Redox

Reactions
 Redox Reactions
Transformation of matter from one form into another form occurs
through the Redox Reactions

Reduction

Oxidation
 CLASSICAL IDEA OF REDOX REACTIONS –
OXIDATION AND REDUCTION REACTIONS

The addition of oxygen to an element or a compound is called Oxidation

2 Mg (s) + O2(g) → 2 MgO (s)

S (s) + O2(g) → SO2(g)

In this the elements magnesium and sulphur are oxidised on account of

addition of oxygen to them.
 The removal of hydrogen from a substance is also called Oxidation
CH4(g) + 2O2(g) → CO2(g) + 2H2O (l)

2 H2S(g) + O2(g) → 2 S (s) + 2 H2O (l)

The addition of electronegative element:
Mg (s) + F2(g) → MgF2(s)

Mg (s) + Cl2(g) → MgCl2(s)

Mg (s) + S (s) → MgS (s)
Removal of electropositive element:
2 𝐾 4 [ 𝐹𝑒 ( 𝐶𝑁 6 ) ] ( 𝑎𝑞 )+ 𝐻 2 𝑂 ( 𝑎𝑞 ) → 2 𝐾 3 [ 𝐹𝑒 ( 𝐶𝑁 6 ) ] ( 𝑎𝑞 )+ 2 KOH

Hence Oxidation is defined as the “addition of oxygen or electronegative

element to a sub stance or removal of hydrogen or electropositive
element from a substance”
 Reduction
Reduction is defined as the “removal of oxygen or electronegative
element from a substance or addition of hydrogen or electropositive
element to a substance”

The removal of oxygen:

2 HgO (s) → 2 Hg (l) + (g)
The removal of electronegative element:
2 FeCl3(aq) + H2(g) → 2 FeCl2(aq) + 2 HCl(aq)
The addition of hydrogen:
CH2= CH2(g) + H2(g) → H3C –CH3(g)
The addition of electronegative element:
2HgCl2(aq) + SnCl2(aq) → Hg2Cl2 (s)+SnCl4(aq)
 Redox Reactions in terms of Electron Transfer Reactions

If oxidation and reduction occur simultaneously then it is called Redox

reaction
2Na(s) + Cl2(g) 2NaCl (s) or 2Na+Cl–
2 Na(s) 2 Na+(g)+ 2e–
Cl2(g) + 2e– 2 Cl–(g)
The half reactions that involve loss of electrons are called oxidation
reactions.
The half reactions that involve gain of electrons are called reduction
reactions.
Chlorine is Oxidizing agent and sodium is Reducing agent
 Oxidation: Loss of electrons by any compound.

 Reduction: Gain of electrons by any compound.

 Oxidising agent : Acceptor of electrons.

 Reducing agent : Donor of electrons.

 Competitive Electron Transfer Reactions
The reaction between metallic zinc and the aqueous solution of copper
nitrate is : 2+ ¿ ( 𝑎𝑞 )+ 𝐶𝑢( 𝑠) ¿
2 +¿ ( 𝑎𝑞 ) → 𝑍𝑛 ¿
𝑍𝑛 ( 𝑠 ) + 𝐶𝑢
Zinc has lost electrons to form and, therefore, zinc is oxidised. Copper
ion is reduced by gaining electrons from the zinc.
Here, Cu(s) is oxidised to (aq) and (aq) is reduced to Ag(s).

The electron releasing tendency of the metals is in the order:

Zn>Cu>Ag
 Oxidation Number
Oxidation number denotes the oxidation state of an element in a
compound. ascertained according to a set of rules formulated on the
basis that electron in a covalent bond belongs entirely to more
electronegative element.

LEO:
Loss of Electrons is Oxidation

GER:
Gain of Electrons is Reduction
 Rules for the calculation of Oxidation number
The cation is written first in a formula, followed by the anion.
Eg: In NaH, the H is H-1; in HCl, the H is H+1.
The oxidation number of a free element is always 0.

