S-7: Free energy and EMF of cell, Nernst Equation

Electrolytic cell vs Galvanic cell

- -
At anode: Zn (s) Zn2+ (aq.) + 2 e-, E0 = 0.76 V
At anode: Cl ½ Cl2 (g) + e

+ -
At cathode: Cu2+ (aq.) + 2e- Cu (s), E0 = 0.34 V
At cathode: Na + e Na
Net reaction: Zn (s) + Cu 2+ (aq.) Zn2+ (aq.) + Cu (s)

The cell potential, Ecell = 0.34 + 0.76 = 1.1 V

2
 Electrolytic cell Electrochemical cell

Electrical energy is converted to Chemical energy is converted into

chemical energy electrical energy

An input of energy is required for the The redox reactions that take place in
redox reactions to proceed in these cells, these cells are spontaneous in nature
i.e. the reactions are non-spontaneous
Anode is positive and cathode is negative Anode is negative and cathode is
electrode positive electrode

The external battery supplies the The electrons are supplied by species
electrons. The electrons enter through the getting oxidized. They move from anode
cathode and come out through the anode to the cathode in the external circuit

3
 Types of reversible electrodes
1. Metal-Metal ion electrodes: A metal rod dipped in a solution containing its own ions
e.g., A Zn rod dipped in a solution of zinc sulphate
Electrode reaction: Mz+ (aq) + z e- M (s)

2. Gas electrodes
e.g., Hydrogen electrode
Hydrogen gas bubbled in a solution of an acid (HCl) forms this type of electrode.
H+ (aq) + e- H2 (g)

3. Metal- insoluble metal salt electrodes

A metal and a sparingly soluble salt of the same metal dipped in a solution of a soluble
salt having the same anion
e.g., Calomel electrode consists of mercury, mercurous chloride (Hg2Cl2 (s)) and a
solution of potassium chloride
Hg2Cl2 (s) + e- 2 Hg (l) + 2 Cl- (aq)

4. Redox electrodes
The potential is developed in these electrodes due to the presence of ions of the same
substance in two different valence states
e.g., A platinum wire inserted in a solution containing Fe2+ and Fe3+ ions
Fe3+ (aq) + e- Fe2+ (aq) 4
 Representation of the cell

The electrode on the right is written in the order:

Ion, electrode (e.g., Cu2+, Cu) (involving reduction)

e.g., Cu2+ (aq) + 2e- Cu (s)

The electrode on the left is written in the order:

Electrode, ion (e.g., Zn, Zn2+) (involving oxidation)

e.g., Zn2+ (aq) + 2e- Zn (s)

The net reaction: Cu2+ (aq) + Zn (s) Cu(s) + Zn2+ (aq)

Thus, the galvanic cell can be represented as:

Zn (s), Zn2+ (aq) ⎪Cu2+ (aq), Cu (s)

 Determination of cell potential
The half-cell reaction with a lower reduction potential is
subtracted from the one with a higher electrode potential if both
half cell reactions are presented as reduction reactions.

(i) Cu2+ (aq) + 2e- Cu (s); Eel0 = 0.34 V

(ii) Zn2+ (aq) + 2e- Zn (s); Eel0 = -0.76 V

Subtracting Eq. (ii) from Eq. (i), we get

Cu2+ (aq) + Zn (s) Cu(s) + Zn2+ (aq)

The cell potential, Ecell0 = 0.34 – (-0.76) V

= 1.10 V
 Effect of electrolyte concentration on electrode potential
Gibbs and Helmholtz independently pointed out that the electrical energy of a reversible
cell originates from the decrease in free energy (-∆G) of the reaction occurring in the cell.

Thus, -∆G = nFE (E is emf of the cell)

Nernst Equation:
From thermodynamics, it is known that -∆G = -∆G0 – RT ln Q
where Q is reaction quotient of the cell reaction, given by the ratio of concentration of
products and reactants.

Thus, nFE = nFE0 – RT lnQ

or, E= E0 – (RT/nF) lnQ
or, E= E0 – (0.0591/n) log Q at 25 °C
This is known as Nernst equation, which gives the effect of the concentrations of
reactants and products involved in the cell reaction on the EMF of the cell.
For any electrode reaction, Mn+ + ne- M
Nernst equation can be written as, Eel = E0 – (2.303 RT/nF) log ([M]/[Mn+ ])
= E0 – (2.303 RT/nF) log (1/[Mn+])
= E0 + 2.303 RT/nF) log [Mn+]
where E0 is standard electrode potential. 7
 Application of EMF measurements
Determination of pH by using hydrogen electrode

Let us consider a hydrogen electrode in contact with a solution of H+ ions.

