Oxygen Isotope Fractionation in Divalent Metal Carbonates

Equilibrium fractionation factors for the distribution of ¹⁸O between alkaline‐earth carbonates and water have been measured over the temperature range 0–500°C. The fractionation factors $\alpha$ can be represented by the equations $${\mathrm{CaCO}}_3–{\mathrm{H}}_2\mathrm{O}\text{, 1000}\ln {\text{α\hspace{0.17em}=\hspace{0.17em}2.78(10}}^6{T}^{\text{−2}}\text{)−\hspace{0.17em}3.39,}$$ $${\mathrm{SrCO}}_3–{\mathrm{H}}_2\mathrm{O}\text{, 1000}\ln {\text{α\hspace{0.17em}=\hspace{0.17em}2.69(10}}^6{T}^{\text{−2}}\text{)−\hspace{0.17em}3.74,}$$ $${\mathrm{BaCO}}_3–{\mathrm{H}}_2\mathrm{O}\text{, 1000}\ln {\text{α\hspace{0.17em}=\hspace{0.17em}2.57(10}}^6{T}^{\text{−2}}\text{)−\hspace{0.17em}4.73.}$$ Measurements on MnCO₃, CdCO₃, and PbCO₃ were made at isolated temperatures. A statistical‐mechanical calculation of the isotopic partition function ratios gives reasonably good agreement with experiment. Both cationic size and mass are important in isotopic fractionation, the former predominantly in its effect on the internal vibrations of the anion, the latter in its effect on the lattice vibrations.