Acentric Factor

1
Origin of the Acentric Factor

K E N N E T H S. P I T Z E R
Downloaded by 108.21.206.41 on May 8, 2016 | http://pubs.acs.org

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0060.ch001
University of California, Berkeley, Calif. 94720
It was a pleasure to accept Dr. Sandler's invitation to open

this conference by reviewing the ideas and general point of view
which led me to propose the acentric factor in 1955. Although I had
followed some of the work in which others have used the acentric
factor, the preparation of this paper provided the incentive to
review these applications more extensively, and I was most pleased
to find that so much has been done. I want to acknowledge at once
my debt to John Prausnitz for suggestions in this review of recent
work as well as in many discussions through the years.
Beginning in 1937, I had been very much interested in the
thermodynamic properties of various hydrocarbon molecules and hence
of those substances in the ideal gas state. This arose out of work
with Kemp in 1936 on the entropy of ethane (1) which led to the
determination of the potential barrier restricting internal rotation.
With the concept of restricted internal rotation and some advances
in the pertinent statistical mechanicsitbecame possible to calculate rather accurately the entropies of various light hydrocarbons
(2). Fred Rossini and I collaborated in bringing together his heat
of formation data and my entropy and enthalpy values to provide a
complete coverage of the thermodynamics of these hydrocarbons in
the ideal gas state (3). As an aside I cite the recent paper of
Scott (4) who presents the best current results on this topic.
But real industrial processes often involve liquids or gases at
high pressures rather than ideal gases. Hence it was a logical
extension of this work on the ideal gases to seek methods of obtaining
the differences in properties of real fluids from the respective ideal
gases without extensive experimental studies of each substance.
My first step in this direction came in 1939 when I was able to
provide a rigorous theory of corresponding states (5) on the basis of
intermolecular forces for the restricted group of substances, argon,
kryptron, xenon, and in good approximation also methane. This
pattern of behavior came to be called that of a simple fluid. It is
the reference pattern from which the acentric factor measures the
departure. Possibly we should recall the key ideas. The
1
Storvick and Sandler; Phase Equilibria and Fluid Properties in the Chemical Industry
ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

PHASE EQUILIBRIA AND FLUID PROPERTIES IN CHEMICAL INDUSTRY
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

1.
PITZER
i s much l e s s s p h e r i c a l than neopentane.

The e x p l a n a t i o n l i e s i n the
narrower a t t r a c t i v e p o t e n t i a l w e l l . The i n v e r s e - s i x t h - p o w e r a t t r a c t i v e p o t e n t i a l now operates between each p a r t of the molecule r a t h e r
than between molecular c e n t e r s . Thus the a t t r a c t i v e term i s steeper
than i n v e r s e s i x t h power i n terms of the d i s t a n c e between molecular
c e n t e r s . This i s shown i n F i g u r e 1, taken from my paper (8) i n 1955.
We need not bother w i t h the d i f f e r e n c e s between the models y i e l d i n g
the dotted and dashed curves f o r the g l o b u l a r molecule. The important f e a t u r e i s the narrowness of the p o t e n t i a l w e l l f o r e i t h e r of
these curves as compared t o the s o l i d curve f o r the molecules of a
simple f l u i d .
I t was easy t o show that the i n t e r m o l e c u l a r p o t e n t i a l curves f o r
s p h e r i c a l molecules would y i e l d a s i n g l e f a m i l y of reduced equations
of s t a t e . I f one takes the K i h a r a model w i t h s p h e r i c a l c o r e s , then
the r e l a t i v e core s i z e can be taken as the t h i r d parameter i n a d d i t i o n t o the energy and d i s t a n c e s c a l e f a c t o r s i n the t h e o r e t i c a l
equation of s t a t e .
With an adequate understanding of g l o b u l a r molecule b e h a v i o r , I
then showed as f a r as was f e a s i b l e that the p r o p e r t i e s of other nonp o l a r or weakly p o l a r molecules would f a l l i n t o the same f a m i l y . I t
was p r a c t i c a l a t that time only to c o n s i d e r the second v i r i a l c o e f f i cent. The K i h a r a model was used f o r nonpolar molecules of a l l shapes
w h i l e R o w l i n s o n s work provided the b a s i s f o r d i s c u s s i o n of p o l a r
molecules. F i g u r e 2 shows the reduced second v i r i a l c o e f f i c i e n t f o r
s e v e r a l cases. Curves l a b e l e d a / p r e f e r t o s p h e r i c a l - c o r e molecules
w i t h a i n d i c a t i n g the core s i z e , c o r r e s p o n d i n g l y /p i n d i c a t e s a
l i n e a r molecule of core l e n g t h , w h i l e y r e f e r s to a d i p o l a r
molecule w i t h y = u /e ^r
where u i s the d i p o l e moment. The
non-polar p o t e n t i a l i s
1
(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

