(770) Yoshizawa, S., Tsuruta, T., Yamakawa, K., Boshoku Gijutsu, 24, 511 (1975); CA, 85, 116140e. (771) Yudelevich, I. G., Cherevko, A. S., Spectrochim. Acta, Part 6, 31, 93 (1976); CA, 84, 188910h. (772) Yusaf, M., Sixta, V., Sulcek, Z., Collect. Czech. Chem. Commun., 40,3652 (1975); CA, 84, 159 178v. (773) Zabavnikov, V. A,, Sakharnikov, P. A,, Korolev, E. F., Okunev, L. R., Blokhin, M. A,, DuiEvlanov, makaev, S. I., Nikol’skii, A. P., Belitskii. I. Z., I. Y.. Ural. Konf. Spektrosk. (TezisyDokl.),7th 1971, 1, 9 (1971); CA, 81, 114201~. (774) Zaghioul, R., Obeid, M., f a k . J. Sci. lnd
Res., 17, 154 (1975); CA, 83, 1574212. (775) Zakasovskii, G. V., Plotnikov, R. I., Soskin, E. E., Filipov, V. A., Khislavskii, A. G., Appar. Metody Rentgenovskogo Anal., 10, 108 (1972); CA, 82, 7995 1k. (776) Zakharchenko, E. V., Osadchii, V. V., Dronyuk, N. N., Sergeeva, A. A., Rudenko, N. G., Ravich, Y. S., Vysokoproch. Ghugun s Sharovid. Grafitom, 32 (1974); CA, 83, 52047q. (777) Zapletal, L., Kukula, F., Vins, B., Ustav Jad. Vyzk. (Rep.),3163-Ch (1973); CA, 83, 141381a. (778) Zapletal, L., Kukula, F., Vinsh, V., Ustav Jad. Vyzk. (Rep.), UJV-3163-Ch (1973); CA, 82, 92656n. (779) Zhandarova, E. I., Opaleva, L. V., Zavod.
Nonferrous Metallurgy-Light Titanium, and Magnesium
Lab., 41,925 (1975); CA, 84, 2 5 4 4 5 ~ . (780) Zhandarova, E. I., Opaleva, L. V., Zavod. Lab., 42, 153 (1976); CA, 85, 136668m. (781) Zhdanov, A. K., Masiova, V., Jatrudakis, S., Deposited Pub/.,VlNlTl 5367-73 (1972); CA, 85, 56222~. (782) Zheltukhina, L. D. Chernenko, V. I., Grigorkina, V. A., Ural. Konf.Spektrosk. (Tezisy Dokl.), 7th 7971, 1, 100 (1971); CA, 82, 38227k. (783) Ziolowski, 2., Stronski, B., f r . lnst. Hutn., 27,49 (1976); CA, 85, 103331t. (784) Zueva, V. L., Isaev, V. F., Danilovich, Y. A,, Izmanova, T. A., Ignat’ev, V. G., Proizvad. Ferrosplavov, 2, 101 (1973); CA, 82, 50909s.
Metals: Aluminum, Beryllium,
H. J. Seim,” Russel C. Calkins, and Julie A. Macksey Kaiser Aluminum & Chemical Corporation, Center for Technology, Pleasanton, Calif. 94566
This is the sixteenth review on nonferrous metallurgical analysis and covers the two-year period from September 1974 through August 1976 as documented by Chemical Abstracts, Analytical Abstracts, World Aluminum Abstracts, and Government Reports Announcements. The following journals also were surveyed for the same period: Analytical Chemistry,
Applied Spectroscopy, Analytica Chimica Acta, T h e Analyst, and Talanta. Wherever possible, the abstract number of the abstracting service has been included in the bibliographic citation. As in the past (241),this review is limited to those analytical methods of interest in the nonferrous metals industry. Many interesting methods potentially applicable to this field are not included because of space considerations. However, some general methods are included because they appear to the authors to be particularly useful or novel. Recent books related to the analysis of light metals include: Tikhonov’s “Analytical Chemistry of Magnesium (Analytical Chemistry of the Elements)” (268); “Flame Emission and Atomic Absorption Spectrometry: Elements and Matrices,” Volume 3, edited by Dean and Rains, which contains a section on the determination of beryllium and aluminum as reviewed by Chakrabarti (43) and a section by Kriege et al. who review the determination of titanium (150); in “Determination of Gaseous Elements in Metals (Chemical Analysis Series, Volume 40)”, Covington and Miles (52) review the determination of hydrogen, nitrogen, and oxygen in titanium, while Holt reviews the determination of these gases in aluminum (114).
