Chemical Engineering Thermodynamics

CPLMlCAL 8LAC1lCn LCulLl88luM

Mohammad Fadil Abdul Wahab
CuLcomes for 1hls ChapLer
a) 1o dene whaL ls exLend of reacuon and relaLe lL Lo Lhe
mole fracuon (composluon)
b) 1o derlve Lhe equlllbrlum crlLerla for chemlcal reacuon
c) use b) Lo derlve equlllbrlum consLanL (k) and able Lo
calculaLe k
d) 1o relaLe k Lo fugaclLy and mole fracuon and able Lo
calculaLe Lhe equlllbrlum converslon for gas phase
reacuon
e) Analyze Lhe eecL of 1 and on k and equlllbrlum
composluon endoLhermlc and exoLhermlc reacuons
Commerclal Chemlcal-8eacuon
1. Chemical reaction is the heart of chemical processes.
2. Take place in a reactor.
3. A value-added process.
Transform raw materials into products of greater value.
Economic potential or Gross Profit must be positive.
i.e. Main products have a higher price than
the raw materials (reactants).
Gross Profit is based solely on price of reactants and
products , excluding the equipment and operating costs.
SLudy of Chemlcal-8eacuon
2. Chemical Reaction Equilibrium
Determination of maximum possible conversion
in a chemical reaction.
This chapter will cover this part.
1. Reaction Kinetics
The study of rates of reaction
i.e. How fast is the reaction?
You will learn this in your Chemical Reaction Engineering
class.
8eacuon klneucs vs Converslon
1. Both reaction kinetics and equilibrium conversion
are function of T, P and composition
3. So both kinetics and equilibrium conversion must
be considered for optimum reactor design.
2. Example: Exothermic reaction,
An increase in reaction T
will increase in rates of reaction
but decreases the conversion.

Overall Conversion

=
reactant input to process - reactant output from process
reactant input to process
x100
Note:

Single-Pass Conversion
=
reactant input to reactor - reactant output from reactor
reactant input to reactor
x100
lrreverslble 8eacuons
Single direction (from reactants to products).
i.e. forward reaction only.
These reactions highly favor formation of the products.
L + R P + S
Only an extremely small quantity of limiting
reactants (if any) remains in the system at equilibrium.
Usually 100% single-pass conversion (of limiting reactant)
is considered.
8everslble 8eacuons
Appreciable quantities of all reactants and products
species can coexist at equilibrium.
Hence the extent of reaction (also conversion)
is limited by the chemical equilibrium.
A + B C + D
Forward and reverse reactions.
Eventually equilibrium is reached where rate of forward
reaction is equal to rate of reverse reaction
SLolchlomeLrlc Lquauon

!
1
A
1
+ !
2
A
2
" !
3
A
3
+ !
4
A
4

!
1
,!
2
are stoic. coefficients of reactant ( - value)
!
3
,!
4
are stoic. coefficients of product ( + value)
A
1
, A
2
, A
3
, A
4
are molecules or atoms

Example,
CH
4
+ 2O
2
!CO
2
+ 2H
2
O
"
CH4
= #1, "
O2
= #2
"
CO2
= 1, "
H2O
= 2
8eacuon CoordlnaLe (c)
For a reaction, the changes in the number
of moles (n
i
) of the species present in the reaction chamber
are in direct proportion to the stoichiometric numbers (v
i
).

dn
1
!
1
=
dn
2
!
2
=
dn
3
!
3
=
dn
4
!
4
=
dn
i
!
i
= d"
dn
i
= !
i
d" .....(13.3)
Lxample

CH
4
+ 2O
2
!CO
2
+ 2H
2
O
The following reaction consumes 10 mols of methane,

d! =
dn
CH4
"
CH4
=
#10
#1
= 10,
dn
O2
"
O2
=
#20
#2
= 10,

=
dn
CO2
!
CO2
=
10
1
= 10,
dn
H2O
!
H2O
=
20
2
= 10
Reaction coordinate (!) characterizes the extent
or degree to which a reaction has taken place.
Also known as,
the extent of reaction (as used in Felder and Rousseau),
progress variable,
degree of advancement,
degree of reaction.
lor Slngle 8eacuon
For species i, integrate eqn 13.3 from initial state (!=0)
to a state where ! = ! , so

dn
i
n
io
n
i
!
= "
i
d#
0
#
!
n
i
$ n
io
= "
i
(# $ 0)
n
i
= n
io
+"
i
#

n
i
!
= n = n
io
!
+ " #
i
!
= n
o
+#"
Summation over all species,
Note: At initial state prior to reaction, ! = 0

