CHE 401 : ANALYTICAL CHEMISTRY

MODULE
5
TITRIMETRIC METHOD OF ANALYSIS

INTRODUCTION
Analytical Chemistry used titration to determine acids, bases, ixidants, reductants, metal ions and
other species. This was based on the reaction between the analyte and the standard reagents or the
so-called titrant. The volume or the mass of the titrant needed to react essentially completely with
the analyte is determine to stoichiometrically calculate the amount of analyte. The equivalence and
the end point of the titration is being determine which indicates complete reaction.
This module will provide the students the basic principle of titrimetric method, precipitation
titrimetry and neutralization titration. It will describe the regions of pre-equivalence, equivalence
and post equivalence and how it relates to the end point during the experiment. Various chemical
indicator will be discussed to describe the behaviour of reaction and the physical change in colour
upon reaching the equivalence point. The students will learn on how to generate the titrations
curves and learn to interpret experimental results in titration.

INTENDED LEARNING OUTCOMES

At the end of the module, the following learning outcomes are expected to be acquired by the
students:
1. Understand the concepts and be familiar with the steps and techniques employed in
titrimetric method of analysis.
2. Execute calculation techniques used in stoichiometry and titrimetric method of analysis.
3. Acquire skills in laboratory technique required to perform and plan chemical analysis and
systematically collect and interpret data obtained in quantitative analytical process.
4. Understand the current trends and analytical techniques in titrimetric method of analysis.

CONTENT OVERVIEW
Indicative contents included the following topics:
1. Gravimetric method
2. Precipitates and precipitating agents
3. Calculations involved in gravimetric analysis
4. Application of gravimetric analysis

END OF THE MODULE TEST

The following are the assessment provided to evaluate students level of understanding after the
discussion of the modules:

Coursework (100 points )

Solving problems involving gravimetric method of analysis.

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Table of Contents

MODULE 5. TITRIMETRIC METHOD OF ANALYSIS ................................................................... 4

5.1 Some Terms Used in Volumetric Titrimetry ........................................................................... 4

5.1.1 Standard Solution ................................................................................................................ 4

5.1.2 Equivalence Points and End Points ........................................................................................ 4

5.1.3 Indicators ................................................................................................................................ 5

5.1.4 Primary Standards .................................................................................................................. 5

5.1.5 Standard Solutions ................................................................................................................. 5

5.2 Volumetric Calculations ........................................................................................................... 6

5.3 GRAVIMETRIC TITRIMETRY ............................................................................................ 9

5.4 TITRATION CURVES .......................................................................................................... 10

5.4.1 Types of Titration Curves ..................................................................................................... 11

5.4.2 Concentration Changes During Titration .............................................................................. 11

5.5 PRECIPITATION TITRIMETRY ........................................................................................ 12

5.5.1 Precipitation Titration Curves Involving Silver Ion ............................................................. 12

5.6 WAYS OF PERFORMING TITRATION ............................................................................ 15

5.7 ANALYSIS OF THE SAMPLE ............................................................................................. 15

5.7.1 Sources of Error in sample analysis ..................................................................................... 16

5.8 INDICATORS FOR ARGENTOMETRIC TITRATIONS ................................................. 17

5.8.1 Chromate Ion; The Mohr Method ........................................................................................ 17

5.8.2 Adsorption Indicators: The Fajans Method .......................................................................... 18

5.8.3 Iron(III) Ion; The Volhard Method ....................................................................................... 19

5.9 APPLICATIONS OF STANDARD SILVER NITRATE SOLUTIONS ................................. 19

5.10 PRINCIPLES OF NEUTRALIZATION TITRATION ......................................................... 21

5.10.1 Solutions and Indicators for Acids/Bases Titrations ............................................................ 21

5.10.2 Titration errors with Acid/Base Indicators ......................................................................... 23

5.10.3 Variables that Influence the Behavior of Indicators ............................................................. 23

5.10.3 Titration of Strong Acids and Strong Bases ........................................................................ 23

5.10.4 Titrating a Strong Base with a Strong Acid .......................................................................... 26

5.10.5 Titration Curves for Weak Acids ......................................................................................... 28

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5.10.6 Titration Curves for weak Bases ........................................................................................... 31

5.11 APPLICATION OF NEUTRALIZATION TITRATION .................................................... 35

5.11.1 Preparation of Standard Acid Solutions ................................................................................ 35

5.11.2 The Standardization of Acids ............................................................................................... 36

5.11.3 The Standardization of Bases ............................................................................................... 39

5.11.4 Typical Applications of Neutralization Titrations ................................................................. 39

5.12. End of Module Test ................................................................................................................... 47

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MODULE 5. TITRIMETRIC METHOD OF ANALYSIS

Titrimetry includes a group of analytical methods that are based on determining the quantity of a
reagent of known concentration that is required to react completely with the analyte, the reagent
may be a standard solution of a chemical or an electric current of know magnitude.

 Volumetric titrimetry is a type of titrimetry in which the volume of a standard reagent

is the measured quantity.
 Coulometric titrimetry is a type of titrimetry in which the quantity of charge III
coulombs required to complete a reaction with the analyteis the measured quantity

5.1 Some Terms Used in Volumetric Titrimetry

5.1.1 Standard Solution

A standard solution (or a standard titrant) is a reagent of known concentration that is used to carry
out a titrimetric analysis. A titration is performed by slowly adding a standard solution from a buret
or other liquid-dispensing device to a solution of the analyte until the reaction between the two is
judged complete. The volume or mass of reagent needed to complete the titration is determined
from the difference between the initial and final readings.

It is sometimes necessary to add an excess of the standard titrant and then determine the excess
amount by back-titration with a second standard titrant. For example, the amount of phosphate in
a sample can be determined by adding a measured excess of standard silver nitrate to a solution of
the sample, which leads to the formation of insoluble silver phosphate:

Ag+ + PO43- à Ag3PO4(s)

The excess silver nitrate is then back-titrated with a standard solution of potassium thiocyanate:

Ag+ + SCN- à AgSCN(s)

Here, the amount of silver nitrate is chemically equivalent to the amount of phosphate ion plus the
amount of thiocyanate used for the back-titration.

5.1.2 Equivalence Points and End Points

The equivalence point in a titration is a theoretical point reached when the amount of added titrant
is chemically equivalent to the amount of analyte in the sample.

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We cannot determine the equivalence point of a titration 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 the titration. Every effort is made to
ensure that any volume or mass difference between the equivalence point and the end point is
small. Such differences do exist, however, as a result of inadequacies in the physical changes
and in our ability to observe them. The difference in volume or mass between the equivalence
point and the end point is the titration error.

5.1.3 Indicators

Indicators are often added to the analyte solution to produce an observable physical
change (the end point) at or near the equivalence point. Large changes in the relative concentration
of analyte or titrant occur in the equivalence-point region. These concentration changes cause the
indicator to change in appearance. Typical indicator changes include the appearance or
disappearance of a color, a change in color, or the appearance or disappearance of turbidity. As an
example, the indicator used in the precipitation titration of silver ion with potassium thiocyanate
is a small amount of ferric chloride which reacts with thiocyanate ions to give a red color. The
indicator reaction is

Fe3 + SCN- à FeSCN2-

red

5.1.4 Primary Standards

A primary standard is a highly purified compound that serves as a reference material in

volumetric and mass titrimetric methods. The accuracy of a method is critically dependent on the
properties of this compound. Important requirements for a primary standard are the following:

1. High purity. Established methods for confirming purity should be available.

2. Atmospheric stability.
3. Absence of hydrate water so that the composition of the solid does not change with
variations in humidity.
4. Modest cost.
5. Reasonable solubility in the titration medium.
6. Reasonably large molar mass so that the relative error associated with weighing the
standard is minimized.
5.1.5 Standard Solutions

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Standard solutions play a central role in all titrimetric methods of analysis. Therefore, we
need to consider the desirable properties for such solutions, how they are prepared and how their
concentrations are expressed. The ideal standard solution for a titrimetric method will

1. be sufficiently stable so that it is necessary to determine its concentration only once;

2. react rapidly with the analyte so that the time required between additions of reagent
is minimized:
3. react more or less completely with the analyte so that satisfactory end points are
realized; and
4. undergo a selective reaction with the analyte that can be described by a balanced
equation.

Few reagents meet all these ideals perfectly.

The accuracy of a titrimetric method can be no better than the accuracy of the concentration
of the standard solution used in the titration. Two basic methods are used to establish the
concentration of such solutions.

1. Direct method, in which a carefully weighed quantity of a primary standard is dissolved in

a suitable solvent and diluted to an exactly known volume in a volumetric flask.
2. By standardization, in which the titrant to be standardized is used to titrate
a. a weighed quantity of a primary standard,
b. a weighed quantity of a secondary standard, or
c. a measured volume of another standard solution.

A titrant that is standardized against a secondary standard or against another standard

solution is sometimes referred to as a secondary-standard solution. The concentration of a
secondary-standard solution is subject to a larger uncertainty than is that of a primary-standard
solution. If there is a choice, then, solutions are best prepared by the direct method. Many reagents
lack the properties required for a primary standard, however, and therefore require standardization.

5.2 Volumetric Calculations

Calculating the Molarity of Standard Solutions

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The following three examples illustrate how the concentrations of volumetric reagents are
computed.

