Todays lecture

Rate law from batch reactor

Differential Method
Integral Method
Half-lives method
Initial rate method
Linear regression
Non-linear regression

Rate law from differential reactor

Brief description of other reactor types

employed for kinetics study
Collection and analysis of rate data
Batch reactor
for homogenous reactions
measurement during the unsteady-state
operation
Differential reactor
for solid-fluid reactions
measurement during steady state operation
product concentration is usually monitored
for different feed conditions.
Analysing methods
Differential method Batch reactors
Integral method
Initial rate method
Half-lives method
Linear regression
Software packages
Non-linear regression
 Typical Experimental Data Available from
Batch Reactor Experiments

Time (min) t0 t1 t2 t3 t4 t5

Concentration (mol/L) CA0 CA1 CA2 CA3 CA4 CA5

OR

Time (min) t0 t1 t2 t3 t4 t5

Pressure (kPa) PT0 PT1 PT2 PT3 PT4 PT5

 Batch reactor

Differential method of rate analysis

When a reaction is irreversible, it is possible to
obtain the specific rate constant by numerically
differentiating concentration versus time data.
What we want to develop What we measured
dC A
k AC A
dt
For example: decomposition reaction A products

Assuming the rate law as: rA kCA
What about A + B
products ?
 Method of excess
A + B products

Assuming the rate law as: rA k AC A CB

Run in an excess of B, so that CB remains essentially

unchanged during the course of the reaction

rA k C A

After determining , the reaction is run in an excess of A

rA k CB
 Constant-volume batch reactor

rA kCA
constant volume dN A
rA
Vdt
ln (-dCA/dt)
dC A Slope =
k AC A
dt

dC A
ln ln k A ln C A ln CA
dt
Differential method
Methods for the determination of
the derivatives
Graphical differentiation
plotting CA/ t as a function of t
using equal-area differentiation to obtain dCA/dt
Numerical differentiaion
when the data points in the independent variable
are equally spaced
weighted averaged CA
Differentiation of a polynomial fit to the data
Excel, Sigmaplot and other softwares can be used
 Graphical differential analysis time for an example!
Need dCA/dt to get this draw curve through CA/t data that
minimizes differences (i.e. equal area differentiation)

Get dCA/dt
 Differential analysis time for an example!
Numerical differentiation (Finite difference)
dC A 3C Ao 4C A1 C A2 350 438 30.610 3
t=0 min
dt t 0 2 t 100
dC A 4
2.86 10 mol / dm min
3

dt t 0

t=50 min dC

1
C A2 C Ao 30.6 50 10 3
A

dt t 50 100 100
dC A
1.94 10 4 mol / dm 3 min
dt t 50

You get the idea

 Polynomial fit
Finally, can also fit the CA v t to an nth order polynomial

C A ao a1t a2t 2 .. ant n

Pro: have an analytical function which you can differentiate

Con: have to pay attention to order of polynomial (i.e. need
statistical assessment of quality of fit!)
If too low, not capture the trends
If too large, have peaks and valleys, producing significant
errors for

dC A / dt

two fits for the same data

 Differential method example
Gas-phase decomposition of di-tert-butyl peroxide:

O
||
(CH3)3COOC(CH3)3 C2H6 + 2CH3CCH3

Time (min) Total Pressure (mmHg)

0.0 7.5
2.5 10.5
5.0 12.5
10.0 15.8
15.0 17.9
20.0 19.4

Postulate a rate law rA kCA
dC A CA P
Mole balance kCA
dt
For a constant volume batch reactorV V P0 (1 X ) T
0
P T0
For isothermal operation and constant volume
1 1 1
X ( P P0 ) ( P P0 ) ( P P0 )
P0 y A0 P0 PA0
For the reaction =1+2-1
N A0 PA0
C A C A0 (1 X ) (1 X ) (1 X )
VA0 RT0

3P0 P
CA
2 RT dP
k (2 RT )1 (3P0 P)
dt
dP dP
k (2 RT )1 (3P0 P) k (3P0 P)
dt dt

dP
P ln( ) ln k ln(3P0 P)
dt

ln (dP/dt)

ln (3P0 -P)
Analysing methods
Differential method Batch reactors
Integral method
Initial rate method
Half-lives method
Linear regression
Non-linear regression
Integral Method
A trial-and-error procedure to find reaction order
Guess the reaction order Integrate the
differential equation
This method is used most often when the reaction
order is known and it is desired to evalue the
specific reaction rate constants at different
temperatures to determine the activation energy.
We are looking for the appropriate function of
concentration corresponding to a particular rate
law that is linear with time.
For the reaction A products
dC A
For a zero-order reaction - rA = - k k
dt
CA

C A C A0 kt
t
dC A
For a first-order reaction - rA = - k C A kCA
ln (CA0/CA)
dt

C A0
ln kt
t CA
dC A
For a second-order reaction - rA = - k CA2 kCA
2

1/CA
dt

1 1
kt
t C A C A0
 Integral method example
Gas-phase decomposition of di-tert-butyl peroxide:

O
||
(CH3)3COOC(CH3)3 C2H6 + 2CH3CCH3

Time (min) Total Pressure (mmHg)

