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Journalof Low TemperaturePhysics, VoL 21, Nos, 3/4, 1975

A Virial Coefficient Analysis of Helium Adsorption


Isotherms*
Anthony D. Novaco
Lafayette College, Easton, Pennsylvanidf
and
Stevens Institute o f Technology, Hoboken, New Jersey
( R e c e i v e d D e c e m b e r 31, 1974)

A model in which the atoms in the second layer of a monolayer-plus helium


film are assumed to form a quasi-two-dimensional gas is used to analyze the
isotherm data of Goellner, Daunt, and Lerner for helium on Grafoil. The
parameters in the model are determined by a least-squares fit of the model
isotherm to the data. These parameters include the second and third virial
coefficients of the quasi-two-dimensional gas and the binding energy of the
second-layer atoms to the first layer. The empirical values are compared to
recent theoretical predictions for the two-dimensional helium gas. The agreement and discrepancies between theoretical and empirical values are discussed.
The conclusion is that the second layer (at low densities) can be described as an
imperfect two-dimensional gas with perhaps some modification of the interatomic potential due to substrate effects.

1. INTRODUCTION
The virial expansion is a useful technique for studying both bulk and
adsorbed gases, t-3,:~ In this approach, the relevant thermodynamic functions
are expanded in a power series in p, the density of the gas. The fundamental
development of this approach is based upon a cluster expansion of the
partition function, the expansion being in powers of 23p (three dimensions)
or 22p (two dimensions), where 2 = [2nh2/mkT] 1/2 is the thermal wavelength
and p is either the bulk or areal density.
The virial expansion was used in a recently published theoretical
* W o r k s u p p o r t e d , in part, by a g r a n t from the N a t i o n a l Science F o u n d a t i o n .
t P e r m a n e n t address.
:[:See Ref. 3 for a general d i s c u s s i o n o f the t h e r m o d y n a m i c s o f a n d virial e x p a n s i o n for a d s o r b e d
gases.
359
9 1975 Plenum Publishing Corporation, 227 West 17th Street, New York, N.Y. I0011. No part of this publication
may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical,
photocopying, microfilming, recording, or otherwise, without written permission of the publisher.

360

Anthony D. Novaco

investigation of the two-dimensional imperfect gas. 4 This study considered


the first-order correction to the thermodynamics of the ideal Boltzmann gas,
that is, it included the second virial coefficient. Both the effects of realistic
two-body interactions and Bose/Fermi statistics were included. The results
of that calculation agree quite well with the specific heat data for the low
density helium monolayer (first layer of helium adsorbed upon Grafoil)fl*
The conclusion of that study was that the low density helium monolayer
could be treated as an imperfect two-dimensional gas. Comparison between
theory and e -~eriment was made over density and temperature ranges of
0.01 < p < 0.03 atom/A 2 and 0.5 < T < 10K.
The virial expansion, however, has not been as useful in helium adsorption studies as it might be. This is, in part, due to the technical difficulty
of making pressure measurements (particularly precise measurements) at
the most interesting temperatures and pressures for studying the twodimensional imperfect gas. For instance, the use of the virial expansion for
(helium) isotherm analysis has been mostly restricted to relatively high
temperatures, with as much emphasis on the effects of adatom-substrate
interactions as on the effects of adatom-adatom interactions.6,v Use of the
virial expansion to investigate primarily the effects of adatom-adatom
interactions should involve low temperatures and low densities, so that
adatom-substrate effects do not dominate the physics and obscure adatomadatom effects. At these temperatures and densities, the virial coefficients
should be quite sensitive to the adatom-adatom interaction. Furthermore,
if the temperature were low enough, it might be possible to observe the twodimensional liquid-gas transition. 4 Such a study must involve both an
experimental technique capable of precise pressure measurements (free of the
usual thermomolecular corrections) and must involve a smooth homogeneous substrate for which qs,, the isosteric heat, is not very large (if % is large,
then the pressures will be too low).
In a recent experimental study of the adsorption of the helium isotopes
on Grafoil, precise pressure measurements were made using an in situ capacitance gauge to measure the pressure. 8 Although it was not possible to measure
pressures in the imperfect gas region for the first layer (empirical estimates
place this pressure at "10-1~
Torr),9 it was possible to measure"the
pressure for adsorbed volumes V slightly above Vm, the adsorbed volume
corresponding to a "completed" monolayer. Furthermore, the precision of
these measurements is about 0.005 Torr. This raises the possibility of determining the virial coefficients appropriate to a quasi-two-dimensional
imperfect gas of helium atoms adsorbed on a substrate of helium-plated
Grafoil. It is the purpose of this communication to show that such an analysis
is practical and to report the numerical values for the second and third virial
*See Ref. 5 for a s u m m a r y of recent work on helium monolayers,

