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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 Abstract Primary methods of methods according to a general


Accepted: 9 August 1997 measurement have a central func- definition of primary methods re-
tion in metrology. They are an es- cently given by the Comit Consul-
sential component in the realisa- tatif pour la Quantit de Matire
tion of the SI units and therefore (CCQM). Optical absorption spec-
are indispensable for establishing trometry and methods based on
traceability of measurements of all colligative properties are also con-
kinds of physical quantities to the sidered. A general scheme for es-
corresponding SI units. This is also tablishing traceability of chemical
true for chemical analysis. Gravi- measurements to the SI units using
metry, titrimetry, coulometry, and primary methods is discussed.
W. Richter (Y)
Physikalisch-Technische Bundesanstalt,
isotope dilution mass spectrometry
D-Braunschweig, Germany (IDMS) are evaluated with regard Key words Traceability to SI 7
Tel.: c49-(0)531-592-3200 to their potential to be primary Primary methods 7 Comparability

tie a field measurement to the corresponding unit in the


Introduction shortest way possible.

With increasing globalisation of human activities, the


comparability (more precisely: metrological equival- Definition and general description
ence) of measurement results has become an important
issue. Comparability requires traceability to common The Comit Consultatif pour la Quantit de Matire
references; worldwide comparability requires traceabil- (CCQM), the new metrology body under the Conven-
ity of measurement results to the SI units, the only gen- tion du Mtre, which is responsible for all issues relat-
erally accepted reference frame available. This is also ing to the accuracy of chemical measurements and their
true for chemical measurements (measurements for de- traceability to the SI units, has recently given a general
termining chemical composition), the more so as cross- definition of a primary method of measurement [1].
frontier activities in environmental protection, health This reads:
care and trade rely on credible and, hence, accepted A primary method of measurement is a method
analytical results. having the highest metrological qualities, whose opera-
Traceability to the SI units is ultimately accom- tion is completely described and understood, for which
plished by primary methods of measurement. Primary a complete uncertainty statement can be written down
methods tie the realisation of an SI unit to its defini- in terms of SI units, and whose results are, therefore,
tion, or, in other words: the value of a primary meas- accepted without reference to a standard of the quanti-
urement standard of a physical quantity is determined ty being measured.
using a primary method. This is the usual application of The statement that the result of a primary method is
a primary method in metrology in general, at the top of accepted without reference to a standard of the quanti-
the traceability chain. But it can also be used to directly ty being measured is interpreted by the CCQM to mean
355

