In connexion with the analysis of coal ashes and related silicate materials, an investigation has been made of the interference of aluminium, iron, calcium, magnesium, silicate and borate in the determination of sodium and potassium by the EEL flame photometer. The effects of all these constituents, with the exception of calcium, were negligible in the ranges of concentration likely to be met in this work. The interference of calcium in the determination of sodium was eliminated by adding aluminium, incorporated in the hydrofluoric‐sulphuric acid mixture used to decompose the sample. A method is proposed by which sodium and potassium in silicates may be determined in 1 1/2 hours. Results by this method compare favourably with those obtained by the J. L. Smith procedure1, 2 and by the Lundegardh flame spectrographic technique.