Review of
NONFERROUS METALLURGY
APPLIED
G. H. Farrah and M . L. Moss Aluminum Co. of America, A'ew Kensingfon, Pa.
ANALYSIS
T
>eventh review of the literature of analytical chemistry relating to nonferrous metallurgy is based on material received during the 2-year period ending AuguPt 1958. References to foreign publications are drawn largely from abstracting journals, and the present revieli may be as much as a year in arrears in such cases. Several references to work with nuclear materials are included n hich, although no longer new, have only recently been declassified. Because of the continuing growth in the number of publications in the field, the tabular form of presentation used in the preceding review (226') is retained. One change has been made t o increase the usefulness of these tables. A column has been added to indicate the approximate conctmtration range of each method, the division being made arbitrarily a t the 0.05% level. Methods designed primarily for amounts above 0.05% are marked G (gross), while those intended for concentrations less than that are designated by bI (minor). The methods included are reprevntative of current nork and recent developments of gmrral interest although no claim is made to exhaustive coverage. Thf preponderance of foreign publications, noted in the preceding review, holds for this present review period n ith approximately the following dihtribution: Vnited States, 36%; Russia and Eastern Europe, 227,; United Kingdom, 16%; Japan, 12%; 11% ; remainder, chiefly Germnn! France, Italy, and Spanish-speahing countrie,-, 37,. More than 450 referencts were scanned for trcwds in techniques. Cf about GOO separate methods of element determination published during this biennium, 3470 used spectroscopic methods (including direct readers) ; 28% n ere spectrophotometric; 12% polarographic; 127, titrimetric; 6% gravimetric; 47, radiometric; 27, flame spectrophotometric; 11 hile the reniaining 2y0 included nephelometric, fluorometric, x-ray absorption, etc. His
~
SPECTROSCOPIC METHODS
iimong the recent contributions toward standardization of spectrographic methods is the "Methods for Emission Spectrochemical Analysis" published in October 1957 by the Amer-
ican Society for Testing Materials. Included is a suggest'ed method (E-2 Shl 7-10) b y Potter (16), for analyses of aluminum and its alloys. using a recording photoelectric spectrometer and covering 23 elements. This general method is now well established in the aluminum industry. Black and Lemieux have applied the same type of instrument to the analysis of bauxite, alumina, carbon and other nonmetallics used in the aluminum industry (41). Tingle and Matocha also published a comprehensive method for the spectrographic analysis of nonmetallic samples using a recording photoelectric spectromet'er. By a fusion, pellet-spark method, a variety of materials was analyzed, and limits of detection were reported for 17 elements (3%'). Milbourn and Gidley set forth their experience with t'hree different types of direct-reading photoelectric spectrometers, two of them self-recording, in process control analyses of aluminum and copper alloys (213). Yoshinaga, llinanii, and Fujita pointed out the adtantages of spectroscopic analysis in detecting segregation in a variety of metallurgical products (368), Pittwell discussed methods of preparation and testing for homogeneity of disk or pencil spectrographic standards for the analysis of magnesium and aluiuinum (257). Frank, Dallemnnd, and Fry did similar n.ork on homogeneity of zinc-base alloy stanrlsrds proparpd hy 5 continuous-rasting process. These \wre examined for both longitutlinal and transverse segrcgatioii. using a direct-reading spwtronietc'r ( 1 1 8 ) . I n common n i t h other mttliods of annlysis, there is constant necd to extend speetmscopic methods to ever lower concent'rat'ion ranges. ZaIdel reported the determination of 29 elements in which the usual sensitivity (10-2 to 10-470)for emission spectroscopy has been extended 100- to 1000-fold (361). This was done by fractionally distilling the elements under vacuum from a refractory matrix and condcmsing the evaporated elements (or their oxides) directly onto a water-coolcd copper or graphite electrode. This is a n extension of the previously published work of Zaidel and coworkers (362)and covers a greater number of elements in zirconium and uranium oxides as well as aluminum oxide. Mandel'shtam has
applied this technique for thc con(witration of impurities in uranium. aluminum, thorium, and beryllium o\itlce, copper, and nickel (203). Other techniques have been used to effect concentration of trace constituents before spectrographic determination. TVray, in the determination of rare earths in thorium in the fractional parts per million range, removed the bulk of the thorium by solvent extraction (352). Center, Henry, and Householder also analyzed thorium spectrographically, using ccllulose column chromatographic separation before determining individual rare earths a t the 0.05 p.p.m. level (64). Solution techniques for spectroscopic analysis are gaining increasing acceptance, one reason being that standardization is independent of chemical analysis. Pure reagents may be neighed and standard solutions synthesized to match the samples both qualitatively and quantitatively. There i? the additional advantage in metal analysis that dissolution of the sample erases its metallurgical history Lvhich would affect excitation characteristics if sparked dirpctl!-. Erdey, Gegus, and Kocsis have rc1portt.d on a variation of the solutionspray technique for the spectroscopic analysis of pure aluminum in which the sample solution is spraycd into a hollow c3lrctrode 11 ith condensed-spark excitation (103). SPECTROPHOTOMETRIC METHODS
Conccntration range's that can be handled by the various tdorimetric techniques hare been greatly expanded by differential spectrophotoruetry-e.g,, til-o papers on thc dctcrmination of aluminum are cited. Yokosuka (354) used an 8-quinolinol-colorimet'ric method to determine aluminum to a lower limit of 0.0001% in nickel, while Banerjee (8Q) used aluminon to determine aluminum in titanium and its alloys in the range of 0.1 to 17, by conventional colorimetr>-. By differential spectrophotometry he extended the range to 1 to 10% aluminum. Differential spectrophotometry was also used by Bacon and Uilner to determine molybdenum in its uranium alloys with a precision of better than = t l . O % for alloys or synthetic alloy solutions containing 2.5 to 20% molybdenum. VOL. 31,
NO. 4, APRIL
1959
713
Below the 2.5% level, precision 1% as impaired by uranium interference (25). Sutcliffe and Peake determined nickel directly in copper-base alloys using the absorption characteristics of solutions of copper and nickel (313). Samples containing 1.5 to 30% nickel have been satisfactorily analyzed, with a single determination requiring only about 30 minutes. Fletcher and Wardle reported a new spectrophotometric method for the determination of bismuth in lcad and lead alloys (115) which used the absorption of bismuth bromide in hydrobromic acid. Because
Table
I.
