Chem Scand 26, 3386 ( 1972) Me1 nik S M Karal nik S M Ukr Fiz Zh 17, 1913 (1972) Mehlhorn W Proc Int Conf Inner Shell loniz Phenomena Future Appl 1972 (Pub 1973) U S At Energy Comm Oak Ridge Tenn p 4 3 7 Gallon T E Matthew J A D Rev Phys Technoi 3, 31 (1972) Somorjai G A Szalkowski F J Advan Hfgh Temp Chem 4, 137 (1971j Weber R E Chimia 27, 335 (1973) Geiger J S Proc Int Conf Inner Shell loniz Phenomena Future ADPI 1972 (Pub 19731 U S At Energy Comm Oak Ridge Tenn p 5 2 3 Yasko R N Whitrnoyer R D J Vac Sci Techno) 8 733 119711 Coghlan, W. A Ciausing, k. E . : Nuci Sci Abstr.. 26, 2785 (1972). Wagner. C . D : Electron Spectrosc , Proc. Int Conf 1971 (Pub. 1972). North-Holland: Amsterdam, Neth.. p 861 Shirley, D A,; Chem. P h y s . Lett 17, 312 (1972) Shirley, D A,: Phys. Rev. A . 7, 1520 11973) Allen. G C.; Wild, R . K . : Chem Phys L e t t , 15, 279 (1972). Szalkowski, F. J.: Somorjai. G. A : J Chern Phys.. 56, 6097 (1972). Whitaker. M . A. 6 . ; J. Phys. C. 5, L102 (1972). Savchenko, V . I . ; Dokl. Akad Nauk SSSR 208, 1154 (1973) Baker, J M . : McNatt, J . L.; J . Vat. SC;. Technol. 9. 792 (1972). Haas, T. W : Grant, J . T.; Dooley. G J . , I l l : J Appi. P h y s . 43, 1853 (1972). Salmeron. M : Baro, A. M . : Surface Sci 29, 300 (1972) Haas. T W., Grant, J T.: Dooley. G J . ; Adsorption-Desorption Phenomena, Proc. Int. Conf , 2nd. 1971 (Pub 1972), p 3 5 9 . Coad, J P : Riviere, J . C.; Proc Roy SOC London. Ser A. 331,403 (19721 Sickafus. E N.. Steinrisser, F . : J Vac Scf. Techno/. i o . 43 (1973) Thomas. S ; Haas, T . W.: (bid. 9, 840 (1972). Kolaczkiewicz, J , Koziol. C : Mroz, S.: Acta Phys Pol. A 41, 783 (1972) Levine, J . D , Jules, D . : Willis, A,: Surface Sci.. 29, 144 (1972). Ekelund, S . ; Leygraf, C.: ;bid.. 40, 179 (1973) Clarke, T A , Mason, R . ; Tescari. M . ; Proc. Roy. SOC London. Ser A. 331. 321
I
(1972) Perdereau M Oudar J Berthier Y Surface Sei 36, 225 (1973) Kostelitz M Domange J L Oudar J !bid 34, 431 (1973) Vrakking J J Meyer F ibid 35, 34 (1973) Meyer F Vrakkinq J J ibid 33, 271 (1972) Vrakking. J J Meyer. F Ned Tfidschr Vacuumtech 1 1 . 6 (19731 Levenson, L. L.:’Davis, L L : Bryson, C E , I l l , Melles, J . J : Kou, W H : J Vac SCI. Techno/.. 9, 608 (1972) Shell, C A,: Riviere, J . C.: Surface Scf 40, 149 (1973). Tarng. M . L.: Wehner. G K : J Appl P h y s . 44, 1534 (1973). Carriere, E . , Deville. J . P : Goldsztaub, S ; Vacuum 22,485 (1972) Cleff, B , Mehlhorn, W.: Phys. Lett. 4 37, 3 (1971). Holland, B. W : McDonnell, L , Woodruff, D. P : Solid State Commun , 11, 991 (1972). Neave, J . H , Foxon, C. T ; Joyce, B . A . . Surface Scr . 29, 411 (1972) Gallon, T. E , Matthew, J A D : J Phys D 5, L69 (1972) MacDonald, N . C.: Waldrop. J R , Appi Phys Lett.. 19. 315 (19711 Musket, R G . . Bauer, W.: / b i d , 20, 455 (1972) Needham P B Jr Driscoll T J Rao N G ibid 21 502 (1972) Peooer S V Rev Sci instrum 44. 826 (1973) Pepper S V NASA Tech Note NASA TN D-7257, (1973) Nishijima M Murotani T Surface Scr 32, 459 (1972) Beck D E Miyazaki E !bid 39. 37 ( 1 973) Baenninger U Bas E B Heiv Phys Acta 45. 977 (1972) Horgan A M Dalins I Surface Sci 36, 526 (1973) Joyce B A Neave J H ibrd 27, 499 (1971) Perdereau M C R Acad Scf S e i C 274,448 (1972) Lassiter, W S J Phys Chem 76. 1289 119721 , Buckley, D. H.; NASA Tech Note. NASA TN D-7340, (1973). Takasu. Y . ; Shimizu H . : J Catai 29, 479 (1973) Bonzel, H P , Surface Scf 27, 387 ~I
(19711 Joyner R W Lang B Somorjai G A J Catal 27, 405 (1972) Tarng M L Wehner G K J Ago/ Pbys 43, 2268 (1972) Robinson G Y Jarvis N L Appl Phys Le‘t 21, 507 (1972) Nakayama K Ono M Shimizu H J Vac Scr Techno/ 9. 749 (1972) Stoddart C T H Hondros E D Nature (London) Phys Sci 237. 90 j1972) Yasko R N Fried L J Rev S o i n strum 43, 335 (19721 Palmberq P W J Vac Sc! Technol 9. 160 (19721 Holloway D M Apoi Soectrosc 27, 95 119731 , Horgan, A M , Dalins, I . , J Vac Scf Techno/ . 10, 523 ( 1 973) Joyner. R W : Rickman, J.: Roberts, M . W : Surface Sci 39. 445 (1973). Willis, R F , Fitton. B , Skinner, D K : J . Appl Phys 43, 4412 (1972) Maguire. H G , Augustus, P. D , J H e c trochem Soc 119. 791 (1972). Sparnaary. M J . Vana Bommel. A J . : Van Tooren. A , Surface Sci.. 39, 251 (1973) Wilson J M Phil Mag 27, 1467 11973) Lyo K Komiya S Shrnku 16. 41 (19731 Narisawa T Kotai Butsurr 7, 49 (1972) Goldstein B Carlson D E J Amer Ceram Soc 55 51 (1972) Wong R J Adhes 4 171 (1972) Buckley. D H NASA Pepper S V Tech No’e N A S A T N 0-6983 (1972) Din1 J W Musnet R G Platrng 60 811 (1973) Marchus W L Waldrop J R Schuler F T Cain E F C J Electrochem Soc 119. 1348 (1972) Seah M P Hondros E D Met M e t a l Form 39 100 119721 Stein D F HeLor‘ COO-1778.7 11971) Buckley D H Pepper S V ASLE (Amer Soc Lubric E n g 1 Trans 15 252 ( 1 972) Ueda K Shimizu R A o ~ iPhys Le’f 22 393 (19731 Connell G L Schneidmiller R F Kraatz P Gupta Y P Proc Lunar Sci Conf 2nd 1971 MIT Cambridge Mass p 2083 Chou N J Osburn C M Van der Meulen Y J Hammer R ADPI Phvs Le!+ 22. 380 (1973) ~I
Emission Spectrometry Ramon M . Barnes Department of Chemistry. University of Massachusetts. Amherst.
Mass. 0 1002
This 14th review includes publications appearing during 1972-73 and continues the approach taken in previous reviews ( 8 A ) . The initial section considers new books and reviews. New fundamental atomic spectral data are presented in the second section. Spectroscopic instrumentation, including light sources and generators, electrodes, optics, spectrometers, and readout systems constitute the third section. The fourth section reports publications on sampling, standards, calibrations, and computations. Advances in the description and understanding of emission excitation sources are reviewed in the fifth section. Significant spectrochemical analyses developed and described during the past few years conclude the review. The material used in preparing this review comes from major spectroscopic journals and various abstracting sources, although conference proceedings and trade jour150R
nal articles are generally excluded. For material not commonly available in English, reference to alternate sources such as Chemical Abstracts is included.
BOOKS AND REVIEWS New textbooks in emission spectroscopy remain limited although both specialized and comprehensive reviews supplemented published and recorded conference proceedings in spectroscopy during the past two years. Primary among the new textbooks is a two-volume set by Mika and Torok entitled “Analytical Emission Spectroscopy” (63A1. Published in 1973 as an enlarged English translation of the original Hungarian version, the first volume contains sections on line and band spectra fundamentals; excitation generators and arc, spark, laser, and discharge tube exci-
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Ramon M. Barnes, assistant professor of chemistry at the University of Massachusetts, teaches instrumental analysis and spectroanalytical chemistry. He received his BS in chemistry from Oregon State University in 1962, a MA from Columbia University in 1963, and a PhD in analytical chemistry from the University of Illinois in 1966. As a Captain in the U.S. Army, he served during 1967-68 at NASA Lewis Research Center in Cleveland. He was a postdoctoral associate at the USAEC Ames Laboratory at iowa State University from 1968 until he joined the Chemistry Department at the University of Massachusetts at Amherst in the fall of 1969. He is a member of the American Chemical Society, Society for Applied Spectroscopy, Spectroscopy Society of Canada, American Society for Testing and Materials, the Optical Society Of America, the Society of Sigma Xi, and SAS representative to the ANSI measurement and automatic control technical advisory board. His research interests include analytical instrumentation and spectrochemical analysis. Current research projects include investigation of atmospheric radio frequency plasma discharges, low-temperature plasma ashing. and time-resolved spark spectroscopy.
tation processes; and spectral radiation dispersion, measurement, and evaluation. The second volume on applications and practice is planned for publication in the near future. The second part of a multi-volume series edited by Grove and also titled “Analytical Emission Spectroscopy” appeared in 1972 ( 3 7 A ) . This volume emphasizes excitation of spectra, qualitative and semiquantitative analysis, quantitative analysis, and flame spectrometry in individual, detailed chapters by recognized experts. A third part is being prepared for publication in 1974 to include evaluation of photographic emulsions, experimental statistics, temperature measurements, image optics, and direct reading spectrometers. A volume on applications is also anticipated. Addink’s dc arc K - and Q-methods were described in comdete oDeratine detail in the short book “DC Arc Anaiysis” ( i A ) . Toyok and Zimmer provided in English an in-depth description and practical manual for evaluation and use of the l-transformation for spectrographic emulsion calibration ( 8 5 A ) . The 1972 and 1973 editions of the “Annual Book of ASTM standards, Pt. 32,” provide current versions of standard emission spectrochemical analysis methods (4A, 5A). During the past two years, a major new annual review of atomic spectroscopy was begun by the UK’s Society for Analytical Chemistry. The first two “Annual Reports on Analytical Atomic Spectroscopy” review developments for 1971 ( 4 5 A ) and 1972 ( 4 6 A ) . These unique reports, compiled through an extensive board of international correspondents and co-ordinated through editorial evaluation and comment, provide a valuable source for developments in all branches of analytical optical atomic emission, absorpt,ion, and fluorescence spectroscopy. These timely and critical reviews draw from established journal and trade magazines as well as spectroscopic meetings and conferences. Volume I contains 1092 citations and volume I1 reports 1123. In a section on fundamentals and instrumentation, the categories reviewed include light and excitation sources, atomizing systems, optics, defector systems and data processing. In the section on methodology, which constitutes 65% of the text, general techniques and applications in eight major fields are considered. A summary table for each field includes data grouped by element for sample form, concentration, matrix, treatment, technique, wavelength, atomization, and detection limit, and literature reference. Of value are a number of lists of commercial instruments, components, and supplies along with the address of manufacturers and suppliers. The 17th volume in the series “Spectrochemical Abstracts” covers the year 1970 and adds 554 selected abstracts to give a series total of 7578 ( 9 1 A ) .These abstracts are grouped in sections by substances analyzed, apparatus, methods, theory, books and reviews. A valuable index of elements makes location of pertinent abstracts rapid and direct. In complementary use, these two British series
make literature retrieval in analytical atomic spectroscopy convenient and effective. Conference proceedings of interest to emission spectroscopists have been published. The submitted and plenary lectures of the 1973 XVII Colloquium Spectroscopium Internationale in Florence ( 2 0 A ) and papers from the 3rd International Congress of Atomic Spectro-metry in Paris in 1971 ( 7 3 A ) are now available. Perkins et al. edited the tenth volume of “Developments in Applied Spectroscopy,” which includes selected papers from the 10th National Meeting of the Society for Applied Spectroscopy in St. Louis in 1971 ( 7 0 A ) . A novel format for two special ASTM-sponsored symposia at the 1972 and 1973 Pittsburgh Conferences is provided by audio tape cassets, which are accompanied by a booklet of related illustrations. One symposium is optical emission spectrometers ( 5 2 A ) and the other is the analysis of slags and related materials ( 6 0 A ) . The June 1972 ASTM-sponsored symposium on sampling, standards, and homogeneity is available in conventional monograph format ( 5 3 A ) . Simmons and Ewing edited the 6th volume of “Progress in Analytical Chemistry,” which includes two of the four papers presented at a symposium on recent developments in arc emission spectroscopy held during the 1972 Eastern Analytical Symposium (79A). Reviews of metal analysis in particulate pollutants by emission spectroscopy and of plasma diagnostics are included in volume 6 of “Applied Spectroscopy Reviews,” edited by Brame ( 1 5 A ) . Optical emission spectrometry is only one ( 5 6 A ) of nine chapters of measuring techniques described in the comprehensive book “Modern Methods of Geochemical Analysis,” edited by Wainerdi and Uken ( 9 2 A ) . These technique chapters follow two on statistics and chemical analysis and sample preparation in geochemical analysis. Among the topics presented at the Symposium on Analytical Methods in the Nuclear Fuel Cycle @ A ) were papers describing spectrographic methods for trace metals including the carrier distillation technique. A variety of useful books are available in related fields of optics, radiometry, photography, sources, imaging devices, and optical gas diagnostics. Hammond and Mason edited a 690-page volume of selected National Bureau of Standards papers on radiometry and photometry as the seventh volume in a series on precision measurement and calibration ( 3 9 A ) . This extensive volume reprints more than 80 papers in the fields of general and applied photometry and radiometry; standards of emittance, irradiance, and radiance; and measurement of emissivity, emittance, and flux. Three complementary books deal with sources commonly used in both scientific and commercial lighting applications. In “Light Sources,” Elenbaas, formerly of Philips in Einhoven, gives a detailed fundamental and experimental description of incandescent, and low- and high-pressure gas discharge lamps ( 3 1 A ) . In “Electric Discharge Lamps,” Waymouth, of Sylvania, considers these major types of commercial sources and emphasizes practical lamp design ( 9 3 A ) . Henderson and Marsden edited a comprehensive and practical volume on sources and source properties in “Lamps and Lighting” ( 4 1 A ) . The “SPSE Handbook of Photographic Science and Engineering,” edited by Thomas ( 8 8 A ) , is a comprehensive and unique single-volume compilation which sho:ild be an invaluable reference for spectroscopists working with photographic systems and components. In 23 chapters and 1416 pages, this reference handbook provides practical information on light sources, radiometry and photometry, photographic optics, filters, and radiation detectors. The physical and chemical properties of the latent image and processing are described along with photographic sensitometry, densitometry, and image structure evaluation. Concluded by chapters on testing, photographic instrumentation, microphotography, and holography, the handbook includes an extensive guide to photographic information sources. In contrast to the SPSE Handbook, the two volumes of “Photoelectric Imaging Devices,” edited by Biberman and Nudelman (12A). provide a tutorial reference to modern photoelectric imaging systems. Volume 1 surveys the fun-
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damental physical principles underlying imaging devices conduction and breakdown in high vacuum, and in dielecdesign and operation as well as methods for prediction tric liquids are especially related to theoretical and experand analysis of sensor performance in 17 chapters. Volume imental phenomena of interest in emission spectroscopy. 2 describes, in 22 chapters, the operation and characterisCookson’s chapters (22.4,23A) on electrical breakdown of tics of imaging devices along with laboratory methods for gases, for example, cover fundamental ionization protheir evaluation. The optical properties of semiconductors cesses in gases, mobility measurements, breakdown in and their optoelectronic devices are described in “Semiuniform and non-uniform fields, laser induced breakdown, conductor Opto-Electronics” by Moss et al. (67A).Doand application of gas breakdown and gaseous insulation, sanjh edited a useful volume on modern optical methods with approximately 300 references each year. in gas dynamic research, which includes laser and interIn the field of lasers, a number of comprehensive literaferometric diagnostic methods, based upon reports from a ture reviews assist in keeping pace with the past activi1970 international symposium (30A). ties. Arnold and Rojeska surveyed the literature of chemiTolansky published a second edition of “An Introduccal lasers covering the period 1964-71 (7A).Wiswall et al. tion to Interferometry” (89A),and O’Brien wrote a chapcompiled a bibliography through June 1972 (99A),and ter on interferometry in “Techniques of Chemistry” Cheste- reviewed recent work through the end of 1972 (68A).Bell provided an “Introduction to Fourier Trans(I9A).Jensen and Rice (49A),Cool (24A),and Silfvast form Spectroscopy” (IOA),and Fourier transforms and (78A)also surveyed the literature and properties of varitheir physical applications were described by Champeney ous types of chemical lasers. Tunable dye lasers were rein a recent book (18A). viewed by Bloom (14A),Jain (48A),Webb (94A),Haensch In Gerdeman and Hecht’s “Arc Plasma Technology in (%A) and Schaefer (76A,77A).Hsu compiled a Nd:YAG Materials Science,” modern technological and industrial laser bibliography (44A),and Smith reviewed solid state use of arc plasma jets for flame spraying and materials lasers (82A).Magyar compiled a bibliography on dye laevaluation is described (34A).This brief volume also insers (58A). cludes chapters on plasma effluent characterization, and The problems of laser spectroscopy were considered by physical and optical plasma diagnostic techniques. Letokhov and Mandel’shtam (59A).Uses of lasers in Some other recent books on optics and optical compochemistry were reviewed by Moore (66A).High resolution nents include those by Williams and Beckland (96A), laser spectroscopy was discussed by Stroke (84A) and Meyer-Arendt (62A),Home (43A),Palmer (69A),and KaD e m t r a e r (28A). pany and Burke (51A).A variety of spectroscopic compoAmong the tests on laser sources and interactions, nents and instruments were described and reviewed in Demtroder described spectroscopy with lasers (27A); “ODtical Instruments and Techniaues 1969.” edited bv Moenke and Moenke-Blankenburg, (65A),and Delhaye, Diikinson (29A) . Cornu, and Baudin (26A)considered laser applications for Zaidel et al. have written a college-level textbook in spectrochemical analysis. Weber and Herziger also disRussian which surveys practical Atomic spectroscopy cussed lasers (95A)and Schaefer edited a volume dedicat(IOOA). Methods of spectrochemical analysis were deed to dye lasers (76A).Four chapters dedicated to laser scribed by Tarasevich et al. (87A).The analysis of pure microprobe instrumentation and applications to the analsubstances was treated by Zil’bershtein et al. (IOIA);of ysis in geology, and of metals and biological materials rare, trace, and refractory elements by Kul’skaya and were included in a volume on “Microprobe Analysis” editKozak (54A);and of construction materials by Kurbatova ed by Andersen (3A).Williams described the use of laser et al. (55A).Books on spectroscopy of optically dense microprobes in forensic science (98A). plasmas (74A)and gas radiation at elevated temperatures In considering spectroscopy from a historical viewpoint, (50A)were also published in Russian. Meadows completed a bibliography of Sir Norman LockNumerous new materials are available concerning the yer, who discovered helium, founded and edited Nature, fundamental nature and processes in sources of potential and first obtained quantitative spectrochemical results interest in spectroscopy and interactions among atomic with an electrical discharge (61A).The life and work of and molecular species. Mitchell and Zemansky’s classic Fourier were described by