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Research: Science and Education

JChemEd.chem.wisc.edu Vol. 76 No. 11 November 1999 Journal of Chemical Education 1567


The Gibbs phase rule appears to be extremely simple;
indeed, that isthe source of itselegance: F = C P + 2, where C
is the number of components in a chemical system, P is the
number of phases, and F isthe number of degreesof freedom.
Students of physical chemistry usually have little difficulty
counting the number of phasesin the systemsthey encounter.
A phase isdefined asa state of matter that isuniform through-
out, both in chemical composition and in physical properties.
In determining P, students need only realize that there can
be at most one gasphase, but that there can be more than one
solid phase (e.g., a mixture of zinc turnings and iron filings)
and more than one liquid phase (e.g., a mixture of toluene
and water). However, counting components, although a seem-
ingly trivial task, presents unexpected difficulties, especially
in multiphase systems involving chemical reactions.
In this paper, I discuss the problem of counting compo-
nents in multiphase systems involving chemical reactions. No
new principles are required to solve this problem (1, 2). Its
solution simply requires careful attention to the nature of the
constraints that provide relationships among the species con-
stituting the system. As a consequence of this more detailed
examination, we find that the number of componentsdepends
on the phase structure of the system. In some situations, the
number of components can be affected by the temperature
and pressure of the system. In other situations, a system
containing arbitrary amounts of two different chemical
compounds should be regarded as a one-component system.
Counting Components
C, the number of components, isdefined asthe minimum
number of independent chemical species necessary to define
the composition of all of the phases present in the system
(3). The number of independent speciesisequal to the number
of constituents(the total number of chemical speciesused to
characterize the system) minus the number of constraints on
the concentration of these constituents (4). The constraints
include both equationsinvolving equilibrium constants, which
provide relationshipsamong the chemical speciesat equilibrium,
and equations describing stoichiometric relationships among
the speciesirrespective of whether the system isin equilibrium.
In applying these principles, it is important to remember that
the phase rule describes the intensive state of the system; the
relative amounts of the various phases cannot be determined
(5). In other words, the phase rule says nothing about the
total number of moles in each phase.
The number and even the choice of constituents in a
system isto some extent arbitrary, depending on the problem
at hand or on personal choice. However, irrespective of the
choice of constituents, the number of components is an in-
variant. For example, in a problem involving the phase equi-
librium of a system containing liquid water, ice, and water
vapor, there is just one constituent, H
2
O, and thus one com-
ponent. However, in a problem involving the dissociation of
water, there are three constituents, namely, H
2
O, H
3
O
+
, and
OH

. There is still only one component because there are


two constraining relationshipsamong these three constituents:
K
w
= [H
3
O
+
][OH

] and [H
3
O
+
] = [OH

] (1)
In determining the number of components from the
constituents, the textbooksfocuson determining the number
of independent chemical reactions without regard to phase.
In fact, an article appearing in this Journal discussing the
Brinkley method for determining the number of components
notes that this method is best suited for one-phase systems
such as high-temperature mixtures in the gaseous phase or
for complicated aqueous solutions of electrolytes (6). The
Brinkley method uses linear algebra to analyze the matrix
whose (i,j)th entry is the number of atoms of element E
j
in
the chemical species S
i
. The authors do apply the Brinkley
method to a two-phase system, namely a solution of electro-
lytes involving an insoluble species (AlCl
3
dissolved in water
with the formation of Al(OH)
3
(s)). However, they do not
dwell on the effect of the second phase in determining the
number of components.
The compli cati ons i n determi ni ng the number of
components in multiphase systems can be clearly seen in a
comparison between two seemingly similar equilibria
NH
4
Cl(s) = NH
3
(g) + HCl(g) (2)
and
CaCO
3
(s) = CaO(s) + CO
2
(g) (3)
Let us first treat the case in which, for each equilibrium,
we introduce arbitrary amounts of the three constituents into
a closed container. In the first equation, there are three con-
stituents, but only two components. A constraint on the con-
stituents is provided by the equilibrium constant expression,
which relatesthe partial pressuresof the two gaseousproducts:
K1 = p
NH
3

