Unit-3

Titrimetry

1
 3.1. Introduction
Definitions:
 Titration is a controlled addition of a measured volume of reagent of exactly
known concentration to a known volume of a solution of analyte whose
concentration is unknown.

 So it is a technique used to determine the concentration of un known solution

using concentration of known solution, volume of both solution and
stoichiometry of their reaction.
 Titrant: Is a solution of known concentration or standard substance.
 Titrand (Analyte): Is a solution of the unknown concentration.
2
 The Equipment
• Volumetric analysis involves a few pieces of equipment:
− Pipette – for measuring accurate and precise volumes of solutions
− Burette – for pouring measured volumes of solutions
− Conical flask – for mixing two solutions
− Pipette
Wash bottles – these contain distilled filler
water for cleaning equipment
− Funnel – for transfer of liquids without spilling
− Volumetric flasks – a flask used to make up accurate volumes for
solutions of known concentration

3
 Requirements
Known reaction stoichiometry
Rapid reaction
No side reactions
Large (visible) change at equivalence point
Coincidence of equivalence and end points
Quantitative reaction

4
 Advantages Limitation
• Capable of higher degree of precision • Non selective
and accuracy than instrumental • Time consuming if not automated
method. • Require large amount of sample and
reagent
• Robust • Reaction should be rapid and
• Can be automated complete.

• Cheap to perform and not require

specialized instrument
• Absolute method:- not depend on
instrument calibration.

5
 Standard solutions
is a material containing a substance of our interest with a known
concentration.
Functions:
−To determine unknown concentration of solution
−For preparation of secondary standard
−To calibrate an instrument

6
• The ideal standard solution should:
1. be sufficiently stable
2. React rapidly with the analyte.
3. React more or less completely with the analyte, so that satisfactory end
points are realized
4. Undergo a selective reaction with the analyte that can be described by a
balanced equation
• Types: Standards can be divided into two types:
1. Primary standard
2. Secondary standard

7
1. Primary standard:-
A primary standard is a chemical or reagent which has certain properties like:
a) It is extremely pure (>99.95%)
b) Highly stable (does not react easily when kept in its pure form)
c) It is less hygroscopic
d) Has very high molecular weight (weighing error is negligible)
e) Can be weighed easily and easily soluble
f) Should not be expensive
g) Non-volatile
 Titrants can be made directly by accurate weighing of the standard and
subsequent dissolution and dilution to a specific volume.
8
9
2. Secondary standard is a chemical that has been standardized against a primary
standard.
• It is used for standardization of analyte after finding out its exact concentration.

10
 3.1.1. End point and equivalence point
 Equivalence point: is the point in a titration when the amount of added
Titrant
standard reagent (titrant)
Oxalic acid
is equivalent (colorless)
Analyte
(purple)
to the amount
(colorless) of analyte (titrand).
CuCl Titration with NaOH
(colorless)
−It is the point of stoichiometric chemical equivalence (related to amount).
Equivalence
−The point
equivalence occurs
point of awhen 5 moles
titration ofbe
cannot Oxalic acid is experimentally.
determined added to
2 moles of MnO4-
−It can only be estimated from the end point for the titration.
 The end point is the point at which some detection technique tells you that
chemical equivalence has been reached (related to physical sign).
 The equivalence and end points are rarely the same.
Before any After the End
addition of NaOH addition of 8 Point
drops of
NaOH 11
 The end point may occur before or after the equivalence point, giving a
titration error.
 Indicator is a chemical substance that is used to detect the end point by:
Phenolphthalein indicator
colour change
precipitate formation
complex formation

Acid Base

12
 3.1.2. Direct titration and back titration
Direct titration is a process in which a standard reagent is added to a solution
of an analyte until the reaction between the analyte and the reagent is judge to
be complete.
Back-titrations is process in which the excess of standard solution used to
react with an analyte is determined by titration with a second standard
solution.
Back titration is normally employed in the following situations:
1. When the rate of reaction between the analyte and reagent is slow
2. When the standard solution lacks stability.
3. When the substance under determination fails to give a sharp and distinctly
visible end-point with an indicator by direct titration.
13
 Titration process (Setup)
The burette is attached to a clamp stand
above a conical flask
The burette is filled with one of the solutions
(in this case a yellow standard solution)
A pipette is used to measure an aliquot of the
other solution (in this case a purple solution
of unknown concentration) into the conical
flask
Prepare a number of flasks for repeat tests
Last, an indicator is added to the conical
flask
Read the initial level of liquid in the burette.
Turn the tap to start pouring out liquid of the burette into the
flask.
Swirl the flask continuously.
When the indicator begins to change colour slow the flow.
When the colour changes permanently, stop the flow and read
the final volume.
The volume change needs to be calculated (and written down).
This volume is called a titre
Repeat the titration with a new flask now that you know the
‘rough’ volume required. Repeat until you get CONCORDANT
results (volume difference not greater than 0.1ml)
 3.3.1. Calculations in titrimetry
• The first thing we do is to calculate the mean (average) titre.
• Add up concordant result and divide to the number of tests.
• Concordant titres – a titres that differ by more than 0.1mL between the lowest
& highest reading will be discarded.
• Write down the balanced equation and other necessary information.
• Use the following formulas to get amount in mole.
Amount (mol)= concentration (M)  volume (L)
( )
( )=
( / )
16
Example 1: Describe the preparation of 2L of 0.05M AgNO3 (170g/mol) from
the primary standard grade solid.

Ans=by dissolving 17g to form 2 L solution.

Which of this method is

17 right to prepare the above
17
2L solution (0.05M of 2L
2L
AgNO3)

2. Explain how to prepare 2.0L of 0.1M potassium sulfate, (K2SO4). (molecular

weight of K=39, S=32 and O=16). Ans=34.8g
3. Explain how to prepare 10ml of 1 ppb Fe2+ .
17
 3.1.4. Titration curves
Titration curves are constructed by plotting −#$% &' ($)(*)+,-+.$), or pX,
of the analyte versus the volume of titrant added to the reaction solution.
 For acid-base titrations it is a plot of pH on the y axis versus titrant volume
on the x axis.
Strong acid and strong base

19
Example: calculate the pH at 0,10,90,100 and 110% titration for the titration of 50ml of
0.1M HCL with 0.1M NaOH.
Solution: at 0% the pH =-log 0.1= 1

20
21
2. Calculate the pH during the titration of 50ml of 0.05M NaOH with 0.1M HCl
after the addition of the following volume of reagents. a)24.5ml b) 25ml c)
25.5ml.
a) Ans= at 24.5ml the pOH=3.17 so its pH=10.83.
b) At 25ml pH= /0 =7
c) At 25.5ml pH=3.18

22
Titration curve for weak acid and base

23
Example 1. Calculate the pH at 0, 10, 25, 50 and 60ml titrant in the titration of
50ml of 0.1M acetic acid with 0.1M NaOH.

24
25
26
Example 2. generate the hypothetical titration curve and calculate the pH for the
titration 0.1M from HCl with 25ml (0.1M) Ammonia? Kb=1.75 x10-5
NH3 + HCl  NH4+ + Cl-
a. Before addition of HCl c. After addition of 25ml HCl
b. After addition of 10ml HCl d. After addition of 26ml HCl
 Solution. A) [OH-]= 12. 456

27
28
• Concentration of HCl at V=25ml of HCl is = 2.5mmol/50ml= 0.05M
>
78 <= <?
[H]= :; = C 0.05 = 5.34 x 10 − 6 ,
79 <.@AB<=>A

LM =-log5.34x10-6= 5.27

29
 Individual assignment
1. 20ml of 0.5M sodium acetate buffer with a pH of 4.3 was prepared. A) what is the pH of
the buffer if 10ml of 0.1M HCl is added? B) what is the pH of the buffer if 10ml of 0.1M
NaOH is added? C) what is the pH of pure water if 10ml of 0.1M HCl is added to 100ml?
2. A 50ml aliquot of 0.1M NaOH is titrated with 0.1M HCl. Calculate the pH of the solution
after the addition of 0, 10, 25, 40, 45, 49, 50, 51, 55 and 60ml of acid and prepare a
titration curve from the data.
3. A 50ml aliquot of 0.1M HCl is titrated with 0.1M NaOH. Calculate the pH of the solution
after the addition of 0, 10, 25, 40, 45, 49, 50, 51, 55 and 60ml of NaOH and prepare a
titration curve from the data.
4. Calculate the pH after addition of 0, 5, 15, 25, 40, 45, 49, 50, 51, 55 and 60ml of 0.1M
HCl in the titration of 0.1M ammonia of 50ml and prepare a titration curve from the data.
5. 50.0 mL of 0.20 M HC2H5CO2, propanoic acid (Ka = 4.4 x 10-7) are titrated with 0.20 M
NaOH. Calculate the pH after the additions of 0, 10.0, 25.0, 40.0, 49.0, 49.95, 50, 50.05,
51.0, 60.0, and 75.0 mL samples of NaOH. Then, construct a titration curve and label it
properly. 30
 Classification of Titrimetry

Based on the type of chemical reaction

Redox
Acid base
Precipitation Complexation (Oxidation
(Neutralization)
reduction)

31
 3.2. Acid-Base titrations
An acid–base titration involves a neutralization reaction in which an acid is
reacted with an equivalent amount of base.
Most titrations of pharmaceutical ingredients are acid–base titrations.
Acid–base titrations are used to assay basic or acidic pharmaceutical
ingredients.
Acid-Base Titration

Acid-Base titrations in aqueous Acid-Base titrations in non-

media aqueous media
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 3.2.1 Acid-Base titrations in aqueous media
Acid is any substance that ionizes (partially or completely) in water to give
hydrogen (which associate with the solvent to give hydronium ions, H3O+).

A base ionizes in water to give hydroxide ions.

This theory is obviously restricted to water as the solvent.

