Properties of Pure Nitryl Bromide. Thermal Behavior, UV/Vis and FTIR Spectra, and Photoisomerization to trans-BrONO in an Argon Matrix
摘要:
BrNO2 is produced by the heterogeneous reaction of CINO2, highly diluted in He, with an aqueous bromide solution and subsequent trapping at -155 degrees C. The crude product is purified by trap to trap condensation and fractional sublimation in vacuo. At 300 K and a pressure of 1 mbar, a half-life of about 1 h is observed. The decomposition produces Br-2 and NO2. The UV/vis and IR absorption cross sections of gaseous BrNO2 are determined in the ranges 185-600 nm and 2000-400 cm(-1), respectively. Irradiation of matrix-isolated BrNO2 with visible light causes nearly quantitative isomerization to trans-BrONO, while CINO2 is converted by UV light into a mixture of cis- and trans-ClONO. It is possible to assign all fundamentals of BrNO2 and trans-BrONO by comparison to the respective band position of the analogous molecules XNO(2) and XONO(X=Cl, F).
with subsequent experiments conducted with a xenon lamp at are reported. Formation of cis and trans ClONO in equilibrium with ClNO2 is observed after irradiation at 266 nm. At the transformation of trans ClONO into cis ClONO occurs. On prolonged photolysis at 266 nm, ClONO dissociates into ClON and atom and into ClO+NO as evidenced in reactive matrices (solid oxygen and nitrogen).
A Study of the Heterogeneous Reaction between Dinitrogen Pentaoxide and Chloride Ions on Low-Temperature Thin Films
作者:John R. Sodeau、Tristan B. Roddis、Matt P. Gane
DOI:10.1021/jp993763l
日期:2000.3.1
mixtures, infrared spectra indicative of solid D2h-N2O4 are measured, as well as peaks corresponding to nitrate ions and cis-ClONO (chlorine nitrite). Reaction between ClNO2 and its isomer, cis-ClONO, is proposed as an explanation for the formation of dinitrogen tetraoxide in both systems. The proposed reaction mechanism for this hydrolysis is extended to the N2O5/H2O/HCl deposits in order to explain