6.

Redox Reactions
6.1 Introduction Oxidants/ Oxidising agent : A reagent/
substance which itself undergoes reduction and
Can you tell? causes oxidation of another species is called
oxidant /oxidising agent. Now consider some
1. Why does cut apple turn brown when
more examples.
exposed to air ?
Mg(s) + F2 (g) Mg F2(s) (6.5)
2. Why does old car bumper change colour?
Mg (s) + S(s) MgS (s) (6.6)
3. Why do new batteries become useless
The above reactions are also examples
after some days ?
of oxidation though no oxygen is involved
Redox is an abbreviation used for the and thus scope of oxidation can be expanded.
terms 'oxidation and reduction'. A large Combination with electronegative element is
number of phenomena such as respiration, oxidation. Oxidation can also be looked upon
rusting, combustion of fuel involve redox as the removal of electropositive element.
reactions. For example
Hg2Cl2 (s) HgCl2 (s) + Hg(s) (6.7)
Can you recall? Now let us consider some examples of
reduction.
1. What is combustion reaction?
a. Removal of oxygen from mercuric oxide
2. Write an equation for combustion of
2 HgO (s) 2 Hg (l) + O2 (g) (6.8)
methane.
b. Removal of electronegative element from
3. What is the driving force behind reactions
FeCl3 as in
of elements?
2 FeCl3 + H2 (g) 2FeCl2 (aq) + 2 HCl
6.1.1 Classical ideas of redox reactions (6.9)
Classically oxidation refers to combination of c. Addition of hydrogen
an element or a substance with oxygen. CH2 = CH2 (g) + H2 (g) CH3 - CH3 (g)
For example, Oxidation of carbon (6.10)
C (s) + O2 (g) CO2 (g) (6.1) 2 HgCl2(aq) + SnCl2 (aq) Hg2Cl2(s) +
Oxidation of magnesium SnCl4 (aq) (6.11)
2 Mg + O2 2 MgO(s) (6.2) In eq. (6.8) there is removal of oxygen
In reaction (6.1) and (6.2) the carbon from mercuric oxide Eq (6.9) shows removal of
and magnesium are oxidized on reacting with electronegative element from FeCl3 Eq (6.10)
oxygen. Now consider the reaction : involves addition of hydrogen. Equation (6.11)
2 Fe2O3 + 3 C (s) 4 Fe (s) + 3 CO2 (g) involves addition of an electropositive element
(6.3) Hg to HgCl2. All these reactions represent
In this reaction there is removal of oxygen reduction.
from Fe2O3. Hence it is a reduction reaction. Reductant / reducing agent : A reagent /
Further reducing agent is defined as a substance/
2H2S (g) + O2 (g) 2 S (s) + 2 H2O (l) reagent which itself undergoes oxidation
(6.4) bringing about the reduction of another
In this reaction there is removal of species. Now consider again equation (6.11).
hydrogen and is also called oxidation. Here The equation (6.11) involves simultaneous
the sulfur in H2S loses hydrogen and undergoes oxidation and reduction. In this reaction HgCl2
oxidation while oxygen accepts hydrogen and is reduced to Hg2Cl2 and SnCl2 is oxidized to
undergoes reduction. SnCl4. Hence it is redox reaction.
81
Key points oxidation reaction and that involving gain of
Oxidation it is defined as: electrons is called reduction. Thus eq. (6.14) is
a. addition of oxygen. oxidation, eq. (6.15) is reduction and eq. (6.16)
b. addition of electronegative element. is a redox reaction.
c. removal of hydrogen. Key points : Oxidant / oxidizing agent : A
d. removal of electropositive element. reagent / substance which itself undergoes
e. loss of electrons by any species. reduction and causes oxidation of another
Reduction it is defined as: species is called oxidant or oxidizing agent.
a. removal of oxygen. This is an electron acceptor.
b. removal of electronegative element. Reductant / Reducing agent : A reagent /
c. addition of hydrogen. reducing agent is defined as a substance /
d. addition of electropositive element. reagent which itself undergoes oxidation and
e. gain of electrons by any species. brings about reduction of another species. A
6.1.2 Redox reaction in terms of electron reductant is electron donor.
transfer : Redox reaction can be described as Displacement reactions can also be looked
electron transfer as shown below. upon as redox reactions. In such reactions an
Mg + O2 Mg2 + O2 (6.12) ion (or atom) in a compound is replaced by an
Mg + F2 Mg + 2F
2
(6.13) ion (or on atom) of another element.
Development of charges on the species X + YZ XZ + Y
produced suggest the reactions 6.12 and 6.13 The reaction (6.16) is displacement reaction.
can be written as :
Loss of 2e Try this
Mg(s) + O2(g) Mg2 + O2 Complete the following table of displacement
Gain of 2e reactions. Identify oxidising and reducing
Loss of 2e agents involved.
Reactants Products
Mg(s) + F2(g) Mg2 + 2F
Zn (s) + (aq) (aq) + Cu (s)
Gain of 2e
Cu (s) + 2 Ag+ (aq) +
When Mg is oxidised to MgO, the neutral
+ Co (aq) + Ni (s)
2+
Mg atom loses electrons to form Mg2 in
MgO. The elemental oxygen gains electrons 6.2 Oxidation number : Description of redox
and forms O2 in MgO. reaction in terms of electron transfer suggest
Each of the above steps represents a half involvement of only ionic species in it. But
reaction which involves electron transfer (loss many reactions involving only covalent bonds
or gain). Sum of these two half reactions or the also fulfil the classical definition of oxidation
overall reaction is a redox reaction. Now and reduction. For example:
consider the following half reactions. 2H2 (g)+ O2 (g) 2H2O (l) (6.17)
Fe(s) Fe 2 (aq) + 2e (6.14) H2 (g) + Cl2 (g) 2HCI(g) (6.18)
Cu (aq) + 2e
2
Cu(s) (6.15) Eq (6.17) represents oxidation of H2 as it is
combination with oxygen. An electronegative
Fe(s) + Cu2 (aq) Fe 2 (aq) + Cu(s) element Cl is added to H2, and therefore,
(6.16) eq (6.18) also represents oxidation of H2. As
In the half reaction (6.14) Fe acts as a reducing products of both these oxidations are polar
agent whereas Cu 2 acts as oxidising agent covalent molecules, there is an electron shift
which accepts electrons from Fe. The half rather than complete electron transfer from
reaction involving loss of electrons is called one species to the other.

