PHASE RULE

Introduction

Minerals are the monitors of the physical and chemical conditions under
which they formed. The occurrences of minerals, their parageneses (stable
associations), types of reactions, and compositional variation (e.g. zoned
minerals) all provide important information about geologic history and
processes. Of particular importance to geologists are:

Estimates of pressure and temperature (geothermobarometry)

Estimates of other physico-chemical conditions such as acidity (pH) and
oxidation state (eH)
Partial pressures of gases (e.g. fugacities of H2O, CO2 , etc.)
Partitioning of major and trace elements between phases (e.g. minerals,
melts and/or fluids) to characterize and quantify petrogenetic processes; and
Use of minerals in geochronology and thermochronology

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Gibbs' Phase Rule provides the theoretical foundation, based in

thermodynamics, for characterizing the chemical state of a (geologic)
system, and predicting the equilibrium relations of the phases (minerals,
melts, liquids, vapors) present as a function of physical conditions such as
pressure and temperature.

Gibbs' Phase Rule also allows us to construct phase diagrams to represent

and interpret phase equilibria in heterogeneous geologic systems. In the
simplest understanding of phase diagrams, stable phase (mineral)
assemblages are represented as "fields" (see colored areas on the figure to
the right) in "P-T space", and the boundaries between stable phase
assemblages are defined by lines (or curves) that represent reactions
between the phase assemblages.

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Why We Need Phase Diagrams!

•Several phases crystallize sequentially over T and P range

•Minerals that are solid solutions change composition during crystallization sequence

•Melt (magma) composition clearly also changes during this time

•Minerals that form and their sequence of crystallization depend on composition

of magma, T, P etc

•P and presence/nature of volatiles can affect the temperature range of crystallization

•All of the above applies in reverse for melting of a rock (and generation of magma)

•Remember that a rock can form by cooling (quenching) at any time during
crystallization and we need to understand which crystals are present, in what
proportions, and their compositions

•Clearly the above is complicated…hence PHASE DIAGRAMS!!!

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Phase rule predicts quantitatively existing between different phase of a

heterogeneous systems.
Definitions:
Phase
an homogeneous physically distinct and mechanically separable
portion of system. which is separated from other such parts of the
system by definite boundary surfaces.
i) at freezing point , water consists of three phases
ii) a gaseous mixture, being thoroughly misible in all portions, will
constitute one phase only. Thus, a mixture of N2 and H2 forms one
phase only.
iii) if two liquids are immiscible, they will form two separate phases.

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 If 2 solutions are miscible they will form one liquid phase only.
 A solution of a substance in a solvent consists of one phase only.
eg: glucose solution
 Each solid makes up a separate phase.
eg: S can exist together, but these are all separate phases.
 A heterogeneous mixture like
CaCO3(s) ↔ CaO(s) + CO2
consists three phases
Fe(s) + H2O(g) ↔ FeO + H2
Consists three phases.
 A homogenous solid solution of a salt constitutes a single phase.
eg:FeSO4.(NH4)2SO4.6H2O solution constitutes a single phase
although it consists of FeSO4.(NH4)2SO4 &H2O

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COMPONENT:

The smallest number of independent variable constitutes, taking part in the

state of equilibrium , by means of which the composition of each phase can be
expressed in the form of chemical equation.
i) in water system the chemical composition of all the three phases in H2O.
Hence it is one component system.
ii) the sulphur system consists of four phases, rhombic, monoclinic, liquid and
vapour.
the chemical composition of all phases is S. hence, it is one component system.
iii) a system of saturated solution of NaCl consists of solid salt, salt solution and
water vapour.
the chemical composition of all the three phases can be expressed in terms of
NaCl & H2O. Hence it is a 2 component system.

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In the thermal decomposition of CaCO3 is 2 component system.

In the dissociation reaction
CuSO4.5H2O(s) ↔ CuSO4.3H2O(s) + 3H2O(g)

Fe(s) + H2O ) ↔ FeO(s) + H2(g)

it is a three component system.

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Degree of freedom:

The minimum number of independently variable factors, such as T,P &

composition of the phases, which must be arbitrarily specified in order
to represent prefectly the condition of a system.
In case of water system.
if all the 3 phases are present in equilibrium, then no condition need to
be specified, as the 3 phases can be equilibrium only at particular T and
P.
the system is, therefore zero variant or non-variant or invariant or has no
degree of freedom. if the condition is altered, three phases will not
remain in equilibrium and one of the phase disappears.

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 water(l) ) ↔ vapour(g)
we must state either the T or P to define it completely, hence degree
of freedom is one or system is univariant.

 For a system consisting water vapour phase only. We must state

the values of both T & P in order to describe the system completely.
Hence, the system is bivariant.

 NaCl(s) ) ↔ NaCl-water(aq) ) ↔ water vapour(g)

we must state either the Tor P. because the saturation solubility is

fixed at a particular T or P.

