vector mechanics

Aug 16th, 2016
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CYL 100 General ChemistryInorganic PartByS. NagendranSNdDepartment of ChemistryIIT DelhiLecture-03SpinelsThe site preference in spinels can be accounted through CFTSpinels are crystalline materials of general formula AB2O4SpinelsAGroup IIA metalGt l ((or))Transition metal in +2 oxidation stateBGroup IIIA metal (or)Transition metal in +3 oxidation stateOxide ions form cubic close-packed latticeFor one unit of AB2O4 there are 8 Td and 4 Oh holesA2+ ions occupy 1/8 Td holesB3+ ions occupy 1/2 of the Oh holesNormal SpinelA2+ and one-half of the B3+ ionsoccupy Oh holesThe other one-halfone half of B3+ ions occupyTd holesIInversee e Spinelpi eSpinelsTo find out the structure of spinel (normal or inverse), find out thedifference in CFSE for the particular metal ion in Oh and TdenvironmentsThis difference is called as Octahedral Site Stabilization (or) SplittingEnergy (OSSE)As the o values for several hexa-aqua complexes are known, for thecalculation of OSSE it can be assumed that the strengthg of oxide ionsand aqua ligands are almost similarSpinelsExperimental values forhexa-aqua complexesCalculatedCl l d usingit 4/9 oSpinelsMn3O4 (Mn2+Mn3+2 O4)NiFe2O4 (Ni2+Fe3+2 O4)Mn2 + d5 t2g3eg2 CFSE = 0(Oh and Td)Ni2 + d8 e4t24 (td) CFSE =0.8 t = 0.4 oMn3+ d4 t2g3eg1 CFSE = 0.6oNi2 + d8 t2g6eg2 (Oh) CFSE =1.2 oNormal spinel

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