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(164) "Design of Radiotracer Experiments in Marine Biological System", IAEA, 1975. (165) Babu, S. P., Ed., "Trace Elements in Fuel", Ad.. Cbem. Ser., 141, American Chemical Society, Washington, 1975. (166) Lyon, W. S., "Trace Element Measurements at the Coal Fired Steam Plant", CRC Press, Cleveland, Ohio, 1977. (167) Nichol, A. W., Ed., "Physicochemical Methods of Mineral Analysis". Plenum Press, New York, N.Y., 1975. (168) Morse, J. G., "Nuclear Methods in Mineral Exploration and Production", Elsevier, New York, N.Y., 1977. (169) Holzhey, J., "Aktivierungsanalyse. Anwendung in Der Metailurgie", VEB Deutscher Veriag fur Grundstoffindustrie, Leipzig, 1975. (170) Tubis, M., Wolf, W., Ed., "Radiopharmacy", John Wiley and Sons, New York, N.Y., 1976. (171) Eicholz, G. G., "Environmental Aspects of Nuclear Power". Ann Arbor Science Publishers, Ann Arbor, Mich., 1976. (172) "Proceedings of the 8th Radiochemical Conference", Lame, Marianske, Part 1, J . Radioanal. Chem., 30, 1 (1976). (173) "Proceedings of the 8th Radiochemical Conference", Lame, Marianske, Part 2, J . Radioanal. Chem., 30, 307 (1976). (174) "Proceedings of the Sixth International Conference on Atomic Collisions in Solids", Amsterdam, Nucl. Instrum. Methods. 132, 1 (1976). (175) Lyon, W. S.,Braun, T., Bujdoso, E., Ed., "Proceedings of the International and Atomic Activation Analysis Conference and 19th Annual Meeting on Analytical Chemistry in Nuclear Technology", Gatlinburg, Tenn., Akademiai Kiado, Budapest, 1976. (176) "Proceedings of the Symposium on Safeguarding Nuclear Material", 2 volumes, IAEA, Vienna, 1976. (177) "Proceedings of the Symposium on Transuranium Nuclides in the Environment", IAEA, Vienna, 1976. (178) "Proceedings of the Symposium on the Biological and Environmental Effects of Low-Level Radiation", 2 volumes, STI/PUB/409, IAEA, Vienna, 1976. (179) "Proceedings of the Symposium on Nuclear Techniques in Animal Production and Health", STI/PUB/431, IAEA. Vienna, 1976. (180) "Proceedings of the Symposium on Exploration for Uranium Ore Deposits (in Mexico City)", IAEA, Vienna, 1976. (181) "Proceedings of the Symposium on Management of Radioactive Wastes from the Nuclear Fuel Cycle", 2 volumes, STI/PUB/433, IAEA, Vienna, 1976. (182) "Proceedings of the Symposium on Measurement, Detection, and Control of Environmental Pollutants", IAEA, Vienna, 1976. (183) "Proceedings of the Symposium on Exploration of Uranium Ore Deposits (in Vienna)", IAEA, Vienna, 1976. (184) "Proceedings of the International Conference on Particle Induced X-Ray
Emission and Its Analytical Applications", Nucl. Instrum. Methods, 142, 1 (1977). (185) "Proceedings of the Ninth Conference on Electromagnetic Isotope Separators and Related Ion Accelerators", Nucl. Instrum. Methods, 139, 1 (1976). (186) "Proceedings of ERDA Symposium on X- and Gamma-ray Sources and Applications", CONF-760539, 1976. (187) Noujaim, A. A., Ediss, C., Weibe, L. I . , Ed., "Liquid Scintillation Science and Technology", Academic Press, New York, N.Y., 1976. (188) "Proceedings of the First Symposium on Clean Fusion", Nucl. Instrum. Methods, 144, l ( 1 9 7 7 ) . (189) "Proceedings of the 1976 International Conference on Modern Trends in Activation Analysis", Part 1, J . Radioanal. Chem., 37, 1 (1977). (190) Ibid., Part 2, 37, 497 (1977). (191) Ibid., Part 3, 38, 1 (1977). (192) Wagner, F. E., J . Phys. (Paris), Colioq., 6, C6.673 (1976). (193) Lyon, W. S., Radiochem. Radioanal. Lett., 24, 245 (1976). (194) "Proceedings of the Symposium on Nuclear Science, Scintillation and Semiconductor Counters", IAEA, Vienna, 1976. (195) Friedman, A. M., Ed., "Actinides in the Environment". ACS Symp. Ser., 35. American Chemical Society, Washington, D.C., 1976. (196) Campbell, M. H., Ed., "High-Level Radioactive Waste Management", Adv. Chem. Ser., 153, American Chemical Society, Washington, D.C., 1976. (197) Toigyessy, J., Varga, S.,"Nuclear Analytical Chemistry, Vol. V", University Park Press, Publishing House of the Slovak Academy of Sciences, Bratisiova, 1976. (198) Wiernik, M., J . Radioanal. Chem.. 31, 529 (1976). (199) Erdtmann, G., Soyka, W., J . Radioanal. Chem., 27, 137 (1975). (200) Wu, C.