Electrochemistry

It is a branch of chemistry which deals with relationship between electrical energy and chemical
energy taking place in redox reaction.
It splits into three main aspects of study:

1. Electrochemical Cell
2. Electrolytic Conduction
3. Electrolysis

Electrochemical Cell
Converts chemical energy to electrical energy. E.g. Galvanic or Daniel Cell.

Galvanic/Daniel Cell:
Dip a Zn rod in ZnSO4 (aq) and Cu rod in CuSO4 (aq). Connect the two electrodes with a bulb
and we observe bulb glows and then it stop.

Why Bulb Glows?

It is observed that Zn loses 2e- (oxidises) to form Zn2+ ions (which goes into the solution) and
electrons carry current behaving as anode where as Cu2+ (from solution) gains 2e- (reduces) to
form Cu atom (which sticks to Cu electrode) at cathode and leaves SO42- ions in solution.
Daniel Cell

𝑜𝑟𝑑𝑛
𝐴𝑛𝑜𝑑𝑒 ⟹ 𝑍𝑛 (𝑠) – 2𝑒 − → 𝑍𝑛2+ (𝑎𝑞)
𝑅𝑒𝑑
𝐶𝑎𝑡ℎ𝑜𝑑𝑒 ⟹ 𝐶𝑢2+ (𝑎𝑞) + (𝑎𝑔) + 2𝑒 − → 𝐶𝑢 (𝑠)

𝑂𝑣𝑒𝑟𝑎𝑙𝑙 ⇒ 𝑍𝑛 (𝑠) + 𝐶𝑢2+ (𝑎𝑞) → 𝑍𝑛 (𝑠) + 𝐶𝑢2+ (𝑎𝑞)

𝑜𝑟 ⇒ 𝑍𝑛 (𝑠) + 𝐶𝑢𝑆𝑂4 (𝑎𝑞) → 𝑍𝑛𝑆𝑂4 (𝑎𝑞) + 𝐶𝑢(𝑠)

Why bulb stops glowing ?
After some time large number of Zn2+ ions surrounds Zn rod and SO42- ions surround Cu rod,
so these exess ions do not further allow electrons flow and infact repel them. Therefore electrons
flow stops and bulb stops glowing. To get continuous flow of current we insert a U-shaped tube
called salt bridge. It contains inert salt like KCl dissolved in gelatine or agar-agar solution
which remove these excess ion hence give continuous flow of current.
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Cell Representation - Zn(s) / ZnSO4 (aq) || CuSO4 (aq) / Cu(s).

Electrode Potential:
It is the tendency of an element to lose/gain e- when its rod or strip is dipped in its own salt
solution. It is of two types.

1. Oxidation Electrode Potential (OEP): Tendency to lose e-

M(s) → M+n (aq) + ne- E ° (𝑀/𝑀𝑛+ )

2. Reduction Electrode Potential (REP): Tendency to gain e-

M+n (aq) +ne- → M(s) E ° (𝑀𝑛+ /𝑀)

is standard electrode potential at 298K, 1 atm pressure and 1 molar solution

1.We always prefer REP value. REP = -(OEP)
2.Single E.P. values cannot be determined as it is a relative value, hence we need a reference
electrode called Normal or Standard Hydrogen Electrode (NHE) or (SHE) whose E ° is assumed
to be zero.

Normal/Standard Electrode Potential:

H2 gas at 1 bar pressure is passed through 1 M HCl at 298K in which platinum foil is coated
with platinum powder and dipped. This half cell is further connected to another half cell with
the help of potentiometer.
(NHE/SHE)

If NHE acts as anode: H2 → 2H+ + 2e- E ° (𝐻2 /𝐻 +) = 0.0𝑉

Pt, H2 (g) / H+(1M)

If NHE acts as cathode: 2H++2e- → H2 (g) E ° (𝐻 +/𝐻2) = 0.0𝑉

H+ (1M)/H2(g), Pt.
Through this method we calculate electrode potential values of all respective elements or
substances and can arrange them in electrochemical series.

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Electrochemical / Activity Series:
It is a vertical column in which elements are arranged in decreasing REP values.

Application of Electrochemical / Activity Series:

1. To compare relative oxidizing and reducing power: Element with higher REP, has greater
tendency to gain electron, hence higher oxidizing power and vice - versa.

2. To compare activities of Metal: Metals with lower REP and higher OEP has greater
tendency to lose electron, hence more reactive.

3. To calculate standard EMF of cell:

𝜺°𝒄𝒆𝒍𝒍 = 𝜺°𝒄𝒂𝒕𝒉𝒐𝒅𝒆 − 𝜺°𝒂𝒏𝒐𝒅𝒆 (Only REP values)

Nernst Equation: Dependence of E° on concentration.