EXAMPLE 5.1
Describe the preparation of 2.000 L of 0.0500 M AgNO3 (169.87 g/mol) from the primary-
standard-grade solid.

Since the volume is in liters, we base our calculations on the mole rather than the millimole.
Thus, to obtain the amount of AgNO3 needed, we write

Amount AgNO3 = Vsoln (L) x C AgNO3 (mol/L)

= 2.0 L x (0.050 mol Na2CO3/1L)
= 0.1000 mol AgNO3

To obtain the mass of AgNO3

Mass AgNO3 = 0.10 mol AgNO3 (169.87 g AgNO3/mol AgNO3)
= 16.98 g AgNO3
Therefore, the solution is prepared by dissolving 16.98 g AgNO 3 in water and diluting to exactly
2.0L.

EXAMPLE 5.2
A standard 0.0100 M solution of Na+ is required to calibrate a flame photometric method to
determine the element. Describe how 500 mL of this solution can be prepared from primary
standard Na2CO3 (105.99 g/ml.)

We wish to compute the mass of reagent required to give a species molarity of 0.0100. Here, we
will use millimoles, since the volume is in milliliters. Because Na 2CO3 dissociates to give two Na+
ions, we can write that the number of millimoles of Na 2CO3 needed is:

0.0100 𝑚𝑚𝑜𝑙 1 𝑚𝑚𝑜𝑙 𝑁𝑎2 𝐶𝑂3

𝐴𝑚𝑜𝑢𝑛𝑡 𝑁𝑎2 𝐶𝑂3 = 500 𝑚𝐿 𝑥 x = 2.50 mmol
𝑚𝑙 2 𝑚𝑚𝑜𝑙 𝑁𝑎

From the definition of millimole, we write

0.10599 𝑔 𝑁𝑎2 𝐶𝑂3
𝑀𝑎𝑠𝑠 𝑁𝑎2 𝐶𝑂3 = 2.50 𝑚𝑚𝑜𝑙 𝑁𝑎2 𝐶𝑂3 𝑥 = 0.265 𝑔𝑟𝑎𝑚𝑠
𝑚𝑚𝑜𝑙 𝑁𝑎2 𝐶𝑂3

The solution is therefore prepared by dissolving 0.265 g of Na2CO3 in water and diluting to 500mL.
EXERCISE 5.1

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A 50.00-mL portion of an HCI solution required 29.71 mL of 0.01963 M Ba(OH)2 to reach an end
point with bromocresol green indicator. Calculate the molarity of the HCl.

EXERCISE 5.2
Titration of 0.2121 g of pure Na2C2O4 (134.00 g/mol) required 43.31 mL of KMnO4. What is the
molarity of the KMnO4 solution? The chemical reaction is

2MnO4- + 5C2O42- + 16H+ à 2Mn2+ + 10CO2 + 8H2O

EXAMPLE 5.3
A 0.8040-g sample of an iron ore is dissolved in acid. The iron is then reduced to Fe 2+ and titrated
with 47.22 mL of 0.02242 M KMnO4 solution. Calculate the results of this analysis in terms of (a)
% Fe (55.847 g/mol) and (b) % Fe3O4 (231.54 g/mol). The reaction of the analyte with the reagent
is described by the equation

MnO4 + 5Fe2+ + 8H+ Mn2+ + 5Fe3+ + 4H2O

𝑚𝑎𝑠𝑠 𝐹𝑒
(a) % 𝐹𝑒 = 𝑥 100%
𝑚𝑎𝑠𝑠 𝑖𝑟𝑜𝑛 𝑜𝑟𝑒

% 𝐹𝑒
0.02242 𝑚𝑚𝑜𝑙 𝐾𝑀𝑛𝑂4 5 𝑚𝑚𝑜𝑙 𝐹𝑒 55.85 𝑚𝑔 𝐹𝑒
47.22 𝑚𝐿 𝐾𝑀𝑛𝑂4 [ 𝑚𝐿 𝐾𝑀𝑛𝑂4
][
1 𝑚𝑚𝑜𝑙 𝐾𝑀𝑛𝑂4
][
𝑚𝑜𝑙
]
= 𝑥 100%
0.8040 𝑔 𝑖𝑟𝑜𝑛 𝑜𝑟𝑒 ∗ 1000𝑚𝑔/𝑔
% Fe = 36.77%

𝑚𝑎𝑠𝑠 𝐹𝑒3 𝑂4
(b) % 𝐹𝑒3 𝑂4 = 𝑥 100%
𝑚𝑎𝑠𝑠 𝑖𝑟𝑜𝑛 𝑜𝑟𝑒

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0.02242 𝑚𝑚𝑜𝑙 𝐾𝑀𝑛𝑂4 5 𝑚𝑚𝑜𝑙 𝐹𝑒 1 𝑚𝑚𝑜𝑙 𝐹𝑒3 𝑂4 231.45 𝑚𝑔𝐹𝑒3 𝑂4

47.22 𝑚𝐿 𝐾𝑀𝑛𝑂4 [ ][ ][ ][ ]
𝑚𝐿 𝐾𝑀𝑛𝑂4 1 𝑚𝑚𝑜𝑙 𝐾𝑀𝑛𝑂4 3 𝑚𝑚𝑜𝑙 𝐹𝑒 1 𝑚𝑚𝑜𝑙 𝐹𝑒3 𝑂4
% 𝐹𝑒3 𝑂4 = x 100%
0.8040 𝑔 𝑖𝑟𝑜𝑛 𝑜𝑟𝑒∗1000 𝑚𝑔/𝑔

% 𝐹𝑒3 𝑂4 = 50.81%

EXERCISE 5.3
A 100 mL sample of brackish water was made ammoniacal, and the sulfide it contained was titrated
with 16.47 mL of 0.02310 M AgNO3. The analytical reaction is

2Ag+ + S2- Ag2S(s)

Calculate the concentration of H2S in the water in parts per million.

EXERCISE 5.4
The phosphorus in a 4.258-g sample of a plant food was converted to PO43 and precipitated as
Ag3PO4 through the addition of 50.00 mL of 0.0820 M AgNO3. The excess AgNO3 was back-
titrated with 4.86 mL of 0.0625 M KSCN. Express the results of this analysis in terms of % P 2O5.

The chemical reactions are:

P2O5 + 9H2O  2PO43- + 6H3O+

2PO43- + 6Ag  Ag3PO4

Ag+ + SCN-  AgSCN

5.3 GRAVIMETRIC TITRIMETRY

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Weight or gravimetric titrimetry differs from its volumetric counterpart in that the moss of titrant
is measured rather than the volume. Thus, in a weight titration, a balance and a weighable solution
dispenser are substituted for a buret and its markings. Weight titrimetry actually predates
volumetric titrimetry by more than 50 years." With the advent of reliable burets, however, weight
titrations were largely supplanted by volumetric methods because the former required relatively
elaborate equipment and were tedious and time consuming. The availability of sensitive, low-cost,
top-loading digital analytical balances and convenient plastic solution dispensers has changed this
situation completely, and weight titrations can now be performed more easily and rapidly than
volumetric titrations.

CALCULATIONS ASSOCIATED WITH WEIGHT TITRATIONS

The most convenient unit of concentration for weight titrations is weight molarity, Mw,
which is the number of moles of a reagent in one kilogram of solution or the number of millimoles
in one gram of solution. Thus, aqueous 0.1 M; NaCI contains 0.1 mol of the salt in I kg of solution
or 0.1 mmol in I g of the solution. The weight molarity cw(A) of a solution of a solute A is
computed by means of either of two equations that are analogous to Equation 5.1

𝑛𝑜.𝑚𝑜𝑙 𝐴 𝑛𝑜.𝑚𝑚𝑜𝑙 𝐴
𝑊𝑒𝑖𝑔ℎ𝑡 𝑚𝑜𝑙𝑎𝑟𝑖𝑡𝑦 = = (5.1)
𝑛𝑜.𝑘𝑔 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑛𝑜.𝑔 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

𝒏𝑨
𝑪𝒘(𝑨) = 𝒎𝒔𝒐𝒍𝒏

5.4 TITRATION CURVES

An end point is an observable physical change that occurs near the equivalence point of a titration.
The two most widely used end points involve

1) changes in color due to the reagent, the analyte, or an indicator and

2) a change in potential of an electrode that responds to the concentration of the
reagent or the analyte.

To understand the theoretical basis of end points and the sources of titration errors, we calculate
the data points necessary to construct titration curves for the systems under consideration. Titration
curves plot reagent volume on the horizontal axis and some function of the analyte or reagent
concentration on the vertical axis.

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5.4.1 Types of Titration Curves

1. SIGMOIDAL CURVE- p-Function of the analyte is plotted as a function of reagent

volume. It offers the advantage of speed and convenience.

2. LINEAR SEGMENT CURVE– The vertical axis represent the instrument reading that is
directly proportional to the concentration of the analyte or the reagent.

