Nucleonics W . S . lyon, E. Ricci,
T
H. H. ROSS,
Analytical Chemistry Division, Oak Ridge National laboratory, Oak Ridge, Tenn.
literature of nucleonics, like that of all science, continues to expandone is tempted to say alarmingly. During our period of ('overage (October 1963 to October 1965) there have appeared well over two thousand publications related to oursubject; to mention each by name, much less t o describe or evaluate the contribution, would transcend reasonable limits of both journal space and reader patience. Fortunately, machine abstracting and computer retrieval programs (such as the Chemical *Ibstracts and the AEC Technical Information Division services) place exhaustive literature survey and bibliographic compilation within reach, if not grasp, of the searcher. Because of this large volume of published material and the availability of bibliographies and abstracting services, we believe that a comprehensive listing of virtually all publications (as has appeared in past years) is unwarranted. Rather instead we have decided to restrict our discussion to items that appear original, novel, or potentially useful; in other words, to make our report a true review. In attempting this we leave ourselves open to considerable criticism, since it is quite possible that an author may find his own favorite publication missing from this discussion; such a discovery often precipitates unpleasant comments concerning the reviewers' capabilities. This is an occupational hazard of critics and reviewers; we recognize and accept it, trusting the reader will understand that the omission of his paper is the exception that proves the rule. Athough each of the three authors has been responqible primarily for his own field of interest, the entire review is the result of an interrelated effort. We have tried to limit our remarks to material published in borne permanent form (journal or book) and readily available. Table I lists recent books, review articles, and bibliographies that are of general interest but not mentioned specifically elsewhere. References to oral presentations, in-house or government reports, and publications in foreign journals of limited American circulation have been held to a minimum. I t was our feeling that for a review such as this to be useful the material discussed should be timely, topical, and available. The present healthy state of research in nucleonics is demonstrated by the listing of over 300 references that met these rather restrictive requirements. HE
RADIOCHEMISTRY
Most of the radiochemistry noted over the last two year period has been of a rather conventional nature. Recent trends appear to be in the areas of machine separations, rapid separations, and the development of separation schemes for a large number of elements. Mathers and Hoelke (192) have developed a technique for performing a five-group separation of radioelements by cation exchange. A semi-automatic machine is used to prepare counting sources for each group. Twelve samples can be analyzed simultaneously, and five counting sources from each sample are obtained and counted in an 8-hour day. During this period, only 1.5 hours of analyst time is required. Amiel and Yellin (4) have developed some very rapid radiochemical separation techniques used in research reactors. Emphasis is placed on instantaneous and continuous flow methods. A number of areas are discussed. A broad range ion-exchange separation technique for 23 elements was investigated by Wester, Brune, and Samsahl (316). Digests of heart and liver tissue were examined and the trace elements separated by the method. Recovery values 5 9 0 % were obtained for all elements except gold and selenium. -4new approach t o the separation of trivalent actinide elements from the lanthanide elements was proposed by Moore (ROO). The actinide elements are extracted as the thiocyanate complexes with tricaprylmethylammonium thiocyanate dissolved in xylene. An advantage of the method is the high single stage separation factors that are possible. Analytical and process applications are discussed. ilnand and La1 (5) have utilized the reaction of water, COS, and zinc to synthesize methane from water for tritium measurements. The reaction takes place in the presence of a ruthenium-on-aluminum oxide catalyst. Quantitative conversion is obtained in a closed system. -1 technique for incorporating water-soluble tracers in hydrocarbons was devised by Tosch (305). An aqueous solution containing the tracer is solubilized or emulsified by a hydrocarbon surfactant solution. This is then added to the hydrocarbon t o be tagged. NUCLEAR METHODS
A method for determining the thickness of foils and films based on the gBe(a,ny) reaction was indicated by
Plaksin, Belyakov, and Starchik (966). The foil t o be measured is interposed betureen a 210Po alpha source and a beryllium oxide target, and the resulting neutrons and y rays are recorded. A group at Argonne Xational Laboratory (161) has developed a miniature portable fluorescent x-ray instrument utilizing radioisotopic sources. It was found that tritium absorbed in zirconium serves as an excellent excitation source for the generation of x-rays in elements requiring 3 t o 12 k.e.v. The quantitative analysis of a number of mixtures is described. A simple experimental procedure was devised by Gardner and Dunn (106) for the simultaneous analysis of hydrogen, carbon, and oxygen in liquids using beta-particle transmission and backscatter gauges. The technique is capable of a high degree of precision. The use of beta backscattering technique for the analysis of metals in pharmaceuticals has been reported by Schiller (263, 264). Methods are described for the determination of six elements in various types of medicaments. Since the materials require no pretreatment, the analysis can be completed with unusual rapidity. Process control applications are summarized. A very promising field has been investigated by Peisach and Poole (217) and by Patterson, Turkevich, and Franzgrote (215) who used Rutherford scattering of alpha particles and protons to analyze surfaces and surface layers. MOSSBAUER ANALYSIS
Although the Jlossbauer effect has been known for some time, analytical applications are just starting to be developed. d number of general reports have appeared on the subject by Goldanskii (116, 117), Fluck (W), and Fluck, Kerler, and Neuwirth (98). A review (227) and the proceedings of a recent conference (123) have also appeared. Sprenkel-Segel and Hanna (286) have utilized the effect for the analysis of iron in stone meteorites. The absorption of resonant gamma rays by 57Fe nuclei in the meteorites produced patterns characteristic of the various iron compounds in the meteorite. The methods used and the geochemical implications are presented. LIQUID SCINTILLATION COUNTING
Although no books dealing specifically with liquid scintillation counting were published during the review period, the excellent compilation by Birks (28) contains a wealth of information about the VOL. 38, NO. 5, APRIL 1966
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technique. The book mainly covers developments up to early 1963; a final chapter continues coverage to later in the year. A general review by Rapkin (236) has 163 references from 1957 through 1963. Some recent developments are noted by Kicoll and Routley (209). Quenching. Various types of quenching phenomena and ways to correct for quenching are being actively studied. A review article b y Peng (218 ) summarizes the available methods of quench correction and evaluates their usefulness for assaying singly, doubly, and triply labeled samples. variation of the internal standard method was introduced by Dobbs (74). A glass rod, having a fused coating of a long-lived isotope, is inserted into the liquid scintillator rather than the usual “spike” of radioactive solution. The technique has the advantages of the internal standard, but eliminates two disadvantages: the sample is not contaminated mith foreign activity and the personal error is eliminated. A “balanced quenching technique” m s proposed by Ross (247). Here, automatic quench correction is obtained by suitably adjusting instrument operating parameters. The method is well suited for routine counting of similar types of samples. Horrocks (141) has used the relative pulse heights of Compton peaks of lorn energy x- and gamma-rays to evaluate quenching. Ross (246) shows how the individual effects of color and chemical quenching can be resolved. 3lany investigators have tried to circumvent the problem of quenching by using the oxygen-flask combustion procedure for total oxidation of samples. Two studies report the effects of oxygen quenching (15, 67). Quenching effects due to aliphatic alcohols (178), organic solvents ( 2 7 4 , and cation counting systems (88, 156) vvere investigated. Two reports concerning the effect of the purification of solvents on the efficiency of liquid scintillators were noted (298, 299). Convenient purification methods are described for dioxane scintillators. Special Counting Techniques. The problem of counting large amounts of aqueous sample in a liquid scintillator is of considerable interest. Patterson and Greene (216) have developed a number of emulsification techniques for counting 3H and 14C. One very interesting formula can accommodate 43% water and count 14C with 57y0 efficiency. Triton X-100 is used to form stable emulsions of water and toluene. Spenke (282) has used AI stearate and SiOz to form stable gelscintillators for aqueous samples of high specific activity. Similarly, Germai (107) utilized Aerosil2491 to form a scintillating gel for counting mineral salts. These techniques appear to be of
