Acid-Base and Donor-Acceptor Chemistry

CHAPTER 6

Textbook: Inorganic Chemistry

Gary L. Miessler, Paul J. Fischer, Donald A. Tarr
Fifth Edition

Lecturer: Prof. Dr. M. Kasım ŞENER

Concepts of Acid-Base Chemistry

Several models have been developed to classify, rationalize and predict the reactivity of acid-base
pairs (or donor-acceptor pairs).

• Arrhenius Concept- acids give hydrogen ions in aqueous solution and bases give hydroxide in
aqueos solution
• Brønsted-Lowry Concept- acids are hydrogen ion donors and bases are hydrogen ion acceptors
• Lewis Concept- acids are electron-pair acceptors and bases are electron-pair donors
• Electrophile-Nucleophile Concept- acids are electrophilic reagents and bases are nucleophilic
reagents
• Lux-Flood Concept- acids are oxide acceptors (O2-) and bases are oxide donors
• Usanovich Concept- an acid-base reaction is a reaction leading to formation of a salt
Arrhenius Concept

Acids form hydrogen ions in aqueous solution and bases form hydroxide in aqueos solution

HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l) (acid-base reaction)

HCl(aq) → H+(aq) + Cl-(aq) (acid) H+ really more like H3O+
NaOH(aq) → Na+(aq) + OH-(aq) (base)

• Good fundamental definition of acids and bases for aqueous solution

• Of limited use in non-aqueous solvents or the gas phase where dissociation does not ocur
• Also fails to capture analogous reactivity of substances that don’t dissociate into H+ or OH-, what do
you do about NH3?
Brønsted-Lowry Concept

Acids release hydrogen ions and bases take up hydrogen ions

HCl + H2O ↔ H3 O+ + Cl-

acid base acid base
strong weak weaker very weak

• Conjugate acids and bases- when an acid gives up a hydrogen ion, it forms the conjugate base
• Acid-base reactions always proceed to form the weaker acid/base pair
• The Brønsted-Lowry model accommodates non-aqueous solvents and gas-phase reactions

NH4+ + NH2- → 2NH3 (in NH3)

NH4+ → H+ + NH3 (in NH3) NH2- + H+ → NH3 (in NH3)

acid base
Solvent System Concept

This concept for acid-base reactivity was developed for solvents that can dissociate into cations (acid)
and anions (base)

2H2O ↔ H3O+ + OH-

acid base

• Now we can say that sulfuric acid is an acid because it increases the concentration of H3O+

H2SO4 + H2O → H3O+ + HSO4-

• On the other hand, ammonia is a base because it increases the concentration of OH-

NH3 + H2O ↔ NH4+ + OH-

Many solvents dissociate to some degree:
Lewis Acid-Base Concept

A base is an electron-pair donor and an acid is an electron-pair acceptor

• This model is consistent with the Arrhenius and Brønsted-Lowry Models:

acid base
H+ + :NH3 → NH4+
Lewis Lewis
Acid Base

• It also works with molecules that neither give up nor accept a hydrogen ion

BF3 + :NH3 → F3B:NH3

Lewis Lewis Adduct
Acid Base
The Lewis Concept also allows us to describe coordination complexes within acid-base framework.

Ag+ + 2 :NH3 → H3N→Ag+←NH3

Lewis Acid Lewis Base

Coordinate covalent or dative bond- used to show

that both electrons in the bond come from a Lewis base

• Lewis Acid-Base adducts in which the Lewis acid is a metal ion are typically called coordination
compounds
The Lewis Concept and Frontier Orbitals

The Lewis concept of acids and bases is readily interpreted using molecular orbital theory.

N-B σ*

An acid-base reaction occurs

driving force for when HOMO of the base and
adduct formation LUMO of the acid combine to
create new HOMO and
LUMO in the product.
N-B σ

A fascinating aspect of the Lewis model is that a single species can act as an oxidizing agent, a Lewis
acid, a Lewis base, or a reducing agent, depending on the other reactant (Example 1).
Hard and Soft Acids and Bases (Pearson’s HSAB Concept)

The hard-soft acid-base concept seeks to understand the reactivity of Lewis acids and bases
according to the polarizability of their valence electrons (i.e., their deformability by other
molecules/ions).

