UNIT - 8 REDOX REACTION ( BY: JITENDER SIR )

Rules For Calculation Of Oxidation Number

Most electronegative element: F > O > Cℓ = N
1. In uncombine state or free state, oxidation number of an element is zero.
2. In combined state oxidation no. of
a) F is always –1.
Cℓ, Br, I = -1 , +1 , +3 +5 , +7 ( with F , O and N they will show Positive oxidation state )
halogens as halide is always –1.
b) O is always –2 (In peroxides it is –1, in superoxide’s it is –1/2. However, in F2 O it is +2)
c) H is always +1 { Except Hydride ( hydrogen with metal) where it carry –1 }
d) Nitrogen carry -3 oxidation state , but with F, O and Cℓ it carry +3 oxidation state.
e) sulphur as sulphide is always –2 ( H2S) . Otherwise it carry: +2 , +4 ,+6
f) alkali metals (i.e., I A group — Li, Na, K, Rb, Cs, Fr) is always +1.
g) alkaline earth metals (i.e., II A group—Be, Mg, Ca, Sr, Ba, Ra) is always +2.

Q8.1: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) S in SO 24− ion (h) S in HS O3− ion (i) Pt in (PtCl6)2– (j) Mn in (MnO4)– ion

Problem 4: Determine the oxidation no. of following elements underlined:

a) CrO5 b) H2SO5 (c) NCℓ3
-2 -2
O O
a) b) c) NCl3
-O O- +1 -2 -1 -1 +1
Cr H O S O O H
N = +3
-O O- O -2 Cl = -1
S = +6
Cr = +6

Question 8.6: Write the stock notation formulae for the following compounds:
Answer :
(a) HgCl2 : Mercury(II) chloride Hg(II)Cl2 (b) NiSO4 : Nickel(II) sulphate Ni(II)SO4
(c) SnO2 : Tin(IV) oxide Sn(IV)O2 (d) Ti2SO4 : Thallium(I) sulphate Tl2(I)SO4
(e) Fe2(SO4)3 : Iron(III) sulphate (f) Cr2O3 : Chromium(III) oxide Cr2(III)O3
(g) AuCl : Aurous chloride, Au(I)Cl (h) AuCl3 : Auric chloride, Au(III)Cl3
(i) SnCl2 : Stannous chloride, Sn(II)Cl2 (j) SnCl4 : Stannic chloride, Sn(IV)Cl4

Problem 8.3 : Using Stock notation, represent the following compounds:

HAuCl4, Tl2O, FeO, Fe2O3, 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:
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.

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 Oxidation ( Oxidised ) :Reducing agent ( Reductant) :(high reducing power)
1. Addition of oxygen/electronegative element to a substance
2 Mg (s) + O2 (g) → 2 MgO (s)
Mg (s) + F2 (g) → MgF2 (s)
2. Removal of hydrogen/ electropositive element from a substance.
2 H2S(g) + O2 (g) → 2 S (s) + 2 H2O (l)
3. Loss of electron : Eg : Zn → Zn2+ + 2e- means ( Zn ̸Zn2+ )
4. Increase in oxidation number

Reduction (Reduced) : Oxidising agent (Oxidant) :

1. Removal of oxygen/electronegative element from a substance
2 HgO (s) →2 Hg (l) + O2 (g) (b) 2 FeCl3 (aq) + H2 (g) →2 FeCl2 (aq) + 2 HCl(aq)
2. Addition of hydrogen/ electropositive element to a substance.
CH2 = CH2 (g) + H2 (g) → H3C–CH3 (g)
3. Gain of electrons : Eg : Cu2+ + 2e- → Cu means ( Cu2+ ̸ Cu)
4. Decrease in oxidation number

Point`s to be remember for Redox Reaction:

*oxidation takes place on more reactive metal
*reduction takes place on less reactive metal
*for redox reaction solution always be made up of less reactive metal
*in redox reaction solution can be represented in ionic form
eg : CuSO4 solution can be represented by Cu2+ (aq)
* if solution made up of more reactive metal then redox reaction does not takes place

