Part I

The scope of analytical

chemistry: ground rules
and fundamentals
 The scope of analytical
chemistry and the nature 1
of analytical measurements

Skills and concepts

This chapter will help you to understand:
● What is meant by analytical chemistry.
● The scope of analytical chemistry and its applications.
● The importance of high-quality data and the implications of poor
quality or erroneous data.
● How to differentiate between a qualitative and quantitative test.
● What is meant by replicate measurements.
● The concepts of specificity, sensitivity, and accuracy of a test.
● What is meant by the terms analyte, interferent, and aliquot.

1.1 When and where analytical chemistry is used?

1.1.1 What is analytical chemistry?

We might not realize it, but many of us unwittingly carry out analytical
chemistry on a daily basis. It is a common scene: wandering into the
kitchen first thing in the morning, bleary-eyed, to make a cup of coffee to
kick-start the day. While the kettle is boiling, we go to the fridge and take
out the carton of milk. The carton has been sitting there for a few days
and so we are not sure whether it is still fit to use, so we open it up, lift it
to our nose, and gingerly sniff it. In so doing, and whether we realize it or
not, we are carrying out an analytical test. In this case, our nose is evaluating
the products of a variety of bacteria such as Salmonella typhimurium. If the
milk is too old, and the bacteria have had a chance to multiply, then
the action of the chemicals that they produce whilst multiplying will make
the milk unfit to drink. We will know whether the chemicals are there or not
by sniffing—and aiming to detect that characteristic smell of ‘gone-off’ milk.
4 1: The scope of analytical chemistry

You might recognize this test as being a chemical analysis more readily if
you were to use a so called electronic nose. At the time of writing, elec-
tronic noses represent an emerging state-of-the-art technique in the field
of electronic chemical sensors even though there is a long way to go before
they can sense as wide a range of smells as the human nose.
This example demonstrates that Analytical Chemistry encompasses
any type of test that provides information relating to the chemical
composition of a sample.
We all benefit from the activity of analytical chemists. We all eat food,
live in homes, wear clothes, and many of us drive motor cars. These are all
examples that rely on the modern manufacturing chemical industry. This,
in turn, is critically dependent on its quality control processes, the
responsibility for which lies largely with analytical chemists.
Every one of us acts as a consumer and relies on the analytical chemist
to play a major role within the manufacturing process to ensure that the
food we eat, the clothes we wear, and the medicine we take, are of a suit-
able quality. The chemical industry has some input into almost every man-
ufacturing industry, and represents the largest manufacturing sector of
most major industrialized countries. Indeed, many economists say a good
indicator towards the economic health of a nation can be gained by look-
ing at its chemical industry. It follows that the role of the analytical
chemist is a truly fundamental one!
If you are reading this text as an undergraduate chemist, and intend
using your degree following your university studies, there is a greater than
50% chance that you will be employed in some analytically related role.
Many chemists perform analyses as one part of their job even if they do
not think of themselves as analytical chemists. For example, the first thing
synthetic organic chemists will frequently do having made a new com-
pound is to analyse what they have just produced.
It is clear that the population is becoming ever more demanding of
analytical chemistry for ensuring both the quality of the products we
consume and how we treat our environment.
The safety of the food we eat is entwined with many issues relating to
modern farming methods, the use of agro-chemicals such as preservatives,
pesticides, and fertilizers. We are also concerned about issues such as our
cholesterol intake, how much fibre a food contains, its vitamin content,
and the strength of alcoholic drinks. We demand low or ‘acceptable’
benzene contents in the petrol we put into our cars and are then con-
cerned with the quantities of CO and CO2 cars pump into the atmo-
sphere. As the world population increases and our planet becomes ever
more crowded, we can be sure that analytical chemists will be called upon
to provide ever more information upon which future decisions can be
rationally based.
 The nature of data 5

