REDOX REACTION 120

Chapter 2 REDOX REACTION

OXIDATION NUMBER OR OXIDATION STATE

Oxidation state of an element in a particular species (atoms, molecules or ions) is the number of electrons
gained or lost by that element during its change from free state into that species. For example, the
oxidation state of Na in NaCl is +1, of calcium in Ca 3(PO 4)2 is +2, of chlorine in Cl 2 is zero.
(1) Oxidation no. is given positive sign if electrons are lost. oxidation no. is given negative sign if
electrons are gained.
(2) Oxidation no. represents real charge in case of ionic compounds. However, in covalent compounds
it represents imaginary charge.
Rules For Calculation Of Oxidation Number
Following rules have been arbitrarily adopted to decide oxidation no. of elements on the basis of their
periodic properties.
1. In uncombined state or free state, oxidation number of an element is zero.
2. In combined state oxidation no. of
(a) F is always –1.
(b) O is –2. In peroxides it is –1, in superoxides it is –1/2. However in F2 O it is +2.
(c) H is +1. In ionic hydrides it is –1 (i.e., IA, IIA and IIIA metals).
(d) halogens as halide is always –1.
(e) sulphur as sulphide is always –2.
(f) metals is always +ve.
(g) alkali metals (i.e., I A group — Li, Na, K, Rb, Cs, Fr) is always +1.
(h) alkaline earth metals (i.e., II A group—Be, Mg, Ca, Sr, Ba, Ra) is always +2.
3. The algebraic sum of the oxidation no. of all the atoms in a compound is equal to zero,
e.g. KMnO4 .
Oxidation no. of K + Ox. no. of Mn + (Ox. no. of O)  4 = 0
(+1) + (+7) + 4  (–2) = 0
4. The algebraic sum of all the oxidation no. of elements in a radical is equal to the net charge on the
radical, e.g., CO 32 .
Oxidation no. of C + 3  (Oxidation no. of O) = –2
(+4) + 3 x (–2) = –2
5. Oxidation number can be zero, +ve, –ve (integer or fraction)
6. Maximum oxidation no. of an element is = Group number (Except O and F)
Minimum oxidation no. of an element is = Group number –8 (Except metals)
Illustration 1 :
Find the oxidation number of
(a) S in SO 42– ion (b) S in HSO 3¯ ion
(c) Pt in (PtCl 6)2– (d) Mn in (MnO 4)– ion
Solution :
(a) Let the oxidation number of S be x.
We know that Ox. no. of O = –2
So Ox. no S + 4 (Ox. no. O ) = –2  x + 4(–2) = –2
or x – 8 = –2  x = + 8 – 2 = + 6
The oxidation number of S in SO 24 ion is +6.

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(b) Let the oxidation number of S be x in HSO3– ion.

We know that Ox. no. of H = +1
Oxidation number of O = –2
So Ox. no. H + Ox. no. S + 3 (Ox. no. O) = –1
+ 1 + x + 3(–2) = –1  +1 + x – 6 = –1  x – 5 = –1
or x = + 5 – 1 = +4  The oxidation number of S in HS O 3 ion is +4.
(c) Let oxidation number of Pt be x. We know that Ox. no. of Cl = –1
So Ox. no. Pt + 6 (Ox. no. Cl) = –2  x + 6(–1) = –2
or x – 6 = –2  The oxidation number of Pt in [Pt(Cl) 6]2– ion is +4.
(d) Let oxidation number of Mn be x. We know that Ox. no. of O = –2
So Ox.no. Mn + 4 (Ox. no. O) = –1  x + 4(–2) = –1  x – 8 = –1
or x = + 8 –1 = +7. The oxidation number of Mn in [MnO4]– ion is +7.

Special Examples regarding oxidation state

(i) Oxidation state of sulphur in Na2S4O6 (from Structure) :

O O
|| ||
Na  O  S  S  S  S  O  Na
|| 1 2 3 ||4
O O

From the structure, it is clear that the sulphur atom marked 1, 4 have + 5 oxidation state (each).
On the other hand, the sulphur-atom marked 2, 4 involved in pure covalent bond formation has
zero Oxidation number.
(ii) Oxidation number of S in (CH3)2SO (demethyl sulphoxide) :
Here, Oxidation number of O = –2, Oxidation number of each CH3 group is + 1
 + 2 + x – 2 = 0 or x = 0
Thus, sulphur lies in zero oxidation state.
(iii) Oxidation number of sulphur in Hypo (Na2S2O3) (sodium thiosulphate) :

O
||
Na  S  S  O  Na
2
|| 1
O

Oxidation number of sulphur marked 1 has +5 oxidation state on the other hand sulphur atom marked
two has +1 oxidation state.
(iv) Oxidation state of Cr in CrO5 :
CrO5 has butterfly str having two peroxo bonds.

O O
peroxo bond Cr peroxo bond

O O
O

x + 4 ×(–1) + (–2) = 0
x=+6

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(v) Oxidation state of C and N in HCN and HNC : -

1 x
H  C  N 3
1+x–3=0  x = +2
Carbon has +two oxidation state
1 -3 x
C
H N 

1 + (–3) + x = 0
x=+2
Carbon has +two oxidation state

O O
O S O H O S O H
(vi) peroxo bond O (vii) peroxo bond O
O H O
O S O H
caro’s acid O
Marshall acid
(peroxomono sulphuric acid) (peroxo di sulphuric acid)
Oxidation number of sulphur is +6 Oxidation number of sulphur is +7

Difference between valency and oxidation number

S.No. Valency S.No. Oxidation Number

1. It is the combining 1. It is the charge of atom present
capacity of the element. in the compound.
2. No +ve or –ve sign is 2. It may have +ve or –ve sign.
attached to it
3. Valency of element is 3. Oxidation number of element
usually fixed may have different value
depend on nature of compound
4. Valency is always a 4. Oxidation number of element
whole number. may be a whole number or
fractional
5. Valency of element is 5. Oxidation number of element
never zero except noble may be zero.
gas.
For example, in the following compounds of carbon, the oxidation number varies from – 4 to +4 but valency
of carbon is 4 in all the compounds.
Compound CH 4 CH 3Cl CH 2Cl 2 CHCl 3 CCl4
Oxidation number of carbon – 4 – 2 0 + 2 + 4

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DPP # 01
1. Determine the average oxidation no. of following elements given in bold letters :
(a) H 2S2O8 (b) K4Fe(CN)6 (c) OsO4
(d) HNC (e) Fe0.94O (f) Fe3O4
(g) NH2.NH2 (h) FeSO 4.(NH 4)2SO 4.6H2O (i) NOClO4
(j) Na 2[Fe(CN)5NO] (k) [Fe(NO)(H2O) 5]SO4 (l) Na 2S4O6
(m) (CH3)2SO (n) Na 2S2
2. Determine the oxidation number of the following elements given in bold letters :
(a) Ba 2XeO6 (b) C3O2 (c) V(BrO2)2
(d) Cs 4Na(HV10O28) (e) K[Co(C2O4)2.(NH 3)2] (f) [Ni(CN)4]2–
3. Find the oxidation number of bold lettered atoms :
(a) Mn in K 2MnO4, K2MnO3, Mn3O4, MnSO 4, K3MnF6, MnO2
(b) C in CH 4, C2H6, C3H8, C2H4, C2H2, H2C2O4, CO 2
(c) S in Na 2S2O3, S4, S8, Na 2S2O7
(d) N in NH 3, NH 2OH, NaN3, NH 4NO 2
(e) Cl in Cl 2, HOCl, Cl 2O, ClO2, KClO3, Cl 2O7
4. Determine the oxidation number of bold lettered atoms in the following :
(a) 8 KClO3 + 24 HCl 8 KCl + 12 H2O + 9Cl 2 + 6ClO2
(b) 3I2 + 6NaOH NaIO3 + 5NaI + 3H2O
5. Find the oxidation number of bold lettered atoms :
(a) SnS3–2 (b) S2O3–2 (c) S2O7–2 (d) NH4+
(e) ClO2– (f) P 2O7–4 (g) O2–2 (h) C2O4–2
(i) Cr 2O7–2 (j) MnO4– (k) Be3N2 (l) Na 3Fe(CN)5NO
(m) KCrO3.Cl (n) F 2H2 (o) Co(NH 3)6+3 (p) CuH
(q) O2F2

REDOX REACTION
Oxidation : It is a process in which electrons are lost by an atom, ion or molecule.
e.g, Mg  Mg2+ + 2e– Fe 2+  Fe 3+ + e–
2Cl –  Cl 2 + 2e– H2O2  O2 + 2H+ + 2e–

Reduction : Reduction is a process in which electrons are gained by an atom, ion or molecule.
Na + + e–  Na I2 + 2e–  2I–
2H2O + 2e–  H2 + 2 OH –

Redox Reactions : Those reactions in which electrons are transferred from one substance to another
are called Redox Reactions.
Zn + Fe 2+  Zn 2+ + Fe MnO2 + 4HCl  MnCl 2 + Cl2 + 2H2O

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REDOX REACTION 124

OXIDISING AGENTS AND REDUCING AGENTS

(Oxidants and Reductants)
Those species (atoms, molecules and ions) which have tendency to accept the electrons are known as
oxidizing agents or oxidants, whereas those species (atoms, molecules or ions) which releases the
electrons are called reducing agents or reductants. In other words, oxidizing agents are reduced and
reducing agents are oxidized.
(1) Oxidants are substances which :
(a) oxidize other
(b) are reduced themselves
(c) show electronation.
(d) show a decrease in oxidation number during a redox change
(e) has higher oxidation no. in a conjugate pair of redox.
(2) Reductant are substances which :
(a) reduce other
(b) are oxidized themselves.
(c) show de-electronation
(d) show an increase in oxidation no. during a redox change
(e) has lower oxidation no. in a conjugate pair of redox.
(3) A redox change is one in which a reductant is oxidized to liberate electrons, which are then
used up by an oxidant to get itself reduced.
M1  M1+n + ne oxidation
M2+n + ne  M2 reduction

M1 + M2+n  M1+n + M2 Redox reaction

(4) A redox change occurs simultaneously. For example,
2KMnO4 + 10FeSO 4 + 8H2 SO 4  K2SO 4 + 2 MnSO 4 + 5Fe 2(SO 4)3 + 8H2O
Oxidant Reductant
One can see the above equation in the ionic form,

Mn O 4 + 8H+ + 5e  Mn2+ + 4H2O

(As MnO 4 is accepting 5e–, so it is being reduced and hence it is an oxidant.)

Fe 2+  Fe 3+ + 1e–
As Fe 2+ is losing 1e–, so it is being oxidized and hence it is a reducing agent. Similarly,
PbS + 4H2O2  PbSO 4 + 4H2O
Reductant Oxidant
MnO2 + 4HCl  MnCl 2 + Cl 2 + 2H2O
Oxidant Reductant

Cr 2 O 72 + 6I– + 14H+  2Cr 3+ + 3I2 + 7H2O

Oxidant Reductant

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Guidelines for the Identification of Oxidizing and Reducing Agent

1. If an element is in its highest possible oxidation state in a compound, it can function as an oxidizing
agent, e.g. KMnO4, K2Cr 2O7, HNO 3, H2SO 4, HClO4 etc.
2. If an element is in its lowest possible oxidation state in a compound, it can function as a reducing agent,
e.g. H2S, FeSO 4, Na 2S2O3, SnCl 2 etc.
3. If an element is in its intermediate oxidation state in a compound, it can function both as an oxidizing
agent as well as reducing agent, e.g. H 2O2, H2SO 3, HNO2, SO 2 etc.
4. If highly electronegative element is in its higher oxidation state in a compound, that compound can
function as a powerful oxidizing agent, e.g. KClO 4, KClO3, KIO3 etc.
5. If an electronegative element is in its lowest possible oxidation state in a compound or in free state, it
can function as a powerful reducing agent, e.g. I–, Br –, N3– etc.

Common Oxidising and Reducing Agents

Oxidising agent Effective Change Decrease in Oxidation
Number

KMnO4 in acid solution Mn O 4  Mn2+ 5

KMnO4 in neutral solution Mn O 4  MnO2 3

K2Cr 2O7 in acid solution Cr 2 O 72  Cr 3+ 3

dilute HNO3 NO 3  NO 3

concentrated HNO3 NO 3  NO 2 1

concentrated H2SO4 SO 24  SO2 2

manganese (IV) oxide MnO2  Mn 2+ 2

Chlorine Cl 2  Cl – 1

Chloric (I) acid ClO–  Cl – 2

KIO3 in dilute acid IO 3  I2 5
Reducing agent Effective Change Decrease in Oxidation
Number
iron (II) salts (acid) Fe 2+  Fe 3+ 1
tin (II) salts (acid) Sn 2+  Sn 4+ 2
oxalate (acid) C2 O 24  CO 2 1
2
sulphites (acid) SO 32  SO 4 2
sulphide S2–  S 2
iodides (dilute acid) I–  I2 1
iodides (concentrated acid) I–  I+ 2
metals, e.g. Zn Zn  Zn 2+ 2
hydrogen H2  H+ 1

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DPP # 02
1. Identify the reactants, if any, oxidized or reduced .
(a) NaH + H2O  NaOH + H2
(b) 2FeCl 3 + H2S  2FeCl 2 + S + 2HCl
(c) 3Mg + N2  Mg3N2
(d) AgCN + CN –  Ag(CN)2–
(e) SnCl 2 + Br 2  SnCl 2.Br 2
(f) AlCl 3 + K  Al + 3KCl
(g) 2CuSO 4 + 4KI  Cu 2I2 + K2SO 4 + I2
(h) NH 4NO2  N2 + 2H2O
(i) CaC2 + 2H2O  Ca(OH) 2 + C2H2
(j) SnS2 + S –2
 SnS 3–2
(k) 3O2  2O3
2. Select the oxidants and reductants in the given reactions .
(a) Ag(NH 3)2+ + 2H+  Ag+ + 2NH 4+
(b) KIO3 + 5KI + 6HCl  3I2 + 6KCl + 3H2O
(c) 2CuSO 4 + SO 2 + 2KBr + 2H2O  2CuBr + 2H2SO 4 + K2SO 4
(d) C2H4 + Br 2  C2H4Br 2
(e) 2I– + H2O2  2OH – + I2
(f) Si + 2KOH + H 2O  K2SiO3 + 2H2
(g) 2Cu +2 + 4I–  Cu 2I2 + I2

TYPES OF REDOX REACTION

1. Combination reactions: These reactions involve combining of two or more reactants to form
a single product. It can be represented by a reaction of the type,
A + B  AB
For a redox reaction, either A or B or both must be in the elemental form. The combustion
reactions of fuels are generally combination reactions of carbon and hydrocarbons with
elemental dioxygen.
0 0 4  2
C(s)  O 2 (g) 
Heat
 CO 2 (g)
CH4(g) + 2O2(g)  CO2(g) + 2H2O(l)
2C8H18(s) + 25O2(g)  16CO2(g) + 18H2O(l)
Combustion of magnesium metal with dioxygen or lithium with nitrogen are also examples of
combination redox reactions.
0  2 2
2Mg(s)  O2 (g)  MgO2 (s)
1 3
0 1 0
3Li(s)  N 2 (g)  Li3 N(s)
2

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2. Decomposition reactions: These reactions are reverse of combination reactions and involve
breakdown of a reaction to two or more products.
AB  A + B
For these reactions to be redox, at least one of the components formed should be in the
elemental state. For example, the decomposition of potassium chlorate or of hydrogen peroxide
is a redox reaction, whereas the decomposition of calcium carbonate or other metal carbonates
is note a redox reaction because none of the components formed are in the elemental state.
1  5  2 1 1 0
2 KClO3 (s) 
Heat
 2 KCl(s)  3O 2 (g)

1  2 0 0
2 H 2 O 2 (l) 
Heat
 2 H 2 (g)  O2 (g)

2  4  2 2  2 4  2
CaCO3 (s) 
Heat
 CaO(s)  CO 2 (g)

3. Displacement reactions: These reactions are redox reactions in which one element of the
compound is replaced by atom or ion of another element. It can represented as:
AB + C  AC + B
The necessary condition for the reaction is that C is more reactive than B. Since B and C are
in their elemental state, the reaction is a redox reaction, where the main step involves the
movement of electrons from one reactant to another. Displacement reactions can be further
classified on the basis of nature of displacing element, into metal and non-metal displacement.
Activity Series for Some Metals (and Hydrogen)

Element Oxidation Product

3+
Least Active Gold Au
Mercury Hg2+
Silver Ag+
Copper Cu2+
Hydrogen H+
Lead Pb2+
Tin Sn2+
Cobalt Co2+
2+
Cadmium Cd
2+
Iron Fe
3+
Chromium Cr
Zinc Zn2+
Manganese Mn2+
Aluminium Al3+
Magnesium Mg2+
Sodium Na 1+
2+
Calcium Ca
2+
Strontium Sr
2+
Barium Ba
+
Potassium K
Rubidium Rb+
Most Active Caesium Cs2+

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(a) Metal displacement: If one metal is more easily oxidized than another, it can displace the
other metal from its compounds by a redox reaction. Such a reaction can be represented
as:
AX + M  MX + A
These reactions are also called single displacement reactions. The atoms of more active
metals are oxidized and become ions whereas the ions of less active metals are reduced and
become atoms. Some examples are:
Cu(s) + 2AgNO3(aq)  2Ag(s) + Cu(NO3)2(aq)
Zn(s) + HgO(s)  ZnO(s) + Hg(I)
Cr2O3(s) + Al(s)  Al2O3(s) + Cr(s)
2Cr(s) + 3Cu(NO3)2(aq)  3Cu(s) + 2Cr(NO3)3(aq)

2+
FinallyCu is
deposited as Cu.
Zn rod Cu deposited
copper nitrate on Zn rod
solution
Intial stage Intensity of blue Finalo stage
(Blue coloured) colour decreases (Blue colour
disappears)

Blue Coloured
starts
silver nitrate
Cu rod Ag deposited
solution
on Cu rod
intital stage Light blue coloured Final Stage
(Colourless) solution The blue colour
intensity of solution
increases
Metal displacement reactions find wide application in metallurgical process to obtain pure metals from their
ores. In general, a metal can displace and reduce the ions of any of the metals which are below that metal
in the reactivity series. This property is used in the thermite reaction for preparing small quantities of
metallic iron, wherein aluminium reduces iron (III) oxide to iron, thus becoming aluminium oxide in the
process:
2Al(s) + Fe2O3(s)  2Fe(s) + Al2O3(s)
The Kroll proces for preparing titanium is also based on the same property, wherein magnesium is used
to extract titanium from titanium tetrachloride, forming magnesium chloride in the process:
2Mg(s) + TiCl4(l)  Ti(s) + 2MgCl2(s)
(b) Non-metal displacement: The non-metal displacement reactions involve displacement of
hydrogen and in some cases oxygen. The hydrogen displacement reactions are listed as
follow.

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REDOX REACTION 129
(i) Metals replacing hydrogen from cold water: All alkali and some alkaline earth
metals, such as Ca, Sr and Ba, displace hydrogen from cold water and are strong
reducing agents.
2K(s) + 2H2O  2KOH(aq) + H2(g)
Ba(s) + 2H2O  Ba(OH)2(aq) + H2(g)
The hydrogen displaced from water has electropositive character. In the above
reactions, the more electropositive K+ and Ba2+ displace the less positive hydrogen.
(ii) Metals replacing hydrogen from steam: Less reactive metals such as iron displaces
hydrogen from steam to give hydogen gas.
2Fe(s) + 3H2O  2Fe 2O3(s) + 3H2(g)
Similarly, reaction between red-hot iron and superheated steam gives hydrogen gas:
3Fe(s) + 4H2O(g)  Fe3O4(s) + 4H2(g)
(iii) Metals replacing hydrogen from acid: Metals that do not react with cold water can
displace hydrogen from acids. The reaction is also shown by metals that do not react
even with steam. For example, when a piece of zinc is placed into a solution of
hydrochloric acid, bubbling is observed and the zinc gradually dissolves. The chemical
reaction is
Zn(s) + 2HCl(aq)  ZnCl 2(aq) + H2(g)
Similarly,
Mg(s) + 2HCl(aq)  MgCl 2(aq) + H2(g)
Sn(s) + 2HCl(aq)  SnCl2(aq) + H2(g)
The rate of reaction is fast with zinc or magnesium and the reaction is used as a
method for preparation of hydrogen in the laboratory. The rate of evolution of hydrogen
gas is a measure of the reactivity of the metals. Magnesium is the most reactive metal
and iron the least reactive in displacement of hydrogen from an acid. Metals which
occurs in their native state, such as gold and silver do not react with acids to liberate
hydrogen.
Like metals, halogens can also be arranged in the activity series based on their reactivity as oxidizing agents.
Their strength as oxidizing agents decreases as we move down the group from fluorine to iodine. Fluorine is
the most reactive and can displace oxygen from water.
0 1  2  1 1 0
2 F2 (g)  2 H 2 O(l)  4 HF(aq)  O 2 (g)

The displacemet reactions of chlorine, bromine and iodine using fluorine are not carried out in aqueous
medium because of fluorine’s ability to displace oxygen from water. However, chlorine can displace bromine
and iodine in aqueous solutions and bromine can displace iodine.
Cl2(g) + 2NaBr(aq)  2NaCl(aq) + Br2(l)
Cl2(g) + 2Nal(aq)  2NaCl(aq) + I2(s)
Br2(I) + 2NaI(aq)  2NaBr(aq) + I2(s)
Both bromine and iodine dissolve in CCl 4 and impart reddish brown and violet colour to the solution,
respectively. These displacement reactions form the basis of the layer test used in the laboratory for identi-
fication of bromide and iodide ions.

