Theoretical Studies on the Single Water Molecule’s Effect on the Main Channel of H2S+HO2 Reaction†

doi:10.7503/cjcu20140310

Abstract

Abstract:

The reaction mechanism and rate constant for the major channel between HO₂ and H₂S, without and with a water molecule, were investigated theoretically at the CCSD(T)/aug-cc-pVTZ// B3LYP/6-311+G(2df, 2p) level. The goal of the present investigation is to determine how the single water molecule can affect the reaction mechanisms and kinetics for the major channel of HO₂+H₂S reaction and estimate the importance of water effects on the major channel of HO₂+H₂S reaction. The calculated results show that the HO₂+H₂S reaction mainly occurs through the channel of H₂O₂+HS formation with the apparent activation energy of 14.94 kJ/mol. When one water molecule is added, the reaction mechanism of the major channel becomes quite complex yielding three different reaction channels of H₂O…HO₂+H₂S(RW1), HO₂…H₂O+H₂S(RW2) and H₂O…H₂S+HO₂(RW2). For single water-catalyzed the major channel of HO₂+H₂S reaction, channel RW1 is dominant and path RW1 is the most favorable. Additionally, to estimate the importance of channel RW1 in the atmosphere, its rate constant is evaluated using the conventional transition state theory with Wigner tunneling correction. The calculated results show that the effective rate constant of path RW1 increases with the temperature increases. At 298 K, the value of k $' RW 1$ /k_total is up to 54.2%, indicating that the single water molecule has a obvious effect on the major channel of atmospheric reaction of HO₂+H₂S. The present study provides further insight into water effects in the atmospheric chemistry.

Key words: HO2+H2S reaction, Water-catalyzed, Reaction mechanism, Transition state theory

CLC Number:

O643.1

TrendMD:

XU Qiong, WANG Rui, ZHANG Tianlei, ZHANG Haolin, WANG Zhiyin, WANG Zhuqing. Theoretical Studies on the Single Water Molecule’s Effect on the Main Channel of H₂S+HO₂ Reaction^†[J]. Chem. J. Chinese Universities, 2014, 35(10): 2191.

Figures/Tables 11

Fig.1 Optimized geometries of all the species involved in HO2+H2S reaction at B3LYP/6-311+G(2df,2p) level Bond lengths are in nm. The values with parentheses were the experimental data from the NIST chemistry webbook[27]; the values with bracket were obtained at the CCSD/aug-cc-pVTZ level of theory.

Table 1 Zero-point energy(ZPE), entropies(S), relative energies[ΔE and Δ(E+ ZPE)], enthalpies[ΔH(298)], and free energies [ΔG(298)] for the HO2+H2S reaction a

Species	ZPE/ (kJ·mol^-1)	S/(J·mol^-1· K^-1)	ΔE/ (kJ·mol^-1)	Δ(E+ZPE)/ (kJ·mol^-1)	ΔH(298)/ (kJ·mol^-1)	ΔG(298)/ (kJ·mol^-1)
HO₂+H₂S	76.49	439.65	0	0	0^b	0
IM1	80.84	360.23	-8.69	-4.35	-3.22	20.48
TS1	75.07	306.52	63.87	62.45	58.65	98.31
IMF1	89.20	348.53	-10.12	2.59	2.51	29.68
H₂O₂+HS	85.61	418.79	4.85	13.96	13.63, 12.96±2.93^b	19.86
TS2	88.74	293.44	154.58	166.82	161.77	205.36
IMF2	90.83	325.75	-267.94	-253.60	-254.94	-221.00
H₂O+HSO	82.93	429.70	-241.40	-235.00	-234.92	-231.95

Fig.2 Energy diagrams in the naked reaction of HO2+H2S Energies were computed at the CCSD(T)/aug-cc-pVTZ//B3LYP/6-311+G(2df,2p) level, including the zero-point energy correction.

Fig.3 Geometrical parameters for HO2, H2O, H2S and the M1 to M3 complexes optimized at the B3LYP/6-311+G(2df,2p) level Bond lengths are in nm. The values with parentheses were the experimental data from the NIST chemistry webbook[27].

Fig.4 Optimized geometries of the species involved in the reaction of M1+H2S at the B3LYP/6-311+G(2df,2p) level(bond lengths are in nm)

Fig.5 Energy diagrams in the reaction of M1+H2S Energies were computed at the CCSD(T)/aug-cc-pVTZ//B3LYP/6-311+G(2df,2p) level, including the zero-point energy correction.

Fig.6 Optimized geometries of the species involved in the reaction of M2+H2S at B3LYP/6-311+G(2df,2p) level(bond lengths are in nm)

Fig.7 Energy diagrams in the reaction of M2+H2S Energies were computed at the CCSD(T)/aug-cc-pVTZ//B3LYP/6-311+G(2df,2p) level, including the zero-point energy correction.

