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Title: Outer-sphere electron transfer from platinum(II) to Keggin-type 12-tungstocobaltate( III) in the presence and absence of chloride ions
Authors: Bhosale, B D
Gokavi, G S
Issue Date: Apr-2004
Publisher: NISCAIR-CSIR, India
IPC Code: Int. Cl.7 CO1G 55/00; CO1G 41/00; CO1G 51/00
Abstract:   The reaction between Pt(II) and [COIIIW12O40]5- proceeds with two, one-electron steps involving formation of unstable Pt(III) followed by its reaction with another oxidant. The reaction rate is unaffected by the [H+] as there are no protonation equlibria involved with both the reactant s whereas, chloride ion accelerates the reaction and the reaction follows chloride independent and dependent paths leading to a two term rate law, rate= {k1 + Kk2 [Clˉ]} [Pt(II)] [CoIIIW12O40]5-.
  The chloride ion dependent path is due to rapid substitution of chloride ion on PtCl42-. The products formed have been found to be PtCl4(aq) and PtCl62- in the absence and presence of chloride ion respectively. Increase in the ionic strength and decrease in the relative permittivity of the medium increase the rate of the reaction. This is due to the formation of an outer-sphere complex between the two reactants. The activation parameters in the presence and absence of chloride ions have also been determined and the values support the proposed mechanism.
Page(s): 799-802
ISSN: 0975-0975(Online); 0376-4710(Print)
Appears in Collections:IJC-A Vol.43A(04) [April 2004]

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