Volumetric Methods of Analysis Titrimetric Analysis

Introduction

The term titrimetric analysis refers to quantitative chemical

analysis carried out by determining the volume of a solution of
accurately known concentration which is required to react
quantitatively with a measured volume of a solution of a
substance to be determined

The solution of accurately known concentration is called

standard solution
Introduction

The term volumetric analysis was used for this form of

quantitative determination but it has now been replaced by
titrimetric analysis.

In titrimetric analysis the reagent of known concentration is

called titrant and the substance being titrated is termed the
titrand
 Introduction

The standard solution is usually added from a long graduated tube called burette.

The process of adding the standard solution until the reaction is just complete is
termed titration.

The point at which this occurs is called equivalence point or the theoretical (or
stoichiometric) end point.

The completion of the titration is detected by some physical change, produced by

the standard solution itself or, more usually, by the addition of an auxiliary reagent,
known as an indicator
 Introduction

 Alternatively some other physical measurement may be used.

After the reaction between the substance and the standard solution is
practically complete,

the indicator should give a clear visual change (either a color change
or the formation of turbidity) in the liquid being titrated
 Introduction

 The point at which this occurs is called the end point of the titration.

 In the ideal titration the visible end point will coincide with the
stoichiometric or theoretical end point.

 In practice, however, a very small difference usually occurs this

represents the titration error.

 The indicator and experimental conditions should be so selected that

the difference between the visible end point and equivalence point is as
small as possible.
Introduction

●There must be a simple reaction which can be

expressed by a chemical equation; the substance to
be determined should react completely with the
reagent in stoichiometric or equivalent point

●The reaction should be relatively fast. (Most ionic

reaction satisfy this condition.)

●In some cases the addition of a catalyst may be

necessary to increase the speed of a reaction
Introduction

●There must be an alteration in some physical or

chemical property of the solution at the equivalence
point

●An indicator should be available which, by a change

in physical properties (color or formation of a
precipitate), should sharply define the end point of the
reaction
 Definition of some terms

● Titration
Titration is the process in which the standard reagent is added to a solution of an analyte until the
reaction between the analyte and reagent is complete

●Equivalence point and End point

The equivalence point of a titration is a theoretical point that can not be determined
experimentally. Instead, we can only estimate its position by observing some physical change
associated with the condition of equivalence. This change is called the end point for titration

●Titration error
The difference between the observed end point and the true equivalence point in a titration.
 Definition of some terms

Indicators
● Indicators
are often added to analyte solution in order to
give an observable physical change (end point) at or
near the equivalence point

● In other words indicator is a compound having a

physical property (usually colour) that changes abruptly
near the equivalence point of a chemical reaction
 Primary standard

●A primary standard is a highly purified compound that

serve as a reference material in all volumetric method

●The accuracy of method is critically dependent on the

properties of this compound

●Important requirements for primary standard are:

 Characteristics of Primary standard

 High purity
 Stability toward air
 Absence of hydrated water
 Ready availability at modest cost
 Reasonable solubility in titration medium
 Reasonably large molar mass so that the relative error associated with
weighing the standard is minimized
 Secondary standard

●A secondary standard is a compound whose purity has been

established by chemical analysis and serves as the reference material for
titrimetric method of analysis

●Compound such as sodium hydroxide or hydrochloric acid cannot be

considered as primary standard since their purity is quite variable
 Secondary standard

So for instance sodium hydroxide solution must be standardized

against potassium hydrogen phthalate (primary standard),which is
available in high purity

The standardized sodium hydroxide solution (secondary standard)

may be used to standardize solutions
 Standard solution

Standard solution is the reagent of exactly known concentration that is

used in titrimetric analysis.

Standard solutions play a central role in all titrimetric method of

analysis

Therefore we need to consider the desirable properties for such

solutions, how they are prepared and how their concentration are
expressed
 Desirable properties of standard solutions

The ideal standard solution for titrimetric method will:

● be sufficiently stable so that it is only necessary to determine the
concentration once

●React rapidly with the analyte so that the time required between additions of
reagent is minimized

●React more or less completely with the analyte so that satisfactory end
points are realized.

