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(538) Yoshimori, T.; Katoh, N.; Koike. A., Nippon Kinzoku Gakkaishi, 41, 1236 (1977): Chem. Abstr.. 89. 16103i 11978). (539) Yoshisaki, S.; Koizumi, H.. Japan.'Kokai 78 45287(22 Apr 1978); Chem. Abstr., 89, 151160r (1978). (540) Yukawa, K., Kinzoku Zairyo, 17, 42 (1977); Chem. Abstr., 88, 124844q 119781. -, (541) Yuksa, L. K.; Tsvetkov, V. P.; Kochmola, N. M.: Kalosha, V. K., Zavod. Lab., 42, 1348 (1976); Chem. Abstr., 86, 1824479 (1977). (542) Zaboeva, M. I.; Selezneva, L. V.; Verevshchikova, A. P.. USSR Patent 602475(15 Apr 1978); Chem. Abstr., 89, 139944s (1978). (543) Zemplen Papp, E., Magy. Kern. Lapja, 33, 314 (1978); Chem. Abstr., 89, 99231y (1978). (544) Zinevich, T. N.; Batalin, G. I.. Zh. FIZ, Khim., 52, 1210 (1978); Chem. Abstr., 89, 49683b (1978). (545) Zivanovic-Magdic, V.; Primjena Savrem. Metoda Ispit. Celika, Kolok., Ist, 103 (1973); Chem. Abstr.. 86. 25500b (1977). I
~
(546) Zommer-Urbanska. S., Chem. Anal. (Warsaw), 22, 1205 (1977); Chem. Abstr., 89. 16122q (1978). (547) Zuev, B. K.; Kulakov, Y. A.; Kunin, L. L.; Mikhailova. G. V.; Ryaboi. A . Y., Zavod. Lab., 43, 456 (1977); Chem. Abstr., 87, 26703c (1977). (548) Zur Nedden, P., Colloq. Spectrosc. I n t . , (Proc.), W t h , 2, 652 (1975); Chem. Abstr., 87, 210624d (1977). (549) Obrusnik, 1.; Posta, S., Radlochem. Radioanal. Lett.. 32, 161 (1978); Chem. Abstr., 89. 36052v (1978). (550) Belousova, V. V.; Chemova, R. K., Zavod. Lab., 44, 658 (1978); Chem. Abstr., 89, 139838k (1978). (55 1) Lucena Conde, F.;Hernandez Mendez, J.; Sanchez Misiego. A,; Delgado (1976). Zamarreno, M., lon(Madrid), 36,(1976): Chem. Abstr., 85, 1 5 3 4 0 8 ~ (552) Lucena Conde, F.:Hernandez Mendez, J.; Sanchez Misiego, A.; Delgado Zamarreno, M I MetalNectr , 41, 50 (1977); Chem. Abstr., 88, 202494s (1978).
Nonferrous Metallurgy -L ght Meta s: A uminum, Bery Titanium, and Magnesium H. J. Seim" and Russel C. Calkins Kaiser Aluminum & Chemical Corporation, Center for Technology, Pleasanton, California 94566
This is the seventeenth review on nonferrous metallurgical analysis and covers the two-year period from September 1976 through August 1978 as documented by Chemical Abstructs, Analytical Abstracts, W o r l d A l u m i n u m Abstracts, and Gouernment Reports Announcements. The following journals also were surveyed for the same period: Analytical Chemistry, Applied Spectroscopy, Ana1~'ticaChimicu Acta, The AnulJ'st, and Tcilanta. Wherever possible, the abstract number of the abstracting service has been included in the bibliographic citation. As in t,he past (223),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 t o be particularly useful or novel. One book related t o the analysis of light metals was published in Russia by Tikhonov (256) entitled: "Determination of Aluminum in Metals and Alloys." A revised edition of a commonly used reference book by Sandell: "Colorimatric Determination of Traces of Metals" was also issued (4th ed., Wiley, New York, 1978).
PROCEDURES FOR MULTIPLE CONSTITUENTS A compilation of procedures for the determination of multiple constituents in light metal materials is given in Table I. Some of these procedures will be highlighted in the following sections which are arranged according to those instrumental techniques most commonly used in the light metals industry. Atomic Absorption. An improved general method for atomic absorption analysis was proposed by Hansen and Hall (99). The method consists of preparing standards and samples in a common matrix of 0.4% CsCl and 2 % (v/v) HC1. A reduction in matrix effect errors is claimed and the method was applied to the analysis of aluminum alloys. Yoshimura and Morimoto (281) reported that the interference of fluoride and phosphate on the atomic absorption determination of A1 and T i could be reduced with carbon black powder. Preconcentration using precipitation or solvent extraction followed by atomic absorption continues to be a useful technique t o determine trace metals in nonferrous metallurgical materials. Berndt and Jackwerth (34) determined Bi, Cd, Co, Cu, Ni, Pb, and Zn in high purity aluminum by precipitation with APDC and dissolving the precipitate in 2 mL 20% Multiple determinations on this sniall volume of solution were made possible by adapting a com0003-2700/79/035 1- 170R
mercial sampler for automatic injection of 50-100 p L samples into the nebulizer. T h e authors claimed that the peaks obtained were more reproducible than those obtained by manual injection. Chowdhury et al. (54) determined Cu, Ni, and Co in bauxite aft?er extraction of their 2-nitroso-lnaphthalates from citrate media with MIBK. Ochsenkuehn and Parissakis (180) determined Au and Ga in bauxite by extracting the Au with chlorobenzene into tributyl phosphate and the Ga with bis(2-chloroethyl) ether into trioctylphosphine oxide. T h e Au and Ga were then determined in the organic phase by atomic absorption. They also described methods for determining 13 other elements in bauxite by direct atomic absorption or flame emission spectrometry. A method for determining V , Fe, and Cu in TiC1, by atomic absorption after extracting their quinolinolates into isoamyl alcohol was described by Rudnevskii et al. (217). Orlova et al. (187) determined V, Mo, Fe! Cu, and Zn in TiCl, by extracting a HC1 solution trioctyl amine, trialkylbenzylammonium chloride, and NHJ with toluene. The method allows the determination of these elements a t 0.2 ppm or less. Peterson (199) reviewed methods for the determination of nine elements in aluminum alloys by atomic absorption. Results are compared with those obtained by other techniques or with certified values. Zhukova and Solomatin (285) determined > 5 ppm Ca and >1 ppm Mg in T i without separation. Interference from Ti was minimized using Sr and K as release agents. They also described an ion-exchange method for determining lower concentrations of Ca and Mg. The test solution containing 6% HC1 and 3.6% oxalic acid was passed through