Download Electrical Double Layer at a Metal-dilute Electrolyte by G.A. Martynov PDF

By G.A. Martynov

Most of the homes of a metal-electrolyte interface, even the spe­ cific nature of an electrode response, proneness of a steel to cor­ rosion, etc., are essentially made up our minds by means of double layer (EDL) at this boundary. it really is hence no shock that for the final, at the very least, 100 years purpose awareness must have been established on EDL. rather a lot of fabric has been accrued to this point that we're easi­ ly misplaced during this maze of knowledge. a considerable a part of the makes an attempt to systematize those evidence is made at the moment in the framework of thermodynamics. the sort of restricted technique is unquestionably insufficient. The Gouy-Chapman conception and the Stern-Grahame version of the dense a part of EDL constructed 40-70 years in the past, adapted accurately to fit the party, unavoidably underlie any description of EDL. This direction is quite too slim to give an explanation for the entire evidence at our disposal. A dire necessity has hence arisen for widening the foundations of the micros­ copic concept. this is often exactly the aim of our monograph. Fur­ thermore, we will live at size at the comparability of the idea with scan: with no this type of comparative research, any thought, besides the fact that stylish it can be, is simply an empty drum.

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Extra info for Electrical Double Layer at a Metal-dilute Electrolyte Solution Interface

Sample text

AF. Since the latter is known (see Fig. 2), K~Cl(Qe) is also known. Thus, using the experimental dependence of the electrode potential on the charge 4'm = ~m(Qe)' we can calculate the potential of the plane of maximum approach of ions ~~ = ~rn - Qe/Ke (see (11» and then determine the Gouy layer charge Q~GC) by formula (20). Finally, it is J. a simple matter to find the Stern layer charge troneutra1ity condition Q~St) = _(Q J. e Q1St) from the e1ec- + Q~GC». J. Cl holds true in the entire cathodic region.

E e *) To this end, we found the 39 3 I +5 +4 +3 +2 +I o -I -2 Fig. 7. Dependence of the Stern layer charge Q~St) on the adsorption plane potential 4V~ for solutions of LiCl0 4 (curve 1), KN0 3 (curve 2) and NH 4Cl (curve 3) in dimethyl sulfoxide on mercury 79. 40 ting the curves of Fig. 7, we integrated graphically the c~ge curves of papers 62,72. Naturally, in the latter case the accuracy was much lower. Nevertheless, it can easily be seen that all the curves intersect the abscissa axiS, indicative of the existence of the zero-charge point of the Stern layer.

If we introduce the notations (47) the Henry-Stern isotherm for (J Q~St) can be written in the form 39 1. ;p (- -) '"' eon-Shoe - 51.. iff -l/II... (5-£) (48) where l/IJ,. = e -l/1J EJ is the dimensionless potential in the adsorption plane. ~St) = L 01 rei ,we obtain 39 (49) r (the index "i" in Q~St) and ~st) 1. 1. refer to the ionic part of EDL). indicate that these quantities r « -Formulae (42) and (43) correspond to Henry's approximation = kG-n in the theory of monomolecular adsorption of non-charged particles.

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