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Thermodynamic

Functions and
Equilibrium

2.1 Energy Functions 11 1

2.2 Fundamental Equations 111

2.3 Total and Specific Properties 117

2.4 Partial Mold Properties 118

2.5 Derivatives with Respect to Mol Fractions 118

2.6 Homogeneous Functions 125

2.7 Variation of Properties with Temperature and


Pressure 125

2.8 Mixing and Excess Functions 127

2.9 The Gibbs-Duthem Equation and Thermodynamic


Consistency 130

2.10 Conditions of Equilibrium 130


2.10.1 Mixtures 131
2.10.2 Phase Equilibria 132
2.10.3 Chemilcal Equilibria 133
2.10.4 Evaluation of Chemical Potentials 133

2.1 1 Problems 134

109
2.2. Fundamental Equations 111

This chapter reviews those aspects of thermodynamics that d U = d Q - d W = T d S - PdV, (2.10)


are especially pertinent to the study of phase and chemical
and of a steady-iflow open system,
equilibria. Mainly this comprises the evaluation of those
properties that are significant in defming equilibrium states dH=dQ-dB",= T d S + VdP. (2.11)
and the evaluation of energy changes accompanyingtransition
Accordingly, the work transfers of reversible processes at
from one equilibrium state to another. It is beyond the scope of
either isothermal or adiabatic conditions may be derived and
this book to derive all the useful equations in detail. For
summarized as:
convenience, basic relations are extended in summary tables
and in Appendix A.
System Type Condition Work Transfer
Closed Adiabatic -dU (2.12)
2.1. ENERGY FUNCTIONS Closed Isothermal -dA (2.13)
Flow Adiabatic -dH (2.14)
Magnitudes of changes in stored energy functions are deter-
Flow Isothermal -dG (2.15)
mined by net heat, work, and mass transfers. The basic
property of this k i d is the intemal energy U, which is related
A certain histcrrical significance attaches to these work
to other prtoperties in the combined statement of the first and
equations, for example the term maximum work for A and the
second laws of thermodynamics:
term free energqf (for work performance) for G , but all the
energy functions have many applications not directly related
to work and heat transfers.
The integral ,and differential forms of H, A, and G are
where pi is the change in internal energy of the system per mol derived from Eqs. 2.5 and 2.6 by substituting H = U PV, +
of substance i transferred at constant entropy and volume. A = U - TS, and G = U 4- PV - TS, with the results
Other equivalents are given later. The internal energy is a
function of the independent variables S, 6.: n 1, nz, . . . ,which
may be wriitten in functional notation:

Several important results are obtained by manipulation of dH = TdS + VdP -I-Xpidxi, (2.19)
dA = - SdT - PdV + Zpidxi,
Eq. 2.2. With the substitutionsE= n U,&= n S , I = n V , and
(2.20)
jni = nxi, the expanded and rearranged result is
dG = - SdT + VdP i (2.21)
+
d(n U)- T d ( n S ) Pd(n V) - Zpid(nxi)
Zpidxi.

= ( d U - TdS +
PdV - Zpidxi)n Thermodynamic relations are closely interrelated and may
be used to evaluate quantities that are difficult to measure in
+(U- T S + P V - Zxipi)dn = 0 . (2.4) terms of some that are easily measured. Table A.4 lists some
Since n and dn are arbitrary, each quantity in parentheses is of these readily measurable quantities and their formulas,
separately zero so that including compressibility; heat capacity; the Joule-Thomson
dU = TdS - PdV + Zpidxi, (2.5)
coefficient; and, by implication, pressure, temperature,
volume, and composition.
Although few substances approach ideal-gas behavior over
ranges of practic,sl interest, such behavior is of interest as a
When the composition does not change, Eq. 2.5 becomes the
limiting case. The main thermodynamic characteristics of
familiar
ideal gases are collected in Table A.5; Table A.6 summarizes
d U = TdS - P d V . (2.7) the changes in their properties in some common processes.
Other limiting relations, particularly those of mixtures, such as
After differentiation, Eq. 2.6 may be rearranged to
the laws of Hemyr, RaouRt, and Lewis & Randall, are used in
P d V - Z&dxi- (SdT - VdP
d U - TdS .i- + Zxidp+)= 0 . later chapters. Table A.2 lists a few named relations in
(2.8) thermodynamics.
In view of Eq. 2.5, the quantity in parentheses likewise is zero
and rearranges to
2.2. FUNDAIMENT'AL EQUATIONS
Zxidpi = -- S d T + VdP = ( d G l a T ) p d T + (aGIaP)TdP The functional relationship for a system of constant composi-
(2.9) tion,
This relatioin is one form of the Gibbs-Duhem equation; it has
many applications.
u= U(S, V ) , (2.22)
Other useful energy functions are the enthalpy, H,the is known as afund'ame~rtalequation, since all thermodynamic
Helmholtz energy, A; and the Gibbs energy, G , whose information about such a system is derivable from it, as will be
relations to the intemal energy are shown in Table A.3 and shown shortly. The mathematical form of such an equation is
developed further later. It may be shown that the various not prescribed and must be developed empirically, a process
energy functions are related quite simply to work transfers that has been ac~:omplished for very few substances. The
under specific conditions. The energy balance of a closed methods of statistical mechanics (for example, Section 1.7) do
system is lead to theoretical! equations in terms of partition functions,
112 Thermodynamic Functions and Equilibrium

= G(T, P). (2.30)

