International Journal of Thermophysics, Vol. 12, No.

3, 1991

Thermodynamic Properties of 1,1,1,2-Tetrafluoroethane (R 134a) in the Critical Region

S. Tang, 1 G. X. Jin, 1 and J. V. Sengers 1'2
Received August 28, 1990
A theoretically based simplified crossover model, which is capable of representing the thermodynamic properties of fluids in a large range of temperatures and densities around the critical point, is presented. The model is used to predict the thermodynamic properties of R134a in the critical region from a limited amount of available experimental information. Values for various thermodynamic properties of R134a at densities from 2 to 8 mol-L -I and at temperatures from 365 to 450 K are presented. critical phenomena; equation of state; R134a; refrigerants; sound velocity; specific heat.
KEY WORDS:

1. I N T R O D U C T I O N

As a stratospherically safe new refrigerant, 1,1,1,2-tetrafluoroethane (R134a) is considered to be a leading candidate to replace dichlorodifluoromethane (R12) as a working fluid in air-conditioning and refrigeration technology [-1-4]. As a consequence it has become very important to obtain reliable information concerning the thermodynamic properties of R134a [53, and several research groups have recently reported experimental thermodynamic-property data for R134a [6-16]. The critical temperature of R134a is about 100~ Most of the available experimental data pertain to the vapor and liquid phase of R134a. With the exception of some pressure [6, 7] and density [8] data, little information is available for the
~Institute for Physical Science and Technology, University of Maryland, College Park, Maryland 20742, U.S.A. ; Thermophysics Division, National Institute of Standards and Technology, Gaithersburg, Maryland 20899, U.S.A. 515
0195-928X/91/0500-0515506.50/0 9 1991 Plenum Publishing Corporation

516

Tang, Jin, and Sengers

thermodynamic properties of R134a in the critical region. It is known that thermodynamic properties like the compressibility and the specific heat become large in a substantial range of temperatures and densities around the critical point [17]. In this paper we refer to the range where critical enhancements in the compressibility and specific heat are observed as the global critical region. An interesting question is whether the thermodynamic properties of a fluid in the global critical region can be predicted from a limited amount of experimental information. Until recently, this question would have been answered negatively. Asymptotically close to the critical point the thermodynamic properties exhibit singular scaling-law behavior with known universal critical exponents and critical scaling functions [18, 19]. However, the range in temperatures and densities where the asymptotic singular behavior applies is quite small [20]. As a consequence one needs accurate experimental data very close to the critical point to determine the values of the system-dependent coefficients in the asymptotic scaling laws. Furthermore, even if this information is available, a knowledge of the asymptotic scaling laws is insufficient to represent the thermodynamic properties in the region relevant to technological applications, that is, in the global critical region. On the other hand, classical equations, like those used for R134a, to represent the thermodynamic properties far away from the critical point [6, 7, 9, 21], cannot reliably be extrapolated into the critical region. To address this problem one needs a theoretical description of the global behavior of the thermodynamic properties in the critical region that includes the nonasymptotic critical behavior and encompasses the crossover from singular thermodynamic behavior close to the critical point to regular thermodynamic behavior far away from the critical point [ 19]. The asymptotic scaled thermodynamic behavior can be derived on the basis of the Landau-Ginzburg-Wilson theory of critical phenomena [18]. This theory elucidates how the effects of critical fluctuations on the thermodynamic properties can be accounted for by a renormalization procedure. Several investigators have made attempts to extend the Landau-GinzburgWilson theory to a theory for the global critical behavior of the thermodynamic properties [22-32]. Very recently our group has been able to use this approach so as to obtain an actual theoretically based equation of state that is capable of representing the thermodynamic properties of fluids in the global critical region [33]. It is the purpose of the present paper to demonstrate how this new theoretical equation of state can be used to determine the thermodynamic properties of an important technical fluid like R134a from a limited amount of available experimental data.

Thermodynamic Properties of 1,1,1,2-Tetrafluoroethane (R134a) 2. S I M P L I F I E D C R O S S O V E R M O D E L F O R THE CRITICAL R E G I O N

517

Let T be the temperature, P the pressure, p the density, # the chemical potential, and a the specific Helmholtz free energy, i.e., the Helmholtz free energy per unit mass. We use the critical temperature To, the critical pressure Pc, and the critical density po to define dimensionless properties
as

~-

~'

P=P--

Pc'

P=

pcTo.~
Pc

T'

"~ . . . .

Tc pa

Pc T

(1)

In addition, we introduce

3~= 2'+1,

3p=p-1,

3p=p-m(~)

(2)

where rio(T) is an analytic background function such that Aft = 0 at the critical point. ,4 is a reduced Helmholtz flee-energy density, i.e., a reduced Helmholtz free energy per unit volume [34]. To characterize the dependence of this Helmholtz flee-energy density as a function of temperature and density in the critical region, it is decomposed as 7~ = ~.~ + pPo( i') +

~o( ~)

(3)

where Ao(T) is another analytic background function such that -~o = - 1 at the critical temperature. The term AA in Eq. (3) contains the effect of critical fluctuations and it is this term which becomes singular at the critical point. In the classical mean-field theory A~ can be represented by an analytic Landau expansion of the form [33]

AAmf= ~ tM2 + ~. uAM + ~. aosM 5

+ ~ ao6 M6 + ~ a14 t m 4 + ~
1 1 1

a22 t2m 2

(4)

where u, A, a05, a06 , a14 , and a22 are system-dependent coefficients and where the temperature-like variable t and the order-parameter M are related to A T and At~ by the transformation

t = c t 3 7 ",

M = e p ( A # - - d l AT")

(5)

and where ct, Cp, and dl are additional system-dependent coefficients. A term proportional to tM 3 does not need to be included in Eq. (4) since it

518

Tang, Jin, and Sengers

can be eliminated by a transformation of variables [-35]. In principle, the Landau expansion contains an arbitrary number of terms, but for our purpose we terminate the expansion after six terms. As shown by Chen et al. 1-33] in a previous publication, the renormalized A.4, incorporating the effects of critical fluctuations, can be obtained from Eq. (4) by the following transformation: (i) (ii) (iii) replace the variable t by t~--q/

1/2

replace the variable M in the even terms by and replace the variable in the odd M 5 term by M~l/2~t/'l/sql j/5, and add a nonscaling fluctuation-induced contribution of the form
1 2

M-@l/2~[ 1/4

The new functions in this transformation are defined as y = y(2 V-1)/~O,

= y(~,~ 1/2)/o~,
~ = y1/o~,

~ = y-~/,o,

= ~uA ( Y

(6)
~/~o~_ 1 )

where v,r/, and c~= 2 - 3 v are the usual critical exponents [19, 36], co and coa are the symmetric and a s y m m e t r i c correction-to-scaling exponents [19, 37], and ~ is defined as
= u/u* (7)

in terms of the fixed-point coupling constant u* [27, 33, 38]. The critical exponents v, q, ~, co, and coa and the coupling constant u* are universal. For fluids they have the values corresponding to three-dimensional systems with short-range forces and a scalar order parameter, often referred to as Ising-like systems [19]. The values of these universal critical-region constants are given in Table I. The crossover function Y in Eq. (6) is to be determined from [33]

1+(~-1)Y=~ l + - j
T a b l e I.

