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Equations of State
Studying the motions of complex uid media involves determining how local quantities that characterize the behavior of single- or multicomponent,
homogeneous or heterogeneous media evolve over time and space.
The state variables of a mixture are dened in Sect. 2.1. Initially for continuous media at rest and at equilibrium, we introduce extensive quantities
(i.e., quantities that depend on the size of the system) such as the masses and
volumes of the various constituents of gases and ideal liquid mixtures, as well
as their strains for solids. Specic quantities, such as chemical progress variables for reacting mixtures, are extensive quantities too. Intensive (i.e., bulk)
quantities such as temperature, pressure, and strains are also presented. Moreover, when the medium is moving, velocity vectors, uxes, and production rate
terms must also be considered.
Section 2.2 considers thermodynamic aspects, and the notion of entropy
(an extensive quantity) is introduced. Temperature, pressure, and species
chemical potential (all intensive variables) are the conjugates of entropy, volume, and species mass, respectively. For solids, stresses are the intensive conjugates of strains. The laws of state (LOS) that express the relationship between the state variables for one component in a continuous medium at rest
and equilibrium will remain valid even when the local values of these variables
change (this is known as the local state postulate).
The LOS for mixtures are discussed in Sect. 2.3. Section 2.4 focuses on
reactive mixtures, particularly those at chemical equilibrium.
Temperature, pressure (or stresses), and chemical potentials are introduced
as the rst partial derivatives of the internal energy with respect to their
extensive conjugates in Sects. 2.2 to 2.4, while the second partial derivatives of
energy are considered in Sect. 2.5. This leads, together with the second law of
thermodynamics and the concept of stability at thermodynamic equilibrium,
to inequalities involving quantities such as specic heats and characteristic
speeds.
Section 2.6 addresses equilibrium at the uid interface and the concept of
surface tension, and applies this to the behavior of a bubble in a liquid.
2 Equations of State
It should be pointed out that the laws of state can only be applied to equilibrium evolution problems. Other laws are needed to investigate irreversible
processes, and these are described in Chap. 3.
However, the balance equations presented in Chap. 4 are required to completely solve problems involving complex media in motion, while multiphase
media are addressed in Chap. 12.
N
mj ,
(2.1)
j=1
where N is the number of species in the mixture. The total number of moles
in the control volume V is
n=
N
nj .
(2.2)
j=1
(2.3)
(2.4)
N
j = m/V,
(2.5)
j=1
N
j=1
Cj .
(2.6)
N
nj Mj /n.
(2.7)
j=1
(2.8)
(2.9)
and we have
N
Mj Cj = Mj Xj /
j=1
N
Mj Xj .
(2.10)
j=1
Yj = 1.
(2.11)
j=1
j Ej
N
j Ej
(2.12)
j=1
10
2 Equations of State
dj = j Mj d, dCj = j d, C = C 0 + , =
N
j .
(2.14)
j=1
Xj = n0j + j / n0 +
Yj = m0j + j Mj /m0 ,
(2.15)
taking into account the conservation of mass during the reaction N
j=1 j Mj =
0. Xj and Yj can also be written as functions of .
When there are K reactions in total, K progress variables can be used.
Example: The combustion reactions of a H2 O2 mixture are shown below:
H2 2H
chain initiation
H + O2 OH + O
chain branching
O
+
H
OH
+
H
chain
branching
H + OH H2 O
chain breaking
2 1 1 1 1
H
0 1 1 0 0
O
1 0 1 1 0
H
2
species j
ir =
0 1 0 0 0
O2
0 1 1 1 1
OH
0 0 0 1 1
H2 O
R1 R2 R3 R4 R5
reaction j
2.1.3 Denitions Required to Describe a Reactive Fluid
In contrast to the case for the homogeneous mixture considered in Sects. 2.1.1
and 2.1.2, the properties of a ow are seldom uniform, and so it is not sucient to simply provide the values of the quantities T, p, Xj . These quantities
vary over space and time. There are, however, local parameters (specic or
intensive) that dene the state of the system at any point, so we then have
T (x, t), p(x, t); (x, t), Cj (x, t) (for unit volume) and Yj (x, t), nj (x, t) (for
unit mass). This is the local state postulate.1 Moreover, each (innitely small)
particle of uid is also characterized by mechanical parameters. We dene N
velocity vectors vj (x, t), j = 1, ... N and also:
N
The barycentric velocity: v = (1/) j=1 j vj (see (2.5) for the denition
of )
1
Regarding time, the local state postulate stipulates that the current internal
energy state of a homogeneous system at any point during its evolution does not
depend on the rate of evolution, and that it can be characterized using the same
state variables as those that characterize the equilibrium state.
