Simulation and fitting of complex reaction network TPR: The key is the objective function
Abstract
In this research, a method has been developed for finding improved fits during simulation and fitting of data from complex reaction network temperature programmed reactions (CRN-TPR). It was found that simulation and fitting of CRN-TPR presents additional challenges relative to simulation and fitting of simpler TPR systems. The method used here can enable checking the plausibility of proposed chemical mechanisms and kinetic models. The most important finding was that when choosing an objective function, use of an objective function that is based on integrated production provides more utility in finding improved fits when compared to an objective function based on the rate of production. The response surface produced by using the integrated production is monotonic, suppresses effects from experimental noise, requires fewer points to capture the response behavior, and can be simulated numerically with smaller errors. For CRN-TPR, there is increased importance (relative to simple reaction network TPR) in resolving of peaks prior to fitting, as well as from weighting of experimental data points. Using an implicit ordinary differential equation solver was found to be inadequate for simulating CRN-TPR. Lastly, the method employed here was capable of attaining improved fits in simulation and fitting of CRN-TPR when starting with amore »
- Authors:
-
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1271860
- Alternate Identifier(s):
- OSTI ID: 1397364
- Grant/Contract Number:
- AC05-00OR22725; ERKCC96
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Surface Science
- Additional Journal Information:
- Journal Volume: 653; Journal ID: ISSN 0039-6028
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Temperature programmed desorption; Temperature programmed reaction; Microkinetics; Transient kinetics; Parameter optimization
Citation Formats
Savara, Aditya Ashi. Simulation and fitting of complex reaction network TPR: The key is the objective function. United States: N. p., 2016.
Web. doi:10.1016/j.susc.2016.07.001.
Savara, Aditya Ashi. Simulation and fitting of complex reaction network TPR: The key is the objective function. United States. https://doi.org/10.1016/j.susc.2016.07.001
Savara, Aditya Ashi. Thu .
"Simulation and fitting of complex reaction network TPR: The key is the objective function". United States. https://doi.org/10.1016/j.susc.2016.07.001. https://www.osti.gov/servlets/purl/1271860.
@article{osti_1271860,
title = {Simulation and fitting of complex reaction network TPR: The key is the objective function},
author = {Savara, Aditya Ashi},
abstractNote = {In this research, a method has been developed for finding improved fits during simulation and fitting of data from complex reaction network temperature programmed reactions (CRN-TPR). It was found that simulation and fitting of CRN-TPR presents additional challenges relative to simulation and fitting of simpler TPR systems. The method used here can enable checking the plausibility of proposed chemical mechanisms and kinetic models. The most important finding was that when choosing an objective function, use of an objective function that is based on integrated production provides more utility in finding improved fits when compared to an objective function based on the rate of production. The response surface produced by using the integrated production is monotonic, suppresses effects from experimental noise, requires fewer points to capture the response behavior, and can be simulated numerically with smaller errors. For CRN-TPR, there is increased importance (relative to simple reaction network TPR) in resolving of peaks prior to fitting, as well as from weighting of experimental data points. Using an implicit ordinary differential equation solver was found to be inadequate for simulating CRN-TPR. Lastly, the method employed here was capable of attaining improved fits in simulation and fitting of CRN-TPR when starting with a postulated mechanism and physically realistic initial guesses for the kinetic parameters.},
doi = {10.1016/j.susc.2016.07.001},
journal = {Surface Science},
number = ,
volume = 653,
place = {United States},
year = {Thu Jul 07 00:00:00 EDT 2016},
month = {Thu Jul 07 00:00:00 EDT 2016}
}
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Works referenced in this record:
Variations in Reactivity on Different Crystallographic Orientations of Cerium Oxide
journal, July 2013
- Mullins, David R.; Albrecht, Peter M.; Calaza, Florencia
- Topics in Catalysis, Vol. 56, Issue 15-17
Microkinetic simulation of catalytic reactions
journal, October 2000
- Stoltze, Per
- Progress in Surface Science, Vol. 65, Issue 3-4
Molecular-level descriptions of surface chemistry in kinetic models using density functional theory
journal, November 2004
- Gokhale, Amit A.; Kandoi, Shampa; Greeley, Jeffrey P.
