SST 1202: ANALYTICAL CHEMISTRY (3CU)

Course Description

 Introduction to Analytical chemistry.

 Solutions: Concentration terminologies, Standards, Final, Primary and Secondary
preparation and dilution of solutions.
 Separation and purification; Decanting, centrifugation, sublimation, filtration,
evaporation, crystallization, re-crystallisation and fractional crystallization. Diffusion,
fractional, steam and vacuum distillation. Use of activated carbon. Solvent extraction;
separating funnel, continuous extractors. Counter current distribution, chromatography,
ion –exchange, electrophoresis and dialysis.
 Volumetric analysis; calibration of volumetric ware, precipitation and complexometric.
Titration error, end point detection methods.
 Gravimetric analysis; process, digestion, washing, drying and ignition of precipitate, co-
precipitation and post precipitation.

INTRODUCTION

Analytical chemists and others in many disciplines frequently ask questions such as: What is this
substance? How concentrated is this solution? What is the structure of this molecule? The
answers to these and many other similar questions are provided by the techniques and methods
of analytical chemistry. They are common to a wide range of activities, and the demand for
analytical data of chemical nature is steadily growing. Geologists, biologists, environmental and
material scientists, physicists, pharmacists, clinicians and engineers may all find it necessary to
use or rely on some of the techniques of analysis.

If we look back some forty or fifty years, chemical analysis concentrated on perhaps three main
areas: qualitative testing, quantitative determinations, particularly by classical techniques such as
titrimetry and gravimetry, and structural analysis by procedures requiring laborious and time-
consuming calculations. The analytical chemist of today has an armoury of instrumental
techniques, automated systems and computers which enable analytical measurements to be made
more easily, more quickly and more accurately. However, pitfalls still exist! Unless the

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analytical chemist has a thorough understanding of the principles, practice and limitations of
each technique he/she employs, results may be inaccurate, ambiguous, misleading or invalid.

Regardless of the discipline from which the need for chemical analysis arises, common questions
must be asked:

- How should a representative sample be obtained?

- What is to be determined and with what quantitative precision?

- What other components are present and will they interfere with the analytical measurements?

- How much material is available for analysis, and how many samples are to be analyzed?

- What instrumentation is to be used?

- How reliable is the data generated?

ANALYTICAL CHEMISTRY, ITS FUNCTIONS AND APPLICATIONS

Analytical chemistry is a scientific discipline used to study the chemical composition, structure
and behavior of matter. The purpose of chemical analysis is to gather and interpret chemical
information that will be of value to society in a wide range of contexts.

Analytical chemistry involves the application of a range of techniques and methodologies to

obtain and assess qualitative, quantitative and structural information on the nature of matter.

Qualitative analysis is the identification of elements, species and/or compounds present in a

sample.

Quantitative analysis is the determination of the absolute or relative amounts of elements,

species or compounds present in a sample.

Structural analysis is the determination of the spatial arrangement of atoms in an element or

molecule or the identification of characteristic groups of atoms (functional groups).

An element, species or compound that is the subject of analysis is known as an analyte.

The remainder of the material or sample of which the analyte(s) form(s) a part is known as the
matrix.

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Applications of Analytical chemistry

Analytical data is required in a wide range of disciplines and situations that include not just
chemistry and most other sciences, from biology to zoology, but the arts, such as painting and
sculpture, and archaeology. Space exploration and clinical diagnosis are two quite key areas in
which analytical data is vital.

Important areas of application include the following:

Quality control (QC).

In many manufacturing industries, the chemical composition of raw materials, intermediates and
finished products needs to be monitored to ensure satisfactory quality and consistency. Virtually
all consumer products from automobiles to clothing, pharmaceuticals and foodstuffs, electrical
goods, sports equipment and horticultural products rely, in part, on chemical analysis. The food,
pharmaceutical and water industries in particular have stringent requirements backed by
legislation for major components and permitted levels of impurities or contaminants.

Monitoring and control of pollutants.

The presence of toxic heavy metals (e.g., lead, cadmium and mercury), organic chemicals (e.g.
polychlorinated biphenyls and detergents) and vehicle exhaust gases (oxides of carbon, nitrogen
and sulfur, and hydrocarbons) in the environment are health hazards that need to be monitored by
sensitive and accurate methods of analysis, and remedial action taken. Major sources of pollution
are gaseous, solid and liquid wastes that are discharged or dumped from industrial sites, and
vehicle exhaust gases.

Clinical and biological studies.

The levels of important nutrients, including trace metals (e.g., sodium, potassium, calcium and
zinc), naturally produced chemicals, such as cholesterol, sugars and urea, and administered drugs
in the body fluids of patients undergoing hospital treatment require monitoring. Speed of analysis
is often a crucial factor and automated procedures have been designed for such analyses.

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Geological assays.

