where Sieq. =#Si, and (cation equivalents) are the charge-weighed stoichiometric coefficients of each cation, normalized to the charge of the silicon atom, and aX(T) are proportionality coefficients depending on temperature. It is suggested that the effect of cation X on Si isotope fractionation (i.e. aX(T)) will increase with decreasing electronegativity of X. Si isotope fractionation is further correlated with Si–O distances, suggesting a crystal chemical explanation for relation (1) in terms of electron donation effects. This relationship appears valid for quartz, pyrope and enstatite , but forsterite is strongly anomalous (error of 0.7‰ at 600 °C). These models indicate that attention should be given to chemical compositions in Si isotope studies. Relation (1) would explain the enrichment in heavy silicon isotopes accompanying magmatic differentiation.