Atomic Absorption. Preconcentration using solvent extraction or carrier precipitation followed by atomic absorption continues to be a useful technique employed by many authors to determine trace metals in high purity light metals and their alloys and compounds. Malusecka et al. (164) used coprecipitation with La(OH)3 or extraction of the diethyldithiocarbamate complexes in MIBK to determine Cu, Fe, Mg, Ni, Pb, Cr, Cd, Mn, and Zn in high purity aluminum. Musil (188) separated P b and Sn from A1 with trioctyl phosphine oxide and Vicentini (282) separated Fe, Cu, and Zn by extraction with APDC in ethyl acetate. Young (290) used coprecipitation with Zr(0H)d to determine Ca, Fe, Ti, Si, V, Zn, and Mn in A1203and cryolite. Furnace atomic absorption using 0.5 to 10 mg of solid sample was applied to the determination of Ga and In in Al, A1203 and bauxite by Langmyhr and Rasmussen (156). Furnace atomic absorption was also used by Hudnik and Gomiscek (116)to determine Cd, Co, Cu, Fe, Ni, and P b in high purity A1 after extraction with ammonium tetramethylenedithiocarbamate. A different approach to preconcentration was reported by Hoehn et al. (112)whddissolved a 10-25 g A1 sample having a thin coating of Hg in HC1 until a few mg of residue remain. The residue having the trace ele72R
ANALYTICAL CHEMISTRY, VOL. 49, NO. 5, APRIL 1977
ments enriched by lo3a t >95% recovery is then dissolved and determined b atomic absor tion. Detection limits of 0.02-2 Fglg with a refative standartdeviation of 5% are claimed for Bi, Cd, Ga, In, Pb, T1, and Zn. A critical review of atomic fluorescence for the analysis of aluminum alloys using multichannel instrumentation was published by Browner (32). New methods for preparing metallic aluminum samples for atomic absorption were reported by Ghiglione et al. (92) and Human et al. (117).Ghiglione prepared a colloidal suspension by means of a water immersed spark using a new type of disperser. These dispersions show the same behavior as true solutions in atomic absorption and are stable for several hours. Human used a conventional high-voltage spark as a sampling-nebulizing device for metal samples. Gas passing through the spark chamber transports the metal particles into the flame. The technique was also applied t o atomic fluorescence and inductively coupled plasma emission spectrometry. The use of H3P04to dissolve difficultly soluble metal oxides for analysis by atomic absorption was reported by Hofton and Baines (113) and by Tamnev et al. (258). Hofton and Baines used the technique to dissolve MgO and Tamnev determined Na and Mg in P-Al203. Optical Emission Spectroscopy. Emission spectroscopy continues to be one of the more important analytical techniques in the light metal industries. Several papers of a theoretical nature were published during the past two years. Stachova (250) studied the effect of alloying components, the discharge gas, and the state of the electrode surface on the analysis of A1 alloys in a high-voltage spark discharge. Kazennova and Taganov (132) also studied the effect of structure and examined the feasibility of decreasing its effect on the spark spectra of A1 alloys by etching. Studies showing the advantages of an Ar atmosphere for sparking aluminum samples were reported by Strasheim and Blum (252) and by Slickers et al. (247). Both articles claimed better homogeneity in the microfusion area of the sample and, therefore, a marked decrease in interelement effects resulted. Strasheim and Blum used a scanning electron microscope and an energy dispersive x-ray analyzer in their investigations. Kubota and Ishida (151) found that a 20 to 1volume mixture of Ar and 0 2 improved the spectrochemical sensitivity for determining Mg and Zn in A1 alloys using a laser microprobe with auxiliary spark excitation. Berenshtein et al. (22) described a mathematical method for determining the optimum composition of spectrographic buffers for determining Be in carbonate and silicate minerals by comparing calibration curves. Marinkovic et al. (168) developed a gas stabilized arc for determining metals in solution. An accuracy and reproducibility study of spectrometric methods for high purity A1 and A1 alloys was reported by
H. Jerome Seim is Manager of the Analytical Research Department, Center for Technoiogy, Kaiser Aluminum & Chemical Corporation, Pieasanton, Calif. He received his B.A. degree from St. Oiaf College, a M.S. degree from Montana School of Mines and a Ph.D. (1949) from the University of Wisconsin. He was an analytical chemist for Boeing from 1943 to 1945. He was a member of the Chemistry Department at the University of Nevada in Reno from 1949 to 1962. in addition to teaching and directing research in analyticai and inorganic chemistrv. he was also a research consultant for thkU.S. Bureau of Mines. From 1962 to 1969, he was Manager of Chemical Research for Allis-Chaimers in Milwaukee. He assumed his present position in 1969. He is a member of the American Chemical Society, the Electrochemical Society, the American Society for Testing and Materials, Sigma Xi, Phi Kappa Phi, and Phi Lambda Upsilon. His research Interests are centered on trace eiement analyses involving ion exchange, radiochemistry and a variety of instrumental methods and has published numerous papers In this field. Dr. Seim Is currently chairman of ASTM E.03.05.01on the chemical analysis of aluminum and also the chairman of a special analytical task group on polycyciic organic materials for the Aluminum Association. ~~~
~~
~
Russel C. Calkins is a staff research chemist at Kaiser Aluminum & Chemical Corporation’s Center for Technology in Pleasanton. Calif. He received his B.A. from the University of Northern iowa and his R.D. from the University of Wisconsin. His research has been in the development of analytical methods for six years with the Dow Chemical Company, and for the past fifteen years with Kaiser Aluminum & Chemical Corporation. His research interests include appiications of ion exchange separations, atomic absorption spectrophotometry, and electrochemistry. Recent activities have been concerned with methods for the determination of trace metals of environmental interest. Dr. Calkins is listed in American Men of Science, and he is a member of ACS, AAAS, SAS, Sigma Xi, and Phi Lambda Upsilon.
Julie A. Macksey is a Technical information Specialist, Kaiser Aluminum & Chemical Corporation, Center for Technology, Pleasanton, Calif. She received her B.S. in chemistry from Webster College and an M.S. in library science from San Jose State University. From 1953 to 1966, she was employed In the analytical research laboratories of the Titanium Division of National Lead Company, Mallinckrodt Chemical Works, and Petroiite Corporation, all of St. Louis, Mo. In 1966, she entered the technical information field and joined Kaiser in 1967 in her Dresent caoacitv. She is a member of Beta Phi Mu, the American Chemical Society, the American Society for information Science, and is currently serving on the board of directors of the San Francisco Bay Region Chapter of the Special Libraries Association. She is a part-time faculty member in the Librarianship Department of San Jose State University where she teaches a course in the Literature of the Sciences.
