V O L U M E 2 4 , NO. 1, J A N U A R Y 1 9 5 2 Muraki, I., and Ishimaru, S.,J . Electrochem. S O C .J a p a n , 19, 46-9 (1951). Ibid., pp. 155-9. Muratrs, Y., Shioda, K , , and Takahashi, R., Ihid.. 10, 450-1 (1942). Musha, S.,J . Chem. SOC.J a p a n , 68, 25 (1947). Musha, A., and Suzuki, Y., Ibid., 68, 24 (1947). Norwitz, G., Am. Foundryman, 18, 27 (1950). Norwitz, G., A n a l y s t , 75, 473-5 (1950). Ibid., pp. 551-2. Ibid., 76, 113-14 (1951). Ihid., PP. 236-7. Norwitz, G., ASAL. CHEX.,21, 523-5 (1949). Ihid., 23, 386-7 (1951). Norwitz, G., A n a l . C h i m . d c t a , 4, 53&8 (1950). Ihid., 5 , 106-8 (1951). Ibid., pp. 109-14. Norwitz. G.. 2. anal. Chem.. 131. 266-8 (1950). Ibid., pp. 41’&12. Ibid., pp. 412-13. Ihid., 132, 165-7 (1951). Ihid., pp. 168-70. Norwita, G., and Norwitz, I., Metallurgia, 42, 405 (1950). Notvest, R . W.,U. S. Patent 2,544,802 (1951). Oelsen, W., and Gobbels, P., Stuhl u. Eisen, 69, 33-40 (1949). Ogarev, -4.,J . Applied Chem., U.S.S.R.,19, 311-15 (1946) [English translation Metal I d . , 70, 338-40 (1947)l. Osborn. G. H., Metallurgia, 40, 111-13 (1949). Patterson, J. H., and Banks, C. V., ANAL.CHEM.,20, 897-900 (1948). Patterson, J. H., and Banks, C. V., U. S. Atomic Energy Commission. MDDC-1708 (Dec. 29, 1947). Penther, C. J., and Pompeo, D. J., ANAL.CHEM.,21, 178-80 (1949). Phillips, D. F., Metallurgia, 35, 169-71 (1947). Price, J. IT.,and Hoare, W. E., “Determining the thickness of tin coatings,” Greenford, England, Tin Research Institute (1949). Rabbitta, F. T., Can. Chem. Process I n d . , 32, 1023-5 (1948). Rabbitts, F. T., Chem. Canada, 1 , 2 1 (1949). Ramsey, JV. J., Farrington, P. S., and Swift, E. H., ANAL. CHEM.,22, 332-5 (1950). Reilley, C. N., Cooke, W. D., and Furman, N. €I., Ihid., 23, 103G2 (1951). Rogers, L. B., Ihid., 22, 1386-7 (1950). Rogers, L. B., and Stehney, A. F., Atomic Energy Commission, AECD-2239 (1948). I
,
95 (133) Rynesiewioz, J., ANAL.CHEM.,21, 756 (1949). (134) Rynasiewica, J., Atomic Energy Commission, AECD-2240 (1948). (135) Saito, J., J. E l e c t r o c h a . Assoc. Japan, 10, 445-9 (1942). (136) Schleicher, A., Chm.-Ing.-Tech., 22, 11-12 (1950). (137) Schleicher, A., “Naturforschung und Medizin in Deutschland 1939-1946,” Bd. 29, Analytische Chemie, pp. 49-54, \Viesbaden, Dieterich’sche Verlagsbuchhandlung,, 1948. (138) Schleicher, A., 2. anaE. Chem., 128, 381-92 (1948). (139) Ibid., 133, 135-43 (1951). (140) Schleicher, A., Z . Erzbergbau u. Metallhzittenw., 2, 210-12 (1949). (141) Schleicher, A,, and Schlosser, O., 2. anal. Chem., 130, 1-16 (1949). (142) “Scientific Apparatus and Methods,” summer ed., pp. 2-5, Chicago, E. H. Sargent and Co., Section 1, 1948. (143) Ibid., winter ed., pp. 3-5, Section 1, 1948-49. (144) Shaffer, P. A., Jr., Briglio, A., Jr., and Brockman, J. A , , Jr., ANAL.CHEM.,20, 1008-14 (1948). (145) Shaw, W. E., and Moore, E. T., Ihid., 19, 777-9 (1947). (146) Shikhvarger, F. D., Zavodskaya Lab., 15, 1165-71 (1949). (147) Silva Fangueiro, N. da, Engenharia e quim. (Rdo de J a n e r h ) , 2, NO.3, 15-16 (1950.) (148) Silverman, L., Chemiat-Analyst, 37, 62-4 (1948). (149) Skowronaki, S., A S T M BUZZ.,KO. 174, 60-5 (May 1951). (150) Steel, 126, 56-60, 76 (Jan. 23, 1950). (151) Sutton, J., Natl. Research Council Canada, Atomic Energy Project Div., Research (1945), N.R.C. 1591. (152) Syrokomskil, V. S., and Nazarova, T. I., J. Anal. Chem. U.S.S.R., 6, 15-23 (1951). (153) Thomas, E. B., and Nook. R. J., J . Chem. Education, 27, 217-19 (1950). (154) Tsyb, P. P., and KozlovskiI, M. T., Z a v o d s k a y a h b . , 16,147-150 (1950). (155) Veitsblit, G. I., Ihid., 13, 1255 (1947). (156) Wads, I., and IshiI, R., Repts. Sci. Research I n s t . ( J a p a n ) , 24, 3 2 2 4 (1948). (157) Ibid., 25, 211-13 (1949). (158) Wiberley, 5. E., and Bassett, L. G., ANAL.CHEM., 21, 609-12 (1949). (159) Williams, D., and Narchla, F. M., Bull. Inst. M i n i n g Met., No. 533, 257-95 (1951). (160) Wooster, W. S., Farrington, P. S.,and Swift, E. H., ANAL. CHEM.,21, 1457-60 (1949). (161) Zbinden, C., B u l l . soc. chim. b i d , 13, 35-40 (1931). (162) ZivanoviO, D., B u l l . doc. chim. Belgrade, 14, 273-80 (1949). RECEIVED November 26. 1951.
