Fluctuation spectroscopy: determination of chemical reaction kinetics from the frequency spectrum of fluctuations.

The kinetic parameters of a chemical reaction were obtained from analysis of the frequency spectrum of the fluctuations (i.e., "noise") in the concentrations of the reactants. In "fluctuation spectroscopy," no external perturbation is applied and the system remains in macroscopic chemical equilibrium during the experiment. Results obtained by this method for the dissociation reaction of beryllium sulfate agree well with those obtained by relaxation methods in which the approach to equilibrium is analyzed. Other noise sources not originating from a chemical reaction were observed and analyzed. The most prominent of these arose from the flow of an electrolyte through a capillary. The method of fluctuation spectroscopy should be applicable to problems of physical, chemical, and biological interest.