Grattan-Guinness and Ravetz “Resonance Radiation and Excited Atoms” was reprinted (36A),of Fabry by Lecomte et al. (57A),and Michelson after being out-of-print for some years (64A).The princiby Bennett and McAllister (1IA).Daumas described the ples and theory of atomic spectroscopy are presented by “Scientific Instruments of the 17th and 18th Centuries,” Sobel’man (83A)in an English revision of his 1963 Rusincluding the evolution of optical instruments (25A). sian text. A chapter on theory of atomic spectra was preBarnes summarized briefly the historical developments in pared by Hindmarsh (42.4).In the “Physics of Atomic arc emission spectroscopy leading to modern arc techCollisions,” Hasted treated both experimental methods of niques (9A). collisional physics as well as experimental and theoretical Billon summarized the equipment arrangements and approaches to atomic and molecular processes, including provided some examples in a brief review of emission emission and absorption, ionization, excitation, and spectrography applied to chemical analysis (13A).In a c’large transfer collisions (40A).Field and Franklin wrote comprehensive review of the 1970 and 1971 developments a second edition of “Electron Impact Phenomena and the in analytical chemistry, Pilipenko and Volkova mention Properties of Gaseous Ions” (32.4).Franklin also edited a only briefly analysis by spectral methods (7IA, 72A). A two-volume book on “Ion-Molecule Reactions” (33A),as review of analytical research in emission spectroscopy in generally defined by mass spectrometry and including a Hungary was written by Zimmer (I02A).The proceeding chapter on ion-neutral reactions in electrical discharges of a Russian conference on spectroscopy held in 1971 con( S A ) .Armstrong and Nicholls reviewed the basic theory tained more than 60 reports in Russian in the field of of radiative transfer in heated gases pertinent to gas opacemission spectroscopy (9OA).The Japanese biennial review ity calculations (6A). of spectrographic analysis was prepared by Hirokawa and The invited papers presented a t the International ConTakada and included 300 references (103A). ference on Atomic Physics at Oxford in 1970 were edited by Sanders (75A),and at Colorado in 1972 by Smith and SPECTRAL DESCRIPTIONS AND Walters (81A).The abstracts of papers (16A)and invited CLASSIFICATIONS papers (35A) from the 7th International Conference on The production, collection, identification, and classifiPhysics of Electronic and Atomic Collisions in 1971 became cation of atomic spectra continues, and measurement of available in 1972. Smith described some theoretical aplifetimes, transition probabilities, oscillator strengths, proaches for computer methods for cross section in “The electronic configurations, cross sections, and spectral Iine Calculation of Atomic Collision Processes” (80A).The 2nd shapes occupy considerable effort, described only briefly International Conference on Gas Discharges in 1972 inin this section. cluded almost 150 papers on the properties of gas discharges Among the new publications appearing during the past (47A). two years, a reprinted edition of Moore’s 1945 classic Published annually, the “Digest of Literature on Dielec“Multiplet Table of Astrophysical Interest” was prepared trics” includes comprehensive, critical reviews of various as NSRDS-NBS 40 (182B).Although none of these major aspects of electrical insulation and dielectric phenomena lines in 196 atomic spectra of 85 elements was altered, (17A, 2IA). Chapters on electrical breakdown in gases, 152R
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some individual spectra, notably H I, D, and T (184B);C I-VI (185B); N IV-VI1 (186B), and Si I-IV, were revised and compiled under individual sections of “Selective Tables of Atomic Spectra, Atomic Energy Levels and Multiplet Tables,” NSRDS-NBS 3. Moore’s 1950s version of “Atomic Energy Levels, Vol. 1-111,” was also reprinted as NSRDS-NBS 35 (183B). Hagan and Martin continued Moore’s bibliography on the analysis of optical atomic spectra in a compilation with some 1100 references published between July 1968 through June 1971 entitled “Bibliography on Atomic Energy Levels and Spectra” ( 115B). “A Bibliography on Atomic Line Shapes and Shifts,” covering the atomic spectral line broadening literature in about 1400 references egtending from 1889 through March 1972, was assembled by Fuhr, Wiese, and Roszman ( 9 2 B ) . The “Spectrum of Iron from 2206 to 4656 A” was edited by de Gregorio and Savastano and includes 38 photographic charts from a 3.5-m grating spectrograph (74B). Salpeter recorded the first two portions of a five-part work on spectra in a glow discharge lamp, covering the wavelength region of 500-4000 A for noble gases and 1500-4000 A for the remaining elements (223B). Tables of continuum radiation were given for Ar, Nz, 0 2 , and air in the 950-.fi to 6.0-wm range for temperatures 9000-30.000 “K and Dressures of 1-30 atm bv Morris and Yos (190B). Kalinin et al. published in Russian a handbook on the “Identification of SDectra of Elements” (138B). and Ritschl compiled an -index of spectral lines for spectrochemical purposes (214B, 225B). Athay prepared a monograph on “Radiation Transport in Spectra Lines” (14B), and Armstrong described the “Theory of the Hyperfine Structure of Free Atoms” (11B). Garton gave a progress report on the determination of atomic and molecular transition probabilities (98B), Edlen reviewed the present state of term analysis of atoms and ions containing less than 28 electrons (80B), and Steinhaus e t al. critically surveyed the current status of the analysis of the optical spectra of uranium (241B). Laulainen compiled a bibliography of the spectra of atmospheric minor gases (152B). Ms. Moore-Sitterly reviewed the interpretation of atomic spectra (187B), and she surveyed the present status of analyses of IR atomic spectra. (188B). Biemont and Grevesse discussed atomic wavelengths in the infrared, and calculated oscillator strengths based on the Coulomb approximation (31B). The contributions made by Shenstone to the analysis of atomic spectra were reviewed in the nomination for the Meggars Medal (IOB). Progress reports and reviews of many of the developments in theoretical and experimental atomic spectra were presented a t the 3rd International Conference on Beam-Foil Spectroscopy a t Tucson in 1972. Bashkin edited a single, entire volume of Nuclear Instruments and Methods which contains more than 80 papers from that meeting (20B). Topics include optical spectra, measurements of lifetime and transition probabilities (6B, 67B, 233B, 235B), theory of the Hanle effect, experimental techniques, and a number of others (62%). Unfortunately, the extensive literature on beam-foil spectroscopy cannot be completely covered in this review. Identification and classification of spectral lines and energy levels continues, although the lanthanide and actinide elements appear to be receiving greater attention than in the past. The spectra of highly ionized levels, especially those following the isoelectronic series of light elements, generally occur in the vacuum and extreme vacuum ultraviolet regions. As electron spectroscopy continues to develop, identification of spectral transitions in the XUV and electron spectrometry should provide complementary evidence. Table I summarizes some of the atomic spectra reported in wavelength regions most accessible to the spectrochemist. Thus, the vacuum ultraviolet spectra of multiple ionized levels is not included. Table I also includes ionization limits and potentials when reported. Sugar and Reader derived values for the ionization energies of the doubly and triply ionized rare earth atoms (245B),but the values are not included in Table I. Semi-empirical energy level values for double ionization states of atoms were given by
Blokhin and Platkov (38B).Blaise and Wyart reviewed the main features of the spectra of neutral and ionized lanthanide series elements, the experimental and theoretical methods used for analyzing these spectra, and the present status of their classifications (37B, 257B). Cowan also discussed the theory of rare earth energy levels and spectra (69B). Croswhite edited Dieke’s hydrogen molecule wavelength tables (70B). Williams calculated 2513 vacuum ultraviolet wavelengths for Li I1 to Co XXVI using the theory of isoelectronic sequencies with wavelengths from previously identified transitions (97A). Atomic spectra are also measured in absorption to observe autoionized states. In order to provide a complete picture of the atomic states, a more detailed analysis than measurement of wavelengths of the lines of an element is required. The study of autoionization structures and their parameters, and photoionization cross sections is necessary. Autoionized lines are not generally observed a t the same time as the discrete emission lines of atomic spectra, because their appearance is often very diffuse, and they have been mistakenly assigned as continuum or molecular bands. In considering Cu I, Tondello measured the absorption spectra a t wavelengths shorter than the first ionization limit [1604.7 A] a t which value continuous absorption begins and autoionized states mix with the continuum (248B). His study of the continuous and quasi-continuous states of Cu I showed several series, some of which were strongly autoionized, converging to the excited states of the ion. Carter and Hudson measured the absorption cross-section spectra of He and Kr in their regions of autoionization (54B). By using a new continuum light source, Hildum and Cooper obtained the VUV absorption spectra of ions C 11, Si 11, and I11 (120B). Assous confirmed previously known autoionization levels in P b and Bi through the arc emission spectra (13B). M. Mehlman-Balloffett and Esteva measured 8 lines in the principle series of Be I11 by absorption (174B), and Garton et al. studied Y I (100B) and Sc I (99B) autoionization resonances by absorption. Parkinson and Reeves measured autoionization resonances in the Zn I and Cd I emission spectra (199B). Gabriel and Jordan reviewed the interpretation of spectral intensities from plasmas (94B), and Reif et al. critically reviewed theoretical spectroscopic temperature measurements (213B). Kibble e t al. reported the experimental determination of the Rydberg constant value a t R = 109,737.326 f 0.008 cm-1 from the wavelength components of the Balmer -a line (145B). A recommendation for a new determination of the Rydberg constant was made by Series (228B). Carstens et al. showed that the complex electronic absorption spectra of atoms isolated in noble-gas matrices a t low temperatures correlated well with electronic transitions involving the ground state of the analogous gaseous atoms (53B). They provided a series of the line drawings to depict these transitions, and a set of tables which gives the intensities and energies of all experimentally observed gaseous transitions for neutral gas elements. Smith and Wiese compiled the atomic transition probabilities for -750 selected forbidden lines of the iron group elements (234B), and Wiese reviewed the regularities in atomic oscillator strengths (256B).Nicolaides and Sinanoglu reviewed new experimental and theoretical atomic transition probability results (195B). Table I1 lists references to selected lifetimes, transition probabilities, and oscillator strengths. Andersen et al. systematically studied lifetimes of the Ag I, Cd I, Au I, and Hg I isoelectronic sequences ( Z B ) , and Sorenson reported lifetimes in the Cu I, Zn I, Na I, and Mg I sequencies (238B). Cohen and McEachran described systematic trends in oscillator strengths in the He isoelectronic sequence (65B). For additional reports on the description and classification of spectra, papers presented in sessions on atomic and molecular spectroscopy a t the meetings of the Optical Society of America should be consulted (209B). INSTRUMENTATION In a detailed chapter on optical design and selection of spectroscopic instruments, Muller-Herget considered the
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Table I. Selected References t o Atomic Spectra Element isotope
H He
I I I I , I1 I1 I11 I11 I I-VI IV-VI1 I VI VI1 I
Li Be B C N 0
Ne 20.21.22Ne 20,22Ne *'Ne Ne Na
Mg
P S
C1 Ar
Ca
Ionization level
I I I I I1 I11 I11 I11 IV, v , V I IV, V I I11 I11 IV IV IV I1 I I I I I11
sc Ti Cr Mn Fe Ga As
Se Br 86Kr
I11
IV V VI I I , 11, I11 I11 IV V I1 I I IV I I
Wavelength range,
'4
7th series Freeman effect; fine structure energy levels (review)
6000-2000 11,000-200 6200-80 6200-500 2500-1375
6
50 36; 1,241,253 i 10 25; 1,241,242 3~ 15 31 energy levels, multiplets energy levels, multiplets 271; 117,356.46 f 0.12
10,440-885 2896.4 2450.0 743.7195s i 0.0002 743-576 55,000-45,000 6096; 6074 80,000-30,000 3s2 level 11,000-300 2500-1300 380-180
173,929.75 f 0 . 0 6 46 standard wavelengths 27 isotope shift 19; isotope shift hyperfine structure 1250; 330,288.6 i 0 , 3 177 90 577,654 58 44 373; 646,402 i 5 24 -210; 881,190 243; 880,800 -120; 881,285 i 10 223; Zeeman effect, 76 g-factors forbidden transitions
2400-80 2400-80 6600-720 234-157 3500-3300; 2000-100 2100-80 2535-2470; 1130-710 7846-2285 4589.2605 =t0.0005 7725.0461 f 0.0007 40,000-19,000 12,350-3130 2090-2020; 1770-1550 9640-2290
204 -250; 127,190.80 i 0 . 1 230 222; 410,642.3 i 2; 413,760.2 i 2 -50; 199,677.0 i 0 . 5 93; 199,677.37 i 0 . 1 1249 275 130; 69.45 i 0 . 0 4 eV 95; 731,020 f 6 (69.633 eV) 8; hfs
9000-730 9400-550 2310-1500 2423-523 1837-433 2496-144 6000-620 1466-1137; 440-422 2400-400 10,556-2361 33,600-10,090 2400-420 40,000-18,000
merits, intricacies, and disadvantages of classical and modern instrument configurations (261C) . Described without detailed discussion of elaborate design procedures, were spectroscopic collimators, dispersing elements, camera systems, illumination, and monochromators. Bouchareine surveyed briefly some spectroscopic instrumentation with particular emphasis on high-resolving power capabilities in the IR (30C). Yoshinaga et al. also reviewed the development of spectroscopic instruments (420C). Computer automation and applications for analytical instrumentation were described by Veress (390C), Gundelach (137C), Ernst (96C), Minamai (253C, 254C), Szoke (358C, 359C), and Szepesvary (356C). Dessy and Titus described the principles and application of computer interfacing (79C), and Kelly and Horlick considered practical considerations in digitizing analog signals (196C). Per154R
Number lines/ionization limit, cm - 1
190, 620 (524.60 cm -I)
30 39 29 232; Zeeman effect, 80 g-factor 148 3; forbidden trans. 27 150 112,925 i 10
Reference
(117B) (179B) (171B) (1B) (29B) (BIB) (161B) (106B) (185B) (186B) (88B) U8B) U8B) (139B) (189B) (59B) (93B, 142B) (104B) (204B) (181B) (164B) (132B) (108B) (107B) (9B) (163B) (133B) (12B) (132B) (156B) 187b)
(128B) 1180B) (43B) (39B) (123B) (249B) (192B) (82B) 183B) (84B) (162B) I193B) (137B) (137B) ( 1 36B) 1157B) 1103B) 185b1
II02B) (128B) 155B)
one and Jones prepared a handbook on the bases, use, applications, and interfacing of small laboratory minicomputers popular in the U S . (290C). Optics, Gratings, Spectrometers. Harrison reviewed the advances in diffraction grating ruling made in the past 25 years and particularly demonstrated the application of interferometry and electronics to ruling engine control (1432, 146C). Loewen (227C) and Landon and Mitteldorf (215C) also described ruling and properties of modern gratings. Rao discussed the theory of plane gratings for high-infrared spectrographs (306C), and Quintard et al. described a duralumin grating for the far infrared (304C). Kalhor and Neureuther explored the effects of conductivity, groove shape, and physical phenomena on the design of diffraction gratings (19OC) and used a numerical method for analysis of gratings (189C) to study the validity of more approximate techniques (191C). Palmer and Le Brun used a numerical integration
A N A L Y T I C A L C H E M I S T R Y , VOL. 46, NO. 5, A P R I L 1974
Table I (Continued) Element isotope
Rb
Sr In Sn Te l 6T e I Xe
Ce 136,
lace ZCe
140,lt
Ce Pr
Ionization level
Wavelength range,
.i
Number lines/ionization limit, cm-1
I1
741-480 5200-2200: 741-466
I11 I11 I11 I11 IV I I
3600-2300; 820-400 3500-370 9800-350 562-307 7000-340 6454; 3283; 3262 4309.4311; 5419.2284; 7908.8960; 9469.0022
I 1 I 11, 111, IV I, I1 I, I1 I1 I I1 I, I1
40,000-18,000 54,432-36,508 8569-2477 24,200-8200
Gd
Tb DY 160 -164Dy Ho 166,161,180Er Er Tm
Yb
Lu Hg l99Hg T1 Pb
Bi
1 111 1 I1 I11 I I11 I I I 1 I 111 I I1 I1 IV I I I11 I IV I 1
Th U
Pu
I I, I1 I I I1 I11 IV V I, I1
(212B) (211B)
hfs 160
(96B) (128B) (189B) (160B) (253Bj 156B, 57B) 166B) 1134B) I 261 B )
-250
147,149Sm
Eu
14; 27.285 eV -200; 220,070 i 20 127.285 i 0.003 eV); Zeeman effect, 183 lines 137; 314,700 zt 2500 (39.0 i 0 . 3 eVj energy levels 590; 345,879.0 zt 1 . 5 13; 42.87 eV energy levels; 461,875 isotope shift, hfs
43 2076 isotope shifts
24,000-2500 26,000-11000 12,000-3500; 8700-2000
11,400-2700 8752-2468 26,000-14,000
11,000
31 energy levels hyperfine structure hyperfine structure energy levels 5300; Zeeman splitting (-1500) 2200 18
6800-2000 4100-2478 8326-4013 6865-3810 5900-2165 11,750-2513 10,712-2164; 2107-1377 3200-400 5890-1728 9000-340 3250-2536 1000-340 3150-2135 4615 19,080-30,261 cm --I
hyperfine structure >2500 1418 configuration analysis 165; isotope shift energy levels -150; isotope shifts 135 2734; Zeeman effect; 49,891 i 20 configurations; g-factors configurations -105 246; 364,500 I 200 30 hyperfine structure 240,773 2 5 7 341,438 zt 5 9 1;Zeeman effect 0 3 eV 7.5 39,659 9000; 6.22 I 0 . 5 eV 6 3 i0.3 2200; 10 6 1 eV 18.9 i 1 3 2 . 1 I!= 2 47.1 i 2 hyperfine splitting
*
method to determine the approximate location and shape of so-called anomalies of a blazed grating in both polarizations (285C). Multiple diffractions within the single groove accounted for the anomalous behavior. Maystre emphasized that large polarization variations between aluminum and infinite-conductor gratings were expected and blaze effects were observed for cases in which electric field vector was not parallel to grating grooves (214C).Poulsen described the polarization calibration of a grating spectrometer (299C), and Azzam and Bashara applied ellipsometry to obtain polarization properties of various diffraction orders of plane gratings (13C). Agrawal and Lo studied anomalies of dielectric-coated gratings (2C). In order to study the effects of asymmetry in blazed gratings, Ikola et al. developed a rigorous solution for the plane-wave scattering of a corrugated-structure diffraction grating (177C). Tseng derived an equivalent network representation for a rectangular-corrugation profile grating
Reference
(;?lOBj (116Bj (205B) 212B) I 30B) ( 230B j 186B)
161b)
ISRB, 150Bj ( 172B) f 251 B ) j 36B j (135B) (22B, 146B) i175B) (47B ) 1209B, 257B) (220B) /34B, 35B) ‘220B) 1239B) (244B) (46B) 148B,49B) 1140B) (243B) (154B) 1113Bj ‘114B) ( 13B) fI14B) f23b1
(76B) \ 25B) I MOB) 1242B) 115B I
1242B) 12418) 1241B) r241B) 23B j
(379C). Ludwig developed a unified grating ray-tracing procedure using a vector model (228C). Calatroni and Garavaglia developed a new analysis of Rowland ghosts, proposed a better criteria for labeling them, and derived an expression for their intensities (49C). Palenius et al. identified an unusual kind of grating ghosts due to a single periodic error in the ruling machine and not to multiple periodic errors, as in the case of‘ usual Lyman ghosts (283C). Lockwood developed an exact dynamic dispersion formula for photoelectric instruments in which the grating must be rotated to scan the spectrum (226C). tJones and Shaw (188C) corrected Lockwood’s equation, and Best (23C) challenged the meaningful use of the terms static and dynamic dispersion. Giles et al. considered the angular dispersion expression for a fixed grating undergoing a change in angle of incidence as in tuning organic dye lasers ( l 2 4 C ) .
