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:
“Isolation in creative work is an onerous thing. Better to have negative criticism than nothing at all.”
—Anton Pavlovich Chekhov (1860–1904)
“Just as we need to encourage women to test life’s many options, we need to acknowledge real limits of energy and resources. It would be pointless and cruel to prescribe role combination for every woman at each moment of her life. Life has its seasons. There are moments when a woman ought to invest emotionally in many different roles, and other moments when she may need to conserve her psychological energies.”
—Faye J. Crosby (20th century)