Abstract A tubular flow-through electrode system for measuring the response time curves under the step change of concentration using an ammonium ion-selective poly(vinyl chloride) membrane electrode was described. The response time data are analyzed by the curve fitting method using two theoretical equations, which are an exponential type equation based on an assumption of the film diffusion and a square root type one based on that of the diffusion within the membrane, and a semiempirical equation of hyperbolic type. A method of curve fitting in which the equilibrium potential is regarded as an unknown parameter was described in detail. The initial part of the response time curves, where the potential change is large, was fitted by the exponential type equation, while the following part close to the equilibrium potential was fitted by the square root type one. The semiempirical equation could also be fitted to the wide range of the curves. The dependence of the time constant of the exponential type equation upon the flow rate of sample solution is examined; the results firmly supports both the film diffusion as a determining process for the initial part of the curve and the reliability of the present experimental system.
Read full abstract