(169) hlathieson, A. McL., Pure A p p l . Chern. 2 , 505 (1961). (170) Mathieson, A. McL., Taylor, J. C., -4ctn Pryst. 16, 524 (1963). (171) Mathieson, A. McL., Taylor, J. C., Tetrahedron Letfers 1961, 590.
(172) lluirhead, H., Perutz, M. F., Mazzarella, L., Sature 199,633 (1963). (173) Sordman, C. E., ilcta Cryst. 15, 18 (1962). (174) Paul, I. C., Sim, G . A., Morrison,
G . A , , Proc. Cheni. Soc. ( L o n d o n ) 1962,
352. (175) Perutz, AI. F., “Proteinsand Sucleic Acids, Structure and Function,” Anierican Elsevier Publishing Co., Xew York, 1963. (176) Perutz, 31. F., Science 140, 863 (1963). (177) Przybylska, 51.) Acta Cryst. 15, 301 (1962). (178) I b i d . , 16, 871 (1963). 1179) Przvbvlska. M.. Can. J . Cheni. 40. 566 (1962j. (180) Ibzd., 41, 2911 (1963). (181) Rich, A,, Green, D. JV., Ann. Rei’. Bzocheni. 30, 93 (1961). 1182) Robertson. J. RI., Proc. Cheni. SOC. ‘ (London) 1963. 229. (183) Sands, I).’ E., Zalkin, A,, Beta Cryst. 15, 410 (1962).
(184) Scheuerman, R. F., Sass, R. L., I b i d . , 15, 1244 (1962). (185) Schneider, R., Fischer, E. 0 . ) ‘~ntiLr~issenschaften 50, 349 (1963). (186) Siegel, S., Gebert, E., J . .4m.C h e w Soc. 85, 240 (1963).
(187) Simpson, P. G., Lipscomb, \V, S . ,J . Chem. Phys. 39, 26 (1963). (188) Simpson, P. G., Folting, K., 110brott, R. Lipscomb, iV. S . , I h i d . , (1x9) Sixth International Congress and Symposia, International Cniun of Crystallography, Rome, Italy, 9-18 September, 1968, Abstrarts of Conimunications (will be reprinted in revised form as supplementary issue to
Acta Cryst. 16, 1063). (190) Smith, I). L., Ilahl, I,. F., J . A n i . Chem. SOC.84, 1743 (196%). (191) Smith, C;. S.: Alexander, L. E., =icta (’rust. 16, 1015 (1963). (192) Spencer, 11.) Fuller, \V., IVilkins, 11. H. F., Brown, ( i , L., .\atitre 194, 101.1 (1962). (193) Streib, 17. E., Boer, F. P., Lip R. S., J . A r n . Chein. Soc. 8 5 , (1963). (194) Streib, IT. E., Jordan, T H Lipscomb, W. S . , J . Cheni. Phys. 37, 2962 (1962). ~
(195) Strieter, F. J., Templeton, I>. H., dcta Cryst. 15, 1240 (1962). (196) Strieter, F. J., Templeton, 1). H., Scheuerman, R. F., Sans, I:. L.,Ibid., 15, 1233 (1962). (197) Stucky, C;. I ) . > Itundle, R . E., J . -Am. (’hem. SOC.85, I002 (1963).
(198) Sutherland, R. A , , Sirn) G. A , , Robertson, J. LI., P ~ o c . ( ‘ h e m . SOC. ( I d o n d o n ) 1962, 222,
(199) Templeton, 1). H., Zalkin, A , , Forrester, J. I)., JVilliamson, S. Yi.j J . A m . Cheni. Soc. 8 5 , 242-4 (1963). (200) IDid., p. 817. (201) Trotter, J., A c t a (’rust. 16, 571
i 1963 ), (2d2) \-an der Helm, I)., Lessor, A . E., llerritt, L. L., I b i d . , 15, 1227 (1962). (203) Zachariasen, LV. H., I b i d , , 16, 380
(1962). (204) I b i d . , p. 385. (205) Zachariasen, 17. H., Ellinger, F. H., Ibid., 16, 369 (1963). (206) Zachariasen, \V. H., Plettinger, H. A . , I b i d . , 16,376 (1963). (207) Zachariasen, JV. H., Plettinger, H. a., JIarezio, X.> I b i d . , 16, 1144 (1963). ( 2 0 8 ) Zubav. G . , Wilkins, SI. H. F.. J . M O ~ h i 4,444 (1962) (209) Zubay, C; TT-ilkins, 11 H F., Blout, E R , I b i d , 4, 69 (1962) ~
Magnetic Susceptibility: Trends in Instrumentation, Research, Applications 1. N. M u l a y ’ a n d lndumati 1 . M u l a y , 2 Materials Research l a b o r a t o r y a n d Frear Biochemistry l a b o r a t o r y , Pennsylvania State University, University Park, P a .
