Hydrodynamic Spectroelectrochemical Method and its Application

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A new spectroelectrochemical method including forced convection was constructed by setting a channel flow cell possessing a working electrode and a window in the upper and the lower course of the flow, respectively, in a spectrophotometer. The collection efficiency was defined as (absorbance x flow rate)/(current). It was independent on the flow rate in the larger flow-rate region than 100cm/s but became smaller with the increasing distance between the electrode and the light path. This method was applied to determination of sulfonation rate constant of p-benzoquinone. Hydroquinone was electrochemically oxidized to p-zenzoquinone in a sulfite solution, p-bennzoquinone was determined in the light path spectrochemically The pressent method was not disturbed by the presence of sulfite, which makes the anodic oxdation of hydroquinone irrevsible. By analyzing the sulfite concentration dependence of the collection efficiency with digital simulation technique 4.7x10ィイD17ィエD1 MィイD1-1ィエD1 sィイD1-1ィエD1 was obtained as the rate consatant for the sulfonation at pH9.0.