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Evaluation of Analytical Data

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DATA I

Structure

2.1

Introduction

Objectives

2.2

Error

Types of Errors

2.3

Calibration of Equipment and Purification of Reagents etc

Use of Blanks

Addition of a standard

Independent Analysis

Improvement in Methods

2.4

Accuracy

Precision

2.5

Reporting of Results

Chemical Expression of Results

Numerical Expression of Results

2.6

2.7

2.8

2.9

2.1

Significant Figures

Summary

Terminal Questions

Answers

INTRODUCTION

operator mainly takes care of three components: the system, some property being

measured, and the instrument. Errors originate in all three components and need to be

considered in a measurement. It is a real fact that no single physical measurement is

perfectly accurate. The question of accuracy must, in general, receive attention both

before and after an analysis. The aspect which can answer the quality assurance is the

evaluation of analytical data.

The purpose of this unit is to provide sufficient information to the student to enable

him to examine the factors affecting the reliability of results and understand the

contributions of errors, their types, their minimization for accuracy and precision of

the measurement and the proper use of significant figures.

Objectives

After studying this unit, you should be able to:

2.2

The data obtained by a physical measurement should always raise the question of

errors and their nature. Various types of errors are caused in quantitative chemical

26

analysis. It is, therefore, worthwhile to account for these errors. Now first understand

what are error and its types.

2.2.1

Evaluation of

Analytical Data I

Error

The error is an inverse measure of the accuracy of a result. Less the error, more

accurate the result is. Error is mathematically defined as the difference between the

observed value and the true value:

E=OT

(2.1)

where E is the error (absolute error), O is the observed value of a measurement, and T

is the true value. It is with regard to sign, and it is reported in the same units as the

measurements. Let us consider, for example, for the capacity of a measuring flask

whose true value, as given by standard measurements, is 250 ml. For a series of 5

measurements done by an analyst the error is represented in Table 2.1.

Table 2.1: Expression of Error in Measurements in Volume of a Flask

Serial Number of

observations

Observed value

(ml)

249

250

247

250

250

250

248

250

251

250

+1

Total

5 ml

Average

1 ml

The error represented in the above table is the absolute error and the average

5 ml

Total error

error =

=

= 1 ml

Number of Observations

5

However, the absolute error is of little practical significance for a quantitative analysis.

It is the relative error, that is, the error relative to the true value (E/T) expressed in

suitable units, is of the practical importance as a measure of inaccuracy (or as an

inverse measure of accuracy). It is convenient to express relative error in terms of

percentage (parts per hundred), or parts per thousand (ppt), preferably.

To understand the importance of relative error let us consider the measurement of the

capacities of three standard flasks of 10, 100 and 1000 ml by three analysts A, B and C

respectively represented as follows:

Analyst

T=

10 ml

100 ml

1000 ml

O=

11 ml

101 ml

1001 ml

E=

1 ml

1 ml

1 ml

1/10 = 0.1

1/100 = 0.01

1/1000 = 0.001

% R.E. = (E100)/T

10%

1%

0.1%

27

Basic Aspects

You see that the absolute error in all the three cases is the same (1 ml), but the

comparison of the relative errors tells that the error (inaccuracy) in case of the analyst

C is the least and hence his result is the most reliable out of all the three.

However, for a finite measurement the true value is, usually, not known and the scatter

is measured in terms of deviation which is the difference between the observed value

and the mean of the given set of data. You will study about the deviation in detail in

the next unit (Unit 3) of this block.

For a practical point of view, it is useful to classify errors into two categories: (i)

determinate errors, and (ii) indeterminate errors.

i)

Determinate Errors

As the name implies, determinate errors are those whose magnitude can be determined

after assigning a definite cause and thereby they can be corrected for. For example,

weighing of a hygroscopic salt like calcium chloride. Its weight will vary according to

water absorbed by it from atmosphere if it were weighed in open. The error caused due

to absorption of water by the salt can be corrected for if the salt were weighed after

drying and keeping in a desiccator.