telluriuiii is the only interfering element and can be removed by preliminary precipitation with stannous bromide, the method was adapted to the determination of tellurium in lead and its alloys (114). 9 spectrophotometric method for zinc utilizing cu,&-y,&tetraphenylporphine was developed by Banks and Bisque (SO). The method is widely applicable, having been used for the determination of trace amounts of zinc in cadmium, magnesium, rare earths, beryllium, iron, yttrium, and the alkali metals. Two systems of colorimetric analysis have appeared which
Methods for Nonferrous Metallurgical Materials
S. Spectroscopic. C. Chemical Methods Constituents Determined Used
R. Radiochemical.
~~
Material Aluminum
Mn, Gal Na, Cu, Sb, Hf, Sc Pd, Rh, Ir, Pt, Ru Na, P, Cu, Gal Zr, Fe, No, rare earths Zn, Pb, Cu, Fe, Mn Mg, Zn, V, Cr
Aluminum, alloys
Antimony, alloys Bismuth, alloys Chromium Cobalt Copper, alloys
Copper-lead slag Indium Lead Manganese Monazite Nickei, alloys Platinum Rhenium Silicon Silver, alloys Thorium Tin, alloys Titanium, alloys
White metal Zinc, alloys Zircon sand Zirconium
7.14
Cu, Cd, Nil Pb, Zn U, Nd, Pr Na, K, Mg Mol Be, Fe, Cr, Ni H, N,0 Ni, Cu, Fe, Mn, Si Cu, Pb, Sn Fe, Ni, Pb As, Se, Te, Pb, Sn, Bi, Fe All Fe, Nil Mn Al, Si, Ca, Mg Th, Cu, Pb, Cd Cu, Ag, Bi Cu, Cd, Nil Zn Th, Lanthanides Pb, Bi, Sn, Cd Fe, Ni, Pb, Cu, Te Pb, Sn, Cd, Bi Cd, Mg, All Fe, Ti, B As, Sb, Cu Cu, Cd, V, Zn Ag, Cu, Cd, Zn Rare earths Cu, Cd, Ni, Pb, Zn Zn, Pb, Sn, Ni, Fe Sn, Sb, Pb, Bi, As, Fe, Cu Mo, Fe, AI,Cr, M n Ca, Mg, A1 Cr, Ti, V H, NJ Fe,Mn, Mg Pb, Sn, Sb, Cu Pb, Cd, Sn, Fe Pb, Cd, Sn Zr, Si, Fe, Ti, AI, Th, Rare earths Ag, Nil Cu, Mol W, Fe, C1, Mn., Ti., Cd., Co.. V
ANALYTICAL CHEMISTRY
~
~
References
use elution chromatography on a cellulose column for preliminary separations. Ghe and Fiorentini (1P7) determined molybdenum, aluminum, chromium, and manganese in titanium alloys, while Venture110 and Ghe (555) similarly determined manganese, nickel, magnesium, chromium, copper, zinc, and iron in aluminum alloys. POLAROGRAPHIC METHODS
Shinagawa, Imai, and Sunahara uwd multisweep oscillographic polarography for analyses of binary mixtures of metals having similar half wave potentials. Their methods xere applied to lead-thallium and cadmiumindium alloys (288). They used a similar method for the determination of zinc in nickel (289) and the error in all cases was approximately =tZ%,. Kalvoda also studied oscillographic polarography and discussed conditions for the separate as well as simultaneous determination of copper, tin, bismuth, cadmium, indium, lead, thallium, zinc, barium, strontium, sodium, potassium, and ammonium, in the presence of a nonanialgamable element (163). Larrabee and Graham indirectly determined thorium in magnesium alloys containing zirconium by precipitation of thorium as the tetra-(m-nitrobenzoate) (182). Thc precipitate mas decomposed and the resulting m-nitrobenzoic acid was determined polarographically. Zirconium was removed on a n anion exchange resin. Procedures for the polarographic determination of arsenic have been published by Got6 and Iketla (136, 137') for the 0.003 to 0.1% range in lead metal, and by Coulson (80) for the 0.1 to 5% range in zinc and zincsmelting residues. Coulson extended the sensitivity down to 0.0001% of arsenic with a n absolute accuracy of =t0.04% by a preliminary coprecipitation as arsenate with ferric hydroxide. I n a solution aliquot containing 1 to 5 mg. of silver, Bozsai determined silver polarographically in copper alloys and soldering metals containing 0.1 to 95% of silver with a rotating platinum electrode (47'). For the polarographic determination of lead and cadmium in zinc-base alloys, Taylor and Smith used a preliminary separation from zinc by a mercury cathode electrolysis at controlled potential (521). By controlled potential electrolysis of the amalgam, lead and cadmium were redissolved anodically into fresh electrolyte in which the lead and cadmium \\ere then determined polarographically down to a fen- ten thousandths of 1%. Mukhina and Tikhonova reported the polarographic determination of niobium and tungsten in alloys based on nickel, chromium, iron, and cobalt. I n alloys containing niobium-tungsten ratios of 1:l to 1:5, determination of