In above example we took E.P. at standard condition i.e. 1 M, 298K & 1 bar, but it is not true
always, it means any of the above factor if changed then the entire concept becomes on non
standard , so what if concentration is changed. Therefore Nernst Equation gives the relationship:

i.e. Mn+ (aq) + ne- → M(s)

° 𝑅𝑇 [P]
So Nernst Equation is E(𝑀𝑛+/𝑀) = E(𝑀 𝑛+ /𝑀) − In [R]
𝑛𝐹

° 𝑅𝑇 [M](𝑠)
E(𝑀𝑛+/𝑀) = E(𝑀 𝑛+ /𝑀) − In [Mn+ ]
but [M] (s) = 1
𝑛𝐹

° 𝑅𝑇 [1]
∴ E(𝑀𝑛+/𝑀) = E(𝑀 𝑛+ /𝑀) − In [Mn+ ]
𝑛𝐹

° 2.303𝑅𝑇 [1]
E(𝑀𝑛+/𝑀) = E(𝑀 𝑛+ /𝑀) − log
𝑛𝐹 [M n+ ]

where R=8.314 Jmol-1K-1, T=298k, F=96500 C, n is number of electrons gained /lost.

° 0.059 [1]
So E(𝑀𝑛+/𝑀) = E(𝑀 𝑛+ /𝑀) − log [Mn+ ]
𝑛

Nernst Equation for Daniel Cell:

For Cathode:
° 2.303RT 1
E(Cu2+/Cu) = E(Cu2+ /Cu) − log [𝐶𝑢2+]
𝑛𝐹

For Anode:
° 2.303RT 1
E(Zn2+ /Zn) = E(Zn 2+ /Zn) − log [𝑍𝑛2+ ]
𝑛𝐹

E𝐜𝐞𝐥𝐥 = ECathode − EAnode (Under non standard condition)

E𝐜𝐞𝐥𝐥 = E(Cu2+ /Cu) − E(Zn2+/Zn) 22

 ° 2.203𝑅𝑇 1 ° 2.303RT 1
E𝐜𝐞𝐥𝐥 = E(Cu2+ /Cu) − log − [E 2+
(Zn /Zn) − log ]
𝑛𝐹 [𝐶𝑢2+ ] 𝑛𝐹 [𝑍𝑛2+ ]

° ° 2.303RT 1 1
E𝐜𝐞𝐥𝐥 = [E(Cu2+ /Cu) − E(Zn2+ /Zn) ] − [log 2+
− log ]
𝑛𝐹 [𝐶𝑢 ] [𝑍𝑛2+ ]

°
2.303RT [Zn2+ ]
E𝐜𝐞𝐥𝐥 = E𝑐𝑒𝑙𝑙 − log [For Zn(s) + 𝐶𝑢2+ (𝑎𝑞) → 𝑍𝑛2+ (𝑎𝑞) + 𝐶𝑢(𝑠)]
𝑛𝐹 [𝐶𝑢2+ ]

°
0.059 [Zn2+ ]
E𝐜𝐞𝐥𝐥 = E𝑐𝑒𝑙𝑙 − log
𝑛 [𝐶𝑢2+ ]

° 2.303𝑅𝑇 [P]
or in general for any cell E𝐜𝐞𝐥𝐥 = E𝑐𝑒𝑙𝑙 − log [𝑅]
𝑛𝐹

With Stoichiometric coefficient, it becomes raised to the power. i.e.

a A + b B → cC + dD

°
2.303𝑅𝑇 [C]c [D]d
E𝐜𝐞𝐥𝐥 = E𝑐𝑒𝑙𝑙 − log
𝑛𝐹 [A]a [B]b

Equilibrium Constant from Nernst Equation:

For example, in Daniel cell equation, initially conc. of Zn2+ increases & Cu2+ decreases and at
some time voltage of cell decreases. But after sometime we observe there is no change in any
conc., which shows equilibrium has reached and voltmeter shows zero reading.

So for Daniel Cell, Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu (s)

° 2.303𝑅𝑇 [Zn2+ ]
Nernst Equation becomes, Ecell = 0 = E𝑐𝑒𝑙𝑙 − log [𝐶𝑢2+]
𝑛𝐹

° 2.303𝑅𝑇 [Zn2+ ]
i.e. E𝑐𝑒𝑙𝑙 = log [𝐶𝑢2+]
𝑛𝐹

[Zn2+ ]
But at equation [𝐶𝑢2+] = 𝐾𝑐

°
0.059
∴ E𝑐𝑒𝑙𝑙 = log 𝐾𝑐
2

E°𝑐𝑒𝑙𝑙 ×2
i.e. log 𝐾𝑐 = 0.059

1.1 v × 2
log 𝐾𝑐 = = 37.288
0.059

∴ 𝐾𝑐 = 2 × 1037 𝑎𝑡 298 𝐾
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 ° 𝟐. 𝟑𝟎𝟑𝑹𝑻
𝐄𝒄𝒆𝒍𝒍 = 𝐥𝐨𝐠 𝑲𝒄
𝒏𝑭

