交互四元体系K+,NH4+//Cl-,H2PO4--H2O 在313.15 K时相平衡研究

doi:10.19964/j.issn.1006-4990.2022-0050

摘要/Abstract

摘要：

采用等温溶解平衡法研究了交互四元体系K⁺,NH₄⁺//Cl^-,H₂PO₄^--H₂O以及子体系KCl-NH₄Cl-H₂O在313.15 K时的固-液相平衡关系,并根据实验数据绘制了四元体系及子体系的相关相图和水图,采用湿渣法与X射线衍射相结合的方法对平衡固相进行鉴定。实验结果表明,三元体系KCl-NH₄Cl-H₂O是一个部分互溶体系,相图有一个共结晶点、2条单变量曲线、5个结晶区；交互四元体系K⁺,NH₄⁺//Cl^-,H₂PO₄^--H₂O中形成了（K,NH₄）Cl和（K,NH₄）H₂PO₄两种固溶体,该四元相图包括2个共饱和点、5条单变量曲线及4个结晶区。实验结果可为该体系的共结晶研究、相应的模型拟合计算提供必要基础数据。

关键词: 相平衡, KCl, NH₄Cl, KH₂PO₄, NH₄H₂PO₄

Abstract:

The solid liquid phase equilibria of reciprocal quaternary system of K⁺,NH₄⁺//Cl^-,H₂PO₄^--H₂O and subsystem of KCl-NH₄Cl-H₂O at 313.15 K were studied by isothermal solution equilibrium method.According to the experimental data,their relevant phase diagrams and the water diagram of the quaternary system and subsystem were drawn.The equilibrium solid phase was identified by wet residue method combined with X-ray diffraction method.The experimental results showed that the ternary system of KCl-NH₄Cl-H₂O was a partially mutually soluble system,and there were one eutectic point,two univariate curves and five crystallization regions in the phase diagram.Two solid solutions of（K,NH₄）Cl and（K,NH₄）H₂PO₄ were formed in the reciprocal quaternary system of K⁺,NH₄⁺//Cl^-,H₂PO₄^--H₂O.There were two eutectic points,five univariate curves and four crystallization regions in this quaternary phase diagram.The experimental results could provide necessary basic data for the study of co-crystallization of the system and the corresponding model fitting calculation.

Key words: phase equilibrium, KCl, NH₄Cl, KH₂PO₄, NH₄H₂PO₄

中图分类号:

O642.42

樊小娟,朱静,邓文清,陈艳,李天祥. 交互四元体系K⁺,NH₄⁺//Cl^-,H₂PO₄^--H₂O 在313.15 K时相平衡研究[J]. 无机盐工业, 2022, 54(10): 102-108.

FAN Xiaojuan,ZHU Jing,DENG Wenqing,CHEN Yan,LI Tianxiang. Study on phase equilibria of reciprocal quaternary system of K⁺,NH₄⁺//Cl^-,H₂PO₄^--H₂O at 313.15 K[J]. Inorganic Chemicals Industry, 2022, 54(10): 102-108.