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 Acid-Base titrations in
aqueous media

Direct Indirect
titrations titrations

Strong Acid- Weak acid Weak base

Strong Base Strong base Strong acid
34
 A. Strong Acid-Strong Base titrations
 In water, strong acids and bases are entirely dissociated.
 The reaction for titration of a strong acid with a strong base is therefore:
H+ + OH-  H2O
By constructing a titration curve, we can easily explain how the end points of
these titrations can be detected.
When strong acid is titrated with strong base, prior to the equivalence point
(when there is excess acid) the relationship is:
+ PQRST × VQRST >P9QWX V9QWX
4N 6 =
VYZYQ[
The pH remain low until the equivalence point.

35
At the equivalence point the pH rises sharply to high value.
The magnitude of the break will depend on both the concentration of the acid
and the concentration of the base.
The end point signals the completion of the reaction.
Beyond the equivalence point when there is excess base,
P9QWX × V9QWX > PQRST × VQRST
4\N−6 =
VYZYQ[
Note that ] : 0 ^ ] :; + ]2 .
After the equivalence point, the curve levels off at high pH values.
The reverse titration (Base-acid) gives the mirror image of acid-base curves.
There are only a few direct strong acid strong base titration carried out in
pharmacopoeia assay.
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 Detection of the End Point: Indicators
The point at which the reaction is observed to be complete is called the end
point.
The end point should coincides with or is very close to the equivalence point.
The difference between the equivalence point and the end point is referred to
as the titration error.
The most obvious way of determining the end point is to measure the pH at
different points of the titration and make a plot of this versus volume of titrant.
A convenient method is to add an indicator to the solution and visually detect
a color change.

37
An indicator for an acid–base titration is a weak acid or weak base that is
highly colored.
The color of the ionized form is markedly different from that of the
nonionized form.
E.g. Assume the indicator is a weak acid:

The useful range for an indicator is 1pH either side of its pKa value.
E.g. of indicators used in acid base titration
• Phenolphthalein (PP) and methyl orange (MO).

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E.g1. Phenolphthalein (PP) has pKa of 9.4 & ionizes at higher pH.
−So its color change is observed between pH 8.4 and 10.4
− It turns colorless in acidic solutions and pink in basic solutions.

39
Methyl Orange has a pKa value of 3.7
−So its colour change is observed between pH 2.7 and 4.7.
−As the pH decreases the colour changes from yellow to red and vise versa.
−The anion of methyl orange is yellow and the nonionized form is red.
−When we add acid to a solution of methyl orange, the increased hydronium
ion concentration shifts the equilibrium toward the nonionized red form.
In strong acid base titration either the methyl orange or Phenolphthalein can be
used because it cover all the pH (both acid and base, pH 2-12).
In dilute solutions, however, phenolphthalein falls outside the steep portion of
the titration curve.

40
 B) Weak acid strong base titration
If 100 mL of 0.1 M acetic acid titrated with 0.1 M sodium hydroxide:
• As soon as the titration is started, some of the HOAc is converted to NaOAc, and
a buffer system is set up.
• At the midpoint of the titration, [OAc−]=[HOAc], and the pH =pKa.
• At the equivalence point, all [OAc−] is converted to NaOAc.
• the pH at the equivalence point will be alkaline.
• The transition range of the indicator for this titration of a weak acid must fall
within a pH range of about 7 to 10.
• Phenolphthalein is suitable as an indicator in this case.
Which
• TheofpHthewill
above indicators
depend are appropriate
on the concentration on weak acid strong base
of NaOAc
titration?
The greater the concentration, the higher the pH.
• the titration curve beyond the equivalence point follows that for the titration of a
strong acid.
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 C) Weak base Strong acid titration
The titration of a weak base with a strong acid is completely analogous to weak
acid versus a strong base.
But the titration curves are the reverse of those for the above case.
Eg if 100 mL of 0.1 M ammonia titrated with 0.1 M hydrochloric acid.
NH3 + H+ + Cl− → NH4+ + Cl−
At the midpoint of the titration,[NH4+] equals [NH3], and the pH =(14-pKb) or
pH= or pKa for NH4+.
At the equivalence point, we have a solution of NH4+.
Which of the above indicators are appropriate on weak acid strong base
the pH will depend on the concentration; ↑concentration, the lower the pH.
titration?
Because MO changes color at the pKa of a mid strength acid, it is usually used
in the strong acid weak base titration.
42
Either the analyte or the standard has to be a strong acid or base to ensure that the
reaction is virtually complete (analyte is converted to product).
Drugs are often weak bases or acids → strong acids or bases are used as titrants.
For weak acids and bases, the pH changes in the equivalence point are less
noticeable.
Use of visual indicator endpoint detection may not be possible in these cases.
As a rule, titration of acids with pKa> 6.0 and bases with pKa< 8.0 is not possible in
water.
These limits may be extended somewhat using potentiometric endpoint detection.
But generally weak acids and bases must be titrated in non-aqueous solvents instead
of water.
43
 How to calculate a concentration of analyte in direct titration
Example1. What is the unknown concentration of a 25.00 mL HCl sample that requires
average 40.00 mL of 0.450 M NaOH to reach the equivalence point in a titration?
Step 1: First calculate the number of moles of NaOH added during the titration.
0.450moles/LNaOH×0.0400L=0.018 moles NaOH
Step 2: Use stoichiometry to figure out the moles of HCl in the analyte.
The mole ratio between HCl and NaOH in the balanced equation is 1:1.
0.018 moles NaOH×1 mole HCl/1 mole NaOH=0.018 moles HCl
Step 3: Calculate the molar concentration of HCL in the 25.00 mL sample.
=.=<b cZ[XW de[
_ : ^ ` Na = = 0.72M HCl
=.=fA g de[

44
 Solve the following problem
1. Titration reveals that 11.6 mL of 3.0 M sulfuric acid are required to neutralize
the sodium hydroxide in 25.00 mL of NaOH solution. What is the molarity of
the NaOH solution?
H2SO4(aq) + 2NaOH(aq) → 2H2O(l) + Na2SO4(aq) Ans= 2.784M
2. Calculate the molarity of a solution of hydrochloric acid if it requires 24 mL
of a 2.2 M solution of potassium hydroxide to neutralize 15 mL of the
hydrochloric acid solution. Ans=3.52M
3. A 50ml portion of an HCl solution required 29.71ml of 0.01963M Ba(OH)2
to reach an end point with bromocresol green indicator. Calculate the molar
concentration of the HCl. Ans=0.02333M
45
More examples to try
1) What volume of sulphuric acid, concentration 2 mol l-1 is required to
neutralise 25cm3 of KOH, concentration 4 mol l-1? 25 cm3
2) If 50cm3 of KOH solution is neutralised by 17.8cm3 of H2SO4 (2 mol l-1),
what is the concentration of the alkali? 1.42mol l-1
3) What volume of HCl, concentration 1.0 mol l-1 is required to neutralise
100cm3 of NaOH solution concentration 0.5moll-1? 50cm3
4. What is the concentration of ammonium if 25ml of ammonium was titrated
with 0.1M H2SO4. The volume of the acid consumed in rough, 1st,2nd and 3rd
titration to give indicator colour change was 8.25, 8, 9 and 8ml respectively.
2NH3 + H2SO4 → (NH4)2SO4
Answer: average of concordant volume = 8ml
Concentration of NH3 = 0.064M
 D. Indirect titration in aqueous media
Indirect (back) titration is generally two stage analytical technique
1. Analyte A is reacted with excess titrant B
2. A direct titration is then performed between titrant B and titrant T to
determine amount of B in excess.
This titration is used when:
−The analyte is volatile
−The analyte is insoluble salt eg. Calcium carbonate
−The reaction is too slow
−End point of direct titration is very difficult to observe.

47
How to calculate analyte concentration in back titration?
1. A student was asked to determine the concentration of ammonia (volatile
substance) in cloud ammonia solution. First the student pipetted 25ml of
cloud ammonia solution in conical flask. 50ml of 0.1M HCl was
immediately added to the conical flask and reacted with the ammonia. The
excess HCl was then titrated with 21.5ml of 0.05M Na2CO3. calculate the
concentration of ammonia in cloud ammonia solution.
s/n. determine the amount of HCl in excess from HCl and Na2CO3 interaction
2HCl + Na2CO3  2NaCl + CO2 + H2O
Mole of Na2CO3 consumed is 0.05M X 21.5ml = 1.075mmol
Mole of HCl interact with Na2CO3 is 1.075 x2 = 2.15mmol
48
Total mole of HCl added to ammonia solution.
Mol = CV= 0.1M x50ml = 5 mmol
Mol of HCL react with ammonia = total mole of HCl - Mole of HCl interact
with Na2CO3
=5-2.15 = 2.85mmol
Then calculate mol of NH3 from stechiochemistry
HCl + NH3  NH4Cl
which become 2.85mmol
Calculate the concentration of NH3
=mol/volume (L) =2.85mmol/25ml = 0.114M

49
2. If you put 0.125g chalk sample in 50ml of 0.2M HCl. Then back titrated with
32.12ml of 0.25M of NaOH. Calculate the mass of calcium carbonate (g)
present in the chalk and %w/w.
The equation is
HCl + NaOH  NaCl + H2O
CaCO3 + 2HCl  CaCl2 + CO2 + H2O
Molecular mass of CaCO3 is 100g/mol
s/n: mol of total HCl = CV = 0.2M X 50ml =10mmol
Mol of HCl interact with NaOH = CV = 0.25M x 32.12 = 8.03mmol
Mol of HCL interact with CaCO3 = 10- 8.03 = 1.97mmol
Using stechiochemistry mol of CaCO3 is 1.97mmol/2 = 0.985mmol
50
Then the mas of CaCO3 will be calculated from its mole.
0.985mmol= 9.85 x 10-4mol
Mol = mass/ molecular mass
By rearranging we get that: Mass = mol x molecular mass
= 9.85 x 10-4mol x 100g/mol
=0.0985g
cQWW Zi eQejk
%0/0 = × 100
cQWW Zi elQ[m
=.=nbAo
= × 100 = 78.8%
=.<fAo

51
3. 150 ml of 0.2105M nitric acid was added in excess to 1.3415g chalk. The
excess acid was back titrated with 0.1055M NaOH. It required 75.5ml of the
base to reach the end point.
a. Name the suitable indicator used in above titration
b. Calculate the %w/w of calcium carbonate in the chalk.
The reaction:
CaCO3 + 2HNO3 → Ca(NO3)2 + CO2 + H2O Ans: PP or MO
HNO3 + NaOH → NaNO3 + H2O m=1.1805g
%w/w = 87.99%

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 3.2.2 Acid-Base titrations in non aqueuse media
Nonaqueous titration is the titration of substances dissolved in solvents other
than water.
 It is the most common titrimetric procedure used in Pharmacopeial assays.
Water behaves both as a weak acid and a weak base.
Thus in aqueous environment it can compete effectively with very weak acids
and bases with regard to proton donation and acceptance.
The effect of this is that the inflation in the titration curves for very weak acids
and very weak bases is small making end-point detection more difficult.
So various organic solvent may be used.

