May 20, 1057 THERMODYNAMIC

PROPERTIES
OF FLUIDS 2369

[ CONTRIBUTIOX
FROM THE DEPARTMENT A N D CHEMICAL
OF CHEMISTRY UNIVERSITYOF CALIFORNIA,
ENGINEERING,
BERKELEY]

The Volumetric and Thermodynamic Properties of Fluids. 111. Empirical Equation

An equation has been developed t o represent the second virid coefficient of a normal fluid: BP,/RT, = (0.1445 +
0 . 0 7 3 ~ )- (0.330 - 0.46w)TC-' - (0.1385 + +
O.50u)Tr-* - (0.0121 0.097w)Tr-a - 0.0073wTr-8 where u is the acentric
factor (defined by w = -log (P/P,),st - 1,000 at T , = 0.7) which was discussed in an earlier paper. This equation not
ollly fits the volumetric data with considerable accuracy but its second derivative also yields agreement with measureil
values of the pressure derivative of the gas heat capacity.

In 1007 Berthelot2 proposed a simple reduced Selection of the Equation.-Our earlier studies3
equation for the second virial coefficient which has indicated that an equation linear in the acentric
been of great value in correcting the properties of factor was usually adequate and we find this to be
real gases a t low pressures to the ideal gas state. the case for the second virial coefficient. We have
We know, however, that real gases do not follow ac- then, in reduced dimensionless form
curately the principle of corresponding states,
hence any such equation is of limited accuracy.
I n the earlier papers of this series3 we have shown
that the introduction of the acentric factor as an where B(O) and B(l) are functions of the reduced
additional parameter increases the accuracy of pos- temperature, and w is the acentric factor. Although
w was defined as
sible correlation by about one order of magnitude.
In this paper we present an empirical equation w = -logP, - 1.000 (2)
for the second virial coefficient in reduced form where P, is the reduced vapor pressure (PIP,) at
which includes the acentric factor dependence. Tr = 0.7, it may be evaluated readily from any
Basic Data.-In addition to the second virial vapor pressure value well removed from the critical
coefficient values based on volumetric measure- point by the use of Table VI of Paper I1 of this se-
m e n t ~ we
, ~ calculated the volume of the saturated ries.
vapor from vapor pressure, heat of vaporization The simple fluids of zero acentric factor are the
and liquid volume data in several cases5 heavier inert gases A, Kr, Xe. We know their
We also used the information on the change with properties are quite well represented by a Lennard-
pressure of the gas heat capacity.'j If the second Jones intermolecular potential. Consequently, we
virial coefficient is B , thermodynamics yields the took the equation of Stockmayer and Beattie' as
equation a point of departure. This was converted from the
molecular potential constants to the macroscopic
critical constants and then modified slightly to
improve the fit a t the lowest temperatures by the
Consequently, the pressure dependence of the heat addition of a small T-3 term and other small ad-
capacity offers a very sensitive test of any equation justments. The resulting equation is
for B.
(1) This research was part of the program of Research Project 50 of
the American Petroleum Institute.
(2) D.Berthelot, Traw. et Mbm. Bur. I n f . Poid e l Mes., 13 (1907). Figure 1 shows the reduced virial coefficient data
(3) K. S. Pitzer, D. 2. Lippmann, R. F. Curl, Jr., C. M. Huggins
and D. E. Petersen, THISJOURNAL, 77,3427, 3433 (1955). for a number of substances together with calcu-
(4) A, Kr, Xe: E. Whalley and W. G. Schneider, J . Chem. Phys., lated curves. The agreement of the curve for w =
23, 1644 (1955); N2: values of Holborn and Otto given by T. Kihara, 0 with the points for A, Kr and Xe demonstrates
Rev. Mod. Phys., 26, 831 (1953); COS: K. E. MacCormack and W. G. the adequacy of equation 3.
Schneider, J . Chem. Phys., 18, 1269 (1950); n-heptane: J. 0.Hirsh-
felder, el al., ibid., 10, 201 (1942); benzene: P. G. Francis, M. L. It is impractical to show all of the data consid-
McGlashan, S. D. Hamann and W. J. MchIanamey, ibid., 20, 1341 ered in the development of the equation for B(".
(1952). The resulting fit with the data for benzene and for
( 5 ) Kr: A. Michels, T. Wassenaar and Th. N. Zwietering, Physica,
18, 63 (1952), K , Clusius, A. Kruis and F. Konneitz, Ann. Physik,
n-heptane is shown on Fig. 1 for B and on Fig. 2 for
33, 642 (1938); Xe: A. hlichels and T. Wassenaar, Physica, 16, 253 the pressure derivative of the heat capacity. Simi-
(1950); K. Clusius and L. Riccoboni, 2. phyrik. Chem., B38, 81 lar agreement is obtained for other substances.
(1937); hydrocarbons: F. D. Rossini, et ai., "Selected Values of The resulting equations are
Physical and Thermodynamic Properties of Hydrocarbons and Re-
lated Compounds," Carnegie Press, 1953; n-heptane: G. Thodos, B = B(O) + wg(l) (4)
I n d . E n g . Chem., 42, 1514 (1950); G. Waddington, S. Todd and H .
Huffman, THIS JOURNAL, 69, 22 (1947); benzene: D. W. Scott, G.
Waddington, J. C. Smith and H. M. Huffman, J . Chem. Phys., 16, 565
(1947).
(6) %Heptane: G. Waddington, S. Todd and H. Huffman, THIS The selection of a term in T,-8 is, of course, some-
J O U R N A L , 69, 22 (1947); CsHs: D.W. Scott, G. Wsddington, J. C. what arbitrary, but a very high power is required
Smith and H. M. Huffman, J . Chem. Phys., 16, 565 (1947); 2,2,3-
trimethylbutane: G . Waddington, S. Todd and H. Huffman, THIS
to fit the data a t low temperatures.
J O U R N A L , 69, 22 (1947); ethanethiol: J. P. McCullough el a!., ibid., (7) W. H. Stockmayer and J. A . Beattie, J . Chem. Phys., 10, 470
74,2801 (1952). (1942).
 -1
-8
Simple Fluid