A N A L Y T I C A L C H E M I S T R Y , V O L . 46, NO. 5, A P R I L 1974
155R
Table 11. Selected References to Lifetimes Element
H He Li
Be B C
N
0
F Ne
Na Mg
AI Si
P S c1
Ionization level
Type
References
7
(45B) (28B, 50B, 203B, 208B, 260B) (19B) (29~) (45B, 227B) (7B) (41B, 124B, 125B) (42B) (41~) (219B) (105B) (231B) (194B) (168B) (41~) (200B) (158B) (168B) ( 79B1 (197B) (231B ) (68B, 147B, 168B, 194B) (91B, 158B) 163B) (231B ) 1130B) (4B, 51B, 52B, I l l B , 141B, 153B, 208B, 225B, 229B, 250B) (IlOB, 226B) 1121B, 153B) (4B (llOB, 112B) (5B, 170B, 224B) (25B) (5B, 224B) illOB) (170B) 17B) (170B) (101B ) (25B) (27B, 131B) 171B) (25B) (16B) (25B) (131B) (21B) (25B) (4B, 191B, 250B, 262B) (258B, 259B) (167B) (131B) (247B, 252B) (149B) (97B, 165B) (159B) (221B j 126B, 246B)
I I I I, I1 11,I11 I I, I1 11,I11 I,11,I11 11,I11 I I I I,I1 1-111 1-111 I I,I1 I-v I1 I1 I I I1 I11 I-IV I
I I1 I I1 I I I1 I11 I I1 I I 11,I11 11-IV I-v 11, IV I, I1 11,IIL I11 -VI 11-1-11 I11
Ar
I
K
I I,I1 I-VI11 I1 I1 I1 11-VI I1 I11 I
Oscillator S t r e n g t h s (f), and Transition Probabilities ( A )
(7))
7
f 7 7 7
f 7 7, f 7,
7
A
f 7
7
f
7,
A
f 7
7 7
f 7 f 7
f 7
T
A 7 7
7, 7
f
A 7
f 7 7 7
f
A 7 7
A A A
f
7, 7
A 7
A 7
f
7,
A T
A,
i 7
7
De Biase et al. computed spread and transfer functions, including aberrations, for arrangements of multiple stationary and moving gratings in the evaluation of a method for high resolution spectroscopy ( 7 2 C ) . The deterioration of gold diffraction gratings overcoated with A1 + MgF2 showed loss in efficiency due to interdiffusion of Au and Al. Hunter et al. studied the interdiffusion, and found that it could be eliminated by adding a thin A1203 or S i 0 barrier layer ( 17 4 C ) . Nizhin et al. described a method for preparing copies of 156R
Element
sc Ti V Cr
Mn
Fe
co Ni
cu Zn
Ga Ge Kr
Rb Sr Pd Ag Cd In Sn Te Xe
cs Ba La Nd
Eu Gd Tm W Hg
T1
Pb Bi
Ionization level
Type
f
I I1 1-111 I I-IV 1-111 I I I,I1 I1 I
A A
I
f
I I,I1 1-111 I I I-xv I1 I I I,I1 I I I I-IV I I, I1
7 T
7
f
7, 7 9
f
7
f 7
7 7 7 7 71
A A
f
7
f 7 7
f
A A
f 7
A, f 7
I, I1 I I, I1 I, I1 I1 I I1 I I I I I,I1 I I I I I I,I1 I1 I I I,I1 I I I I I I1 I,I1
A
I
f
7
r
A 7 7 7
f
7) 7
f 7
7,
A
7 7 7 7
f
A 7
T 7,
f
7
A
f f
f 7 7
A 7 7, 7
f
References
(73B) (151B) (44B) (118B) (216B, 218B) (217 B ) (170B) (89B) (207B) (234B) (234B) (33B, 89B) (170B) ( 72B1 (207B) 1126B, 127B, 144B) (119B, 173B) (234B) (236B) (170B) (198B) (207B) (40B, 169B) (198B) 1155B) (234B) (32B, 206B) (8B, 237B) 1237B) (196B) ( 176B) (4B, 250B) ( 75B (177B) (149B, 166B) 126B) (151B) 1143B) (24B) (206B) (5B) (8P, 224B, 237B) (196B! (3B, 122B) (95B) (4B, 60B, 129B) (255B) t 178B) 178B) (222B) (77B) (224B) (90B) f202B) (148B) 1201B ) t254B) (72B) 164B) (232B) (196B) I 17B) (3B1
diffraction gratings (272 C) . Three-dimensional holographic gratings were made in polymethyl methacrylate by Moran and Kaminow, and the diffraction efficiency was measured as a function of thickness, n change, and reconstruction angle (259C). Uchida calculated the efficiency in hologram gratings attenuated along the direction perpendicular to the grating vector (383C). Bruner described a simple visual test, which was twice as sensitive as the Foucault knife edge test, for the evaluation of concave diffraction gratings (42 C). The diffraction
A N A L Y T I C A L C H E M I S T R Y , V O L . 46, NO. 5, A PR IL 1974
created by a slit and a grating provided Theocaris and Liakopoulos with the basis for a simple, versatile method for alignment, orientation, and range finding (367C). Murty and Cornejo described an improved Ronchi test for concave surfaces (266C3. Steinhaus and Brixner described a simple adjustable method to reduce astigmatism from spherical mirrors used at moderate off-angles (341C), and Strezhnev and Andreeva used a concave toroidal grating to correct astigmatism over wide spectral ranges (346C). Murty discussed compensation for coma and anamorphic effect in double monochromators (263C), and produced a coma-corrected double monochromator without intermediate slit by eliminating the anamorphic effect of the grating (264C). The Cary principle, which enables the determination of the minimum off-axis angle required in any in-plane monochromator to eliminate multiply dispersed light, was used by Murty to design a Czerny-Turner monochromator (265'2). Stephenson discussed the optimum slit settings for double spectrometers a t high grating angles (343C). Yates et al. constructed a low-cost double monochromator (418C), and Lipsett et al. described a subtractive double monochromator with a variable central slit (222C). Tubbs and Williams described an evacuated, high-resolution Czerny-Turner spectrograph (380C). Moret-Bailly reviewed the advantages of grille spectrometers along with spectrometer theory, practical problems, and spectral properties (260C). A classroom demonstration to illustrate the wavelength and spatial distribution of the radiation from a monochromator was developed by Bruzzone and Roselli (42C). The properties of the Russian DFS-13 spectrograph with a 400-500 l/mm grating were described by Fain and Vyatchennikova (98C). Bacis and Femelat incorporated a pressure compensating device into the optical path of a high-resolution spectrograph to improve spectra requiring long duration exposures (14C). Fastie related the analysis and experimental performance of an exit slit mirror system for the Ebert spectrometer used to concentrate the energy from a long exit slit onto small detectors (10OC). Francis received a patent for an entrance slit illuminating system using a cylindrical mirror which forms an image of an elongated straight light source that is congruent with the curved Ebert monochromator entrance slit (107C). Haisch et al. applied an array of exit slits consisting of glass fiber optics to read simultaneously the intensities of the spectral line and of the spectral background on both sides of the line (140C). Woodriff and Shrader described a concave grating arrangement with fixed grating and two mobile exit slits for dual-wavelength scanning operation (415C). White and Cremers modified a conventional 2-m dual-grating Ebert spectrograph to provide photoelectric spatial resolution of a fixed image focused a t the entrance slit by mechanically tilting one grating (409C). Moore and Furst described two methods for calibration and wavelength calculation for echelle spectrograms (258C). Elliott (89C, 9OC), Matz (238C), and Cresser et al. (62C) discussed a commercial echelle monochromator and analytical system. Kolesov et al. measured the spread function width of an echelle monochromator with a Fabry-Perot interferometer (203C). A Czerny-Turner echelle spectrometer especially developed for an image dissector tube readout was presented by Danielsson and Lindblom (67C). Cordos and Malmstadt constructed a programmable monochromator for automatic sequential selection of wavelengths at a rate of 200 A/sec with an accuracy of 0.2 A (61C, 232C). De Sa and McCartan described a digitally scanned exit slit for a high-resolution spectrograph (78C). Robertson et al. corrected wavelength errors in a digitally recording spectrophotometer (311C). Wittmann patented a temperature-tunable laser diode spectrograph in which a variation in the GaAs laser diode temperature was used to change its wavelength (414C). Andreev et al. described a nonlinear spectrograph with controllable dispersion based on the temperature dependence of dispersion in a LiNbOa crystal ( I O C ) . Torok and Papp scanned the spectral image across the exit slit with a rotating plane glass plate to obtain an oscilloscopic display of the line profile (37.92).
Maxwell described catadioptric ima ing systems in a brief monograph (239C), and Wetheraf and Rimmer developed a general analysis for catadioptric systems (408C). Gascoigne surveyed recent advances in astronomical optics (114C), and Korsch developed the analysis of threemirror telescopes for common aberrations (204C, 205C). Sullivan analyzed the alignment of Dove and Pechan prisms used to rotate optical images (349C). Malacara developed a Hartmann test for aspherical mirrors (230C). Wenthen and Snowman designed a 10KHz light chopper (407C), and Blevin constructed a sinusoidal chopper (27C). Brosens evaluated dynamic mirror distortions in optical scanning devices ( 3 7 C ) .Michlovic explained qualitatively the purpose and properties of the Fabry lens (252C). The properties and applications of fluid logic gates for electrical light control were examined by Taylor (364C). Yariv reviewed the status of integrated optics (417C). Svoboda et al. described a simple optical bench arrangement (353C). Nagy developed, in place of a rotating sector, a logarithmic filter for continuous attenuation of spectral lines (268C). Szule positioned glass filters in front of selected regions of a spectrographic plate to improve wavelength selectivity in a low-dispersion spectrograph (360C). Herzig and Spencer manufactured neutral density fiit e n with nonlinear density profiles (152C). Malherbe (=IC), Dobrowolski (83C), and Zycha (428C) described methods for thin-film .interference filters. Wemple and Seman computed the transmission through multilayered planar structures (406C). Fiber optics were described in books by Lisitsa et al. (223C), and Allan ( 7 C ) , a review volume edited by Gambling (113C), and a review article by Dislich and Jacobsen (82C). Walters and Goldstein described an external image transfer optical approach which compensates the internal astigmatism of Ebert and Czerny-Turner spectrometers (402C, 109E). Spence recalled the developments at Kodak in spectral sensitization of spectrographic films and plates (339C), and Hamilton described the photographic grain in a review of the photographic process (141C). Romanova and Prorvin hypersensitized spectrographic films by a single preliminary irradiation (314C), and Kalyanam et al. increased emulsion sensitivity by an intensifying treatment after developing (192C). Torok et al. studied the uniform development of spectral plates in manual and mechanical developers (371C-374C). The smallest deviation in blackening was obtained for uniform mixing of developer in a turbulent flow. Zimmer et al. shortened the total analysis time by rapid development followed by reading still wet spectrographic plates (426C), and Helz described a plate processing, washing, and drying apparatus for 102- by 508-mm plates (151C). Swing considered the conditions for linearity in microdensitometry (354C), and Renyolds and Smith described the nonlinearity and coherence effects in microdensitometry (307C, 202C). Computer data processing and microphotometer automation were developed by Abbasov ( I C ) , Brouwer and Jansen (38C), Helz (151C), Kupo (211C). Le Clainche (220C), Mason (237C), Pellet and Quivy (288RC), Taylor and Birks (362C, 363C) and Torok (370C). For example, Brouwer and Jansen developed a deconvolution method for identification of peaks in a digitized photographic spectrum (38C), whereas, Goto et aE. (34C), Taylor and Birks (362C, 363C), Brooks et al. (36C), and Kupo (211C) identified analysis lines by computer methods. A conversational-mode computer was used by Davis et al. to resolve overlapping spectral lines through an optical fitting procedure (68'2). The microphotometer described by Helz permitted a 1000 readings/sec for a 500-mm long plate in 900 seconds (151C). Klockenkamper and Laqua proposed a method for the preparation of spectral cards for any grating or prism spectrograph and any enlargement of a spectrum projector by a computer controlled plotter (200C). Spectrometer Readout Systems. Spectroradiometric measurements and instrumentation continue under development. The collection of reprints on radiometry and photometry, edited by Hammon and Mason ( 3 9 A ) , and series of NBS technical notes on optical radiation measurements
A N A L Y T I C A L C H E M I S T R Y , V O L . 46, NO. 5, APRIL 1974
157R
by Bums e t al. ( 4 6 C ) , Geist (117C), Zalewski et al. (423C), and Steiner (340C) provide both historical and current descriptions of instrumentation, research, and practice. Rutgers surveyed standard sources available for spectroradiometry (318C). Latyev et al. tabulated normal monochromatic emissivity of W (218C), and Vujnovic proposed a method for self-calibration of W-ribbon lamps (396C). Ott et al. described a method that utilizes the continuum emission from a wall-stabilized arc discharge as a radiometric standard in the VUV (280C, 281C). Stuck and Wende compared two calculable VUV standard radiation sources for the calibration of VUV secondary standard lamps (348C). An active-cavity radiometer, which is a pyrheliometer that accurately defines the absolute radiation scale, was described by Wilson (413C). Photoemission diode standards for accurately measuring monochromatic UV intensities were described by Fisher e t al. (105C). Canfield et al. reviewed the NBS program leading to practical stable transfer detector standards for the far UV (50C). Phelan and Cook described an electrically calibrated detector based on the pyroelectric response of polyvinylfluoride plastic (294C), and Geist and Blevin developed a null radiometer with the detector (118C). Seim and Prydz constructed an automated spectroradiometer (331C). Walker reviewed existing methods and explored new systems for defining the viewing and measuring fields in luminance/ radiance meters (398C). Geist et al. conducted an intercomparison of the instruments used to maintain NBS laser power and total irradiance scales (119C). Nicodemus treated a generalized normalization process for quantities and parameters in classical radiometry (269C). Bennetti e t ai. described a method cor measuring the relative efficiency for a spectroscopic system in the UV to near IR regions based upon known emissivity of W lamps (22C). Included as one of five speakers in the ASTM symposium on optical emission spectrometers (52A), Carrol discussed the descriptions and specifications required in standardizing direct reading spectrometer analysis and hardware performance (52C). Davison (69C) and Turner (382C) described some present commercial equipment and procedures and some future prospects. The 8th and 9th biennial German-language Spektrometertagung were held in Linz and Dortmund in 1970 and 1972. Although the proceedings of these conventions are not published, many of the recent spectrochemical developments in Europe which utilize emission direct reading spectrometers were discussed. Trilesnik compared the technical parameters of five Russian-made spectrometers to two western instruments (378C). Menzies (249C), Riegler (310C), Pfundt (293C) and Stephens (342C) described different applications of computers or calculators to direct reading spectrometers. Hieftje and Sydor explored the application of a wavelength modulation vibrating refractor plate as a means of correcting or minimizing the need for critical alignment stability in direct reading spectrometers (156C). The effects of spectrometer misalignment can be reduced by signal (ensemble) averaging and subsequent peak determination of a repetitively scanned line image. The approach also permitted dynamic background correction, computer compatibility, and feedback adjustments to control spectrometer alignment. A rotating quartz refractor plate was employed by Nordmeyer at the monochromator exit slit in a simple arrangment to measure spectral line and background intensities and to stabilize the spectrum display to. 3~0.005
A (272C).
