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 Bureau International des Poids et Mesures Metrologia

Metrologia 55 (2018) L25–L33 https://doi.org/10.1088/1681-7575/aaace8

Letter to the Editor

The evolution of chemical metrology:

distinguishing between amount of
substance and counting quantities, now
and in the future
Richard J C Brown1
Chemical, Medical and Environmental Science Department, National Physical Laboratory, Teddington,
TW11 0LW, United Kingdom

E-mail: richard.brown@npl.co.uk

Received 14 December 2017, revised 1 February 2018

Accepted for publication 5 February 2018
Published 30 May 2018

Abstract
This discussion article begins by highlighting the benefits of the mole’s incorporation within
the International System of Units (SI), in particular by bringing chemical measurement
within formal metrology structures. The origins of the confusion that has consistently
existed between amount of substance (the base quantity of which the mole is the SI base
unit) and counting quantities are examined in detail and their differentiating characteristics
fully elaborated on. The importance and benefits of distinguishing between these different
quantities and the role that the Avogadro constant plays in doing this are highlighted. It is
proposed that these issues are becoming increasingly important for two reasons. First, as
chemistry and biology consider increasingly small size domains, measurements are being
made of significantly reduced collections of entities. Second, the proposed re-definition
of the mole makes the link between amount of substance and the number of elementary
entities more transparent. Finally, proposals for new ways of expressing very low amounts
of substance in terms of new prefixes based on the numerical value of the Avogadro constant
are presented as a way to encourage the use of the mole, when appropriate, even for ultra-low
level chemical measurement.

Keywords: mole, amount of substance, counting, SI prefixes, SI revision

Introduction ‘gram-molecule’, as defined in English in the Encyclopedia

Probably since Gay-Lussac’s law of combining volumes of
gases in 1808 scientists have grappled with the concept of
stoichiometric chemical amounts, rather than equal masses,
reacting together. The ongoing requirement to realize chem-
ical amounts practically in terms of mass led to the coexistence
of these two concepts through the use of ‘kilogrammolekuel’,
as outlined in the textbooks of Ostwald and Nernst, and
1
The views of the author are expressed and do not necessarily reflect those
of NPL Management Ltd.
Britannica, both occurring in 1893 [1]. The evolution of this
idea to recognize that any equal number of ‘gram-molecules’
contained the same number of molecules was a step forward,
but introduced a further way in which the terms for the chem-
ical amount, now abbreviated in texts to ‘mole’, was used. On
one hand this led to the concept of the ‘chemical mass unit’
and on the other this suggested a ‘number of moles’. In 1942
Guggenheim noted that ‘it can sometimes be useful in dimen-
sional analysis to regard the number of atoms as having dimen-
sions different from a pure number’ [2]. This was the first step

1681-7575/18/030L25+9$33.00 L25 © 2018 BIPM & IOP Publishing Ltd  Printed in the UK
Metrologia 55 (2018) L25
towards the separation of the chemical amount and the number
of elementary entities, which had become entwined. Thus
began the process that led to the eventual acceptance of the
mole within in the International System of Units (SI) in 1971.
However, the lack of clarity between amount of substance
and number of elementary entities remained largely undimin-
ished by this decision. As science has progressed to include
serious studies of enumeration, or counting2, of entities that
are non-identical and non-elementary this has developed into
more serious confusion about quantities being measured and
expressed.
There are several excellent and fulsome texts that describe
the origins, evolution and usage of amount of substance and
the mole [3–6]. There are few if any that address the differ-
ences between amount of substance and counting quanti­ties.
This paper aims to address that deficiency, highlighting the
benefits and drawbacks of each and considering what effect
advances in science and the likely revision of the SI will have
on the relationship between amount of substance and counting
quantities in the future. First it is necessary to understand why
the presence of the mole within the SI is so valuable.
In this paper, where possible, the term ‘elementary entities’
is used to describe items which could be considered together
as amount of substance, whereas the term ‘entities’ is used to
describe items in the most general sense (a specific subset of
which are elementary entities). Hopefully the meaning is also
clear from the context of usage.
