176) Semenchuk, 0. V., Stulova, L. M., Tr. Vses. .Vnuch.-Isaled. Znst. Zvukorapisi 1959, No. 6, 139-44. 1 7 7 ) Shankaranarayana, M. L., Patel, C. C., ANAL. CHEM. 33, 1398-400 (1961). li8) Sharp, J., Anal. Chim. Acta 25, 13-45 (1961). 179) Shurygin, V . E., Zavodsk. Lab. 28, 289 (19621. 190) Siggia; S., Hanntt, J. G., Serencha, N. R I . , ANAL.CHEM.35, 362-5 (1963). 181) Simon, A,, Serdaroglu, N., Wiss. %. Tech. Hochschule Lbresden 7, 1093-102 ( 1!),57/58).
182) Singh, B., Sahotri, S. S., J. Zndian Chem. SOC.38, 569-75 (1961). 183) Siiigh, E., T’erma, B. C., Zbid., 40, 39-41 (1963). 184) Singh, B., Vermit, B. C., 2. Anal. C h m . 194, 112-15 (1963). 1%) Singh, B., Verma, B. C., Saran, SI. S., J . Zndian Chcm. SOC.39, 490-2 (1962). 186) Skvortsova, A. E., Petrova, L. N., Sovikova, E. N., Zh. Analit. Khim. 17, 896-7 (1962). 187) Smith, B., Haglund, A., Acta Chem. Scand. 15, 6 7 S 7 (1961). 1%) Stetzler, R. S., Smiillin, C. F., AXAL.CHEM.34, 194-5 (1962). 189) Ytudeny, J., Uhrova, D., Chem. Prumysl 12, 5Fi3-4 (1962). l!lO) Sully, B. I)., Analyst 87, 940-3 i 1962). \ - - - - ,
1 i n x-ray diffractomet,er for diffractometry and/or spectroscopy was described a t the second national meeting of the Society for Applied Spectroscopy, Oct’ober 14 to 18, 1963, in San Diego, Calif. attachment for a Philips powder camera \%-hichpermits the use of a single-crystal goniometer head and allows accurate determination of the Bragg angles of reflections obtained on zero-layer Weissenberg phot’ographs has been described by Carter and Vent,urino (21). A new Guiniertype camera in which the diffracted rays strike the film perpendicularly, enabling simultaneous gathering of data for particle size and lattice distortion determinations, is presented by Schrader and Tetsner (85). A sample holder which uses Peltier couples fed by siliconcontrolled rectifiers controlled by a magnetic amplifier to maintain a constant temperature in the range -20” to +SO” C. has been described by Petz (73). High temperature x-ray diffraction technology continues to receive attenA thermocouple sample holder tion. (49),a furnace and associated equipment (56), high temperature cameras (58, 82), techniques for t’he hightemperature x-ray diffraction investigation of active metals (do), and a vacuum diffractometer for studies of metals sensitive to contamination by oxygen and nitrogen (104) appear in the literature. Likewise, Thompson and Xallett (95) have constructed a simplified specimen holder which maintains a constant, controlled atmosphere over a solid specimen. One of the exciting new fields of research in x-ray diffraction is the investigation of structures under very high pressure. Jamieson (47’)has described two experimental techniques using miniature diamond cells and a new, t,wo-diamond piston technique for use at very high pressures. .In apparatus with a high-pressure beryllium chamber whirh is portable. comparatively simple to build. provided with systems for a,djusting and checking the x-ray camera, and allows turning the sample and changing the film without releasing the pressure (ui) to 18,000 kg. per sq. cm.) is described by Russian workers (36). 1\YO cameras for small-angle scattering studies are mrntionrd in the literature (31, 60‘). Sewral different mrthods of mounting samples for x-ray r ,
400 R *
ANALYTICAL CHEMISTRY
diffraction observations have also been described (28, 58,67, 69, 96). One of the main uses of x-ray diffraction in analytical chemistry is the identification of substances by observation of the powder diffraction pattern. The ASTX X-Ray Powder Data File (5) and the “Comments on the ASTM Powder Data File” (46)are well known to workers in this field. The American Society for Testing Materials, the American Crystallographic Association, and the British Institute of Physics are sponsoring a project a t the Kational Bureau of Standards on the measurement and publication of standard x-ray diffraction powder patterns. The new NBS publication of this series is designated as Monograph 25 (93), superseding Circular 539, Volumes 1 through 10. Two sections of the new Monograph 25 have been published. The first section contains a