Fluid Phase Equilibria, 68 (1991) 263-280 263

Elsevier Science Publishers B.V., Amsterdam

Solubilities of theobromine and caffeine in supercritical

carbon dioxide: correlation with density-based models

Shufen Li, G.S. Varadarajan ’ and Stanley Hartland *

Department of Chemical Engineering and Industrial Chemistry,
Swiss Federal Institute of Technology, CH-8092 Zurich (Switzerland)
(Received November 6, 1990; accepted in final form July 1, 1991)

ABSTRACT

Li, S., Varadarajan, G.S. and Hartland, S., 1991. Solubilities of theobromine and caffeine in
supercritical carbon dioxide: correlation with density-based models. Fluid Phase Equilib-
ria, 68: 263-280.

Solubilities of theobromine and caffeine in supercritical carbon dioxide at several

different temperatures (40, 60, 80 and 95°C) and pressures from 80 to 300 bar were
measured using a dynamic method. The solubilities of theobromine were two orders of
magnitude less than those of caffeine even though both compounds are xanthines with very
similar chemical structures. The reasons are considered from a thermodynamic viewpoint.
The applicability and limitations of three density-based models used to correlate the data
are discussed.

INTRODUCTION

Extraction of caffeine from coffee with supercritical fluid carbon dioxide

has been investigated and patented by numerous researchers and has
become commercially viable during the past twenty years (McHugh and
Krukonis, 1986). However, only one patent exists for the removal of the
stimulant theobromine from cocoa with supercritical carbon dioxide
(Margolis et al., 1982).
Cocoa beans provide the raw materials for chocolate and other foods.
They contain small amounts of the stimulant theobromine and some

i Institute of Polymer Chemistry, Swiss Federal Institute of Technology, Zurich, Switzer-

land.
’ Author to whom correspondence should be addressed.

03783812/91/$03.50 0 1991 Elsevier Science Publishers B.V. All rights reserved

264

caffeine, which it is desirable to remove from the food product, especially

as they are themselves pharmaceutically important.
Theobromine and caffeine have similar chemical structures, both being
methyl-substituted xanthine stimulants. The question arises as to whether
theobromine can be extracted with CO,. In order to assess the possibility
of extracting theobromine and caffeine from cocoa beans, the solubilities of
pure theobromine and caffeine in CO, were measured using a dynamic
method. Published data for the solubility of caffeine have been graphically
presented by Stahl and Schiltz (1979), Gaehrs (1984), Ebeling and Franck
(1984), McHugh and Krukonis (1986) and Lentz et al. (1986). However, no
solubility data for theobromine exist.
In order to find the optimal design and operating conditions for further
development of a practical commercial process, it is useful to extend
theoretical models for correlating and predicting solid-fluid equilibrium.
Although equations of state are generally used, the lack of both fundamen-
tal thermodynamic data for some organic substances and a full understand-
ing of the supercritical fluid state limit their accuracy. Other kinds of
models, such as density-based correlations have been developed in recent
years (Chrastil, 1982; Ziger and Eckert, 1983; Schmitt and Reid, 1985). In
this study, three density-based models are used to correlate the data for the
theobromine + CO, and caffeine + CO, binary systems; their applicability
and limitations are discussed.

EXPERIMENTAL

A schematic diagram of the equilibrium solubility experimental appara-

tus is shown in Fig. 1, which is similar to that of Krukonis and Kurnik
(1985) and Kurnik et al. (1981).
The heated feed gas, carbon dioxide, was compressed with a single-stage
compressor and then charged into a 2 1 on-line heated surge tank. The
desired pressure was controlled by a pressure regulator (series 44-1100,
Tescom Corp.), which was fitted at the outlet of the surge tank. The
high-pressure fluid CO, passed through a tube preheater to reach the
desired temperature before entering the extraction column. This was 4.5
cm in diameter and 31 cm long, being packed with alternate layers of the
test solid and glass wool. The inlet and outlet of the column were closed by
metal filter discs (threshold 7 pm) to minimize entrainment of the test
solid. The column was heated electrically and the temperature was moni-
tored and controlled by a thermocouple combined with a PID regulator
(Eurotherm type 070) to within & 1°C. The pressure was measured with a
calibrated pressure gauge mounted at the outlet of the column, to an
 265

