UNITED STATES DEPARTMENT OF COMMERCE PETER G. PETERSON, Secretary For sale by the Superintendent of Documents, U.S. Government Printing Office, Washington, D.C. 20402 (Order by SD Catalog No. C 13.10:349) Price 45 cents Foreword The National Standard Reference Data System was established in 1963 for the primary purpose of providing critically evaluated numerical data in the physical sciences. The System comprises a complex of data centers and other activities located in government laboratories, universities, and other institutions. These components of the NSRDS produce compilations of critically evaluated data, critical reviews of the state of quantitative knowledge in specialized areas, and compilations of useful functions derived from such reference data. In addition, the centers and projects establish criteria for evaluation and compilation of data and make recommendations on needed improvements in experimental techniques. A necessary step in the operation of each of these data centers is the generation of comprehensive, thoroughly indexed bibliographies covering the fields of interest of the center. In most cases, these bibliographic files are computer-based. In the interest of making the full resources of the data centers of maximum utility to the scientific and technical community, selected bibliographies are published from time to time in the NBS Special Publication Series. Further information on the program and publications of the National Standard Reference Data System may be obtained by writing to the Office of Standard Reference Data, National Bureau of Standards, Washington, D.Č. 20234. DAVID R. LIDE, JR., Chief Office of Standard Reference Data Heavy-Atom Kinetic Isotope Effects Marvin J. Stern** and Max Wolfsberg*** A bibliography of heavy-atom kinetic isotope effects has been compiled covering the complete literature from the earliest entry found (1911) through 1965. Review articles and theoretical papers are listed through 1968. The bibliography is divided into a list of the references, an author index and a subject index. The subject index has been annotated to describe, in brief, the type of reaction being observed. The following areas have been excluded: geochemistry (except for specific laboratory reactions), living systems, mass spectrometry and electron impact, electrochemistry, diffusion-controlled processes, hot-atom chemistry, photochemistry involving selective excitation of isotopes, and processes involving no chemical change. Key words: Author index; bibliography; heavy-atom isotope effects; isotope effects; kinetic isotope effects; reaction kinetics; subject index. Introduction Background The authors at first considered writing a critical review monograph on kinetic isotope effects. The literature embraced by this field was believed to be sufficiently large to be divisible into two parts: (1) isotope effects due to the substitution of hydrogen by deuterium or tritium; (2) isotope effects due to heavyatom substitutions. To make the project manageable, only the latter aspect of the subject was chosen for the critical review. However, after a bibliography containing approximately 500 references had been assembled, it was found that usually each experimental system was suf ficiently different from the others to warrant separate analysis. In addition, the early papers contained many contradictory data which appeared to make critical analysis very difficult. As a consequence, the authors decided to reduce the scope of their effort and prepare an annotated index to the literature in the field. This endeavor has involved a thorough reading of the selected papers, and classification and indexing of the pertinent information. It is hoped that researchers engaged in kinetic isotope effect studies or others wanting to make use of such studies will find this indexed bibliography useful. Description and Classification Scheme The main, but by no means only, sources of pertinent references for the bibliography were Chemical Abstracts and Nuclear Science Abstracts through the * Work carried out in part under the auspices of the U.S. Atomic Energy Commission. ** Present address: Chemistry Department, Belfer Graduate School of Science, Yeshiva University, New York, N.Y. 10033. *** Present address: Chemistry Department, University of California, Irvine, Calif. 92664. year 1965. The search was extended through the year 1968, but only for review articles and theoretical papers. One review article published in 1969 is also included. The bibliography was checked against reprints in the files of the authors; references within the articles collected for the bibliography were checked for appropriateness of inclusion; and other appropriate bibliographies or partial bibliographies of the field were checked. Many of the authors' colleagues helped by submitting reprints of their articles. The papers finally included were generally restricted to those appearing in formally published literature (journal articles, chapters in books, proceedings of symposia, etc.). Thus, works such as doctoral theses, technical reports, and abstracts of talks presented at scientific meetings were, with rare exceptions, omitted. It is the belief of the authors that, for the period covered and topics considered (vide infra), the bibliography is better than 98 percent complete (except, perhaps, for Chinese literature). Articles that might have been missed probably fall into one of three categories: (1) papers published prior to 1966 but not appearing in the abstract journals until a later date; (2) reviews of reaction mechanisms containing very limited discussions of isotope effect studies; (3) papers on isotopic tracer studies which note only in passing the observation of kinetic isotope effects. The study of the effect of isotopic substitution on a rate constant (kinetic isotope effect) serves to elucidate the reaction mechanism. There is strong interplay between experiment and theory in this area, and the experimental data are often interpreted by applying transition state theory (absolute reaction rate theory). The area of interest has been defined to include only in vitro reactions of well-defined reactants which are in thermal equilibrium. Isotope effects in the fol lowing areas have been specifically excluded: (1) geochemistry (unless the work involves specific labo |