OH, HO sub(2), and Ozone Gaseous Diffusion Coefficients

The diffusion of OH, HO sub(2), and O sub(3) in He, and of OH in air, has been investigated using a coated-wall flow tube reactor coupled to a chemical ionization mass spectrometry. The diffusion coefficients were determined from measurements of the loss of the reactive species to the flow tube wall as a function of pressure. On the basis of the experimental results, D sub(OH- He) = 662 plus or minus 33 Torr cm super(2) s super(-1), D sub(OH-air) = 165 plus or minus 20 Torr cm super(2) s super(-1), D sub(HO2)-He= 430 plus or minus 30 Torr cm super(2) s super(-1), and D sub(O3)-He = 410 plus or minus 25 Torr cm super(2) s super(-1) at 296 K. We show that the measured values for OH and HO sub(2) are in better agreement with measured values of their polar analogues (H sub(2)O and H sub(2)O sub(2)) compared with measured values of their nonpolar analogues (O and O sub(2)). The measured value for OH in air is 25% smaller than that for O (the nonpolar analogue). The difference between the measured value for HO sub(2) and O sub(2) (the nonpolar analogue) in air is expected to be even larger. Also we show that calculations of the diffusion coefficients based on Lennard-Jones potentials are in excellent agreement with the measurements. This gives further confidence that these calculations can be used to estimate accurate diffusion coefficients for conditions where laboratory data currently do not exist.