chemical relaxation

Also contains definition of: T-jump
If the equilibrium mixture of a @[email protected] is disturbed by a sudden change, especially of some external parameter (such as temperature, pressure or electrical field strength), the system will readjust itself to a new position of the @[email protected] or return to the original position, if the perturbation is temporary. The readjustment is known as chemical @[email protected] In many cases, and in particular when the displacement from equilibrium is slight, the progress of the system towards equilibrium can be expressed as a first-order law: \[C_{t}- \left(C_{\text{eq}}\right)_{2} = [\left(C_{\text{eq}}\right)_{1}- \left(C_{\text{eq}}\right)_{2}]\ \text{e}^{\frac{-t}{\tau }}\] where \(\left(C_{\text{eq}}\right)_{1}\) and \(\left(C_{\text{eq}}\right)_{2}\) are the equilibrium concentrations of one of the chemical species involved in the reaction before and after the change in the external parameter, and \(C_{t}\) is its concentration at time \(t\). The time parameter \(\tau \), named @[email protected], is related to the rate constants of the chemical reaction involved. Measurements of the @[email protected] times by @[email protected] methods [involving a @[email protected] (T-jump), @[email protected], electric field jump or a periodic disturbance of an external parameter, as in ultrasonic techniques] are commonly used to follow the kinetics of very fast reactions.
PAC, 1994, 66, 1077. (Glossary of terms used in physical organic chemistry (IUPAC Recommendations 1994)) on page 1096 [Terms] [Paper]