A2)1/2y1/co

(8)

Universal Critical-Region Constants

v = 0.630 r / = 0.0333 ~=2-3v=0.110 ~o = 0 . 5 1 / v = 0 . 8 0 9 5 2 ~o. = 2.1 u* = 0.472

Thermodynamic Properties of l,l,l,2-Tetrafluoroethane (R134a)

519

with

1(, = t J + 89 2

(9)

After application of the above transformation to the Landau expansion given by Eq. (4) the renormalized AA is obtained as [-33, 39]
_ 1 1 1 1 AA = ~ tmZJ-~ + ~ u 9 ~AM 4 ~ 2 ql + ~ aosmS~5/2~ql + ~.. ao6M6~3~ll3/2

+ ~ a14 I M 4 y ~

2~

~ 1 a22/2M23--e~@~t

1/2 _ 1

2 t2Lg'f

(10)

The variable ~c, defined by Eq. (9), serves as a measure of the distance from the critical point. As ~c~0, Y ~ 0 and one recovers from Eq. (10) the scaled asymptotic critical behavior. As x--. o% Y--. 1 and Eq. (10) reduces to the classical Landau expansion given by Eq. (4). To specify the total Helmholtz free-energy density A, defined by Eq. (3), we represent the analytic background functions Ao(T) and /~o(7") by truncated Taylor expansions [32, 33]
4

Ao(7") = - 1 + ~ .~j(A]') j
j=l 3

(11) (12)

/~o(T)= ~. fij(AT) i
j=0

where Aj and/~j are system-dependent coefficients. Unlike the three-dimensional Ising model, a fluid near the vapor-liquid critical point is asymmetric in the order parameter M. This asymmetry is reflected in the presence of a term proportional to M s in the Landau expansion, Eq. (4), and by the presence of an additional term d~ AT in the relation (5) between M and AZ'. The theory predicts that the asymmetry also induces an additional mixing transformation of the form [32, 33, 35]

t = c ' A T + c \ (c3 M J / c 3 A.7t~

M=cp(Afi_dlA~)+ c(C3at' ~/M \ A

(13)

where the coefficient c is a measure of the magnitude of the mixing transformation. In practice, however, we find that the effect of mixing is quite small for simple fluids, except for a strongly asymmetric fluid like steam [33]. For R134a an equally good representation of the available experimental information is obtained with c = 0. An added advantage is that setting c = 0 greatly simplifies the fundamental equation for A. In this

520

Tang, Jin, and Sengers

paper we therefore use the simplified crossover model given by Eq. (10) with c = 0. Equation (10) with Eqs. (11) and (12) completely specifies our simplified crossover model. The corresponding equations for the various derived thermodynamic properties are obtained from those presented in Ref. 33 with c = 0. In the previous work of our research group the thermodynamic properties of fluids in the vicinity of the critical point were represented by a so-called revised and extended parametric equation of state [40-42]. As documented elsewhere [39], the range of validity of the crossover model used here is much larger than that of the revised and extended parametric equation of state and yields an accurate representation of the thermodynamic properties in essentially the entire global critical region [33]. An added advantage, explored in the present paper, is that the systemdependent coefficients in the new equation of state can be determined from experimental information, even if little of it is inside the range of asymptotic critical scaling behavior.

3. A P P L I C A T I O N T O R134a

In order to apply our crossover model we first need the critical parameters Tc, Pc, and Pc- Values for the critical parameters of R134a as reported by a number of investigators are listed in Table II. For our purpose it is important that the values of the critical parameters adopted be consistent with other experimental thermodynamic-property data in the near-vicinity of the critical poinL The only available information of this nature is the saturated vapor and liquid densities reported by K a b a t a et al. [8]. We therefore selected T c ~ 374.30 K and Pc = 5.050 m o l - L - ' , which we found to be consistent with the coexisting density data of K a b a t a et al., even though K a b a t a et al. quoted a lower value for Pc; the critical pressure

Table II. Critical Parameters Reported for R134a

Reference Basu and Wilson [7] Kabata et al. [8] Kubota et al. [10] McLinden et al. [ 11] Morrison and Ward [15] This work

T~ (K) 374.25 _+0.15 374.30 _+0.01 374.25 374.205 _+0.01 374.205 374.30

p~ (mol. L-l) 5.020 + 0.05 4.979 + 0.03 5.051 _+0.01 5.050 5.050

Po (MPa) 4.067 _+0.003 4.065 4.056 + 0.01 4.068 4.065

Thermodynamic Properties of 1,1,1,2-Tetrafluoroethane (R134a)

521

Pc = 4.065 M P a was subsequently selected as providing the best fit to the available P - p - T data as discussed below. In addition to the critical parameters the crossover model contains the following system-dependent constants: the crossover constants ~/and A, the coefficients ct, c o, and dl in the expressions for the scaling fields, the classical coefficients air the coefficients ~j in the background contribution to the equation of state, and the coefficients/~j in the background contribution to the caloric properties. With the exception of the caloric background coefficients/~j, they can be determined from a fit to experimental P - p - T data [33]. Since for R134a most of the available P - p T data are not asymptotically close to the critical point, we applied our crossover model in as large a range of temperatures and densities as possible, where an acceptable representation could be obtained. This range is indicated by the shaded area in Fig. 1. The most accurate P p - T data for R134a are those reported by Weber [9], but they cover the gas phase up to a density of 2 . 3 3 m o l - L -1 only, which is still well below the critical density of 5.05 m o l . L 1. We therefore determined the system-dependent parameters in the equation of state from a fit to the more comprehensive set of pressure data from Piao et al. [12], supplemented with pressure data from Weber [9] to the extent they are inside the range shown in Fig. 1. The values obtained for the system-dependent coefficients are presented in Table III. With the error estimates assigned by the experimenters [9, 12], the combined set of pressure data (94 data from Piao et al. and 22 data
, ,ll i ~ l l , , , i l l ii~ , , , ~ l J l i F i , I I I I I I F I ,, ,~ iJl

9 :Critical

Point

450

[-,
~9

400

350

.
2

.
4

.
6 Density,

.
8 mol'L -I

""
I0

Fig. 1. Range of temperatures and densities of our crossover model for R134a as indicated by the shaded area. The solid curve represents the two-phase boundary.

