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Chapter 13
The Reaction Coordinate
Application of Equilibrium Criteria to Chemical Reactions
The Standard G and the Equilibrium Constant
Effect on Temperature on the Equilibrium Constant
Evaluation of the Equilibrium Constant
Relation of Equilibrium Constant to Composition
Equilibrium Conversion for Single Reactions
Introduction
Transformation of raw materials into products having commercial use and value
is a major industry.
Raw Materials
Products
This often involves chemical reactions and subsequent separation of the products.
The rate and maximum (or equilibrium) conversion of chemical reaction are of
important concern in its commercial development.
Degree of reaction
st
With cataly
th
Wi
ou
Uultimate
conversion
t
lys
a
t
a
tc
Time
Chemical Engineering Thermodynamics II
ChE 342
12-2
ChE 342
12-3
1 A1 + 2 A2 + ........ 3 A3 + 4 A4
(I)
where |i| are stoichiometric coefficients and Ai denotes the chemical formulas of
species.
i themselves are stoichiometric numbers
Sign Convention
For products: i is positive (+)
N.B. The reaction, as written above, does not represent any mechanisms. It
represents only the overall macroscopic picture. It does not tell us what is happening
at the microscopic level.
Example:
H2O = -1
CH4 = -1
CH4 + H2O CO + 3H2
CO = +1
H2 = +3
The stoichiomertric number of an inert species is zero.
Chemical Engineering Thermodynamics II
ChE 342
12-4
In all reactions, the change in the number of moles of the species present are related to
each other through the stoichiometric number.
For example, for the reaction CH4 + H2O CO + 3H2, if 0.5 mole CH4
reacts, then 1.5 moles H2 and 0.5 mol CO generated, thats ratio of change in
number of moles to the stoichiometric number of CH4 is the same as that for H2.
Thus, in general for reaction (I), we can write:
dn 2 dn 1
=
2
1
or, in general:
dn 3 dn 1
=
3
1
, etc
dn 1 dn 2 dn 3
=
=
= ......... = d
(II)
1
2
3
where d = the amount of reaction.
It will be observed that the sign of i allows for the fact that:
ChE 342
12-5
dn i = i d
moles
dimensionless
(III)
moles
By convention, = 0 at the initial state (before the reaction occurs). Integration yields:
ni
dn i = i d
ni 0
= f(t)
n i = n i0 + i
ni
= i
n = n 0 +
where,
n0 =
ni
&
ni
+ i
The quantity tells us whether there is a net increase or decrease in the total number
of moles in the system.
The mole fraction of species i at any time, or stage of reaction, is by:
n i n i0 + i
yi =
=
n
n 0 +
Chemical Engineering Thermodynamics II
12-6
y CH 4
2-
=
8 + 2
y H 2O
yi =
1-
=
8 + 2
n i0 + i
n 0 +
yCO
1+
=
8 + 2
yH 2
4 + 3
=
8 + 2
ChE 342
12-7
Multireaction Stoichiometry
In this case, we allocate a reaction coordinate, j, to each reaction (j = 1, 2, 3, R),
where R = number of separate reactions.
The stoichiometric numbers are now identified as:
i,j
dn i =
i , j d j
(i = 1, 2, .N; j = 1, 2, . , R)
Integration yields; n i = n i0 + ( i , j j )
j
i , j
Mole fraction,
n
yi = i
n
ni = n 0 + ( i , j j ) = n 0 + ( i , j j )
i j
j i
n = n 0 + ( j j )
j
n i0 +
=
( i , j j )
n0 +
j j
(i = 1, 2, . , N)
ChE 342
12-8
Example:
(1)
(2)
j=1
j=2
There are present 2 mol CH4 and 3 mol H2O. Obtain expressions for yi = f(1, 2).
Construct the following table for i,j:
i=
j
CH4
H2O
CO
1
2
-1
-1
-1
-2
1
0
CO2
H2
0
1
3
4
j
1 = 2
2 = 2
n = n 0 + ( j j ) = 5 + 21 + 22
j
y CH 4
2 - 1 - 2
=
5 + 2 1 + 2 2
y CO 2
y H 2O
3 - 1 - 2 2
=
5 + 2 1 + 2 2
2
=
5 + 2 1 + 2 2
yH2
ChE 342
y CO
1
=
5 + 2 1 + 2 2
3 1 + 4 2
=
5 + 2 1 + 2 2
12-9
ChE 342
12-10
d ( nG ) = ( nV ) dP - ( nS ) dT + i dn i
i
dn i = i d
d ( nG ) = ( nV ) dP - ( nS ) dT + i i d
i
( nG )
At equilibrium state, according to the
[
]T , P = i i = 0.0
previous figure.
