Computational methods in organic chemistry. 3. Correction of computed enthalpies for multiple conformations

Enthalpy changes are typically tabulated for reactions in which both the reactants and products are at the same conditions. A standard state is a commonly accepted set of conditions used as a reference point for the determination of properties under other different conditions. For chemists, the IUPAC standard state refers to materials under a pressure of 1 bar and solutions at 1 M and does not specify a temperature. Many thermochemical tables list values with a standard state of 1 atm. Because...

Hess’s law can be used to determine the enthalpy change of any reaction if the corresponding enthalpies of formation of the reactants and products are available. The main reaction may be divided into stepwise reactions : (i) decompositions of the reactants into their component elements, for which the enthalpy changes are proportional to the negative of the enthalpies of formation of the reactants, −ΔHf°(reactants), followed by (ii) re-combinations of the elements (obtained in step 1) to give...

For a chemical reaction (the system) carried out at constant pressure – with the only work done caused by expansion or contraction – the enthalpy of reaction (also called the heat of reaction, ΔHrxn) is equal to the heat exchanged with the surroundings (qp).

In an organic molecule, free rotation about the carbon-carbon single bond results in energetically different conformers of the molecule. Due to this rotation, called the internal rotation, ethane has two major conformations — staggered and eclipsed.
Staggered conformation is a low energy and more stable conformation with the C-H bonds on the front carbon placed at 60°dihedral angles relative to the C-H bonds on the back carbon, leading to a reduced torsional strain. In staggered ethane, the...

The enthalpy change of a chemical reaction is the difference between the total enthalpy of the products and the reactants. This energy change for the molecules involved in a chemical reaction can be visualized through an energy diagram, where the lines represent the total enthalpy of the reactants and products, and the gap between them signifies the enthalpy change for the reaction. In an exothermic reaction, the system's enthalpy decreases, whereas it increases in an endothermic reaction.The...

There are two ways to determine the amount of heat involved in a chemical change: measure it experimentally, or calculate it from other experimentally determined enthalpy changes. Some reactions are difficult, if not impossible, to investigate and make accurate measurements for experimentally. And even when a reaction is not hard to perform or measure, it is convenient to be able to determine the heat involved in a reaction without having to perform an experiment.