Nonferrous Metallurgy 11. Zirconium, Hafnium, Vanadium, Niobium, Tantalum Chromium, Molybdenum, and Tungsten Robert Z. Bachman and Charles V. Banks, Institute for Atomic Research and Department of Chemistry, Iowa State Universify, Ames, Iowa 500 7 0
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as did the previous two reviews in this series, attempts to cover a cross section of the methods for the determination of zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, and tungsten. Procedures using all of the more common techniques are mentioned along with a few novel techniques which will probably never gain wide application. The references were collected without regard for type of determination; however, there are far more spectrophotometric methods reported than any other type indicating, perhaps, that this is the area of greatest interest a t the present time. The period covered by this review is roughly July 1966 to July 1968. Because of the over 800 references describing new methods and new applications of established methods, it was decided to omit papers which reported only a sepmation or studies which could serve as the basis for a n analytical procedure rather than an actual procedure which could be applied in its present form. The papers included are from the periodical literature; reports of meetings and documents issued by governmental agencies were omitted because of the rather common practice of also publishing such work in the periodical literature. I n this review zirconium and hafnium are considered together because the same procedures serve equally well for both, while niobium and tantalum are considered together because they are found together in nature and many papers describe methods for both elements. The other four elements are considered singly. HIS REVIEW,
ZIRCONIUM AND HAFNIUM
The literature of analytical chemistry continues to show evidence of a lively interest in the determination of zirconium and hafnium by several techniques in a great many different materials. As in the previous reviews in this series, airconium and hafnium will be considered together because of the close similarity shown by their reactions in aqueous solution. Even though hafnium will not be specifically mentioned in most cases, many of the methods for zirconium will work equally well for 112 R
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ANALYTICAL CHEMISTRY
hafnium. Zirconium and hafnium were discussed in a recent book (206) along with many aspects of the analytical chemistry of the other elements considered by this review. It appears that in the past two years considerably less emphasis has been placed on gravimetric methods for zirconium. Cupferron was used for the separation and determination of zirconium in silicozirconium (50) and was also used for the precipitation of zirconium from a homogeneous solution b y preparation of the reagent from phenylhydroxylamine and sodium nitrite in the solution containing the zirconium (168). Zirconium in a silicon-aluminum-titanium alloy was determined by precipitation as the phospate (508). Other reagents which were studied and found to be useful for the precipitation and gravimetric determination of zirconium were 2-nitrobenzoic acid (416), 2-mercaptopropionic acid (520), and vanillin (525),all of which form precipitates which must be ignited to the oxide for weighing. Titrimetric methods for the determination of zirconium are largely the application of the titration with EDTA to various situations. Zirconium was included in a recent review of complexometric methods for determination, separation, and control of interferences (608). A direct titration of zirconium with E D T A using xylenol orange as the indicator is possible provided the zirconium solution is first made 1N in nitric acid, boiled for several minutes, and the titration then carried out while the solution is hot (718). With a hydrochloric acid solution being used instead of nitric acid, the method was used to determine zirconium in the presence of titanium following an ionexchange separation from niobium (116). By adding excess EDTA and back-titrating with bismuth to the xylenol orange end point, zirconium was determined in the presence of yttrium (609) and after ion-exchange separation from ore samples (401). A back titration of the excess EDTA with zinc to the xylenol orange end point was used to titrate molybdenum and zirconium in a mixture and then the EDTA equivalent to the zirconium after masking the
zirconium with fluoride (524). A continuous flow automatic potentiometric titrator was used for the back titration of excess EDTA with copper or zinc (76). Indicators used for detecting the end point in the direct titration of zirconium with E D T A are Eriochrome Black T (509), pyrocatechol violet (288), and Stilbazogall I1 (165). The use of a potentiometric back titration with either magnesium, calcium, or cadmium and a silver electrode was also reported (700) as well as the determination of zirconium in zirconium diboride b y an E D T A titration (89). The zirconium in an ammonium hexafluoride solution was determined by titrating with sodium hydroxide and following the course of the titration with a recording potentiometric titrator (496). Trilon B was used as the titrant for the determination of zirconium in fission fragments following a precipitation separation (409) and in leather (788).
Trilon B was also used for the determination of zirconium by a technique called “titration without a buret” in which measured amounts of reagentimpregnated paper are added to the solution (186). The method was used for the determination of zirconium in leather (187). Zirconium can be determined indirectly by dissolving zirconium mandelate in sulfuric acid and then titrating the mandleic acid with vanadium (485). Diethylamine was also used for the titration of zirconium with phenolphthalein as the indicator (714). hmperometric titrations have also been found to be useful for the determination of zirconium. I n one reported method, the reaction observed is the oxidation of EDTA on a graphite electrode (750). I n another case, an excess of E D T A was back-titrated with thallium(II1) and either the oxidation of free E D T A or the reduction of thallium(II1) mas observed (565). Two amperometric titrations involving the use of cupferron were also reported. One procedure described the use of a potassium permanganate electrode (776); the other relied on the catalytic reduction of hydrogen peroxide on the dropping mercury electrode (680). Zirconium was determined polaro-
graphically in dimethylsulfoxide and dimethylsulfoxide-water mixtures (657) and b y the use of water-ethanol-lithium chloride mixtures as the supporting electrolyte (27). The latter system was also studied and found t o be useful for the determination of hafnium (656). The catalytic reduction of hydrogen peroxide on the dropping mercury electrode was used for the determination of zirconium in nickel-aluminum alloys (682) and for the determination of hafnium (683). The zirconium-alizarin red S complex gave well formed oxidation and reduction waves at a rotating pyrolytic graphite electrode (816, 817). Spectrophotometric methods for the determination of zirconium and hafnium have continued to be frequently published with most of the emphasis being on the application of well known methods to various materials. Zirconium was discussed in a review of recent spectrophotometric methods (367). Of thirteen spectrophotometric reagents studied, arsenazo 111 was found t o be the best with nitrosulfophenol S and picramine R also recommended (17 4 ) . Picramine R and nitrosulfophenol S were used for the determination of zirconium in natural substances b u t there was interference from niobium and titanium if the amounts present were too large (173). Arsenazo I11 was found to be useful for the determination of zirconium in high-alloyed steels containing niobium while 2,4-sulfochlorophenol S and picramine R were found to be unsuitable (208). B y using masking agents on three separate portions of sample, uranium, thorium, and zirconium were all determined with arsenazo 111 in phosphate rocks (762). A cation exchange separation was also used t o separate thorium from zirconium prior t o determination with arsenazo I11 (24). Arsenazo I11 was also successfully applied to the determination of zirconium in aluminum alloys (517), along with titanium in molybdenum alloys (593) and in steel after dissolution in nitric acid, with the latter method working equally well for hafnium (346). Either arsenazo I11 or xylenol orange could be used for the determination of hafnium in steel after first removing the iron b y extraction of the chloride into ether (53). The factors affecting the complex formation of zirconium and hafnium with xylenol orange were studied (144) as was the extraction of the zirconium-xylenol orange complex or the zirconium-methylthymol blue complex into butyl alcohol from a solution containing diphenylguanidine (758). Zirconium can also be determined with xylenol orange after a reversed-phase chromatographic separation of niobium (3459, in the presence of niobium and tantalum (537) and in steel (143). Zirconium in ceramic materials (387) and alkali metal hydroxides (253) was
Table I.
Element Zirconium, hafnium, and zirconium plus hafnium
Spectrophotometric Methods
Reagent: Material (References) Review of spectrophotometric methods (367) Arsenazo 111, nitrosulfophenol S, picramine R: comparison of reagents (174) Nitrosulfophenol S, picramine R: Th, Te, Nb (173) Arsenazo 111,. 2,4-sulfochloropheno1 S,. picramine R: . steel (208) Arsenazo 111: Phosphate rock (762); Th (24); A1 alloys (517‘); Mo alloys (593); steel (346) Arsenazo 111, xylenol orange: steel (53) Xylenol orange: study of complex (144); with extraction (7‘58); Nb (342); Nb, Ta, Ti, Th, V, W, U, Fe (537); steel (143) Alizarin red S: ceramic materials (387); alkali hydroxides (253); Zr-Ni alloys (692) Pyrocatechol violet: steel (733); HpSO4 solution (787, 799
Zirconin (Gallocyanine MS): study of complex (515); hlg, Al, Ni, Cu (613); Nb, Mo, Fe, Sn, Ti (516) Stilbazogall 11: study of complex (154): Me: (616) ‘ Chromeaxurol S: stidy of cchditions’(302)Chloranilic acid: study of conditions (336) Methylthymol blue: study of complex (751) Chlorosulfophenol S: study of conditions (665) p-Chloromandelic acid: study of conditions (381); A1 (388) Phenylfluorone: T a (628) Robinetin: study of conditions (355) Alberon: Cu (514) Thorin: study of conditions (658) n’-methylanabasine-a’-azoresorcinol : study of conditions ’
(738) N-methylanabasine-a’-azc-p-naphthol:study of conditions ( 3 ) 3’,4’,7,RTetrahydroxyflavonol: study of conditions (354) Cyanoformazan-2: study of conditions (421)
Vanadium
N-phenylbenzohydroxamic acid: Nb (688) Molybdosulfatozirconic acid: study of conditions (273) 3’,4’,5’,6’-Tetrahydroxyfluoran:study of reactions (604) 1,l’-Dihydroxyazo dyes: study of reactions (394) Azo dyes: comparison of reagents (396) Review of spectrophotometric methods (286, 567, 646, 821 )
V(V): vzos (437). H202: Ti (753); iron ore (163) Molybdovanadophosphate: study of conditions (386), steel (102) Phosphovanadotungstate: A1 (388),TiC14 (754), coal (731) Borax bead: study of method ( 5 ) 4-(2-Pyridylazo)-resorcinol: study of conditions and interferences (13, 131, 236, 358, 690), crude oil (697) 4-(2-Pyridylazo)-resorcinol-HzOz:study of complex (689) Xylenol orange: study of complex (14, 18, @I), water (535) Methylthymol blue: study of complex (761); Ti (752) Chrome azurol S: study of complex and interferences (660. 661) Pyrocatechol: study of conditions and interferences (125, 563, 739) Pyrocatechol violet: study of complex (512) Pyrogallol: study of conditions and interferences (186) Pyrogallolsulfonic acid : study of conditions and interferences (126) Tribromopyrogallol: study of conditions (124) Gallic acid: study of conditions and interferences (191) Tris-( l,l0-phenanthro1ine)-iron(I1): alkaline aluminates (39) Tiron: study of conditions (547); study of complex (764) &Hydroxyquinoline; study of conditions (483, 743), steel (460) 8-Aminoquinoline: study of conditions (800) 5,7-Diiodo-8-hydroxyquinoline: study of conditions ($891 Hydroxamic acids: survey (67) Benzohydroxamic acid: study of interferences (494) N-phenylbenzohydroxamic acid: A1 (666); rocks (662) 4-Methoxybenzothiohydroxamic acid: steel (780);. U (781), petroleum products (782); study of condltlons ( 723) (Continued on page 114 R )
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Table 1. Element Vanadium (Cont’d.)
Spectrophotometric Methods (Cont’d.)
Reagent: Material (References) N-(o-tolyl)-benzohydroxamic acid: study of conditions and interferences ( 4 6 7 ) ;silirate rocks (332)
Salicylhydroxamic acid: biological materials (428) N-Phenylcinnamohydroxamic acid: Fe, U (812) ‘V-Phenyl-2-furohydroxamic acid: brines (583); steels and ores (584) N-Phenyl-p-phenylazobenzohydroxamicacid: study of complex (142) Caprohydroxamic acid: study of conditions (602) Arsenazo I: stitdy of Conditions (457) Gossipol: study of conditions and interferences (363) hlorin: study of conditions and interferences (390) Ferron: ores (469) Azoxine S: study of conditions and interferences (261) Thenoyltrifliioroacetone: study of conditions (311) Cyanoformazan-2 : ore concentrate (819); heat-resistant alloys (820) Formazon : Ti concentrate (411 ) Srilfosalicyclic acid: study of conditions and interferences (150)
Salicylaldehyde: study of conditions and interferences (424)
Salicylaldehyde-anthranilic acid: steel (62) Nicotinic acid hydrazide: study of conditions (412) p-Anisidine: study of conditions and interferences (673)
3-Hydroxyflavone: study of extractants (391) Pyridine-2,6-dicarboxylic acid-Ht02: study of conditions (602)
Benzidine: alkali hydroxides (253) 3,3’-I)iaminobenzidine: sea water (630) 3,3‘-llimethylnaphthidine:steel (643) p-Phenetidine: A120g A1 (436) l-Arnino-il-naphthol-3,6-disiilfonicacid and salicyclaldehyde: study of conditions (589) 2-(2-Thiazolylazo)-S-(diethylamino)-phenol: study of conditions (306) 7-Amino-1-naphthol-3,6-disiilfonic acid: study of conditions and interferences (15) A’-hIethylanabasirie-ol’-azoheptyl resorcinol : study of conditions (687) 5-(2-Pyridylazo)-2-monoethylamino-p-cresol: study of conditions (271) Diantipyryl-( 3,4-dimethoxyphenyl)-methane-thiocyanate: study of conditions (587) N,n’-Dimethyl-pphenylenediamine hydrochloride; ODianisidine: 3.3’-dimethvlna~hthidine: comuarison “ . of reagents,’~l(382) b-(lXantipyririylmethy1)-styrene; ~,a-diantipyrinyl-3,4dimethoxytoluene: comparison of reagents, steel iriRR1
3-Ak&1-4 [ 3- ( l-methyl-2-piperidyl)-2-pyridylazo] -phenol: study of conditions (769) Ascorbic acid-bromate-iodide: studv of conditions (84. . , 86 )
Niobium
Ascorbic acid-chlorate-iodide or chlorate-iodide-sinc: study of conditions (85) Chlorate-chloride-tin : study of conditions (87) Chlorate-chloride-hydrazine-sulfuric acid: study of conditions (88) pchloraniline-Hi02: study of conditions (543) Diphenylcarbazide-HsOs: study of conditions (644) Benzidine-HssO: study of conditions (545) Aniline-HpOz: study of conditions (546) 4-Amino-5-naphthol-2,7-disulfonicacid-bromate: study of conditions (406); NaC1, KC1 ( 4 9 Thiocyanate-bromate: study of conditions (331) AnilineH10~:rocks (231) Phenylhydrazine-p-sulfonic acid-chlorate: study of conditions and interferences (741) Review of spectrophotometric methods: (26, 59, 36Y 684)
CNY: Review (645); study of conditions (129); study of extraction (646); Ta (169); F (133); Zr minerals (384); rocks (498); molybdenite (49s); steel (11, 108, 239, 285, 425) 4-(2-Pyridylazo)-resorcinol:
study of conditions (19); oxalate, tartrate (200); Ta (202); Zr (555); steel (166, 201, 554, 733)
Niobate: steel (180) H202: Pb, Ca, Sr (257) (Continued on page 115 R )
114 R
ANALYTICAL CHEMISTRY
determined using alizarin red S. Alizarin red S was also used for the dctcrmination of zirconium in zirconiurnnickel alloys following electrographic dissolution (6.92). Zirconium in steel (733) and either zirconium or hafnium in sulfuric acid solution (787, 799) were determined using pyrocatechol violet as the chromogenic reagent. A reagent for zirconium or hafnium known as both zirconin and gallocyanine MS has been studied (516) and found to be useful for the determination of zirconium in the presence of magnesium, aluminum, nickel, and copper (513) as well as for the differential spectrophotometric determination of zirconium in the presence of niobium, molybdenum, iron, tin, and titanium (516). Stilbazogall I and I1 have been prepared and studied (154) and used for the determination of zirconium in magnesium alloys (615). Other reagents used for the spectrophotometric determination of zirconium or hafnium are chrome azurol S (Sod), chloranilic acid (336), methylthymol blue (7‘51), chlorosulfophenol S (665), p-chloro- or p-bromomandelic acid (381, 388), phenylfluorone (528), robinetin (355),alberon (514), thorin (658), N - methylanabasine - a’ - azoresorcinol (738), iV-methylaiiabasine-a’-azo-/3naphthol (3), 3’,4’,7,8-tetrahydroxyflavonol (%id), cyanoformazan-2 (421), N-phenylbenzohydroxamic acid (688), molybdosulfatozirconic acid (US),3’,4’5’,6’-tetrahydroxyfluoran (504), and various azo dyes (394, 396). The fluorescence of the zirconium-morin complex has been used as a sensitive method for the determination of zirconium in trichlorosilane (101, 516). Another optical method for zirconium in zircon utilizes the relative dispersion of double refraction of the crystal (430). Zirconium has been included in several studies of atomic absorption sensitivities of refractory metals using an acetylene-nitrous oxide burner (SO, 330, 617, 725). A plasma jet has also been used for the determination of zirconium by atomic absorption (128). The determination of zirconium in thorium oxide (774) and aluminum alloys (797) was also reported. As with most other techniques for the determination of zirconium, the spectrographic methods which were published simply apply well known methods t,o different materials. Zirconium in refract.ory-metal alloys (443) and hafnium in tungsten (57.9) were determined by the vacuum cup method. The optimum conditions for the determination of zirconium and hafnium in tantalum oxide were found through consideration of the volatilization curves (107). Spectrographic methods using: a dc arc were found useful for the determination of zirconium in rare earth oxides (goo), zirconium concentrates (392), varnishes and enamels (119), ce-
Table I. Element Niobium (Cont’d.)