53
We need to perform an acid-base titration in nonaqueous solvent due to:

The analyte is too weak acid or a base to be titrated in H2O

Reactants or products are insoluble in H2O

Reactants or products react with H2O

Titration in H2O doesn’t allow a sharp end point

54
 Solvents used in non aqueous titration
 Non aqueous solvents may classified as:
1. Protophillic (Basic solvents)
2. Protogenic (Acidic solvents )
3. Amphiprotic (Acid/Base nature)
4. Aprotic (Neutral Solvents)

55
 1. Protophillic (basic) solvent
 Protophillic solvents are the substances that possess a high affinity for
protons.
 Example:- Acetone, dioxane, amines
 React with acid and form a solvated proton and conjugate base.
HA + S ⇌ SH+ + A- ( Conjugate base )
Acid Basic solvent Solvated proton a

 The equilibrium in this reversible reaction will be generally influenced by the

nature of the acid and the solvent.
 Weakly basic solvents has less tendency than strongly basic one to accept a
proton.
 Weak acid has less tendency to donate proton. 56
 2. Protogenic Solvents
 They are proton donating acidic substances such as formic, acetic, sulfuric
acids.
 They have high dielectric constant and ionized because of their strength and
ability to donate protons.
 They exert a levelling effect on all bases dissolved in them
 They enhance the strength of weak bases.

57
 Levelling Solvents

In general, strongly protophillic solvents are important to force equilibrium

equation to the right.

This effect is so powerful that, in strongly protophillic solvents, all acids act as
of similar strength.

The converse occurs with strongly protogenic solvents, which cause all bases to
act as they were of similar strength.

Solvents, which act in this way, are known as Leveling Solvents.

58
 3. Amphiprotic Solvents:
 Amphiprotic solvents have both protophillic and protogenic properties, so acts as
both proton donor and acceptor.
Example:- alcohols, glacial acetic acids, water
They are capable of slight dissociation. E.g. CH3COOH ⇌ H+ + CH3COO-
If a very strong acid such as perchloric acid is dissolved in acetic acid, the latter
can function as a base and combine with protons donated by the perchloric acid to
form protonated acetic acid, an onium ion: HClO4 ⇌ H+ + ClO4−
CH3COOH + H+ ⇌ CH3COOH2+ (onium ion)
Since the CH3COOH2+ ion readily donates its proton to a base, a solution of
perchloric acid in glacial acetic acid functions as a strongly acidic solution.
59
4. Aprotic (Neutral) Solvents:
 Have low dielectric constant
 Chemically inert and do not favor ionization.
 Neither accept nor donate protons, (do not react with either acids or bases)
 Used for studying the reactions of acids and bases free of solvent effect.
Example: chloroform, benzene, Carbon tetrachloride and toluene

60
 INDICATORS IN ACID BASE TITRATION
Acid base indicators are sensitive to pH change.
For most acid base titrations, it is possible to select indicators which exhibit colour
change at pH close to the equivalence point.
E.g. phenolphthalein and methyl orange.
Phenolpthalein
is a weak acid, therefore it does not dissociate in the acidic medium and remains in
the unionized form, which is colourless.
but in alkaline media it dissociate and found in ionized form, imparts pink colour
to the solution
HPh ⇌ H+ + Ph–
Unionized Colourless Ionized Pink
The principles are identical for non aqueous titration also and cristal violate and
methyl red may be used. 61
 3.2.3. Applications
Neutralization titration are widely used to determine the concentration of
analytes that are themselves acid or base or that are convertible to such
species by suitable treatments.
Example:-
Determination of barbiturates.
Determination of nicotinic acid.
Determination of amino acid.
Determination of aspirin.
Assay of benzoic acid.

62
 3.3. Precipitation Titration
It is a type of titration that involves the formation of precipitates during the
course of titration.
The titrant react with the analyte in accordance with defined stoichiometry
forming a precipitant and the titration continues till the very last amount of
analyte is consumed.
The first drop of titrant in excess will react with an indicator resulting in a
color change and announcing the termination of the titration.
Example : titration of AgNO3 with halide ions such as Cl, I or Br
For example determination of concentration of chloride ions (NaCl) in a
solution by using silver ions (AgNO3) of known concentration.
AgNO3 + NaCl AgCl + NaNO3 63
 3.3.1. Limitations
 Co-precipitation may be occurred
The analyte or the titrant species may co-precipitate.
The indicator may also be adsorbed on the precipitate formed during the
titration and thereby be unable to function appropriately at the end point.
 Precipitation frequently proceeds slowly or starts after some time.
 If a precipitate is highly colored, visual detection of colour change at the end
point may be impossible
 Applicable for only few number of ions such as halide ions (Cl-, Br-, I-).
 So, precipitation titrations are not so popular in present–day routine analysis.

64
 3.3.2. Solubility product
The solubility of a substance is the amount of that substance that will
dissolve in a given amount of solvent.
Ksp (solubility product) is the mathematical product of its dissolved ion
concentrations raised to the power of their stoichiometric coefficients.
MyXz (s) ⇌ yMZ+(aq) + zXY-(aq)
Ksp= [MZ+]y[Xy-]z
Molar solubility of the ions

65
Solubility product constant (Ksp) describes the equilibrium between a solid
and its constituent ions in a solution.

 The amount of substance dissolved

remains constant
 The system appears macroscopically
static

RATE OF DISSOLVING = RATE OF CRYSTALIZATION

66
The value of the constant (Ksp) identifies the degree to which the compound
can dissociate in water.
The higher the Ksp, the more soluble the compound is.
A saturated solution is in a state of equilibrium between the undissolved solid
and the ionic compound.
Example 1: Barium Carbonate (BaCO3)
BaCO3(s) ⇌ Ba2+(aq) + CO32-(aq)
1st = 4Ba2+64CO32−6

67
1. Calculate the solubility, in mol /L, of AgCl(s). [Ksp(AgCl)=1.8×10-10]
AgCl (s) ⇌ Ag+(aq) + Cl-(aq)
Ksp = [Ag+][Cl-]
1.8 × 10-10 =x2
x=1.3410-5mol/L
2) Calcium carbonate, CaCO3, has a solubility in water of 0.0180 g /L at 25 oC.
Calculate the Ksp for CaCO3. [Mwt of CaCO3 = 100.1 g/mol]
CaCO3 (s) ⇌ Ca2+(aq) + CO32-(aq)
Ksp=[Ca2+][CO32-]
To use Ksp the concentration must be in mol/L, so Convert this value to mol/L.
<
0.0180 /y  / = 1.798 x 10-4mol/L
<==.<
Ksp=(1.798 x 10-4mol/L)2= 3.210-8 68
3) Calcium fluoride (CaF2), dissolves in water to the extent of 0.00170 g per 100 mL.
What is the Ksp for CaF2? (Mwt for CaF2 =78.1 g/mol
CaF2(s) ⇌ Ca2+(aq) +2F-(aq)
x 2x
Ksp= [Ca2+][F-]2  ksp=(x)(2x)2 = 4x3
Calculate for amount in mol = mass/mwt = 0.00170 g/78.1 g/mol = 2.1810-5mol
Calculate concentration in mol/L=2.18x10-5mol/0.1L = 2.18x10-4mol/L
Ksp=4x3=4(2.18x10-4)3 x= 4.14  10-11
4) If solid PbCl2 equilibrates with pure water, what are [Pb2+] and [Cl-] in the solution
at equilibrium? [Ksp(PbCl2) = 1.7 × 10-5]. Ans, [Pb2+]=1.62 x10-2 mol/L and
[cl-]=2x=2x1.62x10-2= 3.24x10-2 mol/L
69
5. Calculate no. of grams of Ba(IO3)2 that can be dissolved in 150ml of water
in 25oC, K.sp = 1.75x10-9. Mwt=487.13 g/mol. Hint: first calculate solubility
>n
z <.A@×<=
conc= = 7.59 x 10-4mole/L, then find mass= 55 mg
?

6. Describe concentration of Bi3+ and S2- with respect to the ksp of Bi2S3
2.

3. [Bi3+ ]=2x and [S2-]=3x

70
 -5
7) Calculate the solubility in mole/L for AgCl , KSP= 1.8 x 10-10? 1.34 ×10
8) A saturated solution of BaSO4 (Mwt=233 grams per mole) contains 0.0025
grams in one liter. Calculate the Ksp for barium sulfate. Ans=1.2 x10-10
9) Find the concentration of dissolved Al(OH)3 in a saturated solution. Ksp =
-9
1.9 x 10-33. Ans=2.9 x 10 M
10) What is the solubility of Ca(OH)2 if the Ksp is 7.9 x 10-6. Ans=1.25 x10-2M
11) Which one of the following salts is more soluble in water ? CaCO3: Ksp =
2.8 x 10-9 and Ag2CO3: Ksp = 8.1 x 10-12
12) Calculate the solubility product constant for PbCl2 (Mw= 278.1), if 50.0
mL of a saturated solution of PbCl2 was found to contain 0.2207 g of PbCl2
dissolved in it? Ans, Ksp=1.61x10-5 71
 3.3.3. Factors affecting solubility of precipitate
a) Effect of temperature:
Increasing of temperature will causes an increase in solubility of precipitate , leading to an
increase in Ksp value for precipitates with slight solubility.
b) Effect of solvent: like dissolve like
Solubility of inorganic salt is reduced by addition of organic solvent such as ethanol,
methanol, propanol and acetone.
but in presence of only water, hydration of ions of salt increases due to the high dipole
moment of water molecule.
This hydration produces energy called hydration energy which is sufficient to overcome the
attractive force between ion of solid lattice.

