V O L U M E 25, NO. 1, J A N U A R Y 1 9 5 3
17
(143) Thompson, A. R., Australian J . S c i . Research, 3A, 128
(1950). (144) TomiCek, O., BlaBek, A , , and Roubal, z., C h e m , z r e s t i , 4, 479 (1950). (145) T’andenheuvel, F. A . , and Hayes, E. R., d s a ~CHEW, . 24, 960 (1952). (146) Variochem VVB Schimmel, Ber. z’on T’ariochem V V B Schimmel, 1950.
(147) Varma, K. C., Burt, J. B., and Schwarting, A. E.,J. -4m.P h a r m . Assoc., 41, 318 (1952). (148) JVaY, R. M . , and Gailey, W.R., J . Assoc. O&. Agr. Chemists 34, 726 (1951). (149) Wegner, E., P h a r m . Zentralhalle, 91, 43 (1952). (150) TT-iberley,J , S,, ANAL. CHEM,, 23, 656 (1951), (151) Williams, M. B., and Reese, H. D., Ibid., 22, 1556 (19.50). (152) M’ilson, J. B., J . Assoc. Ofic. A g r . Chemists, 33, 995 (1950). (153) Zahn, H., and Wura, A , , 2. anal. Chem., 134, 183 (19.51).
FERTILIZERS G. L. BRIDGER Department of Chemical and Mining Engineering, Iowa State College, Ames, Iowa
T
HIS review covers the literature on analysis of fertilizers since the two previous reviews on this subject, published in the February 1949 and February 1950 issues of ANALYTICAL CHEMISTRY (120, 121). As in the previous reviews, this review is not limited to procedures used directly for fertilizer analysis but includes other methods that may have possible application to the analysis of fertilizers. Since publication of the last review, the seventh edition of the “Official Methods of Analysis” of the Association of Official Agricultural Chemists has appeared (6). iimong the more important changes in this revision are adoption of the formaldehyde titration method for nitrogen in ammonium nitrate, deletion of the citric acid solubility method for available phosphorus pentoxide, adoption of the air flow, vacuum drying, and vacuum desiccation methods for free water, deletion of the toluene distillation method for moisture, and appearance of a new procedure for sulfide sulfur in calcium silicate slags. SAMPLING AND SAiMPLE PREPARATION
In a report on sampling fertilizers, Allen ( 3 ) submitted unground samples of mixed fertilizer to state control officials for ’ grinding and sieving tests. I n 16 of the 39 samples more than 1% of the material was coarser than 1 mm. in particle size. Nissen and associates ( 185) discuss the problem of getting thoroughly representative samples. Snedecor (241) discusses increasing the efficiency of sampling investigations. WATER
Hill, Caro, and Kumagai (109) studied four methods for the determination of water in fertilizers: air flow a t 60°, vacuum desiccation a t room temperature, oven drying a t looo, and oven drying a t 130’ C. It was concluded that additional data on ammonia and fluorine losses m-ere needed before recommendation of :I.single drying temperature. RIitchell ( 1 7 1 ) studied the rate of rvaporation in the detcrmination of water. NITROGEN
In a collaborative study of the determination of nitrogen in fertilizers, Etheredge (63) concludes that ( a ) potentiometric titration in the formaldehyde procedure for total nitrogen in ammonium nitrate is satisfactory, ( b ) the Devarda method is superior to the Kjeldahl method for nitrogen in nitrates, and (c) the quantity of salicylic acid used in the determination of nitrogen in high nitrate-chloride mixtures is more important than msnipulative technique or whether zinc or thiosulfate is used for the reduction. Shuey (234)describes determination of total nitrogen in fertilizers containing chlorides, similar to the methods of Dyer and Hamence ( 5 9 )and Davisson and Parson (44). The proposed method is reported to be more accurate than the official method. Dnvis ( 4 3 ) rqiortq that thr Shucx- mothod givrs resultq higher
than those by the official method for high-nitrate fertilizer mixtures. Hamence (98) describes a method for the determination of the relative availability of nitrogen in fertilizers based on the determination of nitrate ion produced when the fertilizer is mixed with soil under conditions giving the maximum nitrification rate. Clark and Gaddy (54)compare the official permanganate methods for the quality of ~-ater-insolublenitrogen in fertilizers for a large number of samples of mixed fertilizers. Urusovskaya and Shiryaeva (262) describe a micro-Kjeldahl procedure for determination of total nitrogen in calcium cyanamide. -4s in previous years, a large number of articles appeared on the Kjelda’il method for nitrogen in various other materials. Kirk (133) reviews the more important unsolved problems of the Kjeldahl method. Lake, McCutchan, Van Meter, and See1 (146) report on the effects of digestion temperature. de Groot and Mighorst ( 9 4 ) describe a U-shaped tube as the distillation apparatus, whereas Norgrady ( 1 8 7 ) uses a wash bottle in conjunction with the usual Kjeldahl flask. The direct titration of ammonia in Kjeldahl determinations with nickel ammonium sulfate solutions as an absorbent is described by Blom and Schwarz (20). Perchloric acid for decomposition of vegetable substances in the Kjeldahl procedure is used by Koch ( I % ) , whereas potassium persulfate and hydrogen peroxide are used for this purpose by Marque2 and Alliota (164). .4 microaeration technique is described by Day, Bernstorf, and Hill (45). Microdigestions in sealed tubes a t 470” are used by White and Long ( 2 7 8 ) . The use of selenium catalysts in the Kjeldahl procedure was studied by Garcia (80),Schwab and SchFab-Agallidis (227),Ribas and Capont (214), and Dupuy (57‘). McCutchan and Roth (154) use thiosalicylic acid to assist the conversion of nitrogen to ammonia in nitro-type compounds. Various oxidizing compounds in the Kjeldahl procedure were studied by Quartaroli (106) arid it was concluded that the most useful oxidizer is pyrolusite. Application of the Kjeldahl method to various organic compounds is reported by Tirouflet (2.56), Ploquin (197),and F’anetten and JViele (265). Further developments in the Dumas method for nitrogen determination are reported by Kao and Woodland (129) and Kirsten (134). Several articles appeared on determination of nitrate nitrogen. A microtitrimetric method is described by Leithe (149). Use of organic substances is reported by Gritsyuta (93). Indigo is used by Zamyatina (290). Determination of nitrate in plant material is described by Johnson and Ulrich ( 1 2 7 ) . -4titrimetric method depending on reduction of nitrogen by ferrms hydroxide in the presence of silver diammine sulfate is used by Szab6 and Bartha (246). An alkalimetric determination of nitrate by coppercatalyzed reduction is described by Szab6 and Barthn (247) who also gave a procedure using silver ammonium sulfate (246). Determination of nitrate by the Devarda method is described by Miura and Ueno ( 1 7 2 ) .
