Chapter 4

Acid-Base Chemistry and

Bonding

4.1 Review of Acid-Base

definitions

4.2 Hard and soft acids and

• 4.1 Review of Acid-Base definitions
• Arrhenius acids form hydronium ions
in water, and bases form hydroxide
ions.
 definition assumes This that water is the
solvent.
 Definitions
• Brønsted and Lowry defined acids as
proton donors and bases as proton
acceptors. They also introduced the
concept of conjugate acid-base pairs.
 Other
Solvents
• For any solvent that can dissociate into a
cation and an anion, the cation is the
acid, and the anion is the base.
• Any solute that causes an increase in the
concentration of the cation is an acid,
• those that increase the concentration of
the anion are bases.
 Lewis Acids & Bases
• The Lewis definition further expands the
definitions.
• base is an electron-pair donor, and
• an acid is an electron-pair acceptor.
• The two combine to form an adduct.

A +
:B  A-B
 Lewis Acids & Bases
1. This definition includes the “s t a n d a r d”
Brønsted-Lowry acid-base
reactions:

H+(aq) + :NH3(aq)  NH4+(aq)

2. It also includes the reactions of metal
ions or atoms with ligands to form
coordination compounds:

Ag+(aq) + 2 :NH3(aq)  Ag(NH3) 2

+
 Lewis Acids & Bases

3. In addition, electron-deficient
compounds such as trivalent boron is
categorized as a Lewis acid.
B(CH3)3 + :NH3  (CH3)3B←NH3
• The HOMO on the Lewis base interacts
with the electron pair in the LUMO of the
Lewis acid.
• The MOs of the adduct are lower in
energy.
Lewis Acids & Bases

• The LUMO and HOMO

are called frontier orbitals.
• If there is a net lowering
of energy, the adduct is
stable.
 Donor–Acceptor Bonding in BF3 - NH3.
• The empty LUMO of the BF3 interact with electron of HOMO of
the NH3.
 Lewis Acids & Bases

• A Lewis base has an electron pair in its

highest occupied molecular orbital
(HOMO) of suitable symmetry to interact
with the LUMO of the Lewis acid.
• The closer the two orbitals are in energy,
the stronger the bond in the adduct.
2.2 hard and soft acids and bases (HSABs)
• The HSAB concept is a useful guide to explain acid–
base chemistry and other chemical phenomena
• Pearson designating polarizable acids and bases as
soft and non polarizable acids and bases as hard.
• The ability of a cation to distort an anion is
known as its polarization power
• the tendency of the anion to become
polarized by the cation is known as its
polarizability.
Polarizing power and
polarizability
• Much of the hard–soft distinction depends on
polarizability, the degree to which a molecule or
ion is distorted by interaction with other molecules
or ions.
• Electrons in polarizable molecules can be attracted
or repelled by charges on other molecules, forming
slightly polar species that can then interact with
the other molecules
 Hard and Soft Acids and Bases

• The polarizability of an acid or base plays a

role in its reactivity.
• Hard acids and bases are small, compact, and
non- polarizable.
• Soft acids and bases are larger, with a more
diffuse distribution of electrons.
 Hard and Soft Acids and Bases

• Soft Lewis base are those in which the

donor atoms are easily polarized and have
low electronegativity.
• While Hard Lewis base are those in which
the donor atoms have low polarisabilities
and high electronegativities.
 Hard and Soft Acids and Bases
• A hard Lewis acid, like hard base, is
 difficult to polarize,
 small size, high positive charge,
 having small size and a noble gas electronic
configuration.
 Should have vacant d- orbital or approximate
vacant d- orbital configuration (in
 Hard and Soft Acids and Bases
soft acid, like soft base, are
 readily polarized these have large size,
 low positive or zero charge and
 do not have a noble gas configuration.
 Should have filled d-orbital or approximate filed
d-orbital configuration (in the case of d-black
dements) .
Hard and Soft Acids and
Bases
In addition to their intrinsic strength,

• Hard acids react preferentially with

hard Bases, and

• soft acids react preferentially with

soft bases
 Classification of the Lewis’s
acid
Hard acid: Li+, Na +, K +, Mg, +2 Ca +2, Al+3
,Ba +2, Ga +3, La +3, Cr +3, Cr +6, Co +3, Fe
+3
, Si +4, Ti +4, Sn +4, SO3, BF3, BCl3,
B(OR)3, Al(CH3)3, I +7, I +5
Soft acid: Cu +, Ag +, Au +, Hg +, Pt +2,
Hg +2, Pd +2, I +, Br +, Metal atoms at
zero oxidation states
Borderline acids: Fe +2, Co +2, Ni +2,
Cu +2, Zn +2, Pb +2, Sn +2, SO2, Bi +3, Sb
+3
, NO + GaH3, B(CH3) 3
 Classification of the Lewis’s
acid
Hard base: H2O, OH- , CH3COO- , PO4
–3
, SO4 -2, CO3 -2, ClO4 - NO3 - , ROH, R-
O- , R2O (Donor O), NH3, R-NH2, N2H4
(donor N), F- , Cl –
Soft base: R2S, R-SH, R-S- , I- , SON- ,
S2O3, R3P, (RO)3P, CN- , RNC, CO,
C2H4, C6H6 , H- , R- , S- 2
Borderline base: C6H5-NH2, C5H5N, Br-
Applications of HSAB principle:
1. Solubility Silver Halides
Compound solubility
AgF product 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)
those compounds which have more stable H-H & SS
combinations, exhibit less solubility in the aqueous
medium in compare to the compounds which have less
stable H-S & S-H combinations.
 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.
2. Nature of the doner site in the ambident
ligand
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.
3. Occurrence of the chemical reaction
According to HSAB principle,
if the reactants present in the chemical
reaction have less stable H-S & S-H
combinations, then they will have the tendency
to react with each other to generate the more
stable H-H & S-S combinations i.e. in such
condition chemical reaction will be possible

both the reactants have less stable H-S & S-H combinations
and the products have the more stable H-H & S-S combination
3. Occurrence of the chemical reaction
According to HSAB principle,
If the reactants have more stable H-H & S-S
combinations, then they will not have the tendency to
convert into the less stable H-S & S-H combinations by
the reaction i.e. in such condition reaction will not
be possible.

