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Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

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Front. Chem. Sci. Eng.    2016, Vol. 10 Issue (2) : 245-254    https://doi.org/10.1007/s11705-016-1569-z
RESEARCH ARTICLE
The solubility of cefquinome sulfate in pure and mixed solvents
Rongbao Qi1,2,Jingkang Wang1,2,Junxiao Ye1,2,Hongxun Hao1,2,*(),Ying Bao1,2
1. State Key Laboratory of Chemical Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China
2. Collaborative Innovation Center of Chemical Science and Chemical Engineering (Tianjin), Tianjin 300072, China
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Abstract

Solid-liquid equilibrium data of cefquinome sulfate is important to develop industrial crystallization processes for cefquinome sulfate. The solubilities of cefquinome sulfate in five pure solvents (methanol, ethanol, ethylene glycol, acetic acid and water) from 277.15 to 305.15 K and in a binary acetone-water solvent from 278.15 to 293.15 K were measured at atmospheric pressure. The pure-solvent solubility data was correlated to the modified Apelblat and Van’t Hoff equations whereas the mixed-solvent system data was correlated to the modified Apelblat, Van’t Hoff, CNIBS/R-K and Jouyban-Acree models. It was found that the solubilities of cefquinome sulfate in all tested solvents decreased with the increasing of temperature. In addition, the thermodynamic properties of the dissolution processes, including standard Gibbs free energy, enthalpy and entropy changes, were calculated using the Van’t Hoff equation. It was found that the dissolution of cefquinome sulfate is exothermic.
Keywords cefquinome sulfate      solubility      thermodynamic properties     
Corresponding Author(s): Hongxun Hao   
Just Accepted Date: 14 April 2016   Online First Date: 29 April 2016    Issue Date: 19 May 2016
 Cite this article:   
Rongbao Qi,Jingkang Wang,Junxiao Ye, et al. The solubility of cefquinome sulfate in pure and mixed solvents[J]. Front. Chem. Sci. Eng., 2016, 10(2): 245-254.
 URL:  
https://academic.hep.com.cn/fcse/EN/10.1007/s11705-016-1569-z
https://academic.hep.com.cn/fcse/EN/Y2016/V10/I2/245
Fig.1  Chemical structure of cefquinome sulfate
Fig.2  Typical PXRD pattern of cefquinome sulfate
Fig.3  Chromatogram of cefquinome sulfate
Concentration/(mg•mL–1) Sample 1Area Sample 2Area Sample 3Area Average
0.02 152.80 161.52 161.95 158.76
0.10 745.39 750.59 721.38 739.12
0.20 1406.3 1350.9 1347.8 1368.4
1.00 6747.3 6707.0 6626.3 6693.6
2.00 12047 12062 12063 12057
10.00 63467 63115 61209 62597
Tab.1  Cefquinome sulfate HPLC peak areas for different concentrations in water
Fig.4  Calibration curve for cefquinome sulfate in water
Solvent T /K 103×xexp a) 103xcal b)
Apelblat 102×RD/% c) Van’t Hoff 102×RD/% c)
Methanol 277.15 56.2 56.8 ?106.8 58.1 ?338.1
281.15 53.2 52.1 206.8 52.2 188.0
285.15 47.1 47.6 ?106.2 47.1 0.000
289.15 43.6 43.3 68.81 42.6 229.4
293.15 38.9 39.3 ?102.8 38.7 51.41
