Theoretical calculations of the thermal decomposition kinetics of several tert-nitroalkanes in the gas phase

Armando Jose Serrano; Marcos Loroño; Tania Cordova; Gabriel Chuchani

doi:10.1016/j.theochem.2008.03.001

Theoretical calculations of the thermal decomposition kinetics of several tert-nitroalkanes in the gas phase

Armando Jose Serrano, Marcos Loroño, Tania Cordova, Gabriel Chuchani

Research output: Contribution to journal › Article › peer-review

15 Scopus citations

Abstract

The theoretical study of the gas-phase pyrolysis kinetics of several tert-nitroalkanes, 2-methyl-2-nitropropane, 2-methyl-2-nitrobutane, and 2, 3-dimethyl-2-nitrobutane, has been carried out at the MP2/6-31G(d), B3LYP/6-31G(d), B3PW91/6-31G(d), levels of theory. The nitroalkanes yield the corresponding alkene and HNO₂ gas in a rate determining step. The B3PW91/6-31G(d) method was found to give a reasonable good agreement with the experimental kinetic and thermodynamic parameters. The elimination of these reactions suggest a concerted non-synchronous five-membered cyclic transition state type of mechanism.

Original language	English
Pages (from-to)	69-72
Number of pages	4
Journal	Journal of Molecular Structure: THEOCHEM
Volume	859
Issue number	1-3
DOIs	https://doi.org/10.1016/j.theochem.2008.03.001
State	Published - 30 Jun 2008
Externally published	Yes

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Copyright:
Copyright 2008 Elsevier B.V., All rights reserved.

Keywords

2,3-Dimethyl-2-nitrobutane
2-Methyl-2-nitrobutane
2-Methyl-2-nitropropne
B3PW91/6-31G(d)
Calculations
DFT B3LYP/6-31G(d)
Gas-phase decomposition
MP2/6-31G(d)
Mechanism
Pyrolysis

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10.1016/j.theochem.2008.03.001

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title = "Theoretical calculations of the thermal decomposition kinetics of several tert-nitroalkanes in the gas phase",

abstract = "The theoretical study of the gas-phase pyrolysis kinetics of several tert-nitroalkanes, 2-methyl-2-nitropropane, 2-methyl-2-nitrobutane, and 2, 3-dimethyl-2-nitrobutane, has been carried out at the MP2/6-31G(d), B3LYP/6-31G(d), B3PW91/6-31G(d), levels of theory. The nitroalkanes yield the corresponding alkene and HNO2 gas in a rate determining step. The B3PW91/6-31G(d) method was found to give a reasonable good agreement with the experimental kinetic and thermodynamic parameters. The elimination of these reactions suggest a concerted non-synchronous five-membered cyclic transition state type of mechanism.",

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author = "Serrano, {Armando Jose} and Marcos Loro{\~n}o and Tania Cordova and Gabriel Chuchani",

year = "2008",

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T1 - Theoretical calculations of the thermal decomposition kinetics of several tert-nitroalkanes in the gas phase

AU - Serrano, Armando Jose

AU - Loroño, Marcos

AU - Cordova, Tania

AU - Chuchani, Gabriel

PY - 2008/6/30

Y1 - 2008/6/30

N2 - The theoretical study of the gas-phase pyrolysis kinetics of several tert-nitroalkanes, 2-methyl-2-nitropropane, 2-methyl-2-nitrobutane, and 2, 3-dimethyl-2-nitrobutane, has been carried out at the MP2/6-31G(d), B3LYP/6-31G(d), B3PW91/6-31G(d), levels of theory. The nitroalkanes yield the corresponding alkene and HNO2 gas in a rate determining step. The B3PW91/6-31G(d) method was found to give a reasonable good agreement with the experimental kinetic and thermodynamic parameters. The elimination of these reactions suggest a concerted non-synchronous five-membered cyclic transition state type of mechanism.

AB - The theoretical study of the gas-phase pyrolysis kinetics of several tert-nitroalkanes, 2-methyl-2-nitropropane, 2-methyl-2-nitrobutane, and 2, 3-dimethyl-2-nitrobutane, has been carried out at the MP2/6-31G(d), B3LYP/6-31G(d), B3PW91/6-31G(d), levels of theory. The nitroalkanes yield the corresponding alkene and HNO2 gas in a rate determining step. The B3PW91/6-31G(d) method was found to give a reasonable good agreement with the experimental kinetic and thermodynamic parameters. The elimination of these reactions suggest a concerted non-synchronous five-membered cyclic transition state type of mechanism.

KW - 2,3-Dimethyl-2-nitrobutane

KW - 2-Methyl-2-nitrobutane

KW - 2-Methyl-2-nitropropne

KW - B3PW91/6-31G(d)

KW - Calculations

KW - DFT B3LYP/6-31G(d)

KW - Gas-phase decomposition

KW - MP2/6-31G(d)

KW - Mechanism

KW - Pyrolysis

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U2 - 10.1016/j.theochem.2008.03.001

DO - 10.1016/j.theochem.2008.03.001

M3 - Artículo

AN - SCOPUS:43949147210

SN - 0166-1280

VL - 859

SP - 69

EP - 72

JO - Journal of Molecular Structure: THEOCHEM

JF - Journal of Molecular Structure: THEOCHEM

IS - 1-3

ER -

Theoretical calculations of the thermal decomposition kinetics of several tert-nitroalkanes in the gas phase

Abstract

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