(ACS Symposium Series 329) Thomas G. Squires and Michael E. Paulaitis (Eds.) - Supercritical Fluids. Chemical and Engineering Principles and Applications-American Chemical Society (1987) PDF

Supercritical Fluids
In Supercritical Fluids; Squires, T., et al.;

ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
ACS SYMPOSIUM SERIES 329
Supercritical Fluids
Chemical and Engineering
Principles and Applications
Thomas G. Squires EDITOR
Michael E. Paulaitis, EDITOR

University of Delaware
Developed from a symposium sponsored by

the Division of Fuel Chemistry
at the 190th Meeting
of the American Chemical Society,
Chicago, Illinois,
September 8-13, 1985
American Chemical Society, Washington, DC 1987

Library of Congress Cataloging-in-Publication Data
Supercritical fluids.
( A C S symposium series, ISSN 0097-6156; 329)
"Developed from a symposium sponsored by the
Division of Fuel Chemistry at the 190th Meeting of the
American Chemical Society, Chicago, Illinois,
September 8-13, 1985."
Bibliography: p.
Includes index.
1. Separation (Technology)—Congresses. 2. High
pressures (Technology)—Congresses.
I. Squires, Thomas G . , 1938-
Michael Ε. III. American Chemica
Fuel Chemistry. IV. American Chemical Society.
Meeting (190th: 1985: Chicago,Ill.)V.Series.
TP156.S45S872 1987 660.2'842 86-26480
ISBN 0 - 8 4 1 2 - 1 0 1 0 - 1
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Preface
SCIENTISTS HAVE BEEN AWARE of the novel properties of supercritical

fluids for more than a century Early investigators were fascinated by the
"schizophrenic" behavio
disconcerting but coincidental that research activities also split into two
disparate areas. Fundamental interactions in simple systems were meticu-
lously investigated to correlate and predict phase behavior. At the other
extreme, scientists applied supercritical fluids with Edisonian zeal, seeking
miraculous solutions to complex problems in extraction and fractionation.
The explosion of interest in supercritical fluids during the past decade
has seen a bridging of these extremes, a movement toward balance.
Investigators have sought to understand and develop applications on the
basis of underlying physicochemical principles, and recent reports of semi-
empirical treatment of supercritical solvent properties have shifted these
fluids squarely into the mainstream of chemical research.
We have sought to maintain this balance by probing the principles
underlying supercritical fluid behavior in the first three sections and
examining applications from the perspective of these principles in the last
three sections. Within each section, there is also a flow from fundamentals
to applications; the initial chapter provides the basis and the focus for
ensuing chapters.
The first section features new approaches to investigating physico-
chemical properties. Its final two chapters facilitate the transition to the
second section, on chemical reactions, a new topic of fundamental
importance. Phase equilibria are described in thefinalsection of principles.
Here initial chapters are devoted to modeling, and thefinalchapters report
solubility studies. The final three sections are devoted to important
applications of supercritical fluids: chromatography, fractionation and
separation, and fuel applications. The chapters in each of these sections are
also arranged so that there is a transition to more applied topics in the later
chapters.
The contributions to this volume are representative of the exciting
work under way in supercritical fluid research and attest that there is still
much to be done. It is clear that there are abundant opportunities for
ix

enhancing our understanding of supercriticalfluidbehavior and extending
the useful application of their properties.
1
THOMAS G . SQUIRES
Ames Laboratory
Iowa State University
Ames, IA 50011
MICHAEL E. PAULAITIS
Department of Chemical Engineering
University of Delaware
Newark, DE 19716
August 28, 1986
1
Current address: Associated Western Universities, 142 East 200 South,
Suite 200, Salt Lake City, UT 84111

Chapter 1
Effect of Critical Phenomena on Transport Properties

in the Supercritical Region
Es. Gulari, H. Saad, andY.C.Bae
Department of Chemical and Metallurgical Engineering, Wayne State University,

Detroit,MI48202
The transport properties of supercritical fluid mixtures

are strongly affecte
f i r s t step in testin
range of the existing theories of c r i t i c a l phenomena, we
have used photon correlation spectroscopy to measure the
decay rate of density fluctuations in dilute supercritical
solutions of heptane, benzene, and decane in CO . The 2
results along c r i t i c a l isochores were analyzed in terms of

the mode-coupling and the dynamic renormalization-group
theories. The values of v, the temperature exponent of
the size of the fluctuations, were in very good agreement
with its ideal value. The relative magnitudes of the
background contributions in different systems indicated
the effects of molecular diffusion and solute-solvent
interactions.
I n t r o d u c t i o n and Background
In supercritical extraction, the dissolution step is
diffusion-controlled and t h e t r a n s p o r t properties o f the
supercritical phase govern the rate o f extraction. Due to
difficulties i n measuring time-dependent phenomena at high
p r e s s u r e s , t h e r e a r e v e r y few d a t a and t h e r e f o r e t h e r e i s a need
f o r e x p e r i m e n t a l i n v e s t i g a t i o n s o f t r a n s p o r t p r o p e r t i e s o f dense
s u p e r c r i t i c a l f l u i d s which c a n be c o r r e l a t e d f o r u s e i n p r a c t i c a l
a p p l i c a t i o n s (1, 2 ) .
The s u p e r c r i t i c a l phase i s a s o l u t i o n o f h i g h l y asymmetric
components, e.g., CO and a h y d r o c a r b o n , a t t e m p e r a t u r e s and
p r e s s u r e s v e r y c l o s e t o t h e c r i t i c a l p o i n t o f the s o l u t i o n . F o r
example, f o r p u r e CO , Τ = 31°C and Ρ = 7.3 MPa, b u t f o r a
(
m i x t u r e o f CO w i t h 2 mol \ benzene, Τ = 3 9 . 3 ° C and Ρ = 8 . 1 MPa,
0
and f o r a m i x t u r e o f C 0 w i t h 2 mol % Secane, Τ = 4 6 . 8 C a n d P =
2 Q c
8.9 MPa. T h e r e f o r e , f r e q u e n t l y a p r o c e s s o p e r a t i n g a t 40 C and a t

a c e r t a i n pressure i n order t o a t t a i n a given s o l u b i l i t y i s c l o s e
to a c r i t i c a l l i n e o r surface.
In t h e v i c i n i t y o f a c r i t i c a l p o i n t , even a t e q u i l i b r i u m ,
domains o f d i f f e r e n t density o r concentration exist i n a f l u i d .
0097-6156/87/0329-0002$06.00/0
© 1987 American Chemical Society

1. GULARI ET AL. Critical Phenomena in the Supercritical Region 3
These fluctuations, which are r e f e r r e d t o as order-parameter

f l u c t u a t i o n s i n s t u d i e s o f c r i t i c a l phenomena ( 3 ) , comprise t h e
d r i v i n g f o r c e s f o r t r a n s p o r t i n t h e system. For l i q u i d mixtures
near a c r i t i c a l m i x i n g p o i n t , t h e o r d e r parameter i s c o n c e n t r a t i o n ,
and f o r pure gases n e a r t h e v a p o r - l i q u i d c r i t i c a l p o i n t , t h e o r d e r
parameter i s density. F o r gas m i x t u r e s such as supercritical
s o l u t i o n s near t h e c r i t i c a l l i n e , t h e o r d e r parameter i s a g a i n
density, which is a function of c o m p o s i t i o n and temperature
compared t o a pure gas where d e n s i t y i s a function of only
temperature a t c o n s t a n t p r e s s u r e .
These fluctuations manifest themselves as optical
i n h o m o g e n e i t i e s i n t h e f l u i d which can be most e a s i l y d e t e c t e d by
light scattering techniques (4). Relatively f a r away from a
c r i t i c a l point, Τ - Τ ~ 10 C, t h e c h a r a c t e r i s t i c s i z e s o f domains
are ~ 1 nm and t h e y grow t o s 100 nm i n t h e immediate v i c i n i t y o f a
c r i t i c a l point, Τ - Τ < 1°C. I f t h e domains a r e comparable t o o r
less than the visible wavelengths and the refractive index
increment i s a p p r e c i a b l e
ideal nonintrusive probes
s u p e r c r i t i c a l s o l u t i o n s two t y p e s o f experiments can be performed,
namely t h e t i m e - a v e r a g e d i n t e n s i t y measurements t o d e t e r m i n e t h e
magnitude o f the order-parameter fluctuations and the Photon
C o r r e l a t i o n S p e c t r o s c o p y (PCS) t o measure t h e i r decay r a t e .
The order-parameter fluctuations are temperature- and
system-dependent and t h e i r decay r a t e i s r e l a t e d t o t h e t r a n s p o r t
coefficients (5). U s u a l l y t h e magnitude o f t h e f l u c t u a t i o n s a r e
c h a r a c t e r i z e d by a c o r r e l a t i o n length ξ . Along a critical
i s o c h o r e o r i s o p l e t h , t h e c o r r e l a t i o n l e n g t h d i v e r g e s as
where ε = (Τ - Τ )/T , ξ 0 i s a system-dependent a m p l i t u d e and V=

0.63 i s a u n i v e r s a l exponent.
The decay rate of the order-parameter fluctuations is
p r o p o r t i o n a l t o t h e t h e r m a l d i f f u s i v i t y i n c a s e o f pure gases near
the v a p o r - l i q u i d c r i t i c a l p o i n t and i s p r o p o r t i o n a l t o t h e b i n a r y
d i f f u s i o n c o e f f i c i e n t i n case o f l i q u i d m i x t u r e s near t h e c r i t i c a l
m i x i n g p o i n t _(6J_. R e c e n t l y , we r e p o r t e d (7) s i n g l e - e x p o n e n t i a l
decay rate of the order-parameter fluctuations in dilute
s u g e r c r i t i c a l s o l u t i o n s o f l i q u i d h y d r o c a r b o n s i n C0_ f o r Τ - T^ <
10 C. T h i s i m p l i e d t h a t the time s c a l e s a s s o c i a t e d w i t h t h e r m a l
d i f f u s i o n and mass d i f f u s i o n a r e s i m i l a r i n t h e s e systems.
The mode-coupling theory £8^ and the dynamic
r e n o r m a l i z a t i o n - g r o u p t h e o r y (9) a r e t h e two t h e o r e t i c a l approaches
f o r t h e i n t e r p r e t a t i o n o f t h e decay r a t e o f t h e o r d e r - p a r a m e t e r
fluctuations. The mode-coupling t h e o r y y i e l d s a r e l a t i o n among the
decay rate or the t r a n s p o r t coefficient, the v i s c o s i t y , the
c o r r e l a t i o n l e n g t h , and t h e temperature o f t h e system. The dynamic
r e n o r m a l i z a t i o n - g r o u p t h e o r y p r e d i c t s how transport coefficients
w i l l d i v e r g e o r converge on v a r i o u s paths o f approach t o t h e
c r i t i c a l point.
The t r a n s p o r t p r o p e r t i e s o f a n e a r - c r i t i c a l system c o n t a i n an
enhancement o r a r e d u c t i o n due t o c r i t i c a l f l u c t u a t i o n s i n a d d i t i o n
t o t h e c o n t r i b u t i o n s o f m o l e c u l a r t r a n s p o r t p r o c e s s e s which a r e
strictly a f u n c t i o n o f t h e thermodynamic s t a t e . T h e r e f o r e , the
transport coefficients in the critical region are usually

4 SUPERCRITICAL FLUIDS
p a r t i t i o n e d i n t o a c r i t i c a l p a r t and a background which c o r r e s p o n d s

t o the v a l u e o f the t r a n s p o r t c o e f f i c i e n t extrapolated from a
r e g i o n f a r away from the c r i t i c a l p o i n t ( 1 0 ) . The b i n a r y d i f f u s i o n
c o e f f i c i e n t can be e x p r e s s e d as D = L/χ , where L i s mass
c o n d u c t i v i t y and χ = ( δ ΰ / δ μ ) ^ , the c h e m i c a l p o t e n t i a l d e r i v a t i v e
of concentration. Then L can be w r i t t e n as
= 1 AL D = t/y AD (2)
where ÎI, t , and AL, A D denote the background and the c r i t i c a l

contributions respectively. The p r e d i c t i o n o f t h e mode-coupling
theory for AD is
A D = k T / ( 6 i r ηζ
B )Ω(ςξ ) (3)
where kg i s Boltzmann's c o n s t a n t , η is viscosity, q = 2q sin(9/2), o
with q and θ b e i n g the wave number o f the i n c i d e n t l i g h t and the

s c a t t e r i n g angle. In
u n i v e r s a l dynamic s c a l i n
The effect of the background contributions are quite
s i g n i f i c a n t f o r gases and must be d e t e r m i n e d ( 3 ) . Unfortunately,
d i f f u s i v i t y d a t a a t h i g h e r temperatures and s u p e r c r i t i c a l p r e s s u r e s
are not available for mixtures of h y d r o c a r b o n s w i t h CO^ and
therefore there i s no easy way of estimating the background
contribution independently. Using the scaling prediction for
ε-dependence o f (δϋ/δμ) , we i n t r o d u c e d the temperature dependence
o f the background term i n the f o l l o w i n g form:
Î)=ï/X =A/ V
(4)
where A i s a system-dependent a m p l i t u d e which can be t r e a t e d as a

c o n s t a n ? over the temperature range o f our measurements.
A f t e r s u b s t i t u t i n g the background and the c r i t i c a l terms from
e q u a t i o n s 3 and 4 i n t o e q u a t i o n 2, the d i f f u s i o n c o e f f i c i e n t i n the
s u p e r c r i t i c a l r e g i o n i s g i v e n by
D = A^ ^ 2
kgT/(6ττηξ ) (5)
The above e q u a t i o n p r o v i d e s a basis for correlating the

temperature dependence o f a t r a n s p o r t c o e f f i c i e n t such as mass
diffusivity in the supercritical region. The effects of
composition, solute, and solvent c h a r a c t e r i s t i c s can also be
introduced into the correlations via ξ and A which are
system-dependent a m p l i t u d e s . However, a r i g o r o u s %est of the
a p p l i c a b i l i t y o f e q u a t i o n 5 r e q u i r e s independent measurements o f
the decay r a t e o f t h e o r d e r - p a r a m e t e r f l u c t u a t i o n s , the c o r r e l a t i o n
l e n g t h , and the v i s c o s i t y .
In t h i s s t u d y , we employed PCS t o measure the decay r a t e o f
the o r d e r - p a r a m e t e r f l u c t u a t i o n s i n d i l u t e s u p e r c r i t i c a l s o l u t i o n s
o f heptane, benzene, and decane i n CO^. The r e f r a c t i v e index
increment w i t h c o n c e n t r a t i o n i s much l a r g e r t h a n the r e f r a c t i v e
index increment w i t h temperature i n t h e s e systems. T h e r e f o r e the
order-parameter fluctuations detected by light scattering are
r s
mainly concentration fluctuations and t h e i r decay rate^ *
p r o p o r t i o n a l t o the b i n a r y d i f f u s i o n c o e f f i c i e n t , D = Γ/q . The

r e s u l t s a l o n g c r i t i c a l i s o c h o r e s were a n a l y z e d i n terms o f e q u a t i o n
5. The v a l u e s o f t h e exponent ν and t h e s i g n i f i c a n c e o f t h e
background term a r e d i s c u s s e d .
Experimental
The l i g h t - s c a t t e r i n g s p e c t r o m e t e r was s i m i l a r t o t h e one d e s c r i b e d
i n a p r e v i o u s paper ( 1 1 ) . The d e s i g n o f t h e h i g h - p r e s s u r e c e l l
a l l o w e d t h e range o f t h e s c a t t e r i n g a n g l e s t o be 6-11 degrees w i t h
homodyne d e t e c t i o n . The sample c e l l was machined out o f a s o l i d
b r a s s b l o c k , f i t t e d w i t h f l a n g e d 1.25 cm t h i c k q u a r t z windows, and
t e s t e d up t o 20 MPa. The o p t i c a l p a t h l e n g t h o f t h e c e l l was 7 cm.
The i n s i d e s u r f a c e s o f t h e c e l l were b l a c k e n e d and a r e d g l a s s tube
was i n s e r t e d i n t o t h e c e l l t o absorb t h e r e f l e c t e d l i g h t . The c e l l
was f i t t e d i n t o a b r a s s j a c k e t . The temperature o f t h e c i r c u l a t i n g
water i n t h e j a c k e t was c o n t r o l l e d w i t h i n 0.002 C i n two s t e p s by
u s i n g a N e s l a b RTE-8 c i r c u l a t i n g b a t h and T r o n a c PTC40 t e m p e r a t u r e
controller i n series. The temperature was measured by a t h e r m i s t o r
embedded i n t h e c e l l b l o c k
D y n i s c o Model PT520-5M p r e s s u r
reproducibility of whic ,
respectively.
The amounts o f t h e h y d r o c a r b o n and CO^ charged i n t o t h e c e l l
were d e t e r m i n e d gravimetrically. For a fixed amount o f the
h y d r o c a r b o n , t h e CO^ charge was a d j u s t e d c a r e f u l l y so t h a t t h e
r e l a t i v e amounts o f t h e l i q u i d and gas phases were e q u a l as t h e
system c r o s s e d from t h e two-phase r e g i o n t o t h e dense gas r e g i o n .
Then t h e p r o c e s s was r e v e r s e d t o check whether t h e meniscus
appeared a t t h e c e n t e r p o s i t i o n o f t h e c e l l . Based on t h e v a l i d i t y
o f t h e law o f r e c t i l i n e a r d i a m e t e r , t h i s p r o c e d u r e e n s u r e d such a
l o a d i n g t o be v e r y c l o s e t o t h e c r i t i c a l p o i n t o f t h e m i x t u r e .
R e s u l t s and D i s c u s s i o n
C o r r e l a t i o n f u n c t i o n measurements were made a l o n g f o u r critical
isochores for each of the three systems: CO^-n-heptane,
C0 -benzene, and CO^-n-decane.
2 The c r i t i c a l d e n s i t i e s and t h e
c o r r e s p o n d i n g c o m p o s i t i o n s a r e p l o t t e d i n F i g u r e 1. The t h r e e
h y d r o c a r b o n s i n o r d e r o f h i g h e r t o lower s o l u b i l i t y i n CCL were
heptane, benzene, and decane. The measured b i n a r y diffusion
c o e f f i c i e n t s o r t h e decay r a t e s o f t h e o r d e r - p a r a m e t e r f l u c t u a t i o n s
at v a r i o u s temperatures and p r e s s u r e s a r e l i s t e d i n T a b l e s I, I I ,
and I I I f o r C0 -heptane,
2 C0 -benzene,
2 and C0 -decane
2 systems
respectively. In F i g u r e 2, t h e c r i t i c a l l i n e s o f the t h r e e b i n a r y
systems i n the dilute hydrocarbon range are shown in the
p r e s s u r e - t e m p e r a t u r e space. dP/dT a l o n g t h e c r i t i c a l lines of
CO -heptane and CO -benzene systems a r e s i m i l a r and lower t h a n
dP/dT a l o n g t h e c r i t i c a l l i n e o f C 0 - d e c a n e system, which i n d i c a t e s
2
that C0 2 and decane form more asymmetric m i x t u r e s r e l a t i v e t o C 0 2
w i t h heptane o r benzene.
The measured decay r a t e s were a n a l y z e d i n terms o f e q u a t i o n 5,
which becomes
2 ν
Γ/q = A ^ ' + ( k B T / 6 ^ )ε (6)
when t h e temperature dependence o f ξ i s substituted i n . η was

taken t o be t h e v i s c o s i t y o f pure CO evaluated at the system

6n
Ο
X
ο
s
ci / /
Ε
ο
ο Η / /
—• ^""'"7—
0.45 0.47 0.4
Critical Density
F i g u r e 1: P l o t o f the hydrocarbon content of v a r i o u s mixtures

versus t h e i r c r i t i c a l d e n s i t i e s . Triangles, circles,
and s q u a r e s denote heptane-, benzene-, and decane-CO^
solutions respectively. The s o l i d c i r c l e marks t h e
c r i t i c a l d e n s i t y o f pure CO .
10 π
9H
S.
300 310 320 ~530

τ (°κ)
F i g u r e 2: The c r i t i c a l l i n e s o f h e p t a n e - C 0 ( t r i a n g l e s ) , benzene-
2
CO ( c i r c l e s ) , and d e c a n e - C 0 ( s q u a r e s ) systems.
2 The
s o l i d c i r c l e marks t h e c r i t i c a l t e m p e r a t u r e and p r e s s u r e
o f p u r e CO .

1. GULARI E T AL. Critical Phenomena in the Supercritical Region 1
2
T a b l e I: Measured Γ/q a t V a r i o u s Temperatures and P r e s s u r e s :
CO -Heptane System
2 5 2
T(°C) P(MPa) Γ/q · 10 (cm /s)
3
94. 4 mol % C 0 , o p,= 0.561 g/cm
Τ = (53. 31 + 0 . 0 2 ) °c, Ρ = 9. 2411Pa
53. 74 c 9. 29 c 1. 03 + 0.03
54. 12 9. 35 1. 30 + 0.02
54. 76 9. 45 1. 52 ± 0.02
55. 58 9. 57 1. 92 + 0.02
56. 69 9. 75 2. 49 + 0.03
58. 15 9. 97 3. 39 + 0.04
60. 76 10. 41 4. 71 + 0.04
63, 39 10. 84 5. 96 + 0.05
3
95. 8 mol % CO P= 0.544 g/cm
Τ (50. 14 +
50. 61 c
50. 90 9. 07 1. 28 + 0.02
51. 57 9. 18 1. 63 + 0.02
52. 18 9. 27 2. 13 + 0.02
52. 72 9. 37 2. 40 + 0 . 0 2
53. 65 9. 52 3. 02 + 0.02
54. 38 9.,64 3.,52 + 0.03
55. 45 9.,83 4., 16 + 0.03
56. 52 10.,01 4.,83 + 0.05
57. 98 10.,26 5.,62 + 0.05
59. 98 10.,61 6,,74 + 0.07
3
96,.9 mol % CO P = 0.538 c g/cm
Τ (44..24 + 0.02) °c, Ρ = 8.,46 MPa
Z
44.,49 c 8..50 c 0.,74 + 0.01

44.,94 8..57 1..16 + 0.01
45.,36 8..64 1..48 + 0.01
46.,37 8..79 2..25 + 0.01
47. 70 8..96 2..97 + 0.02
48..47 9..08 3..61 + 0.02
49..52 9,.25 4,.41 + 0.02
50..95 9,.49 5,.33 + 0.03
52..48 9,.74 6,.36 + 0.06
54..31 10..04 7,.51 + 0.05
3
98 .1 mol % CO 0^= 0.525 g/cm
Τ (39 .13 + 0 . 0 1 ) °c, Ρ = 8,
.00 MPa
39..43 c 8 .05 c 1 .13 + 0.02
40,.15 8 .17 1 .83 + 0.02
41,. 11 8 .32 2 .71 + 0.02
42 .26 8 .51 3 .78 + 0.02
43 .51 8 .74 4 .81 + 0.03
45 . 14 9 .00 6 .17 + 0.05
47 .64 9 .33 7 .71 + 0.05
49 . 12 9 .57 8.82 + 0.05

Table I I : Measured Γ/q a t V a r i o u s Temperatures and P r e s s u r e s :

CO -Benzene System
2 5 2
Τ (°C) P(MPa) Γ/q · 10 (cm /s)
95. 5 mol % CO , ffc= 0.579 g/cm 3
Τ (48.48 + 0 . 0 2 ) °C Ρ = 8. 78 MPa
48. 81 c 8.86 c 0. 88 + 0.04
49. 37 8. 95 1. 32 + 0.03
49. 98 9. 05 1. 87 + 0.03
50. 64 9.,16 2. 34 + 0.03
51. 15 9. 22 2. 84 + 0.03
52. 76 9. 51 4. 03 + 0.02
54. 38 9. 82 5. 02 + 0.04
56. 57 10. 19 6. 69 + 0.03
58. 19 10. 48 7. 58 + 0.05
96. 8 mol % C
Τ (45.,98
46. 00 c 8. 62 c
1.12 + 0.03
46. 72 8. 69 1. 24 + 0.03
48. 56 8. 84 2. 39 + 0.03
49. 29 8. 95 2. 87 + 0.03
50.03 9.,06 3. 38 + 0.02
51. 25 9. 22 4. 30 + 0.02
52. 29 9. 35 4. 98 + 0.02
53. 36 9.,50 5. 84 + 0.04
54.,41 9.,64 6. 61 + 0.05
55.,97 9.,85 7. 78 + 0.05
3
97. 9 mol % CO., P = 0.546 g/cm
c
Τ (39,.30 + 0. 02) °C Ρ = 8.,06 MPa

39.,40 c 8..08 c 0. 99 + 0.03
39. 51 8..10 1. 19 + 0.02
39..79 8..15 1. 34 + 0.02
40..08 8..19 1. 65 + 0.03
40..48 8..23 1. 95 + 0.03
41. 25 8..31 2. 51 + 0.02
44..00 8..70 5. 40 + 0.02
46..96 9..08 8. 18 + 0.02
49..34 9..32 10. 0 + 0.10
51..74 9,.56 12. 3 + 0.10
98..6 mol % CO , Ρ = 0.533 g/cm 3
Τ = (36 .31 + 0. 02) °c, Ρ = 7,.78 MPa

Z
36..56 c 7,.82 c 1. 05 + 0.02

37,.12 7,.91 1.,72 + 0.02
37,.63 8,.00 2.,28 + 0.02
38,.48 8,.14 3.,18 + 0.03
39,.48 8 .28 4.,20 + 0.02
41,.14 8 .55 5.,82 + 0.04
43,.03 8 .84 7. 62 + 0.04
46,.32 9 .35 10..45 + 0.05

1. GULARI ET AL. Critical Phenomena in the Supercritical Region
2
Table I I I : Measured Γ/q a t V a r i o u s Temperatures and P r e s s u r e s :
CO^-Decane System
2 5 2
Τ (°C) P(MPa) Γ/q · 10 (cm /s)
Τ = mol
97.2 (50.22 + 0 . 0 3 ) C, Ρ
% CO., ρ = MPa
= 9.61 0.607 g/cm 3
50.31 C
9.63 C
0. 80 ± 0. 06
50.77 9.70 0. 99 ± 0. 04
51.02 9.75 1. 15 ± 0. 02
51.42 9.84 1. 37 ± 0. 02
52.42 10.06 1. 76 ± 0. 02
53.56 10.26 2. 14 ± 0. 03
54.34 10.39 2. 50 ± 0. 02
55.15 10.56 2. 80 ± 0. 02
56.60 10.86 3. 32 ± 0. 03
57.88 11.12 3. 83 ± 0. 04
59.29 11.4
59.88 11.5
3
97.9 mol % CO , p„ 592 g/cm
Τ = (45.95 ± 0 . 0 3 ) °C, Ρ = 8 . f t MPa
46.20 C
9.91 C
0. 86 ± 0.,04
46.65 9.27 1. 10 ± 0.,01
47.59 9.37 1. 40 ± 0.,01
48.28 9.52 1. 62 ± 0.,02
49.94 9.81 2. 52 ± 0. 02
51.42 10.10 3. 11 ± 0.,06
52.84 10.37 3. 78 ± 0.,06
55.50 10.88 4. 80 ± 0., 10
3
99.0 mol % CO , P = 0.^564 g/cm
c
Τ = (43.05 ± 0 . 0 2 ) °C, Ρ = 8.73 MPa

43.38 C
8.77 C
1. 15 ± 0,.02
44.32 8.95 1. 76 ± 0,.02
45.30 9.09 2. 30 ± 0,.02
46.33 9.29 2. 97 ± 0,.02
48.35 9.55 3. 78 ± 0,.05
50.06 9.86 4. 86 ± 0,.05
51.44 10.12 5. 63 ± 0,.06
52.83 10.37 6. 40 ± 0 .10
3
99.6 mol % CO , P = 0.537 g/cm
c
Τ = (35.86 ± 0 . 0 2 ) °C, Ρ = 7.82 MPa

C C
35.99 7.84 1.01 ± 0.02
36.35 7.91 1.35 ± 0.02
36.85 8.00 1.80 ± 0.02
37.71 8.14 2.61 ± 0.04
38.75 8.32 3.64 ± 0.03
39.81 8.51 4.52 ± 0.02
40.99 8.71 5.66 ± 0.09
42.31 8.95 6.73 ± 0.12
45.60 9.28 9.00 + 0.10

density using η = 42.58p+ 661.7p + 82.89p + 152 + 1 2 5 G from

r e f e r e n c e £ 3 ) . . I n t h e f i r s t p a r t o f t h e a n a l y s i s , t h e background
1
c o n t r i b u t i o n was n e g l e c t e d and a two-parameter f i t f o r V and
was performed. In t h e second p a r t , v f
was f i x e d a t 0 . 6 7 and t h e
background term was i n c l u d e d . A g a i n a two-parameter f i t f o r A and
ξ 0 was performed. The r e s u l t s a r e summarized i n T a b l e IV.
When t h e background term was n e g l e c t e d , we o b t a i n e d V = 0 . 7 1 1
+ 0 . 0 4 f o r heptane i n CO , V 1
= 0 . 7 6 + 0 . 0 5 f o r benzene i n CO , and
v' = 0.66 + 0.05 f o r decane in C0 - 2 We have denoted t h e
temperature exponent o f t h e c o r r e l a t i o n l e n g t h V i n equation 6
1
f
i n s t e a d o f v , and v v a l u e s s h o u l d be compared t o a u n i v e r s a l v a l u e
of 0 . 6 7 i n s t e a d o f 0 . 6 3 because i n o u r a n a l y s i s v ' i n c l u d e s t h e
ξ-dependence o f t h e v i s c o s i t y . When we used t h e background
v i s c o s i t y 9f f o r pure C O ^ , we d i d n o t t a k e i n t o account t h e weak
2
d i v e r g e n c e o f v i s c o s i t y which i s η α ξ , where z i s a u n i v e r s a l
exponent. In f a c t , there i s a p o s t u l a t e t h a t the v i s c o s i t y r a t i o
η /η e x h i b i t s a power-law b e h a v i o r as
η =îf (Q ξ )
and Q, which i s a system-dependent amplitude, i s r e l a t e d t o t h e

background contribution of the c o n d u c t i v i t y t (12). I f the
d i v e r g e n c e o f t^he . v i s c o s i t y ^ i s .taken i n t o account, Δ ϋ s h o u l d go t o
z e r o as ξ εor ^ . The t h e o r e t i c a l p r e d i c t i o n f o r z
i s 0 . 0 5 and t h e e x p e r i m e n t a l l y determined v a l u e f o r CO i s 0 . 0 5 6 +
0.005 ( 1 3 ) . Therefore, ν ' = v ( 1 . 0 6 ) = 0 . 6 7 .
S t i l l s l i g h t l y higher ν' v a l u e s c a n be a t t r i b u t e d t o t h e
e f f e c t s o f i m p u r i t i e s on t h e c r i t i c a l exponents which were a n a l y z e d
on g e n e r a l grounds by F i s h e r ( 1 4 ) . When t h e p e r t u r b e d critical
point o f a pure species i s studied at a constant impurity
c o n c e n t r a t i o n x, t h e r e n o r m a l i z a t i o n o f t h e c r i t i c a l exponents i s
expected. F o r example, ν g o v e r n i n g t h e temperature v a r i a t i o n o f ζ
when χ = 0 becomes n o r m a l i z e d t o ν == v / ( l - a ) . a i s t h e
temperature exponent o f t h e s p e c i f i c heat and t h e t h e o r e t i c a l and
experimental predictions f o r α give ~ 0.1. I f the d i l u t e
hydrocarbon c o n t e n t i n o u r systems were t r e a t e d as an i m p u r i t y
p e r t u r b i n g t h e c r i t i c a l p o i n t o f pure CO , ν ' would have t o be
n o r m a l i z e d t o ν' = v ' / ( l - a ) o r ν' = 0 . b 7 / 0 . 9 = 0 . 7 4 . The new
v a l u e o f ν ' s h o u f d become e v i d e n t o n l y f o r Τ - Τ < ΔΤ where t h e
c χ
c r o s s o v e r temperature Δ Τ becomes s m a l l e r w i t h x'and v a n i s h e s as χ
tends t o z e r o . A l t h o u g h îhere i s n ' t an easy way f o r c a l c u l a t i n g
Δ Τ , i t i s expected t o v a r y as a h i g h power, such as 1/α ~ 1 0 , o f
t h e c o n c e n t r a t i o n x. P r i m a r i l y f o r CO^-benzene systems and a l s o
f o r CO -heptane systems we o b s e r v e d ν 1
v a l u e s which were l a r g e r
than the i d e a l ν ' value. T h i s was i n q u a l i t a t i v e agreement w i t h
the renormalization of the c r i t i c a l exponents a t c o n s t a n t x,
p a r t i c u l a r l y i f the hydrocarbon c o n t e n t i n v a r i o u s systems was
taken into account. The maximum benzene and heptane content
d i s s o l v e d i n CO was 5 mol %, whereas t h e maximum decane c o n t e n t i n
CO was 2 . 8 moi %. However, t h e a c c u r a c y o f o u r measurements i s
not s u f f i c i e n t and t h e temperature and c o m p o s i t i o n ranges a r e n o t
wide enough t o determine t h e changeover from t h e i d e a l power-law
b e h a v i o r t o t h e r e n o r m a l i z e d power-law b e h a v i o r q u a n t i t a t i v e l y .
The r e l a t i v e magnitudes o f t h e background c o n t r i b u t i o n s f o r
a t
the three systems were e v a l u a t e d by f i x i n g ν' 0 . 6 7 and

T a b l e IV: V a l u e s o f Parameters O b t a i n e d
from T h e o r y o f C r i t i c a l F l u c t u a t i o n s
1
Without Background y f i x e d a t 0.67
f
ξ' χ 10 cm v ξ' χ 10° cm Α χ 10 (cm / s )
ο ο
System: CO^-n-Heptane
98.1 m o l % CO 0.68 + 0.06 0.69 _+ 0.02 0.76 + 0.04 0.51 + 0.15

p = 0.525 g/cm
c
96.9 m o l % CO 0.60 + 0.07 0.76 + 0.03 1.09 + 0.08 1.80 + 0.25

p = 0.538 g/cm
c
95.8 m o l % CO 0 . 7 9 + 0.07
3 0.71 + 0.02 1.06 + 0.06 1.09 + 0.20
p =
0.544 g/cm
c
94.4 mol% CO 0 . 9 8 + 0.17

3 0.68 + 0.04 1.10 + 0.13 0.48 + 0.20
p = 0.561 g/cm
c
System: CO^-Benzene
98.6 mol% CO 0.53 + 0.04 0.72 + 0.02 0.74 + 0.02 2.07 + 0.14
p = 0.533 g7cm
c
0 4 4
97.9 m o l % CO 3 · ± 0-07 0.75 + 0.04 0.76 + 0.09 2.23 + 0.54
p = 0.546 g7cm
c
96.8 m o l % CO 0.42 + 0.11 0.85 + 0.07 1.21 + 0.03 2.95 + 0.07

P = 0.559 g/cm
c
95.5 m o l % CO 0.58 + 0.05 0.74 + 0.02 0.92 + 0.01 1.17 + 0.05

P = 0.579 g/cm"
c
System: CO^-n-Decane
99.6 m o l % CO 0.62 + 0.08 0.69 + 0.03 0.73 + 0.02 0.82 + 0.11

Ρ = 0 . 5 3 7 g7cm
&
c
99.0 m o l % CO 0.91 + 0.19 0.67 + 0.04 0.95 + 0.12 0.23 + 0.55

Ρ = 0 . 5 6 4 g7cm
& /
c
97.9 m o l % C 0 1 . 1 6 ± 0.28 0.67 + 0.05 1.23 + 0.18 0.50 + 0.52

1
o 0
ρ = 0.592 g/cm 3
c
97.2 m o l % CO 1.60 + 0.17 0.59 + 0.02 1.02 + 0.02 -0.82 + 0.05

Ρ = 0 . 6 0 7 g/cm

determining the corresponding values o f A and ξ which a r e a l s o

listed i n Table IV. The background contribution was more
s i g n i f i c a n t f o r benzene i n CO^ than heptane and decane i n CO^. The
r e l a t i v e c o n t r i b u t i o n s t o t h e background and t h e c r i t i c a l p a r t o f
t h e decay r a t e a r e shown i n F i g u r e s 3 and 4 aông two i s o c h o r e s , a
benzene-CO isochore with p =c 0.546 g/cm and a decane-C0 2
5
i s o c h o r e w i t h ρ = 0.592 g/cm r e s p e c t i v e l y , which were a t t h e same
o v e r a l l composition. A l o n g any c r i t i c a l i s o c h o r e t h e background
c o n t r i b u t i o n i s l a r g e s t f o r d a t a p o i n t s f a r t h e s t away from the
c r i t i c a l p o i n t . F o r t h e benzene-CO m i x t u r e shown i n F i g u r e 3, t h e
background amounts t o about 25% ot t h e t o t a l decay r a t e a t about
10 C away from t h e c r i t i c a l p o i n t and d i m i n i s h e s as t h e c r i t i c a l
p o i n t i s approached. However, f o r t h e decane-CO m i x t u r e shown i n
F i g u r e 4, t h e background c o n t r i b u t i o n i s s m a l l e r a t t h e same
temperature d i s t a n c e to t h e c r i t i c a l p o i n t and amounts t o about 10%
of t h e t o t a l decay r a t e . The d i f f e r e n t background c o n t r i b u t i o n s
f o r t h e t h r e e s o l u t e s can be e x p l a i n e d as f o l l o w s : S i n c e benzene
i s t h e most compact s o l u t
would expect t h e d i f f u s i o
f a s t e r , r e s u l t i n g i n t h e h i g h e r v a l u e f o r t h e background term. On
t h e same b a s i s , t h e d i f f u s i o n o f heptane s h o u l d be f a s t e r t h a n
decane and hence y i e l d a h i g h e r A f o r heptane t h a n decane.
In our a n a l y s i s ξο i s a f i 8 t e d parameter. I t i s r e l a t e d to
i n t n e
ξ i n ecgiation 1 by = ^ Q · Values of ξ ο
Q range
1.8 χ 10 t o 1.2 χ 10 cm were°obtgined from t h e f i t s and a r e i n
f a i r agreement w i t h ξ = 1.5 χ 10 cm r e p o r t e d f o r pure CO^ i n
t h e l i t e r a t u r e (3) and i n d i c a t e s t h a t Q i s an a m p l i t u d e o f o r d e r
1
one. In t h e l i m i t e d c o m p o s i t i o n range o f t h i s s t u d y , ζ appeared
to i n c r e a s e w i t h the hydrocarbon content i n the mixture. ξ can
be i n d e p e n d e n t l y determined from t u r b i d i t y measurements ( 1 5 ^ and
t h e s e measurements a r e i n p r o g r e s s and w i l l e n a b l e us t o d e t e r m i n e
t h e c o m p o s i t i o n dependence o f ξ and t h e r e l a t i o n between Q and A
quantitatively. °
Independent measurements o f t h e v i s c o s i t y , t h e decay r a t e , and
t h e c o r r e l a t i o n l e n g t h f o r t h e same f l u i d a r e n e c e s s a r y i n o r d e r t o
t e s t t h e t h e o r y o f c r i t i c a l f l u c t u a t i o n s and determine i t s range o f
v a l i d i t y i n s u p e r c r i t i c a l f l u i d mixtures. As a f i r s t s t e p , we have
measured the decay r a t e o f d i l u t e m i x t u r e s o f t h r e e hydrocarbons
with C0 . ? The results showed t h a t t h e c r i t i c a l fluctuations
dominatea t h e o v e r a l l t r a n s p o r t p r o c e s s e s w i t h i n a 10 C d i s t a n c e t o
the critical p o i n t of a mixture. The size of the critical
f l u c t u a t i o n s d e s c r i b e d by t h e c o r r e l a t i o n l e n g t h ξ decayed w i t h
i n c r e a s e d temperature d i s t a n c e from t h e c r i t i c a l p o i n t . The v a l u e s
1
o f t h e temperature exponent V were i n v e r y good agreement w i t h t h e
i d e a l v a l u e o f 0.67. I f t h e d i l u t e amounts o f h y d r o c a r b o n were
1
c o n s i d e r e d as i m p u r i t i e s , s l i g h t l y h i g h e r v a l u e s o f V c o u l d be
F
e x p l a i n e d by t h e renormal i z a t i o n o f V due t o i m p u r i t i e s . The
results also indicated that the relative magnitudes of the
background c o n t r i b u t i o n s c o u l d be used t o c o r r e l a t e t h e e f f e c t s o f
m o l e c u l a r d i f f u s i o n and s o l u t e - s o l v e n t i n t e r a c t i o n s .

5
; 1er
10-
0.1
(T-T )
c (C)
F i g u r e 3: P l o t o f t h e measured decay r a t e s and t h e c a l c u l a t e d

c r i t i c a l and background c o n t r i b u t i o n s a l o n g a c r i t i c a l
i s o c h o r e o f t h e b e n z e n e - C 0 system a t 97.9 mol % C 0 and
3 2 2
p = 0.546 g/cm .
4
ΙΟ" ,
H
10 I 1—ι—ι ι Μ ι r η 1—ι—ι ι ι ι ι
0.1 1 10
F i g u r e 4: P l o t o f t h e measured decay r a t e s and t h e c a l c u l a t e d

c r i t i c a l and background c o n t r i b u t i o n s a l o n g a c r i t i c a l
i s o c h o r e o f t h e d e c a n e - C 0 system a t 97.9 mol % CO^ and
2
P = 0.592 g/cm .
c

Acknowledgments
T h i s work was s u p p o r t e d by N a t i o n a l S c i e n c e F o u n d a t i o n Granjt No.
CBT-8419755.
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Rev. in Chem. Engineering 1983, 1, 179.
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RECEIVED July 17, 1986

Chapter 2
Transport and Intermolecular Interactions

in Compressed Supercritical Fluids
J. Jonas and D. M. Lamb
Department of Chemistry, School of Chemical Sciences, University of Illinois, Urbana,

IL 61801
General overview of several studies of transport

and intermolecular interactions in compressed
supercritical fluids is presented The unique
aspects of the
studies are emphasized
studies of self-diffusion in supercritical ethyl-
ene and toluene are discussed. These experiments
used the fixed field gradient NMR spin-echo
technique. Second, the novel NMR technique for
the determination of solubility of solids in
supercritical fluids is described.
R e s e a r c h on the p r o p e r t i e s o f s u p e r c r i t i c a l f l u i d s and s u p e r -
c r i t i c a l f l u i d m i x t u r e s h a s become v e r y i m p o r t a n t i n r e c e n t
y e a r s due t o t h e g r e a t p r o m i s e o f s u p e r c r i t i c a l f l u i d e x t r a c t i o n
techniques. These t e c h n i q u e s and t h e i r a p p l i c a t i o n s have been
r e v i e w e d by s e v e r a l a u t h o r s ( 1 - 4 ) . T h e r e a r e many a d v a n t a g e s o f
using s u p e r c r i t i c a l f l u i d e x t r a c t i o n over c o n v e n t i o n a l e x t r a c -
tion techniques. Many l o w v o l a t i l i t y m o l e c u l a r s o l i d s show
g r e a t l y enhanced s o l u b i l i t i e s i n s u p e r c r i t i c a l dense f l u i d s .
S o l v e n t r e c o v e r y i s e a s i l y a c c o m p l i s h e d by m a n i p u l a t i n g the
d e n s i t y , and t h e r e f o r e the s o l v a t i n g power, o f the s u p e r c r i t i c a l
f l u i d to p r e c i p i t a t e the s o l i d . In a d d i t i o n , a l t h o u g h the d e n s i -
t i e s o f the s u p e r c r i t i c a l f l u i d s a r e comparable t o l i q u i d d e n s i -
t i e s , the v i s c o s i t i e s a r e g e n e r a l l y an o r d e r o f magnitude
s m a l l e r , and d i f f u s i v i t i e s an o r d e r o f magnitude l a r g e r than
liquids. A more e f f i c i e n t s e p a r a t i o n c a n t h e r e f o r e be a c h i e v e d .
U n f o r t u n a t e l y , t h e r e i s a l a c k o f fundamental d a t a on
t r a n s p o r t and r e l a x a t i o n i n model f l u i d s a t s u p e r c r i t i c a l c o n d i -
t i o n s . Not s u r p r i s i n g l y , t h e r e i s a c o r r e s p o n d i n g l a c k o f t h e o -
r e t i c a l models to e x p l a i n the dynamics o f s u p e r c r i t i c a l f l u i d s
on a m o l e c u l a r l e v e l , p a r t i c u l a r l y a t the i n t e r m e d i a t e d e n s i -
ties.
0097-6156/87/0329-0015$06.00/0

T h e main p u r p o s e o f o u r w o r k i s t h e i m p r o v e m e n t o f m o l e c u -
l a r l e v e l u n d e r s t a n d i n g o f s o l u t e - s o l v e n t i n t e r a c t i o n s under
supercritical conditions. Unique n u c l e a r magnetic resonance ( 5 )
t e c h n i q u e s a r e employed t o o b t a i n new i n f o r m a t i o n about dynamics
of m o l e c u l e s i n s u p e r c r i t i c a l f l u i d s a t h i g h p r e s s u r e s .
The m a i n r e s u l t s o f s e v e r a l o f o u r s t u d i e s w i l l b e
discussed. F i r s t , t h e r e s u l t s o f NMR s t u d i e s o f s e l f - d i f f u s i o n
i n s u p e r c r i t i c a l e t h y l e n e (_6) a n d t o l u e n e (7) w i l l b e d i s c u s s e d .
T h e s e e x p e r i m e n t s used the f i x e d f i e l d g r a d i e n t NMR s p i n - e c h o
technique. Second, the movel NMR t e c h n i q u e ( 8 ) f o r t h e d e t e r -
mination of s o l u b i l i t y of s o l i d s i n s u p e r c r i t i c a l f l u i d e s w i l l be
described.
Experimental
The s e l f - d i f f u s i o n c o e f f i c i e n t s i n s u p e r c r i t i c a l e t h y l e n e w e r e
m e a s u r e d u s i n g t h e p u l s e d NMR s p e c t r o m e t e r d e s c r i b e d e l s e w h e r e
( 9 , 1 0 ) , automated for
by t h e Hahn s p i n e c h o
a t t h e p r o t o n r e s o n a n c e f r e q u e n c y o f 60 MHz u s i n g a 1 4 . 2 k G
electromagnet.
T h e p r e s s u r e was g e n e r a t e d u s i n g t h e g a s c o m p r e s s i o n s y s t e m
described previously (12). A H e i s e - B o u r d o n p r e s s u r e gauge was
i n s t a l l e d between the c o m p r e s s i o n system and the h i g h p r e s s u r e
v e s s e l to supplement the 30,000 p s i pressure t r a n s d u c e r . The
o x y g e n s c a v e n g e r s y s t e m was b y p a s s e d a s t h e a m o u n t o f o x y g e n i n
t h e e t h y l e n e was b e l o w t h e m i n i m u m d e t e c t i o n l e v e l ( 1 0 ppm) o f
the oxygen a n a l y z e r (Beckman I n s t r u m e n t s , I n c . ) . In order to
d e p r e s s t h e e x t r e m e l y l o n g T-j v a l u e s o f p u r e e t h y l e n e ( 1 3 ) a t
t h e e x p e r i m e n t a l c o n d i t i o n s s t u d i e d , s m a l l q u a n t i t i e s (< 1 0 0 0
ppm) o f o x y g e n w e r e m i x e d w i t h t h e e t h y l e n e b e f o r e measurement
o f the d i f f u s i o n c o e f f i c i e n t . The a d d i t i o n o f o x y g e n b r o u g h t
t h e T-j v a l u e s down t o 2 - 3 s e c , b u t s h o u l d n o t a f f e c t t h e v a l u e
of the d i f f u s i o n c o e f f i c i e n t . The s h o r t e r T v a l u e s a l l o w e d a
1
much s h o r t e r m e a s u r e m e n t t i m e .
The s e l f - d i f f u s i o n c o e f f i c i e n t s i n s u p e r c r i t i c a l t o l u e n e - d g
were measured a t t h e d e u t e r i u m r e s o n a n c e f r e q u e n c y o f 9.21 MHz,
u s i n g a 14.1 kG e l e c t r o m a g n e t w i t h a w i d e gap ( 3 - 8 " ) t o accommo-
date the h i g h p r e s s u r e v e s s e l . The p u l s e d NMR s p e c t r o m e t e r a n d
r e c e i v e r s y s t e m were d e s c r i b e d i n d e t a i l e l s e w h e r e ( 1 0 ) . The
a r g o n p r e s s u r i z e d h i g h p r e s s u r e , h i g h t e m p e r a t u r e NMR p r o b e ( 1 4 )
was u s e d p r e v i o u s l y f o r s t u d i e s o f r e l a x a t i o n ( 1 5 ) a n d d i f f u s i o n
(16) i n compressed s u p e r c r i t i c a l w a t e r . I t c o n s i s t s o f two h i g h
pressure vessels: the p r i m a r y v e s s e l , c o n t a i n i n g an i n t e r n a l
f u r n a c e , t w o t h e r m o c o u p l e s a n d t h e RF c o i l a n d s a m p l e , a n d t h e
secondary v e s s e l , c o n t a i n i n g the s t a i n l e s s s t e e l sample b e l l o w s .
Q u a r t z sample c e l l s were u s e d r a t h e r t h a n c e r a m i c c e l l s , a s
c o r r o s i o n i s not a problem. The RF c o i l was c o n s t r u c t e d b y
w i n d i n g 14 1 / 2 t u r n s o f 2 2 g a u g e n i c h r o m e ( C h r o m e l A) w i r e . The
c o i l was s i l v e r s o l d e r e d t o n i c h r o m e c o n d u c t o r c o a x i a l h i g h
pressure leads. The t u n i n g c i r c u i t c o n s i s t e d o f a s i x f o o t
impedance t r a n s f o r m i n g c o a x i a l c a b l e t e r m i n a t e d w i t h a
t a p p e d - p a r a l l e l c a p a c i t o r box w i t h b o t h f i x e d and v a r i a b l e

JONAS AND LAMB Transport and Intermolecular Interactions
c a p a c i t o r s t o t a l l i n g 7 0 p F i n s e r i e s a n d 10 p F i n p a r a l l e l . T h e
o b s e r v e d s i g n a l peak t o rms n o i s e r a t i o i n l i q u i d t o l u e n e - d g
( 3 0 ° C ) was 60:1 a f t e r one s c a n .
The s o l u b i l i t i e s f o r n a p h t h a l e n e i n s u p e r c r i t i c a l c a r b o n
d i o x i d e (_8) w e r e m e a s u r e d a t 60 MHz u s i n g t h e NMR s p e c t r o m e t e r
d e s c r i b e d e l s e w h e r e ( 1 0 ) . The h i g h p r e s s u r e , h i g h t e m p e r a t u r e
NMR p r o b e a n d g a s c o m p r e s s i o n s y s t e m w e r e t h e same a s t h a t u s e d
i n t h e s u p e r c r i t i c a l e t h y l e n e e x p e r i m e n t (6). The s o l u b i l i t y
s a m p l e c e l l a s s h o w n i n F i g u r e 1 was o f c y l i n d r i c a l d e s i g n w i t h
0 . 2 5 0 i n . i n n e r d i a m e t e r a n d was m a c h i n e d from a h i g h t e m p e r a
t u r e p o l y i m i d e p l a s t i c ( V e s p e l , DuPont C o . ) . An e x c e s s o f s o l i d
n a p h t h a l e n e was l o a d e d i n t o t h e c e l l b e f o r e a s o l u b i l i t y d e t e r
m i n a t i o n a n d t h e c e l l was c l o s e d w i t h a c l o s e - f i t t i n g p i s t o n .
P r e s s u r i z e d C 0 e n t e r e d t h e sample r e g i o n t h r o u g h two s m a l l
2
h o l e s (0.016 i n . ) d r i l l e d through the sample c e l l w a l l s . To

a s s u r e t h a t e q u i l i b r u m s o l u b i l i t i e s were o b t a i n e d , enough s o l i d
n a p h t h a l e n e was i n i t i a l l y p l a c e d i n t h e s a m p l e c e l l s o t h a t a n
e x c e s s w o u l d be p r e s e n
sary to separate the c o n t r i b u t i o
d i s s o l v e d naphthalene and the r e m a i n i n g s o l i d . T h i s s e p a r a t i o n
i s e a s i l y a c c o m p l i s h e d due t o the r a d i c a l l y d i f f e r e n t s p i n - s p i n
r e l a x a t i o n r a t e s o f d i s s o l v e d a n d s o l i d m a t e r i a l ( T , s o l i d <<
2
T , dissolved).
2 We u s e d t h e 9 0 ° - τ - ΐ 8 0 ° s p i n - e c h o s e q u e n c e w i t h
a p u l s e s e p a r a t i o n o f τ - .007 s; t h i s ensured t h a t no c o n t r i b u
t i o n t o t h e NMR e c h o s i g n a l c o u l d r e s u l t f r o m t h e q u i c k l y r e l a x
ing protons o f s o l i d naphthalene. I n t h i s w a y we w e r e a b l e t o
m o n i t o r t h e NMR s i g n a l f r o m t h e n a p h t h a l e n e d i s s o l v e d i n t h e
supercritical solution exclusively. This experimental approach
for s e p a r a t i n g t h e s i g n a l from m o b i l e and immobile n u c l e i h a s
been used p r e v i o u s l y i n our l a b o r a t o r y ( 1 7 ) .
The u s e o f NMR s p e c t r o s c o p y a s a n a n a l y t i c a l t e c h n i q u e i s
w e l l established ( 1 8 ) . In order to quantitate our spin-echo
h e i g h t t o t h e n u m b e r o f p r o t o n s p r e s e n t , we p e r f o r m e d a n i n d e
pendent c a l i b r a t i o n u s i n g standard s o l u t i o n s o f naphthalene i n
carbon t e t r a c h l o r i d e . C o n c e n t r a t i o n s f o r t h e s t a n d a r d s were
chosen to correspond to the a n t i c i p a t e d s u p e r c r i t i c a l C 0 2
s o l u b i l i t i e s , and a l l c a l i b r a t i o n measurements were performed

u s i n g a s a m p l e c e l l o f t h e same d i m e n s i o n s a s t h e s o l u b i l i t y
sample c e l l p r e v i o u s l y d e s c r i b e d . The r e s p o n s e o f o u r s p e c
t r o m e t e r t o t h e s t a n d a r d s o l u t i o n s was l i n e a r o v e r t h e c o n c e n
t r a t i o n range. The r e p r o d u c i b i l i t y f o r i n d e p e n d e n t measurements
o f t h e c a l i b r a t i o n c u r v e was ± 3/6. T h r o u g h o u t t h e e x p e r i m e n t ,
a l l spectrometer c o n d i t i o n s (pulse lengths, phases, r e c e i v e r
a m p l i f i e r g a i n , e t c . ) were c l o s e l y m o n i t o r e d , and frequent
c h e c k s on t h e c a l i b r a t i o n o f t h e s p e c t r o m e t e r were p e r f o r m e d . I n
t h i s way we w e r e a b l e t o o b t a i n t h e m o l a r s o l u b i l i t y o f s o l i d
naphthalene i n s u p e r c r i t i c a l carbon d i o x i d e t o an estimated
e x p e r i m e n t a l a c c u r a c y o f ± 6%.
O u r NMR t e c h n i q u e f o r t h e d e t e r m i n a t i o n o f t h e s o l i d - l i q
u i d - g a s p h a s e l i n e t h a t e n d s a t t h e UCEP a g a i n m a k e s u s e o f t h e
f a c t t h a t t h e NMR s i g n a l f r o m n u c l e i w i t h d i f f e r e n t r e l a x a t i o n
r a t e s c a n be e a s i l y s e p a r a t e d . I n t h i s c a s e we a r e d i s t i n g u i s h
ing between t h e s i g n a l from t h e n a p h t h a l e n e - r i c h l i q u i d phase
f o r m e d when t h e S-L-G l i n e i s c r o s s e d a n d s o l i d n a p h t h a l e n e .

SUPERCRITICAL FLUIDS
S i n c e the s p i n - s p i n r e l a x a t i o n o f the l i q u i d phase naphthalene

p r o t o n s i s much l o n g e r t h a n t h a t o f t h e s o l i d n a p h t h a l e n e p r o
t o n s , b y o n c e more u s i n g t h e s p i n - e c h o s e q u e n c e w i t h τ = . 0 0 7 s
we a r e a b l e t o m o n i t o r t h e NMR s i g n a l f r o m t h e l i q u i d p h a s e
only.
The t e c h n i q u e was i m p l e m e n t e d a s f o l l o w s . With s o l i d
n a p h t h a l e n e i n o u r s o l u b i l i t y c e l l we b r o u g h t t h e s y s t e m t o a
d e s i r e d t e m p e r a t u r e and C 0 p r e s s u r e such t h a t s o l i d - s u p e r
2
c r i t i c a l gas e q u i l i b r i u m e x i s t e d . T h e t e m p e r a t u r e was t h e n
slowly increased (heating rate approximately 1°C/hour) at con
s t a n t p r e s s u r e , w h i l e t h e NMR s i g n a l was m o n i t o r e d . When t h e
S - L - G l i n e was i n t e r s e c t e d , t h e s o l i d n a p h t h a l e n e i n t h e c e l l
would melt w i t h the f o r m a t i o n o f the n a p h t h a l e n e - r i c h l i q u i d
p h a s e , and t h i s r e s u l t e d i n a l a r g e and r a p i d i n c r e a s e i n o u r
NMR s i g n a l . T h e t e m p e r a t u r e a t w h i c h we saw t h i s d i s c o n t i n u o u s
j u m p i n o u r NMR s i g n a l g a v e t h e l o c a t i o n o f t h e p h a s e l i n e a t
that pressure.
The m a i n s o u r c e
finite rate of heating
t i o n o f t h e S - L - G l i n e t o be ± 0 . 4 ° C and ± 2 b a r .
R e s u l t s and Discussion
S e l f - D i f f u s i o n i n Compressed S u p e r c r i t i c a l E t h y l e n e . The m a i n
p u r p o s e o f o u r w o r k (_6) was t o p r o v i d e t r a n s p o r t d a t a o n d e n s e
s u p e r c r i t i c a l e t h y l e n e and t o a n a l y z e the d a t a i n terms o f c u r
rently available theories. E t h y l e n e was c h o s e n f o r t h e s t u d y
f o r a number o f r e a s o n s . F i r s t , i t i s one o f t h e most w i d e l y
u s e d s o l v e n t s i n i n d u s t r y due t o i t s e a s i l y a c c e s s i b l e c r i t i c a l
t e m p e r a t u r e , i t s r e l a t i v e l y low c o s t and wide a v a i l a b i l i t y .
Highly accurate c o m p r e s s i b i l i t y data are a v a i l a b l e (19-21) i n
the l i t e r a t u r e over a wide range o f temperature and p r e s s u r e s .
These d a t a a r e n e c e s s a r y f o r a complete a n a l y s i s o f the t r a n s
port data.
Some m e a s u r e m e n t s h a v e b e e n made o f s e l f d i f f u s i o n i n p u r e
e t h y l e n e and i n e t h y l e n e - s u l f u r h e x a f l u o r i d e m i x t u r e s ( 2 2 ) , but
t h e s e m e a s u r e m e n t s w e r e made v e r y c l o s e t o t h e c r i t i c a l t e m p e r a
t u r e a n d up t o p r e s s u r e s o f o n l y a b o u t 100 b a r . Proton spin-
l a t t i c e r e l a x a t i o n t i m e s (T-. ) o f e t h y l e n e h a v e b e e n m e a s u r e d a t
t e m p e r a t u r e s f r o m 0 ° C t o 5 0 ° C a n d p r e s s u r e s up t o a b o u t 2 3 0 0 b a r
( 1 j 3 ) . T h e r e l a x a t i o n t i m e v a l u e s w e r e 4 0 - 5 0 s e c f o r much o f t h e
region studied. S e v e r a l r e l a x a t i o n mechanisms c o n t r i b u t e t o
t h i s l o n g r e l a x a t i o n t i m e a n d make b o t h t h e m e a s u r e m e n t a n d
a n a l y s i s o f the r e l a x a t i o n times very d i f f i c u l t . For these
r e a s o n s , we d e c i d e d t o l i m i t o u r s t u d y t o t h e m e a s u r e m e n t o f t h e
s e l f - d i f f u s i o n c o e f f i c i e n t i n s u p e r c r i t i c a l e t h y l e n e (60.
T h e m e a s u r e m e n t s w e r e made a s a f u n c t i o n o f d e n s i t y f o r
p r e s s u r e s f r o m 1 - 2000 b a r and a t 5 0 ° , 7 5 ° , 1 0 0 ° and 1 2 5 ° C .
The t e m p e r a t u r e s c h o s e n c o r r e s p o n d t o t h o s e f o r w h i c h d e n s i t y
d a t a (19-21) f o r e t h y l e n e and e t h y l e n e - C 0 are a v a i l a b l e .
2 The
experimental s e l f - d i f f u s i o n c o e f f i c i e n t s o f ethylene as a func
t i o n o f t e m p e r a t u r e and d e n s i t y a r e p r e s e n t e d i n F i g u r e 2 . The
p r e s s u r e s c o r r e s p o n d i n g t o the c h o s e n d e n s i t i e s were d e t e r m i n e d
from the c o m p r e s s i b i l i t y d a t a o f M i c h e l s and Geldermans ( 2 0 ) .

JONAS A N D LAMB Transport and Intermolecular Interactions
^CLOSURE PISTON
j ^ ; — \ PISTON STOP PIN
"0" RING
0.016 C 0 2
ENTRANCE HOLE
3.0
SAMPLE REGION
0.4
F i g u r e 1. Schematic drawing o f NMR sample c e l l for super

c r i t i c a l s o l u b i l i t y measurements.
250 Γ 1
0
ο 50 °C
ο • 75°C
• Δ I00°C
200 ν I25°C
ο 150
α> 7
</>
C\J A
ο
ε
- •
7
-
'g 100
α 8
50 i
,
g
1 1 1
0.2 0.4 0.6
3
Density (g/cm )
Figure 2. D e n s i t y and temperature dependence of the experimen

t a l s e l f - d i f f u s i o n c o e f f i c i e n t s of compressed s u p e r
c r i t i c a l ethylene.

The v a r i a t i o n i n t h e s e l f - d i f f u s i o n c o e f f i c i e n t i s p r i m a r i l y
d e t e r m i n e d by the change i n d e n s i t y v a r i e d over a wide r a n g e .
T h e r e i s no s i g n i f i c a n t t e m p e r a t u r e dependence w i t h i n t h e e r r o r
o f t h e m e a s u r e m e n t s . The d a t a c o v e r a r a n g e o f d e n s i t i e s 0 . 3 4 <_
p/p c <_ 2 . 5 , a n d t e m p e r a t u r e 1 . 1 4 < T / T c £1.41.
The d e n s i t y d e p e n d e n c e o f t h e e t h y l e n e s e l f - d i f f u s i o n coef
f i c i e n t s was a n a l y z e d u s i n g t h e E n s k o g t h e o r y ( 2 3 ) o f d i f f u s i o n
of hard spheres c o r r e c t e d f o r the e f f e c t s o f c o r r e l a t e d motion
( 2 4 ) . The c o r r e c t e d E n s k o g t h e o r y c o n s i d e r s o n l y r e p u l s i v e
f o r c e s b e t w e e n m o l e c u l e s , b u t i t h a s p r o v e d t o be i n e x c e l l e n t
agreement w i t h experiment f o r the t r a n s p o r t c o e f f i c i e n t s o f
s u p e r c r i t i c a l d e n s e g a s e s s u c h a s a r g o n , k r y p t o n , methane and
carbon t e t r a f l u o r i d e (25). At d e n s i t i e s l e s s than the c r i t i c a l
d e n s i t y ( p ) , t h e a t t r a c t i v e f o r c e s b e t w e e n t h e m o l e c u l e s become
c
i m p o r t a n t and d e v i a t i o n s from the t h e o r y a r e o b s e r v e d . We

c a l c u l a t e d the hard sphere d i a m e t e r from the c o m p r e s s i b i l i t y
d a t a based on the concept t h a t at h i g h d e n s i t y and h i g h tempera
t u r e , the van der W a a l '
l e n t to the hard spher
density are p l o t t e d against r e c i p r o c a l temperature. The h i g h
temperature i n t e r c e p t o f the tangent to t h i s curve at a g i v e n
temperature i s equated to the hard sphere v a l u e o f PV/NkT. From
t h i s v a l u e a n d t h e known h a r d s p h e r e e q u a t i o n o f s t a t e , t h e h a r d
sphere diameter i s c a l c u l a t e d .
The h a r d s p h e r e d i a m e t e r s w e r e t h e n u s e d t o c a l c u l a t e t h e
t h e o r e t i c a l Enskog c o e f f i c i e n t s at each d e n s i t y and temperature.
The r e s u l t s a r e s h o w n i n F i g u r e 3 a s p l o t s o f t h e r a t i o o f t h e
e x p e r i m e n t a l to c a l c u l a t e d c o e f f i c i e n t s v s . the p a c k i n g f r a c
t i o n , a l o n g w i t h the m o l e c u l a r dynamics r e s u l t s (24) f o r com
parison. The a g r e e m e n t b e t w e e n t h e c a l c u l a t e d r a t i o s a n d t h e
molecular dynamics r e s u l t s i s e x c e l l e n t at the intermediate
d e n s i t i e s , e s p e c i a l l y for those r a t i o s c a l c u l a t e d with diameters
d e t e r m i n e d f r o m PVT d a t a . D i s c r e p a n c i e s a t t h e i n t e r m e d i a t e
d e n s i t i e s c a n be e a s i l y a c c o u n t e d f o r by e r r o r s i n measured
d i f f u s i o n c o e f f i c i e n t s and c a l c u l a t e d d i a m e t e r s . The c o r r e c t e d
Enskog t h e o r y o f h a r d spheres g i v e s an a c c u r a t e d e s c r i p t i o n o f
the s e l f - d i f f u s i o n i n dense s u p e r c r i t i c a l e t h y l e n e .
The b i g g e s t d i f f e r e n c e s a r e o b t a i n e d f o r t h e l o w e r (p _< p ) c
d e n s i t y p o i n t s a t each t e m p e r a t u r e , where the c a l c u l a t e d r a t i o s

a r e up t o a p p r o x i m a t e l y 2 0 ? s m a l l e r t h a n t h e m o l e c u l a r d y n a m i c s
results. T h i s r e s u l t i s not s u r p r i s i n g ; at the lower d e n s i t i e s ,
t h e e f f e c t s o f a t t r a c t i v e f o r c e s become i m p o r t a n t a n d c a u s e
d i f f u s i o n i n a r e a l g a s t o be s l o w e r . Dymond ( 2 5 ) h a s f o u n d
t h a t the t h e o r y p r e d i c t e d the e x p e r i m e n t a l s e l f - d i f f u s i o n coef
f i c i e n t s f o r d e n s i t i e s down t o a b o u t 0 . 7 P f o r Τ > T .
c Q
The more o b v i o u s a n d c o n s i s t e n t d e v i a t i o n s f r o m t h e h a r d
s p h e r e t h e o r y o c c u r , a t t h e l o w d e n s i t y v a l u e s , due t o t h e
e f f e c t s o f a t t r a c t i v e f o r c e s i n t h e r e a l s y s t e m . We c a n a t t e m p t
t o c o r r e c t f o r t h e s e e f f e c t s u s i n g a method d e s c r i b e d p r e v i o u s l y
( 2 7 - 3 0 ) f o r t h e a n a l y s i s o f a n g u l a r momentum c o r r e l a t i o n t i m e s
i n s u p e r c r i t i c a l CF^ and CF^ m i x t u r e s w i t h a r g o n and neon. We
r e p l a c e the h a r d sphere r a d i a l d i s t r i b u t i o n f u n c t i o n at c o n t a c t
g w i t n a
hs function g ( σ ) w h i c h u s e s t h e more r e a l i s t i c

Lennard-Jones p o t e n t i a l . T h e new r a d i a l d i s t r i b u t i o n f u n c t i o n
i s estimated u s i n g the e x p o n e n t i a l approximation t o the
optimized c l u s t e r theory :(31)
C. ( σ )
gp(o) = g ( o ) e n s (1)
where C ( σ ) i s t h e r e n o r m a l i z e d i n t e r m o l e c u l a r p o t e n t i a l a s d e
L
s c r i b e d a n d g i v e n i n R e f e r e n c e ( 3 2 ) . T h i s c o r r e c t i o n was s u c
c e s s f u l l y used t o extend the rough hard sphere model (29) t o the
intermediate and low d e n s i t y r e g i o n s f o r the i n t e r p r e t a t i o n o f
a n g u l a r momentum c o r r e l a t i o n t i m e s .
I f one c o r r e c t s f o r t h e e f f e c t s o f a t t r a c t i v e f o r c e s , t h e
c o r r e c t e d v a l u e s a r e much s m a l l e r t h a n t h e o b s e r v e d v a l u e s ; t h e
c o r r e c t i o n o v e r e s t i m a t e s the importance o f a t t r a c t i v e f o r c e s on
the v a l u e o f the d i f f u s i o n c o e f f i c i e n t . Although a t t r a c t i v e
f o r c e s have an e f f e c t on t h e d i f f u s i o n c o e f f i c i e n t a t low d e n
s i t y , they a r e not n e a r l y as important as they a r e i n d e t e r m i n
ing the value o f the angula
sion i s p r i m a r i l y determine
molecules, even a t the lowest d e n s i t i e s .
S e l f - D i f f u s i o n i n Compressed S u p e r c r i t i c a l T o l u e n e - d g . Our
i n v e s t i g a t i o n was m o t i v a t e d b y t h e i n t e r e s t i n s u p e r c r i t i c a l
toluene as a solvent i n the e x t r a c t i o n o f thermally generated
c o a l l i q u i d s (33,34). T y p i c a l l y , c o a l i s heated to temperatures
between 3 5 0 ° and 450°C i n t h e presence o f a s u p e r c r i t i c a l f l u i d
a t a p r e s s u r e o f 100-200 atm. As t h e l a r g e m o l e c u l a r w e i g h t
components d e p o l y m e r i z e t h e r m a l l y , the r e s u l t i n g hydrogen r i c h
m a t e r i a l d i s s o l v e s i n the s u p e r c r i t i c a l s o l v e n t and i s removed.
Toluene i s a convenient s o l v e n t t o use f o r the e x t r a c t i o n , as
i t s c r i t i c a l t e m p e r a t u r e i s 3 1 9 ° C , a n d c r i t i c a l p r e s s u r e i s 41
atm. Recent experimental s t u d i e s o f s u p e r c r i t i c a l f l u i d e x t r a c
t i o n i n the process o f c o a l l i q u e f i c a t i o n i n v e s t i g a t e the basic
s t e p s i n v o l v e d by v a r y i n g s o l v e n t s , pressure and temperatures
(35). T h e g o a l o f o u r e x p e r i m e n t was t o p r o v i d e f u n d a m e n t a l
data on t r a n s p o r t i n s u p e r c r i t i c a l t o l u e n e - d g . These data
should h e l p i n the d e s i g n and i n t e r p r e t a t i o n o f e x t r a c t i o n
processes using s u p e r c r i t i c a l toluene.
We h a v e m e a s u r e d t h e s e l f - d i f f u s i o n c o e f f i c i e n t i n s u p e r
c r i t i c a l toluene-d 8 f o r temperatures from 300°C t o 450°C ( 0 . 9 7 £
T r < 1 . 2 2 ) f o r p r e s s u r e s o f 1 0 0 , 500 and 1000 b a r .
S e l f d i f f u s i o n c o e f f i c i e n t s o f d e u t e r a t e d t o l u e n e were
measured, r a t h e r than protonated toluene i n order t o minimize
the e x p e r i m e n t a l d i f f i c u l t i e s a s s o c i a t e d w i t h very long p r o t o n
s p i n l a t t i c e r e l a x a t i o n t i m e s ( T ^ . S i n c e t h e v a l u e o f t h e T-j
d e t e r m i n e s the l e n g t h o f time between p u l s e sequences, a long
r e l a x a t i o n t i m e l e a d s t o p r o h i b i t i v e l y l o n g measurement t i m e s .
P r e v i o u s measurements (36-38) o f p r o t o n and d e u t e r i u m r e l a x a t i o n
t i m e s i n l i q u i d t o l u e n e h a v e b e e n made a s a f u n c t i o n o f t e m p e r a
t u r e a n d p r e s s u r e . The r e l a x a t i o n i s due t o d i p o l a r i n t e r a c t i o n s
i n protonated toluene and quadrupolar i n t e r a c t i o n s i n t o l u
ene-dg. T h e r e f o r e , t h e r e l a x a t i o n t i m e s c a n be e x p e c t e d t o
i n c r e a s e w i t h i n c r e a s i n g t e m p e r a t u r e . However, the q u a d r u p o l a r
r e l a x e d d e u t e r i u m T^ v a l u e s a r e s m a l l e r t h a n t h e p r o t o n T-j

v a l u e s , r e s u l t i n g i n a c o m p a r a t i v e l y s h o r t e r measurement time.
The s e l f d i f f u s i o n c o e f f i c i e n t s o f d e u t e r a t e d t o l u e n e s h o u l d not
be s i g n i f i c a n t l y d i f f e r e n t from t h o s e o f p r o t o n a t e d t o l u e n e a t
the temperatures o f the measurement and w i l l p r o v i d e an e x c e l -
lent estimate.
Our p r e v i o u s study (16) o f s e l f d i f f u s i o n i n compressed
s u p e r c r i t i c a l water compared the e x p e r i m e n t a l r e s u l t s t o the
p r e d i c t i o n s o f the d i l u t e p o l a r gas model o f Monchick and Mason
(39). The model, u s i n g a Stockmayer p o t e n t i a l f o r the e v a l u a -
t i o n o f the c o l l i s i o n i n t e g r a l s and a temperature dependent h a r d
sphere d i a m e t e r s , gave a good d e s c r i p t i o n o f the temperature and
p r e s s u r e dependence o f the d i f f u s i o n . Unfortunately, a similar
d e t a i l e d a n a l y s i s o f the s e l f d i f f u s i o n o f s u p e r c r i t i c a l t o l u e n e
i s p r e v e n t e d by the l a c k o f d e n s i t y d a t a a t s u p e r c r i t i c a l c o n d i -
tions. V i s c o s i t i e s o f t o l u e n e from 320°C t o 470°C a t c o n s t a n t
volumes c o r r e s p o n d i n g t o d e n s i t i e s from p/p = 0.5 t o 1.8 have
c
been r e p o r t e d (*\0). However, w i t h o u t PVT d a t a , we cannot c a l c u -

l a t e the c o r r e s p o n d i n
The d i f f u s i o n d a t
v a l u e s o b t a i n e d u s i n g v a r i o u s e s t i m a t i o n schemes f o r the s e l f
d i f f u s i o n c o e f f i c i e n t o f t o l u e n e . No attempt was made t o e s t i -
mate c o e f f i c i e n t s a t 500 and 1000 bar, as these c o r r e s p o n d t o
reduced p r e s s u r e s (P = 11.9 and 24.7) w e l l beyond the range o f
the a p p r o x i m a t i v e methods. The r e s u l t s o b t a i n e d u s i n g the g e n e r -
a l i z e d c h a r t s o f S l a t t e r y and B i r d (4]_) and o f T a k a h a s h i (42) do
not g i v e a v e r y good agreement w i t h the e x p e r i m e n t a l r e s u l t s .
The p r e d i c t e d v a l u e s a r e c o n s i s t e n t l y lower than the measured
v a l u e s , and the temperature dependence i s not s t r o n g enough.
The e x p e r i m e n t a l temperature dependence i s much more c l o s e l y
reproduced by the e m p i r i c a l c o r r e l a t i o n s o f Dawson e t a l . (43)
and o f Mathur and Thodos ( 4 4 ) . The e x a c t e x p e r i m e n t a l v a l u e s
a r e not r e p r o d u c e d by any o f the methods. However, c o n s i d e r i n g
the d i f f e r e n c e i n m o l e c u l a r weight between t o l u e n e and t o l u -
ene-dg,the a p p r o x i m a t i o n s i n v o l v e d , a n d the e r r o r i n the e x p e r i -
mental v a l u e s (which g e t s h i g h e r as the d e n s i t y d e c r e a s e s ) , the
c o r r e l a t i o n o f Mathur and Thodos g i v e s a v e r y good e s t i m a t i o n o f
the s e l f d i f f u s i o n c o e f f i c i e n t i n s u p e r c r i t i c a l t o l u e n e .
NMR Measurements o f Naphthalene S o l u b i l i t y i n S u p e r c r i t i c a l

Carbon D i o x i d e . The p a r t i c u l a r phase b e h a v i o r o f the
n a p h t h a l e n e - C 0 system makes i t a v i a b l e c h o i c e f o r s t u d i e s o f
2
solid s o l u b i l i t i e s in supercritical fluids. The system i s known

as a c l a s s I I I m i x t u r e ( 4 5 ) Î i t s p r e s s u r e - t e m p e r a t u r e diagram i s
d e p i c t e d i n F i g u r e 5. T h i s type o f phase b e h a v i o r o c c u r s f o r
h i g h l y asymmetric b i n a r y m i x t u r e s where the m e l t i n g p o i n t o f the
heavy component i s g r e a t e r than the c r i t i c a l temperature o f the
v o l a t i l e component. Here the t h r e e phase s o l i d - l i q u i d - g a s
(S-L-G) f r e e z i n g p o i n t d e p r e s s i o n c u r v e i n t e r s e c t s the m i x t u r e
c r i t i c a l l i n e a t two l o c a t i o n s : the lower c r i t i c a l end p o i n t
(LCEP) and the upper c r i t i c a l end p o i n t (UCEP). The LCEP i s
t y p i c a l l y v e r y near the c r i t i c a l p o i n t o f the pure l i g h t compo-
nent; the l o c a t i o n o f the UCEP must be e x p e r i m e n t a l l y d e t e r -
mined. The e x i s t e n c e o f the end p o i n t s i s o f g r e a t importance:
between these two c r i t i c a l end p o i n t s and the a s s o c i a t e d

1.6
- 50°C
1.2
Ο \
0.8 -ô γ
ο
Ο
0.4 1 1 1 1 1 1 1 1
_I00°C * A Û Ι25^ Δ Δ
Δ
Δ " Δ
ο a^ôV
1.2 - Δ / ^ \
-—#° \
0.8
> γJ γ
0.4 1 1 1 1 I I I I
0.2 0.4 0 0.2 0.4
Packing Fraction
F i g u r e 3. The r a t i o D/D
s u p e r c r i t i c a l ethylene. Δ indicates r a t i o s calcu
l a t e d u s i n g h a r d sphere d i a m e t e r s d e t e r m i n e d from
d i f f u s i o n data. 0 indicates ratios calculated using
h a r d sphere d i a m e t e r s d e t e r m i n e d from c o m p r e s s i b i l i t y
data. The s o l i d l i n e s a r e the m o l e c u l a r dynamics
r e s u l t s , e x t r a p o l a t e d to i n f i n i t e systems, o f A l d e r ,
Gass and Wainwright (Ref. 2 4 ) .
F i g u r e 4. Comparison o f e x p e r i m e n t a l d i f f u s i o n c o e f f i c i e n t s (o)
f o r t o l u e n e - d g a t 100 b a r w i t h p r e d i c t i o n s o f t o l u
ene d i f f u s i o n : ( - - - - ) , method o f S l a t t e r y and
Bird; ( ) , method o f T a k a h a s h i ;
(- ) , method o f Dawson e t a l . ; ( ),
method o f Mathur and Thodos. The e r r o r b a r s r e p r e
s e n t d i f f e r e n c e s o f p l u s o r minus one s t a n d a r d d e v i a
tion. See the t e x t f o r d e t a i l s .

b r a n c h e s o f the S-L-G l i n e s o l i d - s u p e r c r i t i c a l gas e q u i l i b r i u m

e x i s t s a t a l l p r e s s u r e s . C o n s e q u e n t l y the c r i t i c a l end p o i n t s
d e f i n e the r e g i o n where s o l i d - s u p e r c r i t i c a l f l u i d e x t r a c t i o n
would take p l a c e . A l s o , s o l i d s o l u b i l i t i e s a r e enhanced and
v e r y s e n s i t i v e t o changes i n temperature and p r e s s u r e near the
end p o i n t s ( £ 6 ) , making them t e c h n o l o g i c a l l y i n t e r e s t i n g .
The n a p h t h a l e n e - C 0
2 system has been p r e v i o u s l y i n v e s t i -
gated. Tsekhanskaya e t a l . (47) have measured s o l u b i l i t i e s o f
n a p h t h a l e n e i n s u p e r c r i t i c a l C 0 a t t e m p e r a t u r e s o f 35, 45, and
2
55°C and p r e s s u r e s up t o 324 bar, and McHugh and P a u l a i t i s (48)

have r e p o r t e d s o l u b i l i t i e s a t 35, 55°C, and two h i g h e r tempera-
t u r e s t o p r e s s u r e s o f about 290 b a r . However, n e i t h e r s t u d y has
c l e a r l y d e f i n e d the s o l i d n a p h t h a l e n e s o l u b i l i t i e s near the
UCEP. In a l a t e r paper by McHugh and Yogan (j49) i n which the
S-L-G phase l i n e s were d e t e r m i n e d f o r v a r i o u s systems, i t was
p o i n t e d out t h a t the h i g h e r temperature s o l u b i l i t y d a t a r e p o r t e d
by McHugh and P a u l a i t i s (48) was i n f a c t f o r l i q u i d n a p h t h a l e n e -
supercritical fluid equilibria
the f a c t t h a t the p r e v i o u
e x t e r n a l s a m p l i n g t o d e t e r m i n e the s o l u b i l i t i e s — i m p o r t a n t phase
i n f o r m a t i o n can t h e r e f o r e be o b s c u r e d .
The NMR method we have d e v e l o p e d g i v e s a d i r e c t , i n s i t u
d e t e r m i n a t i o n o f the s o l u b i l i t y and a l s o a l l o w s us t o o b t a i n
phase d a t a on the system. In t h i s study we have measured the
s o l u b i l i t i e s o f s o l i d naphthalene i n s u p e r c r i t i c a l carbon d i o x -
ide a l o n g t h r e e i s o t h e r m s (50.0, 55.0, and 58.5°C) n e a r the UCEP
temperature over a p r e s s u r e range o f 120-500 b a r . We have a l s o
determined the p r e s s u r e - t e m p e r a t u r e t r a c e o f the S-L-G phase
l i n e t h a t t e r m i n a t e s w i t h the UCEP f o r the b i n a r y m i x t u r e .
F i n a l l y , we have performed an a n a l y s i s o f our d a t a u s i n g a
q u a n t i t a t i v e theory of s o l u b i l i t y i n s u p e r c r i t i c a l f l u i d s to
h e l p e s t a b l i s h the l o c a t i o n o f the UCEP.
The e x p e r i m e n t a l s o l u b i l i t y d a t a f o r s o l i d n a p h t h a l e n e i n
s u p e r c r i t i c a l c a r b o n d i o x i d e , g i v e n a s moles n a p h t h a l e n e d i s -
s o l v e d per l i t e r , a r e shown i n F i g u r e 6. Q u a l i t a t i v e l y the t h r e e
p r e s s u r e - c o m p o s i t i o n i s o t h e r m s show c h a r a c t e r i s t i c b e h a v i o r f o r
a s o l i d - s u p e r c r i t i c a l f l u i d system. Each i s o t h e r m i n i t i a l l y
shows a l a r g e i n c r e a s e i n s o l u b i l i t y w i t h i n c r e a s i n g p r e s s u r e ,
and then a l i m i t i n g v a l u e i s r e a c h e d a t h i g h e r p r e s s u r e s .
Diepen and S c h e f f e r (_46) were the f i r s t t o show t h a t n e a r
e i t h e r the lower o r upper c r i t i c a l end p o i n t the s o l u b i l i t y o f a
s o l i d i n a s u p e r c r i t i c a l f l u i d i s enhanced and a l s o v e r y s e n s i -
t i v e t o changes i n temperature and p r e s s u r e ; our s o l u b i l i t y
i s o t h e r m s show t h i s e f f e c t f o r both end p o i n t s . F i r s t , the
i s o t h e r m s c r o s s a t about 140 b a r so t h a t the s o l u b i l i t y a t the
l o w e s t temperature (50.0°C) i s l a r g e s t a t 120 b a r . T h i s i s a
r e s u l t o f a p p r o a c h i n g the lower c r i t i c a l end p o i n t r e g i o n (which
s h o u l d be c l o s e t o the c r i t i c a l p o i n t o f pure C 0 a s p r e v i o u s l y
2
mentioned). At t e m p e r a t u r e s and p r e s s u r e s near t h i s LCEP the

s o l u b i l i t y enhancement r e s u l t s i n lower temperature i s o t h e r m s
h a v i n g the g r e a t e r s o l u b i l i t i e s . The e f f e c t o f the upper c r i t i -
c a l end p o i n t i s a l s o w e l l shown by our d a t a . The 58.5°C i s o -
therm shows a l a r g e i n c r e a s e i n s o l u b i l i t y a t about 235 b a r ; the
s l o p e o f the i s o t h e r m i s n e a r z e r o . As Van Welie and Diepen

JONAS A N D L A M B Transport and Intermolecular Interactions
TEMPERATURE
F i g u r e 5. Pressure-temperatur
system. and a r e t h e c r i t i c a l p o i n t s o f pure
carbon d i o x i d e and n a p h t h a l e n e , r e s p e c t i v e l y . The
c r i t i c a l mixture l i n e ( ) i s i n t e r s e c t e d at the
lower (LCEP) and upper (UCEP) c r i t i c a l end p o i n t s by
the s o l i d - l i q u i d - g a s (S-L-G) f r e e z i n g p o i n t d e p r e s -
s i o n c u r v e . P o i n t M i s t h e t r i p l e p o i n t o f pure
n a p h t h a l e n e , and. t h e l i n e S = L i s t h e m e l t i n g c u r e
o f t h e pure s o l i d .
F i g u r e 6. Experimental s o l u b i l i t i e s f o r s o l i d naphthalene i n
s u p e r c r i t i c a l carbon d i o x i d e e x p r e s s e d i n moles
naphthalene d i s s o l v e d per l i t e r s o l u t i o n .

240 1ι— —ι 1 τ 1 1
<?
200 -
BAR)
_ < )
160
UJ
tr 120 - S-L-G -
CO
CO
cr 80 — -
Q_
40 -
Ο 1 1 1 1 1
56 60 64 68 72 76 80 84
TEMPERATURE CC)
F i g u r e 7. E x p e r i m e n t a l p r e s s u r e - t e m p e r a t u r e t r a c e of the
t h r e e - p h a s e s o l i d - l i q u i d gas l i n e t h a t t e r m i n a t e s at
the UCEP f o
S-L-G line
80.3°C (Δ).
demonstrated i n the n a p h t h a l e n e - s u p e r c r i t i c a l e t h y l e n e system

(50), e x a c t l y a t the UCEP temperature a s o l u b i l i t y i s o t h e r m
s h o u l d show a h o r i z o n t a l p o i n t o f i n f l e c t i o n a t the UCEP p r e s
s u r e . Our 58.5°C i s o t h e r m i n f l e c t i o n p o i n t t h e r e f o r e shows t h a t
we a r e o p e r a t i n g i n c l o s e p r o x i m i t y t o the UCEP.
The l o c a t i o n o f the UCEP i s q u i t e important i n these mix
t u r e s : t h i s c r i t i c a l p o i n t g i v e s the maximum temperature a t
which s o l i d - g a s e q u i l i b r i u m e x i s t s a t a l l p r e s s u r e s . In o r d e r
t o o b t a i n i t s l o c a t i o n , we f i r s t used our NMR method t o d e t e r
mine the S-L-G l i n e . The r e s u l t s o f our e x p e r i m e n t a l d e t e r m i n a
t i o n o f the p r e s s u r e - t e m p e r a t u r e t r a c e f o r the s o l i d - l i q u i d - g a s
e q u i l i b r i u m l i n e t h a t t e r m i n a t e s a t the UCEP f o r the naphtha
l e n e - c a r b o n d i o x i d e system i s shown i n F i g u r e 7.
T h i s phase l i n e and the l o c a t i o n o f the UCEP have been
p r e v i o u s l y d e t e r m i n e d by McHugh (51_) and McHugh and Yogan ( 4 9 ) .
However, our d a t a d i f f e r from the r e s u l t s o f those s t u d i e s . The
p r e v i o u s s t u d i e s have found a s u b s t a n t i a l temperature minimum i n
the phase l i n e a t about 57.5°C and 117 bar ( i . e . , as p r e s s u r e
i n c r e a s e s , the S-L-G l i n e b e g i n s w i t h a n e g a t i v e s l o p e (dP/dT),
r e a c h e s the temperature minimum, and then proceeds w i t h a p o s i
t i v e s l o p e t o the UCEP). T h i s would suggest, f o r example, t h a t
as p r e s s u r e was i n c r e a s e d a l o n g a 58.5°C i s o t h e r m the S-L-G line
would be c r o s s e d and a l i q u i d phase would be p r e s e n t . On the
c o n t r a r y , our s o l u b i l i t y measurements a l o n g t h i s i s o t h e r m showed
no l i q u i d phase f o r m a t i o n . As can be seen i n F i g u r e 6, we
o b t a i n e d o n l y a s l i g h t temperature minimum f o r the S-L-G l i n e ,
and a 58.5°C i s o t h e r m does not i n t e r s e c t our S-L-G phase bound
a r y . We thus b e l i e v e our S-L-G l i n e r e s u l t s t o be more a c c u r a t e
s i n c e they b e t t e r c o r r e l a t e w i t h our s o l u b i l i t y d a t a .
The h i g h p r e s s u r e t e r m i n a t i o n o f the S-L-G l i n e g i v e s the
p r e s s u r e - t e m p e r a t u r e l o c a t i o n o f the upper c r i t i c a l end p o i n t .
The v a l u e f o r the UCEP temperature shown by the h i g h p r e s s u r e
p o r t i o n o f our S-L-G l i n e i s 60.1°C. T h i s a g r e e s w i t h the v a l u e
f o r the UCEP temperature r e p o r t e d by McHugh and Yogan ( 4 9 ) .
Next, i n o r d e r t o d e t e r m i n e the UCEP p r e s s u r e , we have used the

2. JONAS AND LAMB Transport and Intermolecular Interactions 27
t h e o r y o f G i t t e r m a n and P r o c a c c i a ( 5 2 ) . T h i s a n a l y s i s gave the

UCEP p r e s s u r e a s P =* 2 2 7 b a r .
Q I n t h i s way we h a v e b e e n a b l e
f o r t h e f i r s t t i m e t o d e t e r m i n e t h e l o c a t i o n o f t h e UCEP f o r t h e
naphthalene carbon dioxide system. T h e s e r e s u l t s show t h a t o u r
n o v e l NMR m e t h o d c a n y i e l d b o t h s o l u b i l i t y d a t a a n d p h a s e i n f o r
m a t i o n when s t u d y i n g e q u i l i b r i a i n s u p e r c r i t i c a l f l u i d m i x t u r e s .
Acknowledgments
T h i s w o r k was p a r t i a l l y s u p p o r t e d b y t h e Department o f Energy

under Grant DE-FG-82PC50800.
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RECEIVED June 24, 1986

Chapter 3
Application of Solvatochromic Probes to Supercritical

and Mixed Fluid Solvents
S. L. Frye, C. R. Yonker, D. R. Kalkwarf, and R. D. Smith
Chemical Methods and Separations Group, Chemical Technology Department, Pacific

Northwest Laboratory, Battelle Memorial Institute, Richland, WA 99352
Changes of the polarity/polarizability of supercritical

CO2, N20, Freon-13, NH3, and CO2/methanol mixtures, were
measured by observing the shift of the UV absorption of
2-nitroanisole as a function of temperature and pres
sure. The polaritie
are compared to those of liquid solvents through use of
the Kamlet-Taft π* polarity scale. In pure supercritical
solvents the polarity was found to correlate primarily
with density. The data for CO2 indicate that a change in
the cybotatic region occurs at a fluid density of
~0.3 g/cm3. Adding methanol as a modifer to supercritical
CO2gradually increases the polarity of the solvent and in
solutions with over 10% methanol the composition of the
cybotatic region appears to be enriched in methanol (com
pared to the bulk composition).
Supercritical fluids are increasingly being used as solvents in both

analytical and process applications. The increasing interest in the
use of supercritical fluid solvents is partially due to the depend
ence of fluid solvent properties on temperature and pressure. One
is able to change to a "different" solvent simply by changing the
fluid temperature or pressure. This variability in solvent proper
ties adds an extra degree of freedom in solvent use. However, there
are a variety of complex interactions between the solvent and solute
which complicate understanding the behavior of supercritical sol
vents. Some of the interactions are nonspecific, occurring between
any solvent-solute pair, while other interactions (such as hydrogen
bonding) are dependent upon the specific solvent and solute.
Because the strength of such interactions depends on intermolecular
distances, the relative importance of each contribution is density
dependent. A large body of work exists that studies the various
solvent-solute interactions using liquid solvents; however, very few
results have been reported for supercritical fluid solvents.
This study was aimed at investigating solvent-solute interac
tions in the supercritical fluid (dense gas) regime, particularly
0097-6156/87/0329-0029$06.00/0

t h e dependence o f s p e c i f i c s o l v e n t i n t e r a c t i o n s on t e m p e r a t u r e and
pressure. A s p e c t r o s c o p i c t e c h n i q u e has been used t o o b t a i n i n f o r
mation about t h e s o l v e n t environment i n t h e v i c i n i t y of a s o l u t e
m o l e c u l e and t o m o n i t o r changes i n t h a t r e g i o n as the f l u i d t e m p e r a
t u r e and p r e s s u r e a r e v a r i e d . The r e s u l t s show t h a t t h e r e g i o n s u r
r o u n d i n g a s o l u t e m o l e c u l e can change more d r a s t i c a l l y than the bulk
s o l v e n t d e n s i t y and p r o v i d e a means f o r comparison of l i q u i d and
supercritical f l u i d solvents. T h i s method s h o u l d be p a r t i c u l a r l y
u s e f u l i n e x p l o r i n g mixed f l u i d s y s t e m s .
Approach
The wide v a r i e t y of p o s s i b l e s o l v e n t - s o l u t e i n t e r a c t i o n s r e q u i r e s
t h a t any s c a l e used t o q u a n t i f y s o l v e n t p r o p e r t i e s w i l l be com
plex. U n f o r t u n a t e l y , no u n i v e r s a l l y a c c e p t e d s c a l e of s o l v a t i n g
power has been d e v i s e d . It does not seem r e a s o n a b l e t o develop an
e n t i r e l y new s c a l e f o r s u p e r c r i t i c a l f l u i d s o l v e n t s , e s p e c i a l l y
since i t is desirable t
cal f l u i d s with that o
Of the e x i s t i n g s o l v e n t s c a l e s , the Kami et and T a f t π* s c a l e
(JL) appears a p p r o p r i a t e f o r use with s u p e r c r i t i c a l f l u i d s o l v e n t s .
The b a s i s of t h e Kami et and T a f t s c a l e i s t h e e f f e c t of s o l v e n t
p o l a r i t y and p o l a r i z a b i l i t y on the energy of the % + π* e l e c t r o n i c
t r a n s i t i o n of a s o l u t e probe m o l e c u l e . S o l v e n t m o l e c u l e s i n p r o x
i m i t y t o a s o l u t e (the c y b o t a t i c r e g i o n ) d i f f e r e n t i a l l y a f f e c t t h e
e l e c t r o n i c energy l e v e l s of s o l u t e s (the s o l v a t o c h r o m i c e f f e c t )
(_2_). In t h i s manner, t h e e l e c t r o n i c t r a n s i t i o n s o f some m o l e c u l e s
a r e s e n s i t i v e probes of t h e s o l u t e e n v i r o n m e n t . S i n c e the probe
m o l e c u l e s s e l e c t e d by Kamlet and T a f t have π * e l e c t r o n i c s t a t e s
which a r e more p o l a r than the ground s t a t e , a change i n the p o l a r -
i t y / p o l a r i z a b i l i t y of the s o l v e n t medium changes the e l e c t r o n i c
energy gap, and thus the p o s i t i o n of the a b s o r p t i o n band. Kamlet
and T a f t have d e v e l o p e d an e m p i r i c a l r e l a t i o n s h i p between measured
s o l u t e a b s o r p t i o n maxima i n a s o l v e n t and the p o l a r i t y / p o l a r -
i z a b i l i t y of t h a t s o l v e n t :
ν = v Q + sic*
ν = a b s o r p t i o n maximum i n t e s t s o l v e n t
v =Q a b s o r p t i o n maximum i n r e f e r e n c e s o l v e n t
s = s o l u t e dependent parameter
π* = measured s o l v e n t p o l a r i t y / p o l a r i z a b i l i t y parameter
In subsequent work Kamlet and T a f t added a d d i t i o n a l terms t o t h i s

r e l a t i o n s h i p t o account f o r hydrogen bonding and o t h e r t y p e s o f
s o l v e n t - s o l u t e i n t e r a c t i o n s (3>_4).
S i n c e i t s i n t r o d u c t i o n t h e K a m l e t - T a f t π * s c a l e has been
a p p l i e d t o a l a r g e number of d i v e r s e l i q u i d s o l v e n t s (_5). Several
s t u d i e s have shown t h a t the π * s o l v e n t s c a l e i s c o n s i s t e n t w i t h
o t h e r p o p u l a r measures of s o l v e n t s t r e n g t h ( 6 J . It has a l s o been
shown t h a t t h e r e a r e good c o r r e l a t i o n s between t h e e m p i r i c a l meas
urements of t h e Kamlet and T a f t s c a l e and s e v e r a l t h e o r e t i c a l models
o f s o l v e n t b e h a v i o r (7_). Use o f t h e s o l u t e s chosen by Kamlet and

3. FRYE ET AL. Application of Solvatochromic Probes 31
T a f t p e r m i t s d i r e c t comparison between t h e r e s u l t s f o r s u p e r c r i t i c a l
f l u i d s o l v e n t s and the known b e h a v i o r of l i q u i d s o l v e n t s .
Experimental
The s o l v a t o c h r o m i c probe m o l e c u l e chosen f o r t h i s work was

2 - n i t r o a n i s o l e ( A l d r i c h Chemical C o . ) . The s value r e p o r t e d i n t h e
l i t e r a t u r e f o r 2 - n i t r o a n i s o l e i s - 2 . 4 2 8 + 0.195 (J_). A known s
v a l u e f o r the s o l u t e a l l o w s one t o c a l c u l a t e the change i n t h e
s u p e r c r i t i c a l f l u i d s o l v e n t s ' π* v a l u e as temperature or p r e s s u r e
changes. The r e f e r e n c e a b s o r p t i o n maxima f o r 2 - n i t r o a n i s o l e i s
32.56 χ 10^ c m " ( v ) i n c y c l o h e x a n e ( 1 ) .
1
Q
A b s o r p t i o n s p e c t r a of 2 - n i t r o a n i s o l e i n s u p e r c r i t i c a l C 0 , N 0 ,
2 2
F r e o n - 1 3 , ammonia and C 0 - m e t h a n o l m i x t u r e s were o b t a i n e d on a Cary

2
model 1605 s p e c t r o p h o t o m e t e r o p e r a t e d i n the dual beam mode. The

gases used as s u p e r c r i t i c a l s o l v e n t s were of t h e h i g h e s t p u r i t y
a v a i l a b l e from t h e s u p p l i e r (Matheson) and were f u r t h e r f i l t e r e d
p r i o r to use. The mixe
from S c o t t S p e c i a l i t y Gase
were made i n t h e l a b o r a t o r y . S p e c t r a of 2 - n i t r o a n i s o l e i n
n - p e n t a n e , m e t h a n o l , t e t r a h y d r o f u r a n and a c e t o n i t r i l e (Burdick &
J a c k s o n ) were o b t a i n e d u s i n g q u a r t z c e l l s with a 1-cm l i g h t path and
with a pure s o l v e n t blank i n the r e f e r e n c e beam. Vapor phase and
s u p e r c r i t i c a l f l u i d s p e c t r a were o b t a i n e d u s i n g an a i r r e f e r e n c e .
The c y l i n d r i c a l h i g h - p r e s s u r e c e l l was c o n s t r u c t e d from s t a i n
l e s s s t e e l (SS 304) and had dimensions of 1 i n . d i a m e t e r by 2 i n .
l e n g t h , with a 3 / 1 6 - i n . - d i a m e t e r h o l e d r i l l e d along t h e a x i s . High-
p r e s s u r e 1 / 1 6 - i n . O.D. s t a i n l e s s s t e e l i n l e t and o u t l e t c o n n e c t i o n s
were s i l v e r s o l d e r e d i n t o the c e l l , which allowed f o r s u p e r c r i t i c a l
f l u i d to flow through and purge t h e c e l l . Each end of the c e l l had
a seat f o r a 1 / 4 - i n . O.D., 1 / 4 - i n . - t h i c k q u a r t z window, and was
t h r e a d e d to a c c e p t a b r a s s compression n u t . A 1 / 4 - i n . O.D. T e f l o n
o - r i n g was p l a c e d on each s i d e of each window t o p r o v i d e c u s h i o n i n g
and make a g a s - t i g h t s e a l . The o p t i c a l path l e n g t h o f t h e assembled
c e l l was a p p r o x i m a t e l y 1.5 cm with a t o t a l volume of 350 μ λ . The
a b s o r p t i o n c e l l was e l e c t r i c a l l y heated and the temperature moni
t o r e d with a t h e r m o c o u p l e . F o r the mixed f l u i d s o l v e n t systems a
s i m i l a r , l a r g e r volume h i g h - p r e s s u r e c e l l was u s e d . E i t h e r assembly
c o u l d be p l a c e d i n the sample compartment of the s p e c t r o p h o t o m e t e r ,
and a s i n g l e mode t e m p e r a t u r e c o n t r o l l e r (West) p r o v i d e d temperature
regulation to within ±0.5°C. The s u p e r c r i t i c a l s o l v e n t was d e l i v
ered t o t h e c e l l by a h i g h - p r e s s u r e s y r i n g e pump (High P r e s s u r e
Equipment) and was connected t o the c e l l v i a a h i g h - p r e s s u r e l i q u i d
c h r o m a t o g r a p h i c sampling v a l v e (Rheodyne I n c . ) . The sampling v a l v e
c o n t a i n e d a 10 μ £ sample l o o p ; t h i s allowed f o r easy i n t r o d u c t i o n of
2 - n i t r o a n i s o l e i n t o the a b s o r p t i o n c e l l . A pressure transducer
(Model 204, S e t r a Systems) p r o v i d e d p r e s s u r e measurement ( ± 1 0 p s i ) .
The experiments were conducted as f o l l o w s : the sample was
loaded i n t o the sample loop of the i n j e c t i o n v a l v e and a v a l v e at
t h e c e l l o u t l e t was opened t o a l l o w f l u i d from the pump t o f l o w
through the c e l l . The sample loop was then switched i n l i n e and the
absorbance monitored t o d e t e c t the appearance of the sample i n t h e
cell. The s o l u t e (probe) c o n c e n t r a t i o n was d i l u t e d by i n t r o d u c t i o n
of a d d i t i o n a l s o l v e n t t o o b t a i n the d e s i r e d c o n c e n t r a t i o n (and

absorbance). The o u t l e t v a l v e was then c l o s e d and t h e a b s o r p t i o n

spectrum of t h e 2 - n i t r o a n i s o l e was r e c o r d e d . Subsequent scans at
d i f f e r e n t p r e s s u r e s o r t e m p e r a t u r e s were made a f t e r a p p r o p r i a t e
equilibration periods. In a l l cases t h e pure f l u i d s p e c t r a were
r e c o r d e d t o ensure t h a t t h e r e were no i n t e r f e r e n c e s .
Results and D i s c u s s i o n
Pure F l u i d s . Table I gives the c r i t i c a l p r o p e r t i e s f o r the four

pure f l u i d s s t u d i e d . T a b l e II l i s t s t h e a b s o r p t i o n maxima f o r t h e
probe m o l e c u l e ( 2 - n i t r o a n i s o l e ) i n a v a r i e t y of l i q u i d and s u p e r -
c r i t i c a l f l u i d solvents. Comparing t h e r e s u l t s f o r t h e l i q u i d s , i t
i s o b v i o u s t h a t i n c r e a s i n g t h e p o l a r i t y o f t h e s o l v e n t causes t h e
a b s o r p t i o n t o be s h i f t e d t o l o n g e r wavelengths ( i . e . , red
shifted). As e x p e c t e d , t h e vapor phase c o r r e s p o n d s t o t h e l e a s t
p o l a r or p o l a r i z a b l e " s o l v e n t " . The r e s u l t s f o r t h e s u p e r c r i t i c a l
f l u i d s o l v e n t s at t h e reduced d e n s i t of 1.5 g i v e n i n T a b l e II
show them t o be comparabl
not as p o l a r as the s u b c r i t i c a
the s u p e r c r i t i c a l s o l v e n t s i s u n d e r s t a n d a b l e when the much lower
d e n s i t y o f t h e s e f l u i d s (at t h e s e e x p e r i m e n t a l c o n d i t i o n s ) i s taken
into account. In f a c t , at a reduced d e n s i t y of 0.8 a l l t h e f l u i d s
g i v e s o l v a t o c h r o m i c s h i f t s l e s s than t h a t observed f o r p e n t a n e .
At more " l i q u i d - l i k e " d e n s i t i e s , t h e s o l v a t o c h r o m i c s h i f t s i n
s u p e r c r i t i c a l f l u i d s approach t h o s e observed i n t h e c o r r e s p o n d i n g
liquids. F i g u r e s 1 and 2 d e p i c t the p r e s s u r e dependence of t h e
wavelength o f t h e a b s o r p t i o n maximum o f 2 - n i t r o a n i s o l e i n s u p e r c r i t -
i c a l C0 2 , N 2 0, CCIF3 ( F r e o n - 1 3 ) , and NH3. These measurements
r e f l e c t t h e e f f e c t of p r e s s u r e ( f l u i d d e n s i t y ) on t h e c y b o t a t i c
r e g i o n of t h e s e s o l v e n t s . It i s c l e a r t h a t t h e f l u i d d e n s i t y
a f f e c t s t h e c y b o t a t i c r e g i o n , as e v i d e n c e d by t h e s h i f t i n t h e
a b s o r p t i o n maximum w i t h p r e s s u r e ; and i t i s a l s o e v i d e n t t h a t t h e
magnitude o f t h e s h i f t i s f l u i d dependent.
A more d i r e c t comparison of t h e r e s u l t s from t h e d i f f e r e n t f l u -
i d s i s o b t a i n e d by p l o t t i n g t h e peak p o s i t i o n vs reduced d e n s i t y , as
shown i n F i g u r e 3. With F r e o n - 1 3 as t h e s o l v e n t t h e peak maximum i s
at g r e a t e r wave numbers, which i s c h a r a c t e r i s t i c o f a l e s s - p o l a r
solvent. There i s o n l y a small s h i f t i n t h e peak p o s i t i o n as t h e
d e n s i t y i s changed. C 0 and N 0 e x h i b i t q u i t e s i m i l a r peak p o s i -
2 2
t i o n s and s h i f t s at a p p r o x i m a t e l y equal reduced d e n s i t i e s , which i s

c o n s i s t e n t w i t h t h e i r s i m i l a r p h y s i c o c h e m i c a l b e h a v i o r and c r i t i c a l
points. F i n a l l y , t h e r e s u l t s f o r NH i n d i c a t e t h a t i t i s t h e most
3
TABLE I. C r i t i c a l properties for f o u r pure fluids
Supercritical
Fluid P (atm)
c p (g/cm )
c
3
C0 2 304.2 72.8 0.46

N02 309.6 71.7 0.45
C&IF3 302.0 38.1 0.58
NH 3 405.6 111.3 0.24

TABLE II. π* Solubility Scale Parameters and t h e Peak Position of Absorbance Maximum f o r 2-Nitroanisole
v b s e r v d
Q max Q Ç
J 6 1
Sol vent Τ (Κ) Ρ (atm) ρ (g/cm ) χ W' (cm" ) 71*
Vapor 34.97 35.13 -1.060>>

CCIF3 ( c ) 303 90 33.26 0.07 -0.29 ± 0.03
CClF e) g
296 270 33.07 0.10 -0.21 ± 0.04
f
323 180 0.68< ) 33.85 0.09 -0.12 + 0.03
d
Pentane 298 1 0.626 4

32.89 32.75 -0.08( )
f -0.07 ± 0.04
c 323 180 0.69 33.73 0.10
co 2
296 270 Ο.95Ο 32.63 0.05 -0.03 ± 0.02

f
296 270 0.95 32.47 0.05 0.04 ± 0.03

f
Mil 413 170 0.36( ) 31.75 0.25 0.34 ± 0.07
b
Ν Η 3 ^ 298 1 0.888 31.45 31.15 0.58j J
b
Tetrahydrofuran 298 1 0.791 31.06 31.10 0.60
Methanol 298 1 0.777 30.86 30.74 0.75(b)
Acetonitrile 296 270 0.62(0 30.63 ± 0.04 0.80 ± 0.02
e

NH ( ) 3
3 1
Q
v a l u e s c a l c u l a t e d based on v = 32.56 χ 1 0 " cm'
(a)
(b) v a l u e s from r e f e r e n c e 5.
(c) p
S u p e r c r i t i c a l f l u i d , p = 1.5.
(d) E s t i m a t e π * v a l u e f o r pentane from r e f e r e n c e 5.
(e) determined f o r s u b c r i t i c a l l i q u i d .

