,

Presented at the 56th Nationa l Me et ing of the AIChE

San Francisco , California

May 16-19, 1965

APPLICATION OF THE
BENEDICT-WEBB- RUBIN EQUATION OF STATE TO ARGON

David Zudkevitch
and
Thomas G. Kaufmann

Esso Research and Engineering Co.

Florham Park, New J ersey

0
American Institute of Chemical
Engineers
GMELIN .REFERENCE NID.ffiER
- 56th National Meeting
San Francisco, California
AED-Conf- t;-o~~ - !t> May 16-19, 1965

0
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 DISCLAIMER

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..

ABSTRACT

The coefficients of the Benedict-Webb-Rubin equation of state

have been developed for argon. Employing these coefficients, the volu-.
metric behavior of argon has been predicted with an average deviation of
0.241% for 597 smoothed and experimental data points in the superheated
region. At temperatures below the critical two sets of C0 's, one for the
liquid and one for the vapor, were needed to relate the vapor pressure to
the densities of saturated argon.

Using the experimental data of Holst(l8) and Wilson(28) the re-

liability of the BWR coefficients were demonstrated by predicting the
phase behavior of the argon-nitrogen system down to -326°F, Further im-
provement of the results was obtained when another set of C0 's were de-
veloped by equating the pure component vapor and liquid fugacities along
the·vapor pr~isure·~urves;:·: ·

In calculating enthalpy deviations from the ideal state the

original BWR expression was modified to include explicitly the temperature
dependence of the coefficient C0 . Predicted values of enthalpy deviations
obtained with this expression showed good agreement with values from Din's
compilation.

c
 -~------- -- -----~-----------------

..

APPLICATION OF THE
BENEDICT-WEBB-RUBIN EQUATION OF STATE TO ARGON

The empirical equation of state of Benedict, Webb and Rubin(3) was

originally developed to correlate and predict the fugacities of light hydro-
carbon mixtures. Since the first publication, it has been ~sed extensively
to represent· the volumetric and phase relations of light hydrocarbons and
some nonhydrocarbons. Several papers(3,4,5,8,13) have been published de-
scribing success in predicting high pressure phase behavior of multicompo-
nent sys terns. /

As the BWR technique gained widespread use, more and more short-
com1ngs were reported(8,13). Most of the difficulties have been observed
at (1) predicting P-V-T relationship within the critical region and (2) pre-
dicting vapor liquid equilibrium ratios at low temperatures. As a result,
it is widely believed that the BWR equation is inadequate for systems at
low temperatures. Attempts have been made to modify the equation and the
combining rules for mixtures in order to use it for low temperature predic-
tions. The limitations of the BWR method and suggested modifications have
been summarized by Canjar(8), Ellington(l3) and Lin(20).

The application of the BWR approach to the cryogenic systems

nitrogen-methane(26) and nitrogen-carbon monoxide(24) at temperatures below
200°R established that temperatm!e is not a li'miting condition for use of
the technique. The results of the present work extend the application of
the BWR method to another cryogenic material, namely argon.

As was recently stated by Thodos(25), argon is a good substance

to test the validity of an equation of state. Its molecule is monatomic
and, therefore, its properties should resemble th'ose expected from a
11
Simple fluid 11 as defined by Pitzer(23) •. Furthermore, its relatively high
atomic weight provides a good test for any equation employing a high power
series in density. Beattie: and Bridgeman(2) showed that such an equation
can apply to argon.

The BWR equation requires the determination of eight coefficients

by a lengthy trial and error·process. Once the coefficients are established
they have to .be tested. Application of the equation also requires a compli-
cated trial and error procedure to find the phase densities. Publications
concerning the BWR equation and its application describe methods to evaluate
the coefficients(?) and its various uses(4,5,13,14,20,25,26). However, the
literature does not give a clear procedure for evaluating the effect of tem-
perature on the coefficient which is necessary for the prediction of vapor
pressure. This presentation discusses this aspect of the problem.

a
.

- 2 -

The present work involves the following steps:

Q Establish the eight coefficients for the BWR equation by regression

analysis of the P·V-T data in the superheated gas phase.

o Test th.e accuracy of pressure predictions in the superheated range.

o Evaluate the temperature effect on the coefficients of the equation

at temperatures below the critical and quantitatively account for it
by varying one of the coefficients, C0 •

o Test the validity of the above by calculating isothermal pressure ef-

fects on enthalpy.

o Test the validity of the coefficients and of the original BWR method
(4,5) to predict the vapor liquid equilibrium ratios (K values) in
the nitrogen-argon system.

Evaluation of BWR Coefficients for Argon

The equation of state of Benedict, Webb and Rubin(3) describes

the P-V-T properties of bot~ vapors and liquids and therefore is suitable
for calculaiing densities, fugacities ~nd isothermal effects on enthalpy
and entropy. In all its applications the indepe~dent variable, at ~ given
temperature, is the density.

The basic formula expresses the pressure, P, as a function of

the ~olal density, d.