Fig.8 Optimized geometries of the species involved in the reaction of M2+HO2 at B3LYP/6-311+G(2df,2p) level(Bond lengths are in nm)

Fig.9 Energy diagrams in the reaction of M3+HO2 Energies were computed at the CCSD(T)/aug-cc-pVTZ//B3LYP/6-311+G(2df,2p) level, including the zero-point energy correction.

Table 2 Kinetic results for formation process of H2O2+HS occurring through channels R1 and RW1*

h/km	T/K	k_R1/(cm³· molecule^-1·s^-1)	k_RW1	[H₂O]^[22]	K_eq(A)	k $' RW 1$	k_total	k $' RW 1$ /k_total(%)
0	298.2	6.01×10^-23	6.82×10^-18	2.59×10¹⁷	4.02×10^-23	7.1×10^-23	1.31×10^-22	54.2
0	288.2	3.55×10^-23	5.48×10^-18	2.59×10¹⁷	4.24×10^-23	6.02×10^-23	9.57×10^-23	62.9
2	275.2	1.76×10^-23	4.04×10^-18	1.11×10¹⁷	4.59×10^-23	2.06×10^-23	3.82×10^-23	53.9
4	262.2	8.69×10^-24	3.10×10^-18	5.38×10¹⁶	5.04×10^-23	8.4×10^-24	1.71×10^-23	49.1
6	249.3	4.25×10^-24	2.44×10^-18	1.16×10¹⁶	5.61×10^-23	1.59×10^-24	5.84×10^-24	27.2
8	236.3	2.08×10^-24	2.03×10^-18	3.50×10¹⁵	6.38×10^-23	4.53×10^-25	2.53×10^-24	17.9
10	223.3	1.02×10^-24	1.78×10^-18	9.23×10¹⁴	7.42×10^-23	1.22×10^-25	1.14×10^-24	10.7
12	216.7	7.08×10^-25	1.71×10^-18	2.15×10¹⁴	8.10×10^-23	2.97×10^-26	7.38×10^-25	4

Table 2 Kinetic results for formation process of H2O2+HS occurring through channels R1 and RW1*

h/km	T/K	k_R1/(cm³· molecule^-1·s^-1)	k_RW1	[H₂O]^[22]	K_eq(A)	k $' RW 1$	k_total	k $' RW 1$ /k_total(%)
0	298.2	6.01×10^-23	6.82×10^-18	2.59×10¹⁷	4.02×10^-23	7.1×10^-23	1.31×10^-22	54.2
0	288.2	3.55×10^-23	5.48×10^-18	2.59×10¹⁷	4.24×10^-23	6.02×10^-23	9.57×10^-23	62.9
2	275.2	1.76×10^-23	4.04×10^-18	1.11×10¹⁷	4.59×10^-23	2.06×10^-23	3.82×10^-23	53.9
4	262.2	8.69×10^-24	3.10×10^-18	5.38×10¹⁶	5.04×10^-23	8.4×10^-24	1.71×10^-23	49.1
6	249.3	4.25×10^-24	2.44×10^-18	1.16×10¹⁶	5.61×10^-23	1.59×10^-24	5.84×10^-24	27.2
8	236.3	2.08×10^-24	2.03×10^-18	3.50×10¹⁵	6.38×10^-23	4.53×10^-25	2.53×10^-24	17.9
10	223.3	1.02×10^-24	1.78×10^-18	9.23×10¹⁴	7.42×10^-23	1.22×10^-25	1.14×10^-24	10.7
12	216.7	7.08×10^-25	1.71×10^-18	2.15×10¹⁴	8.10×10^-23	2.97×10^-26	7.38×10^-25	4

