2
0
2019
yao
li
0
journal
Original
Yao, M.[Menghui]
Li, W.[Wenlong]
Shi, P.[Peng]
Li, W.[Wanya]
Wang, L.[Lingyu]
Zhou, L.[Lina]
Tang, W.[Weiwei]
J. Chem. Eng. Data
2019
2020-09-29
Solid-Liquid Phase Equilibrium and Thermodynamic Analysis of N,N'-Diethylthiourea in Different Solvent Systems
In this work, the solid-liquid phase equilibrium of N, N'-Diethylthiourea (DETU) was investigated in different solvent systems from both solid-state structure and solution thermodynamics. The single crystal structure of DETU was determined for the first time, and the intermolecular hydrogen bonding N-HS interactions are dominant in the crystal packing. The thermodynamic equilibrium solubility was determined by the gravimetric method in twelve solvents (methanol, ethanol, n-propanol, isopropanol, nbutanol, sec-butylalcohol, n-pentanol, acetone, butanone, methyl acetate, ethyl acetate, and acetonitrile) from 283.15 K to 323.15 K. It was found that the solubility in alcohols decreases with increasing the length of carbon chain and follows the rule of "like dissolves like", whereas in non-alcohol solvents the rule does not apply. The experimental data were further correlated by the modified Apelblat equation, h equation and NRTL model. All the correlation derivations are lower than 5%, and the NRTL model receives the best fitting performance. Furthermore, the thermodynamic functions of mixing including enthalpy, entropy, and Gibbs energy were derived, and the results expectedly suggest a spontaneous and entropy-driven mixing process. All the crystallographic and thermodynamic data reported in this study will provide the fundamental data for designing and optimizing the crystallization of DETU.
Solid-liquid phase equilibrium
Solubility
Intermolecular interactions
Solution thermodynamics
N, N'-Diethylthiourea
10.1021/acs.jced.9b00854
12
64
6031-6040
1
InChI=1S/C5H12N2S/c1-3-6-5(8)7-4-2/h3-4H2,1-2H3,(H2,6,7,8)
FLVIGYVXZHLUHP-UHFFFAOYSA-N
N,N'-diethylthiourea
1,3-diethylthiourea
C5H12N2S
1
Commercial source
1
98
3
Stated by supplier
2
InChI=1S/CH4O/c1-2/h2H,1H3
OKKJLVBELUTLKV-UHFFFAOYSA-N
methanol
methyl alcohol
CH4O
1
Commercial source
1
99.5
3
Stated by supplier
3
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
4
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
99.5
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/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
99.5
3
Stated by supplier
7
InChI=1S/C4H10O/c1-3-4(2)5/h4-5H,3H2,1-2H3
BTANRVKWQNVYAZ-UHFFFAOYSA-N
butan-2-ol
(RS)-2-butanol
2-butanol
DL-2-butanol
dl-2-butanol
dl-sec-butyl alcohol
sec-butanol
sec-butyl alcohol
C4H10O
1
Commercial source
1
99.5
3
Stated by supplier
8
InChI=1S/C5H12O/c1-2-3-4-5-6/h6H,2-5H2,1H3
AMQJEAYHLZJPGS-UHFFFAOYSA-N
pentan-1-ol
1-pentanol
amyl alcohol
n-amyl alcohol
n-pentyl alcohol
pentyl alcohol
C5H12O
1
Commercial source
1
99.5
3
Stated by supplier
9
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
99.5
3
Stated by supplier
10
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
99.5
3
Stated by supplier
11
InChI=1S/C3H6O2/c1-3(4)5-2/h1-2H3
KXKVLQRXCPHEJC-UHFFFAOYSA-N
methyl ethanoate
acetic acid, methyl ester
ethanoic acid, methyl ester
methyl acetate
C3H6O2
1
Commercial source
1
99.5
3
Stated by supplier
12
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
13
InChI=1S/C2H3N/c1-2-3/h1H3
