Imperial College London
Alternate

Prof Amparo Galindo

Faculty of Engineering, Department of Chemical Engineering

Co-Director Institute for Molecular Science and Engineering
 
 
 
//

Contact

 

+44 (0)20 7594 5606a.galindo

 
 
//

Location

 

604Roderic Hill BuildingSouth Kensington Campus

//

Summary

 

Publications

Citation

BibTex format

@article{Diamanti:2016:10.1021/acs.iecr.6b03443,
author = {Diamanti, A and Adjiman, CS and Piccione, PM and Rea, AM and Galindo, A},
doi = {10.1021/acs.iecr.6b03443},
journal = {Industrial & Engineering Chemistry Research},
pages = {815--831},
title = {Development of Predictive Models of the Kinetics of a Hydrogen Abstraction Reaction Combining Quantum-Mechanical Calculations and Experimental Data},
url = {http://dx.doi.org/10.1021/acs.iecr.6b03443},
volume = {56},
year = {2016}
}
Download

RIS format (EndNote, RefMan)

TY  - JOUR
AB  - The importance of developing accurate modeling tools for the prediction of reaction kinetics is well recognized. In this work, a thorough investigation of the suitability of quantum mechanical (QM) calculations to predict the effect of temperature on the rate constant of the reaction between ethane and the hydroxyl radical is presented. Further, hybrid models that combine a limited number of QM calculations and experimental data are developed in order to increase their reliability. The activation energy barrier of the reaction is computed using various computational methods, such as B3LYP, M05-2X, M06-2X, MP2 and PMP2, CBS-QB3, and W1BD, with a selection of basis sets. A broad range of values is obtained, including negative barriers for all of the calculations with B3LYP. The rate constants are also obtained for each method, using conventional transition state theory, and are compared with available experimental values at 298 K. The best agreement is achieved with the M05-2X functional with cc-pV5Z basis set. Rate constants calculated at this level of theory are also found to be in good agreement with experimental values at different temperatures, resulting in a mean absolute error of the logarithm (MAEln) of the calculated values of 0.213 over a temperature range of 200–1250 K and 0.108 over a temperature range of 300–499 K. Tunnelling and vibrational anharmonicities are identified as important sources of discrepancies at low and high temperatures, respectively. Hybrid models are proposed and found to provide good correlated rate-constant values and to be competitive with conventional kinetic models, i.e., the Arrhenius and the three-parameter Arrhenius models. The combination of QM-calculated and experimental data sources proves particularly beneficial when fitting to scarce experimental data. The parameters of the model built on the hybrid strategy have a significantly reduced uncertainty (reflected in the much narrower 95% confidence intervals) compa
AU  - Diamanti,A
AU  - Adjiman,CS
AU  - Piccione,PM
AU  - Rea,AM
AU  - Galindo,A
DO  - 10.1021/acs.iecr.6b03443
EP  - 831
PY  - 2016///
SN  - 0888-5885
SP  - 815
TI  - Development of Predictive Models of the Kinetics of a Hydrogen Abstraction Reaction Combining Quantum-Mechanical Calculations and Experimental Data
T2  - Industrial & Engineering Chemistry Research
UR  - http://dx.doi.org/10.1021/acs.iecr.6b03443
UR  - http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000393354700001&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=1ba7043ffcc86c417c072aa74d649202
UR  - http://hdl.handle.net/10044/1/49007
VL  - 56
ER  -
Download