Electrochemical Cell & Gibbs Energy of Reaction:

In electrochemical cell, the system does work by transferring electrical energy through an
electric circuit. Electrical work done in one second is equal to the electrical potential multiplied
by the total charge passed.

i.e. ∆r G =Max. Work

But Maximum work =nFEcell
In voltaic cell, work done is as electrical energy flows the external circuit and should be taken
-ve.

°
∆r G° = 𝑊𝑚𝑎𝑥 = −𝑛𝐹𝐸𝑐𝑒𝑙𝑙

∆r G° =-2.303RT log Kc

For cell to be spontaneous, ∆r G° must be –ve.

Q1. Calculate the emf of the cell.

Mg(s) / Mg2+ (0.001M ) || Cu2+ (0.0001M) / Cu (s) .
° °
Given: 𝐄(𝐂𝐮𝟐+ /𝐂𝐮) = 𝟎. 𝟑𝟒𝑽 𝐄(𝐌𝐠 𝟐+ /𝐌𝐠) = −𝟐. 𝟑𝟕𝟓𝑽

Q2.For concentration cell Cu(s) / Cu2+ (0.0 1M) || Cu2+(0.1M) / Cu (s).

(a) Calculate the cell potential.
(b) Will the cell generate emf when concentration becomes equal.

Q3.Write the Nernst equation and calculate the emf of the following cell at 298K.
Cu(s) | Cu2+ (0.130M) || Ag+ (0.01 M) | Ag(s)
° °
Given. 𝐄(𝐂𝐮𝟐+ /𝐂𝐮) = 𝟎. 𝟑𝟒𝑽 , 𝐄(𝐀𝐠 + /𝐀𝐠) = 𝟎. 𝟑𝟒𝑽 .

Q4.With the following reactions given, find the standard cell potentials of galvanic
cells with given reactions.
(i) 2Cr(s) + 3Cd2+(aq) → 2Cr3+(aq) + 3Cd
(ii) Fe2+(aq) + Ag+(aq) → Fe3+(aq) + Ag(s)
Calculate the ∆rGθ and equilibrium constant of the reactions.
ECr3+/Cr = 0.74 V, ECd2+/Cd = -0.40 V
° °
𝐄(𝐀𝐠 + /𝐀𝐠) = 𝟎. 𝟖𝟎𝑽 𝐄(𝑭𝒆 𝟑+ /𝐅𝐞𝟐+) = −𝟎. 𝟒𝟒𝑽

Q5.A zinc rod is dipped is 0.1M solution of ZnSO4. The salt is 95% dissociated at this
°
dilution at 298K. Calculate the electrode potential. Given 𝐄(𝐙𝐧 𝟐+ /𝐙𝐧) = −𝟎. 𝟕𝟔𝑽.

Q6.For the electrode Pt, H2(1 atm) | H+ (aq) (xM), the reduction electrode potential at
25°C is – 0.34V. Write the electrode reaction equation and calculate the value of x. How
will you deduce the pH of solution from this result?
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Q7.Calculate the equilibrium constant for the reaction at 25°C.
Cu(s) + 2Ag+ (aq) Cu2+ (aq) + 2Ag (s).
The standard cell potential for the reaction at 25°C is 0.46V.

Q8Write the Nernst equation and emf of the following cells at 298 K:
(i) Mg(s) | Mg2+(0.001M) || Cu2+(0.0001 M) | Cu(s)
° °
𝐄(𝐌𝐠 𝟐+ /𝐌𝐠) = −𝟐. 𝟑𝟕𝑽 𝐄(𝐂𝐮𝟐+ /𝐂𝐮) = 𝟎. 𝟑𝟒𝑽 Ans: 2.67 V

(ii)Fe(s) | Fe2+(0.001M) || H+(1M)|H2(g)(1bar) | Pt(s)

°
𝐄(𝐅𝐞 𝟐+ /𝐅𝐞) = −𝟎. 𝟒𝟒𝑽 E° (𝑯𝟐 /𝑯+) = 𝟎. 𝟎𝟎𝑽 Ans: 0.53 V

(iii) Sn(s) | Sn2+(0.050 M) || H+(0.020 M) | H2(g) (1 bar) | Pt(s)

°
𝐄(𝐒𝐧 𝟐+ /𝐒𝐧) = −𝟎. 𝟏𝟒𝑽 E° (𝑯𝟐 /𝑯+) = 𝟎. 𝟎𝟎𝑽 Ans: 0.08 V

(iv) Pt(s) | Br−(0.010 M) Br2(l) | || H+(0.030 M) | H2(g) (1 bar) | Pt(s).

