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Decomposition of methylamino and aminomethyl radicals. The heats of formation of methyleneimine (CH_2=NH) and hydrazyl (N_2H_3) radical

Grela, M. A. and Colussi, A. J. (1988) Decomposition of methylamino and aminomethyl radicals. The heats of formation of methyleneimine (CH_2=NH) and hydrazyl (N_2H_3) radical. International Journal of Chemical Kinetics, 20 (9). pp. 713-718. ISSN 0538-8066. http://resolver.caltech.edu/CaltechAUTHORS:20150731-092100944

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Abstract

A kinetic analysis of the thermal decomposition of methylamino and aminomethyl radicals into methyleneimine, reactions (1) and (2): (1) CH_3N^•H → CH_2=NH + H (2) C^•H_2NH_2 → CH_2=NH + H leads to ΔH_f^0(CH_2=NH) = 25.0 ± 3 kcal/mol in excellent agreement with ion cyclotron resonance spectroscopy measurements and to a pi bond energy of E_π = 55.0 kcal/mol in CH_2=NH which is comparable but smaller than to the corresponding value in CH_2=CH_2 (63.7 kcal/mol). Assuming that E_π (CH_2=NH) = 0.5 [E_π (CH_2=CH_2) + E_π (NH=NH)] then requires that E_π (NH=NH) = 46.8 kcal/mol in diimine and BDE(N_2H_3-H) = 87.5 kcal/mol i.e. about 11.5 kcal/mol larger than current data for hydrazine but otherwise consistent with additional evidence. The entropy and heat capacity of methyleneimine, calculated from recent infrared and microwave spectroscopic data using the rigid rotor harmonic oscillator approximation, are also reported.


Item Type:Article
Related URLs:
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http://dx.doi.org/10.1002/kin.550200905DOIArticle
http://onlinelibrary.wiley.com/doi/10.1002/kin.550200905/abstractPublisherArticle
ORCID:
AuthorORCID
Colussi, A. J.0000-0002-3400-4101
Additional Information:© 1988 John Wiley & Sons. Received November 9, 1987; Accepted April 4, 1988.
Record Number:CaltechAUTHORS:20150731-092100944
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20150731-092100944
Official Citation:Grela, M. A. and Colussi, A. J. (1988), Decomposition of methylamino and aminomethyl radicals. The heats of formation of methyleneimine (CH2=NH) and hydrazyl (N2H3) radical. Int. J. Chem. Kinet., 20: 713–718. doi: 10.1002/kin.550200905
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:59100
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:07 Aug 2015 15:30
Last Modified:07 Aug 2015 15:30

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