Computer Science
Scientific paper
Sep 1989
adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=1989gecoa..53.2269s&link_type=abstract
Geochimica et Cosmochimica Acta, vol. 53, Issue 9, pp.2269-2276
Computer Science
Scientific paper
The oxidation of Cu(I) with H 2 O 2 in seawater and in NaCl solutions has been measured as a function of pH (6 to 9), temperature (5 to 45°C), ionic strength (0.5 to 6 m) and composition. The seawater rate constants, K ( M -1 s -1 ), for the oxidation d [ Cu ( I )]/ dt = - k [ Cu ( I )][ H 2 O 2 ] have been fitted to the equation log K = 11.55 - 2250/ T - 3.71 I 1/2 + 2.06 I with a = 0.04. The energy of activation was 43.1 ± 1.0 kJ mol -1 . At a constant ionic strength ( I = 1, 3, and 6 m) in NaCl-NaClO 4 mixtures, the Cl - dependence has been attributed to the oxidation of various forms of Cu(I) in the solution. At a fixed Cl - concentration, the addition of Mg 2+ causes the rate to decrease, and the addition of HCO - 3 causes the rate to increase. The increase due to HCO - 3 may be due to the formation of CuHCO 0 3 which has a faster rate of oxidation than CuCl 0 . The decrease caused by Mg 2+ may be due to the slow exchange of MgEDTA or MgCO 3 with Cu 2+ , which may cause the overall oxidation rates of Cu(I) to be slower due to back reactions of Cu(II) with H 2 O 2 . Empirical equations for the rate of oxidation of Cu(I) with H 2 O 2 in natural waters are given. The H 2 O 2 results are compared with the kinetics of Cu(I) oxidation with O 2 in natural waters. At the levels of O 2 (200 M) and H 2 O 2 (0.1 M) in surface sea waters, the oxygen oxidation is 130 times faster than peroxide oxidation. In rainwaters, however, the concentration of hydrogen peroxide (100 M) is great enough so that H 2 O 2 is the dominant oxidant for Cu(I).
Millero Frank. J.
Sharma Virender K.
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