p
HCl
(4)
where K1 is the equilibrium constant and p
X
denotes the par-
tial pressure of the species X.
The same reasoning applies to the second equation. The
equilibrium expression is
K2 = p
CO
2
(5)
and again, C = 2.
Now consider the case in which, for each equilibrium, we
introduce the reactant only into the container. For the first
equilibrium, there isan additional stoichiometric relationship,
n(NH
3
) =n(HCl), where the notation n(X) meansthe number
of moles of X. We conclude that the number of components
is reduced to one. This reasoning is correct. C=1, P =2 (one
gaseous and one solid phase), and so, and the number of
degrees of freedom is F = 1. This degree of freedom can be
taken to be the temperature. Specifying the temperature
determines K1, which together with the stoichiometric rela-
tionship determines p
NH
3
and p
HCl
.
The Gibbs Phase Rule Revisited:
Interrelationships between Components and Phases
J oseph S. Alper
Department of Chemistry, University of MassachusettsBoston, Boston, MA 02125; j.alper@umb.edu
Research: Science and Education
1568 Journal of Chemical Education Vol. 76 No. 11 November 1999 JChemEd.chem.wisc.edu
If we apply the same reasoning to the second equilibrium,
we note that n(CaO) = n(CO
2
) and again conclude that C=1.
However, this reasoning is false. If we apply the phase rule
to the decomposition of CaCO
3
, we have C = 1, P = 3 (two
solid phases and one gaseous phase), and thus F = 0. This
result cannot be correct. There is certainly more than one
temperature at which CO
2
(g) exists in equilibrium with
CaCO
3
(s) and CaO(s).
Clearly, the source of the problem lies in the additional
solid phase in the second equilibrium. After the equilibrium
has been established, we can add arbitrary amounts of CaO
without affecting the equilibrium. Thus C = 2. Note that in
the equilibrium expression K2, CaO(s) doesnot appear. Since
it is in a phase by itself, the composition (concentration) of
the solid CaO phase is independent of the amount of that
phase. For the usual choice of standard states, this con-
centration can be set equal to 1. Thus the existence of the
stoichiometric relationship n(CaO) = n(CO
2
), relating the
number of moles of the two species, is irrelevant in deter-
mining the number of components. In the NH
4
Cl example,
on the other hand, addition of either HCl or NH
3
drives
the equilibrium to the left. Both HCl and NH
3
appear in
the equilibrium expression K1, and the stoichiometric re-
lationship between the two species does affect the number
of components.
The general principle becomesclear from these examples.
The only stoichiometric relationships that reduce the num-
ber of components are those in which every species in the
relationship appears in an equation involving an equilibrium
constant. Stoichiometric relationships involving at least one
species in a solid phase or at least one pure liquid species in
a phase by itself are irrelevant in determining the number of
components.
This approach to the determination of the number of
components clarifies the example mentioned above involving
an aqueous solution of AlCl
3
. Let us take as constituents the
species H
2
O, Al
3+
, Cl

, H
+
, OH

, and Al(OH)
3
(s). There are
two relevant equilibrium constants: K
w
and K
sp
, the solubility
product constant for Al(OH)
3
. There is only one stoichio-
metric constraint involving species all of which appear in the
equilibrium equations involving K
w
and K
sp
. This constraint
is the charge balance equation
3[Al
3+
] + [H
+
] = [Cl

] + [OH

] (6)
which comprises all the charged species in solution. Thus the
number of components is 3 (6 constituents, 2 equilibrium
constants, 1 stoichiometric constraint). These components
can be chosen to be H
2
O, AlCl
3
, and Al(OH)
3
. This result
can also be obtained by noting that the component Al(OH)
3
is required to specify the composition of the solid phase.
Suppose now, contrary to fact, that Al(OH)
3
were soluble
and appeared in the aqueousphase. In thiscase, the equation
involving K
sp
would be replaced by
K = [Al
3+
][OH

