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 metrologia

Toward a revival of classical analysis

C. M. Beck II

Abstract. Among the analytical methods used to determine chemical composition, there are two special methods
based on reaction chemistry. These are gravimetry and titrimetry, and taken together they are called classical
analysis. They are special because they lead directly to independent values of chemical quantities expressed in SI
units. Gravimetry and titrimetry can be performed in such a way that their operation is completely understood, and
all significant sources of error in the measurement process can be evaluated and expressed in SI units together with
a complete uncertainty budget. Such chemical measurements are metrologically valid and stand alone. They have
no need to be compared with a reference material of the quantity being measured and therefore are called definitive
or primary methods. In this paper the basic equations and terms of gravimetry and titrimetry are discussed, together
with detailed examples of each. This is followed by a discussion of the errors associated with gravimetry and
titrimetry, and instrumental techniques that can be used for evaluating these errors. There is also a discussion of
the uncertainties associated with both systematic and random errors in gravimetry and titrimetry. The paper is
underpinned by historical sketches of several important issues and scientists connected with the development of
classical analysis. A case is made for a revival of the use of classical analysis in chemical metrology, together
with some suggestions as to how such a revival might be implemented.

Introduction reactions) involving that elementary chemical entity.

Among the analytical methods used to determine
chemical composition, there are two special methods
based on reaction chemistry. These are gravimetry
and titrimetry, and taken together they are called
classical analysis. They are special because they lead
directly to independent values of chemical quantities
expressed in SI units. Gravimetry and titrimetry can
be performed in such a way that their operation is
completely understood, and all significant sources of
error in the measurement process can be expressed in
SI units together with a complete uncertainty budget.
Such chemical measurements are metrologically sound
and stand alone. They have no need to be compared with
a reference material of the quantity being measured, and
therefore are called definitive or primary methods.
Part 1: Gravimetry
1.1 Basic equations and terms of gravimetry
Gravimetry is the determination of the amount of
substance of an elementary chemical entity through
the measurement of the mass of an insoluble
product of a stoichiometric chemical reaction (or
C. M. Beck II: Standard Reference Materials Program, National
Institute of Standards and Technology, Gaithersburg, MD
20899 USA.
In gravimetry, the general equation describing the
measurement is
(1)
where
d = the amount of substance of the elementary
chemical entity being determined, which may be
an element (e.g. Al), an ion (e.g. Ca2+ ), a radical
(e.g. SO ), or a compound (e.g. NH3 ).
w = the amount of substance of the insoluble
elementary chemical entity whose mass is being
determined, which may be: a gas evolved from
a heated solution, a gas evolved from an ignited
or fused solid, a non-volatile solid residue from a
low temperature volatilization or high-temperature
ignition, or, as it is in most cases, a precipitate
formed from an aqueous solution.
and
a, b = small whole integers appearing in the stoichio-
metric chemical reaction (or reactions) which
define the stoichiometric relationship between the
elementary chemical entity being determined and
the elementary chemical entity being weighed.
These small whole integers arise directly from
the law of definite proportions, which was initially
suspected by chemists at the end of the eighteenth
century and was brought into sharp focus by

Metrologia, 1997, 34, 19-30 19

C. M. Beck II
Stanislao Cannizzaro (1826-1910) in 1860 with
this statement: “The different quantities of the
same element contained in different molecules are
all whole multiples of one and the same quantity,
which, always being entire, has the right to be
called an atom” [1].
In addition to being stoichiometric, the reaction must
proceed in only one manner (i.e. reactions other than the
one indicated by the equation must not occur), and the
reaction must proceed as completely as possible in the
direction of the precipitate (i.e. the solubility-product
constant of the precipitate must be very small).
It can be seen from (1) that gravimetry is based
on the amount of substance of chemical entities
reacting and combining in simple proportions of
numbers. However, the classical analyst has no way
of determining amount of substance directly. Instead,
the analyst must determine the mass of a chemical entity
(which does not take into account the particulate nature
of that chemical entity) and then “correct” that mass by
dividing it by its molar mass. In this way, numbers are
obtained which are proportional to the simple ratios in
which atoms, ions, and molecules react. Applying this
concept, (1) becomes
(2)
where
d = mass of the elementary chemical entity being
determined;
= mass of the elementary chemical entity being
w
weighed;
and
(d) = molar mass of the elementary chemical entity
being determined;
(w) = molar mass of the elementary chemical entity
being weighed.
Rearranging (2) gives
(3)
or
(4)
where
(5)
Equation (5) is the definition of what analytical chemists
call the gravimetric factor.
20
1.2 Basic example of a gravimetric determination
Consider the following example of a gravimetric
determination. Suppose it is desired to assay an aqueous
solution of K2 SO4 for SO . The SO contained in
a known mass of the K2 SO4 solution is precipitated as
BaSO4 by adding a dilute HCl solution containing an
amount of substance of dissolved BaCl2 in excess of
that needed to complete the precipitation. The resulting
BaSO4 precipitate is separated from the solution by
filtration. The BaSO4 precipitate is dried, ignited to
constant weight at 1100 C, and its mass is determined.
The chemical reaction is
(r-1)
It can be seen that one SO in the original
sample matrix produces one BaSO4 “molecule”, and
consequently both a and b are unity. Therefore the
gravimetric factor, f, for this example is
(6)
Knowing both the gravimetric factor and the mass
of BaSO4 produced, the mass of SO in the specimen
can be calculated using (4). The mass fraction of SO
in the sample is
(7)
The amount of substance of SO in the sample
appears as a natural consequence of its known mass
and relative molecular mass:
(8)
1.3 Sources of error in gravimetry
In order to illustrate sources of error in gravimetry, it
is helpful to consider briefly some topics in the history
of gravimetry and, in particular, the quest for relative
atomic masses by gravimetry that went on from the late
1850s to the 1930s.
By the late 1850s the development of classical
analysis had reached an impasse because of the
confusion over the nominal values of relative atomic
masses. Chemists had no way of knowing if the
nominal atomic mass of H was 1 or 2; or that of
C was 6 or 12; or that of K was 32 or 64. Nominal
relative atomic masses could have been determined
if correct stoichiometric formulas had been known.
