Chapter 13
Chapter 13
Chapter 13
Commercial
Chemical-ReacCon
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.
Study
of
Chemical-ReacCon
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.
Note:
Overall Conversion
reactant input to process - reactant output from process
=
x100
reactant input to process
Single-Pass Conversion
Irreversible
ReacCons
Single direction (from reactants to products).
i.e. forward reaction only.
These reactions highly favor formation of the products.
L
Reversible
ReacCons
Forward and reverse reactions.
Eventually equilibrium is reached where rate of forward
reaction is equal to rate of reverse reaction
A
Stoichiometric
EquaCon
1 A1 + 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)
A1 , A 2 , A 3 , A 4 are molecules or atoms
Example,
CH 4 + 2O2 CO2 + 2H 2O
CH4 = 1, O2 = 2
CO2 = 1,
H2O = 2
ReacCon
Coordinate
()
For a reaction, the changes in the number "
of moles (ni) of the species present in the reaction chamber"
are in direct proportion to the stoichiometric numbers (vi)."
.....(13.3)
Example
The following reaction consumes 10 mols of methane,
CH 4 + 2O2 CO2 + 2H 2O
d =
dnCH 4
CH 4
10
=
= 10,
1
dnCO2 10
=
=
= 10,
CO2
1
dnO2
O2
20
=
= 10,
2
dnH 2O 20
=
= 10
H 2O
2
nio
dni = i d
ni nio = i ( 0)
ni = nio + i
Note: At initial state prior to reaction,
=0
ni = n = nio + i
= no +
yi or xi =
ni
=
n
nio + i
no +
Example
CH 4 +H 2O CO +3H 2
Initial composition (prior to rxn):
2 mol CH4, 1 mol H2O, 1 mol CO and 4 mol H2.
Express yi as functions of .
yi =
yCH 4
nio = 2 + 1 + 1 + 4 = 8
= i = 1 + 3 1 1 = 2
nio + i
no =
no +
2
=
8 + 2
y H 2O
1
=
8 + 2
yCO
1+
=
8 + 2
yH 2
4 + 3
=
8 + 2
ni nio = ij ( j 0)
j
ni = nio + ij j
j
ni = n = nio + ij j
i
yi or xi
ni
=
=
n
nio + ij j
j
nio + ij j
i
Main reaction,
C2 H 6 C2 H 4 + H 2
Side reactions,
C2 H 6 + H 2 2CH 4
C2 H 4 + C2 H 6 C3 H 6 + CH 4
Selectivity
(11.2)
T , P
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)
T , P
Hence,
i i = 0
i
(contant T)
f
i Gio = RT ln io
(contant T)
fi
fi
o
i = Gi + RT ln o
fi
Substitute into the criteria of chem rxn equilibrium (eqn 13.8),
fi
i i = i (G + RT ln f o ) = iG + RT ln f o = 0
i
i
i
i
i
i
o
i
fi
o
i
Rearrange:
fi
o
iGi + RT ln o
i
i
fi
fi
o
= iGi + RT ln o
i fi
i
e.g.
Let
ai = a1a2 a3a4 a5 .
i=5
fi
f o
i i
=K
(13.10)
=0
So,
G
i i + RT ln K = 0
i
ln K =
iGio
i
RT
G o
=
RT
where,
iGio = G o
(13.12)
EXAMPLE
CH 4 +H 2O(g) CO +3H 2
Calculate Go at 298K,
G o =
G
i i
i
o
o
o
= H 2GHo 2 + CO GCO
+ CH 4GCH
+
G
4
H 2O H 2O
G o
ln K =
RT
(13.11b)
G o
K = exp
RT
(13.11a)
for T=T0
K0
G0o
= exp
RT0
(13.21)
Eect
of
T
on
K
To calculate K at T other than the standard state T
of 298K. Lets use van Hoffs eqn,
H o
d ln K =
dT
2
RT
(13.14)
R T T
K
(13.15)
We could rearrange,
1 1
H
'
K = K exp
'
R T T
T
RT0
R T T0
= K 0 K1
where,
H 0o T0
K1 = exp
1
T
RT0
(13.22)
K
H o 1 1
ln ' =
'
R T T
K
Eqn (13.15) can also be written as,
H o 1 H o 1
ln K =
+
+ ln K '
'
R T R T
1
Plot of ln K vs
is a straightline as shown
T
in Figure 13.2.
(13.15a)
H o
= slope
R
where,
G0o
K 0 = exp
RT
H 0o T0
K1 = exp
1
T
RT0
1
1
( 1)2
)] + BT0
+
A[ln (
K 2 = exp
2
2
1
(
1)
(
+
2)
1
D
(
1)
CT02
+
2 T02 2
where,
T
T0
(13.24)
RelaCon
of
K
to
equilibrium
composiCon
(yi)
Gas-Phase Reactions.
From definition of K,
fi
K = o
i fi
i yi P
= o
i P
P
= o
P
(
i
i yi
i =
also
P
K = o
P
(
i
i yi
so
(
i
i yi
P
= o
P
(13.26)
( yii )
P
= o
P
(13.27)
( yi )
P
= o
P
(13.28)
nio + ij j
j
nio + ij j
i
( yi )
P
= o
P
(13.28)
H o 1 H o 1
ln K =
+
+ ln K '
'
R T R T
Effect of TEMPERATURE
( yi )
( yi )
yc c y d d
| |
| |
y a a yb b
P
= o
P
Effect of TEMPERATURE
For exothermic rxn, an increase
in T will result in a decrease in
K, therefore a decrease in,
( yi )
yc c y d d
| |
| |
y a a yb b
( yi )
P
= o
P
Effect of PRESSURE
( yi )
If is negative* value, an
increase in P (at constant T)
causes an increase in,
V V
yc y d
( yi ) = |V | |V |
y a yb
i
c
P
= o
P
Effect of PRESSURE
( yi )
If is positive* value, an
increase in P (at constant T)
will result in a decrease in,
( yi )
yc c y d d
|V |
|V |
y a a yb b
P
= o
P
RelaCon
of
K
to
equilibrium
composiCon
(xi)
Liquid-Phase Reactions.
From definition of K,
f
K = io
i fi
To find
fi
fi
Gi = i (T ) + RT ln f i
(11.31)
Gio = i (T ) + RT ln f i o
The difference,
Gi G = RT ln
o
i
fi
fi o
From FPR,
dG = VdP SdT
at constant T
Vi dP
Gi Gio =
Po
Combine ,
RT ln
fi
fi
Vi dP
Po
RT ln
fi
fi o
= Vi (P P o )
So,
Vi (P P o )
ln o =
RT
fi
fi
Vi (P P o )
=exp
o
RT
fi
fi
i xi f i
Vi (P P )
K =
= i xiexp
o
RT
f
i
i
i
o
o
o
V
(P
P
)
(P
P
)
i
i
i i
= ( i xi ) exp
=
exp
(
V
)
(
x
)
RT i i i i
RT
i
i
i
So,
(P0 P)
( i xi ) = Kexp RT ( iVi )
i
i
i
(13.31)
( i xi ) i = K
(13.32)
(xi ) i = K
Exercise
Calculate
K
in
Example
13.5a
and
for
equilibrium
reacCon,
determine
the
fracConal
conversion
of
steam.
FracConal
conversion
of
steam
=
/
(iniCal
mol
of
steam)
Thank You