1.1.2 So when and where is analytical chemistry used?

Many people will think of analytical chemistry as involving high-tech
instrumentation such as state-of-the-art mass spectrometry, high
performance liquid chromatography, and infrared techniques. Perhaps,
on the other hand, we remember our school laboratory where we learnt
the basics of titimetric analysis and spot chemical tests. While each of
these techniques play their role within the arsenal of the modern analytical
chemist, we should not forget simpler approaches using, for example,
pH meters, litmus paper, and analytical balances; these are often used
prior to the more elaborate approaches that sometimes come to mind more
readily. The important thing is to view the subject as a whole.
Sensors reflect the push towards developing highly simplified analytical
tests that may be performed by non-chemists. Every time we take our car
for a fuel emission test, the mechanic will place a CO gas sensor within the
exhaust outlet pipe to determine whether or not the levels of CO exceed a
legal threshold. In another context, diabetics may use an electrochemi-
cally based sensor to monitor their blood glucose levels, and by this read-
ing, determine the insulin dosage required prior to the next meal.
Automated instrumental techniques are also being ever more widely used
as more interest is being shown towards environmental chemistry and
pollution issues; for example, weather reports often contain some refer-
ence to ‘air quality’—analytical chemistry is at work here too.
This discussion makes two things clear; first, the use of analytical
chemistry touches upon almost every aspect of our lives—and, if any-
thing, our reliance on analytical chemists is set to increase further. Second,
the subject is responding to changing needs and is therefore a truly
dynamic subject; this is reflected by the vast research effort that is being
channelled into this subject.

1.2 The nature of data

In general terms, there are two stages to chemical analysis: data collection
and data analysis—in other words, gathering information and determining
what that information is telling us. Broadly speaking, data will come in
two forms: qualitative and quantitative. Likewise, the analysis of this
data will either give a qualitative or a quantitative result.
Qualitative analyses are those that give negative/positive, or yes/no
types of data; in other words, they say whether or not some substance (the
analyte) is present in a sample but do not actually measure the quantity of
the substance(s) present. A home pregnancy test represents a good example
of a qualitative analysis since the result will either indicate the presence
(positive result) or lack (negative result) of a pregnancy.
6 1: The scope of analytical chemistry

Quantitative analyses determine how much of a particular substance

there is within a sample rather than just its presence or absence. An
example of a quantitative test is the measurement of the pH of an aqueous
solution; here the result can range from 0 to 14.
Quantitative data are inherently normally expressed in a numerical
format; the sign (negative or positive) and the magnitude both give
meaningful information. The accurate use of units when quoting numeri-
cal data is also of paramount importance, yet often overlooked by
students. Even the yes/no or negative/positive types of qualitative data can
be mathematically handled by statistics. So almost all data demand some
mathematical treatment, even if at a rudimentary level.

1.2.1 The limitations of data

Both qualitative and quantitative data analyses face limitations. In the case
of a qualitative test, there may be a threshold below which the test may not
be able to identify the presence of the substance. For example, a pregnancy
test may give a false negative result if performed too early during the preg-
nancy if the level of the hormone human chrorionic gonadotrophin (hCG)
within the urine is at too low a concentration to cause a colour change
within the test strip. Therefore, even though the mother will be pregnant,
the test will fail to detect this, and will give a false negative result. The im-
portant point to be noted here is that even a qualitative test has a lower limit
of detection below which it will fail to detect the presence of the analyte.
Absolute accuracy is also impossible with quantitative data—there will
always be a margin of error that must be accounted for. For example, no
two pH meters will give absolutely the same measurement of pH; no two
electronic balances will measure absolutely the same mass of substance
being weighed. The treatment of quantitative data demands that error
limits be determined. In this way a data point or set of data may be quoted
to within a known range of possible error. A tap water supply may be
quoted as containing 100 ⫾ 10 parts per million (ppm) Pb. It is therefore
possible to fix the concentration range to be between 90 ppm at the lower
limit to 110 ppm at the upper limit. Information of this kind may often be
highly useful for ensuring that the correct and most appropriate informa-
tion may be derived from an analysis. More on the determination of error
limits is given in Chapter 2.

1.3 Should a qualitative or quantitative test

be chosen?
Analytical chemistry should always be performed for a purpose; this
may sound obvious yet this fact is often forgotten. It has been estimated
that up to 10% of tests performed each year world-wide are unnecessary.
 Should a qualitative or quantitative test be chosen ? 7

