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This chapter is a review of the equilibrium state of a system that can undergo
chemical reaction
Operating reactors are not at chemical equilibrium, so why study this?
Find limits of reactor performance
Find operations or design changes that allow these restrictions to be changed
and reactor performance improved
Thermodynamic system
T , P , nj
Specifying the temperature, pressure, and number of moles of each component then completely specifies the equilibrium state of the system.
Gibbs Energy
dG = SdT + V dP +
j dnj
Consider a closed system. The nj can change only by the single chemical
reaction,
X
-*- 3A3 + 4A4
1 A1 + 2 A2 )
j Aj = 0
j
Reaction extent.
dnj = j d
Gibbs energy.
X
dG = SdT + V dP +
j j d
(1)
Partial derivatives
X
dG = SdT + V dP +
j j d
j
G
S=
T P ,
G
V =
P T ,
X
G
j j =
T ,P
j
(2)
(3)
(4)
G X
=
j j = 0
j j = 0
(5)
j = Gj + RT ln aj
aj is the activity of component j in the mixture referenced to some standard
state
Gj is the Gibbs energy of component j in the same standard state.
The activity and fugacity of component j are related by
aj = fj /fj
fj is the fugacity of component j
fj is the fugacity of component j in the standard state.
9
The standard state is: pure component j at 1.0 atm pressure and the system
temperature.
Gj and fj are therefore not functions of the system pressure or composition
Gj and fj are strong functions of the system temperature
10
j = Gj + RT ln aj
j j =
j Gj
+ RT
(6)
j ln aj
P
The term j j Gj is known as the standard Gibbs energy change for the
reaction, G.
G + RT ln
j
aj
=0
(7)
11
Equilibrium constant
K = eG
/RT
(8)
j
aj
(9)
12
-*- 2, 2, 3trimethylpentane
isobutane + 1butene )
I
-*)
13
Solution
K=
aP
aI aB
(11)
(12)
14
Solution (cont.)
K = eG
/RT
K = 108
K=
yP
PP
=
PI PB
yI yBP
yj = 1
nI = nI0
nB = nB0
nP = nP0 +
(13)
17
The total number of moles decreases with reaction extent because more
moles are consumed than produced by the reaction. Dividing both sides of
Equations 13 by nT produces equations for the mole fractions in terms of the
reaction extent,
nI0
yI =
nT 0
nB0
yB =
nT 0
nP0 +
yP =
nT 0
Dividing top and bottom of the right-hand side of the previous equations by
nT 0 yields,
yI0 0
yB0 0
yP0 + 0
yB =
yP =
yI =
1 0
1 0
1 0
in which 0 = /nT 0 is a dimensionless reaction extent that is scaled by the initial
total number of moles.
18
(yP0 + 0)(1 0)
K=
(yB0 0)(yI0 0)P
(yB0 0)(yI0 0)KP (yP0 + 0)(1 0) = 0
Quadratic in 0. Using the initial composition, yP0 = 0, yB0 = yI0 = 1/2 gives
2
0 (1 + KP ) 0(1 + KP ) + (1/4)KP = 0
The two solutions are
0 =
1 1/(1 + KP )
2
(14)
19
yI = 5.73 102
yB = 5.73 102
yP = 0.885
The equilibrium at 400K favors the product trimethylpentane.
20
Second derivative of G.
21
Evaluation of G.
G=
j nj
(15)
j =
G=
X
j
Gj
nj Gj
+ RT ln yj + ln P
+ RT
nj ln yj + ln P
(16)
X
j
nj Gj
nj0Gj + G
(17)
23
e , P , 0) =
G(T
nj0Gj
nT 0RT
(18)
i
X nj h
e=
ln yj + ln P
G
+
RT
n
T0
j
0 G
(19)
1+
j
24
X
yj0 + j 0
0
0
0
e = ln K + (1 +
) ln P + (yj0 + j ) ln
G
0
1
+
!
(20)
25
-*- P
I+B )
(21)
P
= 1.
For this stoichiometry: j j =
Equimolar starting mixture: yP 0 = 0, yI0 = yB0 = 0.5
e , P , 0) = 0 ln K(T ) + (1 0) ln P +
G(T
0 ln(0) + 2(0.5 0) ln(0.5 0) (1 0) ln(1 0) (22)
26
-1.88
-1.89
0.5
-1.9
-1.91
-1.92
-1.93
e
G
-0.5
-1.94
-1.95
0.45
0.46
0.47
0.48
0.49
0.5
-1
-1.5
-2
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5
0
27
A closer look
-1.88
-1.89
-1.9
-1.91
-1.92
-1.93
-1.94
-1.95
0.45
0.46
0.47
0.48
0.49
0.5
Effect of pressure
From Equation 20, for an ideal gas, the pressure enters directly in the Gibbs
energy with the ln P term.
