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 Quality Assurance
and Quality Control
in the Analytical
Chemical Laboratory
A Practical Approach
Second Edition
A N A LY T I C A L C H E M I S T R Y S E R I E S

Quality and Reliability in Analytical Chemistry, George E. Baiulescu,

Raluca-Ioana Stefan, Hassan Y. Aboul-Enein
HPLC: Practical and Industrial Applications, Second Edition, Joel K. Swadesh
Ionic Liquids in Chemical Analysis, edited by Mihkel Koel
Environmental Chemometrics: Principles and Modern Applications,
Grady Hanrahan
Analytical Measurements in Aquatic Environments, edited by Jacek Namieśnik
and Piotr Szefer
Ion-Pair Chromatography and Related Techniques, Teresa Cecchi
Artificial Neural Networks in Biological and Environmental Analysis,
Grady Hanrahan
Electroanalysis with Carbon Paste Electrodes, Ivan Svancara, Kurt Kalcher,
Alain Walcarius, and Karel Vytras
Quality Assurance and Quality Control in the Analytical Chemical Laboratory:
A Practical Approach, Second Edition, Piotr Konieczka and Jacek Namieśnik
 Quality Assurance
and Quality Control
in the Analytical
Chemical Laboratory
A Practical Approach
Second Edition

Piotr Konieczka
Jacek Namieśnik
CRC Press
Taylor & Francis Group
6000 Broken Sound Parkway NW, Suite 300
Boca Raton, FL 33487-2742

© 2018 by Taylor & Francis Group, LLC

CRC Press is an imprint of Taylor & Francis Group, an Informa business

No claim to original U.S. Government works

Printed on acid-free paper

International Standard Book Number-13: 978-1-138-19672-8 (Hardback)

This book contains information obtained from authentic and highly regarded sources. Reasonable efforts
have been made to publish reliable data and information, but the author and publisher cannot assume
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Contents
Preface.......................................................................................................................ix
About the Authors......................................................................................................xi
List of Abbreviations.............................................................................................. xiii

Chapter 1 Basic Notions of Statistics..................................................................... 1

1.1 Introduction................................................................................1
1.2 Distributions of Random Variables............................................ 1
1.2.1 Characterization of Distributions.................................. 1
1.3 Measures of Location.................................................................3
1.4 Measures of Dispersion.............................................................. 5
1.5 Measures of Asymmetry............................................................ 7
1.6 Measures of Concentration......................................................... 8
1.7 Statistical Hypothesis Testing....................................................9
1.8 Statistical Tests......................................................................... 10
1.8.1 Confidence Interval Method........................................ 10
1.8.2 Critical Range Method................................................ 13
1.8.3 Dixon’s Q Test............................................................. 14
1.8.4 Chi Square Test........................................................... 16
1.8.5 Snedecor’s F Test........................................................ 16
1.8.6 Hartley’s Fmax Test....................................................... 17
1.8.7 Bartlett’s Test............................................................... 18
1.8.8 Morgan’s Test..............................................................20
1.8.9 Student’s t Test............................................................. 21
1.8.10 Cochran–Cox C Test................................................... 23
1.8.11 Aspin–Welch Test........................................................24
1.8.12 Cochran’s Test.............................................................25
1.8.13 Grubbs’ Test.................................................................26
1.8.14 Hampel’s Test..............................................................28
1.8.15 Z-Score........................................................................ 29
1.8.16 En Score....................................................................... 30
1.8.17 Mandel’s h Test............................................................ 30
1.8.18 Kolmogorov–Smirnov Test......................................... 32
1.9 Linear Regression..................................................................... 32
1.10 Significant Digits: Rules of Rounding......................................34
References........................................................................................... 35

Chapter 2 Quality of Analytical Results.............................................................. 37

2.1 Definitions................................................................................ 37
2.2 Introduction.............................................................................. 37

v
vi Contents

2.3 Quality Assurance System....................................................... 38

2.4 Conclusion................................................................................ 42
References........................................................................................... 42

Chapter 3 Internal Quality Control...................................................................... 45

3.1 Definition.................................................................................. 45
3.2 Introduction.............................................................................. 45
3.3 Quality Control in the Laboratory............................................ 45
3.4 Control Charts.......................................................................... 47
3.4.1 Shewhart Charts.......................................................... 47
3.4.2 Shewhart Chart Preparation........................................ 48
3.4.3 Shewhart Chart Analysis............................................. 49
3.4.4 Types of Control Charts.............................................. 55
3.4.5 Control Samples.......................................................... 62
3.5 Conclusion................................................................................ 63
References...........................................................................................64

