V O L U M E 2 2 , NO. 1, J A N U A R Y 1950
89
1306) Vasil’eva, E. V., Zhur. A n d . Khim., 2, 167-72 (1947). Detec-
tion of silver and mercury ions and their quantitative (colorimetric) determination. (307) Virasoro, E., and Berraz, G., Anales inst. invest. ca’ent. y tecnol. (Univ. nacl. litoral, Santa F6, arg.), 14/15, No. 23, 41-8 (1946). Photometric determination of copper and nickel. (308) Vorokhobin, I. G., and Filyanskaya, E. D., Zavodskaya Lab., 14, 106-7 (1948). Rapid method for determining hydrogen sulfide in air. ,309) Vorontsov, R. V., I b i d . , 13, 1155-7 (1947). Ferrocyanide photometric determination of vanadium. 1310) Watson. R. W., and Tom, T. B., Znd. Eng. Chem., 41, 918 (1949). Relation of structure and effectiveness in copper deactivators. ,311) Wehrli, S., and Kanter, M.. Helv. C h i m Acta, 31, 1971-4 (1948). Microchemical determination of prussic acid for forensic purposes. &312)Wells, J. E., and Hunter, D. P., A n a l y s t , 73, 671-3 (1948). Amyl acetate, a solrent for separation of iron in metallurgical analysis. : 4 1 3 ) Wenger, P. E., and Duckert, R., “Reagents for Qualitative Inorganic Analysis,” New, York, Elsevier Publishing Co.. 1948. ,314) West, P. W., A s . 4 ~ .CHEM.,21, 121 (1949).
Inorganic micro-
chemistry.
W.,and Compere, Maria, Ibid., metric determination of copper in water.
$315) West, P.
p. 628.
(316) West, P. W., Proc. 10th Ann. Short. Course Water Sewerage Plant Supts. and Operators, 1947, La. State Univ. Eng. Expt. Sta., B u l l . Ser. 11, 41-3 (1948). Methods used for de-
termination of chlorine residuals in water. (317) Whitnack, G. C., and Holford, C. J., ANAL.CHEM.,21, 801 (1949). Determination of water in nitrogen tetroxide. (318) Wiberley, S. E., and Bassett, L. G., I b i d . , pp. 609-12. Colorimetric determination of aluminum in steel. Use of 8-
hydroxyquinoline. (319) Willard, H. H., Mosher, R. E., and Boyle, A. J., Ibid., pp. 598-9. (320) (321) (322) (323) (324)
Determination of copper by dithio-oxamide in magnesium and magnesium alloys. Wilson, C. L., Analyst, 73, 585-96 (1948). Some physicochemical methods in microchemistry. Molecular weight. Woldan, Alfred, Mikrochemie w r . Mikrochim. Acta, 34, 192-200 (1949). Detection of silver in silicates. Yakovlev, P. Ya., and Pen’kova, E. F., Zavodskaya Lab., 15, 34-6 (1949). Determination of molybdenum and titanium in ferrous alloys and steel by amalgam method. Young, R. S., and Barker, C. W.,Chemist-Analyst, 37, 81-3 (1948). Rapid test for small concentration of cadmium in zinc solutions. Zemanv. P. D.. TT’inslow. E. H.. Poellmitz, G. S.,and Liebhafsky,-H. A., ANAL.CHEM?.. 21, 493 (1949). X-ray absorption measurements.
ColoriRECEIVED h’ovember 7, 1949.
INORGANIC GRAVIMETRIC ANALYSIS F. E. BEAillISH L’niversity of Toronto, Toronto, Canada
T
HIS revie\v follows t h r :iri:tngement adopted for the fir\t issue ( 6 ) , although in the section dealing with general prowdures there has been some alteration of subheadings. During the past year there has been an increased number of publications communicating progress of great interest t o analytical chemists. Perhaps of primary importance are the researches dcaling with the application of Amberlite resins to chemical +parations. This field of investigation is only in the initial .tages of development and much further knoirledge of great value \ r i l l be forthcoming in future yrarq. The work of Duval and his associates meritb attention. These investigators have been making an organized effort t o ascertain the dissociation temperaturrs of numerous precipitates used for Kravimetric purposes GENERAL PROCEDURES
Preparation of Samples. Uaryshev (51 discussed the experimental basis of a sampling method and the preparation of laboratory samples for analysis. Herteland (57)dealt with the preparation of samples of metals and alloys for analysis. He rejected the use of borings or shavings and recommended melting under pre-cribed conditions. With certain alloys this treatment resulted in a change in the proportions of ronstitueiits. This author (57)alqo tliscussed the losses incident to the formation of a mist during the dissolving of metals and alloys. The use of cover glasses did not eliminate the loss. I n the analysis of clays, bauxite, feldspar, cstc., Cadariu ( 2 1 ) suggested preliminary sintering with calcium rwbonate. Tkachenko and Khripach (131) recommended drying .amples of iron ore for 5 minutes a t 150” to 160” C. in prpference t o drying a t 105 ’. Method of Selective Separations. Lur’c and Filippova (82) used cationites for absorption followed by selective extractioii 81th alkali solution to separate antimony, molybdenum, tungsten, dinc, and aluminum from anions, iilw from elements that form basic hydroxides-e g., iron and copper --and from arsenic in the arsenite form. By this procedure the coprecipitation incident to hydrolytic precipitation was avoided Later the authors (85) reported the successful application of Wolfatit P for the separation
of zinc and aluminum from iron, antimony and tin from arbem(*,
bismuth from copper or lead, and bismuth from antimony. Anion-exchange experiments were made with guanidine anionite Chromate was absorbed and subsequently extracted with sodium hydroxide. Directions were given for the separation of chromate ion from nickel. Under specific ronditions tin could be absorbed but not separated from antimony. Bismuth was efficiently wparated from copper. I n neutral or alkaline solution permanganate was reduced to mmganese dioxide, absorbed, and subsequently extracted with sulfuric acid. Kostrikin (75)stated that absorption by organolites was incomplete if a definite portion of the solution was mixed with a given amount of the sorbent. Filtering through a layer of the sorbent wa5 preferable. Lur’e (81), dealing with small concentrations, rejertcd filtration through a layer of sorbent in favor of mixing the solution with the organolite followed by extraction. Osborn (96) recorded some analytical applications of m-nitrobenzoic acid t o the separation of quadrivalent elements from the rare earth elements, etc. Excluding the interference of mercury and the possible interference of hyd tin salts, rn-nitrobenzoic acid appeared to be a specific pre ng reagent for all quadrivalent ions except titanium. Ostroumov (98) discussed in considerable detail thc methods of separation by pyridine, a-picoline, and hexamethylenetetramine. Pyridine was used as a regulator of the aridity of solutions during hydrolysis and for the formation of complrxei This xvork appears to be worthy of extended study Vanosii (139) published a review of his work on the separation and identification of elements which are distilled by acids. Included were the separation and identification of osmium, ruthrniuni, and germanium : and the identification of germanium, rhenium, and tin. 11Iusante (94)examined the reactions between certain hydroxamic acids and metal ions with a view to analytical applications. The benzo derivative of hydroxamic acid ma5 a vnsitive reagent for copper and to a less degree for cobalt and nickel. Copper also formed insoluble anisohydroxamates. Gaspar y Arnal and Rojo ( 4 6 ) dealt with the applications of sulfites and sulfates t o chemiral analysis. They obtained quantitative separations of calcium and strontium, calcium and barium, and calrium and lead, and thev (4.5)described the use of sulfites for