297.15 35.7 35.5 56.02 35.2 140.1
301.15 31.7 31.9 ?63.09 32.1 ?126.2
305.15 28.8 28.7 34.72 29.3 ?173.6
10ARD/% d) 9.314 15.58
Ethanol 277.15 4.50 4.50 0.000 4.50 0.000
281.15 4.21 4.20 23.75 4.20 23.75
285.15 4.01 4.00 24.94 4.10 ?224.4
289.15 3.90 3.90 0.000 3.90 0.000
293.15 3.70 3.70 0.000 3.70 0.000
297.15 3.60 3.50 277.8 3.50 277.8
301.15 3.40 3.40 0.000 3.40 0.000
305.15 3.20 3.30 ?312.5 3.30 ?312.5
10ARD/% 7.987 10.48
Water 277.15 228 230 ?87.72 229 ?43.86
281.15 222 219 135.1 219 135.1
285.15 211 210 47.39 210 47.39
289.15 201 201 0.000 201 0.000
293.15 191 193 ?104.7 193 ?104.7
297.15 185 185 0.000 185 0.000
301.15 178 178 0.000 178 0.000
305.15 173 172 57.80 172 57.80
10ARD/% 5.410 4.861
Acetic acid 281.15 51.0 50.4 117.6 50.9 19.61
285.15 44.7 45.4 ?156.6 45.4 ?156.6
289.15 40.9 40.9 0.000 40.7 48.90
293.15 36.6 36.8 ?54.64 36.5 27.32
297.15 33.6 33.0 178.6 32.9 208.3
301.15 29.7 29.7 0.000 29.7 0.000
305.15 26.5 26.7 ?75.47 26.9 ?150.9
10ARD/% 8.328 8.739
Ethylene glycol 281.15 535 535 0.000 540 ?93.46
285.15 513 512 19.49 512 19.49
289.15 488 488 0.000 485 61.48
293.15 463 464 ?21.60 461 43.20
297.15 443 441 45.15 438 112.9
301.15 416 417 ?24.04 418 ?48.08
305.15 395 394 25.32 398 ?75.95
10ARD/% 1.937 6.493
Tab.2  Mole fraction solubility of cefquinome sulfate in pure solvents at different temperatures ( p = 0.1 MPa)
Fig.5  Experimental cefquinome sulfate mole fraction solubility in pure solvents: (n) Ethanol; (?) Acetic acid; (l) Methanol; (□) Water; (○) Ethylene glycol. The solid lines are the fitted curves from the modified Apelblat equation
Fig.6  Experimental cefquinome sulfate mole fraction solubility in acetone-water mixtures: (n) 278.15 K; (l) 283.15 K; (?) 288.15 K; (?) 293.15 K. The solid lines are the fitted curves from the CNIBS/R-K model
Solvent Methanol Ethanol Water Acetic acid Ethylene glycol
Apelblat A 54.62 11.93 14.57 42.60 25.70
B ?764.3 43.74 36.03 ?73.98 ?233.5
C ?9.730 ?3.110 ?2.880 ?8.040 ?4.520
Tab.3  Modified Apelblat equation parameters for cefquinome sulfate in pure solvents
T/K xBa) 103×x1exp b) 103×x1cal c)
Apelblat 102×RD/%d) Van’t Hoff 10×RD/%d) CNIBS/R-K 102×RD/%d) Jouyban-Acree 10×RD/%d)
278.15 0.1 1.69 1.70 ?59.17 1.66 17.75 1.70 ?59.17 0.393 767.5
0.2 4.57 4.58 ?21.88 4.69 ?26.26 4.40 372.0 3.11 319.5
0.3 9.82 9.84 ?20.37 10.1 ?28.51 10.3 ?488.8 10.8 ?99.80
0.4 22.5 22.6 ?44.44 22.9 ?17.78 22.6 ?44.44 24.4 ?84.44
0.5 50.1 50.0 19.96 51.0 ?17.96 47.7 479.0 47.3 55.89
0.6 94.7 95.2 ?52.80 96.0 ?13.73 95.8 ?116.2 90.7 42.24
0.7 171 171 0.000 172 ?5.848 177 ?350.9 174 ?17.54
0.8 293 295 ?68.26 295 ?6.826 285 273.0 299 ?20.48
0.9 365 366 ?27.40 357 21.92 368 ?82.19 361 10.96
283.15 0.1 1.16 1.14 172.4 1.16 0.000 1.17 ?86.21 0.262 774.1
0.2 3.48 3.47 28.74 3.39 25.86 3.37 316.1 2.07 405.2
0.3 7.39 7.36 40.60 7.19 27.06 7.70 ?419.5 7.26 17.59
0.4 16.1 16.0 62.11 15.7 24.84 16.0 62.11 16.8 ?43.48
0.5 34.1 34.3 ?58.65 33.6 14.66 33.0 322.6 33.4 20.53
0.6 67.7 66.7 147.7 66.2 22.16 68.1 ?59.08 65.7 29.54
