The rates of thiourea oxidation with Fe(VI) were determined
as a function of pH (8.8−11.5) and temperature (10−35
°C). The rate law for the oxidation of thiourea was found
to be −d[Fe(VI)]/dt = k
0{[H+]/[H+]+K
9)}[Fe(VI)][thiourea]
where k
0 = 5.9 × 104 M-1 s-1, pK
9 = 7.8. The activation
energy, ΔE
≠, obtained was 32.2 ± 1.8 kJ mol-1. The rate
constant for the reaction of Fe(VI) with the thiourea radical
was determined by using a premix pulse radiolysis
technique and was found to be 8.5 × 108 M-1 s-1 at pH
= 9.0. The stoichiometric ratio of Fe(VI) and thiourea was
found to be 1:0.38 ± 0.02 at pH = 9.0. Sulfate and urea
were identified as the products of the reaction. Tests were
conducted on the oxidative destruction of thiourea by Fe(VI) in synthetic boiler chemical cleaning wastes (BCCW)
and are discussed.
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