Milton Margai College 0f Education and Technology, Freetown.

Environmental Science Facaulty, Chemistry Depatment

CHEM- 211
ANALYTICAL CHEMISTRY
Lecture notes

Moriba J. Rogers
[email protected]

B. Sc. Intermediate

Introduction
Analytical chemistry involves the identification and use of laboratory equipments and chemicals and
to perform titrations and analysis of the contents of samples of interest.

Definition
Analytical Chemistry is the study of the separation, identification and quantification of
chemical components of natural and artificial materials. Qualitative analysis gives an
indication of the identity of the chemical species in the sample and quantitative
analysis determines the amount of one or more of these components. The separation
of components is often performed prior to analysis.
Analytical method can be separated into classical and instrumental. Classical method
also known as wet chemistry method used separations such as precipitation,
extraction and distillation and qualitative analysis by colour, odour or melting points.
Quantitative analysis is achieved by measurement of weight or volume.

Instrumental method uses apparatus to measure physical quantities of the analyte

such as light absorption, fluorescence of conductivity. The separation of materials is
accompanied using chromatography, electrophoresis or flow fractionation method.

Analytical chemistry also focuses on improvement in experimental design,

chemometrics and the creation of new measurement tools to provide better chemical
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information. Analytical chemistry has application in forensics, bio-analysis, clinical
analysis, environmental analysis and material analysis.

Classical Methods

Although modern analytical chemistry is dominated by sophisticated instrumentation,

the root of analytical chemistry and some of the principles used in modern
instruments are from traditional techniques many of which are still used today. These
techniques also tend to form the backbone of most undergraduate analytical
chemistry educational laboratories.

Qualitative analysis

A qualitative analysis determines the presence or the absence of a particular

compound but not the mass or concentration, i.e; if it is not related to quantity.

CHEMICAL TEST
These are numerous qualitative chemical test for example, the acid test for gold and
the Kastle-Meyer test for the presence of blood. In chemistry, a chemical test is a
qualitative or quantitative procedure designed to prove the existence of or quantify a
chemical compound or chemical group with the aid of a specific reagent. A
presumptive test is specifically used in medical science.

PURPOSES OF CHEMICAL TEST

Chemical testing might have a variety of purposes such as:

 Determine if or verify that, the requirements of a specification, regulation

or contract are met.
 Decide if a new product development program is on tract.
 Demonstrate proof of concept.
 Demonstrate the utility of a proposed patent.
 Determine the interactions of a sample with other known substances
 Determine the composition of a sample.
 Provide standard data for other scientific, medical and quality assurance
functions.
 Validate suitability for end use.
 Provide a basis for technical communication.
 Provide a technical means of comparison of several options.
 Provide evidence in legal proceedings.

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 BIO-CHEMICAL TEST
Uses or purposes to perform experiment

 Clinstrips qualitatively test for sugar in urine.

 The Kastle- Meyer test tests for the presence of blood.
 Salicylate testing is a category of drug testing that is focused on detecting
salicylate such as acetylsalicylic acid for either biochemical or medical
purposes.
 The Phadebas test tests for the presence of saliva for forensic purposes.
 Iodine solution test for starch.
 The Van Slyke determination test for specific amino acids.
 Test for lipids; add ethanol to sample then shake; add water to the
solution and shake again. If fat is present, the product turns milky white.
 Selivanoff’s test for differentiating between aldose and ketose sugars.