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REDOX REACTION 130

4. Disproportionation reactions: These reactions are redox reactions in which an element in a

compound is simultaneously oxidized as well as reduced. In the reactant, the element is in one
oxidation state while in the products it appears in more than one oxidation state, one reflecting
oxidation and the other reduction. The essential condition for this type of redox reaction is that
an element in the reactant should be able to exist in at least three oxidation states and in the
reactant it should be in the intermediate oxidation state. Consider the example of reaction of
chlorine gas with sodium hydroxide to form sodium chloride, sodium hypochlorite and water. In
the reactant, the elemental chlorine has oxidation state zero and in the products oxidation state
of chlorine in sodium chloride is –1 (reduction) and in sodium chlorate it is +1 (oxidation).
Cl2(g) + 2NaOH(aq)  NaCl(aq) + NaClO(aq) + H2O(l)
The halogens bromine and iodine also exhibit the same reaction on treatment with alkali. However, the
reaction of fluorine with alkali shows a deviation and the reaction proceeds as follows:
2F2(g) + 2NaOH(aq)  2NaF(aq) + OF2(g) + H2O(I)
This behavior of fluorine is attributed to the fact that it is the most electronegative element and can exhibit
only the – 1 oxidation state in all its compounds. Hence, the tendency to undergo disproportionation redox
reactions is not possible in the case of fluorine. Phosphorus and sulphur also undergo disproportionation reactions
alkaline medium.
0 3 1
P4 (s)  3NaOH(aq)  3H 2 (I)  PH 3 (g)  3NaH 2 P O 2

0 2 2
S8 (s)  12NaOH(aq)  4Na 2 S(aq)  2Na 2 S 2 O 3 (aq)  6H 2 O(I)

S.No. Reaction Oxidant Reductant

(Getting Reduced) (Getting Oxidised)
1. C + O2  CO2 O [0   – 2] C [0  + 4]
2. PbS + 4O3  PbSO4 + 4O2 O [+ 2  0] S [ – 2  + 6]
3. PbS + 4H2O2  PbSO4 + 4H2O O [–1  –2] S [– 2  + 6]
4. Sn + 2F2  SnF 4 F [0  –1] Sn [0 + 4]
5. SO 2 + 2H2O +Cl 2  2HCl + H2SO4 Cl [0  –1] S [+ 4  + 6]
6. I2 + 10HNO3  2HIO3 + 10NO2 + 4H2O N [+ 5  + 4] I [0  + 5]
7. CuO + H2  Cu + H2O Cu [+ 2  0] H [ 0  + 1]
8. 2KMnO4 + 3H2SO4 + 5H2S  Mn [+ 7  + 2] S [–2  0]
K2SO4 + 2MnSO4 + 8H2O + 5S
9. H2O2 + Ag2O  2Ag + H2O + O2 Ag [+ 1  0] O [–1  0]
(Oxygen of H2O2)
10. H2SO4 + 2HI  SO2 + I2 + 2H2O S [+6  +4] I [–1  0]

NOTE : In reaction 2 oxygens of ozone have different oxidation state.

Structure of ozone is O OO
2 1

Oxidation state of oxygen marked 1 = +2

Oxidation state of oxygen marked 2 = – 2

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REDOX REACTION 131

BALANCING OF A REDOX REACTION

(i) Ion electron method - It involves following steps :
(i) Write down the redox reaction in molecular from or ionic from
(ii) To seperate oxidation and reduction half reaction.
(iii) To calculate loss of electron in oxidation half & gain of electron reaction in half reaction
(iv) To equate loss and gain of electron with multiply a suitable least number.
(v) Balance each half reaction. For this purpose.
(a) Balance the atoms other than H and O for each half reaction using simple multiples.
(b) Add water molecular to the side deficient in oxygen and add H + to the side deficient in
hydrogen. Thus is done in acidic or nertra solution.
(c) In alkaline solution, adding OH – for each excess of hydrogen. In basic solution the
concentration of H+ is very small the dominant species are water and OH–
(vi) Add the two balanced half reaction and cancel any common term to both side.
(vii) To recheck and ensure to atom balance and to charge balance on both side of reaction.
(viii) Write down a word balanced as a root suffix reaction
Illustration Balance the following eqn by10n - electron method.

Cr2O7 2  I   H   Cr 3   I 2  H 2O (acidic medium)

Solution 1st step : H
Cr2O7– – + I–  Cr3+ + I2 + H2O
Oxidation half Reaction Reduction half Reaction
2nd step : 2I–  I2 + 2e– Cr2O7– – + 6e–  2Cr3+
3rd step : ×3 ×1
6I–  3I2 + 6e– Cr2O7– – + 6e–  2Cr3+
4th step : 6I–  3I2 + 6e– Cr2O7– – + 14H+ + 6e–  2Cr3+ + 7H2O
5th step : adding two half reaction
6I– + Cr2O7– – + 14H+ + 6e–  3I2 + 2Cr3+ + 7H2O + 6e–
6th step : 6I– + Cr2O7– – + 14H+  3I2 + 2Cr3+ + 7H2O
Charge on left side Charge on right side
–6 2 × + 3 = +6
–2 +0
+ 14 +0
= +6 = +6
7th Step: 6I– + Cr2O7– – + 14H+  3I2 + 2Cr3+ + 7H2O
Balanced.

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REDOX REACTION 132


Illustration Cr(OH)3 + IO3– OH  I– + CrO42– (Alkaline Medium)
Separate the two half reactions.
(Oxidation half reaction) (Reduction half reaction)
+3 +6 +5
[Cr(OH)3  CrO42– + 3e– ] × 2 [IO3– + 6e–  I–] × 1
2Cr(OH)3 +2H2O  2CrO42–+10H++6e– IO3– + 6H+ + 6e–  I– + 3H2O
adding two half reaction
2Cr(OH)3+IO3–+2H2O+6H++6e–+4OH–  2CrO42–+10H++6e–+I–+3H2O+4H+ + 4OH–
(iii)Balance H–atoms by adding H 2 O to side having deficiency and OH – to side
having deficiency of H–atoms.
5OH– + H2O + Cr(OH)3  CrO42– + 5H2O or 5OH– + Cr(OH)3CrO42– + 4H2O
IO3– + 6H2O  I– + 3H2O + 6OH–
or IO3– + 3H2O  I– + 6OH–
(iv) Balance the charges by electrons
5OH– + Cr(OH)3  CrO42– + 4H2O + 3e–
IO3– + 6H2O + 6e–  I– + 3H2O + 6OH–
(v) Multiply first equation by 2 and add to second to give
10OH– + 2Cr(OH)3  2CrO42– + 8H2O + 6e–
IO3– + 6H2O + 6e–  I– + 3H2O +6OH–
___________________________________________________

4OH– + 2Cr(OH) 3 + IO3–  5H2O + 2CrO42– + I–

(ii) Oxidation Number method involve following step
(i) Write the selector equation
(ii) Find change in O.N. in each equation & equate the change in Oxidation Number by multiply
with suitable leant no.
(iii) Assign Oxidation Number to the atom in equation and find out which atoms are undergoing
oxidation & reduction. Write saperate equation for the atoms undergoing oxidation and reduction.
(iv) Complete the balance by inspection. First balance those substances which have undergone
change in oxidation number and then other atoms except H and O. Finally balance H and O by
putting H2O molecule wherever needed.
(v) In ionic equation, the net changes on both side of the equation mmt be exactly the same use
H+/10m in acidic reaction and OH – ion in basic reaction balance the charge and no. of H and
O.
Illustration Balance the following equation by oxidation number method.
Cu  HNO 3  Cu(NO 3 ) 2  NO 2  H 2 O
0 1 5  2  2 5  2  4  2 1 2
Solution Step- 1 Cu  H N O 3  Cu(NO 3 ) 2  NO 2  H 2 O

0 2 5 4
Step-2 Cu  Cu  Cu(NO3 ) 2  HNO3  NO 2
Imc. in oxidation number of Cu = 2 unit per mulerlecu
Dec in oxidation number of nitrogen = 1 unit per mulertion of NHO3
Step-3 To equate mc and dec of oxidation number with multipled by suitable least no.
Cu  2HNO 3  Cu( NO 3 ) 2  2NO 2  H 2 O
Step-4 Balance nitrate ion, H and O
Cu  4 HNO3  Cu  NO3  2  2 NO2  2 H 2O

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REDOX REACTION 133

Solved Example based on Balancing of Equations

1. What will be the value of x, y and z in the following equation –
H2C2O4 + xH2O2  yCO2 + zH2O
(A) 2, 1, 2 (B) 1, 2, 2 (C) 2, 2, 1 (D) None
Sol. (B) (i) The half reaction for oxidation is, H2C2O4  CO2
Balancing carbon atoms on both sides, H2C2O4  2CO2
Balancing hydrogen atoms on both sides, H2C2O4  2CO2 + 2H+
Balancing the charge on both sides, H2C2O4  2CO2 + 2H+ + 2e–
(balanced)
(ii) The half reaction for reduction is – H2O2  H2O
Balancing oxygen atoms on both sides, H2O2  2H2O
Balancing hydrogen atoms, H2O2 + 2H+  2H2O
Balancing the charge, H2O2 + 2H+ + 2e–  2H2O
(balanced)
Now, adding both equation, H2C2O4 + H2O2  2CO2 + 2H2O
This is balanced equation.
2. What will be the value of x, y and z in the following equation –
x2 + yOH–  O3– + z– + 3H2O
(A) 3, 5, 6 (B) 5, 6, 3 (C) 3, 6, 5 (D) 6, 3, 5
Sol. (C) 0 +5
2  O3 ... (i) Oxidation
0 –1
  –... (ii) Reduction
Balancing atoms of Iodine on two sides,
we get,
 2  2  O3 –
or, 2 + 12OH  2O3– + 6H2O
Balancing change,
2 + 12OH–  2O3– + 6H2O + 10e–
2  2  –
and (2 + 2e–  2–) × 5
————————————————————–
Adding, 62 + 12OH–  2O3 + 10– + 6H2O
or, 32 + 6OH –  O3– + 5– + 3H2O
It is balanced equation.
3. What will be the value of a, b, c, d, e and f in the following equation –
aMnO4– + bC2O4– – + cH+  dMn++ + eCO2 + f H2O
(A) 2, 2, 10, 8, 5, 16 (B) 2, 5, 16, 2, 10, 8
(C) 2, 5, 10, 2, 8, 16 (D) 2, 8, 16, 2, 5, 10
Sol. (B) (i) The half reaction for reduction is, MnO4–  Mn++
Balancing with respect to oxygen by adding 4H2O on R.H.S.,

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 REDOX REACTION 134

MnO4–  Mn++ + 4H2O

Balancing with respect to hydrogen by adding 8H+ on L.H.S.,
MnO4– + 8H+  Mn++ + 4H2O
Balancing charge by adding electrons,
MnO4– + 8H+ + 5e–  Mn++ + 4H2O
(ii) The half reaction for oxidation is, C2O4– –  2CO2
Balancing with respect to electrical charge by adding electrons on R.H.S.
C2O4– –  2CO2 + 2e–
Now, to equalise the number of electrons, the reduction half reaction is multiplied by 2
and oxidation half reaction by 5, so on adding, we get
(C2O42 –  2CO2 + 2e–) × 5
(M nO 4– + 8H+ + 5e–  Mn++ + 4H2O) × 2
———————————————————————————
2MnO4– + 5C2O4– – + 16H+ 2Mn++ + 10CO2 + 8H2O
This is the balanced equation.
4. In the reaction Al + Fe 3O4  Al 2O3 + Fe – what is the total no. of electrons transferred
during the change –
(A) 16 (B) 24 (C) 8 (D) 12
Sol. (B) 2Alº  Al2 +3
 6e¯ ............. (A)
8e + Fe3+8/3 3Feº ............. (B)
Multiplying Eq. (A) by 4 and Eq. (B) by 3, then on addition
8Alº  4Al 2+3 + 24e
24e + 3Fe 3+8/3  9Feº
—————————————————————

8Alº + 3Fe 3+8/3  9Feº + 4Al 2+3

————————————————
or 8Al + 3Fe 3O4  4Al 2O3 + 9Fe
Therefore, it is clear that total no. of electrons transferred during change = 24
5. In the redox reaction –
10FeC2O4 + x KMnO4 + 24H2SO4 
5Fe 2 (SO4)3 + 20CO2 + y MnSO4 + 3 K2SO4 + 24H2O.
The values of x and y are respectively –
(A) 6, 3 (B) 3, 6 (C) 3, 3 (D) 6, 6
Sol. (D) The balanced redox reaction given above can be written as :
10FeC2O4 + 6KMnO4 + 24H2SO4 
5Fe 2 (SO4)3 + 20CO2 + 6 MnSO4 + 3 K2SO4 + 24H2O

so the value of x = 6 and y = 6

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REDOX REACTION 135

DPP # 03
1. Which one of the following is a redox reaction ?
(A) H2 + Br2 = 2HBr (B) 2NaCl + H2SO4 = Na2SO4 + 2HCl
(C) HCl + AgNO3 = AgCl + HNO3 (D) NaOH + HCl = NaCl + H2O
2. White P reacts with caustic soda forming PH3 and NaH2PO2. The reaction is -
(A) Redox (B) Oxidation
(C) Reduction (D) Neutralisation
3. The reaction Co(s) + Cu2+(aq)  Co2+(aq) + Cu(s) is -
(A) Oxidation (B) Reduction (C) Redox (D) Hydrolysis
4. A redox reaction is -
(A) Proton transfer reaction (B) Electron transfer reaction
(C) Ion combination reaction (D) A reaction in a solution
5. Which of following is not a redox change ?
(A) 2H2S + SO2 = 2H2O + 3S (B) 2BaO + O2 = 2BaO2
(C) BaO2 + H2SO4 = BaSO4 + H2O (D) 2KClO3 = 2KCl + 3O2
6. Which of the following examples does not represent disproportionation ?
(A) MnO2 + 4HCl  MnCl2 + Cl2 + 2H2O
(B) 2H2O2  2H2O + O2
(C) 4KClO3  3KClO4 + KCl
(D) 3Cl2+ 6NaOH  5NaCl + NaClO3 + 3H2O
7. Which of the following is a disproportionation reaction ?
(A) Cu2O + 2H+   Cu + Cu2+ + H2O (B) 2CrO 24 + 2H+   Cr2 O 72 + H2O

(C) CaCO3 + 2H+   Ca 2+ + H2O + CO2 (D) Cr2 O 72 + 2OH¯  2CrO 24 + H2O
8. H2O2 + H2O2  2H2O + O2 is an example of disproportionation because-
(A) O.N. of oxygen only decreases
(B) O.N. of oxygen only increases
(C) O.N. of oxygen decreases as well as increases
(D) O.N. of oxygen neither decreases nor increases
9. For the redox reaction
MnO4– + C2O4– – + H+  Mn2+ + CO2 + H2O
the correct coefficients for the balanced reaction are –
MnO4– C2O42– H+ MnO4– C2O42– H+
(A) 2 5 16 (B) 16 5 2
(C) 5 16 2 (D) 2 16 5
10. For the redox reaction
MnO4– + Fe++ + H+  Mn2+ + Fe3+ + H2O
in the balanced equation, correct coefficient are –
MnO4– Fe2 + H+ MnO4– Fe2 + H+
(A) 1 5 8 (B) 16 5 2
(C) 5 16 2 (D) 2 16 5

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REDOX REACTION 136
11. In the chemical reaction,
K2Cr2O7 + XH2SO4 + YSO2  K2SO4 + Cr2(SO4)3 + ZH2O
X, Y and Z are –
(A) 1, 3, 1 (B) 4, 1, 4 (C) 3, 2, 3 (D) 2, 1, 2
12. What will be the value of x, y and z in the following equation –
H2C2O4 + xH2O2  yCO2 + zH2O
(A) 2, 1, 2 (B) 1, 2, 2 (C) 2, 2, 1 (D) None
13. What will be the value of x, y and z in the following equation –
x2 + yOH–  O3– + z– + 3H2O
(A) 3, 5, 6 (B) 5, 6, 3 (C) 3, 6, 5 (D) 6, 3, 5
14. Cu + X  Cu (NO3)2 + 2H2O + 2NO2. Here X is-
(A) 4HNO3 (B) 2HNO3 (C) 4HNO2 (D) 6HNO3
15. In the redox reaction – 10FeC2O4 + x KMnO4 + 24H2SO4 
5Fe 2 (SO4)3 + 20CO2 + y MnSO4 + 3 K2SO4 + 24H2O.
The values of x and y are respectively –
(A) 6, 3 (B) 3, 6 (C) 3, 3 (D) 6, 6
16. Which of the following equations is a balanced one-
(A) 5 BiO3– + 22H+ + Mn2+  5Bi 3+ + 7H2O + MnO4–
(B) 5 BiO3– + 14H+ + 2Mn2+  5Bi 3+ + 7H2O + 2MnO4–
(C) 2 BiO3– + 4H+ + Mn2+  2Bi 3+ + 2H2O + MnO4–
(D) 6 BiO3– + 12H+ + 3Mn2+  6Bi 3+ + 6H2O + 3MnO4–
17. In the reaction: A–n2 + xe  A–n1 Here x will be –

(A) n1 + n2 (B) n2 – n1 (C) n1 – n2 (D) n1.n2

18. In which of the following reaction is called induced oxidation
(A) Na2SO3 + Na3AsO3 + O2  Na 2SO4 + Na3AsO4
(B) CuO + H2  Cu + H2O
(C) 2KMnO4 + 3H2SO4 + 5H2S  K2SO4 + 2MnSO4 + 8H2O + 5S
(D) H2O2 + Ag2O  2Ag + H2O + O2
19. In which of the following reaction is not redox
(A) NaOH + HCl  NaCl + H2O
(B) BiO3– + H+ + Mn2+  Bi3+ + H2O + MnO4–
(C) CuO + H2  Cu + H2O
(D) H2O2 + Ag2O  2Ag + H2O + O2
20. In which of the reaction is a disproportionation reaction
(A) P4 + 12NaOH + 12H2O  4PH3 + 12NaH2PO2
(B) MnO2 + 4HCl  MnCl2 + Cl2 + 2H2O
(C) 2FeCl3 + SnCl2  2FeCl2 + SnCl4
(D) 2S2O3– – + I2  S4O6– – + 2I–

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REDOX REACTION 137

NOMENCLATURE (Stock notation method)

The oxidation number/state of a metal in a compound is sometimes presented according to the notation given
by German chemist, Alfred Stock. It is popularly known as Stock notation. According to this, the oxidation number
is expressed by putting a Roman numeral representing the oxidation number in parenthesis after the symbol of the
metal in the molecular formula. Thus aurous chloride and auric chloride are written as Au(I)Cl and Au(III)Cl3.
Similarly, stannous chloride and stannic chloride are written as Sn(II)Cl2 and Sn(IV)Cl4. This change in oxidation
number implies change in oxidation state, which in turn helps to identify whether the species is present in oxidised
form or reduced form.
Thus, Hg2(I)Cl2 is the reduced form of Hg(II) Cl2.
Illustration Using Stock notation, represent the following compounds : FeSO4, Fe 2 (SO 4 ) 3 , Na 2 CrO 4 ,
K2CrO7, Cr 2O3, Mn2O7, V2O5. Stock notation method is used in type of metals which have
more than one oxidation states e.g.
(1)FeSO4 as iron (II) sulphate
(2)Fe2(SO4)3 as iron (III) sulphate
(3)Na2CrO4 as sodium chromate (VI)
(4)K2CrO7 as Potassium dichromate (VI)
(5)Cr2O3 as Chromium (III) oxide
(6)Mn2O7 as Manganese (VII) oxide
(7)V2O5 as Vanadium (V) oxide
Generally stock notation is used for metals but not for non metals.
Illustration Using Stock notation, represent the following compounds :HAuCl 4, Tl2O, FeO, Fe 2O3, CuI,
CuO, MnO and MnO2.
Solution By applying various rules of calculating the oxidation number of the desired element in a
compound, the oxidation number of each metallic element in its compound is as follows:
HAuCl4  Au has 3
Tl2O  Tl has 1
FeO  Fe has 2
Fe2O3  Fe has 3
CuI  Cu has 1
CuO  Cu has 2
MnO  Mn has 2
MnO2  Mn has 4
Therefore, these compounds may be
represented as:
HAu(III)Cl4, Tl2(I)O, Fe(II)O, Fe2(III)O3, Cu(I)I, Cu(II)O, Mn(II)O, Mn(IV)O2.
The idea of oxidation number has been invariably applied to def ine oxidation, reduction,
oxidising agent (oxidant), reducing agent (reductant) and the redox reaction.

