Equilibrium and non-equilibrium studies on certain chemical systems I. Equilibrium thermochemical investigations on selected sugars and spiranes. II. Shear viscosity studies on [alpha]-olefins and normal alcohols

Abstract

Precision oxygen-bomb calorimetry measurements have been conducted in three areas of investigation. The areas of investigation are: 1) the construction of a predictive standard enthalpy of formation correlation procedure for spriroalkane compounds and, specifically, the nature and contribution of the spiro-carbon atom; 2) the enthalpies of combustion and formation of aldopentoses; and 3) the enthalpies of combustion and formation of maltose and lactose sugars. Enthalpies of vaporization have been determined for selected spiroalkanes and the enthalpies of melting and desorption for the hydrated sugars have been determined by a dynamical method. High precision kinematic shear viscosities have been measured for certain normal alcohols and α-olefins from -20°C to about 80°C. The experimental data are analyzed with respect to the Andrade equation, the Eyring density dependent equation, the Batschinski-Hildebrand equation, and a generalized empirical equation. In order to understand the energy-structural relations in the spiroalkanes, the enthalpies of combustion for spiro[4.5]decane, spiro[5.5]lundecane, spiro[5.6]dodecane, and 7-n-hexadecyl-spiro[4.5]decane were determined by static oxygen-bomb calorimetry. From these measurements, the spiro-carbon atom contribution to the strain energy of the spirane molecules has been ascertained. ...