72
c) Formation of complex ion:
 The solubility of precipitate may be greatly altered with presence of some
species that forms a soluble complex with anion or cation of the precipitate.
Al(OH)3 ⇌ Al3+ + 3OH- + 6F- ⇌ AlF6
The precipitate of (Al+3) with base is never complete in the presence of F- ion
even thought Al(OH)3 has low solubility,
 Therefore, the computation between F- and OH- for Al+3 is high
 When F- concentration is increased, more of Al(OH)3 is dissolved and
converted to AlF6 ions that will be more stable than Al(OH)3 .

73
d) Common ion effect :
 In chemical equilibrium , Le Chatelier principle predicted that the solubility of
ionized substances or electrolyte is reduced with extent of excess amount of
ions that formed the substance in a solution.
 Eg. what happens to the position of equilibrium if we add some extra iodide ion,
I- or silver ion, Ag+? AgI (S) ⇌ Ag+ + I-

 The common ion effect is reduce the solubility of the solid. 74

Example 1: Calculate the solubility in mole/L for Ba(IO3)2 in a solution of 0.02M
KIO3, Ksp(BaIO3)2 = 1.57x10-9
Solution: Ba(IO3)2 ⇌ Ba+ + 2IO3-
x 2x
KIO3 ⇌ K+ + IO3-
0.02 0.02
Ksp = [ Ba+] [ IO3-]2
Ksp = (x) (2x + 0.02)2 ………..( 2x is ignored because it is very small)
1.57x10-9 = (x)(0.02)2
1.57x10-9 = 0.0004x
x= 3.9x10-6 mole/L
If KIO3 is not in the solution the solubility of Ba(IO3)2 become 7.32 x 10-4M which
is 188 folds grater than the above value.
75
2) Solid AgCl (Ksp = 1.8 × 10-10) is equilibrated with 0.010 M NaCl solution.
a) How many moles of AgCl will dissolve in 1.0 L of the NaCl solution ?
Ans=1.810-8 mol/L
b) What is the solubility of AgCl in pure water? Ans=1.3 × 10-5 mol/L.
In the NaCl solution: only 0.138% of the solubility in water alone!
3) What is the concentration of F-(aq) in mol/L, in a solution made by
equilibrating CaF2(s) with 0.20M KF solution? [Ksp for CaF2 = 4.1 × 10-11].
Ans=1.02510-9 mol/L
4) Calculate the solubility of PbCl2, in mol/L, in a solution of 0.15 M MgCl2.
[Ksp for PbCl2 is 1.7 x 10-5] Hint: concentration of Cl- from MgCl2= 2x0.15=0.3.
Ans=1.910-4 mol/L
76
5. Calculate the solubility of silver chloride in pure water and in a 0.10 M NaCl
solution. Compare the results. Ksp = 1.8 x 10-10
Ans, for pure water=1.3 x 10-5 M, for solution= 1.8 x 10-9M
6. Calculate the solubility of copper(I) iodide, CuI (Ksp = 1.1x10-12) a) water
b) 0.05 M sodium iodide. Ans, a=1.05 x10-6 M, b=2 x 10-11M

77
 3.3.4. Indicators
Indicators for argentometric titrations are selected to produce a color change at
or near the equivalence point.
Normally the indicator is selected to react with the added titrating agent, not
the analyte.
If A is the analyte, R the titrating agent and In is the indicator.
A +R → AR
In (color) + R → InR (new color)
To make the indicator change color, excess R must be added.
The smaller the excess added to cause the color change, the smaller the
endpoint error.
78
 3.3.5. Argentometric titrations
Argentometric titrations is a type of precipitation titration which involve the
use of silver (Argentum) ion.
It is called “Argentometric process” because it utilize standard solution of
silver nitrate (AgNO3) as a precipitating agent.
Conditions required for argentometry :
Precipitates should be practically insoluble
Precipitation reactions should be rapid and quantitative
Precipitate should not interfere in the sharp detection of the end point
The precipitate formation is stochiometric.
79
According to end point detection method, there are three main argentometric
titration methods.
Karl Friedrich Mohr
These are : (1806-1879)

Jacob Volhard
(1834-1910)

Kazimierz Fajans
(1887-1975)
80
 I. Mohr Method
This is a direct precipitation method that utilizes chromate as an indicator.
Chromate forms a precipitate with Ag+
but this precipitate has a greater solubility than that of AgCl, for example.
Therefore, AgCl is formed first and after all Cl- is consumed, the first drop of
Ag+ in excess will react with the chromate indicator giving a reddish
precipitate end point.
 The reaction:
Ag+ + Cl– ⇌ AgCl(s) [titration rxn  White precipitate]
2Ag+ + CrO42- ⇌ Ag2CrO4(s) (indicator rxn End point -reddish prpt)
81
 The pH of the reaction mixture is critical and neutral medium (pH about 7)
should be used.
 Increasing acidy enhance solubility of ppt(Ag2CrO3) and conversion of an
indicator chromate ion in to dichromate (Cr2O72-)
2CrO42-(aq) + 2H+(aq) Cr2O72- +H2O
In alkaline solutions, silver will react with the hydroxide ions forming AgOH
precipitate.
 Indicator: soluble chromate salt (Na2CrO4, K2CrO4)
 NB: – formation of colored precipitate at the end point.

82
 II. The Volhard Method
This is a back titration (indirect titration) type that must be performed in
acidic media to avoid the formation of Fe(OH)3.
The analyte is 1st titrated with excess AgNO3
Ag- + Cl–  AgCl + Ag+ (in excess) (titration rxn)
Then excess silver (Ag+ ) is titrated with standard solution of potassium (or
sodium) thiocyanate using iron ion (Fe3+) as indicator.
Ag+ + SCN– ⇌ AgSCN(s) (back titration rxn)

83
 Finally, as SCN- will be in excess in titration, red colour appear due to
formation of FeSCN2+.
Fe3+ + SCN-  FeSCN2+ (brick-red) (End point rxn)
 Indicator- Ferric ammonium sulfate or ferric nitrate
The indicator system is very sensitive and usually good results are obtained.
It is an indirect (back titration) method of precipitation.

Among Argentometric titrations methods, the Volhard Method is widely used

because we can detect the end point of precipitation titration very well.

NB: formation of a soluble, colored complex at the end point.

84
 III. Fajan's Method
It is a direct titration of chloride with silver ions (from silver nitrate).
Ag+ + Cl − ⇌ AgCl(s)
Fluorescein and its derivative are used as an indicator.
Fluorescein is a weak acid, which partially dissociates in water to form
fluoresceinate anion (A-).
After all chloride is used, the first drop of Ag+ will react with fluorescein
forming. Ag+ + Indicator  Ag indicator
This Ag indicator are adsorbed on AgCl forming Red color.
NB: adsorption of a colored indicator on the precipitate at the end point.
85
 3.3.6. Mercurimetric titrations as substitutes for
precipitation methods
These are an alternative method for titration of halides, thiocyanides and
cyanides.
Here mercuric ions are used in place of silver ions.
End point: determined by colour change from yellow to blue-violet due to
diphenyl carbazone or bromophenol blue indicator interaction with mercury.
In aqueous solution end point is not very sharp.
So 80% ethanolic solution is used (shows sharp end point).

86
 3.3.7. Applications
• It is used for the determination of halide ions (Br-, I-, Cl-) in the solution
• Used to measure salt content in food, beverage and water
• Used to analyze drugs like:
Phenylepherine hydrochloride Aminophyline
Succinylcholine.  Ammonium chloride
Tubocurine chloride  Dextrose and sodium chloride injection
Hydroxy amphetamine bromide  Dimenhydrinate tablet
 Carbromal  Potassium chloride infusion
Thiamine Hydrochloride  Sodium chloride infusion
87
 III) Complexometric titrations
1 Introduction
 A complexometric titration is the type of volumetric analysis involving the formation of
complexes which are slightly ionized in solution, like weak electrolyte and sparingly soluble salt.
The complexes are formed by the reaction of a metal ion (cation) with a legend which may be
either an anion or a neutral molecule.
The metal ion is known as Central metal atom.
The anion or neutral molecule is known as Ligand (L)
Example of molecule complex: Cu2+ + 4NH3 ⇌ Cu(NH3)42+

Example of ions complex: Ag+ + 2CN- ⇌ [Ag(CN)2]-

Fe3+ + 6SCN- ⇌ [Fe(SCN)6]3- 88
 This titration is particularly useful for the determination of a mixture of
different metal ions in solution.
 In complexometric titration the formation of a colored complex is used to
indicate the end point of a titration.
 An indicator capable of producing a definite color change is usually used to
detect the end-point of the titration.
 A ligand is an ion or molecule, which donates a pair of electrons to the central
metal ion to form complex.
 A chelating agent is a substance whose molecules can form several bonds to
a single metal ion.
 In other words, a chelating agent is a multidentate ligand. 89
M+ + L ↔ ML
Ag+ + 2 CN- ↔ [Ag(CN)2]-
Cu2+ + 4 CN- ↔ [Cu(CN)4]2-
Ag+ + 2 NH3 ↔ [Ag(NH3)2]+
Cu2+ + 4 NH3 ↔ [Cu(NH3)4]2+
Central metal atom = acts as Lewis acid (electron acceptor)
 Ligand = acts as Lewis base (electron donor), it share a paired electron.
So, it forms a Coordinate bond (dative) = The bond formed between central
metal atom (ion) (acceptor) and the Ligand (donor).
Molecules composed of metal and ligands (chelating agent) are known as
coordination complex.
90
* Coordination number = The no. of coordinate bonds formed to a metal ion
by its ligands.
* Characters of coordination number *
It is even number: 2 e.g. Ag+ , 4 e.g. Ni2+ , Cu2+ , 6 e.g. Fe3+ , Cr3+
It is usually double the charge of the metal.
The charge of a complex is the algebraic sum of the charges of the central ion
and ligand .. e.g.
 [Ag(CN)2] -  Ag+ + 2 CN -
 1 (+ve) + 2 (-ve) = 1 (-ve)
e.g. [Fe(CN)6]3-  Fe3+ + 6 CN -
3 (+ve) + 6 (-ve) = 3 (-ve)
The higher the valence of metal ion the more stable the complex
e.g.Ferricyanide is more stable than Ferrocyanide
 Types of complexing agents
Ligands can be classified depending on the number of sites of attachment
to the metal ion
1. Unidentate (Monodentate) Ligand: contain only one center of donation
The ligand attached to metal at one site e.g. H2O, NH3, CN-, Cl-, I-, Br- (i.e.
forming one coordinate bond, or capable of donating one unshared pair of
electrons). H3N:Ag:NH3
2. Bidentate Ligand-The ligand attached to metal at two sites (contain 2
centers of donation).