Inorganic Gravimetric Analysis F. E. BEAMISH AND W. A. E. MCBRYDE University of Toronto, Toronto, Canada
LRING the period under review (June 1950 to June 1951) significant contributions in the field of gravimetric analysis have come from three foreign laboratories. At the Institute of Obslichei, Pshenitsyn and coworkers recorded the results of an extensive lnvestigation of determination of platinum metals. At the Sorbonne, Dupuis, Duval, and coworkers contributed considerable data dealing with safe ignition temperatures of precipitates Rao and coq-orkers at Andhra University have materially increased the literature dealing with the determination of the earth elements of column four. T h e number of organic precipitants used in inorganic analysis continues to increase; however, there has been relatively little progress in establishing relationships between structure and efficiency as a precipitating reagent. Out of such investigations might come many much needed specific reagents. GENER4L PROCEDURES
Preparation of Samples and Precipitates. An automatic pipetype sampler, suitable for coal, ores, fertilizers, etc., was discussed b y J‘isman (176). Westwood (186) recorded precautions t o be taken during sampling of pig iron and cast iron. The low temperature decomposition of various corrosion-resisting materials
was discussed b y Seelye and Rafter (169) and Rafter (150) Effective decomposition and more easily dissolved products were obtained b y heating with sodium peroxide at 480” & 20”. Iridosmine required four treatments. Except in the case of sulfide, the platinum crucible was not attacked. By fusing with sodium carbonate and sulfur Sarudi (158) converted arsenic, antimony, and tin into water-soluble products. Some copper passed into the aqueous extract, and if large amounts of arEenic mere present there was some loss by volatilization. Martinez (116) stated t h a t calcinations of the hydrates of iron and aluminum oxides could be replaced by infrared desiccation, although empirical factors were required to obtain the weights of metal, and the precision was poor. Lead dishes Rere used by Fainberg and Iiedrova (50) in determining tin in poor ores and tailings. Proskuryakova (136) discussed accelerated filtrations of solutions containing silica. At p H less than 4 stable and easily filtered solutions were obtained. Methods of Selective Separations and General Gravimetric Reagents. GalmBs and hlataix (70) measured the p H at which the sulfides of cadmium, zinc, cobalt, and nickel could be precipitated. Zinc and cadmium were separated quantitatively a t p H of 0.4. Acridine in dilute acetic acid was used by Fidler (54) for the gravimetric estimation of vanadates, chromates, molybdates, and
ANALYTICAL CHEMISTRY
96 tungstates. The yellow precipitates obtained a t room temperature contained more water than precipitates obtained a t the boiling point. The precipitates could be dried and weighed directly or ignited to oxide. Peltenburg (131) used pyridine to separate iron, aluminum, and chromium from zinc. The separation from chromium was imperfect. R$y and Bhaduri (165) used cystine in ammoniacal solution for the estimation of copper, cadmium, cobalt, nickel, and zinc. The precipitates u ere ~5 eighed directly. T h e separation of zinc from iron and aluminurn was accomplished only by using a large excess of reagent in a tartrate or sulfosalicylic acid medium. Draney, Yanowski, and Cefola ( 6 5 ) found that the Cu++, Bg+, Hg,++, PtC16--, P d + + , and Au+++ions in acidic solutions were precipitated by potassium dicyanoguanidine. The application of ammonium benzoate for the estimation of some of column four elements was described by Jewsbury and Osborn ( 9 2 ) . Quantitative precipitations were obtained for tin(IV), titanium, zirconium, and thorium, and interference from many associated metals n-as avoided by the use of thioglycolic acid or salicyclic acid, or by controlling the acidity. Gleu and Schwab ( 7 6 ) published a review dealing with the use of dithiocarbamates in place of hydrogen sulfide for the precipitation of metal ions. Haissinsky and Yang ( 7 9 ) examined the stability of the oxalates, tartrates, and citrates of the metals of columns four and five. Their method v a s to determine the p H a t the first appearance of a precipitate on adding hydroxide ion to solutions of the complexed metal. Borrel and P h i s ( I S ) determined the stable heating ranges of the principal metallic precipitates of 8-quinolinol (8-hydroxyquinoline). The data obtained are contrary in some instances to the findings of other investigators. This is an important paper and should be examined by those interested in the analytical aspects of quinolinol Precipitates of the follon ing metals \?ere examined: magnesium, copper, zinc, cadmium, manganese, nickel, cobalt, titanium, zirconium, vanadium, molybdenum, tungsten, thorium, iron, aluminum, and thallium. T h e solubility products of the hydroxyquinolates of aluminum, magnesium, zinc, copper, and iron, and the effects of acidity and excess cations or anions were investigated by Tinovskaya (167). T h e application of pyramidone for the detection and determination of copper, zinc, cadmium, lead, bismuth, antimony, and the metal ions of column eight was discussed by Fungairifio (66). Colin (20) used modifications of Schoeller's tannin methods for the analysis of radioactive minerals. Procedures in outline form were described for the analysis of tantalum-niobium minerals uranium in davidite and samarskite, titanium in complex minerals, and vanadium in roscoelite. The applications of thioorganic compounds as precipitating reagents have been entended further. Thioformamide ( 6 9 ) for arsenic and thioacetamide for arsenic, copper, cadmium, lead (58),and tin ( 6 2 )are added to the already formidable list. Analytical Methods for Specific Materials. The determination of copper sulfate in sulfide ores by diethyl dithiophosphate was described by Iiakovskii and Fedorova ( 9 6 ) . Benzene was used to extract the copper precipitate; zinc could be determined in the aqueous layer. Emblem and Davy ( 4 8 ) determined silicon in silicon tetrachloride by esterifying the dioxane solution with absolute alcohol. The resulting silica gel was dried a t 95" to 100" and ignited to silicon dioxide. A procedure for the sampling and analysis of tool and magnetic steels was recorded by Mazor (114). Young (187)published procedures for the determination of some two dozen elements in copper-refinery slimes. Jean ( 8 9 ) published the first installment of a review of the chemical analysis of siderurgical products. Baron ( 4 ) described procedures, which he preferred to carry out on separate samples, for the determination of water of constitution and of carbon dioxide in ferrous minerals. Theories of Precipitation, New Aids, etc. K e s t and Conrad (181) found t h a t cation impurities tended to coprecipitate to a greater extent with organic precipitants. They suggested that
I
the mechanism involved the flocculation of colloidal particles by electrolytes in the immediate zone of reaction. This was substantiated by the greater degree of coprecipitation of the trivalent cations, chromium and aluminum. The absorption of bivalent metals during the precipitation of hydrated oxides of iron, aluminum, and chromium by ammonia x a s discussed by OkAE and BezdEk (128). The experiments showed that some of the methods of separation were not quantitative even after several precipitations. Kjegovan (126) purified precipitates of barium sulfate and ammonium magnesium and ammonium manganese phosphates by a process of dispersion and digestion. Beck ( 7 ) described a new gravimetric technique which was especially suitable for amorphous and gelatinous precipitates. T h e crucible was attached to a precipitating tube by a ground-glass joint and washing was accomplished by centrifuging. Automatic gravimetric analysis in inorganic chemistry was discussed b y Duval (49). LIGHT 4LLOY ELEMENTS
Beryllium. Osborn (129) investigated the factors affecting the sodium carbonate fusion of beryl. Reliable results were obtained with a fusion ratio of two parts of sodium carbonate to one of beryl, while incomplete extraction with dilute phosphoric or sulfuric acids resulted if higher ratios were used. Qualitative and quantitative analytical methods for copper-beryllium alloys were studied by S6guin and Gramme (160). Systematic experimental comparison of the hydroxide, phosphate, and oxime methods indicated that the best results were obtained by precipitating beryllium as the phosphate after iron and aluminum had been removed as oximes. High values nere always obtained nhen beryllium ITas precipitated by ammonium hydroxide. From a cr:tical study of several recommended procedures Quadrat and Svejda (149) selected the precipitation of beryllium by ammonium nitrite and its separation from aluminum by 8quinolinol. A new method of separation was described which involved formation of an unstable alkali tartrate of beryllium while the aluminum complex remained stable. PPibl and Kucharsky (134) separated beryllium from aluminum in ammoniacal solution by forming a complex with the latter with ethylenediamine tetraacetic acid. Folloiving destruction of the excess of the 01ganic complex, aluminum could be determined in the filtrate. Furuhata ( 6 7 ) separated beryllium and aluminum by dissolving the latter in an alkaline medium. The small