Interpretation of Batch

Reactor Data
• A rate equation characterizes the rate of reaction, and its form
may either be suggested by theoretical considerations or
simply be the result of an empirical curve-fitting procedure.
• The determination of the rate equation is usually a two-step
procedure; first the concentration dependency is found at fixed
temperature and then the temperature dependence of the
rate constants is found, yielding the complete rate equation.
• Equipment by which empirical information is obtained can be
divided into two types,
– Batch Reactor
– Flow Reactor
 Batch Reactor
• The batch reactor is simply a container to hold the contents while
they react.
• All that has to be determined is the extent of reaction at various
times, and this can be followed in a number of ways, for example:
1. By following the concentration of a given component.
2. By following the change in some physical property of the fluid,
such as the electrical conductivity or refractive index.
3. By following the change in total pressure of a constant-volume
system.
4. By following the change in volume of a constant-pressure system.

This reactor is a relatively simple device adaptable to small-scale laboratory set-

ups, and it needs but little auxiliary equipment or instrumentation. Thus, it is
used whenever possible for obtaining homogeneous kinetic data.
 Interpretation of Batch
Reactor Data
There are two procedures for analyzing kinetic data,
• Integral and the
• Differential methods.
 CONSTANT-VOLUME BATCH
REACTOR
• Constant-volume batch reactor we are really
referring to the volume of reaction mixture,
and not the volume of reactor.
• Constant-density reaction system
• In a constant-volume system the measure of
reaction rate of component i becomes
Conversion
 Graphing conc. Vs time

• Shows the effect of

reactants being used
up on the rate of
reaction
• If constant = zero order
– Decreasing
concentration is not
affecting the rate
Graphing first order

• If the reaction rate is

halved when the
concentration is
halved, then the
reaction is first order
 Graphing second order

• If halving the
concentration causes
the rate to decrease by
a factor of 4, the
reaction is second
order
• (1/2 )2 = ¼
Rate vs. conc graphs
Integral Method of Analysis of Data
• The integral method of analysis always puts a
particular rate equation to the test by
integrating and comparing the predicted C
versus t curve with the experimental C versus t
data. If the fit is unsatisfactory, another rate
equation is guessed and tested.
 Irreversible Uni-molecular Type First-
Order Reactions
• Consider the reaction
Irreversible Bimolecular-Type Second-Order
Reactions
Thus, for the second-order reaction with equal initial concentrations of A and B, or for
the reaction
The integrated expression depends on the stoichiometry as well as
the kinetics

When a stoichiometric reactant ratio is used the integrated form is

Irreversible tri-molecular type Third-
Order Reactions
Overall Order of Irreversible Reactions
from the Half-Life t1/2
 Graphical determination of rate
The variation in rate can be investigated by measuring the change in concentration of one of the
reactants or products, plotting a graph and then finding the gradients of the curve at different
concentrations.

RATE CALCULATION
In the reaction…
The rate of reaction at
A(aq) + B(aq) ——> C(aq) + D(aq) any moment can be
found from the gradient
the concentration of B was measured of the tangent at that
every 200 minutes. The reaction is point. The steeper the
gradient, the faster the
obviously very slow!
rate of reaction
Place a rule on the
outside of the curve and
draw a line as shown on
the graph.

x
gradient = y / x
 GRAPHICAL DETERMINATION OF RATE
The variation in rate can be investigated by measuring the change in concentration of one
reactants or product, plotting a graph and then finding the gradients of tangents to the curve at
different concentrations.

concentration = 1.20 mol dm-3 RATE CALCULATION

The rate of reaction at any
gradient = - 1.60 mol dm-3 moment can be found from
1520 min the gradient of the tangent
at that point. The steeper
rate = - 1.05 x 10-3 mol dm-3 the gradient, the faster the
rate of reaction
Place a rule on the outside
of the curve and draw a
line as shown on the
graph.

x
gradient = y / x
 Graphical determination of rate
The variation in rate can be investigated by measuring the change in concentration of one of
the reactants or products, plotting a graph and then finding the gradients of the curve at
different concentrations.

The gradients of tangents at several other RATE CALCULATION

concentrations are calculated. The rate of reaction at any
moment can be found from
Notice how the gradient gets less as the reaction the gradient of the tangent
proceeds, showing that the reaction is slowing at that point. The steeper
the gradient, the faster the
down.
rate of reaction
The tangent at the start of the reaction is used to Place a rule on the outside
calculate the initial rate of the reaction. of the curve and draw a
line as shown on the
graph.

x
gradient = y / x
 First order reactions and half life

One characteristic of a FIRST ORDER REACTION is that it is

similar to radioactive decay. It has a half-life that is
independent of the concentration.
It should take the same time to drop to one half of the
original concentration as it does to drop from one half to
one quarter of the original.