°
𝐄(𝐁𝐫𝟐 /𝐁𝐫_)
= 𝟏. 𝟎𝟗𝑽 E° (𝑯𝟐 /𝑯+) = 𝟎. 𝟎𝟎𝑽 Ans: -1.298 V

Electrolytic Conduction:
Tendency of electrolyte to carry current is called conductance of conductivity. Resistance
offered by a conductor is directly proportional to length of conductor and inversly proportional
to area of cross section.
𝑙
Now, 𝑅∝𝑎 ρ is resistivity and defined as resistance offered by a conductor
of length 1 cm and having area of cross-section 1 cm2. S.I. unit is
Ω cm
𝑙
So R =ρ …1
𝑎

If 𝑙 = 1 cm & a = 1 cm2
Then R = ρ
Now, if we calculate reciprocal of equation 1.
1 1 𝑎
i.e. =𝜌 where G is conductance i.e. ease with which current flows (unit
𝑅 𝑙
is Siemen(S) & 1 S = 1Ω-1)
𝜅
So G = 𝐺∗ κ (kappa) is conductively i.e. conductance of 1cm3 of solution
of electrolyte. (Unit is Ω-1 cm-1 or Scm-1.
𝑙
G* is called cell constant = 𝑎 (𝒄𝒎−𝟏 )
➢ We cannot calculate directly, amount of conductance but can find the R of cell, hence we
make use of ohm’s law and calculate first R and then we reciprocal it to get G.
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Molar Conductivity (Λm):
It is the conducting power of all the ions obtained from 1 mole of electrolytic solution.
κ
Λ m = C where C is molar conc.
If C is in units of M.
𝜅×1000 𝜅×1000
then Λm= 𝐶 𝑜𝑟 𝑀
If C is the conc. of the solution in moles per litre i.e. molarity, then M mole of electrolyte is
present in 1000 cm3
𝑆𝑐𝑚−1 ×𝑐𝑚3
Units of Λm = 𝑚𝑜𝑙 𝐿−1

Λm = Scm2 mol-1
1000
So 1 mole of electrolyte is present in = 𝑐𝑚3 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑀

Measurement of Conductance and Conductivity of Ionic Solution:

The conductance of a solution is reciprocal of the R, ∴ experimental determination of G of
solution involves measurement of R which can be done with the help of Wheatstone bridge.
Wheatstone bridge

𝑅 𝑅 𝑅1 ×𝑅4
I.e. 𝑅1 = 𝑅3 so R2 =
2 4 𝑅3

R2 is unknown R.
But measuring R2 we face two problem
1. Passing DC changes the composition of solution i.e. causes electrolysis, so we use A.C.
and
2. A solution cannot be connected like a metallic wire or any other solid conductor,
therefore we use a specially designed cell called conductivity cell.

26
Conductivity Cell
Variation of conductivity(κ )
For strong or weak electrolyte conductivity(κ) depends on number of ions per unit volume. It
decreases with dilution and increases with increase in concentration of electrolyte.

Variation of Λm with conc. of strong and weak electrolyte:

1. Strong Electrolyte:
In case of strong electrolyte, at higher concentrations, the greater interionic attractions retard
the motions of the ions and therefore molar conductance falls with increasing concentrations.
With dilution, the ions are far apart and therefore interionic attractions decreases and
conductance increases with dilution and reaches maximum limiting value at infinite dilution Λ°m
.

Hence it can be expressed as Λm = Λ°m − 𝐴𝑐 1⁄2

when C→0 (i.e. infinite dilution)

Λm = Λ°m
A is constant depend upon type of electrolyte
Λm is molar conductivity at given concentration.
where Λ°m is molar conductivity at infinite dilution.

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2. Weak Electrolyte:
For weak electrolyte dissociation is very less as compared to strong electrolyte, therefore its
conductance is much lower than strong electrolyte at same concentration, but on dilution
dissociation (𝛼) of weak electrolyte increases, hence no. of ions increases, therefore Λm
increases sharply. However, it does not reach a limiting value.

