Binary diffusion coefficients were measured by a steady-state method in which a gas was introduced at a constant rate into one end of a tube through which it moved by mass flow and diffusion into a semi-infinite volume of air. The Stefan correction for mass flow was modified to allow for initial gas concentrations < 100 per cent, conferring four advantages: errors in the total flow rate are relatively unimportant; density gradients are small so that convection is inhibited; the gas analysis is more sensitive; and diffusion coefficients are measured at the small concentrations that are encountered in soils. Measured diffusion coefficients (cm2 s−1 at NTP) in air for carbon dioxide (0.139), nitrous oxide (0.143), ethylene (0.137) and ethane (0.128) are compared with measured and calculated values from other sources.