INVESTIGADORES
ROMANO Rosana Mariel
artículos
Título:
Kinetics and Mechanism of the Thermal Gas-Phase Reaction between NO2 and Trifluorochloroethene
Autor/es:
ROSANA M. ROMANO; CARLOS O. DELLA VÉDOVA; JOANNA CZARNOWSKI
Revista:
Zeitschrift für Physikalische Chemie
Referencias:
Año: 2002 vol. 216 p. 1203 - 1217
ISSN:
0942-9352
Resumen:
The reaction of NO2 with CF2CFCl has been studied at 322.8, 332.2 and 342.2K, using
a conventional static system. The initial pressure of CF2CFCl was varied between 13.0 and
90.2 Torr and that of NO2 between 9.3 and 89.5 Torr. Several experiments were carried
out in presence of CF4, varying its pressure from 277.6 to 458.5 Torr. Three products
were formed: O2NCF2CFClNO2 and equimolecular amounts of ClNO and O2NCF2C(O)F.
The product distribution was independent of the initial pressures of the reactants and the
total pressure, but the ratio of O2NCF2C(O)F to that of O2 NCF2CFClNO2 increased with
temperature. The reaction is homogeneous and independent of the total pressure. The
following mechanism was postulated to explain the experimental results:
1. NO2 +CF2CFCl→O2NCF2CFCl2 with CF2CFCl has been studied at 322.8, 332.2 and 342.2K, using
a conventional static system. The initial pressure of CF2CFCl was varied between 13.0 and
90.2 Torr and that of NO2 between 9.3 and 89.5 Torr. Several experiments were carried
out in presence of CF4, varying its pressure from 277.6 to 458.5 Torr. Three products
were formed: O2NCF2CFClNO2 and equimolecular amounts of ClNO and O2NCF2C(O)F.
The product distribution was independent of the initial pressures of the reactants and the
total pressure, but the ratio of O2NCF2C(O)F to that of O2 NCF2CFClNO2 increased with
temperature. The reaction is homogeneous and independent of the total pressure. The
following mechanism was postulated to explain the experimental results:
1. NO2 +CF2CFCl→O2NCF2CFCl2CFCl was varied between 13.0 and
90.2 Torr and that of NO2 between 9.3 and 89.5 Torr. Several experiments were carried
out in presence of CF4, varying its pressure from 277.6 to 458.5 Torr. Three products
were formed: O2NCF2CFClNO2 and equimolecular amounts of ClNO and O2NCF2C(O)F.
The product distribution was independent of the initial pressures of the reactants and the
total pressure, but the ratio of O2NCF2C(O)F to that of O2 NCF2CFClNO2 increased with
temperature. The reaction is homogeneous and independent of the total pressure. The
following mechanism was postulated to explain the experimental results:
1. NO2 +CF2CFCl→O2NCF2CFCl.2 Torr and that of NO2 between 9.3 and 89.5 Torr. Several experiments were carried
out in presence of CF4, varying its pressure from 277.6 to 458.5 Torr. Three products
were formed: O2NCF2CFClNO2 and equimolecular amounts of ClNO and O2NCF2C(O)F.
The product distribution was independent of the initial pressures of the reactants and the
total pressure, but the ratio of O2NCF2C(O)F to that of O2 NCF2CFClNO2 increased with
temperature. The reaction is homogeneous and independent of the total pressure. The
following mechanism was postulated to explain the experimental results:
1. NO2 +CF2CFCl→O2NCF2CFCl4, varying its pressure from 277.6 to 458.5 Torr. Three products
were formed: O2NCF2CFClNO2 and equimolecular amounts of ClNO and O2NCF2C(O)F.
The product distribution was independent of the initial pressures of the reactants and the
total pressure, but the ratio of O2NCF2C(O)F to that of O2 NCF2CFClNO2 increased with
temperature. The reaction is homogeneous and independent of the total pressure. The
following mechanism was postulated to explain the experimental results:
1. NO2 +CF2CFCl→O2NCF2CFCl2NCF2CFClNO2 and equimolecular amounts of ClNO and O2NCF2C(O)F.
The product distribution was independent of the initial pressures of the reactants and the
total pressure, but the ratio of O2NCF2C(O)F to that of O2 NCF2CFClNO2 increased with
temperature. The reaction is homogeneous and independent of the total pressure. The
following mechanism was postulated to explain the experimental results:
1. NO2 +CF2CFCl→O2NCF2CFCl2NCF2C(O)F to that of O2 NCF2CFClNO2 increased with
temperature. The reaction is homogeneous and independent of the total pressure. The
following mechanism was postulated to explain the experimental results:
1. NO2 +CF2CFCl→O2NCF2CFCl2 +CF2CFCl→O2NCF2CFCl
2. O2NCF2CFCl+NO2 +M→O2NCF2CFClNO2 +M
3. O2NCF2CFCl+NO2 →O2NCF2C(O)F+ClNO2NCF2CFCl+NO2 +M→O2NCF2CFClNO2 +M
3. O2NCF2CFCl+NO2 →O2NCF2C(O)F+ClNO2NCF2CFCl+NO2 →O2NCF2C(O)F+ClNO
k1 = (1.7±0.4)×106 exp(−(10.8±1) kcalmol−1/RT)dm3 mol−1 s−11 = (1.7±0.4)×106 exp(−(10.8±1) kcalmol−1/RT)dm3 mol−1 s−1
k3 = (9.8±3)×1010 exp(−(1.1±0.2) kcalmol−1/RT)dm3 mol−1 s−1.3 = (9.8±3)×1010 exp(−(1.1±0.2) kcalmol−1/RT)dm3 mol−1 s−1.