LABORATORY METHOD
How to write laboratory report
Laboratory reports are essential part of all laboratory courses and usually a significant
part of your grade. If your instructor gives you an outline for how to write laboratory
report, use that. Some instructors required a laboratory report, they included a
laboratory note book while others request a separate report. Here is a format of a
laboratory report you can use if you aren’t sure of what to write or need an
explanation of what to include in the different part of the report.
A laboratory report is how you explain what you did in an experiment, what you want
and what the result meant. Here is a standard format:
1. TITLE PAGE: the title of the experiment, your name and the names of laboratory
partners; your instructor’s name; the date the laboratory work was performed or the
date the report was submitted.
2. THE TITLE: says what you did, you should be brief (aim for 16 words or less) and
describe the main aim of the experiment or investigation. Eg; Effect of ultra violet light
on borax crystal growth rate.
3. Introduction ; 4. Materials ; 5. Method; 6. Data ;
7. Result : what you achieved at the end of the experiment ;
8. Discussion or analysis ; 9. Conclusion ; 10. Figures and result ;
11. Reference : where you get your materials from.

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 HOW TO READ MENISCUS
Meniscus is the curve seen at the top of liquid in response to it container. The
meniscus can be either concave or convex. A concave meniscus example; water in a
glass, occurs when the molecules of the liquid are more strongly attracted to the
container than to each other. A convex meniscus example; mercury in a glass is
produced when the molecules of the liquid are more strongly attracted to each other
than to the container. In some cases, the meniscus appears flat example; water in
some plastics.
When you read a scale on the side of a container with a meniscus such as a rehydrate
cylinder or volumetric flask, it is important that the measurement account for
meniscus measures so that the line you are reading is even with the centre of
meniscus. For water and most liquid, this is the bottom of meniscus. For mercury, take
the measurement from the top of the meniscus. In either case, you are measuring
base on the centre of the meniscus.

HOW TO CLEAN LABORATORY GLASS WARE

Cleaning basics
It’s generally easier to clean glass ware if you do it right away when the detergent is
used (it’s usually one designed for laboratory glass ware such as liquinox or alcohnox).
These detergents are preferable to any dish washing detergent you might use for
dishes at home.
Much of the time detergent and tap water are neither required nor desiring. You can
rinse the glass ware with the proper solvent then finish up with couples of rinses with
deionized water.

How to wash our common laboratory glass ware

1. For water soluble solutions (eg: NaCl, Sucrose solution), rinse 3 – 4 times with
deionized water then put the glass ware away.
2. For water insoluble solutions (eg: solutions in hexane or chloroform), rinse 2- 3
times with ethanol or acetone, rinse 3 – 4 times with deionized water, then put the
glass ware away. In some situations, other solvents need to be used for the initial
rinses.
3. For strong acids (eg: Conc. HCl or H2SO4)under the few good, carefully rinse the glass
ware with copious volume of tap water. Rinse 3 – 4 times with deionized water then
put the glass ware away.

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4. For strong bases (eg: NaOH or NH4OH) under the few good, carefully rinse the glass
ware with copious volume of tap water. Rinse 3 – 4 times with deionized water then
put the glass ware away.
5. For weak acids (eg: acetic acid solution or dilution of strong acids such as 0.1M or
1M HCl or H2SO4), rinse 3- 4 times with deionized water before putting the glass ware
away.
6. For weak bases (eg: 0.1M or 1M NaOH or NH4OH), rinse thoroughly with tap water
to remove the base, then rinse 3 – 4 times with deionized water before putting the
glass ware away.

Washing Specific / Special Glass ware

1. Glass ware used for organic chemistry: Rinse the glass ware with the appropriate
solvent. Use deionized water for water soluble content. Use ethanol for ethanol
soluble content followed by rinses with deionized water. Rinse with other solvent as
needed followed by ethanol and finally deionized water. If the glass ware requires
scrubbing, scrub with tap water followed by rinses with deionized water.

2. Burette : Wash with hot soapy water, rinse thoroughly with tap water, then rinse 3 –
4 times with deionized water. Make sure that the final rinses are sheet off the glass.
Burette need to be thoroughly clean in order to be used for laboratory qualitative
work.

3. Volumetric Flask and Pipette : In some cases you may need to soak the glass ware
overnight in a soapy water. Clean pipette and volumetric flask using warm soapy
water. The glass ware may need scrubbing with a brush. Rinse with tap water followed
by 3 – 4 times with deionized water.

