PATTERNS IN THE LEWIS ACID-BASE

BEHAVIOR IN AQUEOUS SOLUTION

1
The HSAB Behavior
 It is a matter of fact that Lewis acids and bases can be
assigned as hard, soft, or intermediate in a classification
called HSAB clasification.

 It is generally accepted that soft metal ions prefer to

combine with ligands of soft donor atom, and hard metal
ions prefer to combine with ligands of hard donor atom.

 Thermodynamically, formation (stability) constant, K, is

the experimental measure of such chemical combination,
as it is related to the change in (free) energy involved.

- ∆Go = RT ln K

2
HSAB Approach to the Ionic and Covalent Character of
Chemical Bonds :

HARD - HARD ~ Electrostatic

interactions

SOFT - SOFT ~ Electron sharing

interactions

3
SMALL METAL
ION SMALL LIGAND

OH2
DA  large
H2O M F-
DB  small

OH2 H-bond?

No steric hindrance as the ligand is about the same size

as the displaced water
4
SMALL METAL
LARGE LIGAND
ION

OH2
DA  large
H2O M I-
DB  large

OH2 Steric hindrance

of solvation

Serious steric hindrance

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LARGE METAL
ION LARGE LIGAND

OH2
DA  small
H2O M I-
DB  large

OH2

No steric hindrance of the weakly solvated large metal ion

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EDWARD EQUATION (1954) :

[M-L]
M+ + L-  M-L K=
[M][L]

log Ko = αE + βH
A constant : E = the oxidation potential
Ko = 55.5 x K of the ligand L

H = pKa + 1.74

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 DRAGO (1971) :

[A-B]
A + B  A-B KAB =
[A][B]

log K 1 = EE
A B + C C +DD
A B A B

A constant Tendency for electro- Correction for

related to KAB static interaction steric hindance

Tendency for covalent

interaction
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The tendency for ionic binding of Lewis acids
as measured by IA = EA/CA

Lewis Acid IA= EA/CA EA CA DA

Au+ - 16.00 - 3.00 0.190 0.0

Ag+ - 10.60 - 1.52 0.143 0.0
Cu+ - 1.30 - 0.56 0.430 2.0
Hg2+ + 1.63 + 1.35 0.826 0.0
Pd2+ + 1.85 + 1.72 0.929 6.0
CH3Hg+ + 2.50 + 1.60 0.640 0.0
Tl3+ + 2.66 + 2.55 0.960 0.0
Cu2+ + 2.68 + 1.25 0.466 6.0
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Lewis Acid IA= EA/CA EA CA DA

H+ + 3.04 + 3.07 + 1.009 20.0

Cd2+ + 3.31 + 0.99 + 0.300 0.6
Ni2+ + 3.37 + 1.20 + 0.300 4.5
Co3+ + 3.77 + 3.30 + 0.875 7.0
Zn2+ + 4.26 + 1.43 + 0.312 4.0
Co2+ + 4.34 + 1.33 + 0.276 3.0
Fe2+ + 5.94 + 1.40 + 0.256 2.0
In3+ + 6.30 + 4.49 + 0.714 0.5
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Lewis Acid IA= EA/CA EA CA DA

Bi3+ + 6.39 + 5.91 + 0.926 0.0

VO2+ + 6.42 + 3.81 + 0.593 3.5
Pb2+ + 6.69 + 2.76 + 0.413 0.0
Mn3+ + 7.09 + 1.64 + 0.223 1.0
Ga3+ + 7.07 + 5.72 + 0.809 1.5
Cr3+ + 7.14 + 5.15 + 0.721 1.5
Am3+ + 7.21 + 4.29 + 0.595 0.0
Fe3+ + 7.22 + 6.07 + 0.841 1.5
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Lewis Acid IA= EA/CA EA CA DA

U4+ + 7.80 + 7.55 + 0.968 3.0

Sn2+ + 8.07 + 5.65 + 0.700 0.0
Pu4+ + 8.31 + 7.90 + 0.950 -
UO22+ + 8.40 + 4.95 + 0.589 1.0
Be2+ + 8.84 + 5.43 + 0.614 -
Lu3+ + 10.07 + 4.57 + 0.454 0.0
La3+ + 10.30 + 3.90 + 0.379 0.0
Mg2+ + 10.46 + 1.86 + 0.178 1.5
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Lewis Acid IA= EA/CA EA CA DA

Sc3+ + 10.49 + 7.03 + 0.671 0.0

Al3+ + 10.50 + 6.90 + 0.657 2.0
Ca2+ + 10.53 + 0.98 + 0.093 0.0
Y3+ + 10.64 + 4.76 + 0.477 0.0
Th4+ + 10.94 + 8.44 + 0.771 0.0
Ba2+ + 12.70 + 0.54 + 0.043 0.0
Na+ + 14.60 + 0.20 + 0.014 0.0
Li+ + 22.20 + 0.57 + 0.026 0.0
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 The tendency for ionic binding of Lewis bases
as measured by IB = EB/CB

Lewis Base IB = EB/CB EB CB DB

F- ∞ + 1.00 + 0.00 0.0

CH3COO- + 0.0 + 0.00 + 4.76 0.0
OH- + 0.0 + 0.00 + 14.00 0.0
N3- - 0.064 - 0.067 + 10.40 0.2
SCN- - 0.082 - 0.76 + 9.30 0.2
NH3 - 0.088 - 1.08 + 12.34 0.0
C5H5N - 0.102 - 0.74 + 7.00 0.0
Cl- - 0.100 - 1.04 + 10.04 0.6
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Lewis Base IB = EB/CB EB CB DB

SO32- - 0.107 - 1.94 + 18.20 0.4

Br- - 0.108 - 1.54 + 14.20 1.0
S2O32- - 0.119 - 3.15 + 26.50 1.1
I- - 0.122 - 2.43 + 20.00 1.7
NCS- - 0.128 - 1.83 + 14.30 1.0
HOCH2CH2)2S - 0.135 - 1.36 + 10.10 0.6
(NH2)2C=S - 0.135 - 2.46 + 18.20 0.6
CN- - 0.148 - 4.43 + 30.00 0.3
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 DRAGO (1971) :

[A-B]
A + B  A-B KAB =
[A][B]

log K 1 = EE
A B + C C +DD
A B A B

A constant Tendency for electro- Correction for

related to KAB static interaction steric hindance

Tendency for covalent

interaction
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