SimplyChem | Furqan Farooqi 27

CHAPTER 2
ELECTROCHEMISTRY
Electrochemistry is the study of production of electricity from energy released during spontaneous
chemical reactions and the use of electrical energy to bring about non-spontaneous chemical
transformations.
There are two types of cells
Electrochemical cells or Galvanic cell Electrolytic cells
Converts chemical energy of a spontaneous Uses electrical energy to carry out a non-
redox reaction into electrical energy. spontaneous redox reaction.
Used in - Used in -

Electrochemical cells or Galvanic cell

it is an electrochemical cell that converts the chemical energy of a spontaneous redox reaction into
electrical energy.
Example - In a Daniell Cell the energy of zinc - copper redox reaction is converted into electrical energy.

The following reactions occur at each electrode.

At Anode (oxidation) –

At Cathode (Reduction) –

Overall cell reaction –

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Cell representation
Oxidation half-cell || Reduction half-cell

The oxidation and reduction reactions occur in two different portions of the Daniell cell called half cells
or redox couple.

Salt bridge
It is a U-shaped tube filled with electrolyte fused in a gel. It helps complete the circuit by transfer of ion
between oxidation and reduction half cells.

Electrode potential (𝑬𝑴𝒏+/𝑴 )

A potential difference that develops between the electrode and the electrolyte is called electrode potential

Standard electrode potential (𝑬°𝑴𝒏+/𝑴 )

When the concentrations of all the species involved in a half-cell is unity (1 molL-1) then the electrode
potential is known as standard electrode potential.

There are two types of electrode potentials – oxidation potential and reduction potential. They are equal
for a species but have opposite signs.
Reduction potential = - Oxidation potential
According to IUPAC convention, standard reduction potentials are now called standard electrode
potentials.
Examples –

• Substances with higher E0 values tends to get reduced. Thus, acting as good oxidising agents.
• While the substance with lower E0 values tends to get oxidised. Thus, acting as reducing agents.

LEBRA
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Standard Electrode Potentials (Reduction Potentials) at 298 K

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Questions
1. Arrange these metals in their increasing order of reducing power.
K+ /K = –2.93V
Ag+ /Ag = 0.80V
Hg2+/Hg = 0.79V
Mg2+/Mg = –2.37 V
Cr3+/Cr = – 0.74V
2. Can you store ZnSO4 solution in a copper pot? Explain.
3. Using the standard electrode potentials, predict if the reaction between the following is feasible:
(i) Fe3+(aq) and I–(aq)
(ii) Ag+ (aq) and Cu(s)
(iii) Fe3+(aq) and Br–(aq)
(iv) Ag(s) and Fe3+(aq)
(v) Br2(aq) and Fe2+(aq).
4. Out of Zn and Sn, which metal should we coat iron with to protect it better from rusting? Give
reason.
5. Depict the galvanic cell in which the reaction
Zn(s) + 2Ag+ (aq) → Zn2+(aq) + 2Ag(s)
takes place. Further show:
(i) Which of the electrode is negatively charged?
(ii) The carriers of the current in the cell.
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Standard cell potential (𝑬°𝒄𝒆𝒍𝒍 )

It is defined as the potential difference between the two electrodes.

For example, in a Daniell cell –

For a cell to be feasible, 𝑬𝟎𝒄𝒆𝒍𝒍 must be positive.

Applying external voltage to galvanic cell

If an external opposite potential is applied in the Daniell cell and increased slowly, the reaction continues
to take place till the opposing voltage reaches the value 1.10 V when, the reaction stops altogether and no
current flows through the cell.
Any further increase in the external potential again starts the reaction but in the opposite direction. It now
functions as an electrolytic cell, which uses electrical energy to carry out a non-spontaneous redox
reaction.

Standard hydrogen electrode (SHE)

The potential of individual electrode cannot be measured. We can measure only the difference between
the potentials of the two electrodes.

If we arbitrarily choose the potential of one electrode (half-cell) as zero, then that of the other can be
determined with respect to this.

According to convention, a half-cell called standard hydrogen electrode (SHE) represented by

Pt(s)|H2(g)|H+(aq), is assigned a zero potential at all temperatures.

