The Radio Chemistry of Vanadium.us AEC

8/6/2019 The Radio Chemistry of Vanadium.us AEC

1/82

.. . .. .-- . - . . .vI SciencesNat ional Researc h Counc i lNUCLEAR SCIENCE SERIES

The Radiochemistryof vanadium

r----\

=. _._. ._

. . ..


2/82

COMMITTEE ON NUCLEAR SCIENCE4.

L.F.CURTISS,Chairnaun ROBLEY D.EVANS,ViceCkuirmanNat i ona lBureayofStandards MaesaohusettsnstitutefTechnology

J.A.DeJUREN,SecretaryWestinghouselectricorporationC.J.BORKOWSKI J.W. fRVINE,JR.OakRidgeNationalaboratory MassachusettsnstitutefTechnologyROBERT G.COCHM ~~TexasAgriculturalndMechanicalCollegesAMUEL EPSTEINCalifornianstitutefTechnologyU.FANONationalureauofStandardsHERBERT GOLDSTEINNuclearDevelopmentorporationfAmerica

E.D.KLEMANorthwesternniversityW. WAYNE MEINKEUniversityfMichiganJ.J.NfCKSONMemorialHospital,ew YorkROBERT L.PLATZMANLaboxiatoireeCbimiePhysiqueD.M. VAN PATTERBartolesesrohFoundation

LIAISON MEMBERSPAUL C.AEBERSOLD CHARLES K.REEDAtomicEnergyCommlsaion U.S.AirForceJ.HOWARD McMILLEN WILLIAM E.WRIGHTNationalcienceoundation Officef NavalResearch

SUBCOMMITTEE ON RADIOCHEMISTRYW.WAYNE MEINKE,Cha i rman HAROLD KIRBYUniversityfMichigan MoundLaboratoryGREGORY R.CHOPPIN GEORGE LEDDICOTTEFloridatateniversity OakRidgeNationalaboratoryGEORGE A.COWAN JULIANNIELSENLosAlamosScientificaboratory HanfordLaboratoriesARTHUR W. FALRHALL ELLISP.STEINBERGlJntversi@fWashington ArgonneNationalaboratoryJEROME HUDIS PETER C.STEVENSONBrookbavenationalaboratory UniversityfCaliforniaLivermore)EARL HYDE LEO YAFFEUniversityfCaliforniaBerkeley) McGU1 University

CONSULTANTSNATHAN BALLOU JAMES DeVOECentredEtudeelEnergieucleaire UniversityfMichiganMol-Donk,elgium WILLIAM MARLOW,NationalureauofStandardfl


3/82

CHEMISTRY

c +

The Radioc hem ist ry of vanadium

By J . L. BROWNLEE, J R.Depart ment of Chem ist ryUniv ersit y of M ichigunAnn Arbo r, MichiganDecember1960

subcommitteeon RadicichemistryNa tio na l Ac ad em y o f Sc ie nc es Na tio na l Re se ar ch Cou n cil

Printed inUSA. Price $0.75. Availablefrom the Officeof TechnicalServices,Departmentf Commerce, Waddngtcm 25,D. C.


4/82

FOREWORD

The Subcommittee on Radlochemlstry 16 one of a number ofsubcommittees working under the Committee on Nuclear Sciencewithin the National Academy of Sciences - National Researchcouncil . Its members represent government, industrial, anduniversity laboratories In the areas of nuclear chemistry andanalytical chemistry

The Subcommittee has concerned Itself with those areas ofnuclear 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, theplace of radlochemlstry In the undergraduate college program,etc.

This series of monographs has grown out of the need forup-to-date compilations of radiochemlcal information and pro-cedures. The Subcommittee has endeavored to present a serieswhich will be of maxtium use to the working scientist andwhich contains the latest available information. Each mono-graph collects In one volume the pertinent information requiredfor radlochemical work with an individual element or a group ofclosely related elements.

An expert in the radiochemistry of the partictiar elementhas written the monograph, followlng a standard ~ormat developedby the Subcommittee. The Atomic Energy Commlsslon has sponsoredtheprinting of the series.

The Subcommittee Is confident these publications wI1l beuseful not only to the radlochemlst but also to the researchworker h other fields such as physics, biochemistry or medicinewho wishes to use radiochemlcal techniques to solve a specificproblem.

W. Wayne Melnke, ChairmanSubcommittee on Radlochemistry

111


5/82

INTRODUCTIONThis volume which deals with the radiochemlstry of vanadiumis one of a series of monographs on radiochemistry ofthe elements.There Is Included a review of the nuclear and chemical featuresof particular Interest to the radiochemist,a discussion of prob-lems of dissolution of a sample and counting techniques, andfinally, a collection of radiochemlcal procedures for the elementas found in the literature.

Th@ seriesof monographs will cover all elements for whichradlochemlcal procedures are pertinent. Plans include revisionof the monograph periodically as new techniques and procedureswarrant. The reader Is therefore encouraged to call to theattention of the author any published or unpublished material onthe radlochetnistryof vanadium which might be included in a re-vised version of the monograph.

iv


6/82

CONTENTSI. General Reviews of the Inorganic and Analytical Chemistryof Vanadium.II. General RevlewE of the Radlochemi6try of Vanadium.III . Table of Isotopes of Vanadium.Iv. Review of Those Features of Vanadium Chemistry of C.hlefInterest to Radiochemists.

1 .2.3.4.5.6.

7.a.

Metallic Vanadium,Soluble Salts of Vanadium,Insoluble Salts of Vanadium - Precipitation andCo-precipitation Characteristics.Complex Ions of Vanadium.Chelate Complexes of Vanadium,Extraction of Thenoyltrifluoroacetone Complexes ofVanadium into Organic Solvents,Extraction of Vanadium into Organic Solvents.Ion-Exchange Behavior of Vanadium,

v. Problems Associated with Dissolving Vanadium-ContainingSsmples.VI. Counting Techniques for Vanadium Isotopes.

VII . Collected Radiochemical Procedures for Vanadium.

123

445

7u1 6

23243 9

4 85 05 4

v


7/82

The Radiochem istry of VanadiumJ . L. BROWNLEE, J R.

De pa rt m e nt o f Ch em is t r yUn ive rs it y o f Mic higa n, An n Ar bo r, Mic higa n

I. GENERAL REVIEWS OF THE INORGANIC AND ANALYTICALOF1.

2.

3.

4.

5.

6.

7.

8.

9.

CHXMISTRYVANADIUMFriend, J. N., A Textbook of Inorgsnlc Chemistry, Vol. VI, Pt. III, Charles Griffin and Co., Ltd.,London, 1929, PP. g-li6.Ephralm, F., Das Vanadln und Seine Verblndungen, SanmilungChemlsche und Chemlsche-Technlsche Vortr~ge,Stuttgart, 1904, pp. 81-192.FeEter, G., Die Chemlsche technologiesdes Vanadlns,Ssmmlung Chemlsche und Chemlsche-Technlsche Vortr&e,Stuttgart, 1914, pp. 417-495.Fischer, S., Contributions to the Knowledge of theElectrolysis of Aqueous Solutions of Vanadium Salts,Ph.D. Thesis, Columbia University, New York, 1916.Hendel, J. M.~ A New Type of Reductor and itsApplication to the Determination of Iron and Vanadium,Ph.D. Thesis, Columbia University, New York, 1922.Nlcolardot, P., Le Vanadium Encyclopedle Sclentlflquedes Aide-Memoire, Paris, 1904.Menancke~ H., Die Quantitative Untersuchungsmethodendes Molybd!lns, Vanadium, und Wolfrsms, PrektlschesHandbuch, M. Krayn, Berlin, 1913.Frank, A. J., Chemistry of Vanadium; A Summary ofNon-Project Literature through November, 1952, TopicalReport ACCO-49, American Cyanamid Company, Raw MaterialsDevelopment Laboratory, Winchester, Massachusetts, 1952.Sldgwlck, N. V., The Chemical Elements and theirCompounds, Vol. I, Oxford Unlverslty Press, Oxford,1950, pp. 804-835.

1


8/82

10.

11.

12.

13.

14.

15.

16.

17.

Ephralm, F., Inorganic Chemistry, Gurney and Jackson,London, 1939.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.Chariot, G., Bezler, Quantitative Inorganic Analysis,Methuen and Company, Ltd., London, 1957, PP. 622-628.McAlplne, R. K. and Soule, B. A., Qualltatlve ChemicalAnalysls, D. van Nostrand Co., New York, 1933, PP.391-4.Noyes, A. A., Bray, W. C., A S~stem of QualitativeAnalysis for the Rare Elements, The MacMillan Co.,New York, 1948.Mellor, J. W., A Comprehensive Treatise on Inorganic andTheoretical Chemistry, Vol. IX, Lon~ans, Green andco., London, 1929, pp. 714-836.Gmelln-Kraut, Handbuch anorganische Chemle, Band III,Abtellung 2, C. Winter, Heidelberg, 19@, pp. 55-216.Moore, R. B., Llnd, S. C., Marden, J. W., Bonardi, J. P.,Davis, C. W., and Conley, J. E., Analytical Methods forCertain Metals, Department of the Interior, Washington,D.C., 1923, pp. 239-28o.

II. GENERAL REVIEWS OF THE RADIOCHEMISTRY OF VANADIUM1.

2.

3.4.

5.

Ra6mnussen, S. W., and Rodden, C. J., In Rodden, C. J.(Ed.) Analytical Chemlstm of the Manhattan Pro ect,icGraw-Hill Book Co., Inc., New York, 1950, Pp. 59-465.Stevenson, P. C. and Hicks, H. G., Separation,Techniques Used In Radlochemlstry, in Beckerley, J. C.,Annual Reviews of Nuclear Science, Vol. 3, AnnualReviews, Inc., Stanford, California, 1953, pp. 221-234.Flnston, H. L. and Mlskel, Radlochemlcal SeparationTechnlquea, 10C. cit., Vol. 5, 1955, pp. 269-296.Home, R.A., Coryell, C. D., snd Goldrlng, L. S.,Generalized Acldlty In Radlochemlcal Separations,10C. cit., VO1. 6, 1956, pp. 163-178.Kraus, K. A., and Nelson, F., Radlochemlcal Separationsby Ion Exchange, 10C. cit., Vol. 7, 1957, PP. 31-46.

Note: References 2 through 5 contain generalradlochemlcal separations, and are notvanadium separation sources.

2

information onspecifically


9/82

111. Table of Isotopes ofVanadlum*

Methad ofPreparation46 (2)146(p,n)V

T146(d,2m)#6

Ralf ILfe($ Kmrdance~0.4 flea.

Decay Scheme (1~Ieotope4623V

#7 ,,2.-4?-147vq16d)

EC2$

4+2+o+ ~i48

p+1.9Mev cu(p,3)**3)T147(d,2n)V47Ti46(d,n)v47

31 min.

