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OVERVIEW
Raw materials are transformed into products by chemical reaction.
A chemical equilibrium has been established when a chemical reaction reaches
a state where the concentrations of reactants and products remain constant.
At equilibrium, the rate of the forward reaction is equal to the rate of the
reverse reaction.
Both the rate and the equilibrium conversion of a chemical reaction depend on
the temperature, pressure and composition of reactants.
The study of thermodynamics give the equilibrium values. The study of rate
gives speed of reaching those values.
The purpose of this chapter is to determine the effect of temperature, pressure
and initial composition on the equilibrium conversion of chemical reactions.
1 A1 2 A2 3 A3 4 A4 (13.1)
where i is stoichiometric coefficient
Ai is chemical formula.
i is stoichiometric number, and it is
positive (+) for product negative (-) for reactant
Example: CH4 H2O CO 3H2
the stoichiometric numbers are
CH 1
4
H O 1
2
CO 1 H 3
2
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CHE553 Chemical Engineering Thermodynamics 5/13/2016
Applied to differential amount of reaction, this principle provides the Integration of eq. (13.3) from an initial unreacted state where = 0 and ni =
equations: nio to a state reached after an amount of reaction gives
dn2 dn1 dn3 dn1
etc. ni
2 1 3 1
ni 0
dni i d
0
The list continues to include all species. Comparison yields or ni ni 0 i i 1, 2, ..., N (13.4)
dn1 dn2 dn3 dn4 Summation over all species yields
...
1 2 3 4 n ni ni 0 i
All terms being equal, they can be identified collectively by a single quantity i i i
5 6
7 8
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CHE553 Chemical Engineering Thermodynamics 5/13/2016
Integration from ni = ni0 and j = 0 to ni and j gives where the numbers (1) and (2) indicate the value of j, the reaction index. If
ni ni 0 i , j j i 1, 2, ..., N (13.6) there are present initially 2 mol CH4 and 3 mol H2O, determine expressions
Summing over all species yields j for the yi as functions of 1 and 2.
n ni 0 i , j j n0 i , j j Solution:
i i j j i
The stoichiometric numbers i,j can be arrayed as follows:
The definition of a total stoichiometric number i i for a single
reaction has its counterpart here in the definition:
i= CH4 H2O CO CO2 H2
j i , j thus n n0 j j
i j j j
Combination of this last equation with eq. (13.6) gives the mole fraction
1 -1 -1 1 0 3 2
ni 0 j i , j j 2 -1 -2 0 1 4 2
yi i 1, 2, ..., N (13.7)
n0 j j j
9 10
ni 0 j i , j j
yi i 1, 2, ..., N The Gibbs function serves as variable that determines whether a given
n0 j j j chemical change is thermodynamically possible.
11 12
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CHE553 Chemical Engineering Thermodynamics 5/13/2016
Fig. 13.1 shows that this quantity is zero at the equilibrium state. A criterion of Combining eq. (13.8) with eq. (13.9) to eliminate i gives for the equilibrium
chemical reaction equilibrium is therefore state of a chemical reaction:
i i 0 (13.8)
i
i
G io RT ln fi f i o 0
i
or
i
Recall the definition of the fugacity of a species in solution: G i
i
o
i RT ln fi f i o
i
0
i i T RT ln fi (11.46) or
RTi
i i G io
ln fi f i o
In addition, eq. (11.31) may be written for pure species i in its standard state i
at the same temperature: where i signifies the product over all species i.
