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Progress in elemental quantitative organic analysis: 1958
MICROCHEMICAL
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1958
AI, STEYERMARK, Hoflmann-La Nutley, New Jersey
Roche Inc.,
This review includes only those articles that were published during 1958* and which deal with the quantitative microanalysis of an element, or elements, present in an organic compound. As a further limitation, the sample size must be in the milligram or submilligram range rather than just the end product as would be the case in trace analyses, the exceptions being the occasional articles of the latter type that the reviewer feels are applicable to the former. A number of reviews,5~34~35~5g~60~81-*3~85~100~113 both general and on specific phases of this field in question, were published, and the article by Steyermark113 listed reviews for previous periods of time. Kuck74 discussed developments in microchemistry in contrast to those in instrumentation in an article which gives much food for thought. Ma reviewed the literature of organic microchemistry,*l covering all phases during the two year period of 1956-57, and in another article he reviewed the literature on the analysis (C, H, N, halogen, sulfur, fluorine, etc.) of fluorine-containing compounds*3 through 1957. Another review,85 although appearing in 1957, is worthy of listing. The historical developments in quantitative organic microanalysis from the days of Pregl to the present were described in an article by Steyermark.l13 The role played by the various groups in the United States working on standardization of methods and apparatus was emphasized. One hundred and five references, including the reviews for previous periods, were given. * Several articles which available are also included.
appeared
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General In order to avoid the use of micro apparatus, a technique was developed whereby macro equipment can be used.le2 In the opinion of the reviewer, this would seem to be of interest only in localities where macro and not micro apparatus is available. The results of long term analyses were recorded by Kono.e*,69 The test sample used and statistical data on the results for the carbonhydrogen, nitrogen, sulfur, and oxygen determinations were included. This type of material is always of value. Smith107 described the preparation of 5-chloro-4-hydroxy-3-methoxy-benzylisothiourea phosphate, a multipurpose test compound which can be used for the determination of C, H, Cl, P, N, S, and methoxyl. The reviewer prefers the use of test substances having critical values of the elements to be determined and such is not the case with the Smith compound. It does have great value for occasional checking of the various pieces of the apparatus with a compound containing many interferences. Kirsten59f60 and Belcher7,*0 continued to explore various determinations using samples below the milligram scale. This work, although not yet as accurate and precise as ordinary micro work, is extremely valuable and eventually will compete with the latter. A new international journal of analytical chemistry, Talanta,ll* was published for which C. L. Wilson is Editor-in-chief, and L. Gordon, R. Pribil, and T. Takahashi are regional editors. The seventh editionlOa of the Roth-Pregl book on quantitative organic microanalysis was published. The book is written in the style used for previous editions. The subjects covered are: (a) general information, (b) determination of the elements, usually encountered (CH, N, halogens, sulfur, etc.), (c) determination of a large number of groups, and (d) determination of physical constants. In view of the recent literature on the subject, the method described for the determination of fluorine might not be expected to give reliable results with certain compounds, particularly the perfluoroones. Also, in the opinion of the reviewer, well dimensioned drawings In general, the would have been preferable to those used by Roth. book is an excellent contribution to the literature of the field.
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Carbon-Hydrogen For very obvious reasons, the carbon-hydrogen determination Various continues to be the subject of a number of investigations. improvements in the method have been tried,7K~88*Sg including the absorption of nitrogen oxides by hydroxylamine sulfate@ and ammonium sulfamate.8g Kirsten5g w as successful with samples weighing 0.1 mg. Elimination of the Mariotte bottle and pressure regulator as well as modified absorption tubes are the basis of a rapid procedure.lo2 ‘*A simple technique for handling volatile materials,gg as well as one for pyrophoric and hygroscopic samples, making use of polyethylene bagslo have been described. Excellent results were reported by replacing the Pregl filling with cobalto-cobaltic oxide126,12g,130 as the combustion catalyst. A temperature of 650 to 700°C. is required. Silver dichromate also has been used as the catalyst.lO* Modifications of the Kijrbl silver perma,nganate filling have been described by several workers.47~4g~64~80~100~105 This type of filling is rapidly gaining favor, particularly in Europe, speed and accuracy being claimed through its use. Pella’OOmade an extensive study of the Kiirbl method, confirmed its effectiveness, and listed references to other papers on the method. Kiirbl has also used mixed oxides of silver and cobalt, cerium, iron, or manganese. 48 A number of articles described the determination of carbon and hydrogen in the presence of interfering elements in the compound to be analyzed. These elements include silicon,63 fluorine,*2,73 and selenium.133 The simultaneous determinations of carbon-hydrogen and other elements were also described. These include fluorine,73 silicon and sulfur,63 nitrogen,36s62 and sulfur and halogen.s7 The results claimed are usually of the same accuracy as for the individual determinations. Combustion under reduced pressure2g was found to give good results with volatile and readily decomposable substances. A new horizontal-type tube for the so-called “empty tube” technique has been described.46 This procedure is in extensive use in England, but such is not, the case in the United States where fillings are still preferred. The titrimetric procedure of determining the carbon dioxide has been studied12 in England by Belcher and his co-workers. Carbon alone was determined using a wet combustion.6 Succinyl chloride has been used for the determination of the water.ll
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The British Standards Institution continued its extremely valuable work of standardization and published revised specifications for the carbon-hydrogen determination.16 These are changes thought necessary since the original publication of 1950.
Nitrogen Methods for the simultaneous determination of nitrogen along with carbon and hydrogen have been referred to above.36*62 The same holds true for the ultramicro determination of nitrogen using 0.1 mg. samples by Kirsten.5g Reference has also been made to a statistical evaluation of results.6g Raney nickelgo has been employed in the micro-Dumas determination and was found to effect the removal of oxygen and complete reduction of nitrogen oxides without the dissociation of carbon dioxide. The micro-Dumas-Sch6niger106 procedure was adapted to the semi-micro scale for determining nitrogen in coke.8 A simplified novel apparatus for a swift Dumas determination was described by Otter.g7 A wet ashing method using iodic acid followed by collection of the nitrogen in an azotometer was described,gs as well as the determination of nitrogen and fluorine41 and of nitrogen, sulfur, and halogens in a single sample.30 Hydrogenation has also been used for the determination of nitrogen both on the micro- and semimicro scales.40 The Kjeldahl determination has received the attention of a number of workers. Reduction with zinc and hydrochloric acid followed by reduction with iron and hydrochloric acid previous to Kjeldahlization was very successfully used on a variety of compounds containing nitrogen to nitrogen and nitrogen to oxygen linkages.l”j These included azo and nitro compounds, oximes, isoxazoles, hydrazines, and hydrazones. Where nitrogen was connected to nitrogen in a ring, such as in pyrazolones, 1,2-diazines, and 1,2,3-triazoles, some good values were obtained, but the results were not reliable. The same authorsll6 described another procedure for nitrates which gives equally very reliable results. In the process, salicylic acid is first nitrated, then reduced with thiosulfate, and finally kjeldahlized. Rapid Kjeldahlization on the semimicro scale was carried out by using, for 20-50 mg. samples, 0.15 g. HgO, 1.2 g. K2SO4, and 1.5 ml. cont. HzSO4.76 This procedure is very similar to that resulting from the collaborative studies conducted by Willits and Ogg years ago and MICROCHEMICAL
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used rather extensively in this country, 114the only exception being the slightly higher ratio of HgO and K$304 to HzS04 which would raise Tin or stannous chloride32 have been the boiling point of the mixture. used successfully as a catalyst for the semimicro-Kjeldahl procedure. The value of mercury as a catalyst as well as longer digestion periods have been confirmed.131 The Kjeldahl method has been successfully used on fluorine compounds 31 coke,g1 biological fluids,77,120 and petroleum fractions.86 The efficiency of the microdistillation of ammonia developed by micro-Kjeldahlization has been the subject of a study.22 An ultramicro diffusion method employing white transparent plastic cells has been successfully used for ammonia in the range of 0.01-10.0 pM in 0.01-0.02 ml. samples.38 This has value in connection with the ultramicro-Kjeldahl determination.
