CHM 256 : BASIC

ANALYTICAL CHEMISTRY

CHAPTER 2:
EVALUATION OF
EXPERIMENTAL DATA
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Evaluation of
Analytical Data
Objectives :
Obtain any result as near to the true value as
possible. Knowledge of accuracy and precision of
method used, aware of sources of error.

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Significant
Figures

RULES:
All non zero digits are significant
ex : 1.234 kg = 4 significant figures
Zeros between nonzero digits are significant
ex : 606 m
= 3 significant figures
If a number is greater than 1, then all zeros to the right of the
decimal point are significant
ex : 2.0 mg
= 2 significant figures
Leading zeros are not significant
ex: 0.08 L
= 1 significant figure
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 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
ex: 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.
ex: 400 cm
= 1or 2 or 3 significant figures
4 x 102
= 1 significant figure
4.0 x 102
= 2 significant figures
How many significant figures are in each of the following measurements?
24 mL =
0.0320 m3 =
560 kg =
90.7 =
0.0670 =
4

3001 g =
6.4 x 104 molecules =
0.216 =
800.0 =

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Steps in Writing Significant

Figures

Rounding Of
If the last digit to be removed is greater than 5, add
one to the 2nd last digit. Example:
22.486
22.49
If the last digit to be removed is smaller than 5,
then the 2nd last digit does not change. Example:
31.392
31.39
If the last digit is 5 and 2nd last digit is an even num.,
thus the 2nd last digit does not change. Example:
73.285
73.28
If the last digit is 5 and the 2nd last digit is an odd
num., thus add one to the last digit. Example:
63.275
63.28
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Addition or Subtraction
The num. 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 (key number).
89.332
+1.1
90.432
3.70
-2.9133
0.7867
6

one significant figure after decimal point

round off to 90.4
two significant figures after decimal point
round off to 0.79
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Multiplication or Division
The num. of significant figures in this operation should be
the same as the num. with the least significant figure in the
data (key number)
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
7

round to
2 sig figs

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Calculations with numbers having different accuracies

Multiplication or Division: the result can have no more sig figs than the
least accurate number. For example:
If an object has mass of 29.1143 g and a volume of 25.0 cm3, then its
density is given by:
Density
= 29.1143 g
= 1.164572 g cm-3
= 1.16 g cm-3
25.0cm3
Addition or Subtraction: the result must be reported to the same
number of decimal places as the number with the fewest decimal places.
For example:
19.2
g
0.4745 g
+ 127.
g
46.6745 g
8

= 147 g

NOTE: Round off numbers only at

the END of calculations;
otherwise, errors may be
inadvertently carried through
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Types of Errors in
Experimental Data
Errors in experimental data can be divided
into two main categories:
Determinate or systematic errors
Indeterminate or random or accidental errors

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Systematic Error or
determinate error
Definition: A constant error that originates from a fixed
cause, such as flaw in the design of an equipment or
experiment.(Mean value different from accepted/true
value)
Characteristics of determinate errors:
1. Cause of error is known (determinable)
2. Consistency, that is the values are almost the same
3. Will give effect to accuracy of the method
4. Can be corrected and avoided
5. Readings all too high or too low
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Types of determinate or
systematic errors
is caused by clumsiness,
carelessness or not using
the right techniques by
the operators
The faulty
equipments,
uncalibrated
weight and
glasswares

Caused by
the nature of
the methods
used

Will occur if the

reagents used
are not pure
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Instrumental Errors
All measuring devices contribute to systematic errors.
Glassware such as pipets, burets, and volumetric flasks may
hold volume slightly different from those indicated by their
graduations.
Occur due to significant difference in temperature from the
calibration temperature.
Sources of uncertainties:
Increases resistance in circuits due to temperature charge
Decreased power supply voltage

