EXPERT CHEMISTRY CLASSES BY JT SIR Redox Reactions 1

7 REDOX REACTIONS

CLASSICAL VIEWS REGARDING OXIDATION AND REDUCTION

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OXIDATION REDUCTION

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+ Oxygen – Oxygen
+ Electronegative element – Electronegative element

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– Electro positive element + Electro positive element
– Hydrogen + Hydrogen
– Electron + Electron

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Inc in Oxidation Number Dec in Oxidation Number

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MODERN OR ELECTRON TRANSFER CONCEPT OF OXIDATION AND
REDUCTION
Oxidation is defined as a chemical reaction in which a substance (atom, ion or molecule) loses one
or more electrons and is thus converted into more electropositive or less electronegative state.

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Reduction, according to this concept, is a chemical reaction in which a substance gains one or more
electrons and is thus converted into less electropositive or more electronegative state.
The substance which loses the electrons is said to be oxidized which gains electrons is said to be reduced.

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Franklin used the terms de-electronation for oxidation and electronation for reduction.
Thus :

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Oxidation is de-electronation and reduction is electronation.

REDOX REACTION

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1. An overall reaction which involves both oxidation and reduction simultaneously is called an
oxidation-reduction reaction or redox reaction.
2. The two reactions into which a redox reaction can be broken are called half reactions.
3. The half reaction which represents oxidation is called oxidation half-reaction while that which
represents reduction is called reduction half-reaction.
4. The overall (i.e., net) reaction is obtained by adding the two half-reactions.
SnCl2 + 2FeCl3  → SnCl4 + 2FeCl2
(Molecular reaction)
Oxidation half reaction :
Sn2+  → Sn4+ + 2e– (Oxidation of Sn2+ to Sn4+)
Reduction half reaction :
[Fe3+ + e–  → Fe2+] × 2 (Reduction of Fe3+ to Fe2+)
Redox reaction : Sn2+ + 2Fe3+ →Sn4+ + 2Fe2+

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 2 Redox Reactions EXPERT CHEMISTRY CLASSES BY JT SIR

OXIDISING AND REDUCING AGENTS

The substance which undergoes reduction is called an oxidizing agent or oxidant while that which undergoes

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oxidation is called a reducing agent or reductant. Oxidising agent brings about oxidation while reducing brings

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about the reduction.

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OXIDANTS OR OXIDISING AGENTS
According to the electronic concept, oxidizing agent is a substance which contains an element which gains electrons

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or a substance which contains an element whose oxidation number decreases in chemical reactions.
REDUCTANTS OR REDUCING AGENTS

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On the electronic concept, a reducing agent is a substance which contains an element that yields electrons or it is a
substance which contains an element which oxidation number increases in chemical reactions. Thus :

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Oxidising agent (or oxidant) is an electron acceptor and reducing agent (or reductant) is electron donor.
OXIDATION AND REDUCTION OCCURS SIMULTANEOUSLY
Oxidation involves loss of electrons and reduction involves gain of electrons, it is evident that if one substance
loses electrons, another substance at the same time must gain electrons because electrons cannot be the products

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in any chemical change. This means that in any process, oxidation can occur only if reduction is also taking
place side by side and vice versa. Thus, neither oxidation, nor reduction can occur alone. Both the processes

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are complementary like give and take and proceed simultaneously. That is why chemical reactions involving
reduction-oxidation are called redox reactions.

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OXIDATION NUMBER
The number of electrons which the atom of an element loses or gains in going from the free element in its natural

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state to its new state in that particular compound is called the oxidation number (O.N.) of the element in that
compound.
General rules for finding oxidation no :
+1 +2 +3 +4 to –4 +5 to –3 +6 to –2 +7 to –1
Li Be B C N O F
Na Mg Al Si P S Cl
K Ca Ga Ge As Se Br
Rb Sr In +1 Sn Sb Te I
Cs Ba Tl +1 Pb Bi Po At
Fr Ra

RULES FOR ASSIGNING THE OXIDATION NUMBER

The following rules are applied to determine the oxidation number of an atom in an ion or a molecule.
1. The oxidation number of all the atoms of different elements in their respective elementary
states and allotropic forms is taken to be zero. For example, in

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 EXPERT CHEMISTRY CLASSES BY JT SIR Redox Reactions 3

N2,Cl2,H2,He,P4,S8,O2,O3,C (diamond or graphite) Br2 Na, Fe, Ag etc., the oxidation number of each
atom is zero.
2. The oxidation number of a monoatomic ion is the same as the charge on it. For example,
oxidation numbers of Na+, Mg2+ and Al3+ ions are + 1, + 2 and + 3 respectively while those of Cl-,
S2- and N3- are – 1, – 2 and – 3 respectively.
3. The oxidation number of hydrogen is + 1 when combined with non-metals and is – 1 when
combined with active metals called metal hydrides such as LiH, KH, MgH2,CaH2 etc. e.g.,
Na +1 H −1.
4. The oxidation number of oxygen is – 2 in most of its compounds, except in peroxides like H2O2,
BaO2 etc., where it is – 1. Other interesting exceptions are found in the compounds : OF2 (oxygen
difluoride) and O2F2(dioxygen difluoride) where the oxidation number of oxygen are + 2 and +1
respectively. This is due to the fact that fluorine being the most electronegative element known has
always an oxidation number of – 1.
For oxygen
In peroxides ( O22–) O.N. = –1

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In superoxides ( O2–) O.N. = -1/2

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In OF2 O.N. = +2

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In O2F2 O.N. = +1
Otherwise O.N. = –2

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5. For Halogens
F - always (–1)
Cl
Br Generally (–1)

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I but with O2, shows (+ve) number.

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Note :
(i) Sometimes, oxidation numbers have such values which at first sight appears strange. For
example, the oxidation number of carbon in cane sugar (C12H22O11), glucose (C6H12O6),
dichloromethane, etc., is zero
(a) Cane sugar (C12H22O11) (b) Glucose (C6H12O6)

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12 × x + 22 × 1 + 11(–2) = 0 6 × x + 12 × 1 + 6(–2) = 0
12x + 22 – 22 = 0 6x + 12 – 12 = 0

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So x=0 So x = 0
(c) Dichloromethane (CH2Cl2)

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x + 2 × 1 + 2(–1) = 0
x+2–2=0 So x = 0

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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.
DIFFERENCES BETWEEN VALENCY AND OXIDATION NUMBER
Valency Oxidation number
1. Valency is the combining capacity of the element. 1. Oxidation number is the residual charge
It is expressed as the number of hydrogen atoms which an atom has or appears to have
(or double the number of oxygen atoms) which when the other atoms from the molecule
combine with one atom of the element. are removed as ions by counting the shared
electrons with more electronegative atoms.

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2. It is a number only and does not carry any plus 2. It refers to the charge, it can be positive,
or minus sign. For example, in CO2, the valency negative or zero. For example, in CO2 the
of carbon is 4 and that of oxygen is 2. oxidation number of carbon is +4 and that of
oxygen is -2.
3. The valency of an element is always a whole 3. Oxidation number may have fractional
number. value. For example, oxidation number of
sulphur in Na2S4O6 is +2.5.
4. Many elements like C, N and O exhibit constant 4. Even elements like C, N, O which exhibit
valency. constant valency can have variable oxidation
numbers. For example, valency of carbon is
4 but its oxidation number can vary from -4
to +4 as shown below :
-4 –2 0 +2 +4
CH4, CH3Cl, CH2Cl2, CHCl3, CCl4

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THE PARADOX OF FRACTIONAL OXIDATION NUMBER

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1. Sometimes, we come across with certain compounds in which the oxidation number of a particular
element in the compound is in fractional. Examples are :
C3O2 [where oxidation number of carbon is (4/3)],
Br3O8 [where oxidation number of bromine is (16/3)] and Na2S4O6 (where oxidation number of

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sulphur is 2.5).

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2. The idea of fractional oxidation number is unconvincing to us, because electrons are never shared/
transferred in fraction. Actually this fractional oxidation state is the average oxidation state
of the element under examination and the structural parameters reveal that the element for
whom fractional oxidation state is realised is present in different oxidation states.
3. The element marked with asterisk in each species is exhibiting the different oxidation state (oxidation

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number) from rest of the atoms of the same element in each of the species.
4. This reveals that in C3O2, two carbon atoms are present in +2 oxidation state each, whereas the third
one is present in zero oxidation state and the average is 4/3. However, the realistic picture is +2 for

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two terminal carbons and zero for the middle carbon. Likewise in Br3O8, each of the two terminal
bromine atoms are present in +6 oxidation state and the middle bromine is present in +4 oxidation

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state. Once again the average, that is different from reality, is 16/3. In the same fashion, in the
species S4O62–, each of the two extreme sulphurs exhibits oxidation state of +5 and the two middle
sulphurs as zero. The average of four oxidation numbers of sulphurs of the S4O62– is 2.5, whereas

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the reality being + 5,0,0 and +5 oxidation number respectively for each sulphur.
5. The idea of fractional oxidation state should be taken with care and the reality is revealed by
the structures only. Further, whenever we come across with fractional oxidation state of any
particular element in any species, we must understand that this is the average oxidation number
only.
6. In reality (revealed by structures only), the element in that particular species is present in more
than one whole number oxidation states. Fe3O4, Mn3O4, Pb3O4 are some of the other examples of
the compounds, which are mixed oxides, where we come across with fractional oxidation states of
the metal atom. However, the oxidation states may be in fraction as in O2+ and O2– where it is +½
and –½ respectively.
(ii) Fractional values of oxidation numbers are possible as in Na2S4O6, Fe3O4, N3H etc.
Na2S4O6 Fe3O4 N3H
2 × 1 + 4x + 6(–2) = 0 3 × x + 4(–2) = 0 3x + 1 = 0
2 + 4x – 12 = 0 3x – 8 = 0 3x = –1
4x = +10 3x = 8 x = –1/3

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 EXPERT CHEMISTRY CLASSES BY JT SIR Redox Reactions 5

10 8 2
x=+ = 2.5 x= + or + 2
4 3 3
2
Ox. no. of sulphur is + 2.5 Ox. no. of iron is +2 Ox. no. of nitrogen is – 1/3
3

The compound Fe3O4, however, may be made up of FeO and Fe2O3, in which Fe has oxidation
numbers of + 2 and + 3 respectively.
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In Fe3O4, oxidation number is +2 .
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When an element has a fractional oxidation number in a particular compound, this often
means that the compound contains two or more atoms of the element that are not equivalent.
Classification of Redox Reactions

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Redox reactions may be classified into two types :

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(A) Direct redox reactions

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(B) Indirect redox reactions
(A) Direct redox reactions : The reactions in which oxidation and reduction take place in the same

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vessel are termed direct redox reactions. For example,
(i) Reaction between zinc and copper sulphate solution.
(B) Indirect redox reactions : The reactions in which oxidation and reduction take place in different

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vessels are termed indirect redox reactions.
These reactions are the basis of electrochemical cells.

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BALANCING OF REDOX EQUATION
It is done in two ways :
1. HALF-REACTION METHOD
(ION EXCHANGE METHOD)

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2. OXIDATION NUMBER METHOD

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(a) In writing equations for oxidation-reduction reactions, just as for other reactions, the compositions
and formulas must be known for the substances that react and for the products that are formed. The
oxidation number method is now best illustrated in the following steps :

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Step 1: Write the correct formula for each reactant and product.
Step 2: Identify atoms which undergo change in oxidation number in the reaction by assigning the

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oxidation number to all elements in the reaction.
Step 3: Calculate the increase or decrease in the oxidation number per atom and for the entire
molecule/ion in which it occurs. If these are not equal then multiply by suitable coefficients so that
these become equal. (If you realise that two substances are reduced and nothing is oxidised or vice-
versa, something is wrong. Either the formulas of reactants or products are wrong or the oxidation
numbers have not been assigned properly).
Step 4: Ascertain the involvement of ions if the reaction is taking place in water, add H+ or H– ions
to the expression on the appropriate side so that the total ionic charges of reactants and products are
equal. If the reaction is carried out in acidic solution, use H+ ions in the equation; if in basic solution,
use H– ions.
Step 5 : Make the numbers of hydrogen atoms in the expression on the two sides equal by adding
water (H2O) molecules to the reactants or products. Now, also check the number of oxygen atoms.
If there are the same number of oxygen atoms in the reactants and products, the equation then
represents the balanced redox reaction.
Let us now explain the steps involved in the method with the help of a few problems given below :
(b) HALF REACTION METHOD: In this method, the two half equations are balanced separately
and then added together to give balanced equation.