brief account of the arrangement used in reporting the experimental data plus conversion factors for comparison of peak heights and integrated intensities and a cumulative index to the 10 volumes of Circular 539. The first section also contains data for 46 compounds and the second section contains data for 37 compounds. I n each section some of the data replace those previously published and some are completely new. Powder diffraction data for 295 minerals are contained in the Peacock Atlas published by the Geological Society of America (12). h coordinate indexing system for ;iSTM x-ray powder diffraction data using punched cards but which can be used without expensive mechanical sorting equipment has been described by Matthens (63). il series of articles by Shell (88) describes applications of powder methods to pharmaceutical research-e.g., trace element determination by emission methods, quantitative determinations of crystalline compounds, the tableting ability of bulk drugs, and molecular weight determinations. Other survey articles by O’Donnell and Lukaszewski (71) and Prout (7’7) should be mentioned. The quantitative analysis of multicomponent powder mixtures is discussed by Black (15). All scientists continually strive for more and more accurate measurements and x-ray crystallographers are no exception. Beu and llusil (23) have developed a new method, called the likelihood ratio method, for the precise and accurate determination of lattice parameters by film ponder methods. This method involves a statistical test which indicates when systematic errors have been removed from the x-ray data in a valid statistical manner. Beu and Scott (14) further describe an exact eccentricity correction for cylindrical film cameras. The camera radius i q
measured in three directions and from these measurements the eccentricity vector (P,u),the true camera radius, R, and the eccentricity corrections, Ap or AO, are calculated. h front-reflection Weissenberg camera is converted to a back-reflection instrument by Herbstein (43) by adding a simple adaptor and changing the gear ratio on the drive mechanism. With this apparatus reflections can be obtained up to Bragg angles of 86” and with the use of conventional methods for controlling the temperature of the single crystals, the standard deviation for identity period measurements is about 0.1%. The measurement of accurate lattice parameters from ordinary zero-level Keissenberg photographs is given by Main and Woolfson (62). -4zaroff (8) has discussed the necessary conditions for measurements of integrated intensities and has shown how these conditions can be realized in practice. .4 combination photographic and counter technique for determination of the inherent reflecting range of a single crystal without affecting its alignment or the geometry of the diffractorneter for subsequent int,ensity measurement appears in the literature ( 2 ) . Errors caused by finite sample surfaces in x-ray diffractometry of weakly absorbing samples have been described by Vonk (99) and Langford and Wilson (57‘) have derived expressions for the diffracted intensity, the centroid displacement, and the variability applicable to cases in which the specimen is thick and weakly absorbing or of a thickness comparable with the reciprocal of the absorption coefficient. Instrumental faults in three diffractometers. the Guinier transmission type and the Bragg reflection and transmission types, are compared by Simon and Kern (89). The sensitivity of detection of Fe304> Fe8C, and other carbides in metallographic samples was found to be about 0.1 to 0.5% by Kudielka and Noeller (55) using the back-reflection method of Guinier, Cr K, radiation, and 24- to 42-hour exposures. Several applications of x-ray diffraction have been selected to show the wide range of applicability of this method. One “far-out” application is the development of a n instrunient for petrological investigation of the surface of the moon (91, 92.1). The feasibility of such a n instrument’ was developed a t t,he Philips Space Development Co., Rlt. Vernon, X. Y. The identification of mineral types, the determination of their relative quantities, and the detrrmination of the composition of complex minerals are to be carried out with a n instrument basicall>-similar to standard commercial units except that it is inverted, it employs a shorter focusspecimen distance, and its total w i g h t is about 20 pounds. Heisr ( 4 2 ) de~