a cation-exchange column and washed with 9% oxalic acid to remove Ti. T h e Ca and Mg were then eluted with 3 M HC1 and determined by atomic absorption. A method for determining Fe, Al, Ti, and reactive Si02 in bauxite was described by Purushottam and Naidu (207). The sample was fused with K&07 and dissolved with 2 N HC1. The residue was treated with 30% NaOH, acidified with HC1 and the solutions were combined for the measurements by atomic absorption. Total Si02 was determined on a separate sample after fusion with KOH and dissolving in HCl. Methods for the direct injection of solid samples into the flame for atomic absorption measurements were described by Gough (92) and Kantor e t al. (79). Gough determined nine elements in A1 alloys using the atomic vapors produced from the solid alloy by cathodic sputtering in an argon glow discharge. A dual modulation amplifier provided automatic background compensation and reproducibility of * 2 70was claimed. Kantor e t al. ( I 29) determined Na and K in solid Al,O,i using a dc arc nebulizer. Electronic integration of the signal is necessary because arc nebulization is not stationary d 1979 American Chemical Society
ANALYTICAL CHEMISTRY, VOL. 51, NO. 5, APRIL 1979 H Jerome Seim is Manager of the Analytical Research Department, Center for Technology Kaiser Aluminum & Chemical corporation, Pleasanton, Calif He recelved his B A degree from St Olaf 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 H e was a member of the Chemistry Department at the Unlversty of Nevada in Reno from 1949 to 1962 I n addition to teaching and directing research in analytical and inorganic chemistry, he was also a research consuitant for the U S Bureau of Mines From 1962 to 1969, he was Manager of Chemical Research for Allis-Chalmers 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 element analyses involving ion exchange, radiochemistry and a variety of instrumental methods and he has published numerous papers in this fieM Dr Seim is currently chairman of ASTM E 03 05 01 on the chemical analysis of aluminum and also the chairman of a special analytical task group on polycyclic organic materials for the Aluminum Association
Russel C. Calklns 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 h s ph D from the Unlversty of Wisconsin His research has been in the development of anawical methods for six years with the Dow Chemical Company, and for the past nineteen years with Kaiser Aluminum & Chemical Corporation HIS research interests include applications 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
for small samples. Detection limits of 0.8 ppm Na and 6 ppm K were obtained with 10-mg samples. Fuller (79)determined Cu, Fe, Mn, and P b in TiO, by dispersing the pigment i n 0.005 70 sodium hexametaphosphate prior to atomization. Detection limits down to 2 ppm using flame and 0.1 ppm using furnace atomization were achieved. Furnace atomic absorption was applied to the determination of Au, Ag, and Co in milligram quantities of aluminum by McElhaney (158). The two-line method of background correction was used and reproducibility was excellent. Volland et al. (270)also used furnace atomic absorption to determine Fe, Co, Zn, and Bi in high purity Be. Nanogram amounts of the impurities were deposited with constant current by circulating the solution through a cylindrical cathode of pure graphite. The graphite tube was then used directly in the spectrophotometer. Measurements were also made on the tube using neutron activation. Optical Emission Spectroscopy. A method for preparing high alloy aluminum standards by powder compaction was described by Redfield et al. (213). The powder was prepared by the violent disruption of a small stream of molten alloy with compressed air and collecting in H20. After screening, the 28- to 100-mesh fraction was treated to remove surface oxide and the resulting dry powder compacted a t 700 to 930 "C and 100000 psi in a powder press. The technique limits the segregation that occurs when high alloys are cast directly into a mold. A device and procedure for casting aluminum spectrographic standards was also described by Dimitrov et al. (63). T h e device consisted of an electric crucible furnace and a heated split cast mold, both equipped with a low frequency electromagnetic vibrator. Optimum conditions included a mold temperature of 300 350 "C and a stirrer frequency of 20-30 Hz. Gusarskii et al. ( 9 6 )described four methods of preparing Ti alloy samples for spectrographic analysis involving the fusion of alloy chips under an argon atmosphere. Olson and Macy (185) showed that the lack of agreement of emission spectrographic analyses between separately cast aluminum alloy samples is primarily associated with met-
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allurgical history. Acceptable results are obtained for low alloys, but only marginal results for high alloys. They recommend solution methods of analysis using atomic absorption or inductively coupled plasma spectroscopy for more accurate analysis of high alloys. Naganuma et al. (170) investigated the effects of surface roughness, grain size and target thickness on the emission intensities during cathode sputtering of Al alloys in the Grimm glow lamp for spectrochemical analysis. They found that the intensity of some elements changed with time because of selective sputtering of some phases. U'ehr (275) reported results obtained in the spectrographic analysis of A1 alloys using medium voltage excitation in argon. Chao et al. (50) described emission spectrographic methods for the determination of trace elements in aluminum for reactor applications. Many impurities are determined by standard point to plane techniques, but the determination of low level impurities such as B and Cd require conversion of the metal to oxide and the use of carrier distillation with dc arc excitation. KO and Laqua (130) compared the Grimm glow discharge lamp with a medium voltage spark discharge in argon for