A new method for the determination of cooperative hydrogen bonding enthalpy of proton acceptors with associated species of alcohols

Abstract

A calorimetric method for the determination of cooperative hydrogen bonding (HB) enthalpy of proton acceptors (B) with associated species of alcohols is proposed. The average enthalpy of cooperative HB of pyridine with associated species of alcohols was found to be À19.8 AE 0.6 kJ mol À1 for all alcohols investigated. This value exceeds the enthalpy of HB in the complex ROH . . . NC 5 H 5 (the average for all alcohols is À15.8 AE 0.2 kJ mol À1 ) by 20-30%. Cooperativity factors (A b , A Ox ) of hydrogen bonds for (ROH) 2 . . . NC 5 H 5 complexes were determined using the IR-spectroscopic method. The average values for the alcohols under consideration were found to be A b ¼ 1.41 AE 0.04 and A Ox ¼ 1.54 AE 0.05. On the basis of IR-spectroscopic and calorimetric data, the enthalpy of cooperative interactions of pyridine with the dimer (ROH) 2 was estimated. This value for all the alcohols studied is, on average, À20.9 AE 0.1 kJ mol À1 .

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

“…More than 400 values of enthalpies of hydrogen bonding were determined using equation (4) [5,33,39]. The obtained values are in a good agreement with the results of spectral and other methods [39].…”

“…It was shown [33] that the cooperative strengthening of hydrogen bonding in complexes of pyridine with alcohol clusters is about 20-30% comparing with the complexes 1:1 ''alcohol-pyridine''. In this work, we used the solution calorimetry for the investigation of cooperative hydrogen bonding of tertiary aliphatic and aromatic amines with series of aliphatic alcohols.…”

“…Recently, a new empirical method for the estimation of cooperative hydrogen bonding enthalpy of pyridine with aliphatic alcohols [33] was proposed. It was shown [33] that the cooperative strengthening of hydrogen bonding in complexes of pyridine with alcohol clusters is about 20-30% comparing with the complexes 1:1 ''alcohol-pyridine''.…”

A method to determine the Gibbs energy of specific interactions in solutions. Hydrogen bonding of proton donating solutes in basic solvents

“…Widely recognized importance of this phenomenon for biochemical systems determines the necessity to have a method allowing to determine the energy of cooperative hydrogen bonding from experimental data. In a work [21], such method [10] was successfully applied for the enthalpies of cooperative hydrogen bonding. Now we are going to quantify the Gibbs energy of hydrogen bonding in solutions.…”

Effect of halogen substitution on the enthalpies of solvation and hydrogen bonding of organic solutes in chlorobenzene and 1,2-dichlorobenzene derived using multi-parameter correlations

“…This study continues our combined experimental and theoretical examination of gas-toorganic solvent transfer processes for nonelectrolyte solutes [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19]. Such processes govern chemical separations by gas-liquid chromatography, measurement of solubilities and activity coefficients by inert-gas stripping methods, and the removal and pre-concentration of volatile organic solutes from aqueous analytical samples using headspace single drop micro-extraction methods.…”