The commercial value of ores and minerals is determined by the levels of particular metals,
which must be accurately established. Highly accurate and reliable analytical procedures must be
used for this purpose, and referee laboratories are sometimes employed where disputes arise.

Fundamental and applied research.

The chemical composition and structure of materials used in or developed during research
programs in numerous disciplines can be of significance. Where new drugs or materials with
potential commercial value are synthesized, a complete chemical characterization may be
required involving considerable analytical work. A combination of analytical techniques is an
approach used in pharmaceutical research that generates very large numbers of new compounds
requiring confirmation of identity and structure.

ANALYTICAL PROBLEMS AND PROCEDURES

Selecting or developing and validating appropriate methods of analysis to provide reliable data in
a variety of contexts are the principal problems faced by analytical chemists. The most important
aspect of an analysis is to ensure that it will provide useful and reliable data on the qualitative
and/or quantitative composition of a material or structural information about the individual
compounds present. The most appropriate analytical technique and method can then be selected
from those available or new ones devised and validated by the analysis of substances of known
composition and/or structure.

Analytical procedures

The stages or steps in an overall analytical procedure can be summarized as follows.

Definition of the problem: Analytical information and level of accuracy required. Costs, timing,
availability of laboratory instruments and facilities.

Choice of technique and method: Selection of the best technique for the required analysis, such
as chromatography, infrared spectrometry, titrimetry, thermogravimetry. Selection of the method
(i.e. the detailed stepwise instructions using the selected technique).

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Sampling: Selection of a small portion of the material to be analyzed. Special procedures need to
be used to ensure that a genuinely representative sample is obtained.

Sample pre-treatment or conditioning: Conversion of the sample into a form suitable for
analysis by the selected technique and method. This may involve dissolving it, converting the
analyte(s) into a specific chemical form or separating the analyte(s) from other components of
the sample (the sample matrix) that could interfere with detection or quantitative measurements.

Qualitative analysis: Tests on the sample under specified and controlled conditions. Tests on
reference materials for comparison. Interpretation of the tests.

Quantitative analysis: Preparation of standards containing known amounts of the analyte(s) or

of pure reagents to be reacted with the analyte(s). Calibration of instruments to determine the
responses to the standards under controlled conditions. Measurement of the instrumental
response for each sample under the same conditions as for the standards. All measurements may
be replicated to improve the reliability of the data, but this has cost and time implications.
Calculation of results and statistical evaluation.

Preparation of report or certificate of analysis: This should include a summary of the

analytical procedure, the results and their statistical assessment, and details of any problems
encountered at any stage during the analysis.

Review of the original problem. The results need to be discussed with regard to their
significance and their relevance in solving the original problem. Sometimes repeat analyses or
new analyses may be undertaken.

ANALYTICAL TECHNIQUES AND METHODS

Analytical techniques

There are numerous chemical or physico-chemical processes that can be used to provide
analytical information. The processes are related to a wide range of atomic and molecular
properties and phenomena that enable elements and compounds to be detected and/or
quantitatively measured under controlled conditions. The underlying processes define the various

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analytical techniques. The more important of these are listed in Table 1, together with their
suitability for qualitative, quantitative or structural analysis and the levels of analyte(s) in a
sample that can be measured.

Table 1: Analytical techniques and principal applications

Technique Property measured Principal areas of application

Gravimetry Weight of pure analyte or Quantitative for major or minor
compound of known components.
stoichiometry.

Titrimetry Volume of standard reagent Quantitative for major or minor

solution reacting with the components.
analyte.

Atomic and molecular Wavelength and intensity of Qualitative, quantitative or structural

spectrometry. electromagnetic radiation for major down to trace level
emitted or absorbed by the components.
analyte

Mass spectrometry. Mass of analyte or fragments Qualitative or structural for major

of it down to trace level components,
isotope ratios.

Chromatography and Various physico-chemical Qualitative and quantitative

electrophoresis properties of separated separations of mixtures at major to
analytes. trace levels

Thermal analysis Chemical/physical changes in Characterization of single or mixed

the analyte when heated or major/minor components.
cooled.

Electrochemical Electrical properties of the Qualitative and quantitative for major

analysis analyte in solution. to trace level components.

Radiochemical Characteristic ionizing nuclear Qualitative and quantitative at major

analysis radiation emitted by the to trace levels.
analyte.

Atomic and molecular spectrometry and chromatography, which together comprise the
largest and most widely used groups of techniques, can be further subdivided according to their
physico-chemical basis. Spectrometric techniques may involve either the emission or

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absorption of electromagnetic radiation over a very wide range of energies, and can provide
qualitative, quantitative and structural information for analytes from major components of a
sample down to ultra-trace levels. The most important atomic and molecular spectrometric
techniques and their principal applications are listed in Table 2.

