Physics
Scientific paper
Aug 1989
adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=1989gecoa..53.1867m&link_type=abstract
Geochimica et Cosmochimica Acta, vol. 53, Issue 8, pp.1867-1873
Physics
25
Scientific paper
The oxidation of Fe(II) with H 2 O 2 has been measured in seawater as a function of pH (2 to 8.5), temperature (5 to 45°C) and salinity (0 to 35). The effect of pH on the rate constant, k , d [ Fe ( II )]/ dt = - K [ Fe ( II )][ H 2 O 2 ] was found to be a linear function of [H + ] or [OH - ] from pH = 6 to 8. The effect of temperature and ionic strength on k at pH = 6.0 was given by log K = 13.73 -2,948/ T - 1.707 1/2 + 1.20 I with a = 0.12 in log k . If the rates are expressed as d ( Fe ( II )]/ dt = - k 2 [ Fe ( II )][ H 2 O 2 ][ OH - ] the values of k 2 are independent of temperature. This is due to the fact that the energy of activation of k is the same order of magnitude of H w *, the heat of ionization of water. The ionic strength dependence of k 2 was given by log k 2 = 11.72-2.14 I 1/2 + 1.38 I with a = 0.11 in log k 2 . The results of k over the entire pH, temperature and ionic strength were given by k = k 0 Fe + k 1 FeOH where Fe and FeOH , k 0 and k 1 are the rate constants, respectively, for the oxidation of Fe 2+ and FeOH + . The values of k 0 and k 1 are given by log k 0 = 8.37- 1,866/ T log k 1 = 17.26 - 2,948/ T - 1.70 I 1/2 + 1.20 I . The addition of HCO 3 - at a constant pH was found to linearily increase the rate independent of the salinity and temperature. This may be related to FeCO 3 0 reacting faster than FeOH + with H 2 O 2 . At a given pH and ionic strength, the rates in seawater are nearly the same as in NaCl.
Millero Frank. J.
Sotolongo Sara
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