Fluid Phase Equilibria, 68 (1991) 35-46

35

Elsevier Science Publishers B.V., Amsterdam

Influence of size and shape effects on the solubility

of hydrocarbons: the role of the combinatorial entropy *
Krzysztof Kniai
Warsaw University of Technology, Division of Physical Chemistry, Noakowskiego 3,
Warsaw 00-664 (Poland)

(Received January 3, 1991; accepted in final form July 4, 1991)

ABSTRACT
Kniai, K., 1991. Influence of size and shape effects on the solubility of hydrocarbons:
role of the combinatorial entropy. Fluid Phase Equilibria, 68: 35-46.

the

Solid-liquid equilibrium data of the n-alkanes from n-hexane to n-hexatriacontane

dissolved in various alkane solvents have been used to determine the activity coefficients at
infinite dilution. Comparison of the data obtained with vapour-liquid
equilibriums, GLC
and heat of mixing data suggests that almost ideal solubility in some systems results from an
order/disorder
phenomenon known as the Patterson effect. The importance of the combinatorial entropy contribution for the solubility of hydrocarbons has been discussed.

INTRODUCTION

Solid-liquid equilibrium (SLE) has gained increasing interest in the

recent decade. Besides its importance for technological processes such as
crystallisation and purification, SLE provides a good tool for examining the
thermodynamic nature of many systems.
The ultimate aim of this work is to investigate the influence of the
solvent shape and size on the solubility of chain hydrocarbons.
The conclusions arrived at are based on sets of solubility data, extracted
from the literature, including results recently reported by Domaiiska and
Kniai (1990a,b) and the subsequent study has been deliberately confined to
alkane mixtures, because of the importance of conformational effects in
alkane thermodynamics.
* Work dedicated to Dr. Urszula Domadska from the Warsaw University of Technology.
0378-3812/91/$03.50

0 1991 Elsevier Science Publishers B.V. All rights reserved

36

n-Alkanes are highly ordered in the solid state, existing in many crystalline phases which depend on the chain length (Broadhurst, 1962; Denico10 et al., 1983). In the liquid state they still retain much of their order, as
was proved by Barbe and Patterson (1978). Using a light scattering technique Tancrede et al. (1977) showed clearly that globular or spherical
solvents destroy the conformational order in liquid long-chain hydrocarbons, giving high positive values for the enthalpy and entropy of mixing.
According to an early study by Patterson et al. (1972) the thermodynamic
properties of alkane mixtures are made up of combinatorial, free volume
and interactional (field forces + order destruction) contributions, as was
shown when they considered the importance of each contribution to the
activity coefficients at infinite dilution of many short or globular alkanes
dissolved in long-chain n-alkanes.
Because of the high melting temperatures and low volatilities of the long
chain paraffins, heat of mixing, GLC or VLE data for systems with high
paraffin concentrations are very scarce. In this work SLE data have been
used to determine the activity coefficients at infinite dilution for long-chain
n-alkanes.

THE COMPUTATIONAL, PROCEDURE

The solubility of a solid in a liquid can be used to evaluate the activity

coefficient of the solute component in the solution by eqn. (1).
In x, = - 2(+-l)+*(ln$+%-I)-lny

(1)

This equation is valid if no phase transition takes place in the solid phase
between the system temperature T and the solute melting temperature T,,.
When a phase transition takes place between T and Tml, eqn. (1) must
be modified to include the effect of the transition point. For a first-order
phase transition eqn. (1) has the form
In xi=

- 2(-$-l)+*(ln-&+?-I)
Tt,,
-- AH,,, -_
RTtr1 ( T

1 -1n y1
)

Experimental x1 vs. T data therefore permit evaluation of the activity

coefficients of the solute y1 by using eqn. (1) or (2), provided that the
necessary thermochemical properties of the solid are available (Table 1).

