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 decided through double layer (EDL) at this boundary. it really is for this reason no shock that for the final, at the very least, 100 years cause recognition must have been based on EDL. a lot of fabric has been accumulated so far 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 present in the framework of thermodynamics. the sort of constrained procedure is definitely 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 correctly to fit the party, unavoidably underlie any description of EDL. This direction is very too slim to give an explanation for the entire evidence at our disposal. A dire necessity has therefore arisen for widening the rules 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 test: with no any such comparative research, any idea, notwithstanding dependent it can be, is simply an empty drum.
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Extra resources for Electrical Double Layer at a Metal-dilute Electrolyte Solution Interface
For sufficiently low potentials, sh(ke 'I'ct / B ) can be replaced by its argument, which yields Rn 1 is given by (23). This is the basic equation of the where ~ = Onsager-Samaras 10,11 theory, which in turn is a generalization of the equation considered by Wagner 9,11. Since it is a second-order equation, it needs a boundary conqition at z = 0 i. fo(" is a SOluti~n of the Laplace equation I!. = 0 for the region if.. <. 0*); at infinity z =::J. 0 0 , as before, 't (39) *) Strictly speaking, Eqs.
At present, Grahame's ideas have gained unanimous recognition and suppressed almost completely Stern's ideas. The Grahame theory should, therefore, be considered at greater length. A necessity has long arisen to explain why some ions can be adsorbed and the other cannot. Grahame suggested that this is due to solvation. When approaching the electrode surface, strongly solvated cations cannot shed their solvation sheath and, hence, cannot reach the surface of the metal. Therefore, they are not affected by specific adsorption forces, which act efficiently only at very short distances.
Let us only note that formulae (50) and (51) derived in Refs. 39,40 differ only in the form from those presented in Ref. 77 • . 32 layer. Therefore, a "deficit" in one kind of the forces may be compensated by an excess in the forces of the other kind and vice versa. It will be shown in the next paragraph that the "equality" hypothesis is excellently confirmed in experiment. e. if all ~~ 0). This is not the case, however, as can be seen from (51). e. if all ~ are not equal to +0<::'). In practice, however, the contribution of the Stern layer io the total balance of charge and substance is so small for = 'If = 0 and ~ = 0 that it can be neglected.