2
0
2017
li
du
2
journal
Original
Li, X.[Xinbao]
Du, C.[Cunbin]
Cong, Y.[Yang]
Wang, J.[Jian]
Zhao, H.[Hongkun]
J. Chem. Thermodyn.
2017
2020-09-29
Solubility determination and thermodynamic modeling of paclobutrazol in nine organic solvents from T = (278.15 to 318.15) K and mixing properties of solutions
The mole fraction solubility of paclobutrazol ((R,R) and (S,S)) mixture in nine pure solvents including ethanol, isopropanol, n-propanol, 1-butanol, ethyl acetate, toluene, acetone, acetonitrile and 1,4- dioxane was determined experimentally by using the isothermal saturation method over a temperature range from (278.15 to 318.15) K under atmospheric pressure. The mole fraction solubility of paclobutrazol in the selected solvents increased with a rise of temperature. In general, at a certain temperature, they decreased according to the following order in different solvents except for ethyl acetate: toluene greater than 1,4- dioxane greater than acetone greater than 1-butanol greater than n-propanol greater than ethanol greater than isopropanol greater than acetonitrile. The paclobutrazol solubility showed stronger dependency on temperature in ethyl acetate than in the other solvents. The solubility determined for paclobutrazol in the selected solvents was correlated with the modified Apelblat equation, kh equation, Wilson model and NRTL model. The maximum values of root-mean-square deviation (RMSD) and relative average deviation (RAD) were 3.98 10 4 and 1.53%, respectively. On the whole, the four thermodynamic models were all acceptable for describing the systems of paclobutrazol in these solvents. Furthermore, the mixing Gibbs energy, mixing enthalpy, mixing entropy, activity coefficient at infinitesimal concentration (c1 1 ) and reduced excess enthalpy (HE;1 1 ) were obtained. The mixing process of paclobutrazol was spontaneous and exothermic in the solvents studied. The solubility determined and the thermodynamic properties derived should be very helpful for optimizing the purification process of paclobutrazol.
Paclobutrazol
Solubility
Thermodynamic model
Mixing property
10.1016/j.jct.2016.09.038
104
261-273
1
InChI=1S/C15H20ClN3O/c1-15(2,3)14(20)13(19-10-17-9-18-19)8-11-4-6-12(16)7-5-11/h4-7,9-10,13-14,20H,8H2,1-3H3/t13-,14+/m0/s1
RMOGWMIKYWRTKW-UONOGXRCSA-N
2S,3S-Paclobutrazol
(2S,3S)-1-(4-chlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)pentan-3-ol
C15H20ClN3O
1
Commercial source
1
97.9
3
Stated by supplier
2
Crystallization from solution
3
99.3
3
HPLC
2
InChI=1S/C2H6O/c1-2-3/h3H,2H2,1H3
LFQSCWFLJHTTHZ-UHFFFAOYSA-N
ethanol
ethyl alcohol
C2H6O
1
Commercial source
1
99.7
3
Gas chromatography
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
99.5
3
Gas chromatography
4
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
99.7
3
Gas chromatography
5
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
Gas chromatography
6
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
Gas chromatography
7
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
Gas chromatography
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
99.5
3
Gas chromatography
9
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
Gas chromatography
10
InChI=1S/C4H8O2/c1-2-6-4-3-5-1/h1-4H2
