ANUSHA .

CHEMISTRY
ANALYTICAL CHEMISTRY

Titrimetric analysis:
Titrimetric analysis is a method of analysis in which a solution of the substance being
determined is treated with a solution of a suitable reagent of exactly known concentration.
The reagent is added to the substance until the amount added is equivalent to the amount of
substance to be determined.

Introduction: The term titrimetric analysis refers to quantitative chemical analysis carried
out by determining the volume of a solution of accurately known concentration which is
required to react quantitatively with a measured volume of a solution of a substance to be
determined.
The solution of accurately known concentration is called standard solution.
In titrimetric analysis the reagent of known concentration is called titrant.
And the substance being titrated is termed titrand.
The standard solution is usually add from a long graduated tube called burette.
The process of adding the standard solution until the reaction is just complete is termed
titration, the point at which this occurs is called equivalence point.
A very small difference usually occurs this represents the titration error.

Definitions:
Volumetric analysis: Estimation of substance which involve measurement of volumes
of solutions is called volumetric analysis.
The principle of volumetric analysis solutions of equal normality react in equal volumes this
follows from the fat that in a chemical reaction one gram equivalent weight of a substance
react with one gram equivalent weight of another substance.

Titration: Titration is an analytical procedure by which the exact volume of a solution

reacting with a known volume of another solution can be determined.

Indicator: these are generally organic substances used to determine the endpoint in the
titration. or Indicator is a substance that is added to a solution in a titration which indicates
the end point by change of colour.

End point: During a titration the end is a stage at which the reaction between the two
solutions is just complete. The end point is also known as equivalent point.

Primary standard:A primary standard is an ultrapure compound that serves as the

reference material for a titration or for another type of quantitative analysis.
Ex:oxalic acid.

1
 ANUSHA .G

Secondary standard: A secondary standard is a compound whose purity has been

determined by chemical analysis.
Ex:HCl.

Titrations can be classified as:

1.Acid-base Titrations
2.Redox Titrations.
3.Precipitation Titrations.
4.Complexometric Titrations.

1.Acid-base Titrations : An acid–base titration is a method of quantitative analysis for

determining the concentration of an acid or base by exactly neutralizing it with a standard
solution of base or acid having known concentration.

● Acidimetry:
Acidimetry is the specialized analytic use of acid-base titration to determine the
concentration of a basic substances using standard acid.

● Alkalimetry:
Alkalimetry is the same concept of specialized analytic acid-base titration, but for an
acidic substance using standard base.

2.Redox Titrations:
A redox titration is a type of titration based on a redox reaction between the analyte and
titrant.

3.precipitation Titration:
Precipitation titration is a type of titration which involves the formation of precipitate during
the titration technique. In precipitation titration, the titrant reacts with analyte and forms an
insoluble substance called precipitate.

4.Complexometric Titrations:
Complexometric Titration or chelatometry is a type of volumetric analysis wherein the
coloured complex is used to determine the endpoint of the titration.

Preparation and dilution of a solution/reagents:

● A dilute solution is one in which there is a relatively small amount of solute dissolved
in the solution.
● A concentrated solution contains a relatively large amount of solute.

Preparing Stock Solutions:

A stock solution is prepared by weighing out and appropriate portion of a pure solid or by
measuring out and appropriate volume of a few liquid and diluting to a known volume.

2
 ANUSHA .G

Preparing solution by dilution:

Solutions with small concentrations are often prepared by diluting a more concentrated stock
solution a known volume of the stock solution is transferred to a new container and brought
to a new volume.

Dilutions:
When preparing a dilution, decide the volume and molar concentration of the resulting
solution you require. Use the following equation to determine how much of the concentrated
reagent is needed to prepare the diluted solution,

Mreagent × Vreagent = Mdilution × Vdilution

where M is molarity and V is volume.

Slowly add the calculated volume of concentrated reagent to the proper-size volumetric flask
half filled with distilled or deionized water and swirl the flask to mix. Once the solution is at
room temperature, dilute to the mark with water, insert and secure the stopper, and invert the
flask several times to mix.

For example, what volume of 10 M acetic acid is required to prepare 1.0 L of 0.50 M acetic
acid?

10 M × Vreagent = 0.50 M × 1.0 L

Vreagent = 0.050 L = 50 mL
A volume of 50 mL of 10 M acetic acid is required to prepare 1.0 L of 0.50 M acetic acid.

Molarity:
Molarity (M) is defined as the number of moles of solute per litre of solution.

