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
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:

Si (metal) + O2 (gas) = SiO2

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)

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 X 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

1 P1

z z
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

Eq. 1
G (J) eq. 1

SUPCRT

P (MPa)

T (C)

G(J)

V (cm3)

S (J/K)

0.1

25

-856,288 -856,648

22.69

41.36

500

25

-844,946 -845,362

22.44

40.73

0.1

500

-875,982 -890,601

23.26

96.99

500

500

-864,640 -879,014

23.07

96.36

Agreement is quite good

(< 2% for change of 500o and 500 MPa or 17 km)

Thermodynamics

Summary thus far:

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)

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?

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.

We can thus predict that the slope

of solid-liquid equilibrium should
be positive and that increased
pressure raises the melting point.

Does liquid or solid have a

higher entropy?
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 P/T = -S
Slope S < Slope L
Equilibrium at Teq
G
Liq = 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:

dG = VdP - SdT

(again ignoring X)

For a reaction of melting (like ice water)

V is the volume change involved in the reaction (V
water - Vice)
similarly S and G are the entropy and free energy changes
dG is then the change in G as T and P are varied

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)

G for any reaction = 0 at equilibrium

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.