Additive single atom values for thermodynamics II: Enthalpies, entropies and Gibbs energies for formation of ionic solids

Abstract

In part I of this series we established optimised sum values, for each of the chemical elements, of formula volumes, of absolute entropies, and of constant pressure heat capacities, together with their temperature coefficients. These atom values, when summed for a chemical formula, provided zero-level estimates of the corresponding property of that chemical material. Atom sums have the particular advantage of being essentially complete because of the finite number of chemical elements and are of use in prediction and checking of values for chemical materials. However, this is at the expense of an inability to distinguish among isomers and phases with the same chemical formula nor do they allow for effects of atom interactions.

In the present publication, we present optimised atom sums for formation entropies, formation enthalpies and their relation to formation Gibbs energies.

In order to check the reliability of the results, comparison is made among methods of prediction using each of DFT calculations, a proprietary group contribution method, and the proposed single atom sum method. The single atom sum method is found to be most suitable as an initial estimate for large formation entropies and also for large values of formation enthalpies, which includes ionic hydrates.

The energy contributions of the elements group into the Groups of the Periodic Table so that strict atom independence and thus additivity is not predominant while entropy terms are relatively constant (for the non-gaseous elements) implying that the atoms behave independently and thus additively in contributing to the entropy terms resulting from their vibrations within the ionic solids. This is possibly a unique demonstration resulting from this single atom sum collection.

This now comprises a complete set for simple zero-order thermodynamic prediction and for checking, which should be complemented by whatever other resources are available to the researcher.