(1436) Zaitsev, P. hf., Zaitseva, Z. V., (:r’criena i Sanit.. 30. 49 (1965). ( 1 4 3 i ) Zaitsev, P.’ M.’, Zaitbeva: Z. ZavotIsk. Lab., 32, 287 (1866). (1438) Zititsev, P. RI., Zaitseva, Z. V., t’kr. Khirn. Zh., 31,820 (1965). ( 1 4 3 ) Zavada, J., Krupicka, J., Sicher,
(1450) Zhdanov. S. I.. Pozdeeva. A. A.. Collection Czech. Chem. Commun., 30; 4143 (196.5). (14,51) Zhdanov, S. I., Pozdeeva, A. A., Elektrokhim., 2,1067 (1966). ( 1 4 3 ) Zielinski, hl., Kuta, J., Abhandl.
31,4273 (1966). (1440) Zawadirka, T., Rocznicki Panstwowego Zakladu Hig., 17, 15 (1966). (1441) Ibzd., ~ 2 6 3 . (1442) Zawadzka, T., Farm. Polska, 22, 99 (1966). (1443) Zdrazil, J., Picha, F., Kozarslvi, 16,51(1966). (1444) Zembura, Z., Bierowski, M., Wiadomosci Chem., 18,21.5 (1964). (1443) Zhantalai, B. P., U.S.S.R. Patent 168,043 (Cl. G Oln) (Feb. 5, 1965). (1446) Zhantalai, B. P., Ruch’eva, N. I., Zh. Prikl. Khim., 39, 2339 (1966). (1447) Zhantalai, B. P., Tur’yan, Ya. I., Kinetika i Kataliz, 6 , 761 (1965). (1448) Zhdanov, S. I., Usp. Elektrokhim. Organ. Soedin., A k a d . Sauk. SSSR, Inst. Elektrokhim., 1966, p 44. 449) Zhdanov, S. I., Feoktistov, L. G.,
1966.1) 433. (1433) ’Zikan, J., Collection Czech. Chem. Commzm., 31,4260 (1966). (1434) Zikan, J., Kalous, V., Ibid., p 4.513. (14.55) Ibid., 32,246 (1967). (1456) Zikan, J., Sterzl, J., Nature, 214, 1223 11967). (14h7) Zil’berman, E. N., Korotaevskii, K. N., Perepletchikova, E. M., Lazaris, A. Ya., Zh. Prikl. Khim., 38, 2724 (1965). (1438) Zittel, H. E., Florence, T. hf., ANAL.CHEM., 39,320 (1967). (14691 Zolotovitskii. Ya. &I.. Tedoradze.’ G. A., Elektrokhim., 1 , 1339’(1965). (1460) Zolotovitskii, Ya. AI., Tedoradze, G. A., Erl-hler, A. B., Ibid., p 828. (1461) Zuman, P., “Advances in Physical Organic Chemistry,” Vol. 5, V. Gold. Ed.. Academic Press. 1967. (1462) ’Zuman, P., Chemistryj’39,6 (1966). (1463) Zqman, P., Chem. Listy, 60, 807 (1966).
v.,
J., Collection Czech. Chem. Commzin.,
Izv. Akad. Xauk. SSSR, Otd. Kham. iVauk., 1963, p 53.
Deut. Akad. Wiss. Berlin. Kl. Med..
(1464) Zumttn, P., “Polarography 1964,
Proceedings of the Third International Congress Southampton,” G. J. Hills, Ed., Vol. 2, Macmillan, London, England, 1964 (Pub. 1966), p 687. (1465) Zuman. P.. “Substituents in Organic Polarography,” Consultants Bureau, New York, 1965. (1466) Zuman, P., Talanta, 12, 1061 (196j). (1467) Ibid., p 1337. (1468) Zuman, P., 2. Anal. Chem., 216, 151 (1966). (1469)‘Ibid.: 224,374 (1967). (1470) Zuman, P., Barnes, D., .Vature, 215,1269 (1967). (1471) Zweig, A., Hoffman, A. K., J . Org. Chem., 30,3997 (1965). (1472) Zweig, A., Maricle, D. L., Brinen,
J. S., Maurer, A. H., J . Am. Chem.
Soc., 89,473 (1967). (1473) Zweig, A., hlaurer, A. H., Roberts, B. G., J . Org. Chem., 32, 1322 (1967). (1474) Zweig, A., Metzler, G., Maurer, A.,
Roberts, B. G., J . Am. Chem. SOC.,
88,2864 (1966). (1475) Zyabkina, E.
P., Malinovskii, V. Yu., Musakin, A. P., Soklova, R. I., Metody Analiza Radioaktivn. Preparatov., Sb. Statei, 1965, p 46.
Emission Spectrometry’ Marvin Margoshes and Bourdon F. Scribner, National Bureau of Standards, Washington, D. C.
T
the tenth in a series, covers the years 1966 and 1967, with the addition of a few significant references from 1965 which came to our attention too late to be included in the review published two years ago (377). The subject5 included are emission spectrometry and the related techniques of atomic absorption and atomic fluorescence spectrometry. ;is in earlier reviews particular attention is given to contributions of basic importance and relatively few citations are given of publications on applications of emission spectrometry. These applications are summarized in the reviews appearing in alternate years in this Journal. I n earlier years, we have summarized developments in the flame techniques in a separate portion of the review. It is becoming more and more difficult to isolate flame methods from other aspects of emission spectroscopy. Many papers on flame photometry, atomic absorption, and atomic fluorescence spectrometry ale in a separate section in this review, but others are included in the main body of the text, as is appropriate. HIS REVIIX,
BOOKS AND REVIEWS
Mention was made in the last review (377) of the increased interest in studies of the fundamental properties of the dc arc as used in spectrochemical analysis.
Boumans (56) has written a treatise which should serve to increase attention to this important work. A book by Tourin (603) critically reviews methods for the spectrometric measurement of temperatures in hot gases and plasmas. It is not directed primarily t o spectrochemical sources, but will be of interest to analytical spectroscopists. 5 translation has been published of a book on the analysis of silicates, including spectrometric methods, by Voinovitch, Debras-Guedon, and Louvrier (624). Other new translations include a book by Ihchkova and Shreider (50) on the analysis of mixtures of gases, and one by SventitskiI (587) on visual methods of emission spectrometry, a subject also treated by Siebert and Makelt (662). Samson (558) has written a book on techniques of spectroscopy in the vacuum ultraviolet. Noenke and Moenke-Blankenburg (408)have written a monograph on analysis with the laser probe source. A book by Shaevich and Shubina (549) is devoted to spectral analysis of metals in industry. The ASTJI 1966 Book of Standards (8)includes some information on emission spectrometry. Three books are devoted to the determination of trace elements, including spectrometric methods of analysis. One of these is a translation of an earlier French work by Pinta (476).
20234
The others are newer works, one edited by Morrison (419) and the other edited by Meinke and Scribner (395). Three new books and one revised work on atomic absorption spectrometry have been published, two of them in English. Elwell and Gidley (151) have revised their earlier book on this subject, and Robinson (614) has written a new text. The other books are one in Russian by L’vov (365) which, it is hoped, will be available shortly in English, and one by Rousselet (523),in French, with emphasis on applications in biology. Two books on flame photometry have also appeared, one by Pungor (499) which stresses the theory, and one by Poluektov 1485) primarily concerned with techniques. Among the more valuable books for most spectroscopists are tables and atlases of spectral lines. Striganov and Sventitskir (580) have compiled detailed tables of the spectra of atoms and ions of 22 elements, listing for each line its wavelength and intencity, and the energies, term symbols, and J values for the lower and upper energy levels of the transition. A change has been made in the form of publication of the tables of atomic energies and the multiplet tables by the National Bureau of StanContribution of the National Bureau of Standards, not subject to copyright. VOL. 40,
NO. 5,
APRIL 1968
223 R
dards. These are now being published as combined tables, by element, under the auspices of the Sational Standard Reference Data System, with the intention of making possible more frequent updating of the information. Tables available under the new format have been compiled by hIoore for Si I (417) and Si 11, 111, and I V ( 4 1 6 ) . Corliss (105) has published corrections to another set of S B S tables, those by hleggers, Corliss, and Scribner (393). When these tables were published, it was stated that the intensity scale was of questionable accuracy at short wavelengths. Corliss has calibrateda the intensity scale for lines below 2450 A and and has listed revised values of relative intensities. Four spectral atlases have been published, three of them in the U.S.S.R. Galazka (184) has brought out a general atlas, and one by Kolenko (318) is intended for the analysis of ores and minerals. - i n atlas of thg arc spectrum of iron from 2280 to 6430 A was prepared by Kalinin, Marzuvanov, and 1Iukhtarov (287),and the spectrum of carbon in the vacuum ultraviolet is shown in an atlas by Kalinin, Mukhtarov, and Perevertun (288). Among the many review papers, historical surveys of emission spectrometry have been published by E d l h (141) and Nishio (489, 440). Surveys intended as an introduction to emission spectrometry have been written by Bryan (79),Hilton (246),and Kniseley (315). Batiz (35) has given a review of the theory of spectrometric analysis. Applications to the analysis of metals and ceramics were surveyed by Vilnat (621), and the analysis of geological specimens was covered by Kravtsov and Belen’kaya (323). Spectroscopy in the vacuum ultraviolet has been surveyed by Garton (186) and Hilton (247). Scribner (546) and Xargoshes (3’4) summarized recent advances in spectral excitation sources. Techniques for temperature measurements in plasmas were discussed by Tourin (602). Rev i e w on time-resolved spectroscopy were prepared by Strzyzewska (581) and Suzuki (586), and Paksy (448) considered the methods of investigating processes in the analytical spark gap. It is not surprising that many reviews have been published on the relatively new field of atomic absorption spectrometry. General reviews were written by Herrmann (243, 244), Hulanicki (261), Ivanov (267),Massmann (385),hlavrodineanu (389), Petrakev (465), Prugger (492), Rubeska Slavin (669), Suzuki and Takeuchi (585),Walsh (633, 634), and Walsh and Willis (636). Kahn (282, 283) discussed atomic absorption instrumentation. Applications in biology \\ere treated by Girard and Rousselet (196, 197) and by Howe (258). Other fields of application dis-
(&?e),
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ANALYTICAL CHEMISTRY
cussed were agriculture by Schueller (545), metals analysis by Kahn (284), and forensic science by Ramirez-Nufioz (498).
The older field of flame photometry has not been ignored in the preparation of reviews. Discussions of this subject were written by Dean (126), hlavrodineanu (390), and Pungor (494). Kaniada and Isagawa (289) compared chemical and electrical flames in their review. Some authors treated more than one method of analysis with flames. West (643) surveyed the general area of atomic analysis in flames, Dean (124, 125) discussed flame emission and absorption, and Clechet (101) compared atomic absorption and atomic fluorescence. The authors of this article can attest to the difficulty of keeping abreast of the many publications which appear each year. All spectroscopists can be grateful for the continued preparation by van Someren, Lachman, and Birks (662, 563) of the “Spectrochemical Abstracts.” Kaiser (286) has devoted attention to the problem of indexing the literature of this field, and has described a system of index terms equally applicable to peephole card and computer retrieval systems. Rossmassler (520) reported on the National Standard Reference Data System, a relatively new source of information in atomic spectroscopy as well as other fields. I n addition to providing data, the NSRDS also published some bibliographies; two of these of interest here are a bibliography on flame photometry compiled by llavrodineanu (391) with 5113 references, and one by Glennon and Wese (198) on atomic transition probabilities. SPECTRAL DESCRIPTIONS A N D CLASSIFICATIONS
The task of describing and classifying atomic spectra continues, aided considerably by new methods of observing and measuring spectra and increased use of digital computers for reduction of the data. The observation of new lines in the vacuum ultraviolet and infrared regions of the spectrum, where interferometric measurements are often difficult, is assisted by more precise measurement of lines of some elements which then serve as wavelength standards. Kaufman and Ward (297) measured spectra of C I, Cu 11, Ge 11, and Si I1 in the vacuum ultraviolet and studied the suitability of 32 lines of Cu I1 as standards. The suitability of lines of Si I in the vacuum ultraviolet as wavelength standards was evaluated by Radziemski et al. (496). A tabulation of wavelength standards in the infrared was prepared by Rao, Humphreys, and Rank (502).
