The thermal decomposition of 2-chloroethyl methyl ether (2-CEME) was studied in the temperatures between 1175 and 1467 K. The decomposition of 2-CEME happens predominantly via molecular elimination reactions than via C–C and C–O bond fission channels. The major decomposition products are methane, ethylene and methanol. The minor are acetaldehyde and ethane. The Arrhenius expression for the overall decomposition of 2-CEME was obtained to be ktotalexp(1175−1467K)=(4.12±0.42)×1011exp(−(52.2kcalmol−1±2.6)/RT)s−1. To simulate the distribution of reactant and products over the experimentally studied temperatures between 1175 and 1467 K, a reaction scheme was constructed with 45 species and 71 elementary reactions. The pressure and temperature dependent rate coefficients were calculated for various unimolecular dissociation pathways in 2-CEME using RRKM theory. The high pressure limit temperature dependent rate coefficient for the total decomposition of 2-CEME was obtained to be ktotalCCSDT//M06−2X(500–2000 K) = (2.55 ± 0.21) × 1014 exp (−(67.6 kcal mol−1± 3.0)/RT) s−1. © 2017 The Combustion Institute

Balla Rajakumar

Department Of Chemistry

decomposition

dissociation

Ethers

Ethylene

Pyrolysis

Thermolysis

Arrhenius expressions

Decomposition products

KINETIC SIMULATION

Methyl ethers

Pressure and temperature

SINGLE-PULSE SHOCK TUBES

Temperature dependent

UNIMOLECULAR DISSOCIATION

Shock tubes

2 CHLOROETHYL METHYL ETHER

acetaldehyde

carbon

DIMETHYL ETHER

Ethane

Methane

Methanol

Oxygen

unclassified drug

article

chemical bond

controlled study

elimination reaction

enthalpy

entropy

HYPERBARISM

Kinetics

priority journal

reaction analysis

reaction time

Sensitivity analysis

shock wave

Temperature

temperature dependence

Thermal decomposition

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IIT Madras

Combustion and Flame

Thermal decomposition of tetramethylsilane (TMS) diluted in argon was studied behind the reflected shock waves in a single pulse shock tube (SPST) in the temperature range of 1058-1194 K. The major products formed in the decomposition are methane (CH 4) and ethylene (C 2 H 4); whereas ethane and propylene were detected in lower concentrations. The decomposition of TMS seems to be initiated via Si-C bond scission by forming methyl radicals (CH 3) and trimethylsilyl radicals ((CH 3) 3Si). The total rate coefficients obtained for the decomposition of TMS were fit to Arrhenius equation in two different temperature regions 1058-1130 K and 1130-1194 K. The temperature dependent rate coefficients obtained are k total (1058-1130 K) = (4.61±0.70) ×1018 exp (-(79.9 kcal mol -1±3.5)/RT) s -1, k total (1130-1194 K) = (1.33 ± 0.19) ×106 exp (-(15.3 kcal mol -1±3.5)/RT) s -1. The rate coefficient for the formation of CH 4 is obtained to be k methane (1058-1194 K) = (4.36 ± 1.23) ×1014 exp (-(61.9 kcal mol -1±4.9)/RT) s -1. A kinetic scheme containing 21 species and 38 elementary reactions was proposed and simulations were carried out to explain the formation of all the products in the decomposition of tetramethylsilane. © 2016 Indian Academy of Sciences.