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Suppose we are to balance the equation showing the oxidation of Fe2+ ions to Fe2+ ions by dichromate
ions (Cr2O7)2– in acidic medium, wherein, Cr2O72– ions are reduced to Cr3+ ions. The following steps
are involved in this task.
Step 1: Produce unbalanced equation for the reaction in ionic form :
Fe2(aq) + Cr2O72–(aq) → Fe3+(aq) + Cr3+(aq) (8.50)

Step 2: Separate the equation into half reactions :
+2 +3
Oxidation half : Fe 2 + (aq ) → Fe3+ (aq ) (8.51)
+6 −2 +3
2− 3+
Reduction half : Cr2O7 (aq ) → Cr (aq ) (8.52)
Step 3: Balance the atoms other than O and H in each half reaction individually. Here the
oxidation half reaction is already balanced with respect to Fe atoms. For the reduction half
reaction, we multiply the Cr3+ by 2 to balance Cr atoms.
Cr2O72–(aq) → 2Cr3+(aq) (8.53)

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Step 4: For reactions occurring in acidic medium, add H2O to balance O atoms and H+ to

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balance H atoms.

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Thus, we get :

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Cr2O72–(aq) + 14H+(aq) → 2Cr3+(aq) + 7H2O(l) (8.54)

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Step 5: Add electrons to one side of the half reaction to balance the charges. If need be, make the
number of electrons equal in the two half reactions by multiplying one or both half reactions by
appropriate coefficients.
The oxidation half reaction is thus rewritten to balance the charge :

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Fe2(aq) → Fe3+(aq) + e–(aq) (8.55)

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Now in the reduction half reaction there are net twelve positive charges on the left hand side and
only six positive charges on the right hand side. Therefore, we add six electrons on the left side.
Cr2O72 − ( aq ) +14 H + ( aq ) + 6e − → 2Cr 3+ ( aq ) + 7 H 2O ( l ) (8.56)
To equalise the number of electrons in both the half reactions, we multiply the oxidation half

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reaction by 6 and write as :
6 Fe 2 ( aq ) → 6 Fe3+ ( aq ) + 6e − ( aq ) (8.57)

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Step 6: We add the two half reactions to achieve the overall reaction and cancel the electrons on
each side. This gives the net ionic equation as :
6 Fe 2 + ( aq ) Cr2O72 − ( aq ) +14 H + ( aq ) + 6 Fe3+ → 2Cr 3+ ( aq ) + 7 H 2O ( l ) (8.58)

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Step 7: Verify that the equation contains the same type and number of atoms and the same charges
on both sides of the equation. This last check reveals that the equation is fully balanced with respect

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to number of atoms and the charges.
For the reaction in a basic medium, first balance the atoms as is done in acidic medium. Then for
each H+ ion, add an equal number of OH– ions to both sides of the equation. Where H+ and OH–
appear on the same side of the equation, combine these to give H2O.

REDOX REACTIONS AS THE BASIS FOR TITRATIONS

1. In redox systems, the titration method can be adopted to determine the strength of a reductant/
oxidant using a redox sensitive indicator.
The usage of indicators in redox titration is illustrated below:
(i) In one situation, the reagent itself is intensely coloured, e.g., permanganate ion, MnO4–. Here MnO4–
acts as the self indicator. The visible end point in this case is achieved after the last of the reductant
is oxidised and the first lasting tinge of pink colour appears at MnO4– concentration as low as 10–6
mol dm–3 (10–6 mol L–1). This ensures a minimal ‘overshoot’ in colour beyond the equivalence
point, the point where the reductant and the oxidant are equal in terms of their mole stoichiometry.
(ii) If there is no dramatic auto-colour change (as with MnO4– titration), there are indicators which are
oxidised immediately after the last bit of the reactant is consumed, producing a dramatic colour

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 EXPERT CHEMISTRY CLASSES BY JT SIR Redox Reactions 7

change. The best example is afforded by Cr2O72–, which is not a self-indicator, but oxidises the
indicator substance diphenylamine just after the equivalence point to produce an intense blue
colour, thus signalling the end point.
(iii) There is yet another method which is interesting and quite common. Its use is restricted to those
reagents which are able to oxidise I– ions, say, for example, Cu(II) :
2Cu 2 + ( aq ) + 4 I − ( aq ) → Cu2 I 2 ( s ) + I 2 ( aq ) (8.59)
This method relies on the facts that iodine itself gives an intense blue colour with starch and has a
very specific reaction with thiosulphate ions (S2O32–), which too is a redox reaction :
I 2 ( aq ) + 2 S 2O32 − ( aq ) → 2 I − ( aq ) + S 4O62 − ( aq ) (8.60)
I2, though insoluble in water, remains in solution containing KI as KI3.
On addition of starch after the liberation of iodine from the reaction of Cu2+ ions on iodide ions,
an intense blue colour appears. This colour disappears as soon as the iodine is consumed by the
thiosulphate ions. Thus, the end-point can easily be tracked and the rest is the stoichiometric
calculation only.

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LIMITATIONS OF CONCEPT OF OXIDATION NUMBER

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As you have observed in the above discussion, the concept of redox processes has been evolving with time. This
process of evolution is continuing. In fact, in recent past the oxidation process is visualised as a decrease in electron

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density and reduction process as an increase in electron density around the atom(s) involved in the reaction.
REDOX REACTIONS AND ELECTRODE PROCESS
Galvanic or Voltaic cells are those in which chemical reactions are used to produce electrical energy.

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A cell or a device in which energy liberated during a redox reaction is obtained in the form of electric current

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is known as an electrochemical cell.
It is also called Galvanic cell after Luigi Galvani (1780) or a voltaic cell after Alessandro Volta (1800) who first
experimented with the conversion of chemical energy into electrical energy.

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A redox couple may be defined as combination of the oxidized and reduced forms of the same substance taking
part in an oxidation or reduction half reaction.
CONSTRUCTION OF ELECTROCHEMICAL CELL
1. It consists of two half cells
2. The two containers containing metal rods dipped in their respective salt solutions are called half
cells.
3. In one of the half cells, oxidation takes place while the reduction takes place in the other. The
half cell in which oxidation takes place is called the oxidation half cell while the other in which,
reduction takes place is called the reduction half cell.
4. Electrons flow from anode to cathode in external circuit
5. The direction of flow of current is opposite to that of electron

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6. The solutions in the two beakers are connected by an inverted U-tube known as salt bridge.

SALT BRIDGE
The solutions in the two beakers are connected by an inverted U-tube known as salt bridge.
The tube is filled with a solution an electrolyte such as KNO3, KCl or NH4NO3 which does not undergo a chemical
change during the process.
Gelatin or agar-agar is also added to the electrolyte to have a semi-solid mass.
The ends of the V-tube are usually plugged with some porous material such as glass wool or cotton.
Salt bridge allows the movement of ions from one solution to the other without mixing of the two solutions.
Sometimes, instead of a salt bridge, porous partition is used to separate the two solutions.
FUNCTIONS OF THE SALT BRIDGE
(1) It connects the solutions in two half cells and completes the cell circuit.
(2) The salt bridge prevents the physical contact between two electrolytic solutions
(3) It maintains the electrical neutrality

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(4) In the absence of salt bridge, transference of electrons from oxidation half-cell to reduction half-cell
takes place just for a moment

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SALIENT FEATURES OF AN ELECTROCHEMICAL CELL
Some important features of an electrochemical cell are summarized below :

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(i) The zinc rod at which the oxidation occurs is called the anode while the copper rod at which the
reduction takes place is called the cathode.
(ii) The overall reaction taking place in an electrochemical cell is due to two half reaction; one occurring

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in each beaker. Each beaker constitutes a half cell also called the electrode or the redox couple.
Thus, a half cell or an electrode consists of a metal rod dipped in the solution of its own ions.

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(iii) The reaction taking place in a half cell is called a half cell reaction. Thus, equations (i) and (ii)
represent two half cell reactions.
(iv) The half-cell reaction occurring at anode is called oxidation half-cell reaction while that occurring
at the cathode is called reduction half cell reaction. For example, equation (i) represents oxidation
half cell reaction whereas equation (ii) represents reduction half cell reaction. The overall redox

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reaction is then obtained by adding the two half cell reactions.
(v) The two half reactions always take place simultaneously, i.e., half cell reactions cannot take place
independently.

0 1 DANIELL CELL
The Galvanic cell in which Zn – CuSO4 reaction takes place is called Daniell cell. In the commercial
form of this cell, salt bridge is replaced by a porous pot through which the SO42– -ions migrate from

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copper sulphate solution to the zinc sulphate solution.
The EMF of Daniell cell is 1.1 volts
Daniell cell is thus represented as
Zn(s) | ZnSO4 (1M) || CuSO4 (1M) | Cu(s)
Daniell cell : Daniell cell is an example of a galvanic cell. It consists of two half-cells; one
containing an electrode of Zn dipping in 1 molar solution of ZnSO4.
The chemical reactions in the cell are:
Zn  → Zn 2 + 2e − and Cu 2 + + 2e − 
→ Cu
A voltaic cell in which the reaction,
Zn( s ) + CuSO4 (aq )  → ZnSO4 (aq ) + Cu ( s ) can be constructed as follows:
We take zinc sulphate solution and put a zinc rod or strip in it. We also take copper sulphate solution
in another beaker and put a copper rod or strip in it.
These represent the species in the oxidation and reduction half reactions.
The oxidised and reduced forms of a substance present together and which take part in an oxidation
or reduction half reaction is called a redox couple.

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ELECTRODE POTENTIAL
The electrical potential difference set up between the metal and its solution is known as electrode
potential. The electrode potential may be of two types :
(i) Oxidation potential : The tendency of an electrode to loose electrons or to get oxidized is called its
oxidation potential.
eg. Zn - 2e- → Zn++
(ii) Reduction potential : The tendency of an electrode to gain electrons or to get reduced is called its
reduction potential. eg.
Cu++ + 2e- → Cu
Note (Numerical point) : Oxidation potential & reduction potential have difference of sign (-ve or
+ve) only, otherwise their value is same.
eg. Oxidation potential of Zn = +0.76 V
Reduction potential of Zn = –0.76 V
Electrode potential depends upon :
(i)

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The nature of the metal and its ions.
(ii) Concentration of the ions in the solution.

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(iii) Temperature.

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Standard electrode potential : The electrical potential difference set up b/w metal and its solution when molar
concentration of solution is 1 and temperature is 25oC.

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Standard Hydrogen Electrode : It consists of platinum wire sealed in a glass tube and has a platinum foil attached
to it. The foil is coated with finely divided platinum and act as platinum electrode. It is dipped into an acid solution
containing H+ in 1M conc. [1M HCl]. Pure H2 gas at 1 atm and 298 K is continuously passed into solution. The

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surface of platinum foil act as site for the reaction. The following reaction occur in this cell depending upon whether
it act as anode or as cathode.

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If S.H.E. acts as anode
H2 - 2e- → 2H+
If S.H.E. acts as cathode
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2H+ + 2e- → H2

H2   2H+ + 2e-
The electrode potential of an electrode can be determined by connecting this half cell with a standard hydrogen
electrode. This S.H.E. is also regarded as reversible electrode. The electrode potential of the S.H.E. is taken as zero.
The electrode potential of a metal electrode as determined with respect to a standard or normal hydrogen electrode
is called standard electrode potential (E0).

