(223) Uzumasa, Y., Hayashi, K., Ito, S., Bull. Chem. SOC. Japan 36, 301 (1963).

(224) Wagner, J. C., Bryan, F. R., Advan. X-Ray Anal . 6, 339 (1963).

(225) Wakamatsu, S., Japan dnalyst 11, 1151 (1962).

12261 Walker. J. hZ.. Kuo. C. W.. ANAL. ‘ CHEM. 35, 2017 (1963). ’ (227) Watling, J., C.K. At . Energy

Authority, Res. Group AERE-R 3974, 1 n o 0 I Y U L .

(228) Welcher, Frank S., ed., “Standard >\lethods of Chemical Analvsis.” 6th ed., Vol. 11, Van Nostrand, Princeton, X. J., 1963.

(229) West, Philip W., MacDonald, A. 31. G., West, T. S., eds., “Analytical Chemistry 1962,” Fritz Fiegl 70th Birthday Symp. Papers, Elsevier, Amsterdam, 1963.

(230) Weszpremy, B., Kohdsz. Lapok 96, 74 (1963).

(231) White, G., Scholes, P. H., Metal- lurgia 70, 197 (1964).

(232) Wojcik, A., Hutnik 30, 281 (1963). (233) Yakovlev, P. Y., Koeina, G. V.)

Zavodsk. Lab. 29, 920 (1963). (234) Yakovleva, E. F., Belyaeva, Y. A.,

Sb. Tr . Tsentr. AVauchn.-Issled. Inst . Chernoi M e t . 31, 129 (1963).

Nonferrous Metallurgy 1. Light Metals Fritz Will, 111

Alcoa Research laboratories, Aluminum Co. o f America, New Kensington, Pa.

HIS is the tenth review on non- T ferrous metallurgical analysis and covers the two-year period from September 1962 through August 1964, as documented by Chemical Abstracts and Analytical Abstracts. Also, the following journals were surveyed directly for the same period: . ~ N A L Y T I - CAL CHEMISTRY, dnaly t ica Chimica Acta , The Analys t , and Talanta. S o t all of the creditable contributions are mentioned, nor are those that are dis- cussed necessarily the most important.

As mentioned in the last nonferrous metallurgy review (207), because of the increasing diversity of publications in the field of nonferrous metallurgy, the scope of this review surveys methodol- ogy on analysis of only the light structural metals : aluminum, beryllium, magnesium, and titanium. Fifty-five per cent of the references discussed the analysis of aluminum, 14% beryllium; 11% magnesium, and 20% titanium.

In a breakdown of the references as to percentages of the various techniques of analyses mentioned, the following results were found: 27% colorimetric, 22% spectrochemical, 11% activation analysis, 11% classical, 6% gas deter- minations, 5% polarographic, 4% chelo- metric, 3% ion exchange, 3% x-ray, 3% flame photometric, 2y0 atomic absorp- tion, 3y0 miscellaneous. As in the past, the colorimetric and spectrochemical methods of analyses are predominant with an increasing number of papers on activation analysis. Even though there were only four references to atomic absorption spectroscopy, more papers in this field are anticipated.

W700d, Marron, and Lambert (211) discussed the electron-probe micro- analysis of anodic oxide films on aluminum alloys. The oxide films formed by anodizing aluminum alloy in 15% H2S04 were subjected to cleaning

or sealing treatments and examined by electron probe for aluminum, sulfur, chromium, and nickel. This was the only paper on electron-probe analysis.

Van Sandt et al. (193) constructed an automatic, direct-reading spectrograph suitable for the analysis of beryllium samples with a commercially available grating monochromator as its basic unit. Specially designed high-purity graphite electrodes were used.

Ivanova, Kovalenko, and Tsyven- kova (76 ) discussed the spectrographic analysis of an aluminum alloy by fractional exposure. During analysis only one standard was employed and its spectra was photographed for various times. Lemieux (106) recommended an improved spectrochemical analysis of alumina by mineralized calcination. A procedure which converted samples to essentially alpha alumina was out- lined. Calcination with a small amount of aluminum fluoride eliminated many of the striking differences in physical properties of the samples.

Pocze (149) and Brune (15 ) sum- marized the activation analysis of aluminum. Ross (166) described the determination of 62 elemental impurities in beryllium, aluminium, and iron by activation analysis. The gamma activities of radionuclides produced by neutron activation were measured.

Kern (82) critically reviewed im- portant methods for determining hydrogen, nitrogen, and oxygen in beryllium, magnesium, and titanium, among others. The methods discussed were vacuum melting, carrier gas methods, chemical, spectrographic by a carbon d.c. arc, interniolecular viscosity, mass spectrometry, and activation analysis.

Four recent books concerning in part the analysis of light metals are note- worthy. “Chemical Analysis of

(238) Yamaguchi, N., Hasegawa, M., Japan Analyst 11, 126 (1962).

(236) Yatsyk, I. E., Orzhekhovskaya, A. I., Sb. A\Jauchn.-Tekhn. T r . Nauchn.- Issled. Inst . Met. Chelyabinsk. Sovnar- khoza 1961, 205.

(237) Zeuner, H., Giesserei 49, 858 (1962).

(238) Zielinski. E.. Przealad Odlewnictwa 13, 219 (1963). ’

(239) Zindel, E., Zeiher, R., 2. Anal. Chem. 195, 27 (1963).

Eisenhuttenw. 35, 109 (1964). (240) Zitter, H., Schwarz, W., Arch.

Metals,” Part 32 of the American Society for Testing and Materials’ 1964 Book of Standards (S ) , contains sections on the chemical analysis of aluminum, magnesium, and titanium and their alloys and the spectrochemi- cal analysis of aluminum and its alloys. “The Chemistry of Beryllium” (39) in- cludes chapters on chemical reactions of beryllium, extractive metallurgy of beryllium, and analytical chemistry of beryllium. “Treatise on Analytical Chemistry” ( 9 5 ) , Part 11, Vol. 5 , dis- cusses the determination of 24 elements in titanium. “Standard Methods of Chemical Analysis” (50) , Vol. 1, de- scribes the analysis of aluminum, beryl- lium, magnesium, and titanium.

As in the previous nonferrous review (207), the remaining text of this review is arranged alphabetically according to constituents determined. Tables I and I1 list analytical procedures according to materials analyzed and constituents determined.

Aluminum. K o o d , Marron, and Lambert (211) reported the electron- probe microanalysis of anodic oxide films on aluminum alloys. Fedorav and Linkova (41, 4.2) described the deter- mination of alumina in metallic aluminum by hydrochlorination. A quartz boat containing the aluminum was inserted into a molybdenum glass tube. The aluminum was dissolved in a current of hydrogen chloride and hydrogen and was distilled as the chloride. The alumina which remained was dissolved and determined photo- metrically a i t h aluminon. Iron, man- ganese, silicon, <0.5yo tin, and <2.5Y0 copper did not interfere.

Munshi and Dey (127) proposed a paper chromatographic separation and determination of copper and aluminum in aluminum-bronze alloys. The solu- tion of the sample was applied as spots

92 R ANALYTICAL CHEMISTR\!

to a strip of Whatman No. 1 paper, and the chromatogram was developed wit'h a butanol-concentrated HC1-water mix- ture. The strip was cut' in two, each piece was extrarted R ith boiling dilute HC1, and the copper and aluminum were determined colorimetrically. Burke and Davis (18) utilized C D T B [(l,2,- cyclohesylenedinitri1o:)tetracetic acid] for the chelometric determination of aluminum in aluminum-base alloys. .In excess of CDT.1 was added to the solution, the pH was adjusted to 5.5 to 6 with hexamethylenetetramine, and the solution was titrated with zinc using Xylenol Orange as an indicator.

Tikhonov (1 79) recommended the complexometric determination of aluminurn in magnesium alloys by titration of the sum of aluminum and zinc a t pH 3 with Complexon I11 in the presence of PAIS and a small amount of copper complexonate. The solution was titrated hot with Complexon I11 until yellow, boiled again, and the titra- tion was finished. The aluminum con- centration was calculated after the zinc content was deducted. A photometric method for the determination of aluminum in magnesium metals was developed using 8-hydroxyquinoline (188). Iron was complexed with o- phenanthroline a t p H 5.6 t'o 6.0.

hfalevannyi (113) used (4,4'-bis-3,- 4 - dihydroxyphenylazc,) - 2,2' - stilbene- disulfonic acid for the colorimetric determination of aluminum in titanium dioxide pigments. The reagent formed a stable pink complex with Al+3. Ferric iron interfered and was reduced with thiourea. Tikhonov and Grankina (180) investigated the complexometric determination of aluminum in titanium slags and concentrates by titration with Complexon 111 at p H 3 in the presence of P A S as a n indicator and copper complexonate. Potassium, sodium, cal- cium, magnesium, manganese, or chro- mium did not interfere. The inter- ference of titanium and iron was eliminated by extraction of their cup- ferronates. Navyazhskaya and Spory- khina (129) determined alumina in titanium oxide by titrating the excess of Trilon B added with 0.05N FeC13 a t p H 4.5 to 5.0.

