Analytical Chemistry
Analytical Chemistry
ANALYTICAL CHEMISTRY
Introduction
The Scope of Analytical Chemistry
Analytical chemistry has bounds which are amongst the widest of any technological
discipline.
An analyst must be able to design, carry out, and interpret measurements within the
context of the fundamental technological problem with which he or she is presented.
The selection and utilization of suitable chemical procedures requires a wide knowledge
of chemistry, whilst familiarity with and the ability to operate a varied range of
instruments is essential.
Finally, analysts must have a sound knowledge of the statistical treatment of experimental
data to enable them to gauge the meaning and reliability of the results that they obtain.
When an examination is restricted to the identification of one or more constituents of a
sample, it is known as qualitative analysis, while an examination to determine how much
of a particular species is present constitutes a quantitative analysis.
Sometimes information concerning the spatial arrangement of atoms in a molecule or
crystalline compound is required or confirmation of the presence or position of certain
organic functional groups is sought. Such examinations are described as structural
analysis and they may be considered as more detailed forms of analysis.
Any species that are the subjects of either qualitative or quantitative analysis are known
as analytes.
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(b)Product Development
The design and development of a new product will often depend upon establishing a
link between its chemical composition and its physical properties or performance.
Typical examples are the development of alloys and of polymer composites.
(c)Product Quality Control
Most manufacturing industries require a uniform product quality.
To ensure that this requirement is met, both raw materials and finished products are
subjected to extensive chemical analysis.
On the one hand, the necessary constituents must be kept at the optimum levels, while
on the other impurities such as poisons in foodstuffs must be kept below the
maximum allowed by law.
(d)Monitoring and Control of Pollutants
Residual heavy metals and organo-chlorine pesticides represent two well-known
pollution problems.
Sensitive and accurate analysis is required to enable the distribution and level of a
pollutant in the environment to be assessed and routine chemical analysis is important
in the control of industrial effluents.
(e)Assay
In commercial dealings with raw materials such as ores, the value of the ore is set by
its metal content.
Large amounts of material are often involved, so that taken overall small differences
in concentration can be of considerable commercial significance.
(f)Medical and Clinical Studies
The levels of various elements and compounds in body fluids are important indicators
of physiological disorders.
A high sugar content in urine indicating a diabetic condition and lead in blood are
probably the most well-known examples.
Analytical Problems and Their Solution
The solutions of all analytical problems, both qualitative and quantitative, follow the same
basic pattern. This may be described under seven general headings.
(1)Choice of Method
The selection of the method of analysis is a vital step in the solution of an analytical
problem.
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A choice cannot be made until the overall problem is defined, and where possible a
decision should be taken by the client and the analyst in consultation.
Inevitably, in the method selected, a compromise has to be reached between the
sensitivity, precision and accuracy desired of the results and the costs involved.
For example, X-ray fluorescence spectrometry may provide rapid but rather imprecise
quantitative results in a trace element problem. Atomic absorption spectrophotometry,
on the other hand, will supply more precise data, but at the expense of more time-
consuming chemical manipulations.
(2)Sampling
Correct sampling is the corner stone of reliable analysis.
The analyst must decide in conjunction with technological colleagues how, where,
and when a sample should be taken so as to be truly representative of the parameter
that is to be measured.
(3)Preliminary Sample Treatment
For quantitative analysis, the amount of sample taken is usually measured by mass or
volume.
Where a homogeneous sample already exists, it may be subdivided without further
treatment.
With many solids such as ores, however, crushing and mixing are prior requirements.
The sample often needs additional preparation for analysis, such as drying, ignition
and dissolution.
(4)Separations
A large proportion of analytical measurements is subject to interference from other
constituents of the sample.
Newer methods increasingly employ instrumental techniques to distinguish between
analyte and interference signals.
(5)Final Measurement
The fundamental necessity is a known proportionality between the magnitude of the
measurement and the amount of analyte present.
(6)Method Validation
It is pointless carrying out the analysis unless the results obtained are known to be
meaningful.
This can only be ensured by proper validation of the method before use and
subsequent monitoring of its performance.
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whereas other problems might be more easily solved by using another technique, such as
anodic stripping voltammetry or potentiometry with a lead ion-selective electrode.
(Figure 3)
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Protocols are commonly encountered when analytical chemistry is used to support or define
public policy. For purposes of determining lead levels in water under the Safe Drinking
Water Act, labs follow a protocol specified by the Environmental Protection Agency.
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where CA is the concentration of analyte in the sample. Since the solutions in both cylinders
have the same concentration of Cu2+, their analysis yields identical signals.
Analytical methods may be divided into three groups based on the magnitude of their
relative errors.
When an experimental result is within 1% of the correct result, the analytical method is
highly accurate. Methods resulting in relative errors between 1% and 5% are moderately
accurate, but methods of low accuracy produce relative errors greater than 5%.
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The magnitude of a method’s relative error depends on how accurately the signal is
measured, how accurately the value of k in equations 1 or 2 is known, and the ease of
handling the sample without loss or contamination.
Precision
When a sample is analyzed several times, the individual results are rarely the same.
Instead, the results are randomly scattered.
Precision is a measure of this variability. The closer the agreement between individual
analyses, the more precise the results.
For example, in determining the concentration of K+ in serum, the results shown in
Figure 5(a) are more precise than those in Figure 5(b).
It is important to realize that precision does not imply accuracy. That the data in Figure
5(a) are more precise does not mean that the first set of results is more accurate. In fact,
both sets of results may be very inaccurate.