ELECTROCHEMICAL SERIES
Li H
K Cu
Ba Hg displaces H2 from H2O (cold)

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Sr Ag displaces H2 from H2O

Ca Pt
Na Au
Mg I
Al Br
Zn Cl
Fe F
Ni
Sn
Pb

For metals For non metals

Less reduction potential More reduction potential
↓ ↓

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Electron loose easily Electron accept easily

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↓ ↓

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More reactive More reactive
↓ ↓

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Easily oxidized Easily reduced
↓ ↓

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Powerful reducing agent Powerful oxidising agent
↓ ↓

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It will displace the other metal which has It will displace the other Non metal which has
higher reduction potential. lower reduction potential.

Applications of Electrochemical Series

(i) Oxidising and Reducing agent tendencies : All substances appearing at the top of the series

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behave as good reducing agent. Substance present at the bottom of the series are good oxidizing
agent.

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(ii) Comparison of reactivities of metals. A metal present at higher position in the series can displace
other metal present below it from the solution of their salts.

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* In case of non-metals, properties of become reverse. Non metals present in bottom of series
displace other nonmetal.
(iii) Predicting whether a metal can liberate Hydrogen from the acid or not. Those metal can liberate

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hydrogen from the acid which have negative values of reduction potential. Or
Metals present above Hydrogen in E.C.S can displace Hydrogen from acid.
eg. Zn + H2SO4 → ZnSO4 + H2

COMPETITIVE ELECTRON TRANSFER REACTIONS

Take a rod of metallic zinc and clean it well with a sand paper. Now place it in a solution of copper nitrate in a beaker
for about one hour.
Zn( s ) + Cu 2 + (aq ) 
→ Zn 2 + (aq ) + Cu ( s )
The reaction between metallic zinc and the aqueous solution of copper nitrate is
In this reaction, zinc loses electrons to form Zn2+ ions. Therefore, zinc gets oxidized. Evidently, if zinc is oxidized,
losing electrons, there must be some species present in the solution which must get reduced by accepting the
electrons lost by zinc. This species is Cu2+ ions, provided by dissociation of copper nitrate.
The following changes are observed :
(i) Zinc rod gradually starts dissolving.
(ii) Reddish brown copper metal starts depositing on the zinc rod.
(iii) The blue colour of copper nitrate solution starts fading and ultimately becomes colourless.

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 EXPERT CHEMISTRY CLASSES BY JT SIR Redox Reactions 11

The formation of Zn2+ ions, among the products, can be easily detected when the colour of the
solution due to Cu2+ ions starts fading.
If hydrogen sulphide H2S is passed through the solution containing Zn2+ ions, formation of white
zinc sulphide, ZnS can be seen.
(iv) The reaction is exothermic and the solution becomes hot.
(v) The solution remains electrically neutral.
Let us now investigate the state of equilibrium of reaction
(i) For this purpose, place a rod of copper in a zinc sulphate solution. No visible reaction is noticed and
all attempts to detect the presence Cu2+ ions in solution by passing H2S gas fail since no black ppt.
of cupric sulphide CuS is formed.
(ii) Let us now extend the electron transfer reaction to copper metal and silver nitrate solution. For
this purpose, place a copper rod in silver nitrate solution.
The following reaction occurs and the solution acquires blue colour due to the formation of Cu2+
ions.
e-

4
Oxidised (loss of 2 )

R
Cu (s) + 2 Ag+ (aq) Cu2+ (aq) + 2Ag (s)

I 2
e-
Reduced (gain of 2 )

S 64
Here, copper, Cu (s) is oxidized to Cu2+ (aq) while Ag+ is reduced to silver metal, Ag (s). The
equilibrium greatly lies in favour of Cu2+ (aq) and Ag (s).
(iii) For purpose of comparison, let us now place a rod of cobalt metal in nickel sulphate solution. The

T
following reaction occurs :

J 42
5
● At equilibrium, chemical tests reveal that both Ni2+ and Co2+ (aq) are present in moderate
concentration. In other words, in this case, neither the reactants, Co2+ (s) and Ni2+(aq) nor the

1
products, Co2+ (aq) and Ni2+(s) are greatly favoured.
● This competition for loss or gain of electrons by metals or their metal ions is similar to the
competition between various acids to lose a H+ in water. Therefore, we can develop a table in which

0
metals and their ions are listed according to their tendency to lose or gain electrons
● The results of experiments discussed above reveal that zinc releases electrons to copper and copper

9
releases electrons to silver.
Therefore, the electron-releasing tendency of these three metals is in the order : Zn > Cu > Ag.
By conducting more experiments between various other metals and their combinations with suitable
metals ions, we have developed a metal activity series. With the help of this activity series, we can
construct a class of cells in which chemical reactions are used as a source of electrical energy. These
cells are called Galvanic cells

TYPES OF REDOX REACTION

1. COMBINATION REACTIONS. A combination reaction may be denoted in the manner:
A+B→C
Either A and B or both A and B must be in the elemental form for such a reaction to be a redox
reaction.
All combustion reactions, which make use of elemental dioxygen, as well as other reactions
involving elements other than dioxygen, are redox reactions.
Examples of this category are:
0 0 +4 − 2
C ( s ) + O2 ( g ) 
∆
→ CO2 ( g ) (1)

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 12 Redox Reactions EXPERT CHEMISTRY CLASSES BY JT SIR

0 0 +2 − 3
Mg ( s ) + N 2 ( g ) 
∆
→ Mg3 N 2 ( s ) (2)
−4 +1 0 +4 − 2 +1 − 2
CH 4 ( g ) + 2O2 ( g ) 
∆
→ CO2 ( g ) + 2 H 2O ( l ) (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 :
+1 − 2 0 0
2 H 2O ( l ) 
∆
→ 2 H 2 ( g ) + O2 ( g ) (4)
+1 −1 0 0
2 NaH ( s ) 
∆
→ 2 Na ( s ) + H 2 ( g ) (5)
+1+ 5 − 2 +1 −1 0
2 KClO3 ( s )  → 2 KCl ( s ) + 3O2 ( g ) (6)

4
∆

R
It may carefully be noted that there is no change in the oxidation number of hydrogen in methane

I
under combination reactions and that of potassium in potassium chlorate in reaction (5).

2
This may also be noted here that all decomposition reactions are not redox reactions.
For example, decomposition of calcium carbonate is not a redox reaction.

S 64
+2 + 4 − 2 +2 − 2 +4 − 2
CaCO3 ( s ) 
→ CaO ( s ) + CO2 ( g )
∆

3. DISPLACEMENT REACTIONS.

T
In a displacement reaction, an ion (or an atom) in a compound is replaced by an ion (or an atom) of

J 42
another element.
It may be denoted as:
X + YZ → XZ + Y
Displacement reactions fit into two categories:
(a) metal displacement
(b) non-metal displacement

5
(a) METAL DISPLACEMENT : A metal in a compound can be displaced by another metal in the
uncombined state.

1
Metal displacement reactions find many applications in metallurgical processes in which pure
metals are obtained from their compounds in ores.
A few such examples are:

0
+2 + 4 − 2 0 0 +2 + 4 − 2
CuSO4 ( aq ) + Zn ( s ) → Cu ( s ) + ZnSO4 ( aq )

9
+5 − 2 0 0 +2 −1
V2O5 ( s ) + 5Ca ( s ) 
∆
→ Ti ( s ) + 2 MgCl2 ( s )
+4 −1 0 0 +2 −1
TiCl4 ( l ) + 2 Mg ( s ) 
∆
→ Ti ( s ) + 2 MgCl2 ( s )
+3 − 2 0 +3 − 2 0
Cr2O3 ( s ) + 2 Al ( s ) 
∆
→ Al2O3 ( s ) + 2Cr ( s )
In each case, the reducing metal is a better reducing agent than the one that is being reduced which
evidently shows more capability to lose electrons as compared to the one that is reduced.
(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
2 Na ( s ) + 2 H 2O ( l ) → 2 NaOH ( aq ) + H 2O ( g )
0 +1 − 2 +1 − 2 +1 0
Ca ( s ) + 2 H 2O ( l ) → 2 NaOH ( aq ) + H 2 ( g )

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 EXPERT CHEMISTRY CLASSES BY JT SIR Redox Reactions 13

Less active metals such as magnesium and iron react with steam to produce dihydrogen gas:
0 +1 − 2 +2 − 2 +1 0
Mg ( s ) + 2 H 2O ( l ) 
∆
→ Mg ( OH )2 ( s ) + H 2 ( g )
0 +1 − 2 +3 − 2 0
2 Fe ( s ) + 3H 2O ( l ) 
∆
→ Fe2O3 ( s ) + 3H 2 ( g )
Many metals, including those which do not react with cold water, are capable of displacing
hydrogen from acids. Dihydrogen from acids may even be produced by such metals which do
not react with steam. Cadmium and tin are the examples of such metals. A few examples for the
displacement of hydrogen from acids are:
0 +1 −1 +2 −1 0
Zn ( s ) + 2 HCl ( aq ) → ZnCl2 ( aq ) + H 2 ( g )
0 +1 −1 +2 −1 0
Mg ( s ) + 2 HCl ( aq ) → MgCl2 ( aq ) + H 2 ( g )
0 +1 −1 +2 −1 0

4
Fe ( s ) + 2 HCl ( aq ) → FeCl2 ( aq ) + H 2 ( g )

R
These reactions are used to prepare dihydrogen gas in the laboratory. Here, the reactivity of metals

I 2
is reflected in the rate of hydrogen gas evolution, which is the slowest for the least active metal
Fe, and the fastest for the most reactive metal, Mg.

S 64
Very less active metals, which may occur in the native state such as silver (Ag), and gold (Au) do
not react even with hydrochloric acid.
Discussed above that the metals – zinc (Zn), copper (Cu) and silver (Ag) through tendency to lose

T
electrons show their reducing activity in the order Zn > Cu >Ag. Like metals, activity series also
exists for the halogens. The power of these elements as oxidising agents decreases as we move

J 42
down from fluorine to iodine in group 17 of the periodic table. This implies that fluorine is so
reactive that it can replace chloride, bromide and iodide ions in solution. In fact, fluorine is so
reactive that it attacks water and displaces the oxygen of water :
+1 − 2 0 +1 −1 0
2 H 2O ( l ) + 2 F2 ( g ) → 4 HF ( aq ) + O2 ( g )

5
It is for this reason that the displacement reactions of chlorine, bromine and iodine using
fluorine are not generally carried out in aqueous solution. On the other hand, chlorine can

1
displace bromide and iodide ions in an aqueous solution as shown below :
0 +1 −1 +1 −1 0
Cl2 ( g ) + 2 KBr ( aq ) → 2 KCl ( aq ) + Br2 ( l )

0
0 +1 −1 +1 −1 0
Cl2 ( g ) + 2 KI ( aq ) → 2 KCI ( aq ) + I 2 ( s )

9
As Br2 and I2 are coloured and dissolve in CCl4, can easily be identified from the colour of the
solution. The above reactions can be written in ionic form as :
0 −1 −1 0
Cl2 ( g ) + 2 Br − ( aq ) → 2 Cl − ( aq ) + Br2 ( l ) ...(3)
0 −1 −1 0
Cl2 ( g ) + 2 I − ( aq ) → 2CI − ( aq ) + I 2 ( s ) ...(4)
Reactions (3) and (4) form the basis of identifying Br– and I– in the laboratory through the test
popularly known as ‘Layer Test’. It may not be out of place to mention here that bromine likewise
can displace iodide ion in solution :
0 −1 −1 0
Br2 ( l ) + 2 I − ( aq ) → 2 Br − ( aq ) + I 2 ( s ) ...(5)
The halogen displacement reactions have a direct industrial application. The recovery of halogens
from their halides requires an oxidation process, which is represented by :
2 X − → X 2 + 2e − ...(6)
here X denotes a halogen element. Whereas chemical means are available to oxidise Cl–1, Br– and
I–, as fluorine is the strongest oxidizing agent; there is no way to convert F– ions to F2 by chemical

JT SIR CHEMISTRY CLASSES: 12/26 BASEMENT, WEST PATEL NAGAR, NEW DELHI # 9015426424, 8470010621
 14 Redox Reactions EXPERT CHEMISTRY CLASSES BY JT SIR

means. The only way to achieve F2 from F– is to oxidise electrolytically, the details of which you
will study at a later stage.
4. DISPROPORTIONATION REACTIONS
Disproportionation reactions are a special type of redox reactions. In a disproportionation
reaction an element in one oxidation state is simultaneously oxidised and reduced. One of the
reacting substances in a disproportionation reaction always contains an element that can exist in
at least three oxidation states. The element in the form of reacting substance is in the intermediate
oxidation state; and both higher and lower
oxidation states of that element are formed in the reaction. The decomposition of hydrogen peroxide
is a familiar example of the reaction, where oxygen experiences disproportionation.
+1 −1 +1 − 2 0
2 H 2O2 ( aq ) → 2 H 2O ( l ) + O2 ( g ) (7)
Here the oxygen of peroxide, which is present in –1 state, is converted to zero oxidation state in O2
and decreases to –2 oxidation state in H2O.