both elements in the same solution was possible (228). TITRIMETRIC METHODS
Yew developments in titrimetry are mainly applications of familiar reactions to the determination or analysis of the newly important elements, or instrumental detection of end points by various means. Milner and Edwards published a macro volumetric method for the determination of uranium in amounts u p to 20% in binary alloys with bismuth, but also containing traces of copper, nickel, vanadium, cerium, and neodymium (218). Milner and Barnett later made a micro scale application of the same method: ceric sulfate titration of uranium following redurtion on a lrad column (217). Willard and Kriege have shown excellent recoveries in potentiometric titrations with standard ferrous sulfate solution for determination of vanadium and chromium in uranium alloys (346). A volumetric method for the determination of lithium in its alloys v i t h aluminum was reported b y Purcell and O'Conner (269). Lithium was spparated by precipitation with potassium ferric periodate and determined indirectly b y iodometric titration of the ferric iron and periodic acid formed on solution of the precipitate in acid. Malmstadt~and Roberts applied the automatic derivative spectrophotometric end point detection system with electrolytically generated titanous ion to the determination of iron in titanium sponge, alloys, and orrs (201). A similar system was used to determine titanium in titanium ores and metal
(202)*
Table
Methods for Elements in Nonferrous Metallurgical Materials
G. Gross. M. Minor Subject or Constituent ConcenReagent, Method , tration DeterMaterial or or Instrument Used Range References mined Major Constituent AE solder G (1.97) Diethyldithiocarbamate titration Ag Heterometric ICI (49) M (3556) Cupric dithizonate, colorimetric Polarographic titration G (47)
AI
As B
Ba Be
Bi GRAVIMETRIC METHODS
Although the recent major emphasis has been on instrumental methods of analysis, new methods and applications of gravimetry continue to appear. Many publications reporting on gravimetric techniques are concerned with the "neTer metals." Silverman and Trego recommended the sulfate gravimetric method in determining barium in zirconium and hydrated zirconyl chloride at the 0,000 to 0.00470 level (296). Samples RS large as 10 grams were used, the zirconium being completely removed b y a hydrochloric acid double precipitation followed b y cupferron precipitation-chloroform extraction. Recoveries were satisfactory and reproducibility was 0.001%. D a t t a used 1-hydroxy-2-naphthoic acids, or the bromo or nitro derivatives, to precipitate thorium from cerite earths, monazite sand, and from such metals as barium, calcium, strontium, magnesium, zinc, and titanium, b u t not zirconium. The precipitate was ignited and weighed as the oxide (87).
II.
C
spectrograph EDTA, bismuthiol Polarograph Eriochrome cyanine R, colorimetric Stilbazo, colorimetric 8-Quinolinol, colorimetric iZluminon Th( titration Spectrograph cu Molybdate, colorimetric Cu alloys Molybdate, colorimetric Ge-Ge02 Molybdate, colorimetric 1: 1 Dianthrimide, colorimetric A1 alloys Quinalizarin, colorimetric A1 alloys Carminic acid, colorimetric A1-U Electrolytic ion exchange separaNa, Ni tion, colorimetric Hg-cathode separation, coloriNi metric Th-B, U-B Mannito-boric acid titration Ti alloys Quinalizarin titration U-Zr alloys Curcumin, colorimetric Zr, Zr alloys Spectrograph Potentiometric titration Ni alloys Polarograph Pb Zr Gravimetric Alloys, concen- Radiometric titration trates Toron, colorimetric AI, bronze Morin, fluorimetric Be ores Iodometric titration Bronze, alloys Gravimetric Bronze, beryl Ores and minerals Spectrograph Colorimetric U Cr-Ni alloys hlethyl violet, iodide, colorimetric Pb, Pb alloys Bromide, colorimetric Pb and Sn Thionalide, colorimetric Vacuum melting Combustion
Precious metals Be Cu
Silver-acetylene, colorimetric Ca Cd
Ce
c1 co
Cr
hf, G
(56) (197)
M
( 1664) (184)
hf
(107)
M
(354)
M G
(904) (176) (109)
...
. ..
...
M M M M
M M
M M G M
M
...