Kohlrausch's Law of Independent Migration of Ions:

The limiting molar conductivity of an electrolyte is the sum of ionic conductivities of the cation
and anion of the electrolyte each multiplied with the number of ions present in one formula unit
of electrolyte. Mathematically,
Λ°m for Ax By = x Λ°+ +y Λ°−
For example,
Λ°m NaCl = Λ°m (Na+) + Λ°m (Cl-)
Λ°m MgCl2 = Λ°m (Mg2+) + 2 Λ°m (Cl-)

Application:
1. To calculate 𝚲°𝐦 for weak electrolyte
Since it is not possible to determine the value of Λ°m for weak electrolyte by extrapolation of
Λm versus √𝐶, but can be done by Kohlrausch law. E.g. to calculate Λm (CH3COOH) from HCl,
NaCl & CH3COONa.

So Λ°m HCl = Λ°m (H + ) + Λ°m (Cl− ) …1

Λ°m NaCl = Λ°m (Na+ ) + Λ°m (Cl− ) …2

Λ°m (CH3 COONa) = Λ°m (CH3 COO− ) + Λ°m (Na+ ) … 3

∴ for Λ°m (CH3 COOH) = 1 + 3 − 2

1. To Calculate Degree of Dissociation of W.E.:

Λ𝑐m
𝜶 = is molar conductivity at given conc.
Λ°m

𝑐 𝟐
Λ
𝑐( m° )
C∝2 Λm
and also K = = Λ𝑐
where K is dissociation constant.
1−∝
1−( m )
Λ°m

since 1-α = 1, therefore K = C α2

Electrolysis: Splitting of an electrolyte into ions in its molten/ aqueous state on passing current.
Quantitative Aspect of Electrolysis:
Charge on 1e- = 1.6021 x 10-19 C
Charge on 1 mole of electrons = 6.022 x 1023 x 1.6021 x 10-19 C
=96487C/mol. For approximate calculations we use F=96500C/mole = 1 Faraday (1F).

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Faraday’s Laws of Electrolysis:
(i) First Law: The mass of element deposited at electrode is directly proportional to quantity
of electricity passed.
𝑊 ∝ 𝑄 (charge)

𝑊 ∝𝐼 ×𝑡 as Q=I x t

𝑊 ∝𝑍𝐼𝑡 where Z is electrochemical equivalent

𝐴𝑡𝑜𝑚𝑖𝑐 𝑚𝑎𝑠𝑠
𝑍=
𝑛 × 96500
𝐴𝑡𝑜𝑚𝑖𝑐 𝑚𝑎𝑠𝑠 × 𝐼 ×𝑡
𝑊= n is number of electrons gain /charge on ion.
𝑛 ×96500

(ii) Second Law: When same amount of charge is passed through two or more cells connected
in series, then ratio of mass of substance deposited is equal to ratio of their chemical equivalents.
𝑚 𝐸 𝐴𝑡 𝑚𝑎𝑠𝑠
i.e. 𝑚1 = 𝐸1 E(Chemical equivalent) =
2 2 𝑛

Qualitative Aspect of Electrolysis:

(i) Electrolysis of molten𝑵𝒂𝑪𝒍: 𝑁𝑎𝐶𝑙 (𝑙) → 𝑁𝑎+ (𝑙) +𝐶𝑙-(𝑙)

𝐶𝑎𝑡ℎ𝑜𝑑𝑒 ⇒ 2Na+(𝑙) + 2e- →2 Na

𝐴𝑛𝑜𝑑𝑒 ⇒ 2Cl- (𝑙) → Cl2 (g) + 2e-

𝑂𝑣𝑒𝑟𝑎𝑙𝑙 𝑅𝑥𝑛 2NaCl (𝑙) →2Na (𝑠) + Cl2 (g)

Q9.The conductivity of 0.001M CH3COOH is 4.95 × 10–5 Scm–1. Calculate its dissociation
constant. Given for acetic acid °m is 390.5 Scm2 mol–1.

Q10.The conductivity of 0.20 M solution of KCl at 298 K is 0.0248 Scm −1. Find its molar
conductivity.
Ans: 124 Scm2mol-1

Q11.Considering the case of a conductivity cell having 0.001 M KCl solution at 298 K is 1500
Ω. If given, the conductivity of 0.001M KCl solution at 298 K is 0.146 × 10 −3 S, find the cell
constant?
Ans: 0.219 cm−1.

