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org/ on October 29, 2018

The adsorption of non-polar gases on alkali

halide crystals
B y W illiam J . C. O rr
Laboratory of Colloid Science, Cambridge

Communicated by E. K . Bideal, F.R.S.

In recent years many im portant theoretical advances have been made in

the application of quantum statistics to adsorption problems. Fowler (1935),
adopting the Langmuir picture of a monomolecular adsorbed gas layer,
derived from purely statistical considerations the equation

_ J _ {Znm)*{kT)*bg{T)
(1)
l-d h3 va(T)

in which the undetermined constants of Langmuir’s original equation

(1918) are given explicitly in terms of the partition functions, bg(T) and
vs(T) belonging to atoms in the gas phase and in the adsorbed layer res­
pectively and >
xwhich is the difference in energy of an atom in the gas phase
and in the lowest adsorption level on the surface. In subsequent develop­
ments the change in the energy of adsorption as a function of 6 (the fraction
of the surface covered) has been introduced in the above equation using (a)
the Bragg and Williams approximations (Fowler 1936a) and (b) the Bethe
method (Peierls 1936) to determine the configurational energy. Further
applications and extensions of these methods to special adsorption problems
have been carried through by Roberts (1937) and by Wang (1937), and
Rushbrooke (1938) has examined the validity of the assumption, which is
implicit in all this work, namely, that va(T) is independent of the configura­
tion. In addition, an approach to the solution of the statistical configuration
problem when molecules condense in two layers simultaneously has recently
been made by Cernuschi (1938) and developed by Dube (1938). In order to
evaluate correctly the summations vs(T) occurring in equation (1), the
Schrodinger equa tion for an atom moving in the three-dimensional potential
field of the substrate should be solved, but this has so far proved prohibit­
ively difficult. In the past it has been customary, and for practical purposes
it is possibly generally sufficient, to substitute classical partition functions
for these summations. However, valuable studies of particular cases of the
general quantum mechanical problem have been made by Lennard-Jones

Vol. 173. A. [ 349 ] 23

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350 W. J. C. Orr
and Strachan (1935) and Lennard-Jones and Devonshire (1936), who con­
sider a one-dimensional case in which an isolated atom vibrates normal to
the surface, the potential energy of the system being represented by a
Morse curve,
V = D[e-2*(r-re) _ 2e-*<r- re)]. (2)

With this assumption the discrete vibrational levels are known provided the
parameters D and k can be otherwise determined. Considering th at the
effect of the thermal motion of the solid on V is small and may be treated by
first order perturbation theory, they calculate further the probabilities of
atoms making transitions from one discrete vibrational level to another or
evaporating into or condensing from the gas phase by the emission or
adsorption of quanta from the solid. In order to provide data to which these
various theoretical developments would be directly applicable the present
experiments on the adsorption of non-polar gases such as argon, oxygen and
nitrogen on the alkali halide crystals, KC1 and Csl were undertaken. The
choice of non-polar spherically symmetrical gases avoided the complications
which the presence of permanent dipoles would introduce, while the choice
of alkali halide crystals was influenced by the following factors: (1) they were
easily obtained analytically pure, (2) the lattice structures and such pro­
perties of the individual ions as their ionic radii, optical polarisabilities and
magnetic susceptibilities were well known, (3) KC1 was an example of a
simple cubic and Csl of a body centred cubic crystal so th at the influence of
the crystal type on adsorption behaviour could be examined. Further the
previous experimental work on such crystals was very scarce. Durau (1928)
had made some measurements on the adsorption of argon, oxygen and
nitrogen at room temperatures on NaCl crystals but since the adsorption at
these temperatures is extremely small, accurate isotherms could not be
obtained and no heats of adsorption were calculated. Later, Tompkins
(1936) measured the adsorption of oxygen, carbon monoxide, nitrogen and
argon among other gases on NaCl at low pressures and liquid air tem pera­
tures but obtained improbably small values for the heats of adsorption.
Some accurate experiments by Lenel (1933), however, gave heats of ad­
sorption close to the order of magnitude expected for argon on KC1 and
other salts. The variation of the heat of adsorption with the amount adsorbed
was however not examined. Single isotherms for argon on KC1 which show a
qualitative similarity with the present results have been described by
Bradley (1936) and by Brunauer and Em m ett (1937).
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The adsorption of non-polar gases 351

