Emission spectrometry - Analytical Chemistry (ACS Publications)

Emission Spectrometry Ramon M. Barnes, Department of Chemistry, University of Massachusetts, Amherst, Mass. 0 7 002

T

HE HISTORY OF THIS REVIEW dates to the first fundamental review issue in 1949. Five consecutive reviews were written by Meggers (37A) followed by three reviews by Scribner ( M A ) , and four reviews during the past eight years by Scribner and Margoshes (%‘A, 67A). A change in reviewer for this 13th installment is not intended to discontinue the tradition established in previous years. The initial section presents a general summary of new books, review articles, and spectral atlases. New fundamental atomic spectral data are presented in the second section. A section on d e velopments in spectroscopic optics and systems is included with discussion of new instrumentation, techniques, and stelndards. A portion of the review deals with advances made in spec& chemical excitation sources and the understanding of basic processing in these sources. Significant spectrochemical analyses published or d e veloped in the past few years conclude the review. The material used in this review Comes from the major spectroscopic journals and various abstracting sources covering 1970 and 1931. When material is not commonly available in English, reference to alternate sources such as Chemical Abstracts is included.

BOOKS AND REVIEWS

The two-decade absence of books on modern emission spectrochemical analysis appears to have been recognized during the past two years, because a number of books have been published which should be useful to both university instructors and practicing spectroscopists. A textbook entitled “Emission Spectrochemical Analysis” by Morris Slavin includes chapters on spectrochemical history, physical and optical principles, spectroscopic sources, dispersive devices, and readout techniques, as well as practices in qualitative and quantitative analysis (66A). A more comprehensive book or series of books on emission spectroscopy is a three-part volume entitled “Analytical Emission Spectroscopy” (I7A). The first part, published in 1971, includes intensive, complete chapters on historical developments, origins of atomic spectra, prism and grating systems and instruments, and spectroradiometric principles. The second part, available in 1972, emphasizes excitation sources and mechanisms, as well as qualitative and quantitative analyses. Each c h a p 122 R

ter is prepared by a different author or authors, and is tt concise, detailed presentation of material valuable to all spectroscopists. Addink has prepared a short book, “DC Arc Analysis,” presenting a semiquantitative analysis method, which is based upon his years of practical laboratory experience (1A ) . Principal among the books on quantitative techniques is the 6th edition of the ASTM “Methods for Emission Spectrochemical Analysis’’ (XA). Enlarged by more than 18% over the 1968 edition, the book includes 185 arc and spark emission, x-ray fluorescence, and combustion flame methods for most common metals and nonmetals. The book presents methods numerically, although it is indexed by material groupings. May has compiled a second volume of articles published previously between 1966 and 1969 which includes 24 practical aids in emission spectroscopy (38A). Papers presented at various conferences hcqve been collected in a number of books. The proceedings of the XV (60A) and XVI (61A) Colloquia Spectroscopium Internationale in Madrid in 1969 and Heidelberg in 1971 represent a preview of current activity in spectrochemical analysis. Selected papers, including reviews and special symposia, from the 19th, 20th, and 21st Mid-American Spectroscopy symposia have been published (18A-9OA). Two additional volumes of “Spectrochemical Abstracts” covering the years 1968-1969 (66A) and 1969-1970 (67.4) bring the series to sixteen volumes. The almost 500 citations in each volume generally permit a rapid search of selected spectrochemical techniques. A small book on ”Ditrraction Grating Spectographs” was written by Davis (10.4). A booklet (3OA) and a review of ditrraction gratings (31A) collect some of the experience from the laboratory of a leading grating manufacturer. A chapter on diffraction gratings by Richardson (69A), and one by Meltzer (%?A) on spectographs and monochromators have appeared in a series of optical instruments (97A). A variety of foreign books have been translated into English during the past two years. Moenke and MoenkeBlankenburg’s “Laser Micro-Emission Spectroscopy” has been translated from German (4OA), as has Zimmer’s book on “Geometric Optics” (73A). Bous-

ANALYTICAL CHEMISTRY, VOL. 44, NQ. 5, APRIL 1972

quet’s 1969 text on “Spectroscopy and its Instrumentation” has also appeared in English. It contains useful chapters on prism and grating fundamentals and instruments, as well as interference spectroscopy (6-4). Zaidel’s and Shreider’s 1967 book on ‘Vacuum Ultraviolet Spectroscopy” has been translated ( 7 f A ) ,and de Galans’ introductory textbook on spectrometry, originally published in Dutch in 1969, has been translated and contains chapters on discharges, monochromators, and spectra (13 A ) . Moritz and Torok have compiled a five-language dictionary containing about 3500 terms used in spectroscopy and spectral analysis (43A). French, German, and Russian terms are given for an alphabetical listing of English phrases. French, German, Russian, and Spanish terms are tabulated separately with references t80the English list. Proceedings of a number of conferences in the USSR have been published in Russian (IXA, 4OA, 7XA) as have a number of new books of interest to spectroscopists (14A, WBA, XOA, 38A, 47A). Unfortunately much of this material will remain untranslated. Two of the most widely used wavelength atlases have been revised and reissued since the last review. Both the “MIT Wavelength Tables ’’ (31A ) and the Zaidel “Table of Spectral Lines” (7OA) have appeared in enlarged and improved form. The revised “MIT Wavelength Tables” is a reproduction of the original tabulation published 33 years ago with corrections marked directly. Additions and changes are contained in a supplementary table. Unfortunately the revision has not been extended to many new studies, and perhaps the next revision will be compiled with computer assistance in order to present a truly complete tabulation of atomic properties. The Zaidel table is the translation of the third Russian edition published in 1969. The atlas includes a decreasing wavelength tabulation for 60 selected elements in varying detail, individual wavelength tables for 98 elements, various reference materials, and an abbreviated bibliography. A tabulation of working atomic emission spectral lines from a number of flame sources was published as part of a compilation of analytical spectral lines used in combustion flame spectroscopy (46A1. Other fundamental spectral data a p pearing in 1970-1971 included a bibliog-

raphy on atomic transition probabilities compiled through June 1969 (39A), and tables of ionization potentials obtained from measured spectral ionization limits (41A) and calculated for multiple-charged ions (‘7A). The second edition of multiplet tables for C I-VI was also published (42-4). The Thermophysics Properties Research Center (TPRC) a t Purdue University issued in 1970 seven of the thirteen volumes of a substantial thermophysical data series, as part of the Xational Standard Reference Data System (NSRDS). Three volumes are each devoted to thermal conductivity (62A, 64A, 6 5 A ) and specific heat data (59il , 60.4 , 6 3 A ) , and two volumes contain data on thermal expansion. Radiative properties of metallic elements and alloys (61A), nonmetallic solids, and coatings constitute the three other volumes. Reference to these volumes should be satisfying to any spectroscopist who has attempted to comb the literature for the “best value” for thermophysical properties of materials. Large portions of manual data collection and treatment in emission spectroscopy have been automated and computerized. A survey by Perone of computer applications in the chemical laboratory includes many aspects of interest to the spectroscopist, although spectrochemical applications are not treated in specific detail (46.4). The article is a source of references to all phases of computer use and includes, as well, some new ideas. Frazer (16-4) and Margoshes (S4A) discuss approaches to computer automation in a chemical laboratory and the integration of automated functions within the measuring instrument. Applications in spectrochemical analysis are outlined by Margoshes (35.1), Sat0 and Ihinda ( 5 S A ) , and Decker and Eve (119). As Margoshes has emphasized ( S S A ) , computer utilization by both manufacturers and users in spectrochemical analysis is far less than the capabilities available. The rapid development of new and less expensive computers should increase pressure on spectroscopists and manufacturers to take advantage of these devices. Kaiser’s review and discussion of quantitation in elemental analysis (24A) uses many spectrochemical examples to illustrate concepts of information content and application statistics in analytical methoda. The uses of lasers as light sources (15&1)and excitation sources (26sil) have been reviewed, and Baldwin has edited the 3rd, 4th and 5th in a series of bibliographies of laser publications related to spectrochemical analysis (SA). Review papers dealing with spectrochemical analysis in archaeology ( 8 A, 9 A ) , oceanography (583),forensic chemistry ( 4 A )and of metallurgical materials

( M A ) have also appeared. A review of trace elements in clinical chemistry presents a summary of results for 11 essential and 17-22 non-essential element concentrations in human tissues and fluids (64A). Mossotti has written an introductory chapter summarizing the uses and a p plications of various emission spectre scopic techniques including arcs, sparks, and laser sources (44A). A comparison of emission techniques with other instrumental methods for elemental analysis has appeared (68A). An elementary chapter on atomic emission spectroscopy was prepared by Price (&A) as part of an introductory text on spectroscopy. Yoakum (69A) and Boumans ( 5 A ) have taken different approaches to reviewing recent events in emission spectroscopy. Boumans critically evaluated alternate techniques for simultaneous multi-element trace analysis including some work performed in his own laboratory. Other emission reviews not readily accessible in English include the biennial reviews of emission spectroscopy in Japanese (IdA), and a review of high frequency and microwave plasma emission sources in Czech (28A). 1

SPECTRAL DESCRIPTIONS AND CLASSIFICATIONS

Considerable effort is being expended to collect and predict phenomena related to atomic spectra. Much of this activity may not be recognized by spectrochemists, and an introduction as well as a listing of some pertinent atomic spectral properties is presented. The work going on in atomic spectroscopy includes in addition to the production, identification, and classification of atomic spectra for individual elements, the measurement of lifetimes of spectral levels, transition probabilities, oscillator strengths, electronic configurations, and isotope shifts. Reviews of many of these activities were presented a t the 2nd International Conference on Beam-Foil Spectroscopy in June 1970 (100B) which was transcribed in Nuclear Instruments and Methods (48B). Reviews included atomic lifetime measurements (SB, 96B, IOSB), analysis of atomic spectra (48B, 64B), transition probabilities (YB, S9B, 107B, 14SB), developments in atomic f-value (141B), instrumentation (60B) as well as beam-foil spectroscopy (4B, 8B). Reviews of atomic transition probabilities measurement were also published by Kessler (77B)and Sinanoglu (127B). Identification and classification of spectral lines of every element and the majority of ionization states continues, although analysis of atomic spectra would appear to the casual observer to be the most completely documented area of spectroscopy. Table I presents some of the publications in identification of atomic spectra in wavelength

regions most accessible to the spectre chemist. Not included is the extensive work on higher ionization levels of e l e ments, especially those following the isoelectronic series of the light elements. Because of the higher energy transitions, most of these spectral lines occur in the vacuum ultraviolet and the extreme vacuum ultraviolet. Identification and classification of lanthanide and actinide spectra and configurations are being actively pursued. Brewer (28B, 29B), Martin (93B), Nugent and Vander Sluis (108B), and Spector (131B) have discussed energies and configurations of neutral and ionized lanthanidc and actinide elements. One result of spectral classification is determination of ionization limits and ionization potentials such as those included in Table I. Moore has tabulated ionization potentials and limits from which they were derived for 95 elements (41A). The ionization potentials for elements up to Z = 103 for all states of ionization have been calculated based on a simple spherical shell solution for neutral atoms (7A). The average deviation of the calculated from experimental values was determined to be 5%. Lotz has published the electron binding energies for all subshells for all elements up to 2 = 108 (89B). Both the “MIT Wavelength Tables” (21A) and Zaidel’s “Tabie of Spectral Lines’’ (7OA) have appeared in new editions. Recent spectral classifications listed in Table I are not included in these atlases, and little new spectral line material has been added to the M I T tables. DeGregorio and Savastano have compiled an atlas of arc and spark spectra of iron and 314 analysis lines oef 54 elements between 2206 and 4656 A (41B). A method for calculating wavelengths using a dispersion diagram has been described (76B). Valero has demonstrated that when systemic shifts among data from different experimenters are eliminated, a highly accurate set of secondary standards of length from interferometrically measured wavelengths is obtained (1S8B). Spectrochemical analyses have not been undertaken generally a t waveiengtbs shorter than approximately 1800 A, except by Malamand (91B,92B) and activities reviewed by Milazzo and Cecchetti (lO4B). However, as new sources and techniques are developed, spectrochemical analysis in the vacuum ultraviolet will be used more routinely. Bohm and Labs have evaluated radiation from electron bombardment of metallic surfaces as a secondary standard source in the vacuum ultraviolet (87B). Considerable growth has occurred in less than a decade in the field of beam-

ANALYTICAL CHEMISTRY, VOL. 44, NO. 5 , APRIL 1972

*

123 R

Table I.

Ionization level I, I1 I1

I11

I, 11, 111, I V I, 11, 111, IV, v, VI I, 11, 111, IV, v I11 I IV, v, VI, VI1 IV

C

N 0

1

F

IV I11 111-VI1 11-v I, I1 IV, v, V I I IV-VI1 I1 I11 I I1 I1 I1

Ne Ne Mg S c1 Ar Mn Ni cu

Zn 64,66,68,70

As Br

IV 11, I11 I1 I I1

I IV

Selected References to Atomic Spectra

9 ~ 0 - 6 3 0A

Ionization energy 7842-518 Ionization energy 5000-450 Energy levels, multiplets 7000-1100 4 Ionization limit 50,000-10,oO0A Energy levels, multiplets 500-150 A 50,000-10 OOO 1 8000-500 3436-9078, 2206-742 Ionization limit 2000-1050 A 6000-1100 A 2940-940 A 4000-600 A 40532-39603 A 2800-500 A 762-465 A (Ritz standards) 2500-500 Energy levels Ionization liiit 11227-1979 A 9813 4 hyperfine structure Ionization potential 2300-3000 A 5894.35 6214.59,7478.79A ,1216 11064-701 Ionization l i i i t 40414-39317 A 2420-310 A Ionization limit

V

Kr 86 Sr

I, I1 I11

Y

I

Ag

I11

Number linea

Wavelength range 35cm-3800 A

Ionization limit 28,663-3623A Ionization limit Hyperfine structure 2440-380 A

76 202,887.4 f 1.0cm-1 31 305,931,lO& 0 . 8 om-1 100+

Reference (63B1 (1fOB)

386,241.0 f 1.0 cm-1

700 505,777 f 5 em-' 40 17 13 22 100 408 4300 146,541.56cm-l 1968 55.2 V 516 Isotope shifts 198 1034 149,932 f 8 cm-l 9 136 363,395 cm-l 12 502,860 om-' -200 345,866 f 5 cm-' 2500

(Continued)

foil spectroscopy (4B, 8B)as the result of efforts of the Van de G r i d Laboratory in the Department of Physics a t the University of Arizona. In the beamfoil technique, ions are generated and accelerated by a Van de Graaff accelerator (OB), and an ion beam impinged on a very thin foil. The beam ions further ionize and become excited in passing through the few hundred A foil. Ion spectra of spontaneous radiative decay appear in the down-stream side of the foil. Spectroscopic measurements of these ion spectra extend from the extreme vacuum ultraviolet to the infrared and have generated new information on highly ionized spectra, Stark Effect, and excited state lifetimes. For 124 R

the spectrochemist, the beam-foil technique might be considered another light source, although no spectrochemical a p plications have been published, probably as the result of lack of the extensive equipment. Bashkin, the director of the Arizona Van de Graaff laboratory, has reviewed beam-foil activities through June 1970 and makes available on irregular basis a bibliography of all papers related to beam-foil spectroscopy (8B)* The assignment of ionization levels to beam-foil spectra usually requires data from conventional spectroscopic sources such as sparks. However, Carriveau and Bashkin (lOB, 32B) have described a Doppler shift technique for

ANALYTICAL CHEMISTRY, VOL. 44, NO. 5, APRIL 1972

determination of ionization levels with the beam-foil instrumentation. Only recently have reliable methods become available for accurate measure ment of radiative lifetimes for excited states of the more refractory species and their ions. These methods include electron-beam phase-shift, beam-foil, Hanleeffect, and photon-resonance phaseshift techniques ( l 2 4 B ) . Unfortunately references to all recent studies of radiative lifetime and absolute transition probabilities are too numerous to include in this review; however a critical evaluation of these values through June 1969 has been published and tabulated by Miles and Weise (S9A). Table I1 lists a very few selected elements of low

Table 1.