I
N THIS second review on magnetic
susceptibility, u-e propose to summarize some recent developments in the instrumentation, research and applications of this technique; the first review (19.4) appeared in 1962 and was incorporated in a special chapter (21.4) on Magnetic Susceptibility. This review covers selected aspects of the field from Sovember 1961 through November 1963. It is indeed difficult to aroid the elements of arbitrariness, as it’ may appear to some readers, in the selection of the material for this review. I t should not be, therefore, regarded as a comprehensive review on what is commonly reAs a garded as magnetochemistry. matter of fact, with the increasing growth of different branc,hes of science in general and of chemistry in particular and the increasing overlap of many areas, it has become more difficult to define precisely 1 All correspondence concerning this review should be addressed to this author at the hlaterials Research Laboratory, Pennsylvania State University, University Park, Pa. This author contributed to an over-all compilation of reference9 and to the magnetic1 studies on biological and biochemical materials.
404 R
ANALYTICAL CHEMISTRY
the scope of any particular area. The phenomenal growth of research in ferrites and on materials used as “magnet,ic memory devices,” seems to warrant further specialization and classification of areas, which could very well be termed as “ferromagnetochemistry” and “ferrimagnetochemistry” or simply as “magnetics” by those anxious to coin new words. The last category could then embrace a wider scope of researches on magneto-optic rotation, Hall effect., and other magnetic effects. I t is interesting to note that more than a thousand publications appeared in the general area of magnetism bet,ween January 1962 to June 1963 and these include only a small fraction of work on the nuclear and electron magnetic resonance; this fraction include5 resonance studies on materials in t’he solid state which naturally seem to t’ie in closely with studies on magnetic susceptibility. Individuals arid organizations attemliting to compile references on magnetism justifiably overlook the enormous contributions to high resolution nuclear niagnetic resonance made who continue to be the prolific researclierh in chrmistry. Most authors of review articles and
books are confronted not only with the problem of keeping track of the increasing literature but also, and even more so, with the problem of selecting material for a critical review. To t,his we are no exception and yet vie venturb to summarize those trends of magnet,ic susceptibility work which have appeared to be of significance to us. In this review, we have introduced a new section dealing with a recent, classification (18.4, 20.~1) already branded as ”biomagnet,ism” by many researchers and as “magnetobiology” by others. When we disregard the subtle variation in nomenclature, this classification is supposed to deal primarily with the effects of magnetic fields of all types on matter of biological origin and on the studies of their magnetic properties, which as of this day pert,ain to the magnetic susceptibility, and some magnetic resonance work. GENERAL LITERATURE
During the past fen years, the general literature on magnptism has \ho\\n a phenomenal growth. Recent books by Selwood (%‘.I), Goodenough ( f O . l ) > Rado and Suhl ($?-A), Dorfman (84).