E x pe r im e n t a l r esu l ts

The scarcity of accurate experimental data on the adsorption of non­

polar gases on alkali halide crystals, a field with attractive theoretical
possibilities, is no doubt to be explained by the difficulties of measuring the
very small amounts of gas adsorbed on these crystals. In the present experi­
ments the amounts adsorbed at liquid air temperatures varied from 0-20 to
30 cu.mm./g. salt used (calculated for N.T.P.) in the pressure range 10~3 to
70 cm., the dimensions of the crystals being on the average about 0-1 mm.
cube edge. Greater amounts could have been adsorbed by very fine grinding
of the salt but this was considered undesirable as it would have greatly
increased the amount of internal cracking of the crystallites and reduced the
adsorption on the plane faces relative to th at on corners and edges and in
crystal cracks and defects. Liquid air temperatures offered the most con­
venient temperature range for optimum adsorption with the gases argon;
oxygen and nitrogen. In order to survey as wide a range of behaviour as
possible isotherms were measured in the pressure range from 10~3cm. up to
the condensation pressure of the gas. Very low pressures were not investi­
gated because the ordinary McLeod or Pirani gauge technique was not of
sufficient sensitivity. In preliminary experiments isotherms were measured
employing the usual technique of-adsorption measurements at constant
volume. Liquid air baths were used for the low temperatures and pressures
were read on a mercury manometer using a cathetometer. However, since an
error of 0-002 cm. in the pressure caused an error of approximately 10 % in
the calculated amount adsorbed and since a change of temperature of 0-2° K
gave rise to an error of the same magnitude it was necessary to devise an
arrangement whereby the pressure difference due to the amount adsorbed
could be read directly. A diagram of the apparatus finally employed is
shown in figure 1. The two dosers, DR, Ds whose volumes were determined to
0-001 c.c., could be filled between Txand to the same
T2C T2was evacuated and mercury permitted to flow to T2T 2, the gas in
D r and Ds being then displaced by mercury into the reference bulb R and
the salt bulb S respectively. The connecting lines T^M were of capillary
glass and the total volume of each, which was accurately determined, was
only about 1-0 c.c. M was an oil (Apiezon B) manometer on which the differ­
ence in pressure due to the gas adsorbed in S could be accurately determined
to 0-005 cm. (i.e. 0-0004 cm. Hg) with a cathetometer. The pyrex bulbs R
and S were adjusted to have approximately the same free space to within
0-5 c.c. The volume of R was then determined to 0-001 c.c. by weighing with
water at a definite temperature. A few calibration experiments at room
23-2
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352 W. J. C. On-
temperature then gave the volume S to approximately the same accuracy.
In order to determine the change in free volume of the salt in S due to con­
traction, between room and liquid air temperatures, calibrations were
carried out at liquid air temperatures using helium, for which the adsorption
at 80° K is quite negligible.
reservoirs
pumps

capillary
—oil
manometer
„__ oil
manometer

""manometer

suction
pump

F ig ure 1. D iagram o f th e adsorption apparatus.

The equilibrium pressure (p)and the number of mol

are given by the following formulae:

V= p Z P - A „ a,
VR

X= ^FpJ<Ds Z p -Vsl>)>

Vr = vr + V % ^ ,

Is = (% —0*01l£)+ V%-^+or(TA —TL),

where the subscripts!? and Srefer to the reference and salt limbs r
£ being the volumes of the bulbs at room temperature (TA) and vR S the
volumes of the capillaries ^M;
T VR sare
adsorption temperature ( TL).D RS are the volumes of the dos
E P is the sum of the successive pressures admitted via TXT%to the bulbs.
A Ug = 8 is the pressure difference on M in cm. of Hg a t room tempera-
PlLg
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Theadsorption of gases 353

ture. The oil level in limb a was kept adjusted a t an arbitrary level so th a t
vR was kept constant, thus the term 0-011$, where is the difference in oil
levels, gives the decrease in vs due to the oil column, 0-011 being the volume
per unit length of the manometer capillary.
cr is the average volume decrease per 0K of the salt in the range between
room temperature and liquid air temperatures. A linear term was adequate
to express this correction in the range frpm 65 to 90° K.