-C., Yang, M.-H., Anal. Chin?. Acta, 8 4 , 335 (1976). (201) Voight, A. F., IS-4052, Dec. 1976. (202) Seda, J., Radiochern. Radioanal. Lett., 29, 13 (1977). (203) Irifune, T., Onai, Y., Radioisotopes, 25, 552 (1976). (204) Kato, T., Sato, N., Suzuki, N., Talanta, 23, 517 (1976). J . Radioanal. Chem.. 29, 175 (1976). (205) Gryntakis, E. M., Kim, J. I., (206) Rudstam., G., J . Radioanal. Chem., 36, 591 (1977). (207) Gleason, G., Radiochem. Radioanal. Lett., 23, 317 (1975). (208) Krivan, V., Krivan, K., J . Radioanal. Chem., 29, 145 (1976). (209) Krivan, V., Talanta, 23, 621 (1976). (210) DeBrun, J. L., Barrardon, J. N., Benaben, P., Anal. Chem., 48, 167 (1976). (211) Barrandon, J. N., Benaben, P., Debrun, J. L., Anal. Chlm. Acta, 83, 157 (1976). (212) McGinley, J. R., Schweikert, E. A,, Anal. Chem., 48, 429 (1976). (213) Sastri, C. S.,Petri, H., Erdtmann, G., Anal. Chem., 49, 1510 (1977).
Organic Elemental Analysis T. S. Ma* Department of Chemistry, City University of New York, Brooklyn, New York 11210
Milton Gutterson Flavor Application Laboratory, Dragoco, Inc., King Road, Totowa, New Jersey 075 12
GENERAL T h e present review follows the previous one ( I ) and covers the literature from January 1976 to November 1977. During 1976 the writer visited many laboratories in Asia, Eastern and Western Europe, and had t h e opportunity to observe the current practice of organic analysis. For the determination of the elements in organic materials, the former separation into macro, micro, and ultramicro divisions has generally disappeared. The task of the analyst is to obtain the required quantitative data using a suitable method. Understandably, t h e microchemical approach ( 2 ) is frequently applied, since i t saves time and material. The writer saw numerous modifications of existing methods and obtained information on handling special materials. These findings are not included in this review, but will be presented in the monograph scheduled for publication in 1978 (3). While t h e analysis of pure compounds still plays an important role in organic elemental analysis, recent publications have focused attention on the treatment of mixtures. Since complete decomposition of the sample without loss of the element to be determined is crucial, studies were made on wet digestion (4-7) and ashing (8-10). Kunkel (11) used oxyhydrogen flame to determine chlorine, arsenic, and metallic elements in polymers and biological materials. T h e effectiveness of metal oxides (12, 13) and barium chromate (14) as combustion catalysts were reported. Volodina et al. (15) 0003-2700/78/0350-086R$Ol .OO/O
decomposed halogen compounds by means of pulsed radiation from a xenon lamp. For automated operations, Fraisse (16) constructed a device to drop the sample into the pyrolysis tube; Franc and Pour (17)described continuous determination of C-to-N ratios. There is a continuing search for methods to obtain accurate results using the minimal quantities of samples. Thus de Groot et al. (18) determined ng amounts of sulfur in 5-pL solution. McCullough and Vickers (19) determined copper and iron in pL samples of serum. Alder et al. (20) determined trace metals in 1 cm of human hair. Cauwet (21)optimized the determination of 0.7-1.3% of organic carbon in 100 mg of sediments by heating with H3P04.
