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CHAPTER

1
Oxidation Reduction
Redox Reaction (Oxidation-Reduction) : 3. Oxidation number can be zero, whole number or a
fractional value
Many Chemical reactions involve transfer of elec-
Ex. Ni(CO)4 O.S of Ni = 0
trons from one chemical substance to another.
N3H O.S of N = -1/3
These electron-transfer reactions are termed as
HCl O.S of Cl = -1
Oxidation-Reduction or Redox reactions.
Or 4. Oxidation state of same element can be different in
Those reactions which involve oxidation and same or different compounds.
reduction both simultaneously are known as oxi- Ex. H2S O.S of S = -2
dation reduction or Redox Reaction. H2SO3 O.S of S = +4
Or H2SO4 O.S of S = +6
Those reactions which involve increase in oxida- Some helping rules for calculating oxidation number :
tion number and decrease in oxidation number (1) In case of covalent bond-
simultaneously are known as Oxidation Reduction (a) For homoatomic molecule
or Redox Reaction. A A A = A A A

Oxidation State : 0 0 0 0 0 0
Oxidation state of an atom is the charge present (b) For heteroatomic molecule (EN of B > A)
on an atom when it is in combined state. A - B A = B AB

Or

+1 -1 +2 -2 +3 -3
Oxidation state of an element in a compound (2) In case of co-ordinate bond (EN of B > A) :
represents the number of electrons lost or A A B B A B B A
gained during its change from free state into

+2 -2 +2 -2 +2 -2 (neglected)
that compound.
(3) In case of Ionic bond :
Some important points concerning Oxidation Charge on cation = O.S of cation
number :- Charge on anion = O.S of anion
Ex. NaCl Na+ + Cl-
1. Electronegativity values of no two elements are same -
S > C C>H +1 -1
P > H Cl > N MgCl2 Mg+2+ 2Cl-

2. Oxidation number of an element may be Positive or +2 -1
Negative.

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1.2 Chapter 1

(4) Oxidation number is zero in following cases : Ex. H2SO3


(a) The Oxidation number of an element in its free state is If O.S of S is x then
zero. Example- Oxidation number of 2 (+1) +x + 3 (-2) = 0
Na, Cu, I, Cl, O etc. are zero. x-4=0
(b) Oxidation number of atoms present in homoatomic x = +4
molecules is zero. (11) The algebric sum of oxidation number of all the atoms
Ex. H2 , O2 , N2 , P4 , S8 = zero in a polyatomic complex ion is equal to the charge
(c) Oxidation number of an element in any of its allotropic present on the ion.
form is zero. Ex. SO4-2
Ex. C Diamond , C Graphite , S Monoclinic , S Rhombic = 0 If O.S of S is x then
(d) Oxidation number of all the components of an alloy x + 4 (-2) = -2
are 0 x-6=0
(5) Oxidation number of Fluorine in all its compounds is x = +6
-1 Ex. HCO3-
(6) Oxidation number of IA and II A group elements are If O.S of C is x then
+1 and +2 respectively. +1 +x + 3 (-2) = -1
(7) Oxidation number of Hydrogen in most of its com- x-4=0
pounds is +1 except in metal hydrides (-1) x = +4
Ex. NaH LiH CaH2 MgH2 (12) In complex compounds, O. number of some neutral
molecules (ligands) is zero. Example CO, NO, NH3,
+1 -1 +1 -1 +2 -1 +2 -1 H2O.
(8) Oxidation number of Oxygen in most of its compounds Applications of Oxidation Number :
is -2 except in - (1) To compare the strength of acid and base :-
(a) Peroxides (O2-2) Oxidation number (O) = -1 Strength of acid Oxidation Number
Ex. H2O2 , BaO2
1
(b) Super Oxides (O2-1) Oxidation number (O) = -1/2 Strength of base
Ex. KO2 Oxidation Number
Example : Order of acidic strength in HClO, HClO2,
-1/2 HClO3, HClO4 will be.
(c) Ozonide (O3-1) Oxidation number (O) = -1/3 Solution :
Ex. KO3 Oxidation Number of chlorine
HClO (Hypo chlorous acid) +1
-1/3 HClO2 (Chlorous acid) +3
(d) OF2 (Oxygen difluoride) HClO3 (Chloric acid) +5
F - O - F HClO4 (Perchloric acid) +7
Strength of acid Oxidation Number
+2 So the order will be -
(e) O2F2 (dioxygen difluoride) HClO4 > HClO3 > HClO2 > HClO
(2) To determine the oxidising and reducing nature of
+1 the substances :-
(9) Oxidation number of monoatomic ions is equal to the (a) If effective element in a compound is present in
charge present on the ion. maximum Oxidation state then the compound acts as
Ex. Mg+2 Oxidation number = +2 oxidising agent.
(10) The algebric sum of Oxidation number of all the atoms Ex. KMnO4 K2Cr2O7 H2SO4
present in a polyatomic neutral molecule is 0.
Ex. H2SO4 +7 +6 +6
If O.S of S is x then SO3 H3PO4 HNO3 HClO4
2 (+1) + x + 4 (-2) = 0

x-6=0 +6 +5 +5 +7
x = +6

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Oxidation Reduction1.3

(b) If effective element in a compound is present in mini- of electrons gained or lost by that compound in that
mum Oxidation state then the compound acts as reduc- reaction.
ing agent.
PH3 NH3 CH4 EXAMPLE 2
(i) MnO4- Mn+2 (acidic medium)
-3 -3 -4 (+7) (+2)
(c) If effective element in a compound is present in inter- Here 5 electrons are taken so eq. wt.
mediate Oxidation state then the compound can act as
oxidising agent as well as reducing agent. Mol. wt. of KMnO 4 158
= = = 31.6
HNO2 H3PO3 SO2 H2O2 5 5
(ii) MnO4- MnO2 (neutral medium) or (Weak
+3 +3 +4 -1 alkaline medium)
(3) To calculate the equivalent weight of compounds : (+7) (+4)
The equivalent weight of an oxidising agent is that Here, only 3 electrons are gained, so eq. wt.
weight which accepts one mole electrons in a chemical
Mol. wt. of KMnO 4 158
reaction. = = = 52.7
(a) Equivalent wt. of an oxidant (get reduced) 3 3
Molecular weight Note : When only alkaline medium is given consider it as
= weak alkaline medium.
No. of electrons gained by one mole
(iii) MnO4- MnO4-2 (strong alkaline medium)
(+7) (+6)
EXAMPLE 1
Here, only one electron is gained, so eq. wt.
In acidic medium
Mol. wt. of KMnO 4
6e- + Cr2O72- + 14H+ 2Cr3+ + 7H2O = = 158
1
Here atoms which undergoes reduction is Cr. Its O. S.
is decreasing from +6 to +3 Note :- It is important to note that KMnO4 acts as an oxi-
 Eq. wt. of K2Cr2O7 dant in every medium although with different
Mol. wt of K 2 Cr2 O7 Mol. wt. strength which follows the order -
= = acidic medium > neutral medium > alkaline medium
3 2 6
while, K2Cr2O7 acts as an oxidant only in acidic
Note :- [6 in denominator indicates that 6 electrons were medium as follows
gained by Cr2O72- as it is clear from the given bal- Cr2O72- 2Cr3+
anced equation] (2 6) (2 3)
(b) Similarly equivalent wt. of a reducant (gets oxidised) Here, 6 electrons are gained so eq. wt.
Mol. wt. Mol. wt. of K 2 Cr2 O7 294.21