37
TABLE 1
Thermodynamic

data of solutes

Solute

*KY,
&I mol)

AC,,,
(J/mol)

n-C,
n-C,

13.09
20.75
36.86
53.38
61.73
46.65
69.66
48.99
54.93
59.54
64.69
76.00
88.87

46.87 a
53.88 a
64.69 =
73.59 =
71.41=
- 332.6 d
85.56 d
58.50 f
66.60 f
50.50 f
118.90 f

n-Cl2

n-C,6
n-C,8
n-C,9

n-C20
n-C22
n-C,

n-c,,
n-C28
n-C32

n-C36

=
=
=
=
a

c
c
c

177.83
216.37
263.58
291.45
301.40
304.65
309.40
317.05
323.75
329.55
334.45
342.10
349.05

a
a
a
b
b
=
=
a
e
e
e

13.82

295.95

28.22
31.32
32.24
35.46
42.70
30.56
9.92

316.15
321.25
326.45
331.15
338.90
346.95
345.25

a
=
e
e

c
c
c

a Messerly et al., 1967. b Domariska and Kniti, 1990a. Schaerer et al., 1955. d Domariska
et al., 1987a. Domahska et al., 1987b. f Domariska and Wyrzykowska, 1990. g Domanska
and Kniai, 199Ob. h Hexatriacontane reveals two phase transitions in the solid state, data
taken from Schaerer et al. (1955).

Thus, for each system the dependence of the activity coefficient on the
solubility (mole fraction) has been obtained. Activity coefficients at infinite
dilution (and corresponding temperatures)
have been calculated using
polynomial extrapolation of the first, second or third degree. The results,
given as experimental, are listed in Tables 2 and 3.
The error in the activity coefficient estimation exceeds the error obtained from direct experimental techniques and varies from 25% for
systems with lower alkanes as solutes (n-C,, n-C,, n-C,,) to 5% for systems with higher paraffins as solutes (n-C,, n-C,,, . . . , n-C,,).

RESULTS AND DISCUSSION

Mixtures of short n-alkanes with long-chain paraffins reveal negative

deviations from ideality, which become bigger as the difference between
chain lengths of the components increases. Such properties of the systems
under study were predictable, and have been confirmed by the results
obtained from the GLC technique in reversed systems (see Table 3).
Negative deviations from ideality are particularly big for mixtures of
paraffins with cycloalkanes. The values based on SLE data for these

38
TABLE 2
Activity coefficients at infinite dilution for long-chain paraffin as solutes
Solute +
solvent

Reference

c, + c-c,
c, +c-c,
c, + n-c,
c,, + n-c,
c,, + c-c,

Goates et al. (1979)

Ott and Goates (1983)
Hoerr and Hatwood (1951)
Hoerr and Hatwood (1951)
Domanska and Kniai (199Ob)
Domanska and Kniai (1990a)
Domahska and Kniai (1990b)
Domahska and Kniai (1990b)
Domariska and Kniai (1990a)
Domanska and Kniai (1990a)
Dernini and De Santis (1976)
Domanska and Kniai (1990a)
Domadska and Kniai 0990a)
Domahska and Kniai (1990a)
Domahska and Kniai (1990a)
Domanska and Kniti (1990a)
Domanska et al. (1987a)
Domahska et al. (1987a)
Domanska et al. (1987a)
Domanska and Kniai (1990a)
Domanska and Kniai (1990a)
Domadska and Kniai (1990a)
Domanska et al. (1987b)
Domafiska et al. (1987b)
Domadska and Kniai (199Ob)
Domaiiska and Kniai (199Ob)
Domadska and Kniai (199Ob)
Domanska and Kniai (199Ob)
Domanska and Kniai (199Ob)
Kniai (1991)
Kniai (1991)
Demini and De Santis (1976)
Domanska et al. (1987b)
Domanska et al. (1987b)
Domanska et al. (1987b)
Domatrska et al. (1987b)
Lundager et al. (1976)
Domahska and Kniai (199Ob)
Domadska and Kniai (199Ob)
Domariska and Kniai (1990b)
Domanska and Kniai (1990b)
Domanska and Kniai (1990b)
Domanska and Kniai (1990b)
Domariska et al. (1987b)

