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CHAPTER 4

OXIDATION REDUCTION REACTIONS-


REDOX REACTIONS
These reactions can be seen all around us
like burning of fossil fuels to the action of
household bleach. Most elements are
obtained from their ores by oxidation or
reduction process.

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Oxidation and Reduction

An oxidation-reduction reaction

• provides us with energy from food.


• provides electrical energy in
batteries.
• occurs when iron rusts.

4Fe(s) + 3O2(g) 2Fe2O3(s)


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Electron Loss and Gain

An oxidation-reduction reaction involves


• a transfer of electrons from one reactant to another.
• oxidation as a loss of electrons (LEO).
• reduction as a gain of electrons (GER).

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Oxidation and Reduction

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Redox reactions are considered as
electron-transfer reactions
• Many important redox reactions occur in
water.
• Consider the formation of MgO from Mg and
O2
• 2 Mg(s) + O2 (g) → 2MgO(s)
• MgO is an ionic compound made up of Mg2+
and O2- ions. Here two Mg atoms give up or
transfer four electrons and the two O atoms(in
O2) gain these four electrons
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This can be thought of as two Half
reactions- Oxidation and Reduction
• 2Mg→2Mg2+ + 4e- Oxidation half (loss of e-)
O2 + 4e- →2O2- Reduction half (gain of e-)

Half reactions shows the electrons involved in a


redox reaction.
Sum of the half reactions give the overall reaction
2Mg+ O2 + 4e- →2Mg2+ +2O2- + 4e-
2Mg+ O2 →2Mg2+ +2O2-

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Finally Mg2+ and O2- combine to form MgO
2Mg2+ +2O2- → 2MgO
• Magnesium is Oxidised and acts as a Reducing
agent because it donates e- to oxygen and causes
it to be reduced.
• Oxygen is Reduced and acts as an Oxidizing
agent because it accepts e- from magnesium,
causing it to be oxidised.
• The no. of electrons lost by reducing agent must
be equal to the no. of electrons gained by an
oxidizing agent.

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When metallic Zinc is added to CuSO4 (aq)
solution, Zn reduces Cu2+ by donating 2 e- to it

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Zn and Cu2+

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Zn(s) Zn2+(aq) + 2e- oxidation


silver metal

Cu2+(aq) + 2e- Cu(s) reduction


blue solution orange

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Electron Transfer from Zn to Cu2+

Oxidation: loss of electrons

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Reduction: gain of electrons

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Learning Check
Identify each of the following as
1) oxidation or 2) reduction.

__A. Sn(s) Sn4+(aq) + 4e−


__B. Fe3+(aq) + 1e− Fe2+(aq)
__C. Cl2(g) + 2e− 2Cl-(aq)

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Solution
Identify each of the following as
1) oxidation or 2) reduction.

1 A. Sn(s) Sn4+(aq) + 4e−


2 B Fe3+(aq) + 1e− Fe2+(aq)
2 C. Cl2(g) + 2e− 2Cl-(aq)

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Writing Oxidation and Reduction
Reactions
Write the separate oxidation and reduction reactions
for the following equation.

2Cs(s) + F2(g) 2CsF(s)

A cesium atom loses an electron to form cesium ion.


2Cs(s) 2Cs+(s) + 2e−
oxidation

Fluorine atoms gain electrons to form fluoride ions.


F2(s) + 2e- 2F−(s) reduction

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Learning Check

In light-sensitive sunglasses, UV light initiates


an oxidation-reduction reaction.

uv light
Ag+ + Cl− Ag + Cl

A. Which reactant is oxidized?

B. Which reactant is reduced?

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Solution

In light-sensitive sunglasses, UV light initiates


an oxidation-reduction reaction.

uv light
Ag+ + Cl− Ag + Cl

A. Which reactant is oxidized? Cl− Cl + 1e−

B. Which reactant is reduced? Ag+ + 1e− Ag

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Learning Check

Identify the substances that are oxidized and reduced in


each of the following reactions.