F ig ube 2. Diagram Of the low tem perature therm ostat regulator.

In order to obtain automatic temperature control of a liquid air bath at

any specified temperature in the range from 65 to 90° K, the design of vapour
pressure thermometer shown in figure 2 was developed. The mercury of the
manometer operated a relay (connected through the platinum contact at
which switched on and off the motor of a hyvac pump (pumping at B), as
contact was broken or made respectively. As designed the thermometer
could be easily filled with oxygen or nitrogen through tap C, nitrogen being
used for the temperature range 65-77° K and oxygen for 77-90° K. A glass
float at J indicated the liquid level inside the bath. The thermometer could
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354 W. J. C. Orr
be set to regulate at any desired temperature by adjusting the mercury
level at D, the temperature being determined from the vapour pressure
(measured on the millimetre scale E),by referenc
these gases. For the present experiments the vapour pressure data of Cath
(1918) were used for liquid oxygen and those of Giauque and Clayton (1933)
for liquid nitrogen. In operation the temperature was controlled to within
0-02° K and perfectly steady readings of the oil level at M (figure 1) were
obtained.

Series 1. Adsorption of argon, oxygen and nitrogen on KC1

29-74 g. KC1 which was heated for several days at 500° C was transferred
to bulb S, figure 1, in an atmosphere of dry air. I t was then heated in vacuo
for several days at 350° C and to a similar temperature between every
experiment.
Argon (95 % purity) was passed through a liquid air trap over a Cu-CuO
mixture at 350° C through P 20 5 and finally fractionated at reduced pressure,
the middle fraction only being stored.
Oxygen was prepared from K M n04 and fractionated at liquid nitrogen
temperatures.
Nitrogen was purified in the same way as argon.
Helium (80 % initial purity) was treated similarly to nitrogen except th a t
before using it was twice desorbed at 80° K from charcoal.
Isotherms were measured at temperatures spaced approximately a t 3°
intervals between 69 and 87° K. A few representative log a;-log p curves are
given in figure 3. The general behaviour of the x) isotherms in the initial
stages is shown in figure 4, and near the condensation pressure range in
figure 5. The adsorption was found to be perfectly reversible and isotherms
could easily be reproduced to an accuracy of within 1 % in x.

Series 2. Adsorption of argon, oxygen and nitrogen on Csl

The Csl (33-01 g. A.R. reagent) was heated in vacuo at 350° C for several
days before commencing experiments and to a similar temperature between
each experiment.
The purification of gases was exactly the same as in series 1.
Initially isotherms were measured, but since the total temperature range
available, namely, 65-87° K, was rather narrow, a much more rapid and
convenient way of obtaining a large number of values of the heats of ad­
sorption, was to admit a given amount of gas to the bulbs and S and then
to measure the amounts adsorbed at a series of closely spaced temperature
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The adsorption of non-polar gases 355

condensation pressures

^ 10

logio P (cm.)
F ig ure 3. Log x-\og p isotherms for argon, oxygen and nitrogen on KC

p (cm.)
F igure 4. Behaviour of the KC1 isotherms in the low-pressure range.
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356 W. J. C. Orr
intervals. A few results showing the trend and the relative shape of the
log x-log p curves derived from these experiments are given in figure 6.
In all experiments adequate time was given for thermal equilibrium to be
established between the salt and the low temperature bath. The salt was left
in contact with the initial dose of gas for 2-3 hr. before readings were com­
menced. For subsequent doses the pressure became steady within about

*<—N.

1
3
O

p (cm.)
F igure 5. Oxygen on KC1. Behaviour of the isotherms near the
condensation pressure.

15 min. and was observed to remain steady for periods up to 2 hr. No

measurable diffusion process was detected in any experiment within periods
of this duration. As a test th at adequate time was given for thermal equilib­
rium, in series 2, an initial experiment was carried out at temperatures going
progressively in 2 degree steps from 75 to 65° K and then back by the same
intervals to 75° K. The readings on M were exactly repeated at correspond­
ing temperatures in both directions. A satisfactory test of the fact th at the
oxygen and nitrogen thermometers register the same temperature in the
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Theadsorption of non-polar gases 357

range where they overlap, namely, 75-77° K, is afforded by the exact way in
which points on the 75° isotherm for argon shown in figure 6 fit on the same
curve. (The circles represent points obtained with the nitrogen thermometer
and the squares points with the oxygen thermometer.)