Spectrophotometric Methods (Cont’d.) Reagent: Material (References) Molybdoniobophosphate: NblO; (809); A1 (388); steel (102); ores (62) Chlorosulfophenol S: study of complex (115, 666) Cyanoformazan-2: study of conditions (806); heatresistant alloys (420); ores (422) Xylenol orange: study of conditions ( 1 4 , 240) Thiazolyl or pyridylazoresorcinol: rocks (661) N-methylanabasine-a’-azoresorcinol:Tal W, rare earths (740) 2-(2-Thiazolylazo)-5-(diethylamino)-phenol: study of interferences (305) Pyrocatechol-EDTA: study of conditions ( 4 1 , 664) Pyrocatechol violet; study of conditions (471); steel (327, 472) Acid chrome violet K : alkali hydroxides (263) Acid chrome blue K: study of conditions (161) Gossipol: study of conditions and interferences (364) Phenylfluorone: Ta (379) M-Methylanabasine-a’-azo-&M-aminophenol: study of conditions (770) 4Methyl-6,7-dihydroxycoumarin or 6,7-dihydroxycoumarin: study of conditions (324) 5-(2-Pyridylazo)-2-ethylamino-4-methylphenol: alloys (198). Picramine R: Mo, U, Ti, Sn, A1 (203) Eriochrome blue-black B: study of conditions (806) A’-phenylbenzohydroxamic acid: study of conditions (688)
&Hydroxyquinoline: Zr (361) Methylthymol blue: U, W (199) o-Nitrophenylfluorone: Ti, TiClc (798) 2,4Sulfochlorophenol C: steel (209) 1-(2-Pyridylazo)-2-naphthol(236) Lumogallion : iron (343) Pyrogallol: steel (264) Bromo pyrogallol red: steel (796) Nitrosulfophenol S: steel (808) Tantalum
Review of spectrophotometric methods (367, 684) Malachite green: B, U, Zr, zircaloy-2 (193); steel (864, 327) 4(2-Pyridylazo)-resorcinol: study of conditions (13, 339) Brilliant green: study of conditions (636); ferronickel (767) Methyl violet; study of conditions (650); Ta206(178) Crystal violet: study of conditions (129) Rhodamine 6G: study of conditions (668); Sn (371); minerals (384) Butylrhodamine: ore (52) Phenylfluorone: study of conditions (291) Dimethylaminophenylfluorone: rocks (661, 768) yrogallol: Nb, W (671) Pyrocatechol-EDTA: Wolframites, Sn, W (664) KI-HzO~: Industrial waste waters (676, 677)
F Chromium
Review of spectrophotometric methods (367) Review of methods: I (226); ruby (66) s-Diphenylcarbazide: T a (296, 628);. A1 (388); Fe (344); permanent magnet alloys (317); Cr, Ni (264); Cu (159); alkalihydroxides (263); ruby (266); Cr, A1 (380);titanomagnetite (819); nonmetallic inclusions (234); ilmenite (686); cement (121); clay (180); forensic investigations (413); water (46, 290); tannery liquors, skins (99) Cr(II1): Cr(S’1) (361) Cr(III)-H3P04: Ores, steels (729) G O 4 : silicate rocks (310) EDTA: chromite ores (887); refractories (316); study of conditions (312, 684) DCyTA: Th (781); chromic acid (232) Methylthymol Blue: study of conditions (162) Xylenol Orange: study of conditions (162, 769) Pyridine-2,5-dicarboxylic acid: study of conditions (171) 3-Hydroxy-4-(2-hydroxy-l-naphthylazo)-naphthalene-lsulfonic acid: study of conditions and interferences (784)
Pyrocatechol Violet: study of conditions and interferences (170)
Acetylacetone: study of conditions (2.47) Thioglycolic acid: study of conditions (321) Diethyldithiocarbamate: study of complex (476) (Continued on page 116 R )
ramics and raw materials (708), apatite (791), minerals and rocks ( 4 f 4 ) , and abrasive materials (455). Concentration b y precipitation prior to spectrographic determination was used for the determination of zirconium and hafnium in silicate rocks (812) and for zirconium in water (470). Methods were also published for the determination of hafnium in iron and steel (360) and zirconium oxide (642). The simultaneous fluoridization of zirconium and sulfidizetion of molybdenum was used to increase the sensitivity of the determination of zirconium in molybdenum using a n ac arc (229). The ac arc method was also used for the determination of zirconium in ores and concentrates without prior treatment (807), in sandy-argillaceous rocks (499) and, following a fusion, in sands and silicates (707). The determination of hafnium in zirconium was carried out using the point-to-plane spark technique (485), and the powder-spark technique (736). Zirconium was determined in refractory raw materials (179),and both zirconium and hafnium were determined in tungsten-molybdenum alloys (446) and steel ( 5 4 f ) b y using a spark source. A quantometer was used for the determination of zirconium in magnesium (659). Zirconium in complex nickel alloys was determined using a highfrequency plasma source (295). The use of a pulsed solid-state laser was also studied as a source for the spectrographic determination of zirconium (497)*
Another technique which has proved to be useful for the determination of zirconium and hafnium is X-ray fluorescence. The accuracy for high concentrations of zirconium was improved by making readings before and after the addition of diluents (185). Corrections for the determination of zirconium in rocks and minerals were calculated from the mass absorption and background intensity of a line (281). The determination of zirconium b y X-ray fluorescence was applied to condensed water and sodium sulfate (670), niobium (255), rocks (792), sands (297), minerals (233),and high-melting metals (440). An ion-exchange separation was used prior to the determination of hafnium in zirconium or zirconium in hafnium b y X-ray fluorescence (459). The determination of hafnium in zirconium dioxide was preceded b y a concentration b y solvent extraction (221). Hafnium was also determined in zirconium minerals ( 1 ) . Measurements on either side of the X-ray absorption edge were used for the determination of zirconium in uranium-niobium-zirconium alloys (699). Most of the neutron activation methods published during the period covered b y this review describe methods for the determination of hafnium. The use of a coVOL. 41,
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APRIL 1969
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Table 1.
Spectrophotometric Methods (Cont’d.)
Element Chromium (Cont’d.)
Reagent: Material (References) K4Fe(CN)e: study of conditions (486) 2,2’-Bipyridine: study of conditions (557) 8-Aminoquinoline: study of conditions (800) o-Dianisidine, p-amino-N,N-dimethylaniline, or 3,3‘dimethylnaphthidine: Al, comparison of methods (385)
Tetracyanato-(1,lO-phenanthro1ine)-ferrate111:study of reactions (669) Radioisotopic light source: description of method (64.4) Automatic equipment: sewage (66) Borax bead: study of method ( 5 ) Indigo carmine-H*Oz: study of conditions (328) Methyl orange-HZ02: study of conditions (329)
Molybdenum
Reviews of spectrophotometric methods (367, 388) CNS: Review (645); study of reduction methods (7, 481, 606) study of extraction (477, 646); study of differential method (51); Nb (610); Ce (24.5); Se, Te (252); W, A1 (604); steel (29, 177,?46, 3.68, 465); cadaver tissue (637); ores (8); flotation tails (596); molybdate salts (256); rock, soil, sediment (49) CNS-crystal violet: study of conditions (386) Toluene-3,4-dithiol: iron alloys (356); W (695); soils, sediments (734); water, silicates, biological materials (146); sea water (630). Phosphotungstomolybdate: W (628, 629) Mo(V): W, Ni, Cr, T’, Mn, Cu (747) hlo04z-: minerals (192) K,[Fe(CN)e]: Re (748) EDTA: Nb (594) Tiron: electroplating baths (674) Thiosulfate: study of conditions (662) Thiomalic acid: Nb, Ti (595) Stilbazogall I: study of reagent and conditions (614) Pyrocatechol, Pyrocatechol-3,5-disulfonic acid: study of extraction (126) Pyrocatechol: Au (532) Zephiramine-CNS: study of extraction (487) Sulfosalicylic acid: refining catalyst (461) 1,lO-Pheqanthroline: study of conditions (458) Monothioglycol, unithiol: study of conditions and interferences (595) Morin: Ti, In, Ga (378); Cs, K, Na (253) 3-Phenyldaphnet~n:study of conditions and interferences
116 R
VANADIUM
A discussion of the analytical chemistry of vanadium was included in reviews describing methods for the determination of impurities in lead (95) and bismuth (500). Vanadium does not lend itself t o gravimetric determinations and because of the highly colored ions and several oxidation states exhibited in aqueous solution, gravimetric methods (szsj are somewhat unnecessary. Two methMercaptoacetic acid: steel (335, 626) Sulfochlorophenol S: Zr, U, Fe (204, 665) ods recently published are the deterDiethyldithiocarbamate: study of conditions (246); mination b y precipitation with hexaferrous metals (711) amminecobalt (111) chloride (523) and Pyrogallol red: study of extraction (737) with thallium(1) to form thallium deChromotropic acid: study of conditions (765) Alizarin red S: study of separations (313) cavanadate (558). Phenylazoxine S: study of conditions (262) The titrimetric methods published Pyrazine-2,3-dicarboxylic acid: steel (286) for the determination of vanadium are of 5,7-L)ibromo-8-hydroxyquinoline: study of separation both the redox and complexometric (197) 0,O’-Dihydroxyazobenzene: steel (141) types. A redox column containing Thiolactic acid: study of extraction (519) tetrachlorohydroquinone as the reducKI-H202: study of conditions (275) ing agent has been used prior to the Selenate-SnII; -steel (442) titration of vanadium with potassium l-Naphthylamine-bromate: W, Fe, Cu (802) C108--C1--N2H4-H2S04:study of conditions (88) permanganate (60). It was reported that mixtures of vanadium(I1) and vanadium(II1) could be titrated potenReview of spectrophotometric methods (367) tiometrically with hydroxylamine (106). CNS: Review (645); Mo (785); Fe (347, 736); WOa, W02,W20s,W, Ti02 (531);water, sewage (597) Vanadium in vanadium pentoxide was Toluene-3,4-dithiol: Mo (341); Nb (695); Fe (356); titrated with permanganate using a water (393); silicates, water (145) potentiometric titrator (479). Methyl Stilbazogall I : study of conditions (314, 315) orange was used as the titrant for the Pyrocatechol violet: study of conditions (471) Gossipol: study of conditions (364) potentiometric titration of vanadium Tiron: study of conditions (691) in 85y0 phosphoric acid and for the 6,7-Dihydroxy-2,4-diphenyl-chrom-2-en: study of condititration of chromium and vanadium in tions (596) 2-(3,4-Dihydroxyphenylaao)~phenyl-5-bensoyl-thiasole 60% sulfuric acid (272). Methyl study of reactions (397) orange was also used as the indicator Molybdotungstate: study of conditions (274) for the titration of vanadium(1V) with cerium(1V) (621) and for the titration of vanadium(1V) plus iron(I1) after ~
Tungsten
incidence spectrometer for the determination of hafnium was described (458). The minimum detection limits for zirconium and hafnium were determined (665). Several papers described methods for the determination of hafnium in Zirconium (277, 453, 551, 562, 674). Hafnium was also determined in mixtures (276), i n aluminum (21, 47, 3‘70)and in sand (553). Most of these procedures involve a n ion-exchange or precipitation separation. Irradiation by -prays was used for the determination of zirconium in hafnium (549). Radiochemical techniques were used to study global fission contamination ( 9 4 , the precipitation-separation of sirconium with benzenearsonic acid (CSZ), the solvent extraction of sirconium-95 and niobium-95 with 8-hydroxyquinoline in benzene (353), the ion-exchange separation of zirconium-95 from niobium-95 (243) and the solvent-extraction separation of zirconium-95 from niobium-95 b y mono-octyl a-anilinobenzylphosphonate (322). Radiotracer techniques were also used to study radioactive precipitants (613) and paper chromatography with radioactive precipitants (794).