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PHASE RULE

The phase rule is a generalisation given by willard gibbs (1874). It

may be stated as
Provided the equilibrium between any number of phases is not
influenced by gravity or electrical or magnetic forces or by surface
action and only by temperature, pressure and concentraton, then the
number of degrees of freedom (f) of the system is related to the
number of components (c) and of phases (p)
BY THE PHASE RULE EQUATION
P+F=C+2

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Water system

The water system consists of three phases

ice(s) ↔ water(l) ↔ water vapour(g)
C=1
F=C-P+2
=1-P+2
F =3-P
i.e.the degree of freedom depends on the number of
phases present at equilibrium
i) if P=1; F=2 (bivariant system)
ii) if P=2; F=1 (uni variant system)
iii) if P=3; F=0 (in variant system)

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i) Areas
AOB – vapour P=1
AOC – liquid F=2
BOC – ice
Because to locate any point in an area, T aswell as P co-ordinates need to
be known.
ii) Boundry lines
OA, OB, OC P=2
F=1
in order to locate any point on a particular line, either T or P co-ordinate
should be known.
because for fixed value of one co-ordinate, the second is automatically
fixed.

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iii) Triple point

the three curves OA,OB,OC meet at O.
at which solid, liquid and vapour are simultaneously at equilibrium. this
point at 273.16k (0.0098oc) and 4.579mm is called a triple point.
P=3
F=0
i.e.neither P nor T can be altered, even slightly, with act causing the
disappearance of the of the phases.
iv) Metastable curve:
as water doesnot always freeze at0oc, soif the vessel containing water
and vapour is perfectly clean and free from dust, it is possible to super cool
water several degrees below its freezing point O. the dotted curve OA’, a
continuation of vaporization curve AO.

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 Represents the vapour pressure curve of super cooled water.

 This curve represents a metastable system.on slight disturbance the
super cooled water at once changes to solid ice.
 It may be noted that metastable vapour pressure of supercooled water
is higher than the vapour pressure of ice.

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Phase rule for two component alloy systems
 In a two component system when P=1
F=2-1+2
F=3
 since the maximum number of degrees of freedom in a 2 component
system is 3.
 a solid-liquid equilibrium of an alloy has practically no gas phase and the
effect of pressure is small on this type of equilibrium.
 Thus keeping the pressure constant of a system in which vapour is not
considered is known condensed system.
 It will reduce the degrees of freedom of the system by one and for such a
system. The phase rule becomes
F=C-P+1
 this is known as the reduced or condensed phase rule. Having 2 variables T
&concentration ( composition)
 Solid-liquid equilibria are represented on T & composition.
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LEAD-SILVER SYSTEM

 It is 2 component system with 4 possible phase solid Ag, solid

Pb, solution Ag+Pb and vapour.
 At constant atmospheric pressure as the gaseous phase is
practically and one variable pressure is neglected.
F=3-P is applicable.

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i) Curve AO: (freezing point curve of Ag)

 Shows the effect of freezing point of Ag on addition of lead in small
quantities.
 The curve starts from A (961oc).the melting point of Ag, where pure Ag co-
exists as solid and iquid.
 The curve indicates that the melting point of Ag falls gradually on adding Pb,
along AO, till the lowest point O (303oc) is reached.
 At O, no more lead can go in solution and consequently, melting point of Ag
doesnot fall any further and if any lead is added, it separates as the solid
phase.
 F=3-P, F=1,i.e.the system is univariant
 The point O (303oc) corresponds to a fixed composition of (2.6% Ag and
97.4% Pb) is known as eutectic composition.

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ii)Curve BO (freezing point curve of Pb)

 Represents the effect on freezing point of Pb on gradual addition of small
amounts of Ag to it.point B is the meeting point of pure Pb(327oc)
 Along BO the melting point gradually falls on the addition of Ag, till lowest point
O is reached.
 Where the solution gets saturated with respect to Ag and the melting point of Pb
does not fall any more.
iii) Point O (eutectic point)
 The 2 curves AO and BO meet at O
 The point O reprents (303oc) a fixed composition (Ag=2.6%,Pb=97.4%) and is
called eutectic composition.
 No mixture of lead & silver has a melting point lower than the eutectic
temperature.
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 Below the temperature line of eutectic temperature, we have two regions in the
diagram
 The region marked eutectic + solid Ag, in which crystalline silver and solid eutectic
are stable.
 The region marked eutectic + solid Pb, in which crystaline Pb and solid eutectic are
stable.
iv) Area AOB:
 Represents solution of Ag + Pb
 If a sample of solution Pb containing less than 2.6% Ag is taken, say P.
 On allowing the mass to cool, the T gradually falls without any change in
composition, till point p’ is reached on the curve BO.
 On lowering the T, lead begins to separate out and the composition varies along p’o,
till point O is reached.

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Fe-C phase diagram

The Fe-C phase diagram shows which phases are to be expected at metastable
equilibrium for different combinations of carbon content and temperature. The
metastable Fe-C phase diagram was calculated with Thermo-Calc, coupled with
PBIN thermodynamic database.