The
The
The
The
11
diusion velocities: Vj = vj v
species uxes: Jj = j vj
total mass ow: J = v = N
j=1 Jj
diusion uxes: J Dj = j Vj .
Due to the dierence between the specic velocities vj and vi , the domain
common to both species i and j at time t is generally divided into two separate
domains at time t .
Each chemical species then exhibits its own motion (Fig. 2.1), although
it is generally considered that these are not very dierent from the average
motion. At time t, and per unit volume of the mixture, the mass of species j
produced by the chemical reaction per unit time is
j =W
j (x, t).
W
(2.16)
In the absence of diusion (Vj = 0), the following equations are obtained for
only one reaction and for K reactions, respectively:
j = j Mj ,
W
(2.17)
j = K jr Mj r .
W
r=1
2.1.4 The Case for Solids
The state of a solid depends on more variables than the state of a uid. These
additional variables allow us to characterize its strains and corresponding
stresses, and they are most naturally presented in tensorial notation.
12
2 Equations of State
13
(2.18)
where E is a function called the internal energy that depends only on the
equilibrium state of the system (E depends only on the variables of state and
can be regarded as state variable itself). When Q = 0, the transformation is
said to be adiabatic.
For a reversible elementary transformation we have
+ dQ,
dE = dW
(2.19)
and dQ
are dierential forms.
where dW
On the other hand, for an elementary (innitesimal) unspecied transformation,
E = W + Q
(2.20)
(in the general case, W and Q simply indicate small quantities rather than
dierential forms).
We can extend this to a system at equilibrium in Galilean reference frames
with dierent velocities in states 1 and 2:
(E2 + K2 ) (E1 + K1 ) = W + Q,
(2.21)
where K represents the kinetic energy of the system. For a reversible elementary transformation, we have
14
2 Equations of State
+ dQ.
dE + dK = dW
(2.22)
E2
dQ/T
= 0.
E1
Note: It can be shown that, for a simple system (dependent on two variables),
there is always an integrating factor, and so the rst part of the second law is always
obeyed.
(2.23)
(2.24)
In the general case, the main diculty here involves determining the external
variation in entropy e S (the entropy ux from the outside) and the internal
variation i S (the entropy produced). These laws extend to transformations
between nonequilibrium states if we can dene (depending on the case) the
functions E and S as well as the temperature T .
2.2.2 Properties of Simple Fluids at Equilibrium
When the uid undergoes a reversible mechanical transformation, the elementary work done is equal to
15
= p dV.
dW
(2.25)
= T dS,
dQ
(2.26)
we can deduce that, for a closed uid domain (no mass exchange with the
outside),
dE = T dS p dV.
(2.27)
(2.28)
(2.29)
g = E/m or = E/n
(2.30)
We then set
where = Mg, where M is the molar mass. This leads to the Gibbs equation
dE = T dS p dV + g dm or dE = T dS p dV + dn.
(2.31)
(2.32)
E
E
E
S+
V+
m.
S
V
m
(2.33)
16
2 Equations of State
(2.34)
Using this relation and the Gibbs equation, we can deduce the GibbsDuhem
equation
0 = S dT V dp + m dg,
(2.35)
0 = S dT V dp + n d.
(2.36)
or
(2.37)
(2.38)
In the same manner, we obtain the following relations for the Helmholtz free
energy:
F = E T S = p V + g m,
(2.39)
dF = S dT p dV + g dm,
and for the Gibbs free enthalpy we obtain
G = E T S + p V = g m,
dG = S dT + V dp + g dm.
(2.40)
The partial derivative g is thus the free enthalpy per unit mass, just as is
the molar free enthalpy.
For unit mass and = 1/, we get
e = T s p + g = e(s, ), de = T ds p d, 0 = s dT dp + dg,
0 = S dT V dp + d,
H = E + pV = H(S, p), dH = T dS + V dp,
17
(2.42)
(2.43)
(2.46)
0
By deriving with respect to T and p, we can deduce the classical laws of state
for a perfect gas: S = /T = d0T /dT R ln(p/p0 ), V = /p = RT /p.
18
2 Equations of State
0
(2.47)
H = H T = E T + RT.
(2.48)
C v + R, and H 0 = E 0 + RT .