4
Phosphorous, sulphur and chlorine undergo dispropor-tionation in the alkaline medium as

R
shown below:

I
+1

2
0 −3
P4 ( s ) + 3OH − ( aq ) + 3H 2O ( l ) → PH 3 ( g ) + 3H 2 PO2− ( aq ) (8)
0 +1 −1

S 64
Cl2 ( g ) + 2 OH − ( aq ) → ClO − ( aq ) + Cl −
( aq ) + H 2O ( l ) (9)
The reaction (8.48) describes the formation household bleaching agents. The hypochlorite ion
(ClO–) formed in the reaction oxidises the colour-bearing stains of the `substances to colourless

T
compounds.
It is of interest to mention here that whereas bromine and iodine follow the same trend as exhibited

J 42
by chlorine in reaction (8.48), fluorine shows deviation from this behaviour when it reacts with
alkali. The reaction that takes place in the case of fluorine is as follows :
2 F2 ( g ) + 2OH − ( aq ) → 2 F − ( aq ) + OF2 ( g ) + H 2O ( l )
(It is to be noted with care that fluorine in reaction (8.49) will undoubtedly attack water to produce

5
some oxygen also). This departure shown by fluorine is not surprising for us as we know the
limitation of fluorine that, being the most electronegative element, it cannot exhibit any positive
oxidation state. This means that among halogens, fluorine does not show a disproportionation

1
tendency. Lit quos consero velitias quas non comnim nis con pro volorib usaectas nossum quam
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nusam, ut omnihil isto vita dolorep eliciat issimet fuga. Itatur aborest, te officidusam volupta eribusa

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 EXPERT CHEMISTRY CLASSES BY JT SIR Redox Reactions 15

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4
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I 2
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S 64
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T
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J 42
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5
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1
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9
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 16 Redox Reactions

NCERT Exercise
IDENTIFY THE SPECIES UNDERGOING
EXPERT CHEMISTRY CLASSES BY JT SIR
OXIDATION AND REDUCTION REACTION
1. In the reactions given below, identify the species undergoing oxidation and reduction:
(i) H2S(g) + Cl2(g) → 2HCl(g) + S(s)
(ii) 3Fe3O4(s) + 8Al(s) → 9Fe(s) + 4Al2O3(s)
(iii) 2Na(s) + H2(g) → 2NaH(s)
Sol.1 (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.
2. Justify that the reaction :
2Na(s) + H2(g) → 2NaH(s) is a redox change.

4
Sol.2 Since in the above reaction the compound formed is an ionic compound, which may also be represented

R
as Na+H–(s), this suggests that process is :

I 2
2Na(s) → 2Na+(g) + 2e–
and the other half reaction is:

S 64
H2(g) + 2e– → 2H–(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.

3.

Sol.3
T
J 42
STOCK NOTATION
Using Stock notation, represent the following compounds:
HAuCl4, Tl2O, FeO, Fe2O3, CuI, CuO, MnO and MnO2.
By applying various rules of calculating the oxidation number of the desired element in a compound, the

5
oxidation number of each metallic element in its compound is as follows :
HAuCl4 → Au has 3

1
Tl2O → Tl has 1
FeO → Fe has 2

0
Fe2O3 → Fe has 3
CuI → Cu has 1

9
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.
4. Justify that the reaction:
 Redox Reactions 17

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.
Sol.4 Let us assign oxidation number to each of the species in the reaction under examination. This results into:
+1 −2 +1 −2 0 +4 − 2
2Cu 2 O( s ) + Cu 2S( s ) → 6Cu( s ) + SO 2
EXPERT
WeCHEMISTRY CLASSES
therefore, conclude thatBY
in JT
thisSIR
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.

DISPROPORTIONATION
5. Which of the following species, do not show disproportionation reaction and why ?
ClO − , ClO −2 , ClO −3 and ClO 4−
Also write reaction for each of the species that disproportionates.
Sol.5 Among the oxoanions of chlorine listed above, ClO −4 does not disproportionate because in this oxoanion
chlorine is present in its highest oxidation state that is, +7. The disproportionation reactions for the other
three oxoanions of chlorine are as follows :
+1 −1 +5
3ClO − 
→ 2Cl− + ClO3−

R 4
+3 +5 −1
hv
6ClO −2  → 4ClO3− + 2Cl−

I 2
+5 −1 +7
4ClO3− 
→ Cl + 3ClO 4−

S 64
6. Suggest a scheme of classification of the following redox reactions
(a) N2(g) + O2(g) → 2NO(g)

T
(b) 2Pb(NO3)2(s) → 2PbO(s) + 2NO2(g) + 1/2O2(g)
(c) NaH(s) + H2O(l) → NaOH(aq) + H2(g)

J 42
(d) 2NO2(g) + 2OH–(aq) → NO2– (aq) + NO3– (aq) + H2O(l)
Sol.6 In reaction (a), the compound nitric oxide is formed by the combination of the elemental substances,
nitrogen and oxygen; therefore, this is an example of combination redox reactions. The reaction (b)
involves the breaking down of lead nitrate into three components; therefore, this is categorised under

5
decomposition redox reaction. In reaction (c), hydrogen of water has been displaced by hydride ion into
dihydrogen gas. Therefore, this may be called as displacement redox reaction. The reaction (d) involves
disproportionation of NO2 (+ 4 state) into NO2– (+ 3 state) and NO3– (+ 5 state). Therefore reaction (d) is

1
an example of disproportionation redox reaction.
7. Why do the following reactions proceed differently ?

0
Pb3O4 + 8HCl → 3PbCl2 + Cl2 + 4H2O
and

9
Pb3O4 + 4HNO3 → 2Pb(NO3)2 + PbO2 + 2H2O
Sol.7 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 (oxidizing 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)
 18 Redox Reactions

+4 −1 +2 0
PbO 2 + 4HCl → PbCl2 + Cl2 + 2H 2 O (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
EXPERT CHEMISTRY CLASSES BY JT SIR
with HCl.
8. Why do the following reactions proceed differently ?
Pb3O4 + 8HCl → 3PbCl2 + Cl2 + 4H2O
and
Pb3O4 + 4HNO3 → 2Pb(NO3)2 + PbO2 + 2H2O
Sol.8 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 (oxidizing 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
PbO 2 + 4HCl → PbCl2 + Cl2 + 2H 2 O (redox reaction)
Since HNO3 itself is an oxidising agent therefore, it is unlikely that the reaction may occur between PbO2

4
and HNO3. However, the acid-base reaction occurs between PbO and HNO3 as :

R
2PbO + 4HNO3 → 2Pb(NO3)2 + 2H2O

I 2
It is the passive nature of PbO2 against HNO3 that makes the reaction different from the one that follows
with HCl.

S 64
T
J 42
1 5
9 0
 EXPERT CHEMISTRY CLASSES BY JT SIR Redox Reactions 19

QUESTIONS ALIKE

Very Short Answer Type Questions

Q.1. Identify the oxidizing agent and the reducing agent in the following reaction
H2S + HNO3  → NO + S + H2O
−2 +5 ( +2) 0
Sol.1 H 2S + HNO3  → NO + S + H 2 O
In the reaction HNO3 is an oxidizing agent it itself gets reduced from +5 to +2. While H2S is an reducing
agent since it itself gets oxidized from –2 to 0.

4
Q.2. In a binary compound of two non-metals, the positive oxidation state is assigned to which metal?

R
Sol.2 Less electronegative metal amongst the two.

I 2
Q.3. What is the oxidation number of C in C6H6 ?

S 64
Sol.3 It is –1.
Q.4. What does negative electrode potential signify?
Sol.4 It signifies that electrode has larger tendency to loose electrons than hydrogen electrode.

T
Q.5. At what concentration of Cu2+(aq), will its electrode potential become equal to its standard electrode

J 42
potential?
Sol.5 At 1 M concentration.
Q.6. Why is anode called oxidation electrode whereas cathode is called reduction electrode?
Sol.6 At anode, loss of electrons takes place, i.e., oxidation takes place whereas at cathode, gain of electrons

5
takes place, i.e., reduction takes place therefore cathode is called reduction electrode and anode is called
oxidation electrode.

1
Q.7. Zn rod is immersed in CuSO4 solution. What will you observe after an hour? Explain your
observation in terms of redox reaction.

0
Sol.7 Zn + CuSO 4  → ZnSO 4 + Cu
The blue colour will get discharged and reddish brown copper metal will get deposited.

9
Q.8. Why can CuSO4 solution not be stored in an iron vessel?
Sol.8 It is because E oFe2+ /Fe = −0.44 V which is lower than that of Cu
E ocell =E oCu 2+ /Cu − E oFe2+ /Fe =+0.34 V − (−0.44 V) =0.78V.
Since, E ocell =+ ve, ∆G =− ve, i.e., reaction will take place.
We cannot store CuSO4 in an iron container.
Q.9. Fe decomposes steam while Cu does not, why?
Sol.9 Fe is more reactive than hydrogen, it has lower reduction potential than hydrogen whereas Cu has higher
reduction potential than H2.
Q.10. What is meant by inert electrolyte used in salt bridge?
Sol.10 Inert electrolyte is an electrolyte which does not react with any of the solution present in two half cells.
Q.11. What is oxidation state of Cr in CrO5 and why?
Sol.11 Cr has +6 oxidation state because it has 6 valence electrons, therefore, can form 6 covalent bonds.

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 20 Redox Reactions EXPERT CHEMISTRY CLASSES BY JT SIR

Q.12. What is meant by oxidation potential of an electrode?

Sol.12 Oxidation potential measures the tendency of an element or anion to lose electrons.
Q.13. What is relationship between standard oxidation potential and standard reduction potential?
Sol.13 Both are equal in magnitude but opposite in sign.
Q.14. Find the oxidation number of Cl in HCl, HClO, ClO −4 , and Ca(OCl)Cl.
Sol.14 Cl in HCl is +1 + x = 0 ⇒ x = –1
Cl in HClO is +1 + x –2 = 0 ⇒ x = +1
Cl in ClO −4 is x – 8 = –1 ⇒ x = +7

4
In there are two chlorine atoms, one of chlorine is in form of Cl– whose oxidation state is –1,

R
other one is in form ClO– (hypochlorite ion) in which oxidation state is +1 (x – 2 = –1 ⇒ x = +1).

I 2
The average oxidation state of two Chlorine atoms in CaOCl2 is 0(–1 + 1 = 0) or (+2 – 2 + 2x = 0) ⇒ x
= 0.

S 64
Q.15. Find the oxidation number of sulphur in S2O . 7
2–

Sol.15 +6, 2x – 14 = –2 ⇒ 2x = 12 ⇒ x = +6.

T
Q.16. Arrange the following in order of increasing oxidation number of iodine. I2, HI, ICl.