« 05
No67-00°

0,83-00'
Ar8500°

logic P
F igure 6. Log a;-log p isotherms for argon, oxygen and nitrogen on Csl.

Heats of adsorption
The heats of adsorption as a function of were calculated from the above
experiments using the Clausius-Clapeyron equation in the form

2-303AH r 1 in
[logio P lM x R L*i

where AH is the heat liberated when 1 g.mol. of gas is adsorbed on the

substrate at constant pressure.
The variation of AH with x thus obtained in every case after falli
initially, rose to a maximum and then fell steadily to the latent heat of
vaporization of the condensed gas phase. The results are shown plotted as a
function of x/xm in figures 7, 8 and 9, where xm is the ordinate corresponding
to the maximum value of AH and has the values tabulated in tab
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358 W. J. C. Orr
From figures 7, 8 and 9 it is evident th at the maximum experimental
error in AH is ±150 cal. which is of the order expected from a possible error
of ±0-5% in x and ± 0-01° K in T, the heats being calculated from iso­
therms differing only by from 2 to 5°K.
The star in figure 7 which indicates the heat of adsorption found experi­
mentally by Lenel (1933) will be seen to be in good agreement with the
present results.
Table 1

xm
x 106 g.mol.
A 02 n2
KC1 8-3 8-4 7-2
Csl 4-5 4-0 4-0

•s 2500

F ig ure 7. H eats of adsorption as a function of 6 for argon on KC1 <£) and on Csl 0 .

D isc u ssio n

In two recent papers (Roberts and Orr 1938; Orr 1939) detailed theoretical
calculations have been carried out of the adsorption behaviour of argon on
KC1 and Csl surfaces and the following results have been obtained:
(1) The energies of adsorption and the equilibrium distances of an isolated
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A H cal./g.mol. The adsorption of non-polar gases 359

ctbe 8. Heats of adsorption as a function of 6 for oxygen on KC1 (•) and on Csl © .
g
A H cal./g.mol.

F ig u r e 9. Heats of adsorption as a function of 6 for nitrogen on KC1 (£) and

on Csl 0 .
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360 W. J. C. Orr
atom at various positions on these surfaces were calculated directly and are
collected in table 2.
T a bl e 2
~E 0 ~E
»equil. cal./ Surface f'equil. cal./
KCl A g.mol. Csl layer A g.mol.
Above the centre 3-215 1593 Above the centre Cs+ ions (1-75) 3168
of a lattice cell of a lattice cell
Above the m id­ 3-44 1314 I - ions 2-60 2682
point of a lattice
edge
Above a K+ ion 3-48 1423 Above a lattice Cs+ ions 3-65 1100
point
Above a Cl- ion 3-74 1233 I - ions 4-08 1361

(2) In the case of KC1 it was shown that, in the formation of a primary
monolayer, atoms would be adsorbed from 0 to about 0-5 above the
centres of lattice cells but th a t as 0 tended to unity the arrangement would
pass over to a close-packed hexagonal pattern. In this configuration, the
adsorbed atoms being distributed a t random with respect to the lattice
periodicities, the energy of adsorption normal to the surface at = 1 would
av
be a weighted average of values in column 3, table 2, namely —E — 1412 cal.
KCl
The calculated behaviour is shown in figure 7, curve 1. I t should be noted, in
this case, th at the electrostatic field is zero from = 0 to 0-5 and th at from
0 = 0-5 to 1-0 the electrostatic contribution to the mutual energy of the
molecules in the adsorbed layer is less than 3 % of the mutual energy due to
van der Waals forces.
(3) In the case of Csl both Cs+ and I - faces are present in equal amounts.
I t was shown th at in both cases the most stable arrangement over the range
6 = 0 to 1*0 would be that with atoms adsorbed above the centres of lattice
cells. The calculation of the variation in heat in the actual physical case
where the two surfaces are competing for atoms was carried out making use
of equation (1). The result is plotted as curve 2 in figures 7 and 8. The
distinct difference between this curve and curve 1 is due to the important
part played by the electrostatic potential of the crystal in this case. Dipoles
orientated in parallel are induced in the adsorbed molecules and these give
rise to a repulsive potential which, although amounting only to 16 % of the
van der Waals contribution to the mutual energy at 1 in the case of an
I - face, becomes 33 % greater than the van der Waals field in the case of the
Cs+ face at the same value of 6.
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Theadsorption of non-polar gases 361

