Thermochemistry of Bu4NBr solutions in binary solvents containing formamide

Abstract

The heats of solution of tetrabutylammonium bromide have been measured in mixtures of formamide (FA) with methanol (MeOH) and ethylene glycol (EG) at 313.15 K by calorimetric method. The standard enthalpies of solution in binary mixtures have been extrapolated to infinite dilution by Redlich–Rosenfeld–Meyer type equation using the literary data at 298.15 K and the present paper data at 313.15 K. The Debye–Hückel limiting law slope A H required for calculation of the ∆sol H 0 value has been obtained with application the new additive scheme of determination of the physic-chemical characteristics of binaries. The scheme is tested on the example of Bu4NBr solutions in FA–MeOH mixture at 298.15 K. Its application yields the ∆sol H 0 value very closed on the ones determined with the real (non-additive) characteristics of binaries. The standard enthalpies of solution extrapolated by Redlich–Rosenfeld–Meyer type equation are in a good agreement with the ones computed in terms of the Debye–Hückel theory in the second approximation. The heat capacities characteristics of Bu4NBr have been calculated in H2O–FA, MeOH–FA and EG–FA mixtures using the literary and present data. The sequence of solvents H2O > FA > EG > MeOH located on their ability to solvophobic solvation found by us earlier for enthalpic characteristics is confirmed by the ∆C p 0 values. The comparison of thermochemical characteristics of Bu4NBr solutions in aqueous and non-aqueous mixtures containing FA has been carried out. The own structure of water remains in the region of small additions of formamide to co-solvents. It considerably differs the H2O–FA mixture from the investigated non-aqueous systems.