Conversely, correct stoichiometric formulas could have
been determined if nominal relative atomic masses had
been known. The chemists of that era faced the problem
of simultaneously determining both, and both were
unknown. Further confounding the problem was the
diatomic form of the common gases H2 , N2 , O2 , and Cl2 ,
Metrologia, 1997, 34, 19-30

which presented the enigma of 1 volume of hydrogen
gas combining with 1 volume of chlorine gas to give
2 volumes of hydrogen chloride gas. By 1860 relative
atomic mass tables varied from country to country, and
in some cases from laboratory to laboratory.
That this difficult and multilayered problem was
solved as early as 1860 is one of the triumphs of
the human mind [2-5]. Although Amedeo Avogadro
(1776-1856) had proposed the correct solution as early
as 1811, confusion reigned until Friedrich August
Kekulé (1829-1896) invited chemists to an international
chemical congress at Karlsruhe, Germany, in 1860
[6]. Stanislao Cannizzaro, a young professor from
the University of Genoa, was one of the delegates
to this congress. For some time he had realized
the correctness of Avogadro’s hypothesis in resolving
the problems surrounding relative atomic masses, but
his 1858 paper [7] had gone unnoticed. Despite his
skilful and passionate presentations at the congress,
no agreement was reached. Fortunately, a colleague
of Cannizzaro’s distributed copies of his paper to
the delegates as they departed. This paper showed
how Avogadro’s hypothesis could be used to establish
the relative molecular mass of a gaseous compound.
Moreover, it demonstrated that the relative atomic mass
of an element could be determined by comparing the
vapour densities of a series of gaseous compounds
containing that element. Julius Lothar Meyer (1830-
1895) and Dmitri Ivanovitch Mendeléev (1834-1907)
read the paper on their journey home, and both
were immediately convinced. The rest of the scientific
world followed quickly. It is difficult to overestimate
the impact of the events surrounding the Karlsruhe
congress. Without the insight that both Meyer and
Mendeléev gained from Cannizzaro’s paper, it is
doubtful that they independently would have gone on
to work out the periodic table as early as 1869. The
confusion over the nominal values for relative atomic
masses disappeared almost overnight, and chemists
were able to write the correct stoichiometric equations
for the reactions they were using in their gravimetric
assays.
With the problem of the nominal values of relative
atomic masses solved, the next issue was to obtain
accurate values for them. In the years just after
the Karlsruhe congress, Jean Servias Stas (1813-
1891) determined the relative atomic masses of twelve
elements, and his values were considered to be of such
high quality that their accuracy went unquestioned for
several decades. Although Stas was a careful analyst
who far outdistanced his predecessors, there were
significant errors in his work which he could not have
been aware of because he worked some thirty years
before the principles of physical chemistry generally
were understood.
It remained for Theodore William Richards (1868-
1928) to bring to maturity the determination of relative
atomic masses by gravimetry. He accomplished this
Metrologia, 1997, 34, 19-30
Toward a revival of classical analysis
by bringing to the task not only his extraordinary
genius as an experimentalist, but also his developing
knowledge of the latest insights from the new physical
chemistry which was emerging in Europe at that time.
Richards entered Harvard as the youngest member of
the Senior class in 1885, where he worked under
Josiah Parsons Cooke (1827-1894), revising the relative
atomic masses of hydrogen and copper. He earned his
Ph.D. under Cooke in 1888, and on the merits of
his doctoral dissertation, he won a fellowship for a
year of travel and study in Europe where he received
additional exposure to the important new developments
in physical chemistry. Returning to the United States
in 1889, he joined the chemistry faculty at Harvard
where he continued work on the determination of
relative atomic masses. He was granted a sabbatical
in 1895, and spent a semester with Wilhelm Ostwald
(1853-1932) at Leipzig and another with Walter Nernst
(1864-1941) at Göttingen, strengthening his knowledge
of the new physical chemistry. Richards began to realize
the seriousness of errors caused by the adsorption of
gases and retention of water in a solid substance. To
evaluate (and in some cases eliminate) these errors,
he developed a special weighing tube which made
it possible for him to fuse a substance in a quartz
boat under one or more controlled atmospheres and
then place that substance in a weighing bottle under
anhydrous conditions [8]. Richards also realized that
additional serious errors were caused by the occlusion
and coprecipitation of other substances in a precipitate
made from aqueous solution, and also by the solubility-
product loss of that precipitate into the supernatant
solution. To investigate these errors he developed the
nephelometer [9]. He used this instrument in several
ways: to determine the exact equivalence point in
a precipitation titration; to determine the amount of
coprecipitated and occluded impurities in a precipitate;
and to determine the solubility-product loss of a
precipitate into the supernatant solution. With his
invention and use of the nephelometer, he was a
forerunner in the use of instrumental methods for the
evaluation of systematic errors in classical analysis.
This is discussed in more detail below.
In 1904 Richards determined the relative atomic
mass of sodium in a sample of sodium bromide which
he knew to be very pure. He obtained a value for the
relative atomic mass of sodium that was significantly
lower than Stas’s value, assuming Stas’s values for
silver and bromine were correct. This discrepancy
could not be disregarded, because it indicated either
an impurity in Richards’s sodium bromide or a flaw in
Stas’s work. Failing to find impurities in his sodium
bromide after additional careful work, Richards set out
to redetermine the relative atomic masses of Na and
Cl [10]. He launched a very careful quantitative study
to determine three ratios: AgCl:NaCl, Ag:NaCl, and
Ag:AgCl. He found that each step of this work was
critically dependent on both the purity of the materials
21
C. M. Beck II
and the application of physical chemical principles to
the gravimetry involved. Stas had worked with large
masses (about 200 g) of substances in order to reduce
weighing errors, but Richards saw that this approach
suffered from the difficulty of purifying a large mass
of substance. Stas had made his precipitations from
concentrated solutions, but Richards learned that this
led to the occlusion and coprecipitation of impurities
in the precipitates. Stas had dried his substances
under atmospheric conditions, but Richards realized
that this led to the occlusion of oxygen and water
from the air. Richards worked with smaller masses
(3 g to 20 g), and he insisted on applying rigorous
standards for the purification of all substances. He
precipitated from dilute solution to minimize occlusion
and coprecipitation effects. He used his special bottling
apparatus to dry precipitates under carefully controlled
conditions. He used the nephelometer to achieve precise
endpoints and to evaluate the solubility-product losses
of precipitates into the solution. Richards obtained
significantly lower values for the relative atomic masses
of Na and Cl, which eventually necessitated the
recalculation of all relative atomic masses which were
related to Na, Cl, or Ag.
