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Hydrogen‐bond cooperativity in 1‐alkanol + n ‐alkane binary mixtures
Author(s) -
Gupta Ram B.,
Brinkley Ray L.
Publication year - 1998
Publication title -
aiche journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.958
H-Index - 167
eISSN - 1547-5905
pISSN - 0001-1541
DOI - 10.1002/aic.690440122
Subject(s) - cooperativity , hydrogen bond , chemistry , low barrier hydrogen bond , thermodynamics , hydrogen , molecule , computational chemistry , chemical physics , organic chemistry , physics , biochemistry
Hydrogen‐bond cooperativity is an effect when hydrogen bonding is influenced by the previously formed hydrogen bond on the molecules. Using Fourier‐transform infrared spectroscopy, we 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‐association‐fluid theory, lattice‐fluid‐hydrogen‐bonding theory, and associated perturbed‐anisotropic‐chain theory, cannot represent the experimental data accurately. The extended lattice‐fluid‐hydrogen‐bonding theory that includes hydrogen‐bond cooperativity agrees well with the experimental data. Study suggests that the equilibrium constant for the second hydrogen bond on 1‐alkanol molecules is 10 times larger than that for the first hydrogen bond formation. Hence, strong hydrogen bond cooperativity exists in 1‐alkanol self association. Equations of state dealing with 1‐alkanol mixtures need to be modified to account for this strong hydrogen‐bond cooperativity.