Fig 5.1 (a) Sigmoidal Curve (b) Linear Segment Curve

5.4.2 Concentration Changes During Titration

The equivalence point in a titration is characterized by major changes in the relative concentrations
of reagent and analyte. Table 5.1 illustrates this phenomenon. The data in the second column of
the table show the silver ion concentration as a 50-mL aliquot of a 0.1000 M solution of silver
nitrate acid is titrated with a0.1000 M solution of potassium thiocyanate. The precipitation reaction
is described by the equation Ag+ + SCN-  AgSCN(s)

TABLE 5.1.
Concentration Change during the Titration of 50.00 mL of 0.1000 MAgNO3 with 0.1000
M KSCN

Volume of [Ag+] [Ag+] Milliliters KSCN to Cause

pAg pSCN
Milliliters KSCN mmol/L a Tenfold Decrease in [Ag+]

0.00 1.0 X 10-1 1.0

40.91 1.0 X 10-2 40.91 2.0 10.0
49.01 1.0 X 10-3 8.10 3.0 9.0
49.90 1.0 X 10-4 0.89 4.0 8.0
49.99 1.0 X 10-5 0.09 5.0 7.0
50.00 1.0 X 10-6 0.01 6.0 6.0
50.01 1.0 X 10-7 0.01 7.0 5.0
50.10 1.0 X 10-8 0.09 8.0 4.0
51.01 1.0 X 10-9 0.91 9.0 3.0
61.11 1.0 X 10-10 10.10 10.0 2.0

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Fig. 5.2 Titration curve of 50mL of 0.1000 M AgNO3 with

0.1000 KSCN

5.5 PRECIPITATION TITRIMETRY

Precipitation titrimetry, which is based on reactions that yield ionic compounds of limited
solubility, is one of the oldest analytical techniques, dating back to the mid- 1800s. Because of the
slow rate of formation of most precipitates, however, there are only a few precipitating agents that
can be used in titrimetry, By far the most widely used and most important precipitating reagent is
silver nitrate, which is used for the determination of the halides, the halide-like anions (SCN-, CN-
, CNO-), mercaptans fatty acids, and several divalent and trivalent inorganic anions. Titrimetric
methods based on silver nitrate are sometimes called argentometric methods. In this text, we limit our
discussion of precipitation titrimetry to argentometric methods.

5.5.1 Precipitation Titration Curves Involving Silver Ion

The most common method of determining the halide ion concentration of aqueous solutions is
titration with a standard solution of silver nitrate. The reaction product is solid silver halide. A
titration curve for this method usually consists of a plot of pAg versus the volume of silver nitrate
added. To construct titration curves, three types of calculations are required, each of which
corresponds to a distinct stage in the reaction:
(I) pre-equivalence,
(2) equivalence and
(3) postequivalence.

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Example 5.5 demonstrates how pAg is determined for each of these stages.

EXAMPLE 5.5
Perform calculations needed to generate a titration curve for 50.00 mL of 0.0500 M NaCl with
0.1000 M AgN03 (for AgCI, Ksp = 1.82 X 10-10).

Reaction: Ag + (aq) + Cl-(aq) ⇌AgCI(s)

TABLE 5.2. Changes in pAg in the Titration of Cl= With Standard AgN03
50.00 mL of 0.00500 M
50.00 mL of 0.0500 M NaCl
Volume of AgN03 NaCl with 0.01000 M
with 0.1000 M AgN03
AgN03
10.00 8.14 7.14
20.00 7.59 6.59
24.00 6.87 5.87
25.00 4.87 4.87
26.00 2.88 3.88
30.00 2.20 3.20
40.00 1.78 2.78

The Effect of Concentration on Titration Curves

The effect of reagent and analyte concentrations on titration curves was shown by the two sets of
data in Table 5.2 and the two titration curves in Figure 5.3. With 0.1 M AgN03 (Curve A), the
change in pAg in the equivalence-point region is large.

With the 0.01 M reagent, the change is markedly less but still pronounced. Thus, an indicator for
Ag+ that produces a signal in the 4.0 to 6.0 pAg range should give a minimum error for the stronger
solution. For the more dilute chloride solution, the change in pAg in the equivalence-point region
would be too small to be detected precisely with a visual indicator.

The Effect of Reaction Completeness on Titration Curves

Figure 5.4 illustrates the effect of solubility product on the sharpness of the end point in titrations
with 0.1 M silver nitrate. Clearly, the change in pAg at the equivalence point becomes greater as
the solubility products become smaller, that is, as the reaction between the analyte and silver nitrate
becomes more complete. By careful choice of indicator - one that changes color in the region of
pAg from 4 to 6 - titration of chloride ion should be possible with a minimal titration error. Note
that ions forming precipitates with solubility products much larger than about 10 -10 do not yield
satisfactory end points

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Fig. 5.3 Titration Curves fo 50.0 mL of 0.0500M NaCl with 0.10 M AgNO3, and B, 50.00 mL of
0.0500 M NaCl with 0.010M AgNO3

Fig. 5.4. Effect of reaction completeness on precipitation titration curves. For each curve,
50.0mL of a 0.050M solution of the anion was titrated with 0.100 M AgNO3. Note that smaller
values of Ksp give much sharper breaks at the end point.

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5.5.2 Three Types of End Point Encountered With Titration With Silver.

1. POTENTIOMETRIC END POINT – obtained by measuring the potential between a

silver electrode and a reference electrode whose potential is constant and independent of
the added reagent.

2. AMPEROMETRIC ENDPOINT – the current generated between pair of silver

microelectrode in the solution of analyte is measured and plotted as a function of reagent
volume.

3. CHEMICAL INDICATOR – end point usually consist of a color change, or occasionally

the appearance or disappearance of turbidity in the solution being titrated. The
requirements for the indicator for the precipitation titration are that
a) The color change should occur over limited range in p-function of the reagent or
the analyte
b) The color change should takes place within the steep portion of the titration curve
for the analyte.

5.6 WAYS OF PERFORMING TITRATION

1. Direct titration – the analyte reacts with the standard solution directly

2. Back titration – an excess standard solution is added and the excess is determined by the
addition of another standard solution.
3. Replacement titration – the analyte is converted to a product chemically related to it and
the product of such reaction is titrated with a standard solution.

5.7 ANALYSIS OF THE SAMPLE

Required Steps

1. Preparation of standard solution

2. Titration of the sample
a. Dead stop end point
b. Past the end point followed by back titration

3. Computation can be expressed in

a. M, N

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b. Weight of the substance present

c. % of the given constituent in the sample

5.7.1 Sources of Error in sample analysis

1. Loss of sample or solution by spilling in weighing, spilling solution in transfer, leaking

burets, faulty piping, etc.

2. Contamination on dilution of solution by failure to properly rinse burets, pipets and bottles

3. Faulty mixing of solution after they have been diluted

4. Impurities in the primary standard on which the concentration values are based

5. Errors in weighing

6. Use wrong indicators for titration

7. Poor change from buret or pipet

Example 5.6
Direct titration
A 300mg sample containing phosphoric acid and inert gas diluted with water and titrated with
0.05M NaOH according to:
𝑯𝟑 𝑷𝑶𝟒 + 𝟐𝑵𝒂𝑶𝑯 → 𝑵𝒂𝟐 𝑯𝑷𝑶𝟒 + 𝟐𝑯𝟐 𝑶

The end point was reached after 29.00 mL of titrant was added. Calculate the % H 3PO4 in the
sample :

% 𝐻3 𝑃𝑂4
0.05 𝑚𝑚𝑜𝑙 1𝑚𝑚𝑜𝑙𝐻3 𝑃𝑂4 (3 ∗ 1.01 + 30.97 + 4 ∗ 16 𝑚𝑔𝐻3 𝑃𝑂4
29 𝑚𝐿 𝑁𝑎𝑂𝐻 [ ][ ][ ]
𝑚𝐿 2 𝑚𝑚𝑜𝑙 𝑁𝑎𝑂𝐻
= 𝑥100%
300𝑚𝑔

%𝐻3 𝑃𝑂4 = 23.68 %

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Example 5.7
Back titration

An 800 mg sample of chromium ore was dissolved and the chromium oxidized to chromate ion.
The solution was treated with 10.00 mL of 0.20M AgNO3. The resulting precipitate of Ag2CrO4
was removed and discarded. The excess AgNO3 required 14.50 mL of 0.1200M KSCN for
titration. Calculate the %Cr2O3 in the ore.
𝐶𝑟𝑂42− + 2𝐴𝑔+ → 𝐴𝑔2 𝐶𝑟𝑂4(𝑠)
𝐴𝑔+ + 𝑆𝐶𝑁 − → 𝐴𝑔𝑆𝐶𝑁
%𝐶𝑟2 𝑂3 =
1 𝑚𝑚𝑚𝑜𝑙 𝐴𝑔+ 1 𝑚𝑚𝑜𝑙 𝐶𝑟𝑂2− 4 ][1 𝑚𝑚𝑜𝑙 𝐶𝑟2 𝑂3 ][100𝑚𝑔 𝐶𝑟𝑂 ]
{10𝑚𝐿 (0.02𝑀 𝐴𝑔+ )−[14.5𝑚𝐿∗0.12𝑀 𝑆𝐶𝑁 −1][ ]}[ 3
1 𝑚𝑚𝑜𝑙 𝑆𝐶𝑁− 2 𝑚𝑚𝑜𝑙 𝐴𝑔+ 2 𝐶𝑟𝑂4

800𝑚𝑔
x 100%

%𝐶𝑟2 𝑂3 = 1.235%

Example 5.8
Replacement Titration

A 750 mg sample of iron ore was dissolved in acid and treated to oxidize all the iron to ferric iron.
After destroying any remaining oxidizing agent, excess KI was added. The liberated I2 required
28.50 mL of 0.075M Na2S2O3. For titration, what is the % Fe in the sample?
2Fe2+ + 2I-  2 Fe3+ + I2
I2 + 2S2O32-  2I- + S4O6

