A System Of Physical Chemistry - Vol I

A SYSTEM OF PHYSICAL CHEMISTRY BY WILLIAM C. McC. LEWIS, M. A. R. U. I.. D. Sc. Liv. BRUNNER PROFESSOR OF PHYSICAL CHEMISTRY IN THE UNIVERSITY OF LIVERPOOL IN THREE VOLUMES VOLUME I KINETIC THEORY NEW IMPRESSION LONG Vf-A N S, -G R E-E N AND C O. 39 PATERNOSTER ROW, LONDON, E. C 4 NEW YORK, TORONTO BOMBAY, CALCUTTA AND MADRAS All rights reserved SCIENCE is nothing without generalisations. . . . The suggestion of a new idea, or the detection of a law, supersedes much that had previously been a burden upon the memory, and by introducing order and coherence facilitates the retention of the remainder in an available form. LORD RAYLEIGH. BIBLIOGRAPHICAL NOTE First Edition, Two Volumes. February, 1916. The Second Edition was issued in Three Volumes. Volume L September, 1918. New Impressions, March, 1920 June, 1921 and April, 1923. PREFACE TO SECON D EDITION. THE general plan and arrangement followed in the first edition has been adhered to in the present one. A number of changes, however, necessitated by the advances which physical chemistry has made in the last few years, have been introduced, with the r esult that the book has undergone considerable expansion. The principal change is the addition of-a - third volume in place of a single chapter, in which an account is given of the Quantum Theory in its physico-chemical aspect. The rdle which the quantum theory now plays in physical and chemical research makes it imperative for the advanced student to be familiar si n fvr, e extent with the ramifications, of this remarkable concept of energy fcansfer. The swrrjess which has lidded tjje application of this theory, especially in connection with probTems which the kinetic theory andthermodynamics by themselves are incapable of solving, constitutes its main claim to consideration. In view of the rather unique character of the quantum theory many of the problems dealt with in Vol. III. do not find a counterpart in Vols. I. and II. There is, however, no real lack of continuity, as the reader will doubtless perceive for himself. Incidentally the addition of a third volume obviates the necessity of division into the three Parts employed in the previous edition. Among the new additions to Vol. I. may be mentioned the investigation of crystal structure by means of X Rays, various properties of the colloidal state, recent investigations on the dis sociation of ammonium chloride vapour, the Dual Theory of homogeneous catalysis, the Displacement Effect, and Langmuirs theory of heterogeneous reaction velocity, catalysis, and the mechanism of surface effects generally. In Vol. II. a brief consideration of entropy has been included v more particularly with the object of leading up to Boltzmanns probability-entropy relation in statistical mechanics which is dealt with in Vol. IIL f whereby a statistical basis for the second vi PREFACE TO SECOND EDITION law of thermodynamics is obtained. The principal change in Vol. II. is the inclusion of a new chapter dealing with the still debatable subject of osmotic pressure, and the modern theory of dilute solutions. A brief account of the theory of vegetable tanning has also been included in the chapter dealing with adsorption and membrane equilibria. In addition to the books mentioned in the preface to the first edition, I have further to acknowledge my indebtedness to the following Washburns Principles of Physical Chemistry SackursThermochemistry and Thermodynamics translated by Gibson, X Rays and Crystal Structure by W. H. and W. L. Bragg, Tuttons Crystallography and Practical Crystal Measure men Nernsts Solid State of Matter, and Pollitzers article on Nernsts Heat Theorem in Ahrens Sammlung. I am indebted to Professor Bragg and to Messrs. G. Bell Soils for permission to use certain diagrams from the book on Crystal Structure mentioned above. In the same connection I am indebted to the Council of the Chemical Society for permis sion to use two plates from the Transactions, vol. cix, 1916...