92
Tridentate Ligand: The Ligand attached to metal at 3 sites

Tetradentate Ligand: The Ligand attached to metal at 4 sites

93
 Chelation
Chelate : It is a complex formed between the ligand containing two or more
donor groups and metal to form ring structure. (heterocyclic rings or chelate
rings)
Chelating agents: organic molecules containing two or more donor groups
which combine with metal to form complex having ring structure.
Chelates are usually insoluble in water but soluble in organic solvent.
Sequestering agent : Ligands which form water soluble chelates e.g. EDTA.
 Factors affecting stability of complex
A. Effect of central metal ion :
1. (1)- Ionic size (metal radius):
- Smaller an ion (small radius of metal)  greater its electrical field 
more stable complex
2. (2)- Ionic charge (metal charge):
- Metal of higher charge give more stable complexes. e.g. Ferricyanide
[hexacyanoferrate III] is more stable than Ferrocyanide [hexocyanoferrate II].
3. (3)- Electronegativity :
The higher acidity (electronegativity) of metal (Mn+)  the higher stability
of complex.
B. Effect of Ligand:
1. Basic character:
- The higher the basicity (strong base is good electron donor)  the higher
the ability of ligand to form complex. e.g. ligand contain electron donating
atom.
e.g. N > O > S > I- > Br- > Cl- > F-
2. The extent of chelation:
- Multidentate ligands form more stable complexes than monodentate.
3. Steric effect:
- Large, bulky ligand form less stable complexes than smaller ones due to
steric effect. e.g. ethylene diamine complexes are more stable than those of
the corresponding tetramethyl ethylene diamine.
 Basic principles of complexometric analysis
The reaction should reaches equilibrium rapidly.
The reactions in which interfering situations do not arise.
The reaction in which a indicator is capable of locating equivalence point
with fair accuracy is available.
Mn+ should not be precipitated at the pH of titration. If Mn+ is ppt. as MOH,
auxiliary reagent must be added to prevent pptn. of M n+.
Examle: pb2+ salt is ppt. as pb(OH)2 at the pH suitable for titration.
add tartaric acid (auxiliary reagent) which converts pb(OH)2 to soluble lead
tartarate complex.
97
 Complexones
Different chelating agents are available.
Amino polycarboxylic acid compounds used as
complexing agents for many metal ions.
H3Y

EDTA (H4Y) is the most widely used chelone in

metal ion titration.
 General principles in disodium EDTA titrations
EDTA is Ethylene Diamine Tetra Acetic acid.
It has four carboxyl groups and two amine groups.

Structure of EDTA
Commonly EDTA is represented in the acid form as H4Y.

99
Due to low solubility of acid form of EDTA in water, its disodium dihydrate
EDTA salt i.e. Na2H2Y.2H2O is used.

Disodium dihydrate EDTA = Na2H2Y.2H2O

The four carboxyl groups and two amine groups can act as an electron pair
donors.
Note that only fully ionized oxygen (4-charged anion) bind to metal cation.
EDTA is polydentate ligand as it donate its six lone pairs of electrons for the
formation of coordinate covalent bonds with metal cations to form Metal-
EDTA complex. 100
 Metal-EDTA complex

So, EDTA is not a selective reagent as it can complex with all metal ions
(divalent, trivalent, tetravalent) with a ratio 1:1 regardless of the charge on the
cation.
The stoichiometry for all metal ion is the same.
e.g. Ag+ + Y4- ---- AgY3-
Hg2+ + Y4- ----  HgY2-
Al3+ + Y4- ---- AlY-
101
About 2.6g of hydrated nickel sulfate (NiSO4.6H2O) was weight and dissolved
in deionized water and made up too 100ml. 20ml sample of this solution was
titrated with18.15ml of 0.112M EDTA solution using appropriate indicator.
Calculate the %w/w of nickel in hydrated nickel sulfate.
s/n the reaction is Ni + EDTA (1:1 ratio)
Mol of EDTA = CV= 0.112M x 18.15ml = 2.0328mmol which is equal to mol
of Ni in 20ml.
2.0328mmol x 100ml
Mol of Ni in 100ml= = 10.164mmol =1.0164 x 10-2 mol
f=c[
Mass of Ni = mol x M.mass (Ni) = 1.0164 x 10-2 mol x 58.69 g/mol. =
0.59652516g
cQWW Zi {S =.An•AfA<•
%w/w = x 100 = x 100 = 22.94%w/w
cQWW Zi |}ZT~RY 2.6g
102
 Types of EDTA Titrations:

EDTA Titrations

Replacement/ Indirect
Direct Back Displacement/ Alkalimetric Titrations
Titrations Titrations Substitution Titrations
Titrations
 1. Direct Titrations:
• This is a direct determination of a metal ion by adding standard EDTA titrant
EDTA of known concentration
to the sample solution.
 The solution containing the metal ion is buffered to the desired pH and
titrated directly with standard EDTA solution.
 Some auxiliary complexing agent such as tartrate can be added to prevent
the precipitation of the hydroxide of metal ion.
Sample of unknown
 Cu+2, Zn+2, and Ni+2 can be determine by usingconcentration
direct titration method.
and indicator

+
Metal ion + EDTA [ Metal-EDTA ] complex
 2. Back Titrations:
 This is method, an excess of standard EDTA is added to the sample solution
of metal ion.
 The resulting solution will contain unreacted EDTA which is then back
titrated with standard metal ion solution in the presence of indicator.
 ZnCl2, ZnSO4, MgCl2, MgSO4 is used as standard metal ion solution.
 Al+3, Co+2, Pb+2, Mn+2, Hg+2, and Ni+2 can be determine by using Back
titration method
Solution
containing
Al and + +
Sample Excess of Metal-EDTA Unreacted
indicator
Metal standard EDTA Complex standard EDTA
ion M1 M1-EDTA

Metal-EDTA Standard
Complex Metal ion M2
M2-EDTA
 3. Replacement, Displacement or Substitutions Titrations:
Mg-EDTA
 This is method, weak EDTA complex of another metal
EDTAion (M2) is added to
the solution of metal ion (M1) to be determined.
 Mg-EDTA
Solution & Zn-EDTA are frequently used weak EDTA complex
containing
 The
Ca2+ weaker
and metal EDTA complex is replaced with strong metal EDTA
complex.
indicator
+
 The equivalent amount of metal M2 freed from the weaker+ complex can be
Weak Strong Replaced
Sample
titrated with standard EDTA solution.
Metal-EDTA Metal-EDTA Free metal
Metal
Complex Complex ion M2
ion M1
 This method is useful for
M2-EDTA the of Ca+2
determinationM1-EDTA ion.

Metal-EDTA Standard
Complex EDTA solution
M2-EDTA
 4. Alkalimetric Titrations:
EDTA
 This method, use the principle of liberation of free HNaOH
+ ions during the

complexation.
 The reaction between metal ion and EDTA H2Y-2 produce H+.
Solution
containing
Ca2+ and M+n + H2Y-2  MY(n-4)+ + 2H+
indicator +
 The free H ions is titrated with standard solution of alkali like NaOH by
+ +
using suitable acid-base indicator. 2H+
Sample standard EDTA Metal-EDTA Liberated H+
 TheMetal
H+ ions can also
H2Ybe
-2 determined by instrumental
Complex method. ions
ion M+n MY(n-4)+

NaOH

Standard
Acid-Base Alkali solution
Titration product
 5. Indirect Titration:
 This method is used
+ to determine the ions such as Halides,+phosphates,
Ba+2 and
sulphates that do not form complex with EDTA
Anions Excess of ion, SO -2 BaSO +
 In the determination
-2 of sulphate 4 ion 4
solution is Unreacted
treated withBa
excess
like SO4 standard Barium Precipitate
of standard solution of Barium ion. ions
solution
 The formed precipitate of BaSO4 is filtered off and unreacted Barium ions
present in filtrate is titrated with EDTA.
 In this way, we are able to indirectly determine the amount of sulphate ion
present in the sample solution. Standard
Ba-EDTA EDTA solution
Complex
 Methods of increasing the selectivity of
EDTA as Titrations
Methods

Chemical pH Masking Unmasking Kinetic

Separation Control Masking
 1. Chemical Separation
 In this technique, the selectivity is increase by separating the species from
other components from the sample solution.
 The separated species is then dissolved in suitable solvents and then titrated
against EDTA using indicator.
 Eg: Ca+2, Mg+2, Ni+2 and Cu+2 ions can be first separated as Ca-oxalate, Ni-
DMG (Dimethylglyoxime), Mg-ammonium phosphate and Cu-thiocyanide.
 These precipitate are then dissolved in separate suitable solvents and then
titrate against EDTA using indicator.
 Ca+2 Mg+2

