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David Mogk, Montana State University


 
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:

O| stimates of pressure and temperature (geothermobarometry)

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

Gibbs' Yhase 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' Yhase 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 "Y-T space", and the boundaries between stable
phase assemblages are defined by lines (or curves) that represent reactions between the phase
assemblages. The reaction curves actually represent the condition (or the locus of points in Y-T
space) where ǻGrxn =0; for more information on this point see Gibbs Free nergy. A solid
understanding of Gibbs' Yhase Rule is required to successfully master the applications of
heterogeneous phase equilibria presented in this module.
2   
Gibbs Yhase Rule is expressed by the simple formulation:

, where

Y is the number of phases in the system

A phase is any physically separable material in the system. very unique mineral is a
phase (including polymorphs); igneous melts, liquids (aqueous solutions), and vapor are
also considered unique phases. It is possible to have two or more phases in the same state
of matter (e.g. solid mineral assemblages, immiscible silicate and sulfide melts,
immiscible liquids such as water and hydrocarbons, etc.) Yhases may either be pure
compounds or mixtures such as solid or aqueous solutions--but they must "behave" as a
coherent substance with fixed chemical and physical properties.
C is the ë
ëë number of chemical components required to constitute all the phases in the
system
For historical reasons, geologists normally define components in terms of the simple
oxides (e.g. SiO2, Al2O3, CaO, etc.). If two possible components always occur in the
same proportions in multiple phases in a system, these can be combined into a single
component (remember, we are always trying to define the ë
ëë number of
components required to make all the phases in the system). Consider the reaction:


          
ë           
   

Normally we would pick the 4 components: CaO, MgO, SiO2, and CO2 based on the
simple oxides. However, because Ca and Mg are in a 1:1 ratio in both dolomite and
diopside (and not present in quartz or carbon dioxide), we can consider this a ternary
system with components: CaMgO2, SiO2, and CO2

In some geologic systems it is convenient to define the components in terms of end-

member compositions (e.g. binary systems such as carbonates, CaCO3 - MgCO3; alkali
feldspars, NaAlSi3O8 - KAlSi3O8, etc.).

In some cases, a given mineral assemblage may be represented by a sub-set of the whole
system if fewer components are needed to define the compositions of the observed
mineral assemblage--this is known as a 
 system. A good example of this can
be seen on a ternary (3 component) chemographic projection if the phases of interest plot
in a co-linear fashion (i.e. requiring only two components to define the phase
compositions in what is otherwise a three component system).

A more complete discussion of components can be found in the section on Ylotting

Mineral Compositions and Chemographic Yrojections.
F is the number of degrees of freedom in the system (also referred to as the variance of the
system).
 For geologic applications, this generally refers to the number of variables (e.g. pressure
and temperature) that can be independently changed without altering the state of the
system (i.e. the number of phases and their compositions are constant). Three common
types of equilibria are possible:

O| Invariant equilibria, in which neither Y or T can be changed; on a phase diagram,

this is represented as a singular
 


O| Univariant equilibria, in which either Y or T can be changed independently, but to
maintain the state of the system, there must be a corresponding change in the
other variable; on a phase diagram this is referred to as a 
 


and

O| Divariant equilibria, in which both Y and T are free to change independently

without changing the state of the system (but bounded by the conditions defined
by the univariant equilibria).

The integer in the Gibbs Yhase Rule

is related to the number of

  parameters (i.e. those that are independent of mass;
such as pressure and temperature) that are being considered. Note that many phase
diagrams consider only one intensive parameter (e.g. T-Xfluid, where T is intensive, and
the mole fraction of fluid is related to the amount of mass of the fluid components); in
this case, the Gibbs Yhase Rule would be: Y + F = C + 1.
It is generally the case that as the number of components increase, the variance of the system
must also increase. Conversely, as the number of phases increase in the system, the variance of
the system must correspondingly decrease. A corollary to Gibbs' Yhase Rule is c 
   
: f   
  
 !   ë  f  " 
 #$ %
ë f
%   %
  !  %
ë f ë

& Geologic systems are really rather
simple! This means that we have a reasonable expectation that we can successfully interpret the
conditions of formation of rocks in their natural settings, and to model their behavior using the
thermodynamic databases and programs presented at the end of this module.


 !"#
†et's consider the simple 1 component system for H2O:
Yhase diagram for the one component system H2O. This diagram is not to scale; a scale version
looks like the thumbnail in the white box.

O| The system is entirely composed of H2O, so there is only one component present.
O| The phases present represent three states of matter: liquid (water), solid (ice), and vapor
(steam). All have distinct physical properties (e.g. density, structure--or lack of, etc.) and
chemical properties (e.g. ǻGformation, molar volume etc.) so they must be considered
distinct phases.
O| Note that there is only one point on this diagram where all three phases coexist in
equilibrium--this "triple point" is also referred to as an
 

; because Y and T
are uniquely specified, there are zero degrees of freedom.
O| ach of the curves represents a chemical reaction that describes a phase transformation:
solid to liquid (melt/crystallization), liquid to vapor (boiling/condensation), solid to vapor
(sublimation/deposition). There are three 
 
 around the invariant point; it
is always the case that for a C-component system, there will always be C+2 univariant
curves radiating around an invariant point. This relationship is further explained in the
unit on the Method of Schreinemakers. There is only one degree of freedom along each
of the univariant curves: you can independently change either T or Y, but to maintain two
coexisting phases along the curve the second variable must change by a corresponding
fixed amount.
O| There are three distinct areas where only ice, liquid, or vapor exit. These are   

fields. T and Y are both free to change within these fields and you will still have only one
phase (a bit hotter or colder, or compressed or expanded, but nonetheless the same
phase).
O| The end of the "boiling curve", separating the liquid to vapor transition, is called the
"critical point". This is a particularly interesting part of the phase diagram because
beyond this region the physico-chemical properties of water and steam converge to the
point where they are identical. Thus, beyond the critical point, we refer to this single
phase as a "supercritical fluid".

