摘要:

11 Sc Y the Lanthanides and the Actinides By S. J. LYLE Department of Chemistry University of Kent at Canterbury Canterbury Kent CT2 7NH 1 Introduction The division of these elements into sub-groups follows the scheme adapted in previous years. However within each sub-grouping a greater emphasis than in the immediate past has been placed on physical and chemical properties of purely inorganic substances mainly in the solid state. Following a brief introduction which includes mention of any monographs general review articles or treatments of the elements as a whole reported work on hydrides halides chalcogenides pnictides and miscellaneous binary and ternary systems are surveyed in that order. The report concludes with brief reviews of structural and chemical aspects of selected chelates organometallic compounds and their reactions.2 Scandium An e.s.r. investigation' of ScX2 (X = C1 Br or CN) radicals isolated in Ar matrices at 14 K has been carried out. The radicals are highly ionic and appear to be bent with the unpaired electron localized primarily in a 3d orbital of the metal. A study on the dihydride radicals of Sc and Y led to a similar conclusion.* 'H and 45Sc n.m.r. studies on ScH1.98 are consistent with the assumed CaF2-type structure and with a relatively low value of the electron density of states at the Fermi level as expected for this hydridee3 Preparation of hydride phases of the type SCM,H~~ (M = Fe Co or Ni) by reaction of ScM with H has been described thermal stability of the hydride phases increase in the sequence ScNi < ScCo < ScFe,.Changes in magnetic properties of ScFe on H absorption have been studied by Mossbauer spectroscopy and bulk magnetic measurement~.~ The absorption of H (up to 3.2 atoms per formula unit) leads to a large increase in the Fe moment (1.15 pB to 2.35 pB per Fe) and although the hexagonal C14 laves structure does not change volume expansion is about 24%. The dissociation energy of gaseous ScH determined mass spectrometrically,6 is 47.5 f 2 kcal mol-'. ' L. B. Knight jun. M. B.Wise and T. A. Fisher Znorg. Chem. 1981 20 2623. L. B. Knight jun. M. B. Wise T. A. Fisher and J. Steadman J.Chem. Phys. 1981,74,6636. 0. J. Zogal and S. Idziak Physica (B + C),1981 104 365. V. V. Burnasheva A. V.Ivanov V. A. Yartys and K.N. Semenenko Izo. Akad. Nauk SSSR Neorg. Muter. 1981 17,980. ' D. Niarchos P. J. Viccaro G. K. Shenoy B. D. Dunlap and A. T. Aldred Hyperfine Interact. 1981 9 563. A. Kant and K. A. Moon,High Temp. Sci. 1981,14,23. 299 300 S. J. Lyle Reduced ternary halides of the formulae RbScX (X = C1 or Br) and CsScX (X= C1 Br or I) have been prepared7 by reacting A3Sc2X9 (A = Cs or Rb X = C1 or Br) and Cs13 with Sc in Ta containers at 750°C. These compounds have the CsNiC1,-type structure. Attempts to produce KScX (X = C1 Br or I) and RbScI failed. A homogeneity range in ASc,C13 with 0.67 <x <1.0 exists between the end members A3Sc2C19 (Cs,Tl2Clg-type structure) and AScCl but a similar range of composition does not occur for CsSc,Br3 CsSc,13 or RbSc,Br3 because all 3 corresponding A3Sc2X9 phases have the less favourable Cs,Cr2Clg-type structure.The heat of formation of ScF; determined' mass spectrometrically is -2000.8 f 12.6 kJ mol-'. The crystal structures of MnSczS4 and Sc(Mo04) have been reported; the former is a normal spinel' and the latter similar to the corresponding tungstate." A LCAO-tight binding method has been applied'' to calculation of the band structures and density of states in ScP. It is concluded that ScP is a semi-conductor and that the Sc-P bonds have appreciable covalent character. A detailed review of the co-ordination chemistry of Sc" and Sc"' but largely confined to published work in 1979 has appeared.12 However for 1981 there is little to report involving organic ligands.Kinetic data and activation parameters have been p~blished'~ for the exchange of *%c3+ with scandium-N-(2-hydroxy- ethy1)ethylenediamine-N;N',N'-triacetate (Sc-hed3a). The only reaction pathway for exchange consists of a slow rate-determining dissociation of a protonated Sc-hed3a intermediate as has been found previously in several studies of Ln- complexone systems. A 'H n.m.r. study of ligand exchange on complex cations of the form [ScL6I3+ in C2H3CN solution has been de~cribed.'~ The ligands were N-mono- or -di-substituted acetamides or formamides 0=CR'NR2R3 with R2 and R3 as alkyl or aryl groups. Whereas exchange rates for the acetamides (R' = CH,) were within the n.m.r. time scale at 90 MHz those of the formamides (R' = H) occur at a rate in the fast-exchange limit of the time scale.Electron-donor ability is not the major factor determining labilities; instead steric interactions arising from R' seem to be dominant with those arising from R2 and R3 of lesser importance. In a crossed ion and laser beam experiment," photoelectron spectra have been obtained for the anions Sc- and Y-. The spectra are each interpreted in terms of 2 bound terms (lD0and 3D0)of the 3d4s24p and 4d5s25p configurations and from the former it is deduced that the order of sub-shell filling in the first transition series of negative ions is 4s24p 3d4s24p followed by 3dk4s2with k = 3,4 . . .,10. 3 Yttrium and the Lanthanides The chemistry of the trihalides of these elements and Sc has been reviewed;16 the preparation of anhydrous compounds hydrates and other solvates and thermody- ' G.Meyer and J. D. Corbett Inorg. Ckem. 1981 20,2627. M. I. Nikitin L. N. Sidorov E. V. Skokan and I. D. Sorokin Zk. Fiz. Kkim. 1981 55 1944. A. Tomas M. Guittard E. Barthelemy and J. Flahout Muter. Res. Bull. 1981 16 1213. lo V. A. Efremov B. I. Lazoryak and V. K. Trunov Kristallografiya 1981,26,72. P. G. Perkins A. K. Marwaha and J. J. P. Stewart Tkeor. Chim. Acta 1981 59 555. R. C. Fay Coord. Chem. Rev. 1981 37 1. l3 W. D'Olieslager M. Wevers and M. De Jonghe J. Znorg. Nucl. Ckem. 1981 43,423. l4 D. L. Pisaniello and S. F. Lincoln Inorg. Ckem. 1981 20 3689. Is C. S. Feigerle Z. Herman and W. C. Lineberger J. Electron Spectrosc. Relaf. Pkenom. 1981,23,441.l6 J. Burgess and J. Kijowski in 'Advances in Inorg. Chem. and Radiochem.' ed. H. J. EmelCus and A. G. Sharpe Academic Press London 1981 Vol. 24 p. 57. Sc Y,the Lanthanides and the Actinides 301 namic data especially enthalpy of solution are covered. Studies of the thermal degradation of the carbonates and oxalates17 and spectroscopic properties of the metal complexes18 have also been reviewed. There is considerable interest in valence fluctuations in solids and the year has produced a reviewIg and the report of a conference proceedings held in January at Santa Barbara California on experi- mental and theoretical aspects of this field of study.” It has long been known for example from fractional crystallization studies that the position taken up by Y within the Ln series varies from system to system.Siekierski”” has attempted to rationalize the behaviour of Y in isostructural series M,X, through computation of a fractional volume occupied by Y in the unit cell; a linear correlation between this quantity and the electronegativity of X is explained in terms of covalency in the M-X bonds. It has been shown2’ by photoemission spectroscopy that clusters of Sm atoms exhibit mixed-valence [(11) + (III)] behaviour which is sensitive to particle size; the (II)-valent form predominates for small particles with the (111)-valent state becoming more abundant with increasing size and eventually dominant for the bulk metal. The considerable interest in the physical and chemical properties of binary and ternary systems containing Y and Ln represents a large part of the total published output.Because of the importance of solids suitable for the storage of hydrogen interest continues in the hydrides of these elements and their binary alloys. Hydro- genation of intermetallic compounds has been reviewed” with reference to hydro- gen capacity at saturation phases formed energetics of hydride formation and systematic variation of hydride stability within families of intermetallic compounds. The electronic structure of CeH (2 Q x s 3) has been examined using the LCAO method for H occupying various octahedral sites of the f.c.c. lattice and a mechanism proposedz3 for the temperature-dependent metal to semi-conductor transition at x = 2.7. Experimental evidence continues to accumulate consistent with the pres- ence of positively charged metal ions in MH (x 2 2).Thus Er Dy and Gd doped into YH2 and LaHz have e.s.r. spectra consistent with the presence of Ln*II ’* and angular correlation of the two photons emerging from positron annihilation in LaH2.71 YH2.36 EUH~.~~ gave resultsz5 consistent with charge transfer and EuH~.~~ to the H site and also for mixed valency in EuH,. The Raman-active phonon in CeH is anomalously soft when x = 3 compared with that for x = 2; this can be attributed26 to the formation of a new s-like valence band in CeH3 with the valence electrons screening the Raman mode. Further evidence for H occupation of both octahedral and tetrahedral sites in the metal lattice has come from a photoelectron spectroscopic of LaH (1.9 d x d 2.9) using radiation (10 s hy d 50 eV).17 V. A. Sharov and G. V. Bezdenzhnykh Usp. Khim. 1981,50 1197. C. Goerller-Walrand. Verh. K. Acad. Wet. Lert. Schone Kunsten Belg. Kl. Wet. 1981 43 1. 19 J. M. Lawrence P. S. Riseborough and R. D. Parks Rep. Prog. Phys. 1981,44 1. 20 L. M. Falico W. Hanke and M. B. Maple (ed.) ‘Valence Fluctuations in Solids’ North Holland Publ. Co. New York 1981. S. Siekierski J. Solid State Chem. 1981 37 279. M. G. Mason S. T. Lee G. Apai R. F. Davis D. A. Shirley A. Franciosi and J. H. Weaver Phys. Rev. Lett. 1981 47 730. 22 R. S. Craig W. E. Wallace and H. K. Smith Sci. Technol. Rare Earth Muter. 1980 353. 23 A. Fujirnori and N. Tsuda J. Phys. C 1981,14 1427. 24 B.Spencer and N. M. Edelstein Inorg. Chem. 1981 20 2736. 25 W. F. Huang and L. D. Burton J. Chem. Phys. 1981,,75 440. 26 A. Fujimori and N. Tsuda J. Phys. C 1981 14 L69. 302 S. J. Lyle In the preparative field crystals of ErHz much larger than hitherto available have been produced2' by hydriding the metal at 950 "C. The phase relationship in the SmH,-SmH system has been rein~estigated'~ and the phase widths of SmH2 and SmH found to be significantly less extended than formerly believed. Further the SmH,.95-2.30 (cubic fluorite related) and SmH2.82-2.90 (hexagonal tysonite related) phases are separated by a phase of composition Srn3H7 (cf. the SmF2- Sm3F7-SmF3 system). LiH reacts with EuH2 at high pressures and >600 "C to give LiEuH, whereas the dihydrides of La Sc Ce and Y do not react.,' Lattice resilience is important in materials for practical H storage.Evidence for lattice expansion on hydriding in LaNiS comes from n-diffra~tion~l and in Ln6Mn2 (Ln = Sm or Nd) from X-ray diffraction studies,' (cf. ScFe:). Hydrogen absorption and desorption studies have revealed new hydride phases in binary alloy-H systems. Thus two phases are present in the system HoCo,H (0 s x G 4.1) at 0-80 "C in addition to the H-saturation phase.33 A of the hydrides of NdCo and GdCo also reveals 2-phase regions in addition to the H-saturated metal phase. The alloys LnCo (Ln = Er or Tm) absorb H to form ErCo3H4. and T~CO~H,.~ with a weakening of the magnetic moment on the Co and in the Ln-Co intera~tion.~~ Adsorption of H by YNi, LaPt, and ThNi occurs at high H pressure (S1500 atm.) but whereas the first two alloys form definite hydride phases the third dissolves H in a continues series of solid s01utions.~~ H-isotope exchange between the gas-phase and hydrided LaNiS at 167-195 K and gas pressures of 0.05-0.10 MPa occurs3' with an activation energy of 18 kJ mol-' and an anomalously large isotope effect has been for 'H and 'H absorption in Lao.4Ceo.6Ni5.When LaNi is exposed to oxygen it is the La that oxidizes and not the Ni.39 The thermochemistry of gaseous fluorides (LnF LnF2 and LnF,) of Sm Eu and Tm was studied4' by mass spectrometry and thermodynamic data thus derived. The heat of formation of LaF; was also determined41 by mass spectrometry of vapours above LaF3 and found to be -461 f 4 kcal mol-'.Heat capacities of GdF3 LuF, and YF3 have been determined42 from 5 to 350 K; only GdF shows an anomaly (below 15 K). Various phase studies have been described. The EuC13-EuC12 system exhibits a eutectic at 523°C and 36.3mol% EuC1,; a compound composition EuCI3-3EuCl2 (peritectoid temp 555 "C) was isolated and lattice parameters '' D. J. Peterman J. H. Weaver and D. T. Peterson Phys. Rev. B 1981,23 3903. 28 T.A. Grimshaw F. J. Spooner C. G. Wilson and A. D. McQuillan J. Muter. Sci. 1981,16 2855 29 0.Greis P. Knappe and H. Mueller J. Solid State Chem. 1981 39,49. 30 K. N.Semenenko V. N. Verbetskii and V. A. Stupnikov Vestn. Mosk. Univ. Ser. 2 Khim. 1981 22,204(Chem. Abstr. 1981,95 34 511).31 A. V. Irodova M. E. Kost L. N. Padurets V. A. Somenkov E. 1. Sokolova and S. Sh. Shil'shtein Zh. Neorg. Khim. 1982 26 307. 32 K. H. J. Buschov Solid State Commun. 1981 40 207. 33 H.A. Kierstead J. Less-Common Met. 1981,80 115. 34 H.A. Kierstead J. Less-Common Met. 1981,78 29. 35 S.K. Malik E. B. Boltich and W. E. Wallace Solid Stute Commun. 1981 37 329. 36 T.Takeshita K. A. Gschneidner jun. and J. F. Lakner J. Less-Common Met. 1981,78,P43. 37 B.M. Andreev A. N. Perevezentsev and V. V. Shitikov Zh. Fiz. Khim. 1981,55 1993. 38 D.Dayan and M. P. Dariel Muter. Res. Bull. 1981 16 137. 39 L.Schlapbach Solid Stute Commun. 1981 38 117. 40 P.D. Kleinschmidt K. H. Lau and D. L. Hildenbrand J. Chem. Phys. 1981 74 653. 4' A. T.Pyatenko A. V. Gusarev and L.N. Gorokhov Teplofiz. Vys. Temp. 1981,19,329 (Chem. Abstr. 1981 95 13 7551. 42 H. E. Flotow and P. A. G. O'Hare J. Chem. Phys. 1981,74,3046. Sc Y,the Lanthanides and the Actinides 303 determined.43 At O"C apparently Ln13.9H20 is the only solid phase produced in the LnI-HI-H20 systems (Ln = Tb Tm Yb or Lu).~~ Equilibria between liquid mixtures of NdI and LiI and their vapour phases have been studied4' by absorption spectra of the gas phase which at 1100-1200 K can be described by equation (1) with a heat and an entropy of co-ordination of -210 kJ mol-' and 115J mol-' K-' respectively. Nd13(g) + LiI(g) S LiNA14(g) (1) Preparation of LaCl from powdered La and LaCl in nearly quantitative yield is attained by heating for 30 days at 745-820 "C provided either the LaC1 is first fused with the La or the reactants pressed to 1000atm inside a Ta container before reaction Needles of La2C13 are produced in incomplete Electrolysis of GdC13 at 770 "C yields GdCl at both electrodes (Ta cathode Gd anode) and crystals of Gd2C13 form by reaction between GdCl and GdCl on slow cooling.A new cluster compound GdsC1,C2 containing interstitial C2 units is formed if a graphite crucible is used as ~athode.~' The compound Cs3Y219 is prepared48 by reaction of CsI + Y13 + Y at 750-850°C in a Ta container; it has the Cs3Cr2C1,-type struc- ture. Iodination of Ln203 (Ln = La or Nd) by a mixture of HI + CO in the temperature range 437-973 K gives LnOI as the main New preparative methods are described in which S0C12 with Ce02(H20)2 in (MeOCH2CH2)20(L) give H2CeCl6.3L stable in polar non-aqueous solvents and a useful starting material for the preparation of CeCl adducts." Interest continues in vapour-phase complexes between LnC1 and A12C16 par- ticularly Ln = Tb because of potential application in laser systems. The equilibrium (2) (M = Sc or Nd) has been studied mass spectr~metrically~' and complexes containing more than the 1:1ratio AlCl :MCl discussed. The absorption spectrum of the vapour complex between TbCl and A12C16 has been measured at 20 000 to 50 000 cm-'. Molecular absorption does not appear to lead to strong fluorescence from the 5D4(Tb3') level whereas absorption by the 4f75d states does; the radiative lifetime of the 5D4level at low temperatures is 3.8m~.~~ The intensity of Tb3+ ground-state absorption and 5D4fluorescence transitions in the vapour complex were analysed according to the Judd-Ofelt theory of forced electric dipole transi- tions and in this first successful attempt to utilize observations of both absorption and emission spectra to establish parameters of the theory some discrepancies were noted.53 The luminescence of Tb activated oxyhalides MOX (M = Y La Gd or 43 D.M. Laptev N. M. Kulagin I. S. Astakhova and N. V. Tolstoguzov Zh. Neorg. Khim. 1981 26 1023. 44 G.P. Kuznetsova L. F. Yastrebova B. D. Stepin and Z. P. Yakimova Zh. Neorg. Khim. 1981 26 851. 45 T.Foosnaes and H. A. Oeye Acru Chem. Scund. Ser. A 1981,35,81. 46 R.E.Araujo and J. D. Corbett Inorg.Chem. 1981,20 3082. 47 R.Masse and A. Simon Muter. Res. Bull. 1981,16,1007. 48 D.H. Guthrie G.Meyer and J. D. Corbett. Znorg. Chem. 1981 20 1192. 49 0.V. Spektor and Ya. I. Ivashentsov Zh. Neorg. Khim. 1981,26 2035. so J. Barry J. G. H. Du Preez E. Els H. E. Rohwer and P. J. Wright Znorg. Chim. Actu Lett. 1981 53 L17. 51 H. Schaefer and U. Floerke Z. Anorg. Allg. Chem. 1981,479 89. 52 J. A. Caird W. T. Carnall J. P. Hessler and C. W. Williams J Chem. Phys. 1981,74 798;ibid. p. 805. 53 J. A. Caird W. T. Carnall and J. P. Hessler J. Chem. Phys. 1981,74 3225. 304 S.J. Lyle Lu X = F C1 Br or I) have been studied using U.V. excitation. Intensities of -+ 7FJtransitions and thus emission colour depend on the matrix.5D3,4 7F3,4 5D3.4 -P transitions increase with increasing ionic radius of the host cation. Energies of the strong 4f -+ 5d absorption bands generally increase with the electronegativity of v 54 MCI3(s) + 0.5nA12C16(g) + MC13. nA1C13(g) (2) From n-diffraction TbO(0H) and YO(0H) are both monoclinic and the former but not the latter orders magnetically ( TN= 7.6 K). Evidence has been obtained of a pressure-induced valency change in YbO; at pressures >8 GPa the valence changes from 11 to 111 in a continuous manner accompanied by a change from black to yellow in reflected light.56 The heat capacity of Y(OH)3 has been determined over the range 5-350K and is anomaly free.57 A thermochemical study of the phase reaction [equation (3)] has been carried out and enthalpy data indicate 4 distinct compositional regions.58 1 (3) Valency changes in TmSe induced by alloying with TmTe and EuSe have been studied.Valency mixing increases as Se is replaced by Te up to 20% and the material remains metallic but further replacement (TmSel-,Te,) for x 3 0.5 gives semi-conductors containing only Tm'' with structures corresponding to monochal- cogenides of Sm Eu and Yb. As Eu replaces Tm in TmSe it is divalent because of its highly stable 4f7 shell whereas Trn2+4fl3 and Tm3+4fI25d configurations are nearly degenerate; in Tmo.5Euo,,Se they are separated by a small energy gap (0.1eV) which can be driven to zero by a moderate external pressure (15 kbar).59 Valency change at Tm has also been studied in the series of TmS,-,Se single crystals (x G 1).60The influence of pressure (0 to 15 kbar) on Eu3S4 has been studied using "'Eu Mossbauer spectroscopy.The activation energy for electron hopping between Eu sites decreases by -1.8 k 0.3 meV kbar-' at room temperature but the mean valence of Eu remains unchanged.61 It has been shown that the rate of intervalence electron transfer can be determined by time-domain reflectometry which measures the dielectric relaxation properties of a sample. The technique was tested for the first time to determine the transfer rate in Eu3S4 at room temperature with a result in good agreement with a value derived from Mossbauer spectroscopic data.62 Temperature-tunable spin fluctuations associated with electron hopping (Eu2++Eu3+) in Eu3S4 have been detected by Raman scattering on a single On vaporization at 1750 "C in vacuo LuS loses Lu preferentially to give Lu3S4.64From a study of phase equilibrium for 60-15'1'0 S 20-1000 "C,and 54 J.Holsa and M. Leskela Phys. Status Solidi. B 1981 103 797. " A. N. Christensen and B. Lebech Acta Crystallogr. Sect. B,1981 73,425. s6 A. Werner H. D. Hockheimer A. Jayaraman and J. M. Leger Solid State Commun. 1981 38 325. '' R. D. Chirico and E. F. Westrum jun. J. Chem. Thermodyn. 1981 13 519. 58 H. Inaba A. Navrotsky and LeRoy Eyring J. Solid State Chem. 1981 37 77. 59 B. Batlogg Phys. Rev. B 1981 23 650. 6o U. Koebler K. Fischer K. Bickmann and H. Lustfeld J. Magn. Magn. Muter. 1981 24 34. " J. Roehler and G. Kaindl Solid State Commun. 1981 37 737.B. C. Bunker M. K. Kroeger R. M. Richman and R. S. Drago J. Am. Chem. SOC.,1981,103,4254. 63 G. Guentherodt and W. Wichelhaus Solid State Commun. 1981 39 1147. 64 A. V. Hariharan D. R. Powell R. A. Jacobson and H. F. Franzen J. Solid State Chem. 1981,36,148. Sc Y the Lanthanides and the Actinides 305 to 18.8atm pressure fields of stable existence of Gd2S3 and GdS1,84 were estab- li~hed.~' Heats of formation of LnN have been derived; all Ln exhibit a valency of 3.00 except Ce for which the mean valency was 3.05.66Yb dissolves in liquid ammonia and a recent study has revealed that the density of the solutions increase with metal concentration in contrast to solutions of alkali metals and Ca. The Pr-P phase diagram has been constructed.68 In addition to solid solutions of P in Pr the phosphides PrP (n = 1,2,5 or 7) are formed.The structure of monoclinic EuAs is closely related to that of SrAs3 with 2-dimensional infinite polyanionic As:- nets. It undergoes a magnetic phase transition at 10.5 K.69 Thermodynamic properties of HoSb and ErSb have been determined7' at 647-783 and 580-809 K respec- tively. A 121Sb Mossbauer study71 of LnSb (all Ln except Pm and Lu) at 78 K reveals for each substance a single line spectrum with an isomer shift that increases linearly with atomic number. Mossbauer spectroscopy and X-ray diffraction have established7 that EuNi2P2 (ThCr2Si2 structure) is a fluctuating valence compound with a nearly temperature-independent average valence of 2.6 from 300 to 77 K. By way of contrast EuCo2P2 has europium in its stable Eu" state as normal.There is considerable interest in the preparation structure and properties of ortho- and poly-phosphates either because of their potential in nuclear waste containment or for their luminescence. CeP04 a synthetic analogue of monazite has been prepared and the structure determined for comparison with that of the K3Lu(P04) has a distorted glaserite (hexagonal) The limiting solubility of Eu3' and Nd3' in LuPO is higher than in YPO,. There is some evidence that the co-ordination polyhedra in LuP04 are more distorted and elec- tron-density distribution reduced by such substit~tion.~~ New orthophosphates of general formula Na,Ln -Sr3-2x(PO,) seem to be of the Sr3(P04) structure type (Ln = La Nd or Gd).In NaSSr Lal-,-yCe,Tby(P04)2 a new high yield phosphor absorbing light in the U.V. region results from Ce3+ +Tb3+energy tran~fer.~~ Best overlap between Ce3' emission and Tb3+ excitation is obtained for phosphates containing alkali-metal ions.77 The triphosphates Nd5(P3010),-22H20 NH4Nd3(P3010),12H20 and (NH3)3Nd4P3010 * -14H20 are precipitated from aqueous Nd(NO,) solution by addition of (NH,),P301,; decomposition of the phosphate anion accompanies attempts at thermal dehydrati~n.~~ Crystals of a'-CsNdP4012 and P-CsNdP4012 belong to the monoclinic and cubic systems 65 I. G. Vasil'eva and L. N. Kurochkina Zh. Neorg. Khim. 1981 26 1872. " A. M. Mulokozi J. Less-Common Met. 1981,80 235. 67 R. Hagedorn and J. P. Lelieur J. Phys.Chem. 1981,85 275. K. E. Mironov Izv. Akad. Nauk SSSR Neorg Mater. 1981 17 197. 6q W. Bauhofer M. Wittmann and H. G. von Schnering J. Phys. Chem. Solids 1981,42 687. 70 V. I. Goryacheva Ya. I. Gerasimov and V. P. Vasil'ev Zh. Fiz.Khim. 1981 55 1080. 71 P. E. Holbourn and F. W. D. Woodhams J. Solid State Chem. 1981 39 186. 72 R. Nagarajan E. V. Sampathkumaran L. C. Gupta J. Vijayaraghavan V. Prabhawalkar and B. D. Palalia Phys. Lett. A 1981 84 275. 73 G. W. Beall and L. A. Boatner J. Znorg. Nucl. Chem. 1981 43 101. 74 V. A. Efremov P. P. Mel'nikov and L. N. Komissarova Koord. Khim. 1981 7 467. 75 E. N. Murav'ev V. P. Orlovskii A. V. Potemkin L. N. Kargareteli N. S. Dyhabishvili and V. D. Vorol'ev Zzv. Akad. Nauk SSSR Neorg. Mater. 1981 17 121. 76 C.Parent G. LeFlem M. El-Tabirou and A. Daoudi Solid State Commun. 1981 37 857. 77 P. Bochu C. Parent A. Daoudi G. LeFlem and P. Hagenmuller Mater. Res. Bull. 1981,16 883. 78 G. V. Rodicheva I. V. Tananaev and N. M. Romanova Zzv. Akad. Nauk SSSR Neorg. Mater. 1981 17. 126. 306 S. J. Lyle respectively. The former consists of chains of PO4 tetrahedra linked at corners,79 whereas the latter contains cyclic [P4Ol2I4- groups;8o in both substances Nd3+ is co-ordinated to eight oxygens. In contrast KYbP4OI2 crystals consist of infinite tetrahedral PO4 chains and the Yb3+ is co-ordinated to seven oxygens.81 The NaPO,-CeP,O system yieldss2 only a single compound NaCeP4012 which melts in a peritectic reaction at 865 "C whereas the system KP03-CeP;09 gives KCeP4012 and K2CeP5OI5 melting in peritectic reactions at 741 and 880 "C re~pectively.'~ KCeP4012 is monoclinic and isotypic with KNdP4012 83 which consists of ring anions [P4Ol2I4- with K in trigonal-prismatic co-ordination and Nd in distorted 7-co-ordinated antiprism~.~~ The '"Eu Mossbauer spectra of orthorhombic perovskites EuMO (M = Cr Mn Fe or Co) are broadened by unresolved hyperfine effects.The broadening can be attributed to a quadrupole interaction with a coupling constant of e2q Q == -6.5 mm s-' which is in agreement with the value predicted for EuFe0 from a crystal field calculation.85 Carbonates of the type NaM(CO,) (M = La-Nd Sm-Lu or Y) have been prepared by dehydration of NaM(C03)* * xH20at 350-500 "C in C02 under 3 kbar pressure.The crystal system changes from orthorhombic to monoclinic beyond Gd.86 Crystals of [Gd(HC03),(H20)4]. 2H20 are formed in a formate solution of Gd"' on a waterbath. The Gd is ten co-ordinated and HCU; groups act as bidentate ligand~.'~ The crystal and molecular structures of [ASP~~]L~(S~P(OE~)~}~ (Ln = La or Er) have been compared with results obtained in solution from n.m.r. studies. Although the structures are the same in the solid with each Ln co-ordinated to 8 sulphur in almost perfect dodecahedra in C2H2C12 they are quite different. In solution there is a change from dodecahedra1 to square antiprismatic geometry for such compounds beyond Ho in the Ln series.88 Interest continues in the use of P-diketonate complexes in non-aqueous solvents and complexones of the Ln in aqueous systems as shift reagents in n.m.r.structural investigations. Complexes of edta hed3a and trans-l,2-diaminocyclohexanetetra-acetic acid with Ln'" in water and endo-cis-bicyclo[2,2,l]hept-5-ene-2,3-dicar-boxylic acid (1) have been examined by n.m.r. relaxation time measurements. All 3 complexes appear to form adducts with (1) and it is proposed that this behaviour is general for such complexes in water.89 However Ln-induced shift data have been presented for cytidine 5'-monophosphate(cyc1mp) and L-alanine binding to a series of Ln-edta chelates at high pH and because of slow exchange between bound and free-adduct-former the heavier Ln-edta complexes were considered 79 S. 1. Maksimova K. K. Palkina and V. B. Loshchenov Izv.Akad. Nauk SSSR Neorg. Muter. 1981 17 116. K. K. Palkina S. I. Maksimova and N. T. Chibiskova Dokl. Akad. Nauk SSSR 1981 257 357. 81 K. K. Palkina S. I. Maksimova N. N. Chudinova N. V. Vinogradova and N. T. Chibiskova Zzv. Akad. Nauk SSSR Neorg. Muter. 1981 17 110. 82 M. Rzaigui M. Trabelsi and N. Kbir-Ariguib C. R. Hebd. Seances Acad. Sci.,Ser. 2 1981 292 505. 83 M. Rzaigui M. Dabbabi and N. Kbir-Ariguib J. Chim. Phys. Phys.-Chim. Biol. 1981,78 563. 84 B. N. Litvin G. I. Dorokhova and 0.S. Filipenko Dokl. Akad. Nauk SSSR 1981 259 1102. '' T. C. Gibb J. Chem. SOC., Dalton Trans. 1981 2245. 86 H. Schweer and H. Seidel Z. Anorg. Allg. Chem. 1981 477 196. 87 N. G. Furmanova L. V. Sobeleva and L. M. Belyaev Kristallografiya 1981 26 312. A. A. Pinkerton and D.Schwarzenbach J. Chem. SOC.,Dalton Trans. 1981,1470. *9 M. Delepierre C. M. Dobson and S. L. Menear J. Chem. SOC. Dalton Trans. 1981 678. Sc Y,the Lanthanides and the Actinides 307 unsatisfact~ry.~~ A multinuclear (23Na 2H 170 37Cl) n.m.r. study of 3 Ln shift reagents in aqueous solution has been described. Ln complexes with 1,4,7,10-tetra- azacyclododecane-N,N',N",N"-tetra-acetate (dota) 1,4,7-triazacyclononane-N,N,N"-triacetate(nota),and edta were prepared in 2Hz0. The axially symmetric [Ln dotal- complexes were pronounced the best as the shifts measured were purely dipolar in origin." Exchange interaction contributions to energy transfer between ions in the rapid diffusion limit (rdl) has been studied for transfer between Tb"' chelates of edta and hed3a and metal (i.e.Co"' or Cu")-edta energy acceptors.It was concluded that exchange interaction accounts for nearly all energy transfer and in the rdl there is a very strong dependence on distance of approach of donor and acceptor.92 Adduct formation in benzene between Ln shift reagents and organic bases has been studied by calorimetric titration. Stability constants K enthalpies AH' and entropies ASo,were determined for adducts of tris(2,2,6,6-tetramethyl-heptane-3,5-dionato)lanthanide(111)(Ln = Eu Yb or Pr) with pyridine various alkyl pyridines DMSO and pyridine N-oxide. Values mostly lie in the range 2 < log K < 4 and 15 < -AHD< 35 kJ mol-' with some variation due to steric effects. Unusual positive AS' were attributed to the high solubilities of the ad duct^.'^ The structure of the Gd(f~d)~ adduct of [N,N'-ethylenebis(acetylacetoneiminato)] nickel(I1) (2) in C'HCI has been examined by n.m.r.spin-lattice relaxation studies (H f od is 1,1,1,2,2,3,3 -heptafluoro -7,7-dime thyloct ane- 4,6-dione). A Gd(f od)3 * (2) adduct is formed in rapid equilibrium with its components and by assuming Gd binds to both oxygen in (2) the position of Gd relative to (2) is determined from paramagnetic contributions to the relaxation rates.94 The interaction of Eu([~H,]- f0d)3 with a series of Co"' complexes of which pyridine azido[N,N'-ethy- lenebis(acetylacetoniminato)]cobalt(~~~) is the parent has been investigated in C2HC13 by 'H and 13C nmr; 1 1 adducts with lifetimes of to lo- s provide examples of the non-dilute case of fast-exchange line br~adening.'~ Some further work has been reported on complexes with crown ethers and related ligands.Solutions of 12-crown-4(1') and 15-crown-5(Lff) added to Ln(C104) * xH20 (x = 0.1-1) in MeCN under N2 give Ln(C104)3.2L'.(Ln = La-Nd Sm-Gd) Ln(C104)3-2L"(Ln = La-Nd Sm or Eu) and Ln(C104)3 -L'L"(Ln = Pr Nd Sm Eu or Gd) but only in Ln(ClO,) -2L' is there evidence96 for bonded ClO,-. The crystalline 4 :3 complex of 18-crown-6 with Nd(N03)3 of [Nd(N03)6]3- and [Nd(NO,) (18-crown-6)]+. Pentaethyleneglycol HO(CH2CH20)5H forms a ring structure like that of crown compounds around Nd3+ which is co-ordinated to 4 oxygens derived from two NO3- and 6 from the ether in the crystalline nitrate 90 A D.Sherry C. A. Stark J. R. Ascenso and C. F. G. C. Geraldes J. Chem. SOC. Dalton Trans. 1981,2078. 91 C. C. Bryden C. N. Reilley and J. F. Desreux Anal. Chem. 1981 53 1418. 92 C. F. Meares and S. M. Yeh J. Am. Chem. SOC., 1981,103 1607. 93 D. P. Graddon and L. Muir J. Chem. Soc. Dalton Trans. 1981,2434. y4 J. Y. Lee D. A. Hanna and G. W. Everett jun. Znorg. Chem. 1981 20 2004. y5 L. F. Lindoy and H. W. Louie Inorg. Chem. 1981 20,4186. y6 J.-C. G. Buenzli Tham Huyhn Oanh and B. Gillet Inorg. Chim. Acta 1981 53 L219. 97 J.-C. G. Buenzli B. Klein D. Wessner K. J. Schenk G. Chapuis G. Bombieri and G. DePaoli Inorg. Chim.Acta 1981 54 L43. 98 Y. Hirashima K. Kanetsuki J. Shiokawa and N. Tanaka Bull. Chem. SOC. Jpn. 1981 54 1567. 308 S. J.Lyle Total luminescence (TL) and magnetic circularly polarized luminescence (MCPL) spectra are reported for several tris(P-diketonate) europium(II1) chelates in DMSO -D and DMF solutions. Spectra recorded over the 5D0 'F (J = 0-4) emission region with applied magnetic fields from 0-4.2 T show no magnetic field depen- dence and can be interpreted using Faraday B terms associated with non-degenerate crystal-field transition^.^^ Optical activity associated with f-f emission bands of Tb"' mixed complexes containing chiral ligands have been studied using circularly polarized luminescence (CPL) spectroscopy. loo A vicinal effect experienced by the Tb"' is manifested by a purely positive or negative CPL line shape and the sign of the CPL is governed by the absolute configuration of the ligand.The technique has been applied to the study of complexes of the form TbL3 Tb(DPA)L2 and Tb(DPA)2L where DPA is pyridine-2,6-dicarboxylicacid and HL an a-hydroxycar- boxylic acid"' or an amino-acid.'02 Similar studies have been reported with Eu"' chelates of fluorinated P-diketones and phenylalkylamines and phenylalkylamino- alcohols.103 The crystal structure of [Li(tmen)3].[Er(CH3)6](tmen = Me2NCH2CH2NMe2) Ln complex has been rep~rted."~ Single crystals of Na,EuL3 * 2NaBF4-6H20 (L = oxydiacetate) were prepared and X-ray and CD-light absorption data recor- ded from fragments of a single crystal. The crystal structure of [Li(tmen),] * [Er(CH3)6] (tmen = Me2NCH2CH2NMe2) has been determined and it shows that Ln can form organometallic compounds in which all co-ordination sites on the metal are occupied by carbon atoms of monohapto-bonded alkyl groups.1o5 Reactions between ethene propene and propa-1,2-diene and Ln metal vapour (Ln = Yb Sm,or Er) have been studiedlo6 by co-condensation at 77 K followed by isolation of products at room temperature.Several reaction pathways were identified namely Ln insertion into C-H and cleavage of C -C bonds homologation oligomerization and dehydrogenation. Anionic pentamethylcyclopentadienyl complexes of the type [ML,]-[(Me,C,),LnCl,] where M is Li or Na and L is diethylether or tmen and Ln is Nd Sm or Yb have been prepared"' from LnC13 and (Me&-. Oxidation of Yb metal with Me,C,I in the presence of LiI gives Li[Me5C5)2Yb12].'08 4 The Actinides During the past year reviews have been published dealing with production and recovery of transplutonium elements,'09 nitrate complexes,'1o the kinetics and mechanism of substitution reactions of complexes with co-ordination number >6 99 F.S. Richardson and H. G. Brittain J. Am. Chem. Soc. 1981 103 18. loo H. G. Brittain Znorg Chim. Acta 1981 53 L7. lo' H. G. Brittain Znorg. Chem. 1981 20 4267. lo' H. G. Brittain Inorg. Chern.,1981 20 3007. X. Yang and H. G. Brittain Znorg. Chem. 1981 20 4273. Io4 F. R. Fronczek A. K. Banerjee S. F. Watkins and R. W. Schwartz Znorg. Chem. 1981 20 2745. 105 H. Schumann J. Pickardt and N. Btuncks Angew. Chem. Int. Ed. Engl. 1981,20,120. Io6 W. J. Evans K. M. Coleson and S. C. Engerer Znorg.Chem. 1981 20,4320. lo' T. D. Tilley and R. A. Andersen Inorg. Chem. 1981 20 3267. P. L. Watson J. F. Whitney and R. L. Harlow Znorg. Chem. 1981 20 3271. Io9 T. Ishimori K. Ueno and M. Hoshi in 'Transplutonium Elements-Production and Recovery' Am. Chem. SOC. Symp. Ser. 1981 No. 161 p. 223. U. Casellato and P. A. Vigato Coord. Chem. Rcc. 1981,36 183. Sc Y,the Lanthanides and the Actinides 309 and of related fluxional systems."' The crystal chemistry and electronic structure of An compounds have also been covered.'12 Recommended values have been tab~lated"~ for the standard heat of formation free energy enthalpy and heat capacity of atoms ions and compounds of Ac Th and U. First ionization potentials have been meas~red"~ for U Pu Am Cm and Cf deposited on a Re surface heated in the range 2400-2800 K.The chemistry involving halogens has been largely confined to that of the fluorides and fluoro-complexes. Optimum conditions of temperature and H-flow have been determined'15 for the reduction of UF to UF3 and the preparation purification and physical properties of UF in the liquid state have been described.'16 For UF conversion the optimum temperature range is 1070-1125 K at a H-flow which yields a constant H2 :HF ratio in the outlet gas stream. The electrical conductivity and viscosity of liquid UF are comparable to those of typically ionic molten salts. The absorption spectrum of UF in the 350-700 nm range has been ~btainedl'~ following laser photolysis of UF in the gas phase. Photoelectron spectroscopy of ThF and UF in the solid and gas phases indicates''' that the electronic structures are the same except for the presence of two metal 5f electrons in UF,.The Raman spectrum of U02F2 dissolved in anhydrous HF-AsF solutions retains the emission band at 925 cm-' characteristic of the symmetric U-0 stretching frequency thus demonstrating the stability of dioxouranium(v1) in this medium."' The trigonal and orthorhombic BkF crystal systems are distinguishable by their absorption spectra in the 400-1100 nm region.',' Spectroscopic studies121 of EsX3 (X = F C1 Br or I) indicate that in the decay sequence 253E~+a*,'Bk +/3-249 Cf the oxidation state of the parent is maintained by its progeny. Crystalline Na,(UO,),F -6H20 prepared by evaporation of solutions of NaF .with U02F2 or U02(N03),* 6H20 contains complex chains made up from [(UO2)2F -FI3-that are linked by a single bridging F.', A preparation of PuF6 and an account of its reactions with PF, AsF, CCI, BC13 and BBr are rep~rted;'~~ in each instance reaction leads to reduction to PuF,.Mixed methoxy-uranium(v1) fluorides and U(OMe) have been prepared', by reactions of the type shown in equations (4) and (5). 'H and ''F n.m.r. studies indicate that U is six-co-ordinated in these UF6 + n(Me,),SiOMe + U(OMe),F6- + n(Me),SiF (4) UF6 + 6NaOMe + U(OMe)6 + 6NaF (5) P. Moore Inorg. React. Mech. 1981 7 245. D. Damien and C. H. DeNovion J. Nucl. Mater. 1981 100 167. 'I3 D. D. Wagman W. H. Evans V. B. Parker R. H. Schumm and R. L. Nuttall NBS Tech.Note (US) 1981 270-8,l. 'I4 A. P. Chetverikov V. Ya. Gabeskiriya and V. V. Puchkov Zh. Tekh. Fiz.,1981 51 130 (Chem. Abstr. 1981 94 71 7901. 115 K. N. Roy R. Prasad M. Bhupathy V. Venugopal Z. Singh and D. D. Sood Thermochim. Acta 1981 43 333. K. Asada K. Ema K. Tanaka and K. Hayashi J. Inorg. Nucl. Chem. 1981 43 2049. 'I7 K. C. Kim and G.A. Laguna Chem. Phys. Lett. 1981,82,292. J. M. Dyke G. D. Josland A. Morris P. M. Tucker and J. W. Tyler J. Chem. Soc. Faraday Trans. 2 1981 77 1273. 'I9 C. G. Barraclough R. W. Cockman and T. A. O'Donnell Inorg. Nucl. Chem. Lett. 1981 17 83. I2O D. D. Ensor J. R. Peterson R. G. Haire and J. P. Young J. Inorg. Nucl. Chem. 1981 43 1001. 12' J. P. Young R. G. Haire J. R. Peterson D. D. Ensor and R. L.Fellows Inorg. Chem. 1981,20 3979. Nguyen Quy Dao Sadok Chourou and J. Heckley J. Znorg. Nucl. Chem. 1981 43 1835. 123 R. C. Burns T. A. O'Donnell and C. H. Randall J. Inorg. Nucl. Chem. 1981 43 1231. 124 E. A. Cuellar and T. J. Marks Inorg. Chem. 1981 20 2129. 310 S.J. Lyle monomeric compounds which undergo rapid intermolecular exchange of ligand in C2HzClz. Relativistic effective-core-potential calculations have been carried out1" to pro- vide an explanation for the differing geometries of U02'+ (linear) and isoelectronic Tho,( strongly bent). The calculations correctly predict the respective geometries whose differences are ascribed to the relative ordering of the 5f and 6d levels; for U the 5f levels are lower and dominate back-bonding from the 0 in UO2'' whereas for Th the 6d levels are lower and dominate back-bonding.The 5f levels prefer linear the 6d bent geometries. What was formerly thought to be PuO formed on the surface of Pu metal is now ascribed to an oxocarbide PuO,C (x = 0.65 y = 0.45) identified by photoelectron and Auger spectra.126 The forma- tion of a hydrated NH4Np04 stable in air by electrolytic oxidation of Np"' in (NH4)2C03 solution has been described. ''' Raman spectra obtained for dioxouranium(v1) solutions as a function of pH gave v1 symmetric stretching bands at 869 851 and 836 cm-' which were ascribed12* to U022+,(U02)2(OH)22' and (UO,),(OH),' in that order. Compounds MPu02* XO * yH20 and M'(PuO,XO,)~-zH20 (X = P or As; M = H' K' Rb' or NH,'; M' = Ca2' or Sr2') have been prepared and identified by X-ray crystallographic comparison with the corresponding U and Np Further studies of equilibria in the commercially important aqueous uranium(v1)- carbonate system have been p~blished.'~~*'~' C02solubility and pH measurements have indicated that at an ionic strength of 3(NaClO,) with U022+< 0.05 M and log [HCO,-] -1.2 the prevailing metal species is uo2(co3)34-.On acidification and before solid uranium(v1) carbonates precipitate a polynuclear complex is formed according to equation (6) with no evidence for U02(C03)22- or mixed hydroxocarbonates in the range 9 UOz2-d 0.03 M; 0.1 9 Pco2 d 1atm.; -3.0 Q log[HC03-] 9 -0.7. The 13C n.m.r. spectra indicate three equivalent carbonate groups and two different carbonate sites in the mono- and tri-nuclear complexes respectively.Carbonate-exchange rates between the solution and the metal complexes increase with decreasing pH.',' + 3c02(,,+ 3H20 + (U02)3(C03)66-+ 6HC03-(6) Interest has been maintained in luminescence and related energy transfer pro- cesses and photochemistry of An compounds mainly those of uranium. It has been shown that the triboluminescence of U02(N03) . 6H20originates from both UOZ2' and N e~citati0n.l~~ Energy transfer between U"' and Eu'" in aqueous HClO solution apparently involves one or more hydrolytic species134 derived from UOZ2+. Np"' is photochemically reduced to Np" in 0.1-1 M-HNO containing 1M-UO2'' lZ5 W. R. Wadt J. Am. Chem. SOC.,1981,103,6053. D. T. Larson and J. M. Haschke Inorg.Chem. 1981 20 1945. V. I. Dzyubenko S. A. Karavaev and V. F. Peretrukhin Dokl. Akud. Nauk SSSR 1981 257 147. ''13 L. M. Toth and G. M. Begun J. Phys. Chem. 1981,85,547. lZ9 R. Fischer G. D. Werner T. Lehmann G. Hoffman and F. Weigl J. Less-Common Me?.,1981 80 121. 130 L. Ciavatta D. Ferri I. Grenthe and F. Salvatore Inorg. Chem. 1981,20,463. 13' D. Ferri I. Grenthe and F. Salvatore Actu Chem. Scand. Ser. A 1981 35 165. 13' T. E. Strom D. E. Woessner and W. B. Smith J. Am. Chem. SOC., 1981 103 1255. 133 B. P. Chandra and J. I. Zink J. Phys. Chem. Solids 1981,42 529. '34 S. P. Tanner and A. R. Vargenas Inorg. Chem. 1981 20,4384. Sc Y the Lanthanides and the Actinides 311 by a reaction in which nitrate is reduced to nitrite which then reduces NP~'.'~~ It is reported that photochemical decomposition of dioxouranium(v1) complexes of edta and diethylenetriaminepenta-aceticacid irradiated at 254 nm results in a single decarboxylation of the ligand and the formation of U'" Electronic excitation of solutions of the thf adduct of dioxouranium(v1) bis(hexafluoroacety1- acetonate) (3) also gave UIV probably as U[(CF,CO),CH],; it is that the reaction occurs through the intermediacy of a hypothetical UIV peroxide complex (an isomer of U022+).[(3)-thf] undergoes fast reversible displacement of thf by other bases in CHC13 and CF3CH20H.'38 The "F n.m.r spectral behaviour of a mixture of cis-and trans-uranyl trifluoroacetylacetonate complexes indicate that base migration rather than anion rotation is the preferred intramolecular rearrangement path.139 Some work has been reported on the preparation and properties of new Th and U complexes with organic ligands.Thus the tetrakis (N-alkylalkane-hydroxamato)thorium(Iv) complexes Th[(Me),CHN(O)C(O)R] (R = t-butyl or neo-pentyl) are prepared from aqueous solutions of ThIV and the corresponding hydroxamic acid. Both complexes are hydrocarbon soluble and sublime readily at 100"C and T~rr.'~' Air- and moisture-stable dioxouranium(v1) monothiocarbamate alkoxides [R2NH]U02(R2NCOS)20R' (R = Me Et or Pr"; R' = Me or Et) have been prepared; they are soluble in polar solvents like MeCN.',' Air-stable dithiophosphinate complexes Th(S2PR2), are prepared from ThC14.8H20 and M(S2PR2) in ethanol (R = Me Et Pr' Ph or C6Hll; M = Na' or NH,'); each Th is surrounded by eight S in a dodecahedra1 arrangement.'42 A crystal -struct ure determination of h ydridotris[ bis( trime th ylsil yl) amidoluranium (IV) leaves no doubt that it is a 4-co-ordinate monomeric hydride; the ThIV analogue is i~ostructural.'~~ Pyrolysis of these hydrides yields novel 4-membered ring metal- locycles where M = Th or U.', (Me,Si)*M SiMe (4) Interest has been sustained in the organometallic chemistry of U and to a lesser extent Th.Alkyl and aryl homologues of cyclo-octatetraene (COT) have been used to prepare substituted thorocenes. Unlike thorocene (q8-COT),Th these com- pounds are soluble in organic solvents and like corresponding uranocenes they undergo facile ligand exchange with COT2- but not with COT.'45 The uranium 135 H.A. Friedman and L. M. Toth J. fnorg. Nucl. Chem. 1981 43 1611. 136 H. G. Brittain Z. Konteatis S. Janusz and D. L. Perry Inorg. Chim. Acta. 1981 51 39. 13' G. M. Kramer M. B. Dines A. Kaldor R. Hall and D. McClure fnorg. Chem. 1981 20 1421. 13' G. M. Kramer E. T. Maas jun. and M. B. Dines Inorg. Chem. 1981 20 1415; ibid. p. 1418. 139 G. M. Kramer and E. T. Maas jun. Inorg. Chem. 1981 20 3514. 14" W. L. Smith and K. N. Raymond J. Am. Chem. Soc. 1981,103 3341. 14' D. L. Perry fnorg. Chim. Acta 1981 48 117. 14' A. A. Pinkerton A. E. Storey and J.-M. Zellweger J. Chem. Soc. Dalton Trans. 1981 1475. '43 R. A. Andersen A. Zalkin and D. H. Templeton Inorg. Chem. 1981 20 622. 144 S. J. Simpson H. W.Turner and R. A. Andersen Znorg. Chem. 1981 20,2991. 145 C. Levanda and A. Streitwieser jun. Inorg. Chern. 1981 20 656. 312 S. J. Lyle powder method has been adapted to a convenient synthesis of U(C,H,),X (X = C1 Br or I C5H5= the cyclopentadienyl anion).'46 The reaction of cyclopentadiene with imidouranium(1v) compounds such as U(NPr& and U(NPhJ4 leads to part substitution giving compounds of the type (q5-C5H5)2U(NR,) in good yield.'47 The compound U(C,H,),Cl reacts with sodium pyrazolate in thf to give U(C,H,),(C,H,N,) the molecular structure of which consists of discrete molecules in which the U'" is coordinated by three q5-C5H5 rings in nearly trigonal array and both N of the pyrazolate ring so that the local two-fold axis of the pyrazolate ring and the local three-fold axis of the U(C,H5) residue ~0incide.l~~ Lithiated phos- phoylides react with U(C,H5),C1 to give phosphoylide complexes e.g.Li(CH2)2P(Ph)2 reacts to give the novel metallacycle (77,-C5H5)2U[CHP(Ph),CH,],U(q5-C5H5)2 in thf. 149 Dicyclopentadienyl bis(diethy1- amido)uranium(Iv) (q5-C5H5),U(NEt,), reacts with CS, COS and CO to give insertion-type compounds of the form (q5-C,H,),U(XYCNEt,) (X = Y = 0 or S X = 0,Y = S); they are monomeric in benzene except for the compound where X = Y = O.l5OReaction of (q5-C5H5)2U(NEt,)2 with carboxylic and thiocarboxylic acids leads to the acid substitution of the amido-gro~ps.'~' The homoger eous catalytic hydrogenation of M(q5-Me5C5)2(q2-COK)Cl (M = Th R = CH,C(Me),; M = U R = Ph) occurs at room temperature to yield the corresponding alkoxides [M(q ,-COR) -+ MOCH2R] by using Hz at -=1atm pressure and [Th(Me5C5)2H2]2 as ~ata1yst.l~' 14' 14' 146 N.K. Sung-Fu F. F. Hsu C. C. Chang G. R. Her and C. T. Chang Znorg. Chem. 1981,20 2727. A. L. Arduini N. M. Edelstein J. D. Jamerson J. G. Reynolds K. Schmid and J. Takats Znorg. Chem. 1981 20 2470. C. W. Eigenbrot jun. and K. N. Raymond Znorg. Chem. 1981 20 1553. 149 R. E. Cramer R. B. Maynard and J. W. Gilje Znorg. Chem. 1981 20,2466. A. L. Arduini J. D. Jamerson and J. Takats Znorg. Chem. 1981 20 2474. A. L. Arduini and J. Takats Inorg. Chem. 1981 20 2480. E. A. Maatta and T. J. Marks J. Am. Chem. Soc. 1981 103 3576.

