DATA HANDLING IN

ANALYTICAL CHEMISTRY

SIGNIFICANT FIGURES
Two types of numbers:
Exact number consider as number with no
uncertainty e.g. factor in a multiplication (100 in
calculation of percentage), exponent (102, 10-3) etc.
Measured number other than the exact number,
has a degree of uncertainty normally in the last digit
e.g. the wt. of a compound is found to be 12.4567g.
It can simply means 12.45670.0001g.
2

What is the length of the wooden

stick?
1) 4.5 cm
2) 4.54 cm
3) 4.547 cm

Measured Numbers
Do you see why Measured Numbers have
erroryou have to make that Guess!
All but one of the significant figures are known
with certainty. The last significant figure is only the
best possible estimate.
To indicate the precision of a measurement, the
value recorded should use all the digits known with
certainty.
4

Below are two measurements of the mass of the

same object. The same quantity is being described at
two different levels of precision or certainty.

 The weak link in the chain of any analysis is

governed by that measurement that can be made
with the least accuracy.
This means that the least accurate measurement
will determine the number of significant figures of
the results of any analysis.

When a measurement is recorded, only those digits that are

dependable are written down.
If you measured the width of a paper with your ruler you
might record 21.7cm.
To a mathematician 21.70, or 21.700 is the same.
But, to a scientist 21.7cm and 21.70cm is NOT the same.
21.700cm to a scientist means the measurement is accurate
to within one thousandth of a cm.
However, if you used an ordinary ruler, the smallest
marking is the mm, so your measurement has to be
recorded as 21.7cm.
7

 If we weigh a sample with an analytical balance, the wt

can be expressed as e.g. 10.1234g.
If we measure a volume of a solution with a burette, the
volume can be expressed as e.g. 21.25ml
This means that the calculation of final results utilising the
two values should appropriately contain only 2 decimal
points. Why?

10

Analytical balance
Precise up to 4 decimal places in
gram
e.g. 12.0123 g

Top pan balance Precise

up to 2 decimal places in
gram e.g. 12.01 g

11

Number of Significant Figures

23.45 has 4 significant figures
45678 = 4567.8 = 456.78 = 45.678 = 4.5678 = 0.45678
has 5 significant figures regardless of where the decimal
point is.
92067m = 9.2067cm = 0.092067m
All have same number of significant figures, merely
expressed in different unit.

12

The position of zero

13

45.8736
.000239
.00023900
48000.
48000
3.982 X 106
1.00040

6
3
5
5
2
4
6

All digits count

Leading 0s dont
Trailing 0s do
0s count in decimal
form
0s dont count w/o
decimal
All digits count
0s between digits
count as well as trailing
14
in decimal form

 State the number of significant figures in each of these

numbers.
1) 274.03
2) 1.060 x 104
3) 0.00054
4) 600
5) 72000.0
6) 8.000
7) 67.030
15

The General Analytical Problem

Select sample
Extract analyte(s) from matrix

Separate analytes
Detect, identify and
quantify analytes
Determine reliability and
significance of results
16

Introduction
The design of experiments (including
size of sample required, accuracy of
measurements required and the number
of analyses needed) is determined from
a proper understanding of what the data
will represent.
17

Introduction
A knowledge of statistical analysis will be required as
you perform experiments in the laboratory.
To understand the significance of the data that are
collected .

18

Mean

xi

Defined as follows:

x =

i=1

Where xi = individual values of x and N = number of replicate

measurements

Median
The middle result when data are arranged in order of size (for even
numbers the mean of middle two).
Median can be preferred when there is an outlier - one reading very
different from rest.
Median less affected by outlier than is mean.
19

Illustration of Mean and Median

Results of 6 determinations of the Fe(III) content of a solution, known to
contain 20 ppm:

Note: The mean value is 19.78 ppm (i.e. 19.8ppm) - the median value is 19.7
ppm (i.e. (19.6+19.8)/2)

20

Precision
Relates to reproducibility of results..
How similar are values obtained in exactly the same way?

