Sisay K.

Chapter three

Titrimetry

07/09/24
 Outline
2

 INTRODUCTION

 ACID-BASE TITRATION

 PRECIPITATION TITRATION

 COMPLEXOMETRIC TITRATION

 REDOX TITRATION

Sisay K. 07/09/24
 OBJECTIVES
3

 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)
Sisay K. 07/09/24
 Introduction
4

 Definition- titration is the process of slowly adding a

reagent, with a known concentration or whose
concentration can be precisely determined, in to analyte
until the reaction between them is completed.
 Volume is measured
 Standard reagent- titrant
 Analyte- titrand

Sisay K. 07/09/24
 Introduction…
5

Definition of some terms

Titration: this is a gradual addition of solution of accurately

known concentration to the solution containing known volume, but

unknown concentration of analyte.
Titrant: This is the solution of accurately known concentration

which is being employed in the determination (titration) of the

concentration of unknown.
Titrand: this is the solution containing the substance with

unknown concentration which is to be titrated with standard

solution.
Analyte: this is the chemical substance or species which its

concentration is to be determined.
Sisay K. 07/09/24
 Introduction…
6

Definition….
Equivalence point: this is the point in titration exercise where

sufficient amount of titrant has been added to the titrand

(theoretical point where complete stoichiometric reaction takes
place).
End point: this is the point in titration exercise where the

completion of reaction is signed or indicated by color change of

indicator used( it is practical or experimental point of completion
of reaction)
Standard solution: this is a solution of accurately known

concentration that is used in a titrimetric analysis.

Sisay K. 07/09/24
 Introduction…
7

Definitions…
Indicator: it is an auxiliary substance which shows clear visual
changes after the reaction between titrate & titrant is practically
complete.
Titration error: in practice very small difference between
theoretical endpoint and actual endpoint usually occurs. This is
called as titration error.
Primary standard: this is an ultra-pure compound that serves
as a reference material for titrimetric methods of analysis.
Sisay K. 07/09/24
 Introduction …
8

 aA + tT products
 For volumetric titrations, the amount, nA, of analyte in the
sample can be calculated using

nA = a/t CTVT

 The type of reaction provides a simple way to divide

titrimetry into the following four categories:

 Acid-base, precipitation, complexometric and

redox titration Sisay K. 07/09/24
 Introduction …
9

 Despite the difference in chemistry, all titrations share several

common features
A. Requirements for titration
 stoichiometric ratio should be known
 No complicating side reaction
 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
occur at the end-point Sisay K. 07/09/24
 Introduction …
10

 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 accurately known Sisay K. 07/09/24
 Introduction …
11

A primary standard…
 It should be stable at atmospheric conditions

 Should have high molecular weight

 It should be soluble in the conditions applied

 Standards used as a standard that do not meet all these criteria are
called secondary standards
 Exact concentration is determined by standardization
o Standard solutions are prepared in two ways:
 Direct method- weigh and dissolve (eg. KHP)
 Indirect method- standardization (NaOH vs KHP)

Sisay K. 07/09/24
 Introduction …
12

B. Equivalence Point and End point

 Equivalence point- the point where the reaction b/n the
titrant and analyte is completed
 Can not be determined experimentally
 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

Sisay K. 07/09/24
 Introduction …
13

C. Direct titration and Back titration

-Direct titration
- Back titration

mmol reagent reacted = mmol taken-mmol back titrated

mg analyte = mmol reagent reacted x factor (combination ratio)x molecular

weight of analyte

 When do we use back titration?

Sisay K. 07/09/24
 When do we use back titration?
14

 If the end point of the reverse titration is easier to identify 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
Sisay K. 07/09/24
 Introduction cont…
15

Sisay K. 07/09/24
 Introduction cont…
16

D. Calculations in titrimetry
 The calculation involved in solution preparation,
standardization and % constituent calculation can be
summarized as follow:
1. Preparation of a solution a pure, solid chemical:

Example- describe the preparation of 2 liter of 0.108 M Barium

chloride from BaCl2.2H20 (M.wt-244.3 g/mol)

Sisay K. 07/09/24
 Introduction cont…
17

2. Preparation of solution by dilution

Example: how would you prepare 0.5 M of HCl acid in 250ml

from its stock solution having 11.9 M?

