Chemical Kinetics

Text extracted from opening pages of book: THE GEORGE FISHER BAKER NON-RESIDENT LECTURESHIP IN CHEMISTRY AT CORNELL UNIVERSITY Chemical Kinetics BY FARRINGTON Professor of Chemistry in the University of Wisconsin ITHACA NEW YORK CORNELL UNIVERSITY PRESS LONDON: HUMPHREY MILFORD OXFORD UNIVERSITY PRESS 1938 COPYRIGHT 1938 BY CORNELL UNIVERSITY PRINTFD IN THE UNITED STATES OF AMERICA Qtt) t < Eiill* giatr fJreaa C. EORC. E BANTA PXTBMSHING COMPANY, MFNASHA, WISCONSIN PREFACE THIS book is based on lectures delivered at Cornell University under the George Fisher Baker Non-Resident Lectureship in Chemistry from February to June 1935. So rapidly is our under standing of Chemical Kinetics changing that it has been necessary to include additional material up to the time of the completion of the manuscript in 1937. I appreciate the opportunity accorded me by the George Fisher Baker Fund. This lectureship, established a decade ago, has en-, abled Cornell to do much for Chemistry in America. It has brought the stimulus of foreign chemists to us and it is now leading in a much needed visitation of professors among our own universities. Wisconsin University and Cornell University have much in com mon. I am glad to have had the privilege of telling each about the other. Particularly I wish to thank Professor J. Papish and all the members of the chemistry department for their cordial hospitality during our pleasant visit in Ithaca. FAKRINGTON DANIELS Madison, Wisconsin, October, 1936. CONTENTS I. INTRODUCTION 1 II. GENERAL PRINCIPLES .... 8 Order of reaction ........ . . . 8 Specific reaction rate. . . 14 Chemical equilibrium. . . . 15 The Arrhenms equation 18 The kinetic theory of gases . . . . 24 Complicated reactions . ... . 27 III. THEORIES OF UNIMOLECULAR REACTIONS. ... . . 31 The radiation hypothesis . . 31 The collision hypothesis . 37 Chain reactions . 44 Free radicals 49 IV. GAS PHASE REACTIONS 56 Experimental technique ... 57 The decomposition of nitrogen pentoxide 60