โ Scribed by Sidney W. Benson
No coin nor oath required. For personal study only.
There are very few general themes that cover the entire breadth of what is today called "chemistry". One of these is "the relation of molecular structure to chemical reactivity". Its experimental being is subsumed under the title of Kinetics.
Chemical Kinetics is today a fairly mature discipline which has entered a period of development where it is of great fundamental as well as practical importance. I t is at this stage of vital importance that current advances and practices become easily and uniformly available. I t is of special importance that kineticists exploring solution or gas phase reactions realize that rate parameters in the two systems are related, and that radical species in one phase will not have kinetic parameters vastly different in the other phase. I n a similar vein, there are no sharp boundaries, nor should there be, between the kinetic understanding of organic and inorganic systems.
The development of chemical kinetics has been very uneven in the various traditional disciplines of chemistry. Some groups of physical chemists are keenly aware that the enthalpy changes of many elementary step reactions can be estimated, or are known, and that these place a constraint on the rates of such steps. However, not so many are aware that the entropy changes are equally well known and that these place similar constraints on these rates. The same, or greater, differences in awareness exist over the entire spectrum of kineticists-physical, physical organic, organic, biochemical, etc. I t is the hope of the editors that this Journal will become the medium of exchange and communication for kineticists in all fields who, though their allegiances to disciplines may vary, are united by general interest in the quantitative relation between structure and reactivity. One of the benefits which we shall try to realize in the inauguration of this Journal will be a more uniform set of standards for judging kinetic research. Thus, kinetic data are structurally meaningful only when the overall reaction has been identified. Sound kinetic data should rest on the demonstration of stoichiometry, mass balances, and should incorporate knowledge of the effects of impurities (or surface). Reported Arrhenius (or transition state) parameters should be accompanied by statements of error limits which are in turn, critically dependent on the temperature range used as well as on the precision of the rate constants.
It is our purpose to encourage the submission of papers that explore the quantitative relationship between structure and reactivity. These would recognize that no quantitative piece of rate datum is a universe unto itself, but rather that all such data are now capable of being put to the test of quantitative consistency with a large body of experiment and theory.
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