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REDOX REACTION 138
Equivalent Weight: Number of parts by mass of an element which reacts or displaces from a compound 1.008
parts by mass of hydrogen, 8 parts by mass of oxygen and 35.5 parts by mass of chlorine, is known as the
equivalent weight of that element e.g.
2Mg  O 2 
 2MgO
48g 32g
12g 8g
 32g of O2 reacts with 48g of Mg
48  8
 8g of O2 = = 12g
32
 Equivalent weight of Mg = 12
Similarly, Zn  H 2 SO4 
 ZnSO4  H 2
65.5g 2  1.008

 2  1.008g of hydrogen is displaced by 65.5g

65.5
 1.008g of H = = 32.75g
2  1.008
65.5
 Equivalent weight of Zn = = 32.75
2
3
Al  Cl 2 
 AlCl3
2
3
32g  71g  111.5g chlorine reacts with 27g of Al
2
27  35.5
 35.5 g chlorine reacts with = 9.0g of Al
111.5
27
 Equivalent weight of aluminium = = 9.0
3
As we can see from the above examples that equivalent weight is the ratio of atomic weight and a factor (say n-
atomic weight
factor) which is in above three cases is their respective valencies. So, equivalent weight =
n  factor
In a similar way, the equivalent weight of acid/base is the ratio of molecular weight and the basicity/acidity and for
oxidizing agents and reducing agent it is the ratio of molecular weight and the number of moles of electrons
gained or lost. So in case of acid/base the n-factor is basicity/acidity (i.e. number of dissociable H+ ions/
number of dissociable OH– ion and in case of oxidizing agent/reducing agent, n-factor is number of moles
of electrons gained/lost per mole of oxidizing agent/reducing agent. Therefore, in general, we can write.
Atomic or molecualr weight
Equivalent weight (E) =
n  factor

Wt W W
No. of equivalents of solute =  
Eq. wt. E M / n
No. of equivalents of solute = No. of moles of solute ´ n-factor
And also Normality = n-factor ´ molarity of solution

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REDOX REACTION 139

Calculation of n-factor
For calculating the n-factor of any reactant in any reaction. One must know the kind of reaction
it is, the reactions may be classified into the following three types .
(a) Acid-Base Reactions/Neutralization reactions
(b) Redox Reactions
(c) Precipitation Reactions/Double decomposition reactions
(a) Acid-Base Reaction :
According, to the Arrhenius, an acid is a substance that furnishes H + ion(s) in solution, a base
is a substance that furnishes OH– ion(s) in solution and neutralization is a reaction in which H+
ion furnished by acid combines with OH – ions furnished by base. The number of H+ ion(s)
furnished per molecule of the acid is its n-factor also called basicity. Similarly the number of
OH – ion(s) furnished by the base per molecule is its n-factor, also called acidity.
Some Examples
 H   Cl 
HCl  ;  H   HSO 4
H 2SO 4 
( n 1) ( n 1)

 2H   SO 24
H 2SO 4  ;  H   H 2 PO 4
H 3 PO 4 
( n 2 ) ( n 1)

 3H   PO 34
H 3 PO 4  ;  H   H 2 PO 3
H 3 PO 3 
( n 3) ( n 1)

 2H   HPO 3
H 3 PO 3 
( n 2)

The n-factor of H3PO3 cannot be 3 as it has only two dissociable H + ions. So, its n-factor or
dissociable protons is 1 or 2 as one of the H-atoms is linked with P atom directly.
O

HO P OH

Similarly ,  CH 3COO   H 
CH 3COOH 
( n 1)

n-factor of CH3COOH is 1, because it contains only one dissociable H + ion.

Now , we will consider the n-factor of some bases.

 Na   OH 
NaOH 
( n 1)

[Ba (OH)]  OH 
Ba (OH) 2 
( n 1)

 Ba 2  2OH 
Ba (OH) 2 
( n 2)

 Al3  3OH 
Al(OH) 3 
( n 3)

Similarly, n-factor of Al(OH) 3 can also be 1 or 2 or 3, depending upon the number of OH –

released.

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REDOX REACTION 140

DPP # 04
Molecular weight
Equivalent weight =
' n' factor
Note : Molecular weight is the mass of 1 mole of any substance hence ‘n’ factor is always
calculated for 1 mole of substance.
Acids :
1. Calculate the ‘n’ factor of following acids :
(a) H2C2O4 (b) H2SO4
(c) H3PO2 (d) KHC2O4
(e) H3BO3 (f) H3PO4
(g) NaHC2O4.KHC2O4.H2C2O4 (h) HNO2
(i) H2S (j) CH3COOH
(k) Al2(C 2O4)3.5H2C2O4 (l) H3PO3
(m) H2SO3 (n) HNO3
(o) SnC2O4.2NaHC2O4.3KHC2O4.4H2C2O4
2. Find equivalent weight of H2SO4 in the following cases :
(a) H2SO4 NaHSO4 (b) H2SO4 Na 2SO4
(c) H2SO4 Na 3H(SO4)2 (d) H2SO4 KH 3 (SO4)2
Bases :
3. Calculate the ‘n’ factor and equivalent weight of following bases :
(a) NaOH (b) NH4OH (c) Al(OH) 3
(d) Mg(OH)2 (e) MgAl(OH)5 (f) Fe(OH) 3
(g) Na 3Al(OH) 6 (h) KOH (i) Ca2Al 3(OH)13
(j) Zn(OH)2
4. Find equivalent weight of Al(OH) 3 in the following reactions :
(a) Al(OH) 3 Al(OH) 2Cl (b) Al(OH) 3 Al(OH)Cl2
(c) Al(OH) 3 AlCl3 (d) Al(OH) 3 Al 2(OH) 4(NO3)2
(e) Al(OH) 3 Al 3(OH) 3 (PO4)2
(B) Redox Reactions
Those reactions which involve the exchange of electrons are called redox reactions. For the
calculation of n-factor of oxidising agent or reducing agent, the method depends upon the
change in oxidation state of the species considered. We will discuss them one by one.
(i) When only one atom undergoing either reduction or oxidation e.g.
7 2

MnO 4 
H
Mn 2
n 5

In such a case, we consider the change in oxidation state of atom undergoing oxidation or
reduction change per molecule as the n-factor of the species.
n-factor = |(+2) 1 – (+7)  1| = 5
2 3
2 3
Fe 
 Fe n-factor = |(+3) × 1 – (+2) × 1| = 1
n 1

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REDOX REACTION 141

32 42
C2O 42 
 2CO 2 n-factor = |(+4) × 2 – (+3) × 2| = 2
n 2

62 3 2
Cr2 O 72 
 2Cr 3 n-factor = |(+3) × 2 – (+6)× 2| = 6
n 6

(ii) Salts which reacts in such a way that only one atom undergoes change in oxidation
state but appears in two products with the same oxidation state :
In such a case the method of calculation of n-factor remains the same i.e., we will calculate the
change in oxidation state of the atom per mole of that substance (reactant).
6 2 3 3
Cr2 O72 
 Cr 3  Cr 3
In this example, oxidation state of Cr changes from +6 to +3 in both the products. So
n-factor = |(+6) × 2 – (+3) × 2| = 6
(iii) Salts which react in such a way that only one atom undergoes change in oxidation
state but goes in two products with different oxidation state as a result of either only
oxidation or only reduction.
7 2 6
3MnO 4 
 2Mn 2  Mn  6
In such a case, it is impossible to calculate the n-factor until and unless one knows that how
much of MnO 4 is changing to Mn2+ and how much to Mn 6+ and if one knows the balanced
equation then there is no need of calculation of n-factor. Nevertheless in such case the n-factor
can be calculated by deducing the total change in oxidation state divided by total number of
atom undergoing reduction/oxidation change. So, for the calculation of n-factor in the above
example, out of three moles of MnO 4 , two moles are being converted to Mn2+ and one mole
changes to Mn6+. So total decrease in oxidation state of Mn.
= | [2 × (+2) – 2 × (+7)] | + | [1 × (+6) – 1 × (+7)]|
= | 4 – 14 | + | 6 – 7 | = 11

So, n-factor = 113

(iv) Salts which react in such a way that only one atom undergoes change in oxidation
state in two product, in one product with changed oxidation state and in other product
with same oxidation state as that of reactant.
In such case also one cannot calculate the n-factor without knowing the balanced chemical
equation because one must know how much of atom has changed its oxidation state. For
example.
K2Cr2O7 + 14HCl  2KCl + 2CrCl3 + 3Cl2 + 7H2O
Let us calculate the n-factor of HCl. Out of 14 moles of Cl– (in HCl) only 6 moles of Cl–
are changing its oxidation state from –1 to 0 in the product Cl2 and the oxidation state of
remaining 8 Cl – ions remains same in KCl and CrCl3. So, total no. of moles of electrons
lost by 14 moles of HCl is 6. So each mole of HCl takes up 6/14 i.e., 3/7 moles of
electrons and hence n-factor of HCl is 3/7.

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(v) Salts which react in such a way that two or more atoms in the salt undergoes change
in oxidation states as a result of either oxidation or reduction. Let us consider the
following example,
FeC2O4  Fe3+ + 2CO2
In this case, the oxidation of both Fe 2+ and C3+ are changing from + 2 and +3 to +3 and
+4 respectively. In such a case we will calculate the n-factor of the salt as the total
increase or decrease in oxidation state per mole of the salt. As one can see that one mole
of FeC2O4 contains one mole of Fe 2+ and one mole of C2O42– (i.e. 2 carbon atoms per
mole of C2O42–.
Total change in oxidation state
= | 1 × (+2) – 1 × (+3) | + | 2 × (+3) – 2 × (+4) |
=1+2=3
So, n-factor of FeC 2O4 is 3
(vi) Salts which react in such a way that two atoms undergoing change in oxidation state
but one undergoing oxidation and other reduction reaction. In such a case one has to
calculate the change in oxidation state of either the atom being oxidized or the atom
being reduced. For example.
3 2 6 2 0 2 3 2
(N H 4 ) 2 Cr 2 O 7 
 N 2  Cr2 O3  4H 2 O
In this reaction, the oxidation state of N is increasing by 6 units and that of Cr is decreasing
by 6 unit. So, we can consider either oxidation or reduction product for the calculation
of n-factor and it will be the same.
n-factor of (NH4)2Cr2O7 considering oxidation
= |(-3) ×2 – (0) × 2| = 6
n-factor of (NH4)2Cr2O7 considering reduction
= |(+6) × 2 – (+3) × 2| = 6
(vii) Species which undergoes disproportionation reaction: Those reaction in which oxidant
and reductant are the same species or the same element from the species is getting
oxidized as well as reduced.
When the number of moles of atoms being oxidized is equal to the number of moles of
atoms being reduced.
The n-factor can be calculated by knowing the balanced chemical equation and
considering any of the change taking place. Say for example,
2H 2O2  2H2O + O2
Out of 2 moles of H 2O2 consumed in the reaction, one mole of H2O2 is being oxidized
(H 2O2  O2) and one mole of H2O2 is being reduced (H2O2  2H2O). First consider
the oxidation reaction
( 1)2 20
H 2O2  O 2
n-factor = |2 × 0 – (–1) × 2| = 2
Again, considering reduction reaction
( 1)2 ( 2 )2
H 2O2 
 2H 2 O
n-factor = |(-2) × 2 – (-1) × 2| = 2
So, n-factor of H 2O 2 either considering oxidation or reduction reaction is same
i.e. 2.

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DPP # 05
I Calculate n factor of the reactants in the following reaction in which only one type atom
undergo change in oxidation state
H
MnO4– OH
–
1. KMnO4 
 Mn+2 2.  MnO4–2

3. KMnO4 H
2O
 MnO2 4. Cr2O7–2 H Cr+3

K2Cr2O7 OH
–
5.  Cr+3 6. Na 2S2O3 H S4O6–2
S2O3–2 OH
–
OA
7.  SO 4–2 8. H2O2  H2O
RA
9. H2O2  O2 10. C2O4 CO2
–2

11. KI I2 12. CrO 4–2 Cr2O4–2

13. H2S  S 14. H2SO4  S
15. Hg5(IO 6)2  K2HgI4 16. PbCl2  PbCl4
17. Al 2(C 2O4)2  CO 2 18. ClO–  ClO4–
19. I–  I2 20. SO2  SO 4–2
21. Ba(MnO4)2  Mn+2 22. Pb(Cr2O4)2  Cr+6
23. I–  I3– 24. Fe2O3  FeO
25. Pb3O4  PbO 2 26. AN  NO3–
27. Cu3P2  H2PO4– 28. NaClO3  NaCl
29. Fe3O4  FeO 30. Ca3(PO4)2  P –3
31. (NH4)2SO4  N2H4 32. FeSO4  Fe2(SO4)3
33. CO2  CaC 2O4 34. Fe0.93O  FeO
35. Al(MnO4)3  Mn +2
36. Sn(Cr2O7)2  Cr +3
37. PbS  PbSO4 38. Cu2O  CuO
39. Mg 3N2  NO 3– 40. CuS  SO4–2
41. Fe2S3  SO3 42. SnCl2  ClO4–
43. H2SO4  H2S 44. Cu2S  Cu+2
45. H2SO4  SO2 46. Cu2S  SO3
47. PbCl2  Pb +4
48. FeC2O4  Fe +3
49. FeC2O4  CO2 50. Fe(NO3)3  Fe
II Calculate ‘n’ factor of reactants in the following reactions in which more than one type atoms
undergo change in oxidation state :
1. FeC2O4 Fe+3 + CO2 2. Cu2S Cu+2 + SO4–2
3. Pb(N3)2 Pb3O4 + NO 4. As 2S3 H3AsO4 + SO3
5. Cu3P Cu + H3PO4
+2
6. CrI3 CrO 4–2 + IO4–
7. FeS2 Fe+3 + SO2 8. Co(MnO4)3 CoO + MnO2
9. FeCr2O4 Fe 2O3 +K2CrO 4 10. SnC 2O4 Sn+4 + CO2
III Calculate ‘n’ factor of reactants in the following disproportionation reactions
1. Br2  Br   BrO3 2. ClO3  ClO4  Cl 
3. S  S 2  S2O32 4. 2 H 2O2  H 2O  O2
 2
5. 2Cu  Cu  Cu
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REDOX REACTION 144

REDOX REACTIONS AND ELECTRODE PROCESSES

In an earlier experiment discussed, we found that a strip of zinc placed in a Cu 2+ solution forms a coating
of metallic copper on the zinc strip. The electron transfer (redox) reaction converts zinc to zinc ions and some
copper ions are reduced to metallic copper. To generate electricity, however, the oxidation reaction must be
separated from the reduction reaction so taht the electrons exchanged can flow in an external wire where they
can be put to use. We can set such a system by placing a copper rod in a beaker containing solution of copper
salt and another beaker containing zinc rod dipped in solution of zinc salt. The redox reaction takes place in
each beaker and the oxidized and reduced forms of the metal species are present in the same beaker. Each
is referred to as a redox couple and is represented by oxidation or reduction half-reactions.
A redox system consisting of two metals and solutions of their salts can be combined to form a galvanic
cell, which produces electricity. In other words, a galvanic cell consists of an oxidizing agent in one compartment
that pulls electrons trhough a wire from a reducing agent in the other compartment.
One of the earliest voltaic cells put to use the spontaneous reaction discussed above, which is
Zn(s) + Cu2+(aq)  Zn2+(aq) + Cu(s)
This voltaic cell is known as the Daniell cell and was used to generate electrical current for the new
telegraph and doorbells in homes. The Daniell cell is illustrated in fig. A zinc strip is immersed in a Zn2+ solution,
and, in a separate compartment, a copper strip is immersed in a Cu solution. A wire connects the two metal
strips, which are called electrodes. The electrodes are the surfaces in a cell at which the reactants take place.
The electrode at which oxidation takes place is called the anode and the electrode at which reduction takes place
is called the cathode. A redox couple has the oxidized and reduced forms of a substance together which take
part in oxidation or reduction reaction. In the compartment on the left, the strip of Zn serves as the anode,
since the following reaction occurs when the circuit is connected.
Zn(s)  Zn2+(aq) + 2e–
When the circuit is complete, the two electrons travel in the external wire to the Cu electrode, which serves
as the cathode. The reduction reaction occurs at the cathode.
2e– + Cu2+(aq)  Cu(s)

To maintain neutrality in the solution, some means must be provided for the movement of a SO 42– ion (or
some other negative ion) from the right compartment, where a Cu 2+ has been removed, and to the left
compartment, where a Zn2+ has been produced. The salt bridge (a U-tube filled with a saturated solution of
a soluble salt such as KNO3) is an aqueous gel that allows ions to migrate between compartments but does

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REDOX REACTION 145

not allow the mixing of solutions. A porous plate separating the two solutions, as shown in fig. also serves this
functions. (If Cu2+ ions mixed into the left compartment, they would form a coating of Cu on the Zn electrode,
thus short-circuiting the cell.)
The electrodes in this cell are called active electrodes because they are involved in the reaction. As the cell
discharges (generates electrical energy), the Zn electrode becomes smaller but the Cu electrode becomes larger.
The reaction can be stopped by interrupting the external circuit with a switch. If the circuit is open, the electrons
can no longer flow, so no further reaction occurs until the switch is against closed. The transfer of electrons,
thus takes place through the metallic wire connecting the electrodes while the electricity flows through the salt
bridge. The energy of the cell can thus be stored betwee uses.
Electrode potential is defined as the potential that exists between the metal or a gas and its ions in aqueous
solution, at their equilibrium when they are in contact with each other. The electrode potential of a metal is
thus a measure of its tendency to lose or gain electrons when in contact with a solution of its own salt. The
potential associated with each electrode is known as its electrode potential. The tendency of an electrode to gain
electron(s) and to get reduced is known as its reduction potential.
Mn+(aq) + ne–  M(s)
The tendency of an electrode to lose electron(s) and to get oxidized is known as its oxidation potential.
M(s)  Mn+(aq) + ne–
The reduction potential is the reverse of oxidation potential, and this can be shown by the experimentally
determined oxidation and reduction potentials of hydrogen electrode.
Zn(s)  Zn2+(aq) + 2e–
Zn2+(aq) + 2e–  Zn(s)
By electrochemical convention, the half-cell reactions are written in terms of reduction half-cell reactions
and the electrode potential is expressed in terms of reduction potential. The electrode potential of an electrode
is determined by:
1. The nature of metal and its ions (electrolyte)
2. The concentration of the ions in the solution
3. Temperature
The electrode potential when concentration of participating species is taken as unity (or the pressure for a
gas involved in the electrode reaction is 1 atm) and the reaction is carried out at 298 K is known as standard
electrode potential. For example, if the strip of zinc metal is immersed in a 1M solution of the Zn2+ ion and
that the silver wire is immersed in a 1M solution of the Ag+ ion, the electrode potentail is called standard electrode
potential. The reaction should be carried out at 298K. For example,
Zn2+ + 2e–  Zn o
Ered = – 0.7628 V
Ag+ + e–  Ag o
Ered = + 0.7996 V
When we combine these half-reactions to form a voltaic cell, the overall cell potential for the reaction must
be the sum of the potentials for the oxidation and reduction half-reactions.
 Eoxo  Ered or Ecell  Eright  Eleft
o o o o o
Ecell
where E° is reduction electrode potential. The standard cell potential for the voltaic cell the therefore can be
calculated from the standard half-cell potentials of the following half-cell reactions.
Zn(s)  Zn2+(aq) + 2e– Eoxo = + 0.7628 V

2Ag+(aq) + 2e–  2Ag(s) o

Ered = + 0.7996 V

Zn(s) + 2Ag+(aq)  Zn2+(aq) + 2Ag(s) o

Ecell = + 1.5624 V
The larger the difference between the oxidizing and reducing strengths of the reactants and products, the
larger is the cell potential. To obtain a relatively large cell potential, we have to react a strong reducing agent
with a strong oxidizing agent.