Chapter 4 Traceability.......................................................................................... 65
4.1 Definitions................................................................................ 65
4.2 Introduction.............................................................................. 65
4.3 The Role of Traceability in Quality Assurance/Quality
Control Systems........................................................................ 67
4.4 Conclusion................................................................................ 71
References........................................................................................... 72

Chapter 5 Uncertainty.......................................................................................... 73
5.1 Definitions................................................................................ 73
5.2 Introduction.............................................................................. 74
5.3 Methods of Estimating Measurement Uncertainty.................. 75
5.3.1 Procedure for Estimating the Measurement
Uncertainty According to the Guide to the
Expression of Uncertainty in Measurement................ 75
5.4 Tools Used for Uncertainty Estimation.................................... 83
5.5 Uncertainty and Confidence Interval.......................................84
5.6 Calibration Uncertainty............................................................ 86
5.7 Conclusion................................................................................90
References...........................................................................................90

Chapter 6 Reference Materials............................................................................. 93

6.1 Definitions................................................................................ 93
6.2 Introduction.............................................................................. 93
Contents vii

6.3 Parameters that Characterize RMs.......................................... 98

6.3.1 General Information.................................................... 98
6.3.2 Representativeness...................................................... 98
6.3.3 Homogeneity............................................................... 98
6.3.4 Stability.......................................................................99
6.3.5 Certified Value.......................................................... 100
6.4 Practical Application of CRMs.............................................. 101
6.5 Conclusion.............................................................................. 117
References......................................................................................... 118

Chapter 7 Interlaboratory Comparisons............................................................ 121

7.1 Definitions.............................................................................. 121
7.2 Introduction............................................................................ 121
7.3 Classification of Interlaboratory Studies................................ 122
7.4 Characteristics and Organization of Interlaboratory
Comparisons........................................................................... 125
7.5 The Presentation of Interlaboratory Comparison Results:
Statistical Analysis in Interlaboratory Comparisons.............. 126
7.5.1 Comparisons of Results Obtained Using
Various Procedures................................................... 144
7.5.2 Comparison of the Measurement Results
Obtained in a Two-Level Study (for Two
Samples with Various Analyte Concentrations)........ 148
7.6 Conclusion.............................................................................. 154
References......................................................................................... 154

Chapter 8 Method Validation............................................................................. 157

8.1 Introduction............................................................................ 157
8.2 Characterization of Validation Parameters............................ 160
8.2.1 Selectivity.................................................................. 160
8.2.2 Linearity and Calibration.......................................... 162
8.2.3 Limit of Detection and Limit of Quantitation........... 170
8.2.3.1 Visual Estimation...................................... 171
8.2.3.2 Calculation of LOD Based on the
Numerical Value of the S/N Ratio............. 171
8.2.3.3 Calculation of LOD Based on
Determinations for Blank Samples............ 171
8.2.3.4 Graphical Method...................................... 172
8.2.3.5 Calculating LOD Based on the
Standard Deviation of Signals and
the Slope of the Calibration Curve............ 173
8.2.3.6 Calculation of LOD Based on a Given
LOQ........................................................... 173
viii Contents

8.2.3.7 Testing the Correctness of the

Determined LOD....................................... 174
8.2.4 Range......................................................................... 187
8.2.5 Sensitivity.................................................................. 190
8.2.6 Precision.................................................................... 191
8.2.6.1 Manners of Estimating the Standard
Deviation.................................................... 193
8.2.7 Accuracy and Trueness.............................................200
8.2.7.1 Measurement Errors.................................. 201
8.2.8 Robustness and Ruggedness......................................224
8.2.9 Uncertainty................................................................ 225
8.3 Conclusion.............................................................................. 233
References......................................................................................... 243

Chapter 9 Method Equivalence.......................................................................... 247

9.1 Introduction............................................................................ 247
9.2 Ways of Equivalence Demonstration...................................... 247
9.2.1 Difference Testing..................................................... 247
9.2.2 Equivalence Testing.................................................. 253
9.2.3 Regression Analysis Testing...................................... 256
9.3 Conclusion.............................................................................. 258
References......................................................................................... 258

