Accred Qual Assur (1997) 2: 354359

Q Springer-Verlag 1997 GENERAL PAPER

Wolfgang Richter Primary methods of measurement in
chemical analysis
Received: 17 April 1997
Accepted: 9 August 1997
W. Richter (Y)
Physikalisch-Technische Bundesanstalt,
D-Braunschweig, Germany
Tel.: c49-(0)531-592-3200
Abstract Primary methods of
measurement have a central func-
tion in metrology. They are an es-
sential component in the realisa-
tion of the SI units and therefore
are indispensable for establishing
traceability of measurements of all
kinds of physical quantities to the
corresponding SI units. This is also
true for chemical analysis. Gravi-
metry, titrimetry, coulometry, and
isotope dilution mass spectrometry
(IDMS) are evaluated with regard
to their potential to be primary
methods according to a general
definition of primary methods re-
cently given by the Comit Consul-
tatif pour la Quantit de Matire
(CCQM). Optical absorption spec-
trometry and methods based on
colligative properties are also con-
sidered. A general scheme for es-
tablishing traceability of chemical
measurements to the SI units using
primary methods is discussed.
Key words Traceability to SI 7
Primary methods 7 Comparability
Introduction
With increasing globalisation of human activities, the
comparability (more precisely: metrological equival-
ence) of measurement results has become an important
issue. Comparability requires traceability to common
references; worldwide comparability requires traceabil-
ity of measurement results to the SI units, the only gen-
erally accepted reference frame available. This is also
true for chemical measurements (measurements for de-
termining chemical composition), the more so as cross-
frontier activities in environmental protection, health
care and trade rely on credible and, hence, accepted
analytical results.
Traceability to the SI units is ultimately accom-
plished by primary methods of measurement. Primary
methods tie the realisation of an SI unit to its defini-
tion, or, in other words: the value of a primary meas-
urement standard of a physical quantity is determined
using a primary method. This is the usual application of
a primary method in metrology in general, at the top of
the traceability chain. But it can also be used to directly
tie a field measurement to the corresponding unit in the
shortest way possible.
Definition and general description
The Comit Consultatif pour la Quantit de Matire
(CCQM), the new metrology body under the Conven-
tion du Mtre, which is responsible for all issues relat-
ing to the accuracy of chemical measurements and their
traceability to the SI units, has recently given a general
definition of a primary method of measurement [1].
This reads:
A primary method of measurement is a method
having the highest metrological qualities, whose opera-
tion is completely described and understood, for which
a complete uncertainty statement can be written down
in terms of SI units, and whose results are, therefore,
accepted without reference to a standard of the quanti-
ty being measured.
The statement that the result of a primary method is
accepted without reference to a standard of the quanti-
ty being measured is interpreted by the CCQM to mean
355
that for a given quantity, X, the equation describing the
measurement method must include no unknown func-
tions of X of significant magnitude. The determination
of X in terms of a reference value X
ref
, itself deter-
mined by a primary method, does not invalidate the
method as being primary.
An example of a method which is not invalidated as
a primary method by using a reference value of the
same quantity is temperature measurement with a spec-
tral radiation thermometer, in which use is made of a
reference value determined by gas thermometry [2].
The value to be measured is linked to the reference val-
ue (itself determined by a primary method) via the
Planck equation, which completely describes the opera-
tion of the radiation thermometer.
Obviously, such cases of complete calculability are
rare in chemical analysis. Instead, empirical determina-
tion of the measurement function by calibration is the
common way. There are, however, a few analytical
methods which have the potential for being used as pri-
mary methods. These are, for example, gravimetry, ti-
trimetry, coulometry and isotopic dilution mass spec-
trometry (IDMS), according to a proposal of the
CCQM.
The terms definitive or absolute are often used
to characterise methods in chemical analysis which
meet the basic requirements to be fulfilled by primary
methods according to the CCQM definition. What this
definition adds is the requirement that the method be
of highest metrological quality. This means that it must
give results with the smallest uncertainty attainable in a
given field of measurement, also with respect to the
long-term validity of the result. Being definitive or ab-
solute is, in a way, the potential of a method for being a
primary one. The advantage of the CCQM definition is
that it is more general and does not contain terms
which themselves must be defined.
In the following, existing methods are evaluated
with respect to their potential of being primary meth-
ods.