that for a given quantity, X, the equation describing the usually known with sufficient accuracy. In most cases,
measurement method must include no unknown func- the desired final result is not the mass of the analyte in
tions of X of significant magnitude. The determination a given sample but derived quantities like mass fraction
of X in terms of a reference value Xref, itself deter- or amount-of-substance concentration. Calculating
mined by a primary method, does not invalidate the such quantities from the initial mass measurement
method as being primary. usually is a straightforward process. Obviously, gravi-
An example of a method which is not invalidated as metry is completely described and understood (for
a primary method by using a reference value of the problems and imperfections, see below), and no stand-
same quantity is temperature measurement with a spec- ard is needed of the quantity to be measured, for exam-
tral radiation thermometer, in which use is made of a ple a reference material of known composition.
reference value determined by gas thermometry [2]. In this connection, the mass standard necessary for
The value to be measured is linked to the reference val- calibrating the balance is a general standard and does
ue (itself determined by a primary method) via the not count as a standard for solving the analytical task,
Planck equation, which completely describes the opera- even if the mass of the analyte is the final result. It is
tion of the radiation thermometer. the mass of a distinct chemical species which is to be
Obviously, such cases of complete calculability are determined, not a mass in general.
rare in chemical analysis. Instead, empirical determina- An important requirement for a method to be pri-
tion of the measurement function by calibration is the mary is complete knowledge of the uncertainty [3] of its
common way. There are, however, a few analytical results. The uncertainty of gravimetric analyses is main-
methods which have the potential for being used as pri- ly caused by imperfections of the practical realisation of
mary methods. These are, for example, gravimetry, ti- the method. Chemical separations are never complete.
trimetry, coulometry and isotopic dilution mass spec- In the case of a precipitation reaction, some of the sub-
trometry (IDMS), according to a proposal of the stance to be weighed is always lost in the filtrate due to
CCQM. solubility, even if extremely low, and a small part of the
The terms definitive or absolute are often used precipitate weighed does not belong to the substance in
to characterise methods in chemical analysis which question but is made up of other occluded and copreci-
meet the basic requirements to be fulfilled by primary pitated substances. Volatilisation of substance in the fi-
methods according to the CCQM definition. What this nal step of generating the compound to be weighed is
definition adds is the requirement that the method be another imperfection. These deviations from the ideal
of highest metrological quality. This means that it must behaviour are usually small and can be corrected for by
give results with the smallest uncertainty attainable in a use of one of the well-known sensitive instrumental
given field of measurement, also with respect to the methods [4].
long-term validity of the result. Being definitive or ab- Another possible contribution to the uncertainty
solute is, in a way, the potential of a method for being a must be taken into account if there is doubt whether
primary one. The advantage of the CCQM definition is the reaction proceeds exactly stoichiometrically as ex-
that it is more general and does not contain terms pected. Thorough experimental investigation can clari-
which themselves must be defined. fy this problem. As gravimetry as a classical method has
In the following, existing methods are evaluated already been used for a long time, a great number of
with respect to their potential of being primary meth- well-characterised reactions are available.
ods. If enough time, material and measurement equip-
ment are available, the corrections can be determined
with sufficient accuracy to make a complete uncertainty
Gravimetry
statement at the highest metrological quality level. The
A gravimetric analysis is usually carried out according weighing steps (determination of the initial mass of the
to the following principle: The analyte to be deter- sample, determination of the mass of the reaction prod-
mined is separated from the sample in a weighable uct) usually contribute minor uncertainty components.
form (e.g., by precipitation), and its mass or amount of An important correction always necessary here is the
substance is calculated from the mass of the weighed air buoyancy correction. The inputs to the factor f in
compound whose stoichiometric composition must be Eq. 1, the atomic weights, are usually accurate enough.
exactly known. The measurement equation is very sim- In a few cases, like lead, where the isotopic composi-
ple: tion varies considerably according to the origin of the
material and increases the uncertainty of the atomic
ma p f mw , (1)
weight, f can make a discernible contribution to the un-
ma being the mass of the analyte and mw that of the certainty. Relative combined standard uncertainties [3]
weighed compound. The factor f depends only on mean of down to below 10 4 have been achieved [5]. In gen-
relative atomic masses (atomic weights) which are eral, 10 3 can be expected if the method is used in a
356