Molarity = moles of solute / litres of solution

For example: Molecular mass of Sulphuric acid is 98. Now if 98 gram of sulphuric acid is
present in 1 litre of solution then it is 1 molar solution of Sulphuric acid. And therefore
molarity will be 1.

Molality:
Molality (m) is defined as the number of moles of solute per kilogram of solvent.

Molality = moles of solute / kilograms of solvent

If 98 gram of sulphuric acid is present in 1 kg of water then it is 1 molal solution of Sulphuric
acid in water. And therefore molality will be 1.

Normality:
Normality is defined as the number of equivalents per litre of solution.

Normality = number of equivalents / 1 L of solution

3
 ANUSHA .G

A 1 N HCl solution = A one Molar HCl solution because only I mole of H+ is formed per mole
of HCl.
However, with sulphuric acid H2SO4, 2 moles of H+ are formed per mole of acid therefore 1
Molar H2SO4 = 2NH2SO4.

Mole fraction:
Mole fraction represents the number of molecules of a particular component in a mixture
divided by the total number of moles in the given mixture.
Mole fraction = moles of a / total moles.

Use of N1V1 N2V2 formula:

Grams per liter = Normality × Equivalent weight. 2.8 = N1× 56 . N1= 2.8 / 56 = 0.05 N . N1V1(
HCl )= N2V2(NaOH ) or 0.025 ×V1= 0.05 × 25 ∴ V1 = 50 ml .

Salts:
Any chemical compound formed from the reaction of an acid with a base
(neutralization).
HCl+NaOH——>NaCl+H2O

Prepare a 0.1M solution of NaOH in 1L & and 500ml

1000 ml of 1M NaOH requires 40g NaOH
=> 1000ml of 0.1M NaOH requires = 40/10 = 4g NaOH
=> 500ml of 0.1M NaOH requires = 40/2*10 = 2g NaOH.

PPM (parts per million):

Parts per million (ppm) is a commonly used unit of concentration for small values. One part
per million is one part of solute per one million parts solvent or 10-6.
1 PPM is equivalent to the absolute fractional amount multiply by 1 million it can be
expressed in mg/L.
PPM= mass of solute ×106.
total mass of solution

Prepare PPM solution:

100g in 100ml of water

PPM=Mass of solute ×106.
Solution

100 ×1000=1000ppm
100
● 10 PPM solution

100 × 1 × 1000=10ppm
100 100

4
 ANUSHA .G

● 5ppm solution

100 × 5 × 2 ×1000=5ppm
100 100 20

● 15ppm solution

100 × 10 × 3 ×1000=15ppm
100 100 20

Conversion factors:
Conversion factors are quantities that are equal to one another, such as 100cm=1m, in
which both values describe a length. Relationships are between two values that are not
necessarily a measure of the same quantity. For example, the density of water is 1.00g/mL.

Acid base titrimetry:

The acid base titrations involved the determination of the acidity or alkalinity of solutions and
the purity of carbonates and alkaline earth oxides.

A monoprotic acid is an acid that has only one hydrogen ion or Proton to donate per formula.
Example: HCL strong acid .

A polyprotic acid is an acid that has two or more hydrogen ion to donate per formula.
Example :H2SO4 H3PO4.

A monobasic base is one that will accept just one hydrogen ion per formula.
Example: NaOH strong base NH4OH weak base.

A poly basic base is one that will accept two or more hydrogen ions per formula.
Example:Na2CO3,Na3PO4.

A titration is a procedure for carrying out a chemical reaction between two solutions by the
controlled addition from a burette of one solution (the titrant) to the other, allowing
measurements to be made throughout the reaction. For a reaction between an acid and a
base, a titration is useful for measuring the pH at various points throughout the reaction.
A titration curve is a graph of the pH as a function of the amount of titrant (acid or base)
added.

Acid-base titrations estimate acids or bases with unknown concentrations using a standard
acid or alkali solution.

Acidimetry estimates the concentration of an alkali solution using a standard acid solution.

5
 ANUSHA .G

Similarly, alkalimetry determines the concentration of an acid solution using a standard

alkali solution.

Titrating curves:
The titration curve for a precipitation titration follows the change in either the analytes or
titrants concentration as a function of the volume of titrant.
Example: In an analysis for I using Ag+ as a titrant
Ag+ + I- ⇌AgI(s)
Titration curve :We can determine the pH of the solution at the equivalence point through a
titration curve. It indicates the change in the pH of the analyte solution as the titrant is added
from the burette.
The titration curve is a plot between the volume of titrant dripped into the analyte versus the
pH of the analyte solution.

