Chapter 9

Development of rate equation for homogeneous

multiple reactions

Chemical reactions that occur with more than one reaction in a single process to produce a
stable product are called multiple reactions. The majority of chemical products obtained now
a days involve multiple reactions. Multiple reactions are broadly classified in to two main
category of reactions namely series and parallel reactions. These reactions can be irreversible
and reversible and also a combination of the two. Some of the multiple reactions are:

 Reversible reactions

kf
A+B C+D
kr

Where k f and k r are forward and reverse rate constant respectively

As an illustration of such type of reactions is isomerization of butane

kf
n-C4H10 kr i-C4H10

 Series (i.e., consecutive) reactions.

k1 k2
A  B 
 C

An example of series reaction is the decomposition of acetone

k1
(CH 3 ) 2 CO  CH 4  CH 2 CO
k2 1
CH 2 CO   C 2 H 2  CO
2
 Parallel /simultaneous / reactions,
224 Development of rate equation for homogeneous multiple reactions

k1 B

k2 C

An example of reacting system is dehydrogenation of ethanol

k1 C2H4 + H2O

C2H5OH

k2 C2H4O + H2

 Combination of series and simultaneous reactions

HCHO + 2H2O
k1
CH4 + n/2 O2 k2
CO2 + 2H2O

1 k3
HCHO  O2   CO  H 2O
2

 Parallel and concurrent reactions,

k1
A 
 C
k2
B  D

An example of a Parallel and concurrent reactions are the formation of phthalic anhydride
from ortho-xylene oxidation, on vanadium pentoxide as catalyst taken from Belay Woldeye’s
dissertation.

CH3
CH3 O

CHO COOH O
CH3 CH3
O
CHO
CH3 CH2OH O
CHO
O
Expressions of rate equation in multiple reactions 225

In a complex system, it may matter little, whether the reactant is totally converted or not. We
can maintain easily for such type of reaction high conversion by using a larger reactor, a
lower flow rate, or a higher temperature. The main interest in multiple reactions is the
selectivity to form a desire product and the yield of that product. In another word, the
objective of a complex reaction is to boost the wanted and to depress the unwanted products.
This is because poor selectivity requires consumption of more reactant for a given amount of
desired product, and separation of reactants and products and disposal costs increase
markedly as the amount of unwanted product increases. For example, in the air oxidation of
ethylene, we get

k1 CH2OCH2

CH 2  CH 2  O2
k2 2CO2+2H2O

The desired product is ethylene oxide, but complete oxidation leads to carbon dioxide and
dCCH OCH
2 2 but not
dCCH 2 CH 2
water. For this reaction, our sole interest is . In such
dt dt
reactions, our interest is to maximize the formation of ethylene oxide and minimize the
formation of carbon dioxide and water. It can be well understood that the greater the amount
of CO2 and H 2 O formed, the greater will be the cost of separating the unwanted product,
from the wanted product, ethylene oxide. Generally, complex reactions are mainly
characterized by yield and selectivity and these are defined in chapter one..

9.1 Expressions of rate equation in multiple reactions

The characteristics of a multiple reactions are that it forms two or more reactions from a
single and or different reactants. The kinetics interest in such type of reactions is to predict
the conversion as well as of the product distribution / concentration of individual species / as
a function of main parameters like time and space time from the rate equations. Once we
know the concentration / conversion /, it is possible to evaluate the rate constants from
experimental data. The kinetics of such reactions are studied by using the principle of
independency which is explained in chapter three under item “reversible reactions”.

Recalling equation (4.9) the net rates of formation of j for multiple reactions is

R
r j    i , j ri (4.9)
i 1
226 Development of rate equation for homogeneous multiple reactions

As we said, that the rate expression cannot be changed when using a batch or continuous
system provided the order of reaction and concentration is unchanged. Thus combining rate
formation and mole balance equation, we have

Batch reactor
R
1 dn j
V dt
  i, j ri (9.1.1)
i 1
Plug flow reactor
dF j R

dV
  i , j r i (9.1.2)
i 1
Continuous stirred tank reactor
F j,0 - F j R

-V
 
 i, j r i (9.1.3)
i 1

For constant volume batch reactor, equation (9.1.1) becomes

dC j R

dt
  i , j r i (9.1.1.1)
i 1

Example 9.1 For the following reactions, find the formation of species A,B,C,D and E for a
batch reactor at a constant volume:
k1 k4 k6
A   B   D   F

k2 k3

k5
E 
 C

Solution

Using equation (9.1.1.1) the following differential equations are obtained for each
components
dC A
 k1C A  k 2 C A  (k1  k 2 )C A (E.9.1.1)
dt
dCB
 k1C A  k3C B  k 4C B  k1C A  C B (k3  k 4 ) (E.9.1.2)
dt
Expressions of rate equation in multiple reactions 227

dCC
 k 2 C A  k 3C B  k 5 C E (E.9.1.3)
dt
dCD
 k 4C B  k 6C D (E.9.1.4)
dt

dC D
 k 4C B (E.9.1.5)
dt

dC E
 k 5 C E (E.9.1.6)
dt

dCF
 k 6C D (E.9.1.7)
dt

Example 9.2 Write net rates of formation of species A, B, C and D for the following
combined reactions:
A  2B 
 C (1) for which,  r k C C2
1, A 1, A A B

3C  2 A 
 D (2) for which, r k C3 C 2
2, C 2, C C A

Solution
Since the rate of formations of A and C are given, law of definite proportions and the
stoichiometric equations are the sources to solve the problem; hence we have to use the
following general relationship for each reactions:

r r r r
r  A  B  C  D (9.2)
A B C D
Species A:

Species A is participating in two reactions and the net rate of formation is given by,

r A  r1, A  r 2, A (E.9.2.1)

For reaction 2, we have

r r
2, A 2, C
 (E.9.2.2)
2 3
228 Development of rate equation for homogeneous multiple reactions

r  2 (r ) (E.9.2.3)
2, A 3 2, C
and
(r )  k C3 C 2
2, C 2, C C A

or
r  2 (r )2k C3 C 2 (E.9.2.4)
2, A 3 2, C 3 2, C C A

Thus
r  k C C2  2 k C3 C 2 (E.9.2.5)
A 1, A A B 3 2, C C A

For species B:

r B  r1, B (E.9.2.6)
r r
1, A 1, B

1 2
1
r  r (E.9.2.7)
1, A 2 1, B
r  2( r )  (2)( k C C2 ) (E.9.2.8)
1, B 1, A 1, A A B

r  2 k C C2 (E.9.2.9)
1, B 1, A A B
Thus
r  2k C C2 (E.9.2.10)
B 1, A A B

For species C:
r C  r1, C  r 2, C (E.8.2.11)

r r
1, A 1, C

1 3
r  3r (E.9.2.12)
1, C 1, A

r  (3)( k C C2 ) (E.9.2.13)
1, C 1, A A B
or
Expressions of rate equation for simultaneous reactions under constant volume 229

r  3k C C2
1, C 1, A A B
r  k C3 C 2 (E.9.2.14)
2, C 2C C A

Thus
r k C C2  k C3 C 2 (E.9.2.15)
C 1, A A B 2, C C A

For species D:
r r
2, C 2, D

3 1
1
r r (r )  (E.9.2.16)
D 2, D 3 2, C
r  ( 1 )(k C3 C 2 ) (E.9.2.17)
D 3 2, C C A

r  1k C3 C 2 (E.9.2.18)
D 3 2, C C A

Progress Test 9.1. Write differential equations for plug flow reactor under constant
volumetric flow for the above reactions.
Note that in solving multiple reactions problems often use the so called a Steady State
Principle. This principle allows us to express that the concentration of unstable intermediates
are very small and their rates become zero. For an example, if in example 5.1 component D is
unstable, then the rate of formation of D approaches to zero.

