KH2PO4-KCl-H2O、NH4H2PO4-NH4Cl-H2O三元体系283.15 K相平衡研究

doi:10.11962/1006-4990.2019-0639

Abstract

Abstract:

The phase equilibrium of KH₂PO₄-KCl-H₂O and NH₄H₂PO₄-NH₄Cl-H₂O at 283.15 K was determined by using isothermal dissolution equilibrium method.The composition and structure of equilibrium solid phase were identified by analy-sis of wet slag and X-ray diffraction.Results showed that the ternary systems KH₂PO₄-KCl-H₂O and NH₄H₂PO₄-NH₄Cl-H₂O were simple cosaturated,and no solid solution or adduct was formed.Each phase diagram contained one invariant point,two univariate curves and three crystallization regions.The saturated solubility data of simple ternary systems KH₂PO₄-KCl-H₂O and NH₄H₂PO₄-NH₄Cl-H₂O were calculated by Pitzer electrolyte solution theory.Results showed that the relative average deviation and the root mean square error of KH₂PO₄-KCl-H₂O system were 0.046 and 0.29 respectively,and the relative average deviation and the root mean square error of NH₄H₂PO₄-NH₄Cl-H₂O system were 0.044 and 0.31 respectively.The calculated value agreed with the experimental value well.

Key words: ternary system, phase equilibrium, solubility, Pitzer model

CLC Number:

TQ126.35

Wu Qiang,Hu Xue,Zhu Jing,Yang Jiamin,Li Tianxiang. Phase equilibrium of KH₂PO₄-KCl-H₂O and NH₄H₂PO₄-NH₄Cl-H₂O ternary system at 283.15 K[J]. Inorganic Chemicals Industry, 2020, 52(11): 24-28.

Figures/Tables 9

References 19

[1]	周鹂, 鲁剑巍, 李小坤, 等. 我国大量元素水溶肥料产业发展现状[J]. 现代化工, 2013,33(4):9-14.
[2]	张强, 付强强, 陈宏坤, 等. 我国水溶性肥料的发展现状及前景[J]. 山东化工, 2017,46(12):78-81.
[3]	岳焕芳, 程明, 王俊英, 等. 水溶肥应用现状和发展前景[J].蔬菜, 2017(2):28-31.
[4]	Gagnière E, Mangin D, Puel F, et al. Formation of co-crystals:Kine-tic and thermodynamic aspects[J]. Journal of Crystal Growth, 2009,311(9):2689-2695. doi: 10.1016/j.jcrysgro.2009.02.040
[5]	冯先明, 王保明, 彭全, 等. 我国水溶肥的发展概况与建议[J]. 现代化工, 2018,38(1):6-11.
[6]	Guo L, Hu Y, Wang Y, et al. A quasi-ternary wet residue method app-lied to solid-liquid equilibrium systems[J]. Fluid Phase Equilibria, 2018,456:161-167. doi: 10.1016/j.fluid.2017.10.014
[7]	胡雪, 朱静, 王睿哲, 等.(NH₂)₂CO-NH₄H₂PO₄-H₂O三元体系10 ℃相平衡研究[J]. 无机盐工业, 2019,51(5):41-44.
[8]	Li G, Cao J, Chen P, et al. Determination and calculation of phase equilibrium for tetrahydrofuran+sodium sulfate+magnesium sulfate+water system at 5 ℃[J]. Journal of Chemical & Engineering Data, 2013,58(5):1301-1307.
[9]	何贤江, 郭志琴, 苏裕光. 15 ℃ KCl-NaCl-MgCl₂-H₂O四元体系相平衡研究[J]. 化学学报, 1991,49:128-134.
[10]	赵长伟, 马沛生, 郭瓦力, 等. KCl-NH₄Cl-H₂O 三元水盐体系溶解度的研究[J]. 化学工业与工程, 2003,20(3):145-149.
[11]	Pitzer K S. Thermodynamics of electrolytes.I.Theoretical basis and general equations[J]. The Journal of Physical Chemistry, 1973,77(2):268-277.
[12]	Silvester L F, Pitzer K S. Thermodynamics of electrolytes.8.High-temperature properties,including enthalpy and heat capacity,with application to sodium chloride[J]. The Journal of Physical Chemi-stry, 1977,81(19):1822-1828.
[13]	Pitzer K S, Peterson J R, Silvester L F. Thermodynamics of electro-lytes.IX.Rare earth chlorides,nitrates,and perchlorates[J]. Journal of Solution Chemistry, 1978,7(1):45-56.
[14]	Silvester L F, Pitzer K S. Thermodynamics of electrolytes.X.Enth-alpy and the effect of temperature on the activity coefficients[J]. Journal of Solution Chemistry, 1978,7(5):327-336.
[15]	Pitzer K S, Silvester L F. Thermodynamics of electrolytes.11.Pro-perties of 3:2,4:2,and other high-valence types[J]. The Journal of Physical Chemistry, 1978,82(11):1239-1242.
[16]	Bradley D J, Pitzer K S. Thermodynamics of electrolytes.12.Dielec-tric properties of water and debye-hiickel parameters to 350 ℃ and 1 kbar[J]. The Journal of Physical Chemistry, 1979,12(83):1599-1603.
[17]	Pitzer K S, Wang P, Rard J A, et al. Thermodynamics of electrolyt-es.13.Ionic strength dependence of higher-order terms;equations for CaCl₂ and MgCl₂[J]. Journal of Solution Chemistry, 1999,28(4):265-282.
[18]	邓天龙, 周桓, 陈侠. 水盐体系相图及其应用[M]. 北京: 化学工业出版社, 2013.
[19]	Simoes M C, Hughes K J, Ingham D B, et al. Estimation of the pi-tzer parameters for 1-1,2-1,3-1,4-1,and 2-2 single electrolyt-es at 25 ℃[J]. Journal of Chemical & Engineering Data, 2016,61(7):2536-2554.

