Identification

Title

The atmospheric oxidation of ethyl formate and ethyl acetate over a range of temperatures and oxygen partial pressures

Abstract

The Cl-atom-initiated oxidation of two esters, ethyl formate [HC(O)OCH₂CH₃] and ethyl acetate [CH₃C(O)OCH₂CH₃], has been studied at pressures close to 1 atm as a function of temperature (249–325 K) and O₂ partial pressure (50–700 Torr), using an environmental chamber technique. In both cases, Cl-atom attack at the CH₂ group is most important, leading in part to the formation of radicals of the type RC(O)OCH(O•)CH&#8323 [R = H, CH&#8323]. The atmospheric fate of these radicals involves competition between reaction with O2 to produce an anhydride compound, RC(O)OC(O)CH3, and the so-called α-ester rearrangement that produces an organic acid, RC(O)OH, and an acetyl radical, CH₃C(O). For both species studied, the α-ester rearrangement is found to dominate in air at 1 atm and 298 K. Barriers to the rearrangement of 7.7 ± 1.5 and 8.4 ± 1.5 kcal/mole are estimated for CH₃C(O)OCH(O•)CH₃ and HC(O)OCH(O•)CH₃, respectively, leading to increased occurrence of the O&#8322 reaction at reduced temperature. The data are combined with those obtained from similar studies of other simple esters to provide a correlation between the rate of occurrence of the α-ester rearrangement and the structure of the reacting radical.

Resource type

document

Resource locator

Unique resource identifier

code

http://n2t.net/ark:/85065/d74x59c7

codeSpace

Dataset language

eng

Spatial reference system

code identifying the spatial reference system

Classification of spatial data and services

Topic category

geoscientificInformation

Keywords

Keyword set

keyword value

Text

originating controlled vocabulary

title

Resource Type

reference date

date type

publication

effective date

2016-01-01T00:00:00Z

Geographic location

West bounding longitude

East bounding longitude

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Temporal reference

Temporal extent

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End position

Dataset reference date

date type

publication

effective date

2010-07-01T00:00:00Z

Frequency of update

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Conformity

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version of format

Constraints related to access and use

Constraint set

Use constraints

Limitations on public access

None

Responsible organisations

Responsible party

contact position

OpenSky Support

organisation name

UCAR/NCAR - Library

full postal address

PO Box 3000

Boulder

80307-3000

email address

opensky@ucar.edu

web address

http://opensky.ucar.edu/

name: homepage

responsible party role

pointOfContact

Metadata on metadata

Metadata point of contact