Past exam of the year 2 of the earth sciences (geology) course of the University of Oxford / 2023 / Paper 1 / 7

Section D: Thermodynamics.

For pure phases at the reference pressure $P_0=1\mathrm{bar}$, the Gibbs energy of reaction is ${\Delta }_{r}G=\Delta H^{\circ }-T\Delta S^{\circ }$. Chemical equilibrium requires ${\Delta }_{r}G=0$, soThe reaction is muscovite dehydration to sanidine, corundum and water; its positive standard entropy of reaction makes the product assemblage favored at high temperature under this constant-property approximation.

Use the pressure correction to a mineral reaction for the solids, and the gas thermodynamic activity $f/P_0$ for water. These are separate contributions: do not also add a gas-volume pressure correction after including $RT\ln (f/P_0)$. For this reaction,At $7000\mathrm{bar}$ with pure solids and an ideal gas, $f=P$ and the solid-activity ratio is one. ThereforeandThe pressure unit in the solid term is bar, matching the supplied $\mathrm{J}\mathrm{ba}{\mathrm{r}}^{-1}$. The gas logarithm is dimensionless because $P/P_0=7000$. High water chemical fugacity opposes dehydration and raises the equilibrium temperature substantially.

Under ideal independent mixing on crystallographic sites, a mineral endmember's thermodynamic activity is the product of its required site fractions, one factor per mixed site. Muscovite has one K and three Al per formula unit, sanidine has one K and one Al, and corundum has two Al. Interpreting the given Al fractions as the fractions on every relevant Al/Fe site givesThus $A_s=a_{\mathrm{san}}{a}_{\mathrm{cor}}/a_{\mathrm{mus}}=0.6237816764$. The cubic power for muscovite includes its tetrahedral Al site and two octahedral Al sites; if site-specific fractions differed, bulk Al/(Al+Fe) alone would not determine this activity. The calculation uses the uniform-site ideal-mixing interpretation intended by the given data.

At $P=5000\mathrm{bar}$ with ideal water, solvegiving $T_{\mathrm{eq}}=979.40\mathrm{K}=706.25{}^{\circ }\mathrm{C}$. Using the bulk mole fraction only once for a multisite mineral endmember would omit part of its ideal mixing chemical potential.

The fugacity coefficient $\varphi =f/P=0.7$ gives $f=3500\mathrm{bar}$. Keep the same solid thermodynamic activities and pressure correction to a mineral reaction as in part (c), changing only the water chemical fugacity:The lower water chemical fugacity makes the dehydrated assemblage more favorable, so the equilibrium temperature decreases by about $29.0\mathrm{K}$. This direction is a useful independent check on the logarithm's sign.