amount of dissolved sodium beryllate Tvas reprecipitated on heating to 70 '. h procedure for the separation of beryllium from iron and aluminum in the presence and absence of lithium, magnesium, and zinc was included ( 6 8 ) . Minimum safe ignition temperatures for beryllium hydroxide obtained by seventeen methods were recorded by Dupuis (27). Aluminum. For the direct determination of aluminum, Kassner and Ozier ( 9 9 ) used 8-quinolinol in an ammoniacal solution containing tartrate, cyanide, and hydrogen peroxide. Two methods for the determination of aluminum by anthranilic acid were described by Bhaduri ( 1 0 ) . Mills and Hermon (116) determined aluminum in bronze by precipitation of the hydroxide subsequent to the removal of heavy metals by electrolytic separation with a mercury cathode. Bassett and Tomkins (6) described a procedure for thc determination of aluminum in uraniumbearing material. Following removal of the acid sulfide cations, uranium was precipitated by 30y0 hydrogen peroxide. I n this piocedure precipitation of aluminum by ammonium hydroxide was preferred to the 8-quinolinol method. Magnesium. Westwood and Presser (183) discussed the determination of magnesium in cast iron. Iron was removed by extraction n ith ether, and manganese by electrolysis; magnesium was precipitated as ammonium magnesium phosphate after the remaining elements were complexed with citrate. Hague and Shultz ( 7 8 ) also published a procedure for the determination of magnesium in cast iron. They claimed accuracies of the order of 0.002% magnesium in samples n i t h the range of 0.01 to 0.10%
V O L U M E 2 4 , NO. 1, J A N U A R Y 1 9 5 2 magnesium. After iron was removed by ether extraction, magnesium and some manganese were precipitated by addition of phosphate in ammoniacal citrate solution. Manganese was subsequently separated as the quadrivalent oxide. A procedure for the determination of magnesium in nodular cast iron was recorded by Yarne and Sobers (186); standard methods of separation and precipitation were applied. Valentin and Such&rov&(170) separated magnesium from sodium and potassium by treating the sohtion of sulfates with hydrated silver oxide upon which magnesium hydroxide was selectively adsorbed. NATURALLY RADIOACTIVE ELEMERTS
Thorium and Uranium. Venkataramaniah and Rao ( 1 7 3 ) stated t h a t in nearly neutral solution thorium could be precipitated as Th(IOA)4. The precipitate could be weighed directly. In the presence of small amounts of cerite earths thorium was selectively precipitated from a 4 N nitric acid solution containing 3.5'3 periodic acid. Following the isolation of thorium and ceria earths from monazite, these authors (171) separated thorium by precipitation by sodium naphthionate. With 16 times as much ceria earths as thorium, a single precipitation sufficed. T'enkataramaniah, Satyanarayanamurthy, and Rao (1 7 4 ) found t h a t cerium and zirconium interfered in each of six methods for the determination of thorium. The precipitating agents were trimethylgallic acid; phenoxyacetic acid, benzoic acid, ammonium benzoate, tannic acid, and veratric acid. The last reagent gave slightly high results For the separation of thorium from cerite earths, Rao and Rao (151) used 0- and p-aminobenzoic acids. T h e precipitating medium was buffered on the acid side of Congo red. o-Chlorobenzoic acid was also used to precipitate thorium. Dupuis and Duval (31) recorded data on the thermogravimetry of twenty-four methods of precipitating thorium. Goyanes ( 7 7 ) revie\$ed methods for the detection and determination of thorium. Rodden and Warf (154) made a complete review of the analytical methods for uranium; detailed directions for its gravimetric determination as VJ08a ere included. Organic reagents for the determination of uranium xTwe discussed by Ware (179). .Ilthough not an ideal reagent, 8-quinolinol \$-as considered to be the best of the gravimetric reagents. h manual of analytical methods for the determination of uranium and thorium in ores was published (169). Several standard gravimetric procedures for thorium are included. ALKALI AND ALKALIYE EARTH E L E l l E R T S
Sodium, Potassium, and Rubidium. The separation and determination of sodium oxide in the presence of lithium oxide, potassium oxide, and phosphorus pentoxide was investigated by Shell (163). The solution containing not more than 8 mg. of sodium \?as treated to pxecipitate SaZn(U02)a(0.1c)g. 6H20. Lithium salts and phosphates n ere selectively removed by hydrogen chloride-butanol. The residual sodium chloride was reprecipitated as the triple acetate. Miholiit (115)confirmed the findings of earlier woikers t h a t ethanol could replace water of crystallization in sodium magnesium uranyl acetate. Jackson (88) recorded a new method for the determination of sodium in calcined alumina or its hydrate. After the sample \$as heated with hydrochloric acid in a sealed glass tube, the sodium was precipitated by zinc uranyl acetate reagent. Bourdon ( 1 4 ) found that in the precipitation of K2SaCo(N02)6.H20it was desirable to use an empirical curve for each new lot of reagent. The ratio w.as seldom exactly t n o atoms of potassium to one of sodium and the amount of water also varied. Belcher and S u t t e n (8) offered evidence t o show that the ordinary two-solution reagent for potassium prepared in acetic acid by the method of Hamid (80) produced a precipitate whose composition was more constant than t h a t produced by the Wilcox ( 1 8 4 ) method, which required sodium cobaltinitrite in nitric acid solution. However, in agreement with Wilcox, the results Were high and required a factor of 0.97. An improved technique for
97 the precipitation of potassium by sodium cobaltinitrite was recorded by Mason (113). Bourdon and Gielfrich (15) discussed the composition of cobaltinitrite complexes of potassium with and without other metals. A modified method for the isolation of potassium from fluoride and sulfate ions by an acid-alumina exchange-adsorption column was recorded by Dean ( 2 2 ) . d'Ans (21) provided a method for the extraction of rubidium from carnallites and its determination in the presence of potassium. By means of oxalic acid and a combined fractional crystallization, crystals of RbH,(C%O&.2HZO were obtained. After separation of the perchlorates and subsequent reduction] rubidium n-as determined by a chloride method. Barium. During the period under review no researches on the gravimetric determination of calcium and strontium have been published. Buriiel and Caldas ( 1 6 )found that the interference of the vanadate ion in the determination of barium could be eliminated by coprecipitation of vanadium with aluminum hydroxide. Iron and chromium hydroxide were less efficient. S T E E L F O R U I h G ELEMENTS
Niobium and Tantalum. Hayashi and Katsura (83)found that the optimum p H for the formation of tantalum and niobium tannin complex was influenced by the presence of various alkaloids. Mixtures of brucine and tannin were considered to be the best precipitating reagents for the separation of tantalum and niobium. With tannin and cinchonine in oxalic acid solution a t pH 1.6 all of the tantalum was precipitated while most of the niobium remained dissolved (81). Strychnine acted in the same n a y as cinchonine but was less effective (82). Bhattacharya (11) studied the effect of oxalate concentration and the acidity on the precipitation of tantalum and niobium by tannin. Separation of these elements in 2% ammonium oxalate could be effected in one operation, provided that the amount of tantalum oxide was a t least 75% of the total oxides. Tannin was also used for the separation of tantalum and niobium in the presence of titanium, the latter being almost completely precipitated by tannin from ammonium oxalate a t p H 4.0 (12). Gillis, Eeckhout, and Poma (7'5) separated niobium and tantalum n-ith ferroin in hydrogen fluoride solution. Titanium, Zirconium, and Hafnium. S'arious reagents, weighing forms, and safe temperature ranges for the determination of titanium were published by Dupuis and Duval (33). The iodate, 5,7-dichloro-, and 5,7-dibromo-oxine methods were recommended for automatic determinations. Gavioli and Traldi ( 7 2 ) applied the mandelic acid method to the determination of zirconium in steels and cast irons. Good precision was obtained with synthetic mixtures and alloys containing 0.36 to 3.65% zirconium. Titanium did not interfere. According to Jonckers ( 9 4 ) the reactivity of mandelic acid is due t o the -CHOHC02H group. S i n e compounds containing this group {Teere as suitable as mandelic acid. Sarudi (157) recorded an interesting procedure for the separation of zirconium from iron, aluminum, thorium, and trivalent cerium. Disodium hydrogen arsenate in nitric acid medium was used to precipitate ZrO. HAsOl. I n the absence of excess of reagent the precipitate could be weighed as (Zr0)2-Is20,. Three procedures were included which accomplished the distillation from the precipitate of trivalent arsenic chloride followed by precipitation of hydrated zirconium oxide and ignition to the oxide. Rao and coworkers used hydrazine sulfate (1753, phthalic acid ( I @ ) , tannin (f47),and fumaric acid ( 1 7 2 ) for the precipitation of zirconium. Hydrazine sulfate could be used for the separation of zirconium from thorium a t p H 2.8. Beryllium, nickel, and rare earths could be separated in the pH range 2.8 to 3.0. A single precipitation by phthalic acid in 0.35 -V hydrochloric acid effected a separation from thorium, iron, aluminum, beryllium, uranium, manganese. nickel, and cerium earths. I n the case of tannin the authors studied the effects of acidity ~ i t the h hope of reducing a
