On anharmonic and pressure corrections to the equilibrium isotopic constants for minerals
Abstract
Specifies of the calculations of the reduced isotopic partition function ratios (β-factor) of minerals are discussed. Comparative calculations in the framework of the fully harmonic, quasi-harmonic, and intrinsic anharmonic approximations show minor anharmonic corrections to the harmonic values of the β-factor. In the case of calcite, the difference between the fully harmonic and intrinsic anharmonic values of 10 3lnβ varies from 0.60 at 300 K to 0.37 at 1200 K and is close to typical values of the anharmonic correction in gas molecules. A new treatment for calculating isotopic effects in molar volumes of minerals and pressure effects on their β-factors is developed on the basis of the Mie-Grüneisen equation of state. There is no significant difference between the quasi-harmonic and intrinsic harmonic values of (∂lnβ/∂ P) T. For calcite, the pressure derivative of the β-factor is positive, decreases monotonically with temperature, and becomes small at T ∼ 1000 K (10 3(∂lnβ/ ∂P) T ≈ 0.1-0.15 GPa -1). These results contradict the large anharmonic and pressure effects to the β-factor of calcite calculated by Gillet et al. (1996) as well as their conclusion that the pressure correction to the β-factor of calcite is negative at higher temperatures and increases in its absolute value with increasing temperature.
- Publication:
-
Geochimica et Cosmochimica Acta
- Pub Date:
- September 1998
- DOI:
- 10.1016/S0016-7037(98)00220-8
- Bibcode:
- 1998GeCoA..62.3077P