INTERNATIONAL ISO

STANDARD 11843-2

First edition
2000-05-01

Capability of detection —
Part 2:
Methodology in the linear calibration case
Capacité de détection —
Partie 2: Méthodologie de l'étalonnage linéaire
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ISO 11843-2:2000
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Reference number
ISO 11843-2:2000(E)

© ISO 2000
ISO 11843-2:2000(E)

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 ISO 11843-2:2000(E)

Contents

Foreword.....................................................................................................................................................................iv
Introduction .................................................................................................................................................................v
1 Scope ..............................................................................................................................................................1
2 Normative references ....................................................................................................................................1
3 Terms and definitions ...................................................................................................................................2
4 Experimental design......................................................................................................................................2
4.1 General............................................................................................................................................................2
4.2 Choice of reference states............................................................................................................................2
4.3 Choice of the number of reference states, I, and the (numbers of) replications of procedure, J,
K and L ............................................................................................................................................................3
5 The critical values yc and xc and the minimum detectable value xd of a measurement series .............3
5.1 Basic assumptions ........................................................................................................................................3
5.2 Case 1 — Constant standard deviation.......................................................................................................4
5.3 Case 2 — Standard deviation linearly dependent on the net state variable............................................6
6 iTeh STANDARD PREVIEW
Minimum detectable value of the measurement method ..........................................................................9
7 Reporting and use of results ......................................................................................................................10
7.1 (standards.iteh.ai)
Critical values...............................................................................................................................................10
7.2 Minimum detectable values ........................................................................................................................10
ISO 11843-2:2000
Annex A (normative) Symbols and abbreviations .................................................................................................11
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Annex B (informative) Derivation of formulae........................................................................................................14
Annex C (informative) Examples .............................................................................................................................20
Bibliography ..............................................................................................................................................................24

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ISO 11843-2:2000(E)

Foreword
ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO
member bodies). The work of preparing International Standards is normally carried out through ISO technical
committees. Each member body interested in a subject for which a technical committee has been established has
the right to be represented on that committee. International organizations, governmental and non-governmental, in
liaison with ISO, also take part in the work. ISO collaborates closely with the International Electrotechnical
Commission (IEC) on all matters of electrotechnical standardization.

International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 3.

Draft International Standards adopted by the technical committees are circulated to the member bodies for voting.
Publication as an International Standard requires approval by at least 75 % of the member bodies casting a vote.

Attention is drawn to the possibility that some of the elements of this part of ISO 11843 may be the subject of
patent rights. ISO shall not be held responsible for identifying any or all such patent rights.

International Standard ISO 11843-2 was prepared by Technical Committee ISO/TC 69, Applications of statistical
methods, Subcommittee SC 6, Measurement methods and results.

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ISO 11843 consists of the following parts, under the general title Capability of detection:

¾ Part 1: Terms and definitions (standards.iteh.ai)

¾ Part 2: Methodology in the linear calibration case
ISO 11843-2:2000
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Annex A forms a normative part of this part of ISO 11843. Annexes B and C are for information only.
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 ISO 11843-2:2000(E)

Introduction
An ideal requirement for the capability of detection with respect to a selected state variable would be that the actual
state of every observed system can be classified with certainty as either equal to or different from its basic state.
However, due to systematic and random distortions, this ideal requirement cannot be satisfied because:

¾ in reality all reference states, including the basic state, are never known in terms of the state variable. Hence,
all states can only be correctly characterized in terms of differences from basic state, i.e. in terms of the net
state variable.

In practice, reference states are very often assumed to be known with respect to the state variable. In other
words, the value of the state variable for the basic state is set to zero; for instance in analytical chemistry, the
unknown concentration or the amount of analyte in the blank material usually is assumed to be zero and
values of the net concentration or amount are reported in terms of supposed concentrations or amounts. In
chemical trace analysis especially, it is only possible to estimate concentration or amount differences with
respect to available blank material. In order to prevent erroneous decisions, it is generally recommended to
report differences from the basic state only, i.e. data in terms of the net state variable;

NOTE In the ISO Guide 30 and in ISO 11095 no distinction is made between the state variable and the net state
variable. As a consequence, in these two documents reference states are, without justification, assumed to be known with
respect to the state variable.
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¾ the calibration and the processes of sampling and preparation add random variation to the measurement
results. (standards.iteh.ai)
ISO 11843-2:2000
In this part of ISO 11843, the following two requirements were chosen:
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¾ the probability is =  of detecting (erroneously) that a system is not in the basic state when it is in the basic
state;

¾ the probability is >of (erroneously) not detecting that a system, for which the value of the net state variable is
equal to the minimum detectable value (xd), is not in the basic state.