0
0
of the perfect gas can be deduced: S T = S 0 +
T The molar standard entropy
0
(C p (T )/T )dT , where S 0 refers to the standard state dened by (T 0 , p0 ). For
T0
0
the molar entropy we have S = S T R ln(p/p0 ), and for the molar standard free
0
0
enthalpy 0T = H T T S T .
0
Use of a standard volume V : Note that if we use the variables T, V instead
0
of T, p, a similar form is obtained for the entropy S = ST0 + R ln(V/V ), but this
0
0
T
time ST0 = S 0 + T 0 (C v (T )/T )dT = S T R ln(T /T 0 ). For the internal energy,
0
T0 , where E
T0 = E T . For the molar Helmholtz free energy, F =
we have E = E
0
0
0
0
Real Fluids
The state diagram for a pure substance is represented schematically in Fig.
2.3.
The perfect gas domain corresponds to small pressures and large volumes.
We will discuss this point in more depth in the following with respect to van
der Waals EOS (see Fig. 2.4 and the associated discussion).
Another important observation is the existence of the liquidvapor critical
point C (see Appendix A.5.1 for the thermodynamic properties of uids near
the critical point).
Since the law of state is generally given in the form p = p(T, V), where
T is the temperature and V is the molar volume, we will dene a standard
0
molar volume V corresponding to the standard state of an ideal gas at the
0
temperature T 0 , where the standard pressure p0 is given by p0 V = RT 0 .
Such a standard state always exists.
i
Flu
cal
Pressure
Liq
uid
+Va
por
Sol
id
qu
Li
riti
Soli
19
C
per
Su
Solid+Liquid
id+
or
p
Va
Vap
o
ure
rat
e
mp
Vo
lu
Te
me
V
V
pdV.
Here FT0 is the standard value of the molar free energy of the perfect gas at
0
V = V . We write
pdV =
V
(p RT /V)dV + RT ln(V/V ).
(p RT /V)dV =
V
(p RT /V)dV
=
(p RT /V)dV +
(p RT /V)dV,
since the uid is considered to be a perfect gas if V > V . We then deduce that
0
0
F
= FT RT ln(V/V )
(p RT /V)dV.
20
2 Equations of State
(V b) (p + a/V ) = RT.
(2.49)
This equation of state is the simplest one for real gases and liquids. It takes
into account the minimum distance between the molecules and the interactions
2
2
between them. For rareed gases a/V
p, so V b
= (RT /p)(1 a/pV ),
2
and for a perfect gas (for V b aRT /p2 V ) we have V = RT /p. For liquids,
2
2
a/V p (a/V is a few tens of thousands of atmospheres), so we can often
0
ignore p, and thus V
= VT .
Proof: With the reduced variables x = V/V C , y = p/pC , z = T /TC , the van
der Waals state equation can be written as y = 8z/(3x 1) 3/x2 . Using these
variables, the equation of state for a perfect gas becomes ypf t = 8z/3x. The uid can
be considered a perfect gas if y ypf t 1. The isobars z = (3x1)(y +3/x2 )/8, y =
const. are shown in Fig. 2.4. It is clear that these curves tend to become straight
lines when the relative volume increases. This proves that, for a van der Waals uid,
one can dene a standard state on any isotherm at a given temperature T provided
that the values of the parameters are chosen in the appropriate region. This result,
which is related to the denition of a perfect gas, does not depend on the uid
considered. If is an arbitrarily small number, we can assume that the pressure in
the van der Waals law is equal to that of a perfect gas with a relative error if
(y ypf t )/ypf t .
It is easy to see that if x 1/3, we also have z y/8.
We now directly determine the forms of the internal energy, the entropy,
and the molar free enthalpy of a van der Waals uid. We have
2
21
Fig. 2.4. Denition of a standard state: the plot shows isobars of y = p/pc =const.
in the (x, z) plane
22
2 Equations of State
2
Let us start from V = V r [1 L (p pr )] [1 + L (T Tr )] for the molar volume, where pr and Tr are a reference pressure and temperature, and V r is a
reference molar volume; L and L are assumed to be constant. We deduce that
= L / [1 L (p pr )] , = L / [1 + L (T Tr )], and so
= L ,
= L
provided that L |p pr | and L |T Tr | 1. This latter formula corresponds
to the linearization of a more general equation in the vicinity of pr and Tr .
Let us consider the case of a liquid for which the molar volume is only a
0
function of the temperature V
= V T . We will use the function F , meaning
0
that F = F (T, V) is a function of the temperature alone here; i.e., F = F T .
