砷/氢/氧体系中均相反应机理的研究

熊中朴; 于洋; 陈文洋; 陈娟

doi:10.19906/j.cnki.JFCT.2021046

砷/氢/氧体系中均相反应机理的研究

doi: 10.19906/j.cnki.JFCT.2021046

山东大学能源与动力工程学院，山东济南 250061

基金项目: 国家自然科学基金（51776112）和山东省重点研发计划项目（2018GGX104019）资助

详细信息

作者简介:
于洋：202014473@mail.sdu.edu.cn

通讯作者:
E-mail: juanchen@sdu.edu.cn

中图分类号: X511
计量
- 文章访问数: 466
- HTML全文浏览量: 117
- PDF下载量: 39
- 被引次数: 0
出版历程
- 收稿日期: 2020-12-24
- 修回日期: 2021-01-29
- 网络出版日期: 2021-03-30
- 刊出日期: 2021-07-15

Homogeneous reaction mechanism in arsenic/hydrogen/oxygen system

School of Energy and Power Engineering, Shandong University, Jinan 250061, China

Funds: The project was supported by National Natural Science Foundation of China (51776112) and the Shandong Provincial Natural Science Foundation, China (2018GGX104019)

摘要

摘要: 采用量子化学的方法，利用量子化学软件Gaussian09和GaussView，在B3LYP/6-311G(3df, 3pd)理论水平下，对砷/氢/氧体系燃烧反应的微观机理进行研究。优化了13个基元反应的反应物、中间体、过渡态以及产物的构型，并通过振动频率和内禀反应坐标验证反应真实性。采用KiSThelP软件包基于传统过渡态理论拟合计算出动力学参数。本研究对砷燃烧体系中部分重要基元反应进行研究，便于后续建立砷的燃烧动力学模型。
- 燃煤 /
- 砷 /
- 微观机理 /
- DFT
Abstract: Herein quantum chemistry methods were used to discuss the microscopic mechanism in the arsenic/hydrogen/oxygen reaction system during combustion by Gaussian09 and GaussView at the theoretical level of B3LYP/6-311G (3df, 3pd). Configuration of the reactants, intermediates, transition states, and products of 13 elementary reactions were optimized and the authenticity of these reactions were verified by frequency and intrinsic reaction coordinates. Finally, the kinetic parameters were calculated through KiSThelP based on the classic transition state theory. This study focused on some of the most important reations in the arsenic/hydrogen/oxygen system, which makes sense to establish arsenic dynamic model during combustion.
- coal combustion /
- arsenic /
- microscopic mechanism /
- DFT

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FIG. 797. FIG. 797.

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图 1 优化后的AsO、O₂、As₂O₃(D3H)和As₂O₃(GAMCHE)

Figure 1 Optimized AsO, O₂, As₂O₃ (D3H) and As₂O₃ (GAMCHE)

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图 2 AsO₂OH+H₂O = H₃AsO₄反应物、过渡态以及生成物构型

Figure 2 Geometries of intermediate, transition state and product of AsO₂OH+H₂O = H₃AsO₄

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图 3 AsO₂OH+H₂O = H₃AsO₄反应过程示意图

Figure 3 Reactant process analysis of AsO₂OH+H₂O = H₃AsO₄

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图 4 AsO₂OH+H₂O = H₃AsO₄内禀反应坐标

Figure 4 Intrinsic reaction coordinate diagram of AsO₂OH+H₂O = H₃AsO₄

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图 5 AsO₂OH+H₂O = H₃AsO₄反应过程能量变化

Figure 5 Gibbs energy change in AsO₂OH+H₂O = H₃AsO₄ reaction process

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图 6 KiSThelP拟合阿伦尼乌斯曲线

Figure 6 KiSThelP fitting Arrhenius curve

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表 1 计算值与文献值对比

Table 1 Comparison of calculated values and literature values

Species	Bond length(r/Å) and angles(α/°)	Calculated result	Referenced value^[17]
O₂	r(O−O)	1.20255	1.239
AsO	r(As−O)	1.62401	1.624
As₂O₃(D3H)	r(As−O)	1.84376	1.836
	r(As-As)	2.38940	2.375
	α(As−O−As)	80.77769	80.6
As₂O₃(GAUCHE)	r(As−O)	1.61949	1.610
	r(O−As)	1.78284	1.794
	α(As−O−As)	105.77862	106.3
	α(O−As−O)	129.64809	133.8