Element (;sotope) In

Ionization level I, 11, 111, IV, v I

I Xe 136, 134, 131, 130, 129, 128 Xe 136 La Au

I11 I,. 11,. I11

Bi 207 T1

I 111, I V

Pb

IV, v

Pr

IV

Nd

Tb DY

I, I1 IV I, I1 I, I1 I I1 I1 111, IV I I

Ho Er

I, I1 I, I1 I1 I1 I, I1 I

Gd

162

Tm Lu 175

Wavelength range

A

9500-340 40020-38624

Number linea

Reference (84B1 (66B)

4000 14

VOB)

I1 I11 I I11

Th U

Selected References to Atomic Spectra (Continued)

I I, I1

ionization which might be of direct interest to the spectrochemist. Much of the spectral descriptions and classifications work in progress is presented in sessions on atomic and molecular spectroscopy (116B)a t the biannual meetings of the Optical Society of America. INSTRUMENTATION

Many of the advances in spectrochemical analysis depend upon develop ment and application of instrumentation. Often development is reported in the literature of fields associated with spectrochemical analysis and may not be immediately recognized. This section

Isotope shifts 11088-3449,35079-12626 A 221 13894.47,14O96.18,17878.~ A 5d-M 9600-2600 d (I) 74,408.6f 1.0cm-1 Ionization limit (I) 4760-925 R (11) 1760-860 A (111) 3067 A 9000-340 -900 Ionization limit (111) 24,0773 & 5 cm-1 41 ,2500 f 300 cm-1 (IV) -800 9ooo-340 R Ionization limit (IV) 34,2438 f 5 cm-1 2500490 A 186 Ionization limit 314,200k 200 cm-l 40500-2450 2500 --loo00 6700-1180 R 25000-8000 A 966 18000 8752-2468 1% Levels, intensity array -225 11154-2890 A 70 600&1200 R -20,000 Intensity array Levels, intensity array 22000+ 11400-2300 R Configurations 4528-3193 R 6800-4100 A 12500-7847 Levels Levels 5867-1977 A 8008-677 A Ionization limit 12382-2566 A

Zeeman structures 31, Zeeman structure 23 3 848

71 169,024k 10 cm-1 -400 1375

contains a survey of advances in optics, spectrometers, light sources, photoelectric detectors and readout systems, spectroscopic electrodes, and vacuum UV apparatus which may be found useful in further emission spectrometric developments.

Optics, Gratings, Spectrometers. The production and use of gratings has been reviewed in chapters by Richardson (62A), Barnes and Jarrell ( I I C ) , an article by Loewen ( N A ) , and a short book by Davies (10.4). The use of prisms and gratings in various spectrographic instrument configuration has been summarized by Bousquet (6A), Faust (63C),Meltzer (%A), and Barnes and Jarrell (11C). I n the latter chapter,

the authors have reviewed advances in grating spectroscopic instrument design through August 1970. Progress in ruling large dsraction gratings has been reported by Harrison and Thompson. One of the MIT engines can now rule echelle grating up to 8 X 16 inches, with blaze angles from 62' to 79' (66C). Echelle efficiencies between 900 and 4400 A have been reported by Burton and Reay and a 37-m echelle spectrograph was evaluated by Liller (IlOC). Kalhor and Neureuther have presented a generalized numerical method for the analysis of diffraction gratings with arbitrary groove shape to obtain the energies in various radiating orders (88C). Cerutti-


(arc),

0

125R

Table 11.

Element H He Li Be B B C N 0

F

Ne

Selected References to Lifetimes, Oscillator and Transition Probabilities Ionization level Type I lifetimes I lifetimes I transition probabilities I1 lifetimes lifetimes, classifications I1 lifetimes, classifications I, I1 I oscillator strengths I-IV lifetime radiative lifetimes I, 11, I11 I transition probabilities I-v lifetimes I, I1 radiative lifetimes lifetimes, transition I-V robabilities raxiative lifetimes o*+,I I transition probabilities radiative lifetimes I-VI 11, I11 lifetimes, transition prob., oscillator strengths V transition probabilities, oscillator streneths transition probabilities I lifetimes 11-VI I transition probabilities g-factors I radiative lifetimes I1 11, I11 11, I11 I, 11, I11 radiative lifetimes I radiative lifetimes I, I1 radiative lifetimes I, I1 oscillator strengths lifetimes, osc. strengths I, I1 I oscillator strengths radiative lifetimes 11, I11 oscillator strengths I I-VI lifetimes, transition probabilities transition probabilities I lifetimes 11-VI1 I transition probabilities. lifetimes I, I1 transition probabilities lifetimes 11, I11 transition probabilities, I11 lifetimes radiative lifetimes oscillator strengths radiative lifetimes oscillator strengths I lifetimes transition probabilities oscillator strengths oscillator strengths oscillator strengths lifetimes transition probabilities lifetimes lifetimes radiative lifetimes radiative lifetime, transition probabilities lifetimes radiative lifetimes lifetime, oscillator strength I lifetimes oscillator strengths I

Strengths,

Reference (126B) (2OB, 98B) (6B1

~

&yo;;

Na Mg Al

Si S

c1 Ar

Pb Sm

Maori and Petit have discussed scalar theories for grating analysis (29C). One recent development in grating manufacture involves the formation of an holographic image in a photosensitive dielectric followed by suitable processing, to produce a diffraction grating (ZlC, ISC, 66C, 92C, 166C). Although holographic gratings do not have the same groove geometry of ruled gratings, 126R

holographic gratings can be made virtually free of ghosts and aberrations (l28C),exhibit low scattered light, and display high efficiencies in both plane and concave configurations (9SC). The unique characteristic of these gratings is the ability to generate grooves on tiny formed surface including concave spheres, paraboloids, and ellipsoids (11C). Dielectric gratings may repre-


sent the key to the design of either radically new spectroscopic mounting arrangements, which are now limited bv mechanically iuled gratings, or the mork general use conventional mountings. For example, McMahon employed a holographic transmission grating to produce a monochromator that maintained a constant blaze condition as wavelength was altered and yielded an output beam of constant width, direction, and lateral position (1180. I n another example, the absence of ghosts from a 2000 line/mm holographic grating has permitted the construction of a very high resolution 1 . 5 m Czerny Turner, double-pass monochromator, A mounting using a conventional reflecting grating and plane mirror in a corner reflector arrangement to obtain a constant blaze condition was described by Kessler (94C). DeBiase, Sacchetti, and Treverse examined the transfer function of a diffraction grating affected by blank and ruling errors and obtained a w a v e length-dependent transfer function to restore the true grating output (48C). Experiments with concave gratings ruled with variable line spacings indicated the possibility of correcting for astigmatism over a range of wavelengths, depending upon the angie of diffraction (66C). Toroidal gratings have been used in a Seya-Namioka monochromator to increase luminosity with the same resolving power of a spherical grating (176C). Pouey described a corrected Seya-Namioka design (138C). The design of a Monk-Gillieson monochromator has produced a number of detailed theoretical and experimental evaiuations of the mounting, in which a plane grating is substituted for the concave grating of the Wadsworth arrangement (69C, 9Oc, l29C, 158C). An experimental and theoretical comparison of spatial resolution of a CzernyTurner spectrograph with the grating in collimated and in divergent light was made to cwrect for astigmatism in divergent illumination ( I S C ) . Moule, Foo, and Biernacki described a very high resolution echelle spectrograph using an Ebert mounting and a Ceerny-Turner prism predisperser (1SSC). In a comparison of concave grating monochromators for the far ultraviolet, Pouey demonstrated the influence of ruled grating height on resolving power for symmetrical and Rowland mountings (IS7C). When a corrected symmetrical mounting is used with a holographic grating, a substantial gain in luminosity is expected. Pouey has also reviewed the instrumentation of the vacuum ultraviolet region with emphasis on vacuum spectrometers (lS6C). Speer reviewed grating studies a t X-ray wavelengths (I?'&'), and Schmidtke described diffrac-

tion filters for extreme ultraviolet spectroscopy (157C). Codling and Mitchell have described a 2-m constantdeviation grazing-incidence monochromator (SSC). Comes and Thimm used a toroidal mirror to produce a stigmatic image for a grazing-incidence vacuum spectrometer ( 3 5 0 . Litzen described a Czerny-Turner near infrared spectrometer with coma eliminated by an off-axis camera mirror (1llC). A new class of large-area optical filters based on cholesteric liquid crystals was described by Adams et al.

(IC). Basic spectroradiometric principles including the parameters characterizing spectrometers, detectors, sources, and entrance optics have been considered in detail by Betz and Johnson (16C, 8 l C ) . Rutgers has surveyed spectroradiometric standards (15SC), and Heaps has described an automatic recording spectroradiometric system (68C). Shulman has written a text and a report on optical data processing for engineers (166C, 167C). Glass or plastic fiber optics can be useful for illuminating spectroscopic apparatus in the visible for observation of otherwise inaccessible sources or for introducing motion between the spectrometer and the source of illumination. Robben and Fraser summarized various considerations and transmission measurements with fiber optics as illumination optics of a spectrometer (146%’). The arrangement of fiber bundles to match the geometry of the light source and spectrometer entrance slit can compensate intensity loss in the fibers and yield increases in signal compared to a normal optical system without astigmatic components. A portable spectrometer using a fiber optical bundle has been reported for monitoring 0 and H emission from a welding arc (112C). Because of the use of fiber optics as faceplates for cathode-ray tubes, work is under way to increase the transmission in the ultraviolet (14.X’). Alexander described a new UV fiber optic with a quartz core cladded with a special UV-transmitting material which displayed 50% transmission a t 254 nm for a 1-meter-long bundle ($2). Evans and Pasco described a fiber optic arrangement for measuring radial luminosity of an enclosed plasma discharge (51C). DeGalan and Wagenaar considered entrance and exit slit optics for lineprofile studies (47C), and Nilsson described a spectral shift device using two rotating glass plates to produce two beams of different wavelength from a single monochromator (l31C). The conditions for scattering by the transfer image optical train d spatiallyresolved intensity measurements was discussed by Venable (183C).

Through the use of two aspherized plano-convex lenses, Murty has constructed a convenient arrangement to isolate different wavelength images of a source without the use of a diaphragm or the need to adjust the position of the source (127C). Allemand has described a servomechanical slit control to maintain a constant wavenumber bandpass ( 4 C ) for a Czerny-Turner monochromator. A photographic procedure for determining the optimum focal position of the entrance slit of a plane grating spectrograph was described by Hurwitz and Blystone (78C). Torok has discussed some of the problems of using photographic emulsions for spectrographic analysis (I 79C) including a comparison of developing uniformity. Plsko reviewed properties of photographic emulsions in spectrographic analysis (135C). Spectrometer Readout Systems. A variety of photoelectric systems for emission spectroscopy have been reported and examined during the past two years. Not only have key features for low light level detection systems such as photon counting and image intensifiers been developed, but rapid and multi-element readout systems are becoming a reality. I n considering the ideal spectrometer readout system, one approach as yet not accomplished in practice is the “photoelectric” photographic emulsion-ie., a photoelectric readout with the spatial resolution and simultaneous wavelength coverage of an emulsion. Some of the mysteries of the manufacture and operation of multiplier phototubes have been resolved by the long-needed publication of a “RCA Photomultiplier Manual” (141C). The less-than-200-page paperback book contains sections on principles of photomultiplier design, properties of photocathodes and dynodes, considerations of statistical fluctuation and noise, applications, and design of voltage divider chains. Sections on light sources and matching spectral responses of source and detectors are also useful to the spectroscopist. Campbell has reviewed the proper ties of some solar blind photomultipliers for use between 1450-2800 d; (98‘2). Hirschfeld has reviewed the techniques for increasing quantum efficiencies of photomultiplier tubes by using total internal reflection cathode arrangements (72C). Shaw, Grant, and Guntler described the optical enhancement of 5 2 0 photomultipliers (166C). A number of comparisons among photomultiplier tubes and various photodiodes and phototransistors indicate that, except for wavelength regions in the near infrared at which the photcmultiplier sensitivity drops below that * of a photodiode (159C), photomultiplier

tubes still offer superior performance in the ultraviolet, visible, and near infrared wavelength regions in normal applications (14 9 C ) . On the basis of signal-to-noise ratio theory, Ingle and Crouch have developed criteria for choosing between a photomultiplier and a vacuum photodiode (79C). Silicon solar cells have been evaluated as a photometric detector (191C); an equivalent circuit model is used to predict performance, and output voltage is related to illumination level. The performance of a GaAs Shottky-barrier photodiode modulated a t 4 GHz was evaluated by Sharpless (1632). End-on photomultiplier properties such as fatigue, area and wavelength sensitivity (25C, 96C, l l d C ) , dynode gain, and anode output (85C) have been studied (IOC, 17C, 192C). Theoretical and experimental evaluations of photoelectron pulse counting methodology have been undertaken by numerous investigators (5C, 119C). Although the value of pulse counting techniques for weak light signals is recognized, considerable argument exists over the relative capabilities of various photomultiplier readout systems. Muray has reviewed single-photon spectroscopy with conventional, highgain semiconductor and channel photomultipliers (126%‘). The use of quantum light sources for calibration was discussed. Methods for measurement of quantum counting efficiencies for semi-conductor photomultipliers (108C) and monochromator-detector system combinations (1032) using single photon counting techniques have been described. Savage and Maker described a multichannel photon counting spectrometer using an image intensifier, isocon camera tube, and multichannel analyzer (154C). Diament and Teich investigated photon counting distributions for modulated radiation and concluded that an unmodulated amplitude-stabilized source was optimum for pulse-code modulation communications (48C). I n the comparison of readout systems, Anderson and Cleary evaluated the signal-to-noise ratios for four detection systems (7C). Of the four systems, which included dc amplifier, lock-in, noise-power, and combined lock-in-plusnoise-power, the noise power and lockin-plus-noise-power systems provided significantly greater S/N ratios than the other methods. Rolfe and Moore (149C) found no significant difference between pulse counting and dc methods. I n order to compare pulse counting with phase sensitive detection, Robben (147C) correlated the noise properties to parameters of a photomultiplier including two new factors: photoelectron noise factor and effective dark rate. Robben’s conclusion indicated that for


