Lecture 11

Chemical Reaction Engineering (CRE) is the

field that studies the rates and mechanisms of
chemical reactions and the design of the reactors in
which they take place.
  Block 1: Mole Balances
 Block 2: Rate Laws
 Block 3: Stoichiometry
 Block 4: Combine

 Determining the Rate Law from Experimental Data

 Integral Method
 Differential (Graphical) Method
 Nonlinear Least Regression

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 Integral Method
Consider the following reaction that occurs in a constant
volume Batch Reactor: (We will withdraw samples and
record the concentration of A as a function of time.)
A  Products
dN A
Mole Balances:  rAV
dt

Rate Laws: rA  kCA


Stoichiometry: V  V0
dCA
Combine:    kCA
3
dt
 Finally we should also use the formula to plot reaction
rate data in terms of conversion vs. time for 0, 1st and
2nd order reactions.
Derivation equations used to plot 0th, 1st and 2nd order
reactions.
These types of plots are usually used to determine the
values k for runs at various temperatures and then used
to determine the activation energy.

Zeroth order First Order Second Order

dCA dCA dCA
 rA  k  rA  kCA  rA  kCA2
dt dt dt

at t  0, CA  CA 0 at t  0, CA  CA 0 at t  0, CA  CA 0
CA 0 
 CA  CA 0 
 kt  ln   kt 
1

1
 kt
4 CA  CA CA 0
 
 Integral Method
Guess and check for α = 0, 1, 2 and check against
experimental plot.
 0  1  2
 C A0  1 1
rA  C A0  kt ln    kt   kt
 CA  C A C A0
ln(CA0/CA)
CA

1/CA
t t t
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 Differential Method
 dC A 
Taking the natural log of   kCA 
 dt 
 dC A 
ln     ln k   ln C A
 dt 
 dCA 
The reaction order can be found from a ln-ln plot of:   vs CA
 dt 
dC A ln

dt
 dC A 
dC A
  

Slope = α  dt  p
dt P
k 
C Ap
ln
6 CAP CA
 Methods for finding the slope of log-log and semi-log
graph papers may be found at

http://www.physics.uoguelph.ca/tutorials/GLP/

However, we are usually given concentration as a

function of time from batch reactor experiments:

time (s) 0 t1 t2 t3
concentration CA0 CA1 CA2 CA3
(moles/dm3)

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Three ways to determine (-dCA/dt) from concentration-time data
 Graphical differentiation
 Numerical differentiation formulas
 Differentiation of a polynomial fit to the data
1. Graphical

C A

t

8
t
 C A

t

dC A 
 
 dt  0
dC A 
 
dt  t1
dC A 
 
dt t2

t
0 t1 t2
9 The method accentuates measurement error!
 Example – Finding the Rate Law
t(min) 0 1 2 3

CA(mol/L) 1 0.7 0.5 0.35

C A
 0.3 0.2 0.15
t

C A Areas equal for both


t .3 sides of the histogram
.2
.1

t
1 2 3
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 Example – Finding the Rate Law
C A
Find f(t) of  using equal area differentiation
t
CA 1 0.7 0.5 0.35
-dCA/dt 0.35 0.25 0.175 0.12

Plot (–dCA/dt) as a function of CA

ln

dCA/dt
Slope = α
ln
11 CA
 Example – Finding the Rate Law
Choose a point, p, and find the concentration and
derivative at that point to determine k.

ln dCA/dt
 dC A 
 
 dt  p  dC A 
  Slope = α
k  dt  p
C Ap
ln CA
CA p

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 Non-Linear Least-Square Analysis
We want to find the parameter values (α, k, E) for
which the sum of the squares of the differences, the
measured rate (rm), and the calculated rate (rc) is a
minimum.

