The rate constants of hydrolysis of N-tert-butyl-α-phenylnitrone and its derivatives have been determined by UV spectrophotometry at 25℃ and a rate equation which can be applied over a wide pH range was obtained. On the basis of rate equations derived and judging from the hydrolysis products obtained and general base and substituent effects, plausible mechanism of hydrolysis in various pH range have been proposed. Below pH 4.5, the hydrolysis was initiated by the protonation and followed by the addition of water to α-carbon. Above pH 10.0, the hydrolysis was proceeded by the addition of hydroxides ion to α-carbon. In the range of 4.5~10.0 the addition of water to nitrone was rate controlling step.

We have synthesized the water-insoluble chitosan derivative, N-dithiocarboxy chitosan sodium salt, through the reaction of chitosan with carbon disulfide in the presence of alkali metal hydroxide, Chitosan itself has been prepared using chitin, one of the most abundant compounds in nature, as a starting material. To elucidate this natural polymer the capacity of adsorbing heavy metal ions, we have performed adsorption experiments using chitosan derivatives of various average molecular weights with different contents of sulfur. The effect of pH, adsorption time and temperature on adsorption efficiency was also studied. The adsorbent derived from chitosan of average molecular weight ranging 5,700~20,000 was shown to have the highest capacity of adsorbing heavy metal ions. Adsorbing efficiency was increased as the reaction time was increased and as the reaction temperature range of 25~45℃. The adsorption capacity at various pH, however, appeared to vary depending on the heavy metal ions studied.

Chitosan itself has been prepared using chitin, one of the most abundant compounds in nature, as a starting material. We have synthesized the water-soluble chitosan derivative, N-dithiocarboxy chitosan sodium salt, through the reaction of water-soluble chitosan with carbon disulfide in the presence of alkali metal hydroxide. To elucidate this natural polymer capacity of adsorbing heavy metal ions, we have performed adsorption experiments using the water-soluble chitosan derivative various average molecular weight and of different percent contents of sulfur. The effect of pH, adsorption time and temperature on adsorption efficiency was also studied. The adsorbent derived from water-soluble chitosan of average molecular weight ranging 9,000~120,000 was shown to have the highest capacity of adsorbing heavy metal ions. On the whole, adsorbing efficiency was increased as the reaction time goes longer and also increased as the reaction temperture goes higer in temperture range of 15℃~45℃. The adsorption capacity at various pH, however, was appeared to vary depending on the heavy metal ions studied Judging from these finding, water-soluble N-dithiocarboxy chitosan sodium salt, a derivative of a biodegradable nature polymer, is believed to be a potential adsorbent for heavy metal ions since it not only is shown to lower the concentration of heavy metal ions to below the drainage quality standard, but also it would not cause acidification and hardening of soil which is one of the detrimental effects of synthetic macromolecular adsorbents present.

The rate constant of Nucleophilic addition of sodium thiophenoxide to nitrone were determined by UV Spectrophotometry and a rate equation which can be applied over wide pH range was obtained. Base on the rate equation, general base effect, substituent effect and final product, plausible mechanism of addition reaction have been proposed. Blow pH 3.0, the reaction was initiated of thiophenol, and in the range of pH 3.0~10.0, proceeded by the competitive addition of thiophenol and thiophenoxide anion. Above the pH 10.0, the reaction proceeded through the addition of a thiophenoxide anion.

The rate constant of the nucleophilic addition of 1-propanethiol to α-phenyl-N-iso-propylnitrone derivatives were determined at various pH and a rate equation which can be applied over wide pH range is obtained. Final product of the addition reaction was α-thiopropyl-p-phenylbenzylideneamine. Base on the rate equation, general base effect, substituent effect and final product, plausible mechanism of addition reaction have been proposed. Below pH 3.0, the reaction was initiated by the addition of 1-propanthiol, and in the range of pH 3.0-10.0, proceeded by the competitive addition of 1-propanethiol and propanethiolate. Above the pH 10.0, the reaction proceeded through the addition of propanethiolate.

The rate constants of hydrolysis of α-phenly-N-iso-propylnitrone and its derivatives have been determined by UV spectrophotometry at 25℃ and a rate equation which can be applied over a wide pH range was obtained. On the basis of rate equations derived and judging from the hydrolysis products obtained and general base and substituent effects, plausible mechanism of hydrolysis in various pH range have been proposed. Below pH 4.5, the hydrolysis was initiated by the protonation and followed by the addition of water to α-carbon. Above pH 10.0, the hydrolysis was proceeded by the addition of hydroxide ion to α-carbon. In the range of 4.5~10.0, the addition of water to nitrone was rate controlling step.