0

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most experimental conditions, where averaging times are less than 10 seconds, pulse counting, charge integration, synchronous- and dc current measure ment will give similar signal-to-noise ratios. Robben reviewed the importance of a suitable pulse a m p l i e r and experimental technique. Another detailed theoretical and experimental comparison of pulse countr ing and current measurement techniques stimulated by the work of Rolfe and Moore (1490 was published by Jones, Oliver, and Pike ( 8 7 0 . I n addition to including a bibliography of original theoretical and experimental work of the factors influencing photomultiplier noise, these authors indicated that much of the original comparisons of photon counting with other techniques was outdated for newer, high-quality photomultiplier tubes. They disagreed with the work of Rolfe and Moore. Their experimental results compared closely to theoretical integrated charge distributions. Double the time was required to achieve a given accuracy in light-flux measure ment, if a long internal time constant was used instead of digital storage for photon counting technique, and between 2.4-2.9 times longer was required for conventional current measurements compared to photon counting into a digital storage. Although magnetic electron multipliers (MEM) with continuous dynode and field strips are restricted to use in vacuum regions such as found in satellite-borne systems or extreme ultraviolet spectrometers, Macar et al. (1987) have compiled an extensive discussion of these windowless detectors. A modification of a MEM in which a photocathode and grid are added to give a photon-counting, one-dimensional multichannel spectral recording instrument has been proposed (14OC, 171C). Weller and Young have measured the photomultiplier yield of a channel electron multiplier between 304A and 1493A (187C). Ash and Piepmeier have described a double-beam photon counting photometer (SC). An image-dissector photomultiplier system was tested as a detector in a rapid scanning direct reading spectrometer system (67C,100C). The imagedissector tube permits the electrical scanning of a limited region of the spectral plane of a monochromator across an internal entrance slit to the multiplier chain. The combination of an image intensifier and an image dissector was described by Eberhardt and Hertel as a method for improving the signal-to-noise ratio of the image dissector for use in an electronic scanning spectrometer (6OC). Hoag, Ball, and Trumbo applied image dissector systems to area scanning, spectrophotometry, and telescope controls (7%’). 128 R

Robinson employed an image dissector to scan the phosphor of an image intensifier which provide the readout of a spectrometer (1480. A simultaneous 512-channel spectrum can be acquired with a statistical precision approaching the limit of the input photons and photocathode quantum efficiency. Boumans (SA) has attempted to use an array of planar silicon photodiodes and phototransistors as detection devices to convert a monochromator into a multichannel spectrometer. Dark current from these arrays was reduced significantly by using a Peltier-element cooler. Unlike a spectrograph, the difEculty of a monochromator-photomultiplier is that only a small fract.ion of the radiation passing the entrance slit of the monochromator is detected at a given instant. An image intensifier tube can be inserted between the spectrograph focal plane and the photographic emulsion to increase the sensitivity of the spectrograph. Tobin has made a theoretical comparison of light amplifier and photomultiplier detectors (178C). Sharpless and Young described an echelle grating spectrograph with an image intensifier tube usable in the wavelength range between 2500 to 6OOO A (164C). The echelle mounting permits the display of wide spectral ranges in a compact view area. An emission spectrometer also using an echelle arrangement but with a SEC vidicon camera has been proposed by Margoshes (I160. An image orthicon spectrograph with computer control was described by Johnson, Fairbank, and Schawlow (832). The properties of a very sensitive television camera for atmospheric emission, which was constructed by combining a plumbicon camera with a very high gain four-stage image intensifier, were discussed by Mende (1ZOC). This system was particularly well suited to very weak intensity sources and photoelectron counting techniques. Savage and Maker used a combination of a threestage image intensifier, an isocon camera tube, and a multichannel analyzer for multichannel photon counting for hyperRaman spectra (164C). Koppitz studied luminous waves between electrodes during the later stages of Townsend and streamer discharges with an image converterintensifier system of resolution less than 3 nanoseconds (1O4C). Martinkov and Livshits studied the time-space distribution of lines near the cathode surface of a capacitor discharge with an electron optical converter system (116C). Chalmers and DuRy observed the arc-forming stages of spark breakdown using an image intensifier and converter system (30C)* A f/1.5 stigmatic spectrograph for nanosecond exposures using a Kerr-cell


shutter waa described by Borucki ( 1 8 0 , and a time-resolved spectrograph with a rotating mirror system was discussed by Kosrtsa et d. (1060. Sawanda re viewed the instrumentation and applications of timeresolved spectrometry (1660,and Koehler and Morgan used a variable speed rotating disk for time resolution of an exploding wire source (1010. Hirokawa and Goto studied a low voltage impulse discharge with a millisecond time-resolved technique using a hexagonal prism rotating a t 1600 rpm in front of the entrance slit ( 7 0 0 . Minami and Uchida have reviewed ultra-high-speed spectrometry and its applications along with descriptions of various high-speed photoelectric detectors (1990. A versatile timeresolved spectrometer based upon two types of photomultiplier gating systems yielded minimum time resolution of 2 and 10 nanoseconds. A gated photomultiplier was used for time-resolved studies in the vacuum ultraviolet (IZZC). Schoreder et a2. described t i m e resolved photoelectric gating systems for application in spark and laser studies (169C). Treytl et a2. described a time-resolved system to separate continuum from signal radiation from a laser-generated plasma (I80C). Computer-controlled multichannel spectrometers have been described by Rippon (l&C), Bowers and Maxson (IQC),Staats (176C),and Hoeller et al. (740). Bowers and Maxson’s system was employed with an aluminum spark and uranium carrier distillation. An on-line computer which controlled spark analyses for 5 spectrometers in an ironworks was described by Hoeller et a2. Vogel and Ramsden described a spectrometer with fixed multiple slits with periscope mirrors focusing to a single photomultiplier (1840. Shutters between each slit and mirror were sequentially opened and closed to observe each wavelength in turn. A monochromator modification to measure small spectral line shifts in plasma sources was fabricated by Kogelschatz, Brooks, and Hoe11 (IOZC). Honeycutt had used a 1024channel signal averager with a digital driven Monk-Gillieson monochromator to obtain a rapid scanning astronomical spectrometer (76C). Rostas et a2. mixed the light from a reference and sample modulated a t ditrerence frequencies before dispersion in a 7.4-m Czerny-Turner spectrograph equipped with a scanning plate to accomplish 0.7 A/hr scans (16OC). Two synchronous detectors sorted the signals for a simultaneous display of displacement and shape of spectral lines. A high resolution spectrometer based on a piezoelectric scanning Fabry-Perot interferometer was used by Kirkbright and Sargent for evaluation of line sources

for atomic absorption

spectroscopy

(970. Other uses and development of FabryPerot spectrometers and interferometers were described (lWC, 71C, 170C). A rapid scanning spectrometer in the region 2000-8500 A was applied to the study of thermoluminescent emission spectra by Harris and Jackson (64C). Techniques related to derivative spectroscopy have appeared during 1970-71. I n most derivative spectrometers, a small sinusoidal modulation of a wavelength position is used; then the observed dc signal can be made proportional to the first or second derivatives or harmonics of the spectrum signal. The theory of the derivative spectrometer was treated by Hager and Anderson (6C,6SQ. Applicationsof derivative spectrometers have been limited to improving resolution of overlapping spectral bands and lines, reduction of instrumental scattered light, suppression of light source fluctuations, and extraction of weak signals from heavy background (ISSC, 17SC). One instrument built by Williams and Hager (189C) was applied to the determination of blood ammonia (6SC). Smith analyzed the commonly-used first-harmonic, lock-in-detection scheme for superposition of Lorentz and dispersion line shapes (17%). Davies has outlined the potential applications of correlation spectroscopy (40C), in which a spectral mask in the exit focal plane of the spectrometer is used for optical coincidence with a wavelength modulated input radiation. Through the use of a synchronous detector, spectra with high optical coincidence with the spectral mask will produce maximum signals. A correlation interferometer was also described by Davies ( 4 0 0 . Doubly multiplexing dispersive spectrometers, in which different masks are placed a t the entrance and exit apertures, have been discussed and applied by Harwit et al. (66C, 1S3C). If a series of masks are used in place of a cc-incidence spectrum a t either the entrance or exit focal planes of a spectrometer, Hadamard matrices can be used in a computer operation to decode the combination of spectral elements observed by the detector. This spectroscopic technique is called Hadamard spectroscopy, and has been treated in detail by Nelson and Fredman (ISOC), and Decker (194C). If measurements are chosen properly, an effect analogous to Fellgetts’ advantage of Fourier-transform spectroscopy can be obtained with a conventional spectrometer. Decker demonstrated the multiplex advantage of 255slot (46C), and 2047-slot (46C) Hadamard-transform spectrometers, and discussed the application to automobile exhaust analysis (GC,194C).

Spectroscopic Light Sources. Hell has written a short, very generalized discussion of light sources (SQC),and Gabriel has discussed plasma light sources (66C). Semiconductor light emitting diodes light sources were reviewed by Chapman (%C), and the generation and applications of picosecond light pulses with lasers was reviewed by Rentzepis and Mitschelle (14%’). Bedford described a pulsed, intense UV light source with a Bnsec rise time and 7.5nsec pulse width (16C). The extensive use of laser radiation or laser-generated plasmas as light sources excludes a complete review. Baldwin’s (SA) bibliographies along with reports by Felske et al. (16A), Katsuno and Takeuchi (91C), Mandelstam (11SC), and Valero et al. (18WC)should be consulted. A laser book list has been compiled by Siegman (168C). At least two new approaches for direct solid sampling and analysis are under development. Jones, Dahlquist, and Hoyt employed separated tandem arcs for aampling and excitation (86C). The first dc arc samples the solid specimen to produce a particulate aerosol in an inert gas stream. The aerosol is carried up to 17 meters to a capillary dc arc discharge for excitation. The sampling arc device has also been used to supply a solid aerosol for flame analysis (190C). The glowdischarge source (146C), in which the sampling and excitation are combined, has been studied and used for analysis by Dogan et al. (49C). Hollow cathode and other types of low-pressure discharge devices have been used as light sources in atomic absorp tion and fluorescence spectroscopy, and will not be discussed in detail here. Prugger et al. (139C) and Kielkopf (96C) have investigated pulsed hollow cathodes, and Bruce and Hannaford studied the line profile of a calcium hollow cathode tube (2%’). A hollow cathode was used in a magnetic field by Rudnevskii et al. (161C) to increase spectral sensitivities. Semenova and Sukhanova used a hot hollow cathode in flowing helium to obtain a selective population of Cu I and I1 lines (161C). Human and Butler used a 2450.MHz microwave discharge to excite a hollow cathode discharge (77C), and Trinidade investigated the mechanism of operation of hollow cathodes (181C). Bacis determined the instrumental functions of a Fabry-Perot interferometer using a thorium hollow cathode lamp and the emission line profiles (9C). Collins described a variable-phase, reference signal circuit for use with a lock-in amplifier to take advantage of the line-frequency modulation of spectral calibration lamps (36C). The approach proved as sensitive as mechanical modulation.

An E-field high-frequency, low-temperature light source was developed by Grigor’ev et al. (61C). Microwaveexcited plasmas for spectroscopic sources have become more widely used as illustrated by the works of Fallgatter et al. (6ZC), Wildy and Thompson (188C), Aldous et al. (9C), Hattori et al. (67C), and Cooke et al. (96C). The use of high-frequency (99C) and microwave plasmas a-s sources was reviewed in Czech by Kleinmann (%?A, 98C). An inductively augmented flamewaa studied by Johnston and Lawton (84C). An experimental study of the operation of a new type of alkali spectral rf-excited lamp in a strong magnetic field was conducted by Ioli et al. (8OC). Hollister presented a semi-theoretical description of a 900-Torr inductioncoupled xenon discharge light source (76C). Vacuum Ultraviolet Instrumentation. A number of new light sources have been studied for use in the vacuum ultraviolet regions. Critical to the design of an UV light source is the need for very little window deterioration and little or no self absorption. Levy and Huffman used a dc self-stabilized arc for a radiation source in the 300-1000 A region (109C). Govertsen and Anderson described an atomic beam source for resonance line emission of rare or any permanent gases (60C). DeChelle and Merdy (4%’) described a source in which a capacitor discharge through a narrow capillary filled with the gas to be excited produces line spectra in the region 450-1200 A. Kikuchi has used a 2450-MHz microwave discharge to produce an intense vacuum UV atomic line source (96C). Paresce et al. developed a continuous discharge line source for use between lo00 and 100 b (1SXC). Day described a new grazing incidence, multi-beam interferometer suitable for use in the VUV (41C). Johnson used a high pressure (10-20 atm) rare gas short-arc as an UV emission source to about 1150 b, and eliminated many of the disadvantages of low pressure lamps (82C). Becker et al. used Hz and H D (14C) and Mumma and Zipf used Nt and CO (lW4C) band systems in the molecular branching-ratio technique for calibration of vacuum ultraviolet monochromatordetector combinations. Buckley used a tungsten ribbon filament lamp as a photomultiplier quantum efficiency calibration standard between 1200 and 2500 A (X4C), and Branch et al. described a calibrated photodiode detector for the VUV (XOC). A vacuum ultraviolet spectrum was obtained using a holographic method by Kamiya et al. ; however, no particular advantage was found over the conventional approach except for the elimination of stray light (89C).


