Chemical Sciences, Vol -97
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Chemical Sciences, Vol -97


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of the Indian of Sciencesproceedings Academy<;> (Chemical Sciences)Volume 198697,CONTENTSandriorganic Analyticalof nickel and cobalt in naturallorganic complexation watersAnil Kumar 1-7L of borateruthenium(II) complex ^w(l-pyrazolyl)M M K Veera R C and H CTaqui Khan, Reddy, 9-11Bhardwaj Bajajome lanthanide metal ofcomplexes /z-isonicotinamidosalicylamidineT R I A Khan and R CRao, 13-18Aggarwal4ixed of andligand complexes 6w(acetylacetanato) nickel(II) cobalt(II)nth N and N,N'-substituted thioureasG L S B Kokatnur and A S R 19-24Tembe, Murtytructural studies of amino acid I EXAFS ofcomplexes study glutamiccid of CKBhaskareandSYKulkarni 25-32complex coppercharacterization and thermal of rare earth and'reparation, analysisderivatives.ranyl hydrazinecarboxylateG V P Ravindranathan and K C Patil 117-123Mahesh,oxidation of alcohols with3)3 catalysed secondary N-methyl-N-oxide K J andJC Kuriacose 125-132norpholine Vijayasri, Rajaramiffect of dielectric constant of various mixed solvent on theaqueousand formation constants ofiroton-ligand metal-ligand N-methyl-satin K SarkarandB S 133-139/3-amidinohydrazone Gargand studies of with Schiff baseslynthesis spectral tin(IV) complexeslerived from Anil andJP Tandon 141-146sulpha drugs VarshneyVater insoluble XII: based onPolychelates poly (N-polyacrylarnidebenzoic acid)tiethacryloyl-m-aminoKishore Trishar Desai and Bhikhu Suthar 147-152Patel,'-T-TvrlrnYv-1-nanhthaldehvde euanvlhvdrazone as analytical ...


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of the Indian of Sciencesproceedings Academy <;> (Chemical Sciences) Volume 198697, CONTENTS andriorganic Analytical of nickel and cobalt in naturallorganic complexation waters Anil Kumar 1-7 L of borateruthenium(II) complex ^w(l-pyrazolyl) M M K Veera R C and H CTaqui Khan, Reddy, 9-11Bhardwaj Bajaj ome lanthanide metal ofcomplexes /z-isonicotinamidosalicylamidine T R I A Khan and R CRao, 13-18Aggarwal 4ixed of andligand complexes 6w(acetylacetanato) nickel(II) cobalt(II) nth N and N,N'-substituted thioureas G L S B Kokatnur and A S R 19-24Tembe, Murty tructural studies of amino acid I EXAFS ofcomplexes study glutamic cid of CKBhaskareandSYKulkarni 25-32complex copper characterization and thermal of rare earth and'reparation, analysis derivatives.ranyl hydrazinecarboxylate G V P Ravindranathan and K C Patil 117-123Mahesh, oxidation of alcohols with3)3 catalysed secondary N-methyl- N-oxide K J andJC Kuriacose 125-132norpholine Vijayasri, Rajaram iffect of dielectric constant of various mixed solvent on theaqueous and formation constants ofiroton-ligand metal-ligand N-methyl- satin K SarkarandB S 133-139/3-amidinohydrazone Garg and studies of with Schiff baseslynthesis spectral tin(IV) complexes lerived from Anil andJP Tandon 141-146sulpha drugs Varshney Vater insoluble XII: based onPolychelates poly (N-polyacrylarnide benzoic acid)tiethacryloyl-m-amino Kishore Trishar Desai and Bhikhu Suthar 147-152Patel, '-T-TvrlrnYv-1-nanhthaldehvde euanvlhvdrazone as analytical reaeent for identification and of theSynthesis, analytical properties 2-pyrilidenimino acidbenzohydroxamic F M Jimenez-Arrabal and I Durdn Merds 159-Salinas, of of substituted catechols and catecholaminesStudy ternary complexes P K N A Emanuel and N D Kulkarni 529Bhattacharya, reactions of with aminesExchange copper complexes K B Patel 535M N Patel and com-Influence of electrostatic effect on the ofstability mixed-ligand acidplexes: Uranyl-complexone-phenol/phenolic ternary systems S N and M C Saxena 543Anushree Samanta, Limaye Instrumentation forand