V48 16 dOYS T148(d,2n)#8 (4)cu(p,E)** (3)

!9+o.6gMew~ 0.906

1.3142.25

7,2-7V@ 33adaya E.G. 0.62 CU(P,)**(3)~4e(d,n)v49%m48(PJY)vp

V51

4X1014 yearn(0,25$)

E,C.,

Naturally occurrins(99.75*) --B- 2.47-j1.43

52V51(n,i)V (2+)

%

V52 . ~52Cr52(n,p)V52~55(n, a)V .2+ 1.43352Vsl(d,)v o+ oh

23V52 3,76 min.

V53

V54

q

q*

2 min.

55uet.

~(P, B)** (3)- 2.50~ 1.00E!-.3

References for much of the data oontained h this table ere found In Strominger, D,,Hollander, J.M.; Seaborg, G.T., Rev. Mad.Phys.,, Pt. II, 585-9041958).Thetermg isused here to indicate spallation.

3


10/82

Iv. REVIEW OF THOSE FEATURES OF VANADIUM CEEMISTRY OF CHIEFINTEREST TO RADIOCHEMISTS

1. Metallic Vanadium

Pure metalllc vanadium is extremely difficult to obtain, asit combines readily with carbon, nitrogen and oxygen, formingsolid solutions with some of the products. Since vanadium Isoften produced by reduction of vanadium halides with dry hydrogengas at elevated temperatures (5), hydrogen is often present in themetal, in addition to the above elements. The amounts of thesecontaminants may cause some interference or difficulty when theirpresence in an irradlabed vanadium foil Is not lmown.

Pure vanadium Is fairly stable and is generally not subjectto oxidation by moist air. In powdered ~orm it burns In air toproduce vanadium pentoxide; however, the reaction does not go tocompletion and some lower oxides are also formed. Volatilevanadium tetrachlorlde, vcl~, is formed when vanadium metal isburned in an atmosphere offormed on heating vanadiumthionyl chloride or sulfur

Vanadium metal la not

chlorine gas. This compound is alsowith carbonyl chloride, flurfurylchloride,chloride at 6000C.readily attacked by aqueous solutions

of alkali chlorides, bromine water, or cold hydrochloric acid,whether dilute or concentrated. The metal is attacked slowly byhydrofluoric acid and by hot, concentrated sulfurlc acid. At330C, concentrated flulfurlcacid reacts with metallic vanadiumto produce vanadium pentoxide, V205J with evolution of S02] atlower temperatures, vanadium dioxide is formed, but Is convertedto the pentoxide on rslsing the temperature.

Metalllcvanadiun ISconcentrated nitric acid.vanadic acid being formed

readily attackedAqua regla alsoIn either case.

4

by cold dilute orattacks the metal,Vanadic acid is also


11/82

formed by the action onvanadium ofacid, perchlorlc acid, btiomlcacid,

such oxidizing agentsand potassium Iodate.

as chloricSoluble

vanadates of sodium or potassium are produced when powderedvsnadlum metal is fused with sodium carbonate, potassium hydroxideor potast31umnitrate.

2. Soluble Salts of VanadiumVanadlc acid and vanadates of ammonium, lithium snd the

alkali metals are more or less soluble In aqueous solution. Thevsnadates are slmilsr to the phosphates In that both anions srecapable of condensing and forml~ poly-compounds. Starting witha highly alkaline solution of a vanadateand gradually reducingthe PH, the following changes occur: In highly alkaline solution,the stable form Is V043-; between PH 12 and 10, pyrovanadate,

4- 4-27 ~ pred~lnates. .At about pH9, V4012 Is Otable. Theseforms are all colorless. At pH values below 7, the solutionsbecome highly colored, and vanadium pentoxlde may precipitate.Below PH 2, the vanadium exists as pervanadyl ion, V(OH)4+, havinga pale yellow color.

The chlorides, oxychlorldes, fluorides, oxyfluorides, andbromides of vanadium are all fairly soluble In aqueoua solutions.Many of these dissociate In aqu eou s solution to form complexIons .

Vanadium (IV) oxide combines with sulfuric, hydrochloricand hydrofluorlc acids to form salts, which, when dissolved Inwater, give blue solutions.

Vanadium (III) is chemically similar to chromium (III) andIron (III), and forms aqueous soluble salts with most of thecommon acids. Soluble complexes are formed with fluoride, cyanideand ammonia.

Vandium (II) Is similar to the dlvalent states of chromium5


12/82

and irm, and forma soluble salts with mo~t acids, except thosecapable of undergoing reduction. Solutions of uncompletedvanadium (II) are generally violet and are eaOlly oxidized.Soluble complexes are formedand ammonia.

Oxldatlon-Reduction BehaviorPentavalent vanadium is

with cyanide, fluoride, sulfate

reduced In acid solution by sulfiteIon, or by bubbllng S02 gaa through an acid solution; vanadylIon, V02+, 1~ formed, having a blue color. Other methods forthe reduction of vanadium (V) Include: ferrous Ion In acid;evaporation with hydrochloric acid, preferably In the presenceof ferric Iron and sulfuric acid (6); ,passagethrough a Jonesreductor, in which vanadium Is reduced to the blvalent state(7); reduction to the quadrlvalent state by hydrogen aulflde(8), which Is then expelled by bolllngwhlle,C02 Is blown throughthe solution; shaking with mercury in a dilute solution of hydro-chloric or sulfurlc acid (9) containing sufficient sodium chlorideto precipitate the resulting mercury (I); reduction to the quadrl-valent state by hydrogen peroxide In hot acid ~olution (10); andreduction to vanadium (IV) in a silver reductor.

Vanadium can be oxidized to the pentavalent state by nitricacid, but the reaction has been shown (11) to be only 99 per centcomplete. Boiling perchloric acid, persulfate in the presence ofsilver Ions, and hot excess permanganate in acid solution alsooxidizes vanadium to vanadium (V).

In neutral solution, iodine, dlchromate, and permanganateoxidize vanadium (II) to vanadium (III) If the addition IBterminated at the phenosafranln change point. Iodine in a saturatedsolution of sodium carbonate oxidizes vanadium (IV) to vanadium (V).The text by Chariot and Bezier (12) gives several other procedures

6


13/82

for the oxidation and reduction of vanadium compounds, aa do manyof the sources in section I.

3. Insoluble Salts of Vanadlwn - Precipitationand Co-precipitation Characteristics

A. Insoluble SaltsSome of the readily obtainable Insoluble cnmpounds of vanadium

are listed in Table I. Many of the compounds listed offer possiblemeans of separating radlovanadium from solution. The referenceslisted in Parts I and II contain information on the uae ofcertain of the compounds in separation and analytical procedures.

B. Co-precipitation CharacteristicsAmmonium Phosphomolybdate as a Carrier for Vanadium

It has long been known that quinquevalent vanadium can becarried along with smmonium phosphomolybdate precipitates, Impartingto these precipitates an orange or brick red color. That theprecipitation can be made quantitative has been demonstrated byCain and Hostetter (10,13), provided that the amount of phosphorousis five to ten times that of the vanadium. However, none of thevanadium is carried down if it is in the quadrivalent state andprecipitation is made at room temperature (14). Coprecipitationof vanadium with phosphomolybdate affords a good means of separatingvanadium from such elements as copper, chromium (VI), nickel,aluminum, iron, and uraniun~

In order to mske the separation, prepare the solution as foran ammonium phosphomolybdate precipitation, add ten times as muchphosphorous as there is vanadium present, and then a slightlygreater than usual excess of ammonium nitrate. Render nearlyneutral by adding ammonium hydroxide, heat to boiling, add anexcess of sodium molybdate solution, and shake for a few minutes.

7


14/82

Table I. Insoluble Canpounda of VenediumIiemerka (Ref.)eagent (a)

*1*Prmclpltate Solublllty

Insoluble Mdition of U- to neutralalkeli venadate - oollodial whiteprecipitate (17J.@J3Aluminum metavanadate

As+ A~VOh .xH20Silver orthovenadato

soluble in HNand NHum 3 reeh-repWed%vo*matedith oerefully neut al zed AEN03;orange powder (5,17) .Addition of neutral AS+ e.eltto%V?%;lY precipitate

Ag4v207H20Silver pyrovenadate

Ineoluble aaprecipitatedKuP - 5xlo-7EW3Silver metavanadate

Mdition of AsN03 to neutralNH4V03; gelatinous yellow pre-cipitate (5,17,18).Ba(V~)2.H20Barium met avanadate

Precipitate at pH - . 4 . 5by addingSaCl to NWIVO solution in acid.Stabfe up to lhC. Loses H20128-371c to form stable an-hydroue ualt (5,17,18)B~V207Barium pyrovanadate

Insoluble aeprecipitated Addition of BaC12 to solution of%#l%Zei~~~~; hie re-BiVO&Biemuth orthovanadate

Ineoluble asprecipitated Formed by double decompositionof alkeli vermdate an d BI(N03)3;bright yellow (7).ca2v207 .fi20Caloium pyrovenadate Ineoluble ccprecipitated Addition of CeC12 to NCI+V207uolution. Ca2V207.5/2H20 fmmedby drying at 100oC; white pre-cipitate, (17).

C0(H3)6- [cO(ILJ614(v@17)3 PreciDi&ate in aoetic acid d. PH- 5.1;gelatinouO orenge ,precipi:tate. Dry at 100-1270C. Ignitesto MoO .9V205 above X2% (18).[cd~#6](vo+3 Precipitate underneutralramnoniaclcondltions. Driedbetween ~ end 143C,to 2CO0.F*05 between 60%%%9500c,Ye low-pinkrecipitate(10)

--

InsoIuble asprecipitated Precipitate by mixing Cu+ ueltewith uoluble orthovanedates .Greenish-yellow precipitate (17,18).~u++ CU3(V04)2

Cyprlc orthovanadate

Addition of CUS04 to solution ofNH4V0 J greenieh-yellow precipi-?ate 17,18)2v207 .x20Cuprio pyrovanadate Insoluble aeprecipitated

mvo3 )2Oupric metavanadate

Colloidd preci itate formed byaddition of Cu3 to neutralclkeli venadate. Green precipi-tate (17)Insoluble aeprecipitated

eU-i

Fe(o)64

Hg2*

Fe(V~)3Ferric net avanadate

Imoluble in H20and elcohol; acidsolubleOlive-r een colloidal precipitate(17,19

(vo)#(oN)6VanadylferrocyanideHE2(W3)2

Precipitation almoet amuplete;V(V) gives no ~reoipitate.Yeenieh-yellow (15 .--

Addition of Hg2(N~)2 to venadateunder neerly neutral condition;loees weight between 60 cnd6700c; v205 fomed above 675C.Orange precipitate (17,1B,20).