90 separations of cupric ion from the ions of the alkaline earths and lead. Korenman ( 7 4 ) discussed relationships between the structure of various organic compounds and their ability to form colored and insoluble salts with nickel, ferrous iron, palladium, etc. Preparation for Weighing. Duval (31) investigated the behavior toward heat of moist asbestos used in Gooch crucibles. Up to 73" a loss of weight due to uater of imbibition was observed; from 73" to 283" the weight remained constant: at temperatures above 283" a regular loss of weight occurred. I t was concluded that precipitates weighed in Gooch crucibles should not be dried above 283 '. The temperature intervals producing constant weight of some 23 compounds used as precipitates were determined. The author (25) proposed to examine the optimum temperature limits for the ignition of about 600 substances encountered most frequently in gravimetric analysis. Shiokawa (119) determined suitable ignition temperatures for tannin precipitates of aluminum, beryllium, cerium, chromium, copper, iron, manganese, titanium, vanadium, and zirconium. Using tannin, hydrated tungsten(V1) oxide was ignited a t 630 O to 835' C. When both tannin and cinchonine were used, ignition was made at 630' to 830'. Duval (SO) investigated in detail the behavior of filter paper during the burning process. The paper lost water but retained its form as carbon a t 410°, becoming white a t 6 i 5 ' C. Tschirch (134) discussed recent developments in the technique of handling precipitates, especially vacuum drying and treatment with acetone. Matheson (85) recorded various improvements in the technique of weighing. For the calibration of weights, Herbo (66) rejected the method of indirect weighing and suggested an improved procedure. Analytical Methods for Specific Materials. Willey and Caine (146) recorded short, accurate procedures for the analysis of foundry sand. These authors aimed to promote analytical research to assist in solving foundry sand problems. Mohler and Sedusky (92) published a review of various methods used in analysis of plating baths. I n the analysis of iron ores, Baron ( 4 ) regarded as of doubtful value the determination of "loss on ignition," by loss of weight, and preferred to determine carbon dioxide and water directly. Touhey and Redmond (132) discussed the determination of tungsten, titanium, columbium, tantalum, iron, cobalt, and nickel in cemented carbide compositions. Cinchonine precipitated tungstic oxide together with titanium, columbium, and tantalum. The impure precipitate was fused and then treated with cupferron to obtain the weight of the above impurities. Deducting this weight they obtained the weight of tungstic oxide with any molybdenum present. Bowden ( I S ) , criticizing this procedure, stated that molybdenum is partially precipitated by cupferron and upon ignition above 525' is partially volatilized in the presence of tungsten, etc. This author also called attention to the Touhey and Redmond method of collectively precipitating titanium] columbium, tantalum, and iron in the presence of chromium and vanadium. According to Bowden, the potassium carbonate fusion used to separate these constituents would result in dissolution of a large proportion of tantalum and columbium oxides. Touhey and Redmond (133) acknowledged this error and introduced some alterations, but they included no reply to the criticism concerning the distribution of molybdenum. Smith (124) recorded detailed procedures for determining various constituents in magnesia. The methods were largely conventional but some variations were introduced. Krossin (77) published procedures for determining lead sulfate, lead sulfide, and lead oxide in the presence of one another. Directions were given for determining lead oxide in roast material and flue dust. Piquott (109) reviewed analytical techniques used in ferrous metallurgy. General Gravimetric Reagents. Portnov (110) dealt extensively with the application of aromatic-arsenic compounds in chemical analysis. The dissociation constants of six compounds were given together with the insoluble salts produced by various
ANALYTICAL CHEMISTRY cations. The author described two specific procedures: in one, p-4cSHGH~AsO~H2was used to precipitate cobalt in the presence of nickel; in the second, p-HOCeHAsOsH2 was used to precipitate lead in the presence of alkaline earth elements. Jean (65) discussed in considerable detail the effect of acidity on the composition of insoluble salts formed by various metallic cations with heteropoly acids and amino bases. Conditions for analytical applications were favorable when the acidity of the precipitating medium was greater than that a t which hydrolysis occurred. Cattelain ( 2 3 ) reviened the use of organic reagents in inorganic analysis. LIGHT ALLOY ELEMENTS
Lithium, Beryllium, and Magnesium. Boy (14) discussed the determination of lithium in phosphate and silicate minerals. Aluminum was removed as the phosphate. With silicates, phosphoric acid was added before addition of lead acetate. Lithium vias determined as fluoride, and if magnesium was present separation from the mixed fluorides waa effected by ammonium hydrogen phosphate. For separating beryllium from aluminum, Otsuka (100) recommended the sodium hydrogen carbonate and the oxine methods. Matsuura (86) determined magnesium in metallic aluminum by precipitation from an alkaline cyanide solution, thus avoiding interference from copper, nickel, and iron. Gaspar y Arnal and Rojo (44) separated magnesium from the alkaline earths and lead by precipitation as sulfites in ethanol-water medium. Ivanova and Chugunova (63) determined magnesium oxide in magnesium metal ponder by selectively dissolving the former in a solution of chromium(T'1) oxide. Aluminum. Analytical methods for aluminum alloys (26) were published by the Chicago Aluminum Research Institute. Silverman (121) determined aluminum by 8-hydroxyquinoline (8quinolinol), The hexamethylenetetramine precipitate waa treated to remove chromium as volatile chromium dioxydichloride, followed by selective removal of iron and molybdenum by 8hydroxyquinoline in the presence of citric and acetic acids. Lacroix (79) studied as a function of pH the solubilities in water and chloroform of the oxinates of aluminum, gallium, and indium. Wilson (146) used benzoate precipitation to determine aluminum in the presence of iron. Thioglycolic acid as reducing agent formed a soluble complex with divalent iron. Chromium, vanadium, and titanium interfered. Gentry (48) published an analytical scheme for permanent magnet alloy. Following treatment with potassium cyanide in ammoniacal tartrate solution, aluminum was precipitated by oxine aided by sulfonated lorol. Smith and Cagle (1.83) determined aluminum in iron ore by precipitation with 2,2'-bipyridine which simultaneously formed a soluble complex with divalent iron. Edwards (33) determined aluminum in aluminum bronze by precipitation with 8-hydroxyquinoline following separation by treating the sulfuric acid solution of alloy with tartaric acid, iron (111) chloride, ammonium chloride, ammonium hydroxide, potaasium cyanide, and sodium sulfite. Bottger (12) preferred hexamine to ammonia water for precipitation of aluminum and iron. Ivanova and Chugunova (63) determined aluminum oxide in aluminum powder by selectively dissolving the oxide in chromium(V1) oxide and nitric acid, Aluminum was determined in the filtrate as hydroxide. Kimura, Kuroda, and Urakawa (89) determined aluminum oxide in aluminum by isolation with aqueous solution containing tin(1V) chloride, ammonium chloride, and oxalic acid. NATURALLY RADIOACTIVE ELEMENTS
Thorium, Uranium, and Plutonium.