Benefits of the mole’s presence within the SI
The agreement between the International Union of Pure and
Applied Chemistry (IUPAC) and the International Union of
Pure and Applied Physics (IUPAP), finalized in 1961, that
assigned the value 12 exactly to the relative atomic mass
carbon-12 was another step towards unified thinking in the
chemical measurement area. This was quickly followed by a
proposal from the International Standards Organization (ISO),
IUPAC and IUPAP to the International Committee for Weights
and Measures (CIPM) to develop a formal definition of the
mole. The 14th General Conference on Weights and Measures
(CGPM) in 1971 approved this definition, specifying that ‘the
mole is the amount of substance of a system that contains as
many elementary entities as there are atoms in 0.012 kg of
carbon 12; its symbol is mol’ and that it was a base unit of the
SI [5]. There were a number of benefits to adopting the mole
as a base unit of the SI, many of these are as relevant now as
they were in 1971 [7]:
• It formally described a unit which was defined as directly
proportional to the number of elementary entities in a
sample of a substance, a major requirement of chemists
in order to establish stoichiometric relationships not
describable in mass terms.
• With the mole as a base unit it introduced the concept
of amount of substance having its own dimension. This
2 the name of the unit. The use of the adjective ‘enplethic’ has been previously
Countable and counting are used as more accessible terms in place of
enumerable and enumeration, respectively.
L26
Letter to the Editor
convention was in wide use by chemists and met the
requirement to distinguish the ‘number of atoms’ from
a pure number. This also extended the power of dimen-
sional analysis and quantity calculus to chemistry and
provided a clear basis for distinguishing between amount
of substance and number of entities.
• It brought chemistry within the SI and encouraged chem-
ists to adopt the SI and formal metrological structures—a
prescient decision given the extensive efforts now dedi-
cated to chemical metrology across the world3.
• It formally resolved the confusion arising from the dif-
ferent atomic mass scales, which the IUPAC and IUPAP
had begun to address with their agreement ten years
earlier.
• It provided a formal link between the microscopic and
macroscopic interpretations of the same stoichiometric
equation (for instance: C2H4O  →  CH4  +  CO [3]).
• It unified the nomenclature of chemical measurement
rendering obsolete a collection of different units that
were then in use: ‘gram-atom’, ‘gram-molecule’, ‘gram-
equivalent’, ‘gram-formula’, ‘gram-equation’, ‘faraday’,
‘einstein’ and ‘normal’.
In addition this helped to bring the equations of chemistry
and chemical physics within the SI and introduced dimen-
sional analysis to chemistry. This allowed, as a result, inten-
sive and extensive quantities in chemistry to be distinguished,
such as molar4 volume in m3 mol−1 as compared to the volume
of a mole in m3. It also introduced the benefit that chemists
had realized for a long time, namely that chemical quantities
could be expressed with user-friendly numbers, for instance:
0.1 mol dm−3 rather than much larger numbers accompanied
by unclear or unofficial units to express entities. McGlashan
noted [6] that no question arose over the choice of an SI unit
of amount of substance because no other unit was involved:
amount of substance is dimensionally independent. He dis-
missed the argument that the mole should have been consid-
ered as having units of mass since in this case any distinction
between mass and amount of substance or between massic
and molar quantities would have been lost. More importantly,
McGlashan further dismissed the argument that the mole
should be regarded as having the dimension one (or number)
since in this case the mole would have only appeared in the
unit expression as a ‘flag’ in the same way as for the radian.
Furthermore, as previously mentioned, any dimensional dis-
tinction between extensive and intensive quantities involving
amount, would be lost.
Nonetheless the 1971 definition of the mole is clearly
reliant on the definition of the kilogram, although this rela-
tionship rarely causes confusion between the two base units.
More contentious has been the name ‘amount of substance’
for the base quantity of which the mole is the SI base unit
3
Calibration and measurement capabilities (CMCs) relating to chemistry
now constitute 25% of all entries on the International Bureau of Weights and
Measures (BIPM) Key Comparison Database.
4
It is unfortunate that the term ‘molar’, which is in widespread use, violates
the general principle that the name of the quantity should not be mixed with
suggested as an alternative.
Metrologia 55 (2018) L25
[3]. The name is not particularly widely adopted amongst
chemists outside the metrology sphere even over forty years
after the definition of the mole. Quantities are sometimes dif-
ficult to define in words, and lend themselves more easily to
description using the equations  of chemistry and physics in
which they occur [4]. In most physical measurements, we first
conceive of and describe the quantity (for instance length)
before we allocate a measurement unit to it (for instance
the metre) [8]. The fact that this happened somewhat in
reverse for chemistry—the quantity amount of substance was
invented after its unit mole—is often presented as a reason for
the lack of the proper adoption of the quantity name5. Other
reasons include the perceived clumsiness of the name6 and the
unique requirement for amount-related quantities to provide
an extra qualification when they are used, replacing part of the
quantity name, for example ‘amount of sulphur hexafluoride’,
not found with other quantities. This lack of adoption and
understanding often gives rise to deprecated usage such as the
‘number of moles’ for amount and ‘mole fraction’ for amount
of substance fraction where the same offenders would be
appalled by the equivalent ‘number of meters’ or ‘kilogram
fraction’ in place of ‘length’ and ‘mass fraction’, respectively.
