CHM206 – ANALYTICAL CHEMISTRY

DEPARTMENT OF CHEMISTRY

FEDERAL UNIVERSITY OYE-EKITI

CHM206 – ANALYTICAL CHEMISTRY

TOPIC: VOLUMETRIC ANALYSIS

✓ Overview

Titrimetry, in which we measure the volume of a reagent reacting stoichiometrically with the
analyte, first appeared as an analytical method in the early eighteenth century. Unlike
gravimetry, titrimetry was initially not widely accepted as an analytical technique. Many
prominent late-nineteenth-century analytical chemists preferred gravimetry over titrimetry, and
few of the standard texts from that era include titrimetric methods. By the early twentieth
century, however, titrimetry began to replace gravimetry as the most commonly used analytical
method.

✓ Common Terms used in Volumetric Analysis

1. A standard solution (or a standard titrant) is a known concentration reagent used to carry
out a volumetric titration.

2. Titrimetry is any method in which volume is the signal.

3. Titrant is the reagent added to a solution containing the analyte whose volume is the signal.

4. Titrand/Titrate is the solution containing the analyte or the analyte whose identity is known
but of unknown concentration.

5. Equivalence point is the point in a titration where stoichiometrically equivalent amounts of

analyte and titrant react.

6. Endpoint is the point in a titration where we stop adding titrant.

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7. An indicator is a coloured compound whose colour change signals the titration's end point.

8. Titration error is the determinate error in titration due to the difference between the
endpoint and the equivalence point.

✓ Equivalence point and end-point

For a titration to be accurate, we must add a stoichiometrically equivalent amount of titrant to

a solution containing the analyte. We call this stoichiometric mixture the equivalence point.
Unlike precipitation gravimetry, where the precipitant is added in excess, determining the exact
volume of titrant needed to reach the equivalence point is essential. The product of the
equivalence point volume, Veq, and the titrant’s concentration, CT, gives the moles of titrant
reacting with the analyte.

Moles of titrant = Veq x CT

Knowing the stoichiometry of the titration reaction(s), we can calculate the moles of analyte.

Unfortunately, in most titrations, there is no obvious indication that the equivalence point has
been reached. Instead, we stop adding titrant when we reach an end point of our choosing.
Often, this endpoint is indicated by a change in the colour of a substance added to the solution
containing the analyte. Such substances are known as indicators. The difference between the
endpoint volume and the equivalence point volume is a determinate method error, often
called the titration error. If the endpoint and equivalence point volumes coincide closely, then
the titration error is insignificant and can be safely ignored. Clearly, selecting an appropriate
endpoint is critical if a titrimetric method is to give accurate results.

In volumetric methods, the titration error, Et, is given by Et = Vep - Veq

where Vep is the actual volume of reagent required to reach the endpoint, and Veq is the
theoretical volume necessary to reach the equivalence point.

✓ Volume as a signal

Almost any chemical reaction can serve as a titrimetric method, provided that three conditions
are met. The first condition is that all reactions involving the titrant and analyte must be of
known stoichiometry. If this is not the case, then the moles of titrant used in reaching the
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endpoint cannot tell us how much analyte is in our sample. Second, the titration reaction must
occur rapidly. If we add titrant at a rate faster than the reaction’s rate, then the endpoint will
exceed the equivalence point by a significant amount. Finally, a suitable method must be
available to determine the endpoint with an acceptable level of accuracy. These are significant
limitations, and for this reason, several titration strategies are commonly used.

A simple example of a titration is an analysis for Ag+ using thiocyanate, SCN–, as a titrant.

Ag+(aq) + SCN-(aq) ↔AgSCN(s)

This reaction occurs quickly and is of known stoichiometry. A titrant of SCN– is easily prepared
using KSCN. To indicate the titration’s end point, we add a small amount of Fe3+ to the solution
containing the analyte. The formation of the red-coloured Fe(SCN)2+ complex signals the
endpoint. This is an example of a direct titration since the titrant reacts with the analyte.

If the titration reaction is too slow, a suitable indicator is not available, or there is no useful
direct titration reaction, then an indirect analysis may be possible. Suppose you wish to
determine the concentration of formaldehyde, H2CO, in an aqueous solution. This type of
titration is called back titration.

Back titration is a titration in which a reagent is added to a solution containing the analyte,
and the excess reagent remaining after its reaction with the analyte is determined by titration.

✓ Primary and Secondary Standards

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

titrations and other analytical methods. The accuracy of a method critically depends on the
properties of the primary standard. A primary standard is an ultrapure compound that serves
as the reference material for titration or another type of quantitative analysis.

