Chapter 5

BITS, PILANI K. K.
BIRLA GOA CAMPUS

COLLECTION AND ANALYSIS OF RATE DATA
Chapter 5
PROF. SRINIVAS KRISHNASWAMY
PROFESSOR & HEAD OF DEPARTMENT
DEPARTMENT OF CHEMICAL ENGINEERING
BITS PILANI, K. K. BIRLA GOA CAMPUS
What now??
After this chapter you will be able to focus on
ways of obtaining and analyzing reaction rate
data to obtain the rate law for a specific reaction
Understand the Batch Reactor concept
Mole Balance
Rate Laws
Stoichiometry
Pressure Drop
October 21, 2016
BITS, PILANI K. K. BIRLA GOA

CAMPUS
Algorithm for Isothermal Reactor

Design
October 21, 2016

CAMPUS
Evaluating the rate equation
October 21, 2016

CAMPUS
Interpretation of Batch
reactor data
Batch Reactor: Homogeneous data at
constant volume and isothermally
Flow reactor for homogeneous systems
Integral and Differential Method of

Analysis
October 21, 2016

CAMPUS
Requires large amount of accurate data

Develop or build a rate equation to fit data
October 21, 2016

CAMPUS
October 21, 2016

CAMPUS
Differential vs Integral method
October 21, 2016

CAMPUS
Batch reactor data
October 21, 2016

CAMPUS
Batch reactor data
October 21, 2016

CAMPUS
10
Batch reactor data
October 21, 2016

CAMPUS
11
Batch reactor data
October 21, 2016

CAMPUS
12
Batch reactor data
October 21, 2016

CAMPUS
13
Batch reactor data
October 21, 2016

CAMPUS
14
Batch reactor data
October 21, 2016

CAMPUS
15
Batch reactor data
October 21, 2016

CAMPUS
16
Batch reactor data

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.)
Mole balance
Rate Law
Stoichiometry
October 21, 2016

CAMPUS
17
Batch reactor data
PLOT
October 21, 2016

CAMPUS
18
Batch reactor data (Graphical)

time (s)
t1
t2
t3
concentration
(mol/dm3)
CAo
CA1
CA2
CA3
October 21, 2016

CAMPUS
19
Batch reactor data (Graphical)

time (s)
t1
t2
t3
concentration
(mol/dm3)
CAo
CA1
CA2
CA3
October 21, 2016

CAMPUS
20
Batch reactor data (Finite Difference)

Initial Point: (dCA/dt) at t = to
(-3CAo + 4CA1 CA2)/ 2t
Interior points
Final Point: (dCA/dt) at t = tn
Re attempt
problem on Slide
12 using this
method
(CA(n-2) - 4CA(n-1) + 3CAn)/ 2t

October 21, 2016

CAMPUS
21
Constant Volume Batch reactor
October 21, 2016

CAMPUS
22
Analysis of Total Pressure data
October 21, 2016

CAMPUS
23
October 21, 2016

CAMPUS
24
October 21, 2016

CAMPUS
25
Integral Method
Trial and error method to find reaction order

Used normally when order is known and k needs to be
evaluated (for activation energy)
Linear plots of functions of CA vs t for zero, first and second
order reactions
October 21, 2016

CAMPUS
26
Integral Method
October 21, 2016

CAMPUS
27
Irreversible Uni-molecular type First

Order Reaction
Caution
October 21, 2016

CAMPUS
28
Irreversible Bi-molecular type Second

Order Reaction
October 21, 2016

CAMPUS
29

Order Reaction
October 21, 2016

CAMPUS
30

Order Reaction (Caution 1)
Pseudo First Order reaction
October 21, 2016

CAMPUS
31

October 21, 2016

CAMPUS
32

October 21, 2016

CAMPUS
33
Zero order reactions
October 21, 2016

CAMPUS
34
Zero order reactions
October 21, 2016

CAMPUS
35
Empirical rate equations of

nth order
October 21, 2016

CAMPUS
36
Empirical rate equations of

nth order
October 21, 2016

CAMPUS
37
Overall order of irreversible

reactions from half life
n not equal to 1
October 21, 2016

CAMPUS
38
Problem Statement
Reactant A decomposes in a batch reactor
The composition of A in the reactor is measured at

various times with results shown in the following
columns 1 and 2.Find the rate equation to
represent the data.
Problem Solution
Guess: 1st order kinetics
Guess: 2nd order kinetics
Problem Solution
Guess nth order kinetics:
Fractional life method with F = 80%
Taking logarithms
Problem Solution
Accurately plot
Vs
t data
Draw smooth curve
Problem Solution
Pick various concentrations and fill in the
following table from the figure
Problem Solution
Problem Solution
First-Order Reversible
Reactions
Reversible unimolecular-type reaction
Concentration ratio
Reactions
The rate equation is
At equilibrium,
Fractional conversion of A at equilibrium
conditions,
Reactions
Equilibrium constant
Combining the equations
On integration,
Reactions
Compare with 1st

order irreversible
October 21, 2016

CAMPUS
50
Second order Reversible

Reaction
Bimolecular type second order reactions
Second-Order Reversible
Reactions
Restrictions
and
Integrated rate equation
Reactions
A plot is shown in the figure
Reactions of shifting order