(4) Further the difference between the calculated adsorption energies
which refer to absolute zero and the experimental values of a t liquid air
temperatures was shown to be well within the experimental error so th a t the
above direct comparison of the calculated and experimental results is quite
permissible.
(5) Finally, an extension was made to the system, argon on KC1 of Dube’s
(1938) treatm ent of the problem of atoms condensing in the first and second
layers simultaneously and it was shown that a maximum should occur in the
AH,x) curve whose ordinate, xm, should mark to within 1 % the number of
molecules adsorbed at the completion of a first monolayer. Thus it is possible
to express the heat variation in terms of 6 a:/xmasshownin figures 7,8 and 9.
Although it was only in the case of argon th at all the constants of the
attractive and repulsive potentials were known, it is possible to decide to
what extent the calculated values of the energy in the cases of oxygen and
nitrogen should differ from those of argon. In the case of oxygen there is a
very close similarity between the potential energy curves for two argon
(Lennard-Jones 1931) and two oxygen (Fowler 1938) molecules, which have
been derived from Virial coefficient data, namely,

<j>A =- 1-70 x lO-58/r6+ 7-68 x 10~81/r12

and (f)0i = - 1-71 x 10-58/r6+ 7-8 x 10-81/r12.

Further, the diameters of an argon and an oxygen atom derived from the
densities of the liquids at 87° K are 4-05 and 4-00 A respectively. Thus it can
be anticipated th at the behaviour of these two gases in weak van der Waals
adsorption fields will be very similar indeed. A comparison of figures 7 and 8
will show th at this is true of adsorption on KC1 and Csl. In the case of
nitrogen it would be expected from the lower heat of interaction of a pair of
nitrogen molecules and also from the lower heat of evaporation of the
liquid compared with argon or oxygen, that the adsorption heat of nitrogen
would be lower than th at of the other two. A similar conclusion is indicated
from theory, for taking account of the increased diameter of nitrogen
(namely, 4-38 A at 85° K) compared with argon and oxygen, the van der
Waals energy at the equilibrium distance calculated, alike by the London
formula (1930) and the Kirkwood-Muller formula (1936), gives a smaller
negative energy than in the other two cases. I t is thus surprising to find th at
the measured heats of adsorption AH, for nitrogen are on the average about
400 cal. greater than those of oxygen and argon. The result is, however, not
peculiar to the present experiments but has been observed by Barrer (1937)
with adsorption on graphite, by Wilkins (1938) on platinum, by Zeise (1928)
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362 W. J. C. On-
on glass. An observation of possible significance in this connexion is th a t of
Vegard (1934), who finds evidence, from the crystal structure of solid nitro­
gen, of a small polarity comparing very exactly with th at found for the iso-
steric molecule carbon monoxide. Although the explanation of such a
polarity is not clear, if the effect is real, then it might be expected to be
operative also for nitrogen in the adsorbed state and would explain the
observed high heats of adsorption. In some unpublished, adsorption ex­
periments on LiCl, nitrogen and carbon monoxide isotherms behaved very
similarly and differed quite markedly from the shape of argon isotherms.
A direct comparison of the theoretical calculations with the experimental
results may no w be made, taking first the case of argon on KC1. From figure
7 it is evident th at the calculations reproduce quite exactly both the shape
and the absolute magnitude of the experimental curve from d = 0-5 to 1-0.
The divergence of the curves a t lower values of 0 is most probably to be
ascribed to adsorption taking place in cracks and other irregularities in the
crystals. Initially molecules will be adsorbed on the most energetic positions,
th a t is, in the bottoms of deep fissures where the adsorption heat may rise to
av av
a maximum of ^ —2 E —2<x —3060cal. ( —E = 1412 has been previo
KCl K C1
defined and — cl —
240 cal. is the energy of two argon atoms at contact
From the extent of divergence of the experimental curve it may be estimated
th at about 15 % of the surface of the sample of crystals used consists of
cracks of from one to two molecular diameters width. Where the fissures are
wider than this the adsorption energy will not differ significantly from ad­
sorption on the plane surface. The number of molecules which can be ad­
sorbed in a second layer will thus be approximately 85 % of I t is further
evident, comparing figures 7 and 8, th at the same calculation reproduces
equally well the shape of the (AH, 6) curve in the case of oxygen. In absolute
magnitude the values of AFIfor oxygen are only about 100 c
those for argon. A further fact consistent with the interpretation we are
here giving to the results is th at the values of xm for argon and oxygen are
closely equal, being 8-3 and 8-4 x 10~6g.mol. respectively. This would be
expected from the similarity in their radii. In the case of nitrogen on KCl,
besides the fact th at the absolute magnitude of is greater than th at
expected theoretically, the variation of with is somewhat greater than
would be calculated. However, it is not permissible to draw definite conclu­
sions from the latter fact since a consideration of the shape of the isotherms
(see figure 3) in the region near xm will show th at a very slight experimental
error would give rise to large variations in the heat of adsorption. The value
of xm = 7-2 x 10~6g.mol., however, is significantly smaller than that found
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Theadsorption of gases 363

