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Wasserstoffüberspannung Und Struktur Der Doppelschicht

A. Frumkin
Published 1933 · Materials Science

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proportional, wo [H']t die Konzentration der //'-Ionen in der Doppelschicht, φ die Potentialdifferenz Elektrode—Lösung und a t eine Konstante bedeutet. Die Annahme der Proportionalität mit [//'], führt aber, worauf auch diese Autoren selbst hinweisen2), zu gewissen Schwierigkeiten bei der Ableitung der Gleichgewichtsbeziehung, da in der letzten die Konzentration in der Lösung [//'] und nicht die in der Doppelschicht [H']t auftreten muss. Im nachfolgenden möchte ich diese Verhältnisse etwas präzisieren, wodurch die Aufstellung einer Beziehung zwischen dem Abscheidungspotential des Wasserstoffs und dem Bau der Doppelschicht ermöglicht wird. Wir wollen zunächst mit E R D E Y G R U Z und VOLMER annehmen, dass nur die i/'-Ionen entladen werden, welche mit dem Metall in unmittelbarer Berührung stehen. Bezeichnen wir mit ζ das mittlere Potential in der Ebene, welche durch die Zentren dieser Ionen geht (Potential im Innern der Lösung gleich Null), so gilt für eine Doppelschicht die von der Sättigung noch genügend weit entfernt ist, die Beziehung:

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