• hard Lewis acids are small acids with a high positive charge
• soft Lewis acids are larger and typically have a lower positive charge or no charge
• hard Lewis bases are small bases with highly electronegative donor atoms
• soft Lewis bases are larger and typically have smaller electronegativities

• Hard acids prefer to interact with hard bases, soft acids prefer to interact with soft bases

ZnO + 2 LiC4H9 → Zn(C4H9)2 + Li2O

borderline acid hard acid borderline acid hard acid
hard base soft base soft base hard base
HSAB Concept and Exchange Reactions

HSAB theory is consistent with the large differences in Keq for simple exchange reactions:

Hg2+ is soft acid. As the halide becomes softer, the reaction becomes increasingly favorable
HSAB Concept and Solubilities

Because the dissolution of salts in water typically requires the replacement of a Lewis base with water,
HSAB can predict trends in solubilities. Consider the silver halides:

H2O
AgX(s) ↔ Ag+(aq) + X-(aq)

X= F >> Cl > Br >I

very soluble insoluble
• Fluoride and chloride are hard bases; however, so is water. It turns out that water is softer than
fluoride but harder than chloride
• Bromide and iodide are soft bases
• Because Ag+ is a soft acid, it is less prone to give up the halide as we move down the series
HSAB Concept and Solubilities

Lithium halides show the opposite trend:

LiX(s) ↔ Li+(aq) + X-(aq)

X= F << Cl < Br <I

insoluble very soluble
• Fluoride and chloride are hard bases; however, so is water. It turns out that water is softer than
fluoride but harder than chloride
• Bromide and iodide are soft bases
• In this case Li+ is a hard acid and it prefers to interact with the hardest base available
HSAB Concept and Metal Thiocyanate Complexes

In coordination complexes the metal is the Lewis acid. The Lewis base is normally called a ligand.

• Thiocyanate (SCN-) is an interesting ligand because there are two Lewis base sites:

‘linkage isomerism’

M is Hg2+ M is Zn2+
Hg2+ is soft Zn2+ is borderline acid
Pearson’s Absolute Hardness Scale

The absolute hardness is defined as

η=I–A/2

• I is the ionization energy of the molecule in eV, approximately equal to -EHOMO

• A is the electron affinity of the molecule in eV, approximately equal to -ELUMO
• So the absolute hardness is just half the HOMO-LUMO difference
• Hard acids have large values for η, soft acids have smaller values for η
• Softness of a donor atom is given by the inverse of hardness:

σ=1/η
The Nature of Adduct

Hard acid/hard base adducts tend to have more ionic character in their bonding. These are generally
more favored energetically. Soft acid/soft base adducts are more covalent in nature.
Acid/Base Strength

It is important to realize that hard/soft considerations have nothing to the to do with acid or base
strength. An acid or a base may be hard or soft and also be either weak or strong.
In a competition reaction between two bases for the same acid, one must consider both the relative
strength of the bases, and the hard/soft nature of each base and the acid.

ZnO + 2 LiC4H9 → Zn(C4H9)2 + Li2O

borderline acid hard acid borderline acid hard acid
hard base soft base soft base hard base
Zinc ion is a strong Lewis acid, and oxide ion is a strong Lewis base, suggesting the reaction is
unfavorable as written.
However, the reaction proceeds to the right (K > 1), because hard/soft considerations override acid-
base strength considerations.
Drago’s EC Approach

A quantitative system for calculating the termodynamics of acid-base reactions takes account of both
covalent and ionic components of the acid-base interaction. For the reaction
∆H
A + B ↔ AB
-∆H = EAEB + CACB
∆H- enthalpy of reaction in the gas phase or in an inert solvent
EA and EB are the capacity for electrostatic (ionic) interactions of the acid and base
CA and CB are the capacity for covalent interactions of the acid and base
I2 is reference acid with CA = EA = 1.00 kcal/mol
Reference bases are N,N-dimethylacetamide (EB = 1.32) and Diethyl sulfide (CB = 7.40)
Using the EC Model

The enthalpy of a given Lewis acid-base reaction can be determined using tabulated values.

