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Outline

Introduction

Acid-base Titration

Precipitation Titration

Complexometric Titration

Redox Titration

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 OBJECTIVES

• At the end of this chapter, students will be able

to:
• Discuss the principles of the different titrimetric methods

• Explain the different applications of titrimetric analysis

• Operate titremetry using their basic skills of titration

(practical session)

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 Introduction
• Definition- titration is the process of slowly adding a
reagent, with a known concentration or whose concen-
tration can be precisely determined, in to analyte until
the reaction between them is completed.
• Volume is measured
• Standard reagent- titrant
• Analyte- titrand

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 Titrimetry

•Principle:
An analyte is chemically reacted with a standard solution of
reagent of known concentration or with a concentration that
can be precisely determined.
The amount (volume) of a standard solution required to
completely react with the entire sample is used to estimate
the purity or amount of the sample.

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 Introduction cont…

Types of titration
The type of reaction provides a simple way to di-
vide titrimetry into the following four categories:
Acid-base titration
Precipitation titration
Complexometric titration and
Redox titration

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 Titrimetry…
Advantages
₰ Capable of higher degree of precision and accuracy than instrumental
methods of analysis

₰ Analysis can be automated

₰ Cheap to perform and do not require specialized apparatus

₰ They are absolute methods and are not dependent on the calibration of
the instrument
Limitations
l  Insensitive

l  Time consuming if not automated

l  Require large amount of sample and reagent

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 Titrimetry…
• Despite the difference in chemistry, all titrations
share several common features
A. Requirements for titration
 Stiochiometric ratio should be known
 No complicating side reaction, rxn must be specific
 Concentration of the Titrant should be known
 Easy method of end-point detection

 The reaction should be rapid

 The reaction should be quantitative so that sharp change will oc-
cur at the end-point

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 Titrimetry…

Standard solution
A standard solution is reagent used to titrate the analyte
Should have known concentration
Two types-
Primary and
secondary standards
A primary standard is a highly purified compound (99.99%) material that
serves as reference.
Requirements
 Must be easy to obtain, to purify, to dry and preserve in pure state
 It should be 100.00 % pure although 0.01 to 0.02 % impurities is tolerable if accu-
rately known.
 It should be stable at atmospheric conditions
 Should have high equivalent weight
 Low hygroscopicity (to minimize weight changes due to humidity)
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 It should be soluble in the conditions applied 10
 Titrimetry…
 Standards used as a standard that do not meet all these criteria are called secondary
standards
ü Exact concentration is determined by standardization

 Standardization : is the process of finding out the concentration of the

solution (20 standards) by using primary standard.

–– In this process, standard solution is prepared by dissolving a fixed
weight of primary standard substance in solvent to prepare known

volume of solution.

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 Titrimetry…
Equivalence Point and End point
Equivalence Point
is the point in titration where the number of moles of the titrant is exactly the
same as the number of moles of the titrand (Analyte) or
it is the point where the reaction between the titrant and the analyte is com-
pleted.
Is a theoretical point that can not be determined experimentally and
•hence the completion of reaction is usually shown by a change of color caused
by a substance called an Indicator. This point is referred as End Point.
•The difference between the end point volume and the equivalence point
volume is called Titration Error.

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 Titrimetry…

Factors affecting end point detection

Indicator selection
Color change detection
Quantity of indicators Generally, indicators are added in a very small
quantity approximately 0.0001-0.0004% of the solution being titrated.
Presence of colloidal substances: Colloidal particles are having property to
adsorb ions on their surface and this property leads to the problems in detection of
end point.Possibility of either premature delayed indicator color change and
hence, the errors in detection end point.

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 Direct titration Vs Back titration
• Direct titration is a type of
titration where the titrant is allowed directly to
react with the analyte.
 analysis of Cl- in raw materials using Ag+ as titrant

 Back titration is a type of titration where a measured

amount of a reagent is added to the analyte so that there is a
slight excess. After the reaction is allowed to go
completion, the amount of excess (un-reacted) reagent is de-
termined by titration with another standard solution.

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 When do we use back titration?
• If the end point of the reverse titration is easier to iden-
tify than the end point of the normal titration.
• If the reaction between the analyte and the titrant is very
slow.
• Volatile substance e.g- Ammonia, some of w/c would be
lost during the titration.
• Insoluble substance. e.g- require excess volumetric
reagent to effect a quantitative reaction.
• Substance w/c requires heating with a volumetric reagent
during the determinations in which decomposition or loss
of reactant or product would occur in the process.
E.g: formaldehyde solution
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 When?
 the reaction is slow to go to completion
 the sample is volatile (e.g. NH3)
 the sample is insoluble (e.g. ZnO)
 the sample is thermolabile
 the end point of the back titration is clearer than
 the end point of the direct titration

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 Titrimetry…
Standard solutions are prepared
in two ways:

Direct method- Indirect method- a solution is

prepared to give approximately
A primary standard compound is the desired concentration, and this
is standardized by titrating against
carefully weighed and dissolved a weighed quantity of a primary
in exactly known volume of standard. Example; NaOH vs
KHP
solution.

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 Introduction cont…

• Example of back titration: determination of the con-

centration of formaldehyde, H2CO, in an aqueous solu-
tion.

H2CO (aq) + excess I3- (aq) + 3OH- (aq) HCO2- (aq) + 3I- (aq)+ 2H2O

Unreacted I3- (aq) +2 S2O3–(aq) S4O6- + 3I- (aq)

• The difference between the initial amount of I3– and the

amount in excess gives us the amount of I3– reacting
with the formaldehyde.

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 Back titration with Blank determination
 Blank titration is a titration with out the analyte.

 If the procedure involves heating and subsequent cooling of the sample

(e.g. to allow sample to dissolve), some of the volumetric reagents may be lost ei-

ther by evaporation or mechanically due to splashing or bubbling.

The indicator might also react with the reagent.

Therefore blank titration is used to determine the exact amount of the

reagent, added in excess, which would react with analyte.

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 • The blank determination must be identical to the rest of the
test determining in every way except that there is no sample
in the blank. This means that heating times, dilution etc, must
be duplicated exactly

• For example, we can titrate a solution containing no

oxalic acid to see how much is needed to produce ob-
servable purple color. We then subtract this volume of
from the volume observed in the analytical titration

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 Steps in a Titration
• Titrimetric analysis generally involve the following
steps:
• Sampling
• Titrant preparation
• Standard preparation and conversion to a measurable form
• Titrant standardization by titration of an accurately know
quantity of standard
• Sample preparation and conversion to a measurable form
• Sample titration with the titrant solution
• Data analysis

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 Calculations in titrimetry.

N= No. of Eq.Wt/ Vol

M= mol/Vol sol of sol

Mol = G.m/M.Wt

No .of Eq.Wt= F.W/n, where n,

isno of equivalent

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06/12/2024
 Calculation Exercise
1. Calculate the molar concentration of ethanol in aqueous solution that
contains 2.30 g of C2H5OH (46.07 g/mol) in 3.50 L of solution. (Ans.
0.0143 M)
2. Describe the preparation of 2.0 L of 0.108 M BaCl2 from BaCl2. 2H2O
(244.3 g/mol). (Ans. Dissolve 52.8 gm of BaCl2. 2H2O in water and dilute
to 2.00 L)
3. Titration of 0.2121 g of pure NaC2O4 (134 g/mol) required 43.31 ml of
KMnO4. what is the molarity of the KMnO4 solution? The chemical reaction
is
1.(Ans. 0.01462M)

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 Calculation Exercise
4.How would you prepare 0.5 M of HCl acid in 250ml from its stock solution
having 11.9 M?
5. 2 gm of drug “X” was weighed and dissolved in 500 ml of water. The so-
lution was titrated against 0.5 M HCl after adding 3 drops of appropriate in-
dicator. Calculate the percentage of the drug in the sample taken if 22.5 ml
of HCl is consumed to reach the end-point (M.wt of “X” is 160 g/mol)
6. A pharmacist wants to determine the percentage of drug using a titra-
tion. He dissolved 0.5 gm of the drug in 30 ml of 0.1 M NaOH and He
titrated the excess NaOH with 0.1 M HCl. 3 ml of HCl was con-
sumed in the titration. Assuming 1:1 reaction, calculate the percent-
age of drug in the sample taken (M.wt of is 180 gm/mol).

