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DOI	10.5194/acp-22-14589-2022
	Atmospheric breakdown chemistry of the new green solvent2,2,5,5-tetramethyloxolane via gas-phase reactions with OH and Cl radicals
	Mapelli, Caterina; Schleicher, Juliette V.; Hawtin, Alex; Rankine, Conor D.; Whiting, Fiona C.; Byrne, Fergal; McElroy, C. Rob; Roman, Claudiu; Arsene, Cecilia; Olariu, Romeo I.; Bejan, Iustinian G.; Dillon, Terry J.
发表日期	2022
ISSN	1680-7316
EISSN	1680-7324
起始页码	14589
结束页码	14602
卷号	22 期号:22 页码:14
英文摘要	The atmospheric chemistry of 2,2,5,5-tetramethyloxolane (TMO), a promising green solvent replacement for toluene, was investigated in laboratory-based experiments and computational calculations. Results from both absolute and relative rate studies demonstrated that the reaction OH + TMO (Reaction R1) proceeds with a rate coefficient k1(296 K) = (3.1 +/- 0.4) x10(-12) cm(3) molecule-1 s-1, a factor of 3 smaller than predicted by recent structure-activity relationships. Quantum chemical calculations (CBS-QB3 and G4) demonstrated that the reaction pathway via the lowest-energy transition state was characterised by a hydrogen-bonded pre-reaction complex, leading to thermodynamically less favoured products. Steric hindrance from the four methyl substituents in TMO prevents formation of such H-bonded complexes on the pathways to thermodynamically favoured products, a likely explanation for the anomalous slow rate of Reaction (R1). Further evidence for a complex mechanism was provided by k1(294-502 K), characterised by a local minimum at around T=340 K. An estimated atmospheric lifetime of tau 1 asymptotic to 3 d was calculated for TMO, approximately 50 % longer than toluene, indicating that any air pollution impacts from TMO emission would be less localised. An estimated photochemical ozone creation potential (POCPE) of 18 was calculated for TMO in north-western Europe conditions, less than half the equivalent value for toluene. Relative rate experiments were used to determine a rate coefficient of k2(296 K) = (1.2 +/- 0.1) x10(-10) cm(3) molecule(-1) s(-1) for Cl + TMO (Reaction R2); together with Reaction (R1), which is slow, this may indicate an additional contribution to TMO removal in regions impacted by high levels of atmospheric chlorine. All results from this work indicate that TMO is a less problematic volatile organic compound (VOC) than toluene.
学科领域	Environmental Sciences; Meteorology & Atmospheric Sciences
语种	英语
WOS研究方向	Environmental Sciences & Ecology ; Meteorology & Atmospheric Sciences
WOS记录号	WOS:000888216800001
来源期刊	ATMOSPHERIC CHEMISTRY AND PHYSICS
文献类型	期刊论文
条目标识符	http://gcip.llas.ac.cn/handle/2XKMVOVA/273100
作者单位	University of York - UK; Newcastle University - UK; Alexandru Ioan Cuza University; Alexandru Ioan Cuza University; Maynooth University; Swiss Federal Institutes of Technology Domain; Ecole Polytechnique Federale de Lausanne
推荐引用方式 GB/T 7714	Mapelli, Caterina,Schleicher, Juliette V.,Hawtin, Alex,et al. Atmospheric breakdown chemistry of the new green solvent2,2,5,5-tetramethyloxolane via gas-phase reactions with OH and Cl radicals[J],2022,22(22):14.
APA	Mapelli, Caterina.,Schleicher, Juliette V..,Hawtin, Alex.,Rankine, Conor D..,Whiting, Fiona C..,...&Dillon, Terry J..(2022).Atmospheric breakdown chemistry of the new green solvent2,2,5,5-tetramethyloxolane via gas-phase reactions with OH and Cl radicals.ATMOSPHERIC CHEMISTRY AND PHYSICS,22(22),14.
MLA	Mapelli, Caterina,et al."Atmospheric breakdown chemistry of the new green solvent2,2,5,5-tetramethyloxolane via gas-phase reactions with OH and Cl radicals".ATMOSPHERIC CHEMISTRY AND PHYSICS 22.22(2022):14.