Apart from the waste of money (which at the time of writing is estimated to
run to as much as 5% of gross national product for most industrialised na-
tions), there is clearly a huge wastage in human effort and resourcing. What
is often lacking is a clear focus as to why tests are being performed—and in-
deed what useful information may be obtained from them.
One obvious point that should always be kept in mind is who the end
recipient of the information is and what information is actually required—
that is, why the test is to be performed and what useful purpose it may
fulfil this. The most common reason for any project failing is due to a lack of
planning at the outset and this is just as true for chemical analyses. The im-
portant message here is to plan your analysis carefully and appropriately.
In many situations, you may only want a qualitative determination to
be performed. For example, you may wish to only know whether or not a
pollutant is present above a reasonable threshold but not need to know
the quantities at which it is present. In many other circumstances a qualit-
ative test may be performed as a first filtering process—and if the result is
positive then a more complicated analysis may be performed in order to
quantify the measurement. The contamination of water samples with
lead is a good case study to illustrate this point. The lead iodide test (see
Chapter 3) provides a simple positive negative result for the presence of
lead above a concentration of approximately 0.2 g dm⫺3. This technique
provides a simple wet chemical approach which may be carried out at, for
example, the side of a river bank using only rudimentary equipment. If a
sample proves positive then the analyst may wish to quantify how much
lead is actually present. Another approach such as the lead dithiazone test
might be chosen to perform a quantitative analysis. This test provides a
colour change which is proportional to the content of lead present—the
more lead that is present, the deeper red in colour the solution will
become. The colour of the lead dithiazone solution can be measured using
a spectrophotometer to actually quantify the amount of lead present.
(Since the colour of the solution will be proportional to the amount of lead
present, measuring the intensity of the colour will give a direct indication
of the quantity of lead in the solution.) Analyses of this kind are described
in Chapters 5 and 6. Even in this situation, erroneous or incorrect results
may be caused by the presence of other heavy metal ions, and if further
specificity and or sensitivity is required, then the analyst may use atomic
absorption spectroscopy (see Chapter 7).
Above all else it should be remembered that the correct test for any par-
ticular situation is the one which best meets the requirements of the end
user. A prospective mother will be carrying out a pregnancy test to get a pos-
itive/negative result—she will not require a test to give the exact concentra-
tion of hCG present. Using the same argument, many pollutants have limits
specified by legislation, which are deemed to be acceptable or not. In
these situations, the water company (or regulator) is not just interested in a
qualitative result (i.e. whether the pollutant is present or not), but in the
8 1: The scope of analytical chemistry

actual concentrations in which it is present—and it is this figure that will

determine whether or not the water is deemed to be of an acceptable quality.

1.4 Data handling and terminology

Data handling involves using a number of terms and it is important that
these are clearly defined to avoid confusion.
Before data may be handled it must be collected or collated. A sample
is often taken from a larger volume and this sample is often known as an
aliquot if in the form of a solution.
The test is often repeated with two or more samples to evaluate
reproducibility and measurements of this kind are known as replicate
measurements. Precision is the term used to describe the reproducibility of
two or more replicate measurements that have been performed in the
same way. There are several ways in which precision can be expressed and
these are discussed in Chapter 2.
The substance to be analysed within the sample is known as the
analyte, and substances which may cause incorrect or erroneous results
are known as chemical interferents. (If an analysis monitors the concen-
tration of a heavy metal ion, a different metal ion may have very similar
chemical properties and therefore may interfere with the analysis and acts
as a chemical interferent.)
The lowest concentration below which the test will fail to recognize the
presence of an analyte is known as the lower limit of detection.
The specificity of the test defines how the test may respond to the
presence of a particular analyte, so if a test is totally specific then it will
only respond to the analyte of interest and in this case no chemical
interferents will interfere with the analysis.
The sensitivity of a test meanwhile describes how close or similar in
magnitude two readings may be, and still be distinguished from each
other. If a particular technique has a sensitivity of 1 ppm for Pb⫹, then two
determinations for 220 and 222 ppm may be taken as being two distin-
guishably different readings. By contrast two readings of 220.1 and
220.9 ppm Pb⫹ may not be differentiated from each other. Data should
never be quoted beyond the level of sensitivity and/or accuracy which may
be appropriate for the test or instrument. Indeed, inappropriate numbers
after decimal points may imply a level of sensitivity that is in fact
meaningless and can in fact be totally misleading.
Accuracy describes how close the measured value is to the true value,
which may in reality be very hard to determine. Certified reference materi-
als (Chapter 2) are often used to help estimate the levels of experimental
error which might be expected to be associated with a particular analytical
technique.
 The quality of analytical data 9

Once collected, the data will normally contain replicate measurements

for each data point. Sufficient information should also be collected to allow
an estimation of the uncertainty or errors associated with the method. Only
in this way may the experimental error of the technique be quantified.
The data may be collected by human observation and written down by
hand, or be collected by some form of automatic sampling technique. An
instrument may sometimes collect and process the data directly (e.g., by
an autotitrator—Chapter 3). It is becoming increasingly common to use
computers to assimilate and process the data. In each situation, however,
the data must be evaluated or processed for their quality and repro-
ducibility, and finally of course for its meaning. Statistical methods are
frequently used for data handling and processing, and these will be
described in Chapter 2.