Important properties of 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.

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5. Reasonable solubility in the titration medium.

6. A reasonably large molar mass is needed so that the relative error associated with
weighing the standard is minimised.

Very few compounds meet or even approach these criteria, and only a limited number of
primary-standard substances are available commercially. As a consequence, less pure
compounds must sometimes be used in place of a primary standard. The purity of such a
secondary standard must be established by careful analysis.

A secondary standard is a compound whose purity has been determined by chemical analysis.
The secondary standard serves as the working standard material for titrations and many other
analyses.

✓ Standard Solutions

Standard solutions play a central role in all titrations. Therefore, we must consider the desirable
properties of 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
minimised;
3. react more or less completely with the analyte so that satisfactory endpoints are
realised;
4. undergo a selective reaction with the analyte that can be described by a balanced
equation.

Assignments: Mention five examples of each primary and secondary standard.

✓ Types of Volumetric Analysis

Titrimetric methods are classified into four groups based on the type of reaction involved.
These groups are acid-base titrations, in which an acidic or basic titrant reacts with an analyte
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that is a base or an acid; complexometric titrations involving a metal-ligand complexation

reaction; redox titrations, where the titrant is an oxidising or reducing agent; and precipitation
titrations, in which the analyte and titrant react to form a precipitate. Despite the difference in
chemistry, all titrations share several common features, providing the focus for this section.

1. Acid-base titrations

The earliest acid-based titrations involved the determination of the acidity or alkalinity of
solutions, as well as the purity of carbonates and alkaline earth oxides. Before 1800, acid-base
titrations were conducted using H2SO4, HCl, and HNO3 as acidic titrants and K2CO3 and
Na2CO3 as basic titrants. Endpoints were determined using visual indicators such as litmus,
which is red in acidic solutions and blue in basic solutions, or by observing the cessation of
CO2 effervescence when neutralising CO32–. The accuracy of an acid-base titration was limited
by the usefulness of the indicator and by the lack of a strong base titrant for the analysis of
weak acids.

The utility of acid-base titrimetry improved when NaOH was first introduced as a strong base
titrant in 1846. In addition, progress in synthesising organic dyes led to the development of
many new indicators. Phenolphthalein was first synthesised by Bayer in 1871 and used as a
visual indicator for acid-base titrations in 1877. Other indicators, such as methyl orange, soon
followed. Despite the increasing availability of indicators, the absence of a theory of acid-base
reactivity made selecting a proper indicator difficult.

2. Complexometric titration

The earliest titrimetric applications involving metal-ligand complexation were the

determinations of cyanide and chloride using, respectively, Ag+ and Hg2+ as titrants. Both
methods were developed by Justus Liebig (1803–1873) in the 1850s. The use of a monodentate
ligand, such as Cl– and CN–, however, limited the utility of complexation titrations to those
metals that formed only a single stable complex, such as Ag(CN)2– and HgCl2. Other potential
metal-ligand complexes, such as CdI42-, were not analytically useful because the stepwise
formation of a series of metal-ligand complexes (CdI+, CdI2, CdI3–, and CdI42-) resulted in a
poorly defined endpoint.

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Complexation titration is a titration in which the reaction between the analyte and titrant is a
complexation reaction.

The utility of complexation titrations improved following the introduction by Schwarzenbach

in 1945 of amino carboxylic acids as multidentate ligands capable of forming stable 1:1
complexes with metal ions. The most widely used of these new ligands was
ethylenediaminetetraacetic acid, EDTA, which forms strong 1:1 complexes with many metal
ions. The first use of EDTA as a titrant occurred in 1946 when Schwarzenbach introduced
metallochromic dyes as visual indicators for signalling the endpoint of a complexation titration.

3. Redox titration

Redox titrations were introduced shortly after the development of acid-base titrimetry. The
earliest methods took advantage of the oxidising power of chlorine. In 1787, Claude Berthollet
introduced a method for the quantitative analysis of chlorine water (a mixture of Cl2, HCl, and
HOCl) based on its ability to oxidise solutions of the dye indigo (indigo is colourless in its
oxidised state). In 1814, Joseph Louis Gay-Lussac (1778–1850) developed a similar method
for chlorine in bleaching powder.

In both methods, the endpoint was signalled visually. Before the equivalence point, the solution
remains clear due to the oxidation of indigo. After the equivalence point, however, unreacted
indigo imparts a permanent colour to the solution.

Redox titration is a titration in which the reaction between the analyte and titrant is an
oxidation/reduction reaction.