G
9 ... G, M M, G
G" M' . M hf
iLI M hf M
Gravimetric, volumetric Mg M' ' Ni Flame photometer M Oxalate titration V Amperometric titration M Al Zn, Cd, Mn G Oscillographic polarograph Cd-In alloy M Pig lead, Zn alloy Polarograph M Polymetallic ores Dithizone, colorimetric ... Spectrograph Zr, Zr alloys Bi alloys KMn04, colorimetric titration G M Mg alloys HZ02,colorimetric Sulfate, colorimetric ill Pu Th-Ce alloys FeNH4(SO4)2 titration G Ti AgCl turbidimetric G, M Fe(II1)-Hg(NCS),, colorimetric M Ti Zr AgNOs potentiometric titration M Co-Pt alloys Electrodeposition, gravimetric G EDTA titration. cu M'' Mn ores and slags Xanthate, colorimetric Al alloys Chromate, colorimetric Mo-Cr alloys Polarograph G"' Diphenylcarbazide, colorimetric M Ni, Ni-V U-V alloys Potentiometric titration G (Continued on page 716 )
( 506 j (661, 113)
(66) (168) (3.93)
(347) (17s) (656)
(316) (148) (190, lR1) ( 346 )
VOL. 3 1 , NO. 4, APRIL 1959
715
Spacu and Hlevca, in a new rapid method for t h r gravimetric deterTable II. mination of thallium, used Reinecke This salt as the precipitant (%I?). Subject reagent, probably best knoun for its or Conuse in the identification of alpha amino stituent acids, gives a precipitate with thallium Determined in acid, neutral, or slightly alkaline solutions. Precipitation can be made Cu in the presence of some 24 elements without preliminary separations. il simplified gravimetric analysis of uranium-aluminum alloys containing less than 25% of uranium was described by Mechelynck (208). Addition of ammonium carbonate to an acid solution of the alloy complexed the uranium and precipitated aluminum as the h!droxide. Acidification and boiling of the filtrate removed the carbonate, and uranium was then precipitated 11 ith an excess of ammonia. FLAME SPECTROPHOTOMETRIC METHODS
The application of flame spectrophotometric methods to the determination of magnesium in aluminum alloys has been unsatisfactory because of the suppressing effect of aluminum. Ikeda studied the relationship b e h een intensity of the magnesium line a t 371 mp and the concentration of copper, aluminum, manganese, iron, and free acid as found in solutions of aluminum alloys (15s). He reported that the intensity remained constant, without regard to the concentrations of other constituents, in solutions containing more than 0.01 gram of aluminum per ml. and which \\ere less than 2AY in hydrochloric acid. The average deviation was less than 10% for 0.4 to 2% magnesium. Dean and Cain determined copper, nickel, and manganese in aluminum-base alloys by flame photometry (88). They selectively extracted the diethyldithiocarbamates of these metals with chloroform and aspirated the chloroform extract into a n oxyacetylene flame. It was concluded that introduction of the organic solvent adds rather than detracts from the energyof the flame, as is the casewith aqueous solutions, and an increase of emission intensity of four- to sixfold in the case of these three elements was found. Meloche and Beck investigated the effects of iron, aluminum, thallium, indium, and zinc upon the emission of the gallium line at 417.2 mp (20209). They described the determination of gallium in gallium-copper alloys in two concentration ranges: 0 to 1% gallium to within O.OlyG, and 0 to 10% gallium to within 0.1%. RADIOCHEMICAL METHODS
I n a recently declassified report, Eastwood calculated the probable lower limits of determination, by the radioactivation method, for 26 trace impurities
716
ANALYTICAL CHEMISTRY
Eu Fe
Methods
for Elements in Nonferrous Metallurgical Materials (Confinued) G. Gross. ST.IIinor
>faterial or Reagent, SIet hod, Major Constituent or Instrument Used Alloys KSCN, amperometric titration A1 alloys, pig- 2,2'-Diquinolyl, colorimetric ments Rubeanic acid, amperometric AI alloys titration AI alloys Rubeanic acid, turbidimetric AI alloys Triethylenetetramine, colorimetric titration Bearing metal Iodometric titration Brass, rll alloys 2-Furoyltrifluoroacetone chelate, colorimetric Bronze, brass, ores Xi Diethyldithiophoephate, potentiometric titration 1,2-DiaminocyclohexanetetraCo acetic acid, titration Thiosemicarbazide, colorimetric Cu ores Li Diethyldithiocarbamate, colorimetric Xi alloys Diethyldithiocarbamate, colorimetric Pb, AI alloys Diethyldithiocarbamate, colorimetric Pt-Cu, Pd-ilg-Cu Cu-Aq. SHa compley, colorialloys metric Ti Keocuproine, colorimetric Zn, Cd, Pb, Bi, Sn Neocuproine, colorimetric Jon exchange separation, EDTA Zn alloys titration Zr alloys Spectrograph Th, r,Be, Bi, Zr Spectrograph KRInO,, titration A1 Al, Mg, Zn, Pb KCNS, photometric AI, Mg, Zn, Pb KCNS, titration Al, .41 alloys 1 10-Phenanthroline, colorimetric 4,7-Diphenyl 1,lO-phenanthroBi line, colorimetric Bi o-Phenanthroline, colorimetric KCNS, photometric cu Cu alloys Sulfosalicylic acid, colorimetric Cu, Cu alloys Colorimetric Mn ores Polarograph MeCOCH2CHYe2-extractionJ oNi alloys phenanthroline, colorimetric Pu Spectrograph extracPure metals, al- 4-Methyl-2-pentanone tion, 1,lO-phenanthroline, loys, and noncolorimetric ferrous ores o-Phenanthroline, colorimetric Sn-Pb alloys Ti Porous cup, spectrograph o-Phenanthroline, colorimetric T i alloys Ti sponge, alloys, Automatic derivative colorimetric titration ores U colorimetric Zn EDT.4, colorimetric Zr and apatite Bauxites Spectrograph Flame spectrometer Cu-Ga alloys 8-Quinolinol-chloroform extracGe-GeOz tion, colorimetric Spectrograph In-Ga alloys Rhodamine, colorimetric Minerals Th, U,Be, Bi, Zr Spectrograph All AI alloys CS2-Br solvent, AgBr Combustion W, Nb, Ge Vacuum-fusion Na-K alloys, Deuterium exchange, mass spec_ .Zr trometer Pb Vacuum-degassing Ti Hot extraction Zr Zr, Zr alloys %EtEKYiL.tion Ag-Pb-In alloys Polarograph Cd Polarograph (Continued) ~
?&E%;;k,
Ga
Gd H
Hf In
%,
Concentration Range
...
11
... Bf M G
11 G
... G M hl
M G G, M
M G
... M
...
&I M, G G M
M M
A4 ;M M'.
RI G MJ
MI G
M M M bl G M M M M M M M hf M M
4" G G
References
Table II.
