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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.    2015, Vol. 9 Issue (1) : 94-104    https://doi.org/10.1007/s11705-015-1460-3
RESEARCH ARTICLE
Thermodynamic study on dynamic water and organic vapor sorption on amorphous valnemulin hydrochloride
Jinbo OUYANG1,2,Jingkang WANG1,2,Yongli WANG1,2,Qiuxiang YIN1,2,Hongxun HAO1,2,*()
1. School of Chemical Engineering and Technology, State Key Laboratory of Chemical Engineering, Tianjin University, Tianjin 300072, China
2. Collaborative Innovation Center of Chemical Science and Chemical Engineering (Tianjin), Tianjin 300072, China
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Abstract

The sorption of water and organic vapors on valnemulin hydrochloride was determined by dynamic vapor sorption at 25 °C. The adsorption-desorption behavior of water vapor and a series of organic vapors was investigated to probe the structural changes in valnemulin hydrochloride before and after sorption. The isothermal adsorption equilibrium data was evaluated using Guggenheim-Anderson-deBoer (GAB) and Brunauer-Emmett-Teller (BET) models. The BET model is applicable only at low relative pressures (0.1≤RP≤0.4) while the GAB model is applicable in the whole range of RPs (0.1≤RP≤0.9). The sorption kinetics at high RPs was determined by fitting the sorption data to the Avrami equation and the sorption content vs. time relationship could be predicted by the Avrami equation. Finally, the possible sorption mechanism of valnemulin hydrochloride was also discussed.
Keywords valnemulin hydrochloride      water vapor      organic vapors      sorption      kinetics     
Corresponding Author(s): Hongxun HAO   
Online First Date: 02 February 2015    Issue Date: 07 April 2015
 Cite this article:   
Yongli WANG,Qiuxiang YIN,Hongxun HAO, et al. Thermodynamic study on dynamic water and organic vapor sorption on amorphous valnemulin hydrochloride[J]. Front. Chem. Sci. Eng., 2015, 9(1): 94-104.
 URL:  
https://academic.hep.com.cn/fcse/EN/10.1007/s11705-015-1460-3
https://academic.hep.com.cn/fcse/EN/Y2015/V9/I1/94
Fig.1  Relative pressure steps with the corresponding mass change for valnemulin hydrochloride at 25 °C. Relative pressure: stepped line; weight change: the curve
Fig.2  Representative pictures of (a) the powder sample of valnemulin hydrochloride and (b) the gel product after sorption-desorption experiments
Fig.3  Representative x-ray powder di?raction pattern of (a) the powder sample of valnemulin hydrochloride and (b) the gel product after sorption-desorption experiments
RP Equilibrium vapor content, M /(g·g-1 d.s.)
Methanol Dichloromethane Toluene Water
0.0 0.0000 0.0000 0.0000 0.0000
0.1 0.0182 0.0168 0.0103 0.0082
0.2 0.0338 0.0274 0.0178 0.0157
0.3 0.0531 0.0390 0.0234 0.0226
0.4 0.0821 0.0533 0.0307 0.0284
0.5 0.1272 0.0716 0.0757 0.0358
0.6 0.1521 0.0931 0.1471 0.0492
0.7 0.2351 0.1175 0.1739 0.0704
0.8 0.4056 0.1458 0.2130 0.1008
0.9 0.6631 0.1798 0.3038 0.1500
0.8 0.5412 0.1675 0.2708 0.1269
0.7 0.3477 0.1575 0.2482 0.1124
0.6 0.2685 0.1516 0.2358 0.1024
0.5 0.2277 0.1472 0.2275 0.0947
0.4 0.2052 0.1429 0.2203 0.0879
0.3 0.1913 0.1383 0.2157 0.0810
0.2 0.1812 0.1325 0.2111 0.0707
0.1 0.1733 0.1237 0.2061 0.0560
0.0 0.1659 0.0489 0.2028 0.0274
0.1 0.1616 0.0924 0.2005 0.0221
0.2 0.1581 0.1010 0.1993 0.0254
0.3 0.1554 0.0984 0.1987 0.0302
0.4 0.1539 0.0945 0.1988 0.0357
0.5 0.1579 0.0951 0.1986 0.0399
0.6 0.1835 0.0962 0.1970 0.0483
Tab.1  Experimental vapor content in valnemulin hydrochloride at different relative pressuresa)
Fig.4  Experimentally measured equilibrium vapor content in valnemulin hydrochloride in (a) methanol, (b) dichloromethane, (c) toluene, (d) water; □, adsorption 1; ?, desorption 1; ○, adsorption 2
Fig.5  Experimental and BET equilibrium vapor content in valnemulin hydrochloride in (a) methanol, (b) dichloromethane, (c) toluene, and (d) water. The solid lines are the values calculated using the BET model. The arrow represents the upper limit at RP=0.4
Fig.6  Experimental and GAB equilibrium vapor content in valnemulin hydrochloride in (a) methanol, (b) dichloromethane, (c) toluene, and (d) water. The solid lines are the values calculated using the GAB model
RP Experimental vapor content, M /(g·g-1 d.s.) Calculated vapor content, M /(g·g-1 d.s.)
