Determination of the Degree of Hydrolysis

and the Hydrolysis Constant by

Potentiometry

Working
Electrode Reference
Electrode
 Determination of hydrolysis constant (Kh)
Salt of weak acid and strong base The ionic product of water, Kw, is given by,

The general hydrolysis reaction of a salt of weak acid (HA) Kw = [H+][OH-] (2)
and strong base can be written as
For the dissociation of a weak acid, HA
A- + H2O ⇌ HA + OH-
HA ⇌ H+ + A-
This leads to the equilibrium constant expression
The acid dissociation constant, Ka, is expressed as
𝐻𝐴 𝑂𝐻−
𝐾ℎ = − 𝐻 + 𝐴−
𝐴 𝐻2 𝑂 𝐾𝑎 = (3)
𝐻𝐴

The concentration of water, [H2O], is very large and is Dividing (2) by (3)
regarded as practically constant.
Thus, the above equation becomes, 𝐾𝑤 𝑂𝐻 − 𝐻𝐴
= = 𝐾ℎ [by equation 1]
𝐾𝑎 𝐴−
𝐻𝐴 𝑂𝐻 −
𝐾ℎ = (1)
𝐴− 𝐾𝑤
Or, = 𝐾ℎ (4)
𝐾𝑎
Determination of the degree of hydrolysis ()

A- + H2O ⇌ HA + OH-
c 0 0 original molar conc.
c(1-) c c Molar conc. at equilibrium

𝐾𝑤 𝑐𝛼×𝑐𝛼 𝑐𝛼 2
𝐾ℎ = = =
𝐾𝑎 𝑐 1−𝛼 1−𝛼

𝐾ℎ 𝐾𝑤
𝛼= =
𝑐 𝐾𝑎 × 𝑐
 Determination of hydrolysis constant (Kh)
Salt of strong acid and weak base The ionic product of water, Kw, is given by,

The general hydrolysis reaction of a salt of strong acid (HA) Kw = [H+][OH-] (2)
and weak base can be written as
For the dissociation of a weak base, BOH
BA + H2O ⇌ BOH + HA
B+ + A- + H2O ⇌ BOH + H+ + A- BOH ⇌ B+ + OH-
B+ + H2O ⇌ BOH + H+
The dissociation constant, Kb, is expressed as
This leads to the equilibrium constant expression
𝐵+ 𝑂𝐻 −
𝐾𝑏 = (3)
𝐵𝑂𝐻
𝐻+ 𝐵𝑂𝐻
𝐾ℎ =
𝐵+ 𝐻2 𝑂 Dividing (2) by (3)
The concentration of water, [H2O], is very large the above 𝐾𝑤 𝐻 + 𝐵𝑂𝐻
equation becomes, = = 𝐾ℎ [by equation 1]
𝐾𝑏 𝐵+

𝐻 + 𝐵𝑂𝐻 𝐾𝑤
𝐾ℎ = 𝐵+
(1) Or, = 𝐾ℎ (4)
𝐾𝑏
 Determination of the degree of hydrolysis ()

BA + H2O ⇌ BOH + HA
B+ + A- + H2O ⇌ BOH + H+ + A-
B+ + H2O ⇌ BOH + H+

𝐻 + 𝐵𝑂𝐻
Hydrolysis constant, 𝐾ℎ = 𝐵+

If  is the degree of hydrolysis and c is the molarity of the salt BA, then

[B+] = (1-).c and [BOH] = H+ = .c

Hence,
𝐾𝑤 𝑐𝛼×𝑐𝛼 𝑐𝛼 2
𝐾ℎ = = = (<<1)
𝐾𝑎 𝑐 1−𝛼 1−𝛼

𝐾ℎ 𝐾𝑤
𝛼= =
𝑐 𝐾𝑏 × 𝑐
 Determination of hydrolysis constant (Kh)
Salt of weak acid and weak base
Let the initial concentration of the salt be c and  be the degree of hydrolysis of the salt, then

B+ + A- + H2O (excess) ⇌ BOH (aq) + HA (aq)

Initial conc., mol L-1: c c 0 0
Equilibrium conc., mol L-1: c(1-) c(1- ) c c

This hydrolysis constant for the above reaction is given by,

𝐵𝑂𝐻 𝐻𝐴 𝐵𝑂𝐻 𝐻𝐴 𝐾𝑤
𝐾ℎ = = × × 𝐻3 𝑂+ 𝑂𝐻− Hence, 𝐾ℎ = 𝐾
𝐵+ 𝐴− 𝐵 + 𝐴− 𝐴− 𝐻3 𝑂+ 𝑎 𝐾𝑏

𝑐𝛼.𝑐𝛼 𝛼2 𝛼 𝐾𝑤
Kh =𝑐 1−𝛼 .𝑐 1−𝛼 = 1−𝛼 2
Or, 1−𝛼 = 𝐾ℎ = 𝐾𝑎 𝐾𝑏
 Determination of the hydrolysis constant and degree of hydrolysis () of
aniline hydrochloride

Aniline hydrochloride, C6H5NH3+Cl-, is a salt prepared by the reaction of the weak base aniline and hydrochloric acid.

