UV ABSORPTION-SPECTRA AND KINETICS FOR ALKYL AND ALKYL PEROXY-RADICALS ORIGINATING FROM DI-TERT-BUTYL ETHER

被引：32

作者：

NIELSEN, OJ ^{[1
]}

SEHESTED, J ^{[1
]}

LANGER, S ^{[1
]}

LJUNGSTROM, E ^{[1
]}

WANGBERG, I ^{[1
]}

机构：

[1] UNIV GOTHENBURG,DEPT INORGAN CHEM,S-41296 GOTHENBURG,SWEDEN

来源：

CHEMICAL PHYSICS LETTERS | 1995年 / 238卷 / 4-6期

关键词：

D O I：

10.1016/0009-2614(95)00401-O

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Alkyl, (CH3)(3)COC(CH3)(2)CH2, and alkyl peroxy, (CH3)(3)COC(CH3)(2)CH2O2, radicals from di-tert-butyl ether (DTBE), have been studied in the gas phase at 296 K. A pulse radiolysis UV absorption technique was used to measure the spectra and kinetics. Absorption cross sections were quantified over the wavelength range 220-330 nm. At 240 nm, sigma((CH3)3COC(CH3)2CH2) = (3.6 +/- 0.4) X 10(-18) cm(2) molecule(-1) and at 260 nm, sigma((CH3)3COC(CH3)2CH2) = (3.8 +/- 0.3) X 10(-18) cm(2) molecule(-1) have been obtained. The observed rate constants for the self-reaction of (CH3)(3)COC(CH3)(2)CH2 and (CH3)(3)COC(CH3)(2)CH2O2 radicals were found to be (2.9 +/- 0.2) X 10(-11) cm(3) molecule(-1) s(-1) and (2.7 +/- 0.2) X 10(-12) cm(3) molecule(-1) s(-1), respectively. For the reaction of the alkyl radical with O-2 in 1 atm pressure of SF6 a rate constant of (7.2 +/- 1.1) X 10(-13) cm(3) molecule(-1) s(-1) was found. The rate constants for the reaction of the alkyl peroxy radicals with NO and NO2 were determined to be (1.8 +/- 0.2) X 10(-12) and (9.9 +/- 1.3) X 10(-12) cm(3) molecule(-1) s(-1), respectively. As a part of the work the rate constants k(F + DTBE) and k(OH + DTBE) were determined to be (2.6 +/- 0.6) X 10(-10) and (4.0 +/- 0.9) X 10(-12) cm(3) molecule(-1) s(-1), respectively.

引用

页码：359 / 364

页数：6

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