REDOX TITRATION

OXIDATION- REDUCTION TITRATION:

B.KIRUTHIGA
LECTURER
DEPT OF PHARMACEUTICAL CHEMISTRY

What are we doing in

this experiment?
Determine the % of Iron, in a sample by
performing a redox titration between a
solution of the iron sample and potassium
permanganate (KMnO4).

What is redox titration?

A TITRATION WHICH DEALS WITH A
REACTION INVOLVING OXIDATION AND
REDUCTION OF CERTAIN CHEMICAL
SPECIES.

What is a titration?
The act of adding standard solution in small
quantities to the test solution till the reaction
is complete is termed titration.

What is a standard
solution?
A standard solution is one whose
concentration is precisely known.

What is a test solution?

A test solution is one whose
concentration is to be estimated

What is oxidation?
Old definition:
Combination of substance with oxygen

C (s) + O2(g)

CO2(g)

Current definition:
Loss of Electrons is Oxidation (LEO)
Na

Na+ + e-

Positive charge represents electron deficiency

ONE POSITIVE CHARGE MEANS DEFICIENT BY ONE ELECTRON

What is reduction?
Old definition:
Removal of oxygen from a compound

WO3 (s) + 3H2(g)

W(s) + 3H2O(g)

Current definition:
Gain of Electrons is Reduction (GER)
Cl + e-

Cl -

Negative charge represents electron richness

ONE NEGATIVE CHARGE MEANS RICH BY ONE ELECTRON

OXIDATION-REDUCTION
Oxidation and reduction go hand in hand.
In a reaction, if there is an atom undergoing
oxidation, there is probably another atom
undergoing reduction.
When there is an atom that donates electrons,
there is always an atom that accepts electrons.
Electron transfer happens from one atom to
another.

How to keep track of electron

transfer?
Oxidation number or oxidation state (OS):
Usually a positive, zero or a negative number (an integer)
A positive OS reflects the tendency atom to loose electrons
A negative OS reflects the tendency atom to gain electrons

Rules for assigning OS

The sum of the oxidation numbers of all of the atoms
in a molecule or ion must be equal in sign and value
to the charge on the molecule or ion.
Sulfate anion
Potassium Permanganate
KMnO4

SO42-

OS of K + OS of Mn +
OS of S + 4(OS of O) = -2
4(OS of O) = 0
Ammonium cation
NH4+
OS of N + 4(OS of H) = +1

Also, in an element, such as S8 or O2 , this rule

requires that all atoms must have an oxidation
number of 0.
In binary compounds (those consisting of only two
different elements), the element with greater
electronegativity is assigned a negative OS equal
to its charge as a simple monatomic ion.
NaCl

MgS

Na+ Cl-

Mg2+ S2-

When it is bonded directly to a non-metal atom,

the hydrogen atom has an OS of +1. (When bonded
to a metal atom, hydrogen has an OS of -1.)
H2O
2H+ O2-

NH4+
N3- 4(H+)

HCl
H+ Cl-

Except for substances termed peroxides or

superoxides, the OS of oxygen in its compounds is 2. In peroxides, oxygen has an oxidation number of
-1, and in superoxides, it has an oxidation number
of - . Hydrogen peroxide: H O = 2H+ 2O2 2
Potassium superoxide: KO2= K+

2O -1/2

Please Remember !!
In a periodic table,
Vertical columns are called GROUPS
Horizontal rows are called PERIODS
Electronegativity increases as we more left to right
along a period.
Electronegativity decrease as we move top to bottom
down a group.

s- block

p- block
d- block

f- block

Group 1A
Has 1e- in the
outermost shell
Tend to loose 1eOS = +1

Alkali metals

Group
2A
Has 2e- in the
outermost shell
Tend to loose 2eOS = +2

Alkaline-earth
metals

s- block
p- block
d- block

f- block

p - block
Electronegativity Increases

Electronegativity
decreses

Group 3A
Has 3e- in the
outermost shell
Tend to loose 3eOS = +3

Group 4A
Has 4e- in the
outermost shell
Can either loose 4eOr gain 4eExhibits variable
Oxidation state
-4,-3,-2,-1,0,+1,+2,+3,+4

Group 5A
Has 5e- in the
outermost shell
Can either loose 5eOr gain 3eOxidation state
-3,+5