X-coordinate indicates the volume of titrant added before starting the titration.
Y-coordinate represents the pH of the analyte solution during the titration.
The solution’s pH at the equivalence point depends upon the strength of acids, and bases
react in the titration.

● Strong acid-strong base titration (pH = 7 at equivalence point)

● Weak acid-strong base titration (pH > 7 at equivalence point)
● Strong acid-weak base titration (pH < 7 at equivalence point)
● Weak acid-weak base titration (pH varies)

Based on the strength of acids and bases, acid-base titrations are of the following
types:

● Strong acid-Strong base

● Weak acid-Strong base
● Strong acid-Weak base
● Weak acid-Weak base

Strong Acid-Strong Base Titrations:

Here is an example of a titration curve, produced when a strong base is added to a strong
acid. This curve shows how pH varies as 0.100 M NaOH is added to 50.0 mL of 0.100 M
HCl.
The equivalence point of the titration is the point at which exactly enough titrant has been
added to react with all of the substance being titrated with no titrant left over. In other words,
at the equivalence point, the number of moles of titrant added so far corresponds exactly to
the number of moles of substance being titrated .
Note: that the pH increases slowly at first, then rapidly as it nears the equivalence point
.

6
 ANUSHA .G

Calculate the pH at any point, including the equivalence point, in an acid-base titration.
At the equivalence point, the pH = 7.00 for strong acid-strong base titrations. However, in
other types of titrations, this is not the case.

OR
Strong Acid-Strong Base Titration:
In this, the strong acid and strong base dissociate entirely to give a neutral solution. At the
equivalence point, hydronium (H+) and hydroxide (OH–) ions combine to give water.

For this reason, the pH is always 7 at the equivalence point between the strong acid and
strong base. This kind of titration uses a phenolphthalein indicator, as you can quickly notice
the colour change.

Example: Titration of hydrochloric acid (HCl) with NaOH. The reaction between the two gives
neutral salt (NaCl) and water.

EXAMPLE:
What is the pH when 49.00 mL of 0.100 M NaOH solution have been added to 50.00 mL of
0.100 M HCl solution?
Because it is a strong acid-base reaction, the reaction simplifies to:

H+ (aq) + OH- (aq) ⇌ H2O (l)

7
 ANUSHA .G

The original number of moles of H+ in the solution is:

50.00 x 10-3 L x 0.100 M HCl = 5.00 x 10 -3 moles

The number of moles of OH- added is :

49.00 x 10-3 L x 0.100 M OH- = 4.90 x 10 -3 moles

Thus there remains:

(5.00 x 10-3) - (4.90 x 10-3) = 1.0 x 10-4 moles H+ (aq)

The total volume of solution is 0.04900 L + 0.05000 L = 0.09900 L

[H+] = {1.0 x 10-4 moles / 0.09900 L } = 1.0 x 10 -3 M

pH = 3.00

Weak acid -strong base titration:

Here, 0.100 M NaOH is being added to 50.0 mL of 0.100 M acetic acid.

There are three major differences between this curve (in blue) and the one we saw before (in
black):
1. The weak-acid solution has a higher initial pH.
2. The pH rises more rapidly at the start, but less rapidly near the equivalence point.
3. The pH at the equivalence point does not equal 7.00.

POINT OF EMPHASIS : The equivalence point for a weak acid-strong base titration has a
pH > 7.00.
For a strong acid-weak base or weak acid-strong base titration, the pH will change rapidly at
the very beginning and then have a gradual slope until near the equivalence point. The
gradual slope results from a buffer solution being produced by the addition of the strong acid
or base, which resists rapid change in pH until the added acid or base exceeds the buffer's
capacity and the rapid pH change occurs near the equivalence point.

8
 ANUSHA .G

EXAMPLE:
What is the pH when 30.0 mL of 0.100 M NaOH have been added to 50.0 mL of 0.100 M
acetic acid?

We now calculate the resulting molarities :

[HC2H3O2] = { 2.00 x 10-3 mol HC2H3O2 / 0.0800 L } = 0.0250 M

[C2H3O2-] = { 3.00 x 10-3 mol C2H3O2- } / 0.0800 L } = 0.0375 M
STEP 2: Equilibrium calculation, using simplification:

Ka = { [H+][C2H3O2-] / [HC2H3O2] } = 1.8 x 10-5

[H+] = { KA [HC 2H3O2] / [C2H3O2-] } = { (1.8 x 10-5)(0.0250) / (0.0375) } = 1.2 x 10-5 M

pH = -log(1.2 x 10-5) = 4.92.

