Kinetics And Mechanism Of Hgii Promoted Acid Catalyzed And Ligand Induced Dissociation Of Pentacy Ano P-nitrosophenol And Pentacyano P-nitroso-nndimethylaniline Ferra Teii.

The kinetics of dissociation of pentacyano paranitrosophenolrnand 4-nitroso N,N'-dimethyl aniline ferrate(II}rncomplexes was studied under three different conditions:rni) substitution of PNP and PNA with excess pyridine, ii} acidrncatalysed substitution of PNP and PNA and iii) Hg(II) promotedrnaquation of the nitroso complexes.rnThe rates of dissociation of Fe [CN) 5PNA3- and Fe [CN) sPNp3-rnincreased with the concentration of pyridine and reachedrnlimiting values at pyridine concentrations> 0.5 M. The pseudornfirst order rate constants varied asrnk=k1 k2 [PY]rnwhere k, is the dissociation rate constant of the complexes,rnand k_l and k2 are the association rate constants of Fe [eN) 53-rnwith Land py, respectively.rnThe enthalpy and entropy of activation are AH# = 95 ± 4 kJrnmol-1rn, AS# = 22 ± 7 J mol-1 K-1 for Fe[CN)sPNA3- and AH# = 92 ± 3rnkJ mol-1rn, AS# = 14 ± 4 J mol- ' K- 1 for Fe [CN)5PNp3-. The rate

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