Group 6A
Has 6e- in the
outermost shell
Tend to gain 2e-

Chalcogens

Oxidation state
-2

Group number - 8

Group 7A
Has 7e- in the
outermost shell
Tend to gain 1e-

Halogens

Oxidation state
-1

Group number - 8

Group 8A
Has 8e- in the
outermost shell
Tend to gain/loose 0 e-

Inert elements
or
Noble gases

Oxidation state
0

Group number - 8

Sample problem
Find the OS of each Cr in K2Cr2O7
Let the OS of each Cr be = x
OS of K = +1 (Remember K belongs to Gp. 1A)
OS of O = -2 (Remember O belongs to Gp. 6A)
Net charge on the neutral K2Cr2O7 molecule = 0
So we have,
2(OS of K) + 2 ( OS of Cr) + 7 (OS of O)= 0
2(+1) + 2 ( x) + 7 (-2)= 0
2+ 2 ( x) +(-14)= 0

2+ 2 ( x) +(-14)= 0
2 ( x) +(-12) = 0
2 ( x) = (12)
x=6
Find the OS of each C in C2O42Let the OS of each C be = x
OS of O = -2 (Remember O belongs to Gp. 6A)
So we have,
2(OS of C) + 4 ( OS of O) = -2
2(x) + 4 ( -2) = -2
2 ( x) +(-8)= -2

2 ( x) +(-8)= -2
2 ( x) = +6
( x) = +3
Find the OS of N in NH4+
Let the OS of each N be = x
OS of H = +1 (Remember H belongs to Gp. 1A)
So we have,
(OS of N) + 4 ( OS of H) = +1
(x) + 4 ( +1) = +1
( x) +(4)= +1
( x) = -3

Balancing simple redox

reactions
Cu (s) + Ag +(aq)
Ag(s)

Cu2+(aq)

Step 1: Pick out similar species from the equation

Cu(s)
Ag +(aq)

Cu2+(aq)
Ag (S)

Step 2: Balance the equations individually for

charges and number of atoms
Cu0(S)
Cu2+(aq) + 2eAg +(aq) + eAg (S)

Balancing simple redox reactions

Cu0(S)

Cu2+(aq) + 2e-

Cu0(S) becomes Cu 2+ (aq) by loosing 2 electrons.

So Cu0(S) getting oxidized to Cu2+(aq) is the
oxidizing half reaction.
Ag +(aq) + eAg (S)
Ag+(aq) becomes Ag 0 (S) by gaining 1 electron.
So Ag+(aq) getting reduced to Ag (S) is the
reducing half reaction.

LEO-GER

Balancing simple redox

reactions

Final Balancing act:

Making the number of electrons equal in both
half reactions
[Cu0(S)
[Ag +(aq) + eSo we have,
Cu0(S)
2Ag +(aq) + 2e-

Cu2+(aq) + 2e-] 1
Ag (S)] 2
Cu2+(aq) + 2e2Ag (S)

Balancing simple redox

reactions
Cu0(S)

2Ag +(aq) + 2e-

Cu2+(aq) + 2e2Ag (S)

Cu0(S) + 2Ag +(aq) + 2eCu2+(aq) + 2Ag (S) + 2eCu0(S) + 2Ag +(aq)

Cu2+(aq) + 2Ag (S)

Number of e-s involved in the overall reaction is 2

Balancing complex redox

reactions
Fe+2(aq) + MnO4-(aq)
Oxidizing half:
Fe+2(aq)
Reducing half:
MnO4-(aq)

Mn+2(aq) +

Fe+3(aq)

Fe+3(aq) + 1eMn+2(aq)

Balancing atoms:
Balancing
-(aq)+
MnO
4
oxygens:

Mn+2(aq) + 4H2O

Balancing complex redox

reactions
Reaction happening in an acidic medium

Balancing hydrogens:
MnO4-(aq)+8H+

Mn+2(aq) + 4H2O

Oxidation
numbers: Mn = +7,
O = -2

Mn = +2

Balancing electrons:
The left side of the equation has 5 less electrons than the right side

MnO4-(aq)+8H++ 5e-

Mn+2(aq) + 4H2O

Reducing Half

Balancing complex redox

reactions
Final Balancing act:
Making the number of electrons equal in both half reactions

[Fe+2(aq)
[MnO4-(aq)+8H++ 5e5Fe+2(aq)
MnO4-(aq)+8H++ 5e-

Fe+3(aq) + 1e- ] 5
Mn+2(aq) + 4H2O]1
5Fe+3(aq) + 5eMn+2(aq) + 4H2O

5Fe2++MnO4-(aq)+8H++ 5e5Fe3+ +Mn+2(aq) + 4H2O + 5e-

Balancing complex redox

reactions
5Fe2++MnO4-(aq)+8H+
5Fe3+ +Mn+2(aq) + 4H2O
5 Fe 2+ ions are oxidized by 1 MnO4- ion to 5 Fe3+
ions. Conversely 1 MnO4- is reduced by 5 Fe2+ ions
to Mn2+.
If we talk in terms of moles:
5 moles of Fe 2+ ions are oxidized by 1mole of
MnO4- ions to 5 moles of Fe3+ ions. Conversely
1 mole of MnO4- ions is reduced by 5 moles of
Fe2+ ions to 1 mole of Mn2+ ions.