Giavino described a commercial vacuum Czerny-Turner direct reading spectrometer-monochromator ( 1 2 3 0 . A table of commercially available emission spectrometers was given in the "Annual Reports on Analytical Atomic Spectroscopy" (45A, 46A). Hoyte and Hollenbeck patented (169C) a commercially available, portable, direct-reading spectroscope with an ac arc, horizontal electrodes, and built-in standard comparison spectra on Mylar film for which Crook (64C) prepared a fully illustrated application and instruction manual. Computer automation of direct reading spectrometers is becoming widely applied in industrial laboratories. For
example, Schwarz described computer systems for automatic treatment and transmission of spectrometric test data from a vacuum spectrometer in steel mill laboratories (329C), and Cronhjort and Aslund patented a system in which the guesswork in regulating the exposure time for multichannel spectrometers using the internal reference method was eliminated by continuously measuring the intensity integrals corresponding to the components of a metal sample (63C). Cooper et al. obtained a patent on a method and apparatus to compensate or eliminate the background in a dc arc by subtracting the integrated area corresponding to the background from the area corresponding to a metal impurity plus background (58C). Holler et ai. explained the application of multiple regression analysis to the determination analysis of steel (160C). The emphasis in readout detectors for photoelectric recording seems to have shifted during the past few years from photon counting to photoelectric area scanning. The photoelectric readout system with spatial resolution and simultaneous wavelength coverage of photographic emulsion appears to be closer to realization now than any previous time. As an introduction to photoelectric imaging devices and systems. the two-volume book edited by Biberman and Nudelman serves well (12A). The two-volume proceedings of a symposium on photo-electronic imaging, edited by McGee et al., contains introductory and detailed papers on image tubes, photocathodes and phosphors, signal generator tubes, photon counting, and low level light systems (243C). Other reviews introduce applications as well as descriptions of specific devices. For example, Busch and Morrison surveyed multielement detection systems and considered both temporal and spatial multichannel devices (48C). In contrast, Livingston reviewed various available image-tube systems (224'2). Ghosh reviewed optoelectronic electron tubes (122C), Koc described silicon vidicons (201C), and Engstrom and Sternberg described a high-resolution silicon return-beam vidicon camera tube (920.
Rapid scanning applications are developing as well. Santini et ai. reviewed rapid scanning spectroscopy utilizing vidicon tubes, solid state arrays, acousto-optic filters, and electrically controlled refracting elements (323C). Burke described a commercial prototype fast-scanning spectrometer employing a silicon vidicon camera tube (45C). Although these two articles are oriented to absorption measurements. the devices described may be applied for emission spectrometry. Mitchell e t al. applied (184C, 2 Z C ) a commercial silicon-target vidicon tube system (194C, 275C) for multielement analysis, and Zakharov e t al. developed a spectrometer with television recording (421C, 422C).
Many applications of photoelectric imaging systems remain in astronomy, however. An astronomical spectral application of a digital image tube (Digicon) was described by Beaver et al. (19C). and McCord and Westphal constructed an astronomical photometer with a two-dimensional integrating silicon diode array vidicon tube (242C). At the present, the silicon vidicon tube is the most sensitive near-IR image detector available by several orders of magnitude. Taylor and Boot reviewed pyroelectric image tubes (365C). An additional stimulant in the development of photoelectric image systems is the declassification and commercial availability of improved image intensifier systems. An image intensifier operates as a light amplifier, and the gain is proportional to the number of stages of intensification which are cascaded together. Intensified vidicon cameras are available in 1-3 stage intensifier configurations. Introduced in 1969-70, the silicon intensified tube (SIT) combines one stage of image intensification with a silicon diode vidicon in a single tube. The SIT is the most sensitive photoconductive camera tube available. Second generation image intensifiers have been declassified and may provide a basis for imaging systems in spectrochemical analysis. These Gen I1 high-gain image intensifiers incorporate a microchannel plate for electron multiplication between the photocathode and phosphor. These channel intensifier tubes (CIT) may employ proximity focusing, in
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which both photocathode and phosphor are spaced closely to the microchannel plate. In this configuration, CITs are only about 10% of the weight and length of multiple-stage intensifiers. Altin -Mees ( 8 0 discussed these PFCITs, and Fender (IOZC? described the alternative electrostatically focused CITs. Jeffers reviewed applications of image intensifier systems to astronomy (185C), and Williams and Feibelman described the performance characteristics of an UV image converter in conjunction with a SEC vidicon for use as an echelle spectrograph camera (412C).Rose11 et al. concluded that the proximity focused intensified electron-bombarded silicon (I-EBS) camera tube was one of the most promising new sensors available for low-light-level imaging (316C). They discussed the I-EBS performance and characteristics. Smith described the application of image tubes as shutters (335C). Hunter and Harlow compared two types of UV-to-visible image conversion techniques ( I 73C) used in coniunction with a SEC vidicon camera system (376C). An aluminum coated phosphor (p-quaterphenyl) and a channeltron electron multiplier array (CEMA) showed no difference in resolution, although the CEMA displayed a greater gain. Gwaltierti et al. investigated solid state optical materials for UV-to-visible conversion (138C). Burton and Powell measured the fluorescence of tetraphenyl-butadiene in the W V as a useful alternative to sodium salicylate as W V visible converter material (47C). The use of MgFz and LiF photocathodes for CEMs in the UV was evaluated by Lapson and Timothy (226C). Hunter surveyed optics, detectors, and sources used in the vacuum ultraviolet (172C). Semiconductor photoelectric arrays and self-scanning systems may provide in the future a suitable alternative to imaging tubes and photographic emulsions. Although the target of the silicon vidicon is composed of a photodiode array, commercially available self-scanning linear silicon photodiode arrays and charge coupled imaging devices ( 5 1 C ) will probably be more conveniently applied in spectrochemical systems. Because charge injection imaging devices are still in the prototype stage, experimental comparisons with CCDs and PD arrays will be delayed. Boumans et al. (32C, 33C) developed and evaluated two solid state photodetector systems for use in multichannel emission spectrochemical analysis. Boumans and Brouwer (32C) studied a one-dimensional array of 20 equally spaced silicon phototransistors as a detector in a dual channel arrangement which allowed simultaneous line and background measurements. Using a more sophisticated arrangement, Boumans et al. (33C) used various configurations of planar silicon photodiode arrays. They found that spectral resolution was equivalent to that obtained with a conventional exit slit arrangement, but that photodiode S/N-ratio a t low intensity ultraviolet and visible levels was inferior by 100 to that of photomultipliers. Horlick and Codding characterized and applied a selfscanning linear silicon photodiode array as a detector in various emission spectrochemical systems (592, 166C, 167C). When mounted along the focal plane of a 35-cm monochromator with a reciprocal linear dispersion of 20 A/mm, a 256-element linear photodiode array covered 128 A. A typical spectral line was sampled simultaneously by 1C12 photodiodes. Each diode signal is integrated from 10 msec to 2.6 sec (166C), although linearity dropped above 800 msec without cooling. Employing a novel readout system based upon this photodiode array, Horlick and Codding demonstrated smoothing, resolution enhancement, and differentiation of the spectra by means of an analog cross-correlation of the diode array signal with an appropriate electronic waveform (167C). In another novel and potentially valuable application, emission spectra of 35 elements excited in a dc arc were measured over a 140-Arange with the self-scanning arraymonochromator system, reduced to a binary representation, stored in a small number of computer words, and used in AND or exclusive-or logic operations for automatic qualitative analysis ( 5 5 C ) . Expansions of these rather inventive applications of photoelectric arrays may succeed in replacing photographic detection in many routine applications. Codding and Horlick reported the use of an improved
computer-coupled photodiode array spectrometer system for simultaneous multielement quantitative analysis with a dc arc source (56C). They also used a photodiode array spectrometer to measure dye laser intra-cavity enhanced absorption spectra ( 2 6 8 C ) . Two special issues of IEEE Transactions on Electron Devices contain articles on solid-state imaging and imagesensing devices (176C). Frova edited the proceedings of an international conference on semiconductor light emitters and detectors (1lOC). Strull et al. described a solid-state camera composed of a 400 x 500 silicon phototransistor array which exhibited the same resolution as a standard TV camera (347C). Rokos derived the noise performance of photodiode-amplifier combinations (313C). Hamstra and Wendland measured the noise and frequency response of Schottky barrier and diffused PIN non-guard-ring photodiodes and operational amplifier combinations (142C). Mohan et al. studied the stability and temperature characteristics of some silicon and selenium photodetectors (257C). Properties of (Hg, Cd)Te photodetectors were described by Aldrich and Beck ( 4 C ) , and Halpert and Musicant (430C). Because of the unique properties of (Hg,Cd)Te, two or more devices may be coupled in a sandwich configuration instead of being placed side-byside. This simplifies optical and electronic requirements. Dimmock surveyed infrared detectors and their applications (82C). One of the major developments in multiplier phototube technology in the recent past is the design of new photocathodes based on the negative electron affinity concept exhibited by group 111-Va compounds. Bell wrote a monograph describing the principles of this new class of electron emitters, and included a detailed treatment of photocathodes, secondary emitters, and cold cathodes ( 2 I C ) . Developments through early 1973 are described. Williams (4IOC), Rome (315C), Krall and Persyk (207C), Persyk and Crawshaw (292C), and Syms (355'2) reviewed use of these negative electron affinity materials in photomultipliers and imaging devices. Sommer discussed the effects of cathode material. formation process, tube geometry, and other variables on the stability of photocathodes containing alkali metals (338C). Ageing of S-10 photocathodes (43C) and spectral sensitivity measurements (44C)were described by Budde et al. Sackerlotzky and Belanger described a new ceramicenvelope electron multiplier design (320C), and methods and apparatus for improving the quantum efficiency of phototubes by multiple internal total reflection were described by Prydz and Kolberg (302C), Oke and Schild (274C), and Dvorak (87C). The quantum efficiency and detective quantum efficiency of photomultipliers and photographic materials were measured and compared by Thiry with a He-Ne laser (368C). Sauerbrey discussed sources of nonlinear response of photomultiplier tubes (324C). Ingle and Crouch developed a mathematical treatment and comparison of signal-to-noise ratio characteristics of photomultipliers and photodiodes ( I 78C, 322C). Ingle and Crouch also make a critical comparison of photon counting and direct current measurement techniques for quantitative spectrometric methods ( l 8 0 C ) , and described the effects of pulse overlap on linearity and signal-to-noise ratio in photon counting (179C). Malmstadt et al. (233C, 234C) reviewed photon counting systems and applications in spectrophotometry. Hieftje reviewed a number of popular instrumental techniques for signal-to-noise enhancement (253C). Various treatments of photon-counting statistics and distributions were described by Mehta and Mehta (247C), Lachs and Ruggieri (213C), and Coates ( 5 3 C ) . Dagnall et al. described a simplified photon-counting system ( 6 3 3 , and Dawson compared photon counting and dc measurements (70C). Birenbaum and Scar1 measured photomultiplier single photon-counting efficiency (26C), and Preutt developed a photon-counting system for rapidly scanning low-level optical spectra (300C). Amoss and Davidson compared an image scanning optical fiber probe-photomultiplier arrangement employing photon counting to a photographic emulsion ( 9 C ) . The photon-counting technique was 100-fold more sensitive than the emulsion for
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comparable signal-to-noise ratio. Prydz proposed a photomultiplier for which photons impinging at different sites on the photocathode would give rise to pulses of systematically varying heights (301C). In combination with a multichannel pulse height analyzer, the unit would provide a one-dimensional photon-counting image detector. Grekhov et al. proposed the use of a microplasma as a photon counter ( I 3 5 C ) . Techniques and application of derivative spectroscopy were reviewed by Grum et al. i136C, 411C), and Seraphin edited the proceedings of the first international conference on modulation spectroscopy (332C). Instruments incorporating, or techniques for obtaining, spectral wavelength modulation were described by Hager (139C), Hart et al. (147C), Hieftje et al. (156C), Jobe ( I S S C ) , Nitis et al. (270C), Schedewie and Kunz (325C), Schmidt (326C), Welkowsky and Braunstein (405C), and Zucca and Shen (427C). Ewing reviewed the instruments and techniques of multiplex spectroscopy (97C), and Hirschfeld and Wyntjes compared Fourier and Hadamard transform spectroscopies (158C). Hadamard transform spectrometers were designed and described by Hansen and Strong (143C), and Decker (73C-75C). Kowalski and Bender introduced the Hadamard transform as an alternative preprocessing step for spectral analysis by pattern recognition (206C). Patents for correlation spectrometers were obtained by May (240C),and Barringer Research ( I 7 C ) . Wyller and Fay combined an echelle monochromator with a pressure-scanned Fabry-Perot [PSFP] interferometer in a variable-resolution, broad-wavelength (350013,000 A) instrument called URSIES (416C). Astronomical applications required this type of system to increase light efficiency for low level light fluxes collected through a telescope. Photon counting was employed and circular and linear polarization in spectral lines were measured. Bates et al. ( I S C ) coupled a Fabry-Perot [F-PI interferometer with an echelle grating monochromator for use in the middle W. Simultaneous mechanical scanning of interferometer and grating premonochromator provided spectral recording. Meaburn discussed the approach (245C), construction, and performance (246C) of a combined Sisam FabryPerot monochromator. By using slow pressure scanning and piezoelectric modulation a combined Sisam F-P monochromator was operated in the visible instead of the IR. Properties of other combined systems, such as a Pepsios monochromator were discussed and compared (245C). Cooper et al. described a digitally pressure-scanned F P interferometqr [PSFP] coupled with photon counting for studying weak spectral lines (59C), and Gault and Shepherd determined the dispersion and refractivity of gases which may be used for interferometric pressure scanning (115C). Beysens developed a very high resolution confocal F-P spectrometer which maintained resolution over long periods for line-width measurements (24'2). Persin and Vukicevic constructed a quasi-confocal F-P interferometer using a spherical mirror glass block etalon to obtain high resolution (>lo?) and satisfactory instrument finesse (>30), for low intensities (291C). Sokolova characterized nonabsorbing mirrors for the ultraviolet obtained by a chemical method from oxides of Th, Zr, and Hf for F-P interferometers (336C). A new method which uses an electronic imaging tube to record F-P fringes was explored by Gagne et al. (112C). McLaren and Stegeman described stabilized photon counting data collecting systems for a repetitively swept piezoelectrically scanned F-P [PZFP] interferometer (244C). Interferometric measurements of atomic line profiles emitted by atomic line sources including hollow cathode lamps and combustion flames were reported by Wagenaar and De Galan [PSFP] (76C, 397C), Kirkbright et al. [PZFP] (6C, 199C), and Veillon and Merchant [PZFP] (389C). Nitis et al. [PZFP] (270C), and Veillon and Merchant wavelength modulated a continuum source with a PZFP for atomic absorption. Some general apparatus considerations were also described by Veillon and Merchant. Drummond and Gallagher described a low-resolution scanning multiple F P spectrometer for observing very weak extended light sources (84C). Sharma and Singh developed a graphical method to obtain the shape and width 160R
of an isolated emission line from its interferogram (333C). The intensity problems associated with interferometry in the far UV were discussed by Gion (125C). Proper reflective coatings for the far UV proved superior to large increases of source temperature for the hook method (30A) . Yokozeki and Suzuki give the theoretical interpretation and experimental verification of a modified double-beam interferometer using the MoirC technique (419C). Golay concluded that off-axis or cassegrainian parabolic optics offered promise for good field corrections in designing interferometers ( 1 2 7 0 . For use of interferometers in Fourier spectrometers, Girard patented a Michelson arrangement consisting of a solid glass block with a beam splitter embedded (126C); Bottema measured the transfer function of a Williams interferometer (29C), and Kruger et al. designed and tested an all-reflection interferometer (210C). Sanderson surveyed Fourier spectroscopy (321C), and Filler demonstrated that photon-noise-limited Fourier spectroscopy produced a superior signal-to-noise ratio compared to an equivalent scanning spectrometer for line-emission spectra (104C). Codding and Horlick presented several aspects of apodization and use of phase information in Fourier transform spectroscopy (54C). Walmsley et al. corrected offcenter sampled interferograms by a change of origin in the Fourier transform (399C),and Volkava et al. modeled the effects of reading accuracy on the form of the Fourier spectrometer spread function (392C). Horlick employed data handling techniques developed with Fourier transformations to smooth, differentiate, and enhance resolution of line emission spectra (163C, I65C). The calculations were illustrated for a small grating monochromator. A similar resolution enhancement technique was used by Goldman and Alon (129C). Meredith described a new method for the direct measurement of spectral line strengths and widths and numerically evaluated instrument errors by passing an idealized spectrometer slit function over several assumed line profiles (250C). Queffelec et al. applied a deconvolution method to study the influence of spectrometer instrument function on broadening of an Ar emission line profile in an Ar-HZ plasma (303C). Interactive deconvolution methods were applied by Szoke (358C), and Zenitani and Minami (424C), but Sventitskaya used an Gaussian curve as the instrument function in obtaining true spectral line profiles ( 3 5 I C ) . Kapicka et al. measured the instrument function of a Fabry-Perot interferometer (193C). Lagutin studied the effect of operating conditions of recording systems on distortion of line contour (214C). Horlick searched for desired spectral features in a raw spectrum through the application of cross-correlation techniques (164C). Presence or absence of a feature was determined from the resulting cross-correlation pattern. Aitken and Carter developed a real-time optical correlator based on the principle of one-bit correlation which showed a greater immunity to mechanical noise than a comparable analog optical correlator ( 3 C ) . Signal processing by cross-correlation was directly compared by Hieftje e t al. to lock-in amplification for atomic fluorescence signals (154C). An ultra-high-speed stroboscopic spectrometer employing an image converter camera as a single sampling system was described by Uchida and Minami (385C). A prototype instrument showed time resolution of 0.3 nsec. Shchelev et al. investigated the performance of a standard commercial image converter tube for streak-limited time resolution of 35,000 “K (157C). Emission from an aluminum hollow cathode discharge below 1100 A was found superior to other sources by Entzian and Gaebel (93C). Kikuchi described a new VUV microwave atomic line source oper162R