The criterion for chemical reaction equilibrium can be expressed as:
i i
= 0 .0
Since i = G i
(A)
Recall that i = i (T ) + RT ln f i
Write this equation for pure species in its standard state at the same temperature
G io = i (T ) + RT ln f i o
(B)
Chemical Engineering Thermodynamics II
ChE 342
12-11
See section 4.3 (p. 133) for the definition of standard state:
Gases: pure species in ideal gas state at 1 bar (or 1 atm)
Liquids or solids: actual pure liquid or solid at 1 bar (or 1 atm)
Subtracting (B) from (A):
i _ G io = RT ln f i / f i o= RT ln a i
ai
N.B.
the activity coefficient ( i = f i / x i f i )
o
Now, i = G i + RT ln a i & i i = 0 . 0
[ i G i0 + i RT
or
ln
( a i ) vi
or
ln a i ] = 0
=-
i G i0
[ i G i0 ] +
i
ln( a i )
RT
=0
RT
( a i ) vi = Exp[- i G i0 / RT ] = K
- RT ln K =
i G io
= G o
ChE 342
12-12
Note: For a specific species the standard state represented by G o must be the same
i
o
state represented by fi upon which the activity coefficient a i is specified
Case of Gases
The standard state is the ideal gas state of pure species at a pressure of 1 bar.
fio = 1 bar for each species in has phase reaction
f i
ai = o = f i
fi
Example:
K =
v
(f i ) i
A + 2B + 3C D + 4 E
v
(f i ) i
-1
(f A )
-2
-3
=
( f B) ( f C) ( f D) ( f E)4
K =
4
(
f
)
(
f
)
or
D
E
K =
2
3
( f A ) ( f B) ( f C)
Case of liquids and solids
The usual standard state is pure liquid or pure solid at 1 bar and T of the system.
ChE 342
f io
12-13
Ho = i Hio
CPo = i CPio
f(T) only
H
= -T
RT
( G / RT )
]P
T
H io
= - RT
d ( G io / RT )
= f(T)
dT
Why we removed
the partial derivative?
i H io = - RT 2
Chemical Engineering Thermodynamics II
d i G io
[
]
dT
RT
ChE 342
12-14
H
But,
= - RT
d G o
[
]
dT RT
ln K = - G o / RT
d ln K
dT
H o
=
RT 2
Highly important
relation
Assuming Ho is independent of T,
H o 1 1
ln( K / K 1 ) = [ - ]
R T T1
See the next slide for plot of K versus 1/T for several reactions.
ChE 342
12-15
Important Remarks:
This figure allows determination of K
at any temperature.
If K1 is known at T1 K can be
determined at any temperature for a
given Ho.
Slope of the lines are ve or +ve;
-ve for endothermic reactions
+ve for exothermic reactions
ChE 342
12-16
Determination of Go
K can be determined from the previous figure at a given temperature for certain
reactions if Ho is constant ( f(T))
Another alternative method, when Ho = f(T), for determination of K is by using:
G o
= f(T)
ln K = RT
H o
C
= H 0o + R P dT
T0 R
Recall that
Go = f(T)
Go = iGio
Ho = iHio
So = iSio
CPo/R = iGPio/R
T
or:
C
P dT
o
o
S = S0 + R
T
T0 R
Where H0o and S0o is the standard enthalpy and entropy changes at a reference
temperature T0, respectively.
Substituting in (A) gives:
Chemical Engineering Thermodynamics II
ChE 342
12-17
C
G o = H 0o + R P dT - T S 0o - RT
T0 R
C Po dT
R T
T0
According to (A):
o
o
G
0
0
S 0o =
T0
whence:
T
C Po
T
o
o
G = H 0 + R
dT - ( H 0o - G 0o ) - RT
T0
T0 R
Division by RT:
G o H 0o G 0o - H 0o 1
=
+
+
RT
RT
RT 0
T
C Po dT
R T
T0
T
C Po
C Po dT
R dT - R T
T0
T0
T
ChE 342
12-18
Example: calculate the equilibrium constant for the vapor-phase hydration of ethylene
at 145 & 320oC from data given in Appendix C
C2H4(g) + H2O(g) C2H5OH(g)
Data:
Species
C2H4(g)
H2O(g)
C2H5OH(g)
Ho298
-1 52510
-1 -241818
+1 -235100
Go298
68460
-228572
-168490
Ai
Bi 103 Ci 105
1.424 14.394 - 4.392
3.47
1.45
----3.518 20.001 - 6.002
where Cpi/R = Ai + Bi T + Ci T2
o
H 298
=
ChE 342
12-19
@ T = 145oC = 418 K:
G o
- 45792
- 8378 + 45792
1
=
+
+
RT
(8 . 314 )( 418 )
(8 . 314 )( 298 )
418
418
298
418
298
G o
@T=
