CHEMISTRY (XI, XII & Medical) by VIJAY KUMAR (M.Sc.; B.Ed.

)
It is a branch of chemistry that deals with the relationship between chemical energy and electrical energy
and their inter conversions.

ELECTROCHEMICAL CELLS
These are devices that convert chemical energy of some redox reactions to electrical energy. They are also
called Galvanic cells or Voltaic cells.

An example for Galvanic cell is Daniel cell. It is constructed

by dipping a Zn rod in ZnSO4 solution and a Cu rod in
CuSO4 solution. The two solutions are connected externally
by a metallic wire through a voltmeter and a switch and
internally by a salt bridge.

A salt bridge is a U-tube containing an inert electrolyte like

NaNO3 or KNO3 in a gelly like substance. The functions of a
salt bridge are:
1. To complete the electrical circuit.
2. To maintain the electrical neutrality in the two half
cells.
The reaction taking place in a Daniel cell is -
Zn(s) + Cu2+(aq) → Zn2+ (aq) + Cu(s)
This reaction is a combination of two half reactions:
1. Cu2+ + 2 e⸻ → Cu(s) (reduction half reaction)
2+ ⸻
2. Zn(s) → Zn + 2 e (oxidation half reaction)

These reactions occur in two different portions of the Daniel cell. The reduction half reaction occurs on
the copper electrode while the oxidation half reaction occurs on the zinc electrode. These two portions of
the cell are also called half-cells or redox couples. The copper electrode may be called the reduction half
cell and the zinc electrode, the oxidation half-cell.

ELECTRODE POTENTIAL
When a metal rod is dipped in its own salt solution, there is a tendency of metal ions from the solution to
deposit on the metal electrode. At the same time, metal atoms of the electrode have a tendency to go into
the solution as ions. This tendency of a metal to lose or gain electron when it is in contact with its own
solution is called electrode potential.

When the concentrations of all the species involved in a half-cell is unity then the electrode potential is
known as standard electrode potential. According to IUPAC convention, standard reduction potential is
taken as the standard electrode potential.

In a galvanic cell, the half-cell in which oxidation takes place is called anode and it has a negative
potential. The other half-cell in which reduction takes place is called cathode and it has a positive
potential.

In a cell, the electrons flow from negative electrode to positive electrode and the current flows in
opposite direction. The potential difference between the two electrodes of a galvanic cell is called the cell
potential and is measured in volts. The cell potential is the difference between the electrode potentials
(reduction potentials) of the cathode and anode.

The cell electromotive force (emf) of the cell is the potential difference between the two electrodes, when
no current is flow through the cell.

By convention, while representing a galvanic cell, the anode is written on the left side and the cathode on
the right side. Metal and electrolyte solution are separated by putting a vertical line and a salt bridge is
denoted by putting a double vertical line.

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 CHEMISTRY (XI, XII & Medical) by VIJAY KUMAR (M.Sc.; B.Ed.)
For Daniel cell, the cell representation is -

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

Under this convention the emf of the cell is positive and is given by the potential of the half-cell on the
right hand side minus the potential of the half-cell on the left hand side., i.e

Ecell = Ecathode – Eanode

or
Ecell = Eright – Eleft

MEASUREMENT OF ELECTRODE POTENTIAL

The potential of individual half-cell cannot be measured. We can
measure only the difference between the two half-cell potentials that
gives the emf of the cell. For this purpose a half-cell called standard
hydrogen electrode (SHE) is used.

It consists of a platinum electrode coated with platinum black. The

electrode is dipped in an acidic solution of one molar concentration
and pure hydrogen gas at 1 bar pressure and 298 K is bubbled
through it. It is represented as Pt(s) | H2(g) | H+ (aq).

By convention, the electrode potential of SHE is taken as zero. To

determine the electrode potential of an electrode, it is connected in
series with the standard hydrogen electrode and the emf of the resulting cell is determined by the
equation, Ecell = ER – EL

Since the electrode potential of SHE is zero, the value of E cell is equal to the electrode potential of the
given electrode.
• If the standard electrode potential of an electrode is greater than zero (i.e. +ve), then its reduced
form is more stable compared to hydrogen gas.
• If the standard electrode potential is negative then hydrogen gas is more stable than the reduced
form of the species.