Ni+2 Cu+2

Ammonium
Oxalate DMG phosphate thiocyanide

Ca-oxalate Ni-DMG Mg-ammonium Cu-thiocyanide

precipitate precipitate Phosphate precipitate
Precipitate
Ca-oxalate Ni-DMG Mg-ammonium Cu-thiocyanide
phosphate

solvent solvent solvent solvent

Ca+2 Ni+2 Mg+2 Cu+2

EDTA EDTA EDTA EDTA

Ca-EDTA Ni-EDTA Mg-EDTA Cu-EDTA

 2. Control of acidity of pH of the solution
 In this technique, the selectivity is increases by controlling the pH of the
solution.
 The conditional formation constant for metal-EDTA complex is depend on
the hydrogen ion concentration.
 So by adjusting the pH of the sample solution containing several metal ions,
it is possible to allow only a single species to react with EDTA.
 E.g.: Ca+2 can be determined in the presence of Mg+2 in strongly alkaline
solution (pH < 10).
 Trivalent ions like Bi+3, Fe+3 can be selectively determined from the solution
of bivalent metal ions in strongly acidic solution (pH ~ 2).
 Selectivity by pH Control

A+2 B+2 A+2 B+2

Ca+2 Mg+2

Bi+3 Fe+3

EDTA EDTA EDTA

At Alkaline At acidic
At acidic
pH < 10 pH ~2
pH ~2

Metal-EDTA Metal-EDTA Metal-EDTA

Complex Complex Complex
Ca-EDTA Bi-EDTA Fe-EDTA
 3. Use of Masking agent
 Masking is a process in which substance is prevented to take part in the
reaction without physical separation of it.
 The reagent used in masking is known as masking agent.
 Cyanide ion is an effective masking agent for EDTA titrations.
 It forms stable cyanide complex with the metal cation like Cd, Zn, Hg, Cu,
Co, Ni, Ag, Pt
 but does not form complex with alkaline earth metals like Mg, Ca etc as well
as Mn and Pb.
 Thus it is possible to determine Ca, Mg, Pb, Mn in the presence of other
metal cations by masking agents like CN- ion
 Ca+2 Zn+2

Hg+2 Ni+2

CN-

Ca+2 Zn-CN Hg-CN Ni-CN

ions complex complex complex

EDTA

Masked complexes
Metal-EDTA Complex Prevented to take part in reaction
Ca-EDTA
 4. Use of Demasking
In this technique, one of the
Ca+2cation is
Znfirst
+2
masked and remaining free cation
is titrated with standard EDTA.
Masking CN-
Then previously masked cation is demasked by using suitable reagent to get
free cation.
This
+2
free cation is then titrated by using standard EDTA. Zn-CN complex
Ca ions
eg. Formaldehyde is used to demasked Zn-CN complexDemasking
EDTA
[Zn(CN)4] + 4HCHO + 4H Zn+2 + 4HOCH2CN
Zn+2 ion

This free
Metal-EDTA Zn +2 ion is then titrated by using standard EDTA.
EDTA
Complex
Thus it is possible to determine Zn in the presence of Ca.
Ca-EDTA Metal-EDTA
Complex
Zn-EDTA
 5. Kinetic masking
 Some of the metal undergoes fast complexation while some other
undergoes slow complexation with EDTA.
 Hence it is possible to titrate the metal ions which undergoes fast
complexation with EDTA in the presence of those metal ions which
undergoes slow complexation with EDTA .
 eg. Fe+3 can be easily estimated in the presence of Cr+3, because Cr+3 reacts
slowly with EDTA to form complex as compared to Fe+3.
 Kinetic masking

Fe+3 Cr+3

EDTA- EDTA-

FAST- SLOW

Metal-EDTA Metal-EDTA
Complex Complex
Fe-EDTA Cr-EDTA
 Indicators and end point detection
1. Acid-base Indicator.
2. Turbidity end point (appearance of turbidity).
3. Instrumental method.
4. Metal indicator ((Metallochromic Ind.)).
5. Specific Indicator.
 Metallochromic Indicator.
Metallochromic Indicator
 The metallochromic indicators are organic compounds which are capable of
forming intensely
+ coloured complex with EDTA.
 This metal complex is weaker than theMetal-Indicator
–indicatorIndicator
Sample Metal-EDTA complex
Metal
and it has Organic
different colour Weak Complex
from uncomplexed indicator.
ion Compound Colour 2
 During the course of titration,
Colour 1the metal ion from metal –indicator complex
is replaced to form Metal-EDTA complex.

EDTA
Metal-EDTA
Strong Complex
Colour 3
Example: eriochrome black T (EBT) which is dark powder with a
slight metallic luster (A).
A
If it is added to hard water that contain Mg2+
Mg-EBT(aq) which is red-purple in color is formed (B).
Then it was titrated with ethylene diamine tetraacetic acid (EDTA) B
Mg-EBT(aq) + EDTA(aq) = Mg-EDTA(aq) + EBT(aq)
Free EBT in the solution gives a blue color to the solution (C).
C
It is used for the determination of Mg , Zn , Cd , pb , Hg
2+ 2+ 2+ 2+ 2+

& Mn 2+ salt at pH 7 – 11 using ammonia buffer (pH = 10)

ETB cannot be used for the determination of Cu2+ , Fe3+ , Al3+ , Co2+
and Ni 2+ 122
 Specific Indicator
Examples: Thiocyanate (CNS -)
−It is specific indicator for Fe 3+
−When sample of Fe 3+ is treated with CNS – a blood red complex is
formed.
−Upon titration against EDTA, the end point is detected by decolorization of
the blood red color.
 5 Applications
Total hardness of water (Ca2+ and Mg2+).

Determination of Cu2+, Ni2+, Pb2+, and Zn2+ in plating baths.

To titrate the amount of ions available in a living cell.

widely used in pharmaceutical industry to determine metal concentration in

drugs

124
 IV) Redox titrations
 Reactions are mainly based upon the oxidation-reduction reactions by using
oxidizing or reducing agents.
Oxidation Reduction
Loss of Electron Gain of Electron
Oxidant + Loss of Hydrogen ne- ↔ Reductant
Gain of Hydrogen
Gain of Oxygen Loss of Oxygen
 Oxidation: eg. H2 → 2H+ + 2e-
 One positive charge means deficient by one electron
 Reduction: eg. F2 + 2e− → 2F−
 One negative charge means rich by one electron
125
E.g. in 2Mg + O2  2MgO and MgO + H2 → Mg + H2O
 Mg is oxidized to MgO (Mg from 12 electrons to 10 electrons in Mg2+)
 MgO is reduced to Mg (MgO from 10 electrons to 12 electrons in Mg)
When there is an atom that donates electrons, there is always an atom that
accepts electrons.
Eg. In H2 + F2 → 2 HF H is being oxidized and F is being reduced
So, both processes occur simultaneously.
Remember OIL RIG
(Oxidation Is Loss and Reduction Is Gain)

126
 Oxidizing and Reducing agents
Oxidizing agent is a reactant (substance) that:
can gain electron
undergoes reduction
• Eg. In H
oxidizes 2+F
other 2 → 2 HF
reactant
• Oxidation
in a reactionreaction:
undergoes → 2 H+ + 2ine-oxidation
H2decreasing
• Reduction
Reducing agentreaction: e− → 2 F−that :
F2 + 2 (reactant)
is a substance
• In loss
can this reaction
(donate) electron
• H2 actsoxidation
undergoes as an reducing agent and
• F2 acts
reduces a oxidizing
other substancesagent.
(reactants)
undergoes increasing in oxidation number 127
 Oxidation number or oxidation state (OS):
 An oxidation number is total number of electrons that an atom either gains or
loses in order to form a chemical bond with another atom
 A positive OS reflects the tendency atom to loose electrons
 A negative OS reflects the tendency atom to gain electrons
 The oxidation number of an element in its free (uncombined) state is zero. Al.
 The OS of an alkali metal (IA family) in a compound is +1;
 the OS of an alkaline earth metal (IIA family) in a compound is +2.
 The oxidation number of oxygen in a compound is usually –2.
 The oxidation state of hydrogen in a compound is usually +1.

128
 The sum of oxidation numbers of all the atoms in a compound is zero.
 The sum of oxidation numbers of all the atoms in the polyatomic ions is the
charge of the ions
 This rule often allows us to calculate the oxidation number of an atom that may
have multiple oxidation states, if the other atoms in the ion have known
oxidation numbers.
Example 1. find the OS of Cu and N in CuO and NO3-
Oxygen is -2. so Cu is, x+(-2)=0  x=+2, for N, y+3(-2)=-1  x=+5
2. Find the OS of each Cr in K2Cr2O7
Let the OS of each Cr be = x

129
• Net charge on the neutral K2Cr2O7 molecule = 0

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
x = +6
3. Find the OS of S in Na2SO4. Ans= x=+6
4. Find the OS of P in PO43-. Ans=+5

130
 How to balance redox reaction
Half reaction method
1. Identify the species being oxidized and reduced
2. Write the oxidation and reduction reactions separately
3. Balance atoms other than H and O
4. Balance O by adding H2O to the side that need O
5. Balance H by adding H+ to the side that need it
6. Balance charge by adding electrons as necessary
7. Balance number of electrons between two half reaction
8. Cancel any species on both sides and add the half reaction together.

131
 Example 1: 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
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.

132
 Ag +(aq) + e- Ag (S)

 Ag+(aq) becomes Ag 0 (S) by gaining 1 electron.

So Ag+(aq) getting reduced to Ag (S) is the reducing half reaction.