OR

Weak Acid-Strong Base Titration:

Here, the reaction of a weak acid with a strong base reacts in a one-to-one ratio. At the
equivalence point of a weak acid and strong base titration, the pH is larger than 7.
Phenolphthalein is more proffered for this titration.

Example: Titration of acetic acid (CH3COOH) with NaOH. This reaction gives sodium
acetate (CH3COONa) and water.

Strong Acid-Weak Base Titration:

Here, 0.100 M HCl is being added to 50.0 mL of 0.100 M ammonia solution.
As in the weak acid-strong base titration, there are three major differences between this
curve (in blue) and a strong base-strong acid one (in black)
(Note that the strong base-strong acid titration curve is identical to the strong acid-strong
base titration, but flipped vertically.)

1. The weak-acid solution has a lower initial pH.

2. The pH drops more rapidly at the start, but less rapidly near the equivalence point.
3. The pH at the equivalence point does not equal 7.00.

9
 ANUSHA .G

POINT OF EMPHASIS : The equivalence point for a weak base-strong acid titration has a
pH < 7.00.

OR
Strong Acid-Weak Base Titration

Here, the acid and base react to give an acidic solution. A conjugate acid formed during the
titration gives a proton or hydronium ion to the base. At the equivalence point of a strong
acid-weak base titration, the pH is less than 7. Methyl orange is preferred for this titration.

Titrations of Polyprotic Acids

An example of a polyprotic acid is H2CO3 which neutralizes in two steps:

H2CO3(aq) + OH-(aq) —>H2O(l) + HCO3-(aq)

HCO3-(aq) + OH-(aq)—>H2O(l) + CO32-(aq)
The titration curve for these reactions will look like this, with two equivalence points.

Example: Titration of hydrochloric acid (HCl) with ammonia (NH3). This reaction forms a
neutral salt, ammonium chloride (NH4Cl).

10
 ANUSHA .G

Weak Acid-Weak Base Titration:

Here, the acid and base react to give a slightly basic solution. A conjugate base is formed
during the titration. As the OH– reacts with the H+ in the acetic acid during this titration, the
acetate ion (C2H3O2–) is formed.

This conjugate base reacts with water to form a slightly basic solution. In this titration, the pH
gradually changes around the equivalence point (with a pH greater or less than 7).

Example: Titration of acetic acid (CH3COOH) with ammonia (NH3). This reaction forms a
neutral salt, ammonium acetate (CH3CO2NH4).

Uses of Titrations:
The most common use of titrations is for measuring unknown concentrations. This is done
by titrating a known volume of the unknown solution with a solution of known concentration
(where the two react in a predictable manner) and finding the volume of titrant needed to
reach the equivalence point using some method appropriate to the particular reaction. Then,
the volume and concentration of titrant can be used to calculate the moles of titrant added,
which, when used with the reaction stoichiometry, gives the number of moles of substance
being titrated. Finally, this quantity, along with the volume of substance being titrated, gives
the unknown concentration.

For acid-base titrations, the equivalence point can be found very easily. A pH meter is simply
placed in the solution being titrated and the pH is measured after various volumes of titrant
have been added to produce a titration curve. The equivalence point can then be read off the
curve.

Selecting and Standardizing a Titrant:

Standardization is accomplished by titrating a known amount of an appropriate acidic or
basic primary standard. The majority of titrations involving basic analytes, whether
conducted in aqueous or nonaqueous solvents, use HCl, HClO4, or H2SO4 as the titrant.

11
 ANUSHA .G

Inorganic analysis:
Qualitative inorganic analysis is a method of analytical chemistry which seeks to find the
elemental composition of inorganic compounds. It is mainly focused on detecting ions in an
aqueous solution, therefore materials in other forms may need to be brought to this state
before using standard methods. The solution is then treated with various reagents to test for
reactions characteristic of certain ions, which may cause color change, precipitation and
other visible changes.
Qualitative inorganic analysis is that branch or method of analytical chemistry which seeks to
establish the elemental composition of inorganic compounds through various reagents.

Inorganic analysis advantages:

● Techniques are complementary to other methods within Intertek powder X-Ray

Diffraction (pXRD) , X-ray photoelectron spectroscopy (XPS) and Microscopy.
● High sensitivity, high selectivity instrumentation.
● Not limited by sample type.
● Specialist experience and knowledge for crucial sample preparation.
● Work to industry and government regulatory standards, as required.
● Fast response and flexibility.

