ChemRate

A tool for RRKM/Master Equation Modeling

Vladimir Mokrushin, Vladimir Bedanov, Wing Tsang, Michael R. Zachariah, Vadim D. Knyazev, W. Sean McGivern

Current Version: 1.5.10 (April 14, 2011)

Overview

The ChemRate program package enables one to calculate time-dependent and steady-state rate coefficients at different temperatures and pressures. Systems of high complexity involving reversible isomerization, decomposition and thermal and chemical activation can be considered. The density and sum of states are calculated using direct count or Whitten-Rabinovitch algorithms with vibration frequencies and moments of inertia as input parameters. Alternatively, analytical expression with three parameters can be used for k(E). The microscopic rate coefficients k(E) are calculated by using RRKM theory. The collision energy transfer probabilities are taken in the standard form of an "exponential down" model. The time evolution of the population of each the species in the system is described by the master equation.

Development History

The basis for ChemRate was developed about 20 years ago in 1995-1996. A description of the some of the methodology can be found in

Bedanov, V. M.; Tsang, W.; Zachariah, M. R.; "Master equation analysis of thermal activation reactions - reversible isomerization and decomposition." J. Phys. Chem. 99, 11452-11457 (1995).

Tsang, W; Bedanov, V; Zachariah, MR; "Master equation analysis of thermal activation reactions: Energy-transfer constraints on falloff behavior in the decomposition of reactive intermediates with low thresholds." J. Phys. Chem. 100, 4011-4018 (1996).

Knyazev, VD; Tsang, W; "Chemically and thermally activated decomposition of secondary butyl radical." J. Phys. Chem. A 104, 10747-10765 (2000).

Flow Sheet for The Calculation of Unimolecular Reactions

Databases of Transition States
and Molecular Properties Databases for Experimental Results

Calculator for Density and
Sum of States Specific Rates Calculator for High Pressure
Rate Constants Thermal Functions

Master Equation Solver
Distribution Functions
Rate Constants for All Conditions Curve Fitting Routines
Appropriate Forms for Simulation

Features

Calculates high pressure rate constants of all unimolecular reactions on the basis of transition state theory.
Determines specific rate constants on the basis of RRKM theory.
Treats multichannel reactions including chemical activation processes under equilibrium and non-equilibrium conditions. Calculates steady state rate constant as well as time-dependent rate constants.
Carry out calculations with any initial distribution.
Compute thermofunctions (C_p, ΔS°, ΔH°, pK, etc.) at any temperature.
Simple treatment of bimolecular reactions.
Calculates thermodynamic properties and rate constants from Gaussian file.
Treats hindered rotors.
Treats tunneling.
Multicomponent buffer gas.
Fit computed results in various ways.
Compare computed results with experimental data.
Easy to build time-dependent distribution functions, rate constants, and concentration.

Databases

Creates and accesses the database of components and reactions. The database includes: standard heat of formation, frequencies, external and internal rotations, collision parameters, geometry, experimental data. Possibility to define collisional parameters between any pair of collision participants.

Technical

Application contains follow tools:

Content-sensitive help.
3D molecule geometry viewer.
Import data from GAUSSIAN output file.
Find internal rotors and compute moments of inertia.
Compute Lenard-Jones parameters from critical T and P.
Graphical presentation of data including 3D view.
Data exchange between other Windows applications (Word, Excel, Access, etc.) by copy & paste.

Requirements

Pentium II 400 processor or greater
Windows 95/98/NT/2000/XP
Windows 7/Windows 10
128 Mb RAM
100 Mb hard drive space

Sample Images

Workspace
Workspace Image

Database
Database Image

Usage by Researchers

The ChemRate program has been used by a variety of researchers over the last 15-20 years.

1995 Bedanov, V. M.; Tsang, W.; Zachariah, M. R.; "Master equation analysis of thermal activation reactions - reversible isomerization and decomposition." J. Phys. Chem. 99, 11452-11457 (1995).

1996 Tsang, W; Bedanov, V; Zachariah, MR; "Master equation analysis of thermal activation reactions: Energy-transfer constraints on falloff behavior in the decomposition of reactive intermediates with low thresholds." J. Phys. Chem. 100, 4011-4018 (1996).

