CHM421-Topic 3

Statistics - Evaluation of
Experimental data
Dr. Zuraida Khusaimi

Evaluation of data
(Statistics)

Evaluation of experimental
data error, mean, median,
precision and accuracy, std.
deviation and pooled std.
deviation

Significant figures, uncertainty,

confidence limits & significant
tests, gross error and Q test

Statistics Terminology
Error Types
Indeterminate (random error):
evaluate with statistics.
Determinate (systematic error):
evaluate with reference standard.
Gross error: big mistake, like spilling
everything on the floor.

Sytematic / Determinate error

All measuring devices are sources of
determinate errors.
DE have a definite source that usually can
be identified.
DE cause all the results from replicate
measurements to be either high or low.

Significant Figures
Zeros between non zero digits are significant
508 cm has 3 sf
Leading zeros merely locate the decimal point and are never
significant
0.0497 cm equals 4.97 x 10-2 cm and has 3 sf

Trailing zeros are significant as follows:

50.0 mL has 3sf

50. mL has 2 sf
50 mL has 1 sf

Datum
(grams)

Number of
significant
figures

Datum
(milliliters)

Number of
significant
figures

10.034
1.908
0.32
0.00046
150
0.0000160

5
4
2
2
2
3

150.
0.705
0.054
5.86 x 10-7
3040
0.0000730

3
3
2
3
3
3

SF (Addition & Subtraction)

When adding or subtracting do NOT extend the
result beyond the first column with a doubtful
figure.
For example

1.592
2.1
129.4917

0.29462
133.47832

discard

round

133.5

report

What is 16.874

+ 2.6
16.874
+ 2.6
19.474

report

discard

round

19.5

What is 16.874 2.6

16.874
+ 2.6
14.274
round

report
discard

14.3

SF (Multiplication & Division

When multiplying or dividing the answer will have the same
number of significant digits as the least accurate number used
to get the answer.
For example:

2.005 g / 4.95 mL = 0.405 g/mL

What is 16.874 x 2.6?

16.874
x 2.6
43.8724

report
discard

round

44

What is 16.874/2.6?
16.874 / 2.6 = 6.49
discard
round
report
6.5

Statistical Procedures to
handle analytical data
Mean
Standard Deviation
Median

Range
Precise and deviation
Accurate and error

Mean (average), x
Mean is the average reading of all
data or measurements that are
obtained from an experiment.
Mean can be calculated by dividing
the sum of replicate measurements
by the number of measurements in
the set.

Mean for sample

where n is the number of samples

Q.
Five students obtained % of chlorine in sample as follows:
19.82 , 19.57 , 19.68 , 19.71 and 19.75
Calculate
i) mean

Standard Deviation (s)

n-1 = degree of freedom. In
the calculation of standard
deviation, the degree of
freedom is reduced by ONE.

Measures the precision or scatter of

sample data set
Larger std. dev. means more scatter about
the mean, worse precision. Smaller std.
dev. means less scatter about the mean,
better precision. Q.
Five students obtained % of chlorine in sample as follows:
19.82 , 19.57 , 19.68 , 19.71 and 19.75
Calculate ii) standard deviation

Median
Median is a value that is in the middle
of a set of data.
Median of a set of replicate data is
the middle result when the data are
arranged by increasing in size.
Q.
Five students obtained % of chlorine in sample as follows:
19.82 , 19.57 , 19.68 , 19.71 and 19.75
Find median.

Range
The highest value minus (-) the
lowest value.
Q.
Five students obtained % of chlorine in sample as follows:
19.82 , 19.57 , 19.68 , 19.71 and 19.75
Calculate range.

Exercises
Five students obtained % of chlorine
as follows:

19.82, 19.57, 19.68, 19.71 and 19.75

Calculate
i) mean

Ii) standard deviation

Precision
Precision is how close the measured values are to each
other, for measurements that have been made the same
way.

Precision describes the reproducibility of results, that is the

agreement between two or more
Expressed in terms of DEVIATION
If the deviation between the measurements is small, then
the work is precise.
Deviation = (Value obtained Mean value) = (Xi X)

Accuracy
Accuracy is how close a measured value is to the
actual (true) value or expert value which is believed to
be correct.
Expressed in terms of ERROR / ABSOLUTE ERROR ,
E

E = (Value obtained True value)

If the error is small, then the measurements are accurate,
And it shows the accuracy of the results obtained.
Usually the errors are reported as % error or relative error.

Absolute error, E
Where xi value is obtained
experimentally, xt is the
true value.
The sign of absolute error
indicate whether the value
in question is either high or
low as compared to true
value

Relative error, Er

Relative error from mean

is

Percent relative error, % E

Example

High Accuracy Low Precision

Low Accuracy High Precision

High Accuracy High Precision

Exercise
Students results
%Cl

60.50

60.41

60.53

60.54

60.52

If the experts value / true value is 60.66%. Calculate

i) mean

Iii) deviation

ii) median

iv) % relative error

v) absolute error on data 2

vi) absolute error on mean

Statistics Terminology
Groups
Population: A set of all possible
measurements. This can only be
approached ideally.
Sample: A set of actual
measurements. Usually a small
number of measurement (less than
20).