4. Drying or not drying Glass ware : It is not advisable to dry glass ware with a paper
towel or tissue or chemical group with the aid of a specific reagent. A presumptive test
is used specifically in medical science.

OBTAINING A REPRESENTATIVE SAMPLE

A chemical analysis is usually performed on only a small portion of the material
characterised. If the amount of the material is very small and it is not needed for
future use, then the entire sample may be used for analysis. Example; The gunshot
residue on a hand.

The material to be sampled may be solid, liquid or gas. It may be homogeneous or

heterogeneous in composition. In the former case, a simple grab sample taken at
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random will suffice for the analysis. In the later, we may be interested in the variation
throughout the sample, in each case; several individual samples will be required. If the
gross composition is needed, then special sampling techniques will be required to
obtain a representative sample. For example, in analysing for the average protein
content of a shipment of grain, a small sample may be taken from each bag or tenth
bag for a large shipment and combined to obtain a gross sample. The larger the
particle size, the larger should be the gross sample. The gross sample must be reduced
in size to obtain a laboratory sample of several grams from which a few grams to
milligrams will be taken to be analysed.

In the case of biological fluids, the conditions under which the sample is collected can
be important; for example; whether the patient has just eaten. The composition of
blood varies considerably before and after meals and for many analyses, a sample is
collected after a patient has fasted for a number of hours. Preservatives such as
sodium fluoride (NaF) for glucose preservation and anticoagulants may be added to
blood samples when they are collected, these may affect a particular analysis.

Blood samples may be analysed as whole blood or they may be separated to yield
plasma or serum according to the requirement of a particular analysis. Most
commonly, a concentration of the substance external to the red cells (the extracellular
concentration) will be significant indication of physiological condition and so serum or
plasma is taken for analysis.

If whole blood is collected and allowed to stand for several minutes, the soluble
protein fibrinogen will be converted by a complex series of chemical reactions
(involving calcium ion) into the insoluble protein fibrin, which forms the basis of a gel
or clot. The process of clotting can be prevented by adding a small amount of an
anticoagulant such as heparin or citrate salt (i.e; a calcium complexor). An aliquot of
the unclotted whole blood can be taken for analysis or the coloured plasma remaining
can be analysed. Plasma and serum are essentially of identical composition, the chief
difference being that fibrinogen has been removed from the later.

However certain precaution should be taken in handling or storing samples to prevent

or minimize contamination, loss, decomposition or matrix change. In general, one
must prevent contamination or alteration of the sample by the following:
(i) the container
(ii) the atmosphere
(iii) light
The sample may have to be protected from the atmosphere or from light. It may be an
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alkaline substance for example, which may react with carbon dioxide in the air. Blood
samples to be analysed for CO2 should be protected from the atmosphere.

The stability of the sample must be considered. Glucose for example, is unstable and a
preservative such as sodium fluoride (NaF) is added to blood samples. The
preservative must not of course interfere in the analysis. Proteins and enzymes tend to
denature on standing and should be analysed without delay. Trace constituents may
be lost during storage by absorption onto the walls of the container.

Urine samples are unstable and calcium phosphate precipitates out entrapping metal
ions or other substances of interest. Precipitation can be prevented by keeping the
urine acidic (pH of 4.5) usually by adding one or two millilitre of glacial acetic acid per
100ml sample. Store under refrigeration urine as well as whole blood, scrum, plasma
and tissue samples can also be frozen for prolonged storage. Deproteinized blood
samples are more stable than untreated samples.

Corrosive gas samples will often react with the container. Sulphur dioxide for example
is troublesome. In auto mobile exhaust, SO2 is also lost by dissolving in condensed
water vapour from the exhaust. In such cases, it is best to analyse the gas by a stream
process.