2000 Knyazev, VD; Tsang, W; "Chemically and thermally activated decomposition of secondary butyl radical." J. Phys. Chem. A 104, 10747-10765 (2000).

2002 Lee, JW; Chen, CJ; Bozzelli, JW; "Thermochemical and kinetic analysis of the acetyl radical (CH3C center dot O)+O-2 reaction system." J. Phys. Chem. A 106, 7155-7170 (2002).

2002 Lindstedt, RP; Rizos, KA; "The formation and oxidation of aromatics in cyclopentene and methyl-cyclopentadiene mixtures." Proc. Combust. Inst. 29, Published: 2002 (2002).

2003 Bryukov, MG; Kostina, SA; Knyazev, VD; "Kinetics of the unimolecular decomposition of the C2Cl3 radical." J. Phys. Chem. A 107, 6574-6579 (2003).

2003 Lee, J; Bozzelli, JW; "Reaction of H plus ketene to formyl methyl and acetyl radicals and reverse dissociations." Int. J. Chem. Kinet. 35, 20-44 (2003).

2003 Tokmakov, IV; Moskaleva, LV; Paschenko, DV; et al.; "Computational study of the HCCO+NO reaction: ab initio MO/vRRKM calculations of the total rate constant and product branching ratios." J. Phys. Chem. A 107, 1066-1076 (2003).

2004 Li, J; Kazakov, A; Dryer, FL; "Experimental and numerical studies of ethanol decomposition reactions." J. Phys. Chem. A 108, 7671-7680 (2004).

2005 Ismail, H; Park, J; Wong, BM; et al.; "A theoretical and experimental kinetic study of phenyl radical addition to butadiene." Proc. Combust. Inst. 30, 1049-1056 (2005).

2005 Lee, J; Bozzelli, JW; "Thermochemical and kinetic analysis of the allyl radical with O-2 reaction system." Proc. Combust. Inst. 30, 1015-1022 (2005).

2005 Xu, S; Irle, S; Musaev, AG; et al.; "Water clusters on graphite: Methodology for quantum chemical A priori prediction of reaction rate constants." J. Phys. Chem. A 109, 9563-9572 (2005).

2006 McGivern, W. Sean; Manion, Jeffrey A.; Tsang, Wing; "Ring-expansion reactions in the thermal decomposition of tert-butyl-1,3-cyclopentadiene." J. Phys. Chem. A 110, 12822-12831 (2006).

2006 Xu, ZF; Lin, MC; "Ab initio kinetics for the unimolecular reaction C6H5OH -> CO+C5H6." J. Phys. Chem. A 110, 1672-1677 (2006).

2007 Xu, Z. F.; Lin, M. C.; "Computational studies on the kinetics and mechanisms for NH3 reactions with ClOx (x=0-4) radicals." J. Phys. Chem. A 111, 584-590 (2007).

2008 McGivern, W. Sean; Awan, Iftikhar A.; Tsang, Wing; et al.; "Isomerization and decomposition reactions in the pyrolysis of branched hydrocarbons: 4-methyl-1-pentyl radical." J. Phys. Chem. A 112, 6908-6917 (2008).

2009 da Silva, Gabriel; Bozzelli, Joseph W.; "Benzoxyl Radical Decomposition Kinetics: Formation of Benzaldehyde plus H, Phenyl + CH2O, and Benzene plus HCO." J. Phys. Chem. A 113, 6979-6986 (2009).

2009 Huang, Wen-Fei; Chen, Hsin-Tsung; Lin, M. C.; "Density Functional Theory Study of the Adsorption and Reaction of H2S on TiO2 Rutile (110) and Anatase (101) Surfaces." J. Phys. Chem. C 113, 20411-20420 (2009).

2009 Tsang, Wing; McGivern, W. Sean; Manion, Jeffrey A.; "Multichannel decomposition and isomerization of octyl radicals." Proc. Combust. Inst. 32, 131-138 (2009).

2010 Awan, Iftikhar A.; McGivern, W. Sean; Tsang, Wing; et al.; "Decomposition and Isomerization of 5-Methylhex-1-yl Radical." J. Phys. Chem. A 114, 7832-7846 (2010).

