Chemistry of +1 iodine in alkaline solution

The iodine species formed either by adding hypochlorite to a basic iodide solution or by adding triiodide to sodium hydroxide, was identified as hypoiodite ion. The absorption spectrum of IO{sup -} was investigated in the wavelength range from 450 m{micro} to 280 m{micro}. The kinetics of the reaction I{sup -} + ClO{sup -} = IO{sup -} + Cl{sup -} was studied spectrophotometrically in alkaline solution. The forward rate law was found to be d(IO{sup -})/dt = k(I{sup -})(ClO{sup -})/OH{sup -}. At 25 C and an ionic strength of 1.00 M, k is 61 {+-} 3 sec{sup -1}. It was found spectrophotometrically that for certain ratios of the initial iodide to hydroxide concentrations, there was evidence of the presence of I{sub 3}{sup -}, I{sub 2}OH{sup -}, and I{sub 2}O{sup 2-} along with IO{sup -}. The equilibrium constants between IO{sup -} and these three species were evaluated by a graphical method. The formal potential of the cell: Pt:H{sub 2}:1 M NaOH : 1M NaOH, KI, NaIO : Au was found to be 1.297 v at 25 C. The equilibrium constant, K{sub 2} = (I{sub 3}{sup -})(OH{sup -}){sup 2}/(IO{sup -})(I{sup -}){sup 2}, of the reaction IO{sup -} + 2I{sup -} + H{sub 2}O {l_reversible} I{sub 3}{sup -} + 2OH{sup -} calculated from emf measurements agreed well with that from spectrophotometric measurements. The ionization constant of HOI was calculated to be 2.3 x 10{sup -11} at 25 C