WEVYAHXRMPXWCK-UHFFFAOYSA-N
acetonitrile
cyanomethane
ethanenitrile
ethanonitrile
methanecarbonitrile
methyl cyanide
C2H3N
1
Commercial source
1
99.5
3
Stated by supplier
1
1
1
Principal objective of the work
EP
EP
9/30/2019
1
Mass density, kg/m3
X-ray diffraction
Crystal
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Crystal
1
Temperature, K
Crystal
2
Pressure, kPa
Crystal
1
293
3
2
101.325
6
1
1120
5
1
5.8
2
1
1
Principal objective of the work
EP
EP
9/30/2019
1
Triple point temperature, K
DSC
Crystal
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Crystal
Liquid
Air at 1 atmosphere
1
351.28
5
1
0.87
3
1
1
Principal objective of the work
EP
EP
9/30/2019
1
Molar enthalpy of transition or fusion, kJ/mol
DSC
Crystal
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Crystal
Liquid
Air at 1 atmosphere
1
15.67
4
1
0.86
4
1
1
2
1
Principal objective of the work
EP
EP
9/30/2019
1
Mole fraction
gravimetric
1
Liquid
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
Crystal
1
1
Pressure, kPa
Liquid
100
1
1
Temperature, K
Liquid
1
283.15
5
1
0.2323
4
1
0.014
1
288.15
5
1
0.2693
4
1
0.0163
1
293.15
5
1
0.3274
4
1
0.0198
1
298.15
5
1
0.3669
4
1
0.0221
1
303.15
5
1
0.4062
4
1
0.0245
1
308.15
5
1
0.4599
4
1
0.0278
1
313.15
5
1
0.5518
4
1
0.0271
1
318.15
5
1
0.5942
4
1
0.0245
1
323.15
5
1
0.6934
4
1
0.0189
5
1
1
3
1
Principal objective of the work
EP
EP
9/30/2019
1
Mole fraction
gravimetric
1
Liquid
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
Crystal
1
1
Pressure, kPa
Liquid
100
1
1
Temperature, K
Liquid
1
283.15
5
1
0.1997
4
1
0.0121
1
288.15
5
1
0.2424
4
1
0.0147
1
293.15
5
1
0.2887
4
1
0.0174
1
298.15
5
1
0.3224
4
1
0.0195
1
303.15
5
1
0.3865
4
1
0.0233
1
308.15
5
1
0.4125
4
1
0.0249
1
313.15
5
1
0.494
4
1
0.0298
1
318.15
5
1
0.5491
4
1
0.0272
1
323.15
5
1
0.6319
4
1
0.0224
6
1
1
4
1
Principal objective of the work
EP
EP
9/30/2019
1
Mole fraction
gravimetric
1
Liquid
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
Crystal
1
1
Pressure, kPa
Liquid
100
1
1
Temperature, K
Liquid
1
283.15
5
1
0.2057
4
1
0.0124
1
288.15
5
1
0.2353
4
1
0.0142
1
293.15
5
1
0.2947
4
1
0.0178
1
298.15
5
1
0.3233
4
1
0.0195
1
303.15
5
1
0.3743
4
1
0.0225
1
308.15
5
1
0.3986
4
1
0.024
1
313.15
5
1
0.489
4
1
0.0295
1
318.15
5
1
0.531
4
1
0.0283
1
323.15
5
1
0.6272
4
1
0.0227
7
1
1
5
1
Principal objective of the work
EP
EP
9/30/2019
1
Mole fraction
gravimetric
1
Liquid
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
Crystal
1
1
Pressure, kPa
Liquid
100
1
1
Temperature, K
Liquid
1
283.15
5
1
0.1717
4
1
0.0105
1
288.15
5
1
0.215
4
1
0.013
1
293.15
5
1
0.2477
4
1
0.0149
1
298.15
5
1
0.2907
4
1
0.0176
1
303.15
5
1
0.3408
4
1
0.0206
1
308.15
5
1
0.3892
4
1
0.0235
1
313.15
5
1
0.4701
4
1
0.0283
1
318.15
5
1
0.5205
4
1
0.0289
1
323.15
5
1
0.5965
4
1
0.0244
8
1
1
6
1
Principal objective of the work
EP
EP
9/30/2019
1
Mole fraction
gravimetric
1
Liquid
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
Crystal
1
1
Pressure, kPa
Liquid
100
1
1
Temperature, K
Liquid
1
283.15
5
1
0.1754
4
1
0.0106
1
288.15
5
1
0.2104
4
1
0.0127
1
293.15
5
1
0.2523
4
1
0.0152
1
298.15
5
1
0.2943
4
1
0.0177
1
303.15
5
1
0.335
4
1
0.0202
1
308.15
5
1
0.3867
4
1
0.0234
1
313.15
5
1
0.4716
4
1
0.0284
1
318.15
5
1
0.5205
4
1
0.0289
1
323.15
5
1
0.5683
4
1
0.026
9
1
1
7
1
Principal objective of the work
EP
EP
9/30/2019
1
Mole fraction