Q12. The molar conductivity of 0.1M CH3COOH solution is 4.6 Scm2mol–1. Calculate the
conductivity and resistivity of the solution.
[Ans : 0.00046 Scm–1, 2174 ohmcm]

Q13. The molar conductivities of NH4+ ion and Cl- ion are 73.5 S cm2mol-1 and 76.255 S
cm2 mol-1 respectively. The specific conductivity of 0.1 M NH4Cl is 1.288 × 10-2 Scm-1.
Calculate the dissociation constant of NH4Cl.
[Ans : 7.396 × 10-2]
29
Q14. Molar conductivity at infinite dilution for NH4Cl, NaOH and NaCl solution at 298K
are respectively 129.8, 218.4 and 108.9 S cm2mol–1 respectively. If the molar conductivity
of a centimolar solution of NH4OH is 9.33 S cm2mol–1. Calculate the degree of dissociation
of NH4OH.
[Ans. : 3.92%]

Q15. Silver is deposited on a metallic vessel of surface area 800cm2 by passing current of
0.2 ampere, for 3 hours. Calculate the thickness of silver deposited. (Density of silver 10.47
g cm–3, atomic mass of silver = 108 g mol–1]

Q16.How much charge is required for the following reductions of 1 mol of :

(i) Al3+ to Al.
(ii) Cu2+ to Cu.
(iii)MnO4− to Mn2+.
Given 1F= 96487 coulomb/mol
Q17.In terms of Faraday, how much electricity is required to produce :
(i) From molten CaCl2, 20.0 g of Ca. ( atomic mass of Ca=40g/mol)
(ii) From molten Al2O3, 40.0 g of Al. ( atomic mass of Al=27g/mol)
Q18.Calculate the amount of electricity required for the oxidation of 1 mol of the following
in coulombs :
(i) H2O to O2.
(ii)FeO to Fe2O3.
Q19.For 20 minutes, a current of 5 A is applied to between platinum electrodes to
electrolyze a solution of Ni(NO3)2. Find the amount of Ni deposited at the cathode? (atomic
mass of Ni=59g/mol)
[Ans: 1.825 g.]
Q20.Solutions of 3 electrolytic cells are ZnSO4, AgNO3 and CuSO4, cells are connected in
series. Of the cells, A, B, C respectively, after passing a steady current of 1.5 amperes, 1.45
g of silver was found deposited at the cathode of cell B. How much time did the current
flow? What amount of zinc and copper were deposited? (atomic mass of Zn=65.3g/mol,
Ag=108g/mol, Cu=63.5g/mol) [Ans: 14.40 min, 0.439 g of Zn, 0.426 g of Cu. ]
(ii) Electrolysis of aqueous salts:
Products of electrolysis of aqueous salts using Pt electrodes In general, if more than one
substance is present in the electrolytic cell, the substance liberated at the cathode is one which
has highest reduction potential and that liberated at the anode is the one which has the highest
oxidation potential. In view of the above conclusions, some more results are given below:

(i) Na+, K+, Mg2+, Ca2+ and Al3+ have much lower reduction potentials than that of water. Hence,
these ions are not reduced in the aqueous solution. Instead, reduction of water occurs giving H2
gas at the cathode.

30

At cathode:
H2O (l) → H+ (aq) + -OH (aq)
1
H+ + 1 e- → 2 H2

1
H2O (l) + e- → 2 H2 +-OH (aq) E°= -0.83V

(ii)Cu2+, Zn2+ and Ag+ ions have higher reduction potential than that of water. Hence, these ions
are easily reduced and deposited as Cu, Zn and Ag at the cathode.

At cathode:

Cu2+ (aq) +2e- Cu(s)

Zn2+ (aq) +2e- Zn(s)

Ag+ (aq) + e- Ag(s)

Cl-(exception), Br- , I- and conc. SO42- ions have much higher oxidation potential than that of
water. Hence, they are more easily oxidized in the aqueous solution giving Cl2 (g), Br2 (g), I2 (g)
2−
, 𝑆2 𝑂8 (𝑎𝑞) respectively at the anode.

At anode:

2Cl- (aq) Cl2 (g)

2Br- (aq) Br2 (g) +2e-

2I-(aq) I2 (g) +2e-

2𝑆𝑂42− (conc.) → 𝑆2 𝑂82− + 2e- E° = +1.96V

On the other hand, NO3-(aq), dilute SO42-, dilute PO43- and F-(aq) ions have much lower
oxidation potential than that of water. Hence, these ions are not oxidized in the aqueous solution.
Instead, H2O is oxidized to give O2 gas.

At anode:

2H2O (l) → 2H+ (aq) + 2-OH (aq)

1
2-OH →2 O2 + H2O +2e-

1
2H2O (l) O2 (g) + 2H+(aq)+2e- E°(oxid.pot.)= -1.23V
2

Q21. Write the products of electrolysis of aqueous salt using Pt electrodes ,NaCl, AgNO 3,
CuCl2, Na2SO4, concH2SO4, NaOH.