c,, +2,2-c,
C,, +2,3-C,
c,, +2-c,
c 16+ 3-c,
c,, + n-c,
c,, + n-c,
c 16+ c-c,
c,, +2,2-c,
c,, +3-c,
c,, + n-c,
c,, + c-c,
c,, + n-c,
c,, + c-c,
c,, + n-c,
c,, +2,2-c,
c,, +3-c,
c,, + n-c,
c, + c-c,
c, + n-c,
c,, + c-c,
c,, +2,2-c,
C,, +2,3-C,
c,, +2-c,
c,, +3-c,
c,, + n-c,
c,, + c-c,
c, + n-c,
c, + c-c,
c, + n-c,
c, + c-c,
c, + n-c,
c, + n-c,
c, + c-c,
c, +2,2-c,
C,, +2,3-C,
c,, +2-c,
c,, +3-c,
c,, + n-c,
c,, + c-c,

2;
_a
_a
_a
_a

218.3
256.0
253.6
250.5
259.5
_a
250.8
243.6
261.6
262.8
265.0
257.4
262.5
271.3
263.8
269.9
270.6
269.1
264.1
266.3
269.6
280.9
281.6
282.7
277.9
281.4
268.1
_a
270.7
273.5
275.9
273.3
279.7
274.5
285.1
272.0
297.3
273.5
277.4
270.5

In ym
exp.

In ym
F-H

In ym
S-G

In ym
Im. F-H

0.161
0.145
0.111
-0.113
- 0.368
- 0.026
- 0.073
0.037
- 0.194
- 0.089
- 0.058
- 0.747
- 0.037
- 0.232
- 0.248
- 0.284
- 0.094
- 0.430
- 0.341
- 0.030
- 0.228
- 0.163
- 0.409
- 0.177
- 0.968
- 0.008
- 0.254
-0.116
- 0.245
- 0.280
- 0.479
- 0.796
- 0.752
- 0.316
- 0.863
- 0.316
- 0.194
- 1.283
-0.155
- 0.319
- 0.056
- 0.217
- 0.217
- 0.802

0.009
- 0.065
- 0.037
- 0.252
- 1.124
- 0.554
- 0.571
- 0.571
- 0.571
- 0.570
- 0.570
- 0.751
- 0.734
- 0.754
- 0.753
- 0.971
- 0.534
- 1.086
- 0.610
- 0.925
- 0.948
- 0.947
- 1.203
- 0.690
- 2.018
- 1.126
- 1.153
- 1.151
- 1.151
- 1.150
- 1.445
- 1.361
- 1.694
- 1.028
- 1.950
- 1.208
- 2.379
- 2.984
- 1.769
- 1.806
- 1.804
- 1.804
- 1.802
-2.211

0.006
0.077
0.038
0.258
1.130
0.583
0.583
0.583
0.583
0.583
0.583
0.757
0.770
0.770
0.769
0.977
0.544
1.091
0.622
0.948
0.968
0.967
1.208
0.703
2.023
1.175
1.175
1.175
1.175
1.175
1.449
1.390
1.698
1.048
1.954
1.230
2.434
2.988
1.840
1.840
1.840
1.840
1.840
2.215

0.003
o.q33
0.016
0.106
0.429
0.231
0.231
0.231
0.231
0.231
0.231
0.295
0.300
0.300
0.300
0.375
0.216
0.415
0.246
0.372
0.371
0.371
0.456
0.276
0.732
0.445
0.445
0.445
0.445
0.445
0.540
0.519
0.624
0.400
0.709
0.464
0.865
1.039
0.671
0.671
0.671
0.671
0.671
0.794

39
TABLE 2 (continued)
Solute + solvent

Reference

c, + n-c,
c, + n-c,,
c, + n-c,,
c,, + n-c,
c,, + n-c,
c,, + c-c,
c,, + n-c,
c,, + n-c,
c32+ n-Clll

Lundager et
Lundager et
Lundager et
Lundager et
Seyer (1938)
Seyer (1938)
Lundager et
Seyer (1938)
Seyer (1938)
Seyer (1938)
Lundager et
Lundager et
Lundager et
Lundager et
Lundager et
Lundager et

c32

n-C,2

c,,

n-c,

c,,

n-c,

c,,

n-c,

c,,

n-c,

C36

n-C,,

c36

n-Cl2

Error of temperature

al.
al.
al.
al.

