DOCSLIB.ORG

ORGANOMETAT,T,TC CHEMISTRY of URANIUM a Thesis Submitted By

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
ORGANOMETAT,T,TC CHEMISTRY of URANIUM a Thesis Submitted By ORGANOMETAT,T,TC CHEMISTRY OF URANIUM A thesis submitted by R1TN R. SIGURDSON, B.Sc. for the DEGREE of DOCTOR of PHILOSOPHY of the UNIVERSITY of LONDON Royal College of Science Imperial College of Science and Technology London, SW7 ?AY August 1976 TO MY PARENTS 3 ACKNOWLEDGEMENTS I would like to express my gratitude to Professor Geoffrey Wilkinson, F.R.S. for his guidance and enthusiastic support throughout the course of this work. Many thanks are also extended to Drs. Dick Andersen, Ernesto Carmona-Guzman and David Cole-Hamilton for their suggestionS, encouragement and advice, and to Dr. Kostas Mertis for his patient help during the first months. I am indebted to the Canadian Research Council of Canada for financial support during the past three years. 4 CONTENTS ABSTRACT 6 INTRODUCTION I. The Chemistry of Uranium(IV) 8 .II. The Chemistry of Uranium(V) 15 III. The Chemistry of Uranium(VI) 16 CHAPTER I. DILITHIUMHEXAALKYLURANATE(IV) COMPLEXES I. Introduction 19 II. Results and Discussion 27 III. Experimental 35 CHAPTER II. TRILITHIUMOCTAALKYLURANATE(V) COMPLEXES I. Introduction 54 II. Results and Discussion 55 III. Experimental 60 CHAPTER III. ADDITION COMPOUNDS OF URANIUM(VI) HEXAISO-PROPDXIDE WITH LITHIUM, MAGNESIUM AND ALUMINIUM ALKYLS I. Introduction 70 II. Results and Discussion 71 III. Experimental 77 CHAPTER IV. ORGANOMETALLIC CHEMISTRY OF ADAMANTANE I. Introduction 84 II. Results and Discussion 85 III. Experimental 87 REFERENCES 92 5 ABBREVIATIONS Me - methyl Et - ethyl Prn- normal-propyl Pri- iso-propyl Bun- normal-butyl But- iso-butyl But- tertiary-butyl Ph - phenyl CP cyclopentadienyl DME - dimethoxyethane tmed - N,N,NI,N'-tetramethylethylenediamine pmdt - N,N,Nt,N",N"-pentamethyldiethylenetriamine g.l.c. - gas-liquid chromatography i.r. - infrared s - strong m - medium w - weak sh- shoulder n.m.r. - nuclear magnetic resonance s - singlet d - doublet t - triplet q - quartet h - heptet br s - broad singlet 6 ABSTRACT Organouranium compounds with six or eight uranium-to-carbon a-bonds have been synthesized for the first time. The interaction of uranium tetrachloride with lithium alkyls in diethyl ether leads to the isolation of unstable lithium alkyluranate(IV) compounds of stoichiometry Li2UR6.8Et20, R = CH3, CH2SiMe3, C6H5, o-Me2NCH2C6H4. The lithium salts are also obtained as tetrahydrofuran and N,N,NI ,N1-tetramethylethylenediamine solvates. From uranium(V) pentaethoxide similar lithium salts of stoichiometry Li3UR8.3dioxan, R = GH3, CH2SiMe3, CH2CMe3, are obtained. The interaction of uranium(VI) hexaiso-propoxide with lithium, magnesium or aluminium alkyls does not give compounds containing U-C bonds, but addition compounds of stoichiometry (RLi)3U(OPri)6, (R2Mg)3U(OPri)6 and (R3A1)6U(OPri)6 respectively, that appear to be adducts in which the oxygen atom of the iso-propoxide group bound to uranium is acting as a donor. Attempts to prepare binary transition metal adamantyl complexes are described. INTRODUCTION 8 INTRODUCTION I. THE CHEMISTRY OF URANIUM(IV) The organic chemistry of uranium(IV) has been comprehensively 1-4 reviewed . The first organouranium compound, Cp3UC15, was prepared by Reynolds and Wilkinson in 1956 by the reaction of uranium tetrachloride with sodium cyclopentadienide. The proposed 115-coordination of the cyclopentadienyl rings was verified by 6 single crystal X-ray analysis . Anderson and Crisler7 in 1969 employed thallium cyclopentadienide in an improved synthesis of Cp3UC1 from UC14. The compound is decomposed by air and water but is very thermally stable, subliming in good yield at 120-130° in vacuo. A tetrahydrofuran solution of Cp3UC1 is weakly conducting and its reaction with silver perchlorate indicates that the U-Cl bond has ionic character. Wong et al. proposed that the long U-Cl bond (2.559 A) indicates approximately 50% ionic