Problem 1 (35 points)

The gas-phase, irreversible, exothermic reaction A ! B proceeds in a adiabatic PFR.

This is an elementary reaction. The feed to the reactor is comprised of A and inert I at
inlet temperature T0. No B is present in the feed. The reactor will be run adiabatically,
but the maximum allowed temperature due to safety considerations is Tmax.
Reactor and reaction information that you are given:
T0: Feed inlet temperature
Tmax: Maximum allowed temperature due to safety concerns
yA: mole fraction of A in the feed.
"HRx: Heat of reaction per mole A. Assume to be independent of temperature.
CpA: Specic heat capacity of A. Assume to be independent of temperature.
CpB: Specic heat capacity of B. Assume to be independent of temperature.
CpI: Specic heat capacity of I. Assume to be independent of temperature.
k(T) = (# + $(T-%)): Reaction rate constant as a function of temperature.
Part A (10 points):
Find the maximum conversion (XAf) possible in this reactor using the only the variables
given in the problem statement.
To get the maximum conversion, you need to run the reactor at Tmax.
Part B (25 points):
Find the residence time of the PFR. You may leave your answer in integral form (if
applicable), but it must contain only variables given in the problem statement other than
the variable of integration.
The residence time of a PFR is:
Need to write k and T as a function of XA. T is already written as a function of
conversion from above.
T = T
0

H
Rx
X
A

i
c
pi
T
max
= T
0

H
Rx
X
Af
c
pA
+
1y
A
y
A
c
pI
X
Af
= (T
max
T
0
)
c
pA
+
1y
A
y
A
c
pI
H
Rx
= C
A0

X
Af
0
dX
A
r
A
= c
A0

X
Af
0
dX
A
kC
A0
(1 X
A
)
T
0
T
Substitute into the integral equation.
k(X
A
) = + (T ) = +

T
0

H
Rx
X
A
c
pA
+
1y
A
y
A
c
pI

X
Af
0
dX
A

T
0

H
Rx
X
A
c
pA
+
1y
A
y
A
c
pI

T
0

H
Rx
X
A
c
pA
+
1y
A
y
A
c
pI

(1 X
A
)T
0
T(X
A
) = T
0

H
Rx
X
A
c
pA
+
1y
A
y
A
c
pI



3)

What is the rate of methanol formation, if Step 2 is Quasi-equilibrated.

In the solution [*] = [S] (catalyst active site)

L
OH
CH k rate
OH CH
*] [
*] [
3 3
3
=
QE assumption of Step 2:

0 *] *][ [ ][*] [
*] [
3 2
2
4 2
3
= ! = H CH k CH k
dt
CH d
r f

4
2
4
2
2
4
2
2
2
4 2
3
] [
][*] [
*] [
][*] [
*] [
][*] [
*] [
K
H
CH
K
H
CH
K
H k
CH k
CH
r
f
= = =
QE of Step 1 and Step 4 gives us [H*] and [OH*]:
4
2
2
][*] [
*] [
K
H
H =
4
2
2 1
4
2
2
2 1
2
2 1
] [
][*] [
[*]
] [
][*] [
*] [
][*] [
*] [
K
H
O H K
K
H
O H K
H
O H K
OH = = =

Then, we perform an overall site balance
*] [ *] [ *] [ [*] ] [
3
OH H CH L + + + =

4
2
2 1
4
2
4
2
4
2
] [
][*] [
[*]
] [
] [
][*] [
*
K
H
O H K
K
H
K
H
CH
K L + + + =
2
4
2
2 1
4
2
4
2
4
2 2
2 4 4 2 1 3
2
4
2
2 1
4
2
4
2
4
2
4
2
2 1
4
2
4
2 3
4
2
2 1
4
2
4
2 3 3 3
)
] [
] [ ] [
] [
] [
1 ]( [
] ][ [
)
] [
] [ ] [
] [
] [
1 (
)
] [
] [
)(
] [
] [
(
)
] [
][*] [
)(
] [
][*] [
(
*] [
*] [
3
3
K
H
O H K
K
H
K
H
CH
K H
L O H CH K K K k
rate
K
H
O H K
K
H
K
H
CH
K
L
K
H
O H K
K
H
CH
K k
K
H
O H K
K
H
CH
K k
L
OH
CH k rate
OH CH
OH CH
+ + +
=
+ + +
= = =


b) Draw an arrow diagram to show the relative rates of the each forward and reverse
step in the mechanism above.