PREPARING THE SAMPLE FOR ANALYSIS

The first step in analyzing the sample is to measure the amount being analysed
(example; volume or weight of samples). This will be needed to calculate the
percentage composition from the amount of analyte found. The analytical sample size
may be measured to the degree of precision and accuracy required for the analysis. An
analytical balance sensitive to 0.1mg is usually used for weight measurement.

Solid samples are often analysed on a dry basis and must be dried in an oven at 110 –
120oC for 1 – 2 hours and cooled in a desiccator before weighing if the sample is stable
at the drying temperatures. Some samples may require higher temperatures because
of the great affinity of moisture for their sample surface. The amount of sample taken
will depend on the concentration of the analyte and how much is needed for isolation
and measurement. Determination of a major constituent may require only a couple
hundred milligrams of sample, while a trace sample may require a several grams.
Usually, replicate samples are taken for analysis in order to obtain statistical data on
the precision of the analysis and provision of the analysis and provide more reliable
results.

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Analyses may be non-destructive in nature, for example in the measurement of lead in
paint by X-ray fluorescence in which the sample is bombarded with an X-ray beam and
the characteristics remitted X-radiation is measured. More often, the sample may
dissolve. In organic materials may dissolve in various acids, redox or complex media.
Acid resistant materials may require fusion with an acidic or basic flux in the molten
state to tender them soluble in dilute acid or water. Fusion with sodium carbonate foe
example forms acid soluble carbonates.

Organic materials that are to be analysed for inorganic constituents, example; trace
metals may be destroyed by dry ashing. The sample is slowly combusted in a furnace
at 400 – 700oC leaving behind an inorganic residue that is soluble in dilute acid.
Alternatively, the organic matter may be destroyed by wet digestion, by heating with
oxidizing acid. A mixture of nitrate and sulphuric acid is common. Biological fluids may
sometimes be analysed directly. Often however, proteins interfere and must be
removed. Dry ashing and wet digestion accomplish such removal, or proteins may be
precipitated with various reagents and filtered or centrifuged away to give a protein
free filtrate (PFF). If the analyte is organic in nature, these oxidizing methods cannot
be used. Rather the analyte may be extracted away from the sample or dialyzed or the
sample dissolved in an appropriate solvent.

Once the sample is in solution, the solution conditions must be adjusted for the next
stage of the analysis (separation or measurement step). For example; the pH will have
to be adjusted or a reagent added to react with and ‘’mask’’ interference from other
constituents. The analyte may have to be reacted with a reagent to convert it to a
form suitable for measurement or separation. For example, a coloured product may
be formed that will be measured by spectrometry or the analyte will be converted to a
form that can be volatilized for measurement by gas chromatography. The gravimetric
analysis of iron as Fe2O3 requires that all the ions be present as iron (iii) in its natural
form. A volumetric determination by reaction with dichromate ion, on the other hand,
requires that all the ions be converted to iron (ii) before reaction and the reduction
step will have to be included in the sample preparation.

The solvent and reagents used for dissolution and preparation of the solution should
be of high purity (reagent grade). Even so, they may contain trace impurities of the
analyte. Hence, it is important to prepare and analyse replicate blanks particularly for
trace analysis in the same amounts (including water) run through the entire analytical
procedure. The blank result is subtracted from the analytical sample result to arrive at

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a net analyte concentration in the sample. If the blank is appreciable, it may invalidate
the analysis.

PERFORMING NECESSARY CHEMICAL SEPARATIONS

In order to eliminate interferences to provide suitable selectivity in the measurement or to
proconcentrate the analyte for more sensitive or accurate measurement, the analyst must often
perform one or more separation steps. It is preferable to separate the analyte away from the sample
matrix, in order to minimize losses of the analyte. Separation steps may include precipitation,
extraction into an immiscible liquid /solvent, chromatography dialysis and distillation.

PERFORMING THE MEASUREMENT

The method employed for the actual quantitative measurement of the analyte will depend on a
number of factors, not the least important being the amount of analyte present and the accuracy
and precision required. Many available techniques possess varying degrees of selectivity, sensitivity,
accuracy and precision, cost and rapidity.