This hydrogen electrode can act as either cathode or anode depending on the other half cell.
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By taking standard hydrogen electrode as anode (reference half-cell) and the other half-cell as cathode,
gives the reduction potential of the other half-cell.
° ° °
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒
° ° °
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑃𝑡/𝐻 + /𝐻
2

° °
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 −0
° °
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒

Nernst Equation
The standard electrode potential assumes that the concentration of all the species involved is unity. But
this is not always the case.
So, the Nernst equation determine a relationship between electrode potential and concentration of ions.

Nernst equation for a half cell –

𝑀𝑛+ (𝑎𝑞) + 𝑛𝑒 − → 𝑀(𝑠)
The relationship between electrode potential and concentration can be given by the equation –
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When we take the log base 10 by replacing natural log ‘ln’ and put the values of universal gas constant R
= 8.314JK-1mol-1, faradays constant F = 96487Cmol-1 and temperature T =298K. we get,

For example,
In case copper electrode,

In case Hydrogen electrode,

In case of bromine electrode

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Nernst equation for a cell

For example, in case of a Daniell cell,

In case of Mg-Ag cell, Mg(s)|Mg2+(aq)||Ag+(aq)|Ag(s)

In case of Al – Fe cell, Al(s)|Al3+(aq)||Fe3+ (aq)| Fe2+(aq)

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In case of Cr – Cd cell, Cr(s)|Cr3+(aq)||Cd2+(aq)|Cd(s)

Questions
6. Calculate the potential of a copper electrode dipped in 0.01M CuSO4 Solution.
7. Calculate the potential of hydrogen electrode in contact with a solution whose pH is 10.
8. Calculate the emf of the cell in which the following reaction takes place:
Ni(s) + 2Ag+ (0.002 M) → Ni2+ (0.160 M) + 2Ag(s)
Given that E0cell = 1.05 V

9. Write the Nernst equation and emf of the following cells at 298 K
(i) Mg(s)|Mg2+(0.001M)||Cu2+(0.0001 M)|Cu(s)
(ii) Fe(s)|Fe2+(0.001M)||H+ (1M)|H2 (g)(1bar)| Pt(s)
(iii) Sn(s)|Sn2+(0.050 M)||H+ (0.020 M)|H2 (g) (1 bar)|Pt(s)
(iv) Pt(s)|Br – (0.010 M)|Br2 (l )||H+ (0.030 M)| H2(g) (1 bar)|Pt(s).
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Equilibrium constant from Nernst equation

In a Daniell cell –
𝑍𝑛 (𝑠) + 𝐶𝑢2+ (𝑎𝑞) → 𝑍𝑛2+ (𝑎𝑞) + 𝐶𝑢 (𝑠)
As time passes, the concentration of Zn2+ keeps on increasing while that of Cu2+ keeps on decreasing. At
the same time voltage of the cell as read on the voltmeter keeps on decreasing.

After some time, there is no change in the concentration of Cu2+ and Zn2+ ions and at the same time,
voltmeter gives zero reading.
This indicates that equilibrium has been attained. In this situation the Nernst equation may be written as:

Electrochemical cell and Gibb’s energy

Electrical work done in one second is equal to electrical potential multiplied by total charge passed.

The work done by a galvanic cell is equal to decrease in its Gibbs energy.

Therefore, the product of the emf of the cell ‘Ecell’ and the amount of charge passed ‘nF’ gives us Gibbs
energy change of the electrochemical cell ‘∆rG’
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°
If the concentration of all the reacting species is unity, then Ecell = 𝐸𝑐𝑒𝑙𝑙 , and we get,

Combining this with the equation of equilibrium constant, we get,

Questions
10. Calculate the equilibrium constant of the reaction:
Cu(s) + 2Ag+ (aq) → Cu2+(aq) + 2Ag(s)
Eocell = 0.46 V
11. The standard electrode potential for Daniell cell is 1.1V. Calculate the standard Gibbs energy
for the reaction:
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
12. The cell in which the following reaction occurs:
Fe3+(aq) + I-(aq) → Fe2+(aq) + I2(s)
has Eocell = 0.236 V at 298 K. Calculate the standard Gibbs energy and the equilibrium
constant of the cell reaction.
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Electrolytic cell
A cell that uses electrical energy to carry out a redox reaction.
A typical electrolytic cell is made up of a reactive or inert electrodes dipped in an aqueous or molten
electrolyte.
• Oxidation occurs at anode (+ve)
• Reduction occurs at cathode (-ve)

Products of electrolysis
The reactions that occur at anode
and cathode depend on the
following factors –

1.

