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COMMITTEE ON NUCLEAR SCIENCE D. A. Bromley, Chairman Yale University Robley D. Evans, Vice Chairman Massachusetts Institute of Technology C. K. Reed, Executive Secretary National Academy of Sciences Martin J. Berger National Bureau of Standards Victor P. Bond Brookhaven National Laboratory Gregory R. Choppin Florida State University W. A. Fowler California Institute of Technology G. C. Phillips Rice University George A. Kolstad U. S. Atomic Energy Commission John McElhinney Naval Research Laboratory Herman Feshbach Massachusetts Institute of Technology F. S. Goulding Lawrence Radiation Laboratory Bernd Kahn National Center for Radiological Health Members-at-Large George Wet her ill University of California Alexander Zucker Oak Ridge National Laboratory Liaison Members Walter S. Rodney National Science Foundation Lewis Slack American Institute of Physics Subcommittee on Radiochemistry Gregory R. Choppin, Chairman Florida State University Herbert M. Clark Rensselaer Polytechnic Institute Raymond Davis, Jr. Brookhaven National Laboratory Bruce Dropesky Los Alamos Scientific Laboratory Rolfe Herber Rutgers University John A. Miskel Lawrence Radiation Laboratory Julian M. Nielsen Pacific Northwest Laboratory G. O. O'Kelley Oak Ridge National Laboratory Andrew F. Stehney Argonne National Laboratory John W. Winchester University of Michigan
UC-4 NAS-NS-3026(Rev.) Radiochemistry of Mercury by Josef Roesmer Westinghouse Astronuclear Laboratory Pittsburgh, Pennsylvania Revised Edition Issuance Date: September 1970 Subcommittee on Radiochemistry National Academy of Sciences-National Research Co JUN 141974 ! IRBARV
Price $3.00, which is the minimum order price for either one, two, or three randomly selected publications in the NAS-NS series. Additional individual copies will be sold in increments of three for $3.00. Available from: National Technical Information Service U. S. Department of Commerce Springfield, Virginia 22151 Printed in the United States of America USAEC Division of Technical Information Extension, Oak Ridge, Tennessee 1970
Foreword The Subcommittee on Radiochemistry is one of a number of subcommittees working under the Committee on Nuclear Science within the National Academy of SciencesâNational Research Council. Its members represent government, industrial, and university laboratories in the areas of nuclear chemistry and analytical chemistry. The Subcommittee has concerned itself with those areas of nuclear science which involve the chemist, such as the collection and distribution of radiochemical procedures, the radiochemical purity of reagents, the place of radiochemistry in college and university programs, and radiochemistry in environmental science. This series of monographs has grown out of the need for compilations of radiochemical information, procedures, and techniques. The Subcommittee has endeavored to present a series that will be of maximum use to the working scientist. Each monograph presents pertinent information required for radiochemical work with an individual element or with a specialized technique. Experts in the particular radiochemical technique have written the monographs. The Atomic Energy Commission has sponsored the printing of the series. The Subcommittee is confident these publications will be useful not only to radiochemists but also to research workers in other fields such as physics, biochemistry, or medicine who wish to use radiochemical techniques to solve specific problems. Gregory R. Choppin, Chairman Subcommittee on Radiochemistry iii
Preface Since the publication of the Radiochemistry of Mercury monograph (NAS-NS-3026) in 1960, the number of papers on mercury analysis, particularly by activation methods, increased at an almost exponential rate. One explanation for the increasing interest in this element might be the need to know details of the path and fate of mercury which has been and still is spread through the biosphere in fungicides, drugs, and chemicals. The revised edition has been completely rewritten. The chapter on nuclear methods of mercury analysis has been greatly enlarged. The number of detailed radiochemical procedures was increased; these procedures were selected with the intention of presenting tried and proven separation methods from matrices ranging from human blood to meteorites, based on many different properties of mercury. The information presented in this edition includes the pertinent literature up to June 1968. I wish to emphasize that no attempt was made to be exhaustive since that is not the purpose of this monograph. Thus it is likely that some important contributions may have been overlooked. I shall be grateful to readers who call such omissions, as well as suggestions and criticisms, to my attention. The management of Westinghouse Astronuclear Laboratory generously provided secretarial and other assistance which is gratefully acknowledged/! also wish to thank Linda Dudash for patiently converting my illegibly written manuscript into the final draft, ready for printing. Josef Roesmer IV
Contents I. GENERAL REVIEWS OF THE INORGANIC, ANALYTICAL, AND RADIOCHEMISTRY 1 OF MERCURY II. ISOTOPES OF MERCURY 2 TABLE I. Mercury isotopes. 2 TABLE II. Decay schemes of the more important mercury isotopes. 5 FIGURE 1. Section of the chart of nuclides around mercury. 6 III. REVIEW OF FEATURES OF MERCURY CHEMISTRY OF CHIEF INTEREST TO 7 RADIOCHEMISTS 1. Metallic Mercury 7 2. Mercury Compounds 10 a. Mercury (I) Compounds IQ b. Mercury (II) Compounds n 3. Complex Mercury Compounds 13 4. Toxicity Ik 5. Insoluble Mercury Compounds 15 6. Coprecipitation Characteristics of Mercury Traces 15 7. Isotopic Exchange Characteristics 18 8. Amalgam Exchange 21 9. Solvent Extraction 23 a. Chelate Extraction Systems 2k b. Ion Association Extraction Systems 27 c. Other Systems 33 10. Ion Exchange Behavior of Mercury 39 a. Anion Exchange Behavior of Chloro Complexes 14.0 b. Anion Exchange Behavior of Bromo Complexes 14.3 c. Anion Exchange Behavior of Fluoro Complexes 14.3 d. Anion Exchange Behavior of Mercury in the Nitrate System k6 e. Anion Exchange Behavior of Mercury in the Tartrate 14.7 System f. Cation Exchange Behavior of Mercury in Hydrochloric kQ and Perchloric Acid Solution g. Cation Exchange Behavior of Mercury (II) in Hydrobromic 51 Acid h. Cation Exchange Behavior of Mercury (II) in Hydro- 52 fluoric Acid
Contents (Continued) i. Cation Exchange of Mercury in the Thiocyanate System 5!+ j. Cation Exchange of Mercury in the Sulfate System 54 k. Cation Exchange Behavior of Mercury on Inorganic Ion 55 Exchangers from Nitrate Solutions 1. Mercury- ipecifie Ion Exchangers 59 11. Chromatographic Behavior of Mercury 6l 12. Volatilization Analysis for Mercury 66 IV. NUCLEAR METHODS OF MERCURY ANALYSIS 69 1. Activation Analysis of Mercury 69 a. Thermal Neutron Activation 69 b. Preparation of Standards 73 c. Sources of Error 73 d. Re-activation Analysis of Mercury 75 e. Fast Neutron Activation Analysis of Mercury 76 f. Photoactivation Analysis of Mercury 80 g. Analysis by Prompt Gamma Ray Spectrometry 81 h. Tabular Survey on Mercury Analysis by Activation 85 2. Other Nuclear Methods 90 a. Neutron Absorptiometry 90 b. Isotopic Dilution 9! c. Backscattering of Beta Radiation 92 3. Counting 93 V. DISSOLUTION METHODS 98 VI. COLLECTION OF DETAILED RADIOCHEMICAL PROCEDURES FOR MERCURY 101 VII. BIBLIOGRAPHY 190 VIII. APPENDIX I. 199