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Effect of ionic interactions on the rates of reduction of Cu(II) with H2O2 in aqueous solutions

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Abstract

The rates of reduction of Cu(II) with H2O2 have been measured in NaCl and NaBr solutions and mixtures with NaClO4 as a function of pH (6 to 9), temperature (5 to 45°C) and ionic composition (0.1 to 6M). The effect of pH on the rates was found to be independent of temperature and ionic composition. The rates increased as a function of [H+] raised to the power of 1.3 to 1.6. Speciation calculations indicate that this pH dependence can be attributed to Cu(OH)2 being the reactive species. The rate constants in NaCl and NaBr and mixtures with NaClO4 were independent of ionic strength, but proportional to the halide concentration raised to the power of 2.0 (0.2 to 2.6M). These results can be attributed to Cu(OH)2Cl 2−2 being the reactive species to reduction with H2O2. The Cu(I) halide complexes formed from the reduction are not easily oxidized with O2 or H2O2. The faster rates in Br− solutions, which form stronger complexes with Cu+, support this contention. Measurements made in NaCl with added NaHCO3, NaB(OH)4 EDTA, NTA and glycine were also made. These measurements indicate that the CuL complexes (L=B(OH) −4 , CO 2−3 , EDTA, NTA, and glycine) are not very reactive to reduction with H2O2. The addition of Mg2+ or Ca2+ caused the rates to increase due to the formation of MgL or CaL complexes and the resultant release of reactive Cu2+.

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Authors and Affiliations

  1. Rosenstiel School of Marine and Atmospheric Science, University of Miami, 4600 Rickenbacker Causeway, 33149, Miami, FL

    F. J. Millero, V. K. Sharma & S. Sotolongo

  2. Department of Chemistry, Hillsdale College, 49242, Hillsdale, MI

    R. L. Johnson

  3. Department of Chemistry, University of Puerto Rico, 00708, Mayaguez, P.R.

    C. A. Vega

Authors
  1. F. J. Millero
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  2. R. L. Johnson
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  3. C. A. Vega
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  4. V. K. Sharma
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  5. S. Sotolongo
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Millero, F.J., Johnson, R.L., Vega, C.A. et al. Effect of ionic interactions on the rates of reduction of Cu(II) with H2O2 in aqueous solutions. J Solution Chem 21, 1271–1287 (1992). https://doi.org/10.1007/BF00667222

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  • DOI: https://doi.org/10.1007/BF00667222

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