Such representations also may be made in terms of (P, V, T,


cY). For instance, Example 2.2 develops H - H~~ in this
way, whereas Example 2.3 develops expressions for H - HIa
and S - sid and indicates how other properties may be
obtained from them.
Although P and V are interrelated by an EOS, one or the
other may be a preferred variable for representing changes in
the thermodynamic properties, depending on which of them is
solvable for explicitly from the EOS. This topic is considered
in Section 2.7. In Example 2.2 the particular EOS may be
solved explicitly for either P or V , so there is no advantage of
one system over the other; but in most other cases there is a
substantial difference in the ease with which a useful relation
can be developed.
Interrelations of the properties usually involve derivatives,
of which those involving P, 'V, and T are the most easily
obtained. If Eq. 2.26 is valid, all derivatives should be
expressible in terms of those variables and the ideal heat
capacity, and several convenient methods actually have been
worked out for making such transformations. The easiest to
use and the most popular is that of Bridgman (1925).As given
in Table A.7, all derivatives are based on T P, S, and the
three derivatives most susceptible of measurement: ( ~ ? v / ' l d T ) ~ ,
(dV/aP)T,and Cp = (aH/aTlp. Second derivatives also were
covered by Bridgman. Another, perhaps more versatile
system, i.s due to Shaw (1935), which is also explained by
Sherwood & Reed (1939) and simplified by Carroll (1 965).A
system presented by Modell & Reid (1974) involves the
compressibility, z =PV/RT, and is convenient for use with
but the process of developing fundamental equations in this corresponding state correlations or equations of state explicit
way is far from being a working tool. Nevertheless, the in z.
concept of fundamental equations is illuminating. Equivalent As an example, the Bridgman scheme may be applied to
relations between other groups of variables are: fmdimg the isothermal derivatives of U and H with respect to
H = H(S, P ) , (2.23) S. The derivatives are ratios of two terms listed in Table
A.7:
A = A(T, V), (2.24)
G = G(T,P ) . (2.25)
These groups of variables have evolved naturally, but they are
deducible mathematically from the original fundamental
equation, Eq. 2.22, with the Legendre Transformation (e.g.,
Model1 & Reid, 1982). Another group of variables from which
all other thermodynamic data are deducible is

which comprises the PVT equation of state and the heat


capacity at zero pressure or in the ideal-gas state. Since the
quantities of Eq. 2.26 are the most easily measured ones, that
version is the most used of the fundamental relations, usually
not as a single equation but as a group of relations between
these variables.
Although it is not a formal proof of the principle, the entries
of Table 2.1 do indicate that all thermodynamic properties
may be represented in terms of each of the four groups of three
variables each: ( U ; S, V ) ;(H, S, P); (A, I; V ) ;or (G, T, P).
Reading from the table, for example:
2.2. Fundamental Equations 113
114 Thermodynamic Functions and Equilibrium

Pressure, psia

560

Figure 2.1. Gibbs energy of methyl chloride as a function of


temperature and pressure. Points on the surface represent
equilibrium states. Of the two free points shown at P = 50
+
psia and T = 560 R, the one at G = 10 Btu/lb is a possible
nonequilibrium state, whereas the one at T = -1 10 Btu/lb is
not physically possible; the equilibrium value is G = -24.93
Btuflb. (Data of Chemical Engineers Handbook, 1973.)

The usefulness of the Table in handling some uncommon listed in Appendix B also may be helpful in devising relations
combinations of variables is illustrated with problems at the between derivatives.
end of the chapter. Several "rules for partial differentiation"
2.2. Fundamental Equations 115
116 Thermodynamic Functions and Equilibrium

Figure 2.2. Fundamental thermodynamic surfaces: (a)


Gibbs energy-pressure-temperature surface of sodium
(Kubo, 1968); (b) Helmholtz energy-temperature-volume
surface of sodium (Kubo, 1968); (c) Enthalpy-entropy-
pressure surface of ethylene based on the Redlich-Kwong
equation of state and a polynomial equation for the heat
capacity (K. R Jolls, Iowa State University, 1982, submitted
to J. Chem. Education).
2.3. Total and Specific Properties 117

2.3. TO'TAL A N D SPECIFIC PROPERTIES The derivatives of the energy functions U, H, A, and G with
respect to the number of mols are given special symbols,
With processes involving variation in the mass or composition
of a system or its individual phases, it is necessary to
distinguish between a total property, designated M, and its
magnitude per unit mass, M . This distinction was made in
Section 2.1 but will be considered at greater length now.
Two letters can be used to identify the total property, but a and-arecalled cht?micalpotentials. They are also partial mold
single letter with understrike often is convenient. For a pure properties, when the independent properties X and Y are T
substance, and P. The particular forms of Eq. 2.34 corresponding to the
four fundamental equations are
M =nM,
-
and in differential form,

When the property M is a function of two variablesxand Y as


well as the numbers of mols of the several substances,
M = M ( X , Y, n l , n 2 , . . . ), When these equa~tionsare divided through by n, they become
( 2. )
Eqs. 2.5 and 2.1!3-2.21.
the differential is The chemical potential may be expressed in terms of any of
d g = d(n1M) the four fundame~~talgroutps of properties,
118 Thermodynamic Functions and Equilibrium

Because of the importance of T and P as independent which is implied by Eq. 3.15. The logarithmic forms belong in
properties, the chemical potential is most commonly thought this group by reason of their simple relation to the Gibbs
of as the derivative of Gibbs energy with respect to the number energy,
of mols, which is also the partial mold Gibbs energy. The
names and symbols are used interchangeably, d G = R ~ h f + A ( T , x ~ ,...
, x ~ ), (3.8)
+
dGi = ~ T l n $ A(T), (3.9)
as explained in Section 3.1. Applying Eq. 2.50,
Eqs. 2.9 and 2.21 are important relations between Gibbs Inf = Zxih&/xi), (2.51a)
energy and chemical potentials.
Examination of Eq. 2.36 reveals a simple interpretation of or
the physical meaning of the derivatives with respect to mois. f = n($/xi)"i. (2.51b)
For a system of constant composition, energy transfers by
reversible processes are-identified as
A parallel exists between the M and the 4.;
any relation
between properties is convertible to one of the same form in
partial mold properties by a one-to-one replacement of
d Q = TdS = d U (when d W = dn = O), (2.43) extensive properties-for instance:
dU= pdn (when d Q = d W = 0). (2.44) - -
G=H-TS and Gi=Hi-~&,
Since pressure is the potential function for work transfer and d G = VdP and d G i = C;.~P.
temperature that for heat transfer, p may be regarded as the
potential function for internal energy transfer accompanying A more nearly complete list is in Table 2.2.
the transfer of mass across the boundary of the system. A derivation of a partial mold compressibility,Ti, is made
in Example 2.4. Derivatives of properties other than those in
the list just before Eq. 2.49 with respect to ni are sometimes
2.4. PARTIAL MOLAL PROPERTIES needed; but for convenience if they are not made at constant T
and P, they are not called partial mold properties. For
In view of the importance of the properties T and P, which are instance, ( d P / d r ~ ~ ) ~. is
~ ,evaluated
. in Problem 2.19 and in
most readily measured and controlled, the fundamental J+
equation of the Gibbs energy, Example 3.4 for particular cases.
For many purposes it is more convenient to work with
G = G ( T , P, n l , n 2 , . . . )
- (2.45) compositions expressed in mol fractions rather than mols of
is particularly useful. Its differential is each constituent present. This topic is covered in Section 2.5,
where mention also is made of methods for evaluating partid
nolal properties from experimental data.

