1 Module I

ANALYTICAL PROCESS

INTRODUCTION

You can understand easily the concept of Analytical Chemistry if you can define,

classify, and know the function of it. As to where and how to apply the Analytical Chemistry

is also explained here.

In addition, the type of analysis and their steps are both important in this field, that’s

why they are included in this chapter.

UNIT OUTCOMES

At the end of this unit, you should be able to:

1. demonstrate ability to solve problem using different analytical principles,

2. define analytical chemistry, both qualitative and quantitative chemistry,

3. differentiate quantitative and qualitative chemistry , and basic research and target

research,

4. discuss the steps in chemical analysis,

5. perform measurements of physical and chemical properties, and

6. appreciate the contribution of analytical chemistry to the other field of study.

UNIT REQUIREMENTS

1. You must practice your critical thinking skills to answer the case study given.

2. Provide your notebook and ballpen

KEY TERMS

Analytical chemistry, qualitative analysis, quantitative analysis, absolute, relative,

analyte, methods, technique, protocol, procedure

LEARNING PLAN

Discussion

Is there any iron moon dust? How much aspirin is there in a headache tablet? What

trace metals are here in a tin of tuna fish? What is the purity and chemical structure of a

newly prepared compound? These and a host of other questions concerning the composition

and structure of matter fall within the realms of analytical chemistry. The answers may be

given by simple chemical tests or by the use of costly and complex instrumentation. This is

what do you called chemical analysis. Chemical analysis includes any aspect of the chemical

characterization of a sample material. The techniques and methods employed and the

problems encountered are so varied as to cut right across the traditional divisions of

inorganic, organic and physical chemistry as well as embracing aspects of such areas as bio-

chemistry, physics, engineering and economics.

What is Analytical Chemistry?

It is a ―Science of Chemical Measurements‖

Analytical chemistry studies and uses instruments and methods used to separate,

identify, and quantify matter. In practice separation, identification or quantification may

constitute the entire analysis or be combined with another method.

Separation is a process of taking off or to isolates analytes.

Qualitative analysis identifies analytes, while quantitative analysis determines the

numerical amount or concentration of analytes.

Analytical chemistry consists of classical, wet chemical methods and modern,

instrumental methods. Classical qualitative methods use separations such as precipitation,

extraction, and distillation. Identification may be based on differences in color, odor, melting

point, boiling point, radioactivity or reactivity. Classical quantitative analysis uses mass or

volume changes to quantify amount. Instrumental methods may be used to separate samples

using chromatography, electrophoresis or field flow fractionation. Then qualitative and

quantitative analysis can be performed, often with the same instrument and may use light

interaction, heat interaction, electric fields or magnetic fields . Often the same instrument can

separate, identify and quantify an analyte.

Analytical chemistry is also focused on improvements in experimental design,

chemometrics, and the creation of new measurement tools. Analytical chemistry has broad

applications to forensics, medicine, science and engineering. (Wikipedia)

An analysis involves several steps and operations which depend on

 the particular problems

 your expertise

 the apparatus or equipment available.

METHODS OF CHEMICAL ANALYSIS

Absolute Relative

 Cheaper * more expensive

 From 10-3 to 10-6 * shorter analysis time

 More precise * compatible with computer

*can measure conc. From 10-9 to 10-12

Steps in Analysis
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Different methods provide a range of precision, sensitivity, selectivity, and
speed capabilities.

The sample size dictates what measurement techniques can be used.

The Function of Analytical Chemistry

Chemical analysis is an indispensable servant of modern technology

whilst it partly depends on that modern technology for its operation. The two have in fact

developed hand in hand. From the earliest days of quantitative chemistry in the latter part of

the eighteenth century, chemical analysis has provided an important basis for chemical

development. For example, the combustion studies of La Voisier and the atomic theory

proposed by Dalton had their bases in quantitative analytical evidence. Transistor provides a

more recent example of an invention which would have been almost impossible to develop

without sensitive and accurate chemical analysis. This example is particularly interesting as it
7 Module I

illustrates the synergic development that is so frequently observed in differing fields. Having

underpinned the development of the transistor, analytical instrumentation now makes

extremely wide use of it. In modern technology, it is impossible to over-estimate the

importance of analysis. Some of the major areas of application are listed below.