Mannweiler (166). Cylindrical and disk samples containing Mg, Si, Cu, and/or P b were analyzed by 27 laboratories. Reproducibility depended more on sparking conditions and alloy composition than on shape of the sample. Accuracy was dependent mostly on the standards used although it was affected by the sparking conditions. Reproducibility for high alloy materials was better by x-ray spectroscopy, except for Si. Preconcentration was also used by several researchers in emission spectroscopy to increase the sensitivity for determining microcomponents in pure materials. Gregorowicz and Studencki (99) applied a two-step precipitation using 12 N HC1 followed by gaseous HC1 to enrich 10 trace metals in high purity aluminum by factors of 130 to 180 times. Detection limits of 0.1 to 1 kg/g were claimed. Mizuike et al. (182) utilized carrier precipitation with Sn(OH)4to separate 1to 5 kg quantities of Fe, Co, Cu, and Zn from 1g of high purity magnesium. Most of the tin was volatilized as the bromide before subjecting the residue to emission spectrography. Extraction
of the cupferron complexes of Fe, Cu, Co, Ti, and Sn into chloroform was used by Freger et al. (90) for spectrochemical determination in high purity MgC12. Improving the sensitivity of spectrographic analysis by using carrier distillation was applied to AI by Tikhonova et al. (273)using a Ga carrier; to Ti02 by Kat0 et al. (130) using GaF3; to Ti02 by Zakhariya and Turulina (293) using AgCl; and to Ti and Ti02 by Turulina and Zakhariya (275) using AgCl or AgI. The latter two papers also used a 6% mixture of NaCl with graphite in the crater of the counterelectrode to improve volatilization of impurities. Grikit and Galushko (101) significantly improved the distillation effect in the determination of eight impurities in Ti by grinding the sample electrode to a “wine glass” shape. The application of an induction-coupled high frequency plasma source to the emission spectrographic analysis of solutions of A1 alloys was reported by Kirkbright (138) and Kirkbright and Ward (137). Results were also compared to atomic absorption and multielement atomic fluorescence. The plasma source was found to give a wider linear calibration range owing to the greater freedom from self-absorption. The longer residence time of analyte species in the plasma also gives freedom from solute vaporization interferences. All plasma emission results were obtained a t a single dilution (1 g/100 mL) on samples containing up to 4.5%Cu, 5%Mg, and 6% Zn. Several dilutions were required to analyze these Samples by atomic absorption or fluorescence. Simonova and Raikhbaum (244)analyzed beryl by injecting a mixture of the sample powder with C and NaC104 in a gas stream into a torch plasma of an electrodeless ultrahigh frequency plasmatron. Calibration slopes are not affected by particle size with the plasmatron but decrease with increasing particle size when using an arc plasma. X-ray Methods. X-ray techniques continue to assume a more important role in light metals analysis. Dubakina et al. (74) report the direct spectrometric analysis of polished samples of bauxite by comparing to pure reference standards and employing concentration curves to correct matrix errors. Sajo (236) fused bauxite samples in Borax to obtain analyses for Al, Si, Fe, and Ti with a relative error of 2-3% and determined Ca from an additional pelletized powdered sample. Matocha (170) describes an automated lithium tetraborate fusion x-ray spectrometric procedure that is capable of analyzing for eight elements in bauxite, processed mud, clay, and A1 ores. Tertian (264) described a rapid x-ray calibration system employing influence coefficients and illustrates the application of the method in the analysis of bauxites. Luschow (158) employed electron beam excitation to obtain x-ray spectrometric analysis of the Na, Al, Ca, F, and 0 in cryolite bath and advanced the method as a possible way to determine excess AlF3 in reduction cell electrolyte. A method for predicting the anomalies that are evident in the x-ray analysis of aluminum metal was described by Kemper (234).Gurvich et al. (103) describes a system of x-ray excitation and filtration to analyze for contaminants in A1203. Yamamoto et al. (288) employed precipitation reagents to separate Cu, Zn, Fe, and Ni from Mg and Al. The elements collected on a membrane filter are analyzed by a simple XRS procedure. They (289)used a similar procedure to determine Mn and Fe in Ti. Dubinchuk et al. (75) combined electron microscopic and x-ray diffraction data to quantitatively determine the phase composition and relationships and degree of crystallinity of bauxites. Fotic and Misovic (88) used both theoretical and experimental calibration curves to develop a determination for gibbsite and boehmite in bauxite. Habla and Wolanczyk (106)utilized both direct comparison and internal standard x-ray diffraction methods to quantitatively determine the anatase and rutile contents in titanium white. Kramer (148) devised an x-ray diffraction method for determining the phase purity of bauxite to a precision of 5f296. Microanalysis of Surfaces. There was a significant increase in the number of papers on surface and microanalysis of light metals and their oxides in this review period. Young (291) has reviewed instrumentation for the chemical analysis of surfaces including ESCA, electron microprobe, and Auger spectroscopy. Eguchi et al. (80, 81), using ESCA, measured the binding energies of Al, 0, and S atoms in anodic oxide films found on A1 in different electrolytes and also measured the amount of sulfur in the film as a function of anode POANALYTICAL CHEMISTRY, VOL. 49, NO. 5, APRIL 1977