--MercurOua iuetavanadate

8


15/82

Table 1. Insoluble Cempounda of Venadium (Cent.)Preclpitate

HE(V03)2

VONH4P04Vanadylammonium phon-phateV2S3Vanadium trlsulflde

Solubillty Remarka (Ref.~leaent (a)-H~- Additlon HgC12 to neutral vena-date uolution; white precipitate(17).

--

HPo L = +NH p I (15).-

H2S+NH4CEI Insoluble H20;soluble in el-kali uulfldee;sliuhtlY solubleThIo-cemplexea probably formed inexoesa alkali sulfide. V(III)sensitive to air oxidation (19).

In~lk~l, HN03,HC1andH2S042s5Vanadium pentasulfide

In(V03)3 .2H20Iridiummetavanedate

llIio-canplexeE fenned in qxceeeof sulfidee (19).

Addition InCl to NaV~; yellow?recipitate ( 7) .Mn ( v o 3 ) 2 . m1 2 0 - -14angan0uemetavanadate

Addition of MnS04 to NH4v0 - dark?ed, finely divided precip tate(17,18)Ni+F Ni(V~)2.~0

Nickel metavanadate

VO(OH)2Pb3(V04)2 .xH20Lead orthovanadateb2v207 .-20Lead pyrovenadatePb(VC@2 .xH20Lead metavaruadate*( V03)4Stawnic metavenadate

v207 .6H20Thorium pyrovanadateT14V207Thallium pyrovanadate

Tl~ .xH20Thallium metavanadate

--AmnOnium Uranylorthovanadate

--

oH-Pb+t

Brown preoipitate.--Insolubleasprecipitated Lead acetate added to uolubleorthovanadatej white powder (5,17).Insoluble at hightemperature Boil solution of Pb(NO )2 and7H4V03 in aceti. aoid 5,17).Slightly solubleE %:%:%%

Acetic acid solution of vanadateplus lead salt (17,19,21) .Large exceaa of Sn44 requiredfor preci itatiOTljyellow pre-cipitate 715) .

Ineoiuble in H20Jsoluble in con-centrated acidaK140z 6X10-12~?pm~ z.6X10-11np

(5,17,19)Addition of T12S04 to sold.sturated eolutlon of Na3V04;11 ht yellow precipitate (5,17,72 .

K1lOx 8 ,2x10-6K:p~m 4 .13xlo5aP

Tl+

U02*

Greenish-yellow precipitate (22),

Dry at 105C (18).-

9


16/82

Filter the orange or brick red precipitate and wash with a hotsoltitlonof smmonium sulfateacldlfled with dilute sulfuric acid.Titanium Hydroxide as a Carrier for Vanadium

That vanadium can be carried by the precipitation of tltanlumhydroxide can be shown,in the following manner (15): a mixtureof quadrivalent titanium and pentavalent vanadium in hydrofluoricacid is treated with concentrated ammonium hydroxide, fo~ng alarge white precipitate. To this precipitate is added a solutionof ammonium sulfide, (~4)2S, which turhs the precipitate grayish-black . There is no evidence for the reddish color of thiovanadateeither in the filtrate from the ammonium hydroxide precipitation,nor in the excess smmoniiunsulfide added to the precipitate ofTiO(OH)2 which csrries the vanadium. When a solution of vanadateis added to the excess of ammonium sulfide, the characteristicred color of thiovanadate appears.

Vanadium may or may not be coprecipitated quantitatively bytitanium hydroxide, depending upon the ratio of titanium tovanadium; 50 mg of vanadium is completely precipitated in 200 mgof titanium in the ammonium hydroxide precipitation. The methodoffers at least.a partial, if not a complete, separation ofvahadium from antimony, tin, tungsten, molybdenum, tellurium,copper, nickel, cadmium, and cobalt.Other Co-precipitating Agents

The retention of vanadium by alumlnum, ferric, snd chromiumhydroxides has been investigated (16). It has been noted thatthe retention corresponds to the adsorption process. Coprecipita-tion has been shown to take place for semi-micro and micro amountsof vanadium. The relative coprecipitation strengths ,on thehydroxides are Al> Cr>Fe.

10


17/82

4 . Complex Ions of Vanadium

Vanadium form many complex ions with organic and in-organic llgands. Several of these are of use In ion exchangeand solvent extraction procedures. These methods, and theirdependence to a large extent upon complex Ions of vanadium,are discussed In later sections.

Several conplex Ions involving vanadium are listed InTable II, which also lists conditions of complex formationand stablllty constants, where lmown. Vanadium forms severalcomplexes other than those listed in Table II; these are separatedinto complexes involving the major valence states of vanadl.umandare discussed In the sections which follow.

A. Complexes of Pentavalent Vanadium:Sulfate, oxalate and tartrate form complex Ions with

pentavalent vanadium In aqueous solution. These complexesare all of the atO- type, In which the oxygen of the llgandIs coordinated to the V03+ or VO~ species;

The existence of oxalate complexes of pentavalent vana-diumdlum

has been demonstrated clearly by Rosenheim (23). Vana-solutlons treated with alkali or ammonium oxalates form

clear yellow Oolutlons. The complex 18 sufficiently stablethat no precipitate forms on addltlon of solutions containingcalcium salts except In the presence of excess oxalate. Inaddition, vanadium Is found only as the anionic species.Souchay (24) proposed that the complex be written V02(C204)~-;and that the complex-forming reaction be gfven by

V30~- + 6c20:- + 6H++ 3 V0 2 (C2 04 )~-+ 3 H2 0.Souchay has also found (24) that In tartrate medium two

complexes of vanadium are formed. In the presence of a largeexcess of tartrate In neutral solution, a 1:1 complex (structure I)

U


18/82

a*b.a.d.;:g.

CompletingAgent

q

oH-

cN-

scN-

2-02

1=

Table II. Complex Ions of Vanadium*

Reaation~+ +HOH = V(OH)2* + H+

~++ 2HOH * V(OH)] + 2H+V02++HOH q V&& + H+

v- +SCN-* Vsm?+Vd++ scN- = VOSCN+F+ + 6SCN-4v(scN)~-

Vo; + 1+02 * v o ~ + 2 H +~ H2v#4(02)~-3 Hv20J02);-: v204(02):-

~2 + +F-=VOF +

IonicStrengthVariedVariedVariedVariedCerraotedto o

333

VariedVaried

2.62,6;&&r

varied(I+@VariedDilute


19/82

Is formed. If a V:tartrate ratio greater that 1:1 Is maintained, acomplex Iaformed Involvingture II).

yo2H$COO NaH(!-COO Na

IOt1Structure I

two vanadium and one tartrate Ion (struc-

OvokIHC-COONaIHCCOONaIOvoz

Structure II -

Solutions of these complexes are garnet-colored. Addition ofalkli causes conversion of the complex to tartrate and vanadate,while acidification below pH 5 converts the complexes to theacid salts of the complex tartrates.

A recent publication by Feigl (25) points out the maskingeffect of fluoride Ions on some characteristic reactions ofpentavalent vanadium. Reactions occurring In the presence andabsence of fluoride ions are compared In Table III. In orderto account for the anomalous behavior of pentavalent vanadiumIn the presence of fluoride Ions,,Felgl postulates the existenceof a fluoro-complex of a type which allows for only a smallequllbrlum concentration of the slrnplevanadium species In solu-tion. Felgl further postulates that the complex is of the typeformed by replacing one of the oxygen atoms coordinated to thevanadium by two fluoride atoms.

Little information has been reported on the occurrence ofpentavalent vanadium - chloride complexes; however, It is knownthat a brownish-yellow to brown complex Is formed between penta-valent vanadiumsolutions.

and chloride ion in strong hydrochloric acid

13


20/82

Table 111Masking Effect of Fluorlde Ion on Vanadate

Without F-Blue colorYellow precipitateGreen precipitateYellow-red colorGreen precipitateBrown precipitateRed-brown precipitate

ReactionZn + HC1AgN03K4Fe(CN)6202Benzidene8-hydroxyqulnolInecupferron

With F-No reactionNo reactionYellow precipitateNo reactionViolet precipitateBlue-green colorRed-brown precipitate

B.

allare

Complexes of Tetravalent VanadiumTetravalent vanadium forum a large number of complexes,

2+of which Involve the vanadyl group, VO , and most of whichate- complexes. Evidence has been found (26-28) for the

vanadyl thlocyanate complexes VO(SCN)~- and VOSCN+ th?lattercomplex appears not to be very stable. There Is some evidence(28) for the occurrence of higher complexes In very concentratedthlocyanate solutions.

Two series of oxalato complexes have been reported byKoppel and Goldman (26). The complex most readily formed IsOf the form H2(VO)2(C204)3.ag, which gives a positive testfor oxalate In aqueous solution. A large excess of ammonl~moxalate gives rise to the second series of oxalate camplexes,represented by M2VO(C204)2.2H20. Sodium and potassium oxalates,even In high concentrations, do not form complexes of this t y p e .No t e s t for oxalate Ion Is obtained In aqueous solutions of thepure monovanadyl complex.

Sulfate and sulfltecomplexe~ have beenare analogous to thepreparedby treating

oxalate complexes. Thevanadate solutions with

observed (29), whichsulfite complexes aresulfur dfoxlde smd

14


21/82

alkali aulfitea. The first sulfite complex ha6 the compositionM20.3v02.2s02. On adding excess sulfite, a clear green solution,corresponding.to VO(S03)~- , is formed.

Rivenq (30) reports the formation of cyanide complexes fromVO(CN)64- through VO(CN)2. Since a sixfold coordination about acentral V02+ ion would be required, the existence of the VO(CN)64-complex is questionable. No such coordination has been foundfor other ligands, and it is doubtful that it exists in the caseof cyanide.

Ducret (31) has suggested the existence of weak fluorocomplexes at a pH of approximately three. These appear tohave little value in radiochemical separations. A tartrateand two citrate complexes are also formed with the vanadylIon. The stability in alkaline medium of the two citratecomplexes lies between that of the tartrate and the oxalatecomplexes, the oxalate being the less stable of the two.

Malonate, salicylate, catechol, and several other organicligands fo?m complexes of the ate-type with vanadyl ion. Severalof these are insoluble in aqueous medium, and have been used forthe gravimetric estimation of vanadyl vanadium.

c . Complexes of Trivalent VanadiumAmong the camplexes of trivalent vanadium, which exists

3+ (heiahydrated) ion In aqueous solution,nly as a metallic Vthe halogens and halogenoidB are formed most readily. Fluorideions form *he following complexes: V&-, V&. H20, VF4-. 2H20(32). Chloride ion forms the VC1 2-. H20 complex.5 The cyanidecomplex (33) has been isolated, but is unstable In aqueous solu-tion. Several thiocyanate complexes have been reported (28,33)but only the VSCN2+ and the V(SCN)63- appear to be stable inwater, the latter only at high concentrations of thlocyanate.