Remake the plot for P = 2.0.
Remake the plot for P = 1.5.
How does the equilibrium composition change.
Does this agree with Le Chateliers principle?
For single liquid-phase or solid-phase systems, the effect of pressure on equilibrium is usually small, because the chemical potential of a component in a
liquid-phase or solid-phase solution is usually a weak function of pressure.
29
Effect of temperature
The temperature effect on the Gibbs energy is contained in the ln K(T ) term.
This term often gives rise to a large effect of temperature on equilibrium.
We turn our attention to the evaluation of this important temperature effect
in the next section.
30
We usually calculate the standard Gibbs energy change for the reaction, G,
by using the Gibbs energy of formation of the species.
The standard state for the elements are usually the pure elements in their
common form at 25C and 1.0 atm.
1
GH
=
G
GO2
H2
H2 O
2 Of
2
(23)
This gives the Gibbs energy change for the reaction at 25C
Gi
ij Gjf
(24)
31
33
The standard state temperature 25C is often not the system temperature.
Recall from Equation 2 that the change of the Gibbs energy with temperature
is the negative of the entropy,
G
T
= S,
P ,nj
Gj
T
!
= Sj
P ,nj
34
j Sj
Defining the term on the right-hand side to be the standard entropy change of
reaction, S gives
G
= S
(25)
T
Let H denote the enthalpy and recall its connection to the Gibbs energy,
G = H TS
(26)
35
Xj =
X
nj
!
T ,P ,nk
(27)
36
G
G H
=
T
T
37
=
RT T
RT 2
RT 2
Using differentiation formulas, the left-hand side can be rewritten as
G
RT
H
=
T
RT 2
which finally can be expressed in terms of the equilibrium constant
ln K
H
=
T
RT 2
(28)
38
Z T2
T1
ln K
dT =
T
Z T2
T1
H
dT
RT 2
If H is approximately constant
K2
ln
K1
H 1
1
=
R
T2 T1
(29)
39
T = T
P = P
j =
j ,
j = 1, 2, . . . , ns
j = j + RT ln fj
(30)
(31)
If we express Equation 31 for two phases and and equate their chemical
potentials we deduce
fj = fj ,
j = 1, 2 . . . , ns
(32)
One can therefore use either the equality of chemical potentials or fugacities as
the condition for equilibrium.
41
Gaseous Solutions
Let fjG denote the fugacity of pure component j in the gas phase at the
mixtures temperature and pressure.
The simplest mixing rule is the linear mixing rule
fjG = fjG yj
(ideal mixture)
(33)
An ideal gas obeys this mixing rule and the fugacity of pure j at the mixtures
T and P is the systems pressure, fjG = P .
fjG = P yj
(ideal gas)
42
The simplest mixing rule for liquid (and solid) mixtures is that the fugacity of
component j in the mixture is the fugacity of pure j at the mixtures temperature
and pressure times the mole fraction of j in the mixture.
fjL = fjLxj
(34)
44
P2
= fj
"
P1
exp
V j (P2 P1)
RT
#
(36)
45
Nonideal Mixtures
j
For gaseous mixtures, we define the fugacity coefficient,
j
fjG = P yj
The analogous correcting factor for the liquid phase is the activity coefficient,
j .
fjL = fjLxj j
These coefficients may be available in several forms. Correlations may exist
for systems of interest or phase equilibrium data may be available from which
the coefficients can be calculated [2, 3, 6, 4, 1].
46
(37)
47
48
All three phases are in intimate contact and we have the following data:
AAC = 1.4
ACA = 2.0
PA = 0.65 atm
PB = 0.50 atm
PC = 0.50 atm
in which Pj is the vapor pressure of component j at the system temperature.
49
1. Plot the partial pressures of A and C versus xA for a vapor phase that is in equilibrium with only the AC liquid phase. Compute the Henrys law constants
for A and C from the Margules equation. Sketch the meaning of Henrys law
on the plot and verify your calculation from the plot.
2. Use Henrys law to calculate the composition of all three phases for K = 4.7.
What is the equilibrium pressure?
3. Repeat for K = 0.23.
4. Assume K = 1. Use the Margules equation to calculate the composition of all
three phases.
50
51
Part 1.
Equate the chemical potential in gas and liquid-phases. Since the gas phase
is assumed an ideal-gas mixture:
fAG = PA
gas phase,
liquid phase
(38)
PA = PA xAA
(39)
52
53
Part 1.
PT
P (atm)
0.8
PA
0.6
PC
0.4
PC
PA
0.2
0
0
0.2
0.4
0.6
0.8
xA
54
Part 1.
fAL = fALxAA
55
Part 1.