A large share of the effort on description and classification of spectra has been on highly ionized elements. Little of this work is summarized here because these lines are not often observed in spectrochemical analysis. However, there has been a large number of new publications on other spectra which are important in analysis. The first spectrum of carbon was reinvestigated by Johansson (278), who measured s o 5 e 450 lines between 2478 and 25,843 A, revised and extended the energy level assignments, and calculated a number of vacuum ultraviolet wavelengths. Kaufman and Ward (298) made precise measurements of seven lines of S I in the vacuum ultraviolet. By combining these new data with other information on the energy levels of this atom, they were able to calculate wavelengths for 78 lines of Y I between 908 an$ 1745 A with an uncertainty of 0.001 A or less. The second spectrum of fluorine was restudied by Palenius (450), who found about 500 lines of the ion, about half of them new, and identified 27 new energy levels. Schoenheit (64%’) reported on the vacuum ultraviolet spectra of the rare gases neon, argon, krypton, and xenon, including observations of 500 new lines. Risberg (512) made new measurements of the spectrumoof the magnesium atom between 2000 A and 2.6 gm in the infrared. He gave data on 160 lines of the atom and a revision of the terms, as well as data on 16 lines of LIg 11. New measurements on some 200 lines of Si I in the vacuum ultraviolet were made by Kaufman, Radziemski, and Andrew (296) ; the measured wavelengths of 88 of the lines agreed with calculated wavejengths with an average error of 0.0008 A. The same report also contains new data on vacuum ultraviolet wavelengths for C I, Ge 11, K I, and Si 11. Litzen (351) investigated the energy levels of Si I . Banks, Bozman, and Wilson (24) made a detailed study of the spectrum of neutral titanium, resulting in a listing of wavelengths, intensities, and term designations for about 7700 lines. Velasco and Adames (615) investigated the energy levels of singly-ionized cobalt. The near-infrared spectrum of neutral indium was measured by Seguier (547), and wavelengths, intensities, and classifications of the lines observed were tabulated. The spectra of the rare earths and related elements remain a focus of considerable effort. Papp and Szarvas (464) observed the spectra of lantianum and cerium from 2250 to 4000 A and compared wavelengths and intensities from their measurements with published values. A list of 3532 lines was compiled by Zalubas and Wilson (667)in the absorption spectrum of neutral praseodymium between 1741 and 5839
A. Dupont (138) observed approximately 15,000 lines of Sm I11 between 1800 and 9500 A and made some term assignments for the ion. The first spectrum of terbium was analyzed by Klinkenberg (312) and by Klinkenberg and hleinders (313), resulting in assignment of over 2200 lines. Xew measurements and some assignments for H o I11 were reported by McElaney (363). A partial analysis of the first spectrum of erbium was given by Spector (570,571), who has also reported about 40 low energy levels in singlyionized thulium (572). Wavelengths and intensities for approximately 7300 lines of ytterbium were tabulated by Meggers and Corliss (392), together with Zeeman patterns for 1300 lines. The lines were abzigned to the atom and ions of ytterbium. Kew ly-measured near-infrared wavelengths for a few lines of thallium and mercury were listed by Seguier (548). -1study of the first spectrum of polonium by Vernyi (617) resulted in the finding and classification of 12 new energy levels. Giacchetti (191) tabulated the results of interferometric measurements of 701 lines of thorium, and Steers (5:s) listed the wavelengths of 1000 lines of this element in the near infrared and assigned transitions for 300 of the lines. Giacchetti (192, 193) also measured 8617 lines of protactinium, separated many of the lines into the first and second spectra, and found a number of energy levels for the atom and ion. The present knowledge of the first spectrum of uranium was summarized by Steinhaus, Blake, and Diringer (576), mho gave extensive experimental data, including isotope shifts, for many of the lines. Finally, it will not be often that analytical spectroscopists will be called upon to identify einsteinium in a sample, but the wavelengths of nine sensitive spark lines o,f this element between 2500 and 4500 A were made available by Gutmacher, Evans, and Hulet (230). Information on Lotope shifts is usually obtained as an aid in studies of atomic and nuclear structure, but the data are essential for isotopic analysis by atomic spectrometry. Stacey (573) has reviewed this subject. Among the new data on isotope shifts is a tabulation by Heilig, Riesner, and Steudel (239) of the shifts for the isotopes of germanium with even mass numbers from 70 through 76. Huehnermann and Wagner (259) measured isotope displacements of the resonance lines of 133Cs, 13Y!s, and 137Cs,while information on several isotopes of barium was provided by Jackson and Duong-Hong-Tuan (274) and by Comaniciu et a1 (101). Champeau, Gerstenkorn, and Gluck (96) and Champeau and Gerstenkorn (95) made measurements on the 140 and 142 isotopes of cerium.
Isotopic shifts for six lines in five isotopes of neodymium were measured by Gerstenkorn, Helbert, and Chabbal (190), and Hansen, Steudel, and Walther (233) gave information on shifts of a few lines in the even-numbered natural isotopes of samarium. Cajko (87) reported new data for a few lines of ytterbium, as did Golovin and Striganov (210). Extensive data were reported by Gluck (202),including isotopic diifts for 578 lines in five isotopes of tung-trn, 98 lines of osmium, and 56 lines of neodymium. From these new data. he was able to amend the classifications for several energy levels of tungsten and osmium and classify 2000 additional lines of the former element. Davis et al. (121) measured the hyperfine structure of two lines of Ig7Tl and 'g8Tl and their shifts relative to mjT1. The wavelengths of 97 of m8Po and the hyperfine structure of 31 lines of 209P0 were measured by Charles (98),and from these data he was able to derive considerable information, including new values for some energy levels. A similar study on plutonium was reported by Korostyleva and Striganov (SLO), including measurements on 275 lines. The parameters describing line intensities, such as the transition probabilities or oscillator strengths, are other important spectral characteristics, and reliable data of this type have been difficult to find. -4study is under way a t the National Bureau of Standards to critically evaluate these data, and the first result of this effort is a compilation by Wiese, Smith, and Glennon (646) of the best available transition probabilities for about 4000 lines of the atoms
Table 1.
Au I Ba I1 c I1 Ca I1 Co I, Cr I Cr I cuI Fe I Fe I Ga I
Sr I1 T1 I wI
INSTRUMENTATION
A theoretical comparison of dispersion, resolution, and signal-to-noise ratio in single- and double-pass operation of a spectrograph has been made by Lowenthal, Rank, and Wiggins (353), who showed how the theory can be applied when the objective is to optimize the signal-to-noise ratio a t a selected resolving poner. They compared the calculated results with measurements on a large spectrograph and found the agreement to be satisfactory. Several instruments were constructed for time-resolved spectrometry. An exceptionally flexible instrument was described by Walters (636), combining side-by-side and over-and-under Ebert mounts in a single unit. I t can be used photographically or photoelectrically, and either time-resolved or time-integrated measurements can be made. Bardocz (25) reviewed instrumentation for time-resolved spectroscopy. One means of achieving time-resolution is to attach a high-speed streak or framing camera to a spectrograph. Instruments of this type were built by Urixner ( 7 4 , Buttrey (85), and Nahugh (366), and also by Komissarova, Ostrovskaya, and Chelidze (319), who showed the use of
New Measurements of Oscillator Strengths or Transition Probabilities
Element and spectrum Ag I
if: Ar I1
and ions of the first ten elements in the periodic table. Corliss and Warner (106) evaluated published data on oscillator strengths for 20!0 lines of Fe I between 2080 and 4150 A and adjusted the values to a uniform scale. Other new measurements of transition probabilities or oscillator strengths are summarized in Table I.
Method Atomic beam absorption Hook method Hook method Lifetime Atomic beam absorption Lifetime Shock tube emission Lifetime Atomic beam absorption Arc emission Hook method Shock tube emission Furnace absorption Hook method Atomic beam absorption Hook method Lifetime Atomic, beam absorption Arc emission Lifetime Shock tube emission Atomic beam absorption Arc emission Lifetime Atomic beam absorption Lifetime Atomic beam absorption Arc emission
VOL. 40, NO. 5, APRIL 1968
225
R
the iiistruinent to observe the variation in time of the emission of a ruby laser. Another frequently-employed method of time iesolution is to sweep a slot along the slit of a stigmatic spectrograph. Uardoca and Vanjek (27) gave a description of such an instrument and showed how it could be used in a study of self-reversal of spectral lines. Bardocz (26) obtained a U.S. patent on equipment of this type. An instrument for the observation of the apectra of decaying plasmas, designed by Broemer and Hesse (77) employs two slotted rotating disks and a magnetically-driven shutter to permit time resolution of 0.1 msec and repetition frequency of only 0.2 Hz. Another time-redolving spectrometer was described by Bayunov, PodmoshenskiI, and Popov (86). Two rapid-scanning spectrometers meie described. I n the one built by Liberman, Church, and Asars (349),the wavelength was scanned by a rotating mirror near the exit slit of a CzernyTurner mount spsctrometer. Scanning ranges up too600 A and scanning rates as fast as 6 A/psec were demonstrated. D o h , Kruegle, and Penzias (135) built and tested an instrument which scans large regions of the spectrum a t rates up to 800 scans/sec by sweeping corner miriors through an intermediate focal plane in the spectrometer. Siewodniczanski et al. (435) described a mechanism for the simultaneous measurement of any two selected spectral lines, with provision for scanning either detector through the spectrum or for time-resolution studies. An instrument patented by Fruhwirt (177) also provides for the measurement of two lines simultaneously; a servomechanism with a diaphragm controls the light in one channel to equalize the two signals. Sordnieyer (441) suggested the modification of a small Ebert-mount monochromator to add a second exit slit for simultaneous measurement of line and background and to provide a periodic scanning mechanism. An instrument developed by Anderson (10) for the observation of spectra of weak light sources, such as aurora or the night air glow, employs an image orthicon detector. The spectrum of a just visible aiirora can be observed from 2800 to 8200 d at a resolution of 5 to 30 A with a one-second exposure. Taylor, Berg, and Jarnian (595) built a spectronieter for the observation of weak, unstable light sources. The spectrum is scanned repeatedly and the detector output is directed to a 400-channel analyzer, where each channel corresponds to a small wavelength interval. Cook (104) patented a mechanism to compensate for small movements of the light source of a spectrometer by corresponding movements of the exit slit. A portable spectrometer was built by Grove (228) to monitor the oxygen and
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ANALYTICAL CHEMISTRY
hydrogen content of inert gas used in arc welding. Images of two analytical lines and an argon internal standard line are swept cyclically across the exit slits by a rotating optical wedge, producing an ac signal proportional to line intensity above background. Lasers provide convenient light sources for testing and adjustment of spectrometers and spectrographs. Ohlmann and ,Mego (443) gave procedures for the preliminary adjustment of Ebert-mount spectrometers with the aid of an inexpensive gas laser. They reported a considerable saving of time, even though many of the fine adjustments could not be made with the laser source. Kaminskii, Kornienko, and Makarenko (900) advocated the use of lasers in testing gratings for Rowland ghosts. Improvements in spectrograph illumination systems were described in a number of papers. For illumination during trace analysis, Gerbatsch (187) employed a system of two mirrors, with one placed behind the light source to almost double the effective light flux. Strasheim, Brandt, and Kovacs (579) described a system with six lenses, including two raster lenses, for illumination of a photoelectric spectrometer; a significant improvement in analytical precision was found with the new illuminator. An illumination system intended for astronomy may also be of interest to analytical spectroscopists dealing with weak light sources. As built by Richardson (510), the device converts the circular star image into a thin rectangle on the slit of the spectrograph. Illumination systems without mirrors or lenses have also been tested. Loseke, Grove, and Pontarelli (352) employed fiber optics to conduct light from a moving welding arc to a spectrograph. A disadvantage of this system is the present, hopefully temporary, lack of materials for fiber optics which will conduct ultraviolet light efficiently. Peter (464) used a light tube, 5 m m in diameter and 200 mm long, to illuminate a spectrograph. H e was thus able t o avoid the necessity of accurate alignment of the source with the spectrograph, simplifying the task he had of illuminating two spectrographs simultaneously. On the other hand, Kuznetsov (834) described a system for photographing spectra from two light sources simultaneously on a single spectrograph. The increasing use of high grating orders to improve resolution of complex spectra or to increase the line-to-background ratio in trace analysis has led to some new developments in cross-dispersion devices, commonly called order sorters. An order sorter described by Van Rooyen (613) features flexibility in components so that the separation between orders can be adjusted as needed.
Pinnington (474) designed an easilyconstructed order sorter made up of a small prism and a plane mirror. Blackwell et al. (48) tested a grating predisperser for use in the vacuum ultraviolet, where suitable prism materials are not available. An order separation device developed by Gerharz (189) employs a coarse isometric grating within the spectrograph. An advantage of this device is that the isometric grating produces several orders of its own, with predictable intensity relations which can be applied as a photometric calibration scale. Nagy and Sanisoni ($27) discussed ways of producing neutral wedge filters to be mounted at the slit of a spectrograph. Uses of such neutral filters were described by Nagy (426), who also described the production and use of a step filter whose transmittance varies in such a way as to compensate for the variation with wavelength of the contrast of a photographic emulsion. I n this way, a particular difference in density between two steps on the developed emulsion will always correspond to the same intensity ratio. The installation and adjustment of exit slits on photoelectric spectrometers can be a problem for laboratories requiring occasional changes in the line array. d more rapid method of installing exit slits was devised by Tymchuk, et al. (607),and Moriis and Van Staden (418) modified a commercial spectrometer to permit the slit adjustments to be made more easily. Van Der Piepen, Schroeder, and Jacobs (612) devised an attachment for a spectrometer to correct for small shifts in the positions of the line images relative to the exit slits. Devices for this purpose are incorporated in some commercial spectrometers and they may be 2 desirable addition to others. Soules (568) has patented a novel method for making gratings with very small spacings by evaporating aluminum onto a ruby or quartz crystal which is kept at a low temperature and subjected to monochromatic sound waves at a frequency of several GHz. H e claimed to have produced a grating with a spacing of about cni in this way. Most information on spectroscopic light sourceb is summarized in another portion of this review; only a few instrumental developments are covered here. Conover, Peters, and Lalevic (103) designed an inexpensive solid state circuit for regulation of dc arc current; fluctuations were said to be less than 50 n i h with currents of 1 to 15 A. Equipment and methods for oscilloscopic characterization of an electronically ignited spark source were described by Walters and Malmstadt (697). Fedchenko, Fal’kovskiy, and Bobrov (161) designed equipment for measure-
ment of the distribution of temperature in a pulsed arc. The radial distribution of intensity in the spectral lines could be measured during a single pulse or at selected times during a pulse. A gas metering and mixing system described by Kash (451) is intended to help provide controlled atmospheres for spectroscopic light sources. A few publications were concerned with improvements in the photoelectric measurement of very low light fluxes. For this purpose, Pech 1460) developed a detector system in which the signal measured is the time delay between application of a voltage to the electrodes of an optical counter tube and initiation of a discharge. Even with a photocathode of rather low quantum efficiency (4 X 10-4 electron/photon), light signals as low as 2.4 X lo3 photons/sec mere detected. Pao and Griffiths (455) investigated the application in spectroscopy of a novel method of detecting light signals in which the quantity measured is the mean of the square of the fluctuations of the photocurrent. They found that the new method made it possible to discriminate against darkcurrent noise and that the performance appeared to be better than either de or phase-sensitive amplifiers for measurement of low light intensities. Vidal (619) investigated methods of reducing photomultiplier noise, including cooling and the use of a small permanent ring magnet to restrict the sensitive region of the photocathode to approximately the area actually illuminated. llaslov (584)studied the application to spectral analysis of autocorrelation methods of measuring weak photoelectric signals in the presence of noise. He found that detection limits by this method were improved by a factor of two compared to photographic detection, even with relatively simple equipment, and thought that further improvements could be achieved by the use of more sophisticated equipment such as electronic computers. I n emission spectrometry, it is frequently the problem in photographic microphotometry to measure a wide range of intensities rather than to detect low signal levels. Two recent publications offer different approaches to this problem. Lutnes and Davidson (554) investigated the uses of a low-contrast developer and found that plates developed this way gave characteristic curves which covered a 100-fold range of intensities n i t h little increase in granularity and no change in sensitivity compared to plates treated with the customary developers. Another approach is a new type of film which is made up of three emulbion layers of differing sensitivities. Each layer also contains a coupler dye, and after development the three layers can be distinguished by viewing the images through filters of
appropriate color. Bryant, Troup, and Turner (80) studied the properties of this type of film, and reported that it was possible to measure intensities over a range of 10’. Aramu and Rucci (12) advocated the recording of the first derivative of the transmittance to measure weak spectral lines on a film or plate, and described an instrument to make such measurements. Walters and Malmstadt (658) also proposed derivative microphotometry and showed that it is a superior method of determining line positions. In another microphotometer, Poppe, Hoekstra, and Klinkenberg (487) employed an interferometer, rather than a precision screw, to measure line positions and found that a reproducibility of 0.5 pm was possible. Steinhaus, Engelman, and Briscoe (577) described an automatic microphotometer which measures the transmittance a t small, equally-spaced intervals on the plate, and records data in digital format. A computer program is also described which analyzes the data, providing the position, wavenumber, intensity, and shape for each line found. Nakamura and Abe (428) developed a microphotometer which features variable magnification from 5 X to SOX and output of optical density values onto a paper tape. STANDARDS, SAMPLES, CALIBRATION, AND CALCULATION
Kurguzov et al. (5.91) devised a method for the preparation of standards in the form of minute spherical particles by extrusion of molten metal through orifices of 0.04 to 0.1 mni diameter. The technique was recommended for alloys of indium, tin, and lead which do not form solid solutions. Sotnikov et al. (567) employed a similar technique for the analysis of an indium-antimonygold-gallium alloy. Zausznica (669) obtained a patent on a method for preparing spectrometric standards by powder metallurgy. The preparation of a series of copper alloys, available from the Spectroscopy Society of Canada, was described by Dalton, Thomson, and Gillieson (118). Belohlavek and Pribil (45) gave information on standards for l o w , medium-, and high-alloy steels prepared in Czechoslovakia, including the methods of preparation and characterization. Optical metallography and electron probe microanalysis have been applied to study the homogeneity of some National Bureau of Standards standard reference materials to determine their suitability for calibration of instruments for microanalysis. Yakowitz et al. (654, 655) gave the results of such studies on two brasses (NBS 1102 and 1102c), a low-alloy steel (NBS 463), a white cast iron (KBS 1175) and a
stainless steel prepared by powder metallurgy. Flanagan (167) gave information on six new silicate rock standards issued by the U.S. Geological Survey. Information on geochemical standards, including rocks, minerals, and economic raw materials, available from sources throughout the world was compiled by Flanagan and Gwyn (168). Information on geological standards from the Central Geological Institute of Berlin was summarized by Grassmann (622) and by Fuchs et al. (178).
