Phase

Equilibrium
Reporters:
Cruz, Jerico
Caringal, Angelo
Castillanes, Jobert
Dion, Canlas
Candidato, Vince
Taedo, Cassidy
ABSTRACT

The recent interest in the determination of the phase
diagrams for many systems involving water as one
component has been in those systems which are of
greatest importance to clay mineralogy. The importance
of both published and more recent work on synthesis of
the clay is demonstrated in the ability to prepare
chemically pure, mineralogically homogeneous kaolinites,
montmorillonites, micas, and chlorites. The stability and
identification of the clay minerals are discussed in relation
to some of the major problems of clay mineralogy.
INTRODUCTION
Studies of phase equilibria are highly relevant to many areas of geosciences
because in most cases, mineral systems have the time to reach thermodynamic
equilibrium and lack the energy input needed to sustain disequlibrium. With
increasing pressure, most crystal structures that are stable at low pressure (e.g. 1
bar) are replaced by denser structures. This has important implications for Earth's
interior as well as for the synthesis of novel materials for industrial applications. A
significant area of mineral physics research is therefore dedicated towards
discovering new phases that may be present either in the deep earth or within
other planets and characterizing their physical and chemical properties.
Equilibrium relations between phases at high pressure are governed by the same
thermodynamic principles that operate at low pressure.
A given mineral crystallizes as a stable phase only within the
restricted ranges of pressure and temperature. Subjecting the
mineral to conditions that fall outside its stability will cause
another mineral that is table under those conditions to crystallize
in its place.
Testing mineral stability: laboratory experiment looking at the T, P,
water vapour pressure,etc)
Note: Phase diagrams
I. Introduction

Concepts that are particularly important to
understand are: Gibbs Free energy, enthalpy,
entropy, chemical activity, Clausius Clapeyron
equation, endothermic and exothermic reactions
and the phase rule.
II. Description of Terms:
1) Phase part or parts of a system occupying a specific volume and having
a uniform physical and chemical characteristics which distinguish it from all
other parts of the system.
2) System a collection of geological phases
a) Open system one that is free to exchange both matter and energy with its
surroundings
b) Closed system - one that is sealed with respect to the transfer of matter, but that
can still exchange energy with the surroundings.
c) Isolated system - one that is incapable of exchanging both mass and energy with its
surroundings.

II. Description of Terms:
3) Component basic chemical constituents of a system, of which the various
phases are composed; comprises the minimum number of chemical (atomic
and molecular) species required to specify completely the compositions of all
the phases present.

III. Equilibirum
A. Thermal equilibirum
All parts of the system have the same temperature; there is no net transfer of
heat.
B. Chemical equilibrium
Distribution of components among the phases of a system has become
constant, showing no net change with time; the flux of atoms across the
crystal boundary is the same in both directions.
Note: disequilibrium
IV. The Gibbs Phase Rule

Q: How many phases can be in equilibrium with each other at any one time?
(William Gibbs-1870- pioneer of modern thermodynamics)
Phase Rule- expresses the number of phases that can coexist in mutual
equilibrium () in terms of the number of components (C) in the system
and variance (F).
Variance = number of degrees of freedom
+ F = C + 2
Degrees of freedom of a system is the number of variables (i.e., temperature,
pressure and concentration of the components, which must be arbitrarily fixed in
order that the condition of the system may be completely defined.
Phase Characteristic
A phase does not have to be BOTH physically and chemically distinct

Example:
1.Water and ice
2.Oil and water

Equilibrium Assemblages
At equilibrium, the mineralogy (and the composition of each mineral)
is determined by T, P, and X Mineral paragenesis refers to such an
equilibrium mineral assemblage Relict minerals or later alteration
products are thereby excluded from consideration unless specifically
stated
Driving Forces and Gibbs Free Energy

Enthalpy
Enthalpy is a measure of the total energy of a thermodynamic system. It
includes theinternal energy, which is the energy required to create a system,
and the amount of energy required to make room for it by displacing
itsenvironment and establishing its volume and pressure.
Enthalpy is athermodynamic potential. It is a state function and
anextensive quantity. The unit of measurement in theInternational System of
Units (SI) for enthalpy is the joule, but other historical, conventional units are still
in use, such as the small and the large calorie.

