Influence of internal rotation on exothermic reactions between neutral molecules at low temperatures

Ronald McCarroll1

  • 1Laboratoire de Chimie Physique-Matière et Rayonnement, UMR 7614 du CNRS, Université Pierre et Marie Curie, 75231-Paris Cedex 05, France. ronald.mac_carroll@upmc.fr

Related Concept Videos

The Molecular Nature of Internal Energy01:27

The Molecular Nature of Internal Energy

The internal energy of a molecule is determined by its degrees of freedom, including translational, rotational, and vibrational motions. In addition to these kinetic activities, the energy of molecules is also shaped by electronic energy, intermolecular forces, and the rest-mass energy of electrons and nuclei. These factors collectively influence the energy state of the molecules. The equipartition theorem of classical mechanics provides insight into this energy distribution. It posits that the...
Effects of Temperature on Free Energy02:11

Effects of Temperature on Free Energy

The spontaneity of a process depends upon the temperature of the system. Phase transitions, for example, will proceed spontaneously in one direction or the other depending upon the temperature of the substance in question. Likewise, some chemical reactions can also exhibit temperature-dependent spontaneities. To illustrate this concept, the equation relating free energy change to the enthalpy and entropy changes for the process is considered:
Diels–Alder vs Retro-Diels–Alder Reaction: Thermodynamic Factors01:31

Diels–Alder vs Retro-Diels–Alder Reaction: Thermodynamic Factors

The Diels–Alder reaction is thermally reversible, meaning that the reaction reverts to the starting diene and dienophile under suitable temperatures. The forward reaction gives a cyclohexene derivative and is favored at low to medium temperatures. The reverse process, also called retro-Diels–Alder reaction, is a ring-opening process favored at high temperatures.
Radical Reactivity: Intramolecular vs Intermolecular01:33

Radical Reactivity: Intramolecular vs Intermolecular

Radical reactions can occur either intermolecularly or intramolecularly. In an intermolecular radical reaction, a nucleophilic radical adds to an electrophilic alkene or vice versa. In such reactions, the radical and generally the alkene, which is also called the radical trap, are two different molecules. Additionally, for such intermolecular reactions to occur, the radical trap must be active, present in an excess concentration, and the radical starting material must have a weak carbon–halogen...
Radical Anti-Markovnikov Addition to Alkenes: Thermodynamics01:32

Radical Anti-Markovnikov Addition to Alkenes: Thermodynamics

The anti-Markovnikov addition of hydrogen halides to an alkene is thermodynamically feasible only with HBr. The radical addition reaction with other hydrogen halides like HCl and HI is thermodynamically unfavorable.
The Response of Equilibria to the Conditions01:30

The Response of Equilibria to the Conditions

Named after the French chemist Henry Louis Le Chatelier, Le Chatelier's principle states that when a system at equilibrium is subjected to any change (like pressure, temperature, or concentration), the composition of the system adjusts in a way that counteracts the effect of this change, thereby attempting to restore the equilibrium.According to Le Chatelier's principle, for exothermic reactions, when the system's temperature is increased, the system will try to reduce the temperature. This...