Dependence of Surface Tension on Temperature

S. W. Mayer

Citation: The Journal of Chemical Physics 38, 1803 (1963); doi: 10.1063/1.1733879
View online: http://dx.doi.org/10.1063/1.1733879
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 THE JOURNAL OF CHEMICAL PHYSICS VOLUME 38, NUMBER 8 15 APRIL 1963

Dependence of Surface Tension on Temperature*

S. W. MAYER
Laboratories Division, Aerospace Corporation, 2400 E. El Segundo Boulevard, El Segundo, Calijornia
(Received 25 October 1962)

It is shown that the equation of Reiss et al. for the surface tension of liquids composed of hard-core mole-
cules does not usually provide the proper dependence of surface tension on temperature for typical non-
ionic liquids. Because of this, an empirical computation procedure is adopted, whereby the hard-core
diameter is given a temperature dependence similar to that of the collision cross section for gas viscosity.
When Lennard-Jones 6--12 or Sutherland intermolecular-potential data are then used to calculate a hard-core
diameter, the agreement between computed and measured dependence of surface tension on temperature is
usually very good, even for liquids composed of such polar, aspherical molecules as water, ethanol, and
ammonia. As an illustration of the potential value of the empirical use of gas-viscosity data for improving
computations of the dependence on temperature of physical properties and thermodynamic values for
liquids, the Lennard-Jones 6-12 and Sutherland data are applied to two rigid-sphere relationships for
liquid compressibility.

I. INTRODUCTION this, an empirical computation procedure was adopted

HE ideasla used in a radial distribution-function
T theory of liquids consisting of rigid-sphere molecules
(zero attraction potential, impenetrable core) have
been extended by Reiss, Frisch, Helfand, and Lebowitz1b
to develop an approximate treatment of liquids com-
posed of hard-core molecules (finite attraction PO-
tential, impenetrable core). The following relationship
for computing surface tension was obtained from their
treatment 1b :
(1)
where (J" is the surface tension, a is the hard-core di-
ameter of the molecules, T is the absolute temperature,
k is Boltzmann's constant, p is pressure, y is 7ra 3N /6V,
N is Avogadro's number, and V is the molar volume.
The term pa/2 generally is of negligible magnitude and
can be ignored in the calculation. It can be seen that
only a knowledge of the density of the liquid and of the
hard-core diameter of the molecules was needed to
calculate the value of the surface tension. Equation
(1) was applied to nonpolar liquids,1b molten ionic
salts,2 and liquid metals 3 to compute values of the sur-
face tensions, which usually were found to be within
30% of the measured values.
In the present study it will be shown that the de-
pendence on temperature of surface tensions computed
from Eq. (1) is unsatisfactory when compared with the
measured dependence on temperature. 4 Because of
* Based on a paper presented at the American Physical Society
Meeting, Seattle, 27-29 August 1962.
1 (a) H. Reiss, H. L. Frisch, and J. L. Lebowitz, J. Chern.
Phys. 31, 369 (1959); (b) H. Reiss, H. L. Frisch, E. Helfand,
and J. L. Lebowitz, ibid. 32, 119 (1960).
2 H. Reiss and S. W. Mayer, J. Chern. Phys. 34, 2001 (1961).
3 S. W. Mayer, J. Chern. Phys. 35, 1513 (1961).
4 Landolt-Bornstein Tabellen (Julius Springer-Verlag, Berlin,
1956), II Band, 3 Teil.
1803
whereby the parameter a was given a temperature de-
pendence similar to that of the collision cross section
for gas viscosity. Gas-viscosity temperature-dependence
data were selected for this purpose because of the rela-
tively abundant supply of such measurements, which
have been conveniently summarized in terms of inter-
molecular potential functions. 5 It was found that gas-
viscosity data did lead to calculations of the change of
the parameter a with temperature which provided the
proper dependence of surface tension on temperature
when combined with Eq. (1). Moreover, when rigid-
sphere equations for fluid compressibility were com-
bined with the use of gas-viscosity data to calculate
a dependence of the rigid-sphere diameter on temper-
ature, the agreement between computed and measured
temperature dependence of liquid compressibility im-
proved markedly compared to that obtained without
using the gas intermolecular-potential parameters.
Although these computational procedures are of interest
inasmuch as they show that intermolecular potentials
obtained from gas data can furnish good agreement be-
tween computed and measured temperature dependence
of some properties of liquids, it should be emphasized
that providing a temperature dependence for the pa-
rameter a in Eq. (1) and extending two-body collision
data for a gas to the liquid is done empirically.
II. COMPUTATION PROCEDURE
Both the Sutherland mode16 •7 for intermolecular po-
tentials and the Lennard-Jones 6-12 potentialS func-
tion have had considerable success for interpolation of
• J. O. Hirschfelder, C. F. Curtiss, and R. B. Bird, Molectdar
Theory oj Gases and Liquids (John Wiley & Sons, Inc., New
York, 1954).
6 S. Chapman and T. G. Cowling, The Mathematical Theory of
Non-unijorm Gases (Cambridge University Press, New York,
1960), 2nd ed.
7 Reference 5, p. 549 ff. and p. 565 ff.
s Reference 5, p. 552 ff.

