Activation Energy

Thermodynamic calculations and arguments focus only on the initial and final states of a system. The path by which a change takes place is not considered. Intuitively, one might expect strongly exothermic reactions to occur spontaneously, but this is usually not true. For example, the methane combustion described above does not proceed spontaneously, but requires an initiating spark or flame. Once begun, the heat produced by the combustion serves to maintain the reaction until one or both of the reactants are completely consumed. Likewise, benzene has a heat of formation of +11.7 kcal/mol, suggesting that it could decompose spontaneously to hydrogen and carbon. Yet every chemist knows that benzene is a stable liquid that can be purified by distillation at 80 C without decomposition. Clearly, many potentially favorable reactions are prohibited or retarded by substantial energy barriers to the transformation. To understand why some reactions occur readily (almost spontaneously), whereas other reactions are slow, even to the point of being unobservable, we need to consider the intermediate stages through which reacting molecules pass on the way to products. Every reaction in which bonds are broken will necessarily have a higher energy transition state on the reaction path that must be traversed before products can form. This is true for both exothermic and endothermic reactions. In order for the reactants to reach this transition state, energy must be supplied from the surroundings and reactant molecules must orient themselves in a suitable fashion. The heat energy needed to raise the reactants to the transition state energy level is called the activation enthalpy, H. Further treatment of this subject, and examples of reaction path profiles that illustrate transition states are provided elsewhere in this text. However, in these introductory discussions a distinction between enthalpy and "potential energy" is not made. As expected, the rate at which chemical reactions proceed is, in large part, inversely proportional to their activation enthalpies, and is dependent on the concentrations of the reactants. The study of reaction rates is called chemical kinetics.