determining 12870 Si and 14.7% Mg in A1 alloys. Almost no matrix effects were observed with the glow discharge The calibration curve for Si using the spark source was separated into two branches because of the presence of other alloying elements. Lowe (147) modified a Grimm glow discharge source by including a secondary high current, low voltage discharge as used in hollow cathode lamps. This modification gave spectral lines of increased intensity, but simplified the spectra because it required less energetic excitation conditions. The system was applied to the determination of Mg and Zn in A1 alloys. A review comparing optical emission and X-ray methods for the analysis of Al, A1 alloys, and A1203 h a s published by Perman and Pernian (2%). Strzyzewska and Fijalkowski (240) compared the spectra of high purity alumina obtained by dc arc excitation in air, N,, Ar 2,5% 02,and Ar + 25% N,. The use of N, gave the most favorable decrease in continuum and background bands. A spectrographic method fur determining Si and Fe in AlF, using Sn as an internal standard and KC1 as a buffer was described by Tkachenko and Suprunova (257). Borin (40) applied a dual excitation scheme to the spectrographic determination of ten elements in bauxite after a preliminary ignition to remove water. Herkel'ova (102) studied the effect of sample preparation on the spectrochemical determination of Si, Al, Ca, and Fe in MgO using an ac arc and Co as an internal standard. Florian and Jurickova (76)studied the medium voltage spark discharge excitation of emission spectra for determining Ca, Fe, and Si in MgO using Co as the internal standard. The calibration curves obtained indicate that the optimum mode is cathodic polarization with 100 discharges/s. Gromadskaya and Olenovich (93) described spectrographic methods for determining seven impurities in Mg, Mg-A1 and their oxides. Metallic samples were converted to oxides before analysis. Apsher (13) determined W, T a , Nb, Mo, V. and Cr in Mg alloys by emission spectroscopy using the dc arc-powder technique. The alloys were first converted to their sulfates. l-an'kova (261) described the direct determination of nine elements in Mg and Mg alloys by emission spectrometry using a quantometer. Galushko and Grikit (80) determined ten impurities in Ti by emission spectrography using a dc arc without pre-arcing. Spark source excitation was used for determining Zr. Spectrographic methods for the determination of impurities in TiC14 were reported by Devyatykh et al. (60) and by Kapatsina and Lippert (120). Devyatykh et al. removed the matrix by vacuum distillation at 40 "C. The residue was dissolved in HC1 and applied to a graphite hollow cathode and excited in an argon atmosphere. Traces of Al, Cr, Ca, Mn, Fe, and S b were determined. The limits of determination ranged from 0.003 ppb for Fe to 0.6 ppb for Sb. Kapatsina and Lippert (120) determined Fe and A1 in TiC14 in the range of 0.5 to 10 ppm after enrichment of the impurities on a powdered mixture of NaCl, C and T i 0 2 . X-ray Methods. X-ray techniques continue to absume a more important role in the light metal industry. Methods for the analyses of aluminum alloys by X-ray spectroscopy were
+
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Table I. Methods for Nonferrous Metallurgical Materials material de terminations A1
high purity A1
A1 alloys
trace elements 30 elements Sc, Cr, Fe, Co, Cu, Zn, Ga, As, Mo, Cd, La, Sm, Eu, Hf N, p, s Ga, U U, Np R u , Os, Ir 25 trace elements Cu, Pb Bi, Cd, Co, Cu, Ni, Pb, Zn Mg, Zn, Cr, Cu, Mg, Ni, Ti, Fe, Si Si, Cu, Mg, Mn, Fe, Zn, Ti, Ni, Sn, Cr, Pb Ti, Cr, Mn, Fe, Ni, Cu, Zn, Pb Bi, Cr, Cu, Fe, Ga, Mg, Ni, Pb, Si, Sn, Ti, V , Zn Mg, Cu, Zn, M n , Fe, Cr, Zr, Si, Be Li, Cd, Cu Au, Ag, Co Si, Mg
AI-Si alloys Al20;
A1,0, sinter AlC1, A1F aluminate liquors A1 ores bauxite. red mud
Be BeCl, cryolite (bath) dolomite Mg
Mg alloys Mg, MgO MgO
seawater Ti Ti alloys
Zn, Mg, Fe Mg, z n Zr. Hf phase analysis Si, Fe, Ca, Ti, Mg, K , Na, A1 Na, K Ga, Na phase analysis Al, Si, Fe, Ca, Na, K, M g Hg, Zn, Co, Mn, Cr Si, Fe 25 elements Al, Si, Ca, Fe, Ti 22 elements Ti, Fe, Mn, Sr, Y , Zn, Gd As, Ga, Go, Ag, Zn, Ba, Be, Sc, Zr, 'Ti 1 0 elements Si, Fe, Ti, AI, Ca, Na Al, Fe, Ti, Cr, Ni, V, Mn, Cu, Ag, Au, Ga, Si, Ca, M g , K Si, Fe, Al, Ti Si, Al, Fe Al, Si Cu, Ni, C o Fe, Mn Sr, Y, Zr, Ga La, Ce, Sm, Gd, Eu, Yb, Sc phase analysis phase analysis phase analysis phase analysis phase analysis trace minerals Ca, Cr, Mn, Fe, Ni, C u As, Sb, Se, Hg, Sn, G e Fe, Co, Zn, Bi Cu, FP ratio ratio ratio CaO. 1 1 ~ 0 CaCO 1, % I ~ C O Al, Cr, Cu, Fe, Mn, Ni, Pb, Si, Zn Ru, Os, Ir W. Ta. Nb. blo. V. Cr Zr, ~f Al, Cu, Zn, M n , Be, Si, Fe, Ni, Zr B, Si, Fe, M n , Ni, Ti, Cu Al, Ca, FP, Mg, Si Ca, Fe, Si Si, Al, Ca, Fe Ca, M g Al, Mn, Sn, Cr, Ni, Cu, Fe, Si, M o , V , Zr W, M o , Cu, Cr, As, Sb, Fe, Ta Ca, Mg Al, Zr Fe, Co, Mo, AI phase analysis
method" S NA NA P NA R NA NA V AA AA S XRS XRS AA AA FAA S XRS S
P C XRS AA NA
T XRS R S XRS XRS NA
NA, XRS S
XRS XRS AA, FP
AA NA NA AA
NA, XRS XRS NA IR, T, XRD T
IR XRD C T
XRS NA NA, FAA P C
C, XRD XRD C EP, XRS XRS NA S
P S S
XRS S S
C S N-4
AA
reference 50 36
146 148 271 276 220 165
88 34 92 70
266 214 199 150
158 130 153 147 39 13.5
31 119 33 228 279 94 257
98 286 37 57 40 101
156 180 207 108 59, 61 54 8
195 265 124 1 3 2 , 1 9 0 , 194, 210 68, 259 189 45 123 2 38 245 270 103 1 2 , 22, 1 7 5 20 21 229 282 214 220 13 39
264 93 154 76 102 1 0 , 1 4 0 , 1 4 3 , 144 80 233 285
P
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Table I ( C o n t i n u e d ) rn ale ria 1
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reference 60 120
187 217 79 14 258 38
XRS Ti. Zr phase analysis XRD a AA, atomic absorption; C, chemical; EP, electron probe; F A A , furnace atomic atisorption; FP, flame phobmetric; I R , infrared; N A , neutron activation; P, photometric; R , radiochemical; S, spectrographic; T, thermometric; V, voltammetry; XRD, X-ray diffraction; XHS, X-ray spectroscopy. I___._
-.