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great value and we can expect to see them applied t o a large variety of samples in the future. Horrocks and Studier (142) and Koguchi (211) have shown that radioactive noble gases can be conveniently counted in toluene-based liquid scintillators. This results from the relatively high solubility of these gases in toluene. Their methods are probably applicable to counting a wide variety of gaseous samples. A new technique for low-level I4C counting is described by Freeland (101) in which the sample is converted to methyl benzoate, which is used as the scintillator solvent. A few new liquid scintillator materials were investigated. Goldstein and Lyon (119) studied the properties of 1-methyl-naphthlene and showed that no primary solute is required. I n a continuing program, Heller and Rio (139) studied some anthracene derivatives and Heller (158) investigated substituted distyrylbenzenes. Solutions with efficiencies exceeding those of the best-reported liquid systems are described. Working independently a number of researchers have refined and verified extrapolation methods in liquid scintillation counting for absolute assay of beta emitters. Wangermann (311) and Vaninbroukx and Spernol (307) made their measurements on single photomultiplier systems; Goldstein (118) used the dual detectors of the Packard Tri-Carb system. All investigators report excellent precision and accuracy. The increased use of liquid scintillation counting for low level samples has resulted in many studies concerning the statistical aspects of counting. -in extensive discussion on error analysis was presented by Herberg (140); factors affecting the counting of two isotopes in a mixture are discussed. Natthijssen and Goldzieher (194) investigated the use of chi-square as an index of instrument stability. Chemical errors involved in carbon dating are noted by Leclipteur (175). RADIO-REAGENT METHODS
Chleck and eo-workers have developed a n interesting series of tracer materials termed “kryptonates.” Kryptonates can be made from a wide variety of solid substances by the physical incorporation of radioactive krypton within the material. A series of papers describes the preparation (59), properties (57), and applications (56) of kryptonated solids. The practical aspects of these tracers have been demonstrated by using them for the determination of hydrogen gas (64) and for the determination of the acidity of aqueous solutions and water in methanol (58).
Radioactive hydrogen sulfide has been developed as a radio-reagent for the study of gelatin coatings on textile yarn by Ellis and Barrett (81). The gas is reacted with cupric ions, added to the gelatin, and the distribution of radiation from 35Sis determined. X review of current work on the use of isotopes in the new radio-release analytical technique has appeared (151). The method has been applied to a variety of problems. Gillespie and Richter (108) have determined vanadium quantitatively by release of radioactive silver ion from the metal. Reproducibility a t the 1 ppm. level was +2%, Interferences could be suppressed or eliminated by addition of appropriate complexing agents. Ross and Lyon (248) have described a radio-release method for the determination of trace amounts of sulfur dioxide in the atmosphere. The sample is reacted with l3lIO3- in solution resulting in the liberation of 13112. The evolution of tritium from lithium aluminum tritide has been used in active hydrogen analysis (65, 269). The effects of degassing and sample composition are discussed. RADIOMETRIC METHODS
Few new analytical applications of the isotope exchange technique were noted. Tadmor (297) has combined the method with gas chromatography. I n this way, the use of a radioactivity detector is made possible, without the use of radioactive starting materials. GeCL, SnCL, h c l s , and FeC& were investigated using 36Cllabeled Sil-0-Cel as the solid stationary phase. An extremely selective determination of mercury has been developed by Handley (133). Llercuric (203Hg) di-n-butyl phosphorothioate in CCl4 is contacted with an aqueous sample containing mercury until equilibrium is reached. A simple proportional relationship exists between D H ~and mercury concentration. The standard deviation is about 1% for samples containing lo-’ to lo-* gram of mercury. Qureshi and LIeinke (233) have demonstrated a rapid radiochemical separation of thallium by amalgam exchange that requires about six minutes, and Qureshi (232) has developed a n isotope exchange separation for cobalt. Isotope dilution analysis continues to be extensively employed, particularly in substoichiometric determinations, which are based on the addition of strictly controlled amounts of reagent (chelating, extracting, precipitating) in quantities less than those that stoichiometrically correspond to the element t o be separated. General details are given by Ruzicka and Stary (253). These workers often combine the technique with activation analysis, which has resulted in a number of analytical
methods (265-257, 291, 323). Using substoichiometric techniques, Landgrebe, JlcClendon, and DeVoe (171) have determined trace amounts of cobalt; -4limarin and Perezhogin (1) analyzed for gold in zinc, copper, bismuth, and lead. Conventional isotope dilution procedures were extended into the submicrogram regions using the ring oven method (315). =1 technique involving combination of the isotope dilution method with preparative-scale gas chromatography for the analysis of complex reaction mixtures was developed by Aliprandi, Cacace, and Ciranni ( 2 ) . Radioactive-compound gas chromatography has been diqcussed (for lipids) by Dutton (77), and (for radioactive compounds in general) by Karmen (160). The latter suggests a number of possible applications. The saturation assay technique, a variation of isotope dilution methodology, is discussed by Ekins and Sgherzi (79) and is applied to the micro-assay of vitamin 13-12 in human plasma. -1 great amount of interest is being shown in radiometric titrations, esperially in foreign laboratories. -4 rexien article by 13raun and Tolgyessy (40)concerns the basis of, possibilities in, and the present state of radiometric titrations. Several papers published in less readily available journals, or not available a t all, are covered in a relatively detailed manner. Eighty-seven references published from 1941 through 1963 are included. dlso, three papers concerning the theory (153, 304) and new possibilities (38) of the method appeared. Eraun (37) used complexometric titrations to determine tungstate and sodium ions with EDTA using solid 110.\gI03 as the indicator. Redox and complexometric titrations were investigated by Braun and Koroes (39). Indium and cobalt were determined by complexometric titration (292). llaehl, Cucchiara, and Chleck (187) utilized zinc kryptonate as an indicator in the titration of fluoride; levels as low as 0.001 nimole could be reached. d n interesting radiometric technique reported late in 1963 is the development of a radioactive silver microcoulometer by Busulina and Naldi (46, 47). The coulometer, which uses *lOXg,is suitable for the determination of current quantities as high as 5 x IO-* coulombs with a +2% error. The unit was used in polarographic analysis. A study of the poloragraphy of radioactive substances was carried out by Blazek and Wagnerova (31j . ACTIVATION ANALYSIS
The oustanding characteristic of this period has been the effort that many activation analysts have devoted to the improvement of already established