- Chemical Engineering Science, Vol. 59, Issue 22-23
Comprehensive DFT Study of Nitrous Oxide Decomposition over Fe-ZSM-5 †
journal, February 2005
- Heyden, Andreas; Peters, Baron; Bell, Alexis T.
- The Journal of Physical Chemistry B, Vol. 109, Issue 5
Theoretical investigation of the reaction mechanism of the hydrodeoxygenation of guaiacol over a Ru(0 0 0 1) model surface
journal, January 2015
- Lu, Jianmin; Heyden, Andreas
- Journal of Catalysis, Vol. 321
Microkinetic modeling of the decarboxylation and decarbonylation of propanoic acid over Pd(111) model surfaces based on parameters obtained from first principles
journal, September 2013
- Lu, Jianmin; Behtash, Sina; Faheem, Muhammad
- Journal of Catalysis, Vol. 305
Detailed surface reaction mechanism in a three-way catalyst
journal, October 2001
- Chatterjee, Daniel; Deutschmann, Olaf; Warnatz, Jürgen
- Faraday Discussions, Vol. 119, Issue 1
Identity and chemical function of gallium species inferred from microkinetic modeling studies of propane aromatization over Ga/HZSM-5 catalysts
journal, May 2010
- Krishnamurthy, Gowri; Bhan, Aditya; Delgass, W. Nicholas
- Journal of Catalysis, Vol. 271, Issue 2
Microkinetic modeling of propane aromatization over HZSM-5
journal, October 2005
- Bhan, A.; Hsu, S.; Blau, G.
- Journal of Catalysis, Vol. 235, Issue 1
Numerical simulation of temperature-programmed reaction data: an application in surface chemical kinetics
journal, January 1998
- Ellis, Gareth; Sidaway, James; McCoustra, Martin R. S.
- Journal of the Chemical Society, Faraday Transactions, Vol. 94, Issue 17
Microkinetic Simulation of Temperature-Programmed Desorption
journal, March 2013
- Wang, Chia-Ching; Wu, Jyun-Yi; Jiang, Jyh-Chiang
- The Journal of Physical Chemistry C, Vol. 117, Issue 12
Kinetic modeling of nitrous oxide decomposition on Fe-ZSM-5 based on parameters obtained from first-principles calculations
journal, July 2005
- Heyden, A.; Bell, A.; Keil, F.
- Journal of Catalysis, Vol. 233, Issue 1
Applicability of non-isothermal model-free predictions for assessment of conversion vs. time curves for complex processes in isothermal and quasi-isothermal conditions
journal, April 2013
- Budrugeac, P.
- Thermochimica Acta, Vol. 558
Recent advances in numerical modeling of catalytic monolith reactors
journal, August 2005
- Tischer, Steffen; Deutschmann, Olaf
- Catalysis Today, Vol. 105, Issue 3-4
A hybrid genetic algorithm for efficient parameter estimation of large kinetic models
journal, November 2004
- Katare, Santhoji; Bhan, Aditya; Caruthers, James M.
- Computers & Chemical Engineering, Vol. 28, Issue 12
Three-way catalytic converter modelling. Numerical determination of kinetic data
book, January 1998
- Dubien, C.; Schweich, D.
- Catalysis and Automotive Pollution Control IV, Proceedings of the Fourth International Symposium (CAPoC4)
Least squares criteria for the kinetic evaluation of thermoanalytical experiments. Examples from a char reactivity study
journal, February 2001
- Várhegyi, Gábor; Szabó, Piroska; Jakab, Emma
- Journal of Analytical and Applied Pyrolysis, Vol. 57, Issue 2
Evaluation of kinetic parameters from TVA data. A computer simulation approach
journal, December 1974
- Roche, Rodney S.
- Journal of Applied Polymer Science, Vol. 18, Issue 12
Mathematical Modeling of Nitrogen Desorption from an Iridium Surface: A Study of the Effects of Surface Structure and Subsurface Oxygen1
journal, January 2001
- Kurkina, E. S.; Semendyaeva, N. L.; Boronin, A. I.