References 29

[1]	Wallington T. J., Dagaut P., Kurylo M. J., Chem. Rev., 1992, 92(4), 667—710
[2]	Zhu R. S., Lin M. C., Phys. Chem. Comm., 2001, 4(23), 106
[3]	von Ahsen S., Willner H., Argüello G. A., J. Fluorine. Chem., 2004, 125(7), 1057—1070
[4]	Zhou Y. Z., Zhang S. W., Li Q. S., Chem. J. Chinese Universities,2006, 27(8), 1496—1499
	(周玉芝, 张绍文, 李前树. 高等学校化学学报, 2006, 27(8), 1496—1499)
[5]	Lightfoot P. D., Cox R. A., Crowley J. N., Destriau M., Hayman G. D., Jenkin M. E., Moortgat G. K., Zabel F., Atmos. Environ. Part. A,1992, 26(10), 1805—1961
[6]	Bates T. S., Lamb B. K., Guenther A., Dignon J., Stoiber R. E., J. Atmos. Chem., 1992, 14(1—4), 315—337
[7]	Lomans B. P., van der Drift C., Pol A., Op den Camp H. J. M., CMLS Cell. Mol. Life. Sci., 2002, 59(4), 575—588
[8]	Mellouki A., Ravishankara A. R., Int. J. Chem. Kinet., 1994, 26(3), 355—365
[9]	Gonzalez J., Anglada J. M., Buszek R. J., Francisco J. S., J. Am. Chem. Soc., 2011, 133(10), 3345—3353
[10]	Aloisio S., Francisco J. S., J. Phys. Chem. A,1998, 102(11), 1899—1902
[11]	Long B., Tan X. F., Long Z. W., Wang Y. B., Ren D. S., Zhang W. J., J. Phys. Chem. A,2011, 115(24), 6559—6567
[12]	Frost G., Vaida V., J. Geophys. Res., 1995, 100(D9), 18803—18809
[13]	Tao F. M., Higgins K., Klemperer W., Nelson D. D., Geophys. Res. Lett., 1996, 23(14), 1797—1800
[14]	Stone D., Rowley D. M., Phys. Chem. Chem. Phys., 2005, 7(10), 2156—2163
[15]	Gonzalez J., Anglada J. M., J. Phys. Chem. A.2010, 114(34), 9151—9162
[16]	Song G. Y, Su Y., Roy A. P., Han K. L, Robert H. C., Zhang H. J., Li X. W., Angew. Chem. Int. Ed., 2010, 49, 912—917
[17]	Anglada J. M., Gonzalez J., Chem. Phys. Chem., 2009, 10(17), 3034—3045
[18]	Luo Y. M., Ohno K. S., Chem. Phys. Lett., 2009, 469(1—3), 57—61
[19]	Jorgensen S., Kjaergaard H. G., J. Phys. Chem. A,2010, 114(14), 4857—4863
[20]	Zhang T. L., Wang W. L., Zhang P., Lu J., Zhang Y., Phys. Chem. Chem. Phys., 2011, 13(46), 20794—20805
[21]	Gao C. G., Long Z. W., Tan X. F., Long B., Long C. Y., Qin S. J., Zhang W. J., Acta Chim. Sinica,2013, 71, 849—856
	(高成贵, 隆正文, 谭兴凤, 龙波, 龙超云, 秦水介, 张为俊. 化学学报, 2013, 71, 849—856)
[22]	Yung Y.L., Demore W. B., Photochemistry of Planetary Atomspheres, Oxford Univ., Oxford, 1999
[23]	Raghavachari K., Trucks G. W., Pople J. A., Headgordon M., Chem. Phys. Lett.1989, 157(6), 479—483
[24]	Frisch M.J., Trucks G. W., Schlegel H. B., Scuseria G. E., Robb M. A., Cheeseman J. R., Montgomery J. A. Jr., Vreven T., Kudin K. N., Burant J. C., Millam J. M., Iyengar S. S., Tomasi J., Barone V., Mennucci B., Cossi M., Scalmani G., Rega N., Petersson G. A., Nakatsuji H., Hada M. Ehara M., Toyota K., Fukuda R., Hasegawa J., Ishida M., Nakajima T., Honda Y., Kitao O., Nakai H., Klene M., Li X., Knox J. E., Hratchian H. P., Cross J. B., Bakken V., Adamo C., Jaramillo J., Gomperts R., Stratmann R. E., Yazyev O., Austin A. J., Cammi R., Pomelli C., Ochterski J. W., Ayala P. Y., Morokuma K., Voth G. A., Salvador P., Dannenberg J. J., Zakrzewski V. G., Dapprich S., Daniels A. D., Strain M. C., Farkas O., Malick D. K., Rabuck A. D., Raghavachari K., Foresman J. B., Ortiz J. V., Cui Q., Baboul A. G., Clifford S., Cioslowski J., Stefanov B. B., Liu G., Liashenko A., Piskorz P., Komaromi I., Martin R. L. Fox D. J., Keith T., Al-Laham M. A., Peng C. Y., Nanayakkara A., Challacombe M., Gill P. M. W., Johnson B., Chen W., Wong M. W., Gonzalez C., Pople J. A., Gaussian 09, Revision A. 01, Gaussian Inc., Pittsburgh PA, 2009
[25]	Zhang S.W., Truong T. N., VKLab Version 1.0, University of Utah, Salt Lake City, 2001
[26]	Lu Y. X, Wang W. L., Wang W. N., Liu Y. Y., Zhang Y., Acta. Chim. Sinica.2010, 68, 1253—1260
	(卢彦霞, 王文亮, 王渭娜, 刘英英, 张越. 化学学报, 2010, 68, 1253—1260)
[27]	Computational Chemistry Comparison and Benchmark Database,
[28]	Zhang T., Wang W., Li C., Du Y., Lü J., RSC Advances,2013, 3(20), 7381—7391
[29]	Anglada J. M., Gonzalez J., Chem. Phys. Chem., 2009, 10(17), 3034—3045