( f ) E s t i m a t e d from "Gas E n c y c l o p e d i a " ; E l s e v i e r S c i e n t i f i c : Amsterdam, 1976.
• Freon-13
_ Δ C0 2
* *
i 1
i i i i i
£ 300
X
ω 298
Ε
296
292
290 I 1 i 1 I ι ι ι ι · • 1 1 1 1 1 1 1 1 1 1 1 J_._L
1000 1500 2000 3000
Pressure (psi)
F i g u r e 1. Wavelength of maximum absorbance ( ^ ) versus m a x pres

sure ( p s i ) f o r 2 - n i t r o a n i s o l e with C0 and F r e o n - 1 3 . 2
1500 2000 2500
Pressure (psi)
F i g u r e 2. Wavelength of maximum absorbance ( λ ^ χ ) v e r s u s pres

sure ( p s i ) f o r 2 - n i t r o a n i s o l e w i t h N 0 and NH3. 2

p o l a r s o l v e n t examined, d i s p l a y i n g t h e l a r g e s t v a r i a t i o n i n t h e
c y b o t a c t i c r e g i o n as t h e f l u i d d e n s i t y i s changed.
From the p o s i t i o n of t h e absorbance maximum i n d i f f e r e n t f l u
i d s , t h e c o r r e s p o n d i n g π * parameter v a l u e s are r e a d i l y c a l c u l a t e d ,
a l l o w i n g comparison of s u p e r c r i t i c a l f l u i d s at v a r i o u s e x p e r i m e n t a l
c o n d i t i o n s with c o n v e n t i o n a l l i q u i d s o l v e n t s . In F i g u r e 4 the c a l
c u l a t e d π * v a l u e s are p l o t t e d vs the reduced d e n s i t y f o r the v a r i o u s
fluids. Two s e t s of p o i n t s have been p l o t t e d f o r C 0 ; one set of2
measurements were made by v a r y i n g t h e p r e s s u r e at c o n s t a n t t e m p e r a

t u r e , the o t h e r i s f o r v a r i o u s t e m p e r a t u r e s at c o n s t a n t p r e s s u r e .
The two d a t a s e t s f a l l on a s i n g l e c u r v e ( w i t h i n e x p e r i m e n t a l
e r r o r ) , i n d i c a t i n g t h a t t h e f l u i d d e n s i t y i s the prime f a c t o r i n
d e t e r m i n i n g t h e v a l u e of π * . The data f o r the o t h e r f l u i d s was
o b t a i n e d under i s o t h e r m a l c o n d i t i o n s .
The data i n d i c a t e t h a t as the reduced d e n s i t y of a f l u i d i s
i n c r e a s e d the c y b o t a t i c r e g i o n becomes more p o l a r / p o l a r i z a b l e , w i t h
an e s p e c i a l l y l a r g e e f f e c t f o r s u p e r c r i t i c a l NH3 The lo * values
f o r F r e o n - 1 3 at t h e s e d e n s i t i e
p e r f l u o r o - a l k a n e s (_5). Th
range between t h o s e of the p e r f l u o r o - a l k a n e s to t h a t of t h e
n - a l k a n e s ( η - h e p t a n e , e t c . ) (5). Ammonia g i v e s π * v a l u e s which
range from a p p r o x i m a t e l y t h a t of η - h e p t a n e t o t h a t of e t h y l a c e t a t e
or t e t r a h y d r o f u r a n (_5) o v e r the d e n s i t y range s t u d i e d .
Comparison o f %* v a l u e s w i t h s o l u b i l i t y parameters f o r the v a r
i o u s l i q u i d s and f l u i d s , c a l c u l a t e d as d e s c r i b e d by G i d d i n g s and
coworkers ( 1 0 ) , shows a general c o r r e l a t i o n f o r t h e l e s s p o l a r s o l
vents. Ammonia and t h e p o l a r l i q u i d s o l v e n t s d i v e r g e from t h i s c o r
r e l a t i o n , s u g g e s t i n g the o p e r a t i o n of s p e c i f i c i n t e r a c t i o n s which
c o n t r i b u t e t o t h e g r e a t e r magnitude of t h e s h i f t s observed f o r
ammonia.
It i s p o s s i b l e t o compare t h e s e r e s u l t s with t h o s e r e p o r t e d i n
the l i t e r a t u r e f o r s u p e r c r i t i c a l C 0 . 2 Hyatt (8) r e p o r t s π* v a l u e s
f o r C 0 from - 0 . 5 2 t o - 0 . 0 which compares very f a v o r a b l y w i t h t h e
2
p r e s e n t v a l u e of - 0 . 5 5 at a reduced d e n s i t y of 0 . 4 3 . Sigman et a l .
(9_) used a number of s o l u t e s t o determine π * v a l u e s f o r C 0 at f l u i d 2
d e n s i t i e s of 0 . 8 6 , 0 . 6 8 , and 0.46 g / c m of - 0 . 1 2 , - 0 . 2 2 , and - 0 . 4 5 ,

3
respectively. The p r e s e n t v a l u e s at s i m i l a r d e n s i t i e s are - 0 . 0 5 ,

- 0 . 1 0 , and - 0 . 2 5 . The s o u r c e of t h i s d i s c r e p a n c y i s unknown,
a l t h o u g h Sigman et a l . a t t r i b u t e t h e v a r i a t i o n i n π * v a l u e s among
t h e i r various i n d i c a t o r s to s p e c i f i c solute e f f e c t s .
The K a m l e t - T a f t π * p o l a r i t y / p o l a r i z a b i l i t y s c a l e i s based on a
l i n e a r s o l v a t i o n energy r e l a t i o n s h i p between t h e π π* t r a n s i t i o n
energy of t h e s o l u t e and t h e s o l v e n t p o l a r i t y ( 1 ) . The Onsager
r e a c t i o n f i e l d t h e o r y (11) i s a p p l i c a b l e t o t h i s type of r e l a t i o n
s h i p f o r n o n p o l a r s o l v e n t s , and s u c c e s s f u l c o r r e l a t i o n s have p r e v i
o u s l y been demonstrated u s i n g c o n v e n t i o n a l l i q u i d s o l v e n t s (_7). The
Onsager t h e o r y attempts t o d e s c r i b e t h e i n t e r a c t i o n s between a p o l a r
s o l u t e m o l e c u l e and the p o l a r i z a b l e s o l v e n t i n the c y b o t a t i c
region. The t h e o r y p r e d i c t s t h a t t h e s t a b i l i z a t i o n o f t h e s o l u t e
s h o u l d be p r o p o r t i o n a l t o t h e p o l a r i z a b i l i t y of t h e s o l v e n t , which
can be e s t i m a t e d from t h e i n d e x of r e f r a c t i o n . S i n c e carbon d i o x i d e
i s a n o n p o l a r f l u i d i t would be e x p e c t e d t h a t a l i n e a r r e l a t i o n s h i p

Δ C0 2
• Freon-13
• Ν 0
2
Ο ΝΗ 3
i ι
£ 33
υ
CO
ι
Ο
Χ
IL
3 2
Ρ
-I I I I I
J I I LI I L
Pr
F i g u r e 3. ν v e r s u s reduced d e n s i t y ( ρ ) for
Γ 2-nitroanisole
with C 0 , N 0,
2 2 F r e o n - 1 3 and N H . 3
0.6 X C0 2 (P Change)
Δ C0 2 (T Change)
• Freon-13
0.4
• N 0
If
2
Ο NH 3
0.2
ι I ι I ι I ι I ι ι • ι • ι ' I • '
0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2
Pr
F i g u r e 4. π * v e r s u s reduced d e n s i t y (p ) r for 2-nitroanisole

w i t h C 0 , N 0 , F r e o n - 1 3 and N H .
2 2 3

would be o b t a i n e d between t h e measured π * v a l u e s at d i f f e r e n t densi

t i e s and the Onsager r e a c t i o n f i e l d f u n c t i o n L(n ):
L(n )
2
= (η 2
- 1) / (2n 2
+ 1)
The Onsager f u n c t i o n i s dependent on t h e r e f r a c t i v e index o f

the solvent (n). For s u p e r c r i t i c a l C 0 t h e r e f r a c t i v e index i s
2
dependent on the f l u i d d e n s i t y and can be c a l c u l a t e d from t h e

Lorentz-Lorenz r e f r a c t i o n equation:
T ) P+
(V^) Φ = A
R +
V —
η + 2 p K K
where A and B R ( T ) are t h e f i r s t and second r e f r a c t o m e t r i c v i r a l

R
c o e f f i c i e n t s (12,13). K h o l o d o v , Timoshenko, and Yaminov (12) and

Bose and S t . Arnaud (13) have r e p o r t e d v a l u e s f o r t h e s e c o e f f i c i e n t s
for s u p e r c r i t i c a l C0 , enablin
2
at v a r i o u s t e m p e r a t u r e s
A p l o t of the Onsager f u n c t i o n vs the measured π v a l u e s f o r
C 0 i s g i v e n i n F i g u r e 5.
2 A change i n t h e s l o p e of the p l o t o c c u r s
at a d e n s i t y o f ~0.3 g/cm (reduced d e n s i t y of ~ 0 . 7 ) . The n o n l i n e -
a r i t y of t h e p l o t s u g g e s t s t h a t a change i n t h e c h a r a c t e r of the
c y b o t a t i c r e g i o n o c c u r s as the d e n s i t y of CO? i n c r e a s e s . At low
f l u i d d e n s i t i e s t h e s o l v a t i n g power of the s o l v e n t s h o u l d be low,
a p p r o a c h i n g the vapor phase l i m i t as the d e n s i t y i s d e c r e a s e d . A
l i n e a r l e a s t squares f i t t o t h e s e data y i e l d an i n t e r c e p t v a l u e of
- 1 . 0 2 f o r π * , which compares f a v o r a b l y with the vapor phase l i m i t of
- 1 . 0 6 + 0.10 r e p o r t e d by E s s f a r , G u i h e n u e f , and Abboud (JL4). At
h i g h e r f l u i d d e n s i t i e s i t a c t s more l i k e a l i q u i d s o l v e n t as more
complex m u l t i p l e s o l v e n t - s o l u t e i n t e r a c t i o n s become i m p o r t a n t . In
f a c t , data f o r the s u b c r i t i c a l l i q u i d shows t h e π* v a l u e f o r the
f l u i d and l i q u i d , at equal d e n s i t i e s , t o be i d e n t i c a l w i t h i n e x p e r i
mental l i m i t s . At some i n t e r m e d i a t e f l u i d d e n s i t y a t r a n s i t i o n
o c c u r s from the low p r e s s u r e r e g i o n t o s o l v e n t b e h a v i o r more c h a r a c
t e r i s t i c of l i q u i d s , l e a d i n g t o the change i n s l o p e observed i n t h i s
plot. It i s not c l e a r why t h e t r a n s i t i o n t a k e s p l a c e at t h i s d e n
s i t y , however i t i s i n t e r e s t i n g t o note t h a t i n t h i s d e n s i t y r e g i o n
v i r i a l c o e f f i c i e n t s beyond t h e second ( i n d i c a t i n g m u l t i - m o l e c u l e
i n t e r a c t i o n s i n the s o l v e n t ) become s i g n i f i c a n t and s i g n i f i c a n t
enhancements i n s o l u b i l i t y are t y p i c a l l y o b s e r v e d . F u r t h e r work i s
ongoing t o e l u c i d a t e t h i s b e h a v i o r .
Mixed F l u i d s . Adding a d d i t i o n a l components to s u p e r c r i t i c a l f l u i d

s o l v e n t s , e n t r a i n e r s i n s u p e r c r i t i c a l f l u i d e x t r a c t i o n systems and
m o d i f i e r s i n s u p e r c r i t i c a l f l u i d chromatography, can extend o r s i g
n i f i c a n t l y a l t e r the f l u i d s o l v a t i n g p r o p e r t i e s ( 1 5 , 1 6 ) . By v a r y i n g
t h e c o m p o s i t i o n of the f l u i d mixture i t i s p o s s i b l e t o extend t h e
range of f l u i d s o l v e n t p r o p e r t i e s w h i l e r e t a i n i n g the advantages of
supercri t i c a l sol vents.
The n a t u r e of mixed f l u i d s o l v e n t systems and t h e i r r o l e i n
v a r i o u s s u p e r c r i t i c a l f l u i d a p p l i c a t i o n s i s c o m p l i c a t e d by the
i n c r e a s e d c o m p l e x i t y of the phase b e h a v i o r . S e v e r a l d i f f e r e n t types
of mixed f l u i d phase b e h a v i o r have been i d e n t i f i e d ( 1 7 , 1 8 ) , some of

them i n v o l v i n g m u l t i p l e l i q u i d and vapor p h a s e s . Without knowledge

o f t h e s p e c i f i c phase b e h a v i o r of a given mixed f l u i d i t i s not p o s -
s i b l e t o i n t e r p r e t c o r r e c t l y s o l v e n t b e h a v i o r o v e r t h e range o f tem-
p e r a t u r e s and p r e s s u r e s of i n t e r e s t .
M i x t u r e s o f C 0 and methanol were s e l e c t e d f o r t h e i n i t i a l
2
i n v e s t i g a t i o n of the s o l v a t o c h r o m i c b e h a v i o r i n s u p e r c r i t i c a l f l u i d
systems. T h i s c o m b i n a t i o n i s of i n t e r e s t as i t combines t h e low
c r i t i c a l t e m p e r a t u r e and p r e s s u r e of carbon d i o x i d e with a p o l a r ,
less v o l a t i l e modifier. T h i s system e x h i b i t s r e l a t i v e l y s i m p l e
Type I phase b e h a v i o r and s e v e r a l groups have p u b l i s h e d measurements
of mixture c r i t i c a l p o i n t s (19-21). At i n t e r m e d i a t e c o m p o s i t i o n s
the c r i t i c a l p r e s s u r e f o r t h i s f l u i d i s much h i g h e r than t h a t of
e i t h e r pure C 0 o r pure m e t h a n o l , r e a c h i n g a maximum o f a p p r o x i -
2
mately 2400 p s i ( 2 0 ) .
F i g u r e 6 i l l u s t r a t e s t h e e f f e c t of p r e s s u r e on t h e p o s i t i o n o f
t h e 2 - n i t r o a n i s o l e a b s o r p t i o n maximum f o r s e v e r a l d i f f e r e n t s o l v e n t
compositions. It i s apparent t h a t adding methanol causes t h e
a b s o r p t i o n t o be r e d - s h i f t e d
vent p o l a r i t y , as e x p e c t e d
s h i f t t h e a b s o r p t i o n maximum t o the v a l u e measured i n pure methanol
(see T a b l e I I ) . It i s i n t e r e s t i n g t o note t h a t t h e 5.6%-methanol
m i x t u r e appears t o be a f f e c t e d by i n c r e a s i n g p r e s s u r e ( s i m i l a r l y t o
pure carbon d i o x i d e ) , but above 9.5%-methanol p r e s s u r e no l o n g e r
e f f e c t s t h e peak p o s i t i o n . It can be s p e c u l a t e d t h a t at the h i g h e r
methanol c o n c e n t r a t i o n t h e c y b o t a t i c r e g i o n i s e n r i c h e d i n methanol
r e l a t i v e t o t h e bulk c o n c e n t r a t i o n and t h a t t h i s methanol r i c h e n v i -
ronment i s not h i g h l y s e n s i t i v e t o p r e s s u r e e f f e c t s , as would be t h e
case f o r pure methanol s o l v e n t . S i m i l a r b e h a v i o r i s shown i n F i g -
ure 7 i n which peak p o s i t i o n i s p l o t t e d vs p r e s s u r e at d i f f e r e n t
t e m p e r a t u r e s f o r a s o l v e n t which i s 15% m e t h a n o l . A g a i n , the p r e s -
s u r e change r e s u l t s i n no s i g n i f i c a n t e f f e c t s over t h e range s t u d -
i e d , but peak p o s i t i o n j_s_ dependent upon t e m p e r a t u r e . These
thermochromic s h i f t s a r e s i m i l a r i n magnitude t o t h o s e r e p o r t e d by
Suppan and T s i a m i s ( 2 2 ) .
It i s p o s s i b l e t o compare t h e s e s p e c t r o s c o p i c measurements o f a
methanol m o d i f i e r i n s u p e r c r i t i c a l carbon d i o x i d e t o r e s u l t s
obtained v i a chromatographic separations with s i m i l a r f l u i d s y s -
tems. The s p e c t r o s c o p i c r e s u l t s i n d i c a t e t h a t adding methanol does
i n c r e a s e t h e f l u i d p o l a r i t y , but small a d d i t i o n s of methanol do not
d r a s t i c a l l y a l t e r the solvent b e h a v i o r . A s i m i l a r r e s u l t has been
found i n t h i s l a b o r a t o r y by measuring t h e r e t e n t i o n times o f a p o l a r
t e s t m i x t u r e w i t h c a p i l l a r y columns ( 2 3 ) . In c o n t r a s t , p r e v i o u s
r e p o r t s w i t h packed columns found a l a r g e e f f e c t w i t h very small
( l e s s than 1%) a d d i t i o n s of methanol t o C 0 ( 1 6 , 2 4 ) .2 A reasonable
c o n c l u s i o n i s t h a t the methanol m o d i f i e r has a measurable e f f e c t on
t h e s u p e r c r i t i c a l f l u i d m o b i l e phase, but a much more s i g n i f i c a n t
e f f e c t i n m o d i f y i n g t h e packed column s t a t i o n a r y p h a s e . These d i f -
f e r e n c e s can be a t t r i b u t e d t o the t y p i c a l l y l a r g e numbers of a c t i v e
s i t e s on t y p i c a l c h r o m a t o g r a p h i c p a c k i n g s compared t o t h e h i g h l y
i n e r t and d e a c t i v a t e d p o l y m e r i c s t a t i o n a r y phases used i n our c a p i l -
l a r y s u p e r c r i t i c a l f l u i d studies (25,26).

FRYE ET AL. Application of Solvatochromic Probes
Ο 0.05 0.10 0.15

2
L (η )
F i g u r e 5. π * versus Onsager reaction f i e l d function (L(n )) for

C 0 , at 323 K.
2
I ι ι ι ϋ
1000 2000 3000 4000 5000
Pressure (psi)
F i g u r e 6. A b s o r p t i o n maxima versus pressure f o r 2-nitroanisole

i n C 0 - m e t h a n o l systems at 50°C.
2
32.4
ο 100°C
II
Δ 70°C
II
32.2 • Τ = 50°C
ο
1 Ο
32.0
Ε
-
ε-ΟΙ
31.8
X -
>
31.6 — Δ
•
•
31.4 -•
1 1 1 1 1 1 I I I 1 1 1 I . , . , ι
1000 2000 3000 4000 5000
Pressure (psi)
F i g u r e 7. A b s o r p t i o n maxima versus p r e s s u r e f o r 2-nitroanisole

i n 15.4% m e t h a n o l - C 0 at v a r i o u s t e m p e r a t u r e s .
2

Conclusions
T h i s study demonstrates the f e a s i b i l i t y of e x p l o r i n g t h e s o l v a t i n g

p r o p e r t i e s of pure s u p e r c r i t i c a l f l u i d s o l v e n t s and s o l v e n t m i x t u r e s
u s i n g s o l v a t o c h r o m i c measurements. The t e c h n i q u e of measuring
s o l v a t o c h r o m i c s h i f t s i s v a l u a b l e f o r p r o b i n g the s p e c i f i c i n t e r a c
t i o n s between s o l v e n t and s o l u t e m o l e c u l e s under v a r y i n g c o n d i t i o n s
o f t e m p e r a t u r e and p r e s s u r e . By u s i n g the Kamlet and T a f t π* s c a l e
i t i s p o s s i b l e t o d i r e c t l y compare the s o l v a t i o n r e g i o n s f o r s u p e r
c r i t i c a l f l u i d and l i q u i d s o l v e n t s . It was demonstrated t h a t the
p o l a r i t y / p o l a r i z a b i l i t y of the c y b o t a t i c r e g i o n i s dependent on both
the f l u i d and the f l u i d d e n s i t y and t h a t at e q u i v a l e n t d e n s i t i e s
s i m i l a r s h i f t s a r e o b s e r v e d f o r t h e s u p e r c r i t i c a l f l u i d and t h e l i q
uid. Using the Onsager r e a c t i o n f i e l d f u n c t i o n i t i s p o s s i b l e t o
a l s o demonstrate t h a t a q u a l i t a t i v e change i n the n a t u r e of t h e
s o l v a t i o n r e g i o n o c c u r s as the f l u i d d e n s i t y i n c r e a s e s from g a s - l i k e
to l i q u i d - l i k e d e n s i t i e s By s t u d y i n g a mixed s u p e r c r i t i c a l f l u i d
s o l v e n t i t was p o s s i b l e
f i e r i n c r e a s e d the p o l a r i t
study a l s o suggests t h a t at h i g h e r bulk methanol c o n c e n t r a t i o n s t h e
c y b o t a t i c r e g i o n may have a d i f f e r e n t c o m p o s i t i o n than t h e bulk
solution. E x t e n s i o n of t h e s e s t u d i e s i s a n t i c i p a t e d t o i n c r e a s e our
u n d e r s t a n d i n g o f the s o l v e n t - s o l u t e i n t e r a c t i o n s which o c c u r i n
supercritical fluids.
Acknowledgment
T h i s work has been s u p p o r t e d by the U.S. Department of Energy,

O f f i c e o f B a s i c Energy S c i e n c e s , under C o n t r a c t DE-AC06-76RL0 1830.
Literature Cited
1. Kamlet, M. J.; Abboud, J.-L. M.; Taft, R. W. J. Am. Chem. Soc.
1977, 99, 6027.
2. Bayliss, N. S.; MacRae, E. G. J. Phys. Chem. 1954, 58, 1002.
3. Taft, R. W.; Kamlet, M. J. J. Am. Chem. Soc. 1976, 98, 2886.
4. Kamlet, M. J.; Taft, R. W. J. Am. Chem. Soc. 1976, 98, 377.
5. Kamlet, M. J.; Abboud, J.-L. M.; Abraham, M. H.; Taft, R. W.
J. Org. Chem. 1983, 48, 2877.
6. Kamlet, M. J.; Abboud, J.-L. M.; Taft, R. W. Prog. Phys. Org.
Chem. 1981, 13, 485.
7. Brady, J. E.; Carr, P. W. J. Phys. Chem. 1985, 89, 1813.
8. Hyatt, J. Α.; J. Org. Chem. 1984, 49, 5097.
9. Sigman, M. E.; Lindley, S. M.; Leffler, J. E. J. Am. Chem.
Soc. 1985, 107, 1471.
10. Giddings, J. C.; Myers, M. N.; McLaren, L.; Keller, R. A. Sci
ence 1968, 162, 67.
11. Onsager, L. J. Am. Chem. Soc. 1936, 58, 1486.
12. Kholodov, E. P.; Timoshenko, Ν. I.; Yaminov, A. L. Thermal
Engineering 1972, 19, 126.
13. Bose, T. K.; St. Arnaud, J. M. J. Chem. Phys. 1979, 71, 4951.
14. Essfar, M.; Guihenuef, G.; Abboud, J.-L. M. J. Am. Chem. Soc.
1982, 104, 6786.

3. FRYE E T AL. Application of Solvatochromic Probes 41
15. Levy, J. M.; Ritchey, W. M. Proc. 6th Int. Symp. Cap. Chromat.
1985, p. 925.
16. Blilie, A. L.; Greibrokk, T. Anal. Chem. 1985, 57, 2239.
17. Van Konynenberg, P. H. Ph.D. Thesis, University of California
at Los Angeles, 1968.
18. Van Konynenberg, P. H.; Scott, R. L. Phil. Trans. Roy. Soc.
1980, 298, 495.
19. Semenova, A. I.; Emel'yanova, Ε. Α.; Tsimmerman, S. S.;
Tsiklis, D. S. Russian J. Phys. Chem. 1979, 53, 1428.
20. Brunner, E. J. Chem. Thermodynamics 1985, 17, 671.
21. Robinson, D. B.; Peng, D.-Y.; Samuel, Y.-K. C. Fluid Phase
Equil. 1985, 24, 25.
22. Suppan, P.; Tsiamis, C. J. Chem. Soc. Faraday Trans 2 1981,
77, 1553.
23. Wright, B. W.; Smith, R. D. J. Chromatogr. 1986, 355, 367.
24. Gere, D. R. Hewlett-Packard Application Note AN800-2, 1983.
25. Wright, B. W.; Peaden, P. Α.; Lee, M. L.; Stark, T. J.
J. Chromatogr. 1982, 248, 17.
26. Wright, B. W.; Kalinoski
1985, 57, 2823.

Chapter 4
Effects of Supercritical Solvents on the Rates

of Homogeneous Chemical Reactions
Sunwook Kim and K. P. Johnston
Department of Chemical Engineering, University of Texas, Austin, TX 78712
Solvatochromic shift data have been obtained for

phenol blue in supercritical fluid carbon dioxide
both with and without a co-solvent over a wide range
in temperature and pressure. At 45°C, SF CO2 must be
compressed to a pressure of over 2 kbar in order to
obtain a transitio
polarizability per unit volume which is comparable to
that of liquid n-hexane. The ET, data can be used to
predict that the solvent effect on rate constants of
certain reactions is extremely pronounced in the near
critical region where the magnitude of the activation
volume approaches several liters/mole.
It is ironic that the large growth in SF extraction at the Max

Planck Institute in Germany in the 1960f s was the result of a
serendipitous discovery of the solvent power of supercritical
ethylene during the "Aufbau" reaction of triethylaluminum with
ethylene (1). A number of recent articles review supercritical
fluid (SF) extraction (2_,.3,4) ; however, the literature contains
relatively few examples where supercritical fluid solvents have
been used to modify or control reaction rate constants Ç5,6^,7).
Liquid phase reactions have been studied over wide pressure ranges,
e.g. 1-10 kbar, to determine activation volumes, i.e. the pressure
derivative of the rate constant. These studies essentially ignore
the highly compressible near supercritical region where activation
volumes can become infinite, either positively or negatively.
Simmons and Mason (7) observed an abrupt decrease in the activation
volume near the critical conditions for the cyclic dimerization of
C2F3CI. Paulaitis et al. (6) measured activation volumes as low as
-500 cc/mol for the Diels-Alder cycloaddition of isoprene and
maleic anhydride in CO2. These examples provide an indication of
the effects of supercritical solvents on the rate constants of
homogeneous chemical reactions although a much larger data base is
needed.
Supercritical fluid solvents offer some potential advantages
compared with liquids as an environment for chemical reactions. It
0097-6156/87/0329-0042$06.00/0

4. KIM AND JOHNSTON Supercritical Fluid Solvents and Reaction Rates 43
w i l l be d e m o n s t r a t e d t h a t r e a c t i o n r a t e c o n s t a n t s o f c e r t a i n r e a c
t i o n s may b e a l t e r e d m a r k e d l y b y s m a l l m o d i f i c a t i o n s i n t h e
p r e s s u r e o f a SF s o l v e n t . R e a c t i o n p r o d u c t s c o u l d be separated
efficiently using supercritical fluid extraction. Industrial
applications of reactions in SF s o l v e n t s include: the
detoxification of wastewater, ethylene polymerization,
i s o m e r i z a t i o n o f η - p a r a f f i n s , s y n f u e l s p r o c e s s i n g , and t h e r e a c t i o n
of ethylene w i t h t r i e t h y 1 a l u m i n u m ( 5 ) .
S o l v e n t s t r e n g t h s c a l e s b a s e d on s o l v a t o c h r o m i s m , i . e . , shifts
i n the a b s o r p t i o n w a v e l e n g t h o f i n d i c a t o r dyes caused by the
s o l v e n t , a r e u s e d commonly t o c o r r e l a t e and t o p r e d i c t r a t e c o n
s t a n t s f o r l i q u i d phase r e a c t i o n s ( 8 - 1 3 ) . L i n e a r s o l v a t i o n energy
r e l a t i o n s h i p s based on s o l v a t o c h r o m i c p a r a m e t e r s have been used t o
c o r r e l a t e and p r e d i c t s o l u b i l i t y phenomena, a b s o r p t i o n maxima i n
I R , NMR, E S R , a n d U V - v i s i b l e s p e c t r o s c o p y , solvent effects on
r e a c t i o n r a t e c o n s t a n t s and e q u i l i b r i u m c o n s t a n t s , f r e e energies
and e n t h a l p i e s o f f o r m a t i o n o f a c i d - b a s e c o m p l e x e s , retention
i n d i c e s i n g a s - l i q u i d chromatograph
chromatography, and f i n a l l y
quantitative structure-activity relationships (14). Although
1 1
solvatochromic "solvent strength s c a l e s have such widespread
a p p l i c a t i o n , t h e y a r e j u s t b e g i n n i n g t o become a v a i l a b l e f o r
s u p e r c r i t i c a l f l u i d s o l v e n t s (15,16) f o r v e r y l i m i t e d p r e s s u r e and
temperature ranges. Solvatochromic data are presented in this
symposium i n t h e a r t i c l e by F r y e e t a l .
Solvatochromic data, s p e c i f i c a l l y absorption or transition
energies ( E ^ / s ) , have been o b t a i n e d f o r the dye p h e n o l b l u e i n
supercritical f l u i d s as a f u n c t i o n o f b o t h t e m p e r a t u r e and
pressure. These d a t a w i l l be u s e d t o compare t h e "solvent
strength" of these f l u i d s with l i q u i d solvents. We w i l l u s e t h e
terms " s o l v e n t s t r e n g t h " and " E ^ " synonymously i n t h i s paper s u c h
t h a t they i n c l u d e the magnitude o f the p o l a r i z a b i l i t y / v o l u m e as
w e l l as t h e d i p o l e moment. The " s o l v e n t s t r e n g t h " h a s been
c h a r a c t e r i z e d by the s p e c t r o s c o p i c s o l v a t o c h r o m i c p a r a m e t e r , E ^ ,
f o r numerous l i q u i d s o l v e n t s (9,11,17,18).
R e a c t i o n r a t e c o n s t a n t s and a c t i v a t i o n v o l u m e s w i l l be
p r e d i c t e d as a f u n c t i o n o f p r e s s u r e i n the h i g h l y c o m p r e s s i b l e near
c r i t i c a l r e g i o n and i n t h e h i g h l y d e n s e , l e s s c o m p r e s s i b l e r e g i o n
using Ε . In a d d i t i o n , the magnitude of the compression o f a
s u p e r c r i t i c a l f l u i d about a s o l u t e i n the h i g h l y c o m p r e s s i b l e
r e g i o n w i l l be d e t e r m i n e d q u a l i t a t i v e l y . These s p e c t r o s c o p i c d a t a ,
which describe i n t e r a c t i o n s at the m o l e c u l a r l e v e l , w i l l benefit
s i g n i f i c a n t l y the understanding o f b o t h phase e q u i l i b r i a and
s o l v e n t e f f e c t s on r e a c t i o n r a t e s i n the s u p e r c r i t i c a l f l u i d s t a t e .
Experimental
Phenol blue (benzoquinone N-[(4-dimethylamino) phenyl] imine,

A l d r i c h >97%) w a s p u r i f i e d b y r e c r y s t a l l i z a t i o n a n d c h r o m a t o g r a p h i c
separation (30). The p u r i t y was c h e c k e d b y t h e m e l t i n g p o i n t
( 1 6 1 - 1 6 2 ° C ) , a n d t h e a b s o r p t i o n maximum i n a c e t o n e ( 5 8 2 nm) a n d i n
C C l ^ (565 nm). The dye was o f c h r o m a t o g r a p h i c p u r i t y as d e t e r m i n e d
by t h i n - l a y e r c h r o m a t o g r a p h y o n s i l i c a g e l .
3
T h e v o l u m e o f t h e c y l i n d r i c a l h i g h p r e s s u r e c e l l w a s 14 c m ,
and t h e p r e s s u r e and t e m p e r a t u r e r a n g e s were 0 t o 6000 p s i and - 3 0

to 250°C, r e s p e c t i v e l y . The i n s i d e d i a m e t e r was 1.75 cm, and the

w a l l t h i c k n e s s was 1.67 cm. Because o f the l a r g e 6 cm p a t h l e n g t h
of t h e c e l l , t h e s p e c t r a l s h i f t can be measured f o r c o n c e n t r a t i o n s
6
as low as 10 M a t 0.1 Absorbance u n i t s . Each 1 c m - t h i c k by 2.5 cm
i n d i a m e t e r s a p p h i r e window was f l a t t o one w a v e l e n g t h o f y e l l o w
l i g h t , and t h e o p t i c a l a x i s was p e r p e n d i c u l a r t o the f a c e . A
t e f l o n o - r i n g was i n s e r t e d between t h e window and a f l a t s u r f a c e on
the 316 s t a i n l e s s s t e e l v e s s e l . The c e l l was t h e r m o s t a t e d u s i n g a
V copper heat exchange c o i l which was j a c k e t e d w i t h f i b e r g l a s s
insulation.
The temperature was i n d i c a t e d and c o n t r o l l e d t o ±0.1°C w i t h a
p l a t i n u m r e s i s t a n c e probe w h i c h extended 1 mm i n s i d e the i n n e r
s u r f a c e o f the c e l l . The p r e s s u r e was a d j u s t e d u s i n g a 100 cc
Ruska s y r i n g e pump and was measured t o w i t h i n ±0.1% w i t h a 710A
H e i s e d i g i t a l p r e s s u r e gauge w h i c h i s t r a c e a b l e t o an NBS s t a n d a r d .
The p r e s s u r e v a r i e d l e s s than 0.15 b a r (2 p s i ) d u r i n g a s p e c t r a l
scan. The w a v e l e n g t h a c c u r a c y was ±0.2 nm f o r t h e V a r i a n (Cary)
2290 s p e c t r o p h o t o m e t e r
The c e l l was l o a d e
p r e s s u r i z e d w i t h the s o l v e n t . A spectrum was o b t a i n e d a t a g i v e n
p r e s s u r e a f t e r the temperature and absorbance e q u i l i b r a t e d . The
a b s o r p t i o n band was scanned o v e r a range o f 450-600 nm 2-3 times t o
o b t a i n t h e average λ . The r e p r o d u c i b i l i t y i n λ was ±0.2 nm
max majx
w h i c h c o r r e s p o n d s t o a p r e c i s i o n i n E^, o f ±0.02 k c a l / m o l .
S o l v e n t s t r e n g t h i n the c r i t i c a l r e g i o n . A l l o f the experiments

were performed w i t h the dye p h e n o l b l u e w h i c h has been w e l l -
c h a r a c t e r i z e d b o t h e x p e r i m e n t a l l y and t h e o r e t i c a l l y i n l i q u i d
s o l v e n t s (20,21,22). S i n c e t h e d i p o l e moment o f p h e n o l b l u e
i n c r e a s e s 2.5 debye upon e l e c t r o n i c e x c i t a t i o n ( 8 ) , i t i s a
s e n s i t i v e probe of the l o c a l s o l v e n t environment. F o r example the
a b s o r p t i o n maxima o c c u r a t 550 and 608 nm i n n-hexane and m e t h a n o l ,
respectively. The e x c i t e d s t a t e i s s t a b i l i z e d t o a g r e a t e r e x t e n t
than t h e ground s t a t e as t h e " s o l v e n t s t r e n g t h " i s i n c r e a s e d , w h i c h
i s d e s i g n a t e d as a r e d s h i f t .
The t r a n s i t i o n energy, E , o f p h e n o l b l u e i n CO2 i s p l o t t e d
T
v e r s u s p r e s s u r e i n F i g u r e 1 a l o n g the s a t u r a t i o n c u r v e and a t
s u p e r c r i t i c a l c o n d i t i o n s . The b e h a v i o r o f t h e E^ v e r s u s p r e s s u r e
p l o t i s s i m i l a r t o t h a t o f d e n s i t y v e r s u s p r e s s u r e , such t h a t E i sT
f a i r l y l i n e a r i n d e n s i t y as shown i n F i g u r e 2. The e f f e c t ot
temperature i s r e l a t i v e l y s m a l l a t a g i v e n d e n s i t y . I n the h i g h l y
c o m p r e s s i b l e near c r i t i c a l r e g i o n , the E T i s extremely s e n s i t i v e
w i t h r e s p e c t t o p r e s s u r e a l o n g an i s o t h e r m , and l i k e w i s e w i t h
r e s p e c t t o temperature a l o n g an i s o b a r (see F i g u r e 1 ) . At h i g h
reduced p r e s s u r e s where t h e f l u i d i s r e l a t i v e l y i n c o m p r e s s i b l e , E^
i s o n l y a weak f u n c t i o n o f p r e s s u r e and temperature as i s t h e case
f o r l i q u i d s n e a r the t r i p l e p o i n t . S u p e r c r i t i c a l f l u i d solvents
e x h i b i t an i n t e r e s t i n g p r o p e r t y w h i c h i s not o b s e r v e d f o r pure
l i q u i d s o l v e n t s i n t h a t t h e d e n s i t y and thus the " s o l v e n t s t r e n g t h "
( E ) may be a d j u s t e d o v e r a continuum u s i n g s m a l l changes i n
T
temperature and p r e s s u r e .
In T a b l e I , s e v e r a l SF s o l v e n t s a r e compared w i t h l i q u i d
n-hexane a t a reduced temperature (Τ = T/T ) n e a r 1.05. F o r each

KIM AND JOHNSTON Supercritical Fluid Solvents and Reaction Rates
F i g u r e 2 . E o f p h e n o l b l u e i n CO2 v s . d e n s i t y (•= 31
T
Δ = 35 °C, 0 = 40 °C, 0= 45 °C, and i s calculated

using Equation 5).

f l u i d , t h e p r e s s u r e i s chosen t o match t h e Ε w i t h t h e v a l u e f o r
n-hexane, so t h a t t h e comparison i s made a t c o n s t a n t "solvent
strength". Many i n v e s t i g a t o r s have i m p l i e d t h a t t h e s o l v e n t
s t r e n g t h o f a s u p e r c r i t i c a l f l u i d approaches t h a t o f a l i q u i d a t
the p o i n t where t h e d e n s i t y approaches t h a t o f a l i q u i d . This i s
c l e a r l y a m i s c o n c e p t i o n . A t 45°C (T = 1.05), t h e m o l a r d e n s i t y o f
CO2 approaches t h a t o f n-hexane a t ^30 b a r , y e t i t i s a weaker
s o l v e n t f o r a l i p h a t i c and a r o m a t i c h y d r o c a r b o n s a t t h e s e c o n d i t i o n s
(2,3). The r e a s o n f o r t h i s d i f f e r e n c e i s t h a t t h g average 5
p o l a r i z a b i l i t y p a r m o l e c u l e o f CO2 i s o n l y 26.5 χ 10 cm whereas 3
3
i t i s 123 χ 10 cm f o r hexane. A t a g i v e n m o l a r d e n s i t y , t h e
p o l a r i z a b i l i t y p e r u n i t volume i s much g r e a t e r f o r hexane. Iti s
a l s o g r e a t e r f o r hexane a t a g i v e n mass d e n s i t y d e s p i t e t h e
d i f f e r e n c e i n the molecular weights.
Table I. Comparison o f SF S o l v e n t s w i t h n-Hexane
Solvent Τ Τ = Ρ Ρ = Ρ 6<1> a/v ( 2 )
r r
(°c) T/T (bar) P/P (g/cc) (cal/cc)^
c c
C Hi/
2
3 )
25 1.056 1700 33.8 0.57 7.0 0.052
C0 2 45 1.046 2800 37.9 1.32 10.3 0.048
( 3 )
CF C1 3 40 1.037 1300 33.2 1.95 6.9 0.051
n-C Hm 6 25 - 1 - 0.66 7.3 0.057
(1) H i l d e b r a n d s o l u b i l i t y parameter
(2) p o l a r i z a b i l i t y p e r volume
(3) r e f e r e n c e (19)
The Ε s o f t h e n o n p o l a r s o l v e n t s , C F 3 C I and 0 2 ^ , become

f
e q u a l t o t n a t o f n-hexane a t a p r e s s u r e i n t h e range o f 1-2

kilobar. N o t i c e that the Hildebrand s o l u b i l i t y parameters of these
three solvents are roughly equivalent at t h i s c o n d i t i o n of constant
Ε ·
τ The same r e s u l t i s a l s o o b s e r v e d f o r t h e p o l a r i z a b i l i t i e s /
volume o f t h e s e s o l v e n t s . A g a i n , t h e molar d e n s i t i e s o f t h e s e
s u p e r c r i t i c a l f l u i d s a r e c o n s i d e r a b l y h i g h e r t h a n t h a t o f n-hexane
at t h i s equivalence point i n solvent strength, since the
p o l a r i z a b i l i t i e s / m o l e c u l e a r e lower.
The E o f CO2 a t 45°C r e a c h e s t h a t o f n-hexane a t 2.8 k b a r .
T
At t h i s p r e s s u r e , t h e p o l a r i z a b i l i t y / v o l u m e o f SF CO2 i s a l i t t l e
l e s s t h a n t h a t o f n-hexane, w h i c h s u g g e s t s t h a t t h e r e a r e o t h e r
m o l e c u l a r i n t e r a c t i o n s between CO2 and p h e n o l b l u e i n a d d i t i o n t o
d i s p e r s i o n and i n d u c t i o n . The l i k e l y p o s s i b i l i t i e s i n c l u d e e l e c t r o n
d o n o r - a c c e p t o r f o r c e s and d i p o l e - q u a d r u p o l e i n t e r a c t i o n s .
The E ' s o f C O 2 , C2Ht+, and CHF3 a r e compared v e r s u s reduced
T
d e n s i t y a t c o n s t a n t reduced temperature i n F i g u r e 3. The c u r v e s

4. KIM A N D JOHNSTON Supercritical Fluid Solvents and Reaction Rates 47
f o r CO2 and e t h y l e n e c o i n c i d e even though t h e p o l a r i z a b i l i t y /

m o l e c u l e o f e t h y l e n e i s 1.6 times t h a t o f C O 2 . The p r i m a r y r e a s o n
f o r t h i s i s t h a t t h e m o l a r d e n s i t y o f CO2 i s 1.4 times t h a t o f
e t h y l e n e a t c o n s t a n t r e d u c e d d e n s i t y and t e m p e r a t u r e . The s e c o n
d a r y f a c t o r i s t h a t CO2 i s s l i g h t l y a c i d i c and h a s a q u a d r u p o l e
moment o t h e r w i s e i t would g i v e a s m a l l e r r e d s h i f t . F o r nonpolar
s o l u t e s t h a t do n o t e x h i b i t d i p o l a r and a c i d - b a s e i n t e r a c t i o n s , t h e
s o l v e n t s t r e n g t h o f CO2 would be l e s s than t h a t o f e t h y l e n e a t
c o n s t a n t reduced temperature and d e n s i t y . I n a d d i t i o n , a t a g i v e n
r e d u c e d temperature and d e n s i t y , t h e reduced p r e s s u r e s a r e s i m i l a r
( e . g . , see F i g u r e 3 and T a b l e 1) t h u s t h e a c t u a l p r e s s u r e f o r CO2
i s about 1.5 t i m e s t h a t f o r C2Hi+.
The s o l u b i l i t y d a t a f o r n a p h t h a l e n e i n e t h y l e n e and i n CO2 a r e
c o n s i s t e n t w i t h t h e E,j, d a t a i n F i g u r e 3. The p r o p e r way t o make
the comparison i s t o u s e t h e enhancement f a c t o r i n s t e a d o f t h e
solubility. The enhancement f a c t o r e q u a l s > which i s simply
the a c t u a l s o l u b i l i t y d i v i d e d by t h e s o l u b i l i t y i n an i d e a l g a s
The enhancement f a c t o
i s u s e f u l f o r comparin
at d i f f e r e n t a c t u a l temperatures. I n terms o f t h e f u g a c i t y
c o e f f i c i e n t o f t h e s o l u t e , Φ2, t h e enhancement f a c t o r i s g i v e n by
S
Ε = exp(v P/RT)/<|>2
2 (1)
s
where V2 i s t h e molar volume o f t h e s o l i d . I f a comparison i s
made a t c o n s t a n t reduced temperature and reduced d e n s i t y b u t a t
d i f f e r e n t p r e s s u r e s , t h e enhancement f a c t o r removes t h e P o y n t i n g
e f f e c t o f p r e s s u r e on t h e condensed phase. I n summary, t h e
enhancement f a c t o r i s a measure o f t h e s o l v e n t s t r e n g t h i n t h e SF
phase. The enhancement f a c t o r f o r n a p h t h a l e n e i n e t h y l e n e a t 25°C
(T = 1.05) i s about 3 t i m e s t h a t i n C 0 a t 45°C (T = 1.05) f o r a
2
wiSe range i n reduced d e n s i t y . The l a r g e r s o l u b i l i t y i n e t h y l e n e

i s c o n s i s t e n t w i t h t h e above d i s c u s s i o n c o n c e r n i n g F i g u r e 3, s i n c e
n a p h t h a l e n e i s n o t a v e r y s t r o n g Lewis base compared w i t h p h e n o l
blue.
S o l v e n t e f f e c t on r a t e c o n s t a n t s . In this section, the rate

c o n s t a n t w i l l be p r e d i c t e d q u a l i t a t i v e l y i n CO2 f o r t h e D i e l s - A l d e r
c y c l o a d d i t i o n o f i s o p r e n e and m a l e i c a n h y d r i d e , a r e a c t i o n w h i c h
has been w e l l - c h a r a c t e r i z e d i n t h e l i q u i d s t a t e (23,24). In a
p r e v i o u s p a p e r , we used E_ d a t a f o r p h e n o l b l u e i n e t h y l e n e t o
p r e d i c t the r a t e constant o f the Menschutkin reaction of
t r i p r o p y l a m i n e and m e t h y l i o d i d e ( 1 9 ) . The r e a c t i o n mechanisms a r e
q u i t e d i f f e r e n t , y e t t h e s o l v e n t e f f e c t on t h e r a t e c o n s t a n t o f
b o t h r e a c t i o n s c a n be c o r r e l a t e d w i t h Ε o f p h e n o l b l u e i n l i q u i d
solvents. The d i p o l e moment i n c r e a s e s m t h e M e n s c h u t k i n reaction
g o i n g from t h e r e a c t a n t s t a t e t o t h e t r a n s i t i o n s t a t e and i n p h e n o l
b l u e d u r i n g e l e c t r o n i c e x c i t a t i o n , so t h a t t h e two phenomena a r e
correlated. I n t h e above D i e l s - A l d e r r e a c t i o n , t h e r e a c t i o n
c o o r d i n a t e i s i s o p o l a r w i t h a n e g a t i v e a c t i v a t i o n volume ( 8 , 2 3 ) ,
Φ
Δν R (2)
" W *B - - T W l n k / d P )
x

Library
1155 16th St., N.W.
where M i s the t r a n s i t i o n s t a t e , A and Β a r e t h e r e a c t a n t s and

k
χ
i s t h e r a t e c o n s t a n t based on mole f r a c t i o n u n i t s . Using Regular
S o l u t i o n T h e o r y , i t was demonstrated t h a t t h e r a t e c o n s t a n t
2
i n c r e a s e s w i t h the c o h e s i v e energy d e n s i t y ( δ ) o f t h e s o l v e n t f o r
t h i s r e a c t i o n as was o b s e r v e d e x p e r i m e n t a l l y ( 2 3 ) . Since there i s
l i t t l e d i f f e r e n c e i n t h e d i p o l e moment o f the t r a n s i t i o n s t a t e
v e r s u s the r e a c t a n t s , t h e s o l v e n t e f f e c t on t h e r a t e c o n s t a n t i s
s m a l l compared w i t h the M e n s c h u t k i n r e a c t i o n .
The r a t e c o n s t a n t d a t a f o r the D i e l s - A l d e r r e a c t i o n o f
i s o p r e n e and m a l e i c a n h y d r i d e (23,24) may be c o r r e l a t e d w i t h Ε of
p h e n o l b l u e a t 35°C by
In k = -a E_ + b (3)
χ Τ
where the c o n s t a n t s a and b a r e -1.053 and 43.70, r e s p e c t i v e l y .
U s i n g Eqs. 2 and 3, the a c t i v a t i o n volume may be e x p r e s s e d as
Δ ν * = +aRTPk T (3E
where k T i s the i s o t h e r m a l c o m p r e s s i b i l i t y , 1 / ρ ( 9 ρ / 3 Ρ )
τ> and i t i s
assumed t h a t a and b a r e p r e s s u r e independent. The d e n s i t y
d e r i v a t i v e of E i s r e l a t i v e l y c o n s t a n t compared t o pk^, e s p e c i a l l y
T
i n the h i g h l y c o m p r e s s i b l e r e g i o n , and i s s i m i l a r f o r "both l i q u i d s

and s u p e r c r i t i c a l f l u i d s . S i n c | phenol blue e x h i b i t s a red s h i f t ,
( 3 E ^ / 3 p ) i s n e g a t i v e , as i s Δν which r e a c h e s a minimum a t the
T
same d e n s i t y where the c o m p r e s s i b i l i t y i s a maximum.

The l o g a r i t h m o f the r a t e c o n s t a n t of the above D i e l s - A l d e r
r e a c t i o n i s p r e d i c t e d v e r s u s p r e s s u r e i n F i g u r e 4 a t 35°C. The
r a t e c o n s t a n t i n c r e a s e s by a f a c t o r o f t e n f o r t h i s p r e s s u r e range
w h i c h c o r r e s p o n d s t o a d e n s i t y range o f 6.7 t o 21 m o l / £ . The nega
t i v e o f the s l o p e of t h i s p l o t , o r the a c t i v a t i o n volume becomes
l a r g e l y n e g a t i v e i n the h i g h l y c o m p r e s s i b l e n e a r c r i t i c a l r e g i o n as
shown i n T a b l e I I . ξοτ example, Δν r e a c h e s -4000 a t 75 b a r . At
35°C and 300 b a r , Δν i s o n l y m o d e r a t e l y n e g a t i v e , i . e . , -55 cc/mol
compared w i t h -37.4 cc/mol i n l i q u i d e t h y l a c e t a t e a t 35°C. At each
p r e s s u r e i n F i g u r e 4, the a c t i v a t i o n volume i s n e g a t i v e s i n c e the
magnitude o f v ^ i s l e s s than t h a t o f the sum o f ν and v ^ f o r t h i s
c y c l o a d d i t i o n r e a c t i o n (see Eq. 2 ) . In the h i g h l y c o m p r e s s i b l e
1
r e g i o n , the v . s become l a r g e l y n e g a t i v e s i n c e the s o l u t e causes a
compression or the f l u i d s o l v e n t as was e x p l a i n e d i n d e t a i l b o t h
e x p e r i m e n t a l l y and t h e o r e t i c a l l y (26,2^7» 2 8 ) . As a r e s u l t , the
a c t i v a t i o n volume i s a l s o an e x t r e m e l y l a r g e n e g a t i v e number.
T a b l e I I . P r e d i c t i o n of the A c t i v a t i o n volume of the

D i e l s - A l d e r r e a c t i o n between i s o p r e n e and
m a l e i c a n h y d r i d e i n s u p e r c r i t i c a l carbon
d i o x i d e a t 35°C
Pressure
(bar) 75 80 85 100 200 300
AV* -4000 -2000 -950 -225 -70 -55

(cc/mol)

56 • ι
... Ί
Δ
Δ
Ο
54h °*
•
52
•
•
ι
50'
1
1.0 2.0
Reduced Density
F i g u r e 3. E-j- o f p h e n o l b l u e i n s e v e r a l f l u i d s v s . reduced
d e n s i t y (Δ = C0 - 45 °C, Ο = C H - 25 °C ( 1 9 ) , and
2 2 4
• = CHF - 40 °C ( 1 9 ) .
3
-5.6
* -5.8
&0
ο
-6.2
100 200 300

Pressure (bar)
F i g u r e 4. P r e d i c t e d r a t e c o n s t a n t f o r the D i e l s - A l d e r reaction
of i s o p r e n e and m a l e i c anhydride, i n CO2 a t 35 °C.

The e x t r e m e l y pronounced s o l v e n t e f f e c t i n the n e a r c r i t i c a l

r e g i o n can a l s o be e x p l a i n e d u s i n g Eq. 4. As mentioned above,
(3E /3p)
T T i s s i m i l a r f o r b o t h l i q u i d s and s u p e r c r i t i c a l f l u i d s .
However, the magnitude o f a c t i v a t i o n volume can be much l a r g e r i n
s u p e r c r i t i c a l f l u i d s because o f the much h i g h e r c o m p r e s s i b i l i t y .
T h i s a n a l y s i s can a l s o be a p p l i e d t o the M e n s c h u t k i n r e a c t i o n of
t r i p r o p y l a m i n e and m e t h y l i o d i d e , w h i c h has an a c t i v a t i o n volume of
-65 cc/mol i n l i q u i d C C l ^ a t 30°C. In e t h y l e n e a t 66 b a r and 25°C,
Δν i s p r e d i c t e d t o be -5000 c c / m o l . Both of t h e s e r e a c t i o n s
e x h i b i t an e x t r e m e l y pronounced s o l v e n t e f f e c t i n the n e a r c r i t i c a l
r e g i o n s i n c e the r e a c t i o n s have r e l a t i v e l y l a r g e ( i n magnitude)
a c t i v a t i o n volumes even i n l i q u i d s . The s o l v e n t e f f e c t on the
M e n s c h u t k i n r e a c t i o n would be even more pronounced i n a s u p e r c r i t
i c a l f l u i d w i t h a d i p o l e moment where the " s o l v e n t s t r e n g t h " would
be even more s e n s i t i v e t o d e n s i t y . These p r e d i c t i o n s suggest t h a t
f u t u r e measurements o f r a t e c o n s t a n t s i n s u p e r c r i t i c a l f l u i d s c o u l d
p o t e n t i a l l y demonstrate a s o l v e n t e f f e c t of o r d e r s of magnitude.
L o c a l s o l v e n t compression
chromic d a t a w i l l be to d e t e r m i n e the magnitude of the l o c a l
c o m p r e s s i o n of a s u p e r c r i t i c a l f l u i d s o l v e n t i n the immediate
environment of the s o l u t e . The E^ of a dye such as p h e n o l b l u e can
be p r e d i c t e d i n l i q u i d s where no s p e c i f i c i n t e r a c t i o n s are p r e s e n t
by t r e a t i n g the s o l v e n t as a homogeneous p o l a r i z a b l e d i e l e c t r i c
(22,29). The i n t r i n s i c " s o l v e n t s t r e n g t h " , Ε ^ ° , d e s c r i b e s d i s
p e r s i o n , i n d u c t i o n , and d i p o l e - d i p o l e f o r c e s and i s g i v e n by ( 2 2 ) .
T D + 2
2n2 l + n2 + 2
where η i s the r e f r a c t i v e i n d e x and D i s the d i e l e c t r i c c o n s t a n t .

The c o n s t a n t s A, Β and C a r e f u n c t i o n s o f the p r o p e r t i e s of the dye
such as the d i p o l e moment and o s c i l l a t o r s t r e n g t h o f t h e ground and
e x c i t e d s t a t e s and the c a v i t y r a d i u s . The f i r s t term i n Eq. 5
i n c l u d e s d i s p e r s i o n and s o l u t e permanent d i p o l e - s o l v e n t i n d u c e d
d i p o l e f o r c e s , thus i t i s a f u n c t i o n o f the r e f r a c t i v e i n d e x of the
solvent. The second term d e s c r i b e s the e f f e c t s of permanent
d i p o l e - d i p o l e f o r c e s ( o r i e n t a t i o n ) . The Ε^° of p h e n o l b l u e was
c o r r e l a t e d s u c c e s s f u l l y w i t h Eq. 5 f o r 21 non-hydrogen b o n d i n g
l i q u i d s o l v e n t s (20,22,29).
The measured t r a n s i t i o n energy, Ε , i n c l u d e s the i n t r i n s i c
" s o l v e n t s t r e n g t h " g i v e n by Eq. 5 and the s p e c i f i c " s o l v e n t
strength", Ε , w h i c h d e s c r i b e s an e x a g g e r a t e d s o l v e n t e f f e c t such
as hydrogen B o n d i n g such t h a t
E T ( e x p e r i m e n t a l ) = E° + E^ (6)
g
F o r p h e n o l b l u e , the Ε i s z e r o f o r e t h y l e n e and C F C 1 , but non
3
z e r o f o r the Lewis a c i d s C F H and C 0 . 3 2 One of the a t t r a c t i v e

f e a t u r e s of s o l v a t o c h r o m i c s c a l e s i s t h a t the n o n - s p e c i f i c and
s p e c i f i c i n t e r a c t i o n s may be s e p a r a t e d s i n c e the former can be
c a l c u l a t e d s t r a i g h t f o r w a r d l y u s i n g Eq. 5.
The E^ i s not i n f l u e n c e d by f a c t o r s such as r e p u l s i v e f o r c e s

between the s o l u t e and s o l v e n t s i n c e they a r e i d e n t i c a l i n the

ground and e x c i t e d s t a t e s . The l o c a t i o n s of the m o l e c u l e s do not
change d u r i n g the time frame o f e l e c t r o n i c e x c i t a t i o n . The theory
f o r s o l u b i l i t y phenomena i s much more c o m p l i c a t e d ; f o r example, i t
i n c l u d e s r e p u l s i v e f o r c e s . As a r e s u l t , s o l u b i l i t y d a t a g i v e l e s s
i n f o r m a t i o n about the p r o p e r t i e s of the s o l v e n t , o r the l o c a l
s o l v e n t environment about the s o l u t e .
In o r d e r t o a n a l y z e the b e h a v i o r of p h e n o l b l u e i n CO2> i t i s
u s e f u l t o r e v i e w the r e s u l t s f o r e t h y l e n e s i n c e i t has a s p e c i f i c
" s o l v e n t s t r e n g t h " o f z e r o (19, see F i g u r e 5 ) . The dashed l i n e
was c a l c u l a t e d u s i n g Eq. 5 where the c o n s t a n t s A and Β were
o b t a i n e d from the l i t e r a t u r e (20,30) and C was chosen t o f o r c e
agreement w i t h experiment i n the dense i n c o m p r e s s i b l e r e g i o n . The
dashed l i n e f i t s the d a t a at h i g h d e n s i t y where e t h y l e n e i s
r e l a t i v e l y incompressible. At a lower d e n s i t y , e.g. 7 mol/1,
e t h y l e n e i s h i g h l y c o m p r e s s i b l e so t h a t i t " c l u s t e r s " about the
s o l u t e due t o a t t r a c t i v e f o r c e s E c k e r t e t a l (27,28) measured
s o l u t e p a r t i a l m o l a r volume
i n e t h y l e n e i n the h i g h l
l o c a l c o m p r e s s i o n phenomenon which i n c r e a s e s the number of s o l v e n t
m o l e c u l e s n e a r the s o l u t e causes an a d d i t i o n a l r e d s h i f t o f 1
k c a l / m o l a t a d e n s i t y of 7 mol/1. The a d d i t i o n a l r e d s h i f t i s the
d i f f e r e n c e between the e x p e r i m e n t a l p o i n t and t h a t w h i c h i s
p r e d i c t e d u s i n g the t h e o r y f o r a homogeneous l i q u i d shown by the
dashed l i n e . T h i s d i f f e r e n c e becomes s m a l l as the isothermal
c o m p r e s s i b i l i t y d i m i n i s h e s as e x p l a i n e d below.
The l o c a l d e n s i t y of s o l v e n t about the s o l u t e may be
d e t e r m i n e d by comparing the e x p e r i m e n t a l and c a l c u l a t e d c u r v e s .
C o n s i d e r p o i n t s A and Β i n F i g u r e 5 a t a c o n s t a n t v a l u e of E^,
i . e . , 55 k c a l / m o l . A h y p o t h e t i c a l homogeneous f l u i d a t p o i n t Β
g i v e s the same " s o l v e n t s t r e n g t h " as £he a c t u a l f l u i d a t p o i n t A.^
The l o c a l d e n s i t y about the s o l u t e exceeds the b u l k d e n s i t y P^
due t o c o m p r e s s i o n , such t h a t
A
P r
p B
i =VT J
(7)
ij o
where g . . ( r ) i s the u n l i k e p a i r r a d i a l d i s t r i b u t i o n f u n c t i o n .
U s i n g K i i k w o o d - B u f f s o l u t i o n t h e o r y ( 3 1 ) , i t was shown t h a t the
d i f f e r e n c e between the l o c a l and b u l k d e n s i t i e s i s (19)
1 Pk Tk
P l 2 p =
" -1ΪΓ (1
" V 2 / k T
B V ( 8 )
where V12 i s a measure o f the volume of the f i r s t c o o r d i n a t i o n

shell. Based on p r e v i o u s r e s u l t s ( E c k e r t e t a l . , 27, 28), i t i s
r e a s o n a b l e t o assume
_ 00
(9)
V2 = al^ + b

56
\
\
\
\
\
53
Density (mol/L)
F i g u r e 5. E of phenol b l u e i n e t h y l e n e v s . d e n s i t y ( O = 25 °C,
T
Δ = 10 °C, and i s c a l c u l a t e d E using Equation 5). T
U s i n g Eqs. 8 and 9, t h e f i n a l r e s u l t i s
1
! f
(Pl 2 - P)/P = a k T + b (10)
?
where a and b* a r e f u n c t i o n s o f temperature and V . The 1 2
l i n e a r i t y suggested by Eq. 10 has been o b t a i n e d from t h e d a t a i n

Figure 5 (19).
The C 0 d a t a i n F i g u r e 2 a r e more d i f f i c u l t t o a n a l y z e because
2
of t h e a c i d - b a s e i n t e r a c t i o n s . The dashed l i n e i s t h e c a l c u l a t e d
r e s u l t f o r E^° o f a homogeneous p o l a r i z a b l e d i e l e c t r i c ( E q . 5)
u s i n g t h e same v a l u e s o f t h e c o n s t a n t s A, B, and C as o b t a i n e d
above f o r e t h y l e n e . A t h i g h d e n s i t y , where t h e l o c a l compression
e f f e c t d i s a p p e a r s , the s p e c i f i c " s o l v e n t s t r e n g t h " which i s the
d i f f e r e n c e between t h e d a t a and Ε^° i s about 0.7 k c a l / m o l . To p u t
t h i s i n p e r s p e c t i v e , t h e s p e c i f i c " s o l v e n t s t r e n g t h s " a r e 6.3, 1.6,
1.3 f o r p h e n o l b l u e i n t h e l i q u i d s o l v e n t s m - c r e s o l ( s t r o n g Lewis
a c i d ) , m e t h a n o l , and c h l o r o f o r m , r e s p e c t i v e l y ( 2 0 , 3 0 ) ) . In the
h i g h l y c o m p r e s s i b l e r e g i o n , t h e r e d s h i f t exceeds t h e dashed l i n e
due t o two c o u p l e d e f f e c t s , a c i d - b a s e f o r c e s , and l o c a l s o l v e n t
compression.
The f i n a l s e t o f s o l v a t o c h r o m i c d a t a a r e shown i n F i g u r e 6 f o r
p h e n o l b l u e i n SF C 0 doped w i t h v a r i o u s amounts o f t h e c o - s o l v e n t
2
o r entraîner, m e t h a n o l . C o n s i d e r a p r e s s u r e o f 100 b a r where t h e

E T of phenol blue i n C 0 i s 54 k c a l / m o l .
2 The r e d s h i f t i s
i n c r e a s e d more by t h e a d d i t i o n o f 3.5 mole p e r c e n t methanol a t
c o n s t a n t p r e s s u r e t h a n by an i n c r e a s e i n t h e p r e s s u r e o f p u r e C 0 2
of o v e r 200 b a r . The l a r g e s p e c i f i c " s o l v e n t s t r e n g t h " o f methanol

causes t h i s b e h a v i o r . The r e d s h i f t caused by t h e c o - s o l v e n t i s i n

F i g u r e 6. E-p o f p h e n o l b l u e i n C0 -methanol m i x t u r e s
2 (•= pure
C0 , Δ = C0 - 1% CH OH, 0 = C0 - 3.5% CH OH).
2 2 3 2 3

e x c e s s o f t h e amount c a l c u l a t e d i f i t i s assumed t h a t the m i x t u r e

i s random. T h i s i n d i c a t e s t h a t the dye i s s o l v a t e d p r e f e r e n t i a l l y
by methanol such t h a t methanol's l o c a l c o n c e n t r a t i o n exceeds i t s
b u l k c o n c e n t r a t i o n . A l a r g e number o f s o l u b i l i t i e s o f s o l i d s were
measured i n C 0 w i t h and w i t h o u t c o - s o l v e n t by J o h n s t o n and
2
co-workers (32,33). I n many o f these systems, s m a l l amounts o f

c o - s o l v e n t s produced a g r e a t e r i n c r e a s e i n t h e s o l u b i l i t y t h a n
p r e s s u r e i n c r e a s e s o f hundreds o f atmospheres. The r e l a t i o n s h i p
between t h e s p e c t r o s c o p i c d a t a and t h e s o l u b i l i t y d a t a i s t h e
s u b j e c t o f ongoing r e s e a r c h .
Acknowledgment s
T h i s m a t e r i a l i s based on work supported by the N a t i o n a l S c i e n c e

F o u n d a t i o n under Grant No. CPE-8306327. Any o p i n i o n s , f i n d i n g s ,
and c o n c l u s i o n s o r recommendations expressed i n t h i s p u b l i c a t i o n do
not n e c e s s a r i l y r e f l e c t t h e v i e w s o f the N a t i o n a l S c i e n c e Founda
tion.
Acknowledgment i
R e s e a r c h Fund, a d m i n i s t e r e d by the American C h e m i c a l S o c i e t y , f o r
p a r t i a l support o f t h i s work. F u r t h e r support i s acknowledged from
the Dow C h e m i c a l Company F o u n d a t i o n and t h e S e p a r a t i o n s Research
Program a t The U n i v e r s i t y o f Texas.
Literature Cited
1. Zosel, K. Angew. Chem. Int. Ed. 1978, 17, 702.
Rev. in Chem. Eng. 1983 1(2), 179.
3. Johnston, K. P. "Kirk-Othmer Encyclopedia of Chemical
Technology," John Wiley & Sons: New York, 1984.
4. McHugh, M. A. "Extraction with Supercritical Fluids," in
"Recent Development in Separation Science," Li, Ν. N. and
Carlo, J. Μ., Eds., CRC Press: Boca Raton, 1984; Vol. IX.
5. Randall, L. G. Sep. Sci. Technol. 1982, 17(1), 1.
6. Alexander, G.; Paulaitis, M. E. AIChE Annual Meeting, #140d,
San Francisco, 1984.
7. Simmons, G. M.; Mason, D. M. Chem. Eng. Sci. 1972, 27, 89.
8. Reichardt, C. "Solvent Effects in Organic Chemistry," Verlag
Chemie, Weinheim, New York, 1979.
9. Dack, M.R.J., "Solutions and Solubilities Part II," John Wiley
& Sons: New York, 1976.
10. Tamura, K.; Imoto, T. Bull. Chem. Soc. of Japan 1975, 48(2),
369.
11. Reichardt, C. Angew. Chem. Int. Ed. 1979, 18, 98.
12. Kamlet, M. J.; Hall, T. N.; Taft, R. W. J. Org. Chem. 1979,
44, 2599.
13. Kamlet, M. J.; Abboud, J. L.; Taft, R. W. J. Amer. Chem. Soc.
1981, 103(5), 1080.
14. Taft, R. W.; Abraham, M. C.; Doherty, R. M.; Kamlet, M. J.
Nature 1985, 313(31), 384.
15. Hyatt, J. A. J. Org. Chem. 1984, 49, 5097.
16. Sigman, M. E.; Lindley, S. M.; Leffler, J. E. J. Amer. Chem.
Soc. 1985, 107, 1471.
17. Kamlet, M. J.; Abboud, J. L.; Taft, R. W. J. Amer. Chem. Soc.
1977, 99(18), 6027.

18. Kamlet, M. J.; Abboud, J. L.; Abraham, M. H.; Taft, R. W. J.

Org. Chem. 1983, 48, 2877.
19. Kim, S.; Johnston, K. P. "Molecular Interactions in Dilute
Supercritical Fluid Solutions," Submitted to Ind. Eng. Chem.
Fund. 1985.
20. Figueras, J. J. Amer. Chem. Soc. 1972, 93(13), 3255.
21. Kolling, O. W. Anal. Chem. 1981, 53, 54.
22. McRae, E. G. J. Phys. Chem. 1957, 61, 562.
23. Grieger, R. Α.; Eckert, C. A. Trans. Faraday Soc. 1970, 66,
2579.
24. Eckert, C. Α.; Hsieh, C. R.; McCabe, J. R. AIChE J. 1974,
20(1), 20.
25. Silber, E. Ph.D. Thesis, Texas Tech. Univ, 1971.
26. Eckert, C. Α.; Paulaitis, M. E.; Johnston, K. P. J. Phys.
Chem. 1981, 85, 1770.
27. Eckert, C. Α.; Ziger, D. H.; Johnston, K. P.; Ellison, T. K.
Fluid Phase Equilib. 1983, 14, 167.
28. Eckert, C. A.; Ziger, D. H.; Johnston, K. P.; Kim, S. J.
Phys. Chem. 1986 (i
29. Mataga, N.; Kubota, T. "Molecular Interactions and Electronic
Specta," Marcel Dekker, Inc.: New York, 1970.
30. Kolling, O. W.; Goodnight, J. L. Anal. Chem. 1973, 45(1),
160.
31. Kirkwood, J. C.; Buff, F. P. J. Chem. Phys. 1951, 19(6), 774.
32. Johnston, K. P.; Dobbs, J. M.; Wong, J. M.; Lahiere, R. J.
Ind. Eng. Chem. Fund. 1986 (in press).
33. Johnston, K. P.; Dobbs, J. M.; Wong, J. M. J. Chem. Eng. Data
1986 (in press).

Chapter 5
Organic Chemistry in Supercritical Fluid Solvents:

Photoisomerization of trans-Stilbene
1
Tetsuo Aida and Thomas G. Squires
Applied Organic Chemistry, Energy & Minerals Resources Research Institute,

Iowa State University, Ames, IA 50011
The wide range of supercritical fluid properties accessible

through modest manipulations of pressure and temperature
affords a unique approach to investigating and, perhaps,
controlling chemica
phase behavior, th
obtained from photoisomerization of trans-stilbene in
supercritical CO is dependent on system pressure. This
2
behavior is probably attributable to significant changes in
solvent viscosity in this pressure range. Techniques for
investigating reactions under supercritical conditions are
described, and an approach to assessing the "supercritical
fluid effect" is suggested.
The unusual solvent properties of supercritical fluids (SCFs) have

been known for over a century (1). Just above the critical tempera
ture, Τ , forces of molecular attraction are balanced by kinetic
c
energy; and fluid properties, including solvent power, exhibit a
substantial pressure dependence. Many complex organic materials are
soluble at moderate pressures (80 to 100 atmospheres); and SCF sol
vent power increases dramatically when the pressure is increased to
300 atmospheres. The pressure responsive range of solvent properties
thus attainable provides a tool for investigating the fundamental
nature of molecular interactions and is also being exploited in
important areas of applied research (2,3).
In the latter activity, supercritical fluids have been utilized
extensively in the thermochemical solubilization of coal (4), for
selective extraction of naturally occurring materials (5,6), and in
various separation techniques including destraction (7) and super
critical fluid chromatography (8,9). The physicochemical principles
underlying these applications have also been investigated (10). In
view of the high level of interest in manipulating complex organic
mixtures with supercritical fluids, it is surprising that these
fluids have seen little use as solvents for organic reactions
1
Current address: Associated Western Universities, Inc., 142 East 200 South, Salt Lake
City, UT 84111
0097-6156/87/0329-0058$06.00/0

5. AIDA A N D SQUIRES Photoisomerization oftrans-Stilbene 59
(ll 12).
f The p i v o t a l r o l e o f s o l v e n t p r o p e r t i e s i n c o n t r o l l i n g t h e
c o u r s e and r a t e o f c h e m i c a l r e a c t i o n s i s w e l l e s t a b l i s h e d (13) ; a n d ,
t h u s , t h e same k i n d o f p r e s s u r e r e s p o n s i v e s o l v e n t - s o l u t e i n t e r a c -
t i o n s w h i c h c o n t r o l e x t r a c t i o n s a n d s e p a r a t i o n s i n S C F s c a n be e x -
p e c t e d t o d i r e c t c h e m i c a l pathways and i n f l u e n c e r e a c t i o n r a t e s .
Much o f o u r u n d e r s t a n d i n g o f t h e n a t u r e o f c h e m i c a l r e a c t i o n s
h a s b e e n d e r i v e d by o b s e r v i n g t h e r e s p o n s e s o f t h e s e p r o c e s s e s t o
changes i n s o l v e n t p r o p e r t i e s . While i n v e s t i g a t i o n s of t h i s type
have been h i g h l y p r o d u c t i v e , i n t e r p r e t a t i o n o f the r e s u l t s has o f t e n
been b l u r r e d by u n c e r t a i n t i e s i n h e r e n t i n t h e e x p e r i m e n t a l a p p r o a c h .
Heretofore, l i q u i d s o l v e n t s have been used i n t h e s e i n v e s t i g a t i o n s ,
and s o l v e n t p r o p e r t i e s h a v e b e e n c h a n g e d by a d j u s t i n g t h e s o l v e n t
composition. U n f o r t u n a t e l y , no q u a n t i t a t i v e r e l a t i o n s h i p between
b u l k s o l v e n t p r o p e r t i e s and c h e m i c a l phenomena has emerged, p r e s u m a -
b l y due t o s e l e c t i v e s o l v e n t - s o l u t e i n t e r a c t i o n s w h i c h r e s u l t i n
d i f f e r e n c e s between b u l k s o l v e n t c o m p o s i t i o n and m i c r o s c o p i c s o l v e n t
c o m p o s i t i o n (13).
In c o n t r a s t t o l i q u i
s o l v e n t can be a l t e r e d ove
of p r e s s u r e a n d / o r temperature. At c o n s t a n t reduced temperature,
( T = T / T ) , b e t w e e n 1.0 a n d 1.1, s o l v e n t p r o p e r t i e s a r e e x t r e m e l y
R C
r e s p o n s i v e t o v e r y a c c e s s i b l e changes i n p r e s s u r e (800 t o 4000 p s i )

(14). SCFs thus p r o v i d e an u n p r e c e d e n t e d o p p o r t u n i t y t o i n v e s t i g a t e
t h e e f f e c t s o f s o l v e n t p r o p e r t i e s on c h e m i c a l r e a c t i o n s w i t h o u t
c h a n g i n g the s o l v e n t c o m p o s i t i o n .
T h i s a p p l i c a t i o n of S C F s , w h i l e h i g h l y t o u t e d , has r e c e i v e d
s c a n t e x p e r i m e n t a l a t t e n t i o n (15). I n v e s t i g a t i o n s have been l i m i t e d
t o D i e l s - A l d e r r e a c t i o n s ( 1 1 , 1 6 ) , e l e c t r o c h e m i c a l r e a c t i o n s (17,18),
p o l y m e r i z a t i o n s ( 1 9 , 2 0 ) , and h i g h t e m p e r a t u r e p r o c e s s e s (21,22).
R e c e n t s e m i e m p i r i c a l t r e a t m e n t s o f SCF s o l v e n t p r o p e r t i e s (23,24)
have p r o v i d e d a b a s i s f o r i n t e r p r e t i n g s o l v e n t e f f e c t s i n SCFs.
I n v e s t i g a t i o n s of o r g a n i c r e a c t i o n s in s u p e r c r i t i c a l solvents
a r e s u b j e c t t o s e v e r a l c o n s t r a i n t s , one a t t r i b u t a b l e t o s u p e r c r i t i c a l
f l u i d p r o p e r t i e s and o t h e r s imposed f o r i n t e r p r e t i v e and e x p e r i m e n t a l
simplicity. Because s u p e r c r i t i c a l f l u i d p r o p e r t i e s a r e a f f e c t e d by
changes i n t e m p e r a t u r e , a r e a c t i o n s h o u l d be s e l e c t e d which does not
require heat for i n i t i a t i o n and i s n o t h i g h l y exothermic.
A d d i t i o n a l l y , f o r e x p e r i m e n t a l s i m p l i c i t y and c l a r i t y o f i n t e r p r e t a -
t i o n , a c l e a n , w e l l - u n d e r s t o o d r e a c t i o n s h o u l d be c h o s e n ; a n d one
s h o u l d e x p e c t an e x p e r i m e n t a l l y o b s e r v a b l e r e s p o n s e t o c h a n g e s i n
pressure. F i n a l l y , a u n i m o l e c u l a r r e a c t i o n which p r o d u c e s a s i n g l e
p r o d u c t o b v i a t e s the c o m p l i c a t i o n o f c o n t r o l l i n g the c o n c e n t r a t i o n s
o f two r e a c t a n t s and s i m p l i f i e s p r o d u c t a n a l y s i s . The p h o t o i s o m e r i -
z a t i o n o f t r a n s - s t i l b e n e meets t h e s e r e q u i r e m e n t s .
The p h o t o i s o m e r i z a t i o n o f s t i l b e n e i s one o f the most e x t e n s i v e -
l y s t u d i e d p h o t o r e a c t i o n s (25). S o l v e n t e f f e c t s have been t h o r o u g h l y
i n v e s t i g a t e d f o r b o t h the d i r e c t and p h o t o s e n s i t i z e d i s o m e r i z a t i o n s ,
and a m o d e l h a s b e e n d e v e l o p e d w h i c h a t t r i b u t e s t h e s e e f f e c t s t o
s o l v e n t v i s c o s i t y (26). Increased v i s c o s i t y i n h i b i t s d i r e c t p h o t o -
i s o m e r i z a t i o n of the c i s i s o m e r , but f a c i l i t a t e s t h a t of t r a n s -
stilbene. As a r e s u l t , t h e c i s / t r a n s r a t i o o f t h e p h o t o s t a t i o n a r y
s t a t e i n c r e a s e s w i t h i n c r e a s i n g s o l v e n t v i s c o s i t y . The wide range o f
v i s c o s i t i e s which a r e a t t a i n a b l e by p r e s s u r e m a n i p u l a t i o n o f s u p e r -
c r i t i c a l c a r b o n d i o x i d e p r o v i d e s an e x c e l l e n t o p p o r t u n i t y t o p r o b e
t h e e f f e c t o f v i s c o s i t y on s t i l b e n e p h o t o c h e m i s t r y i n t h e same
solvent.

We chose c a r b o n d i o x i d e f o r our i n i t i a l i n v e s t i g a t i o n s b e c a u s e
the p r o p e r t i e s o f s u p e r c r i t i c a l c a r b o n d i o x i d e a r e w e l l known and t h e
s o l u b i l i t y o f a r e l a t i v e l y l a r g e number o f o r g a n i c m a t e r i a l s a r e
known f o r t h i s medium. Although carbon d i o x i d e i s i n t e r a c t i v e w i t h
solute molecules, it is generally unreactive. Furthermore, the
s u p e r c r i t i c a l w o r k i n g r a n g e (1.0 < T R < 1.1), 31.5 t o 6 0 ° C , is
e x p e r i m e n t a l l y c o n v e n i e n t ; a n d many o r g a n i c r e a c t i o n s h a v e b e e n
e x t e n s i v e l y i n v e s t i g a t e d i n t h i s temperature range.
Experimental
P h o t o i s o m e r i z a t i o n s were c a r r i e d o u t u s i n g a 450 w a t t H a n o v i a medium

p r e s s u r e mercury s o u r c e , and each r e a c t i o n was f o l l o w e d t o t h e p h o t o -
stationary s t a t e by g a s c h r o m a t o g r a p h i c d e t e r m i n a t i o n of the
cis/trans ratios. Twice r e c r y s t a l l i z e d t r a n s - s t i l b e n e (Aldrich),
s p e c t r o p h o t o m e t r i c g r a d e c y c l o h e x a n e , and d r y , h i g h p u r i t y c a r b o n
d i o x i d e were used i n t h e s e e x p e r i m e n t s .
A schematic diagram
i n F i g u r e 1. Both the
a d a p t a t i o n s o f t h o s e u t i l i z e d by o t h e r i n v e s t i g a t o r s (27). The
p h o t o c h e m i c a l r e a c t o r was c o n s t r u c t e d f r o m t h i c k - w a l l e d q u a r t z c a p i l -
l a r y t u b i n g (2mm i . d . ) a n d was i n c o r p o r a t e d i n t o t h e s u p e r c r i t i c a l
s y s t e m by a f f i x i n g s t a i n l e s s s t e e l f i t t i n g s t o the t u b i n g w i t h epoxy
resin. E x c e p t f o r an o c c a s i o n a l f a u l t y j o i n t , t h i s s e c t i o n o f t h e
apparatus performed f l a w l e s s l y .
Flow r a t e s t h r o u g h the s y s t e m were c o n t r o l l e d by q u a r t z c a p i l -
l a r i e s c o n n e c t e d i n p a r a l l e l and were measured w i t h a gas b u r e t
c o n n e c t e d t o the c a p i l l a r y t i p s . U s i n g t h i s method, a wide range o f
f l o w r a t e s at v a r i o u s system p r e s s u r e s were a t t a i n e d . To o b t a i n a
p a r t i c u l a r f l o w r a t e , a l l v a l v e s e x c e p t V^' and V ^ i n t h e r e a c t a n t
1
a d d i t i o n s y s t e m (see F i g u r e 2) w e r e c l o s e d ; a n d t h e a p p r o p r i a t e
c o m b i n a t i o n o f c a p i l l a r y t i p s ( i n the e x i t m a n i f o l d ) were v a l v e d o n -
line.
The c o n c e n t r a t i o n of t r a n s - s t i l b e n e f l o w i n g i n t o the p h o t o -
r e a c t o r was c o n t r o l l e d by the r e a c t a n t a d d i t i o n system i l l u s t r a t e d i n
F i g u r e 2. t r a n s - S t i l b e n e was c o a t e d o n t o g l a s s beads and l o a d e d i n t o
the feeder tube. A f t e r i m m e r s i n g the f e e d e r tube i n a c o n s t a n t
t e m p e r a t u r e b a t h , the s y s t e m was s e a l e d and p r e s s u r i z e d . As shown i n
F i g u r e 3, t e m p e r a t u r e was an e f f e c t i v e means o f c o n t r o l l i n g t h e
c o n c e n t r a t i o n o f t r a n s - s t i l b e n e e x i t i n g the f e e d e r t u b e .
If n e c e s s a r y , c o n c e n t r a t i o n s t o the r e a c t o r were further
a d j u s t e d through m a n i p u l a t i o n of the v a l v e system, e.g. opening
v a l v e s V^' and V * t o d i l u t e t h e s o l u t i o n e n t e r i n g the p h o t o r e a c t o r .
2
T h i s c o m p o n e n t was v e r y e f f e c t i v e f o r d e l i v e r i n g a w i d e r a n g e o f
constant c o n c e n t r a t i o n s to the p h o t o r e a c t o r . F u r t h e r m o r e , downstream
c o n c e n t r a t i o n s of s t i l b e n e were c o n s i d e r a b l y below the s a t u r a t i o n
l e v e l , and p l u g g i n g o f the s y s t e m was not a p r o b l e m .
T e m p e r a t u r e i n t h e p h o t o r e a c t o r was c o n t r o l l e d t o + 0 . 1 ° C by
i m m e r s i o n i n a c o n s t a n t t e m p e r a t u r e Dewar f l a s k . For experiments
u s i n g c y c l o h e x a n e a s t h e s o l v e n t , t h e r e a c t o r was f i l l e d w i t h a
s o l u t i o n of t r a n s - s t i l b e n e , l o o s e l y s t o p p e r e d , a n d , a f t e r r e a c h i n g
the d e s i r e d temperature, i r r a d i a t e d . P e r i o d i c a l l y , a l i q u o t s were
w i t h d r a w n and a n a l y z e d by gas c h r o m a t o g r a p h y .
E x p e r i m e n t s u s i n g C 0 were c o n d u c t e d i n the f l o w mode u t i l i z i r
2

AIDA AND SQUIRES Photoisomerization oftrans-Stilbene

t e c h n i q u e s d e s c r i b e d above t o c o n t r o l f l o w r a t e s and c o n c e n t r a t i o n s
of t r a n s - s t i l b e n e s u p p l i e d t o the r e a c t o r . The p r o d u c t s t r e a m from
the r e a c t o r was d i r e c t e d t o e i t h e r a p r o d u c t i s o l a t i o n l o o p o r an o n -
l i n e gas c h r o m a t o g r a p h i c a n a l y s i s l o o p , and the p r o d u c t s were a n a -
l y z e d t o d e t e r m i n e the r a t i o o f c i s - t o t r a n s - s t i l b e n e and t o d e t e c t
other photoproducts. A c o n s t a n t p h o t o s t a t i o n a r y r a t i o was a c h i e v e d
i n one t o f o u r m i n u t e s , w e l l w i t h i n the r e s i d e n c e time i n the
i r r a d i a t i o n zone.
A w i d e l y u s e d method f o r a s s e s s i n g s u p e r c r i t i c a l f l u i d phenomena
consists o f c o m p a r i n g p h y s i c a l and c h e m i c a l b e h a v i o r above the c r i t -
i c a l p o i n t w i t h c o r r e s p o n d i n g b e h a v i o r i n the s u b c r i t i c a l l i q u i d .
Because t h i s a p p r o a c h ( u n r e a l i s t i c a l l y ) seeks to observe d i s c o n t i n -
uous b e h a v i o r b e t w e e n s t a t e s , t h e r e s u l t s o f s u c h e x p e r i m e n t s a r e
o f t e n ambiguous. In the p r e s e n t s t u d y , we have compared the p h o t o -
i s o m e r i z a t i o n of t r a n s - s t i l b e n
and, t o model l i q u i d b e h a v i o r
i z a t i o n s i n cyclohexane. In a l l t h r e e s y s t e m s , the e f f e c t s o f t e m p -
e r a t u r e and c o n c e n t r a t i o n on the c i s / t r a n s r a t i o were compared; a n d ,
f o r the C 0 s y s t e m s , the e f f e c t o f p r e s s u r e on t h i s p h o t o s t a t i o n a r y
2
r a t i o was a l s o p r o b e d . The r e s u l t s from t h e s e e x p e r i m e n t s a r e shown

i n T a b l e s I and II and are p l o t t e d i n F i g u r e s 4 t h r o u g h 6.
3
Table I . Photoisomerization o f t r a n s - S t i l b e n e i n Cyclohexane
Initial Temperature Irradiation Photostationary

Concentration Time State
b
(mg/ml) <°C) (Minutes) (cis/trans)
2.14 21.7 70.0 6.1

2.14 40.0 70.0 6.1
1.07 21.7 20.0 6.9
1.07 40.0 30.0 6.9
0.50 21.7 10.0 6.4
0.50 40.0 15.0 6.7
0.25 21.7 10.0 6.4
0.25 40.0 5.0 6.6
a. Atmospheric pressure; d i r e c t i r r a d i a t i o n with a Hanovia 450

w a t t medium p r e s s u r e mercury v a p o r lamp.
b. Pure t r a n s - s t i l b e n e was u s e d .
From the r e s u l t s o b t a i n e d i n c y c l o h e x a n e (Table I), it is clear

t h a t , i n the condensed p h a s e , we can e x p e c t v e r y l i t t l e e f f e c t on the
p h o t o s t a t i o n a r y s t a t e due t o changes i n t e m p e r a t u r e o r c o n c e n t r a t i o n .
On the o t h e r hand, t h e s e f a c t o r s cause l a r g e changes when the r e a c -
t i o n i s c a r r i e d out i n l i q u i d o r ( e s p e c i a l l y ) SCF C 0 . The c o n t r a s t
2
i n b e h a v i o r i s even more a p p a r e n t f r o m F i g u r e s 4 and 5.