2010 Davis, Alexander C.; Francisco, Joseph S.; "Ab Initio Study of Hydrogen Migration in 1-Alkylperoxy Radicals." J. Phys. Chem. A 114, 11492-11505 (2010).

2011 Guan, Yulei; Yang, Bolun; Oi, Suitao; et al.; "Kinetic Modeling of the Free-Radical Process during the Initiated Thermal Cracking of Normal Alkanes with 1-Nitropropane as an Initiator." Ind. Eng. Chem. Res. 50, 9054-9062 (2011).

2011 Nisar, Jan; Awan, Iftikhar A.; "Kinetics of the gas-phase thermal decomposition of 3-bromopropene." Kinet. Catal. 52, 487-492 (2011).

2011 Tian, Zhenyu; Yuan, Tao; Fournet, Rene; et al.; "An experimental and kinetic investigation of premixed furan/oxygen/argon flames." Combust. Flame 158, 756-773 (2011).

2012 Awan, Iftikhar A.; Burgess, Donald R., Jr.; Manion, Jeffrey A.; "Pressure Dependence and Branching Ratios in the Decomposition of 1-Pentyl Radicals: Shock Tube Experiments and Master Equation Modeling." J. Phys. Chem. A 116, 2895-2910 (2012).

2012 Awan, Iftikhar A.; Burgess, Donald R., Jr.; Tsang, Wing; et al.; "Standard reactions for comparative rate studies: Experiments on the dehydrochlorination reactions of 2-chloropropane, chlorocyclopentane, and chlorocyclohexane." Int. J. Chem. Kinet. 44, 351-368 (2012).

2012 Cord, Maximilien; Sirjean, Baptiste; Fournet, Rene; et al.; "Improvement of the Modeling of the Low-Temperature Oxidation of n-Butane: Study of the Primary Reactions." J. Phys. Chem. A 116, 6142-6158 (2012).

2012 Kislov, V. V.; Mebel, A. M.; Aguilera-Iparraguirre, J.; et al.; "Reaction of Phenyl Radical with Propylene as a Possible Source of Indene and Other Polycyclic Aromatic Hydrocarbons: An Ab Initio/RRKM-ME Study." J. Phys. Chem. A 116, 4176-4191 (2012).

2012 Sirjean, Baptiste; Dames, Enoch; Wang, Hai; et al.; "Tunneling in Hydrogen-Transfer Isomerization of n-Alkyl Radicals." J. Phys. Chem. A 116, 319-332 (2012).

2012 Weng, Meng Hsiung; Chen, Hsin-Tsung; Wang, Yao-Chun; et al.; "Kinetics and Mechanisms for the Adsorption, Dissociation, and Diffusion of Hydrogen in Ni and Ni/YSZ Slabs: A DFT Study." Langmuir 28, 5596-5605 (2012).

2013 Altarawneh, Ibrahem; Altarawneh, Mohammednoor; Rawadieh, Saleh; "Theoretical study on thermochemical parameters and IR spectra of chlorinated isomers of nitrobenzene." Can. J. Chem. 91, 999-1008 (2013).

2013 Davis, Alexander C.; Sarathy, S. Mani; "Computational Study of the Combustion and Atmospheric Decomposition of 2-Methylfuran." J. Phys. Chem. A 117, 7670-7685 (2013).

2013 Manion, Jeffrey A.; Awan, Iftikhar A.; "The decomposition of 2-pentyl and 3-pentyl radicals." Proc. Combust. Inst. 34, 537-545 (2013).

2014 Ahubelem, Nwakamma; Altarawneh, Mohammednoor; Dlugogorski, Bogdan Z.; "Dehydrohalogenation of ethyl halides." Tetrahedron Lett. 55, 4860-4868 (2014).

2014 Wang, Zhandong; Ye, Lili; Yuan, Wenhao; et al.; "Experimental and kinetic modeling study on methylcyclohexane pyrolysis and combustion." Combust. Flame 161, 84-100 (2014).

2015 Al Rashidi, Mariam J.; Davis, Alexander C.; Sarathy, S. Mani; "Kinetics of the high-temperature combustion reactions of dibutylether using composite computational methods." Proc. Combust. Inst. 35, 385-392 (2015).

