DEPARTMENT OF CHEMICAL

ENGINEERING

INTRODUCTION TO REACTOR DESIGN 3A(IRDCHA3)

Collection and Analysis of Rate Data

E Mkhonto
08 May 2023
Learning Unit 5: Collection and Analysis of
Rate Data

Unit Outcomes:

1. Determine the reaction order and specific reaction rate from experimental
data.

2. Use polynomial fitting, numerical difference formulas, graphs and regression

to analyse experimental data to determine the rate law and rate law
parameters.

3. Use regression software to evaluate the rate law parameters given

experimental data.
 Algorithm for Isothermal Reactor Design

Step 1: Mole Balances

Step 2: Rate Laws ???
Step 3: Stoichiometry
Step 4: Combine
Step 5: Evaluate
 Determining the Rate Law Parameters

Rate Law parameters are determined from Experimental Data (Measurable

variable vs time).
• Measurable variable = Concentration, Pressure, Volume etc.

There are 6 different methods of analysing the data collected:

The differential method,

The integral method,

The method of half-lives,

Method of initial rates,

and linear and nonlinear regression (Ieast-squares analysis).

 Determining the Rate Law Parameters

In this Unit we will focus on:

1. Integral Method

2. Differential Method – Graphical and Numerical.

3. Nonlinear Regression
 Integral Method

Consider the following reaction that occurs in a constant volume Batch

Reactor: (Samples were withdrawn at constant time intervals and the
concentration of A as a function of time was recorded.)

A  Products
dN A
Mole Balance: rAV
dt

Rate Law:  rA kCA


Stoichiometry: V V0
dCA
Combine:   kCA
dt

 Integral Method

How do we determine the order and the specific reaction rate constant???

1. A trial-and-error procedure to find reaction order.

2. Guess the reaction order → integrate the differential equation.

3. Rearrange the solution into the form: y = mx + c

Such that, when plotted, the gradient is equal to k

This method is used most often when reaction order is known and it is desired to
evaluate the specific reaction rate constants (k) at different temps to determine
the activation energy
 dCA
For the reaction A  products rA
dt
For a zero-order reaction -r A = k dCA
 k
dt
Plot of CA vs CA
t is a straight
line CA CA0  kt
t
dCA
For a first-order reaction - r A = k CA  kCA
ln (CA0/CA) dt
Plot of ln(CA0/CA)
vs t is a straight C
line ln A0 kt
t CA
dCA
For a second-order reaction - rA = k CA2  kCA 2
dt
1/CA

Plot of 1/CA vs t 1 1
is a straight line
 kt
t CA C A0
 Integral Method

CA0 1 1
CA CA0  kt ln kt  kt
CA CA C A0

𝑦 =𝑚𝑥 +𝑐
CA ln(CA0/CA) 1/CA

t t t
 Method Excess
Used to determine the specific rate and reaction order by focusing on one
reactant.
If one reactant is in excess it can be used as constant as it will not change
throughout the reaction (eg:
 Exercise 1

The liquid phase reaction:

𝑨+ 𝑩→ 𝑷

Given the experimental data below, determine the rate law parameters
using the integral method. With an excess of CBo = 0.5 mol/dm3
 Differential (Graphical) Method

Consider the following reaction that occurs in a constant volume Batch

Reactor: (Samples were withdrawn at constant time intervals and the
concentration of A as a function of time was recorded.)

A  Products
dN A
Mole Balance: rAV
dt

Rate Law:  rA kCA


Stoichiometry: V V0
dCA
Combine:   kCA
dt

 Differential (Graphical) Method

dCA
Combine:  kCA
dt
Taking the natural log on both sides

 dC 
ln   A  ln k   ln C A 𝑦 =𝑚𝑥 +𝑐
 dt 
 dCA 
The reaction order can be found from a ln-ln plot of:   vs CA
 dt 

But how do we get –dCA/dt from CA vs t data???


 Differential (Graphical) Method
But how do we get –dCA/dt from CA vs t data???

a) Plot DCA/Dt as a function of t

b) Determine dCA/dt from the plot by graphical or numerical methods
c) Plot ln(-dCA/dt) vs ln CA
time (s) 0 t1 t2 t3
Concentration (moles/dm3) CA0 CA1 CA2 CA3

CA

t



t
 Differential (Graphical) Method

CA

t

dC A 
 
 dt  0
dC A 
 
dt  t1
dC A 
 
dt  t 2

t
0 t1 t2
 Differential (Graphical) Method - Example

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 0.3 sides of the histogram
0.2

0.1

t
1 2 3
 Differential (Graphical) Method

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  dC A 
ln    ln k   ln C A
 dt 
-dCA/dt
Slope = α
𝑦 =𝑚𝑥 +𝑐
ln
CA
 Differential (Numerical) Method
But how do we get –dCA/dt from CA vs t data??? - Option 2

Numerical differentiation formulas can be used when the data points in the
independent variable are equally spaced, that is,

The three-point differentiation formulas:

Point 1:
 Differential (Numerical) Method

Interior Points:

Last Point:
 Exercise 2

𝑨+ 𝑩→ 𝑷

Given the experimental data below, determine the rate law parameters using
the differential method (Graphical and Numerical).
 Non-Linear Regression Method

We want to find the parameter values (α and k) for which the sum of the
squares of the differences between the measured concentration (Cm), and

the calculated concentration (Cc) is a minimum.

 2 
n
Cim  Cic 2 
S2
i 1 N K N K

That is, we want  2 to be a minimum.


 Non-Linear Regression Method

Consider the following reaction that occurs in a constant volume Batch

Reactor: (Samples were withdrawn at constant time intervals and the
concentration of A as a function of time was recorded.)

A  Products
dN A
Mole Balance: rAV
dt

Rate Law:  rA kCA


Stoichiometry: V V0
dCA
Combine:   kCA
dt

 Non-Linear Regression Method

dC A
 kC A Separate variables and integrate wrt CA
dt
and t.
t 0 C A C A0

C1A0  C1A  (1   )kt Integration solution.

Rearranging to obtain the calculated concentration as a function of

time, we obtain:

1  1/(1  )
C Ac C A [C A0  (1   )kt ]
 Non-Linear Regression Method

1  1/(1  )
C Ac C A [C A0  (1   )kt ]

Now we could use Excel Solver, 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,

 Non-Linear Regression Method

Similarly one can calculate the time at a specified concentration, t c

and compare it with the measured time, tm, at that same concentration.

That is, we find the values of k and α that minimize:

 Non-Linear Regression Method- Example

Guess values for α and k and calculate CA at each t value, then sum
squared differences (between calculated CA and CA in the above table):

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 C Ac C A [C 1A0  (1   )kt ]1/(1  )

for α = 2, k = 2 → s2 = 0.27
etc. until s2 is a minimum
 Exercise 3

𝑨+ 𝑩→ 𝑷

Given the experimental data below, determine the rate law parameters using
the non-linear regression method (Excel and Polymath).

Solution to be uploaded on blackboard as a software demonstration

video!!!