Problem 8.1
In the reactions given below, identify the species undergoing oxidation and reduction:
(i) H2S (g) + Cl2 (g) → 2 HCl (g) + S (s)
(ii) 3Fe3O4(s) + 8 Al (s) → 9 Fe (s) + 4Al2O3 (s)
(iii) 2 Na (s) + H2 (g) → 2 NaH (s)
Solution
(i) H2S is oxidised because a more electronegative element, chlorine is added to hydrogen (or a more
electropositive element, hydrogen has been removed from S). Chlorine is reduced due to addition of
hydrogen to it.
(ii) Aluminium is oxidised because oxygen is added to it. Ferrous ferric oxide (Fe3O4) is reduced
because oxygen has been removed from it.
(iii) With the careful application of the concept of electronegativity only we may infer that sodium is
oxidised and hydrogen is reduced. Reaction (iii) chosen here prompts us to think in terms of another
way to define redox reactions.

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Problem 8.2 : Justify that the reaction : 2 Na(s) + H2(g) → 2 NaH (s) is a redox change.
Solution : Since in the above reaction the compound formed is an ionic compound, which may also be
represented as Na+H– (s), this suggests that one half reaction in this process is :
2 Na (s) → 2 Na+(g) + 2e–
and the other half reaction is: H2 (g) + 2e– → 2 H–(g)
This splitting of the reaction under examination into two half reactions automatically reveals that here
sodium is oxidised and hydrogen is reduced, therefore, the complete reaction is a redox change.

Problem 8.4
Justify that the reaction: 2Cu2O(s) + Cu2S(s) → 6Cu(s) + SO2(g) is a redox reaction. Identify the
species oxidised/reduced, which acts as an oxidant and which acts as a reductant.
Solution
oxidation number to each of the species in the reaction under examination. This results into:
+1 –2 +1 –2 0 +4 –2
2Cu2O(s) + Cu2S(s) → 6Cu(s) + SO2
We therefore, conclude that in this reaction copper is reduced from +1 state to zero oxidation state and
sulphur is oxidised from –2 state to +4 state. The above reaction is thus a redox reaction. Further,
Cu2O helps sulphur in Cu2S to increase its oxidation number, therefore, Cu(I) is an oxidant; and
sulphur of Cu2S helps copper both in Cu2S itself and Cu2O to decrease its oxidation number; therefore,
sulphur of Cu2S is reductant .

Question 8.13: 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) Pb(s) + PbO2(s) + 2H2SO4(aq) → 2PbSO4(s) + 2H2O(l)
Answer
(a) Oxidised substance → C6H6O2
Reduced substance → AgBr ( reduction state change from +1 to 1 )
Oxidising agent → AgBr ( reduction )
Reducing agent → C6H6O2

Q 8.16: 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 Rx.

Ans : The given reaction occurs because XeO64- oxidises F– and F– reduces XeO64- .
+8 -1 +6 0
XeO64-(aq) + 2F– (aq) + 6H+(aq) → XeO3(g) + F2(g) + 3H2O(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 Na2XeO6 that is a stronger oxidising agent than F–.

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Types of Redox reaction

1. Displacement reactions : it is of two type: metal displacement and non-metal displacement.

(a) Metal displacement: CuSO4(aq) + Zn (s) → Cu(s) + ZnSO4 (aq)
(b) Non-metal displacement: The non-metal displacement redox reactions include hydrogen
displacement and a rarely occurring reaction involving oxygen displacement. All alkali metals and
some alkaline earth metals (Ca, Sr, and Ba) which are very good reductants, will displace hydrogen
from cold water.
0 +1 –2 +1 –2 +1 0
2Na(s) + 2H2O(l) → 2NaOH(aq) + H2(g) (1)

0 +1 –2 +2 –2 +1 0
Ca(s) + 2H2O(l) → Ca(OH)2 (aq) + H2(g) (2)

Less active metals such as magnesium and iron react with steam to produce dihydrogen gas:
0 +1 –2 +2 –2 +1 0
Mg(s) + 2H2O(l) → Mg(OH)2(s) + H2(g) (3)

