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Modeling the reactive extraction of carboxylic acids in the presence of inorganic salts requires experimental
data for the thermodynamic properties of aqueous solutions of the single salts as well as of aqueous
solutions of (salt + carboxylic acid) mixtures. The activity of water in such solutions was determined by
isopiestic measurements at 298.15 K for the binary mixture (water + sodium citrate) and the ternary
mixtures of (water + citric acid + salt) for the salts sodium chloride, sodium nitrate, sodium sulfate, and
sodium citrate. The experimental data are correlated with Pitzers Gibbs excess energy model for aqueous
electrolyte solutions.
Introduction
Carboxylic acids are commonly recovered from diluted
aqueous solutions by reactive extraction with a waterinsoluble organic amine. The liquid-liquid phase equilibrium in such systems is strongly influenced by inorganic
salts. The development and parametrization of a model for
correlating and predicting such liquid-liquid phase equilibria requires not only experimental data for the partitioning of carboxylic acids to aqueous/organic two-phase systems in the presence of a chemical extractant and some
inorganic salts, but also of the properties of subsystems.
Here, experimental results are presented for the activity
of water in aqueous solutions of a single salt (sodium
citrate) as well as in aqueous solutions of citric acid which
also contain a single sodium salt (chloride, nitrate, sulfate,
citrate) at 298.15 K. The experimental results are used to
determine parameters of Pitzers equation for the Gibbs
excess energy of electrolyte solutions.
Experimental Section
The activity of water in aqueous solutions of nonvolatile
solutes at 298.15 K was determined in isopiestic investigations using aqueous solutions of sodium chloride as references. The experimental techniques and the equipment are
similar to those used in previous investigations on aqueous
solutions of polymers (Gromann et al.,1 Hasse et al.,2 Kany
et al.3). Therefore, the experimental details are not repeated here. The experimental uncertainties are (0.1 K
for the temperature and (0.35% in the molality of a solute.
Aqueous solutions of sodium chloride were used as references. The correlation of Pitzer et al.4 was used to convert
the experimental results for the molality of sodium chloride
in the reference solution to the activity of water. The
absolute uncertainty of the experimental results for the
activity of water is estimated to (0.0005. However, that
number does not include any contribution that might result
from a bias of the correlation of Pitzer et al.4 (cf. Clark and
Glew,5 Archer,6 and Archer and Carter7).
Materials. Citric acid monohydrate (min. 99.8%), sodium nitrate, sodium chloride, and sodium sulfate (min.
* To whom correspondence may be addressed. Tel.: +49-631-2052410. Fax: +49-631-205-3835. E-mail: gmaurer@rhrk.uni-kl.de.
http://www.mv.uni-kl.de/TD.
(m
H3Cit)min
0.08
0.1
0.2
0.2
(m
H3Cit)max
(m
salt)min
(m
salt)max
3.6
5.7
3.9
3.5
0.5
0.05
0.5
0.2
0.2
1.7
1.6
3.0
3.0
2.4
(ref)