Fig. 1. Schematic diagram of the experimental apparatus: 1, liquid CO, cylinder; 2,

compressor; 3, heated surge tank; 4, preheater; 5, extraction column; 6, ice-water bath; 7,
U-tubes; 8, wet test meter; 9, heating tape; P, pressure gauge; PC, pressure control
regulator; T, temperature meter; TIC, temperature indicating control; V, valve; MV,
micrometer valve.

accuracy of 1% over the measuring range. The pressure drop across the
bed was negligible.
The supercritical carbon dioxide with dissolved solid passed from the
extractor through a heated micrometer valve (SS-4M0, Nupro Co.) which
controlled the flow rate and was subsequently expanded to ambient pres-
sure. The dissolved solids were precipitated in two consecutive tared
U-tubes, which were immersed in ice-water solution and packed with glass
wool at their outlets to reduce entrainment. Most of the solid was usually
trapped in the first U-tube. The total volume of the solute-free low-pres-
sure gas was measured by a calibrated wet test meter at a known tempera-
ture and pressure.
The flow rate was controlled at 0.3 standard 1 min-’ by the micrometer
valve, varying from 0.1 to 0.4 standard 1 min-‘, and the test indicated that
the flow rate did not effect the equilibrium solubility within this range. The
tube from the extractor to the micrometer valve was wrapped with heating
tape to maintain the temperature at that of the extractor.
An equipment reliability test was made with the naphthalene + carbon
dioxide system at 318 K. The mass of solid collected was found by weighing
the U-tube on a Mettler balance accurate to f 1 mg. Comparing the
solubilities measured by us with the data of Tsekhanskaya et al. (1964), the
average deviation is within 7%.
266

For theobromine and caffeine in carbon dioxide, since their melting

points were much higher but their solubilities much lower than those of
naphthalene, UV-spectrometry (Philips PU 8700 series) was used. Less gas
was used and solid plugging inside the micrometer valve was avoided. The
maximum absorption peak for theobromine and caffeine was found to be
272.7 nm and their specific extinction coefficients in water (1 mg in 100 ml)
were 563 and 507 respectively (Li et al., 1990).
The carbon dioxide was 99.9% pure, containing less than 130 ppm water.
The chemicals naphthalene, theobromine and caffeine were supplied by
Fluka Chemie (Switzerland) with individual purities of 99% (GC), 98%
(HPLC) and 99% (HPLC), respectively; all chemicals were used without
further purification.

RESULTS AND DISCUSSION

The experimental solubilities of pure caffeine in supercritical CO, at

different temperatures (40, 60, 80 and 95°C) and a range of pressures from
80 to 300 bar are reported in Table 1. The solubilities of theobromine in
CO, at three temperatures (60, 80 and 95°C) and the same pressure range
are reported in Table 2. If the parameter pressure is replaced by density,
which is taken from IUPAC data (Angus et al., 19731, the relationships are
somewhat simplified, as shown in Figs. 2 and 3. This is because two
competing factors influence solute solubility in a supercritical fluid. Raising
the temperature increases the vapor or sublimation pressure of the solute
and hence the solubility of the solute. However, increasing the temperature
simultaneously decreases the density of the CO, which tends to decrease
the solubility. As the pressure increases, the density of the supercritical
fluid becomes less temperature-sensitive and the vapor pressure of the
solute tends to dominate, so that the solubility of the solute increases with
temperature. A solubility maximum may occur, but the solubility of a solute
always increases with increasing density of the supercritical fluid.
Most previous authors present data on caffeine-CO, in graphical form
(only Ebeling and Franck (1984) tabulate their data). The ranges of
pressure and temperature vary, so we could only make rough comparisons
at 60°C (shown in Fig. 4(a)) and at 40 and 80°C (shown in Fig. 4(b)). It can
be seen that for these temperatures our data agree with those of Stahl and
Schilz (1979) and Ebeling and Franck (1984) at pressures up to 200 bar. At
higher pressures at 60°C one data point of Ebeling and Franck is lower and
two data points of McHugh and Krukonis (1986) are higher than our data.
Gaehrs’ (1984) data (not shown) were even higher, perhaps owing to
different methods of measurement and analysis. However, in general the
trend is consistent.
 267

