SUBMITTED TO:

Md. Kamrul
Hasan

Lecturer

Department of
Pharmacy

Daffodil
International
University
Redox titration in
pharmaceutical analysis
Name of the Course : Pharmaceutical Analysis and QC-1 ;Course
Code : BPH-221 ; Program : B. Pharm.

SUBMITTED BY:
NAME: Rifat Ahmed
Tanvir

ID: 201-29-399
 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) + O 2(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 si

gn and value

to the char

ge on the molecule or ion.

KMnO4 SO42-

Potassium Permanganate Sulfate anion

OS of K + OS of Mn +

4(OS of O) = 0 OS of S + 4(OS of O) = -2

NH4+ Ammonium cation OS of N + 4(OS of H) = +1

Also, in an element, such as S

8 or O
2 , 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 Na+ Cl - MgS 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.)

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 -½ .

2O HCl 2H+O2-NH4+N3- 4(H+) H + Cl

Hydrogen peroxide: H 2 O 2= 2H + 2O

Potassium superoxide: KO 2= 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.

Balancing simple redox

reactions Cu (s) + Ag +(aq) Ag(s) + Cu2+(aq)

Step 1: Pick out similar species from the equation

Cu(s) Cu2+(aq)

Ag +(aq) Ag (S)

Step 2: Balance the equations individually for

charges and number of atoms

Cu 0(S) Cu2+(aq) + 2e

Ag +(aq) + e - Ag (S)

Cu 0(S) Cu2+(aq) + 2e

Ag +(aq) + e - Ag (S)

Cu 0(S) becomes Cu 2+ (aq) by loosing 2 electrons.

So Cu 0(S) getting oxidized to Cu2+(aq) is the

oxidizing half reaction.

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 Redox Reactions using Half

Reaction Method
1- Divide the equation into an oxidation half-reaction and a reduction

half-reaction
2- Balance these – Balance the elements other than H and O

3- Balance the O by adding H2O – Balance the H by adding H+

4- Balance the charge by adding e5- Multiply each half-reaction by an integer

such that the number of

electron lost in one equals the number gained in the other

6- Combine the half-reactions and cancel

7- Balancing Redox Reactions Using the Half Reaction Method

Example-1
Al + HCl = AlCl3 + H2 0 +1 -1 +3 -1 0

Oxidation: (Al = Al3+ + 3e-)  2 = 6 e–

Reduction: (2H+ + 2e = H2 )  3 = 6 e–

Redox: 2Al + 6H+ = 2Al3+ + 3H2

Example-2
MnO4 + C2O4 2 + H+ = Mn2+ + CO2 + H2O

1- Balance each half reaction: MnO4 + 5é = Mn2+C2O42 = 2 CO2 + 2é

2- Use the number of moles so as to make the electrons gained in one

reaction equal those lost in the other one

Measuring the endpoint of a titration

Different methods to determine the endpoint include:
 Indicator: A substance that changes color in response to a chemical change.
An acid–base indicator (e.g., phenolphthalein) changes color depending on the
pH. Redox indicatorsare also used. A drop of indicator solution is added to the
titration at the beginning; the endpoint has been reached when the color
changes.

 Potentiometer: An instrument that measures the electrode potential of the

solution. These are used for redox titrations; the potential of the working
electrode will suddenly change as the endpoint is reached.

An elementary pH meter that can be used to monitor titration reactions

 pH meter: A potentiometer with an electrode whose potential depends on

the amount of H+ ion present in the solution. (This is an example of an ion-
selective electrode.) The pH of the solution is measured throughout the
titration, more accurately than with an indicator; at the endpoint there will be
a sudden change in the measured pH.

 Conductivity: A measurement of ions in a solution. Ion concentration can

change significantly in a titration, which changes the conductivity. (For
instance, during an acid–base titration, the H+ and OH− ions react to form
neutral H2O.) As total conductance depends on all ions present in the solution
and not all ions contribute equally (due to mobility and ionic strength),
predicting the change in conductivity is more difficult than measuring it.

 Color change: In some reactions, the solution changes color without any
added indicator. This is often seen in redox titrations when the different
oxidation states of the product and reactant produce different colors.

 Precipitation: If a reaction produces a solid, a precipitate will form during the

titration. A classic example is the reaction between Ag+ and Cl− to form the
insoluble salt AgCl. Cloudy precipitates usually make it difficult to determine
the endpoint precisely. To compensate, precipitation titrations often have to
be done as "back" titrations (see below).

 Isothermal titration calorimeter: An instrument that measures the heat

produced or consumed by the reaction to determine the endpoint. Used in
biochemical titrations, such as the determination of how substrates bind to
enzymes.

 Thermometric titrimetry: Differentiated from calorimetric titrimetry

because the heat of the reaction (as indicated by temperature rise or fall) is
not used to determine the amount of analyte in the sample solution. Instead,
the endpoint is determined by the rate of temperature change.

 Spectroscopy: Used to measure the absorption of light by the solution

during titration if the spectrum of the reactant, titrant or product is known.
The concentration of the material can be determined by Beer's Law.

 Amperometry: Measures the current produced by the titration reaction as a

result of the oxidation or reduction of the analyte. The endpoint is detected as
a change in the current. This method is most useful when the excess titrant can
be reduced, as in the titration of halides with Ag+ .
 CONCLUSION
In every redox reaction, both reduction and oxidation must occur. Substance
that gives electrons is the reducing agent or reductant. Substance that accepts
electrons is the oxidizing agent or oxidant. Reaction of ferrous ion with
chlorine gas Overall, the number of electrons lost in the oxidation half reaction
must equal the number gained in the reduction half equation.

THE END