We deduce from this that
0
= F T + p VT .
(2.51)
0
FT.
Then,
The term 0T is often used instead of
= 0T + p V T , F = 0T ,
0
0
0
E = + T S pV = 0T (T ) T (d0T /dT,
0
0
0
+p dV T /dT ) = E T pT dV T /dT,
0
0
0
H = + T S = E T p(T dV T /dT V T ).
(2.52)
23
(2.53)
Or, conversely,
p=
B
C
RT
(1 + + 2 + . . .).
V
V
V
(2.54)
= 0T + RT ln(p/p0 ) + Bp,
0
S = (/T )p = S T R ln(p/p0 ) p dB/dT,
0
S T = d0T /dT,
(2.55)
(2.56)
F = F T RT lnV + RT B/V.
(2.57)
(2.58)
6
Other formulae can be found in the literature. So Stephenson [267] gives for
Argon in homogeneous phase, an expansion with seven terms which is slightly different from the virial one.
24
2 Equations of State
which leads to
F = pV = 0T + RT ln(RT /p0 V) + RT B/V RT
and gives the expression for
0
FT
(2.59)
as a function of 0T :
(2.60)
The supercritical uid case is presented in the Appendix (see Sect. A.5.1).
2.2.4 EOS for Solids
The internal energy of a solid is E = E(S, , m), which depends on eight
variables (or seven variables if we assume unit mass or consider one mole of
the solid). The simplest equation of state is obtained for elastic solids. For a
uid, the conjugate of the volume is the negative of the pressure. For a solid,
the conjugate of the strain tensor is the stress tensor . In the framework
of the small perturbation theory, the EOS for thermoelasticity is
= tr()1 + 2 3K1,
(2.61)
1+
tr()1 + 1,
E
E
3 + 2
.
+
(2.62)
where = 0 c /2T0 and c is the specic heat per unit mass of the solid at
1
( (tr()2 + 2 ) 3K tr 2 ,
2
25
(2.63)
(2.64)
(2.65)
(2.66)
so that
dE = T dS p dV +
N
j dnj ,
(2.67)
j=1
N
j nj .
(2.68)
j=1
N
nj dj .
(2.69)
j=1
Note that, for a closed system in moving equilibrium (reversible transformation), it is necessarily the case that
N
j=1
j dnj = 0.
(2.70)
26
2 Equations of State
However, we will consider cases where this relation is not obeyed for closed
systems. Each component will be regarded as being at equilibrium in the
mixture, but there will not be a mutual equilibrium between the components.
There are irreversible evolutions of chemical origin. In this case, we can always
write E = W + Q, but if W is always equal to p V, Q will obey
Q = T (S i S)
with i S 0. Thus,
N
j nj = T i S 0,
(2.71)
j=1
N
H = E + pV = T S + j=1 j nj = H(S, p, nj ),
dH = T dS + V dp + N
j=1 j dnj ,
N
F = E T S = pV +
j=1 j nj = F (T, V, nj ),
(2.72)
N
dF = S dT p dV + j=1 j dnj ,
N
G = E T S + pV = j=1 j nj = G(T, p, nj ),
N
dG = S dT + V dp + j=1 j dnj .
The thermodynamic functions for a given mixture cannot generally be deduced from the thermodynamic functions for the pure substances. Thus j ,
the chemical potential of j in this mixture, is dierent from the thermodynamic potential j of the pure substance j ( of the pure substance j).
2.3.2 Partial Molar Quantities
To express the laws of state in the absence of a known fundamental energy
law E(S, V, nj ) or H(T, p, nj ), one often uses the partial molar quantities.
If is an extensive thermodynamic function, the partial molar quantities of
this extensive quantity will be
(2.73)
Gj = j ,
H j = T S j + j ,
F j = p V j + j .
27
(2.74)
(2.75)
(2.76)
N
nj j =
j=1
N
j .
(2.77)
j=1
N
N
S = j=1 nj S j = j=1 Sj ,
N
V= N
j=1 nj V j =
j=1 Vj ,
N
N
E = j=1 nj E j = j=1 Ej ,
(2.78)
E = T Sj pVj + j nj ,
j
Hj = T Sj + j nj ,
Fj = pVj + j nj .