scribes the production of Kossel line5 by a n elcctron prohc microanalyzer. I.cs the determination of hematite in iron ore.;. Reuland and Voigt (78) have used s-ray powder patterns to determine lattice parameters of cubic sodium tungsten tirorizes and give an equation relating the lattice parameter to the sodium content. Order-disorder phrnomena in quenched, drawn, and annealed polypropylime have been studied by M-yckoff (107); Khittaker (102) drvelopetl a method for the evaluation of asially ;ymmetric distrihutionx of nbers in Ireferred orientations, and Hermans (-44) critically revie\vvs s-ray methods for cryitallinity detcmiinations on polymers. Rittner et nl. ( 7 9 ) have develo,ied a method for the identification of mercaptans and disiilfides hy x-ray diffraction of their respective 2,-l-dinitrophenyl thioethers. Spacing and intensity data are given for 21 thiols:. Application:; of s-ray diffraction to organic analyhis, especially for functional group nnaly.;is, with a list of suitable derivatives for various groups are g i v m t)>- Robin ( 8 0 ) . X-ray diffraction is Ileing widely used to .study the deferts i n single crystals, I)artic*iilarly in nearly perfect c r p t a l s of xpmicaondurtors. During the two year5 cw\-rred hy this review, a large nunilwr of articles have appeared. SpecLial cameras for theGe purposes have been ( I c v i d (35, 69, 6 4 ) . Much theoretical n-(irk has bpen done on the relation.hil)s among difl'racted intensity, ~
line broadening, and shift of s-ray diffraction peaks and iniperfections of various kinds in crj.htals (26, 54, 7 4 , 94, 100,101, 103, 105). Lipplicationsof these techniques have lieen reported for semiconductor crystals (86),aluminum (St), barium titanate ( 1 7 ) ) cadmium sulfide .:ingle rrystals (22) and films ( I O ) , gal\miic deposits of copper (&), col'Iier-al~uniiium alloy.: (9S), copper (106). germanium (27, 30, 30.1, 32), .\laskan ice (arystal> ( l o g ) ! magnesium oxide ( 6 6 ) !silicon (19, 20, 3 7 ) , thorium and cerium (61), zinc sulfide (901, uranium (K'), and uranium dioxide ( 3 4 ) . The reader should consult these or other articles for details on the methods employed and results. STRUCTURAL DETERMINATIONS
Hy far the widest application of s-ray diffraction is in the field of c r p t a l and molecular structure determination. The Sisth International Congress and Symposia of the International I'nion of Crystallography held in Rome recently serves ax a good sampling of the research carried out in the various branches of crystallography during the la'st year. Of the almost 600 cvxnmunications abstracted (I%?), well over 200 describe structure determinations using x-ray diffraction techniques. Obviously a limited review suvh ax this cannot begin to cover all of the current literature and the 1)aper.s cited below are therefore intended to be merely indicative of the structural interests that have been pursued. The material has been categorized as a matter of convenience. T h e Elements. X number of elements, notably metals, have been studied under extreme conditions in order to obtain structural information on their various solid phases. Zr and Hf ( 1 6 l ) , Si and Ge (160). I3a (113), and Sn (114) have been examined a t high pressure, while Sb (125) and U (116, 139) have been studied a t temperatures ranging from 4.2" K. to 600" C., and a single crystal study of 0-32a t 50" K. (194) is reported in which the thermal disorder of t,he strurture is described. The crystal structures of Am (167) and 0-Pu (205) have been determined. Inorganic Structures. Most, chemist,s will rcmcmbcr t h e discovery t,hat xenon was not so inert after all, a n d t h e impr(wivc a m o u n t of literature t h a t i m m d i a t e l y followed. The crystallographers contributed their share by quickly determining the molecular structures of all stable specie. (125, 126, 15?, 186, 199, 200). The crystal structure of hydronium perchlorate (173) has been determined a t - 80" C.. a temllerature low enough so that the structure was well ordered and the hydrogen atoms could he located. The H 3 0 +ion was found to be