] / [Al(OH)
3
] (7)
The species Al(OH)
3
now appears in an equation involving
an equilibrium constant, so that a second stoichiometric con-
straint becomes relevant. This constraint is the mass balance
equation
3[Al(OH)
3
] + 3[Al
3+
] = [Cl

] (8)
reflecting the fact that no matter what aqueous species form,
the ratio of the total (analytical) concentration of Al to that
of Cl must remain 1:3. Thus, assuming Al(OH)
3
is soluble,
there would be just two components, H
2
O and AlCl
3
.
C a s a Function of Tempera ture a nd Pressure
It is obvious that the number of phases present in a sys-
tem depends on the temperature T and pressure p. However,
it is not often appreciated that the number of components is
not an invariant of a system, but that it too is a function of p
and T. As a first example, let us return to the decomposition
of NH
4
Cl. At a pressure of 1 atm and between temperatures
191 and 239 K, NH
3
exists in the liquid phase while HCl
remains a gas. Now only HCl appears in the equilibrium
equation because NH
3
is a pure liquid in a phase by itself.
Consequently, there are no longer any stoichiometric constraints
so that the number of componentsisincreased from 1 to 2. It
seemsstrange that changing the temperature (and by extension,
the pressure) of a system can result in a change in the number
of components as well as a change in the number of phases.
Another situation in which the number of components
can vary depending upon the temperature and pressure occurs
under conditions of metastable equilibrium. An arbitrary
mixture of hydrogen, oxygen, and water vapor at equilibrium
has two components because of the equilibrium constant
relating the three species. I n this case P = 1 and there are
three degrees of freedom: for example, p, T, and the mole
fraction of one of the three constituents.
A mixture of these three gases might also be prepared
by introducing arbitrary amounts of each of the gases into a
container being careful to avoid an explosion. The rate of
reaction is so slow at normal temperatures and pressures that
we can consider the three unreacted gasesto be in equilibrium.
In Richard Feynmans words, a system is in equilibrium if
all the fast thingshave happened and all the slow things not
(7). Under these conditions, C = 3 (there is no equilibrium
constant expression) and there are four degrees of freedom:
p, T, and the mole fractions of two of the three gases.
Distinguishing Components from Pha ses
In most cases, that is, exercises in physical chemistry
texts, there is never any question about whether two species
represent two components or should be considered to be two
phases of the same component. Liquid water and ice are two
phases of the same component. Similarly, C(graphite) and
C(diamond) are also regarded as two phases of the same
component, namely carbon. But are things always so simple?
Under ordinary conditions, C(gr) and C(d) are not in
chemical equilibrium; C(gr) is the more stable form. How-
ever, as we know from ordinary experience, the two forms of
carbon are in metastable equilibrium and can exist indepen-
dently of each other. For all practical purposes, the graphite
diamond system can be regarded as being in equilibrium and
subject to the phase rule, just asisthe case for the hydrogen
oxygenwater vapor system discussed above. Consequently,
under these conditions for the graphitecarbon system, C=2.
It is clear that P = 2. Applying the phase rule, we find F = 2.
The two degrees of freedom are pand T. (Each of the two
solid phases consists of only one species, so the compositions
of both are determined.)
Research: Science and Education
JChemEd.chem.wisc.edu Vol. 76 No. 11 November 1999 Journal of Chemical Education 1569
If however, C(gr) and C(d) are at true chemical equilib-
rium, the chemical potentialsof the two speciesbecome equal.
As a result of this constraint, C = 1. Since P remains equal
to two, there is just one degree of freedom, por T. From
the constraint on the chemical potentials, we can derive the
Clausius equation
dp/dT =
trs
S/
trs
V (9)
where
trs
S and
trs
V are the changesin entropy and volume
across the phase boundary, which provides the functional
relationship between pand T.
In vi ew of thi s di scussi on, consi der a hypotheti cal
isomerization reaction, A = B, that has reached equilibrium.
(We assume that the initial amount of each species is arbi-
trary.) I f one or both of the two isomers are gases, C = 1
because there are two constituent species, one equilibrium
expression, but no stoichiometric relation between A and B.
In the case of one gaseous constituent P = 2, and so F = 1.
If both constituents are gases, P = 1 and F = 2, the mole
fraction of A in the gasphase providing the additional degree
of freedom.
If both A and B are solids, the system istotally analogous
to the graphitediamond example. If the rate of interconver-
sion of the two solids is very slow, A and B are in metastable
equilibrium, and we can take C = 2. There are two different
compoundsA and B with no equilibrium constant expression
relating them. However, there may be some regions of the
pT plane in which pand T take on values for which the
isomerization proceedsand the reaction reachesequilibrium. For
these values of pand T, A and B are in chemical equilibrium.
However, unlike a typical chemical reaction involving gasesor
solutions, there is no equilibrium constant for this reaction
relating the concentrations of A and B. Each of the chemical
speciesA and B isin a phase by itself so that the mole fraction
(or concentration) of each speciesisunity. Even at equilibrium,
the ratio of the number of moles of A and B is arbitrary.
Although there isno equilibrium constant, we can analyze
this equilibrium. Instead of treating the system consisting of
A(s) and B(s) as a two-component system, we treat it as a
one-component system with two phasesthat are in equilibrium.
The reduction in the number of components from 2 to 1
resultsfrom the fact that at equilibrium, the chemical poten-
tials of the two species are equal, just as is the case in the
graphitediamond example. Since C=1 and P =2, the phase
rule tellsusthat F = 1. Consequently, there must be a relation-
ship between pand T. Thisrelationship isgiven by a Clausius
equation which isderived by equating the chemical potentials
of A and B. Starting from d
A
(