for argon and oxygen and this is in agreement with expectation, since
(xm)Ni should be approximately equal to
( xm)A(rAlrN2)2 = 8-3(4-05/4-38)2 x 10-6 = 7*1 x 10_6g.mol.
The case of argon and oxygen on Csl may now be considered. The calcu­
lated variation of AH as a function of 6 is applied directly to the experiment
results, curve 2, in figures 7 and 8. I t is immediately evident th at the calcu­
lated heats exceed the experimental by some 500 cal. This discrepancy may
be ascribed, partly to the use of the Kirkwood-Muller formula for the large
ions, Cs+ and I - , and may be partly due to the somewhat arbitrary choice of
a suitable repulsive constant made in this case. However, the calculated
variation of AH with 6 reproduces the shape of the experimental curve in a
very satisfactory fashion (especially so in the case of oxygen for which the
experimental results are rather less scattered than in the case of argon). In
the case of nitrogen on Csl, as on KC1, although the absolute magnitude of
the experimental results is again some 500 cal. higher than those of argon or
oxygen, the variation of AH with 6, however, follows closely the sha
theoretical curve.

F igure 10. Calculated adsorption isotherms for particular forms of the

heat variation curve.

Connected with the distinct U-shaped appearance of the curves for these
gases on KC1 is the fact th at the (p,x) isotherms all hav
flexion in the region between 6= 0 to 1-00 (see figure 4). It h
by Fowler (19366) and by Wang (1937) that an adsorption isotherm will not
show an inflexion in the range where AH (or y, eqn. (1)) is steadily decreasing.
In figure 10, curves a and 6 represent two simple Langmuir curves, a with
and 6 with y2, where Xi > X2 - Curve c represents the behaviour of an isotherm
where y is falling from yxtowards y2. Further, Fowler (1936a) has shown that
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364 W. J. C. Orr
when the molecules in their equilibrium positions in the first layer attract
one another, the isotherms will always have one inflexion, as shown in curve d.
In the present experiments AH falls initially and subsequently rises due to
lateral interactions. Thus we expect the isotherm first to follow a curve such
as c and later to bend over to one similar to d. The resultant effect will be as
shown in curve e, which reproduces all the essential features of the isotherms
such as those in figure 4, found experimentally in the case of KC1. In the
case of Csl, the very slight maximum in the curves is apparently insufficient
to produce a noticeable inflexion in the initial portion of the isotherms (see
figure 6). I t may be concluded th at for the range 0 to 1*0 all the distinc­
tive features of the results can be quite adequately explained on theoretical
grounds.
I t now remains to discuss the behaviour of the systems in the range from
the completion of a monolayer to the bulk condensation of the gas on the
solid. In table 3 are given values of the ratio of the equilibrium vapour
pressure (p) to the saturation vapour pressure of the bulk gas phase (ps ) for
representative isotherms a t amounts adsorbed corresponding to 1, 2, 3 and 4
apparent layers, the area available in the second and subsequent layers
being assumed equal to 85 % of th at in the first.

