Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
권호 표지
DOI QR코드

DOI QR Code

A Kinetic Study of Br Atom Reactions with Trimethylsilane by the VLPR (Very Low Pressure Reactor) Technique$^1$

  • Choo Kwang Yul (Department of Chemistry, College of Natural Sciences, Seoul National University) ;
  • Choe Mu Hyun (Department of Chemistry, College of Natural Sciences, Seoul National University)
  • 추광율 (서울대학교 자연과학대화학과) ;
  • 최무현 (서울대학교 자연과학대화학과)
  • Published : 1985.08.20
Download PDF
⟨ Previous Next ⟩

Abstract

A Very Low Pressure Reactor (VLPR) is constructed for the kinetic study of atom-molecule bimolecular elementary reactions. The basic principles and the versatility of the method are described. By using the VLPR technique the forward (k1) and the reverse (k-1) rate constants for Br atom reaction with trimethylsilane are studied; Br + $(CH_3)_3$SiH k1 ${\leftrightarrow}$ k-1 HBr + $(CH_3)_3$Si. From the kinetic data and the entropy estimation the bond dissociation energy for Si-H bond in trimethylsilane is calculated to be 90.1 kcal/mole $({\pm}1.1$ kcal/mole). The Arrhenius parameters for k1 are found to be log A = 10.6 l/mole·sec, $E_a$ = 4.4 kcal/mole respectively. For the comparison purpose analogous reaction for carbon compound ; Br + $(CH_3)_3$CH ${\rightarrow}$ HBr + $(CH_3)_3$C was also studied. The corresponding rate constant and equilibrium constant at $25^{\circ}C$ are found to be 2.67 ${\times}$ $10^6l$/mole${\cdot}$sec and 160 respectively.

Keywords

References

  1. Chem. Phys. Lett. v.89 M. Choe;K. Y. Choo
  2. J. Amer. Chem. Soc. v.104 C. R. Park;S. A. Song;Y. E. Lee;K. Y. Choo
  3. J. Amer. Chem. Soc. v.94 K. Y. Choo;P. P. Gaspar
  4. J. Amer. Chem. Soc. v.96 K. Y. Choo;P. P. Gaspar
  5. J. Amer. Chem. Soc. v.102 K. P. Steel;W. P. Weber
  6. J. Amer. Chem. Soc. v.100 W. D. Wuff;Goure;T. J. Barton
  7. J. Amer. Chem. Soc. v.103 R. T. Conlin;D. L. Wood
  8. J. Amer. Chem. Soc. v.103 T. J. Rahnak;J. Michl;R. West
  9. J. Phys. Chem. v.79 K. Y. Choo;P. P. Gaspar;A. P. Wolf
  10. J. Chem. Phys. v.70 J. V. Michael;D. F. Navam;L. J. Stief
  11. J. Chem. Phys. v.45 A. Carrington;D. H. Levy;T. A. Miller
  12. Int. J. Chem. Kinet. v.7 K. Y. Choo;D. M. Golden;S. W. Benson
  13. Int. J. Chem. Kinet. v.6 K. Y. Choo;D. M. Golden;S. W. Benson
  14. J. Amer. Chem. Soc. v.89 S. W. Benson;G. N. Spokes
  15. Angew, Chem. Internat. Edit. v.12 D. M. Golden;G. N. Spoken;S. W. Benson
  16. J. Amer. Chem. Soc. v.100 M. H. Baghal-Vayjooee;A. J. Cloussi;S. W. Benson
  17. Volatile Silicon Compounds E. V. A. Ebsworth
  18. J. Phys. Chem. v.70 F. E. Saalfeld;H. J. Svec
  19. Kinetic Theory of Gases W. Kauzman
  20. J. Chem. Phys. v.51 O. P. Strausz;E. Jakubowski;H.S. Sandhu;H. E. Gunning
  21. J. Chem. Phys. v.52 O. P. Strausz;E. Jakubowski;H.S. Sandhu;H. E. Gunning
  22. J. Phys. Chem. v.76 K. Obi;H. S. Sandhu;H. E. Gunning;O. P. Strausz
  23. Comprehensive Chemical Kinetics v.18 C. H. Bamford(ed.)
  24. J. Chem. Soc., Faraday Trans. 1 v.72 R. Walsh;J. M. Wells
  25. J. Amer. Chem. Soc. v.102 B. J. Cornett;K.Y. Choo;P. P. Gaspar
  26. J. Phys. Chem. v.83 S.K. Tokach;R. D. Koob
  27. Thermochemical Kinetics(2nd Ed.) S. W. Benson
  28. MTP International Review of Science. Inorganic Chemistry. Series One. Vol. 1. Main Group Elements-Hydrogen and Group I-IV v.1 H. J. Emeleus;M. F. Lampert(ed.)
  29. MTP International Review of Science. Inorganic Chemistry. Series Two. Vol. 2. Main Group Elements-Group Elements-Group IV adn V v.2 H. J. Emeleus;d. B. Sowerby(ed.)
  30. J. Chem. Soc., Faraday Trans. 1 v.74 A. C. Baldwin;I.M.T. Davidson;M. D. Reed
  31. J. Chem. Soc., A I.M.T. Davidson;C. A. Lambert
  32. J. Phys. Chem. v.77 A. Hosaka;F. S. Rowland
  33. J. Amer. Chem. Soc. v.87 G.G. Hess;F.W. Lamp;Sommer
  34. J. amer. Chem. Soc. v.84 W.C. Steele;L.P. Nichols;F.G.A. Stane
  35. J. Phys. Chem. v.84 G. Baruch;A. Horowitz
  36. Trans. Faraday Soc. v.66 E. R. Morris;J. C. Thynne
  37. J. Chem. Soc. Faraday Trans. 1 v.72 R. Walsh;J. M. Wells
  38. J. Chem. Soc. Faraday Trans. 1 v.72 A. M. Doncaster;R. Walsh