VIETNAM NATIONAL UNIVERSITY – HO CHI MINH CITY

UNIVERSITY OF TECHNOLOGY
FACULTY OF CHEMICAL ENGINEERING

Chemical Reaction Engineering

(Homogeneous Reactions in Ideal Reactors)

Mai Thanh Phong, Ph.D.

FCE – HCMC University of Technology Chemical Reaction Engineering

 Chapter 2. Interpretation of Batch Reactor Data

1. Rates of reaction
1.1. Description of reaction rates
Reaction rates depend usually in a complex manner on the concentrations, the
temperature and often on the effect introduced by catalysts:
r = f ( ci ,T, catalyst)

The order of a reaction is related to the concentration dependence. Typical

examples are:
Irreversible Reactions:

• First order:
A → Products: r = k(T)CA k in [s-1]

• Second order:
A + B → Products: r = k(T)CACB k in [m3 mol-1s-1]
2A → Products: r = k(T)CA2 k in [m3 mol-1s-1]

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 Chapter 2. Interpretation of Batch Reactor Data

Reversible Reactions:

• First order:
A  R: r = k1CA – k2CR k in [s-1]

• Second order:
A + B  R + S: r = k1CACB – k2CRCS k in [m3 mol-1s-1]
2A  2R: r = k1CA2 – k2CR2 k in [m3 mol-1s-1]
2A  R + S: r = k1CA2 – k2CRCS k in [m3 mol-1s-1]
A + B  2R: r = k1CACB – k2CR2 k in [m3 mol-1s-1]

The dependency of the reaction rate on the temperature can be described using
Arrhenius law:
• EA is the activation energy of the reaction.
 EA 
k (T ) = k0 exp  −  • ko is the pre-exponential factor (not dependent on
 RT  the reaction temperature

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 Chapter 2. Interpretation of Batch Reactor Data

1.2. Rate laws of simple reactions

In this section, rate equations of simple reactions and the corresponding
temporal change of concentration are analyzed. A closed system (isothermic,
batch reactor) and aconstant volume are assumed.
1.2.1. Irreversible first-order reactions (Decomposition reactions)
A → Products
1 dCi
The rate equation is: r= = kCi (2.1)
 i dt
dC A
With i is A and vi = -1, then: r = − = kCA (2.2)
dt
CA t
dC A CA
The integration form: − 
C Ao
CA
= k  dt or − ln
0
C A0
= kt (2.3)

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 Chapter 2. Interpretation of Batch Reactor Data

The eq. (2.3) leads to the temporal course of concentration cA.

C A = C A0e − kt (2.4)

C A0 − C A
With XA = , the eq. (2.3) leads to: (2.5)
C A0

− ln(1 − X A ) = kt or X A = 1 − e − kt (2.6)

1.2.2. Irreversible bimolecular-type second-order reactions

Consider the reaction (A + B → Products) with corresponding rate equation

r= (2.7)

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 Chapter 2. Interpretation of Batch Reactor Data

Noting that the amounts of A and B that have reacted at any time t are equal and
given by CA0XA, eq. (2.7) can be written in terms of XA as

r= (2.8)

(2.9)

(2.10)

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 Chapter 2. Interpretation of Batch Reactor Data

After breakdown into partial fractions, integration, and rearrangement, the final
result in a number of different forms is

(2.11)

For the reaction: 2A → Products, the defining second-order differential

equation becomes

r= (2.12)

which on integration yields

(2.13)

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 Chapter 2. Interpretation of Batch Reactor Data

1.2.3. Empirical rate equations of nth order

When the mechanism of reaction is not known, we often attempt to fit the data
with an nth-order rate equation of the form

(2.14)
which on separation and integration yields
(2.15)

1.2.4. Zero-order reactions

Integrating and noting that CA

can never become negative, (2.16)
we obtain directly:

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 Chapter 2. Interpretation of Batch Reactor Data

1.2.5. Irreversible Reactions in Parallel

Consider the simplest case, A decomposing by two competing paths

The rates of change of the three components are given by

(2.17)

(2.18)

(2.19)

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 Chapter 2. Interpretation of Batch Reactor Data

The k values are found using all three differential rate equations. First of all,
eq. (2.17), which is of simple first order, is integrated to give

(2.20)

Then dividing eq. (2.18) by eq. (2.19) we obtain the following

(2.21)

which integrated gives simply

(2.22)

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 Chapter 2. Interpretation of Batch Reactor Data

1.2.6. Irreversible Reactions in Series

Consider the reaction

Rate eqautions for the three components are

(2.23)

(2.24)

(2.25)

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 Chapter 2. Interpretation of Batch Reactor Data

Assuming that at t = 0, concentration of A is CA0, and no R or S present, integration

of eq. (2.23) gives

(2.26)

To find the changing concentration of R, substitute the concentration of A from

eq. (2.26) into the differential equation governing the rate of change of R, eq.
(2.24); thus
(2.27)

Solving the above differential equation gives

(2.28)

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 Chapter 2. Interpretation of Batch Reactor Data

