Thermal decomposition mechanism of ammonium sulfate catalyzed by ferric oxide

doi:10.1007/s11705-013-1320-y

Front Chem Sci Eng

2013, Vol. 7

Issue (2) : 210-217 https://doi.org/10.1007/s11705-013-1320-y

RESEARCH ARTICLE

Thermal decomposition mechanism of ammonium sulfate catalyzed by ferric oxide

Xingfu SONG(

), Jingcai ZHAO, Yunzhao LI, Ze SUN, Jianguo YU

National Engineering Research Center for Integrated Utilization of Salt Lake Resource, East China University of Science and Technology, Shanghai 200237, China

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Abstract

The decomposition mechanism of ammonium sulfate catalyzed by ferric oxide was investigated in this paper. The decomposition kinetics parameters were determined via a global optimization of the Kissinger iterative method using the non-isothermal thermogravimetric analysis data. The products and intermediates were synchronously characterized by X-ray diffraction and mass spectrometry. The obtained results indicate that the decomposition process of ammonium sulfate catalyzed by ferric oxide can be divided into four stages of which the activation energies are 123.64, 126.58, 178.77 and 216.99 kJ·mol^-1 respectively. The decomposition mechanisms at the first and the fourth stage both belong to Mample power theorem, the second stage belongs to Avrami-Erofeev equation and the third belongs to contracting sphere (volume) equation. The corresponding pre-exponential factors (A) are calculated simultaneously.

Keywords ammonium sulfate decomposition kinetics ferric oxide thermogravimetric analysis

Corresponding Author(s): SONG Xingfu,Email:xfsong@ecust.edu.cn

Issue Date: 05 June 2013

Cite this article:

Xingfu SONG,Jingcai ZHAO,Yunzhao LI, et al. Thermal decomposition mechanism of ammonium sulfate catalyzed by ferric oxide[J]. Front Chem Sci Eng, 2013, 7(2): 210-217.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-013-1320-y
https://academic.hep.com.cn/fcse/EN/Y2013/V7/I2/210

Fig.1 TG curve of the mixture with the mole ratio of 2 ∶ 1

Fig.2 MS curves of the gases generated in the decomposition of the mixture

Fig.3 XRD analysis of the solid residue at different temperatures

Tab.1 Thermal decomposition mechanism of (NH)SO catalyzed by FeO

Fig.4 TG curves of the mixture at different heating rates

Tab.2 Temperatures corresponding to given conversion degrees at different heating rates at the four decomposition stages

Tab.3 Conversion degrees corresponding to given temperatures at different heating rates at the four decomposition stages

Tab.4 Slope, correlation coefficient of plot of ln() ln for 30 kinds of reaction models at the four decomposition stages

Tab.5 The activation energy, pre-exponential factor and the reaction function of the decomposition at four stages

No.	Function name	Mechanism	Integral function G(α)	Differential function f(α)
1	Parabolic line law	One-dimensional diffusion	α2	12α-1
2	Valensi equation	Two-dimensional diffusion	α+(1-α)ln?(1-α)	[-ln?(1-α)]-1
3	Ginstling-Brounstein equation	Three-dimensional diffusion (cylindrical symmetry)	1-23α-(1-α)23	32[(1-α)-13-1]-1
4	Jander equation	Three-dimensional diffusion (spherical symmetry)	[1-(1-α)13]2	32(1-α)23[1-(1-α)13]-1
5	Jander equation	Three-dimensional diffusion	[1-(1-α)13]12	6(1-α)23[1-(1-α)13]12
6	Jander equation	Three-dimensional diffusion	[1-(1-α)12]12	4(1-α)12[1-(1-α)12]12
7	Inverse Jander equation	Three-dimensional diffusion	[(1+α)13-1]2	32(1+α)23[(1+α)13-1]-1
8	Zhuralev-Lesokin-Tempelmanequation	Three-dimensional diffusion	[(1-α)-13-1]2	32(1-α)43[(1-α)-13-1]-1
9	Mample power theorem	nuclei growth (n = 1)	-ln?(1-α)	1-α
10	Avrami-Erofee equation	Random nucleation and nuclei growth (n = 2/3)	[-ln?(1-α)]23	32(1-α)[-ln?(1-α)]13
11	Avrami-Erofee equation	Random nucleation and nuclei growth (n = 1/2)	[-ln?(1-α)]12	2(1-α)[-ln?(1-α)]12
12	Avrami-Erofee equation	Random nucleation and nuclei growth (n = 1/3)	[-ln?(1-α)]13	3(1-α)[-ln?(1-α)]23
13	Avrami-Erofee equation	Random nucleation and nuclei growth (n = 4)	[-ln?(1-α)]4	14(1-α)[-ln?(1-α)]-3
14	Avrami-Erofee equation	Random nucleation and nuclei growth (n = 1/4)	[-ln?(1-α)]14	4(1-α)[-ln?(1-α)]34
15	Avrami-Erofee equation	Random nucleation and nuclei growth (n = 2)	[-ln?(1-α)]2	12(1-α)[-ln?(1-α)]-1
16	Avrami-Erofee equation	Random nucleation and nuclei growth (n = 3)	[-ln?(1-α)]3	13(1-α)[-ln?(1-α)]-2
17	Contracting cylinder (area)	Phase boundary reaction, (cylindrical symmetry)	1-(1-α)12	2(1-α)12
18	Reaction order	Chemical reaction	1-(1-α)3	13(1-α)-2
19	Reaction order	Chemical reaction	1-(1-α)2	12(1-α)-1
20	Reaction order	Chemical reaction	1-(1-α)4	14(1-α)-3
21	Contracting sphere (volume)	Phase boundary reaction, (spherical symmetry)	1-(1-α)13	3(1-α)23
22	Reaction order	Chemical reaction	1-(1-α)14	4(1-α)34
23	Mampel Power theorem	Phase boundary reaction, (One-dimension) n = 1	1-(1-α)11=α	1
24	Mampel Power theorem	Exponential nucleation (n = 3/2)	α32	23α-12
25	Mampel Power theorem	Exponential nucleation (n = 1/2)	α12	2α12
26	Mampel Power theorem	Exponential nucleation (n = 1/3)	α13	3α23
27	Mampel Power theorem	Exponential nucleation (n = 1/4)	α14	4α34
28	Second order	Chemical reaction	(1-α)-1	(1-α)2
29	Reaction order	Chemical reaction	(1-α)-1-1	(1-α)2
30	2/3 order	Chemical reaction	(1-α)-12	2(1-α)32

Tab.6 Thirty common kinetic mechanism functions

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