I2 + C6H6 ↔ I2.C6H6
Lewis acid Lewis base Adduct
-∆H = EAEB + CACB
∆H = -1.21 kcal/mol within 9% of experimental value
Halogen Bonds

The coordinate covalent bonds formed by the halogens (X2, as Lewis acids) and interhalogens (XY, for
example, ICl) to Lewis bases are called halogen bonds.
Summary

• There are several models to describe acids and bases. The Lewis model is one of the most general
since it doesn’t depend on the transfer of a hydrogen ion.
• A dative bond (coordinate covalent bond) is often used to denote a bond between a neutral Lewis
base and a Lewis acid.
• The Lewis model is readily interpreted using MO theory: the HOMO of the Lewis base interacts with
the LUMO of the Lewis acid.
• HSAB provides a semi-quantitative method for understanding trends in acid-base reactivity: hard
acids like hard bases and soft acids like soft bases.
• The Drago EC model provides a more quantitative method for understanding the thermodynamics
of an acid-base reaction.
Acid-Base Strength

We have seen that the reactivity of acids and bases can be viewed through the HSAB model or the
EC model.
• Both of these models try to provide a conceptual framework to explain empirical observations about
acid-base reactivity.
• To determine the actual strength of an acid or of a base, different measurements can be made

o calorimetric measurements of reaction enthalpies (direct)

o temperature dependence of Keq (direct)
o spectroscopic measurements (IR, NMR, UV-Vis) (indirect)
Direct Thermodynamic Measurements

For reactions that go to completion, the enthalpy of the reaction can be determined directly from
calorimetry.

HNO3 + H2O → NO3- + H3O+

If a reaction does not go to completion, the procedure is a little complicated:

CH3COOH + H2O ↔ CH3COO- + H3O+ ∆H = ∆H1 - ∆H2

A traditional strategy is to apply Hess’s law using thermodynamic data from reactions that essentially
go to completion.
CH3COOH + OH- → CH3COO- + H2O ∆H1
H3O+ + OH- → 2 H2O ∆H2
Another alternative is to measure the temperature dependence of Keq

∆G = ∆H - T∆S = -RTlnKeq
lnKeq = - ∆H/RT + ∆S/R (van’t Hoff equation)

So a plot of lnKeq vs 1/T gives a straight line, y = mx + b

slope = m = - ∆H/R intercept = b = ∆S/R

∆H = -mR = 2.8 kJ/mol

∆S = bR = -100 J/mol K
Gas Phase Proton Affinity

Proton affinity is a thermodynamic measurements conducted in the gas phase:

BH+(g) → B(g) + H+(g) ∆H = Proton Affinity (PA)

These mesurements give us a ‘pure’ view of base/acid strength, without complications from solvent
effects (solvation).

Acidity of binary
hydrogen compounds
Trends in acidity and electronegativity of binary hydrides
Substituents Effects-Electronic

Gas phase proton affinity measurements make it easy to examine how substituent changes can
impact acidity/basicity.

highest proton affinity NMe3 > NHMe2 > NH2Me > NH3 lowest proton affinity

This trend is an example of an inductive electronic effect. CH3 is more electron releasing than H,
making the nitrogen lone pair more basic.

Inductive effects tend to be fairly weak and can be overridden by π effects, for example in the boron
halide acids,

weakest acid BF3 < BCl3 ≤ BBr3 strongest acid

The best π bonding occurs between B and F, which overrides any inductive effect from the
electronegative fluorine and quenches the Lewis acidity of BF3
Substituents Effects-Electronic

Another example is both gas-phase and aqueous basicity of aromatic amines:

Substituents Effects-Steric

Gas phase proton affinity measurements make it easy to examine how substituent changes can
impact acidity/basicity.

highest proton affinity NMe3 > NHMe2 > NH2Me > NH3 lowest proton affinity

Sterics can influence or override electronic trends in basicity (or acidity). When the gas phase
measurement is made for bulky Lewis acids, different trends are observed:

highest BF3 affinity NHMe2 > NH2Me > NMe3 > NH3 lowest BF3 affinity

highest BMe3 affinity NHMe2 > NH2Me > NMe3 > NH3 lowest BMe3 affinity

highest BtBu3 affinity NH2Me > NH3 > NHMe2 > NMe3 lowest BtBu3 affinity
Substituents Effects-Steric