Moeller and Schweitzer
(91) determined thorium in monazite and concentrates by pre-
V O L U M E 22, NO. 1, J A N U A R Y 1 9 5 0 cipitation with a measured excess of sodium pyrophosphate containing a known activity of radioactive phosphorus and determining radioactivity of the excess. Yu (150) described a modification of Scott's method for the analysis of uranium ore containing high content of columbium and tantalum. Duval (32) used the thermal balance to study optimum ignition temperatures of precipitates of uranium salts. A table of suitable temperatures for drying or calcination of precipitates was included. This author preferred precipitation of uranium by oxine or oxalic acid. Harvey, Heal, Maddock, and Rowley (64) recorded various reactions of plutonium. Hydrogen peroxide precipitated tetravalent plutonium in the pH range 3 to 4.5. The composition of the precipitate was not known. Heyavalent plutonium was quantitatively precipitated by 8-hydrouyquinoline in the p H range of 3.5 to 9. Other precipitants were recorded. ALKALI AND ALKALIhE E4RTH ELEMENTS
Sodium and Potassium. Klement and Dmytruk (71)discussed the removal of phosphate ion in preparation for sodium determinations, and recommended adsorption of phosphate by Wolfatite 31. The resin required special treatment. Lund ( 8 0 ) investigated methods for the determination of sodium and potassium in silicate minerals and rocks. For low sodium contents the direct determination of sodium as triple acetate was considered superior to the indirect method of J. L. Smith, in which the sodium content is obtained by difference. Belcher ( 8 ) published reviews dealing with inorganic and organic reagents for potassium. Calcium, Strontium, and Barium. Peltier and Duval (101) made a critical study of about a dozen gravimetric methods for calcium in the presence of magnesium. These authors reconimended the tungstate method because of its ease of execution and speed. This finding is contrary to that of Ievins and Grinsteins (61),who reported various difficulties with the tungstate method and stated that, contrary to the literature, this method could not satisfactorily separate calcium from magnesium. Shvedov (120) used radioactive indicators to determine the efficiency of the oxalate method for separation of calcium from magnesium. It was found that coprecipitation of magnesium increased with rise of temperature from 20" to 100" C. and with increasing magnesium content. Other factors such as speed of neutralizing, etc., also affected the results. It was concluded that, although COprecipitation of magnesium could be reduced to a minimum, it was never entirely prevented. Kallmann (67) used hydrogen chloride-butanol solutions t o separate calcium from barium and strontium. Calcium was determined as oxalate. Strontium and barium were n-eighed as chlorides and subsequently separated by butanol in concentrated hydrochloric acid. Correction factors were needed. Osborn (97) reported on the rapid separation and determination of calcium, barium, and strontium in rocks and minerals. Gaspar y Arnal and Rojo (45) separated calcium from barium, strontium, and lead by treatment of the sulfites in dilute ethanol with nitric acid. A t a nitric acid strength of 1.43 A', calcium sulfite was selectively dissolved. Yatagawa and Tei (148) found that the determination of calcium in brass usually resulted in contamination of calcium oxalate by copper. This error was avoided when the solution, after electrolysis, was evaporated and the residue oxidized with bromine. Asari and Watanabe ( 2 ) recommended nitric acid of density 1.445 for the separation of the nitrates of strontium and calcium by Koll's method. When considerable calcium was present three to four reprec'ipitations were necessary. Segnit (117) discussed the behavior of barium in silicate analysis. Complete separation of barium and calcium as oxalates waa not effected in the presence of more than 4 t o 570 of barium oxide. Directions were given for the recovery of barium in the presence of calcium and of magnesium. Kolarow (72) stated that with an experienced analyst, ignition of barium sulfate in the
91 presence of filter paper did not result in the formation of appreciable barium sulfide. Gaspar y Arnal and Poggio Mesorann (39) precipitated barium, calcium, and strontium as sulfite in ethanolwater medium. Gaspar y Arnal and Santos ( 4 7 ) determined barium or thiosulfate by precipitation as barium thiosulfate monohydrate from an ethanol medium. Titration with iodine could be used as an alternative to weighing the monohydrate. Strontium interfered but calcium did not. STEEL-FORMING ELEMENTS
Zirconium. Charlot (25) proposed the use of phosphoric acid in 2 t o 3 Y hydrochloric acid for the characterization of zirconium. Arsenic acid effected a selected separation of zirconium and titanium. Various organoarsenic acids were also suggested for zirconium and associated elements. K a d a and Ishii (142) used hydrofluoric acid to determine zirconium in the elementary state in commercial samples of zirconium. This method gave results favorably comparable to those obtained by the method of weight increment upon oxidation and avoided certain difficulties. Hahn (63) described the precipitation and determination of zirconium by the product of hydrolysis of metaphosphoric acid and of organic phosphates. Willard and Hahn (144) preferred ethyl orthophosphate to diammonium hydrogen phosphate for the precipitation of zirconium. The precipitate of ZrO [ H ( C H J P O ~ ] Z and of ZrO(HZP0& was much denser and much more crystalline. The solutions were adjusted to 3.6 S and ignition was continued to the pyrophosphate. Precipitations with metaphosphoric acid were preferred to the direct ,addition of a soluble orthophosphate. Compared to the cupferron method, determinations were more rapid and required fewer separations and manipulations. Columbium and Tantalum. -4limarin (1) determined columbium and tantalum in an oxalic acid solution by precipitation with a reagent prepared from pyrogallol and urotropine. The complex was ignited at 900" to 1000" C. Slavin and Mendonpa Pinto (122) used a modification of Schoeller's tannin method for the analysis of tantalite-columbite coiicentrate. The time required for an analysis was about 4 to 5 days, compared to about 15 days for the original Schoeller procedure. Rogers (114) discussed the principles involved in the determination of columbium, tantalum, and tungsten in steel. Jaboulay (64) determined tantalum and columbium in ferrotantalum, ferrocolumbium, and steels. The alloy was fused with potassium pyrosulfate, and an extract made with sulfuric acid and sodium sulfite. The mixed pentoxides were treated with ammonium polysulfide, and after filtering and washing, the residue was calcined and the silica volatilized as usual. The separation was repeated and the pentoxides collected from the filtrate were added t o the main residue. The combined precipitates were fused with potassium hydroxide and the tantalum was separated by treatment of the aqueous solution with 12y0hydrogen peroxide and sulfuric acid, After one reprecipitation, columbium was removed from the filtrates by sodium sulfite and sulfuric acid. Barber (3) published a procedure for determining columbium and tantalum in basic Bessemer slag. The procedure was similar to Jaboulay's except that the purified residue of columbium and tantalum pentoxides was fused with potassium carbonate and the earth acids were precipitated by tannin. After final fusion with potassium pyrosulfate and extraction with water and sulfuric acid the mixture of oxides was weighed. Maurer ( 8 7 ) published a procedure for the determination of columbium carbide in stainless steel. The sample was digested n ith sulfuric acid to isolate columbium carbide, which subsequently was dissolved with perchloric and nitric acids. Columbium was finally precipitated in sulfur dioxide-hydrochloric arid medium. Societe GCnerale PYIBtallurgique de Hoboken (126) recorded methods for the separation of columbium and tantalum. Columbium pentoxide was selectively reduced by hydrogen or
