Chapter 3

Statistics and Data Handling

in Analytical Chemistry

Prof Ibrahim H. A. Badr

 OUTLINE

3.1 Accuracy and precision: they are

different

• Random (indeterminate)
3.2, 3.3 Types of Analytical Errors • Systematic (determinate)

3.4, 3.5 Significant Figures and

Rounding

3.6 How to assess accuracy (absolute

and relative errors)

3.7 How to assess precision (Standard

deviation)?
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3.1 Accuracy and precision: they are different
• It is impossible to perform chemical analysis and
obtain results that are totally free from error or
uncertainties.
• So, in chemical analysis the true value is never
known exactly, and all efforts are focused on
obtain results with minimum errors and
estimate the size of error with acceptable
accuracy.
• Chemical analysis is usually performed many
times for the same sample, which is known as
replicate samples (2 – 5 portions of sample).
• Replicate samples are of the same size and
analyzed in exactly the same way.

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• Precision is a measure of the repeatability of data.
• Accuracy is how close is the measurement to the true value (or
the accepted value).
Good precision does not assure good accuracy.

Discus each of the following cases

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Precision=reproducibility Accuracy=correct

Precise  Precise  Imprecise X

Accurate  Inaccurate X Inaccurate X

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3.2, 3.3 Types of Analytical Errors

You are HIV positive!!!

ERRORS
You are COVID-19 positive!!

Systematic/Determinate Random/Indeterminate

Has only one direction (+ve or -ve)
Origin:
Instrument error: faulty
instrument, un-calibrated weights,
un-calibrated glassware
Operative error: Transfer of
solution
Method error: interference
Goes in both direction (+ve and -ve)
Follows natural distribution
Origin:
Instrument limitations
Human limitations
Cannot be avoided but could be
minimized

Can be avoided Affects precision

Affects accuracy.
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Random error follows natural distribution (Gaussian)

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3.4, 3.5 Significant Figures and Rounding

Q: What are significant Figures?

A: Significant figures are the meaningful numbers in a measurement.

27.7?

27.766
The last number in a measured values is uncertain, and all other numbers are
certain.

Number of significant figures = number of certain digits + first uncertain digit

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3.4, 3.5 Significant Figures and Rounding
Apply the following rules:
1. All nonzero digits are significant.
2. Zeros between nonzero digits are significant.

3. Zeros beyond the decimal point at the end of a number are significant.
4. Zeros preceding the first nonzero digit in a number are not significant.
5. Exponential is not significant.
6. Exact numbers do not limit the significant figures.

EXAMPLE:

1.024
8.00
0.002
5 2g
x 10mL 5.00 x 102
5.37 cm
Significant figures = 4
1
3 3

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Significant Figures in Multiplication and Division
The number of significant figures in a result is the same as that in the quantity with the
smallest number of significant figures.

EXAMPLE:
5.6 x 103 km
Calculate to the correct number of
8.50 h significant figures.
SOLUTION:

5.6 x 103 km significant figure = 2

8.50 h significant figure = 3

= 658.8235294 km/h
Round off the result to 2 significant figures.

= 6.6 x 102 km/h

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Significant Figures in Addition and Subtraction
The number of decimal places in the result is the same as that in the quantity with the
smallest number of decimal places.

EXAMPLE:

Calculate 10.21 g + 0.2 g + 256 g

SOLUTION:

10.21 g + 0.2 g + 256 g = 266.41 g

2 decimal places
1 decimal places
0 decimal places

Round off the result to 0 decimal places.

= 266 g
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Significant Figures in Addition and Subtraction

SOLUTION:

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Significant Figures in Addition and Subtraction

SOLUTION:

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Significant Figures in Addition and Subtraction

SOLUTION:

Key number is the number with the least no. of S.F.

If there is more than one number, the key number is one with the smallest value
(greatest relative uncertainty) regardless of the decimal points.
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Significant Figures in Addition and Subtraction

EXAMPLE

SOLUTION:

Note: the answer < key number → retain an additional digit in the answer
(as subscript)
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Rounding off
If the digit following the last significant figure > 5,
the number is rounded up to the next higher number
If the digit following the last significant figure < 5,
the number is rounded to the present value
EXAMPLE:

If the digit following the last significant figure =5,

the number is rounded off to the nearest even digit

EXAMPLE:

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3.6 Ways of expressing accuracy (assessment of accuracy)

Important statistical terms

Mean Average of a set of values

Median Mid-point of a set of values

A collection of an infinite number of measurements

Population
N=infinity

Sample A finite set of measurements

True value (true mean) (μ) mean value for the population (N≥30)

Observed Mean (x) mean value of the sample set (N<30)

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3.6 Ways of expressing accuracy (assessment of accuracy)

