Chemistry class XI

Unit: Electrochemistry Name: _________________________________

12.1.1. define the terms:
a. Reduction: A process during which oxidation state of element decreases called reduction.
i. The reduction may be defined as, “ The reaction in which a substance (atom, ion or
molecule) gains one or more electrons and decrease its oxidation state.
In other words the atom, which accept electron is said to be reduced.
Examples:
i) Fe3+ + e- Fe2+
+ -
ii) 2H + 2e H2
iii) Sn4+ + 2e- Sn2+
–1 + –
iv) MnO4 + 8 H + 5e Mn2+ + 4H2O
v) Cl2 + 2e- 2Cl–
ii. Gain of hydrogen and loss of oxygen are also called reduction.
H2+ Cl2 2HCl
iii. Loss of oxygen may also define as reduction.
e.g. Reduction of ZnO into Zn
ZnO + H2 🡪 Zn + H2O

b. Oxidation:
i. The oxidation may be defined as, “ a chemical reaction in which a substance (atom, ion or
molecule) loses one or more electrons and increase its oxidation state”
In other words, the substance, which loses electrons is said to be oxidized.
Loss of Hydrogen and gain of oxygen also called oxidation.
Examples:
i) Zn Zn2+ + 2e
2+
ii) Fe Fe3+ + e
iii) Pb2+ Pb4+ + 2e
iv) H2+ Br2 2H+1Br–1
v) S–2 S+2e
ii. Loss of hydrogen 2HCl 🡪 H2+ Cl2
iii. Gain of oxygen C + O2 🡪 CO2
c. Oxidation number: The charge appears on atom in a compound molecule or ion called
oxidation number. E.g. Na+ Cl- H2+1S+6O4 4(-2)
d. Reducing agent: The substance which oxidizes itself in reaction and reduces other substance
in reaction called reducing agent. (H2S, H2, C, SO2, HI etc)
(eg) SO2 + 2H2S 3S + 2H2O.
Cl2 + H2S S + 2HCl.

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e. Oxidizing agent: The substance which reduce itself and oxidize other substances in reaction
called oxidizing agent.
(O2, O3, HNO3, H2O2, KMnO4 K2Cr2O7 etc)
(eg) Cu2+O2– + H2 Cu0 + H2O
Here Cu gains two electrons hence it is oxidizing agent.

* 12.1.2 determine oxidation number of an atom in pure substance:

Definition: “The apparent charge or formal charge (not real) positive or negative, which an
atom would have in a compound or ion is called oxidation number.” NaCl
Rules for determination of oxidation number: H2SO4 -8 + 2 +6 =0
1) The oxidation number of all the elements in their free state OR in homo atomic molecules
zero.
Br20, Na0, H20, O20 etc. Fe0
2) The oxidation number of H is always +1, except metallic hydrides where it is –1.
H+1 Cl–1 Na+ H–1
3) The oxidation state of O in most of the compounds is –2
Sr2+O–2, H2+1O–2
Few exceptions are
OF2 =0 O+2F2–1 Na+12 O2–1 K+1O2 –1/2
Peroxide super oxide
4) The oxidation number of each element of IA,IIA and IIIA in a compound is +1, +2, +3
respectively.
5) The oxidation number of F is always –1. While O.N of other halogens is variable in
binary compounds is –1.
H+1 F–1, Na+1 Cl–1, K+1 Br–1,
Few exceptions are.
H+1O2–Cl+1, H+1Cl3+O2–2, H+1Cl+5O3–2, H1+Cl+7O42–
6) The oxidation number of any ion is equal to the charge on the ion.
PO4–3 = – 3 Al+3 = + 3
7) The sum of oxidation number of all atoms in a neutral compound is zero.

Calculate the oxidation number of underlined element in the following compounds.