Table 2: Spectrometric techniques and principal applications

Technique Basis Principal applications

Plasma emission Atomic emission after excitation Determination of metals and some
spectrometry in high temperature gas plasma. non-metals mainly at trace levels

Flame emission Atomic emission after flame Determination of alkali and

spectrometry excitation. alkaline earth metals.

Atomic absorption Atomic absorption after Determination of trace metals and

spectrometry atomization by flame or some non-metals
electrothermal means.

Atomic fluorescence Atomic fluorescence emission Determination of mercury and

spectrometry after flame excitation. hydrides of non-metals at trace
levels.

X-ray emission Atomic or atomic fluorescence Determination of major and minor

spectrometry emission after excitation by elemental components of
electrons or radiation. metallurgical and geological
samples.
γ-spectrometry γ-ray emission after nuclear Monitoring of radioactive elements
excitation. in environmental samples.
Ultraviolet/visible Electronic molecular absorption Quantitative determination of
spectrometry in solution. unsaturated organic compounds.
Infrared spectrometry Vibrational molecular absorption Identification of organic
compounds.
Nuclear magnetic Nuclear absorption (change of Identification and structural
resonance spectrometry spin states). analysis of organic compounds.
Mass spectrometry Ionization and fragmentation of Identification and structural
molecules. analysis of organic compounds.

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Chromatographic techniques provide the means of separating the components of mixtures and
simultaneous qualitative and quantitative analysis, as required. The linking of chromatographic
and spectrometric techniques, called hyphenation, provides a powerful means of separating and
identifying unknown compounds.

Electrophoresis is another separation technique with similarities to chromatography that is

particularly useful for the separation of charged species. The principal separation techniques and
their applications are listed in Table 3.

Table 3. Separation techniques and principal applications

Technique Basis Principal applications

Thin-layer chromatography Differential rates of migration
Qualitative analysis of
of analytes through a
mixtures.
Gas chromatography stationary phase by movement Quantitative and qualitative
of a liquid or gaseous mobile determination of volatile
phase compounds
High-performance liquid Quantitative and qualitative
chromatography determination of non-volatile
compounds.
Electrophoresis Differential rates of migration Quantitative and qualitative
of analytes through a buffered determination of ionic
medium. compounds.

Analytical methods

An analytical method consists of a detailed, stepwise list of instructions to be followed in the

qualitative, quantitative or structural analysis of a sample for one or more analytes and using a
specified technique. It will include a summary and lists of chemicals and reagents to be used,
laboratory apparatus and glassware, and appropriate instrumentation. Many standard analytical
methods have been published as papers in analytical journals and other scientific literature, and
in textbook form. Often, laboratories will develop their own in-house methods or adapt existing
ones for specific purposes. Method development forms a significant part of the work of most
analytical laboratories, and method validation and periodic revalidation is a necessity.

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Selection of the most appropriate analytical method should take into account the following
factors:

- The purpose of the analysis, the required time scale and any cost constraints;
- The level of analyte(s) expected and the detection limit required;
- The nature of the sample, the amount available and the necessary sample preparation
procedure;
- The accuracy required for a quantitative analysis;
- The availability of reference materials, standards, chemicals and solvents,
instrumentation and any special facilities;
- Possible interference with the detection or quantitative measurement of the analyte(s) and
the possible need for sample clean-up to avoid matrix interference;
- The degree of selectivity available: Methods may be selective for a small number of
analytes or specific for only one;
- Quality control and safety factors.

SAMPLING

A complete knowledge of sampling processes eliminates probable errors. The reliability of

analytical data depends upon the kind of sample one is using in chemical analysis. The sample
should be homogeneous. A sample is a portion of material, selected for analysis, which possesses
the essential characteristics of the bulk of the original material.

Sampling theory

An ideal sample is supposed to be identical to the bulk of the material from which it is obtained
in all its respective properties. The factors to be noted are mainly the cost of the test and the
value of the products, the permitted variation in the material, the accuracy of the test method and
the nature of the material used. There are many obvious blunders in sampling which we may
term as pitfalls in sampling. For instance, it is often dangerous to accept any material for analysis
without some knowledge of its history. Operations that change the composition of the sample
must be avoided. Adhesive tapes should not ordinarily be stuck on samples of minerals or ores

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because they give erroneous information about the presence of zinc oxide from the adhesive
tape.

Stratified sampling versus Random sampling

A number of samples can be chosen at random from the bulk of the material or sampling can be
stratified. Stratified sampling is a sampling technique in which the researcher divides the entire
population into different sub groups or strata, and then randomly selects the final subjects
proportionally from the different strata. The strata are formed based on the members’ shared
attributes or characteristics.