129R

Arc-Spark. An automatic control system for positioning the electrodes during arc excitation was described by Schuringa et al. (160A), and a servocontrol system to maintain pre-programmed light intensity from a moderate current dc arc in static argon was described by Gordon and Chapman (68C). The S-2 ac generator for various arc and spark excitation conditions w&s described by Sukhnevich (177C). Walters and Bruhns constructed and characterized a 162-MHz quarter-wave, coaxial-line spark source, which may prove to be one of the most useful sources yet developed (186C). Electrodes. Coulter discussed in general terms the design, processing, and manufacture of spectroscopic carbon and graphite electrodes as a part of a symposium on graphite electrodes a t the 21st Annual MidAmerican Symposium on Spectroscopy (37C, 3 8 3 . The empirical nature of spectrographic electrodes appears to continue to exist, however. Krasnobaeva developed cleaning procedures for 23 types of electrodes (loSC). A crater electrode shape in which heat transfer is reduced by a hole drilled below the crater was described by Kuznetsov et al. (107C). Evaporation patterns with the electrode differed from the conventional undercut electrodes. The spectrographic properties of capillary electrodes were studied by Matherny (ll7C)). In the servo-controlled argon arc system described by Gordon and C h a p man (68C), a spherical tantalumcathode electrode has been developed to give exceptional arc stability as the result of exactly matching the cathode spot dimension to the bead size. De velopment of the geometry of a carbon anode also contributed to increased arc stability and evaporation precision. Muntz has evaluated a tubular electrode configuration for the introduction of aerosols into a dc arc (186C). Curry and Cooley developed a compact gas jet to reduce spectral background and decrease arcing time (39C). Findeisen and Schuffenhauer obtained improved solution analyses with vitreous (glassy) carbon disk electrodes compared to porous electrolytic graphite electrodes (64C). A rotating disk sample holder which moves the flat metal disk sample spark site in a Archimedian spiral was described by Walters and Monaci (186C). STANDARDS, SAMPLES, CALIBRATION, CALCULATION

This section reviews literature related

to the first and last steps in the spectrochemical analysis process: the sample and accumulation, registration and treatment of spectral emission. 130R

0

Standards. The production, characterization, and quantitation of standard reference materials at the National Bureau of Standards continues to represent one of the most reliable sources of primary standards. I n addition to metal alloys standards, the NBS activities have shifted to related fielda such as clinical, biomedical, and botanical materials. Accounts of various aspects of the production and certification of standard reference materials have been published (l8D, 6 9 0 , 67D, 88D, 8 3 0 ) . In the production of alloy standards, for example, emission spectroscopy is generally employed for homogeneity testing

(82D). Odess and Golden described a technique for preparing 30-lb ingots of nickel alloy as chemical and spectrographic standards by adding previously doped nickel buttons in a vacuum furnace (760). Evaluation of four sample p r e p aration techniques, which included mill billets, argon arc melting, button arc melting, and sintered powered sampling, was undertaken for titanium alloys standards. The argon arc melting samples (64D)gave the lowest heterogeneity. Alfaro et al. devised a new aluminum standard preparation technique with a cylindrical sample with approximately 3.0-cm thick walls (1D). Sano et al. studied casting methods for aluminum alloys (160E). Glass reference standards for trace element analysis in and spectrographic analysis rocks (71D), of trace elements in international rock standards (41D ) have been reported. A technique for preparation of molybdenum and tungsten oxide standards was described by Molenda (69D). Galazka defined criteria for evaluation of alloy standards ( 3 l D ) . The use of metal caprates as analytical standards for spectrometric oil analysis was presented by Hearn, Mostyn, and Bedford (38D). A detailed procedure for preparation as well as results from comparative studies with widely-used metal cyclohexanebutyrates as given. No comparison of these new standards with metal alkaryl sulfonate standards is presently available. I n a study of heterogeneity in an NBS zinc standard (No. 629), Skogerboe used statistical and simple graphical techniques to indirectly detect minor element heterogeneity (9UD). The papers illustrate the value of applying good statistical procedures in the evaluation of materials and techniques in the spectrochemical literature. Thompson and Bankston compared the inconsistencies among copper and copper salts in the preparation of powder standards for dc arc excitation (980). Cupric chloride is recommended over cupric oxide or copper. Statistical Studies. Kaiser reviewed the use of statistics for com-

ANALYTICAL CHEMISTRY, VOL. 4 4 , NO. 5, APRIL 1972

pression and evaluation of experimental data (84-4). Bauer has prepared a second edition of a introductory statistical manual for chemists (OD). Statistical evaluation of interlaboratory analyses have been outlined by Mandel and Paule (67D),Mandel (66D), Parreins (77D), and in more general terms by McFarren, Lishka, and Parker (66D). Mandel and Paule presented a technique for evaluations with unequal number replicates, and McFarren et al. proposed a criterion for judging the acceptability of a method based upon a total method error. Visman (lO4D) and Duncan (88D) debated the statistical approaches to sampling theory (106D). Astashkhina and Burkov evaluated the application of a statistical multiple correlation method for evaluation of reproducibility of spectral data (20). Swietoslawska defined the specificity of an instrumental method as the reciprocal of the relative error due to interferences and noise ( 9 6 0 ) . Matherny used scatter diagram parameters in optimizing the selection of homologous line pairs (&ID), and, with Polacek, conditions such as sample prearcing, dilution, excitation source, and method of sample introduction in developing a spectrographic analysis in 85% MgO matrices (68D,63D). I n order to improve precision of analysis with the tape-transport sample introduction, Danielsson et al. used a statistical treatment for the selection of standard concentrations and estimate of parameters (16D).

Detection Limit, Sensitivity Calculations. Detection limits, sensitivity, and signal-to-noise ratios are intimately related to the precision and accuracy of a spectrochemical analysis. McCarthy has presented a summary of signal-to-noise ratio theory as applied to spectrochemical systems ( 6 6 0 ) . The general use of SNR theory to predict optimum conditions for experimental variables as well as estimation of limits of detection and comparison of spectrochemical methods was reviewed. Gabriels presented a general method for calculating detection limits covering any chosen concentration range instead of limitations of the blank level (SOD). Liteanu (66D), Dobbs and Iny ( 2 l D ) , and Shurygin (89D) discussed the techniques for obtaining analysis below the limits of detection based upon the frequency of appearance rather than the amplitude of measured signal. Hubaux and Vos demonstrated a method for estimating decision and detection limits copsidering the confidence limits of a linear calibration curve, and outlined specific approaches for enhancing the sensitivity of an analytical method (400). Detection limits, detectability, precision, and guarantee of purity in emission

analysis were considered using statistical processes by Matherny (61D). Zi1’bershtein reviewed the problems iovolved in determining actual detection limits along with an experimental procedure for determining detection limits (11oD). The effect of the line shape in the focal plane of a spectrometer on calibration curves and detection limits was considered theoretically by Haisch (35D). Two cases of different noise levels determine the selection of reduced widths of entrance and exit slits. Computer Calibration. D a t a acquisition systems for emission spectrometers with computer control have been described by a number of authors ( l l A , 35A, 53.4,140, 4-40, 6 l D ) . Unfortunately many of the computer techniques used by spectroscopic instrument manufacturers never are published, and program documentation is very difficult to obtain. Decker and Eve describe the use of a digital computer to perform emulsion calibration, background corrections, internal standard ratio calculations, arc temperature and electron pressure determinations, and correction for matrix effects (11-4). Gordon and Chapman indicate the use of an extensive computer program designed to accommodate the simultaneous calibration and interference response corrections for 20 elements without the use of comparison standards, using a commercial spectrometer (SSC). The curvefitting program used in part by Gordon and Chapman was documented in detail by Smith (91D) and is applicable to a wide variety of problems. Baldwin has written a versatile program which prepares a calibration function and plot, solves sample concentrations and computes sample statistics, covers results to final units through correction for dilution and blank subtraction, and prepares an analysis report (4D). Surs has described the technique of weighted least squares curve fitting using functional transformations ( 4 6 0 ) . Computer methods for analysis of spectral peaks have been treated by and Molodenkova and Schwartz (84D), Kovalev (700). Both approaches permit resolution of overlapping spectral peaks, but Schwartz’s program is readily accessible and used on a time-sharing computer system. Taylor and Birks described a flexible computer program for calculations in emission spectrographic analysis for a variable number of lines in up to 60 different spectra (97‘0).

Photographic Emulsion Calibration, Computation. Since photographic emulsions remain an essential readout mode in milch of emission spectroscopy, interest continues in improving emulsion sensitization, calibration, transformation, and recording. Computer-controlled, digital recording microphotometers have been described

by Robinson (1@C), Steinhaus et a1. (9BD),and Gratton et aZ. (233D). Compared to analog instruments, the digital, computer-controlled microphotometers provide high speed, ’accuracy, and improved ease of sorting and analyzing photographic data. Swing presented a theoretical analysis of conditions under which a microphotometer performs linearly in radiance, and conditions under which illumination may be considered incoherent (96D). In order to reduce flare light, high numerical-aperture microscope objectives were suggested. Grimes described new design optics for linear microdensitometry (340). Yuster has described the construction and use of a symmetrical cylindrical rotating step sector for emulsion calibration which is more compact and simpler to construct and apply that disk sectors or step filters (1090). A water-driven cylindrical sector was described by Mellichamp and Wilcox (680). I n order to make direct comparisons between spectral line sources and calibrated continuous sources, a method based upon exposure of a continuous light source was used to eliminate the Eberhard effect ( 7 3 0 ) . Fairhead and Heddle used a technique based upon absolute emulsion calibration in the vacuum ultraviolet ( 2 4 0 ) . Dyjak et al. compared the efficiencies in the extreme ultraviolet of photoelectric and photographic detectors (23D). A new paraterphenyl-coated multiplier provided a more nearly constant efficiency than other detectors tested. Plsko (135C) and Torok (179C) have reviewed properties and problems of photographic emulsions for emission spectroscopy. A technique to correct for emulsion shrinkage by using triethanolamine was discussed by Xishida (74D),and Zimmer et al. studied the influence of rapid development on photometric properties (1110).

Skogerboe measured an experimental photometric error (900), and Gerbatsch and Scholze verified predicted influences of photometric error of densitometric spectral line intensity readings on analytical precision (320). Kantor and Erdey found two main sources of systematic error for their microphotometer (470). Stenger compared microphotometric readings with visual observation of line lengths produced by a logarithmic spiral sector to develop a low cost, moderate accuracy installation (930). The transformation of the characteristic emulsion-intensity response curve to improve linearity was discussed by Rossikhin et al. ( 8 0 0 , 850), Lehmann and Navach ( 5 4 0 ) , and W-eingaertner et al. (1080). Computer processing of emulsion calibration data ( 8 0 , 9 7 0 ) and

conversion of microphotometer readings into relative intensities or concentrations have become a part of nearly every automated and computerized operation in the spectrochemical laboratory. Decker and Eve (11A) used a moderate sized computer whereas, Heemstra and others employed a small laboratory computer (l@C, 33D, 39D, 97D), and Lavaud used a time-sharing system ( 5 3 0 ) . Heemstra’s program used a quartic polynomial fit of the two-step preliminary curve and two cubic polynomials for the characteristic Seidel transform curve ( 3 9 0 ) . Nagy-Balogh described a manual calculating device for semi-quantitative analysis (72D).

Internal Standards and Other Techniques. The theoretical principles of internal standardization were treated previously by Barnett, Fassel, and Kniseley (6D), and the experimental study of internal standard lines was published in 1970 ( 7 0 ) . These two works demonstrate that the selection of internal standard lines is much more difficult than implied by the traditional “rules,” and that a more extensive knowledge of the properties of the spectral source to be used is required to apply quantitatively the ideas developed. The qualitative application of these principles should assist in the routine selection of internal standard lines. Suckewer enumerated sources of error in determining atom density ratios in a discharge and in relating them to density ratios in the sample ( 9 4 0 ) . He considered the problem in two aspects: atom populations in the discharge, and relationship of sample to plasma composition. Although the first was treated directly through consideration of spatial atom and electron density, and temperature distributions under equilibrium conditions, the difficulties in describing the physicochemical processes in converting a sample were too complex to treat directly. An experimental solution based upon an induction or dc arc-jet plasma was suggested. The choice of line-pairs for spectrochemical analysis need consider only the similarity of population pathways. The elimination of internal standardization was also suggested through the precise determination of gA ratios for suitable line-pairs in an appropriate discharges. The errors involved in experimentally averaging time-varying intensities used in line-intensity measurements have been described by Weber and Garscadden (204E). Although empirical methods are commonly used to test the homology of spectral line pairs, Matherny has improved this selection with statistical data treatment (SOD). Jamond and Roques employed simultaneous internal and external stan-


131 R

dardisations to reduce chemical and physical effects in geological materials analysis for trace elements (4m. Frank et al. found spectral background intensity to be at least as good a reference as conventional internal standards in a gas-stabilized dc arc discharge ( M D ) . Spectral distribution of background radiation in different arcs were considered. Robinson and Lott tested the standard addition method, a reverse standard addition method, and least squares technique, which minimizes both x and y residual (79D). I n the normal standard addition method, best results were obtained with a 10-30% concentration increment. Shatkay demonstrated that both the standard addition method and the method of successive dilutions were invalid in the presence of matrix interferences ( 8 7 0 ) and suggested that the method of changing parameters be used in the presence of strongly interfering unknown matrix (86D). Torok briefly discussed the use of standard additions in emission spectroscopy (1010). Froonen and Buning found that a number of systematic errors including differences in photographic sensitivity, variation in sample electrode preparation, differences in graphite powder, and variation in arc gap distance affected the long-term precision and accuracy of a multielement spectrographic method (880). Selecting an incandescent lamp as a photometric reference for direct reading spectrometer drift measurements, Franklin and Gordon compared it with a beta-ray light source, a tungstenhalogen lamp, and a tungsten-strip lamp (87D). The drift detection system is used as an integral part of the spectrometer calibration procedure. Sampling, Sample Preparation Techniques. Since sampling, sample preparation, and sample introduction into an spectrochemical discharge represent the major sources of inaccuracy and imprecision in spectrochemical analysis, considerable effort to improve any of these steps is usually rewarding. Since many sample preparation methods involve aqueous solutions, the quality of water is paramount. An excellent review of methods for preparation of ultra-pure water as well as an assessment by emission spectroscopy of trace metal content for eight ultra-pure water preparation techniques was p r e sented by Hughes, Murau, and Gundersen ( 4 0 ) . Conductivity measurements cannot be relied upon as an unequivocal indicator of water quality, and techniques which used inert construction materials produced water superior to that obtained f r o p metal stills. A small monobed deionizer contained in polyethylene and a submicron filter 132 R

appeared to produce minimum cation contamination. Pinta has reviewed the contamination problems in the determination of trace elements ( 7 8 0 ) )and Kershner, Joy, and Barnard described the practical analysis of high purity chemicals (&D, 600). Trace element contaminations introduced by grinding and sieving samples were studied by Thompson and Bankston (99D). Although Lucite grinding vials, boron carbide and agate mortars, and nylon sieves introduced little or no contamination, tungsten carbide, and alumina-ceramic vials, and alumina mortar introduced numerous trace e l e ments. Further contamination was found with stainless steel and brass sieves, and a pregrinding operation was strongly recommended. Cross contamination from previously ground samples was found to be the major source of contamination. A dust-free sample grinding installation for a silicate analysis laboratory was described by Beaulieu (1OD). Findeisen and Schdenhauer showed that a vitreous carbon mortar would contribute lower contamination than either corundum or boron carbide in sample grinding preparations ( 8 6 0 ) . Sampling metal alloys was reviewed by Hurwitz (MA), and Weber et al., r e viewed sampling and sample preparation in cast iron foundries ( 1 0 7 0 ) . Preparation of cast iron as fused buttons ( 1 6 0 ) and pig iron in a centrifugal casting procedure (860, S7D) were studied. The direct analysis of molten iron and steels required special attention to spark atmosphere and optical arrangements ( l l D ) . Specific element losses from lithium tetraborate fusions were studied by Bennett and Oliver (60). Fusions were used to reduce matrix effects (@E, 6OE). Since powders represent one of the major forms of spectroscopic sample, powder particle size and the grinding operation are often important (490). The influence of particle diameter on spectral analysis of sintered cermets was investigated (89D); however, preparation of alloy standards with powder metallurgical techniques appears to receive not much attention (640). Superfine grinding was necessary if powders were introduced directly into the discharge carried by a gas stream ( 8 8 0 ) )although the use of other powder transport techniques such as the tape machine ( 1 8 0 ) and moving electrodes (108D) represent viable alternatives to the routine packed cup technique. The tape machine is particularly useful in the diversity of samples which can be analyzed (18D). The use of a low temperature ashing machine for sample preparation was reviewed by DenBesten and Mancusco (190). Automated sample preparation procedures still remain relatively un-


known in spectrochemical analysis, not because of the computer control, but because of sample manipulations. I n order to collect precipitates in solution for analysis, the outside bottom of a porous cup electrode was used like a filter stick as solutions were drawn through it. Excitation of the collected material required no further treatment (1060). A simple microsample suction device with a micropore filter was described by Schuessler @ I D ) , and Lander et al. developed a procedure in which airborne dirt was collected on a filter paper which was subsequently rolled into a cylinder, placed into a cylindrical graphite electrode, and slowly advanced into the spark gap (68D). A base-vented cupped graphite electrode which prevented ejection of powdered samples upon arcing was d e scribed by Toft and Roworth (lOOO), and Marling (68D). Ultrasonic nebulizers have been used to produce solution and solid aerosols. I n some applications the aerosol is d e solvated prior to introduction into the source. Ultrasonic nebulizers and d e solvation chambers have been described by Uny et al. (lOSD), Dickinson (8OD), Owen (76D), Carrion de Rosa-Brussin ( l S D ) , and Kawaguchi et al. (48D). Two powder feeding devices for an induction plasma were devised by Davies et al. (17D). The direct introduction of solutions into spectrochemical sources, especially high frequency discharges, presents new difficulties not common in flames or solution electrode techniques. Emission techniques such as a microwave plasma have been used as gas chromatographic effluent detectors for mercury ( 8 D ) . EXCITATION SOURCES

