Solute–solute interactions in water. II. An analysis through the Kirkwood–Buff integrals for 14 organic solutes

摘要: From accurate data of activities (a), partial molar volumes (V), and compressibility (K) binary aqueous mixtures, the so‐called Kirkwood–Buff integrals Gij defined by Gij=∫∞0 [ gij(r) −1] 4πr2 dr=f(a,V,K), (i=1,2; j=1,2), have been calculated in whole concentration range. Fourteen water(1)‐organic cosolvent(2) systems [methanol, ethanol, 1‐propanol, 1‐butanol, 2‐methyl‐2‐propanol, acetonitrile, acetone, dimethylsulfoxide, tetrahydrofuran, piperidine, pyridine, 1,4‐dioxane, 2‐aminoethanol, 2‐(dimethylamino)ethanol] studied at 25 °C, two (methanol ethanol) also different temperatures. The functions show these features relation to molecular structures component 2: (1) when this presents a large nonpolar moiety, extrema are exhibited Gij’s certain concentrations more marked larger portion; (2) is bifunctional, trend monotonic with concentration; (3) temperature range 0–90 °C, G22 increases G12...