Gravimetric analysis usually involves the selective separation of the analyte by precipitation, followed
by the varying non-selective measurement of mass (of the precipitate). In volumetric or titrimetric
analysis, the analyte reacts with a measured volume of reagent of known concentration, in a process
called titration. A change in some physical and chemical properties signals the completion of the
reaction. Gravimetric and volumetric analysis can provide result accurate and precise to a few parts
per thousand {tenth of percent) or better. But they require relatively large (millimole or milligram)
quantities of analyte and are well suited for the measurement of major constituents. Volumetric
analysis is more rapid than gravimetric analysis and so is preferred when applicable.

Instrumental techniques are used for many analyses and constitute the discipline of instrumental
analysis. They are based on the measurement of a physical property of the sample, for example; an
electrical property or the absorption of electromagnetic radiation. Examples are spectrophotometry
(ultraviolet, visible or infrared)fluorimetry, atomic spectroscopy ( absorption , fluorescence) electro
analytical chemistry (potentiometric, volumetric, electrometric), chromatography ( gas, liquid) and
radiochemistry. Instrumental techniques are generally more sensitive and selective than the classical
techniques but are less precise, on the order of 1% or so. They are usually more rapid, may be
contaminated and may be capable of measuring more than one analyte at a time. Chromatography
techniques are practically powerful for analyzing complex mixtures. They perform the separation and
measurement step simultaneously. Constituents are separated as they are washed down (eluted
form) a column of appropriate material that interacts with the analyte to varying degrees and
analytes are sensed with an appropriate detector as they emerge from the column to give a transient
peak signal, in proportion to the amount of analyte.

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The various methods of determining an analyte can be classified as either absolute or relative.
Absolute method rely upon accurately known fundamental constants for calculating the amount of
the analyte, for example the atomic weight.

In gravimetric analysis, for example, an insoluble derivative of the analyte of known chemical
composition is prepared and weighed as in the formation of silver chloride (AgCl) for chloride
determination. The precipitate contains a known fraction of the analyte in this case.

atomic weight
Fraction of chloride =
Formula weight

35.453
Therefore, AgCl = = 0.24737
143.32

Hence, it is a simple matter to obtain the amount of chlorine contained in the weighed precipitate.
Most methods however are relative in that they require comparison against for example, the analyte
is reacted with the solution of a reagent of a known stoichiometric ratio. Hydrochloric acid for
example, react with sodium hydroxide in a 1:1 ratio.

HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)

The volume of sodium hydroxide solution required to just completely react with the hydrochloric
acid sample is measured. If we know the concentration of sodium hydroxide solution in moles per
litre, then the number of moles of NaOH added can be calculated ( volume × molarity)

No . of moles of solute
Molarity (m) =
No. of Kg of solvent

No . of moles of solute
Molarity (M) =
No . of litre of solution

And so we know the number of moles of HCl in the sample. Therefore, in this relative method, it is
necessary to prepare a reacting solution (sodium hydroxide) of relatively known concentration.

Most instrumental methods of analysis are relative. Instrument registers a signal due to some
physical property of the solution. Spectrophotometer for example, measures the fraction of
electromagnetic radiation from a light source that is absorbed by the sample. This fraction must be
related to the analyte concentration by comparison against the fraction absorbed by a known
concentration of the analyte. In other words, the instrumentation must be calibrated.

Instrument response may be linearly or non-linearly related to the analyte concentration. Calibration
is accomplished by preparing a series of solution of the analyte at known concentration and
measuring the instrument response to each of these (usually after treating them in the same manner
as the samples) to prepare an analytical calibration curve of response against concentration. The
concentration of an unknown is then determined from the response, using the calibration curve.
With modern computer controlled instruments, this is often done electronically or digitally and direct
read out of concentration is obtained.