__
reported by Martinetti ( I % ) , Verbeke et al. (2661, and Roca Adell and Diaz-Guerra (214). Martinetti investigated the effect of remelting the sample on the determination of Zn, Mg, and Fe. Verbeke et al. (266) used an energy dispersive system for determining eight elements in A1 alloys. Although matrix corrections were applied, agreement with certified values was only fair. Roca Adell ( 2 2 4 ) determined 1:3 impurities in A I and nine iriipwities in Mg. Methods for correcting the spectral interference of Ti on V and of V 011 Cr were described. Limits of detection ranged from 0.8 to 36 pprn. Bennett et al. (31) investigated the fusion method for the determination of eight constituents in A120j by X-ray spectroscopy. 'I'hey found the accuracy t o be equivalent>or better than that obtained by chemical methods for all elements except AI. Yakimova et al. (279) studied the effects of grinding, grain size, and composition on the X-ray analysis for seven elements in sinter cake from the sinter process for the production of A12F13. Haftka (98)developed procedures for the X-ray determination of 25 elements in alkaline aluminate liquors from the Bayer process. Polyolefins, epoxides, and glassy carbon were used for sample holders for hoth norrnal pressure and vacuum operation. T h e difficulties in standard preparation were overcome by dividing the elements determined into five groups. The detection limits were better than 10 m g j L Methods for the application of tiorate fusions to the X-ray analysis of bauxites were reported by Haukka and Thomas ( I O l ) , Matocha (156), and Tertian (2.50). All included procedures for calculating matrix correctioris. Haukka and Thomas (101) used a low ratio of sample to flux (12) and the accurate and precise determination c ~ ften elenients was claitned. Matocha (156) described an automated procedure for the determination of six constituents in hoth bauxite and red mud. Al-Mundheri et al. ( 8 ) and Csikaine and Bacsone (57) compared energy dispersive X-ray spectroscopy source) with neutron activation for the determination of selected elements in bauxite. Pazsit and Buczko (195) also used an source for det,erinining Sr, Y, Zr and Ca in bauxite. Overbey and Scott (189) developed an improved method for determining boehmite and gibbsite in bauxite and red mud by X-ray diffraction. Zirnrnernian and 1,alonde (286)described a fusion-X-ray procedure for the deterniii;ation of Al, Si, ('a, Fe, and T i in rionhauxite sources of A1203 using Tertian's double dilution method. A coniparison of the X-ray diffraction method with t w o titration methods and a conductivity method for determining bath ratio in cryolite electrolytes was made by Baggio and Olavarria 120). They concluded that the X-ray method was much faster and sufficiently accurate for control laboratories. Balashova et al. (22) described a calculated X-ray diffraction method for determining bath ratio in the presence of CaF, and MgF2 in both acid and alkaline cryolite electrolytes. A method using proton induced X-ra nd a Si(1,i) detector for determining Ca, Cr, Mn, Fe, Ni, and C'u in Be was described by Strashinskii et al. (238). Matherny (153) reported a method for determining Al, Ca, Fe, Mg, and Si in MgO using both sequential and multichannel X-ray spectrometers. Austen ( 2 4 ) reported an accurate and precise X-ray method for determining Fe and T i in ilmeriite using a solution technique. Toniskii et al. (258) developed a method for determining T i and Zr in placer ores using a 1('9Cdsource and a proportional counter detector. Bochenin (.?8)described a method for determining ilmenite in T i ore beneficiation products by X-ray diffraction and -/-ray scattering. A
____
. - -.
_____
__
quantitative X-ray diffraction method for the determination of ,j phase in T i alloys was reported by Bekrenev (29). Microanalysis of S u r f a c e s . A new method of empirical calibration for the quantitative ion microprobe analysis of A1 alloys using matrix ion species ratios was developed by Ganjei et al. (84). Kirchheim et al. (127) investigated single crystals of A1 plus other metals using laser microprobe spectrometry. A system for the quantitative characterization of microstructures in A1 alloys by combined image analysis and X-ray discrimination in the scanning electron microscope was reported by Ekelund and Werlefors ( 7 2 ) . Gerlach and Davis (86) reported that semiquantitative analysis of A1 alloys can be performed with secondary ion mass spectrometry (SIMS) if oxygen enhancement is employed. Mathieu and Landolt (155) studied the influence of film thickness, ion beam energy, and impurity absorption on the depth profile analysis of anodic films of A1203and T i 0 2 using Auger electron spectroscopy. Kraft and Lueschow (138) determined oxygen in the surface layer of A1 using a macro-probe for excitation and an X-ray spectrometric analyzer. Barbi and Russ (25) analyzed AI$, particles of various sizes for oxygen by scanning electron microscopy with a windowless energy dispersive X-ray spectrometer. The spectrometer can be used t o determine oxide thickness and is also capable of detecting carbon. hlii and Minami (161) determined COP in carbonate minerals of calcium and magnesium with an electron probe rnicroanalyzer by measuring the X-ray intensities of C and 0 and applying suitable correction factors. Yusa (282) determined CaCO, and hlgCOBin carbonate minerals using an electron microprobe analyzer and applying corrections to the X-ray intensities of Ca and Mg. O t h e r I n s t r u m e n t a l T e c h n i q u e s . Optoacoustic spectrometry was used by Adams et al. ( 4 ) to determine rutile and anatase in Ti02. The instrument is capable of analyzing very small samples and of examining surface layers without interference from the matrix. Raeuerle et al. (25) investigated the sensitivities and interferences in the activation analysis of mag~iesiurnand aluminum using cyclotron produced fast neutrons. The senqitivities achieved were much better than those obtained with 14-MeV neutrons. A rapid method for determining the water content of bauxite by thermal neutron scattering was described by DeBruin et al. (59). Combination of this technique with the activation analysis for A1 and Si allows the calculation of the amount of gibbsite in bauxite.