By 1906 several discrepancies had come to light,
suggesting that Stas’s relative atomic mass of silver
was distinctly too high. This created confusion and
uncertainty throughout the entire table of relative atomic
masses since most of the values were related to oxygen
through silver. Realizing that the relationship between
silver and oxygen had to be known without doubt,
Richards, together with Hobart Hurd Willard (1881-
1974), designed a series of elegant preparations and
gravimetric assays to determine the ratios LiClO4 :LiCl
and LiCl:Ag. Combining these ratios gave the relative
atomic mass of silver directly in terms of 4 oxygen
atoms, in addition to providing a new value for the
relative atomic mass of Li. Richards obtained a relative
atomic mass for silver 0,05 % lower than Stas’s value,
and at the same time got a value for Li which turned
out to be 2 % lower than Stas’s value. This was
probably the most careful of all of Richards’s work,
and remarkably his value for silver, after correction
to r (12 C) = 12 exact, differs from today’s mass-
spectrometrically determined value by only 1 part in
105 . For this and other work on relative atomic masses,
Richards was awarded the Nobel Prize for Chemistry
in 1914.
Richards’s papers, especially [11-13], provide a
clear textbook on how to do metrologically valid
gravimetry. They are beautifully written and will bring
delight and insight to anyone who takes the time to
study them. Richards summarized in two sentences all
that one needs to know about evaluating systematic
errors in gravimetry. “Every substance separating as a
new solid phase tends to retain upon itself or within
itself some of the other substance in the phase from
which it separated” [14]. “All liquids tend to dissolve
22
something from every other phase, solid, liquid, or gas,
with which they come in contact” [15]. In other words,
one must determine the mass of all substances on the
balance pan that do not belong there, and one must
determine the mass of all substances not on the balance
pan that do belong there.
Richards’s use of the nephelometer is one of the
early examples of how an instrumental method was used
in tandem with a classical method for the evaluation
of systematic errors. Since that time analysts have
been combining classical and instrumental methods of
analysis in individual situations. However, two papers
by Silve Kallmann (1915-1989) that appeared in the
mid-1980s advocated a deliberate, systematic approach
to using classical analysis and instrumental analysis
in concert [16, 17]. In many instances, older classical
analyses can be reconstructed and revitalized by using
them together with instrumental determinations. In other
instances, entirely new methods, some of them very
elegant, are possible. Kallmann made an important
contribution by suggesting that the classical analyst
continually consider such possibilities as a part of the
overall analytical approach to methods development.
There are at least two opportunities for combining
instrumental determinations with gravimetry. The first
is in checking the purity of precipitates, i.e. determining
what is on the balance pan that does not belong
there. Despite the fact that every effort is made to
choose optimum conditions for precipitation, many
precipitates are significantly contaminated because
of coprecipitation and occlusion. Such an impure
precipitate can be redissolved and the contaminant
(or contaminants) determined by instrumental analysis
(e.g. atomic absorption spectrometry, inductively
coupled plasma emission spectrometry, x-ray emission
spectrometry, etc.).
The second opportunity is in checking the filtrate
from a gravimetric determination for the solubility-
product loss, i.e. determining what is not on the
balance pan that does belong there. No gravimetric
precipitate is completely insoluble, but the filtrate can
be examined by an instrumental method for the small
amount of the precipitate that has dissolved in the
filtrate. For example, the classical method for silica can
be simplified by isolating the precipitated silica from a
single dehydration, and then determining the remainder
in the filtrate by graphite-furnace atomic absorption
spectrometry. Kallmann points out other examples of
how a method that may have been rejected because of
a slightly soluble precipitate can now be reconstructed.
An example of this increase in accuracy is discussed
in a paper describing the evaluation of all systematic
errors for reaction (r-1) [18].
1.4 Sources of uncertainty in gravimetry
If gravimetry is to be employed in valid chemical
metrology, all the sources of uncertainty in the
analytical process must be understood. The com-
Metrologia, 1997, 34, 19-30

bined uncertainty associated with a gravimetrically
determined value is made up of many components.
Although there can be overlapping effects, uncertainty
components fall into two categories: those arising from
random effects, and those arising from systematic
effects.
In Section 1.3, the major systematic errors
associated with gravimetry were discussed. The
evaluation of each systematic error (usually by an
instrumental method) leads to a correction which is
applied to the gravimetrically determined value. Each
correction has associated with it an uncertainty, and
each of these uncertainties must be propagated into the
complete uncertainty budget.
There are also uncertainty components that arise
from random effects, and the major ones are associated
with the terms of (3) and (7). In addition there is
an uncertainty component from the random effect
of replicate determinations. Let us consider the
uncertainties of the terms in (3) and (7). The terms
a and b in (3) generally are assumed to be small whole
integers with no uncertainty. This is true, of course,
only in so far as the chemical reaction (or reactions)
associated with a particular gravimetric determination
proceeds stoichiometrically as written. The standard
chemical reactions employed in gravimetry have been
exhaustively studied and tested for decades, and in some
cases for well over a century. These chemical reactions
are well understood and have been shown to proceed
stoichiometrically as written.
The next consideration in (3) is the uncertainties
of the molar masses, (d) and (w). Today the
uncertainties of the molar masses of the mononuclidic
elements as determined by mass spectrometry are only a
few parts in 107 . The molar masses of the polynuclidic
elements have only slightly larger uncertainties due
to the experimental uncertainty associated with the
abundance ratios of the various isotopes in the naturally
occurring element. Other polynuclidic elements have
still larger uncertainties in their molar masses due
to the range of isotopic composition of the normal
terrestrial material, and isotopic fractionation occurring
either geologically or by intentional or accidental
human intervention [19]. Therefore, when performing a
gravimetric determination of certain elements, including
among others B, Li, Sr, Pd, and Pb, the analyst must be
sure of the source of the element. If there is doubt as to
the source of the material containing these elements, a
relative atomic mass together with its uncertainty must
be determined for the specific sample at hand. Values
for the molar masses for specific specimens of these
elements can vary by as much as several parts in 102 .