The arrow diagram needs to show that

4
4 4
3
3
2
2 2
1
1 1
! ! ! !
" " "
"
= =
"
=
" r r r r r r r

1
4 3 2 1
= = = = ! ! ! !


r
2
r
-2
r
3
r
1
r
-1
r
4
r
-4
r
2
r
-2
r
3
r
1
r
-1
r
4
r
-4




c) Derive the rate of methanol formation without the assumption that Step 2 is quasi-
equilibrated.

L
OH
CH k rate
OH CH
*] [
*] [
3 3
3
=
Here, we find *] [
3
CH using PSSH:
0
] [
*] [
*] [
] [
*] [
*] [
] [
[*]
] [
*] [
3 3 3 2
2
4 2
3
= ! ! =
L
OH
CH k
L
H
CH k
L
CH k
dt
CH d
r f


*] [ *] [
][*] [
*] [
3 2
2
4 2
3
OH k H k
CH k
CH
r
f
+
=

All other absorbed species were derived from QE assumptions (from part A)
4
2
2
][*] [
*] [
K
H
H =
4
2
2 1
4
2
2
2 1
2
2 1
] [
][*] [
[*]
] [
][*] [
*] [
][*] [
*] [
K
H
O H K
K
H
O H K
H
O H K
OH = = =

Substituting into the *] [
3
CH expression yield:

4
2
2 1
3
4
2
2
4 2
4
2
2 1
3
4
2
2
2
2
4 2
3
] [
] [ ] [
][*] [
] [
][*] [ ][*] [
][*] [
*] [
K
H
O H K
k
K
H
k
CH k
K
H
O H K
k
K
H
k
CH k
CH
r
f
r
f
+
=
+
=


)
] [
][*] [
)(
] [
] [ ] [
][*] [
( *] *][ [
4
2
2 1
4
2
2 1
3
4
2
2
4 2
3 3 3
3
K
H
O H K
K
H
O H K
k
K
H
k
CH k
k OH CH k rate
r
f
OH CH
+
= =
Overall Site Balance (Note: same with Part A, except for the *] [
3
CH expression):

*] [ *] [ *] [ [*] ] [
3
OH H CH L + + + =

4
2
2 1
4
2
4
2
2 1
3
4
2
2
4 2
] [
][*] [
[*]
] [
] [
] [ ] [
][*] [
[*] ] [
K
H
O H K
K
H
K
H
O H K
k
K
H
k
CH k
L
r
f
+ +
+
+ =


2
4
2
2 1
4
2
5
2
2 1
3
4
2
2
4 2
4
2
2 1
4
2
2 1
3
4
2
2
4 2
3
3 3
)
] [
] [ ] [
] [
] [ ] [
] [
1 (
)
] [
] [
)(
] [
] [ ] [
] [
(
*] *][ [
3
K
H
O H K
K
H
K
H
O H K
k
K
H
k
CH k
L
K
H
O H K
K
H
O H K
k
K
H
k
CH k
k
OH CH k rate
r
f
r
f
OH CH
+ +
+
+
+
= =


When
r f f
r r r
2 , 2 3
<<< , ] [ ,
] [
] [
] [
4 2
4
2
2
5
2
2 1
3
CH k
K
H
k
K
H
O H K
k
f r
<< the rate derived from
PSSH collapses into the QE derived rate.