1) NaNO3 2) KMnO4 3) PO4–3
4) K2Cr2O7 5) NH4+ 6) H2SO4
7) Na2S2O3 8) SO3–2

(1) NaNO3 (2) KMnO4 (3) PO4–3

(+1)+ N+ (–2x3)= 0 (+1) Mn (–2x4)=0 PO3 = – 3

N=–1+6 Mn = -1, +8 P (–2x4) = – 3
N=+5 Mn = + 7 p–8=–3
P=+8–3
P=+5
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 (4) K2 Cr2 O7 (5) NH4+ (6) Na2 S2 O3

(7) H2 SO4 (8) SO3–2

12.1.3 determine reducing and oxidizing agent by using oxidation number change method:
i. SO2 + 2H2S 3S + 2H2O.

ii. Cl2 + H2S S + 2HCl.

iii. Cu2+O2– + H2 Cu0 + H2O

iv. Zn + H2 SO4 ZnSO4 + H2

v. H2+ Cl2 2HCl

12.1.4 balance a chemical equation using oxidation number change method.

Balancing of Redox Equations by Oxidation Number Method
Carry out the following steps for balancing of redox equations by oxidation number method.
(i) Write down the skeleton equation of the redox reaction under consideration.
(ii) Identify the elements, which undergo a change in their oxidation number during the reaction.
(iii) Record the oxidation number above the symbols of the element, which have undergone a
change in the oxidation number.
(iv) Indicate the change in oxidation number by arrows joining the atoms on both sides of the
equation. It shows number of electrons gained or lost.
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(v) Equate the increase or decrease in the oxidation number, i.e. electrons gained or lost by
multiplying with a suitable digit.
(vi) Balance the rest of the equation by inspection method.

Example
Balance the following equation by oxidation number method.

Step1:

Step2: Identify, those elements whose oxidation numbers have changed. Equation shows that Cr
goes from + 6 to +3 and it is reduced. Cl goes from -1 to zero and is oxidized. Moreover, the
oxidation number of chlorine remains the same, i.e from -1 to -1 when KCl and CrCl3 are
produced. So, we should write HCl, twice on the left hand side. One of HCI on left side shows
those Cl atoms which do not change their oxidation numbers Other HCI shows those Cl atoms
which undergo a change in their oxidation numbers.

Step3: In order to balance the number of electrons lost and gained multiply HCl with six. In this
way,
the 6 electrons lost by 6 Cl- will be gained by 2Cr+6 to give 2Cr+3. But do not multiply other
HCl
molecules with anything at this moment.

Step4: To balance K atoms, multiply KCl by 2.

Step5: Balance the rest of the equation by inspection method. To balance O atoms multiply H2O
with 7.

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Practice question:
Cu + HNO3 → Cu(NO3) 2 + NO2 + H2O

(ii) Zn + HNO3 → Zn(NO3 ) 2 + NO + H2O

(iii) Br2 + NaOH 🡪 NaBr + NaBrO3 + H2O

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12.1.5 identify oxidation and reduction half reaction.

Oxidation half reaction.

Reduction half reaction:

12.1.6 Balance a chemical equation using half reaction method:

Balancing Redox reaction equations by ion electron method:
This method was introduced by Jatte and Lamer in (1927). In this method equations are
not only balanced with atoms but also with respect to electrical charges. It involves following
steps.
1) Write skeleton equation in which atoms of reactants or products undergoing change in their
oxidation state.
2) Transform the molecular equation into ionic equation. If the equation is already in the ionic
form, then this step is omitted.
3) The ionic equation is broken into two half reaction i.e oxidation and reduction.
4) Balance each half reaction in terms of atoms, as given below.
a) The atoms other than O and H for each half reaction are balanced by using simple
multiples.
b) In acid or neutral medium, H+ and H2O are added for balancing H and O atoms
respectively. The O atoms are balanced first.
c) In case of basic medium, OH– and H2O are added for balancing O and H atoms
respectively.
5) Balance the charges in each half reaction by adding electrons either left or right side of the
equation.
6) Multiply each half equation by a number in order to equalize the number of electrons in each
half reaction.
7) Two balanced half reactions are added and common terms on both sides are cancelled.
\Note: It must be ensured that all electrons are cancelled out.
Balance the following equation by ion electron method
KMnO4 + H2SO4 + FeSO4 MnSO4 + Fe2(SO4)3 + K2SO4 + H2O
Step1: Transfer the equation into ionic form.
MnO4-1 + Fe+2 Mn+2 + 2Fe+3

