REACTION ENGINEERING

EP 319/EP327
CHAPTER 5
COLLECTION AND ANALYSIS OF
RATE DATE
NOOR ROSYIDAH SAJUNI
rosyidah@ucsiuniversity.edu.my
Note: Please make appointment first before
consultations and come fully prepared.
.
• Determine the specific reaction rate (rate constant)

• Determine the order of reaction with respect to each

of the reactants

• In order to perform reactor designs, the reaction rate

equation must be known. Determination of the rate
equation and its associated constants requires
analysis of experimental data
5.1 Differential and integral method for
batch data
5.2 Method of initial rates
5.3 Method of half lives
Batch reactors are often used to determine rate law
parameters for homogeneous reaction.
This is done by measuring concentration as a
function of time.
The data is used to determine reaction order, α and
specific reaction rate, k
There are 4 different methods of analyzing data:
Differential Method
Integral Method
Half –Lives Method
Initial Rates Method
1. The differential method is used for irreversible
reactions

2. Used to determine α and k by numerically

differentiating concentration vs. time data

3. This method is ONLY applicable when reaction

condition is essentially a function of the
concentration of only ONE reactant.
Consider a reaction using a constant volume batch reactor in
which A is converted into products
A Products
Samples are taken and the concentrations of A are recorded
as a function of time.
We know the rate equation can be presented as

To determine reaction order, α and specific reaction rate, k, we

do
Consider the following reaction that occurs in a constant volume batch
reactor

A  Product

Mole Balance:

Rate Law:

Stoichiometry:

Combine:
• Take natural logarithm of both sides to obtain

X-
Y- Axis
Axis Y-Intercept Slope

The reaction order can be

found from plot of:
1. In order to plot the graph, we need to obtain the derivative –
dCA/dt first
2. This is done by using the experimental data of concentration
vs. reaction time from the batch reactor
Reaction Time (s) 0 t1 t2 t3
Concentration (mol/dm3) CAo CA1 CA2 CA3

 However, there are 3 ways on how we can calculate the value

dCA/dt from the experimental data:
 Numerical Differentiation Formulas
 Graphical Differentiation
 Differentiation of a Polynomial Fit to the Data
Methods of analyzing rate analysis
data:

A. Numerical Differential Method

1. Can be used when the data points in the independent variable
are equally spaced, such as t1-t0= t2-t1=Δt

Reaction Time (s) 0 (t0) t1 t2 t3

Concentration (mol/dm3) CA0 CA1 CA2 CA3
Derivative (-dCA/dt) (-dCA/dt) t0 (-dCA/dt) t1 (-dCA/dt) t2 (-dCA/dt) t3

2. The three point differentiation formulas are:

A. Initial Point

 dCA   3CA0  4CA1  CA2

   1
 dt  t 0 2t
 3. Remember t1-t0= t2-t1=Δt
Reaction Time (s) 0 (t0) t1 t2 t3
Concentration (mol/dm3) CA0 CA1 CA2 CA3
Derivative (-dCA/dt) (-dCA/dt) t0 (-dCA/dt) t1 (-dCA/dt) t2 (-dCA/dt) t3

4. The three point differentiation formulas are:

B. Interior Points (Points in between the first and the
last)
 dCA 
  
1

CA i1  CA i1  2
 dt  ti 2t
 dCA   dCA 
Eg :   
1
CA2  CA0  Eg :   
1
C A3  C A1 
 dt  t1 2t  dt  t 2 2t
5. Remember t1-t0= t2-t1=Δt
Reaction Time (s) 0 (t0) t1 t2 t3
Concentration (mol/dm3) CA0 CA1 CA2 CA3
Derivative (-dCA/dt) (-dCA/dt) t0 (-dCA/dt) t1 (-dCA/dt) t2 (-dCA/dt) t3