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 Titration curves
Titration curve is plot of a variable related to a relevant concentration as y-
axis versus some measure of the amount of titrant (e.g. volume) on the X-axis.
A titration curve provides us with a visual picture of how a property of the titra-
tion reaction changes as we add the titrant to the titrand.
Titration curve define the properties required of an indicator and allow us estimate the
error associated with the titration methods.

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 Example

Figure-1: Acid-base titration curve

Titer value – gives the amount of analyte which reacts
with 1 ml of the titrant.

Titer value = N or M × Eq. wt or M.wt

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 Acid-Base Titration

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 Acid Base titration…
• An acid-base titration is a simple experimental technique
that utilizes an acid-base reaction for quantitative or
qualitative purpose
Two types
 Aqueous acid-base titration
 Non-aqueous acid base titration

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 Acid-Base titration…
Detection of the end point: Indicators
• It is usually more convenient to add an indicator to the solution and visually
detect a color change.
•An indicator for acid-base is a weak acid or weak base that is highly colored.
•The color of the ionized form is markedly different from that of the non-ionized
form.
• One form may be colorless, but the other must be colored.
• The substances are usually composed of highly conjugated organic constituents
that give rise to the color

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 Acid-Base Titration…
• Assume the indicator is weak acid, designated HIn, and assume that
the nonionized form is red while the ionized form is blue

HIn H++In-
(red) (Blue)

• One can write a Henderson-Hasselbalch equation for this, just

as other weak acids:
=pKa + log[In-]
pH
[HIn]

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 Acid-Base Titration…
With indicators in which both forms are
colored, generally only one color is ob-
served if the ratio of the concentration of
the two forms is 10:1

When only the color of the non ion- pH= pKa +PH
log1-log10
= pKa-1
ized form is seen, [In-]/[HIn] =1/10

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 When only the color of the ionized form is observed, [In-]/[HIn]

=10/1 pH = pKa + log10 -log 1 = pKa+1

• So the pH in going from one color to the other has changed from
pKa-1 to pKa+1.
• Midway in the transition, the concentrations of the two forms are equal, and pH = pKa

– Obviously, then the pKa of the indicator should be close to the pH of the equivalence
point.

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 Acid-Base Titration…
I. Direct titration of strong acid with strong base
 Characterized with large pH change around the equivalence point. Eq.pt at
pH = 7
I. Before the equivalence point, pH depends on amount of
excess strong acid present
Used in determination of Aldehydes and ketones in essen-
tial oil.
 After equivalence point, pH depends on amount of excess base added.
 Indicator which changes color in pH 4-10 is suitable (Methyl orange)
HCl vs NaOH
36

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 The equivalence point of a strong acid—strong base titra-
tion

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 For our first titration curve let’s consider the titration of 25.0 mL of 0.100 M HCl with 0.100 M NaOH. For the
reaction of a strong base with a strong acid the only equilibrium reaction of importance is :
H3O+(aq) + OH–(aq) → 2H2O(l) …1
At the equivalence point we know from reaction 1 that
Moles HCl = moles NaOH
or
MaVa = MbVb
where the subscript ‘a’ indicates the acid, HCl, and the subscript ‘b’ indicates the base, NaOH.

A) at 0.0 ml of NaOH added:

[H+]= 0.1 M
PH= - log [H+]
=- log (0.1)
=1.00
B) after adding 5 ml of NaOH is added:
Before the equivalence point, HCl is present in excess and the pH is determined by the concentration of
excess HCl.
[H+] = (0.025L )(0.1 mol/liter) – ( 0.005L)(0.1 mol/liter)
( 0.025 + 0.005)L
=0.002mol = 0.0067M
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C) after adding 10 ml of NaOH
[H+]=(0.025 L )(0.1 mol/liter) – (0.01L )(0.1mol/liter)
( 0.025 L + 0.01 L)
=0.0429M
PH= -log (0.0429M)
=1.37

D) after adding 20 ml of NaOH

[H+] = (0.025L)(0.1mol/liter) – (0.02L)(0.1mol/liter)
(0.025L + 0.02L)
=0.0111M
PH = -log(0.0111M)
=1.95
E) at the equivalence point (25mL of NaOH), pH =7
•
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 Acid-Base Titration…
II. Direct titration of weak acid with strong base
Equivalence point, PH > 7
The transition range of the indicator for this titration of a weak acid must fall
within a pH range of 7 to 10.
Most frequently used indicator in such titration is phenolphthalein.
There is small pH change around the equivalence point (Buffer).
If indicator like Methyl red (4-6) is used, there will be change in the color before
the equivalence point.
 Application : determination of  Salicylic acid,
benzoic acid
HA vs NaOH

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 • Curve is similar to strong acid—strong base after eq.
pt. where OH- is major

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 Acid-Base Titration…
III. Direct titration of strong base with strong acid
The pH change in the region of the equivalence point are sufficiently large
Methyl orange is usually used as indicator (4-10).
Before the equivalence point, pH depends on amount of excess strong base present
After equivalence point, pH depends on amount of excess acid added
Sodium carbonate, Thiopentane injection

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 Acid-Base Titration…
IV. Direct titration of weak bases with standard strong acid

The pH of the solution at the equivalence point, pH < 7

Methyl red is the indicator used most frequently

Before equivalence point, a buffer is formed and the pH does not change very
much with added acid
After the equivalence point, pH depends on amount of excess acid added

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 Example: Titrate 100 ml of 0.10 M NH3 (Kb = 1.8
x 10-5) with 0.1 M HCl

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 Acid-base titration cont…

Table-1: some important Acid/base indicators

Common Transition pKa color change Indicator type

name pH

Methyl orange 3.1-4.4 3.46 red-orange base type

Bromocresol green 3.8 -5.4 4.66 yellow-blue base type

Methyl red 4.2-6.3 5.00 red-yellow acid type

Phenol red 6.8-8.4 7.8 yellow-red acid type

Phenolphthalein 8.3-10 9.6 colorless-red acid type

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06/12/2024 47
 Direct Titration
• Interpretation of the data obtained in
volumetric analysis is facilitated considerably
by the use of milliequivalent factor or titer
value.
• TV (titer value) is defined as the weight of a
substance chemically equivalent to one
milliliter(1 ml) of a standard solution( a titrant
of known concentration)
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 Example:
Ca(OH)2 + 2HCl→CaCl2 + 2H2O
1 mole of Ca(OH)2 = 2 mole of HCl
 74.09 g of ca(OH)2 = 2 mole of HCl
 74.09 g of Ca(OH)2 =1000ml of 2 molar HCl
X = 1 ml of 2 molar HCL
 X= 74.09 mg of Ca(OH)2
 Titer value of Ca(OH)2 is 74 .09 mg
A general formula which can be used for the calculation of the
percentage purity of a sample determined by direct titration is given by :

%C =( volume of titrant consumed )(titer value) x 100

•
06/12/2024 Sample weight or volume
Example : Assay of Sodium Bicarbonate
Method: 3 g of sodium Bicarbonate was weighed and mixed with 25 ml of water. The solution
was then titrated with 1M H2SO4 after adding methyl orange test solution to consume 17.7
ml . Calculate its percentage strength.
Solution: 2(NaHCO3) + H2SO4→Na2SO4 + 2 H2O + 2 CO2
2moles of NaHCO3 = 1 mole of H2SO4
168.02 g of NaHCO3 = 1000ml of 1M H2SO4
X = 1 ml of 1M H2SO4
X= 168.02 mg=Titer value
%C= (TV) ( vol. of tit.) X 100
sample weight
= 168.02 X 17.7 X 100; = 99.13%
3000
•