ELECTROCHEMICAL SERIES
It is a series in which various electrodes are arranged in the decreasing order of their reduction potential.
In this table, fluorine is at the top indicating that fluorine gas (F 2) has the maximum tendency to get
reduced to fluoride ions (F–). Therefore fluorine gas is the strongest oxidising agent and fluoride ion is the
weakest reducing agent. Lithium has the lowest electrode potential indicating that lithium ion is the
weakest oxidising agent while lithium metal is the most powerful reducing agent in an aqueous solution.

NERNST EQUATION
Nernst proposed an equation to relate the electrode potential of an electrode (or, emf of a cell) with the
electrolytic concentration.

He showed that for the electrode reaction:

M n+ (aq) + n e– → M(s)

the electrode potential can be given by:

RT [M]
0
E(Mn+/M) = E (Mn+/M) ― ––– ln –––––
nF [M n+]

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 CHEMISTRY (XI, XII & Medical) by VIJAY KUMAR (M.Sc.; B.Ed.)
Since the concentration of any solid is taken as unity, the above equation becomes:

RT 1
0
E(Mn+/M) = E (Mn+/M) ― ––– ln –––––
nF [Mn+]

2.303RT 1
0
E(Mn+/M) = E (Mn+/M) ― –––––––– log –––––
nF [Mn+]

Where E0 is the standard electrode potential, R is the gas constant (8.314 JK –1 mol–1), F is Faraday
constant (96487 C mol–1), T is temperature in Kelvin and [Mn+] is the concentration of the species Mn+.
By taking T = 298 K, R = 8.314 JK–1 mol–1 and F = 96500 C mol―1, the above equation can be simplied
as -
0.0591 1
E(Mn+/M) = E0(Mn+/M) ― –––––– log –––––
n [Mn+]

In Daniel cell, the electrode reactions are:

Cu2+ + 2 e― → Cu(s) (cathode)

Zn(s) → Zn2+ + 2 e― (anode)

The electrode potentials are given as-

0.0591 1
0
For cathode : E(Cu2+/Cu) = E (Cu2+/Cu) ― –––––– log ––––– {n=2}
2 [Cu2+]

0.0591 1
For anode : E(Zn2+/Zn) = E0(Zn2+/Zn) ― –––––– log ––––– {n=2}
2 [Zn2+]

The cell potential, Ecell = E(Cu2+/Cu) – E(Zn2+/Zn)

0.0591 1 0.0591 1
0 0
Ecell = {E (Cu2+/Cu) ― –––––– log –––––} ― {E (Zn2+/Zn) ― –––––– log –––––}
2 [Cu2+] 2 [Zn2+]
On solving the above equation, we get

0.0591 [Zn2+]
Ecell = Eocell ― –––––– log ––––––
2 [Cu2+]

For a general electro-chemical reaction of the type in 'n' number of electron is transferring :
aA+bB→cC+dD
Nerst equation can be represented as :
0.0591 [C]c [D]d
Ecell = Eocell ― –––––– log ––––––––
2 [A]a [B]b

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 CHEMISTRY (XI, XII & Medical) by VIJAY KUMAR (M.Sc.; B.Ed.)
EQUILIBRIUM CONSTANT & NERST EQUATION
For a electrochemical cell, when the cell reaction attains equilibrium,
then Ecell = 0

[C]c [D]d
and, –––––––– = Kc {eq. constant}
[A]a [B]b

Therefore, we can write Nernst equation as -

0.0591
o
0 = E cell ― –––––– log Kc
n

0.0591
o
E cell = –––––– log Kc
n

ELECTROCHEMICAL CELL & GIBBS ENERGY OF THE REACTION

Electrical work done in one second is equal to electrical potential multiplied by total charge passed. The
reversible work done by a galvanic cell is equal to decrease in its Gibbs energy and therefore, if the emf
of the cell is Ecell and nF is the amount of charge passed and ΔG is the Gibbs energy of the reaction, then

ΔG = – nFEcell

If the concentration of all the reacting species is unity, then Ecell = E0cell and we have

ΔG0 = –nFE0cell

Thus, from the measurement of E0cell, we can calculate the standard Gibbs energy of the reaction.