techniques, and to the investigation of new methods of irradiation, counting, and data processing. As usual, an enormous amount of literature has been published on techniques to analyze specific elements in given matrices. However, many authors have given a “long hard look” a t established methods t o eliminate systematic errors and interferences, thereby improving accuracy and precision. The old nuclear glamour of activation analysis has yielded to a conscientious effort aimed a t raising the standards of the technique to enable it to meet the challenge of other new, spectacular analytical tools. Fields that had seen little development so far, e.g., charged-particle and photoactivation analysis, have been searched by the analyst who, at times, obtained somewhat outstanding results. Some original developments, extensions and applications of known, established methods have also been tried, with various degrees of success. Perhaps, forensic activation analysis, among these developments, has attracted the most attention. The study of powder residues in paraffin casts from the hands of President Kennedy’s assassin by the Oak Ridge group (312), plus the increased efforts directed toward criminal identification by activation analysis of hair, have brought this method to the pages of newspapers and magazines. As a penalty for its popularization activation analysis has suffered from the natural exaggerations and inaccuracies of the public press. Contrastingly, during this period, the first formal textbooks of activation analysis have appeared. Conferences. By far the most important event in the field was the 1965 International Conference on Modern Trends in Activation Analysis (199), which gathered about 500 scientists of 25 countries. After the Conference, some of the attendees participated in a Seminar organized by the Geceral Atomic group. Both events were interestingly reviewed by Glos (114 ) . Among the regular meetings of large organizations (American Chemical Society, American Nuclear Society, etc.) in which a t least several activation analysis papers were presented, the 2nd National Meeting of the Society for Applied Spectroscopy deserves special mention. Held in the fall of 1963, it clearly indicated the trend, mentioned above, towards improvement and expansion. Books. The first textbook, “Radioactivation Analysis,” was published in England in 1963 by Rowen and Gibbons (36). Shortly after, seven members of the Oak Ridge group wrote, and Lyon (186) edited, a “Guide to Activation Analysis.” These two books complement each other remarkably well, though they were written independently
and in two different countries. Xn interesting characteristic of a third book, ‘(Neutron Irradiation and Activation ilnalysis,” by Taylor (302) is the concise mention of numerous practical details. The usefulness of activation analysis in different fields has led authors and editors to devote entire chapters to it in specialized scientific and technological books. Cali (49)took this approach in his book on semiconductor analysis. Biological and nonbiological forensic applications of activation analysis were treated by Smith and Lenihan (279) and by Guinn (126), respectively, in Curry’s book on forensic methods. Guinn (124) and also Fleckenstein, Janke, and llarmier (96) discussed analysis of stable tracers in Roth’s compendium of lectures on isotopes in pharmacology. Bibliographies and Reviews. The existence of very good bibliographies is the main reason why no detailed mention of individual activation analysis methods is made in the present review. Perhaps the most comprehensive bibliographies are those compiled annually by Bock-Werthmann (33); the references can be reached by different entries, such as type of publication (journal article., reports, conferences, books, patents), author, element determined, and matrix. The literature search by Raleigh (236) and the bibliography on fast-neutron and charged-particle activation analysis by Rerton (26) also deserve mention. .-I review with some emphasis on conferences was published by Guinn (126) while survey papers were written by Tilbury and Wahl (303)and by JIaslov (191) on activation with high-energy particles and on gas analysis, respectively. Surveys on analyzers, neutron sources and activation-analysis services (as), and on particle accelerators (132) have also appeared, and may prove useful to the analyst. Tables and Aids. Comprehensive compilations of excitation functions for reactions (n,p), (n,a), (n,2n), (n,np), (n,na), (n,n’), have been published by Liskien and Paulsen (181), by Jessen et al. (154), and by Ewing and NcElroy ( 9 s ) . Cross sections for a great number of these neutron reactions at 14-15 MeV were tabulated by Neuert and Pollehn (206)and by Chatterjee (52, 53), while some average fission-neutron cross sections for threshold reactions were redetermined by Boldeman (34) with fission neutrons from 235U. A series of ORNL reports (196)is updating information on charged-particle cross sections, while JIcArthy and Persiani (195) continued their listing of neutron resonance integrals. Experimental sensitivities for activation analysis, though being of less general value than crosssection data, are of more direct use t o the analyst and keep attracting his VOL. 38, NO. 5, APRIL 1966
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attention. Kusaka, Tsuji, and Adachi determined sensitivities for 14 JleV neutrons (166), and also for a low level neutron source (166), while reactorslow-neutron sensitivities were obtained by Yule (320). Also, Ricci and Hahn (244) studied detection limits for a number of reactions induced by 3He ions in low-Z elements. Some authors have been inspired by Heath’s catalog of gamma spectra (137) and have published specialized and comprehensive catalogues of their own. Strain and Ross (295) in the U.S., Aude and Laverlochere (13) in France and Kusaka et al. (167) in Japan have compiled experimental gamma-spectra of nuclides produced by 14 hleT‘ neutron irradiation; in all cases, sensitivities for activation analysis can be inferred from the graphs. Considerable effort was also expended by Girardi, Guzzi, and Pauly (If 2 ) to compile calculated sensitivities and specific activities for most elements in a handbook; the values are given for several thermal fluxes and different irradiation and decay times. STUDY AND CORRECTION OF SYSTEMATIC ERRORS IN ACTIVATION ANALYSIS
Cali and Keiner (50) have evaluated the most frequent activation analysis errors by the propagation method and confirmed their results by experiment. Lyon, Eldridge, and Crowther (186) and Low (182) studied artifacts related to gamma-spectral shapes and deadtime errors, respectively, encountered in counting. The need for biological analytical standards was pointed out by Bowen (35)) who initiated a program to produce them. Generator Neutrons. A number of companies started selling 14-MeV neutron generators a t relatively low prices during this period. This fact, plus the increasing interest in oxygen analysis, caused a considerable expansion of fast neutron techniques. A healthy concern for accuracy and precision in the use of neutron generators accompanied these developments. Xnders (6) suggested the measurement of thermalized-neutron fluxes by a gold wire inserted in the sample axis to minimize the self-shielding error. He and Briden (7, 8) also studied oxygen analysis by the reaction ’60(n,p)W with fast neutrons; they analyzed the self-shielding error and the interference of 16N recoiling from air, and proved that spinning the samples around their axes improves considerably analytical precision. However, local flux variations could still affect sample and standard differently; Matt and Orange (204) studied thoroughly these variations and achieved almost statistical standard deviations hy rotating sample and standard around the generator axis. 254 R
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Finally Vood and Pasztor (318) are developing a system that combines both movements; they show that, in general, activation analysis has advantages over both vacuum and inert-gas-fusion analysis for oxygen. The increasing sophistication of the irradiation port causes distortion of the generator neutron spectrum. The importance of this effect in single-comparator activation analysis was pointed out by Ricci (242) who gave an approximate method to calculate 14-3leV neutron-generator spectra. An experimental comparison of several fastneutron flux measurement techniques was made by Iddings (146). Comparisons of behavior and neutron yields for different tritium and deuterium targets were respectively performed by Cambou and Reme (51) and by Large and Hill (1‘72). Reactor Neutrons. Analysts have tried to enhance the sensitivity of activation analysis, one of its best characteristics, by using higher and higher reactor fluxes. This has brought some new problems, such as target burnup and new types of interferences. Ricci and Dyer ($48) studied the second-order interference error in detail and prepared a number of graphs to correct for it a t different fluxes. Tables to correct for other errors at high fluxes were calculated by Jlaslov (190). The self-shielding error, common to all fluxes, was considered by Reynolds and ;\lullins (241), and by Kamemoto and Yamagishi (158) mho derived semi-empirical correction procedures. Finally, the well recognized difficulties of reactor activation analysis for several elements by using a single comparator (111) or no comparator at all (absolute method) (110)were carefully analyzed by Girardi, Guzzi, and Pauly who derived practical conclusions. ’
N E W DEVELOPMENTS I N ACTIVATION METHODS
Charged Particles and Gamma Rays. The extremely high sensitivities of charged-particle activation have encouraged the analyst to overcome t h e problem posed by the dependence of the cross section on the range of the particle in the sample. Ricci and Hahn (244) developed a general mathematical treatment that solves this problem by defining an average cross section, while Engelmann and Cabane (86, 8’7) defined an “equivalent thickness” traversed by the particles, with the same purpose. The former used 3He ions and the latter, CY particles and protons, in the activation of low-2 elements. Pierce, Peck, and Henry (222) counted prompt gamma rays from charged-particle reactions in analyses for which interferences, the main drawback of this method, could be circumvented.
