Measurement and Prediction of Thermochemical Properties. Improved Benson-Type Increments for the Estimation of Enthalpies of Vaporization and Standard Enthalpies of Formation of Aliphatic Alcohols

Abstract

This work has been undertaken to revise the group-additivity values necessary for predicting standard enthalpies of formation and vaporization enthalpies of aliphatic alcohols by means of Benson's group-additivity scheme at the reference temperature T = 298.15 K. The database on the molar enthalpies of vaporization has been extended with measurements on some linear alcohols (1-hexanol, 1-heptanol, and 1-nonanol) and branched alkanols (2-hexanol, 5-methyl-3-hexanol, 2-methyl-2-hexanol, 3-ethyl-3-pentanol, 2-ethyl-1-hexanol, 2-methyl-2-heptanol, 3,5,5-trimethyl-1-hexanol, and 2,6-dimethyl-4-heptanol) using the transpiration method. The data were obtained from the temperature dependence of the vapor pressure measured by the transpiration method. A simultaneous compilation and evaluation of data for enthalpies in the liquid and in the gaseous phase together with vaporization enthalpies have been performed, thereby giving a basis for the validation of experimental results. The group-additivity parameters useful in the application of the Benson correlation are presented in tabular form, together with a description of their evaluation.

Vapour pressures and heat capacity measurements on the C7–C9 secondary aliphatic alcohols

“…This collection together with the our results helps to ascertain data base for branched aliphatic alcohols. Consistent results from this compilation, together with the critical surveys reported in our recent studies [1][2][3], have encouraged the re-evaluation of the Benson-type increments for calculation of thermochemical properties of the aliphatic alcohols [19].…”

Vapour pressures and enthalpies of vapourization of a series of the γ-lactones

“…As a rule, the members of the homologues series c-butyrolactone and c-valerolactone should have vapourization enthalpies which are different by about 5 kJ Á mol À1 [5]. Unexpected, vapourization enthalpies D g l H m (298.15 K) of c-butyrolactone, (54.4 ± 0.4) kJ Á mol À1 , and c-valerolactone, (53.9 ± 0.2) kJ Á mol À1 , are indistinguishable and explanation for this artefact will be given below.…”

Vapour pressures and enthalpies of vaporization of a series of the linear n-alkyl-benzenes

“…This paper is another in the series of papers concerning the systematic investigation of vapour pressures of homologues. We have contributed to this series in the past by determining vapour pressures and enthalpies of vaporization investigations on branched esters [1,2], amines [3], nitro-compounds [4], nitriles [5,6], alcohols [7,8], aldehydes [9], ketones [10], imines [11], fluoroalkanes [12], carboxylic acids [13], and alkyl ethers, acetals, ketals, orthoesters [14][15][16][17]. This work was initiated to investigate the relationship between vaporization enthalpy and Kovat's indices and it extends our previous [18,19] studies on the alkyl-benzenes with the systematic study of the linear alkyl-benzenes with the alkyl chain length of C 5 , C 7 , C 10 , and C 11 .…”