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 Acid-base titration cont…
Application of Acid-base titration

Water acidity (CO2, S, Fe(SO4)3, FeCl3)

Water alkalinity (Hydroxides, carbonates and bicarbonates)
Water hardness (Ca2+, Mg2+, Fe2+, Mn2+)
Determination of free fatty acids in oils and fats
Analysis of drugs
 Acidic drugs
 Basic drugs

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 Determination of some pharmaceutically important acids

a) Carboxylic acid deriva-

tives; Acexamic acid
(analgesic-anti-inflamatory)
Aceclofenac
Used for treatment of peptic ulcers

b) Carboxylic acid and phenolic deriva-

tives Aspirin, Antipyretic Levodopa, Used for treatment of
parkinson's disease

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 Determination of some pharmaceutically important acids

c) Sulphonic acid deriva-

tives:

Estropipatic acid
Etamsylate, Haemostatic agent

d) Arsenic acid derivatives;

Arsenillic acid, Antibacterial

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 Determination of some pharmaceutically important bases:
a) Primary amine com-
pounds:

Amikacin, antibiotic

Sulphadiazine
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 b) Secondary amine compounds:
Viloxazine, Antidepressant
Xylazine, Analgesic Piprazine hy-
drate

Tulobuterol, Beta-adrenoceptor agonist Pinadolol, Beta-adrenoceptor antago-

nist

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 C- Acid Salts of Basic Drugs

Amiloride hydrochloride

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 Non-aqueous titration

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 Con't…
•Sometimes acid-base titrations are performed using a solvent other than water.
•There are several reasons why non-aqueous acid-base titrations may be used in-
stead of aqueous titrations
• If the sample is insoluble in water.
• If the Sample and/or titrant reacts with water in
undesirable ways.
• For the analysis of very weak acids or bases

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 Cont't…

 .
• Substances which produce, upon reaction, products which cause a problem
e.g. fatty acids which form soap during titration. Fatty acids (water insoluble) + NaOH ==
RCOONa (soap) + H2O
•The soap froth may cause a problem in aqueous media.
Selectivity is sometimes enhanced in non-aqueous solutions (analysis of ana-
lytes with similar dissociation constants).

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 Con't…
• In aqueous solutions, a difference of 2 pK units is necessary to observe
distinct endpoints.
• However, careful choice of solvent can sometimes allow the observation
of distinct endpoints that cannot be measured in aqueous solution
• Some alkali metal salts of organic acids which form aheavy preciptate dur-
ing titrations .
• e.g. sodium benzoate and sodium salicylate

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• HCl gas function as acid only when dissolved in water, but not in dry state (i.e. the abi
ity of a substance to act as an acid or base will depend very much upon the nature o
solvent system which used.
– H2O + HCl=====H3O+ + Cl-

• HCN is very weak acid; it has a low tendency to transfer a proton to

water as a solvent
– H2O + HCN=====H3O+ + CN-
– HCN + NH3=====CN- + NH4+
–The same acid might dissociate to a much greater degree in more basic solvents

• This means that we can enhance the acidity by choosing a solvent more
basic (less acidic) than water.

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 Con't…
• As a rule; a substance which acts as an acid in one solvent does not necessary reacts
in the same way in another solvent or a substance reacts as an acid if it is more
acidic than the used solvent and reacts as a base if it is more basic than the used sol-
vent
• An acidic substance can only function as an acid in the presence of a base, and

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 Solvents for Non-aqueous titrations
• Protophilic solvents:
– They are basic solvents, more basic than water and have high abilityto accept
protons. E.g. liquid ammonia, amines, ethers and ketones

HA + S == SH+
+ A -

– They enhance the strength of weak acids (e.g. acetic and formic acid) so that
they have the same strength as strong acids (perchloric and sulfuric acid). This
effect known as the Leveling effect.

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 Con't…
Protogenic solvents:
– They are acidic solvents, more acidic than water and have the
affinity to donate protons. e.g. anhydrous hydrogen fluoride and
sulfuric acid.

HS+B === + BH+

S-
– They enhance the strength of weak bases so that they have the same
strength as strong bases (Leveling effect).

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 Con't…
Aprotic solvents
–They are chemically inert, un-reactive under the conditions used for determi-
nations.
–E.g. CCl4 and benzene.

–They do not cause ionization of solutes and do not undergo reactions with
acids or bases.
–They are used only as vehicles or diluents.
–They have no leveling effect on acids or bases.

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 Con't…
Amphiprotic solvents

– They are liquids that ionized to a slight extent and exhibit both protogenic and protophilic proper-

ties.

E.g. alcohols, water, acetic acid.

–

They have both leveling and differentiating

effects

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 Leveling effect
• It is impossible experimentally to distinguish
any difference b/n the strength of two acid
such as perchloric and hydrochloric acid in
aqueous media.
• Thus ,water is said to exert leveling effect on
HCIO4 and HCL since both acids are much
stronger acid than H3O+ or b/c H2O is
stronger base than either HCLO4 and HCL

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 Differentiating effect
• It is the capability of a solvent to differentiate the strength of two acids

• Thus acetic acid said to exert differentiating effect on HCLO4 and HCL since

CH3COOH2 is stronger acid than H3O+ or acetic

acid is much weaker base than H2O.
• The reaction of HCLO4 in acetic acid,
however shows a higher degree of completion
than the of HCL with acetic acid.

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 A. Titration of basic substances

• Used for titration of:

– All amine types, alkaloides

– Sulphonamides and purines

e.g. uric acid and its derivatives
–
Halide salts of amines and quaternary ammonium
salts.
– Alkali metal salts of organic acids.

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 Con't…
General Conditions:

– Solvent; glacial acetic acid is used mostly for dissolving sample &
standard.
– Titrant; Perchloric acid (0.1N), prepared by mixing 8.5 ml of 72 %
perchloric acid with 900 ml of glacial acetic acid and 30 ml of
acetic anhydride, then complete to 1 liter with glacial acetic acid.
– Indicator; 0.5% acetous crystal violet solution ( its color is changed
from blue to green)

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 Con't…
Alkali metal salts of
organic acids such
as:phenobarbitone sodium
and sodium salicylate;

they serve as bases in

medium.
acetic

acid
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 B. Titration of acidic substances
– Very weak aromatic and aliphatic acids.
– Phenols and enols
– Imides and sulphonamides

• General conditions :
– Solvents; Benzene-methanol mixture, DMF (Dimethoxyformamide) and
ethylene diamine.

– Titrant; Potassium methoxide (0.1N), prepared by adding 4 gm of

potassium metal to a mixture of 40 ml methanol and 50 ml benzene then

complete to 1 liter with a mixture of both to give clear solution.

– Indicators; thymol blue or azo violet.

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 Q
Methyl Dopa (BP)
– Weigh about 0.2g sample accurately and dissolve in a
mixture of 15ml of anhydrous formic acid, 30ml
anhydrous acetic acid and 30ml of 1, 4- dioxane. Titrate
with 0.1M Perchloric acid using crystal violet solution as
indicator.
– State which type of volumetric assay is used for?
• Non aqueous acid base titration
– Explain why titration of this type is sometimes required
and any precautions
• Dry conditions should always maintained

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 Example

A 0.5130g sample of aspirin prepared by a student re-

quired 27.98 mL of 0.100 M NaOH for neutralization
(used to neutralize all acidic material present in the
sample). An additional 42.78 mL of 0.100 M NaOH was
added, and the sample was heated to hydrolyze the
acetylsalicylic acid. After the reaction mixture was
cooled, the excess base was back-titrated with 14.29 mL
of 0.1056 M HCl.
a. How many grams of acetylsalicylic acid are in the sample?
b. What is the percentage of acetylsalicylic acid (or the purity)?