(a)—Fundamental Research

The first steps in unravelling the details of an unknown system frequently

involve the identification of its constituents by qualitative chemical analysis. Follow-up

investigations usually require structural information and quantitative measurements. This

pattern appears in such diverse areas as the formulation of new drugs, the examination of

meteorites, and studies on the results of heavy ion bombardment by nuclear physicists.

(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.

Accurate and reliable chemical analysis is thus essential.

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. 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 cornerstone 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. However, such distinction is not always

possible and sometimes a selective chemical reaction can be used to mask the interference. If

this approach fails, the separation of the analyte from the interfering component will become

necessary. Where quantitative measurements are to be made, separations must also be

quantitative or give a known recovery of the analyte.

(5)—Final Measurement

This step is often the quickest and easiest of the seven but can only be as

reliable as the preceding stages. 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. The analysis of validated standards is the most

satisfactory approach. Validated standards have been extensively analysed by a variety of

methods, and an accepted value for the appropriate analyte obtained. A standard should be

selected with a matrix similar to that of the sample. In order to ensure continued accurate

analysis, standards must be re-analysed at regular intervals.

(7)—The Assessment of Results

Results obtained from an analysis must be assessed by the appropriate

statistical methods and their meaning considered in the light of the original problem.

Glossary of Terms

The following list of definitions, though by no means exhaustive, will help both in the study

and practice of analytical chemistry.

Accuracy

The closeness of an experimental measurement or result to the true or accepted value.

Analyte

Constituent of the sample which is to be studied by quantitative measurements or identified

qualitatively.

Assay

A highly accurate determination, usually of a valuable constituent in a material of large bulk,

e.g. minerals and ores. Also used in the assessment of the purity of a material, e.g. the

physiologically active constituent of a pharmaceutical product.

Background

That proportion of a measurement which arises from sources other than the analyte itself.

Individual contributions from instrumental sources, added reagents and the matrix can, if

desired, be evaluated separately.

Blank

A measurement or observation in which the sample is replaced by a simulated matrix, the

conditions otherwise being identical to those under which a sample would be analysed. Thus,

the blank can be used to correct for background effects and to take account of analyte other

than that present in the sample which may be introduced during the analysis, e.g. from

reagents.

Calibration

(1) A procedure which enables the response of an instrument to be related to the mass,

volume or concentration of an analyte in a sample by first measuring the response from a

sample of known composition or from a known amount of the analyte, i.e. a standard. Often,

a series of standards is used to prepare a calibration curve in which instrument response is

plotted as a function of mass, volume or concentration of the analyte over a given range. If

the plot is linear, a calibration factor (related to the slope of the curve) may be calculated.

This facilitates the rapid computation of results without reference to the original curve.

(2) Determination of the accuracy of graduation marks on volumetric apparatus by weighing

measured volumes of water, or determinations of the accuracy of weights by comparison with

weights whose value is known with a high degree of accuracy.

Concentration

The amount of a substance present in a given mass or volume of another substance. The

abbreviations w/w, w/v and v/v are sometimes used to indicate whether the concentration

quoted is based on the weights or volumes of the two substances. Concentration may be

expressed in several ways. These are shown in Table 1.1.