The determinate errors may be constant or variable. When the determinate error

possessed the same value from one measurement to another under a variety of

conditions, is called a constant error, for example, error due to uncalibrated weights.

On the other hand, in certain cases the determinate errors may vary in magnitude with

conditions, for example, the errors caused due to expansion or contraction of

volumetric solutions with a change in temperature. The magnitude of the change in

volume can be determined by noting the temperature. These variable determinate

errors are sometimes called systematic errors. Commonly people do not use this

designation of systematic error only for variable errors but frequently call both types

of determinate errors (constant or variable) as systematic errors and we shall also

follow the same nomenclature.

Sources of Determinate Errors

Determinate errors may be caused by numerous sources. It is not needed to enumerate

them all but more important ones are given as follows:

28

a)

uncalibrated devices, for example inequality of the balance arms or insufficient

accuracy of the balance, uncalibrated measurement vessels, or uncalibrated

weights etc.

b)

Errors due to reagents: The quality of the reagents is very important in the

quantitative analysis. Certain reagents may possess impurities that will

interfere in a particular quantitative analysis. Errors are also caused by the use

of incorrectly standardized solutions for titration.

c)

analyst to make certain observations accurately, that is, they are caused due to

some natural weakness of the analyst. For example, some persons always detect

the end point a little past in titration because their inability to judge colour

changes exactly. Personal errors also include the so called psychological errors,

due to certain bias often met within students, for example, some students often

tend to choose in a burette reading the division which is closer to the previous

determination or even to those found by his fellow students rather than the

actual one. Obviously, this makes the results less accurate.

d)

Operational errors: The operational errors are associated with the operation of

an analysis. These errors are independent of the instrument and the apparatus

employed, also these errors are not related to the chemical properties of the

system in hand. Their magnitude depends more upon the analyst himself than

on any other factor. They are mainly caused by carelessness of the operator in a

quantitative work, for example, loss in bumping of uncovered solution while

heating, failure to remove precipitate quantitatively from vessels, underwashing

or overwashing of precipitate, etc.

e)

particular constituent in the given sample may not be accurate because of

improper selection of the procedure in the required range and will give the

inaccurate result. For example, in the determination of iron (present in traces) in

water, the gravimetric method will not give the correct result, and a method

suitable for trace contents, say, a spectrophotometric method should be

selected. The methodic errors are inherent in the method, and cannot be

corrected unless the correct method is applied.

ii)

Indeterminate Errors

Evaluation of

Analytical Data I

Indeterminate errors are the errors for those no exact cause can be assigned, hence

they cannot be corrected. The sources of these errors may be similar to those for the

determinate errors but no definite causes out of these can be assigned for

indeterminate errors. Even after applying every correction for the possible determinate

errors the replicate observations may vary. Such a variation in observations is due to

the indeterminate errors. These errors follow the rules of chance or the laws of

probability and are also known as Random Errors. These errors, which accompany

every determination, are quite irregular and generally small.

Indeterminate errors cannot be prevented or eliminated by corrections. However, they

can be considerably reduced by increased care in work, and increase of the number of

replicate determinations. Their pattern of occurrence can be analyzed by the

techniques of statistics in order to secure a worthwhile insight into their magnitudes,

frequencies of occurrence, and effects on the final expression of results (see Unit 3). A

plot of the normal distribution of occurrence of indeterminate errors can be prepared.

SAQ 1

In an analysis the observed value is 5.24 g compared with the accepted (true) value of

5.28 g. What is the relative error in parts per thousand?

...

...

...

...

2.3

It has been shown in the preceding section that the results are affected by various types

of errors. Now, we will se how the various types of errors are detected and minimized.