12
 ANUSHA .G

Complexometric titration:
Indicators for EDTA titration:

Theory of metal Ion indicators:

A metal ion indicator is a compound whose colour changes when it buyings to a metal Ion.
Example: EriChrome black T (EBT)
This compound must bind metal less strongly than EDTA.

● The success of an EDTA titration depends upon the precise determination of the end
point.
● The colour reaction must be such that before the end point when nearly all the metal
ion is complexed with EDTA the solution is strongly coloured.
● The colour reaction should be specific or at least selective.
● The metal indicator Complex must process appreciable stability but the metal
indicator Complex must however be less stable than the metal EDTA complex.
● The colour contrast between the free indicator and the metal indicator Complex
should be such as to be readily observed.
● The reaction corresponding to use of a metal Ion indicator in an EDTA titration can be
represented as
M-In + EDTA ———>M-EDTA + ln
● This reaction will take place only if the M-EDTA complex is more stable than the M-In
complex.
M + ln ———>M-In
● Stability of the metal indicator complex Kln is given by the equation.
Kln = [M-ln]
[M] [In]

Types of Complexometric Titration

EDTA can be used as a chelating titrant (titrant can be defined as the solution whose
concentration is known in the titration) in many ways. So, EDTA titrations can be performed
in many ways. A few of them are given as follows –

Direct Titration – It is the most convenient and simple method of complexometric titration
using EDTA. It is similar to the acid–base titration technique. In this titration standard, EDTA
solution is added to give sample containing metals using burette till the endpoint is achieved.
Copper, barium, zinc, mercury, aluminium, lead, bismuth, chromium, etc. are metals that can
be determined by using direct complexometric titration.

Back Titration – It is called back titration as in this type of titration, we perform back
titration for the excess amount of EDTA. In this, an excess amount of standard solution of
EDTA is added to the metal solution being examined. Then the excess amount of EDTA is
back titrated by the solution of the second metal ion.

13
 ANUSHA .G

Replacement Titration – It is used when direct titration or back titration don’t give sharp
endpoints. This analyte (containing metal) is added to the metal–EDTA complex. The metal
present in the analyte displaces another metal from the metal–EDTA complex.

Indirect Titration – Some anions form a precipitate with metal cations. These anions do
not react with EDTA. So, these can be analyzed by indirect titration with EDTA. For example,
barium ions can be determined by indirect titration.

Aim
To estimate the amount of total hardness of a given water sample by complexometric
titration using EDTA.

Principle
Indicator Eriochrome Black T becomes wine red in colour when bound with metal ions while
remaining blue in colour when free from metal ions. wWhile EDTA (which is ethylene
diamine tetraacetic acid) is colourless whether it’s bound to metal ions or not. So, the
addition of the EBT indicator in the sample (water containing metal) makes it wine red in
colour as Eeriochrome Bblack T binds with metal ions. Eriochrome Black T binds with metal
ions loosely while EDTA binds with metal ions strongly. So, when all metal ions are bound to
EDTA, indicator EBT remains free in the sample and the solution turns blue.

Procedure
● Take 25ml of the given sample in a conical flask.
● Now add 1ml of buffer solution.
● Now in the sample and buffer solution, add 1ml of inhibitor as well.
● Now add 2 drops of Eriochrome Black – T solution in the mixture which turns the
colour of the solution win red.
● Fill the burette with an EDTA solution. Now start titrating the mixture with a standard
EDTA solution.
● An endpoint can be detected by a colour change from wine red to blue.
● Repeat the titration three times to obtain 3 concordant readings.

Applications of Complexometric Titrations

● Complexometric titration is used for the estimation of the amount of total hardness in
water.
● It is widely used in the pharmaceutical industry to determine the metal concentration
in drugs.
● Titanium dioxide is used in many cosmetic products. This can be analysed by
complexometric titration.
● It is used to analyse urine samples.
● It is widely used in analytical chemistry.

14
 ANUSHA .G

Redox titrimetry:
Balancing Redox equation:
The reduction is the gain of electrons whereas oxidation is the loss of electrons. The
combination of reduction and oxidation reaction together refers to redox reaction/redox
process.
There are generally two methods for balancing redox reactions (chemical equations) in a
redox process. The two methods are- Oxidation Number Method & Half-Reaction Method.

Rules
1. Write the given equation in ionic form.
2. Identifying elements undergoing oxidation.
3. Break the equation into two halves
a. Oxidation half
b. Reduction half
4. Balance e-s and atoms
a. For every extra O add a H2O to the other side.
b. For every extra H+ add an H+ to the other side.
c. Add the ½ reactions ,before adding the e-s in two reactions.