metrologically correct way and at its full capability. pletely stoichiometrially. A great number of such reac-
Gravimetry can therefore be regarded as a primary tions are known. A characteristic feature of titrimetry is
method of measurement in chemical analysis. Because that amounts of substance are directly obtained.
of its high reliability and accuracy, gravimetry is used The measurement equation is:
for certifying SI-traceable reference materials [4] for
na p vt 7 ct , (2)
inorganic chemistry.
It is sometimes advantageous to use gravimetry in a where na is amount of substance of analyte, and vt and
reverse mode: Instead of decomposing the sample, a ct are volume and amount-of-substance concentration,
reference sample of similar composition is synthesised respectively, of the titrant. Titrimetry is closely related
by mixing known amounts of substance (via masses) of to gravimetry, since ct is known from gravimetric pre-
the pure components, and compared with the sample paration. The method is obviously completely de-
using an appropriate instrumental technique. In gas scribed and understood. The result for na is generally
analysis, for example, this approach is widely used. It is used to calculate a compositional quantity of the origi-
also applicable in other fields of analysis [6] if the com- nal sample, e.g. amount-of-substance concentration of
ponents of the sample are known and available in pure the analyte. A standard of this compositional quantity
form and if homogeneous mixtures can be prepared. is not required. The standards required are those of
This kind of gravimetry, i.e. the preparation of the mass and volume. The basic requirements for a primary
reference sample by weighing, is also a primary method method are therefore met. It must not be overlooked
if used at the highest metrological level. that the ultimate reference points of titrimetry are high-
Most kinds of instrumental analytical methods, on purity substances, namely those from which the titrant
the contrary, do not count among the primary methods solutions are prepared. These do not, however, inva-
even if of high precision. In instrumental analysis, a sig- lidate titrimetry as a potentially primary method, be-
nal is usually produced in response to, for example, the cause they can be dealt with in the same way as the
amount-of-substance concentration of an analyte, utilis- reference value in the above-mentioned example from
ing a suitable measuring effect, and compared with the thermometry. As regards the uncertainty, similar con-
signal produced by a reference material of known com- siderations as in gravimetry apply. The main contribu-
position subjected to the same procedure. Given linear tions come from imperfections of realising the method
response with equal slope in both cases, the ratio of the in practice. A typical error in titrimetry is associated
two signals can be used to calculate the analyte concen- with the determination of the equivalence point. For
tration. No measurement equation can, in general, be this and the other errors, corrections can be provided
written down. Any attempt to formulate a mathemati- with auxiliary methods whose accuracy depends on the
cal expression describing the signal of, for example, an effort and outlay invested.
atomic emission spectrometer as a function of the Combined relative standard uncertainties down to
quantity to be measured shows that much more knowl- 10 3 can be achieved if the method is used to its full
edge of the usually complicated processes involved metrological capability. Titrimetry is also used for the
than is available is necessary. The only way is by the certification of SI-traceable reference materials.
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, Coulometry
the high speed, the high sensitivity and the versatility of
modern instrumental techniques. Accuracy, however, Coulometry is a particularly important primary method
can only be achieved by calibrating such secondary of chemical analysis. Amounts of substance are directly
methods with standards, meeting the important re- determined by electrical current and time measure-
quirement that the signal due to these has the same cal- ments in an electrochemical reaction. No reference to
ibration curve parameters as the signal due to the ana- specific pure substances is necessary; instead, reference
lyte in the sample. Very often this requirement is not is made to the amount of substance of electrons. This
fulfilled, which is well known as matrix effect. holds with the same accuracy as that with which the
Faraday constant is known. The current value
F p 96 485.31 (1 B 0,3 7 10 6) C mol 1 is accurate
Titrimetry enough for any coulometric determination. The general
measurement equation is:
In titrimetry, the analyte is determined by measuring 1
the equivalent volume of titrant solution of known con- na p # I dt , (3)
z7F
centration. As with gravimetry, it is an important prere-
quisite for applying the method that the chemical reac- where z is number of electrons exchanged per reaction
tion used for the determination must proceed com- unit, I electrical current and t time. The method is com-
357