(2.79)
and we have7
7
Initially, it is as if each species j constitutes an autonomous subsystem that
is characterized by its own internal energy Ej and its own variables Sj ,Vj ,nj . If
this was really the case, it would be necessary to obey the Gibbs relation for each
subsystem; i.e., dEj = T dSj p dVj + j dnj . However, this is not the case in
general. Indeed, dEj = T dSj p dVj + j dnj + Sj dT Vj dp + nj dj = T dSj
p dV
j + j dnj + nj (S j dT Vj dp + dj ); i.e., dEj = T dSj p dVj + j dnj +
(j /ni )T, p, nk=i dni . It would therefore be necessary, to ensure that the
nj
j
preceding assertion is obeyed, for
(j /ni )T, p, nk=i dni = 0. This is not true
j
for most cases. However, the results are simplied for ideal mixtures.
28
2 Equations of State
(2.80)
S j = j /T = j /T R ln Xj ,
(2.81)
We then nd that
or
S j = S j R ln Xj .
(2.82)
Vj = Vj .
(2.83)
E j = T S j pV j + j = T S j pV j + j = E j ,
H j = T S j + j = T S j + = H j ,
j
F j = pV j + j nj = E j T S j = E j T S j + RT ln Xj ,
= F j + RT ln Xj .
(2.84)
m =
N
nj j .
(2.85)
j=1
(2.86)
29
2.3.5 Activity
The activity8 of species j in a mixture is denoted aj , where
j = j + RT ln aj .
For an ideal mixture, aj = Xj . In the general case,
nj ln aj .
Gm = RT
(2.87)
(2.88)
(2.89)
(2.90)
(2.91)
and
(2.92)
or
dGj = Sj dT + V dpj .
(2.93)
Gj = Gj (T, pj , nj ) = j nj .
(2.94)
Recall that
We can therefore see that the formalism used for simple systems will also
be valid for component j, with the proviso that this component occupies the
8
30
2 Equations of State
E = T Sj pj V + j nj = Ej (Sj , V, nj ),
j
(2.95)
dEj = T dSj pj dV + j dnj ,
0 = Sj dT V dpj + nj dj .
Here, the total system (mixture) can be regarded as the sum of N subsystems
whose extensive properties are additive:
G=
Gj , E =
Ej , H =
Hj , S =
Sj , F =
Fj .
j
Therefore,
T
0
0
E = j nj (E T )j = j nj [(E 0 )j + T 0 C v, j (T ) dT ],
T
0
0
H = j nj (H T )j = j nj [(H 0 )j + T 0 C p, j (T ) dT ],
0
0
(H 0 )j = (E 0 )j + RT 0 , C p, j = C v, j + R,
0
T
0
0
(S T )j = (S 0 )j + T 0 (C p, j /T ) dT ,
0
F = j nj [(F T )j + RT ln(pXj /p0 )],
0
T
0
0
(F T )j = (F 0 )j + T 0 [C p, j (1 T /T ) R (S 0 )j ] dT ,
0
0
0
(F 0 )j = (E 0 )j T (S 0 )j ,
T
0
(0T )j = (00 )j + T 0 [C p, j (1 T /T ) R (S 0 )j ] dT ,
(0 ) = (H 0 ) T (S 0 ) .
0 j
0 j
0 j
(2.96)
31
= 0T + RT ln(p/p0 ) + Bp,
V = RT /p + B.
Starting from statistical thermodynamics, and considering rst-order molecular interactions, it can be shown that
G=
nj [RT ln(p/p0 ) + p
Bk, l Xk Xl + (0T )j + RT ln Xj ]
(2.98)
k, l
in a mixture, which leads to the following expression for the chemical potential
of a binary mixture:
j = j + RT ln Xj p Xi2 (B11 2B12 + B22 ), i = j,
j = (0T )j + RT ln(p/p0 ) + Bjj p.
For N species,
j = (0T )j + RT ln(pXj /p0 ) + p (2
k
Bkj Xk
Bkj Xk Xl ).
(2.99)
k, l
The Bij coecients relate to the interactions between molecules of type i and
j, so Bij = Bji . Note that the mixture is ideal, in the binary case, for B12 =
(1/2) (B11 + B22 ). However, this case is not supported by any experimental
or theoretical justication, so it is a completely arbitrary assumption.
2.3.8 Liquid Solution
Let us consider a mixture of two liquids in the presence of their vapors, constituting an ideal mixture of perfect gases at a given T :
g g
g g
G = 1 n1 + 2 n2 + l1 nl1 + l2 nl2 ,
g
l
n + n1 = n1 = const., ng2 + nl2 = n2 = const.,
1
dG = S dT + V dp + (l1 g1 )dnl1 + (l2 g2 )dnl2 .