2 2 3 6
P = RTd + (B RT - A
0 0
- C /T )d + (bRT - a)d + aad
0

3 2 2 2
+ (cd /T )(1 + yd ) exp(-yd ) (1)

where A , B , C , a, b, c, a, and r.·are empirical coefficients.

0 0 0
R is the gas constant.
T is the absolute temperature
d is density in moles/unit volume.

Except for the last term, equation (1) could be considered as a power series
of d. In order to utilize conventional linea~ regression analysis, a
value of y must be assumed to permit determination of the other seven coeffi-
cients: .B 0 , A0 , C0 , b, a, c, and a. For each assumed value of the 1 the
standard deviation of the dependent variable, in this case (P-RTd); can then
be determined. In selecting the term (P;RTd) as the dependent variable,
this w.ork dif~ers from Brough(7) and others who utilized (Z-l) as the depend-
ent variable.
 - 3 -

For the evaluation, 597 P-V-T points for argon in the gaseous
phase were used. They contained experimental data which had been pub-
lished by Michels et al(21,22) as well as some smoothed values from Din's
tabulation(ll). The data covered the temperature range of 290 to 1080°R
and the pressure range of 14.7 to 7500 psia.

The calculations were carried out on an IBM-7094 computer uti-

lizing a regression analysis technique described by Efroyrnson(l2). The
coefficient of the linear terms were evaluated for different values of 7's.
In each case the standard deviation was plotted ~gainst the corresponding
assumed value of 7 to establish the one having the minimum standard devi-
ation. Table 1 lists the values pertinent to the final determination. The
selection of the best value was done graphically as shown in Figure 1 and
the corresponding set of coefficients is given in Table 2. Numerically
the minimum standard deviation is 18.8 psia.

The ability of .the BWR equation of state to represent the P-V-T

behavior of argon was tested by comparing pressures calculated from sub-
mitted values of temperature and volume. The smoothed values tabulated by
Din(ll) and the experimental data of Whalley(27) were used for this com-
parison. The results for the former are shown in Tabie- 8a'l'<, and for the
latter in Table 8b,'<. Also, Figure 2 shows the results graphically. The
average percentage deviation between Din's values and the predicted pres-
sures was p.214%. The largest deviations were observed along the isotherm
closest to the critical. The. maximum error was 4.26%. The same comparison
using five isotherms of Whalley(27) resulted in a deviation of 0.45%.

It has also been noticed by others(25) that the maximum% devi-

ations in predictions by the method of BWR occur in the vicinity of the
critical point. This subj,~ct will be discussed further under enthalpy
computations.

Fugacity Computations and·

Fitting the BWR Equation td Saturated Argon

<
The original objective in developing the BWR method was to obtain
a procedure for calculating the fugacities of components in both their pure
state· and· in mixture·s. It follows therefore that the equation of state when
applied to either of the phases .at equilibrium must predict the same pressure
and the same fugacity, i.e., ·
c

·p = (2)
L Pv
0 0

and fL = fv (3)

where ·the subscripts L and V refer to liquid and vapor respectively.

* Because of its volume, Table 8 will be submitted to the American Docu-

·mentation Institute as a supplement to this paper.
 - 4 -
The fugacity of either of the phases,related to the fugacity at
unit pressure, is calculated from the following relationship:

2
RTlnf = RTlnRTd + 2(B RT - A
0 0
- C /T )d
0

+ (3/2)(bRT - a)d + (6/5) a~d 5

2

J
yd 2\/exp (-yd 2 ) (4)

The variables in Equation (4), including the density d, are the same as·
those in Equation (1).

For a pure compound, Equation (3) must be satisfied along the

vapor pressure curve. Benedict, Webb and Rubin(5) pointed out that the
coefficients of Equation (1) vary with the temperature along the vapor
pressure curve; but for practicality, they recommended changing only the
coefficient C0 with temperature.

Equation (1)· can be used to evaluate C0 at each temperature from

the vapor pressure and the density of either the saturated vapor, or the
saturat~d liquid. Data on the vapor pressure of argon were published by
Baly(l), Clark et al(9) and Michels et al(22). The properties of saturated
argon were smoothed and are tabulated by Din(ll). These data were utilized
to calculate values of C0 along the vapor pressure curve. The results are
given in Table 3 and are illustrated in Figure 3. Two values of C0 rather
than the ~xpected single value were obtained at each temperature, one for
the vapor and one for the liquid. Furthermore, when these values were used
to calculate fugacities, _the requirement of Equation (3) could not be met.
It was obvious that these C0 's could not be used to calculate phase equilibria
and another approach was necessary.