9.2 Expressions of rate equation for simultaneous reactions under

constant volume
In Simultaneous reactions, the reacting substances, instead of proceeding in one path to yield
a given set of products, also follow one or more other paths to give different products as
shown in the following reaction:
k1 D

A k2 X
k3
Y
and the rate of formation
p
r  k Cn  k Cm  k C (9.3)
A 1 A 2 A 3 A

These reactions can be of many different types and can be distinguished with the following
categories:
i) Parallel reaction with a single reactant of equal reaction order, where
nm p
230 Development of rate equation for homogeneous multiple reactions

ii) Parallel reaction with a single reactant but with different reaction order,
where n  m  p

iii) Parallel reaction where more reactants are involved, such as,

k1 D

A + B

k2 X
and the rate of formation
p
r  k Cn Cm  k C Cr (9.4)
A 1 A B 2 A B

9.2.1 Simultaneous reactions in batch reactor

Conditions: Isothermal and perfectly mixed operation
A) First-order simultaneous reaction
The outcome of this reaction will be to obtain variation of the concentration with time. Let us
consider a reaction , which is first-order in each step:

k1 Y

X
k2 Z

In the reaction, a substance X takes part simultaneously in two reactions resulting into the
formation of two products Y and Z. It is to be noted here that in general, k1  k 2 . The net
rate of formation of X is given using equation (4.9)
R
rj   i, j r i
i 1
r X   1, X r1   2, X r 2 (9.5.1)
Substituting a batch reactor mol balance on species X for constant volume, we get
dC X
  1, X r1   2, X r 2 (9.5.2)
dt
or
dC X
 r1  r 2 (9.5.3)
dt
or
dC X
  k1C X  k 2 C X  C X (k1  k 2 ) (9.5.4)
dt
Expressions of rate equation for simultaneous reactions under constant volume 231

Separation of variables followed by rearrangement and integration gives:

C X  C X ,0 exp  (k1  k 2 )t  (9.6.1)

In terms of conversion

 ln(1 - X )  (k1  k 2 )t (9.6.2)

X

Note that equation (9.6.2) is similar to equation (5.8.2) of first –order single reaction. The
only difference is that, equation (9.6.2) contains the sum of two first – order constants
(k1  k 2 ) .
Kinetics study mainly focuses on determining of order of reaction and rate constant. It is to
observe that by simple analysis of the reactant A versus time data, that is plotting
 ln C C or  ln(1 - X ) versus time t, yields the sum of rate constants
A A,0 X
(k1  k 2 ) and not the separate values of the constants k1 and k 2 . This is demonstrated in
Figure 9.1.

slope  k  k CY
1 2
C
A,0
 ln
C
A
k1
slope 
C Y ,0 k
2

t C
Z ,0
C
Z

Figure 9.1 Finding the rate constants in simultaneous first – order reactions

Additional data to find the rate constant is k k ratio. This is found by computing the
1 2
concentration of each of the products formed in the reaction. Using equation (9.1.1.1):

dC Y
  1,Y r1 (9.7.1)
dt
or
dC Y
 k1C X (9.7.2)
dt
and
232 Development of rate equation for homogeneous multiple reactions

dC Z
  2, Z r 2 (9.8.1)
dt
or
dCZ
 k 2C X (9.8.2)
dt
To facilitate the integration, we can apply two methods namely,

(i) Substituting for Cx from equation (5.6)

Integration for the condition C X  C X ,0 & CZ  CZ ,0 at t  0, which will give us,

C
Y
C
Y ,0
C
X ,0 k k
k
1 1  exp (k 1  k 2 )t (9.7.3)
1 2
similarly

C
Z
C
Z ,0
C
X ,0 k k
k
2 1  exp (k 1  k 2 )t (9.8.3)
1 2
(ii) Using time-free basis,

dC k C k
Y  1 x
 1
(9.9.1)
dC C (k  k ) k k
X X 1 2 1 2

By integrating and rearranging, we get

C
Y
C
Y ,0

k k
k
1 C X
C
X ,0
 (9.9.2)
1 2
or

C
Y
C
Y ,0

k k
k
1 C X ,0
C
X
 (9.9.3)
1 2

Substituting for CX and rearranging, we get, equation (9.7.3). By analogous expression to Y,

we can get equation (9.8.3).
Dividing equation (9.7.3) by equation (9.8.3), and for condition C C  0 we get Y ,0 Z ,0
selectivity ratio of the reaction,

CY k
 1 (9.10.1)
C k
Z 2
Expressions of rate equation for simultaneous reactions under constant volume 233

Plotting C versus C , we obtain as a slope k k . Knowing k  k and k k ,

Y Z 1 2 1 2 1 2
the values of k and k can be determined. This is shown in Figure 8.3
1 2
Equation (9.10.1) also can be obtained immediately from the instantaneous selectivity of
rY
i.e.,
r
Z
dC Y dC Z
 (9.11)
dt dt

Equation (9.10.1) shows that during the entire course of the reaction and also that at the end
of the reaction, the ratio of the concentration of the products remains constant and equal to
the ratio of the rate constants. This leads to the conclusion that the selectivity depends on the
rate constant ratio i.e., it is a function of temperature and does not depend on the type of the
system (batch or continuous). It is extremely important to note that where both simultaneous
reactions are of identical order, the selectivity ratio C C , is totally independent of time
Y Z
(or process) being solely determined by rate constant ratio which is a function of
temperature. This is also demonstrated if we take the definition of selectivity ratio from
equation

C C
S  Y  Y (3.17.2)
Y C  C C  C
X,0 X Y Z

and substituting for these concentrations equations (9.7.3) and (9.8.3) we get

k
S  1
(9.12)
Y k k
1 2

It is clear from equation (9.12) that selectivity to form Y, which is independent of

conversion if both reactions are of first order. Typical concentration profile in simultaneous
reactions is shown in Figure 9.2.

Since the rate constants are only a functions of temperature, the product ratio /Selectivity/
can be increased by altering the temperature. By combining equation (8.35.1) with Arrhenius
equation for the activation energy, we get

C k A exp ( E / RT )
Y  1  1 1
(9.10.2)
C k A exp(  E / RT )
Z 2 2 2
or
C A
1 exp
 E 2  E1 
Y   (9.10.3)
C A  RT 
Z 2  
234 Development of rate equation for homogeneous multiple reactions

If E1>E2, an increase in temperature will increase the rate of first reaction over the second.
However, if E2>E1, then the temperature should be decreased in order to increase the product
Y relative to Z.

The yield can be expressed by taking equation (9.9.3) and dividing both sides by CX,0,

YY 
C Y  C Y ,0

k
1

C X ,0  C X  (9.13.1)
C X ,0 k1  k 2 C X ,0

Equation ( 9.13.1) can, then be expressed in terms of time variable and conversion as
follows:

Y 
Y
1 k1
C X ,0 k 1  k 2
C
X ,0
C
X ,0

exp  (k  k )t
1 2
 (9.13.2)

k
Y  1 X (9.13.3)
Y k k X
1 2

The equation (9.13.3) expresses that in simultaneous reaction, the yield depends upon the rate
constant and conversion i.e., the type of the process.

C X ,0
CY

CZ

C
X

Figure 9.2 Typical simultaneous first order-reaction concentration profile

It is easy to observe that when three or more simultaneous first-order reactions take place, the
result obtained will be similar to equation (9.10.1). Thus, for the reaction,
Expressions of rate equation for simultaneous reactions under constant volume 235

B
k1
k2
A C
k3
D

the concentration of the products remains constant and equal to the ratio of the rate constants
(provided that the original mixture does not contain them), i.e.,

C :C :C :     k : k :k : (9.14)
B C D 1 2 3

Progress Test 9.2 Show how equation (9.14) occurs

Example 9.3 Suppose the following two first-order reaction are occurring in a constant
volume and isothermal batch reactor

k1 B

A
k2 2C

After a reaction time of 50 min, 90% of a reactant A has decomposed and the product is
found to contain 9.1 mol of B per mol of C. Neither B nor C is present initially in the reaction
vessel. Evaluate the rate constants k1 and k2.

Solution

For the reaction, the concentration of A, equation (9.6.1) becomes

C A  C A,0 exp  (k 1  k 2 )t   (9.6.1)

or, in terms of conversion of A

X
A
 1
CA
C A, 0

 1  exp  (k  k )t
1 2
 (E.9.3.1)

Hence
 ln(1  X A )  ln(1  0.90)
k k   (E.9.3.2)
1 2 t 50

 0.0405min 1
Using equation (9.1.1.1)
 236 Development of rate equation for homogeneous multiple reactions

dC j R

dt
  i , j r i
i 1
we can write
dC A
 k 1 C A  k 2 C A  (k 1  k 2 )C A (E.9.3.3)
dt

dC B
 k1C A (E.9.3.4)
dt

dC
C
 k2C A (E.9.3.5)
dt
then
dC k C k
B  1 A  1 (E.9.3.6)
dC k C k
C 2 A 2

Integration with the initial condition C B,0  C C ,0  0 at t = 0, the result is similar to

equation
CB k
 1 (9.10.1)
C k
C 2

for constant volume this equation becomes

n k
B  1 (E.9.3.7)
n k
C 2

It is given that

n  9.1 n (E.9.3.8)
B C

or
nB
 9 .1 (E.9.3.9)
n
C

Using stoichiometry relationship

n n n n n n
A A,0 B B ,0 C C ,0
  (E.9.3.10)
1 1 2
Expressions of rate equation for simultaneous reactions under constant volume 237

n B  n A,0  n A  n 1 (E.9.3.11)

n C  2(n A,0  n A )  2n 1 (E.9.3.12)

then the required relationship is

n n
B  1  1  9.1 (E.9.3.13)
n 2n 2
C 1
nB
 18.2 (E.9.3.14)
n
C

then in equation (E.9.3.7)

n k
B  1  18.2 (E.9.3.15)
n k
C 2
k  18.2k (E.9.3.16)
1 2

Using the value of k1 and k2 obtained from above we have

k  0.0437min 1
1

k  2 x 4 x10 3 min 1
2

Example 9.4 Consider simultaneous reactions

A
 P  W for which, r k C
P 1, A A

A
 C  I for which, r k C
C 2, A A

The reaction is carried out for 10 minutes under constant volume and temperature in batch
reactor. Using the following data:

k 1, A  0.001s -1 ; k 2, A  0.002 s -1; C A,0  4000 moles / m3

Calculate
a) Conversion of A
b) Product distribution
c) The yield of P and C
238 Development of rate equation for homogeneous multiple reactions

d) The selectivity of P and C

e) Plot the product distribution versus time.