Advantages of stratified sampling

i. A stratified sample can provide greater precision than a simple random sample of
the same size.
ii. Because it provides greater precision, a stratified sample often requires a smaller
sample, which saves money.
iii. A stratified sample can guard against ‘unrepresentative’ sample e.g. an all-male
sample from a mixed gender population.
iv. Sufficient sample points to support a separate analysis of any strata may be
obtained.

Disadvantages

i. This method of sampling is not useful when the population cannot be exhaustively
partitioned into disjoint sub groups.
ii. The proportions of the strata must be known and accurate if it is to work properly.

Random sampling

This is a sampling technique where we select a group of subjects (a sample) for study from a
larger group (a population). Each individual is chosen entirely by chance and each member of the
polulation has a known and equal chance of being included in the sample.

Advantages
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 i. Can be used with large sample populations.
ii. Avoids bias.

Disadvantages

i. Can lead to poor representation of the overall parent population or area.

ii. There may be practical constraints in terms of time available and access to certain parts
of the study area.

SAMPLE HANDLING

A representative sample

A representative sample is one that truly reflects the composition of the material to be analyzed
within the context of a defined analytical problem. The importance of obtaining a representative
sample for analysis cannot be overemphasized. Without it, results may be meaningless or even
grossly misleading. Before sampling is done, it is vital that the aims of the analysis are
understood and an appropriate sampling procedure adopted. In some situations, a sampling plan
or strategy may need to be devised so as to optimize the value of the analytical information
collected. A small sample taken for analysis is described as a laboratory sample. Where duplicate
analyses or several different analyses are required, the laboratory sample will be divided into
sub-samples which should have identical compositions. Having obtained a representative sample,
it must be labeled and stored under appropriate conditions. Sample identification through proper
labeling is an essential feature of sample handling.

Sample storage

Due to varying periods of time that may elapse between sample collection and analysis, storage
conditions must be such as to avoid undesirable losses, contamination or other changes that
could affect the results of the analysis. Samples often have to be collected from places remote
from the analytical laboratory and several days or weeks may elapse before they are received by
the laboratory and analyzed. Furthermore, the workload of many laboratories is such that
incoming samples are stored for a period of time prior to analysis. In both instances, sample

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containers and storage conditions (e.g., temperature, humidity, light levels and exposure to the
atmosphere) must be controlled such that no significant changes occur that could affect the
validity of the analytical data. The following effects during storage should be considered:

- Increase in temperature leading to the loss of volatile analytes, thermal or biological

degradation, or increased chemical reactivity.
- Decrease in temperature that lead to the formation of deposits or the precipitation of
analytes with low solubilities.
- Changes in humidity that affect the moisture content of hygroscopic solids and liquids
or induce hydrolysis reactions.
- UV radiation, particularly from direct sunlight, that induces photochemical reactions,
photodecomposition or polymerization.
- Air-induced oxidation.

In addition, containers may leak or allow contaminants to enter. A particular problem associated
with samples having very low (trace and ultra-trace) levels of analytes in solution is the
possibility of losses by adsorption onto the walls of the container or contamination by substances
being leached from the container by the sample solvent. Trace metals may be depleted by
adsorption or ion-exchange processes if stored in glass containers, whilst sodium, potassium,
boron and silicates can be leached from the glass into the sample solution. Plastic containers
should always be used for such samples. Conversely, sample solutions containing organic
solvents and other organic liquids should be stored in glass containers because the base plastic or
additives such as plasticizers and antioxidants may be leached from the walls of plastic
containers.

Sample pretreatment

Preliminary treatment of a sample is sometimes necessary before it is in a suitable form for

analysis by the chosen technique and method. This may involve a separation or concentration of
the analytes or the removal of matrix components that would otherwise interfere with the
analysis. Samples arriving in an analytical laboratory come in a very wide assortment of sizes,
conditions and physical forms and can contain analytes from major constituents down to ultra-
trace levels. Pre-treatment is often used to condition the samples in readiness for the application

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of a specific method of analysis or to pre-concentrate (enrich) the analytes present at very low
levels. Examples of pretreatments are:

- Drying at 100°C to 120°C to eliminate the effect of variable moisture content.

- Weighing before and after drying enables the water content to be calculated or it can be
established by thermo gravimetric analysis.

- Separating the analytes into groups with common characteristics by distillation, filtration,
centrifugation, solvent or solid phase extraction.

- Removing or reducing the level of matrix components that are known to cause interference
with measurements of the analytes.

- Concentrating the analytes if they are below the concentration range of the analytical method to
be used by evaporation, distillation, co-precipitation, ion exchange, solvent or solid phase
extraction or electrolysis.

Sample preparation

A laboratory sample generally needs to be prepared for analytical measurement by treatment

with reagents that convert the analyte(s) into an appropriate chemical form for the selected
technique and method. If the material is readily soluble in aqueous or organic solvents, a simple
dissolution step may suffice. However, many samples need first to be decomposed to release the
analyte(s) and facilitate specific reactions in solution. Sample solutions may need to be diluted or
concentrated by enrichment so that analytes are in an optimum concentration range for the
method.