J 42
Sol.16 I2 has oxidation number zero, in HI. Iodine has oxidation number –1.
In ICl, iodine has oxidation number +1.
HI, I2, ICl is order of increasing oxidation number.
Q.17. Does the redox reaction in a cell go to completion?

5
Sol.17 No, it is not completed.
Q.18. What happens when a silver plate is dipped in copper sulphate solution?

1
Sol.18 No change will be noticed.
Q.19. What is electronation?

0
Sol.19 The process in which gain of electrons takes place is called electronation.
Q.20. Is the valency of an element, same as its oxidation number?

9
Sol.20 No, they are not always same.
Q.21. In the reaction given below which species is called a spectator iron and why?
Zn(s) + Cu2+(aq) + SO42–(aq)  → Zn2+(aq) + Cu(s) + SO42–(aq)
Sol.21 SO 24 − ion is the spectator ion as it does not participate in the reaction.
Q.22. What is a redox couple?
Sol.22 It is defined as having together the oxidised and reduced forms of a substance taking part in oxidation
or reduction half reactions. They are actually conjugate acid base pairs. We can also defined is as: an
oxidizing and reducing agent which appear on opposite sides of a half equation constitute the redox
couple. A redox couple is usually denoted as Mn+/M (oxidised state / reduced state).
Q.23. What is a disproportionation reaction? Give one example.
Sol.23 It is a type of redox reaction in which a compound of intermediate oxidation state converts into two
different compounds, one of higher and one of lower oxidation states.
Examples:

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 EXPERT CHEMISTRY CLASSES BY JT SIR Redox Reactions 21

4H 3 PO3 
→ 3H 3 PO 4 + PH 3
2HCO3 
−
→ CO32 − + H 2 CO3
Q.24. What is the function of platinum electrode?
Sol.24 Platinum electrode is used for non-metals like hydrogen, chlorine, etc. It being a noble metal and have a
large surface area, all the cell reactions can take place on its surface. It acts as a sink for electron transfer
in the cells.
Q.25. Out of zinc and copper vessel, which one will be more suitable to store 1 M HCl solution?
Sol.25 Copper vessel
[In electrochemical series copper lies above hydrogen].
Q.26. A solution of silver nitrate solution was stirred with iron rod. Will it cause any changes in
concentration of silver and nitrate ions?
Sol.26 Concentration of silver ions will change.

R 4
Q.27. What is the oxidation number of C in C12H22O11?

I
Sol.27 Zero
Q.28.

(b) 3CuO + NH3 

→ 6PH3 + P4H2

(c) 3Br2 + 6NaOH 

2
Select which of the following is not an example of disproportionation reaction.
(a) 5P2H4 

S 64
→ 2N2 + 3H2O + 3Cu
→ 5NaBr + NaBrO3 + 3H2O

T
(d) CuS + 2CuO  → 3Cu + SO2

J 42
Sol.28 In equations (b) and (d) the reactants are not undergoing simultaneous oxidation and reduction. Hence (b)
and (d) are not the examples of disproportionation reactions.
Q.29. Can we store copper sulphate solution in a silver vessel? Explain your answer
(Given : EoCu2+ /Cu = 0.34V; EoAg+ / Ag = 0.80V)

5
Sol.29 Yes, copper sulphate solution can be stored in a silver vessel.
From the given Eo values we find that copper is more reactive than silver. Thus silver cannot displace

1
copper from copper sulphate solution and so the following reaction will not occur.
Cu 2 + (aq ) + Ag( s ) 
→ No reaction

0
Short Answer Type Questions

9
Q.30. Explain the difference between the electromotive force and the potential difference.
Sol.30
S. No. E.M.F. Potential Difference
1 It is the potential difference between the It is difference between the electrode potentials
two electrodes when no current is flowing of two electrodes when current is flowing
through the circuit i.e., in the open circuit. through the circuit.
2 It is the maximum voltage obtainable from It is always less than the e.m.f. of cell.
the cell.
3 The work calculated from e.m.f. is the The work calculated from the potential
maximum work obtainable from the cell. difference is less than maximum work
obtainable from the cell.
4 It is responsible for the flow of steady It is not responsible for the flow of steady
current through the circuit. current through the circuit.
Q.31. Zinc liberates hydrogen from [Link] while copper fails to do so. Why?

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 22 Redox Reactions EXPERT CHEMISTRY CLASSES BY JT SIR

Sol.31 We know zinc has a negative reduction potential Zn2+/Zn = –0.76V and it lies below hydrogen in the
electrochemical series. Therefore, the electron accepting tendency of zinc is less than that of hydrogen
thus zinc can loose electrons to H+ ions of the acid, as a result hydrogen gas is liberated. Since copper
has positive reduction potential value (+0.34V) and it lies above hydrogen in the electrochemical series,
therefore, it cannot loose electrons to H+ and thus hydrogen is not liberated.
Q.32. How does the electron and current flow in the Daniel cell?
Sol.32 In Daniel cell Zn/Zn2+ acts as anode while Cu2+/Cu acts as cathode, the electrons flow from Zn electrode
to Cu electrode while current flows from Cu to Zn electrodes. We know that flow of current is possible
only if there is a potential difference between the copper and zinc electrodes.
Q.33. Show that oxidation and reduction go side by side by taking a suitable example.
Sol.33 Oxidation and reduction takes place side by side and they are reversible reaction.
One species is oxidized and the other species is reduced. The electrons released by one species are
accepted by other species.

4
For example in the reaction:

R
 Cu + Zn 2 + , Zn is oxidized to Zn2+ and Cu2+ is reduced to Cu.
Cu 2 + + Zn 

I 2
Q.34. Complete and balance the following skeleton equation for a reaction in acidic solution.

S 64
→ Mn 2 + + H 2 O + O 2
H 2 O 2 + MnO 4 + H + 
Sol.34 MnO contains manganese in its highest oxidation state. Hence, if reaction occurs at all, MnO −4 must be
−
4
reduced. Since the solution is acidic in nature, the reduction product will be Mn2+. The H2O2 therefore act

T
as a reducing agent in this reaction, and its only possible oxidation product is O2. The usual procedure for
balancing may be followed from this point, as follows.

J 42
2 × [MnO −4 + 8H + + 5e − → Mn 2 + + 4H 2 O]
5 × [H 2 O 2 
→ O 2 + 2H + + 2e − ]
2MnO −4 + 16H + + 5H 2 O 2 
→
2Mn 2 + + 8H 2 O + 5O 2 + 10H +

5
After cancelling, 2MnO −4 + 6H + + 5H 2 O 2

1
 → 2Mn 2 + + 8H 2 O + 5O 2
The above equation is an ionic equation. If we have to write an equation in terms of neutral substances,

0
we are free to decide which salt of MnO −4 and which acid to be used. We use KMnO4 and H2SO4, we
obtain
2KMnO 4 + 3H 2SO 4 + 5H 2 O 2  →

9
2MnSO 4 + 8H 2 O + K 2SO 4 + 5O 2
Q.35. MnO42– undergoes disproportionation reaction in acidic medium but MnO4– does not. Give reason.
Sol.35 In MnO −4 , Mn is in the highest oxidation state i.e., +7. Therefore, is does not undergo disproportionation.
MnO 24 − undergoes disprotionation as follows:
3MnO 24 − + 4H +  → 2MnO −4 + MnO 2 + 2H 2 O
Q.36. Nitric acid is an oxidising agent and reacts with PbO but it does not react with PbO2. Explain why?
Sol.36 PbO is a basic oxide and simple acid base reaction takes place between PbO and HNO3. On the other hand
in PbO2, lead is in +4 oxidation state and cannot be oxidised further. Therefore no reaction takes place.
Thus, PbO2 is passive, only PbO reacts with HNO3.
2PbO + 4HNO3 → 2Pb(NO3 ) 2 + 2H 2 O (Acid base reaction)
Q.37. Identify the oxidant and reductant in the following reactions:
(i) 10H+(aq) + 4Zn(s) + NO3–(aq) 
→ 4Zn2+(aq) + NH4+(aq) + 3H2O(l)
(ii) I2(g) + H2S(g) 
→ 2HI(g) + S(s)

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 EXPERT CHEMISTRY CLASSES BY JT SIR Redox Reactions 23

Sol.37 (i)
O.N. of Zn is changing from zero to +2 (increase in O.N.), therefore Zn is a reductant. O.N. of N is
changing from +5 in NO3− to –3 in NH +4 . Therefore, NO3− is oxidant.
(ii) I2 is an oxidant as it is changing its O.N. from zero in I2 to –1 in HI.
H2S is a reductant as S is changing its O.N. from –2 in H2S to zero in sulphur.
Q.38. Balance the following equation using oxidation number method
HNO3(aq) + Cu2O(s)  → Cu(NO3)2(aq) + NO(g) + H2O(l) + 2OH–
Sol.38
HNO3 (aq ) + Cu 2 O( s ) → Cu(NO3 )(aq ) + NO( g ) + H 2 O(l )
(i) The oxidation number of N changes from +5 in HNO3 to +2 in NO.
(ii) The oxidation number of Cu changes from +1 in Cu2O to +2 in Cu(NO3)
(iii) Electron balance diagrams can be written as follows
N+5 +3e– → N+2 …(1)
Cu → Cu + e 
+1 +2 –
…(2)

4
(iv) In order that the number of electrons lost shall be equal the number gained, multiply equation (1) by
2 and (2) by 6

R
2N+5 + 6e– → 2N+2

I 2
6Cu+1 → 6Cu+2 + 6e–
Hence, the coefficients of HNO3 and of NO are 2 and those of Cu2O is 3 and Cu(NO3)2 is 6. Part of

S 64
the skeleton equation can now be written as
2HNO3 + 3Cu 2 O  → 2NO + 6Cu(NO3 ) 2

T
The two atoms of H form one H2O on the right.
2HNO3 + 3Cu 2 O  → 2NO + 6Cu(NO3 ) + H 2 O

J 42
Although the N atoms that change oxidation number have been balanced, other N atoms are present
as NO3− ions in 6Cu(NO3)2, for this reason, we add 12HNO3 to the 2HNO3 already on the left side
and then balance H2O molecule. The complete balanced equation is
14HNO3 (aq ) + 3Cu 2 O( s ) 
→

5
6Cu(NO3 ) 2 (aq ) + 2NO( s ) + 7H 2 O(l )
Q.39. Starting with the correct half-reaction, write the correct overall net ionic reaction in the following

1
changes.
(i) Chromite ion (CrO3–) is oxidised by H2O2 in strongly basic solution.

0
(ii) Iodate ion (IO3–) oxidises the iodide I– and I2 in acidic solution.
(iii) Permanganate ion MnO −4 oxidises the oxalate ion (C2 O 24 − ) to CO2 in acidic solution.

9
Sol.39 (i) Oxidation half reaction:
+5 +6

CrO3− + 2OH −  → CrO −42 + H 2 O + e −

Reduction half-reaction:
−1
H 2 O 2 + 2e − 
→ 2OH −
Over all cell reaction
2CrO3− + H 2 O 2  → 2CrO −42 + H 2 O
(ii)
Oxidation half-reaction
{2I − → I 2 + 2e − } × 5
Reduction half-reaction.
2IO3− + 10I − + 12H + 
→ 6I 2 + 6H 2 O
or IO3− + 5I − + 6H + 
→ 3I 2 + 3H 2 O
(iii) Oxiadtion half-reaction:

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 24 Redox Reactions EXPERT CHEMISTRY CLASSES BY JT SIR

+3 +4

{C2O−42 → 2CO2 + 2e− } × 5

Reduction half-reaction:
{MnO−4 + 8H + + 5e− → Mn +2 + 4H 2O} × 2
Overall cell reaction:
5C2 O −42 + 2MnO −4 + 16H + 
→
10CO 2 + 2Mn +2 + 8H 2 O
Q.40. Explain with example, the oxidation and reduction in terms of change in oxidation number.
Sol.40 Oxidation is the part of an oxidation reduction reaction in which there is an increase in the oxidation
number of an atom. Reduction is a reaction in which there is a decrease in the oxidation number of an
atom.
Example:

I R 2 4
Q.41.