2015 Khaled, Fethi; Giri, Binod Raj; Szori, Milan; et al.; "An experimental and theoretical study on the kinetic isotope effect of C2H6 and C2D6 reaction with OH." Chem. Phys. Lett. 641, 158-162 (2015).

2015 Ning, HongBo; Gong, ChunMing; Li, ZeRong; et al.; "Pressure-Dependent Kinetics of Initial Reactions in Iso-octane Pyrolysis." J. Phys. Chem. A 119, 4093-4107 (2015).

2015 Trong-Nghia Nguyen; Putikam, Raghunath; Lin, M. C.; "A novel and facile decay path of Criegee intermediates by intramolecular insertion reactions via roaming transition states." J. Chem. Phys. 142, 124312 (2015).

2016 Yang, Feiyu; Deng, Fuquan; Pan, Youshun; et al.; "Ab initio kinetics for isomerization reaction of normal-chain hexadiene isomers." Chem. Phys. Lett. 663, 66-73 (2016).

Notes

The Microsoft Visual C++ 2008 Redistributable may be required (if you get an error and the application refuses to start).

ChemRate will not run out of the box on Windows 7 (or 8, or 10), but a simple workaround is available. Programs can no longer write directly to the "Program Files" directory, and the internal data files must be moved to a writable directory.

Workaround:

After installing on Windows Vista or later, copy the files

C:\Program Files\NIST\ChemRate\ChemRate.mdb
C:\Program Files\NIST\ChemRate\Element.dat

to somewhere in your "Documents" directory. (Note that 64-bit Windows will locate these files in "C:\Program Files (x86)\NIST\ChemRate").

Open ChemRate, and click through the repeated error dialogs until you can access the menu bar.

Under View..Preferences in the Directory tab, update the "ChemRate Database" and "Periodic Table of the Elements" text boxes with the new locations for Chemrate.mdb and Element.dat, respectively.

That will put the database files in a writable location, and ChemRate should be able to load and run without error.

Suggestions or comments?

If you would like to get in touch with the developer, leave a comment with the word ChemRate in the title using the NIST Chemical Kinetics Database comment form. Note that this software is not actively supported, but we will try to answer all queries in a timely fashion.

Databases of Transition States and Molecular Properties		Databases for Experimental Results

Calculator for Density and Sum of States Specific Rates		Calculator for High Pressure Rate Constants Thermal Functions

Master Equation Solver Distribution Functions Rate Constants for All Conditions		Curve Fitting Routines Appropriate Forms for Simulation