2.

3.

Example –
1. Molten NaCl with Pt electrodes.
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Similarly, all alkali metals (Li, Na, K, Rb, Cs) and alkaline earth metals (Be, Mg, Ca, Sr, Ba) can be
obtained by electrolysis of their molten salts.

Electrochemical series -
Increasing order of reduction potential of some important species.
Li+
Na+
K+
Ca+2
Mg+2 Species with higher
Al+3 reduction potential is
Zn+2 reduced at cathode.
Fe+2 ↓
Pb+2 ↓
H+ ↓
Increasing
Cu+2
Reduction
Hg+2
potential
Ag+
↓
↓
𝐼− ↓
𝐵𝑟 −
𝐶𝑙 − Species with lowest
𝐹− reduction potential is
𝑶𝑯− oxidised at anode.
𝑆𝑂42−
𝑁𝑂3−
𝐶𝑂32−
𝐶𝑟2 𝑂72−

In case of Aqueous electrolytes

Examples-
Aqueous NaCl with platinum electrodes
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Aqueous AgNO3 with Pt electrodes

Dilute H2SO4 with platinum electrodes

Conc. H2SO4 with platinum electrodes

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In case of Active electrodes

Examples-
Aqueous CuSO4 with Cu electrodes

This can be used for electrolytic refining of low reactive metals like Cu or Ag, by taking impure metal as
anode and a thin strip of pure metal as cathode.
Electroplating
It can also be used for electroplating of metals. For example, plating zinc on iron (galvanization), Silver
plating on utensils, or chrome plating.

Galvanization
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Silver plating on an iron spoon can be done by taking Ag as cathode and the Fe spoon as cathode and a
solution of AgNO3 as electrolyte.

Quantitative aspects of electrolysis

Faraday’s laws of electrolysis
First law – The amount of chemical reaction which occurs at any electrode during electrolysis by a
current is proportional to the quantity of electricity passed through the electrolyte (solution or melt).
Number of moles of a species release or deposited on an electrode is given by the formula-
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Where,
w = mass of a substance deposited/liberated (g)
M = molar mass of a substance deposited/liberated (gmol-)
Q = Charge passed (C)
I = Current (A)
t = Time (s)
n = Number of moles of electron gained/lost
F = Faraday’s constant (96487 Cmol-1)

Second Law – The amounts of different substances liberated by the same quantity of electricity passing
through the electrolytic solution are proportional to their chemical equivalent weights (Atomic Mass of
Metal ÷ Number of electrons required to reduce the cation).

Questions
14. A solution of CuSO4 is electrolysed for 10 minutes with a current of 1.5 amperes. What is
the mass of copper deposited at the cathode?
15. Consider the reaction: Cr2O72– + 14H+ + 6e– → 2Cr3+ + 7H2O
What is the quantity of electricity in coulombs needed to reduce 1 mol of Cr2O72– ?
16. How much charge is required for the following reductions:
(i) 1 mol of Al3+ to Al?
(ii) 1 mol of Cu2+ to Cu?
(iii) 1 mol of MnO4– to Mn2+ ?
17. How much electricity in terms of Faraday is required to produce
(i) 20.0 g of Ca from molten CaCl2?
(ii) 40.0 g of Al from molten Al2O3 ?
18. How much electricity is required in coulomb for the oxidation of
(i) 1 mol of H2O to O2 ?
(ii) 1 mol of FeO to Fe2O3 ?
19. A solution of Ni(NO3)2 is electrolysed between platinum electrodes using a current of 5
amperes for 20 minutes. What mass of Ni is deposited at the cathode?
20. Three electrolytic cells A,B,C containing solutions of ZnSO4 , AgNO3 and CuSO4 ,
respectively are connected in series. A steady current of 1.5 amperes was passed through
them until 1.45 g of silver deposited at the cathode of cell B. How long did the current flow?
What mass of copper and zinc were deposited?
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Conductance of an electrolytic solution

Conductance is the property of a substance that helps the flow of current through it. It is the inverse of
resistance.
The electrical resistance of any object is directly proportional to its length, l, and inversely proportional to
its area of cross section, A.

