The compressibilities and expansion coefficients of

gases at low pressures, and their relation to

molecular volume
B y J. B. M. Co ppo c k
Chemistry Department, Battersea Polytechnic

municated by J. Kenyon, — Received 29 March 1939

S
.R
F
Revised 20 June 1939)

In t r o d u c t io n
The determination of molecular and atomic weights by the limiting
density and limiting pressure methods has furnished considerable data on
the behaviour of gases in the neighbourhood of atmospheric pressure. I t is
customary in this work to express the deviations from the ideal gas laws
U V
in terms of either the compressibility 1 + A = or the compressibility

coefficient A , where 1 Pivx, p 0v0is the limiting value of pv at in­

PoV0
finitely low pressure, p 1v1 the value at 1 atm., and the temperature 0° C.
The present paper describes a simple method of expressing compressibilities
and related low pressure data for non-polar gases in terms of their effective
molecular volume.
In previous papers (Coppock 1933, 1935 a) it has been shown how 1 + A
values and expansion coefficients at low pressures may be calculated with
considerable accuracy from the Beattie-Bridgeman (1928, 1930) equation
of state, in which the constants have been derived from high-pressure
data. This equation may be written in the virial form as follows:

pV m + y+ y + 2 p g ,
(1)
Tic
where P r t b .- a,- ^ ,
R B 0c
—R T B 0b + A 0a
R B 0bc
S

l0, a, B 0, b and c are characteristic constants for each gas.

[ 201 ]
202 J. B. M. Coppock
For condensable gases such as carbon dioxide the major contribution
in representing the deviation from the ideal laws at N.T.P. is contained in
the fi/V term, the other terms affect by about 1 part in 100,000.
Keesom has pointed out th a t many equations of state are of the type

(2)

so th at at 1 atm. pressure we may identify the /?/F of the Beattie equation

with B.
The virial coefficient B in equations of type (2) is related to the van der
Waals constants a and b by the simple relation

thus at constant temperature B is proportional to b —ka, where k is a

constant. In the case of non-polar gases at low pressures the intermolecular
forces would be at a minimum, and a itself may not be of great importance,
hence B should be a function of the molecular volume and deviations of
these gases from the ideal laws expressed in terms of their compressibility
would be a linear function of their actual volume. In this connexion it
should be noted th at Cawood and Patterson (1933) concluded from a
critical study of the van der Waals and Dieterici equations of state th a t
the limiting value of the compressibility of a gas at the critical temperature
is directly proportional to the critical volume, i.e. it depends only on the
volume occupied by the molecules.
Keesom (1921) suggested for non-polar gases th a t B — § 3, where N
is the Avogadro number and d the molecular diameter. For polar gases

B — - N ud^i 1—-_____ — _____

* 3 \ 3 d*R*T*]’
where p is the dipole moment.
If B for non-polar gases were completely represented by the effective
molecular volume, then it would be impossible to account for values of
1 + A for hydrogen, helium and neon less than unity, for here the contribu­
tion of a/R T must exceed th at of b. Nevertheless with increasing molecular
size the term including a will become less im portant and Keesom’s method
of representing B by molecular volume of greater importance. The expres­
sion given for B is based on the argument th at since molecules which
approach one another cannot have their centres within the hemisphere of
radius d, then B =%Nnd3, i.e. the effective volume B is four times
actual volume. Values of d are difficult to assign, because owing to the
 Compressibilities of gases at low pressures 203
m utual repulsion of the electronic shells the radius of the hemisphere will
be greater than the molecular diameter as calculated herein from the
lengths of the links and size of atoms involved. I t will be shown on the
basis of the relations subsequently developed th a t the actual molecular
diameter appears to be approximately *J2 times the calculated diameter.