Antimony. Vinogradova and Vasil'eva (196) reported the deter- mination of small amounts of tin (3 X 10-5%), bismuth (2 X and antimony (3 x loW5%) in high-purity aluminum by anodic voltammetry at a stationary mercury electrode. Opti- mum conditions were developed for the separation of these metals at the electrode, followed by the anodic polarization of the amalgam obtained.

Todd, Cuthbert, and Dickinson (182) recommended the determination of antimony and cobalt in magnesium-base alloys by neutron activation analysis. The method involved remote irradiation

in a nuclear reactor, radiochemical separation of the resulting antimony and cobalt activities, and comparison of these activities with those isolated from standards. Antimony and cobalt were determined down to 0.05 and 0.01 p.p.m., respectively.

Galliford and Yardly (52) studied the colorimetric determination of antimony in titanium dioxide based on the com-

pound developed with sodium hexa- metaphosphate and Brilliant Green. The colored complex was extracted with toluene and the absorbance was measured a t 640 mp. Yakovlev and Malinina (212) investigated the polaro- graphic determination of 0.01 to 0.2y0 antimony in titanium dioxide. Inter- ference by iron was avoided by reduction with ascorbic acid.

Table I . Methods for Nonferrous Metallurgical Materials A. Activation Col. Colorimetric At. Atomic absorption F. Flame photometric C. Chemical P. Polarographic

Material Aluminum Aluminum Aluminum Aluminum

Aluminum Aluminum Aluminum Aluminum Aluminum Aluminum Aluminum Aluminum alloys Aluminum alloys Aluminum Aluminum, beryllium Aluminum-uranium

alloys, titanium- uranium alloys

Alluminum alloys Aluminum allbys Aluminum alloys Aluminum alloys Aluminum alloys

Aluminum alloys Aluminum oxide Aluminum oxide Aluminum oxide

Aluminum oxide Aluminum oxide Aluminum oxide

Aluminum oxide Aluminum oxide Beryllium

Beryllium Beryllium Beryllium Beryllium Beryllium oxide

Beryllium oxide Aluminum, magnesium Magnesium-beryllium

alloys Magnesium

Magnesium alloy Magnesium alloy Titanium Titanium Titanium

Titanium, titanium

Titanium alloys Titanium dioxide

Titanium dioxide Titanium sponge

alloys

Constituents determined Cd, Co, Cu, Fe, Zn Cu, Xi, Zn, Fe, Mn, Sn, Si 45 elements Sc, Co, Np, Fe, Sn, Cd, Ag, Rb, Ho,

Tb, Lu, Ce, Tm, Cr, La, Nd, Yb, Cs, Sm

FeyCo, Zn, Sc Cu, Mn, Zn, Ga, Co, Sc, Fe Cu, Sb, As, Ga, Sc, Fe, Zn, Cd Cu, Zn, Fe, Mn, Pb, Ni, Ag, Bi, Fe, Si, Mg, Mn, Ti, Cu, Pb, Sn, 34 elements Cu, Fe, Mg, Mn Ka, Li, Mg, Ca Cu, Mn, Xi, Fe, Zn, Ti, Cr Zn. Cu. Fe. Mn. 5'. Ti

Cr Ni

, , 62 'elements Al, Fe, Mo, Xb, T', Zr, Cr, Ti, Ni

Pb, Mg, Zn, Cd, Co, Ca, Ag, Na Si, iMg, Cu, Fe Si, Cu, Mn, Mg, Cr, Zn Cr, W, Ti Cu, Mg, Mn, Fe, Si, Ti, Zn, Be, V, Zr,

Si, Mn, Mg, Cu, Fe, Zn Si, Ti, P, Fe Si, Ca, hlg, Fe, Ti, Ya, K Xi, Cr, Ca, Mg, Fe, Si, A1

Cr, Na, Pb, Sn

Cr, Co, Cu, Fe, Mn, Ni, V Si, Nil Te, Xi, Ca, Mg Si, Ti, Fe, Ca, Mg, Cr, Pb, Zn, Mn, V,

Cu, B, Ne, K, Li . . 25 elements Si, Fe, V, Zn, Ti All Bi, B, Ca, Cr, Co, Cu, Fe, Pb, Mg,

Al, V, Mn, Na, K, Cr, Ta Fe, Xi, Cu, All Si, Cr, Mn Fe, Mn, Mg, Cr, Cu, B Mn, Na, Cu, Cr, Sc, Fe, Zn, Co, Ta, Ni B, Fe, Ai, Mg, Ni, Mn, Cr, Ca, Cu, Pb,

Mn, Mo, Xi, Si, Ag, Sn, Ti, V

Si 33 elements Cu, Fe, Nil Pb, V, Zn Be, All Zr, Ca, Cu, Fe, Ni

Ag, Cd, Be, Cu, Li, P, Gal Si, W, Sb, Ni, Sn, Fe, Mn, Na, Co, Bi, In, Mo, Ba, Zn, V, As, T1, Cr, Sr, Pb, A1

Ce, Nd, Pr, La, Zn, Zr All Be, Ca, Fe, Si, Zn Ta, Mn, Fe, Xi, Al, Cr, Mg, P, Si B, Ba, Fe, Si, Sr Al, Cr, Fe, Mn, Mg, Cu, V, Mo, W,

Fe, Si, Ni, Cr, Mn Sn, Bi, Pb

Al, Mo, Cr, Mn, V Cu, Ca, Cr, Al, V, W, Fe, Si, Mg, Mn,

Ni, Nb, Sn, Pb Fe, Si, Nb, Ca,.V, Mg, Al, P Mg, Fe, Mn, Si

S. Spectrographic X. X-ray

Methods used

Col. P C A A

A A A S S S S F X X A Col.

At C Col. S S S Col. C, Col., F c, Col., s,

X S S

S S S A Col. S A S

S Col., P S S

S S c, Col. S S

S

S S S S

s J

Refer-

(806 j ( 7 9 )

VOL. 37, NO. 5 , APRIL 1965 93 R

Arsenic. Steckel and Hall (167) reported a spectrophotometric de- Table It. Methods for Elements in termination of trace arsenic in alu- Con- minum and its alloys using silver diethyldithiocarbamate. The pro- cedure included reducing As(\’) to .Is(III). evolving arsenic as AsHa into a pyridine solution of the reagent to form the stable red As(II1) complex, and measuring the absorbance a t 540 mp. Copper and antimony interfered.

Alikheeva and Kihitill (1 17) pro- posed the determination of arsenic, phosphorus, and sulfur in beryllium oxide by radioactivation analysis. The sample was activated by a stream of l O I 3 neutrons per sq. em. per sec. for 10 minutes and kept for 30 hours. The arsenic was reduced with hydroxylamine hydrochloride, precipitated as the sul- fide, and measured by radioactivity.

Beryllium. Kida et al. (86) de- scribed the photometric determination of beryllium in copper-beryllium and beryllium-aluminum alloys with 8- hydrovylquinaldine in chloroform a t 380 inp. Copper and aluminum were masked with KCN and EDTA, re- spectively, a t pH 8.0. Postma and AlcMurray (152) utilized activation analysis for the determination of beryl- lium in beryllium metal by con- centrically surrounding an Sb124 pencil and counting neutrons produced in beryllium with fission counter tubes.

Bugaeva and Mironenko (17) rec- ommended sulfosalicylic acid for the spectrophotometric determination of beryllium in magnesium alloys. Hy- droxylamine hydrochloride was added to mask iron and Trilon B to mask magne- sium. The complex was developed a t pH 10 to 11 and the absorbance was measured at 320 mp.

Bismuth. DeAngelis and Gerardi described spectrophotometric deter- minations of copper and bismuth separately (26) and simultaneously (27) in aluminum alloys containing lead. In the separate determinations diethyl- dithiocarbamate was used for copper and the cupferron-KI or the HBr method was used for bismuth. In the simultaneous determinations a nitric acid sample solution wa5 treated with thiosemicarbazide for copper, KI for bismuth, and S a C l to complex lead. Copper and bismuth were measured a t 560 and 166 mp. S’inogradova and Vasil’eva (196) reported the determina- tion of small amounts of bismuth, tin, and antimony in aluminum as described under the section on .Intimony.