(2.100)
32
2 Equations of State
l2 = (0T )g2 + RT ln(p2 /p0 ). The equilibrium of each pure liquid with its vapor at the same temperature is given by (1 )l = (1 )g = (0T )g1 +RT ln(p1 /p0 )
and (2 )l = (2 )g = (0T )g2 + RT ln(p2 /p0 ), where pj is the saturated vapor
pressure of species j.
By subtraction,
l1 (1 )l = RT ln(p1 /p1 ), l2 (2 )l = RT ln(p2 /p2 ),
(2.101)
(2.102)
Often, one of the components of a solution obeys Raoults law, but not necessarily the other. How can we determine a2 , knowing that a1 = X1 ? We can
write the GibbsDuhem equation for a given p and T : n1 d1 + n2 d2 = 0 or
X1 d1 + X2 d2 = 0. This gives X1 RT dX1 /X1 + X2 RT da2 /a2 = 0, with
dX1 + dX2 = 0. Then da2 /a2 = dX2 /X2 , and
ln(a2 ) = ln(X2 ) + f (T, p).
We set a2 =
law.
p2 /p2
= b(T,
p) X2 /p2 .
(2.103)
33
Qm =
Xi Xj Qi, j .
(2.105)
i, j
Qii = Qi for the pure substance, and Qij where i and j are dierent corresponds to mixtures. Using this general expression, we can consider the following rules:
Qij =
(Qii + Qjj )/2, which gives Qm
= iXi Qi
Qij = Qii Qjj , which gives Qm = ( i Xi Qi )2 .
More sophisticated rules involve binary interaction parameters ki, j that
are usually independent of temperature, pressure and concentration, such as:
Qij = ki, j (Qii +Qjj )/2, where for example kii = 1 and kij=i is determined
experimentally
Qij = ki, j Qii Qjj , with kii = 1.
a1 = 0.39608(1 +
k)n1 n2 n1 n2 + n22 a2 , nbm = n1 b1 + n2 b2 . The coecients are:
0.72782 T /304.1), b1 = 2.66545 105 , a2 = 4.37138(1 + 0.81576 T /748.4), b2 =
1.19533 104 .
34
2 Equations of State
F
F
F
)V,nj = S, (
)T,nj = p, (
)T,V,ni=j = j ,
T
V
nj
(2.106)
(2.107)
(2.108)
F (T, V, nj ) = F 0 (T, V 0 , nj )
(2.109)
p dV,
(2.110)
V0
F (T, V, nj ) = F 0 (T, V 0 , nj ) 0 p dV V p dV,
V
(2.111)
35
(2.112)
h
)T,p .
(2.113)
(2.114)
where (qf0 )j is the heat of formation per unit mass of the species under stan0
0
(H 0 )j
+
T0
C p, j (T ) dT .
The quantity H is the energy released by the chemical reaction per mole
for an ideal mixture of perfect gases at constant temperature and pressure.
For a combustion reaction, which is exothermic, H is positive. The quantity
H =
(2.115)
j Mj (qf0 )j
j
is then the heat released during the combustion reaction. For a multireactive
mixture (see Eq. 2.17), the heat released becomes11
11
As noted in [206], the full term W T = j Wj hj , including the contributions
from sensible heat enthalpy (i.e., the enthalpy due to an increase in temperature)
terms, is also called the heat released by various authors.
36
2 Equations of State
T =
W
j
j (q 0 )j =
W
f
jr Mj (qf0 )j r =
K
Hr r .
(2.116)
r=1
j,r
i S =
1
j nj .
T j
(2.117)
For a single chemical reaction (as given by Eq. 2.12, with stoichiometric coefcients j ), in the absence of diusion (which is the case for a homogeneous
closed system with uniform properties), we have
dnj = j d,
(2.118)
where is the progress variable for the reaction. The production of entropy
becomes
i S =
j j .
T j
(2.119)
j j .
(2.120)
A
0,
T
(2.121)
In this case,
i S =
where an equals sign would correspond to the equilibrium of the mixture. Two
equilibrium cases are possible:
37
A
> 0.
T
(2.122)
(2.123)
(2.124)
We then derive the expression for the second law for reversible transformations:
+ dW
= T dS p dV.
dE = dQ
For a chemically irreversible transformation,
E = Q + W = T (S i S) p dV,
where the term T i S is equal to A d = j j dnj .