© ISO 2000 – All rights reserved v

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ISO 11843-2:2000
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INTERNATIONAL STANDARD ISO 11843-2:2000(E)

Capability of detection —
Part 2:
Methodology in the linear calibration case

1 Scope
This part of ISO 11843 specifies basic methods to:

¾ design experiments for the estimation of the critical value of the net state variable, the critical value of the
response variable and the minimum detectable value of the net state variable,

¾ estimate these characteristics from experimental data for the cases in which the calibration function is linear
and the standard deviation is either constant or linearly related to the net state variable.

The methods described in this part of ISO 11843 are applicable to various situations such as checking the
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existence of a certain substance in a material, the emission of energy from samples or plants, or the geometric
change in static systems under distortion.
(standards.iteh.ai)
Critical values can be derived from an actual measurement series so as to assess the unknown states of systems
included in the series, whereas the minimum detectable ISO 11843-2:2000
value of the net state variable as a characteristic of the
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measurement method serves for the selection of appropriate measurement processes. In order to characterize a
measurement process, a laboratory or thef973af557b32/iso-11843-2-2000
measurement method, the minimum detectable value can be stated if
appropriate data are available for each relevant level, i.e. a measurement series, a measurement process, a
laboratory or a measurement method. The minimum detectable values may be different for a measurement series,
a measurement process, a laboratory or the measurement method.

ISO 11843 is applicable to quantities measured on scales that are fundamentally continuous. It is applicable to
measurement processes and types of measurement equipment where the functional relationship between the
expected value of the response variable and the value of the state variable is described by a calibration function. If
the response variable or the state variable is a vectorial quantity the methods of ISO 11843 are applicable
separately to the components of the vectors or functions of the components.

2 Normative references
The following normative documents contain provisions which, through reference in this text, constitute provisions of
this part of ISO 11843. For dated references, subsequent amendments to, or revisions of, any of these publications
do not apply. However, parties to agreements based on this part of ISO 11843 are encouraged to investigate the
possibility of applying the most recent editions of the normative documents indicated below. For undated
references, the latest edition of the normative document referred to applies. Members of ISO and IEC maintain
registers of currently valid International Standards.

ISO 3534-1:1993, Statistics — Vocabulary and symbols — Part 1: Probability and general statistical terms.

ISO 3534-2:1993, Statistics — Vocabulary and symbols — Part 2: Statistical quality control.

ISO 3534-3:1999, Statistics — Vocabulary and symbols — Part 3: Design of experiments.

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ISO 11843-2:2000(E)

ISO 11095:1996, Linear calibration using reference materials.

ISO 11843-1:1997, Capability of detection — Part 1: Terms and definitions.

ISO Guide 30:1992, Terms and definitions used in connection with reference materials.

3 Terms and definitions

For the purposes of this part of ISO 11843, the terms and definitions of ISO 3534 (all parts), ISO Guide 30,
ISO 11095 and ISO 11843-1 apply.

4 Experimental design

4.1 General

The procedure for determining values of an unknown actual state includes sampling, preparation and the
measurement itself. As every step of this procedure may produce distortion, it is essential to apply the same
procedure for characterizing, for use in the preparation and determination of the values of the unknown actual
state, for all reference states and for the basic state used for calibration.

For the purpose of determining differences between the values characterizing one or more unknown actual states
and the basic state, it is necessary to choose an experimental design suited for comparison. The experimental units
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of such an experiment are obtained from the actual states to be measured and all reference states used for
calibration. An ideal design would keep constant all factors known to influence the outcome and control of unknown
(standards.iteh.ai)
factors by providing a randomized order to prepare and perform the measurements.

