Beruflich Dokumente
Kultur Dokumente
J. F. Kenney
Joint Institute of the Physics of the Earth, Russian Academy of Sciences ; Gas Resources
Corporation, 15333 JFK Boulevard, suite 160, Houston, T X 77032, USA.
E-mail : JFK=alum.MIT .edu
The thermodynamic stability of the hard-sphere gas has been examined, using the formalism of scaled particle
theory (SPT), and by applying explicitly the conditions of stability required by both the second and third laws
of thermodynamics. The temperature and volume limits to the validity of SPT have also been examined. It is
demonstrated that SPT predicts absolute limits to the stability of the Ñuid phase of the hard-sphere system, at
all temperatures within its range of validity. Because SPT describes Ñuids equally well as dilute gases or dense
liquids, the limits set upon the system stability by SPT must represent limits for the existence of the Ñuid phase
and transition to the solid. The reduced density at the stability limits determined by SPT is shown to agree
exactly with those of that estimated for the AlderÈWainwright, high-density gasÈsolid phase transition in a
hard-sphere system, at a speciÐc temperature, and closely over a range of more than 1000 K. The temperature
dependence of the gasÈsolid phase stability limits has been examined over the range 0.01 KÈ10 000 K. It is
further shown that SPT describes correctly the variation of the entropy of a hard-core Ñuid at low
temperatures, requiring its entropy to vanish as T ] 0 by undergoing a gasÈsolid phase transition at Ðnite
temperature and all pressures.
[
A B A BA B
1 dV
[ 0;
dp dT
[ 0;
n
t
molecular mass ; g is the ““ reduced-density ÏÏ parameter,
g \ V */V \ n(p/6)p3/V \ o(p/6)p3, in which p is the diameter
V dp dT dV
A BA B T V p of the hard-spheres, n the molar abundance.
t
dp dT t The factored partition function, eqn. (4), constitutes implicit
[0 t application of the BakerÈCampbellÈHausdor† lemma,20h24
dT dV
A B V
A B p t
dS dS o (1) Q \ trSexp([bH(p, q))T \ trSexp([b(T (p) ] X(q)))T
T \ C [ 0; T \C [C t
dT V dT p Vt \ trSexp([bT (p))TtrSexp([bX(q))T
A B
dk A BV
[ 0;
d2k
\0
p
t
t
] tr
TA1[
b2
[T , X] ] É É É
BU
dp dp2 t 2
T,n T,n p
The conditions for stability set out in eqn. (1) are concerned D trSexp([bT (p))TtrSexp([bX(q))T. (5)
p \ Nk T
1 C
]
1 2g(2 [ g) D
\ pIG ] phc. (7)
B V V (1 [ g)3
SSPT \ Nk
A 5
] ln
A V B [
B
g(4 [ 3g)
\ SIG ] Shc. (8)
The inadequacies of the local stability conditions set out in
eqn. (1) to predict the AlderÈWainwright transition may be
B 2 nN j3 (1 [ g)2
A noted by calculation of the isothermal compressibility,
If the last term in eqn. (8) is neglected, it becomes SakurÈ [V (dp/dV ) , the isometric thermal variance of the pressure,
T
Tetrode equation, to which the SPT equation for entropy (dp/dT ) , the isobaric thermal variance of the volume,
V
reduces in circumstances of dilute densities. (dV /dT ) , and the isobaric speciÐc heat, C , at the density at
p p
The two leading terms in the entropy, the ideal gas contri- which the system entropy changes sign. All these thermodyna-
bution, SIG, are always positive, and dominate that function in mic variables satisfy the local conditions of stability in the
the region of low and moderate densities. The third term in Ñuid phase at the AlderÈWainwright transition.
the entropy, the hard-core contribution, Shc, is always negative A less widely used determinant of a phase transition is the
and, most importantly, possesses a second-order singularity in isobar inÑection, (dCp/dp) \ 0, the importance of which for
T
the reduced density. Therefore, at sufficiently high densities, investigating the phase stability of Ñuids has been described
the entropy of the hard-core Ñuid must change sign and by Deiters and de Reuck26 and by Bernal,27 who pointed out
become negative. the experimental demonstration of its signiÐcance by Jones
Such behavior by the system would constitute a glaring vio- and Walker.28 When the fourth Clausius equation,
lation of the third law of thermodynamics. Therefore, the (dCp/dp) \ [T (d2V /dT 2) , is applied, the isobar inÑection
T p
density at which the entropy of the hard-core Ñuid changes can be determined from the second isobaric temperature
sign represents an absolute limit for the Ñuid, which cannot derivative of the volume. SPT gives for the second isobaric
exist at that, or higher, densities. This limit determines the temperature derivative of the volume :
AlderÈWainwright, high-density, gasÈsolid phase transition.