CONDUCTANCE OF ELECTROLYTIC SOLUTIONS

Resistance (R): The electrical resistance is the hindrance to the flow of electrons. Its unit is ohm (Ω). The
resistance of a conductor is directly proportional to the length of the conductor (Ɩ) and inversely
proportional to the area of cross-section (A) of the conductor.
i.e. R α Ɩ /A

or, R = ρ x Ɩ/A

where ρ (rho) is a constant called resistivity or specific resistance. Its unit is ohm-metre (Ω m) or ohm-
centimetre (Ω cm).

Resistivity (ρ) : It is defined as the resistance offered by a conductor having unit length and unit area of
crosssection.

Conductance (G) : It is the inverse of resistance. Its unit is ohm―1 or mho or Siemens (S)

i.e. G = 1/R

1×A
or, G = –––––
ρ× Ɩ

ƙ×A
or, G = –––––
Ɩ
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 CHEMISTRY (XI, XII & Medical) by VIJAY KUMAR (M.Sc.; B.Ed.)
Where, ƙ is called conductivity or specific conductance. It is defined as the conductance of a conductor
having unit length and unit area of cross-section. Its unit is Sm―1 or S cm―1.

There are of two types of Conductance - electronic or metallic conductance and electrolytic or ionic
conductance.

Electrical conductance through metals is called metallic or electronic conductance and it is due to the
movement of electrons. It depends on the nature and structure of the metal, the no. of valence electrons
per atoms and temperature. For electronic conductance, when temperature increases, conduction
increases.

The conductance of electricity by ions present in solutions is called electrolytic or ionic conductance.
It depends on i) the nature of electrolyte ii) size of the ion produced and their solvation iii) the nature of
the solvent and its viscosity iv) concentration of the electrolyte and v) temperature (As temperature
increases electrolytic conduction also increases).

Note : Substances which allow the passage of electricity in molten state or in solution state are called
electrolytes. On the passage of electricity, they undergo chemical decomposition.

MEASUREMENT OF THE CONDUCTIVITY OF IONIC SOLUTIONS

We know that, the conductance, G = ƙ × A/ Ɩ

So conductivity, ƙ = G × Ɩ/A

The quantity Ɩ/A is called cell constant (G*). It depends on the distance between the electrodes and their
area of cross-section. Its unit is m―1.

i.e. conductivity = conductance × cell constant

So in order to determine the conductivity of an electrolytic solution, first determine the resistance by
using a Wheatstone bridge. It consists of two resistances R 3 and R4, a variable resistance R1 and the
conductivity cell having the unknown resistance R2. It is connected to an a.c source (an oscillator, O) and
a suitable detector (a headphone or other electronic device, P). Direct current cannot be used since it
causes the decomposition of the solution.

The bridge is balanced, when no current passes through the detector.

Under this condition, R1 R3

––– = –––
R2 R4

Therefore, the unknown resistance, R2 = (R1.R4)/R3

By knowing the resistance, we get the value of conductance and conductivity.

CONDUCTIVITY CELL
It consists of two platinum electrodes coated with platinum black. The electrodes are separated by a
distance 'Ɩ' and their area of cross-section is 'A'.

The cell constant of a conductivity cell is

usually determined by measuring the
resistance of the cell containing a solution
whose conductivity is already known (e.g. KCl
solution).

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 CHEMISTRY (XI, XII & Medical) by VIJAY KUMAR (M.Sc.; B.Ed.)
MOLAR CONDUCTIVITY (Λm)
It is the conductivity of 1 mole of an electrolytic solution kept between two electrodes with unit area of
cross section and at a distance of unit length.