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Table I. Methods for Nonferrous Metallurgical Materials
Material A1
Determinations 21 Impurities
Cr, Cu, Ga, Hf, Co, Fe, Sc Cu, Fe, Mg, Mn, Ti, Zn Ga, In
c,s
Impurities Ga, In Cu, Zn, Fe, Ni 0 ,c , N High purity A1 Zn, Mg, Fe, Cu, Ni, Mn, Cr, Pb, Cd, V, Ti Ti, V, Ni, Mn, Cr, Fe, Ga, Cu, Mg, Zn Trace elements Cd, Co, Cu, Fe, S i , Pb Cu, Fe, Mg, Ni, Pb, Cr, Mn, Cd, Zn Fe, Cu, Zn Ti, V, Cr, Fe, Ni, Cu, Zn A1 alloys Cu, Fe, Mg, Mn, Ni, Zn, Bi Cu, Mg, Mn Cu, Mg, Zn Mg, Zn Au, Ag, Co Pb, Sn Zr, Hf Zn, Cd A1 Compounds Impurities Ca, Fe, Ti, Si, V, Zn, Mn A1203 Na, Mg Na, V, Ca, Zn F, P, B Fe, Cr Fe, Ca, K Ga, In Trace elements Be Cu, Pb, Cd, Ni, Zn, Co, W, Mo, V, Bi, T1, V, U, Fe, A1 Be ores Be, Ba, B Bauxite, red mud Al, Si, Fe, Ti, Ca Si, A1 U, T h Phase analysis Phase analysis Ga, In Si, Fe, Ti, Al, Ca, Na, K, Mg Phase analysis Al, Fe, Si, Ti Cryolite (bath) SiOn, F, Fe, Na, A1 Sa, Al, Ca, F, 0 Dolomite Ca, Mg Fe, Al, Ca, Mg Ca, Mg Ca, Mz Fe, Co, Cu, Zn Mg alloys Al, Zr Cu, Zn, Fe, S i Fe, Cu, Co, Ti, Sn MgCb Chlorides of K, Na, Ba, Ca, Mg MgClz bath Ti Mn, Fe Impurities 0 ,N 0. N 0 : N. H Sn, A1, Si, Fe, Cu, Mn, Cr, Ni 0, N 0 ; N, H Impurities Mn, As, V Ti02 V, Cr, Mn, As Phase analysis Nb, Zr Mn, Cr Impurities Impurities Pb, Sn, Si, Mg, Fe, Al, Cu, Co, Mn, Ni, V 74R
ANALYTICAL CHEMISTRY, VOL. 49, NO. 5, APRIL 1977
Methoda S NA S, AA, AF FAA E S P XRS rA AA S AA FAA AA AA PA AF AA AA, AF, S S FAA AA F P S AA AA P, AA P ESR XRS FAA SA V S XRS NA NA XRD IR FAA XRS T XRS P, C, FP, AA XRS C C T
v
S c,p XRS S E XRS S GC MS S S EP MS SA NA SA XRD
P, XRS AA S S S
Table I (Continued) Material
Determinations
Ti ores
Fe, Ti, V, Ca, Mg, A1 Mn, Cr Phase analysis Impurities
Tic14
Methoda
References
AA, atomic absorption; AF, atomic fluorescence; C, chemical; E, electrochemical; EP, electron probe; ESR, electron spin resonance; F, fluorometric; FAA, furnace atomic absorption; FP, flame photometric; GC, gas chromatography; MS, mass spectrometric; NA, neutron activation; PA, proton activation; ?A, gamma activation; P, photometric; PT, physical test; S, spectrographic; T, thermometric; V. voltammetrv: XRD, x-rav diffraction: XRS. x-ray sDectroscow. (2
Table 11. Methods for Elements in Nonferrous Metallurgical Materials Determination A1° A1
Material A1 carbide General General AlzOa-based catalysts General General General General Mg alloys Mg alloys Bauxite Cryolite electrolyte Cryolite electrolyte Cryolite electrolyte Aluminate solutions Aluminate solutions A1 A1 alloys General Beryl A1 alloys General General Beryl General General General General Genera1 General A1 alloys General Genera 1 General General General General Be-Cu, beryl Beryl General General
B
Ca C Ce Cr cu
General Mg alloys A1 alloys Cryolite electrolyte MgO Ti Mg alloys General A1 A1 alloys A1 alloys
Method Volumetric Furnace atomic absorption Complexometric Complexometric (micro) Photometric-Chromazurol S Photometric-Pyrocatechol Violet-borate Fluorometric-Schiff bases Fluorometric-Sodium-2-quinizarinsulfonate Complexometric Photometric-Chromazurol S and cetyltrimethylammonium bromide Neutron activation Electrochemical Luminosity Dissolution rate Conductometric Nuclear magnetic resonance Microwave emission of AsHz Photometric-Mo(V) Blue Photoneutron Deutron activation Spectrographic Complexometric Volumetric Gravimetric-2'-Hydroxychalcone Gravimetric-N-Benzoyl-o -tolylhydroxylamine Gravimetric-Nitrilotrimethylphosphonate Gravimetric-4-Chloro-2,5-dimethoxyacetanilide Gravimetric-Benzidine-fluoride Atomic absorption Furnace atomic absorption Extraction-Atomic Absorption Fluorometric-2- (2-pyridy1)phenol Fluorometric-1 -Hydroxy-2-carboxyanthraquinone Fluorometric-H ydroxyflavones Fluorometric-3-Hydroxy-2-naphthoicacid Fluorometric-Schiff bases Solid state luminescence Photometric-Pertitanate Photometric-Eriochrome Cyanine R Photometric-Chromazurol S-Hexadecyltrimethylammonium ternary complex Photometric-p-phenylenediaminehexacyanochromate(II1)ternary comp 1ex Photometric-Bisazoic derivatives Solvent extraction Spectrographic Volumetric Complexometric Manometric Amperometric Atomic absorption Spectrographic, glow discharge Electrochemical Coulometric ANALYTICAL CHEMISTRY, VOL. 49, NO. 5, APRIL 1977
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Table I1 (Continued)
Determination
Material A1 alloys A1 alloys Ilmenite
F Ga
He H
In Fe
A1203
HF emissions (Al) A1 A1 A1 A1 A1203 A1 A1 compounds Al, A1 compounds A1 A1 A1 Aluminate solutions A1 Al, A1 alloys Al, A1 alloys Al, A1 alloys Al, A1 alloys A1 A1 Al, Ti, alloys Ti Ti Ti Ti Ti hydride Mg, Mg alloys A1
A1 alloys A1 alloys Ti02
Pb
MgO Mn Ni N 0
Al, A1 alloys A1 Ti02 General High purity A1 A1 alloys General General Mg, Mg alloys A1 A1 Be Ti, Al, Be
A1 A1 Al, A1 alloys A1
.