98 positive error. Fumaric acid (172) in 0.25 N hydrochloric acid produced excellent precipitations of zirconium in the presence of interfering elements. The precipitate could be purified if necessary after dissolving in hot 6 N hydrochloric acid. Borrel and Pbris ( I S ) recorded that 8-quinolinol with titanium or zirconium produced a mixed precipitate which was unsuitable for quantitative analysis. Fujiwara published two procedures dealing with the determination of hafnium in the presence of zirconium. One method ( 8 4 ) involved a calculation from the weight of the mixed oxides and mixed pyrophosphates. In the second procedure ( 6 5 ) the mixed pyrophosphates were dissolved in hydrofluoric acid. Hafnium and zirconium were precipitated by sodium hydroxide, and treated with sulfuric acid and then the hafnium was largely separated by heating the diluted solution in the presence of hydrofluoric acid. Vanadium. Duval and Llorette ( 4 4 , 4 5 )and hIorette (120) examined existing gravimetric methods for the determination of vanadium. Seven acceptable precipitants and the corresponding safe ignition temperatures were recorded. Among other reagents, eatisfactory results were not obtained by the barium vanadate, cobalt(III), hexammine, oxine, and the dicyanodiamidine methods (120). FidlPr ( 5 5 ) stated that the compositions of the precipitates formed a t room temperature by quinoline and vanadate were constant and independent of the quantity of reagent. Increasing the drying temperatures resulted in increased proportions of vanadium pentoxide. The composition of the precipitates formed by vanadate with quinine, strychnine, and brucine, under various conditions, were also recorded. Rasmussen and Rodden (168) precipitated vanadium as ammonium metavanadate and ignited to the pentoxide a t 500 '. Molybdenum and Tungsten. Dupuis and Duval (32) recommended the oxinate for the automatic determination of molybdenum. They recorded also thirteen weighing forms and their temperature limits. Cinchonine was not considered a satisfactory reagent. Liang and Chang (103) reported on suitable ignition temperatures for the sexivalent oxides of molybdenum and tungsten and the determination of tungsten by alkaloids. Pfibl and hlalkt (135) deteimined sexivalent molybdenum by quinolinol in an acetate-buffered solution of the disodium salt of ethylenediaminetetraacetic acid. Titanium, tungsten, vanadium, and uranium interfered. By varying the procedure slightly copper and iron could be determined. Myers, Shoebridge, and Guerin (122) published a method of analysis for tantalum-rich alloj s. For the determination of tungsten the sample was dissolved in a mixture of hydrofluoric and nitric acids v ith a little sulfuric acid. T h e evaporated residue was fused with potassium carbonate, tantalum was removed as magnesium tantalate, and tungsten was recovered by the tannin-cinchonine method. A recipe was included for the treatment of the sample preliminary to the determination of molybdenum \\ hich was isolated as the sulfide and weighed as lead molybdate. The use of benzidine for the determination of tungstophosphoric anhydride in sodium tungstophosphate was discussed by Nazarenko and Shvartsburd (125). Manganese and Rhenium. Dupuis, Besson, and Duval (28) stated that the only precipitates suitable for the automatic determination of manganese were the sulfate, oxalate, anthranilate, and oxinate. Pyrolysis curves for some other compounds were also recorded. Manganese monoxide was stable a t 436" to 610"; and trimanganese tetroxide was found stable a t 946' to 1000". Njegovan and Morsan (1a7) published a procedure which produced pure ammonium manganese phosphate monohydrate. Geilmann and Bode ( 7 3 ) found that in the absence of nitrates septivalent rhenium sulfide could be precipitated by sodium thiosulfate in 2 to 7 AT sulfuric or l to 4 N hydrochloric acids. The precipitate could be dissolved by treatment with 10% sodium hydroxide and 30y0 hydrogen peroxide. Iron, Cobalt, and Nickel. The separation of iron as basic formate from homogeneous solutions with urea was recommended
ANALYTICAL CHEMISTRY by Willard and Sheldon (185). The precipitate was denser, more readily filtered, and adsorbed fewer impurities than the precipitate obtained by any other hydrolytic procedure. A modified two-stage precipitation effected excellent separations from bivalent metals. Gaspary Arnal and Miner Liceaga ( 7 1 ) extended the application of sulfates and sulfites to the determination of tervalent iron. Sodium sulfite in 60% ethanol was added t o a neutral 60% ethanol solution of iron containing ammonium chloride. The precipitate was converted to and weighed as sulfate after final drying a t 405". Koszegi (101)found filtrations of hydrated iron oxide were improved if the hot iron solution was treated with ammonium hydroxide and later with a cold saturated solution of hydrazine sulfate. By complexing titanium with salicylate in the presence of ammonium carbonate Mannelli (110) was able to separate iron by precipitation as sulfide. Titanium was then determined by addition of ammonia. Similar separations of iron from manganese and thallium were recorded. Jean (90) published a bibliography of the chemical analysis of ferrous products. Iiallmann (96) precipitated cobalt as potassium cobaltinitrite. The addition of tartaric acid as a complexing reagent improved the scope and usefulness of the method. The modified procedure served as an excellent separation from virtually any combination of elements encountered in the metallurgical field. In the presence of large quantities of tantalum, niobium, and titanium which could not be held in solution by tartaric acid alone, hydrofluoric acid was of considerable value. I n the precipitation of cobalt(II1) hydroxide, Baker and JIcCutcheon (3) removed adsorbed alkali by dissolving the precipitate in hydrochloric acid, treating with hydrogen peroxide, and precipitating with trimethylbenzylammonium hydroxide, The thermogravimetry of cobalt precipitates was discussed by Duval and Duval (47). The anthranilate method was considered the best of all methods. The rejected methods were: molybdate, l-nitro-2-naphtho1, dinitrosoresorcinol, and dinitrosoorcinol. These authors ( 4 6 ) also determined the safe heating ranges of nickel precipitates. I t is of particular interest that the cyclohexanedione dioxime method was considered particularly efficient. Other preferred methods were iodide-iodate, anthranilic acid, and dimethylglyoxime. The rejected methods were sodium thiosulfate, salicylaldehyde, dicarbamidoglyoxime, diphenylglyosime, a-furildioxinie, zinc, and ammonia. Various publications (93, 136, 178) have dealt with interference of metal ions in the determination of nickel by 1,2-cyclohesanedione dioxime. Feinstein ( 6 6 ) recorded an additional procedure which avoided the interference of iron. Kur&s (103) used oxalendiamidoxime for the determinations of nickel. The reagent was water-soluble and the orange-yellow precipitate was weighed directly. Sapir (155) preferred hot aqueous solutions (85' to 90 ") of dimethylglyoxime for the determination of nickel in steel. Ammoniacal solutions gave low results. NONFERROUS ELEMENTS
Copper, Cadmium, Zinc, and Thallium. Sarudi (166') published a procedure for the determination of copper as copper( I) thiocyanate and its separation from arsenic and zinc. An excess of thiocyanate was found necessary. The purified precipitate could be dried a t 100' t o 180' and weighed. It was considered advisable to use a separate sample for the determination of arsenic. However, both arsenic and zinc could be determined in the filtrate from the copper( I) and thiocyanate precipitation; arsenic was removed as the sulfide and finally weighed as magnesium pyroarsenate; zinc was determined as ammonium zinc phosphate. For samples containing no more than 100 mg. of cadmium, Denk and Denk ( 2 3 ) recommended the sulfide precipitation from perchloric or sulfuric acid solutions. T h e pure cadmium sulfide could be dried a t 120" to 130" and weighed. Flaschka and Jakobljevich (80) used thioacetamide for the quantitative pre-