Expressing accuracy

Absolute error: X − True.value

Relative accuracy: = X
100%
True.value

X − True.value
Relative error (pph): = 100%
True.value

Relative error (ppt): = X − True.value 1000%0

True.value
X .is.the.average.of .several.measurment
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Expressing accuracy

SOLUTION:

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3.7 Expressing precision (standard deviation)

Expressing accuracy

Theoretical Standard deviation (s)

 (xi − )
2

of infinite set of measurements =

N

− 2
Standard deviation (s)  ( x i − x)
of finite set of measurements (N<30) =
N −1
s
= 100%
Relative standard deviation x
(coefficient of variance (CV)

Variance = s2
x.is.the.average.of .several.measurment
 .is.average.of .N = .number 20
Standard deviation

EXAMPLE 3.7

SOLUTION:

Express this value using different expressions of precision!

NOTE: THE SAMALLER THE (s) VALUE THE BETTER IS THE PRECSION OF THE DATA
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3.8 Propagation of errors-Not just additive

3.9 Significant figures and propagation of error

3.10 Control charts

3.11 The confidence limit: How sure we are?

3.12 Tests of significance: is there a difference?

3.13 Rejection of Results

3.20 Use of spreadsheets for analytical calculations

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3.8 Propagation of errors-Not just additive

Absolute and Relative Uncertainty

• Absolute Uncertainty

Example: 12.35 mL measured using a burette is 12.35 ± 0.02 mL

• Relative Uncertainty

Relative uncertainty = 0.02/12.35=0.002 mL

• Percent Relative Uncertainty

Percent relative uncertainty = relative uncertainty x 100%

= 0.002x100=0.2 %

Percent relative uncertainty gives better understanding of the uncertainty.

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3.8 Propagation of uncertainty (error) in (+&-)

Absolute uncertainty

X ± e1
2+ 2+ 2
e4 =
Y ± e2
-Z ± e3 e1 e 2 e 3
(X + Y - Z) ± e4

EXAMPLE
Calculate the absolute uncertainty and the percent relative uncertainty for:
1.76 ± 0.03
+ 1.89 ± 0.02
- 0.059 ± 0.04

SOLUTION 2 2 2
Absolute uncertainty e4 = 0.03 + 0.02 + 0.04 = 0.04

The quantity can be reported as: 3.06 ± 0.04

Percent relative uncertainty=(0.04/3.06) x 100 %= 1 %

The quantity can be reported as: 3.06 ± 1% 24
3.8 Propagation of error in (x and ÷)

X ± e1
* Y ± e2
(X * Y ) ± e3%
1- Covert absolute uncertainty into relative uncertainty:
e1→ (e1)Rel and e2→(e2)Rel

% = (e ) 2 + (e ) 2
e
2- Calculate e3 as follows: 3 1 2

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Propagation of error in (x and ÷)

EXAMPLE
Calculate the absolute uncertainty and the percent relative uncertainty for:
1.76 ± 0.03
* 1.89 ± 0.02
÷ 0.059 ± 0.04
SOLUTION Quantity= 1.76 * 1.89 ÷ 0.059 =56.4

1- Covert absolute uncertainty into relative uncertainty

0.03
= = 0.017 =
0.02
= 0.011 =
0.04
= 0.68
1.76 1.89 0.059
2- Calculate e4
2 2 2
e4 = (0.017) + (0.011) + (0.68) = 0.68

e4 Here is relative error=0.7

The quantity can be reported as: =56.4 ± 0.7 (Relative error)
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SOLUTION:

Percent relative uncertainty

x 100%= 0.06%

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3.9 Significant figures and propagation of error

In propagation of uncertainty error, regardless of the

smallest number of S.F. in multiplication/division or
number of decimal points in addition/subtraction, the
no. of significant figures in an answer is determined by
the uncertainty (error).
Uncertainty sets the number of significant figures
Example:

(73.1 ± 0.2) (2.245 ± 0.008) = 164.1 ± ?

= 164.1± 0.4x10-2 (Rel.)
= 164.1±0.4% (%)
= 164.1± 0.7 (Abs.)
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Significant figures and propagation of error
Example:

(73.1 ± 0.9) (2.245 ± 0.008) = 164.1 ± 2.1 = 164.1 ± 0.012 (Rel.)

=164.1 ± 1.2 % (%)
=164.1 ± 2.1 (Abs.)
=164 ± 2
Now the uncertainty in the answer is the units place,
and so figures beyond that are meaningless.

The number of significant figures in an answer is

determined by the uncertainty due to propagation
of error.

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Significant figures and propagation of error

±0.11 = ± 0.1 Abs. Error

± 0.65 = ± 0.6 Abs. Error

Solution:
(a) The calculated absolute uncertainty in the answer is ±0.11 (±0.1) .

Therefore, the answer is 32.5 ± 0.1.