Past experiencerin utilizing equations of state to calculate P-V-T

for saturated pure compounds has shown that small changes in dsL or dsv can
cause large deviations in pressure predictions. The latter deviations result
in even larger fugacity d~,f'iations. It follows, therefore, that very minute
disagreement between measured densities and those predicted from an assumed
shape for the pressure-density relationship, i.e., an equation of state, may
yiedd inconsistent results. In our case, the inconsistency resulted in the
two different values of C0 at each temperatur~. On the other hand, signifi-
cant cha~ges in pr~ssure, or<fugacity, have._little effects on the density
of the saturated liquid.
c
If satfsfying Equation (3) is the objective, one should solve
Equation (1) twice at each temperature for the densities that are consistent
 - 5 -

with the vapor pressure and a single assumed value of co rather than solve
the same equation for C0 utilizing experimental densities. It could be as-
sumed that the densities thus obtained are not significantly different than
the experimental data.

To develop a set of C0 's which can be used in predicting phase

equilibria, the following procedure was adopted. At each temperature, a
value of C0 was assumed, the densities of the two phases at the vapor
pressure were established by trial and error from Equation (1) and the
fugacity of the component in each of the phases was calculated via Equation
(4) .. This procedure was repeated until the requirement of Equation (3)
was satisfied:

The final values of C0 thus established for argon along its vapor pressure
curve and the corresponding fugacities are given in Table 4.

Fugacities of a saturated "simple fluid" at the same corresponding

state were computed from Pitzer's relationships(23); these are also listed
in Table 4. The comparison of fugacities obtained with the two methods was
needed to verify that the trial and error procedure resulted in coefficients
that will yield thermodynamically acceptable fugacities.

It was noticed that at low temperatures and pressures the fugacity

• to variations in the fourth decimal
of the saturated liquid is sensitive
place of C0 while the vapor fugacity is hardly affected. On the other hand,
variations in C0 within the vicinity of the critical point equally affect
both phases and which make it difficult to zero on the final values of C0 •
Pitzer's fugacities were used as guide for selecting the final values.

The above discussion is illustrated in Figure 4. Almost any value

of C0 within the segments AB and AC would yield results which are close to
satisfying Equation (3) •. The solid curve, however, represents the values
that yield close to lhose calculated by Pitzer's method.

The value of C0 = 1.562 x 108 at the critical point is somewhat

lower than the value established for the superheated region (1.6056 x 108).
Extrapolation of the curve AC beyond the critical point qualitatively in-
dicated a possibility of improving the utilization of the BWR equations on
both sides of the critical point.

Computations of Isothermal Pressure Effects on Enthalpy

The validity of an equation of state undergoes a very severe test

when its derivatives are used to calculate the enthalpy difference, HP-H~"",
which results £rom isothermal pressure effects. Equation (Bll) in Ref. 3
is the form required for calculating these pressure effects from the BWR
equation:
 0

c
- 6 -

4C 2 6 5
0
(B 0 RT - 2A 0 - - ) d + (bRT - 1. 5a)d + - aad
T2 5

2
-yd
e ) (5)

Previously, it was shown that the coefficient C is temperature

dependent. The enthalpy departure from the ideal state c~n be expressed
in terms of the Helmholtz free energy A, and the equation of state
G
-
A T( ~*)d,x + p/d ( 6)

Starting with this expression, the first term of Equation (5) .is modified
in view of the temperature dependency of C •
0

Hp -H-Ie = ...
•
The results of sample computations of Hp - H* are given in Tables
5 and 6. Values of C for these computations were taken from·Table 4. With
the exception of the ~alue at the critical point, relatively good agree-
ment was observed between the calculated values and literature data (11).
The average difference is less than 5 Btu/lb. Some of the results are
illustrated in Figure 6.

Prediction of. VApor-Liguid Equilibrium Data

One of the factors favoring the use of the BWR procedure for
predictions of vapor-liquid K values is that it applies to a wide range of
temperatures and pressures. Without extrapolating ·the liquid fugacity of
a light compound, the method will reliably calculate equilibrium ratios for
that compound in a mixture at temperatures far above its own critical point.
This advantage has been verified for light hydrocarbon mixtures (5) within
the known limitations (13, 20). However, the rules for mixing the co-
efficients (Equations B25 to B33, Ref. 4) were arbitrarily selected and
must be tested for application to· systems containing a nonhydrocarbon, e.g.,
argon.
·-------------------···

- 7 -

The system nitrogen-argon at several low pressure isothermal con-

ditions was studied by Holst(l8). The data were analyzed and correlated by
Latimer(l9). Recently, a new set of data at high pressures was obtained by
Wilson et al(28). Points from these two sources were used to test the BWR
method(4,5) with the new coefficients for argon. To make this test possible
and consistent, a new set of C0 's had to be evaluated for nitrogen in the
saturated region, since the few points in the literature(l4,26) were diffi-
cult fo interpolate (s~e Fig~re 5). The values of C0 for nitrogen obtained
by the 11 fugacity-equalizati"on 11 procedure previously described are shown in
Figure 5. ·

Predicted K values for nitrogen and argon are compared against the
experimental values in Table 7. A ratio~ = Kexp/K?red measures the agree-
ment. In a way this ratio, ~. is similar to an act~vity coefficient. How-
ever, in order for ~ to qualify as an activity coefficient, it would have to
be rigorously related to the excess free energy and other thermodynamic
relationships.