both the reactants have more stable (H-H, S-S)

combinations and products have less stable H-S and S-H
combinations. Hence, according to HSAB principle, this reaction
will not be possible. .
Example: K for ligand
exchange reactions
Compare:
[MeHg(H2O)]+ + HCl MeHgCl + H 3 O +
K= 1.8 x 1012

[MeHg(H2O)]+ + HF MeHgF + H3 O+
K= 4.5 x 10-2
4. Stability of the complexes containing different ligand

According to HSAB principle,

a complex containing more than one type of the
ligands (hard or soft), then the complex will be more
stable.

..
4. Stability of the compound/complexes
(i) AgI2- is more stable than the AgF2-
Explanation: AgI2- containing soft- soft
combination due to which accoding to the HSAB
principle, AgI2- well be more stable while AgF2- -
containing soft –hard combination, will be less
stable or sometime cannot exist

..
 4. Stability of the compound/complexes
(ii) [Co (F)6]-3 is being more stable then [Co(I)6]-3 ion.
-
Explanation: [Co (F)6]-3 ion containing hard-hard
(H-H) combination is more stable while on the
other hand, [Co (I)6]-3 ion having hard-soft (H-S)
combination, will be less stable.

..
5. Occurrence of metal ions on the earth
(Lighter metal ions like Li+ , Na+ , Mg+2 , Ca+2 etc. exist
in the form of there chlorides, carbonates, sulphates,
phosphates (O-2, CO3-2 , SO4-2, PO4-3) on the earth crust
but cannot exist in the form of their sulphides ( S -2)
while on the other hand heavier metal ions like Ag + ,
Hg+ , Cu+ etc. exist in the form of their sulphides on the
earth crust and cannot exist in the form of O -2, CO3-2 ,
SO4-2, PO4-3etc.
Explanation :- Lighter metal ions form the stable hard –
hard combination with the O-2, CO3-2 , SO4-2, PO4-3 on the earth
crust due to which they exist in the form of there oxides,
carbonate, sulphates and phosphates while these lighter metal
ion forms the less stable unstable hard soft combination with the
sulphide ion due to which they connot exist in the form of there
 5. Occurrence of metal ions on the earth
Explanation :- Heavier metal ions. form the
stable soft –soft combination with the S-2 ion
due to which they can exist in the form of their
sulphides on the earth crust while on the other
hand, the heavier metal ions like Ag+ , Hg+ ,
Cu+ etc. form the unstable or less stable soft-
hard combination with the O-2, CO3 -2, SO4 -2,
PO4 -3 etc. due to which they cannot exist in the
form of there oxides, carbonates, sulphates and
phosphates on the earth crust.

..
 Problem

• Predict the solubility (high or low) of silver

fluoride, silver iodide, lithium fluoride and
lithium iodide using the hard-soft acid/base
approach.
• Identify each Lewis acid and Lewis base, and
categorize each as hard or soft.
 Charge Density – Hard Acids

• Hard acids typically have a high charge

density.
• They are often metal ions with a
(higher) positive charge and small ionic
size.
• Their d orbitals are often unavailable to
engage in π bonding.
 Charge Density – Soft Acids

• Soft acids typically have lower charge density

(lower ionic charge and greater ionic
size).Their d orbitals are available for π
bonding. Soft acids are often 2nd and 3rd row
transition metals with a +1 or +2 charge, and
filled or nearly filled d orbitals.
Effect of Oxidation Number

Cu 2+ /Cu + on acid hardness

SO3/SO2 on acid hardness
NO -/ N O - on base hardness
SO 2-/SO 2- on base hardness
4 3
 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
 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.
 Other Considerations
• As the adduct forms, there is usually a
change in geometry around the Lewis acid
site.

BX3 + N(CH3)3 
X3B-NMe3

• The stability of the adduct is:

BBr3 > BCl3> BF3

• This order seems opposite of what would

be expected based on halogen size or
Other Considerations
empty 2p
orbital
The reactivity pattern
suggests some degree
of π bonding in BF3.

filled
orbitals
 Other Considerations
• Steric factors can play a role. An example
is the unfavorable reaction between
:N(C6H5)3 and BCl3.
• The large phenyl groups interact with the
chlorine atoms on boron to destabilize the
product.
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
 Evidence in Nature

• In geochemistry, the elements in the

earth’s crust are classified as
lithophiles or chalcophiles.
• The lithophile elements are typically
found as silicates (bonded via the O
atom):Li+, Mg2+, Ti3+, Al3+ and Cr2+,3+.
• These are hard Lewis acids.
 Evidence in Nature

• The chalcophile elements are typically

found as sulfides or bonded to Se2- or
Te2-.
• They include: Cd2+, Pb2+, Sb3+, and
Bi3+.
• These are soft Lewis acids.
• Zinc ion, which is borderline, is typically
found as a sulfide.