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4981
Solubilities of NaCl, KCl, LiCl, and LiBr in Methanol, Ethanol, Acetone, and
Mixed Solvents and Correlation Using the LIQUAC Model
Miyi Li,, Dana Constantinescu, Lisheng Wang, Andre Mohs, and Jurgen Gmehling,*
School of Chemical Engineering & EnVironment, Beijing Institute of Technology, 100081 Beijing, China,
Technische Chemie, Institut fur Reine und Angewandte Chemie, Carl Von Ossietzky UniVersitat Oldenburg,
D-26111, Oldenburg, Germany
The solubilities of NaCl, KCl, LiCl, and LiBr in pure methanol, ethanol, and acetone were measured over a
temperature range from 293.15 to 333.15 K. Furthermore salt solubilities in the mixed solvents (water +
methanol, water + ethanol, water + acetone, methanol + ethanol, methanol + acetone, ethanol + acetone)
were determined at 313.15 K. For a few systems solubility data are reported for the first time. In a few cases
a comparison with published data stored in the Dortmund Data Bank (DDB)1 showed disagreement. The
LIQUAC model was used to correlate the experimental data. The calculated salt solubilities are in good
agreement with the experimental results for the systems NaCl + water + methanol and KCl + water +
methanol.
2. Experimental Section
1. Introduction
The knowledge of salt solubilities in pure organic and mixed
solvent electrolyte systems is of great importance for the design
and simulation of unit operations such as crystallization,
liquid-liquid extraction, and other industrial processes.2 The
data are also required in connection with theoretical studies
concerning the liquid phase structure and its thermodynamic
properties. Accurate solubility data are also of great interest for
the development of electrolyte models. For the semiempirical
LIQUAC3,4 model, a large database was used for optimizing
the required parameters. LIQUAC can be used to correlate and
predict salt solubilities (SLE), liquid-liquid equilibria (LLE),
mean ion activity coefficients, vapor-liquid equilibria (VLE),
and osmotic coefficients for electrolyte solutions. Unfortunately,
most of the published data are only available for aqueous
systems. For pure organic or mixed solvent electrolyte systems
the number of available data is much smaller, and often the
published data show large scattering. More reliable data are
required in order to enlarge the database for fitting the required
parameters of electrolyte models.
Figure 1. The apparatus applied for solubility measurements: (1) thermostatted syringe; (2) digital temperature display; (3) Pt-100 thermometer;
(4) magnetic stirring rod; (5) jacketed glass cell; (6) magnetic stirrer; (7)
temperature-controlled bath; (8) pump.
4982
mKCl
mLiCl
mLiBr
T (K)
methanol
methanol
ethanol
methanol
ethanol
acetone
methanol
293.15
298.15
303.15
308.15
313.15
318.15
323.15
328.15
333.15
0.241
0.238
0.235
0.231
0.225
0.219
0.217
0.212
0.209
0.0708
0.0736
0.0754
0.0780
0.0811
0.0833
0.0858
0.0888
0.0907
0.0069
0.0064
0.0061
0.0059
0.0054
0.0051
0.0050
0.0046
0.0044
10.26
10.28
10.29
10.30
10.30
10.31
10.32
10.33
10.33
5.901
5.840
5.800
5.737
5.707
5.643
5.628
5.587
5.556
0.2776
0.2556
0.2236
0.1931
0.1730
0.1509
0.1240
0.1037
16.39
16.44
16.47
16.53
16.60
16.67
16.76
16.83
16.90
W2 - W 3
1
W1 - W2 Msalt
RSD % )
1
n-1
i)1
jx
0.5
(x
- jx)2
100
(2)
(1)
4983
(3)
The first term on the right side of eq 4 represents the longrange (LR) interaction contributions caused by the Coulomb
electrostatic forces. The second term represents the middle range
(MR) interaction contributions caused by charge-dipole and
charge-induced dipole interactions. The third term takes into
account the contribution of the noncharge interactions (shortrange (SR) interactions). The UNIQUAC model has been chosen
to describe these specific interactions. The activity coefficients
in electrolyte solutions are calculated by summing up the
following three contributions:
ln i ) ln LR
+ ln MR
+ ln SR
i
i
i
(4)
2AMsdm
b3ds
(5)
soldsol
sol
(6)
4984
xsVs
s )
the parameters between cations (c) and anions (a). B(I) is equal
to dB(I)/dI. Mm is the mean molar mass of the mixed solvents
(kg mol-1).
The SR term is calculated by the UNIQUAC model:
(7)
solVsol
sol
I ) 0.5
ionzion
(8)
{ ( )
(9)
6.35969dm0.5 /(DT)0.5
qx
i i
(10)
qx
Vs ) rs /
Fs ) q s /
s,ion(I)mion
ion
IB'sol,ion(I)]x'solmion - Ms
( )
Ms
Mm
sol
ln *j MR ) (Mm)-1
k,i)
]}
(17)
(18)
qx
(19)
j,sol(I)x'sol
[ ]
zj2
2Mm
sol
ion
i i
(20)
ion
zj2AI
(21)
1 + bI
+
sol
B'sol,ion(I)x'solmion +
( )
zj2
2
j,ion(I)mion
ion
B'ca(I)mcma -
Bj,s(I ) 0)
(22)
Ms
SR
ln *j SR ) ln SR
j - ln j (B)
ln SR
j (B) ) 1 -
(15)
() [
(23)
( )]
rj
rjqs
rj
rjqs
+ ln
- 5qj 1 + ln
+
rs
rs
rsqj
rsqj
qj(1 - j,s - ln s,j) (24)
(16)
solMsol
k k
i i
ln *j LR ) -
[Bsol,ion(I) +
q x
where ri and qi are the van der Waals volumes and surface areas,
and ai,j represents the UNIQUAC interaction parameters,
whereby ai,j is different to aj,i. xi is the mole fraction of species
i in the solution. In these equations, the indices i and j cover all
solvents and ions.