ANALYTICAL CHEMISTRY
18 Determination of nitrites and separation of nitrites and nitrates received the attention of a number of workers. Barnes (12) developed a color reaction for distinguishing nitrites and nitrates based on the use of N-( 1-naphthyl) ethylenediamine hydrochloride reagent. Burriel and Acosta ( 1 7 ) eliminated nitrites from mixtures of nitrites and nitrates by boiling with urea or its derivatives. Brasted (94)determines nitrites in the presence of nitric acid by an iodopermanganate titration. Carson (30) describes a gasometric micromethod for nitrite and sulfamate. Barnes and Folkhard (13)use a colorimetric procedure for nitrites. Vazhenin (166) describes a colorimetric determination of adsorbed ammonia by the phenol method. A semimicrodistillation of ammonia into 4% boric acid solution is used by Machemer and McNabb (155). A rapid method of determining ammonia in ammonium salts based on titration with formaldehyde is described by Rusconi (218). Slavik and Michalec (238) determine nitrogen with Xessler reagent. Donnally ( 5 0 ) determines monomethylol and dimethylo] urea by hydrolysis of these compounds to urea and formaldehyde in neutral sodium phosphate solution; the formaldehyde is then determined iodometrically. Storck (245)determines urea gasometrically by using lO%sodiumhydroxide solution in the hypobromite method. Determination of nitrogen in various organic compounds is described by Brown and Hoffpauir ( W ) ,Thompson and Morrison ( 2 5 4 ) , Rauen, Leonhardi, and Buchka (211), Renard and Deschamps (212), Watanabe and Ichinose (275), and Renard and M6dart (213). Kienitz (139) uses a method based on oxidation with permanganate and titration with ferrous sulfate for the analysis of a mixture of nitrous oxide and nitric oxide. A colorimetric modification of the method is also described. A review which includes recent advances in nitrogen analysis of fertilizers was published by Hamence (97).
PnosPnoRus A study of the solubility of the phosphorus pentoxide content of 92 superphosphates and 420 mixed fertilizers was made by Clark and Hoffman (36). A report on the determination of phosphorus pentoxide in fertilizers including a comparison of the neutral ammonium citrate and 2% citric acid methods for soluble phosphorus pentoxide for alpha-phosphate and fused calcium magnesium phosphate was made by Jacob, Magness, and Whittaker (123). The relation of particle size of calcium metaphosphate to its citrate solubility and fertilizer efficiency u as studied by Jacob, Armiger, Caro, and Hoffman (122). The direct determination of available phosphorus pentoxide by titration of precipitated ammonium phosphomolybdate is proposed by Allen, Swift, Hays, and Kaufman ( 4 ) ;interference by citrate is eliminated by use of a very small aliquot. Saj6 (260)determines phosphorus in Nartin and blast furnace slags. I n the quantitative volumetric analysis of phosphoric acid, Tomoeda (259) studied the effect of various salts on the titration of disodium phosphate n ith phenolphthalein indicator and by use of a hydrogen electrode. Kikronorov (184) replaces paper filters by glass filters in phosphorus analysis. Frey ( 7 2 ) reports on the gravimetric determination of phosphoric acid as ammonium phosphomolybdate. Dupuis and Duval ( 5 3 ) determine phosphorus by means of the Chevenard thermobalance. The precipitation of phosphate with magnesium in the presence of calcium and other cations and its determination x i t h ethylenediaminetetraacetic acid are studied by Huditz, Flaschka, and Petzold (113). Bacon and Davis (7) determine phosphorus in the presence of chromium compounds. A number of improved or new methods of phosphorus determination for various materials are described. Heimann and Heimann-Geierhass (107) report on improvements in Embden's method. The alkalimetric determination of orthophosphoric acid by titration with standard sodium hydroxide solution with the use
of an antimony indicator electrode is used by Fisher and Kraft (66); quinhydrone and glass electrodes are also used. Ubaldini and Guerrieri (d61) studied the argentometric determination of phosphoric acid. Mager (160) determines total phosphorus pentoxide in phosphates by hydrochloric acid and magnesium pyrophosphate precipitation. Thistlet.hw-aite (253) determines soluble phosphate by titration with a standard bismuth solution. Determination of phosphoric anhydride by means of quinoline phosphomolybdate is described by Wilson (284). Gravimetric determination of .phosphorus as magnesium pyrophosphate by alkalimetric titration, iodometric determination, and acolorimetric determination are described by Templeton and Bassett (262), in the National Suclear Energy Series. A conductonietric determination of phosphoric acid and ammonia is described by Gensch and Jander (84). ii potentiometric titration of monoand diamnionium phosphates is described by Vermast (268). Sodium 2,5-cresotate is used as an indicator for phosphate titration by Nutten (188). ii qualitative test for the phosphate ion in which molybdenum blue is used is described by Jaffe (124). Detection of phosphate ions with molybdate and its behavior in qualitative analysis are described by van Dalen and De Vries (39). Numerous colorimetric studies were made on phosphorus determination. Vekman (267)determines phosphorus pentoside in fertilizers and raw phosphates with a photoelectric colorimeter to measure the molybdenum blue color. Gelli (81) review the literature on photometric determination of phosphorus pentoside and suggests a new procedure based on the use of ammonium molybdate and hydrazine sulfate. Hanson 1102) determines phosphorus pentoxide in fertilizers with the phosphovanadomolybdate complex. ilIasurova (168) determines phosphorus pentoxide in basic open-hearth slags. Ikeda ( 1 15) determines phosphate colorimetrically by reduction of phosphomolybdate n-ith sodium thiosulfate. Kato, Okinaka, and Oizumi (130) propose two colorimetric methods; in the first ammonium molybdate is added to the sample, which is then heated with nitric acid; in the second ammonium molybdate and pyrogallol are used. A simple photoelectric colorimeter suitable for phosphorus determination is described by Dechering (46). A stable scale in the colorimetric determination of phosphorus based on acidified potassium dichromate solution containing copper sulfate is proposed by Shcherbov (232). .4 modified colorimetric method in which Metol is used as the reducing agent instead of hydroquinone is described by Zimmermann (294). Nitrate interference in the colorimetric det,erminat,ionof phosphorus is controlled by sodium nitride or by sulfamic acid by Greenberg, Keinberger, and Sawyer (91). The determination and separation of ortho-, pyro-, and nietaS e u (181), phosphates were studied by Straaten and Aten ($44), and Dewald and Schmidt ( 4 7 , 4 8 ) . The review by Hamence (97) referred to in the nit'rogen section also includes references on phosphorus determination POTA SSlUW