2. Decomposition reactions
Decomposition reactions are the opposite of combination reactions. Precisely, a decomposition
reaction leads to the breakdown of a compound into two or more components at least one of which
must be in the elemental state. Examples of this class of reactions are:
i) 2H2O (l) → 2H2 (g) + O2(g)
ii) 2NaH (s) → 2Na (s) + H2(g)
iii) 2KClO3 (s) →2KCl (s) + 3O2(g)

3.Combination Reaction : A combination reaction may be denoted in the manner: A + B → C

i) C(s) + O2 (g) → CO2(g)
ii) 3Mg(s) + N2(g)→ Mg3N2(s)

4. Disproportionation reactions :
In a disproportionation reaction an element in one oxidation state is simultaneously oxidised and
reduced.
Oxidation

2MnO2
4 + 4H+ MnO4 + MnO2 + 2H2O
+6 +7 +4
Reduction

0 Reduction -3 +1
P4(s) + 3OH (aq)+ 3H2O(l) → PH3(g) + 3H2PO2–(aq)
–

Oxidation

Redox couple: A redox couple is defined as having together the oxidised and reduced forms
of a substance taking part in an oxidation or reduction half reaction
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Question 8.21:
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.
Mn3+ (aq) → Mn2+(aq) + MnO2(s) + H+(aq)

Problem 8.5 : Which of the following species, do not show disproportionation reaction and why?
ClO–, ClO2–, ClO3– and ClO4–
Also write reaction for each of the species that disproportionate.
Solution : Among the oxyanions of chlorine listed above, ClO4– does not disproportionate because in
this oxyanion chlorine is present in its highest oxidation state that is, +7. The disproportionation
reactions for the other three oxyanions of chlorine are as follows:
+1 –1 +5
3ClO → 2Cl + ClO3–
– –

+3 +5 –1
6 ClO2– → 4ClO3– + 2Cl–

+5 –1 +7
4ClO3– → Cl + 3ClO4–
–

Question 8.23: 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.
Cℓ2(s) + SO2(aq) + H2O(ℓ) → Cℓ–(aq) + SO42–(aq)

Problem 8.7(Not for this exam 2022)

Why do the following reactions proceed differently?
Pb3O4 + 8HCl → 3PbCl2 + Cl2 + 4H2O
and
Pb3O4 + 4HNO3 → 2Pb(NO3)2 + PbO2 + 2H2O
Solution
Pb3O4 is actually a stoichiometric mixture of 2 mol of PbO and 1 mol of PbO2. In PbO2, lead is
present in +4 oxidation state, whereas the stable oxidation state of lead in PbO is +2. PbO2 thus can
act as an oxidant (oxidising agent) and, therefore, can oxidise Cl– ion of HCl into chlorine. We may
also keep in mind that PbO is a basic oxide. Therefore, the reaction
Pb3O4 + 8HCl → 3PbCl2 + Cl2 + 4H2O
can be splitted into two reactions namely:
2PbO + 4HCl → 2PbCl2 + 2H2O (acid-base reaction)
+4 –1 +2 0
PbO2 + 4HCl → PbCl2 + Cl2 +2H2O
(redox reaction)
Since HNO3 itself is an oxidising agent therefore, it is unlikely that the reaction may occur between
PbO2 and HNO3. However, the acid-base reaction occurs between PbO and HNO3 as:
2PbO + 4HNO3 → 2Pb(NO3)2 + 2H2O
It is the passive nature of PbO2 against HNO3 that makes the reaction different from the one that
follows with HCl.

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Q8.8: 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 SO2 : S in +4 oxidation state.we know, minimum O.N of S is -2 and maximum O.N of S is +6.
It means O.N of S in SO2 can either decreases or increases its oxidation number. so, SO2
can act both as oxidizing as well as reducing agent.
In H2O2:
O.N of O is -1. But we know, minimum O.N of O is -2 and maximum O.N is +2. therefore O
in H2O2 can either decreases or increases its oxidation number. so, H2O2 can act both as
oxidizing as well as reducing agent.
In O3:
O.N of O is zero.it can't increases its oxidation number, it can only decrease its oxidation
number from zero to -1 or -2.so, ozone can act only as oxidizing agent.
In HNO3,
The oxidation number of N is +5. It is maximum. so, N in HNO3 can only decreases its
oxidation number. so, it can act as an oxidizing agent only.

