Waterston's Influence on Krönig's Kinetic Theory of Gases

Author(s): Edward E. Daub

Source: Isis, Vol. 62, No. 4 (Winter, 1971), pp. 512-515
Published by: The University of Chicago Press on behalf of The History of Science Society
Stable URL: https://www.jstor.org/stable/229822
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 NOTES & CORRESPONDENCE

WATERSTON'S INFLUENCE ON KRONIG'S KINETIC THEORY OF GASES

By Edward E. Daub*

A discontinuity persists in our attempts to reconstruct the history of the kinetic

theory of gases: this is that obvious gap between the emergence of those ideas in
Britain, particularly in J. J. Waterston's proposals, and the historically more decisive
beginnings in Germany a decade later, initiated by August Kronig in 1856 and firmly
established by Rudolph Clausius in 1857. When Stephen Brush surveyed the record in
his papers on the kinetic theory' he found one lone contemporary reference to Water-
ston's work in German-a single-sentence comment by Hermann von Helmholtz in
Die Fortschritte der Physik. The article under review was a brief abstract of Waterston's
presentation at the British Association for the Advancement of Science in 1851, en-
titled "On a General Theory of Gases."2 Brush concluded that Kronig, as editor of
this volume of Die Fortschritte, would certainly have read Helmholtz's review, even
though he made no mention of Waterston in his 1856 paper.3
I should like to suggest that Kronig also read Waterston's abstract and that he was
strongly influenced by the ideas he discovered there when he developed his theory. I do
not mean to imply any overt plagiarism on Kr6nig's part. As editor he undoubtedly
scanned a great deal of material and-an experience common to us all-may not al-
ways have been able to distinguish his original thoughts from those derived by reading
others. I am suggesting this possibility because I have found remarkable parallels in the
two papers, with almost every major point made by Kronig already stipulated in the
terse summary of Waterston's ideas.
I will quote Waterston's abstract in its entirety, interspersing the paragraphs with
corresponding passages from Kronig.

Waterston: "On a General Theory of Gases"4

The author deduces the properties of gases, with respect to heat and elasticity, from a
peculiar form of the theory which regards heat as consisting in small but rapid motions of
the particles of matter. He conceives that the atoms of a gas, being perfectly elastic, are
in continual motion in all directions, being restrained within a limited space by their
collisions with each other, and with the particles of surrounding bodies. The vis viva of
those motions in a given portion of gas constitutes the quantity of heat contained in it.

* Engineering Experiment Station, College ofAdvancement of Science, 21st Meeting, 1851,

Engineering, University of Wisconsin, Madison,
Wisconsin, 53706.
IS. G. Brush, "The Development of the
Kinetic Theory of Gases II. Waterston," Annals
of Science, 1957, 13: 273-282.
2 J. J. Waterston, "On a General Theory of
Gases," Report of the British Association for the
1852, in Notes and Abstracts, p. 6.
3 Brush, "Kinetic Theory of Gases II," p. 282.
4Since Waterston's abstract "On a General
Theory of Gases" is limited to a single page in the
BAAS Report, I will not give citations for the
quotations.

512

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 EDWARD E. DAUB 513

Kroniig: "Grundziige einer Theorie der Gase"5

The mechanical theory of heat maintains that the heat in a body consists simply of the
motions of its smallest parts. No clear conception is given, however, as to how those
motions are actually constituted. I will present a hypothesis for gases ... which seems to
meet the hitherto unfulfilled requirement . . . of providing derivations for the usual
equations of gases.... That hypothesis is the following.
Gases consist of atoms which behave like hard perfectly elastic spheres that are moving
with certain velocities in empty space. . . A gas atom does not oscillate about some
equilibrium point but moves in a straight line at a constant velocity until it collides with
another gas atom or against a solid or fluid surface.6
If the temperature of a gas is equal to the vis viva of an atom, then the amount of heat
contained in that gas is equal to the total vis viva of all the atoms.7

Waterston

He shows that the result of this state of motion must be to give the gas an elasticity pro-
portional to the mean square of the velocity of the molecular motions, and to the total
mass of the atoms contained in unity of bulk; that is to say, to the density of the medium.
This elasticity, in a given gas, is the measure of temperature. Equilibrium of pressure and
heat between two gases takes place when the number of atoms in unity of volume is equal,
and the vis viva of each atom is equal. Temperature, therefore, in all gases, is proportional
to the mass of one atom multiplied by the mean square of the velocity of the molecular
motions, being measured from an absolute zero 4910 below the zero of Fahrenheit's
thermometer.