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表 2 砷参与的基元反应

Table 2 Elementary reactions of Arsenic

No.	Elementary reactions
1	As+AsO₂ = 2AsO
2	As+H₂O = AsOH+H
3	AsO+H₂O = AsOOH+H
4	AsOOH+H = AsO₂+H₂
5	AsO₂+H₂O = AsO₂OH+H
6	AsO₂OH+H = AsO(OH)₂
7	AsOOH+H₂O = As(OH)₃
8	AsOOH+H = As(OH)₂
9	As(OH)₃+H = AsO(OH)₂+H₂
10	AsOH+H₂O = As(OH)₂
11	As(OH)₂+H₂O = As(OH)₃+H
12	H₃AsO₄+H = AsO(OH)₂+H₂O
13	AsO₂OH+H₂O = H₃AsO₄

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表 3 AsO₂OH+H₂O = H₃AsO₄反应各稳定点振动频率

Table 3 Frequencies of stable points of AsO₂OH+H₂O = H₃AsO₄

No.	Vibrations frequencies/cm⁻¹
AsO₂OH	245.63, 281.93, 301.64, 459.23, 726.01, 947.36, 1018.14, 1073.63, 3771.60
H₂O	1641.28, 3819.58, 3912.16
TS	−1358.59, 165.93, 255.41, 266.03, 293.69, 370.60, 433.77, 553.71, 689.49,763.14, 806.75, 873.86, 1011.59, 1059.90, 1362.22, 1962.70, 3786.56, 3788.99
H₃AsO₄	123.08, 142.48, 208.18, 220.49, 281.94, 289.95, 300.96, 416.02, 548.75, 617.39, 718.8, 936.82, 1014.39, 1064.23, 1610.44, 3738.20, 3790.15, 3835.85

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表 4 AsO₂OH+H₂O = H₃AsO₄反应过程能量变化

Table 4 Energy change in AsO₂OH+H₂O = H₃AsO₄ reaction process

	B3LYP/(a.u.)	ZEP/(a.u.)	E_tot/(a.u.)	Erel/(kcal·mol⁻¹)
AsO₂OH+ H₂O	−2538.657127	0.041458	−2538.615669	0
Initermediate	−2538.679596	0.045239	−2538.634357	−14.2883
TS	−2538.660815	0.041958	−2538.618857	−2.0000
H₃AsO₄	−2538.723255	0.044405	−2538.678850	−39.6467
E_a, for/(kcal·mol⁻¹)	12.2883
E_a, rev/(kcal·mol⁻¹)	37.6467

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表 5 砷参与的各基元反应反应动力学参数

Table 5 Kinetic parameters of each elementary reaction of Arsenic

No.	Elementary reactions	A	n	E_a/（cal·mol⁻¹）
1	As+AsO₂ = 2AsO	3.312 × 10¹²	0.01	990
2	As+H₂O = AsOH+H	5.74 × 10⁵	2.53	9548
3	AsO₂OH+H₂ = AsOOH+H₂O	8.07 × 10²	2.81	43100
4	AsOOH+H = AsO₂+H₂	5.06 × 10⁷	1.85	7303
5	AsO₂+H₂O = AsO₂OH+H	5.00 ×10⁻²	3.95	48637
6	AsO₂OH+H = AsO(OH)₂	1.38 × 10⁹	1.57	382
7	AsOOH+H₂O = As(OH)₃	1.09 × 10⁹	0.53	7330
8	AsOOH+H = As(OH)₂	6.56 × 10⁸	1.57	119
9	As(OH)₃+H = AsO(OH)₂+H₂	6.62 × 10⁷	1.9	5403
10	AsOH+H₂O = As(OH)₂	3.991 × 10⁻¹	4.04	40720
11	As(OH)₂+H₂O = As(OH)₃+H	3.22 × 10⁻²	4.04	34765
12	H₃AsO₄+H = AsO(OH)₂+H₂O	2.97 × 10⁸	1.67	10179
13	AsO₂OH+H₂O = H₃AsO₄	9.80 × 10⁹	0.52	7982

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