CH 13 Titrations in Analytical Chemistry

2015/9/23
Chapter 13
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: measure the volume of a solution of known

concentration that is needed to react completely with the analyte.
Gravimetric titrations: the mass of the reagent is measured instead

of its volume.
Coulometric titrations, the “reagent” is a constant direct electrical

current of known magnitude that consumes the analyte.
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13A 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.
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.
It can only be estimated by observing some physical change

associated with the condition of chemical equivalence called
the end point for the titration.
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The difference in volume or mass between the

equivalence point and the end point is the titration error.
Indicators are often added to the analyte solution to

produce an observable physical change (signaling the end
point) at or near the equivalence point.
The titration error is given as: Et = Vep  Veq
Where Vep is the actual volume of reagent required to

reach the end point and Veq is the theoretical volume
necessary to reach the equivalence point.
Figure 13-1 The titration process
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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:
High purity, atmospheric stability, absence of hydrate water so that
the composition of the solid does not change with variations in
humidity, modest cost, reasonable solubility in the titration medium,
reasonably large molar mass so that the relative error associated
with weighing the standard is minimized.
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.
13B 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.
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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
(3) a measured volume of another standard solution.
13C Volumetric Calculations
The concentration of solutions may be expressed in several ways. For

standard solutions, either molar concentration (莫耳濃度), c, or normal
concentration (當量濃度), 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.
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)
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Calculating the Molar Concentration of Standard Solutions
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Working with Titration Data

Calculating Molar Concentrations from Standardization Data
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Calculating the Quantity of Analyte from Titration Data
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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.
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. kg soln = no. mmol A/no. g soln = nA /msoln
where nA is the number of moles of species A and msoln is the mass

of the solution. (ex)
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13D-2 Advantages of Gravimetric Titrations
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.
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13E Titration curves
Titration curves are plots of a concentration-related variable versus

titrant volume. 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
(1) A sigmoidal curve in which the p-function of analyte (or

sometimes the titrant) is plotted as a function of titrant volume.
(2) 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.
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Figure 13-2 The two types of

titration curves
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13E-2 Concentration Changes During Titrations (Feature 13-3)
H3O+ + OH-  2H2O
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The equivalence point in a titration is characterized by major

changes in the relative concentrations of reagent and analyte.
The large changes in relative concentration that occur in the

region of chemical equivalence are shown by plotting the
negative logarithm of the analyte or the titrant concentration
(the p-function) against reagent volume.
Titration curves define the properties required of an indicator or

instrument and allow us to estimate the error associated with
titration methods.
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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.
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2015/9/23

Titration methods are based on determining the quantity of a reagent

The reagent may be a standard solution of a chemical or an electric

Volumetric titrations: measure the volume of a solution of known

Gravimetric titrations: the mass of the reagent is measured instead

Coulometric titrations, the “reagent” is a constant direct electrical

13A Some terms used in volumetric titrations

Equivalence Points and End Points

The equivalence point is the point in a titration when the

The equivalence point of a titration cannot be determined

It can only be estimated by observing some physical change

The difference in volume or mass between the

Indicators are often added to the analyte solution to

The titration error is given as: Et = Vep  Veq

Where Vep is the actual volume of reagent required to

Figure 13-1 The titration process

A secondary standard is a compound whose purity has been

13B Standard solutions

1.be sufficiently stable so that it is necessary to determine its

2.react rapidly with the analyte so that the time required

3.react more or less completely with the analyte so that

4.undergo a selective reaction with the analyte that can be

The accuracy of a titration depends on the accuracy of the

The direct method is a method in which a carefully determined

The second is by standardization in which the titrant to be

13C Volumetric Calculations

The concentration of solutions may be expressed in several ways. For

Calculating the Molar Concentration of Standard Solutions

Working with Titration Data

Calculating the Quantity of Analyte from Titration Data

13D Gravimetric titrations

13D-1 Calculations Associated with Mass Titrations

cw = no. mol A/no. kg soln = no. mmol A/no. g soln = nA /msoln

where nA is the number of moles of species A and msoln is the mass

13D-2 Advantages of Gravimetric Titrations

1. Calibration of glassware and tedious cleaning to ensure proper

2. Temperature corrections are unnecessary because the mass

3. Mass measurements can be made with considerably greater

4. Gravimetric titrations are more easily automated than are

13E Titration curves

Titration curves are plots of a concentration-related variable versus

13E-1 Types of Titration Curves

(1) A sigmoidal curve in which the p-function of analyte (or

(2) A linear segment curve in which measurements are made on

The vertical axis represents an instrument reading that is directly

Figure 13-2 The two types of

13E-2 Concentration Changes During Titrations (Feature 13-3)

H3O+ + OH-  2H2O

The equivalence point in a titration is characterized by major

The large changes in relative concentration that occur in the

Titration curves define the properties required of an indicator or

Figure 13-3 Titration curves of pH and pOH versus volume of

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