92 selectively “nitrided.” The nitride was treated with a halogen to form columbium halide, which was separated from tantalum by distillation and condensation. Molybdenum. Buscar6ns Ubeda and Loriente Gonzales (80) stated that o-bianisidine could be used for the gravimetric determination of molybdenum. Feigl and Raake (3.4) discussed the “masking” effect of hydrogen peroxide in precipitations of molybdate, tungstate, and vanadate. All known precipitating reactions of molybdate and tungstate could be prevented, although lead molybdate, once formed, retained its insolubility. Blanco (11) reviewed 22 methods for the determination of molybdenum, seven of which were gravimetric. Tungsten. Buscar6ns Vbeda, Herrera, and Loriente Gonzales (19) recorded three procedures which eliminated interference by carbon dioside in the determination of tungsten by precipitation as barium tungstate. Fomin, Shalyagin, and Starostina (37) stated that tungsten is precipitated quantitatively hy prontosil in the presence of nitric acid or ammonia water. Philipp (106) used an acetic acid solution of totaquinhe. Furey and Cunningham (58) published improvements in established methods for the determination of various constituentg in tungsten carbides. Brintzinger, Rausch, and Backhausen (16) reported a procedure for determining tungsten in ores and slags. The ores were corroded by treatment with sodium sulfate a t 750’ to 850” C. in a current of hydrogen or illuminat,ing gas. After removal of silica and sulfides of divalent iron and manganese, tungstic acid was precipitated by nitric acid. Mendonpa Pinto (89) compared the cinchonine, tannin-antipyrine, and cinchonine-tannin-antipyrine methods for the determination of tungsten in samples of Brazilian scheelite. The three methods gave practically the same results. Vanadium, Chromium, and Manganese. Gomez Ruimonte (60) discussed the determination of vanadium in steel containing more than 5% chromium. Vanadate was precipitated by lead acetate in an ammonium acetate medium. The author recorded the composition of the precipitate as 2PbzVaO7,PbO (5Pb0.2Va05). Burriel and Barcia Goyanes (18) recorded the composition of lead vanadates o b t a i n d a t various acidities-e.g., pII 7 , 3Pb0.V205; pH 9, 5PhO.2VzO5; ~ €10, 1 2PbO.T:,O6. Dupuis and Duval (28) reported suitable ignition temperatures for heating precipitates of chromium hydroxide, phosphate, and oxinatc and of the chrumates of silver, mercury, barium, and lead. Hein and Arvay (55) investigated the use of BisOsH&nOa for rhe gravimetric determination of manganese. The effects due to variations in acid strength, extended heating, excess of BiOC104, etc., were studied. Nickel. G6niez Ruimonte (61) dealt with the interference of cobalt in the determination of nickel in special steels high in cobalt and lorn in nickel. Silica and tungsten were removed prior to precipitation of nickel dimethylglyoxime in an ammoniacal tartrate medium. The precipitate was treated t o remove iron, and the nickel was reprecipitated in the presence of hydrogen peroxide. Voter, Banks, and Diehl (140) recommended 1,2cyclohexanedione dioxime as a reagent for nickel. Although the reagent was water-soluble, some of it was coprecipitated, causing a positive error. KO satisfactory method of separating iron was found. Johnson and Simmons (66),who previously recorded this application of niosime, found that the precipitate did not, crystallize well and that the results were too high for gravimetric work. Peltier, Duval, and Duval (104) tested new analytical reagents and reactions proposed during the period 1937 t o 1947 in preparation for t,he fourth report of the Committee of the Union Internationale de Chimie. They recommended replacing dimethylglyosime by the dioxime of 1,2-cyclohexanedione for the precipitation of nickel, because the latter reagent had been found to react at higher acidity and to be more soluble in water. These data agree with the original work of Vot,er, Banks, and Diehl but there is significant disagreement as to the interference of iron. The latter authors stated that “a method for the satisfactory quantitative separation of nickel from iron was not found. The possibility
ANALYTICAL CHEMISTRY of using tartrate and citrate was exhaustively investigated.” Peltier et al. stated that interference from iron could be prevented by tartrate and that cobalt could be separated in ammoniacal ammonium chloride. Fisher and Simonsen (35)used the electron microscope to study variations in crystal form with conditions of precipitation. Precipitates of dimethylglyoxime with nickel and with bismuth were used, and the authors concluded that the appearance of the crystal should be used with caution for qualitative identification. NONFERROUS METAL ELEMENTS
Copper and Zinc. Bertiaux (9) selected the best known methods for the analysis of copper and copper alloys. Yatagawa ( 1 4 7 ) determined zinc in brass by treating the sulfuric acid solution with aluminum. From the filtrate zinc sulfide was precipitated and determined finally by precipitation with hydroxyquinoline. Gallium and Thallium. Charlot (25) separated gallium from aluminum by chloroform extraction a t pH 2.0 of the gallium compound of 8-hydroxyquinoline. Lacroix (78) reported on ~ o m e of the properties of the oxinates of aluminum, gallium, and indium. One part of gallium could be separated from lo4parts of aluminum by chloroform extraction of the oxinate a t pH 2.0. Raghava Rao (112) precipitated univalent thallium with hydrogeri iodate in ethanol medium, The solubility of the precipitate was appreciable. With the aid of the Chevenard balance, Peltier and Duval (102) determined the temperature limits for drying or igniting compounds of thallium used for its quantitative determination. Thallium(II1) oxides prepared chemically or electrolytically showed evidence of transitory formation of 3T1203.TLO. Smith (125) used tetraphenylarsonium chloride to determine trivalent thallium. The white precipitate of (C6H~)&T1Clr was dried a t 110’. Interfering ions were: hhon-, Io4-, CI04-, Reo4-, CNS-, KO3-, I-, Br-, and complex halides. The method was considered