In particular, the erroneous ‘number of moles’ implies that the
quantity has dimension one or is related to counting—a confu-
sion central to the theme of this article and which is addressed
in the discussion below.
We may consider that amount of substance (n) is used to
quantify material (usually pure materials) in a way that is
proportional to the number of elementary entities (N) in the
sample with the Avogadro constant (NA) as the linking con-
stant of proportionality. They are related by the equation:
n = N/NA .
(1)
(We need not concern ourselves with debates about the nature
of the Avogadro constant and how ‘fundamental’ it is; how-
ever, it may be useful to think of the Avodagro constant as
a ‘concept synthesizer’ [9] relating amount of substance and
the number of elementary entities.) In this consideration it is
important to note that the Avogadro constant is only a con-
stant of proportionality between amount of substance and the
number of elementary entities where those entities could be
considered as part of the definition of the mole. It does not
relate non-elementary or non-identical entities to amount of
substance. This is crucial since there are also things that we
may count that are non-elementary or non-identical, or indeed
have nothing to do with chemical or biological measurement.
We may also think of ‘Amount of substance as a quanti­ty
that measures the size of an ensemble of entities. It is pro-
portional to the number of specified entities and the constant
of proportionality is the same for all substances. The enti-
ties may be atoms, molecules, ions, electrons, other particles,
or specified groups of particles’ [4]. This definition empha-
sizes the nature of amount of substance as distinct from a
5
It should be noted that the German term for amount of substance, ‘Stoff-
menge’, is well established and widely used in German speaking countries.
6
‘Chemical amount’ or ‘enplethy’ have been previously suggested as
alternatives.
L27
Letter to the Editor
specific number of elementary entities and from the defini-
tion of the mole. It is useful because it highlights another
advantage of retaining the quantity amount of the substance:
equations such as
n = m/M
(2)
where m is the mass of a pure sample and M is the molar mass
(mass per amount of substance) can be used to determine the
molar mass or amount of substance without knowledge of the
value of the Avogadro constant. This is useful because relative
atomic masses were known accurately long before similarly
accurate measurements of the Avogadro constant were made.
Counting as a measurement
Counting is a fundamental process that has been undertaken
by humans for many thousands of years, possibly even 20 000
years [10]. Arguably counting represented the first measure-
ment process. However, until quite recently counting was not
considered as a proper measurement—perhaps because of its
perceived simplicity and the lack of fundamental study of the
subject, or perhaps because of distinctions sometimes drawn
between ‘measurement’ as a process and a ‘measurement’
result [11]. Indeed the 2001 National Physical Laboratory’s
(NPL) ‘Beginner’s Guide to Uncertainty of Measurement’
[12] stated, ‘There are some processes that might seem to
be measurements, but are not. […] Counting is not normally
viewed as a measurement’7. There are valid philosophical rea-
sons for sustaining such an argument. There is an ontolog-
ical difference between continuous quantities and countable
aggregates—the distinction being the basis of the differences
between real and natural numbers and the natural lower limit
that exists for countable aggregates (i.e. one entity) that does
not exist for continuous quantities [13]. However, whilst of
some epistemological interest, this distinction in no way pre-
vents counting from being accepted as part of practical mea-
surement—both as a process and as a result. Indeed, arguments
highlighting the differences between counting quantities and
continuous quantities are often used in an attempt to demon-
strate why the mole is different from other SI units. These
arguments fail in their consideration, not only to distinguish
properly between amount of substance and counting quanti-
ties, but also to recognize that the definition and realization of
other units depend on counting. The second relies on counting
of 9192 631 770 periods of the radiation corresponding to the
transition between the two hyperfine levels of the ground state
of the caesium 133 atom and following SI revision a redefined
ampere could be realized directly using a quantized electron
pump involving the counting of single electrons [14].
As the boundaries of metrology expand further into chem-
ical, biochemical and biological measurement there are an
increasing number of measurements that are not compatible
with the use of the mole in their expression of units. As a result,
7
This source also identifies comparative analysis, qualitative analysis and
tolerance testing as not being measurements, although nowadays these
would also be considered as part of mainstream measurement science. Much
has changed in the last seventeen years!