QUALITY OF ANALYTICAL DATA

Accuracy and precision

Accuracy is the closeness of an experimental measurement or result to the true or accepted value.
Precision is the closeness of agreement between replicated measurements or results obtained
under the same prescribed conditions. These two characteristics of numerical data are the most
important and the most frequently confused. It is vital to understand the difference between
them, and this is best illustrated diagrammatically as in the figure below.
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 correct
result
x
xx xx
A

x x x x x
B

x xx x x
C

x
xx xx
D
19.70 20.00 20.30

Titre (cm3)

Four analysts have each performed a set of five titrations for which the correct titer is known to
be 20.00 cm3. The titers have been plotted on a linear scale, and inspection reveals the following:

- The average titers for analysts B and D are very close to 20.00 cm3. These two sets are
therefore said to have good accuracy.
- The average titers for analysts A and C are well above and below 20.00 cm 3 respectively.
These are therefore said to have poor accuracy.
- The five titers for analyst A and the five for analyst D are very close to one another
within each set; these two sets therefore both show good precision;
- The five titers for analyst B and the five for analyst C are spread widely within each set;
these two sets therefore both show poor precision.

It should be noted that good precision does not necessarily produce good accuracy (analyst A)
and poor precision does not necessarily produce poor accuracy (analyst B). However, confidence
in the analytical procedure and the results is greater when good precision can be demonstrated
(analyst D).

Trueness is a term associated with accuracy, which describes the closeness of agreement between
the average of a large number of results and a true or accepted reference value. By repeating an
analysis a number of times and computing an average value for the result, the level of accuracy

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will be improved. The accuracy of data may be described in terms of the error in the reading.
Accuracy cannot be established with certainty where the true or accepted value is not known, as
is often the case.

Precision, which is a measure of the variability or dispersion within a set of replicated values or
results obtained under the same prescribed conditions, can be assessed in several ways. The
spread or range (i.e. the difference between the highest and lowest value) is sometimes used, but
the most popular method is to estimate the standard deviation of the data. The precision of results
obtained within one working session is known as repeatability or within-run precision. The
precision of results obtained over a series of working sessions is known as reproducibility or
between-runs precision.

Examples

1. A sample is known to weigh 3.182 g. Jane weighed the sample five different times and
obtained the data below. Which measurement was the most accurate?
A. 3.200 g
B. 3.180 g – the most accurate √
C. 3.152 g
D. 3.189 g
2. Consider the data (in cm) for the length of an object as measured by three students. The
length is known to be 14.5 cm. Which student had the most precise work, and which
student had the most accurate work?
Trial 1 Trial 2 Trial 3 Trial 4 Trial 5
Student A 14.8 14.7 14.8 14.7 14.8
Student B 14.7 14.2 14.6 14.6 14.8
Student C 14.4 14.4 14.5 14.4 14.5

For an analytical balance to give an accurate reading, the instrument must be

calibrated. Calibration is important because it defines the accuracy and quality of the
measurements that are recorded by the balance. As a result, reliable, accurate and repeatable
measurements will always be achieved.

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The spread (range) of data, the mean and the median

Chemists usually carry two to five portions (replicates) of a sample through an entire analytical
procedure. Replicates are samples of the same size that are carried through an analysis in exactly
the same way. One usually considers the ‘best’ estimate to be the central value for the data set.
Usually the mean or median is used as the central value for a set of replicate measurements.

The spread (or range) of data

This is the arithmetic difference between the greatest and the smallest data points for a set of
measurements. The data must first be arithmetically arranged in ascending order and the smallest
value subtracted from the greatest.

Example 1

An analytical determination for Pb2+ (in ppm) in an aqueous solution gives six replicate
measurements. Find the spread (or range) of the data. (ANS =0.9 ppm)

(a) (b) (c) (d) (e) (f) (g)

20.1 19.5 20.3 19.7 20.0 19.4 19.6

The mean

The mean of a set of replicate measurements is sometimes also known as the arithmetic mean or
average. The mean of a data set is equal to the sum of all the data values divided by the number
of measurements included in the data set. The letter N is normally used to denote the total
number of data values or replicate measurements. i is often used as a subscript to identify each
data value, i may range from i =1 to i =N.

It therefore follows that the Mean of a data set (x) is given by:

∑𝑁
𝑖=1 𝑥𝑖
𝑋 =
𝑁
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If we take the same data set as for example 1, the mean may be calculated. (ANS =19.8 ppm)

The median

If a data set contains an odd number of data values then the median is the data value that lies in
the middle of the data set when arranged in arithmetic order. If, however, the data set contains an
even number of data values then the median is the mean of the two data points that lie in the
middle of the data set when arranged in arithmetic order.