PROCEDURES FOR LIGHT METAL MATERIALS ,4compilation of procedures for light tnetal materials arranged according to the element determined is given in Table 11. Selected procedures are described briefly in the following sections. Aluminum. A gravimetric meLhod for the determination of .41 in bauxite with acetoacetanilide was described by Sarkar (222). The precipitate contains 4.85% A1 and can be weighed after drying at 110 "C. Cr, Ti, and V do not interfere; Cu, Ni, Zn, Cd, and C o can be complexed with cyanide and Fe(II1) mith thioglycolic acid. Coulson (56) developed a procedure for estimating available A1,0, in bauxite by autoclaving the sample at 120 O C with 13.5% NaOH in polypropylene bottles. The A1,Oj is determined by titrating excess EDTA with 0.05 M ZnSO,. Tikhonov (254) compared EDTA. CyDTA, DTPA, and NTA a5 reagents for determining A1 complexometrically by back titration with Zn(I1). The best reagents were EDTA
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N
ANALYTICAL CHEMISTRY. VOL. 51, NO. 5, APRIL. 1979
and CyDTA. The end point with DTPA was less distinct and NTA could not be used. Utrilla Sanchez et aI. (262) studied the homogeneous precipitation of A1 with oxine in a solution buffered with NH3 by using the method of volaiilization of the solvent. Persson e t al. made a theoretical study (197)of the effect of H , 0, N, Ar, C1, S, C, Si, and Fe on the furnace atomic absorption determination of alumirium. This was followed by an experimental study (198)of the effects cf H, 0, C1, S, and N. In general, theoretical predictions were borne out in practice. Suggestions for eliminating or minimizing the effect of potentially interfering elements are given. Several papers were published on photometric methods for aluminum using ternary complexes. Goto et al. ( 9 0 )found that the addition of cetyltrimethylammonium chloride to the Al-ferron complex improved the linearity of the working curve and diminished t h e absorbance of the reagent blank. Mori et al. (167)developed a rapid and sensitive method for Al using gallein and cetylpyridinium chloride. Tananaiko and Vdovenko (246) found t h a t t h e addition of cetylpyridinium chloride to the Al-pyrocatechol violet complex increased the molar absorptivity. Tikhonov and Andreeva (255) found increased selectivity in the photometric determination of A1 with Xylenol Orange using CyDTA or DTPA. A method for determining A1 in T i ores and concentrates by precipitating T i with N H 4 0 H in the presence of Complexon I11 and determining A1 complexometrically in the filtrate was reported by Momirlan (166). A l u m i n a . Investigations continued on electrochemical methods for determining the A120, concentration in cryolite electrolytes. Dewing a n d Van der Kouwe ( 6 2 ) studied chronopotentiometric measurements using Au and Pt wire anodes. Thonstad (252) used a semicontinuous chronopotentiometric method with a graphite electrode to investigate changes in the A1203 concentration of an aluminum electrowinning cell during normal operation. Iuchi ( 1 1 1 ) and Mazza et al. (157) determined AI2O3in cryolite electrolyte from the current and potential a t the appearance of the anode effect. Drobot et al. (69) compared the X-ray diffraction and infrared methods for determining aA120?in reduction grade A1203. T h e two methods were used on eight aluminas from different sources without any significant differences in the results obtained. B e r y l l i u m . An atomic absorption method for the determination of Be in Al alloys was reported by Janousek (115). The depressive effect of A1 was minimized by using 0.3 ?H V F I and the detection limit of Be was -0.3 ppm. Sakamoto et al. (219) determined Be in A1 alloys by extracting with trifluoroacetylacetone in chloroform and analyzing by gas chromatography using a microwave plasma detector. A fluorometric method for determining Be in A1 alloys using 0-(8-hydroxynaphthylideneimino) benzenearsonic acid was reported by Talipov et al. (243). T h e calibration curve was linear for 1 ppb to 1 ppm in solution a t pH 4.5. Alykov and Cherkesov ( 9 )studied a general fluorometric method for Be using 3-amino-5-sulfosalicylic acid. The detection limit was 5 p p b in solution. Optimum conditions for the determination of Be by furnace atomic absorption were studied by Shimomura et al. (227). Hurlbut (106,107) also studied variables in the furnace atomic absorption method for Be and applied the technique to the determination of E e in biological materials. Complexometric methods for the determination of Be were reported by Sergeev and Korenman (224) and Szczepaniak and Staniewska (241). Sergeev used aspartic acid as the titrant with Arsenazo I and I1 as indicators. Szczepaniak used (N,N,N',h."-ethylenediamine)tetramethanephosphon~c acid with Chromazurol S as indicator. Interferences were masked with EDTA. A gravimetric method for Be using N-p-chlorophenylrn-nitrobenzohydroxamic acid was reported by Khadikar et al. (125). The precipitate was weighed after drying at 110 "C. Interferences were masked with cyanide, citrate, oxalate, and EDTA. Morozova et al. (168) also described a gravimetric method for Be using nitrilotrimethylphosphonic acid. Interferences were masked with DTPA. Fluorometric methods for the determination of Be were described by Drevenkar et al. (67) using the ethyl ester of 2,4-dioxo-4(4-hydroxy-6-methyl-2-pyrone-~-yl)butyric acid; by Guiraum and Vilchez (95) using 2-quinazarinsulfonic acid;
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by Meshkova et al. using benzoylmethane and pyridine; and hy Tashkhodzhaev et al. (247, 248) using azomethine compounds. A comparison of photometric and fluorometric methods for determining traces of Be was made by Ackermann and Koenig ( I ) . As shown in Table 11, numerous potentially useful photometric methods for Be have been investigated. Methods using binary complexes were reported by Borisova and Ivanov (41) using Eriochrome Cyanine R; by Capitan et al. (48)using 1-hydroxy-2-carboxyanthraquinone; by Nistreanu (178) using azosalicylic-azochromotropic acid derivatives; arid PresasBarrosa et ai. (205)using uramildiacetic acid. Beschetnova et al. (35)compared the binary complexes of Be with Xylenol Orange and Methylthymol Blue and also investigated the ternary complex with Methylthymol Blue and diphenylguanidine. Methods using ternary complexes were reported by Anisimova and Beschetnova ( 1 1 ) using Chrome Dark Blue and diphenylguanidine; by Marczenko and Kalowska (151, 152) using cetyltrimethylammonium ion with Chromazurol S or Eriochronie Cyanine R; and by Uesugi and Miyawaki (261) using Chroma1 Blue G and cetyltrimethylamtnonium