character6. Unlike the ionic Cp3Ln (Ln = a lanthanide) complexes, Cp3UC1 does not react with FeCl2 to give ferrocene". l0 Fischer et al. reportedthe first synthesis of Cp4U from UC14 and excess KCp in benzene; a lengthy extraction with n-heptane gives the product in low yield. A better synthesi,1 employing excess NaCp in THE increased the yield to 20%7. The dark red complex sublimes at 200° without substantial decomposition but reacts rapidly with air and moisture. A complete structural determination 11 from a single crystal X-ray diffraction study showed the planar C5 rings u-bonded to the uranium atom in a regular tetrahedral array. The bondinc7 probably has some covalent character and involves use of the 5f orbitals. 9 Tricyclopentadienyluranium can be prepared from UC13 and 12 KCp in benzene or from reactive uranium metal and UCp4 . The bronze pyrophoric solid is not very thermally stable, decomposing without sublimation at 120°. The Lewis acid properties of U(III) are indicated by its reaction with such bases as cyclohexylisonitrile and 1-nicotine. The reaction of UC14 and T1Cp in a 1:2 ratio in DME gives a green-brown solid which can also be prepared by reacting equivalent amounts of UC14 and UCI34 in DME. Recent results have shown that the product is probably [Cp3U]2[UC16].2DME 13, not the reported Cp2UCl2. However, if the two cyclopentadienyl rings are joined together the following reaction occurs14: CI U Clb U °- Cl'o U L Li A THE C( Ct 'Li" / \ THF THF X = CH2 , CH2CH2CH2, Me2Si It has been reported that these compounds react with organolithium reagents to form stable alkyls but experimental details have not yet been published. Isoelectronic with these dicyclopentadienyl derivatives, but having a bonding face of two carbon and three baron atoms, is the dicarbollide derivative, [Li(THF)02[U(C2B0-11 02C12]. The 1. structure of the highly distorted tetrahedral molecule has been 15 communicated . Cyclopentadienyluranium trichloride is -relpared as a dimethoxy- ethane adduct, CpUC13.DME, by the reaction c T1Cp with UC14 in 10 -16. Since the Manhattan project began, a great deal of interest has surrounded the preparation of o-bonded uranium alkyls and, indeed, the first alkyl derivative to be synthesized, Cp3UPh, 17-19 was reported independently by three research groups Subsequently a series of alkyl derivatives was prepared by the following reactions: THE Cp3UC1 + RLi Cp3UR + LiC1 18-19 18-19 ru ru t 18 r .5,18 R = Me , Bun ' 2' IL 5 I 18 18 i 18 cis-2-butenyl , trans-2-butenyl , Pr , t 18 18 Bu , vinyl , Pha-7..0. THF Cp 3UC1 + RMgX ------> Cp 3UR + Mgkl 19 18 20 R = n-xyly1 , allyl , p-to1y1 . The complexes are thermally stable, decomposing at elevated 18 temperatures with the liberation of alkane quantitatively . The alkyl group abstracts the proton from the cyclopentadienyl ring, not from the solvent, and evidence excludes a free radical decomposition pathway. A comparable series of alkyl complexes was prepared from Cp3ThC121. Thermolysi.s of Cp3ThR occvz.s in a manner similar to that of Cp3UR and, in the case of Cp3Th(Bun), the thorium-con- taining residue has been identified as the (715::1)-cyclopentadienyl- 22 thorium dimer (I) 18 Variable temperature n.m.r. studies of igally1) and Cp3Th(allyl)21indicate that both contai:: 111-allyl group . A single crystal X-ray study23of the 11 Th (I) uranium derivative confirmed that the allyl group is a-bonded in the solid state although the carbon-carbon double bond is unusually long. An X-ray study of a single crystal of Cp3U(CmCPh)24showed the a-nature of the bond between uranium and the phenylethynyl group. Kinetic studies of the thermolysis of Cp3UR in toluene indicated that the thermal stability is in the order primary > secondary > tertiary due to increasing steric crowding around the metal as the size of the alkyl group increases. Restricted rotation due to steric effects is observed about the U-R bond in Cp3UPri 18 Coordinative saturation is invoked to explain why compounds contain- ing ligands which are not 