Abstract
Biologically active thiol, d-penicillamine (d-PA), based on the hard soft acid base (HSAB) principle, binds strongly with Hg(II) ions leading to the inhibition of the rate of Hg(II) catalyzed substitution of cyanide in hexacyanoruthenate(II) i.e. [Ru(CN)6]4− by nitroso-R-salt (NRS). This formed the basis for the development of a novel kinetic spectrophotometric method for the quantitative determination of d-PA at micro levels. The reaction was followed spectrophotometrically at 525nm (λmax of [Ru(CN)5NRS]3− complex) under optimized reaction conditions at 8.75×10−5M [Ru(CN)64−], 3.50×10−4M [NRS], pH7.00±0.02, ionic strength (μ) 0.1M (KCl) and temperature 45.0±0.1°C. The modified mechanistic scheme is proposed to understand the inhibition caused by d-PA on Hg(II) catalyzed substitution of cyanide by NRS in [Ru(CN)6]4−. The detection limit of the proposed method was found to be 2.5×10−7M. The method has successfully been applied for the determination of d-PA in real samples with quantitative results.
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