gravimetric
1
Liquid
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
Crystal
1
1
Pressure, kPa
Liquid
100
1
1
Temperature, K
Liquid
1
283.15
5
1
0.1713
4
1
0.0104
1
288.15
5
1
0.2082
4
1
0.0126
1
293.15
5
1
0.2519
4
1
0.0152
1
298.15
5
1
0.2842
4
1
0.0171
1
303.15
5
1
0.3335
4
1
0.0201
1
308.15
5
1
0.3829
4
1
0.0232
1
313.15
5
1
0.474
4
1
0.0286
1
318.15
5
1
0.5246
4
1
0.0286
1
323.15
5
1
0.5767
4
1
0.0255
10
1
1
8
1
Principal objective of the work
EP
EP
9/30/2019
1
Mole fraction
gravimetric
1
Liquid
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
Crystal
1
1
Pressure, kPa
Liquid
100
1
1
Temperature, K
Liquid
1
283.15
5
1
0.1522
4
1
0.0093
1
288.15
5
1
0.2003
4
1
0.0121
1
293.15
5
1
0.2286
4
1
0.0138
1
298.15
5
1
0.2792
4
1
0.0168
1
303.15
5
1
0.309
4
1
0.0187
1
308.15
5
1
0.3761
4
1
0.0227
1
313.15
5
1
0.4399
4
1
0.0265
1
318.15
5
1
0.4826
4
1
0.0291
1
323.15
5
1
0.5662
4
1
0.0263
11
1
1
9
1
Principal objective of the work
EP
EP
9/30/2019
1
Mole fraction
gravimetric
1
Liquid
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
Crystal
1
1
Pressure, kPa
Liquid
100
1
1
Temperature, K
Liquid
1
283.15
5
1
0.2559
4
1
0.0155
1
288.15
5
1
0.3115
4
1
0.0188
1
293.15
5
1
0.3449
4
1
0.0207
1
298.15
5
1
0.3751
4
1
0.0226
1
303.15
5
1
0.411
4
1
0.0247
1
308.15
5
1
0.4584
4
1
0.0276
1
313.15
5
1
0.5299
4
1
0.0283
1
318.15
5
1
0.5788
4
1
0.0254
1
323.15
5
1
0.6655
4
1
0.0204
12
1
1
10
1
Principal objective of the work
EP
EP
9/30/2019
1
Mole fraction
gravimetric
1
Liquid
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
Crystal
1
1
Pressure, kPa
Liquid
100
1
1
Temperature, K
Liquid
1
283.15
5
1
0.2669
4
1
0.0161
1
288.15
5
1
0.3107
4
1
0.0187
1
293.15
5
1
0.3555
4
1
0.0214
1
298.15
5
1
0.3958
4
1
0.0238
1
303.15
5
1
0.4214
4
1
0.0253
1
308.15
5
1
0.4662
4
1
0.0281
1
313.15
5
1
0.535
4
1
0.028
1
318.15
5
1
0.5739
4
1
0.0257
1
323.15
5
1
0.6245
4
1
0.0227
13
1
1
11
1
Principal objective of the work
EP
EP
9/30/2019
1
Mole fraction
gravimetric
1
Liquid
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
Crystal
1
1
Pressure, kPa
Liquid
100
1
1
Temperature, K
Liquid
1
283.15
5
1
0.1182
4
1
0.0073
1
288.15
5
1
0.1566
4
1
0.0095
1
293.15
5
1
0.1976
4
1
0.012
1
298.15
5
1
0.2485
4
1
0.0151
1
303.15
5
1
0.3015
4
1
0.0183
1
308.15
5
1
0.3676
4
1
0.0223
1
313.15
5
1
0.4531
4
1
0.0273
1
318.15
5
1
0.4917
4
1
0.0297
1
323.15
5
1
0.5918
4
1
0.0248
14
1
1
12
1
Principal objective of the work
EP
EP
9/30/2019
1
Mole fraction
gravimetric
1
Liquid
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
Crystal
1
1
Pressure, kPa
Liquid
100
1
1
Temperature, K
Liquid
1
283.15
5
1
0.1142
4
1
0.007
1
288.15
5
1
0.148
4
1
0.009
1
293.15
5
1
0.1832
4
1
0.0111
1
298.15
5
1
0.2292
4
1
0.0139
1
303.15
5
1
0.2751
4
1
0.0166
1
308.15
5
1
0.3282
4
1
0.0199
1
313.15
5
1
0.4251
4
1
0.0257
1
318.15
5
1
0.4734
4
1
0.0285
1
323.15
5
1
0.5348
4
1
0.028
15
1
1
13
1
Principal objective of the work
EP
EP
9/30/2019
1
Mole fraction
gravimetric
1
Liquid
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
Crystal
1
1
Pressure, kPa
Liquid
100
1
1
Temperature, K
Liquid
1
283.15
5
1
0.129
4
1
0.008
1
288.15
5
1
0.1826
4
1
0.0111
1
293.15
5
1
0.217
4
1
0.0132
1
298.15
5
1
0.2763
4
1
0.0167
1
303.15
5
1
0.3234
4
1
0.0195
1
308.15
5
1
0.3876
4
1
0.0235
1
313.15
5
1
0.4812
4
1
0.029
1
318.15
5
1
0.5307
4
1
0.0283
1
323.15
5
1
0.6138
4
1
0.0234