Unit 6 - AcidBase Volumetric Analysis

Module 6
Acid-Base Volumetric
Analyses
Titration is a tried-and-true technique, capable of high precision and accuracy.
©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

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.
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.
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.
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.
©Gary Christian,
Analytical Chemistry,
6th Ed. (Wiley)
Fig. 8.4. pH transition ranges and colors of some common indicators.

https://www.coursehero.com/sg/general-chemistry/acid-base-titrations/
The Titration Setup
The Titration Process
A. Pipet a volume of unknown solution (analyte) into the flask

B. Add few drops of indicator
C. Add titrant to the flask with swirling until the color of the indicator
persists.
D. Note the volume of titrant used when the end point is achieved.
Using Phenolphthalein
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. 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.
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.
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.
Gravimetric titrations
Mass (weight) or gravimetric titrations differ from their volumetric counterparts in
that the mass of titrant is measured rather than the volume.
Calculations Associated with Mass Titrations
Concentration for mass titrations is expressed as the weight concentration, c w, in

weight molar concentration units, M w, 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 = 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.
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 nonaqueous 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
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.
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.
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.
Figure 13-2 The two types of titration curves
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.
Strong Acid- Strong Base
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.
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 (mg)/millimolar mass A (mg/mmol)
Amount A (mol) = V(L)  cA (mol A/L)
amount A (mmol) = V (mL)  cA (mmol A/L)
Table 8.1 summarizes the equations governing the different portions of the titration curve.
We use f to denote the fraction of analyte, which has been titrated by titrant.
As the titration proceeds (0<f<1), part of the H+ is removed from solution as H2O. So the concentration
of H+ gradually decreases. At 90% neutralization (f = 0.9) (90 mL NaOH), only 10% of the H+ remains.
However, as the equivalence point is approached (the point at which a stoichiometric amount of base is added),
the H+ concentration is rapidly reduced until at the equivalence point (f=1), when the neutralization is complete,
a neutral solution of NaCl remains and the pH is 7.0
As we continue to add NaOH (f>1), the OH− concentration rapidly increases

Working with Titration Data
Calculating Molar Concentrations from Standardization Data
Strong acid - Strong base Titration

Weak acid - Strong base Titration

… continuation

Calculating the Quantity of Analyte from Titration Data

Unit 6 - AcidBase Volumetric Analysis

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Module 6

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

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

Volumetric titrations involve measuring the volume of a solution of known

In Gravimetric titrations, the mass of the reagent is measured instead of its

In coulometric titrations, the “reagent” is a constant direct electrical current of

The equivalence point of a titration cannot be determined experimentally.

Indicators are often added to the analyte solution to produce an

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

Where Vep is the actual volume

Fig. 8.4. pH transition ranges and colors of some common indicators.

A. Pipet a volume of unknown solution (analyte) into the flask

A primary standard is an ultrapure compound that serves as the reference

A primary standard must fulfill the following requirements:

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

The direct method is a method in which a carefully determined mass of a

The second is by standardization in which the titrant to be standardized is

Calculations Associated with Mass Titrations

Concentration for mass titrations is expressed as the weight concentration, c w, in

cw = no. mol A = no. mmol A = nA

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

2. Temperature corrections are unnecessary because the mass (weight) molar

Titration curves are plots of a concentration-related variable versus titrant volume.

Types of Titration Curves

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

Molar concentration is the number of moles of reagent contained in one liter of

Some Useful Relationships

As we continue to add NaOH (f>1), the OH− concentration rapidly increases

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

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