In exponential form, this equation becomes
G i i T RT ln f i (11.31) Gio i T RT ln f i o
f
i
fio K (13.10)
i
The difference between these two equations is i
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CHE553 Chemical Engineering Thermodynamics 5/13/2016
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CHE553 Chemical Engineering Thermodynamics 5/13/2016
T0
The second integral of eq. (13.18) is
Hence,
D 1
H0o G0o R T0 CRP dT RT T0 CRP dT
o o
T CPo dT
A ln BT0 CT02 2 2
T T T
G o H0o
T0 T0 R T
1
T0 2
(13.19)
Finally, division by RT yields OR
G o G 0 H 0 H0 1
o o o
C o T C
o
dT T
C Po dT T C 2
T T02 2D T12 T12
T
RT
RT0
RT T T0 RP dT T0 RP T (13.18) R T
A ln B T T0
T0 T0 2 o
21 22
H T0 o
(13.22)
K1 exp 1
0
From Table C.1 and C.4:
RT0 T
vi A B (x10-3) C (x10-6) D (x105) Ho298 Go298
1 T C Po T C dT
o
(13.23)
K2 exp dT P
(J/mol) (J/mol)
T T0 R T0 R T
C2H5OH 1 3.518 20.001 -6.002 - -235100 -168490
C2H4 -1 1.424 14.394 -4.392 - 52510 68460
H2O -1 3.470 1.450 - 0.121 -241818 -228572
23 24
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CHE553 Chemical Engineering Thermodynamics 5/13/2016
i
T0 R
dT 22.632
C i C i 1.610 10-6 T C dT
o
i T0 R P T 0.0173
D i Di - 0.121105
i
G593.15
o
8378 45792 45792 22.632
H298
o
i Hio,298 45792 Jmol-1 0.0173 5.8286
i
RT 8.314 298.15 8.314 593.15 593.15
G 298
o
i G io,298 8378 Jmol-1
i
For T = 418.15 K, values of integrals in eq. (13.18) are Finally, by eq. (13.11b)
TC o T C o dT
T0 R P dT 23.121 eqn. 4.19 T0 R P T 0.0692 eqn. 13.19
ln K
G o
RT
Substitute into eq. (13.18) for a reference temperature of 298.15 K gives:
G o G 0 H 0 H0 1
o o o
T C P o T C
o
P dT At 418.15 K, ln K = -1.9356 and K = 1.443 x 10-1
RT
RT0
RT T
T0 R
dT
T0 R T (13.18)
At 593.15 K, ln K = -5.8286 and K = 2.942 x 10-3
G 418.15
o
8378 45792 45792 23.121
0.0692 1.9356
RT 8.314 298.15 8.314 418.15 418.15 Alternative solution by using eq. (13.21), (13.22) and (13.23).
25 26
f
i
i fio K (13.10) P o
K (13.25)
i i
This eq. relates K to fugacities of the reacting species as they exist in the real
equilibrium mixture. These fugacities reflect the non-idealities of the
equilibrium mixture and are functions of temperature, pressure and
composition.
The fugacity is related to the fugacity coefficient by eq. (11.52):
fi i y i P
28
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CHE553 Chemical Engineering Thermodynamics 5/13/2016
Substitute into eq. (13.25) provides an equilibrium expression displaying the Some conclusions based on eq. (13.28) that are true in general:
pressure and the composition: According to eq. (13.14), the effect of temperature on the equilibrium
constant K is determined by the sign of Ho.
y
P
o K
i
(13.26) d ln K H o
i i
P (13.14)
i
dT RT 2
where i i and Po is the standard state pressure of 1 bar. When H is positive, i.e., when the standard reaction is endothermic, an
o
f
fi i x i f i i i P
(11.90) As a result,
xifi
fi P
f i o P o
RT ln Vi dP
The fugacity ratio can be expressed as
fi i x i f i f Because Vi changes little with pressure for liquids (and solids), integration from
o i x i io (13.29)
fio fi fi Po to P gives
f i Vi P P
o
ln (13.30)
Because the fugacities of liquids are weak function of pressure, the ratio fi/fio is fio RT
often taken as unity. With eq. (13.29) and (13.30), eq. (13.10) may be written as
For pure liquid i, eq. (11.31) is written for temperature T and pressure P, and
Po P
for the same temperature T but for standard state pressure Po.
x i iVi
i
i i K exp (13.31)
G i i T RT ln f i i RT
G i o i T RT ln f i o 31 32
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CHE553 Chemical Engineering Thermodynamics 5/13/2016
x
i
K is carried out under the different sets of conditions described below. Calculate
i
i (13.33) the fraction of steam reacted in each case. Assume the mixture behaves as an
ideal gas.
33 34
(a) The reactants consist of 1 mol of H2O vapor and 1 mol of CO. The (b) Same as (a) except that the pressure is 10 bar.
temperature is 1100 K and the pressure is 1 bar.
For the given reaction at 1100 K, 10 4/T = 9.05, and from Figure 13.2, (c) Same as (a) except that 2 mol of N2 is included in the reactants.
ln K = 0 and K = 1. (d) The reactants are 2 mol of H2O and 1 mol of CO. Other conditions are
i i 1 1 1 1 0 the same as in (a).
Because the reaction mixture is an ideal gas, eq. (13.28) applies (e) The reactants are 1 mol of H2O and 2 mol of CO. Other conditions are
0
the same as in (a).
P
o K
1bar
y y y y 1bar
i
i yCO
1 1 1 1
1 (f) The initial mixture consists of 1 mol of H2O, 1 mol CO and 1 mol of
P H2 O CO2 H2
CO2. Other conditions are the same as in (a).
i
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CHE553 Chemical Engineering Thermodynamics 5/13/2016
EXAMPLE 13.6
Fugacity coefficients are evaluated by eq. (11.68).
Pr 0 Pr 0
Estimate the maximum conversion of ethylene to ethanol by vapor-phase ln
Tr
B B1 or exp B B1
hydration at 250oC (523.15 K) and 35 bar for an initial steam to ethylene Tr
ratio of 5. Assume the reaction mixture is an ideal solution. 0.422 0.172
B0 0.083 and B1 0.139
Tr1.6 Tr4.2
Solution: C2 H4 g H2O g C 2H5OH g
The results are summarized in the following table:
The calculation of K for this reaction is treated in Example 13.4.
