1、 SYMPOSIUM ON EXTENSION OF SENSITIVITY FOR DETERMINING VARIOUS CONSTITUENTS IN METALS Presented at the SIXTY-FOURTH ANNUAL MEETING AMERICAN SOCIETY FOR TESTING AND MATERIALS Atlantic City,N.J.,June 28,1961 Reg.U.S.Pat.Off.ASTM Special Technical Publication No.joS Price$3.00;to Members$2.40 Published
2、 by the AMERICAN SOCIETY FOR TESTING AND MATERIALS 1916 Race St.,Philadelphia 3,Pa.BY AMERICAN SOCIETY FOR TESTING AND MATERIALS Library of Congress Catalog Card Number:62-9417 Printed in Baltimore,Md August,1962 FOREWORD In order to review the progress in techniques for determination of trace const
3、ituents in metals,ASTM Committees E-2 on Emission Spectroscopy and E-3 on Chemical Analysis of Metals sponsored this Symposium on Extension of Sensitivity for Determining Various Constituents in Metals.The papers in the symposium were presented on June 28,1961,during the Twentieth and Twenty-fifth S
4、essions of the Sixty-fourth Annual Meeting of the Society at Atlantic City,N.J.The paper Separations in Analysis by J.L.Hague which was presented during the symposium has not been included in this symposium volume.Messrs.L.M.Melnick,U.S.Steel Corp.,and N.E.Gordon,Jr.,Westing-house Electric Corp.,ser
5、ved as Symposium Co-chairmen and presided over the morning and afternoon sessions respectively.NOTE.The Society is not responsible,as a body,for the statements and opinions advanced in this publication.CONTENTS PAGE IntroductionN.E.Gordon,Jr 1 Some Recently Developed Electroanalytical Techniques for
6、 Determination of Traces of MetalsLouis Meites 3 Discussion 19 Radioactivation AnalysisSpecific for Trace Element DeterminationsG.W.Leddicotte 21 Ultratrace Emission SpectroscopyGeorge H.Morrison and R.L.Rupp 44 Discussion 49 Use of the Electron Probe to Measure Low Average But High Local Concentra-
7、tionsL.S.Birks and R.E.Seebold 53 Discussion.56 Extension of Sensitivity in Analysis of Impurities in Solids by Mass Spectrometry C.M.Stevens 58 Discussion 68 STP308-EB/Aug.1962 SYMPOSIUM ON EXTENSION OF SENSITIVITY FOR DETERMINING VARIOUS CONSTITUENTS IN METALS INTRODUCTION BY NEIL E.GORDON,JR.ASTM
8、 Committee E-2 on Emission Spectroscopy and Committee E-3 on Chemical Analysis of Metals jointly sponsored this symposium on Extension of Sensitivity for Determining Various Constituents in Metals.The papers pre-sented dealt with methods for determin-ing extremely small amounts of various elements i
9、n metals,what the limits of detection were for these elements,what obstacles must be overcome to obtain in-creased sensitivity,and what might be done to overcome these obstacles.CJen-eral topics included:(1)separation and Atomic Power Department,Westinghouse Electric Corp.,Pittsburgh,Pa.;Symposium C
10、o-Chairman.concentration techniques,(2)electro-analytical methods,(3)optical emission spectroscopy,(4)X-ray spectroscopy and electron probe analysis,(5)radioactiva-tion analysis,and(6)mass spectrome-try.The formal papers were presented by speakers chosen from men of recognized knowledge of the subje
11、ct in the various fields of testing,and who had extensive experience in practical applications.It is hoped that the efforts of the committee,and the labor of the men who gave gen-erously of their time and energy and made the symposium a success,will have a constructive influence in promoting the int
12、erest of better and more economical methods for the analysis of metals.Copyright 1962 by ASTM Intemational www.astm.org STP308-EB/Aug.1962 SOME RECENTLY DEVELOPED ELECTROANALYTICAL TECHNIQUES FOR DETERMINATION OF TRACES OF METALS BY LOUIS MEITES1 Within the confines of a reasonable length it would b
13、e impossible to describe all of the recent developments in electro-analytical chemistry that may prove to be applicable,or have already been shown to be applicable,to the deter-mination of traces of metallic consti-tuents.This paper is therefore restricted to the description of a few relatively new
14、techniques.Two criteria have been em-ployed in selecting these techniques:one is the probable extent of their utility to the practical analyst,and the other is the degree of interrelationship among the fundamental phenomena that they involve.Though admittedly arbitrary,the second criterion has been
15、imposed for the sake of the simplification and condensation that it permits.The techniques thus selected,and whose conceptual foundations are briefly reviewed here,are square-wave polarog-raphy,mercury-pool voltammetry,ano-dic stripping voltammetry at the mer-cury pool,anodic stripping voltammetry a
16、t a hanging mercury drop electrode,anodic stripping coulometry at controlled potential,and controlled-potential elec-troseparation.For the most part these techniques are so new that nearly all of the research on them has been devoted to the elucidation of their basic theoreti-cal principles;very few detailed practical applications of the majority of them have appeared as yet.Hence special attention 1 Department of Chemistry,Polytechnic In-stitute of Brooklyn,Brooklyn,N.Y.is devoted to outlining
