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Changes in a system are associated with the transfer of energy Natural systems tend toward states of minimum energy
Energy States
q
Unstable: falling or rolling Stable: at rest in lowest energy state Metastable: in low-energy perch
Figure 5.1. Stability states. Winter (2001) An Introduction to Igneous and Metamorphic Petrology. Prentice Hall.
Thermodynamics
a Phase: a mechanically separable portion of a system 3 Mineral 3 Liquid 3 Vapor a Reaction: some change in the nature or types of phases
in a system reactions are written in the form: reactants = products
Thermodynamics
The change in some property, such as G for a reaction of the type: 2A + 3B =C +4D G = (n G)products - (n G)reactants = GC + 4GD - 2GA - 3GB
Thermodynamics
For a phase we can determine V, T, P, etc., but not G or H We can only determine changes in G or H as we change some other parameters of the system
Example: measure H for a reaction by calorimetry - the heat given off or absorbed as a reaction proceeds
Arbitrary reference state and assign an equally arbitrary value of H to it: Choose 298.15 K and 0.1 MPa (lab conditions) ...and assign H = 0 for pure elements (in their natural state - gas, liquid, solid) at that reference
Thermodynamics
In our calorimeter we can then determine H for the reaction:
H = -910,648 J/mol
= molar enthalpy of formation of quartz (at 298, 0.1) It serves quite well for a standard value of H for the phase Entropy has a more universal reference state: entropy of every substance = 0 at 0K, so we use that (and adjust for temperature)
Thermodynamics
For other temperatures and pressures we can use the equation:
dG = VdP SdT
GT
P2
G T
1 P1
z z
P2 P1
VdP
T2
T1
SdT
Thermodynamics
If V and S are constants, our equation reduces to:
Thermodynamics
In Worked Example 1 we used
Agreement is quite good (< 2% for change of 500o and 500 MPa or 17 km)
Thermodynamics
Use? If we know G for various phases, we can determine which is most stable 3 Why is melt more stable than solids at high T? 3 Is diamond or graphite stable at 150 km depth? 3 What will be the effect of increased P on melting?
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 We can then determine G at any T and P mathematically 3 Most accurate if know how V and S vary with P and T dV/dP is the coefficient of isothermal compressibility dS/dT is the heat capacity (Cp)
Does the liquid or solid have the larger volume? High pressure favors low volume, so which phase should be stable at high P?
Figure 5.2. Schematic P-T phase diagram of a melting reaction. Winter (2001) An Introduction to Igneous and Metamorphic Petrology. Prentice Hall.
Does liquid or solid have a higher entropy? High temperature favors randomness, so which phase should be stable at higher T?
We can thus predict that the slope of solid-liquid equilibrium should be positive and that increased pressure raises the melting point.
The phase assemblage with the lowest G under a specific set of conditions is the most stable
Would the slope for the liquid be steeper or shallower than that for the solid?
< Sliquid
A: Solid more stable than liquid (low T) B: Liquid more stable than solid (high T) x Slope P/T = -S x Slope S < Slope L Equilibrium at Teq
x
Figure 5.3. Relationship between Gibbs free energy and temperature for the solid and liquid forms of a substance at constant pressure. Teq is the equilibrium temperature. Winter (2001) An Introduction to Igneous and Metamorphic Petrology. Prentice Hall.
GLiq = GSol
dG = VdP - SdT
(again ignoring X)
For a reaction of melting (like ice water) x V is the volume change involved in the reaction (V water - Vice)
x
G is (+) for S L at point A (GS < GL) G is (-) for S L at point B (GS > GL) G = 0 for S L at point x (GS = GL)
Pick any two points on the equilibrium curve G = ? at each Therefore dG from point X to point Y = 0 - 0 = 0
dG = 0 = VdP - SdT
dP S = dT V
Figure 5.4. Relationship between Gibbs free energy and pressure for the solid and liquid forms of a substance at constant temperature. Peq is the equilibrium pressure. Winter (2001) An Introduction to Igneous and Metamorphic Petrology. Prentice Hall.
Figure 5.5. Piston-and-cylinder apparatus to compress a gas. Winter (2001) An Introduction to Igneous and Metamorphic Petrology. Prentice Hall.