(1976)
(1979)
(1979)
(1976)

al. (1976)

al.
al.
al.
al.
al.
al.

(1976)
(1976)
(1976)
(1976)
(1976)
(1976)

determination

279.4
275.9
278.6
281.4
288.3
288.9
282.5
290.8
294.6
293.9
279.5
280.1
278.5
278.6
280.6
279.8

In ym
exp.

In ym
F-H

In ym
S-G

In ym
Im. F-H

- 0.218
- 0.124
0.035
- 1.121
- 0.752
- 1.878
- 1.049
- 1.076
- 0.813
- 0.774
- 0.685
- 0.681
- 0.713
- 0.921
- 0.794
- 0.623

- 0.529
- 0.274
-0.179
- 1.046
- 0.825
- 0.965
- 0.661
- 0.537
- 0.362
- 0.249
- 1.226
- 0.978
- 0.795
- 0.654
- 0.454
- 0.322

1.419
0.698
0.446
3.009
2.308
2.751
1.809
1.441
0.943
0.631
3.599
2.792
2.215
1.787
1.202
0.831

1.393
0.689
0.441
2.942
2.263
2.748
1.778
1.418
0.930
0.624
3.520
2.738
2.177
1.759
1.186
0.822

too large.

systems are in agreement with results obtained by Letcher and Jerman

(1976) from GLC.
According to Barbe and Patterson (1978) mixtures of chain compounds
with solvents globular in shape should reveal almost ideal behaviour
(provided only aliphatic groups are present) owing to the positive contribution arising from the destruction of order in the longer alkane. The data
reported in this work corroborate this concept, since mixtures with branched
isomers of hexane have very small In ym. It is remarkable, however, that
values of In ym for 2,2-dimethylbutane and 2-methylpentane are closer to
ideality than those for 2,3_dimethylbutane and 3-methylpentane. The destruction of order caused by mixing with 2,2-C, and 2-C, should therefore
be greater. This conclusion is in agreement with Barbe and Pattersons
(1980) interpretation of the heat of mixing data for n-hexadecane with the
isomers of hexane.
The role of the combinatorial entropy

In order to examine the importance of the combinatorial effects the

experimental acitivity coefficients (obtained from SLE data and also from
GLC) have been compared with values predicted using the well known

40
TABLE 3
Activity coefficients at infinite dilution for long-chain paraffins as solvents a
System
solute + solvent

Reference

n-c, + n-c,,
n-c, + n-c,,
c-c, + n-c,,
n-c, + n-c,,

Hicks and Young (1968)

Hicks and Young (1968)
Letcher and Jerman (1976)
Hicks and Young (1968)
Cruickshank et al. (1968)
Cruickshank et al. (1968)
Cruickshank et al. (1968)
Cruickshank et al. (1968)
Cruickshank et al. (1968)
Letcher and Jerman (1976)
Hicks and Young (1968)
Hicks and Young (1968)
Hicks and Young (1968)
Hicks and Young (1968)
Letcher and Jerman (1976)
Hicks and Young (1968)
Hicks and Young (1968)
Hicks and Young (1968)
Letcher and Jerman (1976)
Hicks and Young (1968)
Hicks and Young (1968)
Letcher and Jerman (1976)
Letcher and Jerman (1976)

2,2-c, + n-c,,
2,3-C, + n-C,,
2-c, + n-c,,
3-c, + n-c,,
n-c, + n-c,,
c-c, + n-c,,
n-c, + n-c,,
n-c, + n-c,,
n-c, + n-c,
n-c, + n-c,
c-c, + n-c,,
n-c, + n-c,
n-c, + n-c,,
n-c, + n-c,,
c-c, + n-c,,
n-c, + n-c,,
n-c, + n-c,
c-c, + n-c,,
c-c, + n-c,,

a Exp, experimental; F-H,

proved Flory-Huggins.