RYHBNJHYFVUHQT-UHFFFAOYSA-N
1,4-dioxane
1,4-dioxacyclohexane
dioxane
p-dioxane
tetrahydro-1,4-dioxin
C4H8O2
1
Commercial source
1
99.5
3
Gas chromatography
1
1
1
Principal objective of the work
AB
TRC
4/6/2017
1
Normal melting temperature, K
DTA
Crystal
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Crystal
Liquid
Air at 1 atmosphere
1
433.81
5
1
1.06
2
1
1
Principal objective of the work
AB
TRC
4/6/2017
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
37.86
4
1
1.09
3
7
1
1
1
Principal objective of the work
AB
TRC
4/6/2017
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
0.002394
4
1
0.00012
1
280.65
5
1
0.002668
4
1
0.000134
1
283.15
5
1
0.002954
4
1
0.000148
1
285.65
5
1
0.003305
4
1
0.000165
1
288.15
5
1
0.003662
4
1
0.000183
1
290.65
5
1
0.004052
4
1
0.000203
1
293.15
5
1
0.004486
4
1
0.000225
1
295.65
5
1
0.004947
4
1
0.000248
1
298.15
5
1
0.005436
4
1
0.000272
1
300.65
5
1
0.005962
4
1
0.000298
1
303.15
5
1
0.006528
4
1
0.000327
1
305.65
5
1
0.007092
4
1
0.000355
1
308.15
5
1
0.007761
4
1
0.000389
1
310.65
5
1
0.008456
4
1
0.000423
1
313.15
5
1
0.009165
4
1
0.000459
1
315.65
5
1
0.01005
4
1
0.0005
1
318.15
5
1
0.01096
4
1
0.00055
4
2
1
1
1
Principal objective of the work
AB
TRC
4/6/2017
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
0.007495
4
1
0.000375
1
280.65
5
1
0.008102
4
1
0.000406
1
283.15
5
1
0.008848
4
1
0.000443
1
285.65
5
1
0.009785
4
1
0.00049
1
288.15
5
1
0.01067
4
1
0.00053
1
290.65
5
1
0.01171
4
1
0.00059
1
293.15
5
1
0.01276
4
1
0.00064
1
295.65
5
1
0.01382
4
1
0.00069
1
298.15
5
1
0.01486
4
1
0.00074
1
300.65
5
1
0.016
4
1
0.0008
1
303.15
5
1
0.01729
4
1
0.00087
1
305.65
5
1
0.01853
4
1
0.00093
1
308.15
5
1
0.01999
4
1
0.001
1
310.65
5
1
0.02139
4
1
0.00107
1
313.15
5
1
0.0229
4
1
0.00115
1
315.65
5
1
0.02457
4
1
0.00123
1
318.15
5
1
0.0265
4
1
0.00133
5
3
1
1
1
Principal objective of the work
AB
TRC
4/6/2017
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
0.01238
4
1
0.00062
1
280.65
5
1
0.01308
4
1
0.00065
1
283.15
5
1
0.0139
4
1
0.0007
1
285.65
5
1
0.01463
4
1
0.00073
1
288.15
5
1
0.01548
4
1
0.00077
1
290.65
5
1
0.01628
4
1
0.00081
1
293.15
5
1
0.01718
4
1
0.00086
1
295.65
5
1
0.01819
4
1
0.00091
1
298.15
5
1
0.01925
4
1
0.00096
1
300.65
5
1
0.02029
4
1
0.00102
1
303.15
5
1
0.02152
4
1
0.00108
1
305.65
5
1
0.02285
4
1
0.00114
1
308.15
5
1
0.02411
4
1
0.00121
1
310.65
5
1
0.0253
4
1
0.00127
1
313.15
5
1
0.0265
4
1
0.00133
1
315.65
5
1
0.02784
4
1
0.00139
1
318.15
5
1
0.02914
4
1
0.00146
6
4
1
1
1
Principal objective of the work
AB
TRC
4/6/2017
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
0.007071
4
1
0.000354
1
280.65
5
1
0.007655
4
1
0.000383
1
283.15
5
1
0.008349
4
1
0.000418
1
285.65
5
1
0.009118
4
1
0.000456
1
288.15
5
1
0.009849
4
1
0.000493
1
290.65
5
1
0.01076
4
1
0.00054
1
293.15
5
1
0.01168
4
1
0.00058
1
295.65
5
1
0.01268
4
1
0.00063
1
298.15
5
1
0.01375
4
1
0.00069
1
300.65
5
1
0.01492
4
1
0.00075
1
303.15
5
1
0.01606
4
1
0.0008
1
305.65
5
1
0.01726
4
1
0.00086
1
308.15
5
1
0.01845
4
1
0.00092
1
310.65
5
1
0.01968
4
1
0.00099
1
313.15
5
1
0.02101
4
1
0.00105
1
315.65
5
1
0.02248
4
1
0.00113
1
318.15
5
1
0.02416
4
1
0.00121
7
6
1
1
1
Principal objective of the work
AB
TRC
4/6/2017