The r e s p o n s e s o f the c i s / t r a n s r a t i o t o changes i n p r e s s u r e f o r
l i q u i d ( 2 5 ° C ) and s u p e r c r i t i c a l f l u i d ( 4 0 ° C ) C 0 2are p l o t t e d in
F i g u r e 6. There i s a n o t i c e a b l e e f f e c t i n l i q u i d C 0 , b u t the p h o t o -
2

AIDA A N D SQUIRES Photoisomerization of trans-Stilbene
-20 0 20 40
Temperature (°C)
F i g u r e 3. E f f e c t o f temperature on CCL s o l u b i l i t y of trans-

stilbene.
0.25 0.50 0.75 1.00

Concentration
(mg/mL)
F i g u r e 4. C o n c e n t r a t i o n e f f e c t s i n the photoisomerization of
trans-stilbene.

1
5 »
20 30 40 50
Temperature
(°C)
F i g u r e 5. Temperature e f f e c t s i n the photoisomerization o f

trans-stilbene.
7-
—1
Λ
o
• co . 2 25° C
1
1 • co , 2 40° C
I
I
!
3-
• (?)
1-
500 1000 1500 2000 2500 3000
Pressure
(psi)
F i g u r e 6. Pressure e f f e c t s i n the photoisomerization of trans-

stilbene.

5. AIDA A N D SQUIRES Photoisomerization of trans-Stilbene 65
s t a t i o n a r y r a t i o i s c l e a r l y more r e s p o n s i v e t o p r e s s u r e m a n i p u l a t i o n s
i n the s u p e r c r i t i c a l f l u i d s t a t e . The o b s e r v e d b e h a v i o r i s c o n s i s -
t e n t w i t h t h e m o d e l d e v e l o p e d by S a l t i e l a n d D ' A g o s t i n o (26) w h i c h
a t t r i b u t e s i n c r e a s e s i n the c i s / t r a n s r a t i o to i n c r e a s e s i n s o l v e n t
viscosity. As t h e p r e s s u r e ranges f r o m 1100 t o 3000 p s i , t h e r e i s a
s l i g h t i n c r e a s e i n t h e v i s c o s i t y o f l i q u i d C0 # 2
b
there i s a
u t
t h r e e - f o l d i n c r e a s e i n the v i s c o s i t y o f s u p e r c r i t i c a l C 0 . 2
a
T a b l e I I . P h o t o i s o m e r i z a t i o n o f t r a n s - S t i l b e n e i n Carbon Dioxide
Initial Reactor Temperature Pressure Photostationary

Concentrât i o n Concentration State
b
(mg/NL) (mg/ml) c
<°C) (psi) (cis/trans)
2.00 0.98 25 2000 8.63

2.00 0.87 40 2000 8.68
0.80 0.39
0.40 0.16
0.40 0.16 25 1100 5.51
0.40 0.05 40 1116 1.38 d
0.40 0.17 25 1200 5.82

0.40 0.07 40 1200 5.51
0.40 0.18 25 1300 6.06
0.40 0.11 40 1300 6.24
0.40 0.18 25 1500 6.19
0.40 0.15 40 1500 6.65
0.40 0.20 25 2000 6.42
0.40 0.17 40 2000 6.73
0.40 0.21 25 3000 6.80
0.40 0.19 40 3000 6.91
0.28 0.13 35 2000 5.66
0.28 0.12 40 2000 6.54
0.28 0.11 50 2000 7.04
0.24 0.10 40 2000 6.29
0.12 0.052 40 2000 4.80
a. Irradiation in a flow reactor with a 450 watt Hanovia medium

p r e s s u r e mercury vapor lamp.
b. Pure t r a n s - s t i l b e n e was u s e d . Normal l i t e r (NL) : the q u a n t i t y o f
C0 2 which has a volume o f 1 l i t e r a t 25°C and 1 atmosphere.
c . C a l c u l a t e d from the r e p o r t e d d e n s i t y o f pure C 0 . 2
d . V a l u e a p p r o x i m a t e due t o p r e s s u r e a n d f l o w f l u c t u a t i o n s u n d e r
these conditions.
While the i m p l i c a t i o n s f o r m a n i p u l a t i n g c h e m i c a l pathways,

r a t e s , and e q u i l i b r i a i n s u p e r c r i t i c a l f l u i d s a r e e x c i t i n g , the
e x p e r i m e n t s r e p o r t e d here p r o v i d e no d i r e c t e v i d e n c e about the n a t u r e
o f the i n t e r a c t i o n s r e s p o n s i b l e f o r t h i s b e h a v i o r , and t h i s w i l l be
the f o c u s o f f u t u r e i n v e s t i g a t i o n s .
Acknowledgments
We w i s h to thank P r o f e s s o r R. S. H a n s e n a n d D r . C . G. V e n i e r for

helpful discussions. We g r a t e f u l l y acknowledge the s u p p o r t o f Iowa

S t a t e U n i v e r s i t y t h r o u g h the Energy & M i n e r a l s R e s o u r c e s R e s e a r c h
Institute.
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1879, 29, 324.
2. Paulaitis, M.E.; Krukonis, V.J.; Kurnik, R.T.; Reid, R.C. Rev.
in Chem. Eng., 1983, 1(2), 179.
3. Johnston, K.P. In "Kirk-Othmer Encyclopedia of Chemical
Technology"; John Wiley & Sons: New York, 1984.
4. Maddocks, R.R.; Gibson, J.J. J. Chem. Eng. Prog. 1977, 73(6),
59.
5. Caragay, A.B. Perfumer Flavorist, 1981, 6(4), 43.
6. Hubert, P.; Vitzthun, O.G. Angew. Chem., Int. Ed. Engl. 1978,
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7. Zosel, K. Angew. Chem.
8. Meyers, M.N.; Giddings, J.C. Prog. Sep. Purif., 1970, 3, 133.
9. van Wasen, U.; Swaid, I.; Schneider, G.M. Angew. Chem., Int. Ed.
Engl. 1980, 19, 575.
10. Schneider, G.M., ibid., 1978, 17, 716.
11. Hyatt, J.A. J. Org. Chem. 1984, 49, 5097.
12. Squires, T.G.; Venier, C.G.; Aida, T. Fluid Phase Equil. 1983,
10, 261.
13. Reichardt, C. J. Pure&Appl. Chem. 1982, 54, 1867.
14. Bartmann, D.; Schneider, G.M. J. Chromatogr. 1973, 83, 135.
15. McHugh, M.A.; Krukonis, V.J. "Supercritical Fluid Extraction:
Principles and Applications"; Butterworths: Boston, 1986; Chap.
11.
16. Alexander, G.; Paulaitis, M.E. paper presented at the A.I.Ch.E.
Annual Meeting at San Francisco, CA, November, 1984.
17. Crooks, R.M.; Fan, F.-R.F.; Bard, A.J. J. Am. Chem. Soc. 1984,
106, 6851.
18. Silverstri, G.; Gambino, S.; Filardo, G.; Cuccia, C.; Guarino, E.
Angew. Chem., Int. Ed. Engl. 1981, 20, 101.
19. Cottle, J.E. Supercritical polymerization of olefins. U.S.
Patent 3,294,772. 1966.
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21. Koll, P.; Metzger, J. Angew. Chem. Int. Ed. Engl. 1978, 17, 754.
22. Metzger, J.O.; Hartmans, J.; Malwitz, D.; Koll, P. In "Chemical
engineering at supercritical fluid conditions"; Paulaitis, M.E.;
Penninger, J.M.L.; Gray, R.D.; Davidson, P., Eds.; Ann Arbor
Science: Ann Arbor, MI, 1983; Chap. 14.
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Pap.-Am. Chem. Soc., Div. Fuel Chem. 1985, 30(3), 7.
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R E C ESaltiel, J.;29,D'Agostino,
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969.
Chapter 6
Solvent Effects During the Reaction

of Coal Model Compounds
Martin A. Abraham and Michael T. Klein
Department of Chemical Engineering, University of Delaware, Newark, DE 19716
The reaction of benzylphenylamine in supercritical

water and supercritical methanol is shown to involve
parallel pyrolysi
Reactant conversion passed through a minimum as the
solvent loading increased while the product spectrum
shifted from pyrolysis-1ike to solvolysis-1ike. The
observed kinetics were consistent with two mechanistic
interpretations. The first involves parallel pyrolysis
and solvolysis steps, each having pressure-dependent
rate constants. The second assumes the formation of a
solvent cage, which suppresses the pyrolysis kinetics
as the solvent loading increases from zero to above its
critical density.
The chemical reactions that accompany the extraction of volatiles (1_)
from hydrocarbon resources are frequently obscured by the complexi-
ties of the reaction system. In contrast, the comparative simplicity
of model compound structures and product spectra permit resolution of
reaction fundamentals (2) and subsequent inference of the factors
that control real reacting systems. Herein is described the use of
model compounds to probe the kinetics of pyrolysis and solvolysis
reactions that likely occur during the extraction of volatiles from
coals and lignins.
Previous studies of the reactions of guaiacol (orthomethoxy-
phenol) (3) 9 di benzyl ether (_4 ), and benzyl phenyl ami ne (J>) in dense
water elucidated parallel hydrolysis and pyrolysis pathways, the
selectivity to the latter increasing with water density. Reactant
decomposition kinetics were interestingly nonlinear in water density
and consistent with two mechanistic interpretations. The first
involved "cage" effects, as described for reactions in liquid
solutions (6_). The second led to parallel pyrolysis and solvolysis
reaction pathways wherein associated rate constants were dependent
upon pressure. These two schemes are probed herein through the
reactions of benzyl phenyl ami ne (8PA) in water and methanol.
0097-6156/87/0329-0067$06.00/0

Experimental
T a b l e I summarizes the e x p e r i m e n t a l c o n d i t i o n s of r e a c t a n t ' s c o n c e n

t r a t i o n , s o l v e n t l o a d i n g , t e m p e r a t u r e , and h o l d i n g t i m e . Measured
amounts of the c o m m e r c i a l l y a v a i l a b l e ( A l d r i c h ) s u b s t r a t e b e n z y l -
phenylamine (BPA), t h e s o l v e n t ( t e t r a l i n , water or m e t h a n o l ) , and t h e
i n e r t i n t e r n a l s t a n d a r d b i p h e n y l were loaded at room temperature i n t o
" t u b i n g bomb" m i c r o r e a c t o r s t h a t have been d e s c r i b e d elsewhere ( 5 ) .
Table I. Experimental Conditions f o r Reaction of BPA
BPA Reaction Solvent Holding

Cone. Temp. Loading Time
Solvent (mol/L) (°C) (mol/L) (min)
None (Neat) 0.64 386 — 5 - 50
Tetra l i η 0.59 386 2.95 5-60
Water 0.5
Methanol 0.5
S e a l e d r e a c t o r s were immersed i n t o a f l u i d i z e d sand bath h e l d c o n -

s t a n t at the d e s i r e d r e a c t i o n t e m p e r a t u r e , which was a t t a i n e d by the
r e a c t o r s i n about 2 m i n ; t h i s heat-up p e r i o d was small compared t o
u l t i m a t e r e a c t i o n times (up t o 60 min) and was, i n any c a s e ,
i d e n t i c a l for a l l runs. Products were i d e n t i f i e d by GC-MS and
q u a n t i t a t e d by GC as d e s c r i b e d elsewhere (4_,_5).
Results
T a b l e II summarizes the major r e a c t i o n p r o d u c t s . Neat p y r o l y s i s of

BPA l e d t o t o l u e n e , a n i l i n e , and b e n z a l a n i 1 i n e as major products with
minor p r o d u c t s i n c l u d i n g 1 , 2 - d i p h e n y l e t h a n e , d i p h e n y l m e t h a n e , and
2-benzylaniline. BPA c o n v e r s i o n (x) was n e a r l y 1.0 i n 30 min.
Y i e l d s (yi=n-j/nBp/\ ) of t o l u e n e and a n i l i n e were both a p p r o x i m a t e l y
0
0.5. B e n z a l a n i l i n e , a dehydrogenated BPA a n a l o g , was observed i n a

y i e l d near 0.2, a p p r o x i m a t e l y o n e - h a l f the y i e l d of the major f r a g
m e n t a t i o n p r o d u c t s t o l u e n e and a n i l i n e .
Table II. Selectivity t o Major Products of BPA R e a c t i o n s at 386°C

and 25 min
Reactants
BPA/Neat BPA/Tetralin BPA/Water BPA/MeOH
Product p = 0.81 r Ρ = 1.0
γ
Toluene 0.5 0.63 0.31 0.55

Ani1ine 0.5 0.63 0.62 0.08
Benzalaniline 0.2 0.1 0.02 0.02
Benzyl A l c o h o l — 0.25 0.10
Benzaldehyde — — 0.21 0.06
N-methylaniline — — — 0.20

6. ABRAHAM AND KLEIN Reaction of Coal Model Compounds 69
T h e r m o l y s i s of BPA i n t e t r a l i n was s l o w e r than neat p y r o l y s i s ,

as a c o n v e r s i o n of o n l y 0.8 was reached a f t e r 60 m i n . The y i e l d s of
t o l u e n e and a n i l i n e a s y m p t o t i c a l l y approached 0 . 5 ; b e n z a l a n i l i n e
y i e l d approached 0.1 a f t e r 60 m i n . S e l e c t i v i t y (y-j/x) t o t o l u e n e ,
a n i l i n e , and b e n z a l a n i l i n e was, r e s p e c t i v e l y , 0 . 5 , 0 . 5 , and 0.2 f o r
neat p y r o l y s i s and 0.63, 0.63, and 0.13 f o r t h e r m o l y s i s i n t e t r a l i n .
The i n c r e a s e d s e l e c t i v i t y t o t o l u e n e and a n i l i n e and t h e d e c r e a s e d
s e l e c t i v i t y to b e n z a l a n i l i n e during r e a c t i o n i n t e t r a l i n suggests
t h a t t h i s hydrogen donor competed with BPA as the hydrogen s o u r c e .
The r e a c t i o n of BPA i n water at 386°C and p = 0.8 i s summarizedr
i n F i g u r e 1 and l e d t o benzyl a l c o h o l and benzaldehyde as w e l l as t h e

neat p y r o l y s i s p r o d u c t s . BPA c o n v e r s i o n was a p p r o x i m a t e l y 0.8 a f t e r
40 m i n . A n i l i n e was the major product with a y i e l d of 0.5 a f t e r 40
min. T o l u e n e , a primary and major product of neat p y r o l y s i s , had a
y i e l d near 0.2. T h i s was roughly equal t o t h e y i e l d of benzyl
a l c o h o l , which had a maximum v a l u e of 0.15 at 30 m i n ; the y i e l d of
benzyl a l c o h o l d e c r e a s e d a f t e r 30 m i n . The reduced y i e l d of t o l u e n e
r e l a t i v e t o neat p y r o l y s i
c a t e t h a t water r e a c t e d wit
The e f f e c t of water d e n s i t y on BPA c o n v e r s i o n and product
s e l e c t i v i t y , f o r a c o n s t a n t r e a c t i o n time of 10 min, i s shown i n
F i g u r e 2. BPA c o n v e r s i o n passed through a minimum at a reduced water
d e n s i t y of 0 . 1 . The s e l e c t i v i t y t o a n i l i n e was r e l a t i v e l y u n a f f e c t e d
by the s o l v e n t d e n s i t y , but t h e s e l e c t i v i t y t o t o l u e n e and b e n z a l -
a n i l i n e d e c r e a s e d and the s e l e c t i v i t y t o benzyl a l c o h o l i n c r e a s e d as
the solvent loading increased.
The r e a c t i o n of BPA i n s u p e r c r i t i c a l methanol at 340°C and
p = 0.5 i s summarized i n F i g u r e 3 and l e d t o N - m e t h y l a n i l i n e as a
r
major p r o d u c t . Benzaldehyde and benzyl a l c o h o l were observed i n

y i e l d s l e s s than 0 . 1 . The y i e l d o f t o l u e n e was 0.56, roughly e q u i v -
a l e n t t o t h a t observed from neat p y r o l y s i s , whereas the a n i l i n e y i e l d
was a p p r o x i m a t e l y 0 . 1 , s u b s t a n t i a l l y reduced from t h a t observed i n
t h e neat c a s e . The y i e l d of N - m e t h y l a n i l i n e s u r p a s s e d t h a t of
a n i l i n e , as a v a l u e of 0.4 was a t t a i n e d a f t e r 120 m i n . Reaction in
l ^ C - l a b e l e d methanol showed the l a b e l t o r e s i d e on the methyl group
i n t h e N - m e t h y l a n i l i n e p r o d u c t , d e f i n i t i v e l y i n d i c a t i n g t h a t methanol
r e a c t e d with BPA.
The e f f e c t of methanol d e n s i t y on BPA c o n v e r s i o n and product
s e l e c t i v i t y , at a c o n s t a n t r e a c t i o n time of 60 min and a t e m p e r a t u r e
o f 3 4 0 ° C , was q u a l i t a t i v e l y s i m i l a r t o t h a t observed f o r w a t e r . This
i s i l l u s t r a t e d i n F i g u r e 4, where the minimum c o n v e r s i o n o c c u r s at a
reduced methanol d e n s i t y of 0 . 6 . The y i e l d of t o l u e n e was r e l a t i v e -
l y u n a f f e c t e d by changes i n the methanol d e n s i t y , whereas the y i e l d
o f a n i l i n e d e c r e a s e d and t h a t o f N - m e t h y l a n i l i n e i n c r e a s e d as t h e
solvent loading increased.
Discussion
BPA r e a c t i o n i n water or methanol y i e l d e d s o l v a t i o n p r o d u c t s i n

a d d i t i o n t o t h o s e observed from p y r o l y s i s neat and t h e r m o l y s i s i n the
hydrogen donor s o l v e n t , t e t r a l i n . BPA c o n v e r s i o n passed through a
minimum at a reduced s o l v e n t d e n s i t y o f 0.6 and 0.1 f o r r e a c t i o n i n
methanol and w a t e r , r e s p e c t i v e l y . Results q u a l i t a t i v e l y s i m i l a r to
t h o s e observed i n F i g u r e s 2 and 4 have been noted p r e v i o u s l y f o r

10 20 30
Reaction time (min)
F i g u r e 1. The r e a c t i o n o f BPA i n s u p e r c r i t i c a l water at 386°C and

p = 0.81.
r
Reduced Water Density
F i g u r e 2. E f f e c t o f water d e n s i t y on BPA c o n v e r s i o n and product

s e l e c t i v i t y f o r r e a c t i o n at 386°C a f t e r 10 m i n .

ABRAHAM AND KLEIN Reaction of Coal Model Compounds
~Ί 1 1 1 1 r~
0.5
Reduced methanol density
F i g u r e 4. E f f e c t o f methanol d e n s i t y on BPA c o n v e r s i o n and

product s e l e c t i v i t y f o r r e a c t i o n at 340°C a f t e r 60 m i n .

r e a c t i o n s i n s o l u t i o n with networks c o n t a i n i n g p r e s s u r e - d e p e n d e n t
r a t e c o n s t a n t s (7_). The minimum i n BPA c o n v e r s i o n i s e x p l a i n e d by t h e
s i m u l t a n e o u s d e c r e a s e i n t h e r a t e of t h e p y r o l y s i s r e a c t i o n and
i n c r e a s e i n t h e r a t e of the s o l v o l y s i s r e a c t i o n .
These r e s u l t s are c o n s i s t e n t with the r e a c t i o n pathways shown i n
F i g u r e 5. The major neat p y r o l y s i s pathway, i l l u s t r a t e d i n F i g u r e
5a, r e q u i r e s two molar e q u i v a l e n t s of BPA f o r the f o r m a t i o n of one
mole each of t o l u e n e , a n i l i n e , and c a r b o n - r i c h p r o d u c t s (CRP) which
i n c l u d e t h e observed b e n z a l a n i l i n e . The network f o r t h e r m o l y s i s i n
t e t r a l i n i s a c o m b i n a t i o n of t h e neat p y r o l y s i s pathway ( F i g u r e 5a)
and a pathway wherein t e t r a l i n and BPA r e a c t t o one mole each of
t o l u e n e and a n i l i n e , and 0.5 molar e q u i v a l e n t s of n a p h t h a l e n e .
F i g u r e 5b d e p i c t s a d i r e c t s o l v o l y s i s pathway f o r water and methanol
solvents. Here t h e BPA can e i t h e r ( i ) r e a c t by t h e neat p y r o l y s i s
pathway w i t h t h e consumption of another BPA, t o g i v e one mole each of
t o l u e n e , a n i l i n e , and b e n z a l a n i l i n e o r ( i i ) proceed through t h e
s o l v o l y s i s pathway t o g i v e oxygenated p r o d u c t s and a n i l i n e (or N-
methylaniline for reactio
oxygenated p r o d u c t s woul
The minima i n 3PA c o n v e r s i o n observed f o r r e a c t i o n o f BPA i n
water and methanol can be e x p l a i n e d by a l l o w i n g t h e r a t e c o n s t a n t s o f
F i g u r e 5b t o be dependent on p r e s s u r e . F o r each s o l v e n t l o a d i n g (and
thus pressure) s t u d i e d , the p s e u d o - f i r s t - o r d e r rate constants f o r the
pathways o f F i g u r e 5b are shown i n T a b l e III. These were c a l c u l a t e d
u s i n g a s e q u e n t i a l s i m p l e x s e a r c h based on t h e Complex Method of Box
{8) where the o b j e c t i v e f u n c t i o n was t h e square of the d e v i a t i o n s
between p r e d i c t e d and e x p e r i m e n t a l v a l u e s . The p r e s s u r e g e n e r a t e d by
water was e s t i m a t e d from PVT data (9) and t h e methanol p r e s s u r e was
e s t i m a t e d u s i n g a Peng-Robinson e q u a t i o n of s t a t e .
T r a n s i t i o n s t a t e theory e x p l i c i t l y provides the pressure depen
dence of an nth o r d e r r a t e c o n s t a n t f o r an elementary s t e p through
t h e volume of a c t i v a t i o n , A V * , as i n d i c a t e d i n E q u a t i o n 1.
9lnk ΑΙΙ Φ , 3lnc T
+ 1
« - i r -5Γ (D
Note t h a t Δ η * i s t h e d i f f e r e n c e between t h e number of moles i n
t h e t r a n s i t i o n s t a t e and t h e m o l e c u l a r i t y of the e l e m e n t a r y s t e p . In
E q u a t i o n 3, k i s t h e observed r a t e c o n s t a n t based on c o n c e n t r a t i o n ,
c
and q - i s t h e t o t a l c o n c e n t r a t i o n o f t h e r e a c t i o n m i x t u r e (1_0). The

volume o f a c t i v a t i o n i s the d i f f e r e n c e between the p a r t i a l molar
volumes o f the a c t i v a t e d s t a t e and the r e a c t a n t s .
F o r r e a c t i o n s i n s o l u t i o n , p r e s s u r e s i n t h e range o f k i l o b a r s
are g e n e r a l l y r e q u i r e d before the rate constant i s a f f e c t e d s i g n i f i
cantly. T h i s i s because t y p i c a l v a l u e s of t h e a c t i v a t i o n volume
range from -20 t o +20 cc/mol {U) and, h e n c e , In ( k / k g ) , which i s
equal t o - A V * A P / R T , does not become s i g n i f i c a n t ( e . g . ~1) u n t i l l a r g e
changes i n p r e s s u r e ( e . g . , Δ Ρ = 2.74 kbar f o r Δ ν * = - 2 0 c c / m o l ) o c c u r .
However, Simmons and Mason (1_2) have shown t h a t near t h e c r i t i c a l
p o i n t o f a f l u i d t h e volume of a c t i v a t i o n may approach ± ~ . Moreover,
as can be seen from E q u a t i o n 1, t h e e f f e c t of p r e s s u r e on t h e r a t e
c o n s t a n t i s a t t r i b u t a b l e t o not o n l y t h e i n t r i n s i c volume of a c t i v a
t i o n but a l s o t h e c o m p r e s s i b i l i t y of t h e f l u i d which may be l a r g e i n
a f l u i d near i t s c r i t i c a l p o i n t . Hence, t h e net " a p p a r e n t " volume of

Table III. Apparent Rate C o n s t a n t s f o r BPA R e a c t i o n i n SC S o l v e n t s
Reaction i n water at 386°C

Estimated
Pr Pressure ki χ 1 0 3
k χ 10
2 3
(atm) (min-1) (L(mol)-l(min)-l)

0.0 0 69 —
0.025 22 26 17
0.05 45
0.1 87
0.3 184 14 2.2
0.5 227 15 1.6
0.8 249 17 2.0
1.2 264 18 1.8
R e a c t i o n i n methanol at 386°C
0.1 43.1 22 6.4
0.3 117.3 8.1 2.6
0.5 183.0 8.6 1.5
0.75 264.7 7.7 1.8
1.0 358.9 6.1 1.3
1.25 480.7 2.7 1.0
1.6 739.2 3.2 1.0
R e a c t i o n i n methanol at 340°C
0.0 0.0 22 —
0.1 39.2 5.8 1.7

0.3 101.8 4.0 0.93
0.5 151.6 2.9 1.4
0.75 208.1 2.7 0.87
1.0 271.0 1.3 0.84
1.3 375.9 1.0 0.72
1.6 547.0 0.38 0.50

a c t i v a t i o n i s the sum of an i n t r i n s i c term and a term a r i s i n g from

t h e s o l u t i o n c o m p r e s s i b i l i t y , both o f which may be u n u s u a l l y l a r g e .
T h u s , t h e e f f e c t s of p r e s s u r e on the r e a c t i o n r a t e c o n s t a n t can be
o b s e r v e d at p r e s s u r e s s i g n i f i c a n t l y lower than p r e v i o u s l y noted i n
the l i q u i d - p h a s e l i t e r a t u r e .
The e f f e c t s of s o l v e n t d e n s i t y on the observed r a t e s can a l s o be
i n t e r p r e t e d through the onset of cage e f f e c t s . As the s o l v e n t
l o a d i n g i n c r e a s e s , the system d e n s i t y i n c r e a s e s from a g a s - l i k e t o a
l i q u i d - l i k e value. In dense f l u i d s , an a d d i t i o n r e a c t i o n such as
A + Β -> AB i s c o n s i d e r e d t o f o l l o w , i n s e r i e s , the f o r m a t i o n of an
e c o u n t e r e d p a i r AB* (6_). S i m i l a r l y , the f r a g m e n t a t i o n r e a c t i o n AB ->
A + Β can be l i m i t e d by the r a t e of b r e a k i n g apart t h e e n c o u n t e r e d
p a i r AB*. For the pathways of F i g u r e 6, the e n c o u n t e r e d s p e c i e s i s
BPA*. Rate c o n s t a n t s k^, k_x, and k3 a r e i n t r i n s i c , whereas k2 i s the
i n v e r s e of the d u r a t i o n of an e n c o u n t e r . Rate c o n s t a n t k i s p r o 2
p o r t i o n a l t o the d i f f u s i o n c o e f f i c i e n t of the e n c o u n t e r e d s p e c i e s ,
which w i l l be high i n the gas phase and s e v e r a l o r d e r s o f magnitude
lower i n the l i q u i d phase
s t e a d y - s t a t e permits d e r i v a t i o
o f F i g u r e 6 as:
2k k 1 9
1 ά
+ k S (2)
k_ + k "3
0
x 2
Both terms on the r i g h t hand s i d e of e q u a t i o n 2 depend on

solvent loading. In the f i r s t t e r m , k i s i n v e r s e l y p r o p o r t i o n a l t o
2
t h e time o f e n c o u n t e r , τ/\β, which i n t u r n i s i n v e r s e l y p r o p o r t i o n a l

t o the d i f f u s i v i t y . The d i f f u s i v i t y and thus k2 d e c r e a s e with
i n c r e a s e s i n the d e n s i t y as:
k 2 ~ 1/TAB - D ~ 1/ a P (3)
The second of the terms of the r i g h t hand s i d e o f E q u a t i o n 2, k3S,

i n c r e a s e s with s o l v e n t l o a d i n g . The o v e r a l l r a t e of BPA c o n v e r s i o n
may thus i n i t i a l l y d e c r e a s e as the s o l v e n t l o a d i n g i s i n c r e a s e d due
t o the d e c r e a s e i n r a t e c o n s t a n t k ; as the s o l v e n t l o a d i n g i s
2
i n c r e a s e d f u r t h e r , the r a t e of d i s a p p e a r a n c e of BPA s h o u l d i n c r e a s e
because of the i n c r e a s e i n the term k3S.
Conclusions
1. S u p e r c r i t i c a l s o l v e n t s r e a c t with BPA t o y i e l d p r o d u c t s t h a t are

not observed from neat p y r o l y s i s or t h e r m o l y s i s i n a hydrogen
donor.
2. I n c r e a s i n g the s o l v e n t l o a d i n g s h i f t s the product spectrum from
p y r o l y s i s - l i k e to s o l v o l y s i s - l i k e . In a d d i t i o n , a minimum i n
r e a c t a n t c o n v e r s i o n , a r i s i n g from a d e c r e a s e i n the r a t e of the
p y r o l y s i s pathway, i s o b s e r v e d .
3. The observed k i n e t i c s are c o n s i s t e n t with two m e c h a n i s t i c i n t e r
pretations. The f i r s t i n v o l v e s p r e s s u r e - d e p e n d e n t r a t e c o n s t a n t s
as viewed through t r a n s i t i o n - s t a t e t h e o r y . The volume o f a c t i
v a t i o n may be u n u s u a l l y l a r g e due t o the unique p r o p e r t i e s of a

Neat P y r o l y s i s Pathway
1
BPA TOL + ANL + CRP
+ BPA
Reaction Pathways In S u p e r c r i t i c a l F l u i d s
Ί
BPA TOL + ANL + CRP
+ BPA
3)
Ο R
TOL = QT
PhCH OH2 + PhNHR ANL = 0 " NH
2
PhCH OH = 2 O^ 0 H
^ NHR
PhNHR = (X
Qpp Carbon-Rich
Products
Figure 5. G l o b a l pathways f o r t h e r e a c t i o n o f BPA neat and with

supercritical f l u i d solvents.
AB ^ AB*
d In (AB) 2k,k 2
+ k S 3
dt k_, + k 3
1
a D a —
TAB
F i g u r e 6. Model o f p a r a l l e l BPA s o l v o l y s i s and p y r o l y s i s through

caged r a d i c a l p a i r .

f l u i d near i t s c r i t i c a l p o i n t . The second a l l o w s s o l v e n t cage

e f f e c t s t o s u p p r e s s p y r o l y s i s , such t h a t at i n c r e a s i n g s o l v e n t
l o a d i n g , t h e p y r o l y s i s r e a c t i o n becomes d i f f u s i o n l i m i t e d .
Literature Cited
1. Squires, T. G.; Aida, T.; Chen, Y.; Smith, B. F. ACSDiv.Fuel
Chem. Preprints 1983, 28(4), 228.
2. Simmons, M. B.; Klein, M. T. Ind. Eng. Chem. Fundam. 1985, 24,
55.
3. Lawson, J. R.; Klein, M. T. Ind. Eng. Chem. Fundam. 1985, 24,
203.
4. Townsend, S. H.; Klein, M. T. Fuel 1985, 64, 635.
5. Abraham, Μ. Α.; Klein, M. T. Ind. Eng. Chem. Prod. Res. and
Dev. 1985, 24, 300.
6. Moore, J. W.; Pearson R G "Kinetics and Mechanism"; John
Wiley & Sons: New
7. Kohnstam, G. In "Progres
Jennings, K. R.; Suppan, P.; Eds.; Pergamon Press: New York,
1965, Vol. V, p. 335.
8. Beveridge, G. S.; Schechter, R. S. "Optimization: Theory and
Practice"; McGraw-Hill Book Co.: New York, 1970.
9. Keenan, J. H.; Keyes, F. G. "Thermodynamic Properties of
Steam"; John Wiley & Sons: New York, 1986.
11. Eckert, C. A. Ann. Rev. Phys. Chem. 1972, 23, 239.
RECEIVED August 27, 1986

Chapter 7
Heterolysis and Homolysis in Supercritical Water

Michael Jerry Antal, Jr., Andrew Brittain, Carlos DeAlmeida, Sundaresh Ramayya, and
1
Jiben C. Roy
Department of Mechanical Engineering, University of Hawaii, Honolulu, HI 96822
The reaction chemistry of simple organic molecules in super-

critical (SC) water can be described by heterolytic (ionic)
mechanisms when th
10 - 1 4 and by homolytic (free radical) mechanisms when
Kw«10-14. For example, in SC water with Kw>10-14 ethanol
undergoes rapid dehydration to ethylene in the presence of
dilute Arrhenius acids, such as 0.01M sulfuric acid and 1.0M
acetic acid. Similarly, 1,3 dioxolane undergoes very rapid and
selective hydration in SC water, producing ethylene glycol and
formaldehyde without catalysts. In SC methanol the
decomposition of 1,3 dioxolane yields 2 methoxyethanol,
illustrating the role of the solvent medium in the heterolytic
reaction mechanism. Under conditions where Kw«10-14 the
dehydration of ethanol to ethylene is not catalyzed by
Arrhenius acids. Instead, the decomposition products include a
variety of hydrocarbons and carbon oxides.
Efficient thermochemical processes underlie the conversion of crude
oil and natural gas liquids to higher value chemicals and fuels.
Unfortunately, attempts to develop similar conversion processes for
biomass feedstocks (such as wood chips and bagasse) have been
frustrated by the non-specificity of high temperature pyrolysis
reactions involving biopolymer substrates (1,2). For example, the
pyrolysis of bagasse yields a liquid mixture of carbohydrate sirups
and phenolic tars, a gas composed primarily of carbon oxides and
hydrogen, and a solid charcoal. Variations of the conventional
engineering parameters (temperature, heating rate, residence time
and pressure) do not provide a good control over the complex set of
concurrent and consecutive pyrolysis reactions. Thus it has not
been possible to engineer the pyrolysis reactions to produce a few
high value products from biomass materials.
Recent advances in materials technology, high pressure pumps
and other high performance liquid chromatography (HPLC) equipment,
have created new opportunities (3) for fundamental studies of
'Current address: Gonoshathaya Pharmaceuticals Limited, P.O. Nayarhat via Dhamrai,
Dhaka, Bangladesh
0097-6156/87/0329-0077$06.00/0

c h e m i c a l r e a c t i o n s i n s o l v e n t s at v e r y h i g h p r e s s u r e s (>30 MPa) and

t e m p e r a t u r e s ( > 4 0 0 ° C). For s u f f i c i e n t l y d i l u t e s o l u t e - s o l v e n t
m i x t u r e s at p r e s s u r e s P>P , no l i q u i d - v a p o r phase t r a n s i t i o n o c c u r s
C
as t h e m i x t u r e i s h e a t e d . F u r t h e r m o r e , when t h e t e m p e r a t u r e Τ i s
near t h e s o l v e n t ' s c r i t i c a l t e m p e r a t u r e and P>P many s o l v e n t s
C
m a n i f e s t e x t r a o r d i n a r y p r o p e r t i e s (4,5). T h e s e unusual p r o p e r t i e s
o f f e r o p p o r t u n i t i e s f o r the c o n t r o l o f c h e m i c a l r e a c t i o n s i n v o l v i n g
b i o p o l y m e r s and o t h e r s u b s t r a t e s .
As d i s c u s s e d i n the f o l l o w i n g s e c t i o n s , when t h e d e n s i t y o f
s u p e r c r i t i c a l (SC) water exceeds 0.4 g / c m 3
the f l u i d r e t a i n s i t s
i o n i c p r o p e r t i e s (high d i e l e c t r i c c o n s t a n t and i o n p r o d u c t ) - even
at h i g h t e m p e r a t u r e s . These p r o p e r t i e s p r o v i d e new o p p o r t u n i t i e s t o
c a t a l y z e a v a r i e t y o f h e t e r o l y t i c bond c l e a v a g e s w i t h a h i g h degree
o f s p e c i f i c i t y . Examples d i s c u s s e d i n t h i s paper i n c l u d e the
d e h y d r a t i o n o f e t h a n o l t o e t h y l e n e and the h y d r a t i o n o f 1,3
d i o x o l a n e t o g l y c o l and f o r m a l d e h y d e . In each o f t h e s e examples t h e
s p e c i f i c i t y o f t h e h e t e r o l y t i c bond c l e a v a g e i s h i g h ; whereas t h e
c o n v e n t i o n a l , higher temperature
y i e l d s o f the d e s i r e d p r o d u c t s
f i n d i n g s r e p o r t e d here may have e x c i t i n g i m p l i c a t i o n s f o r the
p r o d u c t i o n o f e t h y l e n e from e t h a n o l .
Prior Work
I n t e r e s t i n t h e use o f SC s o l v e n t s as a r e a c t i o n media i s founded

upon r e c e n t advances i n our u n d e r s t a n d i n g o f t h e i r unique thermo-
p h y s i c a l and c h e m i c a l p r o p e r t i e s . Worthy o f s p e c i a l note are t h o s e
t h e r m o p h y s i c a l p r o p e r t i e s (6) which can be m a n i p u l a t e d as parameters
t o s e l e c t i v e l y d i r e c t the p r o g r e s s o f d e s i r a b l e c h e m i c a l r e a c t i o n s .
These p r o p e r t i e s i n c l u d e the s o l v e n t ' s d i e l e c t r i c c o n s t a n t (7), ion
p r o d u c t (8,9), e l e c t r o l y t e s o l v e n t power (10,11), t r a n s p o r t
p r o p e r t i e s " [ v i s c o s i t y (12), d i f f u s i o n c o e f f i c i e n t s (13) and i o n
m o b i l i t i e s (14)], hydrogen bonding c h a r a c t e r i s t i c s (T5), and s o l u t e -
s o l v e n t "enhancement f a c t o r s " (6). A l l t h e s e p r o p e r t i e s are
s t r o n g l y i n f l u e n c e d by t h e s o l v e n t ' s d e n s i t y Ρ i n t h e s u p e r c r i t i c a l
state.
For e x a m p l e , SC water w i t h ρ =0.47 g / c m 3
at 4 0 0 ° C (Ρ = 35.
MPa) e n j o y s a d i e l e c t r i c c o n s t a n t o f about 10 (comparable t o a poâr
o r g a n i c V i q u i d under normal c o n d i t i o n s ) , an i o n p r o d u c t o f 7x10"*
(vs 10" at room c o n d i t i o n s ) and a dynamic v i s c o s i t y u =0.57
m i l l i p o i s e (vs 10 at room c o n d i t i o n s ) . Under t h e s e c o n d i t i o n s SC
water behaves as a w a t e r - l i k e f l u i d w i t h s t r o n g e l e c t r o l y t i c s o l v e n t
power, h i g h d i f f u s i o n c o e f f i c i e n t s and i o n m o b i l i t i e s , and
c o n s i d e r a b l e hydrogen bonding. These p r o p e r t i e s f a v o r c h e m i c a l
r e a c t i o n s i n v o l v i n g h e t e r o l y t i c ( i o n i c ) bond c l e a v a g e s which can be
c a t a l y z e d by t h e p r e s e n c e o f a c i d s o r bases.
Dramatic changes o c c u r when the t e m p e r a t u r e o f t h e SC water i s
3
r a i s e d t o 5 0 0 ° C at c o n s t a n t p r e s s u r e (P=0.144 g / c m ) . 3
Decreases i n
t h e d i e l e c t r i c c o n s t a n t t o a v a l u e o f 2 and i o n p r o d u c t t o
2.1 χ 1 0 " ^ cause the f l u i d t o l o s e i t s w a t e r - l i k e c h a r a c t e r i s t i c s
υ
and behave as a h i g h t e m p e r a t u r e gas. Under t h e s e c o n d i t i o n s

h o m o l y t i c ( f r e e r a d i c a l ) bond c l e a v a g e s are e x p e c t e d t o dominate t h e
reaction chemistry. Thus by u s i n g t h e e n g i n e e r i n g parameters o f

7. ANTAL ET AL. Heterolysis and Homolysis in Supercritical Water 79
t e m p e r a t u r e and p r e s s u r e one can d r a m a t i c a l l y change t h e c h e m i c a l

p r o p e r t i e s o f t h e s o l v e n t ( d i e l e c t r i c c o n s t a n t and i o n product) t o
f a v o r h e t e r o l y t i c o r h o m o l y t i c bond c l e a v a g e s . T h i s paper
emphasizes t h e m a n i p u l a t i o n o f t h e s e parameters as a means f o r
engineering the r e a c t i o n chemistry of biopolymer m a t e r i a l s .
Apparatus and E x p e r i m e n t a l Procedures
F i g u r e 1 i s a s c h e m a t i c o f the SC f l o w r e a c t o r used i n t h i s work.

P r i o r t o the i n i t i a t i o n o f f l o w , t h e system i s brought up t o
p r e s s u r e by an a i r compressor. A f t e r w a r d s , an HPLC pump f o r c e s a
pure s o l v e n t i n t o t h e r e a c t a n t a c c u m u l a t o r at a measured r a t e o f
f l o w . T h i s f l o w d i s p l a c e s the s o l v e n t / s o l u t e r e a c t a n t m i x t u r e out
o f t h e a c c u m u l a t o r , through the r e a c t o r and a 10 p o r t v a l v e dual
l o o p s a m p l i n g system, and i n t o t h e p r o d u c t a c c u m u l a t o r . The f l o w o f
p r o d u c t s i n t o t h e second a c c u m u l a t o r d i s p l a c e s a i r through a b a c k
p r e s s u r e r e g u l a t o r and i n t o a water d i s p l a c e m e n t a p p a r a t u s which
measures the r a t e o f a i
f l o w i s r a p i d l y heated
g u a r d , and m a i n t a i n e d at i s o t h e r m a l c o n d i t i o n s by a Transtemp I n f r a
r e d f u r n a c e and an e x i t heat guard. Samples c a p t u r e d i n 5.54 ml
sample l o o p s are r e l e a s e d i n t o s e a l e d , e v a c u a t e d t e s t tubes f o r
q u a n t i t a t i v e a n a l y s i s by GC, GC-MS, and HPLC i n s t r u m e n t s w i t h i n the
laboratory. The o u t e r annul us o f t h e r e a c t o r i s a 4.6 mm ID
H a s t e l l o y C-276 t u b e , and the i n n e r a n n u l u s i s a 3.2 mm 0D s i n t e r e d
a l u m i n a t u b e , g i v i n g the r e a c t o r an e f f e c t i v e h y d r a u l i c d i a m e t e r o f
1.4 mm. The a l u m i n a tube accommodates a m o v a b l e t y p e Κ t h e r m o c o u p l e
a l o n g t h e r e a c t o r ' s a x i s , which p r o v i d e s f o r the measurement o f
a x i a l temperature gradients along the r e a c t o r ' s f u n c t i o n a l l e n g t h .
R a d i a l t e m p e r a t u r e g r a d i e n t s are measured as d i f f e r e n c e s between t h e
c e n t e r l i n e t e m p e r a t u r e and t e m p e r a t u r e s measured at 10 f i x e d
p o s i t i o n s along the outer w a l l of the r e a c t o r using type Κ
thermocouples. The l o c a t i o n o f the m o v a b l e t h e r m o c o u p l e w i t h i n the
r e a c t o r i s measured e l e c t r o n i c a l l y t o w i t h i n 0.01 mm by a TRAK
d i g i t a l p o s i t i o n r e a d out system. The e n t i r e r e a c t o r and s a m p l i n g
system i s housed i n a " b u l l e t p r o o f " e n c l o s u r e which can be purged
o f a i r (oxygen) d u r i n g s t u d i e s i n v o l v i n g f l a m m a b l e s o l v e n t s (such as
methanol).
The f o l l o w i n g r e p r e s e n t a t i v e n o n d i m e n s i o n a l numbers
c h a r a c t e r i z e the r e a c t o r o p e r a t i n g at 4 0 0 ° C : Re = 420, Pr = 1.86,
Sc = 0 . 8 6 , P e = 3 5 8 , Peu = 776 and Da = 0.4.
m Figure 2 displays a
t y p i c a l temperature p r o f i l e of the r e a c t o r during o p e r a t i o n .
Because t h e t h e r m a l d i f f u s i v i t y o f SC water i s c o m p a r a b l e t o t h a t o f
many h i g h q u a l i t y i n s u l a t i o n m a t e r i a l s , g r o s s r a d i a l t e m p e r a t u r e
g r a d i e n t s can e a s i l y e x i s t i n a f l o w r e a c t o r . As shown i n F i g u r e 2,
r a d i a l t e m p e r a t u r e g r a d i e n t s w i t h i n t h e a n n u l a r f l o w r e a c t o r are
negligible. A computer program, which a c c u r a t e l y a c c o u n t s f o r t h e
e f f e c t s o f t h e v a r i o u s f l u i d ( s o l v e n t , s o l v e n t and s o l u t e , a i r )
c o m p r e s s i b i l i t i e s on f l o w measurements, c a l c u l a t e s mass and
e l e m e n t a l b a l a n c e s f o r each e x p e r i m e n t . A t y p i c a l experiment
e v i d e n c e s mass and e l e m e n t a l b a l a n c e s o f 1.00+0.05.

F i g u r e 1. S u p e r c r i t i c a l f l o w r e a c t o r . Key: (1) M e t t l e r b a l a n c e ; (2) f l a s k w i t h H 0 ( f i l t e r e d and
2

d e a e r a t e d ) ; (3) HPLC pump; (4) bypass (three-way) v a l v e ; (5) f e e d c y l i n d e r ; (6) weather b a l l o o n
w i t h f e e d s o l u t i o n ; (7) probe thermocouple (type K ) ; (8) c e r a m i c a n n u l u s ; (9) H a s t e l l o y C-276 tube
(10) e n t r a n c e c o o l i n g j a c k e t ; (11) e n t r a n c e h e a t e r ; (12) f u r n a c e c o i l s ; (13) q u a r t z g o l d - p l a t e d IR
m i r r o r ; (14) window (no c o i l s ) ; (15) guard h e a t e r ; (16) o u t l e t c o o l i n g j a c k e t ; (17) t e n - p o r t d u a l -
l o o p sampling v a l u e ; (18) p r o d u c t a c c u m u l a t o r ; (19) a i r compressor; (20) b a c k - p r e s s u r e r e g u l a t o r ;
and (21) o u t f l o w m e a s u r i n g assembly.
Ο 10 12 14 16 20 22 I
A x i a l distance (inches) I

ί
Figure 2. Typical wall (Δ Δ ) and centerline (0 9)
temperature p r o f i l e s of the s u p e r c r i t i c a l flow
reactor.

Results
R e s u l t s o f experiments probing the dehydration chemistry of ethanol

i n SC w a t e r (P = 34.5 MPa) a r e s u m m a r i z e d i n T a b l e 1. If
e q u i l i b r i u m were e s t a b l i s h e d , the c o n v e r s i o n o f e t h a n o l t o e t h y l e n e
at 4 0 0 ° C and 34.5 MPa would be 74%. U n f o r t u n a t e l y , t h e u n c a t a l y z e d
r e a c t i o n i s v e r y s l o w and l i t t l e e t h y l e n e i s formed. M o r e o v e r , many
A r r h e n i u s a c i d c a t a l y s t s e i t h e r decompose o r r e a c t w i t h the e t h a n o l
at t h e s e h i g h t e m p e r a t u r e s , f o r m i n g unwanted b y p r o d u c t s . For
e x a m p l e , n i t r i c a c i d c o m p l e t e l y decomposes and l e a d s t o the
f o r m a t i o n o f CO2, CO and o t h e r b y p r o d u c t s . Formic a c i d a l s o
decomposes i n SC water under t h e s e c o n d i t i o n s , and does not c a t a l y z e
the d e h y d r a t i o n r e a c t i o n . At h i g h c o n c e n t r a t i o n s (0.1M) s u l f u r i c
a c i d s u f f e r s some d e c o m p o s i t i o n and r e a c t s w i t h t h e e t h a n o l , as w e l l
as c a t a l y z i n g t h e d e h y d r a t i o n r e a c t i o n . However, at lower c o n c e n -
t r a t i o n s , t h e a c i d e x e r t s a s t r o n g and s e l e c t i v e c a t a l y t i c i n f l u e n c e
on t h e d e h y d r a t i o n o f e t h a n o l . As shown i n T a b l e 1, i n the p r e s e n c e
o f 0.01 M s u l f u r i c a c i d
a t 4 0 0 ° C , y i e l d i n g 82%
U n l i k e f o r m i c a c i d , a c e t i c a c i d i s a b s o l u t e l y s t a b l e i n SC
water t o 5 0 0 ° C at 34.5 MPa. At 4 0 0 ° C t h e p r e s e n c e o f a c e t i c a c i d
(1.0M) t r i p l e s t h e r a t e o f f o r m a t i o n o f e t h y l e n e from e t h a n o l ;
however, the f o r m a t i o n o f t h e l i q u i d b y p r o d u c t e t h y l a c e t a t e
a c c o u n t s f o r 46% o f t h e e t h a n o l which r e a c t e d . N o r m a l l y the
p r e s e n c e o f a s t r o n g a c i d (such as H S 0 O i s r e q u i r e d t o c a t a l y z e
2
t h e f o r m a t i o n o f the a c e t a t e from e t h a n o l and a c e t i c a c i d .

C o n s e q u e n t l y , the f o r m a t i o n o f t h e a c e t a t e ( a l o n g w i t h d i e t h y l e t h e r
as a m i n o r , <1%, a d d i t i o n a l p r o d u c t ) s u r p r i s e d us. This r e s u l t
seems t o i n d i c a t e t h e a b i l i t y o f SC water t o a c t as an a c i d c a t a l y s t
at h i g h t e m p e r a t u r e s when K > 1 0 ~ \
W
11
As mentioned e a r l i e r , at 5 0 0 ° C and 34.5 MPa s u p e r c r i t i c a l

water has a s m a l l d i e l e c t r i c c o n s t a n t , a v e r y low ion p r o d u c t , and
behaves as a h i g h t e m p e r a t u r e gas. These p r o p e r t i e s would be
expected to minimize the r o l e of h e t e r o l y s i s in the dehydration
chemistry. As shown i n T a b l e 1, t h e c o n v e r s i o n o f e t h a n o l t o
e t h y l e n e a t 5 0 0 ° C i s s m a l l , even i n t h e p r e s e n c e o f 0.01M s u l f u r i c
acid catalyst. The appearance o f t h e b y p r o d u c t s CO, C 0 , CH^ and 2
C 2 H 6 p o i n t s to the onset of n o n s e l e c t i v e , f r e e r a d i c a l r e a c t i o n s in
t h e d e c o m p o s i t i o n c h e m i s t r y , as would be e x p e c t e d i n t h e h i g h
t e m p e r a t u r e gas phase t h e r m o l y s i s o f e t h a n o l .
S i m i l a r e x p e r i m e n t s i n v o l v i n g t h e h y d r a t i o n o f 1,3 d i o x o l a n e i n
water (see F i g u r e 3) at 350° C and 34.5 MPa e v i d e n c e d t h e c o m p l e t e
d e c o m p o s i t i o n o f t h e r e a c t a n t and produced a y i e l d o f 99.8% e t h y l e n e
g l y c o l and f o r m a l d e h y d e (formed i n e q u i m o l a r amounts) w i t h a
r e s i d e n c e time o f 100s. An experiment i n v o l v i n g 1,3 d i o x o l a n e i n SC
methanol at 4 5 0 ° C and 13.8 MPa formed the e x p e c t e d p r o d u c t 2-
m e t h o x y e t h a n o l , s u b s t a n t i a t i n g t h e r o l e o f t h e s o l v e n t medium i n t h e
r e a c t i o n c h e m i s t r y as i n d i c a t e d i n F i g u r e 3. The e x t r a o r d i n a r y
s p e c i f i c i t y and r a t e o f h y d r a t i o n r e a c t i o n r e n d e r e d the use o f
c a t a l y s t s unnecessary. These r e s u l t s c o n t r a s t w i t h e a r l i e r f i n d i n g s
(18) c o n c e r n i n g the h i g h t e m p e r a t u r e ( > 6 0 0 ° C), f r e e r a d i c a l
d e c o m p o s i t i o n o f 1,3 d i o x o l a n e i n steam at 0.1 MPa, where a wide
v a r i e t y o f gaseous p r o d u c t s ( i n c l u d i n g H2, CO, CO2, CHi», C H n and 2
C H ) were o b s e r v e d and no s p e c i f i c i t y i n t h e r e a c t i o n c h e m i s t r y
2 6
c o u l d be r e a l i z e d .

TABLE I. Ethanol (1M) Dehydration i n SC Water
Catalyst Catalyst Temp. Press. Res. Time Conver Gaseous P r o d u c t Y i e l d (%)* Carbon
Conc.(M) (°C) (MPa) (s) sion^) 2
C H 4 ^2^6 C0 H
2
2 CO CH 4
Balance
- - 400 31.7 49 2.6 17 1.6 0.0 15 0.0 0.0 0.98
2
H S0 4 0.01 400 34.5 13 21 82 0.0 0.0 0.0 0.0 0.0 0.96
HN0 3 0.01 400 31.7 48 12 1.2 0.1 57 15 14 0.8 0.93
CH3COOH 1.0 400 31.7 52 9.5 12 0.2 0.1 2.3 0.0 0.0 0.98
- - 500 31.7 66 2.0 25 25 3.0 218 3.5 7.8 1.00
2
H S0 4 0.01 500 34.5 8.5 17 40 0.2 1.1 42. 1.8 2.9 0.91

* Y i e l d = (mole p r o d u c t ) / ( m o l e reactant consumed)
Ά low background c o n c e n t r a t i o n o f H 2 is o b s e r v e d , even i n blank e x p e r i m e n t s w i t h pure water as a reactant.

F i g u r e 3. H e t e r o l y t i
from 1,3
M. J o n e s ) .
Discussion
H e t e r o l y t i c r e a c t i o n s can be d i s t i n g u i s h e d from h o m o l y t i c ( f r e e
r a d i c a l ) r e a c t i o n s by t h e f o l l o w i n g c r i t e r i a :
1) h e t e r o l y t i c r e a c t i o n s u s u a l l y can be c a t a l y z e d by
A r r h e n i u s a c i d s and bases.
2) h e t e r o l y t i c r e a c t i o n s u s u a l l y a r e i n f l u e n c e d by t h e n a t u r e
( p o l a r vs n o n - p o l a r ) o f t h e s o l v e n t medium.
3) h e t e r o l y t i c r e a c t i o n s are often q u i t e s p e c i f i c .
4) h o m o l y t i c r e a c t i o n s a r e not i n f l u e n c e d by A r r h e n i u s a c i d
o r base c a t a l y s t s .
5) because o f t e r m i n a t i o n s t e p s , h o m o l y t i c r e a c t i o n s a r e
often non-specific.
F i n d i n g s r e p o r t e d i n t h i s paper i n c l u d e :
1) t h e c a t a l y s i s o f e t h a n o l d e h y d r a t i o n by two A r r h e n i u s
a c i d s i n SC water a t 400°C where K >10~ w
1 1 1
2) t h e i n f l u e n c e o f t h e s o l v e n t (water vs methanol) on t h e
p r o d u c t s and r a t e s o f t h e u n c a t a l y z e d d e c o m p o s i t i o n o f 1,3
dioxolane.
3) t h e e x t r a o r d i n a r y s p e c i f i c i t y o f t h e s e two r e a c t i o n s when
wK >10- . l h
4) t h e i n e f f e c t i v e n e s s o f H2SCK as a c a t a l y s t f o r e t h a n o l
d e h y d r a t i o n i n SC water at 500°C where K « 1 0 " w .
1 1 +
5) the l o s s of s p e c i f i c i t y of the ethanol denydration

r e a c t i o n at 500°C where K « 1 0 " w
1 1 +
.
These f i n d i n g s cause us t o c o n c l u d e t h a t aqueous phase c h e m i c a l
r e a c t i o n s , u s u a l l y o b s e r v e d at much l o w e r t e m p e r a t u r e s , can be
conducted i n SC water p r o v i d i n g K > 1 0 " . w
11+
When ^ « Η Γ * SC water
1
behaves as a h i g h t e m p e r a t u r e gas and f r e e r a d i c a l r e a c t i o n s

predominate.
The f o r m a t i o n o f the e t h y l a c e t a t e e s t e r from e t h a n o l and
a c e t i c a c i d a l s o p o i n t s t o t h e r o l e o f c a r b o c a t i o n c h e m i s t r y i n SC

7. ANTAL ET AL. Heterolysis and Homolysis in Supercritical Water 85
water when K > 1 0 " .

w
11+
In a d d i t i o n , t h i s r e a c t i o n s u g g e s t s t h e
p o s s i b l e r o l e o f SC water as a c a t a l y t i c medium (due t o the " h i g h "
c o n c e n t r a t i o n s o f H+ and 0H-) at s u f f i c i e n t l y h i g h t e m p e r a t u r e s and
pressures.
The c a t a l y t i c d e h y d r a t i o n o f e t h a n o l t o e t h y l e n e i n SC water
may be c o m m e r c i a l l y i m p o r t a n t (16). A l t h o u g h h i g h q u a l i t y
commercial a l u m i n a c a t a l y s t s e x i s t f o r t h e v a p o r phase d e h y d r a t i o n
o f e t h a n o l , t h e commercial p r o c e s s e s r e q u i r e t h e e t h a n o l f e e d s t o c k
t o be r e l a t i v e l y f r e e o f water. Hence t h e e t h a n o l must be d i s t i l l e d
from t h e e t h a n o l - w a t e r m i x t u r e which i s t h e p r o d u c t o f f e r m e n t a t i o n
processes. By a v o i d i n g t h i s d i s t i l l a t i o n s t e p , and s e c u r i n g phase
s e p a r a t i o n o f t h e e t h y l e n e p r o d u c t from t h e e t h a n o l - w a t e r r e a c t a n t ,
SC d e h y d r a t i o n o f e t h a n o l c o u l d e n j o y a d v a n t a g e s o v e r e x i s t i n g
commercial t e c h n o l o g i e s .
Because o f the p o t e n t i a l commercial s i g n i f i c a n c e o f t h i s work,
we a r e p r e s e n t l y d e v e l o p i n g k i n e t i c e x p r e s s i o n s f o r t h e r a t e o f
e t h y l e n e f o r m a t i o n i n the SC water e n v i r o n m e n t We are a l s o
measuring t h e r a t e o f e t h a n o
c r i t i c a l p o i n t o f wate
near t h e c r i t i c a l p o i n t have any i n f l u e n c e on t h e r e a c t i o n r a t e . In
the near f u t u r e we p l a n t o b e g i n s t u d i e s o f the r e a c t i o n c h e m i s t r y
o f g l u c o s e and r e l a t e d model compounds ( l e v u l i n i c a c i d ) i n SC water.
Conclusions
The s i g n i f i c a n c e o f t h i s work i s i t s i d e n t i f i c a t i o n o f SC water

as a medium which s u p p o r t s and enhances aqueous phase c h e m i s t r y
o r d i n a r i l y o b s e r v e d at much lower t e m p e r a t u r e s . Fundamental s t u d i e s
o f t h e r e a c t i o n c h e m i s t r y o f b i o p o l y m e r r e l a t e d model compounds
d e s c r i b e d i n t h i s paper o f f e r i n s i g h t s i n t o the d e t a i l s o f r e a c t i o n
mechanisms, and f a c i l i t a t e t h e c h o i c e o f r e a c t i o n c o n d i t i o n s which
enhance t h e y i e l d s o f v a l u a b l e p r o d u c t s . Chemical r e a c t i o n
e n g i n e e r i n g i n s u p e r c r i t i c a l s o l v e n t s , based on t h e a b i l i t y t o
choose between h e t e r o l y t i c and h o m o l y t i c r e a c t i o n mechanisms w i t h
f o r e k n o w l e d g e o f r e s u l t s , h o l d s much promise as a new means t o
improve our u t i l i z a t i o n o f t h e v a s t b i o p o l y m e r r e s o u r c e .
Acknowledgments
T h i s r e s e a r c h was s u p p o r t e d by t h e N a t i o n a l S c i e n c e F o u n d a t i o n under
g r a n t CPE 8304381, the Department o f P l a n n i n g and Economic
Development o f the S t a t e o f H a w a i i , and t h e C o r a l _ I n d u s t r i e s
Endowment. The a u t h o r s thank Dr. M a r i a Burka (NSF), Kent K e i t h and
Dr. Tak Y o s h i h a r a (DPED), and D a v i d Chalmers ( C o r a l I n d u s t r i e s ) f o r
t h e i r i n t e r e s t i n t h i s work. The a u t h o r s a l s o thank W i l l i a m Mok f o r
h i s c o n t i n u i n g a s s i s t a n c e w i t h t h e f l o w r e a c t o r , Dr. A l i T a b a t a b a i e -
R a i s s i , and P r o f e s s o r M a i t l a n d Jones ( P r i n c e t o n ) f o r many
stimulating discussions. The comments o f the r e v i e w e r s were
appreciated.
Literature Cited
1. Antal, M.J. "Biomass Pyrolysis. A Review of the Literature -
Part 1: Carbohydrate Pyrolysis" in Advances in Solar Energy,
(Eds. K.W. Boer and J.A. Duffie) Vol. 1, (American Solar
Energy Society, Boulder, CO) 1983.

2. Antal, M.J. "Biomass Pyrolysis. A Review of the Literature -

Part 2: Lignocellulose Pyrolysis" in Advances in Solar Energy,
2, (Plenum Press, N.Y.) 1985.
3. Paulaitis, M.E., Penninger, J.M.L., Gray, R.D, Jr. and
Davidson, P. "Chemical Engineering at Supercritical Fluid
Conditions" Ann Arbor Science, Ann Arbor, 1983.
4. Franck, E.U. "Supercritical Water" Endeavor, 1968,27, 55-59.
5. Marshall, W.L. "Water at High Temperatures and Pressures"
Chemistry, 1975, 48, 6-12.
6. Franck, E.U. "Thermophysical Properties of Supercritical
Fluids with Special Consideration of Aqueous Systems", Fluid
Phase Equilib. 1983, 10(2-3), 211-22.
7. Franck, E.U. "Water and Aqueous Solutions at High Pressures and
Temperatures".
8. Marshall, WL . and Franck, E.U.,J. Phys. Chem. Ref. Data, 1981,
10, 295-304.
9. Quist, A.S., Marshall, W.L., and Jolley, H.R. J. Phys. Chem.,
1965, 69, 2726-2735
10. Marshall, W.L., Rev
11. Quist, A.S., J. Phys. Chem., 1970, 74, 3396-3402.
12. Bruges, E.A. and Gibson, M.R., J. Mech. Eng. Sci., 1969, 11,
189-205.
13. Lamb, W.J., Hoffman, G.A., Jonas, J., J. Chem. Phys., 1981,
74(12), 6875- 80.
14. Franck, E.U., Hartmann, D., and Hensel, F., J. Phys. Chem.,
1968, 72, 200-206.
15. Gorbatyi, Y.E., Probl. Fix.-Khim. Petrol., (Eds. Zharikov,
V.A., Fonarev, V.I., Korikovskii, S.P.) 1979, 2, 14-24.
16. Luchi, N.R. and Trindade, S.C., Hydrocarbon Proc., 1982, 179-
183.
17. Knozinger, H. The Chemistry of the Hydroxyl Group, Part 2, (Ed.
S. Patai), Interscience, London 1971.
18. Cutler, Α., Ph.D. thesis, Princeton University, Princeton,
1984.
RECEIVED October 7, 1986

Chapter 8
A Statistical Mechanics Based Lattice Model

Equation of State
Applications to Mixtures with Supercritical Fluids
Sanat K. Kumar, R. C. Reid, and U. W. Suter
Department of Chemical Engineering, Massachusetts Institute of Technology,

Cambridge, MA 02139
A Statistical-Mechanic
of state (EOS) for modelling the phase behaviour of
polymer-supercritical fluid mixtures is presented.
The EOS can reproduce qualitatively all experimental
trends observed, using a single, adjustable mixture
parameter and in this aspect is better than classical
cubic EOS. Simple mixtures of small molecules can
also be quantitatively modelled, in most cases, with
the use of a single, temperature independent adjustable
parameter.
During the last decade, increasing emphasis has been placed on

the use of the equation of state (EOS) approach to model and correlate
high-pressure phase equilibrium behaviour. More successful applications
have employed some form of cubic EOS (1-3) although others (e.g.,
4) have been proposed. However, as the types of systems studied
have become more complex, the inherent weaknesses of a cubic EOS
have become apparent. We, in particular, are interested in studying
phase behaviour of systems comprising polymer molecules in the
presence of a supercritical fluid. Here the size disparity of the
component molecules can be large. One approach would have been to
adopt the modified perturbed hard chain theory (5,6) which has been
adapted for mixtures of large and small hydrocarbon molecules. We,
however, elected to study whether lattice theory models could be of
value for systems of our interest. Studies based on this approach
have been attempted for different systems (7-15), and an interesting
model has been proposed by Panayiotou and Vera (16.) . Our approach
is similar in many respects to the last reference although significant
differences appear in treating mixtures.
0097-6156/87/0329-0088$06.00/0

8. KUMAR ET AL. Lattice Model Equation of State 89
Pure Components
Theory. M o l e c u l e s a r e assumed t o " s i t " on a l a t t i c e o f c o o r d i n a t i o n

number ζ and o f c e l l s i z e V J J . Each m o l e c u l e ( s p e c i e s 1) i s assumed
to occupy r ^ s i t e s (where r ^ can be f r a c t i o n a l ) , and t h e l a t t i c e h a s
empty s i t e s c a l l e d h o l e s . There a r e N Q h o l e s and m o l e c u l e s . To
a c c o u n t f o r the c o n n e c t i v i t y o f the segments o f a m o l e c u l e , an e f f e c t i v e
chain length i s defined as,
zqi = z r i - 2 r ^ + 2 1)
w h e r e i n i t has been assumed t h a t c h a i n s a r e n o t c y c l i c , z q ^ now

r e p r e s e n t s the e f f e c t i v e number o f e x t e r n a l c o n t a c t s p e r m o l e c u l e . The
i n t e r a c t i o n energy between segments o f m o l e c u l e s i s d e n o t e d by
w h i l e t h e i n t e r a c t i o n energy o f any s p e c i e s w i t h a h o l e i s
zero. Only n e a r e s t neighbour i n t e r a c t i o n s a r e c o n s i d e r e d , and
p a i r w i s e a d d i t i v i t y i s assumed. The c a n o n i c a l p a r t i t i o n f u n c t i o n
f o r t h i s ensemble c a n
Ω = I exp(-0E { n ) ) 2)
all
s t a t e s {n}
w h e r e /3=l/kT. On t h e assumption o f random m i x i n g o f h o l e s and

m o l e c u l e s , and f o l l o w i n g t h e approach o f P a n a y i o t o u and V e r a ( 1 6 ) ,
we o b t a i n an e x p r e s s i o n f o r Ω which i s v a l i d o u t s i d e t h e c r i t i c a l
r e g i o n o f t h e pure component, i . e . ,
_ f j J N
l (Nn + r ^ ) ! f (N + N n i q i )! 1 z / 2
(β _N l 3 j 1
U J N 0 ! N ! L [ (N + 0 Ν 1 Γ 1 ) ! J e X p
[2 z N q
l l £
" - NQ + N I Q I J i }
where S i s t h e number o f i n t e r n a l arrangements o f a m o l e c u l e and σ

a symmetry f a c t o r . U s i n g t h e f o l l o w i n g r e d u c i n g p a r a m e t e r s
(z/2)e n = P*v H = RT* 4)
and d e f i n i n g V, t h e t o t a l volume o f t h e system,
V = v (N +
H 0 r i N ) x 5)
an EOS t h a t d e f i n e s t h e pure component i s o b t a i n e d , i . e . ,

2
?_ IN
l
_Y_ +
J
? in v + (
q/ r )
- 1
-
J
6)
Τ v - l 2 ^ ν Τ
Here ϋ i s t h e e f f e c t i v e s u r f a c e f r a c t i o n o f m o l e c u l e s and t h e t i l d e
(~) denotes r e d u c e d v a r i a b l e s . A l l q u a n t i t i e s , e x c e p t ν i n t h e EOS,
are r e d u c e d b y t h e parameters i n E q u a t i o n 4. The s p e c i f i c volume v ,
i s r e d u c e d by v * , t h e m o l e c u l a r h a r d - c o r e volume,

v β N r v
* i i H 7)
E x p r e s s i o n s f o r t h e c h e m i c a l p o t e n t i a l o f a p u r e component c a n a l s o
be d e r i v e d from E q u a t i o n 3 and s t a n d a r d thermodynamics ( 1 7 ) .
D e t e r m i n a t i o n o f p u r e component p a r a m e t e r s . I n order t o use the

EOS t o model r e a l s u b s t a n c e s one needs t o o b t a i n € and v * . F o r aX 1
p u r e component below i t s c r i t i c a l p o i n t , a t e c h n i q u e s u g g e s t e d b y
J o f f e e t a l . (18) was u s e d . T h i s i n v o l v e s t h e m a t c h i n g o f c h e m i c a l
p o t e n t i a l s o f e a c h component i n t h e l i q u i d and t h e v a p o u r p h a s e s a t
the v a p o u r p r e s s u r e o f t h e s u b s t a n c e . A l s o , t h e a c t u a l and p r e d i c t e d
s a t u r a t e d l i q u i d d e n s i t i e s were matched. The s e t o f e q u a t i o n s so
o b t a i n e d was s o l v e d by t h e u s e o f a s t a n d a r d Newton's method t o
y i e l d t h e p u r e component p a r a m e t e r s . V a l u e s o f c and v* f o r i x
e t h a n o l and water a t s e v e r a l temperatures a r e shown i n T a b l e 1. I n

this calculation v an H
r e s p e c t i v e l y ( 1 6 ) . Th
component VLE was f o u n quit ζ
7 3 χ 5 3 1
(6<z<26) and v ( l . O x 10' m m o l e " < ν < 1 . 5 x 10" m m o l e " ) .
H Η
F o r a s u p e r c r i t i c a l f l u i d (SCF) component, t h e p u r e component

p a r a m e t e r s were o b t a i n e d by f i t t i n g P-v d a t a on i s o t h e r m s (300-
380K). P r e l i m i n a r y d a t a f o r t h e s e s u b s t a n c e s s u g g e s t t h a t a l t h o u g h
t h e computed v* i s a weak f u n c t i o n o f t e m p e r a t u r e , c i s a constant x l
within regression error.
T a b l e 1: Pure Component p a r a m e t e r s f o r e t h a n o l and water

6 3 1
a t s e v e r a l t e m p e r a t u r e s ( z-10, v - 9 . 7 5 χ 1 0 ' m m o l e " )
H
Ethanol Water
Τ (Κ) e 1]L (N-m/mole) v* ( c m g ' )

3 1
€ (N-m/mole)
11 v* ( c m g ' )
3 1
283 1357, .59 1.2018 3596..56 0.9602

293 1355, .47 1.2016 3516. .20 0.9685
303 1314, .34 1.2193 3438..16 0.9767
313 1294, .18 1.2276 3362..54 0.9588
323 1274, .90 1.2358 3289..36 0.9943
333 1256. .49 1.2437 3218. .53 1.0030
343 1238, .87 1.2515 3150. .14 1.0123
353 1222. .04 1.2589 3083..99 1.0216
363 1205. .89 1.2661 3020.,02 1.0310
373 1190. .43 1.2731 2958.,16 1.0406
393 1161. .42 1.2864 2840.,43 1.0602
413 1134. 68 1.2989 2730.,13 1.0804
433 1109. .83 1.3109 2626. 57 1.1011
Discussion. In order to understand q u a l i t a t i v e l y the behaviour o f

t h e l a t t i c e EOS, i t was examined i n t h e l i m i t o f s m a l l m o l e c u l e s
(q»r • ! ) . I n t h i s c a s e E q u a t i o n 6 s i m p l i f i e s t o t h e form,

8)
The f i r s t term c a n be i d e n t i f i e d w i t h a " h a r d - s p h e r e " r e p u l s i o n

term, w h i l e the second a c c o u n t s f o r a t t r a c t i v e f o r c e s . The s e c o n d
term c a n be r e w r i t t e n as,
2
P v
a ( P*v* ) a
z
RT v ν
Thus, t h e a t t r a c t i v e term r e p r e s e n t e d i n E q u a t i o n 9 has t h e same form

as t h e a t t r a c t i v e term i n the v a n d e r Waals EOS (19) . On e x a m i n i n g
the d a t a i n T a b l e 1 and
was f o u n d t h a t f o r a temperatur
v a l u e o f t h i s parameter was always l e s s t h a n 3%, although the
computed v a l u e s o f v * and ey^ t h e m s e l v e s showed a 7% v a r i a t i o n . I n
the l i m i t o f s m a l l m o l e c u l e s , t h e r e f o r e , the l a t t i c e EOS has a term
t h a t a p p r o x i m a t e s the v a n d e r Waals t y p e a t t r a c t i v e term c l o s e l y .
The b e h a v i o u r o f the r e p u l s i v e term o f the l a t t i c e EOS i s more

c o m p l i c a t e d and w i l l n o t be d i s c u s s e d i n d e t a i l . A t liquid-like
d e n s i t i e s t h i s r e p u l s i o n term i s a b e t t e r a p p r o x i m a t i o n t o the h a r d
s p h e r e s r e p u l s i o n t h a n t h e v a n d e r Waals r e p u l s i o n term. At g a s - l i k e
d e n s i t i e s , the r e p u l s i o n term o f the l a t t i c e model and the v a n d e r
Waals EOS have the same f u n c t i o n a l form.
Binary Mixtures
Theory. C o n s i d e r a m i x t u r e o f NQ h o l e s , molecules of species 1

and N 2 m o l e c u l e s o f s p e c i e s 2. F o l l o w i n g P a n a y i o t o u and V e r a (16)
the f o l l o w i n g m i x i n g r u l e s a r e assumed f o r the m i x t u r e p a r a m e t e r s
r , qM and v * .
M M
r M - Σ Xi r i 10)
e u
qM Σ * i qi >
v * " Σ * i
M v*i 12)
L a t t i c e c o o r d i n a t i o n numbers ( z ) and the c e l l volumes (vjj) f o r b o t h

the p u r e components and m i x t u r e l a t t i c e s a r e assumed t o have the
same v a l u e . The p a r t i t i o n f u n c t i o n f o r t h i s ensemble c a n be f o r m u l a t e d
f o l l o w i n g E q u a t i o n 2. I t i s assumed now t h a t the p a r t i t i o n f u n c t i o n ,
f a r f r o m t h e b i n a r y c r i t i c a l p o i n t c a n be a p p r o x i m a t e d by i t s
l a r g e s t t e r m . S i n c e m o l e c u l e segments and h o l e s c a n d i s t r i b u t e
t h e m s e l v e s non-randomly, the p a r t i t i o n f u n c t i o n must i n c o r p o r a t e
terms t o a c c o u n t f o r t h i s e f f e c t . The nonrandomness c o r r e c t i o n r ^ j

a l l o w s f o r d i s t r i b u t i o n o f t h e segments o f s p e c i e s i about t h e segments

o f s p e c i e s j o v e r t h e random v a l u e s o f such c o n t a c t s . I t i s d e f i n e d
through the e q u a t i o n
Ν.. - N9. Γ.. 13)
where N^j i s t h e a c t u a l number o f i - j c o n t a c t s and N§j i s t h e

number o r i - j c o n t a c t s i n t h e c o m p l e t e l y random c a s e . E x p r e s s i o n s
f o r t h e non-randomness c o r r e c t i o n must be o b t a i n e d t h r o u g h t h e
s o l u t i o n o f t h e " q u a s i c h e m i c a l " e q u a t i o n s ( 2 0 ) . These e q u a t i o n s c a n
be s o l v e d i n a c l o s e d a n a l y t i c form o n l y i n t h e c a s e o f a two-
component system ( i n c l u d i n g h o l e s ) . I n o r d e r t o e n s u r e t h e mathematical
t r a c t a b i l i t y o f t h e b i n a r y r e s u l t s , i t i s t h e r e f o r e assumed t h a t
h o l e s d i s t r i b u t e randomly w h i l e m o l e c u l e s do n o t .
The s o l u t i o n f o r t h e q u a s i c h e m i c a l expressions f o r t h e pseudo

two-component system y i e l d
c o r r e c t i o n T j j , which ca
Γ j ^ - (1-j) 14)
J L / j L
1 + [1 - 4<5. β (1 - ê )]
where,
g - exp (flAe/kT), 15)
€
Ae = + t^l " ^ 12 ^)
# i i s t h e s u r f a c e f r a c t i o n o f i m o l e c u l e segments on a h o l e - f r e e
b a s i s and ϋ i s t h e t o t a l s u r f a c e a r e a f r a c t i o n o f m o l e c u l e seg
ments. E q u a t i o n 16 i m m e d i a t e l y s u g g e s t s a c o m b i n i n g r u l e f o r ey^ as
a measure o f t h e d e p a r t u r e o f the m i x t u r e from randomness, i . e . ,
:
Hi • i - j 17)
1j
0.5 ( € 1 1 + € j j ) (1 - k y ) , i-j
The m i x i n g r u l e f o r c a r i s e s n a t u r a l l y t h r o u g h t h e f o r m u l a t i o n o f t h e
canonical p a r t i t i o n function, i . e . ,
e = I l ϋ. ϋ. Γ.. c..
M £ J ι j ij ij
18)
An EOS f o r t h e m i x t u r e and c h e m i c a l p o t e n t i a l s f o r component i in

the m i x t u r e c a n now be d e r i v e d u s i n g s t a n d a r d thermodynamics.

? _ i n f _ J L _ ] + ? i n Γ ν + ( g / r ) -1 Ί . _*! +
J
T 1
ν - 1 J
2 ^ ν t
( 1 / J
kT e [ 1 - 4 ^ 2 ( l - g ) J ^ I r j 2
" i V +(c r) 1
« λ(Τ) + i n q. - intf.tf + r (0.5z -1) i n [ ^ " j
1 1 L v
kT
+
~T ~r~^ ( 2
V i i
Τ Τ
Γ
1 f i i f
,
Γ
11 22Γ
1 ν
Γ
¥2 12<»1
" V22 2ί
i J +
ΙΤ^Γ J ( l - 4 ^ 1 -g)) ( 1 / 2 )
[β (β - ê ^ d -g) - é ^ g - g - « ( i . «)] - in r 1 2 - o.szîèî-r^
Γ è Γ Ô è T
*1 11
x
- 2 22 ί Δ
l l ll
in + ϋ (1- Γ ) in ] + 0.5zq. [ i n — - Γ in ]
1 Γ 1
V l 2 *1 12 *2 V l 2
d Γ
«2 2 22 -
\ <2i u - * j ) + 0.5zq [ i n — 1 - r i n -^-^ ] β
2 2 2 (2« - « )2i 2 20)
Γ
*1 *1 12
where r e p r e s e n t s the c h e m i c a l p o t e n t i a l o f component i i n a b i n a r y

m i x t u r e , j = 3 - i and λ(Τ) i s some u n i v e r s a l t e m p e r a t u r e f u n c t i o n .
i s t h e K r o n e c k e r - d e l t a f u n c t i o n . Parameters u s e d f o r o b t a i n i n g t h e s e
e q u a t i o n s i n a d i m e n s i o n l e s s form a r e d e f i n e d i n manner a n a l o g o u s
to E q u a t i o n 4.
The m i x t u r e EOS [ E q u a t i o n 19] has the t h r e e terms t h a t a r e p r e s e n t

i n the p u r e component EOS. A l s o , i t has an a d d i t i o n a l term w h i c h
a c c o u n t s f o r the non-randomness c o r r e c t i o n s t h a t have b e e n i n c o r p o r a t e d
i n t o the p a r t i t i o n f u n c t i o n e x p r e s s i o n . T h i s l a s t term, f o r a l l
c a s e s t e s t e d , i s always a t l e a s t 4 o r d e r s o f magnitude s m a l l e r t h a n
the o t h e r t h r e e terms and can e f f e c t i v e l y be n e g l e c t e d . However, i t
i s r e t a i n e d f o r the sake o f m a t h e m a t i c a l c o n s i s t e n c y .

The e x p r e s s i o n s d e r i v e d f o r t h e EOS and the c h e m i c a l p o t e n t i a l o f

component i i n a b i n a r y m i x t u r e were u s e d t o model t h e phase e q u i l i b r i a
o f b i n a r y m i x t u r e s . A s e t o f n o n - l i n e a r e q u a t i o n s was o b t a i n e d and
s o l v e d by the use o f a Newton's method.
M i x t u r e s o f s m a l l m o l e c u l e s (acetone-benzene, ethanol-water)
were c o n s i d e r e d f i r s t . I n F i g u r e s 1 and 2, a c o m p a r i s o n i s made between
t h e p r e d i c t e d and e x p e r i m e n t a l l o w - p r e s s u r e VLE d a t a (21,22) f o r t h e s e
systems. An e x c e l l e n t f i t t o the d a t a i s o b t a i n e d i n b o t h c a s e s , w i t h
t h e use o f one a p p a r e n t l y temperature independent parameter ( k j j ) p e r
binary.
The i n t e r e s t i n g a s p e c t o f t h i s m o d e l l i n g i s t h e temperature
independence o f \ h ^ A . I t was shown e a r l i e r t h a t , i f the p u r e components
were s m a l l m o l e c u l e s , the l a t t i c e EOS has an a t t r a c t i v e term w i t h an
e s s e n t i a l l y temperatur
m i x t u r e s r e s u l t s i n th
of k j j f o r b i n a r y mixtures of small molecules.
I n e x a m i n i n g the s e n s i t i v i t y o f the model t o t h e assumed v a l u e

o f z, i t was f o u n d f o r the e t h a n o l - w a t e r system t h a t the goodness
o f f i t o f the model was i n s e n s i t i v e t o t h e ζ v a l u e i n the v i c i n i t y
o f z-10. F o r l a r g e v a l u e s o f ζ (z>15) , however, i t was f o u n d t h a t the
model was i n c a p a b l e o f even q u a l i t a t i v e l y p r e d i c i t i n g m i x t u r e VLE
behaviour.
The a p p l i c a b i l i t y o f the l a t t i c e EOS i n the m o d e l l i n g o f the

VLE o f m i x t u r e s o f m o l e c u l e s o f d i f f e r e n t s i z e s was examined n e x t . The
r e s u l t s f o r the l ^ S - n - h e p t a n e system a t 310K and 352K a r e shown i n
F i g u r e 3 (23.) . F o r the t e m p e r a t u r e s m o d e l l e d , i t i s s e e n t h a t t h e r e
i s a good agreement between the f i t t e d and the e x p e r i m e n t a l d a t a ,
a g a i n w i t h the use o f one temperature independent b i n a r y i n t e r a c t i o n
parameter.
The l a t t i c e model thus p r o v i d e s the c a p a b i l i t y t o o b t a i n good,

q u a n t i t a t i v e f i t s t o e x p e r i m e n t a l VLE d a t a f o r b i n a r y m i x t u r e s o f
m o l e c u l e s below t h e i r c r i t i c a l p o i n t . I t s v a l u e l i e s i n the f a c t t h a t
i t p e r f o r m s e q u a l l y w e l l r e g a r d l e s s o f the s i z e d i f f e r e n c e between
t h e component m o l e c u l e s .
The model was t h e n e x t e n d e d t o the phase e q u i l i b r i u m m o d e l l i n g

o f s o l i d - s u p e r c r i t i c a l f l u i d (SCF) b i n a r i e s . These m i x t u r e s a r e
c o m p o s i t i o n a l l y h i g h l y assymmetric, s i n c e the s o l i d i s c r y s t a l l i n e
and e s s e n t i a l l y p u r e . The phases i n e q u i l i b r i u m a r e t h u s v e r y d i f f e r e n t
i n c o m p o s i t i o n . I n F i g u r e 4, the model b e h a v i o u r i s compared t o
e x p e r i m e n t a l d a t a f o r the n a p h t h a l e n e - c a r b o n d i o x i d e b i n a r y a t 308
and 318K. O u t s i d e the c r i t i c a l r e g i o n , the l a t t i c e EOS p r o v i d e s a
good f i t t o t h e measured d a t a ( 2 4 ) . I n the c r i t i c a l r e g i o n , however,
a t one p r e s s u r e , the e q u a t i o n o f s t a t e p r e d i c t s the p r e s e n c e o f a
t h r e e phase r e g i o n . T h i s i s the cause f o r the d i s c o n t i n u i t y o f the
c u r v e s i n the r e g i o n o f the sharp r i s e i n s o l u b i l i t y . O u t s i d e o f
the c r i t i c a l r e g i o n ( a p p r o x i m a t e l y 7% away from T c o r P ) the model
c

OJ -j I I I ι I I J I
Ο 0.2 0.4 0.6 0.8
Mole Fraction Acetone

F i g u r e 1. Comparison o f l a t t i c e model p r e d i c t i o n and e x p e r i m e n t a l
d a t a o f W e i s p h a r t (21) f o r t h e acetone-benzene b i n a r y a t 303, 313
6 1
and 323 Κ (z=10, ν « 9 . 7 5 χ 1 0 " n A n o l e " , k j j =0.022).
Η
0 0.2 0.4 0.6 0.8 1
Mole Fraction Ethanol
F i g u r e 2. Comparison o f the e x p e r i m e n t a l d a t a o f Pemberton and Mash

(22) f o r t h e e t h a n o l - w a t e r b i n a r y a t 323, 343, and 363 Κ w i t h t h e
l a t t i c e model p r e d i c t i o n s w i t h ζ = 10, v = 9.75 χ 10" m mole"
f l
and k.. = 0.085.
60
Mole Fraction H2S
F i g u r e 3. Comparison o f t h e l a t t i c e model p r e d i c t i o n s and e x p e r i m e n t a l

d a t a o f Ng e t a l . 023) f o r the I^S-n-heptane system a t 310 and 352 Κ
6 1
(ζ = 10, v = 9.75 χ 1 0 " n A n o l e " and k j j = 0.09).
H

-1.4 -
-1.6 -
-1.8 -
-2 -
-2.2 -
-2.4 -
-2.6 -
ι— -2.8 - System: Napthalene(1 ) - C 0 2 ( 2 )
σι Data of Tsekhanskaya et al.,(1964)

-3 -
0
-3.2 - k12(308)«0.14
-3.4 - k12(318)-0.13
-3.6 - Ο 318 Κ
-3.8 - + 308 Κ
-4 -

-4.2 -
-4.4 — ι — — ι —
100 200 300 400
Pressure (bar)

F i g u r e 4. Comparison o f the model p r e d i c t i o n s f o r t h e C02-naphthalene
b i n a r y a t 308 and 318 Κ w i t h the e x p e r i m e n t a l d a t a o f Tsekhanskaya e t
6 1
a l . (24) (ζ = 10, v = 9.75 χ 1 0 " n A i o l e " , k j (308 Κ) = 0.14, and
H ±
k± j (318 Κ) = 0.135).
-1
-10 H 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Γ
20 60 100 140 180 220 260 300 340
Pressure (bar)
F i g u r e 5. L a t t i c e model p r e d i c t i o n s f o r the e q u i l i b r i u m f l u i d phase

c o m p o s i t i o n f o r a C02~polymer system a t 328 K. M o l e c u l a r weight o f
a monomeric u n i t i s 100, w h i l e the degree o f p o l y m e r i z a t i o n , ξ ,
6 1
v a r i e s between 1 and 7 (z = 10, v H= 9.75 χ 1 0 ~ m^mole" ,
k± 1 = 0.10).
predicts results within the a c c u r a c y o f the e x p e r i m e n t a l measure

ments .
The model b e h a v i o u r i n the c r i t i c a l r e g i o n i s n o t s a t i s f a c t o r y . The

main r e a s o n f o r t h i s l i e s i n one o f the f u n d a m e n t a l assumptions
made i n d e r i v i n g t h e model; t h e one where the c a n o n i c a l p a r t i t i o n
f u n c t i o n ( E q u a t i o n 2) i s a p p r o x i m a t e d by t h e l a r g e s t term i n t h e
summation. C l e a r l y , i n t h e c r i t i c a l r e g i o n t h i s assumption i s
i n v a l i d , s i n c e t h e r e i s no one d o m i n a t i n g term i n t h e summation f o r
the p a r t i t i o n f u n c t i o n . The model must, t h e r e f o r e , be u s e d w i t h t h e
f u l l u n d e r s t a n d i n g o f i t s s h o r t c o m i n g s i n the c r i t i c a l r e g i o n .
I n o r d e r t o t e s t the a p p l i c a b i l i t y o f the model t o polymer-SCF

systems, a h y p o t h e t i c a l system o f CO2 and a m o n o d i s p e r s e Ç-mer w i t h
a monomeric u n i t m o l e c u l a r w e i g h t o f 100 was s i m u l a t e d . Pure component
p a r a m e t e r s f o r t h e polymer, p o l y s t y r e n e , were o b t a i n e d from P a n a y i o t o u
and V e r a ( 1 6 ) . C o n s t a n t v a l u e s o f k j * were u s e d f o r t h e polymer
system, where t h e degree o f p o l y m e r i z a t i o n , f , v a r i e d between 1 and
7. I t was assumed t h a t a l l c h a i n s had the same β, and ν s c a l e d as
the m o l e c u l a r w e i g h t o f the c h a i n . F i g u r e 5 shows t h e r e s u l t s o f
the p r e d i c t e d mole f r a c t i o n o f the ξ-mer i n the SCF phase.

8. KUMAR ET AL. Mechanics-Based Lattice Model Equation of State 99
The model s i m u l a t e s a n e x p e r i m e n t a l l y o b s e r v e d t r e n d (2!5) t h a t

the s o l u b i l i t y o f c h a i n s i n a SCF shows a s t r o n g i n v e r s e dependence
on t h e m o l e c u l a r mass o f t h e polymer. F i g u r e 5 shows t h a t c h a n g i n g
the m o l e c u l a r weight o f t h e c h a i n m o l e c u l e from 100 t o 700 causes a
r e d u c t i o n i n s o l u b i l i t y o f n e a r l y 6 o r d e r s o f magnitude. The model
a l s o shows t h a t a l l t h e s o l u b i l i t y p l o t s t e n d t o f l a t t e n o u t a r o u n d
300 b a r , as o b s e r v e d i n e x p e r i m e n t s (25)- C l a s s i c a l EOS l i k e a
m o d i f i e d c u b i c EOS ( 2 6 ) , when a p p l i e d t o such systems, p r o d u c e
s o l u b i l i t y c u r v e s w h i c h t e n d t o show a sharp maximum a r o u n d 200
b a r . F o r polymer-SCF systems, t h e r e f o r e , t h e l a t t i c e EOS i s b e l i e v e d
t o b e s u p e r i o r t o m o d i f i e d c u b i c EOS.
Conclusions
A s t a t i s t i c a l - m e c h a n i c s b a s e d model f o r m i x t u r e s o f m o l e c u l e s o f
d i s p a r a t e s i z e s h a s been p r e s e n t e d i n t h i s p a p e r . R e s u l t s o b t a i n e d
to date demonstrate t h a
f o r m o d e l l i n g polymer-SC
w h i l e f o r t h e o t h e r systems, o u t s i d e t h e c r i t i c a l r e g i o n , i t p e r f o r m s
as w e l l as c l a s s i c a l l y employed t e c h n i q u e s .
The t e m p e r a t u r e independence o f t h e a p a r a m e t e r [ E q u a t i o n 9]
and t h e b i n a r y i n t e r a c t i o n p a r a m e t e r (kj_j) f o r systems o f s m a l l
m o l e c u l e s c o u l d l e a d t o p r e d i c t i v e models t h a t m e r i t c l o s e r examination.
Acknowledgement
The a u t h o r s g r a t e f u l l y acknowledge s u p p o r t from t h e N a t i o n a l S c i e n c e

F o u n d a t i o n , D i v i s i o n o f C h e m i c a l , B i o c h e m i c a l and T h e r m a l E n g i n e e r i n g
under G r a n t No. CBT 85-09945.
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energies for water + ethanol at 303.15 Κ to 363.15 Κ determined
by an accurate static method"., J. Chem. Therm., 1978, 10, 867-88.
23. Ng H-J., Kalra Η., Robinson D.B., Kubota Η., "Equilibrium phase
properties of the toluene-hydrogen sulfide and n-heptane-hydrogen
sulfide binary systems", J. Chem. Eng. Data., 1980, 25, 51-55.
24. Tsekhanskaya Yu. V., Iomtev M.B., Muskina E.V., "Solubility of
naphthalene in ethylene and carbon dioxide under pressure", Russ.
J. Phy. Chem., 1964, 38(9), 1173.
25. Schroeder Ε., Arndt Κ-F., "Loeslichkeitverhalten von Makromolekuelen
in komprimierten Gasen", Faserforschung und Textiltechnik,
1976, 247(3), 135.
26. Panagiotopoulos A.Z., Reid R.C., "A new mixing rule for cubic
equations of state for highly polar, asymmetric systems", in
K.C.Chao and R.L.Robinson (Ed.), "Equations of State- Theories
and Applications", ACS Symposium Series, 300,571-582(1986)

Chapter 9
Van der Waals Mixing Rules

for Cubic Equations of State
Ε. H. Benmekki, T. Y. Kwak, and G. A. Mansoori
Department of Chemical Engineering, University of Illinois, Box 4348,

Chicago, IL 60680
A new concept for the development of mixing rules for

cubic equations of state consistent with statistical
mechanical theory of the van der Waals mixing rules is
introduced. Utilit
its application
Peng-Robinson (PR) equations of state. The resulting
mixing rules for the Red1ich-Kwong and the Peng-
Robinson equations of state are tested through
prediction of solubility of heavy solids in
supercritical fluids and prediction of phase behavior
of binary mixtures of hydrocarbons and
nonhydrocarbons.
There has been extensive progress made in recent years in research

towards the development of analytic statistical mechanical equations
of state applicable for process design calculations 0,2). However,
cubic equations of state are still widely used in chemical
engineering practice for calculation and prediction of properties of
fluids and fluid mixtures Q). These equations of state are
generally modifications of the van der Waals equation of state
(4.5).
RT
(1)
ν-b v2
which was proposed by van der Waals (k) in 1873· According to van
der Waals, for the extension of this equation to mixtures, it is
necessary to replace a and b with the following composition-
dependent expressions:
η η
a = Σ Σ xj Xj . ajj (2)
' J
0097-6156/87/0329-0101 $06.00/0

η η
b = Σ Σ xj X j bjj (3)
' J
E q u a t i o n s 2 and 3 a r e c a l l e d t h e v a n d e r Waals m i x i n g rules. In

these e q u a t i o n s , a;: and b j : (i=j) a r e parameters corresponding
t o pure component \\) w h i l e a | : a n d b j : ( i * j ) arecalled the
u n i i k e - i n t e r a c t i o n parameters. I t i s customary t o r e l a t e t h e uni i k e -
interaction parameters t o t h e pure-component parameters by t h e
following expressions:
ajj = (1 - k , j ) (·,, a j j ) 1 / 2 <l»)
bij = (b M + bjj)/2 (5)
In E q u a t i o n k, k j j i s a f i t t i n g p a r a m e t e r w h i c h i s known a s t h e
coupling parameter. With E q u a t i o n 5 p l a c e d i n E q u a t i o n 3, the
e x p r e s s i o n f o r b wi11 r e d u c
η
b - Σ XJ b M (3.1)
The Redlich-Kwong equation of state (6),
RT a
(6)
ν - b Τ** v ( v - b )
and t h e Peng-Robinson equation of s t a t e (2)t
RT a (T)
(7)
v-b v(v+b)+b(v-b)
a(T) = a(T ) c {1 + *(1 - T^ ) } 2

(8)
a(T ) c = ΟΛ5724 R 2
T 2
/ P c (8.1)
κ = 0.37^64 + 1.5*»226ω - 0 . 2 6 9 9 2 ω 2
(9)
b = 0.0778 R T / P C C (10)
are w i d e l y used f o r thermodynamic p r o p e r t y calculations.
The T h e o r y o f t h e Van Der Waals M i x i n g Rules
L e i and a n d C o - w o r k e r s (8-10) h a v e b e e n a b l e t o r e - d e r i v e t h e v a n d e r
Waals m i x i n g r u l e s w i t h t h e use o f s t a t i s t i c a l mechanical theory o f
radial distribution functions. According t o these investigators,
for a fluid mixture with a pair intermolecular potential energy
function,
Uij(r) = ejjf (r/ajj) (11)

9. BENMEKKI ET AL. Mixing Rules for Cubic Equations of State 103
the f o l l o w i n g mixing rules will be d e r i v e d :
η η
σ3 = Σ Σ χ; X j σ^3 (12)
• J
η η
€cr3 = Σ Σ χ; XJ 6^.σ^.3 (13)
In these equations, € j j i s the interaction energy parameter

between molecule i and j while a j j i s t h e i n t e r m o l e c u 1ar
interaction d i s t a n c e between t h e two m o l e c u l e s . Knowing that
c o e f f i c i e n t s a and b o f t h e v a n d e r Waals equation of state are
p r o p o r t i o n a l t o e and σ a c c o r d i n g t o t h e f o l l o w i n g e x p r e s s i o n s :
a = 1 .1250 R T v c c « N Q ea3 (lit)
b = 0.3333 v c « N
We can see that E q u a t i o n s 12 a n d 13 a r e i d e n t i c a l with

E q u a t i o n s 3 a n d 2, respectively. S t a t i s t i c a l mechanical arguments
w h i c h a r e u s e d i n d e r i v i n g E q u a t i o n s 12 a n d 13 d i c t a t e t h e f o l l o w i n g
g u i d e l i n e s i n u s i n g t h e van d e r Waals m i x i n g r u l e s :
(1) The v a n d e r Waals mixing rules are f o r constants o f an

equation of state.
(2) E q u a t i o n 12 i s a m i x i n g r u l e f o r ( m o l e c u l a r l e n g t h ) 3 , a n d
E q u a t i o n 13 i s a m i x i n g r u l e f o r ( m o l e c u l a r 1 e n g t h ) 3 . ( m o l e c u -
lar energy). I t happens t h a t b and a o f t h e v a n d e r Waals
e q u a t i o n o f s t a t e a r e p r o p o r t i o n a l t o (molecular l e n g t h ) 3 and
(molecular 1ength)3. (molecular e n e r g y ) , r e s p e c t i v e l y , and as
a result, these m i x i n g r u l e s a r e used i n t h e form w h i c h was
p r o p o s e d by v a n d e r W a a l s .
(3) Knowing that a j j (for i Φ j ) , the uni i k e - i n t e r a c t i o n

diameters, f o rs p h e r i c a l molecules i s equal t o
σ = σ +
υ (ϋ σ
η ) η ( l 6 )
This w i l l make t h e e x p r e s s i o n f o r b j j f o r s p h e r i c a l molecules

t o be
bjj = [ ( j .1/3+
b b j j 1/3)/2 ]3 (17)
Then f o r n o n - s p h e r i c a l m o l e c u l e s expression for b j j w i l l be
bjj = (bj ; 1/3+ b j j l / 3 ) ] 3 (18)
With t h e use o f these g u i d e l i n e s , we now d e r i v e t h e v a n d e r

Waals mixing rules f o r t h e Redlich-Kwong and t h e Peng-Robinson
equations of state. S i m i l a r p r o c e d u r e c a n be used f o r d e r i v i n g t h e
van d e r Waals m i x i n g r u l e s f o r o t h e r e q u a t i o n s o f s t a t e .