At T = 523.15 K, K = 10.02 x 10-3 Tc/K Pc/bar i Tri Pri B0 B1 i
For ideal solution, C2H4 282.3 50.40 0.087 1.853 0.694 -0.074 0.126 0.977
P
y o K H2O 647.1 220.55 0.345 0.808 0.159 -0.511 -0.281 0.887
i
i i
P (13.27)
i EtOH 513.9 61.48 0.645 1.018 0.569 -0.327 -0.021 0.827
Because i 1 1 1 1 this equation becomes
i Substitute values of i and P = 35 bar into eqn. (A) gives:
y EtOHEtOH P
y EtOHEtOH P
10.02 103 A 10.02 103 A
yC2H4 C2H4 y H2OH2O P o yC H C H y H OH O P o
2 4 2 4 2 2
EXAMPLE 13.7
By eqn. (13.5),
1 e 5 e e
yC2H4 yH2O yEtOH In a laboratory investigation, acetylene is catalytically hydrogenated to
6 e 6 e 6 e
ethylene at 1120oC (1393.15 K) and 1 bar. If the feed is an equimolar
Substitute these into eqn. (B) yields: mixture of acetylene and hydrogen, what is the composition of the product
stream at equilibrium?
e 6 e
0.367 or e2 6 e 1.342 0
5 e 1 e
Solution:
The solution for the smaller root is e = 0.233. Therefore the maximum The required reaction is obtained by addition of the two formation reactions
conversion of ethylene to ethanol is written as follows:
noC2H4 nC2H4 1 1
C 2 H2 2C H2 I
0.233 23.3% 2C 2H2 C 2 H4 II
noC2H4 1
The sum of reactions (I) and (II) is the hydrogenation reaction:
C2 H2 H2 C2H4
o o
Also, G GI GII
o
39 40
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CHE553 Chemical Engineering Thermodynamics 5/13/2016
Data for both reactions (I) and (II) are given by Fig. 13.2. For 1120 oC (1393.15 The equilibrium composition of the product gas is then
K), 104/T = 7.18, the following values are read from the graph: 1 0.293 0.293
y H2 y C2H2 0.414 and y C2H4 0.172
ln KI 12.9 KI 4.0 105 2 0.293 2 0.293
ln KII 12.9 KII 2.5 10 6
On the basis of one mole initially of each reactant, eq. (13.5) gives
1 e e
y H yC H and yC H
2
2 e
2 2
2 e 2 4
Therefore, e 2 e
1
1 e
2
EXAMPLE 13.8
By eq. (13.11b),
H298
o
i i Hio
Acetic acid is esterified in the liquid phase with ethanol at 100 oC (373.15 K)
1 480000 1 285830 1 484500 1 277690 3640 J
and atmospheric pressure to produce ethyl acetate and water according to the
reaction: G 298
o
i i G io
1 332200 1 237130 1 389900 1 174780 4650 J
CH3COOH l C 2 H5OH l CH3COOC 2 H5 l H2O l
For small temperature change from 298.15 K to 373.15 K, eq. (13.15) is
If initially there is one mole each of acetic acid and ethanol, estimate the mole adequate for estimation of K. Therefore,
fraction of ethyl acetate in the reacting mixture at equilibrium.
G 298
o
4650
ln K298 1.8759 or K298 6.5266
Solution: RT 8.314 298.15
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CHE553 Chemical Engineering Thermodynamics 5/13/2016
REFERENCES
For the given reaction, eq. (13.5), with x replacing y, yields
1 e e
x AcH x EtOH x EtAc x H2O Smith, J.M., Van Ness, H.C., and Abbott, M.M. 2005. Introduction to Chemical
2 2
Engineering Thermodynamics. Seventh Edition. Mc Graw-Hill.
Because the pressure is low, eq. (13.32) is applicable. In the absence of data
for activity coefficients, assume the reacting species form an ideal solution. In http://www.chem1.com/acad/webtext/chemeq/Eq-01.html#SEC1
this case eq. (13.33) is employed, giving http://www.chem1.com/acad/webtext/thermeq/TE4.html
http://www.chem1.com/acad/webtext/thermeq/TE5.html
x EtAc x H2O
x
i
i K (13.33) K
i x AcH x EtOH
2
4.8586 e
1 e
Solution yields
e 0.6879 and xEtAc 0.6879 / 2 0.344
45 46
PREPARED BY:
MDM. NORASMAH MOHAMMED MANSHOR
FACULTY OF CHEMICAL ENGINEERING,
UiTM SHAH ALAM.
norasmah@salam.uitm.edu.my
03-55436333/019-2368303
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