82
 A practical method based on oxidation 5. The oxidation number of F is -1 in all of its
number is developed to describe all the redox compounds. The other halogens Cl, Br and I
reactions, which are either ionic involving usually exhibit oxidation number of -1 in
complete electron transfer or covalent which their halide compounds. However in
refer to shift of electrons. In this method the compounds in which halogens Cl, Br and I
electron pair in a covalent band is assumed to are bonded to oxygen, oxidation number of
belong to more electronegative element, that halogens is +1 For example,
is, it shifts completely to more electronegative H-F KBr Cl-O-Cl H-O-Cl
element.
+1-1 +1-1 +1 -2 +1 +1 -2 +1
Oxidation number of an element in
a compound is defined as the number of 6. The algebraic sum of oxidation numbers of
electrical charges it carries (assuming complete all the atoms in a neutral molecule is zero.
7. The algebraic sum of oxidation numbers of
electron transfer in the case of covalent bond).
all the atoms in a polyatomic ion is equal to
The following rules have been formulated to
net charge of the ion.
determine the oxidation number of an element
8. When two or more atoms of an element are
in a compound.
present in molecule or ion, oxidation number
6.2.1 Rules to assign oxidation number
of the atom of that element will be average
1. The oxidation number of each atom of an oxidation number of all the atoms of that
element in free state is zero. Thus : Each element in that molecules.
atom in H2, Cl2, O3, S8, P4, O2, Ca, etc. has By applying rules 1 to 5 it is possible to
oxidation number of zero. determine oxidation number(s) of atoms of
2. The oxidation number of an atom in a various elements in molecules or ions. For
monoatomic ion is equal to its charge. Thus doing this the rules 6, 7 and 8 are useful.
alkali metals have oxidation number +1 in
all their compounds (NaCl, KCl, etc.).
Problem 6.1: deduce the oxidation number
Alkaline earth metals have oxidation of S in the following species:
number +2 in all their compouds (CaCO3, i. SO2 ii. SO42
MgCl2, etc.). Al is considered to have +3 as Solution:
its oxidation number in all its compounds. i. SO2 is a neutral molecule :
3. The oxidation number of O is usually -2 in Sum of oxidation number of all atom of
all of its compounds except in peroxide or SO2 = 0 = (oxidation number of S)
peroxide ion where it has oxidation number + 2 x (oxidation number of O)
of -1 and in superoxide each oxygen has 0 = (oxidation number of S) + 2 x (-2)
oxidation number -1/2. Oxidation number of S in SO2
Ca-O H-O-O-H (O-O) KO2 = 0 – (2x (-2)) = 0 – (-4) = + 4
ii. SO4 is an ionic species.
2