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The sample matrix may affect the instrument response to the analyte. In such cases, calibration may
be accomplished by the method of standard additions. A portion of the sample is spiked with a
known amount of standard and the increase in signal is due to the standard. In this manner the
standard is subjected to the same environment as the analyte.

CALCULATING THE RESULTS AND REPORTING THE DATA

Once the concentration of the analyte in the prepared sample solution has been determined, the
results are used to calculate the amount of the analyte in the original sample. Either an absolute or a
relative amount may be reported. Usually, a relative composition is given. Example; percent or part
per million. If replicate analyses are performed (three or more), then a precision of the analysis may
be reported for example, standard deviation, along with the mean value. Knowledge of precision is
important because it gives the degree of uncertainty in the result. The analyst must critically evaluate
whether the results are reasonable and relate to the analytical problem as originally stated.

DATA HANDLING
1. ACCURACY AND PRECISION
Accuracy is the degree of agreement between the measured value and the true value. An absolute
true value is seldom known. A more realistic definition of accuracy then, would assume it to be the
agreement between a measured value and the accepted true value.

Precision is defined as the degree of agreement between replicate measurements of the same
quantity. That is, it is the reliability of a result. Good precision does not assure good accuracy. This
would be the case for example, if there were a systematic error in the analysis. A weight used to
measure each of the samples may be in error. This error does not affect the accuracy.

On the other hand, the precision can be relatively poor and the accuracy more or less by chance may
be good. Since all real analyses are unknown, the higher the degree of precision, the greater the
chance of obtaining the true value.

2. SIGNIFICANT FIGURES
Significant figures can be defined as the number of digits necessary to express the results of a
measurement consistent with the measured precision. Since there is uncertainty (imprecision) in any
measurement, the number of significant figures includes all of the digits that are known, plus the first
uncertain one. Each digit denotes the actual quantity it specifies.

Example - 1; 0.216 – has three significant figures

90.7 – has 3 significant figures

0.0670 – has 3 significant figures, only the last zero is significant.

800.0 – has 4 significant figures, all zeros are significant

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Example – 2; Give the answer of the following operations to the maximum number of significant
figures and indicate the key number.

45.741 ×0. 6472 ×0.08500

× 100 % = 115.6602266960838 %
2.1756

Soln. - The key number is 45.741. The answer is therefore 115.66 % and it is meaningless to carry
the operation out to more than six figures(the sixth figure is used to round off the fifth). The 100 % in
this calculation is an absolute number, since it is used only to move the decimal point and it has an
infinite number of significant figures.

Example – 3; Give the answer of the following operation to the maximum number of significant
figures and indicate the key number.

59.326 × 764
= 488.2735
124.5× 0.7456

Soln. – The key number is 764. Since the absolute magnitude of the answer is less than the key
number. It becomes 488. The last 3 is written as a subscript to indicate it is more doubtful. Again, the
key number has a relative uncertainty of about 4 parts in 600, so the answer has an uncertainty of at
least 3 parts in 4900(0.3 parts in 490).

Example – 4; Give the number of the following computation to the maximum number of significant

figures. ( 32.42
97.7
×100.0 )+36.04

687

301, 36+36.04 337.4

Soln. 687 = 687 = 0.491

In the first operation, the key number is 97.7 and the result is 301.36. We carried an additional fifth
figure until the addition step and then rounded to four figures since the division has only 3 significant
figures. In the division step, the key number is 687, but since the absolute magnitude of the answer is
less, we carry one more figure.

NOTE : if in the first we had rounded to 301.4, the numerator would have become 337.5 and the final
answer would be 0.4913(still within the experimental uncertainty).

