Kinetics and Mechanism for [Ni(CN)$_4]^{2-}$ Formation from [Ni(H$_2O)_6]^{2+}$ and [CN]$^-$ in Gelatin Solution

Gelatin 水溶液에서의 [Ni(H$_2O)_6]^{2+}$ 와 [CN]$^-$로 부터 [Ni(CN)$_4]^{2-}$生成에 관한 速度論的 硏究

  • Park Byung-Kak (Department of Chemistry, Yeungnam University) ;
  • Il-Bong Lee (Department of Chemistry, Yeungnam University) ;
  • Joo-Sang Lim (Department of Chemistry, Yeungnam University) ;
  • Gil-Jun Lee (Department of Chemistry, Yeungnam University)
  • 박병각 (嶺南大學校 理科大學 化學科) ;
  • 이일봉 (嶺南大學校 理科大學 化學科) ;
  • 임주상 (嶺南大學校 理科大學 化學科) ;
  • 이길준 (嶺南大學校 理科大學 化學科)
  • Published : 1987.10.20

Abstract

Kinetics studies on the reaction system of $[Ni(H_2O)_6]^{2+}+4CN^-{\rightleftharpoons}[Ni(CN)_4]^{2-}$ have been carried out in 0.005% gelatin solution at $25^{\circ}C$ by means of conductometry. The fifth-order kinetics were observed in the formation rate of $[Ni(CN)_4]^{2-}$ from the reaction of [Ni(H$_2O)_6]^{2+}$ and [CN]$^-$. The reaction was found first order in $[Ni(H_2O)_6]^{2+}$ and fourth order in [CN]$^-$. ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$ were obtained the values of 5.15kcal/mole and -35.07 e.u., respectively. We have proposed the possible mechanism from the data obtained.

反應系 $[Ni(H_2O)_6]^{2+}+4CN^-{\rightleftharpoons}[Ni(CN)_4]^{2-}$를 Counductivity-meter를 이용해서 0.005% Gelatin 水溶額에서 反應速度論을 硏究하였다. $[Ni(CN)_4]^{2-}$와 [CN]$^-$의 反應으로 부터 $[Ni(CN)_4]^{2-}$ 生成速度는 $[Ni(H_2O)_6]^{2+}$에 대해서 1次, [CN]$^-$에 대해서 4次인 총괄反應이 5次로 進行됨을 알았으며, 또한 活性化 파라메타 ${\Delta}H^{\neq}$${\Delta}S^{\neq}$는 각각 5.15kcal/mole , -35.07 e.u가 되었다. 그리고 이들의 資料로 부터 이 反應系의 타당한 生成메카니즘을 제안하였다.

Keywords

References

  1. The Study of Kinetics and Mechanism of Transition Metal Complex R. G. Wilkins
  2. Basic Inorganic Chemistry F. A. Cotton;G. Wilkins
  3. Bull. Chem. Soc. Jpn. v.46 S. Katama
  4. J. Am. Chem. Soc. v.72 A. W Adamson;J. P. Welker;M. Volpe
  5. J. Am. Chem. Soc. v.80 R. C. Calkins;N. F. Hall
  6. J. Am. Chem. Soc. v.72 D. N. Hume;I. M. Kolthoff
  7. J. Am. Chem. Soc. v.73 F. A. Long
  8. Inorg. Chem. v.8 G. B. Kolski;D. W. Margerum
  9. Inorg. Chem. v.83 D. W. Margerum;T. J. Bydalek;J. J. Bishop
  10. Coordination Chemistry F. Basolo;R. Johnson
  11. Reaction Kinetics v.I K. J. Laidler
  12. J. Kor. Chem. Soc. v.30 B. K. Park;J. W. Lee;J. S. Lim
  13. Advanced Inorganic Chemistry F. A. Cotton;G. Wilkins