Metrologia 55 (2018) L25
8
counting (of items or events) is nowadays recognised and fre-
quently employed as a valid measurement, using traditional
measurement models, metrological traceability and uncertainty
analyses, and is underpinned by the metrological structure of the
SI [15]. These quantities are often referred to as those quantities
having the nature of a count, number of (items being counted),
counting number or, simply, counting quantities. There is no
international agreement on the nomenclature for counting
quantities but ISO 80000-1:2013 uses ‘counting number’ [16].
As shall be discussed later, counting quantities have the unit
one, symbol 1, and have dimension one (or number).
How amount of substance differs from counting
quantities
Amount of substance and counting quantities are regularly
confused—such that chemical measurement is often assumed
to be equivalent to counting, rather than quantifying amount
of substance. To understand why this happens and provide
arguments as to why it should not, it is necessary to examine
the current definition of the mole in more detail [17]:
‘The mole is the amount of substance of a system which
contains as many elementary entities as there are atoms
in 0.012 kg of carbon 12; its symbol is ‘mol’.
When the mole is used, the elementary entities must be
specified and may be atoms, molecules, ions, electrons,
other particles, or specified groups of such particles’.
From this definition the link between the mole and the
number of elementary entities is clear, but the importance of
the Avodagro constant (with units ‘1/mol’)9 as the constant
of proportionality between amount of substance and number
of elementary entities is not explicit. As discussed later, the
proposed new definition of the mole makes this much clearer.
Two qualifiers of the definition are crucial to understanding
the properties of amount of substance as distinct from
counting quantities. The first is ‘of a system’. This phrase does
not (necessarily) refer to ‘system’ in the thermodynamic sense
but is used more generally to imply that the entities being con-
sidered are present in the same location, near enough to one
another such that they could take part in a chemical reaction
together. This excludes usages of the mole to express collec-
tions of entities that have large relative separations and no
chance of collective chemical interaction. The second quali-
fier is the second sentence of the definition requiring that the
elementary entities in question be specified. This is an impor-
tant requirement that:
(a) restricts the entities that may be described to those
that can take part in a stoichiometric chemical reaction
together, and
8
‘Items’ is used to show, as discussed later, that the things being counted
may not be elementary entities or be identical, and also to distinguish this
from the counting of events. ‘Things’ could also have been used, among
others, but perhaps sounds too colloquial.
9
The unit ‘1/mol’ better highlights the function of the Avogadro constant as
the link between counting quantities (with the unit ‘1’) and amount of
substance (with the unit ‘mol’) than the more often used ‘mol−1’ where
explicit reference to counting quantities is lost.
L28
Letter to the Editor
(b) restricts the type of entities described to those that have
sufficient elementary nature to be considered identical for
the purposes of such a reaction.
This second qualifier excludes trivially incorrect usages
of the mole to count non-elementary, non-identical enti-
ties such as the distressingly incorrect ‘a mole of apples’, ‘a
mole of chickens’, ‘a mole of planets’, etc. This second quali-
fier implicitly requires a full definition of the quantity being
expressed when a measurement result is presented. This is
important for the expression of any measurement result, but
perhaps is even more crucial for chemical measurements.
For example, the ‘amount concentration of C3H8O’ does not
adequately distinguish between the isomeric forms of C3H8O
(propan-1-ol, propan-2-ol and methoxyethane) which have
different chemical properties. The individual molecule would
need to be specified in the description of the quantity, ‘amount
of propan-1-ol’. There are occasions when we want to consider
the summed amount of the substance across several different
elementary entities but this will generally be as the denominator
in an intensive quantity, such as an amount fraction expressed
in mol/mol, as in the ‘amount fraction of propan-1-ol in a mix-
ture of propan-1-ol, propan-2-ol and methoxyethane’ [18].
The concept of amount of substance describing collections
of elementary entities that might react together stoichiomet-
rically is a useful qualifier that allows isotopic mixtures of
atoms and molecules to be considered either together, e.g. a
mole of Si, or separately, e.g. a mole of 28Si, as appropriate.
There is of course some subtlety in consideration of an iso-
topic mixture of Si atoms. In this case it is the silicon atom (in
all its isotopic forms) that is the chemically identical elemen-
tary component and not the separate silicon isotopes (which
may have different physical characteristics). This concept also
helps in the consideration of more complex molecules which
could exhibit a huge variety of isotopologues. The elemen-
tary entities description also enables the consideration of
amount of substance for more seldom-considered elementary
entities—for example a mole of electrons reducing a mole of
ions in electrochemistry. Meeting these requirements allows
the quantities to be expressed in mol and derived units thereof,
hence conferring the benefits of amount of substance having
its own unit and an independent dimension within this SI.
