ACID-BASE AND

DONOR-ACCEPTOR CHEMISTRY
Acids and Bases

Acid
- characteristic sour taste;
- ability to change the color of litmus from blue to red;
- react with certain metals to produce gaseous H2;
- react with bases to form a salt and water

Base
- bitter taste;
- soapy" feeling when applied to the skin;
- ability to restore the original blue color of litmus ;
- ability to react with acids to form salts.
Acid-Base Definitions
Arrhenius Theory
Arrhenius acids – form hydrogen ions or hydronium
ions in aqueous solution

Arrhenius bases – form hydroxide ions in aqueous

solution

Example:
Bronsted-Lowry Concept
Bronsted-Lowry Acid
- a species with a tendency to lose hydrogen ion

Bronsted-Lowry Base
- a species with a tendency to gain a hydrogen ion

¨ Introduced the concept of conjugate acids and bases.

¨ Described all reactions as occurring between a stronger
acid and base to form a weaker acid and base
Bronsted-Lowry Concept
Examples
Solvent System Concept
Applies to any solvent that can dissociate into a cation
and an anion (auto dissociation).

Acid – the cation resulting from auto-dissociation

Base – the anion resulting from the auto-dissociation

Example
Solvent System Concept
More examples

For non-aqueous systems,

Acid-base reactions
¨ Reverse of auto dissociation (solvent system concept)
Example

¨ Comparison of the neutralization reactions of the

first three acid-base concepts
Checkpoint

IF5 undergoes auto-dissociation into IF4+ + IF6-. SbF5

acts as an acid and KF acts as a base when
dissolved in IF5. Write the balanced chemical
equations for these reactions.
Properties of common solvents
Lewis Concept
Base – an electron-pair donor
Acid – an electron-pair acceptor

¨ Include metal ions and other electron pair acceptors

as acids
¨ Provides a handy framework for non-aqueous
reactions

Example
Lewis Concept
Lewis acid-base reaction
Lewis Concept
Lewis acid-base reaction

Lewis acid-base adducts involving metal ions are

called coordination compounds (bonds formed with
both electrons from one atom are called coordinate
bonds)
 Hard and Soft Acids and Bases
Irving-Williams stability series (1953) –
the stability of dipositive metal ion complexes increases:

Ba < Sr < Ca < Mg < Mn < Fe < Co < Ni < Cu < Zn

 Hard and Soft Acids and Bases
Ahrland et al. (1958) Type A and Type B classification,
Type A metal:
• Alkali metal cations: Li+ to Cs+
• Alkaline earth metal cations:
Be2+ to Ba2+
• Lighter transition M’s/ higher OX. :
Ti4+, Cr3+, Fe3+, Co3+
• The proton, H+

Type B metal: Type A metals prefer to bind to Type

• Heavier transition M’s A ligands
in lower oxidation states:
&
Cu+, Ag+, Cd2+, Hg+,
Ni2+, Pd2+, Pt2+. Type B metals prefer to bind to Type
B ligands
Examples: Aqueous Solubility
Silver Halides
Compound solubility product
AgF 205
AgCl 1.8 x 10-10
AgBr 5.2 x 10-13
AgI 8.3 x 10-17

AgX(s) + H2O(l) Ag+(aq) + X-(aq)

Solubility of Lithium Halides
LiBr> LiCl> LiI> LiF

LiF should have a higher ∆solv than the other

salts, yet it is the least soluble in water. This is due to
the strong hard acid (Li+)/hard base (F-) interaction.
Example: Thiocyanate Bonding
SCN- displays linkage isomerism as the ligand
coordinates to metals via the sulfur or the nitrogen.
Mercury (II) ion bonds to the sulfur (a soft-soft
interaction) whereas zinc ion bonds to the nitrogen
atom.
Example: K for ligand exchange
reactions
Compare:
[MeHg(H2O)]+ + HCl MeHgCl + H3O+
K= 1.8 x 1012

[MeHg(H2O)]+ + HF MeHgF + H3O+

K= 4.5 x 10-2
Hard and Soft Acids and Bases
¨ 1965- Ralph Pearson introduced the hard-soft-acid-
base (HSAB) principle.

