The relative basicity of trioctylamine （TOA）, pKa,BS, in protic polar diluent （1-octanol）, non-protic polar diluent [methyl iso-butyl ketone （MIBK）] and inert diluent （CCl4） were determined for 11 mono-carboxy...The relative basicity of trioctylamine （TOA）, pKa,BS, in protic polar diluent （1-octanol）, non-protic polar diluent [methyl iso-butyl ketone （MIBK）] and inert diluent （CCl4） were determined for 11 mono-carboxylic acids, and the dependence of PKa,BS on the nature of solute and diluent type was discussed. The results show that pKa,BS determined by half neutralization with the solute carboxylic acid is in the order of 1-octanol〉MIBK〉CCl4 for a fixed TOA concentration, and it increases with increasing acidity and hydrophobicity of the carboxylic acid. Compared with two parameters of the solute extracted （acidity and hydrophobicity）, pKa,BS is more sensitive to hydrophobicity of the acid. A mathematic equation representing relationship between the apparent extraction equilibrium （K11） and the system properties （PKa,BS and pKa） was proposed： 1g K11 = 2pKa,BS=pKa. It is proved that the extraction equilibrium of mono-carboxylic acids can be predicted by the above equation with reasonable accuracy.展开更多
基金Supported by the National Natural Science Foundation of China (No. 29836130).
文摘The relative basicity of trioctylamine （TOA）, pKa,BS, in protic polar diluent （1-octanol）, non-protic polar diluent [methyl iso-butyl ketone （MIBK）] and inert diluent （CCl4） were determined for 11 mono-carboxylic acids, and the dependence of PKa,BS on the nature of solute and diluent type was discussed. The results show that pKa,BS determined by half neutralization with the solute carboxylic acid is in the order of 1-octanol〉MIBK〉CCl4 for a fixed TOA concentration, and it increases with increasing acidity and hydrophobicity of the carboxylic acid. Compared with two parameters of the solute extracted （acidity and hydrophobicity）, pKa,BS is more sensitive to hydrophobicity of the acid. A mathematic equation representing relationship between the apparent extraction equilibrium （K11） and the system properties （PKa,BS and pKa） was proposed： 1g K11 = 2pKa,BS=pKa. It is proved that the extraction equilibrium of mono-carboxylic acids can be predicted by the above equation with reasonable accuracy.
