Redox Reactions

Oxidation and Reduction Reactions

 Types of chemical Reactions
1)Non oxidation –reduction reactions
OR
Non Redox Reaction
2)Oxidation-Reduction reactions
OR
Redox Reaction
 Old Concept
Oxidation:Addition of Oxygen
Or Addition of Electronegative Element
Or Removal of Hydrogen
Or Removal of electropositive element
Reduction: Removal of Oxygen
Or Removal of Electronegative Element
Or Addition of Hydrogen
Or Addition of Electropositive Element
 Electronic Concept
Oxidation :Loss of Electron
Reduction : Gain of Electron
Oxidant Or Oxidising Agent : is an
atom,molecule or ion which accepts electron/s
from the other substance
Reductant Or reducing Agent: is an atom,
molecule or ion which donates electron/s to the
Other reactant.
Oxidation-Reduction

7
Oxidation-Reduction

(a): Placing Al in CuCl2 (b): Cu2+ in solution is reduced

dissolved in H2O forms Cu2+ ions to Cu metal
8
 4 Experiments:
1. Burning magnesium
2. Copper in silver nitrate solution
3. Chlorine solution and potassium iodide
solution
4. Exploding hydrogen

• Word equation
•Balanced symbol equation
 Oxidised – gains
oxygen

2Mg(s) + O2(g)  2MgO(s)

Must be a redox!

Oxidised – loss of e- Mg  Mg2+ +2e-

Put the
e- in.
Reduced – gain of e- O +2e-  O2-
 Cu(s) + 2AgNO3(aq)  Cu(NO3 )2(aq) + 2Ag(s)

Complete the half-

Oxidised?
equations
Reduced?

Oxidised – loss of e- Cu  Cu2+ +2e-

Reduced – gain of e- Ag+ +e-  Ag

Oxidation Number Or Oxidation State (ON)

Charge on an atom produced by donating or

accepting electrons is called oxidation number
or oxidation state.
 Valency and Oxidation Number
Valency and Oxidation number concepts are
different.In some cases (mainly in the case of
electrovalent compounds),valency and oxidation
numbers are the same but in some cases may
have different values
Oxidation Number
O.N. is the charge (real or imaginary)
present on the atom of the element when
It is in combination.It may have plus or
minus sign.
O.N. of an element may have different
Values.It depends on the nature of
compound in which it is present.
O.N. of the element may be a whole
number or fractional.
ON of the element may be zero.
Valency
It is the combining capacity of the
element.No plus or minus sign is
attached to it.
Valency of an element is usually fixed.
Valency is always a whole number.
Valency of the element is never zero
except of noble gases.
 Rules for Assigning the oxidation
Numbers
1)The Oxidation number of an uncombined
element is zero.
O atom ON in O2 =0
P atom ON in P4 =0
S atom ON in S8 =0
Na atom ON in Na=0
2)In a compound , the more electronegative
elements are assigned negative oxidation
numbers and the less electronegative elements
(i.e. electropositive elements ) are assigned
positive oxidation numbers
3)Group 1 elements (i.e.the alkali metals )in
their compounds have oxidation number +1 .
Group 2 elements (i.e the Alkaline earth metals )
have +2 Oxidation Number in their compounds.
4)Hydrogen usually has an oxidation number of
+1 in its compounds except in metallic hydrides
where it is -1.Thus in NaH , CaH2 LiH etc
oxidation number of H is -1.

5)Oxygen usually has an oxidation number of -2

except in peroxides where it is -1.Another
exception is the OF2and O2F2 where the
oxidation number oxygen is +2 and +1.
6)Fluorine has the oxidation number -1 in all of
its compound with other elements.

7)The oxidation number of a monoatomic ion is

equal to the charge on the ion.For example
K+1 ON=+1
Mg+2 ON=+2
Al+3 ON =+3
8)The algebraic sum of the oxidation number for
All the atoms combined in a molecule or ion is
equal to the net charge on the species.
 Question
Assign the oxidation of element which is
underlined
1)NO2
2)KMnO4
3)Cr2O7-2
4)Fe3O4
5)CrO5
6)NH4+
 Redox Reaction in terms of Oxidation
Number
Oxidation: is defined as an increase in the
oxidation number of an atom in a molecule or
ion from reactant to product.

Reduction:is defined as the decrease in the

oxidation number of an atom in a molecule or
ion going from reactant to product.
Oxidising Agent : Whose oxidation number
decreases
= Electron receiver
= Itself reduced