= =
= = 49.03
No.of electrons lost by one mole 6 6
(4) To determine the possible molecular formula of
In acidic medium, C2O42- 2CO2 + 2e- compound :
Here, Total electrons lost = 2 Since the sum of Oxidation number of all the atoms
present in a compound is zero, so the validity of the
So, eq. wt. = Mol. wt. formula can be confirmed.
2
(c) In different conditions a compound may have different
equivalent wts. Because, it depends upon the number

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1.4 Chapter 1

OXIDATION AND REDUCTION


There are two concepts of Oxidation and reduction.
(1) Classical/old concept -

OXIDATION REDUCTION

(i) Addition of O2 Addition of H2
2Mg + O2 2MgO N2 + 3H2 2NH3
C + O2 CO2 H2 + Cl2 2HCl
(ii) Removal of H2 Removal of O2
H2S + Cl2 2HCl + S CuO + C Cu + CO
4HI + O2 2I2 + 2H2O H2O +C CO + H2
( iii) Addition of electronegative element Addition of electropositive element
Fe + S FeS CuCl2 + Cu Cu2Cl2
SnCl2 + Cl2 SnCl4 HgCl2 + Hg Hg2Cl2
( iv) Removal of electropositive element Removal of electronegative element
2NaI + H2O2 2NaOH + I2 2FeCl3 + H2 2FeCl2 + 2HCl

(2) Electronic/Modern Concept


OXIDATION REDUCTION

(1) De-electronation Electronation
(2) Oxidation process are those process in which one Reduction process are those process in which
or more e-s are lost by an atom, ion or molecule. one or more e-s are gained by an atom, ion or
molecule.
Cu+2 + 2e- Cu
(3) Examples -
Mn+ + ne- M
(a) Zn Zn+2 + 2e-
M Mn+ + ne-
Fe+3 + (3 - 2) e- Fe+2
(b) Sn Sn + (4-2) e
+2 +4 -
M+x1 +(x1-x2)e- M+x2
M+n1 M+n2+ (n2-n1)e-
O + 2e- O2-
(c) Cl- Cl + e- A + xe- A-x
A-n A + ne-
[Fe (CN)4]3- + (4 - 3)e- [Fe (CN)4]-4
-2
(d) MnO 4 MnO4- + (2-1)e- -
A - n1 + (n2 - n1)e A - n 2
A - n1 A - n 2 + (n1-n2)e
-

OXIDANT REDUCTANT

Oxidant are those substances which :- Reductant are those substances which :-
(a) Oxidises others and reduces themselves. Reduces others and oxidises themselves.
(b) Accepts electron i.e electron acceptors Donates electron i.e., electron donors
(c) Show decrease in Oxidation State Show increase in Oxidation State
(d) Act as lewis acid Act as Lewis base
(e) Ex. All electronegative element like F2 , Cl2 , N2 ,O Some non-metals like- C, H, S
and Compounds which have effective element in Some hydrides like LiH, CaH2 , LiAlH4 etc.
maximum and compounds having effective element in
minimum O.S
Oxidation State (Ex. KMnO4 K2Cr2 O7) (Ex. PH3 , NH3....)

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Oxidation Reduction1.5

TYPES OF REDOX REACTIONS (v) In order to balance oxygen atoms, add H2O molecules
to the side deficient in oxygen.
(1) Intermolecular redox reaction :- When oxidation (vi) Then balance the number of H atoms by adding H+
and reduction takes place separately in different com- ions to the side deficient in hydrogen.
pounds, then the reaction is called intermolecular
redox reaction.
SnCl2 + 2FeCl3 SnCl4 + 2FeCl2 EXAMPLE 3
Sn+2 Sn+4 (Oxidation) Balance the following reaction by the oxidation num-
Fe+3 Fe+2 (Reduction) ber method -
Cu + HNO3 Cu(NO3)2 + NO2 + H2O
(2) Intramolecular redox reaction :- During the chemi-
cal reaction, if oxidation and reduction takes place in SOLUTION
single compound then the reaction is called intramo- Write the oxidation number of all the atoms.
lecular redox reaction. 0 +1+5-2 +2+5-2
Cu + HNO3 Cu(NO3)2
+4 -2 +1 -2
+ NO2 + H2O
There is change in oxidation number of Cu and N.
0 +1+5+2
Cu Cu(NO3)2 ...(1)
(3) Disproportionation reaction :- When reduction and (Oxidation no. is increased by 2)
oxidation takes place in the same element of the same +5 +4
compound then the reaction is called disproportion- HNO3 NO2 ...(2)
ation reaction. (Oxidation no. is decreased by 1)
To make increase and decrease equal, eq. (2) is multi-
plied by 2.
Cu + 2HNO3 Cu(NO3)2 + 2NO2 + H2O
Balancing nitrates ions, hydrogen and oxygen, the fol-
lowing equation is obtained.
Cu + 4HNO3 Cu(NO3)2 + 2NO2 + 2H2O
BALANCING OF REDOX REACTION This is the balanced equation.
(1) Oxidation number change method.
(2) Ion electron method. EXAMPLE 4
(1) Oxidation number change method :- Balance the following reaction by the oxidation num-
This method was given by Johnson. In a balanced ber method -
redox reaction, total increase in oxidation number MnO4- + Fe+2 Mn+2 + Fe+3
must be equal to total decreases in oxidation num-
ber. This equivalence provides the basis for balancing SOLUTION
redox reactions. Write the oxidation number of all the atoms.
The general procedure involves the following +7 -2
steps : MnO4- + Fe+2 Mn+2 + Fe+3
(i) Select the atom in oxidising agent whose oxidation change in oxidation number has occured in Mn and Fe.
number decreases and indicate the gain of electrons. +7
(ii) Select the atom in reducing agent whose oxidation MnO4- Mn+2  ...(1)
number increases and indicate the loss of electrons. (Decrement in oxidation no. by 5)
(iii) Now cross multiply i.e.multiply oxidising agent by Fe+2 Fe+3  ...(2)
the number of loss of electrons and reducing agent by (Increment in oxidation no. by 1)
number of gain of electrons. To make increase and decrease equal, eq. (2) is multi-
(iv) Balance the number of atoms on both sides whose oxi- plied by 5.
dation numbers change in the reaction. MnO4- + 5Fe+2 Mn+2 + 5Fe+3