TABLE 1
Solubility of caffeine in supercritical CO,

Temperature Pressure D&&y Mole fraction Enhancement

(“0 (bar) k 1-l) factor
40 95 573.71 1.51 x 10-5 3.86 x 10’
148 775.99 1.31 x 10-4 5.22 x 106
198 838.43 1.97 x 10-4 1.05 x 107
243 875.04 2.78 x 1O-4 1.82 x lo7
298 909.79 3.60 x 1O-4 2.89 x lo7

60 106 332.34 2.74x 10W6 6.09 x lo3

112 369.78 4.40x 10-6 1.03 x 104
148 594.43 5.05 x 10-5 1.57 x 105
200 725.01 1.80x 1O-4 7.55 x 105
225 756.38 2.68x 1O-4 1.26 x lo6
242 777.70 3.06 x 1O-4 1.55 x 106
265 800.69 3.77x 10-4 2.09 x lo6
298 829.19 4.14 x 10-4 2.59 x lo6

80 105 243.61 1.94x 10-6 4.44 x 102

148 423.00 2.77 x 1O-5 8.94 x lo3
198 589.78 1.51 x 10-4 6.52 x lo4
236 662.12 2.82x 1O-4 1.45 x 105
268 708.96 4.01 x 10-4 2.34 x lo5
298 744.41 4.82x 1O-4 3.13 x 105

95 80 145.83 4.75 x 10-7 1.78 x 10’

150 352.47 2.18 x 1O-5 1.97x 103
198 506.52 1.25 x 1O-4 1.16x lo4
238 588.19 2.80 x 10 -4 3.13 x 104
266 635.93 4.63 x 1O-4 5.78 x lo4
680.83 5.15 x 10-4 7.21 x lo4

Compared with the solubility of caffeine in CO,, the solubility of

theobromine in CO, was much lower. When the pressure was higher than
200 bar, the solubilities of theobromine were even two orders of magnitude
less than those of caffeine. It is thus more difficult to extract theobromine
with CO, than caffeine.
The large difference in the solubilities of caffeine and theobromine in
carbon dioxide may be explained by intermolecular forces. As shown in
Table 3, the only difference between the molecular structures of theo-
bromine and caffeine is that the methyl group (CH,-) in caffeine is
replaced by hydrogen (H-1, which is an electron acceptor in the presence
of sufficiently negative atoms (here nitrogen in the ring and carbonyl
oxygen), so that hydrogen bonds are formed between theobromine
268

TABLE 2
Solubility of theobromine in supercritical CO,

Temperature Pressure Density Mole fraction Enhancement

(“0 (bar) (g 1-l) factor
60 150 606.91 6.29x lo-’ 6.12x 10’
200 725.01 6.90x lo-’ 8.95 x 10’
240 775.19 7.93 x 10-7 1.23 x 10’
300 830.92 1.13 x 10-6 2.18 x lo8

80 150 431.34 6.76x lo-’ 1.86 x 106

200 596.38 1.07x 10-6 3.93 x 106
240 669.43 1.20 x 10-6 5.29x106 *
268 708.96 1.34x 10-6 6.60 x 106
300 746.77 1.77 x 10-6 9.75 x 106
95 100 196.04 2.70x lo-’ 4.50 x 104
200 508.08 1.29 x 10-6 4.30 x 105
240 592.40 1.91 x 10-6 7.64 x 10s
270 641.54 2.16x 1O-6 9.72 x 10s
300 683.63 2.98x W6 1.49 x 106

molecules. The additional cohesive force makes the melting point and
enthalpy of sublimation of theobromine appreciably larger than those of
caffeine. The physical properties listed in Table 3 (Weast, 1975; Martin et
al., 1981) support this explanation.
To a good approximation, the solubility of a solid solute in a liquid
solvent can be expressed (Reid et al., 1988) as
ln (54 = - (&/RT)(l - VL) (1)
where y is the activity coefficient of the solute, x2 is its solubility (mole

6.0

0 4oDc
. 6OoC

4.0: A 8oDc
A 95T

0 200 400 600 600 1000

Density (g/L)

Fig. 2. Experimental solubilities of the caffeine+CO, system as a function of solvent

density.
 269

4.0

l 6OT
A 8OQC
3.0 .