Final Balancing act:

 Making the number of electrons equal in both half reactions

[Cu0(S) Cu2+(aq) + 2e-] × 1

[Ag +(aq) + e- Ag (S)]× 2

Cu0(S) + 2Ag +(aq) Cu2+(aq) + 2Ag (S)

133
 Example : Balancing complex redox reactions
Fe+2(aq) + MnO4-(aq)  Mn+2(aq) + Fe+3(aq)

Oxidizing half: Fe+2(aq)  Fe+3(aq) + 1e-

Reducing half: MnO4-(aq)  Mn+2(aq)

Balancing atoms: Balancing oxygens

MnO4-(aq)+  Mn+2(aq) + 4H2O

Balancing hydrogens: Reaction happening in an acidic medium

MnO4-(aq)+8H+  Mn+2(aq) + 4H2O

134
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)
Final Balancing act:
Making the number of electrons equal in both half reactions

[Fe+2(aq) Fe+3(aq) + 1e- ]× 5

[MnO4-(aq)+8H++ 5e- Mn+2(aq) + 4H2O]×1

5Fe2++ MnO4-(aq)+8H++ 5e-

5Fe3+ +Mn+2(aq) + 4H2O + 5e-
135
5Fe2++MnO4-(aq)+8H+ 5Fe3+ +Mn+2(aq) + 4H2O

5 Fe 2+ ions are oxidized by 1 MnO4- ion to 5 Fe3+ ions.

In terms of moles:

5 moles of Fe 2+ ions are oxidized by 1mole of MnO4- ions to 5 moles of

Fe3+ ions.

Mathematically: Moles of Fe2+ = 5 x [Moles of MnO4-]

136
 Principles and procedures in different types of redox titration
Redox titrations involve solutions of reducing and oxidizing agents.
It is used to determine the concentration of a given analyte by causing a
redox reaction between the titrant and the analyte.
In a redox titration, precisely enough electrons have been removed to oxidize
all of the reducing agent.
Its procedure is the same as with acid/base titrations.

137
 Different types of redox titration
Types of Redox titrations are named according to the titrant that is used:
1. Potassium permanganate methods
2. Ceric sulfate methods
3. Iodimetric and Iodometric methods
4. Bromination methods
5. Potassium iodate methods
6. Potassium dichromate methods

138
 1. Potassium permanganate (KMnO4) methods
KMnO4 is probably the most widely used of all volumetric oxidizing agents.
It is a powerful oxidant and readily available at modest cost.
8H+ + MnO4- + 5e- = Mn2+ + 4H2O
Eg. 2KMnO4 + 10FeSO4 + 8H2SO4  2MnSO4 + K2SO4 + 5Fe2(SO4)3 + 8H2O
It is sulf indicator tha turns from pink to colourless when reduced to Mn2+
KMnO4 is not suitable as primary standard solution.
−It cannot be obtained in pure form (will have MnO2 as an impurity)
−This will catalyze reduction of manganese (vii), auto catalytic
decomposition.
Hence, it need to be standardized first with the a primary standard such as
oxalic acid, sodium oxalate, arsenious oxide, and Mohr's salt. 139
 MnO4 Standardization
Standardization of MnO4 means determining the strength of potassium
permanganate with a primary standard solution (oxalic acid).
Procedure:
1. Preparation of 0.1N MnO4:
Dissolve 3.2g of KMnO4 (Mwt=158g/mol and ne- = 5)in water to get
1000ml solution (8H+ + MnO4- + 5e- = Mn2+ + 4H2O)
Stir the solution well.
Heat it to boil for 15-30min in water bath (to expel the CO2 gas produced
in the reaction).
Cool, filter and transfer to clean brown colored glass.
Standardize the solution after 24hours of its preparation. 140
2. Standardization with standard oxalic acid 0.1N
Dry the sodium oxalate at 105-110oC for 2hrs.
Cool in desiccator and dissolve exactly 1.125g of pure anhydrous oxalic
acid (90g/mol) in distilled water to get 250ml solution.
Mix the solution well
Pipette out 25ml in to titration flask and add 20ml of dilute sulfuric acid
Heat the solution to 60-70oC.
Swirl the solution and titrate with KMnO4 solution from the burette until a
faint pink colour persists for 30sec upon shaking the flask.
Repeat the process until 3 concordant reading will be obtained.

141
The reaction is:
2KMnO4 + 5H2C2O4 + 3H2SO4 → 2MnSO4 + 10CO2 + 18H2O + K2SO4
Calculations:
a2M1V1 = a1M2V2
 Where:
M1 (concentration of potassium permanganate) = ———— M
V1 (average volume of potassium permanganate) = ————mL
M2 (concentration of oxalic acid) = 0.1 molar
V2 (volume of oxalic acid) = 10 mL
a1 (the number of electrons gained per formula unit of potassium permanganate in the
balanced chemical equation of half-cell reaction) =2
a2 (the number of electrons lost per formula unit of oxalic acid in a balanced chemical
equation of half-cell reaction) = 5
Finally calculate for the strength (g/L) using M1 obtained.
Strength = molarity*molecular mass(158g/mol) 142
 Procedure to use KMnO4 standard for titration.
Standard solution (MnO4-) is added to burette and initial volume recorded.
Using pipette, the analyte volume is measured and added to conical flask.
An excess of sulfuric acid (H2SO4) is added to flask to provide H+ ion.
Trial titration carried out.
KMnO4 is added from burette and oxidizes the analyte.
Colour of MnO4- is purple.
It lose its colour when is reduced to Mn+2.
Once all the analyte (Fe2+) is consumed the next drop of MnO4- remain purple
which indicate end point.
Final volume is recorded after colour change is observed in the flask.
Titration is repeated until two consecutive volume consumed are not vary by more
than 0.1cm (excluding trial). 143
Eg1. If 17ml of 0.1M KMnO4 is needed (from burette) to oxidize 25ml of a
FeSO4 solution in acidic solution (diluted H2SO4 is added to conical flask) what
is the molar concentration of FeSO4?
Write the equation: Fe+2(aq) + MnO4-(aq)  Mn+2(aq) + Fe+3(aq)
Balance the equation:
5Fe2++MnO4-(aq)+8H+  5Fe3+ +Mn+2(aq) + 4H2O
Given: for MnO4-, V=17ml C=0.1M from this mol=CV=1.7mmol
<.@ccZ[ B AcZ[
Mol of Fe2+ interact with 1.7mmol of MnO4- is = = 8.5mmol
< cZ[
b.AccZ[
Concentration of Fe is = 0.34M
fAc[

144
2. A sample of metal of mass 2.5g was thought to contain a quantity of iron. To
determine the percentage of iron in the sample the sample was dissolved in
diluted sulfuric acid and the resulting solution made up to 250ml. Of this
25ml was titrated against 0.018mol/L potassium manganate solution. A mean
titre of 24.8ml was recorded. Calculate the percentage by mass of iron in
metal. (Fwt of Fe = 55.8g/mol).
Answer = 49.8%w/w

145
3. 25cm3 of H2O2 reacts with 16cm3 of 0.1M KMnO4 (aq) Calculate the
concentration of the H2O2.
2 MnO4- + 5 H2O2 + 6 H+ 2 Mn 2+ + 5 O2 + 8 H2O

H2O2 n = MnO4- n= ?
?
c= c = 0.1 moll-1
?
v= 0.025 l v = 0.016 l

n = 0.1 x 0.016

n = 0.0016 moles of MnO4-

2 MnO4 : 5 H2O2
H2O2 : c = n/v
2 moles :: 5 moles
= 0.004 / 0.025
1 : 2.5
0.0016 : n
c = 0.16 moll-1
n = 0.0016 x 2.5
1

= 0.004 moles H2O2

 2. Ceric salt (Cerimetry) methods
The titration involving determination with cerium compounds (a titrant) are
called cerimetry.
The titration should carried out in acidic medium.
Cerium exist in two oxidation states (4+& 3+).
In tetra valent state, (Ce4+) eg (NH4)4Ce(SO4)4·2H2O. (Ammonium ceric
sulphate), it act as strong oxidizing agent.
This salt solution is yellow in colour and they become colourless after ceric ion
(Ce4+) is reduced to Cerous ion (Ce3+) forming another salts.

148
 dfj
Eg. C6H5CH2OH + 2Ce(NO3)6(NH4)2
d€
 C6H5CHO +2Ce(NO3)5(NH4)2
Yellow Colour less
Therefore in hot and non so dilute solution it can be used as self indicator.
Ceric solution (Yellow)  on reduction  cerous salt obtained (colorless)
Ce4+ + e- ⇌ Ce3+
But in diluted solution we use an indictor (ferroin) in order to avoid errors.
Some of the compounds of Cerium such as Ceric ammonium nitrate
(NH4)2Ce(NO3)6, Ceric ammonium sulphate (NH4)4Ce(SO4)4 and Ceric
hydroxide Ce(OH)4 can be used for determination.

149
 Standardization of Ceric ammonium sulfate
Ceric ammonium sulfate solution is titrated with arsenic trioxide (primary
standard) in presence of sulfuric and osmic acid utilizing the ferroin sulfate as
indicator.
End point is visually detected by change in color from pink to very pale blue.

150
 Procedure
1. Preparation of 0.1M of Ceric ammonium sulfate
Dissolve 65g of Ceric ammonium nitrate with the help of gentle heat in
mixture of 30ml concentrated H2SO4 and 500ml distilled water.
Cool, filter the solution if turbid, and dilute to 1000ml by distilled water
(Mwt= 632.6g/mol).
2. Preparation of 8%w/v sodium hydroxide
Dissolve 8g of NaOH with distilled water to give 100ml of 8%w/v solution.
3. Prepare 1%w/v osmic acid (catalyst) by dissolving 100mg in distilled water to
get 10ml of 1%w/v.