Al, Ti Pd P
Si Ag Na
Ti Ti Ti alloys
Ti A1203coatings A1 alloys A1 alloys A1-Si alloys (molten) A1203
Cryolite S
A1
Sulfate Ta Sn
A1203 A1203 coatings Tic14 A1 alloys A1 alloys
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Method Extraction, atomic absorption Chemiluminescence Furnace atomic absorption Ion-selective electrode Ion-selective electrode Furnace atomic absorption Amperometric Inverse voltammetry Neutron activation Neutron activation Fluorometric-8-Quinolinethiol Fluorometric-Acridine Orange Extraction, spectrographic Photometric-Rhodamine B Photometric-Phenylenebis(fluor0ne) Photometric-4-Methyl-2-( 2-hydroxyl- 1-naphthylazo)thiazole Photometric-Glycinecresol Red (Y Scattering New methods review Vacuum extraction N2 fusion, thermal conductivity Vacuum gas test, mass spectrometer Spectrographic Reaction gas chromatography N2 fusion, thermal conductivity Spectrographic Spark, furnace, laser microprobe Thermal extraction, mass spectrometer Vacuum extraction Vacuum decomposition Vacuum fusion, capsule method Photometric-4- (6-Methoxy-3-methylbenzothiazolylazo-N-methyldiphenylamine Photometric-Glycinecresol Red Polarographic Photometric, polarographic Atomic absorption 3He activation Furnace atomic absorption Atomic absorption Atomic absorption Complexometric Complexometric Photometric-Hydroxyazo dyes Selective solubility Neutron activation Photometric-Phenanthroline-xanthene dyes y Activation Photometric-Thymol Vacuum fusion 3He activation Neutron activation Proton activation Neutron activation He fusion, gas chromatography Inert gas fusion Photometric-Nitroso-R-salt
Atomic absorption X-ray spectroscopy Neutron activation Extraction, atomic absorption Potentiometric Ion-selective electrode Volumetric Volumetric Photometric-Dimethylphenylenediamine Turbidimetric Photometric-Crystal Violet Photometric-Cationic Pink 2s Photometric-Gallein
ANALYTICAL CHEMISTRY, VOL. 49,
NO. 5,
APRIL 1977
Table I1 (Continued) Determination T1 Tio Ti
Method
Material A1 alloys Ti carbide, nitride General Alunite
General General General General General General A1 alloys A1 alloys Bauxite General Ilmenite Hydrocarbons Ti Tic14 Tic14 Tic14 Rutile HzO (surface) A1203 HzO, OH Al, Be oxides Zn A1 alloys A1 alloys AI alloys Bauxites Mg alloys A1 alloys Zr A1 alloys Ti Ti
Extraction, atomic absorption Selective solubility Complexometric Photometric-1-( 2-Allylphenoxy)-3-(diethylamino)-2-propanol:thiocyanate Photometric-Isonicotinic acid naphthalhydrazide Photometric-2-Carboxyphen ylazopyrogallol Photometric-Trihydroxyfluorones Photometric-Phenylhydroxy1amine:phenylfluorone Photometric-Pyrocatecho1:pachycarpine Photometric-Diantipyrylmethanes Photometric-Diantipyrylmethane Photometric-Cinnamolyphenylhydroxylamine
Neutron activation, x-ray spectroscopy Polarographic Radioisotopic x-ray spectroscopy Polarimetric Spectrographic X-ray spectroscopy Photometric-Anthranilic acid acetonehydrazide Photometric-4-(2-pyridylazo)resorcinolor N phenylbenzohydroxamic acid Photometric-Fe(III), 1,lO-Phenanthroline Methylmagnesium iodide Infrared spectroscopy Atomic fluorescence Atomic absorption Photometric-Dithizone Atomic absorption Photometric-5-( 2-Quinolylazo)-2-monoethylamino-p-cresol Photometric-p -Methylphenols Photometric-Arsenazo(II1)
Photometric-Zirconin Isotope dilution
tential. Croset et al. (54) discussed techniques for the surface analysis of metals including A1 using ion back-scattering by Auger electrons and ions from 1to 7 keV. Smith (248) examined oxide films on aluminum by Auger spectroscopy during ion sputtering and found that the electron and ion beams change the surface chemistry during analysis by reduction of Al(II1) to Al. Using an ion microprobe and Auger electron spectroscopy, Abe et al. ( 1 ) found that a black water stain formed on etched A1 in boiling water was due t o traces of Fe. Doig et al. (69) measured concentration profiles across grain boundaries in A1 alloys using transmission electron spectroscopy combined with electron energy analysis or x-ray microanalysis. The effect of the valence band spectra on the determination of light elements using the electron microprobe was discussed by Grasserbauer (97).Using the additional K, band that appears when oxide is present on Al, Wolfgang (287) determined the oxidation state of A1 from the intensity ratio of the K, band of the sample and a standard oxide. Mitchell and Sewell (180)determined oxygen in thin oxide films on A1 using the electron microprobe. The surface chemistry of highly dispersed A1203 was studied by Chuiko et al. (49) using infrared spectrophotometry. Other Instrumental Techniques. Other noyel techniques applied include the use of high energy Li+ ions to characterize the element distribution in anodic films on A1 by Thomas et al. (265);the measurement of the thickness of oxide films on thin A1 foils using 14 MeV neutron radiation by Dugain and Michaut (77);and the application of electron spin resonance to the determination of Fe and Cr in A1203 by Csermak (55). A compilation of procedures for the determination of multiple constituents in light metal materials is given in Table I. Some of these procedures have been highlighted in the introduction. Table I1 is a compilation of procedures arranged according to the element determined. Selected procedures are described briefly in the following discussion. Aluminum, Methods for the separation of aluminum from