N e w da t a f o r se v e r a l g a se s
Recently Beattie and his co-workers (1935, 1937? 1939) have evaluated
the five constants for their equation of state for ethane, propane and
normal butane, and the previous work of the author (1933, 1935a) has been
extended to these gases, 1 4-A values having been calculated using the
convergence method. The expansion coefficients of methane have been
recalculated, being previously in error. The results are given in table 1
and for comparison the values for ethylene and acetylene are included,
in the latter case the calculation of the expansion coefficients is described
subsequently.
Ta b l e 1
G as 10«a„ 106a„ 1+ A A
c h 4 3684 3680 1*00233 0*00232
36830bs. 3680Obs.1 — —
c 2h 6 3740 3721 1*00964 0*00955
c 3h 8 3813 3772 1*01893 0*01857
wC4H10 3928 3861 1*03427 0*03314
c 2h 4 3724 3711 1*00741 0*00736
— — l*00732obs. 0*00727Obs.;
c 2h 2 3735 3718 l*00892Obs. 0*00884obs.
(T h ro u g h o u t th e p a p e r values of th e coefficients of ex p an sio n a t c o n s ta n t pressu re
a v a n d c o n s ta n t volum e ocv are over th e ran g e 0-100° C unless o th e r te m p e ra tu re s
are specifically s ta te d . T he coefficients ocv are a t, a n d ocv in itially a t, 1 a tm . pressure.
R eferences in ta b le are (1) K eyes a n d co-w orkers (1922, 1927), (2) Caw ood a n d
P a tte rs o n (1933).)

The results obtained for the paraffins are as expected for an homologous
series, the values for n-butane probably represent the maximum deviations
from the ideal laws for a non-polar gas at N.T.P. (b.p. 1° C). The diminution
in 1 + A and a values for ethylene compared with ethane, and the subsequent
approach of the acetylene values towards those of ethane are discussed
later in terms of the spatial structure of these molecules. The reliability
of the 1 + A values for these gases may be demonstrated by calculating
the atomic weight of carbon in each case, taking the normal densities as
cited in the International Critical Tables, i.e. from C2H6, C = 12*03 ; C2H4,
C = 12*02, and C2H 2, C = 12*005 .
204 J. B. M. Coppock
The expansion coefficients of acetylene, nitric oxide and hydrogen
chloride have been calculated from a single 14-A value at 0° C by the
following method. I t has been shown (Coppock 1933) th a t the com­
pressibility of a given gas at any temperature T° abs. may be expressed in
terms of the virial coefficient /? at th a t temperature by the equation

(1 + A)r (3 )
R 2T 2+ /3‘

A
Hence R 2T 2, (4 )
(1+A)
where R = 0*08206 1. atm.
An inspection of the difference ( A)between the
and /?100 shows th at it is approximately proportional to /?0 values provided
the gas is not very compressible, e.g. /?0 for C2H6 = —4*7632, = +1*23
and /?0 for C2H 4 = —3*6770, A = + 1*11. Thus /?0 calculated for acetylene
from its 1+A value (Howarth and Burt 1925) is —4*441 and assuming
A = +1*20, /?100 = —3*24. These values have been used to calculate the
expansion coefficients as previously described giving 106a v = 3735 and
10 6ocp=3718. In the case of nitric oxide 1 + A = 1*00119 (Addingley) and
/?0—0*5971, assuming A = 0*43 as for oxygen 106oq, = 3675 and lO6^ = 3674.
For hydrogen chloride Whytlaw-Gray and B urt (1909) give 1 + A = 1*00748,
fi0= —3*730, which is almost identical with th a t for carbon dioxide for
which A = + 1*20, hence 106o+ = 3726 and 106a p = 3713. The error involved
is probably not greater than 1 part in 2000.
In the discussion of the relation between expansion coefficient and
molecular volume some of the experimental data required were not made
over the temperature interval 0-100° C. The necessary corrections have
been applied based on the fact th a t the (+ ) difference between two
coefficients, say a 0_60 and a 0_100 is a linear function of the divergence of
the coefficient from the ideal value of 0 *003661, the greater the divergence
the larger the difference. The method of evaluating the difference has
been described by Coppock and Whytlaw-Gray (1934) and the values of
the volume coefficients* obtained by these authors for five gases have
been corrected in this way giving 10Gav for NO = 3677 : SFe = 3785 :
dimethyl ether = 3888 : CO = 3673 and N 20 = 3727.