2.0

1 .o

0 200 400 600 600 1000

Density (g/L)

Fig. 3. Experimental solubilities of the theobromine+CO, system as a function of solvent

density.

fraction) in the solvent at the system temperature T,T, is its melting point,
h, its enthalpy of fusion and R the gas constant. If y2 = 1, the ideal
solubility of the solute in the liquid solvent at temperature T will depend
only on the properties of the solute. It is easy to see from eqn. (1) that, at
constant temperature, the higher the melting point and the enthalpy of
fusion, the smaller the solute solubility x2.
Equation (1) can also be used to explain qualitatively the solubility
differences if the supercritical fluid is considered as an expanded liquid. If
we neglect the effect of intermolecular forces between the solute and
solvent (by setting y = l), the ideal solubility of theobromine would then be
about two orders of magnitudes less than that of caffeine, as is also shown
in Table 3.
Actually, the solubility of a solid depends not only on its properties but
also on those of the solvent, as well as the operating conditions, such as
temperature and pressure. The solubility of a solid solute in a gas is much
lower than the ideal solubility. Ways of increasing the solubility of theo-
bromine in supercritical CO, in order to develop a practical process for
extracting theobromine from cocoa beans will be discussed elsewhere. In
this work, only modeling and data correlation are presented.
Prausnitz et al. (1986) have derived an equation for the solubility of a
solid in a supercritical fluid considered as a compressed gas:
y, = (P;ub/P)E (2)
where the enhancement factor E is defined by

/Iu,Vf dP/RT
p2
E= SCF (3)
$2
270

0.250
(a) 0
T=60%
0

s 0.150

6
‘2
:: 0.100

h
2 0.050
.p
3 0.000

-0.050 t I . I I

100 150 200 250 300

pressure (bar)

0.250
(b)
0.200 - /LO%
I

s 0.150 -

s
‘2 0 100 -
::
1=
z 0.050 :
.Ln
g 0.000 [

-0.050 1 a ’ I ’ - -1
50 100 150 200 250 300 350

pressure (bar)

Fig. 4. Comparison of the solubilities of the caffeine+CO, system as measured by the

present authors with the literature values. (a) T = 60 ’ C: 0, this work; A, Stahl and Schilz
(1979); q , Ebeling and Franck (1984); o, McHugh and Krukonis (1986). (b) T = 40 and
80” C: 0, o, this work; A, Stahl and Schilz (1979); 0, Ebeling and Franck (1984).

When the fugacity coefficient of the pure solute, +yb is assumed to be

unity, the variation of the molar volume of the pure solid V$ with pressure
is neglected, and the operating pressure P is much greater than the solid
sublimation pressure, Pyb, the definition may be simplified to
E = ( 1/4zCF) exp( V[P/RT)
or log E = -log 4;“” + V;“P/2.3RT
The value of the fugacity coefficient of a solid in a fluid phase 4;“” is a
function of pressure, temperature and fluid composition, which can be
modeled with an equation of state, such as the Redlich-Kwong or Peng-
Robinson equations. However, these traditional methods require the criti-
cal parameters of both the solvent and solute, and the latter are often
 271

TABLE 3
Schematic molecular structure and properties of caffeine and theobromine

Properties Caffeine Theobromine

C,HUJ,% C,HsWz

Molecular structure

Molecular weight (g mol- ‘I 194.2 180.18

Melting point ( ’ Cl 238 351-357
Sublimation point CC) 178 290
Heat of fusion at melting point (cal mol-‘1 5044 9819
Density at 25°C (g cmm3> 1.321 1.419
1.349 1.453
Dipole moment (Debye) 3.83 a 3.11 a
Ideal mole fraction solubility, Xi
at 25 o C 0.0287 0.00018
60°C 0.0703 0.00103
80°C 0.108 0.00238
a Measured in acetic acid solvent.

