The theory of redoxokinetic effect and a general method for the determination of “a” of absolute reaction rates

Summary

The theory of the redoxokinetic effect has been formulated for smale a.c. fields. One interesting result coming out of the theory is that the redoxokinetic potential is proportional to the square of the a.c. field. Experiments have been done with the ferrous-ferric system which confirm the above theoretical result. From the observed values of the redoxokinetic potential it has been possible for the first time to get a general method for the d-l termination of “a” a factor introduced in the theory of Absolute reaction rates as applied to electrode processes. The magnitude of this quantity comes out to be 0·4987 ± 0·0001 for ferrous-ferric system (both 0·005 M) containing 1·0 M sulphuric acid as the supporting electrolyte. The corresponding value for the ferrous-ferric system (each 0·25 M) without any supporting electrolyte has been found to be 0·39, which is comparatively low. The exact significance of the latter result needs further investigation. The values of “a” given herein are tentative and illustrative of procedure.