Binary Phase Diagrams

Please refer to the phase diagrams handed out in class.

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A phase is a physically homogeneous substance. Phases of interest to petrologists
includeminerals, liquids, and gasses. A phase diagram is a graphical representation
of theequilibrium relations among phases, typically as a function of one or more
intensive variablessuch as chemical composition, temperature, pressure, and the
activity of a chemical component.
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Phase diagrams are used by geologists, chemists, ceramists, metallurgists and other
scientiststo organize and summarize experimental and observational data. Phase
diagrams are also usedto make predictions about processes that involve chemical
reactions among phases. Similar
principles or rules apply to interpretations using phase diagrams for igneous
processes,
metamorphic processes, hydrothermal processes, lacustrian geochemistry, etc.
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Phase diagrams can be grouped according to the number of independent chemical
componentsneeded to represent the chemical compositions under consideration.
Chemical components are
convenient groupings (ratios) of chemical elements, typically theoretical "end-
member" chemicalcompositions. If all the chemical compositions of interest can be
shown on a line (i.e. if all
compositions can be represented as a linear combination of two chemical
components), then thesystem under consideration is a two-component system. If a
plane is needed to represent allcompositions of interest, then the system under
consideration is a three-component system. Et
cetera.
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For each choice of the variables used to construct the phase diagram, the diagram
shouldindicate what phase or assemblage of phases is the equilibrium assemblage. If
compositionaxes are used, the chemical compositions of the phases in equilibrium
should also be given.
Compositions of two coexisting phases are indicated by end points of tie lines,
lines thatconnect the compositions of phases that may be in equilibrium.
Compositions of threecoexisiting phases are indicated by the corner points of three
phase triangles. The relative
proportions of two phases in equilibrium may be determined from the bulk
composition of thesystem, the lever rule, and the tie line. Similarly, the relative
proportions of three phases inequilibrium may be determined from the bulk
composition of the system, the ternary leverrule, and the three phase triangle.
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Isobaric melting and crystallization may be studied using phase diagrams that
involve liquids.
For most geologic systems the liquid is a silicate melt, but the same principles
apply to manyother systems. The system H2O-NaCl provides a convenient "everyday"
analog for a simpletwo-component igneous system like CaMgSi2O6-CaAl2Si2O8
(diopside-anorthite). It is
possible to show the equilibrium assemblages in the H2O-NaCl system as a function
oftemperatures and composition by constructing a phase diagram using temperature as
thevertical axis and using the compositions H2O and NaCl to define a horizontal
compositionaxis . At low temperatures, the "melt" in the H2O-NaCl system is salt
water or "brine."
Brines may be more or less salty depending on the ratio of NaCl to H2O, i.e.
depending onthe bulk composition. However, there are limits to how salty (and how
"wet"!) the brine canbe. The limit of saltiness is the saturation curve or liquidus
for halite. The limit of
"wetness" is the liquidus for ice. A liquidus is the locus of compositions of
liquids that are inequilibrium with solids. For a two component system, a liquidus
will be a curve. For a three
component system, a liquidus will be a surface. For a four or more component
system, aliquidus will be a hypersurface.
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In addition to having limits to its possible composition (saltiness or wetness),
the melt (brine)
in the system H2O-NaCl is limited in terms of the possible temperatures at which it
is stable.
The lowest temperature at which an H2O-NaCl brine can exist at equilibrium is 0�F
(-21.1�C).
Binary Phase Diagram Notes

This is the temperature at which the halite liquidus and the ice liquidus meet. The
point ofintersection is called the eutectic point, the unique liquid composition at
that point is called theeutectic composition, the temperature of the intersection
point is called the eutectic temperature,
and the chemical reaction (Brine --> Ice + Halite) that occurs upon cooling through
thistemperature is the eutectic reaction. For any bulk composition except that of
pure H2O or pureNaCl, the last liquid to crystallize upon cooling will have the
eutectic composition and willcrystallize at the eutectic temperature. Similarly,
any "rock" made of a mixture of halite and ice,
in any proportion, will begin to melt at the eutectic temperature. And the first
liquid to appearwill have the eutectic composition! (Actually, the system H2O-NaCl
has another phase -

hydrohalite (NaCl.2H2O) -- that is stable only below 0.1�C and complicates this
story, butthis phase was ignored in the above discussion and in our experiment.)

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The system CaMgSi2O6-CaAl2Si2O8 (Diopside-Anorthite) is a simple eutectic
system(almost!). All of the concepts discussed above regarding the H2O-NaCl system
apply to theDi-An system. For any rock consisting of a mixture of diopside and
anorthite, in anyproportions, the first liquid will appear at 1274�C, the eutectic
temperature, and will have theeutectic composition. There are limits to the
possible compositions of the silicate melts in thissystem. These limits vary with
temperature and are indicated by the liquidus curves fordiopside and anorthite.
Note that crystals of diopside alone will melt to a liquid of their owncomposition
at 1391.5�C. Similarly, crystals of anorthite alone will melt congruently, that
isto a liquid of their own composition.
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In contrast to ice, diopside, and anorthite, crystals of sanidine melt
incongruently. At 1150�C,
sanidine crystals "melt" to form a mixture of leucite crystals and silicate liquid.
This
incongruent melting is really a chemical reaction (Sanidine --> Leucite + Liquid)
that isterminal for sanidine and for which one of the products happens to be a
liquid. Compare thisreaction with the eutectic reaction for the H2O-NaCl system
(Ice + Halite --> Brine) that isterminal for the liquid. The two types of reaction
look different on the phase diagram becausethe liquid has a variable composition at
temperatures removed from the eutectic temperature,
whereas sanidine has a fixed composition. An incongruent melting reaction is also
called a
Binary Phase Diagram Notes

peritectic reaction. The peritectic point is the point of intersection of two

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If the system under consideration contains minerals that can vary in composition,
then thetemperature at which the first liquid appears upon heating depends on the
composition of thesolid. Plagioclase feldspar exhibits complete solid solution from
albite (Ab) NaAlSi3O8 to
anorthite (An) CaAl2Si2O8. The temperature for which the first liquid appears for
eachplagioclase composition is given by the plagioclase solidus curve. A solidus is
the locus of
compositions of solids that are in equilibrium with liquids and can be a curve,
surface, orhypersurface depending on the number of components in the solid
solution. Just as the
composition of a liquid follows the liquidus with changing temperature, so also
thecomposition of a solid follows the solidus with changing temperature. However,
because it iskinetically mode difficult to change the chemical composition of a
solid (diffusion can bevanishingly slow in a solid), solid compositions may not
change with temperature as predictedby the phase diagram. During crystallization
this resistance to change may lead to chemicallyzoned crystals -- a feature
commonly observed for plagioclase crystals with the petrographicmicroscope.
Other Readings on Binary Phase Diagrams

Blatt and Tracy: p. 81-93, 101-105.