Halogens The determinations of carbon, hydrogen, sulfur, and halogens37 and of nitrogen, sulfur, and halogens 3oin a single sample have been referred to above. A number of investigations on chlorine, bro~~~~~~3,10,14,26,30,37,46,50,55,67,61,66,71,72,78,93,96,108,111,117,121~123,127,128 mine, and were published during the year. Catalytic combustion was used &-&en61 USed nitric, perrather extensively. 3,37,71,93,96,108,121,123,121 chloric, and sulfuric acids for decomposition of iodo compounds followed by iodimetric titration. Carius,“’ sodium peroxide,45,66 Schoniger, 14,26,71,123 lime in sealed tubes, lg and magnesium nitridellg decompositions were also used. Titrimetry has been used as the final stage by a number of investilz3 This has included the use of Variamine gators. 19,26~45,61,7*,93,119,121 B1uez6 and Brilliant Yellow121p123as indicators, thiocyanate,1gs11gr123 automatic coulometric titration,l17 convection amperometry,55 automatic titrator,45 silver-glass electrode system with a pH meter,78 and colorimetry.127 The final stages of the determinations were also carried out gravimetrically.37*66*111 Belcher and co-workers10 determined iodine and bromine in samples weighing only 50 pg. with an accuracy of l tO.4%. Iodine was also determined in blood serum11oand in milk,g2 isothermal diffusion being used in the former. A review by Mag3 of the micro analysis of organic fluorine compounds was referred to above. This discusses the determinations of
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the various elements, including fluorine. His general reviews1 also contains material on this determination and another review by him82 covered the determination of fluorine itself. These articles are invaluable to those working in this field. The simultaneous determination of fluorine, carbon, and hydrogen73 and of fluorine and nitrogen 41 have been referred to above. A micro-Parr bomb assembly suitable for the decomposition of fluoro compounds was described.l15 These units stand up under prolonged heating at 700%. with metallic sodium or potassium and can be used over again for many fusions. For the final stage of one investigation, lead chlorofluoride was dissolved in complexone III solution and its chloride content titrated with silver using variamine blue as indicator.27 Ion exchange using Dowex-1 acetate also has been used for determining fluorine in animal tissue.g4
Sulfur Alicino5 reviewed the various methods used for the determination of sulfur in organic compounds, making comparisons. Ma81 in his general review also covered this subject. Catalytic combustion,3,13,28,30.37,63,84,124,125 SchGniger method,14e79s98peroxide bomb 765 and chromic-phosphoric acid58 were used to destroy organic matter Gravimetric, 13,28,35,7g voluand convert the sulfur to sulfate. metric 13,66,7g,84,98,126and spectrophotometric4s58methods were employed for the final stage. The volumetric methods included barium chloride with tetrahydroxyquinone as indicator,66 potentiometric,g8p125 iodimetric,13 and acidimetric.7g184 Belcher and his co-workers7 extended their important work on submicro methods of analysis of organic compounds to the determination of sulfur. Fifty micrograms of sample are treated with fuming nitric acid and barium chloride. The resulting barium sulfate is dissolved in an excess of EDTA and the excess then titrated with magnesium chloride.
Oxygen Fort reviewed the direct determination of oxygen in organic compounds in two articles34s35and Ma included the subject in his general review.8’ Kono6gs70published the results of his long term routine analyses. His method employed copper at 45O’C. plus hydrogen to Three investigations remove oxygen from the carrier gas, nitrogen. MICROCHEMICAL
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were reported by Imaeda.52-54 He purified the carrier nitrogen by means of reduced copper at 550°C.,52 studied the reaction tube filling.53 and introduced a new internally heated iodine pentoxide tube containing silver granules.54 A potentiometric determination of oxygen as carbon dioxide with automatic titration25 was found to give very good results. Dixonz3 preferred copper oxide to iodine pentoxide since the interferences due to hydrogen and sulfur were thusly eliminated. The results obtained from a collaborative study112 on the determination of oxygen indicated that excellent results may be obtained from a variety of procedures including volumetric, gravimetric, and manometric with either carbon at 112O’C. or Most collaborators used platinized carbon at 92O’C. as tube fillings. copper at about BOO’C. for purifying the carrier gas, which was unanimously nitrogen. The collaborative study is being continued in an effort to obtain a method suitable for adoption by the Association of Official Agricultural Chemists.
Phosphorus Several investigatorsg,20z33preferred the Schijniger flask combustion for conversion of organic phosphorus to phosphate while the nitricsulfuric acid treatment was used by another group.ls Methods were described employing the molybdenum blue, l* heteropoly blue, 33 quinoline phosphomolybdate,g S-quinolinol phosphomolybdate,44 and molybdenum sulfide-chromium ammonium chloride43 reactions. Citric and boric acids were found to prevent interference of fluorine when the quinoline phosphomolybdate reaction was used.g Gravimetric,a3f44 titrimetric,gp33 and colorimetric18J3,56 procedures were employed, one of which used EDTA.33
Arsenic, Mercury, Magnesium, Zinc, and Cadmium Small amounts of arsenic have been determined by means of the color developed by arsine on paper impregnated with mercuric salts17,132and one of the investigators applied internal electrolysis for obtaining the arsine.132 Wet combustion followed by absorption spectroscopy was applied to t,he determination of arsenic in coal and coke.21 Mercury in organomercurials was determined by Schijniger combustion followed by amperometric titration with EDTA. log Chloride interferes with the determination. A method employing
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di-2-naphthylthiocarbazone was also describeda as well as one using sodium and zinc for decomposition followed by either volumetric or calorimetric procedure3g and one employed electrolysis.24 Magnesium in organic compounds in the presence of known amounts of calcium was determined making use of a color comparator.61 For magnesium, zinc, and cadmium, flask combustion was used.ga
Boron, Silicon, and Selenium A flame spectrophotometric method was described for the determination of boron in organic compounds which is applicable to any type sample soluble in naphtha-2-propanol. l6 Flask combustion was also used for boron.9” The simultaneous determination of carbon, hydrogen, silicon, and sulfur has been referred to previously.‘j3 Selenium was determined gravimetrically after decomposing the sample in a sodium peroxide bomb.67 An accuracy of ~0.5% was obtained.
