Theoretical and Experimental Study on the Reaction of tert-Butylamine with OH Radicals in the Atmosphere

TY - JOUR

T1 - Theoretical and Experimental Study on the Reaction of tert-Butylamine with OH Radicals in the Atmosphere

AU - Tan, Jun-Wen

AU - Zhu, Liang

AU - Mikoviny, Tomáš

AU - Nielsen, Claus J.

AU - Wisthaler, Armin

AU - Eichler, Philipp

AU - Müller, Markus

AU - D'Anna, Barbara

AU - Farren, Naomi J.

AU - Hamilton, Jacqueline F.

AU - Pettersson, Jan B.C.

AU - Hallquist, Mattias

AU - Antonsen, Simen

AU - Stenstrøm, Yngve

N1 - © 2018 American Chemical Society. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details

PY - 2018/5/10

Y1 - 2018/5/10

N2 - The OH-initiated atmospheric degradation of tert-butylamine (tBA), (CH3)3CNH2, was investigated in a detailed quantum chemistry study and in laboratory experiments at the European Photoreactor (EUPHORE) in Spain. The reaction was found to mainly proceed via hydrogen abstraction from the amino group, which in the presence of nitrogen oxides (NOx), generates tert-butylnitramine, (CH3)3CNHNO2, and acetone as the main reaction products. Acetone is formed via the reaction of tert-butylnitrosamine, (CH3)3CNHNO, and/or its isomer tert-butylhydroxydiazene, (CH3)3CN=NOH, with OH radicals, which yield nitrous oxide (N2O) and the (CH3)3Ċ radical. The latter is converted to acetone and formaldehyde. Minor predicted and observed reaction products include formaldehyde, 2-methylpropene, acetamide and propan-2-imine. The reaction in the EUPHORE chamber was accompanied by strong particle formation which was induced by an acid-base reaction between photochemically formed nitric acid and the reagent amine. The tert-butylaminium nitrate salt was found to be of low volatility, with a vapor pressure of 5.1 × 10-6 Pa at 298 K. The rate of reaction between tert-butylamine and OH radicals was measured to be 8.4 (±1.7) × 10-12 cm3 molecule-1 s-1 at 305 ± 2 K and 1015 ± 1 hPa.

AB - The OH-initiated atmospheric degradation of tert-butylamine (tBA), (CH3)3CNH2, was investigated in a detailed quantum chemistry study and in laboratory experiments at the European Photoreactor (EUPHORE) in Spain. The reaction was found to mainly proceed via hydrogen abstraction from the amino group, which in the presence of nitrogen oxides (NOx), generates tert-butylnitramine, (CH3)3CNHNO2, and acetone as the main reaction products. Acetone is formed via the reaction of tert-butylnitrosamine, (CH3)3CNHNO, and/or its isomer tert-butylhydroxydiazene, (CH3)3CN=NOH, with OH radicals, which yield nitrous oxide (N2O) and the (CH3)3Ċ radical. The latter is converted to acetone and formaldehyde. Minor predicted and observed reaction products include formaldehyde, 2-methylpropene, acetamide and propan-2-imine. The reaction in the EUPHORE chamber was accompanied by strong particle formation which was induced by an acid-base reaction between photochemically formed nitric acid and the reagent amine. The tert-butylaminium nitrate salt was found to be of low volatility, with a vapor pressure of 5.1 × 10-6 Pa at 298 K. The rate of reaction between tert-butylamine and OH radicals was measured to be 8.4 (±1.7) × 10-12 cm3 molecule-1 s-1 at 305 ± 2 K and 1015 ± 1 hPa.

UR - http://www.scopus.com/inward/record.url?scp=85046398056&partnerID=8YFLogxK

U2 - 10.1021/acs.jpca.8b01862

DO - 10.1021/acs.jpca.8b01862

M3 - Article

AN - SCOPUS:85046398056

SN - 1089-5639

VL - 122

SP - 4470

EP - 4480

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

IS - 18

ER -