p,T ) = d
B
(

p,T ) we obtain
the Clausius-like relation
dp/dT = S/V (10)
where Sand V are the changes in entropy and volume
upon isomerization.
But is it legitimate to call a system containing A(s) and
B(s) a one-component system?In the derivation of the usual
Clausius equation, as in the determination of the number of
constraints in the derivation of the phase rule itself, we equate
chemical potentials of the samesubstance in two different
phases. I have purposely introduced the new word substance
to leave open the question of how the relative similarity
between graphite and diamond compares with that between
the two isomersA and B. Graphite and diamond differ in the
arrangement of their carbon atoms; in graphite the carbon
atoms lie in sheets, in diamond they form a tetrahedral
structure. Supposing for specificity that the two isomers are
hydrocarbons, then the isomersdiffer only in the arrangement
of their carbon and hydrogen atoms. Thermodynamics is
totally independent of the details or even the existence of the
molecular structure. Consequently, if chemical equilibrium
can be established between any two isomers (they need not
be hydrocarbons), these two species are thermodynamically
just as similar to each other as are graphite and diamond. If
the latter pair can be considered to be a one-component
system, so can the former.
Thisisomerization example showsthat there are surprising
subtleties associated with the application of the Gibbs phase
rule. For certain chemical equilibria, such as one involving
the solid phases of two isomers, a seemingly two-component
system should be regarded as a one-component system. More
generally, in determining the number of components, a
thorough understanding of the phase structure of the system
is critical. C is not independent of P.
Acknow ledgments
I would like to thank R. I. Gelb for hiscritical reading of
the manuscript and for several helpful discussions. I would also
like to thank the reviewersfor several valuable suggestions.
Litera ture Cited
1. Denbigh, K. ThePrinciplesof Chemical Equilibrium, 3rd ed.; Cam-
bridge University Press: London, 1971.
2. Findlay, A.; Campbell, A. N.; Smith, N. O. ThePhaseRuleand
ItsApplications, 9th ed.; Dover: New York, 1951.
3. Atkins, P. Physical Chemistry, 6th ed.; Freeman: New York, 1998;
pp 192193.
4. Noggle, J. H. Physical Chemistry, 3rd ed.; Harper Collins: New
York, 1996; pp 332333.
5. Alberty, R. A.; Silbey, R. J. Physical Chemistry, 2nd ed.; Wiley:
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