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 1804 S. W. MAYER

TABLE 1. Measured and computed surface tensions of several between the centers of an interacting pair of molecules,
hydrocarbons. a
E is the maximum attraction energy in ergs, and d is a
Meas- Suther- Lennard- Con- constant exponent. For a rigid-sphere model the co-
Liquid T ured land Jones stant a efficient of gas viscosity TJ is given by 5
283.1 30.2 30.0 29.8 28.2 TJ= 266.93X 10-7 (MT)!/a 2, (3)
293.1 28.9 29.0 28.8 28.2
313.1
where M is the molecular weight, the parameter a is
26.2 26.1 26.2 28.2
in angstroms, and the units of TJ are g cm-1 secl . It has
323.1 25.0 24.7 24.8 28.2 been shown for the Sutherland model that
333.1 23.7 23.6 23.7 28.0
90.7 18.2b 15.7
TJ = 266.93X 10-7 (MT) t/ a2 (1 + S/T) , (4)
18.8 18.5
CH. 111. 7 13.7 b 13.8 14.0 16.3 where S is the Sutherland constant, related to E and
d. 7 Values of S for nonpolar and polar gases have been
CH. 120.0 11.9b 12.3 12.1 16.9
tabulated. 6 ,7
(CH2). 288.1 25.6 25.9 26.0 23.5
(CH2 ). 293.1 25.0 25.2 25.2 23.4 TABLE III. Surface tensions of several elements.
(CH2 ). 308.6 23.2 23.2 23.2 23.3 Meas- Suther- Lennard- Con-
Liquid T ured land Jones stant a
(CH2 ) 6 329.9 20.8 20.8 20.9 23.1
C SH1S 273.1 23.8 25.1 24.4 21.8 Ar 83.9 13.5 a 13.6 13.6 13.1

CSH18 288.1 22.2 22.5 22.5 21. 7 Ar 87.3 12.6a 12.7 12.7 13.1

CSH1S 303.1 20.7 20.3 20.7 21.8 Ar 90.0 11.9 12.1 13.0

CSH18 323.1 18.8 18.0 18.5 21. 7 N. 63.1 12.1a 12.4 12.3 10.3
77 .3 9.0 a 9.1 9.2 10.7
a The measured surface-tension data (in dyn em-I) of Tables I through VI
were obtained from reference 4, except as otherwise noted. 90.0 6.2a 7.4 7.6 10.1
b Reference 9.
62.5 20.3 23.9 23.4 17.9
gas-viscosity-temperature data. The Sutherland inter- 76.7 16.7 16.0 16.1 18.3
molecular-interaction model is characterized by a hard-
81.4 15.5 14.6 14.7 18.4
core repulsion potential and a power-law attractive
potentiaF: Cb 213.1 31.2 31.9 31.6 29.6
<,O(r)=oo, r<a, Cb 233.1 27.3 27.3 27.7 29.3
<,O(r) = -E(a/r)d, r>a, (2) a Reference 9.