The next consideration is the uncertainty in the
determination of the mass of the sample in (7) and of
the precipitate in (3). By the mid-nineteenth century
the analytical balance had been refined to a point
where masses routinely could be determined with an
uncertainty of about 1 part in 105 . Today masses can
Metrologia, 1997, 34, 19-30
Toward a revival of classical analysis
be determined routinely with an uncertainty of about
1 part in 106 .
Finally, there is the uncertainty associated with
replicate determinations. Carefully performed routine
gravimetric determinations have an overall relative
replication uncertainty of about 1 part in 103 . This
uncertainty results in part from a combination of
effects from dust and other particulate contamination,
and losses through splattering, spilling, incomplete
transfers, etc. With special effort and attention to detail,
including clean-room facilities, an experienced analyst
can achieve a replicate uncertainty of a few parts in 104 .
The most painstaking gravimetric assays ever achieved
have had replicate uncertainties of a few parts in 105 ,
and such efforts have taken many months and in some
cases over a year (e.g. some of the gravimetric assays
performed by T. W. Richards in the determination of
the relative atomic mass of Ag).
Part 2: Titrimetry
2.1 Basis equations and terms of titrimetry
Titrimetry is the determination of the amount of
substance of an elementary chemical entity through
the measurement of the volume of a primary standard
solution of another elementary chemical entity of known
amount-of-substance concentration which is necessary
to complete exactly a stoichiometric chemical reaction
(or reactions) involving the two entities. If volumes
are measured, all work must be done at constant
temperature (for ordinary work ± 0,5 C). To reduce
the overall uncertainty, titrimetry can be performed on a
mass basis using a weight buret together with a primary
standard solution made up on a mass/mass basis.
In titrimetry, the general equation describing the
measurement is
(9)
where
dD = the amount of substance of the elementary
chemical entity being determined;
tT = the amount of substance of the elementary
chemical entity contained in that volume of
its standard solution titrant which is necessary
to complete exactly the stoichiometric chemical
reaction (or reactions) being employed in the
determination.
In addition to being stoichiometric, the reaction (or
reactions) must proceed in only one manner, i.e. any
reaction other than the one indicated by the equation
(or equations) must not occur; the velocity with which
equilibrium is reached must be sufficiently great; the
reaction must proceed as nearly completely as possible,
i.e. the equilibrium constant must be very large; and
there must be a suitable indicator for the detection of
the endpoint.
23
C. M. Beck II
Unlike the general expression for gravimetry (1),
the small whole integer terms, a and b, do not appear
in (9). Instead, the coefficients d and t appear, and
their values (which may be integers or fractions)
depend on the amount-of-substance relationship in the
stoichiometric reaction (or reactions) involving D and
T. To illustrate this, consider the general case of
(r-2)
(r-3)
Combining the two reactions
(r-4)
where dD is the elementary chemical entity being
determined, aA is some other reactant, tT is the
elementary chemical entity in the titrant standard
solution, and eE, yY, and zZ are products of the
reactions. In (r-4), the special combinations dD, aA, tT,
eE, yY, and zZ are considered as elementary chemical
entities. This means that a mole of dD plus a mole
of aA plus a mole of tT yields a mole of eE plus a
mole of yY plus a mole of zZ. In other words, the
elementary chemical entities have been chosen in such
a way that the amount of substance of each reactant is
equal to the amount of substance of each product. The
SI system stipulates that the elementary entity must be
indicated by use of its mole. The entities of interest are
dD and tT, and either entity may be an integer quantity
of a real molecule or ion, e.g. H2 O or Fe2+ , or either
entity may be a fractional quantity of a real molecule
or ion, e.g. 1/3 NH3 or 1/6(Cr2 O ). If necessary, the
concentration of a fractional quantity of an entity, c(tT),
can be converted to the corresponding concentration of
the integer value of that entity, c(T), by the equation
(10)
For example, by this relationship
(11)
Suppose that the amount-of-substance concentra-
tion of tT in the titrant standard solution is ctT , and that
VtT is the volume of the titrant standard solution needed
to exactly complete (r-4). The amount of substance of
tT is
(12)
By (9) we know that
(13)
and it follows that
(14)
Substituting (12) into (13) gives
(15)
In many titrimetric determinations the mass of dD
is desired (e.g. in metal and alloy analysis), so that the
24
result of the assay can be expressed as a mass fraction
[see (19)]:
(16)
Substituting (15) into (16) we obtain
(17)
Analysts familiar with titrimetry will recognize (17)
as being in the same form as the traditional expression
for titrimetry which uses the concepts of “normality”
and “equivalent mass”. Although many chemists were
educated using the “normal-equivalent mass” system,
there are several reasons why its use is being
discouraged. The “equivalent mass” of a substance does
not have a unique definition and it is not compatible
with SI units. In contrast, all the terms in (17) are in SI
units. In addition, there are several oxidation-reduction
systems and disproportionation systems where the use
of the “normal-equivalent mass” system is awkward at
best. Furthermore, the old system fails completely with
compleximetric and precipitation titrations. The reader
is urged to consult [20], where there is further discussion
of the basic relationships involved in titrimetry together
with instructive examples.
2.2 Basic example of a titrimetric determination
Consider the following example of a titrimetric
determination. Suppose it is desired to assay an aqueous
sulfuric-acid solution of dissolved vanadium metal,
where the vanadium is in solution as the vanadate ion,
VO . This assay can be performed using a standard
titrant solution of Fe2+ . The reaction is
(r-5)
It has been well established that the vanadate ion,
VO , where V is present as V5+ , is quantitatively
reduced to the vanadyl ion, VO2+ , where V is present
as V4+ . In the reaction, Fe2+ is quantitatively oxidized to
Fe3+ . If the amount-of-substance concentration of Fe2+
is known, then the amount-of-substance concentration
of vanadium can be determined.