better than methods based on determination as thallous chromate. Mercury and Lead. Bottger (12) recorded that a precipitate of mercury sulfide made in the presence of hydrochloric acid contained some Hg&C12. .4 method of correction was given. Burriel and Barcia Goyanes (18) studied the variations in composition of the vanadates of silver and of lead as a function of acidity. The compositions were: a t p H 7,3PbO.Vz06 and 3AgzO.VzOs; a t pH 9, 5Pb0.2V2O5and 2A4gr0.V~05; a t pH 10, 2PbO.Vz05 and Ag2O.V2O5. hlayr (88) determined lead as the salt of gallic acid in a solution buffered with sodium acetate. The precipitate was weighed directly and was appreciably soluble in boiling water. In the presence of bismuth, lead was determined after removing bismuth from a nitric acid medium as CtHZ(OH)pCoOBi(OH),. Nurgulescu and Dobrescu (93) precipitated lead as basic salicylate. The dried organic complex was converted to lead sulfate and the results were found to be excellent. Young, Golledge, and Talbot (149) devised a method for the determination of lead oxide in ores, etc., which avoided errors due t o lead phosphate and lead vanadate counting as sulfides in the separation of the latter from oxidized forms of lead. Lead sulfate, carbonate, and oxide were selectively removed with ammonium acetate. The residue was treated R ith perchloric acid which isolated lead sulfide. Krossin (77) recorded a procedure for the determination of lead sulfate, lead sulfide, and lead oxide in the presence of one another. Total lead was determined after fuming with mixed acids. To determine lead monoxide and lead sulfate, the sample was treated uith ammonium acetate. Lead monoxide in roast material was extracted with ricinoleic acid and ethanol. Gaspar y Arnal, Poggio Rlesorana, and Rodriguez Calleja (42) determined lead by precipitation as lead sulfite in 5070 ethanol and subsequently by converting to sulfate. Brut ( 1 7 ) stated that ethanol was necessary for the separation of lead as sulfate. HOWever, the presence of sulfuric acid in the alcohol solution increased the solubility appreciably. Hubicki and Rys’ (60) discarded tar-
V O L U M E 22, N O , 1, J A N U A R Y 1 9 5 0 taric acid in the determination of lead as phosphate. Diammonium hydrogen phosphate in an ammoniacal medium was recommended. The precipitate was dried a t 130’ C. Tin and Germanium. Jean (65) precipitated tin with tungstosilicic acid in the presence of hexamethylenetetramine in the p H rangr 1 to 3. The precipitation was followed by a nephelometric determination by cupferron. The method was applicable t o steels and was faster and more accurate than older methods. Holness (59) precipitated germanium by tannin in ovalate solution at 0.07 A’ acidity. Clean separations were effected in one precipitation from vanadium, iron, zirconium, thorium, and aluminum. Tin and tantalum precipitations took place a t a higher acidity and titanium a t a lower acidity. The method was superior to precipitation in acid sulfate solution in that titanium could be separated and the precipitate was more tractable. Arsenic and Bismuth. Kolthoff and Carr (73) recorded a procedure for the quantitative collection of traces of arsenic by COprecipitation with ammonium magnesium phosphate. Gaspar y Arnal, Poggio Mesorana, and Rodriguez Calleja (41) separated bismuth and copper by a double precipitation of bismuth with nitric acid and sodium sulfite in 67.27, ethanol. The precipitate could be converted t o bismuth sulfate by heating to 340” to 380” C., or by stronger heating, bismuth oxide could be formed. Jean (65) precipitated bismuth as a complex with thiourea and tungstophosphoric or tungstosilicic acids. The complev was dissolved and bismuth determined colorimetrically. The method was applied t o certain metallurgical products. Bertiaux and Th6ry (10) stated that in the determination of bismuth in industrial lead the preliminary removal of lead as sulfate resulted in loss of bismuth. They recommended the separation of bismuth by potassium bromate in a slightly alkaline medium. A little antimony or tin or small proportions of arsenic, mpper, iron, cadmium, and zinc did not interfere. RARE EARTHS AND RELATED ELEMENTS
Scandium. Beck ( 7 ) reported that phytin could be used t o precipitate scandium, producing a salt whose insolubility was comparable t o that of barium sulfate. Titanium, zirconium, hafnium, and thorium interfered. Ostroumov ( 9 9 ) recommended a buffered solution of pyridine for precipitation of scandium. Separation from rare earth elements was effected by double precipitation a t p H 4.9. Triple precipitations were required to separate scandium from gadolinium, holmium, and ytterbium. NOBLE METAL ELEMENTS
Silver. Peltier and Duval (103) discussed a completely automatic method of analysis of some alloys of silver and copper. The alloy was dissolved in nitric acid and evaporated to nitrates of copper and silver, which were then heated on the thermobalance. From the magnitude of the weight losses in various temperature ranges the composition of the alloy could be determined. The error was of the order of 0.3%. Platinum Group. Voter, Banks, and Diehl (141) used 1,2cyclohexanc dione dioxime (nioxime) for the precipitation of palladium. Vanossi (138) recorded minor improvements in a previously published method for the separation and identification of osmium, ruthenium, and germanium. Pshenitsyn (111) discussed the use of sparingly soluble sulfides in the separation and estimation of platinum and palladium. From a mixture of the sulfides of copper, palladium, rhodium, and platinum, ferric chloride dissolved the copper(1) sulfide completely and platinum sulfides only slightly. Ubaldini (136) used 2-mercaptobenzothiazolr for the preci nitation of platinum, palladium, and rhodium. The platinum complex was precipitated in acid medium. In alkaline solution, sodium hexachloroplatinate, in contrast with hydrogen hexachloroplstinate, did not produce a precipitate. I n alkaline solution, rhodium produced insoluble Rh(CcH4r\’SCS)2while the palladium complex was precipitated in either alkaline or acetic acid media. Based on these data, Ubaldini and Nebbia (137) de-
93 veloped a method for the separation of platinum from rhodium and palladium in potassium hydroxide solution. In the presence of potassium salts. mercaptobenzothiazole precipitated rhodium and palladium. With sodium salts the precipitate was colloidal and occluded part of the platinum. Thiers, Graydon, and Beamish (129) investigated by radioactive means the distribution and losses of ruthenium during fire assays. Losses to the slag and cupel were found, but t,here was n o loss by volatilization. A new lead parting method was developed. The “insoluble” could be dissolved readily by treating the filtered residue and paper with chlorine in sodium hydroside medium. Ruthenium was determined by “thionalide.” NONMETAL ELEMENTS
