—.—. .. — —.-—- — .— - —. .—— . v I Sciences National Research Council NUCLEAR SCIENCE SERIES The Radiochemistry of vanadium r—----\ =. _._. ._— .. COMMITTEE ON NUCLEAR SCIENCE 4. L.F.CURTISS,Chairnaun ROBLEY D.EVANS,ViceCkuirman NationalBureayofStandards MaesaohusettsInstituteofTechnology J.A.DeJUREN,Secretary WestinghouseElectricCorporation C.J.BORKOWSKI J.W. fRVINE,JR. OakRidgeNationalLaboratory MassachusettsInstituteofTechnology ROBERT G.COCHM ~~ E.D.KLEMA TexasAgriculturalandMechanical NorthwesternUniversity College W. WAYNE MEINKE sAMUEL EPSTEIN UniversityofMichigan CaliforniaInstituteofTechnology J.J.NfCKSON U.FANO MemorialHospital,New York NationalBureauofStandards ROBERT L.PLATZMAN Laboxiatoirede CbimiePhysique HERBERT GOLDSTEIN NuclearDevelopmentCorporationof D.M. VAN PATTER America BartolResesrohFoundation LIAISON MEMBERS PAUL C.AEBERSOLD CHARLES K.REED AtomicEnergyCommlsaion U.S.AirForce J.HOWARD McMILLEN WILLIAM E.WRIGHT NationalScienceFoundation Officeof NavalResearch SUBCOMMITTEE ON RADIOCHEMISTRY W. WAYNE MEINKE,Chairman HAROLD KIRBY UniversityofMichigan MoundLaboratory GREGORY R.CHOPPIN GEORGE LEDDICOTTE FloridaStateUniversity OakRidgeNationalLaboratory GEORGE A.COWAN JULIANNIELSEN LosAlamosScientificLaboratory HanfordLaboratories ARTHUR W. FALRHALL ELLISP.STEINBERG lJntversi@ofWashington ArgonneNationalLaboratory JEROME HUDIS PETER C.STEVENSON BrookbavenNationalLaboratory UniversityofCalifornia(Livermore) EARL HYDE LEO YAFFE UniversityofCalifornia(Berkeley) McGU1 University CONSULTANTS NATHAN BA LLOU JAMES DeVOE Centred’Etudedel’EnergieNucleaire UniversityofMichigan Mol-Donk,Belgium WILLIAM MARLOW, NationalBureauofStandardfl CHEMISTRY c’ + The Radiochemistry of vanadium By J. L. BROWNLEE, JR. Department of Chemistry University of Michigun Ann Arbor, Michigan December1960 subcommittee on Radicichemistry National Academy of Sciences —National Research Council Printed in USA. Price $0.75. Available from the Office of Technical Services,Departmentof Commerce, Waddngtcm 25, D. C. FOREWORD The Subcommittee on Radlochemlstry 16 one of a number of subcommittees working under the Committee on Nuclear Science within the National Academy of Sciences - National Research council . Its members represent government, industrial, and university laboratories In the areas of nuclear chemistry and analytical chemistry The Subcommittee has concerned Itself with those areas of “nuclear science which Involve the chemist, such as the collec- tion and distribution of radlochemlcal procedures, the estab- lishment of specifications for radiochemlcally pure reagents, availability of cyclotron time for service irradiations, the place of radlochemlstry In the undergraduate college program, etc. This series of monographs has grown out of the need for up-to-date compilations of radiochemlcal information and pro- cedures. The Subcommittee has endeavored to present a series which will be of maxtium use to the working scientist and which contains the latest available information. Each mono- graph collects In one volume the pertinent information required for radlochemical work with an individual element or a group of closely related elements. An expert in the