Scaled particle theory describes equally the dilute gas and the
dense liquid states. Therefore, the limit determined by SPT for
A B
d2V SPT
\[
V
dT 2 T2
the existence of the system so described must set the boundary p
for a solid phase. This property of the entropy of the hard- (1 [ g)g2(1 ] g ] g2 [ g3)(3 ] 9g [ 6g2 [ 4g3 ] 5g4 [ g5)
core Ñuid is shown graphically in Fig. 1 for a hard-sphere gas, ] .
(1 ] 4g ] 4g2 [ 4g3 ] g4)3
at the temperature 300 K, as a function of its reduced density,
g. The calculated values are represented graphically in Fig. 1 (9)
where are shown also the respective contributions of the ideal
gas and hard-core entropies. Also in Fig. 1 is drawn the verti- The isobar inÑection is determined by the roots of the poly-
cal line which represents the reduced density for the gasÈsolid nomial of eighth degree in the numerator of eqn. (9). Aside
phase transition as estimated by Alder and Wainwright using from its obvious roots at zero and unity, eqn. (9) admits no
the Ðxed value for the reduced-density parameter, real roots for values of the reduced-density parameter, g,
U(T )solid D 3 Nk T
C A B
2p4 T 3 D
] É É É O(exp([T D/T )) , (12)
has been pointed out in the previous section, the contribution
of the low-temperature limit of the melting entropy is approx-
2 B 5 TD imately 3 cal mol~1 K~1, and this value is of the same order
in which T D \ +wD/k represents the e†ective Debye tem- as, and very closely approximates, the entire entropy of
B melting in simple, real materials. Therefore, in order to
perature ; and wD \ kDc where kD represents the geometric,
s examine how inclusion of the entropy of melting might alter
maximal, Debye wave number and c the velocity of sound.
s the details of the AlderÈWainwright transition, as determined
Thus the limit of the entropic change in passing from the
solid to gas phase is : by SPT, the pressures for that transition have been calculated
C
lim (*Ssf)SPT \
D
*L (T )sf
ÈÈÈÕ 3 Nk
using the condition S(p, T ) ] (*S)sf \ 0. In Fig. 6, are shown
the pressures of the AlderÈWainwright transition as deter-
T sf 2 B mined by the vanishing of the system entropy as calculated
T?0 both from the Ñuid phase alone, and also with inclusion of the
B 2.98 cal mol~1 K~1. (13) contribution of the entropy of melting, as estimated from its
This interesting property has not been previously reported low-temperature limit. The data represented in Fig. 6, show
in the extensive literature dealing with SPT. The entropy of clearly that the inclusion of the entropy of melting has no
fusion at the melting point for almost all metals lies in the e†ect upon the qualitative features of the AlderÈWainwright
range 1.7È2.6 cal mol~1 K~1.29 That the entropy of melting transition and produces only very small quantitative change
for real metals should be less than that given by the SPT limit, above the temperature of approximately 100 K. Furthermore,
eqn. (13), should be expected, for the limit to which eqn. (13) the low-temperature behavior of the AlderÈWainwright tran-
refers is that for which the temperature vanishes. Real metals sition as predicted by SPT, characterized by the vanishing of
fuse at high temperatures, at which the calculated entropy the Ñuid phase at all pressures as the temperature goes to
would have subtracted from eqn. (12) contributions for both zero, remains. The magnitude of the calculated reduced-
the binding energy of the metal and also its volume change at density parameter at the density of the AlderÈWainwright
melting. The typically high melting temperature of most transition as predicted by SPT, g(S ] (*S)sf \ 0), deserves par-
metals indicates substantial binding energy, and thereby a sig- ticular attention : In Fig. 6, it may be observed that the
niÐcant contribution to the change in enthalpy from the term reduced-density parameter at the AlderÈWainwright tran-
*Usl/T . An example of a real material composed of volatile sition is essentially indistinguishable from the Ðxed value,
molecules of almost spherical shape, the nonassociating gAW \ 0.67114, estimated by Alder and Wainwright, over a
hydrocarbon tetramethylmethane (2-2-dimethylpropane), range of temperatures extending almost three orders of magni-
C H , melts at 250.2 K and possesses a latent heat tude.
5 12 Because any density at which the system entropy vanishes
*Hsl \ 778 cal mol~1, such that its entropy of transformation
*Hsl/T sl \ 3.0 cal mol~1 K~1.30 Thus, SPT predicts a limit- determines a point of absolute instability for that phase, the
ing value for the transformation entropy which is close to the densities of the AlderÈWainwright transition calculated by
measured values of real materials. SPT should be considered the solid-end points of the gasÈ
solid coexistence line for the phase transition, at each tem-
10. Discussion perature. The positions of the gas-end of the gasÈsolid
coexistence line can be determined only with an exact solution
The purpose of this short paper has been to demonstrate that of the statistical mechanics of the hard-sphere solid, which
SPT accurately predicts the high-density, gasÈsolid AlderÈ does not exist.