(b) The calculated absolute uncertainty is 0.65 (±0.6).

Therefore, the answer is 86.4 ± 0.6

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3.10 Control charts

What is a control chart?

• A quality control chart is a time plot of a measured
quantity
• The purpose of control chart is ascertaining that the
measurement remains within a statistically acceptable
range.
• It may be a day-to-day plot of the measured value of a
standard that is run intermittently with samples.
• The control chart consists of a central line representing the
known or assumed value of the control and either one or
two pairs of limit lines, the inner and outer control limits.
• Standard deviation (σ) is used to establish the control
limits.
• The results are accepted if they exist within limit lines 2,
2.5 or 3 s. 31
Control charts
✓Central line limit: represents the known (assumed)
value of the control.

✓ inner control line limits: 2σ

✓outer control limit: 2.5σ or 3σ

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3.11 The Confidence Limit—How Sure Are You? Student t-test
• Standard deviation (s) provides information about:
• Precision of the measurement
• Closeness of the measured mean (x) to the true mean
() with a desired confidence level within a given range.
• This range is called “Confidence intervals” and the limits of
this range is Confidence limits.
• The likelihood that the true value falls within the range is
called the probability, or confidence level.
• The confidence limit, in terms of the standard deviation (σ)
is given by:

Where t is statistical factor (Table 3.1) depends on confidence level and degree
of freedom n =(N-1). N is the number of measurements.

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The Confidence Limit—How Sure Are You? Student t-test

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The Confidence Limit—How Sure Are You? Student t-test

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3.12 Tests of significance: is there a difference?

• How to compare between the precision of two

methods, laboratories, or analysts?
This can be performed by running the F-test,
2

F 

= s
1
=
Largest va riance
2
s Smallest. variance
2

s12 & s22 are the variances of the first and the second
method (s12 > s22).  is t he degree of freedom (N-1)
Compare the calculated F with the tabulated value:
If F (calculate) < F (table) there is no significant difference
If F (calculate) > F (table) → the method with less (s2) is
more precise 36
Tests of significance: is there a difference?
Example

For the following two sets of analytical data obtained

using different methods determine which method is
more precise.
Method-1: 10.0, 10.2, 10.4, 10.5, 10.6
Method-2: 9.2, 10.5, 10.8, 11.6, 12.1
Solution
2

=s
 1.243
F
2
2
= = 21.4
s 0.058
1

F − Table = 6.39
 F − calculated  F − Table

Then the methods of smaller standard deviation is more precise

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Tests of significance: is there a difference?

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Tests of significance: is there a difference?
THE STUDENT t-TEST—ARE THERE DIFFERENCES IN THE METHODS?
1- You compare your methods with reference standard with
negligible SD. is there a difference between the certified
reference value and the mean value obtained by your method?
2- You compare repeated measurements (just one
concentrations) of the same single sample made by the
reference method whose SD is not negligible, with repeated
measurements made by the test method. This is often referred
to as t-test by comparison of the means.
3- Same as above, but you span concentration range and not
one concentration This is often called paired t-test.
4- You want to compare two sample populations that are
unrelated to each other. Is banana from Alexandria
statistically different in its potassium content compared to
banana from’Al-Menofia? 39
Tests of significance: is there a difference?
Comparison with reference standard with negligible SD

Because tcalc > ttable, the two methods are

statistically. Your procedure will be considered
unacceptable until you can find the source of the
discrepancy and fix it
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F-test and t-test
F-test

The F-test is used to determine if two variances

(standard deviations) are statistically different

t-test

The t-test is used to determine if two sets of

measurements are statistically different

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3.13 Rejection of result (Q-test)

Gross error is that error which is very high/low and the only option
Gross error is to discard them.

Q-test
1- Arrange data in order

2- Find range (W) and the gap (a)

a
a
X1, X2 ……………………………. Xn-1 Xn Q=
W
W
If Q calc  Q table  Retain the value
If Q calc  Q table  Reject the value

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Q-test

EXAMPLE 3.20

SOLUTION:

Arrange in order: 103, 106, 107 117

a = 117 – 107 = 10 W = 117 – 103 = 14

Q(calc) = a/W = 10/14 = 0.71

Q(table) = 0.829

Q(calc) < Q (table), then retain the suspected number

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Q-test

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3. 20 Use spreadsheets for analytical calculations

Table

Graph Excel basics

Calculations

Search the web for tutorials such as:

✓http://www.gcflearnfree.org/excel2010/1
✓http://www.ncsu.edu/labwrite/res/gt/gt-menu.html
✓http://science.csustan.edu/tutorial/Excel/index.htm
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Homework assignment

Read: all solved examples in the covered units

Solve:1, 2, 3, 4, 5, 6, 8, 9, 13, 15, 20, 40

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