By Ian S. Longmuir
Advances in Polarography, quantity 2 covers the lawsuits of the second one overseas Congress held at Cambridge in 1959 in honor of the seventieth birthday of Professor Heyrovsky.
This quantity consists of 35 chapters and starts off with extensive discussions at the theoretical and primary facets, in addition to pertinent equations in polarography. significant chapters are dedicated to the chemical and metallurgical purposes of the process, with emphasis at the hint choice of definite compounds. the rest chapters discover different program of particular polarographic process, akin to nicotinic acid, iso-benzpyrylium salts, and steel complicated research.
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Additional resources for Advances in Polarography. Proceedings of the Second International Congress Held at Cambridge 1959
I Λi r E I/2 - E F I G . 1. Schematic polarogram of p-nitrosophenol in neutral solution. pH. Theoretical curve in Fig. 2 is calculated by use of equation (20), in which AVr = V[380 + 4 · 10(pH~2)] · 10- 2 (22) is assumed and the wave height in alkaline solution is taken to be 2 ia1 (n\ — U2 = 2). The theoretical curve in Fig. 2 and Table 1 show how the TABLE 1. E F F E C T OF K I N E T I C PARAMETER X\/T pH X\/r tdl 1-12 + ΧΛ/Τ JE (mV) = ON THE POLAROGRAPHIC W A V E 2 3 4 5 6 7 0196 0-205 0-280 0-661 2-00 6-37 0149 0155 0-20 0-37 0-64 0-83 20 21 2-8 5-8 12-8 23-8 8 20-0 0-95 36-8 9 63-2 0-98 510 10 200 1-00 65-3 462 ISAMU TACHi a n d MITSUGI SENDA limiting current changes with t h e change of kinetic parameter λ.
These might offer a reason for the change of the slope of polarogram of jp-nitrosophenol in basic solution. Detailed analysis of equation (16) needs further knowledge on 0i. The present discussion on the polarographic behaviour of ^-nitrosophenol does not claim t h a t the reduction mechanism of j9-nitrosophenol is expressed by mechanism (C) or the like. F u r t h e r experimental results are needed. CONCLUSION A theory of polarographic current of stepwise electrode process has been given, in which a reduction product of the first electrochemical step under goes the second one after it suffers chemical change from an electroinactive to electroactive form for the second step.
Some organic sub stances, such as nitro or nitroso compounds, are known to undergo polaro graphic reduction in steps and in some cases these electrochemical steps are connected by chemical reaction with each other. In this paper the theory of polarographic current of stepwise electrode process involving chemical reaction will be given and the polarographic reduction mechanism of pnitrosophenol will be briefly discussed. MATHEMATICAL FORMULATION Let us consider an electrode process given by *i fcl' (A) B ^ C, Ki = — / t h a t is, a depolariser A is reduced to B by consumption of n\ electrons per molecule; the reductant B is electroinactive for further reduction and under goes a chemical reaction into an electroactive depolariser C.