(ii) Electrolysis of aqueous𝑵𝒂𝑪𝒍:

𝑁𝑎𝐶𝑙(aq) →Na+ (aq) + Cl- (aq)

H2O (l) → H+ (aq) + -OH (aq)
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Cathode ⇒ Na+ + 1e- → Na E° = -2.71 V

H2O (l) → H+ (aq) + -OH (aq)
1
H+ + 1 e- → 2 H2

1
H2O (l) + e- → 2 H2 + -OH (aq) E°= -0.83V

Since REP of water is higher than that of Na, dissociation of water occurs liberating H2 gas at
cathode.
1
So net reaction at Cathode: H2O (l) + e- → 2 H2 +-OH (aq)
1
Anode: Cl- (aq) → 2 Cl2 (g) + e- E° (oxid pot.) = -
1.36 V
H2O (l) →O2 (g) +4H+ + 4e- E° (oxid pot.) = -
1.23 V
Since oxidation electrode potential of H2O is slightly more hence, it is supposed to get oxidized
in preference to Cl- (aq), but oxidation of water is slightly slow process therefore some extra
voltage (over voltage) is provided or required to fasten the process and in that case it is Cl- ion
which gets oxidized to give Cl2 (g).
1
Hence net reaction: Cl- (aq) + H2O (l) → -OH (aq) + 2 H2+ Cl2 (g).

(iii) Electrolysis of H2SO4 (aq):

H2SO4 (aq) → 2H+ (aq) + 𝑆𝑂42− (aq)
H2O (l) → 2H+ (aq) + -OH (aq)
1
Cathode: H2O (l) + e- → 2 H2 +-OH (aq) E°= -0.83V

Anode : 2H2O (l) → O2 (g) + 4e- E° (Ox) = -1.23 V………….1

2𝑆𝑂4 (aq) →𝑆2 𝑂82− (𝑎𝑞) + 2e-
2−
E° (Ox) = -1.96 V………….2

Since oxidation electrode potential of H2O is more than 𝑆𝑂42− (aq), water is oxidized at anode
liberating O2 (g). But with conc. of H2SO4, E° of 𝑐𝑜𝑛𝑐. 𝑆𝑂42− is calculated using Nernst
equation. 𝑆2 𝑂82− is obtained at cathode i.e. 2nd reaction occurs at anode.

(iii) Electrolysis of (conc) H2SO4

H2SO4 (aq) → 2H+ (aq) + 𝑆𝑂42− (aq)
H2O (l) → 2H+ (aq) + -OH (aq)
1
Cathode: H2O (l) + e- → 2 H2 +-OH (aq) E°= -0.83V

Anode : 2𝑆𝑂42− (conc.) →𝑆2 𝑂82− + 2e-

Q22. Write the products of electrolysis of aqueous CuSO4 using Cu electrode, aqueous
AgNO3 using Ag electrode?

Q23.Predict the products of electrolysis in each of the following :

(i) An aqueous solution of AgNO3 with silver electrodes.
32
(ii) An aqueous solution of AgNO3with platinum electrodes.
(iii) A dilute solution of H2SO4with platinum electrodes.
(iv) An aqueous solution of CuCl2 with platinum electrodes.
COMMERCIAL CELLS

The various commercial cells may be classified mainly into the following three types:

(A) Primary cells (B) Secondary cells (C) Fuel cells

Primary cells are those in which the redox reaction occurs only once and the cell becomes dead
after some time, and cannot be used again. Two common examples of this type are dry cell and
mercury cell.

Secondary cells are those which can be recharged by passing an electric current through them
and hence can be used over and again. Two well known examples of this type are lead storage
battery and nickel-cadmium storage cell.

Fuel cells are those in which the energy produced from the combustion of fuels such as H2, CO,
CH4, etc. is directly converted into electrical energy.

Primary cells.

Dry cell. It consists of a cylindrical zinc container which acts as the anode. A graphite rod
placed in the centre acts as the cathode. The space between the anode and the cathode is so
packed that zinc container is in touch with the paste of NH4Cl and ZnCl2 and the graphite rod
is surrounded by powered MnO2 and carbon.

The reactions taking place at the electrodes are

At anode: Zn(s) Zn2+ (aq) + 2e-

At cathode: 2MnO2(s) + 2NH4+ (aq) + 2e- MnO(OH) (s) + 2NH3 (g) + H2O

33
The NH3 formed is not liberated as gas but combines immediately with the Zn2+ ions and the
Cl- ions to form complex salt, [ Zn(NH3)2Cl2]. However, they do not have a long life because
the acidic NH4Cl corrodes the zinc container even when the cell is not in use.

Mercury cell: It consists of zinc –mercury amalgam as the anode and a carbon rod as the
cathode and a paste of mercuric oxide mixed with KOH as the electrolyte.

At anode: Zn(s) + 2OH- ZnO(s) + H2O(l) + 2e-

At cathode: HgO(s) + H2O(l) + 2e- Hg(l) + 2OH-

Overall reaction: Zn(s) + HgO(s) ZnO(s) + Hg(l)

1. Since no ions are involved in reaction, hence overall potential remain same through life.
2.Voltage is 1.35 V and is used in hearing aids, watches, cameras etc.

