On the Bridicka Catalytic Wave of Hydrogen(As a subject of panel discussion of protein wave)

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Reviw of the author's researches, with his private opinions, is presented. The problems are claimed to be classified into two groups ; i.e. that of electrode reaction and that of polarographic active pathological substance. Confining to the former, 23 questions are taken out. Along the potential axis, the three regions are coined to facilitate discussion ; capillarity region 0--1.0V., cobalt region -1.0--1.4V., and catalytic region -1.4--2.0V. The sweep velocity of applied voltage for any kind of polarographic methods is requested to be defined and controlled caring for adsorption, dcsorption, change of orientation, transformation, transformation of complex, reformation of different metal complex, and other kind of kinetic factors. The involvement of faradaic current and capacity current are discussed. The complicated behaviors of CoIII the capillarity region which were originally pointed out by Kalous is discussed contrasting the results of A.C. polarographic and oscil-lographic polarographic methods. Current in the catalytic region is understood being much involved accompaning with generation and adhesion of hydrogen gas on the electrode surface and the desorpion of surface active substance, no matter what itself is the depolarizer at the same time or not. From tensammetric consideration, desorption of a surface active substance seems to play a great roll for the doubling of the catalytic wave of hydrogen. The "crossing" of the double peaks was discussed from this point. Redioactivity-potential curve discriminates faradaie current from capacity current, ion-ion redox current, or other kind of current which does not accompany cobalt amalgamation on the electrode surface. It's results (1) show the no disturbance of cobalt reduction even at the potential of the catalytic phenomena, and (2) suggest the reduction of CoII→Co I corresponding the first wave of the splitted cobalt wave at cobalt region. The 3d orbital hydrid complex of CoIII is reduced to the outer orbital (N-shell) CoII complex, after passing through the several transient steps ; disturbance of coordination field by electric field near the working electrode, ligand field theoretical transformation of an activated electron and final acception of reducive electron, followed by reformation of ligand arrangement. The affairs of such complex chemical phenoma is still more complicated by possible mercury complex, π bonded cobalt complex, and desorption from the electrode surface etc.. Morphology of the catalytic wave has been considered in several ways, to explain the mechanism involved. "Chemical differential mechanism" has been taken out for the explanation of the catalytic wave of hydrogenhaving symmetric peak form. The positive current, due to sum of cobalt reduction and catalytic hydrogen reduction, may compensated by the one of following negative current or factors. (1) Atomic hydrogen on the electrode surface is oxidized and the produced H+ is fed to CoSR reforming CoSHR. (2) Hydrogen gas accumulated on the electrode surface protects a part of mass transfer of CoSHR. (3) Due to the desorption and molecular up-set reorientation of CoSHR the chance of H+ reduction is decreased.
日本ポーラログラフ学会の論文

著者

品川睦明
大阪大学工学部

On the Bridicka Catalytic Wave of Hydrogen(As a subject of panel discussion of protein wave)

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