pyramidal, analogous to the isoclectronic ammonia molecule, with an H - 0 - H angle of 112". The n.ork of Zaclhariasen, Plettinger, and Narezio (IfiS,203,204. 206. 207) on the structures of a number of h a t e s is an escellent example of the accuracy that can be attained when data are collected with a counter and Iirocessd by a high speed computer. The>- obtain standard deviations of i-0.005 A . or less for the bond distances between heavy (all escept H) atoms. -1number of niulticarbonyl romplexes have been studied by Dah1 and coworkers (127,130-135,190). They have shown these compounds not only to have estremely interesting geometry, h u t also to be of considerable chemical importance. For example, in determining the structure of Se2Fe3(CO)9 (132) they found evidence for a new t'ype of seven-coordinated metal. There have been a few determinations of the crystal1ograi)hically interesting so-called "mixed crystals." For example, octamethyl cyclotetrasilazone (191) can form crystals in which there are two geometrically different isomers. Other examples include iodoform-1,4diselenone (119), SbC15-(CH3)3P0 (121), and Zn(OH)n-ZnSOI (159). In the last example, there are two different environments for the zinc ions; one of them is octahedrally and the other tetrahedrally surrounded by oxygen. The crystal and molecular structures of several new boron hydrides (187, 188) and boron hydride derivatives (138, 164, 183, 193) have been reported. Organic Structures. -1s an appropriate transition to organic structures we mention some of the organometallic compounds and complexes. Sandwich or ferrocene-type compounds are among the most familiar organometallic complexes. Structures of this t y p e which have been determined include diacetylru thenocene (201) and dicyclopentadienyl beryllium (186), in which the sandwich is made of two identical rings. .I somewhat more unusual variety has also been reported, that of the r-cyclopentadienyl ~-cycloheptatrienyl vanadium (1 $0) in which the two rings are different. Closely related are studies such as cyclopentadienyl manganese tricarhonyl ( l I 8 ) , whose structure, by analogy, might \Tell be described as an openfaced sandwich. Further examples which have heen reported recently include cyclo-octatetraenyl iron tricarbonyl (137) and 1,5cyclo-octadienyl rhodium chloride (I&',). The last example could almost be considered a sandwich, .;ince the molecBules are dimerized through the chlorine atoms. ,Inother \vel1 known type of organometallic compound is that of the Grignard reagent. One of the last Iiublications of the late R. E. Rundle VOL. 36, NO. 5, APRIL 1964
401
R
was on the crystal and molecular structure of phenylmagnesium bromide dietherate and the nature of Grignard reagents (ftY7). Structures of specific interest to analytical chemi.;ts inchide that of dilituric acid (ILO), a barbituric acid and gravimetric agent for nickel and copper, and rhodanine (2O2),an analytical coniplexing agent for nietal ions. Several investigators have been concerned with the structures of overcron-deri or overstrained moleciiles (128. 136. 141, 145, 153. 1.55). One of the most fascinating of these (12,Y) is the structure determination of the diolefin of 2,2-p-cyclophane. The molecule consists of two benzene rings bonded (through two -C"=C"- groups) together a t their para positions. The molecule is under such strain that the benzene rings are bent into boat shapes-i.e., ca,rbon atoms 1 and 4 of each benzene ring are bent as niuch as 14" out of the plane of carbon atoms 2, 3, 5 , and 6. Structure determinations of the organic acids have been very prevalent, the straight-chain carboxylic acids being the most thoroughly exploited (il?, 186, 195, f96). They are of interest. among other ways. in that the molecular packings are varied. Other studies include the structures of acrylic ( I G b ) , oleic (11f ), dihydromalvalic (162), and 2-amino-3-methylbenzoic (122) acids. Natural Products and Molecules of Biological Interest. T h e amount of ivork t h a t has been done on structures of natural products and moderatcsized compounds of biological interest is so abundant and varied t h a t it complrtely defies a n a t t e m p t t o cite a given 3tructure a s bring representative. The xvork of Robertson. Sim, and coworkers (112, 123, i24, 147-158, 165% 166, 174. 