fabrication of an ultravioletDesign photoelectron spectrometer andM S 617the of free moleculesstudy VJayaram Hegde Organic 13 CNMR substituent induced chemical shifts in the side-chain carbons of a,/3-unsaturated sulphones C P K A and N 3Sreenivasan, Ganesan, Shanmugasundaram Arumugam Photo-Fries reaction of cinnamate 1-naphthyl T T Manitnaran and V T Ramakrishnan 4Jayachandran, Reaction of bromoacetate with substituted ionsnaphthoateethyl K and C Gnanasekaran 4Rajasekaran Kinetics of the reaction of bromides withalkyl nucleophiles containing atoms TJanardhan Rao,G Punnaiah andEVSundaram f nitrogen a new biflavanone from anacardiumSemecarpusSemecarpuflavanone Linn. S SN fMurthy Solid of the of E. coli alkalinesynthesis signal sequence phosphatasephase ' G Laxma and RReddy Nagaraj Abietane and a new from Salviaditerpene quinones diterpene epoxide Beena NB MulchandaniandJShankar 16'Bakshi,moorcraftiana in Molecular ofand structurecrystal l-hydroxy-2-methyl-ll-methylene-tri- 2i7 C O-undecan-5-one, 13 2Hi8cyclo ( S and Vasantha Pattabhi 547-553Krishnaswamy Mechanism of the oxidation of andalkyl aryl diphenyl bysulphoxides R PSubramanian andC Srinivasan 555-563Suthakaran,peroxomonosulphate and TheoreticalPhysical of formation of and amines with iso-Enthalpies complex dibutyl tributyl meric butanols ShirishD Pradhan and Pathak 77-81Copal Electronic and vibrational of andspectra 2,4,6-trichloro- 6-chloro-2,4- MSL Prasadand 83-90dimethoxypyrimidine Srivastava, RanjeetSingh QSAR studies on ofestrogen receptor binding affinity 2-phenylindoles Pfirst-order valence molecular 91-95using connectivity Singh ofInfrared and Raman spectra 2,4-dimethylaniline NG BPAsthana andJacob ShamirA R CM 97-115Shukla, Pathak, Dongre, of and mixed ofESR studiesBonding parameter single ligand complexes copper(II) Y NVS R Prabhakara Rao and VGKM 177-184Rao,Anjaneyulu, Pisipati Reaction of with 2-hydrazino-4-methyl-6-substituted quinones ethylaceto- acetate :A structural RadheK Vaidand ShivP 185-189 .reinvestigation Singh + Vibrational-rotational levels of HD evaluated in the adiabatic (v-j) for the electronic stateapproximation ground (lscrg) R S R P P K Srivastava and K V Sane 191-207Saxena,Bhattacharjee, Electron ionization of amines crossed electron-molecularimpact using beams SVKrishnaKumarandD Mathur 565-572 Reaction of the radical with amines A flashphosphate photolysis study P V J and J C Kuriacose 573-580Subramanian, Ramakrishnan, Rajaram studies of on carbondepositionUnderpotential copper glassy S T Prasada Rao and G Prabhakara Rao 581-586Jaya, and structural transition of con-Stereochemistry phase Cu(II) complexes ions andtaining orthophosphate pyridine/picoline M S and M D 587-592Sastry Sastry onSCF Perturbation calculations metalloporphyrins and J H 601-606D P FuhrhopK K J Subramanian, SantryBhattacharjee, IRA 401 Cl anionacid in amberlitestudies ofExchange sulphosalicylic G S 607-615NoomanA Natarajanresin Khalafandexchange on hisdedicated to ProfessorK S G Doss birthdayissue eightiethSpecial in themodel for nuclear photo-Solvation inner-sphere reorganization ionization of univalent anions in solution and Andrew Dziedzic 221-231Paul Delahay in solution PPSchmidt 233-265Proton and transfer reactionshydrogen double at a solutionNew theories for the electric metal/electrolytelayer Levia and Schmickler 267-296interface WolfgangEzequiel hardof the of a of hard near aCalculation system spheresdensity profile wall the Henderson-Plischke and related approximationsusing Michael Plischke 297-305Henderson andDouglas Afunctions and Green's functions: critiqueSpectral A K Mishra and S K 307-331Rangarajan at the interfaceThe ofadsorption D-(+)-xylose mercury-water Parsons and Robert Peat 333-347Roger films on electrodes. 