A Virial Coefficient Analysis of Helium Adsorption Isotherms

361

coefficients which result from the analysis of the G o e l l n e r - D a u n t - L e r n e r


data. From these virial coefficients, the appropriate van der Waals constants
are calculated.
The basic agreement between theory and experiment is good, although
some discrepancies do exist. It is found that the data analysis will produce
reliable values for the monolayer capacity, the binding energy of the adatom
(helium) to the substrate (helium-plated Grafoil), and the second and third
virial coefficients for the imperfect gas.

2. I S O T H E R M ANALYSIS AND T H E VIRIAL E X P A N S I O N


The analysis of the adsorption isotherm via a virial expansion (for the
2D gas) can be found in Ross and Olivier's treatise on adsorption. ~~ We
outline the treatment here for the sake of completeness and to emphasize the
salient points.
The adsorbed gas is treated a s a two-dimensional imperfect gas which is
in equilibrium with an ideal bulk vapor. The interaction of the adatom with
the substrate is described by a single number, the binding energy to the
substrate. This means that the temperature must be low enough so that the
adatoms are in their fundamental vibrational mode perpendicular to the
surface. 11 The interaction between the adatoms and their statistics are
accounted for by a virial expansion in the areal density. The isotherm is
obtained by relating the pressure of the bulk gas to the density of the adsorbed
atoms through the uniqueness of the chemical potential/~. The pressure of
the bulk gas is
P = k T 2 - 3 e ~/kr

(1)

If the adsorbed gas were an ideal Boltzmann gas, then the chemical potential
would be
t~ = e + k T In (p)2)

(2)

where - e is the binding energy (per atom) of the adatom to the substrate
and p is the adatom number density. For a Bose or Fermi system, this is the
leading term at low density. For the imperfect gas and/or for Bose or Fermi
statistics, a correction to the above expression can be written as a power
series in the density p:
/~ = e + kT[ln (p)2) + 2 B p + ~ C p 2 + ~ D p 3 + ... ]
(3)
i
To reduce this to the usual virial expansion for the pressure, it is only necessary
to use
~r

= p ~u/ep

(4)

362

Anthony D. Novaco

where 4~ is the spreading (or two-dimensional) pressure. Thus


~)/kT = p + B p 2 + CO 3 + Dp'* + . . .

(5)

with B as the second virial coefficient, C as the third, etc. These coefficients
are, in general, dependent upon temperature. The resulting isotherm is
P = [ p k T 2 - 1 exp (~/kT)] exp (2Bp + 3Cp2 + -}Dp 3 + . . . )

(6)

At this point it is worthwhile to remind the reader about the way in


which the above treatment is related to the van der Waals equation of state,
and how these considerations affect the isosteric heat. The van der Waals
equation of state is
[tip + ap 2] [1 - bp] = p k T

(7)

where the constants a and b are independent of temperature. Rearranging


the above as a power series in p, we obtain
dp/kT = p + [b - ( a / k T ) ] p 2 + bap 3 + b3p 4 + 9

(8)

from which the virial coefficients can be read.


The isosteric % is defined by
_OInP
% =

t?fl

where

fl

1
= ~

(9)

Therefore, combining (10) and (6), we obtain


qst = - e

+ -}kT - 2p(~B/Ofl) - ~p2(OC/~fl) + . .