The nature of counting quantities
Quantities in chemical and biological measurement attempting
to express quantification, but excluded by the above criteria,
may be considered counting quantities. The more complex
the chemical or biological system is, the less likely it is to be
suitable for description using the mole and related units. For
instance, very large molecules such as DNA are more suit-
able for counting units10, whereas polymers are often more
amenable to mass-based units. Quite apart from being increas-
ingly non-identical in terms of molecular size, collections of
10
For instance DNA may be counted via advanced PCR-based methods.
This is a specific feature of DNA and does not apply to other large
molecules such as proteins.
Metrologia 55 (2018) L25
very large molecules may also start to become unable to take
part in stoichiometric chemical reactions together. In exten-
sion to the discussions above, counting quantities can cover
any collection or collections of entities that may be adequately
specified in the description of the quantity being expressed.
Generally we would count non-identical and non-elementary
sets of entities. Of course, there is no restriction on elemen-
tary entities also being counted, save for unnecessarily surren-
dering the benefits of the use of amount of substance described
above11. (The term ‘entitic quantity’ has been previously pro-
posed to describe quantities that count specified elementary
entities [19].)
Clearly, counting is a broader measurement process than
one simply dealing with chemical and biological situations not
covered by amount of substance12. In theory the items being
counted could be in very different locations relative to their
size since, unlike for amount of substance, there is no require-
ment for them to be close enough to interact. An example
might be the number concentration of planets in the solar
system, although such examples in chemical and biological
measurement are unlikely. Similarly, in contrast to amount of
substance, counting quantities could in theory describe col-
lections of different things with no association to each other.
The usage of counting quantities is only limited by the ability
to unambiguously describe the set of things being counted in
the description of the quantity. This becomes more difficult
as the similarity between the things being counted decreases.
To do so it might be necessary to use generic groupings terms
such as ‘items’ or ‘objects’ rather than list all the different
constituents of the measurements (apples, chickens, planets,
etc). Again, encountering examples of this type in chemical
and biological measurement is unlikely.
Expressing counting quantities
Because the sets of entities being counted will be to some
extent inhomogeneous (certainly with respect to the homo-
geneity of ‘elementary entities’ considered in the discussions
above) it becomes even more important to make the descrip-
tion of the exact quantity being expressed unambiguous. Too
often when expressing results, practitioners will rely on units
to imply the quantity being expressed. Since there are more
quantities than there are units this represents poor practice.
For counting, where the number of quantities is almost limit-
less but there is only one unit, this risks causing dangerous
confusion. Items that are counted use the unit one, symbol 1.
As the draft 9th SI brochure [20] states:
‘The unit one is the neutral element of any system of
units—necessarily and present automatically. There is no
requirement to introduce it formally by decision. There-
fore, a formal traceability to the SI can be established
through appropriate, validated measurement procedures’.
11
The English idiom ‘keeping a dog and barking yourself’ nicely describes
this juxtaposition.
12
Counting also includes quantities not directly related to chemistry or biol-
ogy, for example stochastic process such as activity referred to a radionuclide
(measured in Bq) or periodic processes such as frequency (measured in Hz).
L29
Letter to the Editor
Counting quantities are often referred to as being dimen-
sionless or having the dimension one. More rigorously [21]
we should refer to these as having the dimension ‘number’.
Consider units with respect to the concept of the quantity
they describe and this makes sense. ‘Metre’ is to the concept
‘length’ as ‘1’ is to the concept ‘number’. If we consider the
seven base quantities of the SI having dimensions lying along
seven mutually orthogonal axes in a 7D plot then we might
consider the dimension number to be the origin of that plot,
without magnitude along any of the seven axes but present at
the intersection of all of them.
Important measurements at the cutting edge of chemical
and biological metrology use counting quantities. Topical
examples would include measurements of the number of parti-
cles in air, copies of a DNA sequence or the number of colony
forming units in a sample of cells. Taking the example of par-
ticles in air, an exemplar measurement might be expressed as:
In the air sampled the number concentration of particles
with an aerodynamic diameter of between 10 nm and
1 µm was, C  =  (1.00  ±  0.05)  ×  106 1/m3.