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
0.01351
4
1
0.00068
1
280.65
5
1
0.0145
4
1
0.00073
1
283.15
5
1
0.01551
4
1
0.00078
1
285.65
5
1
0.01672
4
1
0.00084
1
288.15
5
1
0.01812
4
1
0.00091
1
290.65
5
1
0.01939
4
1
0.00097
1
293.15
5
1
0.02089
4
1
0.00105
1
295.65
5
1
0.02234
4
1
0.00112
1
298.15
5
1
0.02388
4
1
0.0012
1
300.65
5
1
0.02534
4
1
0.00127
1
303.15
5
1
0.0269
4
1
0.00135
1
305.65
5
1
0.02838
4
1
0.00142
1
308.15
5
1
0.0301
4
1
0.00151
1
310.65
5
1
0.03173
4
1
0.00159
1
313.15
5
1
0.03345
4
1
0.00167
1
315.65
5
1
0.03534
4
1
0.00177
1
318.15
5
1
0.03724
4
1
0.00186
8
8
1
1
1
Principal objective of the work
AB
TRC
4/6/2017
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
0.04162
4
1
0.00208
1
280.65
5
1
0.04264
4
1
0.00213
1
283.15
5
1
0.04373
4
1
0.00219
1
285.65
5
1
0.04496
4
1
0.00225
1
288.15
5
1
0.04622
4
1
0.00231
1
290.65
5
1
0.04734
4
1
0.00237
1
293.15
5
1
0.04843
4
1
0.00242
1
295.65
5
1
0.0496
4
1
0.00248
1
298.15
5
1
0.05082
4
1
0.00254
1
300.65
5
1
0.05208
4
1
0.00261
1
303.15
5
1
0.05331
4
1
0.00267
1
305.65
5
1
0.0546
4
1
0.00273
1
308.15
5
1
0.05574
4
1
0.00279
1
310.65
5
1
0.05705
4
1
0.00286
1
313.15
5
1
0.0584
4
1
0.00292
1
315.65
5
1
0.05969
4
1
0.00299
1
318.15
5
1
0.06099
4
1
0.00305
9
9
1
1
1
Principal objective of the work
AB
TRC
4/6/2017
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
0.01335
4
1
0.00067
1
280.65
5
1
0.01415
4
1
0.00071
1
283.15
5
1
0.01512
4
1
0.00076
1
285.65
5
1
0.01622
4
1
0.00081
1
288.15
5
1
0.01732
4
1
0.00087
1
290.65
5
1
0.01842
4
1
0.00092
1
293.15
5
1
0.01984
4
1
0.00099
1
295.65
5
1
0.02113
4
1
0.00106
1
298.15
5
1
0.02243
4
1
0.00112
1
300.65
5
1
0.02383
4
1
0.00119
1
303.15
5
1
0.02511
4
1
0.00126
1
305.65
5
1
0.02655
4
1
0.00133
1
308.15
5
1
0.0279
4
1
0.0014
1
310.65
5
1
0.02945
4
1
0.00147
1
313.15
5
1
0.03085
4
1
0.00154
1
315.65
5
1
0.03241
4
1
0.00162
1
318.15
5
1
0.0341
4
1
0.00171
10
5
1
1
1
Principal objective of the work
AB
TRC
4/6/2017
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
0.007831
4
1
0.000392
1
280.65
5
1
0.008955
4
1
0.000449
1
283.15
5
1
0.01043
4
1
0.00052
1
285.65
5
1
0.01176
4
1
0.00059
1
288.15
5
1
0.01333
4
1
0.00067
1
290.65
5
1
0.01531
4
1
0.00077
1
293.15
5
1
0.01752
4
1
0.00088
1
295.65
5
1
0.02009
4
1
0.00101
1
298.15
5
1
0.02284
4
1
0.00114
1
300.65
5
1
0.02555
4
1
0.00128
1
303.15
5
1
0.02903
4
1
0.00145
1
305.65
5
1
0.03238
4
1
0.00162
1
308.15
5
1
0.03593
4
1
0.0018
1
310.65
5
1
0.03954
4
1
0.00198
1
313.15
5
1
0.04441
4
1
0.00222
1
315.65
5
1
0.04969
4
1
0.00249
1
318.15
5
1
0.05522
4
1
0.00276
11
10
1
1
1
Principal objective of the work
AB
TRC
4/6/2017
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
0.01563
4
1
0.00078
1
280.65
5
1
0.01679
4
1
0.00084
1
283.15
5
1
0.01832
4
1
0.00092
1
285.65
5
1
0.02029
4
1
0.00102
1
288.15
5
1
0.02235
4
1
0.00112
1
290.65
5
1
0.02477
4
1
0.00124
1
293.15
5
1
0.02709
4
1
0.00136
1
295.65
5
1
0.02964
4
1
0.00148
1
298.15
5
1
0.03237
4
1
0.00162
1
300.65
5
1
0.03508
4
1
0.00176
1
303.15
5
1
0.03806
4
1
0.00191
1
305.65
5
1
0.04118
4
1
0.00206
1
308.15
5
1
0.04401
4
1
0.0022
1
310.65
5
1
0.04746
4
1
0.00238
1
313.15
5
1
0.05122
4
1
0.00256
1
315.65
5
1
0.05512
4
1
0.00276
1
318.15
5
1
0.05929
4
1
0.00297