Kinetics and Mechanism of Hg[II] Promoted, Acid Catalyzed and Ligand Induced Dissociation of Pentacy Ano P-Nitrosophenol and Pentacyano P-Nitroso-N,N'dimethylaniline Ferra Te[II].
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Date
1994-06
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Addis Ababa Universty
Abstract
The kinetics of dissociation of pentacyano paranitrosophenol
and 4-nitroso N,N'-dimethyl aniline ferrate(II}
complexes was studied under three different conditions:
i) substitution of PNP and PNA with excess pyridine, ii} acid
catalysed substitution of PNP and PNA and iii) Hg(II) promoted
aquation of the nitroso complexes.
The rates of dissociation of Fe [CN) 5PNA3- and Fe [CN) sPNp3-
increased with the concentration of pyridine and reached
limiting values at pyridine concentrations> 0.5 M. The pseudo
first order rate constants varied as
k=k1 k2 [PY]
where k, is the dissociation rate constant of the complexes,
and k_l and k2 are the association rate constants of Fe [eN) 53-
with Land py, respectively.
The enthalpy and entropy of activation are AH# = 95 ± 4 kJ
mol-1
, AS# = 22 ± 7 J mol-1 K-1 for Fe[CN)sPNA3- and AH# = 92 ± 3
kJ mol-1
, AS# = 14 ± 4 J mol- ' K- 1 for Fe [CN)5PNp3-. The rate
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Keywords
Pentacyano P-Nitrosophenol and Pentacyano