This gives an unambiguous description of the quantity
being described and provides a clear number concentration
unit. The use of ‘1/m3’ explicitly highlights the nature of the
unit as a ratio of number (unit ‘1’) to volume (unit ‘m3’) and
is preferred by the author to ‘m−3’ which, whilst also correct,
loses this distinction. This example also highlights that SI pre-
fixes may not be used with the unit one. If we wished to use
SI prefixes they could be used, with a bit of thought, to qualify
the ‘m3’. However, as in the example, most expressions of
counting quantities use powers of ten in the expression of the
numerical result instead of employing SI prefixes. It is also
noteworthy that in the same way amount of substance is quali-
fied for specific use—in the earlier example the ‘amount of
sulphur hexafluoride’—if we think of counting quantities in
the form of the ‘number of items’ then this needs qualification
in a similar way when expressing a result—the ‘number of
sulphur hexafluoride molecules’.
Similarly to measurements of amount of substance that
normally determine the composition of mixtures, counting
measurements are rarely expressed as extensive quantities (in
such cases the unit ‘1’ would not be used on its own but would
be omitted) and so there will generally be the opportunity to
use the unit ‘1’ explicitly for extra clarity. The presence of the
unit ‘1’ in such a way also reminds us not to attempt to use
any description of the quantity in the unit: such as ‘cells/cm2’,
‘particles/m3’ or ‘particles(10nm−1 µm)/m3’. This use is strongly
deprecated as are similar examples for amount of substance,
such as ‘mmol Hg/m3’. Such ‘units’ could prop­agate uncon-
trollably if this usage was allowed with no clear distinction
between them or definitions associated with them. Proposals
to create taxonomies for such counting ‘units’ [22] do not
address these concerns since they neither set any limits for
the number of such units that could be created and used nor
explain how they would be officially controlled within the SI.
Such units also violate the general principle that the name of
the quantity should never be mixed with the name of the unit.
These proposals [23] add no value over and above the use of
Metrologia 55 (2018) L25
the unit one and a proper description of the quanti­ty being
described, save for enabling the use of SI prefixes, which
cannot be used with the unit one.
There are other examples of derived quantities which are
ratios of quantities of the same kind, which have the dimen-
sion one (or number) and whose units cancel to leave the unit
‘1’. In these cases, however, it is best practice to express the
unit ratio in question for clarity, so the use of SI prefixes is pos-
sible, and to displace any deprecated multipliers which often
fill such voids (such as ppb, pbbv, ppt, wt%, w/w, w/v to name
but a few [24]). For example, amount of substance fractions
(often shortened to amount fractions) are best expressed as
‘mol/mol’ rather than omitting these units. This also enables
the use of SI prefixes with these units, which is not possible if
the units are omitted, and avoids any possible confusion with
counting quantities.
More troublesome are ratios of intensive counting quanti­
ties—for example the ratio of number concentrations of par-
ticles with an aerodynamic diameter of between 10 nm and
2.5 µm to those with an aerodynamic diameter of between
10 nm and 10 µm (the ‘fine’ and ‘coarse’ particulate matter
fractions considered in air quality). Most information is
provided with the tolerably inelegant units ‘(1/m3)/(1/m3)’.
Whilst using no units at all here would be correct it would
lose the distinction that the units represent a ratio of number
concentrations. For those that prefer ‘m−3’ to express
number concentration, one faces the prospect of the more
eccentric expression ‘m−3/m−3’, which might be better sim-
plified to ‘m3/m3’. This risks confusion with a volume frac-
tion or volume concentration [25] but does enable the use of
SI prefixes.
An area of remaining possible confusion are extensive
counting quantities (for instance the number of cells in an
organism), and number fractions (the ratio of the number of
living cells to the total number of cells), where the units are
formally ‘1’ and ‘1/1’ respectively, but are omitted in practice.
In these situations there is no clear option save for the unam-
biguous description of the quantity being measured.
As discussed above, there is nothing incorrect with ele-
mentary entities being counted and the results expressed
using counting units. However, the benefits of using amount
of substance as described above are lost. This may become
more prevalent in the future as the frontiers of chemical
measurement are pushed back. This is discussed in the final
sections.
SI revision and the future of the mole
The proposed change to the definition of the mole [4] as part
of the wider revision of the SI [26] is now very likely to be
approved at the 26th meeting of the CGPM and implemented
in May 2019 [27]. The proposed new definition, based on a
fixed numerical value of the Avogadro constant, will have no
practical impact on chemical measurements in the short term,
and all relative atomic and molecular masses will remain
unchanged [3]. Realization of the mole will still be via stated
practical primary methods [28]—mises-en-pratique [18]—we
can no more weigh exactly 12 g of 12C than we can count
L30
Letter to the Editor
exactly the number of elementary entities specified by the
numerical value of the Avogadro constant.