V O L U M E 2 4 , NO. 1, J A N U A R Y 1 9 5 2 cipitation of cadmium sulfide Zhivopistsev (188) used diantipyrylmethane to precipitate cadmium in the presence of copper, cobalt, nickel, aluminum, chromium, iron(II), and alkali and alkaline earth metals. The precipitate was dried a t 110 O to 120 '. The thiosemicarbazone of salicylaldehyde was used by Hovorka and Holzbecher (86) to precipitate cadmium in solutions containing sulfate and nitrate ions. Chloride, fluoride, tartrate, and citrate prevented complete precipitation. Duval ( 4 2 ) published safe ignition temperature ranges for twenty-eight methods for the determination of cadmium. Osborn (130) recorded a method for the determination of zinc oxide in zinc powder. Murakanii (121) used hexamniinecobalt(II1) chloride to determine thallium in chamber muds of sulfuric acid plants and in the flue dust formed during the calcination of ores. The procedure provided for the remofal of lead, bismuth, tin, antimony, mercury, etc. Nakano (123) discussed the determination of thallium as cobaltinitrite. Germanium, Tin, and Lead. Dupuis and Duval(35) recorded safe temperature limits for heating precipitates of tin. The cupferron method was considered best, while the benzenearsonic acid and tannin methods of precipitation were not recommended. These authors (94) published similar data for the determination of germanium. The cinchonine method was considered unsatisfactory. Selenous acid was used by Carvalho (17) for the precipitation of tin. Coprecipitation of titanium and cerium was prevented by the addition of hydrogen peroxide. Flaschka and Jakobljevich (62) found that thioacetamide could be used to precipitate tin sulfide, provided mercury(I1) chloride was added to the suspension of the precipitate. The results were a little low. I n the determination of tin in steels, Bagshawe (2) removed tin sulfide along with molybdenum(I1) sulfide as a gathering agent. Finally iron was added to the solution of the above mixed sulfides, and this and the tin together were precipitated by ammonia. Duval (41) recorded pyrolysis curves for all precipitates which have been proposed for the gravimetric determination of lead. For automatic determination, lead sulfide and the thionalide complex were considered the best of thirteen suitable methods. Dupuis (26) found that colloidal formation of lead tungstate prevented its use for gravimetric determinations. Flaschka and Jakobljevich (61) studied the precipitation of lead sulfide from acid and alkaline solutions by thioacetamide. Although the lead sulfide could be weighed after drying a t 110", conversion of the precipitate to lead sulfate produced more accurate results. Hovorka and DiviB (85) determined lead by &satin oxime. The blue precipitate was dried a t 105" to 110" following a treatment with ethanol and ether. I n the analysis of fusible alloys Etheridge (49) found that fuming a t 250' eliminated contamination of lead sulfate by bismuth, but a t 350' to 400" contamination became significant. Arsenic, Antimony, and Bismuth. ChernyI and Podoinikova (18,19) determined arsenide-sulfide minerals in sulfide and arsenosulfide ores by differential thermal decomposition. Two samples mixed with aluminum oxide were heated a t 400 O and 500 O , respectively. The boat residues were analyzed for nickel, cobalt, and sulfur and the difference between the two sets gave the proportion of these metals present as arsenosulfide minerals. To precipitate trivalent or quinquevalent arsenic sulfide Gagliardi and Loidl (69) used thioformamide, and Flaschka and Jakobljevich (69) used thioacetamide. Dupuis and Duval ( 3 7 ) recorded safe ignition temperatures for arsenic precipitates. They rejected the xanthogenate, uranium arsenate, and molybdoarsenate methods. Thioacetamide was also used by Flaschka and Jakobljevich (69) for the determination of antimony. Either the black or red sulfide could be used, although the former was more convenient and accurate. The red precipitate was dried in carbon dioxide at 280" to 300"; the black modification was dried a t 120'. The thermogravimetry of antimony precipitates was studied by Morandat and Duval (119). The thiocyanate was considered
99
the best of all methods. Tannin and 8-quinolinol were considered to be unsatisfactory precipitants. Majumdar and Sarma (108) stated that under suitable conditions benzenearsonic acid could be used to precipitate bismuth free of zinc, manganese, nickel, cobalt, lead, mercury, thallium, sulfate, alkalies, and alkaline earths. RARE EARTH ELEMEhTS
The precipitation of rare earth elements by ammonia and oxalic acid as applied to minerals was discussed by Serebrennikov (16.2). In the presence of much iron and aluminum the oxalate method produced Ion results and the fluoride method should be used. A recommended alternative was outlined. Beck ( 6 ) stated that scandium produced a salt insoluble in mineral acids with aneurine pyrophosphate, and with adenosine triphosphate a salt insoluble in acetic acid. Zirconium was the only interfering element. Dupuis and I h v a l (SO) determined pyrolysis C U N ~ S for gadolinium oxide. T H E NOBLE ELEMENTS
Silver and Gold. .4 new organic precipitant for silver g-as recorded by Tarasevich (165). The bromine derivative of benzo1,2,3-triazole precipitated silver in the form of CsH3BrN8Ag, which was stable to heat and light, and insoluble in aqueoue ammonia, organic solvents, or dilute acids. Determinations could be made in the presence of copper, nickel, bismuth, thallium, lead, and chlorine. Directions for the preparation of the reagent were included. Wenger (180) recorded a new gravimetric reagent for silver and copper. I-Nitroso-2-naphthol precipitated silver a t p H 8.5 in the presence of a borax-boric acid buffer. The copper compound was precipitated a t p H 5.6 in the presence of an acetic acid-sodium acetate buffer. The p r e cipitation of silver chloride from perchloric acid solutions and other mineral acids was discussed by hIills and Hermon (117). Marin and Duval (111 ) recorded safe ignition temperature limits for precipitation forms of silver. A new compound, HOCH2.NAg , CH,OH, formed by precipitation by formaldehyde and ammonia was recorded. Malowan (109) used morpholine oxalate to precipitate gold Nitric acid interfered. Platinum Metals. VoFiBek and VejdElek (177) used the hydrazide of m-nitrobenzoic acid for the determination of palladium. I n mineral acid solutions only gold interfered, but in neutral solution the reagent also precipitated mercury (11),copper, iron, nickel, molybdenum, platinum, and osmium. The precipitate rras finally ignited to palladium. Jackson and Beamish ( 8 7 ) examined in detail the platinum sulfide precipitation. High results always attended the formation of sulfide from solutions of sodium hexachloroplatinate, but very accurate results were obtained in the absence of complexed sodium chloride. The retention of sulfur in platinum sulfide did not account for positive errors. Hill and Reamish (84) examined the efficiency of chlorination of iridium and iridosmine. A considerable amount of w-ork on the determination of platinum metals has been recorded by Pshenitsyn and coworkers. Of ten publications, five deal with the analysis of copper-nickel slimes. I n general, the methods involve the application of wellknown procedures. For the collection of palladium and platinum, acetylene was used by Pshenitsyn, Ginzburg, and Sal'skaya (149). The method was considered accurate to within 1.5%. The calomel method was used for the same purpose by Pshenitsyn and Yakovleva (146). There were no interferences from copper, nickel, iron, iridium, or rhodium. Precipitation as ammonium chloroplatinate and chloropalladate was used by Pshenitsyn and Gladyshevskaya (144). The platinum metals were selectively extracted by treatment with aqua regia. Perhaps the most significant of the five reports (145) described the selective extraction of the base metals from the slimes by fusion with borax a t 1200". Lead and silica were removed from the platinum metals
ANALYTICAL CHEMISTRY
100 residue by conventional procedures. Attempts to collect platinum and palladium in the flux by means of a silver button failed. Pshenitsyn and Fedorov (139) determined ruthenium in slimes by a procedure which involved the initial removal of base metal impurities by standard procedures followed by a series of fusions, then reduction by alcohol to isolate ruthenium and other platinum metals. Fusions with sodium carbonate and subsequent reduction with zinc or magnesium produced ruthenium with traces of platinum; the latter could be removed by leaching u ith aqua regia. This procedure seems somewhat cumbersome. Procedures for the separation of rhodium from iridium LT-ere also recorded by Pshenitsyn. Chromium(I1) chloride (138) was used to reduce rhodium to metal. This procedure will involve the subsequent difficult separation of iridium and chromium. The second procedure (140) is an application of the lengthy procedure originally described by Gibbs in 1863. Pshenitsyn and Ginzburg (142) used zinc oxide for the hydrolytic separation of platinum metals. The hydrated oxides were contaminated by platinum and two or more precipitations were necessary for its removal. Excess zinc oxide also resulted in adsorption of platinum. I n the separation of platinum from iridium, chlorine was used as the oxidizing reagent. Reviews of methods of analysis of the platinum group metals were also published by Pshenitsyn ( 1 3 7 ) and Pshenitsyn and Ginzburg (141). h7ew rapid methods for determining platinum metals in concentrates and mattes and nonsiliceous ores were developed by Seliverstov (161). Hot sulfuric acid extacts were treated with sulfur and the resulting sulfides were roasted, litharge, silica, etc., were added, and the mixture was subjected to fire assay. The silverplatinum metals bead was treated by known methods. An alternative procedure, applied to rich ores, etc., involved continued wet treatment of the oxidized residue by adaptations of standard methods. For the separation of small quantities of rhodium in platinum catalysts Ubaldini (168) treated the aqua regia extract with ammonium acetate and formic acid to produce a precipitate of rhodium and platinum from which the rhodium was isolated by fusion u i t h potassium pyrosulfate. NONMETALLIC ELEMEhTS