"An analysis of the results, also illustrated in Figures 7 and 8,

indicates the following:

o Basically, good agreement exists between the calculated and the experi-
mental K values for the nitrogen-argon system. An average deviation of
±5% in K was observed.
~
e The average deviation between a calculated and experimental low pressure
K value is not larger in magnitude than the average deviation observed
by comparing Holst's(l8) and Wilson's(28) data.

As illustrated in Figure 7, this conclusion may explain some of

the differences betwe~n Latimer's(l9) and Wilson's(28) correlations.

e In addition to the random deviations, which may be due to experimental

errors, some definite trends in the ratio ~ could be detected. These
trends point out the dependency of w on compositions, At least two
causes of systematic errors exist. Errors in predictions at T < 140°R
result partly from lack of accuracy in fitting C0 's for nitrogen at
these low temperatures. However, it is believed that the major reason
is that the mixing rules for· the BWR coefficients are arbitrary and do
not fully describe the system. This is especially apparent when the
concentration of one of the substances is very low.

o A systematic error can 6e accounted for in the correlation~ In the

present work, the average values of w
using Wilson 1 s(28) high pressure
data were .plotted as dotted curves in Figure 8 and mathematical ex-
pressions were derived~o relate~ to x. When these relationships
were included in the correlation and the results compared with Wilson's
"data, the average deviation inK, at low compositions of either compo-
n~nt, was reduced from 11% to 2%.
 - 8 -

Conclusions

o The set of coefficients developed for argon accurately represents the

volumetric behavior of this gas in the superheated region. Below the
critical point, two different values of C0 at each temperature, one
for the vapor and one for the liquid, are necessary.

o Wnen the BWR procedure with the above values of C0 is used to calc.ulate
the fugacities of saturated vapor and liquid argon, different values
were obtained for each phase. It was concluded therefore that the two
different sets of C0 vs temperature could not be used for predicting
vapor-liquid equilibria.

o A new set of C0 vs temperature values was obtained by setting the

fugacity of the saturated vapor equal to that of the saturated liquid.
The BWR method,,utilizing these C0 values has been used to predict
vapor-liquid equilibria for the nitrogen-argon system in the tempera-
ture range 135° to 265°R. The results are in good agreement with pub-
lished experimental data. However, the deviations in the predictions
indicate some compositiun depend~nce in addition to random errors.

o The BWR method and the coefficients for argon yield fair results when
used to calculate pressure effects on enthalpy. The standard formula
had to be modified to account for the temperature dependence of the
coefficient C0 .

o There is a reason to believe that. extending the C0 vs temperature curve,

obtained from fugacity equalization, slightly above the critical tem-
perature will yield better results both in predicting volumetric be-
havior and enthalpy deviations.
 ,r

REFERENCES

·(1) Ba ly·,
c
c. c. and Donan, F. G.' J. Chern. Soc. JU., 907 (1902)

(2) Beattie, J. A. and Bridgeman, o. c.' J. Am. Chern. Soc. 49, 1665 (1927)

(3) Benedict, M.' Webb, G. B. and Rubin, L. c.' J. Chern. Phys. .§., 337 (1940)

(4) Benedict, M.' Webb, G. B. and Rubin, L. c.' J. Chern. Phys. l.Q, 747 (1942)

(5) Benedict, M., Webb, G. B. and Rubin, L. c.' Chern. Eng. Progr. Symp. Ser.
4 7' 419 (Aug. 1951)
(6) Bridgeman, o. c.' Proc. Am. Ac. Art-Sci. J.Sl, 1 (1935)

(7) Brough, H. w.' Schlinger, w. G. and Sage, B. H.' Ind. Eng. Chern.
43, 2442 ( 195.1)

(8) CaF.jar, L. N.' Pet. Ref. 35' 113 (Feb. 1956)

(9) Clark, A.M. Din, F., Robb, J., (The British O~ygen Co.) and Michels,
A., Wassenaar, T. and Zweitering, Physica XVII No. 10, 876 (1951)

(10) Crommelin, C. A., Commun. Phy1j.·Lab. Uni. of Leiden,118 a (1910)

(11) Din, R. (editor), "The Thermodynamic Functions of Gases," Volume 2,

Butterworth, London (1959)

(12) Efrqymson, M.A., Section 17 of "Mathematical Methods for Digital

Computers" edited by Ralston, A. and Wilf, H.S., John Wiley & Sons
Publishers (1960)

(13) Ellington, R. T., "Notes for Conference on Thermodynamic Properties

of Mixtures," Oklahoma State University, Stillwater, Oklahoma (April
13 and 14, 1964)

(14) Eubanks, L. S. Ph.D. Thesis, Rice Institute, Houston, Texas (May 1957)

(15) Fastowskii, V. G., and Peq;ovskii, Y.. V., Zhur .. Phys. Khim Vol. 30,
: 76 (1956)