1I2 2𝐹𝑒 3+ 55.85 𝑚𝑔 𝐹𝑒

%𝐹𝑒 = 28.5𝑚𝐿 𝑁𝑎2 𝑆2 𝑂3 [2𝑆 2− ] [ ] = 15.92%
2 𝑂3 𝐼2 𝑚𝑚𝑜𝑙

5.8 INDICATORS FOR ARGENTOMETRIC TITRATIONS

5.8.1 Chromate Ion; The Mohr Method

Sodium chromate can serve as an indicator for the argentometric determination of chloride,
bromide, and cyanide ions by reacting with silver ion to form a brick-red silver chromate
(Ag2CrO4) precipitate in the equivalence-point region. The silver ion concentration at chemical
equivalence in the titration of chloride with silver ions is given by:

[𝐴𝑔+] = √𝐾𝑠𝑝 = √1.82 𝑥 10−10 = 1.35 𝑥 10−5 𝑀

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The chromate ion concentration required to initiate formation of silver chromate under this
condition can be computed from the solubility constant for silver chromate,
𝑘𝑠𝑝 1.2 𝑥 10−12
[𝐶𝑟𝑂42−] = = = 6.6 𝑥 10−3 𝑀
[𝐴𝑔+]2 (1.35 𝑥 10−5 )2

In principle, then, chromate should be added in an amount to give this concentration for the red
precipitate to appear just after the equivalence point. In fact, however, a chromate ion
concentration of 6.6 x 10-3 M imparts such an intense yellow color to the solution that formation
of the red silver chromate is not readily detected, and lower concentrations of chromate ion are
generally used for this reason. As a consequence, excess silver nitrate is required before
precipitation begins.

The Mohr method was first described in 1865 by K. F. Mohr. A German pharmaceutical chemist
who was a pioneer in the development of titrimetry, because Cr(VI) has been discovered to be a
carcinogen. The Mohr method is now seldom used.

Mohr method for chloride:

Titration reaction
Ag+ + Cl- ⇌ AgCl(s)
White
Indicator reaction
2Ag+ + CrO42-  Ag2CrO4(s)
Red

5.8.2 Adsorption Indicators: The Fajans Method

An adsorption indicator is an organic compound that tends to be adsorbed onto the surface of the
solid in a precipitation titration. Ideally, the adsorption (or desorption) occurs near the equivalence
point and results not only in a color change but also in a transfer of color from the solution to the
solid (or the reverse).

Fluorescein is a typical adsorption indicator that is useful for the titration of chloride ion with
silver nitrate. In aqueous solution, fluorescein partially dissociates into hydronium ions and
negatively charged fluoresceinate ions that are yellow-green. The fluoresceinate ion forms an
intensely red silver salt. Whenever this dye is used as an indicator, however, its concentration is
never large enough to precipitate as silver fluoresceinate.

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Adsorption indicators were first described by K. Fajans, a Polish chemist, in 1926. His name is
pronounced Fay'yahns.

5.8.3 Iron(III) Ion; The Volhard Method

In the Volhard method, silver ions are titrated with a standard solution of thiocyanate ion:
Iron (III) serves as the indicator. The solution turns red with the first slight excess of thiocyanate
ion:

Fe3+ + SCN-  FeSCN2+

Red
[(𝐹𝑒𝑆𝐶𝑁)2+ ]
𝐾𝑓 = 1.0 𝑥 103 = [𝐹𝑒 3+ ][𝑆𝐶𝑁− ]

The titration must be carried out in acidic solution to prevent precipitation of iron(III) as the
hydrated oxide.

The Volhard method was first described by Jacob Volhard, a German chemist, in 1874.

Volhard method for chloride:

Ag+ + Cl- ⇌ AgCl(s)

Excess white

SCN- + Ag+ ⇌ AgSCN(s)

White

Fe3+ + SCN -⇌ Fe(SCN)2+

Red

5.9 APPLICATIONS OF STANDARD SILVER NITRATE SOLUTIONS

Table 5.3 lists some typical applications of precipitation titrations in which silver nitrate is the
standard solution. In most of these methods, the analyte is precipitated with a measured excess of
silver nitrate, and the excess is determined by a Volhard titration with standard potassium
thiocyanate.

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Both silver nitrate and potassium thiocyanate are obtainable in primary-standard quality. The latter
is. However, somewhat hygroscopic, and thiocyanate solutions are ordinarily standardized against
silver nitrate. Both silver nitrate and potassium thiocyanate solutions are stable indefinitely.

TABLE 5.3. TYPICAL ARGENTOMETRIC PRECIPITATION METHODS

Substance Being
Endpoint Remarks
Determined
AsO , Br -, I-, CNO-,
3/4-
Removal of silver salt not
Volhard
SCN- required.
CO2/3-, CrO2/4-, CN-, Cl-,
Removal of silver salt required
(C2O4)2-, (PO4)3-, S2-, Volhard
before back-titration of excess Ag+
NCN2-
Titration of excess Ag+ following
BH-4 Modified Volhard BH4- + 8Ag++8OH-⇌ 8Ag(s) +
H2BO3 -+5H2O
Titration excess Cl+ following
Epoxide Volhard
hydrohalogenation
K+ Modified Volhard Precipitation of K+with known
excess of B(C6H5)4.
Br -, Cl- 2Ag+ + CrO2+⇌ Addition of excess Ag2+ giving
Ag2CrO red AgB(C6H5)4 and back-titration of
the excess
In neutral solution
Br -, Cl-, I-, SeO2-3 Adsorption indicator
V(OH)4+, fatty acid,
Electroanalytical Direct titration with Ag+
mercaptans
Precipitation as ZnHg(SCN)4
filtration dissolution in acid
Zn2+ Modified Volhard
addition of excess Ag+ back-
titration of excess Ag+
Precipitation as PbClF titration
dissolution in acid addition of
F- Modified Volhard
excess Ag+, back-titration of
excess Ag+

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5.10 PRINCIPLES OF NEUTRALIZATION TITRATION

Neutralization Titrations

 It is a chemical reaction in which an acid and a base react quantitatively with each other.
In a reaction in water, neutralization results in there being no excess of hydrogen or
hydroxide ions present in solution.
 It is used to monitor the progress of reactions that produce or consume hydrogen ions.

Fig. 5.5 Neutralization Titration

 It depends on a chemical reaction between the analyte and a standard reagent. The point of
chemical equivalence is indicated by a chemical indicator or an instrumental method.

Acid base equilibria – ubiquitous in both chemistry and science in general.

Standard solutions of strong acid and strong bases –used extensively for determining
analytes that are themselves acids or bases or that can be converted to such species by chemical
treatment.

5.10.1 Solutions and Indicators for Acids/Bases Titrations

 Standard Solutions- The standard solution used in neutralization titrations are strong acids
or strong bases because these substances react more completely with an analyte than do
their weaker counterparts, and they therefor provide sharper end points.
 Nitric acid –seldom used because its oxidizing properties offer the potential for
undesirable side reaction.
The standard reagents used in acids/bases titrations are always strong acids or bases, most
commonly HCl, HClO4, NaOH, and KOH. Weak acids and bases are never used as
standard reagents because they react incompletely with analytes.

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 Acid / Base indicator

An acid/base indicator is weak organic acid or a weak organic base whose undissociated form
differs in color from its conjugate base or its conjugate acid form. For example, the behavior of an
acid-type indicator, HIn, is described by the equilibrium

HInacid color + H2O  In-base color + H3O+

Here, internal structural change accompanies dissociation and cause the color change. The
equilibrium for a base-type indicator, In, is

HIn base color + H2O  InH+acid color +OH-

The equilibrium constant expression for the dissociation of an acid-type indicator takes the form :

[𝐻3 𝑂+ ][𝐼𝑛−]
𝐾𝑎 =
[𝐻𝐼𝑛]

[𝐻𝐼𝑛]
[𝐻3 𝑂+] = 𝐾𝑎
[𝐼𝑛−]

HIn exhibits its pure acid color when,

[𝐻𝐼𝑛] 10
≥
[𝐼𝑛−] 1

And its base color when,

[𝐻𝐼𝑛] 10
≤
[𝐼𝑛−] 1

For the full acid color,

[H3O+] = [H3O+] = 10Ka

For the full base color,

[H3O+] = 0.10Ka

To obtain the indicator pH range, we e the –log of the two expressions,

pH(acid color) = -log (10Ka) = pKa + 1

pH(basic color) = -log (0.10Ka) = pKa – 1

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5.10.2 Titration errors with Acid/Base Indicators

1. Determinate error –occurs when the pH at which the indicator changes color differs from
the pH at the equivalence point. It can usually be minimized by choosing the indicator
carefully or by making a blank correction.
2. Indeterminate error –originates from the limited ability of the eye to distinguish
reproducibly the intermediate color of the indicator. The magnitude of this error depends
on the change in pH per mL reagent at the equivalence point, on the concentration color of
the indicator, and on the sensitivity of the eye to the two indicator color.