Boron, Carbon, and Silicon. Duval(40) investigated the ignition temperature limits for gravimetric precipitates used in the determination of boron. Kitron fluoborate was recommended for the automatic determination. hIajumdar (106, 107) recorded methods for the analysis of adulterated graphite. Complete combustion of volatile matter and adulterants such as charcoal, coal, and coke required 5 to 20 minutes. Errors of less than 2% were obtainable. The determination of carbon in steel was discussed by Popova and Rybina (135). A procedure was included to obtain the total carbon and the free carbon in the carbide. Dupuis, Besson, and Duval (29) recorded ignition temperature limits for ten silicon precipitates, eight of which were suitable for automatic methods, A procedure for the extraction and determination of silicon in aluminum and its alloys was published by Berthier (9). The alloy was amalgamated by mercury in a sulfuric acid solution. Follo~vingremoval of the latter, the aluminum \vas dissolved by concentrated hydrochloric acid and the silicon Tvas precipitated by dilution. Dodero and Rambeaud ( 2 4 ) recorded some improvement in the procedures for the determination of silicon in chromium steel. Aubry and Turpin (1) treated iron ores with an acetic acid-sodium acetate mixture. To determine silica the residue was selectively extracted with sodium sulfide, then with hydrochloric and nitric acids. In the determination of silicon in ferrous alloys, Jenkins and Webb (91) obtained precise and accurate results through the use of gelatin. Nardell ( 1 2 4 )isolated dodecatungstosilicate by precipitation by benzidene. Phosphorus. Frey ( 6 3 ) studied the relative rates of molybdophosphate precipitation and the formation of polymolybdate as a function of temperature, ratio of molybdate excess to nitric
acid, amount of ammonium nitrate, stirring rate, and total volume. While variations of volume had little effect, increasing any of the other variables resulted in increasing both the rate of precipitation and the polymolybdate formation. Two methods of precipitation were described. Templeton and Bassett (166) recommended precipitation by ammonium molybdate as the most accurate method for the determination of phosphate; the precipitate was dissolved in ammonium hydroxide, converted to ammonium magnesium phosphate, and ignited to the pyrophosphate. In some cases phosphate was precipitated as ammonium uranyl phosphate (UO&H,PO$) and weighed as uranyl pyrophosphate. The degree of interference of arsenic in the determination of phosphorus in steels was investigated by Kitahara (100). The error in the phosphorus values owing to arsenic in excess could be minimized by precipitating ammonium molybdophosphate below 45" and washing with ammonium nitrate and nitric acid solution a t 10" to 15'. Mager (105) described a procedure for the determination of total phosphoric acid in phosphates. Kassner and Ozier (98) extended the analytical usefulness of the doublestrength citromolybdate solution to include the determination of phosphorue in alloys. Kanevskaya (97) recorded a procedure for the rapid determination of phosphorus in iron ore essentially free of titanium, arsenic, and vanadium. Dupuis and Duval (38) investigated ignition temperature limits for phosphorus precipitates. A detailed study was made of the precipitation by molybdic acid reagent. Sulfur. Precipitants, weighing forms, and ignition temperature limits for the gravimetric determination of sulfur and its organic derivatives were discussed by Dupuis and Duval (39). Fischer and Sprague (56) found that the incomplete precipitation of benzidine sulfate in the presence of foreign ions was more probably the result of imperfect crista1 formation than of increased solubility. FigurovskiI and Ushakova (55) examined methods of regulating the dispersion of barium sulfate by addition of picric acid, pyridine, salicylic acid, etc. Liang and Hsu (104) stated that the tendency of manganese, cobalt, and nickel ions to copreripitate with barium sulfate in 0.2 acid was almost negligible. Milner and McXabb (118) recorded a procedure for the determination of sulfur as barium sulfate in the presence of feriir ion. The former was first precipitated in the presence of ferric hydroxide, then filtered after addition of excess hydrochloric acid. K i t h more than 200 mg. of iron, contamination became significant. A method for the determination of sulfur in zinc blende by oxidation by hydrogen peroxide in an oxalic acid medium \vas recorded by Feh& and Heuer (51). The oxides of sulfur were distilled into ammoniacal hydrogen peroxide and subsequently determined as barium sulfate. A procedure for the determination of sulfur trioxide in liquid sulfur dioxide was described by Steinle (164). A frozen mixture of barium chloride and formalin was added to liquid sulfur dioxide previously chilled by dry ice. Halogens. Georch (74) studied the determination of fluorine by precipitation of lead chlorofluoride by lead chloride. Dupuis and Duval (38) recorded pyrolysis curves for precipitates used in gravimetric determinations of halogens, either as simple or complex ions. LlTERATURE CITED
(1) Aubry, J., and Turpln, G., Reo. mdt., 47, 146-7 (1950). (2) Bagshawe, B., J . Iron Steet Inst. (London), 165, 190-7 (1950).
ANAL.CHEM.,22, (3) Raker, L. C. W., and McCutcheon, T. P., 944-5 (1950). (4) Baron, J . , Chzm. anal., 33, 92-4 (1951). ( 5 ) Bassett, L. G., and Tomklns, F. S.,"Analytical Chemistry of the Manhattan Project," pp. 382-91, New York, hIcGrawHill Book Po., 1950. (6) Beck, G., A n a l . Cham Acta, 4, 21-2 (1950). (7) Ibid., pp. 245-6. (8) Belcher, R., and Nutten, A. J., Ibid., 4, t75-81 (1950). (9) Berthier, R. M., Bzdl. soc. chzm. France, 1950, 363-4. (10) Bhaduri, A., J. I n d i a n Chem. Soc., 27, 281-2 (1950).
V O L U M E 2 4 , NO. 1, J A N U A R Y 1 9 5 2
H.,Science and Culture, 16, 69--70 (1960). (12) Ibid., pp. 121-2. (13) Borrel, XI., and Phis, R., -4nal. C h i m . Acta, 4, 267-85 (1950). (14) Rourdon, D., Chim. anal., 32, 273-8 (1950). (15) Bourdon, K., and Gielfrich, .If. L., Bull. soc. sci. Bretagne, 23, 117-22 (1948). (16) Hurriel, F., and Caldas, E. F., Anales real soc. espac. fis. y qzaim., 46B, 37-46 (1950). (17) Carvalho, R. G. de., IZezs. gzrim. p i ~ r ae aplicada, (4) 1, KO. 1. 24-41 (1050). (18) Chernyi, A. T., and Podoinikova, IC. V., Zauodskaya Lah., 16, 775-6 (1950). (19) Ibid., pp. 1031-5. (20) Colin, L. L., 6.Chem. M e t . M i n i n g Soc. S. A f r i c a , 50, 314-19 (1959). (21) d'Ans, J., Angela. Chem., 62, 118-19 (1950). (22) Dean, J. A., ANAL.CHEM..23,202--4 (1951). (23) Denk, G.. and Denk, F., 2. Anal. Chem., 130,383-90 (1950). (24) Dodero, hZ., and Rambeaud, R., Rev. mkt., 47, 315-16 (1950). (25) Draney, J. J., Tanowski. L. K., and Cefola, M., Mikrochemis ver. Mikrochim. Acta, 35, 238-41 (1950). (26) Dupuis, ThkrBse, A n a l . Chim. Acta, 3. 663-4 (1949). (27) Dupuis, 'Ihbrese, Mikrochemie cer. Mikrocham. Acta, 35, 47787 (1950). (28) Dupuis, ThhBse, Besson, J.. and Duval, Clbment, A n a l . Chim. d c t a , 3, 599-605 (1949). (29) Ibid., 4, 50-4 (1950). (30) Dupuis, ThbrBse, and Duval, ClBment, Ibid., 3, 438-9 (1949). (31) Ibid., pp. 589-98. (32) Ibid., 4, 173-9 (1950). (33) I t i d . , pp. 180-5. (34) Ihid., pp. 186-9. (35) r h i d . , D ~ 201-3. . (36) Ibid., pp. 256--61. (37) Ihid., pp. 262-6. (38) Ibid., pp. 615-22. (39) Ibid., pp. 623-8. (40) Duval, Clbment. Ibid., 4, 55-8 (1950). (41) Ibid., pp. 159-72. (42) Ibid., pp. 190-200. (43) Duval, Clbment, Mikrochemie Der. Mikrochim. Acln, 35, 242-61 (1950); Anal. Chim. 4 c t a , 2, 432-4 (1948). (44) Duval, Clbment, and Morette, AndrB, Ibid., 4, 490-7 (1950). (45) Duval, Clbment, and Morette, Andrb, Compt. rend.. 230, 545-7 (1950). (46) Duval, Raymonde, and Duval, C!kmont, Anal. C h i m . Acta, 5, 71-83 (1951). (47) Ibid., pp. 84-97. (48) Emblem, H. G., and Davy, V. I?., J . SOC.Chem. I n d . ( L o n d o n ) , 69, 255-6 (1950). (49) Etheridge, .4.T., Analyst, 75, 279 (1950). (50) Fainberg, 8. Yu., and Kedrora, Yu. K., Zai,odskayn Lab., 16, 624-5 (1950). (51) Fehbr, F., and Heuer, E., Angew. Chem., 62, 162-5 (1950). ( 5 2 ) Feinstein, H. l . ,ANAL.CHEX.,22, 723-4 (1950). (53) Fidler, Josef, Chem. Ohzor, 25, 1-5 (1950). (54) Fidler, J., Collection Czechoslot'. Chem. Communs., 14, 645-54 (1949). ( 5 5 ) Figurovskii, N. A , , and Ushakova, X. K.,Zaaods.kaya Lah., 16, 1063-71 (1950). (56) Fischer, R. S.,and Sprague, R. S., A n a l . Chim. Acta, 5, 98-101 (1951). (57) Flaschka, H.. and Jakobljevich, H., Ibid., 4, 247-55 (1950). (58) Ihid., pp. 482-5. (59) Ibid., pp. 486-9. ( 6 0 ) Ihid., pp. 602-5. (61) Ibid., pp. 60G-9. (62) Ibid., 5, 60-2 (1951). (63) Frey, hfichel, BILIZ.soc. c h m . France, 1950, 685-90. (64) Fujiwara, Shizuo, J . C'hem. Soc. J a p a n . , Pure Chem Sect., 70, 129-31 (1949). (65) Ihid., pp. 132-3. (60) FungairiBo. 1,. V., h a l e s real acad. f a r m . ( M a d r i d ) , 16, 209-16 (1950). (67) Furuhata, Takeshi, R e p t s . S e i . Rcsaarch Inst., 25, 402-4 (1949). (68) Ihid., pp. 405-7. (69) Gagliardi, E.. aud Loidl. A., 2. a n d . Chem., 132, 33-6 (1951). (70) Galmks, P. J.,and hlataix, C.,Afinidad, 27, 401-2 (1950). (71) Gaspary A r n d . T., and Miner Liceaga. J., Anales real. SOC. e s p a i l . ffs. y quim., 46B, 23-36 (1950). (72) Gavioli, G . , and Traldi, E., Met. ital., 42, 179-81 (1950). (73) Geilmann, IT., and Bode, H.,Z.anal. Chem., 130,222-32 (1950). (74) Georoh, F., M u g y a r Chem. Folyoiraf, 56, 126-30 (1950). ( 7 5 ) Gillis, J., Eeckhout, J., and Poma, K., Mcdedeel, Koninkl.