Solution

(a) Conversion of A

Conversion of A is computed using

C A,0  C A
XA 
C A,0

The value of C can be computed using equation (9.1.1.1)

A

dC j R

dt
  i , j r i
i 1
dC A
 k 1, A C A  k 2, A C A  (k 1, A  k 2, A )C A (E.9.4.1)
dt
This integrate to


ln C A  ln C A,0   (k 1, A  k 2, A )t  (E.9.4.2)

 
or
C A  C A,0 exp  (k 1, A  k 2, A )t (E.9.4.3)

C  4000exp (0.001 0.002)(10)(60)  661.19 mol / m3

A
We can calculate conversion

C A,0  C A 4 000  661.19

XA    0.835
C A,0 4000
(b) Product distribution

Product distribution also computed using equation (9.1.1.1)

dC j R

dt
  i , j r i
i 1

With respect to P and W

Expressions of rate equation for simultaneous reactions under constant volume 239

dC dC P
W
  k 1, A C A (E.9.4.4)
dt dt

From equation (E.9.4.1) and (E.9.4.4) we get

dC k 1, A  k 2, A
 A 
(E.9.4.5)
dC P k 1, A

Integration yields

C A  C A,0 - (1  k 2, A k 1, A )(C P  C P,0 ) (E.9.4.6)

or
C A,0  C A
C P  CW  (E.9.4.7)
1  k 2, A k 1, A
4000  661.19
C  C   1113 moles / m 3
P W 1  0.002 0.001
dC dC I
C
  k 2, A C A (E.9.4.8)
dt dt

From equation (E.9.4.1) and (E.9.4.8) we get

dC k 1, A  k 2, A
 A 
(E.9.4.9)
dC C k 2, A

Integration gives

C A  C A,0 - (1  k 1, A k 2, A )(C C  C C,0 ) (E.9.4.10)

or
C A,0  C A
CC  C I  (E.9.4.11)
1  k 1, A k 2, A

4000  661.19
C  C   2226 moles / m 3
C I 1  0.001 0.002

(c) The yield of P and C

Recalling equation (3.22.2) and modifying for constant volume the yield becomes
240 Development of rate equation for homogeneous multiple reactions

CP
  (E.9.4.12)
P C A,0

1113
   0.278
P 4000
Similarly
C
  C (E.9.4.13)
C C A,0
2226
   0.557
C 4000
(d) The selectivity of P and C

Recalling equation (3.16.3) and modifying for constant volume yields

CP
S  (E.9.4.14)
P C A,0  C A
1113
S   0.333
P 4000  661.19
Similarly
C
S  C (E.9.4.15)
C C A,0  C A
2226
S   0.667
C 4000  661.19

(e) Plotting the product distribution versus time

Using equations (E.9.4.3), (E.9.4.7) and (E.9.4.11)

 
C A  C A,0 exp  (k 1, A  k 2, A )t  4000e  0.003 t (E.9.4.16)
C A,0  C A (4 000 - C )
C P  CW   A
(E.9.4.17)
1  k 2, A k 1, A 3
C A,0  C A 4000  C
CC  C I   A
(E.9.4.18)
1  k 1, A k 2, A 1 .5

Equations (E.9.4.16), (E.9.4.17) and (E.9.4.18) are used to plot concentration versus times of
0, 1500 seconds and time approach ∞. This are plotted in Figure 9.3.
Expressions of rate equation for simultaneous reactions under constant volume 241

C
j

4 C C
C I

3
C C
P W
2

1
C
A
0
t
Figure 9.3 Product distribution versus time of exercise 8.6

B) Mixed - order simultaneous reactions

Let us consider the reaction,

k1 Y second order

k2 Z first order

Using equation (8.1.1.1)

dC j R

dt
  i , j r i
i 1

the net rate of disappearance of X is given by,

dC X
  k1C X 2  k 2 C X (9.15)
dt

The rate formation of Y and Z, therefore, can be given as

242 Development of rate equation for homogeneous multiple reactions

dC Y
 k1C X 2 (9.16.1)
dt
and
dC Z
 k2C X (9.16.2)
dt

Expression for C and C can be obtained using a time free basis

Y Z
dC k C 2 k C
Y  1 X  1 X (9.17.1)
dC X k C 2 k C k1C X  k 2
1 X 2 X

Integrating (C  C ; C X  C X ,0 at t  0) for C Y , we get

Y Y ,0

C 
C Y ,0 C  k C X C X ,0  k 2 k 1 C X ,0
Y 
 1 X   2 ln (9.17.2)
C X ,0 C X ,0  C X ,0  k 1 C X ,0 1  k 2 k 1 C X ,0
 
and for C , by the same reasoning we get
Z
C C Z ,0 k 1  k 2 k 1 C X ,0
Z   2 ln (9.18)
C X ,0 C X ,0 k 1 C X ,0 C X C X ,0  k 2 k 1 C X ,0

Selectivity ratio for condition at C

Y ,O
 C Z ,0  0 is
C 1 C / C
Y  X X ,0
(9.19)
C  k  1 k k C
Z  2  ln 2 1 X ,0
k C  C C k k C
 1 X ,0  X X ,0 2 1 X ,0

Taking equations (9.16.1) and (9.16.2), one can show that

CY k C
 1 X (9.20)
C k
Z 2
Maintaining a high concentration of X in the reaction will favor the product of Y over that to
Z. Typical selectivity profiles are shown in Figure 9.4
The selectivity in mixed- order reaction can very easily demonstrate that it can get increased
by altering the temperature and the concentration of the reactants. General observation on
simultaneous reactions of equal order is that the selectivity can be increased by altering the
temperature. In the case of simultaneous reactions which are of mixed order, the selectivity
of one product over another can be increased by altering the temperature and the
concentration of the reactants.
Expressions of rate equation for simultaneous reactions under constant volume 243

10
X  X  Y 2 nd  order
X Z 1st  order
CY 8
K  10 X X  1
CX
CZ C X ,O
6
k1C X ,O
K
k2
4

2 K 1

0
0 0.5 1.0
XX
Figure 9.4 Selectivity profile for mixed – order simultaneous reaction

Let us consider the following reaction,

k1 B -------------------- desired product

k2 C --------------------- undesired product

As per the rate laws, we get

r  k C (9.21)
B 1 A

r k C
 (9.22)
C 1 A
Therefore, the sum of the rate of disappearance of A can be given as,

r  k C  k C
 (9.23)
A 1 A 2 A

where  and  are positive order of the reaction. Thus, maximum desired product is
obtained, when instantaneous selectivity of B as high as possible, i.e the rate of formation of
B is much bigger compared to the rate of formation of C. In this case,
244 Development of rate equation for homogeneous multiple reactions

rB k C k1
S  
1 A  C
 
(9.24.1)
B r k C
 k A
C 2 2
A

or, as we wish this ratio to be as big as possible.

Case 1: when   
In this case the reaction order of the desired product is greater than the undesired product
order. Let     n , a positive number, then the equation (9.24.1) is given as,
k
S  1 Cn (9.24.2)
B k A
2
The ratio of the desired product to the undesired product will be high, if the reactant
concentration can be kept as high as possible. This can happen when: In gas phase run
without inert and conducted under high pressure conditions. In liquid phase, dilution is
avoided.

Case 2: when   
That is where the order of the undesired product is greater than the order of the desired
product,     n, is negative and then the equation (9.24.1) becomes,
k 1
SB  1 (9.24.3)
k 2 Cn
A
In order for equation (9.24.1) to yield highest desired product, the reactant concentration
should be as low as possible. This may be effected by diluting the concentration of A with
inerts.

Case 3: when   
k k
S  1 C A0  1 (9.24.4)
B k2 k
2
Here, the selectivity is of zero order and is not influenced by the reactant concentration but
only can be influenced by the ratio of the rate constants.

Generally, for simultaneous reactions, the concentration level of reactants is the key to proper
control of product distribution. A high reactant concentration favors the reaction of higher
order, a low concentration favors the reaction of lower order, while the concentration level
has no effect on the product distribution for reaction of the same order. If all the above cases
are examined, the factor of the temperature influence is ignored. In other words, it can be
said that it occurs under isothermal conditions. When there is temperature sensitivity, in such
case the selectivity parameters can be determined from the ratio of the specific reaction rates,
Expressions of rate equation for simultaneous reactions under constant volume 245

k
1 
A
1 exp
 
 E 1  E 2 / RT  (9.25)
k A
2 2
where A is the frequency factor and E is the activation energy.