Sample & Population

SAMPLE ( x )
A small set of
data 20

Where n is the
number of
samples usually
20

Mean
POPULATION ()
Large set of data
20

Where N is very
large for real
population
is the true mean

Sample & Population

Standard Deviation (SD)
SAMPLE SD (s)

POPULATION SD ()

The Sample Standard Deviation (S)

Standard Deviation, (s) is a more
significant quantity as it measures the
precision or scatter of sample data set

The n-1 term represents the degree of

freedom. In the calculation of standard
deviation, the degree of freedom is
reduced by ONE.

The Population
Standard Deviation ()
When N , x and s

True Standard deviation, =

Pooled std deviation

Sp =

(xi1 x1)2 + (xi2 x2)2+ . + (xik xk)2

N-k

Uses of statistics

Type a quote here.

Johnny Appleseed

Test of Significance
- is there any difference

t-test
Q-test
F-test

Statistics Terminology
Tests
T-Test: Is used to calculate the confidence
intervals of a measurement when the population
standard deviation () is not known. It is also used
to compare two averages. The t-test corrects for
the uncertainty of the sample standard deviation
(s) caused by taking a small number of samples.

Q-test: Is used to determine if there is a statistical

basis for removing a data point from a data set.

The uses of statistics

Q-test deciding wheter an outlying
value (outliers) in a set of a replicate
results should be RETAINED or
REJECTED in calculating the mean
for the set of data.
T-test determining the number of
replicate measurements required so
that the experimental mean falls in
the range where expected true value
falls.

Q-test

Q-test

xsuspect xnearest
Q =
xmax xmin

Q-test Accepting or
Rejecting An Experimental
Data
The method by which an
experimental data can be rejected
involves the use of a statistical test.
By using the Q-test, it can indicate
with a reasonable probability that a
particular value should be retained or
rejected.

Steps involved in Q-test

Arrange the data in an increasing
order.
Calculate the difference between the
suspect value and its nearest
neighbour, (a).

Calculate the range (difference

between highest and lowest values,
(w)).

Steps involved in Q-test

Calculate Q by using the following
relationship

Qexp = a/w
Qexp is then compared to the Qtable. If
the value of Qexp Qtable, the
questionable result can be rejected
with the indicated degree of
confidence.

Example: Trial A appears incorrect. Check using Q-test at

90% confidence whether trial A should be rejected or
accepted
Trial A
Vol. of
HCl
used
(mL)

I
25.75

II
25.62

III
25.52

IV
25.21

V
25.65

VI
25.60

VII
25.71

Solution:
25.21 25.52 = 0.31 = 0.57
25.75 25.21
0.54
Qexp Qtable i.e. 0.57 0.51, therefore the reading 25.21 should be
rejected

t-test
Finding significant difference between two methods
based on their mean values (and/or pooled SD)

The t-test assesses whether the means of two groups

are statistically different from each other. This analysis
is appropriate whenever you want to compare the
means of two groups.
Determining the number of replicate measurements
required so that the experimental mean falls in the
range where expected true value lies (t-test)

Rules to observe
1.

The possible differences between

the true mean () and the estimated
mean x increases with increasing
standard deviation.

s then x

s also increases with a decreasing

number of data points to average.

2. Probability / chances are called RANGE

RANGE which the true value falls (the highest
- the lowest).
The range is called the confidence interval
and limit of this range is called the
confidence limit.
confidence limit = x ts / N
Where t = N-1 (Degree of freedom from Table
1 and N = number of trials)

Example: The following results were obtained in replicate

analysis for the determination of vitamin C in tablet
samples by titration method. The table below shows the
result. The value on the label is 250.00 mg
Samplle
Weight
of
vitamin
C (mg)

I
250.06

II
249.10

III
249.87

IV
251.15

V
250.21

Use Q-test at 90% confidence to reject any

VI
244.81

VII
250.99

t-test
NH: x = xt

if x1 = x2

ttest =

x xt
s/ N

x1 x2
ttest =
spooled N1 + N2
N1N2

Significance Test Null Hypothesis Testing

COMPARING EXPERIMENTAL MEAN WITH TRUE VALUE

To test bias in analytical method

Use the method to analyse sample of known composition i.e. when
true value is known

Possible for x (mean) xt

Is difference due to random error or systematic error

NH: x = xt

ttest =

x xt
s/ N

Compare t-test with tcrit

tcrit is obtained from table
|ttest | tcrit, reject NH at chosen
confidence level

|ttest | tcrit, accept NH at chosen

confidence level

x xt
i.e. significantly
different than xt
systematic error
is significant

x = xt
i.e. no significant
error is observed
between x & xt
difference may be
due to random
error

t-test Example

NH: x = xt

ttest =

x xt
s/ N

Type a quote here.

Johnny Appleseed

X1=x2

Solution to example 3.18

Type a quote here.

Johnny Appleseed

F-test
Finding significant difference between
two methods based on their std.
deviations
Is s1=s2?

F = s1 2 / s2 2, where s1 2> s2 2

F-test
Example

F-test
Example