Titrations in Analytical

Chemistry

Chem 5: Analytical Chemistry

Lecture
Titrations in Analytical Chemistry
➢ Titration methods 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 known magnitude.

➢ Volumetric titrations involve measuring the

volume of a solution of known
concentration that is needed to react completely with
the analyte.
Titrations in Analytical Chemistry
➢ In Gravimetric titrations, the mass of the reagent is
measured instead of its volume.

➢ In Coulometric titrations, the “reagent” is a constant

direct electrical current of known magnitude that
consumes the analyte. For this titration, the time
required (and thus the total charge) to complete the
electrochemical reaction is measured (see Section
22D-5).

➢ This lecture provides introductory material that

applies to all the different types of titrations
 Before the titration
begins indicator
should be added.

Typical setup for

carrying out a
titration
The reference
point on the meniscus
and the proper position
of the eye for reading are The titrant is added to the
depicted in Figure 2-21. flask with swirling until the
color of the indicator persists
SOME TERMS USED IN VOLUMETRIC TITRATIONS
A standard solution (or a standard titrant) is a reagent
of known concentration that is used to carry out a
volumetric titration.

The 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.
SOME TERMS USED IN VOLUMETRIC TITRATIONS

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.

Back-titrations are often required when the rate of

reaction between the analyte and reagent is slow or
when the standard solution lacks stability.
Equivalence Points and End Points

• The equivalence point is the point in a titration

when the amount of added standard reagent is
equivalent to the amount of analyte.

• The equivalence point of a titration cannot be

determined experimentally.
 Equivalence Points and End Points

• It can only be estimated by observing some

physical change associated with the condition of
chemical equivalence called the end point for the titration
• Indicators are often added to the analyte solution to
produce an observable physical change (signaling the end
point) at or near the equivalence point.
Equivalence Points and End Points

• The difference in volume or mass between the

equivalence point and the end point is the titration error.
The titration error is given as: Et = Vep Veq
Where
Vep is the actual volume of reagent required to reach the
End Point
Veq is the theoretical volume necessary to reach the
equivalence point.

t
Primary Standards
A primary standard is an ultrapure compound that serves as the
reference material for a titration or for another type of quantitative
analysis.
A primary standard must fulfill the following requirements:
1) High purity.
2) Atmospheric stability.
3) Modest cost.
4) Absence of hydrate water so that the composition of the solid
does not change with variations in humidity
5) Reasonable solubility in the titration medium.
6) Reasonably large molar mass so that the relative error
associated with weighing the standard is minimized.
Primary Standards

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 for many other analyses.
STANDARD SOLUTIONS

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;
4. undergo a selective reaction with the analyte
that can be described by a balanced equation.
STANDARD SOLUTIONS

The accuracy of a titration depends on the accuracy of the

concentration of the standard solution used. Two basic methods
that are used to establish the concentration are:
1. Direct method
2. Standardization
The direct method is a method in which a carefully determined
mass of a primary standard is dissolved in a suitable solvent and
diluted to a known volume in a volumetric flask.
The second is by standardization in which the titrant to be
standardized is used to titrate
(1) a known mass of a primary standard,
(2) a known mass of a secondary standard, or
Volumetric calculations
➢ The concentration of solutions may be expressed in several ways. For standard
solutions, either molar concentration, c, or normal concentration, cN, is 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.

13C-1 Some Useful Relationships

For the chemical species A, we can write

amount A(mol) = mass A (g)/molar mass A (g/mol)

amount A (mmol) = mass A (g)/millimolar mass A (g/mmol)

Amount A (mol) = V(L)  cA (mol A/L)

amount A (mmol) = V (mL)  cA (mmol A/L)

Calculating the Molar Concentration of Standard Solutions
13C-3 Working with Titration Data

1. Concentrations of solutions that have been

standardized against either a primary standard or
another standard solution.
2. In the second, we calculate the amount of analyte
in a sample from titration data.
Working with Titration Data

Calculating Molar Concentrations from standardization data

Calculating the Quantity of Analyte from Titration Data
13D GRAVIMETRIC TITRATIONS
➢ Mass (weight) or gravimetric titrations differ from their volumetric counterparts in
that the mass of titrant is measured rather than the volume.
➢ Therefore, in a mass titration, a balance and a weighable solution dispenser are
substituted for a buret and its markings.

13D-1 Calculations Associated with Mass Titrations

Concentration for mass titrations is expressed as the weight concentration, cw, in
weight molar concentration units, 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.

Cw = no. mol A = no. mmol A Cw (A) = nA-

no. kg soln no. g soln msoln

Where:
nA is the number of moles of species A and
msoln is the mass of the solution.
13D-2 Advantages of Gravimetric Titrations

In addition to greater speed and convenience, mass titrations offer certain other
advantages over their volumetric counterparts:

1. Calibration of glassware and tedious cleaning to ensure proper drainage are

completely eliminated.
2. Temperature corrections are unnecessary because the mass (weight) molar
concentration does not change with temperature, in contrast to the volume molar
concentration. This advantage is particularly important in non-aqueous titrations
because of the high coefficients of expansion of most organic liquids (about 10 times
that of water).

3. Mass measurements can be made with considerably greater precision and accuracy
than can volume measurements.

4. Gravimetric titrations are more easily automated than are volumetric titrations.
TITRATION CURVES
➢ A titration curve is a plot of some function of the
analyte or titrant concentration on the y axis versus
titrant volume on the x axis.

13E-1 Types of Titration Curves

There are two types of titration curves:

*A sigmoidal curve in which the p-function of

analyte (or sometimes the titrant) is plotted as
a function of titrant volume. Important
observations are confined to a small region
(typically ± 0.1 to ± 0.5 mL) surrounding
the equivalence point.

*A linear segment curve in which

measurements are made on both sides of, but
well away from, the equivalence point.
The vertical axis represents an instrument
reading that is directly proportional to the
concentration of the analyte or the titrant.
Concentration Changes During Titrations
Concentration Changes During a Titration of 50.00 mL of 0.1000 M HCl

The concentration of HCl is equal to

the original number of millimoles of
HCl (50.00 mL x 0.1000 M) minus the
number of millimoles of NaOH added
(VNaOH x 0.1000 M) divided by the total
volume of the solution:

Figure 13-3 Titration curves of pH and pOH versus volume of base for the titration of
0.1000 M HCl with 0.1000 M NaOH.

The equivalence point in a titration is characterized by major changes in the

Practice Exercise:

Chapter 13, Questions and Problems

13-1, 13-3, 13-6, 13-8, 13-10, 13-11, 13-12, 13-13, 13-14,

13-16, 13-18, 13-20, 13-22, 13-24, 13-26, 13-28, 13-30.

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