¨ This very simple concept was used by Pearson to

rationalize a variety of chemical information.

¨ 1983 – the qualitative definition of HSAB was

converted to a quantitative one by using the idea of
polarizability.

¨ A less polarizable atom or ion is “hard” and a more

easily polarized atom or ion is “soft”
HSAB
Hard and Soft Acids and Bases
Polarizability
Non-polarizable (hard) vs Polarizable (soft) :
Hard and Soft Acids and Bases
Pearson’s Principle of Hard and Soft Acids and
Bases (HSAB) can be stated as follows:

Hard Acids prefer to bond with Hard Bases, and

Soft Acids prefer to bond with Soft Bases.

This can be illustrated by the formation

constants (log K1) for a hard metal ion, a soft
metal ion, and an intermediate metal ion, with
the halide ions in Table 1:
Table 1. Formation constants with halide ions for a representative hard,
soft, and intermediate metal ion .
_________________________________________________
hard soft
Log K1 F- Cl- Br - I- classification
_________________________________________________
soft-soft interaction

Ag+ 0.4 3.3 4.7 6.6 soft

Pb2+ 1.3 0.9 1.1 1.3 intermediate

Fe3+ 6.0 1.4 0.5 - hard

_________________________________________________
hard-hard interaction
Distribution of Hard and Soft Bases by donor
atom in the periodic Table:

C N O F

P S Cl

As Se Br
I

Figure 2. Distribution of hardness and softness for potential donor atoms

for ligands in the Periodic Table.
 Hard and Soft Bases.

HARD: H2O, OH-, CH3COO-, F-, NH3, oxalate (-

OOC-COO-), en (NH2CH2CH2NH2).

SOFT: Br -, I-, SH-, CH3S-, (CH3)2S, S=C(NH2)2

(thiourea), P(CH3)3, PPh3, As(CH3)3, CN- -S-
C≡N (thiocyanate, S-bound)

INTERMEDIATE: C6H5N (pyridine), N3- (azide), -

N=C=S (thiocyanate, N-bound), Cl-

(donor atoms underlined)

Hard and Soft Acids
Fajan’s rule
1. For a given cation, covalent character increases
with increasing anion size.
2. For a given anion, covalent character increases
with decreasing cation size.
3. The covalent character increases
with increasing charge on either ion.
4. Covalent character is greater for cations with non-noble gas
electronic configurations.

A greater covalent character resulting from a soft-soft interaction is related

With lower solubility, color and short interionic distances,
whereas hard-hard interactions result in colorless and highly soluble compounds
Exercise
Explain the following using Fajan’s rules:
1. Ag2S is much less soluble than Ag2O.
2. Fe(OH)3 is much less soluble than Fe(OH)2.
3. FeS is much less soluble than Fe(OH)2.
4. Ag2S is much less soluble than AgCl.
5. Salts of transition metals are usually less soluble
than the corresponding salts of the alkali and
alkaline earth metals.
Exercise
Some of the products of the following reactions will
be insoluble and some form soluble adducts.
Consider only HSAB characteristics in your answers.

1. Will Cu2+ react more strongly with OH- or NH3?

With O2- or S2-?
2. Will Fe3+ react more strongly with OH- or NH3?
With O2- or S2-?
3. Will Ag+ react more strongly with NH3 or PH3?
4. Will Fe, Fe2+, or Fe3+ react more strongly with CO?
Acid or Base Strength
It is important to realize that hard/soft
considerations have nothing 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, you must consider both the relative
strength of the bases, and the hard/soft nature of
each base and the acid.
Acid or Base Strength
Consider the reaction between ZnO and LiC4H9.
ZnO + 2 LiC4H9 = Zn(C4H9)2 + Li2O

Zinc ion is a strong Lewis acid, and oxide ion is a

strong Lewis base.
Acid or Base Strength
Consider the reaction between ZnO and LiC4H9.

