LiF-CrF3二元系的热力学模拟

doi:10.7503/cjcu20140396

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (12): 2668.doi: 10.7503/cjcu20140396

LiF-CrF₃二元系的热力学模拟

阴慧琴^1,^2,³, 王坤^1,², 刘文冠^1,^2,³, 谢雷东^1,²(), 韩晗^1,², 王文锋¹

1. 中国科学院上海应用物理研究所, 上海 201800
2. 中国科学院核辐射与核能技术重点实验室, 上海 201800
3. 中国科学院大学, 北京 100049

收稿日期:2014-04-25 出版日期:2014-12-10 发布日期:2014-11-29
作者简介:联系人简介: 谢雷东, 男, 研究员, 博士生导师, 主要从事高温熔盐传热蓄热、熔盐热化学与相图、新熔盐体系开发与材料相容性及高分子材料辐射改性研究. E-mail:xieleidong@sinap.ac.cn
基金资助:
中国科学院战略性先导科技专项项目(批准号: XD02002400)资助

Thermodynamic Modeling of the LiF-CrF₃ Binary System^†

YIN Huiqin^1,^2,³, WANG Kun^1,², LIU Wenguan^1,^2,³, XIE Leidong^1,^2,^*(), HAN Han^1,², WANG Wenfeng¹

1. Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800, China
2. Key Laboratory of Nuclear Radiation and Nuclear Energy Technology,Chinese Academy of Sciences, Shanghai 201800, China
3. University of Chinese Academy of Sciences, Beijing 100049, China

Received:2014-04-25 Online:2014-12-10 Published:2014-11-29
Contact: XIE Leidong E-mail:xieleidong@sinap.ac.cn
Supported by:
† Supported by the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XD02002400).

摘要/Abstract

摘要：

采用相图计算(CALPHAD)技术对LiF-CrF₃体系进行了相图的优化计算. 对液相分别采用置换熔体模型与缔合物模型进行描述, 中间化合物Li₃CrF₆则采用准化学计量比化合物模型描述. 模型参数的优化选取实验相平衡数据及第一性原理预测的数据, 优化结果表明, 缔合物模型比置换熔体模型更能准确地描述液相的实验相平衡数据.

关键词: 相图计算, 氟化锂-氟化铬, 第一性原理

Abstract:

This paper presents a comprehensive thermodynamic modeling of the LiF-CrF₃ system. The intermediate phase Li₃CrF₆ was described by the stoichiometric compounds model and a comparative treatment of liquid phase was performed with the subregular solution model and associate solution model, respectively. All the model parameters were optimized by the experimental and first-principle predicted data within the framework of calculation of phase diagrams(CALPHAD) method. The final calculated results show that the asso-ciate solution model can better describe the experimental phase equilibrium data than subregular solution model in the liquid phase.

Key words: Calculation of phase diagrams(CALPHAD), LiF-CrF₃, First-principle

中图分类号:

O645
O614

TrendMD:

阴慧琴, 王坤, 刘文冠, 谢雷东, 韩晗, 王文锋. LiF-CrF₃二元系的热力学模拟. 高等学校化学学报, 2014, 35(12): 2668.

YIN Huiqin, WANG Kun, LIU Wenguan, XIE Leidong, HAN Han, WANG Wenfeng. Thermodynamic Modeling of the LiF-CrF₃ Binary System^†. Chem. J. Chinese Universities, 2014, 35(12): 2668.

图/表 9

Table 1 Calculated and experimental lattice constants of all compounds included in LiF-CrF3 system*

Compound	Space group	a/nm	b/nm	c/nm	Cell volume/nm³
Li₄F₄	Fm $3 ˉ$ m	0.4070(0.4030)	0.4070(0.4030)	0.4070(0.4030)	0.067419(0.065451)
Cr₂F₆	R $3 ˉ$ cr	0.5317(0.5264)	0.5317(0.5264)	0.5317(0.5264)	0.097844(0.094966)
Cr₂F₆	R $3 ˉ$ ch	0.5388(0.5206)	0.5388(0.5206)	0.5388(0.5206)	0.097043(0.087527)
Li₃CrF₆	C12/C1	1.4597(1.4381)	0.8734(0.8605)	1.0162(1.0012)	1.290921(1.234530)

Table 1 Calculated and experimental lattice constants of all compounds included in LiF-CrF3 system*