mNaCl
molkg-1
molkg-1
aexp
w
a(exp-corr)
104
w
0.465
0.758
0.804
1.018
1.136
1.137
1.185
1.298
1.457
1.605
1.683
0.653
1.059
1.120
1.429
1.609
1.610
1.698
1.851
2.106
2.338
2.465
0.9785
0.9648
0.9627
0.9520
0.9457
0.9456
0.9425
0.9370
0.9277
0.9190
0.9142
1.6
-1.5
-0.7
0.5
0.8
0.8
-4.6
3.1
1.2
0.9
-1.0
Journal of Chemical and Engineering Data, Vol. 49, No. 4, 2004 945
Table 3. Activity of Water in Aqueous Solutions of
Sodium Chloride and Citric Acid at 298.15 K
m
NaCl
m
H3Cit
(ref)
m
NaCl
molkg-1
molkg-1
molkg-1
aexp
w
a(exp-corr)
104
w
0.506
0.498
0.499
0.499
0.498
0.503
0.503
0.499
0.498
0.499
0.502
0.498
0.500
0.501
0.988
0.995
0.987
0.997
0.988
0.970
0.995
0.997
0.986
0.999
2.001
1.985
1.946
1.974
1.944
1.946
1.981
1.981
2.984
2.975
2.931
2.939
2.924
0.101
0.103
0.301
0.502
0.973
1.562
2.514
2.993
3.486
3.580
4.009
4.489
5.034
5.517
0.493
1.492
2.171
2.506
2.471
2.918
3.483
4.737
4.939
5.647
0.500
1.503
1.945
2.469
2.907
3.410
3.964
4.447
0.675
1.393
1.954
2.450
2.955
0.596
0.544
0.666
0.758
1.103
1.492
2.033
2.341
2.651
2.752
3.029
3.299
3.715
4.031
1.285
1.865
2.295
2.513
2.476
2.752
3.163
3.922
4.031
4.525
2.296
2.786
3.029
3.393
3.596
3.922
4.248
4.525
3.299
3.715
4.001
4.248
4.516
0.9804
0.9821
0.9779
0.9750
0.9633
0.9498
0.9303
0.9188
0.9070
0.9030
0.8921
0.8811
0.8639
0.8503
0.9571
0.9365
0.9206
0.9125
0.9137
0.9030
0.8895
0.8550
0.8503
0.8286
0.9206
0.9017
0.8921
0.8773
0.8689
0.8550
0.8409
0.8286
0.8811
0.8639
0.8513
0.8409
0.8290
-1.0
5.7
2.9
12
-9.3
-18
2.8
2.3
7.0
-7.8
-4.4
14
-4.9
-0.3
-3.3
3.0
-6.0
-4.0
-3.3
-8.2
7.9
1.0
7.2
0.4
-5.6
15
5.0
-8.6
3.1
-6.5
11
19
17
-3.2
-18
-1.0
-1.2
ln aw )
Mw
1000
2AIm
(Im)1/2
1/2
(1 + b(Im) )
S
exp(-R(Im)1/2)
(0)
i,j mimj
(1)
i,j mimj
i)1 j)1
i)1 j)1
i,j,kmimjmk
m
i)1
(1)
m
NaNO3
m
H3Cit
(ref)
m
NaCl
molkg-1
molkg-1
molkg-1
aexp
w
a(exp-corr)
104
w
0.194
0.296
0.379
0.447
0.542
0.620
0.782
0.840
0.907
1.001
1.105
1.203
0.519
0.602
0.719
0.928
1.136
1.226
1.335
1.410
1.631
1.815
2.030
0.506
0.711
0.903
1.107
1.312
1.500
1.915
2.094
2.290
2.480
2.715
2.906
1.742
1.599
1.507
1.389
1.250
1.134
0.892
0.807
0.706
0.561
0.399
0.247
2.663
2.560
2.419
2.155
1.884
1.768
1.623
1.521
1.221
0.962
0.658
3.861
3.638
3.420
3.203
2.975
2.758
2.261
2.043
1.796
1.552
1.257
1.005
1.223
1.223
1.223
1.223
1.223
1.223
1.223
1.223
1.223
1.223
1.223
1.223
2.102
2.102
2.102
2.102
2.102
2.102
2.102
2.102
2.102
2.102
2.102
2.870
2.870
2.870
2.870
2.870
2.870
2.870
2.870
2.870
2.870
2.870
2.870
0.9592
0.9592
0.9592
0.9592
0.9592
0.9592
0.9592
0.9592
0.9592
0.9592
0.9592
0.9592
0.9287
0.9287
0.9287
0.9287
0.9287
0.9287
0.9287
0.9287
0.9287
0.9287
0.9287
0.8984
0.8984
0.8984
0.8984
0.8984
0.8984
0.8984
0.8984
0.8984
0.8984
0.8984
0.8984
5.5
6.2
12
7.1
6.5
5.9
4.4
4.5
3.7
2.4
1.0
0.1
7.0
7.2
8.4
8.2
6.9
6.6
5.9
5.1
3.2
0.5
-1.4
-4.2
-2.5
-3.1
0.2
1.4
0.6
2.4
3.8
-5.9
-8.1
-8.4
-9.7
(0)
(0)
) j,i
. Mw is the molar mass of water; Im is the ionic
i,j
strength
Im )
1
2
mz
2
i i
(2)
i)1
946
Table 5. Activity of Water in Aqueous Solutions of Sodium Citrate and Citric Acid at 298.15 K
m
NaCit
m
H3Cit
(ref)
m
NaCl
molkg-1
molkg-1
molkg-1
aexp.
