Single-Route Linear Catalytic Mechanism: A New, Kinetico-Thermodynamic Form of the Complex Reaction Rate
For a complex catalytic reaction with a single-route linear mechanism, a new, kinetico-thermodynamic form of the steady-state reaction rate is obtained, and we show how its symmetries in terms of the kinetic and thermodynamic parameters allow better discerning their influence on the result. Its reci...
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| Format: | Article |
| Language: | English |
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MDPI AG
2020-10-01
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| Series: | Symmetry |
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| Online Access: | https://www.mdpi.com/2073-8994/12/10/1748 |
| _version_ | 1797550256953491456 |
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| author | Gregory S. Yablonsky Denis Constales Guy B. Marin |
| author_facet | Gregory S. Yablonsky Denis Constales Guy B. Marin |
| author_sort | Gregory S. Yablonsky |
| collection | DOAJ |
| description | For a complex catalytic reaction with a single-route linear mechanism, a new, kinetico-thermodynamic form of the steady-state reaction rate is obtained, and we show how its symmetries in terms of the kinetic and thermodynamic parameters allow better discerning their influence on the result. Its reciprocal is equal to the sum of <i>n</i> terms (<i>n</i> is the number of complex reaction steps), each of which is the product of a kinetic factor multiplied by a thermodynamic factor. The kinetic factor is the reciprocal apparent kinetic coefficient of the <i>i</i>-th step. The thermodynamic factor is a function of the apparent equilibrium constants of the <i>i</i>-th equilibrium subsystem, which includes the <inline-formula><math display="inline"><semantics><mrow><mo stretchy="false">(</mo><mi>n</mi><mo>−</mo><mn>1</mn><mo stretchy="false">)</mo></mrow></semantics></math></inline-formula> other steps. This kinetico-thermodynamic form separates the kinetic and thermodynamic factors. The result is extended to the case of a buffer substance. It is promising for distinguishing the influence of kinetic and thermodynamic factors in the complex reaction rate. The developed theory is illustrated by examples taken from heterogeneous catalysis. |
| first_indexed | 2024-03-10T15:26:44Z |
| format | Article |
| id | doaj.art-9ac2ba792b0b4bebbe9ef606d2a4834d |
| institution | Directory Open Access Journal |
| issn | 2073-8994 |
| language | English |
| last_indexed | 2024-03-10T15:26:44Z |
| publishDate | 2020-10-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Symmetry |
| spelling | doaj.art-9ac2ba792b0b4bebbe9ef606d2a4834d2023-11-20T17:58:48ZengMDPI AGSymmetry2073-89942020-10-011210174810.3390/sym12101748Single-Route Linear Catalytic Mechanism: A New, Kinetico-Thermodynamic Form of the Complex Reaction RateGregory S. Yablonsky0Denis Constales1Guy B. Marin2McKelvey School of Engineering, Department of Energy, Environmental and Chemical Engineering, Washington University in St. Louis, St. Louis, MO 63130-4899, USADepartment of Electronics and Information Systems ELIS, Ghent University, B-9052 Gent, BelgiumLaboratory for Chemical Technology, Ghent University, B-9052 Gent, BelgiumFor a complex catalytic reaction with a single-route linear mechanism, a new, kinetico-thermodynamic form of the steady-state reaction rate is obtained, and we show how its symmetries in terms of the kinetic and thermodynamic parameters allow better discerning their influence on the result. Its reciprocal is equal to the sum of <i>n</i> terms (<i>n</i> is the number of complex reaction steps), each of which is the product of a kinetic factor multiplied by a thermodynamic factor. The kinetic factor is the reciprocal apparent kinetic coefficient of the <i>i</i>-th step. The thermodynamic factor is a function of the apparent equilibrium constants of the <i>i</i>-th equilibrium subsystem, which includes the <inline-formula><math display="inline"><semantics><mrow><mo stretchy="false">(</mo><mi>n</mi><mo>−</mo><mn>1</mn><mo stretchy="false">)</mo></mrow></semantics></math></inline-formula> other steps. This kinetico-thermodynamic form separates the kinetic and thermodynamic factors. The result is extended to the case of a buffer substance. It is promising for distinguishing the influence of kinetic and thermodynamic factors in the complex reaction rate. The developed theory is illustrated by examples taken from heterogeneous catalysis.https://www.mdpi.com/2073-8994/12/10/1748kinetico-thermodynamic rate equationseparation of kinetic and thermodynamic factorsdriving force |
| spellingShingle | Gregory S. Yablonsky Denis Constales Guy B. Marin Single-Route Linear Catalytic Mechanism: A New, Kinetico-Thermodynamic Form of the Complex Reaction Rate Symmetry kinetico-thermodynamic rate equation separation of kinetic and thermodynamic factors driving force |
| title | Single-Route Linear Catalytic Mechanism: A New, Kinetico-Thermodynamic Form of the Complex Reaction Rate |
| title_full | Single-Route Linear Catalytic Mechanism: A New, Kinetico-Thermodynamic Form of the Complex Reaction Rate |
| title_fullStr | Single-Route Linear Catalytic Mechanism: A New, Kinetico-Thermodynamic Form of the Complex Reaction Rate |
| title_full_unstemmed | Single-Route Linear Catalytic Mechanism: A New, Kinetico-Thermodynamic Form of the Complex Reaction Rate |
| title_short | Single-Route Linear Catalytic Mechanism: A New, Kinetico-Thermodynamic Form of the Complex Reaction Rate |
| title_sort | single route linear catalytic mechanism a new kinetico thermodynamic form of the complex reaction rate |
| topic | kinetico-thermodynamic rate equation separation of kinetic and thermodynamic factors driving force |
| url | https://www.mdpi.com/2073-8994/12/10/1748 |
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