522

Tang, Jin, and Sengers

Table III.

System-Dependent Constants in Simplified Crossover Model for R134a ~ Critical parameters Pc = 4.065 MPa,

Tc = 374.30 K,

Pc = 5.050 mol. L-1

Crossover parameters /~ = 0.44970, A = 2.3165 Scaling-field parameters ct = 2.7165, cp = 2.2741,

d 1 = -0.21192

Classical parameters %5 = -1.5021, a06 = 2.1487,

al, = 0.33807,

a22 =0.17213

P-p-T background
A1=-6.6526,

parameters A2=3.5463,

A3=-3.9632,

.44=25.431

Caloric background parameters /20=2.5673, ~1=12.250, f i 2 = - 2 8 . 9 3 9 , ~ 1 m o l . L - 1 = 102.03 k g . m 3.

/73=-25.272

from Weber) are reproduced with a reduced chi-square of 5.5. This value of ehi-square is larger than unity, but some relevant comments can be made. First, there are differences in the pressure data from Piao et al. and from Weber up to about twice the estimated error, indicating that the actual errors may be slightly larger (Fig. 2). Second, a comparison can also be made with pressure data reported by Basu and Wilson [7] which were not used in the fit. With a e = 0 . 1 % , a t = 0 . 0 3 K, and % = 0 . 0 8 % as claimed by Basu and Wilson [7], their 29 data points inside the range considered are reproduced with a reduced chi-square of 3.7, comparable to that obtained previously for carbon dioxide in a range of temperatures and densities somewhat smaller than that adopted here [33]. The actual deviations of the experimental pressure data are shown in Figs. 2 and 3. A comparison of the vapor pressures as calculated from our crossover model with experimental vapor-pressure data reported by Basu and Wilson [7], Weber [9], Kubota et al. [10], Piao et al. [12], and Morrison and Ward [ 15 ] is presented in Fig. 4. As indicated in Fig. 1, the range of our crossover model corresponds to densities from 1.9 to 8.9 m o l . L 1 and temperatures from 364.7 to 450 K. Below 364.7 K the crossover model can still be used in a small range but not at densities very close to the vapor phase boundary. We believe that this limitation is due to the approximate nature of Eq. (9) adopted for the variable K2. Attempts to extend our crossover model to lower temperatures near the phase boundary will be made in the future.

Thermodynamic Properties of 1,1,1,2-Tetrafluoroethane (R134a)

523

0.5

~.,!

9 o O
9

9
~ ~.

|
o8
9
$

|
6
0
9

-0.

360

380

400

420

440

Temperature, K Fig. 2. Percentage deviations of the experimental pressures obtained by Weber (A, p = 1.93 mol. L i and p = 2.33 mol. L 1) and by Piao etal. (O, p = 1 . 9 9 3.72mol. L 1; 9 p = 4 . 5 0 M . 9 9 m o l . L 1; *, p = 5.77-8.87 mol. L 1) from the values calculated with our crossover model.

'l

....

i ....

I ....

' ....

I ....

~ ....

I ....

f ....

I ....

+0.5
i m [] [] []

[] [] roll * , ,
i

[] , 9 [] 9 rn * ~

[]

[] [] [] , *

-0.5
.... , .... I .... , .... ] .... E .... I . . . . ~ .... I ....

360

380

400 420 Temperature, K

440

Fig. 3. Percentage deviations of the experimental pressures obtained

by Basu and Wilson (V1, p = 2 . 5 6 m o l . L 1; ,, p = 3 . 5 m o l . L - l ; ! P = 5.1 tool. L - l ) from the values calculated with our crossover model.

524
..... ~ .... I .... L .... I .... ' .... [ .... E .... I ....

Tang, Jin, and Sengers

I ' ' ' ' l ' ' ' ' t

4.0

3.8

~3.6

3.4
, , I , , , , I , , , , I , , , , I , , , , I , , , , I , , , r ~ , , , l l l l l l l , , , , I , , , l l

a) 366 368 370 372 374

364

Temperature, K

~. +0.61

0'01-

~-o.6/
364 ~ v

,
366

1.
368

I 370

I 372

I (b)
374

Temperature, K

Fig. 4. (a) The vapor pressures of R134a as a function of temperature. The solid curves represent the vapor pressure as calculated from our crossover model. The data points are those reported by Basu and Wilson ([]), Weber ( A ) , Kubota etal. (,), Piao etal. ( 9 and Morrison and Ward (O). (b) Percentage deviations of the experimental vapor pressures from the calculated vapor pressures.

In order to specify the Helmholtz free-energy density completely, specifically to calculate caloric properties, we need also values for the coefficients /~j in Eq. (12). The coefficients /10 and /11 are related to the zero points of entropy and energy and are, therefore, arbitrary. To determine the coefficients/tj for j >/2, we need some information about caloric properties as a function of temperature. The only available information of this nature is the sound-velocity data obtained by Guedes and Zollweg [43]. However, there is only one isotherm inside the range shown in Fig. 1 with some additional data in the liquid at 360 K. Previous experience indicates that to obtain a high accuracy, we need to retain terms in Eq. (12) up to at least j = 4 [33]. However, the sound-velocity data of Guedes and Zollweg do not cover the critical region sufficiently to determine three coefficients/12, #3, and #4. Hence, we terminate the expansion (12) for rio(]')

Thermodynamic Properties of 1,1,1,2-Tetrafluoroethane (R134a)

525

at j = 3, i.e., we approximate the background contribution to the specific heat by a linear function of reduced temperature. The values obtained for #2 and #3 are included in Table III. In Fig. 5 we show the sound velocity as a function of pressures at a number of selected temperatures. The solid curves represent the values of the sound velocity as calculated from our crossover model. It can be seen that the agreement with the sound velocity data of Guedes and Zollweg is excellent, even at the low temperature of 360 K. The speed of sound as a function of pressure or density is known to exhibit a minimum inside the critical region. Guedes and Zollweg did not approach the vicinity of the critical point where these minima can be observed. Our crossover model gives definite predictions of the pressures and temperatures where these minima occur. Saitoh et al. [13] recently reported experimental data for the isobaric specific heat Cp of R134a. The data are all in the liquid phase, but one point at T = 356 K happens to lie just a little bit outside the range shown in Fig. 1. In Fig. 6 we show c v of the liquid at 356 K as a function of pressure. As can be seen from this figure, our crossover model is in excellent agreement with this experimental value for %. Having verified that our crossover model yields a satisfactory representation of the available experimental information that is not really very close to the critical point, what guarantee do we have that the crossover model will also yield reliable thermodynamic-property values in the

,7 300 ~

200

>
100

p~a?q.21 NK,~,
4

,,, 6 8 Pressure, MPa 10 12

Fig. 5. The velocity of sound of R134a at selected temperatures as a function of pressure. The solid curves represent the values calculated from our crossover model. The circles indicate experimental data points obtained by Guedes and Zollweg [43].