The basis upon which one establishes criteria for the classification and assignment of excitation sources appears to be founded less upon an understanding of the electrical, chemical, and physical processes of the plasma than upon historical, empirical, and convenience categories. When is an arc not an arc but a plasma jet, plasma torch, or spark? For example, classification of radio frequency supported discharges as combustion flames appears arbitrary and based upon superficial appearance rather than upon an understanding of the plasma production processes. As the spectrochemist begins to consider each step in the generation of a discharge and obtains detailed descriptions of the processes in excitation sources, conventional approaches to excitation source design and application may become more logical and direct. Unfortunately little work is being conducted by analytical spectroscopists with this goal in sight, for whatever multitude of reasons, and the categories

used in this review reflect the wnventional approach. Sources for spectrochemical analysis can be divided into electrically-generated and supported discharges and radiation-generated and supported discharges. Laser radiation interaction with materials exemplifies the latter. Electrically-generated discharges may be categorized in a variety of ways including among others, the duration and magnitude of electrical signals (dc U8. microwave) the methods of transference of electrical signals to the preplasma discharge support material (graphite electrodes us. an induction coil), the method of sample introduction and form of the sample (solution spray us. powder in a graphite cup), or the distribution of energy among electrons, molecules, atoms, and ions, as the result of discharge gas pressure. Plasma Diagnostics. The recent literature on excitation source plasma diagnostics is too extensive to include in a comprehensive review. The need for plasma diagnostics is critical to understanding spectrochemical plasma processes, however. A substantially abbreviated collection is surveyed here. Optical diagnostic techniques range from spectroscopic measurements of band, line, and background intensities, to line broadening (37E) and shift determinations. Recent advances in o p tical, microwave, and other techniques in plasma diagnostics are included in three volumes by Tolok (181E). Spectroscopic diagnostic techniques were discussed in a chapter by Cabannes and Chapelle (3OE). Magnetic and electrical probe measurements are not commonly used for atmospheric pressure plasmas, although theory is being developed. Swift and Schwar have considered electric probe plasma diagnostics in their recent book (176E). A single chapter reviews alternative plasma diagnostic techniques including conductivity measurements, microwave transmission and reflection methods, and optical interferometry. The Stark Effect, especially of hydrogen, is commonly used for diagnostics (64E, 69E, 7OE, lo@, 196E) when low concentrations of hydrogen probe gas are added to a discharge plasma. Methods based upon Schlieren (68E, IObE), interferometric (73E, l l S E ) , and laser techniques (17E, 86E, 101E, lo@, 111E, I d l E , ,906E) are useful diagnostic approaches. An example of spectrographic plasma diagnostics of a very line-rich uranium discharge used in determining the electron and U I1 partial pressure appeared in the work of Schneider et al. (164E). Two spectral-line techniques for temperature determination (Boltzman plot technique and single-line relative intensity method) were used with Abel

inversions to give radial temperature diatributions. All photographic readings were corrected for emulsion calibration, and all lines were subjected to a full Voigt profile analysis to ensure similar line shapes. Weber and Garscadden have developed an error analysis of lineintensity measurements due to experimental averaging of timevarying intensities (m4E). Drawin considered spectroscopic diagnostics of plasmas not locally in thermodynamic equilibrium

(4lE).

Suckerwer's considerations of sources of errors in the determination of atomic ratios and the conversion of atomic ratios to concentrations included a description of the distribution of atoms and deviations from local thermodynamic equili'urium (040). Thermal Plasma Processes. Recent developments in plasma processes are reported a t technical meetings not often attended by spectrochemists. For example, the International Conference of Phenomena in Ionized Gases is held biennially, and the proceedings of the 9th Conference held in Bucharest were published in 1970 (1,92E), and the report of the 10th held in Oxford in September 1971 has a p peared (8f 7 E ) . The combined Gaseous Electronics Conference and Arc Symposium which was held in Hartford, Conn., in October 1970 and Gainesville, Fla., in October 1971, included topics of spectrochemical interest directly related to plasma processes (&E). Announcements and programs of many of these meetings can be found in the Bulletin of the Physical Sockty. Arc Plasmas. Vukanovic et al. have outlined and reviewed processes in arc plasmas related to spectrochemical analysis (lOOE), including the effect of arc atmosphere, plasma composition, and chemical reactions on plasma parameters such as the radial temperature 134E-137E1 distribution (7@-76E, ,WOE, ,9OlE, b16E). In these reports, the radial temperature distribution was obtained from the Elenbaas-Heller equation for an energy balance on the plasma. For spectrochemical analysis, the residence time of particles in the plasma was dependent particularly upon the radial temperature distribution gradient. Therefore, changes in temperature distribution due to plasma composition or external magnetic fields influenced the spectrochemical result. Decker has considered the variation in temperature of the sample electrode on the ultimate variations in spectrochemical results (36E). The electrode temperature is determined mainly by the power developed in the arc column, the electrode dimensions, and the arc gap. Decker and Eve also considered arc column wandering, which may be controlled to some extent by choice of

electrode diameter, arc current, and buffer compounds (36E>. An extensive study of arc electrode temperatures of and reignition voltages of graphite electrodes in argon a t currents less than 45 A was conducted by Murooke. using a fast photoelectric pyrometer arrangement (12OE). Temperature changes of anode and cathode during initial heating as well as temperature distribution on electrode surfaces were measured. The spectral radiance of a carbon arc between 2500 and 1900 A ( l @ E ) and the millisecond fluctuations of radiance temperature of a graphite arc (31E) have been measured. The increased use of high-speed photoelectric pyrometers can be expected to provide another powerful physical tool for recording electrode temperature changes during spectrochemical processes. Further developments of the use of magnetic fields in spectrochemical dc arcs were reported by Nickel et al. (fOlE-104E) and Petrakiev and Milanova (130E). Close-electrode intensification, especially of ion lines, was observed and the processes were investigated (103E). Nickel et al. recorded interferometric temperature distributions and streaming conditions in the arc. Temperatures were shifted due to the arc rotation. Boumans and Maessen have related the thermochemical and physical conditions in the electrode and the operating conditions of the arc to the relative efficiency of movement of elements into the discharge channel (,ME, W E ) . Bril and Duverneuil made microsecond photographs of material transferred into the arc channel to correlate with simultaneous spectrometric measurement ( M E ) . Processes associated with the entrance and excitation of elements into an ac arc were studied by Shavrin et al. (61E, 166E). Smirnova and Krinberg derived an expression for spatial concentration distributions in an arc (166E). Using gamma spectroscopic techniques, Avni and Goldbart made direct measurements of the transport mechanism of particles in dc arc plasmas in air a t atmospheric pressure by collecting material on a sampling device passed through the arc (8E). Evaporation rate, particle flux, particle velocity, and diffusion coefficients were calculated for urartium particles, and for lanthanum arid samarium particles (9E)* The role of thermal conductivity of alloy electrodes in ac arc discharge sampling was studied by Golitsyn and Rudnevskii (67E). Current density of cathode spots was evaluated by several authors (14E1 87E, 61E, 149E), and determination of arc equilibria also was studied @El f Q E ,M E , 163E).

ANALYTICAL CHEMISTRY, VOL. 4.4, NO. 5, APRIL 1972

r-

133R

Arc Plasma Jets. I n order t o create a stabilized arc plasma stream or column, various approaches have been investigated. One genre of devices is the wall-stabilized arc, and another is the segmented-disk stabilized arc. The properties of these devices, in their various configurations, have been described ( l E , l S E , QOE, 89E, 94E, l l 4 E , dlBE, d16E). Stabilized arc discharges were employed as sources for other than spectrochemical applications (4E, 12El 126E). Kliska and Marinkovic (OOE, 109E) systematically investigated the parameters of a stabilized arc for spectroanalysis. Each arc electrode was stabilized by argon flow and a cooled, segmented metal chamber. Solution injection geometry, arc current, type and concentration of chemical buffer, aerosol flow rate, and organic solvents were studied. Using a Mg-HzO-air plasma produced by a Riemann disk-stabilized arc, Raab and Bogershausen compared radial spectroscopic temperature measurements to theoretical calculations (146E)* Marinkovic and Vickers employed a stabilized argon arc for the production of free atoms in atomic absorption (110E). The arc channel was purposely extended to increase the absorption path length. Malinek and Massmann used a Kranz-type plasma jet as an atomic reservoir for absorption (107E), and Kranz reported detailed studies of the introduction and distribution processes for substances in the plasma jet discharge of his design (91E, 91E). Valente and Schrenk have developed a transfer-type plasma jet with anode and cathode enclosed in separate cylindrical chambers to permit rotation of the electrode axis (190E). The included angle was approximately 30’ during operation. Emission intensity distributions were reported for the discharge plasma. Elliott described an argon plasma jet, which served as the source for a complete spectrochemical apparatus (6OE). Heemstra employed a plasma jet with a controlled atmosphere to exclude air for the analysis of nonmetallic elements in petroleum products (67E). Experimental measurements to test local thermodynamic equilibrium of an argon plasma jet were made by Bourasseau er al. (14E). Oku et al. explained the selective volatilization of metal solid samples in a nitrogen plasma jet as the result of reactions of the solid-alloy sample with nitrogen and the stabilities of individual metal nitrides (lW7E). T i e viscosity (166E) as well as a computer study of nonequilibrium excitation in nitrogen plasma jets (15E) were reported. Spectral distributions in a plasma 134R

jet were obtained by Isagawa and Niki ( W E ) , and plasma jet discharge temperatures were reported by several investigators (f!OE, 69E, 116E, 164E, 209E, HOE). An interference holographic study of a plasma jet was conducted by Burmakov and Ostrovskaya ( B E ) . The structure of the 02 Schumann-Runge system was studied by Wray and Fried in a plasma jet source (806E). High Frequency Discharges. The generation of a plasma discharge a t atmospheric pressure can be accomplished in electrodeless and “near electrodeless” configurations, using electrical field frequencies of KHz to tens of GHz and power levels of 700 KW a t low frequencies (196E) and a few hundred watts a t high frequencies. Often these high frequency discharges are classified as microwave (>500 MHz) and radio frequency (500 KHz-500 MHz), as the result of the instrumentation required to generate the discharge (188A). Applications other than spectrochemical predominate in the literature, and many physical experiments and most theory in plasma physics are often overlooked by the spectrochemist. One industrial application of these as well as dc plasma jet discharges is chemical reactions for synthesis (44E, 132E, 188E, 191E). The development of spectrochemical sources is progressing relatively slowly, however. More systematic or fundamental studies need to be undertaken by spectroanalysts. Unfortunately, high frequency plasma discharges somewhat superficially resemble flames, and have been erroronously given the names “plasma torches” or “plasma flames.” Since the plasma generation process is purely electrical, terminology used which refers to combustion processes and combustion waves does not apply, although Raizer has used a “flame” model to define a reaction zone in the induction discharge (148E). An excellent review of inductiongenerated plasmas by Raizer defines some of the problems which must be investigated (148E). Robin (166E) and Fassel (61E) presented oral reviews of recent techniques and equipment. Various theoretical and numerical treatments of the induction coupled discharge have been presented by Pridmore-Brown (48E1144E), Trekhov et al. (168E, 186E), Apsit (SE), and Eckert (@E, 47E). Chase has made theoretical and experimental studies of the pressure and flow in an atmospheric induction plasma (SSE), and Eckert measured the magnetic field distribution (46E). The equilibrium conditions of induction plasmas have been discussed by Stokes (17OE1, and Dresvin and Klubnikin (41E). Studies of other plasma parameters such as frequency de-

ANALYTICAL CHEMISTRY, VOL. 44,

NO. 5, APRIL 1972

pendence, effective diameter, conductivity, spatial distribution of fields, electron concentrations, temperature, and atom and ion concentrations have been reported by various groups (bE, 16E, 89E, 34E, @ E , 69E, 86E, 96E, W E , i o o ~1,W E , 18 9 ~ ME). 4 The introduction and interactions of sample materials in the plasma discharge and posMischarge (“tailflame”) regions have been considered by Capitelli et al. (%‘E) and Ionin et al. (’77E) for alumina particles, and by Leont’ev and Tsalko for aerosol particles (99E). The effect of external magnetic fields has been measured by Mitin e.! al. (119E), and the relaxation of argon species upon plasma shuMown was studied by Apsit (SE). Particularly noteworthy is the work of Murayama using a coaxial-waveguide plasma-discharge configuration with a single electrode operating a t 2469 MHz (118E, 119E, 20’7E). The addition of sodium to an argon plasma a t atmospheric pressure resulted in modification of spatial distribution of line spectra, due to spatially non-uniform temperatures and diffusion of plasma species. Spark Plasma. Spark plasmas have been used for spectrochemical analysis for almost as long as combustion flames. Kaiser presented a selective and conventional discussion of the development of most common spark sources, operating parameters, and electrode sampling effects including volatilization, transport, and excitation (8SE). Study on the formation of spark channel continues (58E, 87E, 169E), although only Walters (101E) has attempted to carry the observation completely through initiation to spectrochemical result. In an attempt to understand thunder better, Plooster has developed a numerical simulation of spark discharges in air which predicts spark channel radii, temperature, electron pressures, and other parameters (l4SE). Of prime importance to the spectrochemist is the interaction of the discharge with the sample electrode. Latham and Braun have studied prebreakdown cratering (98E), and Augis and Gray used scanning electron microscope techniques (6E, 62E) to observe cratering due to a single nanosecond discharge (7E, 6SE). Electrode sampling and its dependence cpon parameters such as heat flux and duration of current flow, and the comparison of gaseous and solid phase compositions have been studied in some detail (6E, ISE, 66E, !76E, 177E-l80E, 19SE, 197E, 198E). The influence of rete of material sampling on spectrochemical results has also been considered (11E , 66E, 66E, 116E, i 7 l E , 193E, 198E).

