Flushes, neurodermatology, and surroundings

In the quest to identify a property that may reliably predict the spontaneity of a process, a promising candidate has been identified: entropy. Processes that involve an increase in entropy of the system (ΔS > 0) are very often spontaneous; however, examples to the contrary are plentiful. By expanding consideration of entropy changes to include the surroundings, a significant conclusion regarding the relation between this property and spontaneity may be reached. In thermodynamic models, the...

Chemists ordinarily use a property known as enthalpy (H) to describe the thermodynamics of chemical and physical processes. Enthalpy is defined as the sum of a system’s internal energy (E) and the mathematical product of its pressure (P) and volume (V):

The total of all possible kinds of energy present in a substance is called the internal energy (U), sometimes symbolized as E. Suppose a system with initial internal energy, Uinitial, undergoes a change in energy (transfer of work or heat), and the final internal energy of the system is Ufinal. Change in internal energy equals the difference between Ufinal and Uinitial.

One of the challenges of using the second law of thermodynamics to determine if a process is spontaneous is that it requires measurements of the entropy change for the system and the entropy change for the surroundings. An alternative approach involving a new thermodynamic property defined in terms of system properties only was introduced in the late nineteenth century by American mathematician Josiah Willard Gibbs. This new property is called the Gibbs free energy (G) (or simply the free...

As a system undergoes a change, its internal energy can change, and energy can be transferred from the system to the surroundings, or from the surroundings to the system.

Calorimetry is a technique used to measure the amount of heat involved in a chemical or physical process or to measure the heat transferred to or from a substance. The heat is exchanged with a calibrated and insulated device called the calorimeter. Calorimetry experiments are based on the assumption that there is no heat exchange between the insulated calorimeter and the external environment. The well-insulated calorimeters prevent the transfer of heat between the calorimeter and its external...