Photoactivation analysis has attracted the analyst because of its good sensitivity and its resemblance, in practice, with neutron activation. SchFeikert and Albert (267) made an experimental survey of detection limits for 24 elements. Kochevanov and Kuznetsov (162) determined oxygen in several matrices while Engelmann (85) and Berezin et al. (25) developed methods for several low-Z elements and used the thresholds of the reactions to discriminate against interferences. Finally, photoneutrons produced in beryllium and deuterium by highenergy gamma rays from the decay of certain nuclides were used by Amiel (3) to determine some elements selectively. Neutrons. The analytical possibilities of reactor neutrons have not been exhausted yet. Yule and Guinn (321) used a pulsed reactor to enhance analytical sensitivities, while these authors and Lukens (S22) showed that in some cases, reactor fast neutrons have advantages over thermal neutrons. Inelastic scattering of reactor neutrons and gamma rays, as well as other neutron reactions, were used by Kramer and Wahl (f64) to produce isomers useful for activation analysis. Secondary recoil protons were used by Aumann and Born (14) and by Hunt and Miller (145)to determine I8O in water by reactor irradiation, mhile Fabbri, Lazzarini, and Sangiust (94) used recoil deuterons to determine deuterium in organic compounds by the same method. The thermal neutron flux depression caused by lOB was used by Matteson, Waldbillig, and Peterson (193) to determine boron isotope effects and by Spenke, Cless-Bernert, and Karlik (283) to analyze for boron by neutron activation depression, ironically a conimonly undesirable effect. Sonreactor neutrons from a number of accelerators and nuclear reactions were used by StecIe (293) to show that optimal and selrctive activation conditions can be established by adequate choice of neutron energies. Chemistry. Although there is a definite trend towards non-destructive instrumental activation analysis, i t is clear t h a t some problems cannot be solved without chemistry. Interesting innovations tend to make destructive activation analysis simpler, cleaner, more accurate and precise, A number of papers were published by Ruzicka, Stary, and Zeman in Talanta and A n a l . Chim Acta (1963-65) on individual uses of the substoichiometric separations ( I 76, 254) first developed in 1963. Suzuki and Kudo (296) proposed an ingenious combination of isotope diIution with acactivation analysis; remarkably, the method is immune to nuclear-reaction interferences, and it requires neither comparators nor absolute determina-
tions. Complex chemical procedures were developed by Ross (249),Samsahl, Brune, and Wester (262), and Aubouin et al. (12) to separate large numbers of elements (30 to 62) from activated matrices. Girardi et al. (109) automated chemical separations t o make them as simple, reliable, and attractive as non-destructive procedures. The selectivity of controlled potential electrodeposition was used by Mark and Berlandi (189) to separate elements before irradiation, with great improvement of sensitivity. Kamemoto and Yamagishi (159) proposed the further activation of the carrier, Le., re-activation analysis, to determine yields of chemical separations. Biological compounds which lack activatable elements were brought to analysis by Steim and Benson (294),who irradiated chromatograms of adequate derivatives. APPLICATIONS OF ACTIVATION ANALYSIS
It is not within the scope of this review t o list the innumerable applications of activation analysis. However, applications to oxygen analysis and forensic chemistry have influenced the development of the method itself and deserve special attention. Oxygen Analysis. The production of ultra-high purity materials created thf. need for extremely sensitive yet very accurate methods for oxygen analysis. The sharp interest in analysis for microamounts of oxygen and other low-Z elements is responsible for a number of the developments mentioned above ( 7 , 8, 25, 85, 86, 162, 215, 244,318). Rietallurgists are concerned with surface oxygen contamination, Le., the oxygen or oxide layer which covers most low-Z elements, even when kept in the vacuum; analysts also must know how this layer affects determinations of oxygen present inside the sample. Saito et al. (259) studied this problem in the analysis of pure silicon and determined the oxygen layer by successive grinding and counting. Leonhardt (177) measured surface oxygen by the reaction sequence ELi(n,cu)3H, 160(t,n)l*F. The surface contamination of beryllium by oxygen, carbon, and nitrogen was determined by Blake, Martin, and Morgan (SO), who also studied the effects of etching, while Condit and Holt (66) used protons to study oxygen diffusion and oxide inclusions in metal samples. Forensic Chemistry. The high sensitivity of activation analysis, and the possibility of non-destructive testing of samples valuable as court evidence, make this method particularly attractive to forensic science. T h e first acceptance of activation analytical evidence in court in the U.S. was reported by Pro, Schlesinger, and Cohan (229) ; they analyzed samples of soil to identify illicit distilleries. Baum-
gaertner, Staerk, and Schoentag (22) and Ruch, Guinn, and Pinker (252) found interesting results in analysis of gunpowder residues. The latter authors with Buchanan and Bellanca (251), and also Bate et al. (21), published preliminary data on a number of materials of forensic interest including inks, plastics, and automobile grease, tire rubber, and paint, while the reproducibility of results from car paints was studied by Ryttenbach (S19). Perhaps the most intriguing subject in forensic activation is hair analysis. I t s extremely attractive aim is the identification of criminals by analysis of single hairs left a t the scene of the crime. Perkons and Jervis (221) studied correlations between elements present in 1100 samples of hair of people grouped by different criteria (family, environment, occupation, etc.). Lima, Shibata, and Xtalla (180) investigated similar problems, while Bate and Dyer (19) studied the influence of sample washing in the determination of trace elements in hair. However, more research will have t o be done before a criminal can be identified “beyond reasonable doubt.’’ The state of the art, in this respect, is perhaps best presented by Bate and Dyer, in their article. Though they recognize the great promise of the technique, they also believe, as Bate and Pro (20) did in relation to drug identification, that a detailed statistical correlation study should be made, before final conclusions are drawn. During an unscheduled talk a t the Texas Conference (199), Coleman mentioned that such a study has already been initiated in England. T h e Unusual. We should not conclude without reporting two singular applications. Goel (115) provided an interesting example of “cosmic activation analysis” by measuring 3T!l produced in meteorites by cosmic radiation. I n a quite different study, two men were analyzed, in vivo, by Anderson et al. (9) for sodium and chlorine. I n these experiments the subjects were irradiated with a permissible dose of 14-MeV neutrons rind measured in a whole-body counter. INSTRUMENTATION FOR NUCLEAR MEASUREMENT
Semi-Conductor Devices. The most promising and exciting innovation within the past several years has been, of course, t h e lithium-drifted germanium detector for measurement of y rays. Since the first publication describing successful drifting of germanium by Freck and Wakefield (loo), literally hundreds of topical reports, oral presentations, and literature publications have appeared. As is always the case, many of these contributions represent duplication of previously re-