ated at 35 GHz and 9 W (197C). Van Raan developed an absolute intensity calibration method for the VUV based on electron impact excitation and theoretical calculation of the emission cross section of noble-gas resonance lines (387C). Far UV vacuum monochromators were designed by Pouey (298C), Behring et al. (20C), and Dietrich and Kunz (80C). Peacock et al. (159C, 182C) described spectrograph calibration at soft x-ray wavelengths from grating diffraction efficiency and plate response factors (159C) and from branch ratios (182C). Fairchild described aluminum-dielectric Fabrey-Perot interference filters for the 1200-1900 8, range (99C). The improvement in optical properties of vacuum monochromator optics after exposure to atomic oxygen were measured by Johnson (187C),and Hunter et al. (175C). STANDARDS, SAMPLES, CALIBRATION, CALCULATION The IUPAC committee on spectrochemical and other optical procedures for analyses recommended usage of nomenclature, symbols, and units in spectrochemical analysis. Section I concerns general atomic emission spectroscopy (480);section 11, terms and symbols related to analytical functions and their figures of merit ( 4 6 0 ) ; and section 111, analytical flame spectroscopy and associated procedures ( 4 7 0 ) . A number of proposals for standardized nomenclature for radiometry have been discussed by Sinclair (SSD), Geist and Zalewski (3501, Nicodemus ( 8 4 0 ) , and Gravely (390). The proceedings of an ASTM symposium on samplin , standards, and homogeneity record many of the difficuyties and precautions recognized in spectrochemical analysis (53A). A survey of recent publications related to sample preparation in emission spectroscopy is featured in the methodology section of the “Annual Reports on Analytical Atomic Spectroscopy” (45A, 46A). The sixth Materials Research Symposium on Standard Reference Materials and Meaningful Measurements convened in Oct. 1973 at the National Bureau of Standards. Youmans prepared a statistics for chemistry manual to make simple data treatment and experimental design methods available to undergraduate students (1200). Standards. Laurent et al. surveyed the sources of supply, criteria of selection, uses and criticisms of standard reference materials in Europe ( 7 0 0 ) . A list of standard reference ores and rocks available from the Canadian Mines Branch was compiled by Faye ( 3 0 0 ) . Stoch et al. described South African mineral reference materials ( 1 0 5 0 ) , and Stepin et al. described new Russian standard samples produced in 1969 ( 1 0 4 0 ) . Kennedy described the problems in manufacture of NBS cast metal standard reference materials (560). Golightly and Weber evaluated calibration standards used in the DOD equipment oil analysis program ( 3 6 0 ) ,and Okazaki and Kawashima studied Japanese standard iron and steel standards ( 8 5 0 ) . A mold for casting aluminum spectrographic standards was described by Redfield and Wagoner ( 9 2 0 ) . Pliner et al. described the evaluation of homogeneity of standard samples ( 9 0 0 ) , and Buravlev published a book on the effect of composition and sample size on the results of spectrochemical alloy analysis (110).The production of standards was described for pig iron by Gegner and Kunze ( 3 4 0 ) , ferrous alloys by Komar et al. ( 6 1 0 ) and Pliner and Rubinshtein ( 8 9 0 ) , magnesium alloys by Fridman et al. (330),titanium by Vasilevskii et al. (1130), gold by Lantsev (680), noble metal alloys by Ivanov and Mironenko ( 4 9 0 ) , plutonium by Buffereau and Genty ( 9 0 ) , and minerals by Marzuvanov and Baisakdov ( 7 8 0 ) . Yakowitz et al. described the preparation and homogeneity of an austenitic iron-chromium-nickel alloy (1190). Piatek prepared nickel and nickel-iron standards (8430). Sampling, Sample Preparation Techniques. As the effort continues to obtain spectrochemical analysis for elements in extremely low concentration from environments which compound element losses and matrix effects, serious consideration was given during the past few years to
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the preparation of pure reagents, the loss of elements in containers, and the interference-free manipulation of samples Skogerboe and Morrison reviewed essentia1 analytical characteristics and sources of errors in sampling and pretreatment for instrumental methods used in trace analysis (970). Mitchell described practices in ultrapurity necessary for trace analysis (820). Toelg surveyed the methods for the preparation and dissolution of samples and for the isolation of trace elements in the ultra trace range in inorganic and organic matrices (1110). Barnard described the application of emission spectroscopy in a chapter of a book on ultrapurity methods and techniques (30). He also reviewed the importance of high purity reagents and standards for spectrochemical analysis of trace metals ( 4 0 , 1220). Conway et al. described the ultrapurification of water (160), and Mattinson (800) described the preparation of and Kuehner et al. (640) special high-purity acids. The final purification of inert gases for sRectrochemica1 purposes was described by Slickers (980).The losses of trace elements and storage properties of containers were described by Von Ameln et al. (1140), Struempler (1060), Kuroha (650), Coyne and Collins (180), and Feldman (310). The use of a Teflon-lined decomposition vessel was described by Bernas (80), Rantala and Loring (910), and Woltermann (1180). Smith and Parsons listed critically selected compounds used in the preparation of standard solutions (990). Koirtyohann and Wen conducted a critical study of the AF'CD-MIBK extraction system for trace elements (580), and Jackwerth et al. described the application of activated carbon as a collector for trace elements (500). Chalmers reviewed enrichment methods for trace analysis (140). Krasil'shchik and Yakovleva reviewed the use of electrolysis for concentration of impurities for subsequent spectral analysis (630), and Yudelevich et al. applied the method to Ga or GaAs using the end of a graphite electrode for electrolysis followed by excitation in a dc arc (1210). Stateczna reviewed the problems connected with sampling environmental and industrial gases (1020), and Fair et al. described systems for continuously monitoring process streams for trace components (280). Dieleman et al. employed graphite electrodes as substrates for collecting GaSe samples as thin films for analysis instead of using a separate collection substrate followed by sample transfer (230). Cline described the problems in sampling ferroalloys with particular emphasis on ferrosilicon ( 1 5 0 ) , and Jenkins and Soth described the sampling procedures required in a basic oxygen steel facility (510).The sampling of liquid steel from large electric arc furnaces was described by Statham (1030). The remelting of crude iron and steel samples by high-frequency heating in a ceramic crucible was evaluated for precision by Loose and Schmitz (740, 940). Williams and DuBois described the methods for the rapid, continuous analysis of molten steel (1150). Grant and Pelton emphasized the role of homogeneity in sampling powder and concluded that the error contributed by heterogeneity could not be completely eliminated (380).They included a brief discussion of sampling theory. The applications of ultrasonic and vacuum deposition techniques in the mixing of powder samples and preparation of standards were described by Kurteeva et al. ( 6 6 0 ) , Klochkov et al. (570), and Kuzovlev et al. (670). Preparation of nonmetallic samples by means of preliminary fusion in a graphite crucible, followed by grinding both charge and crucible, and compressing final powder into a pellet was developed by Wittmann and Chmeleff (117 0 ) . A new procedure for rapid pulverization of hard ores consisting of rapid heating and subsequent quenching was investigated by Azuma and Yoshida ( 2 0 ) . The effect of crushing ferrous alloys on the sensitivity of determining nonferrous impurities in a dc arc was evaluated by Maiboroda and Raskevich (750). Investigations of ultrasonic nebulization of solutions for spectrochemical analysis were undertaken by Souilliart et al. (1000), Copeland et al. (1701, Denton et al. (220, 6 2 0 ) , and Buraev and Vereshchagin (IOD). Johnson and
Smith measured the supply rate of a nebulized solution (520). Internal Standards a n d Other Techniques. Larsen et al. estimated the uncertainty term expected in the method of standard additions using linear regression analysis as an approximation to the experimental error (690). The method agreed favorably with the standard deviation for values which were not corrected for a blank as well as with the population standard error of difference for corrected samples. Flaschka and Paschal outlined the procedure and wrote a computer program for the method of standard addition with partial sample consumption (320). Litomisky used molecular emission bands as reference lines in the spectrographic analysis of nonconducting materials, and the reference component could either be an inherent constituedt of the sample or could be added (720). Barnes and Malmstadt demonstrated that the solute applied as a thin solution layer on a solid sample during sparking could serve as the internal reference material for point-to-plane spark analysis of alloy samples (50). Schoenfeld described a numerical method for calibration based upon the exposure of a single standard at several different times under conditions for which synthetic standards or the method of standard additions cannot be accomplished (950). A method for the routine analysis of solution aerosols using a single standard solution with varying exposure times was described by Moselhy ( 8 3 0 ) . Pakey described a dual standard method, based upon the time in the determination of an absolute line intensity and the intensity value of the internal standard line, to reduce the interaction of sample elements on the internal standard line for analysis of steel samples (870). Suckewer discussed the sources of error in determining atomic density ratios and spectral line pairs in a discharge, especially under nonthermal conditions, and in relating them to density ratios in the sample (1070, 1080). He also described the theory of excitation and ionization of atoms and ions in nonthermal equilibrium as might be observed for spark and low-pressure discharges (1090). Analytical Functions, Figures of Merit. The IUPACproposed nomenclature in spectrochemical analysis includes a section of terms and symbols related to analytical functions and their figures of merit in which carefully worded, practical definitions established the mathematical meanings of functional, statistical, and operational figures of merit (460). Defined for functional figures of merit were sensitivity, selectivity, specificity, and partial specificity; for statistical figures of merit were precision, limit of detection, power of detection, and limit of guarantee of purity; and for operational figures of merit were accuracy and informing power for a procedure. These concepts and definitions of selectivity, specificity, and sensitivity were developed fully by Kaiser ( 5 3 0 ) who has for more than 25 years stimulated the search for practical, unambiguous quantitative concepts in spectrochemical analysis. In a series of papers, Eckschlager reviewed the applications of mathematical statistics and information theory in the evaluation of analytical methods and results (250); modified the criterion of acceptability of analytical methods (240); discussed the factors responsible for loss of information content in analytical results (260), and compared several alternatives in an analytical procedure based upon the determination of the effectiveness of information (270). Belyaev and Koveshnikova discussed the use of information theory in analytical chemistry ( 7 0 ) , and the evaluation of the information capacity of analytical methods (60).The potential and practically useful information quantities of analytical methods were described by Danzer (200). Wilson suggested an approach to define the range of concentrations covered by an analytical method as an important performance characteristic (11 6 0 ) , and Kaiser gave a system of definitions for units and quantity ranges in analysis (540). Matherny suggested that the definition of the final precision value of concentration values include a method of successive summations of partial errors and that the definition of limit of determination be derived from the function expressing the final relative precision (790). To evaluate the detection limit, Liteanu and Rica used
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the concept of decision level, which was estimated by employing a two-stage model with the Neyman-Pearson criterion used in the statistical theory of signal identification (710). Gottschalk discussed the application of system theory, theory of games, and information theory in modem analysis ( 3 7 0 ) . Buyanov classified the factors influencing sensitivity and accuracy of emission spectrometric analysis ( 1 3 0 ) , and Haisch studied the effect of spectrometer slit width and line profile on calibration curve and detection limits for the situation of simultaneous measurement of line and background (140C, 4 1 0 ) . He discussed the detection limit for cases of constant noise level, a noise level determined by photon noise, and a noise level produced by photomultiplier statistics. Heiftje reviewed techniques for signalto-noise enhancement through instrumental methods (153C), and Ingle and Crouch developed expressions for signal-to-noiseratios (178C). Anders outlined a statistical technique for discovering generic relations among samples based upon the correlations found for matching the ratios of elemental concentrations of a sample with the equivalent ratios of other samples (ID). Currie et al. reviewed statistical and mathematical methods for characterizing the measurement process, for planning and control of experiments, and for curve fitting and use of on-line computers (190). Kojima also surveyed the statistical treatment of analytical data ( 5 9 0 ) . Kelly described methods for data processing, which included direct, graphical, minmax, least squares, maximum likelihood, and methods based on Bayes’ theorem, that might be applied to spectrographic data ( 5 5 0 ) . Olcott discussed the calculation of confidence limits on the product of two uncertain numbers ( 8 6 0 ) . Grinzaid and Nadezhina proposed the use of correlation of random fluctuations of light source temperature with the calibration curve during the spectrographic analysis of pig iron ( 4 0 0 ) . Howarth developed a Monte Carlo simulation of matrix correction effects which could be useful for precise evaluation of the influence of complex systems of matrix correction found in spectrometric analysis ( 4 5 0 ) . Photographic Emulsion Calibration, Computation. In their monograph on quantitative evaluation of spectrograms, Torok and Zimmer reviewed the mathematical formulas developed to describe the characteristic curve which relates the response of a photographic emulsion to exposure (85A). They detailed the concept, characteristics, and applications of the l-transformation, which applies only to the toe of the emulsion calibration curve. Tdrok et al. also studied emulsion processing to obtain a uniformly developed emulsion (371C-374C), and Torok described a fully automated evaluation of photographic spectra (370C). The properties and characteristics of photographic detectors, their theoretical descriptions, and practical manipulations were presented in the “SPSE Handbook of Photographic Science and Engineering” (88A). Srorko and Strizh reviewed spectral transformation obtained by digital computers ( I O I D ) , McCrea commented on the calculation and misnaming of the logistic (“Seidel”) function ( 8 1 0 ) . Burton et al., determined the characteristic curves and absolute sensitivity of photographic emulsions in the vacuum UV ( 1 2 0 ) . Herz developed a computer program for correction of emission data to produce a true emission spectrum ( 4 4 0 ) . Computer Calibrations. Deming and Morgan described the use of simplexes for optimization of experimental variables ( 2 1 0 ) . A method of approximate polynomials was described by Romanova for the optimization of computer solving of emission spectrographic problems ( 9 3 0 ) . Lontsikh et al. used experimental planning methods for improving spectrographic analysis accuracy ( 7 3 0 ) . Fal’kova et al. described a procedure for calculation of the error of grouped analytical results based on the hypothesis of a log-normal distribution of semiquantitative spectral analysis errors ( 2 9 0 ) . Vakhobov and Kesterov applied a random balance method to obtain optimum values of 12 factors in a spectrographic analysis (11 2 0 ) . Thompson and Howarth developed methods for estimating and controlling analytical precision by using precision estimators derived from the difference between dupli164R
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cate determinations (1100). Statistical control and designs in experimental planning were surveyed by Mandel (770). Kollin and Ziemens applied an operational theory of attendance to the discontinuous flow of samples in spectrometric analysis to determine the operator attendance time per sample (600).Malissa and Rend1 proposed a system for the classification of the amount of sample taken for an analysis and the content of the constituent to be determined, and the advantages in the classification of analytical working ranges were specified ( 7 6 0 ) . Hauptmann et al. evaluated several graphical and numerical methods for the determination of residual concentrations in emission spectroscopy ( 4 2 0 ) . Hecq described a computer calculation for emission spectrographic analysis ( 4 3 0 ) .