where <,O(r) is the interaction potential, r is the distance

In order to compute the effective change in a2 when
TABLE II. Surface tensions of organic chlorides. the temperature is changed from Tl to T 2 , Eqs. (3)
and (4) were utilized to obtain the following relation-
Meas- Suther- Lennard- Con-
Liquid T ured land Jones stant a ship:
(5)
CHCla 288.1 27.9 28.0 28.0 26.5
CHCh 293.1 27.2 27.3 27.2 26.6 where the subscripts 1 and 2 indicate the temperatures.
In the computational procedure a1 2 was calculated from
CHCh 303.1 25.9 25.7 25.9 26.3 Eq. (1), using measured values of surface tension4 and
CHCh 313.1 24.6 24.6 24.8 26.4 density 4 at T I • Then a22 was calculated in accordance
with Eq. (5) and substituted into Eq. (1) to obtain
CCI. 288.1 27.5 27.5 27.5 26.9 the computed result for the surface tension at T 2 •
CCI. 303.1 25.5 24.8 25.2 26.9 The Lennard-Jones 6-12 intermolecular potential is
expressed8 by
CCI. 313.1 24.2 23.6 24.1 26.8
<,O(r) =4E[(a/r)IL (a/r) 6]' (6)

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 D E PEN DEN CEO F SUR F ACE TEN S ION 0 N T E M PER A T U R E 1805

It has been shown for this intermolecular potential that TABLE V. Surface tensions of polar inorganic compounds.

'17= 266.93 X H)-7(MT)!jk/a 2n(2,2)*, (7) Meas- Suther- Lennard- Con-

Liquid T ured land Jones stant a
where n(2,2)* is a reduced integral for the transport co-
·efficient and fk is a term in the Enskog series,s n(2,2)* NH3 233.1 35.6 35.1 29.2
and fk are functions of the reduced temperature T*, NH. 243.1 33.3 33.0 28.4
which is equal Tk/ E. Tabulated results for €/k calculated
NH3 253.1 31.0 30.8 27.7
from viscosity data are available,· For the computations
made in this work, fk did not usually deviate signifi- NH3 263.1 28.8 28.7 27.1
-cantly from unity. 283.1 24.3 24.9
NHs 26.2
The change in a2 as the temperature is changed from
Tl to T2 was computed readily from the following re- SO. 253.1 30.3 30.0 30.1 28.5
lationship, which was obtained from Eqs. (3) and (7): So. 273.1 26.5 26.5 26.7 28.4
(8) So. 283.1 24.6 25.3 25.9 28.4
The subscripts 1 and 2 denote the temperatures Tl and H 2O 283.1 74.2 75.1 67.1
T 2 • Eq, (8) is convenient to use since the values of H 2O 293.1 72.8 72.8 69.2
-n(2,2)* andfk are tabulated.· As in the use of the Suther-
land constant for these computations, a12 is calculated H.o 313.1 69.6 69.6 72.8
from Eq. (1) for Tl, and a22 is then obtained from Eq. H 2O 323.1 67.9 68.2 74.1
(8) for the calculation of the surface tension at T 2•
