A new definition for the mole based

on the Avogadro constant;

a journey from physics to chemistry

Martin Milton
NPL

The Royal Society, London

24th January 2012
 Outline
• The development of today’s understanding of:
– the quantity amount of substance,
– the unit mol, and
– the Avogadro constant.
• How have we come to a definition whereby we
know the mass of a mole, but not the number of
entities in it?
– Is there justification for a change?
– What would the consequences be?
• How is the mole realised in practice?
– some examples of the best uncertainties currently
achievable
The concept “amount of substance”
Boyle’s Law (1662)
“For a fixed amount of gas kept at a fixed temperature, P and V are inversely
proportional”

Stoichiometry (Lavoisier)
“the relationship between the amounts of substance that react together, and
the products that are formed”

Law of Multiple Proportions– (Dalton 1803)

“when elements combine, they do so in a ratio of small whole numbers”

Law of Definite Proportions (Proust 1806)

“a chemical compound always contains exactly the same proportion of
elements by mass”

Avogadro’s Law (1811)

“Equal volumes of ideal or perfect gases, at the same temperature and
pressure, contain the same number of particles, or molecules.”
 The gram-molecule
Kilogrammolekuel and g-Molekuel used by Ostwald
and Nernst in their text books in 1893.

Abbreviation to Mol recorded by Nernst.

gramme-molecule - First used in English in the

Encyclopaedia Britannica (1893).

mole – First used in English in the translation of

Ostwald’s “Principles of Inorganic Chemistry”
(1902).
 The gram-molecule in use
“On the Motion of Small Particles Suspended in a Stationary Liquid, as Required by
the Molecular Kinetic Theory of Heat” Einstein, 1905
• Van’t Hoff’s Law for the osmotic pressure Π V = z R T
Where z gram-molecules is dissolved in a a volume V
Let z=n/N where
n suspended particles are present and
N signifies the actual number of molecules contained in a gram-molecule
• The Stokes-Sutherland-Einstein formula RT
aN A =
6πη D
 The gram-molecule in use
“On the Motion of Small Particles Suspended in a Stationary Liquid, as Required by
the Molecular Kinetic Theory of Heat” Einstein, 1905
• Van’t Hoff’s Law for the osmotic pressure Π V = z R T
Where z gram-molecules is dissolved in a a volume V
Let z=n/N where
n suspended particles are present and
N signifies the actual number of molecules contained in a gram-molecule
• The Stokes-Sutherland-Einstein formula RT
aN A =
6πη D
“A new determination of molecular dimensions” Einstein, 1906
• Calculate the change in viscosity when spheres of radius a are dissolved in
a solvent of viscosity η *
η
= (1 + 2.5φ )
η
The total volume of dissolved material per unit volume of solvent
4 N
φ = πa 3 ρ
3 M
The gram-molecule defined

Perrin (1909)

“It has become customary to name as the gram-molecule of a

substance, the mass of the substance which in the gaseous
state occupies the same volume as 2 grams of hydrogen
measured at the same temperature and pressure.

Avogadro's proposition is then equivalent to the following:

Any two gram-molecules contain the same number of
molecules.

This invariable number N is a universal constant, which may

appropriately be designated Avogadro's Constant."

J. B. Perrin, “Mouvement brownien et réalité moléculaire”,

Annales de chimie et de physiqe VIII 18, 5-114 (1909).
trans: F. Soddy “Brownian Movement and Molecular Reality”,
Taylor and Francis (London) 1910.
 The “Mol” in use
Stille (PTB) explained in 1955 that Mol was being used in two conceptually
different ways.

• The ”chemical mass unit” for example

1 mol = 22.991 g of sodium, or
1 mol = 58.448 g of sodium chloride

• The ”number of moles” ( from Molzahl ) given by the equation:

l=ν/L ν = number of entities
L = {NA}

• Stille advocated the use of the Molzahl as a dimensionless quantity rather

than the use of the quantity Stoffmenge (literally “amount of substance”)
1 Mol is “the Stoffmenge that contains as many entities as Ar(O) g of
atomic oxygen”.

Stille “Messen und Rechnen in der Physik” 1955

 Amount of substance
Guggenheim

• ..”for special problems it may be advantageous to increase

the number of fundamental quantities above the usual
number. It can sometimes be useful in dimensional
analysis to regard the number of atoms as having
dimensions different from a pure number”
– Guggenheim, E. A. 1942 Units and Dimensions
• Phil. Mag. 33 pp479-496.

• “This quantity was first named “Stoffmenge” in German

and the English translation is amount of substance”
– Guggenheim, E. A. 1961 The Mole and Related Quantities
• J Chem Ed 38 86-87.
 The 1971 definition of the mole

– “The mole is the amount of substance of a system that

contains as many elementary entities as there are atoms
in 0.012 kilogramme of carbon 12.

