双季戊四醇在3种混合溶剂中的固-液相平衡

doi:10.11949/0438-1157.20191215

摘要/Abstract

摘要：

采用动态平衡法，在293.15～332.80 K、常压下，测定了双季戊四醇(DPE)在水+(甲醇、乙醇、异丙醇)三种混合溶剂中的溶解度数据。结果表明：DPE在不同质量分数的水+(甲醇、乙醇、异丙醇)混合溶剂中的溶解度随体系温度升高而增大；同一温度下，其在所选取溶剂体系中的溶解度随着甲醇、乙醇或异丙醇质量分数的增大而先增大后减小。λh方程、两参数方程与Apelblat方程均能够对所测定的溶解度数据进行较好的关联；通过修正的van’t Hoff方程计算得到DPE在所选取溶剂体系中Δ_sol H ⁰、Δ_sol S ⁰和Δ_sol G ⁰均大于零，表明DPE在所选取溶剂体系中的溶解过程为吸热、熵增的非自发过程。

关键词: 双季戊四醇, 固-液相平衡, 溶解度, 关联, 热力学性质

Abstract:

In this paper, by the dynamic balance method, the solubility of dipentaerythritol (DPE) in water+(Methanol, ethanol, isopropanol) mixed solvents were evaluated from 293.15 K to 332.80 K under atmospheric pressure. The results showed that the solubility of DPE in different mass fractions of water + (methanol, ethanol, isopropanol) mixed solvents increases with the increasing of temperature. At the same temperature, the solubility in the selected solvent system increases first and then decreases with the increase of the mass fraction of methanol, ethanol or isopropanol. Experimental solubility data were correlated by three thermodynamic models including λh equation, the two parameters equation and the modified Apelblat equation. All the selected models give useful result in regression analysis of solubility. By the modified van t Hoff equation, the calculated Δ_sol H ⁰, Δ_sol S ⁰ and Δ_sol G ⁰of DPE in the selected solvent system are all positive, indicating that the dissolution process is endothermic, entropic and non spontaneous.

Key words: dipentaerythritol, solid-liquid equilibrium, solubility, gating characteristics, thermodynamic properties

中图分类号:

TQ 028.8

李涛, 沙娇, 赵瑞, 张鹏帅, 刘士琪, 李玉, 任保增. 双季戊四醇在3种混合溶剂中的固-液相平衡[J]. 化工学报, 2020, 71(1): 245-253.

Tao LI, Jiao SHA, Rui ZHAO, Pengshuai ZHANG, Shiqi LIU, Yu LI, Baozeng REN. Solid-liquid phase equilibrium of dipentaerythritol in three mixed solvents[J]. CIESC Journal, 2020, 71(1): 245-253.

图/表 14

参考文献 29

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Reagent name	Molecular formula	Specifications and grades	Provenance
DPE	C₁₀H₂₂O₇	≥0.98	Aladdin reagent co. LTD
methanol	CH₃OH	analytical purity，0.995	Kemiou chemical reagent co. LTD
ethanol	CH₃CH₂OH	analytical purity，0.995	Kemiou chemical reagent co. LTD
isopropanol	(CH₃)₂CHOH	analytical purity，0.995	Kemiou chemical reagent co. LTD
water	H₂O	double-distilled water	our laboratory

Reagent name	Molecular formula	Specifications and grades	Provenance
DPE	C₁₀H₂₂O₇	≥0.98	Aladdin reagent co. LTD
methanol	CH₃OH	analytical purity，0.995	Kemiou chemical reagent co. LTD
ethanol	CH₃CH₂OH	analytical purity，0.995	Kemiou chemical reagent co. LTD
isopropanol	(CH₃)₂CHOH	analytical purity，0.995	Kemiou chemical reagent co. LTD
water	H₂O	double-distilled water	our laboratory

T/K	x×10⁴	T/K	x×10⁴	T/K	x×10⁴
w=0.1		315.50	4.440	304.80	2.452
295.85	1.187	317.65	5.346	308.20	3.002
298.50	1.406	320.45	6.391	311.45	3.626
301.30	1.675	w=0.4		314.55	4.345
303.90	1.971	295.75	1.121	317.55	5.091
307.45	2.327	298.65	1.393	320.45	5.916
310.20	2.721	300.65	1.679	w=0.7
313.15	3.239	303.30	2.051	294.70	0.7760
315.70	3.939	306.00	2.529	298.75	1.072
318.30	4.765	308.30	3.161	302.05	1.320
321.20	5.638	311.25	3.898	304.75	1.613
w=0.2		314.45	4.693	307.50	1.970
294.50	1.182	317.40	5.670	310.20	2.426
297.20	1.448	320.30	6.728	313.15	3.018
300.50	1.784	w=0.5		316.40	3.698
303.15	2.128	296.35	1.199	319.50	4.453
306.40	2.508	298.80	1.495	322.50	5.303
309.95	2.922	301.55	1.843	w=0.8
312.70	3.426	304.30	2.263	294.05	0.4178
314.90	4.072	307.20	2.758	297.30	0.6285
317.35	4.932	309.85	3.365	300.69	0.8973
320.55	5.880	312.60	4.114	304.00	1.188
w=0.3		315.65	5.019	307.15	1.493
295.25	1.119	318.50	6.046	310.15	1.827
297.85	1.364	321.20	7.102	313.45	2.259
300.75	1.676	w=0.6		315.60	2.641
303.75	2.037	293.50	0.9315	318.55	3.167
307.10	2.515	296.25	1.239	321.15	3.734
310.30	3.072	299.15	1.565
312.90	3.707	301.85	1.972