Table 1.1 Alternative methods of expressing concentration*

Units Name and symbol

moles of solute per dm3 mol dm–3, M

equivalents of solute per dm3 normal, N

milli-equivalents of solute per dm3 meq dm–3

grams of solute per dm3 g dm–3

parts per million ppm (γ)

milligrams of component per kg mg kg–1

milligrams of solute per dm3 mg dm–3

parts per billion ppb

nanograms of component per kg ng kg–1

nanograms of solute per dm3 ng dm–3

parts per trillion ppt

picograms of component per kg pg kg–1

picograms of solute per dm3 pg dm–3

parts per hundred % (w/w, w/v, v/v)

millimoles of solute per 100 cm3 mM%

grams of solute per 100 cm3 g%

milligrams of solute per 100 cm3 mg%

micrograms of solute per 100 cm3 µg%

nanograms of solute per 100 cm3 ng%

* The table includes most of the methods of expressing concentration that are in current use,

although some are not consistent with Sl.

Constituent

A component of a sample; it may be further classified as:

major > 10%

minor 0.01–10%

trace 1–100 ppm (0.0001–0.01%)

ultratrace < 1 ppm

Detection Limit

The smallest amount or concentration of an analyte that can be detected by a given procedure

and with a given degree of confidence.

Determination

A quantitative measure of an analyte with an accuracy of considerably better than 10% of the

amount present.

Equivalent

That amount of a substance which, in a specified chemical reaction, produces, reacts with or

can be indirectly equated with one mole (6.023 × 1023) of hydrogen ions. This confusing

term is obsolete but its use is still to be found in some analytical laboratories.

Estimation

A semi-quantitative measure of the amount of an analyte present in a sample, i.e. an

approximate measurement having an accuracy no better than about 10% of the amount

present.

Interference

An effect which alters or obscures the behaviour of an analyte in an analytical procedure. It

may arise from the sample itself, from contaminants or reagents introduced during the

procedure or from the instrumentation used for the measurements.

Internal Standard

A compound or element added to all calibration standards and samples in a constant known

amount.

Sometimes a major constituent of the samples to be analysed can be used for this

purpose. Instead of preparing a conventional calibration curve of instrument response as a

function of analyte mass, volume or concentration, a response ratio is computed for each

calibration standard and sample, i.e. the instrument response for the analyte is divided by the

corresponding response for the fixed amount of added internal standard. Ideally, the latter

will be the same for each pair of measurements but variations in experimental conditions may

alter the responses of both analyte and internal standard. However, their ratio should be

unaffected and should therefore be a more reliable function of the mass, volume or

concentration of the analyte than its response alone. The analyte in a sample is determined

from its response ratio using the calibration graph and should be independent of sample size.

Masking

Treatment of a sample with a reagent to prevent interference with the response of the analyte

by other constituents of the sample (p. 40).

Matrix

The remainder of the sample of which the analyte forms a part.Method. The overall

description of the instructions for a particular analysis.

Methods

It is an adaptation of a technique to a specific measurement problem.

Precision

The random or indeterminate error associated with a measurement or result. Sometimes

called the variability, it can be represented statistically by the standard deviation or relative

standard deviation (coefficient of variation).

Primary Standard

A substance whose purity and stability are particularly well established and with which other

standards may be compared.

Procedure

A description of the practical steps involved in an analysis.

Protocol

It is a set of definite instructions that must be followed without exception , if the analytical

results are to be accepted for a specific purpose.

Reagent

A chemical used to produce a specified reaction in relation to an analytical procedure.

Sample

A substance or portion of a substance about which analytical information is required.

Sensitivity

(1) The change in the response from an analyte relative to a small variation in the amount

being determined. The sensitivity is equal to the slope of the calibration curve, being constant

if the curve is linear.

(2) The ability of a method to facilitate the detection or determination of an analyte.

Standard

(1) A pure substance which reacts in a quantitative and known stoichiometric manner with

the analyte or a reagent.

(2) The pure analyte or a substance containing an accurately known amount of it which is

used to calibrate an instrument or to standardize a reagent solution.