1
11
1
-
_^*- *^-

if
1
0.5
\J
1.0
1.5
i
2.0
2.5
r/r .
0
Figure 1. Intermolecular potential for molecules of a simple

fluid, solid line; and for globular molecules such as C(CH )
dashed lines
3
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

Figure 3. Check on family relationship of curves of Figure 2. Comparison of

deviations from simple fluid at (T /TJ = 3.5 with that at (T /T) = 2.0
B
w i d e l y measured at l e a s t near the normal b o i l i n g p o i n t . Thus both

the a v a i l a b i l i t y of data and the accuracy of the data f o r the purpose
s t r o n g l y i n d i c a t e d a vapor p r e s s u r e c r i t e r i o n . Since the c r i t i c a l
data have to be known f o r a reduced equation of s t a t e , the reduced
vapor pressure near the normal b o i l i n g p o i n t was an easy choice f o r
the new parameter. The a c t u a l d e f i n i t i o n
a) = -og P
- 1.000
(2)
w i t h P the reduced vapor pressure a t T = 0.700 seemed convenient,

but the a c t u a l d e t e r m i n a t i o n of a) can be made from any vapor pressure
v a l u e well-removed from the c r i t i c a l p o i n t .
Here I should note the work of R i e d e l (9) which was substant i a l l y simultaneous w i t h mine but whose f i r s t paper preceded s l i g h t l y .
His work was p u r e l y e m p i r i c a l , but was e x c e l l e n t and f u l l y complementary. He chose f o r h i s t h i r d parameter a l s o the slope of the
vapor pressure c u r v e , but i n h i s case the d i f f e r e n t i a l s l o p e a t the
c r i t i c a l p o i n t . That seemed to me to be l e s s r e l i a b l e and a c c u r a t e ,
e m p i r i c a l l y , although e q u i v a l e n t o t h e r w i s e . F o r t u n a t e l y R i e d e l and
I chose to emphasize d i f f e r e n t p r o p e r t i e s as our r e s p e c t i v e programs
proceeded; hence the f u l l area was covered more q u i c k l y w i t h l i t t l e
d u p l i c a t i o n of e f f o r t .
A l s o I needed a name f o r t h i s new parameter, and that was d i f f i c u l t . The term " a c e n t r i c f a c t o r " was suggested by some f r i e n d l y
reviewer, p o s s i b l y by a r e f e r e e ; I had made a l e s s s a t i s f a c t o r y
choice i n i t i a l l y . The conceptual b a s i s i s i n d i c a t e d i n F i g u r e 4.
The i n t e r m o l e c u l a r f o r c e s between complex molecules f o l l o w a simple
e x p r e s s i o n i n terms of the d i s t a n c e s between the v a r i o u s p o r t i o n s of
the molecule. Since these f o r c e s between n o n - c e n t r a l p o r t i o n s of the
molecules must be c o n s i d e r e d , the term " a c e n t r i c f a c t o r " seemed
appropriate.
I t i s assumed that the c o m p r e s s i b i l i t y f a c t o r and other propert i e s can be expressed i n power s e r i e s i n the a c e n t r i c f a c t o r and that
a linear expression w i l l usually s u f f i c e .