In reality it may be difficult to proceed in such a way, as the preparations and determination of the values of the
ISO 11843-2:2000
states involved are performed consecutively over a period of time. However, in order to detect major biases
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changing with time, it is strongly recommended to perform one half of the calibration before and one half after the
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measurement of the unknown states. However, this is only possible if the size of the measurement series is known
in advance and if there is sufficient time to follow this approach. If it is not possible to control all influencing factors,
conditional statements containing all unproven assumptions shall be presented.

Many measurement methods require a chemical or physical treatment of the sample prior to the measurement
itself. Both of these steps of the measurement procedure add variation to the measurement results. If it is required
to repeat measurements the repetition consists in a full repetition of the preparation and the measurement.
However, in many situations the measurement procedure is not repeated fully, in particular not all of the
preparational steps are repeated for each measurement; see note in 5.2.1.

4.2 Choice of reference states

The range of values of the net state variable spanned by the reference states should include

¾ the value zero of the net state variable, i.e. in analytical chemistry a sample of the blank material, and

¾ at least one value close to that suggested by a priori information on the minimum detectable value; if this
requirement is not fulfilled, the calibration experiment should be repeated with other values of the net state
variable, as appropriate.

The reference states should be chosen so that the values of the net state variable (including log-scaled values) are
approximately equidistant in the range between the smallest and largest value.

In cases in which the reference states are represented by preparations of reference materials their composition
should be as close as possible to the composition of the material to be measured.

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 ISO 11843-2:2000(E)

4.3 Choice of the number of reference states, I, and the (numbers of) replications of procedure,
J, K and L

The choice of reference states, number of preparations and replicate measurements shall be as follows:

¾ the number of reference states I used in the calibration experiment shall be at least 3; however, I = 5 is
recommended;

¾ the number of preparations for each reference state J (including the basic state) should be identical; at least
two preparations (J = 2) are recommended;

¾ the number of preparations for the actual state K should be identical to the number J of preparations for each
reference state;

¾ the number of repeated measurements performed per preparation L shall be identical; at least two repeated
measurements (L = 2) are recommended.

NOTE The formulae for the critical values and the minimum detectable value in clause 5 are only valid under the
assumption that the number of repeated measurements per preparation is identical for all measurements of reference states
and actual states.

As the variations and cost due to the preparation usually will be much higher than those due to the measurement,
the optimal choice of J, K and L may be derived from an optimization of constraints regarding variation and costs.

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5 The critical values yc and xc and the minimum detectable value xd of a measurement
series (standards.iteh.ai)
5.1 Basic assumptions ISO 11843-2:2000
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The following procedures for the computation of the critical values and the minimum detectable value are based on
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the assumptions of ISO 11095. The methods of ISO 11095 are used with one generalization; see 5.3.

Basic assumptions of ISO 11095 are that

¾ the calibration function is linear,

¾ measurements of the response variable of all preparations and reference states are assumed to be
independent and normally distributed with standard deviation referred to as "residual standard deviation",

¾ the residual standard deviation is either a constant, i.e. it does not depend on the values of the net state
variable [case 1], or it forms a linear function of the values of the net state variable [case 2].

The decision regarding the applicability of this part of ISO 11843 and the choice of one of these two cases should
be based on prior knowledge and a visual examination of the data.

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ISO 11843-2:2000(E)

5.2 Case 1 — Constant standard deviation

5.2.1 Model

The following model is based on assumptions of linearity of the calibration function and of constant standard
deviation and is given by:

Yi j = a + bx i + A i j (1)

where

xi is the symbol for the net state variable in state i;

Ai j are random variables which describe the random component of sampling, preparation and measurement
error.

It is assumed that the A i j are independent and normally distributed with expectation zero and the theoretical

e j
residual standard deviation I : A i j ~ N 0 ; I 2 . Therefore, values Yi j of the response variable are random variables

d i d i
with the expectation E Yi j = a + bxi and the variance V Yi j = I ², not depending on xi .

NOTE In the cases in which J samples are prepared for measurement and each of them is measured L times so that J×L
measurements are performed altogether for reference state i, then Y i j refers to the average of the L measurements obtained on
the prepared sample.
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5.2.2 (standards.iteh.ai)
Estimation of the calibration function and the residual standard deviation

In accordance with ISO 11095, estimates (see note) a, b and I 2 are given by:
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ISO
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I J
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å å ( xi - x )( yi j - y )
i =1 j -1
b = (2)
s xx


a = y - bx (3)

I J
å å e yi j - a - bx i j
1 2
I 2 = (4)
I×J -2
i =1 j =1

The symbols used here and elsewhere in this part of ISO 11843 are defined in annex A.

