A general theoretical description of the transient behavior of the amperometric Clark oxygen electrode based upon a one-dimensional spherical model is given in analytical form and compared with existing data. The resulting expressions relate transient characteristics of the sensor to transport properties of the three layers which determine the rate of oxygen diffusion from ambient flowing liquid or semisolid tissue to the surface of the sensor cathode. Criteria are presented by which the errors associated with earlier, less comprehensive models may be estimated. The effects of variation in hemispherical electrode radius are investigated for sensors exhibiting typical transport characteristics. Decreasing this radius is predicted to lead to complete suppression of sensor sensitivity to flow rate, while the dependence of transient characteristics upon flow rate is only partially diminished. Contrary to what might be believed on the basis of intuition, this model predicts that the response time for a typical electrode will decrease with decreasing electrode radius only until the radius approaches 7 ~m; thereafter, further reductions in electrode radius are shown to cause the response time to increase.Oxygen probes of the Clark type usually consist of noble metal or Ag cathode and of reference Ag/AgC1 or Ag/Ag20 anode immersed in aqueous solution of suitable inorganic electrolyte. The electrode system is separated from a medium measured by a thin plastic membrane permeable to oxygen. These oxygen sensors are finding increasingly wide-spread use in dynamic measurements. Evaluation of the data obtained requires a knowledge of transient characteristics of the probe. The present state of knowledge on dynamic behavior of oxygen probes has been summarized in recent reviews (1, 2).When electrochemical conditions are chosen so as to allow the sensor to operate in the limiting diffusion current region with constant, four electron overall stoichiometry of electrochemical reduction of oxygen at the cathode, the probe dynamics is determined by rates of oxygen transport through the following three layers: (i) a thin layer of the medium in front of the probe membrane, i.e., the concentration boundary layer of the medium, (ii) the membrane, and (iii) the electrolyte layer between cathode and the membrane. Steady-state solutions have been published for two-layer spherical models considering either the membrane and the electrolyte layer (3, 15) or the membrane and the film layer (4,5,16,17). Grunewald (6) has solved the transient characteristics of one-layer spherical model; for the two layer model, he solved the response to a sudden concentration change within a film of infinite thickness. Lee et al. (5) have described unsteady solution based on two-layer spherical model for the case where the probe is switched on after its equilibration with the surrounding medium, Thus, the transient characteristics for the two-layer model for the step change in the concentration of oxygen were not dealt with by the authors (5, 6). The solution de...