* In th e e q u a tio n given to c o rrec t for a d s o rp tio n (p. 503) t2 sh o u ld re a d T —12,

i.e. th e te m p e ra tu re in te rv a l.
 Compressibilities of gases at low pressures 205

Th e r e l a t i o n t o m o l e c u l a r v o l u m e

I t has been suggested th a t a linear relation between 1 + A values and

effective molecular volume B might be expected. Recently, Lewis (1938)
has shown for similar groups of substances th a t critical temperatures,
boiling points, viscosities and molar heats of vaporization are linear
functions of the molecular volume as represented by the parachor.
The molecular volumes used in this paper are obtained from a summation
of atomic radii and bond distances based on the Sidgwick-Pauling addi­
tivity rule. The data used are taken from the summaries given by Sidgwick
(1933), Clark (1934), Glasstone (1936) and Brockway (1937). Sidgwick
(1932) has emphasized the different interpretations of atomic radii de­
pending on the mode of measurement and an attem pt has been made to
compute molecular radii r from comparable data. In many cases these
have been obtained from electron diffraction measurements on the gaseous
molecules. The values of r are given in table 2 together with the effective
volume of one molecule V, and B the volume per gram-molecule as calcu­
lated from the van der Waals-Keesom formula F = § and B = N V ,
corresponding values of 1 + A and a are also tabulated.
This method of calculating B assumes the molecules are spinning rapidly
enough to present themselves as spheres of revolution in the gaseous state.
This is justifiable for diatomic molecules, and in the case of “ long”
molecules Mack and Melaven (1931) believe end-over-end spins are to be
expected and consequently r is taken as the maximum radius for the
hydrocarbons and other similar molecules. This probably leads to some
error in B for propane and butane, the true volume lying between the
spheroidal and spherical condition considerably displaced towards the
latter. The normal tetrahedral angle for the carbon valencies is assumed.
The value of r for C0 2 is based on Wierl’s (see Glasstone 1936a) determina­
tion of the carbon-oxygen link; for N 20 the extreme oxygen and nitrogen
atoms are 2-38 A apart and r is the mean value for the resonance structures
N ~ = N + = 0 and N=N+— 0 ~; r for dimethyl ether, a long molecule,
assumes the oxygen intervalency angle of 111°, and for S0 2 the sulphur
valency angle is taken as 124°. In the case of SF6, rF = 0-64, the observed
S—F distance is 1*58 A hence r —2*22 A (additivity rule 2-32
Comparable values of r for the inert gases are difficult to assign, they
appear to be best represented by the radii of the adjacent alkali metal
ions. The values of Zachariasen and Wasastjerna obtained by independent
methods for these ions are of the same order as the mean of Grimm’s
values for the inert gases (for complete data see Clark (1934)), and the
206 J. B. M. Coppock
former are those assumed. Viscosity measurements would give slightly
larger values not fully comparable with the other data.
It will be observed from figures 1 and 2 th a t for non-polar gases the
compressibilities and coefficients of expansion at constant pressure are
linear functions of B, the molecular volume. The discrepancies which occur

Ta b l e 2
B in
G as r in A V in A 3 c.c./g. m ol. 106a„ 1+ A
He 0-68 5-27 3-19 3659 0-99948
h 2 0-74 6-79 4-12 3660 0-99939
d 2 0-741 6-79 4-12 36592 —

Ne 0-98 15-77 9-56 3660 0-99951

n 2 110 22-30 13-52 3670-5 1-00044
NO 115 25-49 15-45 3677 1-00119
o2 1-20 28-96 17-55 3674 1-00094
CO 1-20 28-96 17-55 3673 1-000483
A 1-33 39-43 23-89 3673 1-00099
HC1 1-37 43-09 26-11 3726 1-00748
n h 3 1-45 51-09 30-96 3847 1-0151
c h 4 1-46 52-16 31-60 3683 1-0024
Kr 1-48 54-33 32-92 3688 1-00279
X 1-75 89-8 54-4 3721 1-00699
co2 1-78 94-51 57-27 3723 1-006844
c 2H4 1-80 97-72 59-23 3724 1-007325
n 20 1*81 99-38 60-21 3727 1-007354
so2 1-86 107-8 65-34 3900 1-02394
C2H 6 1-93 120-5 73-11 3740 1-00964
c 2h 2 2-03 140-2 84-96 3735 1-00892
sf 6 2-22 183-3 111-1 3785 —

(c h 3)2o 2-42 237-5 143-9 3888 1-02815

C3H 8 2-50 261-8 158-7 3810 1-01893
nC 4H 10 314 518-8 314-4 3928 1-03427
(D a ta n o t cited, in th is o r p rev io u s p ap e rs or ca lc u la te d h erein b e a r th e a p p ro p ria te
referen ce: (1) C lark (1939), (2) C oppock (19356), (3) W o o d h ead a n d W h y tla w -G ra y
(1933), (4) B a tu e c a s (1934), (5) Caw ood a n d P a tte rs o n (1933).)

