Week 3 topics

• Review of thermodynamics: Gibbs free energy

• Review of phase diagrams
• Introduction to trace elements
Gibbs free energy
• Allows us to determine the spontaneity of chemical change at
constant pressure
• Mathematically it combines the 1st and 2nd law of thermodynamics
• The Gibbs free energy of a substance i (Gi) is:
Gi = Hi - TSi (H: enthalpy; S: entropy)
But we cannot know Gi directly, and the change in G for a particular reaction is
considered (ΔGr)
• ΔG = ΔH - TΔS
 Gibbs free energy
• Consider the reaction:
aA + bB = cC + dD
• When ΔGr = 0 equilibrium
ΔGr < 0 for spontaneous reaction (from left to right)
ΔGr > 0 for non-spontaneous reaction (from right to left)
CaAl2Si2O8 + H2O + 2H+ = Ca2+ + Al2Si2O5(OH)4
∆𝐺𝑓° -960.15 -56.687 0 -132.3 -908.07
∆𝐺𝑟° = [(-132.3) + (-908.07)] – [(-960.15) + (-56.687)] It is natural, at surface
conditions, for feldspar to
= -23.53 kcal/mol weather to kaolinite
Note ° means for a standard state (pure substance at 1 bar)

Langmuir. Aqueous Environmental Geochemistry

 Gibbs free energy
• Consider the reaction:
aA + bB = cC + dD
• ΔG can be related to the equilibrium constant (Keq) for a reaction
𝑐 𝑑
𝐶 𝐷
ΔGr = ΔGr° + RT ln 𝑎 𝑏 (R: gas constant; T: temperature)
𝐴 𝐵

Q = reaction quotient at equilibrium; Q=Keq

ΔGr = ΔGr° + RT lnKeq “perhaps the single most useful

equation for petrologists” – Putirka (2008)
Keq is only a constant at fixed P and T

Langmuir. Aqueous Environmental Geochemistry

 Application in geothermobarometry
• A good thermometer has a large ΔSr and a good barometer has a
large ΔVr

Putirka, 2008
• Gibbs phase rule
F=C-P+2

P(phases): a phase should be mechanically

separable from a system, with distinct
physical and chemical properties.
Ex.: phases in magma = minerals, liquid, gas
Phases are made up of 1 or 2 components
C(components): simple chemical units that
can be combined to describe the chemical
composition of the substances in a system
Ex.: kaolinite [Al2Si2O5(OH4)] = Al2O3, SiO2, H2O
as components or Al3+ , Si4+ , H+ and O2-
F: variance or the number of independent
variables or degrees of freedom
2 intensive parameters that describe the
system, P and T in this case
Langmuir. Aqueous Environmental Geochemistry
H2O system
Gibbs phase rule
F=C-P+2

Example: at the triple point of water

C=1

P=3

F=0

The triple point of water occurs at fixed T and P

(0.01C and 0.0006 Mpa)

No degrees of freedom, and the state at this

Winter. Igneous Petrology
point is invariant.
Fig. 6.7. After Bridgman
(1911) Proc. Amer. Acad. Arts
and Sci., 5, 441-513; (1936) J.
Chem. Phys., 3, 597-605;
(1937) J. Chem. Phys., 5, 964-
966.
H2O system
Gibbs phase rule
F=C-P+2

Example: at point A

C=1

P=2 A

F=1

One degree of freedom, and the state at this

point is univariant.

Equilibrium between liquid and vapor is

maintained along this line (from above the
triple point to below the critical point)
Winter. Igneous Petrology
Fig. 6.7. After Bridgman
(1911) Proc. Amer. Acad. Arts
and Sci., 5, 441-513; (1936) J.
Chem. Phys., 3, 597-605;
(1937) J. Chem. Phys., 5, 964-
966.
H2O system
Gibbs phase rule
F=C-P+2

Example: at point B

C=1

P=1 B

F=2

Two degrees of freedom, and the state at this

point is divariant.

