Kinetics of Dehydration/Adsorption Reaction of LaCl3

doi:10.12141/j.issn.1000-565X.220352

Abstract

Abstract:

LaCl₃ is one of the most promising hydrated salt thermochemical heat storage materials, and its reaction kinetics plays a crucial role in the study of its reaction characteristics. The study tested the reaction characteristics of dehydration and adsorption of LaCl₃ by experiments and analyzed the reaction kinetics mechanism. The dehydration process of LaCl₃·7H₂O at the heating rates of 1, 10 and 20 K/min was tested by a synchronous thermal analyzer. The results show that the dehydration process of LaCl₃·7H₂O can be divided into three stages, where 4,2 and 1 water molecules are removed respectively.The initial temperature of each stage is different at different heating rates. The activation energy value of three stages was calculated by FWO method and the activation energy of the first stage was the largest. The Doyle method was used to solve the mechanism functions of each stage, in which the first stage conforms to the shrinking cylinder model in the phase boundary reaction, while the second and the third stage conformed to the random nucleation and subsequent growth model. The adsorption process of LaCl₃ was tested at the temperature of 15, 20, 25, 30 ℃ and at the relative humidity of 40%, 60%, 80% by a constant temperature and humidity chamber. The adsorption reaction rate of LaCl₃ is positively correlated with the temperature and humidity. When the relative humidity is 40%, LaCl₃ does not decompose. The reaction rate of LaCl₃ is faster in the initial stage of the adsorption process. As the adsorption process proceeds, LaCl₃·nH₂O crystals formed on the surface restricts the contact between LaCl₃ and water vapor. The kinetic equation of LaCl₃ adsorption reaction was fitted, the adsorption process of LaCl₃ conformed to the chemical reaction series model, and the reaction order was 0.837. The results show that LaCl₃ has good chemical kinetics and high heat release, and is a potential chemical thermal storage material.

Key words: lanthanum chloride, thermochemical heat storage, reaction kinetics, activation energy, mechanism function

CLC Number:

TK02

LOU Bo, ZHOU Daheng, XIA Jun. Kinetics of Dehydration/Adsorption Reaction of LaCl₃[J]. Journal of South China University of Technology(Natural Science Edition), 2023, 51(8): 71-79.

Figures/Tables 14

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Table 1

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Table 3

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Table 5

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Fig.9

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升温速率/（K·min^-1）	阶段	起始温度/℃	失重率/%
1	第1阶段	35.6	19.9
	第2阶段	87.8	9.2
	第3阶段	116.0	4.6
10	第1阶段	45.8	12.2
	第2阶段	112.8	16.7
	第3阶段	161.8	5.4
20	第1阶段	48.5	8.5
	第2阶段	17.8	21.6
	第3阶段	78.5	4.9

序号	反应模型	模型编号	f（α）	G（α）
1	反应级数模型	F0	1	α
2	反应级数模型	F1	1-α	-ln（1-α）
3	反应级数模型	F2	（1-α）²	（1-α）^-1-1
4	反应级数模型	F3	（1-α）³	［（1-α）^-2-1］/2
5	随机成核和随后生长	A2	2（1-α）［-ln（1-α）］^1/2	［-ln（1-α）］^1/2
6	随机成核和随后生长	A3	3（1-α）［-ln（1-α）］^2/3	［-ln（1-α）］^1/3
7	随机成核和随后生长	A4	4（1-α）［-ln（1-α）］^3/4	［-ln（1-α）］^1/4
8	幂函数法则	P0	（3/2）α^-1/2	α^3/2
9	幂函数法则	P2	2α^1/2	α^1/2
10	幂函数法则	P3	3α^2/3	α^1/3
11	幂函数法则	P4	4α^3/4	α^1/4
12	几何收缩模型	R2	2（1-α）^1/2	1-（1-α）^1/2
13	几何收缩模型	R3	3（1-α）^2/3	1-（1-α）^1/3
14	扩散模型	D1	1/（2α）	α²
15	扩散模型	D2	［-ln（1-α）］^-1	（1-α）ln（1-α）+α
16	扩散模型	D3	（3/2）（1-α）^2/3［1-（1-α）^1/3］^-1	［1-（1-α）^1/3］²
17	扩散模型	D4	（3/2）［（1-α）^-1/3-1］^-1	［1-（2/3）α］-（1-α）^2/3

序号	反应模型	模型编号	f（α）
1	随机成核和随后生长	A2	2（1-α）［-ln（1-α）］^1/2
2	随机成核和随后生长	A3	3（1-α）［-ln（1-α）］^2/3
3	随机成核和随后生长	A4	4（1-α）［-ln（1-α）］^3/4
4	几何收缩模型	R2	2（1-α）^1/2
5	几何收缩模型	R3	3（1-α）^2/3
6	几何收缩模型	R4	4（1-α）^3/4
7	扩散模型	D1	1/（2α）
8	扩散模型	D2	-［1/ln（1-α）］
9	扩散模型	D3	［3（1-α）^2/3］/［2（1-（1-α）^1/3）］
10	扩散模型	D4	3/［2（（1-α）^-1/3-1）］
11	反应级数模型	F1	1-α
12	反应级数模型	Fn	（1-α） ⁿ

序号	r²
序号	15 ℃	20 ℃	25 ℃	30 ℃
1	0.317 22	0.293 24	0.329 31	0.336 45
2	0.264 99	0.234 50	0.283 04	0.301 53
3	0.233 96	0.201 91	0.255 53	0.280 57
4	0.944 43	0.913 66	0.919 67	0.950 34
5	0.946 52	0.943 03	0.976 90	0.985 42
6	0.980 88	0.974 68	0.988 25	0.990 03
7	0.189 21	0.183 96	0.088 54	0.071 01
8	0.314 15	0.364 42	0.359 49	0.372 70
9	0.201 12	0.276 78	0.311 54	0.321 32
10	0.274 07	0.334 24	0.350 56	0.359 38
11	0.963 48	0.973 65	0.978 97	0.971 02
12	0.979 90	0.978 75	0.990 69	0.989 56

温度/℃	a	b	n
15	8.040×10^-4	0.946	0.769
20	9.257×10^-4	0.939	0.864
25	1.230×10^-3	0.932	0.825
30	1.290×10^-3	0.924	0.766

Kinetics of Dehydration/Adsorption Reaction of LaCl₃

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