If we take the same data set as for example 1, the median may be calculated. (ANS =19.7 ppm)

Example 2

Calculate the median for the data given below. The following data is the same as that for
example 1 but with an additional replicate reading. (ANS = 19.8 ppm)

(a) (b) (c) (d) (e) (f) (g) (h)

20.1 19.5 20.3 19.7 20.0 19.4 19.6 19.9

ERRORS IN CHEMICAL ANALYSIS

The absolute error

The absolute error of a system is equal to the difference between the actual reading, xi, and the
true (or accepted) value xt.

𝐸𝐴 = 𝑥𝑖 − 𝑥𝑡

It should be remembered here that the true value may be very hard to determine or even agree
upon, which in turn makes the use of the absolute error difficult.

The relative error

The relative error describes the error in relation to the magnitude of the true value. It is normally
described in terms of a percentage of the true value i.e.
𝑥𝑖 − 𝑥𝑡
𝐸𝑟 = 𝑋 100%
𝑥𝑡
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Example

Calculate the relative error in percentage terms for an iron analysis that gives a value of 115 ppm
Fe content when the true value is, in fact, 110 ppm.

115 − 110
𝐸𝑟 = 𝑋 100%
110
𝐸𝑟 = 4.5%

Note that Er may be negative if the measured value is smaller than the true value. The negative
sign serves to indicate that the reading is low. A positive value for Er indicates a reading that is
larger than the true value.

Qn Using the same data as for the example above, calculate the relative error in terms of parts
per thousand for an analysis that gives 115 ppm Fe and the true value is 110 ppm Fe content.
(ANS = 45 ppt)

DETERMINATE, INDETERMINATE AND GROSS ERRORS

Any reading will contain some errors however carefully the measurement is taken. Errors may be
classified as indeterminate or determinate in origin.

Indeterminate errors are those that cause a random distribution of the data around a mean
point. Indeterminate errors are sometimes known as random errors. Errors of this type are
normally associated with the net effect of a number of small unpredictable fluctuations that may
not be readily identified or eliminated. Errors of this type lead to poor precision.

Determinate (or systematic) errors are those that cause all of the data to be shifted in one
direction. The results are, therefore, typically shifted to values that are either too low or too high.
Errors of this type lead to poor accuracy.

A third type of error known as Gross error can also occur. This type of error is normally large
and essentially arises when a significant error has been made with the analytical procedure itself,
so rendering the readings invalid. Gross errors lead to outliers that may under certain
circumstances be rejected so that the data set is not distorted. An outlier is a value that lies
outside (is much smaller or larger than) most of the other values in a set of data.

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The influence of indeterminate, determinate and gross errors may be illustrated in the figure
below:

(a) Indeterminate or random errors

True value

x x x x x x xx x x
Too low Too high

(b) Determinate or systematic errors

True value

x xx xx xxx x x
Too low Too high

(c) A gross error leading to an outlier

One point lies significantly
True value far away from the main data set.

x x x x x xx x x x
Too low Too high

(a) Shows that indeterminate errors simply cause the data to be scattered around a mean
point that is often close to the true value. Taking the mean value of a number of replicate
measurements usually minimizes the effect of errors of this kind.
(b) Shows that determinate errors, on the other hand, shift all of the data in one direction.
(c) A gross error usually causes one data point to lie significantly away from the rest of the
data, and in this way it is often readily identified.

Sources of indeterminate error

Indeterminate errors arise from a number of small unpredictable variations. The source of error
may be due to many factors as human error, fluctuations in temperature, or small differences in

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the quantities of regents used. Since there are several different sources of error that may
sometimes randomly lower or raise the reading, the data is scattered around the true value.

Sources of determinate error

Determinate or systematic errors cause all of the data to be shifted in one direction. The errors
are often of very similar magnitude. This behaviour is caused by the same type of error that
keeps occurring every time a measurement is made. It is easy to see how an error of this type can
occur. Imagine an analytical top-pan balance that is not zeroed or tared prior to the first
measurement, and gives a reading of, for example, 0.5 g when nothing is placed on the pan.
Every mass that is subsequently weighed out will, in fact, be 0.5 g less than the value recorded
on the balance. There are three main sources of determinate errors i.e. instrumental errors,
methodology based errors and personal errors.

Instrumental errors: Errors of this type typically occur as a result of, for example, inadequate
maintenance of instruments or lack of calibration with known standards.

Methodology errors: Errors may occur because the actual method being performed is either at
fault or is carried out incorrectly. An example here might include the use of a glass pipette that
possesses a cracked tip and, therefore, does not allow for the small residual volume of titrant to
be retained. The pipette is calibrated to take this volume into account and if this volume is not
retained, all the titration equivalence points will be displaced by the same value. In a similar
manner, a student may rigorously shake the last drop from the pipette, when good practice
dictates it should be retained; once again the titration equivalence point will be distorted.