unavailable in the literature. Although these can sometimes be accurately

estimated, such as by Lydersen’s technique (1982), large errors occur for
some kinds of solute.
For example, in the systems investigated, theobromine and caffeine
sublime before their melting point, so their boiling points cannot be found.
Furthermore, theobromine and caffeine contain different kinds of nitrogen
bonding in which the group contribution values are either not known or the
accuracy cannot be guaranteed, making estimation of the critical parame-
ters unreliable.
In recent years, three empirical, semi-empirical or theoretical density-
based correlations have been developed which do not need critical parame-
ters (Chrastil, 1982; Ziger and Eckert, 1983; Schmitt and Reid, 198.5).
Gurdial et al. (1989) have made a comparison using a wide range of organic
solutes of different polarity with supercritical CO,. Here we use our
experimental data to discuss further their applicability and limitations.
log c vs. log p
Based on the association viewpoint that one molecule of a solute A can
associate with k molecules of solvent B, forming a solvato complex molecule
272

TABLE 4
Association constant k and intercept (determined from eqn. (4)) for caffeine and theo-
bromine in CO,

Caffeine Theobromine
Temperature ( o C) 40 60 80 95 60 80 95
Slope (k + 1) 6.87 5.60 4.99 4.58 1.64 1.61 1.82
Intercept - 23.8 - 19.7 - 17.6 - 16.2 - 10.8 - 10.4 - 10.7
R value 0.99 0.99 0.99 0.99 0.87 0.98 0.99

AB, which is in equilibrium with its surroundings, Chrastil(1982) derived a

logarithmic relationship between the solute concentration (c, in g 1-l) and
the supercritical fluid solvent density (p, in g 1-l):
c(g 1-l) =pk exp (a/T+b)
where a and b are constants which depend on the heat of solvation. An
equivalent expression may be derived in which c is expressed as a mole
fraction (Gurdial et al., 1989):
c (mole fraction) = p “+‘(M,/M,) exp (a/T+b) (4)
These equations suggest that plots of log c vs. log p should yield parallel
straight lines at different temperatures, the constants a and b being
determined from the intercepts of the isotherms.
The association constant k and intercepts are reported in Table 4. It can
be seen that the linearity is excellent for the caffeine + CO, system (the
regression coefficient R > 0.99). For the theobromine + CO, system, it is
still good (R > 0.97) except for the line at 60 ’ C (R > 0.87). However, the
fact that the slope of the solubility isotherms for the caffeine + CO, system
decreases with increasing temperature indicates that the association con-
stant k is a function of temperature, as found by Wells et al. (1990). The
lines for the theobromine + CO, system, however, are almost parallel and
the k value is less than 1. Gurdial et al. (1989) found that only for
low-polarity compounds were the solubility isotherms parallel and linear.
As the solute polarity increased, the lines became less parallel. The dipole
moments of caffeine and theobromine are about 3.83 and 3.11 Debye
(Aaron et al., 1987) respectively, indicating that their polarity is higher.

log E us. p correlation

If eqn. (2) is rewritten

E = y,/( Pub/P) (5)
 273

TABLE 5
Estimated thermodynamic properties of caffeine and theobromine

Caffeine Theobromine
Boiling point (K) 628.2 750.8
Solubility parameter at 25°C (Cal cm-3)0.5 13.5 14.0
Density at 25 ’ C (g cme3) 1.333 1.430
Sublimation pressure at 40°C (bar) 3.717x 10-9
60°C 4.769x IO-’ 1.542x10-‘2
80°C 4.583 x 1O-7 5.445 x lo-”
95°C 2.129 x 10-6 5.695 x lo- “’

it is clear that the enhancement factor E can be considered as the ratio of

the observed equilibrium solubility ( y,) to the ideal solubility in the gas
(yi = PSUb/P).
Enhancement factors for caffeine and theobromine in CO, at different
pressures and temperatures are listed in Tables 1 and 2, in which the
sublimation pressure for caffeine was calculated according to the equation

log Psub(Pa) = -(A/T) +B A =5781(K) B = 15.031

by Bothe and Cammenga (1979); for theobromine it was estimated from the
modified Watson correlation (1982). The values are reported in Table 5.
A purely empirical correlation of log E vs. p made by Schmitt and Reid
(1985) is based on their observation that plots of log E vs. pure solvent
density exhibit a characteristic fine splitting of the solubility isotherms such
that they form a set of closely spaced, yet distinct, parallel lines. The
correlation is as follows:

where (Yand p represent the slope and intercept at the reference tempera-
ture T = Tref respectively and u represents the isotherm spacing constant
which can be determined from a plot of log E vs. temperature at a chosen
reduced solvent density.
The plots of log E versus solvent density for the caffeine + CO, system
are shown in Fig. 5, in which the regressed data are taken from only
p > 300 (g 1-l). It can be seen that the solubility isotherms at 40 and 6O”C,
and those at 80 and 95X!, are close to parallel. However, if the data from
the solvent density of 100 fg 1-l) are included, some deviation occurs. The
plots for the theobromine -i-CO, system are shown in Fig. 6. Here also it
can be seen that the solubility isotherms at 60 and 80°C are close to
parallel but that at 95°C they deviate somewhat; fine splitting cannot be
seen. The empirical observations of Schmitt and Reid (1985) are limited
274

102
300 400 500 600 700 800 900 1000

Density (g/L)

Fig. 5. Semi-log correlation for the solubility .enhancement factor of caffeine in CO, with
density.

not only to a few non-polar organic substances but also a narrow tempera-
ture range and solvent density range. They may therefore not satisfactorily
correlate solutes with a higher polarity, or over a wider temperature and
density range. If log c vs. density p is plotted, a set of closely parallel lines
can be obtained for the caffeine + CO, system, but not the theobromine +
CO, system. These further indicate that the applicability of the pure
empirical semi-log correlation depends on the system selected.

log E vs.[&A /y,)(2 -A /yl) - logO + s:/P)/

A semi-empirical model based on regular solution theory and the van

der Waals equation of state was developed by Ziger and Eckert (1983) as

109
0 60 “C
108
i
A 80 'C
A 95 “C

107 i

::; 9

104
0 200 400 600 800 1000

Density (g/L)

Fig. 6. Semi-log correlation for the solubility enhancement factor of theobromine in CO,
with density.
 275

follows:

log E = +2”(A/iy ‘1)- 1% (1+ iq/P)f f v2 (71

where 7 and ‘v are regression constants that are characteristic for each
solvent and solute, S, = &~,)*‘~p~is the solubility parameter for the super-
critical fluid solvent in which a, is the van der Waaks constant, A = S,/Szs
and ~2*= (&,j2&f2.3 RT, a dimensionless energy parameter.
Application of eqn. 7 requires evaluation of several pure ~rn~~~~nt
thermodynamic properties. Originally, Ziger and Eckert (1983) treated the
solid solute as a sub-cooled liquid and extrapolated liquid properties from
the melting point using thermal coefficients. Gurdial et al. (19891 suggested
using the atomic and group ~on~but~o~ method proposed by Fedora
(1974). Since the thermal coefficients for caffeine and t~e~bromine are also
not easy to find, the latter method is used. As this gives S, only at 25 a C,
the value of S, at the desired temperature is calculated from the following
formulae suggested by Fedors (19741:

6, = &[l f l.l3ar,(T, - TJ (AR5O”C) (8)

6, = 8Tl(~r,/J$J1.13 = fil.~pr,/PT,)1.13 (AT < 150°C) (91

where cy, is the thermal exp~sion coefficient. Since this is norrn~l~y
un~own~ both Ziger and Eckert ff9$33) and Gurdial et al, ~~989~ use the
published value for naphthalene fa, = 0~~7 K-l: Vargaftik (1975)) for alf
solutes. Since the density at T2 must also be estimated, Grain’s method
(19821 is used, in which the boiling point Tb is estimated by Miller’s
method fl982) combined with Lydersen”s technique (1982). The calculated
density of theobrom~ne at 25°C fl.430 g cm-s> and that of caffeine (1.333 g
cm-? lie between two literature values listed in Table 3, These indicate
that this method of estimating density did not introdu~ much error.
According to the work of Ziger and Eckert, the solid solute solubility
isotherms should collapse into a single straight line, the slope TJfor a given
solvent being almost constant, e-g. about 0.49 for CO,.
The results for the caffeine -t CO, and theobromine i- CO, systems are
shown in Figs. 7 and 8 respectively; the 17 for different temperatures are
listed in Table 6. As can be seen, the slopes for caffeine at 40 and 60aC are
0.497 and 0.493 respectively as described by Ziger and Eckert C1983),
However, for higher temperatures of 80 and 9YC, the slope deviates from
this value,
Another unusual feature is that the value of q for th~obromine f CO, is
much lower and forms three closely spaced straight and parallel lines.
Some authors attribute this feature to the polarity (e.g. v = 0.66 for
276