M i x i n g Rules f o r t h e Redlich-Kwong E q u a t i o n o f S t a t e . The R e d l i c h -

Kwong e q u a t i o n o f s t a t e , E q u a t i o n 6, c a n b e w r i t t e n i n t h e f o l l o w i n g
form:
PV ν a
Ζ - (19)
1
RT v-b R T - ^ (v+b)
In this equation of state, b has the dimension of (molecular

l e n g t h ) 3,
b = 0.26v c « Ν σ3 0
T h e n t h e m i x i n g r u l e f o r b w i l l b e t h e same a s t h e o n e f o r t h e f i r s t
van d e r Waals m i x i n g r u l e s , E q u a t i o n 3· However, mixing rule f o ra
will be d i f f e r e n t from t h e second v a n d e r Waals mixing rule,
E q u a t i o n 2. P a r a m e t e r a a p p e a r i n g i n t h e Red 1ich-Kwong e q u a t i o n o f
s t a t e h a s d i m e n s i o n o f R"
length)3, that i s
( a = 1.2828RT C
]
-5 V c « N Q (e/k) ·5 3)
1
σ
As a r e s u l t t h e s e c o n d v a n d e r Waals m i x i n g r u l e s , E q u a t i o n 13»
cannot be used directly f o r parameter a o f t h e Redi1ch-Kwong
equation of state. However, since [ (Râb^) ] ^ 3 ^ ^ 2
a s t e
dimension o f (molecular energy). (molecular length)3, t h e second

van d e r Waals mixing rules, E q u a t i o n 13» c a n b e w r i t t e n f o r t h i s
term. F i n a l l y t h e v a n d e r W a a l s m i x i n g r u l e s f o r t h e Red 1ich-Kwong
e q u a t i o n o f s t a t e w i l l be i n t h e f o l l o w i n g f o r m :
3 = { Σ Σ Χ ΐ X j a î j 2 /
3b i j
1
/ 3 } 1.5/(Σ Σ χ. X j bjj)I / 2
(20)
« j i j
η η
b - Σ Σ xj X
J b
i j
(3)
• j
These mixing rules, when j o i n e d with t h e Redlich-Kwong

equation of state, will constitute t h e Redlich-Kwong equation of
state f o r mixtures that i s consistent with the statistical
mechanical b a s i s o f t h e van d e r Waals m i x i n g r u l e s .
Mixing Rules f o r t h e Peng-Robinson Equation of S t a t e . In order t o

s e p a r a t e thermodynamic v a r i a b l e s from c o n s t a n t s o f t h e Peng-Robinson
e q u a t i o n o f s t a t e , we w i l l i n s e r t E q u a t i o n s 8 a n d 9 i n E q u a t i o n 7
and we w i l l w r i t e i t i n t h e f o l l o w i n g f o r m :
ν c/RT + d - 2 y/ (cd/RT)
Ζ (21)
v-b (v+b) + (b/v) (v-b)
w h e r e c = a ( T ) (1 + κ)
c
2
and d = a (T ) * / R T c
2
c
This form of t h e Peng-Robinson equation of state suggests that

t h e r e e x i s t t h r e e i n d e p e n d e n t c o n s t a n t s w h i c h a r e b , c , a n d d . Now,
f o l l o w i n g t h e p r e s c r i b e d g u i d e l i n e s f o r t h e v a n d e r Waals m i x i n g
r u l e s , m i x i n g r u l e s f o r b, c , and d o f t h e Peng-Robinson e q u a t i o n o f
s t a t e w i l l be
η η
c = Σ Σ xj Xj c ι j (22)
î J
η η
b = Σ Σ Xj XJ bjj (23)
î J
η η
d = Σ Σ Xj XJ djj (2k)
' j
with thefollowing combining rules:
Cjj = (1-kjj) (CJ
bjj = (1-ljj) { ( b | j 1/3+ b j j l / 3 ) / 2 }3 (26)
d j j = (1-mjj) { ( d j j l / 3 + d j j l / 3 ) / 2 }3 (27)
Applications for Supercritical Fluid Extraction Modeling
A serious test o f m i x t u r e e q u a t i o n s o f s t a t e i s shown t o b e t h e i r

application for prediction of solubility of solutes i n supercritical
f l u i d s (JN ). I n t h e p r e s e n t r e p o r t , we a p p l y t h e R e d l i c h - K w o n g a n d
the Peng-Robinson equations of state for supercritical fluid
extraction of solids and study thee f f e c t of choosing different
m i x i n g r u l e s on p r e d i c t i o n o f s o l u b i l i t y o f s o l i d s i n s u p e r c r i t i c a l
f l u i d s - F i g u r e s 1-5·
Thermodynamic Model. S o l u b i l i t y o f a condensed phase, y , i n a 2
v a p o r p h a s e a t s u p e r c r i t i c a l c o n d i t i o n s (12) c a n b e d e f i n e d a s :
Ρ
a t at n d
y 2 = (P! /P) (1/Φ ) <*>i E x p { /
2 (v|° /RT)dP} (28)
P5- a t
S a t
where < Ê 2 i s t h e f u g a c i t y c o e f f i c i e n t a t p r e s s u r e P. P r o v i d e d we
S 0 , d
assume 2 l
V i s independent o f p r e s s u r e and f o r s m a l l v a l u e s o f
s a t
P2 t h e above expression w i l l be c o n v e r t e d to the following
form:
S a t s o l i d s a t
y = 2 (P 2 / P ) (1/Φ ) E x p { v
2 2 (P-P 2 )/RT} (29)
In o r d e r t o c a l c u l a t e s o l u b i l i t y from E q u a t i o n 29 we n e e d t o
choose an e x p r e s s i o n f o r t h e f u g a c i t y c o e f f i c i e n t . Generally for
calculation of fugacity c o e f f i c i e n t an e q u a t i o n of state with
a p p r o p r i a t e m i x i n g r u l e s i s u s e d (12) i n t h e f o l l o w i n g e x p r e s s i o n :
oo
RT I n ψ]= / [ O P / Ô n j ) - (RT/V) ] d V - R T l n Z T v n (30)
V ' ' j#i

CARBON DIOXIDE - 2.3DMN
0.0 60.0 120.0 180.0 240.0 300.0

PRESSURE (BAR)
F i g u r e 1. S o l u b i l i t y o f 2,3 d i m e t h y l n a p h t h a l e n e (DMN) in
supercritical carbon dioxide using the Redlich-Kwong
equation of s t a t e . , o r i g i n a l mixing rules with
k£j=0; - - -, o r i g i n a l m i x i n g r u l e s w i t h f i t t e d k£j»
sss
, new mixing rules w i t h k£j 0; ·, • and A,
experimental data (13).

BENMEKKI ET AL. Mixing Rules for Cubic Equations of State
10 h • ι ι 1 4- d
0 50 100 150 200 250 300
P R E S S U R E (BAR)
F i g u r e 2. S o l u b i l i t y o f 2,3 d i m e t h y l n a p h t h a l e n e (DMN) i n
s u p e r c r i t i c a l carbon d i o x i d e . , Peng-Robinson e q u a t i o n
of s t a t e with the o r i g i n a l mixing rules; ·, • and A,
e x p e r i m e n t a l d a t a (13).

1
ιό • 1 1 • 1
10 3 1 / 8 J < j ^ -
308K
308Κ//Χ
Si /318K
10
ζ j //328K
s
ο
CM
10
CQ^DMN
ky- 0.1156
•jj s-0.2393
l\ 3 2 8 / h m
y= 0.6094
318 • » 308 K -
10
1\ // A : 318 K
• : 328 K
2 1 1 1 ..ι ι r
50 100 150 200 250 300
PRESSURE (BAR)
F i g u r e 3. S o l u b i l i t y o f 2,3 d i m e t h y l n a p h t a l e n e (DMN) i n
s u p e r c r i t i c a l carbon d i o x i d e . , Peng-Robinson e q u a t i o n
of state with the new m i x i n g rules; ·, • and A,

F i g u r e 4. S o l u b i l i t y o f 2,3 d i m e t h y l n a p h t a l e n e (DMN) i n
supercritical ethylene. , Peng-Robinson e q u a t i o n of
state with the o r i g i n a l mixing r u l e s ; ·, • and A,

1
ιό
328 Κ
0 ^ - 2 3 DMN
if0.1645
k
ljj*0.2723
ηγ0.6602
• « 306 Κ
* 318 Κ
• 328 Κ
-6
10 k_
50 100 150 200 250 300
PRESSURE (BAR;
F i g u r e 5. S o l u b i l i t y of 2,3 D i m e t h y l n a p h t a l e n e (DMN) in
supercritical ethylene. , Peng-Robinson e q u a t i o n of
s t a t e w i t h the new m i x i n g r u l e s ; · , • and A, experimental
d a t a (13).

Applications for Vapor-Liquid Equilibrium calculations
When a p p l y i n g a n e q u a t i o n o f s t a t e t o both vapor and l i q u i d phases,

the v a p o r - l i q u i d e q u i l i b r i u m p r e d i c t i o n s depend on t h e a c c u r a c y o f
the e q u a t i o n o f s t a t e used and, f o r multicomponent systems, on t h e
mixing rules. Attention will be g i v e n t o b i n a r y mixtures of
hydrocarbons and t h e t e c h n i c a l l y i m p o r t a n t nonhydrocarbons such as
h y d r o g e n s u l f i d e a n d c a r b o n d i o x i d e - F i g u r e s 6-7.
Thermodynamic Model. In t h e e q u i l i b r i u m s t a t e , t h e i n t e n s i v e
p r o p e r t i e s - t e m p e r a t u r e , p r e s s u r e and c h e m i c a l p o t e n t i a l s o f each
component- a r e c o n s t a n t i n t h e o v e r a l l system. S i n c e t h e f u g a c i t i e s
are f u n c t i o n s o f t e m p e r a t u r e , p r e s s u r e and c o m p o s i t i o n s , t h e
equilibrium condition
V L
fi (T,P,{y}) = fi (T,P,{x}) i = l,2,...,n (3D
can be e x p r e s s e d by
1
yi V
<*>i = x j Φ\ i = l,2,...,n (32)
The expression for thefugacity c o e f f i c i e n t Φ; d e p e n d s o n t h e

e q u a t i o n o f s t a t e t h a t i s u s e d a n d i s t h e same f o r t h e v a p o r a n d
l i q u i d phases. In c a l c u l a t i n g t h e m i x t u r e p r o p e r t i e s w i t h t h e Peng-
Robinson e q u a t i o n o f s t a t e we h a v e u s e d thefollowing combining
r u l e:
e,j- (1 - k i j ) Ce;, . C j j / b j i . b j j j l / 2 b j j (33)
A t h r e e p a r a m e t e r s e a r c h r o u t i n e was u s e d to evaluate the binary

interaction parameters which minimize the following objective
function:
M P(exp)-P(cal) 2
OF = Σ [ ] Î (34)
i=l P(exp)
w h e r e M i s t h e number o f e x p e r i m e n t a l p o i n t s c o n s i d e r e d .
Acknowledgments
T h i s r e s e a r c h i s s u p p o r t e d by theNational Science Foundation Grant

CPE - 8306808.
Legend o f Symbols
a, b, c , d :equation of s t a t e parameters
f :fugacity
k, 1, m :binary i n t e r a c t i o n parameters
η : number o f c o m p o n e n t s
N 0 : A v o g a d r o number
OF : o b j e c t i v e f u n c t i o n t o be m i n i m i z e d
Ρ :pressure
Τ : temperature

220.0
200.0 H
0.0 0.1 0.4 0.5 0.6

X(D . Yd)
F i g u r e 6. P r e s s u r e - c o m p o s i t i o n diagram of carbon d i o x i d e
and n-decane. , Peng-Robinson e q u a t i o n of s t a t e w i t h the
new m i x i n g r u l e s and t h r e e f i t t e d parameters (k--=0.4290,
l j = 0 . 3 6 5 8 and m j = - 0 . 3 2 1 7 ) ; * ( 4 4 4 . 2 6 Κ ) , ο (310.93 Κ ) ,
£ £
e x p e r i m e n t a l d a t a (16).

BENMEKKI ET AL. Mixing Rules for Cubic Equations of State
10.0-! , 1 1 1 , 1 , ! 1 1
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
X(D . Yd)
Figure 7. pressure-composition diagram o f ethane and
hydrogen s u l f i d e a t 283.15 K. , Peng-Robinson e q u a t i o n
of state with the new m i x i n g rules and t h r e e fitted
parameters O 4 j — 0 . 2 0 6 0 , 1 -=-0.6119 and m j=0.1365);
£ £
• and ο e x p e r i m e n t a l d a t a ( 1 7 ) .

u :intermolecular potential function

ν :molar volume
χ :mole f r a c t i o n
y :mole f r a c t i o n i n t h e v a p o r p h a s e
ζ :compressibi1ity factor
Φ :fugacity coefficient
σ :intermolecular d i s t a n c e parameter
€ : i n t e r a c t i o n energy parameter
ω tacentric factor
κ :a f u n c t i o n o f t h e a c e n t r i c factor
Subscr i p t s
c : c r i t i c a l property
j : component i d e n t i f i c a t i o n
2 :solute
Literature Cited
1. Alem, A. H.; Mansoori
2. Nauman, K. H.; Leland, T. W. Fluid Phase Equilibria 1984, 1,
18.
3. Renon, H., Ed.; Fluid Phase Equilibria 1983, 13.
4. Van der Waals, J. D. Ph.D. Thesis, Leiden, 1873.
5. Rowlinson, J. S.; Swinton, F. L. In "Liquid and Liquid
rd
Mixtures"; 3 Ed.; Butterworths: Wolborn, Mass., 1982.
6. Redlich, O.; Kwong, J. N. S. Chem. Rev. 1949, 44, 233·
7. Peng, D. Y.; Robinson, D. B. Ind. Eng. Chem. Fund. 1976, 5.
59.
8. Leland, T. W.; Chappelear, P. S. Ind. Eng. Chem. 1968, 15,
60.
9. Leland, T. W.; Rowlinson, J. S.; Sather, G. A.
Trans. Faraday Soc. 1968, 64, 1447.
10. Leland , T. W.; Rowlinson, J. S.; Sather, G. Α.; Watson, I. D.
Trans. Faraday Soc. 1969, 65, 2034.
11. Mansoori, G. Α.; Ely, J. F. J. Chem. Phys. 1985, 82, 406.
12. Prausnitz, J. M. In "Molecular Thermodynamics of Fluid Phase
Equilibria"; Prentice-Hall: Englewood Cliffs, NJ, 1969.
13. Kurnik, R. T.; Holla, S. J.; Reid, R. C. J. Chem. Eng. Data
1981, 26, 47.
14. Katz, D. L.; Firoozabadi, A. J. Petrol. Tech. 1978, Nov.,
1649.
15. Firoozabadi, Α.; Hekim, Y.; Katz, D. L. Canadian J. Chem. Eng.
1978, 56, 610.
16. Reamer, H. H.; Sage, Β. H. J. J. Chem. Eng. Data 1963, 8, 508.
17. Kalra, H.; Robinson, D. B.; Krishnan T. R. J. Chem. Eng. Data
1977, 22, 85.

Chapter 10
High-Pressure Phase Equilibria in Ternary Fluid

Mixtures with a Supercritical Component
A. Z. Panagiotopoulos and R. C. Reid
Department of Chemical Engineering, Massachusetts Institute of Technology,

Cambridge, M A 02139
Experimental results are presented for high pressure phase

equilibria in the binary systems carbon dioxide - acetone and
carbon dioxide - ethanol and the ternary system carbon dioxide
- acetone - water at 313 and 333 Κ and pressures between 20
and 150 bar. A hig
recirculation and sampling of all phases was used for the
experimental measurements. The ternary system exhibits an
extensive three-phase equilibrium region with an upper and
lower critical solution pressure at both temperatures. A
modified cubic equation of a state with a non-quadratic mixing
rule was successfully used to model the experimental data.
The phase equilibrium behavior of the system is favorable for
extraction of acetone from dilute aqueous solutions using
supercritical carbon dioxide.
The potential of supercritical extraction, a separation process in

which a gas above its critical temperature is used as a solvent, has
been widely recognized in the recent years. The first proposed
applications have involved mainly compounds of low volatility, and
processes that utilize supercritical fluids for the separation of
solids from natural matrices (such as caffeine from coffee beans) are
already in industrial operation. The use of supercritical fluids for
separation of liquid mixtures, although of wider applicability, has
been less well studied as the minimum number of components for any
such separation is three (the solvent, and a binary mixture of compo
nents to be separated). The experimental study of phase equilibrium
in ternary mixtures at high pressures is complicated and theoretical
methods to correlate the observed phase behavior are lacking.
One important potential application of supercritical extraction is
the recovery of polar organic compounds from aqueous solutions. Such
mixtures arise frequently as products of biochemical syntheses. In
many cases, the costs of the energy-intensive separations are high and
there is substantial incentive for the development of more efficient
processes.
Previous work in the area of high-pressure phase equilibrium of
aqueous solutions of organic compounds with supercritical fluids
0097-6156/87/0329-0115$06.00/0

i n c l u d e s the p i o n e e r i n g work o f E l g i n and W e i n s t o c k (1) c a r r i e d out

i n t h e 1950's. F r a n c i s (9) p r e s e n t e d a l a r g e number o f q u a l i t a t i v e
r e s u l t s f o r t e r n a r y systems o f l i q u i d c a r b o n d i o x i d e a t 298 K. In
the more r e c e n t y e a r s , P a u l a i t i s e t a l . ( 2 , 3 ) , Kuk and Montagna ( 4 ) ,
McHugh e t a l . (5) and Radosz (6) have r e p o r t e d measurements i n systems
w i t h some o f the f i r s t a l c o h o l s , water and s u p e r c r i t i c a l f l u i d s .
Experimental
The e x p e r i m e n t a l s e t u p u s e d i s shown i n F i g u r e 1. The main element

o f the equipment i s a h i g h p r e s s u r e o p t i c a l c e l l ( J e r g u s o n gage model
3
19-TCH-40) w i t h an i n t e r n a l volume o f about 50 cm , t h a t s e r v e s as a
m i x i n g and s e p a r a t i n g v e s s e l , as w e l l as f o r the v i s u a l o b s e r v a t i o n
o f t h e number and q u a l i t y o f t h e c o e x i s t i n g p h a s e s . Connections at
the bottom, top and s i d e o f the v e s s e l p e r m i t w i t h d r a w a l o f the lower,
u p p e r and m i d d l e phases, any two o f which c a n be r e c i r c u l a t e d e x t e r n a l l y
with a dual high pressur
Paar v i b r a t i n g tube d e n s i t
u s e d t o measure the d e n s i t y o f one o f the r e c i r c u l a t i n g p h a s e s . The
d e n s i t y meter c a n be s w i t c h e d t o sample any o f the r e c i r c u l a t i n g streams.
The J e r g u s o n gage i s immersed i n a c o n s t a n t temperature b a t h w i t h
s i l i c o n f l u i d as the h e a t - t r a n s f e r medium, t h a t a l s o t h e r m o s t a t s the
d e n s i t y meter. The b a t h temperature i s c o n t r o l l e d t o ± .01 Κ w i t h a
Thermomix 1460 temperature r e g u l a t o r and temperature i s measured w i t h
a c a l i b r a t e d m e r c u r y - i n - g l a s s thermometer t o w i t h i n .01 K. The l i n e s
e x t e r n a l t o the b a t h a r e m a i n t a i n e d a t the b a t h temperature w i t h the
h e l p o f h e a t i n g t a p e s and temperature a t s e v e r a l p o i n t s i s m o n i t o r e d
w i t h thermocouples. P r e s s u r e i s measured w i t h two c a l i b r a t e d H e i s e
p r e s s u r e i n d i c a t o r s t o w i t h i n ±.16 b a r f o r p r e s s u r e s up t o 160 b a r
and t o w i t h i n ±.4 b a r f o r p r e s s u r e s up t o 350 b a r .
Sampling i s p e r f o r m e d w i t h two h i g h p r e s s u r e s w i t c h i n g v a l v e s w i t h
i n t e r n a l volume .5 μΐ ( f o r the upper phase) and .2 μΐ f o r the lower
or middle phases. The samples a r e d i r e c t l y d e p r e s s u r i z e d i n t o a He
c a r r i e r gas stream and a n a l y z e d w i t h a P e r k i n Elmer Sigma 2 Gas
Chromatograph, u s i n g a Porapak Q column s u p p l i e d by S u p e l c o . The
r e s p o n s e f a c t o r s f o r the m a t e r i a l s u s e d were found t o be c l o s e t o
t h o s e r e p o r t e d by D i e t z ( 7 ) . T y p i c a l r e p r o d u c i b i l i t y o f the a n a l y s i s
i s ±.003 i n mole f r a c t i o n , w i t h somewhat l a r g e r d e v i a t i o n s f o r the
gas-phase c o m p o s i t i o n s a t low p r e s s u r e s .
A f t e r p u r g i n g and e v a c u a t i o n o f the equipment, t h e c e l l i s c h a r g e d
w i t h a l i q u i d m i x t u r e o f known c o m p o s i t i o n and the supercritical
component up t o the d e s i r e d p r e s s u r e . The r e c i r c u l a t i o n pumps a r e
s t a r t e d , and a p p r o a c h t o e q u i l i b r i u m m o n i t o r e d by the s t a b i l i t y o f
p r e s s u r e , d e n s i t y and c o m p o s i t i o n measurements w i t h t i m e . F o r the
m i x t u r e s s t u d i e d , a t y p i c a l e q u i l i b r a t i o n time i s 15 min, b u t a t
l e a s t 30 min a r e a l l o w e d b e f o r e the f i n a l s a m p l i n g . At l e a s t two
samples a r e t a k e n from each phase a t e q u i l i b r i u m . A new pressure
p o i n t c a n be e s t a b l i s h e d i m m e d i a t e l y by i n t r o d u c i n g o r removing
s u p e r c r i t i c a l f l u i d o r l i q u i d , so t h a t the l e v e l o f the i n t e r f a c e s i n
the c e l l a t the new d e s i r e d p r e s s u r e i s a p p r o p r i a t e f o r sampling
t h r o u g h the a v a i l a b l e p o r t s . E n t r a i n m e n t o f the phases i s n o t n o r m a l l y
a problem, e x c e p t n e a r a c r i t i c a l p o i n t . Selective flashing and
a d s o r p t i o n on t h e s w i t c h i n g v a l v e s i s sometimes a d i f f i c u l t y f o r the
u p p e r ( g a s ) phase s a m p l i n g l o o p , b u t i s p r e v e n t e d by h e a t i n g t h e v a l v e .

CONSTANT
' TEMPERATURE
ENCLOSURE
LIQUID
I FEED
PUMP K > i h O PI
A A
SCF N2

CARRIER CARRIER

GAS GAS
F i g u r e 1. Schematic drawing o f t h e equipment.

Results
B i n a r y Systems. As a t e s t o f t h e v a l i d i t y o f t h e equipment d e s i g n and

e x p e r i m e n t a l p r o c e d u r e s , we f i r s t i n v e s t i g a t e d a b i n a r y system f o r
which r e s u l t s have been p r e v i o u s l y published. Knowledge o f the
b e h a v i o r o f the b i n a r y systems i s i n i t s e l f i m p o r t a n t , s i n c e the d a t a
p r o v i d e the a p p r o p r i a t e l i m i t s f o r the c o r r e s p o n d i n g t e r n a r y systems.
In F i g u r e 2, we p r e s e n t e x p e r i m e n t a l r e s u l t s and l i t e r a t u r e d a t a
f o r the system c a r b o n d i o x i d e - acetone a t 313 and 333 Κ ( l i t e r a t u r e
r e s u l t s a r e o n l y a v a i l a b l e f o r the lower t e m p e r a t u r e ) . The agreement
between the two s e t s o f r e s u l t s i s e x c e l l e n t . A l s o shown on the same
f i g u r e as c o n t i n u o u s l i n e s a r e the r e s u l t s o f f i t t i n g the e x p e r i m e n t a l
d a t a u s i n g a m o d i f i e d Peng-Robinson e q u a t i o n o f s t a t e d e s c r i b e d i n
the Appendix. The agreement between e x p e r i m e n t a l and p r e d i c t e d phase
compositions i s w i t h i n the e x p e r i m e n t a l u n c e r t a i n t y o f the d a t a ,
e x c e p t i n the c r i t i c a l r e g i o n .
S e v e r a l o f the f e a t u r e s o f t h e phase b e h a v i o r shown on F i g u r e 2 a r e
quite general. In p a r t i c u l a r
c a r b o n d i o x i d e i n the l i q u i
The system c r i t i c a l p r e s s u r e i s comparable t o t h e c r i t i c a l p r e s s u r e
o f c a r b o n d i o x i d e and i n c r e a s e s w i t h temperature a t the temperature
range s t u d i e d . A l t h o u g h the s o l u b i l i t y o f a c e t o n e i n the gas phase
i s low i n the two-phase r e g i o n , t h e r e i s complete m i s c i b i l i t y between
C0 2 and a c e t o n e a t r e l a t i v e l y moderate p r e s s u r e s . Carbon d i o x i d e a t
l i q u i d - l i k e d e n s i t i e s i s an e x c e l l e n t s o l v e n t f o r a wide range o f
o r g a n i c compounds, as was f i r s t o b s e r v e d by F r a n c i s (9) f o r near
c r i t i c a l l i q u i d C0 .
2
One a d d i t i o n a l example o f the same g e n e r a l type o f b e h a v i o r i s

d e m o n s t r a t e d by the c a r b o n d i o x i d e - e t h a n o l system. T h r e e measured
i s o t h e r m s f o r t h i s system a r e p r e s e n t e d i n F i g u r e 3. No comparable
set o f e x p e r i m e n t a l r e s u l t s appears t o be a v a i l a b l e i n the open
literature. A g a i n , agreement between e x p e r i m e n t a l r e s u l t s and model
p r e d i c t i o n s i s good.
T e r n a r y Systems. As one o f a s e r i e s o f model systems, we s t u d i e d the

c a r b o n d i o x i d e - acetone - water t e r n a r y system a t 313 and 333 K.
The most i n t e r e s t i n g f e a t u r e o f the system b e h a v i o r i s an e x t e n s i v e
three-phase r e g i o n a t both temperatures. The t h r e e - p h a s e r e g i o n i s
f i r s t observed a t a p r e s s u r e o f l e s s t h a n 30 b a r a t 313 Κ and
a p p r o x i m a t e l y 35 b a r a t 333 K, e x t e n d i n g up t o a p p r o x i m a t e l y the
c r i t i c a l p r e s s u r e o f the b i n a r y c a r b o n d i o x i d e - a c e t o n e system. T a b l e
I summarizes our e x p e r i m e n t a l r e s u l t s f o r the c o m p o s i t i o n o f the
t h r e e phases a t e q u i l i b r i u m as a f u n c t i o n o f p r e s s u r e and temperature.
The p h y s i c a l p i c t u r e t h a t u n d e r l i e s t h i s b e h a v i o r , as p o i n t e d out
f i r s t by E l g i n and W e i n s t o c k ( 1 ) , i s the ' s a l t i n g o u t ' e f f e c t by a
s u p e r c r i t i c a l f l u i d on an aqueous s o l u t i o n o f an o r g a n i c compound.
As p r e s s u r e i s i n c r e a s e d , the tendency o f the s u p e r c r i t i c a l f l u i d t o
s o l u b i l i z e i n the o r g a n i c l i q u i d r e s u l t s i n a phase s p l i t i n the
aqueous phase a t a lower c r i t i c a l s o l u t i o n p r e s s u r e (which v a r i e s
w i t h temperature). As p r e s s u r e i s f u r t h e r i n c r e a s e d , t h e second
l i q u i d phase and the s u p e r c r i t i c a l phase become more and more s i m i l a r
to e a c h o t h e r and merge a t an upper c r i t i c a l s o l u t i o n p r e s s u r e . Above
t h i s p r e s s u r e o n l y two phases c a n c o e x i s t a t e q u i l i b r i u m . T h i s p a t t e r n
o f b e h a v i o r was a l s o o b s e r v e d by E l g i n and W e i n s t o c k f o r the system
e t h y l e n e - a c e t o n e - water a t 288 K. I n a d d i t i o n , the same type o f

ο

Mole Fraction C02

F i g u r e 2. Phase e q u i l i b r i u m b e h a v i o r f o r the b i n a r y system c a r b o n
d i o x i d e - acetone. E x p e r i m e n t a l , 313 Κ ( Δ ) ; e x p e r i m e n t a l , 333 Κ
(•) ; l i t e r a t u r e , 313 Κ (χ) ; m o d i f i e d Peng-Robinson e q u a t i o n o f s t a t e
(—). L i t e r a t u r e d a t a a r e from r e f e r e n c e (10).
120
0 0.2 0.4 0.6 0.8 1
Mole F r a c t i o n C02
F i g u r e 3. Phase e q u i l i b r i u m b e h a v i o r f o r the system c a r b o n d i o x i d e

- ethanol. E x p e r i m e n t a l , 308.1 Κ (+) ; 323.1 Κ ( 0 ) ; 338.1 Κ ( Δ ) ;
m o d i f i e d Peng-Robinson e q u a t i o n o f s t a t e ( — ) .

10. PANAGIOTOPOULOS AND REID High-Pressure Phase Equilibria 121
TABLE I : Three phase e q u i l i b r i u m c o m p o s i t i o n s f o r the

system Water (1) - A c e t o n e (2) · CO (3) 2
lower phase upper phase m i d d l e ph ase
Z
X
l X
2 X
3 yi y 2 y 3
Z
l Z
2 3
Τ - 313 Κ
29 3 0 810 0 153 0. 037 0.005 0.025 0. 970 0. 294 0 454 0 252

35 9 0 864 0 106 0. 030 0.006 0.019 0 975 0. 197 0 427 0 376
43 2 0 904 0 075 0. 021 0.003 0.017 0 980 0. 153 0 360 0 487
55 9 0 920 0 052 0 028 0.002 0.015 0 983 0. 119 0 230 0 651
61 1 0 942 0 037 0 021 0.004 0.015 0 981 0 114 0 191 0 695
65 8 0 944 0 032 0 024 0.002 0.015 0 983 0 130 0 148 0 722
75 .2 0 959 0 017 0 024 0.002 0.014 0 984 0 020 0 069 0 911
79 .6 0 966 0 011 0 023 0.002 0.015 0 983 0 049 0 035 0 916
Γ - 333 Κ
39 .4 0 795 0 163 0 042 1 0 400 0 .398 0 202

51 .1 0 880 0 091 0 029 1 0 182 0 .418 0 400
59 .4 0 906 0 068 0 026 0.006 0.030 0 964 0 173 0 .359 0.468
70 .3 0 925 0 049 0 026 0.008 0.035 0 957 0 117 0 .300 0 583
79 .2 0 939 0 039 0 022 0.006 0.032 0 962 0 089 0 .234 0 677
92 .6 0 946 0 029 0 025 0.010 0.046 0 944 0 084 0 .127 0 789
1
We were n o t a b l e to obtain r e s u l t s f o r these s t a t e conditions.

b e h a v i o r , b u t a t q u i t e d i f f e r e n t p r e s s u r e s r e l a t i v e t o the pure s o l v e n t
c r i t i c a l p r e s s u r e was r e p o r t e d by P a u l a i t i s e t a l . (3.) f o r t h e system
c a r b o n d i o x i d e - i s o p r o p a n o l - water, by McHugh e t a l . (5) f o r t h e
system ethane - e t h a n o l - water and by P a u l a i t i s e t a l . (2) f o r the
c a r b o n d i o x i d e - e t h a n o l - water system. T h i s b e h a v i o r appears then
to be q u i t e common.
A more complete p i c t u r e o f the phase e q u i l i b r i u m b e h a v i o r i s g i v e n
i n F i g u r e 4 f o r t h e system under s t u d y a t 333 K. A t t h i s temperature,
we measured t i e l i n e s i n t h e two-phase r e g i o n i n a d d i t i o n t o t h e
three-phase compositions. The d a r k e r l i n e s and s q u a r e s on F i g u r e 4
r e p r e s e n t t h e s e e x p e r i m e n t a l measurements. The l i g h t l i n e s a r e model
p r e d i c t i o n s , u s i n g values o f i n t e r a c t i o n parameters determined s o l e l y
from r e g r e s s i o n o f b i n a r y d a t a (see A p p e n d i x ) . The two s e t s o f r e s u l t s
a r e i n good agreement w i t h each o t h e r . The a b i l i t y t o p r e d i c t t e r n a r y
d a t a from b i n a r y d a t a o n l y i s o f g r e a t p r a c t i c a l importance, s i n c e i t
p e r m i t s t h e e v a l u a t i o n o f a l a r g e range o f p r o c e s s a l t e r n a t i v e s from
l i m i t e d experimental information.
An i n t e r e s t i n g f e a t u r
relative insensitivity o
l i n e s t o v a r i a t i o n s i n p r e s s u r e i n t h e two-phase r e g i o n , as e v i d e n c e d
by c o m p a r i s o n o f t h e diagrams a t 100 and 150 b a r i n F i g u r e 4. This
w o u l d seem t o imply t h a t s i m i l a r s e p a r a t i o n s c a n be a c h i e v e d by
o p e r a t i o n a t a range o f p r e s s u r e s above t h e upper c r i t i c a l s o l u t i o n
p r e s s u r e o f -95 b a r .
From an e n g i n e e r i n g p o i n t o f view, t h e most i m p o r t a n t q u a n t i t i e s
i n t h e e v a l u a t i o n o f a s e p a r a t i o n scheme b a s e d o n a phase b e h a v i o r
p a t t e r n such as t h e one shown, a r e t h e s e l e c t i v i t y o f t h e s e p a r a t i o n
w i t h r e s p e c t t o t h e d e s i r e d component, as w e l l as t h e l o a d i n g o f the
d e s i r e d component i n t h e e x t r a c t a n t phase. I t i s w e l l known t h a t
t h o s e two f a c t o r s u s u a l l y i n c r e a s e i n d i f f e r e n t d i r e c t i o n s . Figures
5 and 6 p r e s e n t e x p e r i m e n t a l d a t a and model p r e d i c t i o n s f o r t h e d i s -
t r i b u t i o n c o e f f i c i e n t o f a c e t o n e and the s e l e c t i v i t y r a t i o a o f acetone
o v e r w a t e r ( d e f i n e d as t h e r a t i o o f d i s t r i b u t i o n c o e f f i c i e n t s o f
a c e t o n e and water i n t h e l i q u i d and f l u i d p h a s e s ) . The d i s t r i b u t i o n
c o e f f i c i e n t shows a maximum a t b o t h t e m p e r a t u r e s , w i t h a h i g h e r v a l u e
at t h e h i g h e r temperature, whereas t h e s e l e c t i v i t y d e c r e a s e s smoothly
from t h e l i m i t i n g v a l u e o f -300 a t low a c e t o n e c o n c e n t r a t i o n s t o 1 as
the p l a i t p o i n t i s approached. The e x p e r i m e n t a l d a t a show t h e same
t r e n d s , a l t h o u g h t h e r e i s some s c a t t e r due t o t h e f a c t t h a t s m a l l
absolute e r r o r s i n t h e low s u p e r c r i t i c a l phase c o n c e n t r a t i o n s o f
a c e t o n e and water r e s u l t i n l a r g e r e l a t i v e e r r o r s f o r t h e d i s t r i b u t i o n
c o e f f i c i e n t and s e l e c t i v i t y f a c t o r s . S e l e c t i v i t i e s are generally
h i g h e r f o r t h e lower t e m p e r a t u r e , b u t l o a d i n g s a r e l o w e r .
I n F i g u r e 7, we p r e s e n t t h e w/w c o n c e n t r a t i o n o f a c e t o n e i n t h e
s u p e r c r i t i c a l phase on a C 0 - f r e e b a s i s v e r s u s t h e c o r r e s p o n d i n g
2
c o n c e n t r a t i o n o f acetone i n t h e l i q u i d phase. The c u r v e shows a

b r o a d maximum a t a range o f c o n c e n t r a t i o n s o f a c e t o n e i n t h e aqueous
phase between 2% and 15% w/w. The maximum c o n c e n t r a t i o n o f acetone
i n t h e s u p e r c r i t i c a l phase i s c l o s e t o 95% w/w. We can, t h e r e f o r e ,
o b t a i n almost pure a c e t o n e from a d i l u t e aqueous s o l u t i o n u s i n g a
s i n g l e - s t e p e x t r a c t i o n with s u p e r c r i t i c a l carbon d i o x i d e .

Acgtong (2) Acetong (2)
Water (1) C02 (3)
;
333 Κ . Ρ = 27. 6 bar
Τ = 333 Κ . Ρ = 40. 0 bar
C02 (3)
Figure 4. Phase equilibrium behavior f o r the system water (1)-

acetone (2) - carbon dioxide (3) at 333 Κ : experimental phase
compositions (•) and t i e - l i n e s (—) ; predicted t i e - l i n e s (—) ;
predicted three-phase equilibrium compositions (Δ).

0.55 0.65 0.75 0.85 0.95
x1/ (x1 + x2)
F i g u r e 5. D i s t r i b u t i o n c o e f f i c i e n t o f a c e t o n e f o r t h e system
water (1) - a c e t o n e (2) - c a r b o n d i o x i d e (3) a t 150 b a r , as a
f u n c t i o n o f the water concentration i n the lower phase.
E x p e r i m e n t a l , 333 Κ (•); p r e d i c t e d , 333 Κ and 313 Κ ( — ) .

0.55 0.65 0.75 0.85 0.95

x1/ (x1 + x2)
F i g u r e 6. S e l e c t i v i t y f a c t o r f o r a c e t o n e o v e r water f o r t h e
system water (1) - a c e t o n e (2) - c a r b o n d i o x i d e (3) system a t 150
b a r , as a f u n c t i o n o f t h e water c o n c e n t r a t i o n i n t h e lower phase.
E x p e r i m e n t a l , 333 Κ ( 0 ) ; p r e d i c t e d , 333 Κ and 313 Κ ( — ) .

Ο 4 8 12 16 20 24 28 ^
m
Acetone in aqueous phase (% w/w) Π
Η

F i g u r e 7. Concentration o f acetone i n the s u p e r c r i t i c a l f l u i d ο
phase as a f u n c t i o n o f the c o n c e n t r a t i o n o f a c e t o n e i n t h e l i q u i d ^
phase ( c o n c e n t r a t i o n u n i t s : % w/w on a C 0 - f r e e b a s i s ) .
2 pE3
E x p e r i m e n t a l , 333 Κ (•); p r e d i c t e d , 333 Κ and 313 Κ ( — ) . G
D
C/5
APPENDIX
Equation of State used
F o r the c o r r e l a t i o n o f the e x p e r i m e n t a l r e s u l t s , we u s e d a m o d i f i c a t i o n
o f the Peng-Robinson e q u a t i o n o f s t a t e d e v e l o p e d by the a u t h o r s . The
e s s e n c e o f the method, w h i c h i s p r e s e n t e d i n d e t a i l i n (8.) i s the use
o f a n o n - q u a d r a t i c m i x i n g r u l e f o r the a t t r a c t i v e p a r a m e t e r a . The m
m i x i n g r u l e i n v o l v e s two b i n a r y i n t e r a c t i o n p a r a m e t e r s t o be d e t e r m i n e d
from r e g r e s s i o n o f e x p e r i m e n t a l d a t a . The e q u a t i o n s f o r the p r e s s u r e ,
the m i x i n g r u l e u s e d and the r e s u l t i n g e x p r e s s i o n f o r the c h e m i c a l
p o t e n t i a l o f a component i n a m i x t u r e a r e g i v e n below f o r the case o f
a g e n e r a l c u b i c e q u a t i o n o f s t a t e ( f o r the Peng-Robinson e q u a t i o n o f
s t a t e , u = 2 and w = - 1 ) .
ρ -
V - b V + uVb + wb
m m m
a = Υ Υ χ. χ. a.. (2)
m . . ι ι ij
ι J
b x b ( 3 )
« - ? i i
a.. - 7 a. a. [1-k..+(k..-k..)x.] (4)
OA ο f
k k b
/ PV Ί x „ P(V-b ) m
= i n i n +
T F - ~b RT " RT
Yx (a +a
) - yyx χ (k -k )7a a + χ Tx k -k )Ja a b
r i ik k i ;
i j ij ji i j i ki ik k i k / V
I ij ι _
a ' b
m m
2
a 2V + b (u-7u -4w)
in = (5)
2
Ju - 4w b R T 2V + b (u+7u -4w)
m m
2
To e s t i m a t e the pure component p a r a m e t e r s , we u s e d the t e c h n i q u e

o f P a n a g i o t o p o u l o s and Kumar ( 1 1 ) . The t e c h n i q u e p r o v i d e s p a r a m e t e r s
t h a t e x a c t l y r e p r o d u c e the v a p o r p r e s s u r e and l i q u i d d e n s i t y o f a
s u b c r i t i c a l component. T a b l e I I p r e s e n t s the pure component p a r a m e t e r s
t h a t were used. F o r the s u p e r c r i t i c a l components, the u s u a l a c e n t r i c
f a c t o r c o r r e l a t i o n was u t i l i z e d .
I t i s i m p o r t a n t t o n o t e , t h a t the i n t e r a c t i o n p a r a m e t e r s between
the components (two p e r b i n a r y ) were e s t i m a t e d s o l e l y from b i n a r y
phase e q u i l i b r i u m d a t a , i n c l u d i n g l o w - p r e s s u r e VLE d a t a f o r the b i n a r y
a c e t o n e - water; no t e r n a r y d a t a were u s e d i n the f i t t i n g . The v a l u e s
o f the i n t e r a c t i o n p a r a m e t e r s o b t a i n e d a r e shown i n T a b l e I I I .

TABLE I I : Pure component p a r a m e t e r s
Component T(K) a 3
(Jxm /mol) 10 6
b 3
(m /mol)
Acetone 313.15 2.1772 62.35

333.15 2.1165 62.65
Ethanol 308.15 2.0292 48.23

323.15 1.9679 48.44
338.1
Water 313.15 .81614 16.07

333.15 .79123 15.99
TABLE I I I : I n t e r a c t i o n parameters
System Τ (Κ) ^12 ^2 1
C0 (1) - acetone(2)
2 313 15 -0.02 0.00
333 15 -0.02 0.00
C0 (1) - ethanol(2)
2 308 15 0.072 0.069
323 15 0.093 0.077
338 15 0.089 0.061
C 0 ( 1 ) - water(2)
2 313 15 -0.205 0.162
333 15 -0.185 0.160
acetone(1) - water(2) 313 15 -0.310 -0.150

333 15 -0.293 -0.132

10. PANAGIOTOPOULOS A N D REID High-Pressure Phase Equilibria 129
Conclusions
A r e c i r c u l a t i o n apparatus f o r the d e t e r m i n a t i o n o f h i g h pressure

phase e q u i l i b r i u m d a t a f o r m i x t u r e s o f water, p o l a r o r g a n i c l i q u i d s
and s u p e r c r i t i c a l f l u i d s was c o n s t r u c t e d and o p e r a t e d f o r b i n a r y and
t e r n a r y systems w i t h s u p e r c r i t i c a l c a r b o n d i o x i d e .
The system c a r b o n d i o x i d e - a c e t o n e - w a t e r was i n v e s t i g a t e d a t 313
and 333 K. The system d e m o n s t r a t e s s e v e r a l o f t h e g e n e r a l c h a r a c -
t e r i s t i c s o f phase e q u i l i b r i u m b e h a v i o r f o r t e r n a r y aqueous systems
with a s u p e r c r i t i c a l f l u i d . These i n c l u d e an e x t e n s i v e LLV r e g i o n
t h a t a p p e a r s a t r e l a t i v e l y low p r e s s u r e s . Carbon d i o x i d e e x h i b i t s a
h i g h s e l e c t i v i t y f o r a c e t o n e o v e r w a t e r and c a n be u s e d t o e x t r a c t
a c e t o n e from d i l u t e aqueous s o l u t i o n s .
A model b a s e d on a m o d i f i e d m i x i n g r u l e f o r t h e Peng-Robinson
e q u a t i o n o f s t a t e was a b l e t o r e p r o d u c e q u a n t i t a t i v e l y a l l f e a t u r e s
o f t h e o b s e r v e d phase e q u i l i b r i u m b e h a v i o r , w i t h model p a r a m e t e r s
determined from b i n a r y data only. The use o f s u c h models may
substantially facilitat
for separations that u t i l i z
Acknowledgments
F i n a n c i a l s u p p o r t f o r t h i s r e s e a r c h was p r o v i d e d b y a g r a n t from t h e
National Science Foundation. One o f t h e a u t h o r s (AZP) was a l s o
s u p p o r t e d by a H a l c o n I n c . F e l l o w s h i p . We g r a t e f u l l y acknowledge
both sponsors.
Literature Cited
1. Elgin, J.C.; Weinstock, J.J. J. Chem. Eng. Data 1959, 4(1), 3-12.
2. Paulaitis, M.E.; Gilbert, M.L.; Nash, C.A. "Separation of Ethanol
- Water Mixtures with Supercritical Fluids", paper presented at
the 2nd World Congress of Chemical Engineering, Montreal, Canada,
Oct. 5, 1981.
3. Paulaitis, M.E.; Kander, R.G.; DiAndreth, J.R. Ber. Bunsenges.
Phys. Chem. 1984, 88, 869-875.
4. Kuk, M.S.; Montagna, J.C. Ch. 4 in Paulaitis. M.E. et al. (ed),
"Chemical Engineering at Supercritical Fluid Conditions", Ann
Arbor Science Publishers, Ann Arbor, Mich., 1983 pp. 101-111.
5. McHugh, M.A.; Mallett, M.W.; Kohn, J.P. "High Pressure Fluid
Phase Equilibria of Alcohol - Water - Supercritical Solvent
Mixtures", paper presented at the 1981 annual AIChE meeting, New
Orleans, Louisiana, Nov. 9, 1981.
6. Radosz, M. Ber. Bunsenges. Phys. Chem. 1984, 88, 859-862.
7. Dietz, W.A. J. Gas Chrom. 1967, 5(2) 68-71.
8. Panagiotopoulos, A.Z.; Reid, R.C., in "Equations of State-
Theories and Applications", Robinson, R.L; Chao, K.C. (ed.), ACS
Symposium Series No. 300, American Chemical Society, Washington,
D.C., 1986; pp. 571-582.
9. Francis, A.W. J. Phys. Chem. 1954, 58, 1099-1114
10. Katayama, T.; Oghaki, K.; Maekawa, G.; Goto, M.; Nagano, T. J.
Chem. Eng. Jpn. 1975, 8(2) , 89-92.
11. Panagiotopoulos, A.Z.; Kumar, S. Fluid Phase Equil. 1985, 22, 77-88.

Chapter 11
Solubilities of Five Solid n-Alkanes

in Supercritical Ethane
Iraj Moradinia and Amyn S. Teja
School of Chemical Engineering, Georgia Institute of Technology,

Atlanta, GA 30332-0100
The effect of solid structure on the solubilities

of n-alkanes in supercritical ethane has been
investigated at a temperature just above the
critical point o
alkanes containing 28 to 33 carbon atoms in ethane
at 308.15K and pressures up to 20 MPa are reported
in this work. The enhancement factor is shown to
exhibit a regular trend with the number of carbon
atoms in the n-alkane, although different trends
are exhibited by the odd and even members of the
series.
The n-alkanes are an interesting homologous series because they

display great regularity in their behavior. Many of their fluid
phase properties, for example, can be correlated with the number of
carbon atoms in the molecules (J_>_2_) · In order to develop general
relations for supercritical extraction, therefore, we have studied
the solubilities of solid n-alkanes containing 28 to 33 carbon atoms
in supercritical ethane.
An additional reason for studying the n-alkane series is that
even-numbered n-alkanes exhibit different trends in their solid
phase properties (e.g. sublimation pressure, heat of fusion, etc.)
than the odd-numbered members of the series (_3^6_)· This is shown
for the heat of fusion in figure 1, and is a consequence of the
different packing arrangements in the solid phase. It may be
possible using supercritical extraction to exploit these differences
in order to separate close-boiling members of the series. Any
generalization for supercritical extraction behavior must,
therefore, take account of these differences in behavior. The
solubilities of solid n-Octacosane (n"*C28H58^' n-Nonacosane
(n-C29H^Q), n-Triacontane (n*"C3oH62^ ' n " D o t r i a c o n t a n e (n"C32H66^'
and n-Tritriacontane (n-C^H^g) in supercritical ethane are reported
below. The solubilities of the even-numbered members of the series
have been obtained from our previous work (7).
0097-6156/87/0329-0130$06.00/0

11. MORADINIA AND TEJA n-Alkane Solubility in Ethane 131

EXPERIMENTAL
The a p p a r a t u s used i n t h i s study was a s i n g l e - p a s s flow system shown

s c h e m a t i c a l l y i n f i g u r e 2. I t i s s i m i l a r i n p r i n c i p l e to t h a t used
by K u r n i k e t a l . ( 8 ) . The e x p e r i m e n t a l p r o c e d u r e has been o u t l i n e d
i n a p r e v i o u s p u b l i c a t i o n (7_).
SOURCE AND PURITY OF THE MATERIALS
n c H a n c n C H 1 1 3 ( 1 a s t a t e d
The s o l i d n - a l k a n e s ( n - C ^ H ^ g , " 3 o 6 2 ' * ~ 32 66^
H
p u r i t y o f 99% o r b e t t e r and n~C29 60 bad a s t a t e d p u r i t y o f 98% o r
better. The n - a l k a n e s were o b t a i n e d from W i l e y O r g a n i c s . S o l i d n-
C H w a s 0 D t a
33 68 ined from F l u k a C h e m i c a l Corp. and had a s t a t e d
p u r i t y o f 97% o r b e t t e r . The s o l i d s were used w i t h o u t f u r t h e r
purification. Ethane was f u r n i s h e d by the Matheson Gas Co. w i t h
99+% p u r i t y and was a l s o used w i t h o u t f u r t h e r p u r i f i c a t i o n .
RESULTS
Our r e s u l t s f o r the b i n a r
C H + n c H C H + n C H a n d C H + n c H a r e l v e n n
2 6 " 30 62» 2 6 " 32 66» 2 6 " 33 68 S *
t a b l e 1.
T a b l e 1. E x p e r i m e n t a l R e s u l t s a t 308.15K
y xl0 2
y xl0 y xl0 3
2
3
2
3
y xl0 2
3
y xl0 2
C H (1)+
2
C H (1)+
6
C H (1)+ 2 6 2 6
C^H (1)+ 6
C H (1)+
2 6
n-C H (2) ηδ Η (2) nC H (2) n C H ( 2 )

nC H (2) 3 3 6 8
2 8 5 8 2 9 6 0 3 0 6 2
32 66
P(MPa)
6.57 1.89 2.32 0.549 0.216 .371
10.10 3.38 4.32 1.24 0.713 .963
12.02 6.43 8.29 1.45 0.801 1.14
13.64 7.53 9.91 1.71 0.959 1.36
16.67 10.80 14.20 2.24 1.26 1.64
20.20 15.18 3.20 1.81 2.37
DATA CORRELATION
E x p e r i m e n t a l data were c o r r e l a t e d u s i n g the P a t e l - T e j a (9) e q u a t i o n

of state. For a pure solid phase i n equilibrium with a
s u p e r c r i t i c a l gas phase, we may w r i t e ( 1 0 ) .
s
v 0
p a P
where I s the s u b l i m a t i o n
2 (vapor) pressure o f the s o l u t e 2,
ap
<f> 2 i s the f u g a c i t y c o e f f i c i e n t o f the s o l u t e a t i t s s u b l i m a t i o n
pressure, V i s the molar volume o f the pure s o l u t e , y
2 i s the 2
composition (solubility) of the s o l u t e i n the supercritical

solvent, φ i s fugacity2 coefficient of the solute in the
s u p e r c r i t i c a l s o l v e n t , Ρ i s the p r e s s u r e and a l l p r o p e r t i e s a r e
evaluated a t the system temperature T. Since the sublimation
ν Ρ
pressure i s u s u a l l y very s m a l l , we may assume φ ~ 1 and the 2
integral to be e v a l u a t e d from zero p r e s s u r e to the p r e s s u r e P.

BACK
PRES. REG.
® r
ETHANE HEAT EQUILIBRIUM

LIQUEFIER MINIPUMP
SUPPLY EXCHANGER I— CELL
TEMPERATURE
r
MEASUREMENT
CONSTANT TEMP. BATH

SEPARATION WET TEST
1 fc ROTAMETER VENT
j — * VESSEL w METER
VALVE

F i g u r e 2. Single-pass supercritical flow apparatus.
Also, since the s o l i d volume i s approximately constant with

p r e s s u r e , we can i n t e g r a t e and r e w r i t e eq. (1) as f o l l o w s :
V a p
P EXP[PV!!/RT]
Q
Thus, i f the s o l i d phase p r o p e r t i e s ( d e n s i t i e s and sublimation

pressures) a r e known, then the s o l u b i l i t y o f the s o l u t e i n the
supercritical solvent a t any pressure and temperature can be
calculated provided an e q u a t i o n o f s t a t e i s a v a i l a b l e f o r the
c a l c u l a t i o n of φ^. The r e s u l t s f o r f i v e b i n a r y systems u s i n g P a t e l -
T e j a e q u a t i o n o f s t a t e shown i n f i g u r e s 3 and 4.
The P a t e l - T e j a e q u a t i o n o f s t a t e i s a b l e to c o r r e l a t e the data f o r
the b i n a r y systems r e a s o n a b l y well provided a binary interaction
coefficient (k-π) i s included i n the c a l c u l a t i o n s . It is
interesting to note that the b i n a r y interaction coefficients
o b t a i n e d from c o r r e l a t i o n o f data f o r the odd members o f the s e r i e s
a r e an o r d e r o f magnitude s m a l l e r than those o b t a i n e d f o r the even
members o f the s e r i e s
carbon number. Thes
sublimation pressures and l e a d to the c o n c l u s i o n t h a t d i f f e r e n t
c o r r e l a t i o n s w i l l be r e q u i r e d f o r odd and even numbered members o f
any homologous s e r i e s . A p l o t o f enhancement f a c t o r (E) a l s o shows
t h i s b e h a v i o r w i t h c a r b o n number ( F i g u r e 5 ) .
Enhancement f a c t o r s a r e g i v e n i n T a b l e 2. S o l i d d e n s i t i e s and
s u b l i m a t i o n p r e s s u r e s used i n the s o l u b i l i t y c a l c u l a t i o n s ( E q . 2)
are given i n Table 3. The d e n s i t i e s were supplied by the
m a n u f a c t u r e r s whereas the s u b l i m a t i o n p r e s s u r e s were e x t r a p o l a t e d
u s i n g data on o t h e r n - a l k a n e s [ 7 ] .
Table 2. Enhancement F a c t o r s a t Τ = 308.15K
n C H
n C
"* 28 58H n C
" 29 60H n C H
"" 30 62 n C
" 32 66 H
" 33 68
Ρ(MPa)
11 11 11 12 12
6, 57 1.947x10 1.216x10 977x10 6.926x10 3.057x10
11 11 12 13 13
10, 10 3.481x10 464x10 3.514x10 1.220x10
12 11 12 13 13
12.02 1.212x10 7.951x10 821x10 4.699x10 1.719x10
12 12 12 13 13
13.64 1.611x10 1.077x10 452xl0 * A
6.364x10 2.327x10
12 12 13 14 13
16.67 2.824x10 1.889x10 037x10 .025x10 3.429x10
20.2 4.809x10
12 1.788x10
13 .784x10 14 6.004x10 13
Table 3. S o l i d P r o p e r t i e s Required i n Eqn. (2)
V a ï >
14 i a
Lit./Mol. P 2 χ 10 MPa
Substance s 308.15K
ν.
n C H 0.4895 6.37619
" 28 58
n C H 0.5058 12.53244
" 29 60
n C H 0.5222 0.36151
~ 30 60
n C H 0.5550 0.02049
" 32 66
n C H 0.5714 0.07973
~ 33 68

PRESSURE.MPa
Figure 3. Experimental and c a l c u l a t e d solubilities of

even-numbered n-alkanes in supercritical ethane at
308.IK. · e x p e r i m e n t a l data for n-C H 2 8 ( k , . = - ·0405); Δ-
5 8
=
e x p e r i m e n t a l data ί θ Γ ( η - 0 Η )
3 0 6 2 —03067; o-experimental
d a t a f o r n - C 3 H ^ ( k ^ = - · 0 3 8 3 ) . C a l c u l a t i o n s u s i n g the P a t e l -
2 6
T e j a e q u a t i o n or s t a t e a r e shown by the s o l i d l i n e s .
-3.0
10 15
PRESSURE.MPa
Figure 4. Experimental and c a l c u l a t e d solubilities of

odd-numbered n-alkanes in supercritical ethane 308.1k.
• e x p e r i m e n t a l data f o r n - C H Q ( k j j = - · 0 0 4 9 ) ; ο e x p e r i m e n t a l
2Q 6
d a t a f o r n-C^Rt^ ( k ^ = - · 0 0 3 7 ) . C a l c u l a t i o n s u s i n g the P a t e l -
T e j a e q u a t i o n o f s t a t e a r e shown by the s o l i d l i n e s .

Figure 5. Enhancement factor ( E ) V S . Carbon number f o r

ethane + n-alkane systems.

Literature Cited
1. Ambrose, D., National Physical Laboratory Report Chem. 57,
December 1976.
2. Chase, J. D., Chem. Eng. Prog., 1984, 80, 63-66.
3. Morawetz, E., J. Chem. Thermo., 1972, 4, 139.
4. Bondi, Α., J. Chem. Eng. Data, 1963, 8, 371.
5. Broadhurst, M.G., J. Res. Nat. Bur. Stand. A, 1962, 66, 241.
6. Muller, Α., Proc. Roy. Soc. Lond. A, 1929, 124, 317.
7. Moradinia, I. and Teja, A. S. Fluid Phase Equil. in press 1986.
8. Kurnik, R. T., Holla
Data, 1981, 26, 47-51.
9. Patel, N. C., and Teja, A. S., Chem. Eng. Sci. 1982, 37, 463-
468.
10. Prausnitz, J. M., "Molecular Thermodynamics of Fluid Phase
Equilibria," Prentice Hall, Englewood-Cliffs N.J., 1969.

Chapter 12
Solubility of meso-Tetraphenylporphyrin
in Two Supercritical Fluid Solvents
T. R. Bergstresser and Michael E . Paulaitis
Department of Chemical Engineering, University of Delaware, Newark, DE 19716
Solubilities of meso-tetraphenylporphyrin (normal

melting temperature = 444°C) in pentane and in toluene
have been measured at elevated temperatures and
pressures. Three-phase, solid-liquid-gas equilibrium
temperatures and pressures were also measured for these
two binary mixture
point of the supercritical-flui
solubility of the porphyrin in supercritical toluene is
three orders of magnitude greater than that in
supercritical pentane or in conventional liquid
solvents at ambient temperatures and pressures. An
analysis of the phase diagram for toluene-porphyrin
mixtures shows that supercritical toluene is the
preferred solvent for this porphyrin because (1) high
solubilities are obtained at moderate pressures, and
(2) the porphyrin can be easily recovered from solution
by small reductions in pressure.
The enhanced solubility of solids in compressed gases at elevated
temperatures and pressures was first noted more than one hundred
years ago. Hannay and Hogarth (1) observed that the solubility of
salts in compressed ethanol was considerably greater than expected
based on the vapor pressure of the salts. Since this early
investigation, numerous authors have discussed the phase behavior of
solids in dense fluids at elevated temperatures and pressures.
Review articles by Paulaitis et al. (2), Luks (3), Streett (4), and
Rowlinson and Richardson (5) document many of the investigations that
have been made.
The phase behavior of solids in supercritical fluids has
practical significance as well as academic interest. Since the mid-
1970's, it has been recognized that supercritical fluids can be
useful as solvents for commercial-scale extractions. While a
variety of applications are documented in the literature (2,6),
supercritical-fluid (SCF) extraction has been particularly useful in
upgrading petroleum fractions (7), extracting volatile components
from coal (8), and deashing oil shale (9) and coal liquids (10). The
0097-6156/87/0329-0138$06.00/0

12. BERGSTRESSER & PAULAITIS Solubility of meso- Tetraphenylporphynn 139
a p p l i c a t i o n o f SCF e x t r a c t i o n i n t h e s e p r o c e s s e s r e q u i r e s
s o l u b i l i t i e s f o r t h e m i x t u r e s of i n t e r e s t i n SCF s o l v e n t s .
S o l u b i l i t i e s can be d i f f i c u l t t o p r e d i c t , however, s i n c e t h e s e
m i x t u r e s are h i g h l y complex i n t h e sense t h a t numerous c o n s t i t u e n t s
are i n v o l v e d which d i f f e r s i g n i f i c a n t l y i n m o l e c u l a r s i z e , shape,
s t r u c t u r e , and p o l a r i t y . E x p e r i m e n t a l s o l u b i l i t i e s on w e l l - d e f i n e d ,
model systems are r e q u i r e d t o develop b e t t e r p r e d i c t i v e methods.
In t h i s p a p e r , we p r e s e n t t h e r e s u l t s of an e x p e r i m e n t a l study
on t h e phase b e h a v i o r o f w e l l - c h a r a c t e r i z e d b i n a r y m i x t u r e s which
r e p r e s e n t t h e more complex m i x t u r e s t h a t a r i s e i n SCF e x t r a c t i o n s of
p e t r o l e u m r e s i d u a and c o a l l i q u i d s . These b i n a r y m i x t u r e s c o n s i s t of
pentane and t o l u e n e w i t h m e s o - t e t r a p h e n y l p o r p h y r i η ( T P P ) . Porphyrins
o c c u r n a t u r a l l y i n crude o i l s (11,12) and r e p r e s e n t an important
c l a s s of high m o l e c u l a r - w e i g h t c o n s t i t u e n t s of t h e s e o i l s , i n c l u d i n g
t h o s e which c o n t a i n heavy m e t a l s , such as n i c k e l and vanadium.
Pentane and t o l u e n e were s e l e c t e d as SCF s o l v e n t s because t h e s e
hydrocarbons have c r i t i c a l t e m p e r a t u r e s c o n v e n i e n t t o t h e d e s i r e d
o p e r a t i n g temperatures f o
liquids, respectively.
S e v e r a l d i f f e r e n t measurements were made as a r e s u l t of the
d i f f e r e n t phase b e h a v i o r observed f o r t h e two b i n a r y m i x t u r e s .
G a s - s o l i d e q u i l i b r i u m was observed f o r m i x t u r e s of TPP and pentane at
c o n d i t i o n s near t h e c r i t i c a l p o i n t of p e n t a n e . Hence, s o l i d
s o l u b i l i t i e s f o r TPP i n s u p e r c r i t i c a l pentane were measured.
However, f o r m i x t u r e s o f TPP and t o l u e n e , a t h i r d ( l i q u i d ) phase
forms i n t h e p r e s e n c e o f t h e gas and t h e s o l i d , at p r e s s u r e s w e l l
below t h e c r i t i c a l p r e s s u r e of t o l u e n e . At h i g h e r p r e s s u r e s ,
g a s - l i q u i d and s o l i d - l i q u i d e q u i l i b r i a were o b s e r v e d , r a t h e r than
gas-solid equilibrium. T h u s , phase c o m p o s i t i o n s f o r g a s - l i q u i d
e q u i l i b r i u m were measured f o r t h i s b i n a r y mixture t o g i v e TPP
s o l u b i l i t i e s i n each o f t h e f l u i d p h a s e s . P r e s s u r e s and t e m p e r a t u r e s
f o r t h r e e - p h a s e , s o l i d - l i q u i d - g a s e q u i l i b r i u m were a l s o measured f o r
both b i n a r y m i x t u r e s .
Experimental Methods
The f o l l o w i n g e x p e r i m e n t a l t e c h n i q u e s were used t o measure t h e

p r e s s u r e s and t e m p e r a t u r e s f o r s o l i d - l i q u i d - g a s e q u i l i b r i u m , phase
c o m p o s i t i o n s (bubble and dew p o i n t s ) f o r g a s - l i q u i d e q u i l i b r i u m , and
s o l i d s o l u b i l i t i e s in s u p e r c r i t i c a l pentane. Experimental procedures
and t h e apparatus a r e d e s c r i b e d i n d e t a i l elsewhere ( 1 3 ) .
S o l i d - l i q u i d - g a s (SLG) e q u i l i b r i u m t e m p e r a t u r e s and p r e s s u r e s
were measured i n a c o n s t a n t - v o l u m e view c e l l . A known amount of
p o r p h y r i n was loaded i n t o t h e c e l l , which was then a t t a c h e d t o t h e
s o l v e n t d e l i v e r y system and heated t o t h e d e s i r e d o p e r a t i n g
temperature. Once thermal e q u i l i b r i u m was o b t a i n e d , s o l v e n t was
metered i n t o t h e c e l l u n t i l t h e p r e s s u r e w i t h i n t h e c e l l reached t h e
SLG p r e s s u r e . E q u i l i b r i u m was o b t a i n e d when t h e p r e s s u r e s t a b l i z e d
and a l l t h r e e phases c o u l d be o b s e r v e d . T h i s p r e s s u r e and t h e
c o r r e s p o n d i n g t e m p e r a t u r e were r e c o r d e d as one p o i n t on t h e SLG
e q u i l i b r i u m l i n e f o r the binary mixture. A d d i t i o n a l p o i n t s were
o b t a i n e d by s e t t i n g a new temperature and r e p e a t i n g t h e p r o c e d u r e .

Bubble p o i n t s f o r g a s - l i q u i d e q u i l i b r i u m were measured at

c o n s t a n t t e m p e r a t u r e by o b s e r v i n g the p r e s s u r e at which the
e q u i l i b r i u m gas phase d i s a p p e a r e d upon i n j e c t i o n of small amounts of
s o l v e n t i n t o the view c e l l . The e q u i l i b r i u m c o m p o s i t i o n of the
l i q u i d phase was o b t a i n e d from t h e known c o m p o s i t i o n i n the c e l l .
Other p r e s s u r e s and c o r r e s p o n d i n g c o m p o s i t i o n s at t h i s temperature
were o b t a i n e d by r e p e a t i n g t h e p r o c e d u r e f o r d i f f e r e n t p o r p h y r i n
loadings.
Dew p o i n t s were a l s o measured u s i n g t h e procedure d e s c r i b e d
above, except t h a t the d i s a p p e a r a n c e of the l i q u i d phase was observed
as s o l v e n t was added t o the view c e l l . Dew p o i n t measurements were
l i m i t e d by low p o r p h y r i n c o n c e n t r a t i o n s i n the gas p h a s e , which
r e q u i r e d l o a d i n g very small amounts of p o r p h y r i n i n t o t h e c e l l .
Measurements of s o l i d s o l u b i l i t i e s i n s u p e r c r i t i c a l pentane
were, i n p r i n c i p l e , i d e n t i c a l t o the bubble p o i n t or dew p o i n t
measurements d e s c r i b e d above. The e q u i l i b r i u m p r e s s u r e and
c o r r e s p o n d i n g s o l i d s o l u b i l i t y at a f i x e d temperature were determined
from the measured p r e s s u r
when the l a s t c r y s t a l of
l i m i t e d at low s o l u b i l i t i e s by the low p o r p h y r i n l o a d i n g s , and at
high s o l u b i l i t i e s by the dark p u r p l e c o l o r of the f l u i d phase which
o b s c u r e d o b s e r v a t i o n of the s o l i d phase.
M e s o - t e t r a p h e n y l p o r p h y r i η (>97% c h l o r i n f r e e ) was purchased from
Man-Win Chemical Company and was used without f u r t h e r p u r i f i c a t i o n .
Pentane and t o l u e n e (ACS c e r t i f i e d grade) were purchased from F i s c h e r
S c i e n t i f i c Company and were degassed b e f o r e u s e .
Experimental Results
The a c c u r a c y of the p r e s s u r e and t e m p e r a t u r e measurements was

v e r i f i e d by measuring the vapor p r e s s u r e curves and c r i t i c a l p o i n t s
f o r pentane and f o r t o l u e n e . Vapor p r e s s u r e s were measured by
o b s e r v i n g the f o r m a t i o n of a l i q u i d phase as pentane or t o l u e n e was
i n j e c t e d i n t o the c o n s t a n t - v o l u m e view c e l l under i s o t h e r m a l
conditions. The o b s e r v a t i o n of c r i t i c a l o p a l e s c e n c e was used t o
determine the c r i t i c a l p o i n t . The measured vapor p r e s s u r e s and
c r i t i c a l p o i n t s are given i n T a b l e I. Vapor p r e s s u r e s d e v i a t e from
Table I. Measured Vapor P r e s s u r e s for Pentane and Toluene
Pentane Toluene
Temperature Vapor P r e s s u r e Temperature Vapor P r e s s u r e
(°C) (atm) (°C) (atm)
84.8 4.6 120.9 1.4
104.5 6.4 159.9 3.4
125.7 10.2 191.9 6.3
134.7 12.2 196.9 7.0
158.3 18.5 224.7 11.1
184.9 28.4 248.9 16.1
196.1 33.9 CP 274.8 23.1
287.6 27.6
299.6 32.1
318.5 40.3 CP
CP = C r i t i c a l Point

12. BERGSTRESSER & PAULAITIS Solubility of meso-Tetraphenylporphynn 141
l i t e r a t u r e values (14,15) by an average of 0.32 atm f o r pentane and

0.10 atm f o r t o l u e n e . C r i t i c a l temperatures and p r e s s u r e s are i n
c l o s e agreement with l i t e r a t u r e values of 197.5°C and 33.6 atm f o r
pentane ( 1 4 ) , and 3 1 8 . 5 7 ° C and 40.6 atm f o r t o l u e n e ( 1 5 ) .
T h r e e - p h a s e , SLG e q u i l i b r i u m temperatures and p r e s s u r e s f o r
b i n a r y mixtures of pentane and t o l u e n e with TPP are given i n T a b l e s
II and III, respectively. A lower c r i t i c a l endpoint (LCEP) was
observed f o r pentane-TPP m i x t u r e s , and i s a l s o denoted i n T a b l e II.
Table II. Measured T h r e e - P h a s e SLG Temperatures and P r e s s u r e s

f o r B i n a r y M i x t u r e s of Pentane
Temperature Pressure
(°C) (atm)
— — 23.0
180.4 25.6
186.9 28.3
192.3
195.0
197.7 33.4
198.3 33.6 LCEP
Table III. Measured T h r e e - P h a s e SLG Temperatures and P r e s s u r e s

f o r B i n a r y M i x t u r e s of Toluene and TPP
Temperature Pressure
(°C) (atm)
286.2 22.2
292.9 24.2
298.8 24.9
299.4 25.1
304.1 26.2
310.6 27.3
315.1 27.7
319.9 28.5
325.0 29.6
325.6 29.5
337.8 30.2
345.2 31.0
350.0 31.1
T h i s LCEP i s a g a s - l i q u i d c r i t i c a l p o i n t i n the presence of t h e s o l i d

phase. A LCEP was not observed f o r t o l u e n e - T P P m i x t u r e s at
temperatures below 3 5 0 ° C . Measurements were not made at h i g h e r
temperatures because of thermal d e g r a d a t i o n of t h e p o r p h y r i n . The
r e s u l t s i n T a b l e s I—III a r e a l s o shown on PT p r o j e c t i o n s i n F i g u r e s 1
and 2. The m i x t u r e c r i t i c a l p o i n t s i n F i g u r e 2 a r e o b t a i n e d from
F i g u r e 4.
S o l i d s o l u b i l i t i e s f o r TPP i n pentane at temperatures of 207°C
and 250°C are given i n T a b l e IV and p r e s e n t e d i n F i g u r e 3. The
maximum e x p e r i m e n t a l u n c e r t a i n t i e s are 3 χ 10"5 f o r p o r p h y r i n mole
f r a c t i o n , 1 atm f o r p r e s s u r e , and 1 degree C f o r t e m p e r a t u r e .

4^
Κ)

140 160 170 200
Temperature ( C)
c
m
70
Figure 1, P r e s s u r e - T e m p e r a t u r e P r o j e c t i o n of Vapor P r e s s u r e o
Curve f o r Pentane and S o l i d - L i q u i d - G a s Equilibrium 73

Curve f o r Pentane-TPP M i x t u r e s . Η
η
>
r
τπ
r
c
DO
m
70
ο
CO
Η
70
m
CO
CO
m
70
SP
>
Ε c
r
>
(Ο
0)
ST

260 270 280 290 360
Temperature ( C) I
"5"
•a
Figure 2. P r e s s u r e - T e m p e r a t u r e P r o j e c t i o n of Vapor P r e s s u r e
Curve f o r Toluene and S o l i d - L i q u i d - G a s Equilibrium

Curve f o r T o l u e n e - T P P M i x t u r e s .
saimj ivDiiiHDHHdns
PORPHYRIN Mole Fraction

no
-B-- 5 0 0 C, Bubble Pts.
• ta. - A - 3 2 5 C, Bubble Pts

525 C , Dew P t s
-Θ- 3 5 0 C, Bubble Pts
• 3 5 0 C , Dew P t s
te-

T" —ι 1 Γ
0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 O.K 0.18 0.20 0.22
Mole Fraction PORPHYRIN
Figure 4, Bubble and Dew P o i n t s f o r T o l u e n e - T P P M i x t u r e s at

300 , 325 , and 3 5 0 ° C .
Table IV. Measured S o l i d Solubilities of TPP i n Compressed Pentane
Pressure Mole F r a c t i o n
(atm) TPP χ 10*
T=207 C U
125 1.0
132 1.3
159 1.4
190 1.6
T=250°C
89 1.1
115 2.1
137 2.7
169 3.0
220 3.1
The normal m e l t i n g p o i n t of TPP was measured u s i n g a

d i f f e r e n t i a l scanning c a l o r i m e t e r
experimental r e s u l t s in Figur
melt at t e m p e r a t u r e s of 3 0 0 - 3 5 0 ° C i n the presence of compressed
t o l u e n e at p r e s s u r e s of 20-30 atm (well below the c r i t i c a l p r e s s u r e
of t o l u e n e ) . At h i g h e r p r e s s u r e s , g a s - l i q u i d and s o l i d - l i q u i d
e q u i l i b r i a , r a t h e r than g a s - s o l i d e q u i l i b r i u m , w i l l be o b t a i n e d f o r
t o l u e n e - T P P m i x t u r e s . Bubble p o i n t s and dew p o i n t s f o r t h i s b i n a r y
m i x t u r e were measured at t e m p e r a t u r e s of 3 0 0 ° , 3 2 5 ° , and 3 5 0 ° , and
p r e s s u r e s above t h e c o r r e s p o n d i n g SLG e q u i l i b r i u m p r e s s u r e s . The
r e s u l t s are given i n T a b l e V and shown i n F i g u r e 4. The maximum
T a b l e V. Measured Bubble and Dew P o i n t s f o r Binary Mixtures of

T o l u e n e and TPP
T= 300°C T=325°C T=350°C

Mole Mole Mole
Pressure Fraction Pressure Fraction Pressure Fraction
(atm) TPPxlO 2
(atm) TPPxlO 2
(atm) TPPxlO 2
Bubble P o i n t s Bubble P o i n t s
27 18.40 32 18.80 39 21.50
28 12.80 34 15.20 40 19.80
29 8.26 35 13.90 43 16.40
30 5.08 37 11.60 46 12.80
31 2.46 39 8.78 48 9.62
32 .70 40 7.36 50 7.18
32 .08 41 4.78 51 4.88
41 3.31 53 3.38
42 1.77 56 1.97
43 .38 57 1.37
43 .15 Dew P o i n t s
43 .12 56 .79
Dew P o i n t s 57 .44
41 .09 52 .30
38 .04 54 .26
38 .02 51 .24
54 .21

12. BERGSTRESSER & PAULAITIS Solubility of mô-Tetraphenylporphynn 147
e x p e r i m e n t a l u n c e r t a i n t i e s f o r bubble and dew p o i n t mole f r a c t i o n s

are 10% o f t h e r e p o r t e d v a l u e s . Maximum e x p e r i m e n t a l u n c e r t a i n t i e s
are 1 atm f o r p r e s s u r e and 2 degrees f o r t e m p e r a t u r e at 3 5 0 ° C .
Discussion
The m e l t i n g b e h a v i o r f o r TPP i n t h e p r e s e n c e o f compressed pentane

( F i g u r e 1) i s c h a r a c t e r i z e d by an i n t e r r u p t e d t h r e e - p h a s e , SLG
e q u i l i b r i u m l i n e which t e r m i n a t e s at a LCEP. This behavior i s
c h a r a c t e r i s t i c o f a gas and a s o l i d with low mutual s o l u b i l i t y , and
i s expected when t h e t r i p l e - p o i n t t e m p e r a t u r e of t h e s o l i d i s much
g r e a t e r than t h e c r i t i c a l t e m p e r a t u r e of t h e gas ( 3 ) . At
t e m p e r a t u r e s j u s t above t h e LCEP t e m p e r a t u r e , TPP does not melt i n
t h e presence of compressed p e n t a n e , and g a s - s o l i d e q u i l i b r i u m i s
o b s e r v e d at p r e s s u r e s up t o two hundred atmospheres ( F i g u r e 3 ) .
The s o l u b i l i t y o f TPP i n s u p e r c r i t i c a l pentane at t h e s e e l e v a t e d
pressures i s also quite low At 2 5 0 ° C t h e maximum s o l u b i l i t y i s
a p p r o x i m a t e l y 2.7 χ 1 0 "
The m e l t i n g b e h a v i o
t o l u e n e i s s i g n i f i c a n t l y d i f f e r e n t ( F i g u r e 2 ) . The t h r e e - p h a s e , SLG
e q u i l i b r i m curve does not show a LCEP, and p r o b a b l y c o n t i n u e s
w i t h o u t i n t e r r u p t i o n t o t h e t r i p l e p o i n t o f TPP. T h i s b e h a v i o r i s
c h a r a c t e r i s t i c o f b i n a r y m i x t u r e s with r e l a t i v e l y high mutual
solubilities. F o r SLG e q u i l i b r i u m , t h e l i q u i d phase would have high
TPP c o n c e n t r a t i o n s ; whereas t h e gas phase would be mostly t o l u e n e and
t h e s o l i d phase would be e s s e n t i a l l y pure TPP. The p r e s s u r e -
c o m p o s i t i o n diagram d e p i c t i n g g a s - l i q u i d e q u i l i b r i u m f o r t o l u e n e - T P P
m i x t u r e s ( F i g u r e 4) i n d i c a t e s t h a t l i q u i d - p h a s e c o n c e n t r a t i o n s of TPP
can be on t h e o r d e r o f 20 mol % at 350°C and 40 atm.
A comparison o f s o l i d s o l u b i l i t i e s f o r TPP i n s u p e r c r i t i c a l
p e n t a n e , s u p e r c r i t i c a l t o l u e n e , and v a r i o u s l i q u i d s o l v e n t s i s given
i n T a b l e V I . The s o l i d s o l u b i l i t y o f TPP i n t o l u e n e c o r r e s p o n d s t o
t h e l i q u i d - p h a s e c o n c e n t r a t i o n f o r SLG e q u i l i b r i u m , e s t i m a t e d from
t h e r e s u l t s i n F i g u r e s 2 and 4. S e v e r a l i m p o r t a n t c o n c l u s i o n s can be
Table VI. Comparison o f S o l i d S o l u b i l i t i e s of TPP i n V a r i o u s

Solvents
Solvent Mole F r a c t i o n Conditions

TPP χ 1 0 4
Toluene 2210.00 T=325°C,f>=3U atm

Pentane 2.71 T=250°C,P=137 atm
P y r i d i n e (16) 6.30 ambient
Benzene (16) 5.20 ambient
Acetone (17) 1.40 ambient
E t h a n o l (17) .01 ambient
drawn from t h i s c o m p a r i s o n . F i r s t , TPP s o l u b i l i t y i n s u p e r c r i t i c a l

t o l u e n e i s t h r e e o r d e r s of magnitude g r e a t e r than t h a t i n
s u p e r c r i t i c a l pentane and i n t h e l i q u i d s o l v e n t s at ambient
t e m p e r a t u r e s and p r e s s u r e s . O b v i o u s l y , the higher temperature
a s s o c i a t e d with s u p e r c r i t i c a l t o l u e n e must be a s i g n i f i c a n t f a c t o r .
However, t h e chemical nature of t h e s o l v e n t i s a l s o i m p o r t a n t , as

Library
1155 16th St., N.W.
demonstrated by the f a c t t h a t t h e enhancement f a c t o r (2) c a l c u l a t e d

f o r TPP i n t o l u e n e i s about one o r d e r of magnitude g r e a t e r than t h a t
c a l c u l a t e d f o r TPP i n s u p e r c r i t i c a l p e n t a n e . Second, the high
s o l u b i l i t y i n t o l u e n e i s o b t a i n e d at a moderate p r e s s u r e , 30 atm,
w e l l below the c r i t i c a l p r e s s u r e of t o l u e n e . This pressure
c o r r e s p o n d s t o the SLG e q u i l i b r i u m p r e s s u r e at 3 2 5 ° C . T h i r d , the SLG
p r e s s u r e of 30 atm r e p r e s e n t s t h e minimum p r e s s u r e f o r high TPP
s o l u b i l i t i e s i n t o l u e n e at t h i s t e m p e r a t u r e — i . e . , the minimum
p r e s s u r e f o r the e x i s t e n c e of the l i q u i d p h a s e . At lower p r e s s u r e s ,
o n l y the gas and s o l i d phases w i l l f o r m , c o r r e s p o n d i n g t o essentially
complete s e p a r a t i o n of t o l u e n e and the p o r p h y r i n . In summary, the
comparison i n T a b l e VI i n d i c a t e s t h a t s u p e r c r i t i c a l t o l u e n e would be
t h e p r e f e r r e d s o l v e n t f o r m e s o - t e t r a p h e n y l p o r p h y r i η based upon the
h i g h TPP s o l u b i l i t i e s , moderate o p e r a t i n g p r e s s u r e s , and the ease
w i t h which the p o r p h y r i n can be r e c o v e r e d from s o l u t i o n by r e d u c i n g
t h e p r e s s u r e below t h e SLG e q u i l i b r i u m p r e s s u r e .
Acknowledgments
F i n a n c i a l support from the N a t i o n a l Science F o u n d a t i o n (CPE

8000276) i s g r a t e f u l l y acknowledged.
Literature Cited
1. Hannay, J. B.; Hogarth, J. Proc. Roy. Soc. (London) 1879, 29,
324.
Rev. in Chem. Eng. 1983, 1, 179.
3. Luks, K. D. Proc. 2nd Intern. Conf. on Phase Equilibria and
Fluid Properties in the Chemical Industry, Berlin, 1980.
4. Streett, W. B. Can. J. Chem. Eng. 1974, 52, 92.
5. Rowlinson, J. S.; Richardson, M. J. "Advances in Chemical
Physics. Vol. II", Interscience Publishers, Inc.: New York,
1959.
6. Williams, D. F. Chem. Eng. Sci. 1981, 36, 1769.
7. Gearhart, J. Α.; Garwin, L. Hydrocarb. Proc. 1976, 55, 125.
8. Maddocks, R. R.; Gibson, J. Chem. Eng. Prog. 1977, 73, 59.
9. Clapper, T. W. U. S. Patent 4 162 965, 1979
10. Baldwin, R. Α.; Davis, R. E.; Wing, H. F. paper presented at the
4th Intern. Conf. on Coal Gasification, Liquefaction, and
Conversion to Electricity, Pittsburgh, 1977.
11. Baker, E. W.; Palmer, S. E. "Geochemistry of Porphyrins" Part
A; Dolphin, D.; Ed.; Academic Press: New York, 1978.
12. Didyk, B.; Alturki, Y. I. Α.; Pillinger, C. T.; Eglinton, G.
Chem. Geology 1975, 15, 193.
13. Bergstresser, T. R.; Ph.D. Thesis, University of Delaware, 1986.
14. Sage, B. H.; Lacey, W. N. Ind. Eng. Chem. 1942, 34, 730.
15. Ambrose, D.; Broderick, B. E.; Townsend, R. J. Chem. Soc. A
1967, 633.
16. Koifman, O. I.; Berezin, B. D.; Zelov, V. V.; Nikitina, G. E.
Russ. J. Phys. Chem. 1978, 52, 1032.
17. Berezin, B. D.; Koifman, O. I.; Zelov, V. V.; Nikitina, G. E.
Russ. J. Phys. Chem. 1978, 52, 1281.

Chapter 13
Supercritical Fluid Adsorption

at the Gas-Solid Interface
1
Jerry W. King
CPC International, Moffett Technical Center, Argo, IL 60501
Adsorption of a supercritical fluid upon the surface

of an adsorbent significantly alters the gas-solid
interface thereby
of bound adsorbates. Such a process can contribute
substantially to the regeneration of adsorbents and
the chromatographic separation of solutes as reported
in the scientific and patent literature. In this
paper, we have characterized the adsorption of dense
gases at solid interfaces in terms of their reported
adsorption isotherms. Particular emphasis has been
placed on the pressure at which maximum differential
adsorption of the gas occurs and its importance in
assuring rapid breakthrough of sorbates from packed
columns. An experimental approach is presented for
determining adsorbate breakthrough volumes as a function
of gas compression using elution pulse chromatographic
techniques. The derived retention volume data define
distinct regions of solute breakthrough characteristics
which are determined by the relative uptake of the
compressed fluid on the sorbent surface. The results
obtained in this study permit an estimation of the
physical conditions required to effectively remove
aliphatic and aromatic hydrocarbons from such sorbents
as alumina and porous organic resins with minimal
compression of the supercritical fluid phase.
The utilization of supercritical fluids in conjunction with
adsorbents and active solids is well documented in the technical
literature. The most frequently cited applications involve the
use of dense gases for the regeneration of adsorbents (1) and as
mobile phases in supercritical fluid chromatography (2). Numerous
'Current address: Northern Regional Research Center, Agricultural Research Service,
U.S. Department of Agriculture, 1815 North University Street, Peoria, IL 61604
0097-6156/87/0329-0150$06.50/0

13. KING Supercritical Fluid Adsorption at the Gas-Solid Interface 151
p a t e n t s a l s o c o n t a i n examples o f the removal o f s p e c i f i c s o l u t e s ,

such as c a f f e i n e o r n i c o t i n e , from s u p e r c r i t i c a l f l u i d media by
activated carbon (3, 4) and ion exchange resins (5, 6 ) .
F r a c t i o n a t i o n o f s o l u t e s from dense gas streams has a l s o been
demonstrated by B a r t o n and H a j n i k (7) u t i l i z i n g m o l e c u l a r s i e v e s
as a s o r b e n t . L e s s w e l l known, b u t o f h i s t o r i c a l i m p o r t a n c e , i s
the s o r p t i o n o f methane by c o a l ( 8 ) , an e q u i l i b r i a o f importance
in p r e v e n t i n g mine e x p l o s i o n s . R e c e n t l y , Findenegg (9) has
s u g g e s t e d t h a t r a d i o a c t i v e gases may be s t o r e d t o advantage on
z e o l i t e s at elevated pressures.
Regeneration o f a d s o r b e n t s was initially demonstrated in
1
the mid-1970 s i n b o t h Japan (10) and the U n i t e d S t a t e s (11, 12).
In r e s e a r c h sponsored by the E n v i r o n m e n t a l P r o t e c t i o n Agency
(13-15), Critical Fluid Systems, Inc. ( A r t h u r D. Little)
demonstrated the f e a s i b i l i t y of regenerating a c t i v a t e d carbon
and o r g a n i c r e s i n s u s i n g s u p e r c r i t i c a l carbon d i o x i d e . Typical
c o n d i t i o n s i n the above s t u d i e s u t i l i z i n g C 0 2 f o r the removal o f
s e l e c t e d s o r b a t e s from
reduced s t a t e i n F i g u r
range o f reduced temperature and p r e s s u r e have been employed
depending upon t h e c h e m i c a l n a t u r e o f t h e compounds b e i n g d e s o r b e d .
Presumably, t h e s e r e g e n e r a t i o n c o n d i t i o n s were s e l e c t e d e m p i r i c a l l y
o r a r e based on independent measurements o f s o r b a t e ( s o l u t e )
s o l u b i l i t y i n the s u p e r c r i t i c a l f l u i d .
More r e c e n t l y , Kander and P a u l a i t i s (16) have s t u d i e d the
a d s o r p t i o n o f p h e n o l onto a c t i v a t e d c a r b o n and measured i t s
sorption equilibria from dense C 0 .
2 These r e s e a r c h e r s found
that temperature c o n t r o l l e d the a d s o r p t i o n e q u i l i b r i a and that
p h e n o l uptake was n e g l i g i b l y e f f e c t e d by changes i n the gas
phase d e n s i t y . Such a r e s u l t i n d i c a t e s t h a t f a c t o r s o t h e r t h e n
a s o l u t e ' s s o l u b i l i t y i n a dense gas p l a y a key r o l e i n d e f i n i n g
the a d s o r p t i o n e q u i l i b r i u m which accompany such p r o c e s s e s .
There i s a s y n e r g i s m between a d s o r p t i o n and c h r o m a t o g r a p h i c
processes which is clearly demonstrated i n the supercritical
fluid literature. Research i n s u p e r c r i t i c a l f l u i d chromatography
can u s u a l l y be divided into analytical applications and the
measurement o f p h y s i c o c h e m i c a l d a t a . Early a n a l y t i c a l separations
methodology performed a t p r e s s u r e s c l o s e t o ambient conditions
showed t h a t the e l u t i o n o r d e r o f i n j e c t e d solutes could be
a l t e r e d by c h a n g i n g the n a t u r e o f the c a r r i e r gas (17-20).
L a t e r , a d s o r b e n t s and c r o s s l i n k e d p o l y m e r i c p a c k i n g s were u t i l i z e d
i n a n a l y t i c a l s t u d i e s t o c i r c u m v e n t the problem o f s t a t i o n a r y
phase v o l a t i l i t y i n the h i g h l y compressed carrier gas. For
example, S i e and R i j n d e r s (21, 22) demonstrated the advantages
o f u s i n g such a d s o r b e n t s as alumina and m i c r o p o r o u s polymers f o r
fractionating a wide v a r i e t y of mixtures i n c l u d i n g polycyclic
aromatics hydrocarbons, alkaloids, and epoxy r e s i n o l i g o m e r s .
R e s u l t s o b t a i n e d i n the above s t u d y i n d i c a t e d t h a t the s o l u t e
distribution coefficients could be v a r i e d as a f u n c t i o n o f
carrier gas p r e s s u r e i n a r a t h e r d r a m a t i c f a s h i o n and that
e l u t i o n peak shape was s u b s t a n t i a l l y m o d i f i e d by the i n t e r a c t i o n
o f the s u p e r c r i t i c a l f l u i d w i t h t h e s o r b e n t s u r f a c e . Kobayashi
and co-workers (23-28) u s i n g t r a c e r p e r t u r b a t i o n chromatography
have s u b s t a n t i a t e d the above f i n d i n g s and d e t e r m i n e d e q u i l i b r i u m
K - v a l u e s , i s o t h e r m s , and thermodynamic f u n c t i o n s o f a d s o r p t i o n
f o r l i g h t h y d r o c a r b o n s on s e v e r a l a d s o r b e n t s .

In t h i s p a p e r , we have u t i l i z e d l i t e r a t u r e d a t a i n tandem
w i t h p u l s e c h r o m a t o g r a p h i c measurements t o d e f i n e t h e r o l e o f
supercritical fluid adsorption a t the g a s - s o l i d i n t e r f a c e . I t
s h o u l d be a p p r e c i a t e d t h a t t h e a d s o r p t i o n o f t h e s u p e r c r i t i c a l
f l u i d on t h e a d s o r b e n t s u r f a c e i s a p p r e c i a b l e a t h i g h e r p r e s s u r e s
leading t o the formation o f a condensed phase (29) i n t h e
microporous adsorbents commonly used i n r e g e n e r a t i o n e x p e r i m e n t s .
The f o r m a t i o n o f such a " l i q u i d - l i k e " f i l m a t t h e i n t e r f a c e c a n
have a p r o f o u n d effect i n determining t h e uptake o f another
adsorbate at the s o l i d surface or i n the c o n d i t i o n s r e q u i r e d f o r
r e g e n e r a t i o n o f the adsorbent surface. The measurements r e p o r t e d
in this study extend o u t t o 1600 atmospheres, a compression
regime p r e v i o u s l y unexplored by g a s - s o l i d chromatography. Such
experiments have permitted us t o c o r r e l a t e chromatographic
retention volume measurements with adsorbate breakthrough
c h a r a c t e r i s t i c s as a f u n c t i o n o f p r e s s u r e f o r s e v e r a l adsorbent/
adsorbate systems. The r o l e o f t h e s u p e r c r i t i c a l f l u i d a t t h e
g a s - s o l i d i n t e r f a c e ha
characteristics, therefor
g o v e r n i n g t h e a d s o r p t i o n o f h i g h p r e s s u r e gases a t t h e a d s o r b e n t
i n t e r f a c e w i l l be g i v e n .
Fundamentals o f S u p e r c r i t i c a l F l u i d Adsorption
Fundamental s t u d i e s on t h e a d s o r p t i o n o f s u p e r c r i t i c a l f l u i d s a t
the g a s - s o l i d i n t e r f a c e a r e r a r e l y c i t e d i n t h e s u p e r c r i t i c a l
fluid extraction literature. This i s most u n f o r t u n a t e since
e q u i l i b r i u m s h i f t s i n d u c e d by gas phase n o n - i d e a l i t y i n m u l t i p h a s e
systems c a n r a r e l y be t o t a l l y a t t r i b u t e d t o s o l u t e s o l u b i l i t y i n
the s u p e r c r i t i c a l f l u i d phase. The p a r t i t i o n i n g o f an adsorbed
s p e c i e between t h e i n t e r f a c e and gaseous phase c a n be governed
by a complex a r r a y o f m o l e c u l a r i n t e r a c t i o n s which depend on t h e
relative intensity of the adsorbate-adsorbent interactions,
adsorbate-adsorbate a s s o c i a t i o n , the s o r p t i o n o f the s u p e r c r i t i c a l
f l u i d a t t h e s o l i d i n t e r f a c e , and t h e s o l u b i l i t y o f t h e s o r b a t e
i n the c r i t i c a l fluid. As we s h a l l demonstrate, competitive
a d s o r p t i o n between t h e s o r b a t e and t h e s u p e r c r i t i c a l f l u i d a t
the g a s - s o l i d i n t e r f a c e i s a s i g n i f i c a n t mechanism which s h o u l d
be considered i n the proper design of adsorption/desorption
methods which i n c o r p o r a t e dense gases as one o f t h e a c t i v e
phases.
I n g e n e r a l , a d s o r p t i o n o f a h i g h p r e s s u r e gas f o l l o w s a
Type I I BET i s o t h e r m . The shape o f t h e i s o t h e r m i s p a r t l y
dependent on t h e u n i t s chosen f o r t h e i s o t h e r m coordinates,
however t h e r e i s a major d i f f e r e n c e i n t h e c h a r a c t e r o f t h e
i s o t h e r m depending on whether a b s o l u t e o r Gibb's a d s o r p t i o n i s
chosen f o r the a b s c i s s a . Whereas a b s o l u t e adsorption i s a
measure o f t h e t o t a l mass o r volume o f t h e gas adsorbed onto t h e
s u r f a c e , Gibb's a d s o r p t i o n ( o r t h e s u r f a c e e x c e s s ) measures t h e
amount o f gas adsorbed on t h e s o l i d s u r f a c e i n excess o f t h a t
corresponding t o t h e d e n s i t y o f gas i n t h e f l u i d phase a t t h e
same temperature and p r e s s u r e . This l a t t e r d e f i n i t i o n provides
some i n s i g h t as t o t h e m o l e c u l a r interactions taking place at
the i n t e r f a c e as a f u n c t i o n o f gas d e n s i t y . A t y p i c a l a d s o r p t i o n
isotherm i l l u s t r a t i n g b o t h t h e a b s o l u t e and d i f f e r e n t i a l (Gibbs)
a d s o r p t i o n i s shown i n F i g u r e 2.

KING Supercritical Fluid Adsorption at the Gas-Solid Interface
REDUCED DENSITY
F i g u r e 1. Reported c o n d i t i o n s f o r the s u p e r c r i t i c a l fluid

desorption o f s e l e c t e d adsorbates from a c t i v a t e d c a r b o n .
PRESSURE • ··
F i g u r e 2. T y p i c a l a d s o r p t i o n i s o t h e r m f o r a s u p e r c r i t i c a l gas
i n w h i c h a b s o l u t e and d i f f e r e n t i a l a d s o r p t i o n a r e e x p r e s s as a
function o f pressure.