5.10.3 Variables that Influence the Behavior of Indicators

a) Temperature
b) Ionic strength of the medium
c) Presence of the organic solvents and colloidal particle

Table 5.4 Common chemical indicators

Common Name Transition Range, pH pKa* Color Change Indicator Type

Thymol Blue 1.2-2.8 1.65 R-Y 1
8.0-9.6 8.96 Y-B
Methyl Yellow 2.9-4.0 R-Y 2
Methyl Orange 3.3-4.4 3.46 R-O 2
Bromocresol Green 3.8-5.4 4.66 Y-B 1
Methyl Red 4.2-6.3 5.00 R-Y 2
Bromocresol Purple 5.2-6.8 6.12 Y-P 1
Bromothymol Blue 6.2-7.6 7.10 Y-B 1
Phenol Red 6.8-8.4 7.81 Y-R 1
Cresol Purple 7.6-9.2 Y-P 1
Phenolphthalein 8.3-10.0 C-R 1
Thymolphthalein 9.3-10.5 C-B 1
Alizarin Yellow
10-12 C-Y 2
GG

5.10.3 Titration of Strong Acids and Strong Bases

The hydronium ion in an aqueous solution of a strong acid has two sources:

a) The reaction of acid with water

b) The dissociation of water itself

In a solution of a strong acid that are more concentrated that about 1x10 -6M, we can assume
that the equilibrium concentration of H3O+ is equal to the analytical concentration of the acid. The
same is true for [OH-] in solutions of strong bases.

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Fig. 5.6 Titrating a Strong Acid with a Strong Base

Three types of calculations must be done to construct the hypothetical curve for titrating a
solution of a strong acid with a strong base.

 Pre equivalence – we compute the concentration of the acid from its starting concentration
and the amount of base added.
 Equivalence –the hydronium and hydroxide ion are present in equal concentration and the
hydronium ion concentration is derived directly from the ion product constant for water.
 Post equivalence –the analytical concentration of the excess base is computed and the
hydroxide ion concentration is assumed to be equal to or a multiple of the analytical
concentration.

Example 5.9

Generate the hypothetical titration curve for the titration of 50.00 mL of 0.0500 M HCl with 0.100
M NaOH.

Initial point

Before any base is added, the solution is 0.0500 M in H3O+, and

pH= -log [H3O+]= -log (0.0500)=1.30

After addition of 10.00 mL of reagent

The hydronium ion concentration is decreased as a result of both reaction with the base and
dilution. So the analytical concentration of HCl is:

𝑛𝑜. 𝑚𝑚𝑜𝑙 𝐻𝐶𝑙 𝑟𝑒𝑚𝑎𝑖𝑛𝑖𝑛𝑔 𝑎𝑓𝑡𝑒𝑟 𝑎𝑑𝑑𝑖𝑡𝑖𝑜𝑛 𝑜𝑓 𝑁𝑎𝑂𝐻

[𝐻𝐶𝑙 ] =
𝑇𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

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𝑂𝑟𝑖𝑔𝑖𝑛𝑎𝑙 𝑛𝑜. 𝑚𝑚𝑜𝑙 𝐻𝐶𝑙 − 𝑛𝑜. 𝑚𝑚𝑜𝑙 𝑁𝑎𝑂𝐻 𝑎𝑑𝑑𝑒𝑑

[𝐻𝐶𝑙 ] =
𝑇𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

0.050𝑚𝑚𝑜𝑙 0.10𝑚𝑚𝑜𝑙
(50.0 𝑚𝐿 𝑥 ) − (10.0𝑚𝐿 𝑥 )
[𝐻𝐶𝑙 ] = 𝑚𝐿 𝑚𝐿
(50.0 + 10.0)𝑚𝐿

(2.500𝑚𝑚𝑜𝑙 − 1.00 𝑚𝑚𝑜𝑙

[𝐻𝐶𝑙 ] = = 2.50 𝑥 10−2 𝑀
60.0 𝑚𝐿

[𝐻3 𝑂+ ] = 2.50 𝑥 10−2 𝑀

And the pH = -log [H3O] = -log (2.500x10-2) = 1.60

pH pH
50.00 mL of 0.0005 M
50.00 mL of 0.0500 M HCl
Volume of NaOH, mL HCl with 0.00100 M
with 0.100 M NaOH
NaOH
0.00 1.30 3.30
10.00 1.60 3.60
20.00 1.15 4.15
24.00 2.87 4.87
24.19 3.87 5.87
25.00 7.00 7.00
25.10 10.12 8.12
26.00 11.12 9.12
30.00 11.18 9.80

We calculate additional points defining the curve in the region before the equivalence point
in the same way. The result of these calculations are shown in the second column of the table
above.

After addition of 25.00 mL of reagent: The equivalence point,

At the equivalence point, neither HCl nor NaOH is in excess, and so the concentrations of
the hydronium and hydroxide ions must be equal. Substituting this quality into the ion product
constant for water yields.

[𝐻3 𝑂+ ] = √𝐾𝑤 = √1.0 𝑥 10−14 = 1.0 𝑥 10−7 𝑀

𝑝𝐻 = − log(1.0 𝑥 10−7 ) = 7

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After addition of 25.10mL of reagent

The solution now contains an excess of NaOH and we can write

𝑛𝑜. 𝑚𝑚𝑜𝑙 𝑎𝑑𝑑𝑒𝑑 − 𝑜𝑟𝑖𝑔𝑖𝑛𝑎𝑙 𝑛𝑜. 𝑚𝑚𝑜𝑙 𝐻𝐶𝑙

[𝑁𝑎𝑂𝐻 ] =
𝑇𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒

(25.10 𝑥 0.10) − (50.0 𝑥 0.050)

[𝑁𝑎𝑂𝐻 ] = = 1.33 𝑥 10−4 𝑀
75.10 𝑚𝐿

And the equilibrium concentration of hydroxide ion is:

[𝑂𝐻 −] = [𝑁𝑎𝑂𝐻 ] = 1.33 𝑥 10−4 𝑀

𝑝𝑂𝐻 = − log(1.33 𝑥 10−4 ) = 3.88

𝑝𝐻 = 14.0 − 3.88 = 10.12

And we compute additional data defining the curve beyond the equivalence point in the same way.
The results of these computations are shown in the table above.

5.10.4 Titrating a Strong Base with a Strong Acid

Fig. 5.7 Titration of a strong base with a strong acid

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Example 5.10

Calculate the pH during the titration of 50.00 mL of 0.0500 M NaOH with 0.1000 M HCl
after the addition of the following volumes of reagent: (a) 24.50 mL (b) 25.00 (c) 25.50 mL.

(a) At 24.50 mL added, [H3O+]is very small and cannot be computed from stoichiometric
considerations but can be obtained from [OH-]

𝑂𝑟𝑖𝑔𝑖𝑛𝑎𝑙 𝑛𝑜. 𝑚𝑚𝑜𝑙 𝑁𝑎𝑂𝐻

[𝑂𝐻 −] =
𝑇𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

(50.00 𝑥 0.05)− (24.5)(0.10)

[𝑂𝐻 −] = = 6.71𝑥 10−4 𝑀
50.0+ 24.5

𝐾𝑤 1.0 𝑥 10−4
[𝐻3 𝑂+] = = −4
= 1.49 𝑥 10−11 𝑀
√6.71 𝑥 10−4 6.71 𝑥 10

𝑝𝐻 = −𝑙𝑜𝑔 (1.49 𝑥 10−11 ) = 10.83

(b) This is the equivalence point where [H3O+] = [OH-]

[𝐻3 𝑂+] = √𝐾𝑤 = √1.0𝑥10−14 = 1.00 𝑥 10−7

𝑝𝐻 = − log 1.00 𝑥 10−7 = 7.0

At 25.50 mL added,

(25.0)(0.10) − (50.0)(0.05)
[𝐻3 𝑂+ ] = [𝐻𝐶𝑙 ] = = 6.62𝑥10−4
75.50
𝑝𝐻 = − log 6.62𝑥 10−4 = 3.18

Fig. 5.8 Titration curve of NaOH with HCl. Curve A: 50.0 mL of 0.050M NaOH with 0.10M
HCl, Curve B: 50.0mL of 0.0050M NaOH with 0.010M HCl

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5.10.5 Titration Curves for Weak Acids

Fig. 5.9 Titration curves for weak acid with strong base

Four distinctly different types of calculations are needed to derive a titration curve for a weak acid:

1. At the beginning, the solution contains only a week acid or a weak base, and the
pH is calculated from the concentration of that solute and its dissociation constant.

2. After various increments, of titrant have been added, the solution consists of a series
of buffers. The pH of each buffer can be calculated from the analytical
concentrations of the conjugate base or acid and the residual concentrations of the
weak acid or base.

3. At the equivalence point, the solution contains only the conjugate of the weak acid
or base being titrated, and the pH is calculated from the concentration of this
product.

4. Beyond the equivalence point, the excess of strong acid or base titrant represses the
acidic or basic character of the reaction product to such an extent that the pH is
governed largely by the concentration of the excess titrant.

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Example 5.11

Generate a curve for the titration of 50.00 mL of 0.1000 M acetic acid with 0.1000 M sodium
hydroxide.

