Identification

Title

Atmospheric chemistry of isopropyl formate and tert-butyl formate

Abstract

Formates are produced in the atmosphere as a result of the oxidation of a number of species, notably dialkyl ethers and vinyl ethers. This work describes experiments to define the oxidation mechanisms of isopropyl formate, HC(O)OCH(CH₃)₂, and tert-butyl formate, HC(O)OC(CH₃)₃. Product distributions are reported from both Cl- and OH-initiated oxidation, and reaction mechanisms are proposed to account for the observed products. The proposed mechanisms include examples of the α-ester rearrangement reaction, novel isomerization pathways, and chemically activated intermediates. The atmospheric oxidation of isopropyl formate by OH radicals gives the following products (molar yields): acetic formic anhydride (43%), acetone (43%), and HCOOH (15–20%). The OH radical initiated oxidation of tert-butyl formate gives acetone, formaldehyde, and CO&#8322 as major products. IR absorption cross sections were derived for two acylperoxy nitrates derived from the title compounds. Rate coefficients are derived for the kinetics of the reactions of isopropyl formate with OH (2.4 ± 0.6) × 10⁻ ¹ ², and with Cl (1.75 ± 0.35) × 10⁻ ¹ ¹, and for tert-butyl formate with Cl (1.45 ± 0.30) × 10⁻ ¹ ¹ cm³ molecule⁻ ¹ s⁻ ¹. Simple group additivity rules fail to explain the observed distribution of sites of H-atom abstraction for simple formates.

Resource type

document

Resource locator

Unique resource identifier

code

https://n2t.org/ark:/85065/d78p622h

codeSpace

Dataset language

eng

Spatial reference system

code identifying the spatial reference system

Classification of spatial data and services

Topic category

geoscientificInformation

Keywords

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keyword value

Text

originating controlled vocabulary

title

Resource Type

reference date

date type

publication

effective date

2016-01-01T00:00:00Z

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date type

publication

effective date

2010-08-01T00:00:00Z

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Conformity

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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

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