526 300
Illl~llLIIJl[~llllJ~lll~lIJ Illllrlllllll~lll

Tang, Jin, and Sengers

IlJllllllll ~

"7

250 2OO
c~

150

100

,I,I,

I,I,Irr~l,l,l,I,E,l,l,l,l~l,l,l,l,l,lEI,E,],l,l,l,I

2.5

3.5 Pressure, MPa

4.5

Fig. 6. The isobaric specific heat cp of R134a in the liquid phase at T= 356 K as a function of pressure. The solid curve represents the values calculated from our crossover model. The circle indicates an experimental value reported by Saitoh et al. [13].

near-critical region where properties like the compressibility and specific heat become very large? As mentioned earlier, Kabata etal. [8J have reported experimental saturated vapor and liquid densities including at temperatures very close to the critical temperature. A comparison of the coexistence curve calculated from our crossover model with experimental data reported by Kabata et al. [8] as well as with some data points reported by Basu and Wilson [,7], Piao et al. [,12], Morrison and Ward [15], Weber [,9], and Maezawa et al. [,14] is presented in Fig. 7. Our crossover model is in very good agreement with the saturated vapor and liquid densities obtained by Kabata et al., although these data were not used in determining the coefficients in the model (except for fixing the location of the critical point as discussed in the beginning of this section). Another check can be obtained by comparing the asymptotic behavior of our crossover model close to the critical point with the asymptotic power-law behavior of the surface tension. The principle of two-scale-factor universality specifies a universal relationship between the asymptotic behavior of the surface tension o- and that of the correlation length 4, which in turn can be related to the asymptotic behavior of the specific heat. We use here this relationship in the form presented by Chaar et al. [--44] and by Moldover and Rainwater [45], who introduced quantities Y+ defined as Y-+ = a[-~(A ~.)2 pcCv +/kB] -2/3/(kB To) (14)

Thermodynamic Properties of 1,1,1,2-Tetrafluoroethane (R134a)

375~- ' ' ~ ~ . . . . I .... ' .... U. . . . i .... h.... _

527

370

6 Density, mol. L-1

Fig. 7.

The curve of coexisting vapor and liquid densities for R134a.

The solid curve represents the coexistence curve as calculated from our crossover model. The data points indicate experimental values reported by Kabata et al. ( 9 Basu and Wilson (D), Piao et al. (9 Morrison and Ward (9 Weber (A), and Maezawa et al. (+).

where c + a n d c~ are the asymptotic singular parts of the isochoric specific heat above a n d below the critical temperature, respectively, a n d where k B is B o l t z m a n n ' s constant. The quantities Y+ a n d Y are universal. The available i n f o r m a t i o n has been reviewed by C h a a r etal. [ 4 4 ] a n d M o l d o v e r a n d R a i n w a t e r [ 4 5 ] , from which they conclude Y+ =5.73-t-0.16, Y =3.741_+0.086

(is)

The surface t e n s i o n near the critical p o i n t goes asymptotically to zero as [46]

G=~o IATI 2v
while the specific heat per unit volume pr

(16)

+ diverges as [ 1 9 ]
(17)

pcCv+ = T ~ I P ~ C # JzlT'l-~
so that (14) can be rewritten in the form [ 4 4 ]

y+_ = Cro(ocpc~ f f )-2/3 (kn T c ) - 1/3

(18)

The surface t e n s i o n of R134a has been m e a s u r e d by Chae et al. [ 4 7 ] ,

528

Tang, Jin, and Sengers

with the result a0 = 0.0608 N . m our crossover model as

V

1. The amplitude C~ is obtained from (19)

C~- = ~ (2 - c~)(1 - e) c 2 ~(~A) 2~-1 while Co is related to C~ through the universal amplitude ratio [33] C + / C o = 0.502

(20)

With the values of ct, ~, and A found for R134a, we obtain C~- = 30.9 and Co = 61.6. Substitution of these values into Eq. (18) yields Y+=6.11, Y =3.86 (21)

to be compared with the universal values quoted in Eq. (15). While we do not reproduce the universal values (15) for Y+ and Y- exactly, we do obtain a reasonable approximation for Y . One should also note a possible uncertainty about the accuracy of the experimental surface-tension amplitude o-0, since it was obtained by fitting Eq. (16) to the surfacetension data over a very large temperature range [47]. The major difference between Eq. (15) and Eq. (21) is a consequence of the fact that our crossover model implies a specific-heat amplitude ratio of 0.50 as given by Eq. (20), while there is evidence from the three-dimensional Ising model that this ratio is 0.52 [36]. It may also be interesting to note that the critical fluctuations not only lead to singular asymptotic critical behavior but also lead to a suppression of the critical temperature Tc from its classical value T'o in the absence of fluctuations. For instance, by fitting the thermodynamic-property data of R134a to a simple classical Carnahan-Starling-DeSantis equation, Morrison et al. find T'o= 386.7 K [21, 48, 49]. The difference T ' c - T o - ~ 12~ is thus a measure of the suppression of the critical temperature as a result of the long-range critical fluctuations. 4. RESULTS Having verified the validity of our crossover model for the Helmholtz free-energy density of R134a to the extent that experimental data are available, we can compute all thermodynamic properties in the global critical region of R134a indicated in Fig. 1. However, before doing so we want to assign values to the coefficients/~o and/~1 in Eq. (12) which are related to the zero points of entropy and energy. This is normally done by selecting a reference point at the boundary of the range of validity of the criticalregion equation at a density and temperature sufficiently far away from the

Thermodynamic Properties of 1,1,1,2-Tetrafluoroethane (R134a)

5 0 0 0 . . . . . , . . . . i . . . . ~ . . . . I . . . . ' . . . . i ~ ' '

529
=.