The concentration of a reactant falls as

the reaction proceeds
 First order reactions and half life

The concentration of reactant A falls as

the reaction proceeds

The concentration drops from

4 to 2 in 17 minutes
 First order reactions and half life

The concentration of reactant A

falls as the reaction proceeds

The concentration drops from

4 to 2 in 17 minutes
2 to 1 in a further 17 minutes
 First order reactions and half life

The concentration of reactant A falls as

the reaction proceeds

The concentration drops from

4 to 2 in 17 minutes
2 to 1 in a further 17 minutes
1 to 0.5 in a further 17 minutes
First order reactions and half life

The concentration of reactant A falls as

the reaction proceeds

The concentration drops from

4 to 2 in 17 minutes
2 to 1 in a further 17 minutes
1 to 0.5 in a further 17 minutes
First order reactions and half life

A useful relationship
k t½ = loge 2
= 0.693
where t½ = the half life

Half life = 17 minutes

k t½ = 0.693
k = 0.693 =0.041 min-1
t½
Irreversible Reactions in Parallel
Irreversible Reactions in Parallel
 Irreversible Reactions in Series

By multiplying through with the integrating factor

Homogeneous Catalyzed Reactions
Suppose the reaction rate for a homogeneous
catalyzed system is the sum of rates of both
the uncatalyzed and catalyzed reactions
 Autocatalytic Reactions
A reaction in which one of the products of reaction acts as a catalyst
is called an autocatalytic reaction.

Because the total number of moles of A and R

remain unchanged as A is consumed, we may
write that at any time
Autocatalytic Reactions
 Example

• Calculate the concentrations at a given

conversion. If the initial mixture consists
solely of sodium hydroxide at a concentration
of 10 mol/lit and of glyceryl stearate at a
concentration of 2 mol/lit, what is the con
centration of glycerin when the conversion of
sodium hydroxide is (a) 20% and (b) 90%?
 Example

Only the reactants NaOH and (C17H35COO)3C3H5 are initially present: therefore, θC=θD=0
Empirical Rate Equations of nth Order

The order n cannot be found explicitly from above Eq. so a trial-and-error

solution must be made.
Just select a value for n and calculate k.
The value of n which minimizes the variation in k is the desired value of n.

One curious feature of this rate form is that reactions with order n > 1 can
never go to completion in finite time.
On the other hand, for orders n < 1 this rate form predicts that the reactant
concentration will fall to zero and then become negative at some finite time.

Since the real concentration cannot fall below zero we should not carry out the
integration beyond this time for n < 1
 Zero-Order Reactions
• A reaction is of zero order when the rate of reaction is
independent of the concentration of materials.

conversion is proportional to time

 Zero-Order Reactions
As a rule,
 Reactions are of zero order only in certain concentration
ranges (the higher concentrations).
 If the concentration is lowered far enough, we usually find
that the reaction becomes concentration-dependent, in which
case the order rises from zero.
 Zero-order reactions are those whose rates are determined
by some factor other than the concentration of the reacting
materials, e.g.,
 The intensity of radiation within the vat for photochemical reactions,.
 The surface available in certain solid catalyzed gas reactions.
Differential method of analysis
 Half-Life
• The decomposition of ethane (C2H6) to methyl radicals (CH3) is a
first order reaction with a rate constant of
5.36 x 104 s1 at 700 oC.
C2H6 →2CH3
Calculate the half-life in minutes.

0.693
t1/2  4 1
 1293 s
5.36  10 s

1 min
1293 s   21.5 min
60 s
 Second–Order Reactions: Integrated
Rate Law
• Rate law: R = k[A]2 and the integrated rate
equation is:
1 1
 kt 
[ A ]t [ A ]o
1
• Plot of vs. t gives a straight line with a
[ A ]t
slope of k.

• Half-life is 1
t1 / 2 
k  [ A ]o
 Calculating Second Order Half-life

At 330°C, the rate constant for the decomposition of NO2 is

0.775 L/(mol*s). If the reaction is second-order, what is the
concentration of NO2 after 2.5x102 s if the starting of
concentration was 0.050 M?