Gravimetry
A gravimetric analysis is usually carried out according
to the following principle: The analyte to be deter-
mined is separated from the sample in a weighable
form (e.g., by precipitation), and its mass or amount of
substance is calculated from the mass of the weighed
compound whose stoichiometric composition must be
exactly known. The measurement equation is very sim-
ple:
m
a
pf m
w
, (1)
m
a
being the mass of the analyte and m
w
that of the
weighed compound. The factor f depends only on mean
relative atomic masses (atomic weights) which are
usually known with sufficient accuracy. In most cases,
the desired final result is not the mass of the analyte in
a given sample but derived quantities like mass fraction
or amount-of-substance concentration. Calculating
such quantities from the initial mass measurement
usually is a straightforward process. Obviously, gravi-
metry is completely described and understood (for
problems and imperfections, see below), and no stand-
ard is needed of the quantity to be measured, for exam-
ple a reference material of known composition.
In this connection, the mass standard necessary for
calibrating the balance is a general standard and does
not count as a standard for solving the analytical task,
even if the mass of the analyte is the final result. It is
the mass of a distinct chemical species which is to be
determined, not a mass in general.
An important requirement for a method to be pri-
mary is complete knowledge of the uncertainty [3] of its
results. The uncertainty of gravimetric analyses is main-
ly caused by imperfections of the practical realisation of
the method. Chemical separations are never complete.
In the case of a precipitation reaction, some of the sub-
stance to be weighed is always lost in the filtrate due to
solubility, even if extremely low, and a small part of the
precipitate weighed does not belong to the substance in
question but is made up of other occluded and copreci-
pitated substances. Volatilisation of substance in the fi-
nal step of generating the compound to be weighed is
another imperfection. These deviations from the ideal
behaviour are usually small and can be corrected for by
use of one of the well-known sensitive instrumental
methods [4].
Another possible contribution to the uncertainty
must be taken into account if there is doubt whether
the reaction proceeds exactly stoichiometrically as ex-
pected. Thorough experimental investigation can clari-
fy this problem. As gravimetry as a classical method has
already been used for a long time, a great number of
well-characterised reactions are available.
If enough time, material and measurement equip-
ment are available, the corrections can be determined
with sufficient accuracy to make a complete uncertainty
statement at the highest metrological quality level. The
weighing steps (determination of the initial mass of the
sample, determination of the mass of the reaction prod-
uct) usually contribute minor uncertainty components.
An important correction always necessary here is the
air buoyancy correction. The inputs to the factor f in
Eq. 1, the atomic weights, are usually accurate enough.
In a few cases, like lead, where the isotopic composi-
tion varies considerably according to the origin of the
material and increases the uncertainty of the atomic
weight, f can make a discernible contribution to the un-
certainty. Relative combined standard uncertainties [3]
of down to below 10
4
have been achieved [5]. In gen-
eral, 10
3
can be expected if the method is used in a
356
metrologically correct way and at its full capability.
Gravimetry can therefore be regarded as a primary
method of measurement in chemical analysis. Because
of its high reliability and accuracy, gravimetry is used
for certifying SI-traceable reference materials [4] for
inorganic chemistry.
It is sometimes advantageous to use gravimetry in a
reverse mode: Instead of decomposing the sample, a
reference sample of similar composition is synthesised
by mixing known amounts of substance (via masses) of
the pure components, and compared with the sample
using an appropriate instrumental technique. In gas
analysis, for example, this approach is widely used. It is
also applicable in other fields of analysis [6] if the com-
ponents of the sample are known and available in pure
form and if homogeneous mixtures can be prepared.
This kind of gravimetry, i.e. the preparation of the
reference sample by weighing, is also a primary method
if used at the highest metrological level.
Most kinds of instrumental analytical methods, on
the contrary, do not count among the primary methods
even if of high precision. In instrumental analysis, a sig-
nal is usually produced in response to, for example, the
amount-of-substance concentration of an analyte, utilis-
ing a suitable measuring effect, and compared with the
signal produced by a reference material of known com-
position subjected to the same procedure. Given linear
response with equal slope in both cases, the ratio of the
two signals can be used to calculate the analyte concen-
tration. No measurement equation can, in general, be
written down. Any attempt to formulate a mathemati-
cal expression describing the signal of, for example, an
atomic emission spectrometer as a function of the
quantity to be measured shows that much more knowl-
edge of the usually complicated processes involved
than is available is necessary. The only way is by the
empirical determination of this relation, i.e. the calibra-
tion curve. In this way, the great majority of chemical
analyses are carried out, relying on the high precision,
the high speed, the high sensitivity and the versatility of
modern instrumental techniques. Accuracy, however,
can only be achieved by calibrating such secondary
methods with standards, meeting the important re-
quirement that the signal due to these has the same cal-
ibration curve parameters as the signal due to the ana-
lyte in the sample. Very often this requirement is not
fulfilled, which is well known as matrix effect.