As with accuracy, precision depends on those factors affecting the relationship between
the signal and the analyte (equations 1 and 2).
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(concentration method)
Selectivity
An analytical method is selective if its signal is a function of only the amount of
analyte present in the sample. In the presence of an interferent, equations 1 and 2 can be
expanded to include a term corresponding to the interferent’s contribution to the signal, SI,
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.
The selectivity of the method for the interferent relative to the analyte is defined by a
selectivity coefficient, KA,I
------5
which may be positive or negative depending on whether the interferent’s effect on the signal
is opposite that of the analyte. A selectivity coefficient greater than +1 or less than –1
indicates that the method is more selective for the interferent than for the analyte. Solving
equation 5 for kI
kI = KA,I × kA -------6
substituting into equations 3.3 and 3.4, and simplifying gives
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KA,I × nI in equation (7) is significantly smaller than nA, or KA,I ×CI in equation(8) is
significantly smaller than CA.
Robustness and Ruggedness
Methods are subject to a variety of chemical and physical interferences that contribute
uncertainty to the analysis.
When a method is relatively free from chemical interferences, it can be applied to the
determination of analytes in a wide variety of sample matrices. Such methods are
considered robust.
Random variations in experimental conditions also introduce uncertainty.
If a method’s sensitivity is highly dependent on experimental conditions, such as
temperature, acidity, or reaction time, then slight changes in those conditions may lead to
significantly different results.
A rugged method is relatively insensitive to changes in experimental conditions.
Scale of Operation
Another way to narrow the choice of methods is to consider the scale on which the
analysis must be conducted.
The scale of operations in Figure 6 shows the analyte’s concentration in weight percent
on the y-axis and the sample’s size on the x-axis.
For convenience, we divide analytes into
a) major (>1% w/w)
b) minor (0.01% w/w – 1% w/w)
c) trace (10–7 % w/w – 0.01% w/w) and
d) ultra trace (< 10–7% w/w) components
we divide samples into
a) macro (>0.1 g)
b) meso (10 mg – 100 mg)
c) micro (0.1 mg – 10 mg) and
d) ultra micro (<0.1 mg) sample sizes.
Note that both the x-axis and the y-axis use a logarithmic scale.
The analyte’s concentration and the amount of sample used provide a characteristic
description for an analysis.
For example, samples in a macro–major analysis weigh more than 0.1 g and contain more
than 1% analyte.
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Diagonal lines connecting the two axes show combinations of sample size and
concentration of analyte containing the same absolute amount of analyte. As shown in Figure
6, for example, a 1-g sample containing 1% analyte has the same amount of analyte (0.010 g)
as a 100-mg sample containing 10% analyte or a 10-mg sample containing 100% analyte.
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Once the solutions and equipment are in place, the number of samples that can be
analyzed per hour differs substantially from method to method.
This is a significant factor in selecting a method for laboratories that handle a high
volume of samples.
Cost
The cost of an analysis is determined by many factors, including the cost of necessary
equipment and reagents, the cost of hiring analysts, and the number of samples that can
be processed per hour.
In general, methods relying on instruments cost more per sample than other methods.
Making the Final Choice
Attempts to minimize cost and analysis time may decrease accuracy.
Selecting a specific method requires a careful balance among these design criteria.
Usually, the most important design criterion is accuracy, and the best method is that
capable of producing the most accurate results.
When the need for results is urgent, as is often the case in clinical labs, analysis time may
become the critical factor.
The best method is often dictated by the sample’s properties. Analyzing a sample with a
complex matrix may require a method with excellent selectivity to avoid interferences.
Samples in which the analyte is present at a trace or ultratrace concentration usually must
be analyzed by a concentration method.
If the quantity of sample is limited, then the method must not require large amounts of
sample.
Determining the concentration of lead in drinking water requires a method that can
detect lead at the parts per billion concentrations. Selectivity is also important because other
metal ions are present at significantly higher concentrations. Graphite furnace atomic
absorption spectroscopy is a commonly used method for determining lead levels in drinking
water because it meets these specifications. The same method is also used in determining lead
levels in blood, where its ability to detect low concentrations of lead using a few microliters
of sample are important considerations.
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Ex: in the iodometric determination of an oxidant like chlorate, another oxidizing agent
such as bromate would cause high results if its presence were unsuspected and not
corrected for. Taking larger samples would increase the absolute error, but the relative
error would remain constant provided the sample was homogeneous.
2. Indeterminate error/ random error:
Indeterminate errors, as the name implies, cannot be attributed to any known cause,
but they inevitably attend measurements made by human beings. They are random in nature
and lead to both high and low results with equal probability. They cannot be eliminated or
corrected and are the ultimate limitation on the measurement. They can be treated by
statistics, & repeated measurement of the same variable can have the effect of reducing their
importance.
Minimization of errors:
Detection of Systematic Instrument and Personal Errors
Some systematic instrument errors can be found and corrected by calibration.
Periodic calibration of equipment is always desirable because the response of most
instruments changes with time as a result of wear, corrosion, or mistreatment.
Many systematic instrument errors involve interferences in which a species present in
the sample affects the response of the analyte.
Most personal errors can be minimized by care and self-discipline.
It is a good habit to check instrument readings, notebook entries, and calculations
systematically.
Errors due to limitations of the experimenter can usually be avoided by carefully
choosing the analytical method.
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