Thermodynamics

a system:
Some portion of the universe that you wish to study

The surroundings:
The adjacent part of the universe outside the system

Changes in a system are associated with the transfer of energy Natural systems tend toward states of minimum energy

Energy States

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.

Gibbs Free Energy

Gibbs free energy is a measure of chemical energy All chemical systems tend naturally toward states of minimum Gibbs free energy G = H - TS
Where:
G = Gibbs Free Energy H = Enthalpy (heat content) T = Temperature in Kelvins S = Entropy (can think of as randomness)

Thermodynamics
a Phase: a mechanically separable portion of a system Mineral Liquid 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 DG = S (n G)products - S(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 DH 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 DH for the reaction:

Si (metal) + O2 (gas) = SiO2

DH = -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)

Then we can use G = H - TS to determine G of quartz = -856,288 J/mol

Thermodynamics
For other temperatures and pressures we can use the equation:

dG = VdP SdT

(ignoring DX for now)

where V = volume and S = entropy (both molar)

We can use this equation to calculate G for any phase at any T and P by integrating

GT

P2

- GT

P1

P2

P1

VdP -

T2

T1

SdT

Thermodynamics
If V and S are constants, our equation reduces to:

GT2 P2 - GT1 P1 = V(P2 - P1) - S (T2 - T1)

which aint bad!

Thermodynamics
In Worked Example 1 we used

GT2 P2 - GT1 P1 = V(P2 - P1) - S (T2 - T1)

and G298, 0.1 = -856,288 J/mol to calculate G for quartz at several temperatures and pressures
Low quartz P (MPa) 0.1 500 0.1 500 T (C) 25 25 500 500 Eq. 1 G (J) eq. 1 -856,288 -844,946 -875,982 -864,640 G(J) -856,648 -845,362 -890,601 -879,014 SUPCRT V (cm3) 22.69 22.44 23.26 23.07 S (J/K) 41.36 40.73 96.99 96.36

Agreement is quite good (< 2% for change of 500o and 500 MPa or 17 km)

Thermodynamics
Summary thus far:

Use? If we know G for various phases, we can determine which is most stable Why is melt more stable than solids at high T? Is diamond or graphite stable at 150 km depth? 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 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?

We can thus predict that the slope of solid-liquid equilibrium should be positive and that increased pressure raises the melting point.

High temperature favors randomness, so which phase should be stable at higher T?

Does the liquid or solid have the lowest G at point A?

What about at point B?

Figure 5-2. Schematic P-T phase diagram of a melting reaction. Winter (2001) An Introduction to Igneous and Metamorphic Petrology. Prentice Hall.

The phase assemblage with the lowest G under a specific set of conditions is the most stable

Free Energy vs. Temperature

dG = VdP - SdT at constant pressure: dG/dT = -S Because S must be (+) G for a phase decreases as T Figure 5.3. Relationship between Gibbs free energy and temperature increases for a solid at constant pressure. T is the equilibrium temperature.
eq

Winter (2001) An Introduction to Igneous and Metamorphic Petrology. Prentice Hall.

Would the slope for the liquid be steeper or shallower than that for the solid?

Free Energy vs. Temperature

Slope of GLiq > Gsol since

Ssolid < Sliquid

A: Solid more stable than liquid (low T) B: Liquid more stable than solid (high T) Slope dP/dT = -S Slope S < Slope L Equilibrium at Teq GLiq = GSol

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.

Now consider a reaction, we can then use the equation:

dDG = DVdP - DSdT

(again ignoring DX)

For a reaction of melting (like ice water) DV is the volume change involved in the reaction (Vwater - Vice) similarly DS and DG are the entropy and free energy changes
dDG is then the change in DG as T and P are varied

DG is (+) for S L at point A (GS < GL) DG is (-) for S L at point B (GS > GL) DG = 0 for S L at point x (GS = GL)

DG for any reaction = 0 at equilibrium

Pick any two points on the equilibrium curve DG = ? at each Therefore dDG from point X to point Y = 0 - 0 = 0

dDG = 0 = DVdP - DSdT

dP DS = dT DV

Figures I dont use in class

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.

Figures I dont use in class

Figure 5.5. Piston-and-cylinder apparatus to compress a gas. Winter (2001) An Introduction to Igneous and Metamorphic Petrology. Prentice Hall.