A. Mg(s) + 2H+(aq) Mg2+(aq) + H2(g)

B. 2Al(s) + 3Br2(g) 2AlBr3(s)

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Solution

A. Mg is oxidized. Mg(s) Mg2+(aq) + 2e−


H+ is reduced. 2H+ + 2e− H2

B. Al is oxidized. Al Al3+ + 3e−


Br is reduced. Br + e− Br −

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Oxidation Number
• The formation of ionic compounds in terms of
OXIDATION and REDUCTION are understandable.
• However for the formation of molecular compounds
like HCl and SO2, no electrons are actually transferred
(as in ionic compound like MgO).
• Yet chemists find it easy to treat these reactions as
redox reactions because experimental
measurements show that there is a partial transfer
of electrons(eg. from H→Cl in HCl and from S→O in
SO2

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Thus Oxidation numbers are assigned to reactants
and products to keep track of electrons in a redox
reaction
• Oxidation number also called Oxidation state
signifies the no. of charges the atom would have in a
molecule ( or an ionic compound) if electrons were
transferred completely.

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Consider the formation of HCl and SO2
• H2 and Cl2 both have oxidation numbers(O.N) of 0 as they are
elements (Note: O.N of H2= 0 implies 0 for each H)
• Hydrogen in HCl has O.N or oxidation state(O.S) +1. Thus, O.S
of hydrogen changed 0 to +1. Hence Oxidised.
• Chlorine in HCl has O.N or oxidation state(O.S) -1. Thus, O.S of
chlorine changed 0 to -1. Hence Reduced.
• Similarly in SO2, S is oxidised and O is reduced.
• The sum of the oxidation numbers of elements in a molecule
is ZERO because molecules are neutral and so charges must
cancel out.
• In HCl, (+1 )+ (-1) = 0
• In SO2, (+4) + (2*-2) = 0

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We use the following rules to assign oxidation
numbers :
1. In free elements or in the uncombined state, each atom has
an O.N=0 ( eg. Na, Be, K, H2, Br2 etc )
2. For ions composed of only one atom (monoatomic), the O.N=
charge on the ion
Eg. Li+ has O.N =+1; Ba2+ has O.N= +2; Fe3+ has O.N = +3, O2- has
O.N=-2
All alkali metals (group 1A) have O.N =+1 in their compounds
All alkaline earth metals(group 2A) have O.N = +2 in their
compounds. Aluminium has O.N =+3 in all its compounds
3. O.N of oxygen in most compound is -2 (eg MgO). But in
H2O2(hydrogen peroxide) and peroxide ion O22- O.N of oxygen=-1

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4. Fluoride has an O.N of -1 all its compounds. Other
halogens ( Cl, Br, I) have negative O.N when they form
halides.
5. In a neutral molecule, the sum of the O.N of all the
atoms must be equal to zero.
In a polyatomic ion, the sum of the O.N of all elements
in the ion must be equal to the net charge of the ion.
Eg. Ammonium ion, NH4+ has a net charge=+1.
O.N of N=-3 , O.N of H =+1. Therefore, (-3)+(4*+1)=
-3+(+4)=+1 which is equal to the charge of the ion
6. O.N do not have to be integers. Eg. The O.N of O in
superoxide O2- is -1/2

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Metallic elements have only positive O.N whereas non-
metallic elements may have either +ve or –ve O.N

• The highest O.N an element in Group 1A to 7A can


have is its group number. For eg halogens of group
7A can have their highest possible O.N =+7
• The transition metals (group 1B, 3B-8B) usually have
several possible oxidation states.
• TYPES OF REDOX REACTIONS
• The most common redox reactions are
• 1. Combination 2. Decomposition 3. Combustion
• 4. Displacement and 5. Disproportionation
reactions

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1. Combination

In a combination reaction,
• two or more elements form one product.
• or simple compounds combine to form one product.

A + B A B

2Mg(s) + O2(g) 2MgO(s)


2Na(s) + Cl2(g) 2NaCl(s)
SO3(g) + H2O(l) H2SO4(aq)

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2. Decomposition

In a decomposition reaction,

• one substance splits into two or more simpler


substances. It is the opposite of combination
reactions.

2HgO(s) 2Hg(l) + O2(g)

2KClO3(s) 2KCl(s) + 3 O2(g)

2NaH (s) 2Na (s)+ H2 (g)

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3. Combustion Reactions
• A combustion reaction is a reaction in which a
substance reacts with oxygen, usually with the
release of heat and light to produce a flame.
• Reactions of magnesium and sulphur with oxygen
described earlier are Combustion reactions.
• Another eg is burning of propane , a component of
natural gas that is used in domestic heating and
cooking
C3H8 (g) + 5O2 →3 CO2 (g) + 4 H2O (l)

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Formation of MgO

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Learning Check

Classify the following reactions as


1) combination or 2) decomposition.