Other intermolecular potential-energy relationships H 2O 333.1 66.2 67.0 75.6
<:an, of course, be used in a similar fashion. For example,
molecules which repel each other according to an in-
verse power law obey an equation of the form: directly by extrapolating gas-viscosity-temperature
(9) measurements to liquid temperatures so as to calculate
'17= cT·,
the changes in a2 at temperatures of interest. Then these
where c and s are constants.7 In this case, values of a2 can be used in conjunction with Eq. (1)
to obtain computed results for surface tensions at the
a22 =a12 ( T1/T2),-l. (10) corresponding temperatures.
The Buckingham potential, its modifications, and sev-
eral angle-dependent potentials could also be used, III. RESULTS
but their parameters have been obtained for relatively In Tables I through V, the computed values of sur-
few molecules.· Alternatively, Eq, (3) can be utilized face tension are compared with the measured values'
for several types of liquids over a range of temperatures.
TABLE IV. Surface tensions of ethanol, methanol, and ether,
The computed surface tensions are in Columns 4 and
Meas- Suther- Lennard- Con-
5; they were obtained from the Sutherland and Lennard-
Liquid T ured land Jones stant a Jones models by using the procedures described in Sec.
II. For comparison, the values obtained by using only
C.H.OH 273.1 24.3 24.3 23.9 22.0 Eq. (1) with the parameter a constant at al are listed
C.H,OH 283.1 23.4 23.3 23.3 22.3 in the last column of Tables I-V. Data used in the
computation procedures are summarized in Table VI.
C.H.OH 288.1 23.0 22.8 22.9 22.4 The reference temperature (in degrees Kelvin), and
C2H.OH 303.1 21. 7 21.8 21.9 22.8 the surface tension and computed rigid-sphere diameter
at the reference temperature are presented in Columns
C.H,OH 323.1 19.9 20.7 20,9 23.3 2, 3, and 4, respectively. The reference temperature
CH.OH 283.1 23.4 23.0 23.0 22.1 was selected merely as some convenient temperature
near the center of the temperature range for which
CH.OH 288.1 22.9 22.7 22.7 22.2
sufficient data for carrying out the computations were
CH.OH 303.1 21. 7 21.8 21.9 22.6 available. In Columns 5 and 6 the Sutherland con-
CHaOH 323.1 20.0 21.1 21.6 23.1
stant and elk for the Lennard-Jones function are listed.
In Column 7, the tabulated5 value for the parameter a
C4H lO 0 283.1 18.2 18.1 17.1 in the Lennard-Jones function is listed for comparison
C4H lO0 303.1 15.9 15.8 17.0 with al. It should be noted, however, that al is com-
puted for a liquid at T 1, whereas the parameter a of