1.5 The quality of analytical data

Reproducibility and accuracy are normally the most important criteria for
the end user of a test. If a blood sample is analysed for its alcohol level in
connection with a possible drink-driving conviction, it is crucially import-
ant that two differing laboratories would come to the same—and
correct—conclusion. In a similar manner, the fuel emission testing equip-
ment used by differing gaseous road-worthy testing stations should be able
to give concordant results to within specified limits. There will always
be experimental error associated with any test (see Chapter 2), however,
the uncertainty of the result should be clearly quantified, if any reliable
judgements are to be made from the data. The scrutiny and assessment of
the quality of the data may be carried out by some form of data validation
process; much effort, time, and money is expended in statistical analysis of
data and validation processes, both of which are discussed in Chapter 2.
Numerous studies have shown how hard it is to attain concordant
analytical information from different laboratories. Poor or unreliable data
are at best useless. If poor data cause the wrong decision to be made, the
result may be very costly indeed. A plant manager, for example, may dispose
of a batch of some product believing it to be contaminated when in fact it
was perfectly acceptable. The mistaken action may even be dangerous or
life threatening, if for example, a clinician administers an inappropriate
drug dosage, due to an erroneous pathology laboratory test.

1.5.1 You as the analytical chemist

The quality of data and their interpretation are of paramount importance
to any analytical chemist. Data are frequently numerical in nature and
their handling and interpretation involves some simple statistics. You may
10 1: The scope of analytical chemistry

well find the mention of mathematics and statistics offputting, yet the
numerical handling of data is intended to add clarity to complex issues
and lies at the very heart of analytical chemistry. If approached slowly and
gently, none of the maths required to become truly confident in any aspect
of data handling should be too problematic! These skills are required
from the point at which the subject is first studied; so Chapter 2 of this
book covers the statistical handling of numerical analytical data. This and
the following chapter have been written to gently aid learning in these
areas and to make the learning experience a non-traumatic and possibly
even a pleasant and enlightening one! It is hard to study or use chemistry
without resource to some form of analysis and so it is worth getting the
basics firmly established at an early stage. By the time you have worked
your way through Chapter 2, and the worked examples it contains, you
should have at your disposal all of the principal mathematical skills you
need to be able to fully grasp all of the material contained within every
other chapter of the book.

Exercises and problems Click here for Solutions

1.1. Discuss how modern society is dependent upon
analytical chemistry.
1.2. What is meant by: (i) a qualitative analysis;
and (ii) a quantitative analysis? Give two examples
of each.
1.5. What is meant by the term ‘replicate measure-
ments’? Why are replicate measurements desirable when
performing analyses?
1.6. Explain what is meant by an interferent. How might
an interferent affect an analysis? Give two examples.

1.3. Explain the difference between what is meant 1.7. What is meant by a data validation process? How
by the specificity, accuracy, and sensitivity of a might a data validation process be performed?
technique.

1.8. What is meant by an aliquot?

1.4. What is meant by the term ‘lower limit of detection’
for a technique and how does this differ from the
‘sensitivity’? 1.9. What are meant by error limits?
 Summary 11

Summary
1. Analytical chemistry encompases any type of test that 7. The specificity of an analytical test describes how
provides information relating to the chemical composi- selective the test is towards a given analyte.
tion of a sample.
8. The sensitivity of an analytical test describes
2. Qualitative analyses are those that provide informa-
how close in magnitude two readings may be and still be
tion relating to the presence of an analyte.
distinguished from each other.
3. Quantitative analyses are those that allow the
concentration of an analyte to be determined. 9. The accuracy of a test describes how close a measured
value is to the true value.
4. All data contain errors—and these should be
estimated—normally by statistical means.
10. Data validation processes are vital if confidence is to
be assigned to data.
5. An interferent is a substance that may erroneously
affect analytical measurements.
11. Poor or unreliable data are at best useless and at
worst may be dangerous or costly.
6. Replicate measurements are multiple measurements
upon the same sample.

Further reading
Anand, S. C. and Kumar, R. (2002). Dictionary of ana- Kennedy, J. H. (1990). Analytical chemistry practice.
lytical chemistry. Anmol Publications. Thomson Learning.