- Kinetics and Catalysis, Vol. 42, Issue 5, p. 703-717
Análise estatística e optimização de perfis de redução termoprogramada (TPR)
journal, January 2006
- Nele, Marcio; Moreno, Esteban Lopez; Andrade, Heloysa Martins Carvalho
- Química Nova, Vol. 29, Issue 4
Mathematical considerations for nonisothermal kinetics in thermal decomposition
journal, March 2005
- Caballero, José A.; Conesa, Juan A.
- Journal of Analytical and Applied Pyrolysis, Vol. 73, Issue 1
Nonlinear parameter estimation: A case study comparison
journal, January 1986
- Biegler, L. T.; Damiano, J. J.; Blau, G. E.
- AIChE Journal, Vol. 32, Issue 1
A general strategy for parameter estimation in differential—algebraic systems
journal, May 1993
- Bilardello, P.; Joulia, X.; Le Lann, J. M.
- Computers & Chemical Engineering, Vol. 17, Issue 5-6
Performance comparison of parameter estimation techniques for unidentifiable models
journal, May 2014
- Graciano, J. E.; Mendoza, D. F.; Le Roux, G. A. C.
- Computers & Chemical Engineering, Vol. 64
A Program for Fitting Rate Constants in Gas Phase Chemical Kinetics Models
journal, September 1984
- Byrne, G. D.; DeGregoria, A. J.; Salane, D. E.
- SIAM Journal on Scientific and Statistical Computing, Vol. 5, Issue 3
Application of stepwise regression for dynamic parameter estimation
journal, October 2014
- Shacham, Mordechai; Brauner, Neima
- Computers & Chemical Engineering, Vol. 69
Mathematical modelling of chemical processes-obtaining the best model predictions and parameter estimates using identifiability and estimability procedures
journal, October 2011
- McLean, Kevin A. P.; McAuley, Kim B.
- The Canadian Journal of Chemical Engineering, Vol. 90, Issue 2
ICTAC Kinetics Committee recommendations for performing kinetic computations on thermal analysis data
journal, June 2011
- Vyazovkin, Sergey; Burnham, Alan K.; Criado, José M.
- Thermochimica Acta, Vol. 520, Issue 1-2
Integral kinetic analysis from temperature programmed reaction data: alkaline hydrolysis of ethyl acetate as test reaction
journal, March 1989
- Ortiz, M. I.; Romero, A.; Irabien, A.
- Thermochimica Acta, Vol. 141
First-Principles Analysis of Structure Sensitivity in NO Oxidation on Pt
journal, January 2015
- Bray, J. M.; Schneider, W. F.
- ACS Catalysis, Vol. 5, Issue 2
A Generalized Approach for Predicting Coverage-Dependent Reaction Parameters of Complex Surface Reactions: Application to H 2 Oxidation over Platinum
journal, October 1999
- Park, Young K.; Aghalayam, Preeti; Vlachos, Dionisios G.
- The Journal of Physical Chemistry A, Vol. 103, Issue 40
DFT comparison of intrinsic WGS kinetics over Pd and Pt
journal, December 2014
- Clay, John P.; Greeley, Jeffrey P.; Ribeiro, Fabio H.
- Journal of Catalysis, Vol. 320
Accurate coverage-dependence incorporated into first-principles kinetic models: Catalytic NO oxidation on Pt (111)
journal, February 2012
- Wu, C.; Schmidt, D. J.; Wolverton, C.
- Journal of Catalysis, Vol. 286
The compensation effect and the manifestation of lateral interactions in thermal desorption spectroscopy
journal, February 1988
- Niemantsverdriet, J. W.; Markert, K.; Wandelt, K.
- Applied Surface Science, Vol. 31, Issue 2
Thermal desorption analysis: Comparative test of ten commonly applied procedures
journal, July 1990
- de Jong, A. M.; Niemantsverdriet, J. W.
- Surface Science, Vol. 233, Issue 3
Temperature-Programmed Desorption and Reaction: Applications to Supported Catalysts
journal, June 1983
- Falconer, John L.; Schwarz, James A.
