Laboratory studies of the OH-initiated photooxidation of di-n-propyl ether

John Sempeles, Jean M. Andino

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

The OH-initiated photooxidation of di-n-propyl ether was investigated in this study. Di-n-propyl ether was mixed with nitric oxide and a hydroxyl radical precursor and irradiated using UV black lamps in a glass environmental chamber. Mass spectrometry was used as the primary analytical technique to monitor the reactants and products. FTIR spectroscopy was used to monitor formaldehyde. The products observed were propyl formate, acetaldehyde, propionaldehyde, and propyl propionate, with molar yields relative to di-n-propyl ether concentration loss of 0.61±0.044, 0.60±0.057, 0.15±0.062, and 0.043±0.015, respectively. Errors represent ±2σ. Nitrates could not be quantified because of a lack of commercially available standards. However, evidence exists for nitrate formation from the photooxidation of di-n-propyl ether. Formaldehyde concentrations were negligible. Mechanism predictions were performed on the di-n-propyl ether/OH system using the Carter kinetic software. Propyl formate and acetaldehyde yields were reasonably predicted (under 11.7% error). However, propionaldehyde and propyl propionate yields were vastly underpredicted, and examination of the experimental data suggested secondary production of both propionaldehyde and propyl propionate. Reactions were proposed for the photolysis and OH-initiated photooxidation of a primary nitrate product (1-propoxy propyl nitrate) that resulted in the formation of propionaldehyde and propyl propionate. Basic semiempirical computational chemistry calculations at the UHF/PM3 level of theory were performed using Hyperchem to investigate pathways for the secondary formation of propionaldehyde in particular.

Original languageEnglish
Pages (from-to)703-711
Number of pages9
JournalInternational Journal of Chemical Kinetics
Volume32
Issue number11
DOIs
Publication statusPublished - Nov 2000

Fingerprint

Photooxidation
photooxidation
formic acid
Propionates
Ethers
ethers
Nitrates
nitrates
Acetaldehyde
acetaldehyde
formates
formaldehyde
Formaldehyde
propyl nitrate
products
Computational chemistry
Environmental chambers
computational chemistry
test chambers
Photolysis

ASJC Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry

Cite this

Laboratory studies of the OH-initiated photooxidation of di-n-propyl ether. / Sempeles, John; Andino, Jean M.

In: International Journal of Chemical Kinetics, Vol. 32, No. 11, 11.2000, p. 703-711.

Research output: Contribution to journalArticle

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