Titrimetry
In titrimetry, the analyte is determined by measuring
the equivalent volume of titrant solution of known con-
centration. As with gravimetry, it is an important prere-
quisite for applying the method that the chemical reac-
tion used for the determination must proceed com-
pletely stoichiometrially. A great number of such reac-
tions are known. A characteristic feature of titrimetry is
that amounts of substance are directly obtained.
The measurement equation is:
n
a
pv
t
7 c
t
, (2)
where n
a
is amount of substance of analyte, and v
t
and
c
t
are volume and amount-of-substance concentration,
respectively, of the titrant. Titrimetry is closely related
to gravimetry, since c
t
is known from gravimetric pre-
paration. The method is obviously completely de-
scribed and understood. The result for n
a
is generally
used to calculate a compositional quantity of the origi-
nal sample, e.g. amount-of-substance concentration of
the analyte. A standard of this compositional quantity
is not required. The standards required are those of
mass and volume. The basic requirements for a primary
method are therefore met. It must not be overlooked
that the ultimate reference points of titrimetry are high-
purity substances, namely those from which the titrant
solutions are prepared. These do not, however, inva-
lidate titrimetry as a potentially primary method, be-
cause they can be dealt with in the same way as the
reference value in the above-mentioned example from
thermometry. As regards the uncertainty, similar con-
siderations as in gravimetry apply. The main contribu-
tions come from imperfections of realising the method
in practice. A typical error in titrimetry is associated
with the determination of the equivalence point. For
this and the other errors, corrections can be provided
with auxiliary methods whose accuracy depends on the
effort and outlay invested.
Combined relative standard uncertainties down to
10
3
can be achieved if the method is used to its full
metrological capability. Titrimetry is also used for the
certification of SI-traceable reference materials.
Coulometry
Coulometry is a particularly important primary method
of chemical analysis. Amounts of substance are directly
determined by electrical current and time measure-
ments in an electrochemical reaction. No reference to
specific pure substances is necessary; instead, reference
is made to the amount of substance of electrons. This
holds with the same accuracy as that with which the
Faraday constant is known. The current value
F p96 485.31 (1 B0,3 7 10
6
) C mol
1
is accurate
enough for any coulometric determination. The general
measurement equation is:
n
a
p
1
z7F
# I dt , (3)
where z is number of electrons exchanged per reaction
unit, I electrical current and t time. The method is com-
357
pletely described and understood. Standards of electri-
cal current, mass and time are required, but no stand-
ard of the quantity to be determined. The result for n
a
is used to calculate the compositional quantity de-
sired.
An important prerequisite is that the current mea-
sured solely originate from the reaction under consider-
ation; additional current-contributing processes must
not occur. This restricts the application of the method
to simple systems, e.g. purity determinations of sub-
stances.
Coulometry in chemical analysis is mainly carried
out in two variants: constant-current coulometry and
controlled-potential coulometry. Titration is mostly
used as the kind of implementation, with electrons
serving as titrant.
With this method also, the accuracy is limited due to
imperfections of the practical realisation. One of them
has already been mentioned: unwanted side reactions.
The limitations due to sample handling are similar to
those in gravimetry and titrimetry. As with the latter,
the end-point detection problem is also involved in
coulometric titration. Electrical potential measure-
ments using auxiliary electrodes are usually applied.
Again, errors can be corrected for using sensitive meth-
ods which themselves need not be primary. Combined
relative standard uncertainties as low as 2 7 10
5
can be
achieved with constant-current coulometric titration
[7].
The main field of application is the direct determina-
tion of the purity of substances to be used as high-level
references [7]. Unlike the usual way of determining
purity by summing up impurities, with coulometry the
abundance of the substance itself is directly deter-
mined, irrespective of the amount and kind of the im-
purities. There is no doubt that coulometry is a primary
method of chemical analysis.
Isotope dilution mass spectrometry (IDMS)
IDMS is a special version of an addition method in
which the known amount of substance of the analyte
added, the so-called spike, is the pure analyte in a dif-
ferent isotopic composition. The amount of substance
of the analyte to be determined is linked to the known
amount of substance of the spike via a measurement
equation (Eq. 4) containing only isotope abundance ra-
tios (isotope amount-of-substance ratios), which can be
measured with high accuracy using a mass spectromet-
er.
In detail, a known amount of substance of the spike,
generally determined by weighing, is added to the sam-
ple before any chemical treatment is started. Care is
taken that complete equilibration is achieved, i.e. that
the same isotopic distribution is reached in every spe-
cies of the analyte if there are more than one. Because
of the close similarity of the isotopes, the initial isotopic
ratio does not change throughout the whole chemical
treatment procedure which may be necessary, including
the mass spectrometric process, even if substance re-
covery is not complete in the intermediate steps.