(2.125)
(2.126)
or, since pj = Cj RT ,
j [(0T )j + RT ln(RT /p0 ) + RT ln Cj ].
A=
j
By setting
(2.128)
38
2 Equations of State
ln KC = (1/RT )
(2.129)
we therefore obtain
N
(Cj )j = KC exp(A/RT ).
(2.130)
j=1
(Cj )j = KC (T ).
(2.131)
j=1
L
li Al , i = (L + 1), . . . N.
(2.132)
l=1
N
li ni = n0l , l = 1, . . . L,
(2.133)
i=l+1
L
Ai = i l=1 li l , i = (L + 1), . . . N,
L
Ai = (0T )i l=1 li (0T )l
0
RT ( L
l=1 li 1) ln(RT /p ) + RT ln( l (Cl /Ci )).
(2.134)
12
Note that there is also an
equilibrium constant of partial pressures Kp (T ),
dened as ln Kp = (1/RT ) j j (0T )j . The chemical equilibrium relation then
becomes
N
(p /p0 )j
j=1 j
= Kp (T ).
39
By setting
L
L
ln KC, i = [
li (0T )l (0T )i + RT (
li 1) ln(RT /p0 )]/RT, (2.135)
l=1
l=1
we obtain
L
(Cl /Ci ) = KC, i exp(Ai /RT ), i = (L + 1) . . . N.
(2.136)
l=1
(2.137)
l=1
Cpf = (
N
dQ
1 S
H
j,
)p,nj = (
)p,nj = (
)p,nj =
nj Cp,
dT
T T
T
j=1
(2.138)
cpf = (
N
dq
1 s
h
j.
)p,nj = (
)p,nj = (
)p,nj =
Yj Cp,
dT
T T
T
j=1
(2.139)
40
2 Equations of State
(2.140)
13
41
(2.143)
1
j nj .
T j
(2.144)
(2.145)
and we nd that
i S = (A/T ) .
This time,
A=
j j RT ln(aj )j .
(2.146)
(2.147)
Setting
ln Ka =
j j ,
(2.148)
we get
N
(2.149)
j=1
and, at equilibrium,
N
(2.150)
j=1
i S = (A/T ) .
(2.151)
Chemical kinetics (see Sect. 3.4) allows us to obtain the expression for the
reaction rate as a function of the state variables and then to determine the
time evolution of the mixture.
42
2 Equations of State
(2.152)
(2.153)
The chemical potential gj per unit mass was also introduced, where gj =
j /Mj , and this leads to results similar to those shown above:
E = E(S, V, m1 , m2 , . . . mN ),
(2.154)
T = E/dS, p = E/V, gj = E/mj .
We see here that the second law of thermodynamics leads, in the case of stable
equilibrium, to conditions on the partial second derivatives with respect to the
extensive variables of the internal energy, and this has consequences for the
usual quantities and relations. This is thermodynamic stability.
2.5.1 The Stability Matrix
We now consider a mixture of N species distributed on both sides of a nondeformable, adiabatic and impermeable surface inside a container. The walls
of the container are isolated from the outside (see Fig. 2.6a).
Each subsystem is at thermodynamic equilibrium, with xed concentrations. If we remove the wall (we assume that this requires a negligible amount
of work and that no chemical reaction takes place during the transformation),
the mixture then occupies the entire container and will naturally reach a new
state of equilibrium. This is a characteristic of a medium with thermodynamic
stability (see Fig. 2.6b).
We then obtain the following relations:
E + E = Ef , S + S Sf ,
(2.155)
V + V = Vf , nj + nj = njf .
Then
E(S, V, nj ) + E(S , V , nj ) = E(Sf , V + V , nj + nj ).
Since T = E/dS 0,
(2.156)
43
Fig. 2.6. A chemical mixture: a in a container with two sections; b after removing
the inner surface
(2.157)
It follows that
E(S, V, nj ) + E(S , V , nj ) E(S + S , V + V , nj + nj ).
(2.158)
(2.159)
. . . 2 E/SnN
. . . 2 E/VnN
. . . 2 E/n1 nN
.
...
...
...
...
2
2
. . . E/nN
(2.160)
Similar results are obtained if the molar amounts of the species nj are replaced
with the masses of the species mj .
44
2 Equations of State
2 E/S 2 = T /S > 0,
(2.161)
What are the consequences of this for a mixture of unit mass? We need
to consider the relation
N
Mj nj = 1.