A novel method for powdering materials such as quartz, corundum, and ceramics for spectrometric analysis was tested by Zil’bershtein, Sanarokov, and Semov (672). The material to be ground was placed in a special cell together with water and subjected to a rapid series of high-voltage capacitor discharges, after which the powder was filtered off. The possibility of performing a quantitative spectrometric analysis without recourse to standards was the subject of a study by de Galan (180). He compared the amounts known to be present with amounts found directly from line intensities in the de arc for seven elements in silica-graphite and silica-lithium fluoride-graphite matrices; the average error was about 35%, which would be adequate accuracy for a semiquantitative method. The state of our present knowledge, particularly with respect to such matters as chemical reactions in the arc plasma, is such that the agreement may well have been fortuitous in part, but certainly studies in this direction should be continued. Investigations of this type are probably more advanced in the flame methods, where there is a more detailed knowledge of the physical and chemical processes involved in an analysis. Vickers, Remington, and Winefordner (618) and Rinefordner et al. (650) studied mathematically and experimentally the shapes of analytical curves in flame emission spectrometry, taking into account such factors as self-absorption, ionization, compound formation, sample flow, and the entrance optics of the spectrometer. Agreement they considered to be excellent was found for the calculated and experimental analytical curves obtained for the yellow sodium doublet in three diverse flame.. The effects of ionization and dissociation of compounds on the shapeq of analytical curves in flame photometry were also discussed by Schillak (641). One difficulty in applying such computations to atomic absorption and atomic fluorescence flame spectrometry is that relatively little is known of the shapes of the lines emitted by the light sources and absorbed in the flames. Computed line widths in flames were VOL 40, NO. 5, APRIL 1968
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tabulated by Parsons, McCarthy, and Rinefordner (455), and Hollander and Broida (255) reported line width peasurements for ihe OH band at 3072 A and for the 3075 A zinc line. Yasuda (658) reported some interferometric measurements oj the profile of the calcium line at 4226.7 A as emitted by a hollow cathode lamp and after passage through a flame containing calcium atoms. H e discussed the relation of the line profiles to measured flame absorbances. McGee and Winefordner (SG4) measured the damping constants, which are related to the line widths, for 12 elements in two flames. Winefordner, et al. (653) treated mathematically the atomic fluorescence signals at high and low element concentrations for the cases of excitation by line and continuum sources and for resonance, stepwise-line, and direct-line fluorescence. Equations applicable to analytical curves in emission spectrometry were considered by Pittwell (477), who included factors such as the method of measuring line intensities, interference on both analytical and internal standard lines, and variable internal standard concentrations. Pedan (461) gave a mathematical treatment of internal standardization in the determination of impurities in a binary matrix. H e concluded that the average of the intensities of lines of the two matrix elements would, with a small correction, be a suitable internal standard. A variation of the method of additions, adapted for the simultaneous determination of several elements, was described by Masuda and Onishi (387), who replaced the normal graphical method of calculation with a new set of equations. Considerable attention has been b'wen to evaluation of limits of detection in emission spectrometry. Two papers, by Hobbs and Smith (250) and Ehrlich (144) treated the important case of samples so close to the limit of detection that a line can be seen in some exposures but not in all. The authors of both papers propose that the amount present still can be estimated by simply counting the fraction of exposures in which a line is detected. The use of signal-to-noise ratio theory in selection of optimum conditions for spectrometric methods was treated by Winefordner, hIcCarthy, and St. John (649),who considered not only detection limits but the more general case of analysis well above the lowest concentration detectable. Salpeter (536) has also given a general discussion of limits of detection as determined from the signal-to-noise ratio, including applications in emission, atomic absorption, X-ray fluorescence, and mass spectrometry. St. John, Alecarthy, and Winefordner (578) evaluated the statistics involved in expressing a limit of de1
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tection as a function of the number of replicate measurements made and the confidence level desired. Considerable attention has been devoted to the effect on detection limits of the photographic emulsion and the method of photometry. Nalyshev and Razdobarin (372) compared detection limits by photographic and photoelectric methods, with particular attention to the effect on photographic detection of the exposure level and the size of the line image. Svoboda (588) evaluated the optimum density of the developed photographic image for detection of weak lines, which is the density a t which the line-plus-background exposure can be distinguished from a nearly equal background exposure with the greatest certainty. Similar treatments were given by Plsko (479), Chamberlain (54), and McCrea (861). The last two papers mentioned were concerned with establishing the optical density giving the best precision of measurement of line intensity, but this should be the same density that is optimum for distinguishing line from background. Boumans and Maessen (58) considered detection limits by photographic spectrometry for the cases of a smooth ound and a background containing spectral structure; they also extended their treatment to include the influence of a blank on the detection limit. Ehrlich and Gerbatsch (146) stressed the advantages of recording microphotometry for the detection of a weak line in the presence of a background that is not smooth, and the same authors (145) concluded that the granularity of the emulsion may be the factor controlling the detection limit under these circumstances. Boumans and Xaessen (59) gave a mathematical treatment of the effects on limits of detection of granularity of the emulsion and fluctuation in the blank. A more general discussion of photographic limits of detection was given by Gerbatsch and Krasnobaeva (188), who studied the influence of the contrast, speed, and granularity of several commercial emulsions on the detection of weak lines. Plsko (482) improved photographically-ineasured detection limits by adding up microphotometer scans of narrow regions near the analytical line. Several papers were concerned with detection limits in the various flame methods of analysis. Parsons, McCarthy, and Winefordner (456) treated the effects of such factors as source intensity and flicker, flame background, and the properties of the monochromator and amplifier on minimum detectable concentrations in flame emission, absorption, and fluorescence spectrometry. The theory and experimental methods for optimizing instrument parameters in flame methods to achieve the best possible detection limits and
precisions in analysis we1 e reviewed by Parsons and Kinefordner (457). Detailed evaluations of conditions that affect signal/noise ratio, and thereby the detection limit, in atomic fluorescence spectrometry were given by Jenkins (276) and by Winefordner et al. (662). Ramirez-Mufioz (497) treated detection limits and sensitivities (concentrations of an element required to give a chosen signal) in atomic absorption spectrometry and their correlation, taking into account the possibility of having only a limited amount of sample available. Other discussions of detection limits in atomic absorption spectrometry were published by Ramirez-hlufioz (495) and Ranifrez-llufioz, Shifrin, and Hell (501), who also discussed the evaluation of the lowest concentration of an element required to give the maximum analytical error that can be accepted in a given case, as well as the selection of the concentration range for which the analytical error is minimized. One of the assumptions in these treatments of detection limits is that the data near the limit of detection follow a normal (Gaussian) distribution. X s chenko (404, 405,@ 7 ) , from a study of the results of large numbers of spectrometric analyses, has concluded that the data actually follow a logarithmically normal distribution of errors. Plsko (480)has reached the same conclusion from a smaller number of measurements. Xshchenko (40s) also derived, from a study of the errors in the spectrometric analysis of minerals, the effects of subjective factors on semiquantitative determinations, and he has discussed methods for selection of those results which are most likelj t o be correct. Another study of the accuracy of semiquantitative spectrometric analyses was made by Kvyatkovsbii ($36). Calibration of photographic emulsions is certainly not one of the most pressing problems in emission spectrometry, but it remains a matter of some interest. Torok and Zimmer (599) reviewed the theory and application of the l-transformation developed in their laboratory, and Zimmer, Torok, and Asztalos (675) studied the accuracy of results obtained with this transformation using several different emulsions. One possible difficulty in calibration of photographic emulsions is the Schsartachild effect: E = I t p , where E is the exposure, I is the intensity, t is time, and p is a parameter depending on the methods of exposure and development and the properties of the emulsion. The influence of the Schmartzchild effect was investigated by Torok et al. (GOO, 601). They reported that the exponent p was less than 1 when the eniuliion was exposed by means of a spark or deuterium lamp, but that it was greater than 1 when the light source was a high-intensity flash lamp. In either
case, it would be necessary to determine the value of p for accurate emulsion calibration. When a rotating sector was used, however, the Schwartzchild effect was compensated by the intermittency effect and p equalled 1. Stable light sources for intercomparison of different emulsions were suggested by Slavin (558), who employed a lowpressure mercury lamp, and by Takahashi (591), who suggested an iron hollow-cathode source. h part of the interest in photographic emulsion calibration arises from the increasing use of automation for evaluation of spectrometric data. For example, Chaney (97) found that the optical density of a line, integrated over the line, is essentially a linear function of the intensity and that the integrated density measurements give analytical curves that are linear over a larger range of concentrations than are curves based on peak intensity measurements. One advantage of the integrated density is that it is possible to construct a microphotometer to measure this value automatically. With the availability of computers and programs for the calculations in photographic photometry, attention turns to speeding the process of reading the plate, particularly in automating the microphotometer. Helz (241) proposed one procedure for automation of the process of reading spectra on photographic plates. Some automated microphotometers have already been mentioned in the section on Instrumentation. In addition, Ditzel and Giddings (131) described an automatic microphotometer and a computer program which performs such functions as locating line positions, smoothing data, and converting microphotometer readings to relative intensities. Franke and Post (173, 174) have also described a microphotometer with automatic readout and computer programs for data reduction, as have Maiorov, Guzeev, and Timofeev (369). Becker and Drawin (39) developed a microphotometer, incorporating a curve follower and integrator, which records intensity or the logarithm of intensity as a function of wavelength and also the integrated intensity of each line. There seems t o be no question any longer that completely automatic evaluation of photographically-recorded spectra is possible, but it will be necessary to explore the different possible methods to find the one which gives the greatest saving in time a t the least cost, while preserving flexibility for nonroutine use. Even without an automatic microphotometer, the computer can save considerable time in spectrometric calculations. Gordon and Gallagher (215) described a computer program which fits an emulsion calibration curve and converts microphotometer readings into intensity ratios. 'rime-sharing com-
puters are often particularly useful for this purpose, since they shorten the time required to obtain the data, and Arrak (16) has published a computer program for this purpose written in the BASIC language employed by one time-sharing system. Krinberg and Smirnova (325) have extended the calculations to first convert the microphotometer readings to relative intensities, with provision for correction for background, and then to calculate concentrations. The application of computers in spectrometric analysis was reviewed by Maiorov (368). X noteworthy paper on this subject was published in this Journal by Hasler (235), who proposed bringing the data from optical and X-ray spectrometers and an X-ray diffractometer together in a single computer to give more accurate analytical results than would be possible from any one of the instruments alone. Pohl (483) has reviewed the use of computers in analytical chemistry, giving applications in spectrometric analysis as one example. Particular computer-spectrometer installations in quality control laboratories were described by LeRoy (347) and by Glover and Orwell (201). Cronhjort (109) presented a mathematical approach to reduction of data from multicomponent analyzers, with particular reference to emission spectrometers. Ramirez-hfuiioz, Malakoff , and iiime (600) summarized some uses of computers in emission and absorption flame spectrometry. One particular use of computers was described by Szivek, Paulson, and Valberg (590), who were concerned with spectrometric analysis of red blood cells. Their program converts the instrument readings to element concentrations, calculates the amount of each constituent present per cell and per unit volume of water, and does a detailed statistical analysis of the resulting data. EXCITATION SOURCES
There is an almost bewildering variety of light sources which have been applied to spectrochemical analysis, employing electrical power in forms ranging from the de arc to several fornis of radiofrequency discharges. The task of evaluating and comparing each of these is certainly formidable, particularly when other instrumental variables may have more effect on the analytical results than does the light source. For example, Buell (81) compared flame excitation with vacuum cup-spark excitation for the analysis of solutions, and reported that, under the conditions of his experiment, the dispersion of the spectrometer appeared to have more influence on the limits of detection than did the differences between the excitation sources. In some cases, even a small change in