radiochemistry of the partictiar element has written the monograph, followlng a standard ~ormat developed by the Subcommittee. The Atomic Energy Commlsslon has sponsored the”printing of the series. The Subcommittee Is confident these publications wI1l be useful not only to the radlochemlst but also to the research worker h other fields such as physics, biochemistry or medicine who wishes to use radiochemlcal techniques to solve a specific problem. W. Wayne Melnke, Chairman Subcommittee on Radlochemistry 111 INTRODUCTION This volume which deals with the radiochemlstry of vanadium is one of a series of monographs on radiochemistry of’the elements. There Is Included a review of the nuclear and chemical features of particular Interest to the radioc”hemist,a discussion of prob- lems of dissolution of a sample and counting techniques, and finally, a collection of radiochemlcal procedures for the element as found in the literature. Th@ seriesof monographs will cover all elements for which radlochemlcal procedures are pertinent. Plans include revision of the monograph periodically as new techniques and procedures warrant. The reader Is therefore encouraged to call to the attention of the author any published or unpublished material on the radlochetnistry of vanadium which might be included in a re- vised version of the monograph. iv CONTENTS I. General Reviews of the Inorganic and Analytical Chemistry of Vanadium. 1 II. General RevlewE of the Radlochemi6try of Vanadium. 2 III . Table of Isotopes of Vanadium. 3 Iv. Review of Those Features of Vanadium Chemistry of C.hlef Interest to Radiochemists. 4 1. Metallic Vanadium, 4 2. Soluble Salts of Vanadium, 5 3. Insoluble Salts of Vanadium - Precipitation and Co-precipitation Characteristics. 7 4. Complex Ions of Vanadium. u 5. Chelate Complexes of Vanadium, 16 6. Extraction of Thenoyltrifluoroacetone Complexes of Vanadium into Organic Solvents, 23 7. Extraction of Vanadium into Organic Solvents. 24 a. Ion-Exchange Behavior of Vanadium, 39 v. Problems Associated with Dissolving Vanadium-Containing Ssmples. 48 VI. Counting Techniques for Vanadium Isotopes. 50 VII . Collected Radiochemical Procedures for Vanadium. 54 v The Radiochemistry of Vanadium J. L. BROWNLEE, JR. Department of Chemistry University of Michigan, Ann Arbor, Michigan I. GENERAL REVIEWS OF THE INORGANIC AND ANALYTICAL CHXMISTRY OF VANADIUM 1. Friend, J. N., “A Textbook of Inorgsnlc Chemistry, “ Vol. VI, Pt. III, Charles Griffin and Co., Ltd. , London, 1929, PP. g-li6. 2. Ephralm, F., “Das Vanadln und Seine Verblndungen, “ SanmilungChemlsche und Chemlsche-Technl sche Vortr~ge, Stuttgart , 1904, pp. 81-192. 3. FeEter, G., “Die Chemlsche technologiesdes Vanadlns,” Ssmmlung Chemlsche und Chemlsche-Technlsche Vortr&e, Stuttgart, 1914, pp. 417-495. 4. Fischer, S., “Contributions to the Knowledge of the Electrolysis of Aqueous Solutions of Vanadium Salts,” Ph.D. Thesis, Columbia University, New York, 1916. 5. Hendel, J. M.~ “A New Type of Reductor and its Application to the Determination of Iron and Vanadium,” Ph.D. Thesis, Columbia University, New York, 1922. 6. Nlcolardot, P., “Le Vanadium “ Encyclopedle Sclentlflque des Aide-Memoire, Paris, 1904. 