EXCITATION SOURCES The objective of this section is to highlight those publications which consider the sampling and excitation processes observed in thermal and nonthermal excitation sources of direct interest for spectrochemical analysis. An extensive chapter written by Boumans surveyed through approximately 1969 the theory and description of spectrochemical excitation sources (31C), and although major new developments have occurred in the past few years, this chapter can serve as an excellent primer. Mika and Torok’s book also described processes occurring in the classical arc, spark, laser, and discharge tubes (63A). Laqua presented a progress report of spectrochemical light sources encompassing arc, spark, laser, and reduced-pressure discharges (183E). A number of potentially useful emission sources do not fall into usual categories. For example, Ritschl and Schuster excited spectra for emission spectrochemical analysis by low energy electron impact (260E, 261E, 2753). The light source consisted of a resistance heater like the King furnace for sample evaporation and an electron impact source for excitation. The arrangement was employed to determine trace elements in spectral-grade graphite and to study the transport of material between electrodes in a high-voltage spark. Electron impact voltages just above the ionization potential of the desired component but below that of the bulk material provided detection sensitivities which were lower than obtained by conventional emission methods. Steichen and Franklin employed a photoelectron spectrometer to investigate the emissions of He, Ne, and Ar discharges to demonstrate the usefulness of the electron spectrometer as a pseudo-UV monochromator (298B). Willis used a quadrupole mass filter and electrostatic lens system for study of laser impact and vacuum spark plasmas and conducted theorewv investigations with computer models of the laser impact and expanding sphere plasma (360E) for the determination of halogens. Gardy et al. discharged a low-voltage capacitor through a very fine filament of graphite saturated with analyte solution (I03E), and Krasil’shchik and Raginskaya analyzed solutions by means of a discharge in a narrow capillary connectine two electrolvte solution comDartments ( I 75E). Kusch-et al. investkated the discharge properties of a high-current pulsed discharge through Plexiglas capillaries (82E. 83E. 179E). Arc Plasmas. The active investigation of arc stabilization by means of applied magnetic fields continues in both Western and Eastern European countries. Lotrian and Johannin-Gilles demonstrated the stabilization effect of a rotating radial magnetic field on an arc discharge in argon a t medium current and high pressure, and they studied the variation of the fluctuation of the arc voltage as a function of current and magnitude and rotation frequency of the magnetic field (295E). Near the optimum value of magnetic field, an improvement in stabilit y and an increase of emission intensity, corresponding to a radial intensity distribution, were observed. Bril et a l . applied a high speed camera technique and simultaneous recording of electrical and optical parameters t o study the behavior of the graphite dc arc discharge in a magnetic field (42E). The arc rotation speed was a linear function of both current and magnetic field, and two different mechanisms were found for the arc rotation. Arc rotation
NO. 5 , APRIL 1974
did not affect plasma temperature or spectral line intensities. Vukanovic et al. investigated various magnetic field arrangements in arcs for trace element analysis and concluded that external fields increased the method sensitivity (104E, 356E). Petrakiev et al. (244E),Kharizanov et al. (155E), and Leushacke (188E) reported spatial studies of magnetic intensifications in dc arcs. Belchev and Kirov studied the influence of different buffers on magnetic intensification (24E). Buyanov et al. considered increasing spectrometric analysis accuracy through magnetic stabilization ( 5 1 E ) , and Kharizanov and Krasnobaeva improved the limits of detection by a factor of 2-3 for the analysis of solution residues in a dc arc with a nonhomogeneous magnetic field (154E). In contrast, Decker observed a definite deterioration in detection limitsfor the cathode layer method when a stationary inhomogeneous magnetic field was applied (67E). This was due apparently to the rotation of the cathode spot about the electrode cavity walls, which burned away preferentially. Nickel and Keintzel observed an increase in reproducibility and a narrowing in lines when a homogeneous magnetic field was applied to a high pressure He arc arrangement (2266). Definition of the electrode and mass transport processes in a dc arc remains the most difficult aspect in describing an entire analytical arc system. Nickel surveyed some thermochemical reactions of sample components a t high temperatures experienced in arc and spark discharges under Ar and Nz atmospheres (2243). He showed that X-ray analysis of products combined with thermodynamic calculations could not safely lead to prediction of the formation reactions of transition element carbides and nitrides. Autoradiographic, fast photographic, and interferometric studies of arc evaporation and streaming indicated that analysis results depended on the physical properties influencing the consumption of the electrodes, as well as the atmosphere. Yudelevich and Volodarskii described a technique for measuring the temperature distribution along an electrode and the temperature fluctuation during sample evaporation in an arc discharge (371E). Avni and Goldbart measured the volatilization rates of free particles from an anode into an arc discharge for U, Th, and Zr matrices by means of two different techniques, one of which involved a moving wire grid ( I I E ) . For the U matrix, the axial distribution. of the transport parameter was calculated after volatilization rate, total free particle concentration, and axial velocity were measured (12E). From these measurements, the total concentration of molecular uranium species in the discharge was obtained. For the U, Th, and Zr oxide matrices, axial and radial temperature field gradients in the arc were also measured, the spatial distribution of electron densities was calculated from the Elenbaas-Heller equation by using mean electrical conductivities and neglecting radiation losses (14E). In the development of an analysis method for silicate materials, Avni et al. evaluated the axial distribution of volatilization rate, temperature, electric field, electron density, and line intensities in selecting a discharge region in which the major constituents exerted a minimum influence on trace and minor components (13E). Mazurkiewicz photographed the evaporation from a carbon arc in Ar and He (202E). High speed photographs showed the developmemt of eddies in Ar which circulate atoms under analysis between the anode and cathode leading to a long residence time in the discharge and, consequently, relatively high line intensities. The arc in Ar was wide with low axial and radial thermal gradients, whereas in He very steep radial and axial gradients lead to lower excitation than in Ar. An Ar-02 ( 4 : l ) mixture displayed results intermediate between Ar and He. Nickel and Keintzel investigated dc arcs with pointed W pencil cathode and cylindrical or spherical graphite anode in He pressures up to 50 atmospheres for use in spectrochemical analysis of impurities in nuclear reactor fuel elements (226E). Vaporization and stability a t different He pressures were studied, and a homogeneous magnetic field applied along the arc axis centralized and stabilized the discharge and reduced the material transport
from the anode. The reproducibility was increased and the lines were narrowed by applying a homogeneous magnetic field. Mannkopff et al. reported the supression of CN band emission during spectrochemical analysis through the shielding of an arc discharge with CO (201E). Ternary copper alloy calibration curves in air and argon showed third-element differences when excited by Grikit and Galushko in spark and ac and dc arc discharges ( I 19E). A thorough study of the operational parameters which affect the dc arc cathode layer was reported by Decker (67E). He found that the sample must evaporate directly into the cathode layer if any benefit is to be obtained, and that any movement of the cathode spot from the sample seriously affected the detection limits. The distribution of atoms in the cathode layer was markedly affected by the increase in concentration of low ionization potential elements. The detection limits were increased and could be slightly better than those obtained with anode techniques. For high concentrations of low ionization potential elements, the position for optimum detection limit was moved away from the cathode, depending on the ionization potential and the degree of suppression of the cathode layer enrichment. The amount of sample required to obtain a given line to background ratio was less with the cathode layer technique than with an anode technique. Controlled atmospheres removed cyanogen bands but contributed little to improved detection limits, and the application of a stationary inhomogeneous magnetic field caused deterioration of detection limits. With samples such as natural materials containing high concentrations of low ionization potential elements, detection limits could be two or three times better than using anode techniques. Pamitokov and Krasovitskii studied the physical mechanism for the formation of the cathode layer (240E). Titarenko investigated the reactions occurring in a chamber electrode during the fractional distillatiop of tin samples (3363). During the spherical arc excitation of palladium standards, Toelle found segregation of phases which hindered the determination of elements in Pd (3373). T o evaluate the dc arc discharge for analysis, Dittrich et al. applied a photographic technique which provided contour maps of equidensity in the arc plasma that were used to evaluate electrode configurations, and particle and intensity distributions of an arc in a magnetic field (74E). By using two movable microprobes inserted directly, Apolitskii measured the structure and potential gradient of the electric field of a dc arc during sample evaDoration (7E, 8 E ) . Smirnova and Krinberg developed (290E, 291E) and experimentally verified (2923) a mathematical model for the mass transport of particles through arc discharges in which the convection transport of particles along the arc radius in outer discharge regions, the changes in transport rate along the discharge axis, and the effect of the upper (cathode) electrode were taken into account. Raikhbaum et al. discussed systematic errors in spectrographic arc analysis due to mass transfer changes caused by incorrect electrode geometry and the diffusion of sample into the electrode walls which results (231E, 2573). Raikhbaum et al. also developed an overall model for the principal processes in arc spectral analysis in which the input current and the output intensity were related through Laplace transforms (2563). An expression for a general transfer function was obtained by linearizing functions corresponding to electrode heating, evaporation, vapor loss, and excitation. The emission of lanthanum and other similar elements in a dc arc is complicated by the existance of stable monoxides a t arc temperature, and Antic ( 6 E ) and Antic and Car0 (5E) studied the behavior of lanthanum and the influence of spectroscopic buffers and gas atmospheres on its excitation in dc arc plasmas. Thermodynamic parameters were measured, and comparison of temperatures derived from different La I1 line pairs indicated perturbation of La populations in the presence of alkaline salts following energy transfers from congruent L a 0 levels. Alkaline chlorides behaved as buffers over a large temperature
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range, L a 0 concentration was greater than for sulfates, and La I1 emission was greatly enhanced. For excited La species which were not perturbed by correspondences with L a 0 energy levels, local thermodynamic equilibrium calculations described the measured degree of ionization. These phenomena were observed only if the arc atmosphere provided sufficient oxygen. Semenenko et al. calculated the degree of dissociation and ionization of VO and T i 0 in a dc arc (2793). Osumi and Miyake investigated the effect of CsC1-C buffer on the analysis of neodymium oxide by measuring the arc temperature, electron density, line intensity, atomic concentration, and residence time of Pr, Sm, and Eu ions and atoms in the arc plasma (2373). Dimitrov and Konstantinova introduced buffers by impregnating C electrodes with buffer solutions ( 7 3 3 ) . The redistribution of axial and radical concentrations of atoms and ions in a dc arc plasma, as affected by the addition of an easily ionizable mixture, was calculated by Polatbekov and Zhukov (2473, 2483). The distribution was studied experimentally for an ore and mineral, and the results were used to increase the sensitivity of analysis. Other studies on the effects of easily ionizable elements during spectrochemical analysis were conducted by Shvangiradze and Vysokova (2833), Tarasevich e t al. (330E, 331E), Alvarez Herrero et al. ( 4 E ) , and Yudelevich et al. (370E). F16riBn and Matherny continued their evaluation of spectral line pairs and efficiency of dc arc excitation of elements in MgO matrix based on scatter diagrams and concentration calibration curve parameters (94E). Diaz-Guerra tested the efficiency of five oxides as spectrochemical buffers in the development of a semiquantitative method which was applied to 47 elements in different matrices (70E). Reactions products for Mo, Ti, V, and W in Li2B407 were found by X-ray diffraction, and their volatilization mechanisms were studied. In a continuing-series of articles, Szab6 e t al. investigated the physical and chemical reactions of electrode materials in binary mixtures of gases, their effect in the discharge, and their role in spectrochemical analysis (312E, 315E, 316E). An asymmetric electrode pair consisting of a rotating A1 disk or rod (3133, 314E) and a Cu or C counter electrode was excited in a polarized ac arc [l-16 A] in binary mixtures of gases ( 0 2 , Ar, COz, Nz). Spectroscopic (315E),chromatographic (3163, 3173, 3193, 324E) and titrimetric (312E, 320E, 321E, 3233) gas analysis method for 0 2 , CO, COz, and NO2 in the discharge were employed. The chemical reactions between the electrode materials and the surrounding gas atmosphere were controlled by the arc current (307E, 318E, 322E), the relative activities of the reactants, the polarities of the electrodes, and the rate of diffusion of the gaseous reactants (316E). By using a special discharge chamber and gas-extraction titration arrangement, the separate reactions a t the cathode and anode spaces were studied (307E-312E). The majority of the reactions occurring between the electrodes and atmosphere are redox reactions. Oxidation predominates in the anode space and reduction in the cathode space. The intensity of spectral lines were also influenced by these reactions. Formation of carbon oxides was due mainly to electrode surface oxidations (3113). Florian and Matherny investigated the influence of the ac intermittent arc on the excitation of elements in a MgO matrix. They studied the evaporation process (92E), and plasma temperature and electron pressure (%E, 2683) as a function of ac pulse rate and electrode polarity; the changes in calibration curve parameters (91E);homology of spectral line pairs (93E);and analysis results with a full-wave ac arc (95E). Wysocka-Lisek reported the effect of mixtures of rare earth elements on the intensity of their spectral lines in an ac arc, and recommended the careful choice of standards for spectral determinations of rare earth elements (361E, 362E). Systematic errors due to compositional fluctuations of sample were eliminated by Panteleva and Rusanov through the introduction of high amounts of S r S 0 4to samples in an ac arc discharge (2413, 242E). Zykova et al. observed the electrode spot formation and electrode erosion in a low-current [5-10 A] ac arc (38231, and Malykh et al. recorded atomic absorption signals for a 166R
10-A ac arc (200E). Calcium interferences were compared by Lesnikova and Khurin in a flame, an ac arc, and a combined flame-arc (187E). Harris investigated the effects of extraneous materials in the point-to-plane uni-arc excitation of copper-base alloys (1253). Theoretical and fundamental investigations of the dc arc electrode processes which may be related to spectrochemical systems were reported by a number of authors. Guile reviewed arc-electrode phenomena (121E), and Edels described the steady-state properties of arc discharges (81E).Uhlenbusch reviewed the calculation of arc properties using balance equations (3443), and Belousova described an approximate solution of the Elenbaas-Heller equation and the calculation of arc characteristics (27E). The cathode spot was discussed by Belkin and Kiselev (%E), Ecker (78E),Lyubimov (1973), Koslov and Khvesyuk (172E), Zykova et al. (3813), and Reeves-Saunders (2583). Sanger and Secker measured cathode arc tracks to obtain the cathode root current density (271E).Rykalin e t al. calculated current density in the anode spot (269E), and Volodarskii and Yudelevich studied stabilization of anode spot as the result of various experimental parameters (3533). Hearne et al. measured arc electrode temperatures and ignition characteristics (127E, 21 7 E ) . Aleksandrov et al. reported an atmospheric pressure He arc between Cd electrodes that deviated from ionization equilibrium a t 2 A due to diffusional loss of charged particles attained equilibrium 20 A ( 3 E ) . Chanin made cataphoresis measurements in dc capillary arc discharges in He-Nz mixtures (57E). Pichler et al. studied the properties and excitation conditions in a free-burning, low-current [l-15 A] arc between copper electrodes (246E). Below 10 A, temperatures for different groups of Cu lines indicated serious deviations from thermal equilibrium. From these and other measurements, an arc model consisting of an extremely narrow and hot core with electrons supplied by air atoms, and a broad luminous region with electrons supplied by copper atoms appeared favored. The effect of arc structure on measured average populations was discussed. and the transition probabilities for copper lines obtained in different laboratories were compared. Korsun et al. and Raikhbaum et al. developed a steel chamber furnace electrode which was preheated by a flame and arced at 14 A (170E, 249E). Braman described the response characteristics of a low-current dc discharge in a flowing He stream as a detector for gas chromatography or with independently vaporized samples for the spectrochemical analysis of air pollutant compounds (40E), mercury (39E),and arsenic and antimony ( 4 1 E ) . Carrier Distillations. Kawaguchi reviewed the carrier distillation technique for determination of trace impurities in high purity materials, and discussed the practice of the method. the role of the carrier, and the applications (151E). Strzyzewska continued her study of the action of carriers in the carrier distillation method and concluded that no general carrier could be found which gave optimum conditions for all elements determined in different samples (301E).However, she characterized suitable oxide and halide carriers, selected from them five optimum carriers, and grouped 14 elements for which each carrier would be common. Optimum carriers for determination of impurities in U308 and MgO-Al203 were illustrated. Boniforti et al. considered the thermochemical reactions between alkali halide and oxide impurities in carrier distillation analysis of U308 (31E, 32E). Anode temperature measurements indicated that the alkali halide carriers were molten during arcing, and Boniforti et al. assumed that the molten carrier salt acted as a solvent for the oxide impurities. X-Ray diffraction data and thermodynamic calculations agreed for reaction products formed during arcing. Among some of the other carrier substances used to obtain the carrier effect was Teflon by Tarasevich et a1 (332E), and Sb203-BaC12 by Dixit et al. (75E). Some spectrochemical analyses using the carrier distillation technique are listed in Table 111. In an investigation of the releasing effect of NH4Cl on chromium in an air-acetylene flame. Roos proposed that
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Table 111. Arc Analysis by Carrier Distillation Matrix U308
Pu
Tho:! CeO? Y?O3 RE oxides w203
wb3, MOO3 ZrOz
Fe alloys Graphite Oxides Ores MgO
+ A1203
Impurities
Carrier
3
Sb201-BaC1? Various GaL03,NaF AgC1, NaCl, NaF LiF-AgC1 AgCI, NaF, Ga?O3 NaF-S AgC1-LiF NaF-AgCl Ga203-NaC1 AgCl NaF-S Teflon Various NaF Kel-F h - 1 ~ 0 3 , Gap03 CdIr-CuIp NaC1, LiF, AgC1, GaF3
18 15
Rare earths, U, Am 12 13 3 12 8 10 B Nb, T a 7 21
B 11 Sn 16
the releasing agent causes fractionation of analyte and interfering ions or molecules similar to the carrier distillation effect in arcs (2623). Arc Plasma Jets. Nachman systematically surveyed the guidelines and problems involving structural and operational parameters for design of gas-stabilized, nontransferred, industrial dc arc plasma jets ( 2 6 7 0 . Elliott described the design considerations, construction, and operation of a commercial, transfer-type plasma jet (85E), which Corcoran et al. applied for the determination of nine elements in coal ash (147E), and of calcium and phosphorus in phosphate rock (60E). Kranz conducted theoretical and experimental studies with the Kranz plasma jet to overcome the electrode independent introduction of analyte material into the plasma (173E). Aersol production and transport in the jet chamber were described in detail. Chapman et al. improved the stability of plasma jet operation by replacing the directinjection nebulizer with a premixed chamber-nebulizer arrangement of the type used in flame spectrometry ( B E ) . Karikh operated an 80-A plasma jet with converging electrodes for the analysis of powders and solutions (376E) and injected solutions under pressure into the internal region of the plasma (148E). Yudelevich and Cherevko studied the axial and radial temperature distribution and degree of ionization in a plasma jet (366E): determined the optimum conditions for determination of 18 elements in rocks (369E): studied the effect of chemical composition on line intensities (368E) and the effect of particle size on calibration curves ( 3 6 5 3 ) ; and suggested the use of buffers to stabilize the ionization process, so that a single standard could be used for samples having different complex compositions (367E). Ishida and Kubota improved the plasma jet source developed in 1963 for practical spectrochemical analysis (135E). They measured temperature distributions and developed a method for analysis of solid sample ( I 3 6 E ) . Merchant measured the axial excitation temperature distribution for a plasma jet in argon which he used for emission and absorption analyses (207E). McElfresh determined wear metals (203E); Taniguchi et al. simultaneously determined Ni, Mn, and Cr in various alloys (329E):and Savinova e t al. measured Zn, P, B, Be, and S in rock powders (272E) using a dc arc plasma jet. Zakharov developed an inexpensive, low-current plasma jet for analysis of aqueous samples of trace metals (375E). Raab developed a disk-stabilized plasma jet with a solution nebulizing and desolvating device for analysis of trace metals in aqueous solutions (254E). Ragaller surveyed the production of thermal and magnetic plasma jets (255E). In order to describe, characterize, and model dc arc plasma discharges in gas streams, a variety of physical and spectroscopic measurements were conducted. For example, Lukens and Incropera measured electric field intensity and wall heat transfer (196E);To-
Reference
(75E) (89E) (69E) 1301E ) 114IE, 296Ei 156E) 1379E, 380E) 1218E, 219E, 3786) 12433) (l0E) ilOOE) 13323) 1198E) (178E) 1263E) 166E) 1335E) 1301E)
nejc et al. measured Stark broadening of Ar lines (338E); Kopainsky studied radiation transport mechanism and transport properties (265E), and Shumaker and Popenoe found departures from equilibrium in Ar based upon line intensity measurements ( 2 8 2 3 ) . Hermann and Schade systematically investigated the radiative-energy balance in cylindrical nitrogen arcs (130E), and Giannaris and Incropera developed a rigorous model to determine the effect of collisional and radiative processes on electron state populations in a cylindrically confined Ar plasma (105E). Shirai and Tabei measured the three-body recombination coefficient in a partially ionized He plasma jet (281E). Guzei et al. studied the stability and reproducibility of radiation intensity of a nitrogen plasma jet (122E), and Hefferlin observed anomalous excitation of N2+ in a Mn(NO&-seeded argon plasma jet (128E). Donskoi et al. studied the electrical and thermal characteristics of an Ar plasma jet as a function of arc parameters (77E), and Vargin and Pasynikova confirmed the presence of local thermodynamic equilibrium in Ar stabilized arcs (352E). The effects of gas flows in the design and modeling of plasma jets was considered by Frolov and Persits (101E), and Voronaev and Dresvin (354E). A mathematic model was developed by Yushkov and Borisov to calculate the motion and heating of powder particles in a plasma jet (372E). Cambray et al. described a method for measuring the average speed of an argon plasma jet (52E), and El’yashevich et al. used high-speed spectrography to measure radial distributions in a plasma jet (86E). Topham presented a model which accounts for the convection in a constant pressure axial flow N arc (339E), and Galimardanov et al. developed a system of equations which described the properties of the arc column stabilized in a channel with gas flow (102E).The velocity and heat characteristics of arc flows were measured by techniques described by Kovalev et al. (171E). Pustogarov et al. measured the surface temperature of plasma jet cathodes by means of a fast-acting photoelectric micropyrometer (252E). Spark Plasmas. Walters and coworkers have thoroughly documented and described many processes occurring in the spark discharge (402C). Walters described how excitation in the classical sense could be due primarily to the relative interaction of the independent, thermally expanding cloud of sampled electrode vapor and the separate current-dependent spark channel (359E). This simplification brings a large measure of order to describing the kinds of radiation observed from the spark. Walters also produced a highly stable discharge by means of a electronically driven, quarter wave, current injection spark source at repetition rates up to 3000 per second (401C), and described the gas-phase chemical mechanisms for discharge formation and growth from electrically generated metastable Ar (400C).
