The X-ray diffraction method and the phosphoric acid method are widely used to determine the fraction of free silica (mainly quartz and other silica polymorphs) in respirable dust sampled in working environments in Japan. In this study, we clarified the size effect of quartz dust for the Xray diffraction method and the phosphoric acid method using size controlled quartz samples. The quartz samples were classified into 6 fractions with different size ranges: 1 µm and smaller, 1 to 3 µm, 3 to 5 µm, 5 to 7 µm, 7 to 10 µm and 10 µm and larger. Both of the determination methods were affected by the particle size, and especially particles smaller than 3 µm fairly dissolved in hot phosphoric acid and reduced X-ray diffraction intensity remarkably. If the content of these fine particles in the standard quartz sample is lower than that of the test samples, the fraction of free silica may be underestimated by these methods. For this reason, the standard quartz sample should have a representative size distribution of the field samples. The dust samples containing quartz were collected at a foundry and dissolved by phosphoric acid to remove non-quartz materials. The size fractions of dissolved samples were 50% for 5-10 µm, 25% for 3-5 µm, 20% for 1-3 µm and 5% for 1 µm and smaller. As the size distribution is similar to the present standard sample widely used in Japan, we concluded that the standard sample is suitable for these determination methods.