The silver cobaltinitrite method received the attent'ion of numerous workers. Court,ois (38) and Chenery ( 3 2 ) describe modifications and improvements to this method. The conditions for the precipitation of potassium-sodium cobaltinitrite and titration of potassium-sodium cobaltinitrate with permanganate (140, 141) are set forth by Kriventsov. Belcher and Nutten (16) compare the i$7ilcoxmethod (279) with the Hamid method (99). .In improved technique for precipitation with 'sodium cobaltinitrite is described by Mason (167). Bassett and Byerley ( 1 4 ) describe determination of potassium as cobaltinitrite, perchlorate, and chloroplatinate, and by a colorimetric method. The V O ~ U metric determination of potassium with cobaltinitrite and potassium dichromate is described by Iritani (117). Flame photometric methods for determination of potassium in fertilizers were worked out bl- Schall and Hagelberg ( 2 2 4 ) . Results comparable to those obtained by chemical procedures were obtained, escept that the flame photometric values were slightly
V O L U M E 25, NO. 1, J A N U A R Y 1 9 5 3 lower than the chemical values and were nearer the theoretical values. Gelli (82) found an experimental error of & l %in the analysis of potassium fertilizers by the flame photometric method. Zoellner (295) lists factors influencing the accuracy of flame photometric determinations of alkali. Colorimetric methods for potassium determination were described by Hanson (101j, n-ho used dipicrylamine, and Blaszkowska and Szperl(19j, who converted the potassium compounds to chlorides and the resulting chlorides into picrates. Proposed new methods for potassium determination include those of Sat0 (221j, who precipitated potassium as a salt of hexyl dipicrylamine, Tananaev and Kozlov (249) which is based on the interaction of cadmium sulfate, lithium ferrocyanide, and potassium ferrocyanide, and Raff and Brotz ( % O r ) , who determined potassium as the salt of tetraphenylboron. A number of reviews on potassium analysis appeared. In a review by Donald ( 4 9 ) ,methods for determination of potassium in fertilizers are found. Robinson (216) published a general review of the analytical chemistry of potassium. Brind ( 2 5 ) reviewed determination of potassium in soils. The review of Hamence ( 9 7 ) includes references to potassium analysis. C4LCIUM
,
The oxalate precipitation method continued to receive attention from several workers. Usatenko and Datsenko (263) reported on the determination of calcium and magnesium in dolomites, magnesites, and open-hearth slags. Levit (150) determined calcium in dolomites containing siderite. Richter (915 ) describes a rapid method for the simultaneous determination and separation of calcium and magnesium based on permanganate titration of the calcium and photometric determination of the magnesium. Vajna and Gabos-Pinter (264) describe an oxalate-permanganate procedure. Aleksandrov and Shevchenko (1) determined calcium and magnesium in potassium minerals by permanganate titration and alkalimetry. Neidrach, hlitchell, and Rodden (180) describe methods for calcium, magnesium, and other alkaline earth materials. Saj6 (220) determines calcium in Martin and blast furnace slags. Colorimetric methods for calcium are described by Cornfield and Pollard ( S T ) , Ostertag and Rinck (192, 193), and Rafflaub (208). Most of these workers use murexide to develop the color. OkkE and Pech (191, 194) describe a colorimetric method in which pyrogallolcarboxylic acid is used to develop the color. Flaschka (67, 68) describes a method for rapid determination of calcium and magnesium based on precipitation of both with potassium ferrocyanide, titration of the calcium with permanganate, and titration of magnesium 8-hydroxvquinolate with bromate. Granovskil and Druzhinin (90) determine calcium in .\Tartin and blast-furnace slags by a fluoride method. Povondra ( ? O f ) uses a tungstate method for determining calcium in carbonate rocks. Triche (260) detects calcium by simultaneous precipitation of silver chromate and calcium carbonate. Keller (131) determines the gypsum dihydrate content of technical semihydrate by a dehydration procedure. Smith, Comrie, and Simpson (239) estimate the calcium content of agricultural lime by a simple titration procedure. Banewicz and Kenner (10) determine calcium and magnesium in limestones and dolomites by the ethylenediaminetetraacetic acid method. Review articles which include references to calcium determination are those of Lazarev (147), Belcher and Goulden (15), and Dupuis (52). MAGNESIUM
19 An arsenate-cerionietric method for determination of magnesium is described by Mehlig and Buell (169). Moret (175) determines magnesium in rocks by a conductometric method. Daubner (42) precipitates magnesium as magnesium ammonium arsenate and titrates the precipitate with sodium thiosulfate. Bovalini and Mannucci (92) used a volumetric method to determine magnesium in the presence of aluminum. Ishihashi, Hayakawa, and Fujinaga (119) determine magnesium in sea water and brine by precipitation as magnesium hydroxide and titration with hydrochloric acid or oxine. A polarographic method for magnesium is described by Monnier, Rusconi, and Kenger (17 3 ) . Several colorimetric procedures for magnesium are described. An absorptiometric method for determination of magnesium is used by Hunter (114). Willson (282) uses 8-quinolinol and bromothymol blue indicator to develop the color. Pochinok (199) uses 3-phenyl-1-p-nitrophenyl-3-hydroxytriazine as a color reagent. Willson and Wander (283) eliminate copper interference in the Titan Yellow method by adding copper to the standard solution and potassium cyanide to the unknown solution. Schneider (225) uses 1,s-dihydroxyanthraquinone as a color reagent for magnesium, whereas Shashkin (231) uses 1amino-2-naphthol-6-sulfonic acid. Knop (137) uses Eriochrome Gray SGL and BL to develop a purple coloration with very small amounts of magnesium. A rapid method for determination of magnesium in dolomite is based on ignition loss, insoluble iron oxide, and aluminum oxide content of the sample (237). Holth (110) describes separation of calcium from magnesium by the oxalate method. Review articles containing references to magnesium determination are those of Irving (118) and Dupuis (51). SULFUR