The proposed new definition does, however, remove the
dependence on mass of the definition of the mole—the mole
will not depend on any other base units (or defining constants)
for its definition and no other base units will depend on the
mole or NA for theirs. It also removes the ‘understanding’
required that the previous definition relied on carbon 12 atoms
that are unbound, at rest and in their ground state—another
impossibility to achieve in practice [30]. For the chemical
metrology purist the equalization of the uncertainties of the
molar mass scale and the atomic mass scale resulting from
redefinition will provide a pleasing symmetry between the
microscopic and macroscopic worlds.
The proposed new definition would, in effect, reverse the
present definition, specifying a fixed number of elementary
entities in a mole, and clearly highlighting the role of the
Avodagro constant in the definition. By analogy, a single ele-
mentary entity will be equivalent to an exact amount of sub-
stance. This highlights a major future benefit of the proposed
new definition. As new techniques develop, the mole will
be realized across many orders of magnitude of the amount
of substance scale with equal uncertainty, and not just with
an uncertainty optimized for a specific artefact with larger
uncertainties away from this fixed point. Such is the benefit of
moving away from a definition reliant on a conversion factor
based on a material property—M(12C)—to one based on a
universal constant of proportionality—NA. Whilst practical
realization in the near future will still involve weighing, as
experimental techniques develop the counting of elementary
entities will become a more viable technique for realization
and quantification. This could be on the macroscale, such as
for the Avogadro Si sphere experiment [30], or on the micro-
scale, such as for single atom or single molecule counting and
accumulation [31].
The new definition of the mole based on a specified number
of elementary entities may not of itself induce any extra con-
fusion within the chemistry community between amount of
substance and counting quantities. Indeed there is some evi-
dence that many chemists have always seen the current defi-
nition of the mole in this way [3]. However a move towards
realization and quantification based on counting experiments
at the microscopic end of the scale, where most benefits of
redefinition will likely be felt, may induce more confusion.
Whilst one of the benefits of the mole discussed above is
for the expression of macro-sized chemical amounts using
user-friendly numbers, similarly the use of counting units
for expressing very small quantities of elementary entities
may also be considered to allow expression in a user-friendly
format. Consider these three equivalent expressions of the
presence of benzene in a given volume of gas (for clarity of
message the usual associated expression of uncertainty that
accompanies a measurement result has been omitted):
(i) The number concentration of benzene molecules is
80 1/m3
(ii) The amount concentration of benzene is 13.28…  ×  
10−23 mol/m3
(iii) The amount concentration of benzene is 132.8… ymol/m3
Metrologia 55 (2018) L25
(The units of expression (i) may also be expressed as
‘m−3’ as per the discussion above.) The presence of the
ellipsis […] indicates in the amount concentration expres-
sions (as in expressions (ii) and (iii)) that additional digits
have been intentionally omitted. Expression (i) immedi-
ately demonstrates the benefit of expressing very small col-
lections of material using counting units: it provides the
possibility to use integer numerical values in the measure-
ment result (given a suitable choice of denominator in the
unit expression13). This is not possible with the amount of
substance expressions—an approximation must be made.
Expression (ii) is also numer­ically more unwieldy than
expression (i), a situation that is resolved somewhat by
employing the rarely used SI prefix yocto, y. The drawback
of (i) is that expression in counting units prevents the asso-
ciated use of SI prefixes because SI prefixes are not allowed
with the unit ‘1’. Instead we would need to vary the prefix
associated with m3 or use powers of 10 in the numerical
expression.
This discussion, considering the very edge of current
quanti­tative chemistry, highlights the previously noted
ontological difference between continuous quantities and
countable aggregates. At these tiny amounts of substance it
seems more sensible to use numerical values associated with
counting that recognize the quantization of the measurement
at its absolute natural limit—a single molecule. Expressions
in terms of amount of substance do not recognize this abso-
lute natural limit. Stating ‘0.166 ymol’ may seem valid, but
represents a tenth of a molecule—a nonsensical concept when
taken out of context. Under these circumstances, amount of
substance still has the outward appearance of a continuous
quantity, but is more clearly exposed as having the character
of a countable aggregate.
It is perhaps worth highlighting at this stage that whilst a
fraction of an entity is a physical impossibility, in the sense of
expressing a measurement result it is still a valid concept. This
is true regardless of whether we are considering elementary
entities, or non-identical non-elementary collections of things,
as discussed earlier. Suppose in the expression (i) above the
experiment had been conducted several times and an average
produced, the statement ‘the average number concentration of
benzene molecules was 80.2 1/m3’ would be quite acceptable,
as would an expression of uncertainty dealing in fractional
entities for similar reasons. Equally an average value over sev-
eral measurements could conceivably return a result of less
than 1 entity. In these cases, however, one would need to con-
sider whether the user of the measurement result would under-
stand the subtlety of this apparent contradiction, and whether
results were better expressed as rounded to the nearest entity
or in some other way.
