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Begin With A Brief Review of Chapter 5: Thermodynamics
Begin With A Brief Review of Chapter 5: Thermodynamics
Stable: at rest in lowest
energy state
Metastable: in low-energy
perch
G = H - TS
Where:
G = Gibbs Free Energy
H = Enthalpy (heat content)
T = Temperature in Kelvins
S = Entropy (can think of as randomness)
Thermodynamics
G for a reaction of the type:
2A + 3B =C +4D
G = (n G)products - (n G)reactants
= GC + 4GD - 2GA - 3GB
The side of the reaction with lower G will be more stable
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 P
1 1 z z
P2
P1
VdP
T2
T1
SdT
from G values for each phase at 298K and 0.1 MPa calculate G298, 0.1 for the
reaction, do the same for V and S
G at equilibrium = 0, so we can calculate an isobaric change in T that would
be required to bring G298, 0.1 to 0
0 - G298, 0.1 = -S (Teq - 298) (at constant P)
Similarly we could calculate an isothermal change
0 - G = -V (P - 0.1) (at constant T)
NaAlSi3O8 = NaAlSi2O6 + SiO2
P - T phase diagram of the equilibrium curve
How do you know which side has which phases?
GP GP
2 1 z P2
P1
VdP
Ideal Gas
– As P increases V decreases
– PV=nRT Ideal Gas Law
• P = pressure
• V = volume
• T = temperature
• n = # of moles of gas
• R = gas constant
= 8.3144 J mol-1 K-1
Figure 5.5. Piston-and-cylinder apparatus to
compress a gas. Winter (2010) An Introduction to
Igneous and Metamorphic Petrology. Prentice Hall.
P x V is a constant at constant T
Gas Pressure-Volume Relationships
Since GP GP
2 1 z P2
P1
VdP
GP GP
2 1 z P2
P1
RT
P
dP
z
and, since R and T are certainly independent of P:
P2 1
GP G P RT dP
2 1
P1 P
Gas Pressure-Volume Relationships
And since
z 1
x
dx ln x
o
GP, T - GT = RT ln (P/Po)
G of a gas at some P and T = G in the reference state (same T and 0.1 MPa)
+ a pressure term
Gas Pressure-Volume Relationships
The form of this equation is very useful
o
GP, T - GT = RT ln (P/Po)
Figure 27.3. Activity-composition relationships for the enstatite-ferrosilite mixture in orthopyroxene at 600 oC and 800oC. Circles are data
from Saxena and Ghose (1971); curves are model for sites as simple mixtures (from Saxena, 1973) Thermodynamics of Rock-Forming
Crystalline Solutions. Winter (2010) An Introduction to Igneous and Metamorphic Petrology. Prentice Hall.
Solutions: T-X relationships
Back to our reaction:
Simplify for now by ignoring dP and dT
For a reaction such as:
aA + bB = cC + dD
At a constant P and T:
G P , T G oP , T RT ln K
where: c d
ac aD
K a b
aA aB
Compositional variations
Effect of adding Ca to albite = jadeite + quartz
plagioclase = Al-rich Cpx + Q
GT, P = GoT, P + RTlnK
Let’s say GoT, P was the value that we calculated for
equilibrium in the pure Na-system (= 0 at some P and T)
GoT, P = G298, 0.1 + V (P - 0.1) - S (T-298) = 0
By adding Ca we will shift the equilibrium by RTlnK
We could assume ideal solution and
Pyx Q
X X
K Jd SiO 2
Plag
All coefficients = 1
X Ab
Compositional variations
So now we have:
X Pyx
GT, P = GoT, P + RTln Jd
Plag since Q is pure
X Ab
Figure 27.4. P-T phase diagram for the reaction Jadeite + Quartz = Albite for various values of K. The equilibrium curve for K = 1.0 is the
reaction for pure end-member minerals (Figure 27.1). Data from SUPCRT (Helgeson et al., 1978). Winter (2010) An Introduction to
Igneous and Metamorphic Petrology. Prentice Hall.