Tumanov and Sidorenko (187) studied the determination of bismuth in titanium dioxide based on the formation of the yellow complex iodide which is stabilized with hydrazine sulfate.

Boron. Ichiryu and Hashimoto (72) studied the spectrophotometric determination of traces of boron in aluminum with 1 ,l’-dianthrimide a t

stituent deter- mined Ag A1

ALOa

As

B

Be

Bi

C

Ca

Cd

Ce

CI

Co Cr c u

Fy Fe

Ga

H

Material Aluminum alloys Aluminum-bronze alloy

Aluminum-base alloy Xagnesium alloy Magnesium metalp Titanium dioxide pig-

ment Titanium slags illuminum Titanium oxide Aluminum, aluminum

alloys Berylliuni oxide Aluminum Alumlnvm alloys Aluminum Aluminum Beryllium oxide Magnesium alloys Magnesium Titanium Copper-beryllium,

Beryllium Magnesium alloys Aluminum alloys Aluminum Titanium dioxide Beryllium Titanium Titanium sponge Aluminum Titanium dioxide Aluminum Aluminum Aluminum, aluminum

alloys Aluminum alloys Copper-aluminum alloys Aluminum oxide Magnesium alloys Beryllium Titanium dioxide Magnesium-base alloys Aluminum black Aluminum alloys

Aluminum alloys

Aluminum alloys Aluminum alloys Aluminum-bronze alloy

beryllium-aluminum

Aluminum alloys High-purity aluminum Aluminum Aluminum alloys Aluminum alloys

Aluminum Aluminum alloys Aluminum Aluminum Aluminum Aluminum alloy Aluminum

Aluminum black Aluminum Aluminum alloys Titanium chips Titanium dioxide

High-purity aluminum Aluminum Aluminum Bauxites Aluminum Aluminum Aluminum

Reagent or method Atomic absorption Paper chromatography,

Chelometric Chelometric Photometric, oxine Photometric

photometric

Chelometric Aluminon, photometric Trilon B, FeC13 Photometric

Activation 1,l ’-Dianthrimide Spectrographic Photometric Acidimetric Photometric Photometric Curcumin Curcumin Photometric

Activation Photometric Photometric Anodic voltammetry Photometric, iodide Activation analysis Combustion, titration High-frequency combustion Flame photometric Photometric, murexide Photometric, dithizone Anodic voltammetry Polarographic

Polarographic Polarographic Photometric Photometric X-ray fluorescence HgC12 Activation analysis Dip henylcarbazide Photometric, diethyl-

dithiocarbamate Photometric, thiosemi-

carbazide Extraction, iodimetric Iodimetric Paper chromatographic,

photometric, Chrome Azurol S

Spectrographic Spectrographic Spectrographic Electrolytic Cation exchange,

electrolytic Activation analysis Square-wave polarographic Activation analysis Photometric Spectrographic Photometric, EDTA, H202 Photometric, 1 , l O -

phenan throline Photometric, haematoxylin Activation analysis Square-wave polarographic Spectrographic Photometric, 1 , l O -

phenanthroline Anodic voltammetry Photometric Activation analysis Extraction, spectrographic Mass spectrometric Vacuum heating Spectral-isotopic

References

(161, 18.9, ZOO) ( 7 7 )

(89, 100) (17%)

94 R a ANALYTICAL CHEMISTRY

Nonferrous Metallurgical Materials 630 mp. Most of the aluminum moved on a column of Dowes-50 resin and the boron was eluted with water. The eluate was heated with the reagent in sulfuric acid. There was no inter- ference from <1Yc chromium and <0.2% vanadium. Kuzovlev and Gusarski (101) proposed a spectral method of determination of thousandths of a per cent of boron in aluminum alloys. Keniodruk, Palei, and Hun-I (132) described a rapid photometric determination of traces of boron (down to in metallic aluminum with acetylquinalizarin a t 620 m l . Kosen- berg (1 55) recommended determining boron present in amounts >lo0 p.p.ni. in aluminum by first removing the aluminum by cation exchange. The

was converted to its complex with mannitol and determined acidi- metrically with CY-naphtholphthalein as indicator.

Karalova and Semodruk (80) pro- posed an extraction and photometric det,ermination of boron in beryllium oxide. The sample was heated with H F and neutralized with urotropine by using Brilliant Green. After estractiori with benzene and centrifugation, the complex was measured at 656 mp.

Pitwell (148) investigated the dis- solution of samples for determining traces of boron without loss of boron as boranes or H3B03. Inclusion of re- sidual acid in the distillation was avoided. The sample was placed in a distillation flask fitted with a dropping funnel and a condenser which dipped below the surface of a solution of S a O H in aqueous glycerol. hnhydrous nieth- anol was added and HeS04 or H3P04 in methanol was added gradually until the sample was dissolved. The distillate contained methyl borate and any borane included was hydrolyzed by the SaOH. The procedure was applicable to boron in magnesium and aluminum.

Gordievskii and I'styugov (57) de- scribed t'he fluorometric determination of boron in magnesium alloys with Anthraquinone blue SVG. In the presence of boron the reagent produced an intense bright red fluorescence. The photometric determination of boron in magnesium metal has also been ac- complished with curcumin (189). Elwell and Wood (35) and Hayes and Metcalfe (67) used curcumin for deter- mining boron in titanium, zirconium, and hafnium with no preliminary separation.

Cadmium. Hashimoto and 'I'anaka (66) determined traces of cadmium in aluminum by extraction with dithizone in chloroform and photometrically a t 517 mp. Hine and Bates described a polarographic determination of 0.1 to 0.35% cadmium in aluminum alloys containing 57 , copper by using the derivative curve with 1.11 HC1 as the supporting electrolyte. Lithium, iron,

Con- stituent deter- mined

H

Hf K Li Mg

Mtl

>!IO

N

Na

Xi

0

P

Ph

Pd

Re s

Sh

sc Si

Sn

Ti

Material

Aluminum, beryllium Magnesium Titanium Aluminum alloys Aluminum Aluminum Aluminum alloys Aluminum alloys Aluminum alloys Aluminum oxide Titanium sponge Titanium dioxide Aluminum, aluminum

alloys Aluminum alloys Aluminum Aluminum alloys Aluminum Magnesium Aluminum alloys Beryllium High-purity titanium Beryllium Titanium High-purity aluminum Aluminum, aluminum

alloys Aluminum alloys Aluminum, magnesium,

their alloys Beryllium, beryllium

oxide Beryllium Beryllium Beryllium oxide

Magnesium Titanium Titanium Titanium, aluminum Aluminum-silicon alloys

Aluminum-silicon alloys Aluminum-silicon alloys Beryllium oxide Aluminum alloys Aluminum-copper alloys Beryllium-copper alloy Titanium alloys Titanium alloys Titanium alloys Beryllium oxide Beryllium oxide Beryllium oxide Titanium Aluminum Magnesium-base alloy Titanium dioxide Titanium dioxide Xragnesiurn alloys

High-purity aluminum Aluminum alloys Aluminum alloys Aluminum-silicon alloy Copper-beryllium alloy High-purity aluminum Aluminum alloys Beryllium-copper alloy Aluminum

Aluminum

-4luminum alloys

Aluminum alloys

Aluminum alloys Beryllium

Reagent or method

Isotopic dillution Pressure, Pd tube Spectrographic Gravimetric, titrimetric Flame photometric Flame photometric C helo met r ic Spectrographic Atomic absorption Photometric, magneson Spectrographic Photometric, magneson Potentiometric titration

Iodometry Spectrographic Spectrographic Activation analysis Photometric Photometric, thiocyanate X-ray absorption Extraction, photometric Activation analysis Spectrographic Activation analysis Flame photometric

Spectrographic Photometric, dimethyl-

glyoxime Ion exchange, photometric,

dimethylgl yoxime Activation analysis Vacuum fusion Vacuum fupion, mass

spectrometric Gas analysis Hydrogen adsorption Spectrographic Activation analysis Photometric, molybdenum

Photometric, gravimetric Activation analysis Activation analysis Polarographic Polarographic Polarographic Photometric, PAN Photometric, SnClt Photometric, thiooxime Combustion, titration Adsorption, titration Activation analysis Iodimetric, Bas04 Anodic voltammetry Activation analysis Photometric Polarographic Photometric, Xylenol

Orange Spectrographic Elemental silicon Titrimetric X-ray fluorescence Photometric, molybdate Anodic voltammetry Photometric, haematoxylin Polarographic Photometric, salicylate,

quinine Photometric, phospho-

titanomolybdate Photometric, isoxanthenone

compound Photometric, dichloro-

chromotropic acid Polarographic Photometric, thymol

blue

(Continued on page Q6R)