A titrant solution of Fe2+ is prepared by dissolving
an appropriate mass of Fe(NH4 )2 (SO4 )2 6H2 O (fer-
rous ammonium sulfate hexahydrate) in dilute sulfuric
acid. The “appropriate” mass is based on the expected
concentration of V in the unknown solution, and on the
need for the volume of titrant used to be sufficiently
large (usually 30 cm3 to 40 cm3 ) that good precision
can be obtained.
An accurate value for the amount-of-substance
concentration of Fe2+ in the titrant solution must now
be determined using a comparison titration to a primary
standard solution made from a primary reference
material such as K2 Cr2 O7 (potassium dichromate).
K2 Cr2 O7 can be obtained in very pure form as a certified
Metrologia, 1997, 34, 19-30

reference material from reference material producers
(e.g. NIST SRM 136e).
The quantitative oxidation-reduction reaction for
this comparison titration is
(r-6)
(Note that in (r-6) and (r-7), the primary reference
material has not been written in its ionic form on the left
side of the reaction (e.g. 2K+ + Cr2 O ). This has been
done to illustrate this specific discussion.) The most
convenient elementary entity in this type of reaction is
one which gains or loses one electron. Choosing Fe2+ as
the elementary entity, the equation can be rewritten as
- of Nicolaas Schoorl (1872-1942), who was teaching
With the equation in this form, we see that
each Fe2+ reduces 1/6(K2 Cr2 O7 ), and so 1/6(K2 Cr2 O7 )
becomes the elementary chemical entity of K2 Cr2 O7 .
An aqueous primary standard solution of K2 Cr2 O7 is
prepared with a known amount-of-substance concentra-
tion of 1/6 K2 Cr2 O7 . The value of this concentration
is chosen such that when a volume consistent with
good precision (i.e. 25,00 cm3 ) is taken, it will require
30 cm3 to 40 cm3 of the Fe(NH4 )2 (SO4 )2 6 H2 O titrant
to complete the reaction. Replicate high-precision
comparison titrations, using sodium diphenylamine
sulfonate as a visual colour indicator, give the volume of
Fe(NH4 )2 (SO4 )2 6 H2 O titrant necessary to complete
(r-7) exactly. By (13) and (14) we know that
(18)
where
tT = the amount-of-substance concentration of the
elementary chemical entity in the titrant (in this
case, Fe2+ );
tT = the volume of the titrant solution used to
complete the reaction exactly;
sS = the amount-of-substance concentration of the
elementary chemical entity in the primary standard
solution [in this case (K2 Cr2 O7 )];
sS = the volume of the primary standard solution
taken for the standardization.
The amount-of-substance concentration of Fe2+ in the
titrant solution can now be calculated.
This Fe2+ titrant is now used to assay the unknown
vanadium solution. Replicate high-precision titrations
with a known volume of the vanadium solution
are made using the Fe2+ titrant with diphenylamine
sulfonate used as the visual colour indicator, and the
Metrologia, 1997, 34, 19-30
Toward a revival of classical analysis
amount of substance of V is calculated by (15). The
mass of V can be calculated by (16), and as is often
desired, especially in metal and alloy analysis, the mass
fraction of V in the solid sample can be calculated by
(19)
2.3 Sources of error in titrimetry
The work of Izak Maurits Kolthoff (1894-1994)
provides perhaps the best example of how physical
chemistry can be applied to titrimetry, and in particular,
to how physical chemistry can be used either to
evaluate, or in some cases to eliminate, systematic
errors in titrimetry.
Kolthoff attended the University of Utrecht in
1911. His lack of certain prerequisites needed to
study in the chemistry department was a blessing in
disguise, because it brought him under the tutelage
in the University’s school of pharmacy. Schoorl
had studied at the University of Amsterdam where
J. H. van’t Hoff (1852-1911), C. A. Lobry de Bruyn
(1857-1904), and Hendrik Bakhius-Roozeboom (1854-
1907) were teaching. (It was Roozeboom who had
introduced the European scientific community to
Gibbs’s phase rule.) Schoorl was aware of all the
recent advances in physical chemistry which he stressed
in his teaching. He immediately recognized Kolthoff’s
talent and encouraged him to carry out independent
research. Kolthoff had trouble understanding the proper
selection of indicators for acid-base titrations, and
he launched his own study into the matter. He had
already acquired a used copy of Wilhelm Ostwald’s
1894 classic, Die wissenschaftlichen Grundlagen der
analytischen Chemie [The Scientific Foundations of
Analytical Chemistry]. This important book began the
process which put classical analysis on a scientific basis.
Kolthoff was further encouraged by the 1909 paper
of the Danish physiological chemist S. P. L. Sørensen
(1868-1939), who introduced the concept of pH. He
was inspired in 1913 by the work of Joel Hildebrand
(1881-1983) who used the hydrogen reference electrode
in electrometric titrations. Kolthoff borrowed pH
measuring equipment from another professor, but within
a year he had devised his own potentiometric apparatus
in Schoorl’s laboratory. He published his first paper in
1915 on the titration of phosphoric acid.
Kolthoff quickly realized how important physical
chemistry would be for the development of analytical
chemistry, but in those beginning years, the going
was sometimes rough. Not realizing the significance
of his early work, faculty members in the chemistry
department sometimes criticized him. One member
went so far as to try to block him from publishing
and lecturing. Kolthoff was disparagingly known by
some as the “pH-er”, which when pronounced in Dutch
came out as “pay-haer” with a as in “haha”. A colleague
¯ ¯
25
C. M. Beck II
publicly criticized him and warned lecture students not
to read any of the junk that Kolthoff published. When
Kolthoff confronted the colleague and asked him to
retract the statements, he was criticized for showing
disrespect. Before his 1924 United States lecture-tour,
this same colleague warned Kolthoff that the Dutch
had an excellent name in the United States, and that he
(Kolthoff) could easily spoil it. Despite the criticism,
Kolthoff forged ahead and in 1918 presented his Ph.D.
thesis on the “Fundamentals of Iodimetry”, a topic he
returned to again and again over the years. In 1914 the
Danish physical chemist Niels J. Bjerrum (1879-1958)
had published a book showing how to calculate both the
shape of neutralization curves and the titration errors
in visual endpoint determinations. This work inspired
Kolthoff to begin the development of a theoretical
interpretation of all the methods of titrimetry. This
work resulted in his well-known two-volume work,
first published in German in 1926 and then translated
as Volumetric Analysis by N. Howell Furman (1892-
1965) in 1928 and 1929. A three-volume revision of
the work appeared between the years 1942 and 1957
[21]. In 1927, Kolthoff accepted a professorship at the
University of Minnesota where he remained for the rest
of his remarkably long and productive career.