(16) Gyorog, D. A. and Obert, E. F., AIChE J. Vol. l.Q, No.5, 621 (1964)

(17) Holborn, L. and Schu-tze, H., Ann. Phys, 47, 1089 (1915)
(18) Holst~ G. and Hamburger, L., Z. Physik Chern. lQ, 513 (1916)

(19) Latimer, R. E., AIChE J. l, No. l, 75 (1957)

f-4/
(20) Lin, M. S. and Naphtali, Lf AIChE J. j, No. 5, 580 (196~)

(21) Michels, A., Wijker, tlub, and Wijker, Hk., Physica, Jl, 627 (1949)

(22) Michels, A., Levelt, J.~M., de Graff, W., Physica 24, 659 (1958)
0

(23) ,Pitzer, K. S. and Curl, R. J. Jr., Ind. Eng. Chern. 50, 265 (1958)

(24)"Schiller, F. C. and Canjar, L. N., Chern. Eng. Progr., Symp. Ser.

49, No. 7, 67 (1953)

(25) Shah, K. K. and Thodos, G., Ind. Eng. Chern. 21_, No .. 3, 30 (1965)
,•,

(26) Stottler, H. H. and Benedict, M., Chern. Eng. Prog. Symp. Ser.
49, No. 6, 25 (19~3)

(27) Whalley, E., Lupien, Y. and Schnider, Can. J. Chern. 33, 633 (1955)

(28) Wilson, G. M., Silverberg, P.M. and Zellner, M. G., A paper presented
. at the c·ryogenic Engineering Conference, Philadelphia, Pa. (Aug. 17-21,
1964) ~

c
 a

TABLE 1
STANDARD DEVIATIONS, (P-RTd) VS y
(J

Number of points used fn the analysis · 597

Range of temperature 280 to 1080 °R
Range of pressure 14.7 to 7500 Psia

Standard Deviation
c (Psia)

0.200 20.5

0.400 20.1

0.500 19.5

0.550 , 19.0

. 0.575 18.9

0.600 18.8

·0.675 19.0
(,

0.700 19;1

0.800 19.7

0.900 20. l
 TABLE 2
CONSTANTS FOR BWR EQUATION
OF STATE FOR ARGON AND NITROGEN

a Units: P = psia·
T = 0 R = °F + 459.688
d = lb mole/cu ft
R = 10.7335 (consistent with Ref. 3,4,5)

,r ·Argon Nitrogen
Constant (Present Work) (20)
B 0.356939 0.733661
0 0

Ao· 3105.10 4496.95

c0 X 10- 8 l. 6'b560 0.71953~

b 0.552433 0.508467
0
a 1741.87 900.069
c X 10- 8 l. 56230 ·1.07267
'
a 0.146285 1.19838
.., 0.60 l. 92541
 TABLE 3
C OF SATURATED ARGON FROM VOLUMETRIC DATA

8
po ;
:
c0 X 10- (English Units)
0 ;
T R Psia '
Liquid ; Vapor
I
15 7 .l 14.696
I
i l. 30876 l 0.460638
:
i i. l
170.0 29.392 I 1.38631 0.610753 I
I

17~.6 44.088
I 1.43974
i
I
I 0.737230
I
I
190.8 73.480
I

I '1.49655.
i .
i
II
i.
0.932964 I
I
I

I. I
I
l
199.8 102.87 1.52731 ·I
l. 03054 I

I !
1
210.3 146 ,~r96 <
1.57536 i 1.174 75 !
• I
I
!
i'
I
i
223.6 220.44• 1.61387 i
I
l. 28421 i
.I :
I
~

0 !
234. 1· 293. 92 l. 63581 1.38829 i
I
. 242. 7 36 7.40 1.63214
·I· 1.43348
I
I
I

II I I

l
250.3 440.88 c l. 62 734 ·I 1.45832 li
I
I
I

263.0 587.84 i l. 62253 1.46 726

c

271.3
.,

I '
705.41 1.52719
1
I

!
0

1.52719 II
 a

. '

TABLE 4
C0 OF SATURATED ARGON
FROM FINAL TRIAL EQUATING FUGACITIES
0

Fugacity 1 Psia
-8 Pitzer')(23)
C0 x 10
pO . f(o BWR
T R 0
)
psia')'< English Units