S 64
Balance the following equation in acidic medium by both oxidation number and ion electron method
and identify the oxidants and the reductants:

T
H2S(aq) + Cl2(g)  → S(s) + Cl–(aq)

J 42
Sol.41 H 2S(aq ) + Cl2 ( g ) 
→ S( s ) + Cl− (aq )
Oxidation number method

Ion-electron method
Oxidation half-reaction:

1 5
Net reaction is H 2S + Cl2 → S + 2Cl− + 2H +

0
H 2S → S + 2H + + 2e −
Reduction half-reaction:

9
Cl2 + 2e − 
→ 2Cl−
Not reaction:
H 2S + Cl2  → S + 2Cl− + 2H +
Oxidant : Cl2 ; Reductant : H2S
Q.42. Is it possible to store:
(i) Copper sulpahte solution in a zinc vessel?
(ii) Copper sulphate solution in a nickel vessel?
(iii) Copper sulphate solution in a silver vessel?
(iv) Copper sulphate solution in a gold vessel?
(Take help from electrochemical series)
Sol.42 (i) No, zinc will displace copper from CuSO4 solution because
E oZn 2+ /Zn < E Cu
o
2+
/Cu

(ii) No, copper sulphate solution cannot be stored in nickel vessel.

(iii) Yes, copper sulphate solution can be stored in silver vessel as

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 EXPERT CHEMISTRY CLASSES BY JT SIR Redox Reactions 25

E oCu 2+ /Cu < E oAg+ /Ag . Silver will not displace copper from CuSO4 solution.
(iv) Yes, gold vessel can easily store CuSO4 solution.
Q.43. Arrange A, B, C, D, E and H is order of increasing electrode potential in the electrochemical series:
A + H2SO4  → ASO4 + H2
ACl2 + C  → CCl2 + A
ECl2 + C  → No reaction
2BCl + D  → DCl2 + 2B
H2SO4 + D  → No reaction
Sol.43 E < C < A < H < D < B.
Q.44. Can we find the reduction potential of a single electrode in an electrochemical cell?
Sol.44 It is not possible to calculate the reduction potential of a single electrode in an electrochemical cell.
Because, a single electrode constitutes a half cell, which can’t work independently.

R 4
Q.45. With the help of the electro-chemical series, check the feasibility of the redox reaction:
Ni(s) + 2Ag+(aq)  → Ni2+(aq) + 2Ag(s)

I 2
Sol.45 Electrochemical series is an arrangement of various redox equilibria in the order of their electrode
potential.

S 64
If a metal (A) is above another metal (B) in the electrochemical series then it can easily reduce B+ ions to
metal (B) by releasing electrons.
E oNi2+ /Ni =
−0.25V and E oAg+ /Ag =
−0.80 V

T
The Eo values indicate that Ni (A) is above Ag (B) in electrochemical series and hence the given redox

J 42
reaction is feasible.
Q.46. Arrange the metals Mg, Na, Ag, Cu, Fe, Zn in the increasing order of reactivity. Which one will be
the strongest reducing agent and which one will be the weakest one?
Sol.46 Ag > Cu > Fe > Zn > Mg > Na

5
Thus, Na is the strongest reducing agent and silver is the weakest reducing agent in the above table.
Q.47. What is meant by electrochemical series? What are characteristics of electrochemical series?

1
Sol.47 The electrochemical series is built up by arranging various redox equilibria in order to their standard
electrode potentials (redox potentials)

0
Characteristics features of electrochemical series
(i) The negative sign of the standard reduction potential indicates that an electrode when joined with

9
SHE acts as anode and oxidation occurs on this electrode.
(ii) The substances, which are stronger reducing agents than hydrogen are placed above hydrogen in
the series and have negative values of standard reduction potentials.
Q.48. The standard electrode potential corresponding to the reaction
Au3+(aq) + 3e– → Au(s) is +1.42 V.
Predict if gold can be dissolved in 1 M HCl solution and on passing H2 gas through gold solution,
metallic gold will be precipitated or not?
Sol.48 As E oAu3+ /Au is greater than E oH+ /H
2
Gold cannot be oxidised by hydrogen ion to give hydrogen. Hence, gold does not dissolve in 1 M HCl
solution. On the contrary, if hydrogen gas is passed through the salt solution of the gold it will reduce Au3+
ion and metallic gold will be precipitated.
3H 2 ( g ) + 2Au 3+ (aq )  → 6H + (aq) + 2Au( s )
Q.49. Determine the oxidation number of elements marked with asterisk.
* *
(a) [Cu(NH 3 ) 4 ](OH) 2 (b) O 2 PtF6

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 26 Redox Reactions EXPERT CHEMISTRY CLASSES BY JT SIR

*
(c) Rb 4 Na(HV10 O 28 )
Sol.49 (a) NH3 is a neutral ligand. Therefore oxidation state of nitrogen is same as in ammonia, i.e.,
x + 3 = 0 or x = –3
(b) In this compound, platinum has maximum oxidation state of +4. Therefore oxidation state of O2 is
determined by taking x.
2x + 4 – 6 = 0 or x = +1
(c) Let oxidation state of vanadium is x, then
+4 + 1 + 1 + 10x – (28 × 2) = 0
or 10x = 50 or x = +5
Q.50. Nitric acid acts only as an oxidising agent while nitrous acid acts both as an oxidising as well as a
reducing agent. Why?
Sol.50 (i) HNO3 : Oxidation number of N is HNO3 = +5

4
Maximum oxidation number of N = +5

R
Minimum oxidation number of N = –3

I 2
Since the oxidation number of N in HNO3 is maximum (+5), therefore, it can only decrease by
accepting electrons. Hence HNO3 acts only as an oxidising agent.

S 64
(ii) HNO2 : Oxidation number of N in HNO2 = +3
Maximum oxidation number of N = +5
Minimum oxidation number of N = –3

T
Thus, the oxidation number of N can either increase by losing electrons or can decrease by accepting
electrons. Therefore, HNO2 acts both as an oxidising as well as reducing agent.

J 42
Q.51. Which of the following are oxidising agents and which are reducing agents? Justify your answer
with half equations.
Br2, Fe3+, NO3 , I–, Na
−

Sol.51 Oxidants : Br2, Fe3+, NO3−

5
Fe3+ + e  → Fe2+
N5+ + 2e  → N3+

1
Br2 + 2e  → 2Br–
Reductants: I–, Na

0
Na  → Na+ + e
2I–  → I2 + 2e

Q.52.
9
Long Answer Type Questions
(i) Balance the following reaction by ion-electron method
K + MnO4– + H+Cl–  → K+Cl– + Mn2+(Cl–1)2 + H2O + Cl2
(ii) Balance the following reaction by oxidation number method
As2S5 + H+NO3–(conc.)  → H3AsO4 + 5H2SO4 + H2O + NO2
2+
Sol.52 (i) MnO 4 + Cl 
− −
→ Mn + Cl2
+7 +2
→ Mn 2 + ,
The half-reactions are: MnO −4 
2+
MnO 4 
−
→ Mn + 4H 2 O
8H + + MnO −41  → Mn 2 + + 4H 2 O  …(i)
Balance total charge with adding electron on higher charge side. As the higher charge is +7 and it
decreases to +2 thus add 5e– to +7 side of reaction so that the total charge for this half reaction is
balanced.

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 EXPERT CHEMISTRY CLASSES BY JT SIR Redox Reactions 27

→ Mn 2 + + 4H 2 O 
5e − + 8H + + MnO −41  …(ii)
2Cl−  → Cl2
2Cl−  → Cl2 + 2e −
Now combine equation (i) and (ii). The electrons should get cancelled out thus multiply eqn. (i) by
2 and eqn. (ii) by 5
10e − + 16H + + 2MnO −41 
→ 2Mn 2 + + 8H 2 O
10Cl−1  → 5Cl2 + 10e −
Combining the half-reactions:
10Cl− + 16H + + 2MnO 4− → 2Mn 2 + + 8H 2 O + 5Cl2
or 16HCl + 2KMnO 4 
→
2MnCl2 + 8H 2 O + 5Cl2 + 2KCl

(ii)

I R 2 4
Here O.N. of ‘N’ decreases from +5 to +4 while that of ‘S’ increases in from –2 to +6. Since there

S 64
are five ‘S’ atoms in reactants as well as in products and one ‘N’ atom in reactants as well as
products in eqn. (i), now balance increase / decrease in O.N. The total increase in O.N. of S is +8
i.e., by a factor 40 since there are 5 ‘S’ atoms and decrease in O.N. of ‘N’ is –1. Multiply As2S5 by

T
1 and HNO3− by 40 we get
Balance the elements which change oxidation state:

J 42
As 2S5 + 40HNO3  →
H 3 AsO 4 + 5H 2SO 4 + H 2 O + 40NO 2
Balance atoms other than “O” and “H”.
As 2S5 + 40HNO3  →

5
2H 3 AsO 4 + 5H 2SO 4 + H 2 O + 40NO 2
Balance the ‘O’ and ‘H’ atoms. Since there are 120 ‘O’ atoms on the reactant side and 109 ‘O’ atoms

1
on the product side add 11 H2O on the product side to balance the equation. There are 40 ‘H’ atoms
on reactant side and 18 ‘H’ atoms on the product side initially but after adding 11 H2O the ‘H’ atoms

0
get balanced.
As 2S5 + 40HNO3  →

9
2H 3 AsO 4 + 5H 2SO 4 + 12H 2 O + 40NO 2
Q.53. (i) Balance the following equations using half-reaction method in the acidic medium.
(a) Zn + NO3–  → Zn2+ + NH4+
(b) MnO4 + H2C2O4 
–
→ Mn2+ + CO2
(c) Cr2O72– + Cl–  → Cr3+ + Cl2
(ii) Balance the following redox reaction in basic medium using the half-reaction method:
(a) Mn2+ + ClO3–  → MnO2 + ClO2
(b) Cl2  → Cl + ClO3–
–

Sol.53 (i)

(a)

Oxidation half-reaction:
+2
[Zn → Zn + 2e ] × 4
−

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 28 Redox Reactions EXPERT CHEMISTRY CLASSES BY JT SIR

Reduction half-reaction:
NO3 + 10H + 8e → NH 4 + 3H 2 O
− + − +

Net balanced redox reaction:

+2
4Zn + NO3 + 10H → 4Zn + NH 4 + 3H 2 O
− + +

(b)

Oxidation half-reaction:
[H 2 C2 O 4 → 2CO 2 + 2H + 2e ] × 5
+ −

Reduction half-reaction:
+2
[MnO 4 + 8H + 5e → Mn + 4H 2 O] × 2
− + −

4
Net balanced redox reaction:

R
+2
5H 2 C2 O 4 + 2MnO 4 + 6H → 10CO 2 + 2Mn + 8H 2 O
− +

(c)

Oxidation half-reaction:
{2Cl → Cl2 + 2e } × 3
− −
I
S 64 2
T
Reduction half-reaction:

J 42
−2 +3
Cr2 O7 + 14H + 6e → 2Cr + 7H 2 O
+ −

Net balanced redox reaction:

Cr2 O7−2 + 6Cl− + 14H + → 2Cr +3 + Cl2 + 7H 2 O
(ii)

(a)

Oxidation half-reaction:

1 5
0
Mn +2 + 4OH − → MnO 2 + 2e − + 2H 2 O
Reduction half-reaction:

9
{ClO3− + H 2 O + e − → ClO 2 + 2OH − } × 2
Net balanced redox reaction:
+2
2ClO3 + Mn → 2ClO 2 + MnO 2
−

(b)

Oxidation half-reaction:
Cl2 + 12OH → 2ClO3 + 10e + 6H 2 O
− − −

Reduction half-reaction:
{Cl2 + 2e → 2Cl } × 5
− −

Net balanced redox reaction:

6Cl2 + 12OH → 2ClO3 + 10Cl + 6H 2 O
− − −

OR

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 EXPERT CHEMISTRY CLASSES BY JT SIR Redox Reactions 29

3Cl2 + 6OH − → ClO3− + 5Cl− 3H 2 O

Q.54. Calculate the oxidation number of the underlined atom in the following species:
(i) Zn(OH) 24 − (ii) C6 H12 O6
3−
(iii) [Fe(CN)6 ] (iv) NH +41
(v) KBr O 4 hd
Sol.54 (i) Zn(OH) −42 = x Zn + 4x OH =−2
= x Zn + 4(−1) =−2

∴ x Zn = +2
(ii) C6 H12 O6= 6x C + 12(1) + 6(−2)= 0
∴ xC = 0
(iii) [Fe(CN)6 ]−3 =x Fe + 6(−1) =−3

4
∴ x Fe = +3

I 2
NH +4 =+
x N 4(1) =
(iv) +1
∴ xN = −3

S 64
(v) K BrO4 =+1 + x Br + 4(−2) =0
∴ x Br =
+7

T
Q.55. (i)
What are the highest oxidation numbers of N, S and Cl?