___A. H2(g) + Br2(g) 2HBr(l)


___B. Al2(CO3)3(s) Al2O3(s) + 3CO2(g)
___C. 4Al(s) + 3C(s) Al4C3(s)

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Solution

Classify the following reactions as


1) combination or 2) decomposition.

1 A. H2(g) + Br2(g) 2HBr(l)


2 B. Al2(CO3)3(s) Al2O3(s) + 3CO2(g)
1 C. 4Al(s) + 3C(s) Al4C3(s)

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4. Displacement reactions can be
a) Single replacement b) Double replacement

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Single displacement reactions can be
classified as
1. Hydrogen displacement: All alkali metals and some
alkaline earth metals (that are most reactive
metallic elements) will displace hydrogen from cold
water.
2 Na (s) + 2 H2O (l) → 2NaOH (aq) + H2 (g)
Ca (s) + 2H2O (l) → Ca(OH)2 + H2 (g)
Many metals that are not capable of reacting with
water displace hydrogen from acids
Zn(s) + 2HCl(aq) → ZnCl2(aq) + H2(g)

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2. Metal Displacement
A metal in a compound can be displaced by another metal in the
elemental state.
Zn (s) + CuSO4 (aq) → ZnSO4 (aq) + Cu (s)
Here Zn replaces Cu2+ ions but the reverse, that is Cu metal will
not displace Zn2+ ions from ZnSO4
An easy way to predict whether a metal or hydrogen
displacement reaction will occur is to refer to an ACTIVITY
SERIES (OR ELECTROCHEMICAL SERIES).

Any metal listed in the series will react with any metal (in a
compound) below it. Thus Zn is above Cu, so Zn metal will
displace copper ions from CuSO4

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ACTIVITY SERIES FOR METALS

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3. Halogen Displacement

Another activity series summarises the halogens’ behaviour


in halogen displacement reactions.
F2 > Cl2 > Br2 > I2
Fluorine can replace chloride, bromide and iodide ions from
solution. But F is so reactive that it also attacks water; thus
these reactions cannot be carried out in aqueous solutions.
Molecular chlorine can displace bromide and iodide in
aqueous solutions .
Cl2 (g) +2 KBr (aq) → 2KCl (aq) + Br2(l)
Cl2 (g) +2 NaI (aq) → 2NaCl (aq) + I2(s)
Br2 (l) +2 I- (aq) → 2Br- (aq) + I2(s)
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Reversing the roles of the halogens produces no reaction.
Thus bromine cannot displace chloride ions and iodine
cannot displace bromide and chloride ions.

5. Disproportionation reactions
In disproportionation reactions,an element in one oxidation
state is simultaneously oxidised and reduced.
One reactant in such reactions always contains an
element that can have at least three oxidation states.
Eg. The decomposition of hydrogen peroxide
oxidised
2 H2O2-1 (aq) → 2H2O-2 (l) + O20 (g)
reduced

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Double Replacement

In a double replacement, (METATHESIS reaction)


• two elements in the reactants exchange places.

AgNO3(aq) + NaCl(aq) AgCl(s) + NaNO3(aq)


ZnS(s) + 2HCl(aq) ZnCl2(aq) + H2S(g)

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Example of a Double
Replacement

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Learning Check

Classify the following reactions as


1) single replacement or 2) double replacement.

A. 2Al(s) + 3H2SO4(aq) Al2(SO4)3(s) + 3H2(g)

B. Na2SO4(aq) + 2AgNO3(aq) Ag2SO4(s) + 2NaNO3(aq)

C. 3C(s) + Fe2O3(s) 2Fe(s) + 3CO(g)

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Solution

Classify the following reactions as


1) single replacement or 2) double replacement.
1 A. 2Al(s) + 3H2SO4(aq) Al2(SO4)3(s) + 3H2(g)

2 B. Na2SO4(aq) + 2AgNO3(aq) Ag2SO4(s) + 2NaNO3(aq)

1 C. 3C(s) + Fe2O3(s) 2Fe(s) + 3CO(g)

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Learning Check

Identify each reaction as 1) combination, 2) decomposition,


3) single replacement, or 4) double replacement.

