Abstract

AbstractThe heat change associated with the uptake of zinc (II) has been examined by using a twin type isoperibol calorimeter in the extraction of zinc (II) from hydrochloric acid solutions by trioctylamine hydrochloride (TOAHCl) and trioctylmethyl‐ammonium chloride (TOMAC) in various organic solvents such as benzene, chlorobenzene, o‐dichlorobenzene, toluene, m‐xylene, nitrobenzene, carbon tetrachloride and 1, 2‐dichloroethane. It was found that the dependence of apparent molar heat change (the value of the heat change detected with regard to the concentration of zinc (II) reacted) on the aqueous chloride concentration could be attributed to the change in the distribution of zinc (II) chloride species in the aqueous phase. Taking account of this fact, variable Y, which constitutes the sum of the change in enthalpies for the relevant steps in the extraction of zinc (II), except the transformation of ZnClj(2‐j)+ to ZnCl42‐, in the aqueous phase, is introduced. From the values of Y obtained, it is concluded that in the extraction by TOMAC, Y correlates with the solubility parameter of diluent, suggesting that the organic phases may be regarded as regular solutions, while in the extraction by TOAHCl, no clear‐cut relation holds between Y and the physico‐chemical constants of the diluent such as dipole moment, dielectric constant and solubility parameters.

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