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i n t e r m o l e c u l a r p o t e n t i a l must be given by a u n i v e r s a l f u n c t i o n w i t h
s c a l e f a c t o r s of energy and d i s t a n c e f o r each substance. By then i t
was well-known that the dominant a t t r a c t i v e f o r c e f o l l o w e d an
i n v e r s e sixth-power p o t e n t i a l f o r a l l of these substances. A l s o the
r e p u l s i v e f o r c e s were known to be very sudden. Thus the i n v e r s e
s i x t h , power term w i l l dominate the shape of the p o t e n t i a l curve at
longer d i s t a n c e s . Even without d e t a i l e d t h e o r e t i c a l reasons f o r
exact s i m i l a r i t y of shorter-range terms, one could expect that a
u n i v e r s a l f u n c t i o n might be a good approximation. I n a d d i t i o n one
assumed s p h e r i c a l symmetry (approximate f o r methane), the v a l i d i t y
of c l a s s i c a l s t a t i s t i c a l mechanics, and that the t o t a l energy was
determined e n t i r e l y by the v a r i o u s i n t e r m o l e c u l a r d i s t a n c e s .
I should r e c a l l that i t was not f e a s i b l e i n 1939 to c a l c u l a t e
the a c t u a l equation of s t a t e from t h i s model. One could o n l y show
that i t y i e l d e d corresponding s t a t e s , i . e . , a u n i v e r s a l equation of
s t a t e i n terms of the reduced v a r i a b l e s of temperature, volume, and
pressure.
One could p o s t u l a t e other models which would y i e l d a c o r r e s ponding-states behavior but d i f f e r e n t from that of the simple f l u i d .
However, most such molecular models were s p e c i a l and d i d not y i e l d
a s i n g l e f a m i l y of equations. Rowlinson (6) found a somewhat more
general case; he showed that f o r c e r t a i n types of a n g u l a r l y dependent a t t r a c t i v e f o r c e s the net e f f e c t was a temperature dependent
change i n the r e p u l s i v e term. From t h i s a s i n g l e f a m i l y of funct i o n s arose.
I had observed e m p i r i c a l l y , however, that the f a m i l y r e l a t i o n ship of equations of s t a t e was much broader even than would f o l l o w
from R o w l i n s o n s model. I t included g l o b u l a r and e f f e c t i v e l y
s p h e r i c a l molecules such as tetramethylmethane (neopentane), where
no a p p r e c i a b l e angular dependence was expected f o r the i n t e r m o l e c u l a r p o t e n t i a l , and f o r elongated molecules such as carbon d i o x i d e
the angular dependence of the r e p u l s i v e f o r c e s seemed l i k e l y to be
at l e a s t as important as that of the a t t r a c t i v e f o r c e s . Thus the
core model of K i h a r a (7) appealed to me; he assumed that the LennardJones 6-12 p o t e n t i a l a p p l i e d to the s h o r t e s t d i s t a n c e between cores
i n s t e a d of the d i s t a n c e between molecular centers. He was a b l e to
c a l c u l a t e the second v i r i a l c o e f f i c i e n t f o r v a r i o u s shapes of core.
And I was a b l e to show that one obtained i n good approximation a
s i n g l e f a m i l y of reduced second v i r i a l c o e f f i c i e n t f u n c t i o n s
f o r cores of a l l reasonable shapes. By a s i n g l e f a m i l y I mean that
one a d d i t i o n a l parameter s u f f i c e d to d e f i n e the equation f o r any
p a r t i c u l a r case. While t h i s d i d not prove that a l l of the complete
equations of s t a t e would f a l l i n t o a s i n g l e f a m i l y , i t gave me enough
encouragement to go ahead w i t h the numerical w o r k o r more a c c u r a t e l y
to persuade s e v e r a l students to undertake the n u m e r i c a l work.
Let me emphasize the importance of f i t t i n g g l o b u l a r molecules
i n t o the system. I f these molecules are assumed to be s p h e r i c a l i n
good approximation, they are easy to t r e a t t h e o r e t i c a l l y . Why aren't
they simple f l u i d s ? Many t h e o r e t i c a l papers ignore t h i s q u e s t i o n .