Consider the reaction
Rate equation
October 21, 2016

CAMPUS
55

To apply the integral method, separate variables and integrate,
Linearize
October 21, 2016

CAMPUS
56
Autocatalytic Reactions
October 21, 2016

CAMPUS
58
October 21, 2016

CAMPUS
59
October 21, 2016

CAMPUS
60
Practice Problems
1. The decomposition of acetaldehyde CH3CHO to
give CH4 and CO is a second order reaction. The
rate at a certain temperature is 0.18 mol/l.sec.
when the acetaldehyde concentration is 0.1
mol/min
a. What is the rate expression for this reaction?
b . What is the value of rate constant?
c. Calculate reaction rate when concentration of
CH3COOH is 0.2 mol/l?
18 lit./mol.sec, 0.72 mol/lit.sec
October 21, 2016

CAMPUS
61
Practice Problems
A certain reaction has a rate given by rA=
0.007CA2
If the concentration is to be
expressed in mol/lit. and time is in hours, what
would be the value and units of the rate
constant? (1.167 10-7 lit./mol/hr). rate
expression has units as mol/cm^3/min.
What is the formula for half life period of a first
order reaction? The half life period of a certain
first order reaction is 2.5 103 sec. How long
will take for 1/4th of the reactant the left
behind?
October 21, 2016

CAMPUS
62
n = 1 + log [ (t1/2 / t1/2) / (CA / CA)]
Practice Problems
Show analytically that the decomposition of N2O5 at 67
oC is a first order reaction. Calculate the value of the rate
constant 0.3477 min-1
Time /
min
CN2O5 /
mol/lit.
0.16
0.113
0.08
0.056
0.040
In a gaseous reaction, time for half change for various

partial pressures is given. What is the rate equation?
0.106 CA
October 21, 2016
Time / min
12
16
PP / mm Hg
760
475
320
240
150

CAMPUS
63
Practice Problems
The half life for the conversion of ammonium
cynate into urea at 303 K at initial
concentrations of ammonium cynate of 0.1 and
0.2 mol/l are 1152 min and 568 min
respectively. What is the order of the reaction?
2
The half lives periods for decomposition of PH3
for different initial pressures is given below: 1
P, Torr
707
79
37.5
t1/2
84
84
84
October 21, 2016

CAMPUS
64
Practice Problems
Decomposition of a gas is of second order
when the initial concentration of gas is 5 10-4
mol/lit. It is 40% decomposed in 50 min. what
is
the
value
of
rate
constant?
26.67 lit./mol.min
At 25 oC the rate constant for the hydrolysis of
ethyl acetate by NaOH is 6.5 lit per mol per
min., starting with a concentration of base and
ester of 0.03 mol/lit. of each. What proportion
of ester will be hydrolyzed in 10 min? 66.1%
October 21, 2016

CAMPUS
65
Practice Problems
The partial pressure of azo-methane (A) was
observed as a function of time at 600 K with
the results given below. Confirm that the
decomposition A B + C is first order with
respect to A and find the rate constant at this
temperature 3.6 10-4 sec-1
Time in
min
1000
2000
3000
4000
Pressure
(Torr)
820
572
399
278
194
October 21, 2016

CAMPUS
66
Practice Problems
The data for a chemical reaction A + B P is
given below
CA
CB
-dCA/dt initial
rate
0.5
0.5
0.02
0.5
0.08
1.0
1.0
0.16
What is the overall order of the reaction? 3

October 21, 2016

CAMPUS
67
Practice Problems
The following data for the decomposition of azoisopropane at 270 oC was obtained:
Time (s)
180
360
540
720
1020
Pressure /
Torr
35.15
46.30
53.90
58.85
62.20
65.50
Treat decomposition reaction as A

B + C for
calculation purpose, find order of reaction and the
rate constant
K = 1/t ln [(Po / 2Po - P)
October 21, 2016

CAMPUS
68
Solution
P / Po = (No + x) / No
x = [P / Po 1]No
October 21, 2016

CAMPUS
69
CA = (No/PoV)(2Po P)
rA = k (No/PoV)(2Po P) = dP/dt
k = (1/t)ln [Po / 2Po P]

