The enol contents and equilibrium constants for keto-enol tautomerism of ethyl acetoacetate in supercritical (SC) CO2 with and without cosolvent ethanol and in various liquid solvents were investigated by UV spectrosc...The enol contents and equilibrium constants for keto-enol tautomerism of ethyl acetoacetate in supercritical (SC) CO2 with and without cosolvent ethanol and in various liquid solvents were investigated by UV spectroscopy. The local dielectric constant about the solute in SC CO2/ethanol system was obtained through the correlation between Gibbs free energy of tautomerism and Onsager-Kirkwood solvent quantity. The great difference between local dielectric constant and that calculated from homogeneous dielectric medium theory suggests clustering of the cosolvent around the solute.展开更多
文摘The enol contents and equilibrium constants for keto-enol tautomerism of ethyl acetoacetate in supercritical (SC) CO2 with and without cosolvent ethanol and in various liquid solvents were investigated by UV spectroscopy. The local dielectric constant about the solute in SC CO2/ethanol system was obtained through the correlation between Gibbs free energy of tautomerism and Onsager-Kirkwood solvent quantity. The great difference between local dielectric constant and that calculated from homogeneous dielectric medium theory suggests clustering of the cosolvent around the solute.