Pressure Effect on the Aquation of trans-[Cr(tn)2Cl2]+ and trans-[Cr(en)(tn)Cl2]+ Complex Ions 


Vol. 31,  No. 5, pp. 375-381, Oct.  1987


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  Abstract

trans-[Cr(tn)2Cl2]+ 및 trans-[Cr(en)(tn)Cl2]+ 이온의 수화반응속도를 분광광도법을 이용하여 온도의 압력을 변화시켜 가면서 측정하였다. 활성화부피는 모두 음의 값을 가졌으며. 이들 착이온의 경우 그 범위는 -1.7 ∼ -2.9cm3mol-1이었다. 활성화엔트로피 및 활성화압축류 계수는 작은 음의 값을 가졌다. 이러한 열역학적 결과로부터 이들 착이온의 수화반응은 교환회합 메카니즘으로 진행됨을 추정할 수 있다. 한편 각중첩모형 체제내에서 가상적 중간체의 총 안정화에너지를 고려하여 반응경로와 전이상태의 구조에 대한 정보를 얻을 수 있는데 추정한 메카니즘과 실험적으로 관찰된 결과가 일치함을 알았다. Rates for the aquation of trans-[Cr(tn)2Cl2]+ and trans-[Cr(en)(tn)Cl2]+ ions in aqueous acidic solution have been measured by spectrophotometric method at various temperatures and pressures. Activation volumes are negative and lie in the limited range -1.7 ∼ -2.9cm3mol-1 or the complex ions. Activation entropies and activation compressibility coefficients are small negative values. From the results of thermodynamic parameters, it can be inferred that the aquation of the complex ions proceed through an associative interchange(Ia) mechanism. Furthermore, the information on possible transition state structure and reaction paths can be obtained by considering total stabilization energy of the hypothetical intermediates within the framework of angular overlap model. It is found that the theoretically predicted mechanism is consistent with the experimentally observed results.

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  Cite this article

[IEEE Style]

J. Chung, J. Choi, D. Kim, "Pressure Effect on the Aquation of trans-[Cr(tn)2Cl2]+ and trans-[Cr(en)(tn)Cl2]+ Complex Ions," Journal of the Korean Chemical Society, vol. 31, no. 5, pp. 375-381, 1987. DOI: .

[ACM Style]

Jong-Jae Chung, Jong-Ha Choi, and Deog-Jin Kim. 1987. Pressure Effect on the Aquation of trans-[Cr(tn)2Cl2]+ and trans-[Cr(en)(tn)Cl2]+ Complex Ions. Journal of the Korean Chemical Society, 31, 5, (1987), 375-381. DOI: .

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ISSN(Print) 1017-2548
ISSN(Online) 2234-8530