Useful for measuring this:

Deviation from the mean:

di xi x
21

Accuracy
Measurement of agreement between experimental mean and
true value (which may not be known!).
Measures of accuracy:
Absolute error: E = xi - xt (where xt = true or accepted value)
Relative error:

x x
t 100%
E i
r
x
t

(latter is more useful in practice)

22

Accuracy and Precision: There is

a difference
Accuracy: the degree of agreement between the
measured value and the true value.
Precision: the degree of agreement between
replicate measurements of the same quantity.
Means the repeatability of a result.
Expressed as the standard deviation.
The more measurements that are made, the more
reliable will be the measure of precision.
Good precision does not assure good accuracy.

23

Illustrating the difference between accuracy and precision

Low accuracy, low precision

Low accuracy, high precision

High accuracy, low precision

High accuracy, high precision

24

Errors in Chemical Analysis

Impossible to eliminate errors.

How reliable are our data?
Data of unknown quality are useless!

Carry out replicate measurements

Analyse accurately known standards
Perform statistical tests on data

25

Types of Error in Experimental Data

Three types:

(1) Random (indeterminate) Error

(2) Systematic (determinate) Error

(3) Gross Errors

Usually obvious - give outlier readings.
Detectable by carrying out sufficient replicate
measurements.
26

Systematic/determinate Error
Readings all too high or too low.
Affects accuracy
Systematic errors can be constant (e.g. error
in burette reading
less important for larger values of reading
Proportional, e.g. presence of given
proportion of interfering impurity in sample
equally significant for all values of
measurement
27
Several possible sources.

Sources of Systematic/determinate Error

Some common determinate errors are:
(1)instrumental errors: these include
faulty equipment, un-calibrated weights
and un-calibrated glasswares.
Need frequent calibration - both for
apparatus such as volumetric flasks,
burettes etc., but also for electronic
devices such as spectrometers.
28

Sources of Systematic/determinate Error

(2) operative errors: includes personal errors and can be
reduced by experience and care of the analyst in the
physical manipulations involved.
Operations include transfer of solutions, bumping during
sample dissolution, incomplete drying of samples etc.
Insensitivity to colour changes for spectrophotometric
methods
Other personal errors mathematical errors in
calculations
Prejudice in estimating measurements: tendency to
estimate scale readings to improve precision;
preconceived idea of true value..
Difficult to correct for.
29

Sources of Systematic/determinate Error

(3) Errors of the method most serious errors of an
analysis.
Errors that are inherent in the method cannot be
changed unless the conditions of the determination
are altered.
Due to inadequacies in physical or chemical
behaviour of reagents or reactions (e.g. slow or
incomplete reactions)
Example nicotinic acid does not react completely
under normal Kjeldahl conditions for nitrogen
determination.
Reagent blank analysis on the added reagents
only. It is standard practice to run such blanks and to
30
subtract the results from those for the sample.

Minimisation of Systematic Errors in

Chemical Analyses
Minimise instrument errors by careful recalibration and good
maintenance of equipment.
Minimise personal errors by care and self-discipline

Method errors - most difficult.

True value may not be known.
Three approaches to minimise:
analysis of certified standards
use two or more independent methods
analysis of blanks
31

Random Errors or Indeterminate Errors

Often called accidental errors.
Data scattered approx. symmetrically about a mean
value.
Affects precision - dealt with statistically
Represent the experimental uncertainty that occurs in
any measurement.
Revealed by small differences in successive
measurements made by the same analyst under
virtually identical conditions and cannot be predicted
or estimated.
32

Treatments of Random Errors

There are always a large number of small,
random errors in making any measurement.
These can be small changes in temperature or
pressure; random responses of electronic
detectors (noise) etc.
Can use statistical treatment for random errors

33

Standard Deviation
s : measure of precision of a population of data,given by
N

2
(
x

)
i
i 1

Where = population mean; N is very large.

The equation for a Gaussian curve is defined in terms of

and s, as follows:

( x ) 2 / 2s 2

s 2

34

Standard Error of a Mean

The standard deviation relates to the probable error in a single measurement.
If we take a series of N measurements, the probable error of the mean is less than
the probable error of any one measurement.
The standard error of the mean, is defined as follows:

sm s

35

Gaussian curve
SAMPLE = finite number of observations
POPULATION = total (infinite) number of observations
Properties of Gaussian curve defined in terms of population.
Modifications needed for small samples of data

Main properties of Gaussian curve:

Population mean () : defined as earlier (N ). In absence of systematic error,
is the true value (maximum on Gaussian curve).
sample mean (

) defined for small values of N.