In the following, an element determination in inor-
ganic analysis is considered as an example. For simplic-
ity of description, it is assumed that the element is
made up of two isotopes only. It is the abundance ratio
of these two isotopes of the element to be determined
which is used as the key to the analysis. This abundance
ratio (equal to the isotope amount-of-substance ratio in
a given substance portion) is measured with a mass
spectrometer in (1) the original sample, (2) the spike,
and (3) the mixture of sample and spike, after the same
pretreatment in all three cases.
The measurement equation in this case is
n
a
p
(R
s
PR
m
) (1cR
a
)
(R
m
PR
a
) (1cR
s
)
7n
s
, (4)
n
a
and n
s
being the amounts of substance of analyte and
spike, R
a
, R
s
and R
m
the isotope abundance ratios of
the two isotopes in the sample, the spike and the mix-
ture of sample and spike. The extension of the consid-
eration to the general case of multi-isotope elements is
straightforward. In all cases, the abundance ratio of two
selected isotopes is measured, i.e., the element must
have at least two isotopes.
The method is completely described and understood
on the basis of a measurement equation which can be
explicitly written down. The measurement is obviously
based on another material, the spike, which is used as a
reference. This does not, however, invalidate IDMS as
a potentially primary method, because the amount of
substance of the spike is itself determined using a pri-
mary method, namely gravimetry, and the amount of
substance of the analyte can be calculated from the
spike with an explicitly known equation. The situation
is similar to the example in thermometry mentioned
above.
With an ideal mass spectrometer, knowledge of the
R values in Eq. 4 could be taken for granted, since the
isotope intensity ratios measured would be equal to the
isotope abundances to a high degree of approximation,
because of the highly similar chemical and physical be-
haviour of the isotopes. This approximation is not val-
id, of course, for different elements which have, among
other differences, different ionisation potentials and
thus ionisation cross sections. The non-ideal behaviour
of real mass spectrometers, which shows up, for exam-
ple, in a mass bias (dependence of the signal on the
mass), even if the isotopes are close together on the
mass scale, can, in general, be corrected for using auxil-
iary methods. This does not devaluate the method but
limits its accuracy.
358
The accuracy achieved in the analytical result de-
pends on the kind of mass spectrometer more precise-
ly, on the kind of ionisation and mass separation used.
The properties of the mass spectrometer must be stable
and exactly known so that the appropriate corrections
can be applied. The accuracy of the total analytical pro-
cedure is usually limited by uncertainty components as-
sociated with the sample pretreatment in particular, if
many steps are involved. In general, IDMS yields more
accurate results than other methods, given the same de-
gree of analytical difficulty. Because of its insensitivity
to substance losses in the sample pretreatment stage,
IDMS particularly shows its superiority in analytical
tasks where complex matrices are involved. This is
what makes IDMS so versatile, at the same time retain-
ing high accuracy comparable to that of gravimetry and
titrimetry.
After these considerations it can finally be stated
that IDMS has all properties of a primary method in
chemical analysis. This statement is not invalidated by
the fact that IDMS can be used in variants in which its
primary capability is not fully used. This can be advan-
tageous if, for example, the spike is not completely
characterised, but a high-purity substance which can be
used as a laboratory standard is available instead. In
such a case, the spike is essentially used as an indicator,
and the analyte is determined iteratively [8]. In organic
analysis, application of IDMS mostly relies on deuter-
ated or
13
C-labelled compounds as spikes. Because of
the higher relative mass separation of
13
C and
12
C and,
in particular, D and H compared with, for example,
206
Pb and
208
Pb, differences in behaviour of the isotopic
substances are more likely to occur, thus requiring
larger corrections associated with higher uncertainties.
A special version of IDMS in organic analysis, which
includes a combustion step converting analyte and
spike into a mixture of
12
CO
2
and
13
CO
2
which is then
analysed using a dedicated mass spectrometer, can be
expected to yield optimum results [9].
Other methods
Methods using colligative properties like freezing-point
depression or boiling-point elevation for amount-of-
substance determinations have, in principle, also the
potential of being primary methods. The basic require-
ments at least are fulfilled. Whether highest metrologi-
cal quality can be reached depends on the results of in-
vestigations currently underway.