Kronig

The pressure on the wall ... neglecting all constant factors ... is
p - nmc2/v.
This equation shows that the pressure of the gas is, as the law of Mariotte states, . . .
inversely proportional to the volume.
I must now introduce another assumption, in addition to those I have already made,
that the product Mc2 or the vis viva (die lebendige Kraft) of an atom is identical with the
temperature when measured from the point of absolute zero.
According to the law of Gay-Lussac, a gas exerts no pressure at -273?C and, at any
temperature t? higher, exerts a pressure proportional to t (the volume of course remaining
constant). These conclusions also follow from the equation
p -=nt/v
obtained when t= mc2 is substituted in the previous expression.
From P1lP2 and tf=t2 and v1=v2, it follows that n1=n2, i.e., different gases contain
equal numbers of atoms in equal volumes at the same temperature and pressure.8

Waterston

If a gas be compressed, the mechanical power expended in the compression is trans-

ferred to the molecules of the gas increasing their vis viva; and conversely, when the gas
expands, the mechanical power given out during the expansion is obtained at the ex-
pense of the vis viva of the atoms. This principle explains the variation of temperature
produced by the expansion and condensation of gases-the laws of their specific heat
under different circumstances, and of the velocity of sound in them. The fall of tempera-
ture found on ascending in the atmosphere, if not disturbed by radiation and other
causes, would correspond with the vis viva necessary to raise the atoms through a given
height.

r A. Kr6nig, "Grundziuge einer Theorie der 7Ibid., pp. 320.

Gase," Annalen der Physik, 1856, 99:315-322. 8 Ibid., pp. 317-318.
8 Ibid., pp. 315-316.

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514 WATERSTON'S INFLUENCE

Kronig

The temperature relations of gases during changes in volume are also easily estab-
lished from these assumptions.
Consider two containers of equal volume which have a common partition-wall, the one
filled with n atoms of gas of mass m and velocity c, the other empty. Let a portion w of
the wall be removed. Now those atoms which would have struck w will pass through the
opening ... [so that] there will soon be as many atoms passing through in one direction
as the other, and the pressures in the two containers will be equal. Obviously c, and
therefore also mc2, are not changed in this process. It follows that if a gas expands with-
out overcoming a resistance, it suffers no change in temperature.
If the pressure of a gas, the impacts of its atoms, act against a moving retreating piston,
the atoms must lose as much of their vis viva, i.e., of their heat, as they impart to the
piston.
Finally, if a gas is compressed by a piston, the atoms will rebound from the approaching
piston with greater velocities than they possessed upon meeting it. The gas therefore will
become warmer.9

Waterston

The author shows that the velocity with which gases diffuse themselves is proportional
to that possessed by their atoms according to his hypothesis.

Kr6nig

If the assumption of continually moving gas atoms should appear somewhat strange, I
need only mention the rapidity with which a small amount of hydrogen sulfide will
diffuse throughout a large room. By assuming that temperature is measured by mc2,
one may demonstrate that a gas will diffuse more rapidly the lower its specific weight.'0

The parallelism between their ideas would have been more complete if I had included
Kronig's discussion of gravity and atmospheric pressure. Those paragraphs proved
difficult to capsule in a few phrases, however, and will be discussed in some detail
below. Comparing the two accounts, we find that Krdnig differs from Waterston only
at two points: Kr6nig considers the topic of free expansion, which is absent from
Waterston's account, and he makes no mention of the various specific heats of a gas
and their relation to the velocity of sound. Actually, if he had attempted to calculate
the difference between the specific heats at constant pressure and at constant volume, he
would not have reached the right answer, and this leads to my second reason for con-
tending that Kronig had read Waterston's abstract. He does not seem to have had
sufficient mathematical powers to originate his theory without some preliminary
intimation of the relationships to seek.
When Kronig omitted all constant factors from his expression for the pressure,
reducing it to p nmc2/v, he covered up a basic flaw in his derivation, namely, that he
had wrongly assigned the quantity mc to the force exerted by an atom colliding with a
wall. Brush believes this was not an oversight. "From the context, it appears that this
error is not merely a misprint. Immediately afterwards it becomes clear that Kronig is
not interested in such trivial matters as factors of two, and he gives the final formula as
p = nmc2/V ... ('wir ... den constanten Factorfortlassen.').""
This lack of attention to mathematical rigor is further apparent when Krinig sought
to show that deviations from the gas laws might be expected from his elastic sphere