J 42
(ii)
Is Cr2O72– + H2O  2CrO42– + 2H+ a redox reaction?
(iii)
Calculate oxidation number of:
(a) Cr in CrO5 (b) S in H2SO5
(c) Fe in Fe3O4.
Sol.55 (i)
The highest oxidation numbers for N, S and Cl are +5, +6 and +7 respectively.

5
(ii)
The reaction
 2CrO 24 −
Cr2 O72 − + H 2 O 

1
+2H+ cannot be regarded as a redox reaction because the O. No. of ‘Cr’ in Cr2 O72 − and CrO 24 − is
same (+6).

0
(a) Cr has +6 oxidation state because it has 6 valence electrons, therefore, can form 6 covalent
bonds.

(b)
9
By conventional method, the O.N. of S in H2SO5 is
2(+1) + x + 5(–2) = 0 or x =+8
This is impossible because the maximum O.N. of S cannot be more than six since it has
only six electrons in the valence shell. This fallacy is overcome if we calculate the O.N. of
S by chemical bonding method.
O

H  O S O  O  H

O
2x(+1) + x + 2(−1) + 3x(−2) = 0 or x = +6
(for H) (for S) for(O − O) (for other O atoms)

(c) By conventional method, Fe3O4

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 30 Redox Reactions EXPERT CHEMISTRY CLASSES BY JT SIR

3x + 4(–2) = 0 or x = 8/3
+2 −2 +3 −2
By Stoichiometry Fe3O4 = Fe [Link] 2 O3
Fe has O.N. of +2 and +3
Q.56. Name one compound each in which Oxidation Number of
(a) Oxygen is +2 (b) Oxygen is –1
(c) Hydrogen is –1 (d) Nitrogen is +1
(e) Cl is +4 (f) Oxygen is –2
Sol.56 (a) F2O (b) H2O2
(c) NaH (d) N2O
(e) ClO2 (f) H2O

I R 2 4
S 64
T
J 42
1 5
9 0

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 EXPERT CHEMISTRY CLASSES BY JT SIR Redox Reactions 31

Single Correct Questions  1 

E o  H + , H 2  = −0,0;
 2 
1. Which of the following involves transfer of five E°(Cu , Cu) = + 0.34V
2+

electrons ? The electrode acting as strong reductant is

(a) MnO −4 → Mn 2 + (b) CrO 24 − → Cr 3+ (a) K (b) Cu
(c) MnO 24 − → MnO 2 (d) Cr2 O72 − → 2Cr 3+ (c) Zn (d) H2

2. The standard reduction potential of Li+/Li, Ba2+/ 9. In the reaction H2S + NO2 → H2O + NO + S.
Ba, Na+/Na and Mg2+/Mg are – 3.05, – 2.73, H2S is
–2.71 and – 2.37 volts respectively. Which one (a) oxidised (b) reduced
of the following is strongest oxidising agent? (c) precipitated (d) None of these
(a) Li+ (b) Na+
10. The oxidation number of C in CH4, CH3Cl,
(c) Mg2+ (d) Ba2+ CH2Cl2, CHCl3 and CCl4 is respectively –

4
(a) + 4, – 2, 0, + 2, + 4

R
3. Which reaction involves neither oxidation nor
reduction? (b) + 2, 4, 0, – 2, – 4

I 2
(a) CrO 24 − → Cr2 O72 − (b) Cr → CrCl3 (c) 4, 2, 0, – 2, – 4

S 64
(c) Na → Na + (d) 2S2 O32 − → S4 O62 − (d) 0, 2, – 2, 4, 4

4. In the following reaction 11. H2C2O4 + KMnO4 in acidic medium reacts to

4P + 3KOH + 3H2O → 3KH2PO2 + PH3 have change in oxidation number of Mn from :

T
(a) phosphorus is both oxidised and reduced. (a) 7 to 5 (b) 2 to 7

J 42
(b) only phosphorus is reduced. (c) 5 to 7 (d) 7 to 2
(c) phosphorus is not oxidised 12. In which of the compounds does ‘manganese’
(d) None of these exhibit highest oxidation number ?
5. H2S acts only as a reducing agent while SO2 (a) MnO2 (b) Mn3O4

5
can act both as a reducing and oxidizing agent (c) K2MnO4 (d) MnSO4
because 13. On reduction of KMnO4 by oxalic acid in acidic

1
(a) oxygen is more – ve in SO2 medium, the oxidation number of Mn changes.
(b) hydrogen in H2S is more + ve than oxygen What is the magnitude of this change?
(c) S in SO2 has one oxidation state

0
(a) From 7 to 2 (b) From 6 to 2
(d) S in H2S has –2 oxidation state (c) From 5 to 2 (d) From 7 to 4

9
6. In the reaction 14. Among the following, identify the species with
Cr2 O72 − + 14H + + 6I −  → 2Cr 3+ + 7H 2 O + 3I 2 an atom in +6 oxidation state
Which element is reduced (a) MnO −4 (b) Cr(CN)36−
(a) I (b) O (c) NiF62 − (d) CrO2Cl2
(c) H (d) Cr
15. The values of standard oxidation potentials of
7. Which one of the following reaction involves following reactions are given below :
oxidation-reduction ? (i) Zn → Zn2+ + 2e–; Eº = 0.762 V
(a) H2 + Br2 → HBr (ii) Fe → Fe2+ + 2e–; Eº = 0.440 V
(b) NaBr + HCl → NaCl + HBr (iii) Cu → Cu2+ + 2e–; Eº = –0.345 V
(c) HBr + AgNO3 → AgBr + HNO3 (iv) Ag → Ag+ + e–; Eº = –0.800 V
(d) 2NaOH + H2SO4 → Na2SO4 + 2H2O Which of the following is most easily reduced
(a) Fe (b) Ag
8. The standard reduction potentials of some
electrodes are (c) Zn (d) Cu
E°(K+, K) = – 2.9 V; E°(Zn2+, Zn) = – 0.76 V

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 32 Redox Reactions EXPERT CHEMISTRY CLASSES BY JT SIR

16. In which of the following compounds the (a) Sn2+ (b) Sn4+
oxidation number of carbon is not zero? (c) As (d) HAsO2
(a) HCHO (b) CH3COOH
26. A compound contains atoms X,Y,Z; the oxidation
(c) C12H22O11 (d) CH3CHO
number of X is +2, Y is +5 and Z is –2, therefore
17. When SO2 is passed through acidified solution of a possible formula of the compound is :
potassium dichromate, then chromium sulphate (a) XY1Z2 (b) X2(YZ3)2
is formed. The change in valency of chromium (c) X3(YZ4)2 (d) X3(Y4Z)2
is
(a) +4 to +2 (b) +5 to +3 27. Stronger is oxidising agent, more is :
(c) +6 to +3 (d) +7 to +2 (a) standard reduction potential of that species
(b) the tendency to get it self oxidised
18. In which of the following transition metal (c) the tendency to lose electrons by that species
complexes does the metal exhibit zero oxidation
(d) standard oxidation potential of that species

4
state ?
28.
Which of the following statements are correct

R
(a) [Co(NH3)6]Cl3 (b) [Fe(H2O)6]SO4
concerning redox properties?

I
(c) Ni(CO)4 (d) [Fe(H2O)6]X3

2
(i) A metal M for which E° for the half life
19. In the reaction reaction

S 64
Ag2O + H2O2  → 2Ag + H2O + O2, the H2O2 Mn+ + ne–   M is very negative will be
acts as: a good reducing agent.
(a) reducing agent (b) oxidising agent (ii) The oxidizing power of the halogens

T
(c) bleaching agent (d) none of the above decreases from chlorine to iodine.

J 42
20. In which of the following compounds, the (iii) The reducing power of hydrogen halides
oxidation number of iodine is fractional ? increases from hydrogen chloride to
hydrogen iodide
(a) IF7 (b) I3−
(a) (i), (ii) and (iii) (b) (i) and (ii)
(c) IF5 (d) IF3
(c) (i) only (d) (ii) and (iii)

5
21. Which of the following behaves as both
oxidising and reducing agents ? 29. In reaction of KMnO4 and Mohr ’s salt, FeSO4 is
oxidised to

1
(a) H2SO4 (b) SO2
(a) Fe2+ (b) Fe3+
(c) H2O (d) HNO3
(c) Fe (d) All of these

0
22. Which of the following substances acts as an
oxidising as well as a reducing agent? 30. The violent reaction between sodium and water

9
is an example of :
(a) Na2O (b) SnCl2
(a) Reduction (b) Oxidation
(c) Na2O2 (d) NaNO2
(c) Redox reaction (d) Neutralization reaction
23. Which of the following reactions depict the
oxidizing behaviour of H2SO4 : 31. The compound that can work both as an
oxidizing and reducing agent is :
(a) 2PCl5 + H2SO4 + → 2POCl3 + 2HCl + SO2Cl2
(a) KMnO4 (b) H2O2
(b) 2NaOH + H2SO4 → Na2SO4 + H2O
(c) BaO2 (d) K2Cr2O7
(c) NaCl + H2SO4 → NaHSO4 + HCl
(d) 2HI + H2SO4 → I3 + SO2 + 2H2O 32. The oxidation number of phosphorus in
pyrophosphoric acid is
24. When NaCl is dissolved in water the sodium ion
(a) +3 (b) +1
becomes
(c) +4 (d) +5
(a) oxidised (b) reduced
(c) hydrolysed (d) hydrated 33. Zn gives H2 gas with H2SO4 and HCl but not
with HNO3 because
25. In the reaction

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 EXPERT CHEMISTRY CLASSES BY JT SIR Redox Reactions 33

(a) Zn acts as an oxidising agent when it reacts Reason: Equivalent weight =

with HNO3 Molecular weight
(b) HNO3 is weaker acid than H2SO4 and HCl number of e − lost or gained
(c) in electrochemical series, Zn is above
hydrogen 39. Assertion: SO2 and Cl2 both are bleaching
agents.
(d) NO3− is reduced in preference to hydronium
ion Reason: Both are reducing agents.

34. The oxidation states of sulphur in the anions 40. Assertion: Fluorine exists only in –1 oxidation
SO32 − , S2 O 42 − and S2 O62 − follow the order state.
(a) S2 O62 − < S2 O 24 − < SO32 − Reason: Fluorine has 2s2 2p5 configuration.
(b) S2 O 42 − < SO32 − < S2 O62 − 41. Assertion: HClO4 is a stronger acid than HClO3.
(c) SO32 − < S2 O 42 − < S2 O62 − Reason: Oxidation state of Cl in HClO4 is +VII
and in HClO3 + V.