Case 4: when E  E
1 2
For such cases, the rate constant of the desired product increases more rapidly with the
increasing temperature than the undesired product i.e., we obtain high rate of formation of B.
Thus, we apply high temperature to maximize selectivity.

Case 5: when E E
2 1
Reactions should be carried out at low temperature up to the level, where the reaction can
proceed.

Example 9.5 Reactant A decomposes by three simultaneous reactions to form three products
given as,
B -------------------- desired product

A C -------------------- undesired product

D --------------------- undesired product

As per rate laws, they can be given as,

   1 1  
rB  0.0012exp 26000  C A  (E.9.5.1)
   300 T  

   1 1  
rC  0.0018exp 25500  C1A.5  (E.9.5.2)
   300 T  

   1 1  
rD  0.00452exp 5000  C A0.5  (E.9.5.3)
   300 T  

In what conditions, would it minimize the unwanted products C and D?

Solution

Since the activation energies of reactions equations (E.9.5.1) and (E.9.5.2) are much greater
than the activation energy of reaction (equation (E.9.5.1)) the rate of formation of D will be
negligible with respect to the rates of formation B and C at high temperatures i.e.,
r
S B  B  Very large (E.9.5.4)
r
D
Now we need only consider the relative rates of formation of B and C at high temperature.
246 Development of rate equation for homogeneous multiple reactions

r 0.66 e 5001 300 1 T 

S  B  (E.9.5.5)
B r
C C 0.5 A
We observe that the amount of undesired product C, can be minimized by carrying out the
reaction at low concentration. Therefore, to maximize the conversion of A to B we would
want to operate our vessel at high temperatures (to minimize the amount of D formed and
low concentration of A to minimize the amount of C formed).

Example 9.6 The following reaction believed to take in the process

k1
A + B k2 C +D

k3
C + B  E + D

k4
2D   F
Where A and B are the reactants, E and F are the products and C and D are reactive
intermediate. Assume r 2  r 3 and use the steady state principle to obtain an expression for
the rate in terms of A and B. What is the total order?

The rate of formation for the reactions are

dC A
 k 1 C A C B  k 2 C C C D (E.9.6.1)
dt
dC B
 k 1 C A C B  k 2 C C C D (E.9.6.2)
dt
dC
C
 k1C A C B  k 2 C C C D  k 3 C C C B (E.9.6.3)
dt
dC D
 k 1 C A C B  k 2 C C C D  k 3 C C C B  2k 4 C D 2 (E.9.6.4)
dt
dC E
 k3CC C B (E.9.6.5)
dt
dC F
 k4CD 2 (E.9.6.6)
dt
From the steady state principle

dC dC D
C
  0 (E.9.6.7)
dt dt
Then
Expressions of rate equation for simultaneous reactions under constant volume 247

k C C k C C k C C  0 (E.9.6.8)
1 A B 2 C D 3 C B
k C C
C  1 A B
(E.9.6.9)
C k C k C
2 D 3 B
and
k 1 C A C B  k 2 C C C D  k 3 C C C B  2k 4 C D 2  0 (E.9.6.10)

Substituting the value of equation (E.9.6.9) into equation (E.9.6.10) we obtain

 k C C   k C C 
k C C k  1 A B C D  k 3  1 A B C B  2k 4 C D 2  0 (E.9.6.11)
1 A B
 2 D  k 3 C B
2 k C
  k 2 C D  k 3 C B 

It is given that r 2  r 3 and thus

k C k C (E.9.6.12)
2 D 3 B

Thus equation (E.9.6.9) and (E.9.6.11) reduced to

k C C
C  1 A B (E.9.6.13)
C k C
2 D
k k C C 2
1 3 A B 2k C 2 (E.9.6.14)
k C 4 D
2 D
a
 k k  3 a
2
a
1
C   C
1 3
C (E.9.6.15)
D  2k k  A B
 2 4 

Substituting this equation (E.9.6.6) yields

23
dC F  k k  23 4
k 
1 3
 C C 3  kC 2 3 C 4
3 (E.9.6.16)
dt 4  2k k  A B A B
 2 4 
23
 k k 
where k  k 4  
1 3
 2k k 
 2 4 

Equation (E.9.6.16) shows the reaction is 2 / 3 – order with respect to A and 4 / 3 – order
with respect to B, making all over reaction to be of second – order.
248 Development of rate equation for homogeneous multiple reactions

9.2.2 Simultaneous reactions in continuous reactor

9.2.2.1 Simultaneous reactions in plug flow reactor

Conditions: Isothermal and steady – state operation

Here, we do not need to repeat the derivative for plug flow reactor, because all expression
derived are simply translated from batch to plug flow by replacing the time t by the space
 , although these times have quite different meanings. As illustration let us consider the
F
same reactions with first – order kinetics

k1 Y

k2 Z

The net rate of formation of X is given using equation (4.9)

R
rj    i, j r i
i 1
r X   1, X r1   2, X r 2 (9.26)

Recalling space time

V
F 
F
V,0

Differentiation with constant volumetric flow rate

dV
d F  (9.27.1)
F
V,0
or
dV  d F F V,0 (9.27.2)
Substituting a plug flow reactor mol balance on species j for constant volumetric flow rate,
we get
dF R

j
  i, j r i (9.28.1)
dV
i 1
Expressions of rate equation for simultaneous reactions under constant volume 249

dF R
  i, j r i
j

d F F V,0
i 1
d (C j F ) R
V,0
d F F V,0
  i, j r i
i 1
or
dC R
  i, j r i
j
 (9.28.2)
d F
i 1

For species X, then

dC
X  r   r (9.29.1)
d 1, X 1 2, X 2
F
or
dC X
 r1  r 2 (9.29.2)
d
F
or
dC
 X k C  k C (9.29.3)
d 1 X 2 X
F
Separation of variables followed by rearrangement and integration gives:

C X  C X ,0 exp  (k 1  k 2 ) F   (9.29.4)

Note that, equation (9.29.4) is identical to equation (9.6.1) of batch reactor, the only thing is
replaced time, t by the space time  . Similarly we can pursue for the other components to
F
get

C
Y
C
X ,0 k k
k
1 1  exp (k 1  k 2 ) F  (9.29.5)
1 2

C
Z
C
X ,0 k k
k
2 1  exp (k 1  k 2 ) F  (9.29.6)
1 2
and
CY k
 1 (9.10.1)
C k
Z 2
Equation (9.10.1) demonstrate that the selectivity ratio does not depend on the system,
whether we are working in batch or plug flow reactor in simultaneous reactions.
250 Development of rate equation for homogeneous multiple reactions

Progress Test 9.2 Derive the rate expression for any mixed - order reactions in terms of
space time versus concentrations of individual species

Example 9.7 Simultaneous first – order irreversible reactions

k1 Y

k2 Z

is carried out in a continues reactor at isothermal and constant volume. For the data given,
FV ,0
 4 x10 -3 m3 / min; C  2000 moles / m3 ; k  0.5 min -1; k  0.1 min -1
A,0 1 2
. Determine  ,C , S Y , and Y Y for 90 % conversion of X in plug flow reactor.
F Y

Solution

Rearranging equation (9.29.4) yields

1 C
X ,0
F  ln (E.9.7.1)
k k C
1 2 X
where
C X  C X ,0  C X ,0 X X  2000 - (2000)(0.9)  2 00 mole /m3
so that
1 2000
F  ln  3.84 min.
0.5  0.1 200
Taking equation (9.29.5)

C C
Y
k1
X ,0 k  k
1  exp  (k  k )
1 2 F
  
1 2
we have
C  (2000)
0.5
1  exp (0.5  0.1)(3.84)  1500 moles / m 3
Y 0.5  0.1
CY
S 
Y
C X ,0 - C X
1500
S   0.83  83 %
Y 2000 - 200
CY
S 
Y C X ,0
Expressions of rate equation for simultaneous reactions under constant volume 251

1500
S   0.75  75 %
Y 2000

9.2.2.2 Simultaneous reactions in continuous stirred tank reactor

Conditions: Isothermal, perfectly mixed and steady-state operation

Taking the same reactions with first – order kinetics, the net rate of formation of X is given
using equation (4.9)
R
rj  
 i, j r i
i 1
r X   1, X r1   2, X r 2 (9.30)
Combining with equation (9.1.3) yields
F F
X ,0 X
 k C  k C (9.31.1)
V 1 X 2 X
F (C C )
V ,0 X ,0 X
 (k C  k C )  C (k  k ) (9.31.2)
V 1 X 2 X X 1 2

(C C )
X ,0 X
C (k  k ) (9.31.3)
F X 1 2

or
C
X ,0
C  (9.31.4)
X ( k   k  1)
F 1 F 2

By combining the mole balance and the rate laws for the other components, we get
C C
Y Y ,0
k C (9.32.1)
F 1 X

CZ  C
Z ,0
 k 2C (9.33.1)
F X

Substituting equation (9.32.1) and (9.33.1) into (9.31.4) and rearranging for
C Y ,0  CZ ,0  0 at t  0, we get

k  C
1 F X ,0
C  (9.32.2)
Y ( k   k  1)
F 1 F 2
 252 Development of rate equation for homogeneous multiple reactions

k  C
2 F X ,0
C  (9.33.2)
Z ( k   k  1)
F 1 F 2

Again division of the number of equations (9.32.2) and (9.33.2) gives us

CY k
 1 (9.10.1)
C k
Z 2

As we have seen here, for other kinetics and for irreversible simultaneous reactions the
expressions are similar and we do not have to repeat the same methods what we have already
gone in batch reactor.