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1.6 Chapter 1

To balance oxygen, 4H2O are added to R.H.S. and to (e) Balance H-atoms by the addition of H+ to another side
balance hydrogen, 8H+ are added to L.H.S. Cr2O72- + 14 H+ 2Cr3+ + 7H2O
MnO4- + 5Fe+2 + 8H+ Mn+2 + 5Fe+3 + 4H2O C2O42- 2CO2
This is the balanced equation. (f) Now, balance the charge by the addition of electron
(e-).
(2) Ion-Electron method :- Cr2O72- + 14 H+ + 6e- 2Cr3+ + 7H2O
This method was given by Jette and La mev in 1972. ...(1)
The following steps are followed while balancing C2O42- 2CO2 + 2e- ...(2)
redox reaction (equations) by this method. (g) Multiply equations by a constant to get the same num-
(i) Write the equation in ionic form. ber of electrons on both side. In the above case sec-
(ii) Split the redox equation into two half reactions, one ond equation is multiplied by 3 and then added to first
representing oxidation and the other representing equation.
reduction. Cr2O72- + 14 H+ + 6e- 2Cr3+ + 7H2O
(iii) Balance these half reactions separately and then add 3C2O42- 6CO2 + 6e-
by multiplying with suitable coefficients so that the Cr2O72- + 3C2O42- + 14 H+ 2Cr3+ + 6CO2 +
electrons are cancelled. Balancing is done using fol- 7H2O
lowing substeps.
(a) Balance all other atoms except H and O. (B) Alkaline Medium :-
(b) Then balance oxygen atoms by adding H2O molecules (a) Consider the reaction
to the side deficient in oxygen. The number of H2O Cr(OH)3 + IO3- OH

I- + CrO42-
molecules added is equal to the deficiency of oxygen
(b) Separate the two half reactions.
atoms.
Cr(OH)3 CrO42-(Oxidation half reaction)
(c) Balance hydrogen atoms by adding H+ ions equal to
IO3- I- (Reduction half reaction)
the deficiency in the side which is deficient in hydro-
(c) Balance O-atoms by adding H2O.
gen atoms.
H2O + Cr(OH)3 CrO42-
(d) Balance the charge by adding electrons to the side
IO3- I- + 3H2O
which is rich in +ve charge. i.e., deficient in electrons.
(d) Balance H-atoms by adding H+ to side having defi-
Number of electrons added is equal to the deficiency.
ciency and add equal no. of OH- ions to the side
(e) Multiply the half equations with suitable coefficients
( medium is known)
to equalize the number of electrons.
H2O + Cr (OH)3 CrO -42 + 5H+
(iv) Add these half equations to get an equation which is
5OH- + H2O + Cr(OH)3 CrO 24 + 5H+ +
balanced with respect to charge and atoms.
5OH-
(v) If the medium of reaction is basic, OH- ions are added
or 5OH- + Cr(OH)3 CrO 2- 4 + 4H2O
to both sides of balanced equation, which is equal to
number of H+ ions in Balanced Equation. IO3- + 6H+ I- + 3H2O
-
I O3 + 6H+ + 6OH- I- + 3H2O + 6OH-
EXAMPLE 5 or IO3- + 3H2O I- + 6OH-
(A) Acidic Medium :- (e) Balance the charges by adding electrons
(a) Cr2O72- + C2O42- Cr3+ + CO2 5OH- + Cr(OH)3 CrO 24 + 4H2O + 3e-
(b) Write both the half reaction. IO3- + 6H2O + 6e- I- +3H2O + 6OH-
Cr2O72- Cr3+ (Reduction half reaction) (f) Multiply first equation by 2 and add to second to give
C2O42- CO2 (Oxidation half reaction) 10OH- + 2Cr(OH)3 2 CrO 24 + 8H2O + 6e-
(c) Atoms other than H and O are balanced.
IO3- + 6H2O + 6e- I- +3H2O + 6OH-
Cr2O72- 2Cr3+ Add there balanced half reaction to give complete bal-
C2O42- 2CO2
anced reaction.
(d) Balance O-atoms by the addition of H2O to another
4OH- + 2Cr(OH)3 + IO3- 5H2O + 2 CrO 2- 4 + I
-
side
Cr2O72- 2Cr3+ + 7H2O
C2O42- 2CO2

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Oxidation Reduction1.7

SOLUTION
SOLVED EXAMPLE
In the above reaction C2O4-2 acts as a reductant because it
is oxidised to CO2 as :
C2O4-2 2CO2 + 2e(oxidation)
EXAMPLE 1 C2O4-2 reduces MnO4- to Mn+2 ion in solution.
Which of the following acts as both oxidant and reductant - EXAMPLE 4
(a)HNO3 (b)HNO2
(c) Both HNO3 and HNO2 Oxidation number of cobalt in [Co(NH3)6]Cl2Br
(d) Neither HNO3 nor HNO2 is -
 (Ans. b) (a) + 6 (b) Zero
(c) + 3 (d) + 2
SOLUTION  (Ans. c)
O.N. of N in HNO2 is + 3
SOLUTION
Max. O.N. of N is + 5
Min. O.N. of N is - 3 Let the O.N. of Co be x
Thus, O.N. of N in HNO2 can show an increase or decrease O.N. of NH3 is zero
as the case may be. That is why HNO2 acts as oxidant and O.N. of Cl is -1
reductant both. O.N. of Br is -1
O.N. of N in HNO3 is + 5, Hence, it can act only as an Hence, x + 6 (0) - 1 x 2 -1 = 0
oxidant. x=+3
so, the oxidation number of cobalt in the given complex
EXAMPLE 2 compound is +3.
State which of the following reactions s neither oxidation EXAMPLE 5
nor reduction -
(a)Na NaOH The order of increasing O.N. of S in S8, S2O8-2 ,
(b)Cl2 Cl- + ClO-3 S2O3-2, S4O6-2 is given below -
(c)P2O5 H4P2O7 (a) S8 < S2O8-2 < S2O3-2 < S4O6-2
(d)Zn + H2SO4 ZnSO4 + H2 (b) S2O8-2 < S2O3-2 < S4O6-2 < S8
 (Ans. c)
(c) S2O8-2 < S8 < S4O6-2 < S2O3-2
SOLUTION (d) S8 < S2O3-2 < S4O6-2 < S2O8-2
In the reaction P2O5 H4P2O7  (Ans. d)
The O.N. of P in P2O5 is
2x + 5 (-2) = 0 or x = +5 SOLUTION
The O.N. of P in H4P2O7 is
The O.Ns. of S are shown below along with the compounds
4 (+1) + 2 (x) +7 (-2) = 0
S8, S2O8-2, S2O3-2, S4O6-2
2x = 10 or x = +5
0 + 6 +2 +2.5
Since there is no change in O.N. of P, hence, the above reac-
Hence, the order of increasing O.N. of S is
tion is neither oxidation nor reduction.
S8 < S2O3-2 < S4O6-2 < S2O8-2
EXAMPLE 3
EXAMPLE 6
In the reaction
Which of the following has least oxidation state of Fe ?
C2O4-2 + MnO-4 + H+ Mn+2 + CO2 the reductants is
(a)C2O4-2 (b)H+
(a) K3[Fe(OH)6]
(b)MnO-4 (d) None of these
(b) K2[FeO4]
(c) FeSO4 . (NH4)2SO4 . 6H2O
 (Ans. a) (d) [Fe(CN)6]3-
 (Ans. c)