15


22/82


23/82

at the time of precipitation must be kept below 20, sincehigher temperatures cause a tarry mass to form, making filtra-tion difficult or Impoaslble. Too long a delay In removingthe supernatant yields the same tarry mass. Vanadium cannotbe separated from titanium or aluminum by this method (37).

Other ions which precipitate with cupferron from acidsolution Include Iron (III), titanium (IV), zirconium, uranium(in 4-8 percent sulfuric acid), copper, gallium and aluminum;from weakly acldlcaolutlons, bismuth, antimony (III), tin (IV),molybdenum (VI), thorium and tungsten also precipitate. TheInterferences of seversl of these element6 can be eliminatedby the use of the various completing agents available, forexample, ethylenediamlnetetra-acetic acid. In order forvanadium to be precipitated quantitatively from any solution,It must be present in the tetravalent or pentavalent state.In highly dilute solution, Iron (III) may be added as a collector(38) for vanadium If not already present in solution.

8-Hydroxyqulnollne (Oxlne): This versatile reagent wasfirst introduced by Hahn (39) and Berg (40). It Is verysolubleIn>alcohol and acetic acid and forms Insoluble chelate complexeswith man y metals. Thea& complexes can often be dried at 105 to140 C and weighed as such in gravimetrlc procedures.

Vanadium, as a vanadate, reacts with 8-hydroxyquinollne Inthe presence of acetic acid to form a yellow precipitate whichchanges color to blue-black on hea.tlngand cooling (41,42).The yellow compound Is the hydroxyqulnolate of tetravanadlc acid:

(C9H7NO)2o Hpv40~~The blue-black compound is the anhydrlde of the acid

(C9H6NO) -v(oH) - (C9H6N0)and has the composition

(C9H6NO)2=V0- o - vo = (C9H6N0)2L7


24/82


25/82


26/82

Ion (52). The reaction appears to take place between a ~errouO-bipyrldyl complex:

[$1

I:Nl


27/82


28/82

ofmanganese (II) and zlrconi.um(IV).N-Benzoylphenylhydroxylamine: This reagent, having

a structure clo~ely resembling that of cupferron, alao re-sembles cupferron closely In its analytical reactions. Un-like cupierron,however, It Is quite ~table toward heat,light, and air. It fonus water insoluble chelate complexeswith tin, tltanlum, zlrconlum, vanadium (V), molybdenum (VI),and tungsten (VI) in acid solution. Copper, Iron, and aluminumprecipitate at a pH of approximately 4.0, while cobalt, cad-mium, lead, mercury, manganese, uranium, and zinc react at pHvalues greater than 4.0 (60-61). The vs,nadatechelate com-plex precipitates as an orange-red mass, insoluble in water,but Boluble In benzene, ethanol or acetic acid (62).

3-Hydroxyl- 1,3-diphenyltriazine: This reagent (63)has the following useful properties: it is stable to heat,light, and air, and is capable of being stored indefinitely.Its chelate complexes with many metals are granular, waterinsoluble, stable thermally, and may be suitable for directweighing. Below pH 3 it forms chelate precipitates onlywith copper, palladium (II), iron (II, 111), vanadium (III,V),titanium (IV), and molybdenum (VI). Except for the copperand palladium chelates, the precipitates are decomposedonheating in acid solution.

Vanadium forms chelate complexes with several otherorganic ligands; ethylenediaminetetra-acetic acid and1,2-diaminocyclohexane-N, N, N, N-tetra-acetic acid chelatecomplexes with vanadium (II, III, and IV) have been reported.(64, 65). h addition, glycollic acid (66) potassium xan-thate (67), and sodium diethyldithiocarbamate (68) allgive precipitates with vanadium salt solutions, and have beenu~ed to some extent in analytical schemes.

22


29/82

6. Extraction of Thenoyltrifluoroacetone Complexesof Vanadium Into Organic Solvents

A survey of the literature indicates that little or nointereat has been EIhownin the chelatlon and extraction ofvanadium by meana of thenoyltrlfluoroacetone. It appearsthat the only information available on this extraction isthat obtained in the laboratories of the Nuclear ChemistryGroup at the University of Michigan (69).

Extraction of vanadium by means of its TTA complex wasundertaken using 0.25 ~ solution of TTA in benzene. E,qualvolumes of the benzene solution of the llgand and carriersolution (10 mg vanadium per ml.) were shaken together forone minute. The extraction of the vanadyl-TTA complex asa function of PH is shown in Figure 1, from the data of

70 I I I I I IEXTRACTIONOF VANAOIUM0.25M TTA IN SENZENE60 - (1 MIN. SHAI( IN6)

*->; 50 -~oazs 40 -k.ozg~ 30 -ai-fx; 20 -:it 10 -

00 Lo 2.0 3.0 ~.O 5.0 60 T.OPH (AFTER EXTRACTION)

Figure 1 Extraction of Vanadium (IV) into TTA,

23


30/82


31/82


32/82

slightly1 x 10-3ether at

extracted are CU(II) and Zn. Approximatelypercent of vanadium (IV) is extracted intohydrobromic acid concentrations of one-and-

six-molar. No information is available for otherHBr solutions.

1q Pm)O As(llll70 x As (Y) /x v m)u v (m60 + Se(m)M Te(JY)u Re(~

50 @ Nb(~~ Ta

40

30

20

10

10 IsMOLES HF/LITER

Figure 2. Distribution of fluorides between HF solutionand ethyl ether.

4. rhiocyanate: Alkali thiocyanates have long beenused in the calorimetric estimation of many metals.Complexes with thiocyanate are formed by iron (III),uranium (VI), bismuth, niobium, and rhenium, as wellas cobalt (II) and ruthenium (III); these can be ex-tracted readily into oxygen-containing organic sol-vents. In the presence of reducing agents and/or

26


33/82


34/82


35/82


36/82

stripped from the organic phase by contacting with areducing agent, such as 0.25 molar oxalic acid solution.Further data on such extractions may be found In recentAtomic Energy Commission reports (e.g., 80-82), andtechniques and procedures (e.g. 83).

6. Heteropoly Acids: A characteristic property of heter-OPOIY acids Is their solubillty In organic slovents.Elements capable of forming this type of complex in-clude Mo, As, P, W, V, and S1.

For the most part, esters, ketones, aldehydes,and ethers are good extractants for heteropoly acids(84) . Carbon dlsulfide, carbon tetrachloride, chloro-form, benzene, and toluene do not make good extractantsfor heteropoly acids (85).

Molybdovanadophosphorlc acid has been found (86,87)to be extractable into mixtures of3-methyl-l-butanoland ether, l-butanol and ether or Isobutyl acetate;l-butanol, and ethyl ether.

IIIaddition to the above extractions of vanadium complexes,vanadium can also be extracted from aqueous solutions by rela-tively high molecular weight amlnes and by alkylphosphoric com-pounds. A great wealth of material on these compounds can befound In recent literature (e.g., 88-96).B. Chelate Systems

Many, If not all, of the chelate complexes consideredIn section 5 can be extracted Into organic solvents. Severalof these chelate systems are discussed below.

Cupferron: The chelate precipitate ofcupferron has been found to be soluble in a

30

vanadium [V) andvariety of organic


37/82


38/82


39/82

Table VII. Extraction of Metal Cupferratea (lCO)z1322

23

25262728293040414248@5050515874

m83903192

=ementAlTi (II)v (Y)m (II)Fe (III)coWI.ou (II)m (Iv)Zr (I@m (v)Ho (VI)cdmsn (II)Sn (IV)9b (III)Ce (IV)n (VI)

~ (11)BiThPau (Iv)

Zxtmctim Hangepa 2-5PH z -0.08PH -0.00 to -0.56PH+7PH -..-0.56dilute BQhcPH-7pll+ 0.08m--7PH . -0.56px


40/82


41/82


42/82


43/82


44/82

the reagent Is water soluble. The chelates, however,In such solvents as chloroform, carbon tetrachloride,

are solubleether, amyl

acetate, benzene, and ethyl acetate. Extractions possible withthe reagent are given In Table X (100). It has been found (107)that the reagent decomposes quite rapidly In solutions of low PH.Extractions carried out at these low PHIS should be performedusing an excess of reagent to affect decompostlon.

Table X. Fxtrac!tlonof Diethyldithiocerbemate Ohel.atee(1~)

z23242526s272823x3133344142474748495051527475768081828392

ElementvCr (VT)Mn (II)w (II)Fe (III)coNICuZnOmAC (III)SeNb (v)MO (VI)&wCdInam (Iv)Eb (In)Te (1-v)u (VI)F@OemT1Pbmu (VI)

PH Range fo rCptlmum &tractIon30-66.54-110-1o6-80-1o1-3.5334-5.83

Weakly acid334-11335+4-9.5

5,~+@9??1-1.512.2 gHcl7-9 (slew;extraotla Incomplete)33

Bvery acictn1-106.5-8.5

%lventEthyl aoetateChlorofonllEthyl aoetateCarbon tetrachlorldeChloroformmllorefomChlorofomChlomfomnEthyl acetateEthyl aoetateCarbon tetmohlorideEthyl acetateCarbon tetrachlorldeEthyl aoetateEthyl aoetate Carbon tetrachlorldeHthYl acetateEthyl aoetate Carbon tetraohlorldeCa rb en t et ra oh lk deChloroform, benzeneCarbon tetraohlorldeEthyl acetateEthyl aaetate-hen tetznohlorldeZthyl aoetateEthyl acetateEther, ethylacetateChloroform, etherChloroform,.ether,CMY1 acetate

38


45/82


46/82


47/82

and vanadium-bearing leach llquor Is placed In one portion ofthe cell, and the sodium carbonate solution in the other. Adirect current is applied, and the uranium precipitates agU308 and/or U02 In the POrtiOn of the cell containing the sodiumcarbonate. The vanadium remains in the leach liquor solution andcan be removed from solution by electrolysis at an amalgamatedlead cathode.

Murthy (120) has also investigated the separations of vana-dium and uranium by ion exchange methods In sodium carbonate solu-tion. A solution containing uranium, as the carbonate complex[U02(C03)314-, and vanadium, as VO~-, in excess sodium carbonateis passed through a cclwnn of Amberlite IRA-UOO anion exchangeresin in the chloride form. All of the uranium, and part of thevanadium ifladsorbed on the column. The vanadium is eluted witha 10-percent solution of sodium carbonate. The uranium Is desorbedwith a sodium chloride solution. The elution of vanadium withsodium carbonate is shown in Figure 7.

