shift).

Uv/vis Spectra of I2 in Donor Solvents N Solution colors in strong donor solvents like methanol, water, or aqueous KI (where I3 forms) are yellow or brown.