ENTROPY
a measure of the unavailable energy in a closed
thermodynamic system that is also usually
considered to be a measure of the system's
disorder, that is a property of the system's state,
and that varies directly with any reversible change
in heat in the system and inversely with the
temperature of the system;
CHEMICAL ACTIVITY
The active mass or chemical activity of any chemical system is
simply the chemical activity of its components, which are the
reactants or the products of a chemical reaction. The rate of the
chemical reaction CaCO3 --> CaO + CO2 is then proportional to the
activity of CaCO3, while the rate of the reverse reaction, CaO + CO2
--> CaCO3 is proportional both to the activity of CaO and to the
activity of CO2. Likewise, the driving force of the reaction of CaCO3
is directly proportional to the activity of CaCO3 while the driving
force of the reverse reaction is directly proportional both to the
activity of CaO and to the activity of CO2.
Clausius Clapeyron equation
The relationship between the temperature of a liquid and its vapor pressure is
not a straight line. The vapor pressure of water, for example, increases
significantly more rapidly than the temperature of the system. This behavior
can be explained with the Clausius-Clapeyron equation.

The Clausius-Clapeyron Relation
Along the phase boundary:
P
T
P
T
phase
boundary
Since S1 - S2 = L/T (L is the latent heat), we
arrive at the Clausius-Clapeyron Relation :
For the slope of the
boundary we have:
ENDOTHERMIC AND EXOTHERMIC
REACTIONS
exothermic:
1. release heat, therefore the room temperature will increase
2. H = negative (kJ mol^-1)
3. bond will be formed, and energy will be release in form of heat, the
molecules that are formed had a lower kinetic energy but very stabil

endothermic:
1. absorb heat, therefore the room temperature will decrease
2. H = positive (kJ mol^-1)
3. bonds will broke down, because the energy of reactants are less than the
energy of products in the chemical reaction
PHASE RULE
The Phase Rule describes the possible
number of degrees of freedom in a (closed)
system at equilibrium, in terms of the
number of separate phases and the
number of chemical constituents in the
system. It was deduced from
thermodynamic principles by J. W. Gibbs in
the 1870s.
PHASE RULE
Phase diagrams in P-T space (Reaction or equilibrium between
compounds)
NaAlSi2O6 + SiO2 = NaAlSi3O8
Jadeite (px)
silica pyroxene
Note: reaction or equilibrium boundary
Gibbs Phase Rule
The Phase Rule- expresses the number of phases that can coexist in mutual
equilibrium
F = C - P+ 2
F is the degree of freedom
P - number of phases
C minimum number of components.
Note: the 2 represent 2 intensive parameters particularly temperature and
pressure.

High Pressure Phase Equilibrium Studies
There are a number of different types of high pressure studies
related to phase equilibria. There are true phase equilibrium
studies that seek to characterize the range of pressure,
temperature or chemical activity (e.g. for O2) over which a given
phase (or phase assemblage) is stable.
Synthesis studies seek to discover and produce new phases.
However, they are distinct from phase equilibrium studies. There
are a number of circumstances that can lead to minerals forming
outside their thermodynamic stability field. Another major area of
interest is phase transformation mechanisms and kinetics.
Reversals: the difference between synthesis
and phase equilibrium studies

One of the most important
features of a good phase
boundary determination is the
reversal. A reversal is a pair of
experiments where the reactants
and products in one experiment
become the products and
reactants in another experiment.




Reversals: the difference between synthesis
and phase equilibrium studies

The position of the phase boundary can be said to be somewhere between
these bracketing experiments. In-situ experiments (e.g. synchrotron x-ray
diffraction) are particularly efficient for conducting phase equilibrium studies
because the transformation from one phase assemblage to the other can be
run first one way and then back the other at a number of pressure and
temperatures during a single experiment.








Since phase boundaries are lines (or curves if volatiles are present) at minimum two
reversal are required to fully describe a phase boundary. Reversals are necessary for two
reasons:

1)Due to kinetics, phases can persist in some cases indefinitely outside of their stability
field. Merely witnessing a phase at a given P and T, especially at lower temperatures,
does not guarantee that it is the stable phase.


2) As mentioned above, phases can be synthesized outside of their stability field. Some
of the reasons that this can occur are related to a phenomena referred to as Ostwald's
step rule which says that the first phase to from in a reaction is not always the one with
the lowest free energy but the phase with a free energy closest to the free energy of the
reactants. In order to start with a sample that is highly homogeneous, experimentalists
may choose a gel or glass; the free energy of these reactants can be quite large.
Reactants ground in a mortar and pestle can be highly strained (e.g. Kingma et al., 1993)
which can also substantially raise their free energy. So for example, coesite can be
produced from highly strained quartz at P and T conditions in the quartz stability field
(Green, 1972). For these reasons if one wants to measure the position of a phase boundary
or confirm that a given phase in fact has a stability field, reversals are required.
Discovery and Synthesis of New Phases
The simplest way to discover a new
phase is to put reactants of interest
together and bring them to some
new pressure temperature condition
and either observe them with x-rays
at temperature and pressure or
quench them and use x-ray
diffraction to identify the phases
present and search for new phases.
However, there are more
sophisticated strategies for searching
P,T chemistry spaces for new phases.