ISSN:0260-1818    

DOI:10.1039/IC9817800299

出版商:RSC    

年代:1981

数据来源: RSC

摘要:

12 Radiochemistry By D. S. URCH Chemistry Department Queen Mary College University of London Mile End Road London El 4NS 1 Introduction The purpose of this Chapter is to review recent progress in those aspects of radiochemistry that are not covered elsewhere in Annual Reports. Thus whereas the general chemistry of the actinides will not be treated here radiochemical topics in this area such as isotope and element separation will be; similarly the general use of labelled compounds as tracers in organic and inorganic chemistry and in biochemistry and in the whole field of nuclear medicine will not be covered but a brief review of methods for incorporating radioactive isotopes into specific molecules will be given. Specifically radiochemical subjects such as the chemistry of species produced in nuclear reactions (including decay processes) will of course be considered here.Recent books have for some reason all been in German an Introduction to Nuclear Chemistry’ and two laboratory texts of experiments in radiochemistry (one for the East Germans2 and one for the West3). The problem of nomenclature for labelled inorganic molecules has been considered and recommendations made in a recent IUPAC p~blication.~ The history of one specific stage of radiochemistry work associated with the reactor at the University of Chicago during and after World War 11 has been ~ompleted,~ and the chemistry of actinide and fission products from a somewhat older reactor about 2 gigayears older at Oklo has been discussed in a recent report.6 Some new data on nuclear properties have appeared (71/2233U 1.504 x lo5~r:~ 249Bk,329 d8) and of rather more chemical interest changes in the half-life of 99mT~ in different valence states and ligand environments have been measured.’ K.H. Lieser ‘Introduction to Nuclear Chemistry’. Verlag. Chemie Weinheim West Germany 1980. * L. Herforth K. Huebner and H. Koch ‘A Practical Course in Radioactivity and Radiochemistry’ V.E.B. Deutscher-Verlag der Wissenschaften Berlin East Germany 1981. C. Keller ‘Experiments of Radiochemistry’ Diesterweb Frankfurt an Main West Germany 1980. W. C. Fernelius T. D. Coyle and W. H. Powell Pure Appl. Chem. 1981 53 1887. G. T. Seaborg ‘History of Met. Lab. Section C-I May 1945-May 1946’ Lawrence Berkeley Lab.(PUB-112) Berkeley CA USA 1980 (NTIS pc A99/MFA01). A. Ogard G. Bentley E. Bryant C. Duffy J. Grisham E. Norris C. Orth and K. Thomas 3rd Annual Meeting of the Materials Research Society 1980 (NTIS PC AOZ/MF A01). ’A. M. Gejdel’man Yu.S. Egorov A. A. Lipovskij A. V. Lovtsyus L. D. Preobrazhenskaya N. C. Ryzhinskij A. V. Stepanov and Yu.V. Khol’nov Zzv. Akad. Nauk SSSR Ser. Fiz. 1979 43 928. V. G. Polyukhov G. A. Timofeev B. I. Levakov Rep. NIIAR-28 (436) 1980; cf. ZNZS Atomindex 1981,12,604251. B. Johannsen and R. Muenze Radiochem. Radioanal. Lett. 1981 47 57. 313 314 D. S. Urch 2 Radioisotopes Radioisotopes can be produced either from deliberately chosen nuclear reactions which will be considered in the first part or from the separation of complex mixtures the techniques for which will be considered in the second part of this Section.Specific Isotopes.-’H and 18Fcan be produced by the neutron irradiation of lithium carbonate. lo Labelled hydrofluoric acid and water were extracted from the target by steam distillation and the isotopes separated on an ion-exchange column. 19Ne a positron emitter for radiopharmaceutical use has been made” by a-particle bombardment of oxygen or by the nuclear reaction of 2H with 19F. Protons accelerated in a cyclotron react with 51V to produce ’lCr and carrier-free 57C0 can be produced in the same way from ”Ni.12 The bombardment of nickel with 32 MeV a-particles produces 62Zn which decays to the pure positron emitter 62Cu.The zinc isotope is adsorbed onto a zirconia column from which the copper-62 can be eluted as desired (61Cu results from 18 MeV a-bombardment).” Tomography using radioisotopes depends upon the emission of annihilation (0.51MeV) radiation from positron emitters such as 68Ga. This isotope is formed by the decay of 68Ge. Pure carrier-free 68Ge can be produced by distillation from hydrochloric acid ~olutions.~~ The usual commercial form of a generator from which 68Ga can be eluted from adsorbed 68Ge produces the gallium as the very stable EDTA complex. Other generators have been proposed15 from which gallium can be obtained either in dilute acid ~oIution~~*~~ or as a 8-hydroxyquinoline complex. l8 Another approach uses irradiated gallium oxide and a zirconia exchange c01urnn.’~ 81mKr is an isotope with considerable medical potential for blood-flow and lung-ventilation studies.It is most conveniently made from the decay of 81Rb which in turn can be made by high-energy (70MeV) proton bombardment of rubidium sulphate” or lower-energy (29 MeV) 3He bombardment of copper bromide.’l The radioactive krypton can either be removed from solution by oxygen carrier or eluted22 from a Dowex resin or zirconium phosphate column2’ which retains the 81Rb. 99mTc is another isotope with widespread use in nuclear medicine. It arises from the decay of 99M~ which can be extracted from fission product~,’~ lo Zahirudding Majalah BATAN 1979 12 23; cf. INISAtomindex 1981 12 591 098. l1 R. S. Tilbury D. A. Rottenberg J.M. McDonald and D. E. Levy J. Labelled Compd. Radiopharm. 1981 18 183. l2 C. H. Collins K. E. Collins G. L. F. Lopez and J. F. Manfredi Proc. 3rd Symposium on Nuclear Chemistry Radiochemistry and Radiation Chemistry Mexico December 1980 p. 38. l3 N. Ramamoorthy P. J. Pao and I. A. Watson Radiochem. Radioanal. Lett. 1981,46 371. l4 S. Mirzadeh M. Kahn P. M. Grant and H. A. O’Brien jun. Radiochim. Acta 1981 28 47. l5 R. E. Lewis and L. L. Camin J. Labelled Compd. Radiopharm. 1981,18,164. l6 D. Comar C. Loc’h and B. Maziere Fr. P. 1980 2 455 334/A/; cf. INISAtomindex 1981,12,615 561. l7 J. Schuhmacher and W. Maier-Borst ‘International Symposium on Medical Radionuclide Imaging Heidelberg September 1980,’IAEA Vienna 1981 Vol. 1 p. 545. M. J. Welch Rep. COO-4318-3 1980; cf.INISAtomindex 1981 12 594 879. l9 P. J. Pao D. J. Silvester and S. L. Waters J. Radioanal. Chem. 1981 64 267. 2o T. Koyama T. Koyama Y. Kirokawa Y. Yoshizawa H. Noma T. Horiguchi Y. Kiso H. Hasai and H. Takemi Eur. J. Nucl. Med. 1980 5 481. 21 M. A. Guillaume in ‘Clinical and Experimental Applications of Krypton 81m’ ed. J. P. Lavender Br. Inst. Radiology London 1978 Ch. 2. 22 G. V. S. Rayudu B. W Fordham A. Friedman and J. Gindler J. Labelled Compd. Radiopharm. 1981 18,65. 23 J. C. Clark P. L. Horlock and I. A. Watson in ref. 21 Ch. 1. 24 R. Mune S. El-Bayoumy K. Mosaad and E. Hallaba Arab Republic of Egypt Atomic Energy Establishment Rep. 235 1980; cf. INIS Atomindex 1981 12,621 350. Radiochemistry 315 but the search for a suitable support material for this isotope continues.Aluminaz5 can be used but multiple layers of controlled and decreasing pH are required to give efficient el~tion;'~*~~ zirconia is also suitable.28 Other approaches have used solvent extraction29 and ~ublimation.~~ can be prepared by a-particle bom- "Ru bardment of molybdenum3' and extracted from the target by ion-exchange chr~matography.~~ Rhodium isotopes were extracted from irradiated ruthenium by solvent extraction after the ruthenium had been isolated as a nitrosyl complex33 and lo3Pd was extracted from a rhodium target using a-furildioxime in chlor~form.~~ 115mInis the decay product of "'Cd and can be separated either by ion exchange35 or ele~trolytically.~~ Ion exchange has also been used to separate 125mTe from its parent 125Sb37 although direct chemical procedures (via chlorides or oxides) are equally effe~tive.~' lZ3Te can be produced by high neutron flux bombardment of 122 Te and is useful as a calibrant for lZ3I dose determination^.^^ The production and purification of 133Xe has been re~iewed.~' Carrier-free 167Tm can be extracted chromatographically from holmium targets which have been bombarded with a-particle^.^^ Similarly the 168-isotope can be extracted from irradiated 168Er.42 The short half-life of 195mA~ (30.5 s) makes it an attractive isotope from medical applications (e.g.angiography). It is formed by the decay of 195mHg 40.5 h) which is prepared by proton (33 MeV) bombardment of gold. The mercury isotope can be fabricated into a generator from which 195mA~ can be eluted with potassium cyanide.43 Proton bombardment of thallium gives rise to *OIPbwhich if separated from the target can be used as a source of 201T1,44 the result of '"Pb decay.45 High-energy proton (660 MeV) bombardment of mercury on the other hand gives rise to a mixture of thallium isotopes 200 201 and 202.46Optimum conditions have been established for the solvent extraction of 225A~ from 225Ra so that the " S.T. Imoto M.Sc. Thesis Instituto de Pesquisas Energeticas e Nucleares Sao Paulo Brazil 1980; cf. ZNZSAtomindex 1981 12 621 351. 26 N. A. Morcos G. A. Bruno T. A. Haney and E. R. Squibb and Sons Can. P. 1980 1091 039/A/. 27 N. A. Morcos G. A. Bruno T. A. Haney and E. R. Squibb and Sons UK P.1981 1582 708/A/. J. Mengatti M.Sc. Thesis Instituto de Pesquisas Energeticas e Nucleares Sao Paulo Brazil 1980; cf. ZNZSAtomindex 1981 12 621 352. 29 0.G. Carvaiho M.Sc. Thesis. Instituto de Energia Atomica Sao Paulo Brazil 1979;cf. ZNZS Atomindex 1981,12 573 020. 30 V. Machan Zsotopenpraxis 1981,17,364. 31 S.Music M. Gessner R. Hoefer and H. Bergmann '14th Fut. Symposium on Radioactive Isotopes in Clinical Medicine and Research Bad Gasten 1980',Egermann Vienna Austria 1980,Vol. 1,p.165. 32 P.J. Pao J. L. Zhou D. J. Silvester and S. L. Waters Radiochem. Radioanal. Lett. 1981 46 21. 33 F.J. Hasbroek F. W. E. Strelow and T. N. Van der Walt S.Afr. J. Chem. 1981,34 50. 34 P. Tarapcik and V. Mikulaj Radiochem. Radioanal. Lett. 1981 48 15. 35 G.J. Ehrhardt W. Volkert and W. F. Goeckeler J. Labelled Compd. Radiopharm. 1981 18,63. 36 V. I. Kershulis in 'Investigation Technique of Radioactive Transformations in Chemical Compounds ed. E. B. Makaryunas Akad. Nauk Litovskoj SSR Vilnus 1979,p. 55; cf. ZNZS Atomindex 1981 12,591 076. 37 Y. Maruyama and Y. Magaoka Radiochem. Radioanal. Lett. 1980,44,249. 38 A. K. Dragunas and Eh. K. Makaryunene in ref. 36,p. 50;cf. ZNZS Atomindex 1981 12 591 007. 39 C. A. Riggs M. A. Kay and D. E. Troutner J. Radioanal. Chem. 1981,62 285. 40 M.Barrachina and M. Ropero Junta de Energia Nuclear Rept. 471,Madrid Spain 1980. 41 V. I. Levin L. N. Tronova P. P.Dmitriev G. I. Savel'ev and Z. M. Potapove Radiokhimiya 1980 22,428. 42 N. A. Lebedev Mo Khen Khan and V. A. Khalkin Radiokhimiya 1980,22,239.43 R. Bette G. H. Coleman J. G. Cuninghame and H. E. Sims Nucl. Med. Commun. 1981 2 75. 44 S.Bajo and A. Wyttenbach J. Radioanal. Chem. 1980,60 173. 45 L. N. Makagohova B. Z. Iofa and Yu.G. Sevost'yanov Radiokhimiya 1980,22,616. 46 A. F. Novgorodov A. Kolachkovski and Nguen Kong Chang Joint Inst. for Nuclear Research Dubna Rep. 6-80-308, Moscow USSR 1980;cf. ZNZSAtomindex 1981 12 604 247. 316 D. S. Urch pure actinium isotope can be used as source of 221Fr.47232U can be produced by high neutron flux irradiations of 230Th and 231Pa.48 3 Separation Techniques for Radioelements and Isotopes Isotopic Enrichment.-Tritium can be enriched during the electrolysis of water (as 3HHO)49or by thermal diffusion5’ and separated as 3HH or 3H2 from other isotopic configurations of dihydrogen by gas chromatography over 4 8 molecular sieves at 63 K.” On the other hand 3HH0 in water can be removed by 3H/’H exchange with surface hydroxyl-group~.~~ The search for economic methods for the separation of uranium isotopes continues concentrating on various ion-exchange tech-nique~~~-” or laser-induced dissociations of specific isotopic molecules (uranyl hexafluoro-acetylacetonate-tetrahydrofuran).56 Fission Products.-Various techniques have been described recently for the removal of specific fission products from spent fuel elements or liquid radioactive wastes.Thus ruthenium can be removed by complexing with thi~urea,~’ zirconium and niobium by acid elution from silica-gel and these elements together with technetium bromine and iodine by multistage solvent e~traction.~~ Solvent extrac- tion together with cobalt dicarbolides has also been proposed for the extraction of caesium and strontium,60 whereas chromatography using dihexyldiethylcarbamyl- methylenephosphonate on Vydac-C resin can be used61 to isolate the rare earths.A pyridine-containing polymer has been proposed as an ion-exchange material for recovering uranium.62 A very different approach to the separation of radioactive elements including fission products is the gas-jet technique in which potassium chloride clusters are used to transport active nuclides from the reactor zone to the front of a thermo- chromatographic column in a stream of nitrogen. The active elements are there volatilized (e.g.as chlorides) and so separated on the column.63 This method can 47 A. V. R. Reddy C. R. Venkatasubramani Y. S. Sayi S. S. Rattan V. S. Mallapurkar and R. J. Singh Radiochem. Radioanal. Lett. 1981 47 45. 48 R. G. Dominguez J. L. Gutierrez and G. M. Ropero Energ. Nucl. (Madrid) 1981 25 14. 49 T. Florkowski Low-Level Tritium Measurement IAEA-TECDOC-246 Vienna Austria 1981 p.133. so W. Roether and W. Weiss in ref. 49 p.165. 51 W. Roether in ref. 49 p.169. s2 M. Nakashima E. Tachikawa M. Saeki and Y. Aratono J. Inorg. Nucl. Chem. 1981,43 369. 53 J. Kahovec Chem. Listy. 1980 74 398. 54 T. Miyake M. Seko K. Inada K. Ochi and T. Sakamoto Aust. P. 1980 506772/B/; cf. INIS Atomindex 1981 12 573 024. 55 R. Nakane Oyo Butsuri 1980,49,754.56 D. M. Cox R. B. Hall J. A. Horsley G. M. Kramer P. Rabinowitz and A. Kaldor Science 1979 205 390. s7 B. Floh and A. Abrao Instituto Pesqui. Energ. Nucl. Sao Paulo 1980 No. 14. 58 E. R. Clark K. A. Al-Zubaidi and Al-Shahristani J. Radioanal. Chem. 1980,60 149. 59 K. Broden G. Skarnemark T. Bjoernstad D. Eriksen I. Haldorsen N. Kaffrell E. Stender and N. Trautmann J. Inorg. Nucl. Chem. 1981 43,765. P. Selucky I. Raid and M. Kyrs Ustav Jad. Vyzk. Cesk. Akad. Ved. Rep. 1979 50069; cf. INIS Atomindex 1981,12 575 087. 61 J. D. Baker R. J. Gehrke R. C. Greenwood and D. H. Meikrantz Radiochim. Acta 1981 28 51. 62 S. Yasuda T. Niwa and T; Kurohara Aust. P. 1980 506 825/B/; cf. INZS Atomindex 1981 12 606 900. 63 U. Hickmann N. Greulich N.Trautmann H. Gaeggler H. Gaeggler-Kock B. Eichler and G. Hermann Nucl. Instrum. Methods 1980,174 507. Radiochemistry 3 17 equally well be used for cyclotron-produced species64 and has the great advantage of being fast and easily adapted to batch work. Actinides (and Lanthanides).-Tracer amounts of uranium neptunium and plutonium can be extracted into organic solution by means of NN'tetrabutylurea and similar but uranium can be separated from plutonium in nitric acid solutions by the addition of lactic acid66 which inhibits the extraction of plutonium(1v) into tributylphosphate. In general B-diketones in the presence of sulphoxides have been found to be effective complexing agents for tetravalent thorium neptunium and plutonium permitting these elements to be extracted into organophosphorus The behaviour of plutonium(1v) in solutions of trio~tylamine~~*~~ in phosphoric acid and methyltrioctylammonium nitrate71 has been extensively studied to determine the nature of the plutonium complexes that are formed.1,2-Diaminocyclohexanetetraceticacid would appear to be suitable reagent for separating plutonium from a mixture of the lighter actinide Americium can be successfully separated from curium and fission-lanthanides by oxidation to the pentavalent state followed by ion-exchange ~hromatography.'~ Separations involving Am'" are however more complex. Trivalent americium can be extracted with europium from alkaline solutions using alkylpyro~atechols~~ or from nitric acid solution using sulphoxides with salting-out reagents.75 Americium and other trivalent elements can be extracted into tetraphenyl methylene diphos- phine dioxide from phosphoric acid and in an attempt to understand the distribution behaviour of Am"' and Eu'",thermodynamic studies have been made.77778 The optimum conditions for the separation of americium from curium using ion-exchange resins have been e~tablished.~~ The behaviour of americium curium berkelium californium and europium in systems of tributylphosphate- trioctylamine-lithium chloride-hydrochloric acid have been studied and optimum conditions for the extraction of californium" or the separation of Cm*" from Bk'" established.81 Solvent-extraction methods have also been studied to separate this 64 Z.Kovacs Proc. 2nd Hungarian Symposium on Radiochemistry Debrecen 1980 p. 122. 65 G. M. Chumakova V. V. Yakshin E. A. Filippov V. A. Belov I. A. Volodin G. G. Arkhipova and B. N. Laskorin Radiokhimiya 1980 22 213. 66 Sh. Nemoto H. Kobayshi and N. Tsunoda Report of Power Reactor and Nuclear Fuel Development Corp. Tokyo Japan 1979 No. 831-79-02. 67 M. A. Sajun V. V. Ramakrishna and S. K. Patil J. Radioanal. Chem. 1981,63 57. 68 S. K. Patil V. V. Ramakrishna and B. Haraprakas J. Inorg. Nucl. Chem. 1981 43 1377. 69 I. Yu L. P. Malysheva A. S. Krivokhatskij G. P. Savoskina and E. A. Smirnova Radiokhimiya 1980 22 363. 70 I. Yu L. P. Malysheva A. S. Krivokhatskij G. P. Savoskina and E. A. Smirnova Radiokhimiya 1980 22 369. 71 N. I. Gusev and E.I. Balashova Radiokhimiya 1980 22 207. 72 T. P. Makarova A. V. Stepanov A. M. Fridkin and K. S. Ivanova Radiokhimiya 1980,22 463. 73 F. H. El-Sweify Diss. Inst. Fur Radichemie K.F.Z. Karlsruhe Germany 1980. 74 B. F. Myasoedov Z. K. Karalova V. S. Kuznetsova and L. M. Rodionova Radiokhimiya 1980 22 347. 75 J. P. Shukla M. S. Nagar and M. S. Subramanian J. Radioanal. Chem. 1981,62,61. 76 M. N. Litvina M. S. Milyukova and B. F. Myasoedov Radiokhimiya 1980 22 374. 77 D. G. Kalina G. W. Mason and E. P. Horwitz J. Inorg. Nucl. Chem. 1981 43 579. 78 G.Yu. Lysenko and V. S. Shmidt Radiokhimiya 1980 22 509. 79 C. Ginisty Report Centre d'Etudes Nucleaires Fontenay-les-Roses 92 France 1981 CEA-R-5 107. N. I. Gusev T. I. Bukina I. E. Veleshko and B. F. Myasoedov Radiokhimiya 1980,22 203.l31 M. S. Milyukova D. A. Malikov and B. F. Myasoedov Radiokhimiya 1980 22 352. 318 D. S. Urch series of elements.82 Californium it has been found can be separated from europium and from berkelium on KRS-8 resin.83 4 Labelled Compounds The purpose of this Section is to give an overview of recent progress in the preparation of labelled molecules to indicate the range of compounds and isotopes studied and the variety of techniques used. Hydrogen.-Most of the methods for introducing tritium (or deuterium) into a molecule involve exchange reactions usually in the presence of a catalyst. Hydroxide is one of the simplest for use in aqueous solutions either alone [e.g. to label 2-chloro-l-(difluoromethoxy)-l,1,2-trifluoroethene,84 phosphamides,86 m~cidin,~~ ketone^^^*^^] or in the presence of platinium (14-proxylstearic acid") or Raney nickel (salicylic acid").Zeolites have been to be potent catalysts in promoting exchange between tritiated water and aromatic hydrogen atoms. Similar exchange can be catalysed by noble metals especially platinium (4-hydroxy- 3-methoxymandelic acid,93 substituted pyrimidine^^^) and palladium (de~ane~~). Acid-catalysed exchange was used to label aflat~xins~~ but the additional presence of tetrachloroplatinate was required for the labelling of tyro~ine.~~ Catalytic reduc- tion using labelled hydrogen gas98 can also be used to introduce tritium and deuterium into specific sites in a molecule (e.g. in ~-glutamine,~~ 3-dehydrohexes-trol"').Pertritio- and tritritio-methane have been made in this way from carbon dioxide."' Another extremely powerful method for introducing a label-atom into a specific site in a molecule is through catalytic dehalogenation in which 3H or 2H is induced to replace a halogen atom.lo2 The technique is equally effective in the gas phase,lo3 using tritium gas and palladium on charcoal (melat~nin,~'~ [12- 82 P. K. Khopkar and J. N. Mathur J. Radioanal. Chem. 1980,60 131. 83 A. A. Elesin and V. M. Nikolaev Nauchno-Issledovatel'skij Inst. Atomnykh Reaktorov Rep. Dimitrovgrad USSR 1980 22(430). 84 T. R. Burke jun. J. Labelled Compd. Radiopharm. 1981,18,663. 85 K. Hiraoka T. Miyamoto S. Baba and T. Furuta J. Labelled Compd. Radiopharm. 1981 18 613.86 M. Jarman and G. N. Taylor J. Labelled Compd. Radiopharm. 1981,18,463. 87 F. Nerud P. Sedmera and.K. Veres Radiochem. Radioanal. Lett. 1981 46 303. D. R. Burfield and C. M. Savariar Eur. Polym. J. 1980,16 1003. 89 A. G. Pinkus A. Sabesan and R. Subramanyam J. Labelled Compd. Radiopharm. 1981,18,459. 90 J. F. W. Keana and S. E. Boyd J. Labelled Compd. Radiopharm. 1981,18,403. 91 D. R. Hawkins and R. W. Pryor J. Labelled Compd. Radiopharm. 1981,18,593. 92 M. A. Long,J. L. Garnett and P. G. Williams J. Am. Chem. SOC., 1981 103 1571. 93 K. F. Faull P. J. Anderson and J. D. Barchas J. Labelled Compd. Radiopharm. 1981 18 1075. 94 S. F. Zakrzewski J. Labelled Compd. Radiopharm. 1981 18 683. 9s P. Bouchet R. Lazare and J. Rouviere J. Labelled Compd. Radiopharm.1981 18 1071. 96 K. Veres Radiochem. Radioanal. Lett. 1980 45 413. 97 M. Kanska and S. Drabarek Radiochem. Radioanal. Lett. 1980,44 207. 98 K.Veres V. Siglerova and P. Dufek Radiochem. Radioanal. Lett. 1981,46 307. 99 M. Stogniew L. A. Geelhaar and P. S. Callery J. Labelled Compd. Radiopharm. 1981 18 897. loo R. Goswami M. R. Kilbourn and J. A. Katzenellenbogen J. Labelled Compd. Radiopharm. 1981 18,407. lo' E. N. Sinotova M. V. Korsakov and V. A. Shishkunov Radiokhimiya. 1980 22 466. lo* B. Verny and J. Hanus J. Labelled Compd. Radiopharm. 1981,18,947. lo3 J. A. Katzenellenbogen T. Tatee and D. W. Robertson J. Labelled Compd. Radiopharm. 1981 18 865. Y. Y. Lui and M. Minich J. Labelled Compd. Radiopharm. 1981 18,791. Radioc hemistry 3 19 3H]camptothecin,105 and [3,5-3H]Tyr2-a-melanotropin'06) and in the liquid (alka- line) phase again using palladium as a catalyst (purinelo7 and pyrimidine'08 nucleo- sides).Boro- and alumino-hydride anions (suitably labelled) are very effective in producing labelled reduced corn pound^'^^^^ lo (e.g.prostaglandins,"' bile acids and alcohols' 12) Dehalogenation of 4,4'-dibr0mo-[~H~]biphenyl with lithium aluminium hydride enabled ['HI atoms to be located in an otherwise wholly deuteriated Tritiated dib~rane"~ can be prepared by adding phosphoric acid to KB3H4. The very simplest method for making tritium-labelled compounds is of course exposure to tritium gas (Wilzbach) but this technique has the grave disadvan- tage of producing a very wide range of tritiated molecules as impurities.A recent patent advocates bombarding tritium gas (not the sample) with an electron beam to produce excited tritium molecules rather than relying upon the natural p emission of triti~m."~ The effect of Wilzbach- ,as opposed to catalytic-exchange- ,labelling can be studied using tritium n.m.r.l16 Other types of compounds that have been labelled with hydrogen isotopes include derivatives of phosph~choline,"~ thymidine piperazine,"' thioxanthenes,'*' phencylidines,12' phenothiazines,'22 imida~olines,'~~ and carbohydrate^."^ Thin-layer chromatography has been found particularly useful in the purification of labelled Palmitic and stearic acids,126 dibromochloropropane lZ7 and a series of cycloheptanolslZ8 have also been labelled in specific positions.The stability during storage of labelled compounds is always a problem optimum conditions have been described for uridine phosphate. ''' lo' P. E. Ronman M. C. Wani and M. E. Wall J. Labelled Compd. Radiopharm. 1981 18 319. D. I. Buckley and J. Ramachandran Znt. J. Pept. Protein Res. 1981,17 514. lo7 N.F.Myasoedov and G. R. Sidorov Radiokhimiya 1980 22 574. N. F. Myasoedov and G. R. Sidorov Radiokhimiya 1980,22 579. lo9 R. K. Hallmark W. B. Manning and G. M. Muschik J. Labelled Compd. Radiopharm. 1981,18,331. 'lo N.Minami J. Labelled Compd. Radiopharm. 1981 18,823. L. A. Blair C. N. Hensby and J. MacDermot J. Labelled Compd. Radiopharm. 1981 18 361. '12 B. Dayal E. Baga G. S. Tint S. Shefer and G. Salen Steroids 1979 34 259.'13 A. M. Clark P. J. Davis and R. V. Smith J. Labelled Compd. Radiopharm. 1981,18,905. '14 Y.Murano G. Izawa and T. Shiokawa Radiochem. Radioanal. Lett. 1980,44,315. T. F. Moran J. C. Powers and M. 0.Lively UK P. 1980,2 044 772/A/; cf. ZNZS Atomindex 1981 12,615 563. P. G.Williams 10th Australian Inst. of Nuc. Sci. and Eng. Radiation Chem. Conf. Abstracts 1980 p. 22. '17 U. Lachmann and D. Murawski Z. Chem. 1980,20 373. 118 Z. Nejedly J. Ekl J. Filip J. Kolina I. Votruba and J. Skoda Jad. Energ. 1980 26 224. G.Zolyomi and Z. Budai J. Labelled Compd. Radiopharm. 1981,18,427. 120 0.Buchman M. Shimoni M. Blitzblau A. Cohen and Y. Hagag Zsr. A.E.C. Rep. 1980,No.1356 224. lZ1 0.Buchman M. Shimoni A. Cohen H. Cohen and Y. Hagag Zsr.A.E.C. Rep. 1980,No. 1356,225. ''' 0.Buchman M. Blitzblau A. Cohen Y. Hagag I. Pri-Bar and M. Shimoni Isr. A.E.C. Rep. 1980, No.1356 223. G.Kloster and J. Odenthal J. Labelled Compd. Radiopharm. 1981 18 287. 0.Buchman M. Shimoni M. Blitzblau A. Cohen and Y. Hagag Zsr. A.E.C. Rep. 1980,No.1356 224. l'' J. Roemer Mitteilungsbl. Chem. Ges. Dtsch. Demokr. Repub. Beih. 1979,24 107. lZ6 R.0.Adlof and E. A. Emken J. Labelled Compd. Radiopharm. 1981 18,419. 127 I. Azran I. Pri-Bar M. Shimoni and 0.Buchman Israe1A.E.C. Rep. 1980,No.1356,226. F. Turecek Collect. Czech. Chem. Commun. 1980,45 1820. 129 D. Brabec Radioisotopy 1980 21 177. 320 D. S. Urch Carbon.-The short-lived "C isotope [T~/~ = 20 mins] continues to excite interest and to stimulate the development of rapid synthesis of specific for radiopharmaceutical use.131 The compounds are used in metabolic studie~'~'-'~~ and in tumour location using tomography.137-'38 Systems are designed that intro- duce "C into small reactive molecules such as methyl i~dide,'~~-'~~ h ydrocy anic acid,' 39~144carbon dioxide 144-'47 formaldehyde 139~148acetone,'49 and even phos- gene,'" often utilizing hot-atom reactions. Clever chemistry then leads to "C labelled molecules such as et~rphine,'~~~~~~ small pep tide^,'^^ 1-aminocyclo-hexanecarboxylic moxestrol and 17-c~-methyloestradiol,'~~ iodoanti-pyrine,14* hexo- barbital,' 43~1' L-[ 3-''Cllactic acid ''* acetate,' 36~145 a range of ether^,'^' ~henethylamine,'~~ paraffin^,'^' and tol~ene.'~'A more leisurely approach can be adopted in the production of 14C-labelled materials e.g.anthra-cycline gly~osides,'~~ glucose and arabino~e,'~~ 3-['4C]methyl D-gluco~e,'~~ amino-acids and their derivative^,'^^-'^^ caff eic acid 160 pentachloronitrobenzene,'61 I3O G. Berger M. Maziere M. M. Godot J. Sastre C. Prenant and G. Comar J. Labelled Compd. Radiopharm. 1981 18 5. 131 M. Maziere G. Berger C. Prenant J. Sastre and D. Comar J. Labelled Compd. Radiopharm. 1981 18 258. 13' D. Comar G. Berger C. Crouzel J. M. Godot M. Mazier and G. Mestelan J. Labelled Compd. Radiopharm. 1981,18 3. 133 M. Maziere G. Berger J. M. Godot C. Prenant and D. Comar J. Labelled Compd. Radiopharm. 1981 18 15. 134 L. C. Washburn R. E. Ringenberg T. T. Sun and R. L.Hayes J. Labelled Compd. Radiopharm. 1981 18 13. 13' W. Vaalburg A. Feenstra T. Wiegman H. D. Beerling S. Reiffers A. Talma M. G. Woldring and H. Wynberg J. Labelled Compd. Radiopharm. 1981,18 100. 136 V. W. Pike M. N. Eakins R. M. Alian and A. P. Selwyn J. Labelled Compd. Radiopharm. 1981 18 249. 137 D. D. Dischino S. L. Wittmer M. E. Raichie and M. J. Welch J. Labelled Compd. Radiopharm. 1981 18 238. 13' M. Jay G. A. Digenis J. E. Chaney L. C. Washburn B. L. Byrd and R. L. Hayes J. Labelled Compd. Radiopharm. 1981,18 237. 139 B. Laangstroem Ph.D. Thesis Uppsala Univ. Sweden 1980 (Abstract No. 55). I4O B. Laangstroem S. Sjoeberg G. Bergson H. Lundqvist P. Maimbor C. G. Staelnacke and B. Larsson J. Labelled Compd. Radiopharm. 1981 18 17. 141 B.Laangstroem and S. Sjoeberg J. Labelled Compd. Radiopharm. 1981 18 671. 142 J. A. Campbell R. D. Finn R. E. Boothe B. Djermouni M. D. Ginsberg A. H. Lockwood A. J. Gilson and H. J. Ache J. Nucl. Med. 1981 22 538. 143 G. Kloster and C. Mueller-Platz J. Labelled Compd. Radiopharm. 1981 18 731. 144 J. S. Laughlin R. S. Benua and A. S. Gelbard Sloan-Kettering Inst. for Cancer Research Rep. COO-4268-7 (80),New York 1980. 14' V. W. Pike M. N. Easkins R. M. Allen and A. P. Selwyn J. Radioanal. Chem. 1981,64 291. R. Iwata and T. Ido Radioisotopes (Tokyo) 1981,30 28. 14' B. Laangstroem S. Sjoeberg and U. Ragnarsson J. Labelled Compd. Radiopharm. 1981 18,479. 14' M. Maziere J. M. Godot G. Bergei C. Prenant and D. Comar J. Radioanal. Chem. 1981,62 279. 149 G.Berger M. Maziere C. Prenant and D. Comar Int. J. Appl. Radiat. Isot. 1980 31 577. G. Westera and D. Roeda J. Labelled Compd. Radiopharm. 1981 18 11. G. Kloster and C. Mueller-Platz J. Labelled Compd. Radiopharm. 1981 18 242. G. Kloster and P. Laufer J. Labelled Compd. Radiopharm. 1981 18 205. G. P. Vicario S. Penco and F. Arcamone UK P. 1980 1 566 330/A/; cf.INIS Atomindex 1981 12,575 091. G. Kloster C. Mueller-Platz and P. Laufer J. Labelled Compd. Radiopharm. 1981,18 855. V. Bilik P. Biely and M. Matulova Chem. Zvesti 1979 33 782. S. S. Yuan and J. Foos J. Labelled Compd. Radiopharm. 1981 18 563. H. R. Tsou J. Labelled Compd. Radiopharm. 1981 18 921. 15' W. E. Adams E. W. Snook and T. J. Curphey J. Labelled Compd. Radiopharm. 1981,18,991. V. K.P. Unny S. Thyagarajan and K. V. Viswanathan Radiochem. Radioanal. Lett. 1981,47 367. B. Helbig and R. Kloecking Z. Chem. 1980 20 339. 161 H. H. Kaegi J. Labelled Compd. Radiopharm. 1981 18 445. Radiochemistry 321 substituted uraci1,16' and sulphonamide valeric etc. The preparation of many other even more exotic organic compounds of biomedical interest (drugs pesticides) has been reported during the past year but using con- ventional and well established procedures that do not call for comment here. It might be of interest however to record the preparation of some small labelled compounds that could be of use in larger syntheses diaz~methane,~~' [3-14C]prop-ionic acid,'66 b~tylmercaptans,'~~ p-hydroxybenz[ ''C]aldehyde,'68 p-hydroxy-ben~yl['~C]cyanide,'~~ 2,3-dihydroxy-[carboxy- 14C]benzoic acid,17' and ring-labelled benzene and t~luene.'~' Enzymes can often be used as catalysts in labelling biochemical molecules and have been used to produce cat echo la mine^,^^^ 2'-desoxyadenosine 5'-monopho~phate,l~~ glucose labelled in various and a diphospho-[ ''C]-~-gluc~~e derivative of uridine.17' There is continued interest in the preparation of 14C-labelled polychloro-compounds of alkanes,'76 ~yridine,'~~ biphenyl,'78 and diben~0furan.I~~ New labelling procedures are rare but the reported use of Wittig reagents bound to polymers may prove to be useful rather than just novel.I8O Nitrogen.-13N-labelled ammonia can be produced by the proton irradiation of water,'81"82 but the incorporation of this short-lived (T',~-10mins) isotope into compounds of medical interest presents problems.Enzymatic often provide the solution e.g. ~-['~N]amino-acids,'~~~~~' [13N]amphetamine has also been prepared."' Fluorine.-Many "F-labelled compounds are prepared from 18FF which is in turn made by the deuteron irradiation [20Ne(d a)18F]of neon containing a few percent difluorine as a carrier.Ig7 The efficiency of this process is very sensitive to traces A. Unverricht S. Diabate and H. R. Schuette Z. Chem. 1980 20 339. 163 A. J. Villani R. G. Pendleton and W. E. Bondinell J. Labelled Compd. Radiopharm. 1981 18 202. 164 R. Tschesche and W. Wirth J. Labelled Compd. Radiopharm. 1981,18,433. 165 S. Fittkau Pharmazie 1980 35 646. 166 E. Koltai and D.Banfi J. Labelled Compd. Radiopharm. 1981 18 809. 167 R. Kanski Nukleonika 1979 24 229. H. L. Holland and N. Sultana J. Labelled Compd. Radiopharm. 1981 18 1067. 169 J. W. Jaroszewski J. Szancer and M. G. Ettlinger J. Labelled Compd. Radiopharm. 1981 18 703. 170 M. G. Sundaram J. Labelled Compd. Radiopharm. 1981 18,489. 171 R. Russow and U. Kosakowsky Isotopenpraxis 1981 17 382. P. Gueguen and J.-L. Morgat J. Pharmacol. 1981 11 116. 173 0.I. Kozyreva E. V. Zueva and E. G. Titkova Radiokhimiya. 1980 22,446. 174 J. P. Longenecker and J. F. Williams J. Labelled Compd. Radiopharm. 1981 18 309. 175 V. Farkas P. Biely and J. Koelbl Czech. P. 1980 183 919/B/; cf. INIS Atomindex 1981 12 618 128. 176 A. Bergman I. Leonardsson and C. A. Wachtmeister Chemosphere 1981,10 857.177 L. H. McKendry J. Labelled Compd. Radiopharm. 1981 18,629. A. Bergman I. Bamford and C. A. Wachtmeister J. Labelled Compd. Radiopharm. 1981 18 1023. A. P. Geay W. J. McClellan and V. M. Dipinto J. Labelled Compd. Radiopharm. 1981 18 507. J. Chocholous Thesis (Dr. techn.) Tech. Univ. Vienna 1980; cf. ZNZSAtomindex 1981,12,609 626. T. Ido and R. Iwato J. Labelled Compd. Radiopharm. 1981 18 244. G. Slegers C. Vandecasteele and J. Sambre J. Radioanal. Chem. 1980 59 585. A. S. Gelbard J. Labelled Compd. Radiopharm. 1981 18 933. 184 J. S. Laughlin R. S. Benua and A. S. Gelbard Sloan-Kettering Inst. for Cancer Research Rep. COO-4268-7 (go) New York 1980. A. J. L. Cooper Anal. Biochem. 1981 111,42. R. D. Finn D. R. Christman and A.P. Wolf. J. Labelled Compd. Radiopharm. 1981 18 909. B. W. Wieland D. J. Schlyer T. J. Ruth and A. P. Wolf J. Labelled Compd. Radiopharm. 1981 18. 27. 322 D. S. Urch of contaminants (air carbon dioxide etc.).lS8 Other techniques have been tried based either on H'8F189 or on the reactivity of 18F atoms produced in pure neon:190 the fluoridation of L-dopamine by means of Xe "FF has been reported.'" Neutron irradiation of lithium hydroxide initiates a sequence of nuclear reactions [6Li(n 3H)4He:160(3H n)I8F] from which the labelled fluoride can be extracted into organic solution as a potassium-crown ether complex.192 The fluoride anion can then be used in nucleophilic substitution reactions to produce labelled molecules e.g. labelled fluoroalkanes from the corresponding iodo-compounds (Ag20 cataly~t).'~~ Various 18F compounds for radiopharmaceutical use have been prepared usually by exposure to labelled fluorine gas e.g.2 deoxy-2-[ '8F]difluoro- D-g"c~se,'~~''~~['8F]fluorospiroperido1,'96 5-[18F]fl~~r~~ridine,'97 7-['sF]fluoropalmitic acid,19' 4-[18F]fluoroantipyrine,199 etc. and techniques for the introduction of fluorine into aromatic rings have been investigated.200*20' Phosphorus.-Adenosine diphosphate reacts with labelled triethylammonium phosphate to produce adenosine S,y-[32P]triphosphate.202 Sulphur.-~-[~~S]cysteinesulphinic acid can be made from 35S-labelled cystine via the thios~lphonate.~~~ Chlorine.-When labelled dichlorine reacts with 1,2-dichloroethylene labelled 1,1,2,2-tetrachloroethaneis formed.204 Chromium-Cobalt.-The labelling of complex organic molecules including pro- teins with 51Cr205 and 57C0 (sulphitocobalamin,206 Co-bleomycin A2 complex2o7) has been reported.Gallium.-Complexes of 68Ga have been prepared which can be used to measure blood volume (Ga-tran~ferrin~~~-~~~) or kidney and liver function (Ga-l'' G. T.Bida R. L. Ehrenkaufer A. P. Wolf J. s. Fowler R. R. MacGregor and T. J. Ruth J. Nucl. Med. 1980 21 758. lS9 J. R. Dahl R. Lee B. Schrnall and R. E. Bigler J. Labelled Compd. Radiopharm. 1981 18 34. I9O J. S. Laughlin R. S. Benua and A. S. Gelbard Sloan-Kettering Inst. for Cancer Research Rep. COO-4268-7 (80) New York 1980. 19' G. Firnau R. Chirakal S. Sood and E. S. Garnett J. Labelled Compd.Radiopharm. 1981 18 7. lg2 B. E.Gnade G. P. Schwaiger C. L. Liotta and R. W. Fink In[.J. Appl. Radiat. Isor. 1981 32 91. 193 S. J. Gatley R. D. Hichwa W. J. Shaughnessy and R. J. Nickles Int. J. Appl. Radiat. hot. 1981 32 211. 194 A. J. Palmer J. Labelled Compd. Radiopharm. 1981 18 264. 195 W. J. Shaughnessy S. J. Gatley R. D. Hichwa I. M. Lieberman and R. J. Nickles Znr. J. Appl. Radiat. Zsot. 1981 32 23. 196 M. Maeda T. J. Tewson and M. J. Welch J. Labelled Compd. Radiopharm. 1981 18 102. 197 C. Y. Shiue J. S. Fowler R. R. McGregor and A. P. Wolf Proc. 2nd Int. Syrnp. Radiopharmaceuticals NY School of Nucl. Medicine New York 1979 p. 60. lg8 M.S.Berridge T. J. Tewson and M. J. Welch J. Labelled Compd. Radiopharm. 1981 18 240. C. Y.Shiue and A. P. Wolf J. Labelled Compd. Radiopharm. 1981 18 1059. 2oo T. J. Tewson M. Maeda and M. J. Welch J. Labelled Compd. Radiopharm. 1981 18 21. 201 M. N. Rosenfeld and D. A. Widdowson J. Labelled Compd. Radiopharm. 1981 18 20. 202 W. Koziolkiewicz J. Pankowski and A. Janecka Prep. Biochem. 1978 8 471. 203 R. M. Spears and D. L. Martin J. Labelled Compd. Radiopharm. 1981 18 1055. 204 G. E. Srnirnova V. A. Shalygin Ya.D. Zel'venskij and N. N. Prosyanov Radiokhimiya 1980,22,469. *05 H. Kuni and U. W. Schmidt Nucl. Med. 1980 19 221. 206 J. A. Begley C. Horch and C. A. Hall Prep. Biochem. 