Noting that

which eqs (2.26) and (2.28) gives

(2.29)

If k2 is much larger than k1, Eq. (2.29) reduces to

(2.30)

If k1 is much larger than k2, then

(2.31)

Thus, in general, for any number of reactions in series it is the slowest step that has
the greatest influence on the overall reaction rate.
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 Chapter 2. Interpretation of Batch Reactor Data

By differentiating Eq. (2.28) and setting dCRldt = 0, the maximum concentration of

R and the time at which it occours can be found:

(2.32)

(2.33)

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 Chapter 2. Interpretation of Batch Reactor Data

Figure 2.1 shows the general

characteristics of the
concentration-time curves Eq. (2.26)
for the three components:
• A decreases exponentially, Eq. (2.29)
• R rises to a maximum and
then falls,
• and S rises continuously, the
greatest rate of increase of S Eq. (2.33) Eq. (2.28)
occurring where R is a
maximum.

Eq. (2.30)

Figure 2.1. Typical concentration-time

curves for consecutive first-order reactions.

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 Chapter 2. Interpretation of Batch Reactor Data

1.2.7. First-Order Reversible Reactions

The simplest case is the opposed unimolecular-type reaction

(2.34a)

Starting with a concentration ratio M = CR0/CA0 th e rate equation is

(2.34b)

At equilibrium dCA/dt = 0. Hence from Eq. (2.34) we find the fractional

conversion of A at equilibrium conditions to be

(2.35)

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 Chapter 2. Interpretation of Batch Reactor Data

and the equilibrium constant to be

(2.36)

Combining the above three equations we obtain, in terms of the equilibrium

conversion gives

(2.37)

Taking integration of the above equation, the following relation can be found:

(2.38)

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 Chapter 2. Interpretation of Batch Reactor Data

1.2.8. Second-Order Reversible Reactions

For the bimolecular-type second-order reactions
(2.39a)

(2.39b)

(2.39c)

(2.39d)

with the restrictions that CA0 = CB0, and CR0 = CS0 = 0, the integrated rate
equations for A and B are all identical, as follows

(2.40)

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 Chapter 2. Interpretation of Batch Reactor Data

2. Determination of kinetic parameters

2.1. Integral method
For the integral method, the concentration-time-course of one commponent is
measured.
A tipycal measurement is depicted in CA
Figure 2.2.
After this measured data are compared CA0 *
with theoretical integrated reaction rate
*
equation, for example: *
− kt
*
C A = C A0 e *
*
the unknown parameters can be calculated *
*
by non-linear regression or using the * *
linearised form of the integrated rate * * *
equation: t
CA Figure 2.2. Typical experimental
− ln = kt concentration-time-course
C A0
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 Chapter 2. Interpretation of Batch Reactor Data

The measured data can be inllustrated in a ln(CA/CA0) vs. T diagram. The slope
of the straight line leads to the reaction rate constant (Figure 2.3).

2.6 of 2.3

Figure 2.3. Determination of the reaction rate constant k using the

integrated method in a linearised formulation
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 Chapter 2. Interpretation of Batch Reactor Data

2.2. Differential method

For the differential method, also measurements of concentration-time courses are
necessary.
By means numerical and/or graphic differentiation of all measuring data of
concentration CA(t) the derivative dCA/dt can be determined. The measured data
can be approximated as a straight line in the reaction rate-concentration-diagram.
The procedure is as follows:
1. Plot the CA vs. t data, and then by eye carefully draw a smooth curve to
represent the data.
2. Determine the slope of this curve at suitably selected concentration values.
These slopes dCA/dt = r, are the rates of reaction at these compositions.
3. Search for a rate expression to represent this rA vs. CA data, either by
(a) picking and testing a particular rate form, rA = kf (CA), see Fig. 2.4, or
(b) testing an nth-order form rA = kCAn by taking logarithms of the rate equation
(see Fig. 2.5).

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 Chapter 2. Interpretation of Batch Reactor Data

log(rA)
Figure 2.4. Test for the particular rate Figure 2.5. Test for an nth-order rate
form rA = kf(CA) by the differential method by the differential method.
form.

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 Chapter 2. Interpretation of Batch Reactor Data

Problems
1. Aqueous A at a concentration CA0 = 1 mol/liter is introduced into a batch reactor
where it reacts away to form product R according to stoichiometry A → R. The
concentration of A in the reactor is monitored at various times, as shown below:

a) For CA0 = 500 mol/m3 find the conversion of reactant after 5 hours in the batch
reactor.
b) Find the rate for the reaction.

2. For the elementary reactions in series

find the maximum concentration of R and when it is reached.

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 Chapter 2. Interpretation of Batch Reactor Data

3. In the presence of a homogeneous catalyst of given concentration, aqueous

reactant A is converted to product at the following rates, and CA alone determines
this rate:

We plan to run this reaction in a batch reactor at the same catalyst concentration
as used in getting the above data. Find the time needed to lower the concentration
of A from CA0 = 10 mollliter to CAf = 2 mol/liter.

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