Progress Test 9.3 Derive the rate expression for second - order reactions of A and B in
terms of space time versus concentrations of individual species in CSTR

Example 9.8 Repeat exercise 8.9 for continuous stirred tank reactor
Solution

The space time for CSTR is calculated rearranging equation (9.31.3)

C C
X ,0 X
F  (E. 9.8.1)
C (k  k )
X 1 2

2000  200
F   15 min.
(200)(0.5  0.1)

Taking equation (9.32.2)

k  C
1 F X ,0
C 
Y ( k   k  1)
F 1 F 2
(0.5)(15)(2000)
C   1500 moles / m 3
Y (0.5)(15)  (0.1)(15)  1
The selectivity and the yield can be computed using the following equations,

CY
S 
Y C X ,0 - C X

1500
S   0.83  83 %
Y 2000 - 200
Expressions of rate equation for consecutive reactions under constant volume 253

CY
S 
Y C X ,0
1500
S   0.75  75 %
Y 2000

As expected, the selectivity and yield are the same with plug flow reactor for the first – order
reaction but the CSTR requires a longer space time.

9.3 Expressions of rate equation for consecutive reactions under

constant volume
Reactions that proceed from the reactants to products not directly but through one or more
intermediate products are called consecutive reactions. They are of general type represented as,
k1 k2
A  B  C

The two sequential steps are characterized by rate constants k1 and k2. Such schemes involves
two independents stoichiometrically chemical equations. The category of such reactions belongs
to, for example, the hydrolysis of esters of dicarboxylic acids.

COOC 2 H 5
H 2C   H 2C  COOH
 H 2O  C 2 H 5OH
COOC 2 H 5 COOC 2 H 5

H 2C  COOH  H 2C  COOH
 H 2O  C 2 H 5OH
COOC 2 H 5 COOH

With the consecutive reactions, the reaction path always ends in the final product (s) of the
reaction chain. In many cases, one of the intermediate products is the one desired. In
consecutive reactions, one of the requirements is to find complete product distribution. This is
done by deriving the kinetic sequence of reactions.

9.3.1 Consecutive reactions in batch reactor

Conditions: Isothermal and perfectly mixed operation

A) First-order consecutive reactions

Consider the following reaction,

k1 k2
A  B 
 C
The concentration of A, B, and C as a function of time are found using the following three
equations
254 Development of rate equation for homogeneous multiple reactions

R
rj    i, j r i (4.9)
i 1
dC A
r   k C (9.34.1)
A dt 1 A
dCB
r   k C k C (9.35.1)
B dt 1 A 2 B
C C  C A,0  C A  C B (9.36.1)

Equation (9.34.1) may be integrated at once to give us,

C A  C A,0 exp (k 1 t ) (9.34.2)

when we substitute CA into equation (9.35.1) the following differential equation is obtained:
dC B
 k 2 C B  k 1 C A,0 exp (k 1 t ) (9.35.2)
dt
Equation (9.35.2) is a linear first-order differential equation. Which gives us the analytical
solution, with the stated initial condition at t  0, C A  C A,0 and CB  CC  0 as follows:
CB k1  k 1 t k t 
  e e 2  (9.35.3)
C A,0 k 2  k1  

The concentration of CC as a function of time may be obtained by substituting equations

(9.34.2) and (9.35.3) into equations (9.36.1) and rearranging we obtain

C 1  k 1 t k t 
C
 k 2 (1  e )  k (1  e 2 ) (9.36.2)
C A,0 k 2  k1  1


Equation (9.35.3) and (9.36.2) shows that the yield of B and the selectivity ratio C B C C
depend on the time as well as on the rate constants. This is in contrast to the result for
simultaneous reactions. Component A shows the same as A decomposing by a first –order
reaction to B, since A has no direct decomposition to C. Thus, the C (t ) profile is an
A
exponential decay. The concentration of B initially increases as time elapses, however, as C
B
continuous to increase and C to decrease, a time is reached at which k C k C , and
A 1 A 2 B
C reaches a maximum, after which it continuously decreases. Figure 9.5.shows the
B
concentration profile of consecutive reactions.

The maximum value of B can be obtained by differentiating equation (9.35.3) with respect to
time and set the derivative equal to zero for C B  0 .
Expressions of rate equation for consecutive reactions under constant volume 255

dC k k t k t 
B 0  k e 1 k e 2 
1
(9.35.4)
dt k k  1 2

2 1

ln(k k )
t  2 1
(9.37)
max, B k k
2 1
The time required for maximum B depends on the value of the rate constants. It can easily be
seen that the larger the value of k at a given constant k , the more rapidly the maximum
2 1
concentration can be attained. Substituting this value of the time equation (9.37) in equation
(9.35.3) gives us the maximum yield of B.

k2
C k  k k
 1  2 1
B, max
(9.35.5)
C k 
A,0  2 

Figure 9.6 illustrate typical concentration- time curve showing maximum B. The selectivity
ratio C B C C can be obtained on dividing equation (9.35.3) by equation (9.36.2). This
becomes very large at low time values and decreases at larger times. The first-order consecutive
reaction is simply carried out also on a time-free basis. For this we combine equation (9.34.1)
and equation (9.35.1), to get

dC k C k C k C
B  1 A 2 B  1  2 B
(9.38)
dC k C k C
A 1 A 1 A
 k2 
  
C k  C A  k 1 C 
which can be readily integrated to, B  1  A (9.39)
C A,0 k 1  k 2  C A,0  C A,0 
  
 
Yield C B C A,0 is then uniquely related to conversion of A and the rate constant ratio k1 k 2 ,
which is as shown in Figure 9.7
The values of rate constants k and k govern the location and maximum concentration of B as
2 1
can be seen in the Figure 9.8
As already known, rate equation is determined through experimental methods. In such type of
reactions also, values of the rate constants k1 and k can be obtained from experimental
2
measurements of C and C at various times. Obtaining these two rate constants can be
A B
simple or complicated. The simple procedure is first to obtain k1 from equation (9.34.2) and
second to obtain k from k1 and either of the coordinate of the maximum value of C .
2 B
These coordinates as shown using equation (9.35.1)
256 Development of rate equation for homogeneous multiple reactions

dCB
 k C  k 2C  0
dt 1 A B
or
k k t
C  1 C e 1 max
B, max k 2 A,0

Cj
CC

CB

CA

Figure 9.5 Concentration – time profiles (product distribution) for A 

k1
B 
k2
C

Overall selectivity

C B, max

C
CC

CB

CA

tmax t

k1 k2
Figure 9.6 Schematic presentation of a typical consecutive-reaction A  B 
 C
 Expressions of rate equation for consecutive reactions under constant volume 257

1 .0
CB
     .locus of maximum
C A,0 K  10
CB 0 .8
Yield
C A,0

0 .6

K 1
0 .4

K  0.1
0 .2

0
0.2 0.4 0.6 0.8 1.0

Conversion of A

Figure 9.7 Relationship of yield C B C A,0 with the conversion of A for the reaction
k1 k2
A   C , where K  k1 k 2
B 

k1=k2 k1>> k2 k2>>k1 CC

CA
C CC C CB C

CA
CB CC CA CB

t t t

Figure 9.8 Behavior of location and maximum concentration of B in relation to the values of
k1and k2 for the reaction A 
k1
B 
k2
C
258 Development of rate equation for homogeneous multiple reactions

Example 9.9 The following reaction,

k1 k2
A  B  C
is carried out in batch reactor. If C B  C B,O  0 initially and C A,O  100 mol m 3 for a given
condition a) k1  1 s 1 ; k 2  2 s 1 b) k1  1 s 1 ; k 2  10 4 s 1 , what is the time at which the
concentration of B is maximum?. What is the maximum concentration of B?