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REDOX REACTION 146
It is not possible to to determine the absolute values of oxidation and reduction electrode potentials because
the oxidation and reduction reactions do not occur in isolation. To assign numerical values for standard reduction
potentials, a reference electrode has been arbitrarily chosen and its standard reduction potential has been defined
as exactly 0.0 V. This reference electrode is called the standard hydrogen electrode.
The redox couple is a stronger reducing agent than the H+/H2 couple, when the electrode potential is negative
and a stronger oxidizing agent than the H+/H2 couple, when the electrode potential is positive. When the
electrodes are arranged in the decreasing order of their standard reduction potential values, the series so formed
o
is termed electrochemical series based on electrode potential. Standard electrode potentials ( Ered ) are given
in Table.
Standard Electrode Potentials, Eroed at 25°C

Half-Reactiona o
E red (V )
F2(g) + 2H+(aq) + 2e –  2HF(aq) +2.87
Co3+(aq) + e–  Co2+(aq) +1.842
Au+(aq) + e–  Au(s) +1.68
MnO 4– (aq) + 8H+(aq) + 5e–  Mn2+(aq) + 4H2 O(l) +1.51
PbO2(s) + 4H+(aq) + 2e  Pb2+(aq) + 2H2O(l) +1.467
Cl2(g) + 2e –  2Cl–(aq) +1.36
Cr2O 7 (aq) + 14H (aq) + 6e  2Cr (aq) + 7H2O(l)
2– + – 3+
+1.33
O2(g) + 4H (aq) + 4e  2H2 O(l)
+ –
+1.23
CrO4 (aq) + 8H (aq) + 3e  Cr (aq) + 4H2 O(l)
2– + – 3+
+1.95
Br2(aq) + 2e  2Br (aq)
– –
+1.07
HNO3(aq) + 3H+(aq) + 3e  NO(g) + 2H2O(l)
–
+0.96
Hg (aq) + 2e  Hg
2+ –
+0.851
Ag (aq) + 2e  Ag(s)
+ –
+0.80
Hg2 (aq) + 2e  2Hg(s)
2+ –
+0.7961
Fe (aq) + e  Fe (aq)
3+ – 2+
+0.7760
O2(g) + 2H (aq) + 2e  H2 O2(aq)
+ –
+0.682
MnO 4 (aq) + 2H2O(l) + 3e  MnO 2(s) + 4OH (aq)
– – –
+0.558
Cu+(aq) + e –  Cu +0.522
O2(g) + 2H2O(l) + 4e–  4OH–(aq) +0.401
Cu2+(aq) + 2e–  Cu(s) +0.34
Sn4+(aq) + 2e –  Sn2+ (aq) +0.15
2H+(aq) + 2e–  H2(g) +0.0000
Fe3+(aq) + 3e –  Fe(s) –0.036
Pb2+(aq) + 2e –  Pb(s) –0.1263
Sn2+(aq) + 2e –  Sn(s) –0.14
Ni2+(aq) + 2e –  Ni(s) –0.25
Co2+(aq) + 2e–  Co(s) –0.28
Fe2+(aq) + 2e –  Fe(s) –0.44
Cr3+(aq) + e –  Cr2+(aq) –0.41
S(s) + 2e  S (aq)
– 2–
–0.508
Cr (aq) + 3e  Cr(s)
3+ –
–0.74
Zn (aq) + 2e  Zn(s)
2+ –
–0.76
Mn (aq) + 2e  Mn(s)
2+ –
–1.18
Al (aq) + 3e  Al(s)
3+ –
–1.66
Mg2+(aq) + 2e–  Mg(s) –2.37
Na+(aq) + e –  Na(s) –2.7
Ca2+(aq) + 2e–  Ca(s) –2.76
K (aq) + e  K(s)
+ –
–2.92
Li (aq) + e  Li(s)
+ –
–3.05

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REDOX REACTION 147
In tables of standar potential, the symbol H+ is used instead of H3O+.
The electrochemical series has several practical applications in chemistry.
1. Higher the reduction potential, greater is the tendency of the element to get reduced. Hence,
the relative oxidizing and reducing abilities of the elements can be compared easily. For instant, among Zn
and Cu systems, zinc system has lower reduction potential (– 0.76 V) than Cu(+ 0.34 V). So, zinc system
has more reducing ability than Cu. Lower the reduction potential, greater is the reducing ability.
2. Metals lying lower in the electrochemical series (having lower electrode potential) can displace metals lying
higher in the series (having higher electrode potential). For example, zinc shavings added to a hot saturated
solution of CuSO4 can displace copper from the salt. In other words, displacement reactions can be predicted.
3. Knowledge of electrochemical series helps is selection of electrode assemblies, to construct the galvanic
cells of the desired EMF.
4. The polarity of the electrode system and the electrode reaction can be easily predicted.
5. Spontaneity and feasibility of the cell under construction can be easily predicted.

POTENTIAL OF A CELL OR EMF

Knowing the single electrode potential of the two electrodes, the potential of the cell formed from them
can be obtained. The difference between the electrode potentials of the two electrodes canstituting an electro-
chemical cell is known as cell potential or electromotive force (emf) of the cell. For example, consider the
cell to be constructed by coupling of an iron and a nickel electrode. If the electrode potentials of the two
electrodes at 298 K are – 0.44 V and – 0.24 V in that order, the EMF of the cell can be obtained. The iron
electrode (Fe2+|Fe) is the electrode at which oxidation takes place and nickel electrode (Ni 2+|Ni) is the electrode
at which reduction takes place.
Fe(s)|Fe2+(aq)||Ni2+(aq)|Ni(s)
So, Ecell  Eright  Eleft  E Ni 2 / Ni  EFe 2 / Fe  0.24  ( 0.44)  0.2V
o o o o

The magnitude of the cell potential is a measure of the driving force behind a reaction. The larger the value
of the cell potential, the farther is the reaction from equilibrium. The sign of the cell potential tells us the
direction in which the reaction must shift to reach equilibrium. The fact that Eo is positive for the nickel-iron
cell tells us that when the system is at standard conditions, it has to shift to the right to reach equilibrium.
Reactions for which Eo is positive, therefore, have equilibrium constants that favor the formation of the products
of the reaction. A reaction with a positive Eo should occur naturally and is reffered to as spontaneous.
Illustration Use the standard cell potential for the following reaction
Cu(s) + 2H+(aq)  Cu2+(aq) + H2(g)E° = – 0.34 V
to predict the standard cell potential for the opposite reaction
Cu2+(aq) + H2(g)  Cu(s) + 2H+(aq)E° = ?
Solution Turning the reaction around does not change the relative strengths of Cu 2+ and H +
ions as oxidizing agents or copper metal and H 2 as reducing agents. The magnitude
of the potential, therefore, must remain the same. But turning the equation around
changes the sign of the cell potential and can therefore turn an unfavourable
reaction into one that is spontaneous, or vice versa. The standard cell potential for
the reduction of Cu2+ ions by H2 gas is therefore + 0.34 V.
Cu2+(aq) + H2(g)  Cu(s) + 2H+(aq)E° = – (0.34) = + 0.34 V
Note that for a spontaneous redox reaction, E° for the cell should be positive. The
negative value of E° tells us why copper does not displace hydrogen from dilute
acids or water.

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REDOX REACTION 148

ANSWER DPP KEY

DPP # 01
Q.1 (a) (+6) (b) (+2) (c) (+8) (d) (+2)
(e) (0) (f) (+8/3) (g) (–2) (h) (+2)
(i) (+7) (j) (+2) (k) (+1) (l) (+5/2)
(m) (0) (n) (–1)
Q.2 (a) (+8) (b) (+4/3) (c) (+2) (d) (+5)
(e) (+3) (f) (+2)
Q.3 (a) [+6, +4, +8/3, +2, +3, +4] (b) [–4, –3, –8/3, –2, –1, +3, +4]
(d) [+2, 0, 0, +6] (e) [–3, –1, –1/3, –3, +3]
(f) [0, +1, +1, +4, +5, +7]
Q.4 (a) [+5, –1, 0, +4] (b) [0, +5, –1]
Q.5 (a) (+4) (b) (+2) (c) (+6) (d) (–3)
(e) (+3) (f) (+5) (g) (–1) (h) (+3)
(i) (+6) (j) (+7) (k) (+2) (l) (+1)
(m) (+6) (n) (–1) (o) (+3) (p) (–1)
(q) (+1)
DPP # 02
Q.1
Rxn. No. (a) (b) (c) (d) (e) (f) (g) (h) (i) (j) (k)
+
Oxidized : NaH, H2S, Mg, none, SnCl2, K, KI, NH 4 , none, none none.
Reduced : H2O, FeCl 3, N2 none, Br 2, AlCl3, CusO4, NO2–, none, none, none
Q.2 (a) not (b) KIO3-oxidant, I– reductant
(c) CuSO4-oxidant, SO2 reductant (d) Br2-oxidant, C2H4 reductant
(e) H2O2-oxidant, I– reductant (f) KOH-oxidant, Si reductant
(g) Cu++-oxidant, I– reductant

DPP # 03
1. (A) 2. (A) 3. (C) 4. (B)
5. (C) 6. (A) 7. (A) 8. (C)
9. (A) 10. (A) 11. (A) 12. (B)
13. (C) 14. (A) 15. (D) 16. (B)
17. (C) 18. (A) 19. (A) 20. (A)

DPP # 04
1. (a) 2 (b) 2 (c) 1 (d) 1
(e) 1 (f) 3 (g) 4 (h) 1
(i) 2 (j) 1 (k) 10 (l) 2
(m) 2 (n) 1 (o) 13
2. (a) 98 (b) 49 (c) 65.34 (d) 49

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3. (a) 1 (b) 1 (c) 3 (d) 2 (e) 5

(f) 3 (g) 6 (h) 1 (i) 13 (j) 2
4. (a) 78 (b) 39 (c) 26 (d) 78 (e) 39

DPP # 05
Q.1 1. 5 2. 1 3. 3 4. 6
5. 6 6. 1 7. 8 8. 2
9. 2 10. 2 11. 1 12. 3
13. 2 14. 6 15. 16 16. 2
17. 4 18. 6 19. 1 20. 2
21. 10 22. 12 23. 2/3 24. 2
25. 4 26. 8 27. 16 28. 6
29. 2 30. 16 31. 2 32. 1
33. 1 34. 0.15 35. 15 36. 12
37. 8 38. 2 39. 16 40. 8
41. 24 42. 16 43. 8 44. 2
45. 2 46. 8 47. 2 48. 1
49. 2 50. 3
Q.2 1. 3 2. 10 3. 44/3 4. 28

5. 11 6. 27 7. 11 8. 10
9. 7 10. 4
Q.3 1. 5/3 2. 3/2 3. 2 4. 2
5. 1

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REDOX REACTION 150

OBJECTIVE EXERCISE
1. Reduction is defined as :
(A) Increase in positive valency (B) Gain of electrons
(C) Loss of protons (D) Decrease in negative valency
2. A compound contains atoms X, Y and Z the oxidation number of X is + 2, Y is + 5 and Z is – 2 therefore a
possible formula of the compound is :
(A) XY Z2 (B) X2(YZ3)2 (C) X3(YZ4)2 (D) X3(Y4Z)2
3. The atomic number of an element which shows the oxidation state of + 3 is :
(A) 13 (B) 32 (C) 33 (D) 17
4. Which of the following is the correct oxidation number of phosphorus in Mg2P2O7 :
(A) – 3 (B) + 2 (C) + 5 (D) + 3
5. Co(s) + Cu2+(aq)  Co2+(aq) + Cu(s). The above reaction is :
(A) Oxidation reaction (B) Reduction reaction (C) Redox reaction (D) None of these
6. Which of the following reactions depict the oxidising behavior of H2SO4 :
(A) 2PCl5 + H2SO4  2POCl3 + 2HCl + SO2Cl2
(B) 2NaOH + H2SO4  Na2SO4 + 2H2O
(C) NaCl + H2SO4  NaHSO4 + HCl
(D) 2HI + H2SO4  I2 + SO2 + 2H2O
7. Oxidation number of sulphur in Na2SO4 is :
(A) – 2 (B) + 6 (C) + 2 (D) – 6
8. Oxidation state of O2 in H2O2 is :
(A) – 2 (B) – 1 (C) + 1 (D) + 2
9. In C + H2O  CO + H2, H2O acts as :
(A) Oxidising agent (B) Reducing agent (C) Both (D) None
10. If three electrons are lost by a metal ion M3+, its final oxidation number should be :
(A) 0 (B) + 6 (C) + 2 (D) + 4
11. Oxidation number of Fe in K3[Fe(CN)6] is :
(A) + 2 (B) + 3 (C) + 1 (D) + 4
12. Reducing agent is that :
(A) Which takes electrons (B) Which takes protons
(C) Which donates electrons (D) Which donates protons
13. HBr and HI reduce sulphuric acid. HCl can reduce KMnO4 and HF can reduce :
(A) H2SO4 (B) KMnO4 (C) K2Cr2O7 (D) None of these
14. The compound which gives oxygen on moderate heating is :
(A) Ferric oxide (B) Zinc oxide
(C) Mercuric oxide (D) Aluminium oxide
15. Oxidation number of sulphur in S2Cl2 is :
(A) + 1 (B) 0 (C) – 1 (D) + 6
16. In a reaction between zinc and iodine in which zinc iodide is formed, what is being oxidised :
(A) Zinc ions (B) Iodide ions (C) Zinc atom (D) Iodine
2–
17. Oxidation number of sulphur in S2O2 is :
(A) – 2 (B) + 1 (C) + 6 (D) 0
18. Oxidation number of nitrogen in NH3 is :
(A) – 3 (B) + 3 (C) 0 (D) + 5
19. In acidic medium equivalent weight of K2Cr2O7 (molecular weight = M) is :
(A) M / 3 (B) M / 4 (C) M / 6 (D) M / 2
20. In the following reactions : 4P + 3KOH + 3H2O  3KH2PO2 + PH3
(A) Only phosphorus is oxidized (B) Only phosphorus is reduced
(C) Phosphorus is both oxidized and reduced (D) Phosphorus is neither oxidized nor reduced

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21. The oxidation number of nitrogen in NH2OH is :

(A) + 1 (B) – 1 (C) – 3 (D) – 2
22. The reaction of Zn++ + 2e–  Zn is an example of :
(A) Oxidation (B) Reduction (C) Redox reaction (D) None
23. Oxidation number of P in KH2PO2 is :
(A) +1 (B) 6 (C) 4 (D) 7
24. In the reaction 3Cl2 + 6OH–  5Cl– + ClO3– + 3H2O chlorine is :
(A) Oxidised (B) Reduced
(C) Oxidised as well as reduced (D) Neither oxidised nor reduced
25. In the compounds KMnO4 and K2Cr2O7, the highest oxidation state is of the element :
(A) Potassium (B) Manganese (C) Chromium (D) Oxygen
26. In the reaction 3Br2 + 6CO32– + 3H2O  5Br– + BrO3– + 6HCO3–
(A) Bromine is oxidised and carbonate is reduced
(B) Bromine is both reduced and oxidised
(C) Bromine is neither reduced nor oxidised
(D) Bromine is reduced and water is oxidised
27. A gas X bleaches a flower by reduction and another gas Y by oxidation these gases are , respectively
(A) NH3 & SO3 (B) NO2 & N2O5 (C) SO2 & Cl2 (D) SO2 & PCl3
28. What will happen when copper rod is dipped in aluminium nitrate solution, if the electropositive
properties are as follows : Al > Zn > Cu > Ag
(A) Aluminium will get deposited on the rod
(B) Colour of the solution will becomes blue
(C) Copper aluminium alloy will be formed
(D) No reaction will occur
29. The normal oxidation state of an element is – 2. The number of electrons in its outermost shell will be
(A) 4 (B) 2 (C) 6 (D) 8
30. For the reaction : 4Fe + 3O2  4Fe + 6O which of the following is a wrong statement ?
3+ 2–

(A) It is an example of redox reaction (B) Metallic iron reduces to Fe3+

(C) Fe is oxidised (D) Metallic iron is a reducing agent
31. Oxidation number of Ni in Ni(CO)4 is :
(A) 0 (B) 4 (C) 8 (D) 2
32. The oxidation number of nitrogen in NH4NO3 is :
(A) + 3 (B) + 5 (C) – 3 and + 5 (D) + 3 and + 5
– 2+
33. In acidic medium, reaction : MnO4 Mn is an example of :
(A) Oxidation by three electrons (B) Reduction by three electrons
(C) Oxidation by five electrons (D) Reduction by five electrons
34. Which of the following halogens always shows only one oxidation state ?
(A) Cl (B) F (C) Br (D) I
35. In the reaction MnO4 + NO2  NO3 + Mn
– – – 2+

one mole of MnO4– oxidises ________ moles of NO2–

(A) 5 (B) 5/2 (C) 3 (D) 3/2
36. In the following reaction As2S5 + NO3  AsO4 + SO4 + NO2
– 3– 2–

The equivalent weight of As2S5 is

(A) M/8 (B) M/6 (C) M/40 (D) M/30
37. In a reaction the equivalent weight of KMnO4 becomes one third of its molecular weight. The oxidation state
of Mn in the final product is
(A) + 6 (B) + 4 (C) + 3 (D) + 2
38. In which of the following compound oxidation number of Cl is + 3 ?
(A) ICl (B) ClO3- (C) ClF3 (D) HClO4

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39. The oxidation number of cobalt in [Co(CN)6]3- is -

