DISCUSSIONS OF THE FARADAY SOCIETY No. 17, 1954 THE STUDY OF FAST REACTIONS THE FARADAY SOCIETY Agents for the Society’s Publications : The Aberdeen University Press Ltd. 6 Upper Kirkgate AberdeenThe Faraday Society reserves the copyright of all Communications published in the " Discussions '' PUBLISHED . . 1954 PRINTED IN GREAT BRITAIN AT THE UNIVERSITY PRESS ABERDEENA GENERAL DISCUSSION ON THE STUDY OF FAST REACTIONS A GENERAL DISCUSSION on The Study of Fast Reactions was held in the Depart- ment of Chemistry, Birmingham University (by kind permission of the Vice- Chancellor) on the 7th, 8th and 9th April, 1954. The President, Prof. R. G. W. Norrish, Sc.D., F.R.I.C., F.R.S., was in the Chair and about 250 members and visitors were present. Among the distinguished overseas members and visitors welcomed by the President were the following :- Mr.J. Adam (Brussels), Dr. and Mrs. E. J. Arlman (Amsterdam), Mr. T. Bak (Copcnhagen), Prof. E. Barany (Uppsala), Prof. S. H. Bauer (Cornell University), Dr. S. A. Bernhard (U.S.A.), Dr. Britton Chance (University of Pennsylvania), Prof. N. Davidson (California Institute of Technology), Prof. P. Delahay (Louisiana State University), Dr. and Mrs. M. Eigen (Gottingen), Dr. F. Hageman (Amsterdam), Prof. H. S. Johnston (Stanford University), Dr. Y . Haven (Eindhoven), Dr. T. Iredale (Australia), Dr. C. Jouwersma (Eindhoven), Prof. W. Jost (Darmstadt), Dr. F. Kaufman (U.S.A.), Prof. G. B. Kistiakowsky (Harvard University), Prof. I. M. Kolthoff (Uni- versity of Minnesota), Dr. G. F.Lanzl (Wilmington, Del.), Dr. J. E. LuValle (Arlington, Mass.), Dr. R. A. Ogg (Stanford University), Dr. R. G. Pearson (Northwestern University), Dr. D. C. Pepper (Dublin), Dr. G. Salomon (The Hague), Dr. M. Sangster (Amsterdam), Dr. R. Schlogl (Gottingen), Dr. K. E. Schulcr (The Johns Hopkins University), Dr. J. J. van Deemter (Amsterdam), Prof. T. Vermeulen (University of California) and Dr. Voetelink (Oklahoma). 3A GENERAL DISCUSSION ON THE STUDY OF FAST REACTIONS A GENERAL DISCUSSION on The Study of Fast Reactions was held in the Depart- ment of Chemistry, Birmingham University (by kind permission of the Vice- Chancellor) on the 7th, 8th and 9th April, 1954. The President, Prof. R. G. W. Norrish, Sc.D., F.R.I.C., F.R.S., was in the Chair and about 250 members and visitors were present.Among the distinguished overseas members and visitors welcomed by the President were the following :- Mr. J. Adam (Brussels), Dr. and Mrs. E. J. Arlman (Amsterdam), Mr. T. Bak (Copcnhagen), Prof. E. Barany (Uppsala), Prof. S. H. Bauer (Cornell University), Dr. S. A. Bernhard (U.S.A.), Dr. Britton Chance (University of Pennsylvania), Prof. N. Davidson (California Institute of Technology), Prof. P. Delahay (Louisiana State University), Dr. and Mrs. M. Eigen (Gottingen), Dr. F. Hageman (Amsterdam), Prof. H. S. Johnston (Stanford University), Dr. Y . Haven (Eindhoven), Dr. T. Iredale (Australia), Dr. C. Jouwersma (Eindhoven), Prof. W. Jost (Darmstadt), Dr. F. Kaufman (U.S.A.), Prof. G. B. Kistiakowsky (Harvard University), Prof. I. M.Kolthoff (Uni- versity of Minnesota), Dr. G. F. Lanzl (Wilmington, Del.), Dr. J. E. LuValle (Arlington, Mass.), Dr. R. A. Ogg (Stanford University), Dr. R. G. Pearson (Northwestern University), Dr. D. C. Pepper (Dublin), Dr. G. Salomon (The Hague), Dr. M. Sangster (Amsterdam), Dr. R. Schlogl (Gottingen), Dr. K. E. Schulcr (The Johns Hopkins University), Dr. J. J. van Deemter (Amsterdam), Prof. T. Vermeulen (University of California) and Dr. Voetelink (Oklahoma). 