Reducing agent : Whose oxidation number

increases
= Electron donor
= Itself oxidised
 Guidelines for identification of oxidising
/reducing agents
a)If an element shows highest possible oxidation
state in a compound or ion,it can act as an
oxidising agent .For example KMnO4, K2Cr2O7,
HNO3, H2SO4, HClO4, KBrO3, KIO3,etc.
b)If an element in its lowest oxidation state or
can increase its O.N. in a compound , it can act
as a reducing agent.For example, H2S, FeSO4,
Na2S2O3 , SO2, SnCl2, many metals (Zn,Fe, Mg etc).
C)If an element shows intermediate oxidation
state in a compound or ion , it can act as both
oxidising and reducing agent.For example
H2O2, H2SO3 , HNO2 etc
 Balancing Redox Equations
A)Oxidation Number Method
1)Determine the oxidation number of each atom
in the eauation in order to identify the oxidising
agent and the reducing agent.
+1+7-2 +1+6-2 +2+6-2
KMnO4 + H2SO4 + FeSO4-----
+1+6-2 +2 +6-2 +3 +6-2 +1-2
K2SO4 + MnSO4 + Fe2(SO4)3 + H2O
2)Write separate half- reactions for oxidation
and reduction reactions.
+7 +2
KMnO4 MnSO4

+2 +3

FeSO4 Fe2(SO4)3
3) Balance the half –reactions with respect to
the atoms which are undergoing changes in the
oxidation .

+7 +2
KMnO4 MnSO4

+2 +3

2FeSO4 Fe2(SO4)3
4)Find the Change in oxidation number per atom
of both the oxidant and reductant.If there are
more than one atom present in the oxidant or
reductant ,then multiply the change in oxidation
number per atom by the number of atoms
present in the oxidant or reductant.Balance the
net oxidation number by adding electrons in
half equation.
 +7 +2
5 e-1+ KMnO4 MnSO4
+7 +2

+2 +3

2FeSO4 Fe2(SO4)3 +2e-1

+4 +6
4)Balance the electrons of two half equations by
cross multiplying by taking LCM of electrons
+7 +2
( 5 e-1+ KMnO4 MnSO4) x 2
+7 +2

+2 +3

( 2FeSO4 Fe2(SO4)3 +2e-1) x 5

+4 +6
5)Put these coefficients in original equation.

2KMnO4 + H2SO4 + 10 FeSO4

K2SO4 + 2MnSO4 +5 Fe2(SO4)3 + H2O

6)Balance the spectator ions.

2KMnO4 + 8H2SO4 + 10 FeSO4

K2SO4 + 2MnSO4 +5 Fe2(SO4)3 +

H2O
7) Balance the oxygen by adding H2O molecules
which is deficient to Oxygen

2KMnO4 + 8H2SO4 + 10 FeSO4

K2SO4 + 2MnSO4 +5 Fe2(SO4)3 + 8 H2O

For the reactions taking place in acidic medium ,
H+ (aq) ion’s may be added to overcome the
deficiency of H atoms
In Basic medium Hydrogen deficiency can be
made by adding H2O molecules on the deficient
Side and an equal number of OH- ions on the
other side of the equation.
 Ion electron Method
1)Write down the equation in the ionic form and
separate half reactions for Oxidation and
reduction half in the ionic forms

K2Cr2O7 + H2SO4 + FeSO4

K2SO4 + Cr2(SO4)3 + Fe2(SO4)3 + H2O

Cr2O7-2 Cr+3

Fe+2 Fe+3
2) Balance all atoms except oxygen and
hydrogen in each reaction (i.e. conservation of
atoms)

Cr2O7-2 2 Cr+3

Fe+2 Fe+3
• 3)Balance Oxygen by adding H2O(l) and
hydrogen by adding H+ ions

14H+ + Cr2O7-2 2 Cr+3 + 7H2O

Fe+2 Fe+3
4)Balance the charges by adding electrons so
that the total charge on both the sides of the
half reaction is equal .(i.e. conservation of
electric charge.

6e-1 +14H+ + Cr2O7-2 2 Cr+3 + 7H2O

Fe+2 Fe+3 + e -1
5)Obtain the final equation by adding the two
partial equations in such a way so that the
electrons are cancelled out.
(6e-1 +14H+ + Cr2O7-2 2 Cr+3 + 7H2O) x1

(Fe+2 Fe+3 + e -1)x6

Cr2O7-2 +14 H+ + 6 Fe+2 2Cr+ +7H2O + 6Fe+3

 Disproportionation Reaction
Disproportionation reactions are those redox
reactions when an element in a reactant shows
Different oxidation states in the products during
the course of chemical reaction.
+3-2 +4-2 +2-2
N2O3----------NO2 + NO
0 +1 -1
Cl2(g) + 2NaOH (aq)-----NaClO(aq)+ NaCl(aq) +H2O

0 +5 -1
3Cl2(g) + 6NaOH (aq)---NaClO3(aq)+ 5NaCl(aq+H2O
 Electrochemical Cells

_____Anodic__ _Cathodic
______half____ half______
__________

spontaneous
redox reaction
 Electrochemical Cells
The difference in electrical
potential between the anode
and cathode is called:
• __EMF__________________
• ____________________
• ____________________

Cell Diagram
Zn (s) + Cu2+ (aq) Cu (s) + Zn2+ (aq)
[Cu2+] = 1 M & [Zn2+] = 1 M
Zn (s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu (s)
anode cathode
 Standard Electrode Potentials

Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s)