ANALYTICAL CHEMISTRY
which the vanadium mas determined b y titration with iron(I1) (626). If the acid concentration is properly controlled, ferroin can be used as the indicator for tmhetitration of vanadium(1V) with ceriuni(1V) (736). Vanadium(II1) can be titrated to vanadium(1V) and then to vanadium(V) in two steps b y potent'iometric titration iii 12M phosphoric acid with potassium dichromate (619). The end-point can also be observed photometrically when the t'itration is carried out in 3.11 phosphoric acid (620). Vaiiadium(1V) can be titrated to vanadium(V) in 2.5 to 4.511 potassium hydroxide with potassium ferricyanide being used as the titrant' and niethylene blue as the indicator (56). Hypochlorite or hypobromite will oxidize vanadium(1V) to vandium(V) in a n inert atmosphere and the reaction serves as a basis for one method of vanadium determination (744). Vanadiuni(I1) and vanadium(II1) in mixtures were d e t e r m i n d by oxidiziiig all of the vanadium t o vanadium(II1) and titrating with vanadiuin(V) (783). The other stel) is to add an excess of iron(II1) and titrate the iron(I1) formed with vanadium(V). Periodate or chlorate can be used to titrate vanadium(I1) (542). Vanadium(I1) has proved to be a useful titrant for vanadiurn(V) (147) while vanadium(I1) itself can be titrated with bromate, iodate, or iodine nionochloride (148). I3y performing two titrations under different conditions, vanadiurn(IV) and vanadimn(V) can also be determined in mixtures b y titration wit,h vanadium (11) (149). The vanadium in vanadium pentoside was determined b y oxidation and then titration with iron(I1) using sodium A'-rnethyldiphenylamine-p-sulfonate as the indicator (627). Slolybdenum and vanadium are determined simultaeously by addition of a n escess of iron(I1) and titration of the excess with potassium dichromate (511). A direct potentiometric titration with iron(I1) can be used for the simultaneous determination of vanadium and chromium (782). The potassium dichroniateiron titration was applied to the determination of vanadium in titanium tetrachloride (755). Thiosulfate directly (665) and potassium iodide followed b y thiosulfate (679) both were used as titrants for vanadium. Vanadium was included in a review of comp!esometric methods for the determination of trivalent and tetravalent, metals (608). Vanadium(1V) was titrated directly with EDTA using either ferron (468), or variamine blue B (742), or hematoxylin (7179, as the indicator. An excess of EDTA was used to dissolve vanadyl hesacyanoferrate(I1) and the excess was titrated with lead to the xylenol orange end-point (410). The end-point of the back titration of the excess EDTA with robalt was de-
tected b y the catalytic production of a color with perborate and tiron (793). An automatic potentiometric titrator with an amalgamated gold electrode was used with a mercury-EDTA solution for the direct titration of vanadium (246) and in another procedure mercury was also used as the titrant for the excess E D T A with the end point being observed potentiometrically (366). A high-frequency titration with cup-ferron as the titrant was also used for the determination of vanadium (634). Vanadium was also titrated b y the heterometric method using 8-hydroxy5,7-diiodoquinoline as the titrant ( 7 9 ) . The coulometric titration of vanadium(V) was carried out using electrically generated molybdenuni(V) as the titrant (216, 803). Vaiiadiuni(I1) was also titrated coulometrically in the presence of chromium(I1) b y using iron(II1) as the titrant (726). A number of procedures describing methods for the amperometric titration of vanadium appeared in the recent literature. A tungsten or silver cathode was used with a platinum anode for the titration of vanadium(V) with iron(I1) (220). An amperometric titration with iron(I1) and potassium permanganate could be used for the determination of vanadium(V) and vanadium(1V) or vanadium(II1) and vanadium(1V) in catalysts (205). By changing the acid concentration between the titration of cerium(1V) and vanadium(V), both elements were determined b y amperometric titration with iron(I1) (716). Iron(I1) was also used for the determination of vanadium in steel (217 , 219, 362) and ores and concentrates (294) b y amperometric titration. The amperometric titration of vanadium with 8-mercaptoquinoline was studied (567, 570) and applied t o the determination of vanadium in steel ( 9 0 ) . Other reagents which were found t o be useful for the titration of vanadium are ascorbic acid (715) and tiron (763). Vanadium was also titrated with iron(11) with the end point determined redosokinetically (408). A supporting electrolyte consisting of E D T A and sodium acetate was used for the polarographic determination of vanadium and molybdenum in mixtures ( 3 3 ) . With a supporting electrolyte of ammonium hydroxide and ammonium chloride and with N-anthranildiacetic acid as a masking agent, vanadium was determined polarographically with no interferance from nickel, copper, manganese, and chromium (181). Phosphoric acid was also useful as a supporting electrolyte (801). The conditions were also described for the polarographic determination of vanadate (248). Methods for the oscillopolarographic determination of vanadium with ferron, sodium acetate, and
acetic acid (633) and with formic acid and ammonium acetate (606) as supporting electrolyte were described. Vanadium in petroleum products was successfully determined b y a n oscillopolarographic method (163). During the period covered by this review, there were more papers describing spectrophotometric methods for the determination of vanadium than any other type of determination for any element. Vanadium was included in several reviews of spectrophotometric methods. One review dealt specifically with methods for vanadium ( @ I ) , another included vanadium in a general review of spectrophotometric methods (367), a third reviewed methods using the thiocyanate ion (645), and a fourth described methods for the determination of impurities in iodine (226). A method for the determination of vanadium in vanadium oxide utilized the spectrophotometric measurement of the vanadium(V) ion in sulfuric and tartaric acids (437). Vanadium was determined along with titanium in solutions of ores and steel by the addition of hydrogen peroxide (153, 753). Molybdovanadophosphate was used to determine vanadium after solvent extraction (326) and in low alloy steel (102). The tungstovanadophosphate complex was used for the determination of vanadium in aluminum alloys (388), titanium materials (754), and coal (731). Very small amounts of vanadium were determined by spectrophotometric measurement of a boras bead ( 5 ) . The use of 4-(2-pyridylazo)resorcinol as a spectrophotometric reagent for vanadium was described in several papers (13, 131, 635, 358, 690, 697). A mixed complex of 4-(2-pyridylazo)-resorcinol and hydrogen peroxide with vanadium was also used (689). Xylenol orange which is used for the spectrophotometric determination of many elements is also useful for the determination of vanadium (14, 18, 241, 555). The complex formed between vanadium and methylthymol blue was studied and found to be suitable for the spectrophotometric determination of vanadium (751, 752). Chrome azurol S also forms a complex with vanadium which obeys Beer's law (660, 661). Chromium, tungsten, and molybdenum in amounts equal to the vanadium do cot interfere with the determination of vanadium with pyrocatechol (563). The pyrocatechol complex with vanadium can also be estracted from aqueous solutions containing large cations such as pachycarpine (739) or diphenylguanidine (125). The latter also cauSes the pyrogallol and pyrogallolsulfonic acid complexes to be extractable. Other complexes which can be used for the determination of vanadium are formed with pyrocatechol violet (512), tribromopyrogallol (124), gallic acid VOL. 41, NO. 5, APRIL 1969
117R
(191) and tiron (647, 764). The reduction of iron(II1) to iron(I1) by vanadium(1V) served as the basis for the determination of vanadium in aluminate solutions by formation of the tris-(1, 10phenanthro1ine)-iron(I1) complex (39). The extraction and spectrophotometric measurement of vanadium as the 8hydroxyquinoline complex was studied (423, 745) and applied to the determination of vanadium in steel (460). Along with 8-hydroxyquinoline, 8aminoquinoline (800) and 5 , 7-diiodo8-hydroxyquinoline (289) were also found to be useful for the determination of vanadium. Other reagents for which the conditions for the determination of vanadium were studied in detail are arsenazo I (467), gossip01 (563), morin (390), ferron (469), azoxine S (261), and thenoyltrifluoroacetone (311). Many hydroxamic acids react with vanadium to form colored species which obey Beer’s law and this fact is reflected in the number of papers published on
these reagents. A general paper on reactions of hydroxamic acids includes vanadium (57). The formation of the vanadium-benzohydroxamic acid complex was studied (494). The determination of vanadium in aluminum (666) and rocks (561) was accomplished using N-phenylbenzohydroxamic acid as the reagent. The use of Cmethoxybenzothiohydroxamic acid was studied (720)and found to be useful for the determination of vanadium in uranium compounds (721) and petroleum products (722). N - (0 - tolyl) - benzohydroxamic acid along with similar compounds N(m-tolyl)-, N-(p-tolyl)-, and N-(p-chlorophenyl)-benzohydroxamic acid and N phenyl-(pheny1aceto)-hydroxamic acid were prepared and the reactions with vanadium were studied (467). Vanadium in silicate rocks and minerals was determined using N-(0-tolyl)-benzohydroxamic acid (332). Several hydroxamic acids were recommended for specific applications. They
Table II. Other Optical Methods Method-reagent : Material (References) Element Fluorometric-morin: SiHC13 (101 , 626) Zirconium, hafnium, and zirconium plus hafnium Atomic absorption spectrophotometry: study of flame and sensitivity (30, 330, 617, 725); plasma jet (228); ThOi (774); A1 (797) Relative dispersion of double refraction: zircon (430) Fluorometric-luminol-HzOi-Co: study of reaction (43) Vanadium Atomic absorption spectrophotometry; study of conditions (651); study of flame and sensitivity (30,2.28, 330, 617); study of solvents (65.2); study of lamps (140); Zr (618); steel, oil (134); sea water (631) Flame photometric: study of flames (172, 719) Atomid absorption spectrophotometry: study of flame Niobium and tantalum and sensitivity (30, 61 7 ) Fliiorometric-dioxyazo compounds: study of reactions Niobium (100)
Tantalum Chromium
Molybdenum
Flame photometric: study of flame characteristics ( 172) Fluorometric-rhodamine 6G: Si, SiHCl3 (23) Atomic absorption spectrophotometry: study of flame and sensitivity (725) Fluorometric-triazinylstilbexone: study of conditions and interferences (749) Atomic absorption spectrophotometry: study of sensitivity (616-618); study of burner and flame (237); effect of amines (287); study of flame (510); study of excitation source and flame (464); description of automatic equipment (724); rare earth and refractory metals (330); A1 (61, 797); Al, Ni (398); Ni (190);iron andsteel (70,249,307,672);ruby (756); minerals (28); urban air (446); waters (490) Flame photometry: study of burner and flame (810); alloys (660); water (690) Atomic fluorescence flame photometry: description of equipment (650) Fluorometric-carminic acid: study of conditions (376); steel (377) Atomic absorption spectrophotometry: study of flame (30, 617); water, plant materials, silicate rocks (127); suppression of interferences (167); Nb, T a (372); steel (375); blood, urine (582); UFa (663); fuels and lubricants (608); sea water (631) Flame photometric: study of flames (373, 374); steel ( 7031
Tungsten
118 R
Fluorometric-flavanol.: steel (97); Th, Co, Ni, Cr (98) Fluorometric-Carminic acid: study of conditions (376) Atomic absorption spectrophotometry : study of flame and sensitivity (30, 61 7, 725); sea water (631)
ANALYTICAL CHEMISTRY
include salicylhydroxaniic acid for vanadium in biological materials (428), N-phenylcinnamohydroxamic acid for vanadium in the presence of iron and uranium (812), and N-phenyl-2-furohydroxamic acid for vanadium in brines (585) and steels and ores (584). Additional reagents of this type which have been studied include p-methosybenzenethiohydroxamic acid (723), N-phenylp-phenylazobenzohydroxamic acid (142) and caprohydroxamic acid (601). The vanadium in titanomagnetite was determined by the use of cyanoformazan-2 (819) as was the vanadium in heat-resistant alloys (820). Titanium concentrates were analyzed for vanadium by the use of formazan (411). Other reagents for which procedures for the determination of vanadium were developed and in some cases interferences were studied were sulfosalicylic acid (150), salicylaldehyde ( 4 2 4 , anthranilic acid with salicylaldehyde (62), 1-amino-8-napht hol-3 , 6-d isulf onic acid with salicylaldehyde (589), nicotinic acid hydrazide (412), p-anisidine (673), 2 - (2 - thiazolylazo) - 5 - (diethylamino)phenol (306), 7-amino-l-naphthol-3,6disulfonic acid (15), N-methylanabasine-a’-azohept’ylresorcinol (687), 5(2-pyridylazo)-2-monoethylamino-p-cresol along with the &bromo- and 3 , s dibrorno-derivatives (271), 3-hydroxyflavone ( % I ) , d-antipyryl-(3,4-dimethoxypheiiy1)-methaiie with potn~sium thiocyanate (5’87) and pyridine-2,G dicarboxylic acid (602). Reagents recommended for the determination of vanadium in specific materials are benzidine for alkali hydroxides (253), 3,3’diaminobenzidine for sea water (630), 3,3’-dimethylnaphthidinc for steel (643), N , N - dimethyl - p - phenylenediamine hydrochloride (582) or p-phenetidine (436) for aluminum materials, 3-amino4-[3-( 1-methyl-2 - piperidyl) - 2 - pyridylasol-phenol for ores (769)and P-(diantipyrinylmethy1)-styrene or a,a’-diantipyrinyl-3,4-dimethosytoluene for steel (588). The so-called catalytic methods in which a metal serves as a catalyst’in the oxidation of a n organic molecule by an oxidizing agent have proved to be quite sensitive methods for the determination of vanadium. I n one series of papers, methods involving various reactions are described. They include the bromateiodide-ascorbic acid (84) or the chlorateiodide-zinc reaction (85), the bromatebromide-ascorbic acid reaction wit,h a fluorescent indicator (86), the chloratechloride-tin(I1) reaction (87) and the chlorate-chloride-hydrazine-sulfuric acid reaction (88). I n another series of papers, hydrogen peroxide was used as the osidizing agent in all cases. The organic molecules involved were p chloroaniline (543), s-diphenylc:trbnzide (544), benzidine (545), and aniline (546). A method involving the osida-
tion of 4-amino-5-hydrosynaphthol-2, 7-disulfonic acid with bromate was proposed (406)and applied to the determination of vanadium in sodium and potassium chlorides (407). The oxidation of phenylhydrazine-p-sulfonic acid by chlorate has also been studied in detail (74f) and the oxidation of thiocyanate by bromate has also been proThe determination of posed (%I). vanadium in rocks was carried out by using the hydrogen peroxide-aniline reaction (231). The quenching of the fluorescence by vanadium of the hydrogen peroxide-5-amino - 2,3 - dihydro phthalaxine-1 ,4-dione reaction in the presence of cobalt is also proposed as a method for the determination of vanadium (43). Atomic absorption spectrophotometry has been examined as a possible technique for the determination of vanadium. Vanadium was included in a study of comparative sensitivities of the oxyacetylene and nitrous oxide-acetylene flames in which the nitrous oxideacetylene mas shown to yield better sensitivities (330). Another study of the nitrous oxide-acetylene flame sensitivities of many elements also included vanadium ( 6 f7 ) . Sensitivities for elements such as vanadium were increased greatly when various organic solvents were added to the sample solution with either the nitrous oxide-acetylene or oxyacetylene flames (652). Vanadium was separated from many other elements by extraction into a solution of cupferron in a mixture of methylisobutylketone and oleic acid before being determined using the oxyacetylene burner or the vanadium cupferrate could be extracted into methylisobutylketone and the nitrous oxide-acetylene bumer used (651). High-brightness lamps were prepared to improve the signal t o noise ratio in the determination of vanadium (ICO),and the use of the nitrous oxide flame for vanadium was described (30). Applications of atomic absorption spectrophotometry for the determination of vanadium include its determination in titanium alloys (518), steels and gas oils (fsj),and sea water (631). The plasma jet was also used as a flame for atomic absorption spectrophotometry (228). Studies of flame emission methods for the determination of vanadium include the establishment of excitation gradients in oxyacetylene flames (172) and the determination of the spectra in a n oxyhydrogen flame ('7f 9). Vanadium was included in a study of the detection limits that could be achieved for difficultly excited elements by the use of a plasma type burner (639). Methods involving excitation by electrodeless discharge have also been found to be useful for the determination of vanadium (109,1fi5). The method of t'irne-resolved spectroscopy was used to
Table 111.
Titrimetric Methods
Element
Reagent: Material (References)
Zirconium, hafnium, and zirconium plus hafnium
Review of titrimetric methods: (608) EDTA: study of reaction (718); Nb (116); Y (609); ores (401)! y o (524), Zr alloys (309), ZrBl (89), study of indicator (155, 288) use of Ag electrode (700), use of potentiometric titrator (75) NaOH: (NH&ZrF6 (496) Trilon B: fission products ( d o g ) , leather (187, 788); study of method (186) Mandelic Acid-V(V): study of method (483) Diethylamine: study of method (714)
Vanadium
KMn04: study of redox column (60); use of automatic titrator (479); study of reactions (611, 619, 620), TiC14 (756) Ce(1V): study of reaction (621), Fe (622), study of indicator (732) Hydroxylamine-KMnOc or Ce(1V) : study of reaction (106)
Fe(I1): Cr (782); VZOS(627) V(I1): study of reactions (147, 149) Thiosiilfate: study of reactions (625) KI-thiosulfate: study of reactions (679) Methyl orange: study of reactions (272) KsFe(CH6): study of reactions (66) Periodate or chlorate: NZHZ(642) Hypochlorite or hypobromate: study of reactions (744) Bromate, iodate or iodine monochloride: studv of reactions ( i 4 8 ) Fe(II1): study of reactions (783) EDTA: review of methods (608); study of reactions (242); study of indicator (717, 742, 793); vanadylhexacyanoferrate (11) (410); Cd, Co, Ni, Ca, Mg, Sr, In, Hg (366) Cupferron: study of end-point detection (634) 8-Hydroxy-5,7-diiodoquinoline: study of interferences (79)
Niobium
8-Hydroxyquinoline-bromate: AI, Mn, Sn, Ti, W (340) Nitrilotriacetic acid or EDTA H202: study of reactions (427)
Nitrilotriacetic acid: refractory materials (426) Tantalum
Khln04-H202: TaFB, NbFS (42)
Chromium
Fe(I1): study of conditions (242); V (782); Ti concentrate ( 4 1 1 ) ; Cr ores (402); minerals (777) KMn04: slags (230) KI-Na2S20a: Cu (176); Fe (636); A1 (104); refractory materials (36, 37); leather (788); Zn, Co, Ni, Cu (636) V(I1): study of reactions (147) SnClz: Fe (31) Methyl orange: V, Ce, Mn (272) EDTA: study of reactions (160, 301, 706); study of indicators (300, 623), use of automatic titrator (76), A1 (656); Fe, Al, Ca, Mg (36); Fe, Zn (162); Zn (603); Fe, A1 (299, 581); steel (161); chromite (460); silicates (38)
Y(N03)s: study of conditions (606) Trilon B: study of method (186); leather (187) Molybdenum
F e ( I I ) - K ~ C r ~ OV~(611) : Ce(1V) or K2Cr207: study of indicator (664) Ce(1V): study of reactions and interferences (667) Ce(1V); V(V); K2Cr20,: KMn04-Fe(I1); Ce(1V)Fe(I1); Fe(II1)-KMn04: study of titrants and reductants (68) V(V): study of indicator (260) Ti(II1): study of conditions (280) Fe(I1): W, Zr, Fe, Re, Nb (782) EDTA: study of conditions (746); Zr, B, Si (624); Ge (600);W (686); Nb, W (594) Pb-EDTA; Fe (701) Pb: study of interferences ( 4 4 1 ) AgNOa: study of conditions (710) &Hydroxyquinoline: study of conditions (350) Cupferron: study of conditions (634)
Tungsten
ICl: study of conditions (676) Pb: study of indicator ( 4 4 1 ) ; study of conditions (268)
VOL. 41, NO. 5, APRIL 1969
119R
study the time evolution of some spectral lines from several elements including vanadium (78). Vanadium in pure alkali metals was determined spectrographically after extraction with diethyldithiocarbamate (156)and in rubidium and cesium arsenates by using the same extractant (214). A mixture of cadmium sulfide and carbon powder was used as the collector in a method of concentration by precipitation in the spectrographic determination of several impurities including vanadium in alkali and alkaline earth salts (578). The vanadium and other impurities in copper were concentrated prior to determination by electrodeposition of the copper (40). An anion-exchange method was used for the separation of impurities from a plutonium-uranium-zirconium alloy before spectrographic determination (504). The impurities including vanadium in natural waters were concentrated by extraction with diethyldithiocarbamate (814). The vanadium and other impurities in silicon tetrachloride and trichlorosilane were determined spectrographically after concentration by extraction into chlorotriphenylmethane (779). Extraction into 8 - h y d r o x y quinoline was used to concentrate the impurities in hydrochloric acid (429). The carrier fractional distillation method was modified to improve the sensitivities for the determination of impurities in uranium (155). The vacuum-cup electrode was used for the determination of vanadium and other metals in refractory metal alloys (443). An excitation technique for the analysis of high-purity metals consisted of blowing the powdered sample into a n ac arc (529). I n the analysis of refractory raw materials, the complex was fused with a mixture of sodium carbonate, potassium carbonate, and sodium tetraborate, the melt was then dissolved and the solution sprayed on a rotating carbon electrode (179). A number of other papers reported the determination of vanadium in various materials without prior separation and in a few cases with no preliminary treatment of any kind. These include the determination of vanadium in beryllium (158), aluminum (189), titanium alloys ( l i d ) , titanium tetrachloride (182), gallium (607), rare earth oxides (400), zircaloy-2 (548), high-silica materials (526, 540), granites (757), rocks, minerals, and petroleum ash (65), sandy-argillacious rocks (499), oil ash (675), oil products (475), and steel products (63, 71, 75, 91, 92, 111). Mass spectrometry was used for the determination of several elements including vanadium in gallium (222). The use of a spark-source mass spectrometer for the determination of a number of elements including vanadium in impurity amounts has been studied 120 R
ANALYTICAL CHEMISTRY
(10, 538) and applied to the determination of vanadium in ruby crystals (696). The determination of vanadium b y X-ray fluorescence has been reported in several papers. The vanadium in petroleum was concentrated by an ionexchange method and then determined by X-ray fluorescence ( 6 4 ) . Precipitation by addition of tartaric acid and cupferron was used to concentrate the impurities present in condensed water and sodium sulfate solutions (670). N o separations were used for the determination of vanadium by X-ray fluorescence in a number of materials including beryllium (139), steel (196), sulfate solutions (175), zeolites (278), and polyolefins (212). The technique of using measurements on both sides of the X-ray absorption edge was proposed for the determination of vanadium (619). Computer techniques were used for the calculation of detection limits for the determination of vanadium b y neutron activation (565). 130th nondestructive and destructive methods were used for the determination of vanadium in iron (473). An ion-exchange concentration was used in conjunction with neutron activation for the determination of vanadium in sodium chloride (771). Vanadium was separated from aluminum by cupferron extraction in the determination of impurities in aluminum (S70). A study was made of the determination of aluminum and vanadium when the aluminum to vanadium ratio was between 1 and 60 ( 1 7 ) . Keutron activation was also used for the determination of vanadium in red phosphorus (559) and crude petroleum ash (454). NIOBIUM AND TANTALUM
Niobium and tantalum will be considered together even though the same methods can not necessarily be used to determine both elements. In the case of niobium and tantalum, the elements frequently occur together in natural materials and as a result many papers describe methods for both elements. Discussions of niobium and tantalum were included in a recent book describing the analytical chemistry of several of the elements included in this review (206). A recent review covers complexes of niobium and tantalum as well as methods of separation and determination (650). The complete analysis of tantaloniobates and tantalotitanates was the subject of another review (585). Methods for the determination of niobium and tantalum in steel (448) and impurities in germanium (526) were also reviewed. Gravimetric methods for niobium and tantalum only very rarely appeared in the literature during the period of this review. The conditions for the pre-
cipitation and gravimetric dcterrnination of niobium with resacctophenone oxime were studied (521). I n order to determine niobium in aluminum-niobium-molybdenum alloys, the niobium was precipitated by the addition of ammonium hydroxide to a solution of the sample to which EDTA had been added (685). Niobium was determined in samples containing molybdenum and zirconium by adding boric acid to complex the fluoride and boiling with hydrochloric acid to precipitate the niobium (559). Niobium-tantalum mineralf were analyzed for the sum of the niobium and tantalum by precipitating them with tannin (591). I n a solution at pH 3, niobium in the presence of hydrogen peroxide can be titrated with either E D T A or nitrilotriacetic acid using xylenol orange as the indicator or an excess of the titrant can be added and back-titrated (427). The nitrilotriacetic acid titration was used for the det,erniination of niobium in niobium carbide and nitride samples (426). Another titrimetric method for niobium consisted of the precipitation of niobium with 8-hydroxyquinoline1 dissolution of the precipitate, and titration of the 8-hydroxyquinoline with bromate (340). Tantalum in the presence of titanium, molybdenum, vanadium, and iron can be titrated by forming the tantalum peroxide complex by the addition of excess peroxide and titrating the excess with potassium permanganate if phosphate is present in the solution ( 4 2 ) . An amperometric titration utilizing cupferron or neocupferron as the titrant can be used for the det,ermination of niobium in the presence of tantalum (775).