151
4. Prepare 10%w/w of sulfuric acid by diluting 57ml of H2SO4 in distilled water
to 1000ml. (Mmas=98.08g/mol and molar concentration of H2SO4 is 18.4M)
5. Weigh accurately 0.2g of arsenic trioxide (previously dried at 105oC for
1hour),
Transfer to 500ml conical flask
Add 25ml of 8%w/v NaOH solution prepared, swirl to dissolve, add 100ml
water and mix.
Add 30ml of 10%w/v H2SO4, 0.15ml of osmic acid and 0.1ml of ferroin
sulfate solution (indicator).
6. Titrate the above mixture with ceric ammonium nitrate until the pink color
disappear.
152
Solution in flask: 0.2g of arsenic trioxide
• 25ml of 8%w/v sodium hydroxide
• 100ml of water
• 30ml of 10%w/v sulfuric acid
• 0.15ml of 0.1% osmic acid solution
Solution in burette: 0.1M ceric ammonium nitrate
Indicator: 0.1ml of ferroin sulphate solution
End point: pink to colorless.
Finally record the volume ceric ammonium nitrate consumed and calculate for
its molarity by the following formula:
8XSolY Zi •‚fjk
Ceric ammonium nitrate concent (M) =
9~}}XYYX }XQTSƒo „ =.==?n?•
Ceric sulphate has advantage over KMnO4 and potassium Dichromate:
Solution remain stable if boiled and over a prolonged period.
Cerous ion is colorless hence does not interfere with the color of a reduction-
oxidation indicator such as Ferroin and can be used as a self-indicator.
Only one oxidation state: Cerous ion (Ce3+) result from ceric ion (Ce4+), but,
MnO4 ion can reduced to several oxidation state (Oxidation number
of Mn in MnO2, MnO42−, MnO4− are 4, +6 and +7 respectively).
Cerium nitrate is available in sufficiently pure form to use directly (without
standardization).
Its ability to be used in a high concentration of Hydrochloric Acid (where
KMnO4 is unsuitable)
154
Disadvantages of Ceric salts
−They are relatively expensive
−Do not dissolve readily in water or dilute acid solutions due to hydrolysis
and precipitation of Ceric Hydroxide.
−Solutions of these salts are difficult to prepare and must be made in stronger
(1 - 2 Normal) acid levels.

155
 3. Iodine titration
i. Iodimetry: iodine solution (titrant) is directly titrated with a reducing agent.
Example: Quantification of Ascorbic Acid (Vitamin C)
C6H8O6 + I2 → C6H6O6 + 2I- + 2H+
Iodine rapidly oxidizes ascorbic acid, C6H8O6.
Starch is used as indicator.
Starch confer blue color to the solution and disapearance of this color
indicate an end point.

156
i. Iodometry: is the titration of iodine (I2) produced when an oxidizing analyte
is added to excess I-(iodide) in acidic medium.
Then the iodine (I2) is usually titrated with standard thiosulfate solution.
It is not a direct titration because there are 2 reactions:
Analyte (oxidizing agent) + I- →I2 (liberated iodine)
2MnO4- + 16H+ +10I-  2Mn2+ +5I2 + 8H2O
I2 + reducing agent (standard sodium thiosulfate) product
I2 + 2S2O32-  S4O62- 2I-

157
• Ex. The number of moles of carbon monoxide in a sample of air can be
measured as follows:
Step 1 The carbon monoxide reacts with iodine(V) oxide, producing iodine.
5CO(g) + I2O5(s) → I2(s) + 5CO2 (g)
Step 2 The iodine is then dissolved in potassium iodide solution and titrated
against sodium thiosulphate solution.
I2(aq) + 2S2O32–(aq) → S4O62–(aq) + 2I– (aq)

If 50.4ml of 0.10M sodium thiosulphate solution was used in a titration,

calculate the number of moles of carbon monoxide in the sample of air.
Step 1: Thiosulphate ion (sodium ion is spectator)

S2O32– n= ?
c= 0.1M
v= 0.0504 L

n = 0.1 x 0.0504
= 5.04 x 10-3 moles S2O32–
Step 2: 2S2O32– : 5CO
2 moles : 5 moles

1 mole : 2.5 moles

5.04 x 10-3 : n

n = 2.5 x 5.04 x 10-3

= 0.013 moles CO
 Direct Indirect
Iodimetric method Iodometric method

Iodine for determination of I- is added to oxidizing agents, the liberated

Titrating agent
reducing agents I2 is titr. with Na2S2O3

Indicator Added at the beginning of Added near the end of titr (when the brown
(Starch) titr. color of I2 becomes pale)

Type of reaction One step reaction Two step reactions

Standard solution Standard solution: Iodine (I2) Standard solution: Sodium thiosulfate

End Point. Permanent blue color disappearance of blue color (color161less)

 4. Potassium dichromate methods
Potassium dichromate is used as in oxidizing agent in acidic medium.
The medium can be maintained acidic by the use of dilute sulphuric acid.
It is mainly used for the estimation of ferrous salts and iodides.
It is obtainable in a state of high purity and can be used as a primary
standard.
The most important application of dichromate is in its reaction with iron (II)
Cr2O72-+ 6Fe2+ + 14H+ → 2Cr3++ 6Fe3+ 7H2O
There are three indicators that may be used for the titration of Fe with
K2Cr2O7.
These are diphenylamine, diphenyl benzidine and diphenylamine sulfonate.
The colour change for all three indicators is green to violet. 162
 Ex1. Iron(ii) chloride reacts with sodium dichromate as follows:

6 Fe 2+ + Cr2O72- + 14 H+ 6 Fe 3+ + 2 Cr 3+ + 7 H2O

a. Calculate the number of moles of iron(ii) ions which will react completely
with 330cm3 of a 0.15 moll-1 sodium dichromate solution.
b. Calculate the mass of Iron(ii) chloride required for the reaction.
A. Step 1:
Fe 2+ Cr2O72-

6 mole 1 mole
n= ? n= ?
c= ? c= 0.33
v= ? v= 0.15 moll-1

n = 0.15 x 0.33
n = 0.05 moles of Cr2O72-
Step 2: Calculate the number of moles of iron(ii) using mole ratios
from the balanced equation:

6 Fe 2+ + Cr2O72- + 14 H+ 6 Fe 3+ + 2 Cr 3+ + 7 H2O
6 Fe 2+ : Cr2O72-

6 moles :: 1 mole

n : 0.05

n = 6 x 0.05
1
= 0.3 moles of iron(II)
B. Mass of Iron(ii) chloride:

m = n x Mwt
m = 0.3 x 126.8

m = 38.04 g
 Redox indicators
• It may be defined as a substance that can be reversibly oxidized or reduced,
having different distinct colour in the individual oxidized and reduced forms.

Types of
Redox
indicator

Internal External Potentiometric

Self indicator
indicator indicator indicator
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I. Self indicator: The titrant itself acts as a indicator in titration.
• Example: KMnO4 is pink while the reduced Mn2+ is colourless.
II. Internal indicator: are the indicators which is used within the solution
(added to analyte).
These indicators takes part in the reaction.
Example: N-phenyl anthranilic acid, Starch.
III. External indicator:
• The indicator are not added to the solution and not take part in the reaction.
Example: Potassium Ferro cyanide K3[Fe(CN)6] can acts as external
indicator during titration of ammonium or ferrous sulphate (FeSO4) with
Potassium dichromate (K2Cr2O7).
168
 Near the equivalence point, drops of solution are removed and brought into
contact with dilute freshly prepared potassium ferricyanide solution on a plate.
• The end point is reached when first drop fails to give blue colour.
• These are almost replaced with internal indicator as there is loss of sample.
IV. Potentiometric methods:
• This is a physico-chemical method that is used when:
• suitable indicator are not available
• the visual indicator methods fails or is of limited accuracy.
• Example: For colored solution or for very dilute solution.
• End point depend on potential at given point.

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 Application of redox titration
Redox titration can accurately determines the concentration of an unknown
solution (analyte) that contains an oxidizing or reducing agent.
It is used to analyze a wide range of inorganic analytes.
It is used for the analysis of organic analytes.

170
 V. Diazotization titration
The process of forming diazonium compounds or salts is called diazotation,
diazoniation, or diazotization.
Diazonium salts are a group of organic compounds sharing a common
functional group with the characteristic structure of R-N2+X- where R can be
any organic residue such as alkyl or aryl and X is an inorganic or organic
anion such as a halogen.

171
 Principle of diazotization titration
Diazotization is used in analysis of aromatic compound containing amino
group in a molecule.
A primary aromatic amine (PAA) present in the sample reacts with sodium
nitrite in acidic medium to form diazonium salt.
First nitrous acid is formed by the interaction of sodium nitrite and
hydrochloric acid.
NaNO2 + HCl  NaCl + HNO2
The obtained nitrous acid is reacted with the PAA to form the diazonium salt.
R − NH2 + NaNO2 + HCl  R − N+ ≡ N − Cl− + NaCl + H2O
The titrant is Sodium Nitrite.
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Different amino compound react with sodium nitrite at different rates
So, Amines are classified as rapidly and slowly diazotisable depending on the
rate of conversion into azo compounds.
Slow diazotisable compounds include compounds that contain sulpha groups,
nitrous oxide group, or carboxylic group in aromatic ring.
Eg: isomeric nitro aniline, sulphanilic acid and anthranilic acid
NaNO2 added from the burette needs time to react with this amino group.
Adding KBr to the solution can increase the rate of titration.
Fast diazotisable compounds do not contain any substituent group other than
amino group but some times they may contain –CH3 or –OH group along with
NH2 group.
Eg : aniline, toluidine and aminophenol
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The diazonium compounds formed are unstable and readily decompose at
elevated temperature
This can lead to side reaction and give wrong result .
Optimum temperature for most amine is 10-150C, when they form relatively
stable diazo compounds.

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 End point detection
After all the primary aromatic amine present in the sample are consumed the
excess nitrous acid formed is shown by instant formation of blue colour with
starch iodide paper.
Starch iodide paper is prepared by immersing a filter paper in starch mucilage
and potassium iodide solution.
The iodine formed reacts with starch mucilage to give the blue colour.
KI + HCl  HI+ KCl
NaNO2 + HCl  HONO + NaCl
2HI +2HONO  I2↑ +2NO +2H2O
I2 + Starch  blue color (end point)
The end point can also be determined by potentiometric technique. 175
 Applications
Diazotization titrations are carried out for the estimation of drugs containing
primary aromatic amino group or can be converted to have such groups by
simple reaction like hydrolysis or reduction.
It is used in the assay of sulpha drugs like dapsone, sulphonamides,
sulphacetamide sodium, sulphadiazine, sulphamethazole, sulphadoxine,
sulphamethoxazole & sulphaphenazone etc.
It is also used in the assay of various drugs like benzocaine, procainamide,
procaine, suramin, sodium amino salicylate, primaquine sulphate etc.

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