Dehydration Process of Ammonium Aluminum Sulfate Dodecahydrate and Its Thermodynamics and Kinetics Research

doi:10.19894/j.issn.1000-0518.230298

Chinese Journal of Applied Chemistry ›› 2024, Vol. 41 ›› Issue (5): 668-676.DOI: 10.19894/j.issn.1000-0518.230298

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Dehydration Process of Ammonium Aluminum Sulfate Dodecahydrate and Its Thermodynamics and Kinetics Research

Biao HU¹^,², Hui WANG¹^,²(), Zhen-Ying ZHANG²(), Dao-Rong XUE³, Qiang LIU³

^1.State Key Laboratory of Multiphase Complex Systems，Institute of Process Engineering，Chinese Academy of Science，Beijing 100190，China
^2.College of Architecture and Engineering，North China University of Science and Technology，Tangshan 063210，China
^3.Hebei Daorong New Energy Technology Co. ，Xingtai 054700，China

Received:2023-09-26 Accepted:2024-03-13 Published:2024-05-01 Online:2024-06-03
Contact: Hui WANG,Zhen-Ying ZHANG
About author:zhangzhenying@ncst.edu.cn
13126591892@163.com；
Supported by:
the S&T Program of Hebei(22294301Z);the Science and Technology Cooperation Program of Chifeng Regional Collaborative Innovation Platform(2022zk002)

Abstract

Abstract:

The dehydration process of NH₄Al（SO₄）₂·12H₂O under the heating stage was tested by thermogravimetric-differential thermal analysis （TG-DTA）， and the dehydration process was analyzed by the thermodynamical and kinetic methods. The results showed that the dehydration process of NH₄Al（SO₄）₂·12H₂O was divided into two steps. In the first step， 9 water molecules were dehydrated from NH₄Al（SO₄）₂·12H₂O to form NH₄Al（SO₄）₂·3H₂O； the remaining 3 water molecules were dehydrated and it became to NH₄Al（SO₄）₂. Thermodynamic analysis of NH₄Al（SO₄）₂·12H₂O dehydration process showed that the shed liquid water molecules were then vaporized. Kinetic analysis of NH₄Al（SO₄）₂·12H₂O dehydration process indicated that the reaction activation energy of 93.53 kJ/mol for the removal of 9 water molecules， and the activation energy of 118.7 kJ/mol for the removal of 3 water molecules.

Key words: Ammonium aluminum sulfate dodecahydrate, Dehydration process, Thermodynamics, Dynamics

CLC Number:

O611.5

Biao HU, Hui WANG, Zhen-Ying ZHANG, Dao-Rong XUE, Qiang LIU. Dehydration Process of Ammonium Aluminum Sulfate Dodecahydrate and Its Thermodynamics and Kinetics Research[J]. Chinese Journal of Applied Chemistry, 2024, 41(5): 668-676.

Figures/Tables 8

Fig.1 TG and DTG curves of NH4Al（SO4）2·12H2O at a heating rate of 5 K/min

Table 1 Thermodynamic data of nine liquid water loss processes for ammonium aluminum sulfate dodecahydrate

Temperture/℃	T/K	ΔG₁/（J·mol^-1）	$K 1 θ$	a_w	p $w 0$ /kPa	p_w/kPa
50	323.15	14 262.65	4.94×10^-3	0.55	12.34	6.84
55	328.15	12 623.05	9.77×10^-3	0.60	15.74	9.41
60	333.15	10 983.45	1.89×10^-2	0.64	19.92	12.82
65	338.15	9 343.85	3.60×10^-2	0.69	25.01	17.28
70	343.15	7 704.25	6.70×10^-2	0.74	31.16	23.08
75	348.15	6 064.65	0.12	0.79	38.55	30.54
80	353.15	4 425.05	0.22	0.85	47.38	40.07
85	358.15	2 785.45	0.39	0.90	57.88	52.16
90	363.15	1 145.85	0.68	0.96	70.14	67.23
95	368.15	-493.75	1.17	1.02	84.56	86.07
100	373.15	-2 133.35	1.99	1.08	101.33	109.35
105	378.15	-3 772.95	3.31	1.14	120.85	138.06
110	383.15	-5 412.55	5.46	1.21	143.31	173.05
115	388.15	-7 052.15	8.88	1.27	169.11	215.54
120	393.15	-8 691.75	14.26	1.34	198.64	266.86