Sisay K. 07/09/24
 Introduction cont…
18

3. Standardization with a primary standard

Example: 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

Sisay K. 07/09/24
 Introduction cont…
19

4. Titration with another standard solution:

Example: titration of 50 ml of HCl requires 45 ml of 0.5 M

NaOH. Calculate the Molarity of HCl.

Sisay K. 07/09/24
 Introduction cont…
20

5. Percentage of constituent, direct titration:

Example: 2 gm of drug “X” was weighed and dissolved in 500 ml

of water. The solution was titrated against 0.5 M HCl after
adding 3 drops of appropriate indicator. 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), (Answer % analyte =90%)
Sisay K. 07/09/24
 Introduction cont…
21

6. Percentage constituent, back titration

Example: A pharmacist wants to determine the percentage of drug

“X” using a titration. 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 consumed in the titration. Assuming 1:1
reaction, calculate the percentage of drug “X” in the sample
taken (M.wt of “X” is 180 gm/mol).
= 97.2%
Sisay K. 07/09/24
 Introduction cont…
22

E. 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 titration reaction changes as we add the titrant to
the titrand.

 Titration curve define the required properties of an indicator

and allow us estimate the error associated with the titration
methods
Sisay K. 07/09/24
 Introduction cont…
23

Example

Figure-1: strong acid- strong base titration curve(a), weak acid- strong
base titration curve(b)
Sisay K. 07/09/24
 Introduction cont…
24

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

ml of the titrant.

Titer value = N × Eq. wt or M .M.wt

Sisay K. 07/09/24
25

Acid-Base Titration

Sisay K. 07/09/24
26 Sisay K. 07/09/24
 Acid-Base Titration …
27

 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

Sisay K. 07/09/24
 Aqueous acid – base titration
28

 Acid – base titration in aqueous media

 It involves neutralization reaction in the presence of water as
a solvent
 The standard solutions (titrants) employed in neutralization
titrations are strong acids or strong bases
 Because the substances react more completely with the analyte than
weaker acids/bases
 And thus yields sharper end - points
Sisay K. 07/09/24
 Contd…
29

Sisay K. 07/09/24
 Contd…
30

 Detection of the end point: Indicators

Δ It is usually more convenient to add an indicator to the

solution and visually detect a color change.

Δ An indicator for acid-base is a weak acid or weak base that

is highly colored.

Δ The color of the ionized form is markedly different from

that of the non-ionized form.

Sisay K. 07/09/24
 Contd…
31

 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:
pH = pKa + log[In-]
[HIn]

Sisay K. 07/09/24
 Contd…
32

 With indicators in which

both forms are colored,
generally only one color
is observed if the ratio of pH = pKa + log 1
10
the concentration of the
two forms is 10:1 = pKa-1

 When only the color of

the nonionized form is
seen, [In-]/[HIn] =1/10

Sisay K. 07/09/24
 Contd…
33

 When only the color of the ionized form is observed,

[In]/[HIn] =10/1
pH = pKa + log10
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. Sisay K. 07/09/24
 Contd…
34

I. Direct titration of strong acid with strong base

 Characterized with large pH change around the
equivalence point. Eq.pt at pH = 7

 Before the equivalence point, pH depends on amount of

excess strong acid present

 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
Sisay K. 07/09/24
 Contd…
35

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
 If indicator like Methyl red (4-6) is used,
there will be change in the color HA vs NaOH

before the equivalence point

Sisay K. 07/09/24
36 Sisay K. 07/09/24
 Contd…
37

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

Sisay K. 07/09/24
 Contd…
38

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 dependes on amount of excess
acid added