I3elov (2.4), D. ter Haar (?LA)s Brown (6.4] 6-1), have made signific,ant contributions to our understanding of magnetism in it5 various aspects. Special books have been written on “Ferrites” by Smit and Wijn (29=1), Gurevich ( I l d ) by Lax and Button (1TA-l). Several authors (4-4, 9.4,12.4, 2K&26.4 Sod) ha1;e contributed to fundamental and tecmhnological aspects of “magnetic rnateri,zls”; no reference will be made here tc cover other technological titles on “magnetic amplifiers,” “magnetic devices,” etc., although these are likely to cover useful investigations on m.tgnetism or magnet,ic materials. Reviews on nuclear and electron magnetic resonance absorption and relaxatilm phenomena are likely to give references to a series of new books on theso subjects which, naturally will ha.ve a bearing on the magnetic transitions 12f nuclei and electrons. The area, of elect,rical superconductivity and superconducting magnets has opened up new areas of research. Kolm and co-workers (16.1) have edited papers dealing with high magnetic fields. The “Index to Literature on Magnetism” (13-4)is expected to provide valuable help to the readers; however. judging from the bibliography, some magnetic investigations of significance to chemists do not seem to have been coverrd. This index is compiled by members of t,he Bell Telephone Laboratories, and very likely this may have heen compiled to meet their special requirements. .\ recent compilation of magnetic susceptibility values and other magnetic properties appeared in the LandohUornstein Tables (16=1). Short rev i e w (1.4, 22.4) and compilation of papers (%&A) on ferro- and antiferromagnetism and related topics, and a chapter (2’1.1) by on(’ of the authors (I>. N. XI.) of this re\iew on magnetic susceptibility which sh3uld be of special interest to chemists also appeared recently. Magnetic properties of ceramics has been covered by I3ickford (3.4). rerent book by Jacobs (14-4) on geomagnetism shocld also prove of interest to scme reader:. References to some i heoretical methods of calculating susceptibility were included in a recent publication (2IA4); these deal with the very simple molecules. Ho\vever. judging the scope and Inirpose of this reviewv,no survey of this aspect will be presented here. ~
INSTRUMENTATION
A distinct trend in microtechniques for the measurement’ of magnetic suscel)tibilities developed during the past three years. Some of these techniques have used an entirely new approach,
quite distinct from the classical GouyFaraday balances and the magnetic resonance methods. These will be reviewed first, and developments in other methods will be covered later. New Concepts. THE GRAVITY21s. ;\IAG~-ETIC FORCE METHOD. This (16B) uses a null method in which basically the force of gravity balances the force on a sample due to an inhomogeneous field. For magnet,ically anisotropic crystals, t,his method measures the largest principal susceptibility. I t is shown that the vert’ical component, F y , of a specially designed inhomogenous field is given by the following relation : F y = -mxH2(2a)-lsin (2y/a) where m is the mass of the sample, x is its specific susceptibility, H is the maximum component of the field, and a is a scale factor (a constant of the inst,rument) to which the field is constructed. I t is further shown that the vertical component, of the force is not a function of the field components z and z, which is very convenient in designing the experiment. The field a t which the sample falls due to gravity is given by
mg
=
imxH2,’2a
where g is the acceleration due to and - signs apply to gravity; the para- and diamagnetics, respectively. The apparatus consists of a specialljdesigned electromagnet with t x o doorknoblike poles and two flat poles a t right angles t o them. In this quadrupolar gap a small “melting point”type capillary tube, containing a small powdered sample gram) is placed. By varying the current and hence the field, a condition of “equilibrium” or balance is reached. Fields in the neighborhood of 16 kilooersted are generally employed. The critical value of the magnet current a t which the sample falls is said to be reproducible to a few t’enths of a per cent, provided the magnet is cycled on and off a fentimes a t the current appropriate to the measurement. -1pai-t from the obvious advantage of microdetermination, the method yields directly the specific (per gram) susceptibility (which is also true in the Faraday technique) and quite strikingly does not seem to involve even an actual measurement of the “niass” of the sample. This arises from the fact that the force of gravity balances the magnetic force, and both depend linearly on mass. The paper discusw several aspects of handling and measuring the maximum anisotropic susceptibility of microcrystals. D E N S I T Y GRADJEXT 2’s. ;\IAGSETIC FORCE;METHOD. I n another paper, Gordon ( 17 B ) describes an extension of the previous method to measurement of
+
paramagnetic suscept,ibility of compounds in solution. Solutions containing less than mole of solut,e were investigated and the triumph of this method lies in increasing the sensitivity to more than lo4over the classical Gouy method. The magnet,ic forces a r i . h g from an inhomogenous field acting on the sample are balanced against the densit,y gradients in the solution, For very dilute solutions the density and magnetic susceptibility are a.. ter Haar, “Fluctuation, Relaxation and Resonance in Magnetic Systems,” Consultants Bureau Enterprises, Plenum, New York, 1962. (8A) Dorfman, Y. G., “The Magnetic Properties and Structure of Matter,” State Publishing House for Technical and Theoretical Literature, Moscow, 1955 (Office of Technical Services, Dept. of Commerce, Washington 25, n r(\ u . u.1.