Menon has n o t e d i n h i s comprehensive review (30) t h a t an

a d s o r p t i o n maxima o c c u r s as a s p e c i f i c gas p r e s s u r e , ρ , when
the Gibbs a d s o r p t i o n i s p l o t t t e d v e r s u s t h e gas p r e s s u r e . These
a d s o r p t i o n maxima a r e q u i t e pronounced when t h e s u p e r c r i t i c a l
fluid i s adsorbed a t reduced temperatures approaching unity.
F u r t h e r c o m p r e s s i o n o f t h e c r i t i c a l f l u i d beyond ρ results i n
a d e n s i t y i n c r e a s e o f t h e adsorbed f i l m and a c o n c o m i t a n t d e c r e a s e
i n t h e s u r f a c e e x c e s s as t h e gas phase approaches a density
e q u a l t o o r e x c e e d i n g t h a t o f t h e adsorbed phase. As we s h a l l
show l a t e r , a t t a i n m e n t o f t h i s s p e c i f i c p r e s s u r e v a l u e i s c r i t i c a l
for s a t u r a t i n g t h e a d s o r b e n t s u r f a c e w i t h t h e compressed fluid
and t h e r e b y l e a d i n g t o c o n d i t i o n s which f a v o r t h e d e s o r p t i o n o f
the bound solute from the surface region. Menon (31) has
c o r r e l a t e d the occurence o f ρ f o r v a r i o u s gases i n terras o f
max
their respective critical properties and has p r o p o s e d the
f o l l o w i n g e m p i r i c a l e q u a t i o n which i s a p p l i c a b l e f o r a d s o r p t i o n
Q
on macroporous a d s o r b e n t
where Ρ = c r i t i c a l p r e s s u r e o f t h e gas
T^ = reduced temperature a t which a d s o r p t i o n o c c u r s
The above r e l a t i o n s h i p p r e d i c t s a monotonie i n c r e a s e i n P m a x
w i t h i n c r e a s i n g temperature as shown i n F i g u r e 3 f o r t h r e e
d i f f e r e n t gases. Hence, t h e maximum amount o f gas (by t h e Gibbs
d e f i n i t i o n ) adsorbed on t h e s u r f a c e o f t h e a d s o r b e n t c a n be
a t t a i n e d a t a lower p r e s s u r e by o p e r a t i n g c l o s e t o t h e c r i t i c a l
temperature o f the adsorbed gas. A p p l i c a t i o n o f even h i g h e r
p r e s s u r e s then ρ will result i n a large increase i n the
ma
c o h e s i o n a l e n e r g y ( ? f t h e a d s o r b e d gas l e a d i n g t o t h e f o r m a t i o n
of a l i q u i d - l i k e l a y e r on t h e s u r f a c e o f t h e porous a d s o r b e n t
(27).
A d d i t i o n a l s t u d i e s by Menon (32) have i n d i c a t e d t h e P m a x
can o c c u r a t lower p r e s s u r e s t h e n t h o s e p r e d i c t e d by E q u a t i o n 1
depending on t h e p o r e s t r u c t u r e a s s o c i a t e d w i t h t h e a d s o r b e n t .
E m p i r i c a l l y , adsorbents p o s s e s s i n g m i c r o p o r o s i t y e x h i b i t a
that i s 0.6-0.8 o f t h e v a l u e p r e d i c t e d by E q u a t i o n 1. This
o b s e r v a t i o n i s a t t r i b u t e d t o the o v e r l a p p i n g o f p o t e n t i a l f i e l d s
i n t h e a d s o r b e n t p o r e s , t h e r e b y e n h a n c i n g s o r p t i o n o f t h e gas a t
lower p r e s s u r e s . E x p e r i m e n t a l s t u d i e s by Ozawa (33) have v e r i f i e d
t h i s t r e n d as shown i n F i g u r e 4 f o r t h e C 0 / a c t i v a t e d c a r b o n
2
system. Here t h e a d s o r p t i o n maxima f o r t h e gas o c c u r s a t a

lower p r e s s u r e t h a n t h e c r i t i c a l p r e s s u r e o f c a r b o n d i o x i d e . I t
s h o u l d a l s o be n o t e d t h a t t h e amount o f gas adsorbed i s d e c r e a s e d
at h i g h e r reduced t e m p e r a t u r e s and t h a t a d d i t i o n a l compression
i s r e q u i r e d t o r e a c h a d e f i n e d a d s o r p t i o n maxima ( i . e . , a t v e r y
high values of Τ i t i s sometimes d i f f i c u l t t o d i s c e r n a w e l l -
defined a d s o r p t i o n maximum). The above t r e n d has a l s o been
found f o r other adsorbent/adsorbate systems, such as silica
gel/C0 . 2
The dependence o f gas a d s o r p t i o n on t h e pore s t r u c t u r e o f

the s o r b e n t has been e x t e n s i v e l y s t u d i e d by Ozawa, Kusumi, and
Ogino (34) and t h e o r e t i c a l l y c o r r e l a t e d by a p p l i c a t i o n o f t h e
P i c k e t t e q u a t i o n . Data o b t a i n e d from t h i s s t u d y has been p l o t t e d

KING Supercritical Fluid Adsorption at the Gas-Solid Interface 155
F i g u r e 4. A d s o r p t i o n i s o t h e r m s f o r the c a r b o n d i o x i d e / a c t i v a t e d
c a r b o n system. Reproduced w i t h p e r m i s s i o n from Ref. 33. Copy-
r i g h t 1972, Chemical S o c i e t y o f Japan.

in Figure 5 where the ρ v a l u e v e r s u s the mean pore diameter

max
of the adsorbent ( a c t i v a t e d c a r b o n ) i s shown f o r C 0 2 sorption.
The a d s o r p t i o n maxima i n t h i s c a s e , i n c r e a s e s w i t h increasing
pore diameter, a s y m p o t i c a l l y approaching a constant value at
l a r g e pore diameters. The v a l u e p r e d i c t e d by Menon's r e l a t i o n s h i p
( E q u a t i o n 1) has a l s o been i n c l u d e d f o r the purpose o f comparison.
Although i t would seem p r u d e n t t o u t i l i z e an a d s o r b e n t o f low
p o r o s i t y t o a v o i d a d d i t i o n a l gas compression, m i t i g a t i n g f a c t o r s
such as a d s o r p t i o n c a p a c i t y and s t e r e o - s e l e c t i v i t y a l s o p l a y a
seminal role i n the f i n a l s e l e c t i o n o f a s u i t a b l e adsorbent.
The pore s i z e dependence o f ρ a t v a r i o u s temperatures has
a l s o been v e r i f i e d f o r above carlfons and shows a s i m i l a r dependence
t o t h a t e x h i b i t e d i n F i g u r e 3.
F u r t h e r d i s c u s s i o n on the t h e o r e t i c a l a s p e c t s o f s u p e r c r i t i c a l
f l u i d a d s o r p t i o n on s o l i d s can be found by c o n s u l t i n g the papers
of Findenegg (35-37). The importance o f the h i g h p r e s s u r e
a d s o r p t i o n maximum as d i s c u s s e
compare t y p i c a l ρ value
with conditions ar y employe regeneratio
of adsorbents ( F i g u r e 1). As shown i n F i g u r e 6, ρ values f o r
C0 2 on typical carbonaceous a d s o r b e n t s occur at c o n s i d e r a b l y
lower reduced p r e s s u r e s (p = 0.5-1.0) t h a n those u t i l i z e d f o r
the d e s o r p t i o n o f common o r g a n i c s o l u t e s (14) o r p e s t i c i d e s ( 1 ) .
T h i s r e s u l t i m p l i e s t h a t p o t e n t i a l l y much lower p r e s s u r e s and
volumes o f s u p e r c r i t i c a l C 0 2 c o u l d be used t o d i s p l a c e adsorbed
s o l u t e s from the a d s o r b e n t s u r f a c e by m a x i m i z i n g the c o m p e t i t i v e
a d s o r p t i o n o f the dense C 0 on the s o l i d s u r f a c e .
2
To provide some e x p e r i m e n t a l verification of the above

h y p o t h e s i s , we have measured v i a p u l s e e l u t i o n chromatography,
breakthrough volumes (the peak maximum retention volume in
l i n e a r e l u t i o n chromatography c o r r e s p o n d i n g t o the 50% breakthrough
volume i n f r o n t a l a n a l y s i s ) o f model a d s o r b a t e s on two d i f f e r e n t
adsorbents over an extended pressure range u s i n g C 0 2 as the
critical fluid. Our e x p e r i m e n t a l r e s u l t s s u g g e s t t h a t t h e r e a r e
d i s t i n c t r e g i o n s i n which the s u r f a c e o f the a d s o r b e n t i s u n d e r g o i n g
m o d i f i c a t i o n due t o the a d s o r p t i o n o f the s u p e r c r i t i c a l fluid
c a r r i e r gas. The i m p l i c a t i o n s o f t h e s e r e s u l t s have p e r m i t t e d
the i d e n t i f i c a t i o n o f d i s t i n c t p r e s s u r e ranges which can be used
f o r the fractionation of d i s s o l v e d moieties i n the critical
f l u i d , a minimum p r e s s u r e which s h o u l d be a t t a i n e d f o r commencement
of adsorbent r e g e n e r a t i o n , and a upper p r e s s u r e l i m i t a t which
sorbate breakthrough volume becomes constant with increasing
pressure.
Experimental Measurements
The experimental apparatus utilized f o r these studies i s of

s i m i l a r d e s i g n t o t h a t r e p o r t e d by G i d d i n g s , Myers, and King
(38) as i s d e p i c t e d i n F i g u r e 7. Compression o f the mobile
phase was accomplished u s i n g an Aminco a i r - a c t u a t e d diaphragm
compressor which was kept i n a heated chamber above the c r i t i c a l
temperature of the carrier gas. Pump p u l s a t i o n s and flow
i r r e g u l a r i t i e s were m i n i m i z e d by s t o r i n g the compressed f l u i d i n
a h i g h p r e s s u r e b a l l a s t chamber which s e r v e d as a s o u r c e o f
m o b i l e phase. P r e s s u r e s up t o 3000 p s i g were a d j u s t e d by u s i n g

F i g u r e 5. R e l a t i o n s h i p between t h e p r e s s u r e a t which maximum

d i f f e r e n t i a l a d s o r p t i o n o f c a r b o n d i o x i d e o c c u r s and t h e mean
pore diameter o f a c t i v a t e d carbons.

REDUCED DENSITY
F i g u r e 6. R e p o r t e d a d s o r p t i o n maxima f o r c a r b o n d i o x i d e /
a d s o r b e n t system on a p l o t o f reduced s t a t e . ( I ) and ( I I )
r e p r e s e n t d i f f e r e n t t y p e s o f a c t i v a t e d carbon (AC) .

KING Supercritical Fluid Adsorption at the Gas-Solid Interface
CARY MODEL 31 •f
RECORDER ELECTROMETER
VOj IfiRATED
VALVE
SPLITTER
F i g u r e 7. E x p e r i m e n t a l h i g h p r e s s u r e gas chromatographic
a p p a r a t u s f o r r e t e n t i o n volume measurements.

an Apco b a c k p r e s s u r e r e g u l a t o r i n c o n j u n c t i o n w i t h a Bourdon
tube gauge. R e g u l a t i o n o f p r e s s u r e s beyond 3000 p s i g was a c h i e v e d
by i s o l a t i n g the low p r e s s u r e gauge from the main f l o w system
and subsequently r e g u l a t i n g the e n t i r e chromatographic system
w i t h a d u a l c o n t a c t e l e c t r i c a l c o n t r o l gauge ( m o d i f i e d Aminco
Model 47-18330). The sampling chamber/valve and column were
p l a c e d i n a h e a t e d , t h e r m o s t a t t e d oven h e l d a t 40°C (dashed l i n e
i n F i g u r e 7) .
Column design and preparation incorporated previously
d e s c r i b e d methods r e p o r t e d i n the l i t e r a t u r e ( 3 9 ) . Two d i f f e r e n t
a d s o r b e n t s were employed: a 100/120 mesh c r o s s l i n k e d s t y r e n e /
divinylbenzene resin ( P o l y p a k P-Waters A s s o c i a t e s ) and a Woelm
aniontropic activity grade alumina. These adsorbents were
packed i n 300 and 94 cm. s t a i n l e s s s t e e l columns h a v i n g a 1 mm.
i n t e r n a l diameter. P r e s s u r e drop a c r o s s the a d s o r b e n t bed was
kept t o a minimum (<0.02 atm.) by u s i n g a h e a t e d p r e s s u r e r e d u c t i o n
v a l v e a t the end o f the column. T y p i c a l l i n e a r flow v e l o c i t i e s
t h r o u g h the columns wer
Pneumatic transpor
the end o f the column t o the d e t e c t o r o r i f i c e was f a c i l i t a t e d by
a p p l i c a t i o n o f a h e a t i n g tape to a s m a l l l e n g t h of narrow bore
tubing. D e t e c t i o n o f the s o l u t e e l u t i o n p r o f i l e was a c c o m p l i s h e d
using a fabricated, non-commercial flame i o n i z a t i o n detector.
Flow rates of the carrier gas were a d j u s t e d under ambient
c o n d i t i o n s by c a l i b r a t i n g a U-tube manometer i n terms o f gas
flow r a t e . T h i s r e q u i r e d o p e n i n g the c a r r i e r gas f l o w s p l i t t e r
so as t o d i v e r t the e n t i r e f l o w t h r o u g h the d e t e c t o r o r i f i c e ,
s u b s e q u e n t l y measuring the f l o w r a t e and d i f f e r e n t i a l p r e s s u r e
on the manometer, and t h e n r e t u r n i n g the c a l i b r a t e d m e t e r i n g
v a l v e t o i t s i n i t i a l s e t t i n g t o r e e s t a b l i s h the s p l i t (1:6-1:10)
o f the c a r r i e r gas flow. C a l i b r a t i o n w i t h and w i t h o u t the
d e t e c t o r gases ( a i r & H ) r e v e a l e d the absence o f any b a c k p r e s s u r e
2
e f f e c t due t o the d e t e c t o r combustion gases.

E x p e r i m e n t a l assessment o f the column v o i d volume p r o v e d t o
be critical since the s o l u t e r e t e n t i o n volume approaches the
void volume as pressure is increased. Following the
recommendations o f K o b a y a s h i ( 2 4 ) , we used an u n r e t a i n e d s o l u t e ,
methane, for this measurement. Values f o r the v o i d volume
d e t e r m i n e d o v e r an extended p r e s s u r e range were 1.8 and 0.5 ml.
for the crosslinked resin and alumina columns, respectively.
These figures were i n excellent agreement w i t h v o i d volume
a p p r o x i m a t i o n s o f 1.4 and 0.45 ml. based upon the g e o m e t r i c
volume o f the column assuming a p o r o s i t y o f 0.6 f o r the packed
beds.
The a d s o r b a t e s and a d s o r b e n t s i n t h i s s t u d y were chosen t o
r e f l e c t a range o f d i f f e r e n t t y p e s o f m o l e c u l a r i n t e r a c t i o n s as
well as t o o b s e r v e whether the r e t e n t i o n volume d a t a t r e n d s
c o u l d be g e n e r a l i z e d . In a d d i t i o n , s o l u t e s were p i c k e d which
would rapidly equilibrate with the chosen adsorbents (no
h y s t e r e s i s ) and whose d i s t r i b u t i o n c o e f f i c i e n t s c o u l d be measured
c o n v e n i e n t l y o v e r as wide a p r e s s u r e range as p o s s i b l e . As
shown i n T a b l e I , the a d s o r b e n t s c o r r e s p o n d e d t o two distinctly
different chemical types as c l a s s i f i e d by the c r i t e r i o n of
Kiselev (40). The alumina r e p r e s e n t e d an a d s o r b e n t c a p a b l e o f
s p e c i f i c i n t e r a c t i o n s with sorbates having l o c a l i z e d p e r i p h e r a l

e l e c t r o n d e n s i t y , s i n c e i t p o s s e s s e s a l o c a l i z e d p o s i t i v e charge
on i t s s u r f a c e . The c r o s s l i n k e d o r g a n i c polymer i s a Type I I I
a d s o r b e n t s i n c e i t s n e g a t i v e charge on the s u r f a c e i s due t o the
p r e s e n c e of an a r o m a t i c p i - e l e c t r o n system w i t h i n i t s m o l e c u l a r
structure. The a d s o r b a t e s employed represented a homologous
s e r i e s o f n - a l k a n e s (Group A s o r b a t e s ) and two Group Β a d s o r b a t e s ,
benzene and naphthalene, which have peripheral pi-electron
density.
T a b l e I. A d s o r b e n t / A d s o r b a t e C l a s s e s
U t i l i z e d i n the Chromatographic E x p e r i m e n t s
A d s o r b e n t Type A d s o r b a t e Type
A1 0 2 3 (Type I) n-Pentane
Styrene/Divinylbenzene Resin Benzene

(Group Β )
(Type 2) Naphthalene
Data R e d u c t i o n
There i s a fundamental r e l a t i o n s h i p d e s c r i b e d i n c h r o m a t o g r a p h i c
t h e o r y between the r e t e n t i o n volume o f a e l u t i o n peak and the
m i d - p o i n t o f a b r e a k t h r o u g h curve a c h i e v e d by o p e r a t i n g the
column under f r o n t a l a n a l y s i s c o n d i t i o n s ( 4 1 ) . I n the Henry's
Law r e g i o n o f the a d s o r p t i o n i s o t h e r m , the n e t r e t e n t i o n volume
and i t s measurement can be used t o d e s c r i b e the v a r i a t i o n o f
s o r b a t e b r e a k t h r o u g h volume as i l l u s t r a t e d i n F i g u r e 8. Utilizing
the e x p e r i m e n t a l a p p a r a t u s d e s c r i b e d i n the l a s t s e c t i o n , r e t e n t i o n
volumes were measured as a f u n c t i o n o f p r e s s u r e a t 40°C (T =
1.03) o v e r as wide a range o f p r e s s u r e as p o s s i b l e t o p e r m i t
e l u c i d a t i o n o f the b r e a k t h r o u g h c h a r a c t e r i s t i c s f o r the s e l e c t e d
sorbates. E x a m i n a t i o n o f the p u l s e p r o f i l e s i n d i c a t e d a h i g h
degree o f symmetry which was i n d i c a t i v e o f the absence o f non
l i n e a r s o r p t i o n i s o t h e r m f o r the systems under s t u d y . T h e r e f o r e ,
the r e p o r t e d r e t e n t i o n volume measurements can be equated w i t h
the b r e a k t h r o u g h and/or d e s o r p t i o n p a t t e r n o f the a d s o r b a t e
d u r i n g i t s passage t h r o u g h the column bed.
R e t e n t i o n volume d a t a were computed u s i n g E q u a t i o n 2:
V = (Τ /Τ )
Ί (Ζ /Ζ _) (ρ - ρ _ /ρ .) F (t - t )
J
(2)
r v
c o l ' a' v
a' c o l ' V i
a ^water'^col' a v
r o
where V = r e t e n t i o n volume o f the a d s o r b a t e

r
Τ , = column temperature
col *
T a = ambient temperature
Z ^c Q = compressibility f a c t o r a t p^

Ζ = c o m p r e s s i b i l i t y f a c t o r a t ambient p r e s s u r e
ambient p r e s s u r e
column p r e s s u r e
col
r
v a p o r p r e s s u r e o f water
water
F ambient f l o w r a t e
t = r e t e n t i o n time (peak maxima)
t = r e t e n t i o n time o f u n r e t a i n e d a d s o r b a t e p u l s e
The r e t e n t i o n d a t a d e s c r i b e d by E q u a t i o n 2 a r e c o r r e c t e d from
ambient c o n d i t i o n s t o the p r e v a i l i n g temperature and p r e s s u r e
c o n d i t i o n s w i t h i n the s o r b e n t column. Use o f the expansion
v a l v e a t the end o f th
n e g l i g i b l e p r e s s u r e dro
s i m p l i f y i n g the p r e s s u r e c o r r e c t i o n f a c t o r used i n the r e t e n t i o n
volume computations (23, 39).
The r e t e n t i o n volume computed by E q u a t i o n 2, V , can be
r e l a t e d t o the a d s o r p t i o n c o e f f i c i e n t and the s u r f a c e a r e a v a l u e
o f the s o r b e n t bed by:
V = Κ Λ A (3)
r A s
where = equilibrium adsorption c o e f f i c i e n t i n the Henry's Law

r e g i o n o f the a d s o r p t i o n i s o t h e r m
A = total s u r f a c e a r e a o f the s o r b e n t bed

s
Unfortunately v a l u e s cannot be d i r e c t l y c a l c u l a t e d from

r e t e n t i o n volume measurements by E q u a t i o n 3 s i n c e the i n t e r f a c i a l
s u r f a c e a r e a i s c h a n g i n g as a f u n c t i o n o f p r e s s u r e due t o the
carbon d i o x i d e s o r p t i o n . However, the r e l a t i v e magnitude o f the
e q u i l i b r i u m s h i f t o f t h e s o r b a t e from the s o l i d a d s o r b e n t i n t o
the gaseous phase can be e s t i m a t e d by c a l c u l a t i n g the c a p a c i t y
f a c t o r , k', a c c o r d i n g t o E q u a t i o n 4 as g i v e n below:
where V i s the column v o i d volume,

ο
The a p p l i c a t i o n o f p r e s s u r e causes a c o n s i d e r a b l e d e c r e a s e i n
the r e t e n t i o n o r b r e a k t h r o u g h volume f o r an a d s o r b a t e t r a n s v e r s i n g
down a s o r b e n t column. T h i s t r e n d i s amply i l l u s t r a t e d i n
F i g u r e 9 where the r e t e n t i o n volume f o r benzene i n C 0 has been 2
p l o t t t e d as a f u n c t i o n o f p r e s s u r e f o r the c r o s s l i n k e d s t y r e n e /
d i v i n y l b e n z e n e r e s i n a t 40°C. In t h i s f i g u r e , there i s a
c o n s i d e r a b l e decrease i n i t i a l l y i n V over a small p r e s s u r e
i n t e r v a l and the b r e a k t h r o u g h volume appears t o become c o n s t a n t

F i g u r e 8. R e l a t i o n s h i p between t h e m i d - p o i n t o f t h e f r o n t a l
b r e a k t h r o u g h p r o f i l e and t h e e l u t i o n peak maxima.
F i g u r e 9. B r e a k t h r o u g h volume as a f u n c t i o n o f carbon d i o x i d e
p r e s s u r e f o r benzene on t h e c r o s s l i n k e d p o l y m e r i c r e s i n .

beyond 200 atmospheres. The o b s e r v e d t r e n d i m p l i e s t h a t f u r t h e r

a p p l i c a t i o n o f p r e s s u r e a f f o r d s no advantage i n removing benzene
from t h e a d s o r b e n t column. In general, a l l of sorbates s t u d i e d
i n our experiments e x h i b i t e d a s i m i l a r t r e n d upon i n j e c t i o n i n t o
the dense C 0 c a r r i e r gas.
2
Close examination o f F i g u r e 9 r e v e a l s t h a t the r a t e o f

change f o r the r e t e n t i o n volume w i t h p r e s s u r e undergoes an
i n f l e x i o n i n the low p r e s s u r e r e g i o n o f the graph. Therefore,
a d d i t i o n a l measurements were t a k e n to confirm t h i s trend at
p r e s s u r e s below 200 atmospheres. F i g u r e 10 shows the r e s u l t s o f
this extended study f o r benzene on the r e s i n a d s o r b e n t . The
d a t a show t h a t the r a t e o f d e c r e a s e i n the b r e a k t h r o u g h volume
is linear up to a pressure of approximately 70 atmospheres,
however beyond this degree o f gas compression, the sorbate
retention volume decreases even more r a p i d l y w i t h increasing
pressure. A t a p r e s s u r e below 100 atmospheres, the breakthrough
volume o f benzene approaches a c o n s t a n t v a l u e e q u i v a l e n t t o the
v o i d volume o f the colum
when V was p l o t t e d as a
To c o n f i r m the above o b s e r v a t i o n s , an a d d i t i o n a l s e t o f
experiments were performed using a different sorbate probe,
η-heptane. Once a g a i n , as w i t h benzene, the r e t e n t i o n volume
was found t o d e c r e a s e i n a s i m i l a r manner w i t h i n c r e a s i n g gas
p r e s s u r e on the c r o s s l i n k e d r e s i n sorbent. As shown i n b o t h
F i g u r e s 10 and 11, the a b r u p t d e c r e a s e i n breakthrough volume
o c c u r s a t a gas p r e s s u r e c l o s e t o the ρ or ρ v a l u e as
0
c a l c u l a t e d by E q u a t i o n 1 f o r carbon d i o x i d e . A sim¥iar i n f l e c t i o n
has a l s o been noted by S i e , Van Beersum, and R i j n d e r s (42) when
the l o g a r i t h m o f the p a r t i t i o n coefficient i s plotted as a
f u n c t i o n of pressure i n high pressure g a s - l i q u i d chromatographic
studies. The above result suggests that the uptake of
s u p e r c r i t i c a l gas by the a d s o r b e n t produces a s i g n i f i c a n t change
i n the b r e a k t h r o u g h volume o f the s o r b a t e p u l s e and t h a t o b s e r v e d
m i g r a t i o n enhancement i s i n p a r t due t o m o d i f i c a t i o n o f the
g a s - s o l i d i n t e r f a c e by the dense f l u i d .
Similar experiments were a l s o conducted on the styrene/
divinylbenzene adsorbent in which the capacity factor and
r e t e n t i o n volumes were determined for a series of n-alkanes
( n - C - C ) a t 40°C.
5 7 I t was found t h a t the c a p a c i t y f a c t o r s f o r
the homologues d e c r e a s e d l i n e a r l y by an o r d e r o f two magnitudes
and in a parallel f a s h i o n up t o a p r e s s u r e o f 1250 p s i g (85
atm.). A t t h i s p r e s s u r e the s o l u t e c a p a c i t y f a c t o r s began t o
change r a p i d l y w i t h p r e s s u r e , s i m i l a r t o the t r e n d o b s e r v e d i n
the breakthrough volume f o r benzene and η-heptane reported
above. I t was a l s o noted i n t h i s t r a n s i t i o n r e g i o n , t h a t the
capacity factors f o r the individual alkanes tended t o merge
t o g e t h e r , and t h a t d i f f e r e n t i a l m i g r a t i o n down the column was
not p o s s i b l e in this higher pressure regime. Such a result
s u g g e s t s t h a t f r a c t i o n a t i o n o f the above homologues can o n l y be
accomplished s u c c e s s f u l l y below the ρ value associated with
X
the a d s o r p t i o n o f the c r i t i c a l f l u i d a r ? t h e g a s - s o l i d i n t e r f a c e .
A p p a r e n t l y , the f o r m a t i o n o f a m u l t i m o l e c u l a r l a y e r o f adsorbed
gas w i t h i n c r e a s i n g p r e s s u r e not o n l y a s s i s t s i n d e s o r b i n g the
injected sorbate but significantly nullifies the potential
f i e l d o f the a d s o r b e n t t o such an e x t e n t t h a t d i f f e r e n t i a l



a d s o r p t i o n o f v a r i o u s a d s o r b a t e s i s no l o n g e r p o s s i b l e . Similar
c o n c l u s i o n s have been r e a c h e d by o t h e r i n v e s t i g a t o r s (43) u s i n g
e l u t i o n chromatographic experiments.
A d d i t i o n a l e v i d e n c e f o r the r o l e o f the s u p e r c r i t i c a l fluid
i n m o d i f y i n g the i n t e r f a c e i s p r o v i d e i n F i g u r e 12. Here the
c a p a c i t y f a c t o r f o r n-pentane on alumina a t 40°C i s shown as a
f u n c t i o n o f p r e s s u r e up t o 700 atmospheres. The c o n s i d e r a b l e
reduction i n k' below 100 atmospheres parallels the solute
breakthrough behavior described e a r l i e r on the o r g a n i c r e s i n .
Also plotted i n F i g u r e 12 i s g r a v i m e t r i c a d s o r p t i o n d a t a f o r
t h r e e gases a d s o r b i n g on a l u m i n a ; c a r b o n d i o x i d e , n i t r o g e n , and
c a r b o n monoxide, as t a k e n from the l i t e r a t u r e . The i s o t h e r m
d e p i c t e d f o r n i t r o g e n and carbon monoxide were a b s t r a c t e d from
the s t u d y o f Menon (44) and r e p r e s e n t the d i f f e r e n t i a l a d s o r p t i o n
o f t h e s e gases a t 50°C. The maximum s o r p t i o n o f C 0 2 on a alumina
i s d e s i g n a t e d w i t h an a s t e r i s k i n F i g u r e 12 f o r c l a r i t y , however
the e n t i r e i s o t h e r m can be found i n the paper o f Ozawa and Ogino
(33). The a c t u a l i s o t h e r
sharp when compared t o
a f e a t u r e i n k e e p i n g w i t h the low reduced temperature a t which
the C 0 2 i s adsorbed (T = 1.03). The a d s o r p t i o n r e c o r d e d f o r
n i t r o g e n and c a r b o n monoxide was t a k e n a t reduced temperatures
o f 2.48 and 2.35, r e s p e c t i v e l y , hence a d d i t i o n a l gas compression
is required to a c h i e v e maximum uptake o f the supercritical
fluid. Despite the different aluminas used i n the cited
e x p e r i m e n t a l s t u d i e s , the g r a v i m e t r i c a d s o r p t i o n d a t a i n F i g u r e
12 suggest that the b r e a k t h r o u g h volume i s controlled by
c o m p e t i t i v e a d s o r p t i o n o f the s u p e r c r i t i c a l f l u i d a t the gas-
solid interface. The c l o s e p r o x i m i t y o f the c a r b o n dioxide
a d s o r p t i o n maximum t o the r e g i o n o f maximum change i n V supports
the above c o n c e p t . L i k e w i s e , the h i g h e r p r e s s u r e s r e q u i r e d t o
r e a c h the a d s o r p t i o n maxim a i n the CO and N 2 c a s e s , would argue
t h a t a more g r a d u a l change i n the b r e a k t h r o u g h volume w i t h
p r e s s u r e s h o u l d o c c u r f o r s i m i l a r s o r b a t e s which a r e d e s o r b e d a t
50°C u s i n g t h e s e s u p e r c r i t i c a l f l u i d s . Maximum d e s o r p t i o n due
to c o m p e t i t i v e a d s o r p t i o n o f the s u p e r c r i t i c a l fluid a t the
g a s - s o l i d i n t e r f a c e i s a c h i e v e d by o p e r a t i n g c l o s e t o the c r i t i c a l
temperature o r ρ o f the d i s p l a c i n g gas.
To t e s t the above c o n c e p t , a r a t h e r r a d i c a l experiment was
performed employing h e l i u m as the c a r r i e r gas a t 40°C ( T ^ =
59.1) w i t h subsequent measurement o f the r e t e n t i o n volumes f o r
several light hydrocarbons ( n - C - C ) on
3 5 the alumina column.
F i g u r e 13 shows the r e d u c t i o n i n the c a p a c i t y f a c t o r w i t h p r e s s u r e
f o r η-butane as a s o r b a t e u t i l i z i n g h e l i u m and c a r b o n d i o x i d e as
c a r r i e r gases. The t r e n d o b s e r v e d i n the c a p a c i t y f a c t o r f o r
η-butane as w e l l as the o t h e r a l k a n e s i n p r e s s u r i z e d carbon
dioxide i s i d e n t i c a l to t h a t observed w i t h alkanes of h i g h e r
carbon number on alumina and the c r o s s l i n k e d organic resin.
However, when h e l i u m i s used as the c a r r i e r f l u i d , t h e r e appeared
t o be a s m a l l i n i t i a l drop i n the c a p a c i t y f a c t o r f o l l o w e d by a
more g r a d u a l d e c r e a s e i n k' w i t h i n c r e a s i n g p r e s s u r e (up t o
10,000 p s i g ) . Examination o f F i g u r e 13 s u g g e s t s t h a t much
h i g h e r p r e s s u r e s must be employed to e f f e c t a f u r t h e r reduction
i n the b r e a k t h r o u g h volume f o r η-butane i n h e l i u m on the o x i d e
sorbent, at l e a s t comparable to t h a t o b s e r v e d when u s i n g c a r b o n

I ' ι ι ι ι ι ι ι ι ι 1 1 ι ι I I I
Γ * C0 - 40.0°C
2
PRESSURE (ATM) X 100
F i g u r e 12. C a p a c i t y f a c t o r f o r n-pentane on alumina column a t

40°C and the d i f f e r e n t i a l a d s o r p t i o n o f t h r e e gases as a f u n c t i o n
o f gas c o m p r e s s i o n .
F i g u r e 13. C a p a c i t y f a c t o r f o r η-butane i n c a r b o n d i o x i d e and

h e l i u m as a f u n c t i o n o f column p r e s s u r e . Temp. = 40°C.

d i o x i d e as the s u p e r c r i t i c a l f l u i d phase. We b e l i e v e t h a t the

observed difference i n sorbate behavior i n the two candidate
gases i s a r e f l e c t i o n o f the degree o f s u r f a c e m o d i f i c a t i o n
caused by the d i f f e r e n t amounts o f a d s o r p t i o n e x h i b i t e d by the
two supercritical gases. S o r p t i o n of helium a t such a h i g h
reduced temperature i s v e r y low, b u t not e n t i r e l y n e g l i g i b l e a t
the p r e s s u r e s employed i n t h i s s t u d y . T h i s l a t e r f a c t o r combined
w i t h the weak s o l v e n t power o f h e l i u m gas [the s o l u b i l i t y parameter
f o r h e l i u m a t 14,000 p s i g i s 1.6 H i l d e b r a n d s (45)] most l i k e l y
accounts f o r the r e c o r d e d g r a d u a l b r e a k t h r o u g h o f the n-butane
p u l s e from the alumina column.
Conclusions
In t h i s s t u d y , we have examined the r o l e o f a s u p e r c r i t i c a l

fluid a d s o r b i n g a t the g a s - s o l i d interface and the p o s s i b l e
implications of such a phenomena on adsorption/desorption
processes. The above
that displacement of a
of the s u p e r c r i t i c a l f l u i d a t the i n t e r f a c e i s a major f a c t o r i n
regenerating a d s o r b e n t s and i n c o n t r o l l i n g the p a r t i t i o n o f the
solute ( s o r b a t e ) i n t o t h e f l u i d phase. A d d i t i o n a l support f o r
t h i s concept can be found i n the r e g e n e r a t i o n s t u d i e s o f E p p i g
and co-workers (14) who demonstrated the r e c o v e r y o f e t h a n o l ,
methyl e t h y l ketone, and toluene from activated carbon beds
u s i n g modest C 0 2 p r e s s u r e s ( l e s s t h a n 100 atms.). Adsorption/
d e s o r p t i o n s t u d i e s o f l i g h t h y d r o c a r b o n / C 0 m i x t u r e s on m o l e c u l a r
2
sieve (46) a l s o indicate that C0

2 is preferentially adsorbed
o v e r the a l k a n e m o i e t i e s , s u p p o r t i n g a s i m i l a r concept advanced
i n t h i s study.
The r e t e n t i o n volume d a t a p r e s e n t e d i n t h i s study imply
t h a t there are d i s t i n c t regions of sorbate breakthrough behavior
t h a t a r e i n p a r t d e f i n e d by the e x t e n t o f compressed gas
a d s o r p t i o n a t the s o l i d i n t e r f a c e . The r e g i o n f o r most p r o f i t a b l e
f r a c t i o n a t i o n o f a d s o r b a t e s would appear t o l i e below the ρ
v a l u e as d e f i n e d by t h e a d s o r p t i o n i s o t h e r m o f t h e s u p e r c r i t i c a l
fluid. P l o t s o f r e t e n t i o n volume v e r s u s p r e s s u r e a l s o a r e o f
g r e a t a i d i n d e f i n i n g a maximum p r e s s u r e beyond which no f u r t h e r
r e d u c t i o n i n breakthrough volume i s p o s s i b l e t h r o u g h i n c r e a s e d
gas compression. Such d a t a i s o f v a l u e i n s p e c i f y i n g the most
e f f i c i e n t c o n d i t i o n s f o r the r a p i d and e c o n o m i c a l supercritical
fluid r e g e n e r a t i o n o f a d s o r b e n t beds. I t would appear t h a t t h e
ρ value discussed above, is a minimal pressure which
investigators should endeavor to attain when a t t e m p t i n g to
desorb compounds w i t h s u p e r c r i t i c a l f l u i d media. However, e x t r a
gas compression may be r e q u i r e d above the ρ value to solvate
and strip s t r o n g l y adsorbed components from adsorbent matrix.
Additional experimental studies should be undertaken in the
f u t u r e t o b e t t e r d e f i n e and v e r i f y the c o n c e p t s p r e s e n t e d i n
this study, particularly utilizing other supercritical fluid
d i s p l a c i n g agents and a d s o r b a t e s o f lower v o l a t i l i t y and a p o l a r
nature.

Literature Cited
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"Supercritical Fluid Regeneration of Activate Carbon for
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2. Klesper, Ε. In "Extraction with Supercritical Gases";
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State College, Pennsylvania, 1980.
8. Yang, R. T.; Saunders, J. T. Fuel 1985, 64, 616.
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10. Shimokobe, I. Japanese Patent 31 679, 1976.
11. Modell, M. U.S. Paten
12. Modell, M. U.S. Patent 4 124 528, 1978.
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Carbon Adsorption of Organics from the Aqueous Phase";
Stuffet, I. H.; McGuire, M. J., Eds.; Ann Arbor Science
Publishers, Ann Arbor, Michigan, 1980; Vol. 1, pp. 447-461.
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Fluid Regeneration of Activated Carbon Used for Volatile-
Organic-Compound Vapor Adsorption," EPA Report 600/2-82-067,
1982.
15. deFilippi, R. P.; Robey, R. J. "Supercritical Fluid
Regeneration of Adsorbents," EPA Report 600/2-83-038, 1983.
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at Supercritical Fluid Conditions"; Paulaitis, M. E.;
Penninger, J. M. L.; Gray, R. D.; Davidson, P., Eds.; Ann
Arbor Science Publishers: Ann Arbor, Michigan, 1983; pp.
461-476.
17. Greene, S. Α.; Roy, Η. E. Anal. Chem. 1957, 29, 569.
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11.

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3, pp. 313-365.
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Chapter 14
Mechanism of Solute Retention in Supercritical Fluid

Chromatography
C. R. Yonker, R. W. Wright, S. L . Frye, and R. D. Smith
Chemical Methods and Separations Group, Chemical Technology Department, Pacific

Northwest Laboratory, Battelle Memorial Institute, Richland, WA 99352
The complicated dependence of retention in super-

critical fluid chromatography as a function of tem-
perature and pressure is examined. Simple thermody-
namic relationships are derived and discussed which
allow the calculatio
tion as a functio
These models are compared to experimental data
obtained over a wide range of temperatures and
pressures.
Solute retention as a function of pressure at
constant temperature is dependent on the partial
molar volume of the solute in the stationary
phase the solubility of the solute in the
fluid and the isothermal compressibility of the
fluid. The model was compared to the experimental
retention data of naphthalene and biphenyl and fit
the data quite well.
Solute retention as a function of temperature at
constant pressure is seen to be dependent on the par-
tial molar enthalpy of solute transfer
between the mobile and stationary phases, the heat
capacity of the supercritical fluid mobile phase and
the volume expansivity of the fluid. The model was
compared to chromatographic retention data for
solutes in n-pentane and CO2 as the fluid mobile
phase and was seen to fit the data well.
The e f f e c t of temperature, p r e s s u r e and d e n s i t y on s o l u t e r e t e n t i o n
f
( k ) i n s u p e r c r i t i c a l f l u i d chromatography (SFC) has been w e l l
studied.(1-6) R e t e n t i o n i n SFC depends upon both s o l u t e s o l u b i l i t y
i n t h e f l u i d and s o l u t e i n t e r a c t i o n w i t h t h e s t a t i o n a r y phase. The
f u n c t i o n a l r e l a t i o n s h i p between r e t e n t i o n and p r e s s u r e a t c o n s t a n t
temperature has been d e s c r i b e d by Van Wasen and S c h n e i d e r . (1_) The
t r e n d i n r e t e n t i o n i s seen t o depend on t h e p a r t i a l molar volume of
0097-6156/87/0329-0172$06.00/0

14. YONKERETAL. Mechanism of Solute Retention 173
the s o l u t e i n t h e m o b i l e and s t a t i o n a r y phases c o u p l e d w i t h t h e i s o

t h e r m a l c o m p r e s s i b i l i t y o f t h e f l u i d m o b i l e phase.
The e f f e c t o f temperature on r e t e n t i o n has been d e s c r i b e d
e x p e r i m e n t a l l y , ( 4 - 8 ) but t h e f u n c t i o n a l dependence o f k' w i t h
temperature has o n l y r e c e n t l y been d e s c r i b e d . ^ 9 ) A thermodynamic
model was o u t l i n e d r e l a t i n g r e t e n t i o n as a f u n c t i o n o f temperature
at c o n s t a n t p r e s s u r e t o t h e volume e x p a n s i v i t y o f the f l u i d , t h e
e n t h a l p y o f s o l u t e t r a n s f e r between t h e m o b i l e phase and t h e s t a
t i o n a r y phase and t h e change i n t h e heat c a p a c i t y o f the f l u i d as a
f u n c t i o n o f temperature.(9) The s o l u b i l i t y o f a s o l i d s o l u t e i n a
s u p e r c r i t i c a l f l u i d has been d i s c u s s e d by G i t t e r m a n and P r o c a c c i a
(10) over a l a r g e range o f p r e s s u r e s . The c o m b i n a t i o n o f s o l u t e
s o l u b i l i t y i n a f l u i d w i t h t h e e q u a t i o n f o r r e t e n t i o n as a f u n c t i o n
of p r e s s u r e d e r i v e d by Van Wasen and S c h n e i d e r a l l o w s one t o examine
the e f f e c t o f s o l u b i l i t y on s o l u t e r e t e n t i o n .
In t h i s work we d e r i v e s i m p l e r e l a t i o n s h i p s between tempera
t u r e , s o l u t e s o l u b i l i t y and r e t e n t i o n The s i m p l e thermodynamic
models d e v e l o p e d p r e d i c t
pressure, given the s o l u b i l i t
phase a t c o n s t a n t temperature and t h e t r e n d i n k' as a f u n c t i o n o f
temperature a t c o n s t a n t p r e s s u r e . Our aim i s t o examine the c o m p l i
c a t e d dependence o f r e t e n t i o n on t h e thermodynamic and p h y s i c a l
p r o p e r t i e s o f the s o l u t e and t h e f l u i d , p r o v i d i n g a b a s i s f o r
c o n s i d e r a t i o n o f more s u b t l e e f f e c t s i n SFC.
Theory
In SFC t h e b a s i c assumption o f i n f i n i t e l y d i l u t e s o l u t i o n s o f t h e
s o l u t e i n the m o b i l e and s t a t i o n a r y phases i s v a l i d . The c o n c e n t r a
X
t i o n o f t h e s o l u t e i n t h e s e phases r e s p e c t i v e l y i s C^ = j / V , where m
X^ i s t h e mole f r a c t i o n o f s o l u t e ( i ) and V i s t h e molar volume o f m
the pure mobile o r s t a t i o n a r y phase. (J^) Solute retention i s deter

1
mined from a d i m e n s i o n l e s s r e t e n t i o n f a c t o r , k , where,
s t a t m o b
. = (c
k ±
s t a t
/c ±
m o h
) . (v /v ) (1)
mob
C i
s t
and C
a t
a r e the c o n c e n t r a t i o n o f s o l u t e ( i ) i n t h e s t a t i o n
±
s t a t 111
ary and mobile phases r e s p e c t i v e l y , v and v a r e the volumes
of the s t a t i o n a r y and mobile phase. S u b s t i t u t i n g f o r c o n c e n t r a t i o n
i n t o e q . 1,
k- = i x . s t a t
/x. r a o b
l · (v raob
/v s t a t
) . (v sta,
7v mob
) (2)
T a k i n g the n a t u r a l logarithm o f both s i d e s of eq. 2 one o b t a i n s ,
„it „ r „ s t a t , . . mob Ν , „ mob „stat ... s t a t r ..mob ^ / Qx

Jink 1
= i n iX. /X. J + An (V V /V K
V J
(3)
^ ι ι ' m m
At e q u i l i b r i u m ; t h e s o l u t e c h e m i c a l p o t e n t i a l i n t h e r e s p e c t i v e
phases a r e e q u a l : μ^ ^ - μ ^ ^ . Ο Ο 1
Therefore,
( u. S t a t
= ,. (
m 0 b
= μ"** RT * n x f a t
= . ™ * + RT
μ in x j ° b
(4)

where μ^°° i s t h e chosen s t a n d a r d s t a t e o f u n i t molar c o n c e n t r a t i o n

of s o l u t e ( i ) i n t h e two p h a s e s . I t s h o u l d be p o i n t e d out t h a t i n
the case o f the s o l u t e i n t h e s t a t i o n a r y phase, t h i s c h o i c e o f
s t a n d a r d s t a t e i s a h y p o t h e t i c a l one which e x h i b i t s t h e p r o p e r t i e s
of an i n f i n i t e d i l u t e s o l u t i o n . ( 1 2 ) R e a r r a n g i n g e q . 4,
_ ^ , mob stat
S t a t m 0 b œ
*n (X 1 /X i ) = ( - μ μ ι ± " )/RT (5)
S u b s t i t u t i n g e q . 5 i n t o 3,
mob stat . ^ _ _ _ ,
b
Jink' = [ H " - H °° ) / RT + Jin ( \ ™ v S t a t
/V m
8 t a t
V m 0 b
) (6)
An assumption can be made t h a t t h e second term on t h e r i g h t - h a n d

m o b
s i d e (RHS) o f eq. 6 i s independent o f p r e s s u r e e x c e p t f o r V , the m
molar volume o f t h e f l u i d m o b i l e phase Therefore d i f f e r e n t i a t i o n

of e q . 6 w i t h r e s p e c t t
(ôJU*7ôP) T = l/RT [ ( ο μ ™ $ Ρ ) 9 τ - (δμ^οΡ) ] Τ + (ôAn V m

m 0 b
/ôP) T (7)
The p a r t i a l molar volume o f the s o l u t e i s d e f i n e d as ( ôu^/dP)-j* (_Li_)

The second term on the RHS o f e q . 7 i s t h e i s o t h e r m a l c o m p r e s s i b i l -
i t y (K) o f the f l u i d mobile phase.(13) Thus, eq. 7 reduces t o ,
mob stat
c
(ôAnk'/dP) T = l/RT [V ° ± - V. °° 1 - Κ (8)
- mob - stat
where V.^ and a r e t h e p a r t i a l molar volumes o f the s o l u t e
( i ) i n t h e mobile and s t a t i o n a r y phases a t i n f i n i t e d i l u t i o n ,
respectively. E q u a t i o n 8 i s t h e same as o b t a i n e d by Van Wasen and
S c h n e i d e r (1) i n t h e i r d e r i v a t i o n o f the t r e n d i n r e t e n t i o n as a
f u n c t i o n o f p r e s s u r e f o r SFC.
The s o l u b i l i t y o f a s o l i d i n a s u p e r c r i t i c a l f l u i d has been
d e s c r i b e d by G i t t e r m a n and P r o c a c c i a . ( 1 0 ) The r e g i o n o f i n t e r e s t
c h r o m a t o g r a p h i c a l l y w i l l be f o r i n f i n i t e l y d i l u t e s o l u t i o n s whose
c o n c e n t r a t i o n i s f a r removed from t h e lower c r i t i c a l end p o i n t
(LCEP) o f the s o l u t i o n . T h e r e f o r e t h e s o l u b i l i t y o f the s o l u t e i n a
s u p e r c r i t i c a l f l u i d a t i n f i n i t e d i l u t i o n f a r from c r i t i c a l i t y can be
approximated a s ,
, mob
m 0 b s
(ôtoX / PJ
i = l/RT [ V - V ~]
ô T (9) 1
s
where V i s t h e molar volume o f t h e pure s o l i d s o l u t e . ( 1 0 ) Equa-
t i o n 9 i s based on t h e assumption t h a t t h e s o l u t e ' s p a r t i a l molar
volume a t i n f i n i t e d i l u t i o n r o u g h l y approximates t h a t o f a s a t u r a t e d
s o l u t i o n a t low mole f r a c t i o n v a l u e s o f t h e s o l u t e i n t h e f l u i d
- mojj
phase ( s e e F i g u r e s 1 and 5 ) . S o l v i n g e q . 9 f o r ,

mob ,
V ±
œ
- -RT (ôln X ^ / Ô P J T + V S
(10)
S u b s t i t u t i n g e q . 10 i n t o e q . 8 and r e a r r a n g i n g ,
stat ,
s m o b
(ôAnk7aP) T - (V - V t °° )/RT - (ôAn X . /ôP) T - Κ (11)
E q u a t i o n 11 s h o u l d be the r e l a t i o n s h i p between r e t e n t i o n - s o l u b i l i t y
and p r e s s u r e a t c o n s t a n t temperature f o r i n f i n i t e l y d i l u t e s o l u
tions. The RHS o f e q . 11 c o n s i s t s of t h r e e terms, t h e f i r s t term
w i l l be a c o n s t a n t whose v a l u e depends on t h e p a r t i a l molar volume
of t h e s o l u t e i n t h e s t a t i o n a r y phase. The second term i s t h e
s o l u b i l i t y of t h e s o l u t e i n t h e s u p e r c r i t i c a l f l u i d mobile phase.
The l a s t term, t h e f l u i d ' s i s o t h e r m a l c o m p r e s s i b i l i t y , can be
r e a s o n a b l y p r e d i c t e d from a two-parameter, c u b i c e q u a t i o n of s t a t e
(EOS) such as t h e Redlich-Kwong EOS o r the Peng-Robinson EOS.(14,15)
The f l u i d ' s i s o t h e r m a
Redlich-Kwong EOS t o e v a l u a t
due t o t h e ease of f i n d i n g an a n a l y t i c a l s o l u t i o n ,
(MU v m
m o b
/ ô p ) T - (i/v m
m o b
) · (a v m
m o b
/ P)ô T - -κ (12)
From t h e Redlich-Kwong EOS,
v mob 0 . 5 T .2 _ ( v mob,2,
J J
/ v mob, ν _ m J; ^ m / , o \
5
1
• =
Ρ Τ °· (3 (V m
m o b
) 2
- b ) - RT 2 3 / 2
t2V™ b
+ b) + a
where R i s t h e gas c o n s t a n t , Ρ i s p r e s s u r e , and Τ i s temperature i n

K. The c o n s t a n t s a and b o f t h e Redlich-Kwong EOS a r e ,
2 2 β 5
a - 0.4278 R Τ /Ρ (14a)
c c
b = 0.0867 RT /P (14b)
c c
where P and T a r e t h e c r i t i c a l p r e s s u r e and t e m p e r a t u r e of the

Q Q
fluid. The molar volume of t h e f l u i d was determined by an EOS, thus

a l l o w i n g one t o s o l v e f o r t h e i s o t h e r m a l c o m p r e s s i b i l i t y of t h e
fluid. T h e r e f o r e , u s i n g e q . 11, we can c a l c u l a t e the t r e n d i n r e t e n
t i o n as a f u n c t i o n o f p r e s s u r e a t c o n s t a n t temperature g i v e n t h e
s o l u b i l i t y of the s o l u t e i n t h e s u p e r c r i t i c a l f l u i d , t h e i s o t h e r m a l
c o m p r e s s i b i l i t y of t h e f l u i d and the p a r t i a l molar volume of t h e
s o l u t e i n t h e s t a t i o n a r y phase a t i n f i n i t e d i l u t i o n .
The d e r i v a t i o n of the dependence of t h e t r e n d i n s o l u t e r e t e n
t i o n w i t h temperature a t c o n s t a n t p r e s s u r e i s s i m i l a r t o t h a t
d e s c r i b e d above f o r the t r e n d i n s o l u t e r e t e n t i o n as a f u n c t i o n of
s o l u t e s o l u b i l i t y and p r e s s u r e a t c o n s t a n t t e m p e r a t u r e . Once a g a i n
making t h e same assumptions t h a t l e d t o e q . 6 and assuming tempera
t u r e has a n e g l i g i b l e e f f e c t on v , V , and V , differentia s t a t
m
t a t m o b
t i o n of eq. 6 with respect to temperature at constant pressure

yields

, _ - 11 r δ<ΔμΤ/Τ)
0 b
,a ink' >
0Ink. ^ i χ •ô l n V
m^ ^ ,. ^ \
l ÔT " ôf Jp ί ôf h
The f i r s t terra on the r i g h t hand s i d e of eq. 15 can be e v a l u a t e d as

, . â stat m b
(where Δ μ = μ^^ ί - μ ), ί
Δμ. ΔΗ
— ^ - Δ5° (16)
where H? and AS? a r e the p a r t i a l molar e n t h a l p y and e n t r o p y of

t r a n s f e r r i n g the s o l u t e m o l e c u l e from the s t a t i o n a r y phase t o t h e
mobile phase a t i n f i n i t e d i l u t i o n . T a k i n g the d e r i v a t i v e o f eq. 16
w i t h r e s p e c t t o temperature a t c o n s t a n t p r e s s u r e and s u b s t i t u t i n g
i n t o eq. 15 one o b t a i n s
oo oo GO ΤΠΩΠ
Δ Η Ο Δ Η Ô A S ô l n V
, lnk'
0 _ -1 - ~ ΐ 1 ι i . - m
("lyr )p - =
" R [~T~ +
f (ÔT"^P " iôT~JpJ +
( âr ^ ( 1 7 )
and upon rearrangement;
OD oo ,,mob
Ι ψ - ) Ρ - - T ( - ^ ) p + T 2
( - ^ ) p ] + - L - (_»-) p (18)
The second and t h i r d terms i n the b r a c k e t on the RHS o f eq. 13 a r e
e q u a l and o p p o s i t e because (ôAHj/dT)p = ACpJ and (ôAS ? / d T ) p =
ACp co/T.
i Thus e q . 18 becomes on s u b s t i t u t i o n ,
fôlJîill) = _ L + J _ rij5_) (19)

Ô T P 2 m b ô T P
RT V °
m
E q u a t i o n 19 i s v a l i d over a l i m i t e d temperature range f a r from the

c r i t i c a l p o i n t of the s o l u t i o n m i x t u r e . T h e r e f o r e , f o r the case of
t y p i c a l gas and/or l i q u i d c h r o m a t o g r a p h i c c o n d i t i o n s , e q . 19 becomes
the l i m i t i n g case where ΔΗ? i s c o n s t a n t and independent of tempera

ture. F u r t h e r , assuming t h a t the second term on the RHS o f eq. 19 i s
s m a l l o r n e g l i g i b l e under normal o p e r a t i n g c o n d i t i o n s f o r l i q u i d and
gas chromatography, eq. 19 on rearrangement reduces t o the f a m i l i a r
case d e s c r i b e d by Van't Hoff ( 1 6 )
(Q 4') = I^jl n
(20)

14. YONKER ET AL. Mechanism of Solute Retention 177
Assuming ΔΗ^°° i s a f u n c t i o n of temperature, (17)
< - ΔΗ
Γ(Το) +
To/' * p i d T ( 2 1 )
where Δ θ ? i s the d i f f e r e n c e i n heat c a p a c i t y of the s o l u t e i n the

ρ
m o b i l e phase as compared t o the s o l u t e i n the s t a t i o n a r y phase.

E q u a t i o n 21 i s v a l i d o v e r the e n t i r e temperature range of i n t e r e s t
f o r chromatographic s e p a r a t i o n s , i . e . , l i q u i d , s u p e r c r i t i c a l f l u i d
and gas chromatography. S u b s t i t u t i n g e q . 21 i n t o e q . 19 one o b t a i n s ,
m o b
Τ - ôV
E q u a t i o n 22 d e s c r i b e s the r e l a t i o n s h i p between temperature and s o l u t e

r e t e n t i o n at constant pressur
A s i m p l i f y i n g assumptio
s o l u t e i n the mobile phase, A C J ° i n e q . 22 can be approximated by the

P
heat c a p a c i t y of the m o b i l e phase. The dependence o f heat c a p a c i t y

on temperature and p r e s s u r e near the c r i t i c a l p o i n t o f a f l u i d i s
complicated.(18) I n t h i s work we f o r m u l a t e an e m p i r i c a l approxima-
t i o n t o the i n t e g r a l i n e q . 22 f o r the heat c a p a c i t y as a f u n c t i o n of
temperature near t h e c r i t i c a l p o i n t o f t h e f l u i d mobile phase.(9)
The second term on the RHS of eq. 22 i s the volume e x p a n s i v i t y
which can be c a l c u l a t e d from a two-parameter, c u b i c e q u a t i o n of s t a t e
such as the Redlich-Kwong EOS.(14) We chose the Redlich-Kwong EOS
because t h e " a " term i s independent of t e m p e r a t u r e , which s i m p l i f i e s
the p r o c e d u r e of s o l v i n g f o r the a n a l y t i c a l s o l u t i o n . U s i n g the
method of i m p l i c i t d i f f e r e n t i a t i o n w i t h the Redlich-Kwong e q u a t i o n of
state,
m o b 2 m 0 b r a o b l e 5 1 5
mob
oV (V ) R + V Rb +0.5 V aT~ - 0.5 abT* *
r m Ν _ m m _m (23)
[ Γ ) ν
~* ~ ô-b-2~7 -ïob v R T _ 2 _
p b R T b + a T -0.5
m m
where R i s the gas c o n s t a n t , P i s p r e s s u r e , and Τ i s temperature i n

K. The c o n s t a n t s a and b o f t h e Redlich-Kwong e q u a t i o n have a l r e a d y
been d e f i n e d i n e q s . 14a and 14b. The d e t e r m i n a t i o n of the d e r i v a
t i v e i n e q . 23 was a c c o m p l i s h e d by t h e use of an EOS t o s o l v e f o r t h e
c o m p r e s s i b i l i t y o f the f l u i d . The molar volume o f the f l u i d m o b i l e
phase can then be c a l c u l a t e d from i t s c o m p r e s s i b i l i t y .
The e n t h a l p y of t r a n s f e r ( Δ Η ^ ^ ) of the s o l u t e between phases

Τ ο
1
can be d e t e r m i n e d from e x p e r i m e n t by a Van't Hoff p l o t of I n k v e r s u s
1/T a t c o n s t a n t d e n s i t y . ( 1 9 ) T h e r e f o r e , the RHS of eq. 22 can be
e v a l u a t e d f o r a p a r t i c u l a r f l u i d m o b i l e p h a s e - s o l u t e c o m b i n a t i o n and
1
the s l o p e of I n k a t c o n s t a n t p r e s s u r e as temperature i s v a r i e d can
be p r e d i c t e d .

Experimental
The e x p e r i m e n t a l a p p a r a t u s and t e c h n i q u e has been d e s c r i b e d i n d e t a i l

e l s e w h e r e . ( 2 0 , 2 1 ) The r e t e n t i o n f a c t o r s of naphthalene and b i p h e n y l
under i s o t h e r m a l c o n d i t i o n s a t v a r i o u s p r e s s u r e s were o b t a i n e d u s i n g
c a p i l l a r y columns c o a t e d w i t h a c r o s s - l i n k e d p h e n y l p o l y m e t h y l p h e n y l -
s i l o x a n e s t a t i o n a r y phase w i t h carbon d i o x i d e as the f l u i d mobile
phase. A V a r i a n 8500 s y r i n g e pump was o p e r a t e d under computer con
t r o l p r o v i d i n g a c c u r a t e , p u l s e f r e e c o n t r o l of the f l u i d p r e s s u r e .
The r e t e n t i o n times of the s o l u t e as a f u n c t i o n of p r e s s u r e were
determined by a r e p o r t i n g i n t e g r a t o r w i t h an a c c u r a c y of a t e n t h of a
second. S o l u b i l i t y d a t a f o r the s o l u t e s i n CO2 was o b t a i n e d from the
literature.(22)
The e f f e c t of temperature on r e t e n t i o n was s t u d i e s u s i n g
n-hexadecane on a 20 m, 50μ I.D. f u s e d s i l i c a c a p i l l a r y column c o a t e d
w i t h an OV-17 phase u s i n g FID d e t e c t i o n . The OV-17 was c r o s s - l i n k e d
i n - s i t u t o d e c r e a s e i t s s o l u b i l i t y i n the s u p e r c r i t i c a l f l u i d The
s t a t i o n a r y phase f i l m t h i c k n e s
e n t h a l p y of t r a n s f e r ( A H w „ (n-heptadecane,
A l l t e c h A s s o c i a t e s ) was o b t a i n e d on a column c o n t a i n i n g a c r o s s -
l i n k e d OV-17 s t a t i o n a r y phase over a range of temperatures at con
s t a n t d e n s i t y (0.38 g/cm ) . The r e t e n t i o n times of the s o l u t e s f o r
the Van't Hoff p l o t s and s o l u t e r e t e n t i o n as a f u n c t i o n of tempera
t u r e were determined by a r e p o r t i n g i n t e g r a t o r .
S o l u t e r e t e n t i o n as a f u n c t i o n of p r e s s u r e has been determined

e x p e r i m e n t a l l y f o r a wide number of s o l u t e s over a range of tempera
t u r e s and p r e s s u r e s . ( 1 , 2 3 - 2 5 ) The t r e n d i n r e t e n t i o n of a s o l u t e
w i t h p r e s s u r e can be p r e d i c t e d w i t h i n the l i m i t a t i o n s of our assump
t i o n s u s i n g eq. 11. The c a l c u l a t i o n s are then compared w i t h e x p e r i
mental d a t a f o r the r e t e n t i o n of naphthalene and b i p h e n y l a t v a r i o u s
temperatures and p r e s s u r e s were o b t a i n e d w i t h s u p e r c r i t i c a l C02»
F o r naphthalene the temperatures i n v e s t i g a t e d were 35.0°C,
60.4°C and 64.9°C w i t h p r e s s u r e s r a n g i n g from 75 atm to 120 atm. The
s o l u b i l i t y of naphthalene a t t h e s e temperatures i n s u p e r c r i t i c a l CO2
has been r e p o r t e d by McHugh and P a u l a i t i s . ( 2 2 ) T h i s d a t a a l l o w s the
t r e n d i n r e t e n t i o n to be p r e d i c t e d from the c a l c u l a t i o n of the s l o p e
f
of ( ô l n k / ô P ) T f o r naphthalene at these temperatures. A p l o t of the
m o b
data ( l n X v e r s u s p r e s s u r e ) from McHugh and P a u l a i t i s (22) i s shown
m o b
i n F i g u r e 1. The s l o p e ( ô l n X / ô P ) T a t the above-mentioned
temperatures was o b t a i n e d through i n t e r p o l a t i o n between the d a t a
p o i n t s . Where n e c e s s a r y , the d a t a range was extended to lower p r e s -
s u r e s than g i v e n i n r e f e r e n c e 22 as shown i n F i g u r e 2 by f i t t i n g the
d a t a u s i n g the method d e s c r i b e d by R e i d e t a l . ( 2 6 ) T h i s t e c h n i q u e
a l l o w s the modeling of the t r e n d i n r e t e n t i o n as a f u n c t i o n of p r e s -
s u r e a t c o n s t a n t temperatures f o r a w i d e r range i n p r e s s u r e s . The
i s o t h e r m a l c o m p r e s s i b i l i t y of s u p e r c r i t i c a l CO2 was c a l c u l a t e d f o r
the temperature and p r e s s u r e range of i n t e r e s t u s i n g eq. 13 and a
two-parameter c u b i c e q u a t i o n of s t a t e to p r e d i c t the molar volume of
the f l u i d . The s o l u t e p a r t i a l molar volume i n the s t a t i o n a r y phase
was assumed c o n s t a n t and independent of p r e s s u r e . ( 2 7 ) The molar

60.4°C
Ο
2h \
E_
><
55°C
35°C
-6 h
' 64.9no
°C
-8
80 _
Atm
Figure 1 The s o l u b i l i t y of n a p h t h a l e n e i n C 0 as a f u n c t i o n of
2
pressure. Data from McHugh and P a u l a i t i s . ( 2 2 )
-2h
0 40 80 120 160 200 240 280

Atm
Figure 2 The s o l u b i l i t y of n a p h t h a l e n e i n C 0 a t 35.0°C as a

2
f u n c t i o n o f p r e s s u r e u s i n g t h e t e c h n i q u e of R e i d e t a l .
(26) t o extend d a t a t o lower p r e s s u r e s .

ο
volume of naphthalene was determined t o be ~130.8 cm /mole. There
f o r e , w i t h the above s i m p l i f y i n g assumptions, e x p e r i m e n t a l s o l u b i l i t y
d a t a and the p r e d i c t i o n of the i s o t h e r m a l c o m p r e s s i b i l i t y of the
f l u i d as a f u n c t i o n of p r e s s u r e at c o n s t a n t temperature, the t r e n d i n
s o l u t e r e t e n t i o n c o u l d be c a l c u l a t e d based on an a p p r o p r i a t e c h o i c e
-s£at
of which g i v e s the b e s t f i t to the e x p e r i m e n t a l d a t a . The
e x p e r i m e n t a l d a t a f o r naphthalene a t 35.0°C and 64.9°C are g i v e n i n
F i g u r e s 3 and 4, where the e x p e r i m e n t a l l y o b t a i n e d Ink' v e r s u s p r e s
s u r e i s p l o t t e d a g a i n s t the p r e d i c t e d s l o p e of the r e t e n t i o n of
naphthalene from eq. 11 ( s o l i d l i n e ) . The s i m p l e thermodynamic model
was found to f i t the d a t a s a t i s f a c t o r i l y f o r t h i s s o l u t e .
The e x p e r i m e n t a l s o l u b i l i t y f o r b i p h e n y l i n s u p e r c r i t i c a l C 0 2 at
d i f f e r e n t temperatures as a f u n c t i o n of p r e s s u r e are shown i n
F i g u r e 5.(22) The s l o p e s of t h e s e p l o t s were used to determine
m o b
(ôlnX /ôP) T f o r b i p h e n y l i n s u p e r c r i t i c a l C 0 , and these v a l u e s
2
were supplemented w i t h s o l u b i l i t i e s p r e d i c t e d f o r lower p r e s s u r e s

from t h e o r y as needed.(26
the temperatures 35.8°C
and 7. The s o l i d l i n e i n t h e s e f i g u r e s i s the t h e o r e t i c a l p r e d i c t i o n
of the s l o p e of the r e t e n t i o n of the s o l u t e based on eq. 11 and the
-s£at
v a l u e which g i v e s the b e s t f i t t o the e x p e r i m e n t a l d a t a . Once
a g a i n the agreement between t h e o r y and experiment i s seen to be q u i t e
good f o r b i p h e n y l , as i t was f o r n a p h t h a l e n e .
The e f f e c t of the p a r t i a l molar volume of the s o l u t e i n the
s t a t i o n a r y phase at i n f i n i t e d i l u t i o n can be seen i n F i g u r e 8. This
-sât
f i g u r e shows how a f f e c t s the t h e o r e t i c a l s l o p e of the s o l u t e
r e t e n t i o n as a f u n c t i o n of p r e s s u r e . F o r the p a r t i c u l a r case of
-stat
b i p h e n y l at 55.2 C, i n c r e a s i n g V. i n c r e a s e s the s l o p e p r e d i c t e d
-stat1
" S,
s a t
from eq. 11, due to (V - ) becoming more dominant as

increases. Thus, the c o m b i n a t i o n of s o l u b i l i t y and chromatographic
d a t a may p r o v i d e a s i m p l e approach t o s t u d y the p a r t i a l molar volume
of s o l u t e s i n condensed p h a s e s .
On e x a m i n a t i o n of eq. 11, one can deduce t h a t as the i s o t h e r m a l
c o m p r e s s i b i l i t y of the s o l v e n t becomes l e s s i m p o r t a n t (temperature
and p r e s s u r e f u r t h e r removed from the c r i t i c a l temperature and p r e s -
s
s u r e ) , ( l n k V ô P ) T * P r o p o r t i o n a l to the s o l u b i l i t y of the s o l u t e i n
the f l u i d phase. T h e r e f o r e , i f s o l u b i l i t y i s found to be a l i n e a r
f u n c t i o n of d e n s i t y , then r e t e n t i o n w i l l m i r r o r t h i s b e h a v i o r and
a l s o be a l i n e a r f u n c t i o n of d e n s i t y . F u r t h e r , the f a r t h e r one i s
from the c r i t i c a l p r e s s u r e and temperature of the s o l v e n t , the more
1
l i k e l y one o b t a i n s a c o n s t a n t s l o p e [ ( b l n k / ôP)-p - c o n s t a n t ] .
The e f f e c t of temperature on s o l u t e r e t e n t i o n i n SFC has been
i n v e s t i g a t e d e x p e r i m e n t a l l y (5,8) and d e s c r i b e d theoretically·(9)
The e f f e c t of temperature as d i s c u s s e d i n the t h e o r y s e c t i o n , based
on the assumptions o u t l i n e d , r e s u l t e d i n eq. 22, where the t r e n d i n
r e t e n t i o n i s dependent on the volume e x p a n s i v i t y of the f l u i d , the
e n t h a l p y of t r a n s f e r of the s o l u t e from the mobile phase to the s t a -
t i o n a r y phase and the change i n the heat c a p a c i t y of the f l u i d m o b i l e
phase.
The volume e x p a n s i v i t y l e a d s to the r e t e n t i o n maxima seen i n SFC
near the c r i t i c a l p o i n t of the s u p e r c r i t i c a l f l u i d m o b i l e phase. The

110 120
Figure 3 R e t e n t i o n as a f u n c t i o n o f p r e s s u r e f o r naphthalene at
35.0°C. Soli
70 80 90 100 110120130140
Atm
Figure 4 R e t e n t i o n as a f u n c t i o n o f p r e s s u r e f o r n a p h t h a l e n e a t
64.9°C. S o l i d l i n e was p r e d i c t e d from e q . 11.
Solubility of Biphenyl in C 0 2
ι • I • I ι I ι L_
120 160 200 240 280
Atm
Figure 5 The s o l u b i l i t y of b i p h e n y l i n C 0 as a f u n c t i o n of
2
pressure. Data from McHugh and P a u l a i t i s . ( 2 2 )

Biphenyl
C0 2
— 1ο \
c -0.8 - \
\ 45.5°C
-1.6 \
-2.4 \35.8°C
1 ι Χ ι ι
70 80 90 100 110 120 130
Atm
F i g u r e 6. R e t e n t i o n a
35.8 and 45.5 °C. S o l i
70 80 90 100 110 120 130

Atm
F i g u r e 7. R e t e n t i o n as a f u n c t i o n o f p r e s s u r e f o r b i p h e n y l a t
55.2 °C. S o l i d l i n e was p r e d i c t e d from eq. 11.
70 80 90 100 110 120 130

Atm
F i g u r e 8. R e t e n t i o n as a f u n c t i o n o f p r e s s u r e f o r b i p h e n y l a t
55.2 °C. S o l i d l i n e w were p r e d i c t e d from eq. 11 u s i n g d i f f e r e n t
G t a t
V-i values.
V
Ί OO

e f f e c t o f temperature on t h e p a r t i a l d e r i v a t i v e i n t h e volume
e x p a n s i v i t y o f t h e f l u i d i s shown i n F i g u r e 9. The p a r t i a l d i f f e r
e n t i a l o f t h e f l u i d molar volume w i t h r e s p e c t t o temperature i s
p l o t t e d f o r n-pentane a t 35.5 atm (Case 1) and 69.1 atm (Case 2 ) .
One can see t h a t near t h e c r i t i c a l p o i n t f o r n-pentane (33.3 atm,
196.4°C) t h e d i f f e r e n t i a l term becomes dominant. A t p r e s s u r e s
f u r t h e r removed from the f l u i d ' s c r i t i c a l p r e s s u r e the d i f f e r e n t i a l
becomes n e g l i g i b l e , as seen i n F i g u r e 9.
F i g u r e 10 d e p i c t s e x p e r i m e n t a l d a t a from r e f e r e n c e 5 p l o t t e d as
Ink' v e r s u s t e m p e r a t u r e . The s o l i d l i n e i s t h e s l o p e i n r e t e n t i o n
p r e d i c t e d from e q . 22. The e n t h a l p y of t r a n s f e r [ A H w \ ] was T o
assumed independent The

thermodynamic r e l a t i o n s h i p o u t l i n e d i n t h e t h e o r y s e c t i o n p r e d i c t s
the major f e a t u r e s f o r t h e temperature dependence of r e t e n t i o n .
However, f u r t h e r d i s c u s s i o n i s needed r e g a r d i n g t h e apparent c o r r e
l a t i o n between t h e r e t e n t i o n maximum and m o l e c u l a r weight e v i d e n t i n
the d a t a of K l e s p e r and
i n v a r i a n t w i t h temperatur
T
f " oo
solvent. E q u a t i o n 22 i n c o r p o r a t e s a c o r r e c t i o n term ( ^ J Q ACp^dT) t o
ΔΗ? which dominates near the c r i t i c a l p o i n t o f t h e f l u i d . Therefore,
two c o n t r i b u t i o n s compete near t h e s o l v e n t ' s c r i t i c a l p o i n t ; ( a ) t h e
volume e x p a n s i v i t y of t h e s o l v e n t and (b) ACp. D e n s i t y e f f e c t s both

of these terms through i t s e f f e c t on t h e s o l v e n t molar volume and the
number of i n t e r m o l e c u l a r i n t e r a c t i o n s o c c u r r i n g i n t h e c r i t i c a l
region. As s t a t e d e a r l i e r , w i t h c o n d i t i o n s of s o l u t e i n f i n i t e
d i l u t i o n which a r e approximated by SFC, AC" can be assumed t o be

e q u a l t o the heat c a p a c i t y of the m o b i l e phase. F o r carbon d i o x i d e
at i t s c r i t i c a l p o i n t , t h e heat c a p a c i t y f o l l o w s a s h a r p l y i n c r e a s i n g
gaussian function.(18) S i n c e no s i m p l e m a t h e m a t i c a l r e l a t i o n s h i p
p r e s e n t l y e x i s t s f o r ACp a t t h e p r e s s u r e s r e l e v a n t t o SFC, t h i s term

can o n l y be e s t i m a t e d c r u d e l y . ( 9 ) O v e r a l l , t h i s approach p r e d i c t s
the t r e n d i n r e t e n t i o n q u i t e w e l l . The a d d i t i o n o f the c o r r e c t i o n
term t o the e n t h a l p y of s o l u t e t r a n s f e r making i t dependent on
t e m p e r a t u r e , a l l o w s s i m u l a t i o n of the e f f e c t of t h e change i n the
number of i n t e r m o l e c u l a r i n t e r a c t i o n s between the s o l u t e and the
s o l v e n t m o l e c u l e s as the d e n s i t y d e c r e a s e s r a p i d l y near the c r i t i c a l
p o i n t of the s o l v e n t .
F i g u r e 11 c o n t a i n s t h e e x p e r i m e n t a l d a t a f o r c h r y s e n e (_5)
r e p l o t t e d as Ink' v e r s u s temperature w i t h t h e s o l i d l i n e b e i n g t h e
t h e o r e t i c a l p r e d i c t i o n of t h e s l o p e from e q . 22. The d a t a i n F i g u r e s
10 and 11 a r e both w i t h n-pentane as the f l u i d m o b i l e phase; t h e
d i f f e r e n c e between t h e two s e t s of d a t a i s t h e e x p e r i m e n t a l
pressure. The model p r e d i c t s t h e t r e n d i n r e t e n t i o n f o r both cases
quite well. I n F i g u r e 11 one can see the d e c r e a s e i n importance of
the volume e x p a n s i v i t y and heat c a p a c i t y of the f l u i d on r e t e n t i o n as
the e x p e r i m e n t a l c o n d i t i o n s a r e f u r t h e r removed from the c r i t i c a l
temperature and p r e s s u r e o f t h e f l u i d .
A d d i t i o n a l e v i d e n c e s u p p o r t i n g the thermodynamic model was
o b t a i n e d u s i n g a c a p i l l a r y column w i t h s u p e r c r i t i c a l C 0 and t h e
2
s o l u t e hexadecane; modeling was u n d e r t a k e n u s i n g a AH"^ ^ v a l u e of

Tn

40 ι Case 1
30
20
\ Case 2
10 -
M
0 ι ι ι ι ι—ι—K~t~h-η—r
20 60 100 140 180 220 260
Figure 9 Plot of ( b V ™ / b T ) p temperatur n-pentan

35.5 atm (Case 1) and 69.1 atm (Case 2 ) .
100 200 300

Temperature, °C
Figure 10 E x p e r i m e n t a l d a t a ( R e f . 5) and theoretical model (solid

—
oo
l i n e ) f o r chrysene w i t h n-pentane, 35.5 atm, ΔΗ · Ί ( Ύ χ =
K }
5.0 K c a l / m o l e .

1
-10.6 Kcal/mole o b t a i n e d from a "Van't H o f f " ( I n k v s . 1/T) p l o t of
heptadecane on the same column. T h i s d a t a i s shown i n F i g u r e 12,
w i t h the s o l i d l i n e b e i n g the t h e o r e t i c a l p r e d i c t i o n from eq. 22.
Once a g a i n the f i t of the e x p e r i m e n t a l d a t a by the model i s q u i t e
good.
Conclusion
The thermodynamic r e l a t i o n s h i p d e s c r i b e d i n t h i s a r t i c l e have been

shown to d e s c r i b e the f e a t u r e s of s o l u t e r e t e n t i o n as a f u n c t i o n of
temperature at c o n s t a n t p r e s s u r e and as a f u n c t i o n of p r e s s u r e at
c o n s t a n t temperature ( g i v e n the s o l u b i l i t y of the s o l u t e i n the f l u i d
mobile p h a s e ) . The dependence of r e t e n t i o n upon temperature can
a p p a r e n t l y be a s c r i b e d to a c o m b i n a t i o n of two e f f e c t s . These
e f f e c t s i n c l u d e the r a p i d change i n the number of i n t e r m o l e c u l a r
i n t e r a c t i o n s of the s o l u t e - s o l v e n t m o l e c u l e s as one p r o g r e s s e s
through the c r i t i c a l p o i n
e x p a n s i v i t y of the s o l v e n t
s o l v a t o c h r o m i c probes ha y explore
i n t e r a c t i o n s and c l a r i f i e d the n a t u r e of the f l u i d phase s o l v a t i o n
phenomena.(28)
The RHS of eq. 22 reduces to the l i m i t i n g case f o r both l i q u i d
and gas chromatography, where ΔΗ^ i s a constant over a narrow
temperature range ( Δ θ ? = 0) and the e f f e c t of the volume e x p a n s i v i t y

ρ
of the mobile phase i s n e g l i g i b l e . F o r t h i s c a s e , s o l u t e r e t e n t i o n

i s dominated by the p a r t i a l molar e n t h a l p y of s o l u t e t r a n s f e r at
i n f i n i t e d i l u t i o n (ΔΗ?). The volume e x p a n s i v i t y and Δ θ ~ become

dominant near the c r i t i c a l temperature of the s o l v e n t , c o n t r i b u t i n g
to the p h y s i c a l and c h e m i c a l phenomenon c o n t r o l l i n g r e t e n t i o n i n the
SFC regime. In d e r i v i n g t h i s r e l a t i o n s h i p we have made the s i m p l i f y
i n g assumption that Δ Η ? ^ ^ i s the same i n both the h i g h

0
temperature (gas chromatography) and low temperature ( l i q u i d chroma

tography) regions. While t h i s assumption i s not s t r i c t l y c o r r e c t ,
(29) i t p r o v i d e s a b a s i s f o r treatment of the i n t e r m e d i a t e s u p e r
c r i t i c a l f l u i d regime.
R e t e n t i o n as a f u n c t i o n of p r e s s u r e at c o n s t a n t temperature
p o i n t s out the importance of the r e l a t i o n s h i p between s o l u t e s o l u
b i l i t y i n the f l u i d mobile phase to the t r e n d i n s o l u t e r e t e n t i o n .
The t r e n d i n s o l u t e r e t e n t i o n i s demonstrated to be dependent on
i s o t h e r m a l c o m p r e s s i b i l i t y , s o l u b i l i t y i n the f l u i d and the p a r t i a l
molar volume of the s o l u t e i n the s t a t i o n a r y phase.
T h i s work p o i n t s to the p o s s i b i l i t y of d e t e r m i n i n g p a r t i a l molar
volumes of d i f f e r e n t s o l u t e m o l e c u l e s i n a wide range of d i f f e r e n t
s t a t i o n a r y phases at i n f i n i t e d i l u t i o n , d e t e r m i n i n g s o l u t e s o l u b i l i t y
i n the i n f i n i t e d i l u t i o n regime and the f u n c t i o n a l dependence of the
heat c a p a c i t y of the f l u i d mobile phase u s i n g r e l a t i v e l y s i m p l e
chromatographic experiments. In f u t u r e work, a more u n i v e r s a l
approach i n f l u i d s w i t h an EOS i s b e i n g c o n s i d e r e d , which w i l l extend
the p r e d i c t i o n of the t r e n d i n r e t e n t i o n to a wider range of s o l u t e s .

1.6
1.2
0.8 — X
0.4
_ χ >
0
X
-0.4
X xi—•
-0.8 X*X
-1.2
-1.6 1 1 I 1 III.
1 1 ! 1 1 1
1 1 1 1 1 1 1 1
0 5
Figure 11 E x p e r i m e n t a l d a t a ( R e f . 5) and t h e o r e t i c a l
model ( s o l i d
-co
s
l i n e ) f o r chrysene i n n-pentane a t 69.1 atm, AHw.p \ 0
-3.0 K c a l / m o l e .
3.0
Temperature, °C
Figure 12 E x p e r i m e n t a l d a t a f o r hexadecane on OV-17 with C0 ,2
—00
76.5 atm and t h e o r e t i c a l model ( s o l i d line), Δ^^/ \ - Τ ο
-10.6 K c a l / m o l e .

Acknowledgments
The a u t h o r s acknowledge t h e t e c h n i c a l a s s i s t a n c e o f R. W. Gale and

the h e l p f u l d i s c u s s i o n s o f R. C. P e t e r s e n and t h e support of t h e U.S.
Department of Energy, O f f i c e o f B a s i c Energy S c i e n c e , under
C o n t r a c t DE-AC06-76RL0 1830.
References
1. Van Wasen, U.; Schneider, G. M., Chromatographia, (1975), 8,
274.
2. Geve, D. R.; Board, R.; McManigill, D., Anal. Chem., (1982), 54,
736.
3. Van Wasen, U.; Swaid, I.; Schneider, G. Μ., Agnew. Chem. Int.
Ed. Engl., (1980), 19, 575.
4. Schmitz, F. P.; Hilger
Setzer, U.; Klesper, E., J. of High Res. Chrom. & Chrom. Comm.;
(1984), 7, 590.
5. Schmitz, F. P.; Leyendecker, D.; Klesper, E., Ber. Bunsenges.
Phys. Chem., (1984), 88, 912.
6. Smith, R. D.; Chapman, E. G.; Wright, B. W., Anal. Chem.,
(1985), 57.
7. Novotny, M.; Bertsch, W.; Zlatkis, Α., J. Chromatogr., (1971),
61, 17.
8. Schmitz, F. P.; Leyendecker, D.; Klesper, E., J. Chromatogr.,
(1984), 315, 19.
9. Yonker, C. R.; Wright, B. W.; Petersen, R. C.; Smith, R. D.,
accepted for publication in J. Phys. Chem.
10. Gitterman, M.; Procaccia, I., J. Chem. Phys., (1983), 78, 2648.
11. Klotz, I. M.; Rosenberg, R. Μ., "Chemical Thermodynamics," 3rd
Ed. W. A. Benjamin, Inc. (1972).
12. Meyer, E. F., J. Chem. Ed., (1973), 50, 191.
13. Van Ness, H. C.; Abbott, Μ. Μ., "Classical Thermodynamics of Non
Electrolyte Solutions with Applications to Phase Equilibria,"
McGraw-Hill Book Company (1982).
14. Redlich, O.; Kwong, J. N. S., Chem Rev., (1949), 44, 233.
15. Peng, D. Y.; Robinson, D. B., Ind. Eng. Chem. Fundam., (1976),
15,59.
16. Horvath, C.; Melander, W.; Molnar, I., J. Chromatogr., (1976),
125, 129.

17. Moore, W. J., "Physical Chemistry", 4th Ed., Prentice-Hall,

Inc., (1972).
18. Gas Encyclopedia, Elsevier Scientific Publishing Company,
(1972).
19. Lauer, H. H.; McManigill, D.; Board, R. D., Anal. Chem., (1983),
55, 1370.
20. Wright, B. W.; Smith, R. D., Chromatographia, (1984), 18, 542.
21. Smith, R. D., Kalinoski, H. T., Udseth, H. R.; Wright, B. W.,
Anal. Chem., (1984), 56, 2476.
22. McHugh, M.; Paulaitis, M. E., J. Chem. Eng. Data, (1980), 25,
326.
23. Sie, S. T.; Rijnders
24. Semonian, B. P.; Rogers, L. B., J. Chromatogr. Sci., (1978), 16,
49.
25. Van Wasen, U.; Schneider, G. Μ., J. Phys. Chem., (1980), 84,
229.
26. Reid, R. C., Kurnik, R. T.; Holla, S. J., J. Chem. Eng. Data,
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28. Yonker, C. R.; Frye, S. L.; Kalkwarf, D. R.; Smith, R. D., to be
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Received July 8, 1986

Chapter 15
Supercritical Fluid Extraction and Chromatography

of Nonpolar Nonvolatile Coal-Derived Products
J. W. Jordan, R. J . Skelton, and L . T. Taylor
Department of Chemistry, Virginia Polytechnic Institute and State University,

Blacksburg, V A 24061
In recent years supercritical fluid chromatography

has gained attention as an alternative technique to
high performance
separation of nonvolatile or thermally labile
compounds, whose analysis with gas chromatography is
impossible. The work presented here demonstrates a
system that allows supercritical fluid extraction of
a high boiling coal-derived material with subsequent
direct introduction of a fraction of each extract
onto a packed column for analysis via supercritical
fluid chromatography. Detection of the eluates
included variable wavelength UV and FTIR
spectrometry. The coal derived products studied were
taken from a bench scale coal liquefaction reactor,
in which the same catalyst was used for twenty-five
consecutive days. Chemical changes that occur as the
catalyst decays were of prime interest. Most
significant changes were noted in the aromatic
fraction analysis, where a trend towards molecules
with higher numbers of condensed rings was observed
as the catalyst decayed.
I t was s u g g e s t e d i n the l a t e 5 0 ' s t h a t s u p e r c r i t i c a l f l u i d s c o u l d

be used as m o b i l e p h a s e s . ( 1 ) S u p e r c r i t i c a l F l u i d Chromatography
(SFC) was i n t r o d u c e d i n 1961 when K l e s p e r ( 2 ) d e m o n s t r a t e d the use
of a s u p e r c r i t i c a l f l u i d as a m o b i l e p h a s e . These "dense g a s e s " or
s u p e r c r i t i c a l f l u i d s have the a b i l i t y t o s o l u b i l i z e n o n v o l a t i l e
compounds, and t h u s cause them to m i g r a t e down a column i n
p a r t i t i o n chromatography. (_3)
T h i s form of chromatography has s e v e r a l advantages t h a t stem
from the p h y s i c a l p r o p e r t i e s t h a t are e x h i b i t e d by the m o b i l e
phase. In g e n e r a l , d i f f u s i v i t i e s and v i s c o s i t i e s are i n t e r m e d i a t e
between t h o s e of a l i q u i d and a g a s , a l l o w i n g more r a p i d a n a l y s i s
when compared t o the analogous methods u s i n g a c o n v e n t i o n a l l i q u i d
mobile phase.
0097-6156/87/0329-0189$06.00/0

Many of the same p r o p e r t i e s t h a t make s u p e r c r i t i c a l f l u i d s

advantageous i n chromatography a l s o enhance t h e i r a b i l i t y t o
e x t r a c t compounds from w i t h i n a sample m a t r i x . ( 4 ) A l s o , s i n c e the
s o l u b i l i t y of most compounds i s dependent on the d e n s i t y of t h e
supercritical f l u i d , selective extraction is possible.(5) These
p r o p e r t i e s a r e w e l l known, and have been e x p l o i t e d i n some c a s e s
where the e x t r a c t i o n was f o r m e r l y done w i t h a l i q u i d . In many
c a s e s , the q u a l i t y o f e x t r a c t i s h i g h e r , and e x t r a c t i o n s a r e of
h i g h e r e f f i c i e n c y than w i t h l i q u i d s . Supercritical fluids,
e s p e c i a l l y C 0 , a r e a l s o o f t e n l e s s e x p e n s i v e , l e s s t o x i c and l e s s
2
flammable than t h e i r o r g a n i c l i q u i d phase c o u n t e r p a r t s .

W i t h the d e m o n s t r a t i o n of s u p e r c r i t i c a l f l u i d e x t r a c t i o n , an
o b v i o u s e x t e n s i o n would be t o e x t r a c t o r d i s s o l v e the compounds of
i n t e r e s t i n t o the s u p e r c r i t i c a l f l u i d b e f o r e a n a l y s i s w i t h S F C . ( 6 )
T h i s would be a n a l o g o u s to the c a s e i n HPLC, where t h e m o b i l e phase
s o l v e n t i s commonly used f o r d i s s o l v i n g the sample. The work
d e s c r i b e d here w i l l employ a system c a p a b l e o f e x t r a c t i n g m a t e r i a l s
with a s u p e r c r i t i c a l f l u i
e x t r a c t onto the column
s e p a r a t e d m a t e r i a l s w i l l be by o n - l i n e UV s p e c t r o s c o p y and i n f r a r e d
spectrometry. The o p t i m i z e d S F E / S F C system has been used to study
selected nonvolatile coal-derived products. The work r e p o r t e d here
i n v o l v e d the a l i p h a t i c and a r o m a t i c h y d r o c a r b o n f r a c t i o n s from t h i s
residuum m a t e r i a l . R e s i d u a at s e v e r a l times were taken from the
r e a c t o r and examined which p r o v i d e d some i n s i g h t i n t o the e f f e c t s
of c a t a l y s t decay on the p r o d u c t s p r o d u c e d i n a p i l o t p l a n t
operation.
Experimental
The samples f o r s t u d y were o b t a i n e d from Conoco R e s e a r c h D i v i s i o n

i n L i b r a r y , P A , as s o l i d m a t e r i a l s capped under n i t r o g e n g a s .
These m a t e r i a l s which were s u b s e q u e n t l y s t o r e d at 5 ° C o r i g i n a t e d
from a H y d r o c a r b o n R e s e a r c h I n s t i t u t e bench s c a l e r u n (#227-20) of
the C a t a l y t i c Two-Stage L i q u e f a c t i o n process.(2) The s a m p l e s ,
which a r e d e s i g n a t e d " p r e s s u r e - f i l t e r l i q u i d s , " a r e t h e s o l i d s f r e e
p o r t i o n of the major second s t a g e p r o d u c t s t h a t have been " t o p p e d "
i n the a t m o s p h e r i c s t i l l , t h e n f i l t e r e d . The p r o c e s s u t i l i z e d a
donor s o l v e n t d e r i v e d from p r e v i o u s r u n s and new c a t a l y s t m a t e r i a l .
I l l i n o i s 6, B u r n i n g S t a r c o a l was u s e d . The p r o c e s s was r u n f o r 25
consecutive days, with operating c o n d i t i o n s held c o n s t a n t , except
f o r the i n i t i a l s t a r t - u p p e r i o d ( i . e . days 1 - 3 ) . Since conditions
were c o n s t a n t , any change i n the p r o d u c t s formed, s h o u l d be a
f u n c t i o n of c a t a l y s t age. The f i l t e r e d p r o d u c t s were d i s t i l l e d by
Conoco i n t o 2 f r a c t i o n s , t h o s e b o i l i n g under 8 5 0 ° F , and t h o s e
above. ( A c t u a l f r a c t i o n a t i o n was a t 3 2 0 ° C P o t / 2 7 0 ° C Column/5 T o r r
(850°F)). F u r t h e r d e t a i l s of the c o a l l i q u e f a c t i o n p r o c e s s a r e
available elsewhere.(7,8)
The m a t e r i a l s b o i l i n g above 8 5 0 ° F , were s u b s e q u e n t l y s e p a r a t e d
i n t o f o u r f r a c t i o n s by a p r e p a r a t i v e s c a l e c h e m i c a l c l a s s
s e p a r a t i o n i n our l a b o r a t o r y . T h i s was done as f o l l o w s : 2 gms of
the r e s i d u a l m a t e r i a l were ground and d i s s o l v e d i n t e t r a h y d r o f u r a n
(HPLC g r a d e , F i s h e r P r o d u c t s , F a i r l a w n N J ) . Ten grams of 30-40ym
s i l i c a gel ("Sepralyte", Analytichem I n t . , Harbor C i t y , C A ) , which
was p r e v i o u s l y washed w i t h methanol and d r i e d , was added t o the THF

15. JORDAN ET AL. Extraction & Chromatography of Coal-Denved Products 191
solution. T h i s s l u r r i e d m a t e r i a l was then r o t a r y e v a p o r a t e d t o

dryness. The d r i e d s i l i c a g e l w i t h a d s o r b e d c o a l - d e r i v e d p r o d u c t
was p l a c e d a t the t o p o f a g l a s s column which was p r e v i o u s l y
s l u r r y - p a c k e d w i t h 40 gms of the same s i l i c a g e l u s i n g h e x a n e . A
f i l t e r paper was used t o s e p a r a t e the l a y e r s . The g l a s s column had
a d i a m e t e r which a l l o w e d the h e i g h t ( 4 . 5 " ) of the packed p o r t i o n of
the column t o e q u a l 3 times i t s d i a m e t e r ( 1 . 5 " ) . The m a t e r i a l s
were e l u t e d w i t h t h r e e column volumes each of hexane, t o l u e n e ,
c h l o r o f o r m and t e t r a h y d r o f u r a n ( c a . 300 mL e a c h ) . The hexane and
t o l u e n e f r a c t i o n s were t a k e n t o be s t u d i e d h e r e . Three s e p a r a t i o n s
of t h i s t y p e were d o n e , r e p r e s e n t i n g the 1 s t , 14th and 2 5 t h day of
the r u n . These a r e samples l a b e l e d 4 4 , 57 and 6 8 , r e s p e c t i v e l y .
The f r a c t i o n s were f i l t e r e d w i t h a 5 ym f i l t e r a p p a r a t u s
( M i l l i p o r e , B e d f o r d , MA) t o remove any s i l i c a o r i g i n a t i n g from the
p r e p a r a t i v e s c a l e c o l u m n . The f r a c t i o n s were then r o t a r y
e v a p o r a t e d t o near d r y n e s s i n t a r e d round bottom f l a s k s . These
were s u b s e q u e n t l y d r i e d o v e r n i g h t i n a vacuum oven at 6 0 ° C and
weighed. The hexane an
mL, r e s p e c t i v e l y , w i t h C C l
i n t h i s s o l v e n t as w e l l as i n THF.
A n a l y s i s of t h e s e two f r a c t i o n s was p e r f o r m e d by s u p e r c r i t i c a l
f l u i d e x t r a c t i o n / c h r o m a t o g r a p h y , u t i l i z i n g the s a m p l i n g p r o c e d u r e s
previously described.(6) T h i s was done by e v a p o r a t i n g the s o l v e n t
from t h e f r a c t i o n i n the p r e s e n c e o f d r y , washed, i g n i t e d sand
which was then used to f i l l the e x t r a c t i o n a p p a r a t u s . Direct
i n j e c t i o n of some samples (THF s o l u t i o n ) was a l s o done f o r
comparison. E x p e r i m e n t s were c a r r i e d out u s i n g a H e w l e t t P a c k a r d
1082B L i q u i d Chromatograph m o d i f i e d f o r use w i t h s u p e r c r i t i c a l
fluids. Columns u t i l i z e d i n c l u d e a H e w l e t t P a c k a r d 15cm χ 4.6mm
i . d . C^g column w i t h 5ym p a c k i n g and a Dupont 25cm χ 4.6mm i . d . NH^
column, a l s o w i t h 5ym p a c k i n g . Pure CO^ was used as the m o b i l e
phase ( S c o t t S p e c i a l t y G a s e s , P l u m s t e a d s v i l l e , P A ) . A l l on-line
e x t r a c t i o n / c h r o m a t o g r a m s u t i l i z e d a 100yL l o o p s i z e . Traditional
s a m p l i n g u t i l i z e d a 10yL s y r i n g e and 20yL l o o p .
A l l e x p e r i m e n t s u t i l i z e d a v a r i a b l e wavelength UV d e t e c t o r .
A n a l y s i s o f the hexane f r a c t i o n was c a r r i e d o u t u s i n g b o t h the UV
d e t e c t o r and an o n - l i n e N i c o l e t 6000 F T I R . The FTIR f l o w c e l l
i n t e r f a c e has been d e s c r i b e d i n d e t a i l e l s e w h e r e . ( 9 ) T h i s same
FTIR was a l s o used t o g a t h e r s t a t i c s p e c t r a on the v a r i o u s
f r a c t i o n s , u t i l i z i n g a l i q u i d c e l l w i t h KBr windows.
T a b l e I shows the r e s u l t s of the c l a s s s e p a r a t i o n of residuum w i t h

a b s o l u t e and p e r c e n t r e c o v e r y f o r each of the f o u r f r a c t i o n s f o r
day 1, 14 and 25. In g e n e r a l , the c o n c e n t r a t i o n of the l e s s p o l a r
(hexane and t o l u e n e ) f r a c t i o n s d e c r e a s e d o r remained c o n s t a n t w i t h
t i m e ; w h i l e , the more p o l a r (CHCl^ and THF) f r a c t i o n s i n c r e a s e d i n
percentage. T h i s i s b e s t n o t e d from d a t a f o r days 14 and 2 5 . Data
from day 1 a r e somewhat v a r i a n t from t h i s t r e n d . This is probably
due to the i n c o n s i s t e n c y i n o p e r a t i n g c o n d i t i o n s t h a t o c c u r r e d
d u r i n g the s t a r t - u p p e r i o d . Such a s s u m p t i o n s s h o u l d be viewed
c a u t i o u s l y s i n c e t h e p e r c e n t weight r e c o v e r y from day 14 and 25 i s
not c o n s t a n t .

The hexane f r a c t i o n s from r u n s 44 and 68 have i d e n t i c a l spec

tral i n CCI . These show a l i p h a t i c C-H (CH- sym s t r = 2872 cm \
-1 -1 -1
asym = 2962 cm ; C H sym s t r * 2853 cm , asym = 2926 cm ) and
0
2 -± -ι -1
b e n d i n g modes (1470 cm - 1350 cm ) as w e l l as a band at 1600 cm
which may be an a r o m a t i c r i n g v i b r a t i o n . No o t h e r functionalities
T a b l e I. R e s u l t s of Residuum C l a s s S e p a r a t i o n *
Fraction R e s i d 44 R e s i d 57 R e s i d 68
(Day 1) (Day 14) (Day 25)
Hexane 0.075
(3.8%)
Toluene 1.071 gms. 0.939 gms. 0.857 gms.

(54.2%) (48.0%) (48.4%)
CHC1 0.085 gms. 0.082 gms. 0.103 gms.

(4.3%) (4.0%) (5.8%)
THF 0.743 gms. 0.755 gms. 0.7 76 gms.

(37.6%) (38.5%) (43.8%)
Total 1.974 gms. 1.958 gms. 1.772 gms.