VOL. 37, NO. 5, APRIL 1965 95 R

To ble II. Methods for Elements in Nonferrous Metallurgical Materials (Continued)

Con- stituent deter- mined

Ti

I:

v

W Zn

Zr

Material

Titanium-aluminum

Titanium slag Aluminurn alloy Beryllium oxide-uranium

oxide .iluminum Aluminum powder

Titanium

Titanium Aluminum alloy Aluminum alloy Aluminum alloy Copper-aluminurn alloys A41uminum alloys High-purity aluminum Aluminum alloys High-purity aluminum Aluminum alloys Bauxite, alumina,

Sickel-magnesium alloy Magnesium alloys LIagnesium alloys llagnesium alloys Magnesium alloys Titanium alloys

alloys

aluminum

Reagent or method

Chelometric

Titrimetric X-ray fluorescence Titrimetric

Activation analysis Photometric, phospho-

tungstate Photometric, phospho-

tungstate Photometric, thiocyanate Photometric, Xylenol Orange Chelometric Ion exchanger, eIectroIytic Polarographic Polarographic Anodic voltammetry Spectrographic Spectrographic Atomic absorption Photometric, dithizone

Ion exchange, chelometric Photometric, tartrazine Photometric, PAN Photometric, morin Photometric, Alizarin S Photometric, Alizarin

Red S

manganese, titanium, vanadium, and lead did not interfere. Fleury and Capelle (46) reported the polarographic determination of lead and 0.001 to 0.25% cadmium in copper-aluminum alloys. Copper was separated by electrodeposition and the lead and cadmium were determined in a chloride medium. In a later paper Fleury and Capelle (46) recommended the polaro- graphic determination of cadmium in aluminum and its alloys by dissolving the sample in HCI, separating the metallic copper and Si02 by filtration and reducing the ferric iron with ascor- bic acid. This method avoids the electrolytic removal of copper, iron, tin, and lead. Vasil'eva and Vinogradova (194) studied the determination of very small amounts of gallium, zinc, and cadmium in high-purity aluminum by anodic voltammetry at a stationary mercury electrode with a silver contact. Cadmium (2 X 10--6yo) was determined in an hlC1, and HC1 (pH 2 to 3) medium.

Klug and Sajo (92) de- scribed the flame photometric de- termination of calcium in analyses in the aluminum industry by the ad- dition of butanol to HC1 solutions of the samples.

Bogatyrev, Savyazhskaya, and Sporykhina (1 0) investigated rapid methods for the colorimetric determina- tion of magnesium and calcium in titanium dioxide. Murexide was used for calcium.

Calcium.

Carbon, Bradshaw, Johnson, and Beard (14) developed a method for the determination of trace amounts of oxygen, nitrogen, and carbon in beryl- lium by gamma-ray activation. I t is the only method available for the determination of carbon contained in beryllium in the range of 10 to 1000 p.p.m.

Fujishima and Takeuchi (49) rec- ommended a rapid combustion (1200' C.) and titration determination of traces of carbon in titanium. An absorber containing a Ba(OH)2 solution and isopentyl alcohol (as a defoaming agent) was fitted on the combustion apparatus. Cresol red and thymol blue were used as the indicators for the final titration. Shimazaki, Nakayama, and Sakamura (162) utilized high- frequency combustion for the deter- mination of microaniounts of carbon in titanium sponge using a crucible made of material containing A I 2 0 3 and SiOz in the ratio of 10 to 8.

Cerium. hlendlina (115) reported a photometric determination of cerium in aluminum oxide by treating the solution with potassium citrate and hydrogen perovide a t p H 8 to 9. Up to 0.05% of Fe20a1 SiO2, Ca, or MgO offered no interference. I n the determination of cerium in mag- nesium alloys by the citrate method, Tikhonov (177) proposed hays of eliminating the effect of rare earths, magnesium, and manganese and

developed a method without physical destruction of the sample.

Chlorine. Keys and Rowan (83) recommended the determination of chloride in beryllium metal by x-ray fluorescence. Microgram quantities were determined by comparing the secondary fluorescent emission from an unknown sample to t h a t from standard pellets.

Tumanov and Sidorenko (187) studied the determination of chloride in titanium dioxide based on the formation

Chromium. Guerreschi and Romita (61) used diphenylcarbazide to deter- mine chromium (5% CrzOg) in aluminum black after the separation of Fe+3 by precipitation as hydroxide from a solution buffered with KOH- (SH4)2S04 in the presence of (n"4)2- U207 as a carrier. Under these con- ditions aluminum and chromium were not precipitated. Iron was determined in a solution of the precipitate.

Cobalt. Todd, Cuthbert, and Dick- inson 1182) proposed a method for the determination of antimony and cobalt in magnesium alloyed with small amounts of aluminum and manganese by neutron activation analysis. The method is described in the Antimony section.

Copper. Dehngelis and Gerardi recommended spectrophotometric de- terminations of copper and bismuth separately (26) and simultaneously (27) in aluminum alloys containing lead. The procedures are summarized in the Bismuth section. Tajima, Kurobe, and Terada (175) investigated the extrac- tion of the copper thiocyanate complex into tributyl phosphate and its applica- tion to the analysis of aluminum alloys. A 0.2M to 0.8M thiocyanate solution a t pH 1 to 5 was used and the tributyl phosphate was dissolved in 1:1 light petroleum-benzene. Copper mas re-ex- tracted into 1 X SH4C1 containing S H 3 and determined iodimetrically. l lunshi and Dey (127) reported a paper chroma- tographic separation and determination of copper and aluminum in aluminum- bronze alloys. The method is described in the Aluminum section. Copper was determined colorimetrically using Chrome Azurol S. Nukai and Mochi- zuki (126) developed a rapid method for the determination of copper in aluminum alloy containing silicon. The saniple was dissolved in nitric acid containing NH4HF2. After complete dissolution SHaHFZ, XH40Ac and urea were added and the copper was titrated iodi- metrically.

Vvedenskii, Shekhobalova, and Novikova (200) found that silicon markedly affected the determination of copper in the analysis of aluminum- copper alloys by spark excitation of the spectra. The effect produced by silicon appeared suddenly a t a concentration of

of HgC12.

96 R e ANALYTICAL CHEMISTRY

27, Si and remained unchanged up to 6% Si. Torok (183) utilized a low- voltage spark excitation for the spectro- graphic determination of 0.1 to 1.0% copper in aluminum alloys. In estab- lishing the spectra below 2300 A, spectral plates were previously sen- sitized with sodium salicylat,e in methanol. Kajzer (77) reported the spectrochemical analysis of high-purity aluminum for iron, silicon, and copper in the concentration range lop3 to 1.4 X 1 0 - * ~ o by t,he intermittent-arc tech- nique. The line A1 2669 A. was used as internal standard, and the lines Si 2516 A., Fe 2599 .I., and Cu 3274 A. were used for the determination. Schroeder and Strasheim (161) studied the synchronized direct-reading spec- trometer-spark system for time-resolved spectra of copper spectral analysis lines used for the determination of copper in aluminum alloys. Oida, Fujita, and Takahashi (137) developed a spectro- chemical method using a quanto- recorder for the determination of 0.0005 to 0.01% silicon, iron, and copper inhigh- purity aluminum. The direct point-to- plane method with excitation with over damped discharge by low voltage was used.

Bertoldi and Tartari (6) reported the electrolytic determination of copper in aluminum alloys in the presence or absence of bismuth from a HKOa- HBF4 or HN03-HF-HBF4 solution. Tin was complexed but bismuth was removed by co-deposition with lead at the anode. Kharin and Soroka ( 8 4 ) developed a n ion exchange-electrolytic determination of zinc and copper in aluminum alloys not containing nickel. Iron, aluminum, manganese, magnesium, chromium, and silicon were complexed with Na4P207 and zinc and copper were complexed with KH3. The solution was passed through a cation exchange resin which allowed the pyrophosphate anions to pass through while the zinc and copper cations were adsorbed. After elution of zinc with NaOH and copper with HC1, they were determined by electrolytic separation.

Kiesl, Bildstein, and Hecht ( 8 9 ) pro- posed activation analysis for the deter- mination of copper and dysprosium in aluminum. The copper complex of 2,2'-diquinolyl was extracted by amyl alcohol, re-extracted into the aqueous layer with "03 and precipitated by benzoin oxime. The 0.51-m.e.v. peak of the annihilation radiation was meas- ured. Dysprosium was determined without destruction by measuring the 91-k.e.v. peak after a short time of radiation. Kukula, Slunecko, and Sim- kova (f 00) recommended the activation analysis of aluminum for copper with Cue4 after separation with ammonium reineckate.

