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(11)
(12)
(13)
(14)
324
8"= %
Ob (wt % )
NBA
NaCl
80.0
81.7
83.0
84.2
85.2
86.0
86.8
88.1
89.1
90.0
90.7
91.3
91.6
92.1
92.5
93.0d
93.46
93.4d
0.048
0.070
0.090
0.102
0.108
0.113
0.130
0.135
0.144
0.150
0.155
0.160
0.163
0.164
0.165
0.165
0.165
pa=
AC(W % )
NBA
NaCl
7.80
6.65
6.00
5.40
5.10
4.25
4.15
3.30
2.95
2.11
2.00
1.65
1.40
1.20
0.98
0.91
0.91
0.91
2.30
3.93
5.65
7.00
8.30
9.51
11.70
13.78
15.70
17.55
19.41
21.15
22.95
24.5
25.8
25.8
25.8
Ob(W % )
NBA
NaCl
80.0
81.5
82.8
83.9
84.6
85.6
86.0
87.1
88.1
88.9
89.7
90.4
91.4
91.9
92.6
93.1
93.4
93.6
94.0d
94.0d
0.024
0.045
0.061
0.074
0.085
0.094
0.109
0.121
0.129
0.136
0.142
0.147
0.151
0.155
0.158
0.160
0.163
0.165
0.165
7.80
7.20
6.29
6.00
5.50
4.90
4.75
3.89
3.70
2.90
2.48
2.22
1.82
1.59
1.39
1.21
1.08
0.95
0.91
0.91
1.14
2.24
3.31
4.36
5.39
6.40
8.39
10.3
12.1
13.9
15.7
17.3
18.9
20.5
22.0
23.6
25.0
25.8
25.8
(wt % )
NBA
NaCl
Ob
80.0
81.9
83.0
83.1
84.6
85.9
86.4
87.5
88.4
88.9
88.9
90.0
90.4
91.4
91.5
92.4
92.8
92.26
93.1
0.016
0.039
0.058
0.072
0.090
0.101
0.118
0.127
0.132
0.140
0.142
0.148
0.152
0.156
0.159
0.163
0.164
0.165
AC(wt Yo)
NBA
NaCl
7.80
7.00
6.30
6.20
5.50
4.74
4.14
3.59
3.35
2.95
2.60
2.00
1.90
1.50
1.45
1.10
0.90
0.94
0.91
0.974
1.94
2.91
3.86
5.75
7.60
9.41
11.2
12.9
14.7
16.3
17.9
19.5
21.1
22.6
24.1
25.6
25.8
~~~
AC(wt % )
NBA
NaCl
8" = 3
0.026
0.045
0.061
0.075
0.086
0.096
0.111
0.123
0.132
0.140
0.146
0.150
0.155
0.158
0.161
0.164
0.166
0.169
78.6
80.3
81.6
82.4
83.1
83.6
84.4
85.4
86.3
87.1
87.9
88.6
89.5
90.4
91.0
91.5
92.0
92.3
92.8a
92.8"
1.15
2.26
3.34
4.41
5.45
6.48
8.50
10.5
12.4
14.2
16.0
17.7
19.1
21.0
22.6
24.1
25.5
26.0
saturation.
0.021
0.041
0.060
0.072
0.085
0.095
0.111
0.122
0.131
0.139
0.146
0.151
0.156
0.160
0.163
0.166
0.170
0.173
0.173
1.19
2.31
3.42
4.53
5.58
6.65
8.69
10.6
12.5
14.4
16.2
17.8
19.4
21.0
22.6
24.1
25.6
26.1
26.1
a At saturation.
(1)
pure water and in the saline solution with salt molarity equal to
C,; the coefficient k, depends only on the solvent-electrolyte
pair and on temperature.
Since eq 1 is generally valid for very low saline concentrations, the correct definition of k, is:
However, the Setschenow equation correlates the experimental results for th,e H20-NBA-NaCI system with good approximation in a large range of salt concentrations for the different temperatures examined.
Consequently the k, value can be determined from all the data
available and not only from those at low concentration. It is,
Journal of ChemicalandEngineeringData, Vol. 21,No. 3, 1976
325
FUHNER 11924)
o HILL, MALISOFF (1926)
A JONES ( 1929 1
A BUTLER
1933)
0 THIS
- 0.16
-s 0.12
f
WORK
140
p 0.08
120
- 0.04
v- 100
WCI
k
B
80
I
I
16
20
A4uEoo PtwaE I W t X )
1
24
12
s2 60
100
40
96
"c
30 "C
20
20
40 "C
5 92
-
88
2
84
z
80
i
10
3
W
80
WEIGHT PERCENT C+ n BUTVL ALCOHM I NBAl
1
90
I
100
+ k$ + k,
(3)
0.20
T (OC)
k,(obsd)
k,(calcd)
20
25
30
40
0.175 f 0.003
0.179 f 0.005
0.186 f 0.005
0.191 f 0.005
0.176
0.179
0.182
0.187
0.16
However, the values of u and d K , obtained by such an expression, are very different if experimental data of second virial
coefficients ( 76)or of transport properties (viscosity) (7) are
used. Molecular diameters of nonelectrolytes obtained from
viscosity data, generally, yield more acceptable results (27)in
the ksevaluation.