Correction of errors of the determinate type can be accomplished through increased

care in the mechanics of analysis, application of theoretical considerations so as to

eliminate inherent weakness of method, and checking of measurements under varying

conditions and with different accepted techniques. However, no correction can be

made in the case of indeterminate errors, but it is possible to use statistical methods to

deduce the most probable value of a series of measurements and the degree of its

reliability.

29

Basic Aspects

The most important thing for analyst is to give a careful thought to the selection of a

method for the particular analysis keeping in mind the relative amount of analyte and

the composition of the sample. The different means of minimizing errors and

improving the accuracy can be discussed in the following paragraphs.

The determinate errors due to equipment and reagents can be minimized in a

quantitative estimation by the self evident means of reducing errors as (i) calibration

of weights, (ii) calibration of volumetric glasswares (iii) use of purified reagents (iv)

use of samples of proper size etc. After calibrating the devices the correction should be

properly applied. The equipment should be recalibrated frequently. The reagents of

desired purity should be taken and purification should be performed whenever

necessary. A comparison should be made with high purity marked reagents, for

example, AnalaR reagents.

Determinate errors are frequently caused in the use of measuring devices powered by

electricity due to the variation in voltage, change in resistance by dirty electrical

contacts and temperature effect. These errors are detectable and correctable.

The use of instrument of adequate sensitivity and reproducibility is essential. Special

methods of minimizing errors are applied in instrumental methods, for example, in

spectrophotometry by measuring absorbance between 0.1 to 1.0 on scale and in X-rays

by proper counting, etc. The size of the sample and the relative amount of the analyte

is also worth to be considered. Trace determinations are almost always carried out by

instrumental methods. At present, modern instruments of high sensitivity and low

detection limit are being developed where many errors are automatically omitted.

Sometimes, the constant errors may be decreased by variation in sample size.

The errors caused due to certain sources as reagents, vessels, solubility of precipitate

etc., can be minimized by the proper use of blanks. Of course in refined work a blank

run is always preferred. A blank contains all other reagents required for a particular

determination except the material to be analyzed and a blank run involves all steps of

the actual analysis as of the sample. The correction is then made in the results known

as blank correction. For example, in a volumetric determination the titrant reading is

often corrected for the volume of the titrant required to cause an indicator (indicator

blank) to change the colour. The blank run is best carried, simultaneously, along with

the sample. The use of blank is not necessary in every determination. In some a blank

can safely be omitted, while in others it is essential. For example, a gravimetric

determination of chloride with silver nitrate hardly requires a blank, on the other hand

the volumetric determination of chloride by silver nitrate using potassium chromate as

indicator essentially requires the correction due to indicator blank.

This method involves addition of a known amount (standard) of constituent to a

sample, which is then analysed for the total amount (sample + standard) of constituent

present. The measurement (of sample + standard) is compared with the reading taken

on the sample (alone) to be analyzed. The correct amount of analyte in the sample is

determined by simple calculation. It has been proved to be very useful in a few

instrumental methods (e.g., radiometric analysis, polarography, etc.).

An important use of standard addition is made in isotopic dilution method. The

technique is suitable where a compound can be isolated in a pure state but with only a

poor yield. A known amount of the same substance (as analyte) containing an active

isotope is added to the unknown (sample) and thoroughly mixed with it. The desired

30

constituent its isolated in a pure form from the mixture (active + inactive sample) and

is activity is measured. The quantity of the desired substance in the sample can be

determined by simple calculation. This technique has the great advantage that the

standard and the unknown are measured under identical conditions.

2.3.4

Evaluation of

Analytical Data I

Independent Analysis

Detection of methodic errors is rather difficult. There may be more than one way to

cause these errors. In one way the determinate errors of method can be detected by

analysis of a synthetic sample whose overall composition is known and closely

resembles that of the analyte. In an other way, to minimize the methodic errors often

analysis of the sample is done by a method of established reliability. Here the results

of one method may be compared by the results of an entirely different method. If the

results obtained by the two radically different methods are concordant, there is high

probability of values being correct within small limits of error.