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9a. R. Belcher, A. M. G. Macdonald, and T. S. West, Tduntu, 1,408 (1958). “The determination of metals in organic compounds by the closed flask method.” 10. R. Belcher, R. A. Shah, and T. S. West, J. Chem. Sot., 1958.2998. “Submicro methods for the analysis of organic compounds. Part IV. The determination of iodine and bromine.” 11. R. Belcher, J. H. Thompson and T. S. West, Anal. C&m. Acta, 19, 148 “Succinyl chloride as a hydrolytic reagent for the determination of (1958). water.” 12. R. Belcher, J. H. Thompson, and T. 5. West, Anal. Chim. Acta, 19, 309 “The titrimetric det,ermination of carbon dioxide with special reference (1958). to the determination of carbon in organic compounds.” 13. E. Bladh, K. J. Karrman, and 0. Andersson, Mikrochim. Ada, 1958, 60. “On the microdetermination of sulphur in organic compounds by the silver gauze method.” 14. M. Boetius, G. Gutbier, and H. Reith, Mikrochim. Ada, 1958, 321. “Bestimmung von Halogen (Cl, Br, J) und Schwefel in Einwaage nach dem Vorbild der Mikromethode von W. Schiiniger.” 15. British Standards Institution, B.S. 1428: Part Al: 1958. “Carbon and hydrogen combustion train (Pregl t,ype). Microchemical apparatus.” 16. B. E. Buell, Anal. Chem., 30, 1514 (1958). “A direct flame photometric determination of boron in organic compounds.” 17. S. P. Bystrov and Y. I. Parshikov, Aptechnoe Delo, 6, 38 (1957); through CA., 52, 6059 (1958). “The determination of small amounts of arsenic II.” 18. R. A. Chalmers and D. A. Thomson, Anal. Chim. Ada, 18, 575 (1958). “A method for the determination of phosphorus in organic compounds.” 19. Fan-Tih Chiang, Chenbistry (Taiwan), 1957, 96; through C.A., 53, 120 “Determination of halogen in organic substances with the sealed tube (1959). lime fusion method.” 20. L. E. Cohen and F. W. Czech, Chenlisl Analyst, 47, 86 (1958). “The determination of phosphorus in organic compounds via flask combustion.” 21. A. Crawford, J. G. Palmer, and J. H. Wood, Mikrochim. Ada, 1958, 277. “The determination of arsenic in microgram quantities of coal and coke.” 22. S. Dittrich and J. X. devries, pR (Montevideo), 5, No. 4, 78D (1955); through CA., 52, 169 (1958). “The microdistillation of ammonia in the Kjeldahl determination.” 23. J. P. Dixon, Anal. Chim. Ada, 19, 141 (1958). “The direct micro determination of oxygen in organic material.” 24. I. G. Druzhinin and P. S. Kislitsin, Trudy Inst. Khim., Aknd. Nuuk Kiiirg SSR, 1957, 21. Ref. Zhur., Khim., 1958, Abstract No. 57237; through Anal. determination of mercury in .4bstmcts, 6, Abstract 587 ( 1959). “Quantitative organic compounds.” 25. F. Ehranberger, S. Gorbach, and W. Mann, Mikrochim. Acta, 1958, 778. “BeitrLge zur mikroa,nalytischen Bestimmung des Sauerstoffes in organischen Substanaen.” 26. L. Erdley, L. M&or, and T. Meisel, Mikrochim. Ada, 1958,140. “Argentometrische Mikrobestimmung organischer Halogenverbindungen nach Verbrennung in Anwesenheit von Variaminblau als Indikator.”
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27. L. Erdey, L. M4zor, and M. P&pay, Mikrochim. Acta, 1958, 482. “Mikrobestimmung des Fluors durch direkte argentometrische Titration des Chloridgehaltes des PbClF Niederschlages.” 28. A. Etienne and J. Leger, Chim. anal., 40, 43 (1958); through Anal. Abstracts, 5, Abstract 3769 (1958); and C.A., 52, 8835 (1958). ‘Semi-micro gravimetric determination of sulphur in organic substances by combustion.” 29. P. N. Fedoseev and L. S. Ignatenko, Z.zv. Akad. Nauk, Tut-km. SSR, 1957, 24; through Anal. Abstracts, 5, Abstract 3764 (1958). “New vacuum method for the determination of carbon and hydrogen in organic substances.” 30. P. N. Fedoseev and N. P. Ivashova, Zhur. Anal. Khim., 13, 230 (1958). “New methods for the quantitative determination of nitrogen and halogens, and also of nitrogen, sulfur, and halogens in a single sample of organic substances. Part 4.” “The 31. T. R. F. W. Fennel1 and J. R. Webb, Analyst, 83, 694 (1958). determination of nitrogen in certain fluorinated compounds by the Kjeldahl method.” “Semimicro32. V. B. Fish and P. R. Collier, Anal. Chem., 30, 151 (1958). Kjeldahl procedure for pyridinium halide and oxyhalide salts.” 33. K. D. Fleischer, B. C. Southworth, J. H. Hodecker, and M. M. Tuckerman, Anal. Chem., 30, 152 (1958). “Determination of phosphorus in organic compounds. Rapid micro and semimicromethod.” through C.B., 52, 972 (1958). 34. R. Fort, Chim. anal., 39, 319 (1957); ‘
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43. C. Gheorghiu and E. Radulescu, Rev. chim. (Bucharest), 8, 779 (1957); “Gravimetric determination of small quantities through C.A., 52, 7013 (1958). of phosphorus.’ ’ 44. G. Gottschalk, Z. anal. Chem., 159, 257 (1958). “Zur Gravimetrischen Halbmikro-und Mikro-Bestimmung des Phosphors als 3-Oxin-I-phosphor-12molybdat.’ ’ 45. J. Haslam and J. I. Hall, Analyst, 83, 196 (1958); through Anal. Abstracts, 5, Abstract 3061 (1958), and C.A., 52, 13522 (1958). “Semi-micro determination of chlorine in poly(viny1 chloride) and related polymers.” 46. W. M. Haeenberg, Mikrochim. Acta, 1958, 709. “A new type of combustion tube for carbon-hydrogen determination by the “rapid combustion method.” 47. J. HoraEek and D. Grtinberger, Chem. listy, 51, 1944 (1957); through “A rapid modified method for the determination of C.A., 52, 1853 (1958). carbon-14.” 48. J. HoraEek and J. Korbl, Chem. & Znd., 1958, 101; through Anal. Abstracts, 5, Abstract 3358 (1958). “New silver-containing catalysts for elemental combustion analysis.” 49. J. Hortiek and J. Korbl, Chem. Zisty, 51, 2132 (1957); through C.S., 52, 2661 (1958). “Analytical applications of silver permanganate. VIII. Micro- and semimicrodetermination of carbon and hydrogen in organic compounds containing fluorine.” 50. W. Hiilsen, J. Chromatography, 1, 91 (1958). “Bemerkung zur Mikrojodbestimmung nach Bowden, Maclagan und Wilkinson.” 51. G. Hunter, Analyst, 83, 93 (1958). “Microdetermination of magnesium in presence of known amounts of calcium.” 