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 1806 S. W. MAYER

TABLE VI. Data used for computations. Inasmuch as Eq. (1) was derived l on the basis of
spherical intermolecular potential fields and neither the
<11 al a." Lennard-Jones 6-12 nor the Sutherland potential are
Liquid TI dynlcm (1) S Elk" (1)
angle-dependent, the question arises as to the appli-
C.H6 303.1 27.5 5.01 3800 440 5.27 cability of this treatment of the liquid state to liquids
100.0 16.2b composed of polar or markedly aspherical molecules.
CH. 3.63 198 0
137 3.82
Nevertheless, relatively good agreement between meas-
(CH2). 303.1 23.8 5.34 330 d 324 6.09 ured and computed surface tensions is obtained for
C SHI8 293.1 21. 7 6.29 460- 320 7.45 such liquids. This gratifyingly wide applicability is
outstanding among theoretical treatments of liquids
C2H.OH 293.1 22.6 3.99 407- 391 4.46 based on molecular parameters; such treatments usually
CHaOH 293.1 22.5 3.32 487- 507 3.59 are applicable only to liquids consisting of mona tonic
or spherical, simple nonpolar species. 5 Of course, it is
C,HIOO 293.1 17.0 4.94 325 d
possible to speculate that rotational averaging in the
CHCla 298.1 26.6 4.76 373- 327 5.43 liquid permits this extrapolation of gas intermolecular
potentials to the liquid via the Lennard-Jones or
CCI. 293.1 26.8 5.17 365- 327 5.88 Sutherland models.
Ar 85.5 13.1b 3.31 156 d 124 3.42 In Table I, the results are summarized for the non-
polar hydrocarbons, benzene, methane, cyclohexane,
N2 70.0 1O.5b 3.53 108 0
92 3.68
and octane. Methane's intermolecular-interaction po-
O2 71.1 18.2 3.41 133 d 113 3.43 tential is essentially spherical, but the agreement found
for methane is not much better than that found for
Cb 223.1 29.2 3.89 325 0
357 4.12
benzene and cyclohexane. Octane was selected as an
NHa 273.1 26.6 2.88 377 c example of a highly aspherical molecule and it did give
S02 263.1 28.4 3.74 416c 252 4.29 the poorest agreement among the hydrocarbons, ex-
hibiting too strong a dependence of surface tension on
H 2O 303.1 71.2 2.89 548d temperature. The organic chloro-compounds of Table
II are relatively spherical and nonpolar. Chloroform
" Reference 5, p. 1110 II. The parameter a in the Lennard-Jones 6-12 potentia'
function as obtained from gas-viscosity data is tabulated under the symbol as.
shows somewhat better agreement than carbon tetra-
in the last column. chloride.
b Reference 9. In Table III argon shows good agreement (as it does
o Reference 6, p. 225.
d E. A. Moelwyn-Hughes, Physical Chemistry (Pergamon Press, Ltd., London,
with other treatments of liquids5,9). The agreement for
1961), 2nd ed., p. 610. nitrogen and chlorine is not quite as good. Oxygen ex-
_ J. R. Partington, An Advanced Treatise on Physical Chemistry (Longmans hibits the poorest agreement among all the liquids in
Green and Company, Ltd., London, 1949), Vol. 1, p. 858 II.
the tables. The computed dependence on temperature
of the surface tension of oxygen is higher than the
the Lennard-Jones function is selected to be constant measured dependence. This result would be expected
over a wide temperature range of gas viscosities. if the intermolecular attraction (on which Elk and S
IV. DISCUSSION are dependent5) were stronger in the gas than in the
liquid or, conversely, if the repulsion were stronger in
It can be seen from these results that the use of gas- the liquid than in the gas. A comparatively high number
viscosity data for calculating the effect of temperature density (equal to N IV) for oxygen molecules in the
on the collision diameter of molecules usually gives the liquid could cause such a stronger repulsion by reducing
proper dependence of surface tension on temperature r sufficiently to emphasize the repulsion component of
when combined with Eq. (1). However, when Eq. (1), Eq. (6). In fact, Yl (equal to 1ral3N16Vl) , which is the
the hard-core expression for liquids, is used alone and ratio of the hard-core volume per mole to the molar
not in combination with the Sutherland or Lennard- volume at the reference temperature, is almost 0.5 for
Jones 6-12 potentials for the gas molecules, the calcu- oxygen, compared to 0.4 or less for the other elements;
lated dependence of surface tension on temperature is this is much the highest value of Yl among the liquids
usually unsatisfactory and, in fact, has the opposite in the tables. It consequently appears possible that the
sign from the measured dependence in some cases (e.g., high value of Yl causes a stronger repulsion for oxygen
methane, ethyl alcohol, methyl alcohol, oxygen, and in the liquid than in the gas. If this is so, high values of
water). For most of the liquids in Tables I through V, Yl for a given liquid would suggest that the approach
the Sutherland model is about as successful as the
Lennard-Jones 6-12 function in producing good agree-
9 S. Chang, T. Ree, and H. Eyring in Second Symposium on
ment between the measured and computed surface Thermophysical, Properties, edited by J. F. Masi and D. H. Tsai
tensions. (Academic Press Inc., New York, 1962), p. 88.

