Effect of a third component on the interactions in a binary mixture determined from the fluctuation theory of solutions

The Kirkwood–Buff (KB) theory of solution is applied to a ternary mixture by deriving explicit expressions for the various Kirkwood–Buff integrals (KBIs) and the corresponding excesses of the number of molecules around central ones. However, the ideal solution should be considered non-aggregated, and the above expressions for the excesses provide non-zero values for such a case. For this reason, in order to obtain information about clustering one must subtract from the traditional excesses those which correspond to a reference state, thus ensuring that for an ideal mixture the excesses are zero. The expressions derived for the latter excesses have been applied to the investigation of the N,N-dimethylformamide–methanol–water mixture, to conclude that: (i) in the vicinity of the water molecules there are excesses of water and N,N-dimethylformamide molecules and a deficit of methanol molecules; (ii) in the vicinity of the methanol molecules there are excesses of methanol and N,N-dimethylformamide molecules and a deficit of water molecules; (iii) in the vicinity of the N,N-dimethylformamide molecules there are excesses of methanol and water molecules and a deficit of N,N-dimethylformamide molecules; (iiii) the excesses of N,N-dimethylformamide around water and methanol molecules and those around N,N-dimethylformamide are weakly dependent on the concentration of the third component in a large range of concentrations of the latter, and these results are compatible with the existence of N,N-dimethylformamide–water and N,N-dimethylformamide–alcohol complexes.