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1.8 Chapter 1

SOLUTION SOLUTION
In mohr salt FeSO4 . (NH4)2SO4. 6H2O, oxidation state of In H2S2O8, two O atoms form peroxide linkage i.e.
iron is +2 which is least. O O
K3[Fe(OH)6] +3 + x - 6 = 0 x = +3
K2[FeO4] +2 + x - 8 = 0 x = +6 H-O-S-O-O-S-O-H

FeSO4.(NH4)2SO4 .6H2O
O O
+2 state in FeSO4 (x - 2 = 0)
2 x 1 + 2a + 6( -2) + 2 (-1) = 0
Fe(CN)3-6 x - 6 = -3 x = +3 a =+6
Thus, the O.N. of S in H2S2O8 is + 6
EXAMPLE 7
The oxid.no. of Cl in NOClO4 is - EXAMPLE 10
(a) + 11 (b) + 9 (c) + 7 (d) + 5 When K2Cr2O7 is converted into K2CrO4 the change in oxi-
 (Ans. c) dation number of Cr is -
(a)0 (b)3 (c)4 (d)6
SOLUTION
 (Ans. a)
he compound may be written as NO+ ClO4
T
For ClO4-, Let Ox. No.of Cl = a SOLUTION
a + 4 x (-2) = -1 When Cr2O7-2 is converted into CrO4-2 the change in oxi-
a = +7 dation number of Cr is zero
Hence, the oxidation no. of Cl in NOClO4 is +7. Cr2O7-2 CrO4-2
+6 +6
EXAMPLE 8 There is no change in oxidation state of Cr, hence, it is
The two possible oxidation numbers of N atoms in NH4NO3 neither oxidised nor reduced and remains in the same
are respectively - oxidation state.
(a) +3, +5 (b) +3, -5
(c) -3, +5 (d) -3, -5 EXAMPLE 11
 (Ans. c) The oxidation number of S in (CH3)2 SO is -
(a)1 (b)2 (c)0 (d)3
SOLUTION
 (Ans. c)
There are two N atoms in NH4NO3, but one N atom has
negative oxidation number (attached to H) and the other SOLUTION
has positive oxid.no. (attached to O). Therefore, evaluation
should be made separately as - Let the oxidation no. of S is a
O.N. of N is NH4+ O.N. of N in NO3- O.N. of CH3 = +1
a + 4 x (+1) = +1 and a + 3 (-2) = -1 O.N. of O = -2
a = -3 a = + 5 2(+1) + a + (-2) = 0
Here the two O.N. are -3 and +5 respectivley. a=0
Hence, the oxidation no. of S in Dimethyl sulphoxide is
zero.
EXAMPLE 9
The oxidation number of S in H2S2O8 is - EXAMPLE 12
(a)+8 (b) -8 (c) +6 (d) +4 What will be the oxidation number of I in the KI3 -
 (Ans. c)
1 1
(a) - (b) - (c) + 4 (d) + 3
3 4
 (Ans. a)

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Oxidation Reduction1.9

SOLUTION SOLUTION
In KI3 1 + 3 (a) = 0 2Al Al2+3 + 6e-  ............. (A)
1 8e + Fe3+8/3 3Fe  ............. (B)
a = - 3 or KI3 is KI + I2 Multiplying Eq. (A) by 4 and Eq. (B) by 3, then on addition
I has two oxidation no. -1 and 0 respectively. However fac- 8Al 4Al2+3 + 24e
tually speaking oxidation number of I in KI3 is on average 24e + 3Fe3+8/3 9Fe

of two values - 1 and 0.
1 + 2 (0) 1 8Al + 3Fe3+8/3 9Fe + 4Al2+3
Average O.N. = =
3 3
or 8Al + 3Fe3O4 4Al2O3 + 9Fe
EXAMPLE 13 Therefore, it is clear that total no. of electrons transferred
during change = 24
Oxidation number of Fe in [Fe(CN)6]-3, [Fe(CN)6]-4,
[Fe(SCN)]+2 and [Fe(H2O)6]+3 respectively would be-
(a) +3, +2, +3 and +3 EXAMPLE 16
(b) +3, +3, +3 and +3 In the redox reaction -
(c) +3, +2, +2 and +2 10FeC2O4 + x KMnO4 + 24H2SO4
(d) +2, +2, +2 and +2 5Fe2 (SO4)3 + 20CO2 + y MnSO4 + 3 K2SO4 + 24H2O.
 (Ans. a) The values of x and y are respectively -
(a) 6, 3 (b) 3, 6 (c) 3, 3 (d) 6, 6
SOLUTION  (Ans. d)
Oxidation number of Fe in-
First Second Third Fourth SOLUTION
x-6 = -3 x-6 = -4 x-1 =+2 x + 60 = +3 The balanced redox reaction given above can be written
x = +3 x = +2 x = +3 x = +3 as :
10FeC2O4 + 6KMnO4 + 24H2SO4
EXAMPLE 14 5Fe2 (SO4)3 + 20CO2 + 6 MnSO4 + 3 K2SO4 +
Which of the following is not a redox reaction- 24H2O
(a)
1 1
H2 + I2 HI so the value of x = 6 and y = 6
2 2
(b) PCl5 PCl3 + Cl2 EXAMPLE 17
(c) 2CuSO4 + 4KI Cu2I2 + 2K2SO4 + I2
(d) CaOCl2 Ca+2 + OCl- + Cl- Oxidation state of carbon in HCOOH will be :
 (Ans. d) (a) +1 (b) +2 (c) -4 (d) 0
 (Ans. b)
SOLUTION
In all the above reaction except (d) there is change in oxida- SOLUTION
tion states of reactant and product atoms, hence, they are Let the oxidation state of carbon be x.
all redox reactions. In reaction (d) the oxidation states of 2 + x - 4 = 0
the atoms of the reactants and products remain unchanged x=2
hence, it is not a redox reaction.