- Catalysis Reviews, Vol. 25, Issue 2
Review and evaluation of the approximations to the temperature integral
journal, January 2007
- Órfão, José J. M.
- AIChE Journal, Vol. 53, Issue 11
A New Method of Analysing Temperature-Programmed Desorption (TPD) Profiles Using an Extended Integral Equation
journal, November 1997
- Koch, K.; Hunger, B.; Klepel, O.
- Journal of Catalysis, Vol. 172, Issue 1
Computational aspects of kinetic analysis
journal, July 2000
- Brown, M. E.; Maciejewski, M.; Vyazovkin, S.
- Thermochimica Acta, Vol. 355, Issue 1-2
Computational aspects of kinetic analysis.
journal, July 2000
- Maciejewski, Marek
- Thermochimica Acta, Vol. 355, Issue 1-2
Computational aspects of kinetic analysis.
journal, July 2000
- Roduit, B.
- Thermochimica Acta, Vol. 355, Issue 1-2
Computational aspects of kinetic analysis.
journal, July 2000
- Vyazovkin, Sergey
- Thermochimica Acta, Vol. 355, Issue 1-2
Elucidation of Intermediates and Mechanisms in Heterogeneous Catalysis Using Infrared Spectroscopy
journal, April 2014
- Savara, Aditya; Weitz, Eric
- Annual Review of Physical Chemistry, Vol. 65, Issue 1
An algorithm for the identification and estimation of relevant parameters for optimization under uncertainty
journal, December 2014
- Müller, David; Esche, Erik; López C., Diana C.
- Computers & Chemical Engineering, Vol. 71
Reactions of methanol on W(100) and W(100)-(5 $times; 1)C surfaces
journal, April 1980
- Ko, E.
- Journal of Catalysis, Vol. 62, Issue 2
Analysing methods for thermal desorption spectra
journal, May 1997
- Kautto, E.; Kuhalainen, J.; Manninen, M.
- Physica Scripta, Vol. 55, Issue 5
ICTAC Kinetics Committee recommendations for collecting experimental thermal analysis data for kinetic computations
journal, August 2014
- Vyazovkin, Sergey; Chrissafis, Konstantinos; Di Lorenzo, Maria Laura
- Thermochimica Acta, Vol. 590
Sample controlled thermal analysis and kinetics
journal, March 2005
- Criado, J. M.; Pérez-Maqueda, L. A.
- Journal of Thermal Analysis and Calorimetry, Vol. 80, Issue 1
Aims and methods in non-isothermal reaction kinetics
journal, May 2007
- Várhegyi, Gábor
- Journal of Analytical and Applied Pyrolysis, Vol. 79, Issue 1-2
Nonlinear parameter estimation technique for kinetic analysis of thermal desorption data
journal, August 1996
- Russell, N. M.; Ekerdt, J. G.
- Surface Science, Vol. 364, Issue 2
Parametric sensitivity of complex temperature-programmed desorption, reaction and reduction
journal, May 1989
- Stuchlý, V.
- Journal of Thermal Analysis, Vol. 35, Issue 3
A new method for the analysis of heterogeneity using a modified temperature-programmed desorption technique
journal, January 1992
- Vásquez, Sergio O.
- J. Chem. Soc., Faraday Trans., Vol. 88, Issue 14
Temperature programming for isothermal desorption rate measurements
journal, November 1992
- DeAngelis, Michael A.; Anton, A. Brad
- Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 10, Issue 6
Analysis of temperature programmed desorption (TPD) data for the characterisation of catalysts containing a distribution of adsorption sites
journal, January 2008
- Barrie, Patrick J.
- Physical Chemistry Chemical Physics, Vol. 10, Issue 12
An iterative model-free method to determine the activation energy of heterogeneous processes under arbitrary temperature programs
journal, August 2011
- Budrugeac, P.
- Thermochimica Acta, Vol. 523, Issue 1-2
Approximate simulation of coupled fast and slow reactions for stochastic chemical kinetics
journal, October 2002
- Haseltine, Eric L.; Rawlings, James B.
