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 basically made up our minds by way of double layer (EDL) at this boundary. it's as a result no shock that for the final, a minimum of, 100 years reason realization must have been founded 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 this time in the framework of thermodynamics. the sort of constrained technique is absolutely insufficient. The Gouy-Chapman thought and the Stern-Grahame version of the dense a part of EDL constructed 40-70 years in the past, adapted properly to fit the party, necessarily underlie any description of EDL. This path is quite too slender to provide an explanation for all of the proof at our disposal. A dire necessity has therefore arisen for widening the foundations of the micros copic concept. this can be exactly the aim of our monograph. Fur thermore, we will stay at size at the comparability of the idea with test: with no one of these comparative research, any concept, even if dependent 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
Example text
To take into account monolayer saturation, Langmuir introduced the saturation factor, assuming r = r ~ 1(1 + So ) = = k G"n/(1 + So-kG-n), where So is the adsorption site of a molecule for complete coverage of the monolayer. Introducing this factor into (48), we obtain the familiar Stern isotherm for the Charge*) rlt *) Actually, Stern suggested the isotherm, which is slightly different from (44). This difference, however, is insignificant and we 31 (50) Similarly, we obtain for adso~ption ( 51) Very few general conclusions can be deduced from (50) and (51).
The limits of applicability of the Poisson-Boltzmann equation (83). Curve 1, an error of 5%; curve 2, 10%. The shaded region corresponds to aqueous solutions of 1-1 electrolytes. 55 Bjerrum radius, and R is the mean ion diameter (it was assumed in 35,36 that the ions a~e spheres of the same diameter, so that all R~ are equal to Ro ). -e-,z. '. is the mean charge of electrolyte ions; '" 01 0/ the fraction of ions of sort 01 • Solid curves in Fig. 8 deliniate the region of applicability of (83), curve 1 corresponding to the accuracy 5% and curve 2 to 10%.
C13 (it) -f. tp(~ -f. ~ {5} +~J . t=O It follows immediately from (76) (cf. (13» (78) where (79) Similarly, we obtain from (71) (cf. (34» ~! ;~,~)=- /r; {~C({(Lj)+f eoftK~{ij)[e:J:p[- J (~;(R~)) +~~~. 4 J -, 'OljIcl -..... :. CI-