Hydrogen peroxide, \(\mathrm{H}_{2} \mathrm{O}_{2},\) is a somewhat stronger
acid than water. Its ionization is represented by the equation \(\mathrm{H}_{2}
\mathrm{O}_{2}+\mathrm{H}_{2} \mathrm{O} \rightleftharpoons \mathrm{H}_{3}
\mathrm{O}^{+}+\mathrm{HO}_{2}^{-}\) In \(1912,\) the following experiments were
performed to obtain an approximate value of \(\mathrm{p} K_{\mathrm{a}}\) for
this ionization at \(0^{\circ} \mathrm{C} .\) A sample of \(\mathrm{H}_{2}
\mathrm{O}_{2}\) was shaken together with a mixture of water and 1 -pentanol.
The mixture settled into two layers. At equilibrium, the hydrogen peroxide had
distributed itself between the two layers such that the water layer contained
6.78 times as much \(\mathrm{H}_{2} \mathrm{O}_{2}\) as the 1 -pentanol layer.
In a second experiment, a sample of \(\mathrm{H}_{2} \mathrm{O}_{2}\) was shaken
together with 0.250 M NaOH(aq) and 1-pentanol. At equilibrium, the
concentration of \(\mathrm{H}_{2} \mathrm{O}_{2}\) was \(0.00357 \mathrm{M}\) in
the 1-pentanol layer and 0.259 M in the aqueous layer. In a third experiment,
a sample of \(\mathrm{H}_{2} \mathrm{O}_{2}\) was brought to equilibrium with a
mixture of 1 -pentanol and \(0.125 \mathrm{M}\) \(\mathrm{NaOH}(\mathrm{aq}) ;\)
the concentrations of the hydrogen peroxide were \(0.00198 \mathrm{M}\) in the 1
-pentanol and \(0.123 \mathrm{M}\) in the aqueous layer. For water at \(0^{\circ}
\mathrm{C}, \mathrm{p} K_{\mathrm{w}}=14.94\)
Find an approximate value of \(\mathrm{pK}_{\mathrm{a}}\) for \(\mathrm{H}_{2}
\mathrm{O}_{2}\) at \(0^{\circ} \mathrm{C}\) [Hint: The hydrogen peroxide
concentration in the aqueous layers is the total concentration of
\(\mathrm{H}_{2} \mathrm{O}_{2}\) and \(\mathrm{HO}_{2}^{-}\). Assume that the 1
-pentanol solutions contain no ionic species.