a large number of metal ions by anion exchange in malonate solutions were described by Sitaram and Khopkar (246).Acid and elemental interferences in the determination of aluminum by atomic absorption were studied by Musil (189).A strong suppressive effect was shown by Si and positive effects by other elements. Maruta et al. (169) studied the determination of aluminum by furnace atomic absorption. Metallic A1 was determined in aluminum carbide by Szabo et al. (256) by dissolving the metal with HgCl2 in anhydrous ethanol and titrating the C1- formed with Hg(N03)Z using diphenylcarbazone as indicator. Aluminum carbide does not react. Increased selectivity in the complexometric determination of A1 with EDTA was claimed by Tikhonov and Budnichenko (269).After the usual titration with excess EDTA and ZnCl2 with xylenol orange indicator, the A1-EDTA complex was decomposed by boiling with fluoride and the released EDTA titrated with ZnCl2. They (272) applied the method to the determination of A1 in Mg alloys. A micromethod for the complexometric determination of A1 in alumina-based catalysts involving back-titration of excess DCTA with lead acetate was described by Sanchez-Pedreno e t al. (238). Fluorometric methods for determination of aluminum were described by Capitan et al. (41), using sodium 2-quinizarinsulfonate, and by Morisige (183)’ who found nine Schiff bases to be sensitive reagents. Several papers were published on photometric methods for the determination of aluminum using ternary complexes. Mal’tsev et al. (163) found that the reaction of A1 with pyrocatechol violet and boric acid was instantaneous and that the color is stable for several hours. The calibration curve is linear from 1 to 56 kg A1/50 mL. Nishida (200) and Tikhonov and Yarkova (271) used the ternary complexes formed with Chromazurol S and quaternary alkylammonium salts. Beer’s law was followed up to 10 Mg A1/50 mL and the molar absorptivity is -lo5. The method was applied to the determination of A1 in Mg alloys (271). ANALYTICAL CHEMISTRY, VOL. 49, NO. 5, APRIL 1977
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Alumina. Three types of methods were described for the determination of Alz03 in cryolite electrolyte used for the production of aluminum. Thonstad (267) and Hannah and Welch (108) used a chronopotentiometric method with graphite electrodes. The Thonstad method is based on a transition time, which is a measure of the time needed to deplete the melt a t the electrode surface with respect to oxygen ions. Hannah and Welch determined Alz03from the current and potential a t the appearance of the anode effect. Iuchi (124) determined Alz03 in cryolite by measuring the luminosity of rapidly solidified melt. Keller and Frei (133) determined Alz03in cryolite melts by measuring the speed of dissolution of solid rods of sintered A1203 The solution rate is measured as the change in diameter after immersion and rotation of rods a t constant speed for a fixed time or by the time required to dissolve a known thickness on an inert substrate. Articles describing improvements in methods or instrumentation for determining the composition of aluminate liquors include those of Averbukh et al. (12),Farkas et al. (85, 86) and Mazumdar and Ray (175). A new instrumental method using nuclear magnetic resonance for determining A1 concentrations and A1 to Na ratios in aluminate solutions was patented by Simpson (245).The method uses a 3-compartment cell, one for the sample and two for two different reference solutions. Arsenic. Tel'nik (262) determined As in A1 alloys by generating arsine and trapping it in iodine solution to form arsenate. The arsenate is treated with molybdate and reduced to molybdenum blue. Sakamoto et al. (237) determined As in A1 by a microwave emission method. They also generated arsine during the dissolution step but trapped the AsH3 in liquid nitrogen using a Nz carrier gas. The AsH3 was introduced into a quartz argon discharge tube, excited with a microwave generator and measured spectrometrically. The detection limit was 0.05 pg/g with a 90% recovery. Beryllium. Methods for separating Be from many other metal ions using a cation exchange resin and elution with 2 M "03 in 70% methanol were described by Strelow and Weinert (254). Strelow and Weinert (253) also studied the photometric method for Be using Chromazurol S and a micelle-forming reagent. They observed a nonlinearity at low concentrations due to a bathochromic shift. They found that an arbitrarily chosen wavelength rather than that of the normal maximum produces a much more linear calibration which passes through the origin. Gorev (96) described a procedure for using a photoneutron radiometer for determining Be in mining cores. A 90-mm core, for example, gave -2500 counts/min for 1%Be with a background of 8-9 counts/min. The threshold sensitivity for a 3-min measurement was 0.003-0.004% Be. Kurginyan et al. (154) and Quandt and Herr (228) developed similar procedures for determining Be in beryl and geological materials. Bell (21) described a volumetric method based on the titration of liberated OH- after addition of K F to a neutral solution complexed with tartrate. Interference of metal ions, except Mg and Al, was suppressed by EDTA. Extraction of the acetylacetonate complex of beryllium followed by atomic absorption was used in several papers to determine traces of beryllium. Korkisch and Sorio (144) used a chloroform extraction followed by cation exchange and atomic absorption to determine ng/g quantities of Be in geological materials. Korkisch et al. (145) used a similar scheme to determine pg/L quantities in various water samples. Terashima (263) also used a chloroform extraction and, after and decomposition of the acetylacetonate complex with " 0 3 HC104, determined Be directly by atomic absor tion. He described procedures for determining 0.04 to 50 pg/pg of Be in geological materials. Matsusaki (173) determined Be in A1 alloys by extracting the complex in MIBK and aspirating the organic phase into the flame. The use of furnace atomic absorption to determine Be in environmental samples was described by Bettger e t al. (24) who determined Be in stack gases; by Hurlbut and Bokowski (119) who determined Be on air filters; and by Owens and Gladney (208) who determined Be in fly ash, coal, and orchard leaves. The results of a collaborative test of EPA Method 104 for determining beryllium emissions from stationary sources was reported by Constant and Sharp (51). The tests were con78R