2 
n
Cim  Cic 2 
S2
i 1 N K N K
That is, we want  2 to be a minimum.
N= number of runs
K= number of parameters to be determined

Cim= measured conc for run i
13 Cic= calculated conc for run i
 Non-Linear Least-Square Analysis
For concentration-time data, we can combine the

mole balance equation forrA  kCA to obtain:
dC A
 kC A
dt
t  0 C A  C A0

C1A0  C1A  (1   )kt

Rearranging to obtain the calculated concentration

as a function of time, we obtain:
C Ac  C A  [C 1
A0  (1   )kt ]
1/(1 )

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 Non-Linear Least-Square Analysis
Now we could use Polymath or MATLAB to find the values of α and k
that would minimize the sum of squares of differences between the
measured (CAm) and calculated (CAc) concentrations.
That is, for N data points,

Similarly one can calculate the time at a specified concentration, tc

and compare it with the measured time, tm, at that same concentration.
That is, we find the values of k and α that minimize:

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 Non-Linear Least Squares Analysis
Guess values for α and k and solve for measured
data points then sum squared differences:
CAm 1 0.7 0.5 0.35
CAc 1 0.5 0.33 0.25
(CAc-CAm) 0 -0.2 -0.17 -0.10
(CAc-CAm)2 0 0.04 0.029 0.01 0.07

for α= 2, k = 1 → s2 = 0.07
for α = 2, k = 2 → s2 = 0.27
16 etc. until s2 is a minimum
 Non-Linear Least Squares Analysis

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 Non-Linear Least Squares Analysis

 
N N
1 1 2
s  CAmi  CAci   CAmi  C  1   kti 
2 2 1
A0
i1 i1

We find the values of alpha and k which minimize s2

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Minimum Sum of Squares
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21
 Residuals

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23
 Method of initial rates
Differential method of data analysis is one of the easiest
method
However, other effects (reverse reaction), could render
differential method ineffective
In such cases, methods of initial rates can be used to
determine reaction order and specific rate constants.
Series of experiments are carried out at different initial
conc (CA0) and initial rate of the reaction (-rA0) is
determined for each run.
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-rA0= kCA0
 Example 5-4 Method of initial rates in solid-
liquid dissolution kinetics

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 Example 5-4 Method of initial rates in solid-
liquid dissolution kinetics

Concentration-time data
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 Example 5-4 Method of initial rates in solid-
liquid dissolution kinetics

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 Example 5-4 Method of initial rates in solid-
liquid dissolution kinetics

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 Method of half-lives (t1/2)
t1/2 is the time it takes for the concentration of the
reactant to fall to half of its initial value.
The method of half lives requires many experiments
When two reactants are involved, half life method is used
in conjunction with method of excess to get rate law of the
form

-rA= kCA

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 Method of half-lives (t1/2)
For irreversible reaction
A Products
Mole balance on species A in constant volume batch
reactor
-dCA/dt=-rA= kCA

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 Method of half-lives (t1/2)
For irreversible reaction
A Products
Mole balance on species A in constant volume batch
reactor
-dC /dt=-r = kC 
A A A

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 Method of half-lives (t1/2)
For irreversible reaction
A Products
Taking natural log of both sides

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 Differential reactors
Differential reactor is normally used to determine rate of
reaction as a function of either conc or partial pressure
It consists of tube containing very small amount catalyst in
the form of thin wafer or disk
The criterion for reactor being differential are
-Conversion of reactant in the bed is extremely small
-Reactor is considered to be gradientless
-Reactor is considered to be isothermal
-No catalyst decay
It is easy to construct at low cost
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 Differential reactors
AP

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 Differential reactors
AP

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 Differential reactors
AP
Mole balance in terms of concentration

Differential reactor design equation

In terms of conversion or product

flowrate, Fp

In terms of concentration product

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 Differential reactors
AP
Mole balance in terms of concentration

Rate as a function of conc of A in the bed

Arithmatic mean of inlet & outlet conc

Bed conc is essentially the inlet conc

Rate as a function of CA0

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 Criteria for evaluation of reactors

1. Ease of sampling and product analysis

2. Degree of isothermality
3. Effectiveness of contact between catalyst and reactant
4. Handling of catalyst decay
5. Reactor cost and ease of construction

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 Types of reactors

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 Summary of reactor rating

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