The use of timeresolved spectroscopic techniques appears to have permitted the most successful and detailed descriptions of the spark plasma. Based on time-resolved intensity measurements, Mailtmder and Krauss proposed a model for cathode-spot sampling processes from which they obtained theoretical predictions and experimental verification of spark current spectral intensity relationships (106E). Diermeier and Krempl measured zinc-line time profiles (39E) and Boettr ger and Krempl measured time-resolved hydrogen line profiles (HE)to determine temperature and electron densities during the relaxation of a spark discharge. Hirokawa and Goto used millisecond resolution time-resolved techniques to study spectra produced in a lowvoltage, high-capacitance impulse discharge (70C, 7 1 E ) . Hirokawa used the discharge to indirectly sample and excite spectra from nonconductive materials by means of energy transfer to the sample from the discharge plasma (78E). Schroeder et al. have used photoelectric time-resolved systems to study spark discharges (134C, 169C), and van der Piepen and Schroeder used a flowing argon-stabilized spark to obtain radial-resolution temperature measure ments of the discharge channel (191E). A similar stabilizing arrangement was developed by Walters (BXE). Temporal and spatial changes of a highcurrent discharge were measured by Ito et al. using time-resolved and framing camera techniques (79E). Source parameters for specific spectrochemical analyses were studied by Sano et ai. (160E),and Ferreira et d. (63E). A study of parameters and electrode reactions was reported by Strasheim and Blum (171E). Perhaps the most significant contributions in defining the action of spark plasma for spectrochemical analysis have come from the efforts of Walters and associates. Through the combination of very careful attention to experimental detail and the application of the appropriate physical principles, a uniquely clear and welldocumented description of spark processes in spectrochemical analysis is emerging. Sacks and Walters effectively combmecl time and spatial resolution not only to observe the radiation processes in a spark discharge, but also to interpret the information in a meaningful way (169E). Just as Walters first made meaningful hypotheses based on timeresolved axial measurements of the transient, spatially-heterogeneous spark channel, recent time- and spatiallyresolved radial measurements have led to a relatively straightforward model of the interaction of expanding electrode material from sampled cathode

with the currentdependent expanding and contracting spark plasma channel. Using a model system composed of an aluminum cathode in a nitrogen a b mosphere, Sacks and Walters demonstrated that the probable radiation controlling processes were charge-transfer excitation of aluminum atoms and ions by nitrogen ions in the discharge channel, and stepwise volume relaxation on the channel boundaries. In addition to an initial charge-transfer excitation in the cathode space charge region, electrode material was apparently maintained in a state of high internal energy by undergoing continual chargetransfer reactions while axially traversing the spark gap. As the spark current fell late in time, volume relaxation t0 lower stages of ionization predominated. Because of the lack of current control, radiation patterns from neutral atoms responded only in an indirect way to instrumental changes in the discharge current. Current controlled the discharge channel shape and amount of material eroded from the electrode, but not the residence time of electrode vapor. Many of these observations have been used by Walters ( N g E ) to propose a straightforward model to predict and describe changes in spectra based upon the change in instantaneous discharge current as the unique spark parameter. The t i m e and current-dependent spectral emission can be predicted based upon a simple model. Features were dependent upon the mass dilution of sampled eIectrode vapor moving radially outward from its original sampling site; maximum radial channel excursion relative to the expanding cloud of electrode vapor; and the rate of decrease of the discharge channel size. Walters demonstrated that the axial spatial dependence of radiation from a steady-current discharge, such as a dc arc, compared to the temporal dependence of the same radiation from a pulsed current discharge--i.e., a sparkas the result of similar and perhaps common discharge excitation phenomena. Changes in source parameters a p parently did not result in changes in fundamental excitation mechanism. Walters concluded that sensitivity may result from the manner in which the radiation is observed and detected instead of the manner in which it is produced. He emphasized that spectrochemical methods might be completely characterized without empirical and rigid standardization of properties of the apparatus. Utilizing a coaxial quarter-wave, currentrinjection source a t 162 MHz (1860, Walters has explored the basis upon which stable discharge plasma operating a low current (e.g., less than &A peak pulse) and high repetition rates (ie., 1500-4000 per second) can he used for qualitative and quantitative

spectrochemical analysis as well as for fundamental studies of plasma processes ( , W E ) . The discharge position, electrode erosion rate, and radiation output were unconventionally stable and contributed to a stable concentration of sample vapor in the discharge. Measures taken to ensure stability of the discharge during formation and initial current acceptance provided the bases for controlled and stable electrode Sampling. Accordingly, spectral intensities displayed a precision of 10-15% during two hours of continuous operation a t discharge repetition rates of 2000 per second. Initial plasma formation, current conduction, and current growth were studied in argon and argonnitrogen plasmas using a framing camera in a sampling mode to provide 5nsec maximum time resolution. Metastable argon species and their reaction pathways appeared to be the key in the discharge processes and in the source stability. The design of the spatially stable plasma source eliminated many of the dSculties inherent in conventional spark sources, and permitted the observation of discharge processes with conventional and state-of-the-art readout systems. Through the elimination of the spark source as the major contributing source of error, prospects for previously impossible controlled and reliable spectrochemical analysis are good, and serious attention should be given Walter’s work. Laser-Produced Plasmas. Ready has treated the effects of high-power laser radiation interacting with materials (162E). Mandelstam (113C), Felske et al. (16A), and Valero et al. (18,90 have discussed the discharge plasma produced by laser interaction as a spectrographic light source. Scott and Strasheim studied with a framing camera the interaction of pulsed laser radiation with metals to show crater and plasma formation stages (163E). Spatial- and time-resolved studies of various laser plasma plumes were investigated. Improved analysis resulted from spatial and time selection of the plasma plume emission. Baldwin investigated the &-switched laser sampling of copper-ainc alloys to determine the relationship between the composition of removed material and the original sample (10E). The material was removed from the crater as both liquid and vapor, which was collected for analysis. The composition of the vapor could be predicted from the liquid-solid equilibrium for the copper-zinc system. Ablation of the molten metal rather than vaporization, as previously accepted in the literature, appeared to be responsible for removal of most of the material. Piepmeier and Osten investigated the influence of atmosphere on Q-


135 R

switched laser sampling and resulting plasma plumes ( l 4 l E ) . Observation of constant crater diameter and amount of material ejected was considered the result of the absorption of laser radiation by the plasma at atmospheric pressure. A radiation-supported shockwave model was evaluated, and a p proaches to minimize plasma absorption were proposed. Piepmeier’s suggestion that short wavelength radiation would help to minimize atmospheric plasma absorption was substantiated by G i b son, Hughes, and Ireland in a comparison of COS and Nd*+ glass lasers (66E). The longer COZ wavelength showed more plasma heating and stronger line emission further distances from the target. Piepmeier and Osten’s experimental measurements indicated that plasmas produced from heterogeneous samples may require time to become homogeneous prior to optimum spectrochemical analysis. Microanalysis by focused laser radiation, especially 6f nonconducting materhls, is an important aspect of laser emission spectrochemical analysis. The suppression of spectral intensities by orgrlnic materials in the sample was studied by Marich et al. (108E), and the influence of atmosphere was investigated by Tretyl et al. (187E). Differences in plasma plumes from metals and nonmetals were observed by Yamane et al. (208E) using cross excitation, and sources of inprecision in laser-microanalyses were determined by Moenke et al. ( l l 6 E ) . Matrix Interactions. Using X-ray diffraction techniques, Nickel determined the IVa, Va, VIa transition element carbide, nitride, and oxide distribution profiles in the matrix formed during arcing a t 10 A in nitrogen and argon ( l 2 4 E ) . Although results with oxygen-containing compounds arced in argon agreed with thermodynamic calculations, those in nitrogen could not be predicted. Spectral intensities varied with compound. Rautschke determined by X-ray analysis the dc arc reaction products for silicon, titanium, zirconium, and manganese oxides in graphite (161E). Thermodynamic calculations for various reactions were used to determine conversion. I n the study of volatization mechanism of Mol Ti, V, and W with different buffers, Diaz-Guerra identified intermediate reaction products by X-ray diffraction (%E). The influence of the addition of ammonium salts (216E) and other cations (93E) on spectrochemical results in an arc was investigated. Effects on analysis by blowing powders into the arc were studied by Kibisov et al. (88E), Kubasova et al. ( N E ) , and Rusanov et al. (167E, 213E). 136R

4

ANALYTICAL

Raikhbaum et d. have formulated a mathematical expression transforming evaporation time-intensity recordings to obtain constants characterizing the kinetics of vaporization (146E, l&‘E). Sano et at. studied the method of preparation of aluminum alloy casts and the effects on spectrochemical as compared to chemical results (161E). Fusions with lithium borate flux have been used to reduce sample matrix effects ( @ E , 6 0 E ) . Arc excitation of copper binary alloys in an ammonia atmosphere reduced interfering background and spectral interferences and altered relative intensities of atomic and ion lines (214E). Pasky studied interelement effects in emission spectrometry of ferrous alloys (IME). Carrier Distillations. The chemical and physical reactions occurring in the arc electrode and gap in the Scribner-Mullin carriek distillation technique have received further attention, although no comprehensive theory has yet been developed. I n order to distinguish between the influence of excitation conditions in the arc plasma and the thermochemical reactions h the electrode, Strzyzewska selected a Mg II/Mg I line ratio as an excitation indicator (1 7 4 E ) in a study of the oxide (172E) and halogen carriers (173E). Impurities in aluminum and silicon oxides were studied using 35 diff erent carriers. I n the development of a method for the determination bf 24 trace elements in M o a , Morris and Worden studied AgCl and GazOa carriers in various atmospheres including air, argon-oxygen, argon, and helium, and demonstrated the effect of CO generation during arcing on differences in excitation (117E). They suggested that the evolution of a CO frbm the matrix produced a suitable temperature in the anode for vaporization of the carrier and impurities, and reduced the electron temperature in the plasma, compared to argon, to promote excitation of vaporized impurities. Neuilly et al. considered the reactionfree energy of a number of carrier combinations for determination of aluminum and iron in uranium oxide, and tested a number of carrier combinations and the granularity of matrix prior to selection of a suitable carrier (123E). Russell et al. used a lead fluorideAgCl carrier to determine alkali metal and alkaline earths in uranium oxide (168E), and Joshi and Pate1 determined nine rare earth elements in uranium samples with Lil-AgCl carrier mixture after a comparison of six other matricies (80E-82E). h n q u e t examined the effect of theoretical predictions on the selection of halogenated carriers in the analysis of

CHEMISTRY, VOL. 44, NO. 5, APRIL 1972

urafiium oxide (160E). Blank et al. described the spectrometric carrier analysis of impurities in uranium (188E) and thorium materials (18E). The importance of humidity and temperature control was demonstrated. Mixed plutonium-uranium oxides were studied using a AgCl-BaFz carrier by Murray et al. ( l S l E ) , and the determination of rare earths in uranium compounds was investigated by Zmbova et al. ( 2 l l E ) . Determination of trace rare earth elements in europium oxide (130E) and yttrium oxide (128E, 129E) using carrier methods was studied by Osumi et al. Tumanov and Petukhova studied the transport reactions of metals and metal oxides in a stream of chlorine in the development of a trace element method for alloys and oxides (189E). Atwell and Golden used a AgC1-LiF carrier to determine lead, tin, and bismuth in nickel-base alloys (bE), and Pevtsov et al. studied the effect of various carriers in the analysis of tung$ten and zirconium oxides ( 1 4 0 ~ ) . Saranathan et al. described a carrier distillation technique for CaO (162E). Krasnobaeva and Zadgorska measured the residence time of atoms in the arc in the presence and absence of carriers in a solution residue technique (&?E). Evaporation of impurities from AlCls was accomplished with a KBr-CGazOs mixture (84E). SPECTROCHEMICAL ANALYSIS

Emission spectroscopy methology is characterized by sp&fkity, since no single technique applies optimally to every material. Various investigators through the years have attempted to develop the “universal” spectroscopic method. The possibilities appear to be increasing for a minimum methodology, which permits analysis of widely diverse sample materials, as the result of the accumulation and application of more fundamental descriptions of the sampling and excitation processes. One of the best recent examples of a wide-range method is that described by Gordon and Chapman (68C). Through a series of experimental developments, which include use of a static argon atmosphere a t 300 Torr; a servo-mechanical, optical-feedback, current-controlled system; a unique tantalum-sphere cathode; and a common-matrix-buffer microsample, an extremely stable dc arc plasma was produced which permits high-precision analysis without an internal standard. Samples were dissolved, and microliter volumes deposited on carbon electodes, which contain 4 mg of AgCl in the carbon matrix. The analysis of 20 programmed elements was accomplished in a material without use of comparison standards, because no matrix effects occurred due to excitation

suppression or enhancement. Standard calibrations were prepared with individual stock element solutions. With automated arcing and data reduction, including computer correction for 20 interelement spectral interferences, analysis time was four minutes per a m ple including electrode preparation and data logging. Odanaka and Idohara briefly reviewed spectroscopic analysis with emphasis on the possibility of a universal method (1678’). Gabler and Peterson described a procedure for miscellaneous inorganic materials in which copper oxide and graphite were used as diluents, and ac arc excitation in a controlled atmosphere was used for minor and trace elements (62F). Spark excitation of pellets of the same material permitted major constituent determinations. I n the development of an improved semiquantitative spectrochemical technique, Long critically examined commonly-used semiquantitative procedures, including a comparison of various matrices, to find that a lithium fluoridegraphite matrix gave optimum results (19SF). Addink’s book “DC Arc Analysis” presented a complete system of semiquantitative analysis (1.4). Kibisov discussed the conditions and fundamentals of quantitative analysis for substances of arbitrary composition (109F). Trace Element Analysis. Reviews considering trace element analysis in clinical chemistry (64A, 7SF1 8 l 4 F ) and geological materials (71D, 74F1 146F) along with a discussion of sampling and preparation errors in trace analysis (78D, 149F) have appeared in the past two years. Trace element analysis in highly purified ( M D ) natural waters (107F, SdOF, S d l F ) , and high purity chemicals ( 4 6 0 , 6 0 0 ) is an important aspect of environmental water quality control. Trace analyses in carbon products (S7F, 68F, l&F) have been reported, and Torok and Ban described a blank-value correction procedure to compensate for impurity interferences in low-grade graphite electrodes (219F, SSOF). A shorepulsed dc arc technique was found superior to the copper spark method for nanogram amounts of elements ( 1 4 l F ) . Trace element analysis in biological materials is becoming increasingly important (87F, 166Fb). Niedermeier et al. described a spectrometric dc arc procedure to determine 14 trace elements in 2 ml of blood, after acid digestion. Noteworthy is the report of Hambidge in which nanogram quantities of chromium in blood, hair, and urine were determined with a relative standard deviation of 6% on sample quantities similar to those in gas chromatography (87F). The use of t h e