Erlenmeyer and Eahn (121) have investigated the use of 8-hydroxyquinollne as an adsorption agent in the chromstographicseparation of several ions, in which the adsorption takes placeby means of chelate formation. The order of adsorption, and thecolor of the various layers formed has been given as:1. Vo- : grayish-black 5. ~i2+ :3 green

2 . Wof- : yellow

3. ~u2+ ; green

4. Bi3+ : yellow

6. ~02+ : pink

7. ~n2+ ; yellow, with intensegreen fluorescence

8. ~e3+ : black

9. m;- reddish-orange

41


48/82


49/82

type of technique ,points the way toward the use of other chelate-forming adsorbantswhere resin exchangers may be ineffective.

Hicks and co-workers (122) have investigated the behavior ofa number of metals toward anion exchange on Dowex-2, a StrOng basictype of resin. The resin is converted to the chloride form by treat-ment with concentrated hydrochloric acid before use, and is alurrledinto a column arrangement such that a bed of resin approximately10 cm. long by 0.4 cm. in diameter is deposited. The elements tobe studied are placed on the column in concentrated hydrochloric acid;approximately 0.1 to 0.4 milliequivalents (- 10 mg) of each metal isused. The solution is passed through the column at a rate of onedrop every 5 to 10 seconds. When the liquid is nearly level withtop of the resin, a drop of concentrated hydrochloric acid is addedto the reservoir. The liquid is passed through until the levelagain approaches the top of the columri,and two additional ml ofconcentrated hydrochloric acid are added as a wash. On complet-ing this wash, which represents approximately five free columnvolumes, the eluate is checked for the metal being studied. Ifthe metal is not eluted by this procedure, 4-ml. of 9 M HC1 arepassed through the colunn, and the eluate rechecked. Hydro-chloric acid of6, 3, 0.1 and 0.001 molarlty Is then tried insuccession until the metal appears In the eluate. Water, 3 Mperchloric acid, molar ammonium hydroxide, and finally, molarsodium hydroxide are used as eluants If the hydrochloric aciddoes not remove the metal from the column. If 4 ml. of eluantdo not remove the metal completely from the column (approximately10 columm volumes), the metal IS considered not to be eluted bythe particular eluant.

The results of this investigation are presented In Table XII,which lists only those elements investigated.(II, III and IV) are eluted with,concentrated

43

Note that vanadiumhydrochloric acid,


50/82

signifying very slight adsorption of these Ions on the column.Vanadium (V), on the other hand, is adaorbed from concentratedhydrochloric acid, and 16 eluted, along with TI (IV), Pt (11),Zr (IV), Hf, and trace amounts of Ag and Ta, by,6-9 ~ HC1.

In the sunmiaryof results in Table XII, it Is well to notethat element6 which are eluted by a given eluant have, In general,rather widely different chemical properties. Subsequent separationof these elements can then be accomplished by other methods.

Studies similar to that of Hicks, et al., have been conductedby Kraus and Nelson (123) and Kraus, Nelson and Smith (124). ~ausand Nelson studied the adsorption of a number of metal Ions Inhydrochloric acid on Dowex-1 anion exchange resin. They foundthat over the range 1-12 ~ hydrochloric acid no region Is foundwhere considerable adsorption takes place-for vanadium (IV). In

Table XII. Elutlon of E1-nts from Euwex-2AnlOn~chenge Real. (122)

Elutlnsgent12 ~HCl Alkali metals, alkaline earths, rare earths,

sc, Y, Ti (III), v (II, rII, rv), Mi,AS (III), Aa (V), Se (IV), T1 (I), Pb, M,OU (II) S1OH1Y, Al, Cr (lXI), Fe (II),Mn (II)

6-9 ~HCl Ti (IV), V (V), Afs*,T,*, Pt (II), Zr, Hf3.6 ~HCl Fe (111), Cm (II), ~, No*1-3 ~HCl fi, u, MO (vI), m= .% (rv), Te (Iv),

~ (~), AU (as AuI~), ~< 0.01 ~HCl an (II), m (II), w, ab (v) slowly3 ~HC104 Po, cd, Sb (III), Sb (v) slowly1 ~ NH40H Pd, A& Sb (III), Sb (v)

Not Eluted To*, Fill,, Re, OE, Ir, Pt (Iv), Au (III),T1 (III)

* m traoe concentratlorm only.

44


51/82

~ .015rGE -12.1 M HCIa-1g .ol@ -.zg~K.005 -+zEzou

+9. IMHCI

L0 25 30 35+1. OMHCI

Fe (III)

AI45 50 55

EFFLUENT VOLUME (ml)Figure 8. Separation of V(IV), TI(IV) and .Fe(III)by anion

exchange (18.6 cm. x 0.49 cm2 Dowex-1 column;1 ml 0.05 ~V(IV), c).018~Tl(IV), 0.025 ~Fe(III)In 12MHC1.

the case of vanadium (III), only slight adsorption Is found to takeplace In 12 ~ hydrochloric acid. Vanadium (V), however, whichforms an intensely brown-colored solution In concentrated hydro-chloric acid, can be adsorbed strongly by an anion exchange resin,giving rise to a dark brown band. Figure 8 (124) shows the separ-ation-of vanadium (IV) from titanium (~) and iron (III) on acolumn of Dowex-1 anion exchange resin. Since vanadium (~) isonly v e r y slightly adsorbed from 12 y hydrochloric acid,.it elutesfirst, while the titanium (IN) and iron (III) are more stronglyadsorbed and hence remainon the column when eluted with concen-trated hydrochloric acid. The dlstrlbutlon of these three ionsfrom hydrochloric acid is shown In Figure 9 (123).

The distribution of vanadium (IV and V) between hydrofluoricacid and Dowex-1 anion exchange resin has been studied by Fsris(125), along with a study ofiodic table. Faris results

many other ionsthroughout the per-are shown in Figure 10; he found45


52/82


53/82

that neither vanadium (IV) nor (V) produced a definite peak intheir elution, indicating possible oxidation o r reduction of thesespecies as a result of contact with the resin.

Anion exchange resins have been employed (126) to separatevanadate from sodium and potassium ions In solution and for thequantitative estimation of the vanadate adsorbed. A mixture ofthese Ions Is passed through a column of .Emwex-2resin In thehydroxide form. Sodium and potassium are not adsorbed, of course,but the vanadate Is adsorbed, displacing hydroxide Ions from theresin. The amount of vanadate present in the mixture can then bedetermined by titrating the liberated hydroxide with standard acid.

Samuelson, Lundenmethod for the removalhg alkali salts. The

and Schramm (127) have devised a usefulof several cations from solutions contaln-method is based on the observation that a

number of cations can be adsorbed on an anion exchange re~ln sat-urated with anions capable of forming strong complexes. Tartrate,citrate, and oxalate are examples of the complex-forming anionsused. Cobalt (II), nfckel (II), copper (II), iron (III), andvanadium (IV) are adsorbed quantitatively on an anion exchangeresin in the citrate form, while the alkali metals are not. Thealkali metals elute with water, leaving the above ions behind onthe column. The adsorbed Ions can be eluted wlchhydrochloricacid solution.

Molybdenum is separated from solutions containing lead,copper (II), Iron (III) and vanadium (IV) In a procedure devisedby Klement (128). Molybdic acid, as the citrate complex, passesthrough a column of sulfonlc acid type cation exchange resin Inthe hydrogen form, while lead, copper (II), Iron (111) and vana-dium (IV) cations are strongly adsorbed. After elutlon of themolybdic-citrate complex and washingadsorbed cations are eluted by means

47

the column withof dilute acid.

water, theFor the elu-


54/82

ti.onof copper and vanadium, 1:9 sulfurlc acid is used. Iron isbest eluted with 4 N hydrochloric acid, and lead with 1:7 nitricacid.

Solutions containing vanadate, chromate, molybdate, tungstateand phosphomolybdate cannot be adsorbed successfully by cationexchanges In the hydrogen form. A portion of these anions Is re-tained on such resins as a result of partial transformation Intocations by reduction (124) or as a result of precipitation (110).Separations of these ions from cations can be performed readily,however, on columns of cation exchanges,In the ammonium form.

A few separation schemes involving ion exchange separationshave been devised specifically for theisolation of radiovanadlumformed during cyclotron bombardments. Schindewolf and Irvine (129)utilize the fluorideform of an anion exchange resin to adsorbtitanium and scandium, while vanadium (IV) passes through (seeprocedure 7, Section VII). Another procedure, due to Walter (130),,separates radiovanadium from tracer amounts of radloscandlum andmilligram amounts of titanium by passing an oxalate solution ofthese elements t~ough a column of Dowex-1. No traces of radio-scandlum actlvlty are found In the eluate, and titanium contamin-ation Is less than 20 micrograms per milliliter of effluent. (cf.procedure 11, SectIon VZI). -

v. PROBLEMS ASSOCIATED WITH DISSOLVINGVANADIUM-CONTAINING SAMFLES

Many minerals containing vanadium are readily attacked bymineral acids, an initial treatment by hydrochloric acid followedby nitric acid usually being all the treatment necessary for com-plete extractionerally devoid ofsodium carbomte

of vanadium (131). Any Insoluble residues, gen-vanatilum,can be made soluble by fusion withand dissolution of the melt in hydrochloric acid.

48


55/82

This solution Is then added to the main body of solution. Ifsilica is not to be determined, the solution of insoluble residuefrom acid treatment of a vanadium-containing sample can be accom-plished by means of hydrofluoric acid, which is then eliminated byevaporation with sulfuric acid or by repeated evaporation withhydrochloric or nitric acids. The usual treatment of a grosssample with hydrofluoric acid, followed by evaporation with sul-furic acid to eliminate the ~,is not recommended since volatilefluorides or oxyfluorldes of vanadium may be formed at red heat.

The materials which readily yield their vanadium content tothe above treatment Include vanadlnlte, carnotite, desclolzite,cuprodesclolzlte, eusynchlte and other naturally occurring van-adates (132),ln addltlon to most of the cormnonvanadlun-contain-Ing alloys. Patronlte may also be dissolved by this method ifmost of the sulfur present Is first removed by ignition.

The vanadium present in mscoellte does not appear to respondto the acid treatment outllned above, possibly because of Its pre-sence in a silicate complex. Material of this sort is best treatedby fusion methods. Many vanadfum minerals which are not attackedappreciably by acids will yield to fusion with sodium or potassiumcarbonate (to which a small amount of nlter Is added),or sodiumperoxide. Certain types are also susceptible to attack by sodiumor potassium hydroxide fusion, conducted In nickel or Iron cruci-bles, followed by dissolution of the melt In acid.