0-elimination-stabilized can be prepared and are, in fact, quite stable. Addition of methanol to solutions of Cp3UR yields Cp3UOMe and alkane, indicating that the uranium-to-carbon a-bond is considerably more ionic than the U-Cp n-bond. Other alkoxides are prepared by the metatheticl:_ reaction of Cp3UC1 with NaOR , i n t 25 R = Me, Et, Pr , Bu , Bu , in :efluxing benzene . An attempted preparation of UCp3 from UC13 NaCp in THF gave the ether- cleavage product, Cp3U(0Bun),3:; the only L:'- able compound26. The n-butoxide derivative -:=In also be pr., 1-ed in good yield 12 by the following method26: UC14 + Na0Bun [UC13(0Bun)] + NaC1 [UC13(0Bun)] + 3NaCp ---> Cp3U(0Bun) + 3NaCl Sodium borohydride reacts with Cp3UC1 in THE to give the volatile, red-orange Cp3UBH47. Infrared evidence indicates that the complex has a triply-hydrogen-bridged structure. The boro- hydride complex reacts with trialkylboranes in benzene to give Cp3U(H 3BR) which is also believed to contain a U(µ-H)3B group27. Cyolopentadienyluranium amides are prepared by the reaction of uranium(IV) diethylamide with two or three equivalents of cyclopentadiene in pentane, giving Cp2U(NEt2)2 and Cp3UNEt2 respectively Four unusual multinuclear complexes have been reported. The reaction of Cp3UC1 with dilithioacetylide and p-dilithiobenzene affords Cp3U-CFiC-UCp3 and R.-(Cp3U)2(C6114), respectively29. Similarly, Cp3UC1 reacts with the mono- and dilithio salts of 30 ferrocene to give (II) and (III) respectively . These are the Fe Fe (II) (III) only uranium complexes which contain a a-bonded cyclopentadienyl ring. The organic chemistry of uranium(IV) has been dominated by cyclopentadienyl derivatives but in an effort to improve the und.:!rstanding of bonding involving f-electrons other r-bonded 13 31 derivatives have been prepared. Triindeny1- and tris(benzylcyclo- 32 pentadienyl)uranium chioride have been examined crystallographically. Both exhibit nearly tetrahedral coordination of the uranium atom - with the latter unambiguously having 715-bonded cyclopentadienyl rings.
Load more

Recommended publications
  • Oct. 14, 1958 J. M. CARTER ET AL 2,856,263 PROCESS for the RECOVERY and PURIFICATION of URANIUM DEPOSITS Original Filed April 21, 1944 ‘7 Sheets-Sheet 1
    Oct. 14, 1958 J. M. CARTER ET AL 2,856,263 PROCESS FOR THE RECOVERY AND PURIFICATION OF URANIUM DEPOSITS Original Filed April 21, 1944 ‘7 Sheets-Sheet 1 IN VEN TORS James M Car/‘er Mar?n D. ?ame/7 BY ATTORNEY Oct. 14, 1958 J. M. CARTER ET AL 2,856,263 PROCESS FOR THE RECOVERY AND PURIFICATION OF URANIUM DEPOSITS Original Filed April 21, 1944 7 Sheets-Sheet 55 QQOUMM,vRMmG w.9386mmE IN VEN TORS James M. Car fer By Marfin 0 Home/7 W4 W ATTORNEY Oct. 14,1958 J. M. CARTER ET AL 2,856,263 PROCESS FOR THE RECOVERY AND PURIFICATION _ OF URANIUM DEPOSITS Origlnal Filed April 21, 1944 7 Sheets-Sheet 4 SCRUBBYING. AND WASHING PARTS OF CALUTRON ' WITH HOT WATER Lf- WASH WATER :FCONDENSATE ' \WATERANDMAKE UP snevmc SOL/D IMPUR/ TIES — WASH WA TER -—p>- CONDENSING To DISCARD I OXIDIZING ORSALVAGE SOLUTION U02” Cu?! Few’! Cr!!! Ni“ FILTERING‘ - '3 PREC/P/TATE 0* |——‘———/ F/LTRA TE _ U024!- TO DISCARD __ EVAPORATING gel”,++ OR SALVAGE PRECIPITATING Z/VH OH AND F'LTER'NG gFlLTRA TE TO FURTHER T REATMENT Fig. 4 I INVENTORS ‘James M Cor fer, BY Mar/7'0 D. Kama/7 ' @ M A TTORNEY Oct. 14,1958 J. M. CARTER ET AL . 2,356,263 PROCESS FOR THE RECOVERY AND PURIFICATION 0F URANIUM DEPOSITS Original Filed April 21, 1944 7 Sheets-Sheet s DISSOLVING URANIUM METAL DEPOSITED ON COPPER COLLECTOR IN COLD HNo3 (8N) CONDENSATE I AND MAKE UP SOLUTION HNO3 U02" ' Cu ** 7—>— CONDENSING ' HN03 . EVAPORATI NG CONCENTRA TED \ soburj'o/v _ F/LTRA TE C35 cu {NHJLF H PRECIPITATING ‘ -[—-~’—NH4OH A ND F ILTERING ' f/RECIP/ TA TES *Cu/‘OHZH4 :0 01 ORTO SALVAGEDISCARD *Trace T__>_ DISSOLVING HN 0 3 ' - SOLUTION U02 +4 *cuvf *Tme F/LTRA TE PRECIPITATING _l—_'_NH OH AND FILTERING 4 { PREClP/TATE NH U 0 TO DISCARD ( ‘)2 2 ’ OR SALVAGE , r---‘“—? TO FURTHER TREATMENT 5 I N V EN TORS' James M Car/‘er ' Mar/"in D.