6. The three point differentiation formulas are:

C. Last Point

 dCA 
  
1

CA i2   4CA i1  3CAi 
 dt  ti 2t
3

 dCA 
Eg :   
1
CA1  4CA2  3CA3 
 dt  t 3 2t
EXAMPLE 1
Reaction
Determine the reaction order, α Time Concentration
(mol/dm3)
for the liquid phase (min)
decompositions of reactant A
0.0 4.0
A Products
This reaction is carried out in a 2.5 2.89
constant volume batch system in 5.0 2.25
which the concentrations was
recorded at various time during 7.5 1.45
the reaction. The data are as
10.0 1.00
following:
12.5 0.65
EXAMPLE 1 (SOLUTION)
Reaction Concentration
• Given the equation as determined Time (min) (mol/dm3)
previously as
X- 0.0 (t0) 4.00 (CA0)
Axis
2.5 (t1) 2.89 (CA1)

Y- 5.0 (t2) 2.25 (CA2)

Axis Y-Intercept Slope
7.5 (t3) 1.45 (CA3)
• In order to determine the order of the
reaction, we need to plot 10.0 (t4) 1.00 (CA4)
 dCA 
ln   vs ln C A 12.5 (t5) 0.65 (CA5)
 dt 

in which α is the slope of the graph

EXAMPLE 1 (SOLUTION)
Reaction
Concentration
3. In order to do so, we first need to Time
(mol/dm3)
determine the derivative –dCA/dt (min)
value first using the numerical 0.0 (t0) 4.00 (CA0)
method as discussed
2.5 (t1) 2.89 (CA1)
t1-t0= t2-t1=Δt = 2.5
5.0 (t2) 2.25 (CA2)
INITIAL POINT : 7.5 (t3) 1.45 (CA3)
 dCA   3C A0  4C A1  C A2
   10.0 (t4) 1.00 (CA4)
 dt t0 2t
12.5 (t5) 0.65 (CA5)

EXAMPLE 1 (SOLUTION) Reaction Time Concentration
t1-t0= t2-t1=Δt = 2.5 (min) (mol/dm3)

0.0 (t0) 4.00 (CA0)

INTERIOR POINTS 2.5 (t1) 2.89 (CA1)
 dCA 
  
1
C A2  CA0  5.0 (t2) 2.25 (CA2)
 dt t1 2t
 7.5 (t3) 1.45 (CA3)

10.0 (t4) 1.00 (CA4)

Continue calculating for (dCA/dt)t2,
(dCA/dt)t3, and (dCA/dt)t4 12.5 (t5) 0.65 (CA5)
EXAMPLE 1 (SOLUTION) Reaction Concentration
t1-t0= t2-t1=Δt = 2.5 Time (min) (mol/dm3)

0.0 (t0) 4.00 (CA0)

LAST POINT
2.5 (t1) 2.89 (CA1)
 dCA 
  
1
CA3  4CA4  3C A5 
 dt t5 2t 5.0 (t2) 2.25 (CA2)

7.5 (t3) 1.45 (CA3)

10.0 (t4) 1.00 (CA4)

12.5 (t5) 0.65 (CA5)

EXAMPLE 1 (SOLUTION)
Substitute values into table
Reaction Concentration
-dCA/dt ln (-dCA/dt) ln CA
Time (min) CA, (mol/dm3)
0.0 (t0) 4.00 (CA0)

2.5 (t1) 2.89 (CA1)

5.0 (t2) 2.25 (CA2)

7.5 (t3) 1.45 (CA3)

10.0 (t4) 1.00 (CA4)

12.5 (t5) 0.65 (CA5)

EXAMPLE 1 (SOLUTION) : Plot ln  dCA  vs ln C A ln
 dt  ln CA
(-dCA/dt)
Graph of ln (-dCA/dt) vs. ln CA
ln CA
0.0
-0.5 0.0 0.5 1.0 1.5

-0.5
ln (-dCA/dt)

