Random Errors in

Chemical Analysis
CHM028 Analytical Chemistry for Teachers
2nd semester 2021-2022
“ “All measurements contain random
errors.”

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Figure 6-1 Three-dimensional plot showing absolute error in Kjeldahl nitrogen determination for four
different analysts.
What Are the Source of Random Errors?
A Gaussian, or normal
error curve, is a curve
that shows the
symmetrical
distribution of data
around the mean of an
infinite set of data.
The spread in a set of replicate measurements is the difference
between the highest and lowest result.
results directly from an accumulation of all random uncertainties in the experiment
Figure 6-3 A histogram (A) showing distribution of the 50 results in Table 6-3 and a
Gaussian curve (B) for data having the same mean and standard deviation as the data in
the histogram.
Sources of random uncertainties in the calibration of a pipet include:
(I) visual judgments, such as the level of the water with respect to the
marking on the pipet and the mercury level in the thermometer;
(2) variations in the drainage time and in the angle of the pipet as it
drains;
(3) temperature fluctuations, which affect the volume of the pipet, the
viscosity of the liquid. and the performance of the balance; and
(4) vibrations and drafts that cause small variations in the balance
readings.
STATISTICAL TREATMENT OF RANDOM ERROR

“Statistical methods allow us to categorize and characterize data in different

ways and to make objective and intelligent decisions about data quality and
interpretation.”
Sample – a finite number of experimental observations; a
tiny fraction of infinite number of observations Population mean –
true mean of the
Population (or universe) - collection of all measurements population; in the
of interest to the experimenter absence of any
systematic error, this
Properties of Gaussian Curves is also the true value
for the measured
Parameters used to define a population or distribution: quantity.
• Population mean, 

• Population standard deviation, 
 x i
= i =1

The sample mean and the sample standard deviation are examples of statistics
that estimate parameters  and , respectively.
 Sample mean, 𝑥ҧ - the mean of a
x i
limited sample drawn from the
population of the data
= i =1


The probable difference between  and 𝑥ҧ decreases rapidly as the number

of measurements making up the sample increases.
Measures of Precision
1. Population standard deviation, 
- a measure of the precision of a population of data and is
mathematically given by: 

 ( xi −  )2

 = i=1

Note that z is the deviation of a data point from the mean relative to
one standard deviation. That is, when x-  = , z is equal to one; when x
-  = 2, z is equal to two; and so forth.
Normal error curve has several general properties:

1. The mean occurs at the central point of maximum frequency.

2. There is a symmetrical distribution of positive and negative about the
maximum,
3. There is an exponential decrease in frequency as the magnitude of the
deviations increases.
Thus, small uncertainties are observed much more often than very large ones.
Areas under a Gaussian Curve
2. Sample standard deviation, 𝒔
- measures how closely the data are clustered about the
mean

 (x − x )
  N−1 is called the number

d
2 2 of degrees of freedom
i i which is said to be an
s= i =1
= i =1 unbiased estimator of
 −1  −1 the population standard
deviation, 

The smaller the s, the more closely the data are clustered about the mean .
Alternatively,
2
 N

 Xi 
 i =1 
N

 X i
2
−
N
s= i =1
N −1
3. Standard deviation of the mean, 𝒔𝒎
- measures how closely the data are clustered about the
mean
s
sm =
N

Improvement of precision is be gained by:

➢ Increasing the number of measurements
- Increase precision by a factor of 10 requires 100
measurements
➢ Decrease 𝒔 → a better way
- by being more precise in individual operations, by changing the
procedure, and by using more precise measurement
Other ways of expressing precision:
• Variance, 𝒔𝟐 – the square of the standard deviation

 (x − x )

2
i
s =2 i =1
 −1
𝑠
• Coefficient of variation, CV 𝑅𝑆𝐷 =
𝑥ҧ
𝒔
𝑪𝑽 = ഥ 𝐱 𝟏𝟎𝟎% 𝑠
𝒙 𝑅𝑆𝐷 𝑖𝑛 𝑝𝑝𝑡 = 𝑥 1000 𝑝𝑝𝑡
𝑥ҧ
• Spread or range, 𝒘
𝒘 = highest value − lowest value
The following results were obtained in the replicate determination of the
lead content of a blood sample: 0.752, 0.756, 0.752, 0.751, 0.760 ppm Pb
Calculate (a) the variance, (b) the relative standard deviation in parts per
thousand, (c) the coefficient of variation, and (d) the spread.
X = 0.754 ppm and s = 0.0038ppm Pb
(a) S 2 = (0.0038) 2 = 1.4  10− 5
0.0038
(b) RSD =  1000 ppt = 5.0 ppt
0.754
0.0038
(c)CV =  100% = 0.50%
0.754
(d ) w = 0.760 − 0.751 = 0.009 ppmPb
Reliability of s as a Measure of Precision

➢ Most of the statistical tests described are based upon sample.