Where,
R = Resistance (Ω) 𝜌 = Resistivity (Ω m )
l = length (m) A = Area of cross-section (m2)

The inverse of resistance is called conductance

Where,
G = Conductance (Ω-1 or mho or Siemens, S)
κ (kappa) = conductivity (Ω-1 m-1 or S m-1)
Conductivity of an object depends on the nature of material, temperature and pressure.
Object can be classified into conductors, insulators and semiconductors on the basis of conductivity.

Metallic conductivity Electrolytic conductivity

It is due the movement of electrons. It is due to the movement of ions
It decreases with increase in temperature. It increases with increase in temperature.
It depends on – It depends on –
• Nature of metal • Nature of electrolyte.
• Number of Valence electrons. • Size of ions.
• Nature & viscosity of the solvent.
• Concentration of the electrolyte.
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Measurement of Conductivity of an electrolytic solution

The conductivity of an electrolytic solution can be obtained by passing an AC current through and
electrolytic solution contained in a specially designed vessel called conductivity cell.

Conductivity of an electrolytic solution is defined as the conductance of a column of solution confined

between two electrodes of unit area of cross-section separated by a unit length.
𝐺×𝑙
𝜅=
𝐴

Cell Constant (G*)

The ratio of length to the area of cross section of a conductivity cell is a fixed quantity and is called the
cell constant (G*). It is also equal to the product of resistance, R and conductivity, 𝜅.

Measuring resistance of a cell using a Wheatstone bridge

It consists of two resistances R3 and R4 , a variable resistance R1 and the conductivity cell having the
unknown resistance R2 . The Wheatstone bridge is fed by an oscillator O (a source of AC power in the
audio frequency range 550 to 5000 cycles per second). P is a suitable detector (a headphone or other
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electronic device) and the bridge is balanced when no current passes through the detector. Under these
conditions:
𝑅1 𝑅4
Unknown resistance 𝑅2 =
𝑅3

These days, inexpensive conductivity meters are available which can directly read the conductance or
resistance of the solution

Molar conductivity (Λm)

Molar conductivity is the conductivity of a solution containing one mole of electrolyte.
Or
It is the conductivity of an electrolytic solution per unit molar concentration.

Questions
21. Resistance of a conductivity cell filled with 0.1 molL–1 KCl solution is 100 Ω. If the resistance
of the same cell when filled with 0.02 molL–1 KCl solution is 520 Ω, calculate the conductivity
and molar conductivity of 0.02 molL–1 KCl solution. The conductivity of 0.1 molL–1 KCl
solution is 1.29 S/m.
22. The electrical resistance of a column of 0.05 molL–1 NaOH solution of diameter 1 cm and
length 50 cm is 5.55 × 103 ohm. Calculate its resistivity, conductivity and molar conductivity.
23. The conductivity of 0.20 M solution of KCl at 298 K is 0.0248 Scm–1. Calculate its molar
conductivity.
24. The resistance of a conductivity cell containing 0.001M KCl solution at 298 K is 1500 Ω.
What is the cell constant if conductivity of 0.001M KCl solution at 298 K is 0.146×10–3Scm–1
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Variation of conductivity and molar conductivity with Dilution

Conductivity Molar conductivity
The conductivity of a solution at any given Molar conductivity of a solution at a given
concentration is the conductance of one unit volume concentration is the conductance of the volume V of
of solution kept between two platinum electrodes solution containing one mole of electrolyte kept
with unit area of cross section and at a distance of between two electrodes with area of cross section A
unit length. and distance of unit length.

Conductivity of an electrolyte decreases with Molar conductivity increases on dilution because

decreases in concentration (dilution). It is due to the decrease in conductivity is more than
the decrease in number of ions per unit volume. compensated by the increases in volume of the
solution.

The relation between conductivity and The relation between molar conductivity and
concentration is the same for both strong and concentration is different for strong and weak
weak electrolyte. electrolyte.