In this example, one might expect 2-tert-butylpyridine to be more basic than 2-methylpyridine on the
basis of inductive effects, but the tertiary butyl steric bulk attenuates the basicity on steric grounds by
making the nitrogen less accessible and more difficult to solvate upon protonation.

basicity ranking in
aqueous solution
Frustrated Lewis Pairs (FLPs)
Metals as Acids

Metals can act as Lewis acids, readily forming adducts with Lewis bases. These adducts are called
coordination compounds. When the ligand (Lewis base) is water, the following secondary acid-base
reactions can occur:

[Cr(H2O)6]3+ + H2O → [Cr(H2O)5(OH)]2+ + H3O+ pKa = 3.8

Salts of small, highly charged metal cations are acidic.

δ+
The alkali metal cations show essentially no acidity, the alkaline
δ-
earth metal cations show it only slightly, 2+ transition-metal
ions are weakly acidic, 3+ transition-metal ions are moderately
acidic, and ions that would have charges of 4+ or higher as
monatomic ions are such strong acids in aqueous solutions that
they exist only as oxygenated ions.
Metals as Acids

[M(H2O)6]3+ + H2O → [M(H2O)5(OH)]2+ + H3O+

Oxyacids

The acid strength of the oxyacids of chlorine in aqueous solution rank as

HClO4 > HClO3 > HClO2 > HOCl

As the number of oxygen atoms increases, oxyacid acid strength increases. Because, The
electronegativity of a terminal oxygen atom is greater than the group electronegativity of OH which
makes the heterolytic cleavage easy. Another reason is that the negative charge of oxyacid conjugate
bases is stabilized by delocalization. The conjugate base is stabilized to great extent as the number
of O atoms increases for this negative charge delocalization. The more effectively the negative charge
is delocalized, the weaker the conjugate base, and stronger the acid.
Superacids

Superacids are acids more acidic than pure sulfuric acid. Some are capable of protonating nearly
anything, including hydrocarbons (they can dissolve candles).

Fluoroantimonic acid
(HF-SbF5)

Strongest superacids are formed by mixing strong Brønsted and Lewis acids.
• strongest known superacid (1016 times stronger than sulfuric acid)
• very loosely held (‘naked’) proton is highly reactive
• very stable conjugate base (SbF6-) promotes proton transfer
Superbases

Superbases have been classified as those with gas-phase proton affinities > 1000 kJ/mol. Examples of
organic superbases which are weak bases in water but exhibit superbasic characteristics in organic
solvents are given below:

PA = 1048 kJ/mol

The alkali metal hydroxides, of equal basicity in aqueous solution, have proton affinities in the order
LiOH (1000 kJ/mol) < NaOH < KOH < CsOH (1118 kJ/mol).
Solvation Effects

Solvents have a huge impact on the observed strength of acids and bases. Compare these trends in
gas-phase proton affinities and aqueous pKb values:

Gas Phase Proton Affinity

highest proton affinity NMe3 > NHMe2 > NH2Me > NH3 lowest proton affinity

Aqueous pKb
strongest base NHMe2 > NH2Me > NMe3 > NH3 weakest base

These differences arise because of water’s ability to solvate and hydrogen bond to the resulting
ammonium cation, NHR3+
Solvation Effects

Because water is a strong hydrogen bond donor and acceptor, it has a strong influence on acid-base
properties. Consider how the following acid pKa values differ between water and DMSO:

water HA pKa (H2O) pKa (DMSO)

Dimethylsulfoxide
HCl -8.0 1.8 (DMSO)

H2SO4 -3.0 1.99

CH3COOH 4.76 12.3

PhOH 9.95 18.0

Leveling Effect

Another role that solvents play is to level the strength of an acid or base. This effect is a function of the
solvent auto-dissociation

2 H2O ↔ H3O+ + OH-

In water, the strongest acid you can have is H3O+. A stronger acid, like HCl, protonates a water
molecule to make H3O+, thus leveling the strength of HCl.

HCl + H2O → H3O+ + Cl-

100% in 0.1 M solution

HNO3 + H2O → H3O+ + NO3-

100% in 0.1 M solution

CH3COOH + H2O ↔ H3O+ + CH3COO-

1.3% in 0.1 M solution