Part I

The scope of analytical chemistry: ground rules and fundamentals

The scope of analytical chemistry and the nature 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 specicity, 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 rst 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 t 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 unt to drink. We will know whether the chemicals are there or not by snifngand aiming to detect that characteristic smell of gone-off milk.

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, electronic noses represent an emerging state-of-the-art technique in the eld 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 benet 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 suitable quality. The chemical industry has some input into almost every manufacturing 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 looking 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 rst thing synthetic organic chemists will frequently do having made a new compound 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 bre 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 concerned with the quantities of CO and CO2 cars pump into the atmosphere. 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

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 reect the push towards developing highly simplied 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 electrochemically based sensor to monitor their blood glucose levels, and by this reading, 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 reference to air qualityanalytical 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 livesand, if anything, 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 reected 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 analysisin 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.

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 numerical 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 pregnancy 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 important 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 datathere 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 x 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 information 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 ?

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 nations), 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 performedand indeed 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 full 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 important 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 qualitative test may be performed as a rst ltering processand 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 dm3. 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 presentthe 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 specicity 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 particular 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 positive/negative resultshe will not require a test to give the exact concentration 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

1: The scope of analytical chemistry

actual concentrations in which it is presentand it is this gure 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 dened 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 concentration 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 specic 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 distinguishably 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. Certied reference materials (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

Once collected, the data will normally contain replicate measurements for each data point. Sufcient 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 quantied. 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 autotitratorChapter 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 reproducibility, and nally 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 important that two differing laboratories would come to the sameand correctconclusion. In a similar manner, the fuel emission testing equipment 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 quantied, 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

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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 condent in any aspect of data handling should be too problematic! These skills are required from the point at which the subject is rst 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 rmly 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. 1.3. Explain the difference between what is meant by the specificity, accuracy, and sensitivity of a technique. 1.4. What is meant by the term lower limit of detection for a technique and how does this differ from the sensitivity? 1.5. What is meant by the term replicate measurements? 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. 1.7. What is meant by a data validation process? How might a data validation process be performed? 1.8. What is meant by an aliquot? 1.9. What are meant by error limits?

Summary

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

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