52. K. Imaeda, Yakugaku Zasshi, 77, 1192 (1957); through C.A., 52, 4395 “Organic microanalysis. XV. Efficiency of reduced copper in the (1958). elimination of oxygen from nitrogen gas used in the direct determination of oxygen.” 53. K. Imaeda, Yakuguku Zasshi, 78, 30 (1958); through C.A., 52, 6065 “Organic microanalysis. XVI. Reaction products in combustion tube (1958). including a modified tube filling in direct determination of oxygen.” 54. K. Imaeda, Yakugaku Zasshi, 78, 386 (1958); through C.A., 52, 11653 “Organic microanalysis. XVII. An improved determinating process (1958). of carbon monoxide for the Schutze method in direct oxygen analysis.” 55. A. L. Juliard, Anal. Chem., 30, 136 (1958). “Automatic titration of micro amounts of chloride by convection amperometry.” 56. M. Jurecek and J. Jenik, Collection Czechoslov. Chem. Commun., 23, 447 “Uber den Magnesiumaufschluss organischer Substanzen. V. Kolor(1958). imetrische Mikrobestimmung von Phosphor in organischen Verbindungen.” “Semimicro57. D. Kaplan and I. Schnerb, Anal. Chem., 30, 1703 (1958). determination of bromides. Application to physiological fluids.” 58. T. Kiba, I. Akaza (nee Kishi), and S. Taki, Bull. Chem. Sot. Japan, 30, 482 (1957); through C.A., 52, 2646 (1958). “Microcolorimetric determination of organic sulfur by the tin(II)-strong phosphoric acid reduction method.” 59. W. J. Kirsten, Chim. anal., 1958, 253. “Methodes de combustion en tube scelle pour l’analyse ultra-micro elementaire organique quantitative.”
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69. W. J. K&ten, Micro&em. J., 2, 179 (1958). “Quantitative organic microchemistry below the milligram scale.” 61. W. Kirsten and S.-E. Rogozinsky, Chemist Analyst, 47,58 (1958). “Rapid method for the determination of iodine in organic substances.” 62. V. A. Klimova and G. F. Anisimova, Izvest. Akad. Naulc S.S.S.R., Otdel. Khim. Nuuk, 1958, 791; through C.A., 52, 16975 (1958). “Simultaneous determination of carbon, hydrogen, and nitrogen.” 63. V. A. Klimova and E. G. Bereznitskaya, Zhur. Anal. Khim., 12, 424 (1957); through C.A., 52, 1853 (1958). “Rapid methods of microelementary analysis. XIII. Simultaneous determination of carbon, hydrogen, silicon, and sulfur in sulfur-containing silicon-organic compounds.” 64. E. Knii&kova and J. Korbl, Chem. &sty, 52, 750 (1958); through C.A., 52, 12662 (1958). “Use of silver permanganate in analysis. IX. Product of the “isothermal” decomposition of silver permanganate as a combustion catalyst in carbon and hydrogen determinations.” 65. A. Kondo, Bunseki Kuguku, 6, 174 (1957); through C.A., 52, 15345 (1958). “Organic elemental analysis by the microbomb. Volumetric microdetermination of organic sulfur.” 66. A. Kondo, Bunseki Kagaku, 6, 238 (1957); through C.A., 52, 15345 (1958). “Organic elemental analysis by the microbomb. II. Separation and semimicrodetermination of iodine in organic compounds containing other halogens.” 67. A. Kondo, Bunseki Kugaku, 6, 583 (1957), through C.A., 52, 15345 (1958). “Organic elemental analysis by the microbomb. III. Gravimetric microdetermination of organic selenium.” 68. T. Kono, ,Mik?ochim. Acta, 1958, 461. “An automatic method for elementary micro analyses.” 69. T. Kono, Nippon NBgei-Kagaku Kaishi, 31, 822 (1957); through C.A., “Automatic micro elementary analyses.” 52,12662(1958). 70. T. Kono, K. Sato, 111.Suzuki, and I. Isobe, Nippon NGgei-Kagaku K&hi, 31,587 (1957); through C.A., 52,12662 (1958). “Microdetermination of oxygen. VI. Results in routine work.” 71. A. Konovalov, Ind. chim. beige, 23, 19 (1958); through C.A., 52, 7944 “Experimental criticism of the different methods for determining (1958). organic iodine.” 72. M. 0. Korshun and E. A. Bondarevskaya, Proc. Acad. Sci. U.S.S.R., Sect. &em., 110, 220 (1956); through C.A ., 52, 4393 (1958). “Simultaneous determination of oxygen and halogens (chlorine, bromine, and iodine).” 73. M. 0. Korshun, N. E. Gel’man, and K. I. Glazova, Proc. Acud. Sci., U.S.S.R., Sect. Chem., 111,1255 (1956); through C.A., 52,6065 (1958). “Simultaneous determination of fluorine, carbon, and hydrogen in heteroorganic compounds.’ ’ 74. J. A. Kuck, Anal. Chem., 30, 1552 (1958). “Perspectives in quantitative organic microanalysis.” 75. B. Kurihara, Yakugaku Zasshi, 77,546 (1957); through Microchem. J., 3, 119 (1959). “Improved method in the microanalysis of carbon and hydrogen.” MICROCHEMICAL
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76. Z. Lada and K. Usiekniewicz, Chem. Anal. (Warsaw), 2, 351 (1957); “Rapid mineralization by a modification of through C.A., 52, 4395 (1958). Kjeldahl’s method on semimicro scale.” “Simple microdetermination 77. C. A. Lang, Anal. Chem., 30, 1692 (1958). of Kjeldahl nitrogen in biological materials.’ ’ 78. I). T. Lcfierts, Microchem. J., 2, 257 (1958). “Microdetermmation of chlorine by nonaqueous potentiometric titration.” “Rapid quanti79. I. Lysyj and J. E. Zarembo, Anal. Chenz., 30,428 (1958). tative determination of sulfur in organic compounds.” “Determina80. I. Lysyj and J. E. Zarembo, Microchem. J., 2, 245 (1958). tion of carbon and hydrogen in organic compounds containing phosphorus and sulfur. A rapid semimicro method using silver permanganate.” “Organic microchemistry.” 81. T. S. Ma, Anal. Chem., 30, 760 (1958). “Determination of fluorine in 82. T. S. Ma, Anal. Chem., 30, 1557 (1958). quantitative organic microanalysis.” “Micro analysis of organic fluorine 83. T. 8. Ma, Micro&em. J., 2,91(1958). compounds.” 84. P. S. Makovetskii and K. 13. Kholodkovskaya, Khim. i Tekhnol. Topliv. i Muse/, 3, 71 (1958). “A rapid method for determining tho sulfur content in liquid fuel.” 85. G. W. C. Milner and J. W. Edwards, Met. Revs., 2, 109 (1957); through “Microchemical analysis.” C.A., 52,9848 (1958). 86. 0. I. Milner, R. J. Zahner, L. 8. Hepner, and W. H. Cowell, Anal. Chem., “Determination of trace quantities of nitrogen in petroleum 30, 1528 (1958). fractions.” 87. H. Miura, Kokumin Eisei, 25, 196 (1956); through C.A., 52, 18083 (1958). “Microdetermination of mercury using di-2-naphthylthiocarbazone.” 