1978 8 411. 207 C. M.Vos and G. Westera J. Labelled Compd. Radiopharm. 1981 18 173. 208 B. Maziere C. Loc'h and D. Cornar J. Labelled Compd. Radiopharm. 1981 18 165. *09 M.Raiszadeh J. F. Harwig and W. Wolf J. Labelled Compd. Radiopharm. 1981 18 167. 19' Radiochemistry 323 tricatecholamide210). The complexing potential of gallium is also used to label albumin microspheres that have edta chelating groups on their surface.211 Citrate complexes (using 67Ga) also appear to have radiopharmaceutical Arsenic.-The potential of labelled arsenic compounds (71A~ 76As) in nuclear 74A~ medicine has been considered.213 Selenium.-It is reported that Na275Se03 reacts with cysteine cystine and gluta- thione to give labelled selenium analogues.214 Selenium-labelled compounds (e.g. 75Se-bile ~-[~~Se]selenomefhionine~~~) have also been prepared for various medical purposes e.g. brain imaging217 and studies of the liver and the gut.218 Bromine.-Most recent interest in bromine-labelled molecules has concentrated on the neutron-deficient isotopes and especially 77Br (7112 = 56 h).Rapid methods for producing p-[77Br]bromospiroperido1,219 5-[77Br]bromo-2'-deoxyuridine,220 and 2-(4[77Br]bromo-2,5-dimethoxyphenyl)isopropylamine221 have been reported. Labelling of (e.g. 16a-[77Br]bromo-17~-oestradiol)224 and pro-teins225.226 with radioactive bromine has also been carried out. Aromatic systems can sometimes be directly Technetium.-99mTc is now one of the most widely used isotopes in nuclear medicine. The starting point for chemical syntheses to produce labelled or tagged molecules is usually sodium pertechnate(vI1). Conventionally this compound is reduced using stannous tin (e.g.SnC12) but it is found that the optimum level of Sn2' is difficult to determine229 and that tin is often incorporated into the final produ~t,~~',~~~ (e.g.to tagged To overcome this problem the follow- 'lo s. M. Moerlein M. J. Welch and K. N. Raymond J. Nucl. Med. 1981 22 710. ''I D. J. Hnatowich and P. Schelgel J. Nucl. Med. 1981 22 623. ''' M. Raiszedeh. J. Harwig and W. Wolf J. Labelled Compd. Radiopharm. 1981 18 217. 'I3 C. Birattari M. Bonardi and A. Salomone J. Labelled Compd. Radiopharm. 1981 18 252. 214 M. Czauderna and K. Samochocka J. Labelled Compd. Radiopharm. 1981,18,829. 'I5 G. S. Boyd M. V. Merrick R. Monks and I. L. Thomas J. Nucl. Med. 1981 22,720. 'I6 M. A. Guillaume and L. Christiaens J. Labelled Compd. Radiopharm. 1981 18,177.'17 H. F. Kung K. Tramposch and M. Blau J. Labelled Compd. Radiopharm. 1981,18 107. 218 P. J. Fourie F. J. Haasbroek J. A. van Wyk and W. H. van Zyl J. Labelled Compd. Radiopharm. 1981 18 178. 219 A. M. Friedman C. C. Huang H. Kulmala R. Dinerstein R. So M. Simonovic and H. Y. Meltzer J. Labelled Compd. Radiopharm. 1981 18 104. '"D. J. Malcolme-Lawes and S. Massey J. Radioanal. Chem. 1981,64 281. H. H. Coenen J. Labelled Compd. Radiopharm. 1981 18 739. 222 D. S. Wilbur and H. A. O'Brien J. Labelled Compd. Radiopharm. 1981 18,47. 223 J. K. Mazaitis B. E. Francis W. E. Eckelman R. E. Gibson R. C. Reba J. W. Barnes G. E. Bentley P. M. Grant and H. A. O'Brien jun. J. Labelled Compd. Radiopharm. 1981,18 1033. 224 J. A. Katzenellenbogen S.G. Senderoff M. J. Welch and K. D. McElvany J. Labelled Compd. Radiopharm. 1981 18,81. 225 K. D. McElvany Ph.D. Thesis Washington Univ. Seattle USA 1980; cf. INIS Atomindex 1981 12,618 123. 226 K. D. McElvany M. J. Welch and J. W. Barnes Int. J. Appl. Radiat. Isot. 1980 31 679. 227 H. H. Coenen A. S. El-Wetery and G. Stoecklin J. Labelled Compd. Radiopharm. 1981 18 114. 228 D. J. Malcolme-Lawes and S. Massey J. Labelled Compd. Radiopharm. 1981 18 116. 229 J. R. Kim 0.D. Awh J. S. Koo and K. B. Park Korean J. Nucl. Med. 1981 15 13. 230 B. Zmbova D. Zivanov-Stakic and I. Tadzer Inr. J. Appl. Radiar. Zsot. 1981 32,459. 231 J.-C.Saccavini Thesis Univ. Rennes-I 35 France cf. INISAtomindex 1981 12 612 761. 232 V. I. Stanko N. N. Ovsyannikov N. P. Zuykova A.F. Gouskov and N. D. Kovalchouk Isotopenpraxis 1978 14 6. 233 M. W. Billinghurst S. Rempel and B. A. Westendorg J. Labelled Compd. Radiopharm. 1981,18,651. 324 D. S. Urch ing solutions have been tried the use of insoluble stannous s~lphide,~~~ stannous ion adsorbed on a cation-exchange resin,235 the use of chromium(I1) electrolytic and not using any reducing agent at all! In this latter case dimercaptosuccinic acid was oxidized and technetium reduced to Tc'" giving rise to a complex of the initial The actual oxidation state of technetium in many of the radiopharmaceutical complexes is often not known but in both 1,4,8,1l-tetra-azacyclotetradecane (cyclan239*240) complex and technetium gluc~heptonate~~~~~~~ it was found to be five.Many 99mTc complexes have been prepared with sulphur- containing ligands e.g. N,N-ethyldithiocarbamate ,243 2-mercap tocarboxylic and amino-thi~ls.~~~ 99m Tc has also been incorporated into various nitrogen-substituted iminodiacetic to give compounds that can be used in medical diagnostic scanning. Complexes have also been made with hydroxy- methylene dipho~phate'~~ and similar which can be used for skeletal imaging. Albumin,256 tran~ferrin,~~~ and other can all be tagged with 99mTc. or R~thenium.-~~Ruand lo3Ru as the hexaquo(~~)~'~the chloropenta-ammine(III)260 cation can be used as a starting point for the preparation of various radiopharmaceuticals. Ruthenocene-carbaldehyde can be complexed with amino- sugars to give reduced labelled compounds.261 234 P.H. Cox in ref. 17 p. 453. 235 K. Horiuchi A. Yokoyama Y. Fujibyashi H. Tanaka T. Odori H. Saji R. Morita and K. Torizuka Int. J. Appl. Radiat. Isot. 1981 32,41. 236 M. Kalincak V. Machan and S. Vilcek Int. J. Appl. Radial. Isot. 1981 32,493. 237 K. Kothari D. V. S. Narasimhan N. Ramamoorthy and R. S. Mani J. Radioanal. Chem. 1980 59 229. 238 J. Galvez R. G. Domenech and L. Moreno In?.J. Appl. Radiat. Isot. 1980,31,715. 239 J. Simon D. E. Troutner W. A. Volkert and R. A. Holmes Radiochem. Radioanal. Lett. 1981 47 111. 240 J. Simon S. Zuckman D. E. Troutner W. A. Volkert and R. A. Holmes J. Labelled Compd. Radiopharm. 1981 18 151. 241 W. de Kieviet J. Nucl. Med. 1981 22 703. 242 W. de Kieviet J. Labelled Compd.Radiopharm. 1981 18 136. 243 P. M. Pojer and J. Baldas Australian Radiation Lab. Rep. TR-025 Melbourne Australia 1980. 244 E. Livni M. A. Davis and V. D. Warner J. Nucl. Med. 1981 22 535. 245 A. R. Fritzberg and D. Eshima J. Labelled Compd. Radiopharm. 1981 18 52. 246 H. D. Burns R. F. Dannals T. E. Dannals A. V. Kramer and L. G. Marzilli J. Labelled Compd. Radiopharm. 1981 18 54. 247 T. Sadeh and M. Juszynsky Isr. A.E.C. Rep. 1980 No. 1A-1356,264. 248 R. W. Nicholson K. J. Heman R. A. Shields and H. J. Testa Eur. J. Nucl. Med. 1980 5 313. 249 J. Weininger J. Trumper and S. Pelah Isr. A.E.C. Rep. 1980 No. 1A-1356 262. 250 A. D. Nunn J. Labelled Compd. Radiopharm. 1981,18 155. 25 1 J. Lang J. Lazar and Z. Nemessanyi Proc.3rd European Congress of Nuclear Medicine Karlory Vary Czechoslovakia 1979 p. 37. 252 J. A. Bevan A. J. Tofe J. J. Benedict M. D. Francis and B. L. Barnett J. Nucl. Med. 1980 21 961. 253 J. A. G. M. van den Brand H. A. Das B. G. Dekker and C. L. de Ligny J. Labelled Compd. Radiopharm. 1981 18 144. 254 N. H. Agha A. M. Al-Hilli and H. A. Hassen J. Labelled Compd. Radiopharm. 1981,18 138. 255 R. W. Heineman and E. A. Deutsch Cincinnati Univ. Department of Environ. Rep. EV/10380-1 1980; cf. INISAtomindex 1981 12 594 882. 256 P. Komarek M. Chalabala and B. Vavejn Cesk. Farm. 1980 29 81. 257 C. H. Paik F. Vieras W. C. Eckelman and R. C. Reba J. Radioanal. Chem. 1980,60 281. 258 K. A. Krohn D. R. Vera and S. M. Steffen J. Labelled Compd.Radiopharm. 1981,18,91. 259 V. Subramanyam K. Linder S. Sivakoff M. P. Liteplo and L. L. Camin J. Labelled Compd. Radiopharm. 1981 18 40. 260 V. Subramanyam F. P. Pratt T. Mysliwy M. P. Liteplo L. L. Camin F. A. Liberatore C. Bilafer S. Nigam and S. Sivakoff J. Labelled Compd. Radiopharm. 1981 18 161. 26 1 M. Schneider and M. Wenzel J. Labelled Compd. Radiopharm. 1981,18 293. Radiochem istry 325 Indium.-"'In can be incorporated into a porphyrin ring262 and complexed by tricatecholamide2" to give compounds sufficiently water soluble to be used medically. 1'3mIn-labelled albumin can be prepared from suitable generator 256 the problem of silicon contamination has been Tellurium.-The preparation of '23mTe labelled long-chain fatty acids such as 17-tellura-9-octadecenoic acid which can be used for myocardial and brain imaging has been Iodine.-Various isotopes are available for the preparation of labelled iodine com- pounds but the radioactive properties of the lighter i~otopes,~~~I and e~pecially'~~1 make these the most popular for medical and biochemical use.Numerous different types of molecule have been labelled recently as summarized below 17-['231]iodoheptadecanoic ['251]iodophenylimine-oxindole,267(2)-1,2-bis(4'-hydroxyphenyl)-1-[lZ51or '"I or '311]iodoprop-l -ene,268 5-(p-[1231]iodo-pheny1)valeric iododerivatives of 4-oxyphenylpyruvic 2'-arachidonic tri-i~dothyronine,~~~ 2-de~xyuridine,~~' 6-iodocholester01,~~~ i~dohistamine~~~ iodo-derivatives of 0estradio1,~~~ and and proge~terone,~~' tamo~ifen,~~~'~~~ and prostaglandins.282 Many papers have also been insulins,280.281 published describing the preparation of labelled iodo-derivatives of and hippuric In the work-up and purification stages chromatography on Sephadex LH-20 dextran gel has often proved Specific strategies that 262 K.M. Lee and A. G. Marshall J. Labelled Compd. Radiopharm. 1981,18 353. 263 J. Cifka A. Rokos and I. Cifkova in ref. 251 p. 14. 264 S. L. Mills G. P. Basmadjian G. R. Parker and R. D. Ice J. Labelled Compd. Radiopharm. 1981 18 721. 265 M. Argentini M. Weidmann M. Zahner K. Zimmermann and P. A. Schubiger Radiochem. Radioanal. Lett. 1980,44 269. 266 H. J. Machulla K. Dutschka and C. Astfalk Radiochem. Radioanal. Lett.1981 47 189. 267 P. Talan J. Mucha and A. Kosturiak Radiochem. Radioanal. Lett. 1980,45 269. 268 R. Flanagan B. C. Lentle D. G. McGowan and L. I. Wiebe J. Labelled Compd. Radiopharm. 1981 18,79. 269 H. J. Machulla K. Dutschka M. Marsmann and D. van Beuningen Radiochem. Radioanal. Lett. 1981 46 317. 270 Zs. Barkai Izotoptechnika 1980 23 158. 27 1 A. Freud D. Solencheck N. Hirshfeld and Z. Teitelbaum Isr. A.E.C. Rep. 1980 No. lA-1356,236. 272 H. M. Zacharis M. I. Thakur and A. Gottschalk J. Labelled Compd. Radiopharm. 1981 18 75. 273 M. R. A. Pillai U. H. Nagvekar C. N. Desai and R. S. Mani Radiochem. Radioanal. Lett. 1981 47 257. 274 B. L. Liu J. Yutai L. Zhenghao S. Zhaoxiang L. Gongx and L. Taihua I. Labelled Compd. Radiouharm.1981 18 112. 27s J. K. Tanchou and W. R. Slaunwhite jun. Prep. Biochem. 1979 9,370. 276 A. Canfi S. Shrem and Z. Teitelbaum Isr. A.E.C. Rep. 1980 No. 1A-1356 240. 277 A. Canfi D. Solencheck Z. Teitelbaum and 0.Buchman Isr. A.E.C. Rep. 1980 No. 1A-1356,230. 278 Z. Teitelbaum and D. Solencheck Zsr. A.E.C. Rep. 1980 No. 1A-1356 231. 279 G. L. Tonnesen R. N. Hanson and D. E. Seitz Int. J. Appl. Radiat. Isot. 1981 32 171. 280 W. Besch K. P. Woltanski S. Knospe M. Ziegler and H. Keilacker Acta Bid. Med. Ger. 1980 39,495. 281 S. Bahrami H. Zahn D. Brandenburg H. J. Machulla and K. Dutschka Radiochem. Radioanal. Lett. 1980,45 221. 282 I. Mucha G. Toth and B. Tanacs in ref. 64 p. 319. 283 L. Kronrad P. Hradilek J. Brousil and P. Svihovcova in ref.251 p. 36. 284 G. H. Hinkle G. P.Basmadjian A. S. Kirschner and R. D. Ice Nucl. Med. Commun. 1980 1,302. 285 L. A. Hawkins A. T. Elliott L. J. Dyke and F. Barker J. Labelled Compd. Radiopharm. 1981 18 126. 2g6 P. M. Wanek Radiochem. Radioanal. Lett. 1981 46,401. 287 S. L. Garcia C. J. Alvarez and M. C. A. Romo Rev. SOC. Quim. Mex. 1979 23 121. 288 G. Toth in ref. 64 p. 268. 326 D. S. Urch. have been adopted in introducing a radioactive iodine atom into a molecule have included surface catalysis on silica gel to promote halogen exchange289 (e.g. for iodoantipyrine) the introduction of aromatic rings227 into molecules to facilitate subsequent iodination (e.g. for folic and the use of chloramine-T as an (uracil derivatives).5 Chemistry of Atoms (and Ions) Produced by Nuclear Transformations There is continued interest in the theoretical and kinetic treatment of ‘hot’-atom chemistry. Shi~gal~~ has shown that the simple Estrup-Wolfgang treatment of hot-atom reactions gives results that are within 20% of his more sophisticated non-equilibrium time-dependent theory. Although there can be no ‘steady-state’ in the conventional kinetic theory sense yet it is possible to construct a time- independent collision-density function in terms of a time-averaged distribution function. Another theoretical approach considers the kinetics of hot- and thermal- atom reactions in systems such as hydrogen bromide and methane with considerable success.294 The main features of recoil-atom chemistry in condensed phases have been reviewed.295 Hydrogen.-A series of detailed ab initio calculations has been carried for the reaction of a hydrogen (or tritium) atom with methane (C‘H or C2H4)in the region of the saddle point for reaction co-ordinates that could lead to either abstraction or substitution.The results which compare favourably with other theoretical calculations and with experiments show that in the reaction of the attacking atom with one hydrogen of methane there is considerable interaction with the vibrational modes of the methyl groups during abstraction (e.g. 3H*+ CH -B ,HH + ‘CH,) but not during substitution (e.g. + CH + ,HCH3 + H*) The vexed problem of the role of so called ‘inert’ moderators in experimental studies of the gas-phase reactions of recoil tritium atoms still attracts attention with the possibility of a new ‘helium anomaly’ having been It would appear that even if collisional deactivation of vibrationally excited ,HH by helium is taken into account it is not possible to explain all the reactions taking place in bromine- ethane mixtures.Recoil tritium reacts with benzene and with fluoroaromatic molecules replacing amongst other reactions hydrogen and fluorine. The relative efficiency 3H for F 3H for H is however only 0.3 so that overall organic yields fall as the degree of fluorination increases.298 A successful calculation of product yields requires the assumption of about five percent of the tritium reacting as ’H+.Tritium atoms with known amounts of translational excitation energy can be made by photolysis (e.g.of hydrogen iodide 254 or 229 nm) and the results of such experi- 289 T. E. Boothe J. A. Campbell B. Djermouni R. D. Finn A. J. Gilson and H. J. Ache Int J. Appl. Radiat. Isot. 1981 32 153. 290 Becton Dickinson and Co. UK P. 1980 1 581 075/A/. 291 P. R. Farina and J. A. Grattan Fr. P. 1980 2 455 602/A/. 292 C. N. M. Bakker and F. M. Kaspersen Int. J. Appl. Radiat. Isot. 1981 32 176. 293 B. Shizgal J. Chem. Phys. 1981 74 1401. 294 S. Aronowitz S. Chang and T. Scattergood J. Phys. Chem. 1981,85 360. 295 C. H. Collins F. M. Lancas J. C. de Andrade and K. E. Collins Quim. Nova 1979 2,4; ibid.,p. 148. 296 G. C. Schatz S. P. Walch and A. F. Wagner J. Chem. Phys. 1980 73 4536. 297 D. J. Malcolme-Lawes Y. Ziadeh and G.Oldham J. Chem. Soc. Chem. Commun. 1981,545. 298 G. A. Brinkman E. Hulsinga J. Visser and A. Cecchi Radiochim. Acta 1980 27 197. Radiochemistry 327 ments compliment recoil tritium work. The abstraction reactions of photolytically- produced hydrogen atoms with a series of specifically deuteriated solid isobutanes (4 K and 77 K) showed remarkable selectivity; the higher energy atoms reacting preferentially at the primary site whereas the lower energy atom abstracted the tertiary hydrogen.299 Conversely labelled recoil atoms can be used as a source of near thermal atoms so that the reactions of such atoms can be easily studied. Rowland and co-workers have established over many years that the yield of 3HH made by the abstraction reaction of near thermal tritium atoms with hydrogen- containing molecules can be correlated with the bond strength with which that hydrogen was bound.Recently it has been ~hown,~" using this technique that the C-H bond in haloethylenes have a remarkably constant dissociation energy of 458 f 8 kJ mol-' (450 cis-CHCl=CHCl 466 CF,=CHF). Carbon,-High-energy proton bombardment of nitrogen initiates 14N(p a)"C. This reaction can therefore be used as a source of "C with cyclotron (or linac301) accelerated protons. "C-labelled compounds are in great demand in nuclear medicine but the short half-life of this isotope (20 min) means that great emphasis is placed on the speed with which chemical reactions can be carried out and of course the incorporation by suitable hot-atom reactions of "C into chemically reactive molecules suitable for use in a wide range of synthetic routes.A detailed of the proton irradiation of nitrogen-alkyl halide and nitrogen-hydrogen halide mixtures has shown that "C reacts directly to produce many labelled alkyl halides and that in particular the N + HI mixture is a potent source of ["Clmethyl iodide.303A wide range of "C-labelled nitrogen-containing organic compounds (cyanamides guanidines etc.) is formed when solid ammonium halides are bombar- ded with high-energy clearly radiation-induced reactions are important not just the (possibly hot) reactions of nascent carbon atoms. [l'C]Guanidine has also been reported from the proton irradiation of liquid ammonia.3o5 Nitrogen.-The longest-lived radioactive isotope of nitrogen (13N rlI2= 10 min) can be made either by proton bombardment of oxygen or deuteron bombardment of carbon i.e.l6O(p cu)13N306or 12C(d n)13N.307 The former reaction in water leads to labelled nitrate and nitrite anions,308 (reduction of these anions to ammonia followed by hypobromite oxidation leads to labelled dinitrogen for medical use). Oxygen.-Deuteron bombardment of nitrogen-water vapour mixtures gives rise to hot I5O atoms [I4N(d n)150] which react to give H2150 (for use in nuclear medicine309). 299 T. Miyazaki A. Wakahara T. Kimura and K. Fueki J. Phys. Chem. 1981,85 564. 300 F.J. Steinkruger and F. S. Rowland J. Phys. Chem. 1981,85 136. 301 E.L.Sattler and U. Wagenbach J. Labelled Compd. Radiopharm. 1981,18,32.302 R. Wagner Thesis Inst. fur Nuklearchemie K.F.A. Julich Germany 1980. 303 R. Wagner and G. Stoecklin J. Labelled Compd. Radiopharm. 1981,18 189. 304 K. Roessler M. Vogt and G. Stoecklin J. Labelled Compd. Radiopharm. 1981 18 190. 305 R. Iwata T. Ido and T. Tominaga J. Labelled Compd. Radiopharm. 1981 18 187. 306 R. D. Finn A. J. Gilson D. R. Christman and A. P. Wolf J. Labelled Compd. Radiopharm. 1981 18,36. 307 G. del Fiore J. C. Depresseux and J. M. Peters J. Belge Radiol. 1979,02 459. 308 W.Vaalburg A. Steenhoek A. M. J. Paans R. Peset S. Reiffers and M. G. Woldring J. Labelled Compd. Radiopharm. 1981,18,303. 309 P. V. Harper and T. Wickland J. Labelled Compd. Radiopharm. 1981 18 186. 328 D. S. Urch Fluorine.-Although the use of recoil fluorine-1 8 atoms to prepare labelled sub- stituted carboxylic and amino-acids has been rep~rted,~" most recent work has centred on the reactivity of "F atoms thermalized in the gas phase by excess sulphur hexafluoride.Both substitution (of H or X by F) and abstraction (of H or X by F) in alkyl halides (CH3X) and perfluoroalkyl halides (CF3X) were studied. Rates for reactions such as F' + CH3Br +HF + CH2Br' F' + CH,I -+ IF + CH,' F' + CF31+ IF + CF,' were all found to be in the range of 5 -20 x 10-lrcm3 mol-' s-',~''whereas reactions such as F' + CH31+ CH3F + I' were slower by two or three orders of rnagnit~de.~'~ A similar investigation of propyne and 3,3,3-trifluoropropyne showed that about a third of the fluorine atoms abstract hydrogen from the former but only a sixth react in this way with the latter.The remainder of the atoms react by addition showing a preference for the terminal position of 2.6 :1 in propyne but 3.7 1 in the fluoropropyne. The fluoropropenes that were eventually formed were found in their thermodynamic cis :trans ratios presumably showing that the intermediate olefinic radical formed by thermal 18F addition to the triple bond had sufficient energy to is~merize.~'~ Silicon.-Recoil silicon chemistry continues to attract attention because of possible similarities with carbon. If formed from PF much of the recoil silicon appears to react as 3'SiF2 with additives such as ethylene and buta-l,3-diene forming 1,l- difluorosilacyclopentaneand 1,l -difluorosilacyclopent-3-ene.314 Sulphur.-The reactions of recoil sulphur atoms [35Cl(n P)~~S] in solid potassium chloride315 and liquid carbon tetra~hloride~'~ have been studied.Chlorine.-Various radioactive isotopes of chlorine have been used to study the reactions of hot and thermal chlorine atoms. The results of neutron [37Cl(n y)"Cl] irradiation of mixtures of aliphatic compounds with chloro-compounds such as chloroform and carbon tetrachloride can be rationali~ed~l' using the one-step 'hot zone' model of Kontis and Urch;,18 it has been confirmed that the presence of an aromatic component introduces a second 'thermal' More detailed studies of labelled products (as 34mCl derivatives) from and ~henyl~~' chlorides (all liquids) shows that only about five percent of the recoil atoms react by a direct 'hot' reaction to give an organic product and that 'cage' reactions contribute about another 20%.In the case of the aromatic systems both thermal exchange- and radiation-induced exchange extensively augment the organic yield; these reactions correspond to the second thermal diffusive stage of the Kontis Urch and Malcolme-Lawes The effect of changing phase from liquid to 310 A. Donnerhack and E. L. Sattler J. Labelled Compd. Radiopharm. 1981 18 30. 311 R. S. Iyer and F. S. Rowland J. Phys. Chem. 1981,85,2493. R. S. Iyer and F. S. Rowland J. Phys. Chem. 1981,85 2488. 313 C. Concannon and F. S. Rowland J. Phys. Chem. 1981,85 89. 314 Y. N. Tang D.O.E. Rep. ER/03898-52 Agricultural and Medical Univ. College Station Texas USA 1981.315 S. Rossi M.Sc. Thesis Instituto de Pesquisas Energeticas e Nucleares Sao Paulo Brazil 1980. 316 R. Davila Thesis Universidad Autonoma de Zacatecas Mexico 1980; cf. ZNIS Atomindex 1981 12,637 470. 317 R. N. Bhave and B. S. M. Rao Radiochem. Radioanal. Lett. 1981 46 389. 318 S. S. Kontis and D. S. Urch Radiochim. Acra 1973 20 39. 319 S. S. Kontis D. J. Malcolme-Lawes and D. S. Urch Radiochim. Acta 1977 24 87. 320 G. A. Brinkman G. A. V. Gerritsen and J. Visser Radiochim. Acta 1980 27 203. 321 G. A. Brinkman F. M. Kaspersen and J. T. Veenboer Radiochim. Acra 1981 28 61. Radiochemistry 329 solid3*’ upon the reactions of 38Cl in chlor~benzenes,~’~ chloroethenes and mixtures containing alcohols and hexaflu~robenzene~’~ has been extensively studied by Berei.95% of the recoil chlorine atoms thermalized by multiple collisions with chlorotrifluoromethane add to propyne with an 8 to 1preference for the terminal showing as might be expected that thermal chlorine atoms are more selective than fluorine atoms. With lead tetramethyl and tetraethyl thermal chlorine atoms are able to displace and react with an alkyl group.326 About 20% react in this way the remainder presumably just abstract hydrogen atoms to form H38Cl. Chromium.-The recoil chemistry of hot chromium atoms in many solid complexes (acetyla~etonates,~’~ dichromate~~’~), thio~yanates,~’~ has been studied including the effect of subsequent annealing upon the final chemical state of the chromium atom.Besides the conventional methods which involve the dissolution of the solid attempts have been made to use other physical methods to determine the valence and environment of the recoil atom at the end of its tract. For isotopes such as 51 Cr that decay by electron capture an investigation of the subsequent X-rays provides a possible method. It is claimed330 that measurement of the Kp :Ka ratio can distinguish between Cr”’ and Cr”’ although the ligand environment may also play a perturbing role upon this ratio. Iron.-Another technique that can be used in suitable circumstances is Mossbauer spectroscopy; for iron it can be used to probe directly the environment of 57Fe iron produced by the electron capture decay of 57C0 [in tris(P-diketonat0)-complexe~~~’].Cobalt.-This method has also been used to study the nature of the annealing reaction in dipyridyl complexes of cobalt (”Co) and the results compared with conventional technique^.^^' Solid-state recoil-annealing studies continue to be made for a range of complexes e.g. tri(ethy1enediamine) nickel [58Ni(y p) 57C0 or p+ decay of 57Ni],333tri(ethy1enediamine)cobalt [59C0(y n)5sCo],333 and tri(benzoy1- acet~nate)cobalt.~~~ Bromine.-Proposals that the yields of specific labelled bromides from the reactions of recoil bromine species with hydrocarbons in the gas phase could be explained by means of ion-molecule reactions have failed to be substantiated by a direct investigation of the ion-molecule reactions between Br’ and hydrocarbon vapo~rs.~~~ In the presence of rare-gas additives it is proposed that ions such as 322 K.Berei L. Vasaros and H. J. Ache Proc. 2nd Hung. Symp. on Radiochernistry Debrecen Hungary 1980 p. 12; cf. INISAtomindex 1981 12 631 871. 323 K. Berei and H. J. Ache J. Phys. Chem. 1981 85 986. 324 K. Berei L. Vasaros and H. J. Ache J. Phys. Chem. 1980,84 1063. 32s F. S. C. Lee and F. S. Rowland J. Phys. Chem. 1980,84 1876. 326 M. Kikuchi F. S. C. Lee and F. S. Rowland J. Phys. Chem. 1981 85 84. 327 C. M. Goetz and C. H. Collins Cienc. Cult. (Sao Paulo) Suppl. 1979 31 309. 328 F. M. Lancas and C. H. Collins Cienc. Cult. (Sao Paulo) Suppl. 1979,31 372. 329 M. de Rocha and C. H. Collins Cienc. Cult. (Sao Paulo) Suppl. 1979 31 309. 330 K. E. Collins C. H. Collins and C. Heitz Radiochim.Acta 1981 28 7. 331 Y. Sakai K. Endo and H. Sano Bull. Chem. SOC.Jpn. 1980 53 1317. 332 C. H. Collins K. E. Collins M. F. de J. Filho and J. M. Friedt J. Inorg. Nucl. Chem. 1981 43 1735. 333 T. Omori S. C. Wu and T. Shiokawa Radiochim. Acta 1980 27 187. 334 T. Omori T. Akimoto and T. Shiokawa Radiochim. Acta 1980,27 191. 335 H. P. Watkins and W. S. Koski in ref. 12 p. 26; cf. D.O.E. Rep. ER/03283-31 1980; and INIS Atomindex 1981 12 591 078; ibid. p. 609 628. 330 D. S. Urch KrBr' and ArBr' must play a vital role in introducing bromine into organic molecules. Such ions have also been to explain the observed yields of bromine-labelled species when 76Kr or 77Kr decays (to 76Br or 77Br) in the gas phase in krypton hydrocarbon mixtures. In pure methane excited CH4Br+ may play a role but radiation effects are also thought to be important.Ion reactions have also been investigated in halogen-substituted me thane^.^^^ On a more practical note it has been that a good yield of labelled perfluoromethylbromide [CF380mBr] was formed by the thermal neutron irradiation of CF31-CH3Br mixtures undoubtedly due to exchange as well as direct hot-atom and ionic reactions. In the solid phase similar preoccupations with the mechanisms of recoil bromine reactions are found. In solid hydrocarbons differences between 76Br and 77Br (from decay of isobaric krypton isotopes) are to differences in charge recoil energy and radiation damage caused by the isotopes. Annealing studies of the labelling of inorganic bromates by 'OmBr and 82Br (n y)340 or by "Br (IT)341 or by 83Br rg2Se(n y)83Se(p-)83Br]342 have been made.The latter work showed that 5% of recoil bromine in a selenate matrix ended up as perbromate. Exchange reactions can also lead to labelled perbromate as was shown by 'annealing' of Kg2Br-KBr04 Other annealing studies have investigated the behaviour of 'OrnBr in 3-bromoacetylacetonate complexes of chromium iron cobalt etc.344 Molybdenum.-The yields of compounds labelled by the [98M~(n reaction Y)~~Mo] are greatest at low neutron ligand environment as in mixed carbonyl- trifluorophosphine complexes is also important (the more carbonyl groups the greater the 'retention'346). Technetium.-Although the 'retention' of technetium activity in pertechnate salts following the isomeric transition of 99rnT~ to the ground state is about 70°/0,347*348 no retention is found in solution indicating that the initial chemical effect of the decay must be the rupture of the original anion.347 Antimony Tellurium.-Mossbauer spectroscopy has been used to show that recoil '19Sb and 'lgmTe atoms are found at minimally disturbed lattice points in tin- antimony tin-tellurium and tellurium-antimony alloys.349 Iodine.-The role of the and other anions3" in controlling the retention of 1281 activity produced by the neutron irradiation of iodates has been reported.336 J. J. Frost S. M. Moerlein and M. J. Welch J. Am. Chem. SOC. 1981 103 4337. 337 S.P.Mishra and N. P. Singh in ref. 12,p. 31. 338 D. de Jong B. E. Van Halteren and J.Th.Veenboer Int. J. Appl. Radiat. Isot. 1981 32 101. 339 J. J. Frost S. M. Moerlein and M. J. Welch J. Am. Chem. SOC.,1981 103 4332. 340 V. G. Dedgaonkar R. S. Lokhande and D. A. Bhagwat Radiochem. Radioanal. Lett. 1981,47,137. 341 J. de la Torre M. Jimenez-Reyes and S. Fernandez-Valverde Rev. SOC. Quim. Mex. 1980 24 256. 342 B.Lopez D. Tenorio S. Bulbulian and J. P. Adloff Radiochem. Radioanal. Lett. 1980,45,35. 343 S.Bulbulian J. J. Schleiffer and J. P. Adloff Radiochem. Radioanal. Lett. 1980 44 385. 344 J. N.Khanvilkar A. T. M. Sharifullah B. R. Kundalkar and A. M. Mukhedkar Radiochim. Acta 1981 28 69. 345 A. Krueger and K. H. Lieser Radiochim. Acta 1981,28 29. 346 T.E.Gedris R. J. Clark and J. Catral-Navarrete J. Inorg. Nucl. Chem.1981 43,431 347 E.Ianovici P. Lerch G. Zahner and A. G. Maddock Radiochim. Acta 1981,28 23. 348 E. Ianovici P. Lerch Z. Proso G. Zahner and A. G. Maddock Radiochim. Acta 1981,28 57. F. Ambe and S. Ambe J. Chem. Phys. 1980 73 2029. 349 350 S.P.Mishra and R. B. Sharma Radiochem. Radioanal. Lett. 1980,44 227. 351 S.K. Sankpal and B. S. M. Rao Radiochem. Radioanal. Lett. 1980,45,289. Radioc hemistry 331 Other recent work has concentrated more on the effects of decay of radioactive iodine in iodo~racil,~~~ and in the failure of high specific activity 13’1 solutions to produce iodate with alkali.3s3 Other Elements.-Neutron irradiation of uranium oxide-metal diketonate mixtures leads to the formation of diketonate complexes of many fission nuclei presumably by hot a similar study of 234Th from a decay of uranium has been In solution the final oxidation state of recoiling fission products would appear to depend upon the concentration of dissolved oxygen as well as radiation 6 Miscellaneous Reactor Waste.-A chromatographic method has been devised3s7 for the isolation of radioactive rare gases from the atmosphere and the effectiveness of a range of zeolites and molecular sieves in adsorbing krypton xenon and water vapour from nuclear power plant gaseous effluent has been determined.3s8 Polymethyl siloxanes have been used SUCC~SS~U~~~~~~ to remove radioactive iodine from reactor gases ways of eliminating methyl iodide have also been considered.360 Methods for decontaminating liquid waste of specific elements (e.g.137Cs,361 Ru using zirconia- silica Sr and Ba by ~o-precipitation,~~~ and Ra by the use of activated barium ~ulphate~~’ as well as techniques for liberating various isotopes from the materials on which they have been continue to be investigated. A report has been issued detailing the level of transuranic nuclides present in solid low-level waste from US power The behaviour of glasses into which radioactive elements might be incorporated under the stress of high radiation has been Decontamination.-Techniques have been developed for the decontamination of metal surfaces (from glove boxes etc.)e.g. chemical etching,369 high pH solution^,^^^ 352 R. Deutzmann and G. Stoecklin Report Nuclear-Radiation- and Radiochemistry Meeting Julich Germany (Sept.) 1980.353 E. Iwanicki and M. Tencer Radiochem. Radioanal. Lett. 1981,47 101. 354 S. Nishikawa Radioisotopes (Tokyo) 1980 29 130. 355 M. Garcia-Rendon M. Solache and D. Tenorio in ref. 12 p. 35. 356 H. Moriyama I. Fujiwara andT. Nishi J. Inorg. Nucl. Chem. 1981 43 731. 357 S. K. Achkasov A. V. Kadushkin V. I. Nekrasov and Yu. A. Serbulov in ‘Experimental Methods of Nuclear Physics No. 5’ ed. V. M. Kolobashkin Moscow 1979 p. 160. 358 I. E. Nakhutin D. V. Ochkin and S. A. Tret’yak At. Energ. 1980 49 286. 35y I. E. Nakhutni L. Rastunov N. M. Smirnova G. A. Loshakov and G. A. Laushkina Proc. Int. Symp. Management of Gaseous Wastes from Nuclear Facilities IAEA Vienna Austria 1980 p. 115. 360 D. G. Andrews and M.Moledina Can. Nucl. SOC. Trans. 1980 1,35. G. E. Sharonov and R. I. Pogodin Radiokhimiya 1980 22 297. 362 K. Ito and T. Kanno Nippon Genshiryoku Gakkai-Shi. 1979,22,413. 363 K. Ito and T. Kanno Tohoku Daigaku Senko Seiren Kenkyusho Iho. 1979 35,93. 364 T. Tsutsui Hoken Butsuri. 1980,15 33. 365 L. Berak Radioaktiv. Zivotn. Prostr. 1980 3 89. 366 H. Prochazka K. Stamberg K. Jilek P. Hulak and J. Katzer Czech. P. 1978 174 971/B/; cf. INIS Atomindex 1981 12 575 090. 367 J. E. Cline K. L. Wright and J. W. Hollcroft Rep. EPRI-NP-1494 1980; cf. INIS Atomindex 1981 12,573 019. 368 J. D. Brocklehurst K. E. Gilchrist R. W. Adam and S. D. Preston High Temp-High Pressures 1980,12 317. 369 R. E. Lerch and J. A. Partridge US P. 1980,4 217 192/A/. 370 J.L. Long and E. L. Childs Rockwell Int. Corp. Golden Co USA Rep. RFP-3101 1979; cf. INIS Atomindex 1981,12 584 166. 332 D.S. Urch and ele~trolytically.~~~ Also much more effort has been expended in attempts to clean up contaminated concrete as reported (14papers) in the Concrete Decontami- nation Workshop.372 Related work has dealt with techniques used to remove radium contamination from and general radioactivity contamination from the General reports have also appeared concerning problems of decontamination and Radionuclides in the Sea.-The chemical state of (60Cois found as Co2+ CoCl’ and C0S04) and the effect of plankton on the states of ruthenium and cerium 378 (no mention of the effect of lo6Ru and ‘44Ce on the state of the plankton though) have both been investigated.But the major effort in this area is concentrated on uranium in the sea,379 with a view to its extraction. Hydrated titania,380-382 hydrated titanium(Iv)-iron(II) and exotic resins385 coated with amid~xime~*~ or hydroxylamine groups387 have all been extensively assessed. Detection.-The problem of scintillation counting of insoluble 14C-labelled materials can be overcome if the radioactive substance can be adsorbed on a suitable substrate such as silica gel.388 A rather different approach involves adsorption onto a cellulose support followed by dispersion using sulphuric acid and hydrogen peroxide.389 When plastic scintillators are used correction for surface adsorption is of course necessary.39o The use of y-rays (and X-rays) for elemental analysis and in the detection of specific radionuclides has been considerably facilitated by the development of a computer program that can be run on a machine as small as a ~~-2100.~~~ 371 E.L. Childs and J. L. Long US P. 1980 4 193 853/A/. 372 J. M. Halter R. G. Sullivan and A. 3. Currier (ed) ‘Concrete Decontamination Workshop’ Seattle WA USA 1980 (NTIS PC AlO/MF A01). 373 J. M. White Am. Ind. Hyg. Assoc. J. 1980 41 49. 374 A. W. Graves ‘Environmental Decontamination Workshop’ Oak Ridge Tenn. USA 1979 (NTIS PC A02/MF A01). 375 R. 0. Gilbert R. R. Kinnison and M. G. Barnes “Environmetrics ‘81” Conf. Washington DC USA 1981; cf ZNZSAtomindex 1981,12 621 357. 376 H. K. Elder and D. E. Blahnik ‘Technology Safety and Costs of Decommissioning a Reference Uranium Fuel Fabrication Plant’ 1980 Vol.1 and 2 (NTIS PC A12/MF A01). 377 S. Hirano and T. Koyanagi Nippon Kaisui Gakkai-Shi. 1980,36 35. 378 A. A. Volkov V. V. Chubarov Yu. A. Sapozhnikov and V. V. Anikiev Radiokhimiya 1980,22,568. 379 Report by Atomic Energy Society of Japan Nippon Genshiryoku Gakkai-Shi. 1980,22,31. 380 H. Yamashita and F. Nakajima Bull. Chem. SOC.Jpn. 1980 53 1331. 381 H. Yamashita and F. Nakajirna Bull. Chem. SOC.Jpn. 1980 53 3050. 382 T. Shirotsuka and E. Inoune Nippon Kaisui Gakkai-Shi. 1980 34 189. 383 Y. Ozawa T. Murata H. Yamashita and F. Nakajima J. Nucl. Sci. Technol. (Tokyo) 1980 17,634. 384 Y. Ozawa T. Murata H. Yamashita and F. Nakajima J. Nucl. Sci. Technol. 1980 17 204. 385 Yu. P.Novikov N. M. Mikheeva B. F. Myasoedov M. V. Akhmanova and V. M. Komarevskij Radiokhimiya. 1980 22 336. 386 H. Egawa H.Harada and T. Shuto Nippon. Kagaku. Kaishi. 1980 1773. 387 H. Egawa H. Harada and T. Nonaka Nippon Kagaku. Kaishi. 1980 1767. 388 W. Reimschuessel and M. Kubik J. Radioanal. Chem. 1980 60 55. 389 M. Takiue and H. Ishikawa Znt. J. Appl. Radiat. Zsot. 1980 31 619. 390 T. N. Seredenko V. M. Ehkkerman V. M. Solomonov and N. S. Gen Radiokhimiya 1980,22,343. 391 V. Roca F. Terrasi R. Moro and G. Sorrentino Nucl. Instrum. Methods. 1981 180 535.

