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Mesoscopic nonequilibrium thermoydnamics

Mesoscopic nonequilibrium thermoydnamics. Application to interfacial phenomena. Miguel Rubi. Dynamics of Complex Fluid-Fluid Interfaces  Leiden, 2011. Interfaces. The interface is a thermodynamic system ; excess properties ; Local equilibrium holds .

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Mesoscopic nonequilibrium thermoydnamics

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  1. Mesoscopicnonequilibriumthermoydnamics Applicationtointerfacialphenomena Miguel Rubi Dynamics of Complex Fluid-Fluid Interfaces Leiden, 2011

  2. Interfaces • The interface is a thermodynamicsystem; excessproperties; Local equilibriumholds. • Transport and activatedprocessestake place • Thestate of thesurface can bedescribedbymeans of aninternalcoordinate shear bound free

  3. Activation shear Examples: Chemicalreactions, adsorption, evaporation, condensation, thermionicemmision, fuel cells…. stick slip Activation: toproceedthesystem has tosurmount a potentialbarrier; nonlinear NET: provides linear relationshipsbetweenfluxes and forces

  4. Nonequilibriumthermodynamics • Global description of nonequilibriumprocesses (k0; ω0) Shorterscales: memorykernels (Ex.generalyzedhydrodynamics, non-Markovian) • Description in terms of averagevalues; absence of fluctuations Fluctuations can beincorporatedthroughrandomfluxes (fluctuatinghydrodynamics) • Linear domain of fluxes and thermodynamicforces

  5. Chemical reactions Law of mass action linearization Conclusion: NET onlyaccountsforthe linear regime.

  6. Activation Unstable substance Final product Naked-eye: Sudden jump Watching closely Diffusion Progressive molecular changes

  7. Translocation of ions (through a protein channel) Biological membrane short time scale: local equilibrium along the coordinate Local, linear Global, non-linear biological pumps, chemical and biochemical reactions Arrhenius, Butler-Volmer, Law of mass action

  8. Protein folding Intermediate configurations, same as for chemical reactions

  9. Molecularmotors Energy transduction, Molecular motors

  10. Activated process viewed as a diffusion process along a reaction coordinate From local to global:

  11. What can we learn from kinetic theory? Boltzmann equation Chapman-Enskog LMA J. Ross, P. Mazur, JCP (1961)

  12. Thermodynamics and stochasticity J.M. Vilar, J.M. Rubi, PNAS (2001) Probability conservation: Entropy production: Fokker-Planck

  13. Molecular changes: diffusionthrough a mesoscopiccoordinate D. Reguera, J.M. Rubi and J.M. Vilar, J. Phys. Chem. B (2005); FeatureArticle Second law

  14. Meso-scale entropy production

  15. Relaxation equations J.M. Rubi, A. Perez, Physica A 264 (1999) 492 hydrodynamic Fick Maxwell-Cattaneo Burnett

  16. References • A. Perez, J.M. Rubi, P. Mazur, Physica A (1994) • J.M. Vilar and J.M. Rubi, PNAS (2001) • D. Reguera, J.M. Rubi and J.M. Vilar, J. Phys. Chem. B (2005); Feature Article • J.M. Rubi, Scientific American, November, 40 (2008)

  17. 1 2 ( ) 2 1 0 Adsorption Chemisorbed Physisorbed

  18. MNET of adsorption

  19. Langmuirequation I. Pagonabarraga, J.M. Rubi, Physica A, 188, 553 (1992)

  20. Evaporation and condensation D. Bedeaux, S. Kjelstrup, J.M. Rubi, J. Chem. Phys., 119, 9163 (2003)

  21. Condensationcoefficient

  22. Stick-slip transition shear stick slip C. Cheikh, G. Koper, PRL, 2003

  23. Conclusions • MNET offers a unified and systematicschemetoanalyzedissipativeinterfacialphenomena. • Thedifferentstates of thesurface are characterizedby a reactioncoordinate. • Chemicalreactions, adsorption, evaporation, condensation, thermionicemmision, fuel cells….

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