Equations:
Oxidation number increases
1) Oxidation
—————————————————
+7 | |
MnO4- + Fe2+ + H+ ——>Mn2+ +Fe3+ +H2O
|___________________|
Oxidation number decreases
Reduction
+7
MnO4-——>Mn2+
MnO4- + 5e-——>Mn2+
MnO4- + 5e- +8H+——>Mn2++4H2O

[Fe2+——> Fe3++e-] ×5
5Fe2+——>5 Fe3++5e-
———————————————————————————————————

MnO4- +5 Fe2+ +8 H+ ——>Mn2+ +5Fe3+ +4H2O

2)
Oxidation number increases
Oxidation
——————————————————
| |
Fe + Cr2O7 ——>Cr +Fe3+
2+ +6 2- 3+

|_________|
Oxidation number decreases
Reduction

15
 ANUSHA .G

+6
Cr2O72- ——>Cr3+
Cr2O72- +6e- ——>Cr3+
Cr2O72- +6e- +14H+ ——>Cr3++7H2O

[Fe2+——> Fe3++e-] ×6
6Fe2+——>6 Fe3++6e-
——————————————————————————————————

Cr2O72- +6Fe2++14H+ ——>2Cr3++ 6Fe3++7H2O

calculation of the equilibrium constant of redox reaction:

The equilibrium constant of an electrochemical cell's redox reaction can be calculated using
the Nernst equation and the relationship between standard cell potential and free energy.
This example problem shows how to find the equilibrium constant of a cell's redox reaction.
Calculate the equilibrium constant for the redox reaction at 25oC,
Sr(s) +Mg2+(aq) →Sr2+(aq) +Mg(s), that occurs in a galvanic cell.
EoMg2+/Mg =−2.37V and EoSr2+/Sr =−2.89V.

Solution
(i) Mg2+(aq) +2e− ⟶Mg(s) ;EoMg 2+ /Mg=−2.37V
Sr2+(aq)+2e−⟶Sr(s);EoSr2+/Sr=−2.89V
(ii) Sr(s)⟶ Sr2+(aq)+2e− ;EoSr/Sr 2+=2.89V
Adding (i) & (ii), we get,
Sr(s) +Mg2+(aq) ⟶ Sr2+(aq)+Mg(s);Eo =−2.37+2.89=0.52V
Now, ΔGo =−RTlnKeq
∴−nFEo =−RTlnKeq
∴lnKeq = nFEo/RT= 2×96500×0.52/ 8.314×298
∴lnKeq=40.507
∴Keq=3.69×1017

Redox (titrimetry) titration curves:

Redox titration is monitored by observing the change of a electrode potential. The titration
curve is a drawn by taking the value of this potential (E) vs the volume of the titrant added.
The redox reaction is rapid and the system is always in equilibrium throughout the titration.

To evaluate a redox titration we must know the shape of its titration curve. In an acid–base
titration or a complexation titration, a titration curve shows the change in concentration of
H3O+ (as pH) or Mn+ (as pM) as a function of the volume of titrant. For a redox titration, it is
convenient to monitor electrochemical potential.
You will recall that the Nernst equation relates the electro- chemical potential to the
concentrations of reactants and products participating in a redox reaction. Consider, for

16
 ANUSHA .G

example, a titration in which the analyte in a reduced state, A red, is titrated with a titrant in an
oxidized state, Tox. The titration reaction is

Ared + Tox < == == > Tred + A ox

The electrochemical potential for the reaction is the difference between the reduc- tion
potentials for the reduction and oxidation half-reactions; thus,

Erxn = ETox/Tred – EAox/Ared

After each addition of titrant, the reaction between the analyte and titrant reaches a state of
equilibrium. The reaction’s electrochemical potential, Erxn, therefore, is zero, and
ETox/Tred = EAox /Ared
Consequently, the potential for either half-reaction may be used to monitor the titration’s
progress.
Before the equivalence point the titration mixture consists of appreciable quan- tities of both
the oxidized and reduced forms of the analyte, but very little unreacted titrant. The potential,
therefore, is best calculated using the Nernst equation for the analyte’s half-reaction.
Although E˚Aox /Ared is the standard-state potential for the analyte’s half-reaction, a
matrix-dependent formal potential is used in its place. After the equivalence point, the
potential is easiest to calculate using the Nernst equation for the titrant’s half-reaction, since
significant quantities of its oxidized and reduced forms are present.

calculate the titration curve for the titration of 50.0 mL of 0.100 M Fe2+ with 0.100 M Ce4+ in
a matrix of 1 M HClO4. The reaction in this case is

The equilibrium constant for this reaction is quite large (it is approximately 6 x 1015), so we
may assume that the analyte and titrant react completely.
The first task is to calculate the volume of Ce4+ needed to reach the equivalence point.
From the stoichiometry of the reaction we know

17
 ANUSHA .G

gives the equivalence point volume as 50.0 mL.