ported data, or incremental advances in technology. Semi-conductor counters are discussed in Dearnaley and S o r t h rop (69),as well as in the second edition of Price (228), but the primary source of information is journal literature. Several 1964 reviews in Kucleonics (55, 113, 120) present the state of the art a t that time. The Ninth Scintillation and Semiconductor Counter Symposium provided an opportunity for scientists primarily engaged in the study and improvement of these devices to discuss progress. These proceedings are recorded (210)in the I E E E Transactions on Nuclear Science. Tavendale and Ewan probably lead the field in publications; their early progress was reported in December 1963 (301). Improvenients were noted in November 1964) (91), at which time efficiency curves were given for a 5 cmz X 8 mm. detector. Later papers discuss construction and performance of larger detectors (SOO), and describe a 16 cm3 device (188) with resolutions (fn hm) of 3.3 and 4.8 k.e.v. at y-ray energies 122 and 1,333 k.e.v. This detector, produced by the coaxial method of lithium drift has an efficiency coiiiparable to that of a 1 in. X 1 in. ?;a1 scintillator. DeLyser, Ziemba, and Van Antlverp (70) have described their fabrication techniques for thin n indow detectors. They ha1 e collected data concerning detector response to various nuclear particles, as well as information on energy requirements for electronhole pair formation in silicon and germanium. Fox, Williams, and Toth (99) compare Ge(Li) and KaI(T1) spectrometers and demonstrate use of the germanium detector as both a single and sum spectrometer. I n France, Stab et al. (285) have worked out methods of preparation and storage of drifted detectors. Ge(Li) detectors are beginning to become available commercially; consequently, greater and more varied use of them as spectrometers should be espected. Originally developed by physicists and/or persons primarily associated with physics, the germanium detector has so far mainly been used in pure science as opposed to applied problems. Ewan and Tavendale (92) have measured high energy gamma rays, and Shirley (276) has performed coincidence and hlossbauer spectroscopy, as well as gamma spectrum analysis. Recently, Prussin, Harris, and Hollander (231) described a Ge(Li) spectrometer permanently assembled in liquid nitrogen in a vacuum system. This assembly has been used for non-destructive neutron activation analysis of impurities in aluminum. Scintillation Counters. Birks’s (28) comprehensive survey of scintillation counting exhaustively covers solid, liquid, and gaseous scintillators up VOL. 38, NO. 5, APRIL 1966
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through 1963. T h e enlarged, revised, and invaluable Siegbahn compilation (277) is a reference must for any serious practitioner of nuclear spectroscopy. Much the same may be said about the second edition of the y Ray Spectrum Catalog of Heath (137). For those interested in high sensitivity or low level counting, the book by W a t t and Ramsden (313) will be of interest. An evaluation of the new bi-alkaliphotocathode photomultiplier has been published by Krall (163); this tube is especially designed for scintillation counting. The problem of stabilization of y spectrometers against zero and gaia drifts is the subject of a paper by Dudley and Scarpatetti (75). Stability of peak channel numbers to 0.1 percent is possible. For the novice an excellent introduction to nultichannel analyzers has been written by Stanford (289); the article is well referenced. Refinements in sophistication of electronics and a general lowering of prices for “standard” analyzer systems measure the progress in gamma-ray spectrometry. The use of computers in conjunction with ganiina measurement is mentioned elsewhere. De Soete and Hoste have described a Compton compensated gamma spectrometer (71, 72) that permits considerable sharpening of gamma photopeaks. The Compton background seen in a large plastic scintillator is subtracted from the output of a YaI(T1) detector. A liquid scintillation counter that uses anticoincidence shielding of plastic has been used by Sprokel (287) to reduce background in counting low energy beta emitters. Lam and Wainerdi (169) have used a CsI-PTaI dual crystal Compton reduction spectrometer in which the 3 in. X 3 in. NaI(T1) detector is surrounded by a 5 in. X 5 in. CsI(T1) crystal. h sum coincidence spectrometer has been applied to activation analysis problems by Wahlgren, King, and Hines (309). O’Kelley (214) describes a multiparameter pulse-height analyzer that uses two KaI(T1) detectors and a 20,000 word ferrite-core memory pulse analyzer. X-Y “maps” of the memory contents and conventional counts us. channel number plots of a selective X or Y plane are possible. The system provides for rapid readout onto magnetic tape. The group using this expensive and sophisticated set-up has been primarily studying decay schemes and meassing half-lives. Perkins (219, 22’0) has combined the techniques of D e Soete and O’Kelley in an anticoincidence shielded-multidimensional gamma-ray spectrometer. Two large SaI(T1) detectors are surrounded by a n anti-coincidence ring of N a I or plastic scintillator. Events not totally absorbed in the two facing NaI(T1) de-
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tectors are cancelled by the third anticoincidence detector. This assembly has been successfully used in a number of non-destructive analytical applications: fallout measurements, health physics monitoring of water, soil, etc., and activation analysis of a number of matrix materials, e.g., sea water and wheat for up to 13 different trace contaminants. The technique represents an exciting and useful new application; major drawback is the expense and complexity of the equipment. I n proportional counter spectrometry, an interesting improvement has been suggested by Hansen et al. (136) who have operated a gas filled counter in coincidence with an escaping fluorescent x-ray for use in low energy xand gamma-ray spectroscopy. COMPUTER APPLICATIONS
The application of computer routines and data processing techniques, though increasing rapidly in nuclear and radiochemistry, remains primarily an individualistic type effort. Thus, many experimenters have written their own codes or modified others; the result is a highly fragmented literature with most written communication in the form of topical reports rather than journal publications. Communication through personal contact a t conferences appears to be a major source of active new information; fortunately, the proceedings of the 1964 Conference on Automatic Acquisition and Reduction of Kuclear Data have been preserved in permanent form (23). The question of on-line computers versus fixed-wire analyzers was thoroughly aired by a number of speakers, primarily Fiebiger, fileadom, and Hall and others in discussion. Much of the technology presented is perhaps too sophisticated for present analytical chemistry applications but, the history of the field shows analytical application to be only a few years behind research. I n an earlier review, Spinrad (284) also discussed the possible replacement of multichannel analyzer systems by digital computers. Computers in Radiochemistry. Spratt (285) writing in Fortran IV language has a program to calculate disintegration rates and quench corrections in liquid scintillation counting. Efficiencies of different kinds of scintillation crystals for y rays have been calculated by Snyder and Gyorey (280). A number of programs have been written to unscramble y-ray spectra; as mentioned above, most of these have appeared as reports and as such will not be listed here. Kicholson, Schlosser, and Brauer (208) describe a weighted least squares method for estimation of contributions of radionuclides in multicomponent pulse height spectra. Blackburn (29) has a program that will handle 20 spectra. Freeman and Mani