controlled dc arc in argon described by Gordon and Chapman ( 5 8 0 abparently contributed to Hambidges’s results. A spectrometric procedure for 26 trace elements in soils and stream sediments was described by Foster (61F). Spectroscopic methods for trace elements in rock and soil materials (16F, 36F, 6SF, 807F), airborne particulates (89F), marine sediments (138F), and other natural materials ( l @ F ) were described. A spectrometer system for analysis of high-purity materials was presented by Cooper and Hobbs (36F), and a brief summary of trace element analysis in some high-purity materials is given in Table 111. Analysis of trace elements in metals is exemplified by the determination of ppb impurities in metallurgical products described by Golden and Atwell. Elements were precipitated as sulfides in the presence of a MOcarrier, which was converted to the Moos for analysis (69F). Another sulfide precipitation was used to separate tin in iron (39F), and a hydroxide carrier precipitation was used in high purity Zn and Cd analysis (116F). Trace analysis in iron and steel (180F) and arsenic and antimony were reported (SS6F). Extraction of elements prior to analysis increased selectivity and sensitivity for a number of materials (llOF, 1 1 l F , 1S6F1 l @ F , 166F, l l O F , W 6 F 1 144F). Geochemical Materials. One major application of emission spectroscopy is in geochemistry (19.4). May (137F) and Shapiro (SOOF) reviewed silicate rock analyses by spectroanalytical methods. Mitchell discussed trends in applied geochemical and biogeochemical analysis (ICIF), in which he considered analytical requirements, review of early methods, solution and concentration techniques, and the use of multichannel spectrometers. Ahrens and Van Michaelis discussed emission and X-ray fluorescence methods for meteorites (SF), and Plastinin reviewed the spectrographic analysis of micas (173F). Ropert determined seven major elements in high concentrations in rocks by means of a glow discharge device (186F). The high-stability discharge showed no self-absorption and permitted analysis without internal standards. Because specific emission spectroscopic analyses of ores, plant dressings, soils, minerals, and rocks are extensive, they will not be included here.

Rare Earth, Actinide Elements. The analysis of rare earth and actinide elements by emission spectroscopy continues to provide rapid multielement results. Alvarez and Roca Adell reviewed application of emission spectroscopy to nuclear materials (1 F ) , and Table IV summarizes some rare

Table 111.

Trace Element Analysis in

Material

Pure Materials Impurities Reference

F’Z

Fi

Ga

NbiOs Pb

Re

Sb, GsSb Ta

... 17

14

10 18 16 16 7

(m6F)

I%{

(199F)

UOF) ( I I O F , 111F)

earth and actinide element determinations published in the past two years. Perhaps the most impressive develop ment in rare earth element analysis a t the part per giga (109) level is the use of X-ray or electron-excited optical fluorescence of atomic line emission (@F, QF, 67F, l W F , SOSF). The techniques for host systems as developed by D’Silva et al. (@F, &F, @F) are relatively direct, although considerable effort was required in the development. The sensitivity is very high, and the actual experimental appatatus is straightforward. Isotopic Analysis. The determination of 15N in the presence of l4N by optical emission spectrography has become widespread and competitive with mass spectroscopy (7OF). Middelboe (139F) suggested the need to study the l4Nl4Nspectrum at 2983 k at various operating conditions to improve accuracy. Perschke et al. compared the results of mass spectrometric and electrodeless discharge emission measurements for the determination of natural abundance of 16N in various materials (169F). Goleb, Middleboe, and Kumazawa studied the distribution and accumulation of ISNin rice plants (708’). Berthelot reported the isotopic analysis of OLi and 7Li using a Fabry-Perot interferometer (1 4F). Zhiglinskii et al. compared the results with a hollow cathode discharge for the analysis of Mg isotope ratios to those obtained from mass spectroscopy (24SF). Nemets et al. described the errors involved in the isotopic analysis of small amounts of hydrogen using a discharge tube (164F). Rossi studied the structures of three uranium atom lines to find the 2s*U 4116.097 A line most suitable for determining 2S6U/2a8U ratios for 286U concentrations between 10 and 93 per cent (186F). Capitini et al. used an electrodeless lamp for the analysis of 2g6U (27F). Zakorina et al. measured the lSC/laC ratio in gases, solids, and plants using an isotopic balancing technique with a


137R

Table IV. Some Rare Earth and Matrix Elements Graphite Eu Gd,Dy,Sm Bauxites RE! elements Monazite La, Th, Gd, Ce, Sm. Y, Nd Tungstates 14 rare earths Sodium rare earth Fe Cu, Sn, Cr, Ni, Mn, molybdenates hlg AI, V, Ca, Si Rare earth Eu, Y‘ mixtures Rare earth Y(1-90%) mixtures Rare earth metals In, Ge La Ce Pr Nd, Sm, Eu, Gd,

b k

k,

Ce, Nd 15 elements La, oxides Sm, Eu, Gd, Dy, Ho, Er, Tm, Lu Ce, La, Y Fe, Gd, M , Ca, Eu, Al, Cu C&08,LazOf, Y208 Ce, Pr, N f Sm, Eu, Gd, Y Laz08, Y14, Ce, Pr, Nd, Sm, Eu, Gd, Y, Fe Cu, Al, Ca, Mg, NdzOi B, Cd LMOa, YzOS, Sa08 rare earth elements Dx, Tm, Ho, Yb, Er, Tm, Ergo8, YbZO, La108

La208

LU

Pu PUOZ Pu(IV), u Th “4Cm oxide Cm-oxide, Cm-Am oxide Table V. Matrix

A1 Al (alloys) Au Ag (fire assay bead) Bi (alloys) Cu (antique) Cu (bronze) Cu (alloys) Cu (noble mud) Cu-Ni (refining Fe (cast) Fe (cast)

Fe (cast) Fe (molten) Fe (oye) Fe (pig) Fe (steel) Fe (steel) Fe (steel) Fe (steel) Fe (steel) Fe (steel) Fe (steel) Fe (steel) Fe (Kovar) Mo W-Mo (alloys) Ni (alloys) Ni (Ta, B alloys) Pt, Pd Sn (plate) Ti Ti Te Zn Zr-Nb (alloys) 138R

dc arc, split burn

txj

dc arc, Ce internal std.

(76F)

spark

(78F)

(40~) copper spark, Cr int. std. (98F) dc arc dc arc, extraction dc arc, extraction

(76F)

spark, solution spark, solution spark, solution

(i6iF) (169F) (i60F)

s ark solution & arI!

(i03F, lO4F) (79F)

rare earth elements

do arc, carrier dist, do arc dc arc dc arc, carrier dist. dc arc do arc review dc arc, carrier dist.

Gd Sm, Dy, Er, Ce 47 {mpurities 18 trace elements 22 elements Ta 22 elements

dc arc, extraction do arc, cathode region dc arc dc arc spark, residue dc arc, carrier dist.

10 elements Sm, Gd, Tb Er, Gd, Ho, Tb, Y 10 elements 25 impurities Gd, Tb, Dy, Ho, Er

EuzOs EuzOs DysOa YZOS Y208 YlO8 Uranium Uranium

Actinide Elements Analyses Technique Reference dc arc, Nd internal std. (S47F) ac arc, Cu electrodes (#43F, 8 G F ) 2 arc procedures (848F)

(8OF) (904F)

SDectrochemical Analysis of Some Metallic Sameles Elements determined Technique Reference impurities review ac arc Be,.B, Ti, Zr, Nb, Ta methods reviewed native samples dc arc Pt, Pd, Rh Au (1-30 P P b dc arc Pb, Te spark, solution 10 elements 8 elements spark, oxide conversion impurities, small sized samples standard addition 0.04-0.4% Au dc arc, co-precipitation plasma jet spark spark, special mold s ark, (inert atm.) arc spark (Ar/H2) mark. arc spark’ spark microspark 1-mm area ac arc, spark Sn, Bi, Zn, h,Cd, Sb Ag, Pb, Sn, Bi, Te, As, Sb arc (magnetic field, COS atm.) spark, solution 8 elements interlab study 10 elements a.rc Ni, Co, Mn arc h c0.01-0.001~) ac arc, chemical dilution w (0.2-1) arc Te (0.3 pg) s ark, solution Ta, B c arc, extraction 18 im urities dc are, carrier Pt,,!P Ru, Rh, Ir Rpark spark, ac arc 7 elements arc 11 elements Dreconcentration imrmrities Fe; Pb arc Zr, Nb spark

Bc

B


hot hollow cathode discharge tube

(289F). Metals.

Spectrographic applications for the analysis of ferrous (91F), and nonferrous (9F,4 i F ) metals were reviewed through Fall 1970 in the a p plications section of these biennial r e views. The reader should consult the specific area of interest for metals d e termination. An abbreviated listing of analyses of metal samples is given in Table V. Hurwitz discussed some recent d e velopments in analysis of metallurgical materials (23Aj, and Paksy has reviewed uses in metallurgy and mechanical engineering (162F). Use of emission spectroscopy in cast iron foundries is discussed by Weber et al. (107D). Malamand described the analysis in the far ultraviolet of refractory carbides in nickel and cobalt-base alloys (9dB),and Jones and Dahlquist analyzed steel samples using a remote arc sampling device (86c). Panteleev et al. compared analysis for nickel alloys using high-voltage and contact sparks, and low-voltage pulse and laser discharges (166F). Metals in Oils. The determination of metals in oils was reviewed by Braier in the biennial applications review covering 1969-1970 (HF). Emission, X-ray fluorescence, and combustion flame techniques constitute the major approaches. Kyuregyan published a book titled “Emission Spectral Analysis of Petroleum Products” in Russian in 1969 (186F), and Rickles and Washbrook included a brief historical review of spectrometric methods for metals in lubrication oils (18%’). Comparisons among optical emission and combustion flame methodologies have been made for iron particles ( I W , 68F) and in general terms (14OF). No doubt that advocates of each technology will continue to make claims and promote various methods until substantial fundamental and systematic improvements are actually accomplished. The development of multielement blends of good metalloorganic oil standards should contribute to reliability of all methods (38D). Nasser and Osman investigated the effects of electrode material, shape, and dimensions, and arc current in the determination of iron, nickel, and vanadium in petroleum crudes (163F). Gases, Gases in Metals. The determination of oxygen in sodium (46F), titanium materials (60F, 83F-86F, 176F), copper (BF), niobium (9@, 63F, 64F), refractory metals (9dB, 64F), and steel (69F)has been reported. Nitrogen analyses in titanium (9dB, 608‘) and steel (69D),and hydrogen determination in titanium alloys (11F) have been discussed. A plasma jet and hollow cathode discharge in He were employed for fluorine

analysis in rocks and minerals using the F 6856.0 %, line (106F, 106F, 193F). A d c arc method for fluorine based on the CaF band emission was adapted for rock samples (196F). Troshkina considered the problem of using this band emission for F analyses from theoretical and practical approaches (222F). Penchev et al. reported the determination of Ne in various gases using the line (168F). Loseke Ne I 5852.5 et al. developed a portable spectrometer to monitor oxygen and hydrogen contaminants in the gas shield of the tungsten arc process (11%). The CH and CD band emissions generated in a low pressure microwave discharge were monitored to determine the presence and extent of labeling in hydrocarbons (134F). The chemiluminescence of the nitric oxide-ozone reaction was studied spectroscopically in the development of an air pollution monitor detector (60F). Sincc a variety of air pollutants can be reacted to produce similar chemiluminescence, the method probably can be extended. Boos studied 19 different gases in a &MHz discharge in the development of a detector for gas analysis (19F), and Shapunov et al. developed a spectrcchromatographic method for detecting microimpurities in gases (801F). Nonmetals. Table VI lists spectrochemical analyses of some nonmetallic materials. Hollow Cathode Excitation. Prakash completed a study of the use of hollow cathode excitation for trace element analysis (177F). Hollow cathode excitation has been applied to the analysis of Se and Te ( I S I F ) , S in CdS and Se in CdSe (188F), impurities in nickel and cobalt oxides (119F), and titanium chloride (17OF), trace elements in solutions (88F),and components in air (86F). High Frequency Plasma Analysis. A number of analyses using highfrequency discharge sources have appeared during the past two years, although many new techniques appear to be in process of development. The reviews by Kleinmann (288A, 98C), Fassel (6,??E),and Robin (166E) included some practical applications, and results obtained by Boumans and de Boer (,??OF),and Carrion de RosaBrussin (13D) verified the potential applications of high frequency discharges. Pforr and Aribot used a 40-MHz inductive plasma for analysis of solids and viscous liquids (172F), and Greenfield and Smith described operating conditions for a 7-MHz, 5-Kw plasma (81F ) . Dagnall et al. studied operating parameters prior to the determination of Be and B in MgO (38F). Korovin and Kuchumov analyzed elements forming refractory oxides by using a 37-

Table VI. Matrix AgCl Aqueous solutions KTafluoride KTaOrKN bO8 Latex LiF Nb oxide Powder Quartz S (vulcanic) Sic, GaAs siliceous material Slag TiCL, TiOl ZrOz

ZnO

ZnS (film)

Spectrochemical Analysis of Some Nonmetallic Materials Elements Desired Technique Reference dc arc arc, solution :impurities

Nb, Ti, Fe, Mol Zr Tal Nb Ca,. Mn, Fe, Cu, Si 10 imDurities 8 elements B B

Mg, Mn, Fe, AI, Si impurities Mg, Fe, Ni, Co, Cu, Mn Hf (100-2000 ppm) 10 impurities Cu. Mn

MHz coaxial, single-electrode plasma arrangement (117F). Savinova and Karyakin determined fluorine concentrations in rocks (193F), and Truitt and Robinson attempted to use the molecular spectra produced from organic compounds introduced into an induction plasma for functional group analysis (223F). Inductive heating of samples to produce atomic vapor reservoirs for analysis was employed by Morrison and Talmi (14787, and Headridge and Smith (90F). Other analysts have used microwaveexcited plasmas for various determinations. April and Hume determined nanogram levels of mercury in water ( 6 F ) , and Taylor et al. analyzed trace molecular impurities in argon (218F). Suzuki determined boron (808F),and W and Mo in binary ferrous alloys (809F) with a magnetron-powered plasma source. Microgram quantities of sulfur were determined in a microwaveinduced plasma in both emission and absorption (813F). West compared a 30-MHz induction with a 2450-MHz microwave discharge for gas analysis as a gas chromatographic detectors (%?OF). Laser Microanalysis. Applications of laser microspectral analysis were included in the book by Moenke and Moenke-Blankenburg (4OA). Hirokawa reviewed the use of lasers in spectrometric analysis (92F). Leutwein described applications in geology (ISOF), and Yamane et al. reviewed applications in metals and nonmetals (208Ej. Analysis of inclusions (148F) and local concentrations (96F, 121F) in steel were described. The sensitivity for nonconductive powders was discussed by Yamane and Matsushita (233F). Other reports included analysis of UOrcermets (,??18F), uranium materials (217F), granite mineral samples (164F), and capacitor paper (26F).