= 418 K:
= 1 .936
RT
o
G
K = exp(-1.936) = 0.1443
ln K =
RT
dT
T
145oC
K = 0.00294
ChE 342
K with T
Exothermic rxn
12-20
K = f(T) only
& f i = f (T , P , y i )
Reflects nonideality of the equilibrium mixture
This means that for a given T, the composition at eqm must change
f i = i y i P K = i ( i y i P ) i
Separate P term, K = i ( i y i ) i [ P ]
Or,
K P - = i ( i y i ) i
where = i
ChE 342
12-21
Special cases:
For equilibrium mixture as an ideal solution
-
whence, K P = i ( i y i )
i = i
i = 1
whence,
K P = i ( y i )
Conclusion remarks
- Dependence of T can be seen through K:
If Ho +ve, ENDO rxn, K with T (yi)i for a fixed P e
rxn shifts to the right
If Ho -ve, EXO rxn,
K with T (yi)i for a fixed P e
rxn shifts to the left
- If (i) -ve, P @ constant T (yi)i rxn shifts to the right, e
If (i) +ve, P @ constant T (yi)i rxn shifts to the left, e
Chemical Engineering Thermodynamics II
ChE 342
12-22
n0 = 2 mol
& = 0.0
From Fig. 13.2: @ 1/T = 1/(1100 K) = 9.09 10-4 for the above rxn lnK = 0 or K = 1.0
=1
K (1) = i ( y i ) = 1
y CO y H 2
=1
y CO y H 2 O
1-
y H 2 = e , y H 2O =
2
2
0 + e e
1-
= ,
y CO =
,
2+0
2
2
2
e
Substituting:
= 1 e = 0.5 fraction of steam reacts = 0.5
2
4 (1 - e ) / 4
y CO 2 =
12-23
n0 = 3 mol
y CO 2
e
= ,
3
y CO
1-
=
,
3
yH2
e
= ,
3
y H 2O
1-
=
3
e2
Substituting:
= 1 e = 0.667 fraction of steam reacts = 0.667/2 = 0.33
( 2 - e )(1 - e )
(e) n0,H2O = 1, n0, CO = 2 mol, T = 1100 K, P = 1 bar
n0 = 3 mol
y CO 2
e
= ,
2
y CO
e
2-
=
, yH2 = ,
3
3
y H 2O
1-
=
3
e2
Substituting:
= 1 e = 0.667 fraction of steam reacts = 0.667
( 2 - e )(1 - e )
1
e
y H 2 = , y H 2O =
n0 = 3 mol
,
y CO 2 =
, y CO =
3
3
3
3
e (1 + e )
Substituting:
= 1 e = 0.0.33 fraction of steam reacts = 0.33
(1 - e ) 2
e2
2 = 0 . 316
(1 - e )
e = 0.36
ChE 342
12-24
Liquid-Phase Reactions
fi
fi
Then K remains as K = ( ai ) vi
For liquid:
f i = i x i f i
where fio 0
ai
Determination of fi/fio:
fi
fi
= o = i x i o
fi
fi
@ T and P: G i = i (T ) + RT ln f i
o
o
@ T and Po: G i = i (T ) + RT ln f i
Subtracting: G i - G io = RT ln f i / f i o
But:
dG i = Vi dP - S i dT
o
Integration at constant T from Po to P: G i - G i =
Substitute (B) in (A): RT ln
fi
o =
fi
Vi dP
(A)
P
Vi dP
(B)
Po
fi
For liquids Vi is weak function of P upon integration RT ln o = V i ( P - P o )
fi
fi
o
or
o = exp[ V i ( P - P ) / RT ]
fi
Chemical Engineering Thermodynamics II
Po
ChE 342
12-25
a i = i x i exp[ Vi ( P - P o ) / RT ]
and K = [ i x i exp{ Vi ( P - P o ) / RT }] i
Vi ( P - P o )
= ( i x i ) i [ e RT ]i
Vi i ( P - P o )
i
= ( i x i ) e RT
o
(
)
V
P
P
i
i
iVi ]
K = [ ( i x i ) ] exp[
RT
i
Special cases
At low P: exp[{Vi(P-Po)/RT}{iVi}] 1.0
K = ( i x i ) i
i
K = ( x i ) i
i
xi = f(e)
Chemical Engineering Thermodynamics II
ChE 342
12-26
Example: Esterification of acetic acid in the liquid phase at 100oC and 1 atm:
CH3COOH(l) + C2H5OH(l) CH3COOC2H5(l) + H2O(l)
Species i
Hof298 (J)
Gof298 (J)
CH3COOH(l), i=1
C2H5OH(l), i=2
CH3COOC2H5(l), i=3
H2O(l), i=4
-1
-1
+1
+1
-484,500
-277690
-480,000
-285,830
-389,900
-174,780
-332,200
-273,129
K = ( x i ) i
i
First, determine K:
i H io, 298
= i G io, 298
o
H 298
=
o
G 298
lnK = -Go/RT
Chemical Engineering Thermodynamics II
K298 = exp[-4650/(8.314)(298)]
ChE 342
K298 = 6.527
12-27
H o 1 1
ln( K / K 1 ) = [ - ]
R T T1
1
3640 1
]
[
8 . 314 373 298
K373 = 4.859
Now:
x 4 x3
K =
x1 x 2
K = 4.859,
n0 = 2, = 0
1 - e
1 - e
n0 i + i e
x
=
,
x1 =
,
2
xi =
2
2
n0
e2 / 4
= 4 . 859 e = 0.6879
2
(1 - e ) / 4
x3 =
e
,
2
x4 =
e
,
2
x3 = 0.344
(see other examples in the textbook)
ChE 342
12-28