Sisay K. 07/09/24
39 Sisay K. 07/09/24
 Contd…
40

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

Sisay K. 07/09/24
 Acid-base titrations in non - aqueous media

41 Sisay K. 07/09/24
 Acid-base titrations in non - aqueous media…
42

 The major limitation of water as a titration medium, is due to

its amphoteric behavior
 Thus, neither weakly acidic nor weakly basic substances can
be titrated easily in aqueous solutions

 Because of the overwhelming effect of the solvent acting as

a competing weak acid or base

 The simplest solution to this problem is to replace the solvent

Sisay K. 07/09/24
 Cont’d…
43

 If the solute is a weakly basic compound, successful titration is blocked by

the basic character of the solvent water
 If the water is replaced by a relatively non-basic solvent, this undesirable
competition is effectively eliminated, or at least reduced, & the solute base
can now be titrated
 Similar situation holds for weakly acidic solutes;
 In this case, the acidic nature of water renders it an undesirable solvent
 Should be supplanted by a solvent with no acidic properties

Sisay K. 07/09/24
 Cont’d…
44

 Titration in non-aqueous media or in total absence of water is

known as non-aqueous titration
 Most common titrimetric procedure used in pharmacopeial assays

 Serves a double purpose:

 It’s suitable for titration of very weak acids & bases, and
 Provides a solvent in which organic compounds are soluble

Sisay K. 07/09/24
 Cont’d…
45

 All the apparatus & glassware for a nonaqueous titration must

be scrupulously dry, as even a drop of water will ruin the
whole assay

 All glassware should be rinsed with distilled water, rinsed

again with a volatile solvent such as acetone, then dried
thoroughly in an oven or hot air dryer.

Sisay K. 07/09/24
 Solvents for non-aqueous titrations
46

 The ability of substances to act as acids or bases will depend

on the nature of the solvent system which is employed
 Solvents can be classified into four groups:
 Protophilic solvents
 Protogenic solvents
 Amphiprotic solvents
 Aprotic solvents

Sisay K. 07/09/24
 Protophilic solvents:
47

 They are basic solvents (proton-loving)

 More basic than water & have high ability to accept protons
 e.g. liquid ammonia, amines, ethers, & ketones

HA + S SH+ + A-
 They enhance the strength of weak acids (e.g. acetic & formic
acids) so that they’ve the same strength as strong acids
(perchloric & sulfuric acids)

Sisay K. 07/09/24
 Protogenic solvents:
48

 They are acidic solvents (proton producing)

 More acidic than water & have the affinity to donate protons
 e.g. sulfuric acid

H2SO4 + 2B SO42- + 2BH+

 They enhance the strength of weak bases so that they’ve the

same strength as strong bases

Sisay K. 07/09/24
 Amphiprotic solvents:
49

 They are liquids that get ionized to a slight extent

 Exhibit both protogenic & protophilic properties

e.g. alcohols, water, acetic acid

Sisay K. 07/09/24
 Aprotic solvents:
50

 They are chemically inert

 Unreactive under the conditions used for determinations

e.g. Toluene, chloroform, CCl4, and benzene

 They do not cause ionization of solutes

 Do not undergo reactions with acids or bases

 Used only as vehicles or diluents

Sisay K. 07/09/24
 Applications of non-aqueous titrations
51

Non-aqueous titrations are used for:

Substances which are of insufficient basic/acidic strengths to
give sharp end points in aqueous solutions
Analysis of mixtures of acids or bases which cannot be
differentiated in aqueous solutions. e.g. HCl & HClO4 in
methyl-isobutyl ketone as solvent
Substances which are insoluble in water

Sisay K. 07/09/24
 Titration of basic substances
52

Used for titration of:

 All amine types
 Nitrogen-containing heterocyclic compounds like purines
 Halide salts of amines & quaternary ammonium salts
 Alkali metal salts of organic acids