88. S. Mizukami, T. Ieki, and H. Kondo, Yakugaku Zusshi, 77, 517 (1957); through Microchem. J., 3, 119 (1959). “Carbon and hydrogen determination. V. Adsorption of nitrogen oxides. 2. Hydroxylamine sulfate.” 89. S. Mizukami, T. Ieki, and N. Morita, Yukugaku Zasshi, 77, 552 (1957); “Carbon and hydrogen determination. through Micro&em. J., 3, 119 (1959). IV. Adsorption of nitrogen oxides. 1. Ammonium sulfamate.” 90. S. Mizukami, K. Miyahara, and K. Numoto, Yakuguku Zusshi, 78, 842 “Nitrogen determination. III. Mod;(1958); through C.A., 52, 18074 (1958). fied micro-Dumas method employing Raney nickel.” “De91. R. A. Mott and H. A. Wilkinson, Fuel (London), 37, 151 (1958). termination of nitrogen in coke by the semimicro Kjeldahl method.” 92. 5. Nemeth and M. Menkyna, Mikrochim. Actu, 1958, 510. “Zur quantitativen Bestimmung von Jod in Milch.” “Deter93. S. W. Nicksic and L. L. Farley, Anal. Chem., 30, 1802 (1958). mination of chlorine and bromine by the high-temperature combustion met,hod.” “Determination of micro94. H. M. Nielsen, Anal. Chem., 30, 1009 (1958). gram quantities of Fluoride.” 95. S. Ohashi, Bull. Chem. Sot. Japan, 28, 177 (1955); through C.A., 52, 15344 (1958). “A rapid determination of nitrogen in organic compounds by the iodic acid decomposition method.”
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96. I. K. H. Otter, Nature, 182, 393 (1958). “Swift combustion of organic compounds for analysis.” 97. I. K. H. Otter, Nature, 182, 656 (1958). “Swift Dumas nitrogen estimation.” 98. R. Ottosson and 0. Snellman, Acta Chem. Stand., 11,185 (1957); through C.A., 52,8835 (1958). “A rapid method to determine sulfur.” 99. A. R. Panicker and N. G. Banerjee, Analyst, 83, 296 (1958). “The rapid determination of carbon and hydrogen in highly volatile combustible organic liquids.” 100. E. Pella, Mikrochim. Acta, 1958, 687. “tiber eine verbesserte Methode der Kohlenstoffund Wasserstoff-Mikrobestimmung nach Kdrbl.” 101. W. P. Pickhardt, L. W. Safranski, and J. Mitchell, Jr., Anal. Chem., 30, “Microdetermination of carbon and hydrogen in pyrophoric and 1298 (1958). hygroscopic organic compounds.” 102. G. I. Robertson, L. M. Jett, and L. Dorfman, Anal. Chem., 30,132 (1958). “Microdetermination of carbon and hydrogen by rapid combustion procedure.” 103. H. Roth, Pregl-Roth Quantitative Organ&he Mikroanalyse, Siehente, vollkommen neu bearbeitete ?Lnd erweiterte aujlage. Wien, Springer-Verlag, 1958. 104. E. Ruf, 2. anal. Chem., 163,21 (1958). “Darstellung von Silberdichromat. und seine Verwendung zur Herstellung eines Katalysators fur die C-H-Verbrennungsanalyse.” 105. V. Satava and K. KGrbl, Collection Czechoslov. Chem. Commun., 22, 1380 “Analytical applications of silver per(1957); through CA., 52, 7929 (1958). manganate. VII. Thermal decomposition of silver permanganate.” 106. W. Schiiniger, Mikrochimie, 39, 229 (1952). “Uber eine Modifikation der Mikrostickstoffbestimmung nach Dumas-Pregl.” 107. W. H. Smith, Anal. Chem., 30, 149 (1958). “Multipurpose standard for microchemical analysis.” 108. N. V. Sokolova and K. T. Loseva, Zhur. Anal. Khim., 13, 349 (I 958); “Micromethod for determination of halides in through C.A., 53, 117 (1959). organic substances. II. Determination of halide by combustion in a stream of oxygen.” 109. B. C. Southworth, J. H. Hodecker, and K. D. Fleischer, Anal. Chem., 30, “Determination of mercury in organic compounds. Micro and 1152 (1958). semimicromethod.” 110. H. Spitzy, M. Reese, and H. Skrube, Mikrochim. Acta, 1958, 488. “Eine neue, einfache Jodbestimmung im Blutserum unter Anwendung der Isothermdiffusion.” 111. Al Steyermark, J. Assoc. Ofic. Agr. Chemists, 41, 297 (1958). “Report on microanalytical determination of iodine. Part II.” 112. Al Steyermark, J. Assoc. O&. Agr. Chemists, 41, 299 (1958). “Report on microanalytical determination of oxygen.” 113. Al Steyermark, Miclochem. J., 2, 21 (1958). “Historical developments in quantitative organic microanalysis.” 114. Al Steyermark, Quantitative Organic Microanalysis. Blakiston, Philadelphia, 1951. 115. Al Steyermark and F. P. Biava, Anal. Chem., 30, 1579 (1958). “MicroMICROCHEMICAL
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Parr bomb assembly suitable for microdetermination of fluorine in organic compounds.” 116. Al Steyermark, B. E. McGee, E. A. Bass, and R. R. Kaup, Anal. Chem., 30, 1561 (1958). “Micro-Kjeldahl method for nitrogen in certain organic compounds containing nitrogen-nitrogen and nitrogen-oxygen linkages.” 117. 0. E. Sundberg, H. C. Craig, and J. S. Parsons, Anal. Chem., 30, 1842 (1958). “Determination of halogen in organic compounds by automatic coulometric titration.” 118. T&T&Z, International Journal of Analytical Chemistry, Pergamon Press, New York, London, Paris, Los Angeles; C. L. Wilson, Editor-in-Chief. Regional Editors: L. Gordon, U.S.A., R. Piibil, Czechoslovakia, T. Takahashi, Japan. 119. A. P. Terent’ev, S. I. Obtemperanskaya, and N. V. Ermolenko, i\rauch. Doklady Vysshei Shkoly, Khim. i Khim. Tekhnol., 1958, No. 1, 83; through C.A., 53, 973 (1959). “Determination of chlorine and bromine in organic compounds with magnesium nitride.” 120. W. W. Tourtellotte, J. A. Parker, R. E. Alving, and R. N. Delong, Anal. “Determination of total protein in cerebrospinal fluid Chem., 30, 1563 (1958). by an ultramicro-Kjeldahl nitrogen procedure.” 121. M. Vereia and J. BuluSek, Chem. &sty, 52, 1526 (1958); through C.A., 52,19712 (1958). “Organic quantitative analysis. XX. Microassay of chlorine in organic compounds by combustion in an empty tube.” 122. M. Vefei-a and J. BuluSek, Collection C. tichoslov. Chem. Common., 23, 257 (1958). “Organische quant.itativc Analyse. X. Mikrobestimmung von Chlor und Brom in organische Substanzen.” 123. M. VeEei-a and J. BuluSek, Mikrochim. Acta, 1958, 41. “Mikrobestimmung von Chlor und Brom in orgnnischen Stoffen. XV. Meitteilung iiber die quantitative organische Analyse.” 