Geothermobarometry
Use measured distribution of elements in coexisting
phases from experiments at known P and T to estimate P
and T of equilibrium in natural samples
Geothermobarometry
The Garnet - Biotite geothermometer
Table 27-2. Experimental results of Ferry and Spear (1978) on a Garnet-Biotite Geothermometer
o
T C Initial Final Final Final Final K T 1/T lnK
X(Fe-Bt) X(Fe-Bt) X(Fe-Grt) (Mg/Fe)Grt (Mg/Fe)Bt Kelvins Kelvins
799 1.00 0.750 0.905 0.105 0.333 0.315 1072 0.00093 -1.155
799 0.50 0.710 0.896 0.116 0.408 0.284 1072 0.00093 -1.258
749 0.50 0.695 0.896 0.116 0.439 0.264 1022 0.00098 -1.330
738 1.00 0.730 0.906 0.104 0.370 0.281 1011 0.00099 -1.271
698 0.75 0.704 0.901 0.110 0.420 0.261 971 0.00103 -1.342
698 0.50 0.690 0.896 0.116 0.449 0.258 971 0.00103 -1.353
651 0.75 0.679 0.901 0.110 0.473 0.232 924 0.00108 -1.459
651 0.50 0.661 0.897 0.115 0.513 0.224 924 0.00108 -1.497
599 0.75 0.645 0.902 0.109 0.550 0.197 872 0.00115 -1.623
599 0.50 0.610 0.898 0.114 0.639 0.178 872 0.00115 -1.728
550 0.75 0.620 0.903 0.107 0.613 0.175 823 0.00122 -1.741
550 0.50 0.590 0.898 0.114 0.695 0.163 823 0.00122 -1.811
601 0.50 0.500 0.800 0.250 1.000 0.250 874 0.00114 -1.386
601 0.25 0.392 0.797 0.255 1.551 0.164 874 0.00114 -1.807
697 0.75 0.574 0.804 0.244 0.742 0.329 970 0.00103 -1.111
697 0.25 0.468 0.796 0.257 1.137 0.226 970 0.00103 -1.487
1/T (K)
-1.900
Geothermobarometry
The Garnet - Biotite geothermometer
H PV 1 S
ln K D
3R T 3R
52 ,090 2.494P MPa
T o
C 273
19.506 12.943 ln K D
Figure 27.5. Graph of lnK vs. 1/T (in Kelvins) for the Ferry and Spear (1978) garnet-biotite exchange equilibrium at 0.2 GPa from Table
27.2. Winter (2010) An Introduction to Igneous and Metamorphic Petrology. Prentice Hall.
Geothermobarometry
The Garnet - Biotite geothermometer
Figure 27.6. AFM projections showing the relative distribution of Fe and Mg in garnet vs. biotite at approximately 500 oC (a) and 800oC (b).
From Spear (1993) Metamorphic Phase Equilibria and Pressure-Temperature-Time Paths. Mineral. Soc. Amer. Monograph 1.
Geothermobarometry
The Garnet - Biotite geothermometer
Figure 27.7. Pressure-temperature diagram similar to Figure 27.4 showing lines of constant K D plotted using equation (27.35) for the garnet-
biotite exchange reaction. The Al2SiO5 phase diagram is added. From Spear (1993) Metamorphic Phase Equilibria and Pressure-Temperature-
Time Paths. Mineral. Soc. Amer. Monograph 1.
Geothermobarometry
The GASP geobarometer
Figure 27.98. P-T diagram contoured for equilibrium curves of various values of K for the GASP geobarometer reaction: 3 An = Grs + 2 Ky +
Qtz. From Spear (1993) Metamorphic Phase Equilibria and Pressure-Temperature-Time Paths. Mineral. Soc. Amer. Monograph
Geothermobarometry
Table 27-3. Mineral Compositions, Formulas, and End-
Members for Sample 90A from Mt. Moosilauke, New
Hampshire
Cations
Si 3.00 5.43 6.17 2.84
IV
Al 2.00 2.57 1.83 1.17
VI
Al 0.98 3.81
Ti 0.15 0.04
Fe 2.19 2.32 0.08
Mg 0.30 2.36 0.10
Mn 0.42 0.02 0.00
Ca 0.09 0.00 0.14
Na 0.08 0.44 0.83
K 1.58 1.42 0.03
Fe/(Fe+Mg) 0.88 0.50 0.46
Prp 10 An 14
Alm 73 Ab 83
Sps 14 Or 3
Grs 3
From Hodges and Spear (1982) and Spear (1993).
Geothermobarometry
Figure 27.10. P-T diagram showing the results of garnet-biotite geothermometry (steep lines) and GASP barometry (shallow lines) for sample
90A of Mt. Moosilauke (Table 27.4). Each curve represents a different calibration, calculated using the program THERMOBAROMETRY, by
Spear and Kohn (1999). The shaded area represents the bracketed estimate of the P-T conditions for the sample. The Al 2SiO5 invariant point
also lies within the shaded area.