Tajima and Kurobe (f7.2) in- vestigated the determinationn of copper,

zinc, and iron in aluminum alloys by square-wave polarography without interference from other constituents. The polarograms for copper and zinc were recorded from an HCI solution at -0.025 and - 1.05 volts, respectively, us. the mercury-pool electrode.

Dysprosium. Kiesl, Bildstein, and Hecht ( 8 9 ) proposed activation analysis for the determination of copper and dysprosium in aluminum. The method is discussed in the Copper section.

Fluorine. Valach (191) described the photometric determination of fluorine in aluminum based on the considerable stability of the chelates of zirconium with Xylenol Orange type dyes in 1 to 2-V HC1O4, H N 0 3 , and HC1 which decomposed interfering fluoroaluminates.

Gallium. Vasil'eva and Vino- gradova (294) studied the determina- tion of very small amounts of gallium, zinc, and cadmium in high-purity aluminum by anodic voltammetry a t a stationary mercury electrode with a silver contact.

Suzuki (170) recommended the spectrophotometric determination of gallium in aluminum with PAN, 1-(2- pyridylazo)-2-naphthol. An HC1 solu- tion of the sample was extracted with isopropyl ether (Fe+3 was reduced to Fe+* with TiClS), the ether was removed, and the residue was adjusted to p H 4.3. This solution was extracted with a chloroform solution of the reagent and its absorbance was measured at 550 mp.

Kiesl, Rildstein, and Sorantin (90) utilized activation analysis for the determination of manganese and gallium in aluminum. Manganese was separated from neutron-irradiated aluminum by extraction of MnOl- with (C&Is)4AsCI and CHC13 and measured by counting the 0.85-m.e.v. photopeaks of M n s . After a cooling period of 17 hours, the Mn56 died out, and the 0.85- m.e.v. peak of Ga7* was determined directly with the aluminum sample.

Landi (102) reported the determina- tion of gallium in bauxites by a com- bined extraction-spectrographic method which consisted of extracting gallium chloride with ethyl ether, evaporation, hydrolysis with NaOH, dehydration at 700' C., and mixing the oxide with graphite for sparking.

Hafnium. Sikes, Wade, and Yamamiira (165) discussed procedures for both a titrimetric and gravimetic determination of hafnium in aluminum alloys. The sample was dissolved in aqua regia and any undissolved hafnium was taken into solution by pyrosulfate fusion. The hafnium was separated from the aluminum and contaminants in the aluminum by precipitation as the mandelate. In the gravimetric pro- cedure the hafnium mandelate was heated to the oxide and weighed. I n

the titrimetric procedure the mandelate was destroyed by acids and the hafnium was determined by back titrating an excess of EDTA with bismuth with Xylenol Orange as indicator.

Hydrogen. Orlovtsev, Krapukhin, and Krestovnikov (140) discussed the mass spectrometric determination of hydrogen in aluminum. Klyachko, Kunin, and Chistyakova (93) reported the determination of hydrogen in aluminum by vacuum heating.

Orlova and Petrov (139) proposed a spectral-isotopic method for the deter- mination of hydrogen in aluminum alloys. The method was utilized at 500" C. on samples 5 to 6 mm. in di- ameter and 10 to 20 grams in weight. The experimental determined time for isotopic equilibration was 25 to 30 minutes. Evans and Herrington (58) recommended the determination of hydrogen in aluminum and beryllium by isotopic dilution with tritium.

Berry and Walker (5) developed a method for determining hydrogen in magnesium alloys involving the simul- taneous sublimation of magnesium from a graphite crucible and the removal of hydrogen from the furnace system. The amount of hydrogen was deter- mined by collecting the gas in a calibrated volume and measuring the pressure with a McLeod gauge before and after diffusion through a palladium tube.

Kalinin, Kondrashova, Slironov, and Yalymov (78) studied the spectral determination of hydrogen in titanium. The optimum conditions for the calibra- tion curve were: inductance, 3 phenry and slit width, 0.06 mm. A small interelectrode gap was recommended to increase the accuracy. Kovalenko (98) investigated the characteristics of the photoamplifying system in the spectral determination of 0.002 to 0.2% hydro- gen in titanium.

Kern (82) critically discussed methods of determining hydrogen, nitrogen, and oxygen in beryllium, magnesium, and titanium.

Iron. Christ (bf) utilized the melt- in-rod technique for the spectro- chemical determination of iron and manganese in aluminum chips, sheet, or foil when only 5 to 7 grams are available. The sample was melted (in a graphite block) and forced into a n aluminum rod having a preformed crater and air outlets. The cool sample was then machined and analyzed. Kajzer (77) reported the spectrochemical analysis of high-purity aluminum for iron, silicon, and copper as described in the Copper section. Oida, Fujita, and Takahashi (f37) developed a spectrochemical method using a quantorerorder for the deter- mination of silicon, iron, and copper as discussed in the Copper section.

Onishi (138) recommended a rapid

VOL. 37, NO. 5 , APRIL 1965 97 R

colorimetric determination of iron in aluminum alloy with E D T A and H202. Absorbance measurements were made a t 517 nip. Jackson and Phillips (76) studied the colorimetric determination of iron in zone-refined aluminum after solvent extraction. Iron was first extracted from the sample solution with isobutyl methyl ketone, which in turn was extracted with a buffer solution con- taining 1,lO-phenanthroline. Guer- reschi and Romita (61) determined iron in aluminum black (containing chromium) spectrophotometrically with haematoxylin. The procedure was dis- cussed in the Chromium section.

Grossmann and Doege (60) described the determination of iron in pure aluminum by activation analysis. The samples are irradiated for 100 hours at a rate of 10'3 neutrons per sq. cm.-sec. Iron was separated by ion exchange, solvent extraction, and precipitation before counting. Tajima and Kurobe (1 72) investigated the determination of copper, zinc, and iron in aluminum alloys by square-wave polarography without interferences from other con- stituents. The polarogram for iron was recorded a t -0.3 volt us. the mer- cury-pool electrode after a solvent extraction separation of the iron.

Gusarskii and Kuzovlev (62) pro- posed a spectrochemical determination of iron in titanium chips using the analytical line pair Fe 2599.40 A . and Ti 2555.99 A. Tumanov and Sidorenko (187) reported the determination of chloride, iron, and bismuth in titanium dioxide. -1 photometric method for iron was employed using 1,lO-phenanthroline.

Lead. Stross and Clark (169) recom- mended the polarographic determination of lead in aluminum alloys containing molybdenum or up to 570 iron. Fleury and Capelle (45) employed a polaro- graphic determination of 0.005 to 0.25% lead and cadmium in copper-aluminum alloys. Copper was separated by elec- trodeposition and the lead and cadmium were determined In a chloride medium.

Kida et al. (88) determined tin and lead in a beryllium-copper alloy polaro- graphically with a salt calomel electrode. Tin and lead were coprecipitated with Be(OH)2 and separated from copper, which was redissolved in excess ",OH. The polarogram of tin and lead was taken on a portion of the acid solution of the precipitate. A second polarogram (of lead) waq taken on a portion of the solution made alkaline. The tin was ob- tained by difference.

Lithium. Pilgrim and Ford (147) reported the determination of lithium in aluminum by an improved flame photo- metric method. The addition of iso- propyl alcohol and acetone to acid colu- tions containing lithium and aluminum permitted the determination of micro- gram levels of lithium without sep- aration.

Magnesium. Costin (22) developed a rapid complexometric method for the determination of 0.3 to 6% mag- nesium in aluminum alloys by titrating a solution (buffered a t p H 10) with Complexon I11 using Eriochrome T as indicator. Smart (166) preferred Calmagite as an indicator for the complesometric determination of magnesium in aluminum alloys. Also, more careful control of pH a t the manganese precipitation sta, oe overcame positive errors.

Peter (144) described a spectro- chemical determination of magnesium in aluminum alloys by differences in line densities. The determination was carried out under two sets of excitation conditions. Wallace (203) recom- mended atomic absorption spectros- copy for the determination of magnesium in aluminum alloys. The serious interference of aluminum was overcome by the use of 8-hydroxy- quinoline. Korenman (96) determined trace amounts of magnesium in aluminum oxide with magneson IREX, sodium 5 - chloro - 2 - hydroxy - 3- (2 - hydroxy - 1 - naphthJ4azo) benzene- sulfonate. By allowing the reaction to proceed for 1 to 2 days, the sensitivity was increased.

Tsuji, Abe, and Ando (184) proposed a spectrographic determination of magnesium in titanium sponge with a simplified reservior-cupped conical electrode. A polyethylene cup was cut and fitted over a graphite electrode so that it could hold the solution to be analyzed. Bogatyrev, Navyazhskaya, and Sporykhina (10, 11) studied rapid methods for the colorimetric determina- tion of magnesium and calcium in titanium dioxide. Magneson was used for magnesium.