+2 -2 +1 -1 -1 +1 -1 -1 +1 -1/2 Sum of oxidation number of all atom of

SO42 = -2
In OF2 oxidation number of oxygen is +2.
= Oxidation number of S + 4 x (Oxidation
4. The oxidation number of H atom is either
number of O)
+1 or -1. When the H atom is bonded to Oxidation number of S in SO42
nonmetals, its oxidation number is +1. When = -2 -4 x (-2) = -2+8 = + 6
it is bonded to metals, it possesses oxidation
number of -1. Remember
(O-H) H-O-H Li-H H-Ca-H
Oxidation number of an element can be
-2 +1 +1 -2 +1 +1 -1 -1 +2 -1 positive or negative and a whole number
or a fraction.
83
6.2.2 Stock notation : Oxidation number (+1) + oxidation number of Mn + 4 x (-2) = 0
represents the oxidation state of an atom and oxidation number of Mn + 1 - 8 = 0
is also denoted by Roman numeral in oxidation number of Mn - 7 = 0
parentheses after the chemical symbol of the oxidation number of Mn = +7
concerned element in the molecular formula. b. K2Cr2O7
This representation is called Stock notation 1. oxidation number of K =+1
after the German Scientist Alfred Stock. For 2. oxidation number of O = -2
example : 3. sum of oxidation number of all atoms = 0
1. Au1 Cl 1 Au(I)Cl 2 x oxidation no. of K + 2x oxidation
2. Au3 Cl3 1 Au(III)Cl3 number of Cr +7x oxidation number of O = 0
3. Sn Cl4
4 1
Sn(IV)Cl4 2 x (+1) + 2 x oxidation number of Cr + 7
4. Sn Cl2
2 1
Sn(II)Cl2 x ( 2) = 0
5. Mn4 O2 2 Mn(IV)O2 +2 +2 x oxidation number of Cr - 14 = 0
The Stock notation is used to specify the 2x oxidation number of Cr + 2 - 14 = 0
oxidation number of the metal. The idea of 2x oxidation number of Cr - 12 = 0
oxidation number is very convenient to define 2x oxidation number of Cr = +12
oxidation, reduction and the substances like oxidation number of Cr = +12 /2
oxidizing agent (oxidant) and reducing agent oxidation number of Cr = +6
(reductant) of the redox reaction. c. Ca3(PO4)2
6.2.3 Redox reaction in terms of oxidation 1. oxidation number of Ca = +2
number : (alkaline earth metal ion)
Oxidation : An increase in the oxidation 2. oxidation number of O = -2
number of an element in a given substance. 3. sum of oxidation number of all atoms = 0
Reduction : A decrease in the oxidation 3 x O.N. of Ca + 2 x oxidation number of
number of an element in a given substance. P + 8 x oxidation number of O = 0
Oxidizing agent : A substance which increases 3 x(+2) + 2 x oxidation number of P
the oxidation number of an element in a given + 8 x (-2) = 0
substance, and itself undergoes decrease in + 2 x oxidation number of P -16 = 0
oxidation number of a constituent element. 2 x oxidation number of P -16 + 6 = 0
Reducing agent : A substance that lowers the 2 x oxidation number of P -10 = 0
oxidation number of an element in a given 2 x oxidation number of P = +10
substance, and itself undergoes an increase in oxidation number of P = +10/2
the oxidation number of a constituent element oxidation number of P = + 5
in it.
Problem 6.2 : Assign oxidation number to Problem 6.3 : Assign oxidation number to
each element in the following compounds the atoms other than O and H in the
or ions. following species.
a. KMnO4 b.K2Cr2O7 c. Ca3(PO4)2 i. SO32 ii. BrO3 iii. ClO4 iv. NH4 v. NO3
Solution : vi. NO2 vii. SO3 viii. N2O5
a. KMnO4 Solution : The oxidation number of O atom
1. Oxidation number of K = +1 bonded to a more electropositive atom is -2
2. Oxidation number of O = -2 and that of H atom bonded to electronegative
3. Sum of the oxidation numbers of all atom is +1. Using these values the oxidation
atoms = 0 numbers of atoms of the other elements in a
Oxidation no. of K + oxidation of Mn given polyatomic species are calculated.
+ 4 x oxidation number of O = 0
84
i. SO32
- 2 = oxidation number of S Do you know ?
+ 3 x (oxidation number of O) Some elements in a particular
Oxidation number of S = - 2 - 3 (-2) compound may possess fractional oxidation
=-2+6=4 number. For example : C3O2, Br3O8,
ii. BrO3 Na2S4O6, C8H18, etc. In these compounds
- 1 = oxidation number of Br oxidation number of C, Br, S, C are 4/3,
+ 3 x (oxidation number of O) 16/3, 2.5, 9/4, respectively. These oxidation
Oxidation number of Br = - 1 - 3 (-2) numbers are actually the average oxidation
=-1+6=5 number of all the atoms of elements in that
Similarly the oxidation number in the compound. Different atoms of the element
remaining species are found to be in such species exhibit different oxidation
iii. Cl in ClO4 : +7 iv. N in NH4 : -3 states. For example : Tertra thionate ion has
v. N in NO3 : +5 vi. N in NO2 : +3 two S atoms with oxidation number +5 and
vii. S in SO3 : +6 viii. N in N2O5 : +5 two with zero (0). Therefore, the average
oxidation number of S in these species is
10/4 = 2.5
Problem 6.4 : Identify whether the following O O+5
+5 0 0
reactions are redox or not. State oxidants
-
O - S - S - S - S - O- structure of S4O62-
* *

