Gibbs energies of transfer of the proton from water into mixtures of water with chain multiple ethers: Equilibria involving changes of solvation of the proton,10.1039/B206085J

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Lactoyl-CoA 全氟丁基戊烷白叶藤碱全氟己基辛烷新白叶藤碱壳寡糖特色专题-生物多肽

Gibbs energies of transfer of the proton from water into mixtures of water with chain multiple ethers: Equilibria involving changes of solvation of the proton

Physical Chemistry Chemical Physics Pub Date : 01/21/2003 00:00:00 , DOI:10.1039/B206085J

Abstract

The solvent reorganisation around the proton has been investigated in mixtures of water with the dimethyl ethers of diethylene glycol and triethylene glycol using spectrophotometric observations on dilute solutions of 4-nitroaniline. The protonation occurs at only one basic site on the multiple ethers and the equilibrium constant is much greater than for simple ethers and alcohols. The Gibbs energy of transfer of the proton from water into the mixture is calculated. Comparing ΔG^o_t(H⁺) with those for simple ethers and alcohols, it is concluded that the end ether group is the preferred basic site in the multiple ethers. ΔG^o_t(H⁺) from this method are compared with ΔG^o_t(H⁺) determined using the TATB method for a range of co-solvents: good agreement is obtained, except where enhanced structure is found in the water + co-solvent mixtures.