the method of operation of the light source can have a considerable effect. Mellichamp (397) reported on the operation of the de arc with a cathode containing in ites core an element with an ionization potential lower than that of carbon. He found that the arc temperature is not lowered, as occurs when a buffer is added to the anode with the sample, but that current and voltage fluctuations were reduced, together with arc wandering, which should improve the precision of analysis with the arc. The effects of magnetic fields of various forms on the shape of the arc column and on line intensities were studied by Vukanovic and Georgijevic (629), who said that line intensities could be increased as much as 3- to 4-fold in this way. Schroll and Sauer (544) developed a graphite beaker for use with a double arc, allowing the use of samples weighing as much as 10 g and giving detection limits in the range of ng/g. Experienced spectroscopists can often identify the major metallic element in a sample by observing the arc during excitation. Mellichamp (396) reported that it is possible to distinguish among simple chemical compounds in the electrode by recording the voltage fluctuations during the burn. By now, a number of methods are available for stabilizing the de arc, and inany of these permit introduction of solutions, giving quite stable emission intensities. Holdt and Hoffmann (254) reviewed magnetic, wall, and disk methods of stabilizing the arc for spectrometric analysis. One property distinguishing the different types of stabilized arcs is that in some the plasma viewed by the spectrograph or spectrometer carries the current, while in others when the plasma is viewed it has been heated by a discharge but has emerged from the discharge zone. In a comparison of these types of arcs, Kaiser, Laqua, and Schirrmeister (286) found that the current-carrying plasma is cooled by addition of elements with low ionization potentials, but the current-free plasmas have temperatures which are affected only by the gas and water supplied by the aerosol. Takeuchi and Sakurai (592) studied the properties of one form of the plasma jet, and compared it wit'h the ac arc. They found that the plasma jet gave more linear analytical curves and less interelement effects than the ac arc, but that the detection limits, as measured photographically, were about the same for the two sources because of the large amount of background in the plasma jet associated with the water introduced with the sample. In photoelectric methods, where the fluctuation of the background is more important than its absolute level, it is reasonable to expect that the plasma jet should give lower detection limits. VOL. 40, NO. 5, APRIL 1968
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Several new types of stabilized arcs for the excitation of solutions have been developed. A wall-stabilized arc was described by Rieniann (511), who listed detection limits and analytical precisions with the source. Hoffniann and Holdt (263) developed a disk-stabilized arc which they said could give analytical precisions of better than 1%. Another stabilized-arc design was given by Roetger (516), who also listed detection limits with the source and showed (517) its application to the determination of silicon in urine. Doerffel and Schlichting (134) also applied a stabilized arc to the determination of silicon, in samples such as limestones, cements, slags, and silumin alloys, and Doerffel and Lichtner (132) reviewed applications of a diskstabilized arc to the determination of silicon and zinc. The hollowcathode lamp can be considered as a special type of de arc which is operated a t a reduced pressure, a relatively high voltage, and lower currents than other arcs. -4hollom-cathode lamp designed by Maierhofer, Reis, and Setz (36‘7) operates a t currents as high as two amperes, permitting exposure times as short as those used with spark sources. Samples can be in the form of metal, or may be powders which are mixed and compacted with a metal powder, and both metallic and gaseous elements can be determined. The stability of the source is said to be good enough to give analytical coefficients of variation as small a3 0.5?&, Knerr, Xaierhofer, and Reis (314) used a hollowcathode discharge for the analysis of metals and glass. Nilazzo (399) debcribed a hollowcathode lamp developed for routine analysis in the vacuum ultraviolet region, permitting the determination of nonmetallic elements, and llilazzo and Sopranzi (400, 402) reported on the use of this source for both qualitative and quantitative analysis. They found that as little as 10 ng of iodine could be detected in potassium chloride, and that iodine could be determined readily in this niatrix a t concentrations from 1 to 100 pg/g. Pevtsov and Krasil’shchik (467) developed a new form of hollow-cathode lamp, in which the evaporation and excitation zones are separated by a membrane, improving the stability of the discharge. Pfeilsticker (470),who has in the past made many contributions to the design of spark excitation sources, described a circuit for generating lowvoltage sparks with a frequency of 1 to 40 kHz; a t this high frequency, he found that background and air lines were less intense than in normal sparks, giving improved detection limits and accuracy. -1 method for determining elements such as sulfur, selenium, and tellurium by spark excitation in a vacuum mas developed by Davletshin, Zakharov, and 230 R
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Xidarov (122). Two copper electrodes, with a 1-mm gap, were used, and the upper one was filled with the powder sample. Lines of the elements mentioned mere photographed in the vacuum ultraviolet. A novel procedure for spark excitation of solutions devised by Vukanovic, Vajgand, and Todorovic (630) provides for simultaneous electrolytic separation. A rotating copper disk is an electrode for two electrical circuits, and one, operated at low voltage de, plates the elements to be determined onto the disk. There has been a very considerable interest in light sources powered by radio-frequency discharges. Four papers mere published on low- or mediumpower discharges suited for trace analysis of very small samples. A device called a helium-glow photometer, developed by Vurek and Boivnian (632), uses a lowpower glow discharge and simple measurement apparatus. Small amounts of solution are dried a t the end of a wire which is then introduced into the discharge. Samples containing as little as lO-’4 *lf of sodium or potassium were analyzed. Vurek (631) reported on analysis of nanoliter amounts of solutions with this device. Runnels and Gibson (531) investigated the properties of a discharge of this type. At a power level of only 25 W, 1O-I’ to gram of silver, copper, iron, chromium, and cobalt mere detected in samples as small as 1 pg, d torch discharge operating a t 200 W at 520 MHz was studied by Yamanioto and Llurayania (656), who gave information on the temperature and stability of the source as well as detection limits for a few elements. The electrodeless lamp is another high-frequency discharge which can be operated a t low power. These lamps, pvhen properly constructed and operated, will emit intense, sharp lines, making them witable for atomic absorption and atomic fluorescence spectrometry provided that adequate stability can be demonstrated. Xethods for making lamps for these purposes were given by Richards (bog), Bazhov and Lazarev (37), Dagnall, Thompson, and West (114), and Ani, Dagnall, and K e s t (11). Atkinson, Chapman, and Krause (17) investigated the spectra of potassium and rubidium emitted from such lamps, with particular attention to the effect of the operating parameters on the intensities, half-widths, and selfreversals of the lines. The use of electrodeless lamps in atomic absorption analysis was studied by Ivanov et al. (272, 273). Bodretsova, L’vov, and llosichev (51) powered a hollow-cathode lamp from a high-frequency supply and found an intensity gain of about two orders of magnitude as compared to lamps excited with de power, with no increase in selfabsorption. The effect of a microwave
field on emission of sodium in a hydrogen-oxygen flame was reported by Rosenthal and Eyer (518), who also found an intensity increase by two orders of magnitude even though the microwave power, a t 2.5 GHz, was estimated to be only about the thermal energy of the flame. Pitet et al. (476) observed spectra of the halogens by excitation of metal halides a t 50 MHz at low pressure. The excitation could be established between the plates of a capacitor or in a coil. There has been considerable interest in inductive radiofrequency discharges, operating typically at powers of a few kilowatts a t frequencies in the megahertz range, for the analysis of solutions. Papers on such torch discharges have been published by Pforr and Langner (472), Dunken and Pforr (136, 137), Britske, Borisov, and Sukach (72), Egorova (142),and Goto, Hirokawa, and Suzuki (218). Hoare and lIostyn (249) employed a torch of this type for the analysis of both solutions and powders. These torches are often compared t o chemical flames, but there have apparently been no direct comparisons with any of the forms of stabilized arcs. The latter comparison would seem more meaningful to the authors of this review, since the torches are more difficult to operate, require considerably more expensive equipment, and generate considerably more complex spectra than do the chemical flames. Increasing interest in measurements of such parameters as temperature distributions, electron concentrations, and element distributions in de arcs was noted in the last review. Such studies have continued. Margoshes (376) reviewed the theories of excitation and ionization in plasmas a t thermal equilibrium, and showed how even our limited present knowledge of temperature and electron density in spectroscopic sources can be applied in practical situations. One important application of knowledge of the properties of discharge plasmas is understanding of matrix effects. Matherny (388) investigated matrix effects in spectrometric analysis of sulfide, oxide, and carbonate ores, and related the effects to the influence of the chemical components of the sample on the temperature of the arc plasma. Krinberg (324) carried out a theoretical treatment of the effect on arc plasma temperature of the addition of potassium, sodium, calcium, magnesium, and carbon. He concluded that small amounts of these elements would have little effect, but that larger amounts will change the temperature, the magnitude of the change decreasing with increasing arc current. Bokova and Semenova (5‘4) treated theoretically the influence of thermal conductivity of the plasma on spectra
emitted by the dc arc. This influence is important because the temperature of the plasma is a result of a balance between the rates of energy input and loss, and thermal conductivity is responsible for the loss of a significant amount of energy from the plasma. Thermal conductivity can be changed by altering the atmosphere around the arc. Another theoretical study, by Diermeier and Krempl (128), was a calculation of the optimum temperature for a number of elements, defined as the temperature a t which the line intensity is a maximum. -it higher temperatures, increasing ionization will decrease the concentration of neutral atoms, in turn decreasing the line intensities. Their calculations covered the temperature range from 3000 to 50,000' K and pressures from 0.1 to 5 atm. They showed that addition to the plasma of an element such as argon, with a high ionization energy, will increase the degree of ionization and shift the optimum temperature to lower values. However, in plasmas having a large excess of argon they predict a second maximum in the plot of intensity us. temperature near 11,000' K, which arises from the onset of significant ionization of the rare gas at that temperature. Any discussion of temperature of a discharge plasma implies that thermal equilibrium exists, a t least within small regions of space. Krysmanski (328) surveyed the data in the literature which have often been taken as evidence of thermal equilibrium in lowcurrent arcs, such as are employed in emission spectrometry, and found the evidence to be insufficient. Strictly speaking, thermal equilibrium cannot be expected in any discharge, and the important question is whether the departure from equilibrium is large enough to invalidate the concept of temperature in practical calculations. Some new data on arc properties were also given. Boumans and Rouws (60) reported new data on temperature and electron concentration in a lithium fluoride-graphite arc, and discussed some implications of the measurements. They found a dependence of the intensity of the background on temperature, with a minimum near 5700' K. Studies of the temperature distiibution of arcs in argon were reported by llariiikovic (378) and Gol'dfarb and L-zdeiiov (205); the latter authors measured electron and heavy particle temperatures and also the radial pre5sure distribution. Doerffel and Lichtiier (133) measured the temperature of a cascade-stabilized arc, and found it to be near 5000' K and to show a dependence on arc current. The temperature and electron density of a free-burning arc were compared by Vukanovic and Georgijevic (628) with the same properties of arcs constrained to burn within or between quartz or
copper tubes. They found that constraining the arc to a smaller diameter increased its temperature but did not affect the electron density. They also related these measurements to relative intensities for several elements in these arcs, and concluded that the atomic mass and degree of ionization of the element had an important effect on intensity. Studies of this type on pulsed discharges, including sparks, require resolution in time as well as in space, and are therefore more difficult. Bardocz and Voros considered the methods for determining spark plasma temperatures from relative line intensities ( S I ) ,Stark broadening (29),and wavelength shifts of lines ( 2 8 ) ; they also (SO) described the spatial and temporal variation of spark plasma temperature as determined from relative line iiiteiisities in time-resolved spectra. Methods of measuring ion concentrations in low-voltage condensed discharges were summarized by Zykova and Zolotukhin (676). They concluded that finding different values for the electron or ion densities from the Stark broadenings of lilies of various elements may arise from the fact that the peak intensities of the various lines are obtained in different, narrow radial zones in the discharge, pointing out again the need for spatial resolution in these measurements. Calker and Lensing (88) studied the emission of light by very brief (less than 1 psec) pulsed discharges, and concluded that such short durations may prevent attainment of thermal equilibrium. Some varieties of radio-frequency discharges were mentioned previously as excitation sources. Johnston (279) found that the region of maximum temperature (9500O K) in an inductioncoupled plasma torch was located well off the axis. He also measured the electron density in this torch. Pforr and Kapicka (471) reported on temperatures in a torch discharge as measured from the rotation and vibration spectra of OH, NO, and CN molecules and from the relative intensities of copper lines. They found temperatures near 3200' K for O H and S O , but near 5000' for C N and Cu, and attributed the differences to departure from thermal equilibrium. While it is possible that their interpretation is correct, it i5 also possible that the differences reflect only the maximum of abundance of the different thermometric species in separate portions of the discharge. Kapicka (291) also reported results of temperature measurements in a torch discharge. The temperature found from the relative intensities of copper lines was 7370' K for a discharge in an argonhydrogen mixture and 7800' in nitrogenhydrogen. However, the rotational spectrum of nitrogen molecules yielded
temperatures of 940' and 1360' in the same gases. Ion concentrations, determined from the Stark broadening of the H line, were also reported. The effect of alkali metals on the temperature of a torch discharge was investigated by Cristescu and Giurgea (108), who found that no detectable temperature change was brought about by addition of sodium or cesium as 0.001M solutions and concluded the determination of other elements would not be affected unless the alkali elements were present in considerably larger amounts. I n addition to the temperature and electron density, another important factor affecting line intensities in spectrometric sources is the concentration of atoms and ions, which is determined by the rate of addition of the elements, usually by evaporation from the electrodes, and the rate of removal by diffusion, convection, and chemical reaction. Much has been written during the period covered by this review about the processes affecting the vaporization of elements and compounds in electrical discharges. Several of these studies were concerned with the chemical reactions which occur in the crater of an arc electrode. The reaction products can be identified by interrupting the arc before complete evaporation and obtaining X-ray diffraction patterns of the material remaining in the crater. Rautschke (606) performed such a study of the reactions of oxides of silicon, titanium, zirconium, vanadium, molybdenum, manganese, and nickel with graphite, and he concluded that the elements in groups IV to VI of the periodic table form stable carbides while those in groups VI1 and VI11 form only unstable intermetallic carbides; he found the results of this study to be in agreement with thermodynamic predictions and with measurements of intensities of emission spectra. Pavlyuchenko, Dubovic, and Zonov (459) carried out similar studies of compounds formed by reaction of the impurity elements being determined with the matrix compounds. The results were interpreted in terms of mechanisms of fractional evaporation. Adamson, Stephens, and Tuddenham (2) identified compounds formed on arcing various minerals from their infrared absorption spectra, and they showed how the results of such an investigation could be applied in the development of an analytical method. The time-intensity curves can also yield information on probable reactions in arc electrodes. Bril and Lore (69) and Bril, Lore, and Vinot (70) have given interpretations of these volatilization-excitation curves in terms of such reactions as reduction of oxides to metal by carbon and the formation of carbides. VOL 40, NO. 5 , APRIL 1968