Wainwright transition in a hard-sphere system. The qualit- The description of the high-density AlderÈWainwright tran-
ative features of the mathematical computations described sition given above by SPT is not restricted to artiÐcial hard-
above remove all doubts on that question. Furthermore, these sphere gases ; it holds equally true in all its qualitative features
results show that SPT additionally describes interesting fea- for real Ñuids. The mathematical description of the entropy of
tures of the hard-sphere system not previously been reported : every real Ñuid system must possess a component which
the temperature dependence of the reduced-density parameter accounts for the entropy of exclusion, as determined by SPT.
at the gasÈsolid phase transition, g(T ) ; and the require-
S/0
ment which SPT appears to place upon the hard-core system,
as the system temperature approaches absolute zero, to con-
dense into the solid phase at Ðnite temperatures and pressures.
The temperature dependence of the density at which the
hard-sphere system undergoes a ÑuidÈsolid phase transition,
g(T ) , should be expected. The phase rule of Gibbs in no
S/0
way depends upon any detail of the intermolecular potential,
and holds true for a hard-sphere system as any other. A
single-component, hard-sphere Ñuid in a single phase must be
described by two independent, intensive variables, and at its
binary-phase transition, one.
Although it has been shown that the Ñuid phase of a hard-
core system, as described by SPT, is characterized by limits
determined by the stability condition imposed by the third
law of thermodynamics, the detailed quantities calculated
above cannot be considered to be strictly accurate, for such
were calculated by considering only the entropy of the gas
state. An exact calculation of the pressures of the AlderÈ
Wainwright transition must include, in addition to the
entropy of the gas phase, that of the solid phase of the hard-
core system. However, the thermodynamics of the hard-sphere
solid have not yet been worked out, and it is therefore not Fig. 6 Pressure of the AlderÈWainwright transition, determined with
possible to calculate exactly either the entropy of the hard- inclusion of the entropy of transformation, (*S)gf B 3/2k .
B
3282 Phys. Chem. Chem. Phys., 1999, 1, 3277È3285
The entropy of exclusion is obtained from the impenetrable given by the Tonks equation :41
property of real molecules, and is a consequence of the mathe-
matics of statistical geometry, and is always negative. Further- pSPT(1vdim) \
Nk T
B
1
\ Nk T
1
]
Cg D
more, the negative term which describes the entropy of L (1 [ g) B L L (1 [ g)
exclusion of a Ñuid will possess always the second-order singu- \ pIG(1vdim) ] phc(1vdim) (14)
larity determined by SPT, Shc(g) D [h(g)/(1 [ g)2, where h(g)
represents any non-singular function of g, usually a poly- where g \ Np/L , in which p represents the length of the hard
nomial. Even when the complications of a non-spherical shape rod and L the system dimension (““ volume ÏÏ). The Helmholtz
of the hard-core have been taken into account, as has been free energy of the one-dimensional hard-rod system is given
done by, for example, Boublik et al.,31 Chapman et al.,32 explicitly as :
Nezbeda et al.,33 Vimalchand et al.,34 and Zhou et al.,35 the
second-order singularity in the reduced density remains. The FSPT(1vdim) \ [ Nk T ln
L CA B
] 1 [ ln(1 [ g)
D
same fact holds also when the temperature dependence of the B Nj
hard core is introduced, as has been done by, for example, \ FIG(1vdim) ] Fhc(1vdim). (15)
Deiters et al.36,37 The entropy of every real gas system is posi-
tive at low and modest pressures at all temperatures, of The hard-core terms in the free energy, and the canonical par-
course, for if not, the gas state would always be unstable tition function, of a hard-rod system in one dimension are
against transition into the solid state and could not exist. purely entropic, as for the three-dimensional case ; and the
However, as stated above, the total entropy of every real gas internal energy, U, of the hard-rod system is exactly 1/2Nk T .
B
system possesses also, at all temperatures, a negative com- The entropy of the hard-rod system, given explicitly by
ponent, the entropy of exclusion attributable to the universal S \ (U [ F)/T , is :
property of impenetrability of its molecules as described by
SPT. The (negative) component, the entropy of exclusion, by SSPT(1vdim) \ Nk
3C] ln
L A B
] ln(1 [ g) .
