Excess heat production of the pair annihilation of ionic vacancies in a copper redox reaction using a double bipolar MHD electrode.

Through a copper double bipolar magnetohydrodynamic (MHD) electrode (MHDE) producing twice the amounts of ionic vacancies than a conventional single MHDE, the molar excess heat of the pair annihilation of ionic vacancies, 702 kJ mol-1 at 10 T on average was obtained in a copper redox reaction. It was about twice as large as that of a single MHDE, 387 kJ mol-1 at the same magnetic field. This result strongly suggests that a multi-channel bipolar MHDE will produce much greater excess heat. To conserve the linear momentum and electric charge during electron transfer in an electrode reaction, ionic vacancies are created, storing the solvation energy in the polarized core of the order of 0.1 nm, and the pair annihilation of the vacancies with opposite charges liberates the energy as excess heat. The promoted excess heat by the double bipolar MHDE with a diffuser at 10 T was 710 ± 144 kJ mol-1, whereas as mentioned above, 702 ± 426 kJ mol-1 was obtained by the same electrode without such a diffuser. From the theoretical excess heat of 1140 kJ mol-1, the collision efficiencies in pair annihilation were 0.623 ± 0.126 and 0.616 ± 0.374, respectively. From these results, the reproducibility of the thermal measurement was experimentally validated. At the same time, it was concluded that at magnetic fields beyond 10 T, the concentration of ionic vacancy and the collision efficiency take constant uppermost values.

Long-Term Electrodeposition under a Uniform Parallel Magnetic Field. 2. Flow-Mode Transition from Laminar MHD Flow to Convection Cells with Two-Dimensional (2D) Nucleation.

Following the analysis of the self-organization of two-dimensional (2D) nuclei in Part 1, the flow-mode transition from laminar magnetohydrodynamics (MHD) flow to convection cells accompanied by 2D nucleation under a uniform parallel magnetic field was theoretically examined using the statistical mechanics of nonequilibrium fluctuation. As a result, it was clarified that secondary nodules of 2D nuclei develop with multiple nucleations during the transition, forming a one-upon-another structure. Then, the evolution of the convection cells as well as the secondary nodules requires unstable growth of the asymmetrical fluctuations by the specific adsorption of an ion. As predicted by the theory, the electrolytic current in copper deposition with specific adsorption of hydrogen ions under a parallel magnetic field developed with time, resulting in a nonlinear steplike curve in a 1200 s deposition time.

Long-Term Electrodeposition under a Uniform Parallel Magnetic Field. 1. Instability of Two-Dimensional Nucleation in an Electric Double Layer.

Under a parallel magnetic field, after long-term copper deposition from an acidic copper sulfate solution, numerous spherical secondary nodules of 10 to 100 µm diameters were formed one upon another in dendritic mode. This is a new type of micro-magnetohydrodynamic (MHD) effect arising from the unstable growth of three-dimensional (3D) and two-dimensional (2D) nuclei by specific adsorption of hydrogen ions (second micro-MHD effect). From the viewpoint of instability in electrodeposition, though 3D nucleation in the diffusion layer is always unstable, with ionic specific adsorption such as hydrogen ions, stable 2D nucleation turns unstable after long-term deposition. The resultant competitive growth of 3D and 2D nuclei produces spherical nodules as their composite, leading to their dendritic growth. Furthermore, though negligibly small, nonequilibrium fluctuations occurring in 2D nucleation migrate with the laminar solution flow caused by Lorentz force (MHD flow). Depending on whether the ionic adsorption is specific or nonspecific, the traveling asymmetrical fluctuation changes the direction to the upstream or downstream side, respectively.

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.

Excess Heat Production by the Pair Annihilation of Ionic Vacancies in Copper Redox Reactions.

In the pair annihilation of ionic vacancies with opposite charges, a drastic excess heat production up to 410 kJ mol-1 in average at 10 T (i. e., 1.5 times larger than the heat production by the combustion of H2,  285.8 kJ mol-1) was observed, which was then attributed to the emission of the solvation energy stored in 0.61 nm radius vacancies with two unit charges. Under a high magnetic field, using Lorentz force, we made ionic vacancies created in copper cathodic and anodic reactions collide with each other, and measured the reaction heat by their annihilation. Ionic vacancy is initially created as a byproduct in electrode reaction in keeping the conservation of linear momentum and electric charge during electron transfer. The unstable polarized particle is stabilized by solvation, and the solvation energy is stored in the free space of the order of 0.1 nm surrounded by oppositely charged ionic cloud. The collision of the ionic vacancies was carried out by circulation-type magnetohydrodynamic electrode (c-type MHDE) composed of a rectangular channel with a pair of copper electrodes and a narrow electrolysis cell.