DETERMINATE ERRORS
The two main classes of errors can affect the accuracy or precision of a measured quantity.
Determinate errors are those that as the name implies, are determinable and that presumably can
be either avoided or corrected. They may be constant, as in the case of an uncalibrated weight that is
used in all weighings. Or they may be variable but of such a nature that they can be accounted for
and corrected, such as a burette whose volume readings are in error by different amounts at
different volumes. The error can be proportional to sample size or may change in a more complex
manner. Examples of determinate errors: 1. Instrumental errors : These include faulty
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equipments, uncalibrated weights and uncalibrated glass wares.
2. Operative errors : These include personal errors and can be reduced by experience and care of
the analyst in the physical manipulations involved. Operations in which these errors may occur
include transfer of solutions, effervescence and bumping during sample dissolution, incomplete
drying of samples and so on. These are difficult to correct for. Other personal errors include
mathematical errors in calculations and prejudice in estimating measurements.
3. Errors of the method: These are the most serious errors of an analysis. Most of the above errors
can be minimized or corrected for but errors that are inherent in the method cannot be changed
unless the conditions of the determination are altered. Some sources of methodical errors include
coprecipitation of impurities, slight solubility of a precipitate, side reactions, incomplete reactions
and impurities in reagents. Sometimes corrections can be relatively simple, for example, by running a
reagent blank. A blank determination is an analysis on the added reagents only. It is standard
practice to run such blanks and to subtract the results from those for the sample. When errors
become intolerable, another approach to the analysis must be made. Sometimes, however, we are
forced to accept a given method in the absence of a better one.

Determinate errors may be additive or multiplicative, depending on the nature of the error or how it
enters into the calculation. In order to detect systematic errors in an analysis, it is common practice
to add a known amount of the standard to a sample and measure its recovery. The analysis of
reference samples also helps guard against method errors or instrumental errors.

INDETERMINATE ERRORS
The second class of errors includes the indeterminate errors often called accidental or random
errors, which represent the experimental uncertainty that occurs in any measurement. These errors
are revealed by small differences in successive measurements made by the same analyst under
virtually identical conditions, and they cannot be predicted or estimated.

These accidental errors will follow a random distribution; therefore mathematical laws of probability
can be applied to arrive at some conclusion regarding the most probable result of a series of
measurements. The indeterminate errors follows a normal distribution Gaussian curve. The symbol
‘S’ represents the standard deviation of a population of measurements and this measure of precision
defines the spread of the normal population distribution as shown below:

- 2S -S +S +2S

Magnitude of deviation

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Figure – 1: Normal error curve

WAYS OF EXPRESSING ACCURACY

There are various ways and units in which the accuracy of a measurement can be expressed, an
accepted true value for comparison being assumed.

1. Absolute Error : The difference between the true value and the measured value, with regard to
the sign is the absolute error and it is reported in the same units as the measurement. If a 2.62g
sample of material is analysed to be 2.52g, the absolute error is -0.10g. If the measured value is the
average of several measurements, the error is called the mean error. The mean error can also be
calculated by taking the average difference with regard to the sign of the individual test results from
the true value.

2. Relative Error : The absolute or mean error expressed as a percentage of the true value is the
Absolute Error
relative error. The relative error is calculated thus: × 100
mass of sample

E.g : If a 4.73g sample of material is analysed to be 4.53g,

the absolute error is (4.53 - 4.73) = - 0.20g.

−0.20
Relative error = 4.73 × 100 = - 4.2 %

the relative accuracy is the measured value or mean expressed as a percentage of the true value.

4.53
i.e, relative accuracy = × 100 = 95.8 %
4.73

The relative error can be expressed in units other than percentages. In very accurate
work, we are usually dealing with relative errors of less than 1% and it is convenient to
use a smaller unit. A 1% error is equivalent to 1 part in 100. It is also equivalent to 10
parts in 1000. This latter unit is commonly used for expressing small uncertainties.
That is, the uncertainty is expressed in parts per thousand, written as ppt. Parts per
thousand is often used in expressing precision of measurement.

Example: The results of an analysis are 36.97g, compared with the accepted value of
37.06g. What is the relative error in parts per thousand?

Soln. - Absolute error = 36.97g – 37.06g = - 0.09g

−0.09
Relative error = 37.06 ×100 = - 2.4 ppt

% indicates parts per thousand, just as % indicates parts per hundred.