0.0 7.5
2.5 10.5
5.0 12.5
10.0 15.8
15.0 17.9
20.0 19.4
 dP dP
k (2 RT )1 (3P0 P) k (3P0 P)
dt dt
Differential method

dP
ln( ) ln k ln(3P0 P)
Integral method

dt

Assuming =1
dP
k (3P0 P)
dt
ln [2P0/(3P0-P)]
Bingo!
2 P0
ln( ) k t
3P0 P

t
For Batch Reactor Data
A-> products A+B-> products

guess order

20
Analysing methods
Differential method
Batch reactors
Integral method
Initial rate method
Half-lives method
Linear regression
Non-linear regression
Method of initial rates
When the reaction is reversible, the method of
initial rates can be used to determine the
reaction order and the specific rate constant.
A series of experiments is carried out at different
initial concentrations and the initial rate of reaction is
determined for each run. The initial rate can be found
by differentiating the data and extrapolating to zero
time.
By various plotting or numerical analysis techniques
relating -rA0 to CA0, we can obtain the appropriate rate
law:

rA0 kC A0
 Initial rate method example

The dissolution of dolomite using hydrochloric acid:

4HCl + CaMg(CO3)2 Mg2+ + Ca2+ + 4Cl-+2CO3 + 2H2O
The concentration of HCl at various times was determined from atomic
absorption spectrophtometer measurements of the calcium and
magnesium ions
4 N HCl

CHCl
1 N HCl

t Example 5-4 p. 279

Evaluating the mole balance on a constant-volume batch reactor
at t = 0:
dCHCl dC
( r )
HCl 0 kCHCl , 0 ln HCl ln k ln CHCl ,0
dt 0 dt 0

2 7
CHCl, 0 (N) Initial reaction rate rHCl,0 (mol/cm s) x 10
1 1.2
4 2.0
2 1.36
0.1 0.36
0.5 0.74

ln -
rHCl,0 Slope =

ln CHCl
Analysing methods
Differential method
Batch reactors
Integral method
Initial rate method
Half-lives method
Linear regression
Non-linear regression
Method of half-lives
The half-life of a reaction, t1/2, is defined as the
time it takes for the concentration of the
reactant to fall to half of its initial value.
By determining the half-life of a reaction as a
function of the initial concentration, the
reaction order and specific reaction rate can be
determined.
 dC A 1 1 1
A products kCA t
1
1
dt k ( 1) C A C A0

C A 1 C A0
2

ln (t1/2)

Slope = 1- 2 1 1 1
t1 1
2 k ( 1) C A0

2 1 1
ln(t 1 ) ln (1 ) ln C A0
ln CA0 2 k ( 1)
Analysing methods
Differential method
Batch reactors
Integral method
Initial rate method
Half-lives method
Differential reactor
Linear regression
Non-linear regression
Differential reactors
The criterion for a reactor being differential is that the
conversion of the reactants in the bed is extremely
small, as is the change in reactant concentration
through the bed.
The reactant concentration through the reactor is
essentially constant (i.e. the reactor is considered to be
gradientless)
The rate of reaction is determined for a specified
number of pre-determined initial or entering reactant
concentrations.
Determine the rate of reaction as a function of either
concentration or partial pressure.

CA0 CA CAe CA0 ~ CA~ CAe

Differential reactors
The reactor is considered to be gradientless
(considered as a CSTR).
They operate essentially in an isothermal
manner.
(Limitation) If the catalyst under investigation
decays rapidly, the differential reactor is not a
good choice because the reaction rate
parameters at the start of a run will be different
from those at the end of the run.
 Differential catalyst bed
The rate of reaction per unit mass of catalyst, rA
flow rate in - flow rate out + rate of generation = rate of L
accumulation

FA0 FAe rA W 0
FA0 FAe
FA0 FAe v0C A0 vCAe
rA CA0 Cp
W W
Fp
When constant flow rate, v0 = v :

v0 (C A0 C Ae ) v0C p Product concentration

rA W
W W

The reaction rate can be determined by measuring the product concentration, Cp

 Differential reactor example
The formation of methane from carbon monoxide and hydrogen using a nickel
catalyst at 500 F in a differential reactor:

3H2 + CO CH4 + 2H2O

3
Run PCO (atm) PH2 (atm) CCH4 (g mol/dm )
-4
1 1 1.0 2.44 x 10
-4
2 1.8 1.0 4.40 x 10
-4
3 4.08 1.0 10.0 x 10
-4
4 1.0 0.1 1.65 x 10
-4
5 1.0 0.5 2.47 x 10
-4
6 1.0 4.0 1.75 x 10

10 g catalyst Product composition was monitored

exit volumetric flow rate: 300
dm3/min
 v0CCH4
rA rCH
4
W
300dm3 2.44 104 gmol / dm3 gmolCH 4
rA rCH
4 7.33 103
min 10 g cat. g cat. min
We can then relate the rate of reaction to the exit methane concentration for
each single run.

For constant hydrogen 4 kPCO f ( PH 2 )
rCH
concentration (excess),
4 k PCO
rCH 4 ) ln k PCO
ln(rCH
the rate law:

We observe:
=1
(1) at low H2 concentration where rCH4 increases as PH2 increases, the rate law may be of the
form: rCH4 ~ PH2 1
(2) at high H2 concentration where rCH4 decreases as PH2 increases, the rate law may be of the
form: rCH4 ~ PH2 1/2
1
PH 2 1=1/2
We suggest that the rate law can be the form: 4 ~
rCH 2
1 bPH 2 2=1
Actually, this is the typical form of the rate law for heterogeneous catalysis.
This predicts that if the rate-limiting step in the overall reaction is the reaction
between atomic hydrogen absorbed on the nickel surface and CO in the gas phase.
 1/ 2 1/ 2
PH 2 aPCO PH 2
4 ~
rCH 4 k PCO
rCH 4
rCH
1 bPH 2
1 1 bPH 2

1/ 2
PCO PH 2
1/ 2
4
rCH PCO PH 2 1 b
PH 2
4
rCH a a

PH 2

1.83 10 2 PCO PH 2
1/ 2

4
rCH
1 1.5PH 2