Calorimetric and thermodynamic analysis of palladium-deuterium electrochemical cells

An analysis is made of the chemical heats liberated from a palladium-deuterium electrochemical cell operating inside a calorimeter. It is important, in such an analysis, to carefully identify the chemical and electrochemical sources of heat, before any “excess heats” can be ascribed to non-chemical reactions.⁽¹⁾ The calorimeter measures the enthalpy (ΔH _r ) of the reaction; whereas, the electrochemical voltage of the cell reflects the free energy (ΔG _r ) of the reaction within the Pd-D electrolysis cell. The heat energy from the calorimeter cell therefore doesnot equal the electrical energy supplied to the cell, as might initially be expected. The magnitudes of the differing calorimetric and electrochemical energies were found to be related through the “thermoneutral potential” (ξ_H) of the electrochemical reaction. The chemical heat theoretically expected from the calorimeter is given by (1) I(ξ_L-ξ_H), the cell current (I), multiplied by the difference between the operating cell voltage (ξ_L) and the thermoneutral potential (ξ_H), rather than (2) Iξ_L, the electrical input power. This was verified empirically using a freon vaporization calorimeter, which operates on the principle of accurate measurement of the vaporization rate of liquid freon which completely surrounds the electrochemical cell. The calorimetrically-measured heats observed from a Pt/D₂O, 0.1M LiOD/Pd electrochemical cell were within 2% of the thermoneutral potential predicted value, I(ξ_L-ξ_H); but were found to be 15–30% less than the electrical work supplied to the cell, Iξ_L. Measurements of D₂O consumed by the cell reactions also verified that essentially no significant recombination of D₂ and O₂ gases occurred within the cell. No “excess heats” were observed from this Pd cell during the 36 days of its electrolytic operation. Likewise, no increase in the neutron flux around the cell was found, using three³He radiation detectors.