Kolthoff’s Volumetric Analysis is perhaps the best
single resource in English on titrimetry, and these
volumes contain a wealth of information on the
systematic titration errors associated with different types
of titrimetry. Various systematic titration errors are
specific for each titrimetric procedure, and they result
from the chemical processes involved and the nature
of the indicator. These errors cannot be diminished
arbitrarily; e.g. the indicator error would be zero only
if the indicator changed exactly at the endpoint –
and that never happens. Stated briefly, titration errors
are those things that cause one either to deliver too
much or not enough titrant. While the best conditions
for keeping the overall titration error small may be
deduced mathematically, they should always be tested
experimentally (Kolthoff’s well-known maxim: “the
theory guides, the experiment decides”).
In the above example of a titrimetric assay of
a vanadium solution, sodium diphenylamine sulfonate
is used as the indicator. This indicator gives a sharp
endpoint both for the reaction involved in the titrant
standardization (r-6), and for the reaction involved
in the assay of the unknown vanadium solution
(r-5). However, when this indicator is used in these
reactions, a significant systematic titration error (called
an indicator error) is introduced. This indicator error
has two components. The first component is the result
of two chemical reactions that take place as soon as
the indicator is added to the solution to be titrated [22].
When the indicator is added to the K2 Cr2 O7 solution
in (r-6), the diphenylamine sulfonate ion (abbreviated
here as H2 dpas– ) enters into an irreversible oxidation-
reduction reaction converting it to the colourless
26
diphenylbenzidine sulfonate ion (abbreviated here as
H2 dpbs2– ). When this indicator is used to determine the
endpoint of the standardization titration, (r-6), a small
amount of Cr2 O is reduced as soon as the indicator is
added to the solution. This can be represented by (r-8):
(r-8)
Next the H2 dpbs2– ion enters into a reversible oxidation-
reduction reaction, producing the diphenylbenzidine
violet ion (abbreviated here as dpbs ). This can be
represented by (r-9):
(r-9)
(Note that the hydrogens indicated in the abbreviations
are either a part of the ring structure of the indicator
molecule or are attached to the nitrogen atoms in
the indicator molecule. They are so indicated in the
abbreviations in order to keep track of the hydrogen
atoms which are oxidized from the indicator molecule
as H3 O+ .)
Because of the small amount of Cr2 O reduced
by (r-8) and (r-9), the volume of titrant used will be
slightly less than the correct volume. This difference is
the first component of the indicator error. In using this
indicator to perform the unknown vanadium solution
titration, (r-5), analogous reactions (r-10) and (r-11)
occur which reduce a small amount of the VO ion:
(r-10)
(r-11)
So (r-8) and (r-9) cause too little titrant to be
dispensed in (r-6), and (r-10) and (r-11) cause too
little titrant to be dispensed in (r-5). What we need
to know for both (r-6) and (r-5) is the volume of
Fe(NH4 )2 (SO4 )2 6 H2 O titrant that would have been
used in each case if no indicator had been present, so
that an appropriate correction can be made. This volume
can be determined by the following technique. The
concentration of the sodium diphenylamine sulfonate
solution used for the indicator solution is 0,01
mol/dm3 ( 2 g/dm3 ). The volume of each of the
solutions being titrated is 300 cm3 . In order to
have sufficient concentration of the indicator in the
solution so that one can see the colour change at the
endpoint in 300 cm3 , one must add 0,2 cm3 of the
indicator solution. One can determine the amount of
Metrologia, 1997, 34, 19-30

Fe(NH4 )2 (SO4 )2 6 H2 O titrant that would be used if
no indicator were present in (r-6), by performing a series
of titrations on the same volume of K2 Cr2 O7 primary
standard solution with 0,20 cm3 , 0,40 cm3 , 0,60 cm3 ,
and 0,80 cm3 of the indicator solution and recording
the volumes of Fe(NH4 )2 (SO4 )2 6 H2 O titrant used
in each case. If the volume of indicator is plotted
against the volume of titrant used, a straight-line
plot is obtained. Extrapolation back to 0,00 cm3 of
indicator gives the volume of titrant solution that would
have been used had no indicator been present. This
experiment also must be performed for the titration
of the unknown vanadium solution (r-5), because the
corrections will be similar but not necessarily identical
for each titration. (A correction of 1,3 parts in 103 was
observed for both reactions when they were carried out
in a recent determination of vanadium in a chromium-
vanadium master alloy. The fact that the correction
value was the same for both reactions in this instance
was a coincidence.)
We have now evaluated the first component of
the indicator error. There is a second component of
the indicator error which also must be determined.
When the titration is begun in both (r-6) and (r-5), the
potential of the solution changes until one approaches
the endpoint potential. Indicators are chosen so that
the colour-change reaction of the indicator occurs very
near the true endpoint of the titration. A problem arises,
however, because the potential at which the indicator
changes colour is never exactly the same as the potential
of the true endpoint of the titration. The half reaction
for the colour change of the sodium diphenylamine
sulfonate indicator (i.e. the colourless diphenybenzidine
sulfonate ion being oxidized to diphenylbenzidine
sulfonate violet ion) can be represented by the half
reaction (r-12):
(r-12)
The standard reduction potential for (r-12) is
0,84 V. The endpoint potentials for (r-6) and (r-5)
can be estimated by calculation [22] or looked up
in potential tables in quantitative analysis textbooks.
