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 2 P2
 GT
1 P1
z P2

P1
VdP z 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 ain’t 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 SUPCRT

P (MPa) T (C) G (J) eq. 1 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?

Does liquid or solid have a

Figure 5-2. Schematic P-T phase diagram of a melting reaction.
Winter (2001) An Introduction to Igneous and Metamorphic
higher entropy?
Petrology. Prentice Hall.
High temperature favors
We can thus predict that the slope randomness, so which
of solid-liquid equilibrium should phase should be stable at
be positive and that increased higher T?
pressure raises the melting point.
 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
increases Figure 5-3. Relationship between Gibbs free energy and
temperature for a solid at constant pressure. T is the equilibrium
eq
temperature. 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
Figure 5-3. Relationship between Gibbs free energy and
< Sliquid 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.
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
 GLiq = GSol
Now consider a reaction, we can then use the equation:
dG = 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

dG 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 don’t 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 don’t 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.