Personal errors: As the name suggests, are normally linked to errors in personal judgement.
Many analyses involve making a judgement. Examples here could include the recording of a
titration equivalence point by eye or the estimation of the position of a reading on a scale. Some
people, for example, will consistently over shoot titration end-points if they are colour blind,
while other people will always tend to round up the position of the needle to the nearest division.

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 VOLUMETRIC METHODS OF ANALYSIS

TITRIMETRIC ANALYSIS

Introduction

In volumetric analysis, a chemical called a titrant is added to a solution of unknown

concentration called analyte (titrand) together with an indicator that will mark the time at which
all of the analyte has been reacted. At this point, the analyst can determine how much analyte is
originally present from the amount of titrant added. It is sometimes called titrimetric analysis
because all experiments under this type of analysis are completed by titration reactions. It is
highly precise, easy process, quick and only simple apparatus is required. Volumetric analysis
takes place in a wide variety of situations such as in industrial laboratories, hospital laboratories
and forensic science laboratories. Titration is also important in environmental chemistry, food,
beverage and the pharmaceutical industries.

The term titrimetric analysis refers to the quantitative chemical analysis carried out by
determining the volume of a solution of accurately known concentration which is required to
react quantitatively with a measured volume of solution of the analyte. The solution of accurately
known concentration is called a standard solution. The process of adding the standard solution
until the reaction is just complete is termed as titration.

Volumetric analysis volumetrically measures the amount of reagent (titrant), required to

complete a chemical reaction with the analyte. A general chemical reaction for volumetric
analysis is:

aA + tT Products

Where a moles of analyte A contained in a sample reacts with t moles of the titrant T in the
titrant solution.

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The reaction is generally carried out in a conical flask containing the liquid or dissolved sample.
Titrant solution is volumetrically delivered slowly with shaking to the reaction flask using a
burette. Delivery of the titrant is called a titration. The titration is complete when equivalent
titrant has been added to react with all the analyte according to the balanced titration reaction
equation. This is called the equivalence point. An indicator is often added to the reaction flask to
signal when all of the analyte has reacted. The titrant volume where the signal is generated is
called the end point volume or titre. The equivalence and end points are rarely the same
(titration error). Volumetric methods have the potential for a precision of up to ± 0.1% or
less.

Calculating volume of titrant at equivalent point (Veq.p)

If the number of moles of the analyte in the conical flask is known then we can calculate Veq.p
as shown by the following examples:

–
1. In the case of titrating 10 mL solution of 0.1 M of Cl (in the conical flask) by 0.2 M
solution of Ag+ (in the burette), calculate Veq.p of Ag+ solution?
2. In the case of titrating 10 mL of 0.1 M of H2SO4 solution by 0.2 M of NaOH solution,
calculate Veq.p of NaOH solution ?

Detection of the equivalent point

The equivalent point can be detected by observing or measuring a sudden and sharp change in
one of the physical properties of the resulting conical flask solution due to sudden and sharp
change of the concentration of one of the reactants or product of the titration reaction. There are
different methods of detecting the equivalence point i.e.

(a) Color change that can be detected by the naked eye:

(1) In some reactions, the solution changes color without any added indicator. This is often
seen in redox titrations, for instance, when the different oxidation states of the product and
reactant produce different colors as the case is with permanganate MnO4 -. This is
sometimes called auto detection.
MnO4- + 5Fe2+ + 8H+ Mn2+ + 5Fe3+ 4H2O
Violet Colourless

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 (2) Specific indicators : Each one of these indicators produce a colored product with only
–
one substance e.g. starch forms blue complex with iodine, and thiocyanate SCN forms a
red complex with iron (III).
(3) Equilibrium Indicators: These indicators are found in two forms of different colors and
depend only on the change in the physical property of the titration solution such as pH (for
acid – base titrations) or potential (redox titrations) regardless of the nature of the titration
reactants or products.
HIn H+ + In-
Colour A Colour B

In(ox) + ne In(red)
Colour A Colour B

(b) Measured properties: This method depends on the measurement of a physical property (not
noticed by the naked eye) of the titration solution during titration by an instrument, such as
electrical conductivity of the solution or its voltage or the intensity of electric current
passing through the solution or absorbance of electromagnetic radiation by the titration
solution, or refractive index of the solution ….etc.

Endpoint and equivalence point

Though equivalence point and endpoint are used interchangeably, they are different terms.
Equivalence point is the theoretical completion of the reaction i.e. the theoretical amount of the
titrant that must be added until the reaction is just complete. But at this point, no change in
the indicator color can be noticed. To notice this color you must add one or two more drops of
titrant solution. Endpoint is what is actually measured when a physical change in the titration
solution as determined by an indicator has occurred.