Conclusion from the

balanced
chemical equation
For one mole of MnO4- to completely react
With Fe2+, you will need 5 moles of Fe2+ ions.
So if the moles of MnO4- used up in the
reaction
is known, then the moles of Fe2+ involved in
the Mathematically written:
reaction will be 5 times the moles of MnO4

Moles of Fe = 5 [moles of MnO4 ]

2+

How does this relationship concern our experiment?

Titration of unknown sample of Iron Vs KMnO4:

The unknown sample of iron contains, iron in Fe2+
oxidation state. So we are basically doing a redox
titration of Fe2+ Vs KMnO4
5Fe2++MnO4-(aq)+8H+

5Fe3+ +Mn+2(aq) + 4H2O

Moles of Fe = 5 [moles of MnO4 ]

2+

Vinitial
Vfinal- Vinital= Vused (in mL)
Important requirement:
The concentration of
KMnO4 should be
known precisely.

KMnO4
Vfinal

End point:
Pale Permanent
Pink color

250mL

250mL

250mL

1L
Vused (in mL)
VKMnO4 Used (in L) =

1
1000mL

Moles of MnO4 = Molarity of MnO4 VKMnO4 Used (in L)

Moles of Fe = 5 [moles of MnO4 ]

2+

2+

55.85 g of Fe
2+
Grams of Fe =
moles of Fe
2+
1 mole of Fe
2+

+2

grams of Fe
% Fe in sample =
100%
mass of sample in grams

Problem with KMnO4

Unfortunately, the permanganate solution,

once prepared, begins to decompose by the
following reaction:
4 MnO4-(aq) + 2 H2O(l) 4 MnO2(s) + 3 O2(g) + 4 OH-(aq)

So we need another solution whose concentration

is precisely known to be able to find the precise
concentration of KMnO4 solution.

Titration of Oxalic acid Vs

KMnO4
Primary
standard

Secondary
standard

16 H+(aq) + 2 MnO4-(aq) + 5 C2O4-2(aq) 2 Mn+2(aq) +

10 CO2(g)
+ 8 H2O(l)

5 C2O42- ions are oxidized by 2 MnO4- ions to 10 CO2

molecules. Conversely 2 MnO4- is reduced by 5 C2O42ions to 2Mn2+ ions.

Titration of Oxalic acid Vs

KMnO4

16 H+(aq) + 2 MnO4-(aq) + 5 C2O4-2(aq) 2 Mn+2(aq)

+10CO2(g) + 8 H2O(l)

If we talk in terms of moles:

5 moles of C2O42- ions are oxidized by 2 moles MnO4ions to 10 moles of CO2 molecules. Conversely 2 moles
of MnO4- is reduced by 5 moles of C2O42- ions to
2 moles of Mn2+ ions.

Conclusion from the balanced

chemical equation
For 5 moles of C2O42- ions to be completely oxidized
by MnO4- we will need 2 moles of MnO4- ions.
Conversely for 2 moles of MnO4- to be completely
reduced by C2O42-, we will need 5 moles of C2O42- ions
2

5 Moles of C2O4 2 moles of MnO4

2

2
1 Moles of C2O4
moles of MnO4
5

Vinitial

Vfinal- Vinital= Vused (in mL)

Important requirement:
The concentration of
KMnO4 should be
known precisely.

KMnO4
Vfinal

End point:
Pale Permanent
Pink color
250mL

0.15 g OXALIC ACID

+ 100 mL of 0.9 M
H2SO4.Heated to 80C

250mL

250mL

1L
Vused (in mL)

VKMnO4 Used (in L) =

1
1000mL

Moles of C2O4

Weight of oxalic acid (in g )

=
)
Mol.Wt of Oxalic acid ( g
mol

2 mol MnO4
1mol C2O4
mol MnO4 =
2 Moles of Ox
5 mol C2O4
1mol Na2C2O4

mol MnO4
[ MnO4 ] =
VKMnO4Used (in L)

When preparing 0.9 M H2SO4

1.Wear SAFETY GOGGLES AND GLOVES
2.Use graduated cylinder to dispense the acid
from the bottle
3. Please have about 100 mL of water in
500 mL volumetric flask, before adding
acid in to it.
4. Add acid to the flask slowly in small
aliquots.

THANKYOU