    [Show full text]
  • Reactor Centrum Nederland
    RCN H-lfS REACTOR CENTRUM NEDERLAND RCX-186 INVESTIGATION'S ON' l'RAN>L CHLORIDE, ITS HYDRATES, AND BAL;I" SALTS by G. Prins RCN does not assume any liabili;;' with respect to the use of, or for damages resulting from the use of any information, apparatus, method or process disclosed in this document. is: >?:'': as o. t><?~ifi, Vr i"verr\ity \T.'J '.•'••:":• Petten, May 1973. St'MMARY 'ibis report describes the preparation and an inwst: .-at io:. physieo-cheniical properties ot uranyl .-hlorivie, its i.y.-.r .*.•. 01 its basic sales. The Methods lor Lhe synthesis ot l'i'.,i\,, l'U .i!L , .'t; ,i , .U'.vi i; li«vo beer. critically reviewed in Chapter Li and L:U: :::a:<> ru been careiulLy checked. In order to obtain more information on phase rv latienshiy :- uranyl chloride - water system, the system I'O - \iC\ - •• ,i been investigated (Chapter III;. Five solubility rogi.ns :. round with the corresponding solid phases ."i>,i:i ..JH.O, l\> ,•.i. : i .•: . 2UO.HCl.4H.vO, 4U0 .HCl ÖH,Ü, and L'O .2ri,0. One oi the throe basie salts, 4U0 .HCL.8H ,0, is tsetastable. This compound has no. heen described before. Since the basic salt ro,(OH)C1.2H,0 is congruently soluhle, it ran '.-.- prepared easily. Vibrational spectra of U0oJio, its hydrates, l'0,<oh)C1.2H,u, i'i',. Jt-,i>. and lour other uranyl compounds have been obtained (Chapt.r l\'). !:;.• interpretation of these spectra has heen restricted to a discussion ot the stretching frequencies of the uranyl group.
    [Show full text]
  • Ms< 3A43 35340 CUSSIFIMTON C W a M Oho73sa
    3A43 1 A £«v> t .My Thie docuarat consists of Jg> pages " Ro. _J} of 2hk copies, 8eries A* ♦ * D*te of Xseue: Kay ?f 19SX R eport fustoer: K-T05 Subject Category: CBBGSTHf^aBBBRAL 4 /0 - . 35340 * . ';: #Ms< gBBfcOBl IliLllliN COMPLEXES • 'SI, John T. Barr and Charles A. Horton Work Supervised by R. H. Lafferty, Jr. Laboratory Diriilon F. V. Hurd, Superintendent CUSSIFIMTON c w a m Sr ATOMIC *■•?«Snrt.i-.wt QW «.oH —*Q " \uiur. nwOMSirioATION HRAMCS F *-. CARBIDE ABB CARBOH CHSKXCALB CtMPAI* K-25 P lan t Oak Bldge, Tennessee RESTRICTS) This document contains rpsgSCS^^atB ae defined in the Atonic Energy Act traneaittal or the disclosure of ita dSSteSta in any manner to an unauthorised person is prohibited. t $ g * ' jf-V §a.*v OHO 73sa ***• v* * i Report Sodwr: K-705 Subject Category: cmCBm-CBBORAL Date of leant: m y 7, 1951 T itle : Uimon-TOB URAHUM COttUDOS Author: J. T. Birr and c. A. Horton ABSTRACT Bight chelated uranium complexes and 7 uranium amines, prepared fraft the reaction of organic aolutlone of uranium ealta with complexlng agents and organic bases, respectively, have been prepared and characterised. Salicylic and lactic acids, acetylacetone, and similar ccmplaxing agents which contain only acidic functional group*, shoved little reaction with uraniua compounds In organic solutions. However, upon the addition of an external base to the solution of the uraniua compound and the com­ pleting agent, the formation of a Werner-type Caspian resulted. For example, uranyl n itra te hexahydrate, sa lic y lic a d d , and pyridine in butyl acetate solution gave a precipitate of aallcylatoaquopyridlnouranyl n itra te .
