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Title: Thermal decomposition of methyl nitrite: kinetic modeling of detailed product measurements by gas-liquid chromatography and Fourier transform infrared spectroscopy

Abstract

The thermal decomposition of CH/sub 3/ONO was studied in a static reactor at temperatures in the range 450-520 K. Stable products were analyzed by FTIR and gas-liquid chromatography to yield concentration-time profiles as functions of temperature and pressure. The species monitored included CH/sub 3/ONO, CH/sub 2/O, CH/sub 3/OH, NO, N/sub 2/O, and CO. The experimental data were kinetically modeled with the aid of Rice-Ramsperger-Kassel-Marcus (RRKM) calculations for pressure-dependent rate constants. The key reactions of this mechanism are the following: CH/sub 3/ONO ..-->.. CH/sub 3/O + NO (1); CH/sub 3/ONO ..-->.. CH/sub 2/O + HNO (2); CH/sub 3/O + NO ..-->.. CH/sub 3/ONO (3); CH/sub 3/O + NO ..-->.. CH/sub 2/O + HNO (4); CH/sub 3/O + HNO ..-->.. CH/sub 3/OH + NO (5); HNO + HNO ..-->.. N/sub 2/O + H/sub 2/O (7). The results showed that the initiation reaction, (1), is clearly pressure dependent in the temperature and pressure ranges investigated. The data are consistent with the value k/sub 1/ = 10/sup 15.3/plus minus/0.30/ exp((-38,700 /plus minus/ 400)/RT) s/sup -1/ at 710 Torr of He and with the extrapolated high-pressure rate constant k/sub 1//sup infinity/ = 10/sup 16.01/plus minus/0.30/ exp((-39,600 /plus minus/ 400)/RT)s/sup -1/. The rate constant ration k/submore » 4//k/sub 3/ for channels 3 and 4 was also found to depend on both temperature and pressure. At 710 Torr, k/sub 3/ = 10/sup 12.96/plus minus/0.30/ exp((0 /plus minus/ 200)/RT) and k/sub 4/ = 10/sup 12.92/plus minus/0.30/ exp((-2050 /plus minus/200)/RT), both in units of cm/sup 3//(mol s). Kinetic modeling of CH/sub 3/OH and N/sub 2/OH formation over the entire range of temperatures and pressures investigated here yielded k/sub 5/ = 10/sup 13.5/plus minus/0.4/ exp((0 /plus minus/ 400)/RT) and k/sub 7/ = 10/sup 8.93/plus minus/0.30/ exp ((-3100 /plus minus/ 300)/RT) cm/sup 3//mol s.« less

Authors:
; ;
Publication Date:
Research Org.:
Catholic Univ. of America, Washington, DC (USA)
OSTI Identifier:
5992224
DOE Contract Number:  
FG05-85ER13373
Resource Type:
Journal Article
Journal Name:
J. Phys. Chem.; (United States)
Additional Journal Information:
Journal Volume: 92:19
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; NITROUS ACID ESTERS; PYROLYSIS; ABSORPTION SPECTROSCOPY; CHEMICAL REACTION KINETICS; EXPERIMENTAL DATA; FOURIER TRANSFORM SPECTROMETERS; GAS CHROMATOGRAPHY; INFRARED SPECTRA; LIQUID COLUMN CHROMATOGRAPHY; METHOXY RADICALS; ALKOXY RADICALS; CHEMICAL REACTIONS; CHROMATOGRAPHY; DATA; DECOMPOSITION; ESTERS; INFORMATION; KINETICS; MEASURING INSTRUMENTS; NUMERICAL DATA; ORGANIC COMPOUNDS; RADICALS; REACTION KINETICS; SEPARATION PROCESSES; SPECTRA; SPECTROMETERS; SPECTROSCOPY; THERMOCHEMICAL PROCESSES; 400800* - Combustion, Pyrolysis, & High-Temperature Chemistry

Citation Formats

He, Y, Sanders, W A, and Lin, M C. Thermal decomposition of methyl nitrite: kinetic modeling of detailed product measurements by gas-liquid chromatography and Fourier transform infrared spectroscopy. United States: N. p., 1988. Web. doi:10.1021/j100330a028.
He, Y, Sanders, W A, & Lin, M C. Thermal decomposition of methyl nitrite: kinetic modeling of detailed product measurements by gas-liquid chromatography and Fourier transform infrared spectroscopy. United States. doi:10.1021/j100330a028.
He, Y, Sanders, W A, and Lin, M C. Thu . "Thermal decomposition of methyl nitrite: kinetic modeling of detailed product measurements by gas-liquid chromatography and Fourier transform infrared spectroscopy". United States. doi:10.1021/j100330a028.
@article{osti_5992224,
title = {Thermal decomposition of methyl nitrite: kinetic modeling of detailed product measurements by gas-liquid chromatography and Fourier transform infrared spectroscopy},
author = {He, Y and Sanders, W A and Lin, M C},
abstractNote = {The thermal decomposition of CH/sub 3/ONO was studied in a static reactor at temperatures in the range 450-520 K. Stable products were analyzed by FTIR and gas-liquid chromatography to yield concentration-time profiles as functions of temperature and pressure. The species monitored included CH/sub 3/ONO, CH/sub 2/O, CH/sub 3/OH, NO, N/sub 2/O, and CO. The experimental data were kinetically modeled with the aid of Rice-Ramsperger-Kassel-Marcus (RRKM) calculations for pressure-dependent rate constants. The key reactions of this mechanism are the following: CH/sub 3/ONO ..-->.. CH/sub 3/O + NO (1); CH/sub 3/ONO ..-->.. CH/sub 2/O + HNO (2); CH/sub 3/O + NO ..-->.. CH/sub 3/ONO (3); CH/sub 3/O + NO ..-->.. CH/sub 2/O + HNO (4); CH/sub 3/O + HNO ..-->.. CH/sub 3/OH + NO (5); HNO + HNO ..-->.. N/sub 2/O + H/sub 2/O (7). The results showed that the initiation reaction, (1), is clearly pressure dependent in the temperature and pressure ranges investigated. The data are consistent with the value k/sub 1/ = 10/sup 15.3/plus minus/0.30/ exp((-38,700 /plus minus/ 400)/RT) s/sup -1/ at 710 Torr of He and with the extrapolated high-pressure rate constant k/sub 1//sup infinity/ = 10/sup 16.01/plus minus/0.30/ exp((-39,600 /plus minus/ 400)/RT)s/sup -1/. The rate constant ration k/sub 4//k/sub 3/ for channels 3 and 4 was also found to depend on both temperature and pressure. At 710 Torr, k/sub 3/ = 10/sup 12.96/plus minus/0.30/ exp((0 /plus minus/ 200)/RT) and k/sub 4/ = 10/sup 12.92/plus minus/0.30/ exp((-2050 /plus minus/200)/RT), both in units of cm/sup 3//(mol s). Kinetic modeling of CH/sub 3/OH and N/sub 2/OH formation over the entire range of temperatures and pressures investigated here yielded k/sub 5/ = 10/sup 13.5/plus minus/0.4/ exp((0 /plus minus/ 400)/RT) and k/sub 7/ = 10/sup 8.93/plus minus/0.30/ exp ((-3100 /plus minus/ 300)/RT) cm/sup 3//mol s.},
doi = {10.1021/j100330a028},
journal = {J. Phys. Chem.; (United States)},
number = ,
volume = 92:19,
place = {United States},
year = {1988},
month = {9}
}