7. Menancke~ H., “Die Quantitative Untersuchungsmethoden des Molybd!lns, Vanadium, und Wolfrsms,” Prektlsches Handbuch, M. Krayn, Berlin, 1913. 8. Frank, A. J., “Chemistry of Vanadium; A Summary of Non-Project Literature through November, 1952,” Topical Report ACCO-49, American Cyanamid Company, Raw Materials Development Laboratory, Winchester, Massachusetts, 1952. 9. Sldgwlck, N. V., “The Chemical Elements and their Compounds,” Vol. I, Oxford Unlverslty Press, Oxford, 1950, pp. 804-835. 1 10. Ephralm, F., “Inorganic Chemistry, ” Gurney and Jackson, London, 1939. 11. Hlllebrand, W. F., Lundell, G. E. F., Bright, H. A., Hoffman, J. I., “Applied Inorganle Analysis,” (2nd Ed.), John Wiley and Sons, Inc., New York, 1955, pp. 452-463. 12. Chariot, G., Bezler, ‘Quantitative Inorganic Analysis,” Methuen and Company, Ltd., London, 1957, PP. 622-628. 13. McAlplne, R. K. and Soule, B. A., “Qualltatlve Chemical Analysls,” D. van Nostrand Co., New York, 1933, PP. 391-4. 14. Noyes, A. A., Bray, W. C., “A S~stem of Qualitative Analysis for the Rare Elements, The MacMillan Co., New York, 1948. 15. Mellor, J. W., “A Comprehensive Treatise on Inorganic and Theoretical Chemistry,” Vol. IX, Lon~an’s, Green and co., London, 1929, pp. 714-836. 16. Gmelln-Kraut, “Handbuch anorganische Chemle,” Band III, Abtellung 2, C. Winter, Heidelberg, 19@, pp. 55-216. 17. Moore, R. B., Llnd, S. C., Marden, J. W., Bonardi, J. P., Davis, C. W., and Conley, J. E., “Analytical Methods for” Certain Metals,” Department of the Interior, Washington, D.C., 1923, pp. 239-28o. II. GENERAL REVIEWS OF THE RADIOCHEMISTRY OF VANADIUM 1. Ra6mnussen, S. W., and Rodden, C. J., In Rodden, C. J. (Ed.) “Analytical Chemlstm of the Manhattan Pro ect,” McGraw-Hill Book Co., Inc., New York, 1950, Pp. i59- 465. 2. Stevenson, P. C. and Hicks, H. G., “Separation, Techniques Used In Radlochemlstry,” in Beckerley, J. C., “Annual Reviews of Nuclear Science,” Vol. 3, Annual Reviews, Inc., Stanford, California, 1953, pp. 221- 234. 3. Flnston, H. L. and Mlskel, “Radlochemlcal Separation Technlquea,” ——10C. cit., Vol. 5, 1955, pp. 269-296. 4. Home, R.”A., Coryell, C. D., snd Goldrlng, L. S., “Generalized Acldlty In Radlochemlcal Separations,” ——10C. cit., VO1. 6, 1956, pp. 163-178. 5. Kraus, K. A., and Nelson, F., “Radlochemlcal Separations by Ion Exchange,” ——10C. cit., Vol. 7, 1957, PP. 31-46. Note: References 2 through 5 contain general information on radlochemlcal separations, and are not specifically vanadium separation sources. 2 111. Table of Isotopes ofVanadlum* Ralf ILfe Methad of Ieotope ($ Kmrdance~ Preparation Decay Scheme (1~ 46 0.4 flea. T146(p,n)V 46 (2) 23V T146(d,2m)#6 #7 31 min. p+1.9Mev cu(p,i3)**(3) T147(d,2n)V47 Ti46(d,n)v47 ,,2.-4?’- T147 V48 16 dOYS !9+o.6gMew T148(d,2n)#8 (4) vq16d) ~ 0.906 cu(p,E)** (3) EC 2$ 1.314 2.25 4+ 2+ o+ ~i48 V@ 33adaya E.G. 0.62 CU(P,E)**(3) ~4e(d,n)v49 m48(PJY)v% 7,2-7 p 4X1014 yearn E,C., (0,25$) V51 (99.75*) -- Naturally occurrins V52 .~ V52 3,76 min. B- 2.47 “V51(n,i)V 52 23 (2+) 52 -j 1.43 Cr52(n,p)V 52 ~55(n, a)V .2+ 1.433 Vsl(d,p)v52 o+ o % h V53 2 min. p- 2.50 ~(P, B)** (3) ~ 1.00 V54 55 ❑ et. E!-3.3 ● References for much of the data oontained h this