108

10’

106

105

104
103
102

10

0 5 10 15

+A / y1)(2 - A,yl) - log (1 + 6;/y)

Fig. 7. Solubility enhancement factor for the caffeine + CO, system, plotted according to the
Ziger-Eckert correlation (1983).

104 -1

0 2 4 6 8 IO

c;(A / y1)(2 - A/y,) - log (1 + 6:/P)

Fig. 8. Solubility enhancement factor for the theobromine+CO, system, plotted according
to the Ziger-Eckert correlation (1983).

TABLE 6
Parameter and enhancement factor correlations according to Ziger and Eckert models
(1983)

Caffeine Theobromine
Temperature (“C) 40 60 80 95 60 80 95
17 0.497 0.493 0.531 0.632 0.240 0.223 0.329
R value 0.99 0.99 0.99 0.99 0.95 0.99 0.99
phenylacetic acid/CO,, 7 = 0.656 for benzoic acid/CO,, 17= 0.43 for
vanillin + CO,, q = 0.42 for phenol + CO,; see Gurdial et al., 1989; Wells
et al., 1990). However, caffeine also has higher polarity, indicating that
polarity alone is not the only reason. The difference may be due to a lack
of thermodynamic data; many parameters (e.g. psub, Tb, 6 and (Y,) had to
be estimated, which limited the accuracy of correlation, especially at higher
temperatures. Another reason could be measurement errors, particularly
for theobromine, which has a (mole fraction) solubility as low as 10e7.

CONCLUSIONS

The solubilities of theobromine and caffeine in supercritical CO, were

measured in the temperature range 40 to 95°C for pressures between 80
and 300 bar. The solubilities of theobromine were two orders of magnitude
less than that of caffeine showing that it is more difficult to extract with
CO, only. The large difference between the solubilities of caffeine and
theobromine is due to the large difference in their melting points and
enthalpies of fusion; hydrogen bonding between theobromine molecules
may occur.
Data have been correlated with three density-based models. The results
show that an empirical semi-log correlation (log E vs. p) is limited,
depending on the system selected. A theoretical log c vs. log p correlation
seems to indicate that the association number of the molecules is not
constant but a function of temperature in the supercritical state, so an
improvement is needed in this approach. The accuracy of the semi-em-
pirical semi-log correlation is limited by the accuracy in the estimation of
each of the thermodynamic properties of solute and solvent. Density-based
models can only give approximate correlations for the caffeine + CO, and
theobromine + CO, systems.

ACKNOWLEDGMENTS

The authors are grateful to Mr. W. Businger for his technical assistance
with the experimental equipment.

LIST OF SYMBOLS

a, b constants
c solute concentration (g 1-l or mole fraction)
278

E solubility enhancement factor

hf enthalpy of fusion (cal mol-‘)
k association constant
A4 molecular weight
P pressure (bar)
R universal gas constant
T temperature (IQ
V molar volume (ml mol - * >
x mole fraction solute solubility in liquid
Y mole fraction solute solubility in gas

Greek Letters

slope at reference temperature in eqn. (6)

thermal expansion coefficient (K-l)
y-intercept at the reference temperature in eqn. (6)
isotherm spacing constant (k-l) in eqn. (6)
activity coefficient
fugacity coefficient
dimensionless energy parameter
solubility parameters ((Cal cm-3)o.5)
ratio of solubility parameters ( = 6,/S,)
slope parameter
intercept parameter
density of solute (g cmM3)

Subscripts

1 supercritical fluid solvent component

2 solid solute component
b boiling point
f fusion point
m melting point
r reduced properties
ref reference value

Superscripts

S solid phase
sub sublimation vapor
SCF supercritical fluid phase
i ideal state
 279

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