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a system:
Some portion of the universe that you wish to study
The surroundings:
The adjacent part of the universe outside the system
Energy States
Metastable: in low-energy
perch
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
Thermodynamics
In our calorimeter we can then determine H for the reaction:
H = -910,648 J/mol
Thermodynamics
For other temperatures and pressures we can use the
equation:
dG = VdP SdT
GT
P2
GT
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
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
Thermodynamics
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?
< 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
dG = VdP - SdT
(again ignoring X)
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.