Errors in Chemical Analysis:

A Review

Jemimah Sanggo, RCh, MSc

CHEMISTRY DEPARTMENT
 Learning Objectives

To be able to enumerate and define the different

types of errors encountered in chemical analysis;
To be able to understand accuracy and precision;
To be able to identify outliers through the Q-test and
Grubbs test;
To be able to compute confidence interval for a given
set of data.
 J. Garcia 2013. Do not copy or distribute 3 7/18/2016
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 How reliable is the data from your analysis?
4
Medical Diagnostics
Environmental
Food Safety
Drug Efficacy
Etc.

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 How to ensure reliability of data
5

Proper sampling techniques samples must

represent the properties of the bulk
Replicate sampling 6 to 10 portions of the
sample treated and analyzed in the same manner as
the rest.
Use of prescribed methods CORRECT
analytical procedure
Use of STATISTICAL METHODS

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 Repeated Measurements

Replicate two or more portions of a sample taken

through an entire analytical method
Repeated measurements or replicates are
needed in the course of a single chemical
analysis:
To confirm the repeatability of the results
To minimize the probability of spurious results
To decrease the uncertainty in the results
To increase the reliability of results

One measurement is no measurement

 Describing the reliability of data
7

Accuracy
closeness of the measurement to the true or accepted value

Measures agreement between a result and the accepted value

Precision
Closeness of each results obtained in the same manner

Measures agreement between results of several replicate

analyses

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 J. Garcia 2013. Do not copy or distribute 8 7/18/2016
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 Absolute and relative errors
9

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 Example
10

A multivitamin sample was assayed for its Fe content

in ppm. The analysis produced an average assay of
19.8 ppm. The actual Fe content of the sample was
known to be exactly 20 ppm Fe. Find the absolute
and relative errors.

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 J. Garcia 2013. Do not copy or distribute 11 7/18/2016
without the authors permission Figure 5-1 p83
 Types of Errors in Experimental
data
12

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 Systematic Errors
13

Determinate errors
Causes mean of data set to differ from accepted value
Types of Systematic Error
Instrumental errors

Method errors

Personal errors

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 Effects of Systematic Error on Analytical Results
14

Can be either CONSTANT or PROPORTIONAL

Constant errors absolute error is constant with
sample size
Proportional errors increase or decrease
according to the size of sample taken for analysis;
absolute error varies with size, but relative error
stays constant with changing sample size

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 Detection of Systematic Errors
15

Instrument Errors periodic calibration of

instruments / proper maintenance of equipment
Personal Errors Proper training; self-discipline,;
proper data recording

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 Detection of Systematic Errors
16

Method Errors
Analysis of standard samples Standard reference materials /
Certified reference materials (CRM)
Independent Analysis

Blank Determinations reveals errors due to interfering

contaminants from the reagents and vessels used in the
analysis
Variation of Sample size

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 Indeterminate Errors

Also called random errors

Random fluctuations in measured quantities that
always occur even under closely controlled
conditions
Cannot be eliminated entirely, but can be
minimized to a tolerable extent
Caused by uncontrollable variables
Also arises when a system of measurement is
extended to its maximum sensitivity
 Indeterminate Errors
A series of measurements
made under the same
prescribed conditions and
represented graphically is
known as a frequency
distribution. The frequency of
occurrence of each
experimental value is plotted
as a function of the magnitude
of the error or deviation from
the average or mean value.
For analytical data, the values
are often distributed
symmetrically about the mean
value, the most common
being the normal error or
Gaussian distribution
curve.
 Gaussian Errors

A Gaussian curve implies the following realizations:

1. Small errors are more probable than larger ones
2. Positive and negative errors are equally probable
3. The maximum of the curve corresponds to the
mean value
 Measures of accuracy and
precision
24

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 Measures of Central Tendency
25

Data tend to bunch-up around a central value

Generalizes data for replicate analysis
Mean or average. The sum of all data divided by
the number of data points
Median middlemost value along a distribution of
data

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 Mean
26

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 Median
27

Arrange data in an orderly manner (descending or

ascending)
If n is odd median is middlemost data
If n is even median is the mean of the 2 middle
values
A 15, 18, 20, 16, 19, 18, 24
B 78, 85, 81, 91, 87, 85, 90, 79, 90, 92

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 Example
28

The results of an analysis for a certain sample is

given below:
20.1, 19.4, 19.6, 20.3, 19.8
Find mean and median

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 Measures of Precision / Dispersion
29

Standard Deviation

Population Sample
SD SD

For n 30 For n <30

Greater the n, smaller the s

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 Example
30

Calculate the mean and standard deviation of the ff.

set of analytical results: 15.67 g, 15.60 g, 16.03 g

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 Ways of expressing s
31

Variance (s2)
Square of the standard deviation

Used for measuring the propagation of error

Relative Standard Deviation (RSD) or

coefficient of variation (COV)
Expressed as %RSD
ppt RSD
ppm RSD
ppb RSD
Most convenient way to express the random error regardless of
concentration or weight of the analyte measured

