Application of EMF measurement

Electromotive Force: -
The electromotive force (EMF) of an electrochemical cell is the disparity in
electrode potentials between its two electrodes. It's measured in volts (V) and
signifies the energy per unit charge provided by the cell to move charge around
a closed circuit.
EMF originates from various sources such as chemical reactions in batteries or
electromagnetic induction in generators. It's essential for driving current
through circuits and powering devices. Real sources of EMF often have internal
resistance, affecting the actual voltage available to the external circuit.
Applications of EMF measurement: -
1. Determination of equilibrium constant
2. Determination of solubility of sparingly soluble salt
3. Determination of valence
4. Determination of thermodynamic functions
5. Determination of pH of a solution
6. potentiometric titrations
7. Determination of activity coefficient
8. Determination of transference number

1.Determination of equilibrium constant: -

In this application, EMF measurement is utilized to determine the equilibrium

constant of a chemical reaction. By measuring the EMF of a cell at various
compositions of reactants and products, the Nernst equation is employed to
relate EMF to concentration.
Through this, the equilibrium concentrations of species involved in the reaction
can be determined, allowing calculation of the equilibrium constant.
This is particularly useful in understanding the extent to which a reaction
proceeds at equilibrium under specific conditions.
Equilibrium constant for a reaction can be determined from the value of cell
potential by employing the following reaction:

where, E° - standard electrode potential,

n = number of electrons transferred in the half-reaction,
K = equilibrium constant for the half-cell reaction.
2. Determination of solubility of sparingly soluble salt: -

EMF measurement can be employed to determine the solubility of sparingly

soluble salts.
By creating a concentration cell with different concentrations of the salt solution
and its ions, and measuring the EMF, one can determine the solubility product
constant (Ksp) using the Nernst equation.
This provides insights into the solubility behavior of the salt under given
conditions.

Cell: - Ag(s) | Ag+(aq)||Br-(aq) | AgBr (s), Ag(s)

3. Determination of valence: -

Valence determination involves the measurement of EMF in electrochemical

cells containing known concentrations of species with different oxidation states.
By relating the measured EMF to the Nernst equation and the known
concentrations, the valence of the element involved in the redox reaction can be
determined.

The expression for the E.M.F. of E, of a concentration cell

where n is the valence of the metallic ion in solution, while C1 and C2 are the
concentrations of the ions in the two half-cells.
Example:
The following cell is constructed
Hg | 0.05N Hg2 (NO3)2 || 0.5N Hg2 (NO3)2 | Hg
and its emf found experimentally is 0.029 Volts.
4. Determination of thermodynamic functions: -
EMF measurements can provide data for calculating various thermodynamic
functions such as Gibbs free energy, enthalpy, and entropy.
By measuring the EMF of cells at different temperatures and concentrations,
thermodynamic relationships like the Van 't Hoff equation can be applied to
derive these functions, offering insights into the spontaneity and feasibility of
chemical reactions.

Free energy:
ΔG = -nFE
Where,
n is the number of moles of electrons transferred and is equal to the valence of
the ion participating in the cell reaction.
F stands for Faraday and is equal to 96,500 coulombs. and E is the emf to the
cell.
Enthalpy: -
Where, (dE/dT)-The temperature coefficient of the emf of the cell
Case 1. (dЕ/dТ)p = 0, then nFE = – ΔΗ
Case 2. (dЕ/dТ)p > 0, then nFE > – ΔΗ
Case 3. (dЕ/dТT)p < 0, then nFE < – ΔΗ
5. Determination of pH of a solution: -

EMF measurements can be used to indirectly determine the pH of a solution by

utilizing ion-selective electrodes.
By measuring the EMF generated by the electrode immersed in the solution,
the activity of hydrogen ions can be inferred, allowing calculation of pH using
the Nernst equation.

➤A half-cell is set up with the test solution as electrolyte. The emf of the cell
depends on the concentration of H+ ions or pH of the solution. The emf of the
half-cell is determined by coupling it with another standard half-cell and
measuring the emf of the complete cell.
➤ The commonly used standard electrodes are: -
(a) The hydrogen electrode
(b) The quinhydrone electrode
(c) The glass electrode
➤ By measuring potential difference, hydrogen ion concentration can be
calculated using the Nernst equation which gives the relationship between
Hydrogen ion concentration and Voltage or Potential.

E = E°+ (RT /nF)In [M+]

By using glass electrode-

6.Potentiometric Titrations: -
Definition: -
A potentiometric titration is the one in which the equivalence point is detected
by measuring the changes in the potential of suitable electrode during the
course of reaction.
Potentiometric titrations involve the use of EMF measurements to monitor the
progress of a titration.
By continuously measuring the EMF as titrant is added to a solution containing
the analyte, the equivalence point can be determined accurately, enabling
precise analysis of the concentration of the analyte.

Experiment process: -
The indicator electrode is paired with a reference electrode and the two
electrodes are connected to an electronic voltmeter. The emf of the indicator
electrode changes gradually with the change of concentration of ions caused
by the addition of titrant from the burette. The equivalence point is indicated
by a sharp change in electrode potential.
Types:
(a) Acid-base titrations
(b) Oxidation-reduction titrations
(c) Precipitation titrations

(a). Acid-Base titration: -

(b). Oxidation-reduction titration: -
(c). Precipitation titration: -

7. Determination of Activity Coefficient: -

 EMF measurements can be used to determine the activity coefficients of ions
in solution.
By measuring the EMF of cells with known concentrations of ions and applying
the Debye-Hückel equation, the activity coefficients can be calculated,
providing information on the behavior of ions in solution.
For example, the mean activity coefficient of the ions in hydrochloric acid of
molality b is obtained from the following equation once E has been
determined:

8. Determination of Transference Number: -

Transference number determination involves measuring the EMF across a cell
while a current is passed through it.
By measuring the rate of change of EMF with time, one can determine the
transference number of ions, which represents the fraction of total current
carried by a specific ion during electrolysis.
This information is crucial in understanding the transport of ions in electrolyte
solutions.
This method employed based on measurement of cell containing the same
electrolyte, with & without transference.

Where the transference number tf refers to the negative on if the extreme

electrodes are reversible with respect to positive ion and vice- versa.

For example; if the amalgam cell without transference

Ag | AgCl(s) LiCl (c₁) | LiHgx | LiCl(c₂) AgCl(s) | Ag

Is under consideration, the corresponding cell with transference is

Ag | AgCl(s) LiCl(c₁) : LiCl(c₂) AgCl(s) | Ag

The ratio of the E.M.F.'S of these cells then gives the transference number of
lithium ion, i.e