EXAMPLE 18
EXAMPLE 15
Which of the following is correctly balanced half reaction -
In the reaction Al + Fe3O4 Al2O3 + Fe -
(a) AsO3-3+ H2O AsO4-3 + 2H+ - 2e-
what is the total no. of electrons transferred during the
(b) H2O2 + 2e O2 + 2H+
change -
(c) Cr2O7-2 + 14H+ 2Cr+3 + 7H2O - 6e-
(a)16 (b)24 (c)8 (d)12
(d) IO-3 + 6H+ I2 + 3H2O + 5e-
 (Ans. b)
 (Ans. c)

1. Redox_[Oxidation reduction].indd 9 19-10-2017 17:22:53


1.10 Chapter 1

SOLUTION (l) a + 3 (-2) = - 2


The correctly balanced half reaction is - a = + 4
Cr2O7-2 + 14H+ 2Cr+3 + 7H2O -6e- (m) a + 4 0 = + 2
It is a reduction half reaction in balancing the equation by a = + 2
ion-electron method. (n) a + 4 0 = 0
a = 0
(o) a + 2 (-2) = 0
EXAMPLE 19 a = + 4
Determine the ox. no. of underlined atom in each of the (p) 1 6 + 7 a + 24 (-2) = 0
following: a = + 6
(a) KCrO3Cl, (b) K2FeO4, (c) Ba(H2PO2)2 (q) a + 4 (-1) = - 1
(d) Rb4Na[HV10O28] a = + 3
(e) Ba2XeO6 (f) Na2S2 (g) K2MnO4 (r) a + 4 (-2) = 0
(h) K2Cr2O7 a = + 8
(s) 4 1 + a + 6 (-2) = 0
(i) MnO42- (j) SO42- (k)
PO43- a = + 8
(t) 1 + a + 3 (-2) + 1 (-1) = 0
(l) CO32- a = + 6
2+
(m) Cu (NH 3) 4 (n) Ni(CO)4 (o) CS2 (u) 2 a + 2 (1) = 0
a = - 1
(p)(NH4)6Mo7O24
(q) [CoF4]- (r) OsO4 (s) Na4XeO6
EXAMPLE 20
(t)
KCrO3Cl
(u) F2H2 Find the oxidation number of carbon in the following
compounds:
SOLUTION
CH3OH, CH2O, HCOOH, C2H2.

(a) Let ox. no. of Cr be a then SOLUTION


1 + a + 3 (-2) + 1 (-1) = 0
a = + 6 CH3OH: a + 3 1 + 1 (-2) + 1 1 = 0
(b) 2 1 + a + 4 (-2) = 0 a=-2
a=+6 CH2O: a + 2 1 + 1 (-2) = 0
(c) 2 + [2 1 + a + 2 (-2)] = 0 a = 0
a = + 1 HCOOH: 1 + a + 2 (-2) + 1 = 0
(d) 4 1 + 1 + [1 + 10 a + 28 (-2)] = 0 a = + 2
a=+5 C2H2: 2 a + 2 1 = 0
(e) 2 2 + a + 6 (-2) = 0 a = - 1
a=+8
(f) 1 2 + 2 a = 0 EXAMPLE 21
a = - 1
Point out the oxidation number of C in the following:
(g) 2 1 + a + 4 (-2) = 0
a = + 6 CH4,C3H8, C2H6, C4H10, CO, CO2 and HCO3- , CO32 -
(h)
2 1 + 2 a + 7 (-2) = 0 SOLUTION
a = + 6
(i) a + 4 (-2) = - 1 8 10
CH4 : -4 ; C3H8 : - C H : -3; C4H10 : - ;
a = + 7 3 2 6 4
(j) a + 4 (-2) = - 1 CO : + 2 CO2 : + 4
a = + 6
(k) a + 4 (-2) = - 3 HCO3 : +4 : + 4 CO32 : +4
a = + 5

1. Redox_[Oxidation reduction].indd 10 19-10-2017 17:22:54


Oxidation Reduction1.11

EXAMPLE 22 (f) 5H2C2O4 + 2KMnO4 + 3H2SO4


What are oxidation numbers of K SO + 2MnSO + 10CO + 8H O
2 4 4 2 2
(a) S in Na2S2
SOLUTION
(b) V in VO +2 (dioxovanadium V)
(i) (a) and (b) represents auto-redox or disproportionation
(c) H in LiAlH4 in which same substance is oxidized and reduced as
(d) V in VO2+ (oxovanadium IV) well.
(e) V in HV6 VO 2+ (ii) (c) and (d) represents intramolecular redox change in
which one element of a compound is oxidized and the
other element is reduced.
SOLUTION (iii) (e) and (f) represents intermolecular redox in which
(a) - 1, (b) + 5, (c) - 1, (d) + 4, (e) + 5 one of the two reactant is oxidized and other is reduced.

EXAMPLE 23 EXAMPLE 25
Arrange the following in order of : Identify the oxidized and reduced species in the following
(a) Increasing oxidation no. of Mn : reactions:
MnCl2, MnO2, Mn(OH)3, KMnO4
(a) CH4(g) + 4Cl2(g)
CCl4(g) + 4HCl(g)
(b) Decreasing oxidation no. of X :
+2+
HXO4, HXO3, HXO2, HXO (b) MnO2(s) + C2H2O4(aq,) 2
H
Mn (aq.)
(c) Increasing oxidation no. of I :
+ 2CO2(g) + 2H2O(l)
I2, HI, HIO4, ICl, IF3, IF5

(d) Increasing oxidation no. of N: (c) I2(aq.) + 2S2O32(aq.) + S4O62
Cl 2( g ) + 2Br(aq.)
N2, NH3, N3H, NH2NH2,NH2OH,
(d) 2Cl(aq .) + 2Br(aq.)
2Cl(aq .) + 2Br(aq.)
KNO2, KNO3, N2O
SOLUTION
SOLUTION
Reduced Oxidised
(a) MnCl2 < Mn(OH)3 < MnO2 < KMnO4
(a) Cl2 CH4
ox. no. of Mn +2 +3 +4 +7 (b) MnO2 C2H2O4(aq.)
(b) HXO4 > HXO3 > HXO2 > HXO
(c) I2 S2 O32-
ox. no of X +7 +5 +3 +1
(c) HI < I2 < ICl < IF3 < IF5 < HIO4 (d) Cl2 Br-
ox. no . of I -1 0 +1 +3 +5 +7
(d) NH3 < N2H4 <NH2OH < N3H < N2< N2O EXAMPLE 26
< KNO2 < KNO3 Identify the substance acting as oxidant or reductant if any
ox. no. of N -3 -2 - 1 -1/3 0 +1 +3 +5 in the following :
(i) AlCl3 + 3K Al + 3KCl
EXAMPLE 24
(ii) SO2 + 2H2 S
3S + H2O
Select the nature or type of redox change in the following
reactions: (iii) BaCl2 + Na2SO4
BaSO4 + 2NaCl
(a) 2Cu+ Cu2+ + Cu0
(iv) 3I2 + 6NaOH
NaIO3 + 5NaI + 3H2O
(b) Cl ClO- + Cl-
2

(c) 2KClO3 2KCl + 3O2 SOLUTION
(d) (NH4)2Cr2O7
N + Cr O + 4H O
2 2 3 2 In a conjugate pair, oxidant has higher ox. no.
(e) 10FeSO4 + 2KMnO4 + 8H2SO4 (i) For AlCl3 : Al3+ + 3e Al0 ;
2MnSO + 5Fe (SO ) + K SO + 8H O oxidation AlCl3
4 2 4 3 2 4 2 For K : K0 K1+ + e and reductant K.

