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Reactivity of the Hydroxyl Radical in Aqueous Solutions

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Reactivity of the Hydroxyl Radical in Aqueous Solutions NSRDS—NBS 46 National Bureau of Standards NATIONAL BUREAU OF STANDARDS 1 The National Bureau of Standards was established by an act of Congress March 3, 1901. The Bureau’s overall goal is to strengthen and advance the Nation’s science and technology and facilitate their effective application for public benefit. To this end, the Bureau conducts research and provides: (1) a basis for the Nation’s physical measurement system, (2) scientific and technological services for industry and government, (3) a technical basis for equity in trade, and (4) technical services to promote public safety. The Bureau consists of the Institute for Basic Standards, the Institute for Materials Research, the Institute for Applied Technology, the Institute for Computer Sciences and Technology, and the Office for Information Programs. THE INSTITUTE FOR BASIC STANDARDS provides the central basis within the United States of a complete and consistent system of physical measurement; coordinates that system with measurement systems of other nations; and furnishes essential services leading to accurate and uniform physical measurements throughout the Nation’s scientific community, industry, and commerce. The Institute consists of a Center for Radiation Research, an Office of Meas- urement Services and the following divisions: Applied Mathematics — Electricity — Mechanics — Heat — Optical Physics — Nuclear Sciences 2 — Applied Radiation 2 — Quantum Electronics 3 — Electromagnetics 3 — Time 3 3 3 and Frequency — Laboratory Astrophysics — Cryogenics . THE INSTITUTE FOR MATERIALS RESEARCH conducts materials research leading to improved methods of measurement, standards, and data on the properties of well-characterized materials needed by industry, commerce, educational institutions, and Government; provides advisory and research services to other Government agencies; and develops, produces, and distributes standard reference materials. The Institute consists of the Office of Standard Reference Materials and the following divisions: Analytical Chemistry — Polymers — Metallurgy — Inorganic Materials — Reactor Radiation — Physical Chemistry. THE INSTITUTE FOR APPLIED TECHNOLOGY provides technical services to promote the use of available technology and to facilitate technological innovation in industry and Government; cooperates with public and private organizations leading to the development of technological standards (including mandatory safety standards), codes and methods of test; and provides technical advice and services to Government agencies upon request. The Institute consists of a Center for Building Technology and the following divisions and offices: Engineering and Product Standards — Weights and Measures — Invention and Innova- tion — Product Evaluation Technology — Electronic Technology — Technical Analysis — Measurement Engineering — Structures, Materials, and Life Safety * — Building Environment 4 — Technical Evaluation and Application 4 — Fire Technology. THE INSTITUTE FOR COMPUTER SCIENCES AND TECHNOLOGY conducts research and provides technical services designed to aid Government agencies in improving cost effec- tiveness in the conduct of their programs through the selection, acquisition, and effective utilization of automatic data processing equipment; and serves as the principal focus within the executive branch for the development of Federal standards for automatic data processing equipment, techniques, and computer languages. The Center consists of the following offices and divisions: Information Processing Standards — Computer Information — Computer Services — Systems Development — Information Processing Technology. THE OFFICE FOR INFORMATION PROGRAMS promotes optimum dissemination and accessibility of scientific information generated within NBS and other agencies of the Federal Government; promotes the development of the National Standard Reference Data System and a system of information analysis centers dealing with the broader aspects of the National Measurement System; provides appropriate services to ensure that the NBS staff has optimum accessibility to the scientific information of the world. The Office consists of the following organizational units: Office of Standard Reference Data — Office of Technical Information and Publications — Library — Office of International Relations. 1 Headquarters and Laboratories at Gaithersburg, Maryland, unless otherwise noted; mailing address Washington, D.C. 20234. 3 Part of the Center for Radiation Research. 