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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

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:

New York, 1997; pp 141143.

6. Zhao, M.; Wang, Z.; Xiao, L. J. Chem. Educ. 1992, 69, 539542.

7. Feynman, R. Statistical Mechanics: A Set of Lectures; Benjamin:

Reading, MA, 1972; p 1.

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