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Certified by Estimation Method for the Thermochemical Properties of Polycyclic Aromatic Molecules by Joanna Yu Bachelor of Science in Engineering, Escola Politcnica-USP, Sao Paulo, Brazil, 2001 Submitted to the Department of Chemical Engineering in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Chemical Engineering Practice at the MASSACHUSETTS INSTITUTE OF TECHNOLOGY September 2004 © Massachusetts Institute of Technology 2004. All rights reserved. Author. · epartment of Chemical Engineering September 1, 2004 Certifiedbyby ............... .............. ,f.\.. ................................... (U)William H. Green, Jr. Texaco-Mangelsdorf Associate Professor Thesis Supervisor Acceptedby............ ................... ..... Daniel Blankschtein Professor of Chemical Engineering Chairman, Committee for Graduate Students MASSACHUSETTS INSTTUTE OF TECHNOLOGY F SEP 12 2005 _ 11"C4,1~e- LIBRARIES Estimation Method for the Thermochemical Properties of Polycyclic Aromatic Molecules by Joanna Yu Bachel)or of Science in Engineering, Escola Polit6cnica-USP, So Paulo, Brazil, 2001 Submitted to tle Departmenlt of Chemical Engineering on September 1, 2004, in partial fulfillment of the requiremlents for tle degree of Doctor of Philosophy in Chemical Engineering Practice Abstract Polycy( lic aromatic molecules, icluding polycyclic aromatic hydrocarbons (PAHs) have attracted c(onsiderable attention in the Ipast few decades. They are formed dur- ing the incomipliete combustion of hydrocarbon fuels and are precursors of soot. Some PAHs are known carcilnogens, and control of their emissions is an important issue. These nlolecules uarefound in Ilany materials, including coal, fuel oils, lubricants, andl carton )l lack. They are also ilmpi)licatedi tle formation of fullerenes, one of the Ilost. chemi(( ally versatile class of molecules known. Clearly, models that p)rovide predic- tive cap:,ability for their formation and growth are highly d(esiral)le. Thlermioclheiical t)ro)erties of the secies in the mlodel are often tle mIlostillmplortanIt )arameter, par- tic(ularly for high temtI)erature processes such a.s the formation of PAH and other aromlati( molecules. Ther1odynlamlic consist ency reqluires that reverse rate const ants b)e c(alculated froil the forward rate constants and fron the equilibriuml constants. The later are obtaiined fromllthe thermnochelnicalproperties of reactants an(dproduc(ts. The I)re(lictive ability of culrrelt kinetic Imlodelsis significantly limited )bythe sca.rcity of available thermoc(lemnical data. IIn this work we )resenit the developmenIlt of a Bond-Centered Group Additivity ethlod for tle estilmation of the therInochlleical properties of polycyclic arolmatic molecul,s, including PAHs, molecules with the furan substructure, miioleculeswith 3 triple bonds, substituted PAHs, and radicals. This method is based on thermochern- ical values of about two hundred polycyclic aromatic molecules and radicals obtained from quantuin chemical calculations at tle B3LYP/6-31G(d) level. A consistent set of homnodesmicreactions has been dleveloped to accurately calculate the heat of for- mation from the absolute energy. The entropies calculated from the B3LYP/6-31G(d) vibrational frequencies are shown to be at least. a.s reliable as the few available ex- perimental values. This new Bond-Centered Group Additivity method predicts the thermochemistry of C60 and C 70 fullereIes, as well as smaller aromatic molecules, with accuracy comparable to both experiments and the best quantum calculations. This Bond-Centered Group Additivity method is shown to extrapolate reasonably to infinite graphene sheets. The Bond-Centered Group Additivity method has been impleImented into a com- puter code within the automatic Reaction Mechanism Generation software (RMG) developed in our group. The database has been organized as a tree structure, making its maintenance and possible extension very straightforward. This computer code al- lows the fast and easy use of this estimation method by non-expert users. Moreover, since it is incorporated into RMG, it will allow users to generate reaction mechanisms that include aromatic molecules whose thermlochemica,lproperties are calculated us- ing the Bond-Centered Group Additivity method. Exploratory equilibrium studies were performle(l. Equilibrium concentrations of individual species depend strongly on the the rnochenlistry of the individual species, emphasizing the importance of consistent therlmochemistry for all the species involved in the calculationls. Equilibrium calculations can provide nlany interesting insights into the relationship between PAH anIldfullerenes in combustion. Thesis Supervisor: Williami H. Green, ,Jr. Title: Texaco-Mangelsdorf Associate Professor 4 Acknowledgments