chloride. A comparison of three sampling methods for measuring Be in a work environment was made hy Donaldson and Stringer (66). No reliable conversion was found to exist between results obtained on a single sample basis. However, for large riunibers of samples, when the concentration is 2 b y the .4EC method, the concentration by the personal respirable method is 1 and by the total personal method is -3 pg Be/ni3. Zdrojewski et al. (283) determined Be in airborne particulate by both atomic absorption and furnace atomic absorption and found the minimum measurable concentration to be 2.5 and 0.05 ng/m3, respectively, in air. Hudson et al. (104) measured Be in simulated aerosol samples by proton scattering. A sensitive photometric method using Chrome Azurol S and cetylpyridinium bromide for the determination of He in airborne particulate was reported by Mulwani and Sathe (169). Measurements down to 1 ppb in solution were claimed which is comparable to the morin fluorometric method. Ross et al. (21.7) determined Be in particulate matter using a chelation-gas chromatography method. Lagas (142) determined Re in water by furnace atomic absorption. He found that problems with reproducibility and memory effects could be avoided by using tubes coated with pyrolytic graphite and carbide. Radiochemical methods for determining Be in ores continue to be investigated. Berezina et al. ( 3 2 ) described a system based on a specially designed detect,or that nieasures the CY particles from the short lived 8Be produced hy the photoneutron reaction with 9Be. The sensitivity of the method was 2.6 X 10-l'g. Kazakevich (122)used an automatic neutron counter with a scintillation detector to determine He in samples irradiated with bremsstrahlung radiation. B i s m u t h . A method for determining Bi in AI alloys by furnace atomic absorption was described by Oht~aand Suzuki (182). They used Mo microtubes and reported that thiourea improved the absorption profiles and increased t.he sensitivity. Thiel and Damm (251) determined Bi in A1 alloys by using cellulose nitrate and cellulose triacetate as c i track detectors for measuring the "'Po produced by the reaction of 2'Y3Bi with thermal neutrons. The detection limit for Bi was 10 ppb. Boron. A comparison of photometric and fluorometric methods for determining B in high purity A1 was reported by Cook and Holan (c55). They found that either technique following an extraction separation was superior to the distillation or direct fluorometric methods. Patricot (193) determined B in A1 alloys by flame emission spectrometry after extraction of the ethyhexanediol complex with chloroform. A photometric method for determining B in A1 alloys using 1,l'-dianthrimide was described by Klitina and Viksne (129). They claimed excellent results for determinations ranging from 0.007 to 0.03'2% B. Calcium. Prager and Graves (204) compared the direct atomic absorption and X-ray spectrometric methods for determining Ca in magnesite. The X-ray method used fused disks with standard addition. Both methods were found to be acceptable substitutes for the gravimetric procedure with the AAS procedure being the simplest and most rapid. A rapid method for determining Ca in magnesite by complexometric titration with EGTA was reported by Adam and Psibi! (2). -I
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A N A L Y T I C A L CHEMISTRY, VOL. 51, NO. 5, APRIL 1979
Excess titrant was back-titrated with Zn(l1) using thymolphthalexon as indicator. A method for determining trace amounts of Ca in T i using an ion-exchange separation was described by Zhukova and Solomatin (284). An HC1 solution of the sample containing oxalic acid is passed through a cation exchange resin, eluting the Ti as an oxalato coniplex while retaining the Ca. The Ca is eluted with 3 N HCl and, after evaporation to dryness, determined photometrically with chlorophosphonazo 111. Carbon. Nikol'skii e t al. (176) determined C in Be by thermal oxidation, followed by a chromatographic determination of the resulting C02. Improved accuracy was claimed when first treating the sample with water vapor a t 1000 "C, separating the C-containing gases and then oxidizing them to CO,. Nikol'skii et al. (177) also determined carbide in Be and Be& by decomposing the sample with solid alkali at 200-300 "C in an inert atmosphere and determining the evolved CH4 by gas chromatography. Borodin et al. (42) determined C in TiOz by combustion in purified air and volumetric measurement of the combustion gas before and after passage through KOH solution. Copper. A device for the isolation of spectral lines based upon atoniic fluorescence generated by a low pressure gas discharge was described by Human et al. (205). A detection limit of 25 ppm Cu in A1 was achieved, but matrix effects encountered with the glow discharge were not eliminated. -4selective complexometric method for the determination of Cu in A1 alloys was described by Raoot et al. (212). Excess EDTA was added to complex Cu and other metal ions and back-titrated with lead nitrate. The Cu was then selectively decomplexed with a binary mixture of ascorbic acid and thiourea or ascorbic acid and thiocyanate by heating to 70-80 "C for 5 minutes. After cooling, the EDTA released was titrated with lead nitrate. An extraction--atomic absorption procedure for determining traces of Cu in A1 alloys was described by Kono (131). The Cu was extracted a t p H 5 as the diethyldithiocarbamate in hexane. The flame instability when aspirating organic solvents was eliminated by using a three-slotted burner in which the air-acetylene flame was sandwiched between pure oxygen. T h e limit of detection was 1 ng/mL in hexane. cJanssen et al. (116)determined traces of Cu in Al alloys by furnace atomic absorption after extraction a t p H 8.5 into a solution of lead diethyldithiocarbamate in chloroform. Several papers were published on extraction- photometric niet,hods for determining Cu in A1 and A1 alloys. Kim and Park (126) extracted Cu from acid solutions into diethyldit,hiocarbamate in toluene and measured the absorbance at 435 nni. Busev and Panova (47) extracted a substituted dithiophosphate complex into chloroform. Gershuns and Grineva ( 8 7 ) extracted the Cu-4,4'-bis(4-ethoxycarbonyl)2 2'-hiquinolyl complex int,o butanol at p H 6.3 and measured the absorbance at 556 nm. Patil and Shinde (192) extracted the Cu with tri-n-octylamine into benzene. The Cu was back-extracted into an aqueous phase and determined photometrically a t 440 nm with n-benzoinoxiine. Silva and Valcarcel (232) formed the Cu coniplex with pyridoin phenylhydroxylamine in 40% aqueous ethanol at pH 6.5. The complex was