149.8 9.99 1.319 9. 725 9.52

157.1 14.696 1.350 14.229 i4. 24

170.0 29.39 1.378 ·27.901 27.62

178.6 44.09 1.399 ·41.192 40.58

180.0 47.00 . 1.404 43.01

73.48 .
41
1.42 7 65.36
lc90. 8

102.87 1.44 7 91.5 7 89.02

199.8

149.96 1.468 127.15 123.3

210.3

.293.92 l. 517 222.51 224.5

234.1

440.88 1.537 315.39 318.1

250.3

587.84 1.553 403.12 399.5

1:,
263.0
I
,, 457.0
271.3 705.41 1.561 470.50
c
.,· >

* Ref. (6 '8)
 a

.. TABLE 5
DEVIATIONS FROM IDEAL GAS STATE ENTHALPIES
Hp-H*, BTU/LB MOLE
ARGON AS SUPERHEATED GAS

Temp. °F P psia Din(7) . BWR

·!
!
c I 279 ,. -1920 ° l
1469.6 I -1819
I 2939.2 -1927 -2006 l
I 4409.7 -1987
i

306
7348.0

1469.6 -1415
-1875

-1599
i
I

I 2339.2
4409.7
-1733
-1815
. -1887
. -1912 l
. 734-8.0 - -1836 -1834 I
I!
342 1469.6 - 920 -1004
2939.2 -1463 -1551
4409.7 -1603 -164 7
7348.0 -1676 -1615
c
378
 - •--------·-·--o ... -----~~-----

(l TABLE 6
ENTHALPY DEVIATIONS FROM THE IDEAL STATE
Hp-H* Btu/lb mole
Two phase region
,.

Liquid ··Vapor
To .P, atm
'
R 6!!-o
-in 6~WR 6 !!-oin at:,~
- WR

157.1 14.696 -2802 -2697 . - 5 '-42.6

170.0 29.29 -2734 -2660 - 18 -73.1

178.7 . 44.09 -2684 -2619 - 40 - 100

199.8 102.87 -2501 -2483 - 137 - 192

210.3 149.96 -2448 -2401 - 169 - 254

' 234.1 293.92 -2226 -2178 - 351 - 450

250.3 440.88 -2007 -1888 - 532 - 669

G

263.0 58 7. 84 -lR24 -1811 - 745 -114 7

271.3 705.41 -1329 -1665 -1329 -1665

 o TABLE 7A
COHPARISON BE'mEEN EXPERIMENTAL AND PREDICTED K-VALUES
Wilson's (28) Data

Nitrogen Argon
Temp. °F P, psia X K K /K X K K
--pred- -exp--pfed
/K
--pred -exp--pred
-3a3. 4a 14. 7a· 0.04620
-3a6.4a 14.70
. 2.644 1.055 0.95380 . 0.87100 0.974 0.937.
0.14110
..
0.33810 2.41a 0.994 o.o589a a.6619a 0. 813 0. 94 7
-31a.4a 14.7a 0.31310 2·.oo1 o.921 0.68690 a.42100 0.626 0.9/8
0.55230 a.78380 1. 50 7 a. 941 0.44770 a.21620 0.480 1.004
-318.2a 14."70 0.93630 1.148 0.964 0.15430 0.06370 0.427 0.965
-319.5a 14.70 0.9A!t3a 1.a4A 0.975 o.a3770 a.01570. 0.422 o.91J5
-32a.aa 14.70 0 .9<)280 a.9973a 1.015 a.989 o~oa720 0.0027a 0.416 o. 899
-316. 7a 14.7a c o. 70770 0.87070 1.2119 a.954 0.29230 0.12930 0.441 1.002

-253.89 146.96 0.24690 2.0n2 a.a24 0.85480 a.75310 0.895 a.983

146.96 0.25150 0.18830 1.5•H 0.970 o.7485a a.61170 a.713 1.146

146.96 0.45020 0.60350 1.451 0.923 a.549Ha a.3965a a. 111 o.926

-265.89 146.96 0.64000 0.76320 1.245 0.957 n.J6aaa 0.23680 a.747_ a.B8a

-262~89 146.96 0.80150 0.87800 1o2H9 Oo849 a.19850 0.1220a a.88l a.696'

0.06710 1.A63 0.825 O.'H290· 0.0968a ·a.948 · 1.a13·

·-227.99

293.92 0.2954a 0.40180 1.4a6 o.Y66 o.7046a a.~9820 a.820 1.a24

-237.99
0.85157. ~ 1.076 0.996 o.2a64a 0.14843 a.830 a.866
-246.89 293.92 0.79360
c
0.57070 a.67a3a 1.1'15 a.982 a.4293a a.3297a 0.836 0.917
-241.99 293.92

0.07670 a.u4aO 1.742 a.853 0.92330 0.886aO 0.94'> 1.a15

-222.99 338.a8
0.20430 a.28140 1.':113 a.91a 0.79<;70 a. 7186a a.906 o.996
-226.99 338.a8
0.41470 a.5160a 1.277 0.973 0.':18510 a.48400 0.867 a.953
-232.99 338.a8

