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Advances in Physical Chemistry
Volume 2013 (2013), Article ID 673065, 7 pages
http://dx.doi.org/10.1155/2013/673065
Research Article

Calculated Entropies for n-Heptane, 2-Methylhexane, 2,3-Dimethylpentane, and Radicals from the Loss of H Atoms

Chemistry, Chemical Engineering and Environmental Science, New Jersey Institute of Technology, Newark, NJ 07102, USA

Received 14 March 2013; Revised 17 May 2013; Accepted 19 May 2013

Academic Editor: Miquel Solà

Copyright © 2013 Jason M. Hudzik and Joseph W. Bozzelli. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Linked References

  1. S. F. Sousa, P. A. Fernandes, and M. J. Ramos, “General performance of density functionals,” The Journal of Physical Chemistry A, vol. 111, no. 42, pp. 10439–10452, 2007. View at Publisher · View at Google Scholar · View at Scopus
  2. H. J. Curran, P. Gaffuri, W. J. Pitz, and C. K. Westbrook, “A comprehensive modeling study of n-heptane oxidation,” Combustion and Flame, vol. 114, no. 1-2, pp. 149–177, 1998. View at Publisher · View at Google Scholar · View at Scopus
  3. H. J. Curran, W. J. Pitz, C. K. Westbrook, C. V. Callahan, and F. L. Dryer, “Oxidation of automotive primary reference fuels at elevated pressures,” Symposium (International) on Combustion, vol. 27, no. 1, pp. 379–387, 1998. View at Publisher · View at Google Scholar · View at Scopus
  4. T. J. Held, A. J. Marchese, and F. L. Dryer, “A semi-empirical reaction mechanism for n-heptane oxidation and pyrolysis,” Combustion Science and Technology, vol. 123, no. 1–6, pp. 107–146, 1997. View at Scopus
  5. K. K. Pant and D. Kunzru, “Pyrolysis of n-heptane: kinetics and modeling,” Journal of Analytical and Applied Pyrolysis, vol. 36, no. 2, pp. 103–120, 1996. View at Publisher · View at Google Scholar · View at Scopus
  6. T. Yuan, L. Zhang, Z. Zhou, M. Xie, L. Ye, and F. Qi, “Pyrolysis of n-heptane: experimental and theoretical study,” The Journal of Physical Chemistry A, vol. 115, no. 9, pp. 1593–1601, 2011. View at Publisher · View at Google Scholar · View at Scopus
  7. J. Zheng, T. Yu, and D. G. Truhlar, “Multi-structural thermodynamics of C–H bond dissociation in hexane and isohexane yielding seven isomeric hexyl radicals,” Physical Chemistry Chemical Physics, vol. 13, no. 43, pp. 19318–19324, 2011. View at Publisher · View at Google Scholar
  8. A. Karton, D. Gruzman, and J. M. L. Martin, “Benchmark thermochemistry of the CnH2n+2 alkane isomers (n=28) and performance of DFT and composite Ab initio methods for dispersion-driven isomeric equilibria,” The Journal of Physical Chemistry A, vol. 113, no. 29, pp. 8434–8447, 2009. View at Publisher · View at Google Scholar · View at Scopus
  9. D. Gruzman, A. Karton, and J. M. L. Martin, “Performance of Ab initio and density functional methods for conformational equilibria of CnH2n+2 alkane isomers n=48,” The Journal of Physical Chemistry A, vol. 113, no. 43, pp. 11974–11983, 2009. View at Publisher · View at Google Scholar · View at Scopus
  10. S. E. Wheeler, K. N. Houk, P. V. R. Schleyer, and W. D. Allen, “A hierarchy of homodesmotic reactions for thermochemistry,” Journal of the American Chemical Society, vol. 131, no. 7, pp. 2547–2560, 2009. View at Publisher · View at Google Scholar · View at Scopus