D (16)
B 2 Nj
virtue of its second-order singularity, is unbounded at high-
densities. Therefore, at some sufficiently high density, the Ñuid The kinetic volume, V , of a D-dimensional system may be
phase of every real gas must become absolutely unstable. That kin
written as (V )Dvdim \ (Nj3)D@3. The condition of validity for
instability is the famous AlderÈWainwright transition. The kin
the hard-core Ñuid in any dimension, D, can be written as
AlderÈWainwright transition is not an artifact of the machine- (Nj3)D@3/LD \ V /V @ 1.
calculated simulations with which Alder and Wainwright Ðrst kin
If the one-dimensional hard-rod system were compressed to
determined the high-density gasÈsolid phase transition ; it is a the length at which the entropy, as given by eqn. (16), would
real phenomenon which occurs in all real Ñuids. vanish, its length would then have to satisfy the equation :
Because there are very few models in quantum statistical
mechanics which admit exact solutions, the constraints of the V AB
kin \ exp
3
(1 [ g) B 4.482(1 [ g). (17)
third law have not often been applied for stability analysis. V 2
S/0
Therefore, and in order to show that such analysis does not However, both eqn. (17) and the condition of validity cannot
predict a spurious instability or phase transition, in two be satisÐed simultaneously. Because the limits of the reduced-
Appendices which follow, the identical analysis as has been density parameter are 0 O g O 1, the value of the system
used for the three-dimensional hard-sphere gas is applied to, length at which the expression for the entropy, as given by
respectively, the one-dimensional hard-body, or ““ hard rod ÏÏ, eqn. (16), vanishes, L , clearly lies outside the limits of
system, and the two-dimensional, or ““ hard-disk ÏÏ, system. In S/0
validity of the equation of state, and of the hard-rod partition
those Appendices is shown that, the constraints of the third function from which it was obtained. (The mathematically
law, when applied to SPT and the one- and two-dimensional valid but physically meaningless values of, say, g \ 0.99999
hard-core systems, do not predict a spurious instability for the . . . , are not considered, for such must be interpreted simply as
Ðrst case, and do predict one-such, and its accompanying Ðrst- the system compressed to close-packing, not as a phase tran-
order, ÑuidÈsolid phase transition, in the second case, exactly sition. For all ÑuidÈsolid phase transitions, the change in
as demonstrated by molecular dynamics computer simula- density at the temperature of transformation is approximately
tions.38h40 10È15%. Therefore, when considering eqn. (17), it would be
Notwithstanding its use of the modern formalism of SPT, reasonable to restrict the reduced-density parameter such that
this prediction of the AlderÈWainwright, ÑuidÈsolid phase g O D0.9.)
transition, above, is very much in the spirit of the analysis of Therefore, the stability condition that the entropy of the
the gasÈliquid phase transition by van der Waals. The tradi- system must always be positive does not predict any phase
tional prediction of the low-temperature gasÈliquid phase transition for the one-dimensional hard-core system at any
transition obtained by the van der Waals equation of state volume within the limits of validity of its description. Applica-
does not strictly describe any liquid conÐguration. When the tion of the constraints of the third law to the one-dimensional
van der Waals equation of state is used to describe a gas, its system does not involve any prediction of instability or phase
isothermal compressibility is observed to change sign at a transition for the one-dimensional hard-rod gas, and is consis-
certain (critical) temperature ; and for all lower temperatures, tent with other stability analyses.
the gasÈliquid phase coexistence line is inferred a fortiori,
using the (appropriately named) ““ Maxwell construction ÏÏ.
Similarly, when SPT is used to describe a hard-sphere gas, its Appendix B Application of the constraints of the
entropy is observed to change sign at a certain density ; and third law to the two-dimensional, hard-disk system :
for all higher densities, the solid state is inferred a fortiori. SPT develops the exact solution also for the equation of state
of the two-dimensional hard-body system, or ““ hard-disk ÏÏ
system :
Appendix A Application of the constraints of the
Nk T 1 1 C
g(2 [ g)
third law to the one-dimensional hard-rod system
The statistical mechanical problem of a one-dimensional hard-
pSPT(2vdim) \ B
A (1 [ g)2
\ Nk T
B A
]
A(1 [ g)2
D
body gas admits an exact solution, and no phase transition.
The equation of state of a one-dimensional hard-body Ñuid is \ pIG(2vdim) ] phc(2vdim) (18)
References
1 J. F. Kenney, Fluid Phase Equilib., 1998, 148, 21.
2 B. J. Alder and T. E. Wainwright, J. Chem. Phys., 1957, 27, 1208.
Fig. 7 Ratio of kinetic to system area (volume) of a two-dimensional 3 J. G. Kirkwood, J. Chem. Phys., 1935, 3, 300.
hard-disk system at the point S \ 0, as a function of reduced density. 4 M. Born and H. S. Green, Proc. R. Soc. L ondon, 1946, 188, 10.