(tetrathionate ion)
and reductants therein.
a. 3H3AsO3(aq) + BrO3 (aq) 6.3 Balancing of redox reactions : Two
Br (aq) + 3H3AsO4(aq) methods are used to balance chemical equation
1. Write oxidation number of all the atoms for redox processes : Oxidation number
of reactants and products method and Half reaction method or Ion
3H3AsO3(aq) + BrO3 (aq) Br (aq) + 3H3AsO4(aq) electron method.
6.3.1 The Oxidation number method is
+1 +3 -2 +5-2 -1 +1 +5 -2
2. Identify the species that undergoes change illustrated in the following steps :
in oxidation number Step I : Write the unbalanced equation for
Loss of 2e
redox reaction. Balance the equation for all
atoms in the reactions, except H and O.
3H3AsO3(aq) + BrO3 (aq) Br (aq) + 3H3AsO4(aq) Identify the atoms which undergo change in
Gain of 6e oxidation number and by how much. Draw the
The oxidation number of As increases bracket to connect atoms of the elements that
from +3 to +5 and that of Br decreases from changes the oxidation number.
+5 to -1. Because oxidation number of one Step II : Show an increase in oxidation number
species increases and that of other decreases, per atom of the oxidised species and hence the
the reaction is therefore redox reaction. net increase in oxidation number. Similarly
The oxidation number of As increases show a decrease in the oxidation number per
by loss of electron. Thus As is a reducing atom of the reduced species and the net
agent and it itself is oxidized. On the other decrease in oxidation number. Determine the
hand, the oxidation number of Br decreases. factors which will make the total increase and
Hence, it is reduced by the gain of electron decrease equal. Insert the coefficients into the
and act as an oxidizing agent. equation.
Result : Step III : Balance oxygen atoms by adding
1. The reaction is redox reaction. H2O to the side containing less O atoms, One
2. Oxidant/oxidizing agent - BrO3 H2O is added for one O atom. Balance H
3. Reductant/Reducing agent - H3AsO3 atoms by adding H ions to the side having
less H atoms.
85
Step IV : If the reaction occurs in basic
Problem 6.6 : Balance the following
medium, then add OH ions, equal to the
reaction by oxidation number mathod.
number of H ions added in step III, on both
CuO+ NH Cu + N2+ H2O
the sides of equation. The H and OH on same
Solution :
sides of reactions are combined to give H2O
Step I : Write skeletal equation and balance
molecules.
the elements other that O and H.
Step V : Check the equation with respect to
CuO + 2 NH Cu + N2+ H2O
both, the number of atoms of each element and
the charges. It is balanced. Step II : Assign oxidation number to Cu and
Note : For acidic medium step IV is amitted. N. Calculate the increase and decrease in
Problem 6.5 : Using the oxidation number the oxidation number and make them equal.
method write the net ionic eqvation for the CuO + 2NH3 Cu+ N2 + H2O
reaction of potassium permanganate, KMnO4,
+2 -2 -3 +1 0 0
with ferrous sulphate, FeSO4.
MnO4 (aq) + Fe2 (aq)
increase in oxidation number :
Mn2 (aq)+ Fe3 (aq) 2NH3 N2
Solution :
Step 1 : The skeletal ionic equaiton is -3 0
MnO4 (aq) + Fe2 (aq) increase per atom = 3
Mn2 (aq)+ Fe3 (aq) decrease in oxidation number
Step 2 : Assign oxidation number to Mn and CuO Cu
Fe, and calculate the increase and decrease in
the oxidation number and make them equal . +2 0
MnO4 (aq) + Fe2 (aq) Mn2 (aq) + Fe3 (aq) decrease per atom = 2
to make the net increase and decrease equal
+7 -2 +2 +2 +3 we must take 3 atoms of Cu and 2 atoms
increase in oxidation number : of N
Fe (+2) Fe (+3)
increase per atom = 1 3CuO+2NH3 3Cu+N2+ H2O