ISSN:0260-1818    

DOI:10.1039/IC9817800313

出版商:RSC    

年代:1981

数据来源: RSC

摘要:

13 Industrial Inorganic Chemistry By R. THOMPSON Borax Holdings Ltd. Cox Lane Chessington Surrey KT9 1SJ 1 Introduction Since the Society of Chemical Industry discontinued in 1978 its Reports on the Progress of Applied Chemistry’ there has been no regular collected review of developments in industrial inorganic chemistry. Even those reports were of necessity scant and intermittent in the treatment their coverage being the whole field of applied chemistry. No attempt had been made by The Royal Society of Chemistry in recent years to deal with the subject in its own Annual Reports but now that this series is subdivided formally into the traditional branches of chemistry it was decided to rectify the omission by including in Section A some reference to industrial aspects.On this occasion it takes the form of a broad review although consideration will be given to treatment of one or more topics in greater depth for future Reports. The Inorganic Chemicals Group of this Society’s Industrial Division recognized the neglect in publicising developments in its sector of the industry and accordingly held as part of the April 1977 Annual Congress in London a Symposium at which current technology in the production of major-tonnage inorganics was described by experts from the respective areas. The basic intent was in fact to produce an authoritative and low-cost book on the subject in order to fill a distinct gap amongst chemical texts and build the symposium around its chapters. The book ‘TheModern Inorganic Chemicals Industry’* was first published in 1977 and demand was such that it sold out quickly and had to be reprinted; the second reprint is now available as the first was exhausted by the end of 1981.Many important inorganic chemicals had for space reasons to be omitted from the first book but the situation was remedied by the appearance late in 1981 of ‘Speciality Inorganic chemical^'.^ The book was also one around which a symposium had been built on that occasion in September 1980 at the University of Salford. Attendances at both of the symposia and the sales of the books indicate a strong interest in industrial inorganic chemistry; perhaps even an awareness of its existence so neglected has it been in recent years in the overcrowded curriculae of many schools and universities.It is hoped that the appearance of these annual reviews might help to foster the renaissance. ’ ‘Reports on the Progress of Applied Chemistry’ The Society of Chemical Industry London. ‘The Modern Inorganic Chemicals Industry’ ed. R. Thompson Special Publication No. 31 The Chemical Society London 1977. ‘Speciality Inorganic Chemicals’ ed. R. Thompson Special Publication No. 40 The Royal Society of Chemistry London 1981. 333 334 R. Thompson Inorganic texts are customarily systemized along the lines of a periodic table relationship or ‘special topics’. The method chosen here now is broadly according to the traditional segmentation of the inorganic sector of the industry and frequent cross-reference is made to the above books.Some of the sub-divisions and associ- ations might appear arbitrary but there are usually sound chemical raw materials and energy-sources logistics reasons as well as historical and business roots Industrial inorganic chemistry is about the inorganic chemicals industry. Although the following text makes reference to announced developments in technology (the underlying chemistry of which is seldom totally novel) an attempt has been made to present also a perspective of the relative importance of the different chemicals tonnages produced environmental influences economic growth (or decline) and the shifting centres of gravity of various parts of the industry. The source material has been in the main the trade journals. Items in these media are rarely attributed hence most of the references are to the journal and page number only.Each nation’s chemical trade journals are usually international in coverage and where a topic has been mentioned in more than one source a selection is given because the depth of treatment can vary. In preparing this Review it became very apparent to the reporter that although many new plants and constructions were announced for Japan the United States and West Germany Great Britain featured distressingly infrequently. 2 Chlor-Alkalis The chlor-alkali sector which embraces chlorine caustic soda and soda ash (anhydrous sodium carbonate) is a cornerstone of the entire chemicals industry. Chlorine and sodium hydroxide are obtained by the electrolysis of brine via an evolutionary variety of cells but latterly reduced to one type of mercury cell and two types of diaphragm cell.4 Although traditionally the salt supply for this industry was from underground deposits the historical reason for the location of the major plants there has been a trend towards other sources notably from the solar evaporation of sea-water lagoons situated in appropriate climes; and with an obvious attendant advantage of ease of ocean shipment to the more industrialized parts of the world.However this is not without its drawbacks and a plant in the Bahamas which had operated since the early 1960’s was closed for economic reasons after a hurricane in 1979 and heavy rains during 1980 had ruined harvest^.^ Large quantities of sodium chloride waste are available as by-product from the potash industry and the French government is supporting a study of a plant in Alsace that would produce 500 000 tonnes per year from this source.6 A more novel by-product source has been developed in Japan where hydrogen chloride is removed from the flue gases of a refuse incinerator plant by scrubbing with caustic The Japanese situation is however peculiar in that the country has no deposits of its own and although some sea-water brine is electrolysed it is entirely dependent upon imported salt.s R.W. Purcell in Ref. 2 pp. 106-133. Baker’s Dig.,1981 February p. 47; Chem. Mark. Rep. 1981 23rd February p. 4; Soap Cosmet. Chem. Spec. 1981 March p. 81; WallSt.J. 1981 18th February. Chem. Age 1981 13th February p. 6; Eur.Chem. News 1981 16th February p. 8. ’Chem. Age 1981 17th July p. 13; Chem. Eng. 1981 10th August p. 17. Chem. Eng. News 1981 27th July p. 22. Industrial Inorganic Chemistry 335 The trend away from the mercury cell has accelerated for both environmental reasons and in order to reduce energy requirements. There is a government mandate for this changeover in Japan,* where caustic-soda production via ion-exchange membrane processes has more than doubled to 172 000 tonnes per year although this is still small compared with 2.85 million tonnes by the diaphragm process.’ But some 1.5 million tonnes or 35.4% of total Japanese production is still by the mercury cell. lo The new and rapidly developing ion-exchange membrane processes are in several instances even replacing the diaphragm cells to reduce electricity needs and one producer claims a reduction from almost 3000 kW h/tonne caustic soda for the asbestos diaphragm technology to approaching 2000 kW h/tonne with the added advantage of complete elimination of the need for steam.” The membrane cell is like a diaphragm cell in which the asbestos diaphragm has been replaced by a cation-exchange membrane through which chloride ions cannot pas4 The membranes must be resistant to chlorine attack and are usually perfluorinated sulphonic acid (‘Nafion’) or carboxylic acid perhaps supported on a Teflon fabric.12 It is claimed to be possible to modify existing diaphragm cells and because of the low voltage needed the rectifiers now employed for the mercury cell process can still be used.13 The first large-scale membrane plant in the USA should begin production in 1983.14 Electrodes have also undergone development and a so-called FM 21 cell uses an anode of titanium coated with ruthenium oxide together in this case with a perfluorocarboxylic (‘Flemion’) membrane.” The cell produces more concentrated caustic soda (35%) and so reduces evaporation energy requirement.Although in the past large quantities of caustic soda were made from sodium carbonate and limited amounts of the latter are still made from the for me^,^ the production of the two is now largely independent. Sodium carbonate (‘soda ash’) occurs naturally as trona and the bulk of the USA’s production of 8.5 million tons per year is from this source much of it in Wyoming.16 New solution mining processes now at the pilot plant stage are expected to reduce production costs by 25’/0.‘~*’~ Immediate by-products of the electrolytic industry are elemental sodium on the one hand and hypochlorite sodium chlorate and chlorine dioxide.More than half of the sodium produced in the USA where the capacity in 1981 was around 140 000 short tons,18 is used for the manufacture of leaded gasoline.” As the use of this motor fuel is quickly being phased-out it is not surprising that the two major producers have recently reduced capacity by 28% but overall demand is predicted to remain level until 1985.’’ Capacity for sodium chlorate production Jpn. Chem. Week 1981 14th May p. 1. lo Chem. Week 1981 1st April p.23. Chem. Age 1981 9th January p. 17; Eur. Chem. News 1981 31st August p. 15; Jpn. Econ. J. 1980 25th November p. 16. DuPont 1980 October p. 7; Jpn. Chem. Week 1980 30th October p. 2; Jpn. Chem. Week 1981 7th May p. 6;Jpn. Chem. Week 1981 22nd October p. 1. l3 Jpn. Chem. Week 1981 7th May p. 6. 14 News Release 1981 21st May p. 11; Chem. Eng. 1981 1st June p. 11; Chem. Eng. News 1981 1st June p. 19; Pap. Trade J. 1981 30th June p. 98; Chem. Week 1981 27th May p. 13. l5 Corpus Chem. Rep. 1981 20th July p. 3; Can. Chem. Process 1981 18th September p. 14. l6 Chem. Eng. News 1981 2nd March p. 15. Bus. Week Znd. Ed. 1981 21st September p. 42. Chem. Mark. Rep. 1981 18th May p. 9. 19 Chem. Mark. Rep. 1981 18th May p. 9. 336 R. Thompson has been increasing rapidly largely in the USA and Canada where it is in demand for pulp bleaching.In a development of the Krebs electrolytic process installed at one pulp mill the use of metal anodes instead of graphite is claimed to reduce electricity consumption by over 20% and give by-product hydrogen for use in steam raising.2o Chlorine dioxide is produced in special generators by the acidification usually with sulphuric acid of sodium chlorate and is absorbed in water to give the C102 solution but the water needs to be chilled to increase absorption in which direction energy cost savings have been made.21 The generators are frequently of the Erco R3 type,22 but a new one known as the R7 has come ~n-stream.~~ In this generator the chlorine from the C102 absorption tower instead of being contacted with caustic to form hypochlorite is reacted with sulphur dioxide to yield a mixed acid giving rise to a smaller proportion of sodium sulphate by-product.A composite process that produces chlorine caustic soda and chlorine dioxide with sodium chloride as the only raw material has been explained in A non-polluting process for calcium hypochlorite having a 75-80% active chlorine content has been described.25 Although readily separated electrolytically soda and chlorine are economically almost inseparable and changes in respective demand patterns can distort the whole chlor-alkali industry. A severe shortage of caustic soda continued into 1981,partly because of a depressed demand for chlorine caused in turn by recessionary weakness in the vinyl chloride and fluorocarbon propellants markets but also in view of increased caustic soda requirements of the oil recovery industry.26 Forecasts of an increase in chlorine demand are only slightly less gloomy while the construction and automobile markets remain in de~line.~' The economics of the industry are affected by the low prices obtainable for chlorine during its over-supply and in the longer term the rising price of electricity is of major concern.28 Energy accounts for 60-70% of the cost of chlorine prod~ction.~~ A further example of the chlorine- caustic imbalance is found in Australia which has an abundance of solar evaporation salt and a need for sodium hydroxide for alumina production but little demand for ~hlorine:~' one suggestion is for an ethylene dichloride unit based on a chlor- alkali plant and using an ethane feed~tock.~' The market for soda ash over half of which is in glass manufacture has also been hit badly by reduction in demand from the construction and automobile industrie~.~~ The scarcity-inflated price for caustic soda is helping the soda ash suppliers where the two alkalis can be used interchangeably giving US producers from trona a further edge over 2o Pap.Trade J. 1981 15th February p. 17; Pulp Pap. 1981 November p. 88. 21 Pulp Pap 1980 October p. 152; Eur. Chem. News 1980 20th October p. 40; Eur. Chem. News 1980 27th October p. 32. 22 Can. Chem. Process. 1980 October p. 12. 23 CPIManag. Serv 1980 10th October p.3; Chem. Mark. Rep. 1981 26th January pp. 5,50. 24 Pulp Pap. 1980 October p. 185. 25 Chem. Eng. News 1981 27th April p. 28. 26 Chem. Week 1981 15th April p. ~12. 27 Chem. Eng. News 1981 2nd March p. 13. Chem. Mark. Rep. Chem. Bus.Suppl. 1981 24th August p. 27. 29 Financial Wkly. 1981 9th April p. 36. 30 Chem. Age 1981 9th January p. 14; Jpn. Chern. Week 1981 2nd July p. 1. 31 Eur. Chem. News 1981 20th April p. 34. 32 Chem. Purchas 1981 January p. 65. 33 Chem. Week 1980,26th November p. 35. Industrial Inorganic Chemistry 337 although West European companies are fighting back with the aid of government backing and protective tariffs.34 Free-world chlor-alkali production in 1980 was quoted (in millions of tons) as chlorine 23.0; caustic soda 24.9; and soda ash 25.7.35 Each showed a decline compared with 1979 but within the USA at least caustic soda output was expected to rise slightly in 1981.36 3 Inorganic Fertilizers The NPK fertilizer industry consumes most of the world’s production of ammonia and potash and accounts for a large proportion of phosphoric acid (and thus sulphuric acid indirectly).It was estimated in 1977 that combined in the forms of ammonium nitrate urea or ammonium phosphate over 50 million tonnes of nitrogenous fertilizers are used each year compared with 10 million tonnes for all other uses for fixed nitrogen compound^.^' Manufacturing processes were described. Recent attention has been paid in Germany and Japan to improvements in the production of ammonium sulphate by the neutralization of sulphurous flue gases.38 Japan continued as a major exporter of both ammonium sulphate and urea but under reduced demand.39 Morocco with extensive phosphate rock deposits has announced plans to almost double its own production of wet-process phosphoric acid to 4 million tons per year by the construction of twelve new plants together with twelve sulphuric acid plants requiring the importation of 1.5 million tons of sulphur per year.4o World capacity at the beginning of 1981 was over 32 million tonnes and plants are increasingly being sited near to phosphate rock The USA had 41y0 and Morocco had 15% of world phosphate in 1978.42 Outlets for US-produced wet- process acid were analysed as ammonium phosphates 60% ;triple superphosphate 20% ;other fertilizers 5% ;and animal feed 5% .43 A major problem of this industry is disposal of the calcium sulphate or ‘phosphogypsum’ by-product of the wet process between four and five tons are created for every ton of P205 Some is used in agriculture where it needs no purification but one company under environmental pressure is building a 15 kilometre pipeline to transport the slurry to a disused quarry.45 The calcium sulphate produced is usually in the form of dihydrate but attempts are being made to popularize the hemihydrate route.46 The latter produces saleable 50% acid directly and as there is no need to boil off the water there is a steam saving especially important as many plants are running at 34 Chem.Age 1981 20th February p.12. 35 Eur. Chem. News 1981 27th April p. 10; Chim. Actual. 1981 24th April p. 29. 36 Chem. Eng. News. 1981 2nd March p. 14. 37 S. P.S. Andrew in ref. 2 pp. 201-231. 38 Eur. Chem. 1981 February p. 74; Chem. Eng. News 1981 16th February p. 24; ErdolKohle 1981 March p. 98. 39 Chem. Week 1981 25th February p. 25; Chem. Week 1981,24th June p. 31. 40 Eur. Chem. News. 1980 1st December p. 27; Inf Chim. 1980 September p. 125; Chem. Age 1981 1st May p. 12; Eur. Chem. News 1981,22nd June p. 24. 41 Inf. Chim. 1981 March p. 139. 42 Chem. Week 1981 16th September p. 12. 43 Chem. Eng. News 1981,15th June p. 10. 44 Phosphorus Potassium 1981 June p. 23. 45 Eur. Chem. News 1981 18th May p. 4; Chem. Age 1981,22nd May p. 7. 46 Chem. Week 1981 14th January p.46. 338 R. Thompson 50% or more above design capacity; but there are disadvantages including the plant blockages owing to the hemihydrate’s instability. The source of potassium for the fertilizer industry is potassium chloride some of which is converted to the sulphate for use. Most potash is won by mining the solid from the relatively deep deposits although there is interest in solution mining when geological conditions are suitable. The KC1 usually occurs with NaC1 from which it is generally separated by froth flotation and fractional crystallisation according to well established technology. A potash-rich brine giving Mexico self- sufficiency by 1984 is the furtunate by-product of a geothermal well in Baja Calif~rnia.~~ Potash capacity has far exceeded demand for more than a decade; world production in 1980 was estimated to be about 28.25 million tons (as K20).48 4 Sulphuric Acid Sulphuric acid is so central to the economy of a nation that its per capita consumption has often been used as a measure of the living standard of its people.Most of it is manufactured by the ‘Contact’ process in which sulphur dioxide is oxidized over vanadium pentoxide to the trioxide prior to absorption in acid solution and much of the sulphur dioxide is produced by burning the element itself.49 That which is not made directly from sulphur is from the roasting of pyrites (mainly the sulphides of copper nickel lead and zinc) where it is essential for environmental reasons to capture the dioxide.It is not unusual for chemicals and fertilizers to be manufac- tured at the sites of metallurgical smelters for this reason. There are many instances of such large integrated chemicals complexes in operation and under construction including those in Canada Greece and Spain announced during 1980/81.50 New plants for manufacturing sulphuric acid from gypsum are rare and are now only built under special local circumstances for example in Tunisia.51 There is little incentive to build plants specifically to use other raw materials because their capital cost is generally higher but also since sulphur is likely to remain in surplus throughout the 1980’~.~* Despite the Contact process now being very well established progressive improvements are still possible and the average size of unit is also increasing.What is claimed to be the world’s largest a 3100 tons per day single-train plant is expected on-stream in the USA early in 1982.53 Technical improvements in this double-absorption plant include both anodically-protected acid coolers and mist eliminators to protect downstream equipment and control emissions. The most effective way to lower SO emissions is by use of the double-contact process in which no end-gas purification is necessary because of the high conversion rate.54 Emission control standards are variable and ‘acid rain’ is very literally an interna- 47 Res. Den Mex. 1981 September p. 13. 48 M. R. Freeman Min. Annu. Rev. 1981 p. 112. 49 A. Phillips in ref. 2 pp. 183-200. Can. Chem. Process 1980 3rd September p.6; Chem. Age 1980 14th November p. 12; Chem. Week 1980 10th December p. 25; Chem. Age 1981 19th June p. 15; Eur. Chem. News 1980 17th November p. 47. ” Chem. Week 1981 14th January p. 43; Chim. Actual. 1981 8th May p. 4. ’‘ Eur. Chem. News 1981 27th July p. 11. 53 Chem. Mark. Rep. 1981 23rd March p. 3; Chem. Eng.,1981 20th April p. 39. s4 Chem. Ind. 1980 October p. 685. Ind us tria 1Inorganic Chemistry 339 tional problem. It has long been discussed in Europe and the Canadians are again protesting about the 6 million tonnes per year which drift across from smoke-stacks in the USA; much comes from electricity generating stations and sulphuric acid plants are by no means the main cause but one copper smelter in Ontario emits 2500 tonnes each day." Thermal efficiency is often crucial to the economics of a sulphuric acid plant and much use is made of by-product steam for power generation and process heating.A 13 000 kW turbo generator is being built integrally with a 2000 ton per day acid plant in Florida; the acid will be used to make ammonium phosphate the power sold to the power company in Tampa and water consumption will also be reduced.56 More modest energy savings are possible by installing improved coolers in which boiler feed-water is ~re-heated.~~ A specialist contractor has developed a double-contact double-absorption process which is claimed to save 40% in heat-transfer In addition to specific installations designed to recover sulphuric acid from fuel-fired power stations for which the merits of the magnesium oxide desulphurization have been rep~rted,'~ there is increasing attention to recycling it from other wastes.At one large chemical plant in Germany both hydrogen sulphide and carbon disulphide-containing gases are burnt to sulphur dioxide;60 in another waste acid with higher-than-usual organic contaminants is regenerated via enamelled steel concentrators after which most of the organics are removed in a corrosion-resistant quartz oxidation reactor before nitric acid treatment.6' Yet another German process separates purification and concentration stages.62 The use of tantalum and other corrosion-resistant materials reduces maintenance. An Israeli process claims to recover mineral acids at unexpected concentration levels by solvent e~traction.~~ Indicative of states of the economy sulphuric acid production in Western Europe was 24.45 million tonnes in 1980,64compared with 27.65 in 1978 and 28.4 in 1979.65Corresponding figures for the USA were 41.3,42.2,and 43.2 million short tons66 and 40.9 is forecast for 1981.67Use patterns vary according to region for example whereas 62% of US 1980 sulphuric acid production went into fertilizers68 (and more than 90% of this was for phosphoric acid) only 36% of European 1980 production was used in this way.69 In the same year the UK used only 30% of its total consumption for fertilizers and remarkably whereas the total of all uses was down by 5.6% on 1979 that for soap and detergent manufacture increased by 15.2Yo .'' " New Sci.1981 8th January p. 51; Chem. Mark. Rep. 1981 6th April p. 7. " Chem. Mark. Rep. 1981,27th July p. 4; Chem. Eng. News 1981,7th September p. 18; Chem. Eng. 1981,7th September p. 33. " Chem. Age 1981.27th February p. 13; Engineer 1981 19th February p. 16. 58 Chem. Eng. 1981 15th June p. 19. 59 Mod. Paint Coat. 1981 May p. 88. Chem. Ind. Berlin 1980 November p. 757. 61 Chem. Eng. 1981 4th May p. 18. '' Eur. Chem. 1981 No. 25 p. 4. 63 Innovation 1981 August p. 4. 64 Chem. Age 1981 10th April p. 22. 65 Br. Sulphur Corp. Stat. Suppl. 1981 February p. 4. 66 Chem. Purchas. 1980 November p. 61. " Chem. Eng. News 1981 15th June p. 9. " Chem. Eng. News. 1981,lSth June p. 8; Chem. Purchas 1981 August p. 63. 69 Chem. Age 1981 10th April p.22. 'O Eur. Chem. News 1981 23rd February p. 14. 340 R. Thompson 5 Other Sulphur Compounds Second to sulphuric acid in terms of tonnages made is sodium sulphate of which world production was 5.9 million short tons in 1979 and expected to rise to 6.2 miliions in 1985.71 Production in the USA is likely to exceed requirements through to the end of this century,72 despite some current tightness in demand.73 Uses in that country include sulphate pulping (48%) and in detergents (39%). Demand for the higher-priced technical grade sodium sulphate (decahydrate) for detergents is expected to surpass that for salt cake (anhydrous) in the paper industry by 1982.73 Detergents took 41% of Japanese Glauber’s salt production in 1980 by far the largest single use there.74 Although much sodium sulphate production is by-product specific plants are under con~truction.~~ US production of sodium sulphite in 1980 was 150 000 tons expected to grow by 1985 to 168 000 About 60% is used in sulphite pulping 15% in boiler water treatment and 12% in photography.An electrolytic process for a product suitable for pulp bleaching has been developed in and a more conventional plant opened in the USA.78 Capacity for sodium hydrosulphite (dithionite Na,S,O,) was also increa~ed:~’ manufacturing details of the alternative processes were described.” A new plant installed in Holland for the production of sulphur dioxide involves cracking sulphuric acid at 1200°C81 but more usually the oxide is a by-product of other operations such as sulphide roasting.” Hydrogen sulphide can be both a nuisance and a valuable source of sulphur.A new industrial process has been developed whereby HzS gas is reacted with SO discharges from a coal-fired power station to make pure elemental Of longer-range interest is a colloidal cadmium sulphide-ruthenium dioxide catalyst in alkaline solution that dissociates hydrogen sulphide in visible light.84 A US oil company is sponsoring development of a process in which activated carbon removes the gas as sulphur from a geothermal stream although the life of the carbon on recycle remains to be Sodium hydrogen sulphide (NaHS) growth in demand is forecast as negligible its main use in ore flotation being likely to grow but its other applications (mainly as a leather depilatory) declining.86 Demand for thionyl chloride is increasing and a 7500 ton per year plant began operation in the USA.87 71 Miner.Facts Probl Prepr. 1980 p. 4. 72 Miner. Facts Probl Prepr. 1980 p. 15. ’)’Chem. Mark. Rep. 1980 17th November p. 9. 74 Jpn. Chem. Week 1981 5th March p. 7. 75 Eur. Chem. 1981 June p. 89; J. Commerce 1981,29th June p. 10a. 76 Chem. Mark. Rep. 1981 13th April I;. 9. ” J. Commercio 1981 13th May p. 1. Chem. Mark. Rep. 1981 6th July p. 7. 79 Chem. Mark. Rep. 1981,4th May pp. 7 58. L. C. Bostian in ref. 3 pp. 59-73. Ned. Chem. Ind. 1981 13th May p. 6. 82 Chem. Age. 1981,13th February p. 5; Eur. Chem. News 1981,2nd February p. 6. 83 Chem. Can. 1981 January p. 21. 84 Chem.Eng. News 1981,20th July p. 28. Chem. Eng. News 1981,7th September p. 30. 86 Chem. Mark. Rep. 1981 2nd February p. 9. Chem. Week 1981 22nd April p. 17; Chem. Purchas. 1981 May p. 11. Industria1 Inorganic Chemistry 341 6 Industrial Gases The relative usage of inorganic industrial gases is well illustrated by US production statistics for 1980." In billions of cubic feet they are oxygen 475; nitrogen 480; carbon dioxide 4060; hydrogen 100; and high-purity argon 10. Not only was carbon dioxide production an order of magnitude greater than any of the others but it had the fastest growth (up from 3181 in 1978). But hydrogen because of its potential demand as a fuel and a wide variety of possible production routes received by far the most research and literature attention.Hydrogen.-There are broadly five basic methods for hydrogen production methane reforming; electrolysis of water; chemical and thermochemical; photo- chemical; and biomass. Catalytic steam reforming of methane is currently the least expensive method in the USA with abundant natural gas a~ailable;'~ purities up to 99% are possible from the partial oxidation of heavier oils and coal which is predicted to take second place. A UK company needing hydrogen to reduce fatty acids to detergent alcohols is replacing its electrolytic plant with a methane- reforming unit capable of 900 cubic metres per hour." Conversely where ample electrical power is available the electrolytic process is preferred and one Canadian company is considering a natural gas-derived hydrogen plant." The specification is to use 100 MW per hour to electrolyse 21 cubic metres per hour of demineralized water to produce 46 tonnes per day of hydrogen and 368 tonnes of oxygen.It has been estimated that France could produce 3 billion cubic feet of electrolytic hydrogen equal to a 20% market share by 1990.92 Research is continuing in Japan into electrolytic hydrogen production using a solid polymer electrolyte instead of ion-exchange membrane processes.93 Work there has also included a ther-mochemical method based on hydrogen and oxygen separation in a gas furnace in the presence of iodine nickel and sulphur One thermochemical cycle developed in the USA involves reaction of manganese(11) titanate with sodium hydroxide and steam at 400-500 "C hydrolysis of the spent mixture at 80 "C yields sodium manganite and hydrous titanium dioxide which when treated with steam at 600 "C generates manganese titanate sodium hydroxide and oxygen.95 Another uses the reaction between cadmium and water the hydroxide being dehydrated to CdO which is then dissociated thermally to the metal for recycle (see ref.277). Photochemical processes designed to generate hydrogen from water and organic substances in the presence of titanium dioxide are receiving attention. It is claimed that a powder of this compound as a semi-conductor changes photo-energy into chemical energy at normal femperat~res.~~ One version uses pellets of a catalyst comprising titanium dioxide ruthenium oxide and platinum which under Kfine SA 1980 p.140. 89 Chem. Eng. News 1981 31st August p. 39. 90 Chem. Age 1981 10th April p. 14; Chem. Znd. 1981 18th April p. 258; Soup Cosmet. Chem. Spec. 1981 May p. 126a; Munu. Chem. Aerosol News 1981 October p. 71. 91 CPIManug. Sera 1980 15th December p. 3; Can. Chem. Process. 1981 13th February p. 10. 92 Inf. Chim. 1981 February p. 115. 93 Jpn. Chem. Week 1981 20th August p. 3. 94 Jpn. Chem. Week 1980 30th October p. 1. 95 Chem. Eng. News 1981 13th July p. 16; US P. 1981,4 276 279. 96 Jpn. Chem. Week 1980 16th October p. 1. 342 R. Thompson illumination oxidizes carbon to carbon dioxide and releases hydr~gen.~' The light and dark sides of the pellets act as positive and negative electrodes of a cell. Illumination with sunlight generates positive holes that oxidize e.g.methanol to carbon monoxide and simultaneously the electrons in the conduction band reduce protons in solution to form gaseous hydrogen in high quantum yield. It is suggested that the carbon may be in a heavy hydrocarbon fuel oil coal or even garbage but a 3% conversion of solar energy is all that is claimed. In another version colloidal titanium dioxide is doped with niobium pentoxide and loaded with platinum and ruthenium pent~xide.~~ Several sensitizers including amphilitic surfactant deriva- tives of tri~(2,2~-bipyridine)ruthenium(11) are being As hydrogen and oxygen are generated in the same vessel during photolysis the mixture is potentially explosive and it is necessary to separate them especially when generating large volumes commercially.One way is to use selectively permeable membranes but that preferred is a bifunctional redox catalyst a semi-conductor such as titanium dioxide microspheres coated and sensitized as described.99 The most promising results are said to have been obtained with an aqueous suspension of strontium titanate loaded with rhodium; the system is completely inorganic and no organic sensitizer or electron relay agent is needed.99 A novel method announced in the USA claimed hydrogen liberation from water by interaction with nitric oxide.100 Because of side-reactions with water the gas is made to react with metaphosphoric acid at 300 "C giving hydrogen and nitrosyl metaphosphate; addition of water allegedly regenerates the starting materials without use of high-grade energy.Reference has already been made to a photochemical dissociation method involving hydrogen ~ulphide.~~ Green plant photosynthesis and the use of algae to produce cheap hydrogen from water are being studied in the USA with some hope of avoiding the many acres of equipment to be exposed to sunlight in order for the method to become In a three-step process the first uses a Chlorellu pyrenoidosu green algae to convert carbon dioxide and water to glycolate and oxygen. A glycolic oxidase enzyme (derived from spinach) then converts the glycolate and some of the oxygen to hydrogen peroxide and glyoxylate. These react to form carbon dioxide water and formate and the formate is finally broken down into hydrogen and carbon dioxide using formic hydrogenylase a bacterial enzyme complex.In other biomass-related work glucose was used as a depolarizing agent in water electrolysis reducing cell voltage from 2.0 to 0.7 V."* Glucose can also be converted into hydrogen photochemically employing photochemical diodes but still very much on a laboratory scale in this case.''* Much is still being written about the 'hydrogen economy' and the use of hydrogen as a fuel not only as an alternative to hydrocarbon fuels but as a much cleaner and less polluting one.'O3 Storage which in the case of use in aircraft must be 97 Chem. Age. 1981 15th May p. 18; New Sci 1980 16th October p. 159. 98 Chem. Eng. News 1981 27th April p. 16. 99 Chem. Eng. News 1981 19th January p.64. IfloChem. Week 1981,2nd September p. 58. lo'Mech. Eng. 1980 October p. 49; Chem. Week 1980 24th December p. 22; Sol. Energy Dig 1981 February p. 4. lo' Alternative Energy Trends Forecasts 1981 August p. 1. lo3 Technof. Forecasts Technal. Surv. 1980 November p. 9; Pet. Econ. 1981 January p. 26; Gaz D'aujourd'hui 1980 March p. 93; Mech. Eng 1981 May p. 24; Mach. Des. 1981 23rd July p. 10. Industrial Inorganic Chemistry 343 refrigerated is possibly a greater problem than generation. One idea is storage in a more dense form but not under high pressure by diffusion in a metal matrix for example a 500 kg cell using coarse magnesium powder has been developed said to be sufficient to propel a car for 300 km.lo4 The more realistic forecasts suggest that hydrogen will not be used as an automotive fuel this and looking farther ahead although by the year 2025 some 85% of all hydrogen produced will be used in the energy industry this will comprise 69% for synfuels and refinery production and only 16% as a direct fue1.'06 But by 1990 NASA will be running forty shuttle flights per year and using thirty times as much hydrogen annually as it does now.lo7 The shuttle consumed some 200 tons of liquid hydrogen in 1980 increasing to 6500 tons in 1990.Overall US production of hydrogen fell 3.2% in 1980. Of its down-to-earth uses some 63% goes into chemical processing for plastics pesticides and chemical intermediates and 37% into metal processes.'o8 It is interesting to note that in Britain the 28 000 tons of hydrogen produced annually as a by-product from the million tons of chlorine is far more than the demands of the industrial gases market."' Oxygen.-Oxygen nitrogen argon helium and neon are separated by fractional distillation of liquid air although not necessarily all at the same time.While this method which replaced Brin's process many years ago is by far the most general differential absorption and differential permeation processes are coming into use for smaller plants. '09 The pressure-swing adsorption ('PSA') process is best suited to the production of concentrated (rather than pure) oxygen and nitrogen and has the advantage of using less energy.'" About 60% of the cost of oxygen production is energy mostly electrical."' Production in the USA fell in 1980 largely because of the depression in the steel industry but even though steel production is declining some esiimates give an annual rate of production increase as 11%during the 1980's compared with only 4% during the 1970's."* US cryogenic plants ran at only 62% of capacity during 1979.Commercial ozonisers which mostly function on the electric discharge principle are becoming more readily available. A German com- pany is to supply a 60 kg per hour plant to the USSR."3 This will be fed with 3000 cubic metres per hour of air in six units and the output will be used to purify 600 cubic metres per hour of waste water. Excess ozone will be removed catalyti- cally. Nitrogen.-Maintaining a balance between nitrogen and oxygen supply and demand is somewhat analogous to the chlorine-caustic soda problem.Air separation is of its nature at best an on-site operation and transportation or storage of the liquified gas not immediately required can be expensive. Scale-factor is still important but it is believed that smaller localized plants will be developed to run economically '04 Engineer 23rd October p. 9. 105 Automot. Eng. 1981 August p. 69. Io6 Chem. Eng.News,1981,24th August p. 21. lo' Chem. Mark. Rep. 1981 13th April pp. 3 36. lo' Chem. Eng.News,1981,27th July p. 19. lo9 W. J. Grant and S. L. Redfearn in ref. 2 pp. 273-301. 'I0 Jpn. Chem. Week,1981,13th August p. 1; Chem. Econ. Eng.News,1980 November p. 40. 'I1 Chem. Eng.News,1981,27th July p. 16. Chem. Mark. Rep.Chem. Bus.Suppl. 1981,4th May p. 17. Eur. Chem 1981 No. 3 p. 28. 344 R. Thompson they will gain by saving the energy that would have been used for liquefaction before tran~portation."~ PSA plants already go some way to meeting this require- ment.'" Large cryogenic plants for the production of liquid nitrogen are under construction at oil and gas production fields for which use technology has also had to be developed to separate the natural gas-nitrogen mixture.'15 It has also been observed that the addition of nitrogen can reduce ten-fold the corrosion rate of drilling fluids on pipes used in geothermal wells and that the cost of making this saving would be halved again if the nitrogen were produced on site.116 Portable equipment to generate nitrogen from diesel engine exhaust gases is also being developed."6 World consumption of nitrogen rose 6% in 1979-1980 to 58 million tons demand having doubled since 1970.117 Rare Gases.-Argon is the most important of the rare gases industrially very largely because of its relative abundance and economy of separation from liquefied air.It is present at the 10-12% level in the concentrated argon fraction of an air still the rest being mainly oxygen.'09 It is also economic to recover it from residual gases which have an argon content of up to 20% .l18 Like argon helium is separated by liquefaction processes and a 250 million cubic foot per year plant is under construction in the USA."9 By contrast mixtures of xenon and krypton have been separated photochemically by selective formation of their fluorides.lZo Sufficient fluorine is introduced to the noble-gas mixture for all of the xenon to react with photochemically-produced fluorine atoms under temperature and pressure condi- tions at which only the xenon can react. XeF2 crystals precipitate from which xenon can be recovered at 99.99% purity. Xenon is easily liquified with a high critical temperature and as it is optically transparent in the ultraviolet visible and infrared regions (and also has wide solubility powers for hydrocarbons etc.) it has been suggested as an ideal solvent for use by spectroscopists.121 Carbon Dioxide.-In the steam-reforming process for ammonia production one mol. of carbon dioxide is produced for every mol. of methane cons~med.~' This gives rise to problems of ammonia-carbon dioxide imbalance and when ammonia production is down the supply of carbon dioxide can be short as this has been its major source.Growth in demand for ammonia has also been much slower.122 US production of carbon dioxide was 3.54 million tons in 1980.122 Fermentation long a traditional source is thus gaining in importance and among new developments are a 350 tons per day unit in Indiana,lz3 associated with an ethanol-from-corn synfuels plant due in 1983 and one in Alabama that has recently come on-stream Chem. Age 1981 19th June p. 18. 'I5 New York Times 1980 7th November p. 5; Chem. Murk. Rep. 1980 10th November p. 5; Chem. Eng. News. 1980 17th November p. 13; Chem. Week 1980 12th Novemberr p.13; J. Commerce 1980 10th November p. 11; Chem. Week 1981 21st October p. 19; J. Commerce 1981 18th October p. 10a. Chem. Eng. 1981 29th June p. 18. Chem. Murk.Rep. 1980 3rd November pp. 5,29. Chem. Ind. (Berlin) 1981 January p. 48 Chim. Actual. 1981 27th February p. 16. 'I9 Solid State Techno/. 1981 April p. 24. "O Chem. Eng. News 1981,7th September p. 68. New Sci.,1981 24th September p. 796. "' Chem. Eng. News 1981 27th July p. 18. lZ3 Chem. Week 1980 5th November p. 9; Chem. Eng. News 1980 1st December p. 13. Industrial Inorganic Chemistry 345 at 300 tons per day.124 Some carbon dioxide occurs naturally in sufficient amount for commercial exploitation and sometimes conveniently close to an oil field.'25 Tertiary oil recovery from old oil fields is one of the major reasons for the growth in demand for carbon dioxide12' but requirements of the convenience food industry are also growing.124 One of the technical problems of use in the oil industry is separation from hydrocarbon gases an area where hollow fibre membranes are being commercialized.'26 7 Hydrogen Peroxide and Persalts The projected increase in demand for hydrogen peroxide in the USA where it is forecast to grow at 8-lO% per annum to 1985 owes much to the paper and pulp industries that now take 20% of the total 130 000 tons per annum prod~ction.'~' One of its attractions is that no residue is left after use which makes it especially acceptable environmentally for the bleaching of both chemical and mechanical pulp; demand increases as more higher-quality paper is produced e.g.in Finland.Iz8 Increased recycling of waste paper is also likely to increase demand but about one-third of the usage in the USA is now in markets that were non-existent six years However hydrogen peroxide is one chemical of which the USA is not necessarily the biggest consumer due largely to the widespread use of perborates as bleaches in domestic washing powders in Sodium percarbonate also made from hydrogen peroxide but somewhat less stable than the perborate is employed ~imilarly,'~' and whiteners and bleaches based on the product are being launched in the USA.13' A plant to produce 20000 tons per year of hydrogen peroxide by French technology is to be built in Japan.133 Capacity for making sodium persulphate is to be raised to 20000 tons by a US man~facturer.'~~ Traditionally used as a bleaching and oxidizing agent and as an initiator for emulsion polymerization the persulphate is finding new applications as diverse as in mineral refining and as an etchant to remove copper in the production of printed circuit boards.8 Halogens Fluorine and Compounds.-Hydrofluoric acid sodium fluoride and fluorocarbons account for most of the value in fluorine chemicals production fluorspar (CaF2) being the most usual basic source. Just over half of that mined is 'acid grade' (as distinct from metallurgical grade) required for the manufacture of hydrofluoric 124 Chem. Mark. Rep. 1980 17th November p. 5. 12' Oil Gas J. 1980 17th November p. 48; Chem.Week 1980,3rd December p. 13; Chem. Eng. News 1980,24th November p. 34. 126 Chem. Mark. Rep. 1981,6th April p. 75. J. Commerce 1981 24th June p. 10a; Chem. Purchas 1981 October p. 23. Eur. Chem. News,1981 13th July p. 24. 129 Chem. Week 1981 30th September p. 35. 130 R. Thompson in ref. 2 pp. 302-319. C. A. Crampton G. Faber R. Jones G. P. Leaver and S. Schelle in ref. 2 pp. 232-272. 132 Chem. Mark. Rep. 1980 24th November p. 58; Chem. Week 1980 26th November p. 21. 133 Inf. Chim. 1980 October p. 85. 134 Chem. Mark. Rep. 1981 4th May p. 5; ibid. 1981 14th September p. 7; Chem. Week 1981 6th May p. 35; ibid. 1981 16th September pp. 1-19; News Release 1981,9th September p. 1; Electron. News. 1981 11th May p. 55; ibid. 1981 21st September p. 52; J.Commerce 1981 29th April p. 10; Chem. Eng. News,1981 27th July p. 20; 1981 2nd November p. 16. 346 R. Thompson acid.135 Construction began on a new plant to produce 10 000 tonnes per annum of the anhydrous product in the UK’36 and a somewhat smaller one in the USA.13’ More than half of the total production of hydrofluoric acid in Japan is for the production of fluorocarbon (where it is known as ‘Flon’).13’ Two new plants (one of which will have a capacity of 20 000 tonnes per annum) will be for Flon-113 and an existing operation will be expanded.139 An azeotropic mixture of Flon-13 snd Flon-23 called Flon 503 has been developed for use as an ultra-low tem- perature refrigerant.14’ Much of the Flon usage is in air conditioners. The US pioneer DuPont has further developed its range and claims superior performance for a mixture of Freon 13B1 and R-152A for a heat pump to extract heat from ‘cold’ outdoor air.’41 An important outlet for hydrofluoric acid in the developed world is for uranium hexafluoride production (for isotope separation).A French plant to process 18 000 tonnes per annum of waste UF6 gas into uranium oxide and hydrofluoric acid is scheduled to become operational in 1984.14’ Bromine and Iodine.-The recovery of bromine from its major sources in brines and seawater has been reviewed e1~ewhere.I~~ World elemental bromine production in 1979 was 380000 short tons of which two-thirds was in the USA and with Israel the second largest pr0d~cer.l~~ US sales showed a 27% increase in tonnage compared with the previous year,’45 but fell back again by 22% in the following year mainly owing to environmental regulations reducing the lead content (where permitted at all) of gasoline from 3 g to 0.5 g per US gal10n.I~~ Nevertheless 100000 tons of ethylene dibromide were used.The second largest use is of organo-bromine compounds as flame retardants of which almost as much is now used. 145,147 At 330000 tons per annum there is now more than ample bromine production capacity in the USA.14* Most developments are in the flame retardant and pesticides fields but a very minor one of interest to spectroscopists is a new grade of stabilized KBr having almost perfect transmission and avoiding the water band. 149 Production and consumption statistics €or iodine and its compounds are most readily available for the USA although the pattern of use is probably reflected in other developed countries.Overall annual consumption remains fairly static at around 4000 tons of which the resublimed element accounts for only about 300 tons. About one-quarter of consumption is in catalyst manufacture and almost 135 H. C. Fielding and B. E. Lee in ref. 2 pp. 149-168. Chem. Age 1981 15th May p. 5; Eur. Chem. News 1981 25th May p. 24; Chim. Actual. 1981 5th June p. 11; Manu. Chem. Aerosol News 1981 August p. 7. 13’ Electron. News 1981 7th September p. 60. 13’ Jpn. Chem. Week 1981 28th May p. 6. 139 Jpn. Chem. Week 1981 29th January p. 7. 140 Jpn. Chem. Week 1980 11th December p. 1. 14’ Air Conditioning Heating Refrigeration News 1981 2nd February pp.1,4. Usine Nouv 1981 23rd April p. 87. 143 R. B. McDonald and W. R. Merriman in ref. 2 pp. 168-192. 144 Miner. Ind. Surv. Bromine 1980 18th August p. 9. 145 Min. Znd. Surv. Bromine 1980 18th August p. 1. 146 J. Commerce 1981 29th June p. 10a. 14’ Chem. Week 1981 25th March p. 26. 