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 Precipitation titration

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 Preciptimetric titration
•• Precipitation titration is a titration in which the entity being titrated is
precipitated from solution by reaction with the titrant. In this case the

titrant forms an insoluble product with the analyte.

Limitations

 Slow rate of formation of precipitate

 Difficult to select a suitable indicator

 Difficult to obtain an accurate precipitate composition

 co-precipitation is a challenge
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 Solubility product

• Solubility is a physical property referring to the ability for a given substance, the
solute, to dissolve in a solvent.

• It is measured in terms of the maximum amount of solute dissolved in a solvent at

equilibrium.

• The resulting solution is called a saturated solution.

• Solubility is commonly expressed as a concentration, mass concentration (g of

solute per kg of solvent, g per 100 ml of solvent), molarity, molality, mole fraction
or other similar descriptions of concentration.

06/12/2024 3
 Con't…
• An oversaturated solution becomes a saturated solution by forming a solid to reduce the dis-
•
solved material.

• The crystals formed are called a precipitate.

– AgNO3 + NaCl====AgCl + NaNO3

•A saturated solution of a slightly soluble salt in contact with an undissolved salt involves

equilibrium like the one below:

– AgCl (s) ========= Ag (aq) + Cl (aq)

06/12/2024 4
•Writing the equilibrium constant expression for heterogeneous equilibria, we ignore the concentrations
of pure liquids (H2O) and solids.
•So the equilibrium constant expression for the equilibria above is: K = [Ag ] [Cl ]
sp
+ -

• This equilibrium constant Ksp is called asolubility-product constant..

• Solubility product is equal to the product of the concentrations of the ions involved in the equilibrium,
each raised to the power of its coefficient in the equilibrium equation.
• The equilibrium constant Ksp called the solubility constant indicates how soluble a substance is. If the
Ksp is low, the solid is not very soluble. If the Ksp is high, the solid is soluble.

06/12/2024 5
 Factors Affecting solubility of equilibria
Temperature effect
• Most of inorganic salts increase its solubility by increasing temperature.
Exception is precipitates which are slighty soluble in hot/warm solution (e.g. Hg 2Cl2,
MgNH4PO4)

Solvent effect

• Most of inorganic salts dissolve in water but not in organic solvent.

• Water molecule has a higher dipole moment and could be attracted by cations or anions
to form hydrated ions.

• In order to form a precipitate, the product formed should be insoluble in the solvent.

06/12/2024 6
 Con't…
The Common Ion Effect

• Precipitate dissolves more easily in water than in solution containing common ions.

• For example, suppose we have a solution of Iron (II) sulfide. If we dissolve some sodium
sulfide in the solution, the presence of the additional sulfide may cause the precipitation
of FeS.
The solution now contains less FeS. The decrease in the concentration of the FeS in a
•
solution of Na2S is an example of the common ion effect.

In general, any ionic equilibrium is affected by a substance producing an ion involved in

•
the equilibrium.

06/12/2024
 Con't…
Example
• Calculate the molar solubility of barium fluoride, BaF2, in water at
25oC. The Ksp at 25oC is 1.0 x 10-6.
– BaF2 (s)=====Ba2+ (aq) + 2F- (aq)
– Ksp = [Ba+2][F-1]2
– 1.0 x 10-6 = (x) (2x)2 = 4x3 solving for x, we get: x = 6.30 x 10-3 M

Since "x" represents the molarity of the Ba+2 ion, and we get one mole of
barium ions for each mole of barium fluoride that dissolves, we obtain
a molar solubility for BaF2 of 6.30 x 10-3 M

06/12/2024 9
 Con't…
Now, to illustrate the common ion effect
What is the molar solubility of barium fluoride in a solution that is 0.15 M NaF at 25 oC
Since the solution is already 0.15 M in F-1 ions, we must make an addition to our equilibrium
concentrations.
– BaF2 (s)=====Ba2+ (aq) + 2F- (aq
2x + 0.15 x
• Because BaF2 is only slightly soluble, you might expect "2x" to be negligible compared to 0.15. In
that case
(2x + 0.15) ~ (0.15) and substituting into the Ksp expression, we get
1.0 x 10-6 = (x) (0.15)2
solving for x, we get: x = 4.44 x 10-5 M
Note that "x" is indeed much smaller than 0.15, so our assumption was correct. Therefore the molar
solubility of barium fluoride in 0.15 M NaF is only 4.44 x 10-5 M. In pure water, the solubility is 6.3 x
10-3 M, which is over 140 times greater.

06/12/2024 84 10
 Con't…
pH effect

• Solubility of weak acid/weak base salt depends on pH of the solution. E.g. oxalic, sulfide, hydroxide,

carbonate, phosphate

• For example, consider the equilibrium between solid calcium fluoride and its ions in aqueous solution.

CaF2 (s) =======Ca2+ (aq) + 2F- (aq)

• Because the fluoride ion is the conjugate base of a weak acid (HF), you would expect it to react with any H+ ion
that is added:

– 2F- (aq) + H- (aq)===== HF(aq)

According to LeChatelier's Principle, as F-1 ions are removed by the reaction with H+ ion, more calcium fluoride

can dissolve to replenish the fluoride ions. Therefore you expect calcium fluoride to be more soluble in acidic
solution than in pure water. In general, salts of weak acids should be expected to be more soluble in acidic solu-
tions .
06/12/2024 85 11
 Con't…
For example

Q. Which salt would have its solubility more affected by changes in pH, silver chloride or silver cyanide?

• Looking at the two dissolution equations

AgCl (s)======Ag+ (aq) + Cl- (aq)

AgCN (s)=====Ag+ (aq) + CN- (aq)

• we can assume that the chloride ion will not undergo hydrolysis since it is the conjugate base
of the strong acid, HCl
• However,. the cyanide ion is the conjugate base of the weak acid, HCN, and consequently will react
with any H+ ions present to reform HCN, thus removing cyanide ions from the solution.

– CN- (aq) + H- (aq) =====HCN

06/12/2024 86 12
 Standard Solutions

• The standard solution employed in official assays by precipitation methods are 0.1 M Silver nitrate

and 0.1 M Ammonium thiocyanate.

• Silver nitrate is obtainable in primary standard. However, Ammonium thiocyanate is somewhat

hygroscopic, and the thiocyanate solutions are ordinarily standardized against silver nitrate.

• Titrations using silver nitrate are termed Argentometric titrations.

End point Detection
• There are two types of commonly used indicators in Argentometric titrations.

– The first type forms a colored compound with the titrant when it is in excess.

– The second type, called adsorption indicator, suddenly becomes adsorbed on the precipitate at

the equivalence point. The indicator changes its color when it is adsorbed.

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 Mohr Method
• The
• indicator directly reacts with the titrant at the equivalence point.
• Mohr titration is used for determination of halides (chloride, bromide, and
cyanide).

• Chromate ion (CrO42-) is added to serve as indicator. At the end point the

chromate ion is combined with silver ion to form the sparingly soluble, red, silver
chromate, Ag2CrO4.

– Ksp Ag2CrO4 = 1.2 x10-12 mol3.L-3

– Ksp AgCl = 1.82 x10-10 mol2.L-2

Example: titration of chloride ion

Before the Eq .pt Ag+ + Cl- == AgCl (white ppt)

At the Eq. pt Ag+ + CrO42- == Ag2CrO4 (red color)

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 Con't…
• Mohr titration has to be performed at a neutral or weak basic solution of pH
7-9 (or pH 6-10).
• In lower pH (acid),

– the chromate dichromate equilibrium decreases the sensitivity of chromate ion

a solution and then inhibits formation of Ag 2CrO4 precipitate.

