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Salt hydrolysis.

It is the reaction of the cation or the anion or both the ions of the salt with
water to produce either acidic or basic solution. Hydrolysis is the
reverse of neutralization.

(1) Hydrolysis constant : The general equation for the hydrolysis of a

salt (BA),

BA  H2 O ⇌ HA  BOH

Applying the law of chemical equilibrium, we get

[HA][BOH]
 K , where K is the equilibrium constant.
[BA][H2 O]

Since water is present in very large excess in the aqueous solution, its

concentration [H2O] may be regarded as constant so,

[HA][BOH]
 K[H2O]  K h , where K h is called the hydrolysis constant.
[BA]

(2) Degree of hydrolysis : It is defined as the fraction (or percentage) of

the total salt which is hydrolysed at equilibrium. For example, if 90% of a
salt solution is hydrolysed, its degree of hydrolysis is 0.90 or as 90%. It is
generally represented by ‘ h ’.

Number of moles of the salt hydrolysed

h
Total number of moles of the salt taken

(3) Salts of strong acids and strong bases do not undergo hydrolysis (they
undergo only ionization) hence the resulting aqueous solution is neutral.
Halides, nitrates and sulphates of Na and K, SrCl 2 and BaCl 2 are of this
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type. As an illustration, let us discuss the hydrolysis of NaCl . We may

write,

NaCl  H2O  NaOH  HCl

or Na   Cl   H2 O  Na   OH  H  Cl  or

H2O  H  OH

Further in the resulting solution, [H ]  [OH ] .

(4) Salts of weak acids and strong bases undergo anionic hydrolysis to
produce basic solutions Na and K salts other than halides, nitrates and
sulphates are of this type, e.g., NaOOCCH3 , Na2CO3 , NaCN , Na3 PO4 ,

Na2 HPO4 , Na2 B4 O7 . 10H2O , etc.

A(aq.)  H2O(l) ⇌ HA(aq.)  OH (aq.)

At start C 0 0

At equil C(1  h) Ch Ch

Where C is the molarity of the salt solution and h is the degree of

hydrolysis.

[HA][OH ] (Ch.Ch)
K h (Hydrolysis constant) = 
[A  ] C(1  h)

Kh
If h  1 , then, K h  Ch2 or h
C

Relation between hydrolysis constant (K h ), K w and Ka is as follows,

Kw
Kh 
Ka

for calculation of hydrogen ion concentration;

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Kw K a
[H  ]  or pH  1/ 2 (pK w  pK a  logC)
C

(5) Salts of strong acids and weak bases undergo cationic hydrolysis to
produce acidic solutions. Halides, sulphates and nitrates of all metals
except alkali metals, alkaline earth metals are of this type, e.g.,

FeCl3 , NH4Cl, CuSO4 ,AlCl3 etc.

B (aq.)  H2O(l) ⇌ BOH(aq.)  H (aq.)

At start C 0 0

At equil C(1  h) Ch Ch

[BOH][H ] (Ch.Ch)
Kh  
[B ] C(1  h)

Kh
If h  1 , then , K h  Ch2 or h
C

Relation between K h , K w and K b is as follows,

Kw
Kh 
Kb

For calculation of H ion concentration,

K wC 1
[H ]  or pH  (pK w  pK b  logC)
Kb 2

(6) Salts of weak acids and weak bases undergo anionic as well as
cationic hydrolysis to produce an aqueous solution which may be neutral
or acidic or basic depending upon the relative strengths of weak acid and
weak base. Such a salt cannot be Na or K salt or it cannot be halide,
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nitrate or sulphate, it could be NH4 OOCCH3 ,(NH3 )3 PO4 ,Ca3 (PO4 )2 ,

aniline acetate,

(NH4 )2 CO3 , AlPO4 etc.

A  (aq)  H2O(l) ⇌ HA(aq)  OH (aq)

B (aq)  H2 O(l) ⇌ BOH(aq)  H (aq)

B (aq)  A  (aq)  H2O(l) ⇌ HA(aq)  BOH(aq)

At start C C 0 0

At equil C(1  h) C(1  h) Ch Ch

If [OH ]  [H ] , possible when K a  K b , there is no net hydrolysis, the

resulting aqueous solution is neutral e.g., NH4 OOCCH3 .

If [OH ]  [H ] , possible when K a  K b , there is net anionic hydrolysis, the

resulting aqueous solution is basic, e.g., NH4CN .

If [OH ]  [H ] , possible when K a  K b there is net cationic hydrolysis, the

resulting aqueous solution is acidic.

[HA][BOH] Ch.Ch
Kh    
[B ][A ] C(1  h).C(1  h)

If [OH ]  [H ] and if h  1 , then, K h  h2 or h  K h

i.e., the degree of hydrolysis of such a salt is independent of the

concentration of salt solution.

Relation between K h ,K w ,K a and K b is as follows,

Kw
Kh 
K a .K b