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Based upon these results and the recent work of Goldstein (109E), Walters and Goldstein put practical spark discharges into a simplified context of “how and what to view” in the spark gap (402C). From many of the previously complex phenomena observed in the spark gap have come relatively simple descriptions. For example, Walters and Goldstein discussed the possibility of obtaining greater optimization of spectrochemical techniques by selectively isolating radiation from the spark gap. They described the techniques necessary to form stable discharges and to view the spark gap in order to isolate classes of lines and reduce background and line interference. Spectral lines from the heterogeneous spatial and temporal spark were grouped into classes according to when and where they appeared in the discharge. The pulsed, unidirectional spark source developed by Walters (359E) was produced commercially, and served as the basis for suggestions by Norris et al. (273C) in the ASTM specification of spark sources. Rezchikov and Rudnevskii described another unipolar discharge with a diode in series or parallel to the discharge capacitor (308C). Barnes and Malmstadt reported spectrochemical and metallurgical effects of the application of a liquid layer on a solid sample electrode surface during sparking (50). Sparked samples showed increased material removal and depth of spark penetration. Both time-integrated and time-resolved spectra showed decreased interference from counter-electrode and atmospheric-line emission and enhanced neutral atom emission. When a solute was added to the flowing liquid layer, solute element emission was used as the internal reference in place of the conventional matrix element for the analysis of aluminum-, iron-, and nickel-base alloys. A mechanism based on gas-phase charge transfer reactions with hydrogen produced from solvent decomposition (21E) was suggested to explain spectral observations. A hypothesis based on the dielectric breakdown of the liquid layer was proposed to explain the electrode sampling. Van der Piepen and Schroeder investigated the formation of electrode spots in single and repetitive argon-jetguided spark discharges (346E). Their approach to spark stabilization with a counter-electrode argon flow is similar to that described by Walters and Goldstein (402C). In contrast to unstabilized, nonguided discharges, the eroded portion of the electrode was independent of the gap distance and configuration of the counter electrode. The formation of spark sites resulted from the branching of the spark channel into individual cathode spots, and this phenomenon was interpreted in terms of the formation of space charges that depended upon the conditions of the electrode surface. Electronic spatial- and temporal-resolution recording techniques were employed to correlate electrode erosion, vapor transport, and spark channel temperature (386C). Strasheim and Blum also studied electrode phenomena (345C) in air using a medium voltage spark (300E).Cathode spots formed in single oscillating and damped-current conditions were investigated by means of high-speed photography, and their formation depended on the conditions of the sample electrode surface. In an earlier study, metallographic and time-resolved spectroscopic techniques were applied to correlate the appearance of sparked areas, the depth of the molten zone under the impact area, and the precision of spectrochemical results (300E). These molten regions were studied by means of a scanning electron microscope combined with an energy dispersive X-ray analyzer (30E, 299E). Zynger and Crouch treated the theory of operation and source spectral characteristics of a coaxial microspark arrangement discharged in air (429C). Fal’kovskii excited a main spark gap by means of a plasma jet discharge created and shaped in a capillary in one of the spark electrodes (BE). Nickel and Stachova investigated the effect of structure and discharge gases in the spectral analysis of aluminum alloys (224E, 227E). Changes in the microstructure of aluminum alloys, both after sparking in N2, Ar, air, He, or Ar-02 or other heat treatment, shifted the calibration curves. Heat developed during sparking melted the electrode surface which caused metallurgical changes in the 168R
original alloy and made the sample spark site more homogeneous during this secondary localized melting process, as indicated by microprobe measurements. Ohls et al. also considered spark crater metallurgical changes and calibration differences which resulted in iron and steel materials by sparking the sample through a confining BN disk (2328, 2336). Slickers et al. studied the effects of spark conditions, including combined high-energy presparking and low-energy exposure (287E-289E), and atmosphere control and purity (2853, 286E) in the medium voltage spark source for analysis of steels and pig iron. Holler et al. demonstrated that an increase of spark source repetition rate during presparking led to improved conditioning of the sample surface like that obtained with higher discharge energies (161C). The effects on analysis time, accuracy, and precision were measured. The influence of sample structure and spark discharge atmosphere were measured by Buravlev e t al. for the analysis of steels with a medium voltage spark source (44E-46E, 48E). Kashima and Uemura demonstrated that the effect of electrode temperature rise on the amount of erosion depended on the oxygen affinity of the electrode element (150E). Zakharov calculated the analysis error due to nonuniform sample distribution in the electrode (374E). Electrode erosion in spark discharges was also studied by Grikit et al. (1I9E, 120E), Kolesnik et al. (163E),Bakuto et al. (19E, 20E), Lopez de Azcona and AlvarezArena (194E), and Lazarenko et al. (184E). The change of total material delivery rate in the spark as a function of composition was considered by Nikitina (228E). Karpenko and Grechanovskii demonstrated the effects of air, Ar, and Nz with additions of 0 2 or water on the line intensities of rare earth oxides in a high-voltage spark discharge ( I 4 9 E ) . Vovk and Rossikhin observed the influence of argon on the intensity of spectral lines in the unipolar arc discharge of samples prepared by the contact electrode spark technique (355E). Grikit and Galushko showed that extensive sparking of brass samples caused preferential removal of zinc from interdendritic structure and produced a specific dendritic etching in pure Ar atmospheres a t three different pressures ( I 19E). Nickel studied radiographically the influence of grain structure of rotating disk solution electrodes for various types of graphite and observed that the reproducibility and detection limit depended on both the physical properties of the graphite and the nature of the acid used (225E). An intensity increase resulted when disks were prepared by covering the graphite matrix with two pyrocarbon layers, one of which was high density and the outermost was porous. Lakatos employed rotating disk and Scheibe-Rivas electrodes to demonstrate that the solution evaporation process depended on the heat of solvent evaporation and the graphite-solvent interface (18IE). Osumi and Miyake measured the effects of alkali metal and alkaline earth elements on the axial distributions of line intensities of rare earth elements in the spark gap during the solution analysis of rare earth materials (2.383). They also studied the rate of vaporization of sample solutions encorporating alcohol in the solvent (236E). Moselhy investigated the effect of acids and organic solvents of the spark solution technique in which an aerosol is injected into the spark gap through the lower electrode (830, 216E). Acids and organic solvents with low surface tension and viscosity increased the rate of fine aerosol production, which increased line intensities. Lisienko et al. studied the intensity change during the aerosol-spark technique analysis of an ore suspension in mixed aqueousalcohol solutions (192E, I93E). Malmand determined Nb in Co- or Ni-base refractory alloys and in steel using a vacuum spark and the Nb IV and Nb V lines in the VUV (199E). Six other constituents were determined simultaneously in this unique use of vacuum discharges for analysis. Michel and Fischer reported the VUV emission from a high-density spark discharge in Ar and He between 1-40 atmospheres (210E), and Rudnevskii e t al. studied the problems of supplying copperalloy samples to a low-voltage pulsed vacuum discharge, and explained calibration curves in terms of sample erosion and discharge temperature change (280E, 264E); Schoenbach used a thermal model to describe the time
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development of the initial electrode erosion in high-current nanosecond spark discharges (2743). Avrustskii et al. studied the effect of electrode roughness on electrical strength and breakdown voltages for air at 1-5 atmospheres (15E, 16E). The characteristics of electrode erosion caused by aperiodic pulsed discharges of various duration and rate of current increase were investigated by Seliverstova and Zaitsev (2773, 278E). Namitokov and Solopikhin showed that structural changes in various electrodes determined by X-ray diffraction depended on the temperature gradient in the electrodes (220E). Kapel’yan and Yudovin studied the kinetics of metal destruction in electrical discharges (1443), and Ageev correlated electrode erosion with physical properties (1,E, 2 E ) . Davydov showed that the erosion of cathodes depended on the energy density evolved on their surfaces (65E). Nekrashevich and Bushik observed by means of highspeed photography a redistribution of space charges in the near electrode space during a pulsed discharge in air (2223, 2233). The initiation of a nitrogen discharge was observed by Koppitz with a streak camera and image intensifier (166E, 167E). Chalmers et al. applied an image converter with a 4-stage image intensifier to the study of spark breakdown in Nz, 0 2 , and SFs (54E, 55E). Mesyats et al. reviewed the development of electron avalanches in different discharge conditions (209E). The spatial and time distributions of photoionization of air by spark radiation was studied by Zhukov (377E). Biryukov et al. measured by means of gas chromatography the gas-phase composition of As and S b in a hydrogen spark discharge (29E). Sultanov and Ageev studied the temporal structure of the channel in a high-powered pulsed discharge and its dependence on near-electrode effects (305E). A stepwise breakdown process in the formation of spark discharges in COz was investigated by Pfeiffer (2453). An equation was derived by Triche for the relation between temperature, number of atoms evaporated, and discharge efficiency of an exploding wire which may be transferable to discharges using a point and plane configuration (340E). High Frequency Plasmas. Substantial developments with inductively coupled, atmospheric-pressure plasma discharges were made during the past few years, and the inductively coupled plasma (ICP) appears to hold promise for becoming a popular spectrochemical source. Microwave discharge plasmas also were studied, improved, and applied. A limited number of groups have contributed to the development and application of the ICP discharge. Using an automatically stabilized, 50-MHz generator (38E), Boumans and De Boer compared the detection limits obtained in a NzO-CzHz flame and an ICP discharge for simultaneous multielement trace analysis (37E). For many elements, detection limits in the 0.02-10 ng/ml range were attained only with the ICP discharge, and simultaneous multielement analyses could be achieved by subdividing all the elements into only two groups depending on the selection of carrier gas flow and observation zone. They concluded that the ICP source was promising, because in multielement analysis of solutions its stability was comparable to that of a flame and its detection power similar to an arc. Scott et al. reported an improved ICP system operating at 27 MHz with a pneumatic nebulizer requiring no external desolvation (276E). Nixon et al. coupled external vaporization of 1-200 111 samples from a tantalum filament arrangement to the ICP to obtain detection limits in ng ml for many elements and wide linear concentration ca ibration curves (230E). Samples could be run a t a rate of 20-30 per hour. Operating an ICP at 5.4 MHz and 6.6 KW, Souilliart and Robin verified and extended to 27 elements including rare earths the detection limits reported previously (295E). Mermet and Robin evaluated the Abel inversion with the view of measuring the temperature distribution in the ICP discharge (208E). One of the pioneers in the development of the ICP for analysis, S. Greenfield (115E) reviewed plasma sources
i
and their operating conditions (117 E ) in spectroscopy, and patented an ICP arrangement for spectrochemical analysis (116E). Greenfield and Smith described the multielement analysis of 1-25 p1 samples of oil, organic compounds, and blood for trace elements provided absolute detection limits of 0.1-1 ng with a precision of 5% (118E). Employing commercial equipment similar to that of Greenfield, Kirkbright et al. determined sulfur, phosphorus (156E), iodine, mercury, arsenic, and selenium (157E) a t wavelengths in the near vacuum UV. Triche et al. measured the distribution of emission (341E),the influence of mass transfer (342E), and the reactions of TiB2 (325E) in an ICP discharge operated a t 6.3 MHz and 12 KW. Among Soviet investigators, Dashkevich and Eilenkrig reviewed the use of high-frequency discharges as spectrochemical sources (&$E),and Pupyshev and Muzgin studied mutual element effects introduced by ultrasonic and pneumatic sprayers in a 20-MHz source (251E). Arefev e t al. produced a large argon discharge ( 9 E ) , and Mitin et al. a high-pressure 150-MHz discharge (2123). Snopov studied the parameters of a low-power 20-MHz generator (294E). Medvid measured the influence of cooling gas layer on the geometric size of an induction plasma (20.533). Busch and Vickers explored the fundamental properties characterizing a low-pressure microwave-induced plasma used as an excitation source in spectrochemical analysis (49E, 50E). They measured the excitation temperature of the argon plasma (1-25 Torr), the relative concentration of metastable argon atoms, the electron temperature and relative electron concentration, proposed an excitation mechanism for the low-power microwave plasma, and studied the analytical utility using mercury. A collisiondominated radiative-recombination mechanism was employed to explain experimental results. Lichte and Skogerboe changed the design of an Evensen cavity to reduce tuning problems and permit emission analysis of desolvated aqueous samples (19IE). Of the detection limits reported for nine elements, all bettered previous microwave results, and five were superior to those in a conventional ICP discharge, but comparable to the T a vaporizer-ICP arrangement. These simple modifications should permit more low-power microwave source applications for solutions samples in a variety of analytical problems. Lichte and Skogerboe also reported the determination of As (I9OE) and Hg (189E) with microwave-induced plasma excitation. Kawaguchi et al. investigated a low-power microwave discharge for detection of trace elements in aqueous solutions nebulized by an ultrasonic arrangement (I52E). Plasma temperature, flow rate, power level, and interferences were studied. Kitagawa and Takeuchi considered Mn solutions sprayed into a microwave-induced discharge (159E). Sermin determined 17 elements in solution by means of an unipolar Kessler-type atmospheric pressure microwave-induced plasma discharge (284E). Plasma properties in a unipolar 27-MHz discharge were measured by Kapoun (145E),Kapounova (146E), and Tesar (3333, 334E). Bachurina et a1. applied a high-power (2.5 KW) microwave discharge for spectrochemical analysis ( I 7E, 18E). For excitation in a microwave source, Van Sandwijk et al. sealed 100-111 samples of metal chlorides in quartz tubes in a manner similar to electrodeless discharge lamps in atomic fluorescence spectroscopy to study the feasibilit y of trace element analysis by emission spectroscopy (351E ) . Microwave-excited emission techniques were used by Kawaguchi et al. (153E), McLean et al. (204E), Natusch and Thorpe (221E),Houpt and Compaan ( 1 3 I E ) and Dagnall et al. (6IE-63E) as detection systems for gas chromatography. A microwave discharge in He provided Freeman and Wentworth an intense 21-eV ionization source for use in gas chromatography systems (99E). Microwave radiation levels were measured by Stanley et al. for several common microwave-source configurations and were found in excess of safety standards, and recommendations for shielding and site survey were made (297E). Kleinmann studied the influence of discharge diameter, graphite support temperature, and sample composition on
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line intensities in a combined low-pressure, 200-W, 40MHz inductively coupled discharge and graphite sample vaporizer (160E, 161E). Talmi and Morrison developed an induction source for direct analysis of solids or evaporated solutions in which an induction-heated graphite crucible served to vaporize and atomize samples into He plasma formed by the rf field (3263-328E). Atomization by induction heating was also used by Iida and Nomiyama (133E), Langmyhr and Thomassen (182E), and Headridge and Smith (126E). Korovin and Kuchumov employed a high-frequency jet as an atomizer (169E). Boos and Winefordner developed an 8-MHz low-power plasma detector for fixed gases (33E). Bordonali and Biancifiori patented an ICP discharge arrangement used for atomic absorption spectrometry (34E). Diagnostic measurements of high frequency plasmas were reported by Eckert (79E, 80E), Gol’dfarb et al. (107E, 108E, IIOE), andLeonard (186E). Laser-Produced Plasmas. In order to obtain the basis for the design of an advanced laser microprobe, Allemand investigated the extent and shape of regions sampled in various materials and the spatial and temporal spectral characteristics of plasmas generated by a true single-spike laser pulse of energy between 0.03 and 15 m J and of 40 nsec half-width (383E). He demonstrated a dependence on material properties, and developed a qualitative relationship to physical properties of the host material. The laser produced sample radiation of high intensity but short duration with a s;lectral bandwidth of approximately 1 nm and, with an auxiliary spark excitation, the radiation was of lower intensity, longer life, and narrower spectral bandwidth. Yamane and Matsushita considered the influence of heat in the plasma produced by auxiliary spark excitation in a laser microprobe on the sample surface (363E, 3643). Korolev and Ryukhin established optimum conditions for the electronic synchronization of sample excitation in laser microanalysis (168E). By compensating for the amount of material vaporized with a laser microprobe, Morton et al. developed semiquantitative analyses of common analytes in dissimilar matrices (215E). Statistical correlations showed that the measured line intensity was a function of weight of material vaporized. Ishida and Kubota classified four types of craters formed by lasers, the volume of which depended on the latent heat of melting (134E). In the development of macrospectral analyses with a laser source, Felske et al. classified nonmetallic samples according to their boiling points and optical transparency and selected appropriate power density and auxiliary cross-excitation as needed, and treated metal samples to provide optimum analysis parameters through a programmable step placement devide, methods of Q-switching, and auxiliary spark cross excitation (101C). Modes of cross-excitation other than spark discharges were explored by Hagenah et al. (123E, 213E, 214E), who generated microwave- and radio-frequency induced discharges in the vapor sampled by a laser. The radiation emitted from the vapor cloud excited in the microwave discharge lasted lo3 longer than radiation of the laser-produced plasma without excitation (123E). Pulsed rf excitation (85 MHz) also extended the radiation emission lifetime and provided limits of detection as low as those observed for analysis with spark cross-excitation (213E, 214E). Other studies of the laser microprobe included the effect of sample composition on spectrochemical results by Buravlev et al. (47E), the effect of background and laser energy corrections on precision by Saffir et al. (270E), and the effects of laser discharge electrical and optical parameters by Bieber et al. (28E). Stupp investigated the properties of the laser microplasma, plasma excitation, and emission by using highspeed photography in methods developed for problems related to reactor materials (304E). Ishizuka studied the emission spectroscopy of rare earth elements in several matrices by using a $-switched ruby laser as an excitation source for microanalysis (137E). Sample erosion for spectrochemical analysis was studied by Mikhnov et al. with an organic dye laser source (211E).