pv
=
= z
RT
( 0 )
(0)
z
= z
-
( 1 )
The preference of P over V as the second independent v a r i a b l e i s

p u r e l y e m p i r i c a l ; the c r i t i c a l pressure i s much more a c c u r a t e l y
measurable than the c r i t i c a l volume.
The e m p i r i c a l e f f e c t i v e n e s s of t h i s system was f i r s t t e s t e d
w i t h v o l u m e t r i c data as shown on F i g u r e 5. Here pv/RT a t a p a r t i c u l a r
r
1.
PITZER
Ar
Ar
i Q \
CH

CH
Figure 4. Intermolecular forces operate

between the centers of regions of substantial electron density. These centers
are the molecular centers for Ar and
(approximately) for CH but are best
approximated by the separate CH and
CH groups in C H hence the name
acentric factor for the forces arising from
points other than molecular centers.
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
Figure 5. Compressibility factor as a

function of acentric factor for reduced
pressure 1.6 and reduced temperature
shown for each line. Where several substances have approximately the same
acentric factor, the individual points are
indistinguishable except for n-C H
C) and H O(Q).
7
16
reduced temperature and pressure i s p l o t t e d a g a i n s t u). The most

important r e s u l t appears only by i m p l i c a t i o n ; the r e s u l t s f o r C(CH^)^,
n-CifiiQ
6 6>
C02 are so n e a r l y equal t h a t they appear as s i n g l e
p o i n t s on these p l o t s . Here we have f o u r w i d e l y d i f f e r e n t shapes of
molecules which happen to have about the same a c e n t r i c f a c t o r , and
they f o l l o w corresponding s t a t e s a c c u r a t e l y among themselves.
A l s o to be noted from F i g u r e 5 i s the f a c t that the h i g h l y p o l a r
molecules NH3 and H2O depart from the system. Furthermore the dependence on a) i s l i n e a r except f o r the c r i t i c a l r e g i o n .
My immediate r e s e a r c h group used g r a p h i c a l methods i n d e a l i n g
w i t h the experimental data and r e p o r t e d a l l of our r e s u l t s i n numeric a l t a b l e s (10). At t h a t time the best a n a l y t i c a l equation of s t a t e
was t h a t of B e n e d i c t , Webb and Rubin (11) which employed e i g h t parameters and s t i l l f a i l e d to f i t v o l u m e t r i c data w i t h i n experimental
accuracy. Bruce Sage suggested f i t t i n g t h i s equation to the data
for the normal p a r a f f i n s both d i r e c t l y f o r each substance and w i t h i n
the a c e n t r i c f a c t o r system. T h i s work (12) was done p r i m a r i l y by
J . B. O p f e l l a t C a l Tech. The r e s u l t s showed that the a c e n t r i c
f a c t o r system was a great advance over the simple p o s t u l a t e of
corresponding s t a t e s , but the f i n a l agreement was i n f e r i o r to that
obtained by g r a p h i c a l and numerical methods.
Thus we continued w i t h numerical methods f o r the f u g a c i t y ,
entropy, and enthalpy f u n c t i o n s (13), although we d i d present an
e m p i r i c a l equation f o r the second v i r i a l c o e f f i c i e n t (14). This
work was done by Bob C u r l ; he d i d an e x c e l l e n t job but found the
almost i n t e r m i n a b l e g r a p h i c a l work very tiresome. Thus I was
pleased t h a t the B r i t i s h I n s t i t u t i o n of Mechanical Engineers
i n c l u d e d C u r l i n the award of t h e i r C l a y t o n P r i z e f o r t h i s work. A
f i f t h paper w i t h H u l t g r e n (15) t r e a t e d mixtures on a p s e u d o c r i t i c a l
b a s i s , and a s i x t h w i t h Danon (16) r e l a t e d K i h a r a core s i z e s to the
acentric factor.
N a t u r a l l y , I am v e r y pleased to note t h a t o t h e r s have extended
the accuracy and range of our t a b l e s and equations w i t h c o n s i d e r a t i o n of more recent experimental r e s u l t s . Of p a r t i c u l a r l y broad
importance i s the 1975 paper by Lee and K e s s l e r (17) which presents
both improved t a b l e s and a n a l y t i c a l equations f o r a l l of the major
f u n c t i o n s i n c l u d i n g vapor p r e s s u r e s , v o l u m e t r i c p r o p e r t i e s , e n t h a l p i e s ,
e n t r o p i e s , f u g a c i t i e s , and heat c a p a c i t i e s . Their equation i s an
e x t e n s i o n of that of Benedict, Webb, and Rubin now c o n t a i n i n g twelve
parameters. They considered more recent experimental data as w e l l
as a number of papers which had a l r e a d y extended my e a r l i e r work i n
p a r t i c u l a r areas. I r e f e r to t h e i r b i b l i o g r a p h y (17) f o r most of
t h i s more d e t a i l e d work, but I do want to note the improved equation
of Tsonopoulos (18) f o r the second v i r i a l c o e f f i c i e n t . This equation
deals a l s o w i t h e f f e c t s of e l e c t r i c a l p o l a r i t y .
In a d d i t i o n to r e f e r e n c e s c i t e d by Lee and K e s s l e r there i s the
work Lyckman, E c k e r t , and P r a u s n i t z (19) d e a l i n g w i t h l i q u i d volumes;
they found i t necessary to use a q u a d r a t i c e x p r e s s i o n i n u). A l s o
Barner and Quinlan (20) t r e a t e d mixtures at high temperatures and
p r e s s u r e s , and Chueh and P r a u s n i t z (21) t r e a t e d the c o m p r e s s i b i l i t y
C
a n d