T/K	x×10⁴	T/K	x×10⁴	T/K	x×10⁴
w=0.1		315.50	4.440	304.80	2.452
295.85	1.187	317.65	5.346	308.20	3.002
298.50	1.406	320.45	6.391	311.45	3.626
301.30	1.675	w=0.4		314.55	4.345
303.90	1.971	295.75	1.121	317.55	5.091
307.45	2.327	298.65	1.393	320.45	5.916
310.20	2.721	300.65	1.679	w=0.7
313.15	3.239	303.30	2.051	294.70	0.7760
315.70	3.939	306.00	2.529	298.75	1.072
318.30	4.765	308.30	3.161	302.05	1.320
321.20	5.638	311.25	3.898	304.75	1.613
w=0.2		314.45	4.693	307.50	1.970
294.50	1.182	317.40	5.670	310.20	2.426
297.20	1.448	320.30	6.728	313.15	3.018
300.50	1.784	w=0.5		316.40	3.698
303.15	2.128	296.35	1.199	319.50	4.453
306.40	2.508	298.80	1.495	322.50	5.303
309.95	2.922	301.55	1.843	w=0.8
312.70	3.426	304.30	2.263	294.05	0.4178
314.90	4.072	307.20	2.758	297.30	0.6285
317.35	4.932	309.85	3.365	300.69	0.8973
320.55	5.880	312.60	4.114	304.00	1.188
w=0.3		315.65	5.019	307.15	1.493
295.25	1.119	318.50	6.046	310.15	1.827
297.85	1.364	321.20	7.102	313.45	2.259
300.75	1.676	w=0.6		315.60	2.641
303.75	2.037	293.50	0.9315	318.55	3.167
307.10	2.515	296.25	1.239	321.15	3.734
310.30	3.072	299.15	1.565
312.90	3.707	301.85	1.972

T/K	x×10⁴	T/K	x×10⁴	T/K	x×10⁴
w=0.1		318.75	7.556	305.25	3.279
296.15	1.658	320.90	8.882	307.45	3.904
298.95	1.877	324.00	10.26	310.60	4.755
302.15	2.105	327.15	11.79	314.65	5.724
305.45	2.389	329.75	13.37	317.65	6.727
307.95	2.761	332.15	15.09	320.25	7.901
310.95	3.213	w=0.4		322.65	9.290
313.30	3.722	294.95	2.137	326.00	10.79
315.70	4.320	298.25	2.408	329.05	12.29
318.25	5.048	300.65	2.795	331.75	13.84
320.40	5.854	303.55	3.247	w=0.7
323.75	6.868	306.05	3.880	296.50	1.386
326.55	7.889	308.05	4.678	299.25	1.654
329.30	9.043	311.75	5.716	301.85	2.016
332.00	10.32	314.95	6.844	304.40	2.501
w=0.2		317.55	7.987	307.70	3.081
296.15	1.800	320.15	9.339	310.75	3.591
298.40	2.061	322.95	10.81	313.85	4.294
302.05	2.458	325.90	12.50	316.35	5.062
304.85	2.877	328.45	14.36	318.25	5.847
307.20	3.360	330.95	16.36	320.75	6.735
310.25	3.989	w=0.5		324.05	7.680
312.40	4.636	296.40	2.402	326.85	8.748
315.10	5.328	299.80	2.795	329.95	10.08
317.60	6.155	303.15	3.240	332.55	11.54
320.15	7.124	305.30	3.735	w=0.8
322.55	8.259	307.90	4.521	294.90	0.5524
325.05	9.530	310.70	5.545	297.50	0.8101
327.75	10.86	313.90	6.735	300.40	1.123
330.55	12.34	317.70	7.944	304.00	1.514
w=0.3		320.85	9.211	307.90	1.965
296.25	2.044	323.65	10.64	311.85	2.448
299.30	2.422	326.55	12.19	315.70	3.037
301.50	2.791	329.30	13.93	319.10	3.741
304.40	3.244	332.20	15.73	322.50	4.528
306.95	3.741	w=0.6		325.90	5.411
309.15	4.243	295.10	2.175	329.05	6.317
311.70	4.808	297.70	2.380	332.55	7.291
313.95	5.518	300.00	2.603
316.10	6.409	302.75	2.844