Manganese. Pohl (150) described the potentiometric titration of man- ganese in aluminum and its alloys. Mn(I1) was titrated with K M n 0 4 in a pyrophosphate solution a t p H 6.5 to form a Mn(II1) pyrophosphate complex. hliyajima (120) investigated the determination of 0.12 to 1.53% manganese in aluminum alloys by io- dometry using EDTA as a masking agent.

Christ (21) utilized the melt-in-rod technique for the spectrochemical deter- mination of iron and manganese in aluminum chips, sheet, and foil when only 5 to 7 grams are available. The method is summarized in the Iron section. Laszlo (103) and Peter (145) reported spectrochemical methods based on the density differences of manganese in aluminum alloys. The density dif- ferences of the pairs of ?*In lines 3547.79- 2798.27A. and 3547.74-2576.10 -1. were used to plot a calibration curve. Kiesl, Rildstein, and Sorantin (90) employed activation analysis for the determina- tion of manganese and gallium in

aluminum as described in the Gallium section.

Tikhonov and Nikitina (181) re- ported the determination of small quantities of manganese in magnesium alloys with rare earths by oxidation with KIO, after extraction with a CCI, solution of sodium diethyldithiocarba- mate.

Molybdenum. Stross and Clark (168) used SaSCX and SnC12 for the spectrophotometric determination of molybdenum in aluminum alloys. Iron was reduced by SnC12, and copper which precipitated was filtered off. Other usual constituents or impurities had no effect.

Karev and Matyuehenko (81) rec- ommended x-ray absorption analysis of beryllium for the determination of molybdenum.

Shustova and Xazarenko (1 6 4 ) determined traces of molybdenum in high-purity titanium by making a chloroform extraction as the 8- quinolinolate and determining the molybdenum colorimetrically as the salicylfluorene or thiocyanate complex.

Nickel. Penner and Inman (143) applied the determination of 0.0005 to 1.Oy0 nickel by spectrophotometric measurement of the chloroform ex- tract of nickel(I1) dimethylglyoximate to the analysis of aluminum and magnesium and their alloys. Zinc and copper, which interfered, were complexed with S a 2 S 2 0 3 a t pH 4.5 to 5.0 and p H 6 .5 , respectively. Large amounts of copper were re- moved electrolytically.

Hibbits and Kallmann (68) described the photometric determination of nickel in beryllium and beryllium oxide after its separation by precipitation and ion exchange. Cadmium was added to the sample solution and was precipitated along with nickel from a chloride- sulfate-tartrate medium at pH 8.5 with benzotriazole. After dissolution of the precipitate in HN03-HC104, the nickel was separated by ion exchange before being determined a t 465 mp as the dimethyl-glyoxime complex.

Nitrogen. Bradshaw, Johnson, and Beard (14) developed a method for the determination of trace amounts of oxygen, nitrogen, and carbon in high- purity beryllium by gamma-ray activa- tion. The method was used to estimate the nitrogen content when the iron and copper contents of the sample were accurately known.

Romand, Balloffet, and Vodar (154) proposed the spectrochemical deter- mination of oxygen and nitrogen in titanium by vacuum sparks. Kern (sa) critically discussed methods of determining hydrogen, nitrogen, and oxygen in beryllium, magnesium, and titanium.

Oxygen. Gamma-ray activation was employed by Bradshaw, Johnson,

98 R ANALYTICAL CHEMISTRY

and Reard (14) for the determination of trace amounts of oxygen (10 to 5000 p.p,in.), nitrogen, and carbon in high- purity beryllium. The technique was used as a standard method for t,he evaluation of analytical techniques for oxygen. AIcCrary, l Iorgan. and Bag- perlv (1 12) recommended the deter-

en in beryllium by analysis. The short

sulting from the re- action 016((n,p)91fi was used to determine

en. Irradiation was carried out with 1.8 X 10" neutrons per sq. cm.-see. Fiijii, SIuto, and Sliyoshi (48) also utilized neutron activation analysis in the determination of 0.002 to 0.5y0 oxygen in titanium and aluminum using the above-mentioned reaction. The neutron intensity in this cape was 1Olo neutrons per sq. cni.-sec. Gilman and Isserow (63) discussed both chemical and radioactivation determinations of osygen in beryllium. Two chemical methods were used: (a) volat'ilization of beryllium as the chloride and (b) selective dissolution of beryllium in bromine-methanol. I n both methods, a residue rontaining oxygen as B e 0 was analyzed for beryllium. In activation analysis oxygen was converted to 0 1 5

by gamma-neutron reaction. l leyer , .\usterman, and Swarthout

(1 16) described a method and apparatus for the determination of small isotopic oxygen variations in beryllium oxide. .I vacuum fusion apparat,us using a 1)latinum flus contained in a graphite crucible a t 2200" C. was used to release the oxygen in B e 0 as CO. The re- sultant CO was analyzed for C0l8-C0lB ratio by mass spectrometry.

Everett and Thompson (40) studied the determination of oxygen in her!-llium by vacuum fusion. Sugges- tions were made with regard to apparatus design and operating tech- nique. llaintenance of high pumping speeds for high pressures a t t'he crucible and the use of capsules to enclose all samples were the most important factors.

Oda, Sorishima, and Kubo (135) determined oxygen in magnesium by placing a sample in a graphite boat, the bottom of which was covered with powdered carbon, and heated a t 900' C. in an HCl stream. The evolved gas was passed onto a platinum-carbon layer a t 1000' C. in a platinized tube, so that the osygen was reduced to CO. After the removal of HC1, CO was osidized to COz with HI3O3, followed by weighing.

Romand, Balloffet, and Vodar (154) proposed the spectrochemical deter- mination of oxygen and nitrogen in titanium by vacuum sparks. Livanov, Ilukhanova, and Kolachev (110) re- ported a method for the determination of oxygen in titanium based on the measurement of equilibrium pressure of hydrogen introduced into the sample.

The method u a s claimed to be faster than the conventional vacuum melting method and required simpler apparatus and less skilled personnel.

Palladium. Sawada and Kat0 pro- posed two spectrophotometric methods for the determination of palladium in titanium alloys. The first was the PAS, 1-(2 pyridylazo)-2-naphthol, method (159) which iq applicable to the concentration range 0.001 to 1% Pd. The sample was dissolved in HCl- citric acid-HF and finally in HxO3- H3B03. EDTA and PAN in methanol were added, the p H was adjusted to 3.0 to 3.5 and the solution was heated to 100' C. After cooling the Pd-PAN complex was extracted with chloroform and the absorbance was read at 675 mp. All elements usually found in titanium alloys did not interfere.

The second method (160) employed SnC12 and was applicable to 0.05 to 5% Pd in titanium alloys. The procedure for dissolution of the sample was similar to the PA4N method except urea was added along with H3B03, The ab- sorbance was measured at 635 mp after the addition of SnC12.

Phosphorus. Davey (25) described the colorimetric determination of phosphorus in aluminum-silicon alloys by development of the molybdenum- blue complex in isobutyl alcohol. Mills and Hermon (118) claimed that a direct photometric determination of phosphorus in hypereutectic aluminum- silicon alloys was not possible because it was first necessary to separate the phosphorus from aluminum and silicon. The apparatus and procedure were described for the separation of phos- phorus from aluminum by distillation as PH3. Also, both gravimetric and photometric procedures were discussed and compared.

Blackburn and Peters (8) recom- mended the determination of 0.001 to O.OlyO phosphorus in hypereutectic aluminum-silicon alloys by neutron activation. The sample was irradiated in a flux of 5 X 10" neutrons per sq. cm.-sec. for 50 hours. After 5 days the irradiated sample was dissolved in HF-HN03 and the converted into the molybdophosphoric acid com- plex, which was extracted into isobutyl alcohol and counted for P32. The method was claimed to be free from the disadvantages of the usual spectro- photometric methods.

Mikheeva and Wihitill (127) re- ported the determination of arsenic, phosphorus, and sulfur in beryllium oxide by radioactivation analysis. The sample was irradiated by a stream of 1013 neutrons per sq. cm.-sec. for 10 minutes and kept for 30 hours.

Potassium. (See Sodium.) Rhenium. Egorova and Gurevich

(33) studied the photometric deter- mination of rhenium in titanium alloys

with 8-mercaptoquinoline (thiooxime) by extracting the complex with chloro- form from a 9 to 1LV HC1 solution and measuring the absorbance at 438 mp. Ti(II1) was oxidized to Ti(1V) with hydroxylamine hydrochloride in order to eliminate its interference.