Now, let's consider a simple 1 component system that describes the mineral phases in the
aluminosilicate system:
Yhase diagram for the one component system Al2SiO5.

O| The entire system is defined by one component: Al2SiO5 (i.e. all the phases can be
completely made of this one component)
O| There are three solid phases shown in this diagram: the polymorphs of Al2SiO5
andalusite, kyanite and sillimanite.
O| There is only one unique place on this diagram where all three phases can coexist in
equilibrium--the invariant point at 3.8 Kb and 500oC; at this point there are zero degrees
of freedom.
O| There are three univariant reactions on this diagram, each representing the phase
transitions: andalusite = sillimanite, andalusite = kyanite, and kyanite = sillimanite. In
each of these reactions,  % pressure or temperature can be changed independently, but
for the state of the system to remain the same (i.e. two solid phases coexisting in
equilibrium), the other variable must change by a fixed amount to maintain the
assemblage on the univariant curve -- so there is one degree of freedom. In a later section,
we will see that the univariant curves represent the condition where ǻGrxn = 0 (i.e. the
intersection of the "free energy surface" with the Yressure-Temperature plane represented
by the phase diagram).
O| There are three divariant fields in which only a single mineral phase is stable. Within
these fields pressure 
 temperature may be changed independently without changing
the state of the system--thus there are two degrees of freedom in the divariant fields.

These principles extend to the more complicated binary, ternary and multi-component systems
presented in the next section(s) of this module on Yhase Diagrams and Yseudosections.

[
 
There are a number of important assumptions that must be considered when applying Gibbs'
Yhase Rule:
 O| The relationships described by the Gibbs' Yhase Rule apply the concepts of equilibrium
thermodynamics. It is assumed that geologic systems have enough time to naturally
equilibrate. It is also assumed that geologic systems are "closed" systems--that is the
mass of the system remains essentially constant, and the system is free to consume or
liberate energy to do work.
O| For geologic systems, heat and work are considered to be the major contributors to the
system's energetics--that is, "Y-V work" is the dominant source of energy
consumed/liberated by the system. We do not consider the effects of external fields (e.g.
electrical, magnetic, gravitational), and we do not consider surface energy or boundary
effects.
O| No kinetic effects are considered. This may present problems with an equilibrium
thermodynamics approach if metastable phases are present in the system. In natural
settings it is common for a given mineral to exist under physical conditions that exceed
its predicted stability limits. A good example is the persistence of kyanite into the
sillimanite stability field. This particular reaction a) has a very small ǻGrxn (and thus, a
small "driving force" to make the reaction go), and b) the polymorphic reaction is of the
"reconstructive" kind, and requires the breaking and reforming of strong covalent bonds.
The presence of metastable phases may complicate matters in trying to determine the
equilibrium conditions for stable mineral assemblages, but they are essential indicators of
changing physical conditions that allow us to interpret Yressure-Temeperature-time Yaths.
O| In some cases, surface reactions (e.g. sorption, catalysis) may operate in geological
environment and contribute to the overall energetics of the system. Surface energies are
not included in the Gibbs Yhase Rule formulation.
O| Gibbs' Yhase Rule cannot be applied indiscriminately. It is important to obtain the best
possible characterization of the identity, composition and structural state of the phases
present. For example, complex materials such as mixed layer silicates may cause
problems, or minerals that exhibit a range of structural states (e.g. the alkali feldspars).
An overview of analytical techniques that are used to characterize minerals, melts and
fluids can be found at the companion website on Geochemical Instrumentation and
Analysis
O| Recognizing these assumptions and limitations, the Gibbs Yhase Rule still provides a
powerful way to analyze and interpret geological systems. Although geologic systems are
dynamic and often in a state of disequilibrium, the equilibrium approach demonstrates
what the state of the system would be given sufficient time and energy to achieve that
equilibrium. It also provides information on the phase changes or reactions that would be
expected in a system that is thrown out of equilibrium due to changes in physical
conditions. Thus a knowledge of the sequence of possible reactions provides important
information about "pathways" in geologic systems that allow interpretations of tectonic
environments, petrogenetic processes, and the evolution of geologic systems (see
following chapters on Yseudosections, Y-T-t Yaths, and Advanced Modeling Yrograms
(ThermoCalc, TW , YRY†X, M†TS).

2 $ 


It is important to recognize that the simple formulation of Gibbs' Yhase Rule is derivative from
fundamental thermodynamic principles. The Gibbs- Duhem equation establishes the relationship
between the intensive parameters temperature (T) and pressure (Y) and the chemical potential of
all components (ȝi) in the system:
c  % !
  &' (
This means that there are

O| C + 2 independent variables that describe the system: Y, T and one each for the chemical
potential for all components, and
O| Y independent equations (of the Gibbs-Duhem form) that describe the energetics of the
system--one equation for each phase.

In mathematical terms, the variance (F) is determined by the difference between (C+2) variables
and (Y) equations. Thus,

! or as originally written, |