Fluctuation Spectroscopy: Determination from the Frequency Spectrum of Fluctua

The kinetic parameters of a chemical reac- tion were obtained from analysis of the frequency spec- trum of the fluctuations (i.e., "noise") in the concentra- tions 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 reac- tion of berylliunm sulfate agree well with those obtained by relaxation methods in which the approach to equilib- rium 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 spec- troscopy should be applicable to problems of physical, chemical, and biological interest. Chemical equilibria are maintained by a balance between the rates of competing reactionss. At equilibrium the average