Ce(x)O(y)â» (x = 2-3) + D2O reactions: stoichiometric cluster formation from deuteroxide decomposition and anti-Arrhenius behavior.
J Phys Chem A
; 118(43): 9960-9, 2014 Oct 30.
Article
em En
| MEDLINE
| ID: mdl-25310627
ABSTRACT
Reactions between small cerium oxide cluster anions and deuterated water were monitored as a function of both water concentration and temperature in order to determine the temperature dependence of the rate constants. Sequential oxidation reactions of the Ce(x)O(y)â» (x = 2, 3) suboxide cluster anions were found to exhibit anti-Arrhenius behavior, with activation energies ranging from 0 to -18 kJ mol⻹. Direct oxidation of species up to y = x was observed, after which, -OD abstraction and D2O addition reactions were observed. However, the stoichiometric Ce2O4â» and Ce3O6â» cluster anions also emerge in reactions between D2O and the respective precursors, Ce2O3Dâ» and Ce3O5D2â». Ce2O4â» and Ce3O6â» product intensities diminish relative to deuteroxide complex intensities with increasing temperature. The kinetics of these reactions are compared to the kinetics of the previously studied Mo(x)O(y)â» and W(x)O(y)â» reactions with water, and the possible implications for the reaction mechanisms are discussed.
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
J Phys Chem A
Assunto da revista:
QUIMICA
Ano de publicação:
2014
Tipo de documento:
Article
País de afiliação:
Estados Unidos