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The method of sifting powders into an arc would appear to be free from any influence of the rate of evaporation of the sample, as long as the particles are evaporated completely. The effects of particle size and of chemical reactions in this method were studied by Rusanov and Batova (532, 533), and Tumanov (605) examined the evaporation of particles in pulsed discharges. -1s particles move through the plasma, individual compoundi vaporize at different times, causing a separation of the elements which caii be different for samples having different ranges of particle size or different chemical histories. Chemical reactions during volatilization can often be affected favorably by simple methods. P l a ~ t i n i n (478) and Tymchuk, Russell, and Berman (608) suggeqted the addition to the sample of copper halides to promote formation of volatile compounda of the elements to be determined, with increased line inteiisities as a result. Such additions are an extra step in the analytical procedure and offer a chance for contamination. n’heii controlled atmoipheres are being used, it would be feasible to add a halogen gas to promote the formation of volatile compounds, but these gases are corrosive aiid thus difficult to handle. Sanibueva and Shipitsyn (537) have suggested the use of tetrafluoroethylene as a convenient gaseous source of fluorine. There have been several studies of the niechaiiiqni of sampling of metal.; in spark discharges, with particular attention to changes in the thin surface layer being sampled. One posqible mechanism of change of this iurface layer is selective diffusion of elemelits from the bulk material. The role of diffusion in spark discharges has been examined by Buravlev (83), Grikit (226), Grikit, Galushko, aiid Chernyshova (227), and Nikitina (436), who all agreed that diffusion is negligibly small i n the spark, although the lastnamed author found that extensive selective oxidation of metal surfaces can have an important effect when metals are analyzed with arc-like discharges. On the other hand, Holler (252) also examined the effect of the spark on the surface layer of an alloy, and concluded that both the constitution and structure vary considerably during the sparking. I t may well be that each of these workers is correct, and that the importance of changes in the surface of the metal depends strongly on the nature of the material being investigated. For example, Palatiiik and Levchenko (449) compared the compositions of the sample and the vapor when binary alloys were sparked; they found that for some alloys the bulk material and the vapor had the same compositions, but for others one component was vaporized 232 R
ANALYTICAL CHEMISTRY
preferentially. The observations were related to the structures of the materials, which may be solid solutions or mixtures of nearly pure elements; the form of the binary mixture can change under the action of the spark, altering the relative fractions of the two components vaporized. Some mathematical models were proposed for sampling by the spark discharge. An equation was derived by Siliii and Taganov (563) for the variation of intensity with time in the spark, and they found that experimental data agreed rather well with their calculations. -\fanas’ev (3) calculated approximately the thickness of the layer sampled, the volume and mass of the evaporated metal, and the time required for the explosive evaporation in an individual spark, based on a particular model of the process. The special case of spark vaporization of residues from the evaporation of solutions onto the end of an electrode was treated mathematically by Zakharov and riidarov (663). The influence of the metallurgical structure of the sample on emission intensities, while already well known, has been t,he subject of some further investigations. Herberg, Holler, and Koster-Pflugmacher (242) found that in an oscillatory discharge the sulfide inclusions are preferred as cathodes, and that therefore the number, size, and shape of the inclusions affect the intensities. The influence of carbon on the spectrometric determination of sulfur was traced to changes in the sulfide inclusions. Hagihara, Muraki, and Taiiaka (232) explained the influence of certain trace components in alloys un emission intensities as being due to alteration by these elements of the metallurgical structure, since the spark was observed to strike preferentially along the boundaries of crystal grains and inclusions. A s was mentioned above, the distribution and mechanisms of loss of elements in the plasma must be understood to explain fully the relation between sample composition and line intensities, and these subjects have been studied extensively during the period covered by this review. A mathematical model for mass transport in dc arcs and laminar flames was developed by Lauwerier and Bavinck (343), taking into account the effects of diffusion and convection. Boumans aiid de Galan ( b y ) , in their theoretical model of element distribution in the arc, also took into account the effect of the electric field, which they found to be particularly important for elements with low ionization potentials. They found good agreement of experimental data with the predictions of the model, although it’ is fair to comment that the experimental data, which are difficult to obtain, exhibit a large enough
random error to obscure some possible imperfections in the model. Normally, element distributions are determined from the radial distributions of line intensities combined with information on the distributions of temperature aiid electron concentrations. An alternative method proposed by Plsko (481) relies on measurement of absorption of light from the arc reflected back through the plasma, the absorption being related to the concentrations of atoms in the ground state. The temperature distribution can then be found from the distribution of atoms in the ground state and the diatribution of excited atoms as shown by the relative intensities of emission lines. Grechikhin and Tyuiiina (265) and Grechikhin and Skutov (264) discussed methods for the measurement of the coiiceiitrations of ions from such information as Stark broadening of emission lines and intensities of forbidden transitions. I n addition to the measurements by Boumaris and de Galan (57) mentioned previously, there were other determinations of atom distributions. Vukaiiovic (626, 627) reported data on the distributions of several elements in a free-burning arc under conditions like those frequently employed in spectrometric aiialysis, and found a separation effect dependent on the degree of ionization of the element. Clearly, this points up the need for matching of ionization potentials in selecting an internal standard. Gol’dfarb and Il’ina (203) discussed some factors which might alter the distribution of atoms in the arc column, and later (204) reported distributions of some atonis along the arc axis for different matrix compounds. The distributions of temperature and of atoms in the arc during the analysis of uranium with gallium oxide, silver chloride, and sodium fluoride carriers, as determined by Kawaguchi (SOO), were not in agreement with earlier measurements. The results mere interpreted in terms of the mechanisms by which the carriers act. Very little is yet known about chemical reactions in discharge plasmas. Troshkina (604) has made some calculations based on thermodynamic data for reactions between calcium, fluorine, and oxygen atoms in an arc which might affect the determination of fluorine from C a F bands. Predictions that the C a F molecule mould be found only in the cooler periphery of the arc column were confirmed in an experimental study. FLAME EMISSION, ABSORPTION, A N D FLUORESCENCE
X a n y papers of interest to those concerned with flame emission, absorption, and fluorescence spectrometry are cited in other portions of this review, but it has been convenient to separate
.
others in this sect'ion. Our philosophy in grouping subjects within this section is (to paraphrase Gertrude Stein) a flame is a flame is a flame, and, to a first approximation, it makes no important difference whether the signal observed is the light emitted or t'he light absorbed. Atomic absorption analysis was reviewed by Girard and Rousselet (195) with emphasis on biological applications, and Goodfellow (213) has assessed atomic fluorescence spectrometry with particular reference to the effects of source intensity, self reversal, sample composition, and solvent on the precision and sensitivity of analysis. A simple method of predicting relative sensitivities (not detection limits) in atomic absorption for many lines of an element was described and compared to experimental measurements by hfargoshes (375). Cellier and Stace (91) gave a method for selection of optimum operating conditions in atomic absorption spectrometry by varying several parameters simultaneously instead of one at a time. Considerable time can be saved by such techniques in setting u p many analyt'ical methods, and the technique is well known to statisticians alt'hough it may m l l be new to niost analytical chemists. Dagnall, Thonipson, and K e s t (112) suniniarized the effects of some experimental parameters in atomic fluorescence spectrometry, including the flame gases, solvent, primary light source, and the effects (negligible) of a number of catioiis and anions on the determination of zinc. Expressions for quantum and power efficiencies in atomic fluorescence spectrometry were derived by McCarthy, Parsolis, and Kinefordner (359), who also discussed the experimental determination of quantum efficiencies. Flame Properties ; Interferences : Alkemade ( 6 ) has given a cogent surnmary of the mechanisms by which sample constituents can affect vaporization of the analyte in a flame. .1careful reading of this brief note is recommended for all spectroscopists using flame methods. A h o t h e r brief, reconimended paper, by de Galan and Winefordner (182) examines the niechanisms by which the flame temperature can affect the analytical signal in atomic emission and absorption flame spectrometry. From a consideration only of the excitation equilibria, it has often been said that atomic absorption spectrometry has the advantage of being less affected than flame emission spectrometry by changes in flame temperature. In fact, the influence of t,he temperature on the processes of droplet evaporation, compound formation, and ionization is equally important, in both techniques. Manning and Capacho-Delgado (373) pointed out that in the nitrous osideacetylene flame, which is used to reduce
interelement effects caused by formation of less volatile compounds, ionization interferences will be more significant than in the cooler air-acetylene flame. Reitzner and Krempl (508) discussed ionization equilibria in t'he acetyleneoxygen flame and interelement effects for the alkali metals. The kinetics and mechanisms of ion formation in flames ,were studied in detail by Bulewicz (82), Sugden (584), Hayhurst (236), Hayhurst and Sugden (237),and Jensen and Padlay (277). dlkeniade and Hooymayers ( 7 ) investigated the role of electrons in the excitation of alkali metals in flames through atom-electron collisions and ion-electron reconibination, and they concluded that neither of these processes plays a significant part. Reactions of atoms and ions with flame gases can, in some cases, reduce significantly the number of free atoms in the flame which are available for excitation or absorption of light. Measurements, for 22 elements, were made by de Galan and Winefordner (183) of that fraction of atonis sprayed into a fuel-rich air-acetylene flame which were present as free atoms. They found that this fraction is close to 1007, for copper, and proposed that this element may be used as a standard for measurements of this type. Ovchar, llishchenko, and Poluektov (445)investigated reactions of rare earth elements with chlorine in the air-acetylene flame; they found a significant forniation of compounds, as evidenced by a reduction of the intensity of atomic lines and oxide bands and by the appearance of new bands in the spectra of europium and lutetium which they attributed to NC1, molecules. General discussions of interferences in flame emission spectrometry were given by Rubeska (523)and ;Irnientrout (14). Britske and Savel'eva (73) discussed the effect of background in flame photometry, particularly the continuum emission observed in the presence of the alkali metals. Interference effects in the determination of the alkaline earths were treated by Rubeska and lfoldan (526) Lvith emphasis on formation of refractory compounds and the use of releasing agents. Koirtyohaiin and Pickett (316) took up the question of the so-called nonspecific light losses in atomic absorption spectrometry, and ascribed them to absorption by halide, oside, and hydroside molecules. Their calculations of scattering of light by particles in a flame and measurements of attenuation of intensity of light passing through sample spray (without a flame) indicated (317) that scattering can account for only a small fraction of the light loss observed when concentrated solutions are introduced into a flame. Goodfellow (21I) studied experimentally the possible effects of foreign cations in atomic fluorescence spectrom-
etry; he found no measureable effect and ascribed this to the very low detection limits of the method, which make it possible to work under conditions of high dilution of the analyte in the flame gases. Hooyniayers and Alkemade (256, 257) gave a theoretical discussion and the results of some measurements of quenching of excited alkali atoms in flame gases. Since the quenching cross sections can be widely different for the various molecules in a flame, these data will be important in the selection of optimum flame conditions for atomic fluorescence spectrometry. The mechanisms of the effects of organic solvents were studied by Elhanan and Cooke (148) and Atsuya ( I @ , and in both cases the conclusion was reached that the principal effect of the solvent is on the rate of aspiration of the sample and the evaporation of the spray droplets. Sample Nebulization and Atomization. Willis (648) discussed the operation of nebulizers and the role of this instrument, component in atomic absorption spectrometry, and I3ritske (71) also discussed the derign of burners and atomizers and gave a design for a n atomizer that could be adjusted to vary the ratio of liquid to gas volumes in the spray. Davies, Venn, and Willis (120) also designed a nebulizer with provision for interchange of the venturi and the capillary as well as for adjustment of the capillary in the venturi to permit control of the rate of sample introduction and the droplet size. Heated spray chambers, which were employed for some time in flame emission photometry, have been rediscovered for atomic absorption spectrometry. Kakano and Takada (429, 430) investigated the effects of heating the sample solution, the air supl)ly, and the chamber on detection limits; they found a sixfold improvement when the spray chamber was heated to about 60' C. Rawson (506) reported a sixteen-fold improvement in detection limits for the atomic absorption determination of several elements by simply heating the air supply to the atomizer. Ultrasonic nebulizers have been used primarily with radio-frequency plasma torches, but their eventual adoption for use with chemical flames probably requires only the development of a design which will be as convenient to use as is the pneumatic nebulizer. Kirsten and Bertilsson (310) described a relatively convenient design, but with a maximum spray rate of only 0.3 nil/iniii; even with this restricted flow, they found that the emission signals were about three times as large as with a pneumatic nebulizer. The nitrous oxide-acetylene flame was introduced only recently by Willis (647)and -1mos and Willis (9) for atomic absorption spectrometry, but it has VOL. 40, NO. 5 , APRIL 1968
233 R
