Calorimetric determination of hydrogen‐bonding enthalpy for neat aliphatic alcohols

Abstract

Hydrogen bonding in pure aliphatic alcohols is investigated using a novel calorimetric approach. Average enthalpies of hydrogen bonding were determined for methanol, ethanol, propan‐1‐ol, propan‐2‐ol, butan‐1‐ol, hexan‐1‐ol and octan‐1‐ol. For all the studied alcohols except methanol the average hydrogen‐bonding enthalpies fall in the range from −16.9 to −17.7 kJ mol−1. A slightly smaller value of −15.1 kJ mol−1 was observed for methanol. From the enthalpies of the specific interactions of the alcohols and chloroform (as proton donors) formed with the alcohols and diethyl ether (as proton acceptors), the dimerization enthalpies were determined for the investigated alcohols: −8.6 ± 0.7 kJ mol−1. The specific interaction and dimerization enthalpies obtained are concurrent with the Badger–Bauer rule and the hydrogen‐bond cooperativity effects. The calorimetric data obtained are supported by literature Fourier transform infrared data on dimer and multimer formation for ethanol and octan‐1‐ol in tetrachloromethane solution. Copyright © 2005 John Wiley & Sons, Ltd.

Modeling phase equilibria of alkanols with the simplified PC-SAFT equation of state and generalized pure compound parameters

“…From these eight 1-alkanols the geometric mean of both ε AB (association energy) and the κ AB (association volume) were calculated and were subsequently assumed to be constant for all alkanols. The value of ε AB = 2811.02 K is in fair agreement with the theoretical value obtained by Nath and Bender [13], the values experimentally estimated by Solomonov et al [14]; and also Huang and Radosz [4] and Gross and Sadowski [6] estimated association Table 1 Modifications of the simplified PC-SAFT EoS [2] compared to the PC-SAFT EoS [1] PC-SAFT [1] Simplified PC-SAFT [2] g hs ij = 1…”

“…This has been confirmed by, e.g. Solomonov et al [14] where a lower hydrogen bonding enthalpy compared to C 2 -C 8 1-alkanols was determined experimentally. The determined parameters are referred as 'generalized alkanol parameters' in the following text and presented in Table 2.…”

Enthalpy of cooperative hydrogen bonding in complexes of tertiary amines with aliphatic alcohols: Calorimetric study

“…Studies of hydrogen bond formation in aliphatic alcohols have been carried out with different experimental methods, for example, vapor pressure [3,4] and calorimetric measurements [5][6][7][8], infrared (FTIR) spectroscopy [9][10][11][12][13][14] and nuclear magnetic resonance (NMR) [15][16][17][18][19] techniques. The authors attempted to solve two major tasks in these studies.…”

Determination of solvation and specific interaction enthalpies of adamantane derivatives in aprotic solvents

“…This could be due to the solvents' polarizability capacity which contributes to the solvation process of 2-AdO (with a polarizable = O bond) but not to that of 1-AdBr or 1-AdOH. This fact also excludes the use of benzene as a possible reference solvent, for which the corresponding empirical coefficients are known [18].…”