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35
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
INTRODUCTION
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.
(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
)
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,,).
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,
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.
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,,
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,,
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;
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
entropy:
(3)
the Stavermann-Guggenheim
combinatorial
term:
where
xiri
ai =
x1r1
+x,r,
xi41
q =
x141
+x242
2=4
41
l.al
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).
+ 1- :
1I
(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
CONCLUSIONS
44
ACKNOWLEDGEMENTS
LIST OF SYMBOLS
AC,
2,2-c,
2,3-C,
2-c,
3-c,
c-c,
c-c,
AHIn
AK,
4
;
T,
T,*
x
Greek letters
Yrn
YC
A In ym
6
0
Q,
w
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