already been adopted widely. The advantages are a higher temperature than an air-acetylene flame but a lower burning velocity than the equally hot osygen-acetylene flame, simplifying the task of building a slot-type burner. Some uses of this flame in atomic absorption were summarized by Bowman and JYillis (63). At times, a flame of intermediate temperature is desirable, and Fleming (169) suggested the use of mixtures of air and nitrous oxide as osidants for acetylene to permit adjustment of the flame temperature. Kirkbright, Peters, and West (306) have investigated the emission spectra of the nitrous oxide-acetylene flame. dlthough the higher burning velocity of osygeii-acetylene mixtures makes it more difficult to construct premixing burners than when air or nitrous oxide is used as the oxidant, at least two types of burners for this purpose have been built. Fassel and Golightly (156) tabulated detection limits by emission spectrometry for 67 elements in a premised oxygen-acetylene flame, and Coivley (107) has designed a slot-type burner for safe operation with this mixture. As was mentioned above, flames of uiiusual composition may be preferred in atomic fluorescence spectrometry because of deactivation of excited atoms by the flame gases. Hydrogen flames in which the oxidant is supplied entirely by the ambient atmosphere have been applied successfully in atomic fluorescence by Zacha and Winefordner (660) and Ellis and Demers (150). Kirkbright, Semb, and West (307) devised a separated air-acetylene flame as an emission source, the advantage being that it is possible to observe spect r a only from the interconal zone, where the background emission is relatively low. Relatively low background intensities also led Skogerboe, Heybey, and AIorrison (556) to reinvestigate the hydrogen-oxygen flame as an emission source, and they measured sensitivities and detection limits for some 25 elements which, because they form stable oxideq, are most frequently determined with fuel-rich acetylene flames. Burner designs giving broader flames for atomic absorption spectrometry were developed by Boling (55) and Butler (84); the broader flames were claimed to provide improved sensitivity and precision. Studies with horizontal flames within long tubes were reported by Stupar (583), Rubeska and Stupar (526), and Ivanov and Kozyreva (271). The purpose here, of course, is to improve sensitivities and detection limits by increasing the time that an atom spends in the light path. The need to dissolve solid samples before introducing them into the flame has the twin disadvantages of consuming time and of diluting the sample. Ven234 R
ANALYTICAL CHEMISTRY
ghiattis (616) has shown that atomic absorption analysis of solids can be carried out by mixing powdered samples with a solid rocket propellent, pelleting the mixture,and burning the pellet at the flame position of an atomic absorption spectrometer. Proell (490) was issued a patent on a high-temperature illuminating flare and showed that emission spectra of elements in soils could be obtained by setting off such a flare just under the si rface of the ground. Because of the limitations of chemical flames, there have been several attempts to employ other means of producing high enough temperatures to produce atomic vapor for absorption spectrometry, For example, papers have been published describing research in which the atomizer was a hollowcathode lamp (268), a King furnace (596),an induction-coupled plasma torch (641), and a plasma jet (175). The last two discharges in particular may be too hot for atomic absorption determination of most elements, since at their high temperatures there may be excessive ionization. A particular case of a flameless atomic absorption analysis is the determination of mercury with the mercury vapor meter, consisting only of a mercury lamp, afilter, a detector, and a light path where the mercury vapor niay be introduced. There have been a t least nine papers published on this subject in the past two years, but only two will be mentioned here. Ulfvarson (609) and Brandenberger and Bader (66) determined mercury a t very low levels by collecting it as an amalgam on a wire or foil which was then heated to introduce the mercury vapor into the light path of the instrument. This relatively simple technique and equipment permits the detection of about a nanogram of niercury in a large volume of solution. Light Sources. References were given earlier in this review to a number of papers on hollow cathode lamps and electrodeless lamps which are used in atomic absorption and atomic fluorescence spectrometry. Only a few additional papers are cited here. Tardon, Stibor, and Sali (594) described a power supply for hollowcathode lamps which controls a current of 5 to 10 mA to within 0.05 mA. Goodfellow (612) and Rossi and Omenetto (519) gave designs for demountable hollow cathode lamps and data on their performance. Such devices give the analyst more control over operating parameters than is otherwise possible. The feasibility of using a single-element hollow-cathode lamp for the determination of several elements \vas investigated by Frank, Schrenk, and Rleloan (171), who found significant absorption of light from an iron lamp by magnesium, manganese, nickel, and copper, and less absorption by barium. An
important result of this study may be the realization that atomic absorption spectrometry may not be quite so specific as been supposed. Light sources with increased intensity are essential for atomic fluorescence spectrometry and may be helpful in atomic absorption when, for example, the noise level can be reduced with a brighter source. Dawson and Ellis (123) investigated the emission of light by a hollow-cathode lamp operated with a pulsed, rather than dc, power supply. They found that the intensities of the lines emitted during the pulse were several hundred times higher than with dc excitation, and that there was no significant increase in line width or self absorption. h demountable hollowcathode lamp giving intensities high enough for atomic fluorescence spectrometry was developed by Dinnin and Helz ( I S @ , and Diniiin (129) demonstrated that analytically useful fluorescence signals could be obtained with such lamps for palladium, titanium, zirconium, chromium, aluminum, manganese, cobalt, and iron, although no fluorescence was observed for 11 other elements tested. Considerable interest has been shown in the possibility of using continuum sources for atomic absorption and atomic fluorescence spectrometry. The application of continuum sources may reduce instrument cost, simplify multielement analyses, and make possible qualitative analyses by scanning through a spectrum. Comparisons of hollowcathode lamps with high-pressure senon lamps for atomic absorption were made by de Galan, McGee, and Winefordner (181), who also made a theoretical study, by Fassel et al. (257), and by Frank, Schrenk, and Meloan (172). All agreed that the results obtained mith the coiitiiiuuin source are nearly as good as with line sources, provided that an adequate monochromator i. employed. Ivanov and Kozyreva (269, 270) reported useful results in atomic absorption even with a hydrogen lamp Rource, which has a much lower intensity than the xenon lamp. The xenon lamp vcas applied to atomic fluoresceiice spectrometry by Veillon et al. (614); detection limits were not so good as with a bright line source, but less than 1 ppni could be detected for six of the 13 elements investigated. Other Instrumentation. hIartinek (382) surveyed the properties of commercial flame photometers. A filter flame photometer for the simultaneous determination of sodium and potassium in biological fluids was built by Oberg, Ulfendahl, and Wallin (442). HaagenSmit and Ramirez-LIufioz (232) developed a filter instrument for the determination of sodium, potassium, and calcium in biological materials. I t features a single detector for the three analytes
as well as for a lithium internal standard; this is achieved by employing a rotating disk containing four filters together with circuits to switch the signal from the detector to the proper integrating circuit for each element. X multichannel flame spectrometer described by Fuwa aiid Vallee (179) employs a grating polychromator and has provision for automatic background correction and readout of the signals in sequence 011 a recorder. The application of this instrument to the simultaneous determination of magnesium, calcium, copper, chromium, and manganese in biological materials was demonstrated by Iida and Fuwa (265, 266). A nebulizer system equipped for alternately introducing into the flame a sample, a standard, and a blank was applied by Lang to flame emission (337, 340) and absorption (338, 339) spectrometry. Repeated calibration of the instrument in this way a t 4-sec intervals is said to markedly reduce the effects of changes in gas flows on the analytical results. I n atomic absorption spectrometry, there has been interest in methods of replacing the prism or grating monochromator mobt often employed. Filter photometers \vere built and tested by Goleb ( d o g ) , Hejtmanek aiid Polej (240), and Kawachi and Suzuki (299), demonstrating that such instruments could be usefully employed at least for the alkali and alkaline earth elements. The limitation is, of course, that the resolution may not be adequate in some other caseb. Escellent resolution can be obtained by replacing the monochromator with a cloud of vapor of the analyte and observing the light scattered by resonance fluorescence. The application of monochromators of this type has been reported by Bowman (61) for the determination of lithium in serum, and by Boar and Sullivan (49) for the determination of calcium in coal. Another method for isolating the signal of interest in atomic absorption spectrometry was suggested by Bowman, Sullivan, and Walsh (62), who showed that the analytical line could be selectively modulated by passing the light beam through an ac-operated hollowcathode discharge. A monochromator is still required with this technique, but considerably larger spectral bandwidths can be employed than is otherwise possible. Applications. The supposed limitation of atomic absorption and fluorescence and flame emission in determining the metallic elements has been shown to be untrue by a number of studies, including several published during the period of this review, Goleb (206) studied absorption of light by the rare gases helium, iieon, argon, krypton, aiid xenon in the near ultraviolet and visible regions, and found that atomic
absorption spectrometry provides quite good sensitivities in the determination of these elements. Dagnall, Thompson, and R e s t (113) demonstrated that sulfur could be determined from the emission inten-ity of Szbands in cool flames. The analytical curves are specific for individual compounds of sulfur, but they provide for the determination of sulfur in sulfuric acid or sulfur dioxide at concentrations from a few ppm to a few hundred ppm. Similarly, McCrea and Light (362) determined hydrocarbons in solutions from the intensities of C H and Cs bands in hydrogen-air or hydrogenoxygen flames. Skogerboe, Gravatt, and Morrison (555) made a detailed study of the flame photometric determination of phosphorus and developed a method for the determination of this element in liver, bone, and leaves. A flame emission method for the determination of chlorine and its compounds in air was described by Gilbert (194). Indium was introduced into the flame by evaporation from a n indium-coated copper tube, and InCl bands permitted the detection of chlorine in the air supporting the flame at concentrations well below l pg/l. Indirect methods also extended flame spectrometry to additional elements, although at the expense of extra effort in the analysis and possibly loss of specificity. Phosphorus was determined indirectly by Kuniamaru, Otani, and Yamamoto (330) and Zaugg and Knox (668) by separation as molybdophosphate and atomic absorption determination of molybdenum. Kirkbright, Smith, and K e s t (308) also determined phosphate in this way and extended the method to the determination of silicon. Roe, Miller, aiid Lutwak (515) determined sulfur in biological materials by precipitation of barium sulfate and determination of barium by atomic absorption spectrometry. Determination of chloride by estimation of silver after precipitation of silver chloride was applied by Bechtler, et al. (38) using flame emission and by WesterlundHelmerson (644)uqing atomic absorption spectrometry. -4 further estension of indirect methods was reported from Hiroshima University. Kumamaru et al. (329) determined phthalic acid in the presence of its isomers by extraction of the complex containing this compound, copper, and neocuproine, followed b y atomic absorption determination of copper. Similarly, Yamamoto, Kumaniaru, and Hayashi (657) determined pentachlorophenol by the atomic absorption measurement of iron after extraction of the ion pair formed by the phenol with tris( 1 ,lo-phenanthroline) iron. Some practical applications of atomic fluorescence spectrometry are beginning
to be made, although this relatively new method is still in the exploratory stage. Klaus (311) reported on the determination of zinc and cadmium in biological materials by this method, and showed that these elements could be determined a t concentrations ranging from about 1 ppm down to hundredths of a part per million by a simple and btraightforward procedure. The influence of acids on the atomic fluorescence determination of cadmium was studied b y Bratzel, Mansfield, and Winefordner (67), and Dagnall, West, aiid Young (117) compared atomic fluorescence and atomic absorption for the determination of this element. General information was given on the atomic fluorescence behavior of nickel by Armentrout (13), and for selenium and tellurium (115) and antimony (116) by Dagnall, Thompson, and West. Jaworowski, Keberling, and Bracco (275) investigated the atomic absorption spectrometric determination of some rare earth elements and of aluminum, chromium, vanadiuni, and zirconium. Ovchar and Poluektov (446) reported on the determination of some rare earths from their emiision spectra in the inner cone of an air-acetylene flame, Investigations were alko made of the operating conditions and interference\ for the determination of several other elements by atomic absorption, including a study of antimony by Mostyn and Cunningham (4Z3), ar5enic by ,\Iassmann (386), bismuth by Marshall and Schrenk (379), lead by Chakrabarti, Robinson, and K e s t (9S), rhenium by Schrenk, Lehman, and Keufeld (643), telluriuin by Chakrabarti (92), and tin by CapachoDelgado and Manning (89). llarshall and West (380) reported on the analysib of alumiiium salti for calcium, magnesium, nickel, and iron by atomic absorption spectrometry; thej found that hollow-cathode lamps gave the best rewlts for the firbt three element\, but that a simple electrodeless lamp waq prefeiable for the determination of iron. a4tomic absorption spectrometric methods for the determination of the alkaline earth elements in g1a.s were debcribed by Adam< and Yassmore (1). K h i t e (646) developed an instrument for the direct analysis of metal fumes in industry by atomic absorption spect roniet i y. comparison was made b y Pruden, AIeier, and Plaut (491) of flame emission and absorption methods, fluorimetry, and absorption photometry for the determination of magnesium in serum; there was good agreement between the two flame methods and between fluorimetry and photometry, but the latter two methods gave results which were somewhat higher than those obtained with the flame methods. An VOL. 40, NO. 5, APRIL 1968
235
R
artificial serum was developed by Marsteller, Leifheit, and Wiener (381) for instruction in the use of analytical instruments, including flame photometers. TRACE ANALYSIS
Smales (560), Specker (569) and West (642) have each reviewed methods for the determination of trace inorganic constituents, including spectrometric techniques. Czakow, Cook, and Kosta (111) have summarized the results of an international cooperative program involving 680 spectrographic determinations of impurities in identical samples by 14 laboratories. They conclude that, among the methods employed, carrier distillation gave the best precision while the results may have been more accurate after preconcentration. Spectrometric methods were recommended for routine analyses. Kosta (322)reported on a similar study involving atomic absorption spectrometry, polarography, and activation analysis. The limits of detection for the spectrographic determination of 65 elements in uranium oxide were tabulated by Feldman (165) from data submitted by 15 laboratories using carrier distillation or preconcentration methods. Hume (262) surveyed methods for the analysis of mater for trace metals, including atomic
Table II.