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 Good or bad precision?
33

Depends very much on sample type and

methodology adapted
For routing instrumental analytical method:
% RSD < 2% - usually acceptable
% RSD > 5 % - indicate problems with random noise errors
n minimum of 6; preferable 10 replicates

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 Example
34

The 2 data sets are replicatesof pH values of an

alkaline solution (set A) and acidic solution (set B).
Which is more precise?
A11.2, 10.7, 10.9, 11.3, 11.5, 10.5, 10.8, 11.1, 11.2,
11.0
B5.2, 6.0, 5.2, 5.9, 6.1, 5.5, 5.8, 5.7, 5.7, 6.0

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 Repeatability and Reproducibility

Repeatability within-run precision, the precision

measured when analysis is done by the same analyst in several
replicates using the same apparatus, the same reagents and
the temperature, humidity and other laboratory conditions
remains the same.
Example: An analyst analyzes a sample during the 1st shift
then repeats the analysis in the second shift.
Reproducibility between-run precision, the precision
measured when replicate analysis is done by different analysts
on different times or shifts in the same laboratory or in
different laboratories, using different sets of reagents and
apparatus.
Example: A sample is analyzed by two different laboratories.
Outliers and Confidence Values
 Outliers
37

Data points that are markedly far away from the

other points in the data set
Can significantly alter the accuracy and precision of
the data
Caused by unseen gross errors

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 Determining outliers
38

Dixons Q test
Q = (suspect # - nearest #) / range

If Qcalc Qtab reject suspect #

If Qcalc < Qtab retain

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 J. Garcia 2013. Do not copy or distribute 39 7/18/2016
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 Example
40

Given the data: 30.5%, 29.8%, 30.3%, 30.6%; find if

there are any outliers present at 95% confidence
interval.

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 Outliers
41

Grubbs test
Gcalc = (lsuspect value meanl)/s
If Gcalc Gtab reject data
Else, retain

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 G - table
42

n 95% 99% n 95% 99%

3 1.1543 1.1547 15 2.5483 2.8061
4 1.4812 1.4962 16 2.5857 2.8521
5 1.7150 1.7637 17 2.6200 2.8940
6 1.8871 1.9728 18 2.6516 2.9325
7 2.0200 2.1391 19 2.6809 2.9680
8 2.1266 2.2744 20 2.7082 3.0008
9 2.2150 2.3868 25 2.8217 3.1353
10 2.2900 2.4821 30 2.9085 3.2361
11 2.3547 2.5641 40 3.0361 3.3807
12 2.4116 2.6357 50 3.1282 3.4825
13 2.4620 2.6990 60 3.1997 3.5599
14 2.5073 2.7554 70 3.2576 3.6217
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 Example
43

Students dissolve Zn from a galvanized nail and

measured the mass lost by the nail to tell how much
of the nail was Zn. Here are the results for 12
replicate trials:
Mass lost (%): 10.2, 10.8, 11.6, 9.9, 9.4, 7.8, 10.0, 9.2,
11.3, 9.5, 10.6, 11.6
Find if there are possible outliers and check using
Grubbs test at 95% confidence interval whether this
value should be retained or rejected.

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 Confidence Limit (CL)
44

An estimate of the range within which the true value

might fall within a given probability
Defined by the experimental mean and s
Also called confidence interval

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 Confidence Limits
45

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 J. Garcia 2013. Do not copy or distribute 46 7/18/2016
without the authors permission Table 7-3 p127
 Example
47

A soda ash sample is analyzed in the analytical

chemistry lab by titration with standard HCl. The
analysis is performed in tripicates with the ff. results:
93.50 %, 93.58 %, & 93.43 % Na2CO3. within what
range does the true value fall at 95% confidence
level?

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 Seatwork
48

1. Richards and Willard determined the atomic mass

of Li and collected the ff. data: 6.9391, 6.407,
6.9407, 6.9409, 6.9399, 6.9407, 6.391, 6.9406.
Find the mean and median atomic mass. Also, find
the absolute and % relative error assuming that the
currently accepted value of 6.941 is the true value

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 Seatwork
49

A B C D E F
3.5 70.24 0.812 2.7 70.65 0.514
3.1 70.22 0.792 3.0 70.63 0.503
3.1 70.10 0.794 2.6 70.64 0.486
3.3 0.900 2.8 70.21 0.497
2.5 3.2 0.472
Find the mean, s, %rsd, and CL for each of
the data sets above.
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 Seatwork
50

Apply the Q test and Grubbs test at 95% confidence

level whether the outlying result should be retained
or rejected:
A: 85.10, 84.82, 84.70
B: 4.40, 4.42, 4.60, 4.48, 4.50

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Thanks!!!