-229.99 338.a8 0.30920 a.4a220 1.J80 0.942 0.69080 a.':l9780 0.8114 0.911

-238.99 338.08 0.65740 0.73670 1.121· 0.999 o. -~4260 a.2o33a o.a5o o.9a4

0.84a90 0.88360 1.047 1.003 0.15910 0.1164a o.ssa a.B60

0.9101l0 0.91490 1.026• 1.000 o·. a892a 0.06510 0.854 O.d54

-245.1Y 338.a8 0.94HIIO 0.96350 1.014' 1.000 a.a512a 0.03650 a.A':15 a.BJJ

-245.59 J3A.OA 0.96620 0.97650 ·1.009- 1.000 a. anA a a.02350 a.856 a.812

-245.79 338.08 a.9720a. 0.98010 1.007 1.00~ a.a272a o.Ol99a 0.855 a.S55

-245.99 338.08 a.98210 0.98710 1.004 1.000 a.a17'1a a.a129a a.ll56 a.B41

-246.19 338.08 0.99420 0.99500 1.002 0.998 a.oa5Aa a.oo5aa a.857 ~.ovs
 0 Nitrogen Argon
Temp. °F X
~red ~ex~pred X K K
--pred- -exp--prcd
/K

-218.99 382.17 0.10550 0.14810 1.600 0.877 0.89450 0.85190 0.9}9 1.1.)14
-221.99 382.17' 0-.20040 O.J7000 1.453 0.926 0.79960 0.73000 0.915 0.9-H
0.40800 0.49730 1.243 0.979 . 0.59200 0.~0270 0.8113 0.%0
-233.99 ,, 0.6"H80 0.71090 1.110 1.003 0.36220 0.28910 o.o69 u.918
' e
-l38.49 382. l7 0.83730 0.87530 1.039 1.005 0.16270 0.12470 0.870 0.880
'·
-240.49 382.17 0.93,010 0.94710 1.014 1.003 ,. 0.06990 0.0~290

-240.89 382.17 0.94940 0.96120 1.009 1.002 0.05060 0.03880 o.R75 o.t~76

-241.29 3112.17 0.96540 o.97360 1.oo~ 1.001 0.03460 0.02640 o.8T5 o.a11
-241.49 382.17 0.97390 0.98060 1.003 1.003 0.02610 0.01940 0.875 0.84!1

-241.69 382.17 0.9H640 0.98960 1.001 1.002 0.01360 0.01040 O.R77 O.ll1l

362. l7 0.99660 0.999 1.002 0.00500 0.00}40 0.877 o. 774

-241.89 3!l2.17 0.99490 0.99600 0.999 1.002 0.00')10 0.00400 0.877 0.893

TABLE 7A
COMPARISON BETWEEN EXPERI~lliNTAL AND PREDICTED K-VALUES
Holst's (18) Data

Nitr6gen Argon
Temp. °F P, psia X K /K X K /K
-exp--pred -exp--pred
-313.10 'l.67 0.10000 0.2918~ 2.122 1. 374 0.90000 o. 70815 0.813 0.967 .
-H8.10 9.67 0.31500 0.60606 1.831 1.050 0.6!1500 o. 'j9394
-323. 10 9.67 0.6~300 0.85195 1.293 1.008 o. '}4700 o. ~4805 0.380 1.120
-326.60 9.67 0.99000 0.99504 0.969 1. 0'3 6 0.01001) 0.00496 0.347 1.427
-306.20 14.70 0.10000 0.26932 2.347 1. 14 7 0.90000 O.H06S O.A27 0.91i1
-311.37 14.70 0.31500 0.58421 1.~94 0.979 0.61!500 0.41579 0.588 1.032
-316.80 14. 70 0.65300 0.84065 1.297 0.992 0.34700 0.1~935 0.426 1.077
-3lo.8o 14.70 0.82600 0.92491 1.109 0.17400 o. 07509 0.401. 1.073
-320.50 14.70 0.99000 0.99488 0.963 1.021 0.01000 0.00512 0.39'lo l.2A3
-301~30 19.34 0.10000 0.25010 2.459 1.016 0.90000 0.74990 O.AJ7 0.994
-306.60 1 'l-34 0.31500 0.56208 1.919 0.929 0.68500 0.43792 0.614 1.040
0.65300 0.83263 1.306 0.975 0.)4700 0.16737 0.462 1.043
-314.30 19.34 0.82600 0.92394. 1.120 0.998 0.17400 0.07606
-316.10 19.34 0.9YOOO 0.99505 0.995 1.009 0.01000 0.00495 0.437 1.131
-2'H.50 29.01 0.10000 0.2240~ 2.5S8o 0. 8 7 5• 0.90000 0.7759~ O. BS3• 1.010
-299.00 29.01 0. 8 7 8• 0.68500 0.46825 0.651 1.1.)49'
-304.90. 29.01 0.65300 0.8l111H 1. ~08• 0.34700 0.181S2 0.51S. 1.017.
-'j07.20. 29.1.)1 0.82600 0.91;662 1.126 0.985 o.17400 o.08Ha 0.494 0.969
-309.10 29.01 0.99000 0.99494 1.009 0.995 0.01000 0.00506 0.495 1.021
..... -~~-·~-------~--------~--------

<( . 21.0
(/') 1-.
0..