– If the [CrO42-] is too low then the reaction needs excessive addition of [Ag+]
to precipitate Ag2CrO4; this might be a titration error.

– Dichromate ion, Cr2O7 2-, can not be used as indicator as Ag2Cr2O7 precipitate is
easily dissolved in this ionic solution.
-2 + -2
– 2CrO4 + 2H =========Cr2O7 + H2O

06/12/2024 89 19
 In higher pH (basic)
• Ag2O will be formed as a black precipitate and hence silver ion will be
over consumed there by in titration error.
I-

– Mohr method is not feasible for resulting SCN- because of

• Adsorption problem- the chromate is adsorbed and hence too low
concentration of the chromate will be available to react with excess silver
ion; end point detection is very difficult

• Silver iodide is bright yellow in color which interferes with the end point
color.

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 Volhard Method

• Volhard titration is an indirect (back titration) technique which is used if reac-

tion is too slow or if there is no appropriate indicator selected for determining
the equivalent point.
• Titration principle : Silver solution is added excessively to a halide.

– Br- +Ag+ (excess)=====AgBr (ppt)

• After reaction has completed, the precipitate is filtered, then the

filtrate is titrated with a standardized thiocyanate solution.
– Ag+ + SCN =======AgSCN (Solution)
• Fe(III) indicator reacts with thiocyanate ion to form a red colour so-
lution
– Fe3+ + SCN =========[Fe(SCN)]2+

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 Con't…
•• The reaction requires acid condition, as in basic solution the ferric
• If the precipitate is detected, AgX, is less soluble than AgSCN, it is
• not necessary to remove the precipitate before titrating.

• If the precipitate is more soluble than AgSCN, it will react with the
titrant to give diffuse end point. Such is the case with AgCl:
– AgCl (ppt) + SCN- ===== AgSCN + Cl-

06/12/2024 22
 Fajan's Method
• In this method, the reaction between the indicator and excess silver takes
place on the surface of the precipitate.

• The indicator, which is dye, exists in solution as ionized form, usually an

anion.

• To explain the mechanism of the indicator action, consider the titration of

chloride with silver ion.
Before the equivalence point, chloride is in excess and the primary adsorbed
layer is chloride and the more loosely held secondary layer of the adsorbed
ions are cations, such as Na+.

• Beyond the equivalence point, silver ion is in excess and the surface
of the precipitate becomes positively charged, with the primary layer being
Ag+.
This will now attract the indicator anion and adsorb it in the counter layer.
06/12/2024 93 23
 Con't…

• The color of the adsorbed indicator is

different from that of unadsorbed
indicator and this difference signals
the completion of the titration.

• A possible explanation is that the

indicator forms a colored complex
with silver ion, which is too weak to
exist in solution, but whose formation
is facilitated on the surface of
precipitate (it become insoluble).

06/12/2024 94 24
 Con't…
• Example of adsorption indicators- fluorescein, dichlorofluorescein,
tetrafluorescein and tetraiodofluorescein

• The indicators are limited to pH conditions which will keep them dissociated.

• The fluorescin is limited to neutral or weakly basic solutions, where as

dichlorofluorescein can be used in weakly acidic media to about pH 4

• Tetrafluorescein (eosin) to about pH 2 or 3, and it's usually too strongly adsorbed to

be used for chlorides, whereas tetraiodofluorescein is too strongly adsorbed for
both bromides and chlorides.

• Solvent conditions will affect the choice of the indicator.

• The following are some of the indicators used in fajan's method of precipitation
titration.

06/12/2024 95 25
 Adsorption Indicators

Indicator Analyte Titrant Reaction

Condition
Diclorofluorescin Cl- Ag+ pH=4
Fluorescein Cl- Ag+ pH=7-8
Eosin Br-, I-, SCN- Ag+ pH=2
Thorin SO4-2 Ba2+ pH=1.5-3.5
Bromocresol SCN- Ag+ pH=4-5
Green
Methyl violet Ag+ Cl- Acid Solution
Rhodamin 6G Ag+ Br- HNO 3 upto 0.3M
Orthochrome T Pb2+ CrO4-2 Neutral 0.02 M
Bromocresol Blue Hg2 2+ Cl- Solution of 0.1M

06/12/2024 96 26
 Assay of Aminophylline Injection (BP)

• Transfer 250 mg (10ml) aminophylline injection, add 50ml of water

and 15ml of ammonia, warm and cool. Add excess AgNO3 and mix
thoroughly and heat for boiling, cool 5-10 0C, filter and acidify with
HNO3. Add ferric ammonium sulphate and titrate the excess AgNO 3
using 0.1N ammonium thiocyante.
– What type of volumetric analysis is it?

– Which type of endpoint detection is used?

– What is the purpose of HNO3, and Ferric ammonium Sulphate (FAS)

06/12/2024 97 27
 Complexometric Titration

06/12/2024 98
 Complexometric Titration…
Introduction
• The technique involves titrating metal ions with a complexing agent or
chelating agent (Ligand) and is commonly referred to as complexo-
metric titration.

• In this method, a simple ion is transformed into a complex ion and

the equivalence point is determined by using metal indicators or elec-
trometrically.

06/12/2024 99
 Complexometric Titration…
Introduction…
• Metal ions in solution are always solvated, i.e. a definite number of solvent molecules (usually
2, 4 or 6) are firmly bound to the metal ion.
• However, these bound solvent molecules are replaced by other solvent molecules or ions
during the formation of a metal complex or metal co-ordination compound.

• The molecules or ions which displace the solvent molecules are called Ligands.

• Ligands or complexing agents or chelating agents can be any electron donating entity, which
has the ability to bind to the metal ion and produce a complex ion.

06/12/2024 100
 Complexometric Titration
Introduction…Classification of Ligands
1.Unidentate Ligands: Ligands that are bound to metal ion only at one
place

2.Bidentate and Multidentate Ligands: Many ligands are known that

contain more than one group, capable of binding with metal ions. Such lig-
ands are known as multidentate ligands or chelating agents.

06/12/2024 101
06/12/2024
 Complexometric Titration…
Reagent EDTA
• The chelate most commonly used for complexometric titrations is ethylenediamine
tetraacetic acid (EDTA); an aminopolycarboxylic acid which is an excellent complexing
agent.

• water soluble chelating agent and is always preferred.

• EDTA has the widest general application in analyses because of the following important
properties:
• It has low price.

• It forms stable complex, This means that the endpoint of the EDTA titration will be
sharp
• It reacts in a one to one ratio with most of the metals, meaning that only a single
endpoint
06/12/2024 will be observed. 103
 Complexometric Titration…
Effect of pH on EDTA Titrations

• Since hydronium ion is an acid, it competes with metal cations for binding
sites on the EDTA molecule.

• Thus, the pH of the sample solution will have significant effect on the
sharpness of the titration.

• Besides its properties as a ligand, EDTA is also a weak acid. The fully pro-
tonated form of EDTA, H6Y2+, is a hexaprotic weak acid with successive
pKa values of

• The first four values are for the carboxyl protons, and the remaining two
values are for the ammonium protons.
06/12/2024 104
 Complexometric Titration…

Effect of pH on EDTA Titrations…

• A ladder diagram for EDTA is shown in

Figure below.

• The species Y4– becomes the predominate

form of EDTA at pH levels greater
than10.17.

• It is only for pH levels greater than 12

that Y4– becomes the only significant form
of EDTA.

105
 Complexometric Titration…

Effect of pH on EDTA Titrations…

• For example, imagine we are to titrate a mixture of Cu2+

and Ca2+.