Under the proper conditions, niobium can be determined polarographically. The polarographic reduction of niobium in a hydrochloric acid-ammonium thiocyanate solution was used (478). -1 supporting electrolyte of hydrochloric acid, hydroxylamine, and tartaric acid was studied (706) and applied to the determination of niobium i n bauxite following ion exchange (456). The polarographic determination of as little as 15 pg of niobium per 50 ml in a hydrogen peroxide solution was studied (681) and applied to the determination of niobium in nickel-aluminum alloys (682). Phosphate solutions have been used for the polarographic determination of niobium in refractory alloys ( 6 9 4 , in the presence of copper (418), and in the presence of molybdenum (419). .Z hydrochloric acid-ethylene glycol supporting electrolyte was used for the polarographic determination of niobium in a binary alloy with tin (67) and in a niobium-tin coating on a steel st,rip ( 6 8 ) . An oscillographic polarograph was used for the determination of niobium in zirconium-niobium alloys (698). The niobium in metallic tanta-
luni was determined b y oscillographic polarography in a phosphate solution (416 ) as was the niobium in leach solutions from rare earth titanoniobates (417 ) . With a supporting electrolyte of EDTA niobium was determined in ores and concentrates (789). Niobium in iron and steel was determined b y ac polarography using a n EDTA-acetate solution (367). A voltammetric method was used for determining down to 0.1% niobium in stainless steel (474). I n this section, which covers spectrophotometric methods for the determination of niobium and tantalum, those papers which discuss only niobium will be discussed first, followed b y those papers which discuss both niobium and tantalum, and finally those papers will be discussed which deal only with tantalum. Reagents for the determination of niobium in the presence of tantalum were discussed in one review (59) and the use of azo dyes for the determination of niobium was discussed in another (26). Hydrogen peroxide was used as the reagent for the determination of niobium in niobate samples (257). Niobium in steel was determined by separating the niobium from the iron and forming potassium hexaniobate and then measuring the absorbance a t 234.5 mp and correcting for the other elements present (180). Niobium was discussed in a review of the use of thiocyanate in spectrophotometric analysis (646). The change in the spectrum and the percentage extraction of the niobium-thiocyanate complex were studied using tributylphosphate and various diluents (646:). Niobium was separated from a n escess of tantalum and determined by extraction of the thiocyanate complex. into tributylphosphate (169). Aluminum was used to eliminate the fluoride interference in the thiocyanate procedure for niobium (133). Methyl isobutylketone was used as the solvent for the extraction of the thiocyanate complex in the determination of niobium in rocks (498). Reversed-phase partition chromatography was used to separate niobium from the other components of molybdenite prior to determination with thiocyanate (492). The niobium in steel was determined b y using the thiocyanate complex in acetone solution ( f o g ) , after extraction into tributyl phosphate (239), and after extraction into diethylether (425::). Tetraphenylarsonium chloride forms a complex with niobium and thiocyanate which can be used for the determination of niobium in steel (11). A modified thiocyanate method calls for correcting for interferences b y selectively bleaching the niobium thiocyanate complex (285). The niobium complex with P-(2-pyridy1azo)-resorcinol was studied (200) and applied to the determination of niobium in steel
Table IV.
Element Zirconium or hafnium
Vanadium Niobium Niobium and tantalum Chromium Molybdenum
Tungsten
Gravimetric Methods
Reagent: Material (References) Cupferron: from homogeneous solution (168), Si (60) Phosphate: Si (50), Si, Al, Ti (308) 2-Nitrobenzoic acid: study of conditions (416) 2-Mercaptopropionic acid: study of interferences (680) Vanillin: study of interferences (325) Hexammine cobalt(II1) chloride: study of conditions (523) TlNOJ: Fe or A1 (558) Resacetophenone oxime: study of conditions (681) ",OH: Mo, A1 (685) HaBOa-HC1: Zr, Mo (599) Tamnin: minerals (691) Pyridine-2,5-dicarboxylicacid : study of conditions (171) Thioacetamide: study of conditions (188), steel, W (183) EDTA-Pb-Cr: study of reactions (638) a-Benaoinoxime: W (403) Purpurogallin: Ti, Zr (188) Cupferron: Nb, A1 (685) p-Naphthoquinone-tannin: W (686) Molybdiphosphates: study of reactions (69) &Hydroxyquinoline: Co (663) 8-Hydroxyquinoline: study of accuracy and precision (259); minerals (198) &Naphthoquinone tannin: alloys (686) Variamine blue: steel (207) Pyramidon: sintered carbides (509) Acid dehydration-HCl: Ni, Al, S (573) 1,SNaphthylenediamine: study of conditions (448)
+
(201), and in tantalum (202). The 4-(2-pyridylazo)-resorcinol complex has also been found useful for the determination of niobium in steel (554) and zirconium (655) with no prior separation, and in steel following removal of the iron by extraction (733) and b y ion exchange (166). The molybdoniobophosphate complex was studied and found to be satisfactory for the determination of niobium in niobium and tantalum oxides and fluorides (809) and in steel (102). The yellow form of the complex was used for the determination of niobium in aluminum metal and alloys (388). Chlorosulfophenol S was found t o be a useful chromogenic reagent for the determination of niobium (115, 665). The reaction between niobium and cyanoformazan-2 was studied (805) and used for the determination of niobium in heat-resistant alloys (4.20) and ores (426). Xyleiiol orange formed a colored complex with niobium which has been used as the basis for a spectrophotometric method (14, 240). Tantalum, tungsten, and the rare earths do not interfere with the determination of niobium with N-methy1anabsine-a'azoresorcinol (740). Of some 51 anions and cations tested, only the uranyl, vanadyl, and phosphate ions interfered with the determination of niobium using 2-(2-thiazolylazo)-5(diethylamino)phenol (305). Niobium in fluoride solutions can be determined spectrophotometrically with pyrocatechol and EDTA if the fluoride is masked with boric acid (41). The properties of the
niobium-pyrocatechol violet complex were studied (471), and the reagent was used for the determination of niobium in alloy steel and nickel (472). Acid chrome violet K was used for the determination of niobium in alkali hydroxides (253), and acid chrome blue K was proposed as a chromogenic reagent for niobium (151). Tungsten and tantalum interfere with the determination of niobium with gossip01 but many other metals do not (364). A liquid ion-exchange resin is used to separate the tantalum from niobium in the method for the determination of niobium in tantalum with phenylfluorone (379). T h e conditions and interferences were studied for the determination of niobium by using either N-methylanabsine - a'- azo - 6 - rn - aminophenol (770), 4-methyl-6,7-dihydroxycoumarin (324), or 5-(2-pyridylazo)-2(ethylamino)-4methylphenol (198) as the reagent. Picramine R was used for the determination of niobium in alloys containing molybdenum; uranium, titanium, tin, and aluminum (203). If titanium and zirconium are masked with E D T A , niobium can be determined by using eriochrome blue-black B (806). N-Phenylbenzohydroxamic acid (688) and 8-hydroxyquinoline (361) were recommended for the determination of niobium when zirconium was present. The niobium complex of methylthymol blue was used for the determination of niobium in uranium and tungsten (199). The determination of niobium in titanium and titanium tetrachloride was carried out using o-nitrophenylfluorone VOL. 41, NO. 5, APRIL 1969
121 R
Table V.
Electrometric Methods
Element Zirconium, hafnium and zirconium plus hafnium
Method: Reagent: Material (References) Amperometric: EDTA: organic compounds (750) Amperometric: EDTA-T1: study of method (365) Amperometric: cupferron: study of electrode (776); study of method (680) Polarographic: study of supporting electrolyte (27, 656, 657); Ni, Al (682); study of electrode reaction (683) Voltammetric: Alizarin red S: study of complex (816,
Vanadium
Amperometric: Fe(I1): Study of electrodes (220); catalysts (205); Ce (716); steel (217, 219, 362); ores and concentrates (294) Amperomc$ric: 8-mercaptoquinoline: study of reaction (567, 570); iron and steel (90) Amperometric: Tiron: study of reaction (763) Amperometric: ascorbic acid: Ce (715) Redoxokinetic: KMn04 or Ce(1V): study of reactions
81 7 )
(LO,?)
Ci;iometric: Mo(V): study of reactions (803); Ti (216) Coulometric: Fe(II1): Ti, Mo (726) Polarographic: study of supporting electrolyte (801); study of masking agent (181); study of conditions (248); Mo (33) Oscillopolarographic: study of supporting electrolyte (502); study of complexing agent (688); petroleum (163)
Amperometric: cupferron or neocupferron: natural samples (775) Polarographic: study of supporting electrolyte (478, 681, 706); Ni, A1 (682), heat resistant alloys (894), CLI(418),M o (4!9), Sn (67, 68), bauxite (456) Oscillopolarographic: Zr (698); Ti, W, Fe (416), rare earth titanoniobates (417); ores and concentrates
Niobium
(7891
ac-Polarographic: steel (357) Voltammetric: steel (474) Amperometric: several complexons: study of reactions
Chromium
(157)
Amperometric: H202: study of reactions, Mn, Ce (813) Amperometric: KMnO,: study of conditions (489) Amoerometric: Fe(I1): Ni, W, Mo. Co, Ti (218);
v' (217 )
Molybdenum
.