BET GAB
Methanol
0.0 0.0000 0.0000 0.0000
0.1 0.0182 0.0179 0.0128
0.2 0.0338 0.0348 0.0289
0.3 0.0531 0.0525 0.0497
0.4 0.0821 0.0729 0.0772
0.5 0.1272 0.0987 0.1148
0.6 0.1521 0.1350 0.1687
0.7 0.2351 0.1930 0.2507
0.8 0.4056 0.3061 0.3890
0.9 0.6631 0.6408 0.6660
SSE 0.0133 0.0010
RMSE 0.0365 0.0102
Dichloromethane
0.0 0.0000 0.0000 0.0000
0.1 0.0168 0.0165 0.0126
0.2 0.0274 0.0281 0.0258
0.3 0.0390 0.0386 0.0399
0.4 0.0533 0.0502 0.0555
0.5 0.0716 0.0647 0.0729
0.6 0.0931 0.0851 0.0929
0.7 0.1175 0.1178 0.1164
0.8 0.1458 0.1819 0.1448
0.9 0.1798 0.3724 0.1806
SSE 0.0385 0.0000
RMSE 0.0620 0.0018
Toluene
0.0 0.0000 0.0000 0.0000
0.1 0.0103 0.0105 0.0099
0.2 0.0178 0.0174 0.0223
0.3 0.0234 0.0236 0.0380
0.4 0.0307 0.0305 0.0579
0.5 0.0756 0.0390 0.0836
0.6 0.1471 0.0511 0.1172
0.7 0.1739 0.0705 0.1617
0.8 0.2130 0.1085 0.2220
0.9 0.3038 0.2216 0.3058
SSE 0.0389 0.0022
RMSE 0.0624 0.0147
Water
0.0 0.0000 0.0000 0.0000
0.1 0.0082 0.0082 0.0069
0.2 0.0157 0.0154 0.0137
0.3 0.0226 0.0227 0.0209
0.4 0.0284 0.0311 0.0291
0.5 0.0358 0.0414 0.0388
0.6 0.0492 0.0559 0.0515
0.7 0.0704 0.0795 0.0696
0.8 0.1008 0.1255 0.0983
0.9 0.1499 0.2583 0.1508
SSE 0.0125 0.0002
RMSE 0.0354 0.0018
Tab.2  Experimental and correlated vapor adsorption content in valnemulin hydrochloride at different relative pressures
Parameters Methanol Dichloromethane Toluene Water
BET
Wm /(g·g-1 d.s.) 0.0666 0.0380 0.0225 0.0268
C 2.8700 5.7900 6.4500 3.4300
GAB
Wm /(g·g-1 d.s.) 0.1593 0.1119 0.4814 0.0324
C 0.7890 1.7440 0.0330 2.4440
K 0.9050 0.6310 0.5520 0.8940
Tab.3  Calculated parameters of the BET and GAB models
Fig.7  Experimental and correlated dynamic sorption vapor content in valnemulin hydrochloride in (a) methanol, (b) dichloromethane, (c) toluene, and (d) water. The solid step lines are the RP values and the solid curves are the values calculated from the Avrami equation
Parameter Methanol Dichloromethane Toluene Water
Target relative pressure
0.5
W0 /(g·g-1 d.s.) 0.0469 0.0261 0.0046 0.0130
dW /(g·g-1 d.s.) 0.0562 0.0569 0.0599 0.0045
K 0.1366 0.0100 0.0370 0.0540
SSE 0.0457 0.0014 0.0025 0.0001
RMSE 0.0036 0.0005 0.0008 0.0014
0.6
W0 /(g·g-1 d.s.) 0.1111 0.0511 0.0448 0.0188
dW /(g·g-1 d.s.) 0.0224 0.0702 0.0773 0.0122
K 0.0320 0.0080 0.0980 0.0410
SSE 0.0001 0.0024 0.0055 0.0000
RMSE 0.0001 0.0008 0.0011 0.0000
0.7
W0 /(g·g-1 d.s.) 0.1187 0.0624 0.1196 0.0259
dW /(g·g-1 d.s.) 0.1332 0.0339 0.0284 0.0278
K 0.0250 0.0390 0.0730 0.0460
SSE 0.0107 0.0048 0.0038 0.0067
RMSE 0.0015 0.0011 0.0009 0.0011
0.8
W0 /(g·g-1 d.s.) 0.1874 0.0843 0.1483 0.0541
dW /(g·g-1 d.s.) 0.2507 0.0354 0.0454 0.0275
K 0.0330 0.0651 0.0433 0.0730
SSE 0.0734 0.0225 0.0067 0.0000
RMSE 0.0041 0.0023 0.0012 0.0000
0.9
W0 /(g·g-1 d.s.) 0.3509 0.1095 0.1850 0.0733
dW /(g·g-1 d.s.) 0.4858 0.0433 0.1152 0.0581
k 0.0191 0.0880 0.0352 0.0401
SSE 0.0855 0.0782 0.0038 0.0195
RMSE 0.0044 0.0044 0.0009 0.0016
Tab.4  Calculated Avrami equation kinetic parameters at different RPs
Fig.8  Schematic diagram of two different sorption mechanisms (a) surface adsorption, (b) bulk absorption. The black and white ovals represent solvent molecules and valnemulin hydrochloride, respectively
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