Potentiometry

Potentiometry is measuring the potential or emf [electromagnetic force] of a solution using a

set of indicator and reference electrode.

The potential of a solution depends on the nature and concentration of ions of drug substance.
The potential is measured in mV.

Nernst equation: The Nernst equation is a chemical thermodynamical relationship it permits

the calculation reduction potential of a reaction (half or full cell reaction) from the standard
electrode potential, absolute temperature. The potential of a metal electrode at 25degrees
immersed into a solution of its own ions

Ecell = E0 – [RT/nF] ln C

E = E0 – 0.0592/n log10 C

E0= standard potential of the metal

R = universal gas constant

T = temperature

n = number of electrons transferred

F = Faraday constant

Q = reaction quotient

N= valency of ions

C= concentration of ions
Classification of electrodes:

electrodes

function

type

First type
Indicator
Reference
Second type electrodes
electrodes

Third type Glass

membrane
Redox type electrode

Antimony
antimony
Secondary standard
Primary standard
electrodes
electrodes
Hydrogen
electrode
Silver-silver
Hydrogen
chloride electrode
electrode

Saturated calomel
electrode
Reference electrodes: the reference electrode is a half-cell having a known electrode
potential and remains the at constant temperature and is independent of this composition of
the analyte solution.

1. Hydrogen electrode:

It can be used as indicator and as reference electrode

It consists of platinum foil coated with platinum black and wire contact with mercury
This is assembled with a glass covering through hydrogen [99%purity] is passed at 1 atm
pressure continually

It is dipped into a solution of standard acid or unknown solution

The potential of the electrode is given as: E= -0.0592Ph

Fig. 1 diagram of standard hydrogen electrode

Advantages: it can be used as a reference electrode when dipped with standard acid

Used over entire pH Potentials of electrodes can be measured

Dis advantages: it can be affected by the presence of oxidizing and reducing agent
Difficult to regulate pressure of H2 gas Platinum foil gets easily poisoned
1. Saturated calomel electrode:

It consists of outer sleeve and inner jacket.

Inner tube has wire connected with mercury and plugged with a calomel and Kcl

It is surrounded by an outer sleeve

Tip is filled with the crystals of kcl and plug of asbestos

The space is filled with saturated kcl

Potential of electrode depends on the concentration of kcl solution and temperature

0.2444v and 25 degree

Advantages: Stability of potential

Disadvantages: dependent on temperature

Fig. 2 diagram of saturated calomel electrode

2. Silver-silver chloride electrode:

Widely used reference electrode

It is simple, inexpensive, very stable

It is used with saturated kcl electrode

Ag-wire coated electrolytically with the agcl2 and dipped into kcl
 Potential depends on the concentration of kcl and temperature

E= 0.199V

Advantages: easy to use

Dis advantages: difficult to prepare

Fig. 3 diagram of silver silver- chloride electrode

Indicator electrodes: the potential that can be varies in a known way by with
variations. Used to identify the concentration of oxidized forms
1) Glass membrane electrode:

Glass electrode is most widely used indicator electrode

The glass electrode consists of glass tube with thin ph sensitive glass bulb at tip

It acts as indicator electrode and dipped into solution whose potential is to be known

e=k- 0.0592ph

Advantages: it gives rapid response

Chemically resistant to the oxidizing and reducing agents

Dis advantages: extremely fragile

Damages the electrode

 Fig. 4 diagram of glass membrane electrode

2) Antimony-antimony oxide electrodes:

It consists of antimony rod dipped into solution whose potential has be determined

Antimony oxide is to be formed on exposure to the air

E= 0.255-0.0592 pH

Advantages: used from ph 3 to ph 8

Not easily poisoned or damaged

Disadvantages: this electrode cannot be used in presence of dissolved oxygen

And oxidizing agent

Fig. 5 diagram of antimony-antimony oxide electrode

Reference:

Skoog DA, Holler FJ, Crouch SR. Principles of instrumental analysis. Cengage learning;
2017 Jan 27

Skoog DA, West DM, Holler FJ, Crouch SR. Fundamentals of analytical chemistry. Cengage
learning; 2013

Evans A. Potentiometry and ion selective electrodes