Abstract
The kinetics of the disproportionation of hypoiodous acid to give iodine and iodate ion (5HOI right harpoon over left harpoon 2I(2) + IO(3)(-) + H(+) + 2H(2)O) are investigated in aqueous acetic acid-sodium acetate buffer. The rate of iodine formation is followed photometrically at -log [H(+)] = 3.50, 4.00, 4.50, and 5.00, &mgr; = 0.50 M (NaClO(4)), and 25.0 degrees C. Both catalytic and inhibitory buffer effects are observed. The first process is proposed to be a disproportionation of iodine(I) to give HOIO and I(-); the iodide then reacts with HOI to give I(2). The reactive species (acetato-O)iodine(I), CH(3)CO(2)I, is postulated to increase the rate by assisting in the formation of I(2)O, a steady-state species that hydrolyzes to give HOIO and I(2). Inhibition is postulated to result from the formation of the stable ion bis(acetato-O)iodate(I), (CH(3)CO(2))(2)I(-), as buffer concentration is increased. This species is observed spectrophotometrically with a UV absorption shoulder (lambda = 266 nm; epsilon = 530 M(-)(1) cm(-)(1)). The second process is proposed to be a disproportionation of HOIO to give IO(3)(-) and I(2). Above 1 M total buffer, the reaction becomes reversible with less than 90% I(2) formation. Rate and equilibrium constants are resolved and reported for the proposed mechanism.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.