A. 3Ba(s) + N2(g) Ba3N2(s)


B. 2Ag(s) + H2S(aq) Ag2S(s) + H2(g)
C. SiO2(s) + 4HF(aq) SiF4(s) + 2H2O(l)
D. PbCl2(aq) + K2SO4(aq) 2KCl(aq) + PbSO4(s)
E. K2CO3(s) K2O(aq) + CO2(g)

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Solution

1 A. 3Ba(s) + N2(g) Ba3N2(s)


3 B. 2Ag(s) + H2S(aq) Ag2S(s) + H2(g)
4 C. SiO2(s) + 4HF(aq) SiF4(s) + 2H2O(l)
4 D. PbCl2(aq) + K2SO4(aq) 2KCl(aq) +PbSO4(s)
2 E. K2CO3(s) K2O(aq) + CO2(g)

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Learning Check

Each of the following reactions occur in the formation of


smog or acid rain. Identify the type of reaction and
balance each.
A. NO(g) + O2(g) NO2(s)
B. N2(g) + O2(g) NO(g)
C. SO2(g) + O2(g) SO3(g)
D. NO2(g) NO(g) + O2(g)

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Solution

Each of the following reactions occur in the formation of


smog or acid rain. Identify the type of reaction and
balance each.
Combination
A. 2NO(g) + O2(g) 2NO2(s)
B. N2(g) + O2(g) 2NO(g)
C. 2SO2(g) + O2(g) 2SO3(g)
Decomposition
D. 2NO2(g) 2NO(g) + O2(g)

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Balancing of Redox reactions using Half reaction
method

In this method, two half equations are balanced


separately and then added together to give balanced
equation
Consider the reaction of Fe2+ with Cr2O72- to form Fe3+
and Cr3+ in an acidic media

Step 1: Write the unbalanced reaction with correct


formula for both reactants and products
Fe 2+ (aq) + Cr2O72- (aq) Fe 3+ (aq) + Cr3+ (aq)

Here Fe is oxidised (O.N changed from +2 to +3)


whereas Cr is reduced (+6 to +3)
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Step 2:Separate the equations into half reactions,
balance number of atoms (other than H and O atoms)
and charges

Oxidation half: Fe 2+ (aq) Fe 3+ (aq) +1e-


Reduction half : [Cr2+6O7 ] 2-(aq) + (3e-)*2 2Cr3+ (aq)

Since no. of e- lost by Fe must be the same as the no. of


electrons gained by Cr, we need to multiply oxidation
half with 6
Oxidation half: (Fe 2+ (aq) Fe 3+ (aq) +1e-)*6

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Oxidation half has no O atom whereas
reduction half has

Step 3: balance the no. of O atoms on one side by adding


H2O molecules on the other side. Balance the hydrogen
atoms on one side by adding H+ on the other side.
[Cr2O7 ] 2-(aq) + 14H+ 2Cr3+ (aq)+ 7H2O (l)

This reaction is specified to occur in acidic medium. Hence


Step 4: Sum the balanced half reactions
6Fe 2+(aq) +[Cr2O7 ] 2-(aq) +6e-+ 14H+ 6Fe 3+(aq)+2Cr3+(aq)+6e- + 7H2O (l)

The net ionic equation is

6Fe 2+ (aq) + [Cr2O7 ] 2-(aq) + 14H+ 6Fe 3+ (aq)+2Cr3+ (aq)+ 7 H2O (l)
Verify that the equation contains the same type and no. of atoms and
the no. of charges (+24) on both sides of the equation

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If the reaction is specified to occur in a basic medium,

After Step 3, do this extra step


Step 5 : add as many OH- (on both sides)as to
neutralise the H+ ions on one side , combine OH- ions
and H+ ions that are present on the same side to form
water, cancel out equal no. of H2O from both sides
and thus the net ionic equation will be in basic
medium

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PROBLEMS
(Do HW in NOTE BOOK FOR PROBLEMS IN
BALANCING REDOX REACTIONS IN ACIDIC AND
BASIC solutions (Given below) using Half Reactions)
1.Balance the following redox reaction in basic
conditions.
Ag(s) + Zn2+(aq)→Ag2O(aq) +Zn (s)

Ans:2Ag(s)+Zn2+(aq)+2OH−(aq)→Zn(s)+Ag2O(aq)+H2O(l)

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Problems

 1.Balance the following redox reaction in


acidic conditions.

MnO4 - + SO32- Mn2+ + SO42-


Ans:
2MnO4 - + 5SO32- +6H+ 2Mn2+ + 5SO42- + 3H2O

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CHECK EXAMPLES AND CYL
4.2 TO 4.7 FOR PROBLEMS ON

PRECIPITATION,
ACID BASE AND
REDOX REACTIONS

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