2
0
2017
li
con
0
journal
Original
Li, X.[Xinbao]
Cong, Y.[Yang]
Du, C.[Cunbin]
Zhao, H.[Hongkun]
J. Chem. Thermodyn.
2017
2020-09-29
Solubility and solution thermodynamics of 2-methyl-4-nitroaniline in eleven organic solvents at elevated temperatures
The knowledge of solubility and solution thermodynamics for 2-methyl-4-nitroaniline in different solvents is essential for its purification and further theoretical studies. In this work, the solid-liquid equilibrium for 2-methyl-4-nitroaniline in eleven pure organic solvents (methanol, ethanol, n-propanol, isopropanol, n-butanol, toluene, ethyl acetate, acetonitrile, 2-butanone, acetone and cyclohexane) was established with the isothermal saturation method at temperatures T = (278.15-313.15) K under pressure of 101.2 kPa, and the solubility of 2-methyl-4-nitroaniline in these solvents were determined by a high-performance liquid chromatography (HPLC). In general, the mole fraction solubility obeyed the following order from high to low in different solvents: 2-butanone greater than acetone greater than ethyl acetate greater than acetonitrile greater than methanol greater than ethanol greater than n-propanol greater than n-butanol greater than isopropanol greater than toluene greater than cyclohexane. The modified Apelblat equation, kh equation, Wilson model and NRTL model were employed to correlate the measured solubility values of 2-methyl-4-nitroaniline in the selected solvents. Results show that the largest values of RAD and RMSD obtained with the four models are no greater than 0.71% and 3.27 10 4, respectively. The modified Apelblat equation provided better results than the other three models. Furthermore, the mixing properties, including Gibbs energy, mixing enthalpy, mixing entropy, activity coefficient at infinitesimal concentration (c1 1 ) and reduced excess enthalpy (HE;1 1 ) were computed. The dissolution process of 2-methyl-4-nitroaniline is spontaneous and favourable in the selected solvents. The solubility and associated models would be very useful for optimizing the separation process of the isomeric mixtures of 2-methyl-4-nitroaniline and 2-methyl-6-nitroaniline.
2-Methyl-4-nitroaniline
Solubility
Thermodynamic model
Mixing property
10.1016/j.jct.2016.10.037
105
276-288
1
InChI=1S/C7H8N2O2/c1-5-4-6(9(10)11)2-3-7(5)8/h2-4H,8H2,1H3
XTTIQGSLJBWVIV-UHFFFAOYSA-N
2-methyl-4-nitroaniline
aniline, 2-methyl-4-nitro-
C7H8N2O2
1
Commercial source
1
97.9
3
Stated by supplier
2
Crystallization from solution
3
99.7
3
HPLC
2
InChI=1S/C4H8O/c1-3-4(2)5/h3H2,1-2H3
ZWEHNKRNPOVVGH-UHFFFAOYSA-N
butanone
2-butanone
butan-2-one
ethyl methyl ketone
methyl ethyl ketone
C4H8O
1
Commercial source
1
99.4
3
Stated by supplier
3
InChI=1S/C3H8O/c1-2-3-4/h4H,2-3H2,1H3
BDERNNFJNOPAEC-UHFFFAOYSA-N
propan-1-ol
1-propanol
n-propanol
n-propyl alcohol
C3H8O
1
Commercial source
1
99.4
3
Stated by supplier
4
InChI=1S/C4H10O/c1-2-3-4-5/h5H,2-4H2,1H3
LRHPLDYGYMQRHN-UHFFFAOYSA-N
butan-1-ol
1-butanol
n-butanol
n-butyl alcohol
C4H10O
1
Commercial source
1
99.3