Scandium. Volodarskaya and Der- evyanko (198) proposed the colori- metric determination of scandium in magnesium alloys m ith Xylenol Orange. Ascorbic acid was added to reduce Fe(II1) and Ce(1V).

Silicon. Xeverovsky (13.9) de- scribed the determination of silicon in aluminum alloys. .\fter the sample was dissolved in acid, the remaining elemental silicon was filtered, washed with water, ethanol, and acetone, dried at 120' to 140' C., and weighed. Hasegawa (64) reported a rapid titri- metric determination of silicon in aluminum alloys, which consisted of the formation of K2SiFfi and its titration with XaOH. Titanium, tantalum, and zirconium interfered.

Kajzer (77) used spectrochemical analysis of high-purity aluminum for iron, silicon, and copper. Details are covered in the Copper section. Lihl and Fischhuber (108) utilized x-ray fluorescence analysis in the determina- tion of silicon in aluminum-silicon alloys.

Kida et al. (87) developed a rapid colorimetric determination of silicon in copper-beryllium alloy using am- monium molybdate. The absorbance was measured a t 750 mp.

Silver. Wilson (208) recommended atomic absorption spectroscopy for the determination of 5 to 70 p.p.m. silver in aluminum alloys. A tube current of 5 ma. and d i t width of 0.05 mm. were optimum. The sample solution was aspirated into a nonluminous air- CO plus hydrogen flame and the rig 328.1-mp emission line was measured.

Sodium. Klug and Sajo (92) de- scribed the flame photometric deter- mination of sodium, potassium, and calcium in aluminum. Matelli and Attini (114) discussed the preparation of a sodium-free aluminum sample in the determination of sodium in aluminum by flame photometry. Milos (119) reported a procedure for the flame photometric determination of 0.001 to 0.02yG sodium in aluminum and its alloys. Wallace (204) investigated the addition of methanol to suppress the effect of aluminum on the emission from sodium in the flame photometric deter- mination of sodium in aluminum.

Gusarskii and Tarasevich (63) pro- posed a spectrographic method for the determination of sodium in aluminum alloys. Solutions of the iample were excited in an a x . arc and the line at 5889.92 A. was measured to determine sodium contents of 0.00037c;-,.

Teillac (176) used a new method of

VOL. 37, NO. 5, APRIL 1965 99 R

indirect activation analysis to determine sodium in high-purity aluminum based on the fact that it was possible to pro- duce sodium from aluminum by nuclear reaction and that the impurity itself also produced the radionuclide.

Sulfur. Iloyle, Gregory, and Sun- derland ( I S ) reported a combustion and titration method for the determination of 10 to 2000 p.1i.m. of sulfur in beryl- lium oxide. The sample was burned a t 1500°C. in a high-frequency single-tube induction furnace in a stream of oxygen. The sulfur was converted to Son, carried by the oxygen stream to an acidified starch-iodide solution, and titrated with KI03. Lin (109) de- scribed the determination of milli, oram amounts of sulfate in beryllium oxide. The sample was dissolved in HSOa-HF, and the residue after fuming was dis- solved in water. The sulfate was ad- sorbed on an alumina column, eluted with N H 4 0 H , passed through a Dowex 50-X8 column (to remove NH4+) and the sulfate was determined by pre- cipitating 13aS04 and titrating the escess barium with EDTA.

llikheeva and Wihitill (117) rec- ommended the determination of arsenic. phosphorus, and sulfur in beryllium oxide by radioactirat'ion. The sample was irradiated in a flux of 1013 neutrons per sq. cm.-sec. for 10 minutes and kept for 30 hours. The sulfur was determined in 13aS04 pre- cipitates from the sample solution.

Oda and Kubo (134) investigated the determinat,ion of total sulfur in titanium. The sample was decomposed with HC1 and the evolved gases were absorbed in an ammoniacal CdC12 solution. The sulfur in the precipitate (CdS) and in the solution (SOZ-~) mere determined iodimetrically. Sulfate was determined as 13aS04 after the titanium was precipitated with ",OH.

Tin. Vinogradova and Vasil'eva (196) reported the determination of small amounts of tin, bismuth, and antimony in high-purity aluminum by anodic voltanimetry a t a stationary mercury electrode as discussed in t,he Antimony section. Tanaki (1 7 4 ) rec- ommended the photometric determina- tion of >0.05% tin in aluminum alloys using oxidized haematoxylin a t 570

Kida et al. (88) determined tin and lead in a beryllium-copl)er alloy polaro- graphically with a salt calomel electrode. 3Iore details are given in t'he Lead section.

Titanium. Volkova, Get'inan, and Emtsova (197) determined titanium in aluminum photometrically as the titanium ~ salicylate - quinine cornples, which was extracted with chloroform froin a pH 3 solution. Shkaravskii (163) proposed the photometric deter- mination of small amounts of titanium in aluminum by estraction as phosphoti-

mK.

tanomolybdate with butanol and chloro- form. The absorbance was measured a t 360 mfi. hsmus, Kurzmann, and Wallsdorf (4) recommended the use of 2,3,7 - trihydroxy - 9 - (3,4 - dihydroxy- phenyl)-6-isoxanthenone for the photometric determination of 0.005 to 1.2% t,itanium in aluminum alloys a t a pH of 1.5. Budanova and Pinaeva (16) reported the photometric determination of titanium in aluminum alloys con- taining vanadium with dichlorochronio- tropic acid a t 490 mp.

Khasnobis (86 ) utilized polarography for the estimation of titanium in aluminum and its alloys. Titanium oside was precipitated froin the sample solution and dissolved, after filtration, with oxalic acid. The polarogram was obtained between -0.2 and -0.7 volt.

Pribil and Vesely (153) applied chelo- metric methods to the determination of titanium in titanium-aluminum alloys. Sodium salicylate (to mask aluminum) and triethanolamine were added to the sample solution and the pH was ad- justed to 1 to 2. Bismuth was used to titrate the excess EDTA added with Xylenol Orange as indicat'or. When iron was present, titanium was first precipitated with NaOH in the presence of triethanolamine, which kept Fe(II1) and A1 in solution.

Walkden and Heathfield (202) studied the photometric determination of titanium in beryllium by a chloroform- cupferron extraction, evaporation of the organic layer to dryness and fusion of the residue. The titanium in a solu- tion of the residue was determined by a freshly prepared thymol reagent.

Zinchenko, Ershova, and Gertseva (214) reported the determination of bi- and trivalent titanium in titanium slag. The sample was decomposed with H3P04 and the titanium was titrated with FeSH4(S04)2 wit'h thiocyanate indicator.

Tungsten. Dymov and Kozel (52) described the colorimetric determina- tion of tungsten in titanium based on the extraction of the thiocyanate com- plex with isobutyl alcohol.

Uranium. Slusil (168) developed a n x-ray fluorescence technique for the rapid determination of 100 to 1000 p.1i.m. of uranium in aluminum alloy.

Boyle (12) determined uranium in beryllium oxide-uranium oxide mix- tures by dissolving t,he sample in HC104 and HzS04 overnight, reducing the uranium with Cr(III) , and titrating electrometrically with K2Crz07.

Vanadium. Deyris and Albert (SO) recommended the determination of vanadium in zone-refined aluminum by activation analysis based on ir- radiation of vanadium, coprecipitated by adsorption on Fe(OH)Z, in a flux of 5 X lo1* neutrons per sq. em.-see. The activity of V2 was measured after

extraction of vanadium cupferrate into CC14. Eiechler, Jordan, and Leslie ( 7 ) reported the spectrophotometric deter- mination of vanadium in high-purity aluminum powder by converting the vanadium into the phosphotungstate, which was estracted into n-hexanol.

Zinchenko and Barinova (Bf3) pro- posed the photometric determination of vanadium in titanium by extraction of the vanadium phosphotungstate com- plex with isobutyl alcohol. Fluoride was added to complex the large amount of titanium.

Zinc. Niyaj ima (121) reported the rapid photo metric determination of zinc in aluminum alloys with Xylrnol Orange a t a p H of 0.3. Ions such as calcium were masked with thiourea, ascorbic acid, and SH4F. 3Ionnier and Prod'hom (122) recommended a colori- metric determination of traces of zinc in bauxite, alumina, and refined aluminum with dithizone and a series of CHCI, and CC14 extractions.