Fulltext

Journal of Chemical Sciences

Kinetics of the thermal decomposition of tetramethylsilane behind the reflected shock waves between 1058 and 1194 K

Thermal decomposition of methyl butanoate (MB) diluted in argon was studied behind reflected shock waves in the temperature range of 1229-1427 K using a single pulse shock tube (SPST). The post shock mixtures were analyzed quantitatively using gas chromatography (GC) and qualitatively using Fourier-transform infrared (FTIR) spectroscopy. Methane (CH4), ethylene (C2H4), and acetylene (C2H2) were the major decomposition products. The minor products are ethane (C2H6), propylene (C3H6), 1,3-butadiene (C4H6) and methyl acrylate (C4H6O2). The obtained first order rate coefficient for the decomposition of MB is ktotal (1229-1427 K) = (3.08 ± 1.11) × 1012exp(-(53.6 kcal mol-1 ± 4.7)/RT) s-1, and for the formation of C2H4, the rate coefficient was found to be kethylene (1229-1427 K) = (7.92 ± 2.72) × 109exp(-(47.6 kcal mol-1 ± 4.5)/RT) s-1. Theoretical kinetic calculations were also performed for the unimolecular hydrogen transfer reactions using canonical variational transition state theory (CVT) with small-curvature tunneling (SCT) corrections. The temperature dependent rate coefficients for the overall reaction were computed in the temperature range of 500-2500 K, and were used to derive the Arrhenius expression: ktheorytotal (500-2500 K) = (9.05 ± 1.91) × 1013exp(-(70.7 kcal mol-1 ± 2.0)/RT) s-1. A reaction scheme containing 39 species and 66 elementary reactions was proposed to simulate the reactant and product concentrations over the temperature range of 1229-1427 K. The agreement between the experimental results and the model prediction for all the species is observed to be good. The decomposition of MB happens mostly via intramolecular hydrogen transfer than C-C bond and C-O bond fission. The majority of these intramolecular hydrogen transfer reactions are lower energy barrier reactions than the homolytic bond fission reactions. © The Royal Society of Chemistry.

RSC Advances

Experimental and theoretical study on thermal decomposition of methyl butanoate behind reflected shock waves

The thermal decomposition of 1-chloropropane in argon was studied behind reflected shock waves in a single pulse shock tube over the temperature range of 1015-1220 K. The reaction mainly goes through unimolecular elimination of HCl. The major products observed in the decomposition are propylene and ethylene, while the minor products identified are methane and propane. The rate constant for HCl elimination in the studied temperature range is estimated to be k(1015-1220 K) = 1.63 × 1013exp(-(60.1 ± 1.0) kcal mol-1/RT) s-1. The DFT calculations were carried out to identify the transition state(s) for the major reaction channel; and rate coefficient for this reaction is obtained to be k(800-1500 K) = 5.01 × 1014exp(-(58.8) kcal mol-1/RT) s-1. The results are compared with the experimental findings. © 2014 Indian Academy of Sciences.

Thermal decomposition of 1-chloropropane behind the reflected shock waves in the temperature range of 1015-1220 K: Single pulse shock tube and computational studies

The reactions of CH2 and ketene with CH2 and H have been investigated at elevated temperatures in the postshock region behind reflected shocks. Atomic (ARAS) and molecular resonance absorption spectrometry was used to record simultaneously H-atom and CO-molecule concentration profiles. The thermal decomposition of very low initial concentrations of ketene (2-50 ppm CH2CO/Ar) served as a source for methylene. The experiments were conducted in the temperature range of 1650-2800 K at total densities of 5 × 10-6 to 1.3 × 10-5 mol cm-3. For temperatures above 2000 K the following rate coefficients (k in cm3 mol-1 s-1) were deduced: CH2 + CH2 = C2H2 + 2H, k = (10 ± 2) × 1013; CH2 + H = CH + H2, k = (8 ± 2) × 1012. For temperatures between 1650 and 1850 K a value of (1.8 ± 0.6) × 1013 is deduced for the reaction of ketene with H atoms. © 1986 American Chemical Society.

The Journal of Physical Chemistry

High-temperature reactions of triplet methylene and ketene with radicals

Chemical Reviews

Atmospheric Chemistry of Oxygenated Volatile Organic Compounds: Impacts on Air Quality and Climate

Shock tube study and RRKM calculations on thermal decomposition of 2-chloroethyl methyl ether

Journal	Data powered by TypesetCombustion and Flame
Publisher	Data powered by TypesetElsevier Inc.
ISSN	00102180
Open Access	No