T able 3
P/Ps Bulk
"S condensed
No. of “ layers” 1 2 3 4 phase
Argon Solid
(79-35° K) 0-25 0-69 0-90 0-96 m.p. = 83-9° K
Argon
(86-89° K) 0-22 0-63 0-80 0-90 Liquid
Oxygen
(79-32° K) 0-20 0-65 0-80 0-85 Liquid
Nitrogen
(73-57° K) 0-012 0-44 0-70 0-85 Liquid

The similarity between oxygen and argon and the contrast in their be­
haviour to th at of nitrogen is here very clearly brought out, the relatively
very low value of PiPsat one monolayer, in the case of nitroge
indicative of the much stronger interaction of these molecules with the
surface. I t is also significant to note th at p/ps for nitrogen reaches values
similar to those of oxygen and argon when about three or four apparent
layers are adsorbed, thus illustrating the very rapid falling off in the in­
fluence of the surface field. The fact th at the vapour pressure does not reach
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Theadsorption of gases 365

exactly the saturation vapour pressure in about four layers, as would be
expected from the known range of molecular forces, but tends asymptotic­
ally towards it, as is shown in figure 5, is undoubtedly to be explained by a
lowering of the vapour pressure of the bulk phase due to capillary effects
occurring in wide cracks or holes in the crystal surface. Although rapid
condensation in bulk does not set in till about four or five layers have con­
densed the heat of adsorption, in the case of argon, falls to the sublimation
heat of the solid very close to the completion of a second layer (see figure 7),
while, in the cases of oxygen and nitrogen, it falls-to the heat of vaporization
of the liquid when between two and three layers have been condensed (see
figures 8 and 9). Now applying the Gibbs-Helmholz relation to the data for
argon at the completion of a second layer, where (Hads —Hcrys.) = 0, we
have
^(Sads. ^crys.) = (^ads. 6rcrys ) = T T loge ?•

Using the value PdPs = 0*69 from table 3, we obtain (Sads —Serys) =
entropy units. This figure is comparable with the entropy changes occurring
at transitions between two different crystalline species, and it is a measure of
the increase of disorder in a bimolecular layer over th at of crystalline argon.
This disorder results from the adjustment which must be made in passing
from the hexagonal pattern which we have attributed to the first layer of
argon on KC1, or the cubic pattern in the case of argon on Csl, to the face
centred structure of the bulk crystal. If the second layer were condensing in
the form of localized crystallites no such distinct entropy difference could be
expected. We thus conclude that, subsequent to the formation of a first
layer, which we have already shown has a well defined range of existence, we
must suppose that, in the case of argon below its melting point, a fairly
distinct second layer is also built up. In the cases of oxygen and argon
(above 83-9° K), the second layer is possibly not quite so distinct as in the
previous case, while in the case of nitrogen, where the relative vapour pres­
sure is so much smaller than in the case of argon, it seems likely that the
second layer may be more distinct. By the third or fourth apparent layer the
effect of the surface field must be quite unimportant and the geometric
relations characterizing the bulk phase, whether solid or liquid, should be
almost completely satisfied. From this stage onwards the growth of the
adsorbed phase may take place at random. These results are in harmony
with most recent experiments on multimolecular adsorbed gas layers and
may be considered as lending further weight to the viewpoint that relatively
few layers, no more than four or five at the most, are adsorbed before bulk
condensation of the adsorbed phase sets in and, in particular, as giving

Vol. 173. A. 24
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366 W. J. C. Orr
support to Bangham’s (1938) hypothesis of the laminated character of
these primary surface layers.

I wish to express my thanks to Professor E. K. Rideal, F.R.S., for en­

couragement and advice during the course of the work and to Dr J. K.
Roberts for many helpful discussions. I am indebted to The Carnegie
University Trust for the grant of a Research Fellowship during the tenure of
which this work was carried out.