(9A) Francombe, M. H., Heeger, A. J., “Magnetic Materials Digest,” Lads, Philadelphia (1963). (10A) Goodenough, J. B., “Magnetism and the Chemical Bond,” Wiley, New York, 1963. (1lA) Gurevich, A. G., “Ferrites at hlicrowave Frequencies,” Consultants Bureau Enterprises, Plenum, New York, 1963. 2A)-Hadfield, D. ed., “Pa-manent Magnets and Magnetism, Wiley, New York, 1962. 3A) “Index to the Literature on Magnetism,” published by American Institute of Physics, New York, Vols. I and I1 (1962), Vol. 111, Part I (1963), Part I1 (to be published in 1964). 4A) Jacobs, J. A,, “The Earth’s Core and Geomagnetism,” Macmillan, New York, 1963.5A) Kolm, H., Lax, B., Bitter, F., Mills, R., eds., “Proceedings of International Conference on High Magnetic Fields M.I.T. 1961,” Wiley, New York, 1962. 6A) Landolt & Bornstein, “Zahlenweste und Funktionen aus Physics, Chemie, Astronomie, Geophysik und Technik,” Band 11, Teil 9, 1962, Springer-Verlag, Berlin. also Walter J. Johnson, Kew York. (17A) Lax, B., Button, K. ,J., “Microwave Ferrites and Ferrimagnetics,” McGraw-Hill, New York (1962). (18A) Mulay, Indumati L., Chap. on “Survey of ExqJoratory Research” in “Biomagnetism, Barnothy, ed., Plenum, Xew York, 1964 (in press). (1YA) Mulav, L. N., ANAL.CHEM.,34, 343R (1962). (20A) Mulay, L. X., in “Biomagnetism,” on “Theoretical Princides and ExDerimental Aspects,” Barnothy, ’ed., Plenum, New York, 1964 (in press). (21A) Mulay, L. S . , Chapt. 38 in Vol. I, Part IV, “Treatise on Analytical Chemistry,” Kolthoff and Elving, eds., Wiley, K e a York, 1963. (22A) Ne61, L., French Sczence News, Paris, No, 3, Xovember 1963 (obtainable a t French Consulates). 41 8 R
ANALYTICAL CHEMISTRY
(23A) Osborn, J. A., “Magnetism and Magnetic Materials,” Plenum, New York, 1962. (24A) Parker, R. J., Studders, R. J., “Permanent Magnets and Their Applications,” Wiley, New York, 1962. (25A) Polydoroff, W. J., “High Frequency Magnetic Materials: Their Characteristics and Principal Applications,” Wiley, New York, 1960. (26A) “Proceedings of the International Conference on Magnetism and Crystallography, Kyoto, 1961,” Journal of the Physical Society of Japan, Vol. 17, Su pl. B-1 (also published as a separate vokme in 1962). (27A) Rado, G. T., Suhl, H. (eds.) “Magnetism,” Vol~.I and I11 (Vol. I1 in preparation), Academic, Kew York, 1963. (28A) Se!wood, P. W., “Adsorption and Collective Paramagnetism,” Wiley, New York, 1962. (29A) Smit, J., Wijn, H. P., “Ferrites,” Wiley, New York, 1962. (30A) Standley, K. J., “Oxide Magnetic Materials,” Clarendon, Oxford, 1962. Instrumentation (1B) Bates, L. F., “Modern Magnetism,” Cambridge Univ., London, 1951 (2nd ed. appeared in 1961). (2B) Birss, R. R., Wallis, P. !V J .ISci. ., Instr. 