3 Located at Boulder, Colorado 80302. * Part of the Center for Building Technology. National Bureau m Standard M H \/ U:r\l 1974 Reactivity of the Hydroxyl Radical in Aqueous Solutions Leon M. Dorfman Department of Chemistry The Ohio State University Columbus, Ohio 43210 and Gerald E. Adams Cancer Research Campaign Grey Laboratory Mount Vernon Hospital Northwood, Middlesex, England U.S. DEPARTMENT OF COMMERCE, Frederick B. Dent, Secretary NATIONAL BUREAU OF STANDARDS, Richard W. Roberts, Director Issued June 1973 Library of Congress Catalog Card Number: 72-600321 NSRDS-NBS 46 Nat. Stand. Ref. Data Ser., Nat. Bur. Stand. (U.S.), 46 72 pages (June 1973) CODEN: NSRDAP © 1972 by the Secretary of Commerce on Behalf of the United States Government For sale by the Superintendent of Documents, U.S. Government Printing Office, Washington, D.C. 20402 (Order by SD Catalog No. C13. 48:46) Price: 90 cents, domestic postpaid; 65 cents, GPO Bookstore Stock Number 0303-01088 Foreword The National Standard Reference Data System provides access to the quantitative data of phys- ical science, critically evaluated and compiled for convenience and readily accessible through a variety of distribution channels. The System was established in 1963 by action of the President’s Office of Science and Technology and the Federal Council for Science and Technology, and responsibility to administer it was assigned to the National Bureau of Standards. NSRDS receives advice and planning assistance from a Review Committee of the National Research Council of the National Academy of Sciences-National Academy of Engineering. A num- ber of Advisory Panels, each concerned with a single technical area, meet regularly to examine major portions of the program, assign relative priorities, and identify specific key problems in need of further attention. For selected specific topics, the Advisory Panels sponsor subpanels which make detailed studies of users’ needs, the present state of knowledge, and existing data re- sources as a basis for recommending one or more data compilation activities. This assembly of advisory services contributes greatly to the guidance of NSRDS activities. The System now includes a complex of data centers and other activities in academic insti- tutions and other laboratories. Components of the NSRDS produce compilations of critically evaluated data, reviews of the state of quantitative knowledge in specialized areas, and computa- tions of useful functions derived from standard reference data. The centers and projects also establish criteria for evaluation and compilation of data and recommend improvements in ex- perimental techniques. They are normally associated with research in the relevant field. The technical scope of NSRDS is indicated by the categories of projects active or being planned: nuclear properties, atomic and molecular properties, solid state properties, thermody- namic and transport properties, chemical kinetics, and colloid and surface properties. Reliable data on the properties of matter and materials is a major foundation of scientific and technical progress. Such important activities as basic scientific research, industrial quality con- trol, development of new materials for building and other technologies, measuring and correcting environmental pollution depend on quality reference data. In NSRDS, the Bureau’s responsibility to support American science, industry, and commerce is vitally fulfilled. Richard W. Roberts, Director III ' Contents Page Chapter I. Introduction 1 Explanation of tables 2 Glossary of abbreviations 2 References 3 Chapter II. Experimental Methods 4 Radiation chemical methods 4 Photochemical methods 6 Chemical methods 7 The Fenton reaction 7 Titanous ion 7 References 8 Chapter III. Kinetic Analysis 9 Direct observation of product formation 9 Direct observation of hydroxyl radical disappearance 10 Competition kinetic measurements 10 Stationary state systems 10 Pulse radiolysis methods 11 Intermittent irradiation 12 References 12 Chapter IV. Physical Properties and Chemical Equilibrium 13 Table 1. Physical properties 14 References 14 Chapter V. Addition Reactions 15 Table 2. Addition reactions 17 References 21 Chapter VI. Hydrogen Abstraction Reactions 22 Table 3. Aliphatic alcohols 23 Table 4. Saturated aliphatic acids 25 Table 5. Polybasic and hydroxy carboxylic acids 27 Table 6. Aliphatic carboxylic esters 28 Table 7. Ethers 29 Table 8. Carbonyl compounds 29 Table 9. Substituted hydrocarbons 30 Table 10. Nitrogen compounds 30 References 31 Chapter VII. Inorganic Electron Transfer Reactions 21 Table 11. Inorganic electron transfer reactions 33 References 37 Chapter VIII. Radical Reactions 38 Table 12. Radical reactions 38 References 39 Chapter IX. Reactions of the Oxide Radical Ion 40 Table 13. Reactions of the oxide radical ion 40 References 42 V Page Chapter X. Reactions With Biological Molecules 43 Amino acids 43 Enzymes 44 Nucleic acid derivatives 45 DNA 46 Table 14. Sulfur and selenium compounds 46 Table 15. Amino acids 47 Table 16. Simple peptides 49 Table
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