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Quantum yields of [W(CN)8]4− formation in charge-transfer photochemistry of octacyanotungstate (V)

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Summary

The reactions of monochromatically photolyzed aqueous [W(CN)8]3− solutions in the pH range 1–13 were found to consist of a two-step sequence involving a primary inter-molecular redox process and a consecutive thermal chain process, both leading to the formation of octacyanotungstate(IV) as the main reaction product. The initial quantum yields, φ0, are practically constant for the entire pH range and equal to 0.81±0.05 mole/Einstein. The final quantum yields, φf, for both neutral and alkaline solution, were found to be greater than 1, having also an approximately constant value of 3.42±0.25. The empirical rate law for the post-irradiation reaction under excess of [W(CN)8]3− and at constant pH is given by: rate = kobs[R]2[W(CN) 4−8 ]−2 where R is a one-electron reductant. Kinetic data suggest a mechanism of the Haber-Weiss type for the thermal reduction of [W(CN)8]3− by H2O2.

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Authors and Affiliations

  1. Institute of Chemistry, Jagiellonian University, Krakow, Poland

    Barbara Sieklucka, Aleksandra Kanas & Alina Samotus

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  1. Barbara Sieklucka
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  2. Aleksandra Kanas
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  3. Alina Samotus
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Sieklucka, B., Kanas, A. & Samotus, A. Quantum yields of [W(CN)8]4− formation in charge-transfer photochemistry of octacyanotungstate (V). Transition Met Chem 7, 131–134 (1982). https://doi.org/10.1007/BF01035825

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