(10)

If the gas is described by the van der Waals equation of state, then OC/Ofl = 0
and OB/~fl =- - a , so that
% = - ~ + ~ k T + 2ap

3. S E C O N D - L A Y E R

MODEL

(11)

AND THE DATA ANALYSIS

The application of the isotherm equation in (1) to the experimental


data for V > V,, is based upon the assumption of an inert first layer and the
use of the imperfect gas as a model of the atoms in the second layer. The areal
density of the atoms in the first layer is assumed to be unaffected by the
addition of atoms to the second. Thus the areal density of the atoms in the
second layer is
p = [(V - V,,)/AVo]N o

(12)

A Virial Coefficient Analysis of Helium Adsorption Isotherms

363

where Vis the volume of the adsorbed gas at STP, Vmis the same for a "completed" monolayer, V0 is the volume of one mole at STP, N o is Avogadro's
constant, and A is the area of the surface.
Equation (12) combined with Eq. (6) requires that five constants be
determined. One of these constants, namely the area, serves to scale the
density and so it was calculated using an independent measurement. The
remaining four constants, namely Vm, e, B, and C, are determined by a least
squares fit of Eq. (6) to the data of Goellner e t at. 8 The values for these constants are listed in Table I, and are based on the 4.24 K isotherm for each
isotope.
The area was calculated by using the fitted value of V,, and the experimental value for the density of the completed mono!ayer, and then assuming
that the area for the second layer is the same as that for the first. This density
p,, for the first layer is 0.115/~-2 for 4He.S This particular value is also that
determined by a theoretical study of the adsorption of *He on graphite. *s
For 4He, V,~ is found to be 6.43 cm 3 per gram of Grafoil, implying an area
of 15.0 m 2 per gram of Grafoil. This is the area found by Goellner et al.
using an argon isotherm to determine the area. Internal consistency can be
checked by using the above value of the area and the fitted value of Vm
for 3He (6.022 cm 3 per gram of Grafoil) to calculate the density of the completed 3He monolayer. The result of this calculation is Pm= 0.108 ~-z0
a result which agrees both with theory and with other experiments, s'ts
Equation (6) was fitted to the data of Goellner et aL using a standard
nonlinear least squares fit computer program. The values of the parameters
and their standard deviations were calculated along with the predicted
deviation of each datum from the fitted curve. The standard deviations are
listed in Table I. TabIe II lists the tabulated data 8 and the appropriate values
of the fitted curve. The predicted deviations were used to determine the data
range included in the computer fit.
Since the experimental results extend beyond the region of validity
of the isotherm [Eq. (6)], it is necessary to specify reasonable criteria for the
inclusion or exclusion of data in the least squares fit. These criteria are based
TABLE I
Best Fit Values for V,~(per G r a m Grafoil), e, B, and C
(Based upon the Data in Ref. 8)
4He
Vm, cm 3 (STP)

a/k, K
B, ~2
C, ~4

6.433
-30.0
-0.33
53

_+ 0.004
0.1
0.22
12

3He
6.023
-25.4
7.0
37

0.003
0.1
0.6
28

364

Anthony D. Novaco
TABLE II
Fitted Isotherm vs. Data of Ref. 8
~He

~He

Adsorbed
volumefl
cm 3 STP

Pressure

Pressure

Adsorbed

Pressure

Pressure

(fitted),

(actual),

volume,"

(fitted~,

(actual),

Torr

Torr

cm 3 STP

Torr

Torr

6.681
6.784
6.816
6.883
6.950
7.017
7.157
7.287
7.417
7.547
7.675
7.804

0.3887
0.4947
0.6028
0.7098
0.8176
0.9262
1.155
1.373
1.595
1.821
2.050
2.286

0.388
0.488
0.597
0.703
0.816
0.928
1.159
1.380
1.600
1.821
2.054
2.278

6.265
6.321
6.376
6.429
6.533
6.633
6.732
6.833

0.889
1.111
1.334
1.556
2.009
2.469
2.948
3.463

0.902
1.109
1.323
1.545
2.000
2.477
2.964
3.460

"Values for adsorbed volume are per gram of Grafoil.