So mole fraction of species i,

y
i
or x
i
=
n
i
n
=
n
io
+!
i
"
n
o
+!"
.......... mole fraction of species i is a function of "
Lxample
Initial composition (prior to rxn):
2 mol CH
4
, 1 mol H
2
O, 1 mol CO and 4 mol H
2
.
Express y
i
as functions of !.

n
o
= n
io
!
= 2 +1+1+ 4 = 8
" = "
i
!
= 1+ 3#1#1 = 2

CH
4
+H
2
O!CO +3H
2

y
i
=
n
io
+!
i
"
n
o
+!"

y
CH4
=
2 ! "
8 + 2"
y
H2O
=
1! "
8 + 2"
y
CO
=
1+ "
8 + 2"
y
H2
=
4 + 3"
8 + 2"
lor Muluple 8eacuons
For species i and reaction j, we integrate from initial
state (!=0) to a state where !
j
= !
j
, so

n
i
! n
io
= "
ij
(#
j
! 0)
j
$
n
i
= n
io
+ "
ij
#
j
j
$

n
i
i
!
= n = n
io
i
!
+ "
ij
#
j
j
!
i
!
Summation over all species (i),

dn
i
= !
ij
d"
j
j
#

So mole fraction of species i,
y
i
or x
i
=
n
i
n
=
n
io
+ !
ij
"
j
j
#
n
io
i
#
+ !
ij
"
j
j
#
i
#
Example of multiple rxns,

Main reaction,
C
2
H
6
!C
2
H
4
+ H
2
Side reactions,
C
2
H
6
+ H
2
!2CH
4
C
2
H
4
+ C
2
H
6
!C
3
H
6
+ CH
4

Yield
=
moles of desired product formed
moles that would have been formed if there were no side reactions and
the limiting reactant had reacted completely

Selectivity
=
moles of desired product formed
moles of undesired product formed
Also for multiple reactions,
CrlLerla of Chem 8xn Lqulllbrlum
From FPR for homogenous system of variable composition,

d(nG) = (nV)dP ! (nS)dT +
i
dn
i
i
"
(11.2)
For system with single chemical reaction,
substitute eqn 13.3,

d(nG) = (nV)dP ! (nS)dT + "
i

i
d#
i
$
Apply the criterion of exactness,

d(nG)
d!
"
#
$
%
&
'
T , P
= (
i

i
i
)
Using 1st law, 2nd Law and FPR, we could show that at
equilibrium (see chapter 14 and next slide),

(dnG)
T , P
= 0 (14.68)
So, at chemical rxn equilibrium,
Hence,

d(nG)
d!
"
#
$
%
&
'
T , P
= 0

!
i

i
i
"
= 0 (13.8)
This is the criteria of
Chemical Rxn Equilibrium
All irreversible process occurring at constant T & P proceed in
such a direction as to cause a decrease in the Gibbs energy
of the system.
As derived previously (eqn 11.8, 11.46),

d
i
= dG
i
= RTd ln

f
i
(contant T)
Integrate from standard state of pure species i
to a state of species i in a solution (at equilibrium T),
Substitute into the criteria of chem rxn equilibrium (eqn 13.8),

!
i

i
i
"
= !
i
(G
i
o
+ RT ln

f
i
f
i
o
)
i
"
= !
i
G
i
o
i
"
+ RT ln

f
i
f
i
o
#
$
%
&
'
(
!
i
i
"
= 0

i
! G
i
o
= RT ln

f
i
f
i
o
(contant T)

i
= G
i
o
+ RT ln

f
i
f
i
o
Rearrange:

!
i
G
i
o
i
"
+ RT ln

f
i
f
i
o
#
$
%
&
'
(
!
i
i
"
= !
i
G
i
o
i
"
+ RT ln

f
i
f
i
o
#
$
%
&
'
(
!
i
i
)
= 0

i
!
signifies the product over all species i.
e.g. "
i =5
a
i
= a
1
a
2
a
3
a
4
a
5
.


Let

f
i
f
i
o
!
"
#
$
%
&
'
i
i
(
= K (13.10)
K is known as equilibrium constant.

So,

!
i
G
i
o
i
"
+ RT ln K = 0
ln K =
# !
i
G
i
o
i
"
RT
=
#$G
o
RT


where,
!
i
G
i
o
i
"
= #G
o
(13.12)
= The Std Gibbs Energy Change of Rxn at equi T
The data for G
i
o
is available in the form of "G
o
f,i,298