-1.0

-1.5

-2.0

-2.5
 dCA 
ln     ln C A  ln k A
 dt 
Graphical Method
Step 1: calculate ∆CA and ∆t
Step 2: plot -∆ CA/∆t vs t
Step 3: read –dCA/dt at “t” for which
corresponding CA has been measured
Methods of analyzing rate analysis
data:
B. Integral Method
To determine the reaction order, α we need to guess
the reaction order (0,1 or 2) and integrate the
differential equation used to model the batch system

If the order assumed is correct, the appropriate plot of

the concentration-time data should be linear

Therefore the plot could be used to evaluate α and k

For the reaction A Products
carried out in a constant volume batch reactor, the mole balance is
dC A
 rA 1
dt

A. ZERO ORDER REACTION, -rA = k 2

Combine both to obtain the
mole balance as
dC A
 k 3 CA0
dt
Integrating with CA=CA0 at t=0 to obtain

CA CA0 kt 4
For the reaction A Products
carried out in a constant volume batch reactor, the mole balance is
dC A
 rA 1
dt
B. FIRST ORDER REACTION, -rA = kCA 2
Combine both to obtain the
mole balance as dC
 A
 kC A 3
dt
Integrating with CA=CA0 at t=0 to obtain

C A0
ln  kt 4
CA
For the reaction A Products
carried out in a constant volume batch reactor, the mole balance is
dC A
 rA 1
dt
C. SECOND ORDER REACTION, -rA = kC2A 2
Combine both to obtain the
mole balance as dC A
  kC A
2
3
dt

Integrating with CA=CA0 at t=0 to obtain

1 1
  kt 4
1/CA0
CA CA 0
Methods of analyzing rate analysis
data:
C. Initial Rates Method
 This method is used when reactions is reversible
Used determine α and k
Consider the following reaction A + B C+
D
A series of experiments is carried out at different initial
concentrations of reactant, CA0 and CB0 and the initial rate of
reaction, -rA0 is determined for each run

A. If the rate law is in the form therefore

ln(rA0 )   ln CA0  ln k
Y-Axis X-Axis
Slope Y-intercept
Methods of analyzing rate analysis
data:
D. Half Lives Method
The half life of a reaction, t1/2 is determined as the time it
takes for the concentration of the reactant, CA to fall to half
of its initial value, CA0.
This means t = t1/2 when CA = ½ CA0
Once t1/2 is identified, the α and k can be determined.
The equation that relates t1/2 to α and k is as following

2 1  1  1 
t1/2   
k (  1)  C A 0 
 1

Taking the natural log of both sides to yield

2 1  1
ln t 1/2  ln  1  α ln CA0
(α  1)k
1. From the equation obtained previously
2 1  1
ln t 1/2  ln  1  α ln CA0
(α  1)k

Y-Axis Y-intercept Slope X-Axis

Slope = 1- α
ln t1/2

ln CA0
FROM QUESTION 5.10C PAGE 298 FOGLER 4RD EDITION
FROM QUESTION 5.9C PAGE 272 FOGLER 3RD EDITION

SOLUTION
21  1
1. From earlier discussion, we know that ln t 1/2  ln  1  αln CA0
(α  1)k
2. Therefore we draw a table of
CA0 t1/2
ln t1/2 and ln CA0 from the date ln CA0 ln t1/2
(g mol/L) (min)
and subsequently plot the
graph to determine the
reaction order and rate
constant
FROM QUESTION 5.9C PAGE 272 FOGLER 3RD EDITION

SOLUTION 21  1
3. From the plot we know that ln t 1/2  ln  1  αln CA0
(α  1)k

Graph of ln t1/2 vs. ln CA0 ln t1/2

2.5

Slope  1 -   2.0
y = -1.00x - 2.43
Therefore  
1.5
 1
2 1
intercept  ln  ___________
(  1)k 1.0

Therefore k  0.5

0.0
-5.0 -4.0 -3.0 -2.0 -1.0 0.0
ln CA0