2.5. DERIVATIVES WITH RESPECT TO


MOL FRACTIONS
As shown in the last equation, the derivative with respect to When compositions of mixtures are given in terms of mol
mols at constant T and P is given a special symbol, Gi. It is fractions, the derivatives with respect to mol fractions may be
called the partial mold Gibbs energy, but it also is the obtained directly. Relating such derivatives to those with
chemical potential, pi, of Eq. 2.40. In terms of this symbol, respect to the numbers of mols of individual components,
Eq. 2.18 and 2.21 become however, as in the formulation of partial mold properties,
-
G = ZxiGi, (2.47) requires a little care. Individual mol numbers may be
independent, but the mol fractions are subject to the restriction
Zxi= 1, so that at least two mol fractions must vary
which state that the Gibbs energy of a mixture is the mol simultaneously when a partial derivative is taken.
fraction weighted sum of the partial mold Gibbs energies. For a binary mixture, note that
Other mol derivatives at constant temperature andpressure
likewise are called partial mold properties. The general
definition is and
ndx
d n l = n d x l + x l d n l = ~
1-x1
so that
The properties that are useful in this form include S, V; z, U,
H, A, G, Cp, C, In f , and In q5. Except for the fugacity related
properties, they conform to the relation,

Similarly,
In the case of fugacity, the partial mold relation is
Mz = M + ~ ~ ( d ~ / dM
x -~~ )~ ~( d~ ~ =/ d x ~ ) ~ p .
(2.55)
2.5. Derivatives with Respect to MOL Fractions 119

Table 2.2. Analogies between Partial Mold and Corresponding Parent Properties

Property Paritial Molal Property


-

2. Ui
3. S,;
4. H=U+PV
5. A= U-TS
6. G=U+PV-TS
P
7. z =
RT
v

8. d U = TdS - PdV
9. d i Y = T d S + VdP
10. dl4 = - SdT - PdV
11. dG=-SdT+ VdP

18. (5) P
=-
H - Hid

R ~2

lim (-&/xip)= 1
P-0
120 Thermodynamic Functions and Equilibrium

+ +
Figure 2.3. Excess properties of mixlres of water ethanol and of water methanol (Figure 2.3(f) only) (Imm
International Data Series, Selected Data on Mixtures, 1978): (a) total pressure; (b) excess heat capacity; (c) excess enthalpy;
d ) excess Gibbs energy
I,-, -. at 70 C; (e) excess entropy at 70 C; (f) excess volumes of water + methanol mixtures at 25 C.
(Continued next page)
2.5. Derivati~vesvvith Respect to MOL Fractions 121

Figure 2.3 (continued)

In the general case the partial mold property is Since

(dn/dni)nk= 1
The simplest way to keep track of whichxs are to be allowed
to vary at any one time when differentiating is: and

1. When forming %,
fust eliminate xi from the defining
equation with the substitution xi 1 - Zj+xj.
(2) =--6ij - xj
n '
2. Perfolnn this operation for each Mi that is to be found. "k
Example 2.4 applies this procedure to a ternary mixture and
Example 3.5 does it for the partial fugacities of a four Sij (2.56b)
component mixture.
Eq. 2.561 is derived, for example, by Smith & Van Ness the desired result becomes
(1975, p. (505) and an equivalent one by Model1 & Reid
(1983, p. 183). A simple derivation of an equivalent equation
is based on elimination of the mol fraction x l in favor of the
Mi = (F) =
+
~, = (2S i j - x j )
total mols, ,n. Then the functional relation becomes "k 11,Xk

(,2.56c)
M = M ( n 1 , n 2 , .. . , n , ) = n M ( n , x 2 , x 3 , . . . , x T )
The derivative is For a ternary mixture the equations are:
122 Thermodynamic Functions and Equilibrium

also

+
~ = i l / j ~M
x 2~x 2 + M 3 x 3 .
Manipulation of these equations gives
Comparatively few data of mixtures higher than binary are
complete enough to require this operation very often. A
special case is that of ternary mixtures, which often are made
up by adding varying amounts of a third component to fixed and
proportions of the other two. In a mathematical sense this is
really equivalent to a two-component system. Represent the
ratio of two of the mol fractions by r,
These relations are combined into the final expression:
and note that
X I + X Z +(x3 = 1 . (2.58)
which is of the same form as Eq. 2.54.
The differential of a property, M, at constant temperature and
The binary equations lend themselves to graphical evalua-
pressure is tion of partial molal properties, when the property of the
~ d x ~mixture
d ~ = ~ ~ d x ~ + ~ ~ d x ~ + M (2.59) , is known as a function of the mol fractions, by what is
known as the method of tangent intercepts and which is
which may be written illustrated in Fig. 3.4. On such a diagram, the partial molal
quantities at a certain mol fraction, xl , are the intercepts of the
tangent at that composition with the ordinates at 0 and I.
Graphical methods are of low accuracy, however, so it may be
more accurate and probably more convenient to perform the
2.5. Derivatives with Respect to MOL Fractions 123

required differentiations numerically as in Example 2.6. Absolute values of V; z, Cp, c, In f, and in @ can be
Partial molal volumes are found by analytical differentiation measured, but not ordinarily absolute values of H,A, G, U,
of equations of state in Examples 2.5 and 2.7. Example 2.4 and S where the experimenter is restricted to finding differ-
finds partial molal properties when the compositions are ences, for instance, AAY= H - xlH1 - x2H2, which can be
expressed in mol fractions. found calorimetrically. Clearly, however, Eq. 2.54 may be
124 Thermodynamic Functions and Equilibrium
2.7. Variation of Properties with Temperature and Pressure 125