Anode (oxidation): Zn (s) Zn2+ (1 M) + 2e-
Cathode (reduction): 2e- + 2H+ (1 M) 2H2 (1 atm)
 Standard Electrode Potentials
____________ ____________ ____________ (E0) is the
voltage associated with a reduction reaction at an electrode
when all solutes are 1 M and all gases are at 1 atm.
Any time you see º, think
“standard state conditions”

Reduction Reaction

2e- + 2H+ (1 M) 2H2 (1 atm)

E0 = 0 V

Standard hydrogen electrode (SHE)

 Standard Electrode Potentials
Ecell
0
= 0.76 V

Standard emf (Ecell

0
)

Ecell
0
= E0cathode - Eanode
0

Ecell
0
= E0reduct’n - Eoxid
0

Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s)

Ecell
0
= E0H+/H2 - EZn
0 2+
/Zn

0.76 V = 0 - E0Zn2+/Zn
E0Zn2+/Zn = -0.76 V
Zn2+ (1 M) + 2e- Zn E0 = ____________
 Standard Electrode Potentials

Ecell
0
= 0.34 V
Ecell
0
= E0cathode - Eanode
0

E0cell = E0Cu2+/Cu – EH0 +/H 2

0.34 = E0Cu2+ /Cu - 0

E0Cu2+/Cu = 0.34 V

Pt (s) | H2 (1 atm) | H+ (1 M) || Cu2+ (1 M) | Cu (s)

Anode (oxidation): H2 (1 atm) 2H+ (1 M) + 2e-
Cathode (reduction): 2e- + Cu2+ (1 M) Cu (s)
• E0 is for the reaction as written
• The more positive E0 the
greater the tendency for the
substance to be reduced
• The more negative E0 the
greater the tendency for the
substance to be oxidized
• Under standard-state
conditions, any species on the
left of a given half-reaction will
react spontaneously with a
species that appears on the
right of any half-reaction
located below it in the table
(the diagonal rule)
• The half-cell reactions are
reversible
• The sign of E0 changes when
the reaction is reversed
• Changing the stoichiometric
coefficients of a half-cell
reaction does not change the
value of E0
 Can Sn reduce Zn2+ under standard-state conditions?

How do we find the answer?

Look up the Eº values in Table.
Zn2+(aq) + 2e- —> Zn(s) (Is this oxidation or reduction?)

Which reactions in the table will reduce Zn2+(aq)?

 Equivalent Mass OR Equivalent Weight

Equivalent mass of a substance is the mass of substance which is equivalent to 1 parts

Of Hydrogen or 8 Parts of Oxygen or 35.5 parts of Chlorine .Equivalent mass is a variable

Term.

Equivalent mass of Element = Atomic Mass /Valency

 Equivalent Mass of Non Redox Reaction

Acid

Equivalent mass
Base

Salt
 Equivalent Mass of Acid
Equivalent mass of acid =

Molecular mass of acid

Number of replacable H+ (Basicity)

Example:
Equivalent mass of HCl and H2SO4

� H+ + Cl-
HCl ���
� 2H+ + SO4--
H2SO4 ���
1 + 35.5
Equivalent mass of HCl = = 36.5
1
2 �1 + 32 + 4 �16
Equivalent mass of H2SO4 = = 49
2
 Equivalent Mass of Base

Equivalent mass of base =

Molecular mass
Number of replacable OH- (Acidity)

Example:
Equivalent mass of NaOH and Ca(OH)2

� Na+ + OH-
NaOH ���
� Ca+ + + 2OH-
Ca(OH)2 ���
23 + 16 + 1
Equivalent mass of NaOH = = 40
1
40 + 2 �16 + 2 �1
Equivalent mass of Ca(OH)2 = = 37
2
 Equivalent mass of salt

Equivalent mass of salt =

Molecular mass
Total number of positive or
negative ch arg e
Example:
Equivalent mass of NaCl and MgCl2

NaCl ���� Na+ + Cl-

23 + 35.5
Equivalent mass of NaCl = = 58.5
1
� Mg+ + + 2Cl-
MgCl2 ���
240 + 2 �35.5
Equivalent mass of MgCl2 = = 47.5
2
 Equivalent Mass of Oxidising Or Reducing
Agent

Equivalent Mass of Oxidising = Molecular mass/nf

or Reducing Agent

Nf = Total number of moles of electrons gain or lost by one mole

of substance

= Total change in oxidation number in one mole of oxidising or

reducing substance
 Gram Equivalent Mass

Gram Equivalent is the mass of substance in grams which is

Numerically equal to its Equivalent mass.

Number of gram Equivalents

= Mass of substance in grams/Gram Equivalent mass
 Normality

It is number of gram equivalents in one litre of solution.

Normality = Number of grams equivalents of solute

/Volume of solution in litre

Normality = Number of milliequivalents of solute

/Volume of solution in ml
Law of Chemical Equivalence

According to law of equivalence, whenever two

Substances react ,the equivalents of each reactant and

products are equal.
 Relationship between Molarity and
Normality

Normality/Molarity = number of gram equivalents/number of moles

=Number of milliequivalents/ Number of millimoles

= Molecular Mass/Equivalent Mass= nf