decrease in oxidation number Step III : Balance 'O' atoms by addition
Mn(+7) Mn(+2) 2H2O to the right hand side.
decerase per atom = 5 3CuO+2NH3 3Cu+N2+ 3H2O
to make the net incerase and decrease equal we
must take 5 atoms of Fe2 Step IV : Charges are already balanced
MnO4 (aq) + 5Fe2 (aq) Step V : Check two sides for balanced of
Mn2 (aq) + 5Fe3 (aq) atoms and charges. The equation obtain in
Step 3 : Balance the 'O' atoms by adding step IV is balanced.
4H2O to the right hand side.
MnO4 (aq) + 5Fe2 (aq) 3CuO+2NH3 3Cu+N2+ 3H2O
Mn2 (aq) + 5Fe3 (aq) + 4H2O(l)
Step 4: The medium is acidic. To make the 6.3.2 Ion electron method (Half reaction
charges and hydrogen atoms on the two sides method) : In this method two half equations
equal, add 8H on the left hand side. are balanced separately and then added
MnO4 (aq) + 5 Fe2 (aq) + 8H (aq) together to give balanced equation. Following
Mn2 (aq) + 5Fe3 (aq) + 4H2O(l) steps are involved
Step 5: Check the two sides for balance of Step I : Write unbalanced equation for the
charges and atoms. The net ionic equation redox reaction, Assign oxidation number to all
obtained in step 4 is the balanced equation. the atoms in the reactants and products. Divide
MnO4 (aq) + 5 Fe2 (aq) + 8H (aq) the equation into two half equations. One half
Mn2 (aq) + 5Fe3 (aq) + 4H2O equation involves increase in oxidation number
and another involves decrease in oxidation
86
number (Write two half equation separately)
Step II : Balance the atoms except O and H in Reduction
each half equation. Balance oxygen atom by ClO3 (aq) ClO2 (aq) + H2O (l)
adding H2O to the side with less O atoms. Step III : Balance H- atoms by adding H
Step III : Balance the H- atom by adding H+ ions to the side with less H. Hence add 4H
ions to the side with less H- atoms. ions to the right side of oxidation and 2H
Step IV : Balance the charges by adding ions to the left side of reduction.
appropriate number of electrons to the right Oxidation
side of oxidation half equation and to the left Mn2 (aq) + 2 H2O (l) MnO2 + 4H
of reduction half equation. (aq)
Step V : Multiply half equation by suitable Reduction
factors to equalize the number of electrons in ClO3 (aq) + 2 H (aq) ClO2 (aq)
two half equations. Add two half equations + H2O (l)
and cancel the number of electrons on both Step IV : Now add 2 electrons to the right
sides of equation. side of oxidation and 1 electron to the left
Step VI : If the reaction occurs in basic side of reduction to balance the charges.
medium then add OH- ions, equal to number of Oxidation
H ions on both sides of equation. The H and Mn2 (aq) + 2 H2O(l) MnO2 (s) +
OH- ions on same side of equation combine to 4 H (aq) + 2 e
give H2O molecules. Reduction
Step VII : Check that the equation is balanced ClO3 (aq) + 2H (aq)+ e ClO2 (aq)
in both, the atoms and the charges. + H2O(l)
Step V : Multiply reduction half equation
Problem 6.7 : Balance the following by 2 to equalize number of electrons in two
unbalanced equation (in acidic medium) by half equations. Then add two half equation.
Oxidation
ion electron (half reaction method)
Mn2 (aq) + 2 H2O(l)
Mn2 (aq) + ClO3 (aq) MnO2 (s)
MnO2 + 4H (aq) + 2e Reduction
+ ClO2 (aq)
(1)
Solution : 2 ClO3 (aq) + 4H (aq) + 2e
Step I : Write unbalanced equation for the 2ClO2(aq) + 2H2O (l) (2)
redox reaction. Assign oxidation number to eq. (1) + eq. (2) gives the net reaction
all the atoms in reactants and product then. Mn2 (aq) + 2 ClO3 (aq)
Divide the equation into two half equations. MnO2(s) + 2ClO2 (aq)
Loss of 2e The equation is balanced in terms of
Mn2 (aq) + ClO3 (aq) MnO2(s) + ClO2(aq) number of atoms and the charges.