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..cont
Any glassware used for quantitative measurements (pipettes,
burets, etc) are potential source of systematic error :
(a) if they are not calibrated
(b) the solution temperature is different from the temperature
of the glassware
(c) Inaccuracy in determining the level of meniscus
For electronic measuring apparatus, systematic errors can come
about as the result of low batteries, poor contacts within the device,
sensitivity to temperature and humidity instrument malfunction.
How to avoid/ correct- Always remember to do calibration of the
glassware or on the instruments
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Personal Errors
Involve measurements that require personal judgement.
For example :
i)
ii)
iii)
iv)
v)
vi)
vii)
viii)

estimation of a pointer between two scale divisions.

color of solution.
level of liquids with respect to a graduation in a burette.
prejudice in estimating measurement
Mathematical errors in calculation,
contamination of sample,
incomplete dissolution of sample,
bumping of sample during heating (no boiling chips).

How to avoid/correct : Taking extra care and

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self discipline

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Method Errors
The most serious errors and difficult to detect.

Sources of
methodic
errors

Example of method error:

(a) chemical reagents used in the experiment is unstable
(b) the occurrence of side reactions that interfere with the measurement
process
(c) incomplete reaction
(d) impurities in reagents
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..cont
How to correct the error
i)
Using standard sample
- Analysis using standard reference materials
materials that contain
one or more analyses at exactly known concern.
ii) Performing blank determination.
- In a blank determination, all steps of the analysis are performed
in the
absence of the sample.
(A blank solution is a solution that contains the solvent and all
the
reagents in an analysis except the analyte)
iii)

Variation in sample size.

iv)

Perform second independents and reliable analytical method

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Efect of Systematic Errors

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Detection and Control of

Systematic Errors

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Random Error or
Indeterminate error
occur at all measurements do not have specific values
and are unpredictable
Cause data to be scattered more or less symmetrically
around a mean value.
This error is caused by the many uncontrollable
variables in physical or chemical measurements.

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Characteristics of Random errors

Cause of error is unknown
Spreads randomly around the middle value
Usually small
Have effects on precision of measurement
Cannot be corrected
e.g: the change of humidity and temperature in
the balance room that cannot be controlled.

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Gross Error
Differ from indeterminate and determinate errors
Usually obvious - give outlier readings. results that differs significantly
from the rest of the results
Detectable by carrying out sufficient replicate measurements.
They usually occur only occasionally, may cause a
result to be either high or low.
For example:
i)
part of precipitate is lost before weighing, analytical results will be
low.
ii)
touching a weighing bottle with your fingers after empty mass will
cause a high mass reading for a solid weighed.
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Basic Statistical
Concept
Mean

Mean or average:
is the summation of all data and divided by
the number of measurements.

where:
X= average or mean
Xi=individual value
N= number of replicate measurements
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Median
Is the middle value for a set of data
In a set of even data, the median is the

average of the central pair, whereby the

values are arrange in an ascending order
e.g:

10.06, 10.08, 10.10, 10.20

In a set of odd data, the median is in the middle

e.g:
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5, 7, 9, 11, 12

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Example 1.1
(April 2009)

A batch of nuclear fuel pellets was weighed to

determine if they fell within control guidelines.
The weights were 127.2, 128.4, 127.1, 129.0,
and 128.1 g. Calculate the:
i) mean (127.2 + 128.4 + 127.1 + 129 +128.1)/5
= 127.96
ii) median (127.1, 127.2, 128.1, 128.4,129.0)
odd data, median = 128.1
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(Oct 2010)

The precision of a method is being

established, and the following data are
obtained:
32.23%, 32.18%, 32.25%, 32.09% and
32.17%.
Determine the mean and median from the
set data above.
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Basic Statistical
Concept
Precision is a degree of agreement
between replicate measurements of
the
same quantity.

Accuracy is a degree of measurement

that is approximately close to the

accepted or correct values.
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Result can be precise without being

accurate and accurate without being

precise.
Precise but not accurate
nor precise

Accurate but not precise

Precise

Neither accurate

Accurate and

Illustrating the difference between

accuracy and precision

Low accuracy, high precision

High accuracy, high precision

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Accuracy & Precision

Errors will show the closeness of measurements to the accepted
or correct value.