It is related to conductivity of the solution by the equation,

ƙ
Λm = –– (where C is the concentration of the solution)
C

ƙ × 1000
or, Λm = –––––––– (where M is the molarity and ƙ is conductivity in Scm―1)
M

The unit of molar conductivity is S cm2 mol―1.

VARIATION OF CONDUCTIVITY AND MOLAR CONDUCTIVITY WITH CONCENTRATION

Both conductivity and molar conductivity change with the concentration of the electrolyte.

For both strong and weak electrolytes, conductivity always decreases with dilution. This is because
conductivity is the conductance of unit volume of electrolytic solution. As dilution increases, the number
of ions per unit volume decreases and hence the conductivity decreases.

For both strong and weak electrolyte, the molar conductivity increases with dilution (or decreases with
increase in concentration), but due to different reasons.

1. For strong electrolytes, as dilution increases, the force of attraction between the ions decreases
and hence the ionic mobility increases. So molar conductivity increases.

When dilution reaches maximum or concentration approaches zero, the molar conductivity
becomes maximum and it is called the limiting molar conductivity (Λ0m).

For strong electrolytes, the relation between λm and concentration can be given as:

Λm = Λ0m ― A√c

Where ‘c’ is the concentration and 'A' is a constant depends on the nature of the electrolyte.

2. For weak electrolytes, as dilution increases, the degree of dissociation increases. So the number of
ions and hence the molar conductivity increases.

The variation of Λm for strong and weak electrolytes is shown in the following graphs:

For strong electrolytes, the value of λ0m can be determined by the extrapolation of the graph. But for
weak electrolytes, it is not possible since the graph is not a straight line. So their Λ0m values are calculated
by applying Kohlrausch’s law of independent migration of ions.
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 CHEMISTRY (XI, XII & Medical) by VIJAY KUMAR (M.Sc.; B.Ed.)
KOHLRAUSCH’S LAW OF INDEPENDENT MIGRATION OF IONS
The law states that the limiting molar conductivity of an electrolyte can be represented as the sum of the
individual contributions of the anion and the cation of the electrolyte.

Thus if an electrolyte on dissociation gives n(+) cations and n(-) anions, its limiting molar conductivity is
given as:
Λ0m = n(+)λ0(+) + n(―)λ0(―)

For NaCl, Ʌ0m (NaCl) = λ0(Na+) + λ0(Cl―)

For CaCl2, Ʌ0m (CaCl2) = λ0(Ca2+) + {2 × λ0(Cl―)}

Applications of Kohlrausch’s law

• Determination of Ʌ0m of weak electrolytes
By knowing the λ0m values of strong electrolytes, we can calculate Ʌ0m of weak electrolytes. For
example, we can determine the Ʌ0m of acetic acid (CH3COOH) by knowing the λ0m of
CH3COONa, NaCl and HCl as follows:

Ʌ0m (CH3COONa) = λ0 (CH3COO–) + λ0 (Na+) …………. (1)

Ʌ0m (HCl) = λ0(H+) + λ0(Cl-) ………….. (2)

Ʌ0m (NaCl) = λ0(Na+) + λ0(Cl-) ....……….. (3)

adding equation (1), (2) &(3) gives:

Ʌ0m (CH3COONa) + Ʌ0m (HCl) – Ʌ0m (NaCl)

= λ0(CH3COO-) + λ0(Na+) + λ0(H+) + λ0(Cl-) – λ0(Na+) – λ0(Cl-)

= λ0(CH3COOH)

• Determination of degree of dissociation of weak electrolytes

By knowing the molar conductivity at a particular concentration (Λm) and limiting molar
conductivity (Λ0m), we can calculate the degree of dissociation (α) as,
Λm
α = ––––
Λ0m

By using α, we can calculate the dissociation constant of acid as:

c α2
Ka = ––––
1–α

ELECTROLYTIC CELLS AND ELECTROLYSIS

In an electrolytic cell, the electrical energy is converted to chemical energy. The dissociation of an
electrolyte by the passage of electricity is called electrolysis e.g., when CuSO 4 solution is electrolysed by
Cu electrodes, Cu is deposited at the cathode and Cu2+ ions are liberated from the anode.

