Functions and
Equilibrium
109
2.2. Fundamental Equations 111
Several important results are obtained by manipulation of dH = TdS + VdP IXpidxi, (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 JouleThomson
dU = TdS  PdV + Zpidxi, (2.5)
coefficient; and, by implication, pressure, temperature,
volume, and composition.
Although few substances approach idealgas 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 GibbsDuhem 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
Pressure, psia
560
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
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 andarecalled 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,
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 areidentified 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 onetoone replacement of
d Q = TdS = d U (when d W = dn = O), (2.43) extensive propertiesfor instance:
dU= pdn (when d Q = d W = 0). (2.44)  
G=HTS 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.
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
2. Ui
3. S,;
4. H=U+PV
5. A= UTS
6. G=U+PVTS
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
P0
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
(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 twocomponent 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 IZ 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
pressuresthat is, in the idealgas stateother properties are threestep 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. 2.72ad.
(P2T2), a threestep 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:
Extensive
Proper@ mi id
H, u, v, cp,czr 0 Z xiMi (2.86)
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
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 idealgas
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
Table 2.5. Some Parallel Integral and Derivative Relations of Excess and Partial Molal Excess
Properties
 
Excess Property Partial Mokal Excess Property
 
 
1. GeX=GXxi(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.
2.9. THE GIBBSDUHEM 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 pointbypoint 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
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 mixturefor 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
 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 vaporliquid 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 variablesay, 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
2.16. Find the derivative (aGIdP)H of the JouleThomson 2.22. Excess volumetric data of watermethanol 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
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 xMeeOH2.4.
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 nhexane and n
hexadecane are given by the equation
Hex= xlx2(ao'+ al(l  2x Joules/gmol,
where the coefficients are functions of temperature:
Do these data satisfy the GibbsHelmholtz 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 JouleThomson coefficient, pK/atm, heat
capacity, Cp cal/gmolK 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
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