At the low-carbon end of the metastable Fe-C phase diagram, we distinguish

ferrite (alpha-iron), which can at most dissolve 0.028 wt. % C at 738 °C, and
austenite (gamma-iron), which can dissolve 2.08 wt. % C at 1154 °C. The much
larger phase field of gamma-iron (austenite) compared with that of alpha-iron
(ferrite) indicates clearly the considerably grater solubility of carbon in gamma-
iron (austenite), the maximum value being 2.08 wt. % at 1154 °C. The
hardening of carbon steels, as well as many alloy steels, is based on this
difference in the solubility of carbon in alpha-iron (ferrite) and gamma-iron
(austenite).

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At the carbon-rich side of the metastable Fe-C phase diagram we find cementite
(Fe3C). Of less interest, except for highly alloyed steels, is the delta-ferrite at
the highest temperatures.

The vast majority of steels rely on just two allotropes of iron: (1) alpha-iron,
which is body-centered cubic (BCC) ferrite, and (2) gamma-iron, which is
face-centered cubic (FCC) austenite. At ambient pressure, BCC ferrite is stable
from all temperatures up to 912 °C (the A3 point), when it transforms into FCC
austenite. It reverts to ferrite at 1394 °C (the A4 point). This high-temperature
ferrite is labeled delta-iron, even though its crystal structure is identical to that of
alpha-ferrite. The delta-ferrite remains stable until it melts at 1538 °C.

Regions with mixtures of two phases (such as ferrite + cementite, austenite +

cementite, and ferrite + austenite) are found between the single-phase fields. At
the highest temperatures, the liquid phase field can be found, and below this are
the two-phase fields (liquid + austenite, liquid + cementite, and liquid + delta-
ferrite). In heat treating of steels, the liquid phase is always avoided.

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The steel portion of the Fe-C phase diagram covers the range between 0 and
2.08 wt. % C. The cast iron portion of the Fe-C phase diagram covers the
range between 2.08 and 6.67 wt. % C.

The steel portion of the metastable Fe-C phase diagram can be subdivided
into three regions: hypoeutectoid (0 < wt. % C < 0.68 wt. %), eutectoid (C =
0.68 wt. %), and hypereutectoid (0.68 < wt. % C < 2.08 wt. %).

A very important phase change in the metastable Fe-C phase diagram occurs
at 0.68 wt. % C. The transformation is eutectoid, and its product is called
pearlite (ferrite + cementite):

gamma-iron (austenite) —> alpha-iron (ferrite) + Fe3C (cementite).

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Some important boundaries at single-phase fields have been given special names. These
include:

• A1 — The so-called eutectoid temperature, which is the minimum temperature for

austenite.
• A3 — The lower-temperature boundary of the austenite region at low carbon contents;
i.e., the gamma / gamma + ferrite boundary.
• Acm — The counterpart boundary for high-carbon contents; i.e., the gamma / gamma +
Fe3C boundary.

Sometimes the letters c, e, or r are included:

• Accm — In hypereutectoid steel, the temperature at which the solution of cementite in

austenite is completed during heating.
• Ac1 — The temperature at which austenite begins to form during heating, with the c
being derived from the French chauffant.
• Ac3 — The temperature at which transformation of ferrite to austenite is completed
during heating.
• Aecm, Ae1, Ae3 — The temperatures of phase changes at equilibrium.
• Arcm — In hypereutectoid steel, the temperature at which precipitation of cementite
starts during cooling, with the r being derived from the French refroidissant.
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• Ar1 — The temperature at which transformation of austenite to ferrite or to

ferrite plus cementite is completed during cooling.
• Ar3 — The temperature at which austenite begins to transform to ferrite during
cooling.
• Ar4 — The temperature at which delta-ferrite transforms to austenite during
cooling.

If alloying elements are added to an iron-carbon alloy (steel), the position of the
A1, A3, and Acm boundaries, as well as the eutectoid composition, are changed.
In general, the austenite-stabilizing elements (e.g., nickel, manganese,
nitrogen, copper, etc) decrease the A1 temperature, whereas the ferrite-
stabilizing elements (e.g., chromium, silicon, aluminum, titanium, vanadium,
niobium, molybdenum, tungsten, etc) increase the A1 temperature.

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The carbon content at which the minimum austenite temperature is attained

is called the eutectoid carbon content (0.68 wt. % C in case of the
metastable Fe-C phase diagram). The ferrite-cementite phase mixture of
this composition formed during slow cooling has a characteristic
appearance and is called pearlite and can be treated as a microstructural
entity or microconstituent. It is an aggregate of alternating ferrite and
cementite lamellae that coarsens (or "spheroidizes") into cementite
particles dispersed within a ferrite matrix after extended holding at a
temperature close to A1.

Finally, we have the martensite start temperature, Ms, and the

martensite finish temperature, Mf:

• Ms — The highest temperature at which transformation of austenite to

martensite starts during rapid cooling.
• Mf — The temperature at which martensite formation finishes during rapid
cooling.

DR. E. LAXMINARAYANA