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 D E PEN DEN CEO F SUR F ACE TEN S ION 0 N T E M PER A T U R E 1807

used in this study would not provide good agreement TABLE VII. Dependence of isothermal compressibility
on temperature.
for that liquid. Fortunately, most liquids do not have
such high values of Yl, although some do occur among f3" f3 f3 f3
the molten metals. 3 Meas- Suther- Lennard- Rigid
Tables IV and V contain typical examples of organic Liquid T ured land Jones sphere
and inorganic polar, nonspherical molecules. Theoreti- 283.1 8.7 7.6 8.0 10.2
C6H 6
cal treatments of liquids based on cell and hole models
have been least successful with liquids consisting of C6H 6 293.1 9.4 8.5 9.0 9.9
such molecules since the correlation of physical prop- C6H6 303.1 10.2 9.8 10.0 9.8
erties with the molecular parameters has not been very
good,S although advances show promise.9 It accordingly C6Hs 313.1 11.0 12.2 11.9 9.6
is particularly interesting to note that the typical polar C6Hs 323.1 11.9 12.6 12.3 9.4
liquids in Tables IV and V exhibit rather good agree-
ment between computed and measured dependence of C6H6 333.1 12.8 14.1 13.7 9.2
surface tension on temperature, when the Sutherland CCI. 288.1 10.0 9.2 9.4 10.0
or Lennard-Jones attraction parameters are used to
modify the hard-core relationship [Eq. (1)]. Until CCl. 293.1 10.3 9.9 10.0 9.9
these computational approaches are investigated for CCl. 303.1 11.2 11.3 11.3 9.7
additional liquids and for other physical properties of
CCI. 313.1 12.2 12.6 12.4 9.5
liquids, it is considered preferable not to speculate on
the reasons for the empirical applicability of making "E. B. Fryer, J. C. Hubbard, and D. H. Andrews. J. Am. Chern. Soc. 51. 759
the parameter a in Eq. (1) dependent on temperature (1929). The units for f3 in this table are 10-11 em' dyn- 1 •
and relating that dependence to gas collision cross
sections. lated by using Eq. (12) in combination with Eq. (5)
or Eq. (8). Computed and measured compressibilitie!Y
V. EXTENSION TO OTHER PROPERTIES OF LIQUIDS
are compared in Table VII for benzene and carbon
The significance of the computation procedures of tetrachloride. The parameters used in the computations.
Sec. II would be enhanced if they could be used to were taken from Table VI. Inspection of Table VII:
modify rigid-sphere relationships for liquids through shows that the compressibilities calculated on the basis'
the application of realistic potential functions. Since of the Sutherland and Lennard-Jones models have the
the numerous calculations required to test in detail the proper sign for the dependence of compressibility on
applicability of these computation procedures to rigid- temperature, whereas the rigid-sphere Eq. (12) gives
sphere relationships will require considerable time to the incorrect sign for the dependence of compressibility
complete, this material is presented now with a few on temperature. A series of further computations for a
representative results. variety of liquids will be required to determine the re-
The approach of using the intermolecular potentials liability of Eq. (12) when used with modifying po-
of real fluids to improve relationships for rigid-sphere tentials.
liquids can be extended to all those physical and thermo- The procedures suggested in this paper for modifying
dynamic properties of liquids which can be computed rigid-sphere relationships by using realistic inter-
from an equation of state for liquids. Reiss, Frisch, and molecular interaction potentials can also be applied to
Lebowitzl.. have obtained the contact value of a radial the virial equation of state for rigid spheres6 .1!:
distribution function for rigid-sphere liquids, and have p 1 +bo +0.625bo2 0.287bo3 0. 115bo4
shown how this function can be used to prepare a cor- RT=V V2 ---va-+~+---v;-+"" (13)
responding equation of state, which has been presented
in the following form by StillingerlO : where
bo/V = 27rNa3/3V =4y. (14)
(11)
From Eq. (13), the following expression for the iso-
The isothermal compressibility {3 is one of the properties thermal compressibility can be obtained after differen-
which can be derived from an equation of!state, and tiation with respect to Vat constant T:
can be obtained from Eq. (11) as the following expres-
sionlo: V /{3RT= 1+2bo/V+ 1.875 (bo/V) 2
{3= [V(1-y)4J/[RT(1 +2y)2J. (12) +1.148(bo/V)3+0.575(b o/V)4+.... (15)
Compressibilities for realistic potentials were calcu- The compressibility of liquid methanol has been com-
n B. J. Alder and T. E. Wainright, J. Chern. Phys. 33, 1439
10 F. H. Stillinger, Jr., J. Chern. Phys. 35, 1581 (1961). (1960).