Optical absorption spectrometry is also a candidate
for a primary method. The measurement equation:
t(l) pexp [Pk(l) c l], (5)
often called Lambert-Beers law, is valid under certain
conditions. The lower the concentration of the absorb-
ing centres (e.g. molecules) in the light path and the
narrower the observation band width compared with
the width of the absorption feature (e.g. spectral line or
band) of the substance to be determined, the better the
compliance with these conditions. In Eq. 5, t(l) is the
transmittance of the (homogeneous) optical medium
containing the analyte, k(l) the concentration-related
absorption coefficient, c the concentration of the ana-
lyte to be determined and l the optical absorption path
length. If k(l) is known from independent primary
measurements with known (small) uncertainty, optical-
absorption spectrometry meets the essential require-
ments of a primary method. The overall uncertainty at-
tainable depends on the perfection in which Eq. 5 can
be realised in practice. Important requirements are: ac-
curate knowledge of the effective path length l and
complete symmetry between the two radiative power
measurements constituting t(l), namely the one with
absorbing sample and the one without absorbing sam-
ple in the light path. The symmetry requirement means
here that it must be possible to exchange the sample for
the non-absorbing medium keeping everything else
constant. This is a very demanding requirement.
An important application of optical absorption spec-
trometry is ozone determination in ground-level air and
in the stratosphere using optical absorption in the UV
spectral range. Eq. 5 can be regarded as being applica-
ble here (very low concentrations, between 1 and
10 mmol/m
3
, narrow observation band width due to us-
ing the 254-nm Hg emission line, broad UV absorption
band of ozone with maximum at 255 nm), and the ab-
sorption coefficient is known, at least as a conventional
true value [10]. The measurement instrumentation for
ozone determination has reached a high degree of so-
phistication. Because of its high reactivity, ozone pres-
ents special handling problems even in this low concen-
tration range, so that it is difficult to use optical absorp-
tion spectrometry, being a primary method in principle,
to its full capability in this special case.
Establishment of traceability of chemical
measurements to the SI units using primary methods
As mentioned already in the introduction, primary
methods of measurement serve the important purpose
of establishing traceability of measurement results of
all kinds of physical quantities to the corresponding SI
units. Chemical measurement results, in particular, can
be made traceable to the corresponding SI units using
the primary methods described above to link up inter-
mediate reference points with the SI units. With respect
to such reference points instrumental analytical tech-
niques are calibrated which are nowadays mostly used
for carrying out chemical analyses at the working level,
because of their high sensitivity, speed, versatility and
359
Fig. 1 Possible ways of realising traceability of chemical measure-
ments to the SI units using primary methods and intermediate ref-
erence points
precision and hence cost-advantage, but which are
themselves usually not primary methods. In this way, a
traceability system can be built up, at least for the most
important analytical measurement tasks. Figure 1
shows how this goal can be achieved.
Four routes are distinguished in Fig. 1. Starting on
the left side, reference materials of chemical composi-
tion are shown as intermediate reference points. Refer-
ence materials are most frequently used as measure-
ment standards in chemical analysis. If these are linked
up with the SI units of the corresponding compositional
quantities by means of primary methods and, at the
same time, sufficiently match the sample matrix, the
traceability chain is complete. For many analytical
measurement tasks, local or sectorial comparability is
sufficient. In such cases, of course, traceability to the SI
is not required, and reference materials based on con-
sensus values, for example, can be used as reference
points. But even in such cases, reference materials can-
not solve every analytical problem. Besides matrix mis-
match, mentioned already, limits due to substance in-
stabilities are set, in which case reference materials can-
not be prepared.
Other measurement standards, for example in the
form of measurement devices (including procedures)
which can provide or reproduce chemical compositions
with high accuracy, can be used as intermediate refer-
ence points in such cases. The ozone spectrometer
mentioned above is given as an example in the second
route of Fig. 1. Dynamic calibration gas-generating de-
vices based on primary flow measurement methods are
another example. Reference laboratories specialised
for distinct measurement tasks and themselves tracea-
ble to the SI units via primary methods serve as inter-
mediate reference points in the third traceability route.
Because of the high complexity of many chemical
measurement tasks, specialised laboratories will play an
increasingly important role as reference points. In clini-
cal chemistry, for example, reference laboratories for
many analytical measurands have been established for
a long time. Traceability to the SI units, at least for the
well-defined analytes, is of particular importance and is
increasingly sought by these laboratories.
The fourth route, finally, exemplifies cases in which
a chemical laboratory (in the field) is able to establish a
direct link to the SI units using a primary method for a
particular chemical measurement problem. Of course,
this is not the usual application of a primary method.
Primary methods will mainly be reserved for linking up
reference points to the SI units (e.g. reference materi-
als), thus providing access to the SI units for the work-
ing level in a convenient and economical way, accord-
ing to the principle of division of labour. Direct appli-
cation of primary methods is open, however, to every
well-equipped and experienced laboratory.
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