49

Interpretation & The Use of Rate

Law
ITK-329 Kinetika & Katalisis
Dicky Dermawan
www.dickydermawan.net78.net
dickydermawan@gmail.com

Chapter 3
50
Conversion
fed A of Number
consumed) ( reacted A of Number
A of Conversion
=

Moles of A consumed = Moles of A fed Moles of A IN the reactor

0 A
A 0 A
A
N
N N
X

= ) X 1 ( N N
0 A A
=
Batch Systems
Flow Systems
unit time per fed A of Number
unit time per consumed) ( reacted A of Number
A of Conversion
=

0 A
A 0 A
A
F
F F
X

=
) X 1 ( F F
0 A A
=
51
Typical Questions:
3.9
A first-order polymerization reaction is being run in a batch
reactor. A concentration of 0.007 mol/liter of monomer is
loaded into the reactor, and then a catalyst is added to
initiate the reaction. Experiments show that the reaction is
30% complete in 10 minutes.
a. Calculate the rate constant
b. Calculate the half-life
c. How long will it take for the reaction to be 90% complete?
d. How would the time in (c) change if you increased the
concentration in the reactor to 0.16 mol/liter?
e. Repeat for a second order reaction.
52
Typical Questions (2):
3.10
N
2
O
5
can be made via oxidation of ammonia over a platinum gauze.
You do an experiment and find that you get 50% conversion of the
ammonia with a 0.1 second residence time in the reactor at 1000 K.
a. Calculate the rate constant for the reaction assuming that the
reaction is first-order in the ammonia pressure and zero-order in
oxygen pressure.
b. How long of a residence time will you need to get 90% conversion at
1000 K?
c. Now assume that the reaction is instead secondorder in the ammonia
pressure.
d. Estimate the rate constant for the reaction assuming 50% conversion
in 0.1 second.
Assume a stoichiometric feed at 1 atm pressure
53
Kinetics from Minimal Number of Data

L3.5
In a homogeneous isothermal liquid polymerization, 20% of the
monomer disappears in 34 min for initial monomer
concentration of 0.04 mol/L and also for 0.8 mol/L. What is the
rate of disappearance of the monomer?

L3.10
In units of moles, liters, and seconds, find the rate expression for
the decomposition of ethane at 620
o
C from the following
information obtained at atmospheric pressure. The
decomposition rate of pure ethane is 7.7%/sec, but with
85.26% inerts present the decomposition rate drops to
2.9%/sec.
54
Kinetics from Minimal Number of Data

L3.21
Find the first-order rate constant for the disappearance of A in
the gas reaction 2 A > R if, on holding the pressure constant,
the volume of the reaction mixture, starting with 80% A,
decreases by 20% in 3 min.

L3.22
Find the first-order rate constant for the disappearance of A in
the gas reaction A > 1.6 R if the volume of the reaction
mixture, starting with pure A, increases by 50% in 4 min. The
total pressure within the system stays constant at 1.2 atm,
and the temperature is 25
o
C
55
Kinetics from Minimal Number of Data:
Reversible Reaction
L3.9
The first-order reversible liquid reaction
A R, C
A0
= 0,5 mol/L, C
R0
= 0
Takes place in a batch reactor. After 8 minutes,
conversion of A is 33.3% while equilibrium
conversion is 66.7%. Find the rate equation for
this reaction
56
Integration of a Rate Equation:
Interpretation of Reaction Order
L3.2
Liquid A decomposes by first order kinetics, and in a
batch reactor 50% of A is converted in a 5-minute
run. How much longer would it take to reach 75%
conversion?

L3.3
Repeat the previous problem for second-order kinetics
57
Integration of a Rate Equation
Assume that you are running a reaction A B that follows:
A
13
A
C
T R
kcal/mol 20
exp 10 1 r
(

=
Where r
A
is the rate of reaction in mol/(L.sec), T is temperature in Kelvin, R =
1.987 cal./(mol.K)
The temperatur varies during the course of the reaction according to:
|
.
|

\
|
+ =
10
t
sin 10 300 T
where t is time in second
How long will it take to reduce the A concentration from 1 mol/L to 0,1 mol/L?
dt
dN
V
1
r
A
A
For homogeneous reaction taking place in a batch reactor:
For a constant volume batch reactor: =
dt
) V / N ( d
dt
dN
V
1
r
A A
A
dt
dC
r
A
A

58
Integration of a Rate Equation:
Interpretation of Reaction Order
L3.4
A 10-minute experimental run shows that 75%
of liquid reactant is converted to product by a
order rate. What would be the amount
converted in a half-hour run?

59
Integration of a Rate Equation:
Constant Volume vs Constant Pressure Batch
Reactor
L3.23
A zero-order homogeneous gas reaction
A r R
Proceeds in a constant-volume bomb, 20% inerts, and the
pressure rises from 1 to 1.3 atm in 2 min.
If the same reaction takes place in a constant-pressure
batch reactor, what is the fractional volume change in 4
min if the feed is at 3 atm and consist of 40% inerts?
60
Integration of a Rate Equation:
Constant Volume vs Constant Pressure Batch
Reactor
L3.24
A zero-order homogeneous gas reaction
A r R
Proceeds in a constant-volume bomb, P = 1 at t =
0, and P = 1.5 when t = 1.
If the same reaction, same feed composition, and
initial pressure proceeds in a constant-pressure
setup, find V at t = 1 if V = 1 at t = 0
61
Integration of a Rate Equation:
Constant Volume vs Constant Pressure Batch
Reactor
L3.25
The first-order homogeneous gaseous decomposition
A 2.5 R
Is carried out in an isothermal batch reactor at 2 atm with
20% inerts present, and the volume increases by 60%
in 20 min.
In a constant-volume reactor, find the time required for the
pressure to reach 8 atm if the initial pressure is 5 atm, 2
atm of which consist of inerts.

62
Integration of a Rate Equation:
Constant Volume vs Constant Pressure Batch
Reactor
L3.26
The gas reaction
2 A R + 2 S
Is approximately second order with respect to A. When
pure A is introduced at 1 atm into a constant-volume
batch reactor, the pressure rises 40% in 3 min.
For a constant-pressure batch reactor, find:
a. the time required for the same conversion
b. The fractional increase in volume at that time.

63
Multiple Reactions
L3.16
Nitrogen pentoxide decomposes as follows:

N
2
O
5
O
2
+ N
2
O
4
r
N
2
O
5
= (2.2x10
-3
min
-1
).C
N
2
O
5
N
2
O
4
2 NO
2
K
p
= 45 mmHg

Find the partial pressures of the contents of a constant-
volume bomb after 6.5 hours if we start with pure at
atmospheric pressure



64
Multiple Reactions:
L3.18
For the reactions in series:





Find the maximum concentration of R and when it is
reached if:
a. k
1
= 2 k
2
b. k
1
= k
2


S R A
2 1
k k