  11. D. W. Scott, Chemical Thermodynamic Properties of Hydrocarbons and Related Substances. Properties of the Alkane Hydrocarbons, C1 through C10 in the Ideal Gas State from 0 to 1500 K., U.S. Bureau of Mines, Bulletin 666, 1974.
  12. J. Pfaendtner, X. Yu, and L. J. Broadbelt, “The 1-D hindered rotor approximation,” Theoretical Chemistry Accounts, vol. 118, no. 5-6, pp. 881–898, 2007. View at Publisher · View at Google Scholar · View at Scopus
  13. V. van Speybroeck, D. van Neck, M. Waroquier, S. Wauters, M. Saeys, and G. B. Marin, “Ab initio study of radical addition reactions: addition of a primary ethylbenzene radical to ethene (I),” The Journal of Physical Chemistry A, vol. 104, no. 46, pp. 10939–10950, 2000. View at Publisher · View at Google Scholar · View at Scopus
  14. V. van Speybroeck, Y. Borremans, D. van Neck et al., “Ab initio study of radical reactions: cyclization pathways for the butylbenzene radical (II),” The Journal of Physical Chemistry A, vol. 105, no. 32, pp. 7713–7723, 2001. View at Publisher · View at Google Scholar · View at Scopus
  15. V. van Speybroeck, D. van Neck, and M. Waroquier, “Ab initio study of radical reactions: role of coupled internal rotations on the reaction kinetics (III),” The Journal of Physical Chemistry A, vol. 106, no. 38, pp. 8945–8950, 2002. View at Publisher · View at Google Scholar · View at Scopus
  16. S. Sharma, S. Ramans, and W. H. Green, “Intramolecular hydrogen migration in alkylperoxy and hydroperoxyalkylperoxy radicals: accurate treatment of hindered rotors,” The Journal of Physical Chemistry A, vol. 114, no. 18, pp. 5689–5701, 2010. View at Publisher · View at Google Scholar · View at Scopus
  17. G. Reinisch, J. M. Leyssale, and G. L. Vignoles, “Hindered rotor models with variable kinetic functions for accurate thermodynamic and kinetic predictions,” The Journal of Chemical Physics, vol. 133, no. 15, Article ID 154112, 10 pages, 2010. View at Publisher · View at Google Scholar
  18. K. S. Pitzer, “Thermodynamic functions for molecules having restricted internal rotations,” The Journal of Chemical Physics, vol. 5, no. 6, pp. 469–472, 1937. View at Scopus
  19. K. S. Pitzer, “Energy levels and thermodynamic functions for molecules with internal rotation: II. Unsymmetrical tops attached to a rigid frame,” Journal of Chemical Physics, vol. 14, no. 4, pp. 239–243, 1946. View at Publisher · View at Google Scholar
  20. K. S. Pitzer and W. D. Gwinn, “Energy levels and thermodynamic functions for molecules with internal rotation: I. Rigid frame with attached tops,” The Journal of Chemical Physics, vol. 10, no. 7, pp. 428–440, 1942. View at Scopus
  21. J. E. Kilpatrick and K. S. Pitzer, “Energy levels and thermodynamic functions for molecules with internal rotation. III. Compound rotation,” The Journal of Chemical Physics, vol. 17, no. 11, pp. 1064–1075, 1949. View at Scopus
  22. V. van Speybroeck, P. Vansteenkiste, D. van Neck, and M. Waroquier, “Why does the uncoupled hindered rotor model work well for the thermodynamics of n-alkanes?” Chemical Physics Letters, vol. 402, no. 4–6, pp. 479–484, 2005. View at Publisher · View at Google Scholar · View at Scopus
  23. P. Y. Ayala and H. B. Schlegel, “Identification and treatment of internal rotation in normal mode vibrational analysis,” Journal of Chemical Physics, vol. 108, no. 6, pp. 2314–2325, 1998. View at Scopus
