Thermodynamics of 1-alkanol+cyclic ether mixtures

Thermodynamics of mixtures with strongly negative deviations from Raoult’s law. Part 8. Excess molar volumes at 298.15K for 1-alkanol + isomeric amine (C6H15N) systems

“…From our theoretical analysis of these data [4], and from our experimental V E data for 1-alkanol + linear secondary amine mixtures [5][6][7], it was concluded that interactions between methanol or ethanol and primary or secondary linear amines are stronger than when longer 1-alkanols are involved.…”

“…In this series of papers [1][2][3][4][5][6][7], our general aim is the characterization, using different models, of interactions between unlike molecules in systems which exhibit very strong negative deviations from Raoult's law. We have shown that DIS-QUAC [8,9], a purely physical model based on the rigid lattice theory developed by Guggenheim [10], is a powerful tool to describe thermodynamic properties of the mentioned solutions assuming structure-dependent interaction parameters.…”

“…It is remarkable that DISQUAC gives similar results as when association models are used. This is shown when DIS-QUAC results are compared with those provided by the UNI- QUAC association solution theory for 1-alkanol + propanal systems [1], by the ideal association solution theory for linear ketone [1], or oxaalkane [2] + CHCl 3 mixtures, or by the ERAS model [11] for 1-alkanol + propanal [1], or + primary, secondary or tertiary linear amine [3,4] systems.…”

“…In previous articles of this series [3][4][5][6][7], we have examined mixtures of 1-alkanols with linear amines using the DISQUAC and ERAS models. The extremely negative H E values [16][17][18][19][20][21][22][23][24][25] of these systems are interpreted in terms of two opposing effects [4,18,21]: (a) in the pure state, both, the alcohol and the amine are self-associated by the formation of O-H · · · O and N-H · · · N bonds, respectively.…”

“…The extremely negative H E values [16][17][18][19][20][21][22][23][24][25] of these systems are interpreted in terms of two opposing effects [4,18,21]: (a) in the pure state, both, the alcohol and the amine are self-associated by the formation of O-H · · · O and N-H · · · N bonds, respectively. The disruption of these bonds upon mixing leads to a positive contribution to H E ; (b) strong intermolecular interactions between the hydroxyl and amine groups contribute negatively to H E .…”