Quantitative Aspects of electrolysis – Faraday’s laws

1. Faraday’s first law
It states that the amount of substance deposited or liberated at the electrodes (m) is directly
proportional to the quantity of electricity (Q) flowing through the electrolyte.
Mathematically, mαQ
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 CHEMISTRY (XI, XII & Medical) by VIJAY KUMAR (M.Sc.; B.Ed.)
or, m = z.Q

where z is a constant called electrochemical equivalent {z = equivalent weight/96500}

But quantity of electricity is the product of current in ampere (I) and time in second (t).
i.e. Q = It

Therefore, m= zIt

1 Faraday is the charge of 1 mole of electron and its value is 96500 C/mol.
For the deposition of 1 mole of Na, the amount of charge required = 1 F (Since Na+ + e- → Na)
For Ca, Q = 2F (since Ca2+ + 2e- → Ca)

2. Faraday’s second law

It states that when same quantity of electricity is passed through solutions of different substances,
the amount of substance deposited or liberated is directly proportional to their chemical
equivalence e.g. when same quantity of electricity is passed through solutions of two substances A
and B, then
Mass of A deposited Equivalent mass of A
––––––––––––––––– = ––––––––––––––––––
Mass of B deposited Equivalent mass of B

PRODUCTS OF ELECTROLYSIS
The products of electrolysis depend on the nature of the electrolyte and the type of electrodes used. If the
electrode is inert (e.g. Pt, gold etc.), it does not participate in the electrode reaction. While if the electrode
is reactive, it also participate in the electrode reaction.

If molten NaCl is electrolysed, Na is deposited at the cathode and chlorine is liberated at the anode.
NaCl → Na+ + Cl-
At cathode: Na+ + e- → Na
At anode: Cl- → Cl2 + e-

If NaCl solution is electrolysed, we get H2 gas at the cathode and Cl2 gas at the anode.
NaCl solution contains four ions – Na+, Cl-, H+ and OH-
Cathode reaction: H+ + e- → H2
Anode reaction: Cl- → Cl2 + e-
NaOH is formed in the solution as solution contain only Na+ ions and OH- ions

BATTERIES
A battery is basically a galvanic cell in which the chemical energy of a redox reaction is converted to
electrical energy. They are of mainly two types – primary batteries and secondary batteries.
• Primary batteries: Here the reaction occurs only once and after use over a period of time, they
become dead and cannot be reused. e.g., Dry cell, mercury button cell etc. (Primary cells cannot
be recharged and reused).

1. Dry Cell - It is a compact form of Leclanche cell. It consists of a zinc container as anode and a
carbon (graphite) rod surrounded by powdered manganese dioxide (MnO 2) and carbon as cathode.
The space between the electrodes is filled by a moist paste of ammonium chloride (NH 4Cl) and
zinc chloride (ZnCl2).
The electrode reactions are:
Anode: Zn(s) → Zn2+ + 2e–
Cathode: MnO2 + NH4+ + e– → MnO(OH) + NH3
Ammonia produced in this reaction forms a complex with Zn 2+ and thus corrodes the cell. The cell
has a potential of nearly 1.5 V.

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 CHEMISTRY (XI, XII & Medical) by VIJAY KUMAR (M.Sc.; B.Ed.)
2. Mercury cell
Here the anode is zinc – mercury amalgam and cathode is a paste of HgO and carbon. The
electrolyte is a paste of KOH and ZnO. The electrode reactions are:
Anode reaction: Zn(Hg) + 2OH– → ZnO(s) + H2O + 2e–
Cathode reaction: HgO + H2O + 2e– → Hg(l ) + 2OH–
The overall reaction is : Zn(Hg) + HgO(s) → ZnO(s) + Hg(l )
The cell has a constant potential of 1.35 V since the overall reaction does not involve any ion in
solution.

