High pressure fast‐flow technique for gas phase kinetics studies

A fast-flow technique suitable for measuring elementary rate constants over a wide range of pressures has been developed. The method operates under turbulent flow conditions, in contrast to laminar flow which characterizes the conventional low pressure technique. Flow visualization, velocity profile measurements, and tracer pulse studies have been carried out in a flow tube reactor to investigate the dynamics of both laminar and turbulent flow for chemical kinetics purposes. Furthermore, the wall collision frequency for the reactants has been determined: at the higher pressures it is greatly reduced in comparison with the frequency characteristic of the conventional low pressure laminar flow technique. Also, to test and validate the technique the bimolecular rate constants for the reactions H+Cl2 and H+O3 have been measured at total pressures in the 3–300 torr range; at pressures below 5 torr, as well as above 50 torr in the turbulent flow regime the agreement with the recommended literature values is excellent. © 1993 John Wiley & Sons, Inc.

[1]  R. W. Carr,et al.  Use of tubular flow reactors for kinetic studies over extended pressure ranges , 1971 .

[2]  Carleton J. Howard,et al.  Kinetic measurements using flow tubes , 1979 .

[3]  James G. Anderson,et al.  A new approach to free-radical kinetics: radially and axially resolved high-pressure discharge flow with results for hydroxyl + (ethane, propane, n-butane, n-pentane) .fwdarw. products at 297 K , 1990 .

[4]  J. C. Jaeger,et al.  Conduction of Heat in Solids , 1952 .

[5]  Roger Atkinson,et al.  Evaluated kinetic and photochemical data for atmospheric chemistry: Volume III - gas phase reactions of inorganic halogens , 2006 .

[6]  William J. Massman,et al.  The attenuation of concentration fluctuations in turbulent flow through a tube , 1991 .

[7]  R. A. Cox,et al.  Evaluated kinetic and photochemical data for atmospheric chemistry: Supplement II , 1989 .

[8]  F. Dryer,et al.  Decomposition of 1,3,5-trioxane at 700-800 K , 1992 .

[9]  R. Aris On the dispersion of a solute in a fluid flowing through a tube , 1956, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.

[10]  Robert S. Brodkey,et al.  The phenomena of fluid motions , 1967 .

[11]  M. Clyne,et al.  Atomic resonance fluorescence for rate constants of rapid bimolecular reactions. Part 6.—Hydrogen atom reactions: H + Cl2 from 300 to 730 K and H + NO2 at 298 K , 1977 .

[12]  C.I.M. Beenakker,et al.  A cavity for microwave-induced plasmas operated in helium and argon at atmospheric pressure , 1976 .

[13]  F. Kaufman,et al.  Rates of elementary reactions: measurement and applications. , 1985, Science.

[14]  L. F. Keyser High-pressure flow kinetics - A study of the OH + HCl reaction from 2 to 100 torr , 1984 .

[15]  M. Zahniser,et al.  The temperature dependence of mass accommodation of sulfur dioxide and hydrogen peroxide on aqueous surfaces , 1989 .

[16]  Robert N. Goldberg,et al.  Evaluated activity and osmotic coefficients for aqueous solutions: Bi‐univalent compounds of zinc, cadmium, and ethylene bis(trimethylammonium) chloride and iodide , 1981 .

[17]  D. Toohey,et al.  Rate constant for the reaction Br + O3 → BrO + O2 from 248 to 418 K: Kinetics and mechanism , 1988 .

[18]  R. L. Brown Tubular Flow Reactors With First-Order Kinetics. , 1978, Journal of research of the National Bureau of Standards.

[19]  J. Michael,et al.  Absolute rate of the reaction of hydrogen atoms with ozone from 219–360 K , 1978 .

[20]  Frederick Kaufman Kinetics of elementary radical reactions in the gas phase , 1984 .

[21]  P. Sullivan,et al.  Longitudinal dispersion within a two-dimensional turbulent shear flow , 1971, Journal of Fluid Mechanics.

[22]  M. Clyne,et al.  Atomic resonance fluorescence for rate constants of rapid bimolecular reactions. Part 5—Hydrogen atom reactions; H + NO2 and H + O3 , 1977 .