283.15 K下三元KCl-NH4Cl-H2O和KH2PO4-NH4H2PO4-H2O体系固-液相平衡测定与关联

doi:10.11962/1006-4990.2020-0103

Abstract

Abstract:

The solubility of ternary systems KCl-NH₄Cl-H₂O and KH₂PO₄-NH₄H₂PO₄-H₂O were determined by isothermal dissolution equilibrium method at 283.15 K.The structure and composition of the equilibrium solid phase were determined by the combination of X-ray diffraction and Schreinemakers′ wet residue method.Results showed that the equilibrium solid pha-se of two systems had solid solutions of partially miscible,which respectively contained one co-saturation crystallization point,two univariate curves and six zones.The solubility data of the two systems were correlated and calculated by Pitzer model.Results showed that the maximum relative error and the minimum relative error of calculated data of KCl-NH₄Cl-H₂O ternary system were 3.096 9% and 0.038 3% resepectively,and the maximum relative error and the minimum relative error of calculated data of KH₂PO₄-NH₄H₂PO₄-H₂O ternary system were 5.935 6% and 0.069 8% resepectively.The calculated value of Pitzer model was basically consistent with the experimental value.

Key words: phase equilibrium, solubility, Pitzer model, solid solution

CLC Number:

O642.42

Yang Jiamin,Zhu Jing,Hu Xue,Wu Qiang,Li Tianxiang. Determination and correlation for solid-liquid phase equilibrium of ternary KCl-NH₄Cl-H₂O and KH₂PO₄-NH₄H₂PO₄-H₂O systems at 283.15 K[J]. Inorganic Chemicals Industry, 2021, 53(1): 30-35.

Figures/Tables 12

References 21

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物质	文献值	实验值	物质	文献值	实验值
KCl	31.2	31.04	KH₂PO₄	18.3	18.30
NH₄Cl	33.3	32.77	NH₄H₂PO₄	28.0	28.22

序号	液相组成/%				湿固相/%		平衡固相
	实验值		Pitzer计算值		湿固相/%
	w （KCl）	w （NH₄Cl）	w （KCl）	w （NH₄Cl）	w （KCl）	w （NH₄Cl）
1,a	23.69	0.00	23.67	0.00	—	—	KCl
2	22.46	1.67	22.36	1.77	91.19	1.17	（K,NH₄）Cl
3	20.28	4.54	20.19	4.63	90.09	1.72	（K,NH₄）Cl
4	16.81	8.65	17.04	8.42	88.56	3.18	（K,NH₄）Cl
5	15.32	11.13	15.05	11.40	85.59	5.52	（K,NH₄）Cl
6	13.90	13.48	13.81	13.57	81.03	7.94	（K,NH₄）Cl
7	13.12	15.56	13.07	15.61	79.08	8.36	（K,NH₄）Cl
8	11.77	17.96	11.95	17.78	78.03	10.63	（K,NH₄）Cl
9,b	11.54	18.63	11.42	18.75	63.01	19.44	（K,NH₄）Cl+（NH₄,K）Cl
10	11.48	19.29	11.48	19.29	13.10	64.69	（NH₄,K）Cl
11	6.65	21.59	6.61	21.63	5.63	75.04	（NH₄,K）Cl
12	2.33	23.80	2.38	23.75	3.97	72.98	（NH₄,K）Cl
13,d	0.00	24.68	0.00	24.67	—	—	NH₄Cl

序号	液相组成/%				湿固相/%		平衡固相
	实验值		Pitzer计算值		湿固相/%
	w（NH₄H₂PO₄）	w（KH₂PO₄）	w（NH₄H₂PO₄）	w（KH₂PO₄）	w（NH₄H₂PO₄）	w（KH₂PO₄）
1,a₁	22.01	0.00	22.02	0.00	—	—	NH₄H₂PO₄
2	20.92	4.07	20.68	4.31	87.93	1.68	（NH₄,K）H₂PO₄
3	19.28	6.80	19.51	6.57	79.82	4.25	（NH₄,K）H₂PO₄
4	17.37	8.89	17.39	8.87	70.91	5.40	（NH₄,K）H₂PO₄
5	16.68	9.66	16.97	9.37	69.08	6.88	（NH₄,K）H₂PO₄
6,b₁	15.32	10.43	15.11	10.64	60.98	12.65	（NH₄,K）H₂PO₄+（K,NH₄）H₂PO₄
7	15.33	10.44	15.16	10.61	9.75	60.34	（K,NH₄）H₂PO₄
8	13.35	11.24	13.43	11.16	8.16	68.12	（K,NH₄）H₂PO₄
9	11.50	11.78	11.74	11.54	5.31	79.25	（K,NH₄）H₂PO₄
10	8.34	12.41	8.31	12.44	4.22	74.62	（K,NH₄）H₂PO₄
11	2.36	13.47	2.37	13.46	1.91	74.31	（K,NH₄）H₂PO₄
12,d₁	0.00	15.47	0.00	15.46	—	—	KH₂PO₄

