EVALUATION OF

EXPERIMENTAL DATA
 LEARNING OUTCOME
At the end of this class, you should be able to:

 Define the term of significant figures, accuracy &

precision.

 To explain the types of error, the sources of errors and

how to avoid errors.

 To calculate the mean, median, deviation, standard

deviation, the Q-Test.

2
SIGNIFICANT FIGURES
 SIGNIFICANT FIGURES
Definition: total number of digits that show a certain quantity of
measurement which include zero at the back except if it is in front.

• All non zero digits are significant

3.257 kg 4 significant figures

 Zero between nonzero digits are significant

407 m 3 significant figures

 Leading zeros are not significant

0.09 L 1 significant figure

 If a number is greater than 1, then all zeros to the right of the

decimal point are significant
5.0 mg 2 significant figures
 If a number is less than 1, then only the zeros that are at
the end and in the middle of the number are significant

• 0.00420 g 3 significant figures

 Numbers that do not contain decimal points, zeros after

the last nonzero digit may or may not be significant.

400 cm 1 or 2 or 3 significant figures

4 x 102 1 significant figures
4.0 x 102 2 significant figures
 Exercise
24 mL = 0.216 =
3001 g = 90.7 =

0.0320 m3 = 800.0 =
560 kg = 0.0670 =
 WRITING SIGNIFICANT FIGURES
Rounding Off
 If the last digit to be removed is greater than 5, add one to the 2nd last digit.
(22.48622.49)

 If the last digit to be removed is smaller than 5, then the 2nd last digit does
not change.
(31.392 31.39)

 If the last digit is 5 and 2nd last digit is an even no, the 2nd last digit does
not change.
(73.28573.28)

 If the last digit is 5 and the 2nd last digit is an odd no, add one to the last
digit.
(63.275 63.28)
 Addition or Subtraction

No. of digits to the right of the decimal point in this operation

should remain.

The answer to this operation has a value with the least decimal
point.

89.332
+ 1.1 one significant figure after decimal point
90.432 round off to 90.4

3.70 two significant figures after decimal point

-2.9133
0.7867 round off to 0.79
 Multiplication or division

 The no. of significant figures should be the same as the no. with
the least significant figure in the data.

4.51 x 3.6666 = 16.536366 = 16.5

3 s.f round to
3 sig figs

6.8 ÷ 112.04 = 0.0606926 = 0.061

2 s.f round to
2 sig figs
EVALUATION OF EXPERIMENTAL
DATA

10
 PRECISION

 Definition: the degree of agreement between replicate

measurement of the same quantity.

 Repeatability of a result.

 Express as standard deviation, the coefficient of

variation, the range of data or confidence interval
about the mean value.
 ACCURACY
 Definition: Closeness of a measured value to the
accepted value.

 Example: absolute error

Accuracy versus precision
Example:

Siti, Ahmad and Chan performed a titration experiment.

Below are the data obtained from these three student.

Siti: 12.10, 14.50, 13.00

Ahmad: 15.01, 15.00, 15.01
Chan: 13.10, 13.09, 13.08

If the accepted value for the experiment is 15.00, briefly

explain the precision and accuracy data of Siti, Ahmad
and Chan.

Answer:
Siti: Not accurate, low precision
Ahmad: Accurate, high precision 14

Chan: Not accurate, high precision

 ERRORS IN
EXPERIMENTAL DATA

1) Determinate (systematic errors)

2) Indeterminate (random or accidental
errors)
3) Gross error

15
 1) DETERMINATE (SYSTEMATIC ERRORS)

 DEFINITION: A constant error that originates from a fixed

cause.

 CHARACTERISTICS
 Cause of error is known

 Consistency (values are almost the same)

 Can be effected to accuracy of the method

 Can be corrected and avoided

 HOW TO REDUCE SYSTEMATIC ERROR?
 Frequent calibration of apparatus (6 monthly)

 Run a blank determination

- by omitting sample, a determination is carried out in identical condition
to minimize the errors occurs due to impurities present in reagent.

 Run a control determination

- standard substance is used in experiment in identical experimental
condition to minimize the errors.

 Use of independent methods of analysis

- it is carried out to maintain accuracy of the result e.g. Iron (III) is first
determined gravimetrically by precipitation method as iron (III)
hydroxide and then determined titrimetrically by reduction to the iron
(II) state.

 Run parallel determinations

- instead of single determination, duplicate or triplicate determination is
carried out to minimize the possibilities of accidental errors.
 Personal
errors

Systematic
errors
Instrumental Methods
errors errors
 A) INSTRUMENTAL ERROR

 Caused by:

i. uncalibrated apparatus such as pipette, burrette,

volumetric flask.
ii. faulty equipments such as leakage in vacuum system,
decreases in voltages of batteries with use.
iii. uncalibrated weight (analytical balance).
 b) Method Errors

 Sources of methodic errors:

- Coprecipitation of impurities
- Slight solubility of a precipitate
- Side reactions
- Slow or incomplete reactions
- Impurities in reagents
- Instability of reacting species

 Method to overcome:
- Running a blank determination
 c) Personal Errors
 Caused by clumsiness, carelessness or not using the
right techniques by the operators.

