Optical Absorption, Kinetics and Thermodynamic Studies of Pr(III) and Nd(III) Ions with N-Acetyl L-Cysteine in Presence of Ca(II) ions

Abstract

Interaction of N-acetyl-L-cysteine (NAC) with Pr3+ (Pr(NO3)3·6H2O) and Nd3+ (Nd(NO3)3·6H2O) ions are studied in presence of Ca2+ (Ca(NO3)3·4H2O) ion in an aqueous and organic solvent by applying the spectroscopic technique for quantitative probe of 4f-4f transition. The complexation was determined by the variation in the intensities of 4f-4f absorption spectral bands and by applying the change of symmetric properties of electronic-dipole known as Judd-Ofelt parameters Tλ (λ = 2,4,6). On the addition of Ca2+ ion in the binary complexation of praseodymium and neodymium with N-acetyl-L-cysteine (NAC) there is an intensification of bands which shows the effect of Ca2+ toward the heterobimetallic complex formation. Other parameters like Slater-Condon (Fk), bonding (b1/2), the Nephelauxetic ratio (β), percentage covalency (δ) are also used to correlate the complexation of metals with N-acetyl-L-cysteine (NAC). With the minor change in coordination around Pr3+ and Nd3+ ions, the sensitivity of 4f-4f bands is detected and further used to explain the coordination of N-acetyl-L-cysteine (NAC) with Pr3+ and Nd3+ in presence of Ca2+. The variation in oscillator strength (Pobs), energy (Eobs) and dipole intensity parameter help in supporting the heterobimetallic complexation of N-acetyl-L-cysteine. In kinetics investigation, the rate of the complexation of both hypersensitive and pseudo-hypersensitive transition is evaluated at various temperature in DMF solvent. The value of the thermodynamic parameters such as ΔHo, ΔSo and ΔGo and activation energy (Ea) also evaluated.