Hydrogen, Carbon, and Silicon. Sauerwald (116) determined hydrogen in magnesium metal by chlorination to form hydrogen chloride gas, which subsequently was oxidized with oxygen gas in the presence of cupric oxide. The water vapor was absorbed by magnesium chloride and phosphorus pentoside. Naughton and Uhlig (95) investigated the cause of the discrepancy in results for carbon in steel obtained by the standard combustion method and by the low-pressure combustion method. They concluded that the latter method met present requirements for the analysis of compounds containing little carbon. Kovtun (76) determined carbon in iron alloys a t lowered temperatures by addition of the flux PbO(Cu0)Pb. With low carbon-iron alloys the iron r w s largely removed by selective dissolution with K?CuCla. The author also recommended the multiple combustion method for determining carbon in furnace dust and slags. Shinkai (118) determined silica by precipitation with aluminum hydroside a t a mole ratio of 1 t o 15. Silica was determined by difference after removal by hydrofluoric and sulfuric acids. Cavallaro and Tani (2.4) found that the silicomolybdates of trimethylamine and triethylamine were more easily filtered and washed than was the silicomolybdate of pyridine. The use of the former would facilitate determination of silicon in steels. The compositions of silicomolybdates and silicotungstates were discussed. Stross (127) recorded an improved gravimetric determination of silicon in aluminum alloys that was developed in Germany during the war. The sample was heated in sodium hydroside solution in a nickel beaker, followed by treatment with hydrochloric or sulfuric acid. Copper, etc., were dissolved with hydrogen peroxide, and gelatin was added after initial flocculation of silicic acid. Phillips and Herman (106) determined small amounts of silicon in magnesium alloys by treatment with brominated nitric acid followed by addition of a sulfuric acid solution of hydrogen peroxide. Gelatin and pulped accelerators were used to aid filtration. Brabson, Mattraw, Maxwell, Darrow, and Seedham (16) developed a gravimetric procedure for the determination of silica in compounds such as fluosilicate, cryolite, and fluorspar. T h e silica was weighed as the oxine salt of silicomolybdic acid. Fluorine was “complexed” with boric acid. The method vias suitable for the analysis of complex fluorides in which silica was a major constituent. Phosphates required a correction. Tetravalent germanium, pentavalent vanadium, and arsenic interfered. The determination of silicon and manganese in iron and steel was discussed in a report of the Methods of Analysis Committee, Metallurgy Division, British Iron and Steel Research Association (90). Gurvits and Podgaits (66)recorded a procedure for the determination of quartz in the presence of silicates, which involved an extraction with hydrochloric acid, ignition of residue, treatment with hexafluosilicic acid, and weighing, followed by addition of sulfuric and hydrofluoric acids and a second weighing. The difference in weights was assumed to be the weight of quartz. Phosphorus. Ilesans (68) precipitated phosphoric acid as bismuth phosphate. Separation from various divalent cations was effected satisfactorily. Holder (58) determinrd phosphoric
94 acid in the presence of vanadic acid by reduction to tetravalent vanadium by sulfur dioxide followed by precipitation of phosphate with magnesia mixture in a tartaric acid-ammonium chloride medium. DuBox (27) recorded a procedure for the rapid determination of phosphate in steel bj acid-molybdate solution. An explanation was given for the increased rate of precipitation. Cale (23) discussed the determination of sodium pyrophosphate and triphosphate in commercial tripolyphosphate. Oxygen and Sulfur. Pigott (107‘) discussed Gray and Sander’s method of determining total oxygen in ferrous metals. The sample wm heated a t 1150” in contact with aluminum metal in a graphite boat, followed by determination of aluminum oxide. A single determination required several days, but the apparatus was less costly and complicated than vacuum fusion apparatus. Kitahara (70) determined sulfur in “pure iron” by treating the chloride solution of the sample with ethyl ether saturated with hydrogen chloride to remove iron (111) chloride, reducing the remaining iron with zinc. and finally precipitating as barium sulfate. Isakov and Shipunova (62) used picric acid prior to precipitation of barium sulfate. Mahr and Krauea (84) published a new method for determining sulfate. Co(NHI)6BrSOcwas precipitated from neutral or slightly acid solutions, dried a t 80” C., and weighed. As alternatives, the precipitate could be dissolved in water and the bromine content determined volumetrically, or the color of the aqueous solution could be used to measure the cobalt content. Flint (36) dealt with the determination of small concentrations of sulfur trioxide in the presence of larger concentrations of sulfur dioxide. The two gases were absorbed by a mixture of water and isopropyl alcohol. The sulfur trioxide n-as determined w barium sulfate and the sulfur dioxide was distilled n ith a stream of nitrogen and absorbed in hydrogen peroxide Tkachenko and Khripach (130) described in detail a painstaking procedure for the determination of “free silicon dioxide” in ores and associated rocks. Gaspar y Arnal and Poggio Mesorana (40) discussed the gravimetric determination of sulfites by precipitation of barium salts in ethanol-water medium, followed by conversion to barium sulfate. Sulfur trioxide in soluble sulfites was determined gravimetrically by precipitating by lead nitrate in ethanol-water medium followed by conversion to lead sulfate. Selenium and Tellurium. Tananaev and Murasheva (188) determined selenium in steel by dissolving the residue from a sulfuric acid treatment in nitric acid and converting to chlorides. The selenium was precipitated with sulfur dioxide. Ghosh (49) determined selenium and tellurium in refined copper by dissolving the sample and iron filings in nitric acid, adding ammonia water, and from a hydrochloric acid solution of the mixed hydroxides removing selenium and tellurium by stannous chloride. Fluorine. Wiechert and Burandt (14.3, dealing with the determination of fluorine, found that the precipitate of calcium fluoride was rendered more “filterable” if made in the presence of gelatin. Mixed precipitates of calcium sulfate and calcium fluoride were treated with orthoboric and perchloric acids to volatilize boron trifluoride. Tsubaki (155) published an improved method for the analysis of the mineral fluorite. The sample was fused with potassium sodium carbonate and titanium dioxide, silica was removed, and calcium fluoride was precipitated by a known amount of calcium acetate. The fluorine content waa obtained by determining the excess of calcium. Rinck (113) published a review dealing with the separation and determination of fluorine. Chlorine and Bromine. Pil’nik (108) determined chlorides by titration with mercurous nitrate followed by quantitative recovery of mercury from the precipitate. Sampey, King, and Blitch (115) published an approximate method for the determination of bromine. The bromine compound was dissolved in acetone saturated with sodium iodide. The sodium bromide was determined with an accuracy of 97 to 99%.