Methods of Preliminary Concentration
Matrix A1 Am As
Cd
Elements determined Ag, Cr, Co, Cu, Fe, Mn, S i , Pb Pu, Th, rare earths 12 elements Ag, Bi, Cu, Ga, In,
Cr Cs and Rb arsenates Gap, InP Ga, Sb, TI GeCI4 HI I KC1 IJa2O3 XaI Sb PbS Pu-U-Zr alloy Si, Si02
TT
U
Alkali metals Alkali metals Alkali metals, alkaline earths Rare earths Plant materials Sea water
236 R
absorption and flame and plasma emission spectrometry. Laqua (341) has reviewed spectrometric trace analysis, including the effects of such factors as sample preparation, excitation, dispersion of spectra, measurement of intensities, and evaluation of data. The influence of spectral dispersion on limits of detection was investigated by Laqua, Hagenah, and Waechter (342), who found that, with photographic methods and an unlimited supply of sample, the detection limit will decrease indefinitely with increasing dispersion, though a t a diminishing rate and approaching a limit for infinite dispersion. They confirmed their calculations with measurements on a spec$rograph with a dispersion of 4.45 mm,'A. In a study of the accuracy of the spectrometric determination of impurities in gallium arsenide, Karpel and Fedorchuk (296) concluded that the most serious errors enter during sample preparation and during excitation of the spectrum. Strzyzewska and Radwan (582) stressed the need for isolating the sample from sources of contamination in the spectrographic analysis of high-purity materials. Torok (597, 598) considered the effect on trace analysis of residual impurities in the electrodes, a factor that is not ordinarily under direct control of the spectroscopist. One of the more difficult determinations of industrial importance is the
for Spectrometric Analysis
Method of separation Evaporation of A1Br3
i433)
Ion exchange
(32)
Evaporation of AsBrs Chelate extraction
( 229
Chelate extraction
(19,119)
Evaporation of AsH3, chelate extraction Al, Cd, Cu, hlg, Evaporation of PHI, chelate extraction Mn, Ni, Pb, Zn 16 elements Ether extraction 11 elements Evaporation of GeCla 9 elements Chelate extraction 17 elements Evaporation of I Co, Cr, hlo, Ni, Chelate precipitation Ti, V, W, Z r , Co. CIL Mn. 31 Chelate extract ion 11'elements Chelate extraction Many elements Bu3P04 extraction Ga, In, Sb, Sn, TI Ether extraction Rare earths, 29 Liquid-liquid extraction others 13 elements Evaporations of SiF4 Many elements Ion exchange 18 elements Chelate extraction Extraction of fattyacid salts 14 elements Precipitation with HzS and 22 elements chelates Partition chromatography Cu, Mg, Xi Co, Cu, Ni, Pb, V, Ion exchange Zn
Co, C u , Fe, Mn, Coprecipitation, extraction Xi, Pb, Zn
ANALYTICAL CHEMISTRY
Reference
(561 1
spectrometric analysis of steel for small amounts of boron, the problem being interference by an iron line close to the most sensitive line of boron. Sauer and Eckhard (539) compared two methods for this determination, one involving addition of an alkaline buffer to the electrode t o suppress iron lines and the other employing a carbon monoxide atmosphere for the same purpose. They concluded that the latter method gave lower limits of detection. For the determination of molybdenum in ferrous materials at concentrations down to about 1 ppm, Pometun and Sinyakova (486)employed fluorination reactions for the preferential volatilization of molybdenum. For the analysis of uranium compounds, Kelen and Vorsatz (301) combined differential volatilization in an ac arc with a scanning mirror to permit the measurement of partially-resolved lines in the spectrum. An unusual application of reactions in the arc electrode was made by Frishberg (176) for the determination of small amounts of zirconium in molybdenum. The sample was converted to the oxide and mixed in the electrode with sulfur and ammonium fluoride. During the arcing, molybdenum formed a relatively involatile sulfide, while zirconium evaporated rapidly as the fluoride. Table I1 lists several papers describing methods for spectrometric trace analysis following preconcentratioii. One limiting factor in these procedures is the purity of the apparatus and reagents employed. Wanner arid Conrad (639) gave a method for purifying cation exchange resins for use in preconcentration prior to spectrometric analysis. Another occasional difficulty is devising a suitable technique for exciting the impurities after their separation. Nebesar (432) arced the metal-containing organic residues from liquid-liquid extraction in an oxygen atmosphere and observed emissioii from the cathode layer.
(164) (75) (659) ( 469 1
(33s) (484) (155) ( SOJ )
(83%) ( 555 1
(304) (260) (673, 674) (110) (100) (165)
(468)
(254) (5211 (280)
LASERS A N D MICROANALYSIS
When we reviewed emission spectrometry only two years ago, only eight publications on laser probe analysis were cited; now we are able to cite nearly 40 papers on the use of lasers in emission spectrometry. All but one of these involve the laser as a means of sample vaporization. I n one application, however, the material being analyzed is made to lase. H u n t (263) determined the carbon dioxide content of breath by introducing the sainple into a laser cavity, formiiig a carbon dioxide-nitrogen laser. Aside from this, most a,~plicationsof lasers in emissioii spectrometry have been for microanalysis. Rasberry, Scribner. and Margoshes (503) have reported on the properties of a commercial laser probe, including the nature of the
spectra obtained with and without spark cross-excitation, spectrograph illuminating systems for qualitative aiid quantitative analysis, instrumental problems, and some analytical applications. I n a companion study (504), the same authors investigated laser and spark parameters and their effect on line intensities and on quantitative analysis. General reviews on spectrometric analysis with the laser probe were written by Debras-Guedon (127) and by Vilnat (620), who also considered the use of lasers in Raman and mass spectrometry. Several survey papers have been written by Moenke aiid others (45,408,410-415) who have designed a laser probe being manufactured in East Germany. Glick (199) and Glick and Rosan (ZOO) have discussed some early applications of the laser probe in histochemistry. The elemental analysis of single cells and cell components may develop into one of the more significant applications of the laser probe, since biological samples are rat'her difficult to analyze with competitive microanalysis techniques such as the electron probe. The laser probe offers some advantages in the analysis of other material:: which are now frequently studied with the electron probe. Metallurgical applications of laser spectrometry have been discussed by RIcCormack (360) and by Ryan and Cunningham (535), while Malinek and Minarik (571) considered applications in geology. Vilnat, Liodec, and Debras-Guedon (622) reported on the quantitat'ive determinat,ion of nickel and chromium in steel with the laser probe. Runge, 13onfigli0, and Bryan (530) investigated the determinatioii of the same elements in molten steel, the stated purpose being the eventual perfection of a system for analyzing steel while it is in a furnace. Analysis of copper alloys with a laser was the subject of a study by Panteleev and Yankovski? (451 452), who also investigated the composition of the vapor plume formed by focusing the laser on the sample surface. A two-step process for laser spectrometry was developed by Zhukov (671). The material evaporated by the laser was collected on a thin film of polymer, which \vas then burned in the electrode of an arc. The material evaporated with several laser firings could be collected 011 a single 1)olyner film to improve detection limits when sample sizes or numbers permitted. Lazeeva, Petrov, and Skvortsova (346) tested the use of a laser iii the determination of oxygen in metals. The material being analyzed was evaporated by a laser pulse in a chamber containing carbon dioxide enriched i n lsO; afterwards, isotopic analysis by spectrometric methods gave the oxygen content of the metal. Not all work with lasers in spectrometry is directed to microanalysis. ~
Felske, Hagenah, and Laqua (166) advocated the laser as a replacement for spark excitation in routine analysis. I n their scheme, the sample is moved under the laser so that each firing samples EL fresh portion of the material, and a large number of exposures, perhaps 100, are superimposed to develop an average analysis. Karyakin, Kaigorodov, and Akhmanova (294) investigated the use of the laser to evaporate relatively large amounts of sample for spectrometric analysis; a powerful laser, with an output of 20 joules per flash, evaporated 4 mg of sample. Karyakin arid Kaigorodov (293) compared matrix effects when the laser is used solely for evaporation of material and for evaporation and simultaneous excitation. The matrix effects \yere found to be much less evident in the latter case. One difficulty in the use of the laser without cross excitation is the strong self absorption and self rwersal of the spectral lines, particularly for elements at higher concentrations. Preobrazhenski7, Kolobova, and Terpugova (488)proposed the quantitative determination of elements from the measurements of the distance between the intensity maxima on either side of the reversed line image. The possibility of analysis of the vapor plume produced by the laser through atomic absorption spectrometry was investigated by Mossotti, Laqua, and Hagenah (422). Time-resolved spectra with a flash lamp as the background source were found to give good detection limits, but matrix effects were quite marked, even when the actual amount of sample vaporized was taken into account. A thesis by Piepnieier (473)was also on time-resolved absorption and emission spectra of laser plumes. Such studies will give considerable information on the processes taking place during vaporization with a focused laser. Grechikhin and Min'ko (223) made high-speed streaking-camera photographs of plumes formed by laser vaporization and found that the vaporization process with lasers and that with sparks are apparently similar. The mechanism of vaporization by a laser was also investigated by Korunchikov and Yankovskii (321),along with the spectra emitted by the plume. They found that much of the emission comes from the shock wave zone where the plume, moving a t supersonic velocity, interacts with the air, and they showed changes in the plume jet and in the spectra when the experiments were carried out at reduced pressure. Some attempts have been made to estimate the temperature of a laser plume. Ehler and Weissler (143),from the wavelength of the peak intensity of the continuum radiation, derived a temperature near 100,OOOo K , while Mentall and Xicholls (398) found values of
24,000' and 9000" for the excitation temperature of barium and calcium and 3600" to 5600°K from the rotationvibration structure of A10, CB, and CN bands. Whatever the temperature of the laser plume, it is certainly hot enough, when formed in vacuum, to produce highly-ionized spectra. Esteva and Romaiid (155) observed spectra in the vacuum ultraviolet of singly-, doubly-, and triply-ionized atoms; Fawcett, Burgess, and Peacock (159) found lines in the vacuum ultraviolet ascribed to S X, K X I , X I I , X I I I , C a XII, XIV, Sc X I I I , and Ti XIV; Fawcett et ui. (160) observed spectra down to 25 A including Fe XV, XVI, and Ni XVII, XVIII; and Basov et al. (34) photographed ultraviolet spectra ascribed to Ca X to XIV and A1 VI to XI. In addition to the laser, older methods of spectrometric microanalysis have been applied to various problems. One of the oldest is the microspark. Vogel (623) obtained a patent on a device for local spark analysis in which a fine electrode is mounted on the objective of a microscope to facilitate its positioning. Petrakev and Blagoev (466) also described an apparatus for microanalysis with a spark between the sample and a fine counter-electrode. A microspark apparatus used by Marzuvanov (383) for the analysis of mineral grains employed a microscope with a quartzfluorite lens for illumination of a spectrograph. For the analysis of inclusions and grains in alloys, Voronov and Samoilova (625) restricted the spark by constraining it to burn through a small corundum ring on the surface of the sample. Arnautov (16) analyzed samples weighing about 1 pg by high-frequency impulse discharge excitation in an inertgas atmosphere, which gave spectra even of elements such as sulfur and the halogens. For the analysis of coatings 3 to 28 pm thick on wires, Gorbunov et ul. (214) dissolved the wire base, transferred the coating to an aluminum plate, and excited the spectra with a microspark. I n t,he analysis of small samples which are not included in a larger matrix, handling can be a serious problem. Evans and Waller (154) described two electrode designs and t'echniques for handling samples weighing a few micrograms, and Ellen (149) developed a technique for mounting minute samples in a graphite pellet for arc excitation. Measurement of the effluents from a gas chromatograph is a special case of spectrometric microanalysis. Gas chromatographs often employ flame ionization detectors, so it is logical to look at the spectra from such flames. Winefordner and Overfield (651) adapted the theory of detection limits in flame emission spectrometry to flame emission detectors in gas chromatography. EquipVOL. 40, NO. 5 , APRIL 1968
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ment for and results with flame emission detectors have been described by Bowman and 13eroza (&), Braman (65), 13rody aiid Chaney (76), Juvet and Durbin (281), and Zado and Juvet (661). Ai1 alternative to a flame is a lowpower microwave discharge in the inert carrier gas of the chromatograph. Experience with this type of source has been reported by Bache and Lisk (22023), and by Moye (424). OTHER APPLICATIONS
The development of a universal quantitative spectrometric method of analysis is of great importance to laboratories handling a diversity of materials. Ordelman, Sniit, and Tolk (444) described a de-arc method, which was said to be free of any matrix effect, in which the sample is mixed with a 100-fold or greater excess of a lithium fluoridegraphite buffer and pressed into a pellet. -1method for the analysis of solutions with Tesla spark excitation was described by Paksy (447)as being free from matrix effects. Ryabkova, Narbutovskikh, and Katkova (584)compared several methods for the spectrometric analysis of solutions, including arc and spark excitation of a solution introduced through a hollow cathode, arc- and spark-in-spray, saturation of electrodes with a solution, evaporation of drops of solution on an electrode, and application of the solution to nioving graphite strips; the last method was recommended. -1thesis by Bedrosian (40) was concerned with the effects of acids and surfactants on the analysis of solutions from plant tissues by the graphite spark method. Muntz (425) studied the analysis of alloys with the plasma jet, and concluded that maintenance of the nebulizer is the most serious problem with this source. Birks (47) summarized methods and results in the analysis of the actinide elements, including the problem of containment of radioactive materials, the merits of different excitation sources, aiid line interferences. The influence of electrode shapes and grades of graphite on the analysis of radioactive materials by the solution residue method was described by Svoboda (589). Bromine and iodine, in quantities as small as 0.5 pg, were determined in powdered materials by Eelobragina and KaporskiY (42), who pelleted a mixture of the sample with quartz and aluminum powder, excited the pellet in a lowvoltage condensed spark, and photographed the vacuum-ultraviolet spectra. Photoelectric spectrometry was reviewed by Belyaev and Ivantsov (44), who emphasized methods for improving sensitivity and precision. Nachata (365) surveyed analytical procedures for use in criminalistics, including emission 238 R
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ANALYTICAL CHEMISTRY
spectrometry and flame emission and absorption. Sample Preparation. Three methods have been described for obtaining a sample of steel from a furnace for spectrometric analysis. Goudoever, et al. (221) introduced a mold containing an aluminum strip through the slag layer; a cardboard cover over the mold keeps the slag out but detaches itself once the mold is below the slag. Cavelier (90) obtained a patent on a method of forming pin samples by drawing the molten steel into a refractory tube, and a patent issued to Vanderbeck (611) covers an apparatus which is designed for sampling metal in a basic oxygen furnace. When samples are received in the laboratory in diverse forms with varying metallurgical histories, it is often necessary to convert them into a form suitable for spectrometric analysis. Remelting and casting of samples was studied by Holler (251) for carbon and low-alloy steels, and by Prince, Ellgren, and DeGlopper (489) for low-alloy and stainless steels, high-temperature alloys, and copper and aluminum alloys. When the melting is carried out under an argon atmosphere, the procedure appears to be satisfactory except for the more volatile elements. Lavergne (344) gave detailed instructions for the preparation of rock, soil, stream sediment, mineral concentrate, and biological samples for spectrometric analysis. When large pieces of metal are to be analyzed, contact-spark sampling is a convenient method of obtaining material for arc or spark excitation. Baskov, Berter, and Palladin (33) found that the amount of material sampled could be increased nonselectively by first coating the metal with a salt such as cadmium chloride or sulfate, barium or copper chloride, or ammonium chloride or sulfate. They tested the technique on iron-, titanium-, nickel-, and copperbase alloys. Metals. The determination of the nonmetallic elements in metals remains a subject of considerable interest and importance, especially the gaseous elements. Goto et al. (219) determined oxygen in steel by arcing the sample in a graphite electrode within an argon atmosphere and measuring the intensity ratio fo! the line pair 0 1302.17/C 1721$66A. Lindstrem, Sventitskiy, and Shlepkova (350) measured 0.02 to 1% oxygen in titanium by means ,Of oxygen lines between TOO and 850 A. Webb and Webb (640) developed a photoelectric apparatus for the determination of hydrogen, oxygen, and nitrogen in metals, and gave methods and results for the determination of oxygen and nitrogen in steel, uranium carbide, and tungsten, oxygen in copper, and hydrogen in zirconium. Shubina, Kilina, and Bazanova (550)
were able to determine hydrogen and oxygen in metals by measuring the intensities of lines in the visible spectrum. Hydrogen, oxygen, and nitrogen in surface layers of metals were determined by Fedorova, Korneenko, and Zanina (162) by excitation in helium or argon at reduced pressures. The depth of the layer sampled was only a few hundredths of a millimeter. A method for removing trace amounts of hydrocarbons from argon to be used in a vacuum spectrometer was described by Tanabe, Ishii, and Asai (593). Sorokina and Kondrat’ev (566) determined carbon in steel from the intensities of the C N bands emitted by a 25 to 50 -1ac arc with an exposure of only three to five seconds. Carbide carbon in steels and cast irons was determined by Bieber, Drexlerova, and Vecera (46) by spark excitation between the sample and a copper counter-electrode and m e a y e m e n t of the carbon doublet a t 4267 A. A method for the determination of boron in carbon and low-alloy steels was developed by Hines and Hurwitz (248). Accurate and precise results were obtained by excitation with an overdamped condensed spark with the sample negative and a sharply-pointed graphite rod as the anode. For the same purpose, Goryczka and Klimecki (216) used an aluminum counterelectrode; they reported that reaction of the aluminum with the oxygen in air provided an inert atmosphere. Eckhard (139) determined boron in steel with a vacuum spectrometgr, measuring the boron line a t 1826.4 A. A review of methods for the spectrometric determination of boron in steel was prepared by Eckhard and hlarotz ( I @ ) , and they also described a method, involving melting of the sample with a sodium carbonate flux, which is suitable for the analysis of boron-containing steel fractions which have been isolated electrolytically. The application of time resolution in photoelectric spectrometry was investigated by Goto et al. (220) using rapid switching of the high voltage to the photomultipliers to select the time intervals to be recorded. They found the technique to be helpful in distinguishing between closely-spaced lines which appeared at different times during the spark discharge. Krivosheeva (327) studied the influence on spectrometric analysis of three ways of casting bronze samples, and related the observations to the metallurgical structure of the material. The effect of alkali metals on analysis of copper alloys with arc excitation was investigated by Milenina and RudnevskiI (402, 403); they reported that sodium or potassium compounds added to the sample reduce the surface tension of the molten metal and thus increase its rate of evaporation.