ZnO + 2 LiC4H9 Zn(C4H9)2 + Li2O

soft -hard hard -soft soft -soft hard -hard

Zinc ion is a strong Lewis acid, and oxide ion is a

strong Lewis base. However, the reaction proceeds
to the right (K>1), because hard/soft considerations
override acid-base strength considerations.
The Nature of the 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.
The Hard Soft [Lewis] Acid Base Principle

Klopman's FMO Analysis (1968)

Hard [Lewis] acids bind to hard [Lewis] bases to give charge-controlled (ionic)
complexes.

Interactions: dominated by the +/– charges on the Lewis acid and Lewis base
species.

Soft [Lewis] acids bind to soft [Lewis] bases to give FMO-controlled (covalent)
complexes.

Interactions: dominated by the energies of the FMO, the (HOMO) and the
(LUMO).
The Hard Soft [Lewis] Acid Base Principle
Combining Pearson's and Klopman's Ideas

• Hard Lewis acids:

• Atomic centres of small ionic radius
• High positive charge
• do not contain e- pairs in valence shells
• Low electron affinity
• Likely to be strongly solvated
• High energy LUMO

• Soft Lewis acids:

• Large radius
• Low or partial (delta+) positive charge
• Electron pairs in their valence shells
• Easy to polarise and oxidise
• Low energy LUMOs,
but large magnitude LUMO coefficients
The Hard Soft [Lewis] Acid Base Principle
Combining Pearson's and Klopman's Ideas

• Hard Lewis bases:

• Small, highly solvated,
electronegative centres: 3.0-4.0
• Species are weakly polarisable
• Difficult to oxidise
• High energy HOMO

• Soft Lewis bases:

• Large atoms,
intermediate electronegativity: 2.5-3.0
• Easy to polarise and oxidise
• Low energy HOMOs but
large magnitude HOMO coefficients.

• Borderline species have intermediate properties.

Applications of Hard/Soft Theory

The Qual Scheme, a series of chemical reactions used

to separate and identify the presence of dozens of
metal ions, is based largely on the hard and soft
properties of the metal ions.
The softer metals are precipitated out as
chlorides or sulfides, with the harder ions formed as
carbonates.
Thiocyanate, an ambidentate ligand:
Thiocyanate (SCN-) is a particularly interesting ligand. It is
ambidentate, and can bind to metal ions either through the S or
the N. Obviously, it prefers to bind to soft metal ions through
the S, and to hard metal ions through the N. This can be seen in
the structures of [Au(SCN)2]- and [Fe(NCS)6]3- in Figure 3 below:
Thiocyanate
Complexes showing
a) N-bonding in the
[Fe(NCS)6]3-
complex with the hard
Fe(III) ion, and
b) S-bonding in the
[Au(SCN)2]- complex
(CSD: AREKOX) with
the soft Au(I) ion
Cu(I) and Cu(II) with thiocyanate:
In general, intermediate metal ions also tend to bond to
thiocyanate through its N-donors. A point of particular interest
is that Cu(II) is intermediate, but Cu(I) is soft. Thus, as seen in
Figure 4, [Cu(NCS)4]2- with the intermediate Cu(II) has N-
bonded thiocyanates, but in [Cu(SCN)3]2-, with the soft Cu(I), S-
bonded thiocyanates are present.