I(g) + I(g) → I2(g)

The reaction is second order and has a rate constant of 7.0 x 109
M1 s1 at 23oC.
a) If the initial [I] is 0.086 M, calculate the concentration after
2.0 min.
b) Calculate the half-life of the reaction when the initial [I] is
0.60 M and when the [I] is 0.42 M.
a) Use integrated rate equation for 2nd order
1 1 1 1
 (7.0  10 M s ) 120s 
9

 A  0.086 M 
 8.4  1011 M 1
1 12
[A]  1
 1.2  10 M
8.4  10 M
11

1 10
t1/2  1 1
 2.4  10 s
(7.0  10 M
9
s ) (0.60 M )
1 10
t1/2  1 1
 3.4  10 s
(7.0  10 M
9
s ) (0.42 M )
Summary of Orders
 Rate-Determining Step
• Steps of a mechanism must satisfy two requirements
– Sum of elementary steps must equal the overall balanced
equation
– The rate law must have same rate law as determined from
experimental data

• The decomposition of hydrogen peroxide (2H2O2  2H2O + O2)

• may occur in the following two steps Step 1: H2O2 + I →
H2O + IO
• Step 2: H2O2 + IO → H2O + O2 + I
• If step 1 is the rate-determining step, then the rate law is
• rate = k1[H2O2] [I]
• The decomposition of hydrogen peroxide
(2H2O2  2H2O + O2 )
• may occur in the following
¾ k¾®
1
two steps Step 1:
H2O2 + I H2O +¾ k2¾®IO
• Step 2: H2O2 + IO H2O + O2 + I
• If step 1 is the rate-determining step, then
the rate law is
• rate = k1[H2O2] [I]
• I does not appear in the overall balanced
equation
• I serves as a catalyst in the reaction - it is
present at the start of the reaction and is
present at the end
• IO is an intermediate
 Rate Law for All Reactants
• Order for all components done same way.
E.g. Determine the reaction order for each reactant from the table.
(aq)+5Br(aq)+6H+(aq)3Br2(aq)+3H2O(l)
BrO 3
[BrO 3 ]o [Br]o [H+]o Ro
0.10 0.10 0.10 1.2
0.20 0.10 0.10 2.4
0.10 0.30 0.10 3.5
0.20 0.10 0.15 5.4

Eg. 2: Determine the reaction orders for the reaction indicated from the
data provided.
A + 2B + C  Products.

[A]o [B]o [C]o Ro

2.06 3.05 4.00 3.7
0.87 3.05 4.00 0.66
0.50 0.50 0.50 0.013
1.00 0.50 1.00 0.072
 Integrated Rate Law: First–Order Reaction
• For a first order reaction, Rate = [A]/t = k[A] or RA = d[A]/dt = k[A].
[A] [A] k
• Use of calculus leads to: ln or  kt log  t
[ A ]o [ A ]o 2.303
• Allows one to calculate the [A] at any time after the start of the reaction.
E.g. Calculate the concentration of N2O remaining after its decomposition according to 2N2O(g)
 2N2(g) + O2(g) if it’s rate is first order and [N2O]o = 0.20M, k = 3.4 s1 and T = 780°C. Find its
concentration after 100 ms.
k
• Linearized forms: ln[ A ]  kt orln[ A ] o log[ A ]   t  log[ A ]o
• Plot ln[A] vs t. 2.303
• Slope of straight line leads to rate constant, k.
E.g. When cyclohexane(let's call it C) is heated to 500 oC, it changes into propene. Using the
following data from one experiment, determine the first order rate constant.:

t,min 0.00 5.00 10.00 15.00

[C],mM 1.50 1.24 1.00 0.83
 Reaction Mechanisms
• Give insight into sequence of reaction events leading to product (reaction
mechanism).
• Each of the steps leading to product is called an elementary reaction or
elementary step.
• Consider the reaction of nitrogen dioxide with carbon dioxide which is second
order on NO2:
NO2(g) + CO(g)  NO(g) + CO2(g) Rate = k[NO2]2.
• Rate law suggests at least two steps.
• A proposed mechanism for this reaction involves two steps.
Step 1 2NO2(g)  NO3(g) + NO(g)
Step 2 NO3(g) +CO(g) NO2(g) + CO2(g)
Overall NO2 + CO  NO + CO2

– NO3 is a reaction intermediate = a substance that is produced and consumed in the

reaction so that none is detected when the reaction is finished.
• The elementary reactions are often described in terms of their molecularity.
– Unimolecular One particle in elementary.
– Bimolecular = 2 particles and
– Termolecular = 3 particles
 Numerical
Aqueous A reacts to form R (A→R) and in the first minute in a batch reactor
its concentration drops from CAo = 2.03 mol/liter to CAf = 1.97 mol/liter. Find
the rate equation for the reaction if the kinetics are second order with respect
to A.

In a homogeneous isothermal liquid polymerization, 20% of the monomer

disappears in 34 minutes for initial monomer concentration of 0.04 and also
for 0.8 mol/liter. What rate equation represents the disappearance of the
monomer?
 Numerical
• First order rate constant k, for the rotation about the C-N bond in N, N-
di-methylnicotinamide measured at different temperatures by nuclear
magnetic resonance (NMR) are as follows, Determine the activation
energy, E, and the pre-exponential factor, ko, for the rotation.
E = 78.9×103J/mol
• Reaction between ethylene bromide and potassium
iodide in 99% methanol with the following data.
Determine the second order reaction rate constant.