Negative Activation Energy
In some cases, rates of reaction decrease with increasing temperature. When following an approximately exponential relationship so the rate constant can still be fit to an Arrhenius expression, this results in a negative value of Ea. Elementary reactions exhibiting these negative activation energies are typically barrierless reactions, in which the reaction proceeding relies on the capture of the molecules in a potential well. Increasing the temperature leads to a reduced probability of the colliding molecules capturing one another (with more glancing collisions not leading to reaction as the higher momentum carries the colliding particles out of the potential well), expressed as a reaction cross section that decreases with increasing temperature. Such a situation no longer leads itself to direct interpretations as the height of a potential spot.
Read more about this topic: Activation Energy
Famous quotes containing the words negative and/or energy:
“The idealist’s programme of political or economic reform may be impracticable, absurd, demonstrably ridiculous; but it can never be successfully opposed merely by pointing out that this is the case. A negative opposition cannot be wholly effectual: there must be a competing idealism; something must be offered that is not only less objectionable but more desirable.”
—Charles Horton Cooley (1864–1929)
“A government deriving its energy from the will of the society, and operating, by the reason of its measures, on the understanding and interest of the society ... is the government for which philosophy has been searching and humanity been fighting from the most remote ages ... which it is the glory of America to have invented, and her unrivalled happiness to possess.”
—James Madison (1751–1836)