On ionic limiting partial molal volume calculations in various solvents

Abstract

At present, reasonable progress has been reached in the calculation of different ionic partial molal values by various indirect methods. The use of the non-thermodynamic, so-called extrapolation method to split the limiting partial molal volumes of electrolytes into ionic contributions is discussed in the light of Zana's comments. It is shown that if the extrapolation process is conducted starting from Pr₄NX, an excellent linear relationship between V°(R₄NX) and M(R₄N⁺)(with correlation coefficient r= 0.9999) is observed for all solvents examined. The physical significance of the V°(R₄N⁺) values obtained is demonstrated by analysing the equation V°(Ph₄As⁺)/V°(BPh^–₄)=r³(Ph₄As⁺)/r³(BPh^–₄) for ethylene glycol and acetonitrile solvents.