Notes Rec. R. Soc. Lond.

56 (1), 89–94 (2002) © 2002 The Royal Society

THE CENTENARY OF EINSTEIN’S FIRST SCIENTIFIC PAPER

by

J N. M, F.R.S.,  N G

School of Chemistry, Physics, and Environmental Science, University of Sussex,

Brighton BN1 9QJ, UK

S

Einstein’s first paper was concerned with the interaction potential between
molecules, and although dismissed later by its author, and largely ignored by the
chemical community, it has some relevance to later developments of the subject.

T  

Einstein’s first scientific paper was published in Annalen der Physik in March 1901. 1
This was four years before the series of five papers published in the same journal in
1905 that turned him in very few years from being an unknown student to the most
famous physicist in the world. Einstein himself expressed later the view that this
paper, together with another published in 1902, was worthless (he wrote to Stark in
1907 saying, ‘I am sending you all my papers except for my worthless first two
papers’), and most of his biographers have had the same view, except in seeing the
paper as an indication of Einstein’s lifetime search for universal laws. As the paper is
concerned with the interaction between molecules and would not have looked out of
place in a journal of physical chemistry, it seems particularly appropriate to bring its
centenary to the notice of the chemistry community.
In July 1900 Einstein had completed his studies for a teaching diploma at the
polytechnic in Zürich (the Eidgenössische Technische Hochshule (ETH)), with,
among other marks, a modest 5 out of 6 for theoretical physics. Three other students
gained the same diploma and were all taken on as assistants at the ETH, but
Einstein was unsuccessful in his application and found himself jobless. The reason is
undoubtedly that he crossed swords with his professor of physics, Heinrich Weber;
Einstein later accused him of giving a very old-fashioned course.2
Einstein completed his first paper in December 1900, still jobless, and in 1901 he
was writing to several universities to find an academic position; there is even a letter
from his father to the famous chemist W. Ostwald saying, ‘My son is profoundly
unhappy with his current state of unemployment, and every day the idea becomes
more firmly implanted in him that he is a failure in his career…’. His father’s pleas

89
90 John N. Murrell and Nicole Grobert

were unsuccessful; one can only speculate on the conversation between Ostwald and
Einstein when in 1908 they both appeared at the University of Geneva to receive
honorary doctorates.
Einstein eventually obtained a temporary job as a high-school teacher in
Winterthur, from where he wrote to his friend Marcel Grossman (who is reputed to
have provided notes on the many lectures that Einstein missed in his studies) that he
was working on gas kinetic theory and was pondering the movement of matter
relative to the aether. Later that year he moved to a private school in Schaffhausen,
and stayed there until he obtained his famous job in the Bern patent office in 1902.

E’   

Einstein’s first interests were in the atomic theory of matter (or the reality of
molecules), and although by 1900 this was accepted by physicists and most chemists,
there were still a few doubters, most famously Ostwald himself, who only finally
recanted in 1909. Einstein’s PhD thesis, which was accepted by the University of
Zürich in July 1905, was on the determination of molecular dimensions and
Avogadro’s constant. He deduced these quantities from expressions he derived for
the viscosity and the diffusion coefficient of a hard sphere in a continuous medium,
and with the use of data for dilute solutions of sugar in water he obtained a value of
2.1 × 1023 mol−1 for Avogadro’s constant; after a later correction to one of the
equations the result was 6.6 × 1023 mol−1, which is amazingly close to the modern
value.
Einstein’s first paper, entitled ‘Folgerungen aus den Capillaritätserscheinungen’
(‘Conclusions drawn from the phenomena of capillarity’)1, starts with an analysis of
the thermodynamics of liquid surfaces. He proposes that as experiments reveal that
the surface tension g varies linearly with temperature, then the energy needed to
build a surface unit is independent of temperature; hence the specific heat of the
surface is zero. The energy of the surface can therefore be considered as a potential
energy, and this energy can be expressed by the function3

gT (dg /d T) .

