16. Gupta, Ram B.; Brinkley, Ray L. Hydrogen-bond cooperativity in 1-alkanol + n-alkane binary mixtures. AIChE J. (1998), 44(1), 207-213.
Abstract
Hydrogen-bond cooperativity is an effect when hydrogen bonding is influenced by the previously formed hydrogen bond n the mols. Using Fourier-transform IR spectroscopy, the authors have measured the extent of self hydrogen bonding in 1-hexanol and 1-pentanol dissolved in n-hexane. Conventional theories without hydrogen-bond cooperativity, such as the statistical-assocn.-fluid theory, lattice-fluid-hydrogen-bonding theory, and assocd. perturbed-anisotropic-chain theory, cannot represent the exptl. data accurately. The extended lattice-fluid-hydrogen-bonding theory that includes hydrogen-bond cooperativity agrees well with the exptl. data. Study suggests that the equil. const. for the second hydrogen bond on 1-alkanol mols. is 10 times larger than that for the first hydrogen bond formation. Hence, strong hydrogen bond cooperativity exists in 1-alkanol self-assocn. Equations of state dealing with 1-alkanol mixts. need to be modified to account for this strong hydrogen-bond cooperativity.