• If we buffer the solutions at pH=4, only the cupric ions

would react with the EDTA, since calcium cations would be
effectively out-competed by the hydronium ions.

• However, a pH greater than about 7.5 would allow both ana-

lytes to react with the titrant.

06/12/2024 106
 Complexometric Titration…

Effect of pH on EDTA Titrations…

• Generally, there are actually two opposing effects of pH
on EDTA titrations:
• There is a competition between protons and the analyte for the
EDTA ligand, with higher pH values favoring more complete reaction
of analyte and EDTA;
• Hydrolysis of the analyte at higher pH values, with lower pH values
favoring more complete reaction of analyte with EDTA.
• Some metals react with the hydroxide at higher pH and the hy-
droxo (OH) ligand binds the metal more strongly, they are harder
for EDTA to displace during a titration.

• Due to the effect of pH on the endpoint sharpness, the pH is al-

most always buffered in EDTA titrations
06/12/2024 107
• In complexometric titration, the free metal ions disappear as
they are changed into complex ions.

• in EDTA titration, if we plot pM (negative log of metal ion con-

centration) v/s volume of titrant, we will find that at the end
point, the pM rapidly increases.

06/12/2024 108
 Complexometric Titration…
Factors affecting sharpness of end-point
1. The stability of complex formed: The greater the stability con-
stant for complex formed, larger the charge in free metal concentra-
tion (pM) at equivalent point and more clear would be the end point.

2. The number of steps involved in complex formation: Fewer

the number of steps required in the formation of complex, greater
would be the break in titration curve at equivalent point and clear
would be the end point.

3. Effect of pH: During a complexometric titration, the pH must be

constant by use of a buffer solution.
• Only metals that form very stable complexes can be titrated in acidic solu-
tion, and metals forming weak complexes can only be effectively titrated in
alkaline solution.
06/12/2024 109
 Complexometric Titration…
Methods of End Point Detection
• Dye indicators which are capable of acting as a chelating agent to give
a dye-metal complex are used.

• The latter is different in colour from the dye itself and also has a low
stability constant than the chelate-metal complex.

• The colour of the solution, therefore, remains that of the dye complex
until the end point, when an equivalent amount of sodium EDTA has
been added.

• As soon as there is the slightest excess of EDTA, the metal-dye complex

decomposes to produce free dye; this is accomplished by a change in
colour.

06/12/2024 110
 Complexometric Titration…

• Metal indicators must comply with the following requirements-

Compound must be chemically stable throughout the titration.

It should form 1:1 complex which must be weaker than the metal chelate
complex.

Color of the indicator and the metal complexed indicator must be sufficiently
different.

Color reaction should be selective for the metal being titrated.

The indicator should not compete with the EDTA.

06/12/2024 111
 Complexometric Titration…
Mechanism of action of indicator
• Let the metal be denoted by M, indicator by I and
chelate by EDTA.
• At the onset of the titration, the reaction medium con-
tains the metal-indicator complex (MI) and excess of
metal ion.
• When EDTA titrant is added to the system, a competitive
reaction takes place between the free metal ions and
EDTA.

06/12/2024 112
 • Since the metal-indicator complex (MI) is weaker than
the metal-EDTA chelate, the EDTA which is being added
during the course of the titration is chelating the free
metal ions in solution at the expense of the MI com-
plex.
• Finally, at the end point, EDTA removes the last traces
of the metal from the indicator and the indicator
changes from its complexed colour to its metal free
colour. The overall reaction is given by:

06/12/2024 113
 Complexometric Titration…
Types of Complexometric Titrations
1. Direct Titration:

• In this method, the standard chelon solution is added to the metal

ion solution until the end point is detected.
• E.g.-calcium gluconate injection, calcium lactate tablets

2. Back Titration:

• In this method, excess of a standard EDTA solution is added to the

metal solution, which is to be analyzed, and the excess is back
titrated with a standard solution of a second metal ion.
• Determination of Mn

06/12/2024 114
 Complexometric Titration…
3. Replacement Titration

• Substitution titration may be used for the metal ions that do not react (or re-
act unsatisfactorily) with a metal indicator (e.g., Ca2+, Pb2+, Hg2+, Fe3+),
or for metal ions that form EDTA complexes that are more stable than those
of other metals such as magnesium and calcium

• there is quantitative displacement of the second metal (Mg2+ or Zn2+) from

a complex by the analyte metal.

• When direct or back titrations do not give sharp end points, the metal may
be determined by the displacement of an equivalent amount of Mg or Zn
from a less stable EDTA complex.

• Usually, the determination of the metal ions that form weak complexes with
the indicator and the colour change is unclear and vague.
06/12/2024 115
 • MgY2- + Ca2+ → Mg2+ + CaY2- (more stable)
Mg2+ + CaIn- → Ca2+ + MgIn- (more stable)

• The following steps apply:

1. Replacement step

06/12/2024 116
4. Indirect titration
• Titrant does not react directly with the analyte but to a prod-
uct chemically related to the analyte.
• Example: Barbiturates
Method: Barbiturate to be analyzed is taken in a flask and heated with excess of mer-

cury in alkaline solution. When precipitated Hg-barbiturate complex is formed, it is fil-

tered and dissolved in excess of standard EDTA solution. The unreacted EDTA solution is

then back titrated with a standard Zn solution .

06/12/2024 117
 Complexometric Titration…
Titration Selectivity, Masking and Demasking Agents

• EDTA is a very unselective reagent because it complexes with numerous

doubly, triply and quadruply charged cations.

• Then the ratio of the stability constants of the EDTA complexes of the
two metals M and N must be such that KM/KN ≥ 106 if N is not to inter-
fere with the titration of M……Difficult to achieve

• The following procedures will help to increase the selectivity:

• Use of masking and demasking agents
• pH control.
• Use of selective metal indicators.
• Classical separation
• Solvent extraction
• Removal of anions

06/12/2024 118
 Complexometric Titration…
Titration Selectivity…
i. Use of masking and demasking agents:

• Masking agents: Masking agents are additives that undergo some reaction in
the sample solution that complexes (or precipitates) potential interfering elements
and converts them to a form that does not interfere with subsequent analyte ma-
nipulation or measurement.

Co Hg , Pb
Cu Sulfide or Cd , Bi Dimercapol
Pb sodium sulfide Zn Tn
(CH2SHCHSHCH2OH)
As

Ag, Hg
Ca Fe, Cu
Oxalate Potassium cyanide
Pb Zn, Cd
Co, Ni

Ca
Al
Mg Fluoride Fe Triethanolamine [N(CH2.CH2.OH)3]
Pb Mn

06/12/2024 119
 Complexometric Titration…
Titration Selectivity…

• Demasking: it is a process in which the masked substance regains

its abilty to enter into a particular reaction. This enables to deter-
mine a series of metal ions in one solution conatianing many cations.
Example of using masking and demasking agents in complexome-
try is the analysis of 3 metals: Cu, Cd and Ca. the following method
of analysis is followed:
• Direct titration of the mixture with the EDTA gives the sum of the 3 metals.

• Cu and Cd may be masked with the addition of cyanide to the solution, leaving
only Ca ion.
• When formaldehyde or chloral hydrate is added to the cyanide containing mixture,
only Cd is demasked and the EDTA titrates the sum of Ca and Cd. In this manner,
the concentration of three ions is determined by 3 individual titrations.

06/12/2024 120
 Complexometric Titration…

Titration Selectivity…
Step 1. All three metals are titrated.

Step 2. Only Ca is titrated.

Step 3. Cd and Cu are titrated.

Cd Cd-EDTA
+ EDTA
Ca-EDTA
Ca
06/12/2024 121
 Complexometric Titration…
ii. pH control Method:

• The formation of a metal chelate is dependent on the pH of the reaction

medium.

