Chemical Reaction

Engineering 1
TEKNIK KIMIA – UNIVERSITAS PERTAMINA 2018
Catia Angli Curie, MS.
Obtaining & Analysis of Rate Data

Contents Objectives
 Obtaining rate data ❑ Understand the typical method used to obtain
rate data, esp. for homogeneous reaction
 Determining reaction order – the
method of excess ❑ Able to estimate a satisfactory form of rate law
using integral and differential method
 Algorithm of data analysis
 Estimating the rate law
 Integral method
 Differential method
 Obtaining rate data

Homogeneous reaction Heterogeneous reaction

 Is usually done using batch reactor  Normally we use differential reactor
 Data are collected at transient period  Data are collected at steady state
 Data: concentration, pressure, &/  Data: product concentration for
volume are measured vs time different sets of feed conditions

To analyze the data:

• Differential method • Integral method May be generated from 1 experiment

• Half-lives method • Initial rates method

Determining reaction order –
The Method of Excess

 For irreversible reaction with >1 reactant

A + B → products
𝛽
with rate law: −𝑟𝐴 = 𝑘𝐴 𝐶𝐴𝛼 𝐶𝐵
where the order of reaction and the rate constant is unknown
 First, run the reaction in an excess of B
𝐶𝐵 will be essentially unchanged (𝐶𝐵 = 𝐶𝐵0 )
Rate law will be: −𝑟𝐴 = 𝑘′𝐶𝐴𝛼
𝛽 𝛽
With 𝑘 ′ = 𝑘𝐴 𝐶𝐵 ≈ 𝑘𝐴 𝐶𝐵0
 Use the data & these equations to find 𝛼
Determining reaction order –
The Method of Excess

 For irreversible reaction with >1 reactant

A + B → products
𝛽
with rate law: −𝑟𝐴 = 𝑘𝐴 𝐶𝐴𝛼 𝐶𝐵
where the order of reaction and the rate constant is unknown
 After knowing 𝛼, run the reaction in an excess of A
𝐶𝐴 will be essentially unchanged (𝐶𝐴 = 𝐶𝐴0 )
𝛽
Rate law will be: −𝑟𝐴 = 𝑘"𝐶𝐵
With 𝑘 " = 𝑘𝐴 𝐶𝐴𝛼 ≈ 𝑘𝐴 𝐶𝐴0
𝛼

 Use the data & these equations to find 𝛽

Algorithm for Data Analysis –
homogeneous reaction

𝛽
 Postulate a rate law (eg. −𝑟𝐴 = 𝑘𝐶𝐴𝛼 , or −𝑟𝐴 = 𝑘𝐶𝐴𝛼 𝐶𝐵 , etc)
 The mole balance that is relevant with the type of reactor used in the experiment
𝑑𝐶𝐴
if we use constant volume batch reactor → mole balance of reactant: −𝑟𝐴 = − 𝑑𝑡

→ process the data in terms of the measured variable (𝐶𝐴 , 𝑁𝐴 , or 𝑃𝐴 )

→ look for simplifications
 Solve for reaction order & rate constant (integral / differential method)
Obtaining the rate law

Integral method Differential method

Easy to use, recommended when:  Is used in more complicated situations
 Testing specific mechanisms, (to develop rate equation to fit the data)
especially simple rate law expression
 Require more accurate & larger amounts
 Where the data are so scattered that of data
𝑑𝐶
it is difficult to find 𝑑𝑡𝐴

In general, try the integral method first, if not successful, then try with differential method
Obtaining the rate law –
Integral Method

 Is a trial error procedure (best used to test a reaction order)

The Steps:  Need to guess the order of the reaction

 Use it to integrate the mole balance
 Re-arrange to obtain linear equation
 Plot the concentration function vs time
(based on the linear equation)
 If it is relatively straight
→ the guess is satisfactory,
 otherwise, guess another order
 Obtaining the rate law –
Integral Method

For a reaction of A → products (in a constant volume batch reactor)

 Need to guess the order of the reaction  Eg. for 0th order reaction: −𝑟𝐴 = 𝑘𝐶𝐴0 = 𝑘
 Use it to integrate the mole balance
𝑑𝐶𝐴 𝑑𝐶𝐴
 Re-arrange to obtain linear equation −𝑟𝐴 = − 𝑘=−
𝑑𝑡 𝑑𝑡
 Plot the concentration function vs time 𝑡 𝐶𝐴
𝑘 න 𝑑𝑡 = − න 𝑑𝐶𝐴
(based on the linear equation) 0 𝐶𝐴0
 If it is relatively straight → the guess is 𝑘𝑡 = 𝐶𝐴0 − 𝐶𝐴
satisfactory, otherwise, guess another order
𝐶𝐴 = 𝐶𝐴0 − 𝑘𝑡

Plot 𝐶𝐴 vs time
 Obtaining the rate law –
Integral Method

For a reaction of A → products (in a constant volume batch reactor)

 If the reaction is 1st order: −𝑟𝐴 = 𝑘𝐶𝐴  If the reaction is 2nd order: −𝑟𝐴 = 𝑘𝐶𝐴2