NOTE Estimates are denoted by a symbol ^ to differentiate them from the parameters themselves which are unknown.

5.2.3 Computation of critical values

The critical value of the response variable is given by:

1 1 x2
yc = a + t0,95 (n )s + + (5)
K I × J s xx

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 ISO 11843-2:2000(E)

The critical value of the net state variable is given by:

s 1 1 x2
x c = t0,95 (n ) + + (6)
b K I × J s xx

t0,95 n af is the 95 %-quantile of the t-distribution with n = I × J - 2 degrees of freedom.

The derivation of these formulae is given in annex B.

5.2.4 Computation of the minimum detectable value

The minimum detectable value is given by:

s 1 1 x2
xd = d + + (7)
b K I × J s xx

where

b g
d = n ; a ; b is the value of the noncentrality parameter determined in such a way that a random variable
following the noncentral t-distribution with n = I × J - 2 degrees of freedom and the noncentrality parameter
b g
d , T n ; d , satisfies the equation:

P T bn ; d g u t an f iTeh
=b
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where t1-= (n) is the (1-a )-quantile of the t-distribution with n degrees of freedom.

The derivation of this formula is given in annex B.

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For a = b and n > 3, a good approximationf973af557b32/iso-11843-2-2000
for d is given by

d (n ; a ; b ) » 2t 1-= (n ) (8)

if n = 4 and a = b = 0,05, the relative error of this approximation is 5 %; t1-=(n ) is the (1-a )-quantile of the
t-distribution with n = I×J - 2 degrees of freedom.

Table 1 presents d (n ; a ; b ) for a = b = 0,05 and various values of n.

For a = b and n > 3, xd is approximated by

sˆ 1 1 x2
x d » 2t 0,95 (n ) + + = 2x c (9)
bˆ K I × J s xx

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ISO 11843-2:2000(E)

Table 1 — Values of the noncentrality parameter for a = b = 0,05 and n degrees of freedom

n d (n ; a ; b ) n d (n ; a ; b ) n d (n ; a ; b )
2 5,516 19 3,415 36 3,354
3 4,456 20 3,408 37 3,352
4 4,067 21 3,402 38 3,350
5 3,870 22 3,397 39 3,349
6 3,752 23 3,392 40 3,347
7 3,673 24 3,387 41 3,346
8 3,617 25 3,383 42 3,344
9 3,575 26 3,380 43 3,343
10 3,543 27 3,376 44 3,342
11 3,517 28 3,373 45 3,341
12 3,496 29 3,370 46 3,339
13 3,479 30 3,367 47 3,338
14 3,464 31 3,365 48 3,337
15 3,451 32 3,362 49 3,336
16 3,440 33 3,360 50 3,335
17 3,431 34 3,358
18 3,422 35 3,356

5.3
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Case 2 — Standard deviation linearly dependent on the net state variable
(standards.iteh.ai)
5.3.1 Model
ISO 11843-2:2000
The following model is based https://standards.iteh.ai/catalog/standards/sist/f34208d5-b11b-4f97-8880-
on the assumptions that the calibration function is linear and that the standard
deviation is linearly dependent on the net state variable and is given by:
f973af557b32/iso-11843-2-2000

Yi j = a + bx i + e i j (10)

where

xi, a, b and Yi j are as defined in 5.2.1 and the ei j are independent and normally distributed with expectation
E(ei j) = 0 and variance:

b
V (A i j ) = I 2 ( x i ) = c + dxi g 2
(11)

i.e., the residual standard deviation is linearly dependent on x

I( xi ) = c + dxi (12)

The parameters of the model, a, b, c and d are estimated in a two part procedure as given in 5.3.2 and 5.3.3.

5.3.2 Estimation of the linear relationship between the residual standard deviation and the net state
variable

The parameters c and d are estimated by a linear regression analysis with the standard deviations:

J
1
si = å
J - 1 j =1
( yi j - yi )2 (13)

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