Compound	Space group	a/nm	b/nm	c/nm	Cell volume/nm³
Li₄F₄	Fm $3 ˉ$ m	0.4070(0.4030)	0.4070(0.4030)	0.4070(0.4030)	0.067419(0.065451)
Cr₂F₆	R $3 ˉ$ cr	0.5317(0.5264)	0.5317(0.5264)	0.5317(0.5264)	0.097844(0.094966)
Cr₂F₆	R $3 ˉ$ ch	0.5388(0.5206)	0.5388(0.5206)	0.5388(0.5206)	0.097043(0.087527)
Li₃CrF₆	C12/C1	1.4597(1.4381)	0.8734(0.8605)	1.0162(1.0012)	1.290921(1.234530)

Table 2 Lattice stability parameters in Eq.(2)

Compound	CrF₃(Halite)	CrF₃(Halite)	CrF₃(Liquid)	LiF(Halite)	LiF(Liquid)
a	-1187016.90252566	-1331013.90106899	-1164040.39856127	-628236.009803213	-613717.637783202
b	430.727124515671	1535.13049498254	787.630622067394	258.443290482102	386.871452514307
c	-75.9002712554932	-227.117506286621	-129.999999038696	-42.689352	-64.18256
d	-0.0201758825492859	0.0437786975402832		-0.008708996
e	6.91557308038075×10^-7	-3.39209290822347×10^-6
f	392132.289886474	24686955.0628662		265056.4
T/K	298—1100	1100—1698	298—2500	298—3000	298—3000
Ref.	[27]	[27]	[27]	[28]	[28]

Table 3 Thermodynamic parameters of LiF-CrF3 system

Subregular solution model		Associate solution model
Parameter	Ref.	Parameter	Ref.
^o $G Cr F 3 Liq$	[27]	^o $G Cr F 3 Liq$	[27]
^o $G LiF Liq$	[28]	^o $G LiF Liq$	[28]
^o $L Cr F 3, LiF Liq$ =-58070.6+4.70461T	This work	^o $L LiF, L i 3 Cr F 6 Liq$ =-3374.45	This work
¹ $L Cr F 3, LiF Liq$ =-79539.4+44.7525T	This work	^o $L Cr F 3, L i 3 Cr F 6 Liq$ =-33321.4-4.22148T	This work
		¹ $L Cr F 3, L i 3 Cr F 6 Liq$ =15471.7-25T	This work
^o $G L i 3 Cr F 6$ =3^oG_LiF+^o $G Cr F 3$ -41379-8.22884T	This work	^o $G L i 3 Cr F 6$ =3^oG_LiF+^o $G Cr F 3$ -41379-17.55	This work
		$G L i 3 Cr F 6 Liq$ =3^o $G LiF Liq$ +^o $G Cr F 3 Liq$ -101956+21.9637T	This work

Table 3 Thermodynamic parameters of LiF-CrF3 system

Subregular solution model		Associate solution model
Parameter	Ref.	Parameter	Ref.
^o $G Cr F 3 Liq$	[27]	^o $G Cr F 3 Liq$	[27]
^o $G LiF Liq$	[28]	^o $G LiF Liq$	[28]
^o $L Cr F 3, LiF Liq$ =-58070.6+4.70461T	This work	^o $L LiF, L i 3 Cr F 6 Liq$ =-3374.45	This work
¹ $L Cr F 3, LiF Liq$ =-79539.4+44.7525T	This work	^o $L Cr F 3, L i 3 Cr F 6 Liq$ =-33321.4-4.22148T	This work
		¹ $L Cr F 3, L i 3 Cr F 6 Liq$ =15471.7-25T	This work
^o $G L i 3 Cr F 6$ =3^oG_LiF+^o $G Cr F 3$ -41379-8.22884T	This work	^o $G L i 3 Cr F 6$ =3^oG_LiF+^o $G Cr F 3$ -41379-17.55	This work
		$G L i 3 Cr F 6 Liq$ =3^o $G LiF Liq$ +^o $G Cr F 3 Liq$ -101956+21.9637T	This work

Fig.1 Calculated phase diagram using subregular solution model

Fig.2 Calculated phase diagram using associate solution model

Table 4 Comparation with calculated value and experimental data of key points in LiF-CrF3 system

Fig.3 Calculated mixing enthalpy in liquid phase

Fig.4 Calculated mixing entropy in liquid phase

Fig.5 Species distribution with system composition in liquid phase

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LiF-CrF₃二元系的热力学模拟

Thermodynamic Modeling of the LiF-CrF₃ Binary System^†

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