Methods for Elements in Nonferrous Metallurgical Materials (Continued)
G. Gross. M. Minor Subject or Constituent DeterMaterial or Reagent, Method, or Instrument Used mined Major Constituent In 8-Quinolinol-chloroform extracGe-Ge02 tion, colorimetric Polarograph Zn, Zn alloys Spectrograph Ca Li Spectrograph cu Potassium ferric Deriodate, voluLi-Al alloys metric Mg-Li-Zn alloys Flame photometer Ores Flame photometer A1 Complexometric titration A1 8-Quinolinol, colorimeter Al, A1 alloys Eriochrome Black T, photometric A1 alloys EDTA, titration EDT.4, titration Al alloys A1 alloys 8-Quinolinol, titration A1 alloys Flame photometer Ni, electronic 8-Quinolinol, colorimetric Ni, Zn, Zn alloys Eriochrome Black T, colorimetric Complexometric titration Ti Ti EDTA, titration Ti Porous-cup, spectrograph p-Xitrophenylazoresorcinol, Ti, Ti alloys colorimetric h1n Al, A1 alloys Permanganate, colorimetric Arsenite, titration Al alloys Polarograph Cu alloys Polarograph Mn ores Ni, A1 alloys Permanganate, colorimetric Ti Bismuthate, titration 1\10 Binary U alloys H202, colorimetric T i alloys Thioacetamide, gravimetric U-Mo alloys X-ray absorption W metais and Phenylhydrazine, colorimetric compounds W ores Colorimetric 1,i N -~ Sessler, colorimetric MO Kjeldahl separation colorimetric Yacuum-fusion Mo-W-Nb BrFa Ti, T i alloys Zr, Zr alloys Sessler, colorimetric Ka A1-Cu alloys Flame photometer ill-Si alloys Porous-cup, spectrograph Na Methanol, gasometric Pb Flame photometer Nb Binary Xb alloys H,Oz, colorimetric hlinerals Spectrograph Xi, Cr, Fe, Co, Polarograph steel Ores Pyrocatechol, colorimetric Solutions Hydroquinone, colorimetric U-Nb alloys H2S03, gravimetric U-Nb alloys Tannate, gravimetric CO Ni EDTA, titration 60-Cr alloys Dimethylglyoxime, gravimetric Cr-V Dimethylglyoxime, colorimetric Cu ores Thiosemicarbazide, colorimetric Li metal, hydride, Dimethylglyoxime, colorimetric hydroxide 0 Be, Ti, Zr, Th, U Micro-vacuum fusion Cr Isotope dilution cu Vacuum fusion cu Coulometric reduction Ge, single crystal Vacuum fusion La, Ni, steel Spectrograph Mo-W-Nb F'acuum fusion Na Butyl bromide Na-NaK Distillation, acid-base titration Nb Diff usion-extraction Pb Vacuum-degassing Pu P t bath, capillary trap Ti Conductometric Ti HZOZ, colorimetric Ti Micro bromination Ti P t bath, vacuum fusion (Continued on page r18)
mz
Concentration Range References bf (191)
1\I
(272-4, 368)
bl
;\I G G
&I, G
G
M
nr G" G G
...
lll
G"' G hl, G
hl, G G G"' llf
...
G G
G
G
&I G
11
...
hi'
*
M 51
G
&I G G
...
hi' G G
'
G..
...
...
hI
...
iG' '
AI
...
hI
ivi'
'
M.. hl M
pvl
E,
G
in high-purity lead, zinc, cadmium, indium, and tin (98). The calculations were based on stated assumptions as to sample size, irradiation time, time requirement and yield of the chemical separations, disintegration rate, etc. Iredale described radioactivation methods for the determination of manganese, gallium, copper, sodium, antimony, hafnium, and scandium in aluminum (155). A two-crystal y-ray spectrometer was used in determining quantities of these elements in the order of 10-5 to 10-6 gram without chemical separations. Thompson, Strause, and Leboeuf used neutron activation methods to determine some 29 elements, with detection limits in the parts per billion range in most cases, in ultrapure (transistor-grade) silicon (324). Gamma spectrometry and radiochemical separations with beta counting were used, and the applicability of each method was evaluated. dlimarin and Gibalo adapted a method previously developed for the titration of zirconium, to the determination of beryllium in its alloys and concentrates (10). The sample solution, containing 0.7 to 9 nig. of beryllium as the sulfate, is titrated with a standard solution of diamnlonium phosphate containing phosphorus-32. Periodically during the titration the solution is centrifuged and the activity of the clear solution is measured. The equivalence point is determined graphically after the establishment of only t n o points of the titration curve. SEPARATIONS
T h e use of solvent extraction t o effect separations in metallurgical analysis is receiving well-merited attention. T h e volume b y Morrison and Freiser, "Solvent Extraction in Analytical Chemistry," published in 1957, is t h e first comprehensive work in this field (225). Included are discussions of the principles of solvent extraction as well as selected procedures classified by elements. Specker and Doll used a n extraction technique for a simplified determination of iron in a variety of nonferrous materials (308). An equal volume of 4methyl-2-pentanone was used to extract more than 99.9% of iron(II1) from 5.5 to 7 N hydrochloric acid, followed b y a single extraction with water to remove the iron from the organic solvent. The determination was completed colorimetrically with 1,lO-phenanthroline. Determinations of 0.001 t o 0.1% iron in brasses, copper, zinc, and nickel were cited. Umland and Hoffmann found that magnesium oxinate, which normally does not dissolve in nonpolar organic solvents, can be quantitatively extracted by chloroform in the presence of 2% butylamine in the pH range 10.5 to 13.6 (331). This has been made VOL. 31,
NO. 4, APRIL 1959
717
the basis for a specific, colorimetric method for magnesium (concentration range 0.05 to 10 y of magnesium per ml.) and has been applied to calcium minerals, aluminum alloys, and a zinc alloy. An interesting example of the specificity of solvent extraction was reported by Aliniarin and Gibalo who extracted only beryllium with carbon tetrachloride from a solution containing disodium (ethylenedinitrilo) tetraacetate (EDTA, disodium salt) and the acetylacetone complexes of aluminum, chromium, cobalt, iron, nickel, manganese, zinc, cadmium, lead, copper, calcium, magnesium, and beryllium (11). Following the removal of beryllium, aluminum, and iron were extracted from the same solution after making it strongly ammoniacal. Geilmann, Keeb, and Eschnauer separated zinc from minerals and metallurgical products by a distillation method (126). The sample, mived with an accelerator such as carbon black, was heated in a stream of hydrogen at 1100" C. and the zinc distilled and determined by any convenient mcthod.