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Klasse Wetemchap.. 6, S o .
101 (76) Gleu, K., and Schwab, R., Angew. Chem., 62A, 32C-4 (1950). (77) Goyanes, C. B., Ret. geofis., 8, 183-97 (1949). (78) Hague, J. L., and Shultz, J. I., Foundry, 78, No. 10, 92-3,
210-11 (1950). (79) Haissinsky, hl., and Yang, Jeng-Tsong, A n a l . Chim. Acta, 3, 422-7 (1949). (80) Hamid, M. A,, Analyst. 51, 450-3 (1926). (81) Hayashi, Shigehiko, J . Chem. Soc. J a p a n , Pure Chem. Sect., 70, 376-9 (1949). (82) Hayashi, Shigehiko, and Katsura, Tetsuo. Ibid., 70, 435-7 (1949). (83) Ihid., pp. 437-9. . 22, 590-4 (1950). (84) Hill, M.A., andBeamish, F. E., h . 4 ~ CHEM., (85) Hovorka, V., and DiviS, L., Collection C2cchoslov. Chem. Communs., 14, 473-89 (1949). (86) Hovorka, V., and Holzbecher, Z., Ibid., 15, 275-80 (1950). (87) .Jackson, D. S.,and Beamish, E'. E., .\SAL. CHEM.,22, 813-17 (1950). (88) Jackson, H., Analyst. 75, 414--20 (1950). (89) Jean, M.,Chim. anul., 32, 133-8 (1950). (90) Ihid., pp. 179-84. (91) Jenkins, hl. H., and Webb, J. A . V.,Analyst, 75, 451-5 (1950). (92) Jewsbury, A., and Oshorn, G. H., A n a l . Chim. Acta, 3, 642-55 (1949). (93) Johnson, W.C., and Simmons, hI., Analynt, 71, 554-6 (1946). (94) Jonckers, hl. D. E., Chim. anal., 32, 207-12 (1950). (95) Kakovskii, I. A., and Fedorova, hZ. K.,Zavodskaga Lab., 16, 414-17 (1950). (96) Kallmann, Silve, ASAL. C m m , 22, 1519-21 (1950). (97) Kanevskaya, R. I., Z a u o d s k a w Lab., 16, 35C-7 (1950). (98) Kassner, J . L., and Ozier, hi. .4.,A s . 4 ~ CHEM., . 22, 1216-17 (1950). (99) Kassner, J. L., and Ozier. bl. A , J . Am. Ceram. Soc., 33, 250-2 (1950). (100) Kitahara, Saburo, R e p l s . Sei. Research Inst. ( J a p a n ) , 24, 385-7 (1948). (101) Koszegi, Denes, 2. anal. Chem., 130, 401-2 (1950). (102) Kur&s,hl., Chem. L i ~ t y38, , 54-5 (1944). (103) Liang, S.-C., and Chang, K.-N., Science Rccwd, 2, 295-302 (1949). (104) Liang, S.-C., and Hsu, H. H. P., J . Chinese Chem. Soc., 17,18-29 (1950). (105) hlager, Dora, 2.anal. Chem., 131, 270-3 (1950). (106) hlajunidar, K. K., J . Sci. &. I n d . Research ( I n d i a ) , 8B, 168-9 (1949). (107) Ihid., 9B, 22-3 (1950). (108) hlajumdar, A. K., and Sarma, R., J . I n d i a n Chem. Soc., 26, 477-82 (1949). (109) hfalowan, L. S.,Mikrochemie Der. Mikrochim. Acta, 35, 104-8 (1950). (110) Mannelli, G., Ann. chim. applicata, 38, 594-601 (1949). (111) hfarin, Y., and Duval, C., A n a l . Chim. Acta, 3, 303-400 (1949). (112) Martinez, F. B., Anales real. SOC. espafi. fis. y q u h . , 46B, 399402 (1950). (113) Mason, .4. C., A n a l y s t , 75, 176-7 (1951). (114) Mazor, L., M a g y a y Chem. L o p j a , 4, 507-10 (1949). O C . 271, 41-4 (1948). (115) Wiholii., S., Rad. J U ~ O S ~Akad.. (116) Mills, E. C., and Hermon, S.E., M e t a l I n d . (London),76, 343-4 (1050). (117) Mills, E. C., and Hermon, S. E., Metallurgia, 42, 157-8 (1950). (118) Xfilner, 0. I., and McKabb, K. M., A n a l . Chim. Acta, 4, 386-8 (1950). (119) hlorandat, J., and Duval, C., Ibid., 4, 498-503 (1950). (120) Rforette, A, B u l l . soc. chim. France, 1950, 526-32. (121) Murakami. Yukio. Bull. Soc. Chem. Javan. 22. 206-12 (1949). (122) Myers, R. H., Shoebridge, R., and Gucrm, B. D., Metallurgiu, 42, 8-9 (1950). (123) IYakano, S.,J . Chem. Soc. J a p a n , Pure Chem. Sert., 70, 60-1 (1949). (124) Naidell, hI., Ann. chtm npplzcata, 40, 490-3 (19501. (125) Iiazarenko, V. A., and Shvartsburd, L. E., Zavodskayn Lab.. 16, 357-8 (1950). (126) IijegoTaii, V. N.,A n a l . Chzm. Acta, 5 , 55-9 (1951). 1127) Sjegovan, V. N., and Mnrsan, B., 2. anal. Chem., 131, 187-91 (1950). (128) OkBE, A., and Bezdek, RI., Chem. Listu, 44, 30G5 (1950) (129) Osborn, G. H., Analyst, 72, 475-8 (1947). (130) Ihzd., 76, 114-15 (1951). (131) Peltenburg, E., Re?.facultad cicnc. quim.. 22, 175-82 (1949). (132) Peshkova, V. AI., 1-edernikova, M. 1 , and Gontaeva, N. I., Zhur. A n a l . Khtm., 3, 366-72 (1948) (133) Popova, N. M., and Rybina, AI. F., Zazodakaya Lab., 16,280-3 (1950). (134) Pri'bl, R., and Kucharsky, K., Collection Czechoslov. Chem. Commzcns., 15, 132-46 (1950). (135) Pribl, R., and MalPt, hf.. Ihid.. 15, 120-31 (1950).
