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n
A
n
=
n
A
(n
A
+ n
B
+ n
C
+ )
,
where X
A
is called the mole fraction of
component A in some phase.
If the same component is used in more than one phase,
Then we can define the mole fraction of component
A in phase i as
X
A
i
For a simple binary system, X
A
+ X
B
= 1
Partial Molar Volumes & Mixing
Temperature Dependence
of Partial Molar Volumes
Partial Molar Quantities
Defined because most solutions DO NOT mix
ideally, but rather deviate from simple linear
mixing as a result of atomic interactions of
dissimilar ions or molecules within a phase.
Partial molar quantities are defined by the true
mixing relations of a particular thermodynamic
variable and can be calculated graphically by
extrapolating the tangent at the mole fraction of
interest back to the end-member composition.
Partial Molar Gibbs Free Energy
As noted earlier, the change in Gibbs free energy function determines the
direction in which a reaction will proceed toward equilibrium. Because of
its importance and frequent use, we designate a special label called the
chemical potential, , for the partial molar Gibbs free energy.
cG
A
cX
A
|
\
|
.
|
P,T,X
B
,X
C
,
We must define a reference state from which to calculate differences in
chemical potential. The reference state is referred to as the standard state
and can be arbitrarily selected to be the most convenient for calculation.
The standard state is often assumed to be pure phases at standard atmospheric
temperature and pressure (25C and 1 bar). Thermodynamic data are tabulated
for most phases of petrological interest and are designated with the superscript ,
for example, G, to avoid confusion.
Chemical Thermodynamics
dG = VdP SdT +
i
dX
i
i
i
dX
i
i
=
A
dX
A
+
B
dX
B
+
C
dX
C
+ +
n
dX
n
MASTER EQUATION
This equation demonstrates that changes in Gibbs free energy are
dependent on:
changes in the chemical potential, , through the
concentration of the components expressed as mole
fractions of the various phases in the system
changes in molar volume of the system through dP
chnages in molar entropy of the system through dT
Equilibrium and the Chemical Potential
Chemical potential is analogous to gravitational or electrical
potentials: the most stable state is the one where the overall
potential is lowest.
At equilibrium the chemical potentials for any specific
component in ALL phases must be equal. This means that the
system will change spontaneously to adjust by the Law of
Mass Action to cause this state to be obtained.
H
2
O
melt
=
H
2
O
gas
=
H
2
O
biotite
= =
H
2
O
n
CaO
melt
=
CaO
gas
=
CaO
biotite
= =
CaO
n
If
H
2
O
me lt
>
H
2
O
gas
then system will have to adjust the mass
(concentration) to make them equal:
H
2
O
me lt
=
H
2
O
gas
Gibbs Free Energy of Mixing
Activity - Composition Relations
The activity of any component is always less than the
corresponding Gibbs free energy of the pure phase, where the
activity is equal to unity by definition (remember the choice
of standard state).
A
< G
A
;
B
< G
B
A
i
= G
A
+ RTlna
A
i
a
A
i
=
A
i
X
A
i
For ideal solutions (remember dG of mixing is linear),
A
i
1
such that the activity is equal to the mole fraction.
A
i
= G
A
+ RTln X
A
i
P, T, X Stability of Crystals
Equilibrium stability
surface where G
l
=G
c
is defined by three
variables:
1) Temperature
2) Pressure
3) Bulk Composition
Changes in any of these
variables can move the
system from the liquid
to crystal stability field
Fugacity Defined
For gaseous phases at fixed temperature: dG
T
= VdP
- Assume Ideal Gas Law
PV = nRT;n = 1
V =
RT
P
dG
T
= VdP =
RT
P
|
\
|
.
dP = RTlndP
P
A
= X
A
P
total
and the fugacity coefficient is defined as f
A
/P
A
, which
Is analogous to the activity coefficient. As the gas component
Becomes more ideal, f
A
goes to unity.
A
= G
A
+ RTln f
A
Equilibrium Constants
Mg
2
SiO
4
+ SiO
2
= 2MgSiO
3
olivine melt opx
AG =
2
MgSiO
3
opx
Mg
2
SiO
4
ol
SiO
2
melt
= 0
SiO
2
melt
= G
SiO
2
glass
+ RTlna
SiO
2
melt
Mg
2
SiO
4
ol
= G
Mg
2
SiO
4
ol
+ RTln a
Mg
2
SiO
4
ol
MgSiO
3
opx
= G
MgSiO
3
opx
+ RTln a
MgSiO
3
opx
Equilibrium Constants, cont.
2G
MgSiO
3
opx
G
Mg
2
SiO
4
ol
G
SiO
2
glass
=
RT ln(a
MgSiO
3
opx
)
2
(a
Mg
2
SiO
4
ol
a
SiO
2
melt
)
K
eq
=
(a
MgSiO
3
opx
)
2
(a
Mg
2
SiO
4
ol
a
SiO
2
melt
)
AG
F
= RT lnK
eq
where dG
F
is referred to as the change in standard state
Gibbs free energy of formation, which may be obtained
from tabulated information
Silica Activity, Buffers, and Saturation
Mg
2
SiO
4
+ SiO
2
= 2MgSiO
3
olivine melt opx
NeAlSiO
4
+ SiO
2
= NaAlSi
3
O
8
nepheline melt albite
Oxygen Buffers
<--- Calculated fO
2
from Fe-Ti oxides
Fe
2
TiO
4
+ Fe
2
O
3
= FeTiO
3
+ Fe3O4
Arrhenius Equation and Activation Energy
Kinetic Rate = A exp
-E
a
/RT
log D = log A - E
a
/2.303RT
y = b + m x
Slope = dy/dx = -E
a
/2.303R
Intercept = b = log A
All processes that are
thermally activated have
similar form!
Gibbs Free Energy - Temperature Relations
State A is stable for T > T
e
because G
A
< G
B
Metastability for polymorphs A & B
Undercooling
allows metastability
of phase A over B
State B is stable for T < T
e
because G
B
< G
A
Irreversible Path
SYSTEM STATE CHANGES YIELD REACTION OVERSTEPPING
Silica Polymorph Free Energy Relations
and Reaction Progress
Ostwalds Step Rule: In a change of state the kinetically most
favored phase may form at an intermediate step rather than
the most thermodynamically favored (lowest G) phase!
Glass -> Qtz (favored)
Glass -> Cristobalite or
Tridymite