- The Journal of Chemical Physics, Vol. 117, Issue 15
Partitioning ODE systems with an application to air pollution models
journal, September 2001
- Zlatev, Z.
- Computers & Mathematics with Applications, Vol. 42, Issue 6-7
Direct and adjoint sensitivity analysis of chemical kinetic systems with KPP: Part I—theory and software tools
journal, November 2003
- Sandu, Adrian; Daescu, Dacian N.; Carmichael, Gregory R.
- Atmospheric Environment, Vol. 37, Issue 36
A predictor–corrector algorithm for the coupling of stiff ODEs to a particle population balance
journal, May 2009
- Celnik, Matthew; Patterson, Robert; Kraft, Markus
- Journal of Computational Physics, Vol. 228, Issue 8
Implicit–explicit Runge–Kutta methods applied to atmospheric chemistry-transport modelling
journal, September 2000
- Wolke, Ralf; Knoth, Oswald
- Environmental Modelling & Software, Vol. 15, Issue 6-7
Explicit methods for stiff ODEs from atmospheric chemistry
journal, September 1995
- Verwer, J. G.; Simpson, D.
- Applied Numerical Mathematics, Vol. 18, Issue 1-3
Benchmarking stiff ode solvers for atmospheric chemistry problems-I. implicit vs explicit
journal, October 1997
- Sandu, A.; Verwer, J. G.; Van Loon, M.
- Atmospheric Environment, Vol. 31, Issue 19
Benchmarking stiff ode solvers for atmospheric chemistry problems II: Rosenbrock solvers
journal, October 1997
- Sandu, A.; Verwer, J. G.; Blom, J. G.
- Atmospheric Environment, Vol. 31, Issue 20
Gauss–Seidel Iteration for Stiff ODES from Chemical Kinetics
journal, September 1994
- Verwer, J. G.
- SIAM Journal on Scientific Computing, Vol. 15, Issue 5
Efficient formulation of the stochastic simulation algorithm for chemically reacting systems
journal, September 2004
- Cao, Yang; Li, Hong; Petzold, Linda
- The Journal of Chemical Physics, Vol. 121, Issue 9
A constant-time kinetic Monte Carlo algorithm for simulation of large biochemical reaction networks
journal, May 2008
- Slepoy, Alexander; Thompson, Aidan P.; Plimpton, Steven J.
- The Journal of Chemical Physics, Vol. 128, Issue 20
Quasiequilibrium approximation of fast reaction kinetics in stochastic biochemical systems
journal, May 2005
- Goutsias, John
- The Journal of Chemical Physics, Vol. 122, Issue 18
Overcoming stiffness in stochastic simulation stemming from partial equilibrium: A multiscale Monte Carlo algorithm
journal, October 2005
- Samant, A.; Vlachos, D. G.
- The Journal of Chemical Physics, Vol. 123, Issue 14
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Microkinetic simulation and fitting of the temperature programmed reaction of methanol on CeO2(111): H2 and H2O + V production
journal, January 2020
- Savara, Aditya
- Reaction Kinetics, Mechanisms and Catalysis, Vol. 129, Issue 1
A Hybrid Kinetic Analysis of the Biosolids Pyrolysis using Thermogravimetric Analyser
journal, December 2018
- Patel, Savankumar R.; Kundu, Sazal K.; Halder, Pobitra K.
- ChemistrySelect, Vol. 3, Issue 47
Theoretical Parameter-Free Analysis Model for Temperature-Programmed Desorption (TPD) Spectra
journal, February 2020
- Xu, Jian; Deng, Junyi
- ACS Omega, Vol. 5, Issue 8
Dynamic vs static behaviour of a supported nanoparticle with reaction-induced catalytic sites in a lattice model
journal, February 2020
- Korobov, Alexander
- Scientific Reports, Vol. 10, Issue 1
TAPsolver: A Python package for the simulation and analysis of TAP reactor experiments
preprint, January 2020
- Yonge, Adam; Kunz, M. Ross; Batchu, Rakesh
- arXiv