w
0.032
0.063
0.100
0.130
0.162
0.197
0.226
0.261
0.297
0.327
0.396
0.130
0.237
0.325
0.392
0.448
0.484
0.519
0.554
0.590
0.626
0.134
0.245
0.331
0.402
0.462
0.497
0.606
0.644
0.132
0.252
0.356
0.445
0.518
0.581
0.632
0.678
0.715
0.752
0.782
0.051
0.137
0.264
0.376
0.466
0.613
0.667
0.715
0.755
0.794
0.822
0.856
0.101
1.052
0.986
0.900
0.826
0.743
0.652
0.571
0.481
0.386
0.307
0.140
1.315
1.081
0.867
0.689
0.536
0.443
0.347
0.256
0.166
0.080
1.345
1.105
0.895
0.711
0.551
0.455
0.173
0.083
1.844
1.634
1.424
1.224
1.038
0.872
0.731
0.594
0.484
0.374
0.284
2.048
1.922
1.708
1.488
1.291
0.919
0.768
0.620
0.506
0.389
0.296
0.200
2.501
0.653
0.653
0.653
0.653
0.653
0.653
0.653
0.653
0.653
0.653
0.653
0.919
0.919
0.919
0.919
0.919
0.919
0.919
0.919
0.919
0.919
0.948
0.948
0.948
0.948
0.948
0.948
0.948
0.948
1.226
1.226
1.226
1.226
1.226
1.226
1.226
1.226
1.226
1.226
1.226
1.284
1.284
1.284
1.284
1.284
1.284
1.284
1.284
1.284
1.284
1.284
1.284
1.609
0.9785
0.9785
0.9785
0.9785
0.9785
0.9785
0.9785
0.9785
0.9785
0.9785
0.9785
0.9696
0.9696
0.9696
0.9696
0.9696
0.9696
0.9696
0.9696
0.9696
0.9696
0.9686
0.9686
0.9686
0.9686
0.9686
0.9686
0.9686
0.9686
0.9591
0.9591
0.9591
0.9591
0.9591
0.9591
0.9591
0.9591
0.9591
0.9591
0.9591
0.9571
0.9571
0.9571
0.9571
0.9571
0.9571
0.9571
0.9571
0.9571
0.9571
0.9571
0.9571
0.9457
a(exp-corr)
w
104
1.7
0.9
0.4
0.2
0.2
0.4
-0.7
-2.1
-6.0
-0.1
-8.4
1.5
2.5
3.9
1.2
-4.4
-8.7
-14
-13
-4.5
<0.1
-1.0
0.4
1.6
-0.5
-5.6
-11
-6.0
-1.7
2.4
3.0
6.5
9.7
9.4
7.2
3.2
-2.9
-8.6
-10
-4.3
2.0
0.2
1.0
5.2
9.0
8.6
4.7
-2.9
-7.1
-8.6
-3.4
1.5
2.0
m
NaCit
m
H3Cit
(ref)
m
NaCl
molkg-1
molkg-1
molkg-1
aexp.
w
a(exp-corr)
104
w
0.200
0.298
0.404
0.933
0.977
1.061
0.164
0.441
0.345
0.293
0.234
0.171
0.108
0.050
0.049
0.111
0.162
0.239
0.301
0.354
0.443
1.191
1.246
1.288
1.321
1.353
0.264
0.516
1.197
1.247
1.296
1.330
1.360
0.049
0.101
0.153
0.202
0.264
0.310
0.373
0.462
1.455
1.494
1.531
1.578
1.547
1.570
1.590
1.607
1.624
1.642
1.655
1.670
2.375
2.240
2.070
0.757
0.613
0.289
2.961
2.641
2.761
2.823
2.893
2.961
3.021
3.075
3.093
3.038
2.988
2.910
2.837
2.774
2.660
0.845
0.625
0.427
0.265
0.120
2.901
2.581
0.855
0.623
0.432
0.266
0.124
3.643
3.609
3.567
3.528
3.476
3.435
3.371
3.287
0.895
0.695
0.470
0.183
0.891
0.760
0.628
0.526
0.407
0.299
0.197
0.096
1.609
1.609
1.609
1.609
1.609
1.609
1.954
1.954
1.954
1.954
1.954
1.954
1.954
1.954
1.971
1.971
1.971
1.971
1.971
1.971
1.971
1.971
1.971
1.971
1.971
1.971
1.983
1.983
1.983
1.983
1.983
1.983
1.983
2.338
2.338
2.338
2.338
2.338
2.338
2.338
2.338
2.338
2.338
2.338
2.338
2.465
2.465
2.465
2.465
2.465
2.465
2.465
2.465
0.9457
0.9457
0.9457
0.9457
0.9457
0.9457
0.9332
0.9332
0.9332
0.9332
0.9332
0.9332
0.9332
0.9332
0.9326
0.9326
0.9326
0.9326
0.9326
0.9326
0.9326
0.9326
0.9326
0.9326
0.9326
0.9326
0.9322
0.9322
0.9322
0.9322
0.9322
0.9322
0.9322
0.9190
0.9190