A ma~or dlsadvamtageof most fusion techniques l~es In therather long period of heating required for complete fusion. A veryuseful and short method for effecting solution of many vanadium-contalnlng materials, including biological tissue, involves asodium peroxide fusion In nickel or Iron (requiring approximatelytwo minutes for-completion), followed by rapid cooling of the meltand crucible and subsequent dissolution of the melt in acid (133)

49


56/82


57/82

0.511ANNIHILATIONRADIATION)0.986


58/82


59/82

5

2

10

I0I

1= 3x3-2 NO I7-e-57ABSORBER 1.34 g/cm2 nSOURCE DIST. 10 cm(c)ENERGY SCALE = 2 Kev/PHU

5

2

.1~ 200 400 600 800 I000 1200PULSE HEIGHT

Figure 12. Gamma Spectra of Vanadium-s2. (139)

53


60/82

VII . Collected Radlochemlcal ProceduresFor Vanadium

PROCEDURE 1Source: J. L. Brownlee, Jr.

Target material: Petroleum cracking Time for Separation: 10 min.catalyst (Al O - Si02 base)irradiated 1~ Zelatin capsule Equipment required: StandardType ofbombardment: Neutron (fission Yield: Variable (18-7@)spectrum); 10 min. at reactor powerlevel of 1000 KWDegree of purification: Sufficient for gamma spectrometryAdvantages:

m

Complete removal of aluminum and gamma activitieshaving energies greater than 1.4 Mev; rapid separationProcedure

Place a known amount of vanadium-48 activity in a 30 mlnickel crucible and evaporate to dryness. Add 3-4 gm of sodium.peroxideand bring to the molten state before the sample Irradiation has beencompleted.

- Fuse 40-100 mg finely ground sample (note 1) and gelatlncapsule with sodium peroxide for two minutes (note 2). Cool crucibleand contents rapidly by dipping base of crucible into cold water untilthe contents have solidified (note 3).

m Dissolve the solidified melt in a solution containing16.7 ml concentrated HC1, 3 ml aluminum carrier, 0.5 ml vanadium (V)carrier, and 15 ml of ~ hydrogen peroxide, diluted to 50 ml (note 4),.

saw To this solution, add 30 ml of a 10~ solution of8-hydroxyquinoline in 1:4 acetic acid, followed by approximately 60 mlof concentrated ammonia (note 5). A large yellow-green precipitate ofaluminum 8-hydroxyquinolinate Is formed.

mglass funnel.

Filter the precipitate through a 120-mm medium sinteredWash the precipitate with a minimum of dilute ammonia.

54


61/82


62/82

PROCEDUREseparator funnel is shaken, orsufficient to break the funnel.

8. The cupferron solution

1 (Continued)the pressure created on shaking may be

should be made fresh daily and keptunder refrigeration If possible.

PROCEDURE 2Source: J. L. Brownlee, Jr.

Target material: Titanium Foil Time for separation: 4-6 hoursType of bombardment: Deuteron, + 7.8 Mev Equipment required: Standard(Univ. of Mlchlgan Cyclotron) Yield; Undetermined (m 0.1 mc)Degree of purification: Sufficient forgamma spectrometry and half-life

determinationAdvantages:

m

Apparently good decontamination - no foreign gammaphotopeaks present In gamma spectrum of separatedvanadi.um-~.Procedure

Dissolve the titanium foil target In a minimum volumeof concentrated HF containing scandium and vanadium carriers. Dis-solution Is carried out In a polyethylene beaker.

EEL? The solution is transferred to a Lustroid centrifugetube and the scandium fluoride removed by centrlfugation. The pre-cipitate is washed with a small volume of dilute HF; the washingsare added to the centrifugate.

- A dilute solution of sodium aalicylate Is added to theclear centrlfugate (note 1). Pb(V03)2 IS precipitated by addition ofa l@ solution of Pb(Ac)2 acidified slightly with HAc (note 2).

Step 4. Filter the precipitated Pb(V03)2, and wash with a s~llvolume of dilute ammonium hydroxide. Dissolve the precipitate in asmall volume of HC1, neutralize with dilute ammonium hydroxide, andrepeat Step 3.

%


63/82

PROCEDURE 2 (Continued)

m Dissolve the Pb(V03)2 precipitate in a minimum of con-centrated HC1. Dilute this solution to approximately 6 ~ in HC1.

Step 6. Cool the solution (note 3), and add a 6 per centaqueous solutinn of cupferron (note 4). Filter the brown-coloredvanadium cupferrate and wash with a small volume of 0.05 ~ HC1.

m Transfer the precipitate and filter paper (note 5)to a small beaker. Add a small volume of fuming nitric acid andconcentrated flulfuricacid to destroy organic matter (note 6).When the solution is clear, heat to fumes of S03.

Step 8. Cool the solution, and dilute cautiously 1:1 withwater. Add 6 per cent aqueous cupferron (note 4).

w Filter the vanadium cupferrate and wash with 0.05 ~HC1. Transfer the precipitate and filter paper to a small beaker.Add the minimum amount of fuming nitric acid to destroy the filterpaper and the cupferrate.

Step 10. Allow the acid solution to cool. Dilute with de-ionized water to a convenient volume. Solution can be ufledasvanadium-48 tracer. The yield is approximately 1 PC.

Notes:1.

retards2.

of lead3.

Sodium salicylate complexes the dissolved titanium andits carrying on the precipitate.The solution must be kept slightly acid If the precipitationhydroxide is to be prevented.The solution is cooled somewhat since vanadium cupferrate is

sensitive to heat. 4. The cupferron solution is best kept in a refrigerator to

retard decomposition.5. h ashless gmde

used for this filtration.of analytical filter paper should be

57


64/82

PROCEDURE 2 (Continued)6. Ordinary concentrated nitric acid attackB

and precipitate more slowly - In ~me cases takinghalf hour to decompose the organic matter. Thisrled out In covered beakers. Safety glaases are

Source: Cassatt, W. A.,Department of

PROCEDURE 3

the filteras long as

step Is bestrecommended.

paperone-car-

Ph.D. Thesis University of Michigan,Chemistry, 24 September 1954Target material: Titanium foil (2 .,lils Time of separation:thick) 4Type of bombardment: Deuteron (m 7.8 Mev) Equipment required:Degree of purification: Not klOWTl Yield: Undetermined

mscandium and

Step 2.

Frocedu?e

Approx.hoursStandard

Dissolve the target in a minimum volume of HF; addvanadium carriers (10 mg/ml).Transfer the solution to a Lustroid centrifuge tube.

Remove scandium fluoride precipitate by centrifugatlon. Wash theprecipitate with a small volume of HF; add the washings to thecentrlfugate.

m Make the filtrate basic with approximately 6 ~ NaOHto precipitate T:02 . x H20. Filter; make the filtrate 6 N In HC1.

e Add a 6 percent aqtieouasolution of cupferron to pre-cipitate with dilute HC1. Transfer the precipitate to a beaker,and destroy the organic material by adding fuming nitric acid. Adda small volume of acetic acid to the clear solution.

Step 5. Neutralize the above solution with ammonium hydroxide.Add a solution of Pb(Ac)2 to precipitate Pb(V03)2. Wash the pre-cipitate with dilute ammonium hydroxide.

58


65/82

PROCEDURE 3(Continued)Step 6. Dissolve the Pb(V03)2 In the mlnlmum volume of con-

centrated HC1. Add scandium and titanium carriers (10 mg/ml).Repeat steps G and 5 twice more.

E@M Precipitate purlfled vanadium as Pb(V03)2. Filteronto a 15 mm filter disc. Mount the precipitate and count.Remarks:

The decay of the beta-ray activity waO followed by countingthe beta particles emitted In the regionray spectrometer. Analysis of the decaypresence of a 35? 3-minute activity, andGamma photons emitted by the sample wereaclntillatlon counter, and the resultlng

of 1.35 Mev with a beta-curve obtained showed thea four-hour activity.analyzed with a gamma-raycurves resolved. These

data indicated a 30 ~ 3-minute activity an d a 3.5 & O.S-houractlvlty. Gamma-ray energies, determined with a gamma scintillationspectrometer, were found at 0.329, 0.422, 0.515, 0.588, 0.682, 0.795,and 0.897 Mev with a precision of ~~. It was estimated that the0.588 Mev line decayed with a half-life between 20 and 40 minutes,and that the other lines decayed with a half~life between 3 and 5hours.

PROCEDURE 4

Source: Fukal, R., in AECU- 3887Target material: Biological ash Time for Separation: *4 min.(Seaweed andmarlne life)Typeof bombardment: Neutron (In Equipment required: Standardpneumatic tube) 10 tin. atreactorpower level of 100 KW Yield: 41.5$? 1$Degree of purification: Enough for V-spectroscopyAdvantage: Rapid separation

59


66/82

PROCEDURE 4 (Coqtinued)Procedure

m Irradiated ash is digested for 30 sec. In 15 ml. ofhot 4 ~ NaOH solution containing 10 mg-V-carrier.

m Add 10 ml of cone. HC1 to dissolve the ash. Dilutethe solution to 50 ml with water.

Step 3. Transfer the solutlon to a separator funnel Inwhich 10 ml of chloroform is already placed.

Step 4. Add 2.s ml of 6% cupferron aqueous solution andshake vigorously for 30 sec.

Step 5. Let stand for 40-60 sec. to separate the layers.Step 6. Transfer the organic layer to ,mrked tubes and

count. (See remarks.)Remarks

In this case both the scintillation well counter (l x 1-1/2NaI(Tl) crystal) and 100-channel T-spectrometer (3 x 3 NaI(Tl)crystal) were used for counting. Two 5 ml counting samples wereused, one for each counter. \

PROCEDURE 5

Source: Fukai, R., In AECU - 3887

Target material: Blologlcal ash Time for Separation: -10 min.(seaweed andmarlne life) Equipment required: StandardType of bombardment: Neutron (Inpneumatic tube) 10 min. at Yield: .30$reactor power level of 100 kw.Degree of purification: Enough for y-spectroscopyAdvantages: Rapid separation

60


67/82

PROCEDURE 5 (Continued)Procedure

m Place the irradiated aah in a beaker containing 15 mlof hot 4 M NaOH solution and 10 mg Vanadium (V)-carrier. Heat 30sec. on a burner to digest the ash.

Step 2. Add 5-6 ml of concentrated HC1 to dissolve the ash.Heat for a while if necessary.

Step 3. Add 3 drops of 10~ SnC12 solutlon to reduce V5+toV4+ (blue solution should be obtained).

Step 4. Dilute the solution to approximately 50 ml with dis-tilled water.

Step 5. Adjust pH of the solution to approximately 5 byusing 1 ~ NaOH solution and testing with Hydrlon pH-paper. (FaTntgrey-white precipitate of tin should appear.)

Step 6. Transfer the contents of the beaker to a separatorfunne1. Add approximately 50 ml of 0.25 y TTA-benzene solution andshake vigorously for 30 sec. (Green color appears In organic layer).

Step 7. Add 25 ml of 6 ~ HC1 to the separated organic layer4+and shake 30 sec. to recover V in inorganic layer.

Step 8. Add 5-10 @ops of 1 y KMn04 solutlon to oxidize V4coV5 .