When the mole is used, the elementary entities must be specified

and may be atoms, molecules, ions, electrons, or other particles,
or specified groups of such particles”.
– 14th CGPM, 1971

• resolved the confusion arising from the use of both

• g-mol and kg-mol

• 12C and 16O basis

• introduced dimensional analysis to chemistry.

McGlashan, Metrologia, 1995, 31, 447-455.

The atomic mass scale

The N measured atomic masses are related by

the N-1 ratios Ar(X)/Ar(Y).
So we fix the value of the Nth ratio Ar(12C).

mu m(12C) m(X)
Ar(12C) Ar(X)
 Atomic masses and fundamental constants

ron

nit
n-1
t
lec

ss u
rbo
ee

ma
ca
th

of

mic
of

ss

At o
ss

Ma
Ma

Ar(e)/Ar(12C) Ar(12C)
atomic me m(12C) mu
level

Fixed Mass
value
 the mole (present definition)

Ar(12C)
M(12C) Mu
macroscopic

10-3 kg mol-1

Ar(e)/Ar(12C) Ar(12C)
atomic me m(12C) mu
level

Fixed Mass
value
 the mole (present definition)

Ar(12C)
M(12C) Mu
macroscopic

NA NA

Ar(e)/Ar(12C) Ar(12C)
atomic me m(12C) mu
level

Fixed Mass
value
 Why change
the definition of the mole?

• There is very little initiative for any change from the

communities of users of the mole.
– there is momentum behind the proposal for a “new SI”
– which could include a fixed value for NA
A possible rationale for change
• The mole has been derived from the gramme-molecule
– the amount of substance of 12g of 12C.
– We know the exact mass of a mole (of 12C),
– do not know the exact number of entities

NA has some uncertainty

Is this sufficient to motivate a change?
 the mole (present definition)

Ar(12C)
M(12C) Mu
macroscopic

NA NA

Ar(e)/Ar(12C) Ar(12C)
atomic me m(12C) mu
level

Fixed Mass
value
 the mole (new definition)

Ar(12C)
M(12C) Mu
macroscopic

Fixing NA means that

another quantity in this
NA NA
system has to be
determined
experimentally.

Ar(e)/Ar(12C) Ar(12C)
atomic me m(12C) mu
level

Fixed Mass
value
 A new definition for the mole
• The proposed new definition would reverse the
present definition
– specify the number of entities in one mole
• equal to NA exactly.
– some uncertainty in the mass of one mole
• one mole of carbon-12 = 12g +/- u(α2).
• The molar masses and the atomic masses will have
the same (relative) uncertainties.
• A single entity will be an exact amount of substance.
• Both approaches will be the same in practice
• to within +/- u(α2)
 Possible definition 201X ?
201X
– “The mole is the unit of amount of substance of a
specified elementary entity, which may be an atom,
molecule, ion, electron, any other particle or a specified
group of such particles; its magnitude is set by fixing the
numerical value of the Avogadro constant to be equal to
exactly 6.022 14X 1023 when it is expressed in the unit
mol-1.”
1971
– “The mole is the amount of substance of a system that
contains as many elementary entities as there are atoms
in 0.012 kilogramme of carbon 12.
When the mole is used, the elementary entities must be specified
and may be atoms, molecules, ions, electrons, or other particles,
or specified groups of such particles”.
 The debate about a new
definition for the mole
• Many users are confused about the existing use of the mole.

• The mole has always been used in conceptually different, but

equivalent ways

“chemical mass unit” “number of moles” “amount of substance”

n= m / Ar(X) Mu l = ν / {NA} n= ν / NA

• Much of the discussion originates from authors who believe that one
of these is correct to the exclusion of the others.
• Would a change in the definition put an end to this discussion?
 The Avogadro constant
Invention of new physical
methods: diffusion, Brownian
motion, oil drop

Improvement in X-ray
wavelength measurements

Atomic weight and chemical

purity problems with Silicon

U(MM) contributes 61% of the

published uncertainty of the
2003 natural Si result

Becker, Rep Prog Phys 2001

 High accuracy measurements (I)
the composition of the atmosphere
Compound
CIPM 81/91 formula
Revised values (2004) To be published 2011
Measurement Nitrogen mole fraction in dry
Giacomo et al (1982)
air directly by GC/TCD
0.78082 ± 0.00012 0.780 93 ± 0.00006 Pure N2
N2 0.78101 Pure CH4 Pure CO2 Pure Ar Pure O2
(Calculated by difference) Measured
10 % CH4/N2
0.20945 ± 0.00012 0.209 45 ± 0.00012 5 % CO2/N2
O2 0.20939
NIST (1970) NIST (1970) 0.7 % CH4/N2

0.045 % CH4/N2 0.43 % CO2/N2

Ar 0.00917 0.009332 ± 0.000006 0.009 331 ± 0.000006
Kim et al (2004) 0.028 % CH4/N2