(102) describe a simple method for analysis of y-ray spectra using an IBJ1 7090. A least squares resolution program developed by Schonfeld (266) has been tested on a variety of radioactive samples. The method takes into account errors due to contributions from each component in a mixture and permits decay measurement of spectra over periods of time. Emery et aZ. (84) have evaluated three computer programs with respect to the capabilities of both library and composite sample, performance, time of running, and cost. Computers in Activation Analysis. A number of applications have been reported in activation analysis, since the large number of samples handled make automatic d a t a handling quite profitable. Shideler (275) has described a system for interfacing a teletypewriter to nuclear systenis for use in computer coupled activation analysis; data from a variety of investigators requiring quite different treatment can be handled. A general purpose digital computer has been used as both memory and control unit in an on-line data acquisition system developed by Cohan (64). Computer programs were developed by Isenhour, Morrison, and Evans (149, 150) to determine the optimum times of irradiation and decay in mono- and multi-elemental activation analysis. Salmon (261)described his program a t the Salzburg Conference; it has been applied to activation analysis problems as has that of Aubouin et al. ( 1 2 ) . Salmon has analyzed for C1, l I n , Cu, and Ka. JIunzel (205) a t the same conference described two calculational programs, one that analyzes decay curves containing five components, and the second that computes activity percentages of up to 5 components in a gamma spectrum. The Texas A & AI system for automated and computed programmed activation analysis (310) has been tested with a variety of known and unknown samples. Such a system would seem to offer routine activation analysis for a reasonable financial and manpower expenditure. At the Salzburg meeting, the question of on-line us. off-line data handling was discussed (48)by Butler. Coniputer routines have been written for reduction of neutron activation foil data (32’5), analysis of lubricating oils ( 1 4 4 , and meteorites (62). It thus is apparent that machine processing of analytical data is immediately upon us, and one can anticipate increased interest in use of computer techniques in the future. ABSOLUTE MEASUREMENT OF RADIOACTIVITY
Reporting on a panel discussion concerned with radioactivity assay, Lyon (184) has indicated some of the prob-
lems presently hampering users of radioactive standards. Applications of the method of 4ap-y coincidence counting have been reported by a number of workers; for cy-y coincidence counting on 24l.-lm, Japanese investigators (260) have used a silicon p-n junction type semi-conductor detector to measure cy particles and a NaI('I'1) detector to count y rays. Several groups have attempted to improve measurement techniques in y-ray spectroscopy. I n a series of five papers discussing absolute standardizations with SaI(T1) crystals, Brinkman and coworkers (41-45) describe a number of techniques for determining absolute disintegration rates through measurement of peak areas of single and sum photopeaks in y-ray spectra. Although interesting, much of the material has only limited practical usefulness. For those attempting t o count large aqueous samples by spectrometry, Verheijke (308) has calculated efficiencies of XaI(T1) crystals for such samples. Redon et al. (237) have measured absolute photopeak efficiencies for welltype XaI(T1) crystals; the efficiencies are given as a function of well depth. Perhaps the most useful tabulation of photopeak efficiencies t o appear is that of Green and Finn (122) who consider three different crystal sizes: 8 in. X 4 in., 5 in. x 4 in., and 3 in. X 3 in. Their data are compared to those of earlier experimenters. Croft, Pct,tersson, and Hamilton (68) have made a very precise measurement of the I< conversion coefficient of the 279-k.e.v. y-ray transition following decay of 2O3Hg, employing a coincidence technique with a magnetic lens spectrometer. They suggest that their value, E K = 0.162 + 0.003, could be used as a st,andard for such measurements. Another measurement of importance to analytical radiochemists is the number of 0.662-k.e.v. y-ray quanta per disintegration in the decay of the 137Ua daughter of 137Cs; Merritt and Taylor (198) have determined this value to be 0.857 i 0.009. For up to date inforination concerning other y-ray branchings, half-lives, and similar nuclear constants, the reader is referred to Kuclenr D a t a Sheets (314). Of particular interest is the new journal, Nuclear Data, edited by E;.Way. Two interesting papers concerned with special measurement techniques are those of Joshi, Lewis, and Smith (167) and Eulitz (90); the former use internal source scintillator spectrometry to determine L/Ii and K/U+ ratios and beta spectral shapes, while in the latter a sericitive method for counting tritium is described. Additional inforination concerning tritium counting is supplied in another article on that subject (147). Lukens and Lasch (183) propose the
use of Cerenkov counters for counting the high energy betas from 16N in the presence of a high background of y rays and low energy betas. Such counting techniques have been applied in the determination of oxygen by activation analysis. The direct non-destructive determination of *Wf through measurement of its prompt y rays from spontaneous fission has been demonstrated by Moore and Eldridge (201). Two 4a beta spectrometers have been described that should be of interest for those engaged primarily in research. The techniques employed are probably too laborious and expensive (in each method the sample is placed directly on the detector) for routine use. Snyder and Beard (281) sandwich a thin liquid source between two specially prepared plastic scintillators. Beta and conversion electron spectra are both shown; in addition, Fermi plots were made. Two lithium-drifted silicon solid state detectors were used in a 4a counting arrangement by Reynolds and Persson (239). 143Pr was measured a t 10,000 ohm-cm resistively and 1500 volts bias; 32P was measured at 13,000 ohm.cm and 1800 volts bias. -4 group in Canada (168) have studied back-scattering and self-absorption of beta particles in - 2 r geometries. BURNUP MEASUREMENT
Several publications of interest have recently appeared concerning the general subject of flux monitoring and burnup determinations. H a r t et al. (134) have surveyed five different niethods of burnup measurement: 23iUdepletion, cobalt monitoring, lSiCs production, plutonium production, and calorimetry. Within f5%, all gave agreement with the best value. Diggle and Blackadder (73) have described fuel element scanning using ?;a1 (Tl) ganimaray spectrometry. Gross gamma measurements and measurement of 140Laby the (y,n) reaction on deuterium have been used by at least one reactor operator to monitor fuel elements (18). Considerable improvement in direct nondestructive gamma-ray spectroscopy for burnup analysis can be anticipated as more use is made of germanium detectors. Finally, it should be mentioned t h a t the ASTM has approved two standard methods for atom percent fission in uranium fuel (10). NEW TECHNIQUES
Physicists in Israel (24) have used capture y rays (produced by reactor neutrons on metals) to escite target nuclei of other elements to energies between 6 and 10 MeV. When the energy of the capture y-ray line happens to lie close to a suitable resonance level in a target nuclei, a peak is observed in the spectrum of gamma rays
obtained from the target. McIntyre and Randall (197) have continued these investigations by studying reactions involving a number of elements. Some twenty elements have been observed to show this effect, which occurs predominately a t or near closed shell nuclei. Consequently, Pb, Hg, Bi, and Cu have been studied. The method would seem to offer promise for analytical determinations since the energy resolution is quite high. *Another potentially useful technique comes also from physics research, this time in Sweden. Hagstrom, Nordling, and Siegbahn (128) have called attention to the method of electron spectroscopy for elemental determinations, as well as chemical valence state elucidation. Radiation from an x-ray tube is used to eject electrons froni a sample. The photoelectron spectrum is analyzed magnetically in a high resolution double focusing beta-ray spectrometer; each element gives a contribution characteristic of itself and the spectral distribution of exiting radiation. These authors describe atomic ratio measurements of surfaces in NaF, S i c , and Na2C03 (128) with accuracy of about 5%. Valence states may also be distinguished in certain instances; peak shifts were observed for sulfur in three different compounds (127). The method appears to warrant consideration by analytical chemists.
