Phase Rule and Binary Phase Diagrams相律与二元相图.pptVIP

* Thermodynamics and the Phase Rule GLY 4200 Fall, 2013 * Thermodynamic Background System: The portion of the universe that is being studied Surroundings: The part of the universe not included in the system * Free Energy Any change in the system involves a transfer of energy All chemical systems tend naturally toward states of minimum Gibbs free energy * Gibbs Free Energy G = H - TS Where: G = Gibbs Free Energy H = Enthalpy (heat content) T = Temperature in Kelvin S = Entropy (a measure of randomness) * Alternative Equation For other temperatures and pressures we can use the equation: dG = VdP – SdT where V = volume and S = entropy (both molar) This equation can be used to calculate G for any phase at any T and P by integrating GT2P2 - GT1P1 = ∫P1P2VdP - ∫T1T2SdT * Using Thermodynamics G is a measure of relative chemical stability for a phase We can determine G for any phase by measuring H and S for the reaction creating the phase from the elements (SiO2 from silicon and oxygen, for example) We can then determine G at any T and P mathematically How do V and S vary with P and T? dV/dP is the coefficient of isothermal compressibility dS/dT is the heat capacity at constant pressure (Cp) * Applying Thermodynamics If we know G for various phases, we can determine which is most stable With appropriate reactions comparing two or more phases, we can answer questions like: Why is melt more stable than solids at high T? Which polymorphic phase will be stable under given conditions? What will be the effect of increased P on melting? * High Pressure High pressure favors low volume, so which phase should be stable at high P? Hint: Does the liquid or solid have the larger volume? Figure 5-2. Schematic P-T phase diagram of a melting reaction. Winter (2001) An Introduction to Igneous and Metamorphic Petrology. Prentice Hall. * High Temperature High temperature favors randomness, so w