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 1808 S. W. MAYER

puted by combining Eq. (15) with the Lennard-Jones
6-12 potential as in Eq. (8) at the following temper-
atures: 283.1 0 , 288.1 0 , 303.1 0 , and 323.1°K. The com-
puted compressibilities are: 11.4, 11.8, 12.9, and 14.6X
10-11 cm2/dyn, respectively, compared to the measured
compressibilities of 11.4, 11.8, 13.0, and 14.8X 10-11
cm2/dyn. The agreement between computed and meas-
ured values is seen to be excellent, although the meth-
anol molecule is polar and nonspherical. Accordingly,
this approach, although empirical, appears to offer
promising possibilities for the treatment of the liquid
state. It could lead, furthermore, to the determination
of intermolecular potentials from liquid state data.
The use of the rigid-sphere Eq. (15) without modifying
it by the Lennard-Jones function provided calculated
compressibilities of 12.5, 12.3, 11.9, and 11.SX 10-11
cm2/dyn, respectively; thus, the unmodified rigid-
sphere virial equation of state gave a dependence of
compressibility on temperature which had the reverse
sign from that of the measured value.
ACKNOWLEDGMENT
The author wishes to acknowledge with gratitude
Dr. Howard Reiss' valuable discussions of liquid theory
during the research involved in preparing the papers
which comprise references 2 and 3.

THE JOURNAL OF CHEMICAL PHYSICS VOLUME 38, NUMBER 8 15 APRIL 1963

Gaseous Diffusion in Porous Media. III. Thermal Transpiration

E. A. MASON
Instuutefor Molecular Physics, University of Maryland, College Park, Maryland
AND
R. B. EVANS, III, AND G. M. WATSON
Oak Ridge National Laboratory,· Oak Ridge, Tennessee
(Received 14 December 1962)

A previously proposed model for the diffusion of gases in porous media at uniform and nonuniform
pressures has been extended to allow for temperature gradients. The porous medium is visualized as a col-
lection of "dust" particles constrained to remain stationary in space. As before, by formally treating the
"dust" particles as giant molecules, it is possible to cover the entire range of intermediate mechanisms
from the Knudsen to the normal region by varying the mole fraction of the real gas. For binary systems
(a single gas and "dust"), the phenomenon of thermal transpiration is accounted for by the model in a
consistent way for all aspects which are diffusive in character but, as before, needs modification at high
pressures by the addition of an expression to account for the viscous backflow. With this modification, an
equation is obtained which describes thermal transpiration over the entire pressure range. This equation
discloses two new relationships not previously noticed: one between the maximum in the thermal trans-
piration curve and the Knudsen minimum in the permeability curve, and one between the height of the
thermal transpiration maximum and the translational heat conductivity of the gas.
It was found that it was possible to extend the model to include capillaries as well as porous media. This
extension disclosed that the relationships applicable to porous media would also describe the analogous
behavior that occurs in capillaries with definite geometry. The capillary results reproduce previous semi-
empirical and empirical equations of Weber and Liang for thermal transpiration, and the permeability
equation of Knudsen. The present equations, however, have fewer adjustable parameters than do the
previous equations. A simple connection, not previously mentioned, between Weber's and Liang's equations
was also noticed: Liang's equation is really a special form of Weber's equation written in a differential-
approximation form.
A remarkable feature of the results, as applied to capillary systems, is that one can calculate rotational
relaxation times in gases from the height of the thermal transpiration maxima, which suggests much simpler
experimental techniques than those previously employed for the measurement of this phenomenon.

I. INTRODUCTION some of the consequences of the model. In I, the pres-

N two previous papers (hereafter denoted I and
I II) ,1,2 we have proposed a model for describing the
diffusion of gases in porous media and have explored
.. Operated by Union Carbide Corporation for the U. S. Atomic
Energy Commission.
1 R. B. Evans III, G. M. Watson, and E. A. Mason, J. Chem.
Phys. 35,2076 (1961). .
t R. B. Evans III, G. M. Watson, and E. A. Mason, J. Chem.
Phys.36, 1894 (1962).
sure and temperature were uniform and concentration
gradients alone were considered. In II, the effects of
pressure gradients were investigated. The present
paper considers the obvious next step, the effects of
temperature gradients. For the simplest case of a single
gas in a porous medium, the physical phenomenon
which occurs is thermal transpiration (also sometimes
called thermomolecular pressure difference), in which a

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