are not large, particularly as B involves the cube of the molecular diameter
and determinations of 1 + A and ocv are frequently affected by adsorption
errors. The volume coefficient was chosen to illustrate the relation owing
to its greater sensitivity to adsorption errors in its measurement than the
corresponding pressure coefficient. It was not expected th at such a simple
relation would hold so well in the case of expansion coefficients where T,
and hence the attraction term a/BT, is variable. That it does hold supports
the view of the minor importance of a and its subsequent evaluation in
terms of B in the calculation of 1 + A for non-polar gases.
 Compressibilities of gases at low pressures 207
The deviations from the linear relations shown by the polar gases is
well marked, and expressed in terms of B the divergence appears to be
proportional to the dipole moment, the values lying on a smooth curve as
may be anticipated.

1-024
1-022

polar gases
1+ A

-CO NO,

1000
0-998

B (c .c./g. m ol.)
F ig u r e 1. P lo t of 1 + A ag a in st B.

The interesting result has been pointed out that 1+A and a values for
acetylene are apparently abnormal, falling between those for ethane and
ethylene. It is clear that shortening of the carbon-carbon distance due
to the double bond will diminish r as we pass from C2H6 to C2H4, but in
the case of acetylene the further diminution caused by the triple bond is
208 J. B. M. Coppock
more than counterbalanced by the “ end-on” positions of the hydrogen
atoms. Thus r and B are greater than for ethylene, actually they are larger
than for ethane which is not in accordance with the 1+A values. Two
explanations are possible: (1) Indeterminancy in the value of rH in the

3860-

B (c.c./g. m ol.)
F ig ur e 2. P lo t o f a v a g a in st B.

C—H link which affects only slightly rmaxlmum for C2H6 and C2H 4 owing to
the spatial distribution of the hydrogen atoms, but is of major importance
for C2H 2. (2) C2H 2 is a thinner molecule than either C2H6 or C2H 4 and
B calculated from the spherical formula is probably too large. Never­
theless, in spite of these defects the anomalous position of acetylene is
explained simply and without the need of postulating an abnormal struc­
ture for the molecule.
No experimental value of 1 + A for isobutane is known, but compared
with w-butane (B = 184-7 and 314-4 respectively) the former should deviate
 Compressibilities of gases at low pressures 209
less from a perfect gas (estimated 14-A = 1*022) as may be seen by a com­
parison of boiling points ( —17 and 1° C). In this connexion it is suggestive
th a t in the case of buatadiene which has been ascribed the resonance
structure CH2^i CH,^i CH„^:CH2, the boiling point is 3*6 ° lower than th a t
of w-butane ( —2*6 and 1° C). This is 3° short of the value anticipated
by comparing B for the formula CH2= C H —C H =C H 2 (268*7 ) with the
values for w-butane and isobutane where the difference in boiling points
is 18° C. The resonance formula would suggest a slightly longer molecule
(i.e. greater B value) than the older mode of writing the structure.
The position of sulphur hexafluoride in figure 2 is more normal when r
is based on the measured S—F bond distance rather than on the additivity
rule. There is also evidence from both curves, particularly in the expansion
coefficient case, of the more polar tendencies of N—O than for C—O
attributed to the additional electron centred on the nitrogen atom.
In view of the linear relations obtained values of B were inserted in the
Keesom equation (2) and 1 + A values calculated therefrom, but the results
were in considerable error. Obviously the true “ effective ” volume L must
be of the same magnitude as the fijV term of the Beattie equation, and
the corresponding term of the Keesom equation likewise. By evaluating
1 + A for definite values of L and determining from the slope of the curve
in figure 1 the corresponding B values it is found th at B must be multiplied
by 2*85 to give L. This means th at the actual diameter is very nearly .^2
times the calculated diameter, and suggests th at the nearest distance of
approach of non-polar molecules at low pressures is conditioned by their
size and is not a uniform amount as represented by an envelope of say
0*5 A thick. It also explains the apparent lessening of the van der Waals
a effect with increasing molecular volume. It was suggested earlier th at
the a/BT term is important in the cases of hydrogen, helium and neon, and
as it is found that 1 + A and <x are linear functions of B, the correction for a
has been evaluated in terms of B. Thus for non-polar gases we may write