182. 1-98), Mathieson, Fridrichsons, and their coworkers (142-144, 169, 170, 1.71). Przybylska (177 - 180). and Hodgkin and her coworkers ( II O , 156) is particularly impressive. For further review in this category, a comprehensive 40page review by Rich and Green (181), whirh covcrs the period prior to 1961, is highly rrcommended. The most prominent work in the field of very large biological molecules was of course the Sobel Prize-winning work of Crick, It-atson, and Wilkins on nucleic acids (192, 2OR, 209) and that of Kendrew and I'erutz on globular proteins (12.9;163, 112,115,176). JVe close on a note of optimism. With all due res1iect for the efforts of the inany scientists who have \\-orked on the deve1ol)n ent of better methods with n-hich to solve diffraction problems, it seems that. at lea5t potentiallj-, the mo-t iniportant contribution is a paper by Goldberg, Lewis, and Katson (f@) on the use of intensity correlations to
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ANALYTICAL CHEMISTRY
determine the phase of a scattering amplitudc. Basically they wggest an experinient in which two independent sources---e.g., s-rays-and two correlated detectors are used to record scattering amlilitudes simultaneously. They qhow that such an experiment n-ould provide the observer with the phase of the amplitude. Should this esperinicnt ~ i r o v e to be feasible in pracatice, it \\-auld reprezent the most funtlanirntal breakthrough since x-ray diffraction was first discovered. It n.ould mean that virtually any niolecular structure. regardlcss of it? complexity. could be solved so long as the compound could be crystallized. The paper appeared just before this manuscript was due and n-e admittedly have not had time to study thcir work carefully. This, and the f w t that the experiment has not been demonstrated, lend a note of caution to our statements. The Iirosprct is nonetheless exciting. LITERATURE CITED General
( 1 ) Abrahams. S . C , C'heni Eng -Yeu,s 41, TO.22, 108-16 (1963). ( 2 ) Alexander, I,. E., Smith, G. S., Brorvn, P. E., Acta Cryst. 16, 773-7 (1963). ( 3 ) Ani. Sor. Testing lIaterials, 1916 Iiace St,, Philadelphia 3 , PR., "ASTbI S-Ilay Powder 1)ata File." ( 4 ) Armbruster, J. E., H u l l . Soc. Franc. Jlineral ('ryst. 86, 190-2 (1963). ( 5 ) Arndt, U. \V., Hilger J . 7, 6!)-74
(1963). (6)/bid.,8, 4-13 (1963). (7) -krndt, U. LV., Phillips, I>. C., Brit. J . A p p l . P h y s . 14, 229 (1963). (8) hzaroff, I,. \.., Z. Krl'st. 115, 256-60 (1961). (9) Bardossy, G., P o m p t . Rend. 256, 2437-8 (1063).
(10) Behringer, A. J . , Corrsin, L., J . Electrochevi. Soc. 110, 108:3-5 (1963). (11j BeletskiI, M. S., Tspetn. Jletcd, 35, S O .2, 56-9 (1062). (12) Berry, L. G , Thompson, R. 11;; " 5 - R a y Powder Ilata for Ore Minerals Peacock Atlas, (;eologiral Society of hnieri(*a, 419 \Test 117th St., Nevi Tork 27. h-.\-.. 1962. ( 1 3 ) Beu, 'ICE.,'Nusil, F. J . , .letu Cryst. 15, 1292-801 (1962). ( 1 4 ) Beu, K. E., Scott, 1). L., / b i d . , 15, 1301-4 (1962). ( 1 5 ) Black, 11, H.,S o r e l c o Kept?. 10, 14-15, 18 (1963) (16) Rlokhin, bl. A , , "The Physics of SRays," rev. ed.: translated from Russian for U. S. Atomic Energy Commission (XEC-tr-l502), Office of Tec,hnicnl Servicmes, Washington 25, I). C. (17) Bouquet, C.,I,amhert, XI., Quittet, A. M.,Guinier, A , Acta C r p t . 16, >-93 (196:3). Bro\\-n, G . , "The X-Ray Identification and Crystal Structures of (:lay XIinerals," lIinrralogira1 Society, London, 1061. (19) Burgeat, J., C o m p t . Rend. 257, 1070-2 i106:3). (20) Carruthers, J. R , Hoffman, R. B., shner, J . I ) , , J . A p p l . Phly.5. 34, 389-93 ( 1963j. ( 2 1 ) Carter, F. I,., 1-enturino, h. L., .I. Sci. Instr. 40, 328-9 (1963). (22) Chikawa, J . , J . Phys. Soc. J a p a n 18, 148-9 (1963).