Sulfur in Martin and blast furnace slags is determined by Saj6 (290). Precipitation of sulfur as barium sulfate was reported by Liang and Shen (151) to be improved by the presence of
tartaric and especially citric acid. Sulfur was determined colorimetricallv by Roth (217) who used dimethyl-p-phenylenediamine and ferric alum, and Takagi and Yamada (148). An iodometric titration of sulfate is described by Elsermannand Wunderlich (61). Conditionsfor quantitative precipitation of various sulfates are described by Dupuis and Duval (66). A colorimetric micromethod for sulfur is described by Walter (273). Various combustion procedures for sulfur are described by Kirsten (133, Siegfriedt, I%-iberley, and Moore (235), and Chudinov (33). Several methods for sulfur determination are described by McKenna and Templeton (159). Sulfate is determined volumetrically with barium and disodium dihydrogen ethylenediaminetetraacetate solution by Munger, Nippler, and Ingols (17'6). Sulfate is determined by reduction with stannous chloride by Rancke-Madsen (209). A volumetric procedure for elemental sulfur is described by Funck, Wackernagel, and Frober (73). Sulfidic sulfur in inorganic compounds is determined by Schulek and Koros (226), based on titration with hydrochloric acid in the presence of p-ethoxychrysoidine. A rapid method for free sulfur based on sublimation is described by Libina, Miller, and Musakin (152). Hydrosulfides are determined by thiosulfate titration by FehBr, Klug, andEmmerich (64). Mixtures of inorganic sulfur compounds are separated by differences in solubility of the lead salts by Mangan (162). Various compounds of sulfur in commercial alkali polysulfides are determined by Carrer6 (29).
A number of the articles referred to in the preceding section on calcium also contain procedures relating to magnesium deter-
BORON
mination (1, 10, 67, 180, 915, 263). Magnesium in fertilizers w-as determined by Smith (240).
Borax in mixed fertilizers is determined by the identical pH titration principle by Taylor (251). Boron and fluorine when
ANALYTICAL CHEMISTRY
20 present together are determined by Ryabchikov and Danilova (619), by distillation of the boron as the trifluoride from a sulfuric acid solution and separation of the fluorine from the distillate by adsorption on a synthetic resin. The boron is then determined colorimetrically with carmine, and the fluorine is displaced with sodium carbonate and determined colorimetrically. Duval (58) tests the ignition temperature limits for various boron precipitates. Luchini (163) uses a rapid titrimetric method for boron. Tokuoka, Matsuo, and Mori (267) use a potentiometric titration. Colorimetric determinations of boron include those of Aleksandrov and Tsvik ( d ) , and Hatcher and Wilcox (103), who used carmine, Hegedus (105, 1067, who used turmeric and chromotrop 2 B, Ellis, Zook, and Baudisch (60), who tested 60 organic compounds and recommend dianthrimide (1,l '-dianthraquinoylamine), and Hazel and Ogilvie (IO,$),who used p-nitrophenol. MANGANESE
Manganese in Martin and blast furnace slags f a s determined by Saj6 (620). Manganese in various fertilizers was determined by Smith (240). Manganese was determined as manganese ammonium phosphate by Njegovan and Morsan (186). A persulfate method is described by Datsenko (41). A ferricyanide oxidimetric determination was used by Piibil and Simon (205). Trivalent and tetravalent manganese is determined by Fyfe (77) by reaction with acetylacetone. A reductometric determination of trivalent manganese is described by Piibil and HorAEek (202). Dupuis, Besson, and Duval (52) conclude that the only precipitates suitable for the automatic determination of manganese are the sulfate, oxalate, anthranilate, and oxinate, but they also determine pyrolysis curves for some other compounds. Manganese and copper are determined by a potentiometric method by Kievas and Berges (183), and manganese and cobalt are determined similarly by Gladushko (88). Colorimetric procedures for manganese are described by Zhuravskaya (293) who uses the persulfate-silver nitrate method, Bombelli ( 2 1 ) who uses periodate of lead and bismuth, Murakami (177) who uses silver peroxide, Piibil and Hornychova (203) who use Complexones, Young and Hiskey (288) who use periodate oxidation, and Grosdenis (95) who uses persulfate ovidation COPPER
The iodometric determination of copper is described by Hammock and Swift (100). Thioacetamide is used by Flaschka and Jakobljevich (70) to precipitate copper quantitatively. A macro and micromethod for copper is described by Tarasevich (250). W-enger, Monnier, and Jaccard (276) use l-nitroso-2naphthol as a reagent for copper determination. TomiEek and Mandelik (258) describe a potentiometric method in which vanadyl sulfate is used. Gagliardi and Loidl (78) use thioformamide for the separation of copper and arsenic. Pochinok (198) determines copper volumetrically after its separation with thiosulfate. Various colorimetric methods are described. blurakami ( 178) uses sodium diethyldithiocarbamate in the presence of hydroxylamine. Gordieveff (89) determines copper with pyridine and salicylic acid. Pinte and Essertel (196) use Direct Green B as a colorimetric reagent for copper. Hoste,_Heiremans, and Gillis (112) use 2,2-biquinoline. OkBC and CelechovskS. (189, 190) evaluate several color tests. Sedivec and Vasak ( 2 '8) use Complexones, in particular, sodium diethyldithiocarbamate. Simultaneous spectrophotometric determination of cobalt, copper, and iron is described by Kitson (136). ZIhC
The ferrocyanide method of determining zinc with an outside indicator is described by Finkel'shteln and Benevolenskaya (66).
