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Dehydrogenation of N2HX (X=2-4) by nitrogen atoms: thermochemical and kinetics
Rene Felipe Keidel Spada1, Luiz Fernando de Araujo Ferrão, Orlando Roberto-Neto
1Departamento de Química, Instituto Tecnológico de Aeronáutica, São José dos Campos 12.228-900, São Paulo, Brazil.
Abstract:
Thermochemical and kinetics of sequential hydrogen abstraction reactions from hydrazine by nitrogen atoms were studied. The dehydrogenation was divided in three steps, N2H4 + N, N2H3 + N, and N2H2 + N. The thermal rate constants were calculated within the framework of canonical variational theory, with zero and small curvature multidimensional tunnelling corrections. The reaction paths were computed with the BB1K/aug-cc-pVTZ method and the thermochemical properties were improved with the CCSD(T)/CBS//BB1K/aug-cc-pVTZ approach. The first dehydrogenation step presents the lowest rate constants, equal to 1.22 × 10(-20) cm(3) molecule(-1) s(-1) at 298 K.
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