Kwame Nkrumah University of

Science & Technology, Kumasi, Ghana

CHEM 261

TITRIMETRIC METHODS OF ANALYSIS

Prof Godfred Darko

Department of Chemistry
Faculty of Physical and Computational Sciences
COURSE OUTLINE
a) Basic concepts of analytical chemistry:
i. Introduction and treatment of analytical data
ii. Statistical treatment of analytical data

b) Titrimetric analysis
i. Acid-Base titration
ii. Complexometric titration
iii. Precipitation titration
iv. Redox titration
References
 Harris, D.C. Quantitative Chemical Analysis. 6th Edition
 Miller, J.C. and Miller, J.N. Statistics for Analytical Chemistry. 3rd Edition
 Harvey, D. Modern Analytical Chemistry. 1st Edition.

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Analytical Chemistry Language
Analysis
• A process that provides chemical or
physical information about the
constituents in the sample or the
sample itself
• An analysis provides chemical or
physical information about a sample

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Analyte and Matrix
The components of interest in the sample
are called analytes, and the remainder of
the sample is the matrix

• Analytes: the constituents of interest

in a sample
• Matrix: all other constituents in a
sample except for the analytes

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Determination: An analysis of a sample to
find the identity, concentration, or
properties of the analyte

Measurement: An experimental
determination of an analyte’s chemical or
physical properties

Technique: A chemical or physical

principle that can be used to analyze a
sample
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Examples of techniques

Gravimetry Chromatography
Titrimetry Electrophoresis
Spectroscopy Electrochemical
Potentiometry Spectrophotometry

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Home work 1

Prepare a 5-minute lecturette on one of

the techniques outlined

Delivery: 10/02/2021

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Method
A method is the application of a
technique for the determination of a
specific analyte in a specific matrix

Eg., a gas chromatographic method for

analyzing organochlorine pesticides
residues in cocao is different from that
for PAH in air

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Procedure
• A set of written directions detailing
how to apply a method to a particular
sample, including information on proper
sampling, handling of interferents, and
validating results

• Written directions outlining how to

analyze a sample

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Procedure
A method does not necessarily lead to a
single procedure, as different analysts
or agencies will adapt the method to
their specific needs

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Chart showing hierarchical relationship among a technique, methods using that
technique, and procedures and protocols for one method
APHA = American Public Health Association, ASTM = American Society for Testing
Materials, EPA = Environmental Protection Agency
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Protocol
A set of written guidelines for analyzing a
sample specified by an agency

Protocols are usually validated procedures

Protocols are used to when an analysis is

to support or define public policy

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Signal
An experimental measurement that is
proportional to the amount of analyte (S)

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Signal
For techniques that respond to the
absolute amount of analyte in the sample,
the signal due to the analyte, (SA), is
directly proportional to the amount of the
analyte

where nA is the moles or grams of

analyte in the sample, and k is a
proportionality constant
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Signal
For techniques that respond to the
relative amount of analyte

where CA is the concentration of analyte in

the sample, and k is a proportionality constant

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Types of techniques
Total analysis technique
• A technique in which the signal is
proportional to the absolute amount of
analyte
• Most early analytical methods used total
analysis techniques
• Eg., gravimetry, titrimetry, and
coulometry
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Types of techniques
Total analysis techniques

• The signal results from one or more

chemical reactions involving the analyte

• These reactions may involve any

combination of precipitation, acid–base,
complexation, or redox chemistry

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Types of techniques
Concentration/Instrumental techniques
• Techniques in which the signal is
proportional to the relative amount of
analyte in a sample
• Concentration techniques rely on
measuring an optical or electrical signal,
so they are also known as “instrumental”
techniques
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Types of techniques
Class exercise (5 min)

Give 1 example each of i) total analysis

techniques and ii) concentration techniques

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Selecting Analytical Method
Choice of a method depends on:

Accuracy Ruggedness
Precision Scale of operation
Sensitivity Analysis time
Selectivity Availability of equipment
Robustness Analysis cost

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Accuracy
Accuracy is a measure of how closely the
result of an experiment agrees with the
expected result

Accuracy is measured in term of the

error associated with the measurement
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Accuracy
Analytical methods may be divided into
three based on the magnitude of their
relative errors
• Highly accurate: < 1% relative error
• Moderately accurate: 1 - 5% relative error
• Low accuracy: > 5% relative error

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Accuracy
The magnitude of a method’s relative
error depends on how accurately the
signal is measured, and the ease of
handling the sample without loss or
contamination
In general, total analysis methods
produce results of high accuracy, and
concentration methods range from high
to low accuracy
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Precision
• Precision is how close a series of
measurements are to one another or
how far out a measurement is taken

• An indication of the reproducibility of

a measurement or result

• Precision is a measure of this

variability
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 Accuracy and Precision

A measurement can have high precision, but not be as

accurate as a less precise one
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Precision
Precision depends on uncertainty in
measuring the signal and the ease of
handling samples reproducibly

Signal for a total analysis method can be

measured with a higher precision than
the corresponding signal for a
concentration method

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Sensitivity
It is the ability to demonstrate that
two samples have different amounts of
analyte

Sensitivity is the change in signal per

unit change in the amount of analyte
and is equivalent to the proportionality
constant, k

