Electron Radiolysis of Ammonium Perchlorate: A Reflectron Time-of-Flight Mass Spectrometric Study.
J Phys Chem A
; 121(20): 3879-3890, 2017 May 25.
Article
em En
| MEDLINE
| ID: mdl-28445648
ABSTRACT
Thin films of ammonium perchlorate (NH4ClO4) were exposed to energetic electrons at 5.5 K to explore the radiolytic decomposition mechanisms. The effects of radiolysis were monitored on line and in situ via Fourier transform infrared spectroscopy (FTIR) in the condensed phase along with electron impact ionization quadrupole mass spectrometry (EI-QMS) and single-photon photoionization reflectron time-of-flight mass spectrometry (PI-ReTOF-MS) during the temperature-programmed desorption (TPD) phase to probe the subliming molecules. Three classes of molecules were observed (i) nitrogen bearing species [ammonia (NH3), hydroxylamine (NH2OH), molecular nitrogen (N2), nitrogen dioxide (NO2)], (ii) chlorine carrying molecules [chlorine monoxide (ClO), chlorine dioxide (ClO2), dichlorine trioxide (Cl2O3)], and (iii) molecular oxygen (O2). Decay profiles of the reactants along with the growth profiles of the products as derived from the infrared data were fit kinetically to obtain a reaction mechanism with the initial steps involving a proton loss from the ammonium ion (NH4+) yielding ammonia (NH3) and the decomposition of perchlorate ion (ClO4-) forming chlorate ion (ClO3-) plus atomic oxygen. The latter oxidized ammonia to hydroxylamine and ultimately to nitrogen dioxide. Molecular oxygen and nitrogen were found to be formed via recombination of atomic oxygen and multistep radiolysis of ammonia, respectively.
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Bases de dados:
MEDLINE
Idioma:
En
Revista:
J Phys Chem A
Assunto da revista:
QUIMICA
Ano de publicação:
2017
Tipo de documento:
Article
País de afiliação:
Estados Unidos