 Involve measurements that require personal judgement.

 Examples:
i) estimation of a pointer between two scale
divisions.
ii) color of solution.
iii) level of liquids in burette.
iv) prejudice in estimating measurements.
 2) Indeterminate (random or accidental
errors)

 Error that occur randomly and affect measurement in

an unpredictable manner.

 Cause data to be scattered more or less symmetrically

around mean value.

 Caused by many uncontrollable variables in physical or

chemical measurements.
 CHARACTERISTICS OF RANDOM
ERRORS

Cause of error is unknown

Spreads randomly around the middle value
Effects on precision of measurement
Cannot be corrected

Examples:
- change of humidity
- temperature in the balance room that cannot be
controlled.
 RANDOM ERROR SYSTEMATIC ERROR

 Affect measurement  Affect accuracy of the

precision results
 3) Gross Error
 Occur occasionally and often large.

 May cause result to be either high or low.

 Examples:

- part of precipitate is lost before weighing, analytical results

will be low.
- touching a weighing bottle with your fingers after empty
mass will cause a high mass reading for a solid weighed.

 Lead to outliers (results in replicate measurements that

differs significantly from the rest of the results).
CALCULATIONS
 SAMPLE POPULATION

finite number of infinite number of data /the

experimental observation collection of all
or a subset of measurement of interest,
measurement selected >20
from population
 1) MEAN
sample population
n N
 xi  xi
µ i1
x = i1
=

N
n

where:
X= average or mean
Xi=individual value
N= number of replicate measurements
EXAMPLE
 Calculate the mean of the following data:

15.67 15.69 16.03

n
 xi
x = i1
n
= 15.67 + 15.69 + 16.03
3
= 47.39
3
= 15.80
 2) MEDIAN
 The middle value for a set of data.
 Example:
A set of data consists of 127.2, 128.4, 127.1, 129.0, and
128.1. Calculate the median.

i. Rewrite the list in numerical order:

127.1, 127.2, 128.1, 128.4, 129.0

ii. The middle one will be the 3rd number

127.1, 127.2, 128.1, 128.4, 129.0

Median = 128.1
Example:

3, 13, 7, 5, 21, 23, 23, 40, 23, 14, 12, 56, 23, 29

When we put those numbers in order we have:

3, 5, 7, 12, 13, 14, 21, 23, 23, 23, 23, 29, 40, 56

There are now fourteen numbers and so we don't have just one middle
number, we have a pair of middle numbers:

3, 5, 7, 12, 13, 14, 21, 23, 23, 23, 23, 29, 40, 56

In this example the middle numbers are 21 and 23.

To find the value halfway between them, add them together and divide by
2:
21 + 23 = 44
then 44 ÷ 2 = 22

Median = 22
 3) DEVIATION

di = l Xi – x l
Xi = experimental value (individual result)

x = mean value

32
4) STANDARD DEVIATION
n 2
s=  (xi  x )
i 1
n 1
For n (num. of measurements) < 30

N 2
 (xi  μ)
σ= i 1
N
For N > 30
 Example:

Calculate the standard deviation of the following set of analytical

results: 15.67, 15.69 and 16.03 g

xi
15.67 15.67 - 15.80 = -0.13 (-0.13)2 = 0.0169
15.69 15.69 - 15.80 = -0.11 (-0.11)2 = 0.0121
16.03 16.03 - 15.80 = 0.23 (0.23)2 = 0.0529
 47.39  0.0169 + 0.0121 + 0.0529 = 0.0819

Num. of measurements < 30

n 2
 (xi  x )
s = i 1
s = 0.20 g
n 1
EXERCISE
The following replicate weighing were obtained:
29.8, 30.2, 28.6, and 29.7 mg. Calculate the mean,
median & standard deviation of the data.

Answer:

Mean = 29.6
Median = 29.75
s = 0.69
5) RELATIVE STANDARD DEVIATION (RSD)


6) ABSOLUTE ERROR, E

E = (Xi – Xt)
Xi = experimental value
Xt = true value
 7) RELATIVE ERROR, ER
Er= (Xi – Xt)
Xt
Xi = experimental value
Xt = true value

Can also be expressed in term of:

 %

 ppt (thousand) – times 1000

EXAMPLE:
The following results were obtained in analysis of water samples
for its Na content. The actual concentration of Na in the sample
was given as 32.20.

Sample 1 2 3 4
No.
Na content 31.10 33.20 31.90 34.40
(ppm)

Calculate the absolute error and relative error (in % and ppt) for
sample no. 2.
Solution:
Absolute error = Xi – Xt
= 33.20 – 32.20
=1

Relative error (in %) = Xi – Xt x 100

Xt
= 33.20 – 32.20 x 100
32.20
= 3.1%

Relative error (in %) = Xi – Xt x 1000

Xt
= 33.20 – 32.20 x 1000
32.20
= 31.0 ppt
EXERCISE:
The following results were obtained in analysis of water samples for its
Na content. The actual concentration of Na in the sample was given as
32.20.

