Phillip R. Westmoreland
Phillip R. Westmoreland, Professor
157A Goessmann Lab
Chemical Engineering Department
University of Massachusetts Amherst
686 N. Pleasant Street
Amherst, MA 01003-3110
413-545-1750 (Office)
413-545-1647 (FAX)
[On leave, 2006-09: National Science Foundation, Arlington VA]
westm@ecs.umass.edu
Prof. Westmoreland's vita is available separately. View a list of our group members and alumni.
Education
B.S., Chemical Engineering, North Carolina State University, 1973
M.S., Chemical Engineering, Louisiana State University, 1974
Ph.D., Chemical Engineering, Massachusetts Institute of Technology, 1986
Recognitions & Awards
George R. Lappin Award, AIChE, 2006
Outstanding Senior Faculty Award, College of Engineering, 2006
David A. Shirley Award for Outstanding Scientific Achievement, Lawrence Berkeley National Laboratory, 2005
William H. Corcoran Award, ASEE, 2002
MSI Materials Science Award, 2001 (with S.I. Stoliarov and M.R. Nyden)
Editorial Advisory Boards: I&EC Research, 1998-2000; International Journal of Chemical Kinetics, 2000-2002
BCR / R. A. Glenn Award for Best Paper, ACS Fuel Chemistry Division, 1992
Outstanding Junior Faculty Award, College of Engineering, 1992
NATE Award (Central New England AIChE Tribute to Excellence), 1991
Presidential Young Investigator, 1990-95
General Electric Outstanding Teaching Award, 1990
AIChE Public Relations Award, 1977
Current Focus of Research
We focus on understanding and using kinetics at a molecular scale, theoretically and experimentally.
Molecular Modeling and Reaction Theory
We are working to make computational quantum chemistry become a tool for analysis and design in chemical engineering. Ab initio wavefunction and density-functional theories are evolving rapidly as quantitative accuracy is sought. We exploit these developments to evaluate chemical equilibria, reaction rates, and product channels.
Typically, we first identify reactants or products of interest. We search for structures that might satisfy the experimental constraints, initially applying a modest level of theory like Hartree-Fock or B3LYP/6-31G(d). Transition states are analyzed along their internal reaction coordinates, which confirms the reactants and products. Finally, we get accurate energies from high-level calculations like CBS-QB3.
With this information, we predict high-pressure-limit rate constants. For gas-phase reactions, we also predict rate expressions with products and temperature and pressure dependences using quantum reaction theories such as Bimolecular Quantum-RRK, RRKM, and Master Equation theory.
Combustion Research
Our combustion research is driven both by the interesting chemistry and the practical need to avert unwanted environmental effects. Aromatics formation is of particular interest because polycyclic aromatics lead to soot and are themselves mildly carcinogenic. Likewise, kinetics of oxidation is needed to insure efficient fuel usage and effective incineration. This information is also relevant to chemical manufacturing, including catalytic oxidation.
Molecular-beam mass spectrometry (MBMS) is a key tool for us, used to measure concentrations of free radicals and molecules in low-pressure flames. With these data, we have evaluated and developed elementary-reaction mechanisms of pyrolysis, oxidation, and growth. Rate constants are both measured in the experiments and predicted by quantum reaction theories, and concentrations are predicted from the full mechanisms by solving coupled transport equations. This work has revealed unusual pressure dependences and new reactions that are now supported by data. The results are being used at GE and United Technologies to design new gas turbines.
Fire-safe Polymers
Theory and experiment are both being used to develop new, fire-safe polymers. Theoretically, we are predicting reaction pathways and bond dissociation energies using ab initio and semi-empirical quantum chemistry calculations. We also study polymer decomposition experimentally using new apparata that combine flash pyrolysis or TGA/DSC with GC-MS. This work has yielded useful correlations with standard, large-sample flammability tests, allowing us to predict the flammability of new polymers with only micrograms of sample. Through collaborations with faculty in Polymer Science and Engineering, several of these new polymers have been developed and are now moving toward commercialization.
Selected Publications
M.E. Law, P.R. Westmoreland, T.A. Cool, J. Wang, N. Hansen, T. Kasper. "Benzene Precursors and Formation Routes in a Stoichiometric Cyclohexane Flame," Proceedings of the Combustion Institute, 31, xxx (2007).
N. Hansen, S.J. Klippenstein, J.A. Miller, J. Wang, T.A.Cool, M.E.Law, P.R. Westmoreland, T. Kasper, K. Kohse-Hoeinghaus. "Identification of C5Hx Isomers in fuel-rich flames by photoionization mass spectrometry and electronic structure calculations," J. Phys. Chem. A, 110(13), 4376-4388 (2006).
C.A. Taatjes, N. Hansen, A. McIlroy, J.A. Miller, J.P. Senosiain, S.J. Klippenstein, F. Qi, L. Sheng, Y. Zhang, T.A. Cool, J. Wang, P.R. Westmoreland, M.E. Law, T. Kasper, K. Kohse-Hoeinghaus, "Enols Are Common Intermediates in Hydrocarbon Oxidation," Science, 308(5730), 1887-9 (2005) [cover article].
B. Ruscic, J.E. Boggs, A. Burcat, A.G. Czaszar, J. Demaison, R. Janoschek, J.M.L. Martin, M. L. Morton, M. J. Rossi, J. F. Stanton, P. G. Szalay, P.R. Westmoreland, F. Zabel, T. Berces, "IUPAC critical evaluation of thermochemical properties of selected radicals - Part I," J. Phys. Chem. Ref. Data 34(2), 573-656 (2005).
M.R. Nyden, S.I. Stoliarov, P.R. Westmoreland, Z.X. Guo, and C. Jee. "Applications of Reactive Molecular Dynamics to the Study of the Thermal Decomposition of Polymers and Nanoscale Structures," Materials Science and Engineering A, 365, 114-121 (2004).
S.I. Stoliarov and P.R. Westmoreland. "Mechanism of the Thermal Decomposition of Bisphenol C Polycarbonate: Nature of Its Fire Resistance," Polymer, 44, 5469-5475 (2003).
P.R. Westmoreland, P.A. Kollman, A.M. Chaka, P.T. Cummings, K. Morokuma, M. Neurock, E.B. Stechel, and P. Vashishta. Applying Molecular and Materials Modeling: An International Comparative Study, Kluwer Academic, New York (2002).
P.R. Westmoreland. "Chemistry and life sciences in a new vision of chemical engineering," Chemical Engineering Education, 35(4), 248-255 (2001).
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