For NBA the value derived from these data is unavailable.
Its value was, therefore, deduced by extrapolating similar data
pertaining to the series methanol, ethanol, and 1-propanol. The
resulting value is close to 5.1 X
cm.
With regard to the energy parameters, on the other hand, the
best results were obtained by using, both for ions and nonelectrolyte, the Mavroyannis-Stephen expression ( 7 7), instead of
the values deduced from the Stockmayer potential ( 70, 27).The
value thus obtained for NBA is: E I K = 224 K.
The polarizability of NBA was predicted by a method based
on the addition of bond contributions( 72). This procedure yields
satisfying results for alcohol molecules. The value obtained for
NBA is 8.6 X
cm3/mol. The molecular parameters of the
salt, needed to evaluate k, are reported by Masterton and Lee.
The calculated k, values are reported in Table IV at the four
temperatures considered.
The agreement of the theoretical values with the observations
(Figure 5 ) is good, especially considering the uncertainties in
evaluating the molecular parameters.
As a consequence, the ks dependence on temperature, which
can be derived by the scaled-particletheory, is verified as a first
approximation.
For a small range of temperatures this theory yields:
k, = a
4-b/T
(4)
log - = log
X
YO
Ir,
= ksCs
1
I
3.2
3.3
3.4
&,%-I
_
dk, - - -A"
dT
RF
where A" is the partial derivative, with respect to the salt concentration, of AH calculated at infinite salt dilution.
If A" can be considered independent of temperature, or for
small variations of the latter, eq 4A can be integratedto obtain
an expression formally identical with that derived by the scaled
particle theory:
A"
ks=-+B
RT
Literature Cited
(1) Butler, J. A., Thomson, D. W., Mac Lennon, W. H., J. Chem. SOC., 674
(1933).
(2) Davison, R. R.. Isbell, A. F., Smith. Jr., A. H., Hood, D. W., Office of Saline
Water Research and Development Progress, Rept. No. 55 (1961).
(3) Davison, R. R., Smith, Jr.. A. H.. Hood, D. W., J. Chem. Eng. Data, 11,304
(1966).
(4) De Santis. R., Marrelii, L., Muscetta, P. N., Chem. Eng. J., in press.
( 5 ) Fuhner, F., Ber., 57, 514(1924).
(6) Hill, A. E., Malisoff, W. M., J. Am. Chem. SOC., 48, 918 (1926).
(7) Hirschfelder, J. O., Curtiss, C. F., Bird, R. B. "Molecular Theory of Gases
and Liquids", Wiley, New York. N.Y., 1965.
(8) Jones, D. C.,J. Chem. SOC.,799 (1929).
(9) Long, F. A., McDevit. W. F., Chem. Rev., 51, 119 (1952).
(10) Masterton, W. L.. Lee, T. P., J. fhys. Chem., 74, 1776 (1970).
(11) Mavroyannis, C., Stephen, M. J., Mol. fhys., 5, 629 (1962).
(12) Moeiwyn-Hughes, E. A., "physical Chemistry". Pergamon Press, New York,
N.Y., 1961.
(13) Patterson, J. A.. Chem. Eng. News, 48 (1963).
(14) Pierotti. R. A., J. Phys. Chem., 67, 1840 (1963).
(15) Pierotti. R. A.. J. Phys. Chem., 69, 281 (1965).
(16) Poiak, J., Lu 8. C.-Y., Can. J. Chem. Eng., 50, 553 (1972).
(17) Reber, L. A., McNabb, W. M., Lucasse. W. W., J. fhys. Chem., 46,500
(1942).
(18) Reid, V. W., Salmon, D. G., Analyst, 80, 704 (1955).
(19) Setschenow, J.. 2.fhys. Chem., 4, 117 (1889).
(20) Shoor, S.K., Gubbins, K. E., J. Phys. Chem.. 73, 498 (1969).
(21) Wilcox. F. L., Schrier, E. E., J. fhys. Chem., 75, 3757 (1971).
Received for review October 14, 1975. Accepted February 18, 1976.
327