Table II. Methods for Elements in Nonferrous Metallurgical Materials (Continued)
G. Gross. M. Minor Subject or Constituent Determined 0
P Pa Pb
(y;
GASES AND NONMETALS
Interest in t h e determination of gases and other nonmetals in metals and alloys has continued at a high level with nearly half t h e papers on this subject being concerned exclusively, or in part, with t h e determination of oxygen. T h e major emphasis, methodwise, has been on various modifications of t h e vacuum-fusion technique. Booth, Bryant, and Parker studied the micro-vacuum-fusion method as applied to the determination of oxygen, nitrogen, and hydrogen in boron, beryllium, copper, chromium, iron, silicon, tantalum, thorium, titanium, uranium, and zirconium (44). Their method of determining oxygen and hydrogen using 10- to 100-mg. samples was comparable in precision and accuracy t o procedures requiring samples as large as a gram. However, the vacuum-fusion method was often unreliable for the determination of nitrogen in thorium, titanium, zirconium, and uranium. Hansen, Mallett, and Trzeciak investigated the accuracy and precision of vacuum-fusion techniques for the determination of oxygen in titanium and its alloys (144). A new platinum flux technique gave as good accuracy as the dry crucible technique. Both were claimed to give better reproducibility than the platinum bath method. Bennett and Covington, using a n improved vacuum-fusion apparatus and employing the platinum bath, obtained reliable determinations of oxygen in titanium and reported no interference from tin, aluminum, manganese, chromium, vanadium, molybdenum, nickel, iron, or zirconium (34). Sviley described a variation of this method for
718
ANALYTICAL CHEMISTRY
ConcenMaterial or Reagent, Method, tration Major Constituent or Instrument Used Range References Ti Pt flux, vacuum fusion ... (144) Ti Vacuum fusion M (330) Hydrogen evolution G (309) TI-oalloys BrF3 Ti, Ti alloys (242) Ti, Ti alloys Chlorination, gravimetric G" (101) Ti, Ti alloys Pt bath, spectrograph G (110) Ti, Zr, Cr, V, Bromination-carbon reduction ... (77) steels Zr Iodine, colorimetric G (294) Molybdate, colorimetric ill (357) cu Cu alloys Molybdovanadophosphoric acid, M (27) colorimetric U residues Gamma spectrometry M (282) Candies and A1 Colorimetric M (366) foils Polarograph ... (20) Cd Spectrograph M (236) Cr-CrzOa Cu alloys Colloidal PbS, colorimetric (174) Cu allovs Electrolytic, gravimetric M'. ($80) Dithizone, extractive t'itration M ( 336 ) In Polarograph M (829) In nf (136) Rfn (electrolytic) Dithizone, colorimetric and ferromanganese Pb-TI Polarograph G (288) Sn, Babbitt Dithizone, colorimetric G" Polaronraoh Sn alloys Polarograph M (64,il) Tinning alloy Zn alloy Electrolysis, polarograph hl (321) Zn (high purity) Polarograph M (318) spectrograph U Phenothiazine, gravimetric Pt salts, alloys Colorimetric Pu Spectrograph U Radiochemical Pb, Sn, Bi alloys Iron-flux, spectrograph Pu alloys Colorimetric Pu Thiourea, colorimetric Pu Pd alloys and Spectrograph steels Evolution, iodometric titration ... (78) Ti, Ti alloys Iodometric titration, or colori- M (63) U metric Ce(S0,)Z hydrazine, colorimetric h'I (138) Ge-GeOz Cu, stainless steels 3,3'-Diaminobenzidine, colori- M (67) metric Nondestructive, molybdate, G (%a A1 alloys colorimetric G (121) Gravimetric AI alloys M (123) Li metal, hydride, Molybdate, colorimetric hydroxide Molybdate, colorimetric M (366 ) Ni Ni, Ni alloys Reduced silicomolybdate, colori- M (18) metric Molybdate, colorimetric, graviM, G (76) Ti, Ti alloys metric U Spectrograph M (86) Th, U, Be, Bi, Zr Spectrograph M (363) 4Hydroxy-3-nitrobensenearsonic M cu acid, turbidimetric G EDTA, titration Cu alloys G Iodide, titration Cu alloys Morin, fluorescent and phenyl- M Ores fluorene, colorimetric M Phenylfluorone, colorimetric Pb G Polarograph Pb alloy G Gravimetric Sn-Pb alloy G Iodimetric, titration Sn solder Hypophosphite reduction, KIOI, M, G Ti alloys titration Oxidized hematoxylin, colori- M Zn, Pb metric ... 4Hydroxy-3-nitrobeneenearsonic Zn, Zn alloys acid, turbidimetric (Continued)
Pd Pt Pu Rh Ru S
Sb Se Si
Sm Sn
Table
II.