1.
PITZER
of l i q u i d s . Reid and Sherwood (22) g i v e an e x t e n s i v e t a b l e i n c l u d i n g

a c e n t r i c f a c t o r s as w e l l as c r i t i c a l constants f o r many substances.
On the t h e o r e t i c a l s i d e , one great advance has been i n the
development of p e r t u r b a t i o n t h e o r i e s of a g e n e r a l i z e d van der Waals
type. Here one assumes t h a t the molecular d i s t r i b u t i o n i s d e t e r mined p r i m a r i l y by r e p u l s i v e f o r c e s which can be approximated by
hard cores. Then both the s o f t n e s s of the cores and the a t r a c t i v e
f o r c e s a r e t r e a t e d by p e r t u r b a t i o n methods. Barker and Henderson
(23) have r e c e n t l y reviewed t h e o r e t i c a l advances i n c l u d i n g t h e i r own
outstanding work. Rigby (24) a p p l i e d these modern Van der Waals
methods t o n o n - s p h e r i c a l molecules which represent one type of
molecules w i t h non-zero a c e n t r i c f a c t o r s . I n a somewhat s i m i l a r
manner Beret and P r a u s n i t z (25) developed equations a p p l i c a b l e even
to h i g h polymers and r e l a t e d the i n i t i a l departures from simple
f l u i d s t o the a c e n t r i c f a c t o r .
But i n my view the most e f f e c t i v e approach would concentrate
f i r s t on g l o b u l a r molecules. These could be modeled by K i h a r a potent i a l s w i t h s p h e r i c a l cores or by other p o t e n t i a l s a l l o w i n g the w e l l
to be narrowed. The great advantage would be the r e t e n t i o n of spheri c a l symmetry and i t s t h e o r e t i c a l s i m p l i c i t y . Rogers and P r a u s n i t z
(26) made an important beginning i n t h i s area w i t h c a l c u l a t i o n s based
on K i h a r a models a p p r o p r i a t e f o r argon, methane, and neopentane w i t h
e x c e l l e n t agreement f o r the p r o p e r t i e s s t u d i e d . While they do not
d i s c u s s these r e s u l t s i n terms of the a c e n t r i c f a c t o r , the t r a n s formation of s p h e r i c a l core r a d i u s t o a c e n t r i c f a c t o r i s w e l l
e s t a b l i s h e d (16, 27), Rogers and P r a u s n i t z were a l s o able to t r e a t
mixtures very s u c c e s s f u l l y although those c a l c u l a t i o n s were burdensome even w i t h modern computers. I b e l i e v e f u r t h e r t h e o r e t i c a l work
using s p h e r i c a l models f o r g l o b u l a r molecules would be f r u i t f u l .
The move to an a n a l y t i c a l equation by Lee and K e s s l e r was
undoubtedly a wise one i n view of the marvelous c a p a c i t y of modern
computers to d e a l w i t h complex equations. I would expect f u t u r e work
to y i e l d s t i l l b e t t e r equations.
There remains the q u e s t i o n of the u l t i m a t e accuracy of the
a c e n t r i c f a c t o r concept. How a c c u r a t e l y do molecules of d i f f e r e n t
shapes but w i t h the same a c e n t r i c f a c t o r r e a l l y f o l l o w corresponding
s t a t e s ? Apparently t h i s accuracy i s w i t h i n experimental e r r o r f o r
most, i f not a l l , present data. Thus the a c e n t r i c f a c t o r system
c e r t a i n l y meets engineering needs, and i t i s p r i m a r i l y a matter of
s c i e n t i f i c c u r i o s i t y whether d e v i a t i o n s a r e p r e s e n t l y measurable.
I t has been a pleasure to review these aspects of the " a c e n t r i c
f a c t o r " w i t h you and I look forward to your d i s c u s s i o n of recent
advances i n these and other areas.