1. Redox_[Oxidation reduction].indd 11 19-10-2017 17:22:55


1.12 Chapter 1

(ii) For SO2 : S4+ + 4e


S0 ; M Cr O 2
(c) E 2 = 2 7
(Cr26+
2Cr 3+ + 6e)
Cr O
For H2S : S2-
S0
+ 2e
2 7 6
( iii) No change in ox. no. of either of the conjugate pair. MCrO2
(d) EC O2 = 4
None is oxidant or reductant. 2 4 (C32+
2C 4+ + 2e)
2
M FeC2O4
(iv) For I2 : I 02
2I5+ + 10e and I 02 + 2e
(e) E FeC O =
2I1- 2 4
3
I2 acts as oxidant and reductant both.
(Fe 2+ + C32+
Fe3+ + 2C 4+ + 3e)
M CuSO 4
EXAMPLE 27 (f) E CuSO = (2Cu 2+ + 2e
Cu +2 )
4
1
Write the half reactions for the following redox reactions:
(a) 2Fe3+(eq.) + 2I-(aq.)
2Fe2+(aq.) + I2(eq.) EXAMPLE 29
(b) Zn(s) + 2H+(aq.)
Zn2+(aq.) + H2(g) The number of electrons lost or gained during the change,
(c) Al(s) + 3Ag+(aq.)
Al3+(aq.) + 3Ag(s) Fe + H2O Fe3O4 + H2
(a) 2 (b)4 (c)6 (d)8
SOLUTION  Ans. d
(a) Fe3+ + e
Fe2+ ; I-
I2 + e
SOLUTION
(b) Zn
Zn2+ + 2e; H+ + e
H2
3Fe + 4H2O
Fe3O4 + 4H2
Al3+ + 3e; Ag+ + e
(c) Al Ag 3Fe0
(Fe8/3+)3 + 8e

EXAMPLE 28 EXAMPLE 30
Evaluate equivalent weight of reductant or oxidant given on Oxidation number of C in HNC is:
left hand side of each reaction: (a) + 2 (b) -3 (c) + 3 (d) Zero
 Ans. a
2AsO34 + 10H+ + 4e
(a) As2O3 + 5H2O
SOLUTION
(b) MnO 4+ 8H+ + 5e
Mn2+ + 4H2O
2 1 + (-3) + a = 0
(c) Cr2 O 7 + 14H+ + 6e
2Cr3+ + 7H2O
a = + 2
(d) C 2O 24-
2CO2 + 2e EXAMPLE 31
(e) FeC2O4
Fe3+ + 2CO2 + 3e The equivalent weight of the salt KHC2O4. H2C2O4.4H2O
1+ 2
used as reducing agent is:
Cu 2 + SO 4
(f) 2CuSO4 + 2e (a) Mol. wt./1 (b) Mol. wt./2
Mol. weight of reduc tan t or oxidant (c) Mol. wt./3 (d) Mol. wt./4

Number of elements gained or lost by  Ans. d
SOLUTION
SOLUTION
Ered./oxi. = one molecular of reductant or oxidant or value 2(C2+)2
(2C4+)2 + 8e
factor. Mol. wt. M
M Eq. wt. = =
(a) E As2O3 = As2O3 (As32+ 2As5+ + 4e) No. of electrons lost or 4
4
M MnO gained by one molecule
(b) E MnO 4 = 5 (Mn7+ + 5e Mn2+)
4

1. Redox_[Oxidation reduction].indd 12 19-10-2017 17:22:57


start from here
Oxidation Reduction1.13

EXAMPLE 32 SOLUTION
Oxidation number of Cl in CaOCl2 is: Ag+ + e
Ag; Hydroquinol reduces Ag+ to Ag.
(a) -1 and +1 (b) +2
(c) -2 (d) None of these EXAMPLE 36
 Ans. a In the balanced chemical reaction,

3 + aI + bH+ cH2O + dI2
IO
SOLUTION
a, b, c and d respectively correspond to :
OCl (a) 5, 6, 3, 3 (b) 5, 3, 6, 3
CaOCl2 is Ca
Cl (c) 3, 5, 3, 6 (d) 5, 6, 5, 5
Thus, one Cl has + 1 and other -1 ox. no.  Ans. a
EXAMPLE 33
SOLUTION
Oxidation number of carbon in carbon sub-oxide is:
The balanced equation will be :
(a) +2/3 (b) +4/3 (c) +4 (d) -4/3
IO3 + 5I + 6H+ 3I2 + 3H2O]
 Ans. b
EXAMPLE 37
SOLUTION
Equivalent weight of FeC2O4 during its reaction with
C3O2 is carbon sub-oxide KMnO4 is:
Thus, 3a + (2 - 2) = 0 (a) M/3 (b) M/1
a = + 4/3 (c) M/2 (d) M/4
EXAMPLE 34  Ans. a
In a reaction, 4 mole of electrons are transferred to 1 mole SOLUTION
of HNO3, the possible product obtained due to reduction is:
(a) 0.5 mole of N2 (b) 0.5 mole of N2O Fe2+
Fe3+ + e
(c) 1 mole of NO2 (d) 1 mole of NH3 (C3+)2
2C4+ + 2e
 Ans. b Fe3+ + 2CO2 + 3e
FeC2O4
SOLUTION
EXAMPLE 38
2N5+ N +2 + 8e; Thus, 1 mole of HNO3 will give half
mole of N2O. In CH2 = CCl2, the two carbon atoms have oxidation num-
ber respectively:
EXAMPLE 35 (a) -2, +2 (b) -2, -2
During developing of an exposed camera film, one step (c) +2, +2 (d) +2, -2
involves in the following reaction;  Ans. a

HO OH + 2AgBr + 2OH
SOLUTION

(Hydroquinol) - 2 in CH2 and +2 in CCl2

EXAMPLE 39
O O + 2Ag + 2H2O + 2Br
On combustion of CH4 to CO2 and H2, the oxidation num-
Which of the following best describes the role of ber of carbon changes by:
hydroquinol: (a)8 (b)Zero
(a) It acts as an acid (c)4 (d)3
(b) It acts as reducing agent  Ans. a
(c) It acts as oxidant
(d) It acts as a base SOLUTION
 Ans. b C4-
C4+ + 8e