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Changes in pH during the titration of a weak acid with strong base

pH pH
50.00 mL of 0.00100 M
50.00 mL of 0.1000 M HOAc
Volume of NaOH, mL HOAc with 0.00100 M
with 0.1000 M NaOH
NaOH
0.00 2.88 3.91
10.00 4.16 4.30
25.00 4.76 4.80
40.00 5.36 5.38
49.00 6.45 6.46
49.90 7.46 7.45
50.00 8.73 7.73
50.10 10.00 8.09
51.00 11.00 9.00
60.00 11.96 9.96
70.00 12.22 10.25

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5.10.6 Titration Curves for weak Bases

Fig. 5.10 Titration curves for weak base with strong acid

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Example 5.12.

A 50.00 mL aliquot of 0.0500 M NaCN is titrated with 0.1000 M HCl. The reaction is

CN- + H3O+  HCN + H2O

Calculate the pH after the addition of (a) 0.00, (b) 10.00, (c) 25.00, and (d) 26.00 mL of acid.

(a) 0.00mL of reagent

The pH of a solution of NaCN can be derived here;

Substitution into the dissociation constant expression gives, after rearrangement,

a.) 10 mL of reagent

These values are then substituted into the expression for the acid dissociation constant of
HCN to give [H3O+] directly.

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b.) 25.00 ml of reagent

This volumes corresponds to the equivalence point, where the principal solute species
is the weak acid HCN. Thus,

c.) 26.00ml of reagent

The excess of strong acid now present represses the dissociation of the HCN to the
point where its contribution to the pH is negligible. Thus,

The composition of solutions during acid/base titrations

We are often interested in the changes in composition that occur while a solution of a weak
acid or a weak base is being titrated. These changes can be visualized by plotting the relative
equilibrium concentration as of the weak acid as well as the relative equilibrium concentration of
the conjugate base
a1 as function of the pH of the solution.

Acidimetry and Alkalimetry - acid base titration

Strong acid HCl + H2O → H3O+ + Cl-

Weak acid HCN + H2O → H3O+ + CN-

Strong base NaOH + H2O → H3O+ + Cl-

Weak base NH3 + H2O → NH4+ + OH-

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pH Calculations

Strong acid HCl + H2O → H3O+ + Cl-

Initial CSA
Δ - CSA CSA CSA
Equilibrium 0 CSA CSA

pH = -log CSA

Weak acid HCN + H2O → H3O+ + CN-

Initial CWA
Δ -X X X
Equilibrium CWA – X X X

pH = -log X

X2 = Ka CWA – Ka X
X2 + Ka X = Ka CWA

Strong base NaOH + H2O → H3O+ + Cl-

Initial CSB
Δ - CSB CSB CSB
Equilibrium 0 CSB CSB

pOH = -log CSB

pH = 14 – pOH
pH = 14 + log CSB

Weak base NH3 + H2O → NH4+ + OH-

Initial CWB
Δ -X X X
Equilibrium CWB – X X X

pOH = -log X

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5.11 APPLICATION OF NEUTRALIZATION TITRATION

Neutralization titrations are widely used to determine the concentration of analytes that are
themselves acids or bases or are convertible to such species by suitable treatment.

Water is the usual solvent for neutralization titrations because it is readily available,
inexpensive, and nontoxic. Its low temperature coefficient of expansion is an added virtue. Some
analytes, however, are not titratable in aqueous media because their solubilities are not low or
because their strengths as acids or bases are not sufficient great to provide satisfactory end points.
Such substances can often be treated in a solvent other than water.

Nonaqueous solvents, such as methyl and ethyl alcohol, glacial acetic acid, and methyl
isobutyl ketone often make it possible to titrate acids or bases that are too weak to titrate in aqueous
solution.

Reagents for Neutralization Titrations

Strong acids and strong bases cause the most pronounced change in ph at the equivalence
point. For this reason, standard solutions for neutralization titrations are always prepared from
these reagents.

5.11.1 Preparation of Standard Acid Solutions

Hydrochloric acid is widely used for titration of bases. Dilute solutions of the reagent are
stable indefinitely and do not cause troublesome precipitation reactions with most cations.
Standard acid solutions are ordinarily prepared by diluting an approximate volume of primary
standard base.

Solutions of perchloric and sulfuric acid are also stable and are useful for titrations were
chloride ion interferes by forming precipitates. Standard solutions of nitic acid are seldom
encountered because of their oxidizing properties.

Solutions of HCL, HClO4, and H2SO4 are stable indefinitely. Restandardization is not
required unless evaporation occurs.

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Standard acid solutions are ordinarily prepared by diluting an approximate volume of the
concentration reagents and subsequently standardizing the diluted solution against a primary -
standard base. Less frequently, the composition of the concentrated acid is established through
careful density measurement; a weighed quantity is then diluted to a known volume. A stock
solution with an exactly known hydrochloric acid concentration can be prepared by dilution of a
quantity of the concentrated reagent with an equal volume of water followed by distillation.

Under controlled conditions, the final quarter of the distillate which is known as constant-
boiling HCl, has affixed and known composition, its acid content being dependent only on the
atmospheric pressure. For a pressure P between 670 and 780 torr, the mass in air of the distillate
that contains exactly one mole of H30+ is ^3
Mass of constant − boiling HCl in g
= 164.673 + 0.02039 P
mol H3 O+

Standard solutions are prepared by diluting weighed quantities of this acid to accurately
known volumes.

5.11.2 The Standardization of Acids

1. SODIUM CARBONATE

a. Acids are frequently standardized against weighed quantities of sodium carbonate.

Primary standard grade sodium carbonate is available commercially or can be
prepared by heating purified sodium hydrogen carbonate to 270 degree Celsius to
300 degree Celsius for one hour:
2NaHCO3(s)  Na2CO3(s) + H2O (g) + CO2(g)

b. Sodium carbonate occurs naturally in large deposits as washing soda, Na2CO3  10

H2O, and as trona,. Na2CO3  2H2O. These minerals find wide use in the glass
industry as well as many others. Primary-standard sodium carbonate is
manufactured by extensive purification of these minerals.

2. OTHER PRIMARY STANDARDS FOR ACIDS

a. A high mass per proton consumed is desirable in a primary standard because a

larger mass of reagent must be used thus decreasing the relative weighing error.

b. Tris-(hydroxymethyl) amino methane, (HOCH2)3CNH2, known as TRIS or THAM,

is available primary-standard purify from commercial sources. It possesses the
advantage of substantially greater mass per mole of protons consumed than sodium
carbonate. The reaction of TRIS with acids is

(HOCH2)3CNH2 + H3O+ (HCOH2)3CNH3+ + H2O

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Sodium tetraborate decahydrate and mercury (II) oxide have also been
recommended as primary standards. The reaction of an acid with the tetraborate is

B4O72- + 2H3O+ +3 H2O 4H3BO3

Borax Na2B4O7  10 H2O is a mineral that is mined in the desert and is widely used
in cleaning preparations. A highly purified form of borax is used as a primary standard for
bases.

Preparation of Standard Solutions of Base

Sodium hydroxide is the most common base for preparing standard solutions.

1. THE EFFECT OF CARBON DIOXIDE ON STANDARD BASE SOLUTIONS

In solution as well as in the solid state the hydroxides of sodium, potassium, and
barium react rapidly with atmospheric carbon dioxide to produce the corresponding
carbonate:

CO2(g) + 2OH-CO32- + H2O

Although production of each carbonate ion uses up two hydroxide ions, the uptake
of carbon dioxide by a solution of base does not necessarily alter its combining capacity
for hydronium ions. Thus, at the end point of a titration that requires an acid-range
indicator, each carbonate ion produced from sodium or potassium hydroxide will have
reacted with two hydronium ions of the acid:

CO32- + 2H3O+  H2CO3 + 2H2O

Absorption of carbon dioxide by a standardized solution of sodium or an indicator

with a basic range is used; no systematic error is incurred when an indicator with an acidic
range is used.

Most applications of standard base require an indicator with a basic transition range.
Here, each carbonate ion has reacted with only one hydronium ion when the colour change
of the indicator is observed:

CO32- + H3O+  HCO3-+ H2O

The effective concentration of the base is thus diminished by absorption of carbon

dioxide, and a systematic error (called a carbonate error) results.

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Example 5.13

A carbonate free NaOH solution was found to be 0.05118 M immediately after preparation.
Exactly 1.000 L of this solution was exposed to air for some time and absorbed 0.1962 g CO 2.
Calculate the relative carbonate error that would arise in the determination of the acetic acid with
the contaminated solution if phenolphthalein were used as an indicator.

2NaOH + CO2  Na2CO3 + H2O

1 mol CO2 1 mol Na2CO3 1

CNa2CO3= 0.1962 g CO2 x 44.01 g CO2 x x 1.000 L soln
mol CO2

cNa2CO3 = 4.458 x 10-3M

The effective concentration for cNaOH of NaOH for acetic acid is then

mol NaOH 4.458 x 10−3 mol Na2CO3 1 mol HCl 1 mol NaOH
CNaOH = 0.05118 - x mol Na2CO3 x
L L mol HCl

CNaOH = 0.04672 M

0.04672−0.05118
Relative error = x 100% = 8.7%
0.05118

The solid reagents used to prepare standard solutions of base are always contaminated by
significant amounts of carbonate ion. Carbonate ion on standard base solutions is undesirable
because it decrease the sharpness of end points.