14’ Chem. Purchas. 1981 July p. 40. 149 Opt. Spectra 1981 July p. 48. Miner. Yearb. Prepr. 1979 p. 3; Chem. Purchas 1981 April p. 54. Industrial Inorganic Chemistry as much goes into animal feed.151*152 Supplies currently are tight with the USA a net importer and the biggest growth area is seen to be in catalysts used in the production of chemicals from ~oal.”~*~’~ Incentive for increased US capacity led to plants for the annual production of 120-160 tonnes of iodine from oil brine in Oklah~rna,”~ 500-1000 tons in California,”’ and 1500 tons at an undisclosed l~cation.”~ Japan has problems of having iodine sources but being unable to exploit fully for local environmental reasons.’57 Research has led to more powerful germi- cides and sanitizers enabling less of the costly iodine to be u~ed.”~~”~ One of these is described as a nonylphenoxypoly(ethy1eneoxy)ethylene-iodine complex.159 9 Boron The boron products industry is reviewed else~here.’~~,~~~ Total production of boron minerals and direct compounds in the USA for 1980 is reported as 1.57 million short tons equivalent to 783 000 tons of B203 contained.16’ This is forecast to rise to 954000 tons in 1985.’62Energy conservation (use in thermal insulation) has increased demands but this market is approaching saturation.The USA is the major producer of borates from deposits in California and 40% is exported.’62 A 200000 tons per annum plant to manufacture boric acid directly from sodium borate ore was brought 0n-st~eam.l~~ The manufacture and uses of sodium borohy- dride and its derivatives were well reviewed. 164 Sodium borohydride itself whose principal use is in the bleaching of paper pulp was described as cost-efficient in the purification and stabilization of soap. 16’ 10 Aluminium The production and use of aluminium compounds were reviewed.166 By far the most important commercially is the oxide made from bauxite by the Bayer process and used as feedstock for aluminium refining by fused salt electrolysis.Production is on a very large scale often close to ore deposists and frequently by consortium companies in order to share the vast costs for example at a plant in Queensland Australia where capacity is being extended to 2.75 million tons per ann~m’~~ and 15’ Chem. Week 1980 12th November p. 44; Chem. Purchas. 1981 April p. 54. 15* News Release 1980,6th November p. 1; Chem. Week 1980 12th November p. 44. Chem. Purchas. 1981 April p. 53; J. Commerce 1981 31st July p. 9a. lS4 Jpn. Chem. Week 1981 18th June p. 2; ibid. 1981 3rd September p. 8; J. Commerce 1981 17th July p. 5a; Jpn. Econ. J. 1981 11th August p. 14; Chem. Purchas. 1981 August pp. 14 18. Chem. Eng.1980 17th November p.65; Soap Cosmet Chem. Spec. 1980 November p. 100. News Release 1980 27th October p. 1; Chem. Mark. Rep. 1980 3rd November p. 7; Chem. Eng. 1981 26th January p. 36. 15’ Min. Ind. Suro. Iodine 1980 11th July p. 1; Jpn. Chem. Week 1981 5th March p. 7; ibid. 1981 16th April p. 7. J. Commerce 1981 16th June p. 10a; Household Personal Prod. Ind.,1981 August p. 73; USP 4 271 149. lS9 Chem. Purchas. 1981 April p. 96. P. A. Lyday Miner. Yearb 1980 ‘Boron’ US Bureau of Mines. Miner. Muter. Month. Suru. 1981 June p. 3; Miner. Ind. Suru. Boron 1980 31st December p. 1. Chem. Mark. Rep. 1981 30th March p. 9. Chem. Eng. 1981 1st June p. 17. R. C. Wade in ref. 3 pp. 25-58. 16’ Chem. Purchas. 1981 August p. 85. 16‘ K. A. Evans and N. Brown in ref.3 pp. 164-195. Aluminium 1981 March p. 257; ibid. 1981 April p. 319; ibid. 1981 August p. 589. 348 R. Thompson in Jamaica where it was to be doubled to 0.96 million,'68 although one partner in this venture later had second th0~ghts.l~~ There was similar reconsideration by an Italian consortium170 and in Indone~ia,'~' while an Irish group faced rising Considerable confidence is needed to expand capacity while the state of the metal market is depressed. Requirements by the electronics industry led to the develop- ment of processes for higher-purity alumina in Japan173 and an alumina hydrate plant in Germany is to be doubled to meet catalyst needs in oil refining.'74 Capacity for aluminium sulphate used extensively in paper manufacture and for water treatment increased notably in Japan,175 India,'76 and Me~ic0.l~~ A plant to produce 20000 tonnes per year of aluminium fluoride is to be built in Jordan to use indigenous by-product fluorsilicic acid (from phosphate operations) along with imported aluminium hydr0~ide.I~~ One twice that size is planned for Canada to feed local aluminium smelters with the fl~0ride.l~~ A joint operation in West Germany will produce a range of speciality aluminium chemicals.'80 The Western World's annual consumption of aluminium alkyls now exceeds 20 000 tonnes,181 although their use in high-density polyethylene production has fallen (but not in polypropylene polymerization).Alkyl aluminium hydrates are mainly used as reduc- ing agents the di-isobutyl derivative being usefully soluble in hydrocarbons (in contrast to lithium aluminium hydrate).11 Silicon The sodium silicates produced by the fusion of quartz sand with caustic soda soda ash or other sodium salts and their derivatives such as precipitated silica are major products of the inorganic chemicals industry. la2 World actual production of precipi-tated silica now exceeds a quarter-of-a-million tonnes annually mainly for rubber reinforcement.lS3 West European capacity for synthetic silicic acid is elsewhere quoted at this figure half of it being in West Germany where a new 18000 tonnes per year unit is being built in association with a 60000 tonnes sodium silicate plant.'84 It has long been realized that certain vegetable matter accumulates silica with rice being a particularly good concentrator.In certain developing countries such as India this can be an attractive 16' Aluminium 1981 March p. 263. Aluminium 1981 August p. 590. 170 Eur. Chem. 1981 No. 18 p. 306. 17' Aluminium 1981 April p. 319; ibid. 1981 June p. 451. 17* Aluminium 1981 March p. 263. 173 Aluminium 1981 April p. 317; Jpn. Chem. Week 1981 11th June p. 3. 174 Aluminium 1981 April p. 319; Eur. Chem 1981 No. 7 p. 108. 175 Jpn Chem. Week 1981 5th February p. 7. 176 Chem. Age 1981 31st July p. 13. 177 Chem. Mark. Rep. 1981 2nd February; Chem. Week 1981 4th February p. 13; Chem. Age 1981 6th February p. 4; Chim. Actual 1981 13th February p. 11. Eur. Chem. 1980 No. 34 p. 601; ibid. 1981 No. 13 p. 220. 179 Am. Met.Mark. 1981 18th June p. 5. Eur. Chem. 1981 No. 24 p. 405. '" Chem. Ind. (Berlin) 1980 November p. 738. ''' D. Barby T. Griffiths A. R. Jacques and D. Pawson in ref. 2 pp. 320-353. 183 Elastomerics 1981 August p. 40. Eur. Chem. 1981 No. 23 p. 390; Farbe Lack 1981 September p. 809; Seifen Ole Fette Wasche 1981 17th September p. 493. Eur. Chem. News 1981 12th January p. 24. Industrial Inorganic Chemistry 349 Fumed silicas although more costly are much more attractive than precipitated silica as fillers for plastics and rubbers largely on account of their high surface area. They are made by the flame hydrolysis of silicon tetrachloride and production methods and uses were described in some Conventional precipitated silicas with low salt (sodium sulphate) content were found to provide economical reinforce- ments for silicone rubber when used to dilute fumed silica.187 The silicone filler market is especially well served by fumed ~ilica.~~~*"~ A thixotropic gel formed by the dispersion of fumed silica in silicone oil has been developed to protect fibre cables from It is claimed to require no vulcanization or heating have an unlimited pot-life and be particularly useful in connection with fibre optics.US and West German companies appear to dominate this field. Capacity in the USA is now 20 000 tons per annum and demand there is expected to increase by 50% by 1985;188,190 hence several announcements of new ventures often by subsidiaries of German c~mpanies.'~~-'~~ One company compacts its vapour-phase hydrolysis product into shapes that can subsequently be fused to make optical components and microwave The cheapest grades of all siliceous fillers and adsor- bents are the natural or mineral products.Total consumption by the plastics industry is estimated to reach 3.5 million tons by 1985 with a growth rate of 15% per year.192 The growth for surface-modified silicas (in which treatments increase the bonding strength with the plastics or rubber matrix) will increase even faster at 25%. The overall objective is to use less of the increasingly scarce and expensive petrochemically-derived materials without detracting from the desired properties of the end-product. Fine grinding can substantially increase the usefulness of silica mine~a1s.l~~ One of the most important of these extracted products is Fullers Earth which finds greatest use in the catalyst and adsorbent fields particularly for the purification of oils and Important as naturally-occurring zeolites are much attention is being given to their synthesis.Mineral zeolites were used for water- softening before the advent of ion-exchange resins and in recent years the exchange property of particular alumino-silicate structures has been exploited again. The incentive has been the need to replace polyphosphates as detergent builders on environmental pollution grounds. Finely-divided zeolites (natural but mainly syn- thetic) in admixture with sodium perborate and a biodegradable synthetic detergent increasingly provide the basis of domestic washing powders; the soil-suspension agents take care of the removal of spent zeolite powder along with the dirt in the wash water and no problem is created in sewage systems.The zeolite thus takes over from phosphate the role of calcium ion sequestration although its ability to accept magnesium ions is more limited. Construction of plants to make these zeolites P. Kleinschmit in ref. 3 pp. 196-225. Rubber Plast. News 1981 31st August p. 20. *'' Rubber Plasr. News 1981 20th April p. 8. 189 Laser Focus 1981 February pp. 56 58. 190 Chem. Mark. Rep. 1981 6th April p. 5; Soap Cosmet. Chem. Spec. 1981 April p. 95; Chem. Purchas 1981 April p. 14. I9l Rubber Plast. News 1980 10th November p. 7; Chem. Mark. Rep. 1981 10th November p. 7; ibid. 1981 23rd February p.7; Chem. Eng. News 1980 1st December p. 13; Am. Paint J. 1981 11th May p. 58; News Release 1981 4th February p. 1; Electron. NPWS 1981 4th May p. 133; Chem. Eng 1981 20th April p. 54. 192 Plast. Eng 1980 October p. 13. 193 Eur. Chem. News 1981 11th May p. 17; Soap Perfum. Cosmet 1981 July p. 365. 350 R. Thompson has been announced in Italy,’94 Japan,195 USA,196 and West Germany.I9’ A principal German plant will be capable of 85 000 tonnes per year.19’ Although this detergent- builder application is attracting current attention the considerable and developing usage as a metal-exchanged heterogeneous catalyst in the petroleum products industry should not be Zeolites also have qualities suitable to their use as an adsorbent for animal feed nutrients but an ‘other end’ application has been found droppings from zeolite-fed chickens contain 25 YO less moisture with less odour less free ammonia and a reduced maggot pop~1ation.l~~ Elemental silicon is an increasingly important item of commerce both in the highly pure form for the electronics semi-conductor and solar batteries industries and in bulk (and not quite so pure) for metal alloys.Heavy investment is planned in Italy for production of both monocrystalline and polycrystalline silicon and wafers,200 with other new plants announced for these grades in Japan201 and the USA.202.203 One of the latter202 will combine locally-available silane feedstock with licenced-in Japanese technology. Japan’s silicon demand was estimated to rise to 75000 tons in 1981 of which about 750 tons is high-purity grade and around one-third is In anticipation of Japan’s continuing need to import silicon a 27 000 tonnes per year plant is being built in Australia; rising energy costs in Japan itself were behind closure of some domestic Although annual world silicon consumption is half-a-million tonnes that in Australia is (perhaps surpris- ingly for an aluminium-producing country) only 6000 rising to 9000 by 1985.A government-backed project for semi-conductor grade will boost this in value if not tonnage.206 Erroneous forecasts of semi-conductor industry’s chip needs and a failure to increase its trichlorsilane capacity could lead to a silicon shortage in the 1980’~.~’~ 194 Chem. Mark. Rep. 1981 23rd February p.4; ibid. 1980 29th December p. 7; Eur. Chem. News 1981 16th February p. 16; ibid. 1981 1st June p. 24; ibid. 1981 15th June p. 6; ibid. 1981 23rd March p. 6; Eur. Chim. 1981 No. 2 p. 8; ibid. 1981 No. 5 p. 67; Chim. Actual. 1981 13th February p. 11; ibid. 1981 20th March p. 16; Chem. Age 1981 13th February p. 10; Chem. Ind. 20th June p. 398; Chem. Ind. (Berlin) 1981 April p. 236; J. Commerce 1981 19th May p. 10; If. Chim. 1981 June p. 36; Soap Cosmet. Chem. Spec. 1981 July p. 80b; Chem. Week 1981 7th January p. 23. 19’ Eur. Chem. News 1981 5th January p. 19; Chem. Mark. Rep. 1981 12th January p. 7; Jpn. Chem. Week 1981 1st January p. 8; ibid. 1981 19th February p. 7; ibid. 1981 27th August p. 27; Household Personal Prod. Ind. 1981 February p.42; Chim. Actual 1981 30th January p. 12; Eur. Chem. 1981 No. 2 p. 8. 196 Chem. Week 1980 5th November p. 39; ibid. 1981 1st July p. 40; Chem. Eng. News 1980 3rd November p. 17; Chem. Eng. 1981 1st December p. 30; Chem. Mark. Rep. 1980 3rd November p. 7; J. Commerce 1980 6th November p. 5; Chem. Purchas. 1981 July p. 13; Soaps Cosmet. Chem. Spec. 1981 July p. 80B; J. Am. Oil Chem. SOC. 1981 August p. 698a. 197 Eur. Chem. News 1981 15th June p. 8; 1981 29th June p. 34. 19* Chem. Eng. News 1981 13th April p. 32. 199 Feedstuffs,1980 27th October p. 9. ’O0 Chim. Actual. 1980 24th October p. 16; Eur. Chem. News. 1980 27th October p. 10; ibid. 1980 10th November p. 10; J. Commerce 1980 18th November p. 5; Chem. Murk. Rep. 1980,24th November pp. 5 21; Chem.Age 1980 31st October p. 6; Eur. Chem. 1980 No. 30 p. 526; ibid. 1981 No. 20 p. 342; Metall 1981 January p. 10. ‘01 Eur. Chem. News 1981 9th March p. 20. *02 Chem. Week 1981 13th May p. 70; Chem. Mark. Rep. 1981 11th May p. 5; Chem. Eng. News 1981 18th May p. 19; Jpn. Chem. Week 1981 14th May p. 6; Chem. Purchas. 1981 July p. 13; Chem. Eng.,1981 15th June p. 40. 203 Chem. Eng. News 1981 9th March p. 25; Wall. St. J. East. Ed. 1981,3rd December p 19. ’04 Jpn. Chem. Week 1981 12th March p. 11; Met. Bull 1981 10th March p. 15. ‘05 Metall 1981 March p. 195. 206 Electron. News 1981 20th July P.X. ’07 Forbes 1980 10th November p. 66. Industrial Inorganic Chemistry 351 Amongst new technology is a fused salt electrolytic process said to be analogous to the Hall process for aluminium using diatomaceous earth as feed-stock and operating at above the 1420°C melting point of silicon.2o832o9 Claims are for a purity of 99.98% Si compared with 98-99% of present metallurgical grade and adequate for solar cells.Costs are estimated in the $1-2 per kg range. Another process under development is via potassium fluosilicate made from the fluosilicic acid by-product of the fertilizer industry.2o8 Production of silicon ribbon was described.' lo Probably best known as an abrasive silicon carbide is becoming increasingly applied to engineering uses such as turbine blades as composition is improved and fabrication methods are developed.211*212 Normally a non-conductor of electricity doping with boron can increase this a hundred-fold.211 The alpha variant can be sintered into complex shapes of more than 96% of theoretical density.212 A manufacturing process for the granules that uses less energy normally a major cost item in reacting silica sand with coke has been deve!oped in the USA.213The energy cost can be as much as 60% of the total and a Dutch manufacturer has begun to use (instead of flaring) the waste heat as well as the by-product carbon monoxide.214 A commercial plant for the production of siiicon carbide fibres for reinforcing aluminium components was under constructior in Japan.215 'Sialons' special ceramics containing Si Al 0,and N have continued to attract world-wide interest for a wide variety of engineering West European annual production of silicones is estimated at 100 000 tonnes compared with 75 000 in the USA; the business is said to be profitable for the small number of companies engaged in it and competition from outside is unlikely because of the high capital costs 12 Nitrogen Sodium cyanide is one of the more important inorganic nitrogen compounds industrially.A new French plant capable of an annual production of 60 000 tonnes of 32% solution was brought on-stream mainly as feedstock for amino-acid production.218 One of the major uses of the salt is in metal mining (for gold extraction and froth flotation) and 5000 tonnes of local production are used each year for this purpose in Canada.219 The importance of this class of chemical is put into perspective by the 1979 West European production of 225 000 tons of hydro- cyanic acid of which only 29 000 tonnes were consumed in the manufacture of the inorganic salts.22o One of the applications of the alkali-metal salts is in the production Alternative Energy Trends Forecasts 1981 July p.1. '09 Chem. Eng. 1981 13th July p. 35; Chem. Mark. Rep. 1981 6th July pp. 7 23; Chem. Week 1981 8th July p. 40; Ind. Res. 1981 October pp. 88 90. 21n NASA Tech. Briefs 1981 No. 1 p. 88. 211 Am. Ceram. SOC.,Bull. 1981 May p. 549. 212 Ceram. Ind. 1981 January p. 21. '13 Chem. Week 1981 22nd July p. 45;Chem. Eng. News,1981 20th July p. 28. 214 Eur. Chem. 1981 No. 26 p. 450. 215 Eur. Chem. News,1981 13th July p. 21. '16 Chem. Age 1981 10th April p. 7. 'I7 Chem. Age 1981 20th March p.12. 'I8 Eur. Chem 1981 No. 12 p. 203; Eur. Chem. News,1981 6th April p. 17; Chim. Actual. 1981 10th April p. 20; Chem. Age 1981 3rd April p. 10; Chem. Murk. Rep. 1981 10th April p. 4. 219 CPIManag. Serv. 1980 17th November pp. 4,s. 22n Chem. Mark. Rep. 1980 10th November p. 40. 352 R. Thompson of ferrocyanides usually en route to Prussian blue pigments but a highly purified form of potassium feroocyanide as an etchant in the electronics industry was announced.221 Otherwise there appears to have been no significant change in this field of applied inorganic chemistry since an earlier review.222 13 Phosphorus Orthophosphoric acid may be produced by either ‘wet’ or ‘dry’ (thermal) pro- ce~ses.~~~ By far the greater proportion is made by the former involving the decomposition of phosphate rock with sulphuric acid (see above Section 3 Inor-ganic Fertilizers).A purer grade is manufactured by the dry process in which the rock is reduced with coke in high-temperature furnaces the phosphorus vapour then being burnt to the oxide which is afterwards dissolved in water. Demand for phosphorus chemicals in the USA is forecast to increase relatively little from 450 000 tons in each of 1979 and 1980 to 465 000 in 1985.224 This stems largely from the trend away from phosphate-based sequestrants in detergents for environ- mental (eutrophication) reasons. The use is banned in some parts of the USA and in certain other countries to which Holland will be added by 1985.225 US demand for sodium tripolyphosphate the form used in most household laundry powder detergents is forecast to grow from 758 000 tons in 1980 to 837 000 in 1984.226 Two factors prevent the growth rate from being less the ‘save-energy’ drive washing in cooler water requiring more phosphate builder; and growth in the dishwashing and institutional detergent markets which are not affected by this legislation.Tetrapotassium pyrophosphate which is highly water-soluble and hence was a popular component of liquid cleaners fares worse halved by 1984 from the 40 000 tons level of 1979.227 Not all countries have or are as concerned with the environmental problem for a 50 000 tonnes per annum sodium tripolyphosphate plant is to be built in Iraq228 and one of 30000 tonnes began operation in Production capacity for sodium hexametaphosphate also a sequestrant for calcium ions but used on a smaller scale and mostly industrially is to be doubled at a Canadian plant.230 There is considerable over-capacity for the tripolyphosphate and it has been estimated that the world-record production level of 1.2 million tons in 1969 will not be reached again until the mid-1990’~.~~~ This will doubtless add impetus to trading in phosphoric acid itself.Only 5% of total US production was exported in 1980,224 against a world trade of 2 million tonne^.'^^ A US-South African consortium has set its sights on 60% of Phosphorus is also shipped as the element223 and technical improvements will enable a Newfoundland plant to increase its capacity by half by 1985.233 Demand for the orthophosphates for Manuf.Chem. Aerosol News,1980 November p. 19. 222 J. B. Farmer in ref. 2 pp. 403418. 223 A. F. Childs in ref. 2 pp. 375402. 224 Chem. Mark. Rep. 1981 9th March p. 9. 22s Chim. Actual. 1980 21st November p. 12. 226 Chem. Mark. Rep. 1980 3rd November p. 9. 227 Chem. Mark. Rep. 1980 1st December p. 9. Chim. Actual. 1981 10th April p. 9. 229 Household Personal Prod. Ind. 1980 November p. 75; Chim. Actual 1980 10th October p. 20 230 Manuf. Chem. Aerosol News,1981 August p. 21. 231 Milling Feed Fert. 1980 September p. 35. 232 Chem. Week 1980 5th November p. 14. 233 Eur. Chem. News,1981 14th September p. 38. Industrial Inorganic Chemistry 353 food additive and other purposes continues and a tricalcium phosphate plant was started-up in the USA.234 Lower-volume industrial inorganic compounds from elemental phosphorus were reviewed in an article of this title.235 Tests in the USA indicate the possibility of using sodium hypophosphite for the preservation of smoked meat products replacing sodium nitrite and thus avoiding possible nitrosamine formation.236 A 10 000 tonnes per annum phosphorus trichloride plant came on stream in France using chlorine from an electrolytic chlorine-soda plant237 and a smaller unit for the tribromide was announced for the UK.238 A new 20000 tons per year plant for phosphorus pentasulphide was started up in the USA239 and an older one Capacity for making phosphine and its derivatives was increased both thereZ4l and in Canada.242 Two companies announced new series of chiral phosphine~.~~~ These compounds are used to prepare transition-metal complexes which can be highly efficient homogeneous catalysts for asymmetric synthesis of optically active compounds at yields over 90%.14 Arsenic and Antimony Arsenic.-Despite its being a nuisance by-product of metallurgical and related industries and being often an emotively more toxic waste than is justified scientifically arsenic and its compounds are in short supply.244 Major use is in wood preservation usually as the established copper-chrome-arsenate (‘C.C.A.’) compo- sition which is cheaper and more acceptable than creosote or pentachlorophenol. Demand for C.C.A. products has increased by 30% per annum in recent years and it is estimated that it will rise 300% by 1990 to 41 000 tons .244 Current annual refining capacity for the trioxide (of which 20% is used in C.C.A.) is 71 000 tons.Other uses are in the glass industry where it is gradually being substituted in cotton production and as a herbicide. Sweden and the USA dominate produc- tion,244*245 with some export from China.246 Efforts are being made to differentiate between various forms of arsenic in relation to its toxicity. Arsenites and the by-products of metal smelting are more toxic than arsenates although certain organic derivatives like methanearsonates and cacodylates are still less Improvements have been made to techniques for monitoring arsenic contents of air involving separation by ion-exchange chromatography followed by conversion uia arsine into the element which is then measured by atomic absorption spec- trophotometry.234 Plust. Eng. 1981 February p. 19. 23s J. C. McCoubrey in ref. 3 pp. 74-97. 236 Chem. Eng. News 1981 30th March p. 16; News Release 1981 7th August p. 1. 237 Inf. Chim 1981 February p. 95; Chim. Actual. 1980 19th December p. 16; Chem. Age 1981 9th January p. 6. 238 Chim. Actual. 1981 5th June p. 14. 239 Chem. Eng. 1981 20th April p. 44. 240 J. Commerce 1981 1st July p. 10a. 241 J. Commerce 1980 13th November p. 5. 242 Eur. Chem. News 1981 6th July p. 23; Corpus Chem. Rep. 1981 22nd June p. 2. 243 Chem. Mark. Rep. 1981 5th January p. 67; Chem. Purchas. 1981 April p. 99. 244 Met. Bull. 1981 17th July p. 17.245 Met.bul1. 1980 19th December p. 21. 246 Met. Bull. 1981 11th September p. 17. 247 Chem. Eng. News 1981 16th February p. 29. 354 R. Thompson Antimony.-Antimony oxide used mainly as a synergistic (with organo-halogen compounds) fire-retardent additive to paints and plastics is the most important compound commercially. Consumption in the USA in 1980 was just over 10 000 and three producers there have announced increases in plant capacity.249 15 Metal Compounds Lithium.-The manufacture and uses of lithium compounds were reviewed.250 Major sources are within the USA but preparations are being made to produce 6000 tons per annum from brines in Chile.25’ Lithium is used to lower energy consumption of aluminium smelters and its inclusion increases throughput by about 10%.About one-third of all lithium produced in the USA goes for this application other major outlets being to the glass and ceramics industries and in the production of greases.252 Magnesium.-The oxides and salts have widespread and high-tonnage uses in the refractories and chemicals industries. These uses and the manufacturing methods available for magnesium compounds were World-production capacity in 1979 was 6.9 million tons of which 1.2 million was in North America and 2.2 million in Dolomite is an important source for steel industry refractory grades and production technology has been Good quality dolomite can be suitable for the production of high-purity oxide and Brines and dried-out salt lakes are exploitable sources when other salts are co-prod~ced;~~~ where none is available locally the routes from sea water are attractive and a 100000 tonnes per annum magnesium oxide plant has been completed in Hol- About one-third of US magnesium oxide production is of ‘chemical’ grade.259 The fastest-growing market there is as a fertilizer additive and animal feed supplement heavy usage of nitrogeneous fertilizers reduces the magnesium uptake causing deficiency in fodder crops and leading to fatal cattle diseases.259 Use of a magnesium chloride solution can reduce nitrogen loss and enhance the effectiveness of urea; a similar material through deliquescence of the compound binds surface soils and reduces dust loss in fields and on dirt roads.260 Fused magnesium phosphate is also used agriculturally and a Brazilian company has raised its annual production to 180 000 tonnes.261 Magnesium sulphonate is used 248 Am.Met. Mark. 1981 10th September p. 7. 249 Chem. Mark. Rep. 1981 25th May p. 5; ibid. 1981 24th August p. 4;Chem. Purchas. 1981 April p. 14. 250 J. E. Lloyd in ref. 3 pp. 98-122. ”’ Ceram. Ind. 1980 November p. 13; Chem Week 1981 21st October p. 87; Chem. Mark. Rep. 1981 19th October pp. 5 38. 252 Chem. Eng. News 1981 19th October p. 10. 253 T. P. Whaley in ref. 3 pp. 123-163. 254 Min. Facts Probl. Prepr. 1980 p. 2. 255 Iron Age Metalwork. Int. 1981 January p. 12; Pit Quarry 1980 November p. 61. 256 Rubber World 1980 December p. 8; Chem. Mark. Rep. 1980 10th November p. 5; Am. Paint J. 1980 10th November p.20; Rubber Plast. News 1980 10th November p. 25. 257 Chem. Ind. (Berlin) 1981 August p. 498. 258 Inf. Chim. 1980 August p. 101. 259 Chem. Week. 1981 7th January p. 43. 260 J. Commerce 1981 16th September p. 10a. 261 Jpn. Chem. Week 1981 13th August p. 2. Industrial Inorganic Chemistry 355 as an anti-rust and detergent additive for engine and construction of a 16 500 tonnes per annum plant in France was announced.26z Copper.-Cuprous oxide production was begun or extended at three separate plants in Japan.263 The intended use is mainly for marine paints. Calcium and Barium.-Apart from calcium sulphate for which the sources are natural the phosphogypsum by-product from phosphoric acid manufacture and the neutralized waste from the sulphate process for titanium dioxide the chloride is in tonnage terms the leading calcium salt.US capacity in 1982 is projected to double the 1980 figure of 1.1 million About 75% is used in snow and ice control but the fastest-growing use is in oil well drilling fluids for which ‘liquid’ calcium chloride of 38% solids content is produced.26s There are civil engineering applications as concrete additives and soil stabilizers266 and food grades are made.267 A plant for the manufacture of 100 tons per day of calcium hypochlorite in the USA was announcedz6* and ‘clean technology’ for the production of a neutral salt with 75-80% active chlorine content was described.25 Barium salts have experienced a severe reduction in demand since the 1960’s and in the USA that for the carbonate is now less than half the level of the late 1970’~~~~’ Intense competition led to a sustained allegation of ‘dumping’ from West German prod~cfion~~’~~~~ and several manufacturers have closed their plant^.^^''^^^ Against this background it is interesting that Japanese imports of the carbonate from China rose to over 10 000 tonnes in 1980 and that 30% of this total is used for radiation prevention in the cathode ray tubes of colour television Television tube production provided a major outlet for barium carbonate in the USA and Western Europe in earlier years.Zinc Cadmium and Lead.-These metals usually occur together with cadmium in lowest amount as mixed sulphide ores and are separated in the metallurgical refining process.Demand for zinc oxide hitherto widely used in paint pigments and as a rubber filler has continued to decline.z73 Its use in sensitizing photocopying paper has also fallen as more sophisticated copying techniques for offices have been introduced. US production fell from 206 000 tons in 1978 to 140 000 in 1980.274 Lead oxide was also used extensively as a paint pigment and drier but has been surpassed for toxicity and technical reasons. A use which remains is lead-acid batteries and a new process for lead oxide for this purpose was ’” Usine Nouv. 1981 7th May p. 53; Chim. Actual. 1981 10th April p. 6. 263 Jpn. Chem. Week 1980 23rd October p. 7; ibid. 1980 13th November p. 7; ibid. 1981 17th September p. 15. 264 J. Commerce 1981,7th May p. 10. 265 Chem.Eng. 1981,18th May p. 58; Chem. Mark. Rep. 1981,12th January pp. 3,32; ibid. 1981,27th April p. 7; Chem. Eng. News 1981 16th March p. 11. 266 Jpn. Chem. Week 1981 17th September p. 2. 267 Chem. Purchas. 1981 January p. 100. 268 Chem. Purchas. 1981 September p. 15; Pulp Pap. 1981 October p. 267; Pap. Trade J. 1981 15th October p. 45; Soaps Cosmet Chem. Spec 1981 September p. 106. 26q Chem. Week 1981 5th August p. 26. 270 Chem. Mark. Rep. 1981 2nd March p. 16; ibid. 1981 11th May p. 4. 271 Chem. Mark. Rep. 1981 18th May p. 5; Chem. Week 1981 20th May p. 9. 272 Jpn. Chem. Week 1981 12th March p. 11. 273 Chem. Purchas. 1980 October pp. 55-59. 274 Chem. Purchas 1980 October p. 56. 275 Eur. Chem. 1981 No. 24 p. 407; Metall 1981 September p. 826.356 R. Thompson Cadmium is more highly toxic than lead and although important as a colour pigment in ceramics paints and plastics it is rapidly being replaced under pressure of legislation; for example Sweden has banned the import of toys and other goods containing cadmium A cyclic process for generating hydrogen has been developed in the USA cadmium is reacted with water and the resulting hydroxide is re-converted to the metal by a high-temperature thermal decomposi- tion process.277 Chromium Molybdenum and Tungsten.-Trends and technology in industrial chromium chemicals were reviewed.278 Chromic acid demand in the USA is forecast to rise from the 43 000 tons of 1980 to 49 000 tons in 1984.279 Two thirds of this is for metal finishing (chromium plating) and 18% goes into wood preservation mainly as the copper-chrome-arsenate (C.C.A.) composition already referred to.Usage in leather tanning has declined in many countries (largely for environmental reasons) but a plant to produce 18 000 tons per year of sodium dichromate principally for this purpose has started up in Argentina.280 The main use of tungsten compounds is in the production of tungsten metal and the carbide ammonium paratungstate and tungstic oxide being the important ones.281 The chemical uses of molybdenum and its compounds as well as their production were reviewed.282 Many of the applications are in the catalyst field. Molybdenum disulphide is best known as a solid lubricant or lubricating oil additive and two plants to produce 500 and 450 tons per year of a suitable grade for this purpose were started up in Canada.283 Molybdenum is an important alloying element and perhaps three-quarters of all production is used metallurgically.Its importance to an industrial economy is indicated by several companies having established strategic stockpiles of molybdic oxide in Japan where total demand is 11000 tons per year.284 Manganese.-Uses for manganese compounds tend to be in the agricultural battery and metallurgical areas. Manganese is an essential trace element for plants and animals and the sulphate is often used for fertilizer purposes. Supply and demand in the USA are about in balance at 50 000 tons per year projected to rise by 10% by 1985.285 Construction was announced of a US plant to produce 25 000 tonnes per year of a battery-grade manganese dioxide interestingly for use in alkaline cells.286 The dioxide has long been used as a depolarizer for zinc-carbon and zinc chloride batteries and a so-called Faradiser plant completed in Belgium has a 276 Eur.Chem. News 1980 15th December p. 26; Playthings 1981 April p. 9. 277 Mach. Des. 1980 6th November p. 16. 278 W. H. Hartford in ref. 3 pp. 31 1-345. 279 Chem. Mark. Rep. 1980 22nd December p. 9. 280 Eur. Chem. News. 1980 1st December p. 14; Chem. Week 1980 17th December p. 29; Chem. Age 1980 21st November p. 10; Chim. Actual. 1980 21st November p. 8; Furbe Lack 1981 February p. 152; Chem. Eng. 1981 19th February p. 35. Chem. Week 1981 6th May p. 11. 282 E. R. Braithwaite in ref.3 pp. 346-374. Met. Bull. 1981 13th February p. 19; Can. Chem. Process. 1980 3rd September p. 12. 284 Met. Bull. 1981 21st August p. 17. 285 Chem. Mark. Rep. 1981 14th September p. 74. 286 Am. Met. Mark. 1981 6th February p. 8; Chem. Mark. Rep. 1981 2nd February p. 7; Chem. Eng. News 1981 30th March p. 9. Industrial Inorganic Chemistry 357 capacity of 40000 tonnes per year making it the world's largest for synthetic Mn02.287A Japanese plant has been extended to a capacity of 25 000 tonnes2" and one of 20 000 tonnes is to be built in South Potassium permanganate finds applications as an oxidizing agent in chemicals manufacture and in water treatment where it is effective in the destruction of organic compounds e.g. grease removal.290 Iron Cobalt and Nickel.-The highest-tonnage iron salts produced are the sulphate and the chloride often as by-products of the titanium dioxide pigment industry or as waste from pickling of iron and steel.One West German company is now selling 110 000 tonnes per year of the sulphate recycled from the titanium dioxide waste in part reducing the 240 000 tonnes dumped in the North Sea.291 Some sulphate is used in the production of Prussian blue.222 80% of ferric chloride usage in the USA is in 'recession-proof' sewage treatment for phosphate Overall demand there is forecast to grow from 209000 tons in 1981 to 306000 tons in 1985 but other uses are declining. Cobalt chemicals are employed for catalyst production including homogeneous applications of the hydrocarbon-soluble metal- organics as paint driers and in rubber curing.Cobalt naphthenate is being used in Japan to increase adhesion between rubber tyres and the wheel rims.293 The chemical uses of nickel and its compounds and their production were reviewed.294 Nickel is an important electroplating metal and a highly concentrated nickel sulpha- mate solution has been developed for this Rare Earths.-The manufacture and use of rare-earth inorganic chemicals was reviewed.2969297 These are materials of usually low-volume production but very high value mainly for the electronics optical and catalyst industries. Production is intricate involving solvent extraction separations of suites of elements which occur together and in the hands of a few specialist companies.One French company's sales of europium and yttrium account for 50% of the world's total.298 A new plant was built in the USA for gadolinium and samarium recovery299 and a Malaysian plant under construction will supply material for fluid-cracking catalyst produc- ti~n.~" Japanese demand is forecast to rise at 8-9'10 per annum with cerium oxide accounting €or most of this but there will also be some increase in yttrium oxide for colour television 287 Chem. Mark. Rep. 1981 2nd February p. 7; Chem. Age. 1981 6th March p. 15; Chem. Ind. (Berlin),1980 December p. 847. 288 Met. Bull. 1980 30th September p. 25; Chem. Znd. (Berlin),1980 December p. 847. 289 Chem. Ind. (Berlin),1980 December p. 847. 290 Water Eng. Manag. 1981 March p.14. 291 Chem. Age 1981 20th February p. 7. 292 Chem. Mark. Rep. 1981 26th January p. 9. 293 Jpn. Chem. Week 1980 20th November p. 7. 294 E. R. Braithwaite in ref. 3 pp. 375402. 295 Chem. Purchas. 1981 April p. 99. 296 K. A. Gschneidner in ref. 3 pp. 403433. 297 K. A. Gschneidner 'Industrial Applications of Rare Earth Elements' Am. Chem. Soc. ACS Symp. Ser. 1981 No. 164. 298 Jpn. Chem. Week 1980 13th November p. 5. 299 Chem. Eng. 1980 17th November p. 65. 300 Chim. Actual. 1980 5th December p. 5. 301 Jpn. Chem. Week. 1981 24th September p 1. 358 R. Thompson Uranium.-Uranium chemistry is nowadays almost entirely directed to the extrac- tion and enrichment necessary for nuclear fission purposes. The inorganic chemistry of the nuclear fuel cycles was reviewed by U.K.A.E.A.author^.^^^*^^^ Uranium ore is usually up-graded as far as ‘yellow cake’ or uranium oxide at or near the mine site. Major producing countries are Australia Canada Southern Africa and the USA. A 500 tonnes per vear UF6 plant is to be built in Brazil using French technology304 and the feasibility of constructing one in Australia with British participation is being st~died.~” A refinery in Canada that will produce 18 000 tonnes per year of uranium trioxide destined for hexafluoride manufacture is due on-stream in 1983.306 Production of uranium hexafluoride is an important outlet for hydrofluoric Small but significant amounts of uranium occur in phosphate rock; extraction is feasible and under certain circumstances could be economic.178 Other Metals.-Reviews were published on the production and applications of inorganic compounds of titanium,307 zirconium,3o8 tin,309 and the precious metals.310 14 Pigments Pigments and fillers for the surface coatings paper plastics and rubber industries constitute a major part of the inorganic chemicals sector.Titanium dioxide is one of the most important of those synthesized and is made by two processes ‘sulphate’ and The former is the older and has the disadvantage of being both energy-intensive and creating disposal problems for the ferrous sulphate and calcium sulphate waste products. Accordingly some plants are being pha~ed-out,~** a process hastened by the recession and existing ones are enlarged only if the local waste problem can be dealt with economically.313 New capacity thus tends to be of the chloride route and several titanium tetrachloride plants were announced in the Although most of the tetrachloride is for pigment manufacture some is used in the production of titanium Consumption of titanium dioxide in the USA is estimated to reach 900 000 tons per year by 1985.316 At $1 per pound it is still not an inexpensive material and although its whiteness and opacity render it cost-effective in many applications throughout the history of its use the benefit has been maximized by blending with white diluents or ‘extenders’.302 J. R. Findlay K. M. Glover I. L. Jenkins N. R. Large J. A. C. Marples P. E. Potter and P. W. Sutcliffe in ref. 2 pp. 419466. 303 J.A. C. Marples R. L. Nelson P. E. Potter and L. E. J. Roberts in ‘Energy and Chemistry’ ed. R. Thompson Special Publication No. 41 London Royal Society of Chemistry 1981. 304 Inf. Chim. 1981 February p. 32; Electr. Rev. Int. 1981 6th February p. 6; Chem. Mark. Rep. 1981 12th January pp. 7,48. 3n5 News Release 1981 22nd June p. 1; Met. Bull. 1981 3rd July p. 19; Chem. Ind. (Berlin) 1981 September p. 570. 3n6 Chem. Mark. Rep. 1981 6th April p. 49. 307 G. F. Eveson in ref. 3 pp. 226-247. 308 F. Farnworth S. L. Jones and I. McAlpine in ref. 3 pp. 248-284. 309 P. A. Cusack and P. J. Smith in ref. 3 pp. 285-310. 310 P. E. Skinner and L. P. Vergnano in ref. 3 pp. 444459. 311 R. S. Darby and J. Leighton in ref. 2 pp. 354-374. 312 Chem. Ind.1981,7th March p. 129. 313 Pap. Trade J. 1981 30th June p. 24; Mod. Paint Coat 1981 August p. 66. 314 Am. Met. Mark. 1980. 7th November p. 20. 315 Chem. Mark. Rep. 1980 10th November p. 4;Chem. Week 1980 12th November p. 27; Chem. Eng. News 1980 December p. 13. 316 Adhesives Age 1981 May p. 49; Am. Ink Maker 1981 May p. 53. IndustriaI Inorganic Chemistry 359 There is still considerable research in the field.317 Mineral fillers are often and include siliceous materials already referred to as well as precipitated and fumed silica^,^^^^*^^ calcium kaolin,316 talc,316 and As the cost of petrochemical products increases and with it the incentive to use higher proportions of fillers so does the need to surface-treat the inorganic particles with 'coupling agents' in order that the desirable physical properties of the plastic or rubber are maintained.186,320,321 Carbon black is also an important filler especially for the rubber industry but its rising cost is incentive to seek alternatives among which are the silicas and calcium carbonate provided they are surface-treated in this way.183,184.186.321.322 Iron oxide has long been used as a pigment although the still comparatively small use of the magnetic variants in computer audio and video tapes is growing 1980 world consumption for magnetic tapes was estimated as 26 000 tons which is about one-sixth of the amount used as a pigment. Obviously a much purer form of iron oxide is necessary for magnetic purposes implying a better-quality starting material; a Japanese company has developed suitable refinery technology from ferrous ~ulphate.~~~ An American company already well entrenched in various grades of iron oxide has announced plans to increase production of cobalt-doped gamma ferric oxides for premium quality recording Other metal oxides used for pigmentary purposes either as filler or for effects such as corrosion inhibition include those of copper lead and zinc.Cuprous oxide is used in marine paints263 and zinc oxide for a variety of although its use is declining.273 Zinc-rich protective paints in which zinc metal dust is dispersed in sodium silicate continue to be developed and a new one is based upon an alkyl silicate binder as a single package.326 17 Electronic Chemicals The electronic and telecommunications industries are high-value consumers of inorganic chemicals in which purity or controlled impurity is paramount.Gallium and gallium arsenide continue to attract considerable attention. The world market for gallium and its oxide is expected to grow 20% by 1985.327About one-third of total production 7.5 tonnes per year derived from 600000 tonnes of bauxite is from a plant in France. It is obtained there by liquid-liquid extraction of the spent aluminate liquor from the Bayer process.328 Other production processes include extraction as the silicate from such liquors and electrolysis between nickel anodes and tinfoil cathodes with which the gallium alloys.329 Free-world production capacity 'I7 J. Coat. Technol. 1981 September p.75. 3'R Chem. Purchas. 1981 March p. 96. 319 PaintManuf. 1980 November p. 7; Sven. Papperstidn. 1980 25th November p. 497. 320 Am. Paint J. 1981 28th September p. 36; Mod. Paint Coat 1981 November p. 82. 321 Plast. Rubber Wkly. 1981 21st February p. 2. 322 Chem. Rundsche 1981 21st January p. 1. 323 Chem. Mark. Rep. Chem. Bus. Suppl. 1981 1st Jun p. 33. 324 Jpn. Chem. Week 1981 17th May p. 7. 325 Chem. Purchas 1981 September p. 15; Electron. News,1981 10th August p. 57. 326 Mod. Paint Coat. 1981 January p. 80. '27 Chim. Actual. 1980 19th December p. 9. '28 Eur. Chem. 1981 No. 4 p. 53. 329 Met. Bull. Mon. 1981 February p. 65. 360 R. Thompson in 1978 was 25 tons per year,329 with 1.5 tonnes in Czechoslovakia helping to bring total capacity to perhaps 40 The potential US annual demand for gallium in photovoltaics could be 2000 tons by early next century,331 Gallium-aluminium- arsenide cells in 5000 MW satellite power system projects would require 390 tons per unit an ambitious demand that would clearly be difficult to meet.329 Gallium arsenide is forecast as a supplement to or even replacement for silicon in the semi-conductor A production plant opened in Canada employs a highly automated crystal-growing furnace in which crystals up to 20 inches long and 3 inches in diameter can be grown in 36 Wafer-production capacity is rapidly being expanded in Japan,334 and a new chemical vapour deposition (CVD) technique enables the growth of very thin epitaxial slabs on re-usable single-crystal sub- strate~.~~~ There appears to be some confusion in the gadolinium gallium garnet (GGG) market arising from user companies entering or withdrawing from the bubble memory field but the longer-term view is one of business growth (to some extent at the expense of silicon).336 Fibre optics is also a growth industry and US capacity for the production of phosphorus oxychloride silicon tetrachloride and germanium tetrachloride of suitably high purity for CVD application has been expanded.337 Production of synthetic gemstones both for industrial-electronic and jewellery applications is increasing Here again value rather than volume is important but the synthetic gem whether diamond or emerald can be made by modern high-temperature crystal-growing techniques for about one-hundredth of the cost of the natural ~tones.~~~*~~~ A new high-temperature method for producing zinc selenium of better infrared transparency for use in lasers is also cheaper than the other 330 Met.Bull. 1981 9th October p. 15. 331 J. Mer. 1981 September p. 33. 332 New Sci.,1981 19th March p. 747; News Release 1981 27th February p. 1; Electron. Bus. 1981 August p. 102; News Release 1981 8th January p. 1. 333 Can. Electron. Eng. 1981 August p. 32. 334 Met. Bull. 1981 20th October p. 17. 33s Electronics 1981 19th May p. 38. 336 Electron. News 1981 6th April pp. 18 56; ibid. 1981 28th September p. 58. 337 Opt. Spectra 1981 April p. 16. 338 Chem. Mark. Rep. Chem. Bus. Suppl. 1981 4th May p. 37. 339 Inf. Chim. 1981 May p.115. 340 Chem. Week 1981 15th April p. 54.