Sample No. 1 2 3 4
Na content 31.10 33.20 31.90 34.40
(ppm)

Calculate the absolute error and relative error (in % and ppt) for
sample no. 1.

Answer:
Absolute error = -1.1
Relative error = -3.4%, -34 ppt
8) RELATIVE ACCURACY

Er= Xi x 100
Xt

Xi = experimental value
Xt = true value
 9) CONFIDENT LIMIT
 Statistical theory can be used to estimate the range
within which the true value might fall, within a given
probability.

 Confidence interval: the range on both sides of the mean

in which the probability of the true value exists.

 Confidence limit: the limit of the confidence interval.

 Confidence level or probability: the likelihood that the

true value falls within the confidence limit. Express as a
percent.
Confidence limit :

ts
x
n
s= standard deviation
t = from the t-table (depends on the number of degree of freedom
and confidence level desired
n = number of measurements
 Factor for Confidence Interval
Degrees of freedom 90% 95% 99%

1 6.31 12.7 63.7

2 2.92 4.30 9.92
3 2.35 3.18 5.84
4 2.13 2.78 4.60
5 2.02 2.57 4.03
6 1.94 2.45 3.71
7 1.90 2.36 3.50
8 1.86 2.31 3.36
9 1.83 2.26 3.25
10 1.81 2.23 3.17
11 1.80 2.20 3.11
12 1.78 2.18 3.06
13 1.77 2.16 3.01
14 1.76 2.14 2.98
 1.64 1.96 2.58

Degrees of freedom (df) = n - 1

 Example
The true mean and standard deviation obtained from the 5 times
measurements of ascorbic acid in vitamin C tablet is 68.35% and
0.12%. Calculate the confidence limit at 95% confidence interval.

ts
x t = refer to table (95% CI)
and 4 degrees of freedom
n (n-1)

Confidence limit = 68.35% ± 2.78(0.12%)/√5

= 68.35% ± 0.14%
= 68.20% and 68.50%

Confidence interval = 68.20% ≤ μ ≤ 68.50%

μ = true value of ascorbic acid content in vitamin C tablet

At 95% confidence level, the true value falls within 68.20% and
68.50%.
EXERCISE
Consider the following set of replicate measurement:

3.5, 3.1, 3.1, 3.3 and 2.5

Calculate the mean and standard deviation for each

data sets. Calculate the 95% confidence limit for each
data set.

Answer: mean = 3.1

standard deviation = 0.37
95% confidence limit = 3.1 ± 0.46

47
 10) ACCEPTING OR REJECTING
AN EXPERIMENTAL DATA (Q-TEST)

 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.

 Q-test is used to determine if an outlier is due to a determinate error.

 Num. of measurements (n) is 3 to 10.

 STEPS IN Q-TEST

 The questionable result (outlier) accepted
→ may be due to the random error.
→ the outlier can be include in the calculation of
mean, standard deviation etc

 The questionable result (outlier) rejected

→ may be due to the determinate error.
→ the outlier have to be excluded in the calculation
of mean, standard deviation etc
 Critical Values
Number of 90% Confidence 95% Confidence 99% Confidence
Observations
3 0.941 0.970 0.994
4 0.765 0.829 0.926
5 0.642 0.710 0.821
6 0.560 0.625 0.740
7 0.507 0.568 0.680
8 0.468 0.526 0.634
9 0.437 0.493 0.598
10 0.412 0.466 0.568
Example

Volume of 0.1 M NaOH used for the titration with 0.1 M HCl
(repeated for 4 times, n=4) are 27.33, 27.56, 27.37, 27.30.

i. Determine the outlier of the given data above.

ii. By using the Q-test, predict whether the outlier in the

data should be accepted or rejected at 90% confidence
level.
 Solution
i. Determine the outlier of the given data above.

a. Arrange in increasing order: 27.30, 27.33, 27.37, 27.56

b. Calculate gap between each data

0.03 0.04 0.19

27.30 27.33 27.37 27.56

c. Data with the biggest gap value → OUTLIER

So, the outlier is 27.56 mL

27.30, 27.33, 27.37, 27.56
 Example:

A set of data is obtained as follow:

7.43 7.57 7.38 7.44 7.40

i. By using Q-test, predict whether the outlier in the

data set should be rejected or accepted at a 90%
confidence level.

ii. Determine the mean of the data set.

 Solution:
i. By using Q-test, predict whether the outlier in the data set
should be rejected or accepted at a 90% confidence level.
0.02 0.03 0.01 0.13

7.38 7.40 7.43 7.44 7.57

Q exp = 7.57 – 7.44

7.57 – 7.38
= 0.684

Qtable = 0.642

Qexp (0.684) > Qtable (0.642)

Outlier is rejected
ii. Determine the mean of the data set.

Since the outlier is rejected, the data is excluded

in any calculation.

Mean = (7.38 + 7.40 + 7.43 + 7.44)

4
= 7.41