Water that is in equilibrium with atmospheric constituents contains only about 1.5 x 10 -5
mol CO2 /L an amount that has a negligible effect on the strength of the most standard bases. As
an alternative to boiling to remove CO2 from supersaturated solutions of CO2 the excess gas can
be removed by bubbling air through the water for several hours. This process is called sparging
and produces a solution that contains the equilibrium concentration of CO 2 .

Sparging is the process of removing a gas from a solution by bubbling an inert gas through
the solution.

Solutions of bases are preferably stored in polyethylene bottles rather than glass because
of the reaction between bases and glass. Such solution should never be stored in glass-stoppered
bottles; after standing for a period, removal of the stopper often becomes impossible.

Standard solution of strong bases cannot be prepared directly by mass and must always be
standardized against a primary standard with acidic properties.

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5.11.3 The Standardization of Bases

Several excellent primary standards are available for the standardization of bases. Most are
weak organic acids that require the use of an indicator with a basic transition range.

 Potassium Hydrogen Phthalate- Potassium hydrogen phthalate, KHC8H4O4is an ideal

primary standard. It is a non-hygroscopic crystalline solid with a high molar mass (204.2
g/mol).
 Other Primary Standards For Bases- Benzoic acid is obtainable in primary standard
purify and can be used for the standardization of bases. Because its solubility in water is
limited, this reagent is ordinarily dissolved in ethanol prior to dilution with water and
titration.

Potassium hydrogen iodate, KH(IO3)2 is an excellent primary standard with a high

molecular mass per mole of protons. It is also a strong acid that can be titrated using virtually any
indicator with a transition range between a pH of 4 and 10.

KH(IO3)2 in contrast to all other primary standards for bases has the advantage of being a
strong acid, thus making the choice of indicator less critical.

5.11.4 Typical Applications of Neutralization Titrations

Neutralization titrations are used to determine the innumerable inorganic, organic, and
biological species that possess inherent acidic or basic properties.

Two major types of end points find widespread use in neutralization titrations. The first is
visual end point based on indicators. The second is a potentiometric end point, in which the
potential of a glass/calomel electrode system is determined with a voltage-measuring device. The
measured potential is directly proportional to pH.

1. ELEMENTAL ANALYSIS

Several important elements that occur in organic and biological systems are
conveniently determined by methods that involve an acid/base titration as the final step.
Generally, the elements susceptible to this type of analysis are non-metallic and include carbon,
bromine, and fluorine, as well as a few other less common species.

 NITROGEN
 Nitrogen occurs in a wide variety of substances of interest in research; industry,
and agriculture. Examples include amino acids, proteins, synthetic drugs,
fertilizers, explosives, soils, portable water supplies, and dyes. Thus, analytical
methods for the determination of nitrogen, particularly, in organic substrates, are of
singular importance.
 The most common method for determining organic nitrogen is the Kjeldahl method,
which is based on a neutralization titration. The procedure is straightforward,
requires no special equipment, and is really adapted to the routine analysis of large

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numbers of samples. It is standard means of determining the protein content of

grains, meats, and other biological materials.
 Hundreds of thousands of Kjeldahl nitrogen determinations are performed each
year, primarily to provide a measure of the protein content of meats, grains, and
animal feeds.

 DETERMINING TOTAL SERUM PROTEIN

 The determination of total serum protein is an important clinical measurement used
in diagnosing liver malfunctions.
 The Kjeldahl procedure, however, has historically been the reference method
against which other methods are compared. Methods commonly used include the
biuret method and the Lowry method.
 The Kjeldahl method was developed by a Danish chemist who first described it in
1883.
 In the Biuret method, a reagent containing cupric ions is used, and a violet-colored
complex is formed between the Cu2+ ions and peptide bonds. The increase in the
absorption of visible radiation is used to measure serum protein. In the Lowry
procedure, the serum sample is pre-treated with an alkaline copper solution
followed by a phenolic reagent. A colour develops because of reduction of
phosphotungstic and phophomolybdic acid to a blue heteropoly acid. Both the
biuret and Lowry methods use spectrophometry for quantitative measurements.
 The critical step in Kjeldahl method is the decomposition with sulphuric acid,
which oxidizes the carbon and hydrogen in the sample to carbon dioxide and water.

TABLE 5.5 Elemental Analyses Based on Neutralization Titrations

Element Converted to Adsorption or Precipitation Products Titration

Excess HCl with
N 𝑁𝐻3 𝑁𝐻3 (𝑔) + 𝐻3 𝑂+ → 𝑁𝐻4 + + 𝐻2 𝑂
NaOH
S 𝑆𝑂2 𝑆𝑂2 (𝑔) + 𝐻2 𝑂2 → 𝐻2 𝑆𝑂4 NaOH
𝐶𝑂2 (𝑔) + 𝐵𝑎 (𝑂𝐻 )2 Excess Ba(OH)2 with
C 𝐶𝑂2
→ 𝐵𝑎 (𝐶𝑂)3 (𝑠) + 𝐻2 𝑂 HCl
Cl (Br) 𝐻𝐶𝑙 𝐻𝐶𝑙(𝑔) + 𝐻2 𝑂 → 𝐶𝑙 − + 𝐻3 𝑂+ NaOH

F 𝑆𝑖𝐹4 𝑆𝑖𝐹4 (𝑔) + 𝐻2 𝑂 → 𝐻2 𝑆𝑖𝐹6 NaOH

12𝐻2 𝑀𝑜𝑂4 + 3𝑁𝐻4 + + 𝐻3 𝑃𝑂4

→ (𝑁𝐻4 )3 𝑃𝑂4 ⋅ 12𝑀𝑜𝑂3 (𝑠)
+ 12𝐻2 𝑂 + 3𝐻 + Excess NaOH with
P 𝐻3 𝑃𝑂4
(𝑁𝐻4 )3 𝑃𝑂4 ⋅ 12𝑀𝑜𝑂3 (𝑠) + 26𝑂𝐻 − HCl
→ 𝐻𝑃𝑂4 2− + 12𝑀𝑜𝑂4 2−
+ 14𝐻2 𝑂 + 3𝑁𝐻3 (𝑔)

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CHE 401 : ANALYTICAL CHEMISTRY

 KJELDAHL METHOD (determination of organic nitrogen) – common method for

determining organic nitrogen requires no special equipment and is readily adapted to the
routine analysis of large number of samples.
Step 1 → Digestion – the sample is oxidized in hot concentrated sulphuric acid
(H2SO4) and turns black.
Step 2 → Distillation – the solution is cooled and then treated with NaOH to liberate
ammonia gas
Step 3 → Titration

Calculations:

% Protein = % N(f) f = 5.70 (cereals)

= 6.25 (meat products)
= 6.38 (dairy products)
Example 5.14

A 0.7121 g sample of wheat flour was analyzed Kjeldahl method. The ammonia formed by
addition of concentrated base after digestion with H2SO4 was distilled into 25.00 mL of 0.04977
M HCl was then back titrated with 3.97 mL of 0.04012 M NaOH. Calculate the percent protein in
the flour.

𝑚𝑚𝑜𝑙 𝐻𝐶𝑙
amount HCl = 25.00 mL HCl x 0.04977 = 1.2443 mmol
𝑚𝐿 𝐻𝐶𝑙

𝑚𝑚𝑜𝑙 NaOH
amount NaOH= 3.97mL NaOH x 0.04977 = 0.1593 mmol
𝑚𝐿 NaOH

amount N = 1.0850 mmol

0.014007 𝑔 𝑁
1.0850 𝑚𝑚𝑜𝑙 N x
𝑚𝑚𝑜𝑙 𝑁
%N = 0.7121 𝑔 𝑠𝑎𝑚𝑝𝑙𝑒
x 100% = 2.1341

5.70% 𝑝𝑟𝑜𝑡𝑒𝑖𝑛
%protein = 2.1341% x = 12.16
%𝑁

 SULFUR
 Sulphur in organic biological materials is conveniently determined by burning the
simple in a stream of oxygen.
 The sulphur dioxide formed during the oxidation is collected by distillation into a dilute
solution of hydrogen peroxide: SO2(g) + H2O2 H2SO4
 Sulphur dioxide in the atmosphere is often determined by drawing a sample through a
hydrogen peroxide solution and then titrating the sulphuric acid that is produced.

2. THE DETERMINATION OF INORGANIC SUBSTANCES

Numerous Inorganic species can be determined by titration with strong acids or
bases.

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 AMMONIUM SALTS
 Ammonium salts are conveniently determined by conversion to ammonia with
strong base followed with distillation. The ammonia is collected and titrated as in
the Kjeldahl method.
 NITRATES AND NITRITES
 The method just described for ammonium salts can be extended to the
determination of inorganic nitrate or nitrite. These ions are first reduced to
ammonium ion by Devarda’s alloy. Granules of the alloy are introduced into a
strongly alkaline solution of the sample in a Kjeldahl flask. The ammonia is
distilled after reaction is complete. Arnd’s alloy has also been used as the reducing
agent.
 CARBONATE AND CARBONATE MIXTURES
 The qualitative and quantitative determination of the constituents in a solution
containing sodium carbonate, sodium hydrogen carbonate and sodium hydroxide,
either alone or admixed, provides interesting examples of how neutralization
titrations can be employed to analyze mixtures. No more than two of these three
constituents can exist in appreciable amount in any solution because reaction
eliminates the third. Thus, mixing sodium hydroxide with sodium hydrogen
carbonate results in the formation of sodium carbonate until one or the other of the
original reactants is exhausted. If the sodium hydroxide is used up, the solution will
contain sodium carbonate and sodium hydrogen carbonate; if sodium hydrogen
carbonate is depleted, sodium carbonate and sodium hydrogen carbonate will
remain; if equimolar amounts of sodium hydrogen carbonate and sodium hydroxide
are mixed, the principal solute species will be sodium carbonate.