The electrode potential associated with the reaction, H+ + e- ½ H2 (1 atm) can be
given by Nernst equation, i.e.,

Eel = Eel0 – 2.303 (RT/F) log 1/[H+]

= 2.303 (RT/F) log [H+] {as Eel0 = 0}
= -2.303 (RT/F) pH
= -0.0591 pH at 25 °C

By combining with a reference electrode, e.g., calomel electrode, the EMF of the cell
can be determined as

E = Ecalomel – EH2
or E =0.242- (-0.0591 pH)
or 0.0591 pH =E - 0.242
or pH = (E-0.242)/0.0591
Thus, the pH can be evaluated by knowing the value of EMF of the cell.
8
 Solubility Product
The solubility product of a sparingly soluble salt forming a saturated solution in
water is given by the product of concentration of the ions raised to a power equal to the
number of times ions occur in the equation representing the dissociation of electrolyte.
Consider a salt MX is in equilibrium with its ions in a saturated solution

MX (s) M+ (aq)+ X- (aq)

The solubility product of the salt is given by

Ksp = a M+ x a X- = [M+] [X-] assuming an ideal solution

The half-cell reactions are:

LHE: M M+ (aq) + e-
RHE: MX (s) + e- M + X-
Overall: MX (s) M+ (aq) + X- (aq)

Knowing that ∆G0 = -nFE0 = -2.303 RT log Ksp, we get

log Ksp = nFE0/ 2.303 RT
Thus, knowing the value of E0, Ksp can be calculated
S-9: Corrosion, Dry and Wet corrosions
 Corrosion
Corrosion refers to the unwanted deterioration of a metal as a result of
chemical reactions between it and the surrounding environment.
Example: Rusting of iron

Most of the corrosions involve in the formation of metal oxides.

This means that any metal (with the exception of gold) will be
oxidized in any environment that contains oxygen.

There are several types of corrosion, including wet corrosion and

dry corrosion.
❖ Dry corrosion occurs when there is no water or moisture to aid
the corrosion, and the metal gets oxidized with the atmosphere
alone.

❖ Wet corrosion of metals occurs through electron transfer,

involving two processes, oxidation and reduction
There are many factors that dictate how corrosive an environment
is.

❖ The amount of oxygen available to form corrosion products or the

presence of water or moisture which greatly accelerate the rate of
corrosion.

❖ Another is the presence of other elements, ions and compounds

that can limit or enhance corrosion rates. Therefore corrosion rates
are often considered in different atmospheres: industrial, rural and
marine.
 Dry corrosion
It is also known as chemical corrosion

This corrosion is due to the direct chemical attack on the metal

surface by the atmospheric gases such as

oxygen, halogen, hydrogen sulphide, sulfur dioxide

Different types:

❖ Oxidation corrosion

❖ Liquid metal corrosion

❖ Corrosion by other gases

 Oxidation corrosion
Direct attack of oxygen on metal surfaces in the absence of moisture

e.g., Alkali metals (Li, Na, K etc.) and alkaline metals (Mg, Ca etc.)
are rapidly oxidized at low temperature

Mechanism:

Oxidation takes place at the surface of metal forming metal ions

M Mn+ + ne-
Oxygen is converted to oxide by accepting the electron from the metal

(n/2) O2 + 2ne- nO2-

M + O2 Metal oxide (corrosion product)

 Liquid metal corrosion

When a liquid metal is allowed to flow over a solid metal at high

temperature is called liquid metal corrosion

This is due to the chemical action of flowing liquid metal on solid metal
or alloy
Example: In nuclear reactor, sodium metal is used as the coolant and leads
To corrosion of Cd

Corrosion by other gases

Some gases reacts with certain metal and forms a protective or non-protective layer on
metallic surface. Thus, metals undergo corrosion due to the reaction of gases.

Ex: When steel is exposed to hydrogen gas at high temperature

H2 + heat 2 H, C+4H CH4
The presence of methane gas in the voids of steel develops high pressure, which causes
cracking of steel.
 Wet corrosion
Also known as electrochemical corrosion

This type of corrosion occurs due to the flow of electron

from the metal anodic surface towards cathodic area through
a conducting solution

Electrochemical corrosion involves

❖ The formation of anodic and cathodic areas or parts in

contact with each other
❖ presence of a conducting medium
❖ corrosion of anodic areas only
 Types of Wet corrosion

1. Galvanic corrosion

2. Concentration cell corrosion

Galvanic corrosion

❖ When two dissimilar metals (e.g., Zn and Cu) are electrically connected and
exposed to an electrolyte, the metal higher in electrochemical series undergoes
corrosion

Mechanism:
In acidic solution, the corrosion occurs by the hydrogen evolution process,
whereas in neutral or slightly alkaline solution, oxygen absorption occurs.

The electron-current flows from the anode metal, Zn to cathode metal Cu.

At anode: Zn Zn2+ + 2e- (oxidation)

 Concentration cell corrosion
❖ This is due to the electrochemical attack on the metal surface exposed
to an electrolyte of varying concentration or of varying aeration

❖ When one part of metal is exposed to a different air concentration from

the other part

If a metal is partially immersed in a conducting solution, the metal part

above the solution is more aerated and becomes cathodic.

The metal part inside the solution is less aerated and thus becomes anodic
and suffers from corrosion

At anode: M M2+ + 2e- (oxidation)

At cathode: ½ O2 + H2O + 2e- 2OH-

Concentration cell corrosion
Pourbaix diagram for Iron