Limiting molar conductivity (𝚲𝒐𝒎 )

It is the molar conductivity of a solution as its concentration approaches zero (at infinite dilution)

Variation in molar conductivity of strong and weak electrolyte with concentration

Strong electrolyte Weak electrolyte
Λm increases slowly with dilution and can be Weak electrolytes like acetic acid have lower
represented by the equation: degree of dissociation at higher concentrations
and hence for such electrolytes, the change in Λm
with dilution is due to increase in the degree of
dissociation and consequently the number of ions
in total volume of solution that contains 1 mol of
electrolyte.
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The value of the constant ‘A’ for a given solvent

In such cases Λm increases steeply on dilution,
and temperature depends on the type of especially near lower concentrations. Therefore,
Λ𝑜𝑚 cannot be obtained by extrapolation of Λm to
electrolyte i.e., the charges on the cation and
anion produced on the dissociation of the zero concentration.
electrolyte in the solution. At infinite dilution (i.e., concentration c → zero)
electrolyte dissociates completely (α =1), but at
By extrapolating Λm to zero concentration, we such low concentration the conductivity of the
can obtain limiting molar conductivity, Λ𝑜𝑚 solution is so low that it cannot be measured
accurately.
Therefore, Λ𝑜𝑚 for weak electrolytes is obtained
by using Kohlrausch law of independent
migration of ions.

Degree of dissociation of weak electrolyte

At any concentration c, if α is the degree of dissociation

Dissociation constant of weak electrolyte

Kohlrausch law of independent migration of ions

The law states that limiting molar conductivity of an electrolyte can be represented as the sum of the
individual contributions of the anion and cation of the electrolyte.
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Questions

25. Calculate Λ𝑜𝑚 for CaCl2 and MgSO4.

26. Λ𝑜𝑚 for NaCl, HCl and NaAc are 126.4, 425.9 and 91.0 S cm2mol–1 respectively. Calculate
Λ𝑜𝑚 for HAc.
27. The conductivity of 0.001028 mol L–1 acetic acid is 4.95 × 10–5 Scm–1. Calculate its
dissociation constant if for acetic acid Λ𝑜𝑚 is 390.5 S cm2mol–1 .
28. The molar conductivity of 0.025 mol L–1 methanoic acid is 46.1 S cm2mol–1. Calculate its
degree of dissociation and dissociation constant. Given λ0(H+ ) = 349.6 S cm2mol–1 and
λ0(HCOO– ) = 54.6 S cm2mol –1 .
29. Conductivity of 0.00241 M acetic acid is 7.896 × 10–5 Scm–1. Calculate its molar
conductivity. If Λ𝑜𝑚 for acetic acid is 390.5 S cm2mol–1, what is its dissociation constant?
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Batteries
Batteries are electrochemical cells or galvanic cells that convert chemical energy of a spontaneous redox
reaction into electrical energy. This electrical energy can be used to run several electrical devices.
The batteries can be of two types – Primary and secondary batteries.

Primary batteries – In the primary batteries, the reaction occurs only once and after use over a
period of time battery becomes dead and cannot be reused again.
Examples –

Dry cell (Leclanche cell)

At Anode-

At Cathode

• The cell has a potential of 1.5V but this potential decreases over time because of the decrease
in concentration of NH4+ ions.
• The cell can not be recharged because NH3 forms a complex with zinc ions.

Used for –
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Mercury cell

At Anode-

At Cathode

The cell gives a constant potential of 1.35V throughout its life. This is because the cell reaction does not
involve any ions whose concentration can change.

Used for-
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Secondary batteries – A secondary cell after use can be recharged by passing current through it in the
opposite direction so that it can be used again

Examples –

Lead storage battery

Cell reactions while the battery is being used-

At Anode-

At Cathode
Cell reactions are reversed when the battery is charged

At Anode-

At Cathode

Used for -
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Nickel cadmium cell

At Anode-

At Cathode

It has a longer life than lead acid battery but it is expensive to make.

Used for -

Fuel cell

At Anode-

At Cathode –

It has a fuel efficiency of 70 % compared to thermal power plant which has a fuel efficiency of 40% only.
Used for -
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Electrochemical theory Corrosion

Corrosion of iron (commonly known as rusting) occurs in presence of water and air. It is an
electrochemical process.

A particular spot on the surface of iron behaves as anode and oxidation reaction occurs at this spot –

Oxidation-

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 hydrogen ions come from H2CO3 formed due to dissolution of carbon dioxide from air into water.
Hydrogen ion in water may also be available due to dissolution of other acidic oxides from the
atmosphere).

Reduction -

This is followed by atmospheric oxidation of ferrous ion to give hydrated ferric oxide, which comes out
as rust.

Atmospheric Oxidation-
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Summary