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Quantum mechanical relations in interface processes at electrode systems of the second kind
Author(s) -
Winzer A.
Publication year - 1979
Publication title -
kristall und technik
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.377
H-Index - 64
eISSN - 1521-4079
pISSN - 0023-4753
DOI - 10.1002/crat.19790140318
Subject(s) - nernst equation , electrode , chemistry , electrochemistry , ionic bonding , ion , quantum , electrode potential , reference electrode , thermodynamics , analytical chemistry (journal) , physics , quantum mechanics , organic chemistry , chromatography
It is shown that the difference of the electrochemical standard potentials between Ag/AgCl(s), KCl (aq, a = 1 mole l −1 ) and Ag/AgBr(s), KBr (aq, a = 1 mole l −1 can be attributed to the ion exchange from the AgCl phase to the AgBr phase. In this process, quantum mechanical relations play an essential part. A relation derived from Einstein's equation for calculating the inner energy of an ionic crystal and from the AC‐Josephson equation allows the calculation of the difference of the electrochemical standard potentials between the electrode systems Ag/AgCl(s), Cl − ‐Ag/AgBr(s), Br − ; Cu/CuCl(s), Cl − ‐Cu/CuBr(s), Br − and Hg/Hg 2 Cl 2 (s), Cl − ‐Hg/Hg 2 Br 2 (s), Br − from the frequency of the longitudinal optical phonons. An equation for the quantum mechanical calculation of the nernst factor ( RT/zF ) in the so‐called Nernst equation is given. Thus, the structural parameters of the respective solid state electrodes are in close relation with the transport processes in electrode systems of the second kind.