Electr Chemistry

Electrochemistry
Electrochemical cell
The device, which produces electrical energy at the expense of chemical energy is known
as a galvanic cell or voltaic cell or electrochemical cell.
Galvanic cell
A galvanic cell consists of two electrodes along with some reagents. An electrode itself
and the reagent involved with it is called the half cell. The Daniel cell is a typical example of a
galvanic cell.
It consists of a copper rod dipped in 1M copper sulphate solution. This is separated from
1M zinc Sulphate solution with the help of a porous pot. A zinc rod is inserted in the zinc
sulphate solution. The porous pot prevents the diffusion of the two solutions. But it allows the
passage of ions when the flow of an electric current takes place, on connecting the two rods, Cu
and Zn, by a metallic wire.
Actually what happens is that zinc passes into solution as zinc ions (Zn2+ ) liberating
electrons according to the following equilibrium reaction.
The electrons thus set free at the zinc electrode travel along the external circuit s shown
in figure. These electrons are used at the copper electrode where copper ions (Cu 2+) gain these
electrons and are discharged (reduced) as metallic copper.
The movement of electrons from zinc to copper produces current in the circuit. The net
chemical change described as the cell reaction is the sum total of equations (1) and (2) as
follows
Cell Representation
A Galvanic cell consists of two electrodes- anode and cathode. According to the present
conventions, a galvanic cell is represented by keeping in view of the following points-
(1) Anode is written on the left hand side while cathode is written on the right hand side.
(2) The electrode on the left (i.e) the anode is written by writing the metal (or solid
phase) first and then the electrolyte.
These two are separated by a vertical line (l) or a semicolon (;)
The electrolyte may be represented by the formula of the whole compound or by ionic
species.
Additional information regarding concentration may also be mentioned in bracket.
These points will be made clear by the following examples of representing anode
half cell as-
(3) The cathode of the cell (at which reduction takes place) is written on the right hand
side.
In this case, the electrolyte is represented first and the metal or solid phase thereafter.
These two are separated by a vertical line or a semicolon.
A few examples of representing cathode half cell are given below-
(4) A salt bridge is indicated by two vertical line (ll) separating the two half cells. Thus,
applying above considerations to Daniel cell, we may represent it as-
Cell potential
Electrode potential
The equilibrium potential difference established between metal and its solution is
called the electrode potential of the metal.
Single Electrode Potential (E)
It is the measure of tendency of a metallic electrode to lose or gain electrons, when it is in

contact with a solution of its own salt.
Standard electrode potential ( Eᵒ)
It is the measure of tendency of a metallic electrode to lose or gain electrons, when it is in

contact with a solution of its own salt of 1 molar ( 1M) concentration at 25ᵒC. (298K)
Electricity cannot flow from one point to another unless there is a potential difference
between the two points. Hence, the flow of electricity from one electrode to another electrode in
a galvanic cell indicates that the two electrodes have different potentials.
The difference of potential which cause the flow of current from one electrode (which
is at a higher potential) to another electrode (which is at a lower potential) is called the
electromotive force (emf) or cell potential or cell voltage.
Relationship between cell potential and free energy (no derivation)
ΔG = -nFEcell
n = No. of electrons involved in the process.
F= Faraday = 96,500 Coulombs.
Eᵒ = Energy in volts.
ΔGᵒ= -nFEᵒcell
Nernst Equation for Single potential
Consider the following redox reaction occurring in an electrode:
For this equilibrium, the free energy change (ΔG) and the equilibrium constant (K) are
given by van’t Hoff isotherm as,
The decrease in free energy (-ΔG) will produce electrical energy.
As per the equation (1), this reaction involves the transfer of n number of electrons.
Hence, n Faraday of electricity (nF) will flow. If E is the emf of the electrode, then the total
electrical energy will be, nFE Joule.
This equation is known as Nernst equation for single electrode potential. (reduction
potential) when reduction reaction occurs at this electrode ( cathode).
Similarly, for oxidation potential,

Nernst Equation for reversible cell
Suppose the reaction occurring in a reversible cell is represented by the equation,
The decrease in free energy, -ΔG, accompanying the process is given by the well known
van’t Hoff reaction isotherm,
Where, -ΔG is the decrease in the free energy accompanying the same process when all
the reactants and products are in their standard state of unit activity.
J stands for the reaction quotient of the activities of the products and reactants at any
given stage of reaction.
Substituting the values of J, we have
If E is the emf of cell in volts and the cell reaction involves the passage of n Faradays,
i.e., nF coulombs, the electrical work done by the cell is, nFE joules.
Hence, the decrease in the free energy change of the system, -ΔG, is given by the
expression,
Where, Eᵒ is the emf of the cell in which the activity or as an approximation, the concentration of
each reactant and each product of the cell reaction is equal to unity. Eᵒ is known as the standard
emf of the cell.
Equation (8) is often referred to as the Nernst equation.
Replacing activities by concentrations, the Nernst equation may be written as,
The quantities given in paranthesis represent the concentrations of the species involved.
Nernst Equation applications
1. Oxidation reduction reaction
Indicator electrode – Platinum electrode;

Reference electrode – Calomel electrode
On applying Nernst equation
2. Acid-Base titration
HCl(aq)+NaOH(aq)→H2O(l)+NaCl(aq)
Indicator electrode – Platinum electrode

Reference electrode – Calomel electrode
3. Precipitation titration
Indicator electrode – sliver wire

Reference electrode – Calomel or silver electrode
Hydrogen, glass or antimony electrodes are used as indicator electrodes. Calomel
electrode is generally used as reference electrode.
Mixture of acids having different strengths like acetic acid and hydrochloric acid
can be titrated. In these cases the first break appears in the curve when the
stronger of the two acids is neutralized and the second when neutralization is
complete.

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Electrochemistry

These two are separated by a vertical line (l) or a semicolon (;)

Additional information regarding concentration may also be mentioned in bracket.

Single Electrode Potential (E)

It is the measure of tendency of a metallic electrode to lose or gain electrons, when it is in

Standard electrode potential ( Eᵒ)

It is the measure of tendency of a metallic electrode to lose or gain electrons, when it is in

Relationship between cell potential and free energy (no derivation)

n = No. of electrons involved in the process.

F= Faraday = 96,500 Coulombs.

Nernst Equation for Single potential

Consider the following redox reaction occurring in an electrode:

The decrease in free energy (-ΔG) will produce electrical energy.

Similarly, for oxidation potential,

Suppose the reaction occurring in a reversible cell is represented by the equation,

Substituting the values of J, we have

Equation (8) is often referred to as the Nernst equation.

Replacing activities by concentrations, the Nernst equation may be written as,

Nernst Equation applications

1. Oxidation reduction reaction

Indicator electrode – Platinum electrode;

Indicator electrode – Platinum electrode

Indicator electrode – sliver wire

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