Electrochemical Microcalorimetry
Electrochemical Microcalorimetry Kai Etzel, Katrin Bickel and Rolf Schuster Physical Chemistry, Karlsruhe Institute of Technology, Germany research interests: -Surfaces in vacuum and electrochemical environment structure, phase transition, ordering processes 10 nm ‚electronic structure‘, scanning tunneling spectroscopy (electrochemical STM, XPS, …) -Electrochemical microstructuring 0 -Thermodynamics and kinetics of electrochemical reactions metal deposition, H-adsorption/evolution (electrochemical STM, [mK] Temperature -0.3 0 0.1 0.2 microcalorimetry, surface plasmon resonance,…) Time [s] 1 Rolf Schuster Institute of Physical Chemistry, Physical Chemistry of Condensed Matter Electrochemical Microcalorimetry Kai Etzel, Katrin Bickel and Rolf Schuster Physical Chemistry, Karlsruhe Institute of Technology, Germany Historical: E. J. Mills, „On Electrostriction“, Proc. Roy. Soc. Lond. 26, 504 (1877) E. Bouty, „Sur un phénomène analogue au phénomène de Peltier“, Comptes Rendus 89, 146 (1879) Cu-deposition Cu-dissolution ⇒ decreasing temperature ⇒ increasing temperature „electrochemical Peltier heats“ 2- SO4 Cu2+ Cu-plated 2 Rolf Schuster Institute of Physical Chemistry, Physical Chemistry of Condensed Matter What do we learn from electrochemical microcalorimetry? In „conventional“ calorimetry: qm = Δ R H; p,T = const. In electrochemical calorimetry: electrical work: wel,m = z ⋅ F ⋅φ = −Δ RG = −(Δ R H −TΔ R S); from the ‚chemical reaction‘ heat transfer from surrounding ⇒ qm = Δ RG − Δ R H = −TΔ R S; Ostwald (1903) We measure the reaction entropy,
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