Solution

Taking equation (9.37) the maximum time to obtain maximum CB will be calculated
1 k
a) t max,B  ln 2 (E.9.9.1)
k 2  k1 k1
1 2
 ln  0.693 s
2 1 1
1 k
b) t max,B  ln 2 (E.9.9.2)
k 2  k1 k1

1 10 4
 ln (E.9.9.3)
10 4  1 1
ln104  9.2 x10 4 s
1

10 4
The maximum concentration of B will be calculated using equation (9.35.5)
k2
 k  k k
C C  1  2 1 (E.9.9.4)
B, max A,0  k 
 2 
1
a) C B ,max 100   25 mol m 3
2
1
 1 
b) C B ,max  100 4   0.01mol m 3
 10 

B) Higher-order consecutive reactions

Let us consider a mixed-order reaction,

k1
A  B         First  order
k2
A  B 
 C      Second  order

The net rate of disappearance of A can be given as using equation,

Expressions of rate equation for consecutive reactions under constant volume 259

R
rj    i, j ri (4.9)
i 1
dC
A  k C k C C (9.40)
dt 1 A 2 A B

and the net rate of disappearance of B as,

dC B
 k1C A  k 2 C A C B (9.41)
dt

Applying time –free basis, we get

dC k C k C C C k k
B  1 A 2 A B  B 1 2
(9.42.1)
dC k C k C C C k k
A 1 A 2 A B B 1 2

then, by integrating for the condition C B  C B 0 at C A  C A0 , we get

CB K  1 K  CB  
 B  1  A
C C 
 ln (9.42.2)
C A, 0 C A, 0 K  C B , 0 C A, 0  C A, 0 
 

where K  k1 k 2

It is to be noted here, that equation (9.42.2) cannot be explicit of C B C A, 0 , but the behavior of B
in the reaction as a function of conversion of A can be graphically demonstrated for the various
values of K C A, 0 . On the other hand, some high-order consecutive reactions can be easily
worked out using time-free basis. For example, let us consider the reaction,

k1
A  B  C         Second  order
k2
B  C 
 D         Second  order

then, we have the rate of A,B,C and D as,

dC A
 k 1 C A C B
dt
dC B
 k 1 C A C B  k 2 C B C C
dt
260 Development of rate equation for homogeneous multiple reactions

dC
C
 k1C A C B  k 2 C B C C ;
dt
dC D
 k 2C ACC
dt

Applying time-free basis, we get

dC k C
C
 1  2 C (9.43.1)
dC k C
A 1 A

Note that equation (9.43.1) is identical to equation (9.38) for the reaction A
 B 
 C , a
consecutive of the first-order reaction. Integration for the condition

C A,0  C A , C C,0  C C at t  0
gives
 k2  k2
 k  C  C k
CC 1  C A  1  C A   C ,0  A  1
 (9.43.2)
C A,0 1  k 2 k 1  C A,0  C A,0  C A,0 C 
    A,0 
 

when k1= k2, we have as in the first-order consecutive case

CC C C C 
 A  C ,0
 ln A  (9.44)
C A,0 C A,0  C A,0 C A,0 
 

9.3.2 Consecutive reactions in continuous reactor

9.3.2.1 Plug flow reactor

Conditions: Isothermal and steady-state operation

We do not need to repeat the derivation of consecutive reactions for the plug flow reactor,
because the transformation of t   into equation gives a plug flow reactor.
F

Progress Test 9.4 Derive the rate expression for second - order consecutive reactions of A and
B in terms of space time versus concentrations of individual species in CSTR

Example 9.10 Consider the following consecutive reaction

A 
k1
1 B 
k2
 2C
Expressions of rate equation for consecutive reactions under constant volume 261

Reaction is carried out isothermally at 1000 K in a plug flow reactor. The rate constants for the
reaction are
  81300 1
k1  1.81x10 4 exp  in h
 RT 
 50000 1
k 2  1.16 x101 exp  in h
 RT 
where 1 = 0.90

Neglecting the change in the total number of moles,

a) Calculate the conversion of A and the concentration of B product per

concentration of A fed for space time of 2 hours.
b) Determine the yield of B and the maximum product of B per concentration of A
fed.

Solution

Using equation (9.28.2), the rate equations are

dC
A  k C (E.9.10.1)
d 1 A
F
dC
B  k C   k C (E.9.10.2)
d 1 1 A 2 2 B
F

a)
  81300 
k1  1.8 x104 exp   (E.9.10.3)
 8.3141000 
1.0253 h 1
  50000 
k 2  1.16x101 exp   (E.9.10.4)
 8.3141000 
 0.0284 h 1

Integration of equation (E.9.10.1)

 k 1 F
C C e (E.9.10.5)
A A,0
or
CA
 e  k1 F (E.9.10.6)
C A,0
262 Development of rate equation for homogeneous multiple reactions

and conversion
C A,0  C A C
XA   1 A
(E.9.10.7)
C A,0 C A,0
it follows that
X
A
 1  exp  k  1 F
 (E.9.10.8)
 1  exp 1.0253x2  0.8713

b)

The net rate of appearance of B

dC
B  k C  k C (E.9.10.9)
d 1 1 A 2 B
F
dC
B k C  k C (E.9.10.10)
d 2 B 1 1 A
F
dC  k 1 F
B k C  k C e (E.9.10.11)
d 2 B 1 1 A,0
F
then differential equation for the condition C 0
B,0

CB  1 k 1  k  k 2  F 
 e 1 F e  (E.9.10.12)
C A,0 k 2  k1  


0.91.0253 exp 1.0253x2
0.0284 1.0253
 exp (0.0284x 2)
CB
 0.7554 (E.9.10.13)
C A,0

At the maximum value of C C

B A,0

d (C C )
B A,0
0 (E.9.10.14)
d
F

By use of this condition and equation (E.9.10.12), it is found that

Expressions of rate equation for consecutive reactions under constant volume 263

ln k 2 / k1
F  (E.9.10.15)
k 2  k1
ln 0.0284 1.0253

0.0284  1.0253
 F  3.60 h

At this value of  F

X A  1  exp (1.0253x3.60)  0.7363

 0.9750
and
C
B 
0.91.0253 exp (1.0253x3.60)  exp (0..0284x3.60)
C 0.0284  1.0253
A,0
 0.8126mol of B produced per A fed

9.3.2.2 Consecutive reactions in continuous stirred tank reactor

Conditions: Isothermal, perfectly mixed and steady-state operation

Consider the reaction

k1 k2
A  B 
 C

The net rate of formation for multiple reactions can be written,

R
r j    i , j ri (4.9)
i 1

The net rate of formation for component A becomes

r A   1, A r1

C C
A,0 A
k C (9.45.1)
F 1 A

C
A,0
C  (9.45.2)
A 1  k 
1 F

Similarly for component B,

264 Development of rate equation for homogeneous multiple reactions

r  r   r
B 1, B 1 2, B 2

C C
B B ,0
k C k C (9.46.1)
F 1 A 2 B

CB
 k 2 C B  k1C A
F
C C
B k C k A,0
F 2 B 1 1  k 
1 F

k C
1 A,0
F
C  (9.46.2)
B (1  k  )(1  k  )
1 F 2 F
rC   r
2, C 2

C C
C ,0 C
 k C (9.47.1)
 2 B
F
or
C
C  k C
F 2 B

k 1 k 2 C A,0  2 F
C  (9.47.2)
C (1  k  )(1  k  )
1 F 2 F

The maximum value of C , C , we can find by differentiating C (t ) with respect to

B, max B B
F using equation (9.46.2) as

dC k C k 21C F k k C F
1 A,0 A,0 1 2 A,0
B
0  
d (1  k  )(1  k  ) (1  k  ) 2 (1  k  ) (1  k  )(1  k  )2
F 1 F 2 F 1 F 2 F 1 F 2 F


k 1 C A,0k  k  
0 1  1 F
 2 F
 (9.48)
(1  k  )(1  k  )  (1  k  ) (1  k  )
1 F 2 F  1 F 2 F 

The term in the larger parentheses must be equal to zero, after rearranging
1
 F , max  (9.49)
(k k )1 2 1 2
 Expressions of rate equation for consecutive reactions under constant volume 265

Substituting back into the equation (9.46.2) yields

k C
1 A,0
C  (9.46.3)
B, max
( k 1 2  k 1 2 )2
1 2
The components A, B and C against is given in Figure 9.9

k  k2 k  k 2 k  k1
1 1 2
C
A Cj C
Cj C
Cj C C C
C A B C A,0
C A,0
C A,0
C C
C C A
B
C
B

k 1 F k 1 F k 1 F

Figure 9.9 Behavior of location and maximum concentration of B in relation to the values of
k1and k2 for the reaction A 
k1
B 
k2
C in CSTR

Example 9.11 Consecutive first – order irreversible reactions

k1 k2
A  B  C

is carried out in a continues reactor at isothermal and constant volume. For the data given,
F
V ,0
 4 x 10 - 3 m3 / min; C  2 000 moles / m3 ; k  0.5 min -1; k  0.1 min -1 .
A,0 1 2
Determine  ,C , S , and Y for 90 % conversion of X in continuous reactor.
F Y Y Y
Solution
A) Plug flow reactor
Rearranging equation (E.8.11.5) gives
1 C A,0
F  ln (E.9.11.1)
k C
1 A
1 2000
F 
ln  4.61 min
0.5 200
Slightly modifying equation (E.8.11.12) yields
k   k 1 F k  
C C 1
e e 2 F  (E.9.11.2)
B A,0 k  k
2 1  