1, 0.00206
October 21, 2016

CAMPUS
70
Practice Problems
The first order reversible liquid reaction A R
CAo = 0.5 mol/lit, CRo = 0 takes place in a batch
reactor. After 8 minutes the conversion of A is
33.3%. While the equilibrium conversion is
66.7%, find the rate expression dCA/dt =
0.0577CA - 0.0288CR
Liquid B decomposes by first order kinetics and
in a batch reactor. 50% of B is converted in a 5
min run. How much longer would it take to
reach 75% conversion?
October 21, 2016

CAMPUS
71
Varying Volume Batch Reactor

Volume is linearly related to conversion
Where
is the fractional change in the volume
of the system

Example
Pure reactant
But with 50% inerts present at the start, two
volumes of reactant mixture yield, on complete
conversion, five volumes of product mixture
The general rate of reaction
Integral method of Analysis

Zero-order reactions:
Integrating gives,
As shown in the following figure, the log of

fractional change in volume versus time yields a
straight line with slope

(Zero order)

(First Order)
First order reaction
Replacing
by V
Semi logarithmic plot of this equation yields a

straight line of slope k

(First Order)

(Second Order)
Second order reaction
Or
The rate is given by

(Second Order)
Replacing
by V and integrating
The following figure shows

how to test for those
kinetics
Practice Problems
Find the first order rate constant for the disappearance
of A in a gas phase reaction
2A R, if on holding the pressure, the volume of the
reaction mixture starting with 80% A decreases by 20%
in 3 mins 0.231 min-1
The gas reaction 2A = R + 2S is approximately 2nd order
with respect to A. When pure A is introduced at 1 atm
into a constant volume batch reactor the pressure rises
by 40% in 3 mins. For a constant pressure batch reactor
find the time required for the same conversion and
fractional increase in volume at that time 3.906 min,
increase in volume 40%
Final two
A gas A decomposes irreversibly to form gas A = 2C. The
decomposition is a first order reaction carried out in a
constant pressure batch reactor. Derive an expression
for the volume of the system as a function of time.
Assume that the reacting gases behave ideally
The decomposition of ammonia on a tungsten wire at
856 oC gave the following results
Total Pressure
/ Torr
228
250
273
318
Time / sec
200
400
600
1000
Determine order and rate constant: 0. 0.112

October 21, 2016

CAMPUS
83
Objective Assessment of Chapter

Determine the reaction order and specific reaction rate
from experimental data obtained from either batch or
flow reactors.
Describe how to use equal-area differentiation,
polynomial fitting, numerical difference formula
There are two ways of meeting difficulties:

you alter the difficulties or you alter
yourself meeting them
October 21, 2016

CAMPUS
84

Chapter 5

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Chapter 5

Uploaded by

Copyright:

Available Formats

BITS, PILANI K. K.

BIRLA GOA CAMPUS

BITS, PILANI K. K. BIRLA GOA

Algorithm for Isothermal Reactor

October 21, 2016

BITS, PILANI K. K. BIRLA GOA

Evaluating the rate equation

October 21, 2016

BITS, PILANI K. K. BIRLA GOA

Integral and Differential Method of

BITS, PILANI K. K. BIRLA GOA

Requires large amount of accurate data

October 21, 2016

BITS, PILANI K. K. BIRLA GOA

October 21, 2016

BITS, PILANI K. K. BIRLA GOA

Differential vs Integral method

October 21, 2016

BITS, PILANI K. K. BIRLA GOA

Batch reactor data

October 21, 2016

BITS, PILANI K. K. BIRLA GOA

Batch reactor data

October 21, 2016

BITS, PILANI K. K. BIRLA GOA

Batch reactor data

October 21, 2016

BITS, PILANI K. K. BIRLA GOA

Batch reactor data

October 21, 2016

BITS, PILANI K. K. BIRLA GOA

Batch reactor data

October 21, 2016

BITS, PILANI K. K. BIRLA GOA

Batch reactor data

October 21, 2016

BITS, PILANI K. K. BIRLA GOA

Batch reactor data

October 21, 2016

BITS, PILANI K. K. BIRLA GOA

Batch reactor data

October 21, 2016

BITS, PILANI K. K. BIRLA GOA

Batch reactor data

October 21, 2016

BITS, PILANI K. K. BIRLA GOA

Batch reactor data

October 21, 2016

BITS, PILANI K. K. BIRLA GOA

Batch reactor data (Graphical)

October 21, 2016

BITS, PILANI K. K. BIRLA GOA

Batch reactor data (Graphical)

October 21, 2016

BITS, PILANI K. K. BIRLA GOA

Batch reactor data (Finite Difference)

Final Point: (dCA/dt) at t = tn

(CA(n-2) - 4CA(n-1) + 3CAn)/ 2t

BITS, PILANI K. K. BIRLA GOA

Constant Volume Batch reactor

October 21, 2016

BITS, PILANI K. K. BIRLA GOA

Analysis of Total Pressure data

October 21, 2016