21. Electrochemical behaviour of tetramethyl-Polymer tetraselenafulvalene into a Nafion-coated electrode incorporated D Allen J Bard and Jack M Williams 349-357Moulton,Roger electrode materials for the evolution reactionperformance hydrogenHigh from alkaline media BV A C andBE 359-393Tilak, Ramamurthy Conway of 2-nitrobenzidineElectrochemical reduction in methanol-water mixtures M SS Aravamuthan, Sashidar, C Kalidas and C S Venkatachalam 395-401 Electrochemical reduction of some in molten acetamidebenzophenones at85C R SaraswathiandR 403-416Narayan voltametric studies of dinuclearCyclic dioxygen-bridged cobalt(II) S andPcomplexes 417-430Ilangovan Natarajan The translocation of cobalt dicarbamide anions across a lipid bilayer membrane: the effect of solution resistance in anodic volt-Jse of inputsprogrammed time-potential stripping with in situ sodiummmetry amalgamation G Prabhakara Rao and A 449-455Varadharaj n situ resistance measurement of a electrodeconducting polymer M Gholamian, T N Suresh Kumar and A Contractor 457-464Q of relaxation methods for corrosion studies and Applications exponential orrosion rate measurement V and S R 465-477Lakshminarayanan Rajagopalan ilectrobioluminescence a novel method for biolumines-understanding ent mechanisms KS VSanthanam 479-494 Corrosion of austenite stainless steel in environmentsaqueous J B 495-511Gnanamoorthy r uel cells: andproblems prospects A K Shukla, K V Ramesh and A M Kannan 513-528 Communicationstapid lolution of difficult structures: New, economic and timecrystal simple, SS Tavale and TN GuruRow 209-21 1aving approaches Reactions of withhalogens 2,2'-azinobis-(3-ethylbenzothiazole-6-sul- kinetics of formation of radical cations and>honate) stopped-flow lications P L Venkatasubramanian and P 213-218Maruthamuthu, Dharmalingam of Ca FeMagnetic properties 2 2^Mnj:O5" A K and J 627-630Ganguli Gopalakrishnan in oxides derived from CuOTV La|.sSro.2 4iigh superconductivity P and CNR RaoGanguly 631-633 Index 635-643Jubject Vuthor Index 643-647 of nickel and cobalt in natural watersInorganic compiexation ANILKUMAR Chemical Division, National Chemical Pune 411 IndiaEngineering Laboratory, 008, ofPresent address: Professor Franck, Institute ofLaboratory Physical Chemistrj ofElectrochemistry, University Karlsruhe, D 7500 Karlsruhe, West Germany MS received 25 revised 2 1985February 1985; September Abstract. The distribution of nickel and cobalt has been based ospecies computed, model ofZirinoand Yamamoto.The media used in the of7 topH-dependent pH range natural waters like fresh sea water and a mixture ofthem at differentwater, compositio 25C and 1 atm In fresh both nickel and cobalt dominate atemperature pressure. water, cations at lower and ascarbonate at In sea chloropH, complexes higherpH. water, comj are In mixtures of the two kinds of as be found in a rsignificant. water, might totally chloro are with Seawater anestuary, complexes important,varyingslowly pH. plays impc role in The results are in excellent withcompiexation. present agreement experimental obtained the resin exchange naturalKeywords. Nickel; cobalt; pattern; waters.species pH; compiexation; 1. Introduction calculations are of in the fate oftracemetaSpeciation great significance evaluating ' In recent theoreticaland studiesbiogeochemical cycles. years,many experimental on the of and active rnetaappeared equilibrium speciation major electrochemically natural waters. a few studies et al Turner et al 1981However, (Mantoura 1978; on the behaviour of trace metals in fresh and sea water media.reported In this ofwe the results of cent ofnickelpaper, report computations per species cobalt in natural waters like fresh water sea at 25 1and water C andtemperature amodified modelofZirino andYamamoto n pressure, using pH dependent (1972) of 7 to 9. This us in the nature of the varrange maypH help understanding and their behaviour in natural waters.The calculations are further exteicomplexes to mixtures ofdifferent offreshand sea water for the chacompositions observing in the distribution of in a mixedspecies completely estuary. 