See Table C.4 pg 686

!G
o
= "
i
G
i
o
i
#
= "
H2
G
H2
o
+"
CO
G
CO
o
+"
CH4
G
CH4
o
+"
H2O
G
H2O
o

Calculate "G
o

at 298K,

CH
4
+H
2
O(g) !CO +3H
2
EXAMPLE

= !
H2
"G
f , H2,298
o
+!
CO
"G
f ,CO,298
o
+!
CH4
"G
f ,CH4,298
o
+!
H2O
"G
f , H2O,298
o
=3(0) + 1(-137169) + (-1)(-50460) + (-1)(-228572)
=141863 Joules/mol CH
4
reacted #

ln K =
!"G
o
RT
(13.11b)
K = exp
!"G
o
RT
#
$
%
&
'
(
(13.11a)

for T=T
0
K
0
= exp
!"G
0
o
RT
0
#
$
%
&
'
(
(13.21)
Note: Data for standard state is
usually available at T
0
=298.15K
or 25
o
C and P
o
=1 bar
LecL of 1 on k
To calculate K at T other than the standard state T
of 298K. Lets use van Hoffs eqn,

d ln K =
!H
o
RT
2
dT (13.14)

If !H
o
(std heat of rxn) could be assumed CONSTANT,
integration gives,
ln
K
K
'
= "
!H
o
R
1
T
"
1
T
'
#
$
%
&
'
(
(13.15)

K = K
'
exp !
"H
o
R
1
T
!
1
T
'
#
$
%
&
'
(
)
*
+
,
-
.

Let's use "H
o
= "H
0
o
and T
'
= T
o
We could rearrange,

K = K
0
exp !
"H
0
o
R
1
T
!
1
T
0
#
$
%
&
'
(
)
*
+
+
,
-
.
.
= K
0
exp
"H
0
o
RT
0
1!
T
0
T
#
$
%
&
'
(
)
*
+
+
,
-
.
.
= K
0
K
1

where,
K
1
= exp
!H
0
o
RT
0
1"
T
0
T
#
$
%
&
'
(
#
$
%
&
'
(
(13.22)

Eqn (13.15) can also be written as,
ln K = !
"H
o
R
1
T
+
"H
o
R
1
T
'
+ ln K'
#
$
%
&
'
(
(13.15a)
Exothermic reaction, slope positive,
(K decrease with increasing T)
Endothermic reaction, slope negative,
(K increase with increasing T)

!
"H
o
R
= slope

ln
K
K
'
= !
"H
o
R
1
T
!
1
T
'
#
$
%
&
'
(


Plot of ln K vs
1
T
is a straightline as shown
in Figure 13.2.

If !H
o
could not be assumed constant,
K = K
0
K
1
K
2

Note: Data for standard state is
usually available at T
0
=298.15K
or 25
o
C and P
o
=1 bar

where, ! =
T
T
0
For heat capacity constant, "A = #
i
A
i
i
$
etc.

where,
K
0
= exp
!"G
0
o
RT
0
#
$
%
&
'
(
K
1
= exp
"H
0
o
RT
0
1!
T
0
T
#
$
%
&
'
(
#
$
%
&
'
(

K
2
= exp
!A[ln" # (
" #1
"
)] +
1
2
!BT
0
(" #1)
2
"
+

1
6
!CT
0
2
(" #1)
2
(" + 2)
"
+
1
2
!D
T
0
2
(" #1)
2
"
2
$
%
&
&
'
&
&
(
)
&
&
*
&
&
(13.24)
8elauon of ! Lo equlllbrlum
composluon ("
#
)
Gas-Phase Reactions.
From definition of K,

K =

f
i
f
i
o
!
"
#
$
%
&
'
i
i
(
Let the standard state be the ideal-gas state of
pure species i at P
o
(= 1 bar).

K =

f
i
P
o
!
"
#
$
%
&
'
i
i
(
=

)
i
y
i
P
P
o
!
"
#
$
%
&
'
i
i
(
=
P
P
o
!
"
#
$
%
&
'
i *

)
i
y
i
( )
'
i
i
(

also !
i
"
= !
K =
P
P
o
#
$
%
&
'
(
!

)
i
y
i
( )
!
i
i
*

so

!
i
y
i
( )
"
i
i
#
=
P
P
o
$
%
&
'
(
)
*"
K (13.26)

If the mixture is an ideal mixture,
y
i
!
i
( )
"
i
i
#
=
P
P
o
$
%
&
'
(
)
*"
K (13.27)

If the mixture is an ideal mixture at low pressure,
it becomes an ideal-gas mixture, so
y
i
( )
!
i
i
"
=
P
P
o
#
$
%
&
'
(
)!
K (13.28)

Remember, we can express y
i
in terms of !,
For single rxn,
y
i
=
n
io
+ !"
i
n
io
#
+ ! "
i
#