Standard Addition

A method of quantitative analysis whereby the response from an analyte is measured before

and after adding a known amount of that analyte to the sample. The amount of analyte
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originally in the sample is determined from a calibration curve or by simple proportion if the

curve is linear. The main advantage of the method is that all measurements of the analyte are

made

Table 1.3 Physical quantities and units including SI and CGS

Physical quantity SI CGS Unit Symbol Unit Symbol

length, l metre m ,centimetre cm

mass, m kilogram kg gram g

time, t second s second s

energy, E joule J erg —

electron volt eV

calorie cal

thermodynamic

temperature, T kelvin K kelvin K

amount of substance, n mole mol mole mol

force, F newton N dyne —

volume, V cubic metre m3 cubic

centimetre cm3 (ml) cubic

decimetre dm3 litre \l

electric current, I or i ampere A ampere A

electric potential difference, E volt V volt V

electric resistance, R ohm Ω ohm Ω

electric conductance, G siemens S mho Ω–1

quantity of electricity, Q coulomb C coulomb C

electric capacitance, C farad F farad F

frequency, ν hertz Hz cycles per

second cp
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Learners Activity: Role of Analytical Chemistry in Modern Science

• Nuclear Waste Disposal Case Study

• Nuclear Waste Disposal

– Nuclear Power Plants

– Nuclear Reactors

– Weapons Processing

– Weapons Disposal

 One Disposal Plan:

 seal waste in corrosion-resistant containers

 bury 1000’s of feet underground (rocky strata above water table)

 Must remain contained for> 20,000 years

 Technical Problems:

 Metal Package Corrosion:

 M + water, oxygen, oxidizers M ions + products

 Repository above water table, but some water present

 Model exists for chemical reactions, rates, and time-dependent dispersion of products

and waste
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 Predicted containment time depends on very accurate measurements of microscopic

corrosion processes over short periods (weeks, months)

 Corrosion Model:

 M + H2O, SO42-, O2  M+ + OH- , H2

 CO3=, H+, F-, Cl-,  MXn+ :

 NO2-, NO3-, S=,etc.MYm+, MZj + Prod.

 What Do We Need To Know?

 Laboratory Simulation Studies

 Water Composition at site before container placement.

 Water Composition after exposure to container

 Time dependence (rate of product growth over weeks/months)

 Small changes must be measured very precisely


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• What species to be measured?

• What precision is required?

• What measurement technique?

• What are the sources of error?

• Example: CO3= Analysis

• Species? CO3=, HCO3-, H2CO3 ?

• Precision? +/- ( 0.1%, 0.01%, 10%)

• Technique?

• +/- 1-2% Ion Chromatography

• +/- 0.1% Acid-Base Titration

• Error Sources?

• Acid-Base (Other Bases Interfer)

• Ion Chromatography (pH – Dependent Results)

• What Carbonate Species?

• CO3= + H2O  HCO3- + OH-

• HCO3- + H2O  H2CO3 + OH-

• H2CO3  CO2(g) + H2O

• Temperature, Pressure Dependence

• If Need [CO3=] only

• Specify pH, Temperature, Pressure

• Use Technique Selective for CO3=

• (Ion Chromatography)

• If Need S [CO3=]+ [HCO3-] + [H2CO3]

• Remove Interferences

• Acid-Base Titration
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• What does the Analytical Chemist need to know to solve these problems?

• Measurement Techniques Available

– Titrations, Optical Spectroscopy, Chromatography; etc.

• Strengths/Weaknesses of Techniques

– Accuracy, Precision, Interferences, Range, Detection Limits, etc.

• Underlying Chemistry/Physics of the Sample Material

• Solution Chemistry (Acid/Base)

• Solids Homogeneity, Structure

• Error Analysis

• Sources

• Solutions
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SUGGESTED READING MATERIALS:

Skoog, D.A. & West, D.M., Fundamentals of Analytical Chemistry (4th edn), CBS College

Publishing, New York, 1982.

Reference:

F.W.Fitfield and D. Kealey , Principles and Practice of Analytical Chemistry, (5th edn) 2000,

Blackwell Science Ltd.