ISSN:0260-1818    

DOI:10.1039/IC9817800333

出版商:RSC    

年代:1981

数据来源: RSC

摘要:

Author Index Abashkin V. M. 16 Abdel-Mequid S. 243 Abdesaka F. 78 Abdullaev G. K. 23 Abe T. 136 Abel E. W. 120 226 280 Abel T. J. 285 Abrams M. J. 197 Abrao A. 316 Abruna H. D. 255 Ache H. J. 320 326 329 Acher F. 121 Achkasov S. K. 331 Adam M. J. 126 Adam R. W. 331 Adams G. S. B. 192 Adams R. D. 258 Adams W.-E. 320 Adcock P. A. 255 Addison A. W. 285 Adeyemo A. 295 Adlof R. O. 319 Adloff J. P. 330 Ad’yaasuren P. 84 Adzamli I. K. 233 Aggarwal R. C. 230 Agha N. H. 324 Aharon-Shalom E. 123 Ahlberg P. 14 Ahmad M. M. 117 Ahn B. T. 282 Ahrland S. 132 Aime D. 241 Aime S. 235 252 253 259 Ainscough E. W. 281 Airoldi C. 296 Aizman A. 214 Akhmanova M.V. 332 Akhtar M. 113 Akimoto T. 329 Akitt J. W. 57 58 Akiyama M. 187 Aktalay Y. 102 103 Alagna L. 150 Al-Allaf T. A. K. 95 Albech M. 123 Albers M. O. 217 Albertin G. 230 Albertini J. 213 Albinati A. 266 Albright T. A. 95 223 Aldashin S. M. 11 Aldred A. T. 299 Aldrich P. D. 129 Alei M. jun. 295 Aleksandrov G. G. 217 226 244 245 Aleksanyan V.-T. 219 Alekseev F. P. 68 Alekseev N.-V. 85 Alekseev V. I. 84 Alemdaroglu T. 295 Al-Essa R. J. 277 Alexandrov G. 235 Alexeichuk I. S. 139 Algra G. P. 138 214 Al-Hilli A. M. 324 Alian R. M. 320 Alikhanova Z. M. 39 Aliotta F. 132 AI-Jibori S. 267 Allcock H. R. 51 Allegretti V. 157 Allen D. W. 121 Allen R.M. 320 Allred W. P. 67 Almeida J. F. 6 Almeida R. M. 143 Almenningen A. 28 Al-Obaidi Y. N. 265 Al-Ozaibi Z. 142 Alper H. 254 Ahead C. 290 Al-Shahristani 316 Al-Shatti N. 214 284 Altnau G. 86 Alvarez C. J. 325 Alvarez J. R.G. 16 Alves A. S. 261 Alway D. G. 254 Alyea E. C. 292 Al-Zubaidi K. A. 316 Ambe F. 330 Ambe S. 330 Amirkhalili S. 59 Amiraslanov I. R. 92 Arnirzaden-Asl D. 101 Amoh K. N. 200 Amstutz R. 5 6 Anand V. K. 227 Anderegg G. 200 Andersen E. L. 40 239 Andersen J. L. 184 Andersen R. A. 308 3 11 Anderson A. B. 219 Anderson P. J. 318 Anderson R. K. 279 Ando V. 78 Ando W. 80 Andreev B. M. 302 Andrew S. P. S. 337 Andrews D. G.265 331 Andrews L. 131 Andrews M. A. 270 Ang K. P. 282 Angelici R. J. 111 188 218 231 286 Angell C. A. 143 Angoletta M. 268 Anikiev V. V. 332 Anis M. K. 62 Annis G. D. 219 Ansell G. B. 236 Anslow S. E. 65 Anson F. C. 165 Anst J. M. 288 Antebi S. 219 Antipin M. Yu. 84 226 Antoli L. 283 Anton K. 28 Antonini E. 213 Antonio M. R. 205 Anzai K. 213 Aoai T. 122 Aono K. 50 Apai G. 301 Appel R. 99 Appelman E. H. 125 132 291 Arakawa K. 129 Araki T. 118 170 Aratono Y. 316 Araujo R. E. 303 Arcamone F. 320 Arduini A. L. 312 Aresta A. 291 Argentini M. 325 361 Arkhipova G. G. 317 Armentrout P. B. 227 Armstrong J. E. 261 Armstrong W.H. 182 Arnold A. P. 298 Arnold D. E. J. 121 Aronowitz S. 326 Arthur C. D. 125 Asada K. 140 309 Asao T. 2 19 Ascenso J. R. 307 Ascenzi P. 213 Ashby E. C. 52 61 Ashe A. J. 108 Ashworth J. V. 194 217 Aspinall H. C. 202 Astakhova I. S. 303 Astakhova N. M. 260 Astfalk C. 325 Astruc D. 225 Atherton N. M. 131 Atovmyan L. O. 11 Atwood J. L. 58 91 111 153 154 155 192 197 201 202 246 Ault B. S. 100 133 134 Aumann R. 220 Averill B. A. 180 205 Avramenko A. A. 146 Awh 0.D. 323 Aymonio P. J. 186 Azam K. A. 111 Azran I. 319 Baba S. 318 Babar M. A. 142 Babcock L. M. 136 Babkina L. S. 53 Baccolini G. 188 Bachmann P. 103 105 Back T. G. 122 Backs S. J.96 Baenziger N. 213 Baenziger N. A. 167 Baenziger N. C. 165 180 Baer C. D. 107 Baetzold R. C. 292 Baga E. 319 Bahrami S. 325 Baidini I. A. 84 Bailey P. M. 265 266 268 Baiocchi F. A. 129 Baird M. C. 218 Bajo S. 315 Baker E. N. 281 Baker J. D. 316 Baker P. K. 265 Baker R. T. 44 46 Bakker C. N. M. 326 Bako P. 10 Bakum S. I. 52 Balashova E. I. 317 Balasubramanian V. 26 Balbach B. 264 Balbach B. K. 201 Balch A. L. 271 Baldas J. 197 324 Baldwin B. J. 216 Baldwin C. M. 143 Balestrieri F. 226 Ballantine J. A. 116 Balt S. 138 214 Baluka M. 128 Bamford I. 321 Banci L. 288 Bandara B. M. R. 219 Bandy J. A. 13 Banek M. 101 Banel S. 295 Banerjea D.284 Banerjee A. K. 308 Banerjee P. 121 Banfi D. 321 Banister A. J. 97 115 Bankhardt W. 214 Banks R. E. 134 Barantseva I. G. 19 Barby D. 348 Barchas J. D. 318 Barck D. D. 215 Barefield E. K. 198 247 Barefoot A. C. III. 222 278 Barkai Zs. 325 Barker F. 325 Barker G. K. 49 50 234 235 Barker K. 37 Barker M. G. 57 Barker P. E. 53 Barley M. 256 Barner-Thorsen C. 253 Barnes C.-E. 256 Barnes J. W. 323 Barnes M. G. 332 Barnett B. L. 324 Barone V. 39 Barrachina M. 315 Barraclough C. G. 128 309 Barriola A. M. 37 Barrow M. J. 83 Barry J. 303 Bartak D. 228 Bartell L. S. 141 Barthelemy E. 300 Bartl K. 241 Bartlett N. 136 145 Bartoli J. F. 213 Bartsch R.135 Bartsch R. A. 16 Baryshok V. P. 85 BaSe K. 37 Bashkin J. 95 Basinger M. A. 296 298 Basmedjian G. P. 325 Bassett J.-M. 50 235 265 Batail P. 225 Batlogg B. 304 Author Index Bats J. W. 93 Battaglia L. P. 110 283 Battioni J.-P. 21 3 Battioni P. 213 Ban R. 40 243 290 Baudler M. 102 103 104 105 Bauer C. 191 237 265 Bauer H. 21 Bauer S. H. 24 Bauhofer W. 305 Baxter S. G. 101 226 Bayerl B. 195 Beachley 0.T. jun. 59 67 68 Beagley B. 83 Beall G. W. 305 Beard L. K. 224 Beauchamp A. L. 295 297 Beauchamp J. L. 227 Beaudet R. A. 34 Beck W. 21 Becker G. 99 Becker J. Y. 256 Beddoes R. L. 114 289 Beerling H. D. 320 Beery J. W. 58 Beesk W.291 Begbie C. M. 233 Begley J. A. 322 Begley M. J. 57 Begolli B. 157 Begun G. M. 310 Beheu D. V. 213 Behr J. P. 10 Behrens U. 5 Beincel E. 297 Beinert H. 289 Beisky V. K. 107 Belamas A. 296 Belin C. 62 130 Bellon P. L. 268 Belov N. V. 23 Belov V. A. 317 Belser P. 255 Belyaev I. N. 4 Belyaev L. M. 306 Bencini A. 288 Bendow B. 143 Benedict J. J. 324 Benfield R. E. 235 253 Benner L. S. 53 Bennett D. W. 85 Bennett M. A. 257 Benno M. A. 236 Benoit A. 235 240 Benson I. B. 203 Benson R. 99 Bentley G. 313 Bentley G. E. 323 Benton A. J. 158 Benua R. S. 320 321 322 Berak L. 331 Berdyukova V. A. 4 Author Index Berei K. 329 Berezin B.D. 152 Berg J. M. 119 182 Berger G. 320 Bergerhoff G. 133 Bergman A. 321 Bergman R. G. 227 228 229 246 Bergmann H. 315 Bergson G. 320 Berke H. 214 Bernal I. 111 201 202 231 257 283 Berndt A. 19 Bernhard P. 257 Bernheirn M. Y. 51 Berridge M. S. 322 Berry F. J. 119 205 Berry J. A. 140 Berry J. M. 126 Berthon G. 290 295 Bertini I. 231 Besch W. 325 Bette R. 315 Beurich H. 244 Bevan J. A. 324 Beyendorff G. 139 Beyendorff-Gulba G. 152 Bezdenzhnykh G. V. 301 Bezems G. J. 228 Bhagwat D. A. 330 Bhagwat V. W. 11 Bhatia S. C. 131 Bhattacharjee M. N. 195 Bhattacharya A. 130 Bhave R. N. 328 Bhupathy M. 309 Bianchini C. 214 230 240 Bibiloni A. G.68 Bickley D. G. 151 Bickmann K. 304 Bida G. T. 322 Bidzilya V. M. 12 Biely P. 320 321 Biffar W. 28 Biggin S. 132 Bigler R. E. 322 Bigoli F. 231 Bilafer C. 324 Bilik V. 320 Bilinski H. 151 Billaud D. 146 Billinghurst M. W. 323 Binnewies M. 143 Bino A. 183 186 Birattari C. 323 Birch A. J. 219 220 Birchall T. 93 126 151 Bird P. H. 175 239 267 Birdy R. 213 Birge R. P. 111 Birkel I. 130 Birker P. J. M. W. L. 20 120 281 289 291 Birkhahn M. 108 Birks J. W. 131 Bishop V. L. 33 Biswas P. K. 230 Bjerre N. 132 Bjerrum N. J. 122 Bjoernstad T. 316 Blachnik R. 105 Blahnik D. E. 332 Blair L. A. 319 Blais M. J. 290 Blake A. J. 100 Blakeney A. J.88 223 Blanch S. W. 221 Blasius E. 3 Blau M. 323 Blauenstein P. 200 Blecher A. 94 Bleeke J. R. 227 Blitzbau M. 319 Block A. 116 Blosl S. 109 Blote H. W. J. 287 Bloom H. 133 144 Bloomquist D. R. 283 287 294 Blount J. F. 192 Blurock E. S. 66 Blyholder G. 205 Boag N. M. 280 Boatner L. A. 305 Bochkarev M. N. 81 86 Bochu P. 305 Bock H. 81 82 96 Bockmeulen H. A. 221 Bodner T. 222 Bogge H. 149 Bohland H. 4 Bohm M. C. 31 Bonisch J. 133 Boerio-Goates J. 196 Boese R. 30 241 Bogaard M. P. 127 Boggess R. K. 196 Bogsanyi D. 220 Bohman O. 14 Bojes J. 98 114 Boltich E. B. 302 Bombieri G. 307 Bombin F. 202 Bonardi M. 323 Bond A. C. 41 Bond A.M. 221 296 Bondars A. 23 Bondinell W. E. 321 Bondyuk L. V. 68 Boniface S. M. 21 Bonner 0.D. 128 Bonnet J. J. 257 Bonnetain L. 145 Bonnyrnan J. 197 Boo W. 0. J. 155 Boocock S. K. 38 39 42 43 275 Boorman P. M. 186 Boos D. 143 Booth M. 120 226 280 Boothe T. E. 320 326 Borcham C. J. 233 Bordignon E. 230 Borgarello E. 254 Borghi F. 231 Borisenkov V. I. 22 Borisov A. P. 39 Borisov S. V. 84 Bortolini O. 156 Bosman W. P. 245 Bosnich B. 121 290 Bostian L. C. 340 Bottomley F. 153 163 Bottomley L. A. 175 213 294 Boucher H. 232 Bouchet P. 318 Bougon R. 134 Boulos M. 143 Bour J. J. 245 Bowen M. 213 Bowen P. 119 205 Bowmaker G. A. 114 120 293 Bowser W.M. 263 Bowsher B. R. 9 112 Boxhoorn G. 172 Boyd G. S. 323 Boyd I. W. 167 Boyd P. B. W. 248 Boyd S. E. 318 Boyer D. 65 Brabec D. 319 Bradbury J.-R. 170 Bradley C. B. 66 Bradley D. C. 178 Bradley J. S. 236 Bradley P. G. 173 255 Brady F. 71 73 Braithwaite E. R. 356 357 Brandenburg D. 325 Branman J. T. 210 Braterman P. S. 228 255 Braunstein P. 243 Brawer S. A. 143 Breeze P. A. 221 Breitrnaier E. 7 Brett M. E. 119 205 Breunig H. J. 189 Brevard C. 165 166 Brewer G. A. 169 Briant C. E. 120 263 272 Bricker J. C. 254 Briggs A. 145 Briggs J. R. 277 Brindza H. E. 228 Brinkman G. A. 326 328 Brint P. 35 234 Brintzinger H. H. 228 Brion F. 219 Brittain H.G. 308 311 364 Brnitevid N. 151 Broadhurst P. V. 236 Broadley K. 222 Brocklehurst J. D. 33 1 Brodack J. W. 193 Broden K. 316 Brodie A. M. 281 Brook A. G. 78 Brook L. 298 Brookhart M. 218 220 Broomhead J. A. 177 Brothers P. J. 256 Brough L. F. 86 Brousil J. 325 Brown C. A. 226 Brown D. 140 Brown D. B. 205 277 Brown G. M. 135 189 214 Brown J. N. 133 231 296 Brown K. E. 196 Brown K. L. 281 Brown K. R. 293 Brown M. P. 279 Brown N. 347 Brown N. M. D. 24 Brown R. D. 82 Brown T. L. 229 Browning J. 270 Brownlee R. T. C. 179 192 Brownstein S. K. 20 Brubaker C. H. jun. 154 Bruce A. E. 116 Bruce M. I. 254 256 257 266 Bruck M. A. 243 Bruckner R.29 Brugger P. A. 254 Bruncks N. 85 308 Bruno G. A. 315 Brunon M. 213 Brunschwig B. S. 195 214 Bryan R. F. 226 Bryant E. 313 Bryden C. C. 307 Bubnis B. P. 10 Buchanan R. M. 230 Buchler J. W. 262 Buchrnan O. 319 325 Buckingham D. A. 233 Buckingham M. J. 195 Buckley D. I. 319 Buckner M. T. 282 Budai Z. 319 Budarin L. I. 11 Buder R. 287 Budge J. R. 176 Budrowski C. 146 Buduan P. V. 112 205 Buenker R. J. 32 Bueno C. 68 191 194 195 26 1 Buenzli J.-C. G. 307 Burgi H. B. 200 Bui Huy T. 134 Bukina T. I. 317 Bukovec P. 156 Bulbulian S. 330 Bullen G. J. 27 Bulychev B. M. 39 56 Bunel E. 116 286 Bunker B. C. 304 Bunker M. J. 111 162 Bunton C.A. 226 286 Burch R. R. 227 266 Burckett-St. Laurent J. C. T. R. 106,273 Burdett J.-K. 171 221 282 Burdina K. P. 25 Burfield D. R. 318 Burford N. 99 Burg A. B. 34 99 101 Burger M. 97 Burgers H. 247 Burgess J. 139 140 300 Burke P. J. 73 Burke T. R. jun. 318 Burmeister J. L. 293 Burnasheva V. V. 299 Burnett M. G. 209 Burns H. D. 324 Burns J. W. 67 Burns R. C. 69 140 309 Burrows J. P. 131 Burt R. J. 162 Burton L. D. 301 Busch D. H. 211 Buschov K. H. J. 302 Busetto L. 188 194 Bushnell G. W. 270 Buslaev Yu. A. 53 Buss B. 197 206 Butcher R. J. 248 287 Butler I. S. 121 187 204 Butler J. 213 Butler J. E. 140 Butler R. J. 209 Butters T. 219 Butler W.108 Butler W. M. 51 Buxton L. W. 129 Byberg J. R. 132 Byers L. R. 242 Bykovets A. L. 244 Bynum R. V. 154 Byrd B. L. 320 Byrn M. P. 212 Cady G. H. 137 Cahill P. C. 292 Cairns C. 116 209 Caird J. A. 144 303 Calabrese J. C. 6 41 Calabro D. C. 293 Calado J. C. G. 154 Calder M. R. 113 Calderazzo F. 111 201 202 228 Author Index Calderon J. L. 154 Callaghan R. 214 Callahan K. P. 158 180 249 Callery P. S. 318 Callot H. J. 71 292 Calverley M. J. 12 Cameron J. H. 126 214 Cameron T. S. 90 280 Camin L. L. 314 324 Cammack R. 119 206 Campbell J. A. 320 326 Campbell M. L. 11 Canfi A. 325 Canivet P. 128 Cannas M. 297 Canty A. J. 297 Canziani F. 269 Capella L.64 Caranoni C. 64 Carlin R. L. 229 249 Carmona E. 246 Carnall W. T. 144 303 Carr C. 69 133 Carr P. A. G. 111 Carrasco N. 226 Carrassquillo G. 92 Carriedo G. A. 202 Carson G. K. 296 Carter R. O. tert 131 Carty A. J. 215 238 252 253 298 Carvaiho 0.G. 315 Carvalho M. F. N. N. 197 Cary L. W. 193 Casadonte D. J. 282 Casas J. S. 298 Case D. A. 214 Casella L. 281 284 286 295 Casellato U. 308 Casey J. B. 32 Cashion J. D. 120 Cass M. E. 193 266 Cassens A. 226 Cassie R. 218 Castel A. 81 Catral-Navarrete J. 330 Caulton K. G. 200 Cava M. P. 123 Cavasino F. P. 206 Cavell R. G. 103 Cavinato G. 274 Cecchi A. 326 Cecconi F. 210 237 Cefalu R.64 Ceulemans A. 255 Chacko K. K. 8 Chadha R. 33 Chaga A. P. 296 Chaichit N. 297 Chakravorty A. 170 289 Chalabala M. 324 Chalyi V. P. 64 Champion R. 82 Author Index 365 Chandler T. 119 Chandra B. P. 310 Chandrasekaran K. 233 Chaney J. E. 320 Chang B.-H. 154 Chang C. 220 Chang C. A. 275 Chang C. C. 312 Chang C. K. 212 Chang C. T. 312 Chang S. 205 326 Chantooni M. K. jun. 15 Chappell S. D. 256 Chapuis G. 307 Charbonnel M. 130 Charles A. D. 219 Charlton S. C. 219 Chastain S. K. 232 Chatgilialoglu C. 134 Chatt J. 118 197 Chatterjee K. K. 66 Chaudhuri M. K. 195 Chaudhuri N. R. 230 Chaudret B. 255 Chauncy B. 219 Chausse T. 20 Chauveau F.165 Che C. M. 256 Cheang S. K. 297 Cheek Y. M. 38 Cheetham A. K. 114 195 206 Chen G. J.-J. 191 Chen L. M. L. 207 Chen Y. 220 Chetcuti M. J. 194 242 Chetverikov A P. 309 Chetwynd-Talbot J. 204 Cheung T.-T. P. 296 Chevrier B. 211 Chhor K. 224 Chi Y. 87 Chiang L. 116 Chibiskova N. T. 306 Chieh C. 297 298 Chien M.-W. 121 Chieux P. 128 Chihi A. 76 Chikira M. 213 Childs A. F. 352 Childs E. L. 331 332 Ching Y. Y. 285 Chirakal R. 1?6 322 Chirico R. D. 249 304 Chisholm M. H. 173 177 182 183 185 186 187 Chisholm M. L. 157 Chiu K. W. 186 189 Chivers T. 97 98 99 114 115 Chi Wi Ong 218 Chocholous J. 321 Choi H. W. 19 260 Chong K. S. 64 65 Chopra S.-K.220 Chottard G. 213 Chottard J. C. 213 Choukroun R. 151 Christe K. O. 96 125 128 132 134 164 Christensen A. N. 304 Christensen J. J. 3 Christensen K. A. 167 Christiaens L. 323 Christian B. H. 107 Christian G. 216 Christian P. A. 235 Christman D. R. 321 327 Christou G. 119 179 206 Chuang M. 231 Chubarov V. V. 332 Chudinova N. N. 306 Chui D. E. 285 Chum H. L. 208 Chumakova G. M. 317 Chund C. S. 286 Chung K. H. 143 Church S. P. 200 Churchill M. R. 60 68 107 162 163 190 191 194 195 200 203 231 258 261 269 282 Chwojnowski A. 61 Ciani G. 170 263 Ciavatta L. 310 Cichon E. J. 180 249 Cifka J. 325 Cifkova I. 325 Ciminale F. 291 Cimolino M. C.172 Cini R. 229 294 Clack D. W. 31 Clark A. M. 319 Clark D. T. 282 Clark E. R. 316 Clark G. R. 21 Clark H. C. 279 Clark H. W. 141 Clark J. C. 314 Clark J. H. 130 Clark P. E. 290 Clark R. J. 330 Claudy P. 142 Clauss A. D. 259 Clegg W. 83 99 119 179 180 197 206 Cline J. E. 331 Cline S. J. 177 Clive D. L. J. 113 Cloke F. G. N. 95 Co M. S. 289 290 Coates J. H. 249 Cobbledick R. E. 219 239 Cockman R.W. 128 309 Codding P. W. 97 115 Coenen H. H. 323 Cohen A. 319 Cohen H. 319 Cole A. J. 114 195 206 Cole-Hamilton D. J. 172 256,274 Coleman G. H. 315 Coleman W. M. 196 Coleson K. M. 6 41 308 Colin J. 176 Collet A. 213 Collins C. H. 314 326 329 Collins K.E. 314 326 329 Collins R. L. 226 Collins T. J. 21 210 256 Collman J. P. 210 256 Colomer E. 203 Colquhoun H. M. 174 177 218 272 Colquhoun I. J. 37 121 297 Colton R. 63 133 221 296 Coltrain B. K. 286 Coman G. 222 Comar D. 314 320 322 Compton D. A. C. 134 Concannon C. 328 Conlin R. T. 77 Connelly N. G. 221 222 264 Connick R. E. 284 Connolly J. W. 95 Connor J. A. 230 289 Conrad Z. 151 Cook J. 262 Cook J.-E. L. 131 Cooke M. 252 Cooksey C. J. 259 Cooper A. J. L. 321 Cooper K. D. 9 Cooper M. K. 6 188 274 Cooper S. J. 279 Cooper S. R. 200 Cooper T. A. 25 123 Coppens P. 52 Corbett J. D. 69 90 150 300 303 Corbin D. R. 153 Corcoran E. W. jun.222 278 Corden B. P. 210 Cordes A. W. 98 99 102 114 115 Cordfunke E. H. P. 140 Corina D. L. 113 Coronas J. M. 246 Corradi A. B. 283 Corradi A. M. 110 Corrigan P. A. 265 Corrion J.-P. 113 Corriu R. J. P. 203 Corsi J. 257 Cot L. 142 Cotton F. A. 100 154 156 159 161 170 183 184 186 187 202 Cotton R. 297 366 Coucouvanis D. 165 179 180 206 Coudeau-Ducourant D. 109 Coughlin P. K. 287 Coulman C. L. 227 Coville N. J. 217 Cowley A. H. 54 91 100 101 116 223 224 226 Cox B. G. 15 Cox D. M. 316 Cox D. N. 42 234 Cox P. H. 324 Cox R. A. 131 Coyle T. D. 313 Crabtree R. H. 268 Cradock S. 83 100 121 122 Craig R. S. 301 Cram D. J. 3 11 14 Cramer R.E. 295 312 Cramer S. P. 289 Crampton C. A. 345 Creber K. A. M. 201 Cresshull I. D. 73 Cresswell P. J. 233 Crichton B. A. L. 118 Critchlow S. C. 90 Crocker C. 267 277 Crook J. E. 43 269 Crosby G. A. 255 Cross R. J. 136 274 Crouzel C. 320 Cuellar E. A. 139 309 Cuendet P. 254 Cullen W. R. 219 Cummings J. M. 111 201 Cummings S. C. 285 Cuninghame J. G. 315 Cunningham D. 93 Curic M. 93 Curphey T. J. 320 Cusack P. A. 358 Cushman B. M. 277 Cushner M. C. 54 Cutler A. 222 Czauderna M. 323 Czugler M. 10 13 Dabbabi M. 306 Darr E. 103 Daffe V. 232 Dagdigian J. V. 290 Dahl J. R. 322 Dahl L.-F. 242 Dahler P. 219 Dahlstrom P. L. 117 181 Dain C. J.34 41 Dakternieks D. 63 133 296 297 Dale J. 12 Dalibart M. 54 55 Dalley N. K. 11 Dallinger R. F. 255 Dalton M. S. 202 Damewood J. R. 192 Damien D. 309 Dammel R. 96 Dance N. S. 239 Daniel M. F. 224 Danis J.-H. 236 Dannals R. F. 324 Dannals T. E. 324 Daoudi A. 305 Daran J. C. 179 180 Darby R. S. 358 Darensbourg D. J. 100 202 216 223 241 Darensbourg M. Y. 187 223 Dariel M. P. 302 Darmon L. M. 282 Dartiguenave M. 246 Dartiguenave Y. 246 Dartmann M. 165 180 Das H. A. 324 Das A. K. 130 Das K. 130 Das M. 58 Dasgupta H. S. 195 Dasgupta T. P. 231 Dash A. C. 232 233 Datta D. 289 Davan T. 34 Davanzo C. U. 94 Davey P. N. 39 Davidson F. 24 25 Davidson G.27 30 Davidson I. M. T. 76 Davidson J. L. 190 Davidson R. S. 113 Davies D. H. 17 Davies D. L. 252 Davies D. M. 213 Davies G. 174 Davies J. A. 149 279 Davila R. 328 Davis D. M. 213 Davis M. A. 324 Davis M. S. 212 Davis P. J. 319 Davis R. E. 54 101 222 223 239 262 264 269 Davis R. F. 301 Davis S. C. 245 Davis W. M. 288 Davison A. 196 197 198 Davoudazedeh F. 226 Dawoodi Z. 258 260 Dax C. S. 244 Day C. S. 152 216 Day L. 142 Day R. O. 85 94 101 103 123 282 Day V. W. 227 243 244 Dayal B. 319 Dayan D. 302 Deacon G. B. 71 Dean P. A. W. 296 Dean W. K. 108 Author Index de Andrade J. C. 326 Deaton J. C. 187 De Boer B. G. 154 de Boer E.282 Debreczeri F. 284 de Cian A. 176 Decinti A. 295 Decock P. 55 Dedgaonkar V. G. 330 Dedieu A, 263 De Dobetis A. 296 Deeming A. J. 111 202 252,259 De Frees D. J. 66 Dehmlow E. V. 216 Dehnicke K. 139 149 152 197 Dei A. 249 288 Deiseroth H. J. 62 105 de Jong B. H. W. S. 3 de Jong D. 330 De Jonghe M. 300 de Kieviet W. 324 Dekker B. G. 324 Dekock R. L. 40 239 Delaney M. S. 46 49 de la Torre J. 330 Delepierre M. 306 del Fiore G. 327 de Ligny C. L. 324 Dell W. 192 Delville A. 5 Demartin F. 268 269 Demazeau G. 138 Demerseman B. 153 Demidov M. P. 85 De Morco D. 296 DemSar A. 156 Denbs G. 151 Denisevich P. 255 Denisovich L. T. 225 DeNovion C.H. 309 Denton D. L. 36 De Paoli G. 307 De Pape R. 53 Deplano P. 121 209 Depresseux J. C. 327 De Priest R. N. 52 Dergachev Yu. M. 62 de Rocha M. 329 Derouault J. 54 55 Desai C. N. 325 Desauvage S. 122 Desbat B. 129 Deschamps B. 227 Deschamps C. 72 Deschler U. 105 Deshmukh S. 296 DesMarteau D. D. 134 135 Desreux J. F. 307 Dessy G. 208 Detellier C. 5 Deutsch E. A. 198 233 324 Deutzmann R. 331 Author Index Devia D. H. 151 Devillanova F. A. 297 Dewan J. C. 191 288 Diabate S. 321 Dias A. R. 118 154 171 Dias G. H. M. 280 Dias S. A. 292 Dickinson N. 134 Dickman M. H. 287 Dickson R. S. 265 Di Dio E. 206 Diehl M. 93 Diemann E. 149 Diemann F.186 Diephouse J. R. 108 Dieter J. 223 Dietrich-Buchecker C. 219 Digenis G. A. 320 Dijck W. M. 152 Dikshitula L. S. A. 122 Dillon K. B. 100 136 Dilworth J. R. 118 174 175 Dinerstein R. 323 Dines M. B. 311 Dipinto V. M. 321 Dischino D. D. 320 Di Vaira M. 210 240 Diversi P. 219 Dixneuf P. H. 153 214 215 Dixon K. R. 270 Dixon T. A. 129 Djermouni B. 320 326 Dlabal M. L. 127 Dmitriev P. P. 315 DobEnik D. 173 Dobler M. 3 Dobson B. C. 120 293 Dobson C. M. 306 Dodgen H. W. 249 283 Doedens R. J. 287 Doesburg H. M. 5 287 Doetschman D. C. 213 Doi J. A. 44 Doi J. D. 294 Dolan P. J. 35 Dolanski J. 37 Dolcetti G. 39 D’Olieslager W. 300 Doll K. H. 247 Dolphin D.213 256 Domazetis G. 120 256 Dombek B. D. 251 Domenech R. G. 324 Domenech V. 23 Dominguez R. G. 316 Dommrose A. M. 179 Donati D. 294 Donnerhack A. 328 Donohue J. 40 Donovan D. L. 223 Donovan P. W. 88 223 Donovan-Mtunzi S. 175 Doppelt P. 165 Dore J. C. 128 Dori Z. 166 186 Dorokhova G. I. 306 Dory T. S. 95 Douglade J. 195 Downer J. M. 121 274 290 Downs A. J. 34 41 Dozzi G. 62 Drabarek S. 318 Drager M. 87 93 94 Draganjac M. 165 Drago R. S. 210 304 Dragunas A. K. 315 Drahnak T. J. 76 Drake A. F. 230 Drake J. E. 21 22 Drew M. G. B. 9 116 119 158 167 206 207 209 281 286 Drexhage M. G. 143 Droege M. 165 DromzCe Y. 190 Druy M. A. 146 Duax W.L. 17 Dubois B. 55 DuBois D. L. 118 DuBois M. R. 118 Dubowski D. 289 Duckworth P. A. 6 188 Ducourant B. 109 Dudin A. S. 139 Dufek P. 318 Duffield K. 21 Duffy C. 313 Duffy D. N. 89 244 Duggan M. 282 du Mont W. W. 85,91 du Mony W. W. 91 Dunitz J. D. 5 6 Dunks G. B. 37 Dunlap B. D. 299 Du Preez A. L. 237 Du Preez J. G. H. 303 Durand J. 4 Durbut P. 176 Durig J. R. 20 66 Dutschka K. 325 Dwyer M. A. 133 231 296 D’yachenko 0.A, 11 D’yakov V. M. 84 85 Dyhabishvili N. S. 305 Dyke A. F. 252 Dyke J. M. 140 309 Dyke L. J. 325 Dymova T. N. 62 Dzhafarov N. Kh. 92 Dziobkowski C. T. 205 Dzyubenko V. I. 310 Eaborn C. 83 85 86 95 Eakins M. N. 320 Eaton D.R. 151 Eaton G. R. 287 292 Eaton S. S. 287 292 Ebeid F. M. 122 Ebert L. B. 145 Ebner S. R. 286 Ebsworth E. A. V. 82 83 89 90 121 135 279 Eccles T. E. 289 Eckelman W. C. 323 324 Eda K. U. 191 Edelstein N. 128 Edelstein N. M. 39 301 312 Eden J. G. 127 Edwards D. S. 247 Edwards J. O. 107 Edwards P. P. 4 Edwin J. 31 Effenberger F. 219 Efraty A. 200 Efremov V. A. 300 305 Egawa H. 332 Egelstaff P. A. 128 Egorov Yu. S. 313 Eguchi T. 263 Ehkkerman V. M. 332 Ehrenkaufer R. L. 322 Ehrhardt G. J. 315 Eichler B. 316 Eichner M. 10 Eigenbrot C. W. jun. 312 Eilbracht P. 226 Einstein F. W. B. 89 219 239 253 283 Eisman G. A. 209 Ekl J. 319 El-Awady A.A. 232 El-Bayoumy S. 314 Elder H. K. 332 Elding L. I. 293 Elesin A. A. 318 Elfring W. H. 255 Elguero J. 65 Elias H. 284 Ellermann J. 107 Ellert 0.G. 245 Elliott A. T. 325 Ellis C. D. 255 Ellis D. E. 219 Ellis J. 230 Ellis P. D. 296 El Murr N. 224 227 El-Nasr M. S. 233 Els E. 303 Elschenbroich C. 163 El Steifel 116 El-Sweify F. H. 317 El-Tabirou M. 305 Eltzner W. 168 El-Wetery A. S. 323 Elyntin V. P. 25 Ema K. 140 309 Emge T. 116 Emken E. A. 319 Emmi S. 267 Ernsley J. 23 130 Enckrnann N. C. 289 368 Enderby J. E. 132 Endicott J.-F. 235 Endo I. 230 Endo K. 329 Enemark J. H. 119 158 167 Engelbrecht A. 137 Engerer S. C. 308 English A.M. 121 187 English R. B. 244 263 Engman L. 123 Engst P. 141 Ennis C. A. 131 Ennis M. 237 Ensor D. D. 140 309 Ercolani C. 213 Ercolani G. 9 Erdman A. A. 52 Eremenko I. L. 173 245 Ereshko S. F. 52 Eriksen D. 316 Eriksen T. E. 131 Erler B. S. 191 Ertl G. 206 Escudie J. 81 Eshima D. 324 Esho F. S. 281 Eshtiagh-Hosseini H. 106 272 Espenson J. H. 214 Espinet P. 271 Etemadi B. 219 Ettlinger M. G. 321 Evans B. J. 211 Evans J. 251 Evans K. A. 347 Evans W. H. 309 Evans W. J. 32 308 Everett G. W. jun. 293 307 Eveson G. F. 358 Ewer K. P. 30 Extine M. W. 183 187 Eyring M. W. 192 Fabbrizzi L. 249 Faber G. 345 Fachinetti G. 228 Fackler J.P. 121 Faggiani R. 275 Fajare D. E. 236 Falico L. M. 301 Falius H. 102 Fallab S. 233 Falshoud C. P. 17 Fanchiang Y. T. 96 Fanes V. 208 Fang A. 187 Farina P. R. 326 Farina R. D. 233 Farkas V. 321 Farmer J. B. 352 Farnworth F. 358 Farr J. P. 271 Farrah D. H. 273 Farrar D. H. 254 260 261 Farrugia L. J. 242 261 Farthing A. 57 58 Fastrez J. 232 Faull K. F. 318 Faury L. 213 Fava G. G. 170 Fawcett J. 139 167 Fay R. C. 171 300 Fayer J. 212 Fearnley D. P. 292 Febvay J. 188 Federer W. D. 208 Feenstra A, 320 Feher M. 103 Fehlhammer W. P. 216 Fehlner T. P. 40 236 239 Fehrmann R. 122 Feigerle C. S. 300 Feinstein I. 200 Fellmann J. D. 161 Fellows R.L. 309 Felthouse T. R. 183 184 186 Fenichel L. 10 Fenske R. F. 204 Fenton D. E. 10 296 Ferguson G. 287 292 Fernandez J. 205 Fernandez J. M. 260 Fernandez-Valverde S. 330 Fernelius W. C. 313 Fernholt L. 58 Ferragina C. 150 Ferrari M. B. 170 Ferri D. 310 Ferrier H. M. 89 121 Ferris J. P. 99 Fettes D. J. 221 Fichtner W. 189 Fielding G. A. 199 Fielding H. C. 346 Figgis B. N. 199 248 Filho M. F. de J. 329 Filho M. N. 296 Filip J. 319 Filipenko 0. S. 306 Filippov E. A. 317 Finch A. 100 135 Findlay. J. R. 358 Fine D. J. 230 Finholt J. E. 135 189 Fink M. J. 80 Fink R. W. 322 Finke R. G. 165 193 235 266 Finkelstein A. 209 Finn R. D. 320 321 326 327 Finster D.C. 44 46 234 297 Firman P. 15 Firnam G. 126 322 Fischer B. E. 284 285 Fischer G. 78 Author Index Fischer J. 193 227 Fischer J. E. 145 Fischer K. 304 Fischer M. B. 152 216 Fischer R. 310 Fisher J. A. 133 299 Fittkau S. 321 Fitzgerald G. 219 Fitzpatrick P. J. 204 Fjare D. E. 243 Fjeldberg T. 66 Fladerer E. 247 Flahout J. 300 Flanagan R. 325 Flandrois S. 145 Fleet G. W. J. 39 Floerke U. 54 143 303 Floh B. 316 Flood T. C. 203 Floriani C. 282 Florkowski T. 316 Flotow H. E. 302 Fluck E. 101 105 Flygare W. H. 129 Foley H. C. 254 Folting K. 182 183 185 186 Fomenko V. V. 64 Fontaine A. 132 294 Foos J. 320 Foose D. S. 195 269 Foosnaes T.303 Forbus N. P. 229 Ford P. C. 232 251 Fordham B. W. 314 Forel M. T. 54 Foreman T. K. 244 255 Foresti E. 188 ForniCs J. 271 Forshey P. A. 213 Forsling W. 57 Forster M. J. 73 Forsyth J. B. 199 Fourcade R. 109 Fourie P. J. 323 Fourquet J. L. 53 Fowler J. S. 322 Fowles G. W. A. 167 Fox,J. R. 243 244 Francesconi L. C. 153 Franciosi A. 301 Francis A. H. 196 Francis B. E. 323 Francis C. G. 245 Francis M. D. 324 Franck-Newmann M. 219 Franco M. A. 226 Frank A. 107 Franzen H. F. 304 Fraser T. E. 89 90 121 Fratini A. V. 40 Frazier C. C. 215 Frederick L. A. 17 Fredrich M. F. 100 Author Index 369 Freeman G. M. 198 Galvez J. 324 Gervais D.151 Freeman H. C. 289 Galvin R. P. 116 Geselowitz D. A. 233 Freeman M. R. 338 Gamara R. M. 287 Gessner M. 315 Freud A. 325 Games D. E. 14 Gessner W. 58 Frew A. A. 279 Ganguli P. 208 Getices U. 116 Frey H. M. 78 Fridkin A. M. 317 Gans P. 292 Gansow O. 165 Geurts P. 247 Gheller S. F. 170 Friedman A. 314 Friedman A. M. 323 Friedman H. A. 311 Ganyushkin A. V. 83 84 Gaplovskl K. 70 Gar T. K. 85 Gheller S. T. 179 Ghilardi C. A, 237 249 Gibb T. C. 306 Friedman R. M. 263 Garcia M. P. 49 50 234 Gibson D. H. 204 Friedt J. M. 329 Garcia S. L. 325 Gibson R. E. 323 Friend C. M. 245 Garcia-Rendon M. 331 Gielen M. 32 Frihart C. R. 287 Garcia Rosas J. 15 Gieren A. 98 Fritzberg A. R. 324 Gardner A. B. 224 Gilbert R. O. 332 Frohlich C. 247 Garlaschelli L.263 269 Gilchrist K. E. 331 Frolich R. 103 Garneir-Suillerot A. 213 Giles J. R. M. 32 52 Frolov Yu. L. 84 85 Garner C. D. 119 179 206 Gilje J. W. 312 Frolow F. 120 Garnett E. S. 126 322 Gill J. B. 292 Fronczek F. R. 308 Garnett J. L. 318 Gill T. P. 224 Frost D. C. 20 127 Gary G. 295 Gill U. S. 225 Frost J. J. 330 Gassend R. 65 Gillespie R. J. 97 98 107 Fuchita Y. 272 Gatehouse B. M. 297 Gillet B. 307 Fueki K. 327 Gatehouse B. M. K. 176 Gillies D. G. 73 Fiirstenberg G. 104 Fuess H. 93 Gates B. C. 269 Gates P. N. 100 135 Gilson A. J. 320 326 327 Gima S. 108 141 Fujibyashi Y. 324 Fujimori A. 301 Fujimoto M. 176 Gatley S. J. 322 Gatteschi D. 288 Gaudemer A. 198 Gindler J. 314 Ginisty C. 317 Ginsberg M. D. 320 Fujino T. 139 Fujita J. 231 Gaughan G. 193 266 Gaultier J.145 Giordano F. 278 Girardet C. 129 Fujiwara I. 123 331 Fumagalli A, 40 264 Fumagalli H. 243 Funabiki T. 228 Gavens P. D. 235 Gavin R. M. 266 Gavmestani S. K. 233 Gavrilova L. A. 32 Giraudeau A. 71 292 Girgis N. N. 122 Girolami G. S. 184 Gitekunst G. 78 Funahashi S. 284 Furdin G. 145 Gay R. R. 289 Gauane P. A. 179 Gladfelter W. L. 236 243 244 248 254 Furia F. D. 156 Furin G. G. 146 Furmanova N. G. 306 Gboji E. 143 Geay A. P. 321 Gebert E. G. 266 Gladysz J. A. 87 88 203 223 Glaser J. 69 71 133 Furuta T. 318 Gedris T. E. 330 Glavas M. 233 Fu-Son H. 62 Geelhaar L. A. 318 Glavincevski B. 20 Fusstetter H. 28 Gehrke R. J. 316 Gleiter R. 97 Fyles T. M. 17 Gabe E. J. 231 Geike W. A. 247 Gejdel’man A. M. 313 Gelbard A. S. 320 321 322 Gleizes A. 246 Glerup J.177 Glick M. D. 235 Gabeskiriya V. Ya. 309 Gell K. I. 154 Glover K. M. 358 Gabiond R. 219 Gen N. S. 332 Glowiak T. 11 Gable R. W. 94 Gaccia J. 292 Geoffroy G. L. 243 244 254 258 Gnade B. E. 322 Goates S. R. 141 Gadd P. G. 57 Gaeggler H. 316 Gaeggler-Kock H. 316 George E. E. 297 George T. A. 174 Georgion A. S. 130 Goddard J. D. 247 Gode H. 22 Godfrey P. D. 82 Gaft Yu. L. 39 Geraldes C. F. G. C. 307 Godst J. M. 320 Gagne R. R. 208 249 Gerasirnov Ya. I. 305 Goeckeler W. F. 315 Gaines D. F. 6 41 Gerdom L. E. 167 Goedken V. L. 159 Gaizer F. 294 Gal A. W. 161 Gergely A. 295 Gerlach R. F. 88 Goel A. B. 52 61 Goel R. G. 271 295 296 Galas A. M. 236 Gerloch M. 229 248 Goerller-Walrand C. 301 Gales A. M. R. 186 189 Gerritsen G. A. V. 328 Goerz H. 58 264 267 Gershikov A.G. 20 Goetz C. M. 329 Galinos A. G. 63 69 Gerstein B. C. 296 Goetze R. 30 Gallucci J. 256 Galpin I. J. 99 114 Gerstenberger M. R. C. 125 Gerstmans A. 5 Goff H. M. 167 199 213 Goggin P. L. 69 133 271 Gold A. 213 Gold V. 23 128 130 235 Goldberg H. A. 145 Goldschmidt Z. 219 Golembeski N. M. 258 GoliE L. 156 Golovkova L. P. 12 Golubinskii A. V. 83 Gomis D. B. 16 Gongx L. 325 Gonser U. 213 Gonzalez F. 246 Gonzalez G. 105 Goodfellow R. J. 271 Goodin D. B. 196 Goodman B. A. 285 Goodwin H. A, 207 Gordon M. S. 79 Gorelik M. V. 63 Gorgues A. 214 215 Gorokhov L. N. 302 Goryacheva V. I. 305 Gospodinov G. 70 Goswami R. 318 Goto T. 159 Gottschalk A. 325 Gould E.S. 167 Gouskov A. F. 323 Gowenlock B. G. 78 Graddon D. P. 294 307 Gratzel M. 254 255 Graf C. 98 Graham W. A. G. 21 216 Grainger C. T. 23 Grand A. 106 Grandjean D. 235 240 242 Granger P. 55 Granier W. 142 Granozzi G. 249 Grant M. 206 Grant P. M. 314 323 Grant W. J. 343 Grate J. H. 235 Grattan J. A. 326 Graves A. W. 332 Graves B. J. 297 Gray H. B. 164 232 248 267 289 Gray J. L. 55 Grebenik P. 203 Grebenik P. D. 192 Grec D. 188 Gree R. 218 219 Greedan J. E. 150 Greegor R. B. 263 Green B. E. 40 Green M. 49 50 191 194 234 235 261 265 280 Green M. L. H. 95 111 162 192 Greenaway A. M. 287 Greenwood N. N. 38 39 42 269 275 Greenwood R. C. 316 Gregory N.W. 144 214 Gregson A. K. 199 213 Greis O. 302 Grenthe I. 310 Grenz M. 91 Greulich N. 316 Grevels F. W. 221 251 Grewe H. 103 Grey R. A, 257 Griend L. V. 103 Griffin M. 292 Griffith W. P. 172 Griffiths T. 348 Griffiths T. R. 206 Grigor’eva E. A. 4 Grimes R. N. 44 46 233 234 297 Grimme W. 219 Grimmett D. 212 Grimshaw T. A. 302 Grisham J. 313 Grishin Y. K. 260 Grobe J. 152 187 Grodzinski J. J. 112 Groenedijk H. A. 287 Groning O. 293 Gromek J. M. 40 Groning A. B. 293 Groome P. 78 Grooshens T. G. 228 Gropen O. 59 Gross M. 71 292 Grossev M. 91 Groth P. 11 Groves J. T. 175 211 Grundsteins V. 23 Grushkin V. V. 127 Gschneidner K.A. 357 Gschneidner K. A. jun. 302 Gubanova L. I. 84 Gueguen P. 321 Guenot P. 242 Gunther W. H. H. 11 Guentherodt G. 304 Guerchais J. E. 195 252 Gutlich P. 208 Guggolz E. 191 264 Guillaume M. A. 314 323 Guittard M. 300 Gulliver D. J. 274 Gulloti M. 170 295 Gulotti H. 286 Gundersen G. 23 24 28 Gunter M. J. 290 Gupta J. P. 150 296 297 Gupta L. C. 305 Gupta N. D. 294 Gupta S. S. 206 Gupta Y. K. 206 Gurkova S. N. 85 Gurprasad N. P. 17 Gusarev A. V. 302 Gusbeth P. 245 Gusev A. I. 85 Author Index Gusev N. I. 317 Gushikem Y. 94 Gutekunst B. 78 Guthrie D. H. 303 Gutierrez J. L. 316 Guy S. C. 4 Haaland A. 58 59 66 Haas A. 85 125 Haasbroek F. J. 323 Habashi F.206 Habeeb J. J. 67 158 Hackett P. A. 141 Haddad M. S. 208 Hadi D. A. 249 Hadicke E. 98 Haeuseler H. 143 Hagag Y. 319 Hagedorn R. 305 Hagen A. F. 114 Hagenmuller P. 305 Hahn E. 86 Hahn J. 102 103 Haight G. P. jun. 167 Hails M. J. 42 275 Haines R. J. 237 244 263 Haire R. G. 140 309 Haitko D. A. 182 183 187 Haldorsen I. 316 Hall C. A. 322 Hall J. H. jun. 131 Hall L. D. 126 Hall R. B. 311 316 Hall W. T. 161 Hallaba E. 314 Halle L. F. 227 Haller K. J. 40 212 239 Hallmark R. K. 319 Hallock R. B. 68 Halpern J. 214 262 Haltiwanger R. C. 118 Hamilton J. A. 17 Hamlin J. E. 262 Hamon J. R. 225 Hanay W. 4 Haney T. A. 315 Hanke W. 301 Hankey D.R. 261 Hanlon D. J. 216 Hanna D. A, 307 Hanousek F. 37 Hsnsen J. J. 287 Hansen N. P. 193 Hanson I. R. 14 174 Hanson L. K. 212 Hanson R. N. 325 Hansson E. 132 Hanton L. R. 248 Hanumantha Rao V. 122 Hanus J. 318 Hao N. 151 Harada H. 332 Harami T. 213 Harano K. 219 Author index Haraprakas B. 317 Harcourt R. D. 114 Harding P. J. C. 39 Hardwick S. J. 195 269 Hargittai M. 58 Hariharan A. V. 304 Harland J. J. 85 Harlow R. L. 56 151 166 Harper P. V. 327 Harpp D. N. 239 Harris G. M. 231 232 233 Harris R. K. 121 Harris T. V. 154 Harris W. R. 206 Harrison B. A, 293 Harrison P. G. 94 95 Harrison W. D. 282 Hartford W. H. 356 Hartley F.R. 149 Hartmann G. 197 206 Hartner F. W. jun. 61 Hartstock F. 215 Haruna M. 122 Harwig J. F. 322 323 Hasai H. 314 Hasbroek F. J. 315 Haschke J. M. 310 Haser R. 64 Hashem K. E. 254 Hashimoto T. 87 Hassen H. A. 324 Hatane K. 213 Hathaway B. J. 282 Hattori M. 150 Hauenstein J. 63 133 Hauptman Z. V. 97 115 Haushalter R. C. 51 175 21 1 Hauw C. 145 Havenmann H. 86 Hawkes G. E. 195 241 Hawkins D. R. 318 Hawkins L. A. 325 Haworth D. T. 58 Hawthorne M. F. 44 46 49 Hay R. W. 121 Hayashi K. 140 309 Hayes R. L. 320 Hayhurst G. 297 Healy E. F. 35 Healy M. de S. 9 Heath E. 156 Heath G. A. 255 Heaton B. T. 263 Heckley J. 309 Hedaya E. 37 Heeg M. J.235 Heeger A. J. 146 Heek J. 163 Hefford R. J. W. 285 Hefner C. 37 Hehre W. J. 66 Heineman W. R. 198 324 Heinemann M. G. 146 Heinlein T. 102 Heiser B. 228 Heitz C. 329 Helbig B. 320 Heldrich F. J. 108 Helgeson R. C. 11 14 Hellmann J. 102 103 Helus F. 201 Hem S. L. 57 Heman K. J. 324 Hencher J. L. 22 Henderson R. A. 174 Henderson S. G. 90 Hendrick K. 177 Hendrickson D. N. 153 208 230 248 Hendriks H. M. J. 20 281 285 289 Hendriksson U. 69 Hengge E. 87 Henkel G. 98 Henne B. 228 Henrici-OlivC,G. 53 Henrick K. 6 71 188 Henriksson U. 133 Henry W. P. 295 296 Hensby C. N. 319 Her G. R. 312 Herak R. 93 Herber R. H. 92 205 Herberich G. E. 31 266 Herbert I.R. 271 Herforth L. 313 Herlinger A. W. 133 231 296 Herman Z. 300 Herrnanek S. 37 Hermann G. 316 Herold A. 145 Herrmann W. A. 191 264 265 Herron N. 211 Herschbach D. R. 126 Hertz H. G. 130 Hesse M. 30 Hessler J. P. 144 303 Hessner B. 31 194 266 Heumann K. G. 21 Hevesi L. 122 Hewes J. D. 49 Heywood G. C. 218 Hezemans A. M. F. 172 Hichwa R. D. 322 Hickmann U. 316 Hider R. C. 113 206 Higginson W. C. E. 214 Higuchi T. 101 171 Hildenbrand D. L. 140 302 Hilgenfeld R. 11 Hill A. V. 5 Hill C. L. 199 Hill E. W. 236 Hillman M. 226 Himmelwright R. S. 289 Himpsl F. L. jun. 34 41 Hinckley C. C. 262 Hinke A. 135 Hinkle G. H. 325 Hioki A.284 Hipler B. 246 Hirabayashi T. 81 82 Hiraki K. 272 Hirano S. 332 Hiraoka K. 318 Hirashima U. 307 Hiratani K. 17 Hirota F. 21 Hirotsu K. 101 171 Hirshfeld N. 325 Hisatorne M. 226 Hitchcock P. B. 59 106 161 197 273 Hitze R. 85 Hiura M. 108 141 Hladyshevsky E. I. 11 Hnatowich D. J. 323 Hoberg H. 247 Hobson R. J. 158 Hochella M. F. jun. 3 Hockheimer H.