1995	Bedanov, V. M.; Tsang, W.; Zachariah, M. R.; "Master equation analysis of thermal activation reactions - reversible isomerization and decomposition." J. Phys. Chem. 99, 11452-11457 (1995).
1996	Tsang, W; Bedanov, V; Zachariah, MR; "Master equation analysis of thermal activation reactions: Energy-transfer constraints on falloff behavior in the decomposition of reactive intermediates with low thresholds." J. Phys. Chem. 100, 4011-4018 (1996).
2000	Knyazev, VD; Tsang, W; "Chemically and thermally activated decomposition of secondary butyl radical." J. Phys. Chem. A 104, 10747-10765 (2000).
2002	Lee, JW; Chen, CJ; Bozzelli, JW; "Thermochemical and kinetic analysis of the acetyl radical (CH3C center dot O)+O-2 reaction system." J. Phys. Chem. A 106, 7155-7170 (2002).
2002	Lindstedt, RP; Rizos, KA; "The formation and oxidation of aromatics in cyclopentene and methyl-cyclopentadiene mixtures." Proc. Combust. Inst. 29, Published: 2002 (2002).
2003	Bryukov, MG; Kostina, SA; Knyazev, VD; "Kinetics of the unimolecular decomposition of the C2Cl3 radical." J. Phys. Chem. A 107, 6574-6579 (2003).
2003	Lee, J; Bozzelli, JW; "Reaction of H plus ketene to formyl methyl and acetyl radicals and reverse dissociations." Int. J. Chem. Kinet. 35, 20-44 (2003).
2003	Tokmakov, IV; Moskaleva, LV; Paschenko, DV; et al.; "Computational study of the HCCO+NO reaction: ab initio MO/vRRKM calculations of the total rate constant and product branching ratios." J. Phys. Chem. A 107, 1066-1076 (2003).
2004	Li, J; Kazakov, A; Dryer, FL; "Experimental and numerical studies of ethanol decomposition reactions." J. Phys. Chem. A 108, 7671-7680 (2004).
2005	Ismail, H; Park, J; Wong, BM; et al.; "A theoretical and experimental kinetic study of phenyl radical addition to butadiene." Proc. Combust. Inst. 30, 1049-1056 (2005).
2005	Lee, J; Bozzelli, JW; "Thermochemical and kinetic analysis of the allyl radical with O-2 reaction system." Proc. Combust. Inst. 30, 1015-1022 (2005).
2005	Xu, S; Irle, S; Musaev, AG; et al.; "Water clusters on graphite: Methodology for quantum chemical A priori prediction of reaction rate constants." J. Phys. Chem. A 109, 9563-9572 (2005).
2006	McGivern, W. Sean; Manion, Jeffrey A.; Tsang, Wing; "Ring-expansion reactions in the thermal decomposition of tert-butyl-1,3-cyclopentadiene." J. Phys. Chem. A 110, 12822-12831 (2006).
2006	Xu, ZF; Lin, MC; "Ab initio kinetics for the unimolecular reaction C6H5OH -> CO+C5H6." J. Phys. Chem. A 110, 1672-1677 (2006).
2007	Xu, Z. F.; Lin, M. C.; "Computational studies on the kinetics and mechanisms for NH3 reactions with ClOx (x=0-4) radicals." J. Phys. Chem. A 111, 584-590 (2007).
2008	McGivern, W. Sean; Awan, Iftikhar A.; Tsang, Wing; et al.; "Isomerization and decomposition reactions in the pyrolysis of branched hydrocarbons: 4-methyl-1-pentyl radical." J. Phys. Chem. A 112, 6908-6917 (2008).
2009	da Silva, Gabriel; Bozzelli, Joseph W.; "Benzoxyl Radical Decomposition Kinetics: Formation of Benzaldehyde plus H, Phenyl + CH2O, and Benzene plus HCO." J. Phys. Chem. A 113, 6979-6986 (2009).
2009	Huang, Wen-Fei; Chen, Hsin-Tsung; Lin, M. C.; "Density Functional Theory Study of the Adsorption and Reaction of H2S on TiO2 Rutile (110) and Anatase (101) Surfaces." J. Phys. Chem. C 113, 20411-20420 (2009).
2009	Tsang, Wing; McGivern, W. Sean; Manion, Jeffrey A.; "Multichannel decomposition and isomerization of octyl radicals." Proc. Combust. Inst. 32, 131-138 (2009).
2010	Awan, Iftikhar A.; McGivern, W. Sean; Tsang, Wing; et al.; "Decomposition and Isomerization of 5-Methylhex-1-yl Radical." J. Phys. Chem. A 114, 7832-7846 (2010).
2010	Davis, Alexander C.; Francisco, Joseph S.; "Ab Initio Study of Hydrogen Migration in 1-Alkylperoxy Radicals." J. Phys. Chem. A 114, 11492-11505 (2010).
