Thermodynamic cycle integration by computer simulation as a tool for obtaining free energy differences in molecular...

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).

Sigmatropic rearrangements are a class of pericyclic reactions in which a σ bond migrates from one part of a π system to another. These are intramolecular rearrangements where the total number of σ and π bonds remain unchanged.
Sigmatropic shifts are classified based on an order term [i, j ], where i and j indicate the number of atoms across which each end of the σ bond migrates. Below are examples of a [3,3] sigmatropic shift in 1,5-hexadiene, referred to as...

A thermodynamic system is a set of objects whose thermodynamic properties are of interest. The system is considered to be embedded in its surroundings or the environment. The system and its environment can exchange heat and do work on each other through a boundary that separates them. However, the immediate surroundings of the system interact with it directly and therefore have a much stronger influence on its behavior and properties.
Consider an example of  tea boiling in a kettle. The tea and...

Thermodynamic potentials are state functions that are extremely useful in analyzing a thermodynamic system. They have dimensions of energy. The four important thermodynamic potentials are internal energy, enthalpy, Helmholtz free energy, and Gibbs free energy. These thermodynamic potentials can be expressed using two of the following variables: pressure, volume, temperature, and entropy. These two variables are expressed as the rate of change of the thermodynamic potential with respect to other...

The effective concentration of a species in a solution can be expressed precisely in terms of its activity. Activity considers the effect of electrolytes present in the vicinity of the species of interest and depends on the ionic strength of the solution. The activity of a species is expressed as the product of molar concentration and the activity coefficient of the species.
The thermodynamic equilibrium constant is more accurately defined in terms of activity rather than concentration.

A thermodynamic process is a path through a sequence of states that takes a system from an initial state to a final state. In a cyclic process, the system returns to its initial state, so the changes in state properties and state functions (ΔT, Δp, ΔV, ΔU, ΔH) over one complete cycle are zero. However, heat and work transfers can still occur during the cycle, and the net heat and net work over the cycle need not be zero.A reversible process occurs when the system is infinitesimally close to...