For multiple rxns,
y
i
=
n
io
+ !
ij
"
j
j
#
n
io
i
#
+ !
ij
"
j
j
#
i
#
LecL of 1 and on Lqulllbrlum
Converslon
Consider an ideal gas reaction,

y
i
( )
!
i
i
"
=
P
P
o
#
$
%
&
'
(
)!
K (13.28)

ln K = !
"H
o
R
1
T
+
"H
o
R
1
T
'
+ ln K'
#
$
%
&
'
(
And eqn 13.15a gives the
relation of K wrt. T,
Effect of TEMPERATURE
For endothermic rxn, an
increase in T will result in
an increase in K,
therefore an increase in,

y
i
( )
!
i
i
"
=
y
c
!
c
y
d
!
d
y
a
|!
a
|
y
b
|!
b
|

y
i
( )
!
i
i
"
=
P
P
o
#
$
%
&
'
(
)!
K
The composition or fraction
of products will be higher.
An increase in !
e.
Shift of rxn to the right.
Higher equilibrium conversion.
Effect of TEMPERATURE
For exothermic rxn, an increase
in T will result in a decrease in
K, therefore a decrease in,

y
i
( )
!
i
i
"
=
P
P
o
#
$
%
&
'
(
)!
K

y
i
( )
!
i
i
"
=
y
c
!
c
y
d
!
d
y
a
|!
a
|
y
b
|!
b
|
The composition or fraction
of products will be reduced.
A decrease in !
e.
Shift of rxn to the left.
Lower equilibrium conversion.
Effect of PRESSURE
If ! is negative* value, an
increase in P (at constant T)
causes an increase in,

y
i
( )
!
i
i
"
=
P
P
o
#
$
%
&
'
(
)!
K

y
i
( )
!
i
i
"
=
y
c
V
c
y
d
V
d
y
a
|V
a
|
y
b
|V
b
|
The composition or fraction
of products will be higher.
An increase in !
e.
Shift of rxn to the right.
Higher equilibrium conversion.
*reduction in mole number
Effect of PRESSURE
If ! is positive* value, an
increase in P (at constant T)
will result in a decrease in,

y
i
( )
!
i
i
"
=
P
P
o
#
$
%
&
'
(
)!
K

y
i
( )
!
i
i
"
=
y
c
V
c
y
d
V
d
y
a
|V
a
|
y
b
|V
b
|
The composition or fraction
of products will be reduced.
A decrease in !
e.
Shift of rxn to the left.
Lower equilibrium conversion.
*increase in mole number
8elauon of ! Lo equlllbrlum
composluon (x
l
)
Liquid-Phase Reactions.
From definition of K,

K =

f
i
f
i
o
!
"
#
$
%
&
'
i
i
(
Let the std state be the pure liquid of
species i at the system temperature and 1 bar.
Substitute eqn 11.90,

K =
!
i
x
i
f
i
f
i
o
"
#
$
%
&
'
(
i
i
)
To find in term of measured variable,

G
i
= !
i
(T) + RT ln f
i
(11.31)
Apply at T and std state pressure of P=1 bar,

f
i
f
i
o

G
i
o
= !
i
(T) + RT ln f
i
o

The difference,
G
i
" G
i
o
= RT ln
f
i
f
i
o

From FPR,

dG = VdP ! SdT at constant T
Integrate at constant T for pure liquid i from P
o
to P,
G
i
! G
i
o
= V
i
dP
P
o
P
"


Combine ,
RT ln
f
i
f
i
o
= V
i
dP
P
o
P
!

For V
i
=V
i
liq
" constant
RT ln
f
i
f
i
o
= V
i
(P # P
o
)
So,

ln
f
i
f
i
o
=
V
i
(P ! P
o
)
RT

f
i
f
i
o
=exp
V
i
(P ! P
o
)
RT
"
#
$
%
&
'

K =
!
i
x
i
f
i
f
i
o
"
#
$
%
&
'
(
i
i
)
= !
i
x
i
exp
V
i
(P * P
o
)
RT
"
#
$
%
&
'
"
#
$
%
&
'
(
i
i
)
= (!
i
x
i
)
(
i
exp
(
i
V
i
(P * P
o
)
RT
"
#
$
%
&
'
i
)
= exp
(P * P
o
)
RT
((
i
V
i
i
+
)
"
#
$
%
&
'
(!
i
x
i
)
(
i
i
)
So,
Substitute and rearrange,

(!
i
x
i
)
"
i
i
#
= Kexp
(P
0
$ P)
RT
("
i
V
i
i
%
)
&
'
(
)
*
+
(13.31)
The exponent term is usually 1, except for high
pressure system, so,

(!
i
x
i
)
"
i
i
#
= K (13.32)
For ideal liquid solution,

(x
i
)
!
i
i
"
= K (13.33) Known as the law of mass action
As shown earlier, x
i
can be written in term of !
Lxerclse
CalculaLe k ln Lxample 13.3a and for
equlllbrlum reacuon, deLermlne Lhe fracuonal
converslon of sLeam.
lracuonal converslon of sLeam
= c / (lnlual mol of sLeam)
1hank ?ou