40. 551 (1963). (3B) Broeisma, k., kev. Sci. Instr. 20, 660 (1949). (4B) Ibid., 34, 277 (1963). (5B) Candela, G. A., Mundy, R. E. I R (Inst. Radio Engrs.) Trans. Instr. 11, 106 (1962). (6B) Chadrasekhar. B. S...Rev. Sci. Instr. . 27, 967 (1956). ‘ (7B) Collinson, D. W., Molyneux, L., Stone, D. B., J . Sci. Instr. 40, 310 (1963). (8B) DeSa, A., Molyneux, L., Ibid., p. 163. (9B) Douglas, D. C., Fratiello, A., J . Chem. Phys. 39, 3161 (1963). (IOB) Foner, S., Rev. Sci. Instr. 30, 548 f19.59). \ - - - - ,
(11B) Frei, K., Bernstein, H. J., J . Chem. Phys. 37, 189, (1962). (12B) Garaleshko, N. P., Ukr. F i t . Zh. 7, 1068 (1962). (13B) Gerritsen, A. S., Damon, D. H., Rev. Sci. Instr. 33. 30 (1962). (14B) Ghosh, P. K.; Ind. J . Phys. 35,319 i1961 ). -, (15B) Gill, S. J., Malone, C. P., Rev. Sci. Instr. 34, 788 (1963). (16B) Gordon, R. G., Rev. Scz. Instr. 33, 729 (1962). (17B) Ibid., 33, 1167 (1962). 118B) Heaton. J. W.. Rose-Innes.’ A. C.. J . bci. Instr: 40,369 (1963). (19B) Henry, P. K., Hoyt, G. D., Rev. Sci. Instr. 34, 446 (1963). (20B) Hofer, L. J. E., Toor, E. W., Ibid., 33, 417 (1962). (21B) Kessler, J . O., Moore, A. R., Ibid. p. 47s. (22B) Lewis, G. N., Calvin, M., Kasha, M., J . Chem. Phys. 17, 804 (1949). (23B) Li, X . C., Johnson, L., Shoolery, J . S . ,J . Phys. Chem. 65, 1902 (1961). (24B) McGuire, T. R., “Methods of Experimental Physics,” K. Lark Horovitz and V. A. Johnson, eds., Academic, New York Vol. VIB, 171, 1959. (25B) Mulay, L. N., Haverbasch, Martha, Rev. Sci. Instr. 35 (1964))in press. (26B) hfulay, L. K., Keys, L. K., further details to be published separately. (27B) Neogy, D., Lal, R. B . , J . Sci. Ind. Res., India 21 B, 103 (1962). (28B) Pankey, T., Rev. Sci. Instr. 33, 431 (1962). (29B) Richardson, J. T., Beauxis, J. O., Ibid., 34, 877 (1963). \ - -
\
-
(30B) Sato, H., Chadrasekhar, B. S., J. Chem. Phys. Solids 1, 228 (1956). (31B) Seanor, D. A., Amberg, C. H., Rev. Sci. Instr. 34, 917 (1963). (32B) Shiraiwa, Y., Kikuchi, K., Kishi E., Nagano, H., Oshima, K., Bull. SOC. Chem., Japan 35, 2040 (1962). (33B) Zahn, C. T., Rev. Sci. Instr. 34,285 (1963). Commercial Instruments and Temperature Control ( I C ) Ashmead, R. R., Rudham, R., Chem. Ind. (London),p. 401 (1962). (2C) Buchanan, A. S., Creutzberg, F., Australian J. Chem. 14, 744 (1961 ). (3C) Daunt, J. G., Pillinger, W. L., Jastram, P. S., Rev. Sci. Instr. 29, 159 (1958). (4C) Hellwege, K. H., Johnson, V., Schneider, B., Z. Angew. Phys. 14, 481 (1962). ~ ----