T=376.3

4000
'7 O

3000

2000

1000

6 D e n s i t y , m o l . L -1

Fig. 8. The isobaric specific heat cp, calculated from our crossover model for R134a, at selected temperatures as a function of density

critical point; at this reference point the calculated entropy and enthalpy are then identified with the values calculated from a comprehensive equation which is preferably valid all the way down to the ideal-gas limit [40, 50]. Here we have selected as the reference point the point with T = 373.15 K (100~ and p = 1.9 m o l . L ', which is at the low-density side of the range of our crossover model. However, the comprehensive
150
~ , , , , , , ,, [ 1 , , , , i , ,, I '' ' , i E , ,, i ~ i , ,

T=376.3 K

"7

140

"7.2

~;
>

13o

120

110 2

i ,

i,

6 D e n s i t y , tool. L -1

Fig. 9. The isochoric specific heat Cv, calculated from our crossover model for R134a, a'~ selected temperatures as a function of density_

840/12/3-7

530

Tang, Jin, and Sengers

classical equations currently available for R134a [6, 7, 9, 21] are not very accurate. Hence, we prefer to calculate the specific-energy difference u - u r and the specific entropy difference s - s t , where u r and sr are the specific energy and entropy at the reference point. This goal is obtained by selecting/~0 and/~1 so that u r = s ~ = 0 ; these values of/~o and pl are included in Table III. In Table IV we present calculated values of the pressure P, the internal energy u, the entropy s, the enthalpy h, the isochoric specific heat Cv, the isobaric specific heat cp, and the velocity of sound as a function of temperature and density. The behavior of Cp and Cv of R134a in the critical region is illustrated by isotherms shown in Figs. 8 and 9. Table V lists the saturation properties as a function of temperature, specifically the vapor pressure, the saturated vapor and liquid densities, and the latent heat. From the information presented in Section 3, we conclude that our crossover model yields a reliable representation of the P-p-T surface of R134a in the global critical region. The equation of state also specifies the singular parts of the specific heats. The most serious approximation was introduced in approximating the background contribution to the specific heats by a linear function of temperature, since velocity-of-sound data did not permit us to establish the magnitude of higher-order terms in Eq. (12). As can be seen from Fig. 5, we have velocity-of-sound data at two temperatures only for determining the caloric background contribution. If more experimental information becomes available in the future, it is likely that some adjustments in this background contribution must be made at temperatures above 380 K, where no experimental information for any caloric property of R134a is currently available.

ACKNOWLEDGMENTS We thank J. S. Gallagher, M. O. McLinden, G. Morrison, and L. A. Weber for stimulating discussions and for helping us with collecting the relevant information for R134a. We benefited from the expertise of A. Abbaci in handling crossover equations of state. We also are indebted to J. A. Zollweg for providing velocity-of-sound data prior to publication. The research was supported by the Division of Chemical Sciences of the Office of Basic Energy Sciences of the U.S. Department of Energy under Grant DE-FG05-88ER13902.

Table IV.

Calculated T h e r m o d y n a m i c Properties

Temp. Energy 1) ( J . m o l - l ) Phase region Enthalpy (J.mol 1) Cv (J.mol 1.KL)(J-tool Cp l-K-t)

(K)

Density (mol. L 1)

Pressure (MPa)

Entropy (J.mol-l.K

Velocity of sound ( m . s 1)

"~ ~o

1 1 1 1 1 1
1

-1 1 1 1 1 1 1

107.7 109.8 111.5 113.0 113.7 114.4 115.1 115.8 116.5 117.1 118.5 119.8 121.2 122.5 125.8 129.1 132.3
135.5

1
1 I
1

138.6 141.6 144.5 147.4 150.1 152.8

155.3

1 1 1 1 1 1
i

365.0 367.0 369.0 371.0 372.0 373.0 374.0 375.0 376.0 377.0 379.0 381.0 383.0 385.0 390.0 395.0 400.0 405.0 410.0 415.0 420.0 425.0 430.0 435.0 440.0 445.0 450.0 -3.3 -2.7 -2.0 -1.4 -1.1 -0.8 -0.5 -0.1 0.2 0.5 1.1 1.7 2.3 3.0 4.5 6.0 7.5 8.9 10.3 11.7 13.0 14.3 15.6 16.8 17.9 19.1 20.1 157.8 160.1 -1146.0 -904.3 -667.8 -432.8 --315.5 -198.2 -80.8 36.7 154.3 272.0 507.8 743.9 980.4 1217.1 1809.0 2399.6 2986.8 3568.8 4143.9 4710.7 5267.8 5814.0 6348.6 6870.5 7379.2 7874.1 8354.7 476 747 1012 1276 1408 1539 1671 1803 1935 2066 2330 2595 2859 3124 3785 4444 5099 5748 6390 7023 7645 8255 8853 9437 10007 10562 11101 124 119 118 117 117 117 117 118 118 118 118 118 118 118 118 118 117 116 114 112 110 108 106 103 100 98 95 276 256 244 236 232 228 225 222 219 217 212 208 204 201 193 186 180 174 168 163 157 152 147 141 136 130 125

2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0

3.243 3.302 3.360 3.418 3.447 3.475 3.504 3.532 3.561 3.589 3.645 3.702 3.757 3.813 3.951 4.088 4.224 4.359 4.492 4.624 4.754 4.883 5.009 5.134 5.256 5.376 5.493

1 1

,.,n

Table IV.

(Continued)

Temp.
Cv (J- mol

(K)
a . K -1) ( J . m o l - l . K -1)

Density ( m o l . L 1)

Pressure (MPa)

Entropy (J.mol 1-K

Energy 1) ( J . m o l 1)

Enthalpy (J.mol-l)

Cp
Phase region

Velocity of sound ( m . s -1)

"~ ~, ~~

365.0 367.0 369.0 371.0 372.0 373.0 374.0 375.0 376.0 377.0 379.0 381.0 383.0 385.0 390.0 395.0 400.0 405.0 410.0 415.0 420.0 425.0 430.0 435.0 440.0 445.0 450.0 834 717 642 584 539 502 471 423 387 359 336 295 267 246 230 217 206 196 188 180 172 166 159 153 95.4 96.9 97.9 98.8 99.6 100.5 101.3 103.0 104.7 106.3 108.0 112.1 116.3 120.3 124.3 128.2 132.0 135.7 139.4 142.9 146.4 149.7 153.0 156,1

3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0

3.370 3.509 3.653 3.794 3.844 3.893 3.942 3.991 4.039 4.087 4.183 4.278 4.372 4.465 4.697 4.926 5.153 5.379 5.602 5.824 6.043 6.261 6.477 6.690 6.901 7.110 7.316

-12.5 -10.9 --9.2 -7.7 -7.3 -7.0 -6.6 -6.3 -6.0 -5.6 -5.0 -4.3 -3.7 -3.0 1.4 0.1 1.7 3.2 4.6 6.1 7.5 8.8 10.1 11.4 12.7 13.9 15.1

--3917.6 --3330.6 --2724.5 --2154.6 -2023.9 --1895.3 --1767.8 --1640.9 --1514.5 --1388.6 --1137.7 --888.0 --639.1 --391.0 226.4 839.7 1448.2 2051.4 2648.4 3238.3 3820A 4394.0 4958.4 5513.1 6057.7 6591.8 7114.9

