Sie sind auf Seite 1von 45

CHE502: REACTION ENGINEERING 1

CHAPTER 2: DETERMINATION OF RATE LAW

FAIZNUR MOHD FUAD

faiznur@uitm.edu.my
LECTURE OUTLINE

INTERPRETATION OF
BATCH REACTOR DATA

METHODS OF ANALYSIS OF
BATCH REACTOR DATA

CHE502: Reaction Engineering 1 2


BATCH REACTOR

Batch Reactor
mainly used for small scale
operation
suitable for slow reactions
mainly used for liquid-phase
reaction
charge-in/clean-up times can be
large

CHE502: Reaction Engineering 1 3


GENERAL MATERIAL BALANCE We lead

CHE502: Reaction Engineering 1 4


CONSTANT-VOLUME BATCH REACTOR
From the material balance

CHE502: Reaction Engineering 1 5


BATCH REACTOR
DATA

CHE502: Reaction Engineering 1 6


ANALYZING RATE DATA
1. In batch systems, the usual procedure is to collect concentration-time data
2. These data will be used to determine the rate law

Postulate Rate Law

Identify reactor type and mole balance

Data in terms of measurable variable

Simplify

Analyze data using


differential/integral/initial rates/half lives
CHE502: Reaction Engineering 1 7
Postulate Rate Law

A P
rA kCA

Identify reactor type and mole balance

Batch reactor

Simplify

If one of the reactants is in excess, assume its concentration is constant.

CHE502: Reaction Engineering 1 8


We lead

Data in terms of measured variable

Combining the mole balance and rate law


dC A
k AC A
dt

Analyze data using differential/integral/initial rates/half lives

CHE502: Reaction Engineering 1 9


METHODS OF DATA ANALYSIS
TO IDENTIFY THE REACTION ORDER, AND REACTION RATE CONSTANT, k

Differential

Integral
Half lives

Initial Rates

CHE502: Reaction Engineering 1 10


Differential
For irreversible reaction, the reaction order and specific rate
constant can be determined by numerically differentiating
concentration versus time data.

It is applicable when the rate is essentially a function of the


concentration of only one reactant.

Consider a reaction carried out isothermally in a constant


volume batch reactor and the concentration is as a function of
time

A P
rA kCA

CHE502: Reaction Engineering 1 11


Differential
Combine mole balance and rate law:

dC A
k AC A
dt

The reaction order and k can be found by taking the natural


logarithm of both side

dC A
ln ln k A ln C A
dt

y = c+m x

CHE502: Reaction Engineering 1 12


Differential

dC A
ln ln k A ln C A
dt
How do we get this value
from CA vs t data?

CHE502: Reaction Engineering 1 13


Differential

1. Graphical differentiation
2. Numerical differentiation

CHE502: Reaction Engineering 1 14


-dCA/dt data : Graphical Method
time (s) 0 t1 t2 t3
concentration
CAo CA1 CA2 CA3
(mol/dm3)

Equal area graphical differentiation : Draw a smooth curve that best approximates
the area under the histogram.

CHE502: Reaction Engineering 1 15


-dCA/dt data : Numerical Method
Can be used when the data points in the independent
variable are equally spaced. t1 t0 t 2 t1 t

time (s) 0 t1 t2 t3 t4 t5
concentration
CAo CA1 CA2 CA3 CA4 CA5
(mol/dm3)

dCA/dt can be calculated by


dCA 3C A0 4C A1 C A 2
Initial point
dt t0 2t

Interior points dC A

1

C Ai 1 C Ai 1
dt ti 2t
Last point
dC A

1
C A3 4C A4 3C A5
dt 5 2t
16
CHE502: Reaction Engineering 1
Example

17
Example

CHE502: Reaction Engineering 1 18


Example

CHE502: Reaction Engineering 1 19


Example

CHE502: Reaction Engineering 1 20


Example

CHE502: Reaction Engineering 1 21


Example

CHE502: Reaction Engineering 1 22


Example

CHE502: Reaction Engineering 1 23


Example

CHE502: Reaction Engineering 1 24


Example

25
CHE502: Reaction Engineering 1 26
Example

CHE502: Reaction Engineering 1 27


Example

CHE502: Reaction Engineering 1 28


Integral Method

Guess the
reaction order

If not linear, try Integrate the


guess other differential
reaction order equation

Plot
concentration-
time data

CHE502: Reaction Engineering 1 29


Integral Method

A P

Order guessed: zero Order guessed: first

rA k rA kC A
Combine rate law & MB: Combine rate law & MB:

dC A dC A
k kC A
dt dt
Integrate:
Integrate:
C AO
C A C AO kt ln kt
CA 30
Integral Method

A P

Order guessed: zero Order guessed: first

Plot: Plot:

C A C AO kt ln
C AO
kt
CA

31
Integral Method

A P

Order guessed: second

rA kC A2
Combine rate law & MB:

dC A
kC A2
dt
Integrate:

1 1
kt
C A C AO
32
33
CHE502: Reaction Engineering 1 34
35
Half lives
Half life of reaction, t1/2: time taken for the reactant concentration to
fall to half of its initial value

For example,

y = c+m x
CHE502: Reaction Engineering 1 36
Initial Rates

Method of initial rates requires a series of experiments to be


carried out at different initial concentrations, CAO and the initial
rate of reaction, -rAO is determined for each run.

Next, the reaction order and specific reaction rate will be


determined from the plot of ln (-rA0) vs ln CA0

y = c+m x

CHE502: Reaction Engineering 1 37


CONSTANT VOLUME BATCH REACTOR We lead

CONVERSION (X)

Number of moles of a chemical species, i that have reacted


per mole of i fed to the system

Suppose that NA0 is the initial amount of A in the reactor at


time t = 0, and that NA is the amount of A present at time t.

The conversion of A in the constant volume system is given:

CHE502: Reaction Engineering 1 38


EXAMPLE ON INTEGRAL METHOD We lead

A P
Guess order = 1

Express CA in terms of XA


= (1 )
0

39
We lead

CHE502: Reaction Engineering 1 40


Plotting:
We lead

A plot of In (1 - XA) or In (CA/CAo) vs t, as shown in the figure gives a straight line


through the origin for this form of rate of equation.
41
VARYING VOLUME BATCH REACTOR

CHE502: Reaction Engineering 1 42


VARYING VOLUME BATCH REACTOR
Much complex than simple constant-volume batch reactor.

Usually main use would be in the micro processing field.

Example

43
VARYING VOLUME BATCH REACTOR
Example

CHE502: Reaction Engineering 1 44


THANK YOU

CHE502: Reaction Engineering 1 45

Das könnte Ihnen auch gefallen