In some instances the determinate error of the method may be minimized by carrying

out the analysis by a method of high accuracy. For instance, for gravimetric

determination of aluminium, the old procedure involves the precipitation of aluminium

as hydrous aluminium oxide and ignition of precipitate at high temperature to

aluminium oxide and weighed. In the newer procedure aluminium is precipitated as

aluminium 8-hydroxyquinolinate, precipitate is dried at (low temperature) 130C and

weighed as hydroxyl quinolinate. The newer method requires a much lower

temperature heating as compared to the older method. The high molecular weight

weighing form of the quinolinate precipitate reduces the weighing error increasing the

accuracy as is evident by the calculation ratios:

2 Al

= 0.5291

Al 2 O 3

2.3.5

and

Al

= 0.05872

Al (C 9 H 5 ON ) 3

Improvement in Methods

You can recall about the determinate errors where we considered that such errors can

be minimized by proper control of conditions but requires an understanding of the

effect of variables on the analytical systems. We can, therefore, make the

improvements in the analytical methods in which determinate errors can be reduced in

magnitude. Such work is chiefly the task of analytical chemist to modify the methods

in the light of demands. Especially in applied analysis, methods are essentially needed

to be modified to minimize the errors. For example, suitable separations may be

adopted in the given procedure for the determination of analyte. The proper

combination of methods of separation and determination can do much to minimize the

errors due to interferences.

2.4

You have experienced that a single measurement cannot be taken as an accurate result.

A single result could be in error of one kind or the other. Our confidence in an

analytical result is increased by increasing the number of parallel determinations

(replicate determinations). When assessing the final results it is necessary to judge

(i) their accuracy, and (ii) their precision. It will be worth while to understand the

meanings of these two terms while evaluating the analytical data.

2.4.1

Accuracy

The term accuracy is defined as the nearness of a measurement to its true value

(or accepted value). It is expressed in terms of error. Error (defined in section 2.2) is

an inverse measure of accuracy. Less the error greater is the accuracy. Thus, after

knowing the relative error the loss in accuracy can be estimated.

31

Basic Aspects

There are various ways and units to express the accuracy of a measurement. The most

common being either in terms of percent relative error or in terms of relative accuracy

in percentage. Consider the illustration.

Example 2.1

A sample was analyzed for desired constituent having 2.62 g as the true value. The

results of three measurements were 2.50 g, 2.54 g, and 2.52 g. Find the error of the

mean (mean error), the percent relative error and the relative accuracy of the mean of

the measurements.

Solution

Measurement (O)

Error (O-T)

2.50 g

2.62 g

0.12 g

2.54 g

2.62 g

0.08 g

2.52 g

2.62 g

0.10 g

Total 7.56

Total 0.30 g

% Relative Error =

Mean Error

0.10

100 =

100 = 3.8%

True Value

2.62

Mean

2.52

100 =

100 = 96.2%

True Value

2.62

2.4.2 Precision

Precision is defined as the reproducibility of measurements. It tells an agreement

between the numerical values of replicate measurements. The magnitude of random

errors determines the precision of the analytical results. It follows that the closer the

results of replicate determinations are to each other, the more precise is the analysis

considered to be. Precision in a common way is expressed in terms of deviation. Less

the deviation more precise the result is. Deviation or apparent error is defined as the

difference between the measured value and the mean (average) of the series of

measurements. The deviation bears a relationship to the mean value of a series similar

to that which exists between the absolute error and the true value. Mathematically,

d = Xi x

(2.2)

xi

x + x + ...+ xn

measurements, x = 1 2

=

where symbol represents summation

n

n

(add all). Deviation is, generally, taken without regard to sign.

deviation relative to the mean expressed in suitable units.

( xi x)

d + d2 + dn

Thus, average deviation (a.d.) = 1

=

n

n

32

and % a.d. =

a.d.

100

x

The most important measures of precision are the standard deviation and the variance.