0.5   (0.5)(4.61)
C  2000 e  e  (0.1)(4.61)   1333 moles / m 3
B 0.1  0.5  
266 Development of rate equation for homogeneous multiple reactions

Selectivity computed using equation

CB
S  (E.9.11.3)
B C A,0  C A
1333
S   0.74  74 %
B 2000  200

The yield of B is defined as

CB
Y  (E.9.11.4)
B C A,0
1333
Y   0.66  66 %
B 2000

B) Continuous stirred tank reactor

Application of equation (9.45.1) yields

C C
A,0 A
F  (E.9.11.5)
k C
1 A
2000  200
F   18 min
(0.5)(200)
Taking equation (9.46.2) the concentration of B can be computed
k C 
1 A,0 F
C 
B (1  k  )(1  k  )
1 F 2 F
(0.5)(2000)(18)
C   640 mole / m 3
B (1  (0.5)(18))(1  (0.1)(18))
The selectivity is
CB
S 
B C A,0  C A
640
S   0.36  36 %
B 2000  200
The yield is
CB
Y 
B C A,0
640
Y   0.32  32 %
B 2000
 Multiple reactions with variable volume 267

Note that, working in CSTR requires a longer residence time for the same conversion and
kinetics than PFR. It is also obtained in CSTR much lower selectivity and yield than PFR to the
intermediate product. The main reason is that in CSTR the residence time is higher and due th
this high time in the reactor the product B decompose to the product C. Products distribution
profile for CSTR and PFR is given for comparison in Figure 9.10.

k  k2 k  k 2 k  k1
1 1 2
C
A Cj C
Cj C
Cj C C C
C A B C A,0
C A,0
C A,0
C C
C C A
B
C
B

k 1 F k 1 F k 1 F

Figure 9.10 Comparison of concentrations in the reactions A 

k1
B 
k2
C in PFR (dashed
curves) and CSTR (solid curves)

9.4 Multiple reactions with variable volume

So far in this chapter we were taking constant volume multiple reactions, where the total number
of moles is not a linear function of conversion. In such cases any problem can be solved using
only concentration parameter. When density varies, we need to find another variable to express
the progress of a reaction. One of the variables might be conversion. We halve often express
conversion in the reaction. In multiple reactions conversion can be defined for single reactions as
well as for the overall reactions.

Consider the following parallel reactions

k1
A  B        r k C        X
1 1 A A,1
k2
A 
 D        r k C        X
2 2 A A,2

Recalling equation (3.7.1) concentration for multiple reactions for constant volume
R
  i, j
C C C i 1 
j j ,0 A,0 i, A
 i, A
268 Development of rate equation for homogeneous multiple reactions

Taking initially pure concentration of A, we can write the species in terms of conversion as

C A  C A,0 (1 -  1, A -  2, A )
C B  C A,0  1, A
C D  C A,0  2, A
The overall conversion for these parallel reactions become

X A   1, A   2, A

Using individual conversion for each path of reaction, we can write concentration of each species

at constant volume for CSTR using

R
rj  
 i, j r i (4.9)
i 1
or
C - C R
  i, j r i
j ,0 j
 (9.1.3)
 F
i 1

hence
C A,0 ( 1, A   2, A )   F (r1  r 2 )   F (k 1  k 2 )C A,0 (1 -  1, A -  2, A ) (9.50.1)
C B  C A,0  1, A   F r1   F k 1 C A,0 (1 -  1, A -  2, A ) (9.50.2)

C C  C A,0  2, A   F r 2   F k 2 C A,0 (1 -  1, A -  2, A ) (9.50.3)

Eliminating C from these equations, we get

A,0

 1, A   2, A   F (k 1  k 2 )(1 -  1, A -  2, A ) (9.51.1)
 A,1   F r1   F k 1 (1 -  1, A -  2, A ) (9.51.2)
 2, A   F r 2   F k 2 (1 -  1, A -  2, A ) (9.51.3)

These gives
 F k1
  (9.51.4)
1, A 1  k   k
F 1 F 2
F k2
  (9.51.5)
2, A 1  k   k
F 1 F 2
Multiple reactions with variable volume 269

Equations (9.51.4) and (9.51.5) can be inserted into the expression of each concentration species
to obtain
C
A,0
C C (1 -  -  ) (9.52.1)
A A,0 1, A 2, A 1  k   k
F 1 F 2

C
A,0
 F k1
C C   (9.52.2)
B A,0 1, A 1  k   k
F 1 F 2
C
A,0
F k2
C C   (9.52.3)
C A,0 A,2 1  k   k
F 1 F 2

The concentrations expressions we found are identical with equations (9.31.4), (9.32.2), and
(9.33.2) derived previously, hence there is no need to derive the concentration expressions for
the others multiple reactions and reactors.

Concentration of individual species for variable density reactions follow the same procedure as
we did above the only things we have to consider here is the change of volume. Let us consider
the following consecutive reactions
k1
A  2B         r  k C         X
1 1 A 1, A
k2
2 B 
 2C        r k C        X
2 2 B 2, B
Here the total moles vary with conversion because 1 mole of A is converted into two moles of C
when the reaction goes to completion. In this case we cannot use the equation as we did for a
constant density for CSTR
R
C j ,0 - C j   F  i, j r i 
i 1

and we need to use the variable density equation of the system

R
F j ,0 - F j  V  i, j r i (9.53.1)
i 1
For the above reaction the molar flow rate in terms of a basis F moles initially
A,0
F F (1  X )
A A,0 1, A
F  2F (X  X )
B A,0 1, A 2, B
F  2F X
C A,0 2, B

FT  F A,0 (1  X 1, A ) (9.54)
The volume occupied by the species is given recalling equation for variable volume
270 Development of rate equation for homogeneous multiple reactions

FV , f  FV ,0 (1  X 1, A ) (9.55)

Then the concentration of each species

F F (1  X ) 1  X
A,0 1, A 1, A
C  A  C
A F V, f FV ,0 (1  X 1, A ) 1  X 1, A
A,0

F 2F (X  X ) X  X
A,0 1, A 2, B 1, A 2, B
C  B   2C (9.56)
B F F (1  X ) A,0 1  X
V, f V ,0 1, A 1, A
F 2F X X
A,0 2, B 2, B
C  C
  2C
C F F (1  X ) A,0 1  X
V, f V ,0 1, A 1, A

The mole balance for CSTR using equation (9.53.1) for each species

1  X 1, A
F A,0 - F A  F A,0 X 1, A  V ( 1, A ) r1  Vr1 Vk 1 C Vk 1 C A,0 (9.57.1)
A 1  X 1, A
- F B   F A,0 ( X 1, A  X 2, B )  V (2)(r1 - r 2 )  V (k 1 C  k 2C )
A B
 1  X X  X  (9.57.2)
 V k 1 C A,0 
1, A 1, A 2, B
- k 2 C A,0
 1  X 1  X 
 1, A 1, A 
- F  F X  V (1)r  - Vk C
C A,0 2, B 2 2 B

 X 1, A  X 2, B 
 V k 2 C A,0  (9.57.3)
 1  X 1, A 
 

Solving these equations for the volume mixture of the reactions we obtain

1, A (1  X 1, A ) 1, A (1  X 1, A )
X X
V F F
A,0 k C V ,0
1 A,0 (1  X 1, A ) k (1  X 1, A )
1
X X
1, A 2, B
V F
V ,0 1 X X  X
1, A 1, A 2, B
k - k
11  X 2 1 X
1, A 1, A
Multiple reactions with variable volume 271

X 2, B (1  X 1, A )
V  FV , 0 (9.58.1)
k 2 ( X 1, A  X 2, B )

These equations are used to compute and X

X and then we can insert the values to
1, A
2, B
compute C , C , and C C . One can see, the equations in variable density are not
A B
simple and require considerable manipulations.