He further concludes that this function is a better unit with which to analyse
‘stoichiometric aspects’ than g, which had been used so far. Now stoichiometry is
based on the law of conservation of matter, but it is clear later in the paper that
Einstein is interested in the possibility that the surface energy can be expressed by
additive contributions from the atoms making up the molecules in the surface. This
was not an original idea, because R. Schiff4 had previously derived atom-additive
contributions to g / M, where M is the molecular mass, and Partington5 gives earlier
references to people who had shown that there were regularities in the surface
tensions of liquids from molecules related within a homologous series (for example
those related by additional CH2 groups).
 The centenary of Einstein’s first scientific paper 91

I 

Einstein continues:
I started from the simple idea of attractive forces amongst the molecules, and I test the
consequences experimentally. I took gravitational forces as analogues. Therefore the
relative potential of two molecules is:
P = P∞ − c1c2 f(r). (1)
In this case, c is a characteristic constant of the molecule, f(r), however, is a function of
the distance of the molecules, which is independent of the nature of the molecule.

We can see immediately the limitations of this model because there are no angular
variables, to allow for electrostatic contributions to the potential, for example.
However, there have been many subsequent models that do no better, employing, for
example, a Lennard-Jones functional form for the potential. Indeed, the analysis of
gas imperfections has commonly ignored angular variables by considering only
spherically averaged potentials.
The total potential is a sum of all pair interactions, and if all the molecules are
the same, Einstein could write

P = P∞ − 12 c2 ∑a ∑b f (r) . (2)

He continues: ‘We also assume that the potential of the molecular forces is the
same as if the matter were to be evenly distributed in space. This, however, is an
assumption which we can expect to be only approximately true.’ In this way he could
replace the double sum in (2) by a double integral over all space, with a multiplying
factor that is the number of molecules per unit volume, or the reciprocal of this, the
molecular volume v. This would indeed be a very poor approximation because
molecules are kept apart at short distances by a repulsive branch of the potential,
and any model in which the distribution of matter is assumed to be uniform would
greatly overestimate the attractive forces.
To introduce stoichiometric properties Einstein then expresses the constant c as a
sum of constants ca, one for each of the atoms a in the molecule. This does not
introduce angular variables, but he could have been much closer to a popular
potential used today if instead of writing for a pair of molecules

P = P∞ − (∑a c1a) (∑b c2b) f12 (r) (3)

he had written
P = P∞ − ∑a ∑b c1ac2bfab (r ab) , (4)

which is a sum of atom–atom potentials. This model does introduce non-central

terms into the intermolecular potential.
The paper then contains some dubious analysis of the integrals introduced by the
uniform matter assumption, and the interesting comment, ‘We need to be aware that
92 John N. Murrell and Nicole Grobert

we do not know whether the weight of the molecule of the liquid exhibits the n-fold
weight of the molecule of the gas’, suggesting that Einstein is not clear about the
normal molecular structure of gases and liquids. He defines an integral (K') of the
potential taken over a surface layer (which has some unjustified limits), and then
comes to the key formula

K′ (∑a ca)2 / v2 = g − Y (d g / d T) , (5)

which he uses in the form

∑a ca = v ( (g − T (d g / d T)) / K′)2 .
1
(6)

A  O

Einstein goes on to say, ‘Since it is possible to calculate the unit of the boiling
temperature (for most materials) according to R. Schiff’s observations, we now have
many tools to determine ca. I took all information from a book about General
Chemistry by W. Ostwald.’6 He does not specify further this information, but the
assumption is that it is values of g, the molecular volume (v) and the boiling point
that go into equation (6). As K' is unknown, the unit for ca was chosen arbitrarily.
He used a least-squares method for optimizing the ca parameters, and for a series of
hydrocarbons he obtained the values

cH = −1.6, cC = 55.0, cO = 46.8.

He used data from 17 compounds in his least-squares analysis, the smallest

molecule being formic acid (fitted Σaca was 140; observed was 145), and the largest
being carvol, C10 H14O (fitted Σaca was 587; observed was 574). He then proceeded to
examine data for a series of 24 halogenated compounds (such as chlorobenzene,
ethylbromide and allyliodide) and obtained the ‘less accurate’ values for the halogen
parameters

cCl = 60, cBr = 152, cI = 198.

He writes, ‘I have the impression that there are greater deviations (from the
theoretical values ) for substances exhibiting a relatively large molecular mass and a
small molecular volume’.
From the fact that his model fitted the experimental data quite well he concludes
that (3) is a good basis for understanding intermolecular potentials, and he tries to
confirm this (unsuccessfully) by comparing Σaca with a quantity based on the heat of
evaporation.
 The centenary of Einstein’s first scientific paper 93

A    

Einstein then goes on to use a different method for determining ca:

If the liquid is compressed at a constant temperature and its heat content does not change,
which we are now assuming, then the heat resulting from compression equals the sum of
the compression work and the work carried out by the molecular forces.
After some thermodynamic analysis he arrives at the formula

(Tav2 / c) = (∑a ca)2 , (7)

where a is the thermal expansion coefficient and c the compressibility coefficient.