(5C) Hohlneicher, G., Angew. Chem. 74, 490 (1962). (6C) Lawrence, J. J., Stuart, W. I., J . Sci. Instr. 39, 172 (1962). (7C) Leask, M. J. M., Wolf, W. P. Proc. 10th Intern. Congr. Refrig. Copenhagen, 1, 179 (1959) (Pub. 1980). (8C) ?eyer, J. W., Rich, A. M., Electronzcs 36 (35), 29 (1963). (9C) RAND.M. J.. ANAL. CHEM. 34. 444 (1962). (1OC) Shanelield, D., Rev. Sci. Znstr. 32, 1403 (1961). (11C) Smith, H. M., Dissertation Abstr. 23, 4551 (1963). Trends in Research (1D) Arajs, S., Calvin, R. V., Rare Earth Res., Seminar, Lake Arrow Head, Calif., 178 (1960). (2D) Arajs, S., Calvin, R. V., J . Appl. Phys. 33, 2517 (1962). (3D) Ballestracci, R., Bertaut, E. I?., Pauthenet, R., J . Phys. Chem. Solids 24, 487 (1963). (4D) Belova, V. I., Syrkin, Ya. K., Golovnya, V. A., Xi, Tszya-Tszyan. Zh. Neorgan. Khim. 7, 479 (1962). (5D) Bereyen, B. D., Sisnikova, N. I., Dokl. Akad. Nauk SSSR 146. 604 (1962). (6D) Bleany, B., Appl. Phys. 34, 1024 (1963). 17D) Blinova. N. I.. Romonov. G. A , . ‘ Solutsev, V. M.,- Tolmachev,’ V. M.: Dokl. Akad. dVauk SSSR 147, 1112 (1962). (8D) Brodersen, K., Macher, P. Z., Naturforsch 176, 127 (1962). (9D) Busey, R. H., Sonder, E., J . Chem. Phys. 36, 93 (1962). (10D) Cafasso, F. A., Gruen, D. M., Malm, J . H., J . Chem. Phys. 36, 3440 (1962). ( l l D ) Chechernikoo, V. I., Pop, I., Saumkin, 0. P., Terebhova, V. F., Zh. Eksperim. i Teor. Fit. 44, 387 (1963). (12D) Cooke, A. H., Lazenby, R., Leask, J . J . M., U . S. Dept. Comm. Ofice Tech. Serv. P. B. Rept. 155,474 (1960). (13D) Crosswhite, H. M., Dieke, G. H., J . Chem. Phys. 35, 1535 (1961). (14D) Eisenstein, J. C., Ibid., 34, 1628 (1961) (this lists reference to the earlier work). (15D) Evdokimov, V. B., Kobozev, N. I., Vestn. Mosk. Univ., N o . 6. Ser. TI, Khim. 16 (1962). (16D) Faeth, P. A., Clifford, A. F. J., Phys. Chem. 67, 1453 (1963). (17D) Gerstein, B. C., Jennings, L. D., SDedding. F. H.. J . Chem. Phvs. ” 37.. I.496 (i962). (18D) Giauque, W. F., Hornung, E. W., I
I
