TY - JOUR
T1 - Computational study for the second-stage cracking of the pyrolysis of ethylamine
T2 - Decomposition of methanimine, ethenamine, and ethanimine
AU - Almatarneh, Mansour H.
AU - Barhoumi, Lina
AU - Al-Tayyem, Ban
AU - Abu-Saleh, Abd Al Aziz A.
AU - AL-A'qarbeh, Marwa M.
AU - Abuorabi, Faten
AU - AlShamaileh, Ehab
AU - Altarawneh, Mohammednoor
AU - Marashdeh, Ali
N1 - Publisher Copyright:
© 2015 Elsevier B.V.
PY - 2016/1/1
Y1 - 2016/1/1
N2 - The mechanism that accounts for the observed experimental activation energy for the decomposition of ethylamine (EA) is still unknown. This paper reports the first detailed study of possible mechanisms for the pyrolysis of second-stage cracking product of ethylamine: the decomposition reaction of methanimine, ethanimine, and aminoethylene. Investigated reactions characterize either H2 elimination or 1,3-proton shift. These pathways result in the removal of H2, CH4, and NH3; and the formation of hydrogen cyanide, acetylene, acetonitrile, ethynamine, and ketenimine. The IRC analysis was carried out for all transition state structures to obtain the complete reaction pathways. The stationary points were fully optimized at B3LYP and MP2 levels of theory using the 6-31G(d), 6-31G(2df,p), and 6-31++G(3df,3dp) basis sets. Based on comparing energetic requirements, we find 1,3-proton shift is the most probable pathway for the decomposition of ethanimine. The decomposition reaction of ethenamine was the most plausible reaction with an activation energy of 297 kJ mol-1 calculated at the composite method of G4MP2.
AB - The mechanism that accounts for the observed experimental activation energy for the decomposition of ethylamine (EA) is still unknown. This paper reports the first detailed study of possible mechanisms for the pyrolysis of second-stage cracking product of ethylamine: the decomposition reaction of methanimine, ethanimine, and aminoethylene. Investigated reactions characterize either H2 elimination or 1,3-proton shift. These pathways result in the removal of H2, CH4, and NH3; and the formation of hydrogen cyanide, acetylene, acetonitrile, ethynamine, and ketenimine. The IRC analysis was carried out for all transition state structures to obtain the complete reaction pathways. The stationary points were fully optimized at B3LYP and MP2 levels of theory using the 6-31G(d), 6-31G(2df,p), and 6-31++G(3df,3dp) basis sets. Based on comparing energetic requirements, we find 1,3-proton shift is the most probable pathway for the decomposition of ethanimine. The decomposition reaction of ethenamine was the most plausible reaction with an activation energy of 297 kJ mol-1 calculated at the composite method of G4MP2.
KW - Decomposition reaction
KW - Ethanimine
KW - Ethenamine
KW - Methanimine
KW - TS optimization
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U2 - 10.1016/j.comptc.2015.10.032
DO - 10.1016/j.comptc.2015.10.032
M3 - Article
AN - SCOPUS:84947750183
SN - 2210-271X
VL - 1075
SP - 9
EP - 17
JO - Computational and Theoretical Chemistry
JF - Computational and Theoretical Chemistry
ER -