Table 1 Thermodynamic data of nine liquid water loss processes for ammonium aluminum sulfate dodecahydrate

Temperture/℃	T/K	ΔG₁/（J·mol^-1）	$K 1 θ$	a_w	p $w 0$ /kPa	p_w/kPa
50	323.15	14 262.65	4.94×10^-3	0.55	12.34	6.84
55	328.15	12 623.05	9.77×10^-3	0.60	15.74	9.41
60	333.15	10 983.45	1.89×10^-2	0.64	19.92	12.82
65	338.15	9 343.85	3.60×10^-2	0.69	25.01	17.28
70	343.15	7 704.25	6.70×10^-2	0.74	31.16	23.08
75	348.15	6 064.65	0.12	0.79	38.55	30.54
80	353.15	4 425.05	0.22	0.85	47.38	40.07
85	358.15	2 785.45	0.39	0.90	57.88	52.16
90	363.15	1 145.85	0.68	0.96	70.14	67.23
95	368.15	-493.75	1.17	1.02	84.56	86.07
100	373.15	-2 133.35	1.99	1.08	101.33	109.35
105	378.15	-3 772.95	3.31	1.14	120.85	138.06
110	383.15	-5 412.55	5.46	1.21	143.31	173.05
115	388.15	-7 052.15	8.88	1.27	169.11	215.54
120	393.15	-8 691.75	14.26	1.34	198.64	266.86

Table 2 Thermodynamic data of nine gaseous water processes for ammonium aluminum sulfate dodecahydrate loss

Temperture/℃	T/K	ΔG₂/（J·mol^-1）	$K 2 θ$	a_w	p_w/kPa
50	323.15	50 353.66	7.23×10^-9	0.12	12.62
55	328.15	45 003.91	6.84×10^-8	0.16	16.20
60	333.15	39 654.16	6.04×10^-7	0.20	20.64
65	338.15	34 304.41	5.01×10^-6	0.26	26.11
70	343.15	28 954.66	3.90×10^-5	0.32	32.80
75	348.15	23 604.91	2.87×10^-4	0.40	40.93
80	353.15	18 255.16	1.99×10^-3	0.50	50.77
85	358.15	12 905.41	1.31×10^-2	0.62	62.58
90	363.15	7 555.66	8.17×10^-2	0.76	76.71
95	368.15	2 205.91	0.49	0.92	93.50
100	373.15	-3 143.84	2.75	1.12	113.37
105	378.15	-8 493.59	14.87	1.35	136.76
110	383.15	-13 843.34	76.95	1.62	164.17
115	388.15	-19 193.09	381.82	1.94	196.15
120	393.15	-24 542.84	1 818.92	2.30	233.30

Table 2 Thermodynamic data of nine gaseous water processes for ammonium aluminum sulfate dodecahydrate loss

Temperture/℃	T/K	ΔG₂/（J·mol^-1）	$K 2 θ$	a_w	p_w/kPa
50	323.15	50 353.66	7.23×10^-9	0.12	12.62
55	328.15	45 003.91	6.84×10^-8	0.16	16.20
60	333.15	39 654.16	6.04×10^-7	0.20	20.64
65	338.15	34 304.41	5.01×10^-6	0.26	26.11
70	343.15	28 954.66	3.90×10^-5	0.32	32.80
75	348.15	23 604.91	2.87×10^-4	0.40	40.93
80	353.15	18 255.16	1.99×10^-3	0.50	50.77
85	358.15	12 905.41	1.31×10^-2	0.62	62.58
90	363.15	7 555.66	8.17×10^-2	0.76	76.71
95	368.15	2 205.91	0.49	0.92	93.50
100	373.15	-3 143.84	2.75	1.12	113.37
105	378.15	-8 493.59	14.87	1.35	136.76
110	383.15	-13 843.34	76.95	1.62	164.17
115	388.15	-19 193.09	381.82	1.94	196.15
120	393.15	-24 542.84	1 818.92	2.30	233.30

Table 3 Thermodynamic data of ammonium aluminum sulfate dodecahydrate losing three gaseous water processes