Methods for Elements in Nonferrous Metallurgical Materials (Confinued)
G. Gross. M. hlinor Subject or Constituent Deterniined
SI1
Ta
Te Ti
Th
T1
U
V
77'
Reagent, Method, or Instrument Used A1 reduction, KIOI, titration Pb reduction, KIOI, titration Polarograph Polarograph Dithiol, colorimetric Pyrogallol, colorimetric Extraction, hydroquinone, colorimetric Ores Pyrogallol or pyrocatechol, colorimetric Arsenazo, colorimetric Ti alloys Pyrogallol colorimetric Ti alloys Gravimetrh U-Ta alloys Hydrobromic acid, colorimetric Pb, Pb alloys Chromotropic acid, colorimetric Cu alloys Polarograph Minerals Automatic colorimetric titration Ti, ores Hydrogen evolution Ti-0 alloys EDTA, colorimetric U acids, Ba, Ga, Sr, hlg, 1-Hydroxy-2-naphthoic gravimetric Zn, Ti Bi alloys EDTA, titration Complexometric titration Mg alloys Polarograph Mg alloys APANS-mesotartaric acid, coloriOres metric EDTA, colorimetric titration Th, high grade Th-B alloys EDTA, titration EDTA, titration Th-Ce alloys Thorin, colorimetric U U-Th minerals Radiochemical Cd Polarograph Polarograph Cd, Fe-Cd In Polarograph blethvl violet, colorimetric Ores Gravimetric Pb Carbaminate, colorimetric Pb, Zn, Cd T1 Polarograph Polarograph Zn Ph reduction, ceric sulfate titraBi-U alloys tion Volumetric and polarographic Bi-U-Th alloys Hexone extraction and isotope Irradiated Th dilution X a Diethyldithiocarbamate, solIrradiated T h vent extraction Lowgrade ores Radiochemical NRU A1 sheathing Neutron activation 8-Quinolinol, colorimetric Th, Bi, ores Polarograph u minerals ( SH4),C02 separation, graviU-A1 alloys metric Radiochemical Gravimetric
hlaterial or Major Constituent Zr alloys Zr alloys Zr alloys Zr allovs Zr, Zr-U alloys Nb Nb-free alloys
Colorimetric Radiochemical U-Zr Fuel dates Spectrograph Pb reduction, ceric sulfate, POZr tentiometric titration EDTA, variamine blue, coloriAI metric Tungstovanadophosphate, coloriCr metric High Cr materials Colorimetric coloriMinerals and ores Tungstovanadophosphate, - metric Oxyquinolate, colorimetric U compounds FeS04, potentiometric titration V-U alloys Ni, Cr, Fe, Co, Polarograph steels Ta, Ti, Zr Dithiol, colorimetric Ti, Zr, alloys Thiocyanate, colorimetric; toluene-3,4-dithiol, colorimetric Dithiol, colorimetric Ti alloys, steels (Continued on page 720)
Concentration Range M, G
G" G
...
G G
... G"' G M G G
' '
G G M
G G G G G G M G G"
...
M G
M
G 11 G
G
.., ,
,
,
G M G, h l G G M G G G G
M
L1 M G,'?;l hl G
... bl
M, G G, hl
oxide in metals in which the oxygen is measured as carbon dioxide by a capillary manometer (300). The method, originally developed for use with 50mg. samples of plutonium, has a sensitivity of 0.3 y of oxygen and a time requirement of only about 12 minutes per sample. I n the determination of oxygen in titanium, Kilkins and Fleischer found the platinum bath preferable to the iron bath or dry bath because the blank from added iron or tin is avoided and more samples can be analyzed in a bath without gettering or solidification (348). A direct-current arc excitation method combining platinum bath fusion in a special carbon electrode holder with spectrographic determination of oxygen in titanium and its alloys was published by Fassel and Gordon. Precision is comparable to the vacuum-fusion or bromination-reduction methods, but the time required has been greatly reduced; a team of two operators can perform about 70 determinations per day (110). Tabeling used a similar spectrographic technique for the determination of oxygen in lanthanum, a nickel bath in a carbon electrode being employed in reduction of the oxides (316). In both methods, a n argon atmosphere is used in the electrode chamber. Spectrographic methods have been described b y Sventitskii and coworkers for nitrogen (0.003 to 0.3%), oxygen (0.1 to l.O%), and hydrogen (0.005 to 0.15%) in titanium alloys, and hydrogen in titanium powder. Comparisons were made rvith chemically analyzed standards (814). Koehler used a low-voltage high-current spark between silver electrodes in a partial vacuum to determine sulfur in palladium alloys with a detection limit of 0.05yo. Carbon and chlorine were also determined b y this method (170). Halogenation methods of various types have received a full share of attention. For the determination of oxygen in titanium and its alloys, Elwell and Peake mixed the sample with graphite and chlorinated it in a n argon atmosphere. The purified carbon monoxide was oxidized and m-eighed as carbon dioxide, The time required per determination is approximately the same as for the macro-vacuumfusion procedure, b u t the cost of the apparatus is estimated to be only about one twentieth the cost of the latter (101). Codell and Korwitz investigated the bromination-carbon reduction method for the determination of oxygen in titanium and titanium alloys (77). Purification of the bromine considerably reduced the blank. The method was also used for oxygen in zirconium, chromium, and vanadium n i t h the observation that the graphite residue from vanadium alloys containing aluminum must be ignited and the unattacked VOL. 31, NO. 4, APRIL 1959
719
Table II.
