Thermodynamic Modeling of the LiF-CrF3 Binary System†

doi:10.7503/cjcu20140396

Abstract

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

CLC Number:

O645
O614

TrendMD:

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

Figures/Tables 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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Thermodynamic Modeling of the LiF-CrF₃ Binary System^†

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