Step2: Split the equation into two half reactions;

MnO4-1 Mn+2 (Reduction)
Fe+2 2Fe+3 (Oxidation)

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Step3: Balance the atoms.
MnO4-1 + 8H+ Mn+2 + 4H2O
+2
2Fe 2Fe+3
Step:4 Balance the charge.
MnO4-1 + 8H+ + 5e- Mn+2 + 4H2O
+2 +3 -
2Fe 🡪 2Fe +2e
Step5: Multiply both equations with opposite number of electrons.
2 ( MnO4-1 + 8H+ + 5e- 🡪 Mn+2 + 4H2O )
5( 2Fe+2 🡪 2Fe+3 +2e- )
2MnO4-1 + 16H+ + 10e- 🡪 2Mn+2 + 8H2O
10 Fe+2 🡪 10Fe+3 +10e-
Step6: Add both equations after cancelling common species.
2MnO4-1 + 16H+ + 10 Fe+2 🡪 2Mn+2 + 8H2O + 10Fe+3
Step7: Transfer the equation into skeleton form:
2 KMnO4 + 8H2SO4 + 10FeSO4 🡪 2MnSO4 + 8H2O + 5Fe2(SO4)3 + K2SO4

Example
Cr(OH)3 + SO4-2 🡪 C rO4-2 + SO3-2 (Basic medium)

Step1: Split the equation into two half reactions;

Cr(OH)3 🡪 CrO4-2 (Oxidation)
SO4-2 🡪 SO3-2
Step2: Balance the atoms;
Cr(OH)3 + 5OH- 🡪 CrO4-2 + 4H2O
SO4-2 + H2O 🡪 SO3-2 + 2HO-
Step3: Balance the charge by adding electrons:
Cr(OH)3 + 5OH- 🡪 CrO4-2 + 4H2O + 3e-
SO4-2 + H2O + 2e- 🡪 SO3-2 + 2HO-
Step4: Multiply both equations with opposite number of electrons:
2 (Cr(OH)3 + 5OH- 🡪 CrO4-2 + 4H2O + 3e-)
3 (SO4-2 + H2O + 2e- 🡪 SO3-2 + 2HO-)
Step: 5 Add both equations after cancelling common species.
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Practice questions
H3AsO3 + Cr2O72-🡪 3H3AsO4 + 2Cr3+ (acidic media)

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CN- + MnO4-1 🡪 CNO- + MnO2 (basic media)

12.1.7 discuss the uses of redox reactions in daily life:

make a bubble chart from the ppt uploaded in GCR

12.1.8 solve problems based on oxidation-reduction titrations;

Redox titration is based on an oxidation-reduction reaction between the titrant and the analyte. It
is one of the most common laboratory methods to identify the concentration of unknown
analytes.

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In order to evaluate redox titrations, the shape of the corresponding titration curve must be
obtained. In these types of titration, it proves convenient to monitor the reaction potential instead
of monitoring the concentration of a reacting species.

12.2.1 define the terms:

a. cathode: The electrode at which reduction takes place.
b. anode: The electrode at which oxidation takes place.
c. electrode potential: The potential set up when an electrode is in contact with one molar
solution of its own ions at 298 K is known as standard electrode potential or standard reduction
potential of the element. It is represented as E°.

d. standard electrode potential: "The value of the standard emf of a cell in which molecular hydrogen
under standard pressure is oxidized to solvated protons at the left-hand electrode"

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e. electrochemical series: When elements are arranged in the order of their standard, electrode
potentials on the hydrogen scale, the resulting list is known as electrochemical series.