    [Show full text]
  • Sources, Effects and Risks of Ionizing Radiation
    SOURCES, EFFECTS AND RISKS OF IONIZING RADIATION United Nations Scientific Committee on the Effects of Atomic Radiation UNSCEAR 2016 Report to the General Assembly, with Scientific Annexes UNITED NATIONS New York, 2017 NOTE The report of the Committee without its annexes appears as Official Records of the General Assembly, Seventy-first Session, Supplement No. 46 and corrigendum (A/71/46 and Corr.1). The report reproduced here includes the corrections of the corrigendum. The designations employed and the presentation of material in this publication do not imply the expression of any opinion whatsoever on the part of the Secretariat of the United Nations concerning the legal status of any country, territory, city or area, or of its authorities, or concerning the delimitation of its frontiers or boundaries. The country names used in this document are, in most cases, those that were in use at the time the data were collected or the text prepared. In other cases, however, the names have been updated, where this was possible and appropriate, to reflect political changes. UNITED NATIONS PUBLICATION Sales No. E.17.IX.1 ISBN: 978-92-1-142316-7 eISBN: 978-92-1-060002-6 © United Nations, January 2017. All rights reserved, worldwide. This publication has not been formally edited. Information on uniform resource locators and links to Internet sites contained in the present publication are provided for the convenience of the reader and are correct at the time of issue. The United Nations takes no responsibility for the continued accuracy of that information or for the content of any external website.
    [Show full text]
  • Preparation of Anhydrous Uranium Tetrachloride and Measurements on Its Magnetic Susceptibility
    Journal of NUCLEAR SCIENCE and TECHNOLOGY, 8 〔9〕, p. 498～502 (September 1971). Preparation of Anhydrous Uranium Tetrachloride and Measurements on Its Magnetic Susceptibility Tetsuhiko YOSHIMURA*, Chie MIYAKE* and Shosuke IMOTO* Received May 24, 1971 The reaction of UO2 with CCl4 vapor was carried out in a vacuum of 10-5 mmHg at 500℃ in order to prepare UCl4 of high purity. The lattice parameters were calculated from X-ray analysis to be a0=8.278±0.002, c0=7.460±0.009. The product thus ohtained was verified by chemical and X-ray analyses to be of anhydride form. The magnetic susceptibility was measured over the temperature range from liquid N2 to liquid He temperature, which revealed a deviation from the straight 1/X-T relation toward lower temperature. and that the anhydrous compound had ortho- I. INTRODUCTION rhombic symmetry. Since the same morpho- In the U-Cl system, there are known to logy may also exist for the chloride also, the exist four compounds, UCl3, UCl4, UCl5 and UCl4 is required to be of high purity. UCl6. Their chemical, physical and thermo- Table 1 Physical properties of UCl4 dynamic properties have been extensively investigated(1)(2) as well as those of the fluo- rides. Among these compounds UCl4 is used as the starting material for the synthesis of various uranous complexes, for its high solubility in many organic polar solvents such as methanol, ethanol, acetone, as reported by Selbin et al. (3)～(5) and Bagnall et al. (6) This com- pound is also used as the starting material for the preparation of UC(7), UN, US2(1)(8),USe2(1) etc.