upon the statistical analysis of the data. The maximum number of points
was included in the analysis subject to two constraints. First, the quality
of the fit was not significantly altered by the inclusion of a datum. Second, a
datum was excluded if its actual deviation from the curve was more than three
times its predicted deviation. These constraints were relaxed on a number of
trial fits in order to determine the sensitivity of the isotherm parameters to
the data range used. Increasing the data range by about 25 ~ had, at most, a
20 ~ effect upon any parameter. However, such an increase had about an
order-of-magnitude effect upon standard deviations and the general quality
of the fit. The final values for the parameters were determined from 12 points
(4He) and 8 points (3He) with the typical deviations between data and the
fitted curve being 0.005 Torr (4He) and 0.008 Torr (3He). All points within a
given range were included. However, data corresponding to second-layer
densities less than 0.03pro or greater than 0.3pro were excluded.
The exclusion of high density data points can be justified by estimates of
the effects of D, the fourth virial coefficient. The exclusion of points near the
monolayer completion point implies that the assumption of the inert first
layer may not be valid for very low second-layer densities. Both of these points
are examined in the last section.
The assumption that the effective area for the second layer is the same
as the area of the first layer could be a source of a systematic error in the
values of the coefficients. This uncertainty does place a limit upon the reliability of the values for the virial coefficients which we estimate to be about

A Virial Coefficient Analysis of Helium Adsorption Isotherms

365

10-15 ~o. The effect upon e is much smaller. If several isotherms (at different
temperatures) are analyzed, then the area for the second layer can be determined directly.
4. C O M P A R I S O N O F T H E R E S U L T S W I T H T H E O R Y
Since only one isotherm was analyzed for each isotope, it is not. possible
to do a detailed comparison between l:heory and the least squares analysis.
However, it is possible to compare the theoretical and the empirical virial
coefficients on the basis of predicted van der Waals constants, at least for
4He. This is a reasonable comparison since the theoretical B(T) behaves in
the manner predicted by the van der Waals form: B ( T ) = b - a/kT. 4 It is
also possible to compare the empirical results for the binding energies with
theoretical predictions and other experiments.
A quick check of the theoreticaP value of the 4He B at T = 4.24 K
( - 4 . 3 2) shows that the empirical value ( - 0 . 3 3 A 2) is a factor often smaller.
Furthermore, trial fits of the data using the theoretical value of B were not
satisfactory. The typical deviation for such a fit is 0.1 Torr instead of the
0.005 Torr found for the best fit. The theoretical values for the van der Waals
constants a and b are a/k = 53/~ZK and b = 8 A 2. The resulting Boyle
temperature [temperature where B(T) = 0] is 6.6 K. The empirical values of
a and b are a/k = 32 A 2 K and b = 7.3 A 2. The corresponding Boyle temperature is 4.2 K. Theory and analysis differ, then, on the value of a but not
on the value of b, since the difference in the value of b is less than the standard
deviation for the empirical value. The difference in the value for a is significant, but this term could be sensilive to the behavior of the a d a t o m adatom potential in the region of the minimum and the potential could be
sensitive to substrate mediated interactions 12 and/or the averaging of the
interatomic potential due to vibrational motion perpendicular to the
surface.13 A major consequence of the smaller value of a is a lowering of the
estimated critical temperature from f i e theoretical range 4 of 1.4-2.0 K to
the range of 0.9-1.2 K. This kind of effect in the second layer was seen by
Bretz, ~4 who measured the heat capacil y of the second layer. The maximum
in the heat capacity for this layer occu~rred at a lower temperature than the
corresponding maximum in the first-layer heat capacity. Since the substrate
potential tends to localize the first layer (in the direction normal to the surface)
more than the second layer, it is the first layer which should be more like
the theoretical two-dimensional calculation.* Furthermore, the second layer
rides on a layer of helium, and this "substrate" might cause important
modifications in the a d a t o m - a d a t o m interaction in the second layer.
*Compare the substrate potential in Ref. 11 (Fig. 2) to that in Ref. 15 (Fig. 3).