图/表 11

表1

图1

图2

图3

图4

表2

交互四元体系K+,NH4+//Cl-,H2PO4- -H2O 313.15 K时溶解度数据

编号	液相质量分数/%						耶涅克指数J/%			平衡固相
编号	H₂PO₄^-	Cl^-	NH₄⁺	K⁺	H₂O		NH₄⁺	Cl^-	H₂O	平衡固相
1（A）	3.19	12.04	0.00	14.53	70.24	0.00		91.19	1 043.95	KCl+KH₂PO₄
2	3.41	12.80	0.95	14.22	68.62	12.70		91.15	958.94	KNl+KNP
3	4.07	13.59	1.66	13.14	67.54	21.51		90.15	879.24	KNl+KNP
4	5.37	14.20	2.39	12.54	65.50	29.23		87.89	795.22	KNl+KNP
5（E）	6.01	14.52	3.13	11.63	64.71	36.82		86.89	760.00	KNl+KNP+NKP
6	6.37	15.48	3.78	11.45	62.91	41.72		86.95	693.29	KNl+KNP+NKl+NKP
7	7.49	16.37	4.91	10.39	60.84	50.58		85.70	625.05	KNl+KNP+NKl+NKP
8	7.56	16.31	5.16	9.55	61.43	53.96		85.55	632.38	KNl+KNP+NKl+NKP
9	6.92	17.89	6.42	9.67	59.10	58.99		87.64	568.05	KNl+KNP+NKl+NKP
10	6.97	18.64	6.81	9.29	58.29	61.37		88.00	540.02	KNl+KNP+NKl+NKP
11（F）	6.99	19.34	7.38	8.15	58.14	66.26		88.36	521.30	KNl+NKl+NKP
12（B）	31.16	0.00	3.73	4.47	60.64	64.40		0.00	1 047.74	KNP+NKP
13	18.93	3.43	3.01	4.89	69.73	57.14		33.23	1 323.88	KNP+NKP
14	18.08	5.15	3.18	6.09	67.51	53.06		43.87	1 128.26	KNP+NKP
15	16.04	6.19	3.03	6.73	68.01	49.36		51.41	1 108.97	KNP+NKP
16	14.30	7.77	3.19	7.42	67.32	48.21		59.85	1 017.53	KNP+NKP
17	13.40	9.85	3.69	8.26	64.79	49.20		66.85	862.75	KNP+NKP
18	11.96	11.25	3.64	9.33	63.82	45.85		72.08	802.28	KNP+NKP
19	10.60	13.10	3.96	10.14	62.20	45.83		77.22	719.60	KNP+NKP
20	9.14	14.00	3.68	11.03	62.14	41.96		80.77	703.66	KNP+NKP
21	8.18	14.17	3.66	11.25	62.74	41.33		82.61	717.86	KNP+NKP
22	7.97	14.01	3.64	11.16	63.21	41.44		82.82	733.08	KNP+NKP
23（E）	6.01	14.52	3.13	11.63	64.71	36.82		86.89	760.00	KNl+KNP+NKP
24（C）	6.21	18.86	10.75	0.00	64.18	100.00		89.29	596.20	NH₄Cl+NH₄H₂PO₄
25	12.47	17.52	9.34	4.08	56.59	83.24		79.40	503.13	NKl+NKP
26	11.86	17.99	8.70	5.72	55.73	76.72		80.63	490.16	NKl+NKP
27	10.76	18.20	7.90	7.43	55.71	69.75		82.27	494.24	NKl+NKP
28	8.32	18.65	7.50	7.64	57.88	68.03		86.02	523.85	NKl+NKP
29	8.66	19.18	7.58	7.63	56.95	68.28		85.87	500.38	NKl+NKP
30	7.95	19.28	7.55	8.11	57.11	66.86		86.93	505.32	NKl+NKP
31（F）	6.99	19.34	7.38	8.15	58.14	66.26		88.36	521.30	KNl+NKl+NKP
32（D）	0.00	22.03	7.86	7.25	62.86	70.15		100.00	559.91	KNl+KNP
33	2.66	21.10	6.99	9.18	60.05	62.27		95.60	533.78	KNl+KNP
34	5.46	20.52	6.91	9.87	57.24	60.28		91.16	498.85	KNl+KNP
35	7.03	19.86	6.78	9.65	56.68	60.36		88.57	496.00	KNl+KNP
36	7.41	19.54	6.94	9.56	56.55	61.13		87.85	498.99	KNl+KNP
37	7.23	19.71	6.95	9.64	56.47	60.96		88.20	495.82	KNl+KNP
38（F）	6.99	19.34	7.38	8.15	58.14	66.26		88.36	521.30	KNl+NKl+NKP

表2

图5

图6

图7

图8

图9

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编号	液相				湿渣			平衡固相
编号	w （KCl）	w （NH₄Cl）	w （H₂O）		w （KCl）	w （NH₄Cl）	w （H₂O）	平衡固相
1（B）	28.72	0.00	71.28	—		—	—	KCl
2	25.31	4.95	69.74	73.14		2.22	24.64	（K,NH₄）Cl
3	22.26	11.04	66.70	76.56		9.43	14.01	（K,NH₄）Cl
4	20.58	14.12	65.30	54.41		12.00	33.59	（K,NH₄）Cl
5	17.81	18.14	64.05	50.18		15.32	34.50	（K,NH₄）Cl
6	15.37	20.67	63.96	40.53		19.62	39.85	（K,NH₄）Cl
7	13.83	23.05	63.11	35.36		21.03	43.61	（K,NH₄）Cl
8（D）	13.85	23.30	62.85	20.80		40.00	39.20	（K,NH₄）Cl+ （NH₄,K）Cl
9	12.01	24.48	63.51	19.00		47.70	33.30	（NH₄,K）Cl
10	11.44	24.48	64.09	17.56		48.00	34.44	（NH₄,K）Cl
11	6.44	27.47	66.09	16.39		70.00	13.61	（NH₄,K）Cl
12	5.29	27.53	67.18	11.00		57.43	31.57	（NH₄,K）Cl
13	2.73	29.67	67.60	6.00		60.08	33.92	（NH₄,K）Cl
14	2.38	29.80	67.82	1.03		65.16	33.81	（NH₄,K）Cl
15（C）	0.00	31.41	68.59	—		—	—	NH₄Cl

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交互四元体系K⁺,NH₄⁺//Cl^-,H₂PO₄^--H₂O 在313.15 K时相平衡研究

Study on phase equilibria of reciprocal quaternary system of K⁺,NH₄⁺//Cl^-,H₂PO₄^--H₂O at 313.15 K

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