➢ Standard deviations and the probability of correctness of the results of these
tests improves as the reliability of s becomes greater.
➢ Uncertainty in the calculated value of s decreases as N increases. When N is
greater than 20, s and  can be assumed identical for all practical purposes

Pooling Data to Improve the Reliability of s

• data from a series of similar samples accumulated over time can often be
pooled to provide an estimate of s superior to the value of the individual
subset
  (x − x ) +  (x ) ( )
1 2 3
− x 2 +  x j − x3 + ...
2 2 2
i 1 j
i =1 j =1 k =1
spooled =
1 +  2 +  3 + ... −  T

where: N1 = number of data in set 1

N2 = number of data in set 2
NT = number of data sets that are pooled
N1 + N2 + …−NT degrees of freedom
STANDARD DEVIATION OF CALCULATED RESULTS
1)

2)
3)

The relative standard deviation

of y = a3 is not the same as the
relative standard deviation of
the product of three
independent measurements y =
abc, where a = b = c.
4)
REPORTING COMPUTED DATA

A numerical result is worthless to users of the data unless they know something
about its quality.

Ways of Indicating reliability:

• give a confidence interval at the 90% or 95% confidence level
• report the absolute standard deviation or the coefficient of variation of the
data
• use significant figures
The SIGNIFICANT FIGURE in a number are all the certain digits plus the first
uncertain digit.

➢ Express data in scientific notation to avoid confusion in determining whether

terminal zeros are significant.

➢ Rules for determining the number of significant figures:

1. Disregard all initial zeros.

2. Disregard all final zeros unless they follow a decimal point.

3. All remaining digits including zeros between nonzero digits are significant
Sum and Differences
➢ The result should contain the same number of decimal places as the number
with the smallest number of decimal places.
➢ When adding and subtracting numbers in scientific notation. express the
numbers to the same power of 10. For example,
2.432 X 106 = 2.432 X 106
+6.512 X 104 = +0.06512 X 106
- 1.227 X 105 = -0.1227 X 106
2.37442 X 106 (round to 2.374 X 106)

Products and Quotients

➢ round off the answer so that it contains the same number of significant digits as
the original number with the smallest number of significant digits.
Logarithms and Antilogarithms

1. In a logarithm of a number. keep as many digits to the right of the decimal point
as there are significant figures in the original number.

2. In an antilogarithm of a number, keep as many digits as there are digits to the

right of the decimal point in the original number.

➢ The number of significant figures in the mantissa, or the digits to the right of the
decimal point of a logarithm, is the same as the number of significant figures in
the original number.

Thus, log (9.57 X 104) = 4.981. Since 9.57 has 3 significant figures, there are 3 digits
to the right of the decimal point in the result.
Rounding Data

➢ In rounding a number ending in 5. always round so that the result ends with an
even number. Thus. 0.635 rounds to 0.64 and 0.625 rounds to 0.62.

We should note that it is seldom justifiable to keep more than one

significant figure in the standard deviation because the standard
deviation contains error as well.

➢ It is especially important to postpone rounding until the calculation is

completed. At least one extra digit beyond the significant digits should be
carried through all of the computations in order to avoid a rounding error.
References
1. Christian, G.D. Analytical Chemistry. 6th ed John Wiley & Sons, Inc.
2. Harris, D.C. and Lucy, C.A. Quantitative Chemical Analysis. 9th ed. W.H.
Freeman and Company.
1. Harvey, D. Modern Analytical Chemistry. Int’l ed. The McGraw-Hill
Companies, Inc.
1. Skoog, D.A., West, D.M., Holler, F.J., and Crouch, S.R. Fundamentals of
Analytical Chemistry. 9th ed. Brooks/Cole.
THANKS!
Any questions?
You can reach me thru:
[email protected]

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