ANALYTICAL CHEMISTRY, VOL. 49, NO. 5, APRIL 1977
ducted simultaneously by four different organizations over a 13-day period. Statistical analysis provides estimates of the variance of repeated observations and the accuracy of the method. As shown in Table 11, numerous potentially useful fluorometric methods for Be have been investigated (42, 126, 129, 184,233) but none has a relevant application as yet. The same can be said for some of the photometric methods (15, 122, 162).Matsubara (171,172) determined Be in beryl and Be-Cu alloy based on the formation of the peroxotitanium complex by the reaction of beryllium with a reagent composed of NasTiFs, NaF, and HzOz in a molar ratio of 1:4:1. Kalyanaraman and Khopkar (127) determined Be in beryl photometrically with Eriochrome Cyanine R after extraction of the thiocyanate complex with 50% tributyl phosphate in toluene. Boron. Zhivopistsev et al. (294) determined B in A1 alloys spectrographically after preconcentration by extracting with 3% 1,l-diantipyrinylheptanein chloroform from a solution containing fluoride. Zinchenko and Zhilina (295) determined B in cryolite electrolyte volumetrically by the mannitol method after a chemical separation of the fluoride and aluminum. Chromium. A paper having great significance on the determination of chromium in light metals by atomic absorption was published by Green (98). He found that chromium in sample and standard solutions must be in the same oxidation state, preferably Cr(III), especially when using air-acetylene flames. He also found an increase in response with the addition of NH4C1. Copper. A dual gated integration system is reported by Butler et al. (40) to improve the spectrographic detection limits of Cu in A1 by a factor of 50 over the synchronous detection system when using the Grimm glow discharge. A coulometric method for determining Cu in A1 alloys based on the reduction of Cu(I1) and Sn(I1) which is electrogenerated at a Sn electrode in SnC14 was described by Kostromin et al. (147). Dubovenko and Pilipenko (76) developed a chemiluminescent method for determining Cu in A1 alloys based on the reaction of luminol with HZ02 in the presence of phthalic acid dinitrile. A sensitivity of 1 ng/mL of copper in solution is claimed. An atomic absorption method for Cu in A1 alloys based on the extraction of Cu(I1) into propylene carbonate from aqueous thiocyanate solutions was investigated by Stephens and Felkel(251). Sychra et al. (255) determined Cu in ilmenite by furnace atomic absorption without separation or concentration. Fluoride. A method for the determination of small amounts of fluoride in alumina using the fluoride selective electrode was described by Chang et al. (45,46).The sample was fused in NaOH-NazO2, extracted with H20, and filtered. An aliquot was complexed with Tiron, the pH adjusted to 7 , and the potential measured and compared to standards. Gallium. Methods for the separation of gallium from aluminum by anion exchange were developed by Shmanenkova et al. (243) and Kazantsev et al. (131). The former used a column of PTFE and trioctylamine and passed a 2 M NHdSCN solution of the metals through the column, eluting the Al(II1) with 2 M NHdSCN. The Ga(II1) was then eluted with 0.1 M HC1. Kazantsev et al. made the separation using a 2.5 M NaOH solution on an AV-16 anion-exchange resin. Ohta and Suzuki (204) determined gallium in aluminum by extracting the gallium chloro-complex from 6.5 M HC1 into isopropyl ether after reducing Fe(II1) with Ti(1II). An appropriate aliquot of the extract was atomized by furnace atomic absorption for the determination of gallium. Busev et al. (39) determined Ga in A1 by titrating amperometrically with uramil-N,N-diacetic acid at pH 2-3 using the anodic oxidation wave of the titrant at 0.8 V with a graphite microelectrode. Gallium was determined in high purity A1 by inverse voltammetry by Neiman and Trukhacheva (194) in 1M KC1 at pH 5-6 and a preelectrolysis potential of -1.5 V vs. SCE. Watanabe and Kawagaki (285) developed a fluorometric method for Ga in A1 by extraction of the Ga complex with 8-quinolinethiol into MIBK and measuring the fluorescence at 505 nm. To determine Ga in A1 salts, Grigoryan et al. (100) made a preliminary separation from 6 N HC1 solution with
butyl acetate. After stripping with water, a complex of Ga was formed with Acridine Orange in 6 N HCl, extracted with dichloroethane, and the fluorescence measured at 525 nm. A detection limit of 10 ng/g was claimed. Kreshkov et al. (149) determined Ga in A1 spectrographically after extraction of the chloro complex of Ga in butyl acetate. A photometric method for the determination of Ga in aluminate liquors was described by Babenko and Sukhorukova (13). After acid decomposition and pre-extraction of the chloro complex in butyl acetate, gallium was determined photometrically with Glycinecresol Red. Inoue et al. (121) determined Ga in A1 by extraction of the Rhodamine B complex with 1:6 MIBK-benzene in -6 N HC1 and measuring the absorbance at 563 nm. For a sample containing 0.015% Ga, the relative standard deviation was -1%. Hydrogen. A review of improved methods for the determination of hydrogen in aluminum was written