Reinvestigation of the Henry's law constant for hydrogen peroxide with temperature and acidity variation.

Hydrogen peroxide is not only an important oxidant in itself; it also serves as both sink and temporary reservoir for other important oxidants including HOx (OH and HO2) radicals and O3 in the atmosphere. Its partitioning between gas and aqueous phases in the atmosphere, usually described by its Henry's law constant (K(H)), significantly influences its role in atmospheric processes. Large discrepancies between the K(H) values reported in previous work, however, have created uncertainty for atmospheric modelers. Based on our newly developed online instrumentation, we have re-determined the temperature and acidity dependence of K(H) for hydrogen peroxide at an air pressure of (0.960 +/- 0.013) atm (1 atm = 1.01325 x 10(5) Pa). The results indicated that the temperature dependence of K(H) for hydrogen peroxide fits to the Van't Hoff equation form, expressed as lnK(H) = a/T - b, and a = -deltaH/R, where K(H) is in M/atm (M is mol/L), T is in degrees Kelvin, R is the ideal gas constant, and deltaH is the standard heat of solution. For acidity dependence, results demonstrated that the K(H) value of hydrogen peroxide appeared to have no obvious dependence on decreasing pH level (from pH 7 to pH 1). Combining the dependence of both temperature and acidity, the obtained a and b were 7024 +/- 138 and 11.97 +/- 0.48, respectively, deltaH was (58.40 +/- 1.15) kJ/(K x mol), and the uncertainties represent sigma. Our determined K(H) values for hydrogen peroxide will therefore be of great use in atmospheric models.