Appendix................................................................................................................ 261
Index....................................................................................................................... 273
Preface
The aim of this book is to provide practical information about quality assurance/
quality control (QA/QC) systems, including the definitions of all tools, an under-
standing of their uses, and an increase in knowledge about the practical application
of statistical tools during analytical data treatment.
Although this book is primarily designed for students and teachers, it may also
prove useful to the scientific community, particularly among those who are inter-
ested in QA/QC. With its comprehensive coverage, this book can be of particular
interest to researchers in the industry and academia, as well as government agencies
and legislative bodies.
The theoretical part of the book contains information on questions relating to
quality control systems.
The practical part includes more than 80 examples relating to validation param-
eter measurements, using statistical tests, calculation of the margin of error, estimat-
ing uncertainty, and so on. For all examples, a constructed calculation datasheet
(Excel) is attached, which makes problem solving easier.
The eResource files available to readers of this text contain more than 80 Excel
datasheet files, each consisting of three main components: Problem, Data, and
Solution. In some cases, additional data, such as graphs and conclusions, are also
included. After saving an Excel file on the hard disk, it is possible to use it on differ-
ent data sets. It should be noted that in order to obtain correct calculations, it is nec-
essary to use it appropriately. The user’s own data should be copied only into yellow
marked cells (be sure that your data set fits the appropriate datasheet). Solution data
will be calculated and can be read from green marked cells.
We hope that with this book, we can contribute to a better understanding of all
problems connected with QA/QC.

ix
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About the Authors
Piotr Konieczka (MSc, 1989; PhD, 1994; DSc, 2008-GUT;
Prof., 2014) has been employed at Gdańsk University of
Technology since 1989 and is currently working as a full
professor.
His published scientific output includes 2 books, 10 book
chapters, and more than 80 papers published in international
journals from the JCR list (∑ IF = 188), as well as more
than 100 lectures and communications. His number of cita-
tions (without self-citations) equals 957 and his h-index is
19 (according to the Web of Science, December 31, 2017).
Dr. Konieczka has been supervisor or co-supervisor of six PhD theses (completed).
His research interests include metrology, environmental analytics and monitor-
ing, and trace analysis.

Jacek Namieśnik (MSc, 1972-GUT; PhD, 1978-GUT;

DSc, 1985-GUT; Prof., 1998) has been employed at Gdańsk
University of Technology since 1972. Currently a full professor,
he has also served as vice dean of the Chemical Faculty (1990–
1996) and dean of the Chemical Faculty (1996–2000 and 2005–
2012). He has been the head of the Department of Analytical
Chemistry since 1995, as well as chairman of the Committee of
Analytical Chemistry of the Polish Academy of Sciences since
2007, and Fellow of the International Union of Pure and Applied
Chemistry (IUPAC) since 1996. He was director of the Centre
of Excellence in Environmental Analysis and Monitoring in
2003–2005. Among his published scientific papers are 8 books, more than 700 papers
published in international journals from the JCR list (∑ IF = 1975), and more than 400
lectures and communications published in conference proceedings. Dr. Namieśnik has
10 patents to his name. His number of citations (without self-citations) equals 9415 and
his h-index is 47 (according to Web of Science, October 31, 2017). He has been the
supervisor or co-supervisor of 64 PhD theses (completed).
Dr. Namieśnik is the recipient of various awards, including Professor honoris
causa from the University of Bucharest (Romania, 2000), the Jan Hevelius Scientific
Award of Gdańsk City (2001), the Prime Minister of Republic of Poland Awards
(2007, 2017), the award of the Ministry of Science and Higher Education Award for
young scientists’ education (2012), the award of the Ministry of Science and Higher
Education Award for outstanding achievements in the field of society development
(2015), and doctor honoris causa of the Military Technical Academy (Warsaw) and
Medical University of Gdańsk (Gdańsk, 2015).
Dr. Namieśnik was elected as a rector of Gdańsk University of Technology for
the period of 2016–2020. His research interests include environmental analytics and
monitoring, and trace analysis.