0.9190
0.9190
0.9190
0.9190
0.9190
0.9190
0.9190
0.9190
0.9190
0.9190
0.9142
0.9142
0.9142
0.9142
0.9142
0.9142
0.9142
0.9142
0.6
2.0
4.6
4.2
-2.0
2.2
-1.6
1.8
-0.4
-1.1
-0.2
<0.1
-0.4
-0.4
-1.6
-1.7
-2.1
-1.4
-1.9
-1.5
0.2
6.2
-1.2
4.3
5.5
6.0
-1.4
3.2
6.2
-4.9
4.6
6.3
6.3
-1.5
<0.1
0.2
0.9
1.5
1.9
0.9
2.8
1.9
-2.6
1.7
3.3
-2.8
-0.6
-3.7
-1.0
<0.1
1.8
0.1
<0.1
(I)
(II)
(III)
(IV)
K(m)
R (T)
) exp -
1
RT
SR
i)1
i,R(ref)
i
(V)
SR
[a ]
i,R
(3)
i)1
Journal of Chemical and Engineering Data, Vol. 49, No. 4, 2004 947
Table 7. Aqueous Phase Chemical Reaction Equilibrium
Constants at 298.15 K
chemical reaction
equilibrium constant
log
log
log
log
log
K(m)
I
K(m)
II
K(m)
III
K(m)
IV
K(m)
V
source
Bates and Pinching10
Bates and Pinching10
Bates and Pinching10
Pitzer et al.11
Schmidt12
) -3.128
) -4.761
) -6.396
) -1.9788
) -14.0
ln i )
z2i
m
Na2SO4
m
H3Cit
(ref)
m
NaCl
molkg-1
molkg-1
molkg-1
aexp
w
a(exp-corr)
104
w
0.213
0.311
0.410
0.517
0.609
0.726
0.816
0.916
1.001
1.095
0.542
0.641
0.736
0.850
1.044
1.224
1.319
1.410
1.574
1.754
1.841
1.934
2.027
0.682
0.936
1.234
1.487
1.666
1.901
2.060
2.201
2.346
2.480
1.677
1.514
1.357
1.175
1.024
0.821
0.662
0.492
0.348
0.199
2.655
2.506
2.374
2.219
1.915
1.625
1.472
1.317
1.039
0.731
0.585
0.436
0.293
3.541
3.219
2.804
2.423
2.141
1.736
1.455
1.198
0.933
0.698
1.233
1.233
1.233
1.233
1.233
1.233
1.233
1.233
1.233
1.233
2.137
2.137
2.137
2.137
2.137
2.137
2.137
2.137
2.137
2.137
2.137
2.137
2.137
2.820
2.820
2.820
2.820
2.820
2.820
2.820
2.820
2.820
2.820
0.9589
0.9589
0.9589
0.9589
0.9589
0.9589
0.9589
0.9589
0.9589
0.9589
0.9265
0.9265
0.9265
0.9265
0.9265
0.9265
0.9265
0.9265
0.9265
0.9265
0.9265
0.9265
0.9265
0.9004
0.9004
0.9004
0.9004
0.9004
0.9004
0.9004
0.9004
0.9004
0.9004
4.0
4.9
7.1
7.9
7.8
6.1
4.0
2.4
0.3
-0.8
1.7
0.1
1.8
5.6
5.3
5.2
5.5
4.2
2.6
-0.9
-2.8
-3.8
-4.0
-14
-11
-6.7
-2.0
2.2
3.1
3.1
1.2
-2.3
-4.5
(1)
i,j
ln(1 + b(Im) ) +
2
2
R Im
(Im)1/2
1/2
(1)
i,j
mimj
R Im
2
z2i
R2I2m
]
[
{
}
(1 + b(Im)1/2)
exp(-R(Im)1/2) 1 +
(1)
i,j
mimj + 2
i)1 j)1
m
j)1
(0)
i,j
+
[1 - (1 + R(Im)1/2) exp(-R(Im)1/2)] +
S
i,j,kmjmk
(5)
j)1 k)1
G(T,ni) )
i i
(6)
ai ) mii
-z2i A
(4)
taking the side conditions (mass balance for the components water, salt, and citric acid, chemical reaction equilibrium) into account. ni and i are the number of moles
and the chemical potential of component i, respectively. The
calculations require information on binary and ternary
interaction parameters of the Pitzer model at 298.15 K.
As usual, parameters for interactions between cations and
cations as well as between anions and anions were set to
zero. The parameters for interactions between sodium ions
on one side and chloride ions, nitrate ions, and sulfate ions
on the other side were taken from Silvester and Pitzer13
15
(Na+/Cl-), Pitzer14 (Na+/NO3 ), and Rogers and Pitzer
(Na+/SO2),
respectively.