12.2.2 describe Standard Hydrogen Electrode (SHE);

A standard hydrogen electrode which is used as a standard is shown in Fig. (10.4). It consists of
a piece of platinum foil, which is coated electrolytically with finely divided platinum black, to
give it a large surface area and suspended in one molar solution of HCl.
Pure hydrogen gas at one atmosphere pressure is continuously bubbled into 1M HCl solution.
The platinum acts as an electrical conductor and also facilitates the attainment of equilibrium
between the gas and its ions in solution. The potential of this electrode is arbitrarily taken as
zero.

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12.3.1 define the term ‘cell potential’; *
The difference between reduction potential value and oxidation potential value.

12.3.2 determine the potential of an electrochemical cell from the given standard electrode
potential values of substances.

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12.3.3 describe chemical reactions occurring within lead storage batteries; *

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12.3.4 explain the process of production of electrical energy in a fuel cell; *

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12.4 Faraday’s Law
12.4.1 explain Faraday’s first and second law of electrolysis;

First law of electrolysis : The mass of any substance deposited or liberated at any
electrode is directly proportional to the quantity of electricity passes. Thus if wg of the
​

substance is deposited on passing Q coulombs of electricity,

then W∝Q or W=ZQ where Z is a constant of proportionally called electrochemical
equivalent of the substance deposited. If a current of C amperes is passed for t seconds
then
Q=C×t
so at W=Z×C×t

Second law of electrolysis : When the same quantity of electricity is passed through
solutions of different electrolytes connected in the series, the weight of the substance

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produced at the electrodes is directly proportional to their equivalent weights.
For example, for CuSO4 solution and AgNO3 connected in the series if the same
​ ​

quantity of electricity is passed then,

12.4.2 calculate the quantity of charge passed in an electrochemical cell during electrolysis;
The coulomb is a measure of the quantity of electricity. If a current of 1 amp flows for 1 second,
then 1 coulomb of electricity has passed. That means that you can work out how much electricity
has passed in a given time by multiplying the current in amps by the time in seconds.

Example 1. Calculate the amount of charge transferred when a 5 A current is used for 2 minutes
during electrolysis.

2 minutes = 2 × 60 = 120 s

Charge = current × time

Charge = 5 × 120 = 600 C

The faraday

One faraday represents one mole of electrons. 1 farady equal to 96,500 coulombs. The use of the
faraday lets us work out how many moles of a substance is produced during electrolysis,
provided we know the total charge transferred.

Practice question:

12.4.3 calculate the mass or volume of substance produced during electrolysis.

Example 1. Bromine is produced during the electrolysis of molten lead(II) bromide:

2Br– → Br2 + 2e–

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A current of 13.4 A was used for 0.5 hours. Calculate the mass and volume of bromine produced.
1 F = 96,500 C. Ar of Br2 = 160.

Solution: charge = current × time

Charge = 13.4 × 1,800 = 24,120 C

Remember: One faraday represents one mole of electrons. It is equal to 96,500 coulombs.

Number of moles of electrons = 24,120 ÷ 96,500 = 0.25 mol

Amount of bromine produced = 0.25 ÷ 2 = 0.125 mol

Mass of bromine produced = Ar × mol = 0.125 × 160 = 20 g

Calculating volumes

The volume of a gas produced during electrolysis can be calculated from the charge transferred
and the faraday. You also need to know the molar volume of a gas. This is the same for any gas
at room temperature and pressure (rtp) and is 24 dm3 or 24,000 cm3.

Example 2. During electrolysis of molten sodium chloride, 0.125 mol of chlorine gas was
produced. Calculate the volume of chlorine at rtp.

Volume = amount of gas × molar volume

Volume of chlorine = 0.125 × 24 = 3 dm3 (or 3,000 cm3)

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