(2.162)
j=1
This relation does not modify the convexity of the function E, which then
becomes e and depends on N + 1 independent variables instead of N + 2.
This result can be generalized if an additional condition on concentration
variations is given. For a certain number R of independent progress variables,
we have
R
nj = n0j +
jr r ,
(2.163)
r=1
with
N
Mj n0j = 1
(2.164)
Mj jr = 0.
(2.165)
j=1
and
N
j=1
N
jr j ,
(2.166)
j=1
and we have
e = e(s, , 1 , 2 , . . . R ),
R
de = T ds p d r=1 Ar dr .
(2.167)
(2.168)
The convexity of the internal energy function results in positive denite character for the matrix
ess
evs
e1 s
...
...
eR s
es
e
e1
...
...
eR
es1
e1
e1 1
...
...
eR 1
. . . esR
. . . eR
. . . e1 R
.
... ...
... ...
. . . eR R
45
(2.169)
(2.170)
Specic Heats
)p = T (s/T )p,
cp = (dq/dT
(2.171)
dp = 0 = es ds + e d,
dT = ess ds + es d = (ess e2s /e ) ds.
(2.172)
(2.173)
(2.174)
Moreover,
Characteristic Speed
(p/)s = 2 (p/)s = v 2 e > 0.
(2.175)
c2 = (p/)s .
(2.176)
We therefore set
46
2 Equations of State
A = 0,
c2 = 2 (e e2 /e ) c2 .
e
f
(2.178)
On the other hand, we cannot say anything about the signs of quantities such
as
a = (p/)s = e
(2.179)
b = (p/A)s = e /e .
(2.180)
or
(2.181)
47
(2.182)
(2.183)
0 = S a dT + d + da .
For the liquidvapor interface of a pure substance, it is generally assumed
that the surface tension is a function of temperature alone. We then have
= (T ). The usual thermodynamic properties are easily deduced using the
interfacial free energy Fa . For one mole,
F a = E a T S a = + a = F a (T, ),
(2.184)
d F a = S a dT + d .
Therefore, S a / = d/dT is a function of T only. d/dT is usually
negative. We deduce from this relation that
0
S a = (d/dT ) + (S T )a .
(2.185)
Then
d F a = [(d/dT ) (S T )a ] dT + d,
T 0
0
F a = (F 0 )a + T 0 (S T )a dT,
0
(F 0 )a = const.
T 0
0
0
Or, setting (F T )a = (F 0 )a T 0 (S T )a dT ,
0
(2.186)
F a = (F T )a + .
(2.187)
a = F a ,
(2.188)
it follows that
0
a = (F T )a ,
(2.189)
15
It is more common to consider unit area, in which case we get ea = T sa + +
a na , and then the relations can be deduced from (2.183) and na = 1. However,
we will retain the present formalism, which is also valid.
48
2 Equations of State
0
E a = (E T )a + ( T d/dT ),
(2.190)
with
0
(E T )a = (F 0 )a + T (S T )a
T0
(S T )a dT.
(2.191)
g
g
g
g
g
g
dE = T dS p dV + dn ,
dE l = T dS l pl dV l + l dnl ,
(2.192)
E = E g + E l + Ea , S = S g + S l + Sa ,
V = V g + V l , n = ng + nl + n ,
a
dE = T dS p dV + (pl pg )dV g + d,
49
(2.193)
+ dQ,
=
For a reversible transformation we always have dE = dW
dW
= T dS. Therefore, for an unspecied innitesimal transformap dV, dQ
tion, E = T S p V T i S, assuming that the piston displacement is
reversible. It follows that
T i S = (pl pg )V g + (g l )ng + (a l )na + 0. (2.194)
Because
V g = 4/3 r3 , V g = 4 r2 r,
= 4 r2 , = 8 r r = 2 V g /r,
(2.195)
(2.197)
Exercise:
Calculate the saturated vapor pressure of a vapor bubble in a liquid at a pressure
p and temperature T , and then compare it with that obtained for a liquid with a
planar surface (p ).
RT ln(pg /p ) = (pl p )V .
l
However,
pg = pl + 2 /r,
RT ln(pg /p ) = (pl p 2 /r)V .
l
50
2 Equations of State
Remark: We now invert the above problem by considering a liquid drop suspended
N
Ea = T Sa + + j=1 j nja ,
dEa = T dSa + d + N
j=1 j dnja ,
N
0 = Sa dT + d + j=1 nja dj .
(2.198)
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