Temperature dependence of rate constants for the reaction of atomic oxygen with hydrogen chloride

Abstract

A phase-shift method has been used to determine the rate constant for the reaction of ground state oxygen atoms with HC1 over the temperature range of 33W300 K. Oxygen atoms were generated by modulated mercury photosensitized decomposition of NzO, and monitored by the chemiluminescence from their reaction with NO. After correction for diffusion of oxygen atoms from the viewing zone, the rate constants can be represented by the Arrhenius equation k , = (3.06 f 1.43) X 10l2 exp[(-3160 f 184)/T] cm3/mol-s. The indicated uncertainties are 95% confidence limits for 15 degrees of freedom. Also, the third-body efficiency of HC1 relative to NzO in the reaction 0 + NO + M -NO2 + M was determined to be 1.9 f 0.2 over the temperature range of 298-360 K.

New Stress Test for Ring Polymer Molecular Dynamics: Rate Coefficients of the O(3P) + HCl Reaction and Comparison with Quantum Mechanical and Quasiclassical Trajectory Results

“…The experimental measurements by Singleton et al in the high-temperature limit also exhibit a strong deviation from the Arrhenius behavior at T > 2000 K that cannot be reproduced by any of the theoretical approaches.…”

“…These results are compared with the QM and the semiclassical treatment of improved canonical variational TST including tunneling on the rate constant (ICVT/μOMT) data from ref . The column with k ( T ) exp corresponds to the empirical expression: The results from Table are also shown as an Arrhenius-type plot in Figure , along with the available experimental data. − The lower panel of the figure is an enlargement of the high-temperature region (1000–3200 K) of the results.…”

“…Comparison of experimental rate coefficients with those obtained with RPMD (black line with solid circles), QCT (red solid line), and QM (green short-dash line) from ref for the O­( 3 P) + HCl reaction between 200 and 3200 K. Symbols represent the experimental results from refs − . The bottom panel is a blowup of the inset of the upper panel covering the 1000–3200 K temperature range.…”

Surface-Catalyzed Reaction between the Gases Hydrogen Chloride and Isoprene

“…37,48−53 Hydrogen chloride (an atmospheric chlorine reservoir 41 ) has not generally been implicated in the production of atmospheric chlorinated carbon compounds (in contrast to their degradation) although, as noted above, it is one of the class of reactive halogen compounds found (surface associated) in the troposphere and whose concentration is relatively large. 37,48,48,54−56 Indeed, it is interesting to note that despite the interaction of hydrogen chloride with atomic oxygen, 57 with different ice forms, 58−60 as well as with water and other species on surfaces, 41,61−63 its reaction, as noted above, with unsaturated alkenes and alkynes, known to be present in the troposphere, has been largely ignored.…”

“…New chlorine containing compounds in the atmosphere related to refrigerants have been reported and it is likely that they and others intrude into the overall atmospheric chlorine balance. Additionally, in this vein, although a number of the chlorinated organic compounds found in the atmosphere have been attributed to industrially produced materials, some of these compounds are the result of the introduction of chlorine into living systems in the sea, where incorporation into aerosol and hence into the atmosphere is expected, and on land from halogens in the soil and their subsequent degradation. ,− Hydrogen chloride (an atmospheric chlorine reservoir) has not generally been implicated in the production of atmospheric chlorinated carbon compounds (in contrast to their degradation) although, as noted above, it is one of the class of reactive halogen compounds found (surface associated) in the troposphere and whose concentration is relatively large. ,,,− Indeed, it is interesting to note that despite the interaction of hydrogen chloride with atomic oxygen, with different ice forms, − as well as with water and other species on surfaces, ,− its reaction, as noted above, with unsaturated alkenes and alkynes, known to be present in the troposphere, has been largely ignored.…”