Sisay K. 07/09/24
 General conditions:
53

 Solvent: mostly glacial acetic acid for dissolving sample &

standard

 Titrant: perchloric acid (HClO4) in glacial acetic acid

 Stock solution: 72% perchloric acid

 Acetic anhydride is used to eliminate the water added with
HClO4 solution

 Indicator: 0.5% acetous crystal violet solution (color changes from

blue to green)
Sisay K. 07/09/24
 Exercise
54

 A perchloric acid solution is prepared by adding 17.0 mL of

72% (w/w) perchloric acid to enough glacial acetic acid to
make 1000 mL. Calculate the volume of acetic anhydride
(MWt = 102 gm/mol) required to react with all of the water
added with the perchloric acid. The density of 72% perchloric
acid is 1.6 gm/mL & that of acetic anhydride is 1.02 gm/mL.

Sisay K. 07/09/24
 Contd…
55

Application of Acid-base titration

 Water acidity (CO , S, Fe(SO ) , FeCl )
2 4 3 3

 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

Sisay K. 07/09/24
 Titration of basic substances
56

Examples of basic drugs

 Antihistamines
 Local anaesthetics
 Morphine
 Alkali metal salts of organic acids such as phenobarbitone
sodium & sodium salicylate etc…

Sisay K. 07/09/24
 Titration of acidic substances
57

Examples:
 Very weak aromatic & aliphatic acids
 Phenols & enols
 Imides & sulphonamides

General conditions:
 Solvents: benzene-methanol mixture, DMF, & ethylenediamine
 Titrant: potassium (or lithium) methoxide
 Indicators: thymol blue or azo violet
Sisay K. 07/09/24
 Determination of some pharmaceutically important acids

a) Carboxylic acid derivatives;

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

b) Carboxylic acid and phenolic derivatives

Aspirin, Antipyretic Levodopa, Used for treatment of
parkinson’s disease

58 Sisay K. 07/09/24
 Determination of some pharmaceutically important acids

c) Sulphonic acid derivatives:

Estropipatic acid
Etamsylate, Haemostatic agent

d) Arsenic acid derivatives;

Arsenillic acid, Antibacterial

59 Acetarsol
Sisay K. 07/09/24
60

Determination of some pharmaceutically important bases:

a) Primary amine compounds:

Amikacin, antibiotic

Sulphadiazine
Sisay K. 07/09/24
 b) Secondary amine compounds:
Viloxazine, Antidepressant
Xylazine, Analgesic Piprazine hydrate

Tulobuterol, Beta-adrenoceptor agonist Pinadolol, Beta-adrenoceptor antagonist

61 Sisay K. 07/09/24
 C- Acid Salts of Basic Drugs
62

Amiloride hydrochloride

Sisay K. 07/09/24
63

Precipitation titration

Sisay K. 07/09/24
 Precipitation titration
64

 Precipitation titration - 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, the
co-precipitation is a challenge

Sisay K. 07/09/24
 Precipitation titration
65

 Solubility product
o Solubility is a physical property referring to the ability for a
given substance, the solute, to dissolve in a solvent
o It is measured in terms of the maximum amount of solute
dissolved in a solvent at equilibrium-saturation
o Solubility is commonly expressed as a concentration
o An oversaturated solution becomes a saturated solution by
forming a solid to reduce the dissolved material- precipitate

Sisay K. 07/09/24
 Precipitation titration…
66

 Solubility product
o A saturated solution of a slightly soluble salt in contact with
an undissolved salt involves equilibrium like the one below:

o So the equilibrium constant expression for the equilibria

above is:

o This equilibrium constant Ksp is called a solubility-product

constant
Sisay K. 07/09/24
 Precipitation titration…
67

 Example-1
o What is the concentration of silver chloride ions in a
saturated silver chloride solution at 25 degrees? Ksp =
1.8 x 10-10
 Example-2
o Calculate the solubility in g/L of calcium sulfate, CaSO4,
given that its Ksp is 2.4 x 10-5.