Several methods for determining zinc are described by Furman and Jensen (74),including precipitation as the double phosphate, ferrocyanide titration, deposition on a mercury cathode, precipitation of zinc sulfide, and the use of organic reagents. Dithizone is used by Mehlig and Guill (170) as an indicator in titrimetric determination of zinc with ferrocyanide. Numerous colorimetric methods are described. Yoe and benzylideneRush (286) use o- [a-(2-hydroxyl-5-suIfophenylazo) hydrazino] benzoic acid to serve as a colorimetric reagent. Murakami (179) uses sodium diethyldithiocarbamate. Frey (71) titrates with potassium hesacyanoferrate. Barnes (11) uses dithizone. Belcher and Nutten (17) use substituted benzidines. Mahr and Denck (161) use picric acid. Bishop (18) determined the influence of various anions on the morin test for zinc. COBALT
h volumetric method for determination of cobalt and nickel with a,a'-dipyridyl is described by Cavicchi (31). Laitinen and Burdett (146) use an iodometric method. Kallman (128) precipitates cobalt as potassium cobaltinitrite. Baker and McCutcheon ( 8 ) separate and determine cobalt in the presence of nonvolatile radicals by the use of quaternary ammonium hydroxides. A gravimetric method based on precipitation of cobalt as its mercuric thiocyanide is studied by Sierra and Carceles (236). Modifications in the o-nitrosocresol method for use with a large number of samples are described by Gregory, Morris, and Ellis (92). Burriel and Perez (28) describe a volumetric technique for cobalt based on its transformation into cyanide and titration with standard acid. Bane and Grimes (9) used the conventional precipitation with 1-nitroso-2-naphthol method, but as the quantities present were unusually small, the colorimetric determination with tetraphenylarsonium chloride was preferred. Gladushko (88) determined cobalt and manganese in one sample by potentiometric titration. Colorimetric methods are described by Shome (233) who used the orange red color of the cobalt-isonitrosodimethpldihydroresorcinol (isonitrosodimedon) complex, Perry and Serfass (195) who used 3-nitrososalicylic acid, Polya and Wilson (200) who used a benzidine dimethylglyoxime reagent, Lee and Diehl (148) who studied 20 amines with dimethylglyoxime and concluded that benzidine was the best, -Hall and Young (96) who used nitroso R salt, and OkcX and Celechovsk4. (189) who used antipyrine. Simultaneous spectrophotometric determination of cobalt, copper, and iron is described by Kitson (136). MOLYBDENUM
A volumetric determination of molybdenum in Tvhich reduction with zinc and titration with permanganate are used is described by Gagliardi and Pilz (79). A field method for semimicrodetermination of molybdenum in soils and rocks is described by Ward (274). -4potentiometric determination in which sodium molybdate is reduced with zinc and titrated with ceric sulfate or potassium permanganate is described by Stehllk (242). Gravimetric procedures are compared by Dupuis and Duval (54), who list several possible molybdenum precipitants. Flaschka and Jakobljevich (69) use thioacetamide as a precipitant. Ikegami (116) uses a standard manganese acid pyrophosphate solution for titration of molybdenum solutions. Pi-ibil and Makit (604) determine molybdenum by means of 8-quinolinol. Jensen and Weaver (126) consider gravimetric procedures in . which lead molybdate or molybdenum trioxide is weighed. % titrimetric procedure is used in which thorium molybdate is titrated after reduction with ceric sulfate. Colorimetric procedures are based on the reaction with stannous chloride and ammonium thiocyanate or formation of a color with phenylhydrazine in dilute sulfuric acid. Several colorimetric methods are described. Yoe and Will (287) use disodium 1,2-dihydroxy-3,5-benzenedisulfonate(Tiron)
a
V O L U M E 25, NO.
1, J A N U A R Y 1 9 5 3
to develop a bright yellow color which is very sensitive. Shapiro (230) uses pyrocatechuic aldehyde. Seifter and Novic (229) use catechol. Rasin-Streden and Popoff-Asotoff (210) give detailed instructions for obtaining consistent results with the thiocyanate-stannous chloride method. Zaichikova (289) uses thiourea to develop the color. CHLORINE
Various methods for chlorine determination are considered by Mansfield and Templeton (163). The conventional gravimetric determination is preferred when accurate results are required and 0.1 to 0.2 gram of chloride is present. Potentiometric titration of silver nitrate, electrometric titration, i'olhard titration with silver nitrate and sodium nitroprusside, thiosulfate titration with iodine, nephelometric and turbidimetric methods, and the o-toluidine diffusion micromethod are carefully described. Furutani (75) describes a rapid potentiometric method. Vyakhirev and Guglina (269) describe a potentiometric method without the use of silver nitrate. Martin (166) and Wurzschmitt (285) use a sodium peroxide bomb method. James and Belser (125) fuse the sample with potassium pyrosulfate and titrate with silver nitrate. Dupuis and Duval (55) studied pyrolysis curves of precipitates used in gravimetric determination of chlorine. A large number of color reagents for chlorides are described by Iluznetsov (143), Schafer (223), who uses n-methyldiphenylamine red as an adsorption indicator, and Kuroda and Sandell (142), who determine chlorine in silicate rocks by fusion with sodium carbonate and measurement of the color developed by sodium sulfide. FLUORINE
