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A Linear Free Energy Relationship for Gas‐Solid Interactions: Correlation between Surface Rate Constant and Diffusion Coefficient of Oxygen Tracer Exchange for Electron‐Rich Perovskites
Author(s) -
Merkle Rotraut,
Maier Joachim,
Bouwmeester Henny J. M.
Publication year - 2004
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.200460081
Subject(s) - enthalpy , diffusion , tracer , chemistry , thermodynamics , oxygen , energy exchange , constant (computer programming) , activation energy , physics , organic chemistry , nuclear physics , atmospheric sciences , computer science , programming language
The variation of the activation enthalpy for surface oxygen exchange ${{{^1 \hskip-1mm{{ /}}\hskip-0.5mm_2}}}$ O 2 + ${\rm V}^{\bullet\bullet}_{\rm O}$ ⇄ ${{{\rm {\rm O}}{{{\rm x}\hfill \atop {\rm {\rm O}}\hfill}}}}$ +2 h . with sample composition in (Ln,Sr)(Mn,Fe,Co)O 3− z perovskites is rigidly coupled to the variation of the overall reaction enthalpy (see picture). This is the first mechanistically well‐established example of a Hammett‐like relationship for inorganic gas‐solid reactions.