(A) + 3 (B) - 3 (C) + 6 (D) - 6
40. In which of the following compound oxidation number of iron is not +3
(A) Fe3O4 (B) Fe2O3 (C) FeCl3 (D) FePO4
41. The oxidation number of Mn in MnC2O4 is -
(A) + 3 (B) + 8/3 (C) + 1 (D) +2
42. In the following equation ClO3- + 6 H+ + X  Cl- + 3H2O, then X is
(A) O (B) 6e– (C) O2 (D) 5e–
43. The correct oxidation number of phosphorus in magnesium pyrophosphate [Mg2P2O7] is -
(A) + 2 (B) + 3 (C) - 3 (D) + 5
44. Oxidation number of sulphur in H2SO5 is -
(A) + 2 (B) + 4 (C) + 8 (D) + 6
45. In which of the following compound, iodine is in its highest oxidation state -
(A) KI (B) KIO4 (C) KI3 (D) IF5
46. Oxidation number of chlorine in Hypochlorous acid is–
(A) –1 (B) zero (C) + 1 (D) + 2
47. Which one of the following compounds can act as an oxidising as well as reducing agent -
(A) KMnO4 (B) H2O2 (C) BaO (D) K2Cr2O7
48. When acidic solution of ferrous ammonium sulphate is treated with potassium permanganate solution then
the ion which is oxidised is -
(A) MnO4– (B) NH4+ (C) Fe2+ (D) SO 42–
49. The violent reaction between sodium and water is an example of -
(A) Reduction (B) Oxidation (C) Redox reaction (D) Neutralization
50. The equivalent weight of reducing agent in the reaction
2[Fe(CN)6]3– + 2OH– + H2O2  2[Fe(CN)6]4– + 2H2O + O -
(A) 17 (B) 212 (C) 16 (D) 6/8
51. In the formation of Pb(NO3)2 form PbO2 -
(A) PbO2 is oxidised (B) PbO2 is reduced
(C) PbO2 is both oxidised and reduced. (D) PbO2 is neither oxidised nor reduced
52. The compound in which oxidation state of metal is zero -
(A) Fe2(CO)9 (B) Ni(CO)4 (C) Fe3(CO)9 (D) All the above
53. The oxidation state of phosphorus is + 3 in -
(A) Orthophosphorous acid (B) Orthophosphoric acid
(C) Pyrophosphoric acid (D) Metaphosphoric acid
54. Which of the following is a true statement -
(A) Oxidation state of oxygen in HOF is zero.
(B) Oxidation state of fluorine in HOF is – 1.
(C) Oxidation state of chlorine in HOCl is + 1.
(D) All of the above.
55. The following reaction is used in the extraction of chromium from its ore
2Fe2O3.Cr2O3 + 4Na2CO3 + 3O2  2Fe2O3 + 4Na2CrO4 + 4CO2
What is true about the oxidation states of the substance in the reaction -
(A) Chromium is oxidised from + 3 to + 6 oxidation state.
(B) Iron is reduced from + 3 to + 2 oxidation state.
(C) Carbon is oxidised from + 3 to + 4 oxidation state
(D) There is no change in the oxidation states of the substances.
56. Oxidation state of nitrogen is incorrectly given for -
Compounds Oxidation states Compounds Oxidation states
(A) [Co(NH3)5Cl]Cl2 –3 (B) NH2OH –1
(C) (N2H5)2SO4 +2 (D) Mg3N2 –3

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57. Which of the following is an example of reduction -

(A) CuO  Cu2O (B) [Fe(CN)6]4–  [Fe(CN)6]3–
(C) KI  I2 (D) H2S  S
58. Out of the following acids which has different oxidation state of phosphorus as compared to others -
(A) Phosphorous acid (B) Orthophosphoric acid
(C) Metaphosphoric acid (D) Pyrophosphoric acid
59. Reaction [Ag(NH3)2] + 2H  Ag + 2NH4 is an example of -
+ + + +

(A) Oxidation (B) Reduction

(C) Neither oxidation nor reduction (D) Oxidation and reduction both
60. The brown ring complex compound is formulated as [Fe(H2O)5NO+]SO4. The oxidation state of iron is -
(A) 1 (B) 2 (C) 3 (D) zero
61. Which of the following reactions involves neither oxidation nor reduction -
(A) CrO42–  Cr2O72– (B) Cr–  CrCl3
(C) VO  V2O2
2+
(D) 2S2O32–  S4O62–
62. When KMnO4 is reduced with oxalic acid in acidic solution, the oxidation number of Mn changes from -
(A) 7 to 4 (B) 6 to 4 (C) 7 to 2 (D) 4 to 2
63. What would happen when a small quantity of H2O2 is added to a solution of FeSO4 -
(A) Colour disappears (B) H2 is evolved
(C) An electron is added to Fe++ (D) An electron is lost by Fe++
64. The oxidation number of each sulphur in Na2S4O6 is -
(A) 2.5
(B) 2 and 3 (two S have + 2 and the other two have + 3)
(C) 2 and 4 (three S have + 2 and one S has + 4)
(D) 5 and 0 (two S have + 5 and the other S have 0)
65. In a redox reaction K2Cr2O7 changes to Cr2(SO4)3. If the molecular weight of K2Cr2O7 is M and equivalent
weight E then -
(A) M = 3E (B) M = 6E (C) E = 2M (D) E = 6M
66. Fe3O4 is oxidised to Fe2O3. If the molecular weight of Fe3O4 is M and equivalent weight E then -
M 2 3
(A) E = M (B) E  (C) E  M (D) E  M
3 3 2
67. In a triatomic molecule the oxidation states of atoms A, B and C are + 6, + 1 and – 2 respectively. The
molecular formula of the compound will be -
(A) B2AC4 (B) B2A2C7 (C) Both of the above. (D) None
68. The reaction 2TiCl3  TiCl2 + TiCl4 example of -
(A) dissociation (B) disproportation
(C) reversible reaction (D) exothermic reaction
69. The anodic reaction in the electrolysis of the aqueous solution of NaCl is -
(A) Oxidation of chloride ion (B) Evolution of oxygen
(C) reduction of chloride ion (D) Oxidation of sodium ion.
70. Which of the following statements is not correct -
(A) Two mole of electrons are used in the reduction of MnO4– to MnO3–
(B) Three electrons per chromium atom are used in the reduction of dichromate by Fe (II)
(C) The oxidation state of oxygen is –1/2 in potassium superoxide.
(D) The oxidation number increases in the process of reduction.
71. In the reaction -
2FeCl3 + H2S  2FeCl2 + 2HCl + S
(A) FeCl3 is used as an oxidant. (B) FeCl3 and H2Sboth are oxidised.
(C) FeCl3 is oxidised and H2S is reduced. (D) H2S is used as an oxidant.

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72. Which of the following are oxidation-reduction reaction ?

(A) CH4 + 2O2  CO2 + 2H2O (B) Zn + 2HCl  ZnCl2 + H2
(g) (g) (g) (s) (aq) (aq) (g)
(C) O3 + NO  O2 + NO2 (D) All of these
(g) (g) (g) (g)
73. The Ostwald process for the commercial preparation of nitric acid involves the following three steps -
(i) 4NH3 + 5O2  4NO + 6H2O (ii) 2NO + O2  2NO2
(g) (g) (g) (g) (g) (g) (g)
(iii) 3NO + H2O  2HNO3 + NO
(g) ( I) (aq) (g)
Which reaction is redox reaction -
(A) i (B) ii (C) iii (D) i and iii
74. Which of the following statements statements is correct for the periodic table ?
(A) Reducing agents are placed at the left and oxidising agents are placed at the right hand
side of the table
(B) Reducing agents are placed at the right and oxidising agents are placed at the left hand
side of the table
(C) Reducing and oxidising agents, both are placed in the middle of the table
(D) None of the above
75. Strongest oxidising agent is -
(A) Na (B) F2 (C) Cl2 (D) Br2
2 2
76. The oxidation number of S in S2O3 and S 4 O 6 is respectively -
(A) +2, +2 (B) +2.5, +2.5 (C) +2, +2.5 (D) +2, –2.5
77. Which of the following can never has positive oxidation number ?
(A) F (B) Cl (C) O (D) N
78. The oxidation number of Fe in K4[Fe(CN)6] and K3[Fe(CN)6] is respectively -
(A) +2 in both (B) +3 in both (C) +2 and +3 (D) +3 and +2
79. The oxidation number of phosphorus in Ba(H2PO2) is
(A) +3 (B) –2 (C) +1 (D) –1
80. Which of the following acts both as an oxidising agent as well as reducing agent ?
(A) SO2 (B) HNO2 (C) H2O2 (D) All of these
81. When KMnO4 acts as an oxidising agent and finally forms MnO24 , MnO2 , Mn2O3 and Mn2+, then the
number of electrons transferred in each case respectively is -
(A) 4, 3, 1, 5 (B) 1, 5, 3, 7 (C) 1, 3, 4, 5 (D) 3, 5, 7, 1
82. What is the value of W, X, Y and Z respectively in the following reaction ?
H2O + WMnO4– + XlO3–  YMnO2 + ZlO4– + 2OH–
() (aq) (s) (aq)
(A) 2, 3, 2, 3 (B) 3, 3, 2, 2 (C) 2, 3, 3, 2 (D) 2, 2, 3, 3
83. Iodine reacts with aq thiosulphate ion in neutral solution according to the balanced equation,
I2 + 2S2O32– S4O62– + 2I–
(aq) (aq) (aq) (aq)
How many grams of I2 are present in a solution of 35.20 mL if 0.150 M Na2S2O3 solution is needed to
titrate the I2 solution ?
(A) 1.48 g (B) 0.67 g (C) 2.20 g (D) 0.22 g
84. What is the molar concentration of As (III) in a solution if 22.35 mL of 0.10 M KBrO3 is needed to titrate
50.00 mL of the As (III) solution ? The balanced equation is -
3H3AsO3 + BrO3– Br– + 3H3AsO4
(aq) (aq) (aq) (aq)
(A) 1.34 M (B) 4.31 M (C) 0.134 M (D) 0.431 M
85. Which one of the following is not a redox reaction -
(A) CaCO3  CaO + CO2 (B) 2H2 + O2  2H2O
1 1
(C) Na + H2O  NaOH + H2 (D) MnCl3  MnCl2 + Cl2
2 2

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86. In the reaction - MnO4– + SO32– + H+ SO42– + Mn+2 + H2O
(A) MnO4– and H+ both are reduced (B) MnO4– is reduced and H+ is oxidised
– 2–
(C) MnO4 is reduced and SO3 is oxidised (D) MnO4– is oxidised and SO42– is reduced
87. In which of the following compounds iron has lowest oxidation state -
(A) FeSO4(NH4)2SO4.6H2O (B) K4Fe(CN)6
(C) Fe(CO)5 (D) Fe 0.94O
88. Match List- I (compound) with list II (Oxidation state of N) and select the correct answer using the codes
given below the list -
List I List II
(A) KNO3 (a) – 1/3
(B) HNO2 (b) – 3
(C) NH4Cl (c) 0
(D) NaN3 (d) + 3
(e) + 5
Codes are -
A B C D A B C D
(A) e d b a (B) e b d a
(C) d e a c (D) b c d e
89. In which of the following pair oxidation number of Fe is same -
(A) K3Fe(CN)6, Fe2O3 (B) Fe(CO)5,Fe2O3
(C) Fe2O3,FeO (D) Fe2(SO4)3,K4Fe(CN)6
90. In the reaction - 3Br2 + 6CO3 + 3H2O  5Br + BrO3– + 6HCO3– bromine is -
–2 –

(A) Oxidised (B) Reduced (C) Both (D) None of these

91. In which of the following reaction H2O2 is reducing agent -
(A) 2FeCl2 + 2HCl + H2O2  2FeCl3 + 2H2O (B) Cl2 + H2O2  2HCl + O2
(C) 2HI + H2O2  2H2O + I2 (D) H2SO3 + H2O2  H2SO4 + H2O
92. Oxidation state of cobalt in [Co(NH3)4(H2O)Cl]SO4 is -
(A) 0 (B) 4 (C) 2 (D) 3
93. Which of the following reaction involves oxidation reduction -
(A) NaBr + HCl  NaCl + HBr (B) HBr + AgNO3  AgBr + HNO3
(C) 2NaOH + H2SO4  Na2SO4 + 2H2O (D) H2 + Br2  2HBr
94. In substance Mg(HXO3), the oxidation number of X is -
(A) 0 (B) +2 (C) +3 (D) +5
95. In which of the following reactions hydrogen peroxide is a reducing agent -
(A) 2 FeCl2 + 2HCl + H2O2  2FeCl3 + 2H2O (B) Cl2 + H2O2  2HCl + O2
(C) 2HI + H2O2  2H2O + I2 (D) H2SO3 + H2O2  H2SO4 + H2O
96. The oxidation number of phosphorus in PH4+, PO23–, PO43– and PO33– respectively -
(A) –3, +1, +3, +5 (B) –3, +3, +5, +1 (C) +3, –3, +5, +1 (D) –3, +1, +5, +3
97. In which of the following compounde are arranged in increasing oxidation number of S -
(A) H2SO3, H2S, H2SO4, H2S2O3 (B) H2S2O3, H2SO3,H2S, H2SO4
(C) H2S, H2SO3, H2SO4,H2S2O3 (D) H2S,H2S2O3,H2SO3,H2SO4
98. Cr2O7 + I + H  Cr + I2 + H2O
–2 – + +3

The equivalent weight of reductant in the above equation is - (At. wt. of Cr = 52, I = 27)
(A) 26 (B) 127 (C) 63.5 (D) 10.4
99. In the reaction 8Al + 3Fe3O4  4Al2O3 + 9Fe the number of electrons transfered from reductant to oxidant
is -
(A) 8 (B) 4 (C) 16 (D) 24
100. 1 mole of hydrozine loses 10 mole of electron to form a new compound (y) Assuming that all nitrogen
appears in the new compound. The oxidation state of nitrogen in the new compound is
(A) +6 (B) 4 (C) 8 (D) 3

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SUBJECTIVE EXERCISE
1. Determine the oxidation no. of following elements given in bold letters:
(a) KMnO4: (b) H2SO5: (c) H2S2O8 (d) NH4NO3
(e) OsO4 (f) HCN (g) HNC (h) HNO3
(i) KO2 (j) Fe3O4 (k) KI3 (l) N3H
(m) Fe0.94O (n) NH2.NH2 (o) FeSO4.(NH4)2SO4.6H2O
(p) NaClO (q) NaClO4 (r) Na2S4O6
(s) Dimethyl sulphoxide or (CH3)2SO (t) Na2S2O3
(u) CrO5 or CrO(O2)2 (v) CaOCl2
2. Determine the oxidation number of following elements given in bold letters:
(a) CuH (b) Na2S3O6 (c) N2O (d) Ba2XeO6
(e) C3O2 (f) V(BrO2)2 (g) Ca(ClO2)2
(h) Cs4Na(HV10O28) (i) LiAlH4 (j) K[Co(C2O4)2.(NH3)2]
(k) [Ni(CN)4]2– (l) Na2S2
3. Find the oxidation number of bold lettered atoms :
(a) NaNO2 (b) H2 (c) Cl2O7 (d) KCrO3Cl
(e) BaCl2 (f) ICI3 (g) K2Cr2O7 (h) CH2O
(i) Ni(CO)4 (j) NH2OH (k) (N2H5)2SO4 (l) Mg3N2
(m) [Co(NH3)5Cl]Cl2 (n) K2FeO4 (o) Ba(H2PO2)2 (p) H2SO4
(q) CS2 (r) S–2 (s) Na2S4O6 (t) S2Cl2
–2
(u) CH3NO2 (v) Pb3O4 (w) S2O8 (x) C6H12O6
(y) Mg3P2O7 (z) KClO3
4. Find the oxidation number of bold lettered atoms :
(a) Mn in K2MnO4 , K2Mn3O4, MnSO4 , K3MnF6, MnO2
(b) Cr in CrO2Cl2 , Na2Cr3O10, Cr2(SO4)3
(c) C in CH4 , C2H6 , C3H8 , C2H4 , C2H2 , H2C2O4 , CO2
(d) O in O2 , O3 , OF2 , BaO2 (e) S in Na2S2O3 , S4 , S8 , Na2S2O7
(f) N in NH3 , NH2OH , NaN3 , NH4NO2
(g) Cl in Cl2 , HOCl , Cl2O , ClO2 , KClO3 , Cl2O7 (h) P in H3PO4 , H3PO3 , HPO3 , P2O5
5. Which of the reactants act as oxidant or rdductant if any :
(a) [Ag(NH3)2]+ + 2H+  Ag+ +2NH4+
(b) PCl3 + 5KI + 6HCl  PCl5
(c) KIO3+5KI+6HCl 3I2 + 6KCl+3H2O
(d) 2CuSO4 + SO2 + 2KBr + 2H2O  2CuBr + 2H2SO4 + K2SO4
(e) C2H4 + Br2  C2H4Br2
(f) Si + 2KOH + H2O  K2SiO3 + 2H2
(g) Ca + Cl2  CaCl2
(h) 2 Cu2+ + 4I–  2CuI + I2
(i) 2I– + H2O2  2OH– + I2
6. Indentify the reactants if any oxidized or reduced.
(a) NaH + H2O  NaOH + H2 (b) 2FeCl3 + H2S  2FeCl2 + S + 2HCl
(c) 3Mg + N2  Mg3N2 (d) AgCN + CN–  Ag(CN)2–
(e) SnCl2 + Br2  SnCl2Br2 (f) AgCl + K  Ag + KCl
(g) 2CuSO4 + 4 KI  Cu2I2 + K2SO4 + I2 (h) NH4NO2  N2 + 2H2O
(i) CaC2 + H2O  Ca(OH)2 + C2H2 (j) SnS2 + S2  SnS32
7. Balance the following equations :
(a) H2CO2 + KMnO4  CO2 + K2O + MnO + H2O
(b) H2C2O4 + KMnO4  CO2 + K2O + Mn2O3 + H2O
(c) H2C2O4 + K2MnO4  CO2 + K2O + Mn2O3 + H2O

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REDOX REACTION 157
8. Write complete balanced equation in basic medium
(a) Cu2+ + I–  Cu + + I2

(b) MNO4– + Fe2+ H Cl–+Fe3 + H2O
(c) I2 + OH–  I– + IO3– (d) ClO2 + Sb2–  ClO2– + Sb (OH)6–
OH 
(e) H2 + ReO4–   ReO2 + H2O (f) Cl2 + OH–  Cl– + ClO–
9. Balance the following in acidic medium :
(a) KClO3 + H2SO4  KHSO4 + HClO4 + ClO2 + H2O
(b) HCl + KMnO4  Cl2 + KCl + MnCl2 + H2O
(c) IO4– + I– + H+  I2 + H2O
(d) HNO3 + HBr  NO + Br2 + H2O
(e) H2S + Cr2O72– + H+  Cr2O3 + S8 + H2O
(f) Br– + BrO3– + H+  Br2 + H2O
(g) I2 + Cr2O72– + H+  Cr3 +IO3– + H2O
(h) Au + NO3– + Cl– + H+  AuCl3– + NO2 + H2O
(i) Cu2O + H+ + NO2–  Cu2+ + NO + H2O
(j) MnO42–  MnO4– + MnO2
(k) Cl2 + I2  IO3– + Cl–
(l) Cu2+ + SO2  Cu+ + SO42–
10. Balance the following reactions :
(a) SbCl3 + KIO3 + HCl  SbCl5 + ICl + H2O + KCl
(b) H2O2 + PbS  PbSO4 + H2O
(c) IO3– + HSO3–  SO42– + HSO4– + I2
(d) ClO3– + SO2  Cl2 + HSO4–
(e) H2S + Cl2  H2SO4 + HCl
(f) As2S5 + HNO3  H3AsO4 + H2SO4 + NO2
(g) HI + HNO3  H3AsO4 + H2SO4 + NO2
(h) S + OH–  S2– + S2O32–
(i) Na2S2O3 + KMnO4 + H2O  Na2S4O6 + MnO2 + KOH + NaOH
(j) FeC2O4 + KMnO4 + H2SO4  Fe2(SO4)3 + CO2 + MnSO4 + K2SO4 + H2O
(k) AsH3 + KClO3  H3AsO4 + KCl
(l) I2 + S2O32–  I– + S4O62–
(m) Cr2O72– + C2H4O + H+  C2H4O2 + Cr3+
(n) HNO3 + HCl  NO + Cl2 + H2O
(o) H2S + SO2  S + H2O
11. What is the weight of 1 gram-equivalent of the oxidising and the reducing agent in the following reaction?
5Zn + V2O5  5ZnO + 2V (V = 50.94, Zn = 65.38 and O = 16)
12. Write the following oxidising agents in the increasing order of equivalent weight:
KMnO4  Mn2+
K2Cr2O7  Cr3+
KMnO4  MnO2
KIO3  I–
KClO3  Cl–
13. Find the equivalent weight of H3PO4 in each of the following reactions:
H3PO4 + OH–  H2PO4– + H2O
H3PO4 + 2OH–  HPO42– + 2H2O
H3PO4 + 3OH–  PO43– + 3H2O
14. Calculate the equivalent weight of SO2 in the following reactions:
(a) SO2 + 2H2S = 3S + 2H2O
(b) 5SO2 + 2KMnO4 + 2H2O = K2SO4 + 2MnSO4 + 2H2SO4
15. How many grams of H2S will react with 6.32 g of KMnO4 to produce K2SO4 and MnO2?