I
Coulometric: Fe(II), Mn04-: Fe (772) Coulometric: Fe(II1): V, M o (726) Coulometric: Pb(I1): study of conditions (773) Coulometric: Mo(V): study of conditions (215,803) Voltammetric: NazWO4 (404) Polarographic: metallurgical materials (641); antistatic additive (158), study of supporting electrolyte (491),study of conditions (248); CdS (630) Squarewave polarographic: study of conditions (279) Amperometric: 8-mercaptoquinoline: study of reactions (702); ferromolybdenum, steel (669) Amperometric: K3[Fe(CNjs]: ores, Ti, Ni, A1 (766) Amperometric: ascorbic acid: Ce (716) Amperometric: diantipyrylmethane: study of conditions (816)
Amperometric: 8-hydroxyquinoline: study of conditions (106)
Amoerometric: KI-H202: W (117): W, Cu, Co, Ni, An, Z i ,Pb (118); study of conditions (677, 678) Coulometric: Ti(II1): Sn. Pb. Cd., Cr,, Ni.. Mn, W, ME .~.~~ . (804); study of reactions (74) Coulometric: Fe(II1): V (726) Coulometric: Fe(I1): study of conditions (16) Coulometric: Pb: study of conditions (773) Polarographic: Sn, Zn (712); Ca (463); study of supporting electrolyte (130,.869, 801);study of complex ( 1 2 ) ; study of separatlons (183, 184); W (6%); ores, alloys, concentrates (294, 298); V (33, 270); Nb (419), study of conditions (248); steel, brass, Ni ~
~
(6411
Tungsten
122 R
Oscillopolarographic: study of conditions (505, 633) Amperometric: CNS-diantipyrylmethane: study of conditions (815) Amperometric: KI-H202: CdS, LiF (118) Coulometric: Pb: study of conditions (773) Polarographic: study of conditions (248); study of supporting electrolyte ( 8 1 ) ; heabresistant alloys (694); alkali chlorides (484);steel, brass (641) Oscillopolarographic: study of conditions (244); Ta (416)
ANALYTICAL CHEMISTRY
('798). Several reagents which can be used for the spectrophotometric determination of niobium in steel are 2,4sulfochlorophenol C (209), 1-(2-pyridylazo)-2-naphthol (136), lumogallion (S4S), bromopyrogallol red (796), and nitrosulfophenol S (808). Niobium and tantalum are both included in a n extensive review of recent spectrophotometric methods (367). Another recent review classifies the organic chromogenic reagents which are useful for niobium and tantalum into five groups (684). A tannin precipitation was used for the separation of niobium and tantalum from interfering elements prior to determination of the niobium with thiocyanate and the taqtalum with crystal violet (129). Both niobium and tantalum can be determined spectrophotometrically with pyrocatechol and EDTA after separation from the interfering elements in wolframites and tin-tungsten concentrates by extraction with 7,g-dihydroxy4-methylcoumarin (564). Another reagent which can be used for both niobium and tantalum is 4-(2-pyridylazo)resorcinol (IS). Zirconium minerals were analyzed for niobium by using thiocyanate and for tantalum by using rhodamine 6G after separation by tannin precipitation (384). The molybdoniobiophosphate heteropoly acid was used for niobium and butylrhodamine for tantalum in the determination of these elements in ores (56). Kiobiuni was determined by thiaaolyl- or pyridylazoresorciriol and tantalum by p-dimethylarninophenylfluorone in the analysis of rocks (561). I n two papers describing methods for the determiiiation of niobium and tantalum in steel, the tantalum was determined by using malachite green while in one case the niobium was deterrnined by using pyrocatechol and EDTA (827) and in the other pyrogallol (264). Tantalum was determined by extraction of the methyl violet complex into benzene (650). This reagent was used for the determination of tantalum in technical-grade tantalum oxide (178). Brilliant green also was used as a reagent for tantalum by extraction of the complex into benzene (536). Other workers used the method for the determination of tantalum in ferro-nickel and niobium metal (767). -4 separation by extraction into butyl-rhodamine C in benzene was used prior to determination with rhodamine 6G (568). Rhodamine 6G was also used for the determination of tantalum in tin-containing solutions ($71) and malachite green was used for tantalum in boron, uranium, zirconium, and zircaloy-2 (103). One of the few spectrophotometric reagents for tantalum which is used without extraction is 4-(2-pyridylazo)-resorcinol (339). The pyrogallol complex was extracted into tetrahexylammoniuni iodide in ethyl
acetate (671), the phenylfluorone complex into methylisobutylketone (291), and the p-dimethylaminophenyl-fluorone complex into isobutyl alcohol (768). Tantalum was determined in silica and trichlorosilane b y measuring the fluorescence of the rhodamine 6G complex (23). Niobium was included in a general study of reagents for fluorometric analysis (100). The catalytic effect of tantalum on the oxidation of iodide by hydrogen peroxide was used for the determination of tantalum in natural and industrial waste water (576). It was subsequently reported that the addition of calcium or aluminum to the solution increased the sensitivity of the determination (577). Niobium and tantalum were included in experiments to determine the sensitivity of various elements when using the nitrous oxide-acetylene flame for atomic absorption analysis (30, 617, 725). The position of maximum emission and optimum acetylene to oxygen ratio were established for the aspiration of ethanol solutions of several elements including niobium in a flame photometric method of determination (172). I n the spectrochemical determination of niobium and tantalum in rocks, cobalt chloride was added to reduce the effect of niobium on the tantalum sensitivity (649). Copper chloride was added to cause distillation of niobium and tantalum chloride during spectrochemical determination of these elements in quartz (598). Concentration of niobium and tantalum was effected b y precipitation with salicylfluorone and bis(salicyla1)bianisidine in the spectrochemical analysis of silicate rocks (20, 811). Another technique used for the concentration of niobium and tantalum for spectrochemical determination was to co-precipitate them with ammonium molybdiphosphate and then volatilize the molybdenum and phosphorus (746). Niobium and tantalum were determined without prior separation in refractorymetal alloys (443), steel (541) and wolframites (506). The sensitivity of the method for determination of impurities including niobium in cesium and rubidium arsenates was increased by extraction of the diethyldithiocarbamates and 8-hydroxyquinolates into chloroform (214). Spectrochemical methods without prior separation were used for the determination of niobium in tantalum oxide ( l o r ) ,ores and concentrates (807), rocks and minerals (,$Id), and quartz rocks (505). Tantalum was included in a review of methods for the determination of impurities in reagents (778). Tantalum and tungsten were separated from plutonium b y precipitation of the plutonium as the fluoride prior to spectrochemical determination (54). A pulsed, solid-state laser was used for excitation in the spectrochemical determination of niobium and tanta-
lum in various high boiling and high melting materials (497). The determination of niobium and tantalum b y the use of X-ray fluorescence techniques was also reported in several papers during the period covered b y this review. The standard deviations for the determination of niobium and tantalum in hard metals by several methods are tabulated (438). Procedures were recommended for the determination of the constituents including niobium and tantalum in 16 different hard metals and other hard materials (440). Other X-ray fluorescence methods for niobium and tantalum described the analysis of hard metals (586), metal powders (224), and
tantalum oxide-niobium oxide mixtures (405). Seven methods for the X-ray fluorescence determination of niobium in heterogeneous materials were compared statistically (727). A modification of the external standard method was proposed for the determination of niobium in minerals (128). The niobium in corrosive water was concentrated by precipitation with cupferron prior to determination b y X-ray fluorescence (670) Methods were reported for the determination of tantalum in niobium metal (225), in silver metal after extraction into hexone (282), and in steel (110). The possibility of determining tantalum b y X-ray absorption was studied (612). Niobium was deterI
Table VI. Spectrochemical
Zirconium
Material (References) Refractory metal alloys (443); Tan05 (107); Tal Mo (446); steel (641); silicate rocks (811); study of laser source (497) M O (229); Mg (669); Ni (296); rear earth oxides (400); Zr concentrates (392); paint (119); ceramics (708); apatite (791); rocks and minerals (41.4); ores and concentrates (807); abrasive materials (466); sandyargillacious rocks (499); sands and silicates (707); refractory raw materials and products (179); waters
Hafnium
Zr (486, 736); ZrOz (642);
Vanadium
Studys of excitation method (78, 209, 196, 639); .alkali metals (166); alkali arsenates (214); alkali and alkaline earth metals (678); Cu (40); Pu, U, Zr (304); water (814); SiCL, SiHCls (779); U, (136); refractory metals and alloys (443, 529); refractory raw materials (179); Be (138); A1 (189); Ti alloys (114); Tic14 (182); Ga (607); rare earth oxides (400); zircaloy-2 (648); SiO,, quartz (526, 640). granites (767); sandyar illacious rocks (499); rocks minerals, petroleum asf (66); oil ash (676); oil products (476); H I (429); steel (63, 71, 73, 91, 92, 111) Rocks (20, 649, 746, 811); quartz (698); refractory metal alloys (443); steel (641); wolframite8 (606) RbaAsOd, CsaAsOi (214); Tat.0P5(107); ores and concentrates (807); rocks and minerals (414,606) Reagents (778); Pu (64); study of laser excitation (497) Study of laser excitation (497); method of introducing sample (348); study of plasma excitation (639, 648); alkali metals, arsenates (213,214); Be (138); Ga (607); As (728); GeClr (679); rare earth oxides (666); Ni (69). Cu (40); Ti02 (227); NbzOa (709); Tat05 (107); La (f96); Si (626, 786); Pt (760); zircaloy-2 (495); U (136); UF4 (136); U, Mo (638); Pu, U, Zr (304); steel (48, 63, 71, 72, 82, 91, 92, 111, 647); reagents (778); rubies (263, 36g); refractory raw materials (179). refractory-metal alloys (443, 629); ores and minellals (194); rocks (499, 6/01; H I (429); HzS04 (704); water (470, 666, 814); organic liquids (433-
Element Zirconium and hafnium
(470)
Niobium and tantalum Niobium Tantalum Chromium
(366)
w
(672); iron and steel
456,680,668)
Molybdenum
Tungsten
Metallurgical materials (46); wire (868); alkali, alkaline earth metals (678); alkali arsenates (214); Be (138); Ga, Gaz03 (607); Cu (40); Si (786);. U (136, 638); U, Pu, Zr (304); W (446, 607); zircaloy-2 (548); refractory metal alloys (443); refractory metals (629); steel (63, 71, 73, 111); granite (319); ores, rocks, minerals (194, 318); H I (429); biological materials (266); plants (96); blood serum (226); mineral waters (671); natural water (814); solutions (633); study of excitation method (109, 196); study of laser source (497) M o (369, 446); Si, Cr, Nil Fe (349); refractory metal alloys (443); steel (71, 111); rocks and minerals (318); granite (319, 380, 431); study of laser source (497)
VOL. 41,
NO. 5, APRIL 1969
a
123R
mined in uranium-niobium-zirconium alloys using the X-ray absorption edge technique (699). A neutron activation method was used for the determination of niobium in rocks (34). Substoichiometric extraction was used to remove interferences in the neutron activation method for tantalum (25). The detection limits of a number of trace elements including tantalum, were calculated using computer techniques (565). Metals in which tantalum was determined by neutron activation analysis included niobium without a separation (4), niobium following an extraction (22),and tungsten following an ion exchange separation (211). Tantalum in sand was also determined following an ion exchange separation (563), while in rocks a solvent extraction with methylisobutylketone was used (482). Tantalum was determined in diborane by neutron activation analysis (293). CHROMIUM
With the exception of gravimetric methods, the papers describing methods for the determination of chromium are more evenly distributed among the various types of methods than are the papers for the other elements covered by this review. Chromium was included in several reviews of methods for the determination of impurities in a particular substance. The materials considered were semiconductor compounds (251), bismuth (500), lead (95), germanium (525),and sulfur (19). The lone gravimetric procedure describedp recipitation with pyridine2,5dicarboxylic acid (171). Chromium can be determined by both oxidation-reduction titrations and complexometric titrations using E D T A as the titrant. I n the analysis of titanium concentrates, the chromium was oxidized with peroxidisulfate and titrated potentiometrically (411). Chromium(V1) was titrated with iron(I1) using a n automatic potentiometric titrator (242). Mixtures of chromium and vanadium were titrated potentiometrically using iron(I1) as the titrant (782). Chromium(V1) is completely reduced to chromium(II1) before the vanadium(V) is reduced. Chromiumcontaining ores and minerals were analyzed for their chromium content by oxidation with peroxydisulfate and reduction with iron(I1) (402, 777). Chromium(I1) was determined in slags which contained iron(II1) chloride but not iron oxide by dissolving the slag with hydrochloric acid and titrating the iron(I1) formed with potassium permanganate (230). The titration of chromium(V1) by the addition of potassium iodide and titration of the liberated iodine with sodium thiosulfate was used for the determination of chromium in a number of different materials. These 124 R
ANALYTICAL CHEMISTRY
include refractory materials following a n ion exchange separation (36, 3 7 ) , copper following a solvent extraction separation (176), iron (635), aluminumchromium alloys (rod), leather following decomposition of the organic material (788), and solutions containing zinc, cobalt, nickel, and copper following an ion exchange separation (636). Vanadium(I1) was proposed as a titrant for several oxidizing agents including chromium(V1) in a n alkaline sodium carbonate solution (SI),the conditions for the determination of chromium(VI), cerium(IV), manganese(VII), and vanadium(V) when all were present by potentiometric titration with methyl orange were reported (272). E D T A has also found wide application for the titrimetric determination of chromium even though the complex forms too slowly a t room temperature for a direct titration to be practical. A comparison was made of various complexometric methods for the determination of chromium in silicates, firebrick, and carbonates (38). The excess E D T A was backtitrated with zinc in a method used for chromium following a n ion exchange separation from aluminum (556). B y selecting the proper conditions chromium-iron and chromium-aluminum mixtures were analyzed for both components using a back-titration with zinc and eriochrome black T (581). The chromium in refractory metal alloys was determined by a potentiometric back-titration with zinc with potassium ferricyanide and potassium ferrocyanide being present in the solution (36). .4n automatic-potentiometric titrator was used for the backtitration of chromium with either copper or zinc being used as the titrant (75). The copper-PAN system was used for the back-titration of chromium in petroleum industry catalysts which also contained zinc and iron (162). Bismuth is also a very satisfactory backtitrant for the excess E D T A in the chromium determination. The indicators used were methylthymol blue (SO@, xylenol orange for solutions in which chromate had been reduced ( S o l ) , and xylenol orange also for chromium in ferrochrome (299). Sulfosalicylic acid was used as the indicator and iron as the titrant for the determination of chromium with E D T A in chromate solutions (160), steel (161), and chromite ore (460). An indirect method calls for the precipitation of lead chromate and the subsequent dissolution of the precipitate and titration of the lead with E D T A (160). The titrimetric determination of zinc and chromium in mixtures of the two was carried out using lead for the back-titration and xylenol orange as the indicator (603). Nickel was also used for the titration of the excess EDTA with murexide as the indicator (623). Another indirect method
involves reaction of the chromium(II1) with potassium permanganate which precipitates an amount of manganese dioxide equivalent to the chromate formed. The manganese dioxide is separated by filtration, dissolved, and titrated with E D T A (705). A conductometric titration of chromate with yttrium nitrate was successfully carried out in a 35% ethanol solution (605). A field method for chromium involving the addition of measured pieces of paper which had been impregnated with a known amount of Trilon B was proposed (186), and applied to the determination of chromium in leather (187). One method proposed for the coulometric titration of chromium called for the reduction of the chromium to chromium(I1) with zinc amalgam and then titration of the chromium(I1) with electrically generated iron(II1) (726). Dilute hydrochloric acid was used in one procedure to reduce permanganate prior to titration of dichromate with electrically generated iron(I1) (772). I n a coulometric titration with an amperometric end point, advantage was taken of the insolubility of lead chromate by titration with electrically generated lead(I1) (773). Electrically generated molybdenum(V) was also found to be a suitable titrant for chromium(V1) (215, 803). An amperometric end point was found to be satisfactory for the titration of chromium with EDTA and other similar compounds (157). Chromium in steel was determined without interference by manganese using an amperometric end point for the titration of chromium(V1) with hydrogen peroxide (813). I n the titration of chromium(II1) with potassium permanganate, barium was added to precipitate the chromium as barium chromate, thereby preventing reduction, and the end point was detected using a platinum wire indicator electrode and no externally applied voltage (489). Chromium in steel was titrated amperometrically using iron(I1) as the titrant and two indicator electrodes (217, 218). Chromium was determined voltammetrically by anodic oxidation of a film of chromium(I1) formed on a graphite electrode (404). Chromium in steel and brass samples was determined using a differential cathode ray polarograph with ammonium chloride and ammonium nitrate as the supporting electrolyte (641). An antistatic additive for combustible liquids was analyzed for chromium, without separation, using potassium chloride as the supporting electrolyte (158). The optimum conditions and detection limits for the polarographic determination of several anions including chromate were determined (248). The determination of traces of chromium in cadmium sulfide was achieved by first electrolyzing the chromium onto
a stationary mercury electrode as mercury chromate (640),and a square-wave polarographic determination of chromium utilized the fact that chromium will replace cadmium in the cadmiumE D T A complex and release cadmium which can readily be measured (279). A rotating platinum electrode was also found to be suitable for the determination of chromium (491). The spectrophotometric methods for the determination of chromium were included in a review of recent spectrophotometric methods (367),and a compilation of methods for the determination of impurities in iodine included chromium (226). Chromium was determined in a number of ruby samples by four different methods and the results were tabulated and coinpared ( 5 5 ) . If the spectrophotometric determination of chromium using s-diphenylcarbazide as the chromogenic reagent is not the most frequently published single method in the analytical chemistry literature, it certainly must rank very near the top. Additioiial applications of this method which appeared in the literature during the period of this review include the determination of chromium in tantalum (296, 528), aluminum alloys ( 3 8 9 , iron (344), permanent-magnet alloys ( S l y ) , chromium-nickel alloys (254), nonmetallic inclusions (234),copper plating solutions (159). alkali hydroxides (253), laser-rubies (265), chromia-alumina catalysts (580), titanomagnetite (819), ilmenite (585), cement products (121), clays (120), forensic investigations (413), waste water (46, 290), and in liquid samples using an automatic analyzer (99). Chroniium(II1) was determined in industrial solutions which also contained chroniiuni(V1) by measuring the absorbance of the chromium(111) in sulfate solution ( % I ) , while measurement of the absorbance of chroniium(II1) in phosphate solution was used for the determination of chromium in ores and steels (729). Chromium in silicates was determined by Oxidizing it to chromium(V1) and measuring the absorbance (310). Chromium in chromite ores was determined by measuring the absorbance of either chromium(V1) or the chromium(II1)-EDTA complex (527). The chroniiuin(II1)-EDTA complex was also used for the determination of chromium in basic refractories (316). Rapid formation of the chromium(II1)-EDTA complex could be induced without boiling by the addition of sodium bicarbonate (624) or zinc dust (312). DCyTA was used in place of E D T A for the spectrophotometric detcrmination of chromium(II1) in the presence of thorium (781) and after separation from chrorniuni(V1) (232). Methylthymol blue and xylenol orange were compared as chromogenic reagents for the spectrophotometric determination of chromium and xylenol orange
was found to be the more sensitive of the two (152). I n other studies xylenol orange formed two complexes with chromium which exhibit absorption maxima at different wavelengths (759). Pyridine-2,5-dicarboxylic acid can be used for the spectrophotometric as well as gravimetric determination of chromium (171). The interference of aluminum, iron, and beryllium in the determination of chromium with 3-hydroxy4-(2-hydroxy-1 - naphthylazo) - naphthalene-1-sulfonic acid can be eliminated by extracting them with 8-hydroxyquinoline or acetylacetone in chloroform (784).