Flory-Huggins

Temp.

Flory-Huggins;

(K)

In ym
exp.

In ym
F-H

303.15
303.15
298.15
303.15
308.15
308.15
308.15
308.15
308.15
308.15
308.15
308.15
313.15
313.15
313.15
313.15
333.15
333.15
328.15
343.15
343.15
338.15
343.15

- 0.087
-0.101
- 0.233
7 0.074
- 0.058
- 0.131
- 0.094
- 0.131
- 0.131
- 0.294
-0.113
- 0.090
-0.186
-0.161
- 0.368
- 0.133
- 0.234
- 0.219
- 0.454
- 0.329
- 0.308
- 0.531
- 0.631

-0.418
-0.411
-0.316
-0.311
- 0.382 - 0.380
- 0.236 - 0.233
- 0.387 - 0.373
- 0.386 - 0.381
- 0.386 - 0.381
- 0.386 - 0.381
- 0.386 - 0.380
- 0.457 - 4.455
- 0.300 - 0.296
- 0.231 - 0.228
- 0.568 - 0.558
- 0.454 - 0.447
- 0.527 - 0.526
- 0.362 - 0.357
- 0.636 - 0.626
-0.517
-0.510
- 0.657 - 0.656
-0.818
- 0.807
- 0.691 - 0.682
- 0.773 - 0.773
- 0.878 - 0.878

In ym
S-G

S-G, Stavermann-Guggenheim;

expression for the combinatorial

In ym
Im. F-H
- 0.206
-0.154
- O.i87
-0.113
- 0.190
-0.190
-0.190
-0.190
-0.190
- 0.226
- 0.146
-0.111
- 0.284
- 0.224
- 0.263
- 0.177
- 0.321
- 0.258
- 0.332
- 0.420
- 0.350
- 0.395
- 0.453

Im. F-H, im-

entropy:

(3)
the Stavermann-Guggenheim

combinatorial

term:

where
xiri

ai =
x1r1

+x,r,

xi41

q =
x141

+x242

2=4

41

l.al

1.m 0.80 0.a

0.40 .

am -

0-M
-0.M

am

@_I2

a25

,e

0.Y

a50
0

0.62

ai5

a@?

1.m

Fig. 1. Values of A In ym = In ~2, - In rCm,tvs. size factor OJ= rr / rz, where In r,,r has been
calculated using the Flory-Huggins
expression for combinatorial entropy. Filled circles
represent mixtures of long-chain n-alkanes as solutes and short-chain, globular or cyclic
alkanes as solvents (SLE data); open circles pertain to reversed systems (VLE or GLC data).

and the improved Flory-Huggins

In $ = In :
[

+ 1- :
1I

term (Kikic et al., 1980):

(5)

where

The values of the group volume and surface parameters (Y, g) applied in
this paper have been taken from the work of Kehiaian and Marongiu
(1988).
The results of the predictions are listed along with the experimental data
in Tables 2 (SLE data) and 3 (GLC data). Figures 1, 2 and 3 present the
difference between the experimental and predicted activity coefficients
(A In y) vs. solvent/solute size ratio o. Filled circles represent systems in
which a long-chain compound is the solute (SLE data), while open circles
represent systems in which a long-chain compound is the solvent. Figures 1
and 2, presenting the results of the Flory-Huggins term and StavermannGuggenheim term respectively, are almost similar, indicating that both

1.w -

am .
0.a

ha
b

cii,

oGL.