adapted to the partial mold AH as functions are obtained in the same way. The variables are
- identified with those of the type equation, Eq. 2.6'1, in this
AH1 = AAY + ( 1 - x ,)(dAH/dx I ) T P , (2'65) table:
so there i s no complication in principle by working with
differences of properties rather than with their absolute values. Function a b x
- -y -z
Mixing anti excess properties are considered at length in a
later section. E@,V,n) - - S
- v
- n
H e , P, n )
- - P -
S - n
2.6. H O M O G E N E O U S F U N C T I O N S
A(T,V , n ) T - - v
- n
G(T,P,n)
- 2' P - n
Thermodynamic properties whose magnitudes are propor- Application of the Euler theorem gives these results:
tional to the mass, which includes all the common properties
except z, 17 and P, are a mathematical class called homo- +
U = T S PV -I-Z x i p , , (2.6)
geneous functions of the first degree. The functional relation- H = TS + Z X ~ ! , ~ , (2.16)
ship is
A=-PV+Zxipi, (2.17)
G = Zxipi. (2.18)
where 27, Y, and Z are the variables proportional to mass At constant com~lositionsthe summations are replaced by p-
.
and a, b, . . are independent of mass. An important theorem for example,
due to Euler relates such a function and its derivatives in this
G=p.
manner:
Some of these rel,ations were obtained in a different manner in
Section 2.1, but it is interesting to know that they are part of a
general pattern. Example 2.8 is devoted to some less familiar
where only derivatives with respect to mass proportional results obtained by application of this theorem.
properties are included.
Taking, for example, the enthalpy, H = H e , P, n l ,
n2, . . . ), the variables S and ni are extensive ones, but P is 2.7. VARlATllOhl OF PROPERTIES WITH
not. Accordingly, TEMPERATURE A N D PRESSURE
H =g ( d g ! d a p ,
- + Xni(dg/dni)Spnj= T z + Xnipi, The effects of temperature and pressure (or volume) on
(2.68) various thermodynamic properties are covered in detail in
which is a familiar result. Similar results for the other energy Chapter 11, but tlhe basic relations will be presented here.
126 Thermodynamic Functions and Equilibrium

Since heat capacities usually are known only at low (zero) S when the process is (PITI) -+ (P2T2) in accordance with the
pressures-that is, in the ideal-gas state-other properties are three-step process described earlier. The procedure for en-
conveniently referred to zero pressure as a basis. Thus, in thalpy change is outlined in Example 2.2, whereas that for
order to find the effect of going from state (PITl) to state entropy consists of Eq. 2.72a-d.
(P2T2), a three-step process is employed, as diagramed for AS1 = - ( S - s i d ) p l T 1 - R ln(Po/P1), (2.72a)
enthalpy in Example 2.2:

1. Reduce the pressure of the system from P1 to zero


isothermally at TI. AS3 = ( S - -R ln(P2/Po). (2.72~)
2. Evaluate the effect of changing the temperature from T1
Overall,
to T2 in terms of ideal-gas heat capacities.
3. Raise the pressure to P2isothermally at T2. S, - S = ( S - sidlPZT2
- ( S - sid)pl - R ln(P21Pl

The difference between the values of a property in the real


and ideal-gas states is called a residual and is represented as
where AH,, is the enthalpy of phase change at temperature T,,
when that is between T I and T2. Reference pressure Po goes
Since the internal energy and enthalpy of an ideal gas are to zero in the limit, but cancels out of Eq. 2.726.
independent of pressure, their residuals may be written: In Table 11.1 may be found the expressions for evaluating
M - M~~from either pressure-explicit or volume-explicit
equations of state. The basic relations are for enthalpy and
entropy. Thus:
where the subscript 0 refers to zero pressure. Since the
entropy, and hence the Helmholtz and Gibbs energies, of
d H = (8HIdT)pdT + ( d H / a P ) T d P = CpdT
ideal gases does depend on ,the pressure, the quantities - ( V - T(d V/dT)p)dP, (2.73)
S - s i d , A - A ' ~ , and G - Bd remain the differences be-
tween the real and ideal-gas properties but at agivenpressure,
dH=d(PV) + d U = d ( P V ) + (dU/dT)vdT
although, as wiIl be seen, they also involve integration of + ( a u ~ v),dv
a (2.74)
particular expressions over the interval from zero to P: = d(PV) + C,dT + (T(dP/dT)v- P)dV, (2.75)
For convenience, H - H ' = ~ H - Ho and S - s ' ~ fre-
quently have been evaluated from several P V T correlations and for entropy:
and tabulated or graphed over practical ranges of reduced
temperatures and pressures; some examples are in Chapter
d S = (dS/aT)pdT + (dS/aP)TdP
11. Such information is used for evaluating changes in H and = (Cp/T)dT - (dV/aT)pdP. (2.76)
2.8. Mixing and Excess Functions 127

dS = ( d S / a T ) v d T + (dSldV)&V weighted sum OF the properties of the pure constituents at the


same conditions;.
= (Cv/T)dT + (dP/dT)VdV. (2.77) 2. The excess propejv
Also, when only the pressure is varied,
d ( S - s'")=(RIP - ( d V / d T ) p ) d P (2.78)
is the difference between the magnitude of the actual property
= ( ( d P / d T ) v- R / V ) d V . (2.79) and the value it would have at the same conditions if it were
ideal. In this definition, the ideal mixture property is related to
Note that S - sid= 0 when P = 0. the weighted suim of the pure constituent properties by
When the composition remains constant, the preceding
equations of this section apply to mixtures. For variable
composition, relations between partial mold quantities are For all properties except the entropy and those defined in
analogous. Those for partial mold entropy, for instance, are terms of entroEy, the mi= 0 . For the others, the (change in
entropy accompanying the formation of an ideal solution is
taken into account:

The derivation d this equation is obtained in Example 2.9.


Accordingly, the valnes of mi of various properties may be
summarized as:

Extensive
Proper@ mi id
H, u, v, cp,czr 0 Z xiMi (2.86)

- :I(-- )..+ v)"( dnidT dv.


