principle of microscopic reversibility

physics
Also known as: principle of detailed balancing
Related Topics:
chemical equilibrium

principle of microscopic reversibility, principle formulated about 1924 by the American scientist Richard C. Tolman that provides a dynamic description of an equilibrium condition. Equilibrium is a state in which no net change in some given property of a physical system is observable; e.g., in a chemical reaction, no change takes place in the concentrations of reactants and products, although the Dutch chemist J.H. van’t Hoff had already recognized that this condition results from the equality of the forward and backward rates of a reversible reaction. According to the principle of microscopic reversibility, at equilibrium there is continuous activity on a microscopic (i.e., atomic or molecular) level, although on a macroscopic (observable) scale the system may be considered as standing still. There is no net change favouring any one direction, because whatever is being done is being undone at the same rate. Thus, for a chemical reaction at equilibrium, the amount of reactants being converted to products per unit time is exactly matched by the amount being converted to reactants (from products) per unit time. The principle of microscopic reversibility, when applied to a chemical reaction that proceeds in several steps, is known as the principle of detailed balancing. Basically, it states that at equilibrium each individual reaction occurs in such a way that the forward and reverse rates are equal.

time reversal, in physics, mathematical operation of replacing the expression for time with its negative in formulas or equations so that they describe an event in which time runs backward or all the motions are reversed. A resultant formula or equation that remains unchanged by this operation is said to be time-reversal invariant, which implies that the same laws of physics apply equally well in both situations, that the second event is indistinguishable from the original, and that the flow of time does not have any naturally preferred direction in the case of fundamental interactions. A motion picture of two billiard balls colliding, for example, can be run forward or backward with no clue to the proper time direction of the event.

Interactions among the subatomic particles under the operation of time reversal were thought to be invariant in the same way, but evidence to the contrary was discovered in 1964 in weak nuclear interactions (see CP violation). There is, however, a more general inversion operation that does leave the physical laws invariant, called in its mathematical expression the CPT theorem. It comprises time reversal T combined with interchange of antiparticles and particles, called charge conjugation C, and a mirror reflection, or inversion, of space, called parity reversal P. When all these are performed simultaneously, the resultant process or interaction is indistinguishable from the original.