Weight
Recovered
% Sample (98.7%) (97.8%) (88.5%)

Recovered
•Number i n p a r e n t h e s i s e q u a l s p e r c e n t o f r e c o v e r e d m a t e r i a l .
a r e p r e s e n t which c a n be d e t e c t e d . In b o t h c a s e s , t h e amount of CH^

1
s t r e t c h i n g i s much g r e a t e r than C H s t r e t c h i n g .
3 This indicates that
the a l i p h a t i c u n i t s a r e e i t h e r l o n g i n l e n g t h o r a r e i n t h e form of
saturated r i n g s .
The t o l u e n e f r a c t i o n s from d i f f e r e n t days a r e a l s o v e r y similar
t o each o t h e r . A g a i n , by f a r t h e most i n t e n s e modes of absorbance
a r e a l i p h a t i c C-H s t r e t c h i n g and b e n d i n g , however a g r e a t d e a l of
1 1
a r o m a t i c C-H s t r e t c h i n g between 3000 cm and 3100 cm also exists.
There i s a l s o a v e r y s m a l l amount of a b s o r b a n c e i n the N~H s t r e t c h
1 1 1
ing (3740 cm ) and 0-H s t r e t c h i n g (3610 cm and 3550 cm ) regions.
In g e n e r a l , compounds w i t h t h e s e f u n c t i o n a l i t i e s s h o u l d e l u t e i n the
last two f r a c t i o n s . However, v e r y h i n d e r e d f u n c t i o n a l i t i e s often

15. JORDAN ET AL. Extraction & Chromatography of Coal-Derived Products 193
e l u t e i n the a r o m a t i c f r a c t i o n , and i t i s probable that absorbances

i n t h e s e r e g i o n s a r e due to these molecules. A g a i n , t h e r e i s more
CH 2 than CH^ absorbance. There i s a l s o some i n c r e a s e i n a r o m a t i c
C-H i n sample 68 (day 25) when compared t o sample 44 (day 1 ) .
F u r t h e r s e p a r a t i o n of t h e s e m a t e r i a l s i s needed f o r a b e t t e r
u n d e r s t a n d i n g of t h e i r c o m p o s i t i o n . SFC o f Hexane F r a c t i o n s . The
hexane f r a c t i o n s were a n a l y z e d w i t h an a m i n o - p r o p y l derivatized
silica column under moderate d e n s i t y C 0 2 conditions. Other columns
investigated i n c l u d e d cyano, p h e n y l , and C derivatized silica.
-LO
No m o d i f i e r s were used i n any o f t h e s e s e p a r a t i o n s . F i g u r e 1 shows

the chromatograms a c h i e v e d f o r sample 57 (Day 14) wherein the top
chromatogram was produced by m o n i t o r i n g 254 nm and the bottom
chromatogram by m o n i t o r i n g 280 nm. D e t e c t i o n at 210 nm was also
employed, but no absorbances were s e e n L a t e r e l u t i n g peaks a r e
more i n t e n s e i n a l l c a s e
( e a r l y peaks d e c r e a s e i
i n t e n s e l y f o r the same amount i n j e c t e d ) . T h i s would i n d i c a t e that
t h e l a t e r e l u t i n g m a t e r i a l s p r o b a b l y have more e x t e n s i v e
c o n j u g a t i o n , and represent molecules like the PAHs. There i s ,
however, v e r y l i t t l e a r o m a t i c C-H stretching i n the s t a t i c infrared
s p e c t r a of t h e whole f r a c t i o n , a l t h o u g h t h e r e i s the band c e n t e r e d
at approximately 1600 cm which i s a s s o c i a t e d w i t h a r o m a t i c ring
vibration. The absence of C-H a r o m a t i c s t r e t c h i n g c o u l d be
explained i f : (a) t h e r e i s a c o n s i d e r a b l e number of aliphatic
s u b s t i t u e n t s on the a r o m a t i c n u c l e i or n u c l e u s o r (b) many
s a t u r a t e d r i n g s a r e f u s e d t o an a r o m a t i c n u c l e u s . An e x t e n s i v e
number of a l i p h a t i c s u b s t i t u e n t s may have caused i n c r e a s e d
solubility i n hexane, which e n a b l e d t h e s e m a t e r i a l s t o e l u t e from
the silica.
To g a i n f u r t h e r i n f o r m a t i o n c o n c e r n i n g the hexane f r a c t i o n s ,
o n - l i n e s u p e r c r i t i c a l f l u i d e x t r a c t i o n / S F C was c o u p l e d w i t h o n - l i n e
FTIR d e t e c t i o n . FTIR s h o u l d have an advantage i n t h a t i t i s more
s e n s i t i v e t o a l i p h a t i c hydrocarbons than the UV d e t e c t o r .
B a s i c a l l y , a f l o w c e l l i s p l a c e d i n the FTIR i n s t r u m e n t and
i n f r a r e d s p e c t r a a r e g a t h e r e d i n t h e form of i n t e r f e r o g r a m s c a .
e v e r y 0.5 second. The d a t a o b t a i n e d can be used t o c r e a t e a
chromatogram, u t i l i z i n g absorbance o v e r the e n t i r e i n f r a r e d
spectrum, r a t h e r than a s i n g l e w a v e l e n g t h . T h i s a n a l y s i s was done
on samples 44 and 68 ( 1 s t and 25th d a y ) . F i g u r e 2 shows one of
t h e s e "chromatograms" (day 25), known as Gram-Schmidt
R e c o n s t r u c t i o n s (GSR). One major peak i s seen, which, when
compared w i t h the UV c h r o m a t o g r a p h i c t r a c e o b t a i n e d s i m u l t a n e o u s l y ,
shows maximum IR absorbance w e l l b e f o r e any absorbance i n the UV.
A spectrum c o n s i s t i n g of 8 coadded f i l e s taken near the peak
maximum r e v e a l s t h a t the o n - l i n e spectrum i s almost e x a c t l y the
same as the s t a t i c spectrum of the whole jample. The e x c e p t i o n i s
t h e d i s a p p e a r a n c e of the band a t 1600 cm i n the f i l e spectrum.
T h i s o b s e r v a t i o n a l o n g w i t h the l a c k o f UV r e s p o n s e i n t h i s e l u t i o n

0 1 4 · · 10 M 14 η Ι· 90
TIME. MINUTES
F i g u r e 1. SFC s e p a r a t i o n (3 mL/min) o f hexane f r a c t i o n Day 14

(Sample 57) on an a m i n o p r o p y l d e r i v a t i z e d 5 ym s i l i c a column (25
cm χ 4.6 mm, i . d . ) a t 4 0 ° C . M o b i l e phase i s C 0 a t an average
2
p r e s s u r e of 2800 p s i . Top t r a c e c o r r e s p o n d s t o d e t e c t i o n a t 254

nm; bottom t r a c e - 280 nm.
Data P o i n t s
F i g u r e 2. Gram-Schmidt R e c o n s t r u c t i o n o b t a i n e d from
S F E / S F C / F T I R of hexane f r a c t i o n o f Day 25 s a m p l e .

15. JORDAN ET AL. Extraction ά Chromatography of Coal-Derived Products 195
volume i n d i c a t e s t h a t t h e s e components a r e t o t a l l y a l i p h a t i c i n
n a t u r e ; whereas, t h e l a t e r e l u t i n g m a t e r i a l s a r e a r o m a t i c and a r e
of i n s u f f i c i e n t c o n c e n t r a t i o n t o be d e t e c t e d by o n - l i n e FTIR
detection.
A l t h o u g h o n l y one peak i s i n d i c a t e d by the GSR, a c o m p a r i s o n
of s p e c t r a o b t a i n e d from the f r o n t of the peak w i t h t h o s e which
e l u t e i n the l a t e r h a l f of the peak can be made. When t h i s
t e c h n i q u e was a p p l i e d to t h e s e d a t a , i t was found t h a t c e r t a i n
changes i n the s p e c t r a were o b s e r v e d . F i g u r e 3 shows the f i r s t 6
s p e c t r a i n the C-H s t r e t c h i n g r e g i o n o b t a i n e d o v e r t h e major peak
i n the GSR. Each of t h e s e s p e c t r a r e p r e s e n t 8 coadded f i l e s ,
r e s u l t i n g i n a time r e s o l u t i o n of about 4 seconds per f i l e .
I n f r a r e d s p e c t r a taken from the f r o n t of the peak show the l o w e s t
m e t h y l t o methylene r a t i o . As each subsequent f i l e i s r a t i o e d to
keep the methylene peak c o n s t a n t , the a b s o r b a n c e s due t o m e t h y l s
i n c r e a s e o v e r the w i d t h of the p e a k . Subsequent f i l e s show a
l e v e l i n g of t h i s r a t i o .
unfortunately, analysi
n o t r e v e a l any s i g n i f i c a n
p o s s i b l e t h a t the r e l a t i v e amount of each component p r o d u c e d i s
e q u i v a l e n t , but t h a t the t o t a l p r o d u c t i o n s u f f e r s as the c a t a l y s t
becomes l e s s e f f e c t i v e .
SFC o f T o l u e n e F r a c t i o n s
To a i d i n u n d e r s t a n d i n g the components i n the t o l u e n e f r a c t i o n , a

l i m i t e d SFC s t u d y of model c o n d e n s e d - r i n g a r o m a t i c systems was
performed. Because few f u n c t i o n a l i t i e s a r e IR d e t e c t a b l e i n t h i s
f r a c t i o n o t h e r than C-H u n i t s , the t o l u e n e e l u t e d f r a c t i o n of the
residuum p r o b a b l y c o n s i s t s p r i m a r i l y of a r o m a t i c r i n g s w i t h s h o r t
a l i p h a t i c s u b s t i t u e n t s and/or fused saturated r i n g s . Because of
the d i s t i l l a t i o n parameters e m p l o y e d , compounds w i t h 4 o r fewer
f u s e d r i n g s s h o u l d have been removed. The t o l u e n e f r a c t i o n s h o u l d ,
t h e r e f o r e , r e p r e s e n t compounds w i t h a t l e a s t 5 r i n g s . Figure 4
shows a s e p a r a t i o n of s e v e r a l PAH compounds on a 15cm ODS column
with a C 0 mobile phase.
2 A l l compounds w i t h t h r e e or g r e a t e r r i n g s
are separated to b a s e l i n e r e s o l u t i o n . R e l a t i v e l y high density C0 2
and a h i g h f l o w r a t e were used to e l u t e l a r g e m o l e c u l e s f a s t e r .

These compounds e l u t e l o g a r i t h m i c a l l y w i t h i n c r e a s i n g r i n g numbers
which i s e x p e c t e d f o r a homologous s e r i e s w i t h i s o c r a t i c e l u t i o n .
The t o l u e n e f r a c t i o n s of the residuum samples were s u b j e c t e d
t o the same a n a l y s i s c o n d i t i o n s as the PAH model compounds. The
chromatogram c o r r e s p o n d i n g t o Day 14 i s shown i n F i g u r e 5.
T r a d i t i o n a l o f f - l i n e s a m p l i n g (top) and an o n - l i n e C O . e x t r a c t i o n
(bottom) were e m p l o y e d . D e t e c t i o n at 300 nm wavelength was used t o
emphasize the l a r g e r PAHs which were e x p e c t e d t o be p r e s e n t . This
wavelength was chosen f o r the c h r o m a t o g r a p h i c p r e s e n t a t i o n h e r e ;
however, d u r i n g d e v e l o p m e n t , o t h e r wavelengths were u s e d . A t 254
nm, f o r example, the e a r l y e l u t i n g peaks a b s o r b i n t e n s e l y ,
i n d i c a t i n g t h a t n o n c o n j u g a t e d systems a r e a l s o p r e s e n t . Several
i n t e r e s t i n g f e a t u r e s are seen i n t h e s e chromatograms. The l a t e r
e l u t i n g peaks become more i n t e n s e at l a t e r r u n - d a y s . T h i s i s most
r e a d i l y n o t e d i n the second g r o u p i n g o f peaks i n each chromatogram.
The t h i r d g r o u p i n g of p e a k s , which e l u t e where coronene e l u t e s , a r e

WAVENUMBERS
F i g u r e 3. S t a c k p l o t of C-H s t r e t c h r e g i o n f o r the 7 f i l e s
(Nos. 30-36) t a k e n a c r o s s the major GSR peak i n F i g u r e 2.

JORDAN ET AL. Extraction & Chromatography of Coal-Derived Products 1
0 1 2 3 4 5 6 7 8 9
TIME. MINUTES
F i g u r e 4. S e p a r a t i o n of some PAH compounds: ODS column (5 μ ι η ) ,

pressure: 4200 i n l e t , 3700 o u t l e t . Mobile phase: C 0 a t 3.7
2
mL/min. Detection: 300 nm, 500 nm r e f e r e n c e . Column: 15cm χ

4.6 mm ODS.

TIME. MINUTES
F i g u r e 5. SFC s e p a r a t i o n (2 mL/min) of t o l u e n e f r a c t i o n o f
r e s i d u u m Day 14 comparing o n - l i n e (bottom) and t r a d i t i o n a l
(top) s a m p l i n g methods. ODS (5 ym) column (15 cm χ 4 . 6 mm,
i . d . ) , 4 0 ° C , C 0 (3800 p s i ) , 300 nm.
2
Ο Ϊ 2 5 4 S t 7 ·ft' it 12 M Μ • » 22 24 26
T I M E , MINUTES
Figure 6. SFC s e p a r a t i o n a f t e r SFE o f t o l u e n e f r a c t i o n o f

residuum Day 25 (Sample 6 8 ) : N H column (5 ym, 25 cm χ 4 . 6 mm,
2
i . d . ) , 2 m L / m i n , 4 0 ° C , CO (3200 p s i ) , 300 nm.

15. JORDAN ET AL. Extraction & Chromatography of Coal-Derived Products 199
p r o b a b l y s i x - r i n g compounds. A b r o a d l a t e e l u t i n g peak ( c a . 15
minutes) i s p r o b a b l y a s e v e n - r i n g compound. R e t e n t i o n time f o r
t h i s component f i t s t o the p r e v i o u s l y a l l u d e d l o g a r i t h m i c p l o t v e r y
well. The second group o f p e a k s , which e l u t e s b e f o r e the s i x - r i n g
compounds a r e p o s s i b l y f i v e - r i n g compounds whose r i n g s are o r i e n t e d
i n a " s t r e t c h e d " o r i e n t a t i o n , or the e l u t e d m a t e r i a l may be
components which c o n t a i n f i v e a r o m a t i c r i n g s and one p a r t i a l l y
hydrogenated r i n g . Other d e t e c t o r s , such as d i o d e a r r a y UV and
f l u o r e s c e n c e d e t e c t o r s may y i e l d more s e l e c t i v e i n f o r m a t i o n about
these s t r u c t u r e s .
The i n c r e a s e i n a p p a r e n t c o n c e n t r a t i o n of the l a r g e r a r o m a t i c s
as a f u n c t i o n o f time i s p r o b a b l y a d i r e c t r e s u l t of c a t a l y s t
fouling. The new c a t a l y s t demonstrated the g r e a t e s t a b i l i t y t o
h y d r o g e n a t e t h e fragments formed by t h e r m o l y s i s ; however, t h i s
p r o c e s s p r o b a b l y becomes l e s s e f f i c i e n t w i t h t i m e , a l l o w i n g f o r
r e f o r m a t i o n o f C - C bonds which r e s u l t s i n h i g h e r a r o m a t i c i t i e s and
l a r g e r PAH compounds.
The chromatograms g e n e r a t e
s p e c i f i c a l l y used t o determin
show a h i g h d e g r e e of r e s o l u t i o n . An a m i n o p r o p y l column was used
a t a somewhat lower d e n s i t y t o s p r e a d the peaks of the t o l u e n e
f r a c t i o n out o v e r a l a r g e r p e r i o d of t i m e . Other workers have
shown t h i s m a t e r i a l t o s e p a r a t e compounds i n the o r d e r of r i n g
number a l s o . F i g u r e 6 shows the chromatogram a c h i e v e d w i t h the
f r a c t i o n from Day 25. T h i s was o b t a i n e d w i t h UV 254nm d e t e c t i o n ,
r a t h e r than 300nm, as l a r g e a r o m a t i c s w i l l not e l u t e i n a
r e a s o n a b l e amount of time under t h e s e c o n d i t i o n s . There a r e s t i l l
many u n r e s o l v e d p e a k s , which a l l u d e s to the extreme c o m p l e x i t y of
the s a m p l e . L a r g e a r o m a t i c m o l e c u l e s have many i s o m e r s , and
e x c e l l e n t r e s o l u t i o n of t h e s e w i t h a packed column may be
impossible.
The o n - l i n e e x t r a c t i o n t e c h n i q u e does not p e r f o r m as w e l l as
t r a d i t i o n a l methods f o r the t o l u e n e f r a c t i o n i n c o n t r a s t t o the
hexane f r a c t i o n . The l a t e r e l u t i n g peaks are much more i n t e n s e f o r
the t r a d i t i o n a l s a m p l i n g i n a l l c a s e s . I t seems t h a t CO f a v o r s
t h e lower m o l e c u l a r w e i g h t m o l e c u l e s , even a t h i g h d e n s i t i e s . On
l i n e FTIR d e t e c t i o n d i d not y i e l d any new i n f o r m a t i o n f o r the
aromatic f r a c t i o n s . H i g h l y a r o m a t i c m a t e r i a l does not a b s o r b
infrared radiation greatly. In c o n t r a s t , UV d e t e c t o r s a r e q u i t e
s e n s i t i v e and y i e l d s i g n i f i c a n t i n f o r m a t i o n f o r a r o m a t i c compounds.
Acknowledgment
The f i n a n c i a l a s s i s t a n c e of the Commonwealth of V i r g i n i a and

Department o f E n e r g y G r a n t DE-FG22-84PC70799 i s g r e a t l y
appreciated.

Literature Cited
1. Ν. M. Karayannis, Rev. Anal. Chem., 1971, 1, 43.
2. Ε. Klesper, A. H. Corwin, D. A. Turner, J. Org. Chem., 1962,
27, 700.
3. D. R. Gere, Science, 1983, 222, 253.
4. C. Grimmet, Chem. Ind., 1981, 6, 359.
5. E. Stahl, K. W. Quirin, A. Glatz, D. Gerard, G. Rau, Ber.
Bunsenges Phys. Chem., 1984, 8, 900.
6. R. J. Skelton, L. T. Taylor, Chromatographia, 1986, 21, 3.
7. A. G. Conolli, J. B. MacArthur, J. B. McLean, "HRI's Two Stage
Catalytic Coal Liquefaction Program - A Status Report",
presented at the 1984 DOE Direct Liquefaction Contractors'
Review Meeting, Albuquerque, NM, October 1984.
8. F. P. Burke, R. A. Winschel, "Recycle Slurry Oil
Characterization - Second Annual Report", DOE Contract No. DE-
AC22-80PC30027, August, 1983.
9. J. W. Jordan, C. C. Johnson and L. T. Taylor, Chromatographia,
1985, 20, 717.
Received July 1, 1986

Chapter 16
Supercritical Carbon Dioxide Extraction of Lemon Oil

1
Steven J . Coppella and Paul Barton
Department of Chemical Engineering, Pennsylvania State University,

University Park, PA 16802
Vapor-liquid-equilibrium was measured for lemon oil

and carbon dioxide from 303 to 313 Κ and from 4 to 9
MPa using a nonvisual, constant-volume static cell.
Two-phase behavior was verified visually in separate
experiments. Phase samples were depressurized into
cold traps; carbo
test meter, and liquids were analyzed by gas
chromatography. The Peng-Robinson equation of state
reproduced the P-x diagram by modeling the system as
a carbon dioxide-limonene binary with a
temperature-dependent interaction parameter.
Solubilities of oil in the vapor phase were in the
range of 1 to 3 wt%. Relative v o l a t i l i t y of
limonene to geranial decreased from 2.2 to 1.3 over
this solubility range; relative volatility for
geranial to β-caryophyllene decreased from 1.5 to
1.1.
6
I n 1 9 8 3 - 1 9 8 4 , A r i z o n a and C a l i f o r n i a p r o d u c e d a n n u a l l y o v e r 1 0 kg
of c o l d - p r e s s e d l e m o n o i l . A f t e r b e i n g c o n c e n t r a t e d by d i s t i l l a
t i o n o r l i q u i d e x t r a c t i o n , lemon o i l i s used as a f l a v o r i n g a n d / o r
f r a g r a n c e a g e n t i n b e v e r a g e s and c o s m e t i c s . However, d i s t i l l a t i o n
t h e r m a l l y d e g r a d e s lemon o i l , and e x t r a c t i o n w i t h o r g a n i c s o l v e n t s
only p a r t i a l l y reduces thermal degradation (since the s o l v e n t s must
be r e c o v e r e d by d i s t i l l a t i o n ) a n d i n t r o d u c e s s o l v e n t c o n t a m i n a t i o n .
E x t r a c t i o n with s u p e r c r i t i c a l carbon d i o x i d e near i t s critical
3
p o i n t ( 3 0 4 . 3 Κ, 7 . 3 8 M P a , 0 . 4 6 7 g / c m ) o f f e r s a cheap, n o n t o x i c
s o l v e n t t h a t does not i m p a r t f l a v o r s nor t h e r m a l l y degrade the
product. S u p e r c r i t i c a l e x t r a c t i o n i s a hybrid unit operation i n
the domain between e x t r a c t i v e d i s t i l l a t i o n a n d l i q u i d e x t r a c t i o n .
S o l v e n t r e c o v e r y i s a c c o m p l i s h e d by d e p r e s s u r i z a t i o n a t a m b i e n t
temperature.
y
Current address: Department of Chemical Engineering, University of Delaware,
Newark, D E 19716
0097-6156/87/0329-0202$06.00/0

16. COPPELLA AND BARTON Carbon Dioxide Extraction of Lemon Oil 203
P r o c e s s e s f o r s u p e r c r i t i c a l e x t r a c t i o n o f o i l s have been
d e s c r i b e d i n numerous l i t e r a t u r e r e f e r e n c e s , i n c l u d i n g P a u l a i t i s e t
al. ( 1 ) , E l y and Baker ( 2 ) , G e r a r d ( 3 ) , S t a h l et a l . ( 4 ) , and Robey
and Sunder ( 5 ) . The l i t e r a t u r e l a c k s d e t a i l e d p h a s e e q u i l i b r i u m
d a t a on mul t i component e s s e n t i a l o i l s w i t h s u p e r c r i t i c a l solvents
i n the p r o x i m i t y o f the s o l v e n t c r i t i c a l temperature.
The p u r p o s e s o f o u r r e s e a r c h were t o e v a l u a t e t h e f e a s i b i l i t y
of s u p e r c r i t i c a l c a r b o n d i o x i d e e x t r a c t i o n o f lemon o i l near
ambient temperature, generate e q u i l i b r i u m d a t a f o r c a r b o n d i o x i d e
w i t h mul t i component e s s e n t i a l o i l c o n s t i t u e n t s , and e v a l u a t e the
a b i l i t y of the Peng-Robinson e q u a t i o n of s t a t e (6) t o model t h i s
mul t i component s u p e r c r i t i c a l s y s t e m .
C o n c e n t r a t i n g Lemon O i l
S t a r o s c i k a n d W i l s o n (7) h a v e a n a l y z e d v a r i o u s l e m o n o i l s a n d
i d e n t i f i e d 38 c o m p o u n d s T h e s e compounds c a n be s u b d i v i d e d i n t o
t h r e e major c l a s s i f i c a t i o n s
f r a c t i o n (oxygenated C
hydrocarbons). Lemon o i l i s u s u a l l y c o n c e n t r a t e d t o remove the
t e r p e n e s and s e s q u i t e r p e n e s from the d e s i r e d C - C oxy f r a c t i o n
8 1 2
(8).
When c o n c e n t r a t i n g t h e l e m o n o i l by m u l t i s t a g e fractional
d i s t i l l a t i o n under vacuum, column performance coupled with
c o n d e n s e r p r e s s u r e , c o l u m n p r e s s u r e d r o p , r e b o i l e r d e s i g n , a n d mode
of o p e r a t i o n ( b a t c h or c o n t i n u o u s ) d i c t a t e s t h e d e g r e e o f t h e r m a l
exposure. O v e r h e a d t e m p e r a t u r e s r a n g e f r o m 320 t o 340 K , r e b o i l e r
t e m p e r a t u r e s r a n g e f r o m 330 t o 370 K , a n d e x p o s u r e t i m e s o f 1 5 t o
20 h o u r s may b e e x p e c t e d d u r i n g b a t c h d i s t i l l a t i o n . In continuous
d i s t i l l a t i o n , exposure times are l o w e r but r e b o i l e r t e m p e r a t u r e s
may be h i g h e r .
In e x t r a c t i v e d i s t i l l a t i o n w i t h a s u p e r c r i t i c a l s o l v e n t ,
e x t r a c t i o n r a t h e r t h a n vacuum i s u s e d t o v o l a t i l i z e t h e components
i n t o t h e vapor phase. Operating t e m p e r a t u r e s c a n be l o w e r t h a n i n
c o n v e n t i o n a l d i s t i l l a t i o n , and the d e s i r e d C - C 8 l 2 oxy f r a c t i o n w i l l
t h e n h a v e been s u b j e c t e d t o l e s s t h e r m a l d e g r a d a t i o n . Carbon
d i o x i d e has a c r i t i c a l t e m p e r a t u r e t h a t meets t h i s g o a l .
In order t o make data c o r r e l a t i o n p r a c t i c a b l e i n
supercritical carbon dioxide e x t r a c t i o n , i t i s convenient to
r e p r e s e n t each major c h e m i c a l c l a s s i f i c a t i o n by a s i n g l e c o m p o u n d .
E a c h s e l e c t compound s h o u l d h a v e a v a i l a b l e g o o d v a p o r p r e s s u r e d a t a
a n d s h o u l d be a p r e d o m i n a n t c o n s t i t u e n t i n i t s g r o u p w i t h r e g a r d to
s t r u c t u r e and c o n c e n t r a t i o n . F o r c o r r e l a t i o n p u r p o s e s , we s e l e c t e d
l i m o n e n e , g e r a n i a l , and 3 ~ c a r y o p h y l l e n e . Their structures are
shown i n F i g u r e 1.
S t a h l et a l . ( £ ) p r e s e n t e d s o l u b i l i t y d a t a f o r l i m o n e n e and
c a r y o p h y l l e n e w i t h c a r b o n d i o x i d e ; G e r a r d (3) i n c l u d e d c a r v o n e .
Temperatures i n t h e r a n g e o f 279 t o 377 K , a n d p r e s s u r e s i n t h e
r a n g e o f 1 . 5 t o 11 MPa w e r e c o v e r e d . Robey and Sunder ( 5 ) p r o v i d e d
s o l u b i l i t y and r e l a t i v e v o l a t i l i t y d a t a for carbon dioxide with
c o n c e n t r a t e d l e m o n o i l and w i t h l i m o n e n e and c i t r a l (geranial/
n e r a l ) f r o m 323 t o 353 Κ a n d 9 . 4 t o 10.6 M P a .
G e r a r d (3) d e s c r i b e d a c o n t i n u o u s m u l t i s t a g e c o l u m n p r o c e s s
for c a r b o n d i o x i d e e x t r a c t i o n ( d i s t i l l a t i o n ) of e s s e n t i a l o i l s at

a m b i e n t t e m p e r a t u r e and 8 MPa, w i t h s o l v e n t r e c o v e r y a t 273 Κ and 3

MPa. R o b e y and S u n d e r ( 5 ) p r o p o s e d a l e m o n o i l fractionator
w h i c h w o u l d o p e r a t e a t 3 3 3 Κ a n d 1 0 MPa w i t h an e f f i c i e n c y
e q u i v a l e n t t o 1 2 s t a g e s ; s o l v e n t r e c o v e r y would be at 2 9 3 Κ and 5.5
MPa.
Experimental Section
C o l d - p r e s s e d o i l f r o m A r i z o n a e a r l y d e s e r t lemons was s u p p l i e d by
Α. M. T o d d Company, K a l a m a z o o , MI. D e g a s s e d l e m o n o i l and d r y
c a r b o n d i o x i d e w e r e charged i n t o the o n e - l i t e r i s o t h e r m a l c o n s t a n t
volume c e l l shown i n F i g u r e 2 . A f t e r t h e o p e r a t i n g t e m p e r a t u r e was
r e a c h e d , t h e s y s t e m was s t i r r e d f o r one h o u r , t h e n a l l o w e d t o
s e t t l e f o r 15 m i n u t e s b e f o r e s a m p l i n g . A c o u p l e of e x p e r i m e n t s
were made w i t h l o n g e r m i x i n g a n d s e t t l i n g t i m e s t o c o n f i r m t h a t
e q u i l i b r i u m had b e e n r e a c h e d . P a r a l l e l phase visualization
e x p e r i m e n t s were c o n d u c t e d i n a s i g h t gauge t o i n s u r e that
o p e r a t i o n was i n t h e t w o - p h a s
adequate. Experiment
to 9 MPa.
A s a m p l e o f t h e e q u i l i b r a t e d l i q u i d phase was removed ( a f t e r
p u r g i n g ) by d e p r e s s u r i z a t i o n t h r o u g h a v a l v e and h y p o d e r m i c tubing
i n t o a t w o - s t a g e t r a p c o o l e d by d r y i c e - a c e t o n e . A wet t e s t meter
measured the carbon d i o x i d e o f f - g a s . A sample of t h e vapor phase
was t h e n s i m i l a r l y removed. Purge and sample s i z e s were kept s m a l l
t o m i n i m i z e d i s t u r b a n c e s of e q u i l i b r i u m . P r e s s u r e changes i n t h e
c e i l were 0 - 0 . 1 MPa d u r i n g s a m p l i n g o f l i q u i d phase and 0 - 1 . 2 MPa
d u r i n g s a m p l i n g of vapor phase. Special high-pressure sample
v a l v e s w i t h m i c r o l i t e r - s i z e d t r a p s were t r i e d i n an e f f o r t t o
reduce p r e s s u r e d i s t u r b a n c e , but r e l i a b i l i t y was i n a d e q u a t e .
E s t i m a t e d r e l a t i v e e r r o r s a r e 0.2% f o r t e m p e r a t u r e , 5% f o r
p r e s s u r e , H% f o r c a r b o n d i o x i d e mole f r a c t i o n i n t h e l i q u i d phase,
and 10% f o r lemon o i l mole f r a c t i o n i n t h e v a p o r p h a s e . Relative
e r r o r i s d e f i n e d a s e x p e r i m e n t a l e r r o r d i v i d e d by sample average
v a l ue.
The r e c o v e r e d lemon o i l samples were a n a l y z e d by gas chromato
graphy. A 0 . 5 mm i . d . χ 3 0 m t h i n f i l m ( 0 . 1 ym) S E - 3 0 glass
c a p i l l a r y c o l u m n ( S u p e l c o , I n c . , B e l l e f o n t e , PA) was used w i t h a
flame i o n i z a t i o n d e t e c t o r . The t e m p e r a t u r e was programmed f r o m 348
to 4 7 3 K. Peak i d e n t i f i c a t i o n was based on i n f o r m a t i o n o f S u p e l c o ,
Inc., A. M. Todd Company, and S t a r o s c i k and W i l s o n ( 7 ) . Staroscik
( 9 ) p r o v i d e d us w i t h t h e r e s p o n s e v a l u e s used i n h i s work and we
assumed t h a t our d e t e c t o r would g i v e p r o p o r t i o n a t e r e s p o n s e s .
S t a r o s c i k f o u n d i n h i s work t h a t r e l a t i v e s t a n d a r d d e v i a t i o n s of
the r e s p o n s e v a l u e s were g e n e r a l l y l e s s than 3%.
Results
Lemon o i l - c a r b o n d i o x i d e e q u i l i b r i u m was measured a t 3 0 3 , 3 0 8 , and

313 Κ and i n the p r e s s u r e range of 4 t o 9 MPa. Below 6 MPa, t h e r e
was i n s u f f i c i e n t l e m o n o i l i n t h e vapor phase t o o b t a i n good
samples f o r a n a l y s i s . Above 9 . 0 MPa at 313 K, above 7 . 8 MPa a t 3 0 8
K, a n d above 7 . 4 MPa a t 303 K, the system e x h i b i t e d a s i n g l e phase.
Nine e x p e r i m e n t s p r o v i d e d two-phase, v a p o r - l i q u i d e q u i l i b r i u m d a t a

CHD
H,C
CH.
LIMDNENE GERANIAL β - CARYDPHYLLENE
F i g u r e 1.
VACUUM PUMP
HEATED
PRESSURE
GAUGE
•IL CHARGE AND
DEGASSING VESSEL
SAMPLE OF GAS
COLD TRAP VAPOR PHASE METER
WARMED COg
CHARGE TANK
25 Kg BALANCE
THERMOSTATIC
HEATER
1.11 - LITER EQUILIBRIUM CELL

HASTELLDY C
RATING' 34 MPa AT 700 Κ
F i g u r e 2. Vapor-Liquid Equilibrium Apparatus.

s u i t a b l e f o r c o r r e l a t i o n s and f o r g e n e r a t i n g c o e f f i c i e n t s f o r the
Peng-Robinson e q u a t i o n . D e t a i l e d e x p e r i m e n t a l data can be f o u n d i n
C o p p e l l a (JTj).
The r e s u l t s o f an e x p e r i m e n t a t 308 Κ and 6.98 MPa are
d e t a i l e d here. T h e l i q u i d p h a s e c o n t a i n e d 48 wt% (74 m o l e %)
c a r b o n d i o x i d e and the vapor phase c o n t a i n e d 99.5 wt% (99.8 mole %)
carbon d i o x i d e . A gas c h r o m a t o g r a m f o r t h e l e m o n o i l f r o m t h e
l i q u i d p h a s e s a m p l e i s shown i n F i g u r e 3. Peak i d e n t i f i c a t i o n ,
r e t e n t i o n , r e s p o n s e v a l u e , and c o n c e n t r a t i o n a r e g i v e n i n T a b l e I .
C o m p o s i t i o n o f the lemon o i l i n t h e vapor phase i s a l s o l i s t e d .
Average m o l e c u l a r weight o f l e m o n o i l i s 137.9 i n t h e l i q u i d and
136.4 i n the vapor .
The r e l a t i v e v o l a t i l i t y , o r s e l e c t i v i t y f a c t o r , f o r e a c h
component i n the presence of carbon d i o x i d e i s a l s o g i v e n i n T a b l e
I. R e l a t i v e v o l a t i l i t y i s d e f i n e d as t h e r a t i o o f K - v a l u e f o r
component i t o K - v a l u e f o r l i m o n e n e . The K - v a l u e f o r component i
i s d e f i n e d as m o l e f r a c t i o n i i n the vapor ( e x t r a c t ) phase t o mole
f r a c t i o n i i n the l i q u i
3y comparing t h e r e l a t i v
t h e e a s e o f s e p a r a t i o n between t h e s e components can be d e t e r m i n e d .
F o r example, a key terpene-oxy s e p a r a t i o n i n v o l v e s t e r p i n o l e n e w i t h
a r e l a t i v e v o l a t i l i t y w i t h r e s p e c t t o l i m o n e n e o f 0.7 and
c i t r o n e l l a l with r e l a t i v e v o l a t i l i t y w i t h r e s p e c t t o l i m o n e n e of
0.4. The r e l a t i v e v o l a t i l i t y o f t e r p i n o l e n e t o c i t r o n e l l a l i s then
0.7/0.4 or 2.
The s e c o n d cut p o i n t i n the s e p a r a t i o n i s between g e r a n y l a c e -
t a t e and g - c a r y o p h y l l e n e . T h i s s e p a r a t i o n f a c t o r i s 0.06/0.07 o r
0.9. T h i s i s o p p o s i t e that f o r g e r a n i a l to 3-caryophyllene:
0.2/0.07 or 3. S i n c e t h e r e i s some o v e r l a p i n t h e v o l a t i l i t i e s o f
C i 2 oxygenated hydrocarbons and sesquiterpenes, some
β - c a r y o p h y l l e n e w i l l be e x t r a c t e d i n t o t h e d e s i r e d C - C 8 l 2 oxy
product.
Solubility and Selectivity
S o l u b i l i t y d i a g r a m s were p r e p a r e d f o r the phases t h a t s e p a r a t e d i n

the lemon o i l e x t r a c t i o n s performed i n t h i s s t u d y w i t h carbon
dioxide. S u c h d i a g r a m s can s e r v e o n l y as g u i d e s , s i n c e s o l u b i l i t y
i s composition-dependent and i s a f u n c t i o n of the amount e x t r a c t e d .
The d a t a a r e shown i n F i g u r e s 4, 5, and 6 a t 303, 308, and 313 K,
respectively.
E x t r a c t i o n s or e x t r a c t i v e d i s t i l l a t i o n s with s u p e r c r i t i c a l
s o l v e n t need to be performed a t as h i g h as p o s s i b l e a s o l u b i l i t y o f
o i l i n t h e e x t r a c t or vapor phase i n o r d e r t o r e d u c e the s o l v e n t or
c a r r i e r gas r e q u i r e m e n t . From our l e m o n o i l - c a r b o n d i o x i d e p h a s e
d i a g r a m s , i t appears t h a t the h i g h e s t p r a c t i c a l s o l u b i l i t y l e v e l i s
0.9 mole % (2.8 wt%) e s s e n t i a l o i l . T h i s i s o b t a i n a b l e a t 313 Κ .
At lower t e m p e r a t u r e , s e n s i t i v i t y of s o l u b i l i t y to pressure
r e q u i r e s t h a t s o l u b i l i t y be lower (e.g., 0.3 mole % a t 308 K ) .
At 313 Κ and 8.4 MPa, t h e s l o p e o f e x t r a c t p h a s e s o l u b i l i t y
v e r s u s p r e s s u r e i s 0.06 w e i g h t f r a c t i o n o i l / M P a . For a 15-m tall
3
e x t r a c t i o n tower o p e r a t e d at a d e n s i t y o f 0.5 g / c m , t h e p r e s s u r e
a t t h e b o t t o m i s h i g h e r t h a n t h a t a t t h e t o p by 0.075 MPa. The
s o l u b i l i t y at the bottom w i l l then be 0.15 wt£ h i g h e r at t h e b o t t o m

to
ο
Sample.
Phase
of Lemon O i l i n L i q u i d
Gas Chromatogram
F i g u r e 3.

Table I. Lemon O i l V a p o r - L i q u i d Analyses a t E q u i l i b r i u m i n CO2
Retention 3
Volatility
Relative Weight 0
Relative
Peak to Relative Mole % to
No. Compound Limonene Response Vapor Liquid Limonene
ref acetone 0.00 — ~

1 α-thuj ene 0.55 0.75 0.61 0.35 1.8
2 a-pinene 0.58 0.75 2.80 1.68 1.7
3 camphene 0.63 0.70 0.09 0.06 1.6
4 sabinene 0.76 0.74 17.27 13.06 1.34
3-pinene J
5 myrcene 0.79 1.87 1.59 1.2

6 octanal
phellandrenej
7 a-terpinene 0.92 1.19 1.21 1.10 1.1
8 limonene 1.00 0.75 67.14 68.22 1.0

9 Ύ-terpinene 1.09 0.78 7.59 8.45 0.91
10 terpinolene"^ 1.19 0.78 0.47 0.67 0.7
1 inalool I
nonanal
11 citronellal 1.40 1.06 0.02 0.04 0.4

12 terpinenen-4-01 1.51 0.92 0.02 0.04 0.4
13 a-terpineol 1.55 0.92 0.06 0.20 0.3
14 decanal 1.60 0.97 0.01 0.08 0.1
15 neral 1.70 0.96 0.24 0.92 0.3
16 geranial 1.80 0.96 0.29 1.45 0.2

17 nonyl acetate 1.95 1.24 0.00 0.03 — -
18 neryl acetate 2.12 1.02 0.03 0.25 0.1

19 geranyl acetate 2.18 1.02 0.009 0.15 0.06
20 3-caryophyllene 2.36 0.78 0.013 0.18 0.07
21 t r ans-ot
her gam ot ene 2.40 0.78 0.016 0.26 0.06
22 α-humalene 2.53 0.71 0.00 0.05
23 β-bisabolene 2.60 0.77 0.013 0.38 0.03
d e t e n t i o n t i m e f o r limonene averaged 8.7 minutes

°Peak a r e a m u l t i p l i e r

0.001 0.01 0.1 1.0

Mole fraction lemon oil
F i g u r e 4. Phase E q u i l i b r i u m f o r Carbon Dioxide:Lemon O i l at

303 Κ. E x p e r i m e n t a l Two-Phase: 0 - Vapor t - Liquid.
Δ - E x p e r i m e n t a l One-Phase. Peng-Robinson e q .
0.0001 0.001 0.01 0.1


308 Κ. E x p e r i m e n t a l Two-Phase: 0 - Vapor · - Liquid.
A - E x p e r i m e n t a l One-Phase. Peng-Robinson e q .
10 I 1
I 1
1 1
Δ
8 -*
CP/'
ν /
/
</>
«
- /
/
\-
I \
ι 1
2 - \
\
. 1 . 1 1
0.0001 0.001 0.01 0.1 1.0

313 Κ. E x p e r i m e n t a l Two-Phase: 0 - Vapor · - Liquid.
Λ - E x p e r i m e n t a l One-Phase. - - Peng-Robinson e q .

( i g n o r i n g composition e f f e c t s ) . At 308 Κ and 7.69 MPa, an i n c r e a s e

i n p r e s s u r e of 0.15 MPa causes t h e two-phase s y s t e m t o r e v e r t t o a
one-phase system. I t i s i m p e r a t i v e t h a t temperature and p r e s s u r e
p r o f i l e s i n t h e s u p e r c r i t i c a l e x t r a c t i o n t o w e r be m a i n t a i n e d
accurately. Windows i n t h e tower a r e recommended t o c o n f i r m t h a t
o p e r a t i o n remains i n the two-phase domain.
The s e l e c t i v i t i es i n t h e s u p e r c r i t i c a l c a r b o n dioxide
e x t r a c t i o n o f t e r p e n e s from the oxy f r a c t i o n , and the oxy f r a c t i o n
from s e s q u i t e r p e n e s , f o r l e m o n o i l a r e shown i n F i g u r e s 7 and 8,
respectively. F i g u r e 7 shows t h e r e l a t i v e v o l a t i l i t y , or
s e l e c t i v i t y f a c t o r , o f l i m o n e n e t o g e r a n i a l as a f u n c t i o n o f o i l
s o l u b i l i t y i n the vapor phase. O p e r a t i o n o f the e x t r a c t o r at 308 Κ
and 1 wtyÊ s o l u b i l i t y (the h i g h e s t p r a c t i c a l l e v e l at t h i s
t e m p e r a t u r e ) p r o v i d e s a r e l a t i v e v o l a t i l i t y o f 2. O p e r a t i o n at 313
Κ and 2.8 ut% s o l u b i l i t y p r o v i d e s a r e l a t i v e v o l a t i l i t y o f 1.3-
The s e l e c t i v i t y f a c t o r s a r e an o r d e r o f magnitude lower than t h e
vapor p r e s s u r e r a t i o s at 303 t o 313 K
F i g u r e 8 shows t h
β - c a r y o p h y l l e n e as a f u n c t i o
At 313 Κ and 1 w t j s o l u b i l i t y , r e l a t i v e v o l a t i l i t y i s 1.4. A t 308
Κ and 1 wt56 s o l u b i l i t y , t h e s e c o n s t i t u e n t s a r e i n s e p a r a b l e by s u p e r
c r i t i c a l carbon d i o x i d e e x t r a c t i o n . The r a t i o of vapor p r e s s u r e s
f o r t h i s p a i r i s i n t h e v i c i n i t y o f 2 ( a t 392 Κ, t h e l o w e s t
temperature w i t h vapor p r e s s u r e d a t a ) .
Modeling of E q u i l i b r i a
The c a r b o n d i o x i d e / l e m o n o i l P-x b e h a v i o r shown i n F i g u r e s 4, 5,

and 6 i s t y p i c a l of b i n a r y carbon d i o x i de: h y d r o c a r b o n s y s t e m s , s u c h
as t h o s e c o n t a i n i n g h e p t a n e (Im and K u r a t a , V\), decane ( K u l k a r n i
et a l . , 1_2), or benzene (Gupta et a l . , 1_3 ). Our l e m o n o i l s a m p l e s
c o n t a i n e d i n e x c e s s o f 64 m o l e % limonene; so we modeled our d a t a
as a r e d u c e d b i n a r y o f l i m o n e n e a n d c a r b o n d i o x i d e . The
Peng-Robinson (6^) e q u a t i o n was u s e d , w i t h c r i t i c a l t e m p e r a t u r e s ,
c r i t i c a l p r e s s u r e s , and a c e n t r i c f a c t o r s o b t a i n e d f r o m D a u b e r t and
D a n n e r (V4 ) , a n d R e i d e t a l . (J5_). For c a r b o n d i o x i d e , ω = 0.225;
f o r l i m o n e n e , ω = 0.327, T c = 656. 4 Κ, P c = 2.75 MPa. I t was
n e c e s s a r y t o v a r y the i n t e r a c t i o n parameter w i t h temperature i n
order to c o r r e l a t e the data s a t i s f a c t o r i l y . The v a l u e s o f d-| 2 a r e
0.1135 a t 303 K, 0.1129 a t 308 Κ, and 0.1013 a t 313 K. Comparisons
of c a l c u l a t e d and e x p e r i m e n t a l r e s u l t s a r e g i v e n i n F i g u r e s 4, 5,
and 6.
A t t e m p t s t o model the r e l a t i v e v o l a t i l i t i e s of the minor
o r g a n i c c o n s t i t u e n t s t o limonene u s i n g t h e P e n g - R o b i n s o n e q u a t i o n
proved u n f r u i t f u l .
Proposed P r o c e s s
L e m o n o i l can be c o n c e n t r a t e d by s u p e r c r i t i c a l c a r b o n d i o x i d e
e x t r a c t i o n i n t h e t e m p e r a t u r e range o f 308 t o 313 K. Pressure i n
t h e e x t r a c t o r w i l l be i n t h e range o f 7.7 t o 8.5 MPa. Solubilities
of o i l i n the e x t r a c t or v a p o r p h a s e w i l l r a n g e f r o m 1 t o 3 wt%.
S e l e c t i v i t y f a c t o r s n e a r 1.4 w i l l be o b t a i n e d f o r t h e terpene-oxy
s p l i t and t h e o x y - s e s q u i t e r p e n e s p l i t . T h e o p e r a t i o n c a n be

COPPELLA AND BARTON Carbon Dioxide Extraction of Lemon Oil
0.2 0.4 0.6 1 2 4
Solubility, wt 7. oil in v a p o r
F i g u r e 7. Lemon O i l : Car bon D i o x i d e V a p o r - L i q u i d Equilibria

Δ - 303 K, • - 308 Κ, 0 - 313 Κ.
I 1
I 1
I 11 Γ
Ratio o f vapor p r e s s u r e s a t 392 Κ
0.1 0.2 0.4 0.6 1 2

Solubility, wt '/ oil in vapor
F i g u r e 8. Lemon O i l : C a r b o n D i o x i d e V a p o r - L i q u i d Equilibria
Δ - 303 Κ, π - 308 Κ, 0 - 313 Κ.

performed i n a m u l t i s t a g e extractor with r e f l u x . O p e r a t i o n can be

e i t h e r i n t h e b a t c h o r c o n t i n u o u s mode. Solvent recovery is
p e r f o r m e d at c o n d i t i o n s s l i g h t l y below the c r i t i c a l p o i n t o f carbon
dioxide. F l a s h e v a p o r a t i o n can be used; r e f l u x i n g i n an e n r i c h i n g
c o l u m n can be a d d e d t o d e c r e a s e t h e o i l c o n t e n t i n the r e c y c l e d
carbon d i o x i d e . R e s i d u a l carbon d i o x i d e i n the product o i l s is
removed by f l a s h i n g t o a t m o s p h e r i c p r e s s u r e .
S o l u b i l i t y limitations require that the s o l v e n t - t o - o i l feed
r a t i o be h i g h ; an economic a n a l y s i s i s needed t o e s t a b l i s h p r o c e s s
feasibility. The use of c o s o l v e n t s o r h i g h e r t e m p e r a t u r e s can be
u s e d t o i n c r e a s e o i l s o l u b i l i t y and t o d e c r e a s e s o l v e n t - t o - o i l f e e d
ratio. These p r o c e s s m o d i f i c a t i o n s , however, cause a d d i t i o n a l
thermal degradation. W i t h c o s o l v e n t s , thermal degradation occurs
d u r i n g the d i s t i l l a t i o n s t e p needed to remove t h e s e unwanted
components (and f l a v o r s ) from the d e s i r e d e x t r a c t .
Literature Cited
1. Paulaitis, Μ. Ε.
Reviews in Chemical Engineering 1983, 1, 179.
2. Ely, J. F.; Baker, J. Κ. NBS Technical Note 1070 1983.
3. Gerard, D. Chem. Ing. Tech. 1984, 56, 794.
4. Stahl, E.; Quirin, K. W.; Glatz, Α.; Gerard, D.; Rau, G.,
BBPCAX 1984, 88, 900.
5. Robey, R. J.; Sunder, S. "Application of Supercritical
Processing to the Concentration of Citrus Oil Fractions",
Annual Meeting of American Institute of Chemical Engineers,
San Francisco, 1984.
6. Peng, P. Y.; Robinson, D. B. I.E.C. Fund. 1976, 15, 59.
7. Staroscik, J. Α.; Wilson, Α. Α., J. Agric. Food Chem. 1982,
30, 507, 835.
8. Zeigler, E. "Production, Application and Analysis of
Concentrates of Citrus Oils in the Food, Pharmacy, and
Perfumery Industries"; VIII International Congress of
Essential Oils, Cannes, 1980.
9. Staroscik, J. Α., Sunkist Growers, Inc., Ontario, CA,
personal communication, 1984.
10. Coppella, S. J. M.S. Thesis, The Pennsylvania State
University, University Park, PA, 1985.
11. Im, U. Κ.; Kurata, F. J. Chem. Eng. Data 1971, 16, 412.
12. Kulkarni, A. A.; Zarah, B. Y.; Luks, K. D.; Kohn, J. P. J.
Chem. Eng. Data 1972, 19, 92.
13. Gupta, M. Κ.; L i , Y. H.; Hulsey, B. J.; Robinson, R. L., Jr.,
J. Chem. Eng. Data 1982, 27, 55.
14. Daubert, T. E.; Danner, R. P., Eds. "Technical Data Book -
Petroleum Refining", 4th ed.; American Petroleum Institute:
Washington, DC, 1983.
15. Reid, R. C.; Prausnitz, J. M.; Sherwood, T. K. "The
Properties of Gases and Liquids", 3rd ed.; McGraw-Hill Book
Co.: New York, 1977.

Chapter 17
Near-Critical Separation of Butadiene-Butene

Mixtures with Mixtures of Ammonia and Ethylene
D. S. Hacker
Amoco Chemicals Company, Naperville, IL 60566
The results of an experimental investigation are

presented for the separation of mixtures of
1,3-butadiene and 1-butene at near critical conditions
with mixed and single solvent gases. Ammonia was used
as an entrainer t
non-polar solvent
ethane and carbon dioxide, as well as mixtures of each
of these gases with ammonia in concentrations of 2, 5,
8 and 10% by volume. Each solvent and solvent mixture
was studied with respect to its ability to remove
1-butene from an equimolar mixture of 1,3-butadiene/
1-butene. Maximum selectivities of 1.4 to 1.8 were
measured at a pressure of 600 psia and a temperature
of 20 C in mixtures containing 5%-8% by volume of
ammonia in ethylene. All other solvents showed little
or no success in promoting separation of the mixture.
The experimental results are reported for ethylene/
ammonia mixtures and are shown to be in fair agree-
ment with VLE flash calculations predicted indepen-
dently by a modified two parameter R-K type of
equation of state.
A s e p a r a t i o n p r o c e s s i s sought t h a t c a n s a t i s f y b o t h o u r p r e s e n t
economic and e n v i r o m e n t a l c o n s t r a i n t s . I t would a l s o p r o v i d e an
a l t e r n a t i v e t o p r e s e n t p r a c t i c e t h a t r e l i e s on e x p e n s i v e azeo-
t r o p i c o r e x t r a c t i v e d i s t i l l a t i o n processes used i n the r e c o v e r y
o f p r o d u c t s from low r e l a t i v e v o l a t i l i t y streams. As an example,
v i r t u a l l y a l l i n d u s t r i a l b u t a d i e n e r e c o v e r y p r o c e s s e s now r e l y on
extractive d i s t i l l a t i o n using a c e t o n i t r i l e or other equivalent
agent t o enhance t h e r e l a t i v e v o l a t i l i t y o f t h e C4 components. The
use o f s u p e r c r i t i c a l o r near c r i t i c a l s e p a r a t i o n o f t h e s e streams
may s a t i s f y t h e s e r e q u i r e m e n t s p r o v i d e d c e r t a i n p r e s s u r e , temper-
a t u r e and r e c o m p r e s s i o n c r i t e r i a c a n be met. Such a p r o c e s s would
a l s o reduce t h e need f o r a complex t r a i n o f d i s t i l l a t i o n towers.
0097-6156/87/0329-0213$06.00/0

L i q u i d ammonia has been s u g g e s t e d as a s o l v e n t f o r t h e C4

separation(l). A drawback t o i t s use i n t h e l i q u i d s t a t e , however,
i s t h e need f o r c o s t l y r e f r i g e r a t i o n . I t s u s e as a s u p e r c r i t i c a l
s o l v e n t would a l s o be a c c e p t a b l e were i t n o t f o r i t s h i g h c r i t i c a l
t e m p e r a t u r e (405.45 K ) . H i g h temperature f a v o r s t h e p o l y m e r i z a -
t i o n o f t h e b u t a d i e n e ; hence, i t s l i m i t a t i o n i n t h i s r o l e . In this
s t u d y , a method was d e v e l o p e d t h a t seeks t o c i r c u m v e n t t h i s problem
and y e t a c h i e v e t h e d e s i r e d s e p a r a t i o n o f t h e C4's. Prausnitz(2)
d i s c u s s e s t h e u s e o f a m i x t u r e o f s u p e r c r i t i c a l s o l v e n t s whose
p r o p e r t i e s provide the optimal p h y s i c a l conditions f o r e f f i c i e n t
extraction. I t i s equally p o s s i b l e to prepare mixtures o f solvents
t h a t n o t o n l y m o d i f y those c r i t i c a l p r o p e r t i e s o f t h e i n d i v i d u a l
s o l v e n t component, b u t a l s o i n t r o d u c e t h e c h e m i c a l f e a t u r e s needed
t o maximize t h e s e p a r a t i o n o f t h e f e e d m i x t u r e .
I n v i e w o f t h e i n t e r e s t i n t h i s f i e l d , an e x p e r i m e n t a l investi-
g a t i o n was u n d e r t a k e n t o d e t e r m i n e t h e a p p l i c a b i l i t y o f super-
c r i t i c a l phenomena t o t h e s e p a r a t i o n o f b u t a d i e n e from C4 m i x t u r e s .
In p a r t i c u l a r , the separatio
key f a c t o r i n t h e s e p a r a t i o
c o n s i d e r e d i n l i g h t o f p r e d i c t i o n s o b t a i n e d from a r e p r e s e n t a t i v e
e q u a t i o n o f s t a t e i n t h e r e t r o g r a d e r e g i o n o f t h e SC s o l v e n t - s o l u t e
VLE e n v e l o p e .
Theoretical Discussion
The a b i l i t y t o s e p a r a t e s p e c i f i c s o l u t i o n components from t h e l i q u i d

phase w i t h a s u p e r c r i t i c a l o r n e a r - c r i t i c a l s o l v e n t component has
been d e m o n s t r a t e d f o r a few s e l e c t e d s y s t e m s Q ) . Generally, the s o l -
v e n t s a r e s i n g l e component i n o r g a n i c gases o r l i g h t h y d r o c a r b o n s .
I n common u s e have been c a r b o n d i o x i d e , ammonia, ethane, e t h y l e n e
o r propane. W e i n s t o c k and E l g i n ( 4 ) u s e d p r e s s u r i z e d e t h y l e n e t o
promote t h e s e p a r a t i o n o f a number o f m i s c i b l e a q u e o u s - o r g a n i c l i q u i d
mixtures. More r e c e n t l y , P a u l a i t i s and o t h e r s have u s e d c a r b o n
d i o x i d e to dehydrate ethanol(5.6). The s e p a r a t i o n o f a s p h a l t i n e s
w i t h s u p e r c r i t i c a l propane has been c o m m e r c i a l l y d e m o n s t r a t e d by
Kerr-McGee(7). S t a r l i n g , e t a l . , have s u g g e s t e d t h a t t h e r e t r o g r a d e
regime may be e x p l o i t e d by t h e a d d i t i o n o f s u f f i c i e n t s o l v e n t t o
separate a l i g h t l i q u i d hydrocarbon mixture(8).
I n a d d i t i o n , s e v e r a l e q u a t i o n s o f s t a t e have been d e v e l o p e d t o
p r e d i c t t h e VLE b e h a v i o r o f a s u b c r i t i c a l l i q u i d m i x t u r e w i t h a
s u p e r c r i t i c a l component. These t h e o r e t i c a l models a r e o f c u r r e n t
research interest. I n a d d i t i o n , s e v e r a l approaches have been form-
u l a t e d t o e x t e n d t h e a n a l y s i s t o multicomponent systems u t i l i z i n g
c o n c e p t s o f c o n t i n u o u s thermodynamics(9. 10).
R e i d and o t h e r s ( 1 1 . 12) have shown t h a t s u p e r c r i t i c a l s o l v e n t s
e x h i b i t v a r y i n g degrees o f s p e c i f i c i t y towards a p a r t i c u l a r s p e c i e .
F u r t h e r m o r e , t h e s m a l l number o f SC s o l v e n t s a v a i l a b l e l i m i t s t h e
p o t e n t i a l u s e SC e x t r a c t i o n . The use o f e n t r a i n e r s o r m i x t u r e s o f
s o l v e n t s , may remove t h e l i m i t a t i o n imposed by t h e narrow c h o i c e o f
l i k e l y solvents. Moreover, i t i s p o s s i b l e t h a t t h r o u g h t h e p r o p e r
c h o i c e o f entraîner and s o l v e n t t h e d e s i r e d c h e m i c a l a c t i v i t y c a n be
a d j u s t e d t o improve t h e s e l e c t i v i t y o f t h e s o l v e n t . F o r example,
m i x t u r e s o f s o l v e n t gases w i t h e n t r a i n e r s c a n p e r m i t a m o d i f i c a t i o n
o f c r i t i c a l p r o p e r t i e s as w e l l as c h e m i c a l p r o p e r t i e s , so t h a t Ρ and
Τ a d j u s t m e n t c a n be u s e d t o maximize some p h y s i c a l p r o p e r t y o f t h e
system(2).

17. HACKER Separation of Butadiene-Butène Matures 215
B r u n n e r ( 1 3 ) s t u d i e d t h e i n f l u e n c e o f e n t r a i n e r s on model
m i x t u r e s by i n t r o d u c i n g a c e t o n e i n t o a p o l y g l y c e r i d e m i x t u r e , thus
enhancing i t s s e p a r a t i o n with carbon d i o x i d e . The entraîner s e r v e d
as a s o u r c e o f h y d r o g e n b o n d i n g t o augment t h e s e p a r a t i o n o f t h e
d e s i r e d component. The p r i n c i p l e o f t h e entraîner h a s been w i d e l y
known i n l i q u i d e x t r a c t i o n p r o c e s s e s i n i m p r o v i n g s e p a r a t i o n and
was d e s c r i b e d by T r e y b a l ( 1 4 ) .
I t i s known t h a t t h e a d d i t i o n o f a s t r o n g l y i n t e r a c t i v e t h i r d
component t o a m i s c i b l e b i n a r y m i x t u r e c a n a l t e r t h e phase b e h a v i o r
o f t h i s n o r m a l l y s t a b l e system. T h i s o c c u r s by a m i n i m i z a t i o n o f
the G i b b s f r e e energy. By m o d i f y i n g t h e p a i r p o t e n t i a l s between
the components c o m p r i s i n g t h e system, changes i n t h e p a i r w i s e
activity coefficients w i l l result(15). The a d d i t i o n o f a f o u r t h
s o l v e n t component, i f p r o p e r l y s e l e c t e d , c a n f u r t h e r a l t e r t h e
a c t i v i t y c o e f f i c i e n t s o f the s o l u t e , p r e f e r e n t i a l l y i n c r e a s i n g i t s
c o n c e n t r a t i o n i n a g i v e n phase(16. 17). An e x t e n s i o n o f t h e s e
p r i n c i p l e s t o multicomponent s o l i d o r l i q u i d systems i s s t i l l t o be
determined i n the s u p e r c r i t i c a
We have a p p l i e d som
1-butene from a b i n a r y m i x t u r e o f 1,3-butadiene/1-butene. V a r i o u s
m i x t u r e s o f s c s o l v e n t s ( e . g . , ethane, c a r b o n d i o x i d e , e t h y l e n e )
a r e used i n c o m b i n a t i o n w i t h a s t r o n g l y p o l a r s o l v e n t g a s l i k e
ammonia. The p h y s i c a l p r o p e r t i e s o f t h e s e components a r e shown i n
T a b l e I . The e x p e r i m e n t a l r e s u l t s were t h e n compared w i t h VLE
p r e d i c t i o n s u s i n g a newly d e v e l o p e d e q u a t i o n o f s t a t e ( 1 8 ) . The key
f e a t u r e o f t h i s e q u a t i o n i s a new s e t o f m i x i n g r u l e s based on
s t a t i s t i c a l m e c h a n i c a l arguments. We have been a b l e t o demonstrate
i t s agreement w i t h a number o f b i n a r y and t e r n a r y systems d e s c r i b e d
i n t h e l i t e r a t u r e , c o n t a i n i n g v a r i o u s h y d r o c a r b o n compounds, a
number o f s e l e c t e d p o l a r compounds and a s u p e r c r i t i c a l component.
It predicts quite well vapor-liquid-phase equilibria for a multi-
component system i n t h e r e t r o g r a d e r e g i o n b u t cannot p r e d i c t t h e
f o r m a t i o n o f a second l i q u i d phase.
The m i x i n g r u l e s u s e d i n t h e e q u a t i o n o f s t a t e a r e d e f i n e d as
follows :
1 / 2
a- - (a., χ a ) (1-k- )
lm 11 mm lm
and (1)
where a and b a r e t h e average Van d e r Waal c o n f i g u r a t i o n a l

c o e f f i c i e n t s f o r m i x t u r e s , and 1 and m a r e t h e p a i r w i s e s p e c i e s which
can be a d j u s t e d f o r t h e d i p o l e c o n t r i b u t i o n o f ammonia-butene t h r o u g h
the i n t e r a c t i o n p a r a m e t e r s , k. and . A l l o t h e r k and b v a l u e s
o f t h e i n t e r a c t i o n c o e f f i c i e n t s were s e t t o 0 and 1, r e s p e c t i v e l y .
T h i s model h a s some s e r i o u s l i m i t a t i o n s i n r e p r e s e n t i n g t h e e f f e c t s
o f p o l a r compounds, s i n c e q u a d r u p o l e and s t r o n g i n t e r a c t i o n f o r c e s
are ignored. Nevertheless, one c a n o b t a i n a " b a l l p a r k " e s t i m a t e
o f t h e l i k e l y degree o f s e p a r a t i o n .

TABLE I
Properties of C4 Components
Property l-Butene 11 3 - B u t a d i e n e
M o l e c u l a r Wt. 56.11 54*09

C r i t i c a l Temp* C 146.4 152*20
C r i t i c a l Press.MPa 4*019 4*32?
C r i t i c a l Vol» c c / m o l e 4*276 4*083
N o r m a l BP.C -0.25 -4.411
S o l u b i l i t y Param. 4.7504xE04 4*8694xE04
D i p o l e Mom* D e b y e 0.34 0.0
Acentric Factor 0*1867 0*1932 I
Properties of Solvents
Property Ethane Ethylene Carbon Dioxide Ammonia

M o l e c u l a r Wt* 30.07 28*05 44.01 17.03
C r i t i c a l Temp>C 3 2 * 2 7 9*21 31 .04 132.50
C r i t i c a l Press*
MPa 4*88 5.03 7.38 11.27
C r i t i c a l V o l . c c 4.919 4.601 2.136 4.255
N o r m a l BP*C -88*60 103*7 -33.43
S o l u b i l i t y Coeff*

3*9134xE04 3.932xE04 4.605xE04 9.239xE04
D i p o l e Mom.Bebye 0*0 0.0 0.0 1 .47
Acentric Factor 0*09896 0.085 0.2276 0.2520
17. HACKER Separation of Butadiene-Butène Mixtures 217
E x p e r i m e n t a l A p p a r a t u s and Materials
A l l s o l v e n t gases were s u p p l i e d as c y l i n d e r gases h a v i n g a s p e c i f i e d

minimum p u r i t y o f 99.0%. Butene, b u t a d i e n e and ammonia were u s e d
as r e c e i v e d w i t h o u t f u r t h e r p u r i f i c a t i o n .
E x t r a c t i o n e x p e r i m e n t s were c a r r i e d o u t i n a o n e - l i t e r , s t i r r e d ,
s t a i n l e s s s t e e l A u t o c l a v e v e s s e l ( A ) r a t e d a t 5000 p s i g a t 600 F. A
complete s c h e m a t i c o f the assembly i s shown i n F i g . 1. A l l
c o n n e c t i o n s w i t h s t a i n l e s s s t e e l 0.025 I.D. t u b i n g were made w i t h
Autoclave E n g i n e e r i n g Speedbite f i t t i n g s . The présure v e s s e l was
m a i n t a i n e d a t c o n s t a n t temperature by means o f e x t e r n a l e l e c t r i c a l
h e a t i n g and an i n t e r n a l c o o l i n g c o i l . C o o l i n g was f u r n i s h e d by
water c h i l l e d and c i r c u l a t e d by a Blue-M f r e o n r e f r i g e r a t i o n u n i t .
An A u t o c l a v e magnetic s t i r r i n g u n i t powered by an a i r motor (M) was
u s e d t o ensure adequate m i x i n g o f the c e l l c o n t e n t s . The p r e s e n c e
o f phase i n t e r f a c e s were v i e w e d t h r o u g h the windows o f a 50 c c
J e r g u s o n gauge(J) ( r a t e d a t 5000 p s i g a t 72 F ) , i n p a r a l l e l w i t h
the main c e l l . The s i g h
l e v e l i n d i c a t o r , had an
measure the t o t a l volumes o f the l i q u i d s i n the c e l l .
Butene and b u t a d i e n e were pumped i n t o the the r e a c t o r t h r o u g h
a common LP10 Whitey d i s p l a c e m e n t pump(Cl). A 30-pound n i t r o g e n
head was u s e d t o p r e s s u r i z e each h y d r o c a r b o n c y l i n d e r t o m a i n t a i n
adequate pumping e f f i c i e n c y . Ammonia was pumped as a l i q u i d
t h r o u g h a second Whitey pump(C2), e q u i p p e d w i t h a r e f r i g e r a t e d
head t o a v o i d v a p o r i z a t i o n d u r i n g c o m p r e s s i o n . The ammonia l i n e
was i n d e p e n d e n t l y c o o l e d t o p r e v e n t v a p o r i z a t i o n d u r i n g t r a n s f e r to
the r e a c t o r . A s l i g h t h e l i u m p r e s s u r e was m a i n t a i n e d i n the v e s s e l
d u r i n g c h a r g i n g t o f u r t h e r ensure a minimum o f v a p o r i z a t i o n a t the
l i q u i d s u r f a c e and ease the measurement o f the l i q u i d l e v e l .
E t h y l e n e , c a r b o n d i o x i d e , o r ethane were compressed t o the
d e s i r e d p r e s s u r e t h r o u g h a H a s k e l Model AG-62, gas c o m p r e s s o r ( C 3 ) ,
w i t h a 25-1 c o m p r e s s i o n r a t i o and a maximum r a t e d o u t l e t p r e s s u r e
o f 9000 p s i g . The mass o f the gases u s e d i n each r u n was
d e t e r m i n e d by w e i g h t l o s s o f the gas c y l i n d e r mounted on a Dayton
d i g i t a l s c a l e . A redundant volume check was made by m e a s u r i n g the
d i f f e r e n c e between the l i q u i d l e v e l s b e f o r e and a f t e r gas a d d i t i o n
to the l i q u i d c h a r g e and the t o t a l volume o f the v e s s e l . The
p r e s s u r e o f the system and i n each o f the r e c e i v e r v e s s e l s , E l and
E2, was measured w i t h c a l i b r a t e d h i g h p r e s s u r e p r e c i s i o n Bourdon
tube gauges o f a p p r o p r i a t e range (G1,G2,G3).
The e x t e r i o r o f the A u t o c l a v e v e s s e l w a l l was d i v i d e d i n t o
t h r e e h e a t i n g zones, each c o n t r o l l e d by one Eurotherm 103
temperature c o n t r o l l e r ( T C ) . The r e m a i n i n g s e c t i o n s were h e a t
t r a c e d w i t h s e l f - l i m i t i n g "Autotrace" h e a t i n g tapes to prevent
v a p o r c o n d e n s a t i o n i n the l i n e s . H e a t i n g c o n t r o l s were a d j u s t e d
m a n u a l l y and a l l temperatures were measured w i t h c o p p e r - c o n s t a n t a n
thermocouples a t t a c h e d t o the c e l l and r e c e i v e r v e s s e l s . The
thermocouple o u t p u t v o l t a g e s were i n d i c a t e d on a 1 0 - p o i n t Acromag
d i g i t a l v o l t m e t e r . A c a l i b r a t e d p l a t i n u m - 1 0 % rhodium thermocouple
was u s e d t o measure the temperature o f the c o n t e n t s i n the
autoclave reactor.

F i g u r e 1. Experimental Apparatus

17. HACKER Separation ofButadiene-Butene Mixtures 219
P r o c e d u r e . Sampling and Analysis
Each e x p e r i m e n t was c o n d u c t e d as f o l l o w s : The system was e v a c u a t e d

to remove r e s i d u a l f l u i d s . N i t r o g e n was t h e n f l u s h e d t h r o u g h the
system and the system once a g a i n e v a c u a t e d . The h y d r o c a r b o n and
ammonia were t h e n pumped i n t o the c e l l as l i q u i d s . The d e s i r e d
l i q u i d was m o n i t o r e d from the l e v e l on the s i g h t g l a s s . The composi-
t i o n was d e t e r m i n e d by volume p e r c e n t o f the h y d r o c a r b o n s and
entraîner added. The s o l v e n t gas was t h e n i n t r o d u c e d . The tempera-
t u r e o f the c o n t e n t s i n the c e l l was a d j u s t e d t o the d e s i r e d v a l u e
and s t i r r e d v i g o r o u s l y . The p r e s s u r e o f the s o l v e n t gas was s l o w l y
i n c r e a s e d u n t i l the l i q u i d i n t e r f a c e d i s a p p e a r e d and an o p a l e s c e n c e
regime appeared, i n d i c a t i n g the a t t a i n m e n t o f the c r i t i c a l r e g i o n .
The gas p r e s s u r e was t h e n r e d u c e d by a s l i g h t d e p r e s s u r i z a t i o n i n
the chamber u n t i l the i n t e r f a c e j u s t r e a p p e a r e d . I t was e s t a b l i s h e d
t h a t t h i s p r o c e d u r e p e r m i t t e d the c o n t e n t s t o be a d j u s t e d l e s s t h a n
2 t o 3 p e r c e n t o f the c r i t i c a l p r e s s u r e . S t i r r i n g was d i s c o n t i n u e d
about two minutes b e f o r
the v a p o r and l i q u i d phases
An e s t i m a t e o f the volume o f s o l v e n t added t o the h y d r o c a r b o n
m i x t u r e was o b t a i n e d by c a l c u l a t i n g the d i f f e r e n c e i n the l i q u i d
l e v e l b e f o r e and a f t e r gas a d d i t i o n , which i s a p p r o x i m a t e l y e q u a l
to the volume o f gas d i s s o l v e d i n the l i q u i d phase. This value i s
added t o the volume above the l i q u i d i n t e r f a c e t o o b t a i n the t o t a l
s o l v e n t volume added t o the system. The r a t i o o f ethylene/ammonia
s o l v e n t m i x t u r e added to the volume o f b u t a d i e n e / b u t e n e s o l u t i o n
was a p p r o x i m a t e l y 5:1.
The c o n t e n t s o f the r e a c t o r were sampled b e f o r e and a f t e r the
i n t r o d u c t i o n o f the s o l v e n t gas. T h i s was done by t r a p p i n g approx-
i m a t e l y 0.5 c c o f the m i x t u r e from the r e a c t o r volume i n a p r e c a l -
i b r a t e d l o o p o f 1/16 i n c h i . d . sample l i n e l o c a t e d between two h i g h
p r e s s u r e v a l v e s ( S ) a d j a c e n t t o the v e s s e l . The volume o f the sample
withdrawn was s u f f i e n t l y s m a l l t o m i n i m i z e any changes i n the p r e s -
s u r e (< 0.1 p s i ) o f the main c o n t e n t s o f the v e s s e l . The h i g h
p r e s s u r e sample was f u r t h e r expanded i n t o a p r e - e v a c u a t e d 300 c c
Hoke c y l i n d e r ( E l ) t o about 5 atm. T h i s volume o f sample was a g a i n
expanded t o about 1 atm i n a p r e - e v a c u a t e d , f i n a l 70-cc Hoke
cylinder(E2). P o r t i o n s o f t h i s volume were t h e n i n j e c t e d by means
o f an automated V a l c o v a l v e ( V I ) i n t o the V a r i a n 920 gas chromato-
g r a p h i c ) . A l l sample l o o p s were a l s o h e a t t r a c e d t o p r e v e n t conden-
s a t i o n i n the l i n e s . T h i s p r o c e d u r e was a l s o f o l l o w e d i n s a m p l i n g
the l i q u i d phase from the bottom o f v e s s e l as w e l l . S y r i n g e sam-
p l i n g t h r o u g h diaphram p o r t s l o c a t e d a t s t r a t e g i c p o s i t i o n s i n the
system p r o v i d e d a d d i t i o n a l checks on the automated s a m p l i n g
procedures.
A l l samples were a n a l y z e d i n an A l l T e c h 1/8"I.D, 20 f o o t column,
packed w i t h VZ-7 r e s i n , u s i n g h e l i u m as the c a r r i e r gas. T h i s column
p r o v e d more e f f e c t i v e f o r the measurement o f the C4 components t h a n
the Poropak- Ν column. Ammonia was n o t d e t e c t e d by t h i s column and
as a r e s u l t some o f the assumptions employed t o t r e a t the s o l v e n t
phase a r e d e s c r i b e d i n a l a t e r p a r a g r a p h . The G.C. was r u n w i t h the
i n j e c t o r chamber s e t a t 115 C, the column oven temperature a t 60 C
and the f i l a m e n t c u r r e n t s e t a t 150 ma. Column a n a l y s e s were p e r
formed by an A u t o l a b I n t e g r a t o r . A Leeds and N o r t h r u p s t r i p c h a r t
r e c o r d e r was u s e d t o p l o t the o u t p u t o f the i n t e g r a t o r and t o

p r o v i d e a v i s u a l d e t e r m i n a t i o n o f the time t r a c e and the magnitude

peak h e i g h t s f o r r a p i d c o m p a r i s o n o f the r e l a t i v e e f f e c t i v e n e s s o f
the s e p a r a t i o n . A sample s t r i p c h a r t r e c o r d o f the G.C. o u t p u t i s
shown i n F i g . 2.
Results
T i e l i n e s o f the system can be g e n e r a t e d from the e q u i l i b r i u m

c o m p o s i t i o n s f o r each r u n and s e l e c t i v i t i e s computed. The r e s u l t s
o f measurements o b t a i n e d f o r the 5% by volume o f ammonia/ethylene
a r e r e p r e s e n t e d i n the b i n o d a l diagram i n F i g . 3. Butene i s
r e p r e s e n t e d as the d i s t r i b u t e d component between the s o l v e n t phase
and the b u t a d i e n e - r i c h phase. The ammonia-solvent gas m i x t u r e was
c o n s i d e r e d t o behave as a p s e u d o - s o l v e n t o f f i x e d c o m p o s i t i o n . The
r a t i o o f the i n t e g r a t e d peaks f o r b u t e n e ( i ) and b u t a d i e n e ( j ) was
u s e d t o compute the s e l e c t i v i t y , Β ( b e t a ) , d e f i n e d on a s o l v e n t -
f r e e b a s i s , as:
(y.)solven
3
Β (2)
v
(x^)heavy phase χ ( j ) s o l v e n t phase
R e p r e s e n t a t i v e r e s u l t s a r e shown i n T a b l e I I and I I I f o r e t h y l e n e
and ethylene/ammonia and ethane and ethane/ammonia s o l v e n t m i x t u r e s .
S i n c e our d e t e c t i o n c a p a b i l i t y was l i m i t e d t o h y d r o c a r b o n s gases
o n l y , ammonia c o u l d n o t be d i r e c t l y measured i n e i t h e r phase.
However, the s e l e c t i v i t y as d e f i n e d i n Eqn. 2 can be c o n s i d e r e d as
a measure o f the r a t i o o f the d i s t r i b u t e d components o n l y ; hence,
i n d e p e n d e n t o f the a b s o l u t e c o n c e n t r a t i o n o f the s o l v e n t components.
A l l e x t r a c t i o n runs were made w i t h e q u i m o l a r m i x t u r e s o f
b u t e n e / b u t a d i e n e u s i n g e t h y l e n e , ethane o r c a r b o n d i o x i d e as the
s o l v e n t w i t h v a r i o u s c o n c e n t r a t i o n s o f ammonia from 0 - 1 0 vol%.
I n the absence o f ammonia, s e p a r a t i o n o f the m i x t u r e o f h y d r o
c a r b o n s was n e g l i g i b l e . T a b l e IV summarizes the d a t a f o r pure
s o l v e n t s and shows a comparison w i t h some s e l e c t e d d a t a f o r ammonia
/ p u r e gas m i x t u r e s . Ammonia/ethylene m i x t u r e s appear t o be more
e f f e c t i v e as s o l v e n t m i x t u r e s , w i t h a marked s e p a r a t i o n o f butene
achieved. 2,3-Butadiene i s c o n c e n t r a t e d i n the heavy phase, i n
agreement w i t h the f i n d i n g s r e p o r t e d f o r l i q u i d ammonia ( 1 ) .
A s e r i e s o f e x p e r i m e n t s was c o n d u c t e d t o d e t e r m i n e whether
t h e r e e x i s t s an ammonia c o n c e n t r a t i o n f o r which maximum s e p a r a t i o n
c o u l d be a t t a i n e d . A t a p r e s s u r e o f 600 p s i a and 20 degrees C. and
between 5 and 8 v o l % ammonia, a maximum i n the s e l e c t i v i t y i s
o b t a i n e d and i s shown i n F i g . 4. The s e l e c t i v i t y , however,
d e c r e a s e s w i t h i n c r e a s i n g temperature, w i t h o t h e r v a r i a b l e s h e l d
c o n s t a n t as shown i n F i g . 5. The t r e n d o b s e r v e d t h e s e e x p e r i m e n t s
a r e i n agreement w i t h the f i n d i n g s o f B r i g n o l e , e t a l . ( u ) . An
e r r o r o f +/- 5% was e s t i m a t e d i n the c a l c u l a t i o n o f the e x p e r i
mental s e l e c t i v i t i e s . The e x p e r i m e n t a l r e s u l t s were compared w i t h
p r e d i c t i o n s o b t a i n e d from the e q u a t i o n o f s t a t e , assuming t h a t the
i n t e r a c t i o n parameter, k ^ m » 0.2 f o r ammonia and 1-butene dominated
the n o n - i d e a l i t y o f the system. A c o m p a r i s o n o f the c a l c u l a t e d
s e l e c t i v i t i e s o b t a i n e d f o r the ethylene/ammonia m i x t u r e s a r e g i v e n
i n T a b l e I I w i t h the r e s u l t s i n T a b l e I I I f o r the ethane system.

H AC KER Separation of Butadiene-Butene Mixtures 22
-50
-60
-70
-80
Lower Phase -90
-100
Upper Phase CH
2 4
-90
Time
F i g u r e 2. T y p i c a l Gas Chromatographs from a VZ-& Column w i t h

Column Temperature a t 98 C. Ammonia Not D e t e c t e d i n t h i s Column.
F i g u r e 3. T e r n a r y Phase Diagram f o r the System. 8% Ammonia

C o n c e n t r a t i o n i n E t h y l e n e . P r e s s u r e = 600 p s i a , Temp = 20 °C.
E x p e r i m e n t a l P o i n t s Shown as Dots.

TABLE I I . Butadiene-Butene-Ethylene-Ammonia E q u i l i b r i u m Composition
PHASE PHASE
PRES- SOLVENT BUTA- BUTADIENE BUTA-
TEMP SURE NH 3 C H 2 4 BUTENE DIENE C H 2 4 BUTENE DIENE BETA
C PSIA % y i y yk X l x x
fc β
20 600 0 88. 351 3. 768 7. 881 45.940 17. 47 36. 584 1.00
0 88. 425 3. 763 7. 839 38.338 19. 765 41. 901 0.99
0 69. 694 14. 932 15. 374 71.997 13.092 14. 911 1.10
2.3 82. 199 8. 828 8. 973 58.461 17. 483 20. 879 1.17
5.0 89. 063 6. 936 4. 001 52.675 23. 890 23. 435 1.70
5.0 88.879 6. 903 4. 218 40.109 30.149 29. 742 1.61
5.0 76. 970 15.069 7. 961 58.039 22. 047 19. 914 1.71
5.0 75. 469 15. 505 8.448 55.886 23. 201 20.913 1.61
5.0 89. 132 8. 805 2.064 38.799 47. 751 13.450 1.20
5.0 90.259 8 066 1 675 34.527 50 693 14.780 1.40
5.0 90. 003
8.0 91.066 2. 629 6. 305 46.473 12. 884 39. 303 1.27
8.0 85. 908 3. 288 8. 151 44.928 13. 157 40. 645 1.24
8.0 86. 668 11. 710 1. 622 47.847 41. 382 10. 771 1.88
8.0 86. 775 11. 737 1. 488 49.963 39. 604 10.433 2.08
8.0 69. 579 19.803 10. 618 49.100 27. 951 22. 949 1.53
8.0 70. 150 19. 600 10. 249 61.617 21. 157 17. 226 1.56
8.0 92. 786 2. 932 4. 238 48.052 17. 872 34.075 1.30
8.0 92. 468 3. 101 4. 430 52.335 16. 484 31. 182 1.32
8.0 90.478 7. 865 1. 657 37.229 48. 002 14. 769 1.46
8.0 90.092 8. 193 1. 716 38.954 46. 955 14.091 1.43
8.0 71.455 8.,932 19.,613 44.076 13.,800 42. 124 1.39
8.0 70. 326 8.,981 20.,693 42.661 14.,033 43. 306 1.34
8.0 71. 296 9.,006 19,.698 40.781 14.424 33.,795 1.42
10.0 59.,583 27,.028 13,.389 39.981 36 .671 23,.348 1.29

10.0 60,,217 26 .028 13 .389 41.815 35 .692 22.493 1.32
10.0 74,.642 19 .423 5 .984 66.140 25 .400 8 .451 1.10
10.0 74.960 19.222 5.818 65.523 25 .784 8 .694 1.10
20 800 2.3 70 .166 13 .873 15 .960 34.716 28 .791 36 .493 1.10

2.3 69 .498 14 .112 16 .389 43.984 24 .539 31 .477 1.10
5.0 76 .947 12.740 10.312 74.065 14 .520 11.415 1.05

5.0 77 .599 12 .566 9.835 74.093 14 .494 11.413 1.00
5.0 85 .538 3.497 10 .965 68.631 7 .017 24.352 1.11
5.0 85 .908 3 .354 10.738 68.631 7 .017 24 .392 1.06
10.0 81 .026 7 .044 11 .930 67.741 11 .236 21 .021 1.10

10.0 80 .266 3 .354 12 .183 67.009 11 .767 21 .224 1.12
20 1100 0 69 .694 14 .932 15 .374 71.997 13.092 14 .911 0.90

0 81 .759 8 .583 8 .713 73.607 12 .124 14 .270 0.86
5.0 84 .760 8 .380 6 .860 77.316 11 .457 11 .227 0.84

5.0 84 .074 8 .457 7.451 74.816 12 .849 12 .335 0.92
40 600 5.0 85 .128 8 .416 6 .456 34.556 34.501 30 .943 1.17

5.0 86 .617 7 .812 5 .571 29.325 37 .302 33 .372 1.25
60 600 5.0 75 .099 11 .814 8 .756 19.215 42 .621 38 .163 1.21

5.0 74 .163 12 .412 9.471 20.693 41 .856 37 .451 1.17

17. HACKER Separation of Butadiene-Butene Mixtures 223
TABLE III. Butadiene-Butene-Ethane-Ammonia Composition
Solvent Phase Butadiene Phase
Temp Pressure NH3 C2H6 Butene Butadiene C2H6 Butene Butadiene Beta
C psia % wi wj wk xi xj xk
20 900 4.18 76.258 10.925 12.817 74.367 11.568 14.065 1.0

4.18 76.505 10.834 12.661 74.993 12.079 12.929 1.09
4.18 74.654 11.232 14.113 75.137 12.667 12.169 1.31
620 6.97 90.406 3.998 5.596 85.647 5.830 8.523 1.04

640 6.97 90.107 4.123 5.770 83.324 6.804 9.871 1.03
17 725 6.97 87.224 5.220 7.556 88.497 4.817 6.686 1.00
725 6.97 87.387 5.181 7.432 88.766 4.497 6.737 1.05
1060 6.97 88.840 4.489 6.689 93.178 2.751 4.071 1.00
1060 6.97 88.90 4.443 6.657 93.086 2.801 4.113 1.00
19 675 6.97 85.525

675 6.97 86.137
18 600 6.97 88.024 6.135 5.841 85.503 7.379 7.117 1.01
600 6.97 87.722 6.201 6.077 85.812 7.185 7.002 1.00
16 550 6.97 95.867 2.252 1.977 76.208 11.624 12.168 1.19
18 600 6.97 83.134 10.507 6.358 80.277 11.959 7.577 1.05
600 6.97 82.572 10.834 6.594 80.176 12.228 6.044 1.02
20 700 6.97 87.532 7.907 4.561 84.122 9.834 6.044 1.06
700 6.97 87.295 8.009 4.696 83.794 10.026 6.180 1.05
22 525 1.85 89.169 5.166 5.664 69.808 15.252 14.939 1.0

525 1.85 93.286 3.828 2.886 67.462 16.489 16.049 1.28
525 1.85 92.362 3.900 3.737 78.235 11.064 10.701 1.01
1100 1.85 88.100 6.345 5.555 78.508 11.205 10.288 1.04
1100 1.85 87.700 6.328 5.973 78.581 11.078 10.341 1.00
23 550 0 82.754 8.164 3.668 53.113 22.449 24.438 1.00

550 0 92.243 9.091 4.089 55.308 21.121 23.570 1.00
1075 0 77.928 10.663 11.438 72.545 13.088 14.367 1.00
1075 0 77.279 11.078 11.693 75.175 12.095 12.730 1.01
TABLE IV. Separation of Equimolar Mixtures of Butene-Butadiene

with Various Solvents
Experimental Values
TEMP PRESSURE SOLVENT SELECTIVITY

C psia
6.0 750 C2H4 1.23
40.0 1100 C02 1.0
22.0 1000 ft 1.0
22.0 700 ft 1.0
1.0
20.0
23.0
500
1100
«
C2H6/5* NH3 1.0
18.0 700 C2H6/7* NH3 1.06
20.0 900 C2H6/4$ NH3 1.09
23.0 550 C2H6 1.0

Entraîner Concentration-% Ammonia; Ethylene-(free basis)
F i g u r e 4. S e l e c t i v i t y as a F u n c t i o n o f Ammonia C o n c e n t r a t i o n a t
Temp - 20 C, P r e s s u r e - 600 p s i a .
F i g u r e 5. The I n f l u e n c e o f E x t r a c t i o n Temperature on t h e
S e l e c t i v i t y o f 5% Ammonia - E t h y l e n e S o l v e n t on M i x t u r e s o f
Butene and B u t a d i e n e .

S o l v e n t t o f e e d r a t i o s as w e l l as t h e e f f e c t o f ammonia
c o n c e n t r a t i o n i n t h e s o l v e n t were i n d e p e n d e n t l y v a r i e d t o match t h e
e x p e r i m e n t a l d a t a . The e f f e c t o f i n c r e a s i n g ammonia c o n c e n t r a t i o n
a t c o n s t a n t p r e s s u r e and temperature i n b o t h ethylene/ammonia and
ethane/ammonia s o l v e n t m i x t u r e s a r e shown i n T a b l e V.
Discussion
T h i s s t u d y i s by no means comprehensive and c o v e r s o n l y a narrow

range o f v a r i a b l e s . However, i t does demonstrate t h e i n f l u e n c e o f
entraîner i n t h e improvement o f s e p a r a t i o n o v e r a s i n g l e super-
c r i t i c a l solvent. The i n c r e a s e i n s e l e c t i v i t y (1.4 t o 1.8) f o r
b u t e n e / b u t a d i e n e m i x t u r e s i s compared w i t h t h e v a l u e o f 1.63
o b t a i n e d w i t h l i q u i d ammonia f o r t h e same b i n a r y s y s t e m ( l ) . More-
o v e r , i t has been demonstrated t h a t a m i x t u r e o f a p u r e s o l v e n t and
an entraîner p e r m i t s an improvement i n t h e s e p a r a t i o n a t temperatures
and p r e s s u r e s lower t h a n would have been o t h e r w i s e p r e d i c t e d w i t h a
s i n g l e gas s o l v e n t ( 2 0 )
component, such as ammonia
the l a r g e s e l e c t i v i t i e s o b s e r v e d i n t h e s e e x p e r i m e n t s . At present,
a l l t h e o r i e s are inadequate i n e x p l a i n i n g the chemical i n t e r a c t i o n s
between t h e entraîner and t h e m i x t u r e . The s t a t e o f t h e a r t i s
comparable t o l i q u i d phase s o l v e n t e x t r a c t i o n .
The d i s t r i b u t i o n o f t h e mixed s o l v e n t s between t h e phases
might p r o v i d e some a d d i t i o n a l u n d e r s t a n d i n g o f t h e r e a s o n f o r t h e
e f f e c t i v e n e s s o f t h e ammonia as an e n h a n c i n g agent. The s o l u b i l i t y
o f l i q u i d ammonia i n t h e l i q u i d h y d r o c a r b o n phase has been shown t o
be h i g h ( 2 1 ) because o f i t s s t r o n g b a s i c i t y as compared w i t h t h e
n o n - p o l a r h y d r o c a r b o n gases such as ethane and e t h y l e n e a t normal
c o n d i t i o n s ( 2 2 ) . A t h i g h e r p r e s s u r e s , however, s o l u b i l i t i e s o f a l l
compounds i n c r e a s e d r a m a t i c a l l y and, a c c o r d i n g l y , t h e d i f f e r e n c e s
between t h e p o l a r and n o n - p o l a r s o l u b i l i t i e s a r e somewhat
reduced(22). N e v e r t h e l e s s , even f o r a r e l a t i v e l y d i l u t e p o l a r
m i x t u r e i n a n o n - p o l a r gas, t h e s o l u b i l i t y o f t h e p o l a r component
exceeds t h e n o n - p o l a r component. A t t h e s e p r e s s u r e s , i t i s l i k e l y
t o be c o m p l e t e l y a b s o r b e d p r e f e r e n t i a l l y i n t o t h e l i q u i d phase. As
a r e s u l t , i t i s estimated t h a t the composition o f the s u p e r c r i t i c a l
phase w i l l c o n t a i n l i t t l e ammonia and p r e d o m i n a n t l y s o l v e n t gas
with extracted solute. F o r t h i s m i x t u r e t h e s o l v e n t phase w i l l
c o n s i s t o f e t h y l e n e o r ethane and butene w i t h a s m a l l c o n c e n t r a t i o n
o f ammonia. T h i s i s c o n f i r m e d i n t h e VLE f l a s h c a l c u l a t i o n s f o r a
10:1 s o l v e n t e x t r a c t i o n w i t h a e q u i m o l a r m i x t u r e o f e t h y l e n e and
ammonia. The d i s t r i b u t i o n o f ammonia t o e t h y l e n e i n t h e l i q u i d
phase i s 2.5:1, whereas i n t h e v a p o r i t i s 1:2.
The s e p a r a t i o n o f t h e l i q u i d components i n t h e p r e s e n c e o f a
s u p e r c r i t i c a l s o l v e n t o c c u r s much as i t does i n l i q u i d e x t r a c t i o n
w i t h t h e entraîner, ammonia, c o n c e n t r a t i n g i n t h e l i q u i d t o i n c r e a s e
the r e l a t i v e v o l a t i l i t y o f t h e butene t o b u t a d i e n e . The b u t a d i e n e
m i g r a t e s t o t h e ammonia-rich phase w h i l e t h e s o l v e n t gas phase o r
"vapor" w i l l c o n t a i n t h e butene.
The e x p l a n a t i o n f o r the h i g h e r s e l e c t i v i t y o f the e t h y l e n e /
ammonia m i x t u r e over the ethane/ammonia system i s somewhat
surprising. The e f f i c i e n c y o f s c e x t r a c t i o n o f a g i v e n s o l v e n t
toward a p a r t i c u l a r s o l u t e i s r e l a t e d t o the s u p e r c r i t i c a l

Table V
S e p a r a t i o n o f 1-Butene 2,3-Butadiene M i x t u r e s
C o m p u t a t i o n a l R e s u l t s by t h e E l y - M a n s o o r i
Equation of State
k.. = 0.2, a l l o t h e r k =0.

n
wèire i = ammonia , j 2 i - b u t e n e
Mixture Solvent-Fee Temp Vapo Liqui y

Ratio Ratio C psia yi xi Β
NH3/Ethylene
0.25 20 27 735 0..011 0.405 1..54
37 735 0,.0208 0.460 1..87
10 29 735 0..0175 0.385 1.,29
32 735 0..024 0.393 1.,37
37 735 0..0317 0.407 1.,40
0.50 10 47 735 0..0332 0.641 2.,86
57 735 0..426 0.786 3.,10
37 588 0..339 0.635 3.,94
47 588 0..433 0.834 4.,29
NH3/Ethane
0.0 2 22 294 0..5501 0.228 1.,04
0.50 10 47 588 0,.0250 0.544 1.,96
57 735 0,.252 0.606 1..65
77 853 0..0348 0.931 1..10
20 42 588 0,.0129 0.579 2..26
47 588 0,.0173 0.679 2..48
1.0 10 117 1190.7 0,.0331 0.900 0..91
97 955 0 .3636 0.512 1,.13

s o l u b i l i t y parameter, d e f i n e d i n terms o f the r e d u c e d p r o p e r t i e s o f

the s o l u t e and s o l v e n t ( 2 3 ) . The r e d u c e d t e m p e r a t u r e , d e f i n e d i n
terms o f t h e temperature a t which e x t r a c t i o n i s c a r r i e d o u t , s h o u l d
be c l o s e t o u n i t y t o maximize s e p a r a t i o n ( 2 4 ) .
S i n c e b o t h e t h y l e n e and ethane have r e d u c e d t e m p e r a t u r e s
n e a r l y e q u a l t o u n i t y a t t h e e x t r a c t i o n c o n d i t i o n s o f 20 C, (T =
.98) and e t h y l e n e (T — 1.04), t h e i r r e s p e c t i v e s o l v e n t capaciïies
f o r butene s h o u l d be about t h e same. T h i s i s t h e c a s e as i s
r e f l e c t e d i n t h e same v a l u e s f o r t h e s e l e c t i v i t y a g a i n s t b u t e n e f o r
a l l pure s o l v e n t gases. One c a n c o n c l u d e t h a t t h e p r i m a r y e f f e c t
o f t h e n o n - p o l a r s o l v e n t i s t o i n c r e a s e t h e c a p a c i t y o f t h e "vapor"
phase f o r t h e e x t r a c t e d s o l u t e n e a r t h e c r i t i c a l . The i n f l u e n c e o f
the second s o l v e n t p r o v i d e s o n l y t h e o p t i o n o f m o d i f y i n g t h e
p h y s i c a l p a r a m e t e r s ; namely, p r e s s u r e and t e m p e r a t u r e , under which
the o p t i m a l e x t r a c t i o n i s t o be c o n d u c t e d . The e v i d e n c e f o r t h i s
i s t h e e f f e c t o f t h e ammonia on the s e l e c t i v i t y as c a l c u l a t e d by
the EOS i n T a b l e V. The h i g h e r v a l u e s f o r t h e s e l e c t i v i t i e s i n t h e
e t h y l e n e m i x t u r e s a r e pronounced
solvent mixture i n t e r a c t i o
o f butene i n t h e v a p o r phase.
The s i m p l e model u s e d i n t h e EOS, however, does n o t c o m p l e t e l y
i n d i c a t e t h e p r e s e n c e o f a maximum i n t h e q u a n t i t y o f ammonia u s e d
as an entraîner. That t h i s i s i n c o n t r a s t t o o u r e x p e r i m e n t a l
o b s e r v a t i o n s s u g g e s t s t h a t o t h e r f a c t o r s such as c h e m i c a l syner-
g i s t i c e f f e c t s cannot be i g n o r e d and a r e l i k e l y t o have a g r e a t e r
e f f e c t t h a n a n t i c i p a t e d . While t h i s f e a t u r e o f t h e system was
e n t i r e l y unexpected, i t does s u g g e s t t h a t t h e Η-bonding o r o t h e r
s t r o n g p o l a r i n t e r a c t i o n t h a t o c c u r s w i t h many s e l e c t i v e s o l v e n t s
and s o l u t e s i n l i q u i d e x t r a c t i o n , may be e q u a l l y a p p l i c a b l e i n s c
e x t r a c t i o n where s t r o n g p o l a r - p o l a r i n t e r a c t i o n s (as between
ammonia and 1-butene) e x i s t .
Conclusions
1. A maximum v a l u e i n t h e s e l e c t i v i t y o f 1.4 - 1.8 c a n be a c h i e v e d

w i t h a 5 - 8 v o l % ammonia c o n c e n t r a t i o n i n e t h y l e n e f o r t h e
b u t a d i e n e - butene s e p a r a t i o n . The h i g h e r s e l e c t i v i t y found i n
the s u p e r c r i t i c a l e x t r a c t i o n i s comparable t o the s e l e c t i v i t y
r e p o r t e d f o r the same s e p a r a t i o n w i t h l i q u i d ammonia.
3. Ethylene/ammonia m i x t u r e s appear t o be a more e f f e c t i v e as
s o l v e n t s f o r the s e p a r a t i o n o f a b u t a d i e n e - b u t e n e m i x t u r e t h a n
are ethane/ammonia m i x t u r e s w i t h t h e same c o n c e n t r a t i o n o f
ammonia. T h i s i s v e r i f i e d i n d e p e n d e n t l y by t h e p r e d i c t i o n s o f
the E l y - M a n s o o r i e q u a t i o n o f s t a t e . The c o m b i n a t i o n o f
enhanced s o l u b i l i t y o f t h e ethylene/ammonia m i x t u r e , a c c o r d i n g
to J o s h i and P r a u s n i t z , as a s o l v e n t and t h e s y n e r g i s t i c
c h e m i c a l e f f e c t between t h e h i g h l y p o l a r ammonia and e t h y l e n e
may e x p l a i n the o b s e r v e d o v e r a l l i n c r e a s e d e f f e c t i v e n e s s o f the
solvent mixture.

