Oxidation / Cluster / p-Phenylenediamines / Silver / Photographic development The redox reaction between p-phenylenediamines and silver nitrate in aqueous acid solution was observed optically in a double wavelength photometer. In presence of a noble metal plate or larger clusters of silver, production of p-semiquinonediimines respective silver starts immediately, whereas without clusters present at the beginning of the reaction the maximum reaction rate is attained only after a certain induction period. The length of this induction period depends on the pH and the concentration of pphenylenediamine, but not on the silver ion concentration. It is not the number of the clusters that influences the induction period, but their size. The rate of the main reaction, however, is proportional to the number of the clusters formed. In dilute solutions the main reaction is of first order concerning both of the two reactants, in concentrated solution, however, it is of smaller order. Die Redoxreaktion zwischen p-Phenylendiaminen und Silbernitrat in saurer waBriger Losung wurde optisch in einem Zweiwellenlangenphotometer untersucht. In Gegenwart von Edelmetallblech oder groBeren Silberclustern setzt die p-Semichinondiimin -bzw.Silberbildung sofort ein, dagegen wird ohne besonderen Clusterzusatz die maximale Reaktionsgeschwindigkeit erst nach einer Induktionsperiode erreicht, deren Lange vom pH und von der p-Phenylendiamin-Konzentration, nicht aber von der Silberionenkonzentration abhangt. Die Zahl der entstehenden Cluster nimmt dabei kaum EinfluB auf die Dauer der Induktionsperiode, wohl aber ihre GroBe. Die Geschwindigkeit der Hauptreaktion ist demgegeniiber der Zahl der gebildeten Cluster proportional und in verdiinnter Losung 1. Ordnung hinsichtlich jedes der beiden Reaktanten, in konzentrierter Losung jedoch von kleinerer Ordnung.
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