The use of laser-produced plasmas for atomic absorption measurements was studied by Osten and Piepmeier (234E, 235E), Vul’fson et al. (357E), and Nikolaev and Podgornaya (229E). Vanderborgh and Ristau (3453), and Frad and Leach (97E) investigated the laser pyrolysis of various solids through the formation of low molecular weight molecules. Zahn et al. examined the possibility of determining mass spectrographically the parameters of the plasma produced by a laser microprobe (72E, 3 7 3 0 . Other investigations of laser erosion of materials were conducted by Putrenko and Yankovskii (253E), Fersman et al. (ME), El’yashevich et al. (87E), Fradlin (%E), Glass and Guenther (106E), and Batanov et al. ( B E ) . Other studies of the plasmas produced by laser irradiation of solids were conducted by Stumpfel et al. (302E, 303E), Koopman (164E), Puell et al. (ZOE),Dick et al. (71E), and Batanov et al. (22E). Hollow Cathode Discharges. Krasil’shchik observed intensification of He filler gas and cathode elements line intensities upon application of a magnetic field (174E) and of impurity elements in samples placed in the hollow cathode upon mixing AgCl with the samples (176E). Rudnevskii et al. also observed improved limits of detection for cadmium dried residues in the hollow cathode with the application of sufficiently high magnetic fields (265E267E). A continuously dried atomized solution was blown into a hollow cathode discharge and deposited on the cathode by Menge and Maierhofer, and the deposited substance was volatilized by cathode sputtering for spectrochemical analysis (206E). Carstens et al. combined physical and chemical sputtering of a hollow cathode as a source for atoms or molecules for matrix-isolated studies of high temperature species (53E), and Walsh et al. described the use of cathodic sputtering as a source of atomic vapor for analysis by atomic absorption or fluorescence techniques ( I I2E, 353E). In a study of the effect of resonance and recombination processes on radiation in a high-current He hollow cathode, Semenova et al. observed marked increase in Cu and Au line intensities attributed to resonance and recombination processes (280E). Smith measured the cathode and electronic excitation temperature of an iron hollow cathode glow discharge lamp (2933). In hollow cathode discharges in Ar, the physical parameters of the negative-glow plasma were measured by Howorka et al. (132E) and Brunet (43E). The excitation mechanisms of argon and electron temperature and density profiles in a hollow cathode discharge were defined in a series of papers by Van der Sijde (347E-350E). Lebedeva et al. measured the shape of Ar I1 lines excited in a hollow cathode discharge (185E). The contribution of‘ hyperfine structure to the measured widths of Au hollow-cathode lines was documented by Hannaford (124E). The excitation mechanism of Ne and A1 lines in a hollow-cathode discharge was investigated as a function of gas pressure and cathode dimensions by Pacheva and Zhechev (2393). Kagan e t . al. suggested a mechanism leading to the electron distribution function and absolute spectral intensities in a He discharge (142E, 143E). The non-thermal equilibrium in the negative glow of a He hollow-cathode discharge was determined by Schmid (273E), and the concentration of metastable He during a pulsed hollow-cathode discharge was measured by Kravchenko and Papakin ( I 77E). The electrical and optical characteristics of a discharge in a cooled hollow cathode were studied by Boshnyak et al. (35E), and the characteristics of hot hollow cathodes were considered by Gorbunova and Semenova (1I I E ) , Trishin et al. (343E), and Helm et al. (129E). The effect of the properties of the cathode material, the pressure, and the interelectrode spacing on the appearance and structure of a ring discharge glow near the cathode was investigated by Suzdalov (158E, 306E). Time-resolved spectra of a pulsed discharge through streaming HzO vapor were interpreted by Remy (259E). The operating conditions and parameters for program-controlled demountable hollow cathode arrangement were described by Maierhofer and Metz (229C). Glow Discharge Lamps. Glow discharge lamps of the type originally described by Grimm have undergone de-
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tailed inspection as alternative excitation sources for rapid multielement analysis of solid samples during the past few years. Dogan e t al. conducted a comprehensive study of the electrical and spectral behavior and analytical conditions of the Grimm glow discharge lamp in spectrochemical analysis of conducting and nonconducting samples (76E).El Alfy et al. continded this development and described a universal method for the determination of main constituents in electrically nonconducting powder samples ( 8 4 E ) .When the grain size of the samples was made sufficiently fine, calibration curves were obtained with a single master-standard composed of calcium carbonate and oxides. Boumans reviewed the sputtering literature, measured the sputtering rates in a Grimm lamp, and found a linear relationship between the mass sputtering rate per current strength and the operating voltage (36E). These and other results were useful for describing various spectrochemical properties and prospects of the glow discharge. Belle and Johnson reported the sequential analysis of metal alloys in depths of 0.1-40 pm by means of the Grimm discharge lamp (26E). This approach provided compositional profiles in depth related to specific depletion and enrichments in the alloys. Jaeger developed a method to analyze gold alloys based on the glow discharge lamp (138E-140E) and applications of the glow discharge to analysis of steels were described by Dehrendorf and De Laffolie (68E) and Koch et al. (162E).Greene and Whelan developed a technique for the analysis of thin GaAs films based upon the electroluminescence observed in a glow discharge arrangement (113E, 114E). Coburn and Kay determined elements in thin surface films by means of rf sputtering glow discharge sampling for a quadrople mass spectrometer (59E). SPECTROCHEMICAL ANALYSIS The sensitivity, precision, speed, accuracy, dynamic range and simultaneous multielement capabilities of emission methods continue to account for their large number of applications in all fields. The techniques and methods of qualitative and semi-quantitative emission spectrochemical analysis were described in detail by Wang et al. (379F). This chapter provides a good start for the novice in emission methods. Complementing this chapter was one on quantitative analysis considerations by Rosza (306F). A good example of the universal capabilities of emission spectroscopy was presented by Addink in a short book giving the complete operating details of the K- and Qmethods of dc arc analysis ( 1 A ) . These methods provided quantitative results for a wide variety of inorganic materials, and for duplicate exposures, the Q-method was semiquantitative, but the K-method gave an accuracy of 210%. Through the application of the Grimm glow discharge lamp, El Alfy et al. developed a universal method for the determination of main constituents in electrically nonconducting powder samples ( 8 4 E ) . Non-conducting samples were ground and mixed with copper powder, then pressed into sample pellets. Single linear calibration curves for elements in rocks, minerals, ores, glasses, slags, and cement were obtained. Kashima and Yamaguchi described a simple emission method with an average error of 30-50% based upon comparison with NBS Tables of Spectral Line Intensities under fixed conditions (164F). Diaz-Guerra developed a semiquantitative arc method for the determination of 47 elements in different matrices (74F). Mosier described a dc arc method for semi-quantitative analysis of plant ash based on a visual comparison technique employing a split slit arrangement to detect 35 elements from a single exposure (248F). The concentration ranges were optimized for most plant materials and results were reported as six possible logarithmically spaced intervals per order of magnitude. With this method, a two-man team could analyze 80 samples a day for 35 elements each. Gordon et al. described the recent developments and applications of the Gordon arc technique (131C). Dorrzapf determined 68 elements in silicate rocks by means of a dc arc method with computer analysis (84F). Trace Element Analysis. One of the major objectives in the development of spectrochemical methods is the im-
provement of sensitivity and limits of detection, because of the practical importance of trace and ultratrace element analysis. Kaiser discussed the concepts and relations in trace analysis with emphasis on terminology, sample size, blanks, analytical signals and noise, calibration, information provided, the analysis scheme, selectivity, and sensitivity (154F).Mitchell described the need and practices in ultrapurity for trace element analysis ( 8 2 0 ) , and Skogerboe and Morrison reviewed analytical characteristics and sources of error in trace analysis methods ( 9 7 0 ) . Chakrabarti reviewed trace, ultratrace, and ultramicro analysis (55F). Zil’bershtein et al. devoted 15 chapters to the techniques and practical problems related to spectral analysis of trace elements in pure materials (IOIA), and Belcher reviewed a variety of methods, including emission spectroscopy, employed for the determination of elements in trace amounts (24F). Kane et al. discussed the techniques for trace analysis of solids, especially semiconductors, and the challenges for future developments (155F, 156F). Pinta edited a series of papers on the detection and determination of trace elements, which were translated into English from French (286F), and Koch and KochDedic prepared a handbook of trace analysis in German (1903’). Mainka and Mueller described two quantitative emission methods for trace determination in nuclear fuels ( = I F ) , and Yudelevich surveyed spectrochemical methods for the analysis of high purity alkali and alkaline earth metal halides (392F). Korenman and Rudnevskii described the proceedings of the Russian conference on methods for production and analysis of special purity materials (194F). The preparation of pure reagents and trace element losses were described in a previous section on sampling and sample preparation techniques. Blackburn et al. determined 20 trace elements in 6 new silicate rock standards (31F), and Davoine et al. determined 8 trace elements in standard granites GA and GH and standard basalt BR (69F). Webb et al. described the determination of 13 trace metals in biological tissues by means of dc arc excitation (410F, 411F). Wang developed a dc arc method for determination of 21 trace and ultratrace impurities in group 111-V compounds based upon their preferential volatilization (378F). Table IV lists some of the high-purity materials analyzed by emission spectroscopy for trace element content. A book on the analytical chemistry of pure substances was prepared in Russian by Sjevchuk et al. (331F). Preconcentration techniques, such as solvent extraction, precipitation, and ion exchange, are used with emission methods for improved sensitivity, but in trace and ultratrace analysis, solvents, reagents, or apparatus required in the preconcentration and analytical manipulations can often lead to serious contaminations. Selective volatilization, often directly from the graphite electrode, is less susceptible to contamination. Some examples of chemical complexation-extraction methods applied to trace elements include three-phase extraction of Sc in bauxite (404F) and fig amounts of Ga, In, and T13+ in 10 metals (45F), and six other elements with diantipyrylmethane (46F) as extracting reagent as described by Zhivopistsev et al. Zolotov surveyed in Russian the analytical aspects of extractions used in trace element analysis (409F), and Schilt et al. described the solvent extraction of metal 1,lO-phenanthroline complexes to facilitate separation and concentration of trace quantities of metals (319F). Mizuike et al. described extraction of trace impurities from metal chlorides (244F), and Zolotareva et al. removed tungsten from a high purity W material by extraction with trialkylbenzylammonium nitrate prior to analysis of the residual trace elements (408F). Kantcr et al. reviewed the use of organic solvents and chelating agents for separation prior to arc or spark analysis (158F). Joshi et al. removed Se with dithizone from high-purity Se (151F), and Goryanskaya et al. concentrated trace impurities in high-purity T a on a Teflon column (120F). Extraction procedures were also used by Sizonenko et al. for analysis of alkali metal halides (336F), by Kuz’min et al. for alkali and alkaline earth halides (211F), and by Bykova and Manova for phosphorus-containing compounds of alkali metals (50F). For very pure GaAs, Nazarova distilled As and extracted Ga to concentrate trace elements (257F). Sublimation, fractional distillation or volatiliza-
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Table IV. Trace Element Analysis in Pure Materials Material
AgBr AgCl A1 As AsC13 B, B compounds Bi Cd Cd, Zn electrolytes Ga, GaAs GaAs Gap03 Hg In In, Bi, P b Nb LiF Pb, electrolytes Pb S Sb Se
Impurities
(200F) (255F) (360F) (395F)
11 13 6 12 17
(276F) (19F) (200F) (252F) (218F)
10 14 13 14 17
(366F) (258F) (317F) (2743) (57F) (56F) (400F) (8F) (386F)
Cd, Zn, Hg 14
13 4, 11 7 10 13 23
Te Sn Ta Te
T1 W Zn
Reference
6 15 3 16 2 6 7 21
13 17 15 14 9 3 5 16 23
Cd 12
10
(2.W
(1671s) (330F) ( I 76F)
(148F) (166F) (41F) (150F, 153F) (152F) (151F) (179F) (120F) (400F) (393F) (208F) (147F) (58F) (408F) (321F) (146F) (32PF)
tion techniques to remove matrix materials were used by Joshi for Se (150F, 152F, 153F), by Brodskaya for S b (41F), by Shemet et al. for AsC13 (330F), by Chalkov et al. for T1 (58F) and In (57F), by Zakhariya et al. for Nb and T a (400F),and by Kat0 et al. for As (167F). Ion exchange techniques were applied by Ku for traces in iron and steel (203F), by Tikhonova et al. for high purity Ga and GaAs (366F), and by De Albuquerque for thallium in silicate rocks (708’). Lebedinskaya and Chuiko concentrated microelements by coprecipitaton (221F), and Krasil’shchik et al. isolated impurities from solutions by electrolysis (197F, 198F). Krasnobaeva et al. reviewed methods for the increase of sensitivity of arc analysis and described the influence of Ba(N0& and NaCl on the sensitivity during analysis of solution residues (199F), and Shvangiradze e t al. measured the change in sensitivity with NaCl with 24 common trace elements in various samples (334F). Table I11 and the discussion in the previous section on carrier distillation methods emphasize the determination of trace elements in various refractory matrices by means of selective carrier vaporization during arcing. Christopher described a technique in which samples were attached to a graphite electrode with C fibers which acted as a bridge between upper and lower electrode for the qualitative spectrographic analysis of very small samples (62F). Lichte and Skogerboe determined trace amounts of As (29OE) and Hg (189E) by means of microwave plasma excitation of vaporized arsene and Hg. Dagnell determined trace Hg by using a Hg microwave-excited electrodeless discharge lamp (65F). Marcus and Jamison reported the 172R
application of a He glow source to the determination of picomole quantities of calcium (234F). Barnard outlined selected challenges in trace analysis of specific elements in various materials (40).An English translation of Kawaguchi et al. description of the spectrographic determination of ultratrace elements in a short-time, high current [30 A] argon arc became available (I6 9 0 . Geological Materials. Langheinrich and Roberts surveyed the techniques and methods of emission spectroscopy in the analysis of geological materials (56A). The “Annual Reports on Analytical Atomic Spectroscopy” for 1971 (45A) and 1972 (46A) tabulated and discussed the spectrochemical analysis of minerals. A number of Russian publications concentrated on the spectral analysis of geological materials. Rusanov described the principles of quantitative spectrographic analysis of ores and minerals (310F), and Fain described the spectrographic determination of rhenium in ores (IOOF).Raikhbaum edited a volume of articles on the spectral analysis of trace elements in rocks ( 3 4 3 0 , and Baskov edited another on methods of analysis of minerals and raw materials (21F). Papers on the spectral analysis of geological materials were also compiled in Russian (344F).Keil and Snetsinger described the application of the laser microprobe to geoldgy (171F). For the analysis of silicates, Quintin et al. compared emission spectroscopy with alternative spectrochemical approaches on the basis of matrix effects ( 2 9 6 0 . Govindaraju developed a new scheme for the routine analysis of 16 major, minor, and trace elements in silicate rocks and minerals which included a borate fusion and ion exchange steps (122F). Dorrzapf employed a controlled-atmosphere dc arc for a semiquantitative method for 68 trace and minor elements in silicate rocks (84F). The effects of matrix composition and arc atmosphere and electrode polarity were considered by Vecsernyes (374F) and Ul’yanova et al. (371F) for silicate materials. Optimum conditions for analysis of 13 trace elements in silicate minerals by means of an ac arc were selected statistically by Golubeva ( I 18F). Eftekhari and Maghssoudi compared various solution methods for analysis of various minerals (92F); Besnus and Rouault employed a rotating disk solution electrode for 7 elements in rocks (27F); Matherny and Pliesvoska measured 8 elements in limestone by means of ac arc excitation of solutions in a vacuum cup electrode (237F) and Lisienko analyzed titanomagnetite ores by an aerosolspark method ( 2 2 5 0 . Kothari determined thoria in monazite sand (196F);Delavault and Marshall detected Mo in rocks using Tennant’s bead-forming buffer (7227);Panteleeva et al. measured 25 elements in different minerals (275F); Martin and Roca analyzed Ge in lignite and coal by-products (236F);and Izmailova and Zakhariya assayed Nb, Ta, and Zr in various ores (145F). Eight elements in zirconium and disthene concentrates were measured by Efimenko and Kushnareva in an ac arc using the powderpouring method (92F). Govindaraju described the spectrochemical determination of major and minor elements in two samples of lunar fines dusts (122F). The determination of P in rocks and ores was accomplished by Polivanova et al. (290F),Dutra (88F),and Corcoran et al. (60E). O’Gorman et al. measured Hg by various spectroscopic methods and 21 trace elements by dc arc emission in American coals (267F, 268F). Luedke and Holdt determined trace contents in lignite-tar pitch coke using a dc arc (228F). R a r e Earth, Actinide Elements. The analysis of nuclear fuel materials by emission spectroscopy was among topics presented at the Symposium on Analytical Methods in the Nuclear Fuel Cycle ( 2 A ) . The preparations of U, Pu, and Pu oxide reference materials were described by Buffereau et al. (42F), Ganivet et al. ( I l O F ) , and Neuilly (262F). Examples of emission spectrometric methods were presented by Alkire et al. ( 4 F ) , Tolk and Van Raaphorst (367F), and Taylor et al. (365F). Chaney described the spectrographic procedures for analysis, preconcentration, and semiquantitative techniques for high-temperature gas-cooled reactor fuels and materials ( 6 1 F ) . Hashitani and Adachi reviewed the literature concerning the analysis of nuclear fuels and reactor materials (136F). Tables I11 and V list some analysis by carrier distillation and
A N A L Y T I C A L C H E M I S T R Y , V O L . 46, NO. 5, A P R I L 1974
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~~
T a b l e V. S o m e R a r e E a r t h (RE) and Actinide E l e m e n t Analyses Alloys Ceramics Yag, Yig garnets CaF2, CdF,, SrF2crystals Calcite, siderite Steel Piezoelectric materials Nd, Gd molybdates Rocks Monazite Minerals R E minerals Mineral R E base La CeO?
NdrO:
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(397F) (398F) (399F) (400F) (401F) (402F)
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Flame Spectrometry J.
D. Winefordner'
Department of Chemistry, U n i v e r s t y of Fiords, Gaineswlle. F / a 3267 I
T. J. Vickers2 Department o f Chemistry, Florida State Unwersity. Tallahassee. Fla. 32306
This is the third fundamental review on flame spectrometry prepared by the present authors. This review covers books, chapters, and articles published in the time W o r k supported by
USAF-AFOSR-74-2574.
* W o r k supported by f u n d s f r o m PHS G r a n t R01-GM15996. 192R
A N A L Y T I C A L C H E M I S T R Y , VOL. 46,
NO. 5,
period between Xovember 1971 and October 1973. Because of the large number of articles in the area of flame spectrometry (over ZOOO), it was necessary to use a filtering process to reduce the unwieldy number to a more manageable size. The guidelines used for this review are similar to those used in the previous review (92A). The
A P R I L 1974
