The " Instrument Function " of Isoperibolic Calorimeters; Excess Enthalpy Generation Due to the Parasitic Reduction of Oxygen

Two criticisms which are frequently advanced to counter observations of the generation of excess enthalpy in the cathodic polarisations of Pd-based electrodes in D2O-based electrolytes (e.g. see (1), (2)) are usually based on the assertion that the isoperibolic calorimeters used in these studies are imprecise and inaccurate. Furthermore, any excess enthalpy generation is then attributed to the reduction of electrogenerated oxygen although such assertions have not been accompanied by appropriate measurements. There is naturally a link between these two assertions. The first step in the development of any investigative methodology should be the determination of the relevant “instrument functions” of the instrumentation used, here the isoperibolic calorimeter illustrated in Fig. 1.