2011	Guan, Yulei; Yang, Bolun; Oi, Suitao; et al.; "Kinetic Modeling of the Free-Radical Process during the Initiated Thermal Cracking of Normal Alkanes with 1-Nitropropane as an Initiator." Ind. Eng. Chem. Res. 50, 9054-9062 (2011).
2011	Nisar, Jan; Awan, Iftikhar A.; "Kinetics of the gas-phase thermal decomposition of 3-bromopropene." Kinet. Catal. 52, 487-492 (2011).
2011	Tian, Zhenyu; Yuan, Tao; Fournet, Rene; et al.; "An experimental and kinetic investigation of premixed furan/oxygen/argon flames." Combust. Flame 158, 756-773 (2011).
2012	Awan, Iftikhar A.; Burgess, Donald R., Jr.; Manion, Jeffrey A.; "Pressure Dependence and Branching Ratios in the Decomposition of 1-Pentyl Radicals: Shock Tube Experiments and Master Equation Modeling." J. Phys. Chem. A 116, 2895-2910 (2012).
2012	Awan, Iftikhar A.; Burgess, Donald R., Jr.; Tsang, Wing; et al.; "Standard reactions for comparative rate studies: Experiments on the dehydrochlorination reactions of 2-chloropropane, chlorocyclopentane, and chlorocyclohexane." Int. J. Chem. Kinet. 44, 351-368 (2012).
2012	Cord, Maximilien; Sirjean, Baptiste; Fournet, Rene; et al.; "Improvement of the Modeling of the Low-Temperature Oxidation of n-Butane: Study of the Primary Reactions." J. Phys. Chem. A 116, 6142-6158 (2012).
2012	Kislov, V. V.; Mebel, A. M.; Aguilera-Iparraguirre, J.; et al.; "Reaction of Phenyl Radical with Propylene as a Possible Source of Indene and Other Polycyclic Aromatic Hydrocarbons: An Ab Initio/RRKM-ME Study." J. Phys. Chem. A 116, 4176-4191 (2012).
2012	Sirjean, Baptiste; Dames, Enoch; Wang, Hai; et al.; "Tunneling in Hydrogen-Transfer Isomerization of n-Alkyl Radicals." J. Phys. Chem. A 116, 319-332 (2012).
2012	Weng, Meng Hsiung; Chen, Hsin-Tsung; Wang, Yao-Chun; et al.; "Kinetics and Mechanisms for the Adsorption, Dissociation, and Diffusion of Hydrogen in Ni and Ni/YSZ Slabs: A DFT Study." Langmuir 28, 5596-5605 (2012).
2013	Altarawneh, Ibrahem; Altarawneh, Mohammednoor; Rawadieh, Saleh; "Theoretical study on thermochemical parameters and IR spectra of chlorinated isomers of nitrobenzene." Can. J. Chem. 91, 999-1008 (2013).
2013	Davis, Alexander C.; Sarathy, S. Mani; "Computational Study of the Combustion and Atmospheric Decomposition of 2-Methylfuran." J. Phys. Chem. A 117, 7670-7685 (2013).
2013	Manion, Jeffrey A.; Awan, Iftikhar A.; "The decomposition of 2-pentyl and 3-pentyl radicals." Proc. Combust. Inst. 34, 537-545 (2013).
2014	Ahubelem, Nwakamma; Altarawneh, Mohammednoor; Dlugogorski, Bogdan Z.; "Dehydrohalogenation of ethyl halides." Tetrahedron Lett. 55, 4860-4868 (2014).
2014	Wang, Zhandong; Ye, Lili; Yuan, Wenhao; et al.; "Experimental and kinetic modeling study on methylcyclohexane pyrolysis and combustion." Combust. Flame 161, 84-100 (2014).
2015	Al Rashidi, Mariam J.; Davis, Alexander C.; Sarathy, S. Mani; "Kinetics of the high-temperature combustion reactions of dibutylether using composite computational methods." Proc. Combust. Inst. 35, 385-392 (2015).
2015	Khaled, Fethi; Giri, Binod Raj; Szori, Milan; et al.; "An experimental and theoretical study on the kinetic isotope effect of C2H6 and C2D6 reaction with OH." Chem. Phys. Lett. 641, 158-162 (2015).
2015	Ning, HongBo; Gong, ChunMing; Li, ZeRong; et al.; "Pressure-Dependent Kinetics of Initial Reactions in Iso-octane Pyrolysis." J. Phys. Chem. A 119, 4093-4107 (2015).
2015	Trong-Nghia Nguyen; Putikam, Raghunath; Lin, M. C.; "A novel and facile decay path of Criegee intermediates by intramolecular insertion reactions via roaming transition states." J. Chem. Phys. 142, 124312 (2015).
2016	Yang, Feiyu; Deng, Fuquan; Pan, Youshun; et al.; "Ab initio kinetics for isomerization reaction of normal-chain hexadiene isomers." Chem. Phys. Lett. 663, 66-73 (2016).