Voids are frequently generated and dispersed in oxide scales formed in high temperature oxidation of metals. The divergence of ionic flux may play an important role in the void formation in a growing scale. Kinetic equations were derived for describing chemical potential distribution, ionic fluxes and their divergence in the scale. The divergence was found to be the measure of void formation. Defect chemistry in scales is directly related to the sign of divergence and gives an indication of the void formation behavior. The quantitative estimation on the void formation was successfully applied to a growing magnetite scale in high temperature oxidation of iron at 823 K.