(2.81) S
A
G
-RRTInlnxi
xi
RT lnxi
Xx,(Ai +
Zxi(Si - R
RTInInxi)
+
Zxi(Gi RTlnxi)
xi) (2.87)
(2.88)
(2.89)
When the summation dS = Exid$ is made, Eqs. 2.76 and A/RT= IJ 111xi +
Zxi(AiIRT In xi) (2.90)
2.77 result. GIRT= ln xi +
ZxAGi/RT Inxi) (2.91)

2.8. MIXING AND EXCESS FUNCTIONS Relations of identical form hold between original properties,
the excess and the excess partial mold properties. Some of the
data are more informative and easier to when basic analogies are collected in Table 2.4, and those involving
expressed ]relativeto some kind of ideal behavior, the obvious derivatives and integrals are in Table 2.5. Nomenclature for
example being the difference between the volume of a real gas properties of mixtures is summarized in Table 2.3.
and that of one to the law at the same In terms of the several contributions, a property, M , is given
and P. Two kinds of differences are used widely for mixtures:
by
1. The mixing property

is the difference between the property of the mixture and the = Zxi(21?y + M i 4- mi), (2.93)
128 Thermodynamic Functions and Equilibrium

Table 2.3. Nomenclature for Properties of Mixtures where the relation


Mex = xxi&j7
M = a gensral property of a mixture: U, H, V; Cp. Cy,S, A, G
= ZxiMi. has been incorporated. The Gibbs energy has received
Mi =property of substance i. particular attention,
Mi = property of ideal gas i.
M'~ = property of an ideal solution
+
G = GeX G~~= Cxi(dfx + Gi + R T Inxi), (2.95)
= Z xi(Mi mi),+ and special terms have been invented for convenient descrip-
tion of this behavior. These are covered in detail in Chapters 3
mi = 0 except for S, A, G, and 4 but may be mentioned here also. The terms in question
are the fugacity and the activity and the related fugacity and
activity coefficients.
At constant temperature, for an ideal gas,
d ' ~= R T d In P.
~= VdP (2.96)
= partial molal property The hgacity, f, is defmed by
dG=RTdlnf. (2.96a)
Integrating from a lower limit of P = 0 at which G = G~~and
all properties listed under M plus 1n(&/xi), In &, S/P= I,
h(ai/xi), In Yi.
AM' = residual property = (property with components in the
ideal gas . state) - (true property). The notation Similarly, the excess partial Gibbs energy is
AM' = M ' - ~ M sometimes-i used. -
=MI-M=Zxi[M;+mi-Mi] Gex = Gi- = R T lnCf;/xi) - R T In P = R T ln(&/xip)

M~~~= the difference between the property of the mixture =R TI~$~. (2.98)
and the weighted sum of the properties of the Condensed phases are not naturally referred to the ideal-gas
components state, but to the pure substance at the system condition.
= AM in some books - Accordingly,
= M - ZxiMi = Zxi(Mi - Mi)
+
= MeX Zximi.

Mex = the difference between the property of the real mixture and
and that of an ideg mixture. -
= & f - & f i d = ~ ~I . ( ~I . - MI . - ~ .I) GFX= di- GEf=~T1n(.$/xi) -RTInf=RTln(&/xif)
= mix - xxI.mi = R T In yi, (2.100)
mi is defied in Section 2.8 for various properties. For those where
properties having the mi = 0, for the gaseous state
-
AM' = Mex. yi = ~ , / ~ ~ f (2.101)
is the activity coefficient. The excess Gibbs energy becomes

Table 2.4. Analogous Relations of Excess Properties and Partial Molal Excess Properties

Properly Excess Property Partial Molal Excess Property


- - - V.
vex = V.
v vex =v - zxivi - -1 1
(1
U uex= U - z x i u i ex = U . - U.
I I (2)
H=U+PV HeX= Uex + P Yex *x
-
=e
-
x
-
+ pF;x (3)
A=U-TS ex = ex - T S ~ X Aex = v x - TSex (4)
- -
G=H-TS Gex = H e x - TSex G;X = - TZF (5)
G/T= HIT- S GeX/T= HeX/T- S e x G;x/T= @/T - SFX (6)
Note: V; could be written vf and Ui could be ufef, but these superscripts usually are omitted
for convenience.
2.8. Mixing and Excess Functions 129

Table 2.5. Some Parallel Integral and Derivative Relations of Excess and Partial Molal Excess
Properties
-- -
Excess Property Partial Mokal Excess Property
- --
- -
1. GeX=G-Xxi(Gi+RTlnxi) G f X = (?i-(G:if R T l n x i )

-
-..- ?I(; -- )vx

Note: P* is a low pressure at which gas behavior becomes ideal; contril~utionsof this term cancel out
when differences are taken.

natural gas liquids. A concise paper by Nakanishi et al.


(1975) reports on the effects of ring structure and aromaticity
which is a fundamental relation in the thermodynamics of on excess functions.
solutions. The fugacity coefficient and the activity coefficient Binary excess functions of course vanish at x , = 0 and
are determined experimentally and are functions of composi- x2 = 0. AccorQingly if it is desired to fit an equation in terms
tion, temperature, and pressure. Some experimental excess of the composition, the form
function data are in Figure 2.3 and more are in Chapter 4. The
literature is quite extensive; the bibliography of Wisniak &
Tamir (1978) is 1,500 pages long. An extensive compilation satisfies these requirements. The form of f(xl, x2) is empiri-
of heats of mixing is in the book by Christensen et al. (1 982). cal and a variety has been used, particularly for Gibbs energy-
Experimental techniques and literature data on mixing vol- related functions. The I D S Selected Data on Mixtures
umes of two liquids are reviewed by Handa & Benson (1 978). (Kehiaian, 1971-date) commonly uses
A pair of recent papers may be mentioned to emphasize
current activity in this area: Low-temperature techniques are
used by Miller & Hiza (1978) for measuring volumes of
130 Thermodynamic Functions and Equilibrium