S um m ary

An experimental technique sufficiently sensitive to measure accurately

the very small amounts of non-polar gases which are adsorbed on alkali
halide crystals is developed. Isotherms for argon, oxygen and nitrogen on
KC1 and Csl are described and the heats of adsorption as a function of the
amount adsorbed are derived.
For these systems a maximum occurs in the curve of the heat of adsorption
plotted as a function of the amount adsorbed and this, it is shown, marks
precisely the position a t which a first monolayer is completed. The results are
compared with theoretical calculations of the adsorption behaviour of
argon on KC1 and Csl and very good general agreement is obtained. Prob­
able explanations are advanced for specific deviations.
In the range between the completion of a single monolayer and the bulk
condensation of the gas an amount equal to three to four times th at in the
first layer is adsorbed. I t is concluded th at the molecules in this region tend
to arrange themselves in layers rather than in localized aggregates.

R eferences

Bangham and Mosallam 1938 Proc. Roy. Soc. A, 166, 658.

Barrer 1937 Proc. Roy. Soc. A, 161, 476.
Bradley 1936 J . Chem. Soc. p. 1799.
Brunauer and Em m ett 1937 J . Am er. Chem. Soc. 59, 2682.
Cath 1918 Commun. Phys. Lab. Univ. Leiden, no. 152c/.
Cernuschi 1938 Proc. Camb. P hil. Soc. 34, 392.
Dube 1938 Proc. Camb. P hil. Soc. 34, 587.
Durau 1928 A n n . P hys., L pz., 87, 307.
Fowler 1935 Proc. Camb. P hil. Soc. 31, 260.
— 1936a Proc. Camb. P hil. Soc. 32, 144.
— 19366 Statistical Mechanics, 2nd ed. p. 833. Camb. Univ. Press.
— 1938 Physica, 5, 44.
Giauque and Clayton 1933 J . Am er. Chem. Soc. 55, 4879.
Langmuir 1918 J . Am er. Chem. Soc. 40, 1361.
 Downloaded from http://rspa.royalsocietypublishing.org/ on October 29, 2018

The adsorption of gases 367

Lenel 1933 Z . phys. Chem. B, 23, 379.
Lennard-Jones 1931 Proc. P hys. 43, 461.
Lennard-Jones and Devonshire 1936 Proc. Roy. Soc. A, 156, 6.
Lennard-Jones and Strachan 1935 Proc. Roy. Soc. A, 151, 442.
London 1930 Z . phys. Chem. B, 11, 222.
Muller 1936 Proc. Roy. Soc. A, 154, 624.
Orr 1939 Trans. Faraday Soc. 35, 1247.
Peierls 1936 Proc. Camb. P hil. Soc. 32, 471.
Roberts 1937 Proc. Roy. Soc. A, 161, 127.
— 1938 Proc. Camb. P hil. Soc. 34, 577.
Roberts and Orr 1938 Trans. Faraday Soc. 34, 1346.
Rushbrooke 1938 Proc. Camb. P hil. Soc. 34, 424.
Tompkins 1936 Trans. Faraday Soc. 32, 643.
Vegard 1934 P hys. 88, 235.
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— 1938 Proc. Camb. Phil. Soc. 34, 238.
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The magnetic susceptibilities of some cupric salts

B y J ames R eek ie
Royal Society Mond Laboratory, Cambridge

( Communicated by J. D. Cockcroft, F.R.S.— Received 22 July 1939)

1. I ntroduction

The crystalline field theory of paramagnetic salts has been applied by

ordahl (1934) to the determination of the magnetic susceptibilities of certain
cupric salts, and from a comparison with the existing experimental data it
has been concluded that the Cu++ ion in these salts can be regarded as acted
on by a predominantly cubic crystalline electric field due to the surrounding
ions of the crystal. The cupric salts considered by Jordahl were cupric
sulphate pentahydrate, CuS04.5H 20, and the potassium and ammonium
double sulphates, CuS04.K 2S04.6H 20 and CuS04.(NH4)2S04.6H20 re­
spectively. In the case of the first of these, X-ray investigations (Beevers
and Lipson 1934) have shown that the Cu++ ion is surrounded by an approxi­
mately regular octahedron of six negatively charged oxygen atoms, which
gives rise to an electric field of nearly cubic symmetry. In the case of the
double sulphates no structure determinations have been made but it is again
probable that the Cu++ ion is acted on by a cubic field arising from a regular
octahedral arrangement of the six water molecules around it.
24-2