The standard deviation s of a measurement is theoretically given by:

s=

d12 + d 22 + ... + d n2

n 1

Evaluation of

Analytical Data I

(2.3)

Variance V is the square of the standard deviation,

V = s2 =

(2.4)

n 1

The accuracy should not be confused with the precision. Good agreement in parallel

determinations signifies that the determinations have been made under closely similar

conditions, it does not guarantee the accuracy of the results. A method may be precise

but may not be accurate if a large systematic error is made. On the other hand it is

nearly impossible to have accuracy without good precision. The difference of the

terms accuracy and precision can be illustrated by considering the shooting of series of

bullets on the targets by three riflemen (A, B, C), shown in Figure 2.1

.....

...

A

Both Accurate and Precise

B

Precise but not accurate

.

.

..

C

Neither precise nor

accurate

Rifleman A has the ideal marksmanship. His all hits are in centre. His results are both

accurate and precise. The shooting by rifleman B shows a good grouping of hits which

indicate that the marksman is undoubtedly consistent, but in this target the grouping is

centered at 3 Oclock hence cannot be considered as representing accurate shooting.

His results agree well mutually means precise, but the final result (obtained as their

mean value) differs somewhat from the actual value, therefore not accurate. This

illustrates the effect of a constant error such as poorly adjusted sights and, since

precise marksmanship is evidenced, it is reasonable to assume that if the source of

error can be located and corrected, accurate shooting should be forthcoming.

The shooting by rifleman C shows that the hits are spotted all over the face of the

target in a display of poor reproducibility. It seems that the rifleman has no experience

of shooting, his hits result only as an accident. We say that the mean value is of low

reliability. Hence, these results are neither precise nor accurate. Also we see that good

precision is needed for good accuracy.

Of course the most favourable methods are those which give precise and at the same

time accurate results. In practice results that are precise but subject to small systematic

33

Basic Aspects

error are often more useful than results with an accurate mean value but low precision,

since in first case we can actually find out how much they differ from the true value,

while in the second case we know nothing but that the mean value is of low reliability.

In the following example you can see the difference of accuracy and precision for the

results of burette reading of a titration.

Example 2.2

The burette readings of titrations carried out by three students A, B and C are given

below. Compare the accuracy and precision of the three students, if the true reading is

22.22 ml.

Student

Burette readings

ml

ml

ml

22.22

22.28

22.38

22.24

22.27

22.12

22.23

22.29

22.32

22.21

22.28

22.30

22.20

22.28

22.18

22.22

22.28

22.18

Mean value

You can understand from the observed values and calculated mean values of titrations

of three students that the results of student A are reproducible and the mean value

resembles the true value. Hence the results of student A are both precise and accurate.

A look of the titration results of student B shows that his results are reproducible but

the mean value is slightly on the higher side than the true value. May be he might be

taking the end point (colour change) on the higher side. Therefore, the results of

student B are precise but not accurate. The readings of students C are spread in a wide

range with a poor reproducibility. Hence his results are neither precise nor accurate.

SAQ 2

Define accuracy and precision.

...

...

...

2.5

REPORTING OF RESULTS

An analytical result is reported in two parts: (i) chemical, and (ii) numerical.

As far as possible, the result of the element determined should be reported in the

chemical form in which it is present in the sample analyzed. For example, in reporting

the result of a determination of nitrogen, it should be reported as nitrate, nitrite or

ammonia depending upon the chemical form in which the element (nitrogen) is

present. The analysis of a solution of electrolytes is generally expressed in terms of

the ions present (as Fe3+, Ca2+, Cl , CO32, etc.).

34

However, when the actual form is not known or some other specific purpose is to be

solved, the expression may be modified. Often the purpose for the analysis decides the

form in which the constituents are reported. For example, when limestone is used for

the purpose of manufacture of lime, its calcium content is expressed as calcium oxide.

The hardness of water is usually expressed in terms of calcium carbonate (although a

number of ions other than calcium are present in water).