Before the equivalence point the concentration of unreacted Fe2+ and the con- centration of
Fe3+ produced by reaction 9.16 are easy to calculate. For this reason we find the potential
using the Nernst equation for the analyte’s half-rea

At the equivalence point, the moles of Fe2+ initially present and the moles of Ce4+ added
are equal. Because the equilibrium constant for reaction 9.16 is large, the concentrations of
Fe2+ and Ce4+ are exceedingly small and difficult to calculate without resorting to a
complex equilibrium problem. Consequently, we cannot cal- culate the potential at the
equivalence point, Eeq, using just the Nernst equation for the analyte’s half-reaction or the
titrant’s half-reaction. We can, however, calculate Eeq by combining the two Nernst
equations. To do so we recognize that the poten- tials for the two half-reactions are the
same; thus

Adding together these two Nernst equations leaves us with

At the equivalence point, the titration reaction’s stoichiometry requires that

The ratio in the log term of equation 9.18, therefore, equals one and the log
term is zero. Equation 9.18 simplifies to

18
 ANUSHA .G

After the equivalence point, the concentrations of Ce3+ and excess Ce4+ are easy to
calculate. The potential, therefore, is best calculated using the Nernst equation for the
titrant’s half-reaction.

Theory of Redox indicator:

A redox indicator is an indicator compound that changes color at specific potential

differences.
A redox indicator compound must have a reduced and oxidized form with different colors
and the redox process must be reversible.
Example:
The molecule 2,2'-Bipyridine is a redox indicator. In solution, it changes from light blue to red
at an electrode potential of 0.97 V.
The requirement for fast and reversible color change means that the oxidation-reduction
equilibrium for an indicator redox system needs to be established very quickly. Therefore,
only a few classes of organic redox systems can be used for indicator purposes.[1]

There are two common classes of redox indicators:

Metal complexes of phenanthroline and bipyridine. In these systems, the metal changes
oxidation state.

19
 ANUSHA .G

organic redox systems such as methylene blue. In these systems, a proton participant in the
redox reaction. Therefore, sometimes redox indicators are also divided into two general
groups: independent or dependent on pH.
The most common redox indicator are organic compounds.

Calculation of standard potential using Nernst equation:

Calculate using Nernst equation cell potential of the following electrochemical cell at 298K.
Zn(s)∣Zn2+(eq) ∣∣ Sn2+(eq) ∣Sn(s)
(0.04 M) (0.03M)
(Given E =−0.76 V, E∘=−0.14 V).
∘

Solution

Nernst equation for the electrochemical process at 298 K:

Zn(s)∣Zn2+(eq) ∣∣ Sn2+(eq) ∣Sn(s)
(0.04 M) (0.03M)
E=E − 0.0592 log10​ ([Zn2+]​)
∘

2 [Sn2+]
E∘ =E∘cathode −E∘anode
Given : E∘Zn(s)∣Zn2+(eq)=−0.76 V,E∘Sn2+(eq) ∣Sn(s)=−0.14 V
E∘ =E∘Sn2+(eq) ∣Sn(s)−E∘Zn(s)∣Zn2+(eq)
E∘ =−0.14−(−0.76)=0.62 V
Also, [Zn2+]=0.04 M and [Sn2+]=0.03 M
Upon substitution in Nernst equation we get
E=0.62− 0.0592 log10 ( 0.04 )
2. 0.03
E=0.616 V

Applications:
● Redox titrimetry is used to analyse a wide range of inorganic analytes.
● A redox titration can accurately determine the concentration of an unknown analyte
by measuring it against a standardized titrant.
● It is used for the analysis of organic analytes.
● It is usually used to determine medium and high concentrations of elements.
● the determination of the chemical oxygen demand (COD) of natural waters and
wastewaters.

