Non-Equilibrium Thermodynamics and Stochastic Dynamics of a Bistable Catalytic Surface Reaction
Catalytic surface reaction networks exhibit nonlinear dissipative phenomena, such as bistability. Macroscopic rate law descriptions predict that the reaction system resides on one of the two steady-state branches of the bistable region for an indefinite period of time. However, the smaller the catal...
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| Format: | Article |
| Language: | English |
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MDPI AG
2018-10-01
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| Series: | Entropy |
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| Online Access: | https://www.mdpi.com/1099-4300/20/11/811 |
| _version_ | 1798039651152297984 |
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| author | Miguel Pineda Michail Stamatakis |
| author_facet | Miguel Pineda Michail Stamatakis |
| author_sort | Miguel Pineda |
| collection | DOAJ |
| description | Catalytic surface reaction networks exhibit nonlinear dissipative phenomena, such as bistability. Macroscopic rate law descriptions predict that the reaction system resides on one of the two steady-state branches of the bistable region for an indefinite period of time. However, the smaller the catalytic surface, the greater the influence of coverage fluctuations, given that their amplitude normally scales as the square root of the system size. Thus, one can observe fluctuation-induced transitions between the steady-states. In this work, a model for the bistable catalytic CO oxidation on small surfaces is studied. After a brief introduction of the average stochastic modelling framework and its corresponding deterministic limit, we discuss the non-equilibrium conditions necessary for bistability. The entropy production rate, an important thermodynamic quantity measuring dissipation in a system, is compared across the two approaches. We conclude that, in our catalytic model, the most favorable non-equilibrium steady state is not necessary the state with the maximum or minimum entropy production rate. |
| first_indexed | 2024-04-11T21:56:49Z |
| format | Article |
| id | doaj.art-73e2cfab31af457e99c4301c51441355 |
| institution | Directory Open Access Journal |
| issn | 1099-4300 |
| language | English |
| last_indexed | 2024-04-11T21:56:49Z |
| publishDate | 2018-10-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Entropy |
| spelling | doaj.art-73e2cfab31af457e99c4301c514413552022-12-22T04:01:05ZengMDPI AGEntropy1099-43002018-10-01201181110.3390/e20110811e20110811Non-Equilibrium Thermodynamics and Stochastic Dynamics of a Bistable Catalytic Surface ReactionMiguel Pineda0Michail Stamatakis1Department of Chemical Engineering, University College London, Roberts Building, Torrington Place, London WC1E 7JE, UKDepartment of Chemical Engineering, University College London, Roberts Building, Torrington Place, London WC1E 7JE, UKCatalytic surface reaction networks exhibit nonlinear dissipative phenomena, such as bistability. Macroscopic rate law descriptions predict that the reaction system resides on one of the two steady-state branches of the bistable region for an indefinite period of time. However, the smaller the catalytic surface, the greater the influence of coverage fluctuations, given that their amplitude normally scales as the square root of the system size. Thus, one can observe fluctuation-induced transitions between the steady-states. In this work, a model for the bistable catalytic CO oxidation on small surfaces is studied. After a brief introduction of the average stochastic modelling framework and its corresponding deterministic limit, we discuss the non-equilibrium conditions necessary for bistability. The entropy production rate, an important thermodynamic quantity measuring dissipation in a system, is compared across the two approaches. We conclude that, in our catalytic model, the most favorable non-equilibrium steady state is not necessary the state with the maximum or minimum entropy production rate.https://www.mdpi.com/1099-4300/20/11/811fluctuationschemical master equationbistabilityentropy production ratenon-equilibrium steady state |
| spellingShingle | Miguel Pineda Michail Stamatakis Non-Equilibrium Thermodynamics and Stochastic Dynamics of a Bistable Catalytic Surface Reaction Entropy fluctuations chemical master equation bistability entropy production rate non-equilibrium steady state |
| title | Non-Equilibrium Thermodynamics and Stochastic Dynamics of a Bistable Catalytic Surface Reaction |
| title_full | Non-Equilibrium Thermodynamics and Stochastic Dynamics of a Bistable Catalytic Surface Reaction |
| title_fullStr | Non-Equilibrium Thermodynamics and Stochastic Dynamics of a Bistable Catalytic Surface Reaction |
| title_full_unstemmed | Non-Equilibrium Thermodynamics and Stochastic Dynamics of a Bistable Catalytic Surface Reaction |
| title_short | Non-Equilibrium Thermodynamics and Stochastic Dynamics of a Bistable Catalytic Surface Reaction |
| title_sort | non equilibrium thermodynamics and stochastic dynamics of a bistable catalytic surface reaction |
| topic | fluctuations chemical master equation bistability entropy production rate non-equilibrium steady state |
| url | https://www.mdpi.com/1099-4300/20/11/811 |
| work_keys_str_mv | AT miguelpineda nonequilibriumthermodynamicsandstochasticdynamicsofabistablecatalyticsurfacereaction AT michailstamatakis nonequilibriumthermodynamicsandstochasticdynamicsofabistablecatalyticsurfacereaction |