P i vi = p 0v0+ (0-027— a2-85B

) t 0° C,

v and B are in litres per g. mol., and 22*4131 1. atm., the constants
are of course tentative. Values of 1+A calculated from this equation are
given in table 3 and as errors in the molecular diameter are greatly
magnified in calculating B the agreement is regarded as satisfactory.
Thus by utilizing this simple relation it should be possible to predict for
non-polar molecules accurate values of the physical constants discussed
in this paper from a knowledge of their molecular radii.
210 J. B. M. Coppock

Ta b l e 3
G as 1 + ^calc. 1 + A>bs.
h2 0-99932 0-99939
n2 1-00052 1-00044
o2 1-00103 1-00094
c h 4 1-00291 1-0024
Kr 1-00317 1-00279
co2 1-00617 1-00684
C3H 8 1-0193 1-0189

The author wishes to express his indebtedness to Dr J. Kenyon, F.R.S.,

Professor R. Whytlaw-Gray, F.R.S., and Dr J. W. Smith for helpful
criticism and advice.

Su m ma r y
A linear relation is shown to exist for non-polar gases at low pressures
between their compressibilities and expansion coefficients and the corre­
sponding molecular volumes.
I t is suggested th at the nearest distance of approach of such gaseous
molecules a t low pressures is dependent on their size and is not a uniform
amount as represented by an envelope of about 0*5 A thick.
Additional data have been calculated for certain hydrocarbons and the
behaviour of some of them discussed in the light of their spatial structure.

Re f e r e nc e s
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B a tu e cas, T . 1934 J . Chim. Phys. 31, 65.
B e a ttie , J . B. a n d B rid g e m an , O. C. 1928 Amer. Chem. 50, 3151.
----- --
-1930 Z . Phys. 62, 95.
B e a ttie , J . B . a n d co-w orkers. 1935 J . Chem. Phys. 3, 93.
— 1937 J . Am er. Chem. Soc. 59, 1589.
— 1939 J- Am er. Chem. Soc. 61, 26.
B ro ck w ay, L. O. 1937 A n n . Rep. Chem. Soc. p. 196.
Caw ood, W . a n d P a tte rs o n , H . S. 1933 J . Chem. Soc. p. 619.
C lark, C. H . D . 1934 Electronic structure and properties of matter, 1. L o n d o n :
C h ap m an a n d H all.
— 1939 Phil. Mag. 27, 389.
Coppock, J . B . M. 1933 J . Phys. Chem. 37, 995.
— 1935 a Phil. Mag. 19, 446.
— 19356 Trans. Faraday Soc. 31, 913.
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G lasstone, S. 1936 A n n . Rep. Chem. Soc. p. 65.
— 1936a Recent advances in general chemistry, p. 209. L o n d o n : C hurchill.
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 Compressibilities of gases at low pressures 211
K eeso m , W . H . 1921 Phys. Z. 22,129.
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— 1927 J .Am er. Chem. Soc. 49, 1403.
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Sidgw ick, N . V. 1932 A n n . Rep. Chem. Soc. p. 67.
— 1933 The covalent link. Cornell U n iv . P ress.
W h y tlaw -G ra y , R . a n d B u rt, F . P . 1909 J . Chem. Soc. 95, 1633.
W o o d h ead , M. a n d W h y tla w -G ra y , R . 1933 J . Chem. Soc. p. 846.

On relativistic wave equations for particles of arbitrary

spin in an electromagnetic field
B y M. F i e r z a n d W. P a u l i
PhysikalischesInstitut der ETechnische
Hochschule, Zurich

(Communicated by P.A. M. Dirac, F.R.S.— Received 31 May 1939)

1. I n t r o d u c t i o n
The investigations of Dirac (1936) on relativistic wave equations for
particles with arbitrary spin have recently been followed up by one of us
(Fierz, 1939, referred to as (A)) It was there found possible to set up a
scheme of second quantization in the absence of an external field, and to
derive expressions for the current vector and the energy-momentum tensor.
These considerations will be extended in the present paper to the case when
there is an external electromagnetic field, but we shall in the first instance
disregard the second quantization and confine ourselves to a c-number
theory.
The difficulty of this problem is illustrated by the fact that the most
immediate method of taking into account the effect of the electromagnetic
field, proposed by Dirac (1936), leads to inconsistent equations as soon as
the spin is greater than 1. To make this clear we consider Dirac’s equations
for a particle of spin 3/2, which in the force-free case run as follows:

K b = p^PaPp = p0Pa“p,
(1)
K at/3 = V * p b f = P p pb P i,

Vol. 173. A. 14