ANALYTICAL CHEMISTRY ACKSOW LEDGMEVT
The author is indebted to W. A. E. McBryde for assisting in the Iireparation of this manuscript. LITER4TURE CITED (1) Alimariti, I. P., Zasodskaya Lab., 13, 547-8 (1947). (2) Asari, Tamiya, and Watanabe, Hisa, Bull. I n s t . P h y s . Chem. Research ( T o k y o ) , 23, 614-19 (1944). (3) Barber, H., Berg- u. hiittenmann. Monatsh. montan. Hochschule Leoben, 92, 114-15 (1947). (4) Baron, J . , Chim. anal., 30, 250-1 (1948). (5) Baryshev, N. V . , Zasodskaya Lab., 13, 521-32 (1947). (6) Beamish, F. E., ANAL.CHEM., 21, 144 (1949). (7) Beck, G., Mikrochemie vet mikroehim. A c t a , 34, 62-6 (1948). (8) Belcher, R., I n d . Chemist, 24, 213-16, 473-5 (1948). (9) Bertiaux, L., C h i m . anal., 30, 108 (1948). (10) Bertiaux, L., and ThBry, R., Bull. soc. chim. 1948, 1017-19. (11) Blanco, Alberto, Quimiea ( M e r . ) ,6, 52-7 (1948). (12) Bottger, Wilhelm, 2. anal. Chem., 128, 421-31 (1948). (13) Bowden, W. C., Jr., AXAL.CHEM.,20, 989 (1948). (14) Boy, Carl, Z . Erzbergbau u. Metallhiittenw., 1, 112-13 (1948). (15) Brabson, J. A., hlattraw, H. C., Maxwell, G. E., Darrow, Anita, and Needham, M. F., ANAL. CHEM.,20, 504-10 (1948). (16) Brintzinger, Herbert, Rausch, Fritz, and Backhausen, Martin, Z . anorg. Chem., 255, 323-4 (1948). (17) Brut, M . , C h i m . anal., 30, 273-4 (1948). (18) Burriel, F., and Barcia Goyanes, C., Anales fis. y q u h ( M a d r i d ) ,921-8 (1947). (19) Buscar6ns Ubeda, I., Herrera, A., and Loriente Gonzales, Eladio, Ibid., 42, 1139-46 (1946). (20) Buscar6ns Ubeda, I., and Loriente Gonzales, Eladio, Ibid., 40, 1312-21 (1944). (21) Cadariu, I., Z . anal. Chem., 128, 270-1 (1948). (22) Cale, W.R., C a n . Chem. Process Inds.. 32. 741-5 (1948). (23) Cattelain, E., Rev. sci., 86, 234-41 (1948). (24) Cavallaro, Leo, and Tani, Angelo, A t t i accad. sci. Ferrara, 24, NO.2 (1946-47). (25) Charlot, G., A n a l . C h i m . A c t a , 1, 2 1 8 4 8 (1947). (26) Chicago Aluminum Research Inst., Am. Foundryman, 14, No. 2, 63 (1948) (review). (27) DuBox, E. J., Anales asoc. q u t m . Argentina, 36, 41-3 (1948). (28) Dupuis, Therese, and Duval, Clement, Compt. Tend, 227, 7 7 2 4 (19481. (29) Dubal, Clement, A n a l . C‘him. Acta, 1, 3 4 1 4 (1947). (30) Ibid., 2, 92-3 (1948). (31) Duval, Clement, Compt. rend., 226, 1276-8 (1948). (32) Ibid., 227, 679-81 (1948). (33) Edwards, W. T., A n a l y s t , 73, 556-7 (1948). (34) Feigl, F., and Raake, I. D., A n a l . C h i m . Acta, 1, 317-25 (1947). (35) Fisher, R. B., and Simonsen, S. H., ANAL.CHEM.,20, 1107-9 (1948). (36) Flint, D., J . SOC.C h i m . I n d . ( L o n d o n ) , 67, 2-5 (1948). (37) Fomin, V. V., Shalyagin, V. IT., and Starostina, V. G., Zauodskaya Lab., 13, 679-80 (1947). (38) Furey, J. J., and Cunningham, T. G., ANAL.CHEM.,20,563-70 (1948). (39) Gaspar y Arnal, T., and Poggio Mesorana, J. M., A n a l e s f b . y qu2m. ( M a d r i d ) , 43, 437-70 (1947). (40) Ibid., pp. 763-72; P u b s . inst. q u i m . “Alonso Barba” ( M a d r i d ) , 1, 298-338 (1947). (41) Gaspar y Arnal, T., Poggio Mesorana, J. M., and Rodrigues Calleja, Hipolite, Anales fh.y q u i m . ( M a d r i d ) , 43, 571-608 (1947). (42) Ibid., pp. 609-16. (43) Gaspar y Arnal, T., and Rojo, A. M., Anales real soc. espafi. fie. 2/ quam., 44B, 851-6 (1948). (44) Ibid., pp. 857-62. (45) Ibid., pp. 863-71. (46) Ibid., PP. 941-6. (47) Gaspar y Arnsl, T., and Santos, M., Anales Ps. g quim. ( M a d r i d ) , 40, 660-70 (1944). (48) Gentry, C. H. R., Metallurgia. 38, 108-13 (1948). (49) Ghosh, K. P., J . I n d i a n Chem. Soc. I n d . & News Ed., 11, 61-2 (1948). (50) Gomes Ruimonte, I., Anales fts. g quim. (Madrid), 41, 1457-62 (1945). (51) Ibid., 43, 907-ll(1947). (52) Gurvits, S. S., and Podgaits, V. V., Zavodskaya Lab., 14, 935-8 (1948). (53) Hahn, R. B., Unis. iliicrofilms (Ann Arbor, Mich.), Pub. 964 (1948). (54) Harvey, B. G., Heal, H.G., Maddock,A.G., and Rowley, E. L., J . Chem. Soc. ( L o n d o n ) , 1947, 1010-21.
V O L U M E 2 2 , N O . 1, J A N U A R Y 1 9 5 0
95
Hein, Fr., and Arvay, D., Angew. Chem., A60, 157 (1948). Herbo, C. L., Anal. Chem. Acta, 1, 254-9 (1947). Herteland, L., 2. anal. Chem., 128, 115-27, 129-40 (1948). Holder, Gerard, Ibid., 128, 231-3 (1948). Holness, H., Anal. Chim. Acta, 2, 254-60 (1948). Hubicki, Wlodzimierz, and Rys’, Raymond, Ann. Univ. Mariae Curie-Sklodowska Lublin-Polonia, Sect. aa, 2, No. 4, 55-68 (1947). Ievins, -4., and Grinsteins, V., Z . anal. Chem., 124, 288-300 (1942). Isakov, P. M., and Shipunova, L. G., Nauch. ByulE, Leningrad Gosudarts Univ., No. 13, 8-10 (1946). Ivanova, A. P., and Chugunova, V. I., Russian Patents 67,91112 (Feb. 28,1947). Jaboulay, B. E., Rev. mBt., 45, 343-6 (1948). Jean, Marcel, Ann. Chem. (12), 3, 470-526 (1948). Johnson, W.C., and Simmons, &I., Analyst, 71, 554-6 (1946). Kallmann, Silve, ANAL.CHEM.,20, 449-51 (1948). Kesans, August, 2. anal. Chem., 128, 215-21 (1948). Kimura, Kenjiro, Kuroda, Kazuo, and Urakawa, Mario, Bull. Inst. Phys. Chem. Reseaich (Tokyo),23, 517 (1947). Kitahara, Saburo, Ibid., 23, 659-68 (1947). Klement, Robert, and Dmytruk, Rudolf, Z . anal. Chem., 128, 106-9 (1948). Kolarow, Nikola, Ibid., 128, 225 (1948). Kolthoff, I. M., and Carr, C. W.,ANAL.CHEM.,20, 728-30 (1948). Korenman, I. M., Zhur. Anal. Khim., 1, 64-72 (1946). Kostrikin, T . M.,Zavodskaya Lab., 14, 173-5 (1948). Kovtun, M. S.,Ibid., 14, 487-90 (1948). Krossin, Erwin, Z . Erzbergbau u. Metallhiittenw., 1, 177-8 (1948). Lacroix, S.,Anal. Chim. Acta, 1, 260-9 (1947). Ibid., pp. 260-81. Lund, Lars, J. Geol., 59, 490-1 (1948). Lur’e. Y. Y.. Zavodskaua Lab.. 14. 176-8 (1948). Lur’e, Y . Y , and Fillppova, N. A., Ibid., 13, 539-47 (1947). Ibid., 14, 159-72 (1948). Mahr, C., and Krauss, K., Z . anal. Chem., 128,477-84 (1948). Matheson, D. H.. Chemist-Analyst, 37, 18 (1948). Matsuuia Jiro, Bull. Inst. Phys. Chom. Research (Tokyo), 23, 523 (1947). Maurer, W.C., U. S.Patent 2,447.763 (dug. 24, 1948). M a y r , C., Monatsh, 77, 65-72 (1947). Mendonpa Pinto, Cassio, Anais aasoc. qulm. Brasil, 7, 6588 (1948). Metallurgy Division, British Iron & Steel Research Assoc., Metallurgia, 38, 346-52 (1948). Moeller, Therald, and Schweitzer, G. K., ANAL.CHEM.,20, 1201-4 (1948). Mohler, J . B., and Sedusky, H. J., Metal Finishing, 46, No. 11, 68-75 (1948). Murgulescu, I . G., and Dobrescu, Filofteia, Z . anal. Chem., 128,203-6 (1948). Musante, Carlo, Gazz. chim. ital., 78, 536-50 (1948). Nauahton, J. J.. and Uhlia, H. H., ANAL.CHEM.,20, 477-80 (1948). Osborn, G. H., Analyst, 73, 381-4 (1948). Osborn, G. H., Mineralog. Mag., 27, 258-62 (1946). Ostroumov, E. A., Zavodskaya Lab., 13, 404-10 (1947). Ostroumov, E. A., Zhur. Anal. Khim., 3, 153-61 (1948). Otsuka, Yoshiji, J . Soc. Chem. Ind. Japan, 46, 568-70 (1943). Peltier, Simone, and Duval, Clement, Anal. Chim. Acta, 1, 408-16 (1947). Ibid., 2, 210-17 (1948). Peltier, Simone, and Duval, Clement, Compt. rend., 226, 1727-9 (1948). Peltier, Simone, Duval, Therese, and Duval, Clement, Anal. Chim. Acta, 2, 301-6 (1948). Philipp, Paul, An& assoc. qutm. Brasil, 6, 161-6 (1947).