Values for these two quantities were taken from the tables of Landolt and Börnstein.
He then continues: ‘In this way we obtain the following values: Xylol 1.71 × 104,
ethylalcohol 1.70 × 104, etc.’. Although it is not clear from the paper what these
1
values refer to (most probably they are ca in heat units (calories 2 )), Einstein goes on
to say ‘It is important to note that both coefficients obtained using different methods
are in relatively good agreement with each other, although the two methods are
based on different phenomena’. He finds some variation in the values for alcohols
with high carbon content, and concludes that the molecules of these compounds are
dependent on temperature.
Einstein’s last paragraph is as follows:
Finally, it is noteworthy that the constants ca in general increase with increasing atomic
weight, but not always proportionally. The question whether and how the forces are related
to the forces of gravity cannot be answered yet. In addition, the introduction of the
function f(r), which should be independent of the nature of the atoms, and the
substitution of the sums by integrals are both approximations. In fact, our theory does not
apply for substances exhibiting small molecular volumes, as shown by the example of
water. Further research needs to be carried out to solve these questions.

C   

The paper is very difficult to understand, not least because of the large number of
obvious misprints; from its lack of clarity we can only assume that it had not been
independently refereed. We could well imagine Ostwald depositing it in the bin when
the paper was received from Einstein’s father. Yet it was an extraordinarily advanced
paper for a recent graduate who was receiving no independent scientific advice. The
idea behind a stoichiometric analysis of surface tension goes back to the work of
R. Schiff, and this was well discussed in Ostwald’s book, but to suppose that one
could obtain some information about intermolecular potentials by such an analysis
is probably Einstein’s own idea. It is interesting that the stoichiometric analysis of
surface tension and its interpretation through molecular structure became very
popular from the work on the parachor, a quantity introduced by Sugden7 and
others in the 1920s. The parachor is equal to the fourth root of the surface tension
94 John N. Murrell and Nicole Grobert

divided by the difference between the liquid and gas densities, and multiplied by the
molecular mass, and is a quantity that is largely independent of temperature. The
parachor was subjected to a large number of analyses and interpretations in
subsequent years, but the subject died a rapid death in the 1940s.

N

1 A. Einstein, ‘Folgerungen aus den Capillaritätserscheinungen’, Annalen Phys. 4, 513–523

(1901); English translation, ‘Conclusions drawn from the phenomena of capillarity’, in The
collected papers of Albert Einstein, supplementary volumes, vol. 2, pp. 1–11 (Princeton, New
Jersey, Princeton University Press, 1989). There is a short analysis of this paper entitled
‘Einstein on the nature of intermolecular forces’ in these collected papers (not the
supplementary volumes), vol. 2, pp. 3–8.
2 Probably more biographies have been written on Einstein than on any other scientist. Two
that have been found very useful in writing this article are: A. Pais, Subtle is the Lord
(Oxford University Press, 1982), and M. White & J.R. Gribben, Einstein: a life in science
(Dutton, New York, 1994).
3 This function was later chosen for analysis by several workers, for example G.M. Bennett &
A.D. Mitchell, ‘Total surface energy and chemical constitution’, Z. Phys. Chem. 84, 475–497
(1913).
4 R. Schiff, ‘Ueber die Capillaritätsconstanten der Flüssigkeiten bei ihrem Siedepunkten’,
(Liebig’s) Annln Chim. 223, 47–106 (1884); R. Schiff, ‘Über einige physicalische
Eigenschaften des Thiophenes’, Berichte 18, 1601–1606 (1885).
5 J.R. Partington, An advanced treatise of physical chemistry, vol. 2, p. 195 (London,
Longmans Green & Co., 1951).
6 W. Ostwald, Lehrbuch der allgemeinen Chemie, vol. 1 (Stöchiometrie) (Engelmann, Leipzig,
2nd edn, 1891).
7 S. Sugden, ‘The variable of surface tension with temperature and some related functions’,
J. Chem. Soc. 125, 32–41 (1924); S. Sugden, The parachor and valence (London, Routledge,
1930).