0.40 .

am

-0.20

am

au

a25

,m

0.27

am

a62

ai5

a87

1-m

Fig. 2. Values of A In ym = In y&, -In y,,, vs. size factor w = rl /r2, where In yc,,has been
calculated using the Stavermann-Guggenheim
expression for combinatorial entropy. Filled
circles represent mixtures of long-chain n-alkanes as solutes and short-chain, globular or
cyclic alkanes as solvents (SLE data); open circles pertain to reversed systems WLE or GLC
data).

0-m

0.12

ai3

0.33

a5I

cl62

lx75

@.a?

LDI

Fig. 3. Values of A In ym = In y& -1n y,,, vs. size factor w = rl /r2, where In yc,rhas been
calculated using the improved Flory-Huggins (Kikic et al., 1980) expression for combinatorial entropy. Filled circles represent mixtures of long-chain n-alkanes as solutes and
short-chain, globular or cyclic alkanes as solvents (SLE data); open circles pertain to
reversed systems (VLE or GLC data).

43

models overestimate the role of the combinatorial entropy, especially in the

range 0 < o < 0.5. It is significant that the A In ym is much higher for
systems with long-chain alkanes as solutes. There must be a positive
contribution to the activity coefficient reflecting the destruction of the
orientational order. In Fig. 3, however, the points are more scattered. The
improved Flory-Huggins expression underestimates the combinatorial effects in many systems: long-chain paraffins-cycloalkanes,
cycloalkaneslong-chain paraffins, long-chain paraffins-long-chain
solvents. Nevertheless for many systems the predictions made by the improved Flory-Huggins
model are very good, owing to the more suitable mathematical form of the
model. One should remember that Kikic et al. (1980) altered the classical
Flory-Huggins expression in an attempt to improve VLE and GLC data
predictions. For the data reported in this work the modified Flory-Huggins
model behaves similarly to the correlation functions like Wilson or UNIQUAC if interaction parameters correlated for VLE data are applied to
SLE systems (see, for example, Domanska (1986) or Domaiiska (1988)).

CONCLUSIONS

Addition of a short, globular or cyclic solvent to an ordered long-chain

paraffin leads to destruction of the conformational order. The values
calculated from the Flory-Huggins (or Stavermann-Guggenheim)
combinatorial term are far more negative than the experimental results, indicating that for systems in which a long-chain hydrocarbon is a solute the
positive contribution from the Patterson effect must be considered. Systems
in which the destruction of order is greatest (2,2-C, or 2-C,) reveal almost
ideal solubility, owing to a larger-order contribution.
Classical formulae for the combinatorial entropy do not take into account any order/disorder
phenomena, giving rise to systematic deviations
between calculated and experimental values. These deviations increase
with the solute chain length. The frequently used Kikic version of the
Flory-Huggins formula predicts the activity coefficient at infinite dilution
with smaller error, but the results are still unsatisfactory.
Existing discrepancies between theory and experiment could be resolved
either by introducing a new entropy formula similar to the expression of
Kikic et al. (19801, but based on VLE, GLC and SLE data or by incorporating into the classical entropy equations terms accounting for order/disorder phenomena.

44
ACKNOWLEDGEMENTS

The author would like to express his highest gratitude to Professor D.

Patterson and Professor H. Buchowski for their useful comments.

LIST OF SYMBOLS

AC,

2,2-c,
2,3-C,
2-c,
3-c,
c-c,
c-c,
AHIn
AK,
4
;
T,
T,*
x

heat capacity of melting at the melting point

2,2-dimethylbutane
2,3-dimethylbutane
2-methylpentane
3-methylpentane
cyclopentane
cyclohexane
enthalpy of fusion
enthalpy of phase transition
relative molecular surface
relative molecular volume
gas constant
at melting point temperature
transition point temperature
mole fraction (solubility)

Greek letters

Yrn
YC
A In ym
6
0
Q,
w

the activity coefficient at infinite dilution

the combinatorial part of the activity coefficient
the difference between the experimental and calculated ym
Kikic-Alessi parameter
relative molecular surfaces ratio
relative molecular volumes ratio
solvent/solute size ratio

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45

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