Thiocyanate
complexes of the
intermediate Cu(II) ion
and soft Cu(I) ion. At a)
the thiocyanates are
N-bonded in [Cu(NCS)4]2-
with the intermediate
Cu(II), but at b) the
thiocyanates in
[Cu(SCN)3]2-, with the soft
Cu(I), are S-bonded
(CSD: PIVZOJ).
Quantitative Measurements
I-A I+A
h= c=
2 2
Absolute hardness Mulliken’s absolute electronegativity
(Pearson) (Pearson)

1 EHOMO = -I
s =
h ELUMO = -A

Softness
Energy levels
for halogens
and relations between
c, h and HOMO-LUMO
energies
Exercise
The Drago & Wayland Parameter

Empirical 4-parameter to predict enthalpy change of weak neutral acids with weak
neutral bases (gas phase/inert solvent)

-DH = EAEB + CACB

Example
Exercise
Measurement of Acid-Base Interactions

1. Changes in bp or mp can indicate the presence of

adducts.
2. Direct calorimetric methods or temperature
dependence of equilibrium constants.
3. Gas phase measurements of the formation of
protonated species.
4. IR spectra and NMR coupling constants can provide
indirect measures of bonding in acid-base adducts
5. UV or visible spectra can show changes in energy
levels in the molecules as they combine.
Thermodynamic Measurements
¨ Hess’s law
Exercise
Proton Affinity
A large proton affinity means it is difficult to remove
the hydrogen ion; this means that B is a strong base
and BH+ is a weak acid in the gas phase.

For example,

Pyridine and Aniline versus Ammonia

Acidity and Basicity of Binary
Hydrogen Compounds
¨ Acidity increases with increasing number of
electrons in the central atom.
¨ Gas phase acidities
Acidity and Basicity of Binary
Hydrogen Compounds
 Inductive Effects
¨ Electron donating substituents
enhance base strength and
electron-withdrawing groups
P P
enhance electron acceptor Me Me
Me
H
H
H
(acid) strength
PMe3 stronger base than PH3

gas-phase
base strengths NMe3 > NHMe2 > NH2Me > NH3
strongest base weakest base
This plays a role in bond lengths also
Strength of Oxyacids
¨ The more electronegative atom(s) surrounding the
central atom, the more acidic the oxyacid.
Strength of Oxyacids
Exercise
Acidity of Cations in Aqueous Solutions

¨ Many positive ions exhibit acidic behavior in

solution.

In more basic solutions,

Acidity of Cations in Aqueous Solutions

¨ Metal ions with larger charges and smaller radii

are stronger acids.
¨ Alkali metals – no acidity, Alkaline Earth metals –
slightly acidic, TM w/ +2 - weakly acidic, TM w/
+3 – moderately acidic, TM w/ +4 or more - strong
acids in aqueous solution
Acidity of Cations in Aqueous Solutions

¨ The stronger the cation acid, the less soluble the

hydroxide.
Acidity of Cations in Aqueous Solutions

¨ At the highly charged extreme, the free metal

cation is no longer a detectable species.

Examples:
- -
¨ Permanganate (MnO4 ), chromate (CrO4 ), uranyl

(UO2+), dioxovanadium (VO2+) and vanadyl (VO2+)

Steric Effect
¨ Reaction with H+

¨ Reaction with BF3 or B(Me)3

Steric Effect
Solvation and Acid-Base Strength
¨ In aqueous solution

¨ Solvation energies of the cations (absolute values)

Acid-Base Strength in Non-Aqueous
Solvents
¨ In water solvent

And

Hence, water is amphoteric.

¨ Strongest acid in H2O is H3O
+
-
¨ Strongest base in H2O is OH .
Acid-Base Strength in Non-Aqueous
Solvents
¨ In acetic acid solvent

¨ The strongest base in HOAc is the acetate ion.

¨ Leveling effect
¤ Acids or bases are brought down to the limiting
conjugate acid or base of the solvent.
Solvent pH range
Superacids
¨ Acid solutions more acidic than sulfuric acid.
¨ George Olah (1994)
¨ Hammett acidity function

¨ The stronger the acid, the more negative its Ho

value.
Superacids
Superacids