56
Part 2.
For K = 4.7, one expects a large value of the equilibrium constant to favor the
formation of the product, C. We therefore assume that xA is small and Henrys
law is valid for component A.
The unknowns in the problem: xA and xC in the AC mixture, yA, yB and yC
in the gas phase, P .
We require six equations for a well-posed problem: equate fugacities of each
component in the gas and liquid phases,
the mole fractions sum to one in the gas and AC liquid phases.
The chemical equilibrium provides the sixth equation.
57
Part 2.
K=
LA
a
C
a
Aa
B
a
fAL
kAxA
= =
fA
fA
fA is the fugacity of pure liquid A at the system temperature and 1.0 atm.
Again, this value is unknown, but we do know that PA is the fugacity of pure liquid
A at the system temperature and the vapor pressure of A at this temperature.
The difference between 0.65 and 1.0 atm is not large, so we assume fA = PA .
58
fCL
fCLxC
= =
fC
fC
Now fCL and fC are the fugacities of pure liquid C at the system temperature
and the system pressure and 1.0 atm, respectively.
If the system pressure turns out to be reasonably small, then it is a good
assumption to assume these fugacities are equal giving,
LC = xC
a
Since component B is in a pure liquid phase, the same reasoning leads to
LB
a
fBL
fBL
= = =1
fB
fB
59
Part 2.
xC
xAkA/PA 1
(40)
kA K
1+
PA
!1
PA 1
xC = 1 +
kAK
xC = 0.95
60
61
Part 2.
The vapor compositions now are computed from the phase equilibrium conditions.
PA = k A xA
PB = PB
PC = PC xC
Substituting in the provided data gives
PA = 0.13 atm,
PB = 0.50 atm,
PC = 0.48 atm
yB = 0.45,
yC = 0.43
63
Part 3.
For K = 0.23 one expects the reactants to be favored so Henrys law is assumed for component C. You are encouraged to work through the preceding
development again for this situation. The answers are
xA = 0.97,
yA = 0.51,
xC = 0.03
yB = 0.40,
yC = 0.09
P = 1.24 atm
Again the assumption of Henrys law is justified and the system pressure is low.
64
Part 4.
xC C
xAA
K=
(1 xA) exp
2
xA
(ACA
+ 2(AAC
i
ACA)(1 xA))
(41)
65
Part 4.
Pj = Pjxj j ,
j = A, C
The solution is
xA = 0.35,
yA = 0.36,
xC = 0.65
yB = 0.37,
yC = 0.28
P = 1.37 atm
66
Part 5.
Finally, if one assumes that the AC mixture is ideal, the equilibrium condition becomes
xC
K=
xA
which can be solved to give xA = 1/(1 + K). For K = 1, the solution is
xA = 0.5,
yA = 0.30,
xC = 0.5
yB = 0.47,
yC = 0.23
P = 1.08 atm
The ideal mixture assumption leads to significant error given the strong deviations from ideality shown in Figure .
67
Multiple Reactions
ij Aj = 0,
i = 1, 2, . . . , nr
ij i
(42)
j dnj
j
68
Multiple Reactions
Using dnj =
i ij di ,
gives
dG = SdT + V dP +
ij di
X X
ij j di
= SdT + V dP +
i
(43)
G
i
= 0,
i = 1, 2, . . . , nr
T ,P ,li
69
Multiple Reactions
G(i )
2
1
X
G
=
ij j = 0
i
j
70
ij j = 0,
i = 1, 2, . . . , nr
(44)
71
Multiple Reactions
ij j =
ij Gj
+ RT
ij ln aj
ij j = Gi + RT
ij ln aj
j
ij Gj
Ki = eGi /RT
(45)
72
Ki =
ij
aj ,
i = 1, 2, . . . , nr
(46)
73
-*- 2, 2, 4trimethylpentane
isobutane + 1butene )
(47)
K2 = 284
74
nI = nI0 1 2
nB = nB0 1 2
nP1 = nP10 + 1
nP2 = nP20 + 2
yB0 10 20
yB =
1 10 20
yP1
yP10 + 10
=
1 10 20
yP2
yP20 + 20
=
1 10 20
yP2
K2 =
yI yB P
75
Substituting in the mole fractions gives two equations for the two unknown
reaction extents,
P K1(yI0 10 20 )(yB0 10 20 ) (yP10 + 10 )(1 10 20 ) = 0
P K2(yI0 10 20 )(yB0 10 20 ) (yP20 + 20 )(1 10 20 ) = 0
76
Numerical solution
yI = 0.031,
yB = 0.031,
2 = 0.351
yP1 = 0.258,
yP2 = 0.680
Optimization Approach
j nj
(48)
78
j nj =
nj0Gj
Gj
X
i
ij i + nj0 +
ij i RT ln aj
(49)
n
G
j0
j
j
e , P , 0) =
G(T
(50)
i
nT 0RT
in which i0 = i/nT 0.