Chiral Symmetry Breaking in Magnetoelectrochemical Etching with Chloride Additives.

Magnetoelectrolysis (electrolysis under magnetic fields) produces chiral surfaces on metal thin films, which can recognize the enantiomers of amino acids. Here, the chiral surface formation on copper films is reported in magnetoelectrochemical etching (MEE) at 5T with chloride additives. In the absence of additives, the surface chirality signs of MEE films depended on the magnetic field polarity. On the contrary, the MEE films prepared with the additives exhibited only d-activity in both magnetic field polarities. This result implies that the specific adsorption of chloride additives induces the chiral symmetry breaking for the magnetic field polarity.

Magneto-Dendrite Effect: Copper Electrodeposition under High Magnetic Field.

Ionic vacancy is a by-product in electrochemical reaction, composed of polarized free space of the order of 0.1 nm with a 1 s lifetime, and playing key roles in nano-electrochemical processes. However, its chemical nature has not yet been clarified. In copper electrodeposition under a high magnetic field of 15 T, using a new electrode system called cyclotron magnetohydrodynamic (MHD) electrode (CMHDE) composed of a pair of concentric cylindrical electrodes, we have found an extraordinary dendritic growth with a drastic positive potential shift from hydrogen-gas evolution potential. Dendritic deposition is characterized by the co-deposition of hydrogen molecule, but such a positive potential shift makes hydrogen-gas evolution impossible. However, in the high magnetic field, instead of flat deposit, remarkable dendritic growth emerged. By examining the chemical nature of ionic vacancy, it was concluded that ionic vacancy works on the dendrite formation with the extraordinary potential shift.

Origin of Nanobubbles Electrochemically Formed in a Magnetic Field: Ionic Vacancy Production in Electrode Reaction.

As a process complementing conventional electrode reactions, ionic vacancy production in electrode reaction was theoretically examined; whether reaction is anodic or cathodic, based on the momentum conservation by Newton's second law of motion, electron transfer necessarily leads to the emission of original embryo vacancies, and dielectric polarization endows to them the same electric charge as trans- ferred in the reaction. Then, the emitted embryo vacancies immediately receive the thermal relaxation of solution particles to develop steady-state vacancies. After the vacancy production, nanobubbles are created by the collision of the vacancies in a vertical magnetic field.

Lifetime of Ionic Vacancy Created in Redox Electrode Reaction Measured by Cyclotron MHD Electrode.

The lifetimes of ionic vacancies created in ferricyanide-ferrocyanide redox reaction have been first measured by means of cyclotron magnetohydrodynamic electrode, which is composed of coaxial cylinders partly exposed as electrodes and placed vertically in an electrolytic solution under a vertical magnetic field, so that induced Lorentz force makes ionic vacancies circulate together with the solution along the circumferences. At low magnetic fields, due to low velocities, ionic vacancies once created become extinct on the way of returning, whereas at high magnetic fields, in enhanced velocities, they can come back to their initial birthplaces. Detecting the difference between these two states, we can measure the lifetime of ionic vacancy. As a result, the lifetimes of ionic vacancies created in the oxidation and reduction are the same, and the intrinsic lifetime is 1.25 s, and the formation time of nanobubble from the collision of ionic vacancies is 6.5 ms.

Surface chirality induced by rotational electrodeposition in magnetic fields.

The surfaces of minerals could serve important catalytic roles in the prebiotic syntheses of organic molecules, such as amino acids. Thus, the surface chirality is responsible for the asymmetric syntheses of biomolecules. Here, we show induction of the surface chirality of copper metal film by electrodeposition via electrochemical cell rotation in magnetic fields. Such copper film electrodes exhibit chiral behaviour in the electrochemical reaction of alanine enantiomers, and the rotating direction allows control of the chiral sign. These findings are discussed in connection with the asymmetric influence of the system rotation on the magnetohydrodynamic micro-vortices around the electrode surfaces.

Chirality of magneto-electrodeposited metal film electrodes.

The chiral electrode behaviors of magneto-electrodeposited (MED) Ag and Cu films were examined for the electrochemical reactions of D-glucose, L-glucose and L-cysteine. The Ag and Cu films were electrodeposited under a magnetic field of 2 T parallel (+2 T) or antiparallel (-2 T) to the faradaic current. For MED films of both Ag and Cu, the oxidation current of L-glucose was larger than that of D-glucose on the +2 T-film electrodes, and the results were opposite on the - 2 T-film electrodes. These facts demonstrate that the MED metal films possess the ability of chiral recognition for D- and L-glucoses. The MED Ag film electrodes also exhibited chiral behavior for the oxidation of L-cysteine.