Methods for Elements in Nonferrous Metallurgical Materials (Continued)
G. Gross. M. Minor Subject or Constituent Material or Determined Major Constituent
\v Zn
Zr
U-W alloys U-W-Ta alloys Al, silumin Al, Zn, Cd, Mn Al' alloys AI alloys AI alloys A1 bronze Brass Brass, bronze Cd Cd, Mg, Rare earths, Be, Fe, Y, alkali metals Ni Pb Zn oxide hlg alloys Pu alloys Ti alloys Zr-Ce alloys
Reagent, Method, or Instrument Used 8-Quinolinol, gravimetric Hydroquinone, colorimetric Polarograph, dithizone titration
-44yZytric itration
EDTA, titration EDTA. titration Polarograph EDTA, titration EDTA, titration Polarograph Tetraphenylporphine, colorimetric
G hi
References (8.21) (49)
G
G G G M
hl
Polarograph Dithizone, colorimetric Hydrogen evolution Complexometric titration Chloranilic acid, colorimetric Halomandelate, gravimetric EDT.4, colorimetric
aluminum oxide weighed. I n a variation of this method, these authors absorbed the evolved carbon dioxide in barium hydroxide solution and measured the change in electrical conductance (74). hfillner, Hegedus, and Drorszky determined magnesium, iron, nitrogen, and carbon in titanium by bromination in a sealed tube (915). Oxygen was fixed as titanium oxide and determined colorimetrically, as were magnesium and iron. Xitrogen was determined by a semimicro-Kjeldahl method, while carbon was oxidized, absorbed in aqueous barium hydroxide, and determined by titration with acid. O'Neill found bromine trifluoride effective in the determination of oxygen and nitrogen and its alloys (24%'). Nitrogen values were in good agreement with those b y the Kjeldahl method except for alloys containing aluminum and iron, in which case recovery of nitrogen tended to be lorn. Little pioneering work was done with electroanalytical methods for the determination of nonmetals, although several papers presented new applications or further investigations of older techniques. Dean and Hornstein found electrode potential measurements a quick and accurate method for the determination of oxygen at concentrations below 0.06% in high-purity titanium (89). For the determination of oxygen in lead a t concentrations of about O.OOl%, Zag6rski dissolved the sample in mercury, electrolyzed it, then periodically determined lead polarographically. Extrapolation to zero time made possible the calculation of oxidized lead (359). Lambert and Trevoy studied films of cuprous and
720
Concentration Range
ANALYTICAL CHEMISTRY
... 31 G G
(270)
(48) (251)
(m 91
cupric oxides, cuprous sulfide, and cupric hydrogen phosphate by coulometric reduction. By pre-electrolysis of the electrolyte with a granular electrode to remove traces of oxygen and plateable cations, sensitivity was increased so that as little as a quarter of a monolayer of reducible film could be detected. The method provided information about the topography of surface films and the effectiveness of various techniques for removing them (181). Two electrolytic separation techniques, both developed for the determination of boron, may have applications in separation of other trace constituents. The first uses a divided cell in IThirh the two electrode compartments are separated by a cation exchange membrane. Electrolysis of the sample solution causcs cations to migrate irreverqibly into the cathode compartment simplifying the isolation and deterniination of the anion. Logie used this type of separation in the dctermination of boron in sodium metal and suggested several modifications of the apparatus (186). The second method of separation, used by Chirnside, Cluley, and Proffitt to find boron contents of 2 to 23 p.p.m. in nickel sheet, used the sample as the anode of a mercury-cathode electrolysis apparatus (70). I n this way, the nickel was simultaneously dissolved and deposited in the mercury pool, leaving the boron in the electrolyte. New applications of conventional chemical methods and reagents were used extensively in determinations of nonmetals. Harter, Perrine, and Rodgers, for example, determined nitrogen in zirconium and zirconium-base alloys
in the range 5 to 120 p.p.m. with Xessler's reagent (146). Clinton used sodium phenate-sodium hypochlorite reagent for determination of nitrogen in molybdenum metal following a Kjeldah1 separation, and found the method suitable for a concentration range of 0.002 t o 0.5% (73). Codell, Normits, and Clemency have applied the evolution-iodate titration method to the determination of sulfur in titanium a i t h good accuracy and precision in the 0.05 to 1% concentration range (78). Cellini and Sanchez also used the evolution method for sulfur in uranium metal. The final measurement was made either by iodometric titration or colorimetrically with a limit of sensitivity of 0.2 y (63). Babko, Yolkova. and Drako determined oxygen colorimetrically in copper, nickel, chromium, and molybdenum with fuchsine-formaldehyde reagent following reaction with sulfur vapor in vacuo to convert metal oxides to sulfur dioxide (24). The well-known molybdate colorimetric method for silicon has been applied in the analysis of lithium metal (123), and titanium and its alloys (75). I n the latter application, the method n as recommended for a concentration range of 0.003 to 1.5% silicon. Several published methods for determining oxides are based on volatilization of the matrix metal. Allsopp recommended vacuum sublimation of magnesium metal and volumetric determination of magnesium oxide in the residue by use of EDTA-disodium salt after removal of any iron or aluminum (12). For the determination of oxygen in sodium and sodium-potassium alloy, White sampled the liquid metal a t temperatures as high as 1400" F., performed a vacuum distillation, and titrated the residue with standard acid (344). There has been a small amount published on isotopic methods for oxygen and hydrogen in metals. Kirshenbaum has extended the isotopic method for determining oxygen to the analysis of chromium with an accuracy of at least 99% (168). ZaIdel and Petrov, who had previously developed a n isotopic equilibration method for the determination of hydrogen in zinc, iron, and nickelchromiuni alloys, have extended this method to include the analysis of zirconium. Results were stated to agree w l l with those obtained by vacuum extraction for hydrogen concentrations of 1 x 10-4% (364). LITERATURE CITED
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E.
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c.,
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