Ion Name Ion Name

MnO4─ Permanganate ion BrO3─ Bromate ion
MnO42─ Manganate ion IO3─ Iodate
Cr2O72─ Dichromate ion ClO3─ Chlorate ion
CrO42─ Chromate ion Br─ Bromide
SO42─ Sulphate ion PO43─ Phosphate
SO32─ Sulphite ion NH4+ Ammonium

Balancing Redox Reaction by ion-Electron Method (ACIDIC MEDIUM):

1.Separate the reactants and products into half-reactions involving the elements that changes its
oxidation number. Write the skeleton equations for each half-reaction.
2. Balance each half-reaction separately involving given steps.
i)First balance the atoms of the element other than hydrogen and oxygen .
ii) To balance oxygen atom , Add H2O Molecule on that side where oxygen atoms are less .
iv) To balance Hydrogen atoms we have to add H+ Ion to that side where H atoms are less .
3.)Add electrons to balance the charges on the both side .

Balancing Redox Reaction by ion-Electron Method ( BASIC MEDIUM ) :

1.Separate the reactants and products into half-reactions involving the elements that changes its
oxidation number. Write the skeleton equations for each half-reaction.
2. Balance each half-reaction separately involving given steps.
i)First balance the atoms of the element other than hydrogen and oxygen.
ii) To balance oxygen atom , Add H2O.
iv) To balance Hydrogen atoms we have to add H+ ion.
v) Now add OH― to balance H+ ion on both side.
3.)Add electrons to balance the charges on the both side .

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Question 8.18: Balance the following redox reactions by ion-electron method:
Acidic medium:
i. MnO4– (aq) + SO2 (g) → Mn2+ (aq) + SO42-(aq) (in acidic solution)
ii. H2O2 (aq) + Fe2+ (aq) → Fe3+ (aq) + H2O (l) (in acidic solution)
iii. Cr2O7 2–+ SO2(g) → Cr3+ (aq) + SO42–(aq) (in acidic solution)
iv. I─ + IO3─ + H+ → I2 + H2O ( acidic medium )
v. MnO4– (aq) + C2H2O4 (g) → Mn2+ (aq) + CO2 + H2O(aq) (in acidic solution)
Answers
(i) 2MnO4– + 5SO2 + 2H2O → 2Mn2+ + 5SO42- + 4H+
(ii) H2O2 (aq) + 2Fe2+ (aq) + 2H+ → 2Fe3+ (aq) + 2H2O
(iii) Cr2O7 2–+ 3SO2(g) + 2H+ → 2Cr3+ (aq) + 3SO42– + H2O
(iv) 5I─ + IO3─ + 6H+ → 3I2 + 3H2O
(v) 2MnO4– (aq) + 5C2H2O4 (g) 6H+ → 2Mn2+ (aq) + 10CO2 + 8H2O(aq)

Basic medium
1. MnO4– (aq) + I– (aq) → MnO2 (s) + I2(s) (in basic medium)
2. P4(s) + OH–(aq) → PH3(g) + H2PO2– (aq)
3. N2H4 + CℓO3(aq) → NO(g) + Cℓ(g)
4. Cℓ2O7(g) + H2O2(aq) → CℓO2- (aq) + O2
Answer:
1.
2MnO4– (aq) + 6I– (aq) + 4H2O →2 MnO2 (s) + 3I2(s) + 8OH─
2. P4 + 3OH- + 3H2O → PH3 + 3H2PO2-
3. 3N2H4 + 4CO3 → 6NO + 4C + 6H2O
4. Cl2O7 + 4H2O2 + 2OH- → 2ClO2- + 4O2 + 5H2O