• This method is based upon the differences in stability of the chelates

formed between the metal ions and the chelating agent.

Example: A mixture of bismuth and lead ions can be successfully

titrated by first titrating the bismuth at pH 2 with xylenolorange as indica-
tor, and then adding hexamine to raise the pH to about 5, and titrating
the lead.
iii. Use of selective metal indicators:

• These indicators are the metal complexing agents which react with differ-
ent metal ions under various conditions. Several selective metal indicators
have been used and they are specific for a particular ion.
06/12/2024 122
 Complexometric Titration…

Applications

06/12/2024 123
 Some Important Applications of Complexo-
metric reactions:

(1)Determination of Water Hardness by EDTA titrations:

(2)1- Titration using eriochrome black-T indicator and ammonia

buffer at pH 10, gives total hardness (Ca2+ + Mg2+).

(3)2-Titration using murexide indicator and (2N) NaOH at pH 12,

gives calcium hardness only.
(4)Magnesium hardness = total - calcium hardness.

06/12/2024 124
 (2) Determination of Pharmaceutical compounds having
Chelating properties:
Examples:

Apomorphine Carbidopa

R
N
OH
Adrenaline 8-Hydroxyquinolines
06/12/2024 125
(3) Determination of Pharmaceutical compounds which
containing metal ions that undergo complexation reac-
tions

Examples:
• Aluminum, Calcium, magnesium and zinc salts of pharmaceutical impor-
tance:
(A) Inorganic salts:
• Aluminum potassium sulfate, Aluminum chloride hexa-hydrate, dried Alu-
minum hydroxide, Aluminum acetate, dried Aluminum phosphate & Alu-
minum magnesium silicate.
• Calcium sulfate, Calcium carbonate & Calcium Oxide
• Barium sulfate
• Magnesium sulfate, Magnesium oxide & Magnesium carbonate, Zinc sul-
fate and Zinc Oxide

06/12/2024 126
 (B) Organic Salts :

Aluminium Glycinate Zinc undecenoate

Zinc acexamate
Calcium folinate

06/12/2024 127
 (B) Organic Salts …

Calcium levulinate dihydrate

Calcium gluconate

Calcium pantothenate

Calcium ascorbate

Calcium dobesilate
06/12/2024 128
 REDOX TITRATION

06/12/2024
 REDOX TITRATION

• Redox titration: is titration in which the reaction between the

analyte and titrant is an oxidation/reduction reaction.
• These titrations involve the titration of an oxidizing agent (or
oxidant) with a reducing agent (or reductant) or vice versa.
• The chemical reaction proceeds with transfer of electrons (si-
multaneous loss or gain of electrons) among the reacting ions
in aqueous solutions.
• Oxidation process involves loss of electrons
• Reduction process involves gain of electrons.
• An oxidizing agent oxidizes the other substance by
stripping off electrons from it.
• A reducing agent reduces the other substance by donat-
ing electrons to it.

06/12/2024 130
 REDOX TITRATION…
Example

• Here, the ferrous ions are getting oxidized to ferric ions by the
loss of one electron.

• The chlorine gets reduced to chloride ions by gaining elec-

trons

• Further, oxidation and reduction are always found to occur to-

gether in a reaction.

• In other words, electron loss of one substance is always accom-

panied by an electron gain on the part of the other and conse-
quently there are no free electrons in a chemical system.

06/12/2024 131
 REDOX TITRATION…
• Oxidation of a substance leads to increase in its oxidation
number while Reduction of a substance lead to decrease in
the oxidation number.

• The relative tendency to accept or lose electrons by any

reagent is measured in terms of their standard reduction po-
tential values.
• Reduction potential is the measure of how thermodynamically fa-
vorable it is for a compound to gain electrons.
• A high positive value for reduction potential indicates that a com-
pound is readily reduced and hence is a strong oxidizing agent.

• Nernst equation, which relates the electrochemical potential to the concentra-

tion of reactants and products participating in a redox reaction is often used in
determining the concentration of an analyte.
06/12/2024 132
 REDOX TITRATION…
REDOX TITRATION CURVES

• By plotting the redox potential corresponding to different points in the titra-

tion, a titration curve similar to the curve obtained in an acid-base method is ob-
tained.

Example: titration of 100 cm3 of 0.1M iron (II) with 0.1 M cerium (IV) in the pres-
ence of dilute sulphuric acid.

06/12/2024 133
 REDOX TITRATION…
REDOX INDICATORS
• A redox indicator is a compound which can undergo a redox reaction
and change colour depending on the potential of the solution.

• The oxidised and reduced forms of the indicator have different

colours.

• The redox indicator will show colour X if the intensity of this colour
(oxidised form) is at least 10 times greater than the intensity of the
colour Y.

• Similarly, the indicator will show colour Y if the intensity of the

colour is 10 times more than that of the colour X.
06/12/2024 134
 REDOX TITRATION…
REDOX INDICATORS…
• The following table shows the colour of the oxidized and re-
duced form of some redox indicators.

06/12/2024 135
 REDOX TITRATION…
i.A. OXIDIMETRIC REAGENTS

ii.Permanganate titrations (KMnO4): titrations in which

potassium permanganate is used as an oxidizing agent.
• Oxidizing agent in all medium but it is strong in acidic
medium
• The medium is maintained by the use of dilute sulfuric acid
• Potassium permanganate acts as a self-indicator (colorless to
pink )
• The potential equation, when potassium permanganate acts
as an oxidizing agent, is:

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 REDOX TITRATION…
i. Permanganate titrations (KMnO4)…
• KMnO4 is not primary standard. It is difficult to ob-
tain the substance perfectly pure and completely free
from manganese dioxide.
• More over, ordinary distilled water is likely to contain
reducing substances which will react with the potas-
sium permanganate to form manganese dioxide.
• The presence of the latter is very objectionable be-
cause it catalyses the auto decomposition of the
permanganate solution on standing.

KMnO4 + 2H2O = 4MnO2 +3O2 + 4 OH-

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 REDOX TITRATION…
i. Permanganate titrations (KMnO4)…
• For this reason, potassium permanganate solution is rarely
made up by dissolving weighed amounts of the purified
solid in water:
• It is more usual to heat freshly prepared solution to boiling
and keep it on the steam bath for an hour or so, and then
filter the solution through a non-reducing filtering
medium.
• Solutions of permanganate should be protected from
unnecessary exposure to light.
• The solution so obtained is then standardised against
sodium oxalate or Arsenic(III) oxide.

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 REDOX TITRATION…
i. Permanganate titrations (KMnO4)…
• Standardization of KMnO4 by oxalic acid can be repre-
sented by the following equation,

• Standardization of KMnO4 by Arsenic oxide can be repre-

sented by the following equation,

• The oxidant is commonly used for the analysis of iron(II),

As(III), H2O2 and NO2− ion, the corresponding equations
being as follows.

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 REDOX TITRATION…
ii. Potassium dichromate titrations
• Potassium dichromate is also a very strong oxidizing agent

• However it is not as strong oxidizing agent as permanganate is

• Still it is widely used in redox titrations because of several ad-

vantages over permanganate.

• Unlike potassium permanganate, potassium dichromate is

available in high purity and is highly stable

• Its aqueous solutions are not attacked by oxidisable impurities

and thus composition of aqueous solution does not change on
keeping.
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 REDOX TITRATION…
ii. Potassium dichromate…
• The aqueous solutions are quite stable towards light.

• It is thus an excellent primary standard and its standard

solutions can be prepared by direct weighing of an amount
of it and dissolving in a known volume of distilled water.

• Potassium dichromate acts as oxidizing agent in acidic

medium only

• The neutral aqueous solution of Potassium dichromate is

1:1 equilibrium mixture of dichromate and chromate, a
consequence of hydrolysis of dichromate ions.