Table 1.
Books, Bibliographies, and General Reviews
Advances and Surveys. (82, 8S, 95, 105, 250, 271, 272) General Texts of Nuclear Chemistry, Radiochemistry, Nuclear Physics (60,103,104, 130, 131, 136, 155, 207, 212, 245) A. Radiochemistry 1. of single elements Tc-(63, 226, 268) Rh-( 61) Po-1189'1
P~-ia~sj
At-( 11, 78) Th-(258) Pm-(76) Cr- (233) 2. of element groups transuraninm-(16, 17) actinides-(202) others-(270) 3. Yurvey-(131) B. Radiochemical techniques 1. generaL(d30, 290) 2. tracer applications a. general-(148, 152, 179, 240, 273, 317) b. chemical analysis-(149, 170, 203, 306)
e. organic chemistry-(121) d. hydrology and soik(27) e. biology and medicine-( 274, 324 1 f. industrial-(%, 80,89,179,224, 234, 235, 267, 278)
VOL. 38, NO. 5, APRIL 1966
e
257 R
LITERATURE CITED
(1) Alimarin, I. P., Perezhogin, G. A., Zh. Analit. Khim. 20, 48 (1965).
(2) Aliprandi, B., Cacace, F., Ciranni, G. ANAL.CHEM.36, 2445 (1964). (3) Amiel, S., in “Radiochemical Methods of Analysis,” p. 101, 1-01. 11, Proceedings of Symposium, Salzburg, October 19-23, 1964, Intern. At. Energy Agency, Salzburg, 1965. (4) Amiel, S., Yellin, E., in “ChemistryResearch and Chemical Techniques Based on Research Reactors,’] pp. 83-93, Vienna, International Atomic Energy Agency, 1963. (5) Anand, J . S., Lal, D., A-ature 201, 775 ( 1964). (6) Anders, 0. U.,AKAL.CHEM.36, 564 (1964). (7) Anders, 0. U.,Briden, D. W.,A x . 4 ~ . CHEM.36, 287 (1964). (8) Ibid., 37, 530 (1965). (9) Anderson, J., Osborn, S. B., Tomlinson, R. JV, S., Yewton, D., Itundo, J., Salmon, L., Smith, J. FY.,Lancet 2, 1201 (1964). (10) ASTb1, “1965 Book of ASTN Standards,” pp. 516-539, 664-669, 1965. (11) Aten, A. H. IT., Advan. Inorgn. Chem. Radaochem. 6, 207 (1964). (12) Aubouin, G., Diebolt, J., Junod, E., Laverlochere, J., in “Modern Trends in Activation,” Proceedings of 1965 International Conference, College Station, Texas, 1966. 13) Aude, G., Laverlochere, J., Commisariat a L’Energie Atomique, Rept. SAR-G-63-38 (1963). 14) Aumann, 11. C., Born, H. J., JYaturwissenschaften 51, S o . 7 , l59A (1964). 15) Baggett, B., Presson, T. L., Presson, J. B., Coffey, J. C., Anal. Bzochem. 10, 367 (1965). 16) Bagnall, K. W.>Chem. Brit. 1 , 143 (1965). (17) Bagnall, K . W.,Sci. Progr. 52, 66 (1964) . (18) Ball, K.ll.,Batch, 11.L., ,Yucleonics 23, No. 3, 72 (1965). (19) Bate, L. C., Dyer, F. F., Sucleonics 23, No. 10, 74 (1965). (20) Bate, L. C., Pro, RI. J., Intern. J . A p p l . Radration Isotopes 15, 111 (1964). (21) Bate, L. C., Emery, J. F., Leddicotte, G. W.,Lyon, JY,S., Pro, hI. J., Intern. J . A p p l . Radiation Isotopes 14, 549 (1963). (22) Baumgaertner, F., Staerk, H., Schoentag, A., 2. Anal. Chem. 197, 424 (1963). (23) Beckurts, K. H., Glaser, W., Kruger, G., eds., “Automatic Acquisition and Reduction of Suclear Data,” pp. 53, 132, 141, Gesellschaft f. Kernforchung, Karlsruhe, 1064. (24) Ben-David, G., Huebschmann, B., Phys. Letters 3, 87 (1962). (25) Berezin, A. K.,, Vitozhentg, G. Ch., Sulin, \-. T’., Shornikov, S.I., in “Radiochemical Rlethods of Analysis,” p. 361, To1. I, Proceedings of Symposium, Salzburg, October 19-23, 1964, Intern. At. Energy Agency, Salzburg, 1965. (26) Berton, AI., Commisariat A L’Energie Atomique, Rept. CEA-Bib-50 (1964). (27) “Bibliography on Radioisotope Applications in Hydrology and Soil lloisture bleasurements,” Union of South Africa, Atomic Energy Board, Pretoria, 1962. (28) Birks, J. B., “The Theory and Practice of Scintillation Counting,” Pergamon Press, IlIacMillan Co., New York (1964). (29) Blackburn, J. -4.,AKAL.C H E h f . 37, 1000 (1965). 258 R
ANALYTICAL CHEMISTRY
(30) Blake, K . R., Martin, T. C., Morgan, I. L., in “RIodern Trends in Activation Analysis,” Proceedings of 1965 International Conference, College Station, Texas, 1966. (31) Blazek, J., Ragnerova, D. Rl., Collection Czech. Chem. Commun. 29, 915 (1964). (32) Blondel, A., Colas, R., Cornuet, R., “Industrial Applications of RadioElements,” Editions Eyrolles and Editions Gauthier-Tillars, 1962. (33) Bock-Werthmann, W.,AED Information Service, Repts. AED-C-14-02 (1963) and AED-C-14-03 (1964). (34) Boldeman, J. W., J . AYuclearEnergy 18, 417 (1964). (35) Bowen, H. J . Ll.,in “RIodern Trends in Activation Analysis,” Proceedings of 1965 International Conference, College Station, Texas, 1966. (36) Bowen, H. J. JI., Gibbons, D., “Radioactivation Analysis,” Oxford Univerbity Press, London, England (1963). (37) Braiin, T., Acta Chim. Acad. Sci. Hung. 41, 199 (1964). (38) Braun, T., Chim. Anal. 4 6 , 6 1 (1964). (39) Braun, T., Koroes. E., Vienna. International Atomic Energy Agency, Premint SM-55/17 119641. (46) Braun, T.’, Tolgyessy, J., Talanta 11, 1277 11964’1. (41) Brinkman, G. A., Aten, A . H. W., Jr., Intern. J . .4ppl. Radiation Isotopes 16, 177 (1965). (42) Ibid., 14, 503 (1963). 