In f l u i d p r o p e r t i e s neopentane departs from the simple f l u i d p a t t e r n
much more than propane and almost as much as n-butane.
But propane
f
Storvick and Sandler; Phase Equilibria and Fluid Properties in the Chemical Industry
ACS Symposium Series; American Chemical Society: Washington, DC, 1977.
1.
PITZER
(i)
where p i s the s h o r t e s t d i s t a n c e between c o r e s . For the p o l a r
molecules I omitted the core, thus p = r .
While the curves i n F i g u r e 2 appear t o f a l l i n t o a s i n g l e f a m i l y ,
t h i s i s i n v e s t i g a t e d more r i g o r o u s l y i n F i g u r e 3 where the reduced
second v i r i a l c o e f f i c i e n t a t one reduced temperature i s compared w i t h
the same q u a n t i t y a t another temperature. Tg i s the Boyle temperature which i s a convenient r e f e r e n c e temperature f o r second v i r i a l
c o e f f i c i e n t s . One sees that the non-polar core molecules f a l l
a c c u r a t e l y on a s i n g l e curve (indeed a s t r a i g h t l i n e ) . While the
p o l a r molecules d e v i a t e , the d i f f e r e n c e i s o n l y 1% a t y = 0.7 which
I took as a reasonable standard of accuracy a t that time. For comparison the y values of c h l o r o f o r m , e t h y l c h l o r i d e , and ammonia are 0.04,
0.16, and 4, r e s p e c t i v e l y . Thus the f i r s t two f a l l w e l l below the 0.7
v a l u e f o r agreement of p o l a r w i t h non-polar e f f e c t s w h i l e ammonia i s
beyond that v a l u e .
The next q u e s t i o n was the c h o i c e of the experimental b a s i s f o r
the t h i r d parameter. The vapor pressure i s the property most s e n s i t i v e t o t h i s t h i r d parameter; a l s o i t i s one of the p r o p e r t i e s most
Storvick and Sandler; Phase Equilibria and Fluid Properties in the Chemical Industry
ACS Symposium Series; American Chemical Society: Washington, DC, 1977.
11
1
-
_^*- *^-
if
1
0.5
\J
1.0
1.5
i
2.0
2.5
r/r .
0
If>
/ T .
Figure 2. Reduced second virial coefficients for several models: solid curve, simple fluid;
curves labeled by a./p , spherical cores of radius a; curves labeled by l/p , linear cores
of length 1; curves labeled by y, molecules with dipoles
0
Storvick and Sandler; Phase Equilibria and Fluid Properties in the Chemical Industry
ACS Symposium Series; American Chemical Society: Washington, DC, 1977.
Storvick and Sandler; Phase Equilibria and Fluid Properties in the Chemical Industry
ACS Symposium Series; American Chemical Society: Washington, DC, 1977.
- 1.000
(2)
pv
=
= z
RT
( 0 )
(0)
z
= z
-
( 1 )
Storvick and Sandler; Phase Equilibria and Fluid Properties in the Chemical Industry
ACS Symposium Series; American Chemical Society: Washington, DC, 1977.
1.
PITZER
Ar
Ar
i Q \
CH
CH
3 8
H
i.O
0.8-
1.30
.25
1.20
1.15
0.6
PV
RT'
' 1.10
0.4
- 1.05
#f 1.00
0.2-
A
Xe
CH
C H
HS
2
C(CH )
n-C H,
3
l6
6 6
H
C0
C H
n-C H
H0
NH
0.1
0.2
CJ.
0.3
0.4
Storvick and Sandler; Phase Equilibria and Fluid Properties in the Chemical Industry
ACS Symposium Series; American Chemical Society: Washington, DC, 1977.
16
a n d
Storvick and Sandler; Phase Equilibria and Fluid Properties in the Chemical Industry
ACS Symposium Series; American Chemical Society: Washington, DC, 1977.
1.
PITZER
Literature Cited
1.
Storvick and Sandler; Phase Equilibria and Fluid Properties in the Chemical Industry
ACS Symposium Series; American Chemical Society: Washington, DC, 1977.
10
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
Storvick and Sandler; Phase Equilibria and Fluid Properties in the Chemical Industry
ACS Symposium Series; American Chemical Society: Washington, DC, 1977.