3
Stated by supplier
5
InChI=1S/C3H8O/c1-3(2)4/h3-4H,1-2H3
KFZMGEQAYNKOFK-UHFFFAOYSA-N
propan-2-ol
2-propanol
isopropanol
isopropyl alcohol
sec-propyl alcohol
C3H8O
1
Commercial source
1
99.5
3
Stated by supplier
6
InChI=1S/C2H6O/c1-2-3/h3H,2H2,1H3
LFQSCWFLJHTTHZ-UHFFFAOYSA-N
ethanol
ethyl alcohol
C2H6O
1
Commercial source
1
99.5
3
Stated by supplier
7
InChI=1S/CH4O/c1-2/h2H,1H3
OKKJLVBELUTLKV-UHFFFAOYSA-N
methanol
methyl alcohol
CH4O
1
Commercial source
1
99.7
3
Stated by supplier
8
InChI=1S/C7H8/c1-7-5-3-2-4-6-7/h2-6H,1H3
YXFVVABEGXRONW-UHFFFAOYSA-N
toluene
methylbenzene
C7H8
1
Commercial source
1
99.6
3
Stated by supplier
9
InChI=1S/C4H8O2/c1-3-6-4(2)5/h3H2,1-2H3
XEKOWRVHYACXOJ-UHFFFAOYSA-N
ethyl acetate
ethyl ethanoate
C4H8O2
1
Commercial source
1
99.5
3
Stated by supplier
10
InChI=1S/C2H3N/c1-2-3/h1H3
WEVYAHXRMPXWCK-UHFFFAOYSA-N
acetonitrile
cyanomethane
ethanenitrile
ethanonitrile
methanecarbonitrile
methyl cyanide
C2H3N
1
Commercial source
1
99.4
3
Stated by supplier
11
InChI=1S/C6H12/c1-2-4-6-5-3-1/h1-6H2
XDTMQSROBMDMFD-UHFFFAOYSA-N
cyclohexane
C6H12
1
Commercial source
1
99.6
3
Stated by supplier
12
InChI=1S/C3H6O/c1-3(2)4/h1-2H3
CSCPPACGZOOCGX-UHFFFAOYSA-N
acetone
2-propanone
dimethyl ketone
propan-2-one
propanone
pyroacetic ether
C3H6O
1
Commercial source
1
99.6
3
Stated by supplier
1
10
1
1
1
Principal objective of the work
AB
TRC
4/21/2017
1
Mole fraction
Chromatography
1
Liquid
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
Crystal
1
1
Pressure, kPa
Liquid
101.2
4
1
Temperature, K
Liquid
1
278.15
5
1
0.03078
4
1
0.0016
1
280.65
5
1
0.03351
4
1
0.00174
1
283.15
5
1
0.0362
4
1
0.00188
1
285.65
5
1
0.03898
4
1
0.00203
1
288.15
5
1
0.04225
4
1
0.0022
1
290.65
5
1
0.04555
4
1
0.00237
1
293.15
5
1
0.04909
4
1
0.00256
1
295.65
5
1
0.05278
4
1
0.00275
1
298.15
5
1
0.0566
4
1
0.00295
1
300.65
5
1
0.06066
4
1
0.00316
1
303.15
5
1
0.06506
4
1
0.00339
1
305.65
5
1
0.06986
4
1
0.00364
1
308.15
5
1
0.07469
4
1
0.00389
1
310.65
5
1
0.07971
4
1
0.00415
1
313.15
5
1
0.0852
4
1
0.00443
2
1
1
9
1
Principal objective of the work
AB
TRC
4/21/2017
1
Mole fraction
Chromatography
1
Liquid
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
Crystal
1
1
Pressure, kPa
Liquid
101.2
4
1
Temperature, K
Liquid
1
278.15
5
1
0.06204
4
1
0.00323
1
280.65
5
1
0.06689
4
1
0.00348
1
283.15
5
1
0.07217
4
1
0.00376
1
285.65
5
1
0.07763
4
1
0.00404
1
288.15
5
1
0.08366
4
1
0.00436
1
290.65
5
1
0.08971
4
1
0.00467
1
293.15
5
1
0.09601
4
1
0.005
1
295.65
5
1
0.1026
4
1
0.0053
1
298.15
5
1
0.11
4
1
0.0057
1
300.65
5
1
0.1172
4
1
0.0061
1
303.15
5
1
0.1251
4
1
0.0065
1
305.65
5
1
0.1334
4
1
0.0069
1
308.15
5
1
0.142
4
1
0.0074
1
310.65
5
1
0.151
4
1
0.0079
1
313.15
5
1
0.1602
4
1
0.0083
3
6
1
1
1
Principal objective of the work
AB
TRC
4/21/2017
1
Mole fraction
Chromatography
1
Liquid
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
Crystal
1
1
Pressure, kPa
Liquid
101.2
4
1
Temperature, K
Liquid
1
278.15
5
1
0.00732
4
1
0.000381
1
280.65
5
1
0.00807
4
1
0.00042
1
283.15
5
1
0.00887
4
1
0.000462