-..
1-

-o .
~
0..
I

......
20.5.I- "'
·y
z
0
1-
<t:
>
20.0

19.5
y
w
c·
Cl
-
~
<(
Cl
19.0
- . ·"
z
~ 18.5 I
(/')
o· 0.1 0.2 0.3 0.4 0.5 0.6. 0.7 0.8 0.9 1.0
BW~ COEFFICIENT o (ENGLISH UNITS)

Figure 1. STANDARD DEVIATION OF PRESSURE VS. AS SUM ED

1( FOR ARG.ON .
 '
i

--...- 588 psi a, data from Din (11)

4410 psia,.
..... ..g. ... data. from Din <11)
+3
· __,_ 5880 psi a, data from Din (11 >
--e-·7348psia, data from.Din <11)

.I p
I
-p
(f) +2· cal ex
2 o;o Deviations = 100
0
1-
<!
>
w +1
c
w
~
=>"
(J')
(/') ()
w
~
Cl.. \
~ .~ "lp'
-1 --+--- T. - I ' - - - - - + - - - - - - + - - - 1
v
-2~--~---~~~----~----~--~----._ ___.____ ~
200 400 600 800 1000
0
TEMP.' R"

Figure 2. DEVIATIONS IN PRESSURE PREDICTIONS FROM LITERATURE

·VALUES FOR ARGON
r c

1:.8
(/)
.....
z
:::>
:I:
·- (/)

-l
<.!J 1.2
z
w
o:)
. 1.0
I
0
r-4 o.a.
~
·x •
(.)
0 0.6 --~--~--~----~--~-~
Data from ,.....
0::: Din (11) N
··~ 0.4 1--+---+---+---+___;~..,;..::..:::...:.,_-+- II
al
0.2
160 180 200 220 240 . 260 280
T0 R

.Figure 3. ARGON C0 VS. TEMPERATURE,

FROM VAPOR PRESSURE AND DENSITIES
 - - - - - - · - - - ..- ~
. !

.,

1.65 I I 1 . , ,
. I I
At T > Tc C0 = 1. 60560 X 10
8 BI .
1.6
-,_.. - - - -.- - -
~ -L- j-:... - -

EEf- I~ /~ l---
(/)
1-
z 1.55
=> I ,......
:c lr---
(/) 1. 5 N
_J · In
z
w
(.!}

co ... · 1.4
1.45
71 . ~
I
0
,.....
X
.
1.35
·V
7]•
Data Source,. Clark
et al (6) ·

1.3 '
1.25 I
120 160 ~00 240 280
0
TEMP., R

Figure 4. VALUES OF BWR Co FOR ARGON, OBTAINED ·

FROM FUGACITY .EQUALIZATION
 ~--~ ·-------

-2400~--~----~----~--~----~----~---.

-.2000 ~I ~r,---~~---4-----+-----+-----r--~
w ~I
.........
_J
0 ~I
2 -1600 ~~,--t-----+-'
ca 1-
_J
..........
~ -1200~----~----1----~---,--4-----+-----+----~
ca
...
~
~ -aoo~----~----~--~----~----~-­
•
0..
~.
".
-4 0 0 1--------1 _ Values from Din
e BWR -1469.6 psi a
s:J BWR- 4409 .. 7 psia
300 340 380
TEMP., 0
R

Figure s. ENTHALPY DEVIATIONS, Hp- H *

SUPERHEATED ARGON
,,
,,

7.3
I . I . 7
0
Ico = 7 .19 534 X 10
,_
(/)
7.2
2
:::>
:I: 7.1 /r I
. Ia:::
I~
(/)

--'
(.!} I..O
.z 7.0 N
UJ
1~-
I'- I~
6;9

t
I
0
r-i , 0 0
X -Trials to obtain fl =fv
0 6.8 e · Stottler + Benedict (26)
u
.A.· Eubanks (14)

6.7 I
100 150 200 250 300

Figure 6.~ VALUES OF BWR C0 FOR NITROGEN, OBTAINED

·FROM FUGACITY. EQUALIZATION
~- --

1.2

r-- ... P
I
=14.7 psia
I l
·1.1 ~ .. i, _
/
-~ A /
...... . .~~.~~ .. · ~~ c
··.!·~~~~~I
--~-
1.0 6. ---
A
.
c t:..
cg . e
·g
1- c a
. . . o. 9 liJ Holst Data Wilson•s Data
A Argon g Argon
1-
t:. Nitrogen· c Nitrogen· -
0.8 I I " I I
0 0.2 0.4 0 .. 6 0.8 1.0
MOL. FRACTION OF ARGON

Figure· 7. NITROGEN-ARGON
, PREDICTED VS. EXPERIMENTAL K VALUES
 1

1.1.-~.-~----r---r---.---~--~--~--~--~
Wilsdn 382 .2 psi~ wdson 3.38 .1 ~sia
1

o Argon • Argon
r- o Nitrogen t:.. Nitrogen -

I d) I I I I 0•

,
-

0.8~--~~~--~--~--~--~--~--~--~--~
0 0.2 0.4 0.6 0.8 1.0
MOLE FRACTION OF ARGON

Figure 8. NITROGEN-ARGON .
PREDICTED VS. EXPERIMENTAL K VALUES