by Degreve (62,63).He also published more detailed information on the vacuum extraction mass spectrometer method (64); on the nitrogen carrier fusion-thermal conductivity method (65);and the quantitative vacuum gas test-mass spectrometer method for liquid metal (66). The N2 fusion-thermal conductivity method was also described by Boillot and Hanin (27) for determining hydrogen in A1 and Ti. Baranovskaya (17) determined hydrogen in A1 spectrographically. Reaction gas chromatography was used by Nersesyants and Gokhshtein (196-198) to study the desorption of hydrogen from aluminum a t various temperatures by connecting the reactor to a chromatograph with a Zeolite NaX column and a thermal conductivity detector. Using an argon carrier gas, three hydrogen peaks were formed: the first at 200-300 "C is attributed to hydrogen originating from adsorbed moisture; the second at 550-640 OC was formed from hydroxyl groups in the oxide surface; and the third at 660-720 "C from atomic hydrogen in the metal. They (196,198) developed a method for determining hydrogen in aluminum by gas ehromatography and reported a detection limit of 0.01 mL/100 g. Spectrographic methods for determining hydrogen in titanium were reported by Barasheva and Lindstrem (18),by Nizel and Shubina (201),and by Grikit and Galushko (102), the last using an argon atmosphere. Das (58)used an ultrasensitive hydrogen detector to determine hydrogen in titanium. Surface hydrogen was extracted with a low energy spark, bulk hydrogen with a furnace and hydrogen gradients using a laser microprobe. The determination of hydrogen in titanium by the thermal extraction-mass spectrometer method was described by Otterson and Smith (207), and Powell et al. (227). Ogahara and Ishikawa (203) studied the effect of temperature on the determination of hydrogen in titanium by vacuum extraction and recommended a higher temperature than is conventional. Kutyreva et al. (155) determined hydrogen in titanium hydride by vacuum decomposition at 1000 OC, adsorption in zeolite 4A at -196 "C, and measuring the pressure after desorption. Huang et al. (115)studied the determination of hydrogen in magnesium by the vacuum fusion, vacuum evaporation, and capsule methods. Vacuum extraction with the sample sealed in a P d tube gave the highest reliability. They also measured the solubility of hydrogen in magnesium at 200 to 750 OC and studied the effect of alloying elements on the solubility. Lead. Lead was determined in high purity aluminum and its alloys by Gomez Coedo and Dorado (94) using atomic absorption after precipitation and extraction with ADPC. Nakahara and Musha (191) investigated chemical interferences in the atomic absorption method for lead and recommended the addition of 1000 ppm MgC12 to eliminate depressing interferences of many diverse elements in the analysis of aluminum and other alloys. Kanda et al. (128)determined P b in Ti02 by furnace atomic absorption using a solid mixture of sample and graphite and atomizing at 2100 OC for 5 s. A relative standard deviation of 3.1% for sample containing 5 pglg was claimed. Magnesium. Several investigators studied interferences and their elimination in the determination of magnesium by atomic absorption. Chen and Winefordner (47) studied the effects of AlCl3, HC1, flame height, and C2H2 flow rate. Cresser and MacLeod (53) investigated the use of less sensitive wavelengths and burner rotation for determining high concentrations of Mg and found that sulfate causes severe depression. They recommended dilution, use of a release agent,
and a fuel-lean flame on a triangular slot burner. Magill and Svehla (161) studied the influence of 54 ions and found that the interference effects can be eliminated by a nitrous oxide-acetylene flame except for silicates or by the use of an alkaline earth metal as a release agent with air-acetylene. Posgay and Borsodi Kovacs (226) determined Mg in high purity A1 by coprecipitating the Mg with Cd(OH)2 from an NaOH solution. After dissolving the precipitate, strontium was added as a release agent and the determination made with either an air-acetylene or nitrous oxide-acetylene flame. A rapid complexometric method for the determination of Mg in A1 alloys was described by Tikhonov et al. (270).After dissolution, an aliquot containing 50 mg of sample is neutralized with NHICI-NH~OH, treated with urotropine, and heated to 80 OC for 10 to 15 min. After addition of sodium diethyldithiocarbamate, and dilution to 250 mL, the mixture is filtered, treated with NH40H, and titrated with Complexon 111. The absolute error ranges from 0.02-0.04% for 0.4-1% Mg to 0.1-0.2% for 2-12% Mg. Hiller and Stenger (110) determined MgO in finely divided magnesium metal using the property that the metal is inert to chromic acid. The oxide is solubilized and the dissolved Mg is determined by atomic absorption. Good agreement is obtained with other methods including neutron activation. Polyak et al. (222) determined MgO in Mg-A1 alloys by dissolving the metal in bromine and an acetate ester. The MgO was determined in the residue. Nitrogen. A method for the photometric determination of nitrogen in Ti, Al, Be, and other metals was described by Hashitani et al. (109).The metal sample is fused in KOH and the volatilized ammonia absorbed in HC1. The ammonia is converted to monochloramine with hypochlorite at pH 10, reacted with thymol, and the absorbance measured at 660 nm. Oxygen. Helium-3 activation was used to determine trace oxygen in aluminum by Debrun and Barrandon (61),Petri and Sastri (213), and Vandecasteele et al. (277), using the 160(3He,p)18Freaction. The first two papers did not use any chemical separations and claimed sensitivities of