Acknowledgments
I would l i k e t o e x p r e s s my a p p r e c i a t i o n t o t h e Amoco C h e m i c a l s Co.

f o r t h e i r s u p p o r t f o r t h i s work. I n p a r t i c u l a r , I w i s h t o e x p r e s s
my thanks f o r t h e i n t e r e s t shown i n t h i s work b y D. E. Hannemann
and P. G. T h o r n l e y and t o Franke Brooks, my t e c h n i c i a n , f o r h i s
i n d u s t r y and c a r e i n c o n d u c t i n g t h e s e e x p e r i m e n t s .
Literature Cited
1. Poffenberger, N.; Horsley, L. H.; Nutting, H. S.; Trans. AIChE,
42:815, (1946)
2. Joshi, D. K.; Prausnitz, J . M.; AIChE Jour. 30:522, (1984)
3. Todd, D. B.; Elgin, J . C.; AIChE Jour. 1:20, (1955)
4. Weinstock, J . J.; Elgin, J . C.; Jour Chem Engr. Data, 4:3, (1959)
5. Paulaitis, M. E.; Kander, R. G.; DiAndreth, J . R.; Berichte der
Bunsen-Gesellschaft f. Phy. Chem. 9:869 (1984)
6. Fogel, W.; Arlie, J
7. Brule, M. R.; Corbett
June
8. Starling, Κ. E.; Khan, Μ. Α.; Watanasiri, S.; Fundamental
Thermodynamics of Supercritical Extraction, Presented Annual
Mtg. AIChE, San Francisco, CA, (1984)
9. Prausnitz, J . M.; Fluid Phase Equil., 14, 1, (1983)
10. Cotterman, R. L.; Dimitrelis, D.; Prausnitz, J . M.; Ber. Bunsen
Gelsch. Phy. und Chem., 9, 796, (1984)
11. Reid, R. C.; Schmitt, N. J.; J . Chem Engr. Data, 31:204, (1986)
12. Vasilakos, N. P.; Dobbs, J . M.; Parisi, A. S.; IEC Process
Design, 24, 121, (1985)
13. Brunner, G.; Fluid Phase Equil., Part II, 10, 289, (1983)
14. Treybal, R. Ε.;, "Liquid Extraction", 2nd Ed., McGraw-Hill, NY
(1963)
15. Prigogine, I.; Bull Soc. Chem, Belg., 52, 115, (1943)
16. Eckert, C. Α.; Greiger, R. Α.; I&EC Process Design. 6, 250,
(1967)
17. Rowlinson, J . S.; Liquids and Liquid Mixtures, 2nd Ed., Plenum
Press London, (1969)
18. Mansoori, G. Α.; Ely, J . F.; Density Expansion Mixing Rules,
Unpublished, (1984)
19. Brignole, Ε. Α.; Skjold-Jorgensen, S.; Fredenslund, J . M.;
ibid. 9:801 (1984)
20. Brunner, G; Fluid Phase Equilibria, 10:289, (1983)
21. Patyi, L.; et a l . , Zhur. Priklad. Khimii., 51:1296 (1978)
22. Prausnitz, J . M.; "Molecular Thermodynamics of Fluid Phase
Equilibria", Chap.10, Prentice Hall, NY (1969)
23. Gidding, J . C.; Myers, M. N.; et a l . , Science 162:67, (1968)
24. Paul, P. M. F.; Wise, W. S.; The Principles of Gas Extraction.
Mills & Boon, Ltd., Monograph CE/5, (1971)
RECEIVED October 3, 1986

Chapter 18
Fractional Destraction of Coal-Derived Residuum

Robert P. Warzinski
U.S. Department of Energy, Pittsburgh Energy Technology Center, P.O. Box 10940,
Pittsburgh, PA 15236
An apparatus has been developed to fractionate

coal-derived residuum by exploiting the solvent
power of fluids near their critical points.
Termed Fractional Destraction, the method
fractionates residuum according to the solubility
of its constituent components in a supercritical
fluid. The novel aspect of the approach is the
incorporation o
less-soluble components onto a packed bed.
Fractionation of residuum will facilitate the
determination of previously unattainable
information concerning the composition and
process-related behavior of this complex material.
This paper describes operation of the unit to
fractionate a residuum sample produced at the
Wilsonville Advanced Coal Liquefaction Test
Facility.
D e s c r i b i n g the b e h a v i o r o f u n d e f i n e d m i x t u r e s , whether from

n a t u r a l o r s y n t h e t i c s o u r c e s , o f t e n b e g i n s w i t h the s e p a r a t i o n
of t h e s e complex systems i n t o e f f e c t i v e pseudocomponents by
d i s t i l l a t i o n (1)· Each pseudocomponent i s then c h a r a c t e r i z e d as
i f i t were a pure compound, and i t s c h a r a c t e r i z a t i o n d a t a a r e
used i n a p p r o p r i a t e c o r r e l a t i o n s . The presence o f n o n v o l a t i l e
residuum poses a s e r i o u s l i m i t a t i o n t o such methodology. F o r
c o a l - d e r i v e d l i q u i d s , heavy crude o i l s , t a r sands, and s h a l e
o i l , more than 50 p e r c e n t o f the f l u i d may not be d i s t i l l a b l e
(1_). S i n c e t h i s n o n v o l a t i l e r e s i d u e cannot be s e p a r a t e d u s i n g
c o n v e n t i o n a l t e c h n i q u e s , new methods o f s e p a r a t i o n and
c h a r a c t e r i z a t i o n must be developed t o p r o v i d e the n e c e s s a r y
i n f o r m a t i o n f o r d e s i g n and o p e r a t i o n o f p l a n t s u t i l i z i n g the
f o s s i l f u e l s mentioned above ( 2 ) .
A p a r t from the need t o f r a c t i o n a t e r e s i d u u m - c o n t a i n i n g
f o s s i l f u e l s f o r the measurement and p r e d i c t i o n o f
t h e r m o p h y s i c a l p r o p e r t i e s , o t h e r i m p o r t a n t problems c o u l d be
r e s o l v e d b e t t e r through the s t u d y o f residuum pseudocomponents.
Two examples i n the a r e a o f c o a l l i q u e f a c t i o n a r e the r o l e o f
This chapter not subject to U.S. copyright.

Published 1987, American Chemical Society

residuum ( a ) i n hydrogen u t i l i z a t i o n and hydrogen t r a n s f e r and

(b) i n t h e m a n i f e s t a t i o n o f h a r m f u l b i o l o g i c a l e f f e c t s .
Work a t t h e P i t t s b u r g h Energy T e c h n o l o g y C e n t e r has been
d i r e c t e d a t t h e development o f n o v e l t e c h n o l o g y f o r t h e
s e p a r a t i o n of f o s s i l f u e l residuum i n t o e f f e c t i v e
pseudocomponents. In t h i s r e s p e c t , a p p l i c a t i o n of s u p e r c r i t i c a l
f l u i d s i n a manner s i m i l a r t o t h a t r e p o r t e d by Z o s e l ( 3 ) i s
being developed. T h i s approach i s s i m i l a r to c o n v e n t i o n a l
d i s t i l l a t i o n i n t h a t an a p p a r a t u s i s used not o n l y t o e x t r a c t
the residuum but a l s o t o cause p a r t o f t h e residuum i n t h e f l u i d
phase t o r e t u r n as r e f l u x onto a packed bed. T h i s l i q u i d r e f l u x
i s caused by i n c r e a s i n g t h e temperature o f t h e s u p e r c r i t i c a l
f l u i d phase a t c o n s t a n t p r e s s u r e , t h e r e b y d e c r e a s i n g t h e d e n s i t y
o f t h e s u p e r c r i t i c a l f l u i d and i t s c a r r y i n g c a p a c i t y f o r t h e
r e s i d u u m . O p e r a t i o n o f a system i n t h i s r e g i o n o f r e t r o g r a d e
c o n d e n s a t i o n has r e c e n t l y been r e p o r t e d i n t h e l i t e r a t u r e ( 4 ) .
O t h e r r e c e n t i n v e s t i g a t i o n s support t h e h y p o t h e s i s t h a t
supercritical solubilit
absence o f s t r o n g a s s o c i a t i n
method i s c a l l e d e i t h e
suggested, F r a c t i o n a l D e s t r a c t i o n . T h i s r e p o r t d e s c r i b e s the
use o f t h i s t e c h n o l o g y t o f r a c t i o n a t e a c o a l - d e r i v e d residuum
from t h e W i l s o n v i l l e Advanced C o a l L i q u e f a c t i o n T e s t F a c i l i t y .
Experimental
The e x p e r i m e n t a l u n i t , c a l l e d t h e F r a c t i o n a l D e s t r a c t i o n U n i t
(FDU), has been d e s i g n e d t o c o n t a c t a 3-4 kg charge o f residuum
w i t h a c o n t i n u o u s f l o w o f s u p e r c r i t i c a l f l u i d a t c o n d i t i o n s up
t o 673 Κ and 27.6 MPa. The h e a r t o f t h e FDU i s t h e F r a c t i o n a l
D e s t r a c t i o n V e s s e l (FDV) shown i n F i g u r e 1. The FDV c o n s i s t s o f
a m o d i f i e d 3.8-L 316 s t a i n l e s s s t e e l p r e s s u r e v e s s e l onto which
i s a t t a c h e d a 78-cm column f a b r i c a t e d o f 316 s t a i n l e s s s t e e l
(6.03-cm o.d., 1.11-cm w a l l ) . The column c o n t a i n s a packed bed
and a condenser s e c t i o n . I n t h e experiments r e p o r t e d h e r e , t h e
30-cm bed s e c t i o n was packed w i t h 0.41-cm s t a i n l e s s s t e e l P r o -
Pak p r o t r u d e d m e t a l d i s t i l l a t i o n p a c k i n g from S c i e n t i f i c
Development Co., S t a t e C o l l e g e , Pa. T h i s i s t h e same p a c k i n g
used i n a c o n v e n t i o n a l P o d b e l n i a k d i s t i l l a t i o n column. The
condenser c o n s i s t s o f a removable 38-cm f i n g e r made o f 316
s t a i n l e s s s t e e l (2.67-cm o.d., 0.78-cm w a l l ) t h a t i s heated by
an i n t e r n a l c a r t r i d g e h e a t e r t o promote r e f l u x . A t r i p l e zone
f u r n a c e i s used t o c o n t r o l t h e temperature i n t h e e x t r a c t i o n
zone. Temperature c o n t r o l on t h e column i s a c c o m p l i s h e d with
i n d e p e n d e n t l y c o n t r o l l e d band h e a t e r s on t h e packed bed and
condenser s e c t i o n s .
The d e s i r e d c h a r g e o f r e s i d u u m i s p l a c e d i n t h e e x t r a c t i o n
s e c t i o n o f t h e FDV, and t h e e n t i r e u n i t i s purged w i t h n i t r o g e n .
The FDU i s then brought up t o t h e o p e r a t i n g temperature b e f o r e
beginning solvent flow. The d e s t r a c t i o n f l u i d i s then pumped as
a l i q u i d through a p r e h e a t e r t o r a i s e i t s temperature above t h e
c r i t i c a l p o i n t b e f o r e i t i s i n t r o d u c e d i n t o t h e FDV through t h e
s p a r g i n g d e v i c e a t t h e bottom. The p r e s s u r e i s c o n t r o l l e d by a
h i g h - t e m p e r a t u r e Badger-Meter c o n t r o l v a l v e l o c a t e d near t h e

WARZINSKI Fractional Destraction of Coal-Denved Residuum
Figure 1. Sectional view of f r a c t i o n a l destraction u n i t .

o u t l e t o f t h e FDV. A f t e r t r a v e l i n g up t h e column, t h e f l u i d
s t r e a m , which now c o n t a i n s d e s t r a c t e d residuum, e x i t s a t the t o p
of t h e FDV and i s p a r t i a l l y d e p r e s s u r i z e d through t h e heated
c o n t r o l v a l v e i n t o a s e p a r a t o r c o n s t r u c t e d of a 2.25 L
( a p p r o x i m a t e l y 10.2-cm o.d., 42.5-cm l o n g ) 304 s t a i n l e s s s t e e l
c y l i n d e r . The s e p a r a t o r i s operated s l i g h t l y above t h e c r i t i c a l
temperature o f t h e s o l v e n t (TR=1.02) a t a p r e s s u r e o f 0.8 MPa.
S e p a r a t i o n o f t h e residuum from the s u p e r c r i t i c a l f l u i d i s
a c c o m p l i s h e d by t h e r e d u c t i o n i n p r e s s u r e . The residuum i s
d r a i n e d and c o l l e c t e d from t h e bottom o f t h e s e p a r a t o r a t
p e r i o d i c i n t e r v a l s , w h i l e the solvent i s f l a s h e d t o atmospheric
p r e s s u r e , condensed, and r e c o v e r e d as a l i q u i d . The o p e r a t i o n
of t h e FDU w i l l be r e p o r t e d i n d e t a i l i n a l a t e r p u b l i c a t i o n .
Toluene ( T = 591.7 K, P = 4.115 MPa) and cyclohexane ( T
c c c
= 553.4 K, P = 4.074 MPa) were used as t h e s u p e r c r i t i c a l f l u i d s

c
i n t h e work r e p o r t e d h e r e . They were o b t a i n e d i n drum

q u a n t i t i e s a t g r e a t e r than 99 percent p u r i t y and used as
r e c e i v e d . Owing t o i n e f f i c i e n c
d e s t r a c t e d residuum i
m a t e r i a l i s recovered i n a r o t a r y evaporator. The d i s t i l l e d
s o l v e n t i s then reused i n t h e FDU. I n t h e f i g u r e s i n t h i s
r e p o r t t h a t d e p i c t residuum overhead d a t a , c o r r e c t i o n has been
made f o r t h e residuum r e c o v e r e d i n t h e spent s o l v e n t .
The residuum used i n t h e work r e p o r t e d here was c o l l e c t e d
from t h e T102 vacuum d i s t i l l a t i o n tower d u r i n g Run 242 a t t h e
W i l s o n v i l l e Advanced C o a l L i q u e f a c t i o n Test F a c i l i t y . This run
was made u s i n g I l l i n o i s No. 6 c o a l from t h e B u r n i n g S t a r mine i n
what i s termed a S h o r t - C o n t a c t - T i m e I n t e g r a t e d Two-Stage
L i q u e f a c t i o n (SCT-ITSL) mode ( 6 ) . D u r i n g the time t h i s
p a r t i c u l a r sample was c o l l e c t e d , t h e T102 u n i t was operated a t
594 Κ and 3.4 KPa. The residuum was crushed t o minus 0.64 cm
and mixed by r i f f l i n g b e f o r e u s e .
Discussion
O p e r a t i o n o f t h e FDU w i t h c o a l - d e r i v e d residuum was preceded by

t e s t s on pure compounds and d i s t i l l a b l e c o a l l i q u i d s u s i n g n-
pentane as t h e s u p e r c r i t i c a l f l u i d ( 7 ) . The r e s u l t s o f t e s t s
w i t h t h e c o a l - d e r i v e d d i s t i l l a t e showed t h a t t h e FDU was
b a s i c a l l y p e r f o r m i n g as expected. L i q u i d r e f l u x was generated
by means o f t h e h o t f i n g e r when t h e d e v i c e was o p e r a t e d a t a
temperature s l i g h t l y above t h e c r i t i c a l temperature o f the
t r a n s p o r t f l u i d . When r e f l u x was e s t a b l i s h e d , f r a c t i o n a t i o n
based upon v o l a t i l i t y was o b s e r v e d . Poorer s e p a r a t i o n was
a c h i e v e d i n t h e absence o f r e f l u x .
The f i r s t work on t h e T102 bottoms i n v o l v e d o p e r a t i o n i n
the n o n - r e f l u x mode t o o b t a i n b a s e - l i n e d a t a on t h e t r a n s p o r t o f
t h i s residuum i n v a r i o u s hydrocarbon s o l v e n t s . U s i n g n-pentane,
c y c l o h e x a n e , and t o l u e n e a t a TR o f 1.02 and a t a PR o f 2, t h e
residuum brought overhead was 23, 54, and 67 percent o f t h a t
c h a r g e d , r e s p e c t i v e l y . Based on t h i s i n f o r m a t i o n , f u r t h e r
s t u d i e s were performed u s i n g c y c l o h e x a n e as t h e s u p e r c r i t i c a l
f l u i d , s i n c e a l a r g e p o r t i o n o f the residuum c o u l d be d e s t r a c t e d
a t a temperature s i m i l a r t o o r l e s s than t h a t i n t h e T102
separator.

18. WARZINSKI Fractional Destraction of Coal-Derived Residuum 233
A two-step d e s t r a c t i o n procedure was developed t o maximize

the amount of T102 residuum brought overhead. I n the f i r s t
s t e p , t o l u e n e i s used i n a manner s i m i l a r t o c o n v e n t i o n a l
s u p e r c r i t i c a l e x t r a c t i o n t o produce a n e a r l y a s h - f r e e m a t e r i a l
f o r subsequent f r a c t i o n a t i o n . T h i s f i r s t s t e p i s c a l l e d the
n o n - r e f l u x mode because the column o f the FDV i s m a i n t a i n e d a t
the same temperature as the e x t r a c t i o n s e c t i o n . I n the second
s t e p , c a l l e d the r e f l u x mode, the column and f i n g e r a r e heated
to a h i g h e r temperature than the e x t r a c t i o n s e c t i o n , which
causes the d e n s i t y of the f l u i d t o d e c r e a s e as i t t r a v e l s up t h e
column and thus promotes r e f l u x o f the l e s s - s o l u b l e components.
These two s t e p s a r e d e s c r i b e d below.
In the n o n - r e f l u x mode, the FDU was used t o p r o c e s s f i v e
800-gram charges of the T102 bottoms. R e p e t i t i v e o p e r a t i o n o f
the u n i t was performed t o produce s u f f i c i e n t q u a n t i t i e s of the
f i n a l f r a c t i o n s f o r subsequent c h a r a c t e r i z a t i o n and
e x p e r i m e n t a t i o n . F i g u r e 2 summarizes t h e o p e r a t i o n of the FDU
during these f i v e d e s t r a c t i o n s
brought overhead as a
2. As p r e v i o u s l y mentioned, the residuum overhead d a t a i n c l u d e
residuum r e c o v e r e d from both the s e p a r a t o r and the spent
s o l v e n t . The FDV was m a i n t a i n e d a t a T R o f 1.02, w i t h o v e r a l l
v a r i a n c e i n temperature f o r the f i v e t e s t s b e i n g ί 5 K.
Temperature v a r i a n c e d u r i n g any one t e s t was ί 2 K. The
d i f f e r e n c e s o b s e r v e d , e s p e c i a l l y i n the f i n a l amounts
d e s t r a c t e d , appear t o be due t o t h i s s m a l l temperature v a r i a n c e
betweeen r u n s . The h i g h e r y i e l d s were c o n s i s t e n t l y o b t a i n e d a t
temperatures n e a r e r the c r i t i c a l p o i n t . T h i s phenomenon appears
to be p a r t i c u l a r l y s e n s i t i v e t o t h e temperature of the
e x t r a c t i o n zone when t h e f l u i d i s f i r s t i n t r o d u c e d . The f a c t
t h a t t h e i n i t i a l d i s s o l u t i o n o f t h e residuum i n the f l u i d
i n f l u e n c e s t h e o v e r a l l y i e l d suggests t h a t components i n t h e
residuum may be a c t i n g as c o s o l v e n t s .
T a b l e I c o n t a i n s t h e e l e m e n t a l a n a l y s i s of the T102
bottoms, t h e m a t e r i a l brought overhead w i t h t o l u e n e , the r e s i d u e
r e m a i n i n g a f t e r the t o l u e n e d e s t r a c t i o n , and the s t a r t i n g c o a l
used a t W i l s o n v i l l e d u r i n g Run 242. The t o l u e n e overhead
r e p r e s e n t e d 66.8 p e r c e n t o f the m a t e r i a l charged t o the FDU, and
the r e s i d u e accounted f o r 27.9 p e r c e n t . Other m a t e r i a l
c o l l e c t e d from the FDU i n c l u d e s 4.2 p e r c e n t i n the spent s o l v e n t
and 2.7 p e r c e n t r e c o v e r e d d u r i n g c l e a n i n g of the FDV and
s e p a r a t o r w i t h t e t r a h y d r o f u r a n . The t o t a l m a t e r i a l b a l a n c e i s
101.6 p e r c e n t . T h i s number a l s o i n c l u d e s any r e s i d u a l t o l u e n e
or t e t r a h y d r o f u r a n i n the v a r i o u s samples. The overhead
c o l l e c t e d from the f i v e d e s t r a c t i o n s was ground and combined
b e f o r e use i n the r e f l u x mode e x p e r i m e n t s .
As p r e v i o u s l y mentioned, c y c l o h e x a n e was chosen f o r t h e
f r a c t i o n a t i o n s o l v e n t f o r the second s t e p , s i n c e i t c o u l d
t r a n s p o r t s u f f i c i e n t q u a n t i t i e s o f residuum a t r e a s o n a b l e
t e m p e r a t u r e s . I n the r e f l u x mode, the column of the FDV i s
o p e r a t e d a t a h i g h e r temperature t h a n the e x t r a c t i o n zone. As
the c a r r y - o v e r o f residuum d e c r e a s e s , t h e temperature of t h e
column i s reduced t o cause the d e n s i t y i n t h i s r e g i o n t o
i n c r e a s e and c o n s e q u e n t l y more residuum i s t r a n s p o r t e d overhead.

TABLE I . A n a l y s i s o f Feed C o a l t o Run 242, T102 Bottoms A f t e r

G r i n d i n g and M i x i n g , and M a t e r i a l s Produced by S u p e r c r i t i c a l
E x t r a c t i o n of T102 Bottoms With T o l u e n e i n the Non-Refl ux Mode
ILLINOIS 3
RUN 242& TOLUENE TOLUENE
NO. 6 COAL T102 BOTTOMS OVERHEAD RESIDUE
C 68.4 79.1 87.4 60.3

H 4.4 5.9 6.7 3.5
0 11.9 C
4.0 C
4.0 d
7.Id
Ν 1.4 1.3 1.3 1.4
S 3.2 1.0 0.7 0.9
Cl 0.1
ASH 10.6 8.7 0.1 29.4
H/C 0.77 0.89 0.91 0.69

M N
(VPO, 353 K,
PYRIDINE)
a
A n a l y s i s from W i l s o n v i l l e r e p o r t , see r e f e r e n c e ( 6 ) .
Âpproximately 8 percent unconverted coal content,
d e t e r m i n a t i o n by d i f f e r e n c e . ^Direct determination.
e
Insufficient solubility in pyridine.
T h i s i s r e p e a t e d u n t i l t h e column i s a t the same temperature as

the e x t r a c t i o n zone. I n t h i s work, f o u r f r a c t i o n s were brought
overhead by o p e r a t i n g t h e column i n i t i a l l y a t 593 Κ and then
d e c r e a s i n g t h e temperature t o 578, 573, and 563 Κ as the
r e s i d u u m c a r r y - o v e r approached 1.0 gram p e r gram-mole o f
cyclohexane. T h i s c o n c e n t r a t i o n v a l u e i s c a l c u l a t e d from the
amount o f residuum c o l l e c t e d from t h e bottom o f the s e p a r a t o r
a f t e r a 30-minute c o l l e c t i o n p e r i o d and from t h e amount o f
c y c l o h e x a n e pumped d u r i n g t h a t p e r i o d . The column t e m p e r a t u r e s
were s e l e c t e d b o t h from d e n s i t y e s t i m a t i o n and from a c t u a l
experimentation. A more d e t a i l e d d i s c u s s i o n o f the development
o f t h e o p e r a t i o n a l parameters f o r t h e r e f l u x mode w i l l be
presented i n a f u t u r e paper.
F i g u r e 3 i l l u s t r a t e s t h e d i f f e r e n c e between o p e r a t i o n o f
the FDU i n the n o n - r e f l u x and the r e f l u x modes w i t h c y c l o h e x a n e .
T h i s f i g u r e d e p i c t s the r e s u l t s i n terms o f the overhead
c o n c e n t r a t i o n o f residuum. The r e f l u x mode d a t a r e p r e s e n t one
o f t h r e e r e p l i c a t e f r a c t i o n a t i o n s t h a t were performed on the
T102 t o l u e n e d e s t r a c t i o n o v e r h e a d . Each p o i n t r e p r e s e n t s a 30-
minute sample c o l l e c t i o n p e r i o d . Owing t o the l i m i t e d q u a n t i t y
o f t o l u e n e overhead produced, no n o n - r e f l u x mode e x p e r i m e n t s
were c o n d u c t e d u s i n g t h i s m a t e r i a l . From the e a r l i e r
development work, however, s e v e r a l n o n - r e f l u x mode e x p e r i m e n t s
were performed on the T102 residuum sample from Run 242. The
n o n - r e f l u x mode d a t a i n F i g u r e 3 were d e r i v e d from one o f t h e s e
e x p e r i m e n t s and a d j u s t e d f o r c o m p a r a b i l i t y t o t h e d a t a from t h e
r e f l u x mode. The adjustment compensates f o r s e p a r a t o r
i n e f f i c i e n c y and f o r residuum i n s o l u b l e i n s u p e r c r i t i c a l

Ω 1
1
801 1
Γ
0 2 4 6
CUMULATIVE TIME ON STREAM AT P = 2,hr R
Figure 2. Comparison of f i v e r e p l i c a t e destractions (non-reflux

mode) of W i l s o n v i l l e Run 242 T102 residuum using toluene.
THE EFFECT O F REFLUX ON THE

O V E R H E A D C O N C E N T R A T I O N O F RESIDUUM
16 -ι 1 1
ο Non-Reflux Mode
• 593 Κ , Fraction I
• 578 K,Fraction 2
0 20 40 60
CUMULATIVE WEIGHT PERCENT OVERHEAD
Figure 3. Comparison of non-reflux and r e f l u x modes o f operation

using cyclohexane. Temperatures indicated are those o f the
column i n the r e f l u x mode. Pot temperature was 563 Κ i n both
modes.

toluene. A l l but t h e l a s t t h r e e d a t a p o i n t s i n t h e n o n - r e f l u x
mode d a t a r e p r e s e n t 15-minute sample p e r i o d s . The o n l y o t h e r
d i f f e r e n c e between t h e two t e s t s was t h e s o l v e n t d e l i v e r y r a t e ,
which was 0.24 mole p e r minute f o r t h e n o n - r e f l u x mode, and 0.43
mole p e r minute i n t h e r e f l u x mode.
As shown i n F i g u r e 3 t h e temperature o f t h e column was
i n i t i a l l y 30 degrees h i g h e r than t h e p o t , which produced t h e
reduced c a r r y - o v e r r a t e by c a u s i n g r e f l u x t o o c c u r . An expanded
view o f t h e c a r r y - o v e r c o n c e n t r a t i o n i s shown i n F i g u r e 4. T h i s
view shows more c l e a r l y how r e s i d u u m c a r r y - o v e r i s m a n i p u l a t e d
by changes i n t h e column t e m p e r a t u r e . Figure 5 contains the
same i n f o r m a t i o n f o r t h e t h r e e r e p l i c a t e c y c l o h e x a n e
f r a c t i o n a t i o n s performed on t h e t o l u e n e o v e r h e a d . Conditions i n
a l l t h r e e e x p e r i m e n t s were s i m i l a r ; however, t h e s m a l l
d e v i a t i o n s due t o i n h e r e n t l i m i t a t i o n s o f t h e p r o c e s s
controllers produced some o v e r l a p between s u c c e s s i v e f r a c t i o n s .
The amount o f o v e r l a p i s e s t i m a t e d a t 2.6 p e r c e n t between
F r a c t i o n s 1 and 2, 2.
3.0 p e r c e n t between F r a c t i o n
s h o u l d have been i n t h e 573 Κ f r a c t i o n were i n a d v e r t e n t l y
c o l l e c t e d i n t h e 578 Κ f r a c t i o n . The r e s p e c t i v e f r a c t i o n s and
r e s i d u e s from t h e t h r e e f r a c t i o n a l d e s t r a c t i o n s were ground and
combined b e f o r e c h a r a c t e r i z a t i o n .
T a b l e I I c o n t a i n s t h e a n a l y s i s o f t h e f o u r overhead
f r a c t i o n s and t h e r e s i d u e . The o v e r a l l m a t e r i a l b a l a n c e was
96.1 p e r c e n t , w i t h 57.2 p e r c e n t o f t h e charge b e i n g brought
overhead ( i n c l u d e s r e s i d u u m r e c o v e r e d from spent s o l v e n t ) and
31.7 p e r c e n t r e m a i n i n g i n t h e r e s i d u e . An a d d i t i o n a l 7.2
p e r c e n t was r e c o v e r e d upon c l e a n i n g t h e u n i t w i t h
tetrahydrofuran. The t r e n d s e v i d e n t from t h e e l e m e n t a l a n a l y s i s
i n d i c a t e t h a t t h e components t h a t have lower m o l e c u l a r w e i g h t s ,
h i g h e r h y d r o g e n - t o - c a r b o n r a t i o s , and lower h e t e r o a t o m c o n t e n t s
are concentrated i n the e a r l i e r f r a c t i o n s . A l s o note that the
separator i n e f f i c i e n c y i s highest f o r the e a r l i e r f r a c t i o n s ,
i n d i c a t i n g t h a t t h e more v o l a t i l e components a r e more r e a d i l y
c a r r i e d through t h e s e p a r a t o r w i t h t h e s o l v e n t . The m a t e r i a l
c a r r i e d through t h e s e p a r a t o r w i t h t h e s o l v e n t was n o t mixed
w i t h t h e r e s p e c t i v e f r a c t i o n s c o l l e c t e d from t h e s e p a r a t o r .
Independent c h a r a c t e r i z a t i o n o f t h e s e samples w i l l p r o v i d e
valuable i n s i g h t i n t o the operation of the separator.
The m o l e c u l a r weight d a t a i n T a b l e I I were d e t e r m i n e d by
vapor p r e s s u r e osmometry (VPO) and g e l p e r m e a t i o n chromatography
(GPC). The m o l e c u l a r weight i n c r e a s e s r e g u l a r l y from F r a c t i o n 1
to t h e r e s i d u e . I n c o m p a r i s o n , t h e VPO m o l e c u l a r weights f o r
s i x f r a c t i o n s c o l l e c t e d i n t h e n o n - r e f l u x mode c y c l o h e x a n e
d e s t r a c t i o n shown i n F i g u r e 3 range from 441 t o 471, w i t h no
consistent trend. The p o l y d i s p e r s i t y v a l u e s (M^/M^) shown f o r
the f o u r f r a c t i o n s i n T a b l e I I a r e l e s s than t h o s e f o r t h e non-
r e f l u x mode f r a c t i o n s , which ranged from 1.47 f o r t h e f i r s t
f r a c t i o n t o 1.88 f o r t h e s i x t h f r a c t i o n . T h i s number i s a
measure o f t h e b r e a d t h o f t h e m o l e c u l a r weight d i s t r i b u t i o n ( 9 )
and shows t h a t o p e r a t i o n i n t h e r e f l u x mode produces f r a c t i o n s
w i t h narrower m o l e c u l a r weight d i s t r i b u t i o n s than those p r e p a r e d
without r e f l u x .

WARZINSKI Fractional Destraction of Coal-Derived Residuum 237
0 20 40 60
Figure 4. Fractional destraction of toluene overhead using

cyclohexane.
REPLICATE FRACTIONAL DESTRACTIONS O F

T O L U E N E O V E R H E A D USING C Y C L O H E X A N E
3.0i 1 1 1 j 1 1 1 | I I Γ
Figure 5. Comparison o f three r e p l i c a t e f r a c t i o n a l destractions

( r e f l u x mode) o f toluene overhead using cyclohexane.

TABLE I I . C h a r a c t e r i z a t i o n of M a t e r i a l s Produced From the

Cyclohexane F r a c t i o n a l D e s t r a c t i o n o f the T o l u e n e Overhead
Sample i n T a b l e I .
FRACTION DESIGNATION*
593 Κ 578 Κ 573 Κ 563 Κ RESIDUE
c 87.8 87.3 87.4 87.0 87.0

H 7.6 7.5 7.2 6.5 5.9
Ob 3.5 3.7 3.3 3.7 4.9
Ν 0.9 0.9 1.2 1.4 1.8
S 0.5 0.6 0.6 0.7 0.9
ASH 0.1
H/C 1.03 1.02 0.98 0.89 0.81

RESIDUAL 0.5 0.5 0.8 0.6 0.5
c
CYCLOHEXANE, %
d
RECOVERY, %
SEPARATOR
e
INEFFICIENCY, %
MELTING RANGE, Κ 333-338 363-373 393-403 448-463 573
f
M , VPO
N 393 479 578 645 1226
M , GPCS
N 407 449 527 564 715
M ,_GPC
W 504 601 851 1010 1996
M /M W N 1.24 1.34 1.62 1.79 2.79
a
T h e temperature r e f e r s to t h e r e f l u x and packed bed zone. The
r e s i d u e i s the m a t e r i a l r e m a i n i n g i n the e x t r a c t i o n zone.
^ D i r e c t d e t e r m i n a t i o n , d e t e r m i n a t i o n by Headspace
d
Chromatography, see r e f e r e n c e ( 8 ) . T o t a l r e c o v e r y of m a t e r i a l
based upon weight o f t o l u e n e overhead charged t o the u n i t .
Except f o r the r e s i d u e t h i s i n c l u d e s both r e s i d u u m r e c o v e r e d
e
from the f r a c t i o n r e c e i v e r and from the spent s o l v e n t . Percent
of t o t a l m a t e r i a l overhead r e c o v e r e d i n the spent s o l v e n t ,
f D e t e r m i n a t i o n i n p y r i d i n e a t 353 K. ^ D e t e r m i n a t i o n on P L g e l
IOOX column w i t h THF e l u e n t .
In F i g u r e 6 the GPC t r a c e s f o r the f o u r f r a c t i o n s and f o r

the r e s i d u e from each o f the t h r e e c y c l o h e x a n e f r a c t i o n a l
destractions are o v e r l a i d . The t r e n d t o h i g h e r m o l e c u l a r weight
d i s t r i b u t i o n s as the f r a c t i o n a t i o n proceeded i s e v i d e n t , as w e l l
as the r e p r o d u c i b i l i t y of the f r a c t i o n a t i o n p r o c e s s . A d d i t i o n a l
c h a r a c t e r i z a t i o n o f s i m i l a r samples produced i n the FDU i s the
s u b j e c t o f a n o t h e r paper ( 1 0 ) .
Conclusions
The main c o n c l u s i o n t o be drawn from the e x p e r i m e n t a l d a t a

p r e s e n t e d h e r e i s t h a t f r a c t i o n a t i o n o f residuum t h r o u g h the use
o f a s u p e r c r i t i c a l f l u i d system i n c o r p o r a t i n g i n t e r n a l r e f l u x
produced by r e t r o g r a d e c o n d e n s a t i o n r e s u l t s i n s h a r p e r f r a c t i o n s
than t h o s e o b t a i n e d by o r d i n a r y s u p e r c r i t i c a l e x t r a c t i o n . The
c a p a b i l i t y o f the FDU t o p r o c e s s c o a l - d e r i v e d r e s i d u u m i n the

RETENTION TIME, min.
Figure 6. Comparison o f the GPC r e s u l t s f o r the three r e p l i c a t e

f r a c t i o n a l destractions o f toluene overhead using cyclohexane.

i n t e r n a l r e f l u x mode has been d e m o n s t r a t e d . The d e n s i t y - d r i v e n

s e p a r a t i o n does appear to f r a c t i o n a t e the r e s i d u u m on the b a s i s
of v o l a t i l i t y , w i t h lower m o l e c u l a r weight s p e c i e s p r e c e d i n g
l a r g e r ones.
O t h e r methods o f f r a c t i o n a t i o n w i t h s u p e r c r i t i c a l f l u i d s
are c o n c e i v a b l e . One such p o s s i b l i l i t y c o u l d i n v o l v e
m a n i p u l a t i o n o f the p r e s s u r e d u r i n g the d e s t r a c t i o n o r upon
subsequent s e p a r a t i o n o f the f l u i d and r e s i d u u m . The r e l a t i v e
m e r i t s o f such p o s s i b i l i t i e s remain to be e x p l o r e d . Successful
development o f such t e c h n o l o g y w i l l r e s u l t i n the a b i l i t y to
f r a c t i o n a t e and c h a r a c t e r i z e m a t e r i a l c u r r e n t l y i n t r a c t a b l e by
c o n v e n t i o n a l methods.
Disclaimer
R e f e r e n c e i n t h i s r e p o r t to any s p e c i f i c p r o d u c t , p r o c e s s , o r
s e r v i c e i s to f a c i l i t a t e u n d e r s t a n d i n g and does not n e c e s s a r i l y
i m p l y i t s endorsement
Department o f E n e r g y
Literature Cited
1. Brule, M.R.; Kumar, K.H.; Watansiri, S. Oil & Gas Journal
Feb. 11, 1985, 87.
2. Brule, M.R.; Rhodes, D.E.; Starling, K.E. Fuel 1981, 60,
638.
3. Zosel, K. Angew. Chem., Int. Ed. 1978, 17(10), 702.
4. Brule, M.R.; Corbett, R.W. Hydrocarbon Processing June,
1984, 73.
5. Vasilakos, N.P.; Dobbs, J.M.; Parisi, A.S. Ind. Eng.
Chem., Process Des. Dev. 1985, 24(1), 121.
6. Technical Progress Report by Catalytic, Inc., DOE Report
No. DOE/PC/50041-19, July, 1983.
7. Warzinski, R.P.; Ruether, J.A. Fuel 1984, 63, 1619.
8. Loffe, B.V.; Vitenberg, A.G. "Head-Space Analysis and
Related Methods in Gas Chromatography"; John Wiley & Sons,
New York, 1984; p. 131..
9. Yau, W.W.; Kirkland, J.J.; Bly, D.D. "Modern Size-Exclusion
Liquid Chromatography"; John Wiley & Sons, New York, 1979;
p. 8.
10. Warzinski, R.P.; Strycker, A.S.; Lett, R.G. Prepr. Pap.-
Am. Chem. Soc., Div. Fuel Chem. 1985, 30(4), 243.

Chapter 19
Isotope Effects in Supercritical Water: Kinetic Studies

of Coal Liquefaction
1 1 1 2
David S. Ross , Georgina P. Hum , Tiee-Chyau Miin , Thomas K. Green , and
3,4
Riccardo Mansani
1
Fuel Chemistry Program, SRI International, Menlo Park, C A 94025
2
Western Kentucky University, Bowling Green, K Y 42102
3
Eniricerche S.p.A., 20097 S. Donato Milanese (MI), Milan, Italy
Coal liquefaction studies with Illinois No. 6 coal in

supercritical water/C
suitable model for liquefactio
Thus coal is partitioned between reducing (i.e. liquefy-
ing) steps, and steps where strictly thermal reactions
consume convertible sites and yield unconvertible char.
In supercritical H2O it was found that the toluene-
soluble products (TS) profile leveled off at about 50%.
However in supercritical D2O, liquefaction was consis-
tently superior to that in the protio medium, and the
ultimate convertibility was about 60%. This inverse
isotope effect can be explained by a model in which the
limits to conversion are solely based on the competition
between the kinetics of the parallel routes to TS and
char, respectively. Conversion is thus limited by the
kinetics of the conversion system, this limitation being
even more severe in conventional donor systems which are
inherently less effective for liquefaction than is
water/CO. In principle the conversion of coal virtually
completely to TS in a single step is feasible in a system
with sufficient reducing potential.
The c h e m i s t r y o f c o a l l i q u e f a c t i o n i s not v e r y w e l l u n d e r s t o o d , even

a f t e r more than two decades o f r e s e a r c h i n t o the k i n e t i c s and mecha-
nism o f the p r o c e s s . There have been a number o f models f o r c o n v e r -
s i o n proposed, most o f them f o c u s e d on t h e s e v e r a l l i q u e f a c t i o n
p r o d u c t s , i n c l u d i n g p r e a s p h a l t e n e s , a s p h a l t e n e s , o i l s , and g a s e s . A
survey o f some o f the models has been p r e s e n t e d ( 1 ) , and a common
f e a t u r e among them i s t h e m u l t i p l i c i t y o f paths c o n n e c t i n g a l l o f
the components.
K i n e t i c model s t u d i e s have i n v a r i a b l y been c a r r i e d out i n
o r g a n i c donor media, and w h i l e the use o f these media may be con-
v e n i e n t i n l a r g e s c a l e c o n v e r s i o n systems, they do not l e n d them-
4
Current address: EniChem Polimeri, Milanofiori-Strada 2-Palazzo F7, Milan, Italy
0097-6156/87/0329-0242$06.00/0

19. ROSS ET AL. Kinetic Studies of Coal Liquefaction 243
s e l v e s w e l l to l a b o r a t o r y study of c o n v e r s i o n . Not the l e a s t s i g n i -

f i c a n t of the problems to be f a c e d i n such a study i s the u n a v o i d -
a b l e p a r t i c i p a t i o n of v a r i o u s i n t e r r e l a t e d and i n t e r l o c k e d f r e e
r a d i c a l c h a i n r e a c t i o n s , most of which h a v i n g no d i r e c t b e a r i n g on,
and perhaps o n l y a secondary r e l a t i o n s h i p w i t h , the l i q u e f a c t i o n
process. The c o m p l i c a t i o n s p r e s e n t e d by t h i s network of i n c i d e n t a l
r e a c t i o n s , c o u p l e d w i t h the m u l t i p l e r e a c t i o n paths to p r o d u c t s ,
prompted the study of the k i n e t i c s of c o a l l i q u e f a c t i o n u s i n g s u p e r -
c r i t i c a l water as the medium.
BACKGROUND
The a c t i o n of CO/water to reduce both low rank and b i t u m i n o u s c o a l s

to upgraded p r o d u c t s has been known f o r more than h a l f a c e n t u r y ,
h a v i n g been i n t r o d u c e d i n the work of F i s c h e r and S c h r a d e r ( 2 ) . A
review o f the CO/water c o n v e r s i o n p r o c e s s has appeared ( 3 ) , and a
summary of the c h a r a c t e r i s t i c s of the medium i s p r e s e n t e d h e r e The
c r i t i c a l temperature and
and 221.3 b a r , at which p o i n
Not s u r p r i s i n g l y , at temperatures and p r e s s u r e s around t h a t p o i n t ,
the medium can be a good s o l v e n t f o r o r g a n i c s o l u t e s o t h e r w i s e not
s o l u b l e at ambient c o n d i t i o n s . The h i g h s o l u b i l i t i e s , however, a r e
m a i n t a i n e d at s u b s t a n t i a l l y lower temperatures; the s o l u b i l i t i e s of
benzene and t o l u e n e f o r example a r e 12% and 7% r e s p e c t i v e l y a t 280°C
(4). The c r i t i c a l c u r v e f o r benzene/water passes through 294°C and
200 atm, at which p o i n t the components form a s i n g l e phase, and the
d e n s i t y of the medium i s 0.74 g/mL, l i k e t h a t of a t r u e l i q u i d .
S i m i l a r b e h a v i o r i s r e p o r t e d f o r t e t r a l i n and n a p h t h a l e n e ,
where s i n g l e phases w i t h water are seen i n the 300-340°C range. In
these cases the c r i t i c a l temperatures f o r the two o r g a n i c s a r e
g r e a t e r than t h a t of water. Thus the c r i t i c a l temperature of water
i s lowered by the a d d i t i o n of a r o m a t i c s l i k e those i n c o a l and c o a l
products.
H y d r o t h e r m a l systems such as these can a l s o s u p p o r t the d i s s o -
l u t i o n of i o n i c s a l t s . There i s a tendency f o r the o r g a n i c compo-
n e n t s i n these systems to be s a l t e d out of s o l u t i o n ; however con-
d i t i o n s e x i s t where a homogeneous system would c o n t a i n both the d i s -
s o c i a t e d i o n i c component and an a r o m a t i c component such as benzene
(2).
At ambient temperatures CO i s o n l y s l i g h t l y s o l u b l e i n water.
T h i s b e h a v i o r i s i n c o n t r a s t to the case f o r carbon d i o x i d e , which
d i s s o l v e s and i s e a s i l y h y d r a t e d to c a r b o n i c a c i d and i t s c o n j u g a t e
bases. The s i m p l e s o l u t i o n of CO i n water i n a c c o r d w i t h i t s
Henry's law c o n s t a n t c o n t i n u e s to about 250°C. At t h a t temperature
the r a t e of h y d r a t i o n becomes s i g n i f i c a n t , and f o r m i c a c i d i s
formed. However the a c i d i s t h e r m a l l y u n s t a b l e , and s u b s e q u e n t l y
decomposes to CO2 and
EXPERIMENTAL
The c o a l used i n t h i s work was an I l l i n o i s No. 6 c o a l , PSOC 1098,

s u p p l i e d by P e n n s y l v a n i a S t a t e U n i v e r s i t y . The c o a l was ground and
s i e v e d under d r y N 2 t o pass -60 T y l e r mesh and then d r i e d under
vacuum a t 105°C o v e r n i g h t .

A l l r e a c t i o n s were performed i n a 300-mL Magne-drive s t i r r e d

Hastelloy C autoclave. The a u t o c l a v e was loaded w i t h about 5 g of
d r y c o a l and 30 g d e i o n i z e d water. Weighed q u a n t i t i e s of KOH were
added to the water to a d j u s t the i n i t i a l pH to the d e s i r e d v a l u e .
The system was s e a l e d and purged w i t h 500 p s i g " N . 2 I t was then
purged t w i c e and charged w i t h the a p p r o p r i a t e p r e s s u r e of d e s i r e d
gas.
The a u t o c l a v e was heated w i t h s t i r r i n g to 400°C (± 5°C) f o r 20
min (± 1 m i n ) . Maximum p r e s s u r e s a t t a i n e d were i n the range 4000-
5000 p s i g . The f u l l heat-up and cool-down times were both about 1 h.
The f i n a l , c o l d p r e s s u r e s were measured a f t e r r e a c t i o n . Quan
t i t a t i v e a n a l y s e s of the p r o d u c t gases CO, C 0 , and H were made
2 2
w i t h a C a r l e gas chromatograph u s i n g s t a n d a r d g a s e s . The aqueous

phase was p i p e t t e d from the a u t o c l a v e and f i l t e r e d . The n o n v o l a t i l e
p r o d u c t s were q u a n t i t a t i v e l y removed w i t h t e t r a h y d r o f u r a n (THF) and
t r a n s f e r r e d to a 500-mL round bottomed f l a s k . THF was removed by
r o t a r y e v a p o r a t i o n and 400-mL of t o l u e n e was added. T h i s m i x t u r e
was r e f l u x e d w i t h s t i r r i n
d i s t i l l a t i o n removed an
f i l t e r e d through a medium p o r o s i t y f i l t e r (10-15 |im) to s e p a r a t e the
t o l u e n e - i n s o l u b l e ( T I ) from the t o l u e n e - s o l u b l e (TS) m a t e r i a l . The
t o l u e n e was removed by r o t a r y e v a p o r a t i o n , and both the TS and TI
p o r t i o n s were d r i e d o v e r n i g h t under vacuum a t 105°C and weighed.
The c o n v e r s i o n to TS m a t e r i a l i n a d r y , m i n e r a l - m a t t e r - f r e e b a s i s
was c a l c u l a t e d as
%TS=(wt TS/wt DMMF c o a l ) χ 100
RESULTS
Working Model. Our working model e v o l v e d from c o n s i d e r a t i o n of the

p r o f i l e s t y p i c a l l y noted i n the modeling l i t e r a t u r e . Products are
seen to grow w i t h time, and then l e v e l o f f at some l e v e l below quan
t i t a t i v e conversion. At the same time the q u a n t i t i e s of " u n r e a c t e d
c o a l " d e c l i n e , and a l s o l e v e l o f f . A p i c t u r e of the c o a l o r g a n i c
m a t r i x d e r i v e d from t h i s view of c o n v e r s i o n would d e p i c t a c o l l e c
t i o n of o r g a n i c u n i t s , connected to each o t h e r through a s e r i e s of
l i n k s i n c r e a s i n g l y more d i f f i c u l t to b r e a k .
On t h i s b a s i s , c o n v e r s i o n i s l i m i t e d by c o a l s t r u c t u r e . And i n
terms of the c o n v e n t i o n a l h o m o l y t i c s c i s s i o n / H - c a p p i n g view of
c o n v e r s i o n , i n c r e a s e d y i e l d s of c o a l l i q u i d s are t h e r e f o r e o b t a i n
a b l e o n l y through i n c r e a s e s i n c o n v e r s i o n temperature or r e s i d e n c e
time. U n f o r t u n a t e l y , i n c r e a s e s i n the t h e r m a l s e v e r i t y of the
p r o c e s s r e s u l t i n p r o d u c t s r e f l e c t i n g the r i s e of d e a l k y l a t i o n and
a r o m a t i z a t i o n r e a c t i o n s at h i g h e r t e m p e r a t u r e s . Thus i n c r e a s e d
p r o d u c t y i e l d s are brought about at a c o n s i d e r a b l e c o s t to p r o d u c t
quality (5).
The f a c t t h a t the p r o f i l e s of both the d e s i r e d s o l u b l e product
and the i n s o l u b l e product l e v e l o f f at i n t e r m e d i a t e v a l u e s suggest a
s i m p l e r model f o r c o n v e r s i o n . T h i s scheme, p r e s e n t e d i n F i g u r e 1,
i s our working model, and i s t e s t e d i n the study d e s c r i b e d h e r e . In
the scheme c o a l i s p a r t i t i o n e d i n p a r a l l e l , c o m p e t i t i v e r o u t e s
between i ) r e a c t i o n w i t h some r e d u c i n g component i n the system t o
y i e l d TS, and i i ) t h e r m a l l o s s of c o n v e r t i b l e s i t e s to y i e l d c h a r .

I n t h i s work we have a v o i d e d c o n s i d e r a t i o n of s p e c i f i c mechanism f o r

d e c r e a s e i n m o l e c u l a r weight w i t h l i q u e f a c t i o n , i n c l u d i n g i n
p a r t i c u l a r the p e r c e i v e d need f o r t h e r m a l s c i s s i o n of C-0 and C-C
bonds d u r i n g c o n v e r s i o n . Thus we view c o n v e r s i o n s i m p l y as a
p r o c e s s r e q u i r i n g some k i n d of n o n s p e c i f i c r e d u c t i o n c h e m i s t r y .
T h i s t w o - r e a c t i o n scheme, i f t r u l y o p e r a t i v e , s u g g e s t s a view
of the p o t e n t i a l u t i l i t y of l i q u e f a c t i o n more o p t i m i s t i c than t h a t
d e r i v e d from the c o n v e n t i o n a l l y a c c e p t e d scheme. The y i e l d of TS i s
a f u n c t i o n of the r a t e s of the two r e a c t i o n s . T h e r e f o r e an i n c r e a s e
i n the r a t e of the TS r o u t e , or a d e c r e a s e i n the r a t e of char f o r -
m a t i o n , would b r i n g about i n c r e a s e d TS y i e l d s . I n t u r n , an i n c r e a s e
i n the r a t e of TS f o r m a t i o n c o u l d be brought about w i t h an i n c r e a s e
i n the r e d u c i n g c a p a c i t y of the system, r a t h e r than through an
i n c r e a s e i n r e a c t i o n temperature. And thus i n p r i n c i p l e , i n c r e a s e s
i n TS y i e l d to p r o d u c t q u a n t i t i e s r e p r e s e n t i n g a l l of the c o n v e r -
t i b l e p o r t i o n of the s t a r t i n g c o a l c o u l d be o b t a i n e d , and at no c o s t
to product q u a l i t y .
CO/Water C o n v e r s i o n s
reducing capacity a v a i l a b l
CO/water system o f f e r e d c o n s i d e r a b l e l a t i t u d e . We had e a r l i e r
demonstrated t h a t changes i n the i n i t i a l pH of the system brought
about wide v a r i a t i o n i n the TS y i e l d s f o r I l l i n o i s No. 6 c o a l ( 6 ) .
In a c c o r d w i t h the f i n d i n g s of s e v e r a l o t h e r groups i n c l u d i n g
A p p e l l , et a l . ( 7 ) , the c o n v e r s i o n s were found to be base promoted.
The p r e s e n t study i n c l u d e d a range of i n i t i a l pH v a l u e s , and f o c u s e d
on a comparison of the r e s u l t s i n H 0 w i t h those from a s u b s t i t u t i o n
2
i n p a r a l l e l experiments of D 0.
2
The r e s u l t s f o r s e v e r a l runs i n the two media a r e p r e s e n t e d i n

F i g u r e 2. The f i g u r e p r e s e n t s a p l o t o f % - t o l u e n e s o l u b l e p r o d u c t s
vs q u a n t i t y of CO consumed. There i s a range of TS y i e l d s up to
around 50% f o r the p r o t i o medium. These c o n v e r s i o n s were a t t a i n e d
by r a n g i n g the i n i t i a l pH from 7 t o 13.
We have p o i n t e d out t h a t the water gas s h i f t r e a c t i o n
CO + H 0 2 • C0 2 + H 2
p a r a l l e l s the c o n v e r s i o n ( 6 ) . A l s o p r e s e n t e d i n the f i g u r e a r e
r e s u l t s f o r runs w i t h H 2 i n p l a c e of CO, and the r e s u l t s of these
runs show c l e a r l y t h a t H 2 i s less e f f e c t i v e i n conversion. It i s
thus the CO, r a t h e r than the H 2 produced d u r i n g the C O - c o n v e r s i o n s ,
that i s r e s p o n s i b l e f o r the p r o d u c t i o n of t o l u e n e - s o l u b l e p r o d u c t .
E f f e c t s of m i n e r a l matter are a l s o shown i n the. f i g u r e . Mineral
matter i s a p p a r e n t l y n e c e s s a r y f o r the s m a l l degrees of c o n v e r s i o n
seen f o r the H / H 0 system, w h i l e the TS y i e l d s i n the CO/water
2 2
system a r e independent of the presence of m i n e r a l m a t t e r .

The major f i n d i n g i n t h i s work i s the i s o t o p e e f f e c t , as d i s -
p l a y e d i n the f i g u r e . The d e u t e r i o system p r o v i d e s s i g n i f i c a n t l y
g r e a t e r TS y i e l d s than does the p r o t i o system. Moreover, the
d e u t e r i o r e s u l t s l e v e l o f f at a s u b s t a n t i a l l y h i g h e r c o n v e r s i o n
level. T h i s r e s u l t , an i n v e r s e i s o t o p e e f f e c t , i s not very common
i n i s o t o p e e f f e c t s t u d i e s , and has r e c e n t l y been d i s c u s s e d by K e e f f e
and J e n e k s ( 8 ) .
P r o d u c t s of C o n v e r s i o n . C o n v e r s i o n product a n a l y s e s are
p r e s e n t e d i n F i g u r e 3. The procedure used here i s that developed by

REDUCT.
TS
COAL
CHAR
F i g u r e 1. Workin
80
CO/D.O
C0/H 0 9
H /H OJ
2 2
500
CO CONSUMED OR H CHARGED
2
(cold, mmole)
F i g u r e 2. C o n v e r s i o n s o f PSOC-1098 and PSOC-26 a t 400°C/20 m i n u t e s .

O C 0 / D 0 ; Ο · C0/H 0; • • Η / Η 0 ; Δ A N /H 0
2 2 2 2 2 2
(The filled symbols r e p r e s e n t d a t a f o r the d e m i n e r a l i z e d coal.)

F a r c a s i u ( 9 ) , w i t h which we have s e p a r a t e d t h e t o l u e n e - s o l u b l e f r a c -
tions i n t o s u b f r a c t i o n s of i n c r e a s i n g p o l a r i t y . The TS f r a c t i o n s
f o r d i f f e r e n t c o a l s y i e l d d i f f e r e n t p r o f i l e s , and y e t we f i n d here
f o r t h e I l l i n i o s No. 6 c o a l t h a t the TS f r a c t i o n s f o r c o n v e r s i o n i n
water o f 29% and 60% a r e v i r t u a l l y the same. F u r t h e r , t h e TS f r a c -
t i o n from the t e t r a l i n r u n i s a l s o e s s e n t i a l l y i d e n t i c a l i n i t s
profile.
The H/C r a t i o o f p r o d u c t s from s e v e r a l CO/RÔ c o n v e r s i o n s a r e
p r e s e n t e d i n T a b l e 1. W i t h i n the s c a t t e r o f the d a t a , both the T I
and TS f r a c t i o n s have r a t i o s unchanging w i t h over a range o f con-
v e r s i o n s from 29 t o 60%.
T a b l e I . H/C R a t i o s f o r C0/H 0 C o n v e r s i o n a t 400°C

2
H/C
%TS TI TS
29
30 0.56 0.95
30 0.53 0.92
44 0.63 0.95
45 0.64 0.92
59 0.61 0.94
60 0.63 0.93
DISCUSSION
Taken a l o n e , the c o n v e r s i o n p r o f i l e from the p r o t i o work i s c o n s i s -

t e n t w i t h the view t h a t the c o n v e r s i o n o f c o a l i s l i m i t e d by i t s
structure. Thus i f the o r g a n i c p o r t i o n o f c o a l c o n t a i n e d a l i m i t e d
network o f b r e a k a b l e l i n k s , the s c i s s i o n o f which would l i b e r a t e
about 50% o f the m a t e r i a l t o TS p r o d u c t , then runs w i t h i n c r e a s i n g
c o n v e r s i o n c a p a c i t y would show i n c r e a s e d c o n v e r s i o n , l e v e l i n g o f f a t
about 50% TS y i e l d .
The i n v e r s e i s o t o p e e f f e c t , however, r e q u i r e s a d i f f e r e n t
picture. Thus a simple change t o the heavy medium b r i n g s about n o t
o n l y i n c r e a s e d c o n v e r s i o n s , but a l e v e l i n g o f f o f c o n v e r s i o n a t a
s i g n i f i c a n t l y higher l e v e l . Whatever the r e d u c t i o n mechanism, i t i s
1 2
h i g h l y u n l i k e l y t h a t i s o t o p i c s w i t c h from H to H would i n c r e a s e
the i n h e r e n t bond b r e a k i n g c a p a c i t y o f the system. And so we con-
c l u d e t h a t the s t a r t i n g c o a l must c o n t a i n many more b r e a k a b l e l i n k s
than supposed above, but t h a t some p o r t i o n of the l i n k s a r e l o s t
through o t h e r r e a c t i o n s . The proposed model i n F i g u r e 1 i s c o n s i s -
tent with t h i s c o n c l u s i o n .
The f u l l scheme f o r c o n v e r s i o n i s p r e s e n t e d i n F i g u r e 4. I n
t h i s scheme, formate i s p a r t i t i o n e d between r e a c t i o n w i t h c o a l , and
a hydrogen i o n t r a n s f e r r e a c t i o n w i t h water t o y i e l d f o r m i c a c i d .
The a c i d i s u n s t a b l e a t the c o n v e r s i o n temperatures ( 1 0 ) , decom-
p o s i n g r a p i d l y t o carbon d i o x i d e and hydrogen. Thus w i t h the s w i t c h
from p r o t i o t o d e u t e r i o , the f o r m i c a c i d f o r m a t i o n e x p e r i e n c e s a

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50
LU
ES! C O / D O - 4 0 0 ° C / 2 0 min/60%
2
I 40
< r~1 C O / H O - 4 0 0 ° C / 2 0 min/29%
2
^ 30 "I 1 Tetralin-400°C/60 min/40%

<
Ο 20
ι—
u_
Ο 10
à?
ο Lia rfl.. J L
10
H
c ο 6
S i >
FRACTIONS
F i g u r e 3. SESC S e p a r a t i o n s of TS F r a c t i o n s .
H 0 + C0 9
CO + O H ^ H C O ;
-
TS
COAL -
CHAR
F i g u r e 4. O v e r a l l Scheme f o r C o n v e r s i o n i n H y d r o t h e r m a l Systems

normal d e u t e r i u m e f f e c t , i . e . p r o t i o > d e u t e r i o , and i s slowed. The

r e s u l t i s an i n c r e a s e i n the s t e a d y - s t a t e c o n c e n t r a t i o n of f o r m a t e ,
and an a c c o r d a n t i n c r e a s e i n the TS y i e l d .
These r e s u l t s , i n c l u d i n g most e s p e c i a l l y the p r o d u c t d a t a , c o n
t r a s t d e c i d e d l y w i t h those d i s c u s s e d by W h i t e h u r s t et a l . , noted
above (5). In the p r e s e n t work, we f i n d t h a t w i t h i n c r e a s e d
r e d u c i n g c a p a c i t y and at c o n s t a n t t e m p e r a t u r e , the system g i v e s
i n c r e a s e d y i e l d s of p r o d u c t , and at no_ c o s t to p r o d u c t q u a l i t y .
In summary, we f i n d t h a t c o n v e r s i o n i s not l i m i t e d by c o a l
s t r u c t u r e , but r a t h e r by the k i n e t i c s of the r e d u c i n g s t e p ( s ) .
Systems w i t h even g r e a t e r r e d u c i n g c a p a c i t y , and where the water gas
s h i f t r e a c t i o n can be s u p p r e s s e d , s h o u l d p r o v i d e even h i g h e r c o n v e r
s i o n s to t o l u e n e - s o l u b l e p r o d u c t s . The p r o d u c t s i n t u r n s h o u l d be
no l e s s r i c h i n hydrogen than those from lower c o n v e r s i o n r u n s .
I t i s s t i l l n e c e s s a r y to b r i n g about an u n d e r s t a n d i n g of the
s p e c i f i c reducing chemistry. From our p r e s e n t d a t a we can c o n c l u d e
t h a t the c o n v e n t i o n a l t h e r m a l s c i s s i o n / H - c a p p i n g sequence does not
apply here. And s i n c e th
d i f f e r e n t from those fro
the r e d u c t i o n i n c o n v e n t i o n a l donors breaks the same l i n k s broken by
the h y d r o t h e r m a l system.
Thus the q u e s t i o n of the n a t u r e of c r i t i c a l l i n k s c i s s i o n i n
c o n v e n t i o n a l c o n v e r s i o n s must be r e c o n s i d e r e d . Brower has r e c e n t l y
q u e s t i o n e d the c o n v e n t i o n a l scheme (11 a , b ) , and i t i s c l e a r t h a t
the d e t a i l e d mechanism of c o a l c o n v e r s i o n i s yet to be d e v e l o p e d .
ACKNOWLEDGEMENT
We acknowledge the generous support of the U . S . Department of

Energy. We a l s o acknowledge the c l o s e c o o p e r a t i o n of ASSORENI
( M i l a n ) , who p r o v i d e d RM w i t h s u p p o r t f o r a s t a y at SRI as an
International Fellow.
REFERENCES
1. Mohan, G. and Silla, Η., Ind. Eng. Chem. Process Des. Dev.,
1981, 20, 349-358.
2. Fischer, F. and Schrader, H., Brennst.-Chem., 1921, 2 161-172;
C.A. 15, 3193.
3. Ross, D. S. In Coal Science; M. Gorbaty, J . Larsen and I.
Wender, eds., Academic Press, Inc., New York, 1984, pp. 301-
338.
4. Schneider, G. M. and Jockers, R., Ber. Bunsenges. Phys Chem.
1978, 82, 576-582.
5. Farcasiu, Μ., Mitchell, T. O. and Whitehurst, D. D., Chem.
Tech. 1977, 7, 680-686.
6. Ross, D. S., Blessing, J . Ε., Nguyen, Q. C. and Hum, G. P.,
Fuel 1984, 63, 1206-1210.
7. Appell, H. R., Miller, R. D. and Wender, I. presented before
the Division of Fuel Chemistry of the American Chemical
Society, 163rd National Meeting of the ACS, April, 1972.
8. Keeffe, J . R. and Jencks, W. P., J . Am. Chem. Soc., 1981, 103,
2457-2459.
9. Farcasiu, Μ., Fuel 56, 1977, 9-14.

10. Stenberg, V. I., Van Buren, R. L . , Baltisberger, R. L. and

Woolsey, N. F., J . Org Chem. 1982, 47, 4107-4110.
11. a) Brower, K. R., J . Org. Chem. 1982, 47, 1889-1893;
b) Brower, K. R. and Pajak, J., J . Org. Chem. 1984, 49, 3970-
3973.

Chapter 20
Effect of Solvent Density on Coal Liquefaction Kinetics

1 2
G. V. Deshpande , G. D. Holder , and Y. T. Shah
Department of Chemical and Petroleum Engineering, University of Pittsburgh,

Pittsburgh, PA 15261
Supercritical fluid extraction is an attractive

process primarily because the density and solvent
power of a fluid changes dramatically with pressure at
temperatures near the critical. In complex
supercritical extractions, such as the extraction of
coal, the density of the supercritical fluid should
also change th
experiment a relatively inert supercritical fluid,
toluene, was studied to determine the effect of
density on the coal extraction/reaction process.
Extractions were carried out for two to 60 minutes at
reduced densities between 0.5 and 2.0 and at
temperatures between 647 and 698K. The data obtained
can be explained by the hypothesis that coal
dissolution is required preceding liquefaction
reactions and that the degree of dissolution depends
upon solvent density and temperature.
E a r l i e r e f f o r t s aimed a t u n d e r s t a n d i n g s u p e r c r i t i c a l e x t r a c t i o n o f
c o a l used b o t h f l o w and b a t c h r e a c t o r s . In the flow reactors 01)-
(_5), c o a l was packed i n t o the r e a c t o r and t h e s u p e r c r i t i c a l f l u i d
was passed through the bed o f c o a l u n t i l t h e condensed e f f l u e n t was
clear. The c o n v e r s i o n was d e f i n e d as t h e t o t a l weight l o s s o f t h e
c o a l due t o e x t r a c t i o n by t h e s o l v e n t . However, p a r t of the c o a l
w i l l be s o l u b l e i n the e x t r a c t i n g f l u i d a t s u p e r c r i t i c a l c o n d i t i o n s
but will be i n s o l u b l e i n standard e x t r a c t i n g solvents such as
toluene or p y r i d i n e . C o n v e r s i o n s measured i n f l o w systems a r e o v e r
e s t i m a t e d because they i n c l u d e t h i s n o r m a l l y i n s o l u b l e f r a c t i o n .
In b a t c h systems ( 7 ) - ( 1 2 ) , the c o a l and s o l v e n t were p l a c e d i n a
reactor and h e a t e d t o g e t h e r t o t h e r e a c t i o n temperature. The
c o n v e r s i o n o f c o a l thus t a k e s p l a c e d u r i n g heat-up and d u r i n g c o o l -
down and t h e n e c e s s a r i l y n o n - i s o t h e r m a l k i n e t i c models which a r e
'Current address: Advanced Fuel Research, P.O. Box 18343, East Hartford, C T 06118
Correspondence should be addressed to this author.
0097-6156/87/0329-0251 $06.00/0

a p p r o p r i a t e f o r such c o n d i t i o n s cannot be developed w i t h any degree

of c o n f i d e n c e . Thus both of these methods have l i m i t a t i o n s i n
e v a l u a t i n g r e a c t i o n k i n e t i c s because the a c t u a l r e a c t i o n time and
the c o n v e r s i o n s a r e u n c e r t a i n . The g e n e r a l t r e n d s o b s e r v e d i n
t h e s e s t u d i e s do, however, p r o v i d e some i m p o r t a n t i n s i g h t s ; h i g h e r
temperatures and higher d e n s i t i e s result i n higher conversions
p a r t i a l l y because more c o a l d i s s o l v e s i n the s u p e r c r i t i c a l s o l v e n t
as temperature and d e n s i t y a r e i n c r e a s e d . A more thorough review
of the l i t e r a t u r e on s u p e r c r i t i c a l e x t r a c t i o n of c o a l has been done
by Deshpande ( 1 3 ) .
More r e c e n t s t u d i e s ( 1 4 ) , ( 1 5 ) have employed a r a p i d i n j e c t i o n
a u t o c l a v e , where c o a l i s i n j e c t e d i n t o a p r e h e a t e d supercritical
solvent. A f t e r the r e a c t i o n i s o v e r , the p r o d u c t s are quenched by
p a s s i n g water through i n t e r n a l c o o l i n g c o i l s . T h i s method a l l o w s
p r e c i s e measurement of the r e a c t i o n times c o r r e s p o n d i n g t o the
conversions. I t i s used i n t h i s s t u d y .
A m e s t i c a and Wolf (12) i n a s t u d y c l o s e l y r e l a t e d to the one
d e s c r i b e d h e r e i n , measure
t o l u e n e and e t h a n o l . T h e i
increased with temperature and s o l v e n t d e n s i t y but were not
d e t a i l e d enough to show the time dependence of the c o n v e r s i o n .
However, a r e s u l t i m p o r t a n t t o t h i s s t u d y was t h a t t o l u e n e c o n v e r t s
coal to l i q u i d s without significantly reacting itself. After
r e a c t i o n , 98% of the t o l u e n e used was r e c o v e r e d v e r s u s o n l y 73 -
85% of the e t h a n o l i n runs u s i n g i t . E t h a n o l i s a hydrogen donor
and r e a c t s e x t e n s i v e l y w i t h the c o a l . While toluene probably
r e a c t s w i t h c o a l to a s m a l l e x t e n t , i t s e f f e c t was primarily
physical i n nature. As such, i t i s a good c a n d i d a t e f o r s t u d y i n g
the effects of a supercritical solvent on coal liquefaction
k i n e t i c s s i n c e the enhancement e f f e c t of s u p e r c r i t i c a l c o n d i t i o n s
is physical i n nature.
F u r t h e r e v i d e n c e of the importance of the p h y s i c a l n a t u r e of
the s o l v e n t i s found i n the work of B e l s s i n g and Ross (6) who
correlated the coal conversion (pyridine s o l u b l e s ) with the
H i l d e b r a n d s o l u b i l i t y p a r a m e t e r , δ, which they d e f i n e d as
1 / 2
δ = 1.25 P c P /P
r A (1)
Here P c i s the c r i t i c a l p r e s s u r e of the medium i n atmospheres, p r
i s i t s reduced d e n s i t y and i s g e n e r a l i z e d reduced d e n s i t y of

liquids, taken t o be 2.66. They found the p r o d u c t p y r i d i n e
s o l u b i l i t y to be a l i n e a r f u n c t i o n of δ. This implies that higher
d e n s i t i e s s h o u l d produce h i g h e r y i e l d s and t h i s concept i s the
m o t i v a t i o n f o r the p r e s e n t s t u d y .
Experimental
Bruceton bituminous, a P i t t s b u r g h Seam c o a l was used i n the
experiment. The c h e m i c a l a n a l y s e s of c o a l i s g i v e n i n T a b l e I .
The c o a l was d r i e d i n vacuum @ 343 Κ p r i o r to use and s t o r e d i n
g l a s s c o n t a i n e r s under n i t r o g e n .

20. DESHPANDE ET AL. Solvent Density & Coal Liquefaction Kinetics 253
Table I. A n a l y s e s of C o a l s Used
Bruceton Bituminous Coal
Old New
a
Ash , X 4.90 3.88
3
Volatile Matter , % - 37.01
b
Carbon , % 82.69 83.68
b
Hydrogen , % 5.56 5.40
b
Sulfur , % 1.46 1.11
5
Nitrogen , % 1.72 1.01
b c
Oxygen > , % 8.57 8.80
a - Moisture free basi

b - M o i s t u r e and as
c - By d i f f e r e n c e
Supercritical Coal L i q u e f a c t i o n Procedure. The experimental

a p p a r a t u s i s shown i n F i g u r e 1 and c o n s i s t s of a 1-L stainless
s t e e l a u t o c l a v e equipped w i t h a Magnedrive s t i r r e r and a coal
i n j e c t i o n system. The r e a c t o r i s charged w i t h a known q u a n t i t y of
t o l u e n e depending on the f l u i d d e n s i t y d e s i r e d f o r the experiment
and i s heated a t 3-4 K/min to the temperature d e s i r e d . Once t h i s
temperature i s reached, ambient c o a l i s i n j e c t e d i n t o the r e a c t o r
from a c o a l r e s e r v o i r u s i n g h i g h - p r e s s u r e Argon. The average
weight of i n j e c t e d c o a l was 30g. R e a c t i o n times are measured from
the time a t tfhich the c o a l i s i n j e c t e d .
The l i q u i d and s o l i d c o n t e n t s were c o l l e c t e d from the r e a c t o r
and p l a c e d i n an e x t r a c t i o n t h i m b l e which was then p l a c e d i n a
soxhlet u n i t . The c o n t e n t s were then e x t r a c t e d w i t h t o l u e n e u n t i l
the e x t r a c t a n t was c l e a r a f t e r which the t h i m b l e was dried and
weighed. The weight of the d r i e d p r o d u c t i s d e s i g n a t e d as t o l u e n e
insolubles.
In t h i s work, the c o n v e r s i o n r e f e r s to the amount of t o l u e n e
solubles present a t the end of the r e a c t i o n . The conversion
p r o d u c t s thus i n c l u d e g a s e s , o i l s and a s p h a l t e n e s (GOA). Some of
the c o n v e r s i o n p r o d u c t s a r e due t o s i m p l e d i s s o l u t i o n o r t o h e a t i n g
of the c o a l , and some a r e due to c o n v e r s i o n of t o l u e n e i n s o l u b l e s
to t o l u e n e s o l u b l e s . Only the l a t t e r p o r t i o n of the c o n v e r s i o n
p r o d u c t s s h o u l d be a f f e c t e d by the t o l u e n e d e n s i t y . The former are
i n h e r e n t l y t o l u e n e s o l u b l e s , h a v i n g n o t h i n g t o do w i t h the d e n s i t y
or presence of s u p e r c r i t i c a l t o l u e n e . These are o n l y combined w i t h
the p r o d u c t s o b t a i n e d by r e a c t i o n f o r e x p e r i m e n t a l c o n v e n i e n c e .
The c o n v e r s i o n i s e x p e r i m e n t a l l y determined a s ,
G0A% = Coal i n j e c t e d ( g ) - toluene i n s o l u b l e s ( g ) χ 1 Q Q ^

Coal i n j e c t e d ( g )

©
Θ
© G A S S A M P L E LINE @THERMOCOUPLE

© R U P T U R E DISC T O H O O D © PUMP
® LIQUID S A M P L E P O R T © G A S LINE
© COAL BOMB @ FURNACE
® C O L D W A T E R (FOR STIRRER) © AGITATOR
© C O L D W A T E R (FOR M A G N E T I C HEAD) ® DRAIN V A L V E
© V E N T LINE T O H O O D © A R G O N CYLINDER
® HELIUM CYLINDER ® DATA LOGGER

® PRESSURE TRANSDUCER ® REACTOR
Figure 1: Experimental Set-up for Supercritical Extraction

where t o l u e n e i n s o l u b l e s r e f e r to the t o t a l mass of reaction

p r o d u c t s which a r e i n s o l u b l e i n toluene at i t s b o i l i n g point.
Toluene solubles, conversion products, and GOA are used
interchangeably·
T o l u e n e i s a non-donor s o l v e n t and as such i t s e f f e c t on c o a l
i s one p r i m a r i l y o f p h y s i c a l d i s s o l u t i o n .
Discussion. E x p e r i m e n t s were c a r r i e d out w i t h B r u c e t o n c o a l and

t o l u e n e at s u p e r c r i t i c a l t o l u e n e d e n s i t i e s i n the range o f 0.157-
0.601 g/cc. The temperature range s t u d i e d was 647-698 Κ and the
r e a c t i o n time was v a r i e d f r o m two minutes t o 60 m i n u t e s . The
e x p e r i m e n t a l r e s u l t s are e x p l a i n e d by a k i n e t i c model, the d e t a i l s
of which can be found e l s e w h e r e ( 1 6 ) .
The model i s summarized b r i e f l y h e r e . As c o a l i s h e a t e d , p a r t
of i t d i s s o l v e s i n the s u p e r c r i t i c a l t o l u e n e and p a r t does n o t .
Note t h a t a d i s t i n c t i o n must be made between the t o l u e n e s o l u b l e s
(GOA) in Equation 2 and the material soluble at reaction
c o n d i t i o n s , because th
s o l u b l e at t o l u e n e ' s boilin
m a t e r i a l s o l u b l e at the r e a c t i o n temperature which i s about 300 Κ
higher. Thus, w h i l e 40% of the c o a l might be d i s s o l v e d , f o r
example, i n the h i g h temperature t o l u e n e j u s t p r i o r to q u e n c h i n g ,
the t o t a l c o n v e r s i o n (GOA), as measured by E q u a t i o n 2, may o n l y be
15%. I t i s m e a n i n g f u l , t h e r e f o r e , to h y p o t h e s i z e t h a t o n l y the
d i s s o l v e d p o r t i o n of the c o a l undergoes c o n v e r s i o n from toluene
insolubles to toluene solubles. As discussed below, this
hypothesis o f f e r s a physical explanation of why the rate of
c o n v e r s i o n i n c r e a s e s w i t h t o l u e n e d e n s i t y , and i t does not r e q u i r e
t h a t t o l u e n e be h i g h l y r e a c t i v e . The model e q u a t i o n s are
1
f r - - V w
= k c l 2 ( 4 )
ïït i - V
2
= K A 2 (5)
Cl/C = S (6)
C - coal
CI - coal dissolved i n s u p e r c r i t i c a l solvent
C2 - coal insoluble i n s u p e r c r i t i c a l solvent
A - g a s e s , o i l s and a s p h a l t e n e s
KpK2 - r a t e c o n s t a n t s , min"*, min"^gm""^lit
S - weight f r a c t i o n which i s s o l u b l e i n t o l u e n e . It i s
c o r r e l a t e d as a f u n c t i o n of temperature and fluid
density (16).
The r e s u l t s of e x p e r i m e n t s at 647K and reduced d e n s i t i e s of

0.5 to 2.0 ( t o l u e n e densities of 0.157 g/cc and 0.601 g/cc) are
given i n Figures 2 and 3. The e x p e r i m e n t a l r e s u l t s show t h a t
toluene solubles (oils, asphaltenes, and g a s e s ) formed at low
r e a c t i o n times i n c r e a s e s w i t h b o t h temperature and density. In
general, solubility s t u d i e s have shown t h a t the amount of a s o l i d

F i g u r e 2: E f f e c t o f R e a c t i o n Time and D e n s i t y on % Toluene

S o l u b l e s (GOA) @ 647 Κ ( D e n s i t i e s of 0.301 and 0.157 g / c c )

F i g u r e 3: E f f e c t o f R e a c t i o n Time and D e n s i t y on % Toluene

S o l u b l e s (GOA) @ 647 Κ ( D e n s i t i e s o f 0.601 and 0.444 g / c c )

which can d i s s o l v e i n a s u p e r c r i t i c a l f l u i d i n c r e a s e s w i t h d e n s i t y
and, g e n e r a l l y , w i t h t e m p e r a t u r e . Hence, we c o n c l u d e t h a t t h e
c o n v e r s i o n o f c o a l t o o i l s + a s p h a l t e n e s + gases i s i n some sense
l i m i t e d by the d i s s o l u t i o n o f the c o a l i n the s o l v e n t .
We h y p o t h e s i z e t h a t the o n l y p a r t o f the c o a l which undergoes
r e a c t i o n t o gas, o i l s and a s p h a l t e n e s i s the d i s s o l v e d f r a c t i o n
( i n c l u d i n g p y r o l y s i s p r o d u c t s ) , which i n c r e a s e s w i t h temperature
and d e n s i t y . I n c r e a s e s i n the d i s s o l v e d f r a c t i o n thus l e a d t o
h i g h e r c o n v e r s i o n s and f a s t e r r e a c t i o n r a t e s . These c o n v e r s i o n
p r o d u c t s then p a r t i c i p a t e i n r e t r o g r e s s i v e r e a c t i o n s ( A m e s t i c a and
Wolf ( 1 2 ) ) f o r m i n g c h a r , so t h a t a t l o n g e r times (15 minutes o r
more) the y i e l d o f gases + o i l s + a s p h a l t e n e s d e c r e a s e s . At lower
temperatures (647 Κ ) , t h e r e t r o g r e s s i v e r e a c t i o n s a r e i n s i g n i f i c a n t
and c o n v e r s i o n does not d e c r e a s e w i t h t i m e .
The above h y p o t h e s i s i s w e l l e x p l a i n e d by the r e s u l t s g i v e n i n
F i g u r e s 2 and 3. At a lower d e n s i t y o f 0.157 g / c c the f r a c t i o n o f
c o a l d i s s o l v e d i n the s u p e r c r i t i c a l f l u i d i s much lower than when
the d e n s i t y o f the s u p e r c r i t i c a
f r a c t i o n o f c o a l , whic
gases, i s a l s o lower.
The r e s u l t s o f experiments a t 673 Κ and reduced d e n s i t y o f 1.0
and 1.5 ( s u p e r c r i t i c a l t o l u e n e d e n s i t y o f 0.301 g / c c and 0.444
g / c c ) a r e g i v e n i n F i g u r e 4. As o b s e r v e d a t 647 K, t h e c o a l
conversion t o gases + oils + asphaltenes (toluene s o l u b l e s )
increase with reaction time and with the d e n s i t y o f the
supercritical fluid. The retrogressive reactions a r e more
s i g n i f i c a n t now and hence, the t o l u e n e s o l u b l e s show a maxima i n
conversion with time.
The r e s u l t s o f experiments a t 698 Κ and reduced d e n s i t i e s o f
1.0 and 1.5 ( s u p e r c r i t i c a l t o l u e n e d e n s i t y o f 0.301 g / c c and 0.444
g / c c ) a r e g i v e n i n F i g u r e 5. As observed a t 647 Κ and 673 K, the
c o a l c o n v e r s i o n t o gases + o i l s + a s p h a l t e n e s ( t o l u e n e s o l u b l e s )
increases with reaction time and d e n s i t y o f the s u p e r c r i t i c a l
fluid. The r e t r o g r e s s i v e r e a c t i o n s a r e more pronounced than t h a t
at 673 Κ but we s t i l l observe a maxima i n the t o l u e n e s o l u b l e s as a
f u n c t i o n of r e a c t i o n time. The i n i t i a l rate of formation of
t o l u e n e s o l u b l e s (as seen from the s t e e p n e s s o f the c u r v e s o f
toluene s o l u b l e s versus r e a c t i o n time) i s higher at higher d e n s i t y
and h i g h e r t e m p e r a t u r e . A l s o note t h a t the amount o f t o l u e n e
s o l u b l e s a t the maxima i s h i g h e r when the temperature and d e n s i t y
of the s u p e r c r i t i c a l f l u i d i s h i g h e r . T h i s i s c o n s i s t e n t w i t h the
h y p o t h e s i s t h a t the s o l u b l e f r a c t i o n o f the c o a l i n c r e a s e s w i t h
temperature and d e n s i t y o f the s u p e r c r i t i c a l f l u i d .
The r e s u l t s o f the model s i m u l a t i o n a r e g i v e n i n F i g u r e s 6, 7
and 8. F i g u r e 6 shows t h e e f f e c t o f d e n s i t y on t h e k i n e t i c s of
c o a l l i q u e f a c t i o n a t temperature o f 698 K. I t i s very c l e a r t h a t
conversion increases with an i n c r e a s e i n d e n s i t y and i t i s
c o n s i s t e n t w i t h t h e h y p o t h e s i s made e a r l i e r on c o a l l i q u e f a c t i o n
with a supercritical fluid. Figure 7 shows t h e e f f e c t of
temperature on the k i n e t i c s o f c o a l l i q u e f a c t i o n a t d e n s i t y o f
0.601 g / c c . I t i s e v i d e n t t h a t c o n v e r s i o n s a r e h i g h e r a t h i g h e r
temperatures and lower r e a c t i o n times but a t l o n g e r r e a c t i o n times
due t o c o n d e n s a t i o n r e a c t i o n s , a d e c r e a s e i n r a t e w i t h temperature
i s observed.

0 10 20 30 40 50 60
Reaction Time, Min.
F i g u r e 4: E f f e c t of Reaction Time and D e n s i t y on % Toluene

S o l u b l e s (GOA) @ 673 Κ

35
I I I I I I I
0 10 20 30 40 50 60
Reaction Time, Min.
F i g u r e 5: E f f e c t of R e a c t i o n Time and D e n s i t y on % Toluene

S o l u b l e s (GOA) @ 698 Κ

F i g u r e 6: Effect o f D e n s i t y and R e a c t i o n Time on % T o l u e n e

S o l u b l e s a t 698 Κ and C o a l C o n c e n t r a t i o n o f 40 g/1

Figure 7: Effect of Temperature and R e a c t i o n Time on %

Toluene S o l u b l e s a t 0.601 g/cra and C o a l C o n c e n t r a t i o n o f 40
g/i

20. DESHPANDE ET AL. Solvent Density ά Coal Liquefaction Kinetics 263
The coal/solvent ratio also affects the initial coal

c o n c e n t r a t i o n and hence the c o n c e n t r a t i o n o f i n t e r m e d i a t e p r o d u c t s
(toluene s o l u b l e s ) i n the r e a c t o r . T h i s i s shown i n F i g u r e 8.
These intermediate products undergo retrogressive/condensation
r e a c t i o n s which f o l l o w second o r d e r k i n e t i c s . The r e t r o g r e s s i v e
r e a c t i o n s become v e r y s i g n i f i c a n t a t h i g h temperatures and h i g h
densities. Hence, the c o n v e r s i o n goes through a maximum and the
conversions a t l o n g e r r e a c t i o n times a r e lower when c o a l / s o l v e n t
r a t i o i s higher. The i n i t i a l p a r t of the k i n e t i c curve i s not
a f f e c t e d by the c o a l / s o l v e n t r a t i o . T h i s i s because r e t r o g r e s s i v e
r e a c t i o n s a r e not predominant a t low r e a c t i o n times and the amount
of c o a l which d i s s o l v e s i n the s u p e r c r i t i c a l f l u i d i s independent
of the c o a l / s o l v e n t r a t i o .
Because c o a l i s heterogeneous i n n a t u r e , as the d e n s i t y i s
i n c r e a s e d , h e a v i e r and h e a v i e r c o a l f r a c t i o n s (as opposed t o more
and more of the same f r a c t i o n ) a r e d i s s o l v e d i n the s u p e r c r i t i c a l
fluid. These would not dissolve i f the d e n s i t y of the
s u p e r c r i t i c a l f l u i d wer
general, u n l i k e l y to b
s u b s t a n t i a l l y d i s s o l v e d ( i . e . e i t h e r z e r o o r 100% o f a f r a c t i o n i s
dissolved). F o r example, i f c o a l i s c o n s i d e r e d t o be composed o f
100 f r a c t i o n s c h a r a c t e r i z e d by i n c r e a s i n g m o l e c u l a r weight, more
and more o f t h e s e f r a c t i o n s d i s s o l v e as d e n s i t y i s i n c r e a s e d , but
the s o l u b i l i t y o f a g i v e n f r a c t i o n goes from ( a p p r o x i m a t e l y ) z e r o
to 100% o v e r a s m a l l change i n d e n s i t y . If a given fraction,
number 46 f o r example, i s d i s s o l v e d , t h e n more o f t h a t m o l e c u l a r
weight group would d i s s o l v e a t t h a t d e n s i t y i f i t were p r e s e n t , but
none o f the u n d i s s o l v e d f r a c t i o n s would d i s s o l v e r e g a r d l e s s o f the
amount o f c o a l p r e s e n t . Hence, the f r a c t i o n o f the c o a l and not
the amount of c o a l which d i s s o l v e s i n the s u p e r c r i t i c a l f l u i d i s a
s t r o n g f u n c t i o n o f d e n s i t y and temperature o f the s u p e r c r i t i c a l
fluid. In o t h e r words, i f the amount of c o a l i n j e c t e d i n t o the
s u p e r c r i t i c a l f l u i d at g i v e n temperatures and d e n s i t y was reduced
to i t s h a l f v a l u e , the a b s o l u t e amount d i s s o l v e d w i l l f a l l by 50%.
If the amount of c o a l i n j e c t e d was i n c r e a s e d indefinitely,
then a p o i n t might be reached where the s u p e r c r i t i c a l f l u i d i s
saturated with d i s s o l v e d c o a l . I f the amount o f c o a l i n j e c t e d i s
i n c r e a s e d beyond t h i s v a l u e , the f r a c t i o n of d i s s o l v e d c o a l and the
f r a c t i o n a l coal conversion w i l l s t a r t decreasing. The amount o f
d i s s o l v e d c o a l i n the s u p e r c r i t i c a l f l u i d w i l L be independent of
the amount o f c o a l i n j e c t e d i n such a c a s e . T h i s phenomena i s very
w e l l i l l u s t r a t e d i n F i g u r e 9.
Conclusions. When c o a l i s c o n t a c t e d w i t h a non-donor s u p e r c r i t i c a l

fluid a part o f the c o a l instantaneously dissolves i n the
supercritical fluid. The d i s s o l v e d c o a l undergoes l i q u e f a c t i o n
r e a c t i o n s which a r e t h e r m a l i n n a t u r e r e s u l t i n g i n t o l u e n e s o l u b l e
p r o d u c t s b e i n g formed from c o a l . These p r o d u c t s c a n s u b s e q u e n t l y
undergo r e t r o g r e s s i v e r e a c t i o n s y i e l d i n g i n s o l u b l e m a t e r i a l . Hence
the t o l u e n e s o l u b l e s show a maxima i n c o n v e r s i o n w i t h t i m e .
The f r a c t i o n of c o a l which d i s s o l v e s i n s t a n t a n e o u s l y i n the
s u p e r c r i t i c a l f l u i d i n c r e a s e s w i t h an i n c r e a s e i n the d e n s i t y and
temperature o f the s u p e r c r i t i c a l f l u i d . This e f f e c t i s s i m i l a r to
that generally observed f o r the s o l u b i l i t y of a s o l i d in a
supercritical fluid. With an i n c r e a s e i n d e n s i t y and temperature

Coal Concentration g / l l t .
I ; i î ; k
ο 1 i i ι i i
O 20 40 60 60 100 120
Reaction Time, [tun.]
F i g u r e 8: E f f e c t o f C o a l C o n c e n t r a t i o n and R e a c t i o n Time on
3
% Toluene S o l u b l e s a t 698 Κ and 0.601 g/cra
Coal/Solvent Ratio
Figure 9: Effect of Coal/Solvent Ratio on Amount and

F r a c t i o n of Coal Dissolved i n a S u p e r c r i t i c a l Solvent

20. DESHPANDE E T AL. Solvent Density & Coal Liquefaction Kinetics 265
higher molecular compounds p r e s e n t i n coal go i n t o solution,

r e s u l t i n g i n an u n d e r s a t u r a t e d s o l v e n t w i t h t h e f r a c t i o n , n o t the
amount, o f the c o a l which i s b e i n g d i s s o l v e d .
Acknowledgments
The authors wish t o tank the U.S. Department of Energy under

c o n t r a c t DE-FG22-PC71257 f o r s u p p o r t o f t h i s work.
Literature Cited
1. Slomka, B.; Rutkowski, A. Fuel Processing Technol. 1982, 5,
247.
2. Jezko, J . ; Gray, David; Kershaw, J.R. Fuel Processing Technol.
1982, 15, 229.
3. Kershaw, J.R. Fuel Processing Technol. 1982, 5, 241.
4. Whitehead, J.C.; Williams, D.F. J . Inst. Fuel (London) 1975,48,
182.
5. Penninger, J.M.L. "Oi
Compressed Aqueous Gas Extractants-Stoichiometry and Mechanism
of Extraction," presented at 1984 Annual AIChE Meeting, San
Francisco, California, November (1984).
6. Blessing, J . E . ; Ross, D.S. "Supercritical Solvents and the
Dissolution of Coal and Lignite," ACS Symposium Series 71,
American Chemical Society: Washington, D.C., 1978.
7. Bartle, K.D.; Calimli, A.; Jones, D.W., Matthews; R.S.; Olcay,
A. Fuel 1979, 58, 423.
8. Tugrul, T.; Olcay, A. Fuel 1978, 57, 415.
9. Bartle, K.D.; Martin, T.G.; Williams, D.F. Fuel 1975, 54, 226.
10. Kershaw, J.R. S. Afr. J . Chem. 1977, 30, 205.
11. Barton, Paul Ind. Eng. Chem. Process Des. Dev. 1983, 22, 589.
12. Amestica, L.A.; Wolf, E.E. Fuel 1984, 63, 227.
13. Deshpande, G.V. Ph.D. Dissertation, University of Pittsburgh,
Pittsburgh, PA, 1985.
14. Deshpande, G.V.; Holder, G.D.; Bishop, Α.Α.; Gopal, J . ; Wender,
I. Fuel 1984, 63, 958.
15. Towne, S.E. M.S. Thesis, University of Pittsburgh, Pittsburgh,
PA 1983.
16. Deshpande, G.V.; Holder, G.D.; Shah, Y.T., Ind. Eng. Chem.
Process Des. Dev., 1986, 25 (3).
Received June 25, 1986

Chapter 21
Extraction of Australian Coals with Supercritical

Aqueous Solvents
John R. Kershaw and Laurence J. Bagnell
Commonwealth Scientific and Industrial Research Organization, Division of Applied

Organic Chemistry, G.P.O. Box 4331, Melbourne, Victoria 3001, Australia
Conversions between 42-68% were obtained for

supercritical water extraction of Victorian brown
coals at 380°C and 22MPa, considerably higher than
using toluene under the same conditions. The
conversions obtaine
bituminous coal wer
marked effect on both the conversion and the
extract composition, whereas temperature had only a
slight effect. Considerably higher conversions
were achieved using dilute sodium hydroxide rather
than water. The composition of the products is
discussed.
The e x t r a c t i o n of c o a l s with s u p e r c r i t i c a l f l u i d s i s a p r o m i s i n g
r o u t e f o r the p r o d u c t i o n of l i q u i d f u e l s from c o a l . Generally,
h y d r o c a r b o n s o l v e n t s , n o t a b l y t o l u e n e , have been used as the
supercritical fluid. S u p e r c r i t i c a l water e x t r a c t i o n has not
r e c e i v e d the same a t t e n t i o n and o n l y r e c e n t l y t h e f i r s t d e t a i l e d
s t u d y was r e p o r t e d . I n t h a t work, Holder e t a l . (I) o b t a i n e d h i g h
c o n v e r s i o n s f o r e x t r a c t i o n of a German brown c o a l (70-75%) and a
B r u c e t o n bituminous c o a l ( c a . 58%) w i t h s u p e r c r i t i c a l water a t c a .
375°C and 23 MPa. These h i g h y i e l d s , however, c o n t r a s t with the
much lower c o n v e r s i o n s b r i e f l y r e p o r t e d (_2_~_5) f o r o t h e r c o a l s and
t h e r e appears to be c o n s i d e r a b l e v a r i a t i o n i n the e x t r a c t i v e power
of s u p e r c r i t i c a l water w i t h d i f f e r e n t c o a l s , even a l l o w i n g f o r the
d i f f e r e n c e s i n the e x t r a c t i o n p r o c e d u r e used. None of the above
r e p o r t s d i s c u s s e d i n any d e t a i l the c h e m i c a l nature of the
p r o d u c t s , nor how the products compare w i t h those o b t a i n e d from
more c o n v e n t i o n a l s o l v e n t s .
The p o t e n t i a l use of s u p e r c r i t i c a l water appears e s p e c i a l l y
a t t r a c t i v e f o r the e x t r a c t i o n of brown c o a l s w i t h t h e i r h i g h water
c o n t e n t , 50-70% f o r V i c t o r i a n brown c o a l s , thus removing the need
for a coal-drying stage. The d r y i n g and e x t r a c t i o n of these low
rank c o a l s would occur i n a s i n g l e p r o c e s s . The purpose of the
p r e s e n t study was t o i n v e s t i g a t e the f e a s i b i l i t y of the e x t r a c t i o n
of A u s t r a l i a n b l a c k and brown c o a l s w i t h s u p e r c r i t i c a l water. The
0097-6156/87/0329-0266$06.00/0

21. KERSHAW AND BAGNELL Extraction of A ustralian Coals 267
c h e m i c a l n a t u r e of the p r o d u c t s i s d i s c u s s e d t o g e t h e r w i t h a
comparison w i t h t o l u e n e e x t r a c t i o n of the same c o a l s . The e f f e c t
of a d d i t i o n of v a r i o u s c o - s o l v e n t s i s a l s o i n c l u d e d .
Experimental
The a n a l y s e s of the c o a l s used are given i n Table I .
S u p e r c r i t i c a l gas e x t r a c t i o n s Method A. E x t r a c t i o n s were c a r r i e d

out f o r 1 h a t temperature i n a 1 I s e m i - c o n t i n u o u s r e a c t o r ( 6 ) .
The r e a c t o r was charged w i t h c o a l (50 g d r y b a s i s ) and s o l v e n t (600
ml) and heated (7°C min"*). When the temperature reached 300°C,
s o l v e n t ( l i b " ) was pumped v i a a d i p tube, which a c t s as a p r e -
h e a t e r , i n t o the bottom of the r e a c t o r and through the c o a l bed. A
15 micron f i l t e r was p l a c e d i n the e x i t l i n e . The p r e s s u r e was
c o n t r o l l e d by a d j u s t i n g t h r o t t l i n g v a l v e s and the gaseous phase was
condensed by a w a t e r - c o o l e d condenser
F o r the t o l u e n e e x t r a c t i o n s
d e s c r i b e d p r e v i o u s l y (6)·
most of the e x t r a c t was i n s o l u b l e i n water, a f t e r c o o l i n g and
l o w e r i n g of the p r e s s u r e , and p r e c i p i t a t e d out i n the condenser and
r e c e i v e r from which i t was c o l l e c t e d by washing w i t h acetone and
then THF. The remainder o f the e x t r a c t was found i n the aqueous
s u s p e n s i o n which was e v a p o r a t e d to dryness on a r o t a r y e v a p o r a t o r
and the r e s i d u e e x t r a c t e d w i t h acetone and THF. The s o l v e n t s were
removed under reduced p r e s s u r e from the combined acetone and THF
s o l u t i o n s t o g i v e the t o t a l e x t r a c t . T h i s was then e x t r a c t e d w i t h
hot t o l u e n e and the c o o l e d s o l u t i o n f i l t e r e d to g i v e the p r e -
asphaltene f r a c t i o n . A f t e r the t o l u e n e was removed under reduced
p r e s s u r e from the f i l t r a t e , the r e s i d u e was r e - d i s s o l v e d i n a s m a l l
volume of t o l u e n e and a 20 f o l d excess of pentane added t o
p r e c i p i t a t e the a s p h a l t e n e which was f i l t e r e d o f f . The pentane and
t o l u e n e were then removed from t h e f i l t r a t e under reduced p r e s s u r e
to g i v e the o i l . F o r the NaOH e x t r a c t i o n s , t h e NaOH s o l u t i o n s were
n e u t r a l i s e d with HCl. The i n s o l u b l e e x t r a c t was washed w i t h water
and then e x t r a c t e d w i t h THF. Removal of the THF gave the t o t a l
extract.
The e x t r a c t i o n r e s i d u e was washed out o f the r e a c t o r w i t h
a c e t o n e , f i l t e r e d , washed w i t h acetone and d r i e d i n vacuum oven.
I n c a l c u l a t i n g the c o n v e r s i o n f i g u r e s , any e x t r a c t which was
i n s o l u b l e i n THF was assumed t o be u n r e a c t e d c o a l , which had been
c a r r i e d over. The c o n v e r s i o n and e x t r a c t y i e l d d a t a a r e t h e
average of d u p l i c a t e d e t e r m i n a t i o n s . Average v a r i a t i o n between t h e
d u p l i c a t e s was 1.8%.
S u p e r c r i t i c a l gas e x t r a c t i o n s Method B. E x t r a c t i o n s were c a r r i e d

out i n a 500 ml r o c k i n g a u t o c l a v e f i t t e d w i t h a s t a i n l e s s s t e e l
liner. The i n t e r n a l volume of the a u t o c l a v e w i t h l i n e r was 420 m l .
The a u t o c l a v e was charged w i t h c o a l and s o l v e n t , heated t o and
m a i n t a i n e d a t temperature f o r 1 h. The r e s i d u e was washed out of
the c o o l e d r e a c t o r w i t h a c e t o n e , f i l t e r e d , washed w i t h p y r i d i n e and
then acetone and d r i e d under vacuum. I n some c a s e s , g . c . a n a l y s e s
of the gases i n the c o o l e d r e a c t o r were c a r r i e d o u t .

