The effects of porosity and composition on the optical thickness of sol-gel films is analyzed using the Clausius-Mossotti relationship. The optical thickness is predicted to decrease with shrinkage approximately linearly. For high density films the predictions agree with experimental data from SiO2 and SiO2-TiO2-Al2O3 coatings. At low densities, however, the optical thicknesses are much higher than predicted by the Clausius-Mossotti analysis. This difference is attributed to residual species in the unfired films. Using an empirical value for the ratio of the electronic polarizability alpha(r) to the molecular weight W-r of the residual species (alpha(r)/W-r = 1.65 x 10(-25) cm(3) mol g(-1)) the difference between experiment and theory is accounted for quantitatively for both the single-component (SiO2) and multicomponent (SiO2-TiO2-Al2O3) coatings. Approaches to fabricating multicolor dichroic filters, which require large changes in optical thickness on heating, are presented.