xi
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List of Abbreviations
AAS Atomic Absorption Spectrometry
ANOVA Analysis Of Variance
BCR Bureau Communautaire de Reference (Standards, Measurements, and
Testing Programme–European Community)
CDF Cumulative Distribution Function
CITAC Cooperation on International Traceability in Analytical Chemistry
CL Central Line
CRM Certified Reference Material
CUSUM Cumulative SUM
CV Coefficient of Variation
CVAAS Cold Vapor Atomic Absorption Spectrometry
D Mean Absolute Deviation
EN European Norm
GC Gas Chromatography
GLP Good Laboratory Practice
GUM Guide to the Expression of Uncertainty in Measurement
IAEA International Atomic Energy Agency
ICH International Conference on Harmonisation
IDL Instrumental Detection Limit
ILC InterLaboratory Comparisons
IQC Internal Quality Control
IQR InterQuaRtile Value
IRMM Institute for Reference Materials and Measurements
ISO International Organization for Standardization
IUPAC International Union of Pure and Applied Chemistry
JCGM Joint Committee for Guides in Metrology
LAL Lower Action (Control) Limit
LOD Limit of Detection
LOQ Limit of Quantification
L-PS Laboratory-Performance Study
LRM Laboratory Reference Material
LWL Lower Warning Limit
MB Method Blank
M-CS Material-Certification Study
MDL Method Detection Limit
Me Median
Mo Mode
M-PS Method-Performance Study
MQL Method Quantification Limit
NIES National Institute for Environmental Studies
NIST National Institute of Standards and Technology
NRCC National Research Council of Canada

xiii
xiv List of Abbreviations

PRM Primary Reference Material

PT Proficiency Test
q Quartile
QA(1) Quality Assessment
QA(2) Quality Assurance
QA/QC Quality Assurance/Quality Control
QC Quality Control
QCM Quality Control Material
R Range
RH Relative Humidity
RM Reference Material
RSD Relative Standard Deviation
S/N Signal-to-Noise Ratio
SD Standard Deviation
SecRM Secondary Reference Material
SI Le Systeme Internationale d’Unités (The International System of Units)
SOP Standard Operating Procedure
SRM Standard Reference Material
UAL Upper Action (Control) Limit
USP The United States Pharmacopeia
UWL Upper Warning Limit
V Variance
VIM Vocabulaire International des Termes Fondamentaux et Généraux de
Métrologie (International Vocabulary of Metrology)
VIRM The European Virtual Institute for Reference Materials
%R Recovery
 1 Basic Notions of Statistics

1.1 INTRODUCTION
Mathematical statistics is a branch of mathematics that applies the theory of prob-
ability to examining regularities in the occurrence of certain properties of material
objects or phenomena which occur in unlimited quantities. Statistics presents these
regularities by means of numbers.
Statistics is not only art for art’s sake. It is a very useful tool that can help us find
answers to many questions. Statistics is especially helpful for analysts, because it
may clear many doubts and answer many questions associated with the nature of an
analytic process, for example:

• How exact the result of determination is

• How many determinations should be conducted to increase the precision of
a measurement
• Whether the investigated product fulfills the necessary requirements or
norms

Yet it is important to remember that statistics should be applied in a reasonable way.

1.2 DISTRIBUTIONS OF RANDOM VARIABLES

1.2.1 Characterization of Distributions
The application of a certain analytical method unequivocally determines the distri-
bution of measurement results (properties), here treated as independent random vari-
ables. A result is a consequence of a measurement. The set of obtained determination
results creates a distribution (empirical).
Each defined distribution is characterized by the following parameters:

• A cumulative distribution function (CDF) X is determined by FX and repre-

sents the probability that a random variable X takes on a value less than or
equal to x; a CDF is (not necessarily strictly) right-continuous, with its limit
equal to 1 for arguments approaching positive infinity, and equal to 0 for
arguments approaching negative infinity; in practice, a CDF is described
shortly by FX(x) = P(X ≤ x).
• A density function which is the derivative of the CDF: f ( x ) = FX′ ( x ).

1
2 QA/QC in the Analytical Chemical Laboratory

Below are the short characterizations of the most frequently used distributions:

• Normal distribution
• Uniform distribution (rectangular)
• Triangular distribution

Normal distribution, also called Gaussian distribution (particularly in physics

and engineering), is a very important probability distribution used in many domains.
It is an infinite family of many distributions, defined by two parameters: mean (loca-
tion) and standard deviation (scale).
Normal distribution, N (μx, SD), is characterized by the following properties:

• An expected value μx
• A median Me = μx
• A variance V

Uniform distribution (also called continuous or rectangular) is a continuous

probability distribution for which the probability density function within the interval
− a, + a is constant and not equal to zero, but outside the interval is equal to zero.
Because this distribution is continuous, it is not important whether the endpoints
–a and +a are included in the interval. The distribution is determined by a pair of
parameters – a and +a.
Uniform distribution is characterized by