单盐参数	β^（0）	β^（1）	C^Φ
KCl	0.039 659	0.196 135	0.006 803
KH₂PO₄	-0.076 87	-0.147 1	0.015 165
NH₄Cl	0.051 032	0.172 93	-0.006 16
NH₄H₂PO₄	-0.072 67	-0.449 8	0.010 95

序号	固溶体中NH₄Cl的物质的量分数/%	液相组成						活度积
		实验值/（mol·kg^-1）		Pitzer模型计算值/（mol·kg^-1）		相对误差/%		实验值	Pitzer模型计算值	相对误差/%
		m	m	m	m	m	m	实验值	Pitzer模型计算值	相对误差/%
1,a	0	4.164 2	4.164 2	4.164 2	4.164 2	0	0	7.708 6	7.708 6	0
2	1.756 8	3.970 9	4.382 4	3.953 1	4.364 6	0.449 9	0.407 7	6.732 0	6.970 3	3.540 1
3	2.591 9	3.618 4	4.747 4	3.603 2	4.732 2	0.419 7	0.319 9	6.723 0	7.086 9	5.413 0
4	4.766 0	3.025 0	5.194 5	3.065 7	5.235 1	1.343 0	0.782 1	6.545 4	6.804 7	3.960 4
5	8.247 3	2.794 0	5.623 1	2.745 5	5.574 5	1.737 1	0.863 2	6.597 9	6.580 2	0.268 3
6	12.015 8	2.567 5	6.037 8	2.550 5	6.020 8	0.662 0	0.281 5	7.354 8	6.929 1	5.788 1
7	12.841 7	2.467 6	6.546 3	2.457 7	6.536 4	0.402 9	0.151 9	7.673 8	7.751 4	1.012 0
8	15.956 9	2.246 8	7.0250	2.281 4	7.059 5	1.539 1	0.492 2	8.363 5	8.277 0	1.034 0
9,b	30.069 6	2.216 7	7.204 4	2.193 7	7.181 4	1.037 9	0.319 4	9.010 8	8.519 5	5.452 4
10	87.313 5	2.224 3	7.433 5	2.225 2	7.410 3	0.038 3	0.312 3	10.621 0	10.444 0	1.666 1
11	94.891 8	1.243 1	6.867 7	1.236 0	6.860 7	0.569 9	0.103 2	8.675 9	9.054 9	4.368 4
12	96.243 5	0.423 1	6.446 4	0.432 5	6.455 8	3.096 9	0.202 9	8.206 2	8.089 8	1.418 8
13,d	100	0	6.225 1	0	6.225 1	0	0	14.154 0	14.154 0	0

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Inorganic Acid-Base-Salt Committee of CIESC

Determination and correlation for solid-liquid phase equilibrium of ternary KCl-NH₄Cl-H₂O and KH₂PO₄-NH₄H₂PO₄-H₂O systems at 283.15 K

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序号	固溶体中NH₄Cl的物质的量分数/%	液相组成						活度积
		实验值/（mol·kg^-1）		Pitzer模型计算值/（mol·kg^-1）		相对误差/%		实验值	Pitzer模型计算值	相对误差/%
		m	m	m	m	m	m	实验值	Pitzer模型计算值	相对误差/%
1,a₁	100	0	2.453 4	0	2.453 4	0	0	0.3864	0.386 4	0
2	86.082 9	0.398 7	2.823 3	0.422 4	2.846 9	5.935 6	0.838 2	0.322 8	0.325 0	0.678 2
3	77.334 2	0.676 0	2.943 4	0.652 9	2.920 4	3.405 8	0.782 1	0.299 8	0.300 3	0.176 6
4	70.160 4	0.885 9	2.933 7	0.883 8	2.931 6	0.231 0	0.069 8	0.287 3	0.287 7	0.125 0
5	67.510 1	0.963 6	2.932 2	0.935 1	2.903 7	2.965 4	0.974 6	0.281 5	0.281 9	0.165 8
6,b₁	63.867 2	1.032 2	2.825 9	1.052 6	2.846 3	1.972 2	0.720 4	0.272 7	0.274 4	0.616 6
7	63.860 2	1.033 5	2.828 8	1.050 0	2.845 4	1.604 4	0.586 2	0.273 0	0.274 3	0.485 5
8	58.835 5	1.095 2	2.634 3	1.087 8	2.626 8	0.684 1	0.284 4	0.232 4	0.238 9	2.783 3
9	54.018 2	1.128 3	2.431 4	1.104 8	2.407 9	2.077 3	0.964 0	0.223 7	0.221 9	0.776 9
10	44.712 2	1.150 7	2.065 5	1.153 9	2.068 7	0.278 2	0.155 0	0.198 2	0.198 3	0.032 8
11	17.412 5	1.175 9	1.419 7	1.174 7	1.418 5	0.103 0	0.085 3	0.176 2	0.176 2	0.006 2
12	0	1.344 8	1.344 8	1.344 8	1.344 8	0	0	0.256 6	0.256 6	0
13,d₁	100	0	2.453 4	0	2.453 4	0	0	0.386 4	0.386 4	0

Determination and correlation for solid-liquid phase equilibrium of ternary KCl-NH4Cl-H2O and KH2PO4-NH4H2PO4-H2O systems at 283.15 K