Geothermobarometry
TWQ and THERMOCALC accept mineral
composition data and calculate equilibrium
curves based on an internally consistent set of
calibrations and activity-composition mineral
solution models.
Figure 27.11. P-T phase diagram calculated by TQW 2.02 (Berman, 1988, 1990, 1991) showing the internally consistent reactions between
garnet, muscovite, biotite, Al2SiO5 and plagioclase, when applied to the mineral compositions for sample 90A, Mt. Moosilauke, NH. The
garnet-biotite curve of Hodges and Spear (1982) Amer. Mineral., 67, 1118-1134 has been added.
Geothermobarometry
THERMOCALC (Holland and Powell) also based on an internally-consistent dataset
and produces similar results, which Powell and Holland (1994) call optimal
thermobarometry using the AvePT module.
Calculates an optimal P-T point within the correlated uncertainty of all relevant
reactions via least squares and estimates the overall activity model uncertainty.
The P and T uncertainties for the Grt-Bt and GASP equilibria are about 0.1 GPa
and 75oC, respectively.
A third independent reaction involving the phases present was found (Figure 27.12b).
Notice how the uncertainty increases when the third reaction is included, due to the
effect of the larger uncertainty for this reaction on the correlated overall uncertainty.
The average P-T value is higher due to the third reaction, and may be considered
more reliable when based on all three.
Figure 27.12. Reactions for the garnet-biotite geothermometer and GASP geobarometer
calculated using THERMOCALC with the mineral compositions from sample PR13 of Powell
(1985). A P-T uncertainty ellipse, and the “optimal” AvePT ( ) calculated from correlated
uncertainties using the approach of Powell and Holland (1994). b. Addition of a third
independent reaction generates three intersections (A, B, and C). The calculated AvePT lies
within the consistent band of overlap of individual reaction uncertainties (yet outside the ABC
triangle).
Geothermobarometry
Thermobarometry may best be practiced
using the pseudosection approach of
THERMOCALC (or Perple_X), in which a
particular whole-rock bulk composition is
defined and the mineral reactions delimit a
certain P-T range of equilibration for the
mineral assemblage present.
Figure 27.13. P-T pseudosection calculated by THERMOCALC for a computed average composition in NCKFMASH for a pelitic
Plattengneiss from the Austrian Eastern Alps. The large + is the calculated average PT (= 650 oC and 0.65 GPa) using the mineral data of
Habler and Thöni (2001). Heavy curve through AvePT is the average P calculated from a series of temperatures (Powell and Holland, 1994).
The shaded ellipse is the AvePT error ellipse (R. Powell, personal communication). After Tenczer et al. (2006).
Geothermobarometry
P-T-t Paths
Figure 27.14. Chemically zoned plagioclase and poikiloblastic garnet from meta-pelitic sample 3, Wopmay Orogen, Canada. a. Chemical
profiles across a garnet (rim rim). b. An-content of plagioclase inclusions in garnet and corresponding zonation in neighboring plagioclase.
After St-Onge (1987) J. Petrol. 28, 1-22 .
Geothermobarometry
P-T-t Paths
Figure 27.15. The results of applying the garnet-biotite geothermometer of Hodges and Spear (1982) and the GASP geobarometer of Koziol
(1988, in Spear 1993) to the core, interior, and rim composition data of St-Onge (1987). The three intersection points yield P-T estimates which
define a P-T-t path for the growing minerals showing near-isothermal decompression. After Spear (1993).
Geothermobarometry
P-T-t Paths
Recent advances in textural geochronology have allowed age
estimates for some points along a P-T-t path, finally placing
the “t” term in “P-T-t” on a similar quantitative basis as P
and T.
Figure 27.17. An illustration of precision vs. accuracy. a. The shots are precise because successive shots hit near the same place
(reproducibility). Yet they are not accurate, because they do not hit the bulls-eye. b. The shots are not precise, because of the large scatter, but
they are accurate, because the average of the shots is near the bulls-eye. c. The shots are both precise and accurate. Winter (2010) An
Introduction to Igneous and Metamorphic Petrology. Prentice Hall.
Geothermobarometry
Precision and Accuracy
Figure 27.18. P-T diagram illustrating the calculated uncertainties from various sources in the application of the garnet-biotite geothermometer
and the GASP geobarometer to a pelitic schist from southern Chile. After Kohn and Spear (1991b) Amer. Mineral., 74, 77-84 and Spear (1993)
From Spear (1993) Metamorphic Phase Equilibria and Pressure-Temperature-Time Paths. Mineral. Soc. Amer. Monograph 1.