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 REDOX TITRATION…
ii. Potassium dichromate…
• Chromate ions are weaker oxidizing agent than dichro-
mate.
• Thus oxidizing strength of dichromate is reduced in neutral so-
lution.
• The above hydrolysis reaction however can be reversed by
adding acid to the solution and this explains the necessity
of acidic medium for the reaction.
• The end point in titrations with dichromate ion is generally de-
tected by using suitable redox indicators such as dipheny-
lamine, sodium diphenylaminesulphonate and N-phenylan-
thranilic acid, etc.
• It can be used in acidic medium to determine most com-
pounds that can be titrated with KMnO4.
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 REDOX TITRATION…
iii. Cerium (IV) titrations
• Cerium (IV) sulphate is a powerful oxidising agent in acidic
medium.

• It can be used only in acid solution. As the solution is neu-

tralized, Cerium(IV) hydroxide or basic salts precipitate.

• Advantages
• Cerium(IV) sulphate solutions are remarkably stable over
prolonged periods. They need not be protected from light.
• It may be used in the determination of reducing agents in
the presence of hydrochloric acid.
• Cerium solutions are not too highly colored to obstruct vi-
sion when reading the meniscus in burettes

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 REDOX TITRATION…
iii. Cerium (IV)
• It can be standardized using Arsenic acid and sodium oxalate
• It can be used for the determination of copper, nitrites, etc.
iv. Potassium bromate titrations
• It is also a strong oxidant in acidic medium.

• Potassium bromate is a primary standard as the reagent can be ob-

tained in a pure state.

• Its standard solution can be prepared by direct weighing.

• The end point in titrations with bromate is indicated by the yellowish

color due to bromine released from the slight excess of reagent
added.

• The end point may also be detected with indicators such as methyl
orange, methyl red etc.

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 REDOX TITRATION…
iv. Potassium bromate…
• The reagent is used in hydrochloric acid for the direct deter-
mination of arsenic(III), antimony(III), tin(II), hydrazine,
etc.

• There are many compounds, which do not react with bromate

as such but with bromine liberated from reaction between
bromate and bromide, and to accomplish this, an excess of
bromide is added to the solution.

• Bromine thus liberated is used for quantitatively saturating

the double bond and in substitution reactions.
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 REDOX TITRATION…
iv. Potassium bromate…

• The unreacted bromine is determined by adding a solu-

tion of potassium iodide and titrating the liberated iodine
with thiosulphate.

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 REDOX TITRATION…
v) Iodine (IODIMETRIC TITRATIONS)
• Iodine is a weak oxidant

• Iodine is sparingly soluble in water and its aqueous solution is

prepared by adding potassium iodide.

• Though in such a solution, iodine is in the form of a tri-iodide

ion I3- , but for sake of simplicity, iodine is usually expressed as
I2 in its reactions.
• Iodine solutions are standardised by means of arsenous oxide
(a primary standard)

• Starch is generally used as an indicator; the solution turns

blue at the end point.

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 REDOX TITRATION…
• With the standard solution of I2. Substances such as hydro-
gen sulphide, stannous, arsenite, Ascorbic acid and sul-
phurous acid can be estimated.

• Iodimetric titration is used in pharmacopoeial assay of

Ascorbic acid, Sodium Stilbigluconate, Dimercaprol injection
and acetarsol.

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 REDOX TITRATION…
VI. Iodometric titrations
• An oxidizing agent is allowed to react in neutral medium or in
acidic medium, with excess of potassium iodide to liberate free io-
dine.

• Free iodine is titrated against a standard reducing agent usually

with sodium thiosulphate.

• The end point can be detected by adding starch. The blue color
disappears at the end point.

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 REDOX TITRATION…
VI. Iodometric titrations…
• Halogen, dichromates, cupric ion, peroxides, etc., can
be estimate by this method.

• Pharmacopoeia-phenol, Methyl hydroxybenzoate, Phenid-

ione
• In general,
• The method in which iodine is used for the determina-
tion of reductants is called iodimetry.
• The method in which iodide is used for the deter-
mination of oxidants is called iodometry.
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 REDOX TITRATION…
B. REDUCTIMETRIC REAGENTS

• Standard solutions of reducing agents are not used as widely

as oxidising agents, because most of them are oxidized by
dissolved and atmospheric oxygen.

• They are, therefore, less convenient to prepare and use.

• Thiosulphate is the only common reducing agent that is stable to

air oxidation and can be kept for long periods of time.

• This is the reason that Iodometric titrations are so popular for

determining oxidising agents.

• However, stronger reducing agents than iodide are some-

times required.

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 REDOX TITRATION…
i) Iron
• It is a weak reductant.

• Iron(II) is slowly oxidized by air in sulphuric acid solution

and finds common use.

• Its standard solution is prepared from Mohr's salt FeSO4.

(NH4)2SO4.6H2O and standardized against primary standard
K2Cr2O7, or by titration with a standardized KMnO4 or
cerium(IV) solution.

• The end point in titrations involving iron(II) is detected by using

redox indicators such as ferroin, N-phenylanthranilic acid etc.

• In the presence of concentrated sulphuric acid at 0oC, iron(II) is

used for the determination of nitrates, nitro compounds,
etc.
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 REDOX TITRATION…
ii) Chromium (II) and Titanium(III)
• These two are very powerful reducing agents, but they are readily
oxidized by air and consequently are difficult to handle.
• The reduction equations are as follows.

• Chromium (II) has been used for the titrations of oxidized forms of
copper, iron, silver, gold, bismuth, uranium, tungsten, etc.

• Titanium (III) has, however, been used for the titrations of

iron(III), copper(II), tin(IV), chromate, vandate and chlorate.

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 REDOX TITRATION…
iii) Sodium Thiosulfate, Na2S2O3
• Thiosulfate is a moderately strong reducing agent

• Thiosulfate solutions are standardized with iodine which has been

prepared by acidifying primary standard potassium iodate in the
presence of a slight excess of potassium iodide:

• The titration reaction between iodine and thiosulfate is fairly

straightforward:

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 Diazotization Titration or Nitrite Titration
• Diazotization is used in the analysis of aromatic com-
pounds containing an amino group in the molecules.

• Aromatic primary amine reacts with sodium nitrite in acid

solution (i.e, nitrous acid) to form diazonium salts.

• Many aromatic primary amine with free –NH2 group can be

analyzed quantitatively by measuring the volume of
NaNO2 solution required to convert them into diazonium
salts.

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 Diazotization Titration…
• Observation of end point depends upon the detection of small
excess of nitrous acid which in turn can be detected by the
starch paper or paste as an external indicator.

• Starch iodide paper or paste is the starch solution plus

equal volume of 5% KI solution in H2O.

• Starch iodide paste with reaction mixture is as follows-

• The liberated I2 reacts with starch to give blue color.

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 Diazotization Titration…
Application of diazotization titration
• An important pharmaceutical application of sodium nitrite
titration is the analysis of sulphonamides by diazotiza-
tion of primary aromatic amino group usually present in
this class of drugs.

• Several sulphonamides require the formation of primary

amine prior to diazotization step.

• List of compounds assayed by sodium nitrite titration:

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 Redox Titrations…

APPLICATIONS

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 Some redox applications
a) Titration with potassium permanganate:

COOH H3C CH OH
Oxalic acid Lactic acid
COOH COOH

b) Titration with potassium dichromate:

CH2OH
Glycerol
CH.OH
CH2OH
c) Titration with Cerium sulfate:

Calcium dobesilate

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 d) Direct titration with standard iodine solution:

Benzylpencillin potas-
sium

Ascorbic acid
Captopril

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 e) Bromometric determinations:

Butylhydroxybenzoate Amylmetacresol Benzylhydroxybenzoate

Chloroxylenol

Chlorocresol

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 •Thank you

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