ANALYTICAL CHEMISTRY Proskuryakora. G. F., Zacodsknuu I,&., 16, 364-5 (1950). Pshenitsyn, S . K . , Izrest. Sektora Platin!! 1‘ Drugilch Blngorod Metal., Inst. Obshchei I . Scorg. I i h i m . A k a d . , S a u k . S.S.S.R., S O .22, 7-15 (1948). Ibid., pp. 16-21, Pshenitsvn. S.IC.. and Fedorov. I. A . . Ibid.. S o . 22.76-9 (1948). Pshenitsyn, T.K., Fedorov, I. A , , and Simanorakiy, P. V., Ibid., KO. 22, 22--7 (1948). Pshenitsyn, N. K., and Ginzburg, S. I., Ibid., N o . 22, 136-44
(1948). Ibid., KO.24, 118-20 (1949). Pshenitsyn, K . K., Ginzburg, S . I., and Yal’skaya, L. G . . Ibid., TO.22, 64-75 (1948). Pshenitsyn, S . K.. and Gladyshevskaya, K. A,, Ibid., T o . 22, 60-3 (1948). Pshenitsyn, N. K., and Lazareva, M.V., Ibid., No. 22, 49-59 (1948). Pshenitsyn, S . K., and I’akovleva, E. A , , Ibid., KO. 22, 43-48 (1948). Puroshottam. A . , and liao, Bh. 9. V. R., Analyst, 75, 555-7 (1950). Ibid., pp. 684-6. Quadrat, O., and Svejda, Z., Chem. Obzor, 25,85-7 (1950). Rafter, T. A , A n n l y s t , 75, 485592 (1950). Rao, B. R.,and Rao, Bh. S.V. R., J . I n d i a n Chem. Soc., 27, 467-8 (1950). Rasmussen, S.W., and Rodden, C. J., “Analytical Chemistiyof the Manhattan Project,” pp. 459-82, New York, McCrawHill Book Co., 1950. Rby, Priyadaranjan, and Bhaduri, Ajitsankar, J . I n d i a n Cheni. SOC.,27, 297-304 (1950). Rodden, C. J., and Karf, J. C., “Analytical Chemistry of the Manhattan Project,” pp. 1-159, New York, McGraw-Hill Book Co., 1950. Sapir, A. D., Zaroddkaya Lab., 16, 494 (1950). Sarudi, Imre, 2. anal. Chem., 130, 301-3 (1950). Ibid.. 131. 416-23 11950). Ibid., pp. ’424-6. Seelyo, F. T., and Rafter, T. A., Xafure, 165, 317 (1950) Seguin, M . , and Gramme, I,., Bull. SOC. chim. France, 1950, 375-84. Seliverstov, K. S., Izrest. Scktora Platiny i Drugikh B l n g o i o d Metal, I n s t . Obshchei i IVeorg. Khim. Akad., S a u k . S.S.S.R., KO. 22, 80-94 (1948). Serebrennikor, V. V., C’chenye Z a p i s k i Tomsk., Gosiidomt Cniz.. im. S.V . Kuibysheca, 1948, S o . 8 , 111-23. ~
Shell, H. R., A K ~ LCHEV., . 22, 575-7 (1950). Steinle, Heins, Z.annl. Chcnc., 129, 340-5 (1949). Tarasevich, K, I., Vestnik M o s k o ~ rnia., 3, N o . 10, 161-8 (1948). Temuleton. D. H.. and Bassett L. G.. “hnalvtical Cheniistrv of the Manhattan Project,” pp. 321-38, S e w York, McGran:Hlll Book Co.. 1950. Tinovskaya, E. S.,Zhzcr. Anal. Khzm., 5, 345-53 (1950). Ubaldini, I., Proc. X I t h Intern. Congr. Pure and Applied Chenr. ( L o n d o n ) , 1, 293-5 (1947). U. S. Atomic Energy Commission, “Manual of Analytical Methods for the Determination of Cranium and Thorium in Their Ores,” Kashington. Gorernnient Printing Office, 1950. Valentin, F., and Suchhrori, Ai., Chem. Zvesti, 4, 68-80 (1950). Venkataramaniah, II.,and Rao. Bh. Y. T’. R., d n o l i p t , 75,. 553-4 (1950). Ibid., 76, 107-9 (1951). Venkataramaniah, RI., and Rao, Bh. S. V. R., J . I n d i a n Chem. Soc., 26, 487-9 (1950). Venkataramaniah, XI., Satyanara~anamurt~iy,T. K., and Rao, Bh. S. V . R., Ibid., 27, 81-6 (1950). T’enkateswarlu, Ch., and Rao, Bh. S. V, R., Ibid., 27, 395-6 (1950). Visman, J., Fuel, 29, KO.5, 101-5 (1950). Vo?iSek, J., and T’ejdslek, Z., Chem. Listy, 37,50-3, 65-70, 91-5 (1943). Voter, R. C., Banks, C. Y.,and Diehl, H., ANLL. CHEY., 20, 458-9 (1948). Ware, E., U. S.Atomic Energy Commission, Rept. MDDC-1432 (August 1945). Wenger, P. E., hionnier. D., and Besso, Z., S n a l . Chini. A d a , 3, 660-2 (1949). West, P. IT.,and Conrad, L. J.. Ibid., 4, 561-5 (1950). Westwood, W,, Brit. Cast I r o n Research Assoc. J . Research & Del;eZo?jment,3 , 377-80 (1950). Westwood, W,, and Presser, R., Ibid., 3, 515-19 (1950). Wilcox, L. V., IND.ENG.(:HEM., ANAL.ED.,9, 136-8 (1937). Willard, H. H., and Sheldon, J. L., ANAL. CHEM.,22, 1162-6 (1950). Yarne, J. I,., and Sobers, W .R., Am, Faundryman, 17, S o . 6 , 33-5 (1950). Young, R.S., A n a l . Chini. Acta, 4, 366-85 (19501. Zhivopistsev, V. P.. D o k l a d ~d k a d . S n i t k . S.S.S.R., 73, 1193-6 (1950). KECE1VE.D October
19 1031
Inorganic Volumetric Analysis CLEMENT J . RODDEN AND CLARA GALE GOLDBECK C’. S. A t o m i c Energy C o m m i s s i o n , New Brunswick, .V. J .
T
HIS review covers the years 1950 and 1951 and follows the pattern of previous reviews. The trend toward instrumental methods has been quite pronounced in t,he past feiv years, with the result t,hat developments in direct volumetric methods have been decreasing to a noticeable extent. BOOKS AND REVIEUS
&-edited methods for ferrous and nonferrous metals by the hinerican Society for Testing Materials (2) have brought this useful volume up to date. Books and pamphlets on the assay of uranium include one containing a review of methods used on the Manhattan Project (186), a handbook of met,hods in use in England ( i o ) , and one in use in the United States (187). .1new edition of the well-knon n monograph on volumetric iodate methods has appeared (203) and a comprehensive review of sampling methods (56) was published. Reviews include those on fluorine ( 7 6 ) ;Kjeldahl nitrogen method as applied to microanalysis (123’); the determination of carbon dioxide from carbonates in agricultural and biological material ( 2 2 7 ) ; and the determination of chlorine in water (106). Reviews on the Karl Fischer method for water have included comparison and preparation of reagents and methods of determinations (114), a round table review discussion
(150), and applications to determination of water in mirrerals (119). STUDIES O F \lETHODS
Studies of titration in glacial acetic acid have shown that salts of strong bases and tveak acids, weak bases and weak acids, and \veak organic bases can be titrated using perchloric acid as a titrating agent (142). The relative merits of ceriometry and vanadiometry have been studied and ammonium vanadate is stated to have certain advantages (632). LIanganese sulfate is stated to have certain advantages over iodine muiiocahloride as a catalyst in ceric sulfate titrations (239). Factors affecting the stability of ferrate(V1) ion in aqueous solutions have been studied to improve the use of the reagent as an oxidizing agent in alkaline solutions (195). During titrations in neutralization reactions the change in volume and also heat of the reaction has an effect on the pH of the solution. Changes in internal resistance are indicated (193). A P P 4 R 4TL S
Considerable interebt has been shorn 11 in the development of instruments for high frequency titrations. Of the various instruments described ( 5 , 21, 23,92),the stable high frequency titriin-
