Excess heat production in the redox couple reaction of ferricyanide and ferrocyanide

In order to establish the universality of the excess heat production in electrochemical reaction, under a high magnetic field, as one of the most fundamental electrochemical reactions, the case of ferricyanide-ferrocyanide redox reaction was examined, where ionic vacancies with ± 1 unit charge were collided by means of magnetohydrodynamic (MHD) flow. As a result, from the pair annihilation of the vacancies with opposite signs, beyond 7 T, excess heat production up to 25 kJ·mol⁻¹ in average at 15 T was observed, which was attributed to the liberation of the solvation energy stored in a pair of the vacancy cores with a 0.32 nm radius, i.e., 112 kJ·mol⁻¹. Difference between the observed and expected energies comes from the small collision efficiency of 0.22 due to small radius of the vacancy core. Ionic vacancy initially created as a by-product of electrode reaction is unstable in solution phase, stabilized by releasing solvation energy. Ionic vacancy utilizes the energy to enlarge the core and stores the energy in it. As a result, solvated ionic vacancy consists of a polarized free space of the enlarged core surrounded by oppositely charged ionic cloud. The accuracy and precision of the measured values were ascertained by in situ standard additive method.