2. Calculations model and massThe balance used in thework are summaiappropriate equations and Yamamotoelsewhere 1972; and(Zirino Long Angino 1977). Thermodyns isassumed to existand the is 7 to an increment of0-2. S9 withequilibrium pH range concentrations of nickel and cobalt are andthe low,very polynuclear org are avoided and Hicompletely 1969;complexes (Helgeson Long Angino 1977). acid are also avoided as their constants are unavailabcomplexes stability presently a function of The of elements was calculated the mod'pH. speciation major by lable i. Una numbers on moiai scale used as input. 6 Fresh water" Sea waterComponent fc Berner 1971."Livingstone 1963; Table 2. constants of various of nickel and cobalt at 25C.Stability (log/?) species log ]5Species Cobalt cr 0-57 - 2-36"SO+ - d HC0 2-43 fCO 4-9 l 3 OH" 4-15" "Sillen and Martell "Sillen and Martell1964; * 'Turner et al Mantoura etd 1978.1971; 1981; offresh water and seawater used areGarrelsand TheThompson (1962). compositions 1. for the are SO~listed in table The used OH", , Cl~, ,ligands complexation HCO^ et al Turner et al Sillen andand their constants 1978; 1981;COl" stability (Mantoura are listed in table 2. Tables 1 and 2 are of calculations.Martell 1964, 1971) inputs constants were also examined Turner et alcritically by (1981).Stability The coefficients of metals and their are calculated the Daviescomplexes byactivity as1962)equation (Davies The use of Maclnneswhere z is the on the ion and / is ioniccharge strength. it was not toconvention in was avoided as(Maclnnes 1919) calculating yf applicable of ion andionic than 0-1. coefficients (Reardonstrengths higher Activity pairs areLangmuir 1976) given by =whereB 0-3and 0-5 for 1-2and 2-2 ion and the0-1, 1-1, pairsrespectively yipis activity coefficient of the ion coefficients of ions are frompair. Activity major calculated Robinsonand Stokes themean saltmethod and Schreiber(1959), using (Millero 1982). The model ofBates was also which unrealistic ^hydration (1978) attempted, gave yMg values and hence was dropped. 9-0 3. Results and discussion The results obtained from are as tocomputations plotted percent aqueous species (0-1 100 ona scale Distributionofdifferent of%) log againstpH. species nickeland cobalt in ++ ++ fresh water is shown in 1. Free Ni and Co both100% figure dominate upto ++ ++ that the of free Co is than free Ni aspH 8-2, except magnitude higher pH increases. carbonate dominate in both cases. OtherBeyond pH 8-2, complexes like bicarbonate and remain belowcomplexes sulphate, hydroxy 4% throughout. Table 3 shows a of values of of of nickel and cobaltpercentsummary aqueous species and theoreticalcalculatedvalues et alalongwith existingexperimental (Mantoura 1978; Turner for1981) comparison. In sea both metals are about in the forms of100% water, complexed by 50% carbonate and chloro 2 shows this while table 3 ourspecies. Figure fact, compares values at 8-2ofsea water. Present values at 8-2 for freeNi arecomputed pH pH slightly etotherwise the is Unlike Turner al the bicarbonatehigher, agreement good. (1981), Table 3. Chemical of nickel and cobalt in fresh and sea water.speciation (%) Fresh water ++Co 90-8 28 474 fc (58), (50) cr 29 (30y, (27)* 3-4 0-20 5SO fc (1) (5), (5) 63-7 0-2HCO^ (6)" CO 1-8 69-3 It a (73)" {6) , (10-5)* +OH 0-3 2-3 1-6 (!)"< (1), (1-5)*