If we sum on j in Equation 49 and introduce this expression into Equations 48
79
e=
G
X
i
0 Gi
i
RT
X
j
yj0 +
ij i0 ln aj
80
e
Expression for G
e=
G
i0 ln Ki
yj0 +
ij i0 ln aj
(51)
We minimize this modified Gibbs energy over the physically meaningful values of the nr extents.
The main restriction on these extents is, again, that they produce nonnegative mole numbers, or, if we wish to use intensive variables, nonnegative mole
fractions. We can express these constraints as
yj0
ij i0 0,
j = 1, . . . , ns
(52)
81
Optimization problem
Our final statement, therefore, for finding the equilibrium composition for
multiple reactions is to solve the optimization problem
e
min G
i0
(53)
82
aj =
P
yj
1 atm
(ideal-gas mixture)
e
G
i0 ln Ki
+ 1 +
ii0 ln P
yj0 +
X
i
#
P
0
yj0 + i ij i
P
ij i0 ln
1 + i ii0
"
(54)
83
Constraints
The constraints on the extents are found from Equation 52. For this problem
they are
yI0 + 10 + 20 0
yB0 + 10 + 20 0
yP10 10 0
yP20 20 0
0 10 ,
0 20
84
Solution
0.5
-2.557
-2.55
-2.53
-2.5
-2
-1
0
0.45
0.4
0.35
0.3
0
2
0.25
0.2
0.15
0.1
0.05
0
0
0.1
0.2
0.3
0.4
0.5
0
1
85
Solution
20 = 0.351,
e = 2.569
G
The solution is in good agreement with the extents computed using the algebraic approach, and the Gibbs energy contours depicted in Figure .
86
Summary
The Gibbs energy is the convenient function for solving reaction equilibrium
problems when the temperature and pressure are specified.
The fundamental equilibrium condition is that the Gibbs energy is minimized.
This fundamental condition leads to several conditions for equilibrium such as
For a single reaction
X
j j = 0
K=
aj
87
Summary
ij j = 0,
i = 1, . . . , nr
ij
aj ,
i = 1, . . . , nr
Ki =
Y
j
Ki = eGi /RT
88
Summary
You should feel free to use whichever formulation is most convenient for the
problem.
The equilibrium constant is not so constant, because it depends on temperature via
ln K
H
=
T
RT 2
or, if the enthalpy change does not vary with temperature,
ln
K2
K1
=
H
R
1
1
T2 T1
89
Summary
The conditions for phase equilibrium were presented: equalities of temperature, pressure and chemical potential of each species in all phases.
The evaluation of chemical potentials of mixtures was discussed, and the following methods and approximations were presented: ideal mixture, Henrys
law, and simple correlations for activity coefficients.
When more than one reaction is considered, which is the usual situation faced
in applications, we require numerical methods to find the equilibrium composition.
Two approaches to this problem were presented. We either solve a set of
nonlinear algebraic equations or solve a nonlinear optimization problem sub90
91
Notation
aj
activity of species j
ajl
Aj
CPj
El
fj
fugacity of species j
Gibbs energy
Gj
enthalpy
Hj
reaction index, i = 1, 2, . . . , nr
92
species index, j = 1, 2, . . . , ns
phase index, k = 1, 2, . . . , np
equilibrium constant
Ki
element index, l = 1, 2, . . . , ne
nj
moles of species j
nr
ns
pressure
Pj
gas constant
entropy
Sj
temperature
volume
Vj
xj
yj
reaction extent
ij
i
j
94
References
[1] J. R. Elliott and C. T. Lira. Introductory Chemical Engineering Thermodynamics. Prentice Hall, Upper Saddle River, New Jersey, 1999.
[2] B. E. Poling, J. M. Prausnitz, and J. P. OConnell. Properties of Gases and
Liquids. McGraw-Hill, New York, 2001.
[3] J. M. Prausnitz, R. N. Lichtenthaler, and E. G. de Azevedo. Molecular Thermodynamics of Fluid-Phase Equilibria. Prentice Hall, Upper Saddle River, New
Jersey, third edition, 1999.
[4] S. I. Sandler, editor. Models for Thermodynamic and Phase Equilibria Calculations. Marcel Dekker, New York, 1994.
[5] D. R. Stull, E. F. Westrum Jr., and G. C. Sinke. The Chemical Thermodynamics
of Organic Compounds. John Wiley & Sons, New York, 1969.
95
96