124. M. Vefefa and 1). Snob& Collection Czechoslov. Chem. Commun., 22, 986 (1957); through C.A., 52, 6056 (1958). “Organic quantitative analysis. VIII. Microestimation of sulfur in organic compounds. Mechanism of formation of silver sulfate.” 125. M. VeEeia and D. Snobl, Mikrochim. Ada, 1958,28. “Mikrobestimmung von Schwefel. XIV. Mitteilung iiber die quantitative organische Analyse.” 126. M. Vefei-a, D. Snobl, and L. Synek, Mikrochim. Acta, 1958, 9. “Bin Schnellverfahren zur C-H-Mikro-Bestimmung in organischen Substanzen. XIII. Mitteilung tiber die quantitative organische Analyse.” 127. M. Vecefa and A. SpEvak, Chem. l&y, 51, 2037 (1957); through C.A., 52, 2648 (1958). “Organic quantitative analysis. XVII. Determination of small amounts of chlorine and bromine in organic compounds.” 128. M. Ve&eFa and A. SpCv4k, Collection Czechoslov. Chem. Commun., 23, 1197 (1958). “Organische quantitative Analyse. XVII. Bestimmung kleiner Chlorund Brommengen in organischen Substanxen.” 129. M. VeEe?a and L. Synek, Chem. Zistv, 51, 2266 (1957); through C.A., 52, 4393 (1958). “Organic quantitative analysis. XVIII. Microdetermination of carbon and hydrogen with cobalt-cobaltic oxide as combustion catalyst.” 130. RI. VeEeFa and L. Synek, Collection Czechoslov. Chem. Commun., 23, 1202 (1958). “Organische Quantitative Analyse. XVIII. Mikrobestimmung von
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Kohlenstoff und Wasserstoff unter Verwendung von Cobalt(I1, III)-Oxyd als Verbrennungskatalysator.” 131. R. F. Gomee Vigide, Inf. Q&m.. Anal., 12, 9 (1958); through Anal. “The Kjeldahl-Roachese method for the Abstracts, 5, Abstract 3767 (1958). rapid determination of organic nitrogen.” 132. C. Yoshimura, Nippon Kagaku Zasshi, 78, 1586 (1957); through C.A., “New microdetermination of arsenic by the application of 52, 16120 (1958). internal electrolysis.” 133. A. S. Zabrodina and S. Ya Levina, Vestnik Moskov. Univ., Ser. Mat., Me&, Astron., 8’i.z. i Khim., 12, 181 (1957); through C.A., 52, 19680 (1958). “Microdetermination of carbon and hydrogen in organoselenium compounds.”
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AI, STEYERMARK, Hoflmann-La Nutley, New Jersey
Roche Inc.,
This review includes only those articles that were published during 1958* and which deal with the quantitative microanalysis of an element, or elements, present in an organic compound. As a further limitation, the sample size must be in the milligram or submilligram range rather than just the end product as would be the case in trace analyses, the exceptions being the occasional articles of the latter type that the reviewer feels are applicable to the former. A number of reviews,5~34~35~5g~60~81-*3~85~100~113 both general and on specific phases of this field in question, were published, and the article by Steyermark113 listed reviews for previous periods of time. Kuck74 discussed developments in microchemistry in contrast to those in instrumentation in an article which gives much food for thought. Ma reviewed the literature of organic microchemistry,*l covering all phases during the two year period of 1956-57, and in another article he reviewed the literature on the analysis (C, H, N, halogen, sulfur, fluorine, etc.) of fluorine-containing compounds*3 through 1957. Another review,85 although appearing in 1957, is worthy of listing. The historical developments in quantitative organic microanalysis from the days of Pregl to the present were described in an article by Steyermark.l13 The role played by the various groups in the United States working on standardization of methods and apparatus was emphasized. One hundred and five references, including the reviews for previous periods, were given. * Several articles which available are also included.
appeared
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to 1958 in journals
not readily
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General In order to avoid the use of micro apparatus, a technique was developed whereby macro equipment can be used.le2 In the opinion of the reviewer, this would seem to be of interest only in localities where macro and not micro apparatus is available. The results of long term analyses were recorded by Kono.e*,69 The test sample used and statistical data on the results for the carbonhydrogen, nitrogen, sulfur, and oxygen determinations were included. This type of material is always of value. Smith107 described the preparation of 5-chloro-4-hydroxy-3-methoxy-benzylisothiourea phosphate, a multipurpose test compound which can be used for the determination of C, H, Cl, P, N, S, and methoxyl. The reviewer prefers the use of test substances having critical values of the elements to be determined and such is not the case with the Smith compound. It does have great value for occasional checking of the various pieces of the apparatus with a compound containing many interferences. Kirsten59f60 and Belcher7,*0 continued to explore various determinations using samples below the milligram scale. This work, although not yet as accurate and precise as ordinary micro work, is extremely valuable and eventually will compete with the latter. A new international journal of analytical chemistry, Talanta,ll* was published for which C. L. Wilson is Editor-in-chief, and L. Gordon, R. Pribil, and T. Takahashi are regional editors. The seventh editionlOa of the Roth-Pregl book on quantitative organic microanalysis was published. The book is written in the style used for previous editions. The subjects covered are: (a) general information, (b) determination of the elements, usually encountered (CH, N, halogens, sulfur, etc.), (c) determination of a large number of groups, and (d) determination of physical constants. In view of the recent literature on the subject, the method described for the determination of fluorine might not be expected to give reliable results with certain compounds, particularly the perfluoroones. Also, in the opinion of the reviewer, well dimensioned drawings In general, the would have been preferable to those used by Roth. book is an excellent contribution to the literature of the field.