ac arc ark gC arc dc arc ac arc ac arc do arc (Ar atm.) ac arc arc (He atm.) spark

(SOF)

g%)

8

arc hollow cathode hollow cathode (He atm.) dc arc dc arc ac arc

(S@)

W) (B11F)

I%[

(160F) (176F)

(17OF) (171F)

W) (86F. ' &7F)

Webb and Webb observed that conventional methods of quantitative spectrochemical analyses cannot be applied to laser microanalysis, and provided an alternative procedure for semiquantitative laser microanalysis without regard for sample form (898F). A semiquantitative method was described by Schroth (197F). Moenke et al. described the main sources of imprecision (116E). Moenke-Blankenburg described the operation and advantages of a Q-switched laser for microanalysis (144F), and Baldwin studied the Q-switched laser sampling copper-zinc alloys (10E). Gibson et al. obtained calibration curves for Si in Ge-Si alloys and in cement samples by means of a COz laser (66E). Spark Spectrochemical Analysis. Study of the removal of t h e suppressing influence of sulfur, lead, and selenium on elements in ferrous alloy spark analysis was undertaken by Rozsa and Wall (187F). Through a combination of selected capacitor pulse duration, pulse repetition rate, 2.5% hydrogen-97.5% argon atmosphere, containment of the spark discharge area, and carbon counter electrodes, resulfurized steels were calibrated with low alloy steel references. Benta and Coltun used an empirical factor to correct for the influence of carbon on sulfur in vacuum spark analysis of steels ( 1 3 ' ) and Bianchi and Andreini corrected S values for Mn and C content (17F). Clarke described a spectrometric method for carbon in all grades of stainless steel after correction for Mn and Cr content (34F). Goto et al. (73F), Dutta and Guha @ I F ) , and Palatnik and Maricheva (163F) also described spark methods for carbon in steel. The application of spark discharge for analysis of localized heatrresistant layers on steel was described by Kriv-


0

139 R

chikova et al. (IMF), and evaluations of vacuum mectrometer analvses of steels were codducted by Buyaniv et al.

W F ,W ) . Dem’yanchuk et al. mixed charcoal with iron powder in the determination of carbon in charcoal Copper spark methods for nanogram amounts of chromium (1S6F) and 27 trace impurities in plutonium (3F) have been described. A spark determination of hydrogencontaining surface contamination, which contributed to weld porosity in aluminum, was described by Loseke et al. using a He-Ar shielded discharge (1SSF). Solution spark analyses have been reported for micro-amounts of Ti, Zr, and Hf in steel and zircon using the spark-in-spray approach (1lSF), and titanium alloys using the aerosol-hollow electrode method (174F). The rotating disk electrode technique was used for analysis of various alloys used in communications (1OIF), refractory alloys (lOOF), and antique copper alloys (829F). In order to determine low concentrations of S and halogens in solution, salts were electrolytically d e posited on a copper rotrode prior to spark excitation in helium (16F). Dagnall e7 al. described a low-resolution solution spark technique for excitation of C, SI N, and halogens in organic molecules (37F). Tlalka obtained a patent for a rotating disk electrode in which solution was fed under controlled pressure through a hollow central shaft and centrifugally forced to electrode circumference (816F). Muenx demonstrated improved atomization by an admixture of organic solvents to the sample solution in a solution analysis of A1 and Si (149F). Schuhknecht and Boellsterling d e scribed a combined spray-rotating disk electrode, in which a solution was sprayed onto a hot rotrode, and solvent evaporated before the electrode rotated the deposited sample into the sparking region (198F).

(w).

ACKNOWLEDGMENT

Preparation of this review was s u p ported in part by the National Science Foundation (Grant GP 25909) and the Petroleum Research Fund, administered by the American Chemical Society (Grant No. 2055G3).

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(196F) Schoenfeld, I., Appl. Spectrosc. 24, 359 (1970). (197F) Schroth, H., Freemius’ 2 . A n d . Chem. 225, 257-60 (1971). (198F) $chuhknecht, W., Boellsterlin M Col Sp&rOSC. Id. [PToc!: ISih, Sup?, 20s (1971). (199F) Sha&uova, V. P., Yudelevich, I. G., Torgov V. G., Kotlyaresvskii, I. L., Zh. A w l . khim., 26, 930-3 (1971). (200F) Shapiro, L., Develop. Appl. Spectrosc., 8 , 143-57 (1970). (201F) Shapunov, L. A., Parnyuk, N. I., Gosteminskaya, T. V., Kuratova, T. S., Zavod. Lab.,37, 1066 (1971). (202F) Shrader, R. E., Larach, S., Kauffunger, R. A., Anal. Chim. A d a , 54, 162-3 (1971). (203F) Sinha, R. C. P. Singhal, K. C., Banerjee, B. K., Tednology, 7, 165-7 (1970). (204F) Slyusareva, R. L., Kondrat’eva, L. I. Peizulaev, Sh. I., Nikolaeva, 0. d., Zh. Anal. Khim., 26, 894-7 (1971). (205F) Somosi, I., Vitez, J., Banyasz. K o b z Lapok. Kohasz., 104, 40-2 (1971); C.A., 75, 14539t (1971). (206F) Sturlese, S., Morello, B., Quaglia, G. B., Met. Ital., 63 (5), 216-24 (1971); C.A., 75, 71059% (1971). (207F) Susini, J., Tatou, R., Cah. ORSTOM Of. Rech. Sci. Tech. Outre Mer, Ser.Pedol., 8,99-109 (1970); C.A., 74, 134628~(1971). (208F) Suzuki, M., Bunseki Kagaku, 19, 204-7 (1970); C.A., 72, 117349~(1970). (209F) Ibid., 207-12; C.A., 72, 117413g (1978r (210F) Szwaja, A,, Lejda W., Brzysko, T., Zesz. Nauk. Akad. Gorn.-Hutn., Cracao, Ceram., No. 17, 67-75 (1971); C.A., 74, 1507275 (1971). (211F) Takahashi, K., Takahashi, T., Sudo, E. Bunko Kenkyu 18, 311-14 (1969); &.A., 73, 31242s (1970). (212F) Taylor, H. E., Gibson, J. H., Skogerboe, R. K., ANAL.CHEM.,42,876 (,-I -Q.~-O,.\ (213F) Ibid., p 1569. (214F) Tipton, I. H., Stewart, P. L., Develop. Appl. Spectrosc., 8 , 40 (1970). G.. (215F) Tbtsova-Yakovleva. V. ‘ Dvortsin, A. G., Zavod. Lab., 37; 676-9 (1971). (216F) Tlalka, R. Ger. Patent 1,798,323, Nov. 5, 1970; &.A., 74, 71375q (1971). (217F) Tlalka, R., Ustav. Jad. Vyzk. [Ref.], No. 2246-Ch, 38 pp (1969); C.A., 74, 604202 (1971). (218F) Tlalka, R., Colloq. S ectrosc. Int. [Proc.], Ibth, 3, 281 (1969f (219F) Torok, T., Ban, S., Acta Chim. (Budapest), 66, 159-64 (1970). (220F) Torok, T., Ban, S., Magy, Kem. Foly., 76 (6), 294-6 (1970); C.A., 73, 115984~(1970). (221F) Not cited in text. (222F) Troshkina, 0. B., Zh. Prikl. Spektrosk., 14, 583-91 (1971). (223F) Truitt. D.. Robinson. J. W.. Anal. C h i k Acta,’49,’401-15 (1970). (224F) Ustimov, A. M., Chalkov, N. Ya., Zavod. Lab., 37, 660 (1971). (225F) Ibid., p 931. (2261) Veres, G. I., ibid., 36, 1151 (1970). (227F) Yydrevich, E. Z., Karasik, N. Ya., Khanukova, E. Sh., ibid., p 1349. (2283) Webb, N. S. W., Webb, R. J., Anal. Chim. Acta, 55,67 (1971). (229F) Werner, O.,Fresaim’ Z. Anal. Chem., 250, 17-23 (1970). (230F) West, C . D., ANAL.CHEM.,42, 811-12 (1970). (231F) Weszpremi, B., Ontode, 21 (ll), 248-9 (1970); C.A., 74, 106836~ (1971). (232F) Whitehead, A. B., Heady, H. H., Appl. Spectrosc., 24, 225-8 (1970). I

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(233F) Yamane, T., Mataushita, S. Buneeki Kagaku, 20 (9), 1202-4 (1971); C.A., 75, 147404s (1971). (234F) Yudelevich, I. G., Bu anova, L.

M., Proptopopova, N. P., Judina, N. G., Zh. Anal. Khim., 25, 1177-81

(1970 (2353) fiudelevich, I. G.

Shelpakova, I. R., Baturina, Z. d., Zh. Prikl. Spektrosk., 14,373-7 (1971). (236F) Yudelevich, I. G., Shelpakova, I. R., Chanysheva, T. A., Sokolovskaya, I. P., ibid., p 706-9. (237F) Yukshnskaya, L. A,, Zavod, Lab., 37, 436 (1971). (238F) Zakhariya N. F., Anbinder I. S., Pashxova, L. i., Vustyanyuk, h. V., Zh. Anal. Khim., 26, 1163-6 (1971).

(239F) Zskorina, N. A,, Lazeeva, G. S.,

(244F) Zimmer, K., Ikrenyi, K., Magy. K w . Foly., 76 (2), 78-83 (1970); C.A., 73,21038r (1970). (245F) Zivanovic-Magdic,V., M&lurg$a (Sisak, ~ u g O S h U N Z ) ,9 (3), 28-9 (1970); (240F) Eksp. d& dovskayal eo~No. ol.,T’ 2, N63-7 *l Tr*(1970); Inst‘ C.A., 74, 134583d (1971). C’A’l 749 124385r (1971)* (246F) Zmbova, B., Isotopenpraxis, 7 (2), 57-9 (1971); C.A., 74, 106827t (241F) Zhigalovskaye, T. N. EgoFv, (1971). V. V., Makhon’ko E. P., fiervunina, R. I., Shilina, A. b’., ibid., pp 45-53; (247F) Zmbova, B., Talanta, 18, 755-9 C.A., 74, 115723h (1971). (1971). (248F) Zmbova B., Tehnika (Belgrade), (242F) Zhiglinskii, A. G., Kalmakov, A. A., Fafurina, E. F., Zh. Anal. Khim., 25, 1165-9 (1970); C.A., 74, 9327x 25, 1297-300 (1970). (1971). (243F) Zimmer, K., Ikrenyi, K., Spectre (249F) Grant, C. L., Deuel. Appl. Specchim. Acta, 25B, 425-35 (1970). trosc., 8, 216 (1970).

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Flame Spectrometry 1. D. Winefordner,’ Department of Chemistry, University of Florida, Gainesville, Fla. 3 2 6 0 I 1. 1. Vickers,2 Department o f Chemistry, Florida State University, Tallahassee, Fla. 3 2 3 0 6

T

HIS IS THE SECOND fundamental review on flame spectrometry prepared by the present authors. This review covers articles published in 1970 and 1971 as well as some appearing too late or overlooked in 1969 and so were not included in the previous review ( H A ) which included primarily articles published in 1968 and 1969. Because of the great wealth of papers in the area of flame spectrometry and because of the nature of this review, it is not possible to review all papers, and so the following guidelines were used in preparing the present review. First, only papers of a fundamental or general methodological nature are included, i.e., few papers concerning applications of flame spectrometric methods are included. Second, only papers directly related to or useful in flame spectrometry are included, e.g., this review contains no references to emission of species in high frequency discharges, in microwave discharges, in dc plasma jets, etc. Third, only papers published in journals having a diversified editorial board and utilizing a review system are included. Therefore, no references to trade journals and to journals published by instrumentation companies are included in this review. This latter decision was difficult to make because several of the instrumentation company journals, e.g., Perkin-Elmer’s Atomic Absorption Newsletter, are probably better edited and reviewed

1 Work supported by AFOSR (AFSO) U.S.A.F. Grant No. 70-188OC. 2 Work sup orted by National Science Foundation &ant GP 24260.

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than some of the journals to be referenced here. Nevertheless, in order to maintain consistency, no references to trade and instrumentation company publications will be given in this review except in part A where general reviews of flame spectrometry will be cited. Fourth, the authors of this review may have overlooked a paper of basic importance to flame spectrometry and we hope it isn’t one of our own or one of the leaders in the field. This review, like the previous one, is divided into five sections: Reviews, Books, and Bibliographies; Fundamental Studies; Atomic and Molecular Emission Spectrometry; Atomic Absorption Spectrometry; and Atomic Fluorescence Spectrometry. During the two years of this review, flame emission seems to have made several giant steps forward and is now considered by many workers to be complementary with atomic absorption spectrometry. The first commercial instrument for multielement analysis by atomic fluorescence spectrometry has appeared, and one would be tempted t o say that atomic fluorescence spectrometry has now found a place in the great array of analytical methods for trace metal analysis. Also during the past two years, nonflame cells have really caught on and are being used by many for analysis of trace metals in biological samples, in petroleum products, etc., despite a rather poor understanding of the processes involved in the atomization process. This review will cover the above concepts and techniques as well as others of fundamental interest to analytical chemists.


REVIEWS, BOOKS, AND BIBLIOGRAPHIES

Several fine books on flame spectrometric methods have appeared during the past two years. Mavrodineanu (46A) is the editor of an extensive volume on analytical flame spectroscopy. This volume contains chapters on theoretical aspects, instrumental requirements, methodology and applications of atomic absorption, atomic fluorescence, and flame emission spectrometry. The various chapters are written by experts in the various areas of flame spectrometry. The first chapter concerning the vaporization and atomization processes as well as excitation of atoms in flames is written by Alkemade. The second chapter by Menis and Rains is concerned with sensitivity, detection limit, precision, and accuracy in flame methods. Mulla-Herget discusses some considerations on optical design and selection of spectroscopic instruments in the third chapter. Cath discusses the principles of electronic instrumentation in Chapter 4. Gilbert discusses flame spectrometry of nonmetals in Chapter 5, and Kniseley, Fassel, and Butler discuss atomic emission and absorption of rare earth elements in Chapter 6. I n Chapter 7, Bleekrode is concerned with spectroscopic investigations of low pressure oxy-acetylene flames. Pinta discusses agricultural applications, and Herrmann discusses biological applications of flame spectrometry in Chapters 8 and 9, respectively. I n Chapters 10 and 11, Willis discusses atomic absorption spectrometry and Winefordner and Smith discuss atomic fluorescence spectrometry, respectively. In Chapter 12, Burger, Gillis, and Yamasaki discuss

Emission spectrometry - Analytical Chemistry (ACS Publications)

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