1
285.65
5
1
0.00974
4
1
0.000507
1
288.15
5
1
0.01068
4
1
0.00056
1
290.65
5
1
0.01167
4
1
0.00061
1
293.15
5
1
0.01274
4
1
0.00066
1
295.65
5
1
0.01391
4
1
0.00072
1
298.15
5
1
0.01521
4
1
0.00079
1
300.65
5
1
0.01652
4
1
0.00086
1
303.15
5
1
0.01804
4
1
0.00094
1
305.65
5
1
0.01965
4
1
0.00102
1
308.15
5
1
0.02133
4
1
0.00111
1
310.65
5
1
0.02314
4
1
0.0012
1
313.15
5
1
0.02505
4
1
0.0013
4
3
1
1
1
Principal objective of the work
AB
TRC
4/21/2017
1
Mole fraction
Chromatography
1
Liquid
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
Crystal
1
1
Pressure, kPa
Liquid
101.2
4
1
Temperature, K
Liquid
1
278.15
5
1
0.006312
4
1
0.000329
1
280.65
5
1
0.007006
4
1
0.000365
1
283.15
5
1
0.007763
4
1
0.000404
1
285.65
5
1
0.008531
4
1
0.000444
1
288.15
5
1
0.00939
4
1
0.000489
1
290.65
5
1
0.01033
4
1
0.00054
1
293.15
5
1
0.01131
4
1
0.00059
1
295.65
5
1
0.01241
4
1
0.00065
1
298.15
5
1
0.01358
4
1
0.00071
1
300.65
5
1
0.01484
4
1
0.00077
1
303.15
5
1
0.0162
4
1
0.00084
1
305.65
5
1
0.01762
4
1
0.00092
1
308.15
5
1
0.01919
4
1
0.001
1
310.65
5
1
0.02094
4
1
0.00109
1
313.15
5
1
0.02275
4
1
0.00118
5
5
1
1
1
Principal objective of the work
AB
TRC
4/21/2017
1
Mole fraction
Chromatography
1
Liquid
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
Crystal
1
1
Pressure, kPa
Liquid
101.2
4
1
Temperature, K
Liquid
1
278.15
5
1
0.00459
4
1
0.000239
1
280.65
5
1
0.005107
4
1
0.000266
1
283.15
5
1
0.005718
4
1
0.000298
1
285.65
5
1
0.006352
4
1
0.000331
1
288.15
5
1
0.007065
4
1
0.000368
1
290.65
5
1
0.007811
4
1
0.000407
1
293.15
5
1
0.008646
4
1
0.00045
1
295.65
5
1
0.009608
4
1
0.0005
1
298.15
5
1
0.01062
4
1
0.00055
1
300.65
5
1
0.01175
4
1
0.00061
1
303.15
5
1
0.01295
4
1
0.00067
1
305.65
5
1
0.01424
4
1
0.00074
1
308.15
5
1
0.01566
4
1
0.00082
1
310.65
5
1
0.01723
4
1
0.0009
1
313.15
5
1
0.01894
4
1
0.00099
6
12
1
1
1
Principal objective of the work
AB
TRC
4/21/2017
1
Mole fraction
Chromatography
1
Liquid
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
Crystal
1
1
Pressure, kPa
Liquid
101.2
4
1
Temperature, K
Liquid
1
278.15
5
1
0.07643
4
1
0.00398
1
280.65
5
1
0.08153
4
1
0.00424
1
283.15
5
1
0.08748
4
1
0.00455
1
285.65
5
1
0.09328
4
1
0.00486
1
288.15
5
1
0.0996
4
1
0.00518
1
290.65
5
1
0.106
4
1
0.0055
1
293.15
5
1
0.1129
4
1
0.0059
1
295.65
5
1
0.1198
4
1
0.0062
1
298.15
5
1
0.1266
4
1
0.0066
1
300.65
5
1
0.1346
4
1
0.007
1
303.15
5
1
0.1422
4
1
0.0074
1
305.65
5
1
0.1506
4
1
0.0078
1
308.15
5
1
0.1592
4
1
0.0083
1
310.65
5
1
0.1681
4
1
0.0087
1
313.15
5
1
0.1774
4
1
0.0092
7
1
1
8
1
Principal objective of the work
AB
TRC
4/21/2017
1
Mole fraction
Chromatography
1
Liquid
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
Crystal
1
1
Pressure, kPa
Liquid
101.2
4
1
Temperature, K
Liquid
1
278.15
5
1
0.001592
4
1
8.3e-05
1
280.65
5
1
0.001779
4
1
9.3e-05
1
283.15
5
1
0.002042
4
1
0.000106
1
285.65
5
1
0.002301
4
1
0.00012
1
288.15
5
1
0.002575
4
1
0.000134
1
290.65
5
1
0.002847
4
1
0.000148
1
293.15
5
1
0.003172
4
1
0.000165
1
295.65
5
1
0.003535
4
1
0.000184
1
298.15
5