Fisher, R. A,, Brodale, G. E., J . Chem. Phys. 37, 2952 (1962). (19D) Hellwege, K. H., Schembs, W., Schneider, B., 2. Physik. 167, 477-86 (1962). (20D) Hutchison, C. A,, Tsang, T., Weinstock, B., J . Chem. Phys. 37, 555 (1962). (21D) Hyman, H. H., “Noble Gas Compounds,” The Vniversity of Chicago Press, Chicago (1963). f22D) Johannesen. R. B.. Candela, G. A., ‘ Inorg. Chem. 2, 67 (1.963). (23D) Kachi, S., Tabitda, T., Goto, Y., Kogyo Kagabu Zasshi 65, 1753 (1963). (24D) Knox, K., Gineberg, A . P., Inorg. Chem. I , 945 (1962). (25D) Leask, M. J. M , Roberts, L. E . J., Walter, A. J., Wolf, W. P., J . Chem. SOC.4788 (1963). (26D) Legrold, S., :Rare Earth Res. Seminar, Lake Arrowhead, Calif., 142 (1960). (27D) Locher, P. R., Gorter, C. J., Physica 28, 797 (19fi2). (28D) Maginn, R. E., Manustyrskyj, S., Dubeck. M.. J . Am. Chem. SOC.85, 672 (1963). ’ (29D) Sheppard, J. C., Wheelweight, E. J., J . Phys. Chem. 67, 1568 (1963). (30D) Slivnik, J., Brcic, B., I‘olavsek, B.. Smale. S.. Frlec. B., Zeml.iic, S., Anzur, A:, Veksli, ‘Z., Croat. Chem. Acta 34, 187 (1962). (31D) Stevenson, R., Can. J . Phys. 40, 1385 (1962). l32D) Trzebiatowska. B. Jezowska-, ‘ Wojciechowski, W.; Bull. Acad. Polon. Sci., Ser. Sci. Chim. 9, 685-791, 693-8, 699-704 (1961). (33D) Trzebiatowski, W.,and Suki, W., Bull. Acad. Polon. Sci., Ser. Sci. Chim. 10, 399 (1962): Trzebiatowski, W., Troc, R., LecrejewicG, J., Ibid., p. 395. (34D) White, J. A., Williams, H. J.,
Sherwood, R. C., Phys. Rev. 128, 581 (1900). 135D) Woodhead. J. L.. Fletcher. J. M.. ‘ AL’Energy Res.’ Esta6. (Gt. Brii.) Rept: R 4295, (1962). (36D) Zanowick, R. L., Dissertation Abstr. 23, 857 (1962). (37D) Zelentsov. V. V.. Dokladv Akad. S S S R i39, iiio-ii (1961). ~
Applications
(1E) Ackerman, E., Brill, A. S., Biophys. Acta. 56 (3), 397 (1962). (2E) Bliumenfeld, L. A., Benderskii, V. A., Biofizika (Trans. English) 6, 4 (1961). (3E) Bottei, R . S., Laubengayer, A. W., J . Phys. Chem. 66, 1448 (1962). (4E) Burgess, J. H., Rhodes, R. S., Mandel, M., Edelstein, A. S., J . Appl. Phys. 33, Suppl. 3, 1352 (1962). (5E) Chernyakovskii, F. P., Machtina, K. A , , Musabekor, Yu. J., Zh. Fiz. Khim. 36, 865 (1962). (6E) Duffy, W., J . Chem. Phys. 36, 490 (1962). (7E) Ehrenberg, A , , Anders, A., Yonetani, T., Acta Chem. Scand. 15 (5), 1071-81 (1961). (8E) Felgentreu, I., paper in “Structure and Biological Function of Proteins,” p. 77-9, H . Kirsch, ed., Gustav Fischer, Jena, Germany, 1962. (9E) Francois, H., Bull. SOC. Chim. France, 506-19 (1962). llOE) French, C. M., Pritchard, R., Arch. Biochem. Biophys. 93 (3), 598 (1961). 1E) Haberditzl, W., Havermann, R., Gelgentren, I., Z. Phys. Chem. (Leipzig) 218, 354 (1961). 2E) Havemann, R., Haberditzl, W., Mader, K. H., Ibid., p. 71 (1962).