Temperature and pressure can be varied

independently within the liquid field and the
phase is maintained.
Winter. Igneous Petrology
Fig. 6.7. After Bridgman
(1911) Proc. Amer. Acad. Arts
and Sci., 5, 441-513; (1936) J.
Chem. Phys., 3, 597-605;
(1937) J. Chem. Phys., 5, 964-
966.
Silicate systems
• In the early 1900, geochemists in the Geophysical Laboratory of the
Carnegie Institution embarked on what was to become a most
extensive experimental program devoted to crystal-melt equilibria.
The influence of the total output of the project on igneous
petrogenesis has been immense.
– Williams, Turner, Gilbert (Petrography: An Introduction to the Study of
Rocks in Thin Sections)
• Let us look at some of the phase diagrams produced from the project.
 2-Component Eutectic System

Example: X
1.) Equilibrium
crystallization of X Y
melt composition T1

2.) Fractional Z
T2
crystallization, with
X as starting
composition, at E
point Z

3.) Equilibrium Y Z X
crystallization of Y
melt composition
Terms
• Liquidus: Above the liquidus line, the existing phase is liquid.
Below and along the liquidus line, solid and liquid phases coexist
• Solidus: Below the solidus line, all existing phases are solid
Above and along the solidus line, solid and liquid phases coexist
• Eutectic point: The point at which the last drop of liquid is left during
crystallization
The point at which the first drop of liquid occurs
during melting
The point where all phases coexist
An invariant point
 2-Component Eutectic System
Gibbs phase rule
F=C-P+1
X
Example:
1.) At point X:
C=2 Y X1 T1
P=1
F=2 Z
T2
2.) At point X1:
C=2 E
P=2
F=1
Y Z X
3.) At point E:
C=2
P=3
F=0
 Binary Phase diagram: 2-component system, plagioclase

At 1450 C,
~An80 pl crystal is in equilibrium with
~An47 liquid
But the phase diagram will change if you change pressure and melt water content

Harder to melt
at higher P

Easier to melt
at higher
water content

Bennett, 2019
Trace elements
● Elements which have concentrations less than 0.1 %
● Usually reported in ppm
● Trace elements are important because they give insights on magmatic
processes, particularly differentiation processes
● Can be classified based on their bahavior in magmatic systems
Trace elements
Compatible elements: elements
that are easily accepted (in the
mineral structure)

Incompatible elements: elements

that are not easily accepted (in the
mineral structure)
: large ionic radius, high ionic
charge elements

Rollinson (Using Geochemical Data)

Trace elements
Goldschmidt Rules

• 2 ions with the same radius and

same charge will tie in their
competition for a lattice site
• If 2 ions have the same charge
and similar radii, the smaller ion
will more favorably move into
the lattice site
• Of 2 ions with similar radii and
unequal charge, the higher-
charged ion will more readily
move into the lattice site
Element substitution

Schematic quartz structure showing the configuration of different trace elements in the quartz lattice. Also
it is proposed that substitution of Si 4+ by four H + is possible (silanol groups). Because of the two-
dimensional illustration the fourth H + is not shown on the figure ( Müller, 2012 ).
Element substitution
Note: this example is for major elements in olivine
Trace elements
• LFS: Low Field Strength
elements
• LIL: Large-Ion Lithophile
elements
• HFS: High Field Strength
elements

Let’s look at a numerical way to

describe compatibility
Trace element
● The Nernst distribution coefficient describes the equilibrium
distribution of a trace element between a mineral and a melt

● Kd = Cci/Cli
● Cci = concentration in mineral of element i
● Cli = concentration in melt of element i
Distribution coefficient
● Example: Sr in plagioclase phenocryst = 500ppm; Sr in the glassy
groundmass = 125ppm; Kd for Sr in plagioclase = 4
● A mineral/melt distribution of 1 means that the element is equally
distributed between crystal and liquid (melt)
● A value greater than 1 implies that the trace element has a preference
for the mineral phase and is a compatible element
● A value less than 1 implies that the trace element has a preference for
the melt and is an incompatible element
 Bulk distribution coefficient
● Di = x1Kd1 + x2Kd2 + x3Kd3
● element i
● x1 = percentage proportion of mineral 1 in the rock
● Kd1 = partition coefficient of element i in mineral 1
● Example: a rock containing 50% olivine, 30% orthopyroxene and 20%
clinopyroxene
● Di = 0.5Kdol1 + 0.3Kdopx2 + 0.2Kdcpx3

https://earthref.org/KDD/
 Distribution coefficient
● Variables that may affect
partition coefficient
– Composition
– Temperature
– Pressure
– Oxygen activity
– Crystal chemistry
– Water content of melt

Rollinson (Using Geochemical Data)

Examples
Mineral/melt partition coefficient (Kd) for Ni

Olivine Orthopyroxene Clinopyroxene

Basaltic and 5.9-29 5 1.5-14

basaltic andesite
liquids
Andesitic liquids 58 8 6

Example of Kd affected by melt composition

Magma differentiation as shown by major and
trace elements
Any process by which a magma is able to diversify and
produce a magma or rock of different composition
• Partial Melting
• Crystallization: Equilibrium and Fractional Crystallization
• Magma Mixing
• Assimilation

*Magma is a mixture of minerals, liquid, and dissolved volatiles