Determination of Inorganic Substances

TABLE 5.6 Volume Relationships in the Analysis of Mixtures Containing Hydroxide,

Carbonate, and Hydrogen Carbonate Ions

Relationship between Vphth and Vbeg in the

Constituents in Sample
Titration of an Equal Volume of Sample*
NaOH Vphth = Vbeg
Na2CO3 Vphth = ½ Vbeg
NaHCO3 Vphth = 0; Vbeg > 0
NaOH, Na2CO3 Vphth > ½ Vbeg
Na2CO3, NaHCO3 Vphth < ½ Vbeg
* Vphth = volume of acid needed for a phenolphthalein end point; Vbeg = volume of acid
needed for a bromocresol green and point.

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Fig. 5.11 Titration curves and indicator transition ranges for the analysis of mixtures containing:
hydroxide, carbonate, and hydrogen carbonate ions.

Double Indicator Method

a) Mixture of Na2CO3 and NaHCO3

Na2CO3 + 2H3O → 2Na + CO2 + 3H2O

NaHO3 + H3O → Na + CO2 + 2H2O

CO2−
3 ----------------------------------------------------

A Vo →ph

HCO3-------------------------- HCO3------------------ Vo →MR

A Vph →MR

CO2----------------------------- CO2--------------------

V0→ ph < Vph→ MR

1 mol Na2 CO3 106 mg Na2 CO3

mg Na2 CO3 = 2(V0 → ph) ( )( )
2 mmol HCl 1 mmol Na2 CO3
1 mmol NaHCO3 84.07 mg
mg NaHCO3 = (Vph → MR − V0 → ph)(MHCl) ( )( )
1 mmol HCl 1 mmol
1 mmol NaHCO3 84.07 mg
mg NaHCO3 = (V0 → MR − 2V0 → ph)(MHCl ) ( )( )
1 mmol HCl 1 mmol

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b) Mixture of Na2CO3 and NaOH

NaOH + HCl → NaCl + H2O

Na2CO3 + 2HCl → 2NaCl + CO2 + H2O

NaOH--------------------CO2−
3 -------------------------

Vo → ph

H2O HCO3 Vo→MR

Vph→ MR

CO2

V0→ ph > Vph→ MR

1 mmol NaOH 40 mg NaOH

mg NaOH = (V0 → ph − Vph → MR )( MHCl ) ( )( )
1 mmol HCl 1 mmol
1 mmol NaOH 40 mg NaOH
mg NaOH = (2V0 → ph − V0 → MR )( MHCl ) ( )( )
1 mmol HCl 1 mmol
1 mmol Na2 CO3 106 mg Na2 CO3
mg Na2 CO3 = 2(Vph → MR )( MHCl ) ( )( )
1 mmol HCl 1 mmol
1 mmol Na2 CO3 106 mg Na2 CO3
mg Na2 CO3 = 2(V0 → MR − V0 → ph)( MHCl ) ( )( )
1 mmol HCl 1 mmol

Example 5.15

A solution contains NaHCO3, Na2CO3, and NaOH, either alone or in permissible

combination. Titration of a 50.0 mL portion to a phenolphthalein end point requires 22.1 mL of
0.100 M HCl. A second 50.0 mL aliquot requires 48.4 mL of the HCl when titrated to a
bromocresol green end point. Deuce the composition, and calculate the molar solute concentrations
of the original solution.

If the solution contained only NaOH, the volume of acid required would be the same
regardless of indicator. Similarly, we can rule out the presence of Na 2CO3 alone because titration
of this compound to a bromocresol green end point would consume just twice the volume of acid
required to reach the phenolphthalein end point. In fact, however, the second titration requires 48.4
mL. Because less than half of this amount is involved in the first titration, the solution must contain
some NaHCO3 in addition to Na2CO3. We can now calculate the concentration of the two
constituents.

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CHE 401 : ANALYTICAL CHEMISTRY

When the phenolphthalein end point is reached, the CO 32- originally present is converted
to HCO3-. Thus,

No. mmol Na2CO3 = 22.1 mL x 0.100 mmol/mL = 2.21

The titration from the phenolphthalein to the bromocresol green end point (48.4 – 22.1 =
26.3 mL) involves both the hydrogen carbonate originally present and that formed by titration of
the carbonate. Thus,

No. mmol NaHCO3 + no. mmol Na2CO3 = 26.3 x 0.100 = 2.63

Hence,

No. mmol NaHCO3 = 2.63 – 2.21 = 0.42

The molar concentrations are readily calculated from these data:

2.21 𝑚𝑚𝑜𝑙
CNa2CO3 = = 0.0422 M
50.0 𝑚𝐿

0.42 𝑚𝑚𝑜𝑙
CNaHCO3 = = 0.084 M
50.0 𝑚𝐿

3. THE DETERMINATION OF ORGANIC FUNCTIONAL GROUPS

Neutralization titrations provide convenient methods for the direct or indirect

determination of functional groups.

A. CARBOXYLIC AND SULFONIC ACID GROUPS

a. Carboxylic and sulfonic acid group are two most common structures that impart
acidity to organic compounds. Most carboxylic acids have dissociation
constants that range between 10-4 and 10-6, and thus these compounds are
readily titrated. An indicator that changes color in the basic range, such as
phenolphthalein, is required. Sulfonic acids are generally strong acids and
readily dissolve in water. Their titration with a base is therefore straightforward.

B. AMINE GROUPS
a. Aliphatic amines generally have base dissociation constant in the order of 10 -5
and can thus be titrated directly with of a strong acid. Aromatic amines such as
aniline and its derivatives are usually too weak for titration in aqueous medium
(Kb = 10-10).

C. ESTER GROUPS
a. Esters are commonly determined by saponification with a measured quantity of
standard base:
R1COOR2 + OH  R1COO + HOR2
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CHE 401 : ANALYTICAL CHEMISTRY

b. The excess base is then titrated with standard acid.

c. Saponification is the process by which an ester is hydrolyzed in alkaline
solution to give an alcohol and a conjugate base.

D. HYDROXYL GROUPS
a. Hydroxyl groups in organic compounds can be determined by esterification
with various carboxylic acid anhydrides or chlorides; the two most common
reagents are acetic anhydride and phthalic anhydride,
(CH3CO)2O + ROH CH3COOR + CH3COOH
b. The acetylation is ordinarily carried out by mixing the sample with a carefully
measured volume of acetic anhydride in pyridine. After heating, water is added
to hydrolyze the unreacted anhydride:
(CH3CO)2O + H2O 2CH3COOH
c. Amines if present are converted quantitatively to amides by acetic anhydride; a
correction for this source of interference is frequently possible by direct titration
of another portion of the sample with standard acid.

E. CARBONYL GROUP
a. Many aldehydes and ketones can be determined with a solution of
hydroxylamine hydrochloride.
b. The liberated hydrochloric acid is titrated with base. Here again, the conditions
necessary for quantitative reaction vary. Typically, 30 minutes suffices for
aldehydes. Many ketones require refluxing with the reagent for one hour or
more.

4. THE DETERMINATION OF SALTS

a. The total salt content of a solution can be accurately and readily determined by an
acid/base titration. The salt is converted to an equivalent amount of an acid or a
base by passage through a column packed with an ion-exchange resin.
b. Standard acid or base solutions can also be prepared with ion-exchange resins.
Here, a solution containing a known mass of pure compound, such as sodium
chloride, is washed through the resin column and diluted to a known volume. The
salt liberates an equivalent amount of acid or base from the resin, permitting
calculation of the molarity of the reagent in a straightforward way.

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5.12. End of Module Test

5.1 A 0.4000g sample that assayed 96.4% Na2SO4 required 41.25 mL of a barium chloride
solution

Reaction: Ba2+ + SO42-→ BaSO4(s)

Calculate the analytical molarity of BaCl 2 in the solution.

5.2 The arsenic in a 1.010 g sample of a pesticide was converted to H3AsO4 by suitable treatment.
The acid was then neutralized, and exactly 40.00 mL of 0.06222M AgNO3 was added to precipitate
the arsenic quantitatively as Ag3AsO4. The excess Ag in the filtrate and in the washings from the
precipitate was titrated with 10.76 mL of 0.1000MKSCN; the reaction was

Ag+ + SCN-→ AgSCN(s)

Calculate the percent AsO3 in the sample.

5.3 A 50.00 mL aliquot of 0.1000 M NaOH is titrated with 0.1000 M HCI. Calculate the pH
of the solution after the addition of 0.00, 10.00, 25.00, 40.00, 45.00, 49.00, 50.00, 51.00, 55.00,
and 60.00 mL of acid, and prepare a titration curve from the data.

5.4 A 50.00-mL sample of a white dinner wine required 21.48 mL of 0.03776 M NaOH to
achieve a phenolphthalein end point. Express the acidity of the wine in terms of grams of tartaric
acid (H2C4H4O6, 150.09 g/mol per 100 mL. (Assume that both acidic protons of the compound
are titrated.)

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48