Sisay K. 07/09/24
 Precipitation titration…
68

 Factors affecting solubility of a precipitate

1. Temperature effect
 Most of inorganic salts increase its solubility by
increasing temperature.
 Exception-Hg2Cl2, MgNH4PO4

2. Solvent effect
 Most of inorganic salts dissolve in water but not
in organic solvent.
 In order to form a precipitate, the product
formed should be insoluble in the solvent.
Sisay K. 07/09/24
 Precipitation titration…
69

 Factors affecting solubility of a precipitate…

3. The Common Ion Effect
 Precipitate dissolves more easily in water than in
solution containing common ions.
 Consider-solution of AgCl in the presence of NaCl

Example: Calculate the molar solubility of barium fluoride,

BaF2, in water at 25oC. The Ksp at 25oC is 1.0 x 10-6.(Ans.
6.3 x 10-3)
 To illustrate the common ion effect
 What is its solubilty in 0.15 M NaF?
(Ans. 4.4 x 10-5 ) Sisay K. 07/09/24
 Precipitation titration…
70

 Factors affecting solubility of a precipitate…

4. The pH effect
 Solubility of weak acid/weak base salt depends on pH of
the solution.

Sisay K. 07/09/24
 Precipitation titration…
71

 Precipitation Calculations
 If we have a given set of concentration conditions we can
calculate a solubility quotient, Qc, and compare it to the Ksp
 The solubility quotient (often called the ion product) has
the same form as the solubility constant expression, but the
concentrations of the substances are not necessarily
equilibrium values

Sisay K. 07/09/24
 Precipitation titration…
72

Example 1: Suppose a solution has Ca+2 and SO4 -2

concentrations of 0.0052 M

and 0.0041 M, respectively. If these concentrations were doubled by

evaporating half the water in the solution, would precipitation of CaSO 4 occur

given that the Ksp for calcium sulfate is 2.4 x 10 -5? (Qc= 8.53 x 10-5)- Qc> Ksp

Example 2: A solution of 0.00016 M lead(II)nitrate, Pb(NO3)2, was poured into

456 mL of 0.00023 M sodium sulfate, Na2SO4. Would a precipitate of

lead(II)sulfate, PbSO4, be expected to form if 255 mL of the lead nitrate

solution were added? (The Ksp for lead(II)sulfate is 1.7 x 10 -8) (Qc= 8.48 x 10-
9
)- (Qc < Ksp)

Sisay K. 07/09/24
 Precipitation titration…
73

 Standard solution
 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. Sisay K. 07/09/24
 Precipitation titration…
74
 End-point detection
 Mohr’s Method

 Chromate ion (CrO42-) is added to serve as indicator.

 Mohr titration has to be performed at a neutral or weak basic
solution of pH 7-9
 At low pH (<6)- over titration

 In higher pH (basic), Ag2O will be formed as a black precipitate and

hence silver ion will be over consumed there by resulting in titration
error.

 After equivalent pt silver chromate(red color) is formed

Sisay K. 07/09/24
 Precipitation titration…
75

 End-point detection
 Mohr’s Method
 Mohr method it is not feasible for I- and 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.

Sisay K. 07/09/24
 Precipitation titration…
76

 End-point detection
 Volhard’s Method
o Volhard titration is an indirect (back titration)
o Titration principle : Silver solution is added excessively to a
halide.

o Back titrated with a standardized thiocyanate solution.

o Fe(III) indicator

o Reddish brown ferric thiocyanate

o Carried in acidic media
Sisay K. 07/09/24
o Sensitive and very precise
77

Sisay K. 07/09/24
 Precipitation titration…
78
 End-point detection
 Fajan’s Method
 The reaction between the indicator and excess silver takes
place on the surface of the precipitate

 The color of the adsorbed indicator is different from that of

unadsorbed indicator and this difference signals the
completion of the titration
Example- fluorescein (at neutral or basic pH)
Sisay K. 07/09/24
 Complexometric titration
79

Titrating metal ions with a complexing agent or chelating

agent (Ligand)
Equivalence point is determined by using metal indicators
or electrometrically.
o chilometric titrations,

o chilometry,

o chilatometric titrations and

o EDTA titrations

Sisay K. 07/09/24
 Complexometric titration …
80

 The negative charge on the complex ion is equal to

the total number of the negative groups minus the
valency of the metal ion

eg, (Fe (CN)6)-3

 When neutral groups only are involved, the charge on

the complex is positive and is equal to the metal ion
e.g. [Cu (NH3)4]2+.