extracted into pentanol and the absorbance measured a t 440 nm. Gallium. A methud for determining Ga in aluminate solutioris was described Ly Mambetkaziev et al. (149). The Ga was extracted with diethyl ether froni a 5.5 M HCI solution and back-extracted with 0.1 M HC,l. The determination was made by oscillopolarography using a supporting electrolyte containing KSCN and NH4C1. De et al. (58) reported an atomic absorption procedure for determining Ga in bauxite. T h e method involved a mixed oxide separation with excess NaOH and solvent extraction of the Ga with cupferron into MIBK. Banateanu and Cost.inescu (23) determined Ga in bauxite by extracting the Pyronine G complex from a 6 M HCl solution with benzene and measuring photometrically at 525 nm. Hydrogen. Studies on inert gas fusion methods for determining H in A1 were reported by Kit,abayashi (128) and Oganezov and Bairamashvili (181). Oganesov used the technique t o determine the temperatures of maximum evolution of different states of H in Al. Watanabe et al. (273) compared the vacuum fusion, vacuum evaporat.ion, and vacuum extraction methods for determining H in Mg. They
found that vacuum extraction of a sample sealed in a P d tube gave the highest reliability. Vacuum methods for determining H in Mg and M g alloys were also described by Gotvyanskii et al. (91). The determination of H in Ti with an ion microanalyzer was investigated by Okajima et al. (184). They used an intensity ratio method and found the H concentration in the surface layer to be much higher than in the bulk of the sample. Indium. An extraction -X-ray spectroscopy method for determining In in A1 alloys was described by Iwasaki (112). The In was extracted from the sample solution at pH 1.5 with a chloroform solution of diethyldithiocarbamate. X-ray measurements were made on a filter paper disk after evaporation of the solvent. For high Zn-containing A1 alloys, the Zn was removed by back-extraction of the chloroform extract with an aqueous solution of 0.2% NaCN. Iron. A coulometric method for determining Fe in bauxite was reported by Sierra et al. (231). The reductant was leucotoluidine blue which was electrogenerated from toluidine blue present in the supporting electrolyte. The absolute error was 0.26% in the determination of 16.69% Fe. Skidmore and Taylor (234) described an atomic absorption procedure for determining Fe in nonferrous materials after extraction from a - 7 M HC1 solution with MIBK. Lead. A furnace atomic absorption procedure for determining traces of P b in TiO? pigments was described by Wilska (277). The pigment is dispersed ultrasonically in water containing isopropanolamine and an aliquot introduced into the graphite atomizer. Magnesium. A method for the determination of metallic Mg in the presence of MgO was reported by Koval'chuck et al. (133). The Mgo was selectively dissolved in 20% CuC1, and separated from the MgO by filtration. After precipitation of the Cu(I1) with diethyldithiocarbamate, the dissolved Mg was determined complexometrically. A study of interferences on the determination of Mg by furnace atomic absorption was described by Ohta and Suzuki (183). Sammour et al. (221) investigated the effect of amines on the photometric determination of Mg with Eriochrome Black T. They found increased sensitivity with hexamine, hydrazine, and di- and triethanolamine. Ammonia, hydroxylamine, and monoethanol decreased the sensitivity. Tikhonov and Kudrvashova (253) described optimum conditions for the photometric determination of Mg with o-cresol phthalexon, including the masking of interfering elements. A fluorometric method for the determination of Mg using 4-hydroxy-3-(5-oxo-2pyrazolin-4-y1)naphthalene-1-sulfonicacid was developed by Pilipenko et al. (200). Molybdenum. A gravimetric method for the determination of Mo in Ti alloys was reported by Naumann (171). After dissolution in HPSOJand oxidation with H 2 0 and HN03, the Mo(V1) is extracted froni 6 M HC1 with butyl methyl ketone. After reextraction with water, the Mo(V1) is precipitated with 8-hydroxyquinoline in acetate buffer. Niobium. A photometric method for the determination of N b in alloys of T i and other metals was described by Elinson et al. (73). After reaction with sulfonitrazo E in the presence of Complexon 111, the absorbance was read a t 560 nm. Nitrogen. A spectrographic method for the determination of N in Be was reported by Egorov (71). A special arc chamber was constructed and the detection limit in Be was 50 ppm of N. Chang et al. (49) developed a method for determining N in T i alloys using the ammonia electrode. After dissolution in acid, measurements are made at p H 1 2 in the presence of tartrate and EDTA. Oxygen. A study of surface effects during the determination of 0 in A1 by fast neutron activation was made by Janczyszyn and Sztwiertnia (114). Samples were etched before and after activation and transported using nitrogen. Vacuum fusion methods for determining 0 in Ti using graphite crucibles containing Ni were described by McLauchlan (159) and Burtsev et al. (46). Burtsev measured the CO by mass spectroscopy. Kraft and Kahles (137) described a technique for determining 0 in Ti alloys in which the sample is wrapped in Pt or Pd foil and heated to 1800 to 2100 "C in a graphite crucible in a stream of He or Ar. Measurement is made by an infrared method. The sandwich technique was preferred to the molten bath technique. Valladon and Debrun (263) determined 0 in T i by activation with 3.5-MeV tritons ac-
ANALYTICAL CHEMISTRY, VOL. 51,
celerated by a Van de Graaff generator. Silicon. An atomic absorption procedure for determining 0.05 to 28% Si in AI-Si alloys was developed by Gomez Coedo and Dorado (89). The sample is treated with HF, "OS and H202,in a Teflon lined pressure reactor at 110 "C for 30 min. After cooling, the sample was added to a boric acid solution and diluted to a n appropriate volume for measurement by atomic absorption. Suitable amounts of A1 were added to the standards. Twelve other elements were also determined in AI-Si alloys using the same dissolution technique. Silver. Methods for the determination of small amounts of Ag in A1 alloys were described by Nomura and Nakagawa (179) and by Parker and Polmear (191). Nomura used the voltammetric wave of the oxidation product formed by the reaction of Ag with 2-aminophenol. Parker used energy dispersive X-ray spectroscopy. Solomatin et al. (236) reported a method for determining Ag in Mg alloys using an amperometric titration based on the reduction of Ag(1) with ferrocene in an aqueous organic medium. Sodium. Continued research on the development of an electrode system for determining