--2794 -2161 --1507 -890 --743 --598 --454 --311 -168 --26 256 538 818 1097 1792 2482 3166 3844 4516 5180 5835 6481 7117 7743 8358 8962 9553

1716 1388 1028 133 129 128 127 127 126 126 125 125 124 124 123 122 121 120 119 117 116 114 112 110 108 106 104

2 2 2 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

-4862 -4322 -3766 -3186 -2882 -2562 -2248 -2085 -1927 - 1773 -1470
,..i

-1173

,..]
.m

87.8 89.4 90.8 92,0 94.3 96.5 98.6 100.7 105.8 110.7 115,6 120,4 125,1
129.7

365.0 367.0 369.0 371.0 372.0 373,0 374.0 375.0 376.0 377.0 379.0 381.0 383.0 385.0 390.0 395.0 400.0 405.0 410.0 415.0 420.0 425.0 430.0 435.0 440.0 445.0 450.0 - 5704.2 -5198.9 - 4679.0 -4136.2 -385L5 -3552.2 -3257.8 -3112,1 -2971,5 -2834,0 - 2564,9 -2301.1 -2040.8 -1783.1 1146.8 -519.0 102.0 716.5 1324.5 1925.8 2519.8 3106.3 3684.8 4255,0 48[6.5 5369.O 5912,3 -880 -589 129 839 1541 2236 2925 3606 4280 4946 5604 6253 6893 7523 8144 1668 1501 1339 1170 1082 992 149 143 139 136 133 131 129 128 126 125 124 122 121 120 118 117 115 113 111 110 108 6113 3045 2076 1589 1098 850 701 602 456 377 328 294 268 249 233 220 209 199 190 182 175 134.2 138.6 142.9 147.0 151.1 155,1 159.0

4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0

3.370 3.509 3,653 3,803 3.880 3,959 4,038 4.108 4.176 4.244 4,378 4.512 4.644 4.776 5.104 5.430 5.755 6.078 6.401 6,722 7,042 7.361 7.678 7.993 8.307 8.618 8,927

-18.1 -16.7 -15.3 -13.9 -13.1 -12.3 -11.5 -11.1 -10.7 - 10.4 -9.7 -9.0 -8.3 -7.6 6.0 -4.4 -2.8 -1.3 0.2 1.7 3.1 4.5 5.8 7.1 8.4 9.7 10.9

Table

IV.

(Continued)

Temp.

(K)

Density (mol. L - 1 )

Pressure (MPa)

Entropy ( J . m o 1 - 1 . K -1)

Energy (J .tool 1)

Enthalpy (J .tool -1)

Cp (J- t o o l - J 9K - I ) (J . m o 1 - 1 . K - 1 )

Cv

Velocity of sound ( m . s -1) Phase region

,.q

~" ="

365.0 367.0 369.0 371.0 372.0 373.0 374.0 375.0 376.0 377.0 379.0 381.0 383.0 385.0 390.0 395.0 400.0 405.0 410.0 415.0 420.0 425.0 430.0 435.0 440.0 445.0 450.0 15880 5515 3224 1733 1188 911 745 527 420 357 315 285 263 245 231 219 208 199 191 184 80.8 85.0 87.7 91.8 95.2 98.3 101.2 107.9 114.3 120.4 126.3 132.0 137.5 142.9 148.2 153.3 158.3 163.2 167.9 172.6

5.0 5,0 5.0 5.0 5.0 5,0 5.0 5.0 5.0 5.0 5,0 5.0 5.0 5,0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5,0 5,9 5.0 5.0

3.370 3.509 3.653 3.803 3.880 3,959 4,040 4.123 4.206 4.290 4.457 4.626 4.795 4.964 5.391 5.820 6.251 6,684 7.118 7.553 7.988 8,424 8,860 9.296 9,731 10,165 10.597

-215 - 20.3 -19.0 -17.7 --17.0 --16.3 --15.5 ~14.9 --14.5 --14.1 --13.4 --12.7 -12.0 --11.4 - 9.7 -8.1 -6.5 -5.0 - 3.5 -2.1 -0,6 0.8 2.1 3.5 4.8 6,0 7,3

-6776.2 -6319.9 --5851.7 --5365.4 --5111.8 --4846.7 --4557.6 --4331.4 --4181.2 --4038.4 --3763.6 --3496.7 -3234.6 -2975.8 -2338.4 --1710.5 --1089.5 --474.6 134.2 737.0 1333,5 1923.3 2506.1 3081.7 3649.7 4209.9 4762.1

-6102 - 5618 --5121 --4605 --4336 --4055 --3750 --3507 --3340 --3180 --2872 --2572 --2276 --1983 -1260 --547 161 862 1558 2248 2931 3608 4278 4941 5596 6243 6882

1356 1258 1170 1088 1052 1025 1059 157 146 140 135 132 130 129 126 125 124 122 121 120 119 117 116 114 113 111 110

2 2 2 2 2 2 2 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

,...]

,..]
,.m

-6929 -6482 -6025 --5551 -5305 -5050 --4781 -4625 -4474 -4325 -4031 -3741 --3453 -3166 -2454 -1746
-1041

82.7 88.9 93.0 96.3 101.6 106.2 110.3 114.2 122.9 130.9 138.4 145.5 152.3 158.9 165.3 171.5 177.5 183.3
189.0

365.0 367.0 369.0 371.0 372.0 373.0 374.0 375.0 376.0 377.0 379.0 381.0 383.0 385.0 390.0 395.0 400.0 405.0 410.0 415.0 420.0 425.0 430.0 435.0 440.0 445.0 450.0 -23.8 -22.6 -21.5 - 20.2 -19.6 19.0 -18.3 -17.9 -17.6 -17.2 -16.5 -15.8 15.2 14.5 -12.9 -11.4 -9.8 -8.3 -6.8 -5.4 -4.0 -2.6 -1.2 0.1 1.4 2.7 3.9 --7490.9 --7067.2 -6633.5 --6184.9 --5952.0 -5709.7 -5454.1 -5314.9 - 5180.4 - 5048.6 --4789.6 --4534.6 --4282.3 --4031.8 --3411.0 -2796.0 -2185.5 - 1579.2 --977.4 - 380.3 211.8 798.5 1379.3 1953.9 2522.1 3083.4 3637.8 -340 358 1052 1741 2425 3103 3776 4443 5102 5755 1087 1025 973 929 913 9O9 143 136 133 131 128 127 126 125 124 123 122 121 120 119 118 117 116 114 113 112 110 5766 2471 1666 1283 905 715 601 524 410 347 307 279 258 242 229 218 208 200 193 186 180 194.6 200.1