Sisay K. 07/09/24
 Complexometric titration …
81

Classification of Ligands
 Unidentate Ligands:
 Ligands that are bound to metal ion only at one place

are called unidentate ligands (one toothed).

 Halide ions, cyanide ions and NH3 are common

examples of unidentate ligands.

 NH3, for example, is a unidentate ligand capable of

complexing with cupric ions.
Sisay K. 07/09/24
 Complexometric titration …
82

Sisay K. 07/09/24
 Complexometric titration …
83

 Bidentate and Multidentate Ligands:

 Many ligands are known that contain more
than one group, capable of binding with metal
ions.
 Called multidentate ligands or chelating
agents.
They include:
 bidentate ligands (2 donar atoms), eg. ethylene
diamine (H2N-CH2-CH2-NH2),
 tridentate ligands (3 donar atoms),
 quadridentate ligands,
 Ethylenediamine tetra acetic acid (EDTA) is
an example of multidentate ligand.

Sisay K. 07/09/24
 Complexometric titration …
84

Chelate Compound or Chelate

 Complexes involving simple ligands, i.e., those forming

only one bond are described as co-ordination compound.

 A complex of a metal ion with 2 or more groups on a

multidentate ligand is called a chelate or a chelate
compound.
Sisay K. 07/09/24
 Chelating agent
85

 Ligands having more than one electron donating groups are

called chelating agents.
 The most effective complexing agent in ligands are amino
and carboxylate ions.

Sisay K. 07/09/24
 EDTA
86

 It forms chelates with nearly all metal ions

 Such titrations are called complexometric or chilometric
or EDTA titrations.

 Disodium salt of EDTA is a water soluble chelating

agent and is always preferred.
 It is non-hygroscopic and a very stable sequestering
agent (Ligands which form water soluble chelates are
called sequestering agents).

Sisay K. 07/09/24
 Complexometric titration …
87

 EDTA and 8-hydroxy quinoline are important reagents

used in analytical chemistry.
 Ethylenediaminetetra-acetic acid forms complexes with
most cations in a 1:1 ratio, irrespective of the valency of
the ion.

Sisay K. 07/09/24
 Complexometric titration …
88

Stability of Complexes : The general equation for the formation

of a 1:1 chelate complex, MX, is

∴ Stability Constant (K) = [MX]/[M][X]

 NOTE: Increase in temperature causes a slight increase in

the ionization of the complex and a slight lowering of K.
The presence of electrolytes having no ion in common with
the complex decreases K, whilst the presence of ethanol
increases K, probably due to the suppression of ionization.
Sisay K. 07/09/24
 Complexometric titration …
89

Principle of Complexometric Titration

In complexometric titration:

 The free metal ions disappear as they are changed into

complex ions.

 End point can be detected usually with an indicator or

instrumentally by potentiometric or conductometric
(electrometric) method.

Sisay K. 07/09/24
 Complexometric titration …
90

 There are three factors that are important in determining the

magnitude of break in titration curve at end point.

1. The stability of complex formed:

 The greater the stability constant for complex formed, the larger the
charge in free metal concentration (pM) at equivalent 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.

Sisay K. 07/09/24
 Complexometric titration …
91

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

constant by use of a buffer solution.

 Control of pH is important since the H+ ion plays an

important role in chelation.

 Most ligands are basic and bind to H+ ions throughout a

wide range of pH. Some of these H+ ions are frequently

displaced from the ligands (chelating agents) by the metal
during chelate formation.
 Equation below shows complexation between metal ion and

H+ ion for ligand:

Sisay K. 07/09/24
 Complexometric titration …
92

Thus, stability of metal complex is pH dependent.