• An expected value μx = 0
• A median Me = 0
• A variance V = a2/3

Triangular distribution over the interval − a, + a is characterized by

• An expected value μx = 0
• A median Me = 0
• A variance V = a2/6

The distribution of a random variable provides complete information on an

investigated characteristic (e.g., concentration, content, physiochemical property).
Unfortunately, such complete information is seldom available. As a rule, character-
istic inference is drawn using the analysis of a limited number of elements (samples)
representing a fragment of the whole set that is described by the distribution. Then,
one may infer a characteristic using an estimation of some of its parameters (statisti-
cal parameters) or its empirical distribution.
Statistical parameters are numerical quantities used in the systematic description
of a statistical population structure.
Basic Notions of Statistics 3

These parameters can be divided into four basic groups:

• Measures of location
• Measures of statistical dispersion
• Measures of asymmetry
• Measures of concentration

1.3 MEASURES OF LOCATION
Measures of location use one value to characterize the general level of the value of
the characteristic in a population [1].
The most popular measures of location are the following:

• Arithmetic mean
• Truncated mean
• Mode
• Quantiles
• Quartiles
• Median
• Deciles

Arithmetic mean is the sum of all the values of a measurable characteristic divided
by the number of units in a finite population:

∑x i

xm = i =1
(1.1)
n

Here are the selected properties of the arithmetic mean:

• The sum of the values is equal to the product of the arithmetic mean and
the population size.
• The arithmetic mean fulfills the following condition:

x min < x m < x max (1.2)

• The sum of deviations of individual values from the mean is equal to zero:

∑ (x − x ) = 0
i =1
i m (1.3)
4 QA/QC in the Analytical Chemical Laboratory

• The sum of squares of deviations of each value from the mean is minimal:

∑ (x − x )
i =1
i m
2
= min (1.4)

• The arithmetic mean is sensitive to extreme values (outliers) of the

characteristic.
• The arithmetic mean from a sample is a good approximation (estimation,
estimator) of the expected value.

The truncated mean xwk is a statistical measurement calculated for the series of
results, among which the extrema (minima or maxima) have a high uncertainty con-
cerning their actual value [2]. Its value is calculated according to the following formula

1 
n − k −1

x wk = ( k + 1) x( k +1) +
n

∑
i= k +2
x(i ) + ( k + 1) x( n− k ) 

(1.5)

where
xwk: Truncated mean
n: Number of results in the series
k: Number of extreme (discarded) results

Mode Mo is the value that occurs most frequently in a data set. In a set of results,
there may be more than one value that can be a mode, because the same maximum
frequency can be attained at different values.
Quantiles q are values in an investigated population (a population presented in
the form of a statistical series) that divide the population into a certain number of
subsets. Quantiles are data values marking boundaries between consecutive subsets.
The 2-quantile is called the median, 4-quantiles are called quartiles, 10-quantiles
are deciles, and 100-quantiles are percentiles.
A quartile is any of three values that divide a sorted data set into four equal parts,
so that each part represents one-quarter of the sampled population.
The first quartile (designated q1) divides the population in such a way that 25 per-
cent of the population units have values lower than or equal to the first quartile q1,
and 75 percent of the units have values higher than or equal to the first quartile. The
second quartile q2 is the median. The third quartile (designated q3) divides the popu-
lation in such a way that 75 percent of the population units have values lower than or
equal to the third quartile q3, and 25 percent units have values higher than or equal
to the quartile.
The median Me measurement is the middle number in a population arranged in
a nondecreasing order (for a population with an odd number of observations), or the
mean of the two middle values (for those with an even number of observations).
Basic Notions of Statistics 5

A median separates the higher half of a population from the lower half; half of the
units have values smaller than or equal to the median, and half of them have values
higher than or equal to the median. Contrary to the arithmetic mean, the median is
not sensitive to outliers in a population. This is usually perceived as its advantage,
but sometimes may also be regarded as a flaw; even immense differences between
outliers and the arithmetic mean do not affect its value.
Hence, other means have been proposed; for example, the truncated mean. This
mean, less sensitive to outliers than the standard mean (only a large number of
outliers can significantly influence the truncated mean) and standard deviation, is
calculated using all results, which transfers the extreme to an accepted deviation
range—thanks to the application of appropriate iterative procedures.
The first decile represents 10 percent of the results that have values lower than
or equal to the first decile, and 90 percent of the results have values greater than or
equal to it.