20
 ANUSHA .G

Precipitation titrimetry
Titration curves:
A precipitation titration curve follows the change in either the titrand's or the titrant's
concentration as a function of the titrant's volume.
AgNO3 + Cl- → AgCI + NO3-

The titration curve for a precipitation titration follows the change in either the analyte’s or
titrant’s concentration as a function of the volume of titrant. For example, in an analysis for I–
using Ag + as a titrant.
Ag+(aq) + I–(aq) < = = = = > AgI (s)
The titration curve may be a plot of pAg or pI as a function of the titrant’s volume. As we
have done with previous titrations, we first show how to calculate the titration curve and then
demonstrate how to quickly sketch the titration curve.
Calculating the Titration Curve
As an example, let’s calculate the titration curve for the titration of 50.0 mL of 0.0500 M Cl –
with 0.100 M Ag+. The reaction in this case is
Ag+(aq)+ Cl–(aq) < = = = = > AgCl (s)

The equilibrium constant for the reaction is

K = (Ksp)–1 = (1.8 x 10–10)–1 = 5.6 x 109
Since the equilibrium constant is large, we may assume that Ag + and Cl– react completely.
By now you are familiar with our approach to calculating titration curves. The first task is to
calculate the volume of Ag + needed to reach the equivalence point. The stoichiometry of the
reaction requires that

shows that we need 25.0 mL of Ag + to reach the equivalence point.

Before the equivalence point Cl– is in excess. The concentration of unreacted Cl– after
adding 10.0 mL of Ag +, for example, is

If the titration curve follows the change in concentration for Cl–, then we calculate pCl as
pCl = –log[Cl–] = –log(2.50 x 10–2) = 1.60
However, if we wish to follow the change in concentration for Ag + then we must first calculate
its concentration. To do so we use the Ksp expression for AgCl
Ksp = [Ag+][Cl–] = 1.8 x 10–10
gives a pAg of 8.14.

21
 ANUSHA .G

At the equivalence point, we know that the concentrations of Ag+ and Cl– are equal. Using
the solubility product expression

At the equivalence point, therefore, pAg and pCl are both 4.89.
After the equivalence point, the titration mixture contains excess Ag +. The con- centration of
Ag+ after adding 35.0 mL of titrant is

Classification of precipitation reaction:

Quantity of reagent added = Quantity of precipitate obtained There are mainly three types of
precipitation titrations:

● Volhard’s Method
● Fajan’s Method
● Mohr’s Method

Volhard’s Method:
Volhard’s method anions like halides, phosphate, and chromate are determined in an acidic
medium by using silver ions. To prevent the precipitation of iron ions as hydrated oxide it is
important to perform this titration in an acidic medium.

In this method of reaction with the excess of silver nitrate, the chloride present in the solution
is converted into silver chloride. The leftover silver nitrate from the reaction is again treated
with potassium thiocyanate solution. The excess of thiocyanate is made to react with an
indicator which gives a red color on reacting with the ferric ammonium sulfate indicator and a
complex is formed.
Example: Ag+ + SCN- → AgSCN

22
 ANUSHA .G

Mohr’s Method:
Mohr’s method of precipitation titration was given by German Chemist Karl Friedrich Mohr.
This is a direct titration method in which silver nitrate is used as titrant and a solution of
chloride ion is used as analyte. The indicator used in the titration is Potassium chromate.
The reddish-brown precipitate is formed at the end of the reaction of silver ions and
chromate ions, after the consumption of all the chloride ions.
Example:
AgNO3 + NaCl →AgCl (White) + NaNO3
2Ag+ + CrO42- → Ag 2CrO4 (Reddish Brown)
Ag2CrO4 + 2Cl- →AgCl + CrO42-

Application of Precipitation Titration:

The different applications of precipitation titration are as follows:

● Precipitation titration is used to determine the halide ions.

● Precipitation titration is used to measure salt content in various food & beverages.
● Precipitation Titration is used to analyze various drugs.
● Precipitation titration is used for analyzing the concentration of the anion in the
analyte.

Difference between Mohr’s Method & Volhard’s Method

Mohr’s Method Volhard’s Method

It is a direct method of titration It is a indirect method of titration

potassium chromate is used as an Ferric Ammonium Sulphate is used

indicator as an indicator

Neutral or alkaline conditions are Acidic conditions are required

required

It is used to determine the It is used to determine iodide

concentration of chlorides in neutral Chloride and Bromide
medium

A red precipitate of silver chromate is A red soluble ferric thiocyanate

forms at the end point forms at the end point

The titration is carried out at room The titration is carried out below 20
temperature because solubility of degree Celsius to prevent the colour
silver chromate increases with of ferric thiocyanate complex from
raising the temperature fading

23
ANUSHA .G

24