Hydrothermal Geochemistry 17 January 2005

Data presentation
A variety of different methods are available for presentation
of data: the choice of method is dependent upon what you
wish to portray, and the data that are available.

Generally, one must fix some of the parameters to make a

diagram useful.

Activity – activity diagrams

Portray phases
present at different
activities of
components of
interest.

Must have reaction

data for mineral
species of interest.

P,T must be fixed.

Data presentation 1
Hydrothermal Geochemistry 17 January 2005

Eh – pH diagram
Useful in that both Eh and pH are
readily measurable under many
lab conditions.
Eh measures activity of electrons
(as voltage changes)
pH measures activity of protons
(H+ ions)

fo2 – pH diagram
Topologically identical to Eh-pH
diagram but easier to read.
Activity of O2 can be related to Eh
through thermodynamic
parameters of the half-cell
reaction:

2H2O = 4H+ + 4e- + O2

Eh = ∆G°H O/2F +
2

(4.5756T)(log aO2)/4F –
(4.5756T)(pH)/F

Data presentation 2
Hydrothermal Geochemistry 17 January 2005

Temperature – composition (TX) diagrams

Isobaric TX diagram: most useful in metallurgy where P is
fixed (usually 1 atm). Not as relevant to geology where P
is fixed by vapor pressure of system components.

Isobaric TX diagram
for Fe-S system

Temperature – composition (TX) diagrams

Condensed TX diagram: topologically similar to isobaric TX
diagram, but shows only condensed phases. Generally
useful for solid phases where compressibility is not an
issue. Usually presented at fairly low P.

Condensed TX diagram
for Fe-S system

Data presentation 3
Hydrothermal Geochemistry 17 January 2005

Condensed TX diagram
for Na-Ca-Al-Si-O system

Condensed TX diagram
for Fe-Zn-S system

Pressure – composition (PX) diagrams

Not particularly useful for most geological conditions, but provides
some information if vapor is a component of the system.
T must be fixed.

PX diagram for
Fe-S system

Activity – composition diagram

Useful for evaluation of thermochemical parameters, but not
particularly geologically relevant (isothermal and isobaric).
Conditions must fall along one of the lines (there are no two-
dimensional fields).

pyrite

pyrrhotite

Data presentation 4
Hydrothermal Geochemistry 17 January 2005

Free energy – composition diagram

Lines represent two-phase fields; curves represent one-phase
fields. Note pyrrhotite has a broad curve because it has a
variable composition.
All systems at equilibrium will approach the minimum free energy.
Can use this diagram to calculate the chemical potential (partial
molar free energy) by extrapolation of tangent lines.

Minimum free energy –

tangent to two phases

Pressure – Temperature (PT) diagram

Incompressibility of most solids and liquids (py, po, SL)
means very little P dependence for these reactions; most
reactions are near-vertical straight lines.

Pressure – temperature (PT) diagram

There is a strong dependence on P for boiling of S because
of the vapor phase) – easiest to see on a log scale.
Note differences in composition for univariant lines.

Data presentation 5
Hydrothermal Geochemistry 17 January 2005

Activity of sulfur – pressure diagram

Incompressibility of most phases results in near-vertical phase
boundaries.

Activity of sulfur – temperature diagram

Reciprocal T used to linearize boundaries.
If T is known or estimable, can calculate the aS2.
Or can establish both T and aS2 by intersecting phase boundaries.
Curved boundaries represent variation in activity of components
in minerals

Activity of sulfur – temperature diagram

Pyrrhotite is a good reactive mineral and allows determination of
aS2 in experimental and natural systems.
These are important baseline data and fix one critical parameter.

Data presentation 6