(13E) Havemann, R., Haberditzl, W., Rabe, G., Ibid., p. 417 (1961). (14E) Hazama. Y.. Hazama. K.. Ehren‘ berg, L., Radliatibn Bot. 3 (1) 7 (1963). (15E) Heit, M. L., Ryan, D. E., Anal. Chim. dcta 29, 524 (1963). (16E) Karimor, Yu. S., Schchegoler, I. F., Dokl. Akad. Nauk SSSR 146, 1370 (1962)
(17E) Lelgrand, D. G., J . Poly Sci. 60, S71 (1962). (18E) Lumry, R., Solbakken, A., Sullivan, J.. Rverson, L. H., J . Am. Chem. Soc. 84, la2 (1962). ’ f19E) Malmstrom. B. G.. Broman. L.. ‘ Mosbach, R., fihrenberg, A., Anders; A,, J . M o l . RioE. 5 (4), 450 (1962). (20E) Mayr, G., Rabboti, G. C., Experientia 13, 252 (1957). (21E) Mulay, L. N., Fox, M. E., J . Am. Chem. SOC.84. 1308 (1962). and J . Chem. Phys. 38; 760 (1963). (22E) Okumura, K., J . Phys. SOC.Japan 18, 69 (1963). (23E) Pacault, P., Poquet, E., Compt. Rend. 255, 2106 (1962). (24E) Sager, W. F., Fatiadi, A,, Parks, P. C.. White. D. G.. Perros. T. P..’ J . Inorg. Nucl. Chem. 25, 187 (1963). (25E) Senftle, F . E., Thorpe, A. N., I S A Transactions 2 (2), 117, (1963); Suture 190, 410 (1961). (26E) Somoilova, 0. P., Blyumenfeld, L. A , , Biofizika (Trans. English) 6 ( l ) , 14 (1961). (27E)‘Sriraman, S., Sabesan, R., Trans. Farad. SOC.58, 1080 (1962). (28E) Liu, Tung Rfing, Hua Hsueh Tung Pao, No. 7, 34. 1962 (29E) Wallman, J. C., Cunningham, B. B., Calvin, M., Sci. 113, 55 (1951). (30E) Ward, R. L., J . Chem. Phys. 38, 2558 (1963). (31E) Woernley, D. L., Arch. Biochem. Biophys., 50, 199 (1954); Ibid., 54, 378 (1955).
Nucleonics G. W . leddicotte, Nuclear Division, Union Carbide Co., Tuxedo, N. Y
A
is presented of the fundamental developments in nuclear methods of analysis for the period from late 1961 to late 1963. It continues to be a rapidly expanding field and the wide diversity in publication media and in the number of analysts reporting results has brought about a marked increme in the number of papers (over 1760) contained in this review. Thus, it has been difficult to attain as complete ccverage as in the prior review (920). A1 though no serious attempt has been made to curtail any area of contribution, some omissions will be evident. Minimal coverage has been given to the reports on nuclear data, instrumentation, and general items such as report5 on conferences. The major portion of this review is concerned with applications of radioisotopes as tracers. Sections on activation analysis, isotope dilution and radiometric methods, separation procedures, and the use of radioisotopes as sources and as tracers in developing analytical GENERAL RE VIE^
methods are presented. I n addition, significant information about investigations in age determinations, radiochemistry measurement, and the use of computer-integrated programs to reduce data from such measurements to an accurate and reliable form is given. The format of this review follows closely that of the prior one (920). General references, survey papers, arid the like are given a t the beginning of each section. Specific references to radioisotope applications are cited either in the text in each section or in one of the tables. Many problems are being solved through the use of nucleonic methods. The ITS;\EC has emphasized their usefulness by providing periodic bibliographies on the use of radioisotopes in world industry (1653, 1654). Individual writers have provided excellent source books. Clark (309), in particular, has edited a major encyclopedia on many areas of radiation measurements and applications. Books by
Chase and Rabinowitz (276), Yesmelanov (1171), O’Kelley (1225), Taylor (1.596), Lindner (962), Overman ( l y l ) , and Peterson and Wymer (1272) give practical information on scientific investigations in such varied fields as instrumentation, radiochemistry, and autoradiography. Other books and articles give information on the production of radioisotopes by either nuclear reactors or charged-particle accelerators (78, 161, 600, 229, 270, 459, 61fi, 687, 843, 1056, 1059-1061, 1169, 1130, 1323, 1405, 1452, 1507, 1.545, 1609, 1635). Hara (616) and others (50, 64, 205, 397, 428, 579, 686, 740, 988, 989, 1025, 104.9, 1061, 1075, 1087, 1187, 1391, 1475, 1682, 1687) report on the applications of radioisotopes and nucleonic methods in such areas as exchange reactions and chemical reaction mechanisms in chemical analysis and technology, and in biology, agriculture, and industry. Specific books by Slater (1528) and Dzhelepov and Peker (398) contain VOL. 36, NO. 5, APRIL 1964
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