Na in molten Al was reported by Fray (77, 78). The probe used $alumina as the electrolyte and a mixture of cu-aluminaand @-aluminaas a reference. The method was applied to the control of the Na modification of AI-Si alloys. A rapid method for the determination of N a 2 0 in industrial A1,0, was described by P o p and Dumitrescu (203). After calcination of the sample a t temperatures up to 600 "C, the NaaO was leached with water and titrated with standard acid. Titanium. Extraction photometric methods for the determination of T i in A1 and A1 alloys were reported by Cherkesov and Krasnov ( 5 3 ) , who extracted the thymolphthalexon complexon into higher alcohols, and by Talipov e t al. (242),who extracted the complex with dimedrol and thiocyanate into benzene. Verdizade and Shiralieva (267,268) used the ternary complexes of Ti with thiocyanate and Pyramidon or Antipyrine extracted into chloroform for its determination in alunite. A photometric method for determining T i in ilmenite based on the complex of Ti(II1) with 2,2'-biquinoxalyl was reported by Baranowski et al. ( 2 3 ) . Before complexation, the T i is reduced with a cadmium amalgam column. Sobhana and Savariar (235) determined Ti in ilmenite by extracting the ternary complex of Ti, morin, and aniline into 3:l benzyl alcohol-butyl alcohol. A rapid method for determining Ti in !aterite ores by energy dispersive X-ray spectroscopy using an 05Fe excitation source was described by La Brecque ( 1 1 1 ) . U'alsh (272) studied the interferences in the determination of Ti in ores and minerals by atomic absorption. Kaneko et al. (118) determined T i in T i c and T i N by complexation with excess EDTA and back-titration with Zn(I1). A gravimetric method for Ti based on its precipitation with 2'-hydroxy-4'-methylpropiophenone oxime was proposed by Jhaveri et al. (117). T h e reagent forms a 1:l chelate with Ti(II1) or Ti(1V) and the precipitate can be weighed after drying a t 120 "C. Dolgorev et al. (64) determined Ti(II1) and V(II1) in a reduction electrolyte for the production of T i alloys by measuring the absorbances of their oxalate complexes a t 400 and 270 nm, respectively. T h e analysis must be carried out in an 0-free atmosphere. An extraction photometric method for the determination of Ti(II1) using its ternary complex with aniline and an o-dihydroxybenzene was studied by Ali-Zade et al. ( 7 ) . Opasova et al. (186) developed a simultaneous photometric determination for Ti(II1) and Ti(1V) using benzoylacetone by measuring the absorbances a t 615 and 382 nm, respectively. In order to stabilize the Ti(II1) complex, a SnCl, solution was added which does not affect the complexation of either oxidation state. As shown in Table 11, numerous potentially useful photometric methods for Ti(1V) have been investigated. Methods using binary complexes in aqueous systems include those of Chavdhary (51) using 7-amino-2-ethylphenothiazine,of Gamidzade et al. (82) using azo derivatives of pyrocatechol, and of Osmanov (188) using lumogallion. Bag and Khastagir investigated four extraction photometric methods for Ti(1V). Reagents and extractants studied include: N-cinnamoylphenylhydroxylamine into chloroform ( 1 6 ) ; cinnamoylhydroxamic acid into amyl alcohol ( 17); phenylacetylhydroxamic acid into isoamyl alcohol (181, and N-salicyloylphenylhydroxylamine (19) into isoamyl alcohol. Other
NO.5, APRIL 1979
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combinations reported include: disulfoethyliminogossypd into butyl alcohol by Inoyatov et al. (109),3-(2-furyl)-2-mercaptoacrylic acid into amyl alcohol or ethyl ether by Izquierdo and Calniet (113), and 1-phenyl-2-methyl-3-hydroxy-4pyridone into chloroform by Vojkovic et al. (269). Photometric methods for Ti(1V) involving ternary complexes in aqueous systems include complexes with: Tiron and diantipyrinylmethane by Bashiruz Zaman and Rahman (26); disulfophenylfluorone and cetylpyridine chloride by Belousova and Chernova (30); diantipyrylmethane and 2,7-dichlorochromotropic acid by Kovaleva and Ganago (134): 4-(2pyridy1azo)resorcinol and hydroxylamine by Mirzaeva and Shalyakina (162);haematoxylin and cetyltrimethylammonium bromide by Leong (145);lumogallion and hydroxylamine by Mirzaeva and Tataev (163);and oxalic and chromotropic acids by Nazarenko and Pyatnitskii ( I 73). Photometric methods for Ti(IV) involving extraction of ternary complexes include the following sysbems: Tiron and diphenylguanidine into isobutyl alcohol by Gambarov (81); diantipyTinylmethane and trihydroxyfluorones into chloroform by Ganago and Mosina (83);thiocyanate and hexamethylphosphoramide into chloroform by Mitra and Mitra (164): 0-bromobutyric acid and l-phenyl-3-methyl-5-pyrazolone into chloroform by Pyatnitskii and Simonenko (208, 209): benzoylphenyl hydroxylamine and phenylfluorone into chloroform by Shpak and Zul'figarov ( 2 3 0 ) ; monooctyl-0-anilinobenzylphosphonate and thiocyanate into chloroform by Tamhina et al. (244); and 2-(2-thiazolylazo)-5-dimethylaminophenol and 1,3-diphenylguanidine into benzyl alcohol by Tsururni and Furuya (260). Vanadium. -4rapid photometric method for the determination of V in bauxite and other ores was reported by Roy et al. (216). The V complex with N-benzoyl-N-phenylhydroxylamine was extracted from a 5-9 M HC1 solution into chloroform and the absorbance measured a t 530 nm. An extraction photometric determination of \' in TiCl, was described by Dolgorev and Pal'nikova (65). The complex of L' with anthranilic acid acetone hydrazide was extracted from 1-6 N H2S04containing trichloroacetate with 1:l acetonechloroform. Agafonov et al. ( 5 ) determined V in TiC14 by X-ray spectroscopy. Zinc. Berndt and Jackwerth ( 3 3 ) applied the automated injection method for dispensing 50-100 uL samples inm the nebulizer for the determination of Zn in A1 alloys by atomic absorption. Rudometkina et al. (218) determined Zn in ,41 by its reaction with 7-(2-thiazolylazo)-8-hydroxyquinoline5-sulfonic acid in 50% acetone solution either after separation of Zn by extraction or using masking agents to eliminate interferences. Kasiura and Boroch (121) made a separation of Zn from AI by extracting the tri-n-octylamine and its determination by extracting wit.h dithizone i n carbon tetrachloride. Pirozhkova and Kikolaeva (2011 determined Zn in Mg alloys by complexing with antipyrylazo compounds in the presence of thiocyanate and extracting with 1:9 tributyl phosphate- benzene. Zirconium. Rapid procedures for the determination of Zr in A1 and M g alloys using Arsenazo I11 were described by Boganova and Nemodruk (39). The effect of various elements was studied and the detection limit was