1. Redox_[Oxidation reduction].indd 13 19-10-2017 17:22:58


1.14 Chapter 1

EXAMPLE 40 EXAMPLE 44
Which does not possess oxidation number of S equal to +6 : Which reaction does not represent auto redox or
(a) Caros acid (b) Marshalls acid disproportionation:
(c) Oleum (d) Hypo (a) Cl + OH-
2
Cl- + ClO3 + H O
2
 Ans. d (b) 2H2O2 H2O + O2
(c) 2Cu
+ Cu2+ + Cu
SOLUTION
(d) (NH4)2Cr2O7
N2 + Cr2O3 + 4H2O
Oxidation number of S in hypo (Na2S2O3) is + 2.
 Ans. d
EXAMPLE 41
SOLUTION
The oxidation number of C in NaOCN and NaCNS are
respectively :
In auto redox or disproportionation, same element
(a) -2, -2 (B) +2, - 2 is oxidized as well as reduced. In (a) Cl2 (b) H2O2
(c) -3, -2 (D) +4, +4 and (c) Cu+ is oxidized as well as reduced. In (d)
 Ans. d
N is oxidized and Cr is reduced in one molecule of
(NH4)2Cr2O7 and thus, it is intramolecular redox.
SOLUTION
EXAMPLE 45
O C N and S C N
Carbon is less electronegative than N, O and S. The average oxidation number of I in KI3, Fe in Fe3O4 are
respectively:
EXAMPLE 42 (a) -1/3, + 8/3 (b) -1, + 8
Maximum oxidation number of under lined atom is shown (c) 0, + 3 (d) 0, + 2
in:  Ans. a
(a) Osmium tetroxide (b) Rutheruim tetroxide
(c) Perxenate ion (d) All of these SOLUTION
 Ans. d Average oxidation no. of I in KI3
1 0 (1 1) + 2 0 1
SOLUTION or KI + I 2 = =
3 3
Os in OsO4 Ru in RuO4 and Xe in Average oxidation no. of Fe in Fe3O4
XeO 64 shows a maximum oxidation state of +8. +3 0 (+3 2) + (+1 1) + 8
or Fe 2O3 . FeO = =
3 3
EXAMPLE 43
Which of the following ion is spectator ion in the reaction Ox.No. No. of atoms
Average ox. no. =
given below: No. of atoms
Zn + 2H+ + 2Cl- Zn2+ + 2Cl- + H
2 EXAMPLE 46
(a) Zn2+
(b) H+ In which of the following metal atom has negative oxida-
(c) Cl- tion state.
(d) None of these uH, [Fe(CO)]2-, NaHg
C
I II III
 Ans. c (a) I, II and III (b) I and II
(c) I and III (d) II and III
SOLUTION  Ans. b
The species present in solution but does not take part in
the reaction is called spectator ion. It may be omitted while SOLUTION
writing the net ionic reaction. Cu in CuH and Fe in [Fe(CO)]2- have -1 and -2 oxi-
Zn + 2H+ Zn2+ + H2 dation state respectively.

1. Redox_[Oxidation reduction].indd 14 19-10-2017 17:22:59


Oxidation Reduction1.15

EXAMPLE 47 Fe2+ Fe3+ + e


In which triplet each species can act as oxidant and reduct- ( C )2
2+ 2C4+ + 4e
ant : Mn in KMnO4 is reduced.
(a) H2O2, HNO2, HClO4 5e + Mn7+
Mn2+
(b) HNO2, SO2, H2O2 EXAMPLE 50
(c) HNO3, SO2, H2SO4
(d) KMnO4, SO3, O3 The oxidation state of iodine in IPO4 is :
 Ans. b (a) +1 (b) +3 (c) +5 (d) +7
 Ans. b
SOLUTION
The species in which an element has oxidation number SOLUTION
lying in between its minimum and maximum values can Let oxidation state of iodine be x
acts as oxidant and reductant both. x - 3 = 0, x = +3,
Mini. Max. PO 34 has combined oxidation number -3.
Ox. No. Ox. No.
N3+ in HNO2 -3 +5 EXAMPLE 51
S4+ in SO2 -2 +6 Which of the following is not intramolecular redox reac-
O1- in H2O2 -2 0 tion :
EXAMPLE 48 (a) (NH4)2Cr2O7
N2 + Cr2O3 + 4H2O
Four Cl2molecules undergo a loss and gain of 6 mole of (b) 2KClO3
2KCl + 3O2
electrons to form two oxidation states of Cl in a auto redox
change. What are the +ve and -ve oxidation state of Cl in (c) 2Mn2O7
4MnO2 + 3O2
the change: (d) 2ClO2 + 5H2O2 2

2Cl + 5O2 + 6H2O
OH -
(a) Cl5+, Cl0 (b) Cl7+, Cl1-  Ans. d
3+ 0
(c) Cl , Cl (d) Cl3+, Cl1-
 Ans. d SOLUTION

SOLUTION An intramolecular redox change involves oxidation of


one element and reduction of other element within one
Cl2 can show the gain of electron by molecule.
2e + Cl2 2Cl-
Since in all six electrons are used by four PASSAGE :
Cl2 molecules. Thus,
The equivalent weight of a species if acts as oxidant or
6e + 3Cl2
6Cl-
reductant should be derived by :
2Cl3+ + 6e
Cl2
Eq. weight of oxidant or reductant

EXAMPLE 49 Mol. wt. of oxidant or reductan t


Which species are oxidized and reduced in the reaction : = Number of electrons lost or gained by one
FeC2O4 + KMnO4 Fe2+ + CO2 + Mn2+ molecule of oxidant or reductan t
( a) Oxidised : Fe, C Reduced : Mn
(b) Oxidised : Fe Reduced : Mn During chemical reactions, equal equivalents of one species
(c) Reduced : Fe, Mn Oxidised : C react with same number of equivalents of other species giv-
(d) Reduced : C Oxidised : Mn, Fe ing same number of equivalent of products. However this is
not true for reactants if they react in terms of moles. Also
Ans. a molarity can be converted to normality by multiplying the
molarity with valence factor or n factor.
SOLUTION

Fe and carbon in FeC2O4 are oxidized

1. Redox_[Oxidation reduction].indd 15 19-10-2017 17:22:59


1.16 Chapter 1

EXAMPLE 52 EXAMPLE 55
Equivalent weight of Fe2O3 in terms of its mol. weight in State the equivalent mass of each reactant and product in
the change Fe3O4 Fe2O3 is : following half-reactions :
( a) M (b) M/2 (c) M/3 (d) 3M/2 (i) 2CuI2
Cu2I2 (ii) As2O3
H3AsO4
 Ans. d
(iii) HNO3
NO (iv) KMnO4
K2MnO4
SOLUTION
(v) PH3
H3PO3
2[Fe+8/3]3
3[Fe3+]2 + 2e
M SOLUTION
E Fe 2O3=
2/3 M M
(i) E CuI 2 = ; E Cu 2 I 2=
1 2
EXAMPLE 53
M M
Equivalent weight of N2 and NH3 in the change N2 (ii) E As2O3= ; E H 3AsO4 =
4 2
NH3 respectively is : M M
(a) 4.67, 12.4 (b) 9.3, 12.4 (iii) E HNO3 = ; ENO =
3 3
(c) 4.67, 5.34 (d) 5.34, 4.67 M M
(iv) E KMnO 4 = ; E K 2 MnO 4 =
 Ans. d 1 1
M M
(v) E PH 3= ; E H 3PO 3 =
SOLUTION 6 6
6e + (N0)2
2(N3-)
28 E NH 17 EXAMPLE 56
E N 2 = ; 3 =
6 3 Select the type of redox reaction from the following on the
basis of type of redox changes (a) intermolecular redox; (b)
EXAMPLE 54 intramolecular redox; (c) auto-redox. If none, write none.
The oxidation states of sulphur in Caros and Marshalls NaOH
acid are :
(i) C6H5CHO C6H5CH2OH + C6H5COONa
(a) +6, +6 (b) +4, +6 2-
2CrO 4 + H2O
(ii) Cr2 O 72+ 2OH-
(c) +6, -6 (d) +6, +4
 Ans. a (iii) 2Mn2O7
4MnO2 + 3O2
+ -
SOLUTION NH 4 + HSO 4
(iv) NO 3+ H2S + H2O + H+
H2SO5 Caros Acid
(v) Fe + N2H4
NH + Fe(OH)
3 2
O
|| (vi) 2KOH + Br2
KBr + KBrO
HOSOOH (+6)
|| State Cu + Cu2+
(vii) 2Cu+
O +