Κ)
OS
00
TABLE I . A n a l y s e s of Coals Used
Loy Yang G e l l i o n d a l e Coolungoolun Morwell Yallourn Morwell Y a l l o u r n Millmerran Liddell

(A) (B) (C) (0) (E) P a l e ( F ) P a l e (G) (H) (D
a a a a a a
a a a
Moisture 10.8 7.3 11.5 52.6 65.0 56.5 57.2 4.9 3.3
b b b b b
b b b
Ash 0.6 5.4 2.2 2.7b 1.3 3.7 1.6 18.l 29.0
b b b b b
b
M i n e r a l s and i n o r g a n i c s 3.0 2.0 1.6 1.0 2.0 1.3
d d d d d e e
e d
V o l a t i l e matter 48.3 51.4 48.9 50.2 51.7 56.0 61.2 50.7 44.6
d d d d e e
e d d
C 71.0 66.5 70.7 69.6 67.3 71.5 71.2 79.0 80.6
d d d d e e
e d d
Η 4.8 4.7 5.1 5.0 4.7 5.8 6.2 6.3 6.0
d d d e e
e d d d
Ν 0.6 0.6 0.6 0.6 0.6 0.6 0.5 1.2 2.1
d d d e e
e d d d
S 0.3 0.8 4.1 0.3 0.2 0.7 0.2 0.7 0.4
d d d e e
e d d d
0 (by d i f f e r e n c e ) 23.3 27.4 19.5 24.5 27.2 21.4 21.9 12.8 10.9
,Η/C atom, r a t i o 0.81 0.85 0.87 0.86 0.84 0.97 1.04 0.96 0.89

Aromatic C (%C) 62 43
b e d
wt%; wt% d r y b a s i s ; wt% d r y ash f r e e b a s i s ; wt% d r y m i n e r a l and i n o r g a n i c free (dmif) b a s i s . g
η
70

Η
η
>
r
τι
r
c
5
21. KERSHAW AND BAGNELL Extraction of Australian Coals 269
A n a l y t i c a l procedures f o r the p r o d u c t s were as d e s c r i b e d

p r e v i o u s l y (_7_)·
S u p e r c r i t i c a l Water E x t r a c t i o n s
Good c o n v e r s i o n s were o b t a i n e d f o r e x t r a c t i o n of a number of

V i c t o r i a n brown c o a l s i n the semi-continuous r e a c t o r (method A) a t
c o n d i t i o n s (380°C and 22 MPa) c l o s e to the c r i t i c a l temperature
(374°C) and p r e s s u r e (22 MPa) o f water (see F i g u r e 1 ) . The
c o n v e r s i o n i n c r e a s e d as the v o l a t i l e matter content of these c o a l s
i n c r e a s e d i n a s i m i l a r manner t o the t r e n d s p r e v i o u s l y shown f o r
t o l u e n e and 5% t e t r a l i n / t o l u e n e e x t r a c t i o n (8_) (see F i g u r e 1 ) . The
h i g h e s t c o n v e r s i o n s were o b t a i n e d f o r the two p a l e l i t h o t y p e s ( F
and G ) , The c o n v e r s i o n of Y a l l o u r n c o a l was n o t i c e a b l y h i g h e r when
e x t r a c t e d i n a semi-continuous m i n i - r e a c t o r (see F i g u r e 1) w i t h a
1
f a s t e r h e a t i n g r a t e ( c a 100°C m i n " ) and o n l y 10 minutes a t
temperature. T h i s agrees w i t h the work o f Holder e t a l . ( l _ ) who
obtained a conversion o
c o a l when the c o a l was
compared w i t h 70-75% when the c o a l was i n j e c t e d i n t o the hot
reactor. The lower c o n v e r s i o n s o b t a i n e d i n the r o c k i n g a u t o c l a v e
(method B) (see T a b l e I I ) , when the v o l a t i l e product i s not removed
from t h e a u t o c l a v e , a r e a l s o i n agreement w i t h these f i n d i n g s .
Except f o r the low a s h Loy Yang c o a l , d a t a f o r the brown c o a l s a r e
g i v e n on a d r y m i n e r a l and i n o r g a n i c f r e e ( d m i f ) b a s i s which i s the
p r e f e r r e d b a s i s f o r r e c o r d i n g d a t a on these c o a l s (9_). The
c o n v e r s i o n s were not as h i g h f o r M i l l m e r r a n ( s u b - b i t u m i n o u s ) and
L i d d e l l ( b i t u m i n o u s ) c o a l s ; 34.7 and 25.5 wt% daf r e s p e c t i v e l y .
The a s p h a l t e n e and p r e - a s p h a l t e n e c o n t e n t s of the e x t r a c t s a r e h i g h
(see F i g u r e 2 ) , as i s the case w i t h s u p e r c r i t i c a l gas e x t r a c t i o n
u s i n g hydrocarbon s o l v e n t s .
E x t r a c t i o n s of t h r e e of the c o a l s were a l s o c a r r i e d out i n a
r o c k i n g a u t o c l a v e (method B) mainly t o a l l o w a n a l y s i s of the gases
to be c a r r i e d o u t . The r e s u l t s of these e x t r a c t i o n s a r e shown i n
T a b l e I I . The h i g h carbon d i o x i d e y i e l d s o b t a i n e d were i n d i c a t i v e
TABLE I I . Water E x t r a c t i o n of Brown C o a l s i n a Rocking Autoclave

a t 380°C
Coal Loy Yang Coolungoolun Yallourn
P r e s s u r e (MPa) 24 23 26
Conversion 45.6 a
39.8 b
46.3 b
a b b
Extract Yield 21.7 21.3 19.3
b
co 2
16.9 a
9.7 ca 1 9 b
b
CO/air 0.3 a
0.9 N.D. C
b
CH^/C H /C3Hg
2 6 0.4 a
0.7 N.D.
CH 0H
3 0.4 a
0.05u b
0.8 b
CH3COCH3 0.6 a
0.2 b
0.8 b
CH3CO C H 2 5 0.1 a
0.05 b
0.1 b
a
Phenols 0.3 0.2 b
0.5 b
a b c
wt% c o a l d a f ; wt% c o a l dmif; N.D.= not d e t e r m i n e d .

Water 380°C 22MPa^

Conv= I-50VM-25 0
(r = 0 9 l )
60A
Mini-Reactor 5 % Tetralin/Toluene
Ε 400°C 10 MPa
Ό Conv=l82VM-45 0
(r«086) •
Ç 50H
£ 40-1 Toluene 380°C Toluene 400°C

2 22 lOMPa
c
I-52VM-42-3
30
Volatile Matter (wt%,dmif)
F i g u r e 1. V a r i a t i o n i n conversion with v o l a t i l e matter

c o n t e n t f o r V i c t o r i a n brown c o a l s .
F i g u r e 2. E x t r a c t c o m p o s i t i o n f o r water (and t o l u e n e )
e x t r a c t i o n s o f brown c o a l s a t 380°C and 22MPa.

of the h i g h c a r b o x y l i c content of the brown c o a l s . The hydrocarbon

gas make was low as was t h e y i e l d of carbon monoxide. Small
amounts of methanol, acetone, e t h y l methyl ketone and phenols were
a l s o formed. S t u d i e s of t h e p y r o l y s i s of V i c t o r i a n brown c o a l s
have shown t h a t s i g n i f i c a n t q u a n t i t i e s of water a r e e v o l v e d
t o g e t h e r w i t h t h e carbon d i o x i d e ( 1 0 ) . Presumably the d i f f e r e n c e
between t h e c o n v e r s i o n f i g u r e s and the sum of the e x t r a c t y i e l d and
o t h e r f i g u r e s i n T a b l e I I i s mainly due t o t h e l o s s of water (and
a l s o hydrogen s u l p h i d e i n the case of Coolungoolun c o a l ) . The
carbon d i o x i d e y i e l d was n o t i c e a b l y lower from C o o l u n g o o l u n c o a l ,
which has the lowest oxygen content of the seven brown c o a l s , than
from the o t h e r two c o a l s i n T a b l e I I .
Product Composition
A n a l y t i c a l data f o r some of the o i l s , a s p h a l t e n e s and p r e -

a s p h a l t e n e s produced a t 380°C and 22MPa from the brown c o a l s a r e
summarised i n T a b l e I I I
s i m i l a r except f o r the
a r o m a t i c i t i e s of the o i l s and a s p h a l t e n e s from c o a l s F and G, which
have h i g h e r H/C atomic r a t i o s than t h e o t h e r c o a l s . The e x t r a c t s
have a h i g h oxygen and h y d r o x y l c o n t e n t , e s p e c i a l l y i n t h e
a s p h a l t e n e and p r e - a s p h a l t e n e f r a c t i o n s , i n k e e p i n g w i t h the h i g h
oxygen c o n t e n t of these c o a l s . The H/C atomic r a t i o s of the o i l s ,
a s p h a l t e n e s and p r e - a s p h a l t e n e s a r e h i g h e r than f o r most c o a l
liquids. The r e l a t i v e l y h i g h H/C atomic r a t i o s of the e x t r a c t s
i n d i c a t e s t h a t the more a l i p h a t i c c o n s t i t u e n t s of the c o a l a r e
e x t r a c t e d under these c o n d i t i o n s and s u p p o r t s the view t h a t h i g h
c o n v e r s i o n s may a d v e r s e l y a f f e c t the l i q u i d q u a l i t y .
A n a l y t i c a l d a t a on the r e s i d u e s from f i v e e x t r a c t i o n s a r e
g i v e n i n T a b l e IV. The h i g h c a l o r i f i c v a l u e of the e x t r a c t i o n
r e s i d u e s , combined w i t h t h e i r s i g n i f i c a n t v o l a t i l e matter c o n t e n t
and r e l a t i v e l y low a s h c o n t e n t , i n d i c a t e s t h a t they s h o u l d be
a t t r a c t i v e m a t e r i a l s f o r combustion.
The n a t u r e of the p r o d u c t s o b t a i n e d on s u p e r c r i t i c a l water

e x t r a c t i o n o f V i c t o r i a n brown c o a l s i s f u r t h e r i l l u s t r a t e d by the
C-NMR s p e c t r a of the v a r i o u s f r a c t i o n s o b t a i n e d from Y a l l o u r n
1 3
P a l e ( c o a l G ) . The s o l i d s t a t e C CP-MAS NMR spectrum of t h e
s t a r t i n g c o a l shows an i n t e n s e a l i p h a t i c s i g n a l c e n t e r e d a t about
30 ppm (see F i g u r e 3 ) , i n d i c a t i v e of l o n g methylene c h a i n s i n t h e
coal. The spectrum of the e x t r a c t i o n r e s i d u e i s p r e d o m i n a n t l y
a r o m a t i c w h i l e t h e p r e - a s p h a l t e n e i s more a l i p h a t i c as i n d i c a t e d by
the peak c e n t e r e d a t a p p r o x i m a t e l y 30 ppm (see F i g u r e 3 ) . The
a l i p h a t i c n a t u r e of both t h e o i l and a s p h a l t e n e i s apparent from
solution C-NMR s p e c t r a of these f r a c t i o n s ( F i g u r e 4 ) . The
presence of l o n g u n s u b s t i t u t e d methylene c h a i n s (>Cg) i s shown by
the i n t e n s e ε o r i n n e r methylene peak a t 29.5 ppm, t o g e t h e r w i t h
the a, 3, Ύ and δ methylene peaks a t 14, 23, 32 and 29 ppm
r e s p e c t i v e l y i n the s p e c t r a of t h e o i l s and a s p h a l t e n e s from a l l
the e x t r a c t s .
The o i l from e x t r a c t i o n of Y a l l o u r n P a l e was f u r t h e r s e p a r a t e d
by e l u t i o n chromatography on s i l i c a g e l i n t o t h r e e f r a c t i o n s , a
pentane e l u a t e , a t o l u e n e e l u a t e and a c h l o r o f o r m / m e t h a n o l e l u a t e .

TABLE I I I . Analyses o f the E x t r a c t s from E x t r a c t i o n o f Brown Coals a t 380°C amd 22MPa
b
Coal B B C D E F G D D
Solvent T o l u e n e «• Water • 0.5M NaOH 2M NaOH
Oil
H/C 1.40° 1.41 1.35 1.34 1.37 1.41 1.48 1.36 1.34
a e
0 (wt%) 9.2 9.5 (9.3) 7.7 9.3 6.0 6.8 7.6 7.9
e
OH (wt%) 4.1 5.1 3.7 4.4 4.7 2.2 2.7 3.3 3.5
e
Mol. Wt. 285 271 314 291 287 326 353 373 361
e
Aromatic H (%) 16 17 17 18 17 13 11 15 16
e
Aromatic C (%) 40 44 47 36 31
Asphaltene
H/C 1.23 1.07 0.99 1.02 1.11 1.18 1.24 1.05 1.06
a
0 (wt%) 13.5 19.4 (18.3) 14.9 18.5 13.4 16.9 13.6 12.7
OH (wt%) 7.2 10.3 9.3 9.2 10.1 6.8 9.2 6.7 6.8
Mol. Wt. 470 374 415 369 323 433 417 432 429
Aromatic H (%) 28 36 34 32 33 24 24 30 29
Aromatic C (%) 53 69 66 51 50
Pre-asphalt ene
H/C 0.88 1.03 0.96 0.93 0.93 0.96 0.94 0.86 0.85

a
0 (wt%) 14.8 19.6 (21.1) 17.1 19.7 19.1 21.5 16.0 15.6
OH (wt%) 8.3 10.8
Mol. Wt. 469 724
Aromatic H (%) 45 42 43 39 39 45 45
Aromatic C (%) 79 71

Λ
oxygen f i g u r e s a r e by d i r e c t d e t e r m i n a t i o n except f o r those i n p a r e n t h e s i s which a r e by
e
difference; see T a b l e I f o r c o a l t y p e ; corrected forbibenzyl.
Coal
Yallourn Pale
ppm
1 3
Figure 3. C CP-MAS NMR spectra.
Asphaltene
Oil
ι ι I I I I I I I I I I—I 1—ι—ι—ι—ι—L_
150 0 90 0 30 0
PPM
13
Figure 4. 62.9 MHz C-NMR s p e c t r a o f o i l and a s p h a l t e n e .

TABLE IV. A n a l y t i c a l Data f o r Residues from Water E x t r a c t i o n a t

22 MPa
Coal Β Β Β C G
Extraction
Temperature (°C) 380 420 460 380 380
M o i s t u r e (wt%) 10.8 10.6 9.8 6.0 N.D.

Ash (wt% dry b a s i s ) 8.9 9.2 9.4 3.6 5.0
V o l a t i l e Matter
(wt% d r y b a s i s ) 31.7 27.1 21.6 26.6 N.D
C (wt% d r y b a s i s ) 71.8 73.9 76.2 76.3 67.7
H (wt% dry b a s i s ) 3.6 3.5 3.2 3.8 3.2
Ν (wt% d r y b a s i s ) 0.7 0.7 0.7 0.7 1.4
S (wt% dry b a s i s ) 0.9 0.9 0.8 3.7 0.3
H/C 0.60 0.57 0.50 0.60 0.57
S p e c i f i c energy
(MJ/kg, dry b a s i s ) 27.5 28.1 28.9 30.4 N.D.
A r o m a t i c carbon (% C)
These f r a c t i o n s c o r r e s p o n d to p r e d o m i n a n t l y a l i p h a t i c h y d r o c a r b o n ,
a r o m a t i c h y d r o c a r b o n and p o l a r f r a c t i o n s . The p r i n c i p a l components
of the pentane e l u a t e a r e n - a l k a n e s w i t h an average c h a i n l e n g t h of
C
17 y b C
"~ N M R
s p e c t r o s c o p y ( F i g u r e 5) and C Q by GC/MS.
2 The
l a t t e r i s i n good agreement w i t h the m o l e c u l a r weight of 281.
Branched c h a i n a l k a n e s , a l k e n e s e s p e c i a l l y 1-alkenes and some
c y c l i c compounds are a l s o p r e s e n t i n t h i s f r a c t i o n . The C-NMR
s p e c t r a of the a r o m a t i c h y d r o c a r b o n and p o l a r f r a c t i o n s a l s o show
the p r e s e n c e of s i g n i f i c a n t amounts of l o n g a l k y l c h a i n s ( s e e
F i g u r e 5 ) . The p o l a r f r a c t i o n of the o i l has a h i g h oxygen and
h y d r o x y l c o n t e n t (see T a b l e V ) .
TABLE V. Data for O i l Fractions from Y a l l o u r n Pale coal
Pentane Toluene CHCI3/CH3OH

eluate eluate eluate
(1) (2) (3)
Yield (wt% c o a l d m i f ) 2.9 4.7 9.3
(wt% o i l ) 17 28 55
H/C 1.84 1.33 1.46
0 (wt%) N.D. 3.3 10.6
OH (wt%) N.D. 0.7 4.5
Mol. Wt. 281 344 365
A r o m a t i c C(%C) N.D. 45 37
A r o m a t i c H(%H) N.D. 11 10
The Effect of P r e s s u r e and Temperature
Pressure. The c o n v e r s i o n and e x t r a c t y i e l d b o t h i n c r e a s e

c o n s i d e r a b l y w i t h p r e s s u r e as do the a s p h a l t e n e and p r e - a s p h a l t e n e

c o n t e n t of the e x t r a c t s (see F i g u r e 6 ) . The H/C atomic r a t i o s of

the o i l and a s p h a l t e n e f r a c t i o n s d e c r e a s e , w h i l e the hydrogen and
carbon ( f o r the o i l ) a r o m a t i c i t i e s i n c r e a s e (see T a b l e V I ) w i t h
i n c r e a s i n g p r e s s u r e . T h i s presumably i n d i c a t e s that the more
a l i p h a t i c products a r e e x t r a c t e d p r e f e r e n t i a l l y a t lower p r e s s u r e s .
TABLE V I . E f f e c t o f P r e s s u r e on E x t r a c t s from Loy Yang C o a l .

Water E x t r a c t i o n at 380°C
P r e s s u r e (MPa) 7 15 22
Oil H/C 1.48 1.45 1.41

Aromatic H (%H) 13 15 17
Aromatic C (%C) N.D. 41 44
Asphaltene H/C 1.26 1.13 1.07
A r o m a t i c H(%H) 27 33 36
Temperature. Extraction
380°C, 420°C and 460°C. There were o n l y s m a l l d i f f e r e n c e s between
the c o n v e r s i o n s , e x t r a c t y i e l d s and n a t u r e of the p r o d u c t s a t these
v a r i o u s temperatures (see T a b l e V I I ) . T h i s i s somewhat s u r p r i s i n g
as i t was e x p e c t e d , e s p e c i a l l y i n l i g h t of the r e c e n t work of
H o l d e r e t a l . Ο ) , t h a t the h i g h e s t c o n v e r s i o n would o c c u r a t t h e
h i g h e s t water d e n s i t y , namely at 380°C. However, t h i s was not the
case. I n c r e a s e d thermal f r a g m e n t a t i o n of the c o a l as the
temperature i s r a i s e d o r s i g n i f i c a n t e x t r a c t i o n o c c u r i n g b e f o r e the
f i n a l temperature ( o f 460°C) i s reached, as i n d i c a t e d by the 60%
TABLE V I I . E x t r a c t i o n of G e l l i o n d a l e C o a l w i t h Water a t V a r i o u s
Temperatures and 22MPa
Temperature (°C) 380 420 460
C o n v e r s i o n (wt% c o a l , dmif) 52.7 56.7 57.2

E x t r a c t Y i e l d (wt% c o a l dmif) 22.6 23.1 20.5
Oil
Y i e l d (wt% c o a l dmif) 9.0 10.7 9.4
H/C 1.41 1.40 1.38
Aromatic H(%H) 17 18 18
Mol. Wt. 271 295 287
OH (wt%) 5.1 4.4 4.8
Asphaltene
H/C 1.07 1.09 1.08
A r o m a t i c H(%H) 36 35 36
Mol. Wt 374 349 350
OH (wt%) 10.3 10.0 11.6
Pre-asphaltene
H/C 1.03 0.99 0.97
Residue
H/C 0.60 0.57 0.50

Oil-1
Oil-2
Oil-3
900
PPM
13
Figure 5. 62.9 MHz C-NMR s p e c t r a o f o i l f r a c t i o n s .
10 20
pressure ( MPa )
F i g u r e 6. E f f e c t o f p r e s s u r e on the e x t r a c t i o n o f Loy Yang

c o a l a t 380°C. · C o n v e r s i o n ; ο e x t r a c t y i e l d ; • o i l y i e l d ; Δ
a s p h a l t e n e y i e l d ; X p r e - a s p h a l t e n e y i e l d f o r water
e x t r a c t i o n ; • conversion f o r toluene e x t r a c t i o n .

c o n v e r s i o n o f Y a l l o u r n c o a l i n the m i n i - r e a c t o r a f t e r o n l y 10
minutes, may e x p l a i n our o b s e r v a t i o n .
G e n e r a l l y , r a i s i n g the temperature i n c r e a s e s t h e a r o m a t i c i t y
of c o a l l i q u e f a c t i o n p r o d u c t s . However, t h e r e were no s i g n i f i c a n t
changes i n e i t h e r the H/C atomic r a t i o s o r the hydrogen
a r o m a t i c i t i e s (see T a b l e V I I ) of t h e o i l s o r a s p h a l t e n e s w i t h
temperature. Though t h e r e was a d e c r e a s e i n the H/C atomic r a t i o
of the e x t r a c t i o n r e s i d u e and p o s s i b l y o f the p r e - a s p h a l t e n e w i t h
temperature (see T a b l e V I I ) . The p r e - a s p h a l t e n e c o n t e n t a l s o
appears t o d e c r e a s e w i t h i n c r e a s i n g e x t r a c t i o n temperature.
Comparison between t o l u e n e and water e x t r a c t i o n s
At 380°C and 22 MPa, the c o n v e r s i o n s f o r the brown c o a l s u s i n g

water were c o n s i d e r a b l y h i g h e r (see F i g u r e 1) but f o r b l a c k c o a l s
s l i g h t l y lower (34.7 ν 38.8 wt% daf f o r Millmerraan and 25.5 ν 30.4
wt% daf f o r L i d d e l l ) tha
c o a l s of v a r i o u s rank i
w a t e r / t o l u e n e m i x t u r e s of a brown, a sub-bituminous and a
bituminous c o a l a t a c o n s t a n t gas d e n s i t y i n a r o c k i n g a u t o c l a v e .
The presence of water was more advantageous f o r the e x t r a c t i o n o f
the brown c o a l than f o r the h i g h e r rank c o a l s (see F i g u r e 7 ) ,
though i n a l l cases the presence o f water i n c r e a s e d c o n v e r s i o n .
The h i g h e s t c o n v e r s i o n s were o b t a i n e d f o r m i x t u r e s of the two
solvents. S i m i l a r t r e n d s were n o t i c e d a t 380°C and at 340°C.
E x t r a c t i o n w i t h water i s more p r e s s u r e dependent than w i t h t o l u e n e
(see F i g u r e 6 ) .
The major d i f f e r e n c e between the t o l u e n e and water e x t r a c t s of
G e l l i o n d a l e c o a l a t 380°C was the h i g h e r oxygen and h y d r o x y l
c o n t e n t of the a s p h a l t e n e and p r e - a s p h a l t e n e from the water e x t r a c t
(see T a b l e I I I ) . The a s p h a l t e n e from t o l u e n e e x t r a c t i o n was l e s s
a r o m a t i c and had a h i g h e r m o l e c u l a r weight than the a s p h a l t e n e from
the water e x t r a c t i o n . The o i l s , however, were s i m i l a r . (The
a n a l y s e s of the o i l from t o l u e n e e x t r a c t i o n were c o r r e c t e d f o r 5%
b i b e n z y l which i s formed on t h e r m o l y s i s of t o l u e n e . P y r o l y s i s o f
t o l u e n e under s i m i l a r c o n d i t i o n s ( 1 1 ) , l e a d s t o the f o r m a t i o n o f
s m a l l amounts o f b i b e n z y l . Though, the r e a c t i o n of hydrogen and
b e n z y l r a d i c a l s from t o l u e n e w i t h c o a l fragments i s p o s s i b l e , i t i s
u n l i k e l y t h a t t h i s would s i g n i f i c a n t l y a f f e c t the a n a l y s i s of the
p r o d u c t s , g i v e n the s m a l l amount of b i b e n z y l formed a t t h i s
temperature.)
E x t r a c t i o n w i t h bases and t e t r a l i n / w a t e r mixtures
A c o n s i d e r a b l e i n c r e a s e i n c o n v e r s i o n of Morwell brown c o a l o c c u r s
when d i l u t e sodium h y d r o x i d e was used i n p l a c e of water (see T a b l e
VIIC and F i g u r e 8 ) . D i l u t e sodium c a r b o n a t e and formate had a
s i m i l a r e f f e c t (see T a b l e V I I I ) as d i d n-pentylamine (see T a b l e
I X ) , but no improvement was found w i t h d i l u t e h y d r o c h l o r i c a c i d ,
sodium c h l o r i d e o r ammonium h y d r o x i d e n o r w i t h 20% phenol/80% water
and methanol/water m i x t u r e s . The c o n v e r s i o n and e x t r a c t y i e l d
i n c r e a s e s w i t h the m o l a r i t y o f the sodium h y d r o x i d e ( F i g u r e 8 ) .
The d i s s o l u t i o n o f low rank c o a l s by sodium ( o r p o t a s s i u m )

80- • ^ " " ^ * Conversion
60- Liquid Yield^

—ο
40- ο ^ Pre-asphaltene -
/ —«7
' V
20- Asphaltene^
0 OiP^
IM 2M
Na OH Molarity
F i g u r e 8. Sodium h y d r o x i d e e x t r a c t i o n of M o r w e l l coal i n a
s e m i - c o n t i n u o u s r e a c t o r (method A ) .

h y d r o x i d e s o l u t i o n s (12 - 14) and primary a l i p h a t i c amines (14) has

been p r e v i o u s l y documented and, t h e r e f o r e , an i n c r e a s e i n
c o n v e r s i o n was e x p e c t e d . I t i s n o t i c e a b l e t h a t the i n c r e a s e i n
e x t r a c t y i e l d w i t h sodium h y d r o x i d e i s m a i n l y due t o an i n c r e a s e i n
the p r e - a s p h a l t e n e f r a c t i o n ( F i g u r e 8 ) . The c o m p o s i t i o n of the
o i l s and a s p h a l t e n e s from the sodium h y d r o x i d e e x t r a c t i o n s appear
s i m i l a r t o those o b t a i n e d from water e x t r a c t i o n but t h e p r e -
a s p h a l t e n e s from the a l k a l i e x t r a c t i o n s have lower H/C atomic
r a t i o s and h i g h e r hydrogen a r o m a t i c i t i e s than from water e x t r a c t i o n
(see T a b l e I I I ) .
Increase i n conversion i s also obtained with t e t r a l i n / w a t e r
m i x t u r e s (see T a b l e V I I I ) i n an analogous manner to the i n c r e a s e d
c o n v e r s i o n w i t h the a d d i t i o n of s m a l l amounts of t e t r a l i n t o
t o l u e n e (see F i g u r e 1 ) . S i m i l a r f i n d i n g s have been r e p o r t e d f o r
the e x t r a c t i o n of Powhatan c o a l w i t h t e t r a l i n / w a t e r and
t e t r a h y d r o q u i n o l i n e / w a t e r m i x t u r e s s i n c e t h i s work was completed
(15).
TABLE V I I I . C o n v e r s i o n s f o r E x t r a c t i o n of Morwell C o a l (15 g d r y )

i n a Rocking A u t o c l a v e (Method B) w i t h Aqueous S o l v e n t s (150 g) a t
380°C
Solvent Conversion (wt% c o a l dmif)
Water 48.7
0.5 M NaOH 66.6
0.25 M N a C 0 2 3 63.8
0.5 M HCOONa 67.0
10% T e t r a l i n / W a t e r 55.3
20% T e t r a l i n / W a t e r 59.8
TABLE IX. C o n v e r s i o n s f o r E x t r a c t i o n of Y a l l o u r n C o a l with

η -Pentylaraine (Method A)
Solvent Conversion (wt% c o a l dmif)

a b
A B
Water 54.4 56.7

2M n-Pentylamine 69.6 95.8
b
r e s i d u e washed w i t h acetone; r e s i d u e washed w i t h pyridine.
Conclusions
T h i s study i n d i c a t e s t h a t e x t r a c t i o n w i t h s u p e r c r i t i c a l water c o u l d
be an a t t r a c t i v e r o u t e f o r l i q u e f a c t i o n of V i c t o r i a n brown c o a l s
(but p r o b a b l y not b l a c k A u s t r a l i a n c o a l s ) . The low c o s t and ready
a v a i l a b i l i t y of t h e s o l v e n t ( w a t e r ) , t h e r e l a t i v e l y h i g h H/C atomic
r a t i o s of the e x t r a c t s , and a l s o as no hydrogen o r c o a l - d r y i n g a r e
required, are p o s i t i v e f a c t o r s . H i g h e r y i e l d s can be o b t a i n e d when
a s t r o n g base o r a hydrogen-donor i s added t o the w a t e r .

I t has been s u g g e s t e d (14) t h a t the b r e a k i n g of e s t e r bonds i s

i m p o r t a n t i n the d i s s o l u t i o n of low rank c o a l s . S u p e r c r i t i c a l
water may h y d r o l y s e e s t e r groups and thus be e f f e c t i v e f o r
e x t r a c t i n g brown c o a l s . The h i g h c o n v e r s i o n s o b t a i n e d w i t h sodium
h y d r o x i d e may be e x p l a i n e d by the a b i l i t y of t h i s s t r o n g base not
o n l y to break e s t e r bonds but a l s o t o a s s i s t i n s o l u b i l i s i n g t h e
r e s u l t a n t fragments. S i m i l a r l y , the p e n t y l group on the r e s u l t i n g
amide may h e l p s o l u b i l i s a t i o n when n - p e n t y l a m i n e was u s e d .
However, i t must be noted that the p h y s i c a l e v i d e n c e f o r
s i g n i f i c a n t amounts of e s t e r bonds i n brown c o a l s i s poor.
Acknowledgme n t s
The a u t h o r s a r e g r a t e f u l t o Mrs. I . S a l i v i n f o r OH and m o l e c u l a r

13
weight measurements, t o Mr.R.I. W i l l i n g f o r s o l u t i o n C-NMR
s p e c t r a , t o Dr. D.J. Çookson (BHP Melbourne R e s e a r c h L a b o r a t o r i e s )
13
f o r the s o l i d s t a t e C-NMR s p e c t r a and t o Dr D.J Brockway (SECV)
f o r a n a l y s e s of the e x t r a c t i o
Literature Cited
1. Deshpande, G.V.; Holder, G.D.; Bishop, A.A.; Gopal, J.;
Wender, I. Fuel, 1984, 63, 956.
2. Scarrah, W.P. In "Chemical Engineering at Supercritical Fluid
Conditions"; Paulaitis, M.E.; Penninger, J.M.L.; Gray, R.D.;
Davidson P. Eds.; Ann Arbor Science: Ann Arbor, 1983, pp. 395-
407.
3. Modell, M.; Reid, R.C.; Amin, S.I. U.S. Patent 4,113,446,
September 12, 1978.
4. Jezko, J.; Gray, D.; Kershaw, J.R. Fuel Processing Technology,
1982, 5, 229.
5. Vasilakos, N.P.; Dobbs, J.M.; Parasi, A.S. Amer. Chem, Soc.,
Div. Fuel Chem. Preprints, 1983, 28(4), 212.
6. Kershaw, J.R.; Overbeek, J.M. Fuel, 1984 63, 1174.
7. Kershaw, J.R. Fuel Processing Technology,, 1984, 9,235.
8. Kershaw, J.R.; Overbeek, J.M.; Bagnell, L.J. Fuel, 1985, 64,
1069.
9. Kiss, L.T.; King, T.N. Fuel, 1979 58, 547.
10. Schafer, H.N.S. Fuel, 1979, 58, 667 and 673.
11. Kershaw, J.R. S. Afr. J. Chem. 1978, 31, 15.
12. Lynch, B.M.; Durie, R.A. Aust. J. Chem., 1960, 13, 567.
13. Brooks, J.D.; Sternhell, S. Fuel, 1958, 37, 124.
14. van Bodegon, B.; van Veen, J.A.R.; van Kessel, G.M.M.; Sinnige
- Nijssen, M.W.A.; Stuiver, H.C.M. Fuel, 1984, 63, 346.
15. Towne, S.E.; Shah, Y.T.; Holder, G.D.; Deshpande, G.V.;
Cronauer, D.C. Fuel 1985, 64, 883.

Chapter 22
Hydrotreating in Supercritical Media

J. Y. Low
Phillips Petroleum Company, Phillips Research Center, Bartlesville, OK 74004
Our research involved the investigation of

catalytic hydrotreating in supercritical media.
The program consisted of essentially two parts--
feasibility studies and the effect of process
parameters of hydrotreating in supercritical
media. Hydrotreating of shale oil has revealed
that this type of hydrotreating is very effective
in heteroatom removal
and sulfur contents (19000 and 7000 ppm, respectively)
were reduced to 120 and 25 ppm in a single pass. It
is also effective for residua conversion. The 650F+
fraction of a petroleum crude was processed to yield
a product with less than 50% in the 65OF+ fraction
and less than 5% in the 850F+ fraction. Supercritical
hydrotreating had been tested for processing heavy
coal liquids, supercritical shale oil extract, and
conventional retorted shale oil. We have investigated
the effects of process parameters in supercritical
hydrotreating. The parameters studied include
temperature, pressure, liquid hourly space velocity,
and crude concentration.
In r e c e n t y e a r s , s u p e r c r i t i c a l f l u i d e x t r a c t i o n has been a v e r y
popular technique f o r separations. R e c e n t l y , t h e energy i n d u s t r i e s
have extended t h i s a p p l i c a t i o n t o c o a l l i q u e f a c t i o n and o i l s h a l e
extraction (1-5)· Phillips P e t r o l e u m Company has a l s o found
t h a t s u p e r c r i t i c a l e x t r a c t i o n o f o i l s h a l e improves t h e o i l y i e l d
compared t o i n s i t u o r above ground r e t o r t i n g , b u t p r o d u c e s a
lower q u a l i t y l i q u i d p r o d u c t . P h i l l i p s i s i n t e r e s t e d i n d e v e l o p i n g
t e c h n o l o g y t o upgrade t h e s u p e r c r i t i c a l l y e x t r a c t e d (SCE) s h a l e
oil to synfuel or clean motor fuels. One p r o j e c t was t o
investigate hydrotreating i n the presence o f the s u p e r c r i t i c a l
f l u i d which i s used i n t h e e x t r a c t i o n s t e p . I f the hydrotreating
s t e p can be i n t e g r a t e d w i t h t h e s u p e r c r i t i c a l e x t r a c t i o n step,
one can p o s s i b l y t a k e advantage o f t h e p r e s s u r e and h e a t a v a i l a b l e
i n the e x t r a c t i o n step.
0097-6156/87/0329-0281 $06.00/0

This investigation consisted of essentially two parts.

The f i r s t i n v o l v e d a f e a s i b i l i t y s t u d y o f c a t a l y t i c h y d r o t r e a t i n g
i n the presence of s u p e r c r i t i c a l f l u i d . The s e c o n d p a r t o f our
i n v e s t i g a t i o n involved the parametric s t u d i e s t o s e e how reaction
parameters a f f e c t s u p e r c r i t i c a l h y d r o t r e a t i n g .
Conclusions
From an e x t e n s i v e i n v e s t i g a t i o n o f t h e p o t e n t i a l o f h y d r o t r e a t i n g
of shale o i l using a solvent under s u p e r c r i t i c a l conditions,
t h e f o l l o w i n g c o n c l u s i o n s a r e made:
A h i g h n i t r o g e n - c o n t a i n i n g , h e a v y o i l s u c h as s h a l e o i l
can be hydrotreated under supercritical conditions to
y i e l d very l o w n i t r o g e n f u e l s a n d s y n c r u d e i n one step,
d e p e n d i n g on t h e c o n d i t i o n s u s e d ;
C o m p a r e d t o no s o l v e n t u s e d , t h e p r e s e n c e o f a l i g h t s o l v e n t
g i v e s a b e t t e r p r o d u c t and r e d u c e s c o k e f o r m a t i o n on the
catalyst surface
Compared t o an a r o m a t i
such as heptane improves nitrogen r e m o v a l and reduces
h y d r o g e n c o n s u m p t i o n ( f r o m 2600 s c f / b b l o f s h a l e o i l t o
1200 scf/bbl);
W i t h A r a b i a n t o p p e d c r u d e , t h e s o l v e n t l o s e s i t s enhancement
e f f e c t for nitrogen removal i f the solvent i s less than
50 w e i g h t p e r c e n t o f t h e f e e d ;
For e x t e n s i v e n i t r o g e n removal, a r e l a t i v e l y l o n g r e s i d e n c e
t i m e ( 3 0 m i n u t e s o r l o n g e r ) i s r e q u i r e d a t 850°F a n d 1^+00
psig;
S u l f u r i s almost completely removed even w i t h t h e mildest
reaction conditions studied.
Experimental
H y d r o t r e a t i n g System. A b e n c h - s c a l e h y d r o t r e a t i n g u n i t was used

for t h e s e e x p e r i m e n t s , a s s h o w n i n F i g u r e 1. The reactor was
a 316 s t a i n l e s s s t e e l t u b e w i t h an i n n e r d i a m e t e r o f 1 i n c h and
a l e n g t h o f 27.5 inches. The t o t a l v o l u m e i s a b o u t 290 ml.
The r e a c t o r was e q u i p p e d w i t h a t h e r m o c o u p l e w e l l ( a 1/4" χ 25"
s t a i n l e s s s t e e l t u b e ) f o r t e m p e r a t u r e measurements. The reactor
was f i r s t f i l l e d w i t h a b o u t 90 m l o f i n e r t p a c k i n g a g a i n t o s e r v e
as t h e p r e h e a t i n g zone f o r t h e o i l and h y d r o g e n . The t e m p e r a t u r e s
w e r e m e a s u r e d by t h e r m o c o u p l e s p l a c e d i n t h e m i d d l e o f e a c h o f
t h e i n e r t beds and t h e c a t a l y s t bed. The u n i t was r u n 2h hours
p e r day, 7 d a y s p e r week.
For the supercritical versus conventional hydrotreating
experiments (the comparison experiments), a fresh catalyst was
used f o r each o f the above e x p e r i m e n t s . For the feedstock t e s t i n g s
and r e a c t i o n parameter s t u d i e s , the same c a t a l y s t was used.
Before data were c o l l e c t e d , the f r e s h c a t a l y s t was lined out
for one w e e k ( l 6 8 h o u r s ) . When t h e f e e d o r r e a c t i o n p a r a m e t e r
was c h a n g e d , t h e c a t a l y s t was l i n e d o u t f o r 2k h o u r s b e f o r e data
were c o l l e c t e d .

22. LOW Hydrotreating in Supercritical Media 283
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PRODUCT TANKS
FEED
PUMP
F i g u r e 1. Supercritical hydrotreating system.

Feeds. During the course of the i n v e s t i g a t i o n , the following

feeds were used: supercritical extracted lignite liquid,
s u p e r c r i t i c a l e x t r a c t e d s h a l e o i l , P a r a h o s h a l e o i l , and Arabian
t o p p e d c r u d e (650F+). Their properties are given i n Table I.
To make t h e f e e d m i x t u r e , t h e h e a v y o i l was usually dissolved
i n a s o l v e n t s u c h as t o l u e n e o r n - h e p t a n e .
Catalysts. The N1-M0/AI2O3 catalyst (Nalco NM 502) was

commercially a v a i l a b l e from Nalco.
Catalyst Presulfurization. The c a t a l y s t was generally heated

to 300F w i t h n i t r o g e n p u r g i n g , and t h e n t h e n i t r o g e n a t m o s p h e r e
was r e p l a c e d w i t h a f l o w o f 1 0 % H2S i n hydrogen. A t t h e same
t i m e , t h e t e m p e r a t u r e was s l o w l y i n c r e a s e d t o 600F a n d was kept
a t t h i s t e m p e r a t u r e u n t i l t h e c a t a l y s t was completely sulfided.
The r e a c t i o n u s u a l l y takes four hours at 600F
a n d 100 l i t e r of
10% H S i n H .
2 2
R e s u l t s and Discussion
In t h i s r e p o r t the r e s u l t s from the i n v e s t i g a t i o n of hydrotreatment

o f s h a l e o i l , A r a b i a n t o p p e d c r u d e , and l i g n i t e e x t r a c t (under
s u p e r c r i t i c a l conditions) are discussed. These experiments were
carried out to i n v e s t i g a t e the p o t e n t i a l of hydrotreatment in
the presence of a l i g h t s o l v e n t under s u p e r c r i t i c a l c o n d i t i o n s
for shale o i l upgrading and the e f f e c t of r e a c t i o n parameters
in supercritical hydrotreating. These experiments are e x p l o r a t o r y
in nature to find whether hydrotreatment under supercritical
c o n d i t i o n s has any advantage i n the upgrading of high nitrogen
h e a v y c r u d e s , a n d i f s o , how do t h e m a j o r p a r a m e t e r s a f f e c t t h e
hydrotreatment under these c o n d i t i o n s . The f i r s t f e w e x p e r i m e n t s
were c a r r i e d out w i t h t h e s h a l e o i l o b t a i n e d by supercritical
extraction. T h i s s h a l e o i l i s a v e r y waxy g r e a s e and almost
f i t s the d e f i n i t i o n of a s o l i d . As shown i n T a b l e I , i t has
a very high nitrogen content (2.3%) a n d a s u l f u r c o n t e n t o f 1.0
wt%. The h y d r o g e n c o n t e n t i n the shale o i l i s r e l a t i v e l y high
w i t h H/C atomic r a t i o o f 1Λ8, e q u a l t o t h a t o f some p e t r o l e u m
crudes. O n l y a l i m i t e d a m o u n t o f t h i s m a t e r i a l was a v a i l a b l e ,
so o n l y a few e x p e r i m e n t s w e r e p e r f o r m e d w i t h t h i s s h a l e o i l .
Table I. Feed P r o p e r t i e s
Feed Elemental Analyses

>300F
Wt? C H N S H/C
SCE S h a l e O i l U ) 100 8^.5 10.U 2.3 1.0 l.hQ
Paraho Shale 0il(_2) 96.9 8^.5 11.Τ 1.9 0.7 1.66
A r a b i a n T o p p e d Crude(_3) 100 Qk.9 11.3 0.18 3.3 1.60
L i g n i t e Extract(h) 100 82.0 9.3 0.91 ΟΛί 1.36
(_l) The SCE s h a l e o i l i s a w a x y b l a c k s e m i - s o l i d .
(2) P a r a h o s h a l e o i l h a s a b o u t 70 vol% o f 65OF+ m a t e r i a l .
(3) T o t a l l y 650F+ m a t e r i a l .
Hard s o l i d a t room t e m p e r a t u r e .

Supercritical Versus Conventional. A series o f hydrotreating

experiments were c a r r i e d o u tunder c o n v e n t i o n a l c o n d i t i o n s ( w i t h o u t
the use o f a light solvent). The r e s u l t s a r e g i v e n i n T a b l e
II, along with some results obtained from a supercritical
hydrotreatment experiment. The e x p e r i m e n t s performed were n o t
under i d e n t i c a l c o n d i t i o n s , b u t t h e y a r e c l o s e enough t h a t t h e
r e s u l t s o b t a i n e d a r e v a l i d enough f o r comparison.
Table I I . Comparison o f Conventional and S u p e r c r i t i c a l

Hydrotreating
(Conditions: 1^00 p s i g , 8 5 0 F ,
H 2GSHV-300, N a l c o N i - M o )
No S o l v e n t With Solvent
Feed Shale O i l (Neat) 20? Shale O i l I n Toluene
LHSV 0.3 TOTAL - 1.6
Gas Y i e l d ( W t ? )
L i g h t (Wt?) 35 55
Heavy O i l (Wt?) 35 35
Coke (Wt?) 3.8 0.3
The results from the supercritical hydrotreatment

experiments a r e superior i n almost every respect t o c o n v e n t i o n a l
hydrotreatment experiments (without t h e use o f solvent). Under
similar conditions, s u p e r c r i t i c a l h y d r o t r e a t i n g produced better
p r o d u c t s , f o r example: l e s s gas y i e l d ( 1 0 ? vs_ 2 5 ? ) , m o r e o f
l i g h t o i l f r a c t i o n , < 3 0 0 F , (55 vs_ 35?) a n d l e s s c o k e f o r m e d o n
the catalyst s u r f a c e ( 0 . 3 v s 3.8? b a s e d on t h e feed). For
c o n v e n t i o n a l h y d r o t r e a t i n g we h a d e n c o u n t e r e d reactor plugging
problems when t h e u n i t was r u n n i n g m o r e t h a n 196 h o u r s . This
p r o b l e m was n o t f o u n d w i t h s u p e r c r i t i c a l h y d r o t r e a t i n g .
S u p e r c r i t i c a l Hydrotreatment o f SCE S h a l e O i l . SCE s h a l e o i l

was h y d r o t r e a t e d a t h i g h s e v e r i t y because o f i t s h i g h n i t r o g e n
content (Table I ) and extremely h i g h v i s c o s i t y . The e x p e r i m e n t a l
r e s u l t s a r e shown i n T a b l e I I I . Based o n t h e s h a l e o i l f e d ,
the product d i s t r i b u t i o n i s t h e f o l l o w i n g : 12? gases, 52? b o i l i n g
l e s s t h a n 300°F ( c a l c u l a t e d b y d i f f e r e n c e ) a n d 36? i n t h e h e a v y
o i l f r a c t i o n (>300°F). The e l e m e n t a l a n a l y s e s o f t h e heavy o i l
f r a c t i o n i n d i c a t e t h a t b e t t e r t h a n 99? o f t h e n i t r o g e n was r e m o v e d .
The s u l f u r r e m o v a l was e q u a l l y h i g h . The l i g h t b o i l i n g f r a c t i o n
(<300°F) u s u a l l y h a s l e s s t h a n 1 0 ppm o f s u l f u r a n d 1 0 ppm o f
nitrogen.
F o r R u n s 2 , 3, and 5 t h e feed entered t h e h y d r o t r e a t e r
directly from t h e s u p e r c r i t i c a l extraction unit. The e x t r a c t
c o n t a i n e d a b o u t k% s h a l e o i l i n t o l u e n e . Runs 2 a n d 3 w e r e c a r r i e d
o u t a t 8 +2F, a n d R u n s h a n d 5, a t T50F.
1
A t t h e lower r e a c t i o n
temperature (750F), t h e y i e l d o f gases dropped t o l e s s t h a n 2 ? ,
and the yield o f heavy o i l f r a c t i o n i n c r e a s e d by about 10?.
The e x t e n t o f n i t r o g e n r e m o v a l w a s r e d u c e d s i g n i f i c a n t l y a t t h e
lower temperature. However, t h e s u l f u r removal seemed t o be
unaffected by t h e l o w e r i n g o f r e a c t i o n temperature f r o m 8^2F

Table I I I . S u p e r c r i t i c a l Hydrotreatment o f SCE Shale Oil*
Run No.(l) Temp. LHSV Gases Heavy O i l (>300F)
wt
°F (Ci-cO # Wt? Ν (ppm) S(?)
1 Qk2 0.5 12 36 52 0.03
2 Qk2 1.6 h6 150 0.03
3 Qk2 1.6 hk 150 0.02
k 750 1.6 <2 5^+ 2300 0.08
750 1.6 <2 3 2 ( 2 ) 2000 0.01+
* A t o t a l o p e r a t i n g p r e s s u r e o f 1^00 p s i g a n d s u l f i d e d N i - M o
AI2O3 c a t a l y s t were used i n t h e s e experiments. The s h a l e
o i l h a d t h e f o l l o w i n g e l e m e n t a l a n a l y s e s : C, 8^.5; H,
1 0 Λ ; N, 2 . 3 ; S, 1.0.
(_l) The f e e d f o r Run 1
t o l u e n e , but f o r
in toluene.
(2) I n t h i s Run t h e f r a c t i o n was d i s t i l l e d u p t o hOOY i n s t e a d
o f 300F as u s u a l .
to 750F. Thus, these experimental results suggest that the

supercritically extracted s h a l e o i l c a n be p r o c e s s e d to y i e l d
v e r y low n i t r o g e n and s u l f u r f u e l s o r s y n c r u d e s .
S u p e r c r i t i c a l Hydrotreatment o f A r a b i a n Topped Crude. A series

o f experiments were performed w i t h A r a b i a n topped crude (65OF+)
to investigate the hydrotreatment o f h i g h s u l f u r crudes i n the
presence of a light s o l v e n t under supercritical conditions.
The experimental results o b t a i n e d a r e summarized i n Table IV.
The overall results are comparable t o those obtained from the
s u p e r c r i t i c a l h y d r o t r e a t m e n t o f SCE s h a l e o i l ( R u n l ) . The s u l f u r
r e m o v a l i s v e r y e x t e n s i v e ( a b o u t 99? r e m o v a l , r e d u c e d f r o m 3.3?
t o 0.02?). The n i t r o g e n c o n t e n t i n t h e h e a v y o i l f r a c t i o n s are
r e l a t i v e l y l o w , l e s s t h a n 60 ppm f o r r u n s w i t h t o t a l l i q u i d h o u r l y
s p a c e v e l o c i t y ( L H S V ) o f 0.5 (Runs 6 a n d 7) a n d a b o u t 770 ppm
f o r Run 8 w i t h a n LHSV o f 1.6. Thus, f o r e x t e n s i v e n i t r o g e n
r e m o v a l , l o w e r LHSV i s n e e d e d .
The effect o f crude o i l concentration i n the feed was
i n v e s t i g a t e d w i t h A r a b i a n 65OF+ t o p p e d c r u d e . Three c o n c e n t r a t i o n s
(20, 50 a n d 8 0 ? o f t o p p e d c r u d e i n t o l u e n e ) w e r e c h o s e n , w h i l e
the o t h e r e x p e r i m e n t a l c o n d i t i o n s were kept c o n s t a n t (see F i g u r e
2 a n d R u n s 9, 1 1 , a n d 12 i n T a b l e I V ). Both the n i t r o g e n removal
and h e a v y o i l c o n v e r s i o n a r e more e x t e n s i v e when t h e c r u d e i s
h y d r o t r e a t e d a t a more d i l u t e d l e v e l s u c h as 2 0 ? . The heteroatom

REACTION CONDITIONS:
850 F. 1400 PSIG
H GHSV 300
A
LHSV OF 1.6
/
/
/

Library
1155 16th St., N.W.
20 50 80
WT % CRUDE IN FEED
F i g u r e 2. Effect o fo i lconcentration i n s u p e r c r i t i c a l
hydrotreatment o farabian topped crude.

removal i s reduced a t higher crude concentrations and levels

off a t 50? o r h i g h e r . The y i e l d o f t h e heavy o i l fraction
increases w i t h i n c r e a s i n g concentration o f crude i n t h e toluene.
T a b l e I V . S u p e r c r i t i c a l H y d r o t r e a t m e n t o f A r a b i a n Topped Crude (ATC)

( 8 5 0 F , ikOO p s i g , H G H S V - 3 0 0 , N a l c o N i - M o C a t a l y s t )
2
Run No. Feed(l) LHSV Heavy O i l

W t ? ATC i n S o l v e n t Wt? TlJ) S (?)
6 20 0.5 3h 0.006 0.02
7 20 0.5 3h 0.001+ 0.02
8 20 1.6 59 0.068 0.01+
9 20 0.5 33 2 ppm 0.02
10 20 0.5 36 3 ppm 0.03
11 50 1.6 61+ 0.091+ 0.17
12 80 1.6 72 0.091+ 0.13
(_l) S o l v e n t f o r R u n s 9 a n d 1 0 was η-heptane; f o r o t h e r s
t o l u e n e was u s e d
Runs 9 a n d 10 w e r e c a r r i e d o u t t o s t u d y t h e e f f e c t o f
an aliphatic solvent such as η-heptane i n supercritical
h y d r o t r e a t i n g o f topped crude. Comparing t h e r e s u l t s f r o m Runs
6 a n d 7 i n w h i c h t o l u e n e was u s e d a s t h e s o l v e n t , t h e n i t r o g e n
c o n t e n t s i n h e a v y o i l f r a c t i o n s a r e much l o w e r f o r t h e h e p t a n e
runs than t h e t o l u e n e runs. The s u l f u r c o n t e n t s a r e a b o u t t h e
same. Thus, one c a n c o n c l u d e t h a t a n a l i p h a t i c s o l v e n t i s b e t t e r
solvent f o r hydrodenitrogenation than the aromatic solvent.
The reason i s that the aromatic solvent was competing f o r
hydrogénation ( a b o u t 1+ w t ? o f t h e t o l u e n e was c o n v e r t e d t o m e t h y l
cyclohexane).
S u p e r c r i t i c a l Hydrotreatment o f L i g n i t e E x t r a c t . Lignite extract

was h y d r o t r e a t e d i n t h e p r e s e n c e o f t o l u e n e u n d e r supercritical
c o n d i t i o n s ( 8 5 0 F , ll+00 p s i g , 2 0 w t ? l i g n i t e i n t o l u e n e , a h y d r o g e n
GHSV o f 3 0 0 , a n d a LHSV o f 1 o r 1 . 6 ) . T h e r e s u l t s a r e t a b u l a t e d
i n T a b l e V. The e l e m e n t a l a n a l y s e s o f t h e h e a v y o i l f r a c t i o n
h a v e i n d i c a t e d t h e f o l l o w i n g c h a n g e s (Runs 13 a n d l l + ) : n i t r o g e n ,
r e d u c e d f r o m 0.91 t o 0.11+?, a n d s u l f u r r e d u c e d f r o m 1+700 ppm
t o a b o u t 1 0 0 ppm.
T a b l e V. S u p e r c r i t i c a l Hydrotreatment of Lignite Extract
Run No. LHSV Heavy O i l F r a c t i o n (>300F)

Wt?(l) N (ppm) S (ppm)
13 1 30 1530 150
11+ 1 36 11+00 90
15 1.6 1+3 1180 100
Lignite Extract Feed 100 9100 1+700

Conditions: 8 5 0 F , ll+00 p s i g , 3 0 0 H 2 GHSV, 2 0 w t ? l i g n i t e
e x t r a c t i n t o l u e n e , N a l c o Ni-Mo c a t a l y s t .
(1) Wt? i s b a s e d o n t h e f e e d .

Run 15 w a s c a r r i e d o u t w i t h a h i g h e r LHSV o f 1.6, a n d

the results a r e n o t t o o much d i f f e r e n t f r o m Runs 13 a n d l H .
The heteroatom removals a r e about t h e same. The heavy o i l
f r a c t i o n , h o w e v e r , w a s i n c r e a s e d t o h3% f r o m 30 a n d 36? ( R u n s
13 a n d lh). Thus, t h e c o n c l u s i o n i s t h a t t h e l i g n i t e e x t r a c t ,
a solid, can also be u p g r a d e d to yield a syncrude by t h e
s u p e r c r i t i c a l hydrotreatment process.
Reaction Parameter Studies. Experiments were c a r r i e d o u t w i t h

conventional shale o i l (direct r e t o r t e d Paraho s h a l e o i l )f o r
the purpose o f studying t h e e f f e c t s o f r e a c t i o n parameters i n
h y d r o t r e a t i n g under s u p e r c r i t i c a l c o n d i t i o n s . I n one group o f
experiments, t h e s p a c e v e l o c i t y was v a r i e d ( 1 . 6 , 3 . 2 , a n d 5)
while t h e other r e a c t i o n parameters were kept constant. For
temperature s t u d i e s , t h e f o l l o w i n g r e a c t i o n temperatures were
investigated: TOO, 7 5 0 , 8 0 0 , a n d 8 5 0 F . The p r e s s u r e effect
was examined a t f o u r l e v e l s — 1000, lk00
9 2 0 0 0 , a n d 2^00 p s i g
a t 800F. We h a v e a l s
r a t i o and solvent types
The l i q u i d hourly space v e l o c i t i e s (LHSV, i n c l u d i n g t h e
s o l v e n t ) o f 1.6, 3 . 2 , a n d 5 w e r e i n v e s t i g a t e d a t 8 5 0 F , lkOO p s i g ,
20 w t ? P a r a h o s h a l e o i l i n t o l u e n e . The r e s u l t s a r e i l l u s t r a t e d
i n F i g u r e 3. W i t h t h e LHSV o f 1.6, t h e h e a v y o i l f r a c t i o n i s
o n l y 3h% b u t w h e n LHSV i s i n c r e a s e d t o 3.2, t h e h e a v y o i l f r a c t i o n
9
i n c r e a s e d t o 63? a n d d i d n o t c h a n g e w i t h further increase i n

LHSV. T h i s seems t o s u g g e s t t h a t o n e - t h i r d o f t h e s h a l e o i l
c a n u n d e r g o a m o l e c u l a r w e i g h t r e d u c t i o n more r a p i d l y ( a r e s i d e n c e
t i m e o f about 12 m i n u t e s ) t h a n t h e s e c o n d - t h i r d , w h i c h needs
a residence time o f up t o an hour, while t h e l a s t - t h i r d survives
l o n g e r t h a n one hour.
For heteroatom removal, t h e r e s u l t s reveal that for a
LHSV o f 1.6 t h e n i t r o g e n c o n t e n t i n t h e h e a v y o i l f r a c t i o n , w h i c h
i s a b o u t 3^ w t ? o f t h e t o t a l p r o d u c t s , i s 3 6 0 ppm (1.9? i n t h e
feed). T h u s , t h e o v e r a l l n i t r o g e n r e m o v a l i s g r e a t e r t h a n 98?.
F o r LHSV o f 3.2 t h e n i t r o g e n c o n t e n t i n t h e h e a v y o i l i s i n c r e a s e d
t o a b o u t 5 0 0 0 ppm. W i t h a f u r t h e r i n c r e a s e i n LHSV t o 5, t h e r e
i s a greater increase i nthe nitrogen content. The s u l f u r r e m o v a l
is very rapid. E v e n w i t h t h e LHSV o f 5, t h e r e i s o n l y 53 ppm
s u l f u r i n the heavy o i l .
Figure h i l l u s t r a t e s t h e r e s u l t s from r e a c t i o n temperature
studies. T h e r e a c t i o n t e m p e r a u r e s u s e d r a n g e d f r o m 7 0 0 F t o 850F,
with an increment o f 50F. The r e m a i n i n g r e a c t i o n parameters
w e r e h e l d c o n s t a n t , s u c h a s lkOO p s i g , LHSV o f 1.6 a n d H 2 GHSV
o f 3 0 0 . T h e s u l f u r seems t o b e r e m o v e d r a t h e r e a s i l y e v e n a t
7 0 0 F ( f r o m 7 0 0 0 ppm i n t h e f e e d t o 2 0 0 ppm i n t h e h e a v y o i l
fraction) o r 97? r e m o v a l . At higher temperatures t h e s u l f u r
content i n t h e h e a v y o i l i s much l o w e r ( 1 0 0 p p m ) . On t h e o t h e r
h a n d , t h e n i t r o g e n r e m o v a l r e q u i r e s a much h i g h e r temperature.
This, o f course, i s not s u r p r i s i n g . F o r t h e purpose o f o b t a i n i n g
r e l a t i v e l y c l e a n s y n c r u d e , we p r o b a b l y have t o operate a t h i g h
t e m p e r a t u r e ( 8 0 0 F ) a n d l o w s p a c e v e l o c i t y (<1.6).

F i g u r e 3. S p a c e velocity effects on s u p e r c r i t i c a l hydrotreatment

of shale o i l .

IL
REACTION CONDITIONS: ^
1400 PSIG. LHSV 1.6
I
Δ
700 750 800 850

TEMPERATURE ° F
F i g u r e h. Effect o f temperature on s u p e r c r i t i c a l hydrotreatment

of shale o i l .

The y i e l d o f h e a v y o i l i n c r e a s e s w i t h a d e c r e a s e o f r e a c t i o n
t e m p e r a t u r e ( F i g u r e h). For example, w i t h the r e a c t i o n temperature
o f 8 5 0 F , t h e h e a v y o i l i s o n l y a b o u t 30? o f t h e t o t a l products
(96.9 wt? i n the feed). While at the other extreme, t h a t i s ,
w i t h t h e r e a c t i o n t e m p e r a t u r e o f o n l y TOOF, t h e h e a v y o i l f r a c t i o n
r e p r e s e n t s 90? o f t h e w h o l e p r o d u c t s . Thus, the h i g h e r temperature
is necessary for the production of l i g h t products.
The effect of pressure on HDN and heavy o i l y i e l d in
s u p e r c r i t i c a l hydrotreating of shale o i l i s given i n Figure 5.
The experimental conditions used for these experiments are:
8 0 0 F , h y d r o g e n GHSV o f 600, LHSV o f 1.6, 20 w t ? shale o i l i n
t o l u e n e , and r e a c t i o n p r e s s u r e o f 1000-2^00 p s i g . I t i s observed
that nitrogen removal increases with increasing r e a c t i o n pressure.
A t t h e h i g h e s t p r e s s u r e s t u d i e d (2^00 p s i g ) , t h e n i t r o g e n content
i n t h e h e a v y o i l i s o n l y a b o u t 300 ppm. T h i s i s a b o u t 98? n i t r o g e n
removal. The nitrogen removal decreased with the decrease i n
reaction pressure. Pressure has some e f f e c t o n t h e h e a v y o i l
yield. At the lowest
was 65 wt?. The heav
i n the pressure. W i t h t h e h i g h e s t p r e s s u r e s t u d i e d (2Î+00 p s i g ) ,
t h e y i e l d was i n c r e a s e d t o 79 w t ? . The i n c r e a s e i n y i e l d must
be d u e t o t h e s u p p r e s s i o n o f h y d r o c r a c k i n g b y t h e p r e s s u r e .
The use o f a n o n - a r o m a t i c s o l v e n t as t h e supercritical
h y d r o t r e a t i n g s o l v e n t was s t u d i e d f i r s t w i t h A r a b i a n t o p p e d c r u d e
and then with Paraho s h a l e o i l i n hope o f r e d u c i n g hydrogen
consumption. The results are tabulated i n Tables IV and VI.
Run l6 used toluene as t h e s o l v e n t , and R u n s 17 a n d 18 used
η-heptane. The experimental results have shown t h a t nitrogen
r e m o v a l i s s l i g h t l y h i g h e r w i t h η-heptane t h a n w i t h t o l u e n e (a
m o r e s i g n i f i c a n t d i f f e r e n c e was found w i t h Arabian topped crude
as t h e f e e d , T a b l e I V ) . The y i e l d o f h e a v y o i l f r a c t i o n i s l o w e r
( 3 7 ? f o r h e p t a n e a n d 57? for toluene) for the saturated solvent.
This means h y d r o c r a c k i n g was more e x t e n s i v e . The H/C atomic
r a t i o o f t h e h e a v y o i l i s a l s o much h i g h e r f o r h e p t a n e t h a n f o r
toluene. Thus, hydrogénation i s d e e p e r with heptane as the
solvent. Hydrogen consumption is also significantly reduced,
1200 s c f / b b l of shale o i l f o r heptane, versus 2600 s c f / b b l f o r
toluene. W i t h e v e r y t h i n g c o n s i d e r e d , h e p t a n e i s by f a r a b e t t e r
hydrotreating solvent than toluene.
Table VI. S u p e r c r i t i c a l Hydrotreatment o f Shale O i l i n Toluene

or n-Heptane
( 8 5 0 F , li+00 p s i g , N a l c o N i - M o C a t a l y s t ,
1.6 LHSV, 300 H 2 GHSV)
Run No. Feed Heavy O i l (>300F) Hp Consumption

Wt? N(ppm) S ( ? ) H7C Scf/Bbl"
16 20? S h a l e O i l 57 3149 <0.01 Ï7F6 2600 +_ 200
i n Toluene
17 20? S h a l e O i l 36 1595 <0.01 1.79 1200 ^100
i n Heptane
18 20? S h a l e O i l 37 1890 <0.01 1.82 1200 + 100
i n Heptane

22. LOW Hydrotreating in SupercHtical Media 293
Figure 5. Effect o f pressure on s u p e r c r i t i c a l hydrotreatment

of shale o i l .

Summary
Extensive r e s e a r c h has been done t o s t u d y the potential of

s u p e r c r i t i c a l hydrotreatment f o rt h e upgrading o f shale o i l and
the effects o f major reaction parameters i n supercritical
hydrotreating. The e x p e r i m e n t a l r e s u l t s have demonstrated that
hydrotreatment i n t h e presence of a light s o l v e n t and under
supercritical conditions h a s some a d v a n t a g e s over c o n v e n t i o n a l
hydrotreatment. Compared with a conventional process, t h e
s u p e r c r i t i c a l h y d r o t r e a t i n g process y i e l d s a better product (less
g a s , more d i s t i l l a t e s ) a n d p r o d u c e s l e s s coke on t h e c a t a l y s t .
S u p e r c r i t i c a l h y d r o t r e a t i n g a p p e a r s t o be a v e r y v e r s a t i l e p r o c e s s
which c a n be o p t i m i z e d f o r a v a r i e t y of different products.
This process c a n be a p p l i e d equally well f o r upgrading other
heavy o i l s , such as c o a l l i q u i d s and h i g h s u l f u r petroleum topped
crudes, to yield low nitrogen and s u l f u r syncrudes and
transportation fuels.
N - h e p t a n e was u s e
solvent. The s a t u r a t e
n i t r o g e n removal and hydrogen consumption. With either solvent,
sulfur removal was v e r y extensive. From reaction parameter
studies, a relatively high severity i s required f o r extensive
nitrogen removal.
Literature Cited
1. Blessing, J. E., and Ross, D. R., ACS Symposium Series
71, "Organic Chemistry of Coal", p. 15, 1978.
2. Whitehead, J. C., "Development of a Process for the
Supercritical Gas Extraction of Coal", paper presented
at the 88th AIChE National Meeting, June 1980.
3. Squires, T. G.; Aida, Tetsuo; Chen, Yu-Ying; Smith, Barbara
F., ACS Fuel Chemistry Preprints, Vol. 28 No. 4 p. 228,
1983.
4. Compton, L. E., ACS Fuel Chemistry Preprints, Vol. 28
No. 4 p. 205, 1983.
5. Williams, D. F., U.S. Patent 4 108 760, 1978.

Author Index
Abraham, Martin A., 67 Kumar, Sanat K., 88

Aida, Tetsuo, 58 Kwak, Τ. Υ., 101
Antal, Michael Jerry, J r . , 77 Lamb, D. Μ., 15
Bae, Y. C , 2 Low, J . Y., 281
Bagnell, Laurence J., 266 Mansani, Riccardo, 242
Barton, Paul, 202 Mansoori, G. Α., 101
Benmekki, Ε. Η., 101 Miin, Tiee-Chyau, 242
Bergstresser, T. R., 138 Moradinia, I r a j , 130
B r i t t a i n , Andrew, 77 Panagiotopoulos, A. Z., 115
Coppella, Steven J., 202 P a u l a i t i s , Michael E., 138
DeAlmeida, Carlos, 77 Ramayya, Sundaresh, 77
Deshpande, G. V., 25
Frye, S. L., 29, 172
Green, Thomas Κ., 242 Roy, ,
Gulari, Es., 2 Saad, H., 2
Hacker, D. S., 213 Shah, Y. T., 251
Holder, G. D., 251 Skelton, R. J., 189
Hum, Georgina P., 242 Smith, R. D., 29, 172
Johnston, K. P., 42 Squires, Thomas G., 58
Jonas, J., 15 Suter, U. W., 88
Jordan, J. W., 189 Taylor, L. T., 189
Kalkwarf, D. R., 29 Teja, Amyn S., 130
Kershaw, John R., 266 Warzinski, Robert P., 229
Kim, Sunwook, 42 Wright, R. W., 172
King, Jerry W., 150 Yonker, C. R., 29, 172
Klein, Michael T., 67
Subject Index
Benzylphenylamine—Cont inued
experimental conditions for
reaction, 6 8 t
n-Alkanes—See Solid n-alkanes major reaction products, 6 8 t
model s o l v o l y s i s and pyrolysis
through caged r a d i c a l
pair, 74,75f
reaction i n s u p e r c r i t i c a l
methanol, 69,71f,72
Batch reactors, use i n s u p e r c r i t i c a l water, 69,70f
extraction of coal, 251-252 reaction pathways neat and with
Benzylphenylamine supercritical fluid
apparent rate constants i n solvents, 72,75f
s u p e r c r i t i c a l solvents, 72,73t thermolysis, 69
effect of methanol density on Binary mixtures, theory, 91-93
conversion and product Binary mixtures of toluene and
s e l e c t i v i t y , 69,71f,72,74 meso-tetraphenylporphyrin, bubble
effect of water density on and dew points, I45t,156f,147
conversion and product Binary systems, phase-equilibrium
s e l e c t i v i t y , 69,70f,72,74 behavior, 118-120
295

Author Index
Abraham, Martin A., 67 Kumar, Sanat K., 88

Aida, Tetsuo, 58 Kwak, Τ. Υ., 101
Antal, Michael Jerry, J r . , 77 Lamb, D. Μ., 15
Bae, Y. C , 2 Low, J . Y., 281
Bagnell, Laurence J., 266 Mansani, Riccardo, 242
Barton, Paul, 202 Mansoori, G. Α., 101
Benmekki, Ε. Η., 101 Miin, Tiee-Chyau, 242
Bergstresser, T. R., 138 Moradinia, I r a j , 130
B r i t t a i n , Andrew, 77 Panagiotopoulos, A. Z., 115
Coppella, Steven J., 202 P a u l a i t i s , Michael E., 138
DeAlmeida, Carlos, 77 Ramayya, Sundaresh, 77
Deshpande, G. V., 25
Frye, S. L., 29, 172
Green, Thomas Κ., 242 Roy, ,
Gulari, Es., 2 Saad, H., 2
Hacker, D. S., 213 Shah, Y. T., 251
Holder, G. D., 251 Skelton, R. J., 189
Hum, Georgina P., 242 Smith, R. D., 29, 172
Johnston, K. P., 42 Squires, Thomas G., 58
Jonas, J., 15 Suter, U. W., 88
Jordan, J. W., 189 Taylor, L. T., 189
Kalkwarf, D. R., 29 Teja, Amyn S., 130
Kershaw, John R., 266 Warzinski, Robert P., 229
Kim, Sunwook, 42 Wright, R. W., 172
King, Jerry W., 150 Yonker, C. R., 29, 172
Klein, Michael T., 67
Subject Index
Benzylphenylamine—Cont inued
experimental conditions for
reaction, 6 8 t
n-Alkanes—See Solid n-alkanes major reaction products, 6 8 t
model s o l v o l y s i s and pyrolysis
through caged r a d i c a l
pair, 74,75f
methanol, 69,71f,72
Batch reactors, use i n s u p e r c r i t i c a l water, 69,70f
extraction of coal, 251-252 reaction pathways neat and with
Benzylphenylamine supercritical fluid
apparent rate constants i n solvents, 72,75f
s u p e r c r i t i c a l solvents, 72,73t thermolysis, 69
effect of methanol density on Binary mixtures, theory, 91-93
conversion and product Binary mixtures of toluene and
s e l e c t i v i t y , 69,71f,72,74 meso-tetraphenylporphyrin, bubble
effect of water density on and dew points, I45t,156f,147
conversion and product Binary systems, phase-equilibrium
s e l e c t i v i t y , 69,70f,72,74 behavior, 118-120
295

Biomass feedstocks, conversion Data reduction—Continued

processes, 77-78 midpoint of frontal breakthrough
Biphenyl p r o f i l e vs. elution peak
s o l u b i l i t y i n CCL vs. maxima, 1o1,l63f
pressure, I 8 0 , l 8 l f retention volume vs. adsorption
solute retention vs. c o e f f i c i e n t and surface area of
pressure, I80,l82f sorbent bed, 162
Butadiene recovery processes, Decay rate of order-parameter
advantages of s u p e r c r i t i c a l or fluctuations
n e a r - c r i t i c a l separation, 213 c r i t i c a l lines of three binary
systems, 5,6f
equation, 5
C
experimental procedures, 5
Cju separation, l i q u i d ammonia as vs. calculated c r i t i c a l and
solvent, 214 background contributions, 12,13f
Canonical p a r t i t i o n function, vs. temperatures and
d e f i n i t i o n , 89 pressures, 5,7,9t
Carbon dioxide-hydrocarbon e q u i l i b r i a , vs. transport c o e f f i c i e n t s , 3-4
modeling, 210 Destraction procedure
3-Caryphyllene, structure,
CO-water conversion
advantages, 245
effectiveness of CO, 245 Diffusion c o e f f i c i e n t i n the
inverse isotope e f f e c t , 247 s u p e r c r i t i c a l region, equation, 4
isotope effect, 245 1,3-Dioxolane, hydration i n
toluene-soluble products vs. CO water, 82,84f
consumed, 245,246f Dynamic renormalization group theory,
CO-water conversion process, description, 3
c h a r a c t e r i s t i c s of the medium, 243
CO-water conversion product analyses
H/C ratios of products, 247t
separations of toluene-soluble Ε
fractions, 245,247,248f
Coal conversion, vs. Hildebrand
s o l u b i l i t y parameter, 252 Enhancement factor, calculation, 47
Coal liquefaction Enskog theory
chemistry, 242 analysis of density dependence, 20
k i n e t i c studies, 242-249 c o e f f i c i e n t s , 20,23f
scheme for conversion in deviations, 20-21
hydrothermal Equation of state for 1-butene
systems, 247,248f,249 extraction, mixing rules, 216
Coal model compounds, reactant Equation of state modeling,
decomposition kinetics, 67 application to high-pressure phase
Coals, chemical analyses, 252,253t equilibrium behavior, 88
Compressed s u p e r c r i t i c a l ethylene, Ethanol dehydration i n s u p e r c r i t i c a l
s e l f - d i f f u s i o n , 18-21,23f water, conversion to
Compressed s u p e r c r i t i c a l toluene-dg, ethylene, 82,83t
s e l f - d i f f u s i o n , 21-22,23f Extraction of 1-butene
Conversion, d e f i n i t i o n , 253 analysis procedure, 219-220
C r i t i c a l densities, vs. corresponding e f f e c t of ammonia
compositions, 5 concentration, 225,226t
C r i t i c a l end points, location and e f f e c t of d i f f e r e n t
phase l i n e , 22,26f,27 solvents, 220,223t
Cubic equations of state, e f f e c t of temperature on
applications, 101-102 s e l e c t i v i t y , 220,224f
effectiveness of ammonia as
enhancing agent, 225
D equation of state, 216
experimental apparatus, 217,2l8f
Data reduction for retention volume experimental procedure, 219
measurements gas chromatographs, 220,221f
computation of retention volume influence of entraîner, 225
data, 161-162 influence of second solvent, 227

INDEX 297
Extraction of 1-butene—Continued H
sampling procedure, 219
s e l e c t i v i t y v s . ammonia
concentration, 220,224f Hard sphere diameters, c a l c u l a t i o n of
ternary-phase diagram, 220,221f theoretical Enskog
ternary phase equilibrium c o e f f i c i e n t s , 20
composition, 222-223t Heterolytic reactions v s . homolytic
reactions, 84
High-pressure gas chromatographic
F analysis of retention volume
adsorbent/adsorbate
classes, 160,161t
Flow reactors, use i n s u p e r c r i t i c a l apparatus, 156,159Γ,160
extraction of c o a l , 251 column design and preparation, 160
Fractional destraction experimental assessment of the
analysis of overhead fractions and column void volume, 160
the residue, 236,238t pneumatic transport of the
comparison of GPC r e s u l t s , 238,239f s o l u t e , 160
comparison of r e p l i c a t e High-pressure phase equilibrium of
destractions, 236,237
effect of temperature on
concentration, 236,237 schematic o equipment, 116,117f
elemental analysis of feed Homolytic v s . h e t e r o l y t i c
c o a l , 233,234t reactions, 84
experimental procedures, 230,232 Hydrotreating i n s u p e r c r i t i c a l media
f r a c t i o n a l destraction u n i t , 230 effect of nonaromatic
f r a c t i o n a l destraction solvent, 286t,293t
vessel, 230,231f effect of o i l
performance of f r a c t i o n a l concentration, 286,287f,288
destraction u n i t , 232 effect of pressure, 289,292f
two-step destraction procedures, 233 effect of space v e l o c i t i e s , 289,290f
vs. conventional d i s t i l l a t i o n , 230 effect of temperature, 289,291f
Fundamentals of s u p e r c r i t i c a l f l u i d experimental procedures, 282,284
adsorption feed properties, 284t
adsorption of a high-pressure hydrotreating system, 282,283f
gas, 152 reaction parameter studies, 289-293
breakthrough volumes, 156 s u p e r c r i t i c a l v s . conventional, 285t
effect of pore structure on treatment of Arabian topped crude
pressure, 154,155f, 156,157f o i l , 286t,288
effect of temperature on treatment of l i g n i t e extract, 288t
pressure, 154,155f treatment of s u p e r c r i t i c a l extracted
plot of reduced-state shale o i l , 285t,286
variables, 156,158f
pressure of adsorption maxima, 154
t y p i c a l adsorption isotherm for a
s u p e r c r i t i c a l gas, 152,153f I
Interaction parameters between binary

G components, values, 127,128t
I n t r i n s i c solvent strength,
d e f i n i t i o n , 50
G a s - l i q u i d equilibrium, measurement of
Isothermal compressibility of
dew and bubble points, 140
supercritical fluids,
Gel permeation chromatography,
determination, 175-177
determination of molecular
weight, 236,238t
Geranial, structure, 203,205f
Gram-Schmidt reconstructions Κ
of hexane, 193,194f
stack plot of C-H stretch Kamlet and Taft s c a l e , application
region, 195,196f and d e s c r i p t i o n , 30

Kinetic model for coal conversion Mode-coupling theory

description, 255 description, 3
e f f e c t of amount of dissolved dynamic renormalization group
fraction, 258 theory, 3-4
effect of coal-to-solvent Model of coal liquefaction
r a t i o , 263,264f effect of k i n e t i c s of reducing
e f f e c t of reaction time and density step, 249
on toluene effect of structure on
solubles, 255,256-257f,258 conversion, 244
effect of temperature, 258,259-2o0f schematic, 244,245f
model simulation, 258,261-262f,264f y i e l d of toluene-soluble
Kinetic studies of coal l i q u e f a c t i o n material, 244-245
CO-water conversions, 245,246f Modeling of e q u i l i b r i a , COp-
conversion products, 245,247,248f hydrocarbon systems, 270
experimental procedures, 243-244
model, 244-245,246f
s o l u b i l i t y , 47,49
Lemon o i l s o l u b i l i t y vs.
advantages of s u p e r c r i t i c a l pressure, 178,179f,l80
extraction, 202 solute retention vs.
c l a s s i f i c a t i o n s , 203 pressure, I80,l8lf
concentration, 203 Naphthalene-COp system
extractive d i s t i l l a t i o n with a c r i t i c a l end points, 22,24,26f,27
s u p e r c r i t i c a l solvent, 203-204 pressure-temperature diagram, 22,25f
gas chromatogram i n l i q u i d phase s o l u b i l i t y measurement, 24
sample, 206,207f Naphthalene s o l u b i l i t y i n
proposed process for s u p e r c r i t i c a l CO,,, NMR
concentration, 204 measurements, 22-27
Lemon oil-carbon dioxide equilibrium 2-Nitroanisole
ease of separation, 206 absorbance maxima, 3 2 , 3 3 t
experimental conditions, 204,206 absorption spectra, 31
r e l a t i v e v o l a t i l i t y , 206,208t e f f e c t of pressure on absorption
s e l e c t i v i t i e s , 210,211f maximum, 38,39f
s o l u b i l i t y diagrams, 206,209f peak position vs. reduced
s o l u b i l i t y l e v e l , 206,210,212 density, 32,35,36f
Limonene, structure, 203,205f pressure dependence of wavelength of
Liquid ammonia, use as solvent for C^ the absorption maximum, 32,34f
separation, 214 values vs. reduced density, 31
Local solvent compression, NMR measurements of naphthalene
determination, 51-52 solubility
Lorentz-Lorenz r e f r a c t i o n equation, experimental s o l u b i l i t i e s , 24,25f
calculation of r e f r a c t i v e isotherms, 24
index, 37 NMR spectroscopy
analysis of s u p e r c r i t i c a l
s o l u b i l i t y , 17-18
technique, 18
M
0
Mixed f l u i d solvent systems
nature, 37
spectroscopic vs. chromatographic Onsager reaction f i e l d theory
measurements, 38 description, 35,37
Mixing rules function vs. measured
Peng-Robinson equation of state, 101 values, 35
Redlich-Kwong equation of state, 104 Order-parameter fluctuations
van der Waals, 101 decay rate, 3-4

INDEX 299
Order-parameter f l u c t u a t i o n s — C o n t i n u e d R
description, 3
photon correlation spectroscopy, 3
time-averaged intensity Rapid i n j e c t i o n autoclave, use i n
measurements, 3 s u p e r c r i t i c a l extraction of
coal, 252
Rate constants
correlation with t r a n s i t i o n
Ρ energy, 48
predicted value for Diels-Alder
reaction, 48,49f
Patel-Teja equation of state, data Redlich-Kwong equation of state, 102
correlation for s o l i d n-alkanes i n Refractive index, calculation, 37
s u p e r c r i t i c a l ethane, 132,134 Regeneration of adsorbents, by
Peng-Robinson equation of state, 102 s u p e r c r i t i c a l f l u i d s , 151,153f
mixing rules, 104-105 Relative v o l a t i l i t y , d e f i n i t i o n , 206
modification, 127 Residue class separation,
Pentane results, 191,192t,193
selection as s u p e r c r i t i c a l f l u i d Residue-containing f o s s i l fuels
solvent, 139
vapor pressures, I40t,l4
Phase behavior of s o l i d s i n Retention volume measurements
supercritical fluids, data reduction, 161-162,l63f
applications, 138-139 high-pressure gas chromatographic
Phase-equilibrium behavior for binary apparatus, 156,159f,160,I6lt
systems, carbon dioxide solute capacity factors vs. column
ethanol, 1l8,120f pressure, I67,l68f,l69
Phase-equilibrium behavior for ternary solute capacity factors vs. gas
systems compression, 164-167,l68f
compositions f o r volume vs. C0 2
water-acetone-COp, 118,121t pressure, 162-166

concentration of acetone i n the
supercritical fluid
phase, 122,126f S
d i s t r i b u t i o n c o e f f i c i e n t for
water-acetone-C0 , 122,124f
2
salting-out e f f e c t , T18,122 Self-diffusion coefficients

s e l e c t i v i t y factor for acetone over i n deuterated toluene, 21-22
water, 122,125f i n s u p e r c r i t i c a l ethylene, 16
Phenol blue i n s u p e r c r i t i c a l toluene-dg, 16
t r a n s i t i o n energy i n COp, 44,45f predicted vs. measured
t r a n s i t i o n energy vs. COp values, 22,23f
mixtures, 52,53f,54 S e l f - d i f f u s i o n i n compressed
t r a n s i t i o n energy vs. s u p e r c r i t i c a l ethylene
density, 51,52f calculation of hard sphere
Photoisomerizations, experimental diameter, 20
procedures, 60 choice of ethylene, 18
Porphyrins, constituent i n crude c o e f f i c i e n t s vs. density and
o i l s , 139 temperature, l8,19f,20
Preparative-scale chemical class Enskog c o e f f i c i e n t s , 20,23f
separation, procedure, 190-191 Enskog theory, 20-21
Pressure-filter liquids, measurement conditions, 18
d e f i n i t i o n , 190 S e l f - d i f f u s i o n i n compressed
Properties of s u p e r c r i t i c a l f l u i d s , s u p e r c r i t i c a l toluene-dg
e f f e c t of pressure and c o e f f i c i e n t s , 21-22,23f
temperature, 59 polar gas model, 22
Pure-component parameters Separation of solution components from
determination, 90t the l i q u i d phase
estimation technique, 127,128t equations of state, 214
values, 90t influence of entrainers, 216
Pure components, theory, 89 solvents, 214

S o l i d n-alkanes Statistical-mechanics-based equation

heat of fusion v s . carbon of state—Continued
number, 130,131Γ behavior, 90-91
reasons for studying, 130 e f f e c t of s o l u b i l i t y of chains, 99
s o l u b i l i t i e s , 132-136 model behavior of
S o l i d - l i q u i d - g a s equilibrium solid-supercritical fluid
temperatures and pressures b i n a r i e s , 94,97f,98
c r i t i c a l endpoint, 141 predicted v s . experimental
measurement, 139 data, 94,95f,96
pressure-temperature projection of prediction for equilibrium f l u i d -
vapor pressure curve, 141 phase composition, 98f
values for binary mixtures, 141t s e n s i t i v i t y , 94
S o l i d s o l u b i l i t i e s in s u p e r c r i t i c a l trans-Stilbene
pentane, measurements, 140 effect of temperature on C0 p
S o l u b i l i t i e s for naphthalene, s o l u b i l i t y , 60,63f

measurement, 17 i n cyclohexane, 62t
S o l u b i l i t y of s o l i d n-alkanes in trans-Stilbene photoisomerization
s u p e r c r i t i c a l ethane concentration e f f e c t s , 62,63f
data c o r r e l a t i o n , 132,134 i n C 0 , 62,65t
2
enhancement factor vs. carbo

number, 134,136f
experimental and calculate Supercritica
s o l u b i l i t i e s , 134,135f of lemon o i l , 203
experimental results at S u p e r c r i t i c a l coal liquefaction
308.15 K, 132t procedure
single-pass s u p e r c r i t i c a l flow conversion products, 253,255
apparatus, 132,133f experimental apparatus, 253,254f
s o l i d properties required i n Supercritical distillation—See
s o l u b i l i t y c a l c u l a t i o n s , 134t Fractional destraction
Solute retention in s u p e r c r i t i c a l S u p e r c r i t i c a l extraction
f l u i d chromatography description, 115
effect of pressure, 172-173 factors influencing rate, 2
effect of temperature, 173 recovery of polar organic compounds
experimental apparatus and from aqueous s o l u t i o n s , 115-116
technique, 178 S u p e r c r i t i c a l extraction of coal
v s . density, 180 use of a rapid injection
v s . pressure for biphenyl, I80,l82f autoclave, 252
vs. pressure for use of batch reactors, 251-252
naphthalene, I 8 0 , l 8 l f use of flow reactors, 251
v s . s o l u b i l i t y and pressure, 175 S u p e r c r i t i c a l flow reactor
vs. temperature, 178 schematic, 79,80f
Solvating power, s c a l e , 30 temperature, 79,8lf
Solvatochromic data, experimental S u p e r c r i t i c a l f l u i d adsorption,
procedures, 43-44 fundamentals, 152-156
Solvatochromic probes S u p e r c r i t i c a l f l u i d chromatography (SFC)
absorbance maxima, 31-32 advantages, 189-190
experimental procedures, 31-32 a n a l y t i c a l applications, 151
Solvent effect on rate constants application as a mobile phase, 189
c o r r e l a t i o n with t r a n s i t i o n assumption of i n f i n i t e l y d i l u t e
energy, 47,48 s o l u t i o n s , 173
prediction of activation volume, 48t hexane separation, 193,194f,195,196f
Solvent strength, description, 43 measurement of physicochemical
Solvent strength in the c r i t i c a l data, 151
region, 44 relationship among solute
Source and purity of n-alkanes, 132 retention, s o l u b i l i t y , and
S p e c i f i c solvent strength, pressure, 175
d e f i n i t i o n , 50 relationship between solute
Spectroscopic solvatochromatic retention and
parameter, d e s c r i p t i o n , 43 temperature, 175-177
Statistical-mechanics-based retention factor, 173
lattice-model equation of state separation of p o l y c y c l i c aromatic
a p p l i c a b i l i t y to mixture of hydrocarbons, 195,197f
different size molecules, 94,96f s o l u b i l i t y of a solute, 174

INDEX 301
SFC—Continued S u p e r c r i t i c a l water—Continued
solute Chemical p o t e n t i a l , 173 role of carbocation chemistry, 84-85
toluene separation, 195,198f,199 thermophysical properties, 78-79
S u p e r c r i t i c a l f l u i d extraction, S u p e r c r i t i c a l water extractions of
advantages over conventional coal
extraction techniques, 15 analysis of o i l
S u p e r c r i t i c a l f l u i d extraction f r a c t i o n s , 271,274t,276f
modeling, applications, 105-110 a n a l y t i c a l data f o r
S u p e r c r i t i c a l f l u i d extraction of 1 λ residues, 271,274t
coal ^C-NMR spectra of
analyses of coals, 267,268t f r a c t i o n s , 271,273f
potential use, 266-267 conversion v s . v o l a t i l e matter
solvents, 266 content, 269,270f
water v s . aqueous effect of pressure, 274,275t,276f
solvents, 277,278f,279t e f f e c t of temperature, 275t,277
water v s . toluene, 277,278f extract analysis, 271,272t
Supercritical fluid extract composition, 269,270f,271
extraction-chromatography
a n a l y t i c a l procedures, 191
d isadvantages, 193
Gram-Schmidt
reconstruction, 193,194f
S u p e r c r i t i c a l f l u i d reactant addition
system, diagram, 60,6lf Ternary systems, phase-equilibrium
S u p e r c r i t i c a l f l u i d reactor, behavior, 118-126
schematic, 60,6lf meso-Tetraphenylporphyrin
S u p e r c r i t i c a l f l u i d solvents melting behavior, 147
advantages, 42-43 s o l i d s o l u b i l i t i e s i n various
properties, 44,46t solvents, I47t,l48
Supercritical fluids Theory of c r i t i c a l fluctuations
applications, 58-59,150-151 effect of impurities, 10
constraints for organic reaction parameter values, 10,11t
investigations, 59 range of v a l i d i t y , 12
c r i t i c a l properties, 32t Thermodynamic model for vapor-liquid
desorption of adsorbates, 151,153f equilibrium calculations
e f f e c t of additional components on pressure-composition
solvating properties, 37-38,39f diagrams, 111,112f-113f
peak position v s . reduced theory, 111
density, 32,35,36f Thermodynamic model of s u p e r c r i t i c a l
pressure dependence of f l u i d extraction
wavelength of the absorption effect of mixing rules on s o l u b i l i t y
maximum, 32,34f of s o l i d s , 105,106-110f
solvent properties, 58 theory, 105
solvent-solute interactions, 29-39 Toluene
use as solvents, 29 effect on c o a l , 255
values v s . reduced density, 35,36f s e l e c t i o n as s u p e r c r i t i c a l f l u i d
S u p e r c r i t i c a l gas extractions solvent, 139
method A procedure, 267 vapor pressures, I40t,l4l
method Β procedure, 267,269 Transition energy
S u p e r c r i t i c a l phase, d e f i n i t i o n , 2 influencing factors, 50-51
S u p e r c r i t i c a l s o l u b i l i t y measurements of nonpolar solvents, 46t
schematic of a l l , 17,19f of phenol blue i n C0 v s . 2
use of NMR spectroscopy as an density, 44,45f

a n a l y t i c a l technique, 17-18 of phenol blue i n C0 v s . 2
S u p e r c r i t i c a l solvents, effects on the pressure, 44,45f

rates of homogeneous chemical of phenol blue v s . CO^
reactions, 42-54 mixture, 52,53f,54
S u p e r c r i t i c a l solvents as a reaction of phenol blue v s . density, 51,52f
medium, thermophysical vs. reduced density, 46
properties, 78 Transport properties
S u p e r c r i t i c a l water background, 4
ethanol dehydration, 82,83t mass conductivity, 4

V Vapor-pressure osmometry,
determination of molecular
weight, 236,238t
π* values Vapor pressures, for pentane and
for s u p e r c r i t i c a l CO^, 35 toluene, I40t,l4l
vs. reduced density, 35,36f Vapor-liquid equilibrium apparatus
van der Waals equation of state diagram, 204,205f
general, 101 estimated r e l a t i v e errors, 204
mixing rules, 101-102 Vapor-liquid equilibrium calculations,
van der Waals mixing rules applications, 111,112—113f
Volume expansivity of a s u p e r c r i t i c a l
guidelines, 103
fluid, vs.
theory, 102-103 temperature, I80,l83,l84f
Production by Paula M. Bérard

Indexing by Deborah H. Steiner
Jacket design by Pamela Lewis
Elements typeset by Hot Type Ltd., Washington, DC

Punted and bound by Maple Press Co., York, PA


(ACS Symposium Series 329) Thomas G. Squires and Michael E. Paulaitis (Eds.) - Supercritical Fluids. Chemical and Engineering Principles and Applications-American Chemical Society (1987) PDF

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(ACS Symposium Series 329) Thomas G. Squires and Michael E. Paulaitis (Eds.) - Supercritical Fluids. Chemical and Engineering Principles and Applications-American Chemical Society (1987) PDF

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Supercritical Fluids

In Supercritical Fluids; Squires, T., et al.;

Thomas G. Squires EDITOR

Michael E. Paulaitis, EDITOR

Developed from a symposium sponsored by

American Chemical Society, Washington, DC 1987

In Supercritical Fluids; Squires, T., et al.;

American Chemical Society

Alan Elzerman W. H. Norton

John W. Finley James C. Randall

Marye Anne Fox W. D. Shults

Martin L. Gorbaty Geoffrey K. Smith

Roland F. Hirsch Charles S.Tuesday

Rudolph J. Marcus Douglas B. Walters

Vincent D. McGinniss C. Grant Willson

In Supercritical Fluids; Squires, T., et al.;

In Supercritical Fluids; Squires, T., et al.;

SCIENTISTS HAVE BEEN AWARE of the novel properties of supercritical

In Supercritical Fluids; Squires, T., et al.;

August 28, 1986

In Supercritical Fluids; Squires, T., et al.;

Effect of Critical Phenomena on Transport Properties

Department of Chemical and Metallurgical Engineering, Wayne State University,

The transport properties of supercritical fluid mixtures

results along c r i t i c a l isochores were analyzed in terms of

8.9 MPa. T h e r e f o r e , f r e q u e n t l y a p r o c e s s o p e r a t i n g a t 40 C and a t

In Supercritical Fluids; Squires, T., et al.;

These fluctuations, which are r e f e r r e d t o as order-parameter

where ε = (Τ - Τ )/T , ξ 0 i s a system-dependent a m p l i t u d e and V=

In Supercritical Fluids; Squires, T., et al.;

p a r t i t i o n e d i n t o a c r i t i c a l p a r t and a background which c o r r e s p o n d s

where ÎI, t , and AL, A D denote the background and the c r i t i c a l

where kg i s Boltzmann's c o n s t a n t , η is viscosity, q = 2q sin(9/2), o

with q and θ b e i n g the wave number o f the i n c i d e n t l i g h t and the

where A i s a system-dependent a m p l i t u d e which can be t r e a t e d as a

The above e q u a t i o n p r o v i d e s a basis for correlating the

In Supercritical Fluids; Squires, T., et al.;

that C0 2 and decane form more asymmetric m i x t u r e s r e l a t i v e t o C 0 2

when t h e temperature dependence o f ξ i s substituted i n . η was

In Supercritical Fluids; Squires, T., et al.;

F i g u r e 1: P l o t o f the hydrocarbon content of v a r i o u s mixtures

300 310 320 ~530

In Supercritical Fluids; Squires, T., et al.;

44.,49 c 8..50 c 0.,74 + 0.01

In Supercritical Fluids; Squires, T., et al.;

Table I I : Measured Γ/q a t V a r i o u s Temperatures and P r e s s u r e s :

95. 5 mol % CO , ffc= 0.579 g/cm 3

Τ (39,.30 + 0. 02) °C Ρ = 8.,06 MPa

98..6 mol % CO , Ρ = 0.533 g/cm 3

Τ = (36 .31 + 0. 02) °c, Ρ = 7,.78 MPa

36..56 c 7,.82 c 1. 05 + 0.02

In Supercritical Fluids; Squires, T., et al.;

Τ = (43.05 ± 0 . 0 2 ) °C, Ρ = 8.73 MPa

Τ = (35.86 ± 0 . 0 2 ) °C, Ρ = 7.82 MPa

In Supercritical Fluids; Squires, T., et al.;

density using η = 42.58p+ 661.7p + 82.89p + 152 + 1 2 5 G from

and Q, which i s a system-dependent amplitude, i s r e l a t e d t o t h e

In Supercritical Fluids; Squires, T., et al.;

98.1 m o l % CO 0.68 + 0.06 0.69 _+ 0.02 0.76 + 0.04 0.51 + 0.15

96.9 m o l % CO 0.60 + 0.07 0.76 + 0.03 1.09 + 0.08 1.80 + 0.25

94.4 mol% CO 0 . 9 8 + 0.17

96.8 m o l % CO 0.42 + 0.11 0.85 + 0.07 1.21 + 0.03 2.95 + 0.07

95.5 m o l % CO 0.58 + 0.05 0.74 + 0.02 0.92 + 0.01 1.17 + 0.05

F i g u r e 1. Schematic drawing o f NMR sample c e l l for super

1. Irani C. A.; Funk, E. W. "Recent Developments in Separa