  24. P. Vansteenkiste, D. van Neck, V. van Speybroeck, and M. Waroquier, “An extended hindered-rotor model with incorporation of Coriolis and vibrational-rotational coupling for calculating partition functions and derived quantities,” Journal of Chemical Physics, vol. 124, no. 4, Article ID 044314, 14 pages, 2006. View at Publisher · View at Google Scholar
  25. C. Y. Lin, E. I. Izgorodina, and M. L. Coote, “How accurate are approximate methods for evaluating partition functions for hindered internal rotations?” The Journal of Physical Chemistry A, vol. 112, no. 9, pp. 1956–1964, 2008. View at Publisher · View at Google Scholar · View at Scopus
  26. P. Vansteenkiste, V. van Speybroeck, E. Pauwels, and M. Waroquier, “How should we calculate multi-dimensional potential energy surfaces for an accurate reproduction of partition functions?” Chemical Physics, vol. 314, no. 1–3, pp. 109–117, 2005. View at Publisher · View at Google Scholar · View at Scopus
  27. P. Vansteenkiste, V. van Speybroeck, G. B. Marin, and M. Waroquier, “Ab initio calculation of entropy and heat capacity of gas-phase n-alkanes using internal rotations,” The Journal of Physical Chemistry A, vol. 107, no. 17, pp. 3139–3145, 2003. View at Publisher · View at Google Scholar · View at Scopus
  28. T. Yu, J. Zheng, and D. G. Truhlar, “Statistical thermodynamics of the isomerization reaction between n-heptane and isoheptane,” Physical Chemistry Chemical Physics, vol. 14, no. 2, pp. 482–494, 2012. View at Publisher · View at Google Scholar
  29. D. R. Stull, E. F. Westrum Jr., and G. C. Sinke, The Chemical Thermodynamics of Organic Compounds, Wiley, New York, NY, USA, 1969.
  30. A. D. Becke, “Density-functional thermochemistry. III. The role of exact exchange,” The Journal of Chemical Physics, vol. 98, no. 7, pp. 5648–5652, 1993. View at Scopus
  31. C. Lee, W. Yang, and R. G. Parr, “Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density,” Physical Review B, vol. 37, no. 2, pp. 785–789, 1988. View at Publisher · View at Google Scholar · View at Scopus
  32. M. J. Frisch, G. W. Trucks, H. B. Schlegel et al., Gaussian 03, Revision D.01, Gaussian, Wallingford, Conn, USA, 2003.
  33. C. Sheng, Elementary, pressure dependent model for combustion of C1, C2 and nitrogen containing hydrocarbons: operation of a pilot scale incinerator and model comparison [Ph.D. dissertation], Department of Chemical Engineering, New Jersey Institute of Technology, Newark, NJ, USA, 2002.
  34. A. P. Scott and L. Radom, “Harmonic vibrational frequencies: an evaluation of Hartree-Fock, Møller-Plesset, quadratic configuration interaction, density functional theory, and semiempirical scale factors,” The Journal of Physical Chemistry, vol. 100, no. 41, pp. 16502–16513, 1996. View at Scopus
  35. T. H. Lay, J. W. Bozzelli, A. M. Dean, and E. R. Ritter, “Hydrogen atom bond increments for calculation of thermodynamic properties of hydrocarbon radical species,” The Journal of Physical Chemistry, vol. 99, no. 39, pp. 14514–14527, 1995. View at Scopus
  36. T. H. Lay, L. N. Krasnoperov, C. A. Venanzi, J. W. Bozzelli, and N. V. Shokhirev, “Ab initio study of α-chlorinated ethyl hydroperoxides CH3CH2OOH, CH3CHClOOH, and CH3CCl2OOH: conformational analysis, internal rotation barriers, vibrational frequencies, and thermodynamic properties,” The Journal of Physical Chemistry, vol. 100, no. 20, pp. 8240–8249, 1996. View at Publisher · View at Google Scholar · View at Scopus