Eg: The atoms in He and N2 have oxidation numbers of 0.

The oxidation number of a monatomic ion equals the charge of the

ion. Eg: The oxidation number of Na+ is +1; the oxidation number of
N3- is -3.
The usual oxidation number of hydrogen is +1. Except in metal
hydrides which is -1.
Eg: In HI, H is +1 but in NaH, H is -1.
 The oxidation number of oxygen in compounds is usually -2.
Exceptions include peroxides and superoxides. In H2O2, it is -1 and in

superoxides(e.g., KO2 , RbO2) each oxygen atom is assigned an oxidation

number of –(½).
When oxygen is bonded to fluorine like oxygen difluoride() and
Dioxygendifluoride () ,the oxygen is assigned an oxidation number of +2
and +1.
The oxidation number of a Group IA element in a compound is +1.
The oxidation number of a Group IIA element in a compound is +2.
The oxidation number of a Group VIIA element in a compound is -1,
except when that element is combined with one having a higher
electro negativity.
The oxidation number of Cl is -1 in HCl, but the oxidation number of
Cl is +1 in HOCl.
The algebraic sum of the oxidation numbers of all of the atoms in a
neutral compound is 0.
The algebraic sum of the oxidation numbers in a polyatomic ion is
equal to the charge of the ion.
Eg: The sum of the oxidation numbers for SO42- is -2.
Oxidation: An increase in the oxidation number of the element in the
given substance.
Reduction: A decrease in the oxidation number of the element in the
given substance.
Oxidising agent: A reagent which can increase the oxidation number of
an element in a given substance. These reagents are called as oxidants
also.
Reducing agent: A reagent which lowers the oxidation number of an
element in a given substance. These reagents are also called as
reductants.
Redox reactions: Reactions which involve change in oxidation number
of the interacting species.
 Types of Redox Reactions

Combination reactions:

A+B C
All combustion reactions which make use of elemental dioxygen and
also other reactions involving elements other than dioxygen, are
redox reactions
Eg: C(s) + O2(g) CO2(g)

3Mg(s) + N2(g) Mg3N2(s)

CH4(g) + 2O2(g) CO2(g) + 2H2O (l)

Decomposition reactions :

The decomposition reaction leads to the breakdown of a compound into

two or more components and one of them must be in the elemental
state
Eg: 2H2O (l) 2H2(g) + O2(g)

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

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

All decomposition reactions are not redox reactions.
Eg: CaCO3(s) CaO(s) + CO2(g)
 Displacement reactions:

An ion (or an atom) in a compound is replaced by an ion (or an atom) of

another element
X + YZ XZ + Y

Metal displacement:
A metal in a compound can be displaced by another metal in the
uncombined state.

CuSO4(aq) + Zn (s) Cu(s) + ZnSO4(aq)

V2O5(s) + 5Ca (s) 2V(s) + 5CaO (s)

Non-metal displacement:

The non-metal displacement redox reactions include hydrogen

displacement
All alkali metals and some alkaline earth metals (Ca, Sr, and Ba) will
displace hydrogen from cold water
0 +1 -2 +1 -2 +1 0

2Na(s) + 2H2O(l) → 2NaOH(aq) + H2(g)

0 +1 -2 +2 -2 +1 0
Ca(s) + 2H2O(l) → Ca(OH)2(aq) + H2(g)
Less active metals such as magnesium and iron react with steam to
produce dihydrogen gas.

Many metals, those which do not react with cold water, are capable of
displacing hydrogen from acids.
 Disproportionation reactions:

In a disproportionation reaction an element in one oxidation state is

simultaneously oxidised and reduced.

