A mechanism-based finite-rate surface catalysis model for simulating reacting flows

Paolo Valentini, Thomas E Schwartzentruber, Ioana Cozmuta

Research output: Chapter in Book/Report/Conference proceedingConference contribution

6 Citations (Scopus)

Abstract

A mechanism-based finite-rate wall boundary condition is implemented in a state-of-the- art finite volume CFD thermochemical nonequilibrium code to study a high enthalpy CO2 flow over blunt bodies. All the relevant surface processes responsible for the catalytic behavior of the wall are accounted for, including adsorption and desorption (both atomic and molecular), and Eley-Rideal and Langmuir-Hinshelwood recombinations. The model only requires the specification of the reaction rates for each of the processes considered, and the law of mass action is used to compute surface coverages and mass fluxes produced or consumed at the wall due to its catalytic activity. The kinetic rates are chosen to describe a platinum surface, with a fairly high degree of catalycity with respect to CO oxidation. As expected, the predicted heat flux is intermediate between the two extrema, namely the non-catalytic and supercatalytic wall assumptions. Because the only input of the model are the reaction rates, which are usually unavailable or affected by a large experimental uncertainty, the use of Molecular Dynamics simulations employing the Quantum Chemistry based reactive force field ReaxFF is proposed as a novel approach to both determine and characterize each of the underlying processes which collectively cause the wall catalytic activity. Because (dissociative) adsorption is a fundamental step leading to surface recombinations, the sticking of O2 on Pt(111) is studied using ReaxFF Molecular Dynamics simulations.

Original languageEnglish (US)
Title of host publication41st AIAA Thermophysics Conference
StatePublished - Dec 1 2009
Event41st AIAA Thermophysics Conference - San Antonio, TX, United States
Duration: Jun 22 2009Jun 25 2009

Publication series

Name41st AIAA Thermophysics Conference

Other

Other41st AIAA Thermophysics Conference
CountryUnited States
CitySan Antonio, TX
Period6/22/096/25/09

Fingerprint

reacting flow
Catalysis
catalysis
Reaction rates
Molecular dynamics
Catalyst activity
catalytic activity
Adsorption
reaction kinetics
Quantum chemistry
molecular dynamics
Computer simulation
blunt bodies
adsorption
Heat flux
quantum chemistry
Platinum
range (extremes)
Enthalpy
Desorption

Cite this

Valentini, P., Schwartzentruber, T. E., & Cozmuta, I. (2009). A mechanism-based finite-rate surface catalysis model for simulating reacting flows. In 41st AIAA Thermophysics Conference [2009-3935] (41st AIAA Thermophysics Conference).

A mechanism-based finite-rate surface catalysis model for simulating reacting flows. / Valentini, Paolo; Schwartzentruber, Thomas E; Cozmuta, Ioana.

41st AIAA Thermophysics Conference. 2009. 2009-3935 (41st AIAA Thermophysics Conference).

Research output: Chapter in Book/Report/Conference proceedingConference contribution

Valentini, P, Schwartzentruber, TE & Cozmuta, I 2009, A mechanism-based finite-rate surface catalysis model for simulating reacting flows. in 41st AIAA Thermophysics Conference., 2009-3935, 41st AIAA Thermophysics Conference, 41st AIAA Thermophysics Conference, San Antonio, TX, United States, 6/22/09.
Valentini P, Schwartzentruber TE, Cozmuta I. A mechanism-based finite-rate surface catalysis model for simulating reacting flows. In 41st AIAA Thermophysics Conference. 2009. 2009-3935. (41st AIAA Thermophysics Conference).
Valentini, Paolo ; Schwartzentruber, Thomas E ; Cozmuta, Ioana. / A mechanism-based finite-rate surface catalysis model for simulating reacting flows. 41st AIAA Thermophysics Conference. 2009. (41st AIAA Thermophysics Conference).
@inproceedings{f8a9a77c815e4b8d81323f7bfa74beb1,
title = "A mechanism-based finite-rate surface catalysis model for simulating reacting flows",
abstract = "A mechanism-based finite-rate wall boundary condition is implemented in a state-of-the- art finite volume CFD thermochemical nonequilibrium code to study a high enthalpy CO2 flow over blunt bodies. All the relevant surface processes responsible for the catalytic behavior of the wall are accounted for, including adsorption and desorption (both atomic and molecular), and Eley-Rideal and Langmuir-Hinshelwood recombinations. The model only requires the specification of the reaction rates for each of the processes considered, and the law of mass action is used to compute surface coverages and mass fluxes produced or consumed at the wall due to its catalytic activity. The kinetic rates are chosen to describe a platinum surface, with a fairly high degree of catalycity with respect to CO oxidation. As expected, the predicted heat flux is intermediate between the two extrema, namely the non-catalytic and supercatalytic wall assumptions. Because the only input of the model are the reaction rates, which are usually unavailable or affected by a large experimental uncertainty, the use of Molecular Dynamics simulations employing the Quantum Chemistry based reactive force field ReaxFF is proposed as a novel approach to both determine and characterize each of the underlying processes which collectively cause the wall catalytic activity. Because (dissociative) adsorption is a fundamental step leading to surface recombinations, the sticking of O2 on Pt(111) is studied using ReaxFF Molecular Dynamics simulations.",
author = "Paolo Valentini and Schwartzentruber, {Thomas E} and Ioana Cozmuta",
year = "2009",
month = "12",
day = "1",
language = "English (US)",
isbn = "9781563479755",
series = "41st AIAA Thermophysics Conference",
booktitle = "41st AIAA Thermophysics Conference",