EE3iQ2 Add 2 ml of 6 percent aqueous cupferron solutionwhile cooling in a dry Ice bath. Allow to stand for approximately1 minute to allow the precipitate to settle.

Step 10. Filter onto l-inch paper. Mount the precipitatefor counting.

Remarks:Chemical yield determined with vanadium-48 tracer or standard-

ized vanadium carrier.

61


68/82

PROCEDURE 6

Source: Kaiser, D., in

Target material: Biological tissue(Wet rat liver andkldney)Type of bombardment: Neutron (Inpneumatic tube) 10 min. at

reactor power level of 1megawatt

AEcu - 4438

Time for Separation: -5 min.Equipment required: StandardYield: 40-45$

Degree of purification: Enough for y-spectroscopyAdvantages: Rapfd separation

ProcedureStep 1. Irradiate sample 10 min. at

~012 -2 -1n-cm -see )-Step 2. Fuse sample In 10 gms Na202

tracer, 10 mg of vanadium carrier, and 10carrier.

1 Megawatt (approximately

containing vanadium-J+8mg of copper holdback

Step 3. Dissolve the melt in 50 ml water, and add 42 ml con-centrated HC1.

&EEELt.filter.

m.filtrate, arid

manalyzer.

Add 10 gms of tartarlc acid, bubble in H2S gas, and

Add 10 ml 6% aqueous Cupferron solution to vanadiumextract with 10 ml CHC13.Collect organic layer, and count with 100-channel

Remarks: Chemical Yield: Determined by means of tracer vanadium-48.

62


69/82

PROCEDURE 7

Source: Schindewolf, U. and Irvine, J. W.,Anal. Chem. ~, 906 (1958)

Target material: Titanium foil Time for Separation: -1-1 1/2 hrs.Type of bombardment: Deuteron Equipment required: Standardplus polyst~ene Ion ex-Yleld: > 90$ change colunns.Degree of purification: Decontamlnatlon factor for Sc and Ti

>5X103Advantages: Carrier-free vanadium-48 tracer.

Procedurem Dissolve bombarded titanium foil in few ml concen-

trated HF in high temperature,polyethylene test tube. Heat onsteam bath if necessary.

w Add few drops of H202. Evaporate to dryness.Step 3. Dissolve material in 0.5-2.5 ~ HF. Saturate with

S02 gas.w Pass solution through anion exchange column in the

fluoride form (obtain fluoride form by equilibration of resin with0.s-2.5 ~HF). Elute vanadium with 5-10 column volumes Of.0.5-2.5M I-IFn polystyrene column:Remarks: For absorptionof 1 gm titanium use polystyrene column1.3 cm in diameter x 25 cm long.

PROCEDURE 8

Source: Lemmerman, R. D., Irving, NP-1797, July 1950, pp. 54-5Target material: Chromium metal Time for Separation: -2-3 hra.

r cr203 Equipment required: StandardType of bombardment: DeuteronYield: -907Degree of purification: Very good

63


70/82

PROCEDURE 8 (Continued)Advantages: Procedure short;~48 radiochemical purity of carrier-freeRood. ~52 C= be se~arated from aaueous nhasefoll~wing V extraction.

Procedurem Dissolve chromium metal

If target is chromic oxide, fuse withtargetsodium

. .

In hydrochloric acid.hydroxide and sodium

peroxide, cool, and dissolve melt In hydrochloric acid. (cAuT1ON!!Safety glasses and shield should be used!!)

Step 2. Make HC1 solution 1 f. in pota~slum thiocyanate, 10-2~. In 8-hydroxyquinollne.

m Adjust the PH to m 2.0 with.potassium hydroxide.= Extract several times with methyl isobutyl ketone

pre-equilibrated with a solution 1 f. in KkCN and at pH 2.0.m Combine methyl isobutyl ketone layers; wash repeated-

ly with 1 f. KSCN to reduce contamination of Mn52.Step 6. The solvent can be removed by careful evaporation and

the residue taken up in dilute acid.

Remarks: Fk152can be isolated from the aqueous phase remaining48after extraction of V in N 95% yield.

PROCEDURE 9

Source: E?atzel(From W. W. Meinke, AECD 2738, 30 Aug. 49, p. 29)

Target Material: Copper foil Time for Separation:(ml gm) Approx.2 hrs.Type of bombardment: 184-inch Equipment required: Standar6cyclotron (all particles)Yield: Fair; UndeterminedDegree of Purification: Undetermined (only probable impurities

are Cr and P)64


71/82

PROCEDURE 9 (Continued)Procedure

Step 1. Dissolve the target In a minimum amount of concen-trated HN03; add carriers Zn through Cl, boll off HN03, and make

w Add H2S, centrifuge off the copper. Wash copper with1 N HC1 and re~aturate with H2S. Add wash to supetiate.

Step 3. Eoil down to 6 ml to remove H2S, add concentratedHN03 and boil down almost to dryness, and make volume toconcentrated HN03; cautiously add KC103 and boil for one

Step 4. Centrifuge off the Mn02.and add wash to the supernate.

Step 5. Bcil down to remove ~03HNo3 Cool to 5-10C and add an equal

Wash Mn02 with 6,

and HC1, and makevolume of dlethyl

5 ml withminute.N 03

lNlnether,

Add 5 drops of 30~ H202 and immediately stir vigorously to extractChromium. Draw off the ether layer, and wash water layer with one-half volume of ether, stirring vigorously to extract any chromium left. Draw off the ether layer and add to the orlglnal ether layer.

Step 6. Almost neutralize the water layer with NaOH and pourinto 10 ml of a hot solution of 1 ~ NaOH. (A small amount of Fe-must be present.) Centrifuge off hydroxides of Ni, Co, Fe, Ti, SC,&nd Ca. Wash the precipitate with 4 ml of hot 1 ~ NaOH,. Add washto supernate.

- Scavenge by adding one drop of Fe- carrier (10w (10 mg/ml)to the hot solution.g/ml) and 500 A Ti Centrifuge

and wash the precipitate with 4 ml of hot 1 ~ NaOH.Step 8. EOil down to 6 ml. Make slightly acid with acetic

acid and add 5 ml of 10~ Pb(Ac)2. Centrifuge off Pb(V03)2, andwash with slightly(containing Zn+).

acidic, dilute Pb(Ac)2. Add wash to s,upernate

65


72/82

PROCEDURE 9 (Continued)m ~ke 2 y with HN03, precipitate Pb as the sulfide by

adding H2S. Centrifuge and wash the precipitate with 2 N HN03.Add wash to supernate. Boil to remove H2S.

Step 10. Neutralize with NaOH, make slightly acid with HACand reprecipitate vanadium as lead vanadate. Weigh.Remarks:Reference: ScottB Standard Methods

PROCEDURE

of Chemical Analysis, p. 10%.

10Source: Haymond, Msxwell, Garrison and Hamilton (UCRL-473)

Target material: Titanium Time for Separation: 4-5 hrs.(ea. lgm) Equipment required: StandardType of bombardment: 60 D2 Yield: 80-95$Degree of purification: At leastfactor of 103.

Advantages: Carrier free. Suitable for use in biological systems

ProcedureStep 1. Mssolve the Ti powder target material In a minimum

volume of 36 ~ H2S04 and evaporate to dryness.SE?u Add 5.0 gm of Na2C03 and 0.1 gm NaN03 and fuse the

mixture at 500C for 30 minutes.Step 3. Extract the carrier free vanadium (presumably as

vanadate) from theinsoluble titanium oxide by repeated washingswith cold water.

To remove any Ca or Sc activities which may have extractedwith the V:

Step 4. Acidify the solution with HC1, add 10 mg of Ca andSc, and ppt from 1 ~Na2S03.

66


73/82

PROCEDURE 10 (Continued)Step 5. Neutralize the solution containing V with 12 N HC1

and evapot?ateto dryness.Step 6. Separate the V activity from most of the NaCl by

extraction with approximately 5 ml of 12 N HC1.m Evaporate the HC1 solution to dryness and dilute

w~th water to give an isotonic galine solution of V which can beused In biological studies.

Remarks:The target consisted of C.P. metal powder supported on a

copper target plate 0.25 mil Tafor 24 hours after bombardment.

foil. The target was cooled

PROCEDURE 11

Source: R. I. Walter (J. ~org.Nucl. Chem., ~, 63 (1993)

Target material: Titanium Time for Separation: -2-3 h37s.Type of bombardment: Deuteron Equipment required: Standard,Yield: -130$V4849 plus ion-exchange columnand apparatus In FLg. I.Eegree of purification: EkcellentAdvantage: 48,49Carrier-free V

ProcedureEksQ Titanium foil target placed folded into V-shape to fit

Into furnace (see Figure 13). Sweep system with helium. Heat to 400C.Step 2. Cool trap I with Ice, trap II with dry ice. Pass through

chlorine gas until target completely converted to TiC140 Cool furnace.Step 3. Warm trap II to room temperature. Sweep system with

helium.

67


74/82

PROCEDURE 11 (Continued)

Figure 13.

T

ApparatuB for the preparation and distillationOf TiC14, and for the separation of dissolved vanadium from thediatlllate. Helium OP hydrogen gas Is admitted through the stop-cock, bubbler B, and drying tower D. Vycor furnace tube F isconnected through a gmded seal S to the Pyrex trap system.Traps T-I and T-II are made from 6 mm right-angle vacuum stop-cocks. The U-tube Is filled with glass wool, and connected toa drying tube. All horizontal connections beyond S shouldslope downward to facilitate dminage of TIC14. Copper @ddle Pis mounted a6 shown an a 24/40 joint which can replace the stop-cock plug ofeither trap, and simultaneously seals the Inlet tolt.

Step 4. Close inlet to trap I. Distill TIC14 into trap II.Step 5. Prepare copper paddle (P) by heating to dllllredness,

Immersing in methanol and drying. Insert into trap II in place ofstopcock.

Step 6. Reflux TIC14 for -.J30 minutes. Cool; rinse paddlein CC14. Immerse In 1 M HC1.

60


75/82

PROCEDURE 11 (Continued)Step 7. Saturate 1 M HC1 solution with H2S, filter, wash and

evaporate filtrate just to dryness.Step 8. Dissolve dry residue in 0.1 M oxalic acid. Saturate

with S02 gas.Step 9. Charge solution to 1 x 15 cm .ion-exchange column with

Dowex-1. Follow with second column of Dowex-1 0.5 x 5 cm. Elutewith 0.1 M oxalic acid. Deetroy oxalic acid in product solutionith 202-

Note: Moisture should be excluded from the system as far as poBsible,since VC14 is decomposed by water.

69


76/82

REFERENCES1.

2.3.4,

5.6.7.

8.

9.10.11.12.

13.

14.15.

16.

