Thermodynamics培训课件.pptVIP

Gas Pressure-Volume Relationships The form of this equation is very useful GP, T - GT = RT ln (P/Po) For a non-ideal gas (more geologically appropriate) the same form is used, but we substitute fugacity ( f ) for P where f = gP g is the fugacity coefficient Tables of fugacity coefficients for common gases are available At low pressures most gases are ideal, but at high P they are not o Dehydration Reactions Mu + Q = Kspar + Sillimanite + H2O We can treat the solids and gases separately GP, T - GT = DVsolids (P - 0.1) + RT ln (P/0.1) (isothermal) The treatment is then quite similar to solid-solid reactions, but you have to solve for the equilibrium P by iteration Dehydration Reactions (qualitative analysis) dP dT S V = D D Figure 27.2. Pressure-temperature phase diagram for the reaction muscovite + quartz = Al2SiO5 + K-feldspar + H2O, calculated using SUPCRT (Helgeson et al., 1978). Winter (2010) An Introduction to Igneous and Metamorphic Petrology. Prentice Hall. Solutions: T-X relationships Ab = Jd + Q was calculated for pure phases When solid solution results in impure phases the activity of each phase is reduced Use the same form as for gases (RT ln P or ln f) Instead of fugacity, we use activity Ideal solution: ai = Xi n = # of sites in the phase on which solution takes place Non-ideal: ai = gi Xi where gi is the activity coefficient n n Solutions: T-X relationships Example: orthopyroxenes (Fe, Mg)SiO3 Real vs. Ideal Solution Models Figure 27.3. Activity-composition relationships for the enstatite-ferrosilite mixture in orthopyroxene at 600oC and 800oC. Circles are data from Saxena and Ghose (1971); curves are model for sites as simple mixtures (from Saxena, 1973) Thermodynamics of Rock-Forming Crystalline Solutions. Winter (2010) An Introduction to Igneous and Metamorphic Petrology. Prentice Hall. Solutions: T-X relationships Back to our reaction: Simplify for now by ignoring dP and dT For a reaction such as: aA + bB = cC