    [Show full text]
  • WO 2016/074683 Al 19 May 2016 (19.05.2016) W P O P C T
    (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date WO 2016/074683 Al 19 May 2016 (19.05.2016) W P O P C T (51) International Patent Classification: (81) Designated States (unless otherwise indicated, for every C12N 15/10 (2006.01) kind of national protection available): AE, AG, AL, AM, AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, (21) International Application Number: BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, PCT/DK20 15/050343 DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, (22) International Filing Date: HN, HR, HU, ID, IL, IN, IR, IS, JP, KE, KG, KN, KP, KR, 11 November 2015 ( 11. 1 1.2015) KZ, LA, LC, LK, LR, LS, LU, LY, MA, MD, ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, OM, (25) Filing Language: English PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA, SC, (26) Publication Language: English SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. (30) Priority Data: PA 2014 00655 11 November 2014 ( 11. 1 1.2014) DK (84) Designated States (unless otherwise indicated, for every 62/077,933 11 November 2014 ( 11. 11.2014) US kind of regional protection available): ARIPO (BW, GH, 62/202,3 18 7 August 2015 (07.08.2015) US GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, ST, SZ, TZ, UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, (71) Applicant: LUNDORF PEDERSEN MATERIALS APS TJ, TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, [DK/DK]; Nordvej 16 B, Himmelev, DK-4000 Roskilde DK, EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, (DK).
    [Show full text]
  • Technology of Uranium Purification. Impurities Decontamination
    TECHNOLOGY OF URANIUM PURIFICATION. IMPURITIES DECONTAMINATION FROM URANYL CHLORIDE BY EXTRACTION WITH TRI-n-OCTYLAMINE IN THE PRESENCE OF THIOUREA AS COMPLEXING LIGAND. AIcídio Abrão PUBLICAÇÃO IEA 458 DEZEMBRO/1976 CEQ 69 PUBL. I EA 45B OEZEMBRO/1976 CEQ 68 TECHNOLOGY OF URANIUM PURIFICATION. IMPURITIES DECONTAMINATION FROM URANYL CHLORIDE BY EXTRACTION WITH TRI-n-OCTYLAMINE IN THE PRESENCE OF THIOUREA AS COMPLEXING LIGAND. Alcidio Abrio CENTRO DE ENGENHARIA QUÍMICA (CEQ) INSTITUTO DE ENERGIA ATÔMICA SAO PAULO - BRASIL APHOVAOO PARA PUBLICAÇÃO EM NOVEMBRO/1976 CONSELHO DELIBERATIVO Eng? HMcio Modnto da Costa Eng? Ivano Humbert Marchesi Prof. Admar Cervellim Prof. Sérgio Matcarenhai de Oliveira Dr. Klaus Reinach Or. Roberto D'Utra Vai SUPERINTENDENTE Prof. Dr, Ròmulo Ribe/r.» Pierori INSTITUTO DE ENERGIA ATÔMICA Caixa Postal 11.049 (Pinheiros) Cidade Universitária "Armando de Sallei Oliveira" SAO PAULO - BRASIL NOTA Este trabalho foi confe-ido p«lo autor depois de composto e sua redação tt'i conforme o original, sem qualquer correçáo ou mudança. TECHNOLOGY OF URANIUM PURIFICATION. IMPURITIES DECONTAMINATION FROM URANYL CHLORIDE BY EXTRACTION WITH TRI-n-OCTYLAMINE IN THE PRESENCE OF THIOUREA AS COMPLEXING LIGAND- Alcidio Abrão ABSTRACT The extraction of jranyl chloride by trinoctyiamme ITOAI and in decontamination from several impurities v»,th the aid of thiourea is investigated The effect of thiourea as a complexing agsnt, giving rise to unextracted canonic species of several metallic ion and its consequence in the extraction of uranyl chlonde from hydrochloric acid with TOA benzene!x'lenel is described Also, the effect of an acidified thiourea solution for scrubbing the organic phase loaded with uranyl chloride is studied INTRODUCTION The long chain amines had shown to be excellent extractants for various inorganic rid organic acds, and for a great number of anionic metallic complexes Smith and Page'441 had indicated the association properties of high weight amines w.th acids.