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Carbon-Hydrogen For very obvious reasons, the carbon-hydrogen determination Various continues to be the subject of a number of investigations. improvements in the method have been tried,7K~88*Sg including the absorption of nitrogen oxides by hydroxylamine sulfate@ and ammonium sulfamate.8g Kirsten5g w as successful with samples weighing 0.1 mg. Elimination of the Mariotte bottle and pressure regulator as well as modified absorption tubes are the basis of a rapid procedure.lo2 ‘*A simple technique for handling volatile materials,gg as well as one for pyrophoric and hygroscopic samples, making use of polyethylene bagslo have been described. Excellent results were reported by replacing the Pregl filling with cobalto-cobaltic oxide126,12g,130 as the combustion catalyst. A temperature of 650 to 700°C. is required. Silver dichromate also has been used as the catalyst.lO* Modifications of the Kijrbl silver perma,nganate filling have been described by several workers.47~4g~64~80~100~105 This type of filling is rapidly gaining favor, particularly in Europe, speed and accuracy being claimed through its use. Pella’OOmade an extensive study of the Kiirbl method, confirmed its effectiveness, and listed references to other papers on the method. Kiirbl has also used mixed oxides of silver and cobalt, cerium, iron, or manganese. 48 A number of articles described the determination of carbon and hydrogen in the presence of interfering elements in the compound to be analyzed. These elements include silicon,63 fluorine,*2,73 and selenium.133 The simultaneous determinations of carbon-hydrogen and other elements were also described. These include fluorine,73 silicon and sulfur,63 nitrogen,36s62 and sulfur and halogen.s7 The results claimed are usually of the same accuracy as for the individual determinations. Combustion under reduced pressure2g was found to give good results with volatile and readily decomposable substances. A new horizontal-type tube for the so-called “empty tube” technique has been described.46 This procedure is in extensive use in England, but such is not, the case in the United States where fillings are still preferred. The titrimetric procedure of determining the carbon dioxide has been studied12 in England by Belcher and his co-workers. Carbon alone was determined using a wet combustion.6 Succinyl chloride has been used for the determination of the water.ll
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The British Standards Institution continued its extremely valuable work of standardization and published revised specifications for the carbon-hydrogen determination.16 These are changes thought necessary since the original publication of 1950.
Nitrogen Methods for the simultaneous determination of nitrogen along with carbon and hydrogen have been referred to above.36*62 The same holds true for the ultramicro determination of nitrogen using 0.1 mg. samples by Kirsten.5g Reference has also been made to a statistical evaluation of results.6g Raney nickelgo has been employed in the micro-Dumas determination and was found to effect the removal of oxygen and complete reduction of nitrogen oxides without the dissociation of carbon dioxide. The micro-Dumas-Sch6niger106 procedure was adapted to the semi-micro scale for determining nitrogen in coke.8 A simplified novel apparatus for a swift Dumas determination was described by Otter.g7 A wet ashing method using iodic acid followed by collection of the nitrogen in an azotometer was described,gs as well as the determination of nitrogen and fluorine41 and of nitrogen, sulfur, and halogens in a single sample.30 Hydrogenation has also been used for the determination of nitrogen both on the micro- and semimicro scales.40 The Kjeldahl determination has received the attention of a number of workers. Reduction with zinc and hydrochloric acid followed by reduction with iron and hydrochloric acid previous to Kjeldahlization was very successfully used on a variety of compounds containing nitrogen to nitrogen and nitrogen to oxygen linkages.l”j These included azo and nitro compounds, oximes, isoxazoles, hydrazines, and hydrazones. Where nitrogen was connected to nitrogen in a ring, such as in pyrazolones, 1,2-diazines, and 1,2,3-triazoles, some good values were obtained, but the results were not reliable. The same authorsll6 described another procedure for nitrates which gives equally very reliable results. In the process, salicylic acid is first nitrated, then reduced with thiosulfate, and finally kjeldahlized. Rapid Kjeldahlization on the semimicro scale was carried out by using, for 20-50 mg. samples, 0.15 g. HgO, 1.2 g. K2SO4, and 1.5 ml. cont. HzSO4.76 This procedure is very similar to that resulting from the collaborative studies conducted by Willits and Ogg years ago and MICROCHEMICAL
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used rather extensively in this country, 114the only exception being the slightly higher ratio of HgO and K$304 to HzS04 which would raise Tin or stannous chloride32 have been the boiling point of the mixture. used successfully as a catalyst for the semimicro-Kjeldahl procedure. The value of mercury as a catalyst as well as longer digestion periods have been confirmed.131 The Kjeldahl method has been successfully used on fluorine compounds 31 coke,g1 biological fluids,77,120 and petroleum fractions.86 The efficiency of the microdistillation of ammonia developed by micro-Kjeldahlization has been the subject of a study.22 An ultramicro diffusion method employing white transparent plastic cells has been successfully used for ammonia in the range of 0.01-10.0 pM in 0.01-0.02 ml. samples.38 This has value in connection with the ultramicro-Kjeldahl determination.