2.5.2

Evaluation of

Analytical Data I

In most of the analyses, it is the relative amount of the constituent in a sample that is

of importance. Therefore, the numerical expression represents the amount of the

desired constituent as parts of the amount of the sample in suitable units. Thus, if Wi is

the amount of the constituent of interest, Ws is the amount of the sample, and C is a

W

factor required to express the results in suitable units, the expression i C is useful

Ws

for the numerical expression of results of an analysis.

For example, if Wi and Ws are in grams and C is 100, the result is given in percent (%)

by weight of the constituent in the sample. If C is set equal to 1000 and Wi and Ws in

same units, the answer is in parts per thousand (ppt) by weight of the constituent in the

sample. And if C is set equal to 1,000,000 the answer is in parts per million (ppm) by

weight of the constituent in the sample, and so on. The quantities Wi and Ws may also

be expressed in volume units. Way of numerical expression of the results also depends

on the physical state (solid, liquid, or gas) of the constituent and of the sample.

Solids

In case of the solid sample, usually, the weight constituent of interest and that of

sample are taken in the same weight units and the result is expressed as percentage by

weight (weight of constituent 100/ weight of sample) to give the number of parts of

analyte in 100 parts of the sample.

Liquids

i)

Weight of constituen t 100

gives the number of parts of the desired constituent

Weight of sample

in 100 parts of the sample. Both weights are taken in same units.

ii)

Weight-volume percentage:

iii)

gives the number

Volume of sample in mL

of parts by weight of constituent in 100 parts by volume of the sample. The

temperature should be mentioned.

Volume of constituen t

100 gives the number of parts of

Volume of sample

volume of desired constituent in 100 volumes of the sample. Both the volumes

should be taken in the same units and the temperature should be specified.

Volume percentage:

Gases

Volume of constituen t

that is,

100. Both the volumes should be taken in the same

Volume of sample

units and the temperature should be specified.

35

Basic Aspects

The percentage representation is very common, but it is useful mainly for major

constituents. When the constituent is in traces, it is advantageous to express in parts

per million by weight or volume. For further lower amounts, parts per billion or parts

per trillion may also be used.

2.6

SIGNIFICANT FIGURES

In the preceding section you learnt how to report the results of measurements of an

analysis. In this section you will learn about the use of correct number of significant

figures. The correct number of significant figures in measurement and calculations is

critical in giving the proper significance to an analysis.

You know that a number is a mathematical expression of a quantity. A figure, or digit,

is any one of the characters 0, 1, 2,, 9 which, alone or in combination, serves to

express a number. The digits of a number which are needed to express the precision of

the measurement from which the number was derived are known as significant figures.

Digits from 1 to 9 are always a part of significant figures, while 0 may or may not be a

significant figure. A digit signifies the amount of the quantity in the place in which it

stands. In case of the number 542, the figures signify that there are five hundreds, four

tens, and two units and are therefore all significant.

The character zero (0) is used in two ways, it may be used as a significant figure or it

may be used merely to locate the decimal place. When zero is the part of the

measurement it is significant. For example, the weight of a crucible is found to be

12.610 g. The terminal zero is significant meaning that the weight can be measured

correctly upto third place of decimal. The zero after 1 is significant because this is the

part of the measurement. Similarly, expressing the concentration of a copper sulphate

solution as 0.1000 N, the three zeros after 1 are all significant.

Consider the number 107.2 cm. The zero between 1 and 7 is significant because zero

placed between two significant figures is significant. This number has four significant

figures regardless of where the decimal point is placed, say 1072 mm, 10.72 dm, 1.072

m and 0.001072 km all have four significant figures, they simply represent the result

in different units. In the last number 0.001072 km, the zeros before 1 are just to locate

the decimal point and therefore are not significant.