366

Anthony D. Novaeo

The binding energy (-z/k) of a 4He atom in the second layer to the
helium-plated Grafoil substrate is 30 K. This number agrees with the
empirical value of Elgin and Goodstein 9 (29 K) and with the theoretical
value (30 K).I 5
The comparison between theory and analysis is not as rewarding for
3He as for 4He. This is due, in large part, to the large standard deviation
found for the third virial coefficient. The empirical values for the second and
third virial coefficients (at 4.24 K) are 7.0/~2 and 37 A 4, respectively. Variations of 50% in the value of C produced only small (< 10%) variations in
the value of B. This indicates that the value of B is reliable even if the value
of C is not. The empirical value of B is only 10 % below the theoretical value
(8.1 A2). The empirical value of -e/k is 25.4 K, which is good agreement
with the theoretical value, x5
5. IMPLICATIONS AND CONCLUSIONS
Estimates of the effects of higher virial coefficients can be made by usiiag
the van der Waals description. Examination of Eq. (8) shows that D = b 3.
The value of b is 7.3 A 2 for 4He. If p is equal to 0.025 A 2 (this is at the high
end of the density range), then the effect of D upon the pressure is less than
0.02 Tort. This is to be compared to a typical deviation of 0.005 Torr,
indicating that the effect of the fourth virial coefficient is just noticeable at
high densities. Thus it is reasonable to exclude data at higher densities in a
fit which excludes the fourth and higher virial coefficients.
The contribution of the third virial coefficient to the pressure is important throughout most of the density range considered. Yet the calculation
of Siddon and Schick (which excludes this term) agrees very well with the
specific heat data in this very range. An explanation of this "paradox"
is suggested by the van der Waals description, for which C = b 2 is independent of temperature. A temperature-independent C does not contribute
to the specific heat, just as it does not contribute to the isosteric heat [see
Eqs. (10) and (11)]. The contributions to % due to the nonideal behavior
can be calculated from Eq. (11). The value of elk is - 3 0 K_3T/2 is about
6 K and pa/k < 1 K. Thus the corrections to qst due to the virial coefficients
is about 3 %.
The necessity of excluding points near the monolayer "completion"
point could be an indication that the first layer is not inert near this point.
In fact, near monolayer "completion," it is reasonable to assume that both
the density of the first and the density of the second layer are affected by
addition of atoms to the film. The analysis then implies that after the density
of atoms in the second layer is greater than about 0.03pro, the density of the
first layer is unchanged by further addition of atoms to the film and only the

A Virial Coefficient Analysis of Helium Adsorption isotherms

367

density of the second layer changes. Furthermore, the overall quality of the
fit indicates that substrate inhomogeneity effects are not important for the
second layer (at least after p > 0.03p,,),
The analysis shows that the low density second layer can truly be
t h o u g h t of as a quasi-two-dimensional imperfect gas on a s m o o t h substrate.
The empirical values for the viriat coefficients and binding energies are in
g o o d agreement with the theoretical values, although there is a g o o d indication that the interatomic potential for a t o m s in this layer is modified by the
substrate. Empirical van der Waals constants were found for *He, and these
values indicate that a liquid gas critical point m a y exist at a b o u t 1 K.
F u r t h e r experimental work needs to be done for both 3He and 4He,
although experiments very close to the (*He) critical point might be impossible since the pressure wilt decrease as exp F.(-30 K)(1/T - 1/4 K)].
This means that at densities near the critical density (about 0.03 A - 2 ) and
even at 2 K, the pressure is a b o u t 10- a Torr. Nevertheless, it is still i m p o r t a n t
that m o r e work be carried out so that the equation of state be determined
(over as large a region as is practical). Such an investigation would be very
useful to the study of low density monolayers.
ACKNOWLEDGMENTS

The a u t h o r would like to thank Prof. J. G. D a u n t and Dr. G. Goellner


for access to their data prior to publication and for m a n y stimulating discussions while the a u t h o r was a guest at the Cryogenics Center at Stevens
Institute of T e c h n o l o g y during the s u m m e r of i974.

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368

Anthony D. Novaco

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