3CONTENTS A. GAS REACTIONS- Introductory Paper. By H. W. Melville . Photoelectric Methods for following Fast Gas-Phase Reactions. By Harold S. Johnston . A Thermal Method of Investigating Fast Gas-Phase Reactions. Part I. -The Mercury Photo-sensitized Decomposition of Ethylene. By A. B. Callear and James C .Robb . The Temperature Pattern Method in the Study of Fast Chemical Reactions. By David Garvin, Vincent P. Guinn and G. B. Kistiakowsky . The Application of Flash Techniques to the Study of Fast Reactions. By R. G. W. Norrish and G. Porter . Reactions of Atomic Oxygen with Molecular Oxygen. By Richard A. Ogg, Jr. and William T. Sutphen . A Mechanical Method for the Activation of Fast Reactions. By T. H. Bull and P. B. Moon . Shock Waves in Chemical Kinetics. The Rate of Dissociation of Molecular Iodine. By Doyle Britton, Norman Davidson and Garry Schott . Relaxation Techniques for Fast Reactions. A Study of the Dis- sociation of Nitrogen Tetroxide. By S. H. Bauer and M. R. Gustavson . GENERAL DrscussroN.-Dr. H. 0. Pritchard, Mr. R. G. Sowden, Dr. A. F.Trotman-Dickenson, Prof. S. H. Bauer, Prof. G. B. Kistiakowsky, Mr. A. R. Callear, Dr. J. C. Robb, Mr. C. R. Patrick, Dr. R. A. Ogg, Jr., Dr. A. D. Walsh, Dr. G. Porter, Dr. N. Davidson, Mr. R. R. Baldwin, Prof. A. R. Ubbelohde, Dr. A. J. B. Robertson, Dr. R. A. Ogg, Dr. J. Weiss, Mr. M. W. Windsor, Mr. J. Dewing, Dr. K. E. Russell, Dr. D. Britton, Mr. G. Boocock, Dr. J. J. Long, Dr. K. W. Sykes, Miss Christie, Prof. R. W. G. Norrish, Dr. K. G. Dcnbigh, Dr. G. Salomon, Dr. Y . Haven, Dr. M. Eigcn, Mr. M. Sangster, Dr. James E. LuValle . B. SOLUTION REACTIONS- Introductory Paper. By R. P. Bell . PAGE 9 14 21 32 40 47 54 58 69 90 114 Rapid Rcactions in Biology. By*F. J. W. Roughton . . 116 56 CONTENTS PAC+$ Regeneration and Recirculation of Reactants in the Rapid-Flow Apparatus.Part 1.-Design Criteria. By Britton Chancc . . 120 Part 2.-Practical Designs. By Britton Chancc and Victor Legallais 123 The Application of Photoelectric Spectrophotometry to thc Constant Flow Method. By K. DaIziel . . 128 A Semi-Automatic Apparatus for the Photometric Measurement of the Rates of Fast Reactions. By E. F. Caldin and F. W. Trowse. 133 Stopped-Flow Apparatus for the Study of Rapid Reactions. By Q. H. Gibson . . 137 A Quenching Method for Studying Rapid Reactions. By B. R. W. Pinsent . . 140 The Measurement of the Rate of Rapid Reactions by a Thermal Method. By L. Pearson, B. R. W. Pinsent and F. W. Roughton . 141 The Capacity Flow Method in Chemical Kinetics. By K. G. Denbigh and F. M. Page . . 145 Developments in the Thermal Maximum Method for Reaction Veloci- By R.P. Bell, V. Gold, J. Hilton and M. H. Rand ties in Solution. 151 Applicability of Megacycle Frequency Oscillator Circuits to Reaction Rate Measurement. By Philip J. Elving . . 156 The Use of Rotating and Stationary Electrodes for Fast Reactions. By I. M. Kolthoff and W. L. Reynolds . . 167 A Photoelectric Rccording Interferometer. By G. M. Burnett, P. J. Deas and H. W. Melville . . 173 Studies of thc Triplet State in Fluid Solvents. By George Portcr and Maurice W. Windsor . . 178 Rates of Ion Recombination in Solution by a Radio-Frequency Dis- persion Method. By Ralph G. Pearson . . 187 Methods for Investigation of Tonic Reactions in Aqueous Solutions with Half Times as short as 10-9 sec. Application to Neutralization and Hydrolysis Reactions. By M. Eigen . . 194 Applications of Voltammetry at Constant Current in Chemical Kinetics. By Paul Delahay . . 205 Study of Ultrarapid Reactions in Nuclear Magnetic Resonance Spectra. By Richard A. Ogg, Jr. . . 215CONTENTS 7 PAGE GENERAL DIscussIoN.-Dr. F. W. Trowse, Prof. F. J. W. Roughton, Dr. H. Gutfreund, Mr. R. P. Bell, Dr. James E. LuValle, Dr. R. G. Pearson, Dr. Y. Haven, Dr. Britton Chance, Dr. K. G. Denbigh, Mr. F. M. Page, Mr. F. Goodridge, Prof. S. H. Bauer, Dr. V. Gold, Dr. N. Uri, Prof. I. M. Kolthoff, Dr. G. Porter, Dr. F. J. Wright, Dr. J. Weiss, Prof. P. Delahay, Dr. G. Salomon, Dr. M. Eigen, Dr. R. A. Ogg, Jr. . . 220 Author Index . . 234 Reviews of Books . . 235