    [Show full text]
  • System Studies of Fission-Fusion Hybrid Molten Salt Reactors
    University of Tennessee, Knoxville TRACE: Tennessee Research and Creative Exchange Doctoral Dissertations Graduate School 12-2013 SYSTEM STUDIES OF FISSION-FUSION HYBRID MOLTEN SALT REACTORS Robert D. Woolley University of Tennessee - Knoxville, [email protected] Follow this and additional works at: https://trace.tennessee.edu/utk_graddiss Part of the Nuclear Engineering Commons Recommended Citation Woolley, Robert D., "SYSTEM STUDIES OF FISSION-FUSION HYBRID MOLTEN SALT REACTORS. " PhD diss., University of Tennessee, 2013. https://trace.tennessee.edu/utk_graddiss/2628 This Dissertation is brought to you for free and open access by the Graduate School at TRACE: Tennessee Research and Creative Exchange. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of TRACE: Tennessee Research and Creative Exchange. For more information, please contact [email protected]. To the Graduate Council: I am submitting herewith a dissertation written by Robert D. Woolley entitled "SYSTEM STUDIES OF FISSION-FUSION HYBRID MOLTEN SALT REACTORS." I have examined the final electronic copy of this dissertation for form and content and recommend that it be accepted in partial fulfillment of the equirr ements for the degree of Doctor of Philosophy, with a major in Nuclear Engineering. Laurence F. Miller, Major Professor We have read this dissertation and recommend its acceptance: Ronald E. Pevey, Arthur E. Ruggles, Robert M. Counce Accepted for the Council: Carolyn R. Hodges Vice Provost and Dean of the Graduate School (Original signatures are on file with official studentecor r ds.) SYSTEM STUDIES OF FISSION-FUSION HYBRID MOLTEN SALT REACTORS A Dissertation Presented for the Doctor of Philosophy Degree The University of Tennessee, Knoxville Robert D.
    [Show full text]
  • 1214 Final Report SF 10 03 06-CS
    AN ASSESSMENT OF SOURCES, PATHWAYS, MECHANISMS AND RISKS OF CURRENT AND POTENTIAL FUTURE POLLUTION OF WATER AND SEDIMENTS IN GOLD-MINING AREAS OF THE WONDERFONTEINSPRUIT CATCHMENT Report to the WATER RESEARCH COMMISSION Compiled by Henk Coetzee Council for Geosience Reference to the whole of the publication should read: Coetzee, H. (compiler) 2004: An assessment of sources, pathways, mechanisms and risks of current and potential future pollution of water and sediments in gold-mining areas of the Wonderfonteinspruit catchment WRC Report No 1214/1/06, Pretoria, 266 pp. Reference to chapters/sections within the publication should read (example): Wade, P., Winde, F., Coetzee, H. (2004): Risk assessment. In: Coetzee, H (compiler): An assessment of sources, pathways, mechanisms and risks of current and potential future pollution of water and sediments in gold-mining areas of the Wonderfonteinspruit catchment. WRC Report No 1214/1/06, pp 119-165 WRC Report No 1214/1/06 ISBN No 1-77005-419-7 MARCH 2006 Executive summary 1. Introduction and historical background The eastern catchment of the Mooi River, also known as the Wonderfonteinspruit, has been identified in a number of studies as the site of significant radioactive and other pollution, generally attributed to the mining and processing of uraniferous gold ores in the area. With the establishment of West Rand Consolidated in 1887 gold mining reached the Wonderfonteinspruit catchment only one year after the discovery of gold on the Witwatersrand. By 1895 five more gold mines had started operations in the (non-dolomitic) headwater region of the Wonderfonteinspruit as the westernmost part of the West Rand goldfield.
    [Show full text]
  • Export Control Handbook for Chemicals
    Export Control Handbook for Chemicals -Dual-use control list -Common Military List -Explosives precursors -Syria restrictive list -Psychotropics and narcotics precursors ARNES-NOVAU, X 2019 EUR 29879 This publication is a Technical report by the Joint Research Centre (JRC), the European Commission’s science and knowledge service. It aims to provide evidence-based scientific support to the European policymaking process. The scientific output expressed does not imply a policy position of the European Commission. Neither the European Commission nor any person acting on behalf of the Commission is responsible for the use that might be made of this publication. Contact information Xavier Arnés-Novau Joint Research Centre, Via Enrico Fermi 2749, 21027 Ispra (VA), Italy [email protected] Tel.: +39 0332-785421 Filippo Sevini Joint Research Centre, Via Enrico Fermi 2749, 21027 Ispra (VA), Italy [email protected] Tel.: +39 0332-786793 EU Science Hub https://ec.europa.eu/jrc JRC 117839 EUR 29879 Print ISBN 978-92-76-11971-5 ISSN 1018-5593 doi:10.2760/844026 PDF ISBN 978-92-76-11970-8 ISSN 1831-9424 doi:10.2760/339232 Luxembourg: Publications Office of the European Union, 2019 © European Atomic Energy Community, 2019 The reuse policy of the European Commission is implemented by Commission Decision 2011/833/EU of 12 December 2011 on the reuse of Commission documents (OJ L 330, 14.12.2011, p. 39). Reuse is authorised, provided the source of the document is acknowledged and its original meaning or message is not distorted. The European Commission shall not be liable for any consequence stemming from the reuse.