Other chromogenic reagents for which the optimum conditions for use and interferences were studied in some detail are pyrocatechol violet (270), acetylacetone ( 2 / 7 ) , thioglycolic acid ( M I ) , diethyldithiocarbamate (476), potassium ferrocyanide (486),2,2’-bipyridine (557), and 8-aminoquinoline (800). Reagents which were used to determine chromium following ion-exchange separation were o-dianisidine, p-aminoN,N-dimethylaniline and 3,3’-dimethylnaphthidine (383). Chromium(V1) was determined along with other oxidizing and reducing agents b y the use of tetracyanato-( 1,lO-phenanthroline) -ferrate(II1) and the corresponding iron(11) complex (669). Dichromate was used as one of the examples to demonstrate the use of a radioisotopic light source for spectrophotometry (644). T h e use of automated analytical techniques for the determination of chromium in sewage was also described (66). The measurement of the absorbance of a borax glass bead was used for the spectrophotometric determination of very small amounts of chromium ( 5 )*
A new reagent prepared for the fluorometric determination of chromium in hydrochloric acid was triazinylstilbexone (749). The optimum conditions were presented for the kinetic determination of chromium(V1) through the catalysis of the oxidation of indigo carmine by hydrogen peroxide in the presence of 2,Z’-bipyridine (328) and the catalysis of the methyl orange-hydrogen peroxide reaction in the presence of citric acid (329). Chromium was included in studies of atomic absorption spectrophotometric methods in which the sensitivities for many elements were determined under several sets of conditions including the use of a nitrous oxide-acetylene burner (616, 617). Various burner designs and flame compositions have been used for the determination of chromium (237, 520). T h e several factors which contribute to a sensitive and accurate atomic absorption spectrophotometric method were discussed (618). Elimination of the interference b y iron in the chromium determination
was achieved by the addition of ammonium chloride (249). Chromium was included in a study of the effect of amines upon the sensitivity of various elements by atomic absorption spectrophotometry (287). An argon-hydrogen-air flame and a continuous excitation source were used to determine the detection limits of 21 elements including chromium (464). T o obtain the optimum conditions for the determination of chromium and other elements in rare earth and refractory metals, both nitrous oxide-acetylene and oxygenacetylene flames were used along with three solvents: water, alcohol, and acetone (330). Isobutyl acetate was used to extract the iron as the chloride prior to the determination of chromium in ferrous metals (672). The sensitivities of several elements in the atomic absorption spectrophotometric analysis of aluminum alloys were determined using air-gas, air-acetylene and nitrous oxide-acetylene flames (797). Chromium in fresh water was concentrated b y extrartion of the ammonium pyrroline dithiocarbamate complex into methyl isobutyl ketone prior to determination by atomic absorption (490). A sample injection-dilution device was coupled to an atomic absorption spectrophotometer for the determination of chromium in used lubricating oils (724). Materials in which chromium was determined b y atomic absorption with very little pretreatment other than sample dissolution were aluminum alloys (61),aluminum-chromium-nickel alloys (398), nickel alloys (190), cast iron and steel ( 7 0 ) , stainless steel (S07), ruby (756), silicate rocks (28), and particles filtered from urban air (445). A hollow-cathode or vapor discharge source and flame excitation were shown to be useful for the determination of chromium by atomic fluorescence (550). The determination of chromium by flame photometry was improved by using an argon-hydrogen-entrained air flame with a total consumption aspirator-burner which provided lower detection limits (810). Chromium was separated by solvent extraction and determined b y emission from a n oxygenhydrogen flame in the analysis of alloys (560). Chromium in water was concentrated and separated from interfering elements b y ion-exchange and extraction with methyl isobutyl ketone prior to determination by flame photometry (590). Chromium has been determined in a variety of materials by spectrochemical methods. However, most of the papers do not consider chromiurn alone but impurities in general. The spectrochemical methods for the determination of impurities in reagents (778) and in silicon and its organic compounds (b’d6) were reviewed. An oscillating spark source which reduces the effect of crystal VOL. 41, NO. 5, APRIL 1969
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structure was proposed for the determination of minor constituents in steel (11I ) . Solid samples were introduced into the spark for the determination of chromium by being fed through a nickel screen (348) and b y a blowing method (529). The optimum conditions for the spectrographic analysis of tantalum were determined from the volatilization curves of the elements to be determined (107). Plasma burners were studied as possible excitation sources for the spectrographic determination of difficultly excited metals (639) and those metals which form volatile chelates (648). Laser excitation was used for the determination of chromium in ruby (353), the determination of the composition of a very small portion of sample (497),and the determination of the composition of the material in a furnace (647). Yttrium oxide was added to inhibit the excitation of uranium during the determination of impurities in uranium tetrafluoride (136). Refractory materials were fused with a mixture of sodium carbonate, potassium carbonate, and sodium tetraborate, dissolved in nitric acid and sprayed on a rotating carbon electrode for the spectrochemical determination of impurities (179). The impurities in copper were determined following removal of the copper b y electrodeposition (40). Niobium was separated from the impurities to be determined in niobium pentoxide by precipitation with ammonium hydroxide after the impurities had been complexed with E D T A and Tiron (709). Germanium tetrachloride was separated from the impurities contained therein simply by volatilization (579). Silicon likewise was separated from the impurities to be determined by volatilization of silicon tetrafluoride (786) and arsenic was removed by distillation of the trichloride or tribromide (728). The impurities in rare earth oxides (566),and uranium-molybdenum alloys (638) were separated b y a carrier distillation using gallium oxide as the carrier. Silver chloride alone or mixed with silver fluoride or gallium oxide was used for the carrier distillation of impurities in uranium (136). Impurities forming volatile fluorides were concentrated by making use of that property (227). Reversed-phase partition chromatography was used to separate and concentrate the impurities in plutonium-uranium-zirconium alloys (304). Aliphatic carboxylic acids were used for the extraction separation of the impurities to be determined in alkali metal salts (213). Precipitation with thioacetamide was used to concentrate trace elements contained in water prior to spectrochemical determination (470). Extraction with diethyldithiocarbamate was also used in the analysis of water samples (814) and extraction with diethyldithiocar126 R
ANALYTICAL CHEMISTRY
bamate and 8-hydroxyquinoline was used to concentrate the impurities in rubidium and cesium arsenates (214). The spectrochemical determination of impurities in hydrochloric acid was coupled with a concentration step consisting of extraction of the impurities into 8-hydroxyquinoline (429). I n a number of papers the determination of chromium with no prior separation was reported. Metals and alloys in which chromium was determined with no separation were beryllium (158), gallium (607), lanthanum (795), Zircaloy-2 (495), refractory metal alloys (443), platinum catalyst (760), and iron and steel (48,63, 71, 72,82,91). Nonmetallic solids in which chromium was determined b y spectrochemical methods with no prior separation included rubies (263), nonmetallic products in metallurgy (92), ores and minerals (19 4 , sandy-argillacious rocks (499), high-silica materials (540), and deposits from oil filters (434, 435). Chromium was also determined in liquid samples such as waste water (655), organic acids (668), the ethyl ester of orthosilicic acid (580), sulfuric acid ( 7 0 4 , hydrochloric acid (69) and liquid or pasty materials (443). Methods for the quantitative determination of elements such as chromium by spark-source mass spectrometry were studied (337) and applied to problems such as the determination of chromium in either aluminum, iron, titanium, or copper (338). Various aspects of the determination of a number of impurity elements such as chromium in aluminum ( f O ) , gallium (222), and ruby crystals (696) by mass spectrographic methods were discussed. Calculations of fluorescent X-ray intensity for chromium-iron and chromium-iron-nickel alloys were made from the theoretical formulas (693). The X-ray fluorescence methods of use in a metallurgical laboratory were reviewed and the interpretation of results was discussed (165). The surface condition of steel samples has an effect on the precision of one method of determining chromium (267). A precise method for the determination of chromium in Zircaloy-2 by X-ray fluorescence was described (522). The samples were dissolved in hydrochloric acid for the determination of several impurities including chromium in beryllium (139). An empirical correction was used in the determination of chromium, iron, and nickel in ternary alloys (283). The method for plotting the calibration curve for the determination of chromium in uranium-chromium alloys is described (223). The use of X-ray fluorescence methods for the determination of chromium in steel is also described (6, 110, 196, 359). Cations, which had been collected by filtration
of the sample solution through an ionexchange paper, were determined by X-ray fluorescence (132). X-ray fluorescence was also used for the determination of trace elements including chromium in Zeolites (278) and lubricating oils (284). Neutron activation methods are also satisfactory for the determination of chromium; however, because of the long half-life of the isotope used, separations are generally necessary. The combining of substoichiometric extraction techniques using the tetraphenylarsonium salt of various cations such as dichromate with neutron activation procedures has been successful (25). The separation of chromium from the matrix and other impurities in the analysis of aluminum was achieved by solvent extraction ( $ I ) , and ion-exchange combined with solvent extraction (47, 370, 530). The impurities in germanium were determined by a nondestructive technique (534). I n the determination of trace elements in iron and steel, the separation from the matrix is effected by the use of anionexchange procedures using hydrochloric acid solutions (292, 473). Chromium was separated from fission products and other interferences in the determination of impurities in uranium by being extracted into ethyl acetate and precipitated as barium chromate (761), b y being passed through an anion exchange column and extracted into ethyl acetate (399), and in the case of uranium concentrates by being passed through a silica gel column and a n ion-exchange column ( 2 ) . An anion-exchange method was also used as the separation procedure for the determination of chromium in tungsten (21 1 ) . A computer was used to calculate the minimum detection limits for the determination of impurities in graphite (665). Nondestructive methods were used for the determination of chromium in red phosphorus ( 7 3 9 , carbazole (77), and diamonds (389) by activation analysis. A preconcentration on an anion-exchange resin was used in the determination of parts per billion amounts of chromium in water (449). Anion-exchange separations were used for the determination of chromium in meteorites (103) and rocks (If,%?), while in the case of magnesium oxide both anion exchange and solvent extraction were used (444) and no separations were used in the case of standard samples of rock (113) and rocks and minerals (452). Several other methods have also been used for the determination of chromium. The detection limits of several elements in steel were determined for the electron microprobe (76). Procedures for the use of p r a y back-scattering for the determination of chromium in metallurgical raw materials,
ores, alloys, and slags were described (333, 334). A thermometric method in which the temperature rise of a solution upon the addition of a certain reagent was correlated with the concentration of a particluar element was suggested for the determination of chromium in slags (654). Gas chromatography was used for the separation and determination of the chromium chelate of heptafluorodimethyloctandione (713).
Table VII. Element Zirconium Hafnium Vanadium Niobium and tantalum
MOLYBDENUM
Reviews in which molybdenum is mentioned include discussions of methods for the determination of impurities in bismuth (500) and lead (96) and precipitants for molybdiphosphates (59). The determination of molybdenum in soil (93) and a comparison of methods for the determination of small amounts of molybdenum (676) are also the subjects of reviews. A study of the precipitation of molybdenum sulfide from homogeneous solution with thioacetamide in the presence of various mineral acids indicated that perchloric was the best (122). Also mixtures of perchloric acid with phosphoric or tartaric acid and mixtures of phosphoric and tartaric acids were studied (123). A somewhat different method for precipitation from homogeneous solution consists of precipitation of lead molybdate by causing chromium(II1) to react with the lead-EDTA complex to form the chromium-EDTA comples and uncomplexed lead ions (538). Molybdenum was determined in molybdenum-tungsten alloys by precipitation with a-benzoinoxime after separation of the tungsten by precipitation as the sulfide (403) Purpurogallin was used to precipitate molybdenum in the presence of titanium and zirconium after which the precipitate was ignited to molybdenum trioxide for weighing (188). Molybdenum was separated from large am0unt.s of cobalt and other interfering cations by ion-exchange prior to gravimetric determination by precipitation with 8-hydroxyquinoline (653). Following precipitation of the niobium, the molybdenum in a niobiummolybdenum-aluminum alloy was precipitated with cupferron and ignited to the oxide (685). When present together tungsten and molybdenum are both precipitated by the addition of pnaphthoquinone and tannin (686). The molybdenum can then be determined by complexometric titration. Molybdenum was titrated in 12M phosphoric acid by reduction with iron(11) and titration with potassium dichromate (512). @-Colubrine was found to be a suitable indicator for the titration of molybdenum(V) with either ceriurn(1V) or potassium dichromate (664). Cerium(1V) was used as the titrant for the determination of molybdeiiu m in [Mo (VI) O&lo (V)0 2 1FeI
Niobium Tantalum Chromium
Molybdenum
Tungsten
X-Ray Fluorescence Material (References) Hf (469); Ni, S (186); high-melting metals (440); corrosive media (670); Zr minerals ( 1 ) ; Nb (265); rocks, minerals, sands (233, 281, 297, 792) Zr (459); ZrOl (221); Zr minerals ( 1 ) Be (139); steel (196); sulfate solutions (175); corrosive media (670); zeolites (278); Polyolefins (212); Petroleum ( 6 4 ) W, 310,Re (438); hard metals (440,586); metal powders (224); Talob, KblO, (405) Ores and concentrates (727); minerals (128); corrosive media (670) Nb (255); Ag (282); steel (110) Theoretical calculations (693); metallurgical samples (165); zircaloy-2 (522); Be (139); Fe, Ni (283); U (223); steel (6, 110, 196, 267, 359); ion-exchange papers (132); zeolites (278); oil (284) Stitdy of high precision technique (137); U (223); titanium carbide (790); steel (6, 110, 196); N b ( 2 5 5 ) ; hard metals and high melting metals (438, 440); ore concentrates ( 8 0 ) ; ores and rocks (238, 466); ore, concentrate, oxide, scrap (439); powder-like products (780); solutions (462) Nb (255); steel, Ni, Cr (196); hard metals (438, 440); ore, concentrate, scrap (439); boric acid (447)
Table VIII. Neutron Activation Analysis Element Material (References) Sand ( 5 5 3 ) ; study of sensitivity (565) Zirconium and hafnium Hafnium Study of coincidence spectrometry (452); Zr (276, 277, 453,551,552,574); A1 (21, 47,370) Vanadium Study of sensit,ivity (565); A1 (17, 370); Fe (473); XaC1 (771 ); P (559); petroleum ash (454) Niobium Granite. diabase Stiidv of extraction ( 2 5 ) : studv of sensitivitv (565): Tantalum N6 (4, 2 2 ) ; W ( Z l l ) , B (293);:and (563); roiks (48ij Study of extraction ( 2 6 ) ; A1 (21, 47, 370, 530); Ge Chromium (534);.iron, steel (292, 473); U (2, 399, 761); w (211); graphite (665); P (730); diamonds (389): Mgo (444): meteorites (103); rocks (112, 113, 4 5 1 ) : carbazole (77); water (449) A1 (530); Fe (473); W (211); U (399); ZnSO4 (164); Molybdenum soil (818); graphite (565) A1 (493, 530); Ge, As ( 3 2 ) ; Si (83); Fe, steel (210, Tungsten 473, 601); U ( 3 ~ 9 ) VzOj ; (9); graphite (665); sand .