4
(d) S2 O 42 − < S2 O62 − < SO32 −

R
42. Assertion: In a reaction Zn(s) + CuSO4(aq) →
35. Oxidation numbers of P in PO34− , of S in SO 24 −

I 2
ZnSO4(aq) + Cu(s), Zn is a reductant but itself
and that of Cr in Cr2 O72 − are respectively
get oxidized.
(a) + 3, + 6 and + 5 (b) + 5, + 3 and + 6

S 64
Reason: In a redox reaction, oxidant is reduced
(c) – 3, + 6 and + 6 (d) + 5, + 6 and + 6 by accepting electrons and reductant is oxidized
by losing electrons.
Assertion & Reason

T
43. Assertion: Oxidation number of carbon in
CH2O is zero.

J 42
The questions given below consist of Assertion (A)
and Reason (R). Use the following key to select correct Reason: CH2O formaldehyde, is a covalent
answer. compound.
(a) If both assertion and reason are correct and 44. Assertion: A reaction between Fe and I2 occurs,
reason is correct explanation for assertion. but a reaction between Fe2+ and I– does not

5
(b) If both assertion and reason are correct occur.
but reason is not correct explanation for Reason: Fe is a better reducing agent than I−.

1
assertion.
(c) If assertion is correct but a reason is PASSAGE BASED/CASE STUDY

0
incorrect. QUESTIONS
(d) If assertion and reason both are incorrect.

9
36. Assertion: The oxidation numbers are artificial;
they are useful as a ‘book-keeping’ device of 1
electrons in reactions.
Reason: The oxidation numbers do not usually Consider the following unbalanced redox reaction:
represent real charges on atoms, they are simply H2O + AX + BY → HA + OY + X2B
conventions that indicate what the maximum The oxidation number of X is –2, and neither X nor water
charge could possibly be on an atom in a is involved in the redox process.
molecule.
45. The element(s) undergoing oxidation is/are:
37. Assertion: H2SO4 cannot act as reducing agent.
(a) A (b) B
Reason: Sulphur cannot increase its oxidation
(c) Y (d) B or Y or both
number beyond +6.
46. The possible oxidation state of B and Y in BY
38. Assertion: Equivalent weight of NH3 in the
are, respectively:
reaction N2 → NH3 is 17/3 while that of N2 is
(a) +1, –1 (b) +2, –2
28/6.
(c) +3, –3 (d) All of these

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 34 Redox Reactions EXPERT CHEMISTRY CLASSES BY JT SIR

47. If the above reaction is balanced with smallest (c) When a negative ion changes to neutral
whole number coefficients, the sum of the species, the process is oxidation.
stoichiometric coefficients of all the compounds (d) The oxidation number of phosphorous can
is: very form –3 to +5.
(a) 9 (b) 8
52. Which of the following is not a disproportionation
(c) 7 (d) 6
reaction?
(a) OH– + Br2 → Br– + BrO3–
2 (b) Cu2O + 2H+ → Cu + Cu2+ + H2O
(c) (CN)– → CO32– + NO3–
Oxidation reaction involves loss of electrons, and reduction (d) (CN)2 + 2OH– → CN– + CNO– + H2O
reaction involves gain of electrons. The reaction in which
a species disproportionate into two oxidation states (lower Answer Key
and higher) is called disproportionation reaction

4
48. Which of the following statements is wrong? 1. (a) 2. (c) 3. (a)

R
(a) A acidified K2Cr2O7 paper on being exposed 4. (a) 5. (d) 6. (d)

I 2
to SO2 turns green. 7. (a) 8. (a) 9. (a)
(b) Mercuric chloride and stannous chloride

S 64
10. (a) 11. (d) 12. (c)
cannot exist as such.
13. (a) 14. (d) 15. (b)
(c) Iron turning on addition to CuSO4 solution
16. (d) 17. (c) 18. (c)
decolourises the blue colour.

T
(d) [CuI4]2– is formed but [CuCl4]2– is not. 19. (a) 20. (b) 21. (b)

J 42
22. (d) 23. (d) 24. (d)
49. Which of the following statements is wrong? 25. (d) 26. (c) 27. (a)
(a) Accidified KMnO4 solution decolourieses
28. (a) 29. (b) 30. (c)
on the addition of sodium oxalate.
31. (b) 32. (d) 33. (d)
(b) In the reaction between Br2 and CsI, Br2 is
34. (c) 35. (d) 36. (a)

5
an oxidizing agent and CsI is a reducing
agent. 37. (a) 38. (a) 39. (c)
(c) In the reaction 2K2S2O3 + I2 → 2KI + K2S4O6, 40. (b) 41. (b) 42. (a)

1
the change in the oxidation number of S is 43. (b) 44. (a) 45. (d)
0.5 46. (d) 47. (b) 48. (d)

0
(d) C has the same oxidation number in both 49. (d) 50. (a) 51. (a)
CH4 and CO2
52. (c)

9
50. Which of the following statements is correct?
(a) An element in the lowest oxidation state acts
only as a reducing agent.
(b) An element in the highest oxidation sate acts
only as a reducing agent.
(c) The oxidation number of V in Rb4K(HV10O28)
is +4.
(d) The oxidation number and valency of Hg in
calomel is +1
51. Which of the following statements is wrong?
(a) The algebraic sum of the oxidation numbers
of all atoms in an ion is zero
(b) The oxidation number is an arbitrary
number. It can have positive, negative, zero,
or fractional values.

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 EXPERT CHEMISTRY CLASSES BY JT SIR Redox Reactions 35

Practice Questions

VERY SHORT ANSWER QUESTIONS

1. Define oxidation and reduction in terms of electrons.

2. When magnesium ribbon is burnt in air, two products are formed, magnesium oxide and magnesium
nitride. Point out the oxidizing and reducing agents.
3. In the reaction MnO2 + 4HCl → MnCl2 + Cl2 + 2H2O, which species is oxidized?

4
4. Write an equation for the reduction of copper(II) ions in aqueous solution to copper metal.

R
5. Natural gas is composed of the hydrocarbon X. When X burns in excess of oxygen, carbon dioxide and

I 2
water are produced. Identify X.
6. → VO 2 + (aq ) + Zn 2 + (aq ) , what is the reducing agent?
Given the chemical equation, VO +2 (aq ) + Zn( s ) 

S 64
7. What is the oxidation number of (a) sulphur in the sulphate ions, SO 24 − and (b) manganese in the
permanganate ion, MnO −4 ?

T
8. What is the oxidation number of S in (a) Na2S4O6 and (b) S2Cl2.

J 42
9. Define equivalent weight of an oxidizing/reducing agent.
10. Given the following, Cr(s) → Cr3+(aq), how many water molecules are required to balance this half-
reaction?
11. Given the following, S2 O32 − (aq ) 
→ SO 42 − (aq ) , how many H+ ions, and on which side of the → are

5
required to balance the half reaction?
12. Write down the anode and cathode half-cell reactions which take place in the Daniell cell.

1
13. When does the cell voltage attain its maximum value?
14. What is the direction of the flow of electrons in the Daniell cell?

0
15. What is standard hydrogen electrode?

9
16. Arrange the following lists Cu, Ni, and Mg in order of increasing reducing strength.
17. Out of Al, Zn2+, Pb and Cl2, which oxidizing agent should be used in conjunction with the oxidation half-
reaction Cu  → Cu 2 + + 2e − in order to ensure aspontaneous redox reaction?
18. In a Daniell cell, what is responsible for allowing the migration of ions between the two compartments?
19. In order to “chrome” the exhaust pipes of a motorcycle, machinists submerged the pre-cut stainless steel
pipes into a Cr2(SO4)3 aqueous bath. What is the process by which the chromium ions are deposited into
a thin coat on the surface of the steel?

SHORT ANSWER QUESTIONS

20. Identify the oxidants and reductants in the following reactions:

(a) CH 4 ( g ) + 4Cl2 ( g )  → CCl4 ( g ) + 4HCl( g )
(b) 2H (aq ) + MnO 2 ( s ) + C2 H 2 O 4 
+
→ Mn 2 + + 2CO 2 ( g ) + 2H 2 O(l )
(c) I 2 (aq ) + 2S2 O32 − (aq ) → 2I − (aq ) + S4 O62 − (aq )

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 36 Redox Reactions EXPERT CHEMISTRY CLASSES BY JT SIR

(d) Cl2 ( g ) + 2Br − (aq ) 

→ 2Cl− (aq ) + Br2 (aq )
21. Comment upon the statement: Oxidation and reduction reactions go side by side.
A solution contains ions of the following metals: Cr3+, Ni2+, Cu2+. Which metal ion will be reduced to the
metal form first? Explain.
22. What are half-reactions? Explain with examples.
23. Define the terms oxidizing agent and reducing agent according to the electronic concept. Give one
example in each case.
24. Discuss briefly types of redox reactions. Give one example in each case.
25. H2O2 acts as reductant as well as oxidant. Explain.
26. The following is an unbalanced equation that represents a redox reaction.
Cr2 O72 − (aq ) + F− (aq ) 
→ Cr 3+ (aq ) + F2 (aq )

4
Using the ion-electron method, write the balanced (mass and charge) reduction and oxidation half-
reactions. Write the total balanced redox equation in a basic solution.

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27. Balance the following equations in an acidic medium by both oxidation number and ion-electron methods

2
and identify the oxidants and the reductants:
(a) Bi( s ) + NO3− (aq )  → Bi3+ (aq ) + NO 2 ( g )

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(b) H 2S( g ) + Fe3+ (aq ) → Fe 2 + (aq ) + S( s ) + H + (aq )
(c) H 2S(aq ) + Cl2 ( g ) → S( s ) + Cl− (aq )

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(d) S + HNO3  → SO 2 + NO 2 + H 2 O
(e) As( s ) + NO3 (aq ) + H + (aq ) 
−
→ AsO34− (aq ) + NO 2 ( g ) + H 2 O(l )

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28. Metallic tin in presence of HCl is oxidized by K2Cr2O7 to stannic chloride. What volume of decinormal
dichromate solution will be reduced by 1 g of tin? (Atomic weight of Sn = 118.7.)
29. Why blue color of copper sulphate solution gets discharged when zinc rod is dipped in it? (Given ECu
o
2+
/Cu
= 0.34 V and EZn/Zn 2+ = 0.76 V.)
o

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30. How will you distinguish between the potential difference and the electromotive force?

1
31. What is a salt bridge? What are its functions?
32. How many millimoles of potassium dichromate is required to oxide 24 mL of 0.5 M Mohr’s salt solution

0
in an acidic medium?

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LONG ANSWER QUESTIONS

33. Discuss the different redox reactions that occur in aqueous solutions.
34. Which of the following reactions are oxidation-reduction reactions?
(a) 2H2 + O2  → 2H2O
(b) CaCO3  → CaO + CO2
(c) 2Na + 2H2O  → 2NaOH + H2
(d) 2HNO3 + Ca(OH)2  → Ca(NO3)2 + 2H2O
(e) AgNO3 + KCl  → AgCl + KNO3
(f) Zn + CuCl2  → ZnCl2 + Cu
State the oxidizing and reducing agents and the species getting oxidized/reduced.
35. Explain (a) oxidation number method and (b) ion-electron method for balancing redox reactions using
one example each.
36. Define and describe the terms (a) oxidation, (b) reduction, (c) oxidizing agent and (d) reducing agent in

JT SIR CHEMISTRY CLASSES: 12/26 BASEMENT, WEST PATEL NAGAR, NEW DELHI # 9015426424, 8470010621
 EXPERT CHEMISTRY CLASSES BY JT SIR Redox Reactions 37

terms of oxidation number. Give an example in each case.

37. What is electrochemical series? Discuss its use in
(a) comparing the oxidizing and reducing strength of different elements and
(b) prediciting whether a metal will react with a mineral acid to liberate hydrogen gas.
Give suitable examples in each case.
38. What is an electrochemical cell? Describe its construction and working. How is it represented?

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JT SIR CHEMISTRY CLASSES: 12/26 BASEMENT, WEST PATEL NAGAR, NEW DELHI # 9015426424, 8470010621