0=.35

-*.O t O \ ' 1
-~

-1 2 3 4
T;'.
Fig. 2.--.1 comparison of calculated and experimeutal
Ti
values of the pressure derivative of the heat capacity. The
Fig. 1.--A comparison of calculated and experimental circles and upper curve are for n-heptane ( w = 0.35); t h e
values of the second virial coefficient. Solid circles are squares and intermediate curve are for benzene ( w = 0,215').
A, Kr or X e points and the line through these points is t h a t The bottom curve is for w = 0, b u t no experimental data
of equation 3. T h e open triangles are COS and solid tri- are available for comparison,
angles are benzene points. These are to be compared with
the line for w = 0.215. The open circles are points for n- Discussion.-This equation should be valuable
heptane ( w = 0.35). It is to be noted t h a t the Berthelot for the estimation of gas imperfection corrections
equation yields excellent agreement for w in the range 0.15 to various data on gases a t low pressures. The sub-
t o 0.20. stances which can be expected to conform are those
forming normal liquids. Metals and hydrogen
The work leading to the selection of equation 5 bonding substances must be excluded. The limita-
indicated certain small changes in the previously tions are discussed in greater detail in Papers I and
published values of dl), the term in the compressi- II.3 The final equations for various properties are
bility factor expression which is multiplied by W . readily derived from thermodynamics. In these
The revised values are given in Table I (the upper equations H*, S*, C,* refer to the properties of the
right-hand portion of each section is unchanged but hypothetical ideal gas a t the same pressure as t h c
included for convenience). real gas; f is the fugacity.

TABLE I
BPC
R-Tc = + 0 . 0 7 3 ~ -) (0.33n - 0.46w)Tt-' -
(0,1445

REVISED\ ~ ~ ~ FACTOR
r OF 2'~ FOR COMPRESSIBILITY ~ CAI,-
~
T ~ - ~ +0.097~)~-
(0.1385 + O . , W ~ ~-~ :o.nizi ~-3
CULATION (SEETABLE IY,PAPER11)
c Pr -
Tr 0.2 0.4 0.6 0.8 1.0
1.20 0 009 0.018 0.028 0.044 0.069
1,25 ,011 ,023 ,036 ,050 ,069
1 3 ,013 ,027 ,041 ,055 ,072
1.4 ,016 ,032 049 ,085 ,082
1.5 ,017 ,035 ,052 .070 ,088
1.6 ,018 ,036 054 ,072 ,090

Tr 1 2 3 4
Pr
.5 6 7 8 9
-
1.7 0.09 0 . 1 6 0 . 2 1 0 24 0 . 2 5 0.26 0.25 0.24 0.22
1.8 .09 ,16 ,21 ,26 .29 .31 .32 .32 .30
1.9 .09 ,I6 .21 .26 .30 .35 .38 ,40 .40
2.0 .OS .15 ,21 .26 .30 .35 .40 .43 .45
2.5 .07 ,13 ,20 , 2 5 .30 .35 .40 .45 .50
3 .O .06 ,11 ,17 ,23 .28 .31 .38 .45 .50
3.5 ,05 ,09 ,14 ,19 .24 ,28 .33 .38 ,42
4 .O ,04 .08 .12 ,16 .20 .23 .27 .31 .35