Wakamatsu (201) proposed a ral)id determination of zinc in aluminuin alloys by titration with EDT.1 at pH 5 to 6 with PAAN as indicator. The inter- ferences of aluminum and tin were masked by XH4F. Dirnitrova (31) studied the chelonietric determination of zinc in aluminum alloys by titrating with EDTA at pH 8.5 to 9.5 with Eriochrome Nack T as indicator. Ishibashi and Komaki (73 ) developed a method for the determination of zinc in aluminum alloy by using a liquid anion exchanger and EDTA titration with Eriochrome Black T as an indicator a t pH 9 to 10. The interfering iron was removed by a methyl isobutyl ketone extraction. Kharin and Soroka (84) described an ion exchange-electrolytic determination of zinc and copper in aluminum alloys not containing nickel. More details are in the Copper section.

Fleury (44) recommended the polaro- graphic determination of 0.01 to 0.357, zinc in copper-aluminum alloys. Copper was separated by electrodeposi- tion, iron was extracted by isobut'yl methyl ketone, and zinc was measured polarographically in a SaOH-EDTA& gelatin mixture. Tajima and Kurobe (172) investigated the determination of copper, zinc, and iron in aluminum alloys by square-wave polarography without interference from other con- stituents. The polarograms for copp er and zinc were recorded from an HCI solution a t -0.025 and -1.05 volts, respectively, us. the mercury pool electrode. Vasil'eva and Vinogradova (194) studied the determination of gallium, zinc, and cadmium in high- purity aluminum by anvdic voltam- metry at a stationary mercury electrode with a silver contact.

Gornaya (68 ) applied emission spec- troscopy to make an approximate deter- mination of 0.2 to 0.87, zinc in

1 0 0 R ANALYTICAL CHEMISTRY

aluminum alloys by using an iron clectrode. S e e b (131) determined small amounts of zinc in high-purity aluminum by vaporization and con- densation on a water-cooled finger- condenser, followed by spark spec- trography.

Wallace (205) employed atomic ab- sorption spectroscopy for the deter- mination of 0.02 to 6.0% zinc in aluminum alloys at 2138 A,, slit width 0.3 mm., lamp current 44 ma., and air pressure 12 lb. per sq. in.

Ishibashi and Komaki (74) used liquid anion exchangers and EDTX titration for the separation and deter- mination of zinc in nickel-magnesium alloy.

Zirconium. SVolna and Studencki (209) determined 0.05 to 1% zirconium in magnesium alloys by precipitating the zirconium with tartrazine and weighing the complex. Crawley (23) described the photometric determination of soluble and insoluble zirconium in magnesium alloys with PAN after extraction with trioctylphosphine oxide. Tuma and Kabicky (186) reported the photometric determination of zirconium in magnesium alloys with morin. The absorbance was measured a t 436 mp after the complex was held at 20°C. for 20 to 60 minutes. Titanium and fluorides interfere. Tikhonov (178) recommended the colorimetric deter- mination of zirconium in magnesium alloys with Alizarin S without weighing the sample. A plexiglas cylinder was glued on the surface of the sample and 2 to 3 drops of concentrated HC1 were added. hfter 5 minutes the solution was transferred to a graduate cylinder and the color was developed.

Wood and McKenna (210) proposed the photometric determination of 0.5 to S70 zirconium in t,itanium alloys with Alizarin Red S at 560 mu.

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(206) Wells, J. R., Carpenter, Ll., U . S. (210) Wood, D. F., McKenna, R. H., Inst. Met. 8 , 251 (1962). BUT. Min. Rep. Invest. 6105, 23 pp. Analyst 87, 880 (1962). (214) Zinchenko, V. A,, Ershova, N. A., 1962. (211) Wood, G. C., Marron, V. J. J., Gertseva, N. M., Titan i Ego Splavy,

(207) Will, Fritz, 111, Moss, M. L., Lambert, B. W., LVature 199,239 (1963). Akad. Yuuk SSSR, Inst. Met. 8 , 242 ANAL. CHEM. 35, 96R (1963). (212) Yakovlev, P. Ya., Malinina, R. D., (1962).

Nonferrous Metallurgy II, Zirconium, Hafnium, Vanadium, Niobium, Tanta= lum, Chromium, Molybdenum, and Tungsten Robert Z. Bachman and Charles V . Banks Institute for Atomic Research and Department o f Chemistry, Iowa State University, Ames, lowa

HIS REVIEW, which is appearing for T the first time, is concerned with methods for the determination of zir- conium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, and tungsten which appeared in the litera- ture between January 1962 and July 1964. ,4 recent review (21) discusses the literature on the analytical chemis- t ry of these elements along with tita- nium for the period from 1950 through 1960. A review of the literature ap- pearing in 1961 was included in the Nonferrous Netallurgy Section of Ana- lytical Reviews-1963. Because this is the first review in Analytical Reviews dealing exclusively with these elements, enough different methods and types of methods are included to try to present a representative cross-section of the mate- rial being published on the determina- tion of these elements. To make this review more useful to those engaged in the determination of these metals, an effort was made to include a brief state- ment as t o the content of each paper.

Those references which appeared in the Ferrous or Nonferrous Metallurgy Sections of Analytical Reviews-1963 were intentionally omitted from this review. Although titanium has been included in some reviews of the analyt- ical chemistry of these elements, i t was felt in this case that better continuity would be maintained by including titan- ium with the other “light-structural metals” in Nonferrous Metallurgy, Par t I. The elements vanadium, chromium, molybdenum, and tungsten are discussed separately; however, it was found to be more satisfactory to discuss zirconium and hafnium together and niobium and tantalum together. Analytical methods are summarized in Tables I-XI.

ZIRCONLUM AND HAFNIUM

Zirconium and hafnium are found together in nature, are usually discussed together in the literature, and most wet chemical methods work equally well for

both. Consequently, they will be con- sidered together in this review to avoid repetition.

Elwell and Wood ($4) have recently authored a book on the analysis of zir- conium entitled “The Analysis of Tita- nium, Zirconium, and Their Alloys.” Recent reviews of the analytical chem- istry of zirconium and hafnium include a two-part review by I to and Hoshino (125, 124) and one by Elinson (80). McKaveney (165) used round-robin analysis on three niobium-base alloys to evaluate several types of procedures for the determination of a number of ele- ments including zirconium in niobium.

Activation analysis is a technique which has proved useful for the deter- mination of zirconium in the presence of hafnium and of hafnium in the pres- ence of zirconium. Oka, Kato, and Sasaki (203) added copper as a n internal standard to mixtures of zirconium and hafnium and then measured the ratio of radioactivity of zirconium-89 to copper- 62 to determine zirconium in hafnium. Zitnansky and Sebestian (293) irradi- ated pure zirconium along with the un- known sample to determine the zirco- nium correction for the determination of hafnium in zirconium. Kamemoto and Yamagishi (132) irradiated a standard along with the sample to determine 0.06 to 1.1% hafnium in zirconium. They used the y-rays from hafnium-181 rather than hafnium-179. Hafnium along with a number of elements was determined by Fournet (89) using ac- tivation analysis in pure zirconium pre- pared by two different methods. Eh- mann and Setser (78) applied activation analysis and radiochemical separations to the determination of both hafnium and zirconium in stone meteorites. Chinaglia e.! al. (55) included hafnium in a discussion of the use of short-lived radionuclides in activation analysis. Girardi and Pietra (97) used a n activa- tion method coupled with separations for the determination of hafnium in

aluminum. Activation analysis tech- niques were used by Gruverman and Henninger (101) for the determination of zirconium in alloy steels and electro- etch residues. Radiochemical methods have also been frequently used to deter- mine the amount of zirconium-95 in various substances under different con- ditions. Seyb (250) proposed a math- ematical treatment of the decay curves which allows the determination of both zirconium-95 and niobium-95 in mix- tures. Overman (210) used a fl-y co- incidence counting technique to resolve mixtures such as zirconium-95 and niobium-95. Maeck, Marsh, and Rein (16’7) utilized zirconium-97 to evaluate critical nuclear incidents in which large levels of fission products were present prior to the incident. Park, Kim, and Suo (215) determined the concentration of zirconium-95 and a number of other elements in air to find the level of fallout from weapons tests. MacDonald et al. (163) determined some y-emitting nu- clides including zirconium-95 in new- borns, infants, and children, and Cofield (60) worked out techniques for the determination of zirconium-95 and other nuclides in human lungs. Techniques for the determination of important fis- sion products including zirconium have been applied to rain water by Buchtela and Lesigang (36); to vegetables by Park, Kim, and Suo (216); to marine sediments by Osterberg, Kulm, and Byrne (209) ; to seaweed and seawater by Hampson (108); and to soil and river-bed samples by Sakagishi, Ueno, and Minami (241).

During the period covered by this review there were also a number of papers published which described gravi- metric methods for the determination of zirconium. Several of these were merely procedures for finishing the determina- tion after a separation had been achieved by some other means, while some involved the use of reagents which were claimed to separate zirconium from

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