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NCERT CORNER
1. Assign oxidation numbers to the underlined elements in each of the following species:
(a) NaH2PO4 (b) NaHSO4 (c) H4P2O7 (d) K2MnO4
(e) CaO2 (f) NaBH4 (g) H2S2O7
(h) KAl(SO4)2.12 H2O
Sol. : (a) NaH2PO4
Let the oxidation number of P be x.
We know that,
Oxidation number of Na = +1
Oxidation number of H = +1
Oxidation number of O = –2
1 1 x 2
 Na H 2 P O 4
Then, we have 1(+1)+ 2 (+1) + 1(x) + 4 (–2) = 0
 1 + 2 + x – 8 = 0  x = +5
Hence, the oxidation number of P is +5.
(b) NaHSO4
1 1 x 2
 Na HSO4
Then, we have 1 (+1) + 1 (+1) + 1(x) + 4(–2) = 0
 1 + 1 + x – 8 = 0  x = +6
Hence, the oxidation number of S is + 6.
(c) H4P2O7
1 x 2
H 4 P2 O7
Then, we have 4 (+1) + 2(x) + 7 (–2) = 0
 4 + 2x – 14 = 0  2x = + 10  x = +5
Hence, the oxidation number of P is + 5.
(d) K2MnO4
1 x 2
K 2 Mn O 4
Then, we have 2 (+ 1) + x + 4 (–2) = 0
 2 + x – 8 = 0  x= + 6
Hence, the oxidation number of Mn is + 6.
(e) CaO2
2 x
Ca O 2
Then, we have (+2) + 2(x) = 0
 2 + 2x = 0  x = –1
Hence, the oxidation number of O is – 1.
(f) NaBH4
1 x 1
Na BH 4
Then, we have 1 (+1) + 1 (x) + 4 (–1) = 0
 1 + x – 4 = 0  x = +3
Hence, the oxidation number of B is + 3.
(g) H2S2O7
1 x 2
H 2 S2 O 7
Then, we have 2 (+1) + 2 (x) + 7 (–2) = 0
 2 + 2x – 14 = 0  2x = 12  x = +6
Hence, the oxidation number of S is + 6.
(h) KAl(SO4)2.12 H2O

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1 3 
 x 2  1 2
K Al  SO 4  .12 H 2 O
 2
Then, we have 1 (+ 1) + 1 (+3) + 2(x) + 8 (–2) + 24 (+1) + 12(–2) = 0
 1 + 3 + 2x – 16 + 24 – 24 = 0  2x = 12  x = +6
Or,
We can ignore the water molecule as it is a neutral molecule. Then, the sum of the oxidation numbers
of all atoms of the water molecule may be taken as zero. Therefore, after ignoring the water molecule,
we have
1(+1) + 1(+3) + 2(x) + 8(–2) = 0
 1 + 3 + 2x – 16 = 0  2x = 12  x = +6
Hence, the oxidation number of S is + 6.
2. What are the oxidation numbers of the underlined elements in each of the following and how do you rationalise
your results?
(a) KI3 (b) H2S4O6 (c) Fe3O4 (d) CH3CH2OH (e) CH3COOH
Ans : (a) KI3
1
In KI3, the oxidation number (O.N.) of K is +1. Hence, the average oxidation number of I is  . However,,
3
O.N. cannot be fractional. Therefore, we will have to consider the structure of KI3 to find the oxidation
states.
In a KI3 molecule, an atom of iodine forms a coordinate covalent bond with an iodine molecule.
1 
 0 0 1
K  I I  I 
 
Hence, in a KI3 molecule, the O.N. of the two I atoms forming the I2 molecule is 0, whereas the O.N.
of the I atom forming the coordinate bond is –1.
(b) H2S4O6
1 x 2
H 2 SO 4 O 6
Now, 2 (+1) + 4 (x) + 6 (–2) = 0
1
 2 + 4x – 12 = 0  4x = 10  x  2
2
However, O.N. cannot be fractional. Hence, S must be present in different oxidation states in the molecule.
The O.N. of two of the four S atoms is +5 and the O.N.of the other two S atoms is 0.
(c) Fe 3O4
On taking the O.N. of O as –2, the O.N. of Fe is found to be. However, O.N. cannot be fractional.
Here, one of the three Fe atoms exhibits the O.N. of +2 and the other two Fe atoms exhibit the O.N.
of +3.
(d) CH3CH2OH
x 1 2
C2 H6 O
Hence, the O.N. of C is –2.
(e) CH3COOH
x 1 2
C2 H 4 O 2
2(x) + 4 (+1) + 2 (–2) = 0  2x + 4 – 4 = 0
 x = 0
However, 0 is average O.N. of C. The two carbon atoms present in this molecule are present in different
environments. Hence, they cannot have the same oxidation number. Thus, C exhibits the oxidation states
of +2 and –2 in CH3COOH.
H O
–2 –2
H C C O H
H
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3. Justify that the following reactions are redox reactions:
(a) CuO(s) + H2(g)  Cu(s) + H2O(g)
(b) Fe2O3(s) + 3CO(g)  2Fe(s) + 3CO2(g)
(c) 4BCl3(g) + 3LiAlH4(s)  2B2H6(g) + 3LiCl(s) + 3 AlCl3(s)
(d) 2K(s) + F2(g)  2K+F– (s)
(e) 4 NH3(g) + 5 O2(g)  4NO(g) + 6H2O(g)
Ans: (a) CuO(s) + H2(g)  Cu(s) + H2O(g)
Let us write the oxidation number of each element involved in the given reaction as:
2 2 0 0 1 2
C u O(s)  H 2(g ) 
 C u (s)  H 2 O(g)
Here, the oxidation number of Cu decreases from +2 in CuO to 0 in Cu i.e., CuO is reduced to Cu.
Also, the oxidation number of H increases from 0 in H2 to +1 in H2O i.e., H2 is oxidized to H2O. Hence,
this reaction is a redox reaction.
(b) Fe2O3(s) + 3CO(g)   2Fe(s) + 3CO2(g)
Let us write the oxidation number of each element in the given reaction as:
3 2 2  2 0 1  2
F e 2 O3(s)  3CO (g ) 
 2 Fe(s)  3CO (g)
Here, the oxidation number of Fe decreases from +3 in Fe2O3 to 0 in Fe i.e., Fe2O3 is reduced to Fe.
On the other hand, the oxidation number of C increases from +2 in CO to +4 in CO2 i.e., CO is oxidized
to CO2. Hence, the given reaction is a redox reaction.
(c) 4BCl3(g) + 3LiAlH4(s) 
 2B2H6(g) + 3LiCl(s) + 3AlCl3(s)
The oxidation number of each element in the given reaction can be represented as:
3 1 1  3 1 3 1 1 1 3 1
4 BCl3(g)  3LiAlH 4 (s) 
 2 B2 H 6(g)  3LiCl(s)  3AlCl3(s)
In this reaction, the oxidation number of B decreases from +3 in BCl3 to –3 in B2H6. i.e., BCl3 is reduced
to B2H6. Also, the oxidation number of H increases from –1 in LiAlH4 to +1 in B2H6 i.e., LiAlH4 is
oxidized to B2H6. Hence, the given reaction is a redox reaction.
(d) 2K(s) + F2(g) 
 2K +F–(s)
The oxidation number of each element in the given reaction can be represented as:
0 0 1 1
 2 K  F (s)
2 K (s)  F2(g) 
In this reaction, the oxidation number of K increases from 0 in K to +1 in KF i.e., K is oxidized to
KF. On the other hand, the oxidation number of F decreases from 0 in F2 to –1 in KF i.e., F2 is reduced
to KF.
Hence, the above reaction is a redox reaction.
(e) 4NH3(g) + 5O2(g) 
 4NO(g) + 6H2O(g)
The oxidation number of each element in the given reaction can be represented as:
3 1 0  2 2 1 2
4 N H 3(g)  5O2(g) 
 4 N O(g)  6 H 2 O(g)
Here, the oxidation number of N increases from –3 in NH3 to +2 in NO. On the other hand, the oxidation
number of O2 decreases from 0 in O2 to –2 in NO and H2O i.e., O2 is reduced. Hence, the given reaction
is a redox reaction.
4. Fluorine reacts with ice and results in the change:
H2O(s) + F2(g)  HF(g) + HOF(g)
Justify that this reaction is a redox reaction.
Ans : Let us write the oxidation number of each atom involved in the given reaction above its symbol as:
1 2 0  1 1 1 2 1
H 2 O  F2 
 H F HOF
Here, we have observed that the oxidation number of F increases from 0 in F2 to +1 in HOF. Also,
the oxidation number decreases from 0 in F2 to –1 in HF. Thus, in the above reaction, F is both oxidized
and reduced. Hence, the given reaction is a redox reaction.

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2– –
5. Calculate the oxidation number of sulphur, chromium and nitrogen in H2SO5, Cr2O7 and NO3 Suggest
structure of these compounds. Count for the fallacy.
1 x 2
Ans : (i) H 2 SO5
2(+1) + 1(x) + 5(–2) = 0
 2 + x – 10 = 0
 x = +8
However, the O.N. of S cannot be +8. S has six valence electrons. Therefore, the O.N. of S cannot be
more than +6.
The structure of H2SO5 is shown as follows:
–2
O
+1 –2 x –1 –1 +1
H O S O O H

O–2
Now, 2(+1) + 1(x) + 3(–2) + 2 (–1) = 0
 2 + x – 6 – 2 = 0
 x = +6
Therefore, the O.N. of S is +6.
x 2
(ii) Cr 2 O72 
2(x) + 7(–2) = –2
 2x – 14 = –2
 x = +6
Here, there is no fallacy about the O.N. of Cr in Cr2O72  .
The structure of Cr2O72  is shown as follows:
–2 –2
O O
–2 +6 2– +6 2–
O Cr O Cr O
– –
O O
1– 1–

Here, each of the two Cr atoms exhibits the O.N. of +6.

x 2
(iii) N O3
1(x) + 3(–2) = –1
 x – 6 = –1
 x =+ 5
Here, there is no fallacy about the O.N. of N in.
The structure of is shown as follows:
–2
O
+5 –1
–
N O
–2
O
The N atom exhibits the O.N. of +5.
6. Write the formulae for the following compounds:
(a) Mercury(II) chloride (b) Nickel(II) sulphate
(c) Tin(IV) oxide (d) Thallium(I) sulphate
(e) Iron(III) sulphate (f) Chromium(III) oxide
Ans : (a) Mercury (II) chloride: HgCl2
(b) Nickel (II) sulphate:NiSO4

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REDOX REACTION 162
(c) Tin (IV) oxide: SnO2
(d) Thallium (I) sulphate: Tl2SO4
(e) Iron (III) sulphate: Fe2(SO4)3
(f) Chromium (III) oxide: Cr2O3
7. Suggest a list of the substances where carbon can exhibit oxidation states from –4 to +4 and nitrogen
from –3 to +5.
Ans : The substances where carbon can exhibit oxidation states from –4 to +4 are listed in the following table.
Substance O.N. of carbon Substance O.N. of carbon
CH2Cl2 0 ClC  CCl +1
HC=CH –1 CHCl3, CO +2
CH3Cl –2 Cl3C – CCl3 +3
H3C – CH3 –3 CCl4, CO2 +4
CH4 –4
The substances where nitrogen can exhibit oxidation states from –3 to +5 are listed in the following table.
Substance O.N. of nitrogen Substance O.N. of nitrogen
N2 0 N2O +1
N2 H 2 –1 NO +2
N2 H 4 –2 N2 O 3 +3
NH3 –3 NO2 +4
N2 O 5 +5
8. While sulphur dioxide and hydrogen peroxide can act as oxidising as well as reducing agents in their
reactions, ozone and nitric acid act only as oxidants. Why?
Ans : In sulphur dioxide (SO2), the oxidation number (O.N.) of S is +4 and the range of the O.N. that S can have
is from +6 to –2.
Therefore, SO2 can act as an oxidising as well as a reducing agent.
In hydrogen peroxide (H2O2), the O.N. of O is –1 and the range of the O.N. that O can have is from 0 to –
2. O can sometimes also attain the oxidation numbers +1 and +2. Hence, H2O2 can act as an oxidising as
well as a reducing agent.
In ozone (O3), the O.N. of O is zero and the range of the O.N. that O can have is from 0 to –2. Therefore,
the O.N. of O can only decrease in this case. Hence, O3 acts only as an oxidant.
In nitric acid (HNO3), the O.N. of N is +5 and the range of the O.N. that N can have is from +5 to –3.
Therefore, the O.N. of N can only decrease in this case. Hence, HNO3 acts only as an oxidant.
9. Consider the reactions:
(a) 6 CO2(g) + 6H2O(l)  C6 H12 O6(aq) + 6O2(g)
(b) O3(g) + H2O2(l)  H2O(l) + 2O2(g)
Why it is more appropriate to write these reactions as:
(a) 6CO2(g) + 12H2O(l)  C6 H12O6(aq) + 6H2O(l) + 6O2(g)
(b) O3(g) + H2O2 (l)  H2O(l) + O2(g) + O2(g)
Also suggest a technique to investigate the path of the above (a) and (b) redox reactions.
Ans : (a) The process of photosynthesis involves two steps.
Step 1:
H2O decomposes to give H2 and O2.
2H2O(l) 
 2H2(g) + O2(g)
Step 2:
The H2 produced in step 1 reduces CO2, thereby producing glucose (C6H12O6) and H2O.
6CO2(g) + 12H2(g) 
 C6H12O6(s) + 6H2O(l)
Now, the net reaction of the process is given as:
2H2O(l) 2H2(g) + O2(g)] × 6
6CO2(g) + 12H 2(g) C6H12O6(g) + 6H2O (l)
6CO2(g) + 12H2O(l) C6 H12 O6(g) + 6H2O(l) + 6O2(g)

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REDOX REACTION 163
It is more appropriate to write the reaction as given above because water molecules are also produced in the
process of photosynthesis.
The path of this reaction can be investigated by using radioactive H2O18 in place of H2O.
(b) O2 is produced from each of the two reactants O3 and H2O2. For this reason, O2 is written twice.
The given reaction involves two steps. First, O3 decomposes to form O2 and O. In the second step, H2O2
reacts with the O produced in the first step, thereby producing H2O and O2.
O3(g) O2(g) + O(g)
H2O2(l) + O (g) H1O (l) + O2(g)
H2O2(l) + O3(g) H2O(l) + O2(g) + O 2(g)

The path of this reaction can be investigated by using H 2 O18 2

or O318 .
10. The compound AgF2 is an unstable compound. However, if formed, the compound acts as a very strong
oxidizing agent. Why?
Ans : The oxidation state of Ag in AgF2 is +2. But, +2 is an unstable oxidation state of Ag. Therefore, whenever
AgF2 is formed, silver readily accepts an electron to form Ag+. This helps to bring the oxidation state of Ag
down from +2 to a more stable state of +1. As a result, AgF2 acts as a very strong oxidizing agent.
11. Whenever a reaction between an oxidising agent and a reducing agent is carried out, a compound of lower
oxidation state is formed if the reducing agent is in excess and a compound of higher oxidation state is formed
if the oxidising agent is in excess. Justify this statement giving three illustrations.
Ans : Whenever a reaction between an oxidising agent and a reducing agent is carried out, a compound of lower
oxidation state is formed if the reducing agent is in excess and a compound of higher oxidation state is formed
if the oxidising agent is in excess. This can be illustrated as follows:
(i) P4 and F2 are reducing and oxidising agents respectively.
If an excess of P4 is treated with F2, then PF3 will be produced, wherein the oxidation number (O.N.) of P is
+3.
3
P4 (excess)  F2 
 P F3
However, if P4 is treated with an excess of F2, then PF5 will be produced, wherein the O.N. of P is +5.
5
P4  F2 (excess) 
 P F5
(ii) K acts as a reducing agent, whereas O2 is an oxidising agent.
If an excess of K reacts with O2, then K2O will be formed, wherein the O.N. of O is –2.
2
4K(excess)  O2   2K 2 O
However, if K reacts with an excess of O2, then K2O2 will be formed, wherein the O.N. of O is –1.
1
2K  O 2 (excess) 
 K 2 O2
(iii) C is a reducing agent, while O2 acts as an oxidising agent.
If an excess of C is burnt in the presence of insufficient amount of O2, then CO will be produced, wherein the
O.N. of C is +2.
2
C(excess)  O2 
 CO
On the other hand, if C is burnt in an excess of O2, then CO2 will be produced, wherein the O.N. of C is +4.
4
C  O2 (excess) 
 CO 2
12. How do you count for the following observations?
(a) Though alkaline potassium permanganate and acidic potassium permanganate both are used as oxi-
dants, yet in the manufacture of benzoic acid from toluene we use alcoholic potassium permanganate as an
oxidant. Why? Write a balanced redox equation for the reaction.
(b) When concentrated sulphuric acid is added to an inorganic mixture containing chloride, we get colourless
pungent smelling gas HCl, but if the mixture contains bromide then we get red vapour of bromine. Why?

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REDOX REACTION 164
Ans : (a) In the manufacture of benzoic acid from toluene, alcoholic potassium permanganate is used as an
oxidant because of the following reasons.
(i) In a neutral medium, OH– ions are produced in the reaction itself. As a result, the cost of adding an acid or
a base can be reduced.
(ii) KMnO4 and alcohol are homogeneous to each other since both are polar. Toluene and alcohol are also
homogeneous to each other because both are organic compounds. Reactions can proceed at a faster rate in
a homogeneous medium than in a heterogeneous medium. Hence, in alcohol, KMnO4 and toluene can react
at a faster rate.
The balanced redox equation for the reaction in a neutral medium is give as below:
CH3 COO–

+ 2MnO3(aq) + 2MnO 2(s) + H2O(l) + OH–(aq)

(b) When conc. H2SO4 is added to an inorganic mixture containing bromide, initially HBr is produced. HBr,
being a strong reducing agent reduces H2SO4 to SO2 with the evolution of red vapour of bromine.
2NaBr + 2H2SO4 
 2NaHSO4 + 2HBr
2HBr + H2SO4   Br2 + SO2 + 2H2O
(red vapour)
But, when conc. H2SO4 is added to an inorganic mixture containing chloride, a pungent smelling gas (HCl)
is evolved. HCl, being a weak reducing agent, cannot reduce H2SO4 to SO2.
2NaCl + 2H2SO4   2NaHSO4 + 2HCl
13. Identify the substance oxidised, reduced, oxidising agent and reducing agent for each of the following
reactions:
(a) 2AgBr (s) + C6H6O2(aq)  2Ag(s) + 2HBr (aq) + C6H4O2(aq)
(b) HCHO(l) + 2[Ag (NH3)2]+ (aq) + 3OH–(aq)  2Ag(s) + HCOO–(aq) + 4NH3(aq) +2H2O(l)
(c) HCHO (l) + 2Cu2+(aq) + 5 OH–(aq)  Cu2O(s) + HCOO–(aq) + 3H2O(l)
(d) N2H4(l) + 2H2O2(l)  N2(g) + 4H2O(l)
(e) Pb(s) + PbO2(s) + 2H2SO4(aq)  2PbSO4(s) + 2H2O(l)
Ans : (a) Oxidised substance  C6H6O2
Reduced substance  AgBr
Oxidising agent  AgBr
Reducing agent  C6H6O2
(b) Oxidised substance  HCHO
Reduced substance  [Ag(NH3)2]+
Oxidising agent  [Ag(NH3)2]+
Reducing agent  HCHO
(c) Oxidised substance  HCHO
Reduced substance  Cu2+
Oxidising agent  Cu2+
Reducing agent  HCHO
(d) Oxidised substance  N2H4
Reduced substance  H2O2
Oxidising agent  H2O2
Reducing agent  N2H4
(e) Oxidised substance  Pb
Reduced substance  PbO2
Oxidising agent  PbO2
Reducing agent  Pb
14. Consider the reactions:
2S2O32–(aq) + I2(s)  S 4O62 (aq) + 2I–(aq)
S2O32–(aq) + 2Br2(l) + 5 H2O(l)  2SO42 (aq) + 4Br–(aq) + 10H+(aq)
Why does the same reductant, thiosulphate react differently with iodine and bromine?