+2 +5 -2 +4 -2 +4 -2

Gain of 1e Problem 6.8 : Balance the following

Oxidation half reaction unbalanced equation by ion electron (half
Mn2 (aq) MnO2 (aq) reaction method)
Reduction half reaction H2O2 (aq) + ClO4 (aq) ClO2 (aq)
ClO3 (aq) ClO2 (aq) + O2 (g)
Step II : Balance half equations for O Solution :
atoms by adding H2O to the side with less O Step I : Write unbalanced equation for the
atoms. Add 2H2O to left side of oxidation redox reaction and assign oxidation number
and one H2O to the right side of reduction. to all the atoms in reactants and products.
Oxidation Divide the equation into two half equations.
Mn2 (aq) + 2H2O (l) MnO2 (s)
87
 Loss of 2e ClO4 (aq) + 4H (aq) + 4e ClO2
H2O2 (aq) + ClO4 (aq) ClO2 (aq) + O2 (g) + 2 H2O(l)
2 H2O2 (aq) + ClO4 (aq)+ 4H (aq) + 4e
+1 -1 +7 -2 +3 -2 0 2 O2(g) + ClO2 (aq) + 4 H (aq) + 4e
Gain of 4e + 2 H2O(l)
Oxidation
2 H2O2 (aq) + ClO4 (aq)
H2O2 (aq) O2 (g)
Reduction 2 O2(g) + ClO2 (aq) + 2 H2O(l)
ClO4 (aq) ClO2 (aq) This equation is balanced in terms of
Step II : Balance the half equation for O atoms and charges.
atoms by adding H2O to the side with less O
atoms. Hence add 2 H2O to the right side of
reduction half equation and none to the Try this
oxidation half equation
Oxidation Classify the following unbalanced half
H2O2 (aq) O2(g) equations as oxidation and reduction
Reduction Example Type
ClO4 (aq) ClO2 (aq) + 2 H2O(l)
Cl (aq) Cl2 (g) oxidation
Step III : Balance H atoms by adding H+
OCl (aq) Cl (g)
ions to the side with less H. Hence add 2H
ions to the right side of oxidation half Fe(OH)2 Fe(OH)3
equation and 4H ions to the left side of VO (aq)
2
V3 (aq)
reduction half equation.
Oxidation 6.4 Redox reaction and electrode potential
H2O2 (aq) O2(g) + 2H (aq) We noted in the section 6.1.1 that
Reduction displacement reaction can be looked upon
ClO4 (aq) + 4H (aq) ClO2 (aq) as redox reaction. Consider the following
+ 2H2O (l) displacement reaction.
Step IV : Add 2 electrons to the right side of Loss of 2e
oxidation half equation and 4 electrons to
the left side of reduction half equation to Zn (s) + Cu2 (aq) Zn2 (aq) + Cu (s)
balance the charges. Gain of 2e
Oxidation (6.17)
H2O2 (aq) O2(g) + 2H (aq) + 2e This reaction can be brought about in
Reduction two ways. The simpler method to observe this
ClO4 (aq) + 4H (aq) + 4e ClO2 + reaction is to take copper sulfate solution in
2H2O a container and dip zinc rod in it. The redox
Step V : Multiply oxidation half equation reaction (6.17) takes place in that container.
by 2 to equalize the number of electrons and Zinc gets oxidized to Zn2 ion and Cu2 ions
then add two half equations. get reduced to metallic Cu. A direct transfer of
Oxidation electron from zinc atom to cupric ions takes
2 H2O2 (aq) 2O2(g) + 4H (aq) + 4e place in this case.
Reduction The electron transfer from Zn atom to
Cu ions can be demonstrated by carrying out
2