The standard reduction potential for (r-6) is 0,97 V,
and for (r-5) it is 0,81 V. The small difference in the
potential of (r-12) and the endpoint potential of (r-6)
gives rise to the second component of the indicator
error for (r-6); and similarly, the small difference in the
potential of (r-12) and the endpoint potential of (r-5)
gives rise to the second component of the indicator
error for (r-5). In the region of the endpoint of (r-
6) and (r-5), the plot of E/ V is nearly a straight
line with a slope very close to 0,50 V/0,10 cm3 of
titrant. For (r-6), the indicator changes to its coloured
form 0,13 V before the endpoint, and therefore a very
good estimate of this part of the indicator error for
(r-6) is 0,13/0,50 (0,10 cm3 ) = 0,03 cm3 . Consequently,
Metrologia, 1997, 34, 19-30
Toward a revival of classical analysis
0,03 cm3 must be added to the volume of titrant to
correct for the second component of the indicator error
for (r-6). For (r-5), the indicator changes 0,03 V after
the endpoint, and therefore, 0,03/0,50 (0,10 cm3 ) =
0,006 cm3 (rounded to 0,01 cm3 ) must be subtracted
from the volume of titrant to correct for the second
component of the indicator error for (r-5).
Each titrimetric assay has to be treated individually
in terms of evaluating systematic errors. Different kinds
of titration errors are associated with the different
types of titrimetric assays, i.e. titrimetry involving
precipitation reactions, neutralization reactions with
strong acids and bases, neutralization reactions with
weak acids and bases, complex-formation reactions,
and oxidation-reduction reactions. Detailed information
can be found in [23, 24].
The other major systematic error in titrimetry arises
from side reactions. Side reactions occur when there is
a trace of another element which reacts with the titrant.
For example, in the assay of a Zn solution by titration
with EDTA, there is almost always a trace of Cd in the
Zn solution. The trace of Cd requires a small amount
of the titrant, thus giving a titration volume which
is slightly high. Errors of this type are most easily
dealt with by titrating both the Zn and the trace of Cd
together. The amount of Cd is determined separately by
an instrumental method, and an appropriate correction
is made.
2.4 Sources of uncertainty in titrimetry
Just as in gravimetry, it is important that all sources
of uncertainty be understood if titrimetry is to be used
in valid chemical metrology. The combined uncertainty
associated with a titrimetrically determined value is
made up of many components, some of which are
the same as in gravimetry. Additionally, there are
some uncertainty components in titrimetry which are
different, and there are some additional uncertainty
components which are not present in gravimetry.
Although there are overlapping effects, the uncertainty
components in titrimetry arise from both random and
systematic effects.
In Section 2.3, the major systematic errors asso-
ciated with titrimetry were discussed. The evaluation
of each of these systematic errors results in a
correction which has an associated uncertainty. Each
uncertainty component associated with each systematic
error correction must be propagated into the overall
uncertainty budget of the titrimetric determination.
The uncertainty components that arise from the
random effects in titrimetry are associated with the
terms in (17). In addition, there is an uncertainty
component from the random effects of replicate
determinations. Considering (17), the coefficient d is
almost always chosen to be unity with no uncertainty,
and in so choosing d, the coefficient t becomes a fraction
whose numerator and denominator are small whole
integers with no uncertainty. For example, in an acidic
27
C. M. Beck II
dichromate titration with Fe2+ , d = 1 and t = 1/6, and in
an acidic permanganate titration with Fe2+ , d = 1 and
t = 1/5 [25]. These fractions result from the coefficients
of the chemical entities in the reaction (or reactions)
employed in the titrimetric assay, and hold true only if
the reaction (or reactions) proceeds stoichiometrically to
the right as written. The chemical reactions employed in
titrimetry have been well characterized, and only those
that have been shown to proceed stoichiometrically to
completion as written are used.
The issues surrounding the uncertainty in the
molar mass, (dD), and the uncertainty associated
with replicate determinations are the same as with
gravimetry. What is different with titrimetry is the
uncertainty of tT and tT because they involve the
measurement of volumes. Typically, tT is determined
by measuring the volume of the titrant delivered from
a buret, which can be read with an uncertainty of
0,01 cm3 to 0,02 cm3 . Therefore, the typical uncertainty
in the volume measurements for the nominal 40 cm3
titration is a few parts in 104 . If a piston-type automatic
buret is used to deliver the titrant, the uncertainty in
the delivered volume is a few parts in 105 . Since
concentration is a mass/volume term, two measurements
are required to obtain the value of tT . The issues
surrounding the determination of the mass of the
primary reference material are the same as with mass
determinations in gravimetry. The specifications for
Class A volumetric flasks call for uncertainties of a few
parts in 104 , however, they should always be checked.
[The analyst can calibrate volumetric ware to a few parts
in 105 by measuring the water contained (or delivered in
the case of a pipet) at a specified temperature, correcting
for buoyancy, and calculating the volume using water
density tables.] When titrimetry is done on a volume
basis, the work must proceed at constant temperature,
or the uncertainty in volumes created by temperature
fluctuations must be determined. In order to reduce
the uncertainty associated with volume measurements,
titrimetry can be conducted on a mass basis. A weight
buret is used and the mass of the titrant is determined,
the titrant having been prepared so that its concentration
is known on a mass/mass basis.
Conclusion – toward a revival
A goal of this paper is to show that gravimetry and
titrimetry can be used for metrologically valid chemical
determinations. Classical analyses are based directly on
the SI units of mass and length, together with the use
of molar masses and stoichiometric chemical reactions.
Gravimetry and titrimetry can be performed in such
a way that their operation is completely understood.
With gravimetry, the important systematic errors of
adsorbed, occluded, and coprecipitated impurities in the
precipitate, and solubility-product losses of precipitate
into the filtrate, must be evaluated so that appropriate
corrections can be made. With titrimetry, the important
systematic errors of “indicator error” and side-reaction
28
error must be evaluated so that appropriate corrections
can be made. All of these systematic errors in
both gravimetry and titrimetry can be evaluated by
instrumental methods. With systematic errors evaluated
and random errors calculated or estimated, a complete
uncertainty budget can be produced.