𝑑𝐶𝐴 𝑑𝐶𝐴 𝑑𝐶𝐴 𝑑𝐶𝐴

−𝑟𝐴 = − 𝑘𝐶𝐴 = − −𝑟𝐴 = − 𝑘𝐶𝐴2 = −
𝑑𝑡 𝑑𝑡 𝑑𝑡 𝑑𝑡
𝑡 𝐶𝐴 𝑡 𝐶𝐴
𝑑𝐶𝐴 𝑑𝐶𝐴
𝑘 න 𝑑𝑡 = − න 𝑘 න 𝑑𝑡 = − න 2
0 𝐶𝐴0 𝐶𝐴 0 𝐶𝐴0 𝐶𝐴

𝐶𝐴0
𝑙𝑛 = 𝑘𝑡 1 1 1 1
𝐶𝐴 − = 𝑘𝑡 = 𝑘𝑡 +
𝐶𝐴 𝐶𝐴0 𝐶𝐴 𝐶𝐴0
𝐶𝐴0
Plot l𝑛 vs time 1
𝐶𝐴
Plot 𝐶 vs time
𝐴
Example of the
plot
 If (relatively) linear →
the guess is OK
 If not, try another order
 If it’s still not linear → try
differential method
 Example – integral method

The reaction of triphenyl methyl chloride (A) and methanol (B):

(C6H5)3CCl + CH3OH → (C6H5)3COCH3 + HCl
A+B→C+D
was carried out in a batch reactor at 25oC in a solution of benzene and pyridine in an excess of
methanol (CB0 = 0.5 mol/dm3). Pyridine reacts with HCl, which then precipitates as pyridine hydro-
chloride thereby making the reaction irreversible. The reaction is first order in methanol. The
concentration of triphenyl methyl chloride (A) was measured as a function of time:

Use the integral method to find the reaction order with regard to triphenyl methyl chloride (A) and
find the true rate constant.
2nd order k = 0.25 L2/mol2.min
 70

60

y = 0,1253x + 20
50
Example –
40
integral

1/CA
method 30

(the plot) 20

10

0
0 100 200 300 400
time
Obtaining the rate law –
Differential Method

For a reaction of A → products (in a constant volume batch reactor)

 Test the fit directly to the differential form of mole balance
𝑑𝐶𝐴 𝑑𝐶𝐴
−𝑟𝐴 = − 𝑘𝐴 𝐶𝐴𝛼 = −
𝑑𝑡 𝑑𝑡

 Doing natural logarithm to the equation yields:

Intercept =ln 𝑘𝐴
𝑑𝐶𝐴
ln(− ) = ln 𝑘𝐴 + 𝛼 ln 𝐶𝐴
𝑑𝑡 Slope = 𝛼
𝑑𝐶𝐴
Plot ln − vs ln 𝐶𝐴
𝑑𝑡
𝑑𝐶𝐴
 Tricky part: finding values of 𝑑𝑡
Finding the derivative
data (dCA/dt)
 Method 1: graphical method (appendix
A.2. of Fogler)
 Method 2: Numerical method
 Can be used when the data points in the
independent variable are equally spaced
 Eg. 𝑡1 − 𝑡0 = 𝑡2 − 𝑡1 = ∆𝑡
 Example – differential method

The reaction of triphenyl methyl chloride (A) and methanol (B):

(C6H5)3CCl + CH3OH → (C6H5)3COCH3 + HCl
A+B→C+D
was carried out in a batch reactor at 25oC in a solution of benzene and pyridine in an excess of
methanol (CB0 = 0.5 mol/dm3). Pyridine reacts with HCl, which then precipitates as pyridine hydro-
chloride thereby making the reaction irreversible. The reaction is first order in methanol. The
concentration of triphenyl methyl chloride (A) was measured as a function of time:

Use the differential method to determine the reaction order with respect to A and the specific
reaction rate constant.
 0
-5 -4 -3 -2 -1 0

-2

Example – -4

ln (-dCa/dt)
differential -6

method y = 1,9959x - 2,092

-8
(the plot)
-10

-12
ln Ca
Illustration of graphical differentiation

(are read
from the
graph)

𝑑𝐶𝐴
Then plot ln − vs ln 𝐶𝐴 , & continue the steps as before
𝑑𝑡
Obtaining the rate law - summary

Integral method Differential method

 Need to guess the order of the  Test the fit directly to the differential
reaction form of mole balance
 Use it to integrate the mole balance (in terms of
𝑑𝐶𝐴
)
𝑑𝑡
 Re-arrange to obtain linear equation 𝑑𝐶𝐴
 Quite tricky in finding values of 𝑑𝑡
 Plot the concentration function vs time
(based on the linear equation)
 If it is relatively straight → the guess is
satisfactory, otherwise, guess another
order
Exercise
References

 Fogler, H. S. 2009. “Elements of Chemical Reaction Engineering”, 4th Ed. Prentice-Hall.

 Levenspiel, O. 1999. “Chemical Reaction Engineering”, 3rd Ed. John Wiley & Sons.