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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 33, Number 4
JKCSEZ 33(4)
August 20, 1989 

Effects of Temperature and Pressure on the Reaction of [Pt(dien)X]+ with NO2- Aqueous Solutions

수용액에서 [Pt(dien)X]+ 와 NO2-와의 치환반응에 미치는 온도 및 압력변화
Sang Oh Oh, Sang Hyup Lee, Hwan Jin Yeo, Jong Wan Lim, Du Hwan Jo

오상오, 이상협, 여환진, 임종완, 조두환
분광광도법을 이용하여 [pt[dien]X]+(X = Cl-, Br-, I-) 와 NO2-와의 치환반응을 20∼35℃, 1∼1500 bar 범위에서 조사했다. 이들 반응의 속도는 모두 온도와 압력이 증가함에 따라 증가하였고, 치환 용이성은 Cl- > Br- > I- 였다. 활성화 부피변화(│ΔV≠│)는 모두 큰 음(-)의 값을 가졌고 온도가 증가함에 따라 감소하였다. 25℃에서 구한 일차속도상수(k1)와 이차속도상수 (k2)는 압력이 증가함에 따라 다같이 증가하였고, k1 경로와 k2 경로에 대한 활성화부피(ΔV1≠ 와 ΔV2≠)는 모두 큰 음(-)의 값을 가졌다. 또한 1 bar에서 k1과 k2를 구했고 온도가 증가함에 따라 모두 증가하였다. 각 반응경로에 대한 활성화파라미터를 결정했고, 모든 실험적 결과로부터 이 반응은 이탈기의 성질과 반응경로에 관계없이 회합(A)메카니즘을 가질 것으로 생각된다.

Kinetics of the substitution reaction of [pt[dien]X]+(X = Cl-, Br-, I-) with NO2- in aqueous solution were investigated by a spectrophotometric method at 20-35℃ and 1-1500 bars. The rates of these reactions were increased with raising temperature and pressure. The relative reactivities of replaceable ligands in [pt[dien]X]+ follow the order (Cl- > Br- > I-). Activation volumes (│ΔV≠│) were large negative values and decreased with raising temperature. First (k1) and second(k2) order rate constants of these reactions were determined at 25℃ and both k1 and k2 were increased with raising pressure and activation volumes (ΔV1≠, ΔV2≠) for the k1 and k2 path were large negative values respectively. The k1 and k2 of these reactions were determined at 1 bar and these values were increased with raising temperature. Activation parameters of k1 and k2 path were determined, therefore it can be inferred frp, these results that the substitution reactions of [pt[dien]X]+ with NO2- proceed through on associative (A) mechanism independent of a leaving groups and reaction paths.

371 - 378
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