대한화학회지 (Journal of the Korean Chemical Society)

  • 제7권4호
  • /
  • Pages.238-244
  • /
  • 1963
  • /
  • 1017-2548(pISSN)
  • /
  • 2234-8530(eISSN)
대한화학회 (Korean Chemical Society)
권호 표지

熱力學函數間의 直線關係 (第2報) 適用性의 檢討

Linear Relationships between Thermodynamic Parameters (Part II) Applicabiliy of New Equations

  • 이익춘 (原子力硏究所 化學硏究室) ;
  • 박용자 (原子力硏究所 化學硏究室)
  • 발행 : 19631200
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초록

前報에서 誘導한 새로운 直線關係式,${\Delta}{\Delta}H^{\neq}=a{\sigma}+b{\Delta}{\Delta}S^\neq$ 및 ${\Delta}{\Delta}F^{\neq}=a{\sigma]+(b-T){\Delta}{\Delta}S^{\neq}$, 의 適用性을 57個反應으로 檢討하였다. 57個反應에 대한 ${\Delta}{\Delta}H^{\neq}-a{\sigma}$, 對 ${\Delta}{\Delta}S^{\neq}$의 直線關係 相關係數의 平均은 0.983이었고 直線으로부터의 標準備差의 平均値는 0.11이었다. 57個反應中 15個反應에 對해서는 Hammett方程式이 成立되지 않었고, 또 大部分의 反應에 對해서 Leffier의 式이 成立하지 않었다. 이와같이 從來의 關係式 이 成立하지 않는 反應도 새로운 關係式으로 設明되며, 그 理由를 檢討해 봄으로써 上記 2式이 더 一般的으로 適用되는 關係式임을 確認하였다.

Linear relationships between thermodynamic parameters, ,${\Delta}{\Delta}H^{\neq}=a{\sigma}+b{\Delta}{\Delta}S^{\neq}$, and $\Delta{\Delta}F^\neq=a\sigma+(b-T)\Delta{\Delta}S^\neq$, which were derived in the previous report have been tested with 57 reactions from literature. Linearities of plots $\Delta{\Delta}H^\neq-a\sigma$ vs. $\Delta{\Delta}S^\neq$ were generally good and the average correlation coefficient was 0.983 and the average of standard deviations from regression lines was 0.11. For 15 out of 57 reactions, Hammett plots were unsatisfactory and most of the reaction did not satisfy the Leffler equation. The general applicability of the new equations has been confirmed by the analysis of each reaction for which existing equations failed to correlate.

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참고문헌

  1. J. Korean Chem. Soc. v.7 Ikchoon Lee
  2. Physical Organic Chemistry L.P. Hammett
  3. J. Org. Chem. v.20 J.E. Leffler
  4. J. Org. Chem. v.27 R.F. Brown
  5. J. Phys. Chem. v.65 L.G. Hepler;W.F.O'Hara
  6. The Proton in Chemistry R.P.Bell
  7. J. Am. Chem. Soc. v.80 Y. Okamoto;T.Inukai;H.C.Brown
  8. J. Am. Chem. Soc. v.80 Y.Okamoto;H.C.Brown
  9. J. Am. Chem. Soc. v.79 Y.Okamoto;H.C.Brown
  10. J. Am. Chem. Soc. v.75 E.Berliner;L.H.Liu
  11. J. Am. Chem. Soc. v.74 E.Berliner;L.H.Altschul
  12. J. Am. Chem. Soc. v.79 F.G.Bordwell;G.D.Cooper;H.Morita
  13. J. Am. Chem. Soc. v.82 R.H.Dewolfe
  14. J.Chem.Soc. J.G.Mother;J.Shorter
  15. J.Chem.Soc. C.K.Ingold;W.S.Nathan
  16. J.Am.Chem.Soc. v.74 R.L.Herbst, Jr.;M.E. Jacox
  17. J.Chem.Soc. E.W.Timmond;C.N.Hinshelwood
  18. Kinetics of Reactions in Solution E.A.Moelwyn-Hughes
  19. Kinetics of Reactions in Solution E.A.Moelwyn-Hughes
  20. J.Am. Chem.Soc. v.76 C.C.Price;W.J.Belanger
  21. J.Am. Chem.Soc. v.73 C.C.Price;D.C.Lincoln
  22. J.Am. Chem.Soc. v.73 C.C.Price;D.C.Lincoln
  23. J.Org.Chem. v.27 R.F.Brown;H.C.Newsom
  24. J.Am.Chem.Soc. v.59 R.J.Hartman;A.M.Borders
  25. J.Am.Chem.Soc. v.62 R.J.Hartman;A.G.Gassman
  26. J.Am.Chem.Soc. v.61 R.J.Hartman;L.B.Storms;A.G.Gassman
  27. J.Am.Chem.Soc. v.74 H.A.Smith;R.B.Hurley
  28. J.Am.Chem.Soc. v.77 M.S.newsom;S.H.Merrill
  29. J.Am.Chem.Soc. v.80 W.N.White;D.G.Gwynn;R.Schlftt;C.GirardW.Fife
  30. J.Am.Chem.Soc. v.83 W.N.White;W.K.Fife
  31. J.Am.Chem.Soc. v.82 P.D.bartlett;C.Ruchardt
  32. J.Am.Chem.Soc. v.72 A.T.Blomquist;A.G.Buselli
  33. J.Chem.Soc. D.A.Blackadder;C.N.Hinshelwood
  34. J.Am. Chem.Soc. v.79 T.Mukayama;M.Iwanami
  35. J.Am. Chem.Soc. v.82 G.G.Smith;F.D.Bayley;R.Taylor
  36. J.Am. Chem.Soc. v.83 G.S.Krishnamurthy;S.I. Miller
  37. J.Am. Chem.Soc. v.81 L.P.Fernandez;L.G.Hepler
  38. Physical Organic Chemistry L.P. Hammett
  39. J.Am.Chem. Soc. v.79 C.H.Gudmundson;W.E.McEwen
  40. J.Chem.Soc. K.J.Laidler
  41. J.Chem.Soc. D.P.Evans;H.B.Watson;R.Williams
  42. J.Am. Chem. Soc. v.82 R.E. Dessy;J.Y.Kim
  43. J.Am. Chem. Soc. v.82 R.E.Dessy;Y.K.Lee
  44. J.Am. Chem. Soc. v.73 S.L.Friess;A.H.Soloway
  45. J. Chem. Soc. H.P.Crocker;B.Jones
  46. J.Am.Chem.Soc. v.85 B.B.P.Tice;Ikchoon Lee;F.H.Kendall
  47. J.Chem.Soc. J.D.Dickinson;C.Eaborn
  48. J.Am.Chem.Soc. v.80 G.M.Santerre;C.J.Hansrote,Jr.;T.I.Cromwell
  49. J.Am.Chem.Soc. v.85 T.C.Bruice;S.J.Benkovic
  50. J.Am.Chem.Soc. v.83 R.M.Laird;R.E.Parker
  51. J.Am.Chem.Soc. v.85 R.L.Carlson;R.S.Drago
  52. J.Am.Chem.Soc. v.85 R.L.Carlson;R.S.Drago
  53. J.Am.Chem.Soc. v.85 D.R.Eaton;W.D.Phillips;D.J.Caldwell
  54. Facts from Figures M.J.Moroney