1.4 MEASURES OF DISPERSION
Measures of dispersion (variability) are usually used to determine differences
between individual observations and mean value [1].
The most popular measures of dispersion are

• Range
• Variance
• Standard deviation
• Average deviation
• Coefficient of variation

The range R is a difference between the maximum and minimum value of an

examined characteristic:

R = x max − x min (1.6)

It is a measure characterizing the empirical variability region of the examined

characteristic, but does not give information on the variability of individual values
of the characteristic in the population.
Variance V is an arithmetic mean of the squared distance of values from the
arithmetic mean of the population. Its value is calculated according to the formula

V=
1
n −1 ∑ (x − x )
i −1
i m
2
(1.7)

Standard deviation SD, the square root of the variance, is the measure of disper-
sion of individual results around the mean. It is described by the following equation:
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6 QA/QC in the Analytical Chemical Laboratory

∑ (x − x )
i m
2

SD = i =1
(1.8)
n −1

SD equals zero only when all results are identical. In all other cases it has
positive values. Thus, the greater the dispersion of results, the greater the value of
the SD.
It must be remembered that dispersion of results occurs in each analytical pro-
cess. Yet it is not always observed, for example, because the resolution of a measur-
ing instrument being too low.
Properties of SD include the following

• If a constant value is added to or subtracted from each value, the SD does

not change.
• If each measurement value is multiplied or divided by any constant value,
the SD is also multiplied/divided by that same constant.
• SD is always a denominate number, and it is always expressed in the same
units as the results.

If an expected value μx is known, the SD is calculated according to the following

formula:

∑ (x − µ )
i =1
i x
2

SD = (1.9)
n

Relative standard deviation (RSD) is obtained by dividing the SD by the arith-

metic mean:

SD
RSD = (1.10)
xm

Obviously, xm ≠ 0.
The SD of the arithmetic mean SD is calculated according to the following
equation:

SD
SD = (1.11)
n

The SD of an analytical method SDg (general) is determined using the results

from a series of measurements:
Basic Notions of Statistics 7

SDg =
1
n−k ∑ SD (n − 1)
i =1
2
i i (1.12)

where k equals the number of series of parallel determinations.

For series with equal numbers of elements, the formula is simplified to the fol-
lowing equation:

SDg =
1
k ∑ SDi =1
2
i (1.13)

The mean absolute deviation D is an arithmetic mean of absolute deviations of

the values from the arithmetic mean. It determines the mean difference between the
results in the population and the arithmetic mean:

D=
1
n ∑x −x
i =1
i m (1.14)

The relationship between the mean and SDs for the same set of results can be
presented as D < SD.
The coefficient of variation CV is RSD presented in percentage points:

CV = RSD[%] (1.15)

The CV is the quotient of the absolute variation measure of the investigated char-
acteristic and the mean value of that characteristic. It is an absolute number, usually
presented in percentage points.
The CV is usually applied in comparing differences:

• Among several populations with regard to the same characteristic

• Within the same population with regard to a few different characteristics

1.5 MEASURES OF ASYMMETRY
A skewness (asymmetry) coefficient is an absolute value expressed as the difference
between an arithmetic mean and a mode.
The skewness coefficients are applied in comparisons in order to estimate the
force and the direction of asymmetry. These are absolute numbers: The greater the
asymmetry, the greater their value.
The quartile skewness coefficient shows the direction and force of result asym-
metry located between the first and third quartiles.
8 QA/QC in the Analytical Chemical Laboratory

1.6 MEASURES OF CONCENTRATION
A concentration coefficient K is a measure of the concentration of individual obser-
vations around the mean. The greater the value of the coefficient, the more slender
the frequency curve and the greater the concentration of the values about the mean.