Methods for determination of fluorine in fused phosphate fertilizers were described by Brabson, Smith, and Darrow ( 2 3 ) . One method suitable for fused tricalcium phosphate involves alkali fusion, sulfuric acid digestion, steam distillation, redistillation of fluorine from perchloric acid, and titration with thorium nitrate. -4second method suitable for either fused tricalcium phosphate or fused calcium magnesium phosphate is similar to the first, except that the sulfuric acid digestion and subsequent distillation are omitted. For calcium metaphosphate, the fusion step in the second method is also omitted. Determination of fluorine in agricultural materials such as fertilizers, fodders, soils, minerals, and plants was studied by Gericke and Kurniies (86, 87) who modify the usual distillation-thorium nitrate method. MacIntire, Hardin, and Jones (156') compare three methods for determination of fluorine in soils. The recommended method is double distillation of the untreated soil from sulfuric acid a t 165', concentration of the distillate, and redistillation from perchloric acid a t 135". Wadhwani (270-272) studied the thorium nitrate titration method, a colorimetric method with ferron, and an oxalate precipitation method. Some 200 materials were tested by Willard and Horton (280)as colorimetric indicators for titration of fluorine with thorium. The best indicators in the order of increasing effectiveness were purpurin sulfonate, Alizarin Red S, Eriochrome Cyanin R, dicyanoquinizarin, and Chromazurol S ; the best fluorescent indicators were pure sublimed morin and quercetin. Zeppelin (291)adapted the zirconium chloride titration method for microdetermination of fluorine. Zeppelin and Fuchs (296) describe preparation of the zirconium chloride standard solution. Georch (85) determines fluorine as lead chloride-fluoride. Sari-aya (922) determines fluorine x i t h a silicic acid titration. Dupuis and Duval (65) studied pyrolysis curves of precipitates used in gravimetric determination of fluorine. Colorimetric determination of fluorine with titanium and hydrogen peroxide was studied by Monnier, Vaucher, and Wenger ( 17 4 ) . Photofluorometric determination of fluoride
21 with p-nitrophenol and quercetin was studied by Willard and Horton (281). Determination of small quantities of fluorine in minerals with a titanium-hydrogen peroxide indicator is described by Koritnig (139). A colorimetric determination depending on use of ferric ions in concentrated sodium bromide solution is described by Erler (62). Hill and Reynolds (108) adapt the titanium hydrogen peroxide titration method for use in the presence of large amounts of phosphate. Lacroix and Labalade (144) use the reaction between ferric ion and sulfo-5-salicylic acid to develop the color. Fuwa (76) determines fluorine 71-ith the band spectra of calcium fluoride; if more than 10% of phosphorus pentoxide is present, removal of the fluorine by distillation is necessary. Horton, Thomason, and Xiller (111) describe a method based on thoron acid reagent, 1-(o-arsonophenplazo)-2-naphthol-3,6-disulfonic McKenna (157, 158) reviews methods for fluorine and fluoride analysis. CARBON DlOXlDE
Clark, Gaddy, Blair, and Lundstrom (35) determined the carbonate- and acid-insoluble ash content of a number of mixed fertilizers. Dallemagne (40) describes an apparatus for determination of carbonate in powdered solids which is based on absorption of the carbon dioxide in barium hydroxide and titration of the standard acid. Iiieuwenburg and Ilegge (182) also absorb carbon dioxide in barium hydroxide but use a mixture of aniline, ethyl alcohol, and water instead of the usual aqueous solution to eliminate large excesses of barium hydroxide. Tinsley, Taylor, and Moore (355) determine carbon dioxide derived from agricultural and biological materials by an acid decomposition-sodium hydroxide absorption procedure. Arnal and Rojo ( 5 ) study the precipitation of carbonates with barium chloride. Maschka and Frauenschill (166) describe a titrimetric determination of carbonate in the presence of nitrite and nitrate. West (277) tests six indicators for the titration of carbonate and concludes that dimethyl yellow-bromocresol green is best. BASICITY
Generozov (83) describes a procedure for the semimicrodetermination of basicity of slag in which a 200-mesh sample is extracted with water and the extract titrated with hydrochloric acid. ACKNOWLEDGME3T