Literature Cited
1.
Kemp, J . D. and P i t z e r , K. S., J . Chem. Phys., (1936) 4, 749;

J. Am. Chem. Soc. (1937) 59, 276.
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.
P i t z e r , K. S., J . Chem. Phys., (1937) 5, 469, 473, 752; (1940)

8, 711; Chem. Rev. (1940) 27, 39.
Rossini, F. D., P i t z e r , K. S., Arnett, R. L., Braun, R. M. and
Pimentel, G. C., "Selected Values of the Physical and Thermodynamic Properties of Hydrocarbons and Related Compounds,"
Carnegie Press, Pittsburgh (1953).
Scott, D. W., J . Chem. Phys. (1974) 60, 3144.
P i t z e r , K. S., J . Chem. Phys. (1939) 7, 583.
Rowlinson, J . S., Trans. Faraday Soc. (1954) 50, 647; "Liquids
and Liquid Mixtures," 2nd ed. Chapter 8, Butterworth, London
(1969).
Kihara, T., Rev. Mod. Phys. (1953) 25, 831 and papers there
cited.
P i t z e r , K. S., J . Am. Chem. Soc. (1955) 77, 3427.
Riedel, L., Chem. Ing. Tech. (1954) 26, 83, 259, 679; (1955)
27, 209, 475; (1956) 28, 557.
P i t z e r , K. S., Lippman, D. Z., Curl, J r . , R. F., Huggins, C. M.
and Petersen, D. E., J . Am. Chem. Soc. (1955) 77, 3433.
Benedict, M., Webb, G. B. and Rubin, L. C., J . Chem. Phys.
(1940) 8, 334.
Opfell, J . B., Sage, B. H. and P i t z e r , K. S., Ind. Eng. Chem.
(1956) 48, 2069.
Curl, J r . , R. F., and P i t z e r , K. S., Ind. Eng. Chem. (1958)
50, 265.
P i t z e r , K. S. and Curl, J r . , R. F., J . Am. Chem. Soc., (1957)
79, 2369.
P i t z e r , K. S. and Hultgren, G. O., J . Am. Chem. Soc. (1958)
80, 4793.
Danon, F. and P i t z e r , K. S., J . Chem. Phys. (1962) 36, 425.
Lee, B. I . and Kesler, M. G., A.I.Ch.E. Journal (1975) 21, 510.
Tsonopoulos, C., A.I.Ch.E. Journal (1974) 20, 263.
Lyckman, E. W., Eckert, C. A. and Prausnitz, J . M., Chem. Engr.
S c i . (1965) 20, 703.
Barner, H. E. and Quinlan, C. W., I . and E.C. Proc. Des. Dev.
(1969) 8, 407.
Chueh, P. L. and Prausnitz, J . M., A.I.Ch.E. Journal (1969)
15, 471.
Reid, R. C. and Sherwood, T. K., "The Properties of Gases and
Liquids," 2nd ed., McGraw-Hill Book Co., New York (1966).
Barker, J . A. and Henderson, D., Rev. Mod. Phys. (1976) 48, 587.
Rigby, M., J . Phys. Chem (1972) 76, 2014.
Beret, S. and Prausnitz, J . M., A.I.Ch.E. Journal (1975) 21,
1123.
Rogers, B. L. and Prausnitz, J . M., Trans. Faraday Soc. (1971)
67, 3474.
Tee, L. S., Gotoh, S., and Stewart, W. E., Ind. Eng. Chem. Fund.
(1966) 5, 363.