Despite the fact that instrumental analysis has
rightfully assumed the overwhelmingly major role in
the analytical laboratory, there remains a limited,
although very important, need for classical analysis
today. The continued need for classical analysis in
industry is well known. As an illustration, consider my
own experiences in government and industry analytical
laboratories in the 1980s and 1990s. While working
for a large corporation engaged in advanced ceramic
research, the analytical laboratory was asked to assay
each of the elements (except oxygen) in the following
compounds: SiC, TiC, WC, BN, AlN, Si3 N4 , TiN,
Al2 O3 , SiO2 , TiO2 , and Y2 O3 . In most cases, the
required uncertainty was 5 parts in 103 or better,
and, in many cases, mixtures of two or more of the
compounds were submitted for analysis. While working
for a major forging company, the analytical laboratory
was asked to assay aluminum-, titanium-, cobalt-, and
nickel-base alloys for Al, Co, Cr, Mo, Sn, V, and
Zn in the 5 % mass fraction to 80 % mass fraction
range with a required uncertainty of 2 parts in 103 or
better. While working for the government, the analytical
laboratory was asked to assay the following compounds
and materials: Si2 Te3 , W5 Si3 , Mo5 Si3 , Mo3 Si, CoSi2 ,
Si3 N4 , the oxides of all the rare-earth elements, the
ores and ore concentrates of Cu, Mn, Mo, and Zn, and
concentrated solutions of Th, Sr, and Li, all with a
required uncertainty of 1 part in 103 or better. All of
these requests finally arrived at the classical analyst’s
bench, either because instrumental methods had failed
to provide the necessary uncertainty, or because, due
to the unavailability of a suitable reference material for
instrumental calibration, a definitive method had to be
used. Without exception, each of the above assays was
of considerable economic importance to industry and
government.
It is doubtful that colleges and universities will
ever again offer sufficient training in classical analysis
to resupply the work-force with well-trained classical
analysts. Because of the fiercely competitive nature
of research grant funding, no “professor of classical
analysis” could long survive in a modern university
chemistry department. Nevertheless, in some important
instances, industry and government laboratories will
continue to depend on the classical analyst to decide
if raw materials meet specifications and finished
products can be released for sale. To an even
greater extent, classical analysis will be needed in
the development of new materials. Most importantly,
however, gravimetry and titrimetry will continue to
be indispensable processes in the production and
certification of the reference materials which are
Metrologia, 1997, 34, 19-30

necessary for the calibration of almost all instrumental
methods. This paper has attempted to demonstrate
that classical analysis, gravimetry and titrimetry, are
metrologically valid analytical procedures. If this is
indeed true, then the use of gravimetry and titrimetry
in the certification of reference materials can rightly be
referred to as “chemical metrology”.
Analytical laboratories, especially national labora-
tories, continue to look for capable people to replace
their retired classical analysts. Most laboratories have
given up after years of unsuccessful searching. The
writer speculates that at the present time thousands
of well-trained classical analysts are needed world-
wide. If there were a “classical analysis teaching
laboratory” where qualified classical analysts were
being trained, recruiters would probably line up at the
door at graduation time. Perhaps the way in which
Karl Remegius Fresenius (1818-1897) established his
laboratory could serve as a model for a similar effort
today.
Fresenius was hired as professor of chemistry,
physics and technology at the Agricultural College at
Wiesbaden, Germany, in 1845. Because the college
administrators repeatedly refused to supply funds for
a chemistry laboratory, he borrowed money from his
father, a prosperous attorney, bought a house, and
remodelled it into a private analytical laboratory. He
opened the doors in 1848 with one assistant [Emil
Erlenmeyer (1826-1909)] and five students. In five years
Fresenius had thirty students, and in eight years he had
sixty students, all of whom were eligible to receive
university credit for their study in his laboratory.
Fresenius had one advantage over us in that he
did have good textbooks for his courses because he,
himself, had written two of the best textbooks available
at that time [26]. Today, the unavailability of textbooks
and reference books is a serious problem for anyone
wanting to study classical analysis. Except for the
reprinting of Vol. I of Scott’s Standard Methods of
Chemical Analysis [27], and the recently published, A
Manual for the Chemical Analysis of Metals by T. R.
Dulski [28], most, if not all, of the comprehensive
textbooks and reference books on classical analysis
in English are out of print. References [22, 29-
33] are landmark classical analysis reference works
which the world-wide analytical community should
attempt to have reprinted. Special mention should be
made of Methods of Quantitative Inorganic Analysis
by Kazunobu Kodama (b. 1914). In this monumental
work, Kodama has written a compendium of all
classical methods (together with all spectrophotometric
methods) that have appeared in all the textbooks and
all the chemical literature up to 1958. This book has
been out of print for over thirty years. Since his
retirement, Kodama has meticulously prepared hand-
written notes annotating the first edition of his book
together with references to all classical methods (and
spectrophotometric methods) appearing in the literature
Metrologia, 1997, 34, 19-30
Toward a revival of classical analysis
since 1958. The world-wide analytical community
should ensure that a second edition of Kodama’s book
is published and maintained in print.
With a few capable and dedicated teachers, a
school with an excellent reputation could be established
in less than a decade. Industry, or a joint venture
by industry and government, will have to bear the
cost, but further delay in addressing the problem will
prove even costlier. In fact, such a venture would not
require a huge financial investment. The building and
equipment requirements for such a teaching laboratory
would be relatively modest, but those in charge of the
administration and instruction would need to be people
of great ability, experience, commitment, and integrity.
The science, the art, and the “state of mind” that are
necessary in order to become a good classical analyst
will have to be carefully imparted to each student.
Students will have to practise until they master the
techniques of common classical analytical operations,
and they will have to analyse the kinds of material used
in industry and government in order to gain proper
experience. From such a school could flow a small but
steady stream of qualified classical analysts to serve
in industrial, governmental and private laboratories.
The graduates of this school would have the mental
and manual skills necessary to do classical analyses.
Perhaps such a school exists. If not, now is the time
to establish one.
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29
C. M. Beck II
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Metrologia, 1997, 34, 19-30