Correlation and estimation of gas-chloroform and water-chloroform partition coefficients by a linear free energy relationship method

A linear free energy relationship, LFER, has been used to correlate 150 val ues of gas-chloroform partition coefficients, as log L-chl with a standard deviation, sd, of 0.23 log units, a correlation coefficient r(2) of 0.985, and an F-statistic of 1919. The equation reveals that bulk chloroform is di polar/polarizable, of little hydrogen-bond basicity, but as strong a hydrog en-bond acid as bulk methanol or bulk ethanol. However, the main influence on gaseous solubility in chloroform is clue to solute-solvent London disper sion interactions. A slightly modified LFER has been used to correlate 302 values of water-chloroform partition coefficients, as log P-chl. The correl ation equation predicts log Pchl for a further 34 compounds not used in the equation with sd = 0.17 log units. When the LEER is applied to all 335 log P-chl values, the resulting equation has sd = 0.25, r(2) = 0.971, and F = 2218.