●Undergo a selective reaction with the analyte that can be described by

Classification of
reaction in
titrimetric analysis
Neutralization reaction or acidimetry and alkalimetry

●These include the titration of free bases, or those formed from salts of weak
acids by hydrolysis with a standard acid (acidimetry),

●and the titration of free acids, or those formed by the hydrolysis of salts or
weak bases, with a standard base (alkalimetry)

●The reaction involve the combination of hydrogen and hydroxide ions to

form water

●Also under this heading must be included titrations in non-aqueous solvents,

most of which involve organic compounds
B. Precipitation reaction

●These depend upon the combination of ions to form a simple

precipitate as in the titration of silver ion with solution of chloride No
change in oxidation state occurs.
C. Complex formation reaction

●These depend upon the combination of ions, other than hydrogen or

hydroxide ion, to form a soluble slightly dissociated ion or compound,

●as in the titration of a solution of a cyanide with silver nitrate

● Ethylendiaminetera-acetic acid, largely as the disodium salt of EDTA,

is a very important reagent for complex formation titration and has
become one of the most important reagents used in titrimetric analysis
D. Oxidation-reduction reaction

●Under this heading are included all reactions involving change in

oxidation number or transfer of electrons among the reactive
substance

●The standard solutions are either oxidizing or reducing agents

 Titration Curves

To find the end point we monitor some

property of the titration reaction that has a
well- defined value at the equivalence point

For example, the equivalence point for a

titration of HCl with NaOH occurs at a pH
of 7.0

We can find the end point, therefore, by

monitoring the pH with a pH electrode or by
adding an indicator that changes color at a
pH of 7.0
 Titration Curves

A titration curve provides us with a visual

picture of how a property, such as pH,
changes as we add titrant

 We can measure this titration curve

experimentally by suspending a pH
electrode in the solution containing the
analyte, monitoring the pH as titrant is
added

We can also calculate the expected titration

curve by considering the reactions
 Titration Curves

 However we arrive at the titration

curve, we may use it to evaluate an
indicator's likely titration error

 For example, the titration curve in the

above figure shows us that an end point
pH of 6.8 produces a small titration error

 Stopping the titration at an end point

pH of 11.6, on the other hand, gives an
unacceptably large titration error.
 Types of Titration curves

Sigmoidal curve - a "z" or "s"-shaped

curve where the y axis is a p-function
of the analyte (or the reagent reacted
with the analyte during titration) or
the potential of an ion-specific
electrode
 Types of Titration curves

Linear-segment curve - a curve generally

consisting of two line segments that intersect at an
angle
 Applications of Titrimetry in Pharmaceutical Analysis

Applications
• Provide standard pharmacopoeial methods for the assay of
unformulated drugs and excipients and some formulated drugs, e.g.
those that lack a strong chromophore

• Used for standardizations of raw materials and intermediates used in

drug synthesis in industry
 Applications of Titrimetry in Pharmaceutical Analysis

● Suppliers of raw materials may provide these materials at a specified

purity which has been assayed titrimetrically to a pharmacopoeial
standard.

● Certain specialist titrations, such as the Karl Fischer titration used to

estimate water content, are widely used in the pharmaceutical industry
Applications of Titrimetry in Pharmaceutical Analysis

Advantages

 Capable of a higher degree of Limitations

precision and accuracy than  Non-selective
instrumental methods of analysis  Time-consuming if not automated and
 The methods are generally robust require a greater level of operator skill
than routine instrumental methods
 Analyses can be automated
 Require large amounts of sample and
 Cheap to perform and do not require reagents
specialized apparatus.  Reactions of standard solutions with
 They are absolute methods and are the analyte should be rapid and
not dependent on the calibration of complete
an instrument.
 Titrations Based on Acid-Base Reactions

●The earliest acid-base titrations involved the determination of the

acidity or alkalinity of solutions, and the purity of carbonates and
alkaline earth oxides

●Various acid-base titration reactions, including a number of scenarios of

base in the burette, acid in the reaction flask, and vice versa, as well as

●various monoprotic and polyprotic acids titrated with strong bases and
various weak monobasic and polybasic bases titrated with strong acids
 Titrations Based on Acid-Base Reactions

A monoprotic acid is an acid that has only one hydrogen ion (or
proton) to donate per formula

Examples are hydrochloric acid, HCl, a strong acid, and acetic acid,
HC2H302, a weak acid

A polyprotic acid is an acid that has two or more hydrogen ions to

donate per formula.

Examples include sulfuric acid, H2S04, a diprotic acid, and

 Titrations Based on Acid-Base Reactions

A monobasic base is one that will accept just one hydrogen ion per
formula. Examples include sodium hydroxide, NaOH, a strong base;
ammonium hydroxide, NH4OH, a weak base;

 and sodium bicarbonate, NaHCO3, a weak base. A polybasic base is

one that will accept two or more hydrogen ions per formula.

Examples include sodium carbonate, Na2CO3, a dibasic base, and

sodium phosphate, Na3PO4, a tribasic base
 Acid-Base Titration Curves

In the overview to the titration we noted that the experimentally

determined end point should coincide with the titration’s equivalence
point.