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23 S u c l e a r Energy Ser., Div. VIII, 1, -4nal. Chem. hfanhattan Project, 350-71 (1950). (181) Neu. R.. 2. anal. Chem.. 131.102-3 (1950). (182) Nieuwenburg, C. J. van, and Hegge, L. A., A n a l . C h i m . Acta, 5,68-70 (1951). (153) Nievas, J. B., and Berges, L. S.,Anales real SOC. espafi. f f s . y &m., 47B, 601-8 (1951). (184) Nikronorov, K. V., Zhur. A n a l . Khim., 5, 124 (1950). (185) Nissen, B. H.. et al.. Bm. Soc. Brewing Chemists, Proc., 1948, 122-8. (186) Xjegovan, V. N., and Morsan, B., 2. anal. Chem., 131, 157-91 (1950). (187) Norgrady, G., M a g y a r Kem. L a p j a , 4, 35&2 (1949). (158) Nutten, A. J., Metallurgia, 42, 407-10 (1950). (189) Okhe, A , , and Celechovskp, J., Chem. L i s t y , 43, 7-8 (1949). (190) Ibid.. 45,52-4 (1951). (191) OkiE. A .and Pech. J.. Ibid.. 42.161-3 (1948). (192) Ostertag; H., and Rinck, E., Compt. rend., 231, 1304-5 (1950). (193) Ihid., 232,629-30 (1951). (194) Pech, J..Ibid., 43,8-11 (1949). (195) Perry, RI. H., and Serfass, E. J., ANLL. CHEM.,22, 565-7 (1950). (196) Pinte, J., and Essertel, B u l l . inst. teztile France, No. 15, 63-8 (1949). (197) Ploquin, J.. Compt. rend., 231, 1066-8 (1950). (198) Pochinok, K. N., Zavodskaya Lab., 13,1012-14 (1947). (199) Pochinok, K. N., and Pochinok, V. Y . , Zhur. A n a l . Khim., 4, 244-7 (1949). (200) Polya. J. B., and Wilson, B., Australian J . Sci., 13, 26-7 11960). .----. (201) Povondra, P., V6stndk Stdt. Geol. dstavu eeskoslou. Rep., 25, 279-80 (in English), 282 (1950). (202) PFibil. R.. and HorBEek, J., Collection Czechoslov. Chem. Comm u n s . , 14,626-44 (1949). (203) PEibil, R., and Hornychova, E., Chem. L i s t y , 44, 101-3 (1950). (204) PEibil, R., and Mal& M.,Collection Czechoslov. Chem. Comm u n s . . 15,120-31 (1950). (205) Pfibil. R., and Simon, V., Ibid.. 14, 454-68 (1949). (206) Quartaroli, A., Ann. f a c . agrar. u n i v . Pisa, 9, 90-9 (1948). (207) Raff, P., and Brotz, TV., 2. anal. Chem., 133, 241-8 (1951). (208) Rafflaub, J., Helv. Physiol. et Pharmacol. A c t a , 9, C33-5 (1951). (209) Rancke-Madsen, E., Acta Chem. Scand., 3, 773-7 (1949). (210) Rasin-Streden, R., and Popoff-Asotoff, IT., Osterr. Chem.-Ztg., 51, 1-9 (1950). (211) Rauen, H. h l . , Leonhardi. G., and Buchka, M.,2. physiol. Chcym.. 284,178-85 (1949). (212) Renard, M., and Deschamps. P., Mikrochemie wr. Mikrochim. Acta, 36/37,665-70 (1951). (213) Renard, M.. and MBdart, J., Bull. sac. roy. sei. Lihge, 18, 40914 (1949). (214) Ribas. I., and Capont, F. L.. Anales real soc. espafi. ~ Z S y. pudm., 46B, 581-94 (1950). (215) Richter, F., Chem. Tech. ( B e r l i n ) , 1,193-200 (1949). (216) Robinson, J. IT,, Chem. A g e ( L o n d o n ) , 66, 447-50, 467-9, 50710,573-7 (1952). (217) Roth. H.. Mikrochemie r e r . Mikrochim. B e t a , 36/37, 379-92 (1951). (218) Rusconi. A,, Chimica ( M i l a n ) , 5 , 107-8 (1950). (219) Ryabchikov, D. I.. and Danilova, V. V., Zhur. A n a l . K h i m . , 5 , 28-31 (1950). (220) Saj6. I., Bdnydsz. Kohdsz. L a p o k , 83, 68-70 (1950). (221) Sato, I. S.,J. Chem. Sac. J a p a n , P u r e Chem. Sect., 72, 4503 (1951). (222) Sawaya, T.,I b i d . , 71,511-14 (1950). (223) Schafer, H.. 2. anal. Chem., 129, 222-9 (1949). (224) Schall. E. D., and Hagelberg, R. R., J . Assoc. Ofic. Agr. Chemists. 35, 757-64 (1952). (225) Schneider, W..Arch. Pharn,., 283, 248-53 (1950). (226) Schulek, E., and Koros, E.. Magyar K h . Folydirat, 56, 421-6 (1950). (227) Schwab, G. AI., and Schwab-Agallidis, E., Saturwissenschaften, 36,254 (1949). (228) Sedivec, V., and Vasak, V.,Collection Czechoslor. Chem. Communs., 15,260-6 (1950). (229) Seifter, S., and Noric. B., - 4 s ~CHEM., ~ . 23, 188-9 (1951). (230) Shapiro, M.Y., Z h u r . A n a l . K h i m . , 6, 371-4 (1951). (231) Shashkin, 11.A., Zavodskaya Lab., 16, 748 (1950). (232) Shcherbov, D. P., Zhur. A n a l . Khim., 4, 152-7 (1949). (233) Shame, S. C., A n a l . C h i m . A c t a , 3, 679-85 (1949). (234) Shuey, P., J. Assoc. Ofic. Agr. Chemists, 33, 1003-8 (1950). (235) Siegfriedt. R. K., Wiberley, J. S., and Moore, R. W., AKAL. CHEY.,23,1008-11 (1951). (236) Sierra, I. F., and Carceles, F., Anales real soc. espafi. f68. u. ~ u Z W L . , 47B, 281-6 (1951).
ANALYTICAL CHEMISTRY Silicates ind., 16,338 (1951).
Slavik, K., and Michalec, C., Chem. L i s t y , 4 5 , 3 8 (1951). Smith, A. M.,Comrie, A,, and Simpson, K., A n a l y s t , 76, 58-65 (1951).
Smith, J. B., J . Assoc. O f i c . A g r . Chemists, 33, 284-7 (1950). Snedecor, G. W., J . A l a b a m a Acad. Sci., 20, 53-7 (1948). Stehlik, B., Chem. L i s t y , 38, 1-3 (1944). Storck, M. J., Ann. biol. clin. ( P a r i s ) , 7,459-60 (1949). Straaten, H. van der, and Aten, A. H. W., Jr., Rec. trav. chim., 69, 561-4 (1950).
Ssab6, Z. G., and Bartha, L., A n a l . Chim. A c t a , 5 , 33-45 (195 1).
Szab6, Z. G., and Bartha, L., Magyar K e m . Folydirat, 56, 81-3 (1950). Ibid., 5 7 , 8 4 6 (1951).
Takagi, K.. and Yamada. M., J . Electrochem. SOC.J a p a n , 18, 9-12 (1950).
Tananaev, I. V., and Koslov, A. S., Z h u r . A n a l . K h i m . , 6, 149-56 (1951).
Tarasevich, N. I., I b i d . , 4 , 108-13 (1949). Taylor, D. S.,J . Assoc. Ofic. A g r . Chemists, 33, 132-9 (1950). Templeton, D. H., and Bassett, L. G., N a t l . Nuclear Energy Ser., Div. VIII, 1 , Anal. Chem. Manhattan Project, 321-38 (1 950).
Thistlethwaite. IT. P.. Analvst. 77. 48-9 (1952). Thompson, J.’F., and Morrison’, G. R., ANAL. CHEM.,23, 1153-7 (1951).
Tinsley, J., Taylor, T. G., and Moore, J. H., A n a l y s t , 76, 300-10 (1951).
Tirouflet, J., B u l l . S O C . sci. Bretagne, 23, 129-31 (1948). Tokuoka, M., Matsuo, H., and Mori, G., J . Sci. Soil M a n u r e J a p a n , 21,90-2 (1950).