Temperture/℃	T/K	ΔG₄/（J·mol^-1）	$K 3 θ$	a_w	p_w/MPa
120	393.15	-58 894.12	6.66×10⁷	405.36	4.11×10¹
125	398.15	-61 810.82	1.28×10⁸	504.24	5.11×10¹
130	403.15	-64 727.52	2.43×10⁸	623.86	6.32×10¹
135	408.15	-67 644.22	4.53×10⁸	767.83	7.78×10¹
140	413.15	-70 560.92	8.31×10⁸	940.30	9.53×10¹
145	418.15	-73 477.62	1.50×10⁹	1 145.94	1.16×10²
150	423.15	-76 394.32	2.69×10⁹	1 390.04	1.41×10²
160	433.15	-82 227.72	8.22×10⁹	2 018.14	2.04×10²
170	443.15	-88 061.12	2.39×10¹⁰	2 881.15	2.92×10²
180	453.15	-93 894.52	6.64×10¹⁰	4 049.08	4.10×10²
190	463.15	-99 727.92	1.76×10¹¹	5 607.44	5.68×10²
200	473.15	-105 561.32	4.49×10¹¹	7 659.43	7.76×10²
210	483.15	-111 394.72	1.10×10¹²	10 328.12	1.05×10³
220	493.15	-117 228.12	2.60×10¹²	13 758.83	1.39×10³
230	503.15	-123 061.52	5.95×10¹²	18 121.34	1.84×10³
240	513.15	-12 8894.92	1.32×10¹³	23 612.25	2.39×10³
250	523.15	-134 728.32	2.83×10¹³	30 457.20	3.09×10³

Table 3 Thermodynamic data of ammonium aluminum sulfate dodecahydrate losing three gaseous water processes

Temperture/℃	T/K	ΔG₄/（J·mol^-1）	$K 3 θ$	a_w	p_w/MPa
120	393.15	-58 894.12	6.66×10⁷	405.36	4.11×10¹
125	398.15	-61 810.82	1.28×10⁸	504.24	5.11×10¹
130	403.15	-64 727.52	2.43×10⁸	623.86	6.32×10¹
135	408.15	-67 644.22	4.53×10⁸	767.83	7.78×10¹
140	413.15	-70 560.92	8.31×10⁸	940.30	9.53×10¹
145	418.15	-73 477.62	1.50×10⁹	1 145.94	1.16×10²
150	423.15	-76 394.32	2.69×10⁹	1 390.04	1.41×10²
160	433.15	-82 227.72	8.22×10⁹	2 018.14	2.04×10²
170	443.15	-88 061.12	2.39×10¹⁰	2 881.15	2.92×10²
180	453.15	-93 894.52	6.64×10¹⁰	4 049.08	4.10×10²
190	463.15	-99 727.92	1.76×10¹¹	5 607.44	5.68×10²
200	473.15	-105 561.32	4.49×10¹¹	7 659.43	7.76×10²
210	483.15	-111 394.72	1.10×10¹²	10 328.12	1.05×10³
220	493.15	-117 228.12	2.60×10¹²	13 758.83	1.39×10³
230	503.15	-123 061.52	5.95×10¹²	18 121.34	1.84×10³
240	513.15	-12 8894.92	1.32×10¹³	23 612.25	2.39×10³
250	523.15	-134 728.32	2.83×10¹³	30 457.20	3.09×10³

Fig.2 DTA curves of ammonium aluminum sulfate dodecahydrate at different heating rates of 1， 2， 5 and 10 K/min

Table 4 Peak temperature of ammonium aluminum sulfate dodecahydrate losing 9 water at different heating rates

Heating rate β/（K·min^-1）	Removing 9 crystal water	Removing the remaining 3 crystal water
Heating rate β/（K·min^-1）	T_p/℃	The first T_p/℃	The second T_p/℃
1	70.20	/	/
2	78.26	/	194.80
5	87.26	/	213.32
10	94.74	138.63	215.39

Fig.3 Kissinger equation：（A） Ammonium aluminum sulfate dodecahydrate loses nine water peak；（B） Ammonium aluminum sulfate dodecahydrate loses three water peak

Table 5 The activation energy and pre-exponential factor of ammonium aluminum sulfate dodecahydrate

Dehydration process	R²	E_k/（kJ·mol^-1）	ln A_k/s^-1
Removing 9 crystal water	0.997 8	93.53	30.37
Removing the remaining 3 crystal water	0.864 1	118.70	28.44

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Dehydration Process of Ammonium Aluminum Sulfate Dodecahydrate and Its Thermodynamics and Kinetics Research

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