H2S2O8 Marshalls Acid (viii) Ag( NH 3 ) +2 2


H +
Ag+ + 2 NH 4

O O (ix) 5KI + KIO3 + 6HCl


3I + 6KCl + 3H O
2 2
|| ||
HOSOOSOH (+6) SOLUTION
|| || State
O O ( a) Intermolecular redox reaction : (iv), (v) and (ix).
(b) Intramolecular redox reaction : (iii); Mn is reduced; O
Both these acids have peroxy link.
is oxidised.
(c) Auto-redox or disproportionation: (i), (vi), (vii).
(d) (ii) and (viii) are not redox reaction.

1. Redox_[Oxidation reduction].indd 16 19-10-2017 17:23:02


Oxidation Reduction1.17

EXAMPLE 57 M 152
Fe 32+ + 2e; E FeSO 4 = =
(d) 2Fe2+ = 152
Arrange the following in the increasing order of oxidation 1 1
state of Mn : M 122 . 5
(i) Mn2+ (ii) MnO2 (iii) KMnO4 6e + Cl5+ Cl-; E KClO3 = = = 20.42
6 6
(iv) K2MnO4 M 232
(8 / 3) + 3+
(a) (i) > (ii) > (iii) > (iv) (e) 2Fe 3 3Fe 2 + 2e; E Fe3O 4= = = 232
1 1
(b) (i) < (ii) < (iv) < (iii)
M 158
(c) (ii) < (iii) < (i) < (iv) 3e + Mn7+ Mn4+; E KMnO 4 = = = 52.67
(d) (iii) < (i) < (iv) < (ii) 3 3
 Ans. b (f) 6e + N 0
2
2N3-

M. mass of N 2 28
SOLUTION E N2 = = = 4.67
6 6
Mn2+ < MnO2 < K2MnO4 < KMnO4
(+2) (+4) (+6) (+7) (g) FeC O
2
Fe3+ + CO
4 2

EXAMPLE 58 Fe 2 +
Fe 3+ + e
Calculate the equivalent mass of each oxidant and reduct- C 32+
2C 4 + + 2e
ant in : Fe 3+ + 2C 4 + + 3e
FeC 2 O 4
(a) KI + K Cr O
2
Cr3+ + 3I
2 7 2 M 144

Na S O + 2NaI E FeC2O 4 = = = 48
(b) Na2S2O3 + I2 2 4 6 3 3
(c) NO 3
N
2 (h) S4+
S6+ + 2e
(d) FeSO4 + KClO3
KCl + Fe (SO )
2 4 3 E Na 2SO 3 M 126
= = = 63
(e) Fe3O4 + KMnO4
Fe O + MnO
2 3 2 2 2
(f) N2
NH
3 3e + Cr6+ Cr3+
(g) FeC2O4
Fe3+ + CO
2 E Na 2CrO 4 M 162
= = = 54
(h) Na2SO3 + Na2CrO4
Na SO + Cr(OH) 3 3
2 4 3
PASSAGE :
SOLUTION Redox reactions are those in which oxidation and reduction
M. mass of oxidant or reductan t take place simultaneously. Oxidising agent can gain elec-
Eoxidant/reductant = No. of ' e' lost or gained by one tron whereas reducing agent can lose electron easily. The
oxidation state of any element can never be in fraction. If
molecule of oxidant or reductan t
oxidation number of any element comes out be in fraction,
M 166 it is average oxidation number of that element which is pre-
I 02 + 2e; EKI =
(a) 2I- = = 166
1 1 sent in different oxidation states.
M 294
6e +Cr26+ 2Cr3+; E K 2Cr2O 7= 6 = = 49 EXAMPLE 59
6
(5 / 2) + M 158 The oxidation state of Fe in Fe3O4 is :
(b) 2S22+ S 4 + 2e; E Na 2S2O3= = = 158 (a) 2 and 3 (b) 8/3 (c) 2 (d) 3
1 1
M 254  Ans. a
2I1-; E I 2 = =
2e + I 02 = 127
2 2
0 Ionic m. mass 62 SOLUTION
(c) 10e + 2N5+ N 2 ; E NO = =
3 5 5 Fe3O4 can be written as FeO.Fe2O3
= 12.4
In FeO, Fe has oxidation state +2, in Fe2O3 has oxidation
state +3.

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1.18 Chapter 1

EXAMPLE 60 EXAMPLE 62
1 Which of the following can be both oxidizing as well as
N 3 reducing agent ?
N H (a) H2 (b) I2
N , In this compound HN3 (hydrazoic acid), (c) H2O2 (d) All of these
2  Ans. d
oxidation state of N1, N2 and N3 are :
SOLUTION
( a) 0, 0, 3 (b) 0, 0,-1
All of them can go to higher as well as lower oxidation
(c) 1, 1, -3 (d) -3, -3, -3 states.
 Ans. b
EXAMPLE 63
SOLUTION The oxidation number of sulphur in K2S2O8 is :
1 (a) +2 (b) +4
N 3
(c) +7 (d) +6
N H
SOLUTION
N
2 O O
N1 and N2
has oxidation state zero because they are linked
to each other. S O O S
For N3, X + 0 + 0 + 1 = 0 X = -1 O O
Answer (B) is correct.
O O
EXAMPLE 61 Since there is peroxide linkage.
2x - 12 - 2 = -2
Equivalent mass of chlorine molecule in the equation :
x = +6
3Cl2 + 6NaOH
5NaCl + NaClO + 3H O
3 2 +7 is wrong
(a) 42.6 (b) 35.5 2x - 16 = -2
(c) 59.1 (d) 71 2x = 14
 Ans. a x = 7 [ of peroxide linkage]
Secondly, sulphur cannot have oxidation number +7
SOLUTION because it has 6 valence electrons.
35.5
5Cl
5Cl- Eq. wt. = = 35.5
1
35.5
ClO3- Eq. wt. =
Cl = 7.1
5
Total for Cl2 = 35.5 + 7.1 = 42.6

1. Redox_[Oxidation reduction].indd 18 19-10-2017 17:23:06

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