TomiEek, O., and Mandelik, J., Chem. L i s t y , 43, 169-76 (1949).
Tomoeda, M., J . P h a r m . SOC. J a p a n , 71,855-7 (1951). Triche, H.. A n a l . C h i m . A c t a , 4,12-20 (1950). Ubaldini, I., and Guerrieri, F., Ann. chim. applicata, 39, 291-7 (1949).
Urusovskaya, L. G., and Shiryaeva, T. M.,Zaaodskaya Lab., 15,16)05 (1949).
Usatenko, Y. I.,and Datsenko, 0. V., I b i d . , 16, 94-6 (1950).
(264) Vajna, S., and Gabos-Pinter, M., Magyar Kem. Folydirat, 56. 63 (1950). (265) Vanetten, C. H., and Wiele, M.B., ANAL.C H E M . , . ~1338-9 ~, (1951). (266) Vashenin, I. G., Pochvovedenie (Pedology), 1949, 359-61. (267) Veltman, G. H., Z . anal. Chem., 135, 340-9 (1952). (268) Vermast, F.A. F., Chroniea Naturae, 106, 104-10 (1950). (269) Vyakhirev, D. A., and Guglina, S.A., Zarodskaya Lab., 15, 1426-30 (1949). (270) Fadhwani, T . K., J. I n d i a n I n s t . Sci., 34, 123-33, 135-47 (1952). (271) Ibid., pp. 149-57. (272) Ibid., pp. 159-61. (273) Walter, R. N., ANAL.CHEM.,22, 1332-4 (1950). (274) Ward, F. N., Ibid., 23,788-91 (1951). (275) Watanabe, I. T., and Ichinose, Y., J . P h a r m . S O C .J a p a n , 63, 36-40 (1943). (276) Weneer. P. E.. Monnier. D.. and Jaccard. F.. H e l t . C h i m . Acta, 33,1458-63 (1950). (277) West, T. S., SchoolSci. Rev., 32, 163-4 (1951). (278) White, L. A f . , and Long, h1. h A L . CHEM., 23, 363-5 (1951). I S D . ENG.CHEM., AN.4L. ED.,9 , 136-8 (1937). (279) \vllCOX, L. IT., 1 Willard, H. H.. and Horton, C. A.. - 4 ~ 4CHEM.. ~ . 22, 119Ck4 (1950). Ibid., pp. 1194-7. Willson, A. E.,I b i d . , 23,754-7 (1951). Willson, A. E., and Wander, I. K., Ibid., 22, 195-6 (1950). Wilson, H. X., A n a l y s t , 76,65-76 (1951). Wurzschmitt, B., Chem.-Ztg., 74,356-60 (1950). Yoe, J. H., and Rush, R. hf., -4naZ. Chzm. d c f a , 6, 526-7 (1952). Yoe, J. H., and Will, F., Ibid., 6,450-1 (1952). Young, I. G., and Hiskey, C. F., ANAL. CHEY., 23, 506-8 (1951). Zaichikova, L. B., Zanodskaya Lab., 15, 1025-7 (1949). Zamyatina, V. B., Soaet. Agron., 1950, S o . 7, 58-64. Zeppelin, H. v., Angew. Chem., 63, 281-2 (1951). Zeppelin, H. v., and Fuchs, J., Ibid., 64, 223-4 (1952). Zhuravskaya, V. I., Zaaodskaya Lab., 16, 1302-4 (1950). Zimmermann, M., Angew. Chem., 62A, 291-2 (1950). Zoellner, H., Glas-Email-Keramo-Tech., 2 , 378-81 (1951).
c.,
FOOD JOHN R. MATCHETT AND HARRY W. VON LOESECKE Bureau of Agricultural & Industrial Chemistry, Agricultural Research Administration, United States Department of Agriculture, Washington, D. C.
T
HIS review covers the period of December 1951 t o October 1952. It is a sequel to the review of methods of food analyses
for the period December 1950 to November 1951 (127). MOISTURE
Rapid and simple methods of moisture determination applicable t o all types of food materials are still sought, b u t i t seems doubtful that such a goal will ever be attained, although i t has been stated that the Karl Fischer method approaches stoichiometrical accuracy for water in most foodstuffs (10). The basic causes of difficulties associated with moisture tests have been the subject of a symposium (35). An electrical apparatus has been developed for Karl Fischer titrations (66) which utilizes the dead-stop principle, automatically adds the reagent, and differentiates between “true” and “false” fleeting end points. The Karl Fischer method has also been used for estimating moisture in dehydrated vegetables by substituting formamide for dry methanol as the extraction solvent (132). A rapid, simple method for moisture in fruits and vegetables, based upon oxidation with a potassium chromate solution (193), has been applied with equal success for moisture determinations in pineapple-rice pudding, rice, prunes, and fresh frozen corn (112).
Though sesame is one of the oldest cultivated oilseed crops, no systematic investigation of moisture and volatile matter methods
has been reported. A proposed method makes use of a forced draft oven at 130’ C. using a 2-gram sample (180), and a rapid dielectric method has been suggested for oilseeds and cakes (If%). However, the relation between the dielectric constant and moisture in the material cannot be expressed by a simple function and a separate calibration is necessary for each kind of seed. Problems of moisture determination in milk products (96), cereals and legumes (56), and meat and meat products (12) have been considered in the light of different methods suggested from past experiences. A modification of the Dean and Stark moisture apparatus makes possible moisture determination in materials containing large amounts of water (89). Modification consists of a graduated receiving column fitted into a small flask of known capacity. S i n e such flasks are used, ranging in capacity from about 20 to 80 ml., according t o the moisture content of the sample being tested . A rapid moisture method for beet pulp is based on the release of moisture from pressed pulp by contact with molasses (36). PROTEINS AND AMINO ACIDS
Although 70 years have passed since Kjeldahl first proposed his method, i t is still being subjected t o modification and discussion. One of the more recent modifications describes a n e v digestion apparatus (206). Chromatographic separation of amino acids continues t o occupy