编号	液相组成/%（质量分数）				湿渣组成/% （质量分数）		固相
	实验值		Pitzer计算值		湿渣组成/% （质量分数）
	w （KH₂PO₄）	w （KCl）	w （KH₂PO₄）	w （KCl）	w （KH₂PO₄）	w （KCl）
1（b）	15.47	0.00	15.52	0.00	—	—	KH₂PO₄
2	10.99	4.49	10.96	4.48	64.28	2.14	KH₂PO₄
3	8.15	8.61	8.05	8.56	52.21	4.26	KH₂PO₄
4	6.27	12.36	6.15	12.30	72.50	3.30	KH₂PO₄
5	4.77	15.95	5.02	16.08	70.70	4.43	KH₂PO₄
6	3.86	19.28	3.86	19.28	62.86	7.35	KH₂PO₄
7	3.06	22.61	3.00	22.58	62.19	8.31	KH₂PO₄
8（d）	2.93	22.99	2.25	22.62	35.50	22.76	KH₂PO₄+ KCl
9	2.87	23.01	2.21	22.65	1.77	58.17	KCl
10	1.58	23.12	2.00	23.35	1.04	56.86	KCl
11（a）	0.00	23.69	0.00	24.22	—	—	KCl

编号	液相组成/%（质量分数）				湿渣组成/%（质量分数）		固相
	实验值		Pitzer计算值		湿渣组成/%（质量分数）
	w（NH₄Cl）	w（NH₄H₂PO₄）	w（NH₄Cl）	w（NH₄H₂PO₄）	w（NH₄Cl）	w（NH₄H₂PO₄）
1（e）	24.98	0.00	25.47	0.00	—	—	NH₄Cl
2	24.54	1.39	24.70	1.74	53.51	0.88	NH₄Cl
3	24.31	2.84	24.05	2.28	57.02	1.57	NH₄Cl
4	24.14	3.35	23.76	2.53	82.89	0.81	NH₄Cl
5（g）	23.64	4.47	23.64	4.48	10.51	61.23	NH₄Cl+ NH₄H₂PO₄
6	21.63	5.04	21.66	5.11	4.76	76.05	NH₄H₂PO₄
7	18.61	6.10	18.61	6.09	4.84	72.45	NH₄H₂PO₄
8	14.98	7.49	15.07	7.69	4.02	70.66	NH₄H₂PO₄
9	11.52	9.60	11.43	9.41	2.91	72.95	NH₄H₂PO₄
10	7.58	12.69	7.41	12.33	2.63	68.95	NH₄H₂PO₄
11	3.78	16.89	3.63	16.57	1.66	60.15	NH₄H₂PO₄
12（f）	0.00	22.01	0.00	22.60	—	—	NH₄H₂PO₄

单盐参数	β^（0）	β^（1）	C^Φ
KCl	0.048 35	0.212 2	-0.000 84
KH₂PO₄	-0.067 80	-0.104 2	0.000 00
NH₄Cl	0.052 20	0.191 8	-0.003 01
NH₄H₂PO₄	-0.070 40	-0.415 6	0.006 69

温度系数	?β^（0）/?T	?β^（1）/?T	?C^Φ/?T
KCl	5.794×10⁴	10.71×10⁴	-5.095×10⁴
KH₂PO₄	6.045×10⁴	28.60×10⁴	-10.110×10⁴
NH₄Cl	0.779×10⁴	12.58×10⁴	2.100×10⁴
NH₄H₂PO₄	1.510×10⁴	22.80×10⁴	-2.840×10⁴

单盐参数	β^（0）	β^（1）	C^Φ
KCl	0.039 659	0.196 135	0.006 803
KH₂PO₄	-0.076 870	-0.147 100	0.015 165
NH₄Cl	0.051 032	0.172 930	-0.006 160
NH₄H₂PO₄	-0.072 670	-0.449 800	0.010 950

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Phase equilibrium of KH₂PO₄-KCl-H₂O and NH₄H₂PO₄-NH₄Cl-H₂O ternary system at 283.15 K

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Phase equilibrium of KH2PO4-KCl-H2O and NH4H2PO4-NH4Cl-H2O ternary system at 283.15 K