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Ag(I)-Promoted Substitution of Cyanide from Hexacyanoferrate(II) with Pyrazine: A Kinetic and Mechanistic Study

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Abstract

The kinetic spectrophotometric study of Ag(I)-promoted production of [Fe(CN)5PZA]3– was performed by monitoring the absorbance at 440 nm, the λmax of yellow-colored complex [Fe(CN)5PZA]3–. The formation of [Fe(CN)5PZA]3– proceeds via the Ag(I) catalyzed substitution of cyanide from [Fe(CN)6]4– with chromogenic ligand pyrazine (PZA). Pseudo-first-order conditions were used to study the reaction rate as a function of ionic strength, [Ag+], [PZA], temperature, pH, and [Fe(CN)64−] by varying one parameter at a time. According to the effect of reaction parameters on the initial rate, it was found that [Ag+] and pH strongly affect the reaction rate. The reaction displays variable order kinetics with [Fe(CN)\(_{6}^{{4 - }}\)] and [PZA] in the studied concentration ranges. Inverse trend in the initial rate with ionic strength exhibits a negative salt effect. An interchange dissociative (Id) mechanistic scheme as predicted by us was also strengthened by the large negative entropy of activation.

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We did not receive any specific grant for this research from any funding agencies in the public, commercial, or not-for-profit sectors.

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Authors and Affiliations

  1. Department of Chemistry, GLA University, 281406, Mathura, UP, India

    Abhishek Srivastava

  2. Department of Chemistry, Lucknow University, 226007, Lucknow, UP, India

    Radhey Mohan Naik & Jyoti Rai

  3. Department of Chemistry, MJS PG College, 477001, Bhind, MP, India

    Abhas Asthana

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  1. Abhishek Srivastava
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  2. Radhey Mohan Naik
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  3. Jyoti Rai
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  4. Abhas Asthana
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Correspondence to Abhishek Srivastava or Radhey Mohan Naik.

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The datasets generated or analyzed during the current study are available from the corresponding author on reasonable request.

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Srivastava, A., Naik, R.M., Rai, J. et al. Ag(I)-Promoted Substitution of Cyanide from Hexacyanoferrate(II) with Pyrazine: A Kinetic and Mechanistic Study. Russ. J. Phys. Chem. 95, 2545–2552 (2021). https://doi.org/10.1134/S0036024421130227

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