Halogens The determinations of carbon, hydrogen, sulfur, and halogens37 and of nitrogen, sulfur, and halogens 3oin a single sample have been referred to above. A number of investigations on chlorine, bro~~~~~~3,10,14,26,30,37,46,50,55,67,61,66,71,72,78,93,96,108,111,117,121~123,127,128 mine, and were published during the year. Catalytic combustion was used &-&en61 USed nitric, perrather extensively. 3,37,71,93,96,108,121,123,121 chloric, and sulfuric acids for decomposition of iodo compounds followed by iodimetric titration. Carius,“’ sodium peroxide,45,66 Schoniger, 14,26,71,123 lime in sealed tubes, lg and magnesium nitridellg decompositions were also used. Titrimetry has been used as the final stage by a number of investilz3 This has included the use of Variamine gators. 19,26~45,61,7*,93,119,121 B1uez6 and Brilliant Yellow121p123as indicators, thiocyanate,1gs11gr123 automatic coulometric titration,l17 convection amperometry,55 automatic titrator,45 silver-glass electrode system with a pH meter,78 and colorimetry.127 The final stages of the determinations were also carried out gravimetrically.37*66*111 Belcher and co-workers10 determined iodine and bromine in samples weighing only 50 pg. with an accuracy of l tO.4%. Iodine was also determined in blood serum11oand in milk,g2 isothermal diffusion being used in the former. A review by Mag3 of the micro analysis of organic fluorine compounds was referred to above. This discusses the determinations of
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the various elements, including fluorine. His general reviews1 also contains material on this determination and another review by him82 covered the determination of fluorine itself. These articles are invaluable to those working in this field. The simultaneous determination of fluorine, carbon, and hydrogen73 and of fluorine and nitrogen 41 have been referred to above. A micro-Parr bomb assembly suitable for the decomposition of fluoro compounds was described.l15 These units stand up under prolonged heating at 700%. with metallic sodium or potassium and can be used over again for many fusions. For the final stage of one investigation, lead chlorofluoride was dissolved in complexone III solution and its chloride content titrated with silver using variamine blue as indicator.27 Ion exchange using Dowex-1 acetate also has been used for determining fluorine in animal tissue.g4
Sulfur Alicino5 reviewed the various methods used for the determination of sulfur in organic compounds, making comparisons. Ma81 in his general review also covered this subject. Catalytic combustion,3,13,28,30.37,63,84,124,125 SchGniger method,14e79s98peroxide bomb 765 and chromic-phosphoric acid58 were used to destroy organic matter Gravimetric, 13,28,35,7g voluand convert the sulfur to sulfate. metric 13,66,7g,84,98,126and spectrophotometric4s58methods were employed for the final stage. The volumetric methods included barium chloride with tetrahydroxyquinone as indicator,66 potentiometric,g8p125 iodimetric,13 and acidimetric.7g184 Belcher and his co-workers7 extended their important work on submicro methods of analysis of organic compounds to the determination of sulfur. Fifty micrograms of sample are treated with fuming nitric acid and barium chloride. The resulting barium sulfate is dissolved in an excess of EDTA and the excess then titrated with magnesium chloride.
Oxygen Fort reviewed the direct determination of oxygen in organic compounds in two articles34s35and Ma included the subject in his general review.8’ Kono6gs70published the results of his long term routine analyses. His method employed copper at 45O’C. plus hydrogen to Three investigations remove oxygen from the carrier gas, nitrogen. MICROCHEMICAL
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were reported by Imaeda.52-54 He purified the carrier nitrogen by means of reduced copper at 550°C.,52 studied the reaction tube filling.53 and introduced a new internally heated iodine pentoxide tube containing silver granules.54 A potentiometric determination of oxygen as carbon dioxide with automatic titration25 was found to give very good results. Dixonz3 preferred copper oxide to iodine pentoxide since the interferences due to hydrogen and sulfur were thusly eliminated. The results obtained from a collaborative study112 on the determination of oxygen indicated that excellent results may be obtained from a variety of procedures including volumetric, gravimetric, and manometric with either carbon at 112O’C. or Most collaborators used platinized carbon at 92O’C. as tube fillings. copper at about BOO’C. for purifying the carrier gas, which was unanimously nitrogen. The collaborative study is being continued in an effort to obtain a method suitable for adoption by the Association of Official Agricultural Chemists.
Phosphorus Several investigatorsg,20z33preferred the Schijniger flask combustion for conversion of organic phosphorus to phosphate while the nitricsulfuric acid treatment was used by another group.ls Methods were described employing the molybdenum blue, l* heteropoly blue, 33 quinoline phosphomolybdate,g S-quinolinol phosphomolybdate,44 and molybdenum sulfide-chromium ammonium chloride43 reactions. Citric and boric acids were found to prevent interference of fluorine when the quinoline phosphomolybdate reaction was used.g Gravimetric,a3f44 titrimetric,gp33 and colorimetric18J3,56 procedures were employed, one of which used EDTA.33
Arsenic, Mercury, Magnesium, Zinc, and Cadmium Small amounts of arsenic have been determined by means of the color developed by arsine on paper impregnated with mercuric salts17,132and one of the investigators applied internal electrolysis for obtaining the arsine.132 Wet combustion followed by absorption spectroscopy was applied to t,he determination of arsenic in coal and coke.21 Mercury in organomercurials was determined by Schijniger combustion followed by amperometric titration with EDTA. log Chloride interferes with the determination. A method employing
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di-2-naphthylthiocarbazone was also describeda as well as one using sodium and zinc for decomposition followed by either volumetric or calorimetric procedure3g and one employed electrolysis.24 Magnesium in organic compounds in the presence of known amounts of calcium was determined making use of a color comparator.61 For magnesium, zinc, and cadmium, flask combustion was used.ga
Boron, Silicon, and Selenium A flame spectrophotometric method was described for the determination of boron in organic compounds which is applicable to any type sample soluble in naphtha-2-propanol. l6 Flask combustion was also used for boron.9” The simultaneous determination of carbon, hydrogen, silicon, and sulfur has been referred to previously.‘j3 Selenium was determined gravimetrically after decomposing the sample in a sodium peroxide bomb.67 An accuracy of ~0.5% was obtained.
References 1. A. I. Adibek-Melikyan and R. S. Sarkisyan, Zhur. Anal. Khim., 12, 265 (1957); through C.A., 52, 170 (1958). “Organic semimicro-elementary analysis carried out in macro-analytical apparatus.” 2. A. I. Adibek-Melikyan and R. 8. Sarkisyan, Zhw. Anal. Khim., 12, 267 (1957); through C.A., 52,7944 (1958). “Organic semimicro-elementary analysis carried out in macro-analytical apparatus.” 3. E. J. Agazzi, E. M. Fredericks, and F. R. Brooks, Anal. Chem., 30, 1566 (1958). “Microdetermination of sulfur and halogens by rapid automatic combustion.” 4. M. W. Ahmed and G. J. Lawson, Talanta, 1, 142 (1958). “A method for the determination of milligram amounts of sulfur with 4-amino-4-chlorodiphenyl.” 5. J. F. Alicino, Microchem. J., 2, 83 (1958). “Determination of sulfur in organic compounds.” 6. F. Allam and A. H. Agiza, Bull. Fat. Agr. Cairo Univ., NO. 28 (1953); “A wet combustion method for macro-, micro-, throughC.A.,52,16975(1958). and submicro-determination of carbon in organic compounds.” 7. R. Belcher, R. L. Bhasin, R. A. Shah, and T. S. West, J. Chenz. Sot., 1958, 4054. “Submicro methods for the analysis of organic compounds. Part V. The determination of sulphur.” 8. R. Belcher and M. K. Bhatty, Fuel, London, 37, 159 (1958); through Anal. Abstracts, 5, Abstract 3802 (1958). “Determination of nitrogen in coke by the Dumas-Schoniger method.” 9. R. Belcher and A. M. G. Macdonald, Talanta, 1, 185 (1958). “A rapid method for the determination of phosphorus in organic compounds.” MICROCHEMICAL
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