    [Show full text]
  • International Conference on Nuclear Power and Its Fuel Cycle Salzburg, Austria • 2-13 May 1977
    INTERNATIONAL CONFERENCE ON NUCLEAR POWER AND ITS FUEL CYCLE SALZBURG, AUSTRIA • 2-13 MAY 1977 "•- "i^. IAEA-CN-36/555 REVIEW OF EXPERIENCE GAINED IN FABRICATING NUCLEAR GRADE URANIUM AND THORIUM COMPOUNDS AND THEIR ANALYTICAL QUALI_ TY CONTROL AT THE INSTITUTO DE ENERGIA ATÔMICA, SÂ*O PAU LO, BRAZIL. AbrSo, A., França Jr., J.M., Ikuta, A., Püschel, C.R., FedergrUn, L., Lordello, A.R., Tomida, E.K., Moraes, S., Brito, J.de, Gomes„ R.P., Araújo, J.A., Floh, B., Matsu_ da, H.T. INSTITUTO DE ENERGIA ATÔMICA Caixa Postal 11.049 (Pinheiros) Cidade Universitária "Armando Salles Oliveira" SÃO PAULO - BRASIL Introduction As part of the national program for developping atomic energy for peaceful uses, directed by Brazilian Nuclear Energy Commission (CNEN), the Instituto de Energia Atômica (IEA),Sao Paulo,has giving great emphasis to a systematic development of research on establishing of the technology of ura nium and thorium, training of chemists and engineers, and production of some nuclear materials for further métallurgie work and fabrication of fuel ele_ ments for nuclear research reactors. This paper reviews the main activities on the recovery of uranium from ores, the purification of uranium and tho rium raw concentrates and their transformation in nuclear grade compounds. The design and assemblage of pilot facilities for ammonium diuranate (ADU), uranium tetrafluoride, uranium trioxide, uranium oxide microspheres, uranyl nitrate denitration, uranium hexaflucride and thorium compounds are discus_ sed. The establishment of analytical procedures as an important support to the technical work is emphasised. Recovery of Dranium from Ores For the establishment of the technology of U recovery from dome£ tic resources, some work has been done on unexploited till now phosphate rock.
    [Show full text]
  • Jan. 15, 1952 C. D., WLDER 2,582,941 PROCESSES of PRODUCING URANIUM CHLORIDES Filed Oct
    Jan. 15, 1952 C. D., WLDER 2,582,941 PROCESSES OF PRODUCING URANIUM CHLORIDES Filed Oct. 2, 1944 d S Q Q Q t 2. INVENTOR. 6ozEMAW Z. WZZZOER ATTORNEY . Patented Jan. 15, 1952 2,582,941 UNITED STATES PATENT OFFICE 2,582,941 PROCESSES OF PRODUCING URANUM CHELORDES - Coleman D. Wilder, Oak Ridge, Tenn., assignor to the United States. of America, as represented bysion the United States Atomic Energy Commis Application October 12, 1944, Serial No. 558,452 8 Claims. (C1. 23-145) 2. - This invention relates to the manufacture of a pating carbon tetrachloride vapor in a speedy uranium chloride product, and more particularly stream of dry air, passing the resultant mixture re of uranium pentachloride over an uranium compound heated to the neigh - - - - - a . g a substantial proportion of borhood of 550° C. whereby uranium pentachlo uranium hexachloride, by a process for chlorinat: ride is formed and vaporized into the current, ing various, compositions comprising uranium moving the resulting vaporous mixture into a compounds, with carbon tetrachloride vapor car collecting receptacle so that most of the uranium ried by a Swift current of air. chloride will condense and settle out, and send This invention has for an object the rapid pro ing the gas stream through a dust separator to duction of a uranium chloride product compris strip it of the residual uranium-containing par ing a large proportion of uranium pentachloride ticles. and various proportions of uranium hexachlo The apparatus employed comprises a device ride. for supplying carbon tetrachloride, a device for A further object of the invention is to provide supplying dry air, a flash boiler in which the a high-yield, low-loss process for the production 5 carbon tetrachloride is vaporized and mixed with of uranium pentachloride which is economical the air, a reaction chamber in which the ai and suitable for large scale production of said carbon tetrachloride admixture is reacted with chloride.
    [Show full text]