水盐体系汽液平衡的热力学模型研究

doi:10.19964/j.issn.1006-4990.2020-0562

Abstract

Abstract:

The phase equilibrium of electrolyte solution systems is the basis of chemical unit operation,and has important research value in in the fields of chemistry and chemical engineering,oceanography,geology and so on.Scholars at home and abroad have studied the experiment and theory on the vapor-liquid equilibrium for electrolyte solution system,and developed the empirical and semi-empirical models with their own characteristics.The extended activity coefficient model with prediction was established in this article,and the model was based on the NRTL theory and the hypothesis of hydration and mixed salt.The feasibility of the model was verified by the correlation calculation of 21 binary electrolyte systems and 14 mixed systems.In addition,the binary system parameters could be used to directly predict the vapor-liquid equilibrium of the mixed electrolyte solution system.

Key words: electrolyte solution, phase equilibrium, thermodynamics, activity coefficient model

CLC Number:

TQ131.1

Liu Zhiguo,Zhang Na,Chen Chuan,Xu Xianzhen. Study on thermodynamic model of vapor-liquid equilibrium of electrolyte system[J]. Inorganic Chemicals Industry, 2021, 53(8): 55-59.

Figures/Tables 10

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References 24

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体系	h	τ_i_,w^（0）	τ_w,_i^（0）	τ_i_,w^（1）	τ_w,_i^（1）
BaBr₂+H₂O	1.50	-4.42	3.52	-228.19	321.73
CaBr₂+H₂O	2.55	-0.40	-33.92	-1 649.09	12 785.70
CaCl₂+H₂O	1.10	781.44	-3 771.77	-98.47	-6 010.44
CsBr+H₂O	0.50	-4.34	4.12	423.85	-480.68
CsCl+H₂O	0.30	-3.38	2.83	-59.70	-20.03
CsI+H₂O	0.10	-3.78	-1.40	9.67	642.89
K₂SO₄+H₂O	0.60	-38.84	70.38	12 703.70	-17 691.81
KBr+H₂O	2.10	1.20	-50.38	-1 340.62	15 952.42
KCl+H₂O	2.00	-2.92	2.38	-81.81	126.71
KI+H₂O	3.00	-3.63	3.64	199.06	-326.81
LiCl+H₂O	2.15	-4.99	13.17	-4.29	16.17
LiBr+H₂O	0.80	-5.47	56.87	510.23	-23 153.41
MgCl₂+H₂O	3.47	-6.26	-58.68	453.19	19 585.20
MgSO₄+H₂O	0.41	-2.63	3.29	-696.95	2 367.36
Na₂SO₄+H₂O	0.10	1.06	-1.45	-1 441.50	1 425.60
NaBr+H₂O	4.00	-1.50	-0.69	-456.26	567.10
NaCl+H₂O	3.10	-2.54	2.06	184.51	-203.49
NaI+H₂O	1.90	-3.50	2.74	-75.40	-137.38
RbCl+H₂O	2.70	-0.94	0.66	-607.71	993.37
SrCl₂+H₂O	2.00	-6.85	30.00	539.38	-8 296.66
ZnCl₂+H₂O	3.00	-3.77	3.26	-1.23	2.83

体系	T/K	数据点	本实验
体系	T/K	数据点	dY/kPa	dP/%
LiCl+H₂O^[1,4]	298.15~394.40	47	0.018	1.250
LiBr+H₂O^[1-2,16]	298.15~377.85	182	0.070	0.860
MgCl₂+H₂O^[1-2,16]	273.15~376.45	151	0.076	0.850
MgSO₄+H₂O^[1,17]	273.15~298.15	30	0.012	0.530
Na₂SO₄+H₂O^[1,2]	298.15~343.15	49	0.048	0.750
NaBr+H₂O^[1,17]	298.15~373.15	69	0.040	0.650
NaCl+H₂O^[1,2]	298.15~343.15	58	0.090	0.929
NaI+H₂O^[1,2]	298.15~343.15	51	0.061	0.690
RbCl+H₂O^[1,2]	298.15~343.15	59	0.068	0.710
SrCl₂+H₂O^[1,4]	298.15~379.80	30	0.030	0.750
ZnCl₂+H₂O^[1,4]	298.15~379.80	30	0.030	0.910
BaBr₂+H₂O^[1,2]	298.15~353.15	55	0.079	0.780
CaBr₂+H₂O^[1,2]	298.15~353.15	63	0.049	1.100
CaCl₂+H₂O^[1-2,18-19]	273.15~423.15	322	0.081	1.820
CsBr+H₂O^[1,2]	298.15~353.15	51	0.097	1.010
CsCl+H₂O^[1,2]	298.15~353.15	63	0.091	0.970
CsI+H₂O^[1,2]	298.15~353.15	42	0.039	0.420
K₂SO₄+H₂O^[1,18]	298.15~383.65	104	0.051	1.150
KBr+H₂O^[1,2]	298.15~343.15	51	0.077	0.870
KCl+H₂O^[1-2,18-19]	273.15~343.15	66	0.044	0.670
KI+H₂O^[1,2]	298.15~343.15	60	0.097	0.950
平均值			0.059	0.880

