The kinetics of chemical reactions were first studied in liquid solutions. These experiments involved mixing two liquids and following the change in the concentration of a reactant or product with time. The concentration was monitored by removing a small sample of the solution and stopping the reaction, for example, by rapidly lowering the temperature, or by following a physical property of the system in situ, for example, its color. Although the experiments were initially limited to slow reactions, they established the basic laws governing the rate at which chemical changes occur. The variables considered included the concentrations of the reactants and of the products, the temperature, and the pressure. Thus, the reacting system was examined using the variables normally considered for a system at equilibrium. Most reactions were found to be complex, that is, to be made up of several elementary steps which involved one or two reactants. As the fundamental concepts of chemical kinetics developed, there was a strong interest in studying chemical reactions in the gas phase. At low pressures the reacting molecules in a gaseous solution are far from one another, and the theoretical description of equilibrium thermodynamic properties was well developed. Thus, the kinetic theory of gases and collision processes was applied first to construct a model for chemical reaction kinetics. This was followed by transition state theory and a more detailed understanding of elementary reactions on the basis of quantum mechanics. Eventually, these concepts were applied to reactions in liquid solutions with consideration of the role of the non-reacting medium, that is, the solvent. An important turning point in reaction kinetics was the development of experimental techniques for studying fast reactions in solution. The first of these was based on flow techniques and extended the time range over which chemical changes could be observed from a few seconds down to a few milliseconds. This was followed by the development of a variety of relaxation techniques, including the temperature jump, pressure jump, and electrical field jump methods. In this way, the time for experimental observation was extended below the nanosecond range.
Theoretical insights into the reaction of Cp*(Cl)Hf(diene) with isonitriles