-D. 304 Hodgkins T. G. 27 Hodgson D. J. 177 297 Hodgson K. O. 289 290 Hoefer R. 315 Honle W. 103 Hofer E. 169 Hoff C. D. 95 Hoffman G. 310 Hoffman G. A. 263 Hoffman M. Z. 267 Hoffmann R. 42 171 175 234 246 Hoggard P. E. 168 Holbourn P. E. 305 Holecek D. R. 227 Holland H. L. 321 Hollander F.J. 199 203 261 Hollands R. E. 226 Hollcroft J. W. 331 Hollis L. S. 275 Holloway J. H. 139 140 167 Holm R. H. 119 182 Holmes R. A. 198 324 Holmes R. R. 85 94 101 103 123 Holmes S. J. 60 190 Holmes-Smith R. D. 90 Holsa J. 304 Holt D. 116 Holton D. M. 4 Holzbach W. 169 Hong Y. S. 155 Hoppe A. 105 Hoppe R. 142 Horhk M. 141 372 Horch C. 322 Horiguchi T. 314 Horikoshi S. 230 Horiuchi K. 324 Horlock P.L. 314 Hornberger B. A, 255 Horner L. 96 Horrmann W. A. 237 Horsley J. A. 316 Horvath I. T. 240 Horwitz E. P. 317 Hoshi M. 308 Hossain M. B. 93 94 216 Hossain S. F. 264 Hosur M. V. 5 Hough E. 108 Hourdakis A. 5 Hout R. F.jun, 66 Hovs F. E. 111 Howard J. 224 Howard J. A. K. 58 194 204 226 235 242 261 280 Howarth 0. W. 57 156 Howell J. A. S. 237 238 239 Howie R. A. 100 Howlader N. C. 167 Hoyte 0.P. A. 130 Hradilek P. 325 Hrncir D. C. 58 Hsu F. F. 312 HSU,W.-L. 204 Huang C. C. 323 Huang W. F. 301 Hubbard L. M. 111 Hubberstey P. 3 Huber H. X.,245 Hubert-Pfalzgraf L. G. 159 Hudson A, 53 215 Huebner K. 313 Huffman J. C. 37 157 173 177 182 183 184 185 186 Hugel H. M. 114 Huggins J. M. 246 Hughes D. L. 162 174 Hughes J. W. 196 Hughes M. N. 156 Hughes R. P. 222 278 Hulak P. 331 Hulsinga E. 326 Hunold H. 233 Hunt C. T. 271 Hunt J. P. 249 Hunter G. 192 Hunter W.E. 91 155 Hunter W. H. 67 Huong P. V. 129 Huppmann P. 138 Hurst J. K. 111 Hurst R. W. 198 Hursthouse M. B. 178 186 189 236 267 Husk G. R. 218 Hutchinson B. 209 Hutchinson J. P. 195 269 Hutchinson J. R. 165 Hutchison C. A, jun. 140 Hutchison D. J. 135 Hutchison S. B. 127 Huttner G. 31 107 214 260 266 Hwang T. L. 75 Hwang W.-S. 235 Hynes M. J. 220 Iaconnianni F. J. 56 Ianovici E. 330 Ibarra C. 286 Ibers J. A. 256 281 295 Ice R. D. 325 Ido T. 320 321 327 Idowu 0. A. 94 Idziak S. 299 Igi K. 231 Ignat’eva T. I. 5 Iijima K. 21 Ikeda H. 87 Ikeda I. 12 Ikeno M. 80 Ilsley W. H. 66 100 170 Imamura T. 176 Imamutdinova V. M. 22 Imoto S. T. 315 Inaba H.304 Inada K. 316 Inamoto N. 101 Incorvia M. J. 241 Inez W. 213 Ingle D. M. 249 Ingold K. U. 134 Inners R. R. 296 Inoue E. 332 Inoue T. 231 Interrante L. V. 145 Iofa B. Z. 315 Ip D. P. 125 Ippolitov E. G. 39 Irler W. 208 Irodova A. V. 302 Irving R. J. 112 285 Isab A. A, 293 Isaeva S. A. 156 Ishigura T. 229 Ishihara H. 108 141 Ishikawa H. 332 Ishikawa M. 87 Ishikawa N. 76 126 139 Ishimori T. 308 Ishizu J. 247 Ishizu K. 9 157 Ishizu T. 219 Ismailov B. A. 51 Isobe K. 265 266 268 Istomin S. P. 53 Ito K. 122 205 331 Ito T. 231 Author Index Itoh H. 206 Itoh K. 256 Ivanov A. V. 299 Ivanova K. S. 317 Ivashentsov Ya. I. 303 Iverfeldt A.132 Iverson B. 210 Iverson D. J. 192 Ivin K. J. 112 Iwanicki E. 331 Iwasaki F. 260 Iwasaki M. 139 Iwata R. 320 327 Iwato R. 321 Iyengar R. R. 26 Iyer K. 295 Iyer R. S. 328 Iyoda J. 87 Izatt R. M. 3 11 Izawa G. 319 Izmailov B. A. 51 Izquierdo A. 192 Izumi A. 146 Izumi T. 226 Jablonski C. R. 215 Jackels S. C. 286 Jackson G. E. 291 Jackson P. F. 254 261 Jackson R. A. 53 Jackson W. G. 232 233 Jacob E. 138 Jacobson K. B. 295 Jacobson R. A. 188 231 304 Jacques A. R. 348 Jaegermann W. 179 Jakobsen H. J. 296 Jamerson J. D. 312 James B. D. 40 120 James B. R. 213 256 James E. J. 152 Jameson G. B. 256 Janecka A. 322 Jang E. S. 294 Janowicz A.H. 227 228 Jansen M. 22 105 Janusz S. 3 11 Janzen K.-P., 3 Jardine F. H. 262 Jarman M. 318 Jaroszewski J. W. 321 Jarvinen G. D. 117 Jason M. E. 278 Jay M. 320 Jayaraman A. 304 Jeanneaux F. 106 Jeannin Y. 165 179 181 190 Jedral W. 15 Jeffers P. M. 24 Jeffrey J. 155 Jeffrey J. C. 194 204 Jenkins A. D. 59 Author Index Jenkins I. L. 358 Jens K. J. 219 Jensen C. F. 296 Jensen G. S. 177 Jensen J. E. 203 Jensen L. H. 206 Jezierska J. 286 Jezierski A. 157 Jezowska-Trzebiatowska B. 11 Jha N. K. 295 Jilek K. 331 Jimenez-Reyes M. 330 Job R. 232 Jobert A, 145 Jochen K. 90 Johannsen B. 198 313 Johansen E. S. 168 Johansson G.57 71 132 John G. R. 220 261 John P. 78 Johnson B. F. G. 219 235 236 253 254 258 260 261 Johnson C. E. 136,219 220 Johnson D. E. 138 Johnson D. L. 87 88 203 223 Johnson G. K. 136 138 Johnson J. J. 93 Johnson K. E. 126 Johnston S. A, 20 Jolvier M. 295 Jonas J. 263 Jones A. C. 289 Jones A. G. 196 197 198 Jones C. W. H. 239 Jones D. F. 242 Jones D. J. 130 Jones M. M. 296 298 Jones P. 213 Jones P. G. 197 206 291 292 Jones R. 345 Jones R. A. 91 186 189 267 Jones R. F. 274 Jones S. B. 154 Jones S. K. R. 49 234 Jones S. L. 358 Jones T. 239 Jones W. 119 205 Jons O. 168 Jonvik T. 24 Jordan R. B. 206 Jordan R. D. 233 Josland G. D. 140 309 Jost K.H. 105 Jostes R. 149 Jourdain J. L. 131 Joyner C. H. 129 Jung C. W. 46 Juri P. N. 262 Juszynsky M. 324 Jutzi P. 91 Kacner M. A. 141 Kaden L. 198 Kaden T. 284 Kadish K. M. 175 213 294 Kadushkin A. V. 331 Kadyrova Z. S. 57 Kaegi H. H. 320 Kaesz H. D. 258 Kaffrell N. 316 Kaftory M. 186 Kafutu K. 219 Kaganovich V. S. 217 Kagansky M. M. 39 Kahjehnassini M. 208 Kahn M. 314 Kahovec J. 316 Kaim W. 61 Kaindl G. 304 Kaiser S. L. 193 Kalashmikov Ya. A. 25 Kalcher W. 265 Kaldor A. 311 316 Kalina D. G. 317 Kalincak M. 324 Kalinin A. E. 226 Kalinin V. N. 50 51 Kalinnikov V. T. 173 245 Kallendorf C. J. 133 Kalluny R. K. 78 Kalnin I. L.145 Kamata M. 171 Kameda M. 35 Kamenar B. 111 Kaminaris D. 63 Kamisawa K. 283 Kamiyama S. 226 Kampmeier J. A. 264 Kan C. T. 175 Kanamatsu K. 219 Kanatzidis M. 165 Kaneda T. 14 Kane-Maguire L. A. P. 14 220 Kaner D. A. 261 Kaner R. B. 113 Kanetsuki K. 307 Kanev A. N. 84 Kanippayoor R. K. 130 Kanno R. 116 158 Kanno T. 331 Kanska M. 318 Kanski R. 321 Kant A. 299 Kanzaki T. 205 Kapon M. 186 Kapoor R. N. 95 Kappenstein C. 105 Kappes M. M. 205 Karalova Z. K. 317 Karavaev S. A. 310 Karayannis N. M. 56 Karel K. J. 220 Kargareteli L. N. 305 Karle I. L. 17 Karle J. 17 Karve R. S. 141 Kasahara A, 226 Kashaev A. A. 84 Kashiwabara K. 231 Kashoulis A.78 Kasper J. S. 145 Kasperson F. M. 326 328 Katahira D. A. 258 Katayama S. 76 Katayama T. 12 Katovic V. 157 Katsura T. 112 205 Katzenellenbogen J. A. 318 323 Katzer J. 331 Kaul B. 288 Kawaguchi M. 144 Kay M. A. 315 Kayali A. 290 Kayo A. 205 Kazantsev A. V. 51 52 Kazarina E. 235 Kbir-Ariguib N. 306 Keana J. F. W. 318 Kececi A. 202 Keck H. 186 Keefer K. D. 3 Keene F. R. 255 Keh-Shink 214 Keil M. 219 Keilacker H. 325 Keiter R. L. 193 Keller C. 313 Keller E. 240 Keller N. 123 128 Kelly H. C. 213 Kelly K. P. 270 Kelly L. F. 219 220 Kelly R. L. 221 Kemp R. A. 224 Kemp T. J. 298 Kempen H. V. 289 Kenamerer G. E. 145 Kennard C.H. L. 40 196 Kennedy D. M. 282 Kennedy F. G. 219 Kennedy J. D. 38 39 42 43 269 275 Kenner G. W. 99 114 Kenney M. E. 53 146 Kent J. P. 97 98 Kergoat R. 195 Kerimova F. R. 92 Kerkeris A. 246 Kerr K. A. 186 Kershaw R. 113 Kershulis V. I. 315 Kessler R. M. 288 Khaassen A. A. 282 Khac T. N. 5 374 Author Index Khalkin V. A, 315 Khan A. H. 214 Khanvilkar J. N. 330 Khasrou L. N. 21 22 Khathing D. T. 195 Khemiss A, 219 Khol’nov Yu. V. 313 Khopkar P. K. 318 Khromova N. V. 85 Kidani Y. 283 Kiejzers C. P. 282 287 Kiel G. 108 Kiernan P. M. 172 Kierstead H. A. 302 Kijowski J. 140 300 Kikindai T. 113 Kikkawa E. 233 Kikuchi M. 329 Kilbourn M. R.318 Kim J. H. 293 Kim J. R. 323 Kim K. C. 141 309 Kimber B. J. 121 Kimura E. 249 286 Kimura K. 12 Kimura T. 327 Kinard W. F. 16 King E. L. 294 King G. 280 King K. 206 King M. A. 25 123 King R. B. 32 135 189 King T. J. 17 Kinnison R. R. 332 Kinomura N. 67 Kinoshita I. 231 Kinoshita K. 219 Kipton Powell H. 285 Kirby C. 20 Kirby J. A. 196 200 Kirk A. D. 167 Kirkpatrick C. C. 185 186 Kirokawa Y. 314 Kirschner A. S. 325 Kiso Y. 314 Kistenmacher T. 116 Kitagawa S. 282 Kitaura K. 246 Kitazume T. 126 Kiwi J. 254 Kizas A. O. 260 Klabunde K. J. 228 245 Klaning U. K. 131 Klautke S. 105 Kleeman G. 137 Kleeman S. 101 Klein B. 307 Klein H. 246 Klein M.L. 128 Klein M. P. 196 200 Kleinschmidt P. D. 140 302 Kleinschmit P. 349 Klemenkova Z. S. 219 Klemperer W. 129 Klendworth D. D. 159 184 Klerks J. M. 60 Kleshchevnikov A. M. 139 Kline G. A. 35 Kline R. F. 215 Klingebiel U. 30 83 Klinger R. J. 235 Kloecking R. 320 Kloster G. 319 320 Klotzbucher W. E. 221 Klouras N. 155 Klusik H. 19 Knappe P. 302 Knerr G. D. 136 Kniep R. 62 Knifton J. F. 251 Knight L. B. jun. 133 299 Knobler C. B. 14 46 49 258 Knochel A. 4 Knospe S. 325 Knoth W. H. 166 Knowles W. 263 Knox C. V. 9 Knox G. R. 218 Knox S. A. R. 203 219 252 Koacher J. K. 115 Kobayashi H. 168 Kobayshi H. 317 Koch H. 313 Kochi J. K. 235 Kodama G.33 35 Kodama M. 249 286 Koebler U. 304 Kohler F. H. 31 163 Koelbl J. 321 Koler F. H. 247 Konig E. 207 Koenig K. 263 Kopf H. 155 Koser H. G. 219 Koster R. 30 Koetzle T. F. 40 243 264 266 Kohara T. 246 Kohl F. X. 91 Koie Y. 273 Koizumi M. 67 116 158 Kojima A. 178 Kokisch W. 262 Kokkes M. 273 Kol M. 125 Kolachkovski A. 315 Kolawole G. A. 157 Kolina J. 319 Kolks G. 287 Koltai E. 321 Kolthammer B. W. S. 183 186 187 202 Kolthoff I. M. 15 16 Komar D. A. 217 Komarek P. 324 Komarevskij V. M. 332 Komarova M. P. 5 Komissarova L. N. 305 Kon H. 213 Konito A. 52 Konteatis Z. 311 Kontis S. S. 328 Koo J. S. 323 Koob R. D. 79 Koola J.D. 228 Koppanol W. H. 213 Koran D. 208 Koridze A. A. 260 Kork H. J. 98 Korneeva T. A, 19 Korobov M. V. 139 Korp J. D. 202 231 257 283 Korper-Colig B. 111 Korsakov M. V. 318 Korsunsky V. I. 86 Kosakowsky U. 321 Koshy K. 231 Koski W. S. 329 Koslova N. 151 Kost M. E. 302 Kostenko A. L. 56 Koster H. 255 KostiC N. M. 204 Kosturiak A. 325 Kotake K. 87 Kotel’mikova A. S. 202 Kothari K. 324 Kotova L. S. 225 Kouinis J. K. 63 69 Kovacs Z. 317 Koval C. A, 288 Kovalchouk N. D. 323 Kovar D. 87 Kovar R. A. 174 Kovredov A. I. 52 Kowalilc T. 292 Kox K. P. 95 Koyama T. 314 Koyama Y.,21 Koyanagi T. 332 Kozhevnikova N. M. 68 Koziolkiewicz W. 322 Kozlowski H.292 Kozlowski J. F. 57 Kozuka M. 229 Kozyreva 0. I. 321 Kramer A. V. 324 Kramer G. M. 311 316 Krantz A. 81 Krause L. J. 270 Krause S. 282 Krause W. 102 Krebs B. 98 103 Kreilick R. W. 231 Kreindlin A.-Z.,226 Kreiter C. G. 201 Kress J. 56 Kress N. 173 255 Krickemeyer E. 179 Kriechbaum G. 191 Author Index Kristine F. J. 150 Krivokhatskij A. S. 317 Kroeger M. K. 304 Krohn K. A. 324 Kromer L. U. 294 Krommes P. 108 Kronrad L. 325 Kropshofer H. 24 Krost D. A. 247 Kroto H. W. 25 106 123 272 273 Krueger A. 330 Kriiger C. 31 Kruger G. 189 Kruglov A. A, 202 Kruse R. 7 Kubas G. J. 117 119 Kubicki M. M. 195 Kubik M. 332 Kuchen W.135 186 Kuctz D. M. jun. 296 Kuksis A. 7 Kulagin N. M. 303 Kulmala H. 323 Kulszewicz I. 146 Kumada M. 76 87 Kumar R. 237 Kumar R. C. 136 Kumar S. 117 181 Kundalkar B. R. 330 Kundu K. K. 130 Kung H. F. 323 Kuni H. 322 Kunu K. 95 Kunz A. B. 206 Kunze K. R. 209 Kupferschmidt W. C. 233 Kurbakova A. P. 39 Kurochkina L. N. 305 Kuroda R. 130 230 283 Kurohara T. 316 Kuroya H. 178 Kutter J. 135 Kuwana T. 213 Kuz’min 0.V. 244 Kuz’mina L. G. 86 Kuznesof P. M. 53 146 Kuznetsov N. T. 39 Kuznetsova G. P. 303 Kuznetsova V. S. 317 Kwik W. L. 282 Kyba E. P. 262 Kyrs M. 316 Laali K. 128 146 Laangstroern B. 320 Labauze G. 231 Labes M. M. 145 Lacelle S.296 Lachmann N. 319 La Croce S. 222 Ladd J. A. 159 Ladd M. F. C. 142 Ladensberg J. M. 219 Lagarde P. 132 294 La Ginestra A. 150 Laguna A. 291 292 Laguna G. A, 141 309 Laguna M. 204 291 292 Lahiriy S. 207 Lai R. D. 272 Lai Y.-H. 53 Laidlaw W. G. 114 Laird B. B. 222 Lakner J. F. 302 Lakshmikantham M. V. 123 Lam W. Y. 135 Lamache-Duhameaux M. 170 Lamb J. D. 3 11 Lambert C. 222 Lampe P. A. 298 Lancas F. M. 326 329 Lance E. A. 294 Landee C. P. 249 287 Landers A. G. 107 Landini D. 6 Landman J. T. 212 Lanfredi A. M. M. 253 Lang J. 324 Lange M. 213 Langlais F. 138 Lappert M. F. 155 161 190 215 Lappin A. G. 214 284 Lapter D. M. 303 Larbot A.4 Large M. R. 358 Larkworthy L. E. 142 Larrazbal G. 295 Larsen N. G. 281 Larson D. T. 310 Larsson B. 320 Lashewycz R. A. 203 231 261 Laskorin B. N. 16 317 Laszlo P. 5 Latscha H. P. 146 Lattman M. 100 Lau K. H. 140 302 Lau S. j.y. 285 295 Laufer P. 320 Laughlin J. S. 320 321 322 Lauher J. W. 243 Laureni J. 81 Laurenson G. S. 34 83 100 122 Laurie S. H. 290 Laushkina G. A. 331 Laussai J. P. 295 Lavallee D. K. 294 Lavayssiere H. 81 Laverdet G. 131 Lavigne G. 181 257 Lawrence J. M. 301 Lazar J. 324 Lazare R. 318 Lazarev V. V. 127 Lazoryak B. I. 300 Lay D. G. 183 184 186 Leach J. B. 34 36 Leadbetter A. J. 224 Leaver G. P. 345 Lebech B.304 Lebedev N. A. 315 Le Borgne G. 238 Le Bozec H. 214 215 Le Bras G. 131 Leck T. J. 131 Lecomte J.-P. 213 Lednor P. W. 215 Ledon H. J. 176 Ledsham R. C. 142 Lee B. E. 346 Lee C. C. 224 225 Lee C.-L. 271 Lee E. 294 Lee F. S. C. 329 Lee H. 123 Lee J.-S. 152 Lee J. Y. 307 Lee K. M. 325 Lee L. 136 Lee M. 116 Lee R. 322 Lee S. T. 301 Lee T. W. 135 189 Lee W.-S. 228 Lee Y. J. 213 Lefebvre J. 165 179 181 Leflem G. 305 Legasov V. A. 139 Leger J. M. 304 Legg J. T. 231 Legon A. C. 129 130 Lehmann H. 257 Lehmann T. 310 Lehn J.-M. 10 14 Leigh G. J. 162 173 197 Leighton J. 358 Lein G. M. 14 Leites L. A. 39 52 Leitnaker J. M. 140 Leitzke O.24 138 168 Lelieur J. P. 305 Lelj F. 39 Lemal D. M. 222 278 Le Marouille J. Y. 235 240 242 Lemenovskii D. A. 226 Lemerle J. 166 Lengel R. K. 282 Lenowicz M. E. 236 Lentle B. C. 325 Lentz D. 132 138 Le Ny J.-P. 56 Leonaldi R. 296 Leonardsson I. 321 Leonelli J. 177 185 187 Leonyuk N. I. 23 Le Page Y. 204 231 Leparulo M. A, 166 376 Leporati E. 231 Lerch P. 330 Lerch R.E. 331 Lerman O. 125 LeRoy Eyring 304 Lesch D. A. 237 Leskela M. 304 Leslie A. E. 228 Lestrina T. V. 86 Leszczynski J. 7 Letoffe J. M. 142 Levakov B. I. 313 Levanda K. 311 Levason W. 139 164 274 Lever A. B. P. 53 113 199 Levesque G. 240 Levin V. I. 315 Levisalles J.190 Levitin I. 235 Levy D. E. 314 Levy D. H. 126 Lewis H. C. 256 Lewis J. 219 236 254 258 260 261 Lewis R. E. 314 Lexa D. 213 Ley S. V. 219 Lhoste J. 213 Li Y. S. 66 Liang B. F. 286 Liberatore F. A, 324 Lichtenberger D. L. 119 Liebelt A. 139 Lieberman I. M. 322 Liese W. 197 Liesegang G. W. 15 Lieser K. H. 313 330 Lietz M. 107 Lifshitz E. 196 Lim Y. C. 258 Lin I. J. B. 153 Lin J. D. 15 Linck R.-G. 172 Lincoln S. F. 249 300 Lind J. 131 Linder K. 324 Lindoy L. F. 115 307 Lineberger W. C. 300 Ling L. M. 78 Linga H. 150 Liotta C. L. 322 Lipovskij A. A. 313 Lippard S. J. 191 275 287 288 Lippert B. 275 Lipps W. 201 Lipscomb W.N. 33 34 35 Lisichkina 1. N. 127 Liteplo M. P. 324 Little D. 187 Litvin B. N. 306 Litvina M. N. 317 Liu B. L. 325 Liu C. S. 75 87 Lively M. O. 319 Livni E. 324 Lloyd J. E. 354 Loc’h C. 314 322 Lock C. J. L. 275 Lockwood A. H. 320 Lodge S. P. 78 Loeb S. J. 288 Lo Giudice M. T. 64 Loitch D. M. 90 Lokhande R. S. 330 Lokshin B. V. 219 Lombard A. 189 Lomora T. N. 152 Long G. J. 114 195 206 Long J. A. 44 Long J. L. 331 332 Long M. A. 318 Longenecker J. P. 321 Lopatin S. N. 139 Lopez B. 330 Lopez G. L. F. 314 Lopez O. 239 Lopez-Garcia A. 68 Lorberth J. 108 Lorenz B. 198 Loshakov G. A, 331 Loshchenov V. B. 306 Lotz S. 189 228 Louati A. 71 292 Loub J.109 Louie H. W. 307 Lourdudoss S. 3 Loutfy R. 54 Louw W. J. 274 Lovtsyns A. V. 313 Lowan D. 116 Lubien C. D. 290 Lucas J. 23 130 Lucazean G. 224 Luchinat C. 231 Lucy A. R. 264 Ludi A. 257 Lutkecosmann P. 104 Lugan N. 257 Lui Y. Y. 318 Lundqvist H. 320 Luong-Thi N. T. 155 Lustfeld H. 304 Lutar K. 127 Lutz H. D. 143 LyEka A. 37 Lyday P. A, 347 Lynch M. W. 208 230 248 Lysenko G. Yu. 317 Lyte F. E. 282 Lytle F. W. 263 Maah M. J. 106 272 Maas E. T. jun. 311 Maatta E. A. 312 McAlees A. J. 287 292 McAlpine I. 358 McArdle P. 220 Author Index McAuley A. 214 McAuliffe C. A. 293 McCann M. 9 286 McCarron E. M. 145 McCarthy T. J. 276 Maccartney D.H. 214 McCelIand G. M. 126 MacClean G. 114 McClellan W. J. 321 McClure D. 311 McCormick F. B. 111 218 McCoubrey J. C. 353 McCrindle R. 287 292 MacDermot J. 319 MacDiarmid A. G. 146 MacDonald C. B. 127 Macdonald E. K. 135 McDonald I. R. 128 McDonald J. M. 314 McDonald J. W. 191 McDonald R. B. 346 McDonald W. S. 42 43 267 269 275 277 McDowell C. A. 20 127 McDowell W. J. 16 McElvany K. D. 323 McFarlane W. 4 37 121 297 McGarvey B. R. 62 133 208 McGinnety J. A. 278 McGlinchey M. J. 151 McGowan D. G. 325 MacGregor R. R. 322 Machan V. 315 324 McHatton R. C. 214 Machulla H. J. 325 Maciel G. E. 55 McIntosh D. F. 247 Mackay K. M. 244 Mackay M.F. 170 197 McKee M. L. 33 34 35 McKee V. 209 290 McKendry L. H. 321 McKenna W. A. 235 McKennis J. S. 223 Mackenzie J. D. 143 McKie G. 109 McKinney B. D. 285 McKinney R. J. 246 248 McLaughlin K. W. 184 MacLaughlin S. A. 252 253 MacLean D. A. 150 MacLean G. 98 McLennan A. J. 126 McManus N. T. 135 McMillan D. R. 282 289 McNaughton D. 82 McNulty G. S. 251 McPartlin M. 6 71 188 254 261 McPhail D. B. 285 McQuillan A. D. 302 McQuillan G. P. 100 Author Index MacQuitty J. J. 215 Madan S. K. 233 Maddock A. G. 330 Maeda M. 322 Maeda T. 12 Maeda Y. 205 211 213 Maeder M. 233 Magaoka Y. 315 Magee R. J. 120 Magill L. S. 231 Magni A. 263 Maguire M.M. 131 Mahe C. 240 Mahmoud F. M. S. 85 86 Maia A. 6 Maier G. 78 Maier N. A. 52 Maier-Borst W. 3 14 Maillard D. 129 Maimbor P. 320 Maiorova L. P. 81 Maire J. C. 65 Maisano G. 132 Maitlis P. M. 262 265 266 Majid A. 21 Majore I. 22 Makagohova L. N. 315 Makarova T. P. 317 Makaryunene Eh. K. 315 Makhaev V. D. 39 Maksimova S. I. 306 Malakar D. 294 Malatesta V. 141 Malcolme-Lawes D. J. 323 326 328 Maleki L. 209 Malik K. M. A. 178 189 Malik S. K. 302 Malik-Diemer V. A. 17 Malikov D. A. 317 Malin J. M. 214 Mallapurkar V. S. 316 Malmquist P. A. 116 Mal’tseva G. V. 68 Malueg D. H. 269 Malysheva L. P. 317 Mamedov Kh. S. 92 Manassen J. 120 Manassero M.268 269 Mance A. M. 228 Mandel M. 219 Mander L. N. 290 Mandolini L. 9 Manfredi J. F. 314 Manfredotti A. 282 Mangani S. 294 Mangerud M. 28 Mangoliashi E. 213 Mani F. 157 Mani R. S. 324 325 Mann B. E. 265 Mann K. R. 224 Manning A. R. 237 245 Manning M. R. 229 Manning W. B. 319 Manohar H. 11 Manoharan P. T. 231 ManojloviC-Muir L. 190 Manriquez V. 103 Mansuy D. 213 Mantsch H. H. 134 Manzar J. 116 Maple M. B. 301 Marais I. L. 237 Marchetti F. 202 228 Marcotrigiano G. 283 Marcotte R. B. 275 Marder T. B. 44 Margerum D. W. 288 Margorskaya D. I. 86 Mark H. B. 115 Markiewicz R. S. 145 Marko L. 240 Marks D. N. 208 Marks T. J. 139 309 312 Marongiu G.297 Marples J. A. C. 358 Marritt W. A. 208 Marshall A. G. 325 Marsili M. 107 Marsmann M. 325 Marston A. 99 114 Martelli J. 218 219 Marten D. F. 216 MArtensson N. 14 116 Martin D. L. 322 Martin R. B. 285 Martin R. L. 248 Martha D. 219 Martinenge C. S. 269 Martinengo S. 263 Martinez F. 27 Martin-Frbre, J. 165 Martinho Sim6es J. A. 154 171 Marty W. 232 Martynova T. N. 84 Marumo F. 133 Maruta T. 272 Maruyama Y. 315 Marwaha A. K. 300 Marynick D. S. 6 Marzilli L. G. 324 Mascharak P. K. 289 Mascherpa G. 109 Masci B. 9 Mashyukov V. S. 83 Mason G. W. 317 Mason J. 175 Mason M. G. 301 Mason R. 199 Mason S. F. 230 283 Mason W. R. 232 Massa W.108 Masse R. 303 Massey S. 323 Massola C. P. 68 Masson J.-M. 145 Masters A. F. 179 192 Masuda H. 256 Matheson T. W. 257 Mathey F. 193 227 Mathiasch B. 94 Mathieu R. 238 240 Mathew J. 186 Mathur J. N. 237 318 Mathur M. A. 97 Mathur P. 239 Matijevic E. 205 Matisons J. G. 254 Matsuda A. 227 Matsuda Y. 159 176 Matsui H. 296 Matsumoto K. 178 283 287 Matsumoto Y. 231 Matsuzaki R. 56 Matthews R. W. 71 73 Matthews T. G. 282 Mattson B. M. 21 216 Matulova M. 320 Matusinovic T. 232 Mavani I. P. 202 Maverick A. W. 164 Maverick E. 14 Mavkay K. M. 88 Maxwell W. M. 122 May C. J. 7 May P. M. 291 Mayerle J. J. 225 Maynard R. B. 46 233 234 312 Maynor P.295 Mayr A. 216 Mays M. J. 201 235 258 260 Mazaitis J. K. 323 Mazaleyrat J.-P. 11 Mazid M. A. 224,293 Maziere B. 314 322 Maziere M. 320 Mazzi U. 202 Mazzocchin G. A. 202 230 Mead K. A. 252 Mealli C. 247 Meares C. F. 307 Mehrotra S. K. 101 116 Meikrantz D. H. 316 Meinema H. A. 108 Meiramov M. G. 52 Meisel A. 4 Meisenhelder J. 54 Meiske L. A. 231 Meli A, 214 230 240 Melin J. 145 Mell E. J. 145 Mellea M. F. 268 Mel’nikov P. P. 305 Meltzer H. Y. 323 Menabue L. 283 Menard K. 222 Menear S. L. 306 378 Mengatti J. 315 Menge G. 102 Mentzen B. F. 106 Mercer M. 139 Mercier R. 195 MerCnyi J. 131 Merrick M. V. 323 Merrill C.L. 208 283 Merriman W. R. 346 Merz A. 10 Messerle L. W. 161 Messmer R. D. 247 Mestelan G. 320 Metrot A. 145 Mews R. 137 197 206 Meyer B. 186 Meyer B. E. 239 Meyer C. A. 115 Meyer G. 300 303 Meyer T. J. 255 Mialki W. S. 116 182 Michaud P. 225 Micheloni M. 294 Michels G. D. 200 Michl J. 76 115 Middleton R. A. 228 Midollini S. 210 237 247 249 Migliardo P. 132 Mignani G. 235 240 Miguel J. A. 202 Mihelcic J. M. 268 Mihm G. 78 Mikheeva N. M. 332 Mikulaj V. 315 Mikulski C. M. 56 Milewski-Mahria B. 105 Milh 0. S. 114 MilicCv S. 156 Millan A. 265 Millefiori A. 249 Millefiori S. 249 Millen D. J. 130 Miller J. M. 130 Miller K. M. 158 Miller P.E. 167 Miller R. M. 206 Milliken J. W. 145 Millington P. L. 109 Mills A. 257 Mills 0.S. 99 114 289 Mills R. M. 194 222 Mills S. L. 325 Milne C. R. C. 161 Milone L. 235 241 253 Milyukova M. S. 317 Minami N. 319 Minelli M. 167 Mingos D. M. P. 42 120 234 263 272 Minich M. 318 Minor P. C. 53 199 Mir Q.-C. 136 Miro N. D. 228 Mironov K. E. 305 Mirzadeh S. 314 Misawa H. 257 Mishra M. N. 70 Mishra S. P. 111 131 330 Mislow K. 192 Mispelter J. 213 Missert J. P. 282 Mitchell P. R. 233 Mitra S. 213 Mitrpachachon P. 242 261 Mitschler A. 193 227 Mitsudo T. 219 257 Mittal J. P. 141 Miyake M. 133 Miyake S. 178 Miyake T. 316 Miyamota T. 318 Miyati K. 282 Miyazaki T.327 Miyoshi K. 231 Mochida Y. 126 Mockler G. M. 230 Modena G. 156 Moerlein S. M. 323 330 Moguel M. K. 293 Mohammed E. S. 290 Mohan N. 168 Mohd-Nor A. R. 113 206 Mohmand S. 81 82 Mohr H. 107 Moinet C. 225 Mo Khen Khaa 315 Mokhosoev M. V. 68 Moledina M. 331 Molloy K. C. 93 94 Molodkin A. K. 63 Mornentan M. 213 Monacelli F. 213 Moneti S. 247 Monks R. 323 Monserrat K. 255 Montanari F. 6 Moody D. C. 35 37 Mooiman M. B. 229 Moon K. A. 299 Moore D. S. 261 Moore I. 194 Moore P. 298 309 Mootz D. 21 128 130 186 Mopert A. 219 Moran M. J. 145 161 Moran T. F. 319 Moras D. 10 Morcos N. A. 315 More K. M. 287 292 Moreno L. 324 Morgan L.O. 295 Morgat J.-L. 321 Mori M. 256 Mori W. 287 Morikawa H. 133 Morimoto M. 181 Morita N. 219 Autho Index Morita R. 324 Morita T. S. 173 Morita Y. 213 Moriyama H. 123 331 Moro R. 332 Morokuma K. 246 Morpert A. 218 Morpurgo G. O. 208 Morris A. 140 309 Morris K. P. 128 Morris M. C. 289 Morris R. H. 197 Morrishima I. 211 Morrison I. E. G. 113 206 226 Morrison J. A. 34 270 Morrison M. M. 111 Morse K. W. 40 Morton J. R. 131 Morton S. 223 Mosaad K. 314 Mosini V. 208 Moss D. S. 219 Mott G. N. 138 Movsumov E. M. 92 Moxon N. T. 199 Moyniha C. T. 143 Mronga N. 197 Mucha I. 325 Miiller A. 149 165 168 179 180 186 Mueller D. 58 Muller E.W. 208 Mueller H. 302 Miiller L. 196 Miiller U. 139 164 197 Mueller-Buschbaum H. 57 64 Mueller-Platz C. 320 Mueller-Westerhoff U. T. 226 Munch V. 134 Muenze R. 313 Muetterties E. L. 19 191 227 236 245 260 266 Muir A. S. 100 135 Muir K. W. 139 190 279 Muir L. 307 Muir L. M. 279 Mukai K. 9 Mukhedkar A. M. 330 Mulazzani Q. C. 267 Mullane J. 282 Mullins F. P. 94 Mulokozi A. M. 305 Munakata M. 282 Mune R. 314 Murai S. 262 Murakarni Y. 159 176 Murano Y. 319 Murata K. 227 Murata T. 332 Murav’ev E. N. 305 Muravina A. G. 138 Author Index Murawski D. 319 Murdoch J. D. 121 Murphy A. 282 Murphy P. D. B. 296 Murphy W. R. 255 Murray E.K. 82 Murray I. E. P. 190 Murray K. S. 290 Murray M. 261 Murray R. W. 255 Murray S. G. 149 Muschik G. M. 319 Musco A. 266 Music S. 315 Muster W. K. 288 Muth H. 284 Myakushev V. D. 51 Myasoedov B. F. 317 332 Myasoedov N. F. 319 Myers R. 292 Myers R. D. 126 Myskiv M. G. 11 Mysliwy T. 324 Nadzhafov G. N. 92 Naegeli R. 266 Nagar M. S. 317 Nagarajan R. 305 Nagel C. C. 254 Nagvekar U. H. 325 Nagypal I. 284 Nair M. S. 284 Najjar R. C. 156 159 Nakajawa K. I. 76 Nakagawa Y. 257 Nakahara A, 287 Nakajima F. 332 Nakajima T. 144 146 Nakamoto K. 229 Nakamoto M. 171 Nakamura A. 118 170 Nakamura H. 16 Nakamura M. 211 Nakane R. 316 Nakae Y. 287 Nakashima M.316 Nakata M. 118 Nakata N. 170 Nakatsu K. 219 Nakhutin 1. E. 331 Nakon R. 294 Nanni E. J. 111 Narasimhan D. V. S. 324 Narayanaswamy R. 139 164 Narbel P. 219 Narten A. H. 132 Narula A. S. 219 Natarajan K. 260 Natarjan P. 233 Navarro R. 204 Navrotsky A, 304 Nawi M. A. 158 Nazar L. F. 245 Nazarchuk T. N. 25 Nazzal A. 226 Negishi E. 60 Negita H. 108 141 Neill P. 209 Nejedly Z. 319 Nekrasov V. I. 331 Nelson G. O. 238 Nelson J. 9 116 207 Nelson M. A. 35 Nelson R. L. 358 Nelson S. M. 9 116 207 209,281 286 Nelson W. J. H. 261 Nemessanyi Z. 324 Nemo T. E. 211 Nemoto Sh. 317 Nerud F. 318 Nesbit M. C. 176 Nesmeyanov A. N. 127 225 Nestle M.O. 241 Neumann W. P. 80 Newton R. F. 10 Newton W. E. 191 Nguen Kong Chang 315 Nguyen Quy Dao 309 Niarchos D. 299 Nicholas K. M. 223 240 264 Nicholls J. N. 254 260 Nicholson B. K. 88 89 215 244 Nicholson D. G. 108 Nicholson R. W. 324 Nickles R. J. 322 Nickleweit-Luke A. 103 Niebon 0.F. 122 Niecke E. 103 104 Niedenzu K. S. 27 Niedernhofer B. 284 Nielson A. J. 178 Nigam S. 324 Nigam S. N. 161 Nikitin M. I. 139 300 Nikolaev V. M. 318 Nikonorov Y. I. 146 Nikonova L. A. 156 Nimry T. 184 Nishi T. 123 331 Nishikawa S. 331 Nishimoto T. 284 Nishimura E. K. 44 Nishizawa M. 232 Niwa T. 316 Nixon J. F. 106 272 273 Noth H. 6 19 26 28 29 30 32 Nohr R.S. 53 63 146 Noltemeyer M. 99 197 206 Noltes J. G. 108 Noma H. 314 Nonaka T. 332 Noordik J. H. 5 245 Norbert A. 4 Norman A. R. 267 Norman J. G. 207 Norman N. C. 191 Norris A. R. 297 Norris E. 313 Norris V. A. 289 Noth H. 100 Nott G. M. 183 Nouet J. 53 Novgorodov A. F. 315 Novikov G. I. 139 Novikov Yu. P. 332 Novotortsev V. M. 245 Nowek A. 7 Nowell D. 297 Nowell D. V. 150 296 Nugent W. A. 151 Numatatsu T. 176 Nunn A. D. 324 Nunn N. M. 128 Nuttall R. L. 309 Nutton A, 262 266 Nuzzo R. G. 276 Nyathi J. Z. 59 Nyburg S. C. 7 152 Nyholm R. S. 14 Oakley R. T. 97 98 99 114 115 Oberdorfer F. 201 Oberhammer H. 128 136 O’Brien H. A. jun.314 323 O’Brien J. P. 51 O’Brien P. 285 Ochi K. 316 Ochkin D. V. 331 Ochrymowycz L. A. 286 O’Connor C. J. 230 248 287 O’Connor M. J. 179 192 Oda M. 219 Odaka Y. 168 Odenthal J. 319 Odiaka T. I. 220 Odom J. D. 20 33 66 O’Donnell T. A. 128 140 309 Odori T. 324 Ohman L.-O. 57 Oeye H. A. 303 Ogard A. 313 Ogasahara K. 224 Ogaura S. 211 Ogden J. S. 139 164 Ogini W. O. 271 Ogino H. 233 Ogoshi H. 256 O’Hare P. A. G. 132 302 Ohms U. 128 Ohtaki H. 129 132 Ohtomo N. 129 Ohwada K. 139 Oikawa H. 232 Oikova T. 70 Okada M. 17 Okahara M. 12 Okano M. 122 Okano T. 262 Oki H. 168 Okolow-Zubkowska M. 156 Okuda T. 108 141 Ol’dekop Yu.A. 52 Oldham G. 326 Olgemoller B. 21 Olivi S. 53 Oliver J. P. 66 Olivier M. J. 297 Olmstead M. M. 271 288 Olsher U. 112 Omori T. 329 O’Neil R. M. 116 Ooi S. 178 283 287 Orazsakhatov B. 245 Orchin M. 227 O’Rear S. P. 247 O’Reilly E. J. 196 Orio A. A, 230 Orioli P. 229 294 Orlandini A. 210 214 230 Orlovskii V. P. 305 Orpen A. G. 191 258 260 261 271 Orrell K. G. 120 226 280 Orth C. 313 Orvig C. 198 Osae E. K. 128 Osaki K. 256 Osborn J. A. 56 Osborne A. G. 226 Osella D. 235 241 253 Osheroff N. 213 Oshima N. 256 Oskam A. 172 Ostah N. A. 76 Osteryoung R. A. 150 208 Otiko G. 293 Otsuka S. 171 262 Otterloo B. F. 245 Ouchi M. 12 Ouweltjes W.140 Overill R. E. 23 130 Overman J. W. 287 Ovsyannikov N. N. 323 Owada H. 122 Owen J. D. 14 Owens G. D. 288 Oxton I. A. 254 Ozaki A. 251 Ozawa Y. 332 Ozin G. A. 245 247 Paans A. M. J. 327 Pabmanabhan S. 240 Pacey G. E. 10 Paderno Yu. B. 19 Padnan-Fillio A. 249 Padurets L. N. 302 Paetzold P. 26 96 Paffett M. T. 165 Page E. M. 167 Page J. A. 218 Paiaro G. 82 264 Paik C. H. 324 Pain G. N. 49 234 Palalia B. D. 305 Palkina K. K. 306 Palmer A. J. 322 Palmer G. T. 293 Palmer M. R. 156 Palmer R. A. 219 Palmer-Ordonez K. 37 Palyi G. 240 Pan W. H. 121 Pandeya K. B. 288 Pandolfo L. 82 264 Pang S. 231 Pankowski J. 322 Pannell K. H. 95 Pannetier J.53 Pao P. J. 314 315 Paoletti P. 249 294 Papatheodorou G. N. 54 136 Pardy R. B. A. 247 Parent C. 305 Parigi K. J. 213 Parish R. V. 293 Park J. T. 194 261 Park K. B. 323 Parker G. R. 325 Parker V. B. 309 Parkin D. 10 Parkins A,-W. 221 Parks R. D. 301 Parry O. 293 Parsons D. G. 7 10 13 14 Partridge J. A. 331 Pascal J.