pletely described and understood. Standards of electri- cies of the analyte if there are more than one. Because
cal current, mass and time are required, but no stand- of the close similarity of the isotopes, the initial isotopic
ard of the quantity to be determined. The result for na ratio does not change throughout the whole chemical
is used to calculate the compositional quantity de- treatment procedure which may be necessary, including
sired. the mass spectrometric process, even if substance re-
An important prerequisite is that the current mea- covery is not complete in the intermediate steps.
sured solely originate from the reaction under consider- In the following, an element determination in inor-
ation; additional current-contributing processes must ganic analysis is considered as an example. For simplic-
not occur. This restricts the application of the method ity of description, it is assumed that the element is
to simple systems, e.g. purity determinations of sub- made up of two isotopes only. It is the abundance ratio
stances. of these two isotopes of the element to be determined
Coulometry in chemical analysis is mainly carried which is used as the key to the analysis. This abundance
out in two variants: constant-current coulometry and ratio (equal to the isotope amount-of-substance ratio in
controlled-potential coulometry. Titration is mostly a given substance portion) is measured with a mass
used as the kind of implementation, with electrons spectrometer in (1) the original sample, (2) the spike,
serving as titrant. and (3) the mixture of sample and spike, after the same
With this method also, the accuracy is limited due to pretreatment in all three cases.
imperfections of the practical realisation. One of them The measurement equation in this case is
has already been mentioned: unwanted side reactions. (RsPRm) (1cRa)
The limitations due to sample handling are similar to na p 7 ns , (4)
those in gravimetry and titrimetry. As with the latter, (RmPRa) (1cRs)
the end-point detection problem is also involved in na and ns being the amounts of substance of analyte and
coulometric titration. Electrical potential measure- spike, Ra, Rs and Rm the isotope abundance ratios of
ments using auxiliary electrodes are usually applied. the two isotopes in the sample, the spike and the mix-
Again, errors can be corrected for using sensitive meth- ture of sample and spike. The extension of the consid-
ods which themselves need not be primary. Combined eration to the general case of multi-isotope elements is
relative standard uncertainties as low as 2 7 10 5 can be straightforward. In all cases, the abundance ratio of two
achieved with constant-current coulometric titration selected isotopes is measured, i.e., the element must
[7]. have at least two isotopes.
The main field of application is the direct determina- The method is completely described and understood
tion of the purity of substances to be used as high-level on the basis of a measurement equation which can be
references [7]. Unlike the usual way of determining explicitly written down. The measurement is obviously
purity by summing up impurities, with coulometry the based on another material, the spike, which is used as a
abundance of the substance itself is directly deter- reference. This does not, however, invalidate IDMS as
mined, irrespective of the amount and kind of the im- a potentially primary method, because the amount of
purities. There is no doubt that coulometry is a primary substance of the spike is itself determined using a pri-
method of chemical analysis. 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
Isotope dilution mass spectrometry (IDMS) is similar to the example in thermometry mentioned
above.
IDMS is a special version of an addition method in With an ideal mass spectrometer, knowledge of the
which the known amount of substance of the analyte R values in Eq. 4 could be taken for granted, since the
added, the so-called spike, is the pure analyte in a dif- isotope intensity ratios measured would be equal to the
ferent isotopic composition. The amount of substance isotope abundances to a high degree of approximation,
of the analyte to be determined is linked to the known because of the highly similar chemical and physical be-
amount of substance of the spike via a measurement haviour of the isotopes. This approximation is not val-
equation (Eq. 4) containing only isotope abundance ra- id, of course, for different elements which have, among
tios (isotope amount-of-substance ratios), which can be other differences, different ionisation potentials and
measured with high accuracy using a mass spectromet- thus ionisation cross sections. The non-ideal behaviour
er. of real mass spectrometers, which shows up, for exam-
In detail, a known amount of substance of the spike, ple, in a mass bias (dependence of the signal on the
generally determined by weighing, is added to the sam- mass), even if the isotopes are close together on the
ple before any chemical treatment is started. Care is mass scale, can, in general, be corrected for using auxil-
taken that complete equilibration is achieved, i.e. that iary methods. This does not devaluate the method but
the same isotopic distribution is reached in every spe- limits its accuracy.
358

The accuracy achieved in the analytical result de- ing centres (e.g. molecules) in the light path and the
pends on the kind of mass spectrometer more precise- narrower the observation band width compared with
ly, on the kind of ionisation and mass separation used. the width of the absorption feature (e.g. spectral line or
The properties of the mass spectrometer must be stable band) of the substance to be determined, the better the
and exactly known so that the appropriate corrections compliance with these conditions. In Eq. 5, t(l) is the
can be applied. The accuracy of the total analytical pro- transmittance of the (homogeneous) optical medium
cedure is usually limited by uncertainty components as- containing the analyte, k(l) the concentration-related
sociated with the sample pretreatment in particular, if absorption coefficient, c the concentration of the ana-
many steps are involved. In general, IDMS yields more lyte to be determined and l the optical absorption path
accurate results than other methods, given the same de- length. If k(l) is known from independent primary
gree of analytical difficulty. Because of its insensitivity measurements with known (small) uncertainty, optical-
to substance losses in the sample pretreatment stage, absorption spectrometry meets the essential require-
IDMS particularly shows its superiority in analytical ments of a primary method. The overall uncertainty at-
tasks where complex matrices are involved. This is tainable depends on the perfection in which Eq. 5 can
what makes IDMS so versatile, at the same time retain- be realised in practice. Important requirements are: ac-
ing high accuracy comparable to that of gravimetry and curate knowledge of the effective path length l and
titrimetry. complete symmetry between the two radiative power
After these considerations it can finally be stated measurements constituting t(l), namely the one with
that IDMS has all properties of a primary method in absorbing sample and the one without absorbing sam-
chemical analysis. This statement is not invalidated by ple in the light path. The symmetry requirement means
the fact that IDMS can be used in variants in which its here that it must be possible to exchange the sample for
primary capability is not fully used. This can be advan- the non-absorbing medium keeping everything else
tageous if, for example, the spike is not completely constant. This is a very demanding requirement.
characterised, but a high-purity substance which can be An important application of optical absorption spec-
used as a laboratory standard is available instead. In trometry is ozone determination in ground-level air and
such a case, the spike is essentially used as an indicator, in the stratosphere using optical absorption in the UV
and the analyte is determined iteratively [8]. In organic spectral range. Eq. 5 can be regarded as being applica-
analysis, application of IDMS mostly relies on deuter- ble here (very low concentrations, between 1 and
ated or 13C-labelled compounds as spikes. Because of 10 mmol/m 3, narrow observation band width due to us-
the higher relative mass separation of 13C and 12C and, ing the 254-nm Hg emission line, broad UV absorption
in particular, D and H compared with, for example, band of ozone with maximum at 255 nm), and the ab-
206
Pb and 208Pb, differences in behaviour of the isotopic sorption coefficient is known, at least as a conventional
substances are more likely to occur, thus requiring true value [10]. The measurement instrumentation for
larger corrections associated with higher uncertainties. ozone determination has reached a high degree of so-
A special version of IDMS in organic analysis, which phistication. Because of its high reactivity, ozone pres-
includes a combustion step converting analyte and ents special handling problems even in this low concen-
spike into a mixture of 12CO2 and 13CO2 which is then tration range, so that it is difficult to use optical absorp-
analysed using a dedicated mass spectrometer, can be tion spectrometry, being a primary method in principle,
expected to yield optimum results [9]. to its full capability in this special case.