two half reactions in two separate containers

as shown in Fig. 6.1
88
 V
electron Voltmeter electron
flow flow
Salt bridge

Ion
Zinc flow
electrode Copper
(anode) electrode
(cathode)
Zinc Copper
salt salt
solution solution
Electrode reactions
Zn (s) Zn2 (aq) + 2e Cu2 (aq) + 2e Cu(s)
Oxidation loss of electrons Reduction gain of electrons
Fig. 6.1 : Daniel Cell
The set up in Fig. 6.1 is that of Daniel In an electrochemical cell electrons flow
cell. The zinc and copper plates are connected in the external circuit from anode to cathode
by an electric wire through a switch and while the conventional current flows from
voltmeter. The solution in two containers are cathode to anode. An electrical potential is
connected by salt bridge (U-shaped glass tube said to be established at the two electrodes of
containing a gel of KCl or NH4NO3 in agar- an electrochemical cell. It is called electrode
agar). When switch is on, electrical circuit is potential. The magnitude and direction of the
complete as indicated by the deflection in the electrode potential depends upon the nature of
voltmeter. The circuit has two parts, one in the the metal and ions, concentration of ions and
form of electrical wire which allows the flow temperature. The reaction associated with an
of electrons and the other in the form of two electrode is called electrode reaction. The
solutions joined by salt bridge. In solution part two chemical species are linked by transfer of
of the circuit, the electric current is carried by electrons forms redox couple.
movement of ions. When a circuit is complete, 6.4.1 Standard electrode potential : When
the zinc atoms on zinc plates spontaneously concentration of each species taking part in the
lose electrons which are picked up in the electrode reaction is unity and the temperature
external circuit. The electrons flow from the is 298 K, observed electrode potential is
zinc plate to copper plate through wire. Cu2 called standard electrode potential (E0). By
ions in the second container receive these convention the standard electrode potential
electrons through the copper plate and are of hydrogen electrode is 0.00 Volt. Standard
reduced to copper atoms which get deposited hydrogen electrode is used as reference
on the copper plate. Here, zinc plate acts as electrode for determination of E0 values of
anode (negative electrode) and the copper various redox couples.
plate acts as cathode (positive electrode). Significance of E0 value : The electrode
Thus, when two half reactions, namely, reaction considered for the electrode potential
oxidation and reduction, allowed to take place is reduction reaction. Therefore, value and sign
in separate container and provision is made of standard electrode potential is a measure of
for completing the electrical circuit, electron the tendency of active species in the electrode
transfer take place through the circuit. This reaction to remain in the oxidized / reduced
results in flow of electric current in the circuit form. A negative E0 means redox couple is a
as indicated by deflection in voltmeter. This stronger reducing agent than the H /H2 couple.
is a simple electrochemical cell called Daniel Table 6.1 shows standard electrode potentials
cell, in which electricity is generated by redox of reduction process of some redox couples.
reaction.
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 Large negative value of E0 means that redox couple is stronger reducing agent. On the other
hand, more positive value of E0 means the redox couple is stronger oxidizing agent. From the
table 6.1 it is seen that alkali metals have high negative value of E0, which means that they are
strong reducing agent. The alkali metals have great tendency to give away electron and form
cations. On the other hand, fluorine has highly positive value of E0 and thus great tendency to gain
electron and is therefore, very strong oxidizing agents.
Table 6.1 : standand electrode protentianls of some redox couples
Oxidised form + ne reduced from E0/V
F2(g)+2e 2F 2.87
H2O2+2H +2e 2H2O 1.78
MnO4 +8H +5e Mn2 +4H2O 1.51
Cl2(g)+2e 2Cl 1.36
Cr2O72 +14H +6e 2Cr3 +7H2O 1.33
O2(g)+4H +4e 2H2O 1.23
Br2+2e 2Br 1.09
2Hg +2e2
Hg22 0.92
Fe3 +e Fe2 0.77
I2(s)+2e 2I 0.54
2H +2e H2(g) 0.00
Zn2 +2e Zn(s) -0.76
Al +3e
3
Al(s) -1.66
Mg +2e
2
Mg(s) -2.36
Na +e Na(s) -2.71
Ca2 +2e Ca(s) -2.87
K +e K(s) -2.93
Li + e Li(s) -3.05
We shall learn more about electrode potential and electrochemical cells in the 12th standard.

Problem 6.9 : By using standard electrode potential table predict the reaction between the
following is spontaneous. a. Fe3 (aq) and I (aq), b. Ag (aq) and Cu(s)
Solution : Write oxidation half reaction for one species and reduction half reaction for the
other species. Change the sign of E0 of oxidation half reaction. Take the sum of two E0 values.
If the sum is positive the reaction between two species is spontaneous.
a. Fe3 (aq) and I (aq)
2 Fe3 (aq) + 2e 2 Fe2 , E0 = 2 x 0.77 = 1.54
2I I2(s) + 2e , E0 = -0.54
+ 1.00
The sum of E values is positive, therefore reaction is spontaneous.
0

b. Ag (aq) and Cu(s)

2 Ag (aq) + 2e 2Ag(s), E0 = 2 x 0.80 = 1.60
Cu (s) Cu2+ + 2e , E0 = -0.34
1.26
The sum of E0 values is positive, therefore reaction is spontaneous.