For ions j, each part of the activity coefficient is given on
the basis of the unsymmetrical convention on molality scale.
Mm )
rx
(12)
qixis,i
sol
ln sMR )
( )]
Vs
Vs
+ ln
Fs
Fs
i i
i,s
qs 1 - ln
D)
ln sSR ) 1 - Vs + ln Vs - 5qs 1 -
ion
Table 2. Salt Solubilities (mol kg-1) in the Mixed Solvents at 313.15 K for Different Salt-Free Mass Fractions (w1)
water(1) + methanol(2)
water(1) + ethanol(2)
methanol(1) +
ethanol(2)
methanol(1) +
acetone(2)
ethanol(1) +
acetone(2)
mLiCl
mLiCl
mLiCl
mLiCl
11.21
13.69
15.55
17.75
19.56
5.75
6.14
6.85
7.35
7.83
8.39
8.87
9.30
9.80
1.04
1.76
2.87
3.91
4.83
5.46
6.77
8.04
8.93
0.486
0.819
1.182
1.470
2.052
2.666
3.417
4.229
5.108
water(1) + acetone(2)
w1
mNaCl
mKCl
mLiCl
mNaCl
mKCl
mLiCl
mNaCl
mKCl
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
0.369
0.601
0.957
1.405
2.000
2.665
3.409
4.255
5.194
0.137
0.256
0.471
0.790
1.235
1.789
2.508
3.334
4.283
11.83
12.76
13.56
14.37
15.46
16.43
17.59
18.64
19.83
0.074
0.286
0.647
1.176
1.786
2.460
3.215
4.038
5.035
0.0295
0.121
0.336
0.672
1.122
1.685
2.346
3.170
4.150
6.94
7.91
9.77
10.98
12.57
14.25
15.89
17.05
19.23
0.0164
0.0097
0.0983
4.210
5.179
2.550
3.352
4.309
ln(Ms /Mm + Ms
ion)
(25)
) ( )
[(
aMX nH2O
) + ln(mM*)
M + - ln(mX*)
X + n ln(xH2OH2O)
(27)
raq+org
1
1
+ ln
+
raq+org
raq
raq
qaq+org
qaq
raqqaq+org
- 5qX ln
+
5rX
raq
raq+org
raq+orgqaq
xaqaq,X + xorgorg,X
+
qX ln
aq,X
BX,aq(I ) 0)
(xaqX,aq + xorgX,org - X,aq) +
Maq
BX,aq+org(I ) 0)
+ ln(Maq /Maq+org) (30)
Maq+org
+ - n
aX aH2O
aM
[(
X(aq/aq+org) ) rX
ln Ksp(T) ) ln
) ( )
raq+org
1
1
+ ln
+
raq+org
raq
raq
qaq+org
qaq
raqqaq+org
- 5qM ln
+
5rM
raq
raq+org
raq+orgqaq
xaqaq,M + xorgorg,M
+
qM ln
aq,M
BM,aq(I ) 0)
(xaqM,aq + xorgM,org - M,aq) +
Maq
BM,aq+org(I ) 0)
+ ln(Maq /Maq+org) (29)
Maq+org
M(aq/aq+org) ) rM
ion
4985
(31)
Bi,aq+org(I ) 0) ) xaq
bi,aq + xorg
bi,org + xaq
ci,aq + xorg
ci,org
(32)
raq+org ) xaq
raq + xorg
rorg
(33)
qaq+org ) xaq
qaq + xorg
qorg
(34)
Li
Li+
BrBrLi+
Li+
bij
cij
aij
aji
dij
H2O
MeOH
H2O
MeOH
ClBr-
-0.25121
-0.27605
0.04002
-0.02844
0.32999
0.40366
0.01648
0.11215
-0.03810
-0.05433
-0.30497
0.52021
-927.39
-1075.56
4179.03
27.59
-887.60
-70.18
-4469.29
-5151.06
1078.11
1101.21
-4297.14
-6532.19
0.15343
0.13686
4986
Figure 4. NaCl solubility in the system methanol + water at different saltfree mole fractions: (9) this work at 313.15 K; (s) LIQUAC model at
313.15 K; (O) Pinho and Macedo8 at 298.15 K; ( ) LIQUAC model at
298.15 K; (4) Pinho and Macedo8 at 323.15 K; (---) LIQUAC model at
323.15 K.
np
nt
Qexp - Qcalc
100
Qexp
) min
(35)
4987
Ndata
i)1
Qcalc
- Qexp
i
i
Qexp
i
100
(36)
Figure 9. LiCl solubility in the system water + methanol at different saltfree mole fractions: (0) this work at 313.15 K; (s) LIQUAC model at
313.15 K; (O) data set in DDB1 at 298.15 K; ( ) LIQUAC model at 298.15
K.
Table 4. AARD and Solubility Product Estimated in the Correlation
AARD (%)
ln Ksp
osmotic
system
coefficient () solubility pressure 298.15 K 313.15 K
LiCl + H2O
LiBr + H2O
LiCl H2O(aq)
LiCl(aq)
LiCl + H2O +
methanol
NaCl + H2O +
methanol
KCl + H2O +
methanol
2.0
2.3
2.6
3.6
-12.06
-15.50
-11.78
-15.10
1.5
2.6
5.1
4988