9 Ibid., pp. 321-322. Kinetic Theory of Gases III. Clausius," Ann. Sci.,
10 Ibid., p. 320. 1958, 14:185-196; p. 189.
11 S. G. Brush, "The Development of the

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 EDWARD E. DAUB 515

model. Consider, he said, two atoms in a rectangular box moving at a velocity c parallel
to the side of length x. Their joint collisions with either of the end walls should occur
with a frequency of 2(c/2x). Suppose, however, Kr6nig continued, that the two atoms
do not traverse the entire interval but collide with one another head-on, so that each
atom is restricted to one of the two walls. Three possibilities might arise. "Either both
of the atoms would take the same amount of time from the wall to their collision and
back, namely, 2(1x/c), or one of them would take a smaller or a larger time. In the first
case the formula originally derived for the pressure would be perfectly correct, but in
the second case the pressurep would be greater than nmc2/v and in the third case less."12
Similar considerations, Kronig suggested, would account for other deviations from the
laws derived.
His example, however, failed to explain deviations from the gas law. He should
have realized, by carrying his analysis one collision further, that there would be no
overall effect on the pressure even if the atoms collided away from the center. If a
collision occurred near one wall at any given moment, then the next collision between
those two atoms would occur at the corresponding location near the other wall. Head-
on collisions between perfectly elastic spheres may be considered as though each
sphere continues with its original motion.
Further evidence that Kronig lacked mathematical perceptiveness appears in his
treatment of the pressure of the atmosphere, where he accepted the value img for
pressure which an atom in the atmosphere would exert on the surface of the earth,
g being the acceleration of gravity. Brush was puzzled by this obvious discrepancy:
"one might have thought that this result, implying that the pressure of a gas is only
one-half its weight, would have led him to discover the original error which introduced
this spurious factor of one-half."'13 These mathematical mistakes suggest to me that
Kronig was only able to reach the relation p nmc2/v because the essential variables
were already known to him from reading Waterston.
My third reason for believing that Krbnig was influenced by Waterston's abstract
is the fact that he considered the effect of gravity on rising atoms. He did so in order to
explain why an atom should not exert a greater pressure at higher temperatures despite
its increased momentum. The issue could have been easily resolved by noting that
according to the relation p = nmc2/v the pressure would be constant if the number of
atoms per unit volume decreased inversely with the temperature Mc2. Instead, Kronig
calculated the time for an atom to rise against gravity and return to earth, demonstra-
ting that the increased impact measured by mc would be countered by the reduced
frequency g/2c, their product yielding the constant value ,mg.14 The fact that Krdnig
adopted this more complicated approach is, I believe, further evidence of Waterston's
influence, since his abstract had suggested such cases: "The fall of temperature found
on ascending in the atmosphere ... would correspond with the vis viva necessary to
raise the atoms through the given height."
If my contention that Kronig read Waterston's abstract should prove acceptable, our
reconstruction of the history of the kinetic theory of gases would be more satisfying
in two respects. It would support George Sarton's dictum that in the realm of scientific
ideas there are no wholly unbegotten fathers. It would also confer upon Waterston a
significant historical role, since Kronig's paper, by inducing Clausius to divulge his
more profound theory, initiated the chain of events which led to Maxwell. Thus,
Waterston would have helped to make the breach in British insularity to his own views.

12 Krxbnig, "Theorie der Gase," p. 321. p. 189.

13 Brush, "The Kinetic Theory of Gases III," 14 Kronig, "Theorie der Gase," pp. 318-319.

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