where the summation usually extends to four or five terms. A


scheme based on the more complex but flexible Legendre
polynomials is adopted for consistency analysis by the
DECHEMA Vapor Liquid Equilibrium Data Collection,
This general form of the Gibbs-Duhem equation relates any
Vol. 1, Pt. 1 (1979). property that is a function of T, P, and the composition to the
Experimental methods for determining mixing and excess
chemical poteltials. Since G = G(T, P ) is a fundamental
properties are quite varied, depending on the accuracy
equation, the Gibbs-Duhem equation is most widely applied
required, the nature of the system, and the range of pressures
with functions closely related to the Gibbs energy. The basic
and temperatures to be covered. Excess volumes of liquids are
form is
measured in some kind of dilatometer. Calorimetric methods
of varying degrees of elaborateness are used for excess -SdT + VdP = Exiddi = Exidpi. (2.1 14)
enthalpies. Phase equilibrium data leading directly to evalua-
Versions in terms of the Planck function, @ = GIRT, and its
tion of activity or fugacity coefficients are the usual method for
mixing and excess forms are collected in Table 2.6. Use will
finding excess Gibbs energies. Excess entropies then are
be made of these in later chapters.
calculated from Sex = (Hex- GeX)/T.Chemical potentials
At constant T and P, Eq. 2.1 14 becomes simply
are known when the activity coeficients are known. Other
partial mold properties are obtained by differentiation of the
parent properties. Details of experimental techniques may be
It is particularly usehl for binary mixtures in the arrangement,
tracked down by consulting recent issues of Journal of
Chemical Thermodynamics or other periodicals. In book
form, the 1,300 pages of the IUPAC sponsored work edited
or the integrated form,
by LeNeindre & Vodar (1975) is the most comprehensive
reference. The book of McGlashan (1979) stresses the
experimental aspects throughout.

2.9. THE GIBBS-DUHEM EQUATION AND which allows evaluation of one chemical potential or partial
THERMODYNAMIC CONSISTENCY molal property of a pair when the other is known as a function
of composition. Eq. 2.1 16 also is useful in the form,
In Section 2.1, the differential of the extensive internal
energy
rr=_U(3,V,n1,nz....)
was rearranged as Eq. 2.4, which is Three characteristics of Eq. 2.118 may be employed to
check the thermodynamic consistency of experimental data-
( d U - TdS + PdV - Epidxi) n namely:
1. The equation predicts that the slopes, d k / d x l , are of
opposite signs for the two components at the same
The homogeneous function theorem will be used to introduce
composition.
a variation on the analysis given there. According to that
2. The slope of yl is zero at xl = 1 and that of p2 is zero at
theorem,
Xl =0.
3. The area test developed from this equation in Example
2.10 must be satisfied, subject to some uncertainty if the
data are not truly isothermal and isobaric, though the
principal effect is that of temperature since pressure
normally has little effect on the behavior of condensed
phases.
Accordingly, the first part of Eq. 2.105 likewise is zero, that Evaluation of the thermodynamic consistency of data has
is
received much attention in the literature. The area test is a
necessary but insufficient condition, since individual data may
be off in ways that compensate each other. Schemes that
The differential of Eq. 2.108 in turn is examine the data point-by-point have been worked out and are
dU - TdS - SdT + PdV + VdP - Cyidxi - Exidpi = 0 . referred to in Chapter 4.
(2.1 10) Although it is a laborious procedure and requires many
data, the consistency test has been applied to mixtures of three
On comparing Eqs. 2.109 and 2.1 10, the conclusion is drawn and more components, for example by Herington (1951).
that
-SdT + VdP - Exidpi = 0 , (2.111)
2.10. CONDITIONS OF EQUILIBRIUM
Thermodynamics is concerned largely with relations between
various properties of systems at equilibrium, and the differ-
Similar equations can be written for any energy function, for ences between these properties in distinct equilibrium states.
which the generic equation is For instance, the PVT equation of state gives the equilibrium
2.10. Conditions of Equilibrium 131

Table 2.6. Some Forms of the Gibbs-Duhem Equation

Properly Gibbs-Duhem Equation

GIRT

Note: In connection with numbers 5 and 8, note that AH' := H - ,U'= Hex = H - H~~ since
H' = Hid.

pressure of an ideal gas at specified T and V , although in Equilibrium and other states may be identified on spatial
practice higher or lower pressures could exist momentarily or diagrams like those of Figures 2.1 and 2.2. On the diagram of
even indefinitely under metastable conditions. All the equa- methyl chloride, for instance, at P = 50 and T = =560 the
tions in tlhis book are valid only at equilibrium. The rate of equilibrium Gibbs energy is -24.93, which is the smallest
attainment of equilibrium is of practical importance, but that is value possible. Only states above the surface are lphysically
another story. possible; thus the point at G = - 110 at the cited T and P is
The state of a pure substance in a single phase is determined impossible to attain, 'whereas that at G = 10 is possible though
when two of its thermodynamic properties are specified. As unstable. On the Helmholtz diagram of sodium, only points
described in Section 2.2, complete information about such a above the surface are possible. On the ethylene diagram, in the
system is embodied in a fundamental equation of state. An direction of the entropy axis only points on and in front of the
equilibriu~mstate is characterized as having a maximum surface are possible, whereas in the direction of the enthalpy
entropy or a minimum energy function, at specified values of axis only points on and above the surface are possible.
the two other properties of the particular fundamental equa-
tion. The possible extrema at equilibrium are identified in the
following tabulation:
2.1 0.1. Mixtures
The numbers of rnols of individual species also are variables in
Property the fundamental equation of a mixture-for instance:
Independent Variables Maximum Minimum
S -
and
- u
S - - = -5dT
dG + Y d P + Xpidni. (2.120)
- H
- A Thus, in additicln to T and P, the chemical potentials are
- G involved in the specificat.ion of an equilibrium state. There are
132 Thermodynamic Functions and Equilibrium