Stromlnger, D., Hollander J. M., Seaborg, G. T., Rev. Mod.Phys., 30, Pt. II, 585-901 (1958).Martin, W. M., Rreckon, S. W., Can. J. Phys., 3&, 643-57 (1952).Frledlander, G., Miller, J. M. Wolfgang, R., Hudis, J., Eaker,E .J Phys. Rev., 94, 727-8 (195~).

U. S. Atomic Energy,commission, ReportU~&~~;9~: ~&b~~a~~:1954).Friend, J. N., A Textbook of Inorganic Chemistry, Vol. VI,Pt. III, Charles Griffin and Co., Ltd., London, 1929, p. 9-116.Campagne, Bn., Compt. Rend., 137, 570 (1903).The bivalent compound Is oxidized quite easily under ordinaryconditions. According to A. S. Russel [J. Chem. Sot., 129,497 (1926)], It Is quite stable in cool 10 ~H2S04. Lundell, G. E. F., Knowles, H. B., [J. Amer. Chem. Sot., @1%6 (1921)] showed that the reduction gives rise to PolY-thionlc compounds.McCay, L. W., Anderson, W. T., Jr.,2372 (1911); & 1018 (1922).Cain, J. R., Hostetter, J. C., Ind.

J. Amer. Chem.

Eng. Chem., ~,

Sot., 4J

250 (1912).Kelley, G. L., Wiley, J. A., Ind. Eng. Chem., ~, 632 (1919).Chariot, G., E!ezler,D., Quantitative Inorganic Analysis,Methuen and Co., Ltd., London, 1957.Cain, J. R., Hostetter, J. C., J. Amer. Chem. Sot., @ 2552(1921).Cain, J. R., Tucker, F. H., Ind. Eng. Chem., ~, 647 (1913).Noyes, A. A., Eray, W. C., A System for the QualitativeAnalysis for the Rare Elements, The MacMillan Co., New York,1948, p. 338.Burrlel-Martf, F., Fern~ndez-Caldas, E., Ramfrez-Mufioz,J.,Anales real sec. espaii.f$s. y qu~m., B 48, 59 (1952); 4&,37 (1950).

70


77/82

17.

18.

19.

20.

21.

22.

23.24.25.26.27.28.29.30.31.32.

33.34.35.36.37.38.39.40,41.

42.

Frank, A. J., Chemistry of Vanadium, Topical Report ACCO-49,November, 1952, , ,Duval, C., Inorganic Thermogravlmetrlc Analysis, Elsevierpublishing Co., Amsterdam, 1953, PP. 170-177.Hodgman, C. D., (Ed.), Handbook of Chemistry and Physics,Chemical Rubber publishing Co., Cleveland, Ohio.~llebrand, W. F., J. Amer. Chem. Sot., ~, 454 (1898); U. S.Geol. Survey Euil. ~, +85.Hillebrand, W. F., Lundell, G. E. F., Bright, H. A., Hoffman,J. I., Applled Inor anic Analysis, John Wiley and Sons, Inc.,New York, 1955, pp. ~52-63.Lange, N. A., (::;~;s;y, Ohioandbook of Chemistry, Handbook Pub-llshers, ~c., .Rosenheim, A., Z. anorg. Chem., ~, 368 (1893).Souchay, P., Eull. SOC. chlm., l&, 122 (1949).Felgl, F., Anal. Chim. Acts, ~, 397 (1948).Koppel, J., Goldman, R., Z. anorg. Chem., ~, 281 (1903).Idngane, J. J., Meltes, L., J..,Amer.Chem. Sot., 69, 1882 (1947).Furman, S., Garner, C. S., J. Amer. Chem. SoC., ~, 4528 (1951).Koppel, J., Behrendt, E., Z. anal. Chem.,~, 154 (1903).Rlvenq, F., Bull. SOC. chlm., 971 (1947).LMcret, L. P., Ann. Chim. (12) ~, 705 (1951).Sidgwick, N. V., The Chemical Elements and Their Compounds,Vol. I, Oxford University Press, Oxford, 1950, PP. 818-832.Iocke, Edwards, Amer. Chem. J., 20, 594 (1898). Ba.udlsch,O., Chem. Zeltung, ~, 1298 (1909); ~y 913 (1911)./Rodeja, V. G., Anales BOC. espafi.f~s. qulm., 12, 305 (1914).Turner, W, A., Amer. J. Scl., & 339 (1916). :Raeder, M. G., Aakre, T., @l. Norske Vldenskab. Selakab.,Forh., 15, 75 (1942).Strock, L. W., Drexler, S., J. Opt. SoC. Amer., 31, 167 (1941).Hahn, F., Z. angew. Chem., ~, 1198 (1926).Berg, R., J. prakt. Chem., (2) 115, 178 (1927) . /Gallego, M., Males soc. esPax. fls. qu~m., ~,3;t&L):.,Komarovskll, A. S., Poluektov, N. S., Z. anal. them., z, 23(1934).

mt-


78/82

43.44.45.46.

47.

48.49.50.51.52.

53.54.

Goto, H., J. Chern.Sot. Japan, 56, 314 (1935).Tzlnberg, S. L., Zavodakaya Lab., No. 1, 18 (1933).Goto, H., J. Chem. Sot. Japan, 54, 725 (1933).Goto, H., Science Repts., Tohoku Imp. Univ. First Ser., ~,391 (1937); C.A. ~, 2863 (1938).Goto, H., Science Repts., Tohoku Jmp. Univ. First Ser., 2&,418 (1938); C.A. ~, 7368 (1938).Fleck, H. R., Ward, A. M., Analyst, ~, 388 (1933).Gutzelt, G., Monnier, Helv. Chim. Acts, 16 239 (1933).~Gutzeit, G., Monnier, ibid., I&, 233 (1933).Fresenius, W., Z. anal. Chem., 9&, 433(1934).Poluektov N. S., Narazenko V. A., J. Appl. Chem, (U.S.S.R.),~, 2105 11938); C.A., ~, i467 (1938).Shemyakin, F. M., Belokon, A. N., Compt. rend., Acad. Sci.(U.S.S.R.), ~, 277 (1938); C.A., ~, 4467 (1938).Terrisse and Lm&ol, in Beard, M., Ann. Chem. anal., I&,41 (1905).

55. Eellucci, I., Chlucini, A,, Gazz. Chim. ital., 49 (II), 187(1919); C.A., ~, 908 (1920). 56. Tanll, K. Hosimlya H., Ikeda T., J. Chem. Sot. Japan, 61,269 (1940); C.A., 34, 4687 (1940). 57. Jean, M., Emil. SOC. chim.,,~, 201 (1943); C.A., 38, 6230(1944).

~: Flagg, J. F., Furman, N. H. J. Ind. ~g. Chem., Anal. Ed.,~, 529 (1940); ~, 663 (19~0).59. Jones, M., J. Amer. Chem. Sot., ~, 5995 (1954).60. Shome, S. C., Analyst, 75, 27 (1950).61. Ryan, D. E., Lutwlck, G. D., Can. J. Chem., ~, 9 (1953).62, Shome, S. C., Anal. Chem., 23, 1186 (1951).63. Soganl, N. C., Fhattacharya, S. C., Anal. Chem., ~, 81 (1956).;&3, 1616 (1956).64. ., Gut, R., Anderegg, G., Helvi Chem. Acts,85;e??;;tJ.G

Schwarzenbach, G., Sandera, J., Helv. Chlm. Acts, ~, 108965. (1953).66. Ahrland, S., Acts Chem. Stand., 7_,485 (1953).67. Hall, D., J. Amer. Chem. Sot., & 1462 (1922).

72


79/82

68.

69.

70.

71.

72.

73.74.75.76.

77.

78.

79.80.81.82.

83.

84.85.86.

87.88.

89.

90.

Erode,H., Z. anal. Chem., 142, 414 (1954); 143, 182 (1954);144, 90, (1955); 144, 165 ~55).Fukal, R., In U. S. Atomic Energy Commission, Rept. AECU-3887(Nov., 1958).Shepherd, E., Melnke, W.W., U. S. Atomic Energy Commission,Rept. AECU-3879 (1958).

Forney, G., Swift, E., J.g;:ig%j.Bock, R., Herrmann, M., Z. anorg. und288 (1956).

Amer. Chem. SOC., 58,allgem. Chemie, 2&,

Bock, R., Kusche, H., ~ck, E., Z. anal. Chem., 138, 167 (1953).Beck, R., Z. anal. Chem., 133, 110 (1951).Lemmerman, R. D., Irvine, J. W., U. S. Atomic ~ergy Commission,Rept. NP-1777 (July, 1950), PP. 54 ff.Furman, N. H., et al., U. S. Atomic Energy Commission, Rept.AECD-2938.

U. S. Atomic Energy Conunlaslon,Rept. MCW-5?Yz?: c -., et al., U. S. Atomic Energy Commission, Rept.~I~2L7R{l:50 ).

Haisten F. D., in U. S. Atomic ~ergy Commission, Rept.TID-10146, pp. 28 ff.U. S. Atomic Energy Commission, Rept. HW-23160.U.,S. Atomic Energy Commission, Repts. ORNL-1260 and 1338.Blake, C. A., Brown, K. B,, Coleman, C. F., U, S. AtomicEnergy Comnisslon, Rept. ORNL-1964.Morrison, G. H., Fre16er, H., Solvent -traction in AnalyticalChemistry, John Wiley and Sons, Inc., New York, 1957.Keggin, J. F., Proc. Roy. Sot. (London), ~, 75 (1934).Scroggie, A. G., J. Amer. Chem. Sot., 51, 1057 (1929).Maksimova, N. V., Kozlovskii, M. T., Zhur. Anal. Khim. (U.S.S.R.),g, 353 (1947).Kinnunen, J., Wennerstrand, B., Chemist-Analyst, .@, 35 (1951).Smith, E. L., Page, E. J., J. Sot. Chem.48 (1948). Ind. (London), 67,Leddicotte, G. W., Moore, F. L., J. Amer. Chern.Sot., 74, 1618(1952). ,Ellenberg J. Y., Leddlcotte, G. W., Moore, F. L., Anal. Chem.,2&, 1045 (1954).

73


80/82


81/82


82/82

137. Coryell, C. D., Sugarrnan,N. (Ed6.), Radlochemical Studies:The Fission Products, Book I, McGraw-~ill Book co., Inc.J~ 1, pp. -135.138. Bell, P.R., in Slegbahn, K. (Ed.), Beta- and Gamma-RaySpectroscopy, Intersclence Publishers, ~c., New York, 1955,

PP. 133-lb4.U. S. Atomic Energy Comnisslon, Rept. ID3-1640839. ~~:j.R. L.,

140. Bcrkowskl, C. J., U. S. Atomic Energy Commission, Rept.OWL-1160 (1951).

The Radio Chemistry of Vanadium.us AEC

Documents

Transcript of The Radio Chemistry of Vanadium.us AEC