6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0

3.370 3.509 3.653 3.803 3.880 3.959 4.041 4.139 4.240 4.343 4.551 4.762 4.977 5.193 5.742 6.300 6.865 7.436 8.011 8.591 9.173 9.758 10.345 10.934 11.524 12.114 12.705

Table IV.
(Continued) u~

Temp. Energy ( J . m o l 1) Cp (J. m o l - 1 - K -1) ( J - m o l 1 . K - l )

Cv

(K)

Density (mol. L - i ) Enthalpy (J.mol-1) Phase region

Pressure (MPa)

Entropy (J-tool 1 . K - 1 )

Velocity of sound ( m - s l)

.~

N" ~-

365.0 367.0 369.0 371.0 372.0 373.0 374.0 375.0 376.0 377.0 379.0 381.0 383.0 385.0 390.0 395.0 400.0 405.0 410.0 415.0 420.0 425.0 430.0 435.0 440.0 445.0 450.0 625 556 507 470 440 416 378 350 328 311 279 257 240 228 217 209 201 195 189 184 179 174 170 115.1 118.8 122.0 125.1 127.9 130.6 135.6 140.2 144.6 148.7 158.3 167.2 175.6 183.7 191.4 198.8 206.0 213.0 219.8 226.4 232.9 239.3 245.5

7,0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0

3.370 3.509 3.653 3.803 3.913 4.046 4.181 4.317 4.455 4.593 4.873 5.157 5.444 5.733 6.467 7.214 7.970 8.736 9.508 10.288 11.072 11.862 12.656 13.453 14.253 15.056 15.861

--25.4 --24.3 --23.2 --22.1 --21.6 --21.3 --21.0 -20.7 --20.3 --20.0 -19.4 -18.8 --18.1 17.5 -16.0 -14.4 -12.9 --11.5 --10.0 -8.6 -7.2 --5.8 --4.5 -3.2 -1.9 0.6 0.6

-8001.3 --7601.0 --7191.9 --6770.2 --6611.7 --6489.9 --6368.6 -6247.6 -6126.8 -6006.3 --5765.8 -5525.8 --5286.0 -5046.5 --4448.4 -3851.5 -3256.0 -2662.5 -2071.6 --1483.8 -899.7 -319.8 255.4 825.4 1390.0 1948.7 2501.3

-7520 --7100 --6670 --6227 --6053 --5912 --5771 -5631 -5490 --5350 --5070 --4789 -4508 --4227 --3525 --2821 -2117 --1415 -713 --14 682 1375 2063 2747 3426 4100 4767

883 843 810 785 122 122 121 121 121 120 120 120 120 120 120 119 119 118 118 117 116 116 115 113 112 111 110

2 2 2 2 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

--26.6 -- 26.0 -- 25.4

ga. -- 24.8 -- 24.5

.,]

,,q
,,m

--7963 --7691 --7419 --7146 --7008 --6871 --6733 --6595 --6456 --6318 --6039 --5760 --5480 --5199 --4494 --3785 --3074 --2363
--1651

365,0 367.0 369.0 371.0 372.0 373,0 374,0 375.0 376.0 377.0 379.0 381.0 383.0 385.0 390.0 395.0 400.0 405.0 410.0 415.0 420.0 425.0 430.0 435.0 440.0 445.0 450.0 -- 24.2 --23.9 --23.6 --23.3 -- 23.0 -- 22.4 --21.7 --21.1 --20.5 - - 19.0 --17.6 16.1 --14.7 --13.2 --11.8 --10.5 --9.1 --7.8 --6.5 --5.2 --4.0 --2.7 --940 --231 475 1179 1879 2575 3267 3953 --8384.2 --8158.4 --7933.1 --7707.0 7593.6 --7480.0 --7366.2 --7252.3 --7138.1 --7023.8 --6794.6 --6564.8 --6334.5 --6103.7 -- 5524.9 --4944.5 --4363.5 --3782.9 3203.4 --2625.8 --2050.8 --1479.0 --911.0 --347.2 211.8 765.9 1314.6 732 112 113 113 113 114 114 114 114 114 115 115 115 116 116 116 116 116 116 115 115 114 113 112 111 110 109 290 275 264 259 254 250 246 243 239 233 228 224 219 211 203 197 192 188 183 179 176 172 169 166 163 160 168.0 173.5 178.6 181.0 183.4 185.7 188.0 190.2 192.4 196.7 200.8 204.8 208.8 218.2 227.3 236.0 244.5 252.7 260.7 268.5 276.1 283.6 290.9 298.1 305.2 312.2

8,0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0

3.370 3.738 4.112 4.491 4.681 4.873 5.066 5.260 5.454 5,649 6.042 6.438 6.836 7.237 8.250 9.275 10.313 11.360 12.417 13.482 14.555 15.635 16.720 17,811 18.906 20.006 21.110

538
Table V. Liquid density ( m o l . L i) 5.770 5.956 6.086 6.191 6.279 6.357 6.426 6.490 6.603 6.702 6.792 6.873 6.949 7.019 7.086 7.148 7.208 7.265 7.320 7.372 7.423 7.471 7.519 7.565 7.609 7.652 7.695 7.736 7.776 7.816 7.854 7.892 7.929 7.966 8.001 8.037 Calculated Saturation Properties Vapor density (mol.L-l) 4.331 4.147 4.018 3.915 3.829 3.753 3.685 3.624 3.516 3.421 3.337 3.261 3.191 3.126 3.066 3.009 2.956 2.906 2.858 2.813 2.769 2.728 2.688 2.649 2.612 2.577 2.542 2.509 2.477 2.446 2.416 2.387 2.360 2.333 2.308 2.284 Vapor pressure (MPa) 4.053 4.040 4.028 4.016 4.003 3.991 3.979 3.967 3.943 3.919 3.896 3.872 3.849 3.826 3.803 3.780 3~757 3.734 3.712 3.690 3.668 3.645 3.624 3.602 3.580 3.559 3.537 3.516 3.495 3.474 3.453 3.432 3.411 3.391 3.370 3.350

Tang, Jin, and Sengers

Temp. (K) 374.15 374.00 373.85 373.70 373.55 373.40 373.25 373.10 372.80 372.50 372.20 371.90 371.60 371.30 371.00 370.70 370.40 370.10 369.80 369.50 369.20 368.90 368.60 368.30 368.00 367.70 367.40 367.10 366.80 366.50 366.20 365.90 365.60 365.30 365.00 364.70

Latent heat (J-tool - i ) 1780 2252 2587 2860 3089 3295 3479 3647 3948 4215 4456 4676 4881 5073 5253 5423 5585 5739 5888 6028 6166 6295 6422 6546 6664 6777 6891 6998 7102 7203 7300 7395 7483 7570 7649 7724

REFERENCES
1. M. O. McLinden and D. A. Didion, A S H R A E J. 29(12):32 (1987). 2. J. M. Steed, Int. J. Thermophys. 10:545 (1989). 3. B. Sukornick, Int. J. Thermophys. 10:553 (1989).