A technique for analyzing surface layers only a few micrometers thick was described by Simova (554) and applied to the determination of manganese, chromium, and silicon on steels. Chentsova and Tiniolova (99)gave some results obtained with a method for characterization of heat-resistant layers of chromium-aluminum, silicon, tungsten, or aluininum on molybdenum; their fiudings agreed with the results of optical metallographic studies. Goryczka and Klimecki (217) employed thin layers of metal on steel in a study of interelement effects. During the excitation period, the composition of the excited vapor changed continuously as more of the substrate and less of the coating was evaporated, permitting a correlation of line intensities with vapor composition. Nonmetals. Some unusual applications of emission spectrometry have been reported during the past two years. Quesada and Dennen (495) showed that it is possible to determine water in minerals by arcing the sample in a boiler-cap electrode and observing the $tensity of the OH bandhead at 3064 A. One would not ordinarily consider spectrometric methods for the detection of slight departures from stoichiometry in compounds, but Rudnevski! and Illakhimov (527) demonstrated that such analyses are possible. They employed a holloiv-cathode diicharge for the determination of excesses of cadmium and zinc in their sulfides, taking advantage of the increased volatility of the excess metals. Excess amounts as small as 0.017, were detected. Rudnevskir, Naksiniov, and I3urakova (528) extended the technique to the determination of excess arsenic in gallium arsenide and antimony in indium antimonide, and Rudnevskii, Naksimov, and Vysotskii (529) applied it to both sulfur and cadmium excesses in cadmium sulfide. The hollow-cathode source was also used by Maksimov and RudnevskiI (370) to determine iodine in germanium. T o prepare standards, they first purified germanium from iodine by heating i t in a hollowcathode discharge and then added potassium iodide. Turovtseva, Ilalyshev, and Koskov (606) determined nitrogen and oxygen in uranium hexafluoride by means of a hollowcathode source; the limits of detection, 0.03% for nitrogen and 0.06% for oxygen, could presumably be improved by measuring more sensitive lines in the vacuum ultraviolet. K h e n a vacuum spectrometer is in use in a steel plant, it is useful to extend its application to the analysis of materials other than iron and steel. Bojic, Bourdieu, and Jorre (52, 53) have eniployed a vacuuni spectrometer for the determination of sulfur, phosphorus, and metallic elements in ores, mineral
agglomerates, and slags; the samples were melted with a flux of lithium tetraborate and boric oxide, ground, pelleted, and excited with a high-voltage spark. Another method for analysis of slags from steel manufacture on a vacuum Spectrometer was developed by Ersepke and Sebestyenova (152), who employed spark excitation of pellets made from a mixture of the sample with graphite. Nikitina, Gudyrina, and Kolomiets (437) determined calcium, silicon, iron, manganese, and magnesium in metallurgical slags and sinters by techniques in which the sample was molten or in the form of a solidified melt. Kessler and Gebhardt (302) investigated the analysis of limestone and dolomite for aluminum, iron, and magnesium with a high-frequency plasma torch, and found that this source permitted more rapid analyses than were possible with arcs or sparks. Herrmann and Roetger (245) described equipment and results for the analysis of biological samples in a clinical laboratory with the plasma jet. Stamm and Roetger (574) gave more detailed information on the determination of phosphorus in a clinical laboratory with the plasma jet, which they found gave results comparable in accuracy to those of chemical methods but with somewhat better precision in considerably less time. il method for the determination of vanadium in petroleum fractions with the plasma jet was described by Heemstra and Foster (238). Raziunas, Loseke, and Grove (607) showed the feasibility of determining small amounts of hydrogen, nitrogen, and oxygen in argon-helium mixtures b y de-arc excitation in a Stallwood jet, The advantage over earlier methods for such analyses, which are normally carried out with radio-frequency excitation a t reduced pressure, is that the new technique requires only equipment commonly available in a spectrometry laboratory. Isotopic Analysis. L’vov and llosichev (358) reviewed some procedures for isotopic analysis, including the analysis of hydrogen and mercury from their atomic lines and of carbon, oxygen, nitrogen, and boron from molecular bands. Isotopic analysis by emission spectrometry depends in part on the production of lines with widths less than the isotopic splitting. Aleksandruk et al. (5) demonstrated good accuracy in the determination of the isotopic composition of natural magnesium by means of a n atomic-beam light source yielding sharp lines. Good resolution is also often needed in isotopic analysis. Pascalau and Weissmann (458) employed a scanning FabryPerot interferometer for this purpose, and showed its application to the determination of deuterium in hydrogen. Absorption filters offer another means of
separating isotopic lines, particularly resonance lines. L’vov and Mosichev (35’7)showed that such filters could also be used for nocresonance lines of helium near 10,830 A by populating excited states with a de discharge through the absorbing gas. De-arc methods for the isotopic analysis of uranium were described by Leys and Perkins (348) and by Nishihara, Matsumura, and Sonoda (438). Such analyses have, of course, been carried out for many years, although they require a fairly large spectrograph to provide the necessary resolution. Goleb (207) has shown that isotopic analysis of uranium can be done by atomic absorption spectrometry pvith considerably less expensive equipment. H e employed two hollowcathode sources, containing uranium highly enriched in 235Uand 238C,and the samples mere vaporized in a third hollowcathode discharge which served as the abaorption cell. Goleb (208) attempted to extend this equipment to the determination of the 11Bj1013 ratio in natural boron, without success. However, Iiri*hnamachari and Vengsarkar (326)and Zakorina, Lazeeva, and Petrov (664) determined the isotopic composition of boron in the trifluoride by observing 1 3 0 2 bandheads excited in an electrodeleqs discharge in a mixture of the fluoride with oxygen. Meier and Mueller (394) developed a photoelectric apparatus for isotopic analysis of nitrogen from K2bands, and Faust (158) reviewed methods for the converqion of nitrogen compounds to nitrogen and recommended the oxidation of ammonium salts with sodium hypobromite. Sommer and Kick (564, 565) determined the nitrogen isotopes in soil, plant, and animal matter with the preparation procedure of Faust, and excitation in a high-frequency discharge. Ungureanu (610) determined 1 to 31y0lSOin oxygen photoelectrically with the aid of a Fabry-Perot spectrometer. Tritium in hydrogen waq measured by Mosichev, L’vov, and Khartsizov (421) with high-frequency discharge escitation. Nosichev and L’vov (420) and L’vov, AIoeichev, and Plyuihch (358) described the determination of Ig9Hg in lg8Hgby excitation in an electrodeless discharge, obtaining the required resolution with a Fabry-Perot interferometer. Zhiglinski? and Fafurina (670) also employed a Fabry-I’erot interferometer combined with a grating monochromator to resolve the isotopic structure of magnesium lines, but they excited the samples in a hollow-cathode 1a:np cooled with liquid air. Kashtan, Bulatov, and Zykova (295) worked out a method for the isotopic analysis of lead with hollowcathode excitation that was said to be suitable for the rapid analysis of geological materials in the field. Methods for estimating geological ages VOL 40, NO. 5, APRIL 1968
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by the rubidium-strontium technique were described by Eichhoff (147); the isotopic composition of strontium in the samples was determined by emissioii spectrometry. The ability to carry out isotopic analyses makes it possible t o use isotope dilution determinations. The advantages of isotope dilution procedures are that they can be made self-calibratiiig and that quantitative recovery is not, required of separation methods. Several papers have appeared in the U.S.S.R. journals on the isotopic method for determination of gases in metals. -4 review on this subject, was written by Zaidel and Petrov (662), Zakorina et al. (666) discussed equiI)ment for this purpose, and -4leksaiidruk, Zhiglinski?, and Kh1ol)ina (4) considered the selection of optimum conditions to improve the Iireciaion of these determiiiations. The determination of hydrogen and nitrogen, either separately or siniultaiieously, in gas mistures by isotope dilution and excitation in an electrodeless discharge was described by Nemets arid Petrov (45’4).Hollow-cathode lamps were used for the determination of oxygen in metals by Zakorina, Lazeeva, and Petrov (666) and Shvangiradze, Oganezov, and Chikhladze (551). In the first of these two papers, 1 8 0 was added a s carbon dioside, while in the second l80 and 1% were added as nitric oxide. SIolecular spectra were measured in both cases. LITERATURE CITED
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Infrared Spectrometry R. 0.Crisler, lvorydale Technical Center, The Procter & Gamble Company, Cincinnati, Ohio
T
covers articles appearing in the two-year period from December 1965 to December 1967, primarily as cited by Chemical Abstracts or located by search of 25 journals which most frequently publish papers on infrared spectroscopy and analytical chemistry. References have been selected to indicate significant developments in those areas of general interest to applied spectroscopists. Chemical, and particularly analytical, applications are emphasized. Many specific areas of spectroscopic interest are reviewed only briefly or not at all-e.g., interferometry or infrared physics-as being most likely well known to those having more specific interests. The choice of headings reflects a subjective division of the articles into coherent topics, and much of the discussion assumes familiarity with the content of the previous reviews and a general knowledge of the state of the art. HIS REVIEW
BOOKS A N D REVIEWS
h number of introductory texts directed at the undergraduate or novice have been published. Among them are 246 R
s
ANALYTICAL CHEMISTRY
books by Conley (9A)and Martin ( f 9A) devoted exclusively to infrared spectroscopy and a general instrumental analysis text by Banwell (4A). Chapters have been written by J. C. Evans and by L. A. Smith for the general analytical series edited by Welcher (S2A) and Kolthoff and Elving ( 1 ?A). Interpretation of spectra is described by Szymanski ( S f A), Brand and Eglinton (6A), and Silverstein and Bassler (24A), the latter two taking an integrated approach using the results of other instrumental techniques. An advanced text on theory and practice has been written by Houghton and Smith ( I S A ) . A collection of monographs on applications has been edited by Kendall ( f 6 A ) and on recent research and selected topics by Szymanski (SOA). A number of papers on spectroscopic techniques have been collected by M a y (2OA) from those published in Applied Spectroscopy. Books on the reflectance techniques have been written by Harrick (IOA) and Wendlandt (SSA), the former exclusively on -4TR. A manual on recommended practices assembled by ASThl Committee E-13
452 17
has been printed ( f i l ) , and a set of quality specifications for infrared spectra ( 8 A ) has been prepared. Both of these should be studied by all spectroscopists along with a paper by Potts and Smith (2fA) on the proper adjustment of an infrared spectrophotometer. A multilingual dictionary of spectroscopic terms has been printed (15A) and three new journals have been started (28, SA, 25A). A compilation of wavelength standards has appeared (%?A), and tables of band assignments for 59 molecules have been prepared by Shimanouchi (23A) for the National Standard Reference Data System (NSRDS-NBS). Two volumes of the series of interpreted spectra and Supplements 3 and 4 to the “Infrared Band Handbook” have been published by Szymanski (27A-29A). Several books and pamphlets on the analysis and interpretation of spectra of polymers have appeared (7A, 1 I A , 12A, I4A, %?A),a book on the spectra of cellulose and derivatives has been translated (SCA), and a comprehensive book on the spectra of adsorbed species has been written by Little ( f 8 A ) . -4n annotated bibliography of the literature