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2–
Ans : The average oxidation number (O.N.) of S in S2O3 is +2. Being a stronger oxidising agent than I2, Br2
oxidises S2O32– to SO42–, in which the O.N. of S is +6. However, I2 is a weak oxidising agent. Therefore, it
oxidises S2O32– to S4O62– , in which the average O.N. of S is only +2.5. As a result, S2O32–reacts differently
with iodine and bromine.
15. Justify giving reactions that among halogens, fluorine is the best oxidant and among hydrohalic compounds,
hydroiodic acid is the best reductant.
Ans: F2 can oxidize Cl– to Cl2, Br– to Br2, and I– to I2 as:
F2(aq) + 2Cl–(s) 
 2F–(aq) + Cl(g)
F2(aq) + 2Br–(aq) 
 2F–(aq) + Br2(l)
F2(aq) + 2I–(aq) 
 2F–(aq) + I2(s)
On the other hand, Cl2, Br2, and I2 cannot oxidize F– to F2. The oxidizing power of halogens increases in the
order of I2 < Br2 < Cl2 < F2. Hence, fluorine is the best oxidant among halogens.
HI and HBr can reduce H2SO4 to SO2, but HCl and HF cannot. Therefore, HI and HBr are stronger
reductants than HCl and HF.
2HI + H2SO4 
 I2 + SO2 + 2H2O
2HBr + H2SO4 
 Br2 + SO2 + 2H2O
Again, I– can reduce Cu2+ to Cu+, but Br– cannot.
4I–(aq) + 2Cu2+(aq) 
 Cu2I2(s) + I2(aq)
Hence, hydroiodic acid is the best reductant among hydrohalic compounds.
Thus, the reducing power of hydrohalic acids increases in the order of HF < HCl < HBr < HI.
16. Why does the following reaction occur?
XeO64–(aq) + 2F– (aq) + 6H+(aq)  XeO3(g) + F2(g) + 3H2O(l)
What conclusion about the compound Na4XeO6 (of which XeO64– is a part) can be drawn from the reaction.
Ans : The given reaction occurs because XeO64– oxidises F– and F– reduces XeO64–.
8 1 6 0
4 
X eO6(aq)  2 F (aq)  6H (aq) 
 X eO3(g)  F2(g)  3H 2 O (l)

In this reaction, the oxidation number (O.N.) of Xe decreases from +8 in XeO64 to +6 in XeO3 and the
O.N. of F increases from –1 in F– to O in F2.
Hence, we can conclude that Na4XeO6 is a stronger oxidising agent than F–.
17. Consider the reactions:
(a) H3PO2(aq) + 4 AgNO3(aq) + 2 H2O(l)  H3PO4(aq) + 4Ag(s) + 4HNO3(aq)
(b) H3PO2(aq) + 2CuSO4(aq) + 2 H2O(l)  H3PO4(aq) + 2Cu(s) + H2SO4(aq)
(c) C6H5CHO(l) + 2[Ag (NH3)2] + (aq) + 3OH–(aq)  C6H5COO–(aq) + 2Ag(s) + 4NH3(aq) + 2 H2O(l)
(d) C6H5CHO(l) + 2Cu2+(aq) + 5OH–(aq)  No change observed.
What inference do you draw about the behaviour of Ag+ and Cu2+ from these reactions?
Ans : Ag+ and Cu2+ act as oxidising agents in reactions (a) and (b) respectively.
In reaction (c), Ag+ oxidises C6H5CHO to C6H5COO–, but in reaction (d), Cu2+ cannot oxidise C6H5CHO.
Hence, we can say that Ag+ is a stronger oxidising agent than Cu2+.
18. Balance the following redox reactions by ion-electron method:
(a) MnO4–(aq) + I– (aq)  MnO2 (s) + I2(s) (in basic medium)
(b) MnO4–(aq) + SO2 (g)  Mn2+ (aq) + HSO4 (aq) (in acidic solution)
(c) H2O2(aq) + Fe2+ (aq)  Fe3+ (aq) + H2O (l) (in acidic solution)
(d) Cr2O72– + SO2(g)  Cr3+ (aq) + SO42–(aq) (in acidic solution)
Ans : (a) Step 1: The two half reactions involved in the given reaction are:
1 0
Oxidation half reaction: I  aq  
 I 2 s 

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REDOX REACTION 166

7 4
Reduction half reaction: M nO 4 aq  
 M nO 2 aq 
Step 2:
Balancing I in the oxidation half reaction, we have:
2Iaq  
 I 2 s 
Now, to balance the charge, we add 2 e– to the RHS of the reaction.
2I aq  
 I2 s   2e
Step 3:
In the reduction half reaction, the oxidation state of Mn has reduced from +7 to +4. Thus, 3 electrons are
added to the LHS of the reaction.
MnO 4 aq   3e 
 MnO2 aq 
Now, to balance the charge, we add 4 OH– ions to the RHS of the reaction as the reaction is taking place in
a basic medium.
MnO 4 aq   3e  
 MnO2 aq   4OH 
Step 4:
In this equation, there are 6 O atoms on the RHS and 4 O atoms on the LHS. Therefore, two water
molecules are added to the LHS.
MnO 4 aq   2H 2 O  3e  
 MnO 2 aq   4OH 
Step 5:
Equalising the number of electrons by multiplying the oxidation half reaction by 3 and the reduction half
reaction by 2, we have:
6Iaq  
 3I 2 s   6e
Step 6:
Adding the two half reactions, we have the net balanced redox reaction as:
6I–(aq) + 2MnO–4(aq) + 4H2O(l) 
 3I2(s) + 2MnO2(s) + 8OH–(aq)
(b) Following the steps as in part (a), we have the oxidation half reaction as:
SO2(g) + 2H2O(l) 
 HSO–4(aq) + 3H+(aq) + 2e–(aq)
And the reduction half reaction as:
2MnO–4(aq) + 5SO2(g) + 2H2O(l) + H+(aq) 
 2Mn2+(aq) + 5HSO–4(aq)
Multiplying the oxidation half reaction by 5 and the reduction half reaction by 2, and then by adding them,
we have the net balanced redox reaction as:
(c) Following the steps as in part (a), we have the oxidation half reaction as:
Fe 2(aq )  
 Fe3(aq)  e
And the reduction half reaction as:
H2O(aq) + 2H+(aq) + 2e– 
 2H2O(l)
Multiplying the oxidation half reaction by 2 and then adding it to the reduction half reaction, we have the net
balanced redox reaction as:
H2O2(aq) + 2Fe2+(aq) + 2H+(aq) 
 2Fe3+(aq) + 2H2O(l)
(d) Following the steps as in part (a), we have the oxidation half reaction as:
SO2(g) + 2H2O(l) 
 SO2–4(aq) + 4H+(aq) + 2e–
And the reduction half reaction as:
Cr2O2–7(aq) + 14H+(aq) + 6e– 
 Cr3+(aq) + 7H2O(l)

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REDOX REACTION 167
Multiplying the oxidation half reaction by 3 and then adding it to the reduction half reaction, we have the net
balanced redox reaction as:
Cr2O2–7(aq) + 3SO2(g) + 2H+(aq) 
 2Cr3+(aq) + 3SO2–4(aq) + H2O(l)
19. Balance the following equations in basic medium by ion-electron method and oxidation number methods
and identify the oxidising agent and the reducing agent.
(a) P4(s) + OH–(aq) 
 PH3(g) + HPO–2(aq)
(b) N2H4(l) + OH–(aq) 
 PH3(g) + HPO–2(aq)
(c) Cl2O7(g) + H2O2(aq) 
 ClO–2(aq) + O2(g) + H+(aq)
Ans : The O.N. (oxidation number) of P decreases from 0 in P4 to – 3 in PH3 and increases from 0 in P4 to + 2 in
HPO–2. Hence, P4 acts both as an oxidizing agent and a reducing agent in this reaction.
Ion–electron method:
The oxidation half equation is:
P4(s)  H2PO2–(aq)
The P atom is balanced as:
0 1
P 4(s)  4H 2 P O 2  (aq)
The O.N. is balanced by adding 4 electrons as:
P4(s)  4H2PO–2(aq) + 4e–
The charge is balanced by adding 8OH– as:
P4(s) + 8OH–(aq)  4H2PO2–(aq) + 4e–
The O and H atoms are already balanced.
The reduction half equation is:
P4(s) 
 PH 3(g)
The P atom is balanced as
0 3
P 4(s) 
 4 P H 3(g)
The O.N. is balanced by adding 12 electrons as:
P4(s) + 12e– 
 4PH3(g)
The charge is balanced by adding 12OH– as:
P4(s) + 12e– 
 4PH3(g) + 12OH–(aq)
The O and H atoms are balanced by adding 12H2O as:
P4(s) + 12H2O(l) + 12e– 
 4PH3(g) + 12HO–(aq) ...(ii)
By multiplying equation (i) with 3 and (ii) with 2 and then adding them, the balanced chemical equation can
be obtained as:
P4(s) + 3OH–(aq) + 3H2O  PH3 + 3H2PO2–(aq)
O.N. of N increases by 4 per atom

–2 +5 +2 –1
(b) N2H4(l) + ClO–3(aq) NO(g) + Cl(aq)

O.N. of Cl decreases by 6 per atom

The oxidation number of N increases from – 2 in N2H4 to + 2 in NO and the oxidation number of Cl
decreases from + 5 in ClO3– to – 1 in Cl–. Hence, in this reaction, N2H4 is the reducing agent and ClO3– is
the oxidizing agent.

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REDOX REACTION 168
Ion–electron method:
The oxidation half equation is:
2 2
N 2 H 4(l) 
 N O(g)
The N atoms are balanced as:
N 2H4(l) 
 2NO(g)
The oxidation number is balanced by adding 8 electrons as:
N2H4(l) 
 2NO(g) + 8e–
The charge is balanced by adding 8 OH– ions as:
N2H4(l) + 8OH–(aq) 
 2NO(g) + 8e–
The O atoms are balanced by adding 6H2O as:
N2H4(l) + 8OH–(aq) 
 2NO(g) + 6H2O(l) + 8e– ...(i)
The reduction half equation is:
5 1
 
ClO3(aq) 
 Cl(aq)
The oxidation number is balanced by adding 6 electrons as:

ClO3(aq)  6e   
 Cl(aq)
The charge is balanced by adding 6OH– ions as:
   
ClO 3(aq )  6e 
 Cl (aq )  6OH (aq)

The O atoms are balanced by adding 3H2O as:


ClO3(aq)  3H 2 O (l)  6e   
 Cl (aq) 
 6OH (aq ) ...(ii)
The balanced equation can be obtained by multiplying equation (i) with 3 and equation (ii) with 4 and then
adding them as:
 
3N2H4(l) + 4Cl O 3(aq ) 
 6NO(g) + 4C l(aq ) + 6H2O(l)
Oxidation number method:
Total decrease in oxidation number of N = 2 × 4 = 8
Total increase in oxidation number of Cl = 1 × 6 = 6
On multiplying N2H4 with 3 and ClO3 with 4 to balance the increase and decrease in O.N., we get:
 
3N2H4(l) + 4Cl O 3(aq ) 
 NO(g) + Cl (aq )
The N and Cl atoms are balanced as:
 
3N2H4(l) + 4Cl O 3(aq ) 
 6NO(g) + 4 Cl (aq )
The O atoms are balanced by adding 6H2O as:
 
3N2H4(l) + 4Cl O 3(aq ) 
 6NO(g) + 4 Cl (aq ) + 6H2O(l)
This is the required balanced equation.
O.N. of Cl decreases by 4 per atom

+7 –1 +3 0
(c) Cl2O7(g) + H2O2(aq) ClO2–(g) + O2(g) + H+

O.N. of O increases by 1 per atom

The oxidation number of Cl decreases from + 7 in Cl2O7 to + 3 in ClO3 and the oxidation number of O
increases from – 1 in H2O2 to zero in O2. Hence, in this reaction, Cl2O7 is the oxidizing agent and H2O2 is the
reducing agent.

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REDOX REACTION 169
Ion–electron method:
The oxidation half equation is:
1 0
H 2 O2(aq) 
 O2(g)
The oxidation number is balanced by adding 2 electrons as:
H2O2(aq) 
 O2(g) + 2e–
The charge is balanced by adding 2OH– ions as:
H2O2(aq) + 2OH–(aq) 
 O2(g) + 2e–
The oxygen atoms are balanced by adding 2H2O as:
H2O2(aq) + 2OH–(g) 
 O2(g) + 2H2O(l) + 2e– (i)
The reduction half equation is:
7 3

Cl2 O7(g) 
 ClO2(aq)
The Cl atoms are balanced as:
Cl2O7(g) 
 2ClO–2(aq)
The oxidation number is balanced by adding 8 electrons as:
Cl2O7(g) + 8e– 
 2ClO–2(aq)
The charge is balanced by adding 6OH– as:
Cl2P7(g) + 8e– 
 2ClO–2(aq) + 6OH–(aq)
The oxygen atoms are balanced by adding 3H2O as:
Cl2O7(g) + 3H2O(l)8e– 
 2ClO–2(aq) + 6OH–(aq) (ii)
The balanced equation can be obtained by multiplying equation (i) with 4 and adding equation (ii) to it as:
Cl2O7(g) + 4H2O2(aq) + 2OH–(aq) 
 2ClO–2(aq) + 4O2(g) + 5H2O(l)
Oxidation number method:
Total decrease in oxidation number of Cl2O7 = 4 × 2 = 8
Total increase in oxidation number of H2O2 = 2 × 1 = 2
By multiplying H2O2 and O2 with 4 to balance the increase and decrease in the oxidation number, we get:
Cl2O7(g) + 4H2O2(aq) 
 ClO–2(aq) + 4O2(g)
The Cl atoms are balanced as:
Cl2O7(g) + 4H2O2(aq) 
 2ClO–2(aq) + 4O2(g)
The O atoms are balanced by adding 3H2O as:
Cl2O7(g) + 4H2O2(aq) 
 2ClO–2(aq) + 4O2(g) + 3H2O(l)
The H atoms are balanced by adding 2OH– and 2H2O as:
Cl2O7(g) + 4H2O2(aq) + 2OH–(aq) 
 2ClO–2(aq) + 4O2(g) + 5H2O(l)
This is the required balanced equation.
20. What sorts of informations can you draw from the following reaction ?
(CN)2(g) + 2OH–(aq) 
 CN–(aq) + CNO–(aq) + H2O(l)
Ans : The oxidation numbers of carbon in (CN)2, CN– and CNO– are +3, +2 and +4 respectively. These are
obtained as shown below:
Let the oxidation number of C be x.
(CN)2
2(x – 3) = 0
 x=3
CN–

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REDOX REACTION 170
x – 3 = –1
 x=2
CNO–
x – 3 – 2 = –1
 x=4
The oxidation number of carbon in the various species is:
 3  
2

4

 C N   2OH (aq) 
 C N (aq)  C NO(aq)  H 2 O(l)
  2(g)
It can be easily observed that the same compound is being reduced and oxidised simultaneously in the
given equation. Reactions in which the same compound is reduced and oxidised is known as dispropor-
tionation reactions. Thus, it can be said that the alkaline decomposition of cyanogen is an example of
disproportionation reaction.
21. The Mn3+ ion is unstable in solution and undergoes disproportionation to give Mn2+, MnO2, and H+ ion.
Write a balanced ionic equation for the reaction.
Ans : The given reaction can be represented as:
 2 
Mn 3(aq) 
 Mn (aq)  MnO 2(s)  H (aq )

The oxidation half equation is:

3 4

M n 3(aq) 
 M nO 2(s)
The oxidation number is balanced by adding one electron as:
Mn 3(aq ) 
 MnO 2(s)  e 
The charge is balanced by adding 4H+ ions as:
  
Mn 3(aq) 
 MnO 2(s)  4H (aq ) e

The O atoms and H+ ions are balanced by adding 2H2O molecules as:
Mn 3(aq )  2H 2 O (l)  
 MnO 2(s)  4H (aq)  e (i)
The reduction half equation is:
2 2
Mn (aq ) 
 Mn (aq)
The oxidation number is balanced by adding one electron as:

Mn 3(aq)  e   
 Mn 2(aq) (ii)
The balanced chemical equation can be obtained by adding equation (i) and (ii) as:
2Mn 3(aq )  2H 2 O (l)  2
 MnO 2(s)  2Mn (aq 
)  4H (aq)

22. Consider the elements:

Cs, Ne, I and F
(a) Identify the element that exhibits only negative oxidation state.
(b) Identify the element that exhibits only postive oxidation state.
(c) Identify the element that exhibits both positive and negative oxidation states.
(d) Identify the element which exhibits neither the negative nor does the positive oxidation state.
Ans : (a) F exhibits only negative oxidation state of –1.
(b) Cs exhibits positive oxidation state of +1.
(c) I exhibits both positive and negative oxidation states. It exhibits oxidation states of – 1, + 1,
+ 3, + 5, and + 7.
(d) The oxidation state of Ne is zero. It exhibits neither negative nor positive oxidation states.
23. Chlorine is used to purify drinking water. Excess of chlorine is harmful. The excess of chlorine is removed
by treating with sulphur dioxide. Present a balanced equation for this redox change taking place in water.
Ans : The given redox reaction can be represented as:
Cl2(s) + SO2(aq) + H2O(l) 
 Cl–(aq) + SO2–4(aq)

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REDOX REACTION 171
The oxidation half reaction is:
4 6

S O 2(aq) 
 S O 24(aq)
The oxidation number is balanced by adding two electrons as:
2
SO2(aq) 
 SO 4(aq ) + 2e–
The charge is balanced by adding 4H+ ions as:
SO2(aq) 
 SO2–4(aq) + 4H+(aq) + 2e–
The O atoms and H+ ions are balanced by adding 2H2O molecules as:
SO2(aq) + 2H2O(l) 
 SO2–4(aq) + 4H+(aq) + 2e– (i)
The reduction half reaction is:
Cl2(s) 
 Cl–(aq)
The chlorine atoms are balanced as:
0 1

Cl2(s) 
 Cl(aq)
The oxidation number is balanced by adding electrons
Cl2(s) + 2e– 
 2Cl–(aq) (ii)
The balanced chemical equation can be obtained by adding equation (i) and (ii) as:
Cl2(s) + SO2(aq) + 2H2O(l) 
 2Cl–(aq) + SO2–4(aq) + 4H+(aq)
24. Refer to the periodic table given in your book and now answer the following questions:
(a) Select the possible non metals that can show disproportionation reaction.
(b) Select three metals that can show disproportionation reaction.
Ans : In disproportionation reactions, one of the reacting substances always contains an element that can exist in at
least three oxidation states.
(a) P, Cl, and S can show disproportionation reactions as these elements can exist in three or more oxida-
tion states.
(b) Mn, Cu, and Ga can show disproportionation reactions as these elements can exist in three or more
oxidation states.
25. In Ostwald’s process for the manufacture of nitric acid, the first step involves the oxidation of ammonia gas
by oxygen gas to give nitric oxide gas and steam. What is the maximum weight of nitric oxide that can be
obtained starting only with 10.00 g. of ammonia and 20.00 g of oxygen?
Ans : The balanced chemical equation for the given reaction is given as:
4NH3(g) + 5O2(g) 
 4NO(g) + 6H2O(g)
4 × 17g 5 × 32 g 4 × 30 g 6 × 18g
= 68 g = 160 g = 120 g = 108 g
Thus, 68 g of NH3 reacts with 160 g of O2.
160  10
Therefore, 10g of NH3 reacts with g of O2, or 23.53 g of O2.
68
But the available amount of O2 is 20 g.
Therefore, O2 is the limiting reagent (we have considered the amount of O2 to calculate the weight of nitric
oxide obtained in the reaction).
Now, 160 g of O2 gives 120g of NO.
120  20
Therefore, 20 g of O2 gives g of N, or 15 g of NO.
160
Hence, a maximum of 15 g of nitric oxide can be obtained.

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26. Using the standard electrode potentials given in the Table 8.1, predict if the reaction between the following is
feasible:
(a) Fe3+(aq) and I–(aq) (b) Ag+(aq) and Cu(s)
(c) Fe3+ (aq) and Cu(s) (d) Ag(s) and Fe3+(aq)
(e) Br2(aq) and Fe2+(aq)
3 
Ans : (a) The possible reaction between F(aq)  I(aq) is given by,,

2Fe3(aq )  2I(aq)

 2
 2Fe (aq )  I 2(s)

 I 2(s)  2e  ;
Oxidation half equation: 2I (aq )  E° = – 0.54 V
3  2
Reduction half equation: [Fe(aq)  e 
 Fe(aq) ] 2 ; E° = + 0.77 V

2Fe3(aq )  2I(aq)

 2
 2Fe (aq )  I 2(s) ; E° = + 0.23V
3 
E° for the overall reaction is positive. Thus, the reaction between Fe (aq ) and I(aq) is feasible.

