Reaction of the nitrate radical with some potential automotive fuel additives. A kinetic and mechanistic study

Journal Article · Thu Jun 09 00:00:00 EDT 1994 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100074a015· OSTI ID:7165941

Langer, S; Ljungstroem, E ^[1]

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1. Univ. of Goeteborg (Sweden)

Rate coefficients for the reaction of NO[sub 3] with ethyl tert-butyl ether (ETBE), diisopropyl ether (DIPE), and tert-amyl methyl ether (TAME) have been determined. Absolute rates were measured at temperatures between 257 and 367 K using the fast flow-discharge (FFD) technique. Relative rate experiments were also performed at 295 K in a reactor equipped with White optics and using FTIR spectroscopy to follow the reactions. Rate data from FFD experiments can be presented as follows: k[sub ETBE] = (2.48 [+-] 0.78) x 10[sup [minus]12] exp[-(1613 [+-] 542)/T], k[sub DIPE] = (2.02 [+-] 0.35) x 10[sup [minus]12] exp[-(1759 [+-] 301)/T], and [kappa][sub TAME] = (1.21 [+-] 0.22) x 10[sup [minus]12] exp[-(1874 [+-] 304)/T] (in units of cm[sup 3] molecule[sup [minus]1] s[sup [minus]1]). The rate coefficients at room temperature from the FFD experiments are in good agreement with the corresponding rate coefficients from the relative rate experiments. Products from simulated atmospheric oxidation of the investigated ethers, initiated by the reaction with the nitrate radical, were identified using FTIR spectroscopy. The degradation of ETBE results in tert-butyl formate, tert-butyl acetate, formaldehyde, and methyl nitrate, that of DIPE in acetone, isopropyl nitrate, isopropyl acetate, and formaldehyde, and that of TAME in tert-amyl formate, formaldehyde, and tert-amyl nitrate. 21 refs., 12 figs., 4 tabs.

• OSTI ID: 7165941
• Journal Information: Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 98:23; ISSN JPCHAX; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

02 PETROLEUM
020900 -- Petroleum-- Environmental Aspects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400102 -- Chemical & Spectral Procedures
400201* -- Chemical & Physicochemical Properties
54 ENVIRONMENTAL SCIENCES
540110
ACETONE
ADDITIVES
ALDEHYDES
ATMOSPHERIC CHEMISTRY
CARBON COMPOUNDS
CARBON DIOXIDE
CARBON OXIDES
CHALCOGENIDES
CHEMICAL REACTIONS
CHEMISTRY
DATA
ESTERS
ETHERS
EXPERIMENTAL DATA
FORMALDEHYDE
FUEL ADDITIVES
INFORMATION
INFRARED SPECTRA
KETONES
KINETICS
NITRATES
NITRIC ACID ESTERS
NITROGEN COMPOUNDS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
OXIDATION
OXIDES
OXYGEN COMPOUNDS
RADICALS
REACTION KINETICS
SPECTRA