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25. Typical i-t curves. (1) Diffusion current; (2) kinetic current; (3) adsorption current. ,,ϊ o o f o o I f,s FIG. 26. Dependence of the mean current (i) on the drop-time. Britton-Robinson buffer of pH 2-8; 1-2 x 10 ~3 M tropylium bromide m = 1*38 mg/sec, regulated drop-time, (a) iUm — ίλ\ (b) log * lim — log tvO—(iai)iim; ·—(hi + h2 + *i)iim; ®—total limiting current. 52 ORGANIC POLAROGRAPHIC ANALYSIS pulse show different forms. The processes controlled by diffusion, rate of chemical reaction, or rate of autocatalytic reaction have recently been shown to be distinguishable.
Examples of such behaviour are the reductions of carbonyl compounds. g. dioxane or dimethylformamide, can disclose whether or not, in the electrode process in aqueous solution, there is interaction with a molecule of water. 4. O T H E R TYPES OF C U R R E N T S IN POLAROGRAPHY Charging or condenser current, due to the charging of the elec trode (each drop) to the respective potential, observed even in pure supporting electrolyte, has already been mentioned (p. 2). This current depends on the magnitude of the surface of the mer cury drop and is thus proportional to the height of the mercury column A, similar to the adsorption current.
Z. Elektrochem. 62, 834 (1958). (49) V O N STACKELBERG, M . , H A N S , W . a n d J E N S C H , W . , Z. Elektrochem. 62, 839 (1958). (50) NÜRNBERG, H . , in Advances in Polarography (Proc. 2 n d I n t e r n a t . Congr. Polarography, C a m b r i d g e 1959) Vol. 2 , p . 694. P e r g a m o n Press, L o n d o n (1960). (51) MAJRANOVSKIJ, S. G . , Dokl. Akad. Nauk SSSR 114, 1272 (1957); 132, 1352 (1960). , H A N U S , V . a n d M A J R A N O V S K I J , S. G . , 2 . fiz. chim. (SSSR) 34, 651 (1960).