CO2 0.00040 0.000369 ± 0.000001 0.00040

0.038 % CO2 + 0.00016 % CH4 + 0.93 % Ar
Metrologia 18 (1982) 33-40 Metrologia 41 (2004) 387–395
+ 20.9 % O2 + N2 Balance
expanded uncertainties (k=2)

Relative uncertainty of 60 parts-per-million achieved

– with respect to standards prepared gravimetrically

Courtesy of
Dr Jin Seog Kim, KRISS, Korea
 High accuracy measurements (I)
the composition of the atmosphere
Compound
CIPM 81/91 formula
Revised values (2004) To be published 2011
Measurement Nitrogen mole fraction in dry
Giacomo et al (1982)
air directly by GC/TCD
0.78082 ± 0.00012 0.780 93 ± 0.00006 Pure N2
N2 0.78101 Pure CH4 Pure CO2 Pure Ar Pure O2
(Calculated by difference) Measured
10 % CH4/N2
0.20945 ± 0.00012 0.209 45 ± 0.00012 5 % CO2/N2
O2 0.20939
NIST (1970) NIST (1970) 0.7 % CH4/N2

0.045 % CH4/N2 0.43 % CO2/N2

Ar 0.00917 0.009332 ± 0.000006 0.009 331 ± 0.000006
Kim et al (2004) 0.028 % CH4/N2

CO2 0.00040 0.000369 ± 0.000001 0.00040

0.038 % CO2 + 0.00016 % CH4 + 0.93 % Ar
Metrologia 18 (1982) 33-40 Metrologia 41 (2004) 387–395
+ 20.9 % O2 + N2 Balance
expanded uncertainties (k=2)

Relative uncertainty of 60 parts-per-million achieved

– with respect to standards prepared gravimetrically

Courtesy of
Dr Jin Seog Kim, KRISS, Korea
 High accuracy measurements (I)
the composition of the atmosphere
Compound
CIPM 81/91 formula
Revised values (2004) To be published 2011
Measurement Nitrogen mole fraction in dry
Giacomo et al (1982)
air directly by GC/TCD
0.78082 ± 0.00012 0.780 93 ± 0.00006 Pure N2
N2 0.78101 Pure CH4 Pure CO2 Pure Ar Pure O2
(Calculated by difference) Measured
10 % CH4/N2
0.20945 ± 0.00012 0.209 45 ± 0.00012 5 % CO2/N2
O2 0.20939
NIST (1970) NIST (1970) 0.7 % CH4/N2

0.045 % CH4/N2 0.43 % CO2/N2

Ar 0.00917 0.009332 ± 0.000006 0.009 331 ± 0.000006
Kim et al (2004) 0.028 % CH4/N2

CO2 0.00040 0.000369 ± 0.000001 0.00040

0.038 % CO2 + 0.00016 % CH4 + 0.93 % Ar
Metrologia 18 (1982) 33-40 Metrologia 41 (2004) 387–395
+ 20.9 % O2 + N2 Balance
expanded uncertainties (k=2)

Relative uncertainty of 60 parts-per-million achieved

– with respect to standards prepared gravimetrically

Courtesy of
Dr Jin Seog Kim, KRISS, Korea
 High accuracy measurements (II)
highly pure metals
“Raw” Vacuum distilled
Zn 99.995% Zn 99.99995%
16 determined
43.0 mg/kg 0.5 mg/kg
impurities

38.5 kg/mm2 Vickers

32.6 kg/mm2
micro hardness

BAM-M601 w [mg/g]
Cd 0.55 ± 0.06
Fe 2.20 ± 0.09 Courtesy of
Cu 1.89 ± 0.11 Dr Heinrich Kipphardt,
Tl 2.25 ± 0.09 BAM, Germany
Pb 15.7 ± 0.3
 High accuracy measurements (II)
highly pure metals
“Raw” Vacuum distilled
Zn 99.995% Zn 99.99995%
16 determined
43.0 mg/kg 0.5 mg/kg
impurities

38.5 kg/mm2 Vickers

32.6 kg/mm2
micro hardness

BAM-M601 w [µg/g]
Cd 0.55 ± 0.06
Courtesy of
Fe 2.20 ± 0.09
Cu 1.89 ± 0.11 Dr Heinrich Kipphardt,
Tl 2.25 ± 0.09 BAM, Germany
Pb 15.7 ± 0.3
 Summary
• The mole and the Avogadro constant
• Emergence of ideas of stoichiometry and thermodynamic
ensemble (18th and 19th centuries)
• Accurate chemical measurement (21st century)
• The mole has been used in conceptually different
ways
• chemical mass unit
• number of moles
• amount of substance
• At present, we know the mass of a mole (of 12C),
but not the number of entities.
– is there sufficient momentum behind proposals to change?
– where should u(α2) lie?
Acknowledgements
• Dr Bernd Güttler (PTB)
• Prof Ian Mills

The National Measurement System is the

UK’s national infrastructure of measurement