tManypeople Iprovidel lhelp and supp)ort that allowed the completion of this work ill such a short time fame. First, I would like to thank mly advisor Prof. Bill Green. He pIrovidle(dine with the fr'eedo to explore and to learn to find Inyown path, while also I)ointilngto the righlt direction when I was at a lost. His insights improved this work conIsi(leral)ly. I amIIlalso grateful to the other embers of llmy thesis ommittee, Prof. Jack Howard and Piof. Larry S('ott, for their tilme, interest., and suggestions. Dr. Sumttlhy Ranlan patiently explainled to I(c almost (everything that I know about qulantuli chemistry andt supplie(d a c ode for the calculation of the thermllocheim- ic:al contril)lltionIs of hindered rotors. She also gave vatllluable advice, both research related and otherwise. Dr. Henning Richter provided the ultimate incenitive for this work by being a user in need of thermochelical lata. He gave Ile guidance andl filled Ile in te relevant c ioml)ustionwork. Dr. Richter also performed soime of the equi- lib)rium calculations and provided Ime the thermocheniistry in Cheimkin format usedl for other equiliblrium calculations. Dr. ing Song introduced Ime(to object orientel p)rogramling, UNIL,and .Jatv. Her RMG program is the backb)one without which the BCG3IKA thermo estinitor program would not. stand. Sally Petway (Ievelope(d alnd itil)lemIented in RAIG the algorithmI for the calculation of the symmlletrynumber of ring (OIl)o(dlIl(s. I havt7ea beeni extremely fortunate with the company that I have had in the past three years, )()othiside and outside tlhe lab. Susan Lanza took care of every administrative hurdle and also of the well-being of the nembers of the Green Group. Paul Yelvington was a glea.t lab comlpanion and was always very helpfull in Unix amid other mIlatters. Bryan Wiong aiswered many of mlyqcluestions about physical chiemistry, and together with ()h(wayemrisi Luwi" Oluwole, was te source of lively discussions about topics ranging froll slt)ac('tri)ps to Mars to pageant contests. All other mIleib('rs of the Green Groupl, past ad prI'esent, are acknowledlge(l for their calaraderie and discussions durinig group seminar. Many others were also key to Imakingthese years a great timle, aIld although te list is lobg, I aml especially grateful to Pia Kohller, Thierry Savinl, 5 Alexander Mitsos, Eva Lambidoni, Anna Pisania, and Yuhua Hu. Finally, I would like to thank my pa.rents for their unwavering support in every matter. This work was supported by the National Science Foundation through research grant CTS-0123345. Support from the National Center for Supercomputing Applica- tions through the allocation of supercomputer resources is acknowledged. 6 Contents 1 Introduction 21 1.1 Thesis ()verview b)y Chapter ....................... 23 1.1.1 Chapter 2: TherimocheIlmicalData for PAHs .......... 23 1.1.2 Chlapter 3: Bond(-Ceiltered Group Additivity Method ..... 24 1.1.3 Chapter 4: BCGA for (ther Aroinatic Molecules ....... 24 1.1.4 Chlapter 5: BCGA for R.adicals. 25 1.1.5 Cllapter 6: R.esoiinance Energy . 25 1.1.6 Clhapter 7: Thler ocllhemistry fol Non-Aroilmatic XMolcllulesandt Radicals. 25 1.1.7 Chapter 8: BCGA i RMG ................... 26 1.1.8 Clhapter 9: Equilibriliuml Calculatios . ... 26 Bibliography 26 2 Thermochernmical Data for Estimation Method for PAHs with Five- and Six-Membered Rings 29 2.1 Itro(luction ...................... ......... 29 2.2 Experimental ThlermochemiicalProperties . .......... .......29 2.2.1 Experiimental Enthalpy of Forimation Values ... .. I... 30 2.2.2 Experiilental Eltropy Values ........ .......... ...40 2.3 Coloputational Metlos . .......... ....41 2.4 Results andi Discussion ................ .......... ......51 Bilbliography .. ... .. .... $......51 7 3 Bond-Centered Group Additivity Estimation Method 61 3.1 Existing Estimation Methods. 61 ........ 3.2 Bond-Centered EstiImation Method ........... ........ 68 3.2.1 Definition of Bond-Centered Groups... ........ 69 3.2.2 Statistical Validation of the Molel ....... 75 3.2.3 Coefficients for the Bond-Centered Group Additi)vity Method 78 3.3 Results and(IDiscussion .................. 79 ..... 3.4 Conclusions ....................... 89 ..... Bibliography 90 4 Other Polycyclic Aromatic Molecules 93 4.1 Introduction . ........... 93 4.2 Furans ................. ........... 93 4.2.1 Introduction . ........... 93 4.2.2 Previous EstiImation Methods . ........... 94 4.2.3 Comlputational Methods . ........... 94 4.2.4 Estimation Method .... .......... 95 4.2.5 Results and Discussion .... ........... 98 4.3 Arynes................. ........... 100 4.3.1 Introduction . ........... 100 4.3.2 Experimenta1 Values. ........... 101 4.3.3 ComnputationalMethods ... ........... 102 4.3.4 Estiniation Method . ..........
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