1
0.003912
4
1
0.000204
1
300.65
5
1
0.004389
4
1
0.000229
1
303.15
5
1
0.004796
4
1
0.00025
1
305.65
5
1
0.005266
4
1
0.000274
1
308.15
5
1
0.005841
4
1
0.000304
1
310.65
5
1
0.006453
4
1
0.000336
1
313.15
5
1
0.007139
4
1
0.000372
8
1
1
11
1
Principal objective of the work
AB
TRC
4/21/2017
1
Mole fraction
Chromatography
1
Liquid
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
Crystal
1
1
Pressure, kPa
Liquid
101.2
4
1
Temperature, K
Liquid
1
283.15
5
1
2.498e-05
4
1
1.3e-06
1
285.65
5
1
2.873e-05
4
1
1.5e-06
1
288.15
5
1
3.368e-05
4
1
1.75e-06
1
290.65
5
1
3.87e-05
4
1
2.02e-06
1
293.15
5
1
4.472e-05
4
1
2.33e-06
1
295.65
5
1
5.271e-05
4
1
2.75e-06
1
298.15
5
1
6.127e-05
4
1
3.19e-06
1
300.65
5
1
6.99e-05
4
1
3.64e-06
1
303.15
5
1
8.08e-05
4
1
4.21e-06
1
305.65
5
1
9.261e-05
4
1
4.82e-06
1
308.15
5
1
0.0001076
4
1
5.6e-06
1
310.65
5
1
0.0001222
4
1
6.4e-06
1
313.15
5
1
0.0001394
4
1
7.3e-06
9
7
1
1
1
Principal objective of the work
AB
TRC
4/21/2017
1
Mole fraction
Chromatography
1
Liquid
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
Crystal
1
1
Pressure, kPa
Liquid
101.2
4
1
Temperature, K
Liquid
1
278.15
5
1
0.00834
4
1
0.000434
1
280.65
5
1
0.00913
4
1
0.000475
1
283.15
5
1
0.01011
4
1
0.00053
1
285.65
5
1
0.01093
4
1
0.00057
1
288.15
5
1
0.01192
4
1
0.00062
1
290.65
5
1
0.01305
4
1
0.00068
1
293.15
5
1
0.01419
4
1
0.00074
1
295.65
5
1
0.01546
4
1
0.0008
1
298.15
5
1
0.01676
4
1
0.00087
1
300.65
5
1
0.01803
4
1
0.00094
1
303.15
5
1
0.01977
4
1
0.00103
1
305.65
5
1
0.02133
4
1
0.00111
1
308.15
5
1
0.02312
4
1
0.0012
1
310.65
5
1
0.02491
4
1
0.0013
1
313.15
5
1
0.02698
4
1
0.0014
10
2
1
1
1
Principal objective of the work
AB
TRC
4/21/2017
1
Mole fraction
Chromatography
1
Liquid
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
Crystal
1
1
Pressure, kPa
Liquid
101.2
4
1
Temperature, K
Liquid
1
278.15
5
1
0.08459
4
1
0.0044
1
280.65
5
1
0.08986
4
1
0.00468
1
283.15
5
1
0.09546
4
1
0.00497
1
285.65
5
1
0.1011
4
1
0.0053
1
288.15
5
1
0.1072
4
1
0.0056
1
290.65
5
1
0.1135
4
1
0.0059
1
293.15
5
1
0.1201
4
1
0.0063
1
295.65
5
1
0.1266
4
1
0.0066
1
298.15
5
1
0.1339
4
1
0.007
1
300.65
5
1
0.1412
4
1
0.0073
1
303.15
5
1
0.1486
4
1
0.0077
1
305.65
5
1
0.1566
4
1
0.0082
1
308.15
5
1
0.1649
4
1
0.0086
1
310.65
5
1
0.1737
4
1
0.009
1
313.15
5
1
0.183
4
1
0.0095
11
4
1
1
1
Principal objective of the work
AB
TRC
4/21/2017
1
Mole fraction
Chromatography
1
Liquid
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
Crystal
1
1
Pressure, kPa
Liquid
101.2
4
1
Temperature, K
Liquid
1
278.15
5
1
0.004922
4
1
0.000256
1
280.65
5
1
0.00552
4
1
0.000287
1
283.15
5
1
0.006182
4
1
0.000322
1
285.65
5
1
0.006907
4
1
0.00036
1
288.15
5
1
0.007782
4
1
0.000405
1
290.65
5
1
0.008582
4
1
0.000447
1
293.15
5
1
0.009508
4
1
0.000495
1
295.65
5
1
0.01065
4
1
0.00055
1
298.15
5
1
0.01183
4
1
0.00062
1
300.65
5
1
0.01309
4
1
0.00068
1
303.15
5
1
0.01448
4
1
0.00075
1
305.65
5
1
0.01602
4
1
0.00083
1
308.15
5
1
0.01774
4
1
0.00092
1
310.65
5
1
0.01959
4
1
0.00102
1
313.15
5
1
0.02165
4
1
0.00113