Theoretical Studies on the Single Water Molecule’s Effect on the Main Channel of H₂S+HO₂ Reaction^†

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 11

References 29

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	ZHOU Zixuan, YANG Haiyan, SUN Yuhan, GAO Peng. Recent Progress in Heterogeneous Catalysts for the Hydrogenation of Carbon Dioxide to Methanol [J]. Chem. J. Chinese Universities, 2022, 43(7): 20220235.
[2]	YANG Dan, LIU Xu, DAI Yihu, ZHU Yan, YANG Yanhui. Research Progress in Electrocatalytic CO₂ Reduction Reaction over Gold Clusters [J]. Chem. J. Chinese Universities, 2022, 43(7): 20220198.
[3]	SUN Cuihong, LYU Liqiang, LIU Ying, WANG Yan, YANG Jing, ZHANG Shaowen. Mechanism and Kinetics on the Reaction of Isopropyl Nitrate with Cl， OH and NO₃ Radicals [J]. Chem. J. Chinese Universities, 2022, 43(2): 20210591.
[4]	CHENG Yuanyuan, XI Biying. Theoretical Study on the Fragmentation Mechanism of CH₃SSCH₃ Radical Cation Initiated by OH Radical [J]. Chem. J. Chinese Universities, 2022, 43(10): 20220271.
[5]	MENG Fanwei, GAO Qi, YE Qing, LI Chenxi. Potassium Poisoning Mechanism of Cu-SAPO-18 Catalyst for Selective Catalytic Reduction of NO_x by Ammonia [J]. Chem. J. Chinese Universities, 2021, 42(9): 2832.
[6]	YANG Yiying, ZHU Rongxiu, ZHANG Dongju, LIU Chengbu. Theoretical Study on Gold-catalyzed Cyclization of Alkynyl Benzodioxin to 8-Hydroxy-isocoumarin [J]. Chem. J. Chinese Universities, 2021, 42(7): 2299.
[7]	LI Xinyi, LIU Yongjun. Theoretical Insights into the Cleavage of β-Hydroxy Ketone Catalyzed by Artificial Retro-aldolase RA95.5-8F [J]. Chem. J. Chinese Universities, 2021, 42(7): 2306.
[8]	LI Yiwei, SHENTU Jiangtao, WANG Jingbo, LI Xiangyuan. Combustion Mechanism Construction Based on Minimized Reaction Network： C1⁃Oxygen Combustion [J]. Chem. J. Chinese Universities, 2021, 42(6): 1871.
[9]	TIAN Shengqiao, WEI Meiju. Reaction Mechanism for Rh（Ⅱ）-catalyzed ［3+3］ Cyclization of Indole Derivatives and Propertis of Product [J]. Chem. J. Chinese Universities, 2021, 42(6): 1899.
[10]	REN Ying, LI Changhua, WANG Tao, XUE Shanshan, ZHANG Tingting, JIA Jianfeng, WU Haishun. Theoretical Studies on Pd-catalyzed Oxidative N─H Carbonylation to Synthesis of 1，3，4-Oxadiazole-2（3H）-one Heterocyclic Compounds [J]. Chem. J. Chinese Universities, 2021, 42(6): 1793.
[11]	QI Guodong, YE Xiaodong, XU Jun, DENG Feng. Progress in NMR Studies of Carbohydrates Conversion on Zeolites [J]. Chem. J. Chinese Universities, 2021, 42(1): 148.
[12]	LI Xiangyuan, SHENTU Jiangtao, LI Yiwei, LI Juanqin, WANG Jingbo. Combustion Mechanism Construction Based on Minimized Reaction Network: Hydrogen-Oxygen Combustion ^† [J]. Chem. J. Chinese Universities, 2020, 41(4): 772.
[13]	LI Xiangyuan,YAO Xiaoxia,SHENTU Jiangtao,SUN Xiaohui,LI Juanqin,LIU Mingxia,XU Shimin. Combustion Reaction Mechanism Construction by Two-parameter Rate Constant Method ^† [J]. Chem. J. Chinese Universities, 2020, 41(3): 512.
[14]	ZHANG Lin, ZHANG Wei, YUE Xin, LI Pengjie, YANG Zuoyin, PU Min, LEI Ming. Theoretical Study on Mechanism of CO₂ Hydrogenation to Formic Acid Catalyzed by Manganese Complex ^† [J]. Chem. J. Chinese Universities, 2019, 40(9): 1911.
[15]	ZHANG Xiaoying,DU Guifang,ZHU Bo,GUAN Wei. Theoretical Mechanistic Study on Nickel-Catalyzed Cycloaddition of Azetidinone with Butadiene^† [J]. Chem. J. Chinese Universities, 2019, 40(4): 770.