To write a result with some degree of certainty the correct use of significant figures

must be made, which depends on various rules for computation. The student should be

familiar about these (the rules have got the limited validity), i.e.

i)

Observed quantities should be recorded with one uncertain figure retained. That

is, there must be as many significant figures in a result or in any data as will

give only one uncertain figure. Thus, in most analyses represent the last

retained significant figure by 1. For example, a value 22.6 ml represented as

22.61 means that this is known to be between 22.5 ml and 22.7 ml.

ii)

the superfluous figures, increase the last retained figure by one if the following

figure (which is dropped) is greater than 5. For example, the number 46.2368

rounded off to four significant figures becomes 46.24.

If the dropped digit is exactly 5 (not 51, 524, etc. which are treated as greater

than 5), the last retained figure is rounded off to the nearest even digit. Thus,

3.55 is rounded off to two significant figures = 3.6

3.65 is rounded off to two significant figures also = 3.6

36

Evaluation of

Analytical Data I

2.652 rounded off to one decdimal place = 2.7

If the dropped figure is less than 5 the last retained figure is not changed. Thus,

26.4332 ronded off to four significant figures = 26.43.

iii)

terms of the least significant unit. It is mainly for decimal places in the numbers

and the number having the fewest decimals is thus the least significant unit.

Thus, the result of sum or difference should have the number of decimals equal

to the number of decimals present in the least significant unit (means the

number having the fewest decimals). Although, all numbers being added or

subtracted can be rounded off to the least significant unit. But again for the

consistency in the answer in practice we keep an extra figure during stepwise

calculations and then the final result is rounded off to one less figure. For

example, summing the numbers: 26.234 + 3.223 + 143.4 + 2.2260, the third

number 143.4 is the least significant unit which contains only one decimal

place. Therefore, all other numbers are rounded off to two decimal places and

the final result is then rounded off to one decimal place (equal to the number

having least decimal places).

26.234 is rounded off to

3.223 is rounded off to

143.4 is retained as

2.2260 is rounded off to

26.23

3.22

143.4

2.23

Sum =

175.08

iv)

In multiplication or division you can retain in each factor one more significant

figure than that of a factor having the least significant figures (that is significant

figures contained in the least precise factor). After calculations the answer is

rounded off to the number of significant figures contained in the least precise

factor. For example, in the multiplication

7.0783 0.00305 6.602

the middle factor has got the least (=3) significant figures hence the values will

be written as

7.078 0.00305 6.602 = 0.1425233

The answer rounded off to 3 significant figures is = 0.143

v)

the individual steps must be treated separately. As good practice one extra

figure may be retained in the intermediate calculations and the final result is

then rounded off by dropping the superfluous figures.

vi)

calculation. The final result is rounded off as desired.

vii)

viii)

composed of two parts (i) the characteristic which is a whole number and is

indicative of the position of the decimal in the given number and hence is not a

significant figure, (ii) the mantissa which is a decimal fraction and is the same

regardless of the position of decimal in the given number. For example, to

express properly the logarithm of 2.4 104, characteristic is 4 and mantissa is

37

Basic Aspects

0.3802 and the logarithm is 4.3802. The result is rounded to 4.38 since the

given number (2.4 104) has only two significant figures.

Example

Solution

The 3 is the characteristic (from 103). The mantissa is 0.6010 (from the logarithm of

4.0). But the concentration is known only upto two significant figures, hence

pH = ( 3 + 0.6010) = 3 0.60 = 2.40 Answer.

SAQ 3

List the proper number of significant figures in the following numbers

i) 0.162

ii) 10.06

iii)

200.0 iv) 0.0260

...

...

...

2.7

SUMMARY

In this unit you have learnt that the errors may be classified as determinate and

indeterminate. The reasons for the determinate errors can be assigned and hence can

be corrected for, whereas no definite reason can be assigned for indeterminate errors

and they follow the rules of chance. The two terms: accuracy and precision are

frequently used in evaluation of analytical data. The accuracy tells the nearness to the

true value and the precision tells the reproducibility of replicate determinations. The

smaller the determinate error in the determination, the more accurate is the result

considered to be. A result may be precise even without being accurate. On the other

hand a result cannot be accurate unless it is precise. Correct use of significant figures,

which is dependent on the application of various computation rules, is of fundamental

importance in the reporting of analytical results. The important computation rules for

correct use of significant figures are discussed.

