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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
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Algorithm for Isothermal Reactor


Design

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Evaluating the rate equation

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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
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Requires large amount of accurate data


Develop or build a rate equation to fit data

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Differential vs Integral method

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Batch reactor data

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Batch reactor data

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Batch reactor data

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Batch reactor data

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Batch reactor data

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Batch reactor data

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Batch reactor data

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Batch reactor data

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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

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Batch reactor data

PLOT

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Batch reactor data (Graphical)


time (s)

t1

t2

t3

concentration
(mol/dm3)

CAo

CA1

CA2

CA3

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Batch reactor data (Graphical)


time (s)

t1

t2

t3

concentration
(mol/dm3)

CAo

CA1

CA2

CA3

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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


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Constant Volume Batch reactor

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Analysis of Total Pressure data

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Analysis of Total Pressure data

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Analysis of Total Pressure data

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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

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Integral Method

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Irreversible Uni-molecular type First


Order Reaction

Caution

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Irreversible Bi-molecular type Second


Order Reaction

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Irreversible Bi-molecular type Second


Order Reaction

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Irreversible Bi-molecular type Second


Order Reaction (Caution 1)
Pseudo First Order reaction

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Irreversible Bi-molecular type Second


Order Reaction (Caution 1)

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Irreversible Bi-molecular type Second


Order Reaction (Caution 2)

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Zero order reactions

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Zero order reactions

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Empirical rate equations of


nth order

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Empirical rate equations of


nth order

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Overall order of irreversible


reactions from half life
n not equal to 1

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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

First-Order Reversible
Reactions
The rate equation is

At equilibrium,
Fractional conversion of A at equilibrium
conditions,

First-Order Reversible
Reactions
Equilibrium constant
Combining the equations
On integration,

First-Order Reversible
Reactions

Compare with 1st


order irreversible

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Second order Reversible


Reaction
Bimolecular type second order reactions

Second-Order Reversible
Reactions
Restrictions
and

Integrated rate equation

First-Order Reversible
Reactions
A plot is shown in the figure

Reactions of shifting order


Consider the reaction
Rate equation

Reactions of shifting order

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Reactions of shifting order


To apply the integral method, separate variables and integrate,

Linearize

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Reactions of shifting order

Autocatalytic Reactions

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Autocatalytic Reactions

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Autocatalytic Reactions

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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
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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?
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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

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Time / min

12

16

PP / mm Hg

760

475

320

240

150

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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

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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%
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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

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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


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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)

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Solution

P / Po = (No + x) / No
x = [P / Po 1]No

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Analysis of Total Pressure data

CA = (No/PoV)(2Po P)
rA = k (No/PoV)(2Po P) = dP/dt

k = (1/t)ln [Po / 2Po P]


1, 0.00206

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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?
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Varying Volume Batch Reactor

Varying Volume Batch Reactor


Volume is linearly related to conversion

Where
is the fractional change in the volume
of the system

Varying Volume Batch Reactor


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

Varying Volume Batch Reactor

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

Integral method of Analysis


(Zero order)

Integral method of Analysis


(First Order)
First order reaction

Replacing

by V

Semi logarithmic plot of this equation yields a


straight line of slope k

Integral method of Analysis


(First Order)

Integral method of Analysis


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

Integral method of Analysis


(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


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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

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