Parameters
for
interactions
be4
tween sulfate and bisulfite ions on one side and hydrogenium ions on the other side were taken from Pitzer et al.11
Only a single binary parameter was considered for interactions between citric acid molecules. That parameter was
taken from Kirsch et al.16 All non-neglected parameters are
given in Table 8.
Three parameters for interactions between sodium ions
(0)
(1)
and citrate ions (Na
+,Cit3, Na+,Cit3, and Na+,Na+,Cit3- were
fitted to the new experimental data. They are given in
Table 8. Figure 1 and Table 2 also give a comparison
between the experimental data and the correlation. The
deviations between the experimental results and the correlation for the activity of water a(exp-corr)
are typically
w
about (10-4; the maximum absolute deviation is below
0.005.
The experimental results for the activity of water in
aqueous solutions of sodium citrate and citric acid were
948
NaNO3
Na2SO4
H2SO4
H3Cit
Na3Cit
Na3Cit + H3Cit
NaCl + H3Cit
NaNO3 + H3Cit
Na2SO4 + H3Cit
parameter
(0)
Na
+,Cl(1)
Na
+,ClNa+,Na+,Cl(0)
Na
+,NO 3
(1)
Na
+,NO 3
Na+,Na+,NO3(0)
Na+,SO42(1)
Na
+,SO 24
Na+,Na+,SO42(0)
H
+
23O ,SO4
(0)
H
+
3O ,HSO4
(1)
H
+,HSO O
3
4
H3O+,H3O+,SO42(0)
H3Cit,H3Cit
(0)
H
+
33O ,Cit
(1)
Na
+,Cit3Na+,Na+,Cit3(0)
Na
+,HCit2(1)
Na
+,HCit2Na+,Na+,HCit2(0)
H
3Cit,H2Cit
(1)
H
Cit,H
Cit
3
2
H3Cit,H3Cit,H2Cit(0)
H
3Cit,Cl
(0)
H
3Cit,NO3
(0)
H
23Cit,SO4
H3Cit,H3Cit,SO42-
source
0.0765
0.2664
0.00042
0.0039
0.2115
-0.00002
0.01869
1.0994
0.00131
0.0027
0.2103
0.4711
0.0098
0.0767
0.2744
5.3772
-0.00525
0.09133
-0.2265
-0.00205
-0.09143
-0.1530
0.00757
0.03435
0.00661
0.02418
0.01430
Silvester and
Pitzer13
Pitzer14
Rogers and
Pitzer15
Pitzer et al.11
Kirsch et al.16
this work
this work
this work
this work
this work
Na ,Na ,HCit
+HCit2
eters for interactions between citric acid and H2Cit(0)
(1)
(H
). These pa-, H Cit,H Cit-, and
H3Cit,H3Cit,H2Cit3Cit,H2Cit
3
2
rameters have no influence on the activity of water in
aqueous solutions of sodium citrate, as there the concentrations of molecular citric acid and univalent as well as
divalent citrate ions are very small. The parameters are
also given in Table 8. As is shown in Table 5, the deviations
between the experimental data for the activity of water and
the correlation are not as small as they are for the system
sodium citrate + water. Nevertheless, in most cases, the
calculated numbers for the activity of water agree with the
experimental data within the experimental uncertainty
((0.0005), but in a few cases, the deviations are larger by
up to a factor of 3.
The experimental results for the activity of water in
aqueous solutions of sodium chloride and citric acid were
(0)
used to determine the binary parameter H
- for
3Cit,Cl
interactions between citric acid and chloride ions (the
(0)
corresponding parameter H
+ for interactions be3Cit,Na
tween sodium ions and citric acid is set to zero; this is no
simplification, as in a binary mixture of sodium chloride
and citric acid these parameters always appear as a sum).
In a similar way, the experimental results for the activity
of water in aqueous solutions of sodium nitrate and citric
acid were used to determine the binary parameter
(0)
H
- for interactions between citric acid and nitrate
3Cit,NO3
ions. Both parameters are given in Table 8. The comparisons between calculated and experimental data for the
Journal of Chemical and Engineering Data, Vol. 49, No. 4, 2004 949
(15) Rogers, P. S. Z.; Pitzer, K. S. High-Temperature Properties of
Aqueous Sodium Sulfate Solutions. J. Phys. Chem. 1981, 85,
2886-2895.
(16) Kirsch, T.; Ziegenfu, H.; Maurer, G. Distribution of Citric, Acetic
and Oxalic Acids between Water and Organic Solutions of Trin-Octylamine. Fluid Phase Equilib. 1997, 99, 235-266.
JE034258R