Discovery and Synthesis of New Phases
However, there are more sophisticated strategies for searching P,T chemistry
spaces for new phases. One strategy that has been around for a long time is
to use one's knowledge of phase relations in one chemical system to make
intelligent guesses about phase relations in another similar chemical system.
For example, the observation that Mg2GeO4 formed in both an olivine and a
denser spinel structured polymorph, led researchers in the 1930's to suggest
that (Mg, Fe)2SiO4 olivine might also have a spinel structured polymorph which
could account for the increase in seismic velocity at ~400 km depth. Many
compounds that share the same stoichiometry have phase diagrams that
share the same topology.
Phase Equilibria Relevant to the Deep Earth
Phase diagrams illustrate the stability of phases in Pressure,Temperature,
chemical activity space. Many igneous and metamorphic systems contain
up to 11 significant chemical components. This means that a full depiction of
phase equilibria in these systems requires 13 dimension. Petrologists have
devised a host of sections, pseudo sections and projections to create
illustrative 2D diagrams from these multi-dimensional spaces. Mineral physics
has mostly confined itself to working in relatively simple chemical systems
(e.g. MgO-SiO2) that serve as a proxy for the chemically more complex Earth.
Another strategy is to look at changes with pressure and temperature in a
single bulk composition (e.g. MORB or pyrolite). A selection of relevant phase
diagrams is given below.
Phases: Kyanite, Sillimanite and Andalusite
Component: Al2SiO5
Pressure and Temperature Phase
Diagram (One component)
Analyze at point X, Y and Z.
Analyze point F
Binary Diagrams
Composition is now variable

Condensed phase rule
P + F = C + 1
Note: pressure is no longer a variable: only Temperature and composition
matter.
Crystallization in systems with no solid
solution
no compounds/solid
solutions in solid state
only single phase liquid
at high temperatures
partial melting at
intermediate
temperatures

Liquidus Curve- specifies
the maximum
temperature at which
crystals can co-exist
with the melt in
thermodynamic
equilibrium

Tie Line- links together
the compositions of two
phases which can
coexist stably

Analyze point x1 and E
Liquidus
Curve
System with a complete Solid Solution
Example would be plagioclase
m, cools down,
encounters liquidus at
a where plag b will
begin to crystallize

Because b is more
calcic, it will deplete
the melt with
anorthite and thereby
enrich it with albite

The changing melt
composition causes a
corresponding
evolution in the
equilibrium
composition of the
plagioclase crystals.

LEVER RULE
The lever rule is a tool used to determine weight percentages of each
phase of a binary equilibrium phase diagram. It is used to determine the
percent weight of liquid and solid phases for a given binary composition
and temperature that is between the liquidus and solidus.

Consider a cooling alloy at the composition and temperature
marked on the diagram. As shown on the phase diagram, the
alloy is, at the given temperature, a mixture of alpha and liquid
phases - but what are their exact compositions at this
temperature?





An isothermal (constant temperature) line through the alloy's position on the phase
diagram when it is in a two phase field, intersecting the two adjacent solubility curves, is
called a tie line (yes, that's the horizontal yellow line on the diagram).The ends of the tie
lines show the compositions of the two phases that exist in equilibrium with each other at
this temperature. From the diagram we know that alpha and liquid phases will exist. The tie
line shows that the alpha phase is 5.2%B and the liquid phase is 34.5%B at this temperature.
Remember, though, that the overall composition of the sample is unchanged - we are only
discovering the compositions of the constituent phases within the sample.

For a cooling alloy at composition C
o
and temperature T
x
, tie lines may
be used to answer questions such as:
what phases are present ?
what are their compositions ?
if the temperature is reduced to T
y
, how do the compositions of the two
phases vary ?

The answer to "what phases are present ?" is easy. Composition C
o
and
temperature T
x
meet in the beta + liquid phase field, so these are the two
phases present.


To answer "what are their compositions ?" we must draw a horizontal tie
line from the point to the nearest phase diagram boundaries. The tie line
shows us that the compositions are:

Liquid: X wt% B
Beta: Y wt% B





To answer the last question "if the temperature is reduced to T
y
, how do the compositions of the
two phases vary?"consider the new tie-line, shown in yellow on the diagram.The compositions of
liquid and beta phase have both decreased in wt%B to:

Liquid: X' wt% B
Beta: Y' wt% B

Thus, both the liquid and the beta phases are getting richer in A as the sample is cooled.