(Sample mean population mean when N 20)

36

Frequency Distribution for

Measurements Containing Random Errors

4 random uncertainties

A very large number of

random uncertainties

10 random uncertainties

This is a
Gaussian or
normal error
curve.
Symmetrical about
the mean.
37

Replicate Data on the Calibration of a 10ml Pipette

No.

Vol, ml.

No.

Vol, ml.

No.

Vol, ml

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17

9.988
9.973
9.986
9.980
9.975
9.982
9.986
9.982
9.981
9.990
9.980
9.989
9.978
9.971
9.982
9.983
9.988

18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34

9.975
9.980
9.994
9.992
9.984
9.981
9.987
9.978
9.983
9.982
9.991
9.981
9.969
9.985
9.977
9.976
9.983

35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50

9.976
9.990
9.988
9.971
9.986
9.978
9.986
9.982
9.977
9.977
9.986
9.978
9.983
9.980
9.983
9.979

Mean volume
9.982 ml
Standard deviation 0.0056 ml

Median volume

9.982 ml
38

Calibration data in graphical form

A = histogram of experimental results

B = Gaussian curve with the same mean value, the same precision (see later)
and the same area under the curve as for the histogram.
39

Standard Deviation & Gaussian Curve

Two Gaussian curves with two different
standard deviations, sA and sB (=2sA)

General Gaussian curve plotted in

units of z, where
z = (x - )/s
i.e. deviation from the mean of a
datum in units of standard
deviation. Plot can be used for
data with given value of mean,
and any standard deviation.
40

Area under A Gaussian Curve

From equation above, and illustrated by the previous curves,
68.3% of the data lie within s of the mean (), i.e. 68.3% of
the area under the curve lies between s of .

Similarly, 95.5% of the area lies between s, and 99.7%

between s.

There are 68.3 chances in 100 that for a single datum the
random error in the measurement will not exceed s.

The chances are 95.5 in 100 that the error will not exceed s.

41

Sample Standard Deviation, s

The equation for s must be modified for small samples of data, i.e. small N
N

2
(
x

x
)
i
i 1

N 1

Two differences cf. to equation for s:

1.

Use sample mean instead of population mean.

2.

Use degrees of freedom, N - 1, instead of N.

Reason is that in working out the mean, the sum of the
differences from the mean must be zero. If N - 1 values are
known, the last value is defined. Thus only N - 1 degrees
of freedom. For large values of N, used in calculating
s, N and N - 1 are effectively equal.

42

Alternative Expression for sample standard deviation, s

(suitable for calculators)

( xi ) 2

i 1

( xi 2 )

i 1

N 1

Note: NEVER round off figures before the end of the calculation

43

Methods for expressing the precision (CV)

COEFFICIENT OF VARIANCE (CV)
(or RELATIVE STANDARD DEVIATION):
Divide the standard deviation by the mean value and express as a percentage:

s
CV ( ) 100%
x
VARIANCE:

This is the square of the standard deviation:

N

s2

2
2
(
x

x
)
i
i 1

N 1

44

Exercise - Sample Standard Deviation

Reproducibility of a method for determining the content of
selenium in foods was studied. 9 measurements were
made on a single batch of brown rice.
Sample
1
2
3
4
5
6
7
8
9

Selenium content (g/g) (xI)

0.07
0.07
0.08
0.07
0.07
0.08
0.08
0.09
0.08

Based on this data, what can you say about the

reproducibility of the method?
45

Answer to exercise
Sample
1
2
3
4
5
6
7
8
9

xi2
0.0049
0.0049
0.0064
0.0049
0.0049
0.0064
0.0064
0.0081
0.0064

Selenium content (g/g) (xI)

0.07
0.07
0.08
0.07
0.07
0.08
0.08
0.09
0.08
Sxi

0.69

Mean = Sxi/N= 0.077g/g

Standard deviation:

Sxi2=

0.0533

(Sxi)2/N = 0.4761/9 = 0.0529

0.0533 0.0529
0.00707106 0.007
9 1

Coefficient of variance = 9.2% Concentration = 0.077 0.007 g/g

46