(b) The possible reaction between Ag (aq)  Cu (s) is given by,,
 2
2Ag (aq)  Cu (s) 
 2Ag (s)  Cu (aq)

Oxidation half equation: Cu (s) 
 2Ag (aq)  2e  ; E° = – 0.34 V
 
Reduction half equation: [Ag (aq )  e 
 Ag (s) ]  2 ; E° = + 0.80 V


2Ag (aq  2Ag (s)  Cu 2  ;
)  Cu (s)  E° = + 0.46V
Here, E° positive for the overall reaction is positive. Hence, the reaction between and is feasible.
(c) The possible reaction between and is given by,
2Fe3(aq )  Cu (s) 
 2Fe 2(s)  Cu (aq
2
)
2 
Oxidation half equation: Cu (s) 
 Cu (aq )  2e ; E° = – 0.34V
3  2
Reduction half equation: [Fe (aq)  e 
 Fe ]  2 ;
(s) E° = + 0.77V

 2 2
2Fe3(aq)  Cu (s) 
 2Fe(s)  Cu (aq) ; E° = + 0.43V
3
E° positive for the overall reaction is positive. Hence, the reaction between Fe (aq ) and Cu(s) is feasible.
(d) The possible reaction betweenand is given by,
  2
Ag (s)  2Fe 3(aq) 
 Ag (aq )  Fe (aq)

Oxidation half equation: Ag (s) 
 Ag (aq)  e ; E° = – 0.80 V
3  2
Reduction half equation: Fe (aq )  e 
 Fe(aq) ; E° = + 0.77V

3  2
 Ag (aq )  Fe(aq) ;
Ag(s) + Fe (aq )  E° = – 0.03V
Here, E° for the overall reaction is negative. Hence, the reaction between and is not feasible.
2
(e) The possible reaction between Br2(aq) and Fe (aq ) is given by,,
2
Br2(s) + 2Fe (aq ) 
 2Br–(aq) + 2Fe3+(aq)
2 
Oxidation half equation: Fe(aq) 
 Fe3(aq)  e ]  2 ; E° = – 0.77V
Reduction half equation: Br2(aq) + 2e– 
 2Br–(aq); E° = + 1.09V

2
Br2(aq) + 2Fe (aq) 
 2Br–(aq) + 2Fe3+(aq); E° = – 0.32V
2
Here, E° for the overall reaction is positive. Hence, the reaction between Br2(aq) and Fe (aq ) is feasible.

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REDOX REACTION 173
27. Predict the products of electrolysis in each of the following:
(i) An aqueous solution of AgNO3 with silver electrodes
(ii) An aqueous solution AgNO3 with platinum electrodes
(iii) A dilute solution of H2SO4 with platinum electrodes
(iv) An aqueous solution of CuCl2 with platinum electrodes.
Ans : (i) AgNO3 ionizes in aqueous solutions to form Ag+ and NO3 ions.
On electrolysis, either Ag+ ions or H2O molecules can be reduced at the cathode. But the reduction potential
of Ag+ ions is higher than that of H2O.

Ag (aq)  e  
 Ag (s) ; E° = + 0.80 V

2H2O(l) + 2e– 
 H2(g) + 2OH (aq) ; E° = – 0.83V
+
Hence, Ag ions are reduced at the cathode. Similarly, Ag metal or H2O molecules can be oxidized at the
anode. But the oxidation potential of Ag is higher than that of H2O molecules.

Ag(s) 
 Ag (aq) + e–; E° = – 0.80 V

2H2O(l) 
 O2(g) + 4H (aq) + 4e; E° = – 1.23V
Therefore, Ag metal gets oxidized at the anode.
(ii) Pt cannot be oxidized easily. Hence, at the anode, oxidation of water occurs to liberate O2. At the
cathode, Ag+ ions are reduced and get deposited.
(iii) H2SO4 ionizes in aqueous solutions to give H+ and SO42 ions.
H2SO4(aq) 
 2H+(aq) + SO2–4(aq)
On electrolysis, either of H+ ions or H2O molecules can get reduced at the cathode. But the reduction
potential of H+ ions is higher than that of H2O molecules.
 
2H (aq )  2e 
 H 2(g) ; E° = 0.0V

2H2O(aq) + 2e– 
 H2(g) + 2OH (aq) ; E° = – 0.83V
Hence, at the cathode, H+ ions are reduced to liberate H2 gas.
On the other hand, at the anode, either of ions or H2O molecules can get oxidized. But the oxidation of
involves breaking of more bonds than that of H2O molecules. Hence, ions have a lower oxidation potential
than H2O. Thus, H2O is oxidized at the anode to liberate O2 molecules.
(iv) In aqueous solutions, CuCl2 ionizes to give Cu2+ and Cl– ions as:
2 
 Cu (aq)  2Cl(aq )
CuCl2(aq) 
On electrolysis, either of Cu2+ ions or H2O molecules can get reduced at the cathode. But the reduction
potential of Cu2+ is more than that of H2O molecules.

Cu 2(aq)  2e  
 Cu (aq) ; E° = + 0.34 V

H2O(l) + 2e– 
 H2(g) + 2OH–; E° = – 0.83V
Hence, Cu2+ ions are reduced at the cathode and get deposited.
Similarly, at the anode, either of Cl– or H2O is oxidized. The oxidation potential of H2O is higher than that of
Cl–.

2Cl (aq)   Cl 2(g)  2e  ; E° = – 1.36V
2H2O(l)   O2(g) + 4H+(aq) + 4e–; E° = – 1.23 V
But oxidation of H2O molecules occurs at a lower electrode potential than that of Cl– ions because of over-
voltage (extra voltage required to liberate gas). As a result, Cl– ions are oxidized at the anode to liberate Cl2
gas.

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28. Arrange the following metals in the order in which they displace each other from the solution of their salts.
Al, Cu, Fe, Mg and Zn.
Ans : A metal of stronger reducing power displaces another metal of weaker reducing power from its solution of
salt.
The order of the increasing reducing power of the given metals is Cu < Fe < Zn < Al < Mg.
Hence, we can say that Mg can displace Al from its salt solution, but Al cannot displace Mg.
Thus, the order in which the given metals displace each other from the solution of their salts is given below:
Mg > Al > Zn > Fe, > Cu
29. Given the standard electrode potentials,
K+/K = –2.93V, Ag+/Ag = 0.80V,
Hg2+/Hg = 0.79V
Mg2+/Mg = –2.37V. Cr3+/Cr = –0.74V
Arrange these metals in their increasing order of reducing power.
Ans : The lower the electrode potential, the stronger is the reducing agent. Therefore, the increasing order of the
reducing power of the given metals is Ag < Hg < Cr < Mg < K.
30 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, and
(iii) individual reaction at each electrode.
Ans : The galvanic cell corresponding to the given redox reaction can be represented as:
2 
Zn | Zn (aq) || Ag (aq ) | Ag

(i) Zn electrode is negatively charged because at this electrode, Zn oxidizes to Zn2+ and the leaving elec-
trons accumulate on this electrode.
(ii) Ions are the carriers of current in the cell.
(iii) The reaction taking place at Zn electrode can be represented as:
2
Zn (s) 
 Zn (aq)  2e 
And the reaction taking place at Ag electrode can be represented as:

Ag (aq)  e  
 Ag (s)
(iv) In aqueous solutions, CuCl2 ionizes to give Cu2+ and Cl– ions as:
2 
CuCl2(aq) 
 Cu (aq )  2Cl (aq )

On electrolysis, either of Cu2+ ions or H2O molecules can get reduced at the cathode. But the reduction
potential of Cu2+ is more than that of H2O molecules.

Cu 2(aq)  2e  
 Cu (aq) ; E° = + 0.34 V
H2O(l) + 2e–   H2(g) + 2OH–; E° = – 0.83V
2+
Hence, Cu ions are reduced at the cathode and get deposited.
Similarly, at the anode, either of Cl– or H2O is oxidized. The oxidation potential of H2O is higher than that of
Cl–.

2Cl (aq)   Cl 2(g)  2e  ; E° = – 1.36V

2H2O(l) 
 O2(g) + 4H (aq) + 4e–; E° = – 1.23V
But oxidation of H2O molecules occurs at a lower electrode potential than that of Cl– ions because of over-
voltage (extra voltage required to liberate gas). As a result, Cl– ions are oxidized at the anode to liberate Cl2
gas.

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REDOX REACTION 175

COMPETITIVE CORNER
IIT - JEE Previous Years Questions
1. The oxidation number of phosphorus in Ba(H2PO2)2 is - [1990]
(A) +3 (B) +2 (C) +1 (D) –1
2. The oxidation state of the most electronegative element in the products of the reaction between BaO2 and
H2SO4 are - [1991]
(A) 0 and –1 (B) –1 and –2 (C) –2 and 0 (D) –2 and +1
3. The compound which could act both as oxidising as well as reducing agent is - [1991]
(A) SO2 (B) KMnO4 (C) Al2O3 (D) CrO3
4. The number of electrons to balance the following equation, the value of x is - [1991]
NO3 + 4H + xe  2H2O + NO is -
– + –

(A) 5 (B) 4 (C) 3 (D) 2

5. The oxidation state of molybdenum in its oxo complex species [Mo2O4(C2H4)2 (H2O2)]2–[1991]
(A) 2 (B) 3 (C) 4 (D) 5
6. For the redox reaction,
MnO4  C2 O42  + H+  Mn2+ + CO2 + H2O
the correct coefficients of the reactants for the balanced equation are - [1992]
 2 +
MnO C2 O 4 4
H
(A) 2 5 16
(B) 16 5 2
(C) 5 16 2
(D) 2 16 5
7. The oxidation number of sulphur in S8, S2F2, H2S respectively, are - [1999]
(A) 0, + 1 and - 2 (B) + 2, +1 and - 2 (C) 0, + 1 and + 2 (D) - 2, + 1 and - 2
8. The reaction, 3CIO–(aq)  ClO3 (aq) + 2Cl–(aq) is an example of - [2000]
(A) Oxidation reaction (B) Reduction reaction
(C) Disproportionation reaction (D) Decomposition reaction
9. Amongst the following, identify the species with an atom in + 6 oxidation state - [2000]
(A) MnO4– (B) Cr(CN)36 (C) NiF62 (D) CrO2Cl2
10. The reaction, [2001]
3ClO–(aq)  CIO3–(aq) + 2Cl–– (aq) is an example of-
(A) Oxidation reaction (B) Reduction reaction
(C) Disproportionation reaction (D) Decomposition reaction.
11. In the standardization of Na2S2O3 using K2Cr2O7 by using iodometry, the equivalent weight of K2Cr2O7 is -
[2001]
(A) (molecular weight) / 2 (B) (molecular weight) / 6
(C) (molecular weight) / 3 (D) same as molecular weight.
12. In the reaction,
3Br2 + 6 CO23 + 3 H2O  5Br–+ Br O3 + 6 HC O3 [1996]
(A) Bromine is oxidised and carbonate is reduced
(B) Bromine is reduced and water is oxidised
(C) Bromine is neither reduced nor oxidised
(D) Bromine is both reduced and oxidised.
13. Among the follow species in which O.S. of the element is + 6 [2000]
(A) MnO4– (B) Cr(CN)3–6 (C) NiF2–6 (D) CrO2Cl2
14. Oxidation number of iron in Na2[Fe(CN)5NO+] is - [2001]
(A) +2 (B) +3 (C) + 8/3 (D) none of the three

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15. The reaction,

3ClO– (aq)  Cl O3 (aq) + 2Cl– (aq) is an example of [2001]
(A) Oxidation reaction (B) Reduction reaction
(C) Disproportionation reaction (D) Decomposition reaction
16. Maximum oxidation state is presented by [2004]
(A) CrO2Cl2 & MnO4¯ (B) MnO2
3 3
(C) [Fe(CN)6] ¯& [Co(CN)6] ¯ (D) MnO
17. Which of the following will not be oxidised by O3 ? [2005]
(A) KI (B) KMnO4 (C) K2MnO4 (D) FeSO4
18. Match the reactions in column I with nature of the reactions/type of the products in Column II.
Column I Column II
(A) O 2  O2 + O 22 (P) redox reaction
(B) CrO 24 + H+  (Q) one of the products has trigonal planar
structure
(C) MnO 4 +NO 2 +H+ (R) dimeric bridged tetrahedral metal ion
(D) NO 3 +H2SO4+Fe2+ (S) disproportionation [2007]
19. White phosphorus on reaction with NaOH gives PH3 as one of the products. This is a [2008]
(A) dimerization reaction (B) disproportionation reaction
(C) condensation reaction (D) precipitation reaction
20. For the reduction of NO3– ion in an aqueous solution, E0 is +0.96 V. Values of E0 for some metal ions are
given below [2009]
V (aq)+2e  V
2+ – 0
E = – 1.19V
Fe3+(aq)+3e–  Fe E0 = –0.04 V
Au3+(aq)+3e–  Au E0= +1.40 V
Hg (aq)+2e  Hg
2+ –
E0= +0.86 V
The pair(s) of metals that is(are) oxidized by NO–3 in aqueous solution is(are)
(A) V and Hg (B) Hg and Fe (C) Fe and Au (D) Fe and V
21. The oxidation number of Mn in the product of alkaline oxidative fusion of MnO2 is [2009]
22. Oxidation states of the metal in the minerals haematite and magnetite, respectively, are [2011]
(A) II, III in haematite and III in magnetite (B) II, III in haematite and II in magnetite
(C) II in haematite and II, III in magnetite (D) III in haematite and II, III in magnetite
23. Reduction of the metal centre in aqueous permanganate ion involves [2011]
(A) 3 electrons in neutral medium (B) 5 electrons in neutral medium
(C) 3 electrons in alkaline medium (D) 5 electrons in acidic medium
24. The difference in the oxidation numbers of the two types of sulphur atoms in Na2S4O6 is [2011]
25. Reaction of Br2 with Na2CO3 in aqueous solution gives sodium bromide and sodium bromate with evolution
of CO2 gas. The number of sodium bromide molecules involved in the balanced chemical equation is
[2011]
26. The reaction of white phosphorous with aqueous NaOH gives phosphine along with another phosphorous
containing compound. The reaction type; the oxidation states of phosphorus in phosphine and the other
product are respectively [2012]
(A) redox reaction; -3 and -5 (B) redox reaction; +3 and +5
(C) disproportionation reaction; -3 and +5 (D) disproportionation reaction; -3 and +3
27. Which ordering of compounds is according to the decreasing order of the oxidation state of
nitrogen? [2012]
(A) HNO3, NO, NH4Cl, N2 (B) HNO3, NO, N2, NH4Cl
(C) HNO3, NH4Cl, NO, N2 (D) NO, HNO3, NH4Cl, N2

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REDOX REACTION 177

AIEEE Previous Years Questions

1. MnO4 is good oxidising agent in different medium changing to –
MnO4 Mn2+

MnO24 
MnO2
Mn2O3
Changes in oxidation number respectively are – [2002]
(A) 1, 3, 4, 5 (B) 5, 4, 3, 2 (C) 5, 1, 3, 4 (D) 2, 6, 4, 3
2. Oxidation number of Cl in CaOCl2 (bleaching powder) is – [2002]
(A) Zero, since it contains Cl2 (B) –1, since it contains Cl–
(C) +1, since it contains ClO– (D) +1 and –1 since it contains ClO– and Cl–
3. Which of the following is a redox-reaction- [2002]
(A) 2Na[Ag(CN)2] + Zn  Na2[Zn(CN)4]+ 2Ag
(B) BaO2 + H2SO4  BaSO4 + H2O2
(C) N2O5 + H2O  2HNO3
(D) AgNO3 + K  Ag + KNO3
4. Which of the following is a redox reaction - [2002]
(A) NaCl + KNO3  NaNO3 + KCl (B) CaC2O4 + 2HCl  CaCl2 + H2C2O4
(C) Mg(OH)2 + 2NH4Cl  MgCl2 + NH4OH (D) Zn + 2AgCN  2Ag + Zn(CN)2
5. When KMnO4 acts as an oxidising agent and ultimately forms MnO42–, MnO2, Mn2O3 and Mn2+ then the
number of electrons transferred in each case respectively is - [2002]
(A) 4, 3, 1, 5 (B) 1, 5, 3, 7 (C) 1, 3, 4, 5 (D) 3, 5, 7, 1
6. In the coordination compound, K4[Ni(CN)4], the oxidation state of nickel is – [2003]
(A) +1 (B) +2 (C) –1 (D) 0
7. What would happen when a solution of potassium chromate is treated with an dilute nitric acid ?
[2003]
(A) CrO24 is reduced to +3 state of Cr (B) CrO24 is oxidized to +7 state of Cr
(C) Cr3+ and Cr2 O72  are formed (D) Cr2 O72  and H2O are formed
8. The oxidation state of Cr in [Cr(NH3)4Cl2]+ is – [2005]
(A) +2 (B) +3 (C) 0 (D) +1
9. The oxidation state of chromium in the final product formed by the reaction between Kl and acidified
potassium dichromate solution is – [2005]
(A) +6 (B) +4 (C) +3 (D) +2
10. Which of the following chemical reactions depicts the oxidizing behaviour of H2SO4 ?
[2006]
(A) Ca(OH)2 + H2SO4  CaSO4 + 2H2O (B) NaCl + H2SO4  NaHSO4 + HCl
(C) 2PCl5 + H2SO4 2POCl3+2HCl+SO2Cl2 (D) 2HI + H2SO4  I2 + SO2 + 2H2O
11. The standard reduction potentials for Zn2+/Zn, Ni2+ /Ni, and Fe2+/Fe are – 0.76, – 0.23 and – 0.44 V
respectively. The reaction X + Y2+  X2+ + Y will be spontaneous when - [2012]
(A) X = Ni, Y= Zn (B) X = Fe, Y = Zn (C) X = Zn, Y = Ni (D) X = Ni, Y = Fe

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ANSWER KEY
OBJECTIVE EXERCISE
1. (B) 2. (C) 3. (A) 4. (C)
5. (C) 6. (D) 7. (B) 8. (B)
9. (A) 10. (B) 11. (B) 12. (C)
13. (D) 14. (C) 15. (A) 16. (B)
17. (B) 18. (A) 19. (C) 20. (C)
21. (B) 22. (B) 23. (A) 24. (C)
25. (B) 26. (B) 27. (C) 28. (D)
29. (C) 30. (B) 31. (A) 32. (C)
33. (D) 34. (B) 35. (B) 36. (C)
37. (B) 38. (C) 39. (A) 40. (A)
41. (D) 42. (B) 43. (D) 44. (D)
45. (B) 46. (C) 47. (B) 48. (C)
49. (C) 50. (A) 51. (B) 52. (D)
53. (A) 54. (D) 55. (A) 56. (C)
57. (A) 58. (A) 59. (C) 60. (A)
61. (A) 62. (C) 63. (D) 64. (D)
65. (B) 66. (A) 67. (C) 68. (B)
69. (A) 70. (D) 71. (A) 72. (D)
73. (D) 74. (A) 75. (B) 76. (C)
77. (A) 78. (C) 79. (C) 80. (D)
81. (C) 82. (A) 83. (B) 84. (D)
85. (A) 86. (C) 87. (C) 88. (A)
89. (A) 90. (C) 91. (B) 92. (D)
93. (D) 94. (C) 95. (B) 96. (D)
97. (D) 98. (B) 99. (D) 100. (D)

SUBJECTIVE EXERCISE
11. 32.69g, 18.2 g 12. (KClO3, KMnO4, KIO3, K2Cr2O7, KMnO4)
13. 98, 49, 32.67 14. 6 15. 0.511 g
COMPETITIVE CORNER
IIT - JEE Previous Years Questions
1. (C) 2. (B) 3. (A) 4. (C)
5. (B) 6. (A) 7. (A) 8. (C)
9. (D) 10. (C) 11. (B) 12. (D)
13. (D) 14. (A) 15. (C) 16. (A)
17. (B) 18. A(P, S); B(R); C(P,Q), D(P) 19. (B)
20. (A, B, D) 21. 6 22. (D) 23. (A, D)
24. (5) 25. (5) 26. (C)
27. (B)
AIEEE Previous Years Questions
1. (C) 2. (D) 3. (A) 4. (D)
5. (C) 6. (D) 7. (D) 8. (B)
9. (C) 10. (D) 11. (C)

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