I
(563)
(CN)a (667). Molybdenum(V) was titrated with either cerium(IV), vanadium(V) or chromium(V1) ; rnolybdenum(II1) was determined either by adding an excess of cerium(1V) or manganese(VI1) followed with a backtitration with iron(I1) or determined by adding an excess of iron(II1) followed by titration of the resulting iron(I1) with manganese(VI1) (58). Chlorpromazine was found to be a suitable indicator for the titration of molybdenum(V) with vanadium(V) (2660). Titanium(111) in the presence of citric acid was found to be useful for the potentiometric determination of molybdenum(VI) (280). Iron(I1) sulfate in the presence of phosphoric acid and methyl yellow was used for the titration of molybdenum(V1) in solutions containing tungsten, zirconium, iron, rhenium,
and niobium (782). Titrations involving molybdenum(V) and E D T A also appeared in the literature. A backtitration with copper to the P.4N endpoint was used for the determination of molybdenum in solutions in which the aluminum and silicon were masked by fluoride (745),in which the tungsten was masked with tartaric acid (686), and in which niobium and tungsten were masked with tartaric acid (694). Zinc and xylenol orange were used for the back-titration of molybdenum in solutions of zirconium boride-molybdenum silicide compounds and molybdenumaluminum alloys (524) and in germanium-molybdenum alloys (600). I n a different version of a back-titration, an excess of lead was added to precipitate lead molybdate and then the excess lead was titrated with EDTA VOL. 41, NO. 5, APRIL 1969
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t o the xylenol orange end point (701). A direct precipitation titration with lead utilized 4-(2-pyridylazo)-resorcinol as the indicator (441). The end point of the titration of molybdate with silver nitrate was observed potentiometrically using a silver electrode (710). Molybdenum was also titrated by the addition of an excess of 8-hydroxyquinoline with the excess being backtitrated with copper using murexide as the indicator (350). A high-frequency method of end-point detection was used for the titration of molybdenum with cupferron (634). Electrically generated titanium(II1) was used for the coulometric titration of molybdenum in the presence of several cations including chromium, tungsten, and nickel (804). An amperometric end point was also used with electrically generated titanium(II1) (74). Following reduction with chromium(II), molybdenum was titrated with electrically generated iron(II1) (726). Iron(11) was also used along with an amperometric end point for the titration of molybdenum(V1) (16). Electrically generated lead was used for the titration of molybdate with the end point being detected amperometrically (773). The formation of the complex between molybdenum and 8-mercaptoquinoline was studied and used as the basis for an amperometric titration (702). The same complex was used for the determination of molybdenum in ferromolybdenum and steel (569). The molybdenum in ores containing, among other things, titanium, nickel, and aluminum was determined amperometrically using potassium ferricyanide as the titrant (766). Ascorbic acid was used as titrant for the successive amperometric titration of cerium and molybdenum in mixtures (716). A precipitation titration utilizing the insoluble molybdenum-thiocyanate-diantipyrylmethane complex was used with an amperometric end point to determine molybdenum (815). An ac polarograph was used to detect the end point in the amperometric titration of several cations including molybdenum with 8-hydroxyquinoline (105). The catalytic effect of molybdenum on certain oxidation reactions has been found to be proportional to the amount of molybdenum present, and therefore a method for the determination of molybdenum can be developed. The most common reaction is the Oxidation of iodide by hydrogen peroxide. An amperometric method of detecting the end point employing two platinum electrodes has been shown to be suitable for use with this reaction (677, 678). This reaction with the end point being determined amperometrically has been used in the presence of tungsten if the tungsten is masked with oxalate or citrate (117) or fluoride (118). 128 R
ANALYTICAL CHEMISTRY
Polarographic methods for the determination of molybdenum were included in reviews of methods for the determination of impurities in tin and zinc (712) and cadmium (463) and the constituents of ores and concentrates (294). Studies of the polarographic behavior of molybdenum with various supporting electrolytes were reported for up to 11.M hydrochloric acid or 1OM sulfuric acid (130), tartaric or succinic acid (269), phosphoric acid-EDTA mixtures (801), and thiocyanate and lithium chloride in diethyl ether (12). Molybdenum was determined using an ammonium nitratenitric acid supporting electrolyte after separation of rhenium on an anionexchange resin (183) and after separation on activated charcoal or alumina (184). Equal amounts of tungsten did not interfere with the polarographic determination of molybdenum using ferron or 8-hydroxyquinoline-5-sulfonic acid in an acetate solution as the supporting electrolyte (632). Tungsten, vanadium, iron, and nickel did not interfere but chromium had to be removed for the polarographic determination of molybdenum using ammonium tartarate as the supporting electrolyte (298). Molybdenum was determined polarographically in a sodium acetateEDTA solution by correcting for the vanadium interference (33). Molybdenum was also determined in the presence of vanadium using a sulfuric acidsodium sulfate supporting electrolyte (270). Phosphoric acid solution was used in the determination of molybdenum in the presence of niobium (419). Molybdenum was also included in the polarographic determination of various anions (248). A differential cathoderay polarograph was used for the determination of molybdenum in materials such as steel, brass, and nickel alloys (641). An oscillopolarographic method for molybdenum was reported in wrhich the supporting electrolyte was either tartaric acid and potassium chloride or a mixture of tartaric acid, 1,lO-phenanthroline, and copper sulfate and of the 23 ions which were tested only lead and zinc interfered and those only in a 100-fold or greater excess (503). A study was also made of the oscillopolarographic behavior of molybdenum in a ferron-sodium acetate-acetic acid solution (633). Reviews including spectrophotometric methods for the determination of molybdenum had as their topic recent developments in spectrophotometric methods (367), the determination of impurities in aluminum (388), and the use of thiocyanate as a chromogenic reagent (645). The most frequently mentioned reagent for the spectrophotometric determination of molybdenuni was thiocyanate. The influence of diluents upon the absorption spectra of
the complex when it was extracted into tributyl phosphate was studied (646). A photochemical reaction was used in place of tin(I1) chloride for the reduction of molybdenum(V1) to molybdenum(V) (606). It was also found that reduction would take place in the absence of a reducing agent if the molybdenum was in sulfuric acid solution (481). Ascorbic acid was successfully used as a reducing agent in place of tin(I1) chloride ( 7 ) . The insoluble molybdenum-thiocyanate-methylene blue complex was used to separate molybdenum from high-purity titanium prior to determination with thiocyanate (477). The complex between molybdenumthiocyanate and either crystal violet (386)or zephiramine (487) was extracted into benzene and the absorbance measured. Tributyl phosphate in chloroform was used for the extraction of the thiocyanate complex prior to the measurement of the absorbance (17'7). The thiocyanate complex of molybdenum was used to demonstrate the usefulness for differential spectrophotometric determinations of a colorimeter with optical compensation (51 ). Applications of the thiocyanate method for molybdenum include the determination of molybdenum in niobium (610), ceriumor molybdenum heteropoly acids (246), selenium and tellurium (252), tungsten or alumiiiurn (God), iron and steel (29, 346, 368, 465), cadaver tissue (637), ores (8), flotation tails (596), molybdate salts (256), and in geochemical samples (49). I n addition to thiocyanate, the other frequently used chromogenic reagent for the determination of molybdenum is toluene-3,4-dithiol. This reagent was used for the determination of molybdenum in iron alloys (356)! niobium (695), siols and sediments (734), natural waters, silicates, and biological materials (149, and sea water (630). The reduced heteropoly phosphorustungsten-molybdenum compound was studied (628) and used for the determination of molybdenum in tungsten containing materials (629). Tungsten, nickel, chromium, and vanadium do not interfere with the determination of molybdenum by the measurement of the absorbance a t 305 mp of the molybdenum(V) chloride complex (747). hlolybdenum was also determined by measuring the absorbance of the molybdate anion a t 230 mp (192). Molybdenum formed complexes with ferrocyanide (748), EDTA (594), and thiosulfate (662) which could be used as the basis of spectrophotometric determinations. Molybdenum in nickel-cobalt-molybdenum alloys was determined using tiron (674). A determination of niolybdenum in niobium and titanium alloys was carried out using thiomalic acid as the chromogenic reagent and sodium fluoride as a masking agent (595). The
preparation of stilbazogall I, and its use as a reagent for molybdenum was described (614). The reactions of molybdenum with pyrocatechol and with pyrocatechol-3,5-disulfonic, mercaptoacetic, mercaptosuccinic, and 2-mercaptopropionic acids were studied in detail along with the extraction of these complexes with diphenylguanidine and benzylthiourone (126). Pyrocatechol was used as a reagent for the determination of molybdenum in gold plating solutions (532) and sulfosalicylic acid was used for the determination of molybdenum in a refining catalyst (461). The complex with 1,lO-phenanthroline which was used for the determination of molybdenum apparently contained equal amounts of molybdenum(V) and molybdenum(V1) (458). Interferences and the conditions for the formation of the molybdenum complexes with monothioglycol and unithiol were studied (395). The morin complex was used for the spectrophotometric determination of molybdenum b y extraction into either butanol (253) or dibutylphosphate (378). Molybdenum could be determined spectrophotometrically b y using the 3-phenyldaphnetin complex but several elements including vanadium, niobium, and tungsten interfered (323). Molybdenum in steel was determined using mercaptoacetic acid as the chromogenic reagent (335, 626). Chlorosulfophenol S was proposed as a reagent for the determination of molybdenum (665) and was used for that purpose in solutions containing uranium, zirconium, and iron (204). Molybdenum in molybdates (246) and ferrous metals (711) was determined by using diethyldithiocarbamate as the reagent. Other compounds which were used as chromogenic reagents for the spectrophotometric determination of molybdenum are pyrogallol red (737), chromotropic acid (765), alizarin red S @ I S ) , phenylazoxine S (262), pyrazine-2,3-dicarboxylic acid (286), 5,7dibromo-8-hydroxyquinoline (197), 2(2-hydroxyphenylazo)-phenol (141),and thiolactic acid (519). The fluorescence of the molybdenumcarminic acid complex (376) was used for the determination of molybdenum in mild steel (377). The catalytic effect of molybdenum on the oxidation of iodide by hydrogen peroxide was used with a n automatic reaction rate apparatus for the determination of very small amounts of molybdenum (275). Other reactions which are catalyzed by molybdenum and suitable for this type of determination are the reaction between selenates and tin(1I) (442), the oxidation of 1-naphthylamine with bromate (802), and the reaction between chlorate, chloride, hydrazine, and sulfate (88). T h e use of the nitrous oxide-acetylene flame for the atomic absorption deter-
~
~
Table IX.
Element Zirconium and niobium Zirconium] hafnium, and niobjum Zirconium
~~
Radiochemical Analysis
Material (References) Air (94); fission products (243, 328,363) Study of paper chromatography (794) Study of precipitates (432, 613)
Table X.
Miscellaneous Methods
Method: Material (References) Activation: Hf (549) X-ray absorption: U, Nb, Zr (699) X-rav absorntion: ores and concentrates (612) &lassspectrographic: study of method (Id, 338); gallium (222); ruby (696) X-ray absorption: U, Zr (699) X-ray absorption: ores and concentrates (612) Electron beam microprobe: study of detection limits (76) &ray backscattering; ores, slags (333); steel (334) Thermometric: slags (664) Gas chromatography: study of chelates (713) Mass spectrographic: study of sensitivity (338); A1 (10, 337); Ga (222); ruby (696) Electron beam microprobe: study of detection limits
Element Zirconium
y
Vanadium Niobium Tantalum Chromium
hlolybdenum
(76)
Microbiological: study of conditions (539) Thermometric: Co (663) Mass spectrographic: nuclear fuels (480) X-Rav absorDtion: Sn (611) : ores. concentrates 1612) p-Raf backicattering: metallurgical raw -materials (333, 334); steel (44); Ca (303)
Tungsten
Table XI.
Element Zirconium and hafnium Vanadium Niobium and tantalum
Chromium
iMolybdenum
Tungsten
Books and General Reviews
Review Book-review of analytical chemistry (206) Impurities in Pb (96) Impurities in Bi (500) Book-review of analytical chemistry (206) General analytical chemistry (260) Analysis of tantaloniobates and tantalotitanates (386) Determination in steel (488) Impurities in germanium (626) Impurities in semiconductor compounds (251) Impurities in bismuth (500) Impurities in lead (95) Inipurities in germanium (526) Impurities in sulfur (19) Comparison of methods (676) Trace constituents in soils (93) Impurities in bismuth (500) Impurities in lead (96) Book-review of analytical chemistry (206)
mination of molybdenum was investigated (SO) and the sensitivity determined (61'7). Molybdenum in water, plant materials, and silicate rocks was determined b y atomic absorption spectrophotometry using an air-acetylene flame following concentration b y solvent extraction (127). The interference caused b y calcium, sulfate, and phosphate in the determination of molybdenum in superphosphate with the airacetylene flame was eliminated b y the addition of aluminum (167). The nitrous oxide-acetylene flame was used successfully for the determination of
molybdenum in niobium and tantalum (372) and steels (375). Additional applications of atomic absorption spectrophotometry for the determination of molybdenum include molybdenum in urine and blood (582), uranium hexafluoride (663),fuels and lubricants (508), and sea water after concentration on chelating resins (631). The emission of molybdenum in a premixed nitrous oxide-acetylene flame was observed at various fuel-oxidant ratios (373) and a separated fuel rich nitrous oxide-acetylene flame was also studied and its usefulness for molybdenum demonstrated VOL. 41, NO. 5, APRIL 1969
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(374). Molybdenum in steel was determined b y flame photometry using a n oxygen-acetylene flame after separation by solvent extraction (703). The majority of the papers dealing with the spectrochemical determination of molybdenum describe the determination in specific materials. I n one case, molybdenum was determined in a wide variety of metallurgical materials following preconcentration by co-precipitation wit,h copper sulfide (45). Molybdenum was determined in coated molybdenum wires by the high-frequency spark technique following dissolution (258). The impurities in alkali and alkaline earth metals were concentrated b y using cadmium sulfide and carbon powder as a collector prior to determination (678). Extraction with diethyldkhiocarbamate and 8-hydroxyquinoline was used to concentrate the impurities found in cesium and rubidium arsenates (914). Molybdenum was determined without prior separation in beryllium metal (158) and in gallium metal and oxide (607). Separation by removal of the matrix was used in the case of electrodeposition of the copper in the analysis of copper and copper compounds (40) and in the volatilization of silicon tetrafluoride in the analysis of elemental silicon (786). Carrier distillation was used in the case of the impurities in uranium metal (135) and the molybdenum in uraniummolybdenum alloys (638). The impurities in plutonium-uranium-zirconium alloys were concentrated b y reversed-phase chromatography prior to spectrochemical determination (804). Spectrochemical methods were also described for the determination of molybdenum in tungsten and tungsten compounds (507), tungsten-molybdenum alloys (446))zircaloy-2 (548),refractory metal alloys (443), and high-purity refractory metals (529). There are a number of applications of spectrochemical methods to the determination of molybdenum in products of the steel industry (65, 71, 75, 111). hfolybdenum was determined spectrographically in such geological materials as granite ( 3 f 9 ) ,ores and minerals (I%$), and rocks and minerals (518). The molybdenum in hydroiodic acid was concentrated by extraction with 8-hydroxyquinoline in chloroform prior to spectrochemical determination (429). hlolybdenum was determined b y spectrochemical procedures in biological materials (266), plants (96), and blood serum (225). Liquid samples in which molybdenum was determined included mineral waters ( 5 7 l ) , natural water (814), and solutions (655). Excitation of various elements by electrodeless discharge was studied and found to be a suitable method for the excitation of molybdenum (109, 196). A laser was used for the excitation of a very small 130 R
ANALYTICAL CHEMISTRY
area of a sample for the spectrochemical determination of the constituents (497). Molybdenum in nuclear fuels was determined by isotope dilution mass spectroscopy following separation from the matrix by solvent extraction (480). By the use of coherent to incoherent scattering ratios, molybdenum and other major constituents were determined b y X-ray fluorescence with a n accuracy claimed to be only slightly less than chemical methods (137). Promethium147 mixed with samarium oxide provided an X-ray emitter for the determination of molybdenum (80). Rlolybdenum was determined in uranium (223) and titanium carbide cermets (790) by X-ray fluorescence. Several procedures were reported for the determination of molybdenum in steel by X-ray fluorescence (6, 110, 196). Other determinations of molybdenum in metallurgical materials by X-ray fluorescence were performed on samples of niobium (255) and hard metals (438, 440). Other materials for which procedures were reported are ores and rocks ( I % ) , ores and clays (466), ores, concentrates, and scrap (459), powder-like products (780) and water or dioxane solutions (462). Neutron activation has also been used by several workers for the determination of molybdenum in various materials. Molybdenum was determined in high-purity aluminum in a procedure involving chemical separations of the impurity elements (650). An anion-exchange separation was used in the procedure for the determination of molybdenum in iron (473). Anionexchange separations and several different irradiation times were used in the procedure for the determination of molybdenum in tungsten (211 ). I n the determination of impurities in uranium by neutron activation, the uranium is separated before the irradiation and the remainder of the separations are made following the irradiation (399). Other applications are the determination of molybdenum in zinc sulfate (164), soil (818), and graphite with no separations but with computer calculated sensitivities (565). Other techniques used for the determination of molybdenum are the electron-bean1 microprobe (76)) an extremely sensitive microbiological method utilizing the effect of trace elements on the growth of microorganisms (639) and a thermometric method in which the temperature rise of the sample solution is measured as the reagent is added (653). TUNGSTEN
Methods for the determination of tungsten were included in a book which also described analytical methods for zir-