Now that we know the compositions of the two phases, we need to
find how much of each phase exists at the given temperature.
The ratio of the two phases present can be found by using the lever
rule.At first sight the lever rule can appear confusing. It is really invoking
the conservation of mass, and can be proved mathematically, as shown
below the diagram.
Essentially, we start off with an overall composition of our alloy - C
o
. From
the tie-line we know that the two phases at a given temperature have
two different compositions, but overall the amounts of these two
compositions must add up to the alloy's overall composition, C
o
.
This is the basis for the lever rule. Using the lever rule itself is very simple,
we'll show you with a diagram.....

Basically, the proportions of the phases present are given by the relative
lengths of the tie line. So, the proportions of alpha and liquid present on
the diagram (showing a portion of the whole phase diagram) are:

X Y
X+Y and X+Y


Simple, isn't it ?
But... which equation corresponds to which phase ?



Now, consider the same alloy as it crosses the liquidus line. It seems
reasonable to assume that, at this point, the alloy will be nearly all liquid.
Looking at the diagram it can be seen that Y1 is very small here and so
must be the proportion of alpha present. Similarly X1 is relatively large and
so it corresponds to the amount of liquid.

So, the left side of the tie line gives the proportion of the liquid phase (the
phase to the right), and the right side of the tie line gives the proportion of
the alpha phase (the phase on the left).

Remember: you use the length of the line which is furthest from the phase in
which you are interested.

Distances along the tie line can be found very simply by using a ruler on
an accurate phase diagram or, more correctly, by using data from the
composition axis (the x-axis).For example, on the diagram shown, the
percentage of alpha present can be calculated from the three pieces of
composition data given:

Fraction of alpha = (34.5 - 23.7) / (34.5 - 5.2) = 0.3686

Thus, percentage of alpha = 0.3686 x 100 = 36.86%

and, as the alpha and the liquid make up 100% of the alloy's
composition:

Percentage of liquid = 100 - 36.86 = 63.14%
Magmatic Processes
Some useful terms:
Primary magma - magma originating in (mantle) source
directly from melting.
Primitive magma - magma that undergo minimal
differentiation.
Parental magma - least differentiated magma in a series
leading to evolved rocks.

Magmatic Differentiation:
the process whereby, magma originally homogeneous
splits up into contrasted parts, which may form separate
bodies of rocks or may remain within the boundaries of
single unitary mass.

It is usually favored by two factors:
a.Rate of cooling.
b.Settling of early crystallized heavy minerals.
Fractional Crystallization
Separation of crystals from liquid
Gravitative settling or flotation play a significant role

ASSIMILATION
It is the method of creating different daughter magmas from a parent is by
having the latter react with its wall rocks
assimilation is accompanied by crystallization, it is likely that both fractional
crystallization and assimilation will take place simultaneously.

Combined Process (AFC = Assimilation +
Fractional Crystallization)

HOT (1200C)
basaltic magma
Blocks of continental
crust fall into basaltic
magma and dissolve.
basaltic magma +
assimilated blocks =
andesitic magma
Heat transfer from
hot, basaltic magma
melts wall rock
magma composition progressively
changes as crystal are physically
removed from the magma
Incongruent Melting
Incongruent melting occurs when a substance does not melt
uniformly and decomposes into another substance. For example,
potassium feldspar (KAlSi3O8) decomposes to leucite (KAlSi2O6)
when it melts. The decomposition is not complete, however. Most of
the feldspar does melt, a portion of it decomposes to leucite and
some quartz (SiO2) is left over, since the chemical formulas of
potassium feldspar and leucite differ by SiO2. Another mineral that
melts incongruently is enstatite (MgSiO3), which decomposes to
forsterite (Mg2SiO4). Enstatite does melt congruently between
pressures of 2.5 and 5.5 kilobars.
Congruent Melting
Congruent melting occurs during melting of a
compound when the composition of the liquid that
forms is the same as the composition of the solid. It
can be contrasted with incongruent melting. This
generally happens in two- component systems.
Congruent melting VS Incongruent melting
In congruent melting of rocks, the
minerals simply melt and join the liquid. In
incongruent melting, a new solid minerals
precipitates from the melt.

For example of a gneiss containing quartz, biotite and
sillimanite is melted, then the result is a liquid plus the
new solid mineral cordierite (magnesium iron aluminum
cyclosilicate)