Table 2.7. Excess Properties of Some Equimolal Binary Mixtures

Mixture "C Ger Hex


+
%-propanone decane
+
methyl acetate cyclohexane
+
dioxane heptane
+
dioxane heptane
+
2-butanone dodecane
+
benzene heptane
+
2-butanone heptane
+
2-butanone hexane
+
cyclohexane dioxane
+
acetone hexane
+
carbon tetrachloride furan
+
methyl acetate benzene
+
cyciohexane 2,3-dimethylbutane
+
cycloheptane 2,3-dimethylbutane
+
dichloromethane furan
+
cycloheptane cyclopentane
cycloheptane cyclohexane
+
cycloheptane cyclooctane
+
cyclopentane 2,3-diiethylbutane
+
1.2-dichloroethane methanol
+
carbon tetrachloride cyclopentane
+
tetrahydrofuran cyclopentane
+
dichloroethane methanol
+
dichloromethane acetone
I-propanol -I-heptane
+
dimethylsulfoxide dibromomethane
+
djmethylsulfoxide dibromomethane
+
water ethanol
+
water ethanol
- -

Data from Selected Data on Mixtures: International Data Series, Thermo-


dynamics Research Center, Texas A&M University, 1973-1981. GeX and Hex in
Jlgmol, S e x in J/(gmol) ( K ) . Some data are interpolated.

some practical differences in the handling of phase equilibria


and chemical equilibria, so they will be discussed separately.
so that from Eq. 2.121,
= pj2). (2.123)
2.1 0.2. Phase Equilibria
When the transfer of more than one substance between more
Equality of temperature of phases in contact is required for than two phases occurs, equality of chemical potentials clearly
thermal equilibrium and equality of pressure for hydrostatic extends to all phases and all substances:
equilibrium. The uniformity of chemical potentials for diffi-
sive equilibrium can be shown readily. In osmotic processes
where an interface is permeable to one of the substances, a
difference in pressure is required to maintain diffisive
equilibrium when the concentrations of the diffisable sub- The equilibrium condition may be found either by direct
stance are different in the two phases. Here hydrostatic minimization of the Gibbs energy or by utilizing the principle
equilibrium is sacrificed to prevent changes in concentration of equality of chemical potentials. In vapor-liquid equilibria,
or chemical potential. for instance, the condition of minimum Gibbs energy may be
For a transfer of dni mols of a substance between two written
phases at the same T and P, the change in Gibbs energy is GIRT= Z li[G$') + Inxi] + ZU~[G~:) + lnyi]
-

- minimum (2.125)
Since G is a minimum at equilibrium, its derivative is where li and vi are the mols of individual constituents in the
zero: liquid and vapor phases. For given overall amounts of the
2.10. Conditions of Equilibrium 133

individual substances the number of independent li or ui equals minimum Gibbs; energy and hence the equilibrium conversion
the number of substances present, so finding the minimum is simpler than finding an equilibrium phase distribution. For
Gibbs energy as a function of distribution between the phases instance, chemical equilibria in the oxidation of sulfur dioxide
is a fairly tedious numerical problem. The work is simplified, at several temperatures and pressures are found as minima on
however, by using the principle of equality of chemical the Gibbs energy plats of Example 2.11. For multiple
potentials in the two phases or, equivalently, the equality of reactions with many participants, calculation methods are
fugacities as explained in Chapter 6. Representation of the available that are simpler sometimes than direct Gibbs energy
Gibbs energy of binary liquid phase systems is easier and minimization; e:wamples are given in Chapter 10.
direct minimization is feasible; several examples are shown in
Chapter 7 .
2.1 0.4. Evaluation of Chemical Potentials
2.1 0.3. Chemical Equilibria
Because of their fundamental character in the identification of
For a chemical reaction between chemical species designated equilibrium states, numerical values of chemical potentials are
by M iand stoichiometric coefficients by vi needed in practi~calvvork. They are functions of T and P as
well as composition. Their evaluation from measured excess
properties such as G r x ,Hex,and V e x ,is simply by mathema-
the total Gibbs energy is tical differentiation of these data. The excess Gibbs energy,
for instance, usually is found from vapor-liquid and other
phase equilibrium data as explained in Chapter 4. The
If a single reaction is taking place, the amounts of all chemical potential is
substances present are related by the stoichiometric equation,
so there is only one independent variable-say, the fractional
conversion of one of the components. Thus finding the or, in binary systems,
134 Thermodynamic Functions and Equilibrium
2.1 1. Problems 135

as explained in Section 2.5. The special functions, fugacity


and activity, have been invented to simplify representation of
2.5. Find equations for the partial mold volumes in binary
Gex, as explained in Chapters 3 and 4.
The chemical potentials also are related to other partial
+
mixtures in tenns of the virial equation, V =B HTIP, and
the van der Waals equation, starting with the polynomial
molal properties, for example
form

Since thelse relations involve differentiations with respect to


compositions over wide ranges of temperature and pressure, 2.6. The fun~damentalequation A =A(T, V) or $ = $(T,
followed by integrations, they are not often used. The p ) is given for water Iby Keenan et al. (1969). Verify the
calorimetric data, particularly, are more difficult to measure equations also given there for P,1% S, H, and G in terms of the
accurately than are vapor-liquid equilibria from which activity variables of the fundamental equation. (See Table 1.22.)
coeficients and chemical potentials are derived most readily. 2.7. Find eqluivalents for the following derivatives at
constant enthalpy in terms of PGTCp data: (aU/aV)H,
(&"/dP)H, and (dG/dTIH.
2.11. PROBLEMS 2.8. Find a :relation between the Joule-Thomson coefi-
2.1. Cc~nstructa thermodynamic diagram of entropy, S , cient, ( C ~ T / ~ Pthe
) ~heat
, capacity at constant pressure, and
vertically and internal energy, U, and log(specific volume) the derivative (i)H/dP)2-.
horizontally for refrigerant 22, using the data given in Bolz & 2.9. Transform (dH/dP)T into groups of derivatives in
Tuve, Haizdbook of Tables for Applied Engineering Science which the two independent variables are selected in turn from
(1973), p. 77. the group P, V , T, and S . The method of Shaw (1 935) will be
2.2. The fundamental equation of a particular substance is convenient. It is presented, for example, by Shenvood &
given as a second-order response surface, namely: Reed, Applied Mathemcztics in Chemical Engineering (1939,
p. 180).
2.10. A differential amount dn, of a substance with
a. Determine the equations for the properties T, P, H, A, properties u,,p,, v,, and T, enters a tank already containing
and (G in terms of the variables U,S, and V. an amount n of the same material with properties U and T.
b. Plot the surface U(S, V ) for the ranges 10 5 S I30 and Heat and work transfers are d Q and dW.
100 5 V 5 300.
a. Show that the energy balance may be written
2.3. Find the partial molal volumes in an equimolal mixture
of carbon dioxide (1) and propylene (2) with the Redlich- d(n U)= nd U 4- ZJdn = d Q - d W (u, p,,v,)dn,.
+
Kwong equation for which these data hold at 400 K and 20 b. Integrate the equation under the assumptions that
atm: U = CUT,AH=CpT, heat capacities are constant, and
(dQ - dW)/dn = a, a constant. This will give a relation
between tht: temperature and the amount n of material in
(332 0.05914 0.0181 the tank.
C3H6 0.1495 0.0348
2.11. Given the fundamental equation
Mixture 0.0992 0.0265
It is convenient to start with the polynomial form
find G and C, in terms of these variables.
2.12. Tabulate or plat the partial molal volumes of mix-
The value of z at the specified conditions is 0.9253.
tures of carbon dioxide (1) and propylene at 400 K and 20 atm
+
2.4. Use the virial equation V =B RTIP to find equations from the van der Waals equation. The values of the param-
for these departures from ideality at a specified temperature: eters are