For an acid-base titration, the equivalence point is characterized by a

pH level that is a function of the acid-base strengths and concentrations
of the analyte and titrant
 Acid-Base Titration Curves

The pH at the end point, however, may or may not correspond to

the pH at the equivalence point

To understand the relationship between end points and

equivalence points we must know how the pH changes during a
titration

Inthis section we will learn how to construct titration curves for

several important types of acid-base titrations
Titrating Strong Acids and Strong Bases

 For our first titration curve let’s consider the titration of 50.0 mL of 0.100 M
HCl with 0.200 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)
►The first task in constructing the titration curve is to calculate the
volume of NaOH needed to reach the equivalence point.
At the equivalence point we know from reaction above that
Titrating Strong Acids and Strong Bases

 Moles HCl = moles NaOH

 or
 Ma V a = Mb V b
where the subscript ‘a’ indicates the acid, HCl, and the subscript ‘b’
indicates the base, NaOH. The volume of NaOH needed to reach
the equivalence point, therefore, is

 Ma V a (0.100 M)(50.0 mL)

 Veq = Vb = --------------- = = 25.0 mL
Mb (0.200 M)
Titrating Strong Acids and Strong Bases

Before the equivalence point, HCl is present in excess and the pH is determined
by the concentration of excess HCl.

Initially the solution is 0.100 M in HCl, which, since HCl is a strong acid,
means that the pH is

pH = -log[H3O+] = -log[HCl] = -log(0.100) = 1.00

Titrating Strong Acids and Strong Bases

 The equilibrium constant for reaction is (Kw)–1, or 1.00 × 1014. Since this is
such a large value we can treat reaction as though it goes to completion. After
adding 10.0 mL of NaOH, therefore, the concentration of excess HCl is
moles excess HCl MaVa - MbVb
 [HCl] = ---------------------------- = ------------------------
total volume Va + Vb

(0.100 M)(50.0 mL) - (0.200 M)(10.0 mL)

= ------------------------------------------------------------ = 0.050 M
50.0 mL + 10.0 mL pH = 1.30
Titrating Strong Acids and Strong Bases

 At the equivalence point the moles of HCl and the moles of NaOH are equal. Since
neither the acid nor the base is in excess, the pH is determined by the dissociation of
water.
 Kw = 1.00 × 10-14 = [H3O+][OH–] = [H3O+]2
 [H3O+] = 1.00 × 10–7 M
 Thus, the pH at the equivalence point is 7.00.

 Finally, for volumes of NaOH greater than the equivalence point volume, the pH is
determined by the concentration of excess OH–. For example, after adding 30.0 mL of
titrant the concentration of OH– is
Titrating Strong Acids and Strong Bases

moles excess NaOH MbVb - MaVa

 [OH] = --------------------------------- = -----------------------
total volume Va + Vb

(0.200 M)(30.0 mL) - (0.100 M)(50.0 mL)

= = 0.0125 M
50.0 mL + 30.0 mL

 To find the concentration of H3O+, we use the Kw expression

Kw 1.00 × 10-14
 [H O+] = ---------- = ------------------ = 8.00 × 10-13
3

[OH-] 0.0125

giving a pH of 12.10.
 Titrating Strong Acids and Strong Bases

 To find the concentration of H 3O+,

moles excess NaOH M b V b - Ma V a we use the Kw expression
 [OH] = --------------------- = ---------------
total volume Va + Vb Kw 1.00 × 10-14
 [H3O+] = -------- = -----------
(0.200 M)(30.0 mL) - (0.100 M)(50.0 mL) =8.00 × 10-13
= 50.0 mL + 30.0 mL [OH-] 0.0125

= 0.0125 M giving a pH of 12.10.

D Data for Titration of 50.00 mL of 0.100 M HCI
with 0.0500 M NaOH
Volume (mL) of Titrant pH
0.00 1.00
5.00 1.14
10.00 1.30
15.00 1.51
20.00 1.85
22.00 2.08
24.00 2.57
25.00 7.00
26.00 11.42
28.00 11.89
30.00 12.50
35.00 12.37
40.00 12.52
45.00 12.62
50.00 12.70
Titrating a Weak Acid with a Strong Base

For this example let’s consider the titration of 50.0 mL of 0.100 M acetic acid,
CH3COOH, with 0.100 M NaOH.

Again, we start by calculating the volume of NaOH needed to reach the

equivalence point; thus
Titrating a Weak Acid with a Strong Base

 Moles CH3COOH = Moles NaOH

 MaVa = MbVb

MaVa (0.100 M)(50.0 mL)

 Veq = Vb = ---------------- = = 50.0 mL
Mb (0.100 M)

Titrating a Weak Acid with a Strong Base

●Before adding any NaOH the pH is that for a solution of 0.100 M acetic acid.

●Since acetic acid is a weak acid, we calculate the pH using this method
CH₃COOH(aq) + H₂O(l) = H₃O⁺(aq) +
CH₃COO⁻(aq)

[H₃O⁺][CH₃COO⁻] (x)(x)
Ka = -------------------- ----- = ------------- = 1.75 × 10 ⁻⁵
[CH₃COOH] 0.100 - x

x = [H₃O⁺] = 1.32 × 10⁼3