Acentric Factor

Hochgeladen von

Dokumentinformationen

Copyright

Verfügbare Formate

Dieses Dokument teilen

Dokument teilen oder einbetten

Freigabeoptionen

Stufen Sie dieses Dokument als nützlich ein?

Sind diese Inhalte unangemessen?

Copyright:

Verfügbare Formate

Acentric Factor

Hochgeladen von

Copyright:

Verfügbare Formate

1

Origin of the Acentric Factor

Downloaded by 108.21.206.41 on May 8, 2016 | http://pubs.acs.org

University of California, Berkeley, Calif. 94720

It was a pleasure to accept Dr. Sandler's invitation to open

Downloaded by 108.21.206.41 on May 8, 2016 | http://pubs.acs.org

PHASE EQUILIBRIA AND FLUID PROPERTIES IN CHEMICAL INDUSTRY

Downloaded by 108.21.206.41 on May 8, 2016 | http://pubs.acs.org

Origin of the Acentric Factor

i s much l e s s s p h e r i c a l than neopentane.

PHASE EQUILIBRIA AND FLUID PROPERTIES IN CHEMICAL INDUSTRY

Downloaded by 108.21.206.41 on May 8, 2016 | http://pubs.acs.org

Figure 1. Intermolecular potential for molecules of a simple

Downloaded by 108.21.206.41 on May 8, 2016 | http://pubs.acs.org

Figure 3. Check on family relationship of curves of Figure 2. Comparison of

PHASE EQUILIBRIA AND FLUID PROPERTIES IN CHEMICAL INDUSTRY

w i d e l y measured at l e a s t near the normal b o i l i n g p o i n t . Thus both

w i t h P the reduced vapor pressure a t T = 0.700 seemed convenient,

Downloaded by 108.21.206.41 on May 8, 2016 | http://pubs.acs.org

The preference of P over V as the second independent v a r i a b l e i s

Origin of the Acentric Factor

Downloaded by 108.21.206.41 on May 8, 2016 | http://pubs.acs.org

Figure 4. Intermolecular forces operate

Figure 5. Compressibility factor as a

PHASE EQUILIBRIA AND FLUID PROPERTIES IN CHEMICAL INDUSTRY

reduced temperature and pressure i s p l o t t e d a g a i n s t u). The most

Downloaded by 108.21.206.41 on May 8, 2016 | http://pubs.acs.org

Origin of the Acentric Factor

of l i q u i d s . Reid and Sherwood (22) g i v e an e x t e n s i v e t a b l e i n c l u d i n g

Downloaded by 108.21.206.41 on May 8, 2016 | http://pubs.acs.org

Kemp, J . D. and P i t z e r , K. S., J . Chem. Phys., (1936) 4, 749;

Downloaded by 108.21.206.41 on May 8, 2016 | http://pubs.acs.org

PHASE EQUILIBRIA AND FLUID PROPERTIES IN CHEMICAL INDUSTRY

P i t z e r , K. S., J . Chem. Phys., (1937) 5, 469, 473, 752; (1940)

Das könnte Ihnen auch gefallen