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 Exercises
1. Choose the most correct option
A. Oxidction numbers of Cl atoms marked b. Fe3 is undergoing oxidation
as Cla and Clb in CaOCl2 (bleaching c. It is not a redox reaction
powder) are d. Both Sn2 and Fe3 are oxidised
F. Oxidation number of carbon in H2CO3 is
Cla
Ca a. +1 b. +2
O Clb c. +3 d. +4
a. zero in each G. Which is the correct stock notation for
b. -1 in Cla and +1 in Clb magenese dioxide ?
a. Mn(I)O2 b. Mn(II)O2
c. +1 in Cla and -1 in Clb
c. Mn(III)O2 d. Mn(IV)O2
d. 1 in each
I. Oxidation number of oxygen in
B. Which of the following is not an example
superoxide is
of redox reacton ?
a. -2 b. -1 c. - 1 d. 0
a.CuO+H2 Cu+H2O 2
J. Which of the following halogens does
b.Fe2O3+3CO2 2Fe+3CO2
always show oxidation state -1 ?
c. 2K+F2 2KF
a. F
d. BaCl2+H2SO4 BaSO4+2HCl
b. Cl
C. A compound contains atoms of three c. Br
elements A, B and C. If the oxidation
d. I
state of A is +2, B is +5 and that of C is
-2, the compound is possibly represented K. The process SO2 S2Cl2 is
by a. Reduction
a. A2 (BC3)2 b. Oxidation
b. A3 (BC4)2 c. Neither oxidation nor reduction
c. A3 (B4C)2 d. Oxidation and reduction.
d. ABC2 2. Write the formula for the following
compounds :
D. The coefficients p, q, r, s in the reaction
A. Mercury(II) chloride
p Cr2O72 + q Fe2 r Cr3 + s Fe3
B. Thallium(I) sulphate
+ H2O
C. Tin(IV) oxide
respectively are :
D. Chromium(III) oxide
a. 1, 2, 6, 6
3. Answer the following questions
b. 6, 1, 2, 4
A. In which chemical reaction does carbon
c. 1, 6, 2, 6
exibit variation of oxidation state from
d. 1, 2, 4, 6 -4 to +4 ? Write balanced chemical
E. For the following redox reactions, find reaction.
the correct statement. B. In which reaction does nitrogen
Sn2 + 2Fe3 Sn4 + 2Fe2 exibitvariation of oxidation state from
a. Sn2 is undergoing oxidation -3 to +5 ?
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 C. Calculate the oxidation number of 4. Balance the reactions/equations :
underlined atoms. A. Balance the following reactions by
a. H2SO4 b. H NO3 c. H3 P O3 oxidation number method
d. K2 C 2O4 e. H2 S 4O6 f. Cr 2O72- a. Cr2O22 (aq) + SO32 (aq) Cr3 (aq)
g. NaH2 PO4 + SO42 (aq) (acidic)
D. Justify that the following reactions are b. MnO4 (aq) + Br (aq) MnO2 (s)
redox reaction; identify the species + 13 CrO3 (aq) (basic)
oxidized/reduced, which acts as an
c. H2SO4 (aq) + C (s) CO2 (g) +
oxidant and which act as a reductant.
SO2 (g) + H2O (l) (acidic
a. 2Cu2O (s) + Cu2S (s) 6Cu (s) + SO2 (g)
d. Bi (OH)3 (g) + Sn(OH)3 (aq) Bi (s)
b. HF (aq) + OH (aq) H2O(l) + F (aq)
+ Sn (OH)6 (aq) (basic)
2

c. I2 (aq) + 2 S2O32 (aq) S4O62 (aq) + 2I (aq)

B. Balance the following redox equation by
E. What is oxidation? Which one of the half reaction method
following pairs of species is in its
a. H2C2O4 (aq) + MnO4 (aq)
oxidized state ?
CO2(g) + Mn2 (aq) (acidic)
a. Mg / Mg2 b. Cu / Cu2
b. Bi (OH)3 (s) +SnO22 (aq) SnO32 (aq)
c. O2 / O2 d. Cl2 / Cl + Bi (s) (basic)
F. Justify the following reaction as redox 5. Complete the following table :
reaction.
Assign oxidation number to the underlined
2 Na(s) + S(s) Na2 S(s) species and write Stock notation of compound
Find out the oxidizing and reducing Compound Oxidation Stock
agents. number notation
G. Provide the stock notation for the AuCl3
following compounds : HAuCl4, Tl2O,
SnCl2
FeO, Fe2O3, MnO and CuO.
V2O74-
H. Assign oxidation number to each atom
in the following species. PtCl62-
a. Cr(OH)4 b. Na2S2O3 H3AsO3
c. H3BO3
I. Which of the following redox couple is
stronger oxidizing agent ?
Activity :
a. Cl2 (E0 = 1.36 V) and Br2 (E0 = 1.09 V)
b. MnO4 (E0 = 1.51 V) and Perform redox reaction experiment
Cr2O72 (E0 = 1.33 V) with the help of Daniel cell under teacher
guidance.
J. Which of the following redox couple is
stronger reducing agent ?
a. Li (E0 = - 3.05 V) and
Mg (E0 = - 2.36 V)
b. Zn (E0 = - 0.76 V) and
Fe (E0 = - 0.44 V)

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