}

TY - GEN

T1 - A mechanism-based finite-rate surface catalysis model for simulating reacting flows

AU - Valentini, Paolo

AU - Schwartzentruber, Thomas E

AU - Cozmuta, Ioana

PY - 2009/12/1

Y1 - 2009/12/1

N2 - A mechanism-based finite-rate wall boundary condition is implemented in a state-of-the- art finite volume CFD thermochemical nonequilibrium code to study a high enthalpy CO2 flow over blunt bodies. All the relevant surface processes responsible for the catalytic behavior of the wall are accounted for, including adsorption and desorption (both atomic and molecular), and Eley-Rideal and Langmuir-Hinshelwood recombinations. The model only requires the specification of the reaction rates for each of the processes considered, and the law of mass action is used to compute surface coverages and mass fluxes produced or consumed at the wall due to its catalytic activity. The kinetic rates are chosen to describe a platinum surface, with a fairly high degree of catalycity with respect to CO oxidation. As expected, the predicted heat flux is intermediate between the two extrema, namely the non-catalytic and supercatalytic wall assumptions. Because the only input of the model are the reaction rates, which are usually unavailable or affected by a large experimental uncertainty, the use of Molecular Dynamics simulations employing the Quantum Chemistry based reactive force field ReaxFF is proposed as a novel approach to both determine and characterize each of the underlying processes which collectively cause the wall catalytic activity. Because (dissociative) adsorption is a fundamental step leading to surface recombinations, the sticking of O2 on Pt(111) is studied using ReaxFF Molecular Dynamics simulations.

AB - A mechanism-based finite-rate wall boundary condition is implemented in a state-of-the- art finite volume CFD thermochemical nonequilibrium code to study a high enthalpy CO2 flow over blunt bodies. All the relevant surface processes responsible for the catalytic behavior of the wall are accounted for, including adsorption and desorption (both atomic and molecular), and Eley-Rideal and Langmuir-Hinshelwood recombinations. The model only requires the specification of the reaction rates for each of the processes considered, and the law of mass action is used to compute surface coverages and mass fluxes produced or consumed at the wall due to its catalytic activity. The kinetic rates are chosen to describe a platinum surface, with a fairly high degree of catalycity with respect to CO oxidation. As expected, the predicted heat flux is intermediate between the two extrema, namely the non-catalytic and supercatalytic wall assumptions. Because the only input of the model are the reaction rates, which are usually unavailable or affected by a large experimental uncertainty, the use of Molecular Dynamics simulations employing the Quantum Chemistry based reactive force field ReaxFF is proposed as a novel approach to both determine and characterize each of the underlying processes which collectively cause the wall catalytic activity. Because (dissociative) adsorption is a fundamental step leading to surface recombinations, the sticking of O2 on Pt(111) is studied using ReaxFF Molecular Dynamics simulations.

UR - http://www.scopus.com/inward/record.url?scp=77958542580&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=77958542580&partnerID=8YFLogxK

M3 - Conference contribution

AN - SCOPUS:77958542580

SN - 9781563479755

T3 - 41st AIAA Thermophysics Conference

BT - 41st AIAA Thermophysics Conference

ER -