Read e-book online Comprehensive Treatise of Electrochemistry: The Double Layer PDF

By Roger Parsons (auth.), J. O’M. Bockris, Brian E. Conway, Ernest Yeager (eds.)

ISBN-10: 1461566843

ISBN-13: 9781461566847

ISBN-10: 146156686X

ISBN-13: 9781461566861

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8. Provided that [HA] is small in comparison with [KA] and that KA is not specifically adsorbed, the concentration of H + in the solution side of the interphase may be neglected and all the adsorbed H + may be regarded as forming the charge on the nonelectrolyte phase. 132) is described as the" Nernst equation" of the interfacial equilibrium. 132) really represents is the measurement of an activity in the bulk electrolyte in terms of the emf of an equilibrium cell, which has in fact nothing to do with the interphase being studied.

1-j,k dmj,k a k=O in order to simplify the writing of these equations. 28) V" dp THERMODYNAMICS OF ELECTROCHEMICAL INTERPHASES 13 It was noted by Everett(13) that the presence of the term y dAs in these equations can lead to the definition of four new thermodynamic potentials: U V" - yA. 29) f, = H" - yA. 30) 'H = = A" - yA. 36) For an ordinary interphase there are consequently eight characteristic equations. 44) (I) - eQcx These definitions lead to eight new characteristic equations, making a total of 16 for an interphase containing charged species: dG e = + y dAs T dS" + Va dp + y dAs - sa dT - p dV" + y dAs - sa dT + Va dp + y dAs dUe = T dS a dHe = TdS a + Va dp - As dy - d~re = -sa dT - p dva - As dy dfS).

Which depend on the placing of the boundary surfaces and have consequently an arbitrary magnitude. When there is a component common to the two phases, it is possible to use this component as the sole reference component. ,(2) for example). The form used here is based on the assumption that no component is common to phases a and {3. 4. 71) r;,k(O) where the subscript ~ indicates that the chemical potentials of all the components of the system are kept constant, while the subscript ~' indicates that all but the chemical potential indicated in the differential coefficient are kept constant.

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Comprehensive Treatise of Electrochemistry: The Double Layer by Roger Parsons (auth.), J. O’M. Bockris, Brian E. Conway, Ernest Yeager (eds.)


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