Problem 8.8
Write the net ionic equation for the reaction of potassium dichromate (VI), K2Cr2O7 with sodium
sulphite, Na2SO3, in an acid solution to give chromium (III) ion and the sulphate ion.
Cr2O7 2– + SO32- → Cr3+ (aq) + SO42– (Reaction will be not given in the exam)
Problem 8.9
Permanganate ion reacts with bromide ion in basic medium to give manganese dioxide and bromate
ion. Write the balanced ionic equation for the reaction.
MnO4– (aq) + Br─ → MnO2 (aq) + BrO3─ ( Reaction will be not given in the exam)
Problem 8.10
Permanganate (VII) ion, MnO4– in basic solution oxidises iodide ion, I– to produce molecular iodine (I2)
and manganese (IV) oxide (MnO2). Write a balanced ionic equation to represent this redox reaction.
MnO4– (aq) + I─ → MnO2 (aq) + I2 ( Reaction will be not given in the exam)

Question 8.4: 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 Rx. above its symbol as:
+1 -2 0 +1 -1 +1 -2 +1
H2O(s) + F2(g) → HF(g) + HOF(g)

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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Q8.14: Consider the reactions: 2S2O32-(aq) + I2(s) → S4O62- (aq) + 2I– (aq)
S2O32-(aq) + 2Br2(l) + 5 H2O(l) → SO42- (aq) + 4Br–(aq) + 10H+(aq)
Why does the same reductant, thiosulphate react differently with iodine and bromine?
Ans: The average oxidation number (O.N.) of S in S2O32- 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 bromin

Question 8.20: What sorts of informations can you draw from the following reaction?
(CN)2(g) + 2OH─ (aq) → CN─(aq) + CNO─ (aq) + H2O(ℓ)
Answer : The oxidation numbers of carbon in (CN)2 , CN– and CNO– are +3, +2 and +4 respectively. It
can be easily observed that the same compound is being reduced and oxidised simultaneously in the
given equation. Reaction in which the same compound is reduced and oxidised is known as
disproportionation reactions. Thus, it can be said that the alkaline decomposition of cyanogen is an
example of disproportionation reaction

Question 8.17: 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) +2H2O(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?
Answer : 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+ .

Question: 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?
Ans : 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.
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 .

Q8.24: 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.
Answer: 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
oxidation states.
(b)Mn, Cu, and Ga can show disproportionation reactions as these elements can exist in three or more
oxidation states.

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Question 8.5 (Few are exception)
Calculate the oxidation number of sulphur, chromium and nitrogen in H2SO5, Cr2O72– CrO5 and NO3-.
Suggest structure of these compounds. Count for the fallacy.

Question 8.15: Justify giving reactions that among halogens, fluorine is the best oxidant and among
hydrohalic compounds, hydroiodic acid is the best reductant.
Answer : F2 can oxidize Cl– to Cl2, Br– to Br2, and I– to I2 as:
F2 + 2X─ → 2F ─ + X2 ( X = Cℓ , Br , I )
Cℓ2 + 2X─ → 2Cℓ ─ + X2 ( X = Br , I )
Br2 + 2I─ → 2Br ─ + I2
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 + 2Cu2+ → Cu2I2 + I2
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.

Q: (X)MnO4─ + (Y) H2O2 → 2Mn2+ + 5H2O + 9O2 + (Z) e─

In this reaction, value of (X), (Y) and (Z) are
(a) 2, 5, 6
(b) 5, 2, 9
(c) 3, 5, 5
(d) 2, 6, 6

Q2: 5H2O2 + (X) ClO2 + 2OH─ → (X) Cl─ + (Y) O2 + 6H2O

The reaction is balanced if
(a) X = 5, Y = 2
(b) X = 2, Y = 5
(c) X = 4, Y = 10
(d) X = 5, Y = 5

Q3. Consider the following reaction:

The value’s of x, y and z in the reaction are, respectively :

(a) 5, 2 and 16
(b) 2, 5 and 8
(c) 2, 5 and 16
(d) 5, 2 and 8