title: Hydrogen bonding in hydrates with one acetic acid molecule.
abstract: Hydrogen bonding (H-bond) interaction significantly influences the separation of acetic acid (HAc) from the HAc/H(2)O mixtures, especially the dilute solution, in distillation processes. It has been examined from the HAc mono-, di-, tri-, and tetrahydrates by analyzing the structures, binding energies, and infrared vibrational frequencies from quantum chemical calculations. For the first coordinate shell the 6-membered head-on ring is surely the most favorable structure because it has (1) the most favorable H-bonding parameters, (2) almost the largest binding energy per H-bond, (3) the biggest wavenumber shifts, and (4) the highest ring distribution (the AIMD simulations). Moreover, the comparison of the calculations with the experiments (the X-ray scattering data and IR frequencies) suggests that the possible structures in dilute aqueous solution are those involving two or more coordinate shells. The H-bonding in these water-surrounded HAc hydrates are the origin of the low-efficiency problem of isolating HAc from the dilute HAc/H(2)O mixtures. It is apparently a tougher work to break the H-bonds among HAc and the surrounded H(2)O molecules with respect to the case of more concentrated solutions, where the dominant structures are HAc or H(2)O aggregates.
authors.affiliation: Separation Engineering Research Center of Nanjing University, Key Laboratory in Meso- & Microscopic Chemistry of Ministry of Education of China, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, China.
authors.forename: Liang
authors.initials: L
authors.lastname: Pu
authors.forename: Yueming
authors.initials: Y
authors.lastname: Sun
authors.forename: Zhibing
authors.initials: Z
authors.lastname: Zhang