(106) Phillips, D. I?., and Herman, S. E., Metallurgia, 38, 179-80 (1948). (107) Pigott, V. E. C., Metallurgia, 37, 263-6 (1948). (108) Pil’nik, R. S., Zavodskaya Lab., 13, 687-9 (1947). (109) Piquott, E. C., Metal Treatment, 15, No. 55, 123-31 (1948). (110) Portnov, A. I., Zhur. Obshchei Khim. ( J . Gen. Chim.), 18, 594607 (1948). (111) Pshenitsyn, N. K., Akad. S a u k . S.S.S.R., Referatory, Otdel. Khim. Nauk, 1945, 51-2. (112) Raghava Rao, Bh. S.I’ , Current Sci. (India). 16, 376 (1947). (113) Rinck, E., Bull. S O C . chim. France, 1948, 305-24. (114) Rogers, B., Metallurgia, 37, 32630 (1948). (115) Sampey, J. R., King, A. B., and Blitch, B. C., J . A m . Chem. Soc., 70, 2606 (1948). (116) Sauerwald, Franz, Z . anorg, Chem., 256, 217-25 (1948). (117) Segnit, E. R., Trans. Roy. Soc., S . Australia, 69, 311-12 (1945). (118) Shinkai, Shigeyuki, J . SOC. Chem. Ind. Japan, 46, 234-6 (1943). (119) Shiokawa, Takanobu, Ibid., 67, 42-4, 53-8 (1946) (120) Shvedov, V. P., Zhur. Anal. Khim., 3, 147-52 (1948). (121) Silverman, G. L., Chemist-Analyst, 37, 11-14 (1948); 29, 28 (1940). (122) Slavin, Morris, and Mendonpa Pinto, Cassio, Brazil, Ministerio agr., Dept. Nacl. producao mineral, Lab. Produpao mineral, Bel. 21, 27-58 (1946). (123) Smith, G. F., and Cagle, F. W.,A x . 4 ~ .CHEM.,20, 574-6 (1948). (124) Smith, G. W., Ibid., 20, 1085-90 (1948). (125) Smith, W. J., Jr., Ibid., 20, 937-8 (1948). (126) Soc. GQnBraleMBtallurgique de Hoboken, Belg. Patent 470,891 (February 1947). (127) Stross, W., Metalliugia, 38, 63-5 (1948). (128) Tananaev, 5 . A., and Murasheva, V. I., Zhur. Anal. Khim., 3, 3-6 (1948). (129) Thiers, R., Graydon, W., and Beamish, F. E., ANAL.CHEM.,20, 831-7( 1948). (130) Tkachenko, K.S.,and Khripach, S. M . , Zavodskaya Lab., 14, 357-8 ( 1948). (131) Ibid., p. 625. (132) Touhey, \.V. O., and Redmond, J. C., ANAL.CHEM.,20, 202-6 (1948). (133) Ibid., p. 989. (134) Tschirch, E., Pharmazie, 3, 532-6 (1948). (135) Tsubaki, Isamu, J . SOC.Chem. Ind. Japan, 47, 504-6 (1944). (136) Ubaldini, Iva, Gazz. chim. ital.,78, 293-301 (1948). (137) Ubaldini, Iva, and Nebbia, Luisa, Ann. chim. applicata, 38, 241-8 (1948). (138) Vanossi, Reinaldo, Anales aaoc. qulm. argentina, 35, 120-30 (1947). (139) Ibid.. 36. 155 (1948). (146 Voter, R. C.,’Banks, C. V., and Diehl, Harvey, ANAL.CHEM., 20, 458-9 (1948). (141) Ibid., pp. 652-4. (142) Wada, Isaburo, and Ishii, Raizo, Bull. Inst. P h w . Chem. Research (Tokyo), 21, 877-923 (1942). (143) Wiechert, Kurt. and Burandt, M .L., 2. anal. Chem., 128, 50817 (1948). (144) Willard, H. H., and Hahn, R. B., A 4 ~CHEM., ~ ~ 21, . 293-5 (1949). (145) Willey, R. A., and Caine, J. B., A m . Foundryman, 14, No. 1, 50-6 (1948). (146) Wilson, H. N., Anal. Chim. Acta, 1, 330-6 (1947). (147) Yatagawa, Shozo, J . SOC.Chem. Ind. Japan, 46, 221-3 (1943). (148) Yatagawa, Shozo, and Tei, Iran, Ibid., 44, 1043-5 (1941). (149) Young, R. S., Golledge, A . , and Talbot, H. L., Am. Inst. Mining Met. Engrs., Mining Technol, 12, No. 2, Tech. Pub. 2303 (1948). (150) Yu, Pe-Nien, J . Chinese Chem. Soc., 15, 170-8 (1948). RECEIVED October
13, 1949.
Merck Analytical Fellowship Applications are being received for the Merck graduate fellowship in analytical chemistry, financed by Mer& & CO.,Inc., Rahway, N. J., and administered b y the AmmICAN CHEMICAL SOCIETY.The annual stipend is $2500. The place of study must be an institution whose undergraduate course of instruction in chemistry is approved by the Society, or in Canada, by the Chemical Institute of Canada. A fellowship will be awarded to the applicant believed capable of contributing most t o the advancement of the theory and prac-
tioe of analytical chemistry during the fellowship and in the future. It will be contingent upon the successful candidate’s obtaining acceptance from the institution and professor selected for the study program proposed,
Application blanks may be obtained from the
AJrERICAN
CHEMICAL SOCIETY,1155 Sixteenth St., S . W . , Washington 6, D. C. Deadline date for receipt of application, letters of recommendation, and transcripts of credits is February 15, 1950.