Define a reference condition ( P *, V*) at which the substance


behaves acr an ideal gas. Start with the relations:
in the units atm, OK, <andliters/gmol.
2.13. Find the Joule coefficient, q = (dT/dV)U, from the
van der Waals equation with the aid of the Bridgman Table.
2.14. Express the derivative ( d G l d T ) ~in terms of
(dH/dP)=, Cp and P V T derivatives.
2.15. Find (dlJ/dV)H for (a) an ideal gas; (b) a gas with
equation of state P(V - h) = RT.
136 Thermodynamic Functions and Equilibrium

2.16. Find the derivative (aGIdP)H of the Joule-Thomson 2.22. Excess volumetric data of water-methanol mixtures,
experiment in terms of the van der Waals equation. ml/gmol at 25" C, aregiven. Fit apolynomial of the second
2.17. Apply the procedure of Example 2.2 with the B-
-
degree in (1 2x1) to these data (IDS Selected Data on
Mixtures).
truncated virial equation in the explicit forms
P = (1 + BIV) RTIV, vex
vex
- 1- 2x1
XlX2

and also with the approximation

2.18. Complete the solution of Example 2.1 when the flow


is outwards, (dQ - dW)ldn = constant, the gas is ideal, and
the heat capacities are constant.
2.19. Show that for the equation of state,
RT
P=
V - ~ l b l -y2b2 '
the derivative is

2.23. The excess Gibbs energy of mixtures of ethanol (1)


and n-heptane (2) is represented by
2.20. Show that for U(S,V) the "change of variable held
constant" rule of Appendix B gives
where
A = 1.8857 exp(-1055.1 l/T),

Verify that this is correct with the Bridgman Table. Also find
(aGl~3T)~ both ways. The data are taken from Table E.7. Some data of excess
2.21. The graph shows excess property data of mixtures of enthalpies of equimolal mixtures are taken from the IDS
methanol and piperidine at 298.15 K by Nakanishi, Wada, & Selected Data on Mixtures, as follows:
Touhara (1975).
a. Find GfX, gy and TS~Xand xMeeOH-2.4.
b. With your values check GeX= C xiG and the other
properties. Evaluate the excess enthalpies from the given equation for GeX
c. Also compare the I?? - G? with the values of TSF and compare with the quoted values.
that were calculated. 2.24. Excess enthalpy data of mixtures of n-hexane and n-
hexadecane are given by the equation
Hex= xlx2(ao'+ al(l - 2x Joules/gmol,
where the coefficients are functions of temperature:

Find the change in excess Gibbs energy resulting from a


change of temperature from 20 C to 50 C with xl = 0.25.
2.25. Excess properties of a mixture containing 25 percent
water in ethanol are, in the units Jlgmol:
2.1 1. Problems 137

Do these data satisfy the Gibbs-Helmholtz equation? may be applicilble. How nearly is this true? Suggest a better
curve fit to these data:
T(dGex/,dT)+Hex= GeX
2.26. Data of Joule-Thomson coefficient, pK/atm, heat
capacity, Cp cal/gmol-K and second virial coefficient, B
ml/gmol, of nitrogen are given.
a. Derive the relation, pCp = -d(B/T)/d(l/T).
b. Assuming the value at 273 to be correct, find values of
the virial coefficient at other temperatures from the data
2.29. Find an integrable relation between temperature and
of p and Cp.
volume in the isentropic expansion of a gas that follows
+
the virial equation, V =RT/P B, with B = a bT and +
+
Cp = c dT.
2.30. The mlolal volumes of a binary mixture are correlated
by
V = 3 + 2(x1 - x2) + (xl - x ~ ) ~ .
Find the partiall molal excess volumes.
2.31. The Gibbs (energyof a mixture is represented by

2.27. Precise measurements of the specific volumes of


G = x l lnylxl + x21ny2x2,
aqueous I-b02 at 25 C are fitted by the equation with In y 1 = 0.5~: and In 72 = 3.0~:. What is the equilibrium
V, ml/g := 0.0030(1- w ) + 0 . 6 9 3 5 ~- 0.0360w(l - w), composition?
2.32. The excess erlthalpy of mixtures of water (1) and
where w is the mass fraction of H202. Find the partial molal
ethanediol (2) is represented by the equation
volumes over the entire range of concentrations.
2.28.- Elnthalpies of mixing of carbon tetrachloride and
Hex= x1x2[-:2,431.9 + 1,925(xl - x2)
cyclohexane at 25 C are given. The solutions are believed to - 1,467.6(~1- . x ~ )+~385.9(x1 - x ~ ) ~ ] ,
be ''regula? so that the symmetrical equation,
J/gmol at 25' C. Derive equations for the partial mold
AIP' = kxlx2 enthalpies. (IDS Series B, No. 67, 1978).