0.7 130 131 ?76.92 130 0.000 135 ?384.6 129 7.692
0.8 236 232 169.5 232 16.95 229 296.6 228 33.90
0.9 282 280 70.92 287 ?17.73 284 ?70.92 284 ?7.092
288.15 0.1 0.794 0.809 ?188.9 0.829 ?44.08 0.800 ?75.57 0.178 775.8
0.2 2.53 2.53 0.000 2.47 23.72 2.45 316.2 1.41 442.7
0.3 5.29 5.32 ?56.71 5.20 17.01 5.48 ?359.2 5.02 51.04
0.4 11.0 11.1 ?90.91 11.0 0.000 11.0 0.000 11.9 ?81.82
0.5 23.1 22.9 86.58 22.5 25.97 22.3 346.3 24.3 ?51.95
0.6 45.9 46.6 ?152.5 46.2 ?6.536 47.3 ?305.0 48.9 ?65.36
0.7 101 100 99.01 99.3 16.83 99.5 148.5 98.9 20.79
0.8 180 184 ?222.2 184 ?22.22 181 ?55.56 179 5.556
0.9 226 227 ?44.25 233 ?30.97 226 0.000 231 ?22.12
293.15 0.1 0.616 0.612 64.94 0.597 30.84 0.615 16.23 0.123 800.3
0.2 1.78 1.78 0.000 1.83 ?28.09 1.79 ?56.18 0.978 450.6
0.3 3.73 3.72 26.81 3.80 ?18.77 3.79 ?160.9 3.55 48.26
0.4 7.66 7.63 39.16 7.74 ?10.44 7.38 365.5 8.61 ?124.0
0.5 14.9 14.9 0.000 15.2 ?20.13 15.0 ?67.11 18.1 ?214.8
0.6 32.6 32.4 61.35 32.7 ?3.067 33.2 ?184.0 37.4 ?147.2
0.7 75.7 75.9 ?26.42 76.5 ?10.57 74.9 105.7 77.7 ?26.42
0.8 148 147 67.57 147 6.757 147 67.57 145 20.27
0.9 195 195 0.000 190 25.64 196 ?51.28 193 10.26
10ARD/%e) 6.581 17.99 19.35 169.9
Tab.4  Experimental (x1exp) and calculated (x1cal) cefquinome sulfate mole fraction solubility in acetone-water mixtures at different temperatures ( p = 0.1 MPa)
T /K
278.15 283.15 288.15 293.15
Apelblat A ?131.5 ?590.4 ?441.8 ?236.8
B 2.992 22.35 16.73 9.307
C 20.65 89.32 66.79 35.44
CNIBS/R-K B0 ?7.490 ?8.250 ?8.860 ?9.100
B1 12.30 18.00 21.56 21.63
B2 ?12.87 ?34.91 ?49.18 ?52.82
B3 17.31 49.51 70.68 78.50
B4 ?10.32 ?25.95 ?36.14 ?40.30
Jouyban-Acree A0 ?126.24
A1 9971.2
A2 14.059
A3 ?428.04
A4 25246
A5 ?27784
A6 33405
A7 ?14892
A8 67.571
ARD 0.16991
Tab.5  Model parameters for the binary solvent systems
Solvent Apelblat Van’t Hoff
Methanol 0.93 1.56
Ethanol 0.79 1.06
Water 0.54 0.48
Acetic acid 0.83 0.87
Ethylene glycol 0.19 0.65
Tab.6  ARD/% of cefquinome sulfate in pure solvents at different temperatures (p = 0.1 MPa)
Apelblat Van’t Hoff CNIBS/R-K Jouyban-Acree
0.66 1.80 1.94 17.0
Tab.7  ARD/% of cefquinome sulfate in binary solvent mixtures at different temperatures (p = 0.1 MPa)
Solvent DHdq /(kJ·mol?1) DSdq /(J·mol?1·K?1) DGdq/(kJ·mol?1)
Methanol ?17.17 8.04 ?83.32
Ethanol ?7.89 14.02 ?72.42
Water ?7.26 4.08 ?37.47
Acetic acid ?18.95 8.05 ?92.15
Ethylene glycol ?9.06 1.88 ?37.35
Tab.8  Dissolution properties of cefquinome sulfate calculated from the Van’t Hoff equation in pure solvents (p = 0.1 MPa)
xB DHdq/(kJ·mol?1) DSdq/(J·mol?1·K?1) DGdq/(kJ·mol?1)
0.10 ?46.11 ?219.01 16.45
0.20 ?42.56 ?197.59 13.88
0.30 ?43.93 ?196.17 12.11
0.40 ?49.05 ?207.74 10.29
0.50 ?54.63 ?221.14 8.54
0.60 ?48.68 ?194.49 6.88
0.70 ?36.73 ?146.68 5.17
0.80 ?31.56 ?123.61 3.75
0.90 ?28.50 ?111.03 3.22
Tab.9  Dissolution properties of cefquinome sulfate calculated from the Van’t Hoff equation in binary solvents (p = 0.1 MPa)
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