(23) Clark, G . I,., ed., "The Enc of 5 - R a y s and (;anima-Itay hold, Yew York, 1963. ( 2 4 ) Cole, H., Okaya, Y., Chambers F. LV., "Conil,uter-Controlled S - I i a y
l)iffrartometer," 1.B.SI. Research IiC890, Feb. 2 5 ) 1963 (to be published elsewhere). ( 2 5 ) Cowan, J. P.]llacIntyre, \V. X l . , Werkema, ( i , J., .-letu C'ryst. 16, 2215 (1963). (26) Cowley, J. >I.> Ibitl, 14, 920-1 (1961). (27) Datsenko: I,. I., F i z . Tcerd. Tela 4, 524-9 (1962). ( 2 8 ) IhFresne, E. R., J f i k r o c h i p . Ichnoanal. .-letu 1963, 416-2 (29) I)'yakonov, Yu. lesletl. Osnrl. Porod i .\aitk S.S.S.II. 1962, 252-6. ( 3 0 ) Efiniov, 0 . S . , F i z . T'cerd. Trln 5, 1466- 76 (1!)63). (:30h)~Efin;ov, t i . H., Elistratov, / h i d . , 5, 1869-7!3 i1963). (31) Eina, S., I'nangst, I).,X. .Yutitrforsch. 17a, 198-209 (1962). ( 3 % ) Ennov, 0 . S . , Eli3tratov, A . M., Fiz. 7 ' w r d . T e l a 4. 2WS-16 ( 1962). 133) Fankuchen. I.: A N ~ I . .CHEV. 30. 593 (1958). (34) Ferguson, I. F., Akt. Energy Res. Estab. iGt. Brit,.j Iterit. R3818, 38-44 ,
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on 1)irec.t Observation of Imperfect,ions in Cryetals, St. I,ouis, 1961. ( 7 7 ) ]'rout, C. I. C., Lindsey, J., Sparks, It. A , Trueblood, K. S . , IVIiite, J. Proc. Roy. Soc. ( I m d o n ) 266A, 494 (1962). (157) Ibers, J. X., Hamilton, t V , C., (;.j
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(158) Ibers, J . A . , Snyder, R. G., A c t a Cryst. 15, 923 (1962). (159) Iitaka, \-. Y., Oswald, H. It., Locc-hi, S., Z M . > 15, 559 (1962). (160) Jarnieson, J. C., Sciencr 139, 762 (196:3). (161) Ibid., 140, 72, (1963). (162) Jeffrey, G. h., Sax, lI,, .-lcta ('ryst. 16, 1196 (l96S). (163) Kendrew, J. C., Science 139, 1259 11963). (164) Lewin, H., Siml)scin, 1'. ( i , , 1,ipscwrnb, \V. S., J . ( ' h e i n . P h y s . 39, 1532 (1963) (165) l I r C a l i r a . F . , Sicmtt, A . I . , Sim, (;, L-\., Young, I).I V . , Proc. C'hw,i. Sor. ( I d o n d o n )1962. 18.5. 66) 1~1~1'1iai1, .i. T , Itobertson, J . A l , , Sim, ( i . A . , .I. f ' h m i . SOC. ( L o n d o n ) 1963, 1821.
6T) lTriVhan, 1). 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., Ibid., 15, 1227 (1962). (203) Zachariasen, LV. H., I b i d , , 16, 380
(1962). (204) Ibid., 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 regarded as magnetochemistry. As a 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.
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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. I n 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).