 Lower the pH of the solution, lesser would be the stability

of complex (because more H+ ions are available to compete
with the metal ions for ligand).

 Only metals that form very stable complexes can be titrated

in acidic solution, and metals forming weak complexes can
only be effectively titrated in alkaline solution.

Sisay K. 07/09/24
 Complexometric titration …
93

Methods of End Point Detection

 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.

 Colour of the indicator and the metal complexed indicator

must be sufficiently different.

 The indicator should not compete with the EDTA.

Sisay K. 07/09/24
 Complexometric titration …
94

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 contains 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.

Sisay K. 07/09/24
 Complexometric titration …
95

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 complex.
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:
Sisay K. 07/09/24
 Complexometric titration …
96

Types of Complexometric Titrations

 Complexometric titrations are of 4 types:

1. Direct Titration:
 It is the simplest and the most convenient method
 The standard chelon solution is added to the metal ion
solution until the end point is detected.

Limitations -slow complexation reaction

-Interference due to presence of other ions
Sisay K. 07/09/24
 Complexometric titration …
97

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

E.g. - Determination of Mn. This metal cannot be directly

titrated with EDTA because of precipitation of Mn(OH)2.
back titrated with a standard Zn solution kept in burette using
Eriochrome blackT as indicator.

Sisay K. 07/09/24
 Complexometric titration …
98

3. Replacement Titration:
 The metal, which is to be analyzed, displaces quantitatively

the metal from the complex

 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

Sisay K. 07/09/24
 Complexometric titration …
99

 The freed Mg metal is then directly titrated with a standard

EDTA solution.
 Mn quantitatively displaces Mg from Mg EDTA chelate.

 This displacement takes place because Mn forms a more

stable complex with EDTA.

By this method Ca, Pb, Hg may be determined using

Eriochrome blackT indicator.

Sisay K. 07/09/24
 Complexometric titration …
100

4. Indirect Titration:
 also known as Alkalimetric titration.
 determination of ions such as anions, which do not react with

EDTA chelate.
 Protons from disodium EDTA are displaced by a heavy metal

and titrated with sodium alkali.

e.g. - Barbiturates do not react with EDTA but are quantitatively

precipitated from alkaline solution by mercuric ions as 1:1
complex.

Sisay K. 07/09/24
 Complexometric titration …
101

Applications of Complexometric Titrations

 Determination of various metals like Ca, Mg, Pb, Zn, Al,

Fe, Mn, Cr etc. in different formulations that are official in
I.P.

 also for the determination of Hardness of water.

Sisay K. 07/09/24
 Redox titration
102
 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
(simultaneous loss or gain of electrons) among the reacting ions
in aqueous solutions.

Sisay K. 07/09/24
103

 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 donating
electrons to it.
Example
 Here, the ferrous ions are getting oxidized to ferric ions by

the loss of one electron.

Sisay K. 07/09/24
 Redox titration…
104

 The chlorine gets reduced to chloride ions by gaining electrons

 Further, oxidation and reduction are always found to occur
together in a reaction.

 In other words, electron loss of one substance is always

accompanied by an electron gain on the part of the other and
consequently there are no free electrons in a chemical system.

Sisay K. 07/09/24
 Redox titration…
105
 The relative tendency to accept or lose electrons by any reagent
is measured in terms of their standard reduction potential
values.
 Reduction potential is the measure of how favorable it is for
a compound to gain electrons.
 A high positive value for reduction potential indicates that a
compound is readily reduced and hence is a strong
oxidizing agent.

Sisay K. 07/09/24
 Redox titration…
REDOX TITRATION CURVES
106

 By plotting the redox potential corresponding to different

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

Example: titration of 100 cm3 of 0.1M iron (II) with 0.1 M

cerium (IV) in the presence of dilute sulphuric acid.