DETERMINATION OF MAJOR CONSTITUENTS The determination of an element which constitutes 1070 or more of the compound or mixture is usually performed in the mg range. An exception may be the Kjeldahl method for nitrogen in agricultural materials in which dg samples are analyzed. Carbon and Hydrogen. Baba (22) determined carbon and hydrogen by vaporizing the sample in a stream of nitrogen and transporting the gases to a nozzle through which oxygen is flushed for subsequent oxidation. Pietrogrande and Dalla Fini (23) prevented the interference due to fluorine by using C 1978 American Chemical Society
ANALYTICAL CHEMISTRY, VOL 50, NO. 5, APRIL 1978 T. S. Ma is professor of chemistry at the City University of New York. He received his P h D in synthetic organic chemistry from the University of Chicago in 1938 and started his career as a teacher of microchemistry in Chicago. Subsequently, he established microchemistry laboratories and taught at Peking University, China: University of Otago, New Zeaiand; and New York University. Prof. Ma has been particularly active in promoting the application of microchemistry to research and education and has lectured widely on this subiect. He SeNed twice as Fullbriaht-Haves leciurer and once as American specialist with the Bureau of Educational and Cultural Affairs of the State DeDartment. He has been visitina Drofessor at Tsinahua Universrtv. Lingnan University, and National Taiwan University. China; Chiangmai UniversiG, Thailand; and University of Singapore, Republic of Singapore. Prof. Ma has published several books and over 130 papers. He is an editor of Mikrochimica Acta, the internationaljournal on microchemistry and trace analysis. His current research interests are concerned with organic synthesis and analysis on the mg to p g scale, microchemical investigation of medicinal plants, and the use of small-scale experiments to teach chemistry. Prof. Ma received the Benedetti-Pichier award in microchemistry in 1976.
Milton Gutterson received his B.S. degree from the City College of the City University of New York in 1949. After graduation he worked for Popsicie Industries (formerly Joe Lowe Co.) Division of Consolidated Foods Corp., Englewood, N.J., where he was chief chemist and then plant manager. He has since worked for Ehlers Division of Brooke Bond Foods Inc. He is now connected with Dragoco, Inc., Totowa, N.J., where he is director, Flavor Application Laboratory. For several years he was a part-time lecturer in the graduate division of Brooklyn College, City University of New York, where he supervised the laboratory for ouantitative elemental and functional orouD microanalysis. He earned his master's'begiee from Brooklyn College in 1956 by attending classes and doing research after working hours. His special interest is in the field of organic microanalysis. He was adjunct professor of chemistry at the New York Institute of Technology, Manhattan Campus, evening division. Mr. Gutterson recently published several monographs on food processing with the Noyes Data Gorp., Park Ridge, N.J. These were tiled ' Baked Gocds Production Processes, 1969", "Confectionary Products Manufacturing Processes, 1969", "Fruit Juice Technology, 1970", "Fruit Processing, 1971", and "Vegetable Processing, 1971". He is a member of the ACS, the American Association of Cereal Chemists, and the Institute of Food Technologists.
a combustion tube containing a section of Co30, a t 950 "C and a section of AgMnO, at 550 "C. Binkowski e t al. (24) confirmed that the interference of phosphorus was due to the deposition of oxides of phosphorus on the combustion tube. Volodina e t al. (25) found that the phthalocyanines were correctly analyzed by using Cr203as combustion catalyst. Heistand and Humphries (25a)determined carbon in oil shales using combustion temperature of 450 "C. Oxygen. Fraisse (26) described an automated oxygen analyzer by converting CO produced a t 1120 "C to C 0 2which was titrated coulometrically. Chumachenko e t al. (27) employed gas chromatography to determine oxygen by measuring t h e peak height for CO; interference by phosphorus was prevented by pyrolyzing the sample in a layer of carbon under static conditions (28). Imaeda e t al. (29) observed that zinc compounds gave poor results due to deposition of ZnO, and t h e results were improved by adding naphthalene to the sample. Kirsten (30) found that the addition of chlorohydrocarbon vapor to the carrier gas enhances the conversion of oxygen to CO. Pella. and Andreoni (31)reported that the overlap of the CO peak by the nitrogen peak could be eliminated by using nickel-coated carbon. Nitrogen. Chudakova e t al. (32) reported t h a t MnOzC0304-Cr203mixture is a suitable oxidant for determining nitrogen using a fast stream of carbon dioxide in the conventional apparatus. Baba (33) described a rapid method using a flush-oxygen combustion tube; the excess of oxygen was removed and the nitrogen oxides were reduced by copper a t 5OC-600 "C. Handling of thermally unstable and difficultly combustible compounds were studied by Mikhailova et al. (34)
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and Chumachenko et al. (35). Fraisse and Schmidt (36) devised an automated system with a sample feeder and vertical reactor which does not require the operator's attention. Kjeldahl digestion using CuS04 (37,527)or TiOz (39)in place of Hg was shown to be satisfactory. Colorimetric determination of ammonia by the indophenol reaction (40) was generally employed in the automated systems (41-44). Other methods involve the use of ",-electrode (45),sodium salicylate (46),or chloramine-T (47).