Thermodynamic Properties of 1,1,1,2-Tetrafluoroethane (R134a)

4. 5. 6. 7. 8. 9. 10.

539

11.

12. 13. 14. 15. 16. 17. 18. 19. 20. 21.

22. 23. 24. 25. 26. 27. 28. 29. 30. 31. 32. 33. 34. 35. 36. 37. 38. 39.

40. 41.

L. E. Manzer, Science 249:31 (1990). M. O. McLinden and D. A. Didion, Int. 3. Thermophys. 10:563 (1989). D. P. Wilson and R. S. Basu, A S H R A E Trans. 94 (Part 2):2095 (1988). R. S. Basu and D. P. Wilson, Int. 3". Thermophys. 10:591 (1989). Y. Kabata, S. Tanikawa, M. Uetmatsu, and K. Watanabe, Int. J. Thermophys. 10:605 (1989). L. A. Weber, Int. J. Thermophys. 10:617 (1989). H. Kubota, T. Yamashita, Y. Tanaka, and T. Makita, Int. J. Thermophys. 10:629 (1989). M. O. McLinden, J. S. Gallagher, L. A. Weber, G. Morrison, D. Ward, A. R. H. Goodwin, M.R. Moldover, J.W. Schmidt, H.B. Chae, T.J. Bruno, J.F. Ely, and M. U Huber, A S H R A E Trans. 95 (Part 2):263 (1989). C. C. Piao, H. Sato, and K. Watanabe, A S H R A E Trans. 96 (Part 1):132 (1990). A. Saitoh, S. Nakagawa, H. Sato, and K. Watanabe, J. Chem. Eng. Data 35:107 (1990). Y. Maezawa, H. Sato, and K. Watanabe, J. Chem. Eng. Data 35:225 (1990). G. Morrison and D. K. Ward, Fluid Phase Equil. 62:(in press) (1991). A. R. H. Goodwin and M. R. Moldover, J. Chem. Phys. 93:2741 (1990). J. V. Sengers and J. M. H. Levelt Sengers, Chem. Eng. News 46(10):104 (1968). M. E. Fisher, in Critical Phenomena, Vol. 186, Lecture Notes in Physics, F. J. W. Hahne, ed. (Springer-Verlag, Berlin, 1982), p. 1. J. V. Sengers and J. M. H. Levelt Sengers, Annu. Rev. Phys. Chem. 37:189 (1986). J. M. H. Levelt Sengers and J. V. Sengers, in Perspectives in Statistical Physics, H.J. Ravech6, ed. (North-Holland, Amsterdam, 1981), p. 239. G. Morrison and J. S. Gallagher, in Proceedings, 1990 USNC/I1R-Purdue Refrigeration Conference and 1990 ASHRAE-Purdue CFC Conference, D. R. Tree, ed. (Purdue University, West Lafayette, IN, 1990), p. 242. J. F. Nicoll and J. K. Bhattacharjee, Phys. Rev. B 23:389 (1981). J. F. Nicoll and P. C. Albright, Phys. Rev. B 31:4576 (1985). C. Bagnuls, C. Bervillier, and Y. Garrabos, J. Phys. Lett. 45:L-127 (1984). C. Bagnuls and C. Bervillier, Phys. Rev. B 32:7209 (1985). C. Bagnuls, C. Bervillier, D. I. Meiron, and B. G. Nickel, Phys. Rev. B 35:3585 (1987). P. C. Albright, J. V. Sengers, J. F. Nicoll, and M. Ley-Koo, Int. J. Thermophys. 7:75 (1986). P. C. Albright, Z. Y. Chen, and J. V. Sengers, Phys. Rev. B 36:877 (1987). V. Dohm, J. Low Temp. Phys. 69:51 (1987). R. Schloms and V. Dohm, Europhys. Lett. 3:413 (1987). R. Schloms and V. Dohm, Nuclear Phys. B 328:639 (1989). Z. Y. Chen, P. C. Albright, and J. V. Sengers, Phys. Rev. A 41:3161 (1990). Z. Y. Chen, A. Abbaci, S. Tang, and J. V. Sengers, Phys. Rev. A 42:4470 (1990). J. V. Sengers and J. M. H. Levelt Sengers, in Progress in Liquid Physics (Wiley, New York, 1978), p. 103. J. F. Nieoll, Phys. Rev. A 24:2203 (1981). A. J. Liu and M. E. Fisher, Physica A 136:35 (1989). F. C. Zhang and R. K. P. Zia, J. Phys. 15:3301 (1982). J. C. Le Guillou and J. Zinn-Justin, J. Phys. 48:19 (1987). Z. Y. Chen, A. Abbaci, and J. V. Sengers, in Properties of Water and Steam: Proceedings of the l l t h International Conference, M. Pichal and O. ~ifner, eds. (Hemisphere, New York, 1990), p. 168. J. M. H. Levelt Sengers, B. Kamgar-Parsi, F. W. Balfour, and J. V. Sengers, 3". Phys. Chem. R e f Data 12:1 (!983). J. V. Sengers and J. M. H. Levelt Sengers, Int. J. Thermophys. 5:195 (1984).

540

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42. P. C. Albright, T. J. Edwards, Z. Y. Chen, and J. V. Sengers, J. Chem. Phys. 87:1717 (1987). 43. H. J. R. Guedes and J. A. Zollweg, Submitted for publication. 44. H. Chaar, M. R. Moldover, and J. W. Schmidt, J. Chem. Phys. 85:418 (1986). 45. M. R. Moldover and J. C. Rainwater, J. Chem. Phys. 88:7772 (1988). 46. J. S. Rowlinson and B. Widom, Molecular Theory of Capillarity (Clarendon, Oxford, 1982). 47. H. B. Chae, J. W. Schmidt, and M. R. Moldover, 3. Chem. Eng. Data 35:6 (1990). 48. G. Morrison and M. O. McLinden, Application of a Hard Sphere Equation of State to Refrigerants and Refrigerant Mixtures, NBS Technical Note 1226 (U.S. Government Printing Office, Washington, DC), 1986. 49. G. Morrison, Personal communication (1990). 50. J. M. H. Levelt Sengers, B. Kamgar-Parsi, and J. V. Sengers, J. Chem. Eng. Data 28:354 (1983).