Example 1.1
Problem: For the given series of measurement results, give the following values:

• Mean
• Standard deviation
• Relative standard deviation
• Mean absolute deviation
• Coefficient of variation
• Minimum
• Maximum
• Range
• Median
• Mode

Data: Result series, mg/dm3:

1 12.34
2 12.67
3 12.91
4 12.02
5 12.52
6 12.12
7 12.98
8 12.34
9 12.00
10 12.67
11 12.53
12 12.34
13 12.79

Solution:
Mean, xm, mg/dm3 12.48
Standard deviation, SD, mg/dm3 0.32
Relative standard deviation, RSD 0.0257
Mean absolute deviation, D 0.264
Coefficient of variation—CV,% 2.57%
Minimum, xmin, mg/dm3 12.00
Maximum, xmax, mg/dm3 12.98
Range, R, mg/dm3 0.98
Median, Me, mg/dm3 12.52
Mode, Mo, mg/dm3 12.34

Excel file: exampl_stat01.xls

Basic Notions of Statistics 9

1.7 STATISTICAL HYPOTHESIS TESTING

A hypothesis is a proposition concerning a population, based on probability,
assumed in order to explain some phenomenon, law, or fact. A hypothesis requires
testing.
Statistical hypothesis testing means checking propositions with regard to a popu-
lation that have been formulated without examining the whole population. The plot
of the testing procedure involves:

1. Formulating the null hypothesis and the alternative hypothesis. The null
hypothesis Ho is a simple form of the hypothesis that is subjected to tests.
The alternative hypothesis H1 is contrasted with the null hypothesis.
2. The choice of an appropriate test. The test serves to verify the hypothesis.
3. Determination of the level of significance α.
4. Determining the critical region of a test. The size of the critical region is
determined by any low level of significance α, and its location is deter-
mined by the alternative hypothesis.
5. Calculation of a test’s parameter using a sample. The results of the sample
are processed in a manner appropriate to the procedure of the selected test
and are the basis for the calculation of the test statistic.
6. Conclusion. The test statistic, determined using the sample, is compared
with the critical value of the test:
• If the value falls within the critical region, then the null hypothesis
should be rejected as false. It means that the value of the calculated
test parameter is greater than the critical value of the test (read from a
relevant table).
• If the value is outside the critical region, it means that there is not
enough evidence to reject the null hypothesis. It means that the value of
the calculated parameter is not greater than the critical value of the test
(read from a relevant table); hence, the conclusion that the null hypoth-
esis may be true.
Errors made during verification:
– Type I error: Incorrectly rejecting the null hypothesis Ho when it
is true
– Type II error: Accepting the null hypothesis Ho when it is false

Nowadays, statistical hypothesis testing is usually carried out using various pieces
of software (e.g., Statistica®). In this case, the procedure is limited to calculating the
parameter p for a given set of data after selecting an appropriate statistical test. The
value p is then compared with the assumed value of the level of significance α.
If the calculated value p is smaller than the α value (p < α), the null hypothesis Ho
is rejected. Otherwise, the null hypothesis is not rejected.
The basic classification of a statistical test divides tests into parametric and
nonparametric ones.
Parametric tests serve to verify parametric hypotheses on the distribution param-
eters of the examined characteristic in a parent population. Usually they are used to
10 QA/QC in the Analytical Chemical Laboratory

test propositions concerning arithmetic mean and variance. The tests are constructed
with the assumption that the CDF is known for the parent population.
Nonparametric tests are used to test various hypotheses on the goodness of fit in
one population with a given theoretical distribution, the goodness of fit in two popu-
lations, and the randomness of sampling.

1.8 STATISTICAL TESTS
During the processing of analytical results, various statistical tests can be used.
Their descriptions, applications, and inferences based on these tests are presented
below. Appropriate tables with critical values for individual tests are given in the
appendix at the end of the book.

1.8.1 Confidence Interval Method [3]

Test Confidence Interval Method

Aim Test whether a given set of results includes a result(s) with a
gross error
Requirements • Set size 3–10
• Unbiased series—an initially rejected uncertain result
• Only one result can be rejected from a given set
Course of action • Exclude from a set of results the result that was initially
recognized as one with a gross error
• Calculate the endpoints of the confidence interval for a
single result based on the following formula:

n
g = x m ± tcrit SD (1.16)
n−2

where
xm: Mean for an unbiased series
SD: Standard deviation for an unbiased series
n: Entire size of a series, together with an uncertain result
tcrit: Critical parameter of the Student’s t test, read for f = n – 2
degrees of freedom—Table A.1 (in the appendix)
Inference If an uncertain result falls outside the limits of the confidence
interval, it is rejected; otherwise, it is compensated for in
further calculations and the values of xm and SD are calculated
again
Requirements • Set size is 3–10
• Unbiased series—an initially rejected doubtful result
• Only one result can be rejected from a given set
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