conium, hafnium, niobium, and tantalum (206). Several gravimetric methods have been described for the determination of tungsten but regardless of the precipitating agent, they all call for ignition of the precipitate to tungsten trioxide. The gravimetric determination of tungsten by precipitation with 8-hydroxyquinoline was used as an example to demonstrate the use of a computer in evaluating analytical results (259). Tungsten was determined in mixtures of tungsten and molybdenum by precipitating both with a-naphthoquinone and tannin, igniting to the oxide, and weighing and then redissolving and determining the molybdenum by a titrimetric procedure after which the tungsten was calculated by difference (686). I n a similar procedure for the determination of tungsten in ores and minerals, both the tungsten and molybdenum were precipitated with 8-hydroxyquinoline, the molybdenum was determined by a spectrophotometric method, and the tungsten was then determined by difference (192). Tungsten in steel was determined gravimetrically by using variamine blue as the precipitant (207). Pyramidon was used to precipitate tungsten from oxalate solution following the dissolution of sintered carbides (509). The determination of tungsten in catalysts was accomplished by precipitation as tungstic acid brought about by boiling the sample in a mixture of nitric and hydrochloric acid (575). Tungsten was also precipitated with 1,&dianiino-naphthylene and the precipitate was ignited to the oxide for weighing (448). A few titrimetric methods for the determination of tungsten have been attempted. Iodine monochloride was used for the potentiometric titration of tungsten(V) which had been obtained by reduction with bismuth amalgam or tungsten(II1) which had been obtained by reduction with zinc amalgam (675). The tungstate anion was titrated with lead causing the precipitation of lead tungstate with the end point being detected by the reaction of the excess lead with 4-(2-pyridylazo)-resorcinol (441). The titration with lead was also followed potentiometrically (268). The insolubility of lead tungstate was also made the basis of a coulometric titration of the tungstate ion in which the titrant was electrically generated lead (773). The end point was determined potentiometrically. An amperometric titration of tungsten was reported in which diantipyrylmethane was the titrant and the reaction resulted in the formation of the insoluble tungstenthiocyanate-diantiypyrylmethane compound (815). The direct amperometric determination of iodine was used t o follow the oxidation of iodide by hydrogen peroxide which is catalyzed by tungsten
with the effect being proportional to the amount of tungsten present (118). Polarographic methods for the determination of tungsten were also reported in the literature during the period of this review. Two of the supporting electrolytes suggested for the determination of small amounts of tungsten were a mixture of perchloric acid with tartaric acid and a mixture of hydrochloric acid with either tartaric or citric acid (81). After a prior separation with tannin, tungsten was determined polarographically in heat-resistant alloys using a mixture of sulfuric and phosphoric acids as the supporting electrolyte (694). The catalytic hydrogen wave was used for the polarographic determination of tungsten in alkali chlorides (484). The tungstate anion was also determined polarographically (248). Tungsten in steel, brass, and nickel alloys was determined by means of a differential cathode-ray polarograph (641). The amounts of molybdenum and rhenium which interfered in the oscillopolarographic determination of tungsten were ascertained (244) and tungsten was determined in tantalum with no separation by an oscillopolarographic method (416). Spectrophotometric methods for the determination of tungsten were discussed in a recent review (367). A review of the use of thiocyanate complexes for the spectrophotometric determination of a number of ions included tungsten (645). Tungsten was determined with thiocyanate following a solvent extraction separation from molybdenum with 8-hydroxyquinoline in chloroform (785). I n one procedure for the determination of tungsten in iron, the thiocyanate complex is formed and then extracted into butyl acetate (347) while in another the tungsten is precipitated from nitric acid solution using metastannic acid as a carrier prior to formation of the thiocyanate complex (735). I n the determination of various oxides of tungsten in mixtures, the tungsten trioxide was first dissolved in sodium oxalate, the tungsten pentoxide was then dissolved in sodium carbonate, and finally the tungsten dioxide and tungsten metal were oxidized with nitric acid and then dissolved in sodium carbonate. The tungsten in each fraction was determined by the thiocyanate procedure (651). The thiocyanate procedure was also used for the determination of tungsten in water and sewage (697). A counter current extraction with methyl isobutyl ketone was used to eliminate the interference of molybdenum in the spectrophotometric determination of tungsten using toluene-3,4-dithiol as the chromogenic reagent (341). I n the procedure for the determination of tungsten in niobium using toluene-3,4dithiol, the molybdenum complex is formed and extracted into chloroform after which the tungsten complex was
formed and extracted into chloroform for measurement (696). An anion-exchange separation was used to remove the iron prior to the determination of tungsten with toluene-3,4-dithiol in iron alloys (566). Tungsten was also determined with toluene-3,4-dithiol in subsurface waters (393) and in silicates and natural waters (146). Stilbazogall I was studied as a possible reagent for the determination of tungsten and the optimum conditions were described (314, 315). Other reagents for the spectrophotometric determination of tungsten for which the optimum conditions were worked out and the interferences determined were pyrocatechol violet (471), gossip01 (364), tiron (691), 6,7-dihydroxy-2,4-diphenyl-chrom2- en (592), and 2-(3,4-dihydroxy-phenylazo)-4-phenyl-5-benzoylthiazole (397). The absorbance of molybdotungstic acid a t 765 mp was also used for the determination of tungsten; however, there are many interferences (274). The fluorescence of the tungsten-flavonol complex was used for the determination of tungsten in steel following a cationexchange separation (97) and in thoriated tungsten and cobalt-nickel-chromium alloys following separation of the thorium, cobalt, and nickel by precipitation as the hydroxide (98). A procedure was also developed for the fluorometric determination of tungsten using carminic acid as the reagent (376). The sensitivity and detection limits were determined for the determination of tungsten by atomic absorption spectrophotometry using the nitrous oxideacetylene flame (30, 617, 725). Chelating resins were used in conjunction with atomic absorption spectrophotometry for the determination of tungsten in sea water (631). A number of spectrochemical methods were used for tungsten. The tungsten in tungsten-molybdenum alloys was determined using a spark source after separation of some of the other constituents by precipitation by the addition of ammonium hydroxide (446). I n the spectrochemical determination of tungsten in molybdenum, the tungsten was concentrated by coprecipitation with the precipitate that formed upon the addition of ammonium orthophosphite t o the solution (369). A tubular copper electrode was used for the spectrochemical determination of tungsten in mixtures with u p to equal amounts of silicon, chromium, nickel, or iron ( 3 @ ) , Tungsten in refractory metals was determined using citric or oxalic acid solutions and a vacuum-cup electrode (443). The tungsten content of various steels was determined using spark excitation and no prior separation (71, 111). Spectrochemical methods were also found to be satisfactory for the determination of tungsten in rocks and minerals (318) and granite (319, $20). The
determination of tungsten in granite was one of the methods used to illustrate a discussion of the principles of spectrographic analysis and the calculation of the results (431). Laser excitation was used for the spectrochemical examination of very small areas of various samples (497). A method for the determination of tungsten and other impurities in niobium by X-ray fluorescence was compared with the spectrochemical and atomic absorption methods on the basis of cost and was recommended for use in the quality control determination of impurities in niobium (266). Research was reported which led to methods for the determination of tungsten in steel, nickel-tungsten, and nickel-chromiumtungsten alloys by X-ray fluorescence (196). The determination of several metals including tungsten in hard metals by X-ray fluorescence was compared to the determination by wet chemical methods with regard to accuracy, precision, time, and cost (438). The tungsten was determined in ores, concentrates, and scrap by X-ray fluorescence following removal of copper, iron, titanium, niobium, and tantalum (439). Procedures were recommended for the analysis of binary alloys containing tungsten and either copper, molybdenum, rhenium, or tantalum (440). Tungsten was also determined in boric acid by X-ray fluorescence (447). Another method proposed for the determination of tungsten was to measure the X-ray absorption on both sides of an X-ray absorption edge and from these measurements calculate the amount of tungsten present (611). This method was applied to the determination of tungsten in ores and concentrates (612). The use of 0-ray back-scattering for the determination of tungsten in a wide variety of metals, ores, and slags was reviewed (333, 334). Tungsten in calcium tungstate (303) and high-speed steel (44) was also determined by this method. Neutron activation was used for the determination of tungsten in highpurity aluminum; in one case with an ion-exchange separation (493) and in another with an ether extraction (530). The impurities, including tungsten, were determined in gallium arsenide by neutron activation in conjunction with a series of solvent extractions (32). The impurities in semiconductor silicon were determined without separation (83). The trace constituents in iron and steel were separated by anion-exchange in chloride solution (473), by reversed-phase partition chromatography @ I O ) , and determined without separation (601). An anion-exchange separation was used prior to irradiation t o remove the uranium, and ion-exchange and solvent-extraction separations were used following irradiation in VOL. 41, NO. 5, APRIL 1969
0
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the determination of tungsten and other impurities in uranium (399). Neutron activation with coincidence spectrometry was used for the determination of tungsten in vanadium pentoxide (9). A computer method was used in the determination of impurities, including tungsten, in nuclear-grade graphite in order to derive the minimum detection limits (666). Neutron activation wm also used for the determination of tungsten in sand (665). LITERATURE CITED
(1) Abdel-Gawad, A. M., Amer. Mineral.
51,464-73 (1966). (2) Abdel-Rassoul, A. A., Wahba, S. S., Abdel-Aziz, A., Talanta, 13, 381-7 (1966). (3) Abdurakhmanov, M., Dzhiyanbaeva, R. Kh., and Talipov, Sh. T., Tr. Tashkentsk. Gos. C'niv., 1967, pp 83-6. (4) Abe, Shigeki, Nippon Kagaku Zasshi, 86,641-3 (1965). (5) Ackermann, Gerhard, Hesse, Dieter, Jena Rev., 11,lO-2 (1966). (6) Adachi, T., Ito, M., Denki Seiko, 34, 384-92 (1963). (7) Adamiec, I., Chem. Anal. (Warsaw), 11,1183-90 (1966). (8) Adamiec, I., Chem. Anal. (Warsaw), 11. 1176-82 - -- (1966). (9)Adams, F:,-Horste, J., Acta Chim. Acad. Sci. Hung., 52,115-22 (1967). (10) Addink. N. W. H., Werner, H. W., Witner, A'. W., Colloq. Spectrosc. Znt.; 1%h, Exeter, Engl., 1965, pp 651-6. (11) Affsprung, Harold E., Robinson, , Jack L., Anal. Chim. Acta, 37, 81-90 (1967). ,- - - . ,. (12) Afghan, B. K., Dagnall, R. M., Talanta, 14,239-43 (1967). (13) Agarwala, Bardi Vishal, Dey, Arun K.. Microchem. J.,12.162-7 (1967). (14) 'Agarwala, B. 'V.,' Dey, A. K., J. Indian Chem. SOC.,44,691-3 (1967). (15) Agarwala, B. V., Sangal, S. P., Dey, Arun K., Mikrochim. Acta, 2, 442-7 (1968). (16) Agasyan, P. K., Tarenova, K. Kh., Nikolaeva, E. R., Katina, R. M., Zavod. Lab., 33,547-50 (1967). (17) Agelao, G., Dardanoni, Z. T., Atti Accad. Sci., Lettere Arti Palenno, Pt. I, 25,333-49 (1964-65). (18) Aleksandrov, Aleksandur, Budevski, Omortag, Nauchni Tr., Vissh Znst. Khranitelna, Vkusova Prom.-Plovdiv, 12,297-300 (1965). (19) Alekseeva, A. N., Metody Analiza Veshchestv Vysokoi Chistoty, Akad. Nauk SSSR, Znst. Geokhim. i Analit. Khim., 1965, pp 422-44. (20) Alekseeva, V. M., Rusanov, A. K., Il'yasova, N. V., Zh. Anal. Khim., 23,202-5 (1968). (21) Alian, A., Haggag, A., Talanta, 14, 1109-19 (1967). (22) Alimarin, I. P., Bilimovich, G. N., Yakovlev, Yu. V., Zavod. Lab., 33, 672-6 il967). iiimarin, I. P., Golovina, A. p., Zh. I
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M.1 (25) Alimarin,, I. P.,-Perezhogin, - . G. A.. palanta, 14,'109-19 (1966). (26) Alimarin, I. P., Savvin, S. B., Tulanta, 13,689-700 (1966). (27) Almagro, J., Pujante, A., Sancho, J., A n , Real SOC.Espan. Fis. Quim., Ser. B , 63,27-33 (1967). (28) Althaus, Egon, Neues Jahrb. Mineral. Monatsh., 8,259-80 (1966). '
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(815) Zhivopistsev, V. P., Sadakov, G. A,, Uch. Zap. Perm. Cos. Univ., 141, 174-8 (1966). (816) Zittel, H. E., Florence, T. M., ANAL.CHEM.,39,320-6 (1967). (817) Zittel, H. E., Florence, T. M., ANAL.CHEM.,39,355-6 (1967). (818) Zmijewska, Wanda, Minczewski, Jerzy, Krajove Symp. Zastosow. Izotop.
Tech., Srd, Stettin, Pol., 1966, 6 pp. (819) Zolotavin, V. L., Fedorova, N. D., Tr., Vses. Nauch.-Issbd. Inst. Stand. Obraztsov Spektr. Etalonov, 2, 92-6 (1965). (820) Zolotavin, V. L., Fedorova, N. D., Tr., Vses. Nauch.-Issled. Inst. Standk. Obraztsov Spetr. Etalonov, 1, 31-5 (1964).
V. L., Podchainova, V. N., Fedorova, N. D., Dolgarev, A. V., Dergachev, V. Ya., Tr., Vses. Nauch.-Zssbd. Inst. Stand. Obraztsov Spektr. Etalonov, 2,99-108 (1965).
(821) Zolotavin,
WORKperformed in the Ames Laboratofy. of the U.S. Atomic Energy Commission. Contribution No. 2511.
Pesticide Residues Wayne Thornburg, Del Monte Corp., San Francisco, Calif., and Herman Beckmanl, University of California, Davis, Calif.
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in the field of pesticide residue methodology has continued a t a high level during the t n o year rerien period from November 1966 through October 1968. I n preparation of this review some selectivity has been exercised to include only those procedures which, in the opinion of the authors, will be most useful to residue analysts. Emphasis has been placed on publications available a t major libraries, and on procedures using commercially available chemicals and instruments. This review follows the general format and pesticide nomenclature established in the 1967 biannual review of Williams and Cook (237). Frear’s “Pesticide Index” (Q5)lists the common, trade, and chemical names of many pesticides, and the authors have tried to use names t h a t can be found therein. Common names ivhich appear in the United States Food & Drug Administration tolerance regulations have been used where possible. I n the past two years there has been increased interest in the metabolism of pesticides. Improvements in instrumental analytical procedures have resulted in the publication of excellent and comprehensive metabolic studies. Most of these contain useful analytical techniques and h a r e been included in this review. However, discussion of metabolic pathways and the authors’ conclusions are beyond the scope of this review-. Publication in the field of pesticide residues has continued during this twoyear period. Gunther (109) has continued his editorship of “Residue Reviews” and 24 volumes have now been published. Volumes I and I1 of the Food and Drug Administration’s “Pesticide ,inalytical XIanual” (18, 7‘8) have undergone continuous revision and offer excellent pesticide analytical procecures. “Health Aspects of Pesticides-Literature Bulletin,” begun as an experi-
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ANALYTICAL CHEMISTRY
mental monthly publication of the Office of Pesticides of the U.S. Public Health Service, started publication in September 1968 on a regular basis and is now called “Health Aspects of PesticidesAbstract Bulletin” (120). This publication should be especially useful to the pesticide residue analyst. Zweig has continued his editorship of “Analytical Methods for Pesticides, Plant G r o v t h Regulators and Food Additives” with the publication of Volume V, “Additional Principles and Methods of Analysis” ( 2 4 5 ) . Preston has published a second edition of “A Guide to the Analysis of Pesticides by Gas Chromtography” (184). This two-year period has seen continued attempts t o automate pesticide residue analysis. I n most systems, the samples must be extracted and cleaned up before they are introduced to the automated instrument. Several procedures were reported using the AutoAnalyzer. Ott and Gunther (174) reported an a u t o m a t e d wet dig est i o n- o xi d a t i on colorimetric procedure for organophosphate pesticides using the AutoAnalyzer system. The total system handled 10 samples per hour with practical precision and sensitivity. Most crop samples required precleanup. T h e system will work on T L C “spots.” O t t (173) described a dual simultaneous AutoAnalyzer total phosphorus and new anticholinesterase system for organophosphates. Results are recorded simultaneously on a two-pen recorder. One of the problems associated with the automated anticholinesterase system for organophosphates is the oxidation of the pesticide and then t h e destruction of the excess oxidant. Gunther et al. (111) used silver oxide to oxidize parathion to paraoxon in aqueous media. This oxidizing agent was superior to the commonly used oxidants. Leegwater and Van Gend (146) developed a n automated enzymic procedure for the detection and determination of organophosphorus pesticides showing cholinesterase inhibition.
Voss and Geissbuhler (226) described a n automated anticholinesterase system for certain organophosphorus pesticides. Friestad (96) used a n AutoAnalyzer t o automate the diazotization and coupling portion of a colorimetric linuron analysis. Sample preparation, extraction procedures, and cleanup of the extracts are a very important part of pesticide residue analysis. Chiba and Morley (59) studied the loss of pesticide residues during sample preparation after extraction. Filtration, partitioning, washing, concentration, and evaporation were examined separately using C11-labeled BHC, p,p‘DDT, and dieldrin. Losses of pesticides duringfiltration, partitioning, and washing are relatively small, b u t they are cumulative. Polar solvents are not completely removed from a nonpolar solvent b y normal washing procedures. The effect of traces of polar solvents on column cleanup was discussed. Evaporation to dryness caused the most significant loss, and was not recommended even in the presence of extractives. Schnorbus and Phillips (203)report,ed a new extraction system for residue analysis. Samples are extracted with propylene carbonate. Extracts were cleaned u p b y Florisil column chromatography. The extracts were suitable for TLC, electron capture, and thermionic and microcoulometric GLC. Root (195) investigated various solvent extraction procedures for pesticide residue recovery from samples of alfalfa and related materials. H e found grinding t o less t h a n 20-mesh and refluxing with acetonitrile for 1 h r t o be the preferred method of extraction. Pionke and coworkers (181) reported the extraction of organochlorine and organophosphate insecticides from lake water. A 250-ml sample of water was extracted b y shaking in a separatory funnel with 25 ml of benzene for 2 min. The separated benzene phase was analyzed without cleanup by electron capture and thermionic GLC. LIcLeod and coworkers (161) compared various carbon adsorbents and