There is a slight difference (one or two drops) between the endpoint and the equivalence point of
the titration. This difference is referred to as the titration error. For example in the titration of
Fe3+ by MnO4– ( see above reaction ); at the equivalence point there will be neither Fe3+ nor
MnO4– in the conical flask because all will have been converted to products, therefore , no color
change. But to notice the violet color of MnO4– in the flask, we must add little (one or two drops)
of its solution, this is what we call endpoint. The indicator and experimental conditions should be
selected in such a way that the difference between the visible end point and equivalence point is
as small as possible.
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Titration Reaction

Not any chemical reaction can be used in the volumetric analysis. There are some conditions to
be met in order for a chemical reaction to be used as a basis for a titration:

i. The reaction must proceed according to a definite balanced chemical equation; the
analyte should react completely with the standard solution in stoichiometric properties.
ii. For volumetric methods to be useful, the reaction must be at least 99% complete.
iii. There must be some method of detecting the equivalent point ( an indicator or a measured
property)
iv. The reaction should be rapid so that the titration can be completed in a few minutes. In
some cases, the addition of a catalyst may be necessary to increase the rate of the
reaction.
v. There must be an alteration in some physical or chemical property of the solution at the
equivalence point.

Classification of reactions used in volumetric analysis:

The reactions employed in volumetric analysis fall into four main classes:

i. Neutralization reactions, or acidimetry and alkalimetry. These include the titration of

free bases, or those formed from salts of weak acids by hydrolysis, with a standard acid
(acidimetry); and the titration of free acids, or those formed by the hydrolysis of salts of
weak bases, with a standard base (alkalimetry). The reaction involves the combination of
hydrogen and hydroxide ions to form water.
ii. Oxidation-Reduction reactions: Under this are included all reactions involving change
in oxidation number or transfer of electrons among the reacting substances. The standard
solutions are either oxidizing or reducing agents.

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 iii. Precipitation reactions: These depend upon combination of ions to form a simple
precipitate e.g. in the titration of silver ions with a solution of a chloride. No change in
oxidation state occurs.
iv. Complex Formation reactions: These depend upon the combination of ions, other than
hydrogen or hydroxide ions, to form a soluble complex ion or compound, as in the
titration of a solution of cyanide with silver nitrate. Ethylenediamminetetraacetic acid,
EDTA, is a very important reagent for complex formation titration and has become one
of the most important reagents used in titrimetric analysis.

Examples

1. 300 mg of a Na2C2O4 (mw = 134) 95 %w/w pure reagent was transferred to a titration
conical flask. After adding acid solution and a suitable indicator, C2O4 2- was titrated with
KMnO4 solution according to the following titration reaction equation:
2MnO4- + 5C2O42- + 16H+ 2Mn2+ + 10CO2 + 8H2O
If the volume of KMnO4 solution at the equivalent point was 34 mL, calculate the
molarity of KMnO4 solution. (0.025 M)
2. 300 mg of a sample containing H3PO4 (mw = 98) was transferred to the titration conical
flask. After dissolving in water and adding a suitable indicator, the resulting solution was
titrated with 0.05 M of NaOH solution according to following titration reaction equation:
H3PO4 + 2NaOH Na2HPO4 + 2H2O

At the equivalent point, the volume of the NaOH solution required was 29 mL. Calculate
the weight percentage %w/w of H3PO4 in the sample? (23.7%)

Back Titration: When a titrant reacts directly with an analyte, the procedure is termed a direct
titration. The alternative technique is called a back titration. Here, an intermediate reactant is
added in excess of that required to exhaust the analyte, then the exact degree of excess is
determined by subsequent titration of the unreacted intermediate with the titrant. Back titration is
used when the analyte either does not react with the standard solution or reacts too slowly or
when there is no suitable indicator.

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 3. 800 mg of a sample containing chromium ore (Cr2O3) was dissolved in a conical flask
and Cr was converted to CrO4 2-. 10 mL of 0.2 M of Ag+ solution was added to the flask
and the following reaction took place:
CrO4 2- + 2Ag+ Ag2CrO4
After separating the Ag2CrO4 precipitate, the excess Ag+ in the filtrate was titrated with
0.12 M of SCN– solution according to the following equation:
Ag+ + SCN- AgSCN
If the volume of SCN solution was 14.5 mL, calculate the %w/w percentage of Cr2O3
(mw = 152) in the sample? (1.24%)

Some applications of titrimetric analysis

- Determination of the alkalinity (HCO3-) content of environmental water samples.

- Determination of the content of acid in foods and pharmaceuticals.
- Determination of the hardness of tap water by compleximetric titration.
- Determination of chloride within environmental water samples; an example of a silver
nitrate titration.
- Iodometric titration to determine the vitamin C (ascorbic acid) content of fruit juice.

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