Other methods Establishment of traceability of chemical


measurements to the SI units using primary methods
Methods using colligative properties like freezing-point
depression or boiling-point elevation for amount-of- As mentioned already in the introduction, primary
substance determinations have, in principle, also the methods of measurement serve the important purpose
potential of being primary methods. The basic require- of establishing traceability of measurement results of
ments at least are fulfilled. Whether highest metrologi- all kinds of physical quantities to the corresponding SI
cal quality can be reached depends on the results of in- units. Chemical measurement results, in particular, can
vestigations currently underway. be made traceable to the corresponding SI units using
Optical absorption spectrometry is also a candidate the primary methods described above to link up inter-
for a primary method. The measurement equation: mediate reference points with the SI units. With respect
to such reference points instrumental analytical tech-
t (l) p exp [Pk (l) c l], (5)
niques are calibrated which are nowadays mostly used
often called Lambert-Beers law, is valid under certain for carrying out chemical analyses at the working level,
conditions. The lower the concentration of the absorb- because of their high sensitivity, speed, versatility and
359

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 Fig. 1 Possible ways of realising traceability of chemical measure-
same time, sufficiently match the sample matrix, the ments to the SI units using primary methods and intermediate ref-
traceability chain is complete. For many analytical erence points
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 measurement tasks, specialised laboratories will play an
points. But even in such cases, reference materials can- increasingly important role as reference points. In clini-
not solve every analytical problem. Besides matrix mis- cal chemistry, for example, reference laboratories for
match, mentioned already, limits due to substance in- many analytical measurands have been established for
stabilities are set, in which case reference materials can- a long time. Traceability to the SI units, at least for the
not be prepared. well-defined analytes, is of particular importance and is
Other measurement standards, for example in the increasingly sought by these laboratories.
form of measurement devices (including procedures) The fourth route, finally, exemplifies cases in which
which can provide or reproduce chemical compositions a chemical laboratory (in the field) is able to establish a
with high accuracy, can be used as intermediate refer- direct link to the SI units using a primary method for a
ence points in such cases. The ozone spectrometer particular chemical measurement problem. Of course,
mentioned above is given as an example in the second this is not the usual application of a primary method.
route of Fig. 1. Dynamic calibration gas-generating de- Primary methods will mainly be reserved for linking up
vices based on primary flow measurement methods are reference points to the SI units (e.g. reference materi-
another example. Reference laboratories specialised als), thus providing access to the SI units for the work-
for distinct measurement tasks and themselves tracea- ing level in a convenient and economical way, accord-
ble to the SI units via primary methods serve as inter- ing to the principle of division of labour. Direct appli-
mediate reference points in the third traceability route. cation of primary methods is open, however, to every
Because of the high complexity of many chemical well-equipped and experienced laboratory.

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