The number of redox titrimetric methods increased in the mid-1800s with the introduction of
MnO4–, Cr2O72– and I2 as oxidising titrants and Fe2+ and S2O32– as reducing titrants. Even with
the availability of these new titrants, the routine application of redox titrimetry to a wide range
of samples was limited by the lack of suitable indicators. Titrants whose oxidised and reduced
forms differ significantly in colour could be used as their own indicator. For example, the
intensely purple MnO4– ion serves as its own indicator since its reduced form, Mn2+, is almost
colourless. The utility of other titrants, however, required a visual indicator that could be added
to the solution. The first such indicator was diphenylamine, which was introduced in the 1920s.
Other redox indicators soon followed, increasing the applicability of redox titrimetry.

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4. Precipitation titration

Thus far we have examined titrimetric methods based on acid–base, complexation, and redox
reactions. A reaction in which the analyte and titrant form an insoluble precipitate also can
form the basis for a titration. We call this type of titration a precipitation titration.

One of the earliest precipitation titrations, developed at the end of the eighteenth century, was
used to analyse K2CO3 and K2SO4 in potash. Calcium nitrate, Ca(NO3)2, was used as a titrant,
forming a precipitate of CaCO3 and CaSO4. The endpoint was signalled by noting when the
addition of titrant ceased to generate additional precipitate. The importance of precipitation
titrimetry as an analytical method reached its zenith in the nineteenth century when several
methods were developed for determining Ag+ and halide ions.

Precipitation titration is a titration in which the reaction between the analyte and titrant
involves precipitation.

✓ Factors Affecting Volumetric Analysis

1. Measurement accuracy

2. Choice of indicator

3. Titration conditions such as Temperature, Pressure, and impurities.

✓ Calculations in Volumetric Analysis

The concentration of solutions can be expressed in several ways. For the standard solutions
used in most titrations, either molar concentration, M, or normal concentration, N, is usually
used. Molar concentration is the number of moles of reagent contained in one liter of solution,
and normal concentration is the number of equivalents of reagent in the same volume.

For the sake of this lecture, we base volumetric calculations exclusively on molar concentration
and molar masses.

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• Some useful relationships

Most volumetric calculations are based on two pairs of simple equations that are derived from
definitions of the mole, the millimole, and the molar concentration. For a chemical species, say
A, we can write

𝒎𝒂𝒔𝒔 𝒐𝒇 𝑨 (𝒈)
Amount of A (mol) = 𝒈 ----------------------------------- (1)
𝑴𝒐𝒍𝒂𝒓 𝒎𝒂𝒔𝒔 𝒐𝒇 𝑨 ( )
𝒎𝒐𝒍

𝒎𝒂𝒔𝒔 𝒐𝒇 𝑨 (𝒈)
Amount of A (mmol) = = 𝒈 -------------------------------- (2)
𝑴𝒊𝒍𝒍𝒊𝒎𝒐𝒍𝒂𝒓 𝒎𝒂𝒔𝒔 𝒐𝒇 𝑨 ( )
𝒎𝒎𝒐𝒍

The second pair of equations is derived from the definition of molar concentration, that is,

Amount of A (mol) = V (L) X CA (mol/L) --------------------------------- (3)

Amount of A (mmol) = V (mL) X CA (mmol/L) -------------------------------- (4)

where V is the volume of the solution.

Equations 1 and 3 are used when volumes are measured in liters, and Equations 2 and
Equations 4 when the units are milliliters.

Examples 1: Describe the preparation of 2.000 L of 0.0500 M AgNO3 (169.87 g/mol) from the
primary-standard-grade solid.

Solution

Amount of AgNO3 = V(L) x cAgNO3(mol/L)

𝑚𝑜𝑙
Amount of AgNO3 = 2.00 L x 0.0500 = 0.100 mol of AgNO3
𝐿

To obtain the mass of AgNO3, we rearrange Equation 2 (above) to give

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169.87𝑔 𝑜𝑓 𝐴𝑔𝑁𝑂3
mass of AgNO3 = 0.1000 mol of AgNO3 x = 16.987g
𝑚𝑜𝑙

Therefore, the solution should be prepared by dissolving 16.987 g of AgNO3 in water and
diluting to the mark in a 2.000 L volumetric flask.

Exercise: A standard 0.0100 M solution of Na+ is required to calibrate an ion-selective

electrode method to determine sodium. Describe how 500 mL of this solution can be prepared
from primary standard Na2CO3 (105.99 g/mL).

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