Kanth, K. M.

Nigam, H. L.

Pandeya, K. B.

English

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INDIAN J. CHEM., VOL. 15A, JANUARY 1977ReferencesD.po(kcal/mole)-12,10-12-49-7,128,859·108·15logK.2·252·852·20logKl6,606·255,95ZrHTh4+UO~+Metal ion1. NIGAM, H. L. & PANDEYA, K. B., Indian J. Chem.,8(1970),454.2. NIGAM,H. L., MATHUR,V. K. & PANDEYA,K. B., IndianJ. Chem.,9 (1971),1292.3. NIGAM,H. L. & PANDEYA, K. B., CurroSci., 41 (1972),449.4. NIGAM,H. L. & PANDEYA,K. B., Proceedings,chemistrysymposium.Chandigarh,Part 2, 1961,147.5. KANTH, K. M., PANDEYA,K. B. & NIGAM,H. L., IndianJ. Chem.,11 (1973),103.6. KANTH, K. M., PANDEYA,K. B. & NIGAM,H. L., IndianJ. Chem., 11 (1973),1034.7. VOGEL,A. 1.,Quantitativeinorganicanalysis (Longmans,Green, London), 1968,539.8. BJERRUM, J .. Metal-ammineformation in aqueoussolu-tions (Haase, Copenhagen),1941,152.9. IRVING, H. M. & ROSSOTTI,H. S., ]. chem.Soc., (1954),2904.10. RossaTTI, H. S. & RaSSOTTI,F. J. C., Determinationofstabilityconstants(McGraw-Hill, New York), 1961,107.11. MELLOR, J. W. & MALEY, G. F., Nature, Lona., 159(1947),370; 161 (1948),43(j.TABLE 1- METAL-LIGANDSTABILITY CONSTANTSOF THE COMPLEXESReferencesThiovanol (Evans Chemetics, New York) wasused as such. Its fresh solutions were preparedin doubly distilled water and estimatt:diodorretri-cally. Stock solutions of metal ions were prfpaffdfrom analytical grade reagentsand standardized byusual methods (Th was precipitated as [Th(C204)2Jand weighed as Th02; Zr, as [ZrH2(P04)2] andweighed as ZrP20 and U02 as (U02(CgR60N)a-CgR70N] and weighedas UaOs)7. A LeedsNorthruppH-meter fitted wiih a general purpose glass elec-trode was used for pH-measurements. All measure-ments were carried out at 25° in a nitrogenatmosphere. The following solutions were titratedagainst 0·1211NaOH solution: (i) 5 ml of 0'01211HCI04+Z'5 ml of 0'04M NaCl04+42'5 ml water,(ii) 5 ml of 0·01211HCl04+2'5 ml of 0·04211NaC104+2'5 ml of 0'009211 thiovanol+17'5 ml water,(iii) 5 ml of 0·01211HCI04+2'5 ml of 0·04211NaCI04+ 25 ml of 0·009211'thiovanol+Z'5 ml of 0·01211metal ion (UOi", Th4+ or Zr4+)+15ml water.The plots of pH versus the volume of alkaliadded gave S-shaped curves. Values of noM> nandpL at different pH values were calculated vsingstandard rclatio!lships8-10.All calculations weremade below pH 5,0. Absence of bydrolytic sidereactiors was also confirmed. A fiB versus pHcurve was obtaimd, wbich yielded the PKlH valuefor thiovanol as 8,75. The values of log Kl weredirectly read from the n-pL formation curVESandthos~of log K2 werecalculatedusing the method ofBjerrumll as modified by Irving and Rossotti12andRossotti and Rossotti10. The results are presentedin Table 1. The stabilities of thorium(IV) andzirconium(IV) complexesobeythe Mellor and Maleyorderll (Th4+>Zr4+).Thanks are due to Messrs Evans ChemeticsInc.,New York, for supplying thiovanol as a gift sample.Error(%)-0·0720·0000,000-0,1830·000Found(mg)2·7514·4065,5085,4988·262Taken(mg)2·7544·4065·5085-5088·2623- DETERMINATIONOF Cd(lI) IN THE PRESENCEOF Hg(lI)Cd (II)sent address: Department of Chemistry, R.D. &allege,Monghyr, Bhagalpur University, Bihar.sent address: Department of Chemistry, Universityhi, Delhi 110007.1. B TLSTEIN,F. & JAWEIN, L., Berichteder Busengesells-haftfur Kalische Chemie,12 (1879),759.2. D VAL, C., Inorganic thermogravimetricanalysis (Else-ier, Amsterdam),1953.3. T NANAEV,1. V. & KOZLOV,A. S., Zhur. anal. Khim.,(1951),149.4. D SHMUKH,G. S. & VENUGOPALAN,M., J. Indian chem.oc.,33 (1956),222.5. B LCHER,R. A., NUTTEN,J. & STEPHEN,W. 1.,J. chem.oc., (1951),3444.6. TOMSON, T. L., Ind. engngChem.analyt.edn,13 (1941),64.7. B LLOMO,A., DEMARCO,D. & CASTLE,A., Talanta, 191972),1236.8. S UDBERG,B., SvenskChem.Tidskr., 58 (1946),197.9. F ULK, C. W. & BOWDEN,A. T., J. Am. chem.Soc.,481926),2045.10. R ILLEY, C. N., SCHMID,R. W. & SADEK, FAWZYS,J.hem.Educ., 36 (1959),555.11. K LTHOFF, 1. M., SANDELL,E. B., MEEHAN, E. J. &RUCKENSTEIN,S., Quantitativechemicalanalysis (The; acmillan Co., London), IV edn, 1969,800, 824.I PotentiometricStudyofCo~plexF rmationbetweenThiovanol&I Th(IV). Zr(IV) & U02(VI)I~. M. KANTH"',K. B. PANDEYAt & H. L. NIGAMDfPartment of Chemistry,University of AllahabadAllahabadII Received13 May 1975;revised5 March 1976;! accepted22 May 1976iCOtPlexformationbetweenthiovanol(1-thioglyce-rol) d Zr(IV).Th(IV) andUO.(VI)hasbeenstudiedpote ometrically.Formatio of 1:2 (me al-li and)com;exhasbeenobservedin eachcase. ThelogKrfort ovanolcomesouttobe8·75.Stabilityconstantsofth metalcomplexesfollowtheorderTh'+>Zr'+>UO:+have recently reported1-epreparation andcharacterization of some transition metalcom~exes of thiovanol. The present note des-cribe the results of pH-metric studies on complexform tion of U02(VI), Zr(IV) and Th(IV) withthio anol in solution.i10.h30·030'f8850, 485 , 4liTh~ authors are grateful to Prof. W. Rahman forfacili ies, and to the CSIR, New Delhi, for financialassis anceto one of them (D.K.S.).

Potentiometric study of Complex Formation between Thiovanol & Th(IV), Zr(IV) & UO2(VI)

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Potentiometric study of Complex Formation between Thiovanol & Th(IV), Zr(IV) & UO2(VI)

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