13
Whilst a count of the number of molecules (as an extensive quantity) must
be an integer, its subsequent expression as an intensive quantity relative to
the frame of reference of the measurement need not be. For instance, had an
odd number of molecules been counted in a volume of 2 m3, its expression
in 1/m3 would not be an integer.
L31
Letter to the Editor
New prefixes for ultra-low level chemical
measurement
One of the propositions of this article is to encourage the use
of amount of substance wherever possible, especially in the
emerging areas of ultra-low chemical and biological quanti­
fication. Under these conditions, the distinction between ele-
mentary entities and other things that could be counted down
to natural limits becomes increasingly important. It may be
that continued use of amount of substance in this regime can
be encouraged if we take a different approach to prefixes in
the future.
The advancement of science in both directions along the
scale of magnitudes may eventually drive the requirement for
new SI prefixes for 1027, 10−27, 1030 and 10−30 (some names
have already been suggested in scientific and popular literature
[32–36]); the last set having been approved over 25 years ago
[37]. (As an aside, the metrology community should act soon
to define what the names and magnitudes of new SI prefixes
should be before they are decided by common usage and prac-
tice in popular science culture and the wider media.) It is prob-
able that chemical measurement would not benefit greatly from
such new prefixes. Larger prefixes are only valuable if one is
describing the amount of substance in a star or other cosmo-
logical bodies. The usefulness of smaller prefixes is limited by
the description of a single elementary entity: one elementary
entity is approximately equivalent to 1.66 ymol, there are no
need for smaller prefixes. In order for SI prefixes to be useful
for ultra-low level amount of substance determination they need
to enable the benefits of the exact expression of results that is
naturally present with counting quantities. To do this we need
to think, not of basing prefixes on powers of 1000, but instead
relating these to the numerical value of the Avogadro constant,
{NA}, sometimes called the ‘Avogadro number [3]’.
Consider, for example, a new prefix ‘s’ which expresses
the multiplier 1/{NA} such that ‘1 smol’ is exactly equiva-
lent to one elementary entity, but retains the dimension of
amount of substance and all the associated benefits. We could
generalize this approach to consider a limited range of addi-
tional prefixes expressing multipliers of 1000n / {NA } with
n = 0, 1, 2, 3 . . . such that they all enable expression of amount
of substance with numerical equivalence to elementary enti-
ties at magnitudes suitable and useful for ultra-low level
chemical measurement. This approach is similar, albeit with
different motivating reasons, to the separate set of prefixes for
binary powers adopted by the International Electrotechnical
Commission in IEC 60027-2:2005. It is also has similarity to
previous proposals that the ‘ent’ should be the amount of a
single elementary entity [38, 39] although the proposal here
more easily aligns with the existing orthodoxy of the SI.
Conclusions
The benefits of establishing and retaining the mole as a base
unit within the SI are clear for the chemical community and all
other stakeholders. Many of these benefits relate to how this
status allows amount of substance (the quantity for which the
Metrologia 55 (2018) L25
mole is the base unit) to be distinguished from the counting
of elementary entities. Much of the discussion presented has
described the properties of these different quantities, how
they may be distinguished and how each is properly applied.
It has been proposed that this is important to do because of
the confusion between amount of substance and counting
quanti­ties both historically and also more recently as counting
is increasingly recognised as a valid measurement, using tra-
ditional measurement models and uncertainty analyses, and
is ­underpinned by the international metrological structure.
It has been highlighted that this issue has been brought into
sharp focus more recently by technological advances that
have allowed the identification and quantification of increas-
ingly small quantities of mat­erial, often down to single mol-
ecule levels. In order to make the continued use of amount
of substance quantities at these ultra-trace levels new prefixes
have been suggested that are based on the numerical value of
the Avogadro constant (to be fixed with zero uncertainty fol-
lowing the proposed SI revision in 2019). This would enable
expression of amount of substance with numerical equiva-
lence to elementary entities at magnitudes suitable and useful
for ultra-low level chemical measurement.
Acknowledgments
The funding of the National Measurement System by the
Department for Business, Energy and Industrial Strategy is
gratefully acknowledged.
ORCID iDs
Richard J C Brown https://orcid.org/0000-0001-6106-0996
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