143) Brinkman. G. A , . Aten. A. H. IT., T’eenboer, J: Th., ’Intern. J . Appl: Radiation Isotopes 14, 153 (1963). (44) Ibid., p. 433. (45) Ibid., 16, 15 (1965). (46) Busiilina, I,., Naldi> E., Ric. Sci., Rend. 3, 807 (1963). (47) Ibid., p. 813. (48) Butler, J. P., in “Radiochemical Methods of Analysis,” pp. 139 and 193, Vol. 11, Proceedings of Symposium, Salzbiirg, October 19-23, 1964, Intern. At. Energy Agency, Salzburg, 1965. (49) Cali, J. P., in “Trace Analysis of Semiconductor Alaterials,” Cali, J. P., ed., pp. 6-140, JIacJIillan Co., Pergamon Press, 1965. (50) Cali, J. P., Weiner, J. R., in “AIodern Trends in .4ctivation Analysis,” Proceedings of 1965 International Conference. College. Station. Texas. 1966. (51) Cambou, p.: Reme, H., j. Phys. (Parts) Suppl. 25, No. 3, 61 (1964). (52) Chatterjee, A., ,Yucleonics 22, No. 8, 108 (1964). (53) Ibzd., 23, No. 8, 112 (1965). (54) Chleck, D., T’ienna, International Atomic Energy Agency, Preprint SM55/41 (1964). ( 5 5 ) Chleck, D., Broiisaides, F. J., Ziegler, C. A., Intern. J . Appl. Radiatzon Isotopes 15, 627 (1064). (56) Chleck, D.,Cucchiara, O., Intern. J . A p p l . IL‘adiatzonIsotopes 14, 599 (1963). ( 5 7 ) Chleck, I)., Jlaehl, R., Intern. J . Appl. Radzatzon Isotopes 14, 593 (1963). (58) Chleck, I)., Llaehl, R., Cucchiara, O., Chemzst-Analyst 54, 84 (1965). (59) Chleck, I).>llaehl, R., Cucchiara, O., Carnevale, E., Intern. J . B p p l . Radiatzon Isotopes 14, 581 (1963). (60) Choppin, G. R., “Siuclei and Radioactivity,” W.A. Benjamin, New York, 1964. (61) Choppin, G. R., Armstrong, J. C., “The Radiochemistry of Rhodium,” N.A.S.-K.R.C., Washington, D. C., 1963. (62) Choy, S. C., Schmitt, R. A., .\htbLre 205, 758 (1965). (63) Cobble, J. W.,Treatise Anal. Chem. 6 , 407 (1964).
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Polarographic Theory, Instrumentation, and Methodology David N. Hurne, Massachusetts Institute of Technology, Cambridge, Mass.
T
review summarizes the literature in the period November 1963 through December 1965 and follows very closely the pattern and organization of the previous review (97). I n 1964 the subject was divided, and papers on newer electroanalytical techniques which could be considered polarographic only by adopting a very broad definition of the term-electrode processes, electrode kinet>ics, and many aspects of electrochemical theory-were treated in a separate review by W. H. Reinmuth (180). This approach showed many advantages and is continued in the present set of reviews. As usual, no attempt is made to discuss papers on applications unless they embody new developments in theory, instrunientation or methodology, or unless they suggest a novel type of approach. Those wishing complete coverage of the polarographic literature are advised to follow the excellent continuing bibliographies founded by Heyrovsky (90, 91) and Semerano (26). These not only give comprehensive lists of publications but also list many theses and papers given at scientific meetings. The number of papers appearing annually continues to grow and the problem of keeping u p grows with it. HE PRESENT
02 139
Hallett (85) has given an account of an ambitious program undertaken by the Polarographic Society of Japan which may simplify matters somewhat. -4bstracts and essential data and figures are being printed on cards (marked to be punched according to the user’s own data retrieval system) starting with the year 1961 and working backwards and forwards. The cards will be available on a subscription basis like a n abstract journal. A number of useful review articles have appeared during the biennium. Muller (152) has surveyed the development of polarography and polarographic instrumentation, Zuman (249) the applications of classical polarography, particularly organic polarography, and Taylor (222) analytical applications. The Heyrovski Honour Issue of Talanta issued in December 1965 (220) consisted of seventeen informative reviews on various aspects of polarography, making the issue an excellent general survey of special topics in the field. A number of the reviews in this issue are cited under their particular topics below. Among the books which have appeared the new edition of Lleites’ wellknown “Polarographic Techniques” (145) is especially welcome. The pro-
ceedings of the first Australian conference on electrochemistry in 1963 (174) contain many interesting papers, particularly on alternating current polarography, and Zunian’s new book (860) gives a good treatment of organic polarographic analysis. Standardization of nomenclature definitions and symbols is always a difficult matter and groups both in C I T C E and IUPAC have been at work on the problem. Reports making suggestions for nomenclature, definitions, and sgmbols in electrochemistry have been issued by these groups for study and discussion ( 5 6 , 5 6 , 2 3 1 ) . CLASSICAL POLAROGRAPHY
Instruments a n d Apparatus. Beckm a n Instruments has entered t h e polarographic field with t h e introduction of a remarkably versatile electroanalytical instrument, t h e Electroscan 30, which has capability not only for ordinary polarography b u t according t o its maker a t least 14 other electroanalytical techniques. These include three-electrode potentiostatic polarography, inverse polarography, alternating current polarography, rapid scan voltammetry, chronoamperometry, and VOL. 38, NO. 5, APRIL 1966
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