Eg:
The oxygen of peroxide, which is present in –1 state, is converted to zero
oxidation state in and decreases to –2 oxidation state in .
 Balancing of Redox Reactions

There are two methods for balancing chemical equations of redox

reactions. They are:
Oxidation Number Method
Half Reaction Method
 Oxidation Number Method:

Step 1: Write the correct formula for each reactant and product.
Step 2: Identify atoms which changes its oxidation number in the
reaction by assigning the 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 number so that these become equal.
Step 4: The involvement of ions in the reaction
• If the reaction is takes place in water, add H+ or OH– 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 then use H + ions in the
equation.
• If in basic solution then use OH– 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.
Half Reaction Method :

The two half equations are balanced separately and then added together
to give balanced equation.
Step 1: Produce unbalanced equation for the reaction in ionic form
Fe2+(aq) + Cr2O72–(aq) Fe3+(aq) + Cr3+(aq)
Step 2: Separate the equation into half-reactions:
Oxidation half :Fe2+(aq) Fe3+(aq)
Reduction half :Cr2O72–(aq) Cr3+(aq)
Step 3: Balance the atoms other than O and H in each half reaction
individually.
In reduction half reaction, multiply Cr3+ by 2 to balance Cr atoms
Cr2O72–(aq) 2Cr3+(aq)
Step 4: For reactions occurring in acidic medium, add H2O to balance O
atoms and H+ to balance H atoms
Cr2O72–(aq) + 14H+(aq) 2Cr3+(aq) + 7H2O(l)
Step 5: Add electrons to one side of the half reaction to balance the
charges.
In oxidation half reaction balance electrons on both sides
6Fe2+(aq) 6Fe3+(aq)+ 6e-
In reduction half reaction there are 12 electrons on left side and 6
electrons on right side. Hence add 6 electrons on left side
Cr2O72–(aq) + 14H+(aq)+ 6e- 2Cr3+(aq) + 7H2O(l)
Step 6: Add two half reactions to achieve the overall reaction and cancel
the electrons on each side.
6Fe2+(aq) + Cr2O72–(aq) + 14H+(aq) 6Fe3+(aq)+ 2Cr3+(aq) +7H2O(l)

Step 7: Verify that the equation contains the same type, charges and
number of atoms on both sides of the equation
 Redox Reactions as the Basis for Titrations
In Redox systems the titration method is used to determine the strength
of a reductant or oxidant using a redox sensitive indicator.
In this the reagent itself is intensely coloured
Eg: Permanganate ion MnO4– which acts as a self indicator
If there is no dramatic auto-colour change. There are indicators
which are oxidised immediately after the last bit of the reactant is
consumed, producing a dramatic colour change.
Eg: Cr2O72– which is not a self-indicator
In this iodine itself gives an intense blue colour with starch and has a
very specific reaction with thiosulphate (S2O32– ) ions

2Cu2+(aq) + 4I–(aq) Cu2I2(s) + I2(aq)

2– – 2–
 Redox Reactions and Electrode Processes
Daniell cell:
Take two beakers in which one beaker contains copper sulphate
solution and the other beaker contains zinc sulphate solution.
The solutions in two beakers are connected by a salt bridge which
provides electric contact between two solutions without mixing them.
The zinc and copper rods are connected by a metallic wire with a
provision for an ammeter and a switch.
When switch is off then no reaction takes place and no current flows
through metallic wire.
Set-up for Daniell cell
Current flow
When the switch is in the on position, the following are observed:
The transfer of electrons takes through the metallic wire connecting
the two rods but not take place directly from Zn to Cu2+
The electricity from solution in one beaker to solution in the other
beaker flows by the migration of ions through the salt bridge.
The flow of current is possible only if there is a potential difference
between the copper and zinc rods (electrodes)
If the concentration of each species taking part in the electrode reaction is
unity and the reaction is carried out at 298K, then the potential of each
electrode is said to be the Standard Electrode Potential.
Standard electrode potential of hydrogen electrode= 0.00 volts
• A negative Standard electrode potential means that redox couple is
a stronger reducing agent than the H+/H2 couple
• A positive Standard electrode potential means that redox couple is
a weaker reducing agent than the H+/H2 couple