• Secondary cells: A secondary cell can be recharged and reused again and again. Here the cell
reaction can be reversed by passing current through it in the opposite direction.

1. Lead Storage Cell - The most important secondary cell is lead storage cell, which is used in
automobiles and invertors. It consists of lead as anode and a grid of lead packed with lead dioxide
(PbO2) as the cathode. The electrolyte is 38% H2SO4 solution.
The cell reactions are:
Anode: Pb(s) + SO42― (aq) → PbSO4(s) + 2e-
Cathode: PbO2(s) + SO42―(aq) + 4H+(aq) + 2e- → PbSO4 (s) + 2H2O (l )
The overall cell reaction is: Pb(s)+PbO2(s)+2H2SO4(aq) → 2PbSO4(s) + 2H2O(l)
On charging the battery, the reaction is reversed and PbSO 4(s) on anode and cathode is converted
into Pb and PbO2, respectively.

2. Ni-Cd Cell - Another e.g. for a secondary cell is nickel – cadmium cell. Here the overall cell
reaction is -
Cd (s) +2Ni(OH)3 (s) → CdO(s) +2Ni(OH)2 (s) + H2O(l )

3. Fuel cells - These are galvanic cells which convert the energy of combustion of fuels like
hydrogen, methane, methanol, etc. directly into electrical energy.
One example for fuel cell is Hydrogen – Oxygen fuel cell, which is used in the Apollo space
programme. Here hydrogen and oxygen are bubbled through porous carbon electrodes into
concentrated aqueous sodium hydroxide solution. To increase the rate of electrode reactions,
catalysts like finely divided platinum or palladium metal are illed into the electrodes.
The electrode reactions are:
Cathode: O2(g) + 2H2O(l ) + 4e– → 4OH– (aq)
Anode: 2H2 (g) + 4OH– (aq) → 4H2O(l) + 4e–
Overall reaction is: 2H2 (g) + O2(g) → 2 H2O(l )

• Advantages of Fuel cells

1. The cell works continuously as long as the reactants are supplied.
2. It has higher efficiency as compared to other conventional cells.
3. It is eco-friendly (i.e. pollution free) since water is the only product formed.
4. Water obtained from H2 – O2 fuel cell can be used for drinking.

CORROSION
It is the process of formation of oxide or other compounds of a metal on its surface by the action of air,
water-vapour, CO2 etc. Some common examples are: The rusting of iron, tarnishing of silver, formation of
green coating on copper and bronze (verdigris) etc.

Most familiar example for corrosion is rusting of iron. It occurs in presence of water and air. It is a redox
reaction. At a particular spot of the metal, oxidation takes place and that spot behaves as anode. Here Fe is
oxidized to Fe2+.
2 Fe (s) → 2 Fe2+ + 4 e–

Electrons released at anodic spot move through the metal and go to another spot on the metal and reduce
oxygen in presence of H+ . This spot behaves as cathode. The reaction taking place at this spot is:

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 CHEMISTRY (XI, XII & Medical) by VIJAY KUMAR (M.Sc.; B.Ed.)

O2(g) + 4 H+(aq) + 4 e– → 2 H2O (l )

The overall reaction is:

2Fe(s)+O2(g) + 4H+(aq) → 2Fe2+(aq)+ 2 H2O (l )

The ferrous ions (Fe2+) are further oxidised to ferric ions (Fe 3+) and finally to hydrated ferric oxide
(Fe2O3.xH2O), which is called rust.

Methods to prevent corrosion

1. By coating the metal surface with paint, varnish etc.
2. By coating the metal surface with another electropositive metal like zinc, magnesium etc. The
coating of metal with zinc is called galvanisation and the resulting iron is called galvanized iron.
3. By coating with anti-rust solution.
4. An electrochemical method is to provide a sacrificial electrode of another metal (like Mg, Zn,
etc.) which corrodes itself but saves the object (sacrificial protection)

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