-L. 20 Pasini A. 170 Pashkova A. V. 23 Pasquall M. 282 Pasquevich A. F. 68 Passaretti J. D. 113 Passmore J. 126 138 Pastor J. 213 Pasynskii A. A. 173 245 Pate B. D. 126 Patel C. C. 26 Patel K. S. 157 Patel V. D. 186 Patil S. K. 317 Patin H. 235 240 Patterson H. H. 275 Paul R. C. 68 Paulen W. 99 Paulus H. 109 Pavkovic S.F. 133 231 296 Pavlov Yu. A. 25 Pawson D. 348 Paxson J. E. 227 Payne N. C. 273 Peacock R. D. 139 230 Author Index Pearson A. J. 218 219 Pearson G. A. 261 Pechentkovskaya L. E. 25 Pedersen C. J. 11 Pedersen E. 177 Pelah S. 324 Pelgrims J. 229 Pelin W. K. 35 234 Pelissier M. 81 Pelizzetti E. 254 Pelizzi C. 94 170 230 Pellacani G. C. 283 Pellerito L. 64 Pellinghelli M. A. 231 Pellizzi G. 94 Pelrims J. 112 Pelz C. 98 Penavic M. 111 Penco S. 320 Pendleton R. G. 321 Pennesi G. 213 Pennington W. T. 99 Pepe G. 64 Peppe C. 67 Perchard J. P. 129 Perego G. 62 Perenboom J. A. A. J. 287 289 Peretrukhin V. F. 310 Perevezentsev A. N. 302 Perez G. 142 PeriC M.32 Peringer P. 24 123 Perkins C. M. 207 Perkins D. C. L. 277 Perkins M. J. 122 Perkins P. G. 300 Perrke-Fauvet M. 198 Perry D. L. 209 3 11 Persson I. 132 Perutz R. N. 204 Pervov V. S. 138 Peset R. 327 Peterman D. J. 302 Peter C. 227 Peters J. M. 327 Peters K.,105 Petersen J. L. 154 Peterson D. T. 302 Peterson J. 127 Peterson J. R. 140 309 Peterson L. K. 89 253 Petit L. D. 292 Petrakova V. A. 225 Petrosyants S. P. 53 Petrovnina N. M. 84 Petrovskii P. V. 225 260 Pettit L. D. 285 Petty R. H. 208 Petz W. 25 224 Peyerimhoff S. D. 32 Pez G. P. 257 Philip J. B. 264 Phillippi M. A, 199 213 Author Index 381 Phillips A. 338 Phillips J.G. 274 Phillips R. J. 71 Phillips S. 27 Picard G. 56 Pickardt J. 85 308 Pickering R. A. 188 Pickett C. J. 118 155 173 Potapove Z. M. 315 Potemkin A. V. 305 Potenza J. A. 205 Potier A. 20 Potier J. 20 130 Potter P. E. 358 Poulet G. 131 Poveda M. Z. 246 Pye P. L. 215 Pytlewski L. L. 56 Quan S. K. 113 199 Quick G. R. 298 Quick M. H. 218 Quirk J. M. 268 Pidcock A. 6 95 237 197 Povey D. C. 142 Powell D. B. 254 Raab K. 21 Pidgeon I. M. 78 Pieper W. 26 96 Pierpoint C. 193 266 Pierpoint C. G. 230 259 Pietro W. J. 66 Powell D. R. 304 Powell J. 7 Powell W. H. 32 313 Power C. 282 Power M. 282 Rabe U. 105 Rabenstein D. L. 96 Rabin R. 56 Rabinovich D. 120 Rabinowitz P. 316 Pike V. W. 320 Power W. J. 247 Radavich J. F. 57 Pillai M. R. A. 325 Powers D. A. 205 Rader R. A. 282 Pines A,,224 Powers J.C. 319 Radlow W. 3 Pinkerton A. A. 120 219 Powles J. G. 128 Radnia P. 223 306 311 Prabhawalkar V. 305 Radonovich L. J. 192 Pinkus D. G. 318 Prasad H. S. 52 Rae A. D. 127 Pippard D. A. 258 Pisaniello D. L. 300 Pisareva S. A. 5 Prasad R. 309 Prasada Rao M. S. 70 Pratt F. P. 324 Rafalko J. J. 269 Ragnarsson U. 320 Raichie M. E. 320 Pitzer R. M. 247 Pratt J. M. 229 Raid I. 316 Plank J. 264 265 Preetz W. 138 Railet R. 219 Platt A. W. G. 100 136 Pregasin P. S. 193 Raimondi C. 269 PleSek J. 37 Preiner G. 78 Raiszadeh M. 322 323 Plet F. 53 Plewa M. 96 134 Prelesnik B. 93 Prenant C. 320 Raithby P. R. 201 219 236 258 260 261 Ploeger F. 252 Ploetz K. B. 57 Preobrazhenskaya L. D. 313 Rajan 0.A. 170 Rakitin Yu. U. 245 Plotkin J. S. 216 Prest D. W.201 Rakov E. G. 139 Plowman K. R. 121 187 Preston K. F. 131 Ralston C. L. 94 109 Podborezskaya N. V. 84 Poehler T. 116 Preston P. N. 190 Preston S. D. 331 Ramachandran J. 319 Ramachar R. G. 294 Potter B. 132 Pri-Bur I. 319 Ramakrishna V. V. 317 Pogodin R. I. 331 Pohl S. 101 127 Price M. G. 231 Price R. 289 Ramarnoorthy N. 314 324 Rarnana K. V. 70 Poilblanc R. 255 Prick P. A. J. 5 Rama Rao K. V. S. 141 Pojer P. M. 197 324 Prijs B. 285 Rambidi N. G. 139 Pola J. 141 Prime D. M. 290 Randall C. H. 140 309 Polanyi P. E. 285 Pring G. M. 120 280 Randall E. W. 241 Poli R. 111 201 Poliakoff M. 200 Pritchard R. G. 83 Pritzkow H. 132 Rankin D. W. H. 34 41 82 83 90 100 121 122 135 Poll W. 128 Prizart L. 297 279 Polm L. H. 252 Polo C. 246 Prochazka H. 331 Proctor K.J. 142 Rao B. S. M. 328 330 Rao M. N. S. 98 Polushin N. I. 25 Prossdorf W. 163 226 Rao P. S. 208 Polyakov V. P. 25 Polyakova V. B. 56 Prokopovich V. P. 52 Pron A. 146 Raoux D. 132 294 Raptis D. 63 Polyanetskaya S. V. 64 Polyuthov V. G. 313 Pombeiro A. J. L. 172 197 Pomeroy R. K. 89 253 Pommerening H. 19 28 30 Poon C. K. 256 Proso Z. 330 Prosperi T. 283 Prosyanov N. N. 322 Prout K. 95 Prow W. F. 233 Pryor R. W. 318 Rastogi M. K. 161 Raston C. L. 109 110 153 Rastunov L. 331 Ratermann A. L. 185 Rattan S. S. 316 190 Poonia N. S. 11 Przyluski J. 146 Raubenheimer H. G. 189 Pope M. T. 166 Pople J. A. 79 Popov A. I. 5 15 Porta P. 208 Porter R. F. 35 Porzio W. 283 Puchkov V. V. 309 Puddephatt R. J. 277 279 Puff H. 93 Purcell R. W. 334 Purnell H. 116 Pyatenko A. T. 302 Rauchfuss T.B. 237 Rausch M. D. 153 Raverty W. D. 219 Ray N. K. 33 Rayanatorn M. 116 Raycheba J. M. T. 288 382 Raymond K. N. 206 248 311 312 323 Raynor J. B. 157 231 286 Rayudu G. V. S. 314 Razay H. 194 204 Razi M. T. 293 Razuvaev G. A. 81 Real F. M. 267 Reba R. C. 323 324 Rebbert R. L. 293 Recktenwald O. 91 Reddy A. V. R. 316 Reddy B. S. R. 112 Redfearn S. L. 343 Reed D. 187 Reed J. L. 232 Reedijk J. 20 281 285 289 Rees B. 227 Rees L. V. C. 113 206 Rehder D. 156 202 Reiff W. M. 208 209 Reiffer U. 284 Reiffers S. 320 327 Reilley C. N. 307 Reilly C. A. 227 Reimer K. J. 294 Reimer M. M. 294 Reimschwessel W. 332 Reinen D. 282 283 Reinsch-Vogell U. 165 Reisenauer H. P. 78 Reisner G.186 Reiss J. G. 106 159 Remadna K. 223 Remec P. 37 Remmel R. J. 36 Rempel S. 323 Rendle M. C. 277 Renfield K. W. 289 Rericha A. 157 Rest A. J. 9 112 139 164 221 Rest J. 9 Rettig S. J. 64 65 Retuert J. 116 Reuschenbach G. 102 Reuveni A. 208 Reuvers J. G. A. 251 Reynolds J. G. 119 312 Reynolds P. A. 248 Reynolds W. L. 233 Rheingold A. L. 60 107 Rhodes R. K. 213 294 Ribeiro da Silva M. A. V. 112,285 Ricard L. 176 Riccieri P. 172 Rice D. A. 158 167 Rice S.F. 232 Richards R. L. 172 175 197 Richardson F. S. 308 Richardson P. F. 231 Richardson R. J. 111 Richardson R. M. 224 Richens D. T. 164 Richman J. E. 101 Richman R. M. 304 Richmond T. G. 220 Richter W. 247 Ridd M. J. 255 Ridley D.D. 121 Riechel T. L. 158 Ried W. 81 Riedel D. 264 Rieger P. H. 107 228 Riera V. 202 Riess J. G. 188 216 Riggs C. A. 315 Riley P. E. 54 101 239 Riley P. I. 155 Rimmelin P. 128 Ringenberg R. E. 320 Riseborough P. S. 301 Ritsko J. J. 145 Ritter G. 207 Rivest R. 297 Riviere P. 81 Roberts B. P. 32 52 Roberts L. E. J. 358 Roberts P. J. 287 Roberts R. M. G. 226 Roberts S. A. 283 Robertson A. S. 196 200 Robertson D. W. 318 Robertson G. B. 257 Robertson H. E. 82 Robinson W. R. 261 Robinson W. T. 88 89 244 Roca V. 332 Rocklage S. M. 161 Rockway T. W. 167 Rodehorst R. M. 264 Rodgers I. R. 179 254 256 266 Rodichova G. V. 305 Rodionova L. M. 317 Rodrigues M. 286 Robisch G.157 Roeda D. 320 Roehler J. 304 Romer C. 180 Roemer J. 319 Rosch L. 86 Roesky H. W. 93 98 99 100 101 116 135 Roesler V. A. 283 Roessler K. 327 Roether W. 316 Roettzer L. J. 213 Rogers D. A. 114 Rogers R. D. 58 111 153 154 197 201 202 246 Rogers W.-N. 218 Rohwer H. E. 303 Rokos A. 325 Roland E. 253 Rolla F. 6 Roman E. 225 Author Index Romanova N. M. 305 Romo M. C. A. 325 Roncari E. 202 Ronman P. E. 319 Rooney J. J. 112 Root M. J. 233 Roper W. R. 21 Ropero G. M. 315 316 Rorabacher D. B. 286 Rosales M. J. 260 261 Rose N. J. 207 Rose-Munch F. 190 Rosen R. P. 243 Rosen S. 125 Rosenberg E. 253 Rosenfeld M. N. 322 Rosenheim L. D. 216 217 Rosolovskii V. Ya. 32 Ross L. 87 Rossa L.13 Rossi G. 213 Rossi S. 328 Roth W. J. 262 Rothwell I. P. 111 173 182 185 259 Rottenberg D. A, 314 RouC J. 252 Rouillon J.-C. 145 Rouse K. D. 260 Rouviere J. 318 Rowan A. J. 237 238 Rowbottom G. L. 94 109 110 Rowland F. S. 327 328 329 Rowland K. A. 272 Roy K. N. 309 Rozen S. 125 Roziere J. 257 Ruben D. J. 224 Rubin B. 108 Ruck A. 165 Rudler H. 190 Rudnitskaya 0.V. 63 Rudolph G. 85 91 Rudolph R. W. 51 69 Riiger R. 103 Ruisi G. 64 Rumpel H. 291 Ruppert I. 126 Rupprecht G. A. 161 Rurlander R. 6 32 Rusinko R. N. 67 Russell C. G. 113 Russell D. R. 139 167 231 Russell J. A, 136 Russo M. V. 190 Russo N. 39 Russo P. J. 145 Russow R. 321 Ruth T. J. 126 321 322 Ryabinina G.A. 19 Ryabov S. A, 138 Ryan R. R. 117 Rybin L. V. 219 Author Index Rybinskaya M. I. 217 226 Rycroft D. S. 126 Ryzhinskij N. C. 313 Rzaigui M. 306 Saak W. 127 Saatjian G. 253 Sabbatini M. 226 Sabesan A. 318 Sabesan M. N. 17 Sabo S. 151 Saburi M. 232 Saccavini J.-C. 323 Sacconi L. 210 230 240 247 249 Sadeh T. 324 Sadler P. J. 293 Sadoc A. 132 294 Sadok Chourou 309 Saeki M. 316 Saeki Y. 56 Saenger K. L. 126 Saenger W. 8 11 Saethre L. J. 116 Safari M. 237 Sagi S. R. 70 Said F. F. 67 158 Saint-Roch B. 81 Saito K. 173 178 Saito R. 283 Saito Y. 273 Saji H. 324 Sajun M. A, 317 Sakai Y. 329 Sakaki S. 246 Sakamoto T. 316 Sakurai H. 157 Saladini M.283 Salema M. S. 154 Salen G. 319 Sales J. 246 Salib K. A. R. 122 Saliby M. J. 233 Salman S. R. 25 Salmon D. J. 184 Salomone A. 323 Salvatore F. 310 Salyn Ya. V. 39 Sambre J. 321 Sameshima K. 246 Sametschek E. 29 Samochocka K. 323 Sampathkumaran E. V. 305 Sanchez F. H. 68 Sanders-Loehr J. 206 Sandstrom M. 69 133 Sangster D. F. 232 Sankpal S. K. 330 Sano H. 329 Sano S. 211 Sansoni M. 269 Santappa M. 284 Santini C. C. 193 Sanui Y. 16 Sanz-Medel A. 16 Sapozhnikov Yu. A. 332 Sappa E. 243 253 Sargeson A. M. 232 233 Sarkar B. 285 295 Sarkar S. 168 179 Sarkar S. K. 141 Sartorelli U. 269 Sasaki T. 219 Sasaki Y. 173 178 Sastre J. 320 Satge J. 81 Sato M. 158 Sato T. 78 Sattelberger A.P. 184 Sattler E. L. 327 328 Sau A. C. 85 94 Saunders M. 136 Saunders W.-D. 222 278 Savage S. 283 Savariar C. M. 318 SavCant J. M. 213 Savel’ev G. I. 315 Savoskina G. P. 317 Sawyer D. T. 111 Sawyer J. F. 97 98 107 Sayer B. G. 151 Sayi Y. S. 316 Sbizolo C. 206 Scapacci G. 214 Scattergood T. 326 Scattolin E. 156 Schachner H. 134 Schak C. J. 96 125 132 Schaefer H. 54 143 217 303 Schaefer H. F. 32 247 Schafer H. G. 103 Schaefer T. 25 Schaefer W. P. 248 Schaeffer R. 35 37 Schappacher M. 176 Schardt B. C. 199 227 Schatz G. C. 326 Scheibe R. 4 Scheidsteger O. 260 Scheidt W. R. 213 Scheld W. 22 Schelgel P. 323 Schelle S. 345 Scheller K. H. 285 Schenk K. J. 307 Scherer 0.J.114 Schieda O. 78 Schiefer H.-P. 4 Schimkowiak J. 100 135 Schings U. 104 Schipper P. E. 232 Schlapbach L. 302 Schleiffer J. J. 330 Schlosser K. 97 Schloter K. 21 Schlyer D. J. 321 Schmall B. 322 Schmehl R. H. 255 Schmid G. 30 241 Schmidbaur H. 30 105 Schmidpeter A. 100 103 104 107 Schmidt A, 109 134 Schmidt E. 5 Schmidt K. 198 Schmidt M. 29 99 Schmidt R. E. 216 Schmidt U. W. 322 Schmidt W. 143 Schmitkons T. 40 Schmitz D. 26 96 Schmutzler R. 135 Schneider B. H. 152 Schneider H. 15 Schneider M. 105 324 Schnockel H. 134 Schoeller W. W. 103 Schonfelder L. 93 98 Schoenherr S. 58 Schoening R. C. 7 263 Schomburg D. 136 Schoonheydt R. A. 112 229 Schrauzer G. N. 156 235 Schriewer M.80 Schriver A, 129 Schrobilgen G. 126 Schrobilgen G. J. 123 128 167 Schrock R. R. 60 152 161 162 190 Schroder K. 138 Schubert B. 5 Schubert U. 105 163 Schubiger P. A. 325 Schuette H. R. 321 Schugar H. J. 205 Schuh W. 93 Schuhmacher J. 314 Schuler T. 3 Schultz A.-J.,266 Schulze A. R. 64 Schulze J. 30 Schumann H. 308 Schumann M. 284 Schurnm R. H. 309 Schwaiger G. P. 322 Schwartz J. 61 154 262 Schwartz R. W. 308 Schwartz S. 128 Schwarz W. 101 109 134 Schwarzenbach D. 120 219 306 Schwarzmann E. 291 Schweda E. 172 Schweer H. 306 Schweizer W. B. 6 Schwerthoffer R. 28 Schwichtenhovel K. 103 Scmid H. G. 107 Scopelianos A. G. 51 Scott R. A. 289 290 384 Seaborg G.T. 313 Sebastian R. 25 SCcheresse F. 179 181 Seddon K. R. 279 Sedlak D. 30 Sedman J. 204 Sedmera P. 318 Sedney D. 208 Seebach D. 5 6 Seeber R. 202 230 Seelig S. S. 27 Segel’man I. R. 85 Sehested K. 131 Seidel G. 30 Seidel H. 306 Seip R. 24 28 58 66 Seitz D. E. 325 Sekiguchi A. 78 Sekiya A. 134 135 Seko M. 316 Selegue J. P. 258 Self C. R. 219 Selig H. 145 146 Selucky P. 316 Selwyn A. P. 320 Semenenko K. N. 25 39 299 302 Sen K. 56 Sena S. F. 226 Senderoff S. G. 323 Sengupta A. K. 56 Seon F. 56 Seppelt K. 132 137 138 Serbulov Yu. A. 331 Seredenko T. N. 332 Serpone N. 267 Sessler J. L. 210 Sethulakshmi C. N. 231 Sethuraman P. R. 166 Severson S. J. 245 Sevost’yanov Yu.G. 315 Seyer A. 104 Seyferth D. 241 Sgamellotti A. 282 Shah I. 192 Shakir R. 192 197 Shalygin V. A. 322 Sham T. K. 195 Shamir J. 127 Shapley J. R. 194 195 258 259 261 269 Sharfin W. 126 Sharifullah A. T. M. 330 Sharipov Kh. T. 57 Sharma R. B. 330 Sharma R. D. 68 Sharonov G. E. 331 Sharov V. A. 301 Sharp D. W. A. 139 Sharp P. R. 60 190 248 Shaughnessy W. J. 322 Shaugumbekova Zh. S. 52 Shaver A. 239 272 Shaw B. L. 267 277 Shaw R. W. 289 Shea J. A. 129 Sheahan R. 282 Shefer S. 319 Sheldrick G. M. 83 99 119 179 180 197 206 291 292 Sheldrick W. S. 100 101 102 223 Shelly J. 223 Shemyakin N. F. 52 Shenoy G. K. 299 Shepherd R. E. 150 Sherry A. D. 307 Sherry R. 139 Shiau C.C. 75 Shibahara T. 178 Shibata S. 21 Shields R. A. 324 Shihada A. F. 109 Shilov A. E. 156 Shil’shtein S. Sh. 302 Shima I. 101 Shimizu I. 226 Shimizu K. 171 Shimomura E. T. 199 Shimomura S. 157 Shimoni M. 319 Shimura M. 233 Shindu L. A. 296 Shimoda S. 273 Shinomura E. T. 273 Shiokawa J. 307 Shiokawa T. 319 329 Shirley D. A. 301 Shirley K. R. 262 Shirotsuka T. 332 Shishkin N. Ya. 139 Shishkunov V. A. 318 Shitikov V. V. 302 Shiue C. Y. 322 Shiue L. R. 294 Shizgal B. 326 Shklover V. E. 83 84 85 Shmidt V. S. 317 Shoji Y. 56 Shono T. 12 Shore S. G. 34 36 40 216 254 Short R. L. 252 Shreeve J. M. 136 Shreider V. A. 151 Shrem S. 325 Shu P. 116 Shukla J. P. 317 Shuto T.332 Siddiqui K. F. 292 Siddiqui S. 150 Sideridu Y. A. 244 Sidorov G. R. 319 Sidorov L. N. 139 300 Siebenman P. G. 53 146 Siebert W. 31 Siecker L. C. 206 Author Index Siefert E. E. 75 Siegbahn K. 14 116 Sieger H. 8 Siegl W. O. 208 Siekierski S. 301 Sievers R. 93 Sievert A. C. 258 Siew R. Y. 292 Sigal I. S. 267 Sigan A. 235 Sigel H. 284 285 Siglerova V. 318 Sigwarth B. 107 Siiman O. 214 Sik V. 120 280 Sikora D. J. 153 Silber H. B. 294 Silver J. 113 206 226 Silvester D. J. 314 315 Silvestre J. 95 223 Silvis H. C. 180 Silvon M. P. 224 Sim P. G. 198 208 Simhon E. D. 165 180 Simmons N. P. C. 34 Simmons R. G. 68 Simoes J. A. M. 118 Simon A. 138 303 Simon D. 87 Simon J.324 Simonovic M. 323 Simonsen O. 278 Simpson S. J. 311 Sims H. E. 315 Sinclair I. 63 Singh H. B. 26 Singh N. 121 Singh N. K. 230 Singh N. P. 330 Singh P. K. 26 11 5 Singh P. P. 121 Singh R. J. 316 Singh R. P. 230 Singh S. 68 Singh Z. 309 Singleton E. 217 Sinn E. 46 169 198 208 209 230 233 234 248 249 287 Sinotova E. N. 318 Sinta R. 16 Sinyavskaya E. I. 5 Sirazhiddinov N. A. 57 Siriwardane U. 239 Sironi A. 170 263 Sisler H. H. 97 Sisley M. J. 232 Sivakoff S. 324 Sivaramakrishnan R. 219 Sizov A. I. 39 Sjoeberg S. 320 Skarnemark G. 316 Skea D. C. J. 121 Skell P. S. 224 Author Index Skelten B. W. 190 256 257 Skinner P. E. 358 Skoda J. 319 Skoda L. 30 Skokan E.V. 300 Sladky F. 24 123 137 138 Slam M. A,,219 Slater S. 187 191 Slaunwhite W. R. jun. 325 Slegers G. 321 Slim D. R. 98 Slivnik J. 127 !lovokhotov Yu. L. 226 240 Smalc A. 127 Small M. A. 121 Small R. W. H. 63 97 115 Smart J. C. 248 Smegal J. A. 244 Smets M. 232 Smid J. 3 16 Smirnova E. A. 317 Smirnova G. E. 322 Smirnova N. M. 331 Smith A. K. 257 Smith B. L. 235 Smith D. E. 232 Smith G. 40 162 196 Smith G. D. 17 Smith G. P. 132 Smith H. K. 301 Smith J. D. 59 Smith J. P. 200 Smith K. G. 274 Smith K. M. 213 Smith P. J. 358 Smith R. J. 115 Smith R. V. 319 Smith S. J. 7 Smith W. B. 310 Smith W. L. 311 Snaathurst D. 287 Snape E. W. 17 Sneddon L. G. 41,44,234 Snegireva T.V. 84 Snell M. S. 238 Snook E. W. 320 Snow M. R. 179 256 So R. 323 Soares A. M. 172 Sobeleva L. V. 306 Sohn M. 198 Sokol L. W. W. L. 286 Sokolov V. B. 139 Sokolova E. I. 302 Solache M. 331 Solans J. 23 Solans X. 23 Solencheck D. 325 Soloman E. I. 290 Solomon E. T. 289 Solomonov V. M. 332 Soloveichik G. L. 56 Somenkov V. A. 302 Somerville R. G. 50 Sommer J. 128 146 Son S. 116 158 Sonoda N. 262 Sood D. D. 309 Sood S. 322 Soper A. K. 128 Soper P. D. 129 Sorai M. 224 Sorokin I. D. 300 Sorokina 0.V. 23 Sorrentino G. 332 Sosinsky B. A. 95 223 Sotiropoulos D. N. 69 Soubeyroux J. L. 138 Sourissean C. 224 Southern T. G. 242 Sowerby D. B. 109 Spalding T. R. 35 234 Spears R.M. 322 Spektor 0.V. 303 Spellane P. J. 267 Spencer B. 301 Spencer J. L. 280 Speranzini R. A. 275 Speth D. 265 Spicer L. D. 85 Spies H. 198 Spiridonev V. P. 20 Spooner F. J. 302 Spreer L. O. 192 Sprinz H. 198 Squibb E. R. & Sons 315 Srinivasan V. S. 167 Srivastava R. C. 271 296 Staal L. H. 252 Staelnacke C. G. 320 Staley R. H. 138 205 Stam C. H. 252 273 Stamberg K. 331 Stanko V. I. 323 Stanley D. R. 197 Stansfield R. F. D. 203 Stark C. A, 307 Starowieyoki K. B. 61 Statler J. A. 203 Staudigl R. 19 28 29 Stavber S. 125 Staves J. 43 Steadman J. 299 Steele B. R. 224 Steele W. V. 132 Steen N. D. C. T. 244 263 Steenhoek A. 327 Steffen M. 21 130 Stetien S. M. 324 Steiert D.245 Stein J. 245 Stein U. 81 Steinbeisser H. 137 Steinkruger F. J. 327 Steinmetz G. R. 243 258 Steinrauf L. K. 17 Stelzer O. 135 223 Stender E. 316 Stenkamp R. E. 206 Stepanov A. V. 313 317 Stephens F. S. 237 Stephenson G. R. 219 Stepin B. D. 303 Sterns M. 177 Stevens J. G. 108 Stevens R. E. 254 Stevens W. C. 296 Stewart B. 230 Stewart C. A. 91 Stewart J. J. P. 300 Stewart R. F. 66 Stibr B. 37 Stillman M. J. 296 Stobart S. R. 90 Stockis A. 246 Stoddart J. F. 218 272 Stoecklin G. 323 327 331 Stosser R. 157 Stogniew M. 318 Stojec Z. 150 Stokes J. 116 Stollmaier F. 55 Stone A. J. 32 Stone F. G. A. 49 50 194 204 234 235 242 261 280 Storch W. 28 Storey A. E. 311 Storr A. 64 65 Strach S.J. 131 Strahle J. 139 149 152 172 Strampach N. 156 Streit G. E. 136 Streitwieser A. jun. 3 11 Strelow F. W. E. 315 Stremple P. 180 Strom T. E. 310 Stromberg R. 155 Strong P. D. 17 Strong R. 223 Strouse C. E. 158 212 Struchkov Yu. T. 51 83 84 86 217 226 235 240 244,45 Strzelbicki J. 16 Stucky G. D. 153 195 269 Stufkens D. J. 172 Stukon R. A. 226 Stults B. R. 263 Stumpp E. 145 Stupnikov V. A. 302 Su,R. T. M. 136 Subramanian M. S. 317 Subramanyam R. 318 Subramanyam V. 324 Suchomet H. 104 Suffolk R. J. 25 123 Suga H. 224 Sugimoto H. 256 Sugise R. 262 Sugiura Y. 211 Author Index Suh J. 294 Sullivan J. C. 232 Sultana N. 321 Sumitoma H. 17 Summers L. J.142 Sun T. T. 320 Sundaram M. G.,321 Sundermeyer W. 134 Sung Fu. N. K. 312 Sutcliffe P. W. 358 Suter P. J. 17 Sutherland CS.,126 138 Sutherland R. G.,224 225 Sutton D. 89 253 Suwalski J. 146 Suzuki K. Z. 178 Suzuki M. 229 Svaracs E. 23 Svatovskaya L. B. 19 Svec H. J. 200 Svensson S. 116 Svihovcova P. 325 Swaddle T. W. 232 Swanson B. I. 141 Sweany R. L. 223 Swepston P. N. 99 102 115 Swincer A. G.,256 Sychev M. M. 19 Sykes A. G.,151 164 213 214 284 Symons M. C. R. 95 11 1 Szafran Z. 20 Szancer J. 321 Tabatabaian K. 257 Tachikawa E. 316 Tachikawa M. 236 259 Tacz W. J. 297 Tadzer I. 323 Taeger T. 29 Taga T. 256 Tagliaferri E. 219 Taihua L. 325 Tajima I. 17 Takagami Y. 219 Takagi M.16 Takagi Y. 133 Takami Y. 227 Takats J. 154 251 312 Takechi K. 272 Takeda Y. 16 Takerni H. 314 Takemoto J. 209 Takeshita T. 302 Takeuchi M. 129 Takine M. 332 Takusagawa F. 40 243 264 Talan P. 325 Talma A. 320 Tamaura Y. 112 205 Tarnblyn W. H. 235 Tan K. D. 227 Tan L.-S. 157 Tanabe K. 205 Tanacs B. 325 Tanaka H. 324 Tanaka K. 140 171 178 181 191 309 Tanaka M. 284 Tanaka N. 233 307 Tanaka T. 178 181 191 Tananaev I. V. 305 Tanchou J. K. 325 Tandoc U. 133 Tandon J. P. 26 115 Taneka N. 231 Tang Y. N. 75 328 Tanner S. P. 310 Tanzella F. L. 136 Taraban M. B. 86 Tarapcik P. 315 Tarasconi P. 94 230 Tarasevich B. N. 226 Tarasov B. P. 39 Tatee T. 318 Tatsumi K.171 175 Tatsuno T. 126 Tatz R. 196 Taube H. 233 256 Tautz H. 103 104 107 Tavanaiepour I. 243 244 Taylor B. F. 121 Taylor D. J. 221 Taylor G. E. 252 265 Taylor G. N. 318 Taylor J. S. 130 Taylor L. T. 196 Taylor M. J. 62 67 106 133 272 Taylor N. J. 215 238 252 253 Taylor P. L. 260 Taylor R. C. 69 Taylor S. E. 297 Teagarden D. L. 57 Teas C. L. 264 Tebbe K. F. 96 102 103 134 Tede B. 66 Teitelbaum Z. 325 Teixeira C. 118 171 Teliatnyk A. I. 11 Teller R. G.,49 266 Tempel N. 109 Templeton D. H. 311 Templeton J. L. 191 Tencer M. 331 Tenorio D. 330 331 Terada H. 18 Terao H. 141 Terao K. 67 Terrasi F. 332 Terrell D. L. 114 Terui M. 176 Testa H. J. 324 Teulon P. 257 Tewson T.J. 322 Thaur M. I. 325 Thaman T. J. 290 Tham Huyhn Oanh 307 The K. I. 103 Theobald B. R. C. 120 263 Thewalt U. 55 97 Thich J. A. 205 Thiel N. 134 Thierry J. C. 10 Thomas I. L. 323 Thomas J. M. 116 Thomas K. 313 Thompson A. C. 200 Thompson A. J. 206 Thompson D. J. 219 Thompson J. I. A. 151 Thompson J. L. 184 187 Thompson L. K. 285 Thompson M. R. 227 Thompson R. 345 Thompson R. C. 132 291 Thompson T. E. 145 Thomson A. J. 119 Thomson M. A. 279 Thorn D. L. 151 246 267 Thorn I. G.,218 Thorn V. 100 Thornback J. 195 Thorneley R. N. F. 174 Thornton-Pett M. 236 Thorup N. 127 Thulin B. 9 Thyagarajan S. 320 Tieke B. 142 Tilbury R. S. 314 Tilley T. D. 308 Timchenko T. I. 23 Timney J.A. 200 Timofeev G. A. 313 Timofeeva T. V. 83 86 Tinner U. 232 Tint G.S. 319 Tipper C. F. H. 277 Tiripicchio A. 243 253 259 Tiripicchio Camellini M. 243 253 259 Titkova E. G. 321 Titov L. V. 32 Titze H. 68 Tiwari G. D. 70 Tkachev V. V. 11 Tkatchenko I. 247 Toby B. H. 205 Toda F. 219 Toke L. 10 Toft M. A. 34 36 Tofe A. J. 324 Toftlund H. 278 Togni A. 193 Tolstaia T. P. 127 Tolstoguzov N. V. 303 Tomahogh R. 10 Tomas A. 300 Tom& M. 271 Author Index Tominaga T. 327 Tomkinson J. 224 Tomlinson A. A. G. 150 Toniola L. 274 Tonnesen G. L. 325 Tor Y. 125 Torantelli T. T. 282 Torizuka K. 324 Toshimitsu A. 122 Tosi L. 213 Totani T. 50 Toth G. 325 Toth L.M. 310 311 Totsch W. 123 Touchard D. 215 Touhara H. 138 Touzain Ph. 145 Towns E. 265 Trabelsi M. 306 Tramposch K. 323 Tranter G. E. 283 Trautmann N. 316 Trautwein A, 213 Traylor T. C. 210 Treichel H. 217 Treichel P. M. 216 217 Tremillon B. 56 Trenel M. 143 Tressaud A. 138 Tret’yak S. A. 331 Trinquier G. 81 Triolo R. 132 Trogler W. C. 219 220 Trogu E. F. 121 209 Tronova L. N. 315 Trooster J. M. 108 Trop H. S. 196 Trotter J. 64 65 Troup J. 11 Troup J. M. 7 100 Troutner D. E. 198 315 Trowell P. L. 20 Trsic M. 114 Trueblood K. N. 3 14 Trumper J. 324 Trunov V. K. 300 Truter M. R. 7 10 13 14 Trytko R. L. 247 Tschesche R. 321 Tsinker I. 84 Tsokur N. I. 5 Tsou H. R. 320 Tsuda N.301 Tsuda T. 282 Tsukube T. 17 Tsumaki H. 80 Tsunodo M. 159 Tsunoda N. 317 Tsutsui T. 331 Tsyganok L. P. 68 Tubino M. 214 Tuck D. G. 62 67 133 158 Tucker J. R. 218 Tucker P. A. 232 257 Tucker P. M. 140 309 Tulip T. H. 267 Tung H.-S. 154 Turecek F. 319 Turevskaya E. P. 151 Turff J. W. 139 164 Turgoose S. 220 Turner E. S. 122 Turner H. W. 311 Turner J. J. 200 221 Turova N. Ya. 151 Tyler D. R. 191 Tyler J. W. 140 309 Tyrer J. D. 98 Uchtman V. A. 242 Ueda Y. 262 Uemura S. 122 Ueno K. 16 146 308 Ueyama N. 118 170 Ugarov V. V. 139 Uhlig E. 246 Ulman A. 120 Umana M. 255 Underhill A. E. 117 Unny V. K. P. 320 Unruh J. 56 Unverricht A. 321 Uppal J. S. 138 Urbina A, 286 Urch D.S. 328 Urdea M. S. 231 Usatov A. V. 50 Ush R. 271 291 292 Usubaliev B. J. 92 Utterback S. G. 213 Utzuno S. 230 Vaalburg W. 320 327 Vahrenkamp H. 240 244 245 253 Valjak V. 157 van Beuningen D. 325 van Buuren G. N. 89 253 Vanchikov A. N. 127 van Dam H. 172 Vandecasteele C. 321 van den Brand J. A. G. M. 324 Van der Avoird A. 247 van der Coolwijk P. J. F. M. 172 van der Heijden H. 161 van der Helm D. 93 94 216 Van der Ploeg A. F. M. J. 72 van der Poel H. 273 Van Derveer D. G. 198 247 Van Derveer M. C. 118 Van der Velden J. W. A. 245 Van der Walt T. N. 315 Vandorpe B. 55 Van Duyneveldt A. J. 287 Van Dyke C. H. 228 van Eldik R. 274 van Haltern B. E. 330 Vani P. 122 Van Koten G.60 72 252 273 Vanquickenborne L. G. 255 Van Santen B. 252 Van Vliet R. 60 Van Wyk J. A. 323 Van Zyl W. H. 323 Varadi G. 240 Varescon F. 176 Vargas M. D. 261 Vargenas A. R. 310 Vasaros L. 329 Vasi C. 132 Vasic P. 93 Vasil’ev V. P. 305 Vasil’eva I. G. 305 Vasil’eva T. V. 84 Vasse R. 145 Vater N. 83 Vaughn J. W. 167 172 Vavejn B. 324 Vdovin V. M. 244 Veenboer J. T. 328 330 Veith M. 91 Veleshko I. E. 317 Venanzi L. M. 193 266 Venkatasubramani C. R. 316 Venturi M. 267 Venugopal V. 309 Vera D. R. 324 Verani G. 297 Verbetskii V. N. 302 Veres K. 318 Vergamini P. J. 119 Vergnano L. P. 358 Verma R. D. 68 Verny B. 318 Verschoor G. C. 20 120 289 291 Vicario G. P. 320 Viccaro P.J. 299 Vichi E. J. S. 214 Victoriano L. 67 Vidal J. L. 7 263 Viehbeck A. 108 Vieras F. 324 Vierling P. 216 Vigato P. A. 308 Vijayaraghavan J. 305 Vilcek S. 324 Viljoen J. C. 189 Vilkov L. V. 83 Villani A. J. 321 Ville G. 227 Vilminot S. 4 142 Vincent M. A. 32 Vincente J. 292 Vinogradova L. E. 52 Vinogradova N. V. 306 Vioux A. 203 388 Visca M. 254 Visco S. 228 Visser J. 326 328 Viswamitra M. A. 5 Viswanathan K. V. 320 Viswanathan N. 228 Vitagliano A. 278 Vitali D. 111 201 202 Vitola I. 23 Vogtle F. 3 8 9 13 Vogel J. 246 Vogel P. 219 Vogt M. 327 VolavSek B. 173 Vol’kenau N. A. 225 Volkert W. 315 Volkert W. A. 198 324 Volkov A. A. 332 Vollano J. F.85 Vollhardt K. 227 Vollhardt K. P. C. 53 Volodin I. A. 317 Volpin M. 235 von Barner J. H. 122 von Bennigsen-Mackiewicz T. 26 von Schnering H. G. 102 103 105 305 von Seyerl J. 107 214 Vorol’ev V. D. 305 Voronkov M. G. 84 85 Vos C. M. 322 Voss M. 105 Votruba I. 319 Voulgaropoulos A. 115 Vouna V. I. 139 Vrieze K. 60 72 252 Vyazankin N. S. 86 Wachter J. 106 Wachtmeister C. A. 321 Wada M. 246 Waddington T. C. 100 136 224 Wade R. C. 347 Wade S. R. 20 Wadt W. R. 310 Wageman W. E. 295 Wagenbach U. 327 Wagman D. D. 309 Wagner A. F. 326 Wagner R. 327 Wahren M. 185 Wakahara A. 327 Wakselman M. 121 Walborsky H. M. 9 Walch S. P. 326 Wald K. 243 Walker D. D. 256 Walker N. 223 Wall M.E. 319 Wallace W. E. 301 302 Wallis H. L. 156 Wallis R. C. 254 256 257 Walls A. 257 Walsh A. 282 Walsh B. 282 Walsh R. 78 Walter K. G. 87 Walton J. K. 257 266 Walton R. A. 116 159 182 184 261 Waluk J. W. 115 Wamamoto H. 282 Wan J. K. S. 201 Wanderlingh F. 132 Wanek P. M. 325 Wang J. T. 86 Wang S. 231 Wang Y. 231 Wanger J. 219 Wani M. C. 319 Wannowius K. J. 284 Wantier H. 122 Ward B. C. 191 Ward M. D. 262 Warner V. D. 324 Warren K. D. 31 Warshel A. 210 Washburn L. C. 320 Washburne S. S. 83 Wasserman H. J. 60 161 162 190 194 200 258 261 Watabe H. 226 Watabe M. 168 Watanabe H. 219 257 Watanabe K. 257 Watanabe N. 144 146 Watanabe Y. 219 257 Watanobe K. 282 Watari F.123 Waterfeld A. 137 Waters S. L. 314 315 Watkins H. P. 329 Watkins S. F. 308 Watson A. D. 232 Watson I. A. 314 Watson P. L. 56 308 Watson P.M.; 269 Watson W. L. 69 Watts R. J. 267 Watts W. E. 224 226 Wautier H. 232 Wayland B. B. 267 Weake A. D. 298 Weaver J. H. 301 302 Webb M. 155 Webber C. T. 272 Weber E. 3 13 Weber G. 13 Weber K.L. 100 135 Weber L. 192 Weber M. J. 143 Weber W. 27 Weber W. P. 76 Wedd A. G. 170 179 192 Wegner G. 146 Author Index Wei C. H. 295 Wei C.-Yu. 40 Weidhammer K. 264 Weidlein J. 58 66 109 Weidmann M. 325 Weigand W. 102 Weigl F. 310 Weinberg W. H. 263 Weiner W. P. 229 Weininger J. 324 Weinmaier J. H. 103 Weiss E. 5 30 219 Weiss J.169 Weiss R. M. 176 210 211 Weiss W. 316 Weitl F. L. 206 Welborn C. H. 213 Welch A. J. 49 50 234 265 Welch M. J. 314 320 322 323 330 Weller F. 109 Wemmer D. E. 224 Wengrovius J. H. 152 Wenk P. K. 285 Wenzel M. 324 Wermer P. 100 134 Werner A. 304 Werner G. 142 Werner G. D. 310 Werner H. 5 228 Werner P. E. 3 Wertheim G. K. 144 Wesolek M. 56 Wessner D. 307 West B. O. 176 West D. 233 West D.-X. 21 West R. 76 80 86 Westendorg B. A, 323 Westera G. 320 322 Westman S. 3 Westrum E. F. jun. 304 Westwood N. P. C. 20 127 Wevers M. 300 Whaley T. P. 354 Wheatley P. J. 260 Whelan J. 121 290 Whelan T. 35 White A. H. 40 94 109 110 190 248,256 257 White C. 257 White J. L. 57 White J.M. 332 White M. A. 229 White M. S. 133 White N. D. 265 White P. S. 126 138 153 163 Whiteley M. W. 221 222 Whitelock J. D. 135 279 Whitesell L. G. 255 Whitesides G. M. 276 Whitfield D. M. 17 Whitney J. F. 56 308 Author Index Whittaker S. B. 282 Whitten D. G. 255 Wiberg N. 78 Wichelhaus W. 304 Wickel U. 105 Wickland T. 327 Wickramsinghe W. A. 175 267 Widdowson D. A. 322 Wiebe L. I. 325 Wieghardt K. 156 169 Wiegman T. 320 Wieland B. W. 321 Wiest R. 227 Wijbenga G. 138 Wilbur D. S. 323 Wilburn J. C. 100 224 Wilczynski R. 44 Wild R. E. 182 Wildbredt D. A. 104 Wilken R. D. 4 Wilkinson G. 186 189 228 236,261 267 Willett R. D. 249 283 287 294 Willey G R. 20 Williams C.W. 144 303 Williams D. J. 108 144 272 Williams D. R. 291 Williams F. 86 Williams G. A. 197 199 Williams J. F. 321 Williams J. M. 236 266 Williams M. 219 Williams M. L. 257 Williams P. A. 220 Williams P. G. 318 319 Williamson A. N. 247 Williamson G. A. 248 Williamson R. F. 155 Willis A. C. 89 253 283 Willis C. 141 Willis C. J. 288 Willis L. J. 285 Willis S. 238 Willmann P. 145 Willsher C. J. 113 Wilms A. 62 Wilshire J. P. 113 199 Wilson C. G. 302 Wilson I. 213 Wilson J. W. 24 25 Wilson L. J. 208 209 283 Wilson R. D. 132 134 Wilson W. W. 134 164 Winans R. E. 125 Winfield J. M. 126 Wingfield J. N. 7 10 Winkler J. R. 232 Winkler M. E. 290 Winsfield I. M. 214 Winter G. 94 Winter M.J. 227 Winter W. 219 Wirth W. 321 Wisbey S. J. 194 242 Wise M. B. 133 299 Witt M. 98 99 Witt S. D. 75 Wittmann M. 305 Wittmer S. L. 320 Woessner D. E. 310 Wojciechowski w. 7 Wold A. 113 Woldring M. G. 320 327 Wolf A. P. 321 322 327 Wolf W. 322 323 Wolff T. 131 Wolff T. E. 119 182 Wolfgarat P. 6 Wolmershauser G. 114 Wolsey W. C. 235 Woltanski K. P. 325 Wong E. H. 36 Wong K. S. 236 Wong W. 236 Wood D. L. 77 235 Wood J. M. 96 Wood J. S. 282 Wood T. G. 244 Woodford R. L. 226 Woodhams F. W. D. 305 Woodruff W. H. 173 255 Woods B. A. 267 Woodward P. 194 203 222 242 252 261 Woolf A. A. 125 Woolley R. G. 229 Worley S. D. 204 Worrall I. J. 63 Wrackmeyer B. 26 28 30 Wreford S.S. 152 Wright J. N. 113 Wright K. L. 331 Wright M. E. 238 Wright P. J. 303 Wright S. 248 Wrobleski J. T. 205 Wu S. C. 329 wu Y. P. 10 Wudl F. 123 Wunderlich H. 186 Wydrzynski T. 196 Wynberg H. 320 Wynne K. J. 53 63 122 146 Wyttenbach A, 315 Yablokov V. A. 83 84 Yadav D. D. S. 121 Yakimova Z. P. 303 Yakobson G. G. 146 Yakshin V. V. 16 317 Yamada A. 231 Yamada K. 108 141 Yamada S. 159 176 Yamada T. 21 Yamaguchi M. 232 Yamaguchi T. 129 205 272 Yamamatsu S. 232 Yamamoto A. 246 247 Yamamoto T. 246 247 Yamanaka S. 150 Yamashita H. 332 Yamashita S. 118 170 Yamashita T. 118 170 Yamazaki T. 126 Yang L. W. 258 Yang X. 308 Yano H. 168 Yano T. 9 Yanovsky A. I. 51 Yanta T.J. 254 Yarrow P. I. W. 155 Yartys V. A. 299 Yastrebova L. F. 303 Yasuda M. 219 Yasuda S. 316 Yatsimirskii K. B. 11 12 Yeh S. M. 307 Yellowlees L. J. 255 Yildirim A. E. 282 Yokoyama A. 324 Yoneda H. 168 Yoneda Y. 231 Yoshida S. 228 Yoshida T. 60 171 262 Yoshifuji M. 101 Yoshikawa K. 18 Yoshikawa S. 232 Yoshikuni T. 231 Yoshizawa Y. 314 Young C. G. 177 Young D. A. 242 Young J. P. 140 309 Youngs W. J. 162 163 Yu I. 317 Yuan S. S. 320 Yutai J. 325 Zacharis H. M. 325 Zador M. 72 Zahn H. 325 Zahner G. 330 Zahner M. 325 Zahradnik R. 37 Zaitsev B. E. 63 Zaitseva L. L. 202 Zakharkin L. I. 50 51 52 Zakharova I. A. 39 Zakrzewski S. F. 318 Zalkin A. 311 Zamankhai H. 101 Zanazzi P.F. 228 Zanderighi G. M. 170 Zaworotka M. J. 155 Zdunek L. Z. 128 Zeeman M. L. 257 Zehnder M. 255 Zel’bst E. A. 84 Zelewsky A. 255 Zellweger J.-M. 311 Author index Zel’venskij Ya. D. 322 Temskova L. A. 39 Zemva B. 127 Zenneck U. 31 Zerbe H.-D. 138 Zhaoxiang S. 325 Zharsky I. M. 139 Zhdanov A. A. 51 Zhenghao L. 325 Zhon J. L. 315 Ziadeh Y. 326 Zido R. F. 11 Ziegler D. C. 143 Ziegler M. 325 Ziegler M. L. 191 192 201 264 265 Zietlow T. C. 184 Zimmer R. 93 Zimmer-Gasser B. 105 Zimmerman G. J. 41 234 Zimmermann H. 152 187 Zimmermann K. 325 Zimmie J. 236 Zinato E. 172 Zink J. I. 310 Zivanov-Stakic,D. 323 Zmbova B. 323 Zogal 0.J. 299 Zolyomi G. 319 Zombeck A.210 Zones S. I. 156 Zonnevijlle F. 166 Zozulin A. J. 33 Zsolnai L. 31 214 260 266 Zubieta J. 181 Zuckerman J. J. 93 94 95 Zuckman S. A. 198,324 Zuerner E. C. 192 Zueva E. V. 321 Zupan M. 125 Zumieta J. 117 Zlirkova L. 70 Zuykova N. P. 323 Zwashka F. 100

ISSN:0260-1818    

DOI:10.1039/IC9817800361

出版商:RSC    

年代:1981

数据来源: RSC