24 Mar.,2023


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The activation by cathodic polarization of passive iron in concentrated nitric acid (d = 1.4) has been investigated.

1. For short current pulses (1 msec. or less) a transient activation occurs when the product of current density and time exceeds a certain value. This limiting value is here designated as the "threshold." It is of the order of magnitude of 200 x 10–6 coulomb/cm.2.

2. After activation and repassivation the threshold is temporarily several times higher than before. This "refractory state" is due to the presence of nitrous acid and of oxide layers. The return of the threshold to normal values occurs in seconds or minutes, depending on the variety of iron wire.

3. Immediately after a subthreshold current pulse the threshold is reduced (summation). However, if the second pulse occurs a certain interval of time after the first the wire exhibits a certain degree of refractoriness (Gildemeister effect).

4. Oscillographic measurements reveal the existence of a latent period between the application of the stimulating pulse and the establishment of the active state. The duration of this latent period depends on the strength of the current pulse.

5. There exists a minimum current density (rheobase) below which no activation occurs however long the current is applied. Depending on the variety of iron used this current density varies between about 1 and 10 ma./cm.2. To produce activation a current of rheobasic strength does not have to be applied for an infinite time but only for about 100 msec. (maximum utilization time). Activation becomes manifest some time after termination of the activating pulse.

6. With currents of slowly increasing strength it is possible to reach current strengths several times higher than rheobase without obtaining activation (accomodation). Accomodation to a large extent depends on the variety of iron used. Details are given for currents increasing with a time constant of 0.5 second.

7. Potential measurements on wires in the refractory state show the existence of after potentials. Wires in the refractory state which are cathodically polarized show peculiar oscillograms. Both types of experiments point to the formation of nitrous acid as an essential element in the course of events.

8. With current densities only slightly above rheobase all wires exhibit simple activations only. With higher current densities certain types of wires exhibit periodic activations. The range of current densities in which such periodic activations occur varies with the type of wire. The lower limit is sometimes quite close to the rheobase.

9. A theory of periodic activations is presented which is modelled on the theory of self-excitatory electrical oscillations. As variables describing the state of the wire, the "degree of activation" and the "degree of refractoriness" are introduced. In the physicochemical system an autocatalytic process corresponds to the "falling characteristic" of electrical oscillations. The theory leads to a rational view of the interrelations between threshold, rheobase, accomodafion, refractoriness, and rhythm. The phenomena of conduction are not discussed here but their relation to the theory is briefly touched upon.

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