2.8

TERMINAL QUESTIONS

1.

crystallization as against the formula BaCl2.2H2O the true value of 14.75%.

Estimate the absolute error, relative error and the relative accuracy.

2.

16.70, 16.68, 16.60, 16.58 and 16.63. The true value of FeO in the sample was

reported to be 16.55%. Calculate the mean error and the relative error in parts

per thousand.

3.

a) 0.062005

4.

c) 0.00625

d) 1.008

e) 6.111

Express the result of each of the following calculations to the proper number of

significant figures.

a)

38

b) 31.4

5.

b)

4.1374 0.0603

c)

4.1374 2.81

d)

14.37 6.44

Evaluation of

Analytical Data I

2.47 Sn, 7.60 Pb, 62.08 Cu, 0.027 Fe & 27.86 Zn.

Calculate the total percentage determined. Apply the rules for correct use of

significant figures.

6.

40.36 0.0999 51.9961

346.6

7.

2.9

Express the result of each of the following calculations to the proper number of

significant figures:

a)

4.178 + 4.032

1.217

b)

2.321

(b)

0.2148

ANSWERS

1.

0.04

RE (ppt) =

1000 = 7.58 ppt

5.28

2.

The accuracy is nearness to true value and the precision tells the reproducibility

of replicate determinations. A result may be precise even without being

accurate. On the other hand a result cannot be accurate unless it is precise.

3.

i) 3

ii) 4

iii) 4

iv) 3

Terminal Questions

1.

E

0.05

Relative Error (% R.E.) = 100 =

100 = 0.34%

T

14.75

14.70

Relative accuracy =

100 = 99.66%

14.75

2.

16.65 + 16.70 + 16.68 + 16.60 + 16.58 + 16.63

= 16.64% FeO

6

Error of the mean (Mean Error) = 16.64 16.55 = 0.09% FeO

Error

0.09

Relative error (ppt) =

1000 =

1000

True Value

16.55

= 5.438

Rounded off to two decimal places = 5.44 ppt

3.

a) 5

b) 3

c) 3

d) 4

e) 4

39

Basic Aspects

4.

a)

numbers can have to a maximum 3 decimal places and then the result will

be rounded off to two decimal places. Thus,

4.1374 is rounded to

4.137

2.81 is retained as

2.81

0.0603 is rounded to

0.060

Total

7.007

b)

4.1374 is retained as

0.603 is retained as

= 4.0771

4.1374

0.0603

c)

4.137

2.81 is retained as

2.81

= 1.327

= 1.33

Since the number 2.81 has only 2 decimal places hence the answer is

rounded off to 1.33.

d)

14.37 6.44

= 14.37 6.44

= 92.5428

= 92.5

5.

The least significant unit has 2 decimal places. Therefore, the sum is = 2.47 +

7.60 + 62.08 + 0.027 + 27.86 = 100.037 = 100.04%

6.

According to the rules of multiplication and division the various factors are

written as

40.36 0.0999 51.996

= 0.6048643

346.6

Rounded off to 3 significant figures, the answer is = 0.605

7.

a)

4.178 + 4.032 = 8.210

Then, 8.210/1.217 = 6.7460969

Rounded off to 4 significant figures, the answer is = 6.746

b)

2.1807 204.2

Then,

= 2073.0863

0.2148

Rounded off to 4 significant figures the answer is = 2073

c)

The number 0.00202 has the least number of significant figures = 3, hence

all other factors can have upto 4 significant figures and the answer should

have 3 significant figures

14.28 0.00202 0.5503

= 0.0068391

2.321

40

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