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MEAN AND STANDARD DEVIATION CALCULATIONS

Each set of analytical results should be accompanied by an indication of the precision

of the analysis. Various ways of indicating precision are acceptable.

The mean (Ẍ) of an infinite set of experimental data is theoretically given by:
∑X
(Ẍ) = N

Where ∑X represents the sum of infinite number of measurements.

N is the number of measurements.

The standard deviation (σ 0r S) of an infinite set of experimental data is theoretically

√
(∑ X i)2
given by: σ =
√ ∑ (X −Ẍ )2
N −1
Or S = ∑ X i 2−
N−1
N

Where Xi represents the individual measurements and Ẍ the mean of the infinite
number of measurements (which should represent the true value). This equation holds
strictly only as N → ∝, where N is the number of measurements.

Example -1 : Calculate the mean and standard deviation of the following set of
analytical results 15.67g, 15.69g, 16.03g.

Soln: Xi Xi - Ẍ (Xi - Ẍ)2 ∑Xi2

15.67 0.13 0.0169 245.55

15.69 0.11 0.0121 246.18

16.03 0.23 0.0529 256.96

∑Xi = 47.39 ∑Xi - Ẍ = 0.47 ∑(Xi - Ẍ)2 = 0.0819 ∑Xi2 = 748.69

∑X 47.39
Ẍ = N = 3
= 15.80

σ =
√ ∑ (X −Ẍ )2
N −1
=
√ 0.0819
3−1
=
√ 0.0819
2
= 0.20g

15
 √ √ √
(∑ X i)2 ( 47.39 ) 2 2245.8121
748.69−
Or S = ∑ X i 2− N = 748.69−
3 = 3 =
N−1 3−1 2

√ 748.69−748.60
2

=
√ 0.09
2
=
√ 0.0819
2
= √ 0.045 = 0.2121 ≅ 0.21g

Example -2: The following replicate weighings were obtained, 29.8mg, 30.2mg,
28.6mg and 29.7mg. Calculate the standard deviation of the individual values and the
standard deviation of the mean. Express these as absolute and relative values.

Soln.: Xi Xi - Ẍ (Xi - Ẍ)2

29.8 0.2 0.04

30.2 0.6 0.36

28.6 1.0 1.00

29.7 0.1 0.01

∑Xi = 118.3 ∑Xi - Ẍ = 1.9 ∑(Xi - Ẍ)2 = 1.41

∑X 118.3
Ẍ = N = 4
= 29.6

value)
S =
√ ∑(X −Ẍ )2
N −1
=
√ 1.41
4−1
0.69
= 0.69 (absolute value); 29.6 X 100 = 2.3% (relative

0.69 0.34
S (mean) = √ 4 = 0.34mg (absolute); 29.6 X 100 = 1.1% (relative)

Example-3: Replicate water samples are analysed for water hardness with the
following results; 102.2, 102.8, 103.1 and 102.3 ppm CaCO3. Calculate
(a) the standard deviation (b) the relative standard deviation
(c) the standard deviation of the mean (d) the relative standard deviation of the
mean
∑X 102.2+ 102.8+103.1+102.3 410.4
Soln.: Mean value (X) =
N
= 4
= 4
= 102.6

X Xi – X (Xi – X)2
102.2 - 0.4 0.16
102.8 0.2 0.04
103.1 0.5 0.25
16
 102.3 -0.3 0.09
2
∑(X – X) = 0.54
∑ (X – X)2
(a) Standard deviation (S) = √
(N−1)
= √ 0.54
4−1
= √
0.54
3
= 0.424

0.424
(b) Relative standard deviation =
102.6
x 100% = 0.41%

S 0.424
(c) Standard deviation of the mean = S(mean) =
√N
=
√4
= 0.212

0.212
(d) Relative standard deviation of the mean =
102.6
x 100% = 0.21%

17