Absolute Error
Definition: The difference between the true value and the measured
value
Error can be positive or negative depending on whether the experimental value is
greater than or less than the accepted value.
E = xi xt
Where xi = measured value
xt = true or accepted value

Measured value
True value

Example: If 2.62 g sample of material is analyzed to be 2.52 g, so the

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absolute error is 0.10g.

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Relative Error/Percent Error

Definition: The absolute or mean error expressed as a
percentage of the true value.
Percent error = xi xt
xt

100%

Also can be expressed in parts per thousand

The percent error will always be a positive value.

The above analysis has a relative error of

-0.10 g
x
100%
= - 3.8%
2.62 g

We are usually dealing with relative errors of less than 1%.

A 1% error is equivalent to 1 part in 100.
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Self-Exercise
The results of an analysis are 36.97 g,
compared with the accepted value of 37.06
g. What is the relative error in parts per
thousand?

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Relative Accuracy
Definition: The measured value or mean expressed as
a percentage of the true value.
Er = xi
xt

100%

The above analysis has a relative accuracy of

2.52 g
2.62 g
32

100%

96.2 %

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Terms used to express

PRECISION
8

Standard
deviation
3
7

4
6

5
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1. Number of Data: N
2.
Data Set: x1, x2, x3, ... ,xN
3. Mean:

4. Median : The center value( after sorting)

5. Range/spread : Max value min value
6. Deviation(d) = How much each
measurement differs from the mean
d = xi
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7. Relative Deviation (% deviation)

% deviation (d) = deviation x 100
mean
d = xi

8. Standard deviation (SD)

1 N
2
xi x
S

N-1 i1

or

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Standard Deviation &

Relative Standard Deviation
For N (num. of measurements) < 30
Relative Standard
Deviation (RSD) =

For N > 30

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s
100
x
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Example
Calculate the mean and the standard deviation of the
following set of analytical results: 15.67, 15.69, 16.03
g.
Solution
Xi

Xi-X

15.67
15.69
16.03
47.39

0.13
0.11
0.23
0.47

(Xi-X)2
0.0169
0.0121
0.0529
0.0819

X = Xi = 47.39 = 15.80
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s= ?

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Example
A student carried out an experiment to measure the

boiling of an organic compound at atmospheric pressure.

The results obtained are as follows.
Exp.1.
54.9 oC
Exp.2
54.4 oC
Exp.3
54.1 oC
Exp.4
54.2 0C

The true boiling for the compound is 54.0 oC. Calculate :

(i)
(ii)
(iii)
(iv)
(v)
(vi)

Error
Percentage error (Relative error)
Mean
Deviation
Percentage/relative deviation
Median
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Solution:
i)

Error = Measured value true value

Exp.1 54.9 54.0 0.9
Exp.2 54.4 54.0 0.4
Exp.3 54.1 54.0 0.1
Exp.4 54.2 54.0 0.2

ii )

100

%/Relative error = Error

Exp.1 0.9

54

100 true
1.7

Exp.2 0.4

54

100 0.7

x
value

Exp.3 0.1

100 0.2
54
Exp.4 0.2
100 0.4
54
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iii) Mean
54.9 54.4 54.1 54.2
4
Mean 54.4 #
Mean

iv) Deviation = Measured value mean

Exp.1 54.9 54.4 0.5
Exp.2 54.4 54.4 0.0
Exp.3 54.1 54.4 0.3
Exp.4 54.2 54.4 0.2

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v) % deviation = deviation x 100

mean
Exp.1 0.5

54.4

100 0.9

Exp.2 0
Exp.3 0.3

54.4

100 0.6

Exp.4 0.2

54.4

100 0.4

vi) median = 54.2 + 54.4 = 54.3

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Continue
..chapter
2b
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