Secondary cells.

Lead storage battery. Each cell consists of a lead anode and a grid of lead packed with lead
dioxide as the cathode. These electrodes are suspended in dilute sulphuric acid (38% by mass)
which acts as the electrolyte.

34
The electrolyte reactions that occur during discharge are as follows:-

At anode: Pb (s) + SO42- (aq) PbSO4(s) + 2e-

At cathode: PbO2(s) + SO42- (aq) + 4H+ (aq) + 2e- PbSO4(s) + H2O
Overall reaction: Pb (s) +PbO2(s)+ 4H+(aq) + SO42- (aq) 2PbSO4(s) + 2H2O

Both electrodes gets covered by white ppt. of insoluble PbSO4, hence cell stops working and
needs recharging (electrolytic cell)
𝐸.𝐶.
Recharging: 2PbSO4 (s) + 2H2O → Pb(s) + PbO2(s) + 2H2SO4

(1) Nickel-Cadmium storage cell (or Nicad Cell). It consists of a cadmium electrode (as
anode) and a metal grid containing nickel oxide (as cathode) immersed in KOH solution.
The electrode reactions occurring during discharge are as follows:-
At anode: Cd(s) +2OH-(aq) Cd(OH)2(s) +2e-
At cathode: NiO2(s) +2H2O +2e- Ni(OH)2(s) +2OH-(aq)

(2) Fuel Cells . It consists of porous carbon electrodes containing suitable catalysts
(generally finely divided platinum and palladium) incorporated in them. Concentrated
KOH or NaOH solution is placed between the electrodes to act as the electrolyte.
Hydrogen and oxygen gases are bubbled through the porous electrodes into the
KOH/NaOH solution.

35
FUEL CELL OR HYDROGEN CELL

The following electrode reactions take place:

At anode: 2H2(g) + 4OH-(aq) 4H2O(l) +4e-

At cathode: O2(g) +2H2O(l) +4e- 4OH-(aq)

Overall reaction : 2H2(g) + O2(g) 2H2O(l)

Advantages of fuel cells. The three main advantages of fuel cells as under:

(i) Because of the continous supply, such cells never become dead. Such a cell is
usually operated at a temperature of 70-1400C and gives a potential of about 0.9 V.
(ii) Theoretically, the fuel cells are expected to have an efficiency of 60-70%.
(iii) They do not cause any pollution problem unlike thermal plants which burn fossil
fuels like coal, gas, oil etc.

Corrosion The process of slowly eating away of the metal due to attack of the atmospheric
gases on the surface of the metal resulting into the formation of compounds such as oxides,
sulphides, carbonates, sulphates etc. is called corrosion.

The most common example of corrosion is the rusting of iron. Rust is hydrated ferric oxide,
Fe2O3.xH2O. Some other examples include tarnishing of silver, development of green coating
on copper and bronze, etc.

36
Rusting of iron

At a particular spot of an iron object, oxidation take place and that spot behaves as anode.

At anode: 2Fe (s) 2Fe2+ (aq) + 4e-

The electrons lost by iron migrate through the metal to another site on the surface and reduce
dissolved oxygen in the presence of H+ ions.

At cathode: O2 (g) + 4H+ (aq) +4e- 2H2O

The ferrous ions are further reduced by oxygen in the presence of water forming ferric oxide
with further production of hydrogen ions.

4 Fe2+(aq) +O2 (g) +4H2O 2Fe2O3 + 8H+

Ferric oxide then undergo hydration to form rust.

Fe2O3 + x H2O Fe2O3.xH2O

37
Q24. Rusting of iron is quicker in saline water than in ordinary water. Explain?

Salt water increases electrical conductance of the electrolyte solution (i.e. faster movement of
electrons from iron to oxygen) formed on the metal surface. This accelerates the formation of
Fe2+ ion and hence that of rust.
Prevention from corrosion

Sacrificial Protection. Sacrificial protection means covering the iron surface with a layer of
metal which is more active (electropositive) than iron and thus prevents the iron from losing
electrons. The more active metal loses electrons in preference to iron and converts itself into
ionic state. The metal which is most often used for covering iron with more active metal is zinc
and the process is called galvanisation.

Galvanised nails.

Electrical protection - Cathodic Protection.

The iron object to be protected from corrosion is connected to a more active metal either directly
or through a wire. The iron object acts as cathode and the protecting metal acts as anode.
Magnesium is oftenly employed in the cathode protection of iron pipes buried in the moist soil,
canals, storage tanks, etc.

38