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Sensitivity
Sensitivity is not the detection limit which
is the smallest amount of analyte that can
be determined with confidence (to be
treated later)

Detection limit is a statistical parameter

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Sensitivity
If ∆SA is the smallest increment in signal
that can be measured, then the smallest
difference in the amount of analyte that
can be detected is

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Selectivity
An analytical method is selective if its
signal is a function of only the amount of
analyte present in the sample
A measure of a method’s freedom from
interferences

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Selectivity
In the presence of an interferent, total
signal produced by a sample is

where Ssamp is the total signal due to constituents in the sample; kA and kI
are the sensitivities for the analyte and the interferent, respectively; and
nI and CI are the moles (or grams) and concentration of the interferent in
the sample

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Selectivity
The selectivity of the method for an
interferent relative to the analyte is
defined by a selectivity coefficient,
(KA,I).

A selectivity coefficient greater than +1 or less than –1

indicates that the method is more selective for the
interferent than for the analyte

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Solving for KI

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Selectivity
Selectivity coefficient tells about an
interferent’s potential effect on an
analysis

An interferent will not pose a problem if

KA,I × nI is significantly smaller than nA,
or KA,I × CI is significantly smaller than
CA

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Robustness and Ruggedness

A method that can be applied to analytes

in a wide variety of matrices is
considered robust

A method that is insensitive to changes in

experimental conditions is considered
rugged

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Selecting a method
Other considerations
Scale of operation
• amount of sample available for the
analysis
• the concentration of analyte in the sample
• absolute amount of analyte needed to
obtain a measurable signal

Equipment, Time, and Cost

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Developing a procedure
Considerations in developing a procedure,
• Compensating for interferences
• Selecting and calibrating equipment
• Standardizing the method
• Acquiring a representative sample
• Validating the method
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Compensating for interferences

Accuracy of a method depends on its

selectivity for the analyte

Potential interferents may be present in

• the sample itself
• the reagents used during the analysis

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Compensating for interferences
In the absence of an interferent, the
total signal measured during an analysis,
Smeas, is a sum of the signal due to the
analyte, and the signal due to the
reagents, Sreag

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Compensating for interferences
The contribution of Sreag is determined by
measuring the signal for a reagent or
method blank that does not contain the
sample

A method blank is a sample that contains

all components of the matrix except the
analyte

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Compensating for interferences
Compensating for an interference in the
sample’s matrix is more difficult

If the identity and concentration of the

interferent are known, then it can be
added to the reagent blank

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Compensating for interferences
In most analyses, however, the identity or
concentration of matrix interferents is
not known, and their contribution to Smeas
is not included in Sreag

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Calibration and Standardization
Standardization is the process of
experimentally determining the
relationship between the signal and the
amount of analyte

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Calibration and Standardization
For a total analysis method,
standardization is the stoichiometry of
the chemical reactions responsible for the
signal

For a concentration method,

it is a theoretical function that cannot be
calculated without experimental
measurements
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Calibration and Standardization
To standardize a method, the value of k is
determined by measuring the signal for one
or more standards, each containing a
known concentration of analyte
Concentration Signal
0 0
3 30
5 50
10 100
15 150
20 200

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Calibration and Standardization
A plot of Smeas versus the concentration
of analyte in the standards is called a
calibration curve
250
y = 10x +0.0021
200
R² = 0.9999
150
Signal

100

50

0
0 5 10 15 20 25
Concentration

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Calibration and Standardization
Balances are calibrated using a standard
weight whose mass can be traced to the
internationally accepted platinum–iridium
prototype kilogram

pH meters are calibrated by adjusting

their readings to standard pH solutions
(usually pH 2, 7 and 14)

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Sampling
A proper sampling strategy ensures that
samples are representative of the
material from which they are taken

Biased or nonrepresentative sampling and

contamination of samples during or after
their collection are two sources of
sampling error

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Sampling
Sampling errors are independent of
analysis errors

As a result, sampling errors cannot be

corrected by evaluating a reagent blank

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Validation
Validation is the process of verifying that
a procedure yields acceptable results
Validation evaluates the precision and
accuracy of a procedure
It also ensures that a written procedure
has a sufficient enough details to be used
by others

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Validation
Validation is carried out by analyzing a
certified reference material (standard
sample whose composition closely matches
the samples) for which the procedure was
developed
Intra-laboratory and inter-laboratory
differences in the procedure also can be
evaluated

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Validation
In the absence of appropriate standards,
accuracy can be evaluated by comparing
results obtained with a new method to
those obtained using a method of known
accuracy

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Validation
A procedure is validated by
• Analysis of certified reference
materials (CRM)
• Intra- and inter-laboratory analysis
• Comparism with a known method

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Quality assurance and quality
control (QA/QC)

Steps taken to ensure that the work

conducted in an analytical lab is capable
of producing acceptable results

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Validation
Quality assurance: The steps taken during
an analysis to ensure that the analysis is
under control and that it is properly
monitored

Quality control: The steps taken to

ensure that an analysis is under statistical
control

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QA/QC
Good laboratory practices
Those general laboratory procedures that,
when followed, help ensure the quality of
analytical work
Good measurement practices
Those instructions outlining how to
properly use equipment and instrumentation
to ensure the quality of
measurements
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 Reading assignment

Read about how to prepare

standard and dilute solutions

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