体系	T/K	数据点	本实验
体系	T/K	数据点	dY/kPa	dP/%
NaCl-Na₂SO₄-H₂O^[20]	298.15	25	0.036	1.58
MgSO₄-Na₂SO₄-H₂O^[20]	298.15	30	0.024	0.82
MgCl₂-Na₂SO₄-H₂O^[21]	298.15	22	0.030	1.60
NaCl-MgSO₄-H₂O^[21]	298.15	30	0.044	1.55
KCl-K₂SO₄-H₂O^[5]	280.15~323.15	50	0.021	0.85
KCl-KBr-H₂O^[5]	279.55~323.35	48	0.075	0.95
KCl-KNO₃-H₂O^[5]	279.05~324.75	46	0.086	1.17
K₂SO₄-MgSO₄-H₂O^[18,19]	310~374.35	360	0.080	1.10
NaCl-KCl-H₂O^[3,5,18-19]	298.15~382.25	180	0.091	1.80
NaCl-CaCl₂-H₂O^[18,19]	313.25~388.25	240	0.091	1.10
NaCl-KCl-MgCl₂-H₂O^[22,23,24]	298.15	136	0.026	0.80
MgCl₂-MgSO₄-H₂O^[20]	298.15	20	0.100	1.70
NaCl-MgCl₂-H₂O^[20]	298.15	20	0.080	1.70
NaCl-KCl-MgCl₂-CaCl₂- MgSO₄^[15,19]	306.75~373.25	60	0.070	1.07
平均值			0.061	1.27

体系	T/K	数据点	本实验
体系	T/K	数据点	dY/kPa	dP/%
NaCl-Na₂SO₄-H₂O^[20]	298.15	25	0.072	2.58
MgSO₄-Na₂SO₄-H₂O^[20]	298.15	30	0.037	1.22
MgCl₂-Na₂SO₄-H₂O^[21]	298.15	22	0.080	2.60
NaCl-MgSO₄-H₂O^[21]	298.15	30	0.074	2.55
KCl-K₂SO₄-H₂O^[5]	280.15~323.15	50	0.031	1.50
KCl-KBr-H₂O^[5]	279.55~323.35	48	0.150	2.50
KCl-KNO₃-H₂O^[5]	279.05~324.75	46	0.160	2.71
K₂SO₄-MgSO₄-H₂O^[18,19]	310~374.35	360	0.180	3.10
NaCl-KCl-H₂O^[3,5,18-19]	298.15~382.25	180	0.170	2.80
NaCl-CaCl₂-H₂O^[18,19]	313.25~388.25	240	0.140	1.90
NaCl-KCl-MgCl₂-H₂O^[22,23,24]	298.15	136	0.046	1.50
MgCl₂-MgSO₄-H₂O^[20]	298.15	20	0.160	2.70
NaCl-MgCl₂-H₂O^[20]	298.15	20	0.180	2.75
NaCl-KCl-MgCl₂-CaCl₂- MgSO₄^[15,19]	306.75~373.25	60	0.070	1.07
平均值			0.117	2.36

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Inorganic Acid-Base-Salt Committee of CIESC

Study on thermodynamic model of vapor-liquid equilibrium of electrolyte system

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