Sisay K. 07/09/24
 Redox titration…
107

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.

Sisay K. 07/09/24
 Redox titration…
108

REDOX INDICATORS…
 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.

Sisay K. 07/09/24
 Redox titration…
109

Redox indicators…
 The following table shows the colour of the oxidized and
reduced form of some redox indicators.

Sisay K. 07/09/24
 Redox titration…
110

A. OXIDIMETRIC REAGENTS

i. Permanganate titrations (KMnO4): these are 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

Sisay K. 07/09/24
111

 Potassium permanganate acts as a self-indicator (colorless

to pink)
 The potential equation, when potassium permanganate acts
as an oxidizing agent, is:

Preparation of KMnO4 reagent (read)

Sisay K. 07/09/24
 Redox titration…
112

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
advantages over permanganate.
 Unlike potassium permanganate, potassium dichromate is
available in high purity and is highly stable
Sisay K. 07/09/24
 Redox titration…
113

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
 Potassium dichromate acts as oxidizing agent in acidic medium
only

Sisay K. 07/09/24
 Redox titration…
114

ii. Potassium dichromate…

 The end point in titrations with dichromate ion is generally
detected by using suitable redox indicators such as
diphenylamine, sodium diphenylaminesulphonate and N-
phenylanthranilic acid, etc.

 It can be used in acidic medium to determine most compounds

that can be titrated with KMnO4.
Sisay K. 07/09/24
 Redox titration…
115

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

Advantages
 stable over prolonged periods. They need not be protected
from light.
 not too highly colored to obstruct vision when reading the
meniscus in burettes Sisay K. 07/09/24
 Redox titration…
116

iv. Potassium bromate titrations

 It is also a strong oxidant in acidic medium.
 is a primary standard as the reagent can be obtained in a pure state.
 Its standard solution can be prepared by direct weighing.
 yellowish color due to bromine released from the slight excess
of reagent added…end point
 The end point may also be detected indicators such as methyl
orange, methyl red etc.
Sisay K. 07/09/24
 REDOX TITRATION…
117

iv. Potassium bromate…

 The reagent is used in hydrochloric acid for the direct
determination of arsenic(III), antimony(III), tin(II),
hydrazine, etc.

Sisay K. 07/09/24
REDOX TITRATION…
VI. Iodometric titrations
118
 An oxidation agent is allowed to react in neutral
medium or in acidic medium, with excess of
potassium iodide to liberate free iodine.

 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 Sisay
endK. point.
07/09/24
 REDOX TITRATION…
119

VI. Iodometric titrations…

 Halogen, dichromates, cupric ion, peroxides, etc., can be
estimate by this method.

 Pharmacopoeia-phenol, Methyl hydroxybenzoate, Phenidione

 In general,
 The method in which iodine is used for the determination of reductants is
called iodimetry.
 The method in which iodide is used for the determination of oxidants is
called iodometry.
Sisay K. 07/09/24
 REDOX TITRATION…
120

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.

Sisay K. 07/09/24
 REDOX TITRATION…
121

Common reductimetric reagents

i) Iron
ii) Chromium (II) and Titanium(III)

iii) Sodium Thiosulfate, Na2S2O3

Sisay K. 07/09/24
 Diazotization Titration or Nitrite Titration
122

 Diazotization is used in the analysis of aromatic compounds

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.

Sisay K. 07/09/24
123

 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.

 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.

Sisay K. 07/09/24
 Diazotization Titration…
124
 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.

Sisay K. 07/09/24
 Application of diazotization titration
125

 Analysis of sulphonamides by diazotization 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:

Sisay K. 07/09/24
 Exersice
126

 What is the ratio of ephedrine to ephedrine HCl (pKa = 9.6) in

the intestinal tract at pH 8.0? and/or 2. What is the percent
ionization of ephedrine HCl in the intestinal tract buffered at
pH 8?

Sisay K. 07/09/24
127

Thank You!!

Sisay K. 07/09/24