NMR STUDY OF LANTHANIDE(III) NITRATE-CMPO EXTRACTION SYSTEM (II)MOLECULAR MOVEMENT OF CMPO AND La(III)(NO3) 3-CMPO COMPLEX AND LIGAND-EXCHANGE REACTION FOR Eu(III)-CMPO AND Gd(III)-CMPO SYSTEMS

ABSTRACT

NMR( Nuclear Magnetic Resonance ) measurements were car ried out to study the molecular movement of CMPO and La(III)(NO₃) _3? CMPO complex and the ligand-exchange reaction for Eu(III) and Gd(III)-CMPO systems. From the ¹³C relaxation time measurement of La(NO₃) ₃ 3CMPO it was found that the T₁ value for the isobutyl CH and CH₂ carbons and the carbonyl carbon became considerably shorter on complexation, indicating that the carbonyl group participates in the bonding between CMPO and La³⁺ ion as well as the phosphoryl group. The numbers of CMPO molecules coordinated to Eu³⁺ and Gd³⁺ ions in CDCl₃ solution were estimated to be 3 and 2, respectively, in the presence of excess CMPO. The activation parameters for the ligand-exchange reaction were evaluated to be ΔH^* = 37.8±1.9kJ/mol],ΔS^* = -59.9±6.5J/molk? K] and ΔH^* = 41.3±1.6kJ/mol], ΔS^* = -44.1±5.3J/mol-K] for Eu(III)-CMPO and Gd(III)-CMPO systems, respectively. The independence of the exchange rate constants on the concentration of CMPO indicates that these ligand-exchange reactions seem to proceed through either a dissociative ( D ) mechanism or an interchange dissociative ( Id ) mechanism characterized by a stability constant of outer-sphere complex( KQ ) ≥ 100.