C6H5NH3+Cl- ionizes to form C6H5NH3+ and Cl- ions when dissolved in water, and the cation establishes the following
hydrolytic equilibrium.

C6H5NH3+ + H2O ⇌ C6H5NH2 + H3O+

The equilibrium constant (or the hydrolysis constant of the salt) for this process is given by,

𝑎𝐻+ ×𝑎𝐵
𝐾ℎ = , where 𝑎𝐻+ is the activity of the acid (H3O+), 𝑎𝐵 is the activity of the free base (C6H5NH2), and 𝑎𝐵𝐻 + is the
𝑎𝐵𝐻+
activity of the unhydrolysed salt (C6H5NH3+Cl-).

For dilute solutions, we may replace activities by concentration terms.

𝐻+ 𝐵
Hence, 𝐾ℎ = 𝐵𝐻 +
 Application of a Potentiometer

Hydrolysis constant can also be related to the dissociation constant, Kb, of the base through the ionic product of water,
Kw as,

𝐾𝑤
𝐾ℎ =
𝐾𝑏

If c equivalents of the salt is dissolved in 1 litre of water, c equivalents each of free base and free acid will be formed
due to hydrolysis ( is the degree of hydrolysis).

Thus, the pH of the solution may be related to the degree of hydrolysis as, pH = -log[H+] = -log (c)

Hence, by measuring the pH of the solution, c can be calculated from which the degree of dissociation  can be
obtained at a given concentration.

Expressing K, in terms , using Kh = c2/( 1 – ), the hydrolysis constant can be calculated.

𝐾𝑤
Substituting for Kh in 𝐾ℎ = and taking Kw = 1.0 x 10-14 at 25°C the dissociation constant of the base, Kb can be
𝐾𝑏
evaluated.
 A Potentiometer

A potentiometer is used to determine the difference

between the potential of two electrodes. Working
Electrode Reference
Electrode
The potential of one electrode (the working electrode)
responds to the activity of the analyte, and the other
electrode (the reference electrode) has a known
potential.
 Apparatus and Procedure

Apparatus : Potentiometer, Platinum electrode and calomel electrode.

Chemicals : Aniline hydrochloride, quinhydrone,

PROCEDURE:

➢ Prepare an N/10 aniline hydrochloride solution by dissolving appropriate quantity of the substance in
distilled water (100 mL).
➢ From this stock solution, dilute appropriately and get 25 mL of N/20, N/50 and N/100 solutions. Then
construct the following cell:

Transfer the 25 mL of the solution to 100 mL beaker; add a pinch of Quinhydrone, stir properly to dissolve
it, dip the electrodes (Pt and Calomel electrodes) into the solution.

 Pt | 0.1M aniline hydrochloride, Quinhydrone || Calomel 

➢ Determine the potential of the cell.

 Quinhydrone electrode

The so-called quinhydrone electrode, containing equivalent amounts of p-

benzoquinone and hydroquinone, is used to determine hydrogen ion
concentrations of unknown solutions → an indicator electrode

Indicator electrode – the potential depends on the activity of ions being

titrated or estimated

A platinum wire electrode is immersed in a saturated aqueous solution of quinhydrone, in which there is the
following equilibrium

C6H6O2 ⇌ C6H4O2 + 2H+ +2e−

The potential difference between the platinum electrode and a reference electrode is dependent on the activity,
𝑎𝐻 + , of hydrogen ions in the solution.

𝑅𝑇
𝐸= 𝐸0 + ln 𝑎𝐻 +
2𝐹

The quinhydrone electrode provides an alternative to the most commonly used glass electrode.
Acid-base titration is titration of hydrogen ions → its concentration
changes during titration → hence in acid-base titration, indicator
should be an electrode reversible to hydrogen ion

Pt | H2Q, Q, H+(aq)

The arrangement for a potentiometric titration

(1) pH meter;
(2) reference electrode;
(3) indicator electrode (calomel electrode);
(4) magnetic stirrer;
(5) burette.
 Results

1. pH is given by pH = (-Eobs + EQH + Ecal) / 0.0591

where EQH = 0.6996 V and Ecal = - 0.242 V (oxidation potential).
From this relation, pH of the solution can be calculated.

2. As pH = - log [H+] = - log (c), the degree of hydrolysis  can be calculated at every given
concentration. pH = - log c - log 

3. From , calculate the hydrolysis constant using the relation, Kh = c2/(1 - )

4. The dissociation constant, Kb can be calculated from the relation Kb = Kw/Kh

C6H5NH3+Cl- Eobs(V) pH  Kh Kb

N/10

N/20

N/50

N/100

Find out, Mean Kh and mean Kb.

Kh for this reaction at 25oC comes in the order of 10-5 mol L-1
 comes in the order of 10-2
Kb comes in the order of 10-10