Progress Test 9.5 Derive the rate expression for the above consecutive reactions to show
variation of volume as a function of concentrations for PFR

Example 9.12 Consider the following reactions

k1
A  B  C   r k C        X  1
1 1 A 1, A 1
k2
A 
 D r k C        X   0
2 2 A 2, A 1

Which are carried out in a plug flow reactor at constant temperature and pressure. Using the
following data:
Feed are a mixture of 75 % A and 25 % inert.
F V ,0
 200 m3 / min; C  0.05 mol / m3 ; k  0.01 min -1; k  0.0025 min -1.
T ,0 1 2

a) Calculate the space time to achieve 50 % conversion of A

b) Calculate the corresponding molar flow rate of the species
Solution

Application of rate laws gives

dF
j
r   r (E.9.12.1)
j dV j

The rate of formation of species is

dF A dF B
   k1C A (E.9.12.2)
dV dV

dF A dF D
   k2C A (E.9.12.3)
dV dV

The molar flow rate and conversion are defined by

272 Development of rate equation for homogeneous multiple reactions

F F  F X -F X
A A,0 A,0 1, A A,0 2, A
F F X
B A,0 1, A
F F X
C A,0 1, A
F F X
D A,0 2, A

FT  FT ,0  F A,0 X 1, A (E.9.12.4)
and

FT
1  y X
F T ,0 A,0 1, A

or

FT
1  y  X
F T ,0 A,0 1 1, A

FT
1   X
F T ,0 1 1, A

The final volumetric flow rate for constant temperature and pressure can be determined using
equation of state
F
F F ( T )
V, f V ,0 F
T ,0
FV , f  FV ,0 (1   1 X 1, A ) (E.9.12.5)

a) The space time

Recalling equation (9.27.1), we have

dV
d F 
F
V,0
or using equation (E.9.12.2), the rate equations are
Multiple reactions with variable volume 273

dF B
 k1C A
dV
dF B (E.9.12.6)
 k1C A
d ( FV , 0   F )
dF B FA
k (E.9.12.7)
FV , 0 d  F 1 F
V, f
or
dF F A,0 (1  X - X 2, A )
1, A
B k (E.9.12.8)
F d 1 F (1   X )
V ,0 F V ,0 1 1, A
On the other hand

F F X
B A,0 1, A
dFB  F A,0 dX 1, A (E.9.12.9)

Substituting equation (E.9.12.9) into equation (E.9.12.8) we get

FV ,0 dX 1, A F A,0 (1  X - X 2, A )
1, A
k
F d 1 F (1   X )
V ,0 F V ,0 1 1, A
or

dX 1, A (1  X 1, A - X 2, A )
k (E.9.12.10)
d 1 (1   X )
F 1 1, A
Similarly we have

dX 2, A (1  X 1, A - X 2, A )
k (E.9.12.11)
d 2 (1   X )
F 1 1, A

Combining equations (E.9.12.10) and (E.9.12.11) and integrating gives us

X k
1, A
 1 (E.9.12.12)
X k
2, A 2
k
X 2, A  X 1, A 2 (E.9.12.13)
k
1

We combine equations (E.9.10.10) and (E.9.10.13) to obtain

274 Development of rate equation for homogeneous multiple reactions

dX 1, A
 k1
1  (1  k 2 k 1 ) X 1, A  (E.9.12.14)
dF 1   1 X 1, A

For isothermal operation we can integrate this equation,

X 1, A 1   X F
1 dX
1 1, A
 k d
1 
(E.9.12.15)
0  (1  k 2 k 1 ) X 1, A 1, A
0
F

Integrating yields

 
1  (1   1 ) k 2 k 1 ) 1  1 X 1, A 
F  ln( ) - (E.9.12.16)
k  2 1  (1  k k ) X 1  k k 
1  (1  k k ) 2 1 1, A 2 1 
 2 1 

From the problem statement we have

k
2  0.25 , k  0.01 min -1,   0.75
k 1 1
1

Substituting in equation (E.9.12.16) yields

 1 
 F  128ln - 60 X 1, A  (E.9.12.17)
 1  1.25 X 1, A 
 
The conversion is

X A  X 1, A  X 2, A  0.5 (E.9.12.18)
k
X  2 X  0.5
1, A k 1, A
2
 k 
X  1  2   0.5
1, A
 k2 

 X 1, A 1  0.25   0.5

X  0.4
1, A
Multiple reactions with other kinetics in batch reactor 275

Substituting the conversion to equation (E.9.12.17) yields

 1 
 F  128ln - 60(0.4)   64.7 min -1
 1  1.25(0.4) 

b) Molar flow rate of the species

Using our definition, we have

F T ,0 F A,0 1
C T ,0   (E.9.12.19)
FV ,0 y A,0 FV ,0
or

F A,0  y A,0 FV ,0 C T ,0  (0.75)(200)(0.05)  7.5 mol min

Stoichimetric equations give

F
A
F
A,0
1 - X
1, A
- X
2, A
  7.5 1 - 0.5  3.75 mol min
F  F  F X  7.5(0.4)  3 mol min
B C A,0 1, A
F 7.5(0.1)  0.75 mol min
2, A 
F X
D A,0

9.5 Multiple reactions with other kinetics in batch reactor

For other kinetics in multiple reactions the procedure is identical except that the expressions
become differ. It is also important that, we do not need to repeat the derivation for all types
of reactors, what we have done so far. Here we restrict our selves only to batch reactor.

9.5.1 Parallel or concurrent reactions

Let us consider the reaction,

k1
A 
 B
k2
R 
 Y

Where by the combination of mass balance and application of rate laws gives
R
rj  
 i, j ri (4.9)
i 1
276 Development of rate equation for homogeneous multiple reactions

Hence,
dC dC
 A  B k C
1 A
(9.59.1)
dt dt
and
dC R dC Y
   k2CR (9.60.1)
dt dt

By integrating and rearranging equation (9.59.1), we get

k t
C C e 1 (9.59.2)
A A,0
Substituting CA in equation (9.59.1), followed by integration and rearrangement for the
condition CB = 0 at t = 0, we get
 k t 
C C 1 e 1  (9.59.3)
B A,0 
 
In the same manner, equation (9.60.1) can be integrated and rearranged to give

k 2 t
C C e (9.60.2)
R R,0

Substituting C R in equation (9.60.1) followed by integration and rearrangement for the

conditions C  0 at t  0 , we get
Y

 k 2 t 
C C 1 e (9.60.3)
Y R ,0  
 
CB CB
then the overall selectivity and yield can be expressed as,
CY C A,0

k 1 t 

C 1 e
C A,0  
B    (9.61.1)
C  k t 
Y C 1 e 2 
R ,0
 

CB k 1 t CA
 1 e  1 X (9.61.2)
C A,0 C A,0 A

It can be clearly seen that, overall selectivity and yield in the concurrent reactions depend
upon time as well as the rate constants.
Progress Test 9.6 Derive the rate expression for the above reactions to show variation of
volume as a function of concentrations for PFR and CSTR
Multiple reactions with other kinetics in batch reactor 277

9.5.2 Combination reactions

By combination reactions, we mean a combination of parallel and consecutive reactions,
such as

k1 k4
A 
 B 
 D

k2 k3

k5
E 
 C

A great number of combination reaction schemes, often complex, occur in industrial practice.
These reactions usually involve simultaneous, consecutive, and parallel reaction types. Our
aim is to derive and integrate the equations which can define the overall selectivity and yield
of B, C and D as a function of conversion of A. Following combination of material balance
on the species and the rate laws applied for the above scheme of reaction, we get
R
rj    i, j r i (4.9)
i 1
dC A
 (k 1  k 2 )C A (9.62)
dt
dC B
 k 1 C A  (k 3  k 4 )C B (9.63)
dt
dC
C
 k 2C A  k3C B  k5C E (9.64)
dt
dC D
 k4CB (9.65)
dt
dC E
 k 5 C E (9.66)
dt

Applying time –free basis, we obtain

dC k k 3  k 4 C B
 
k 1  k 2 C A
B 1
(9.67.1)
dC k k
A 1 2
dCC k2 k3 CB k5 CE
   (9.68.1)
dC A k1  k 2 k1  k 2 C A k1  k 2 C A
dC k C
D  4 B
(9.69.1)
dC k k C
A 1 2 A
278 Development of rate equation for homogeneous multiple reactions

dC k C
E  5 E
(9.70.1)
dC k k C
A 1 2 A
Equation (9.67.1) is a linear differential equation, which can be solved as under,
K   1 K1  
 C  1 C   
2 
C K C
B  A  B ,0
 A  
 1 (9.67.2)
C C 
 C K  1  C 
A,0  A, 0  A , 0 1  A, 0  
  
k k k
where K 1  3 4
and K  1
k k 2 k k
1 2 1 2
C CE
In order to get a solution for the yield, C , we have to first find out by solving
C A,0 C
A
equation (9.70.1). Therefore, by integrating equation (8.89.1), we get

k 1
CE C E ,0  C  5
  A  (9.70.2)
C A C A,0  C A,0 
 
Substituting this equation to equation (9.68.1) and integrating gives the yield of C,
C C C ,0 K K  K K  k  C   K 3 C B ,0 K K 
5 
C
  2 3 1 5
1 A     2 3 
C C 1 K  C  K C K (1  K ) 
A,0 A,0 1  A,0   1 A,0 1 1 

   1 
K
 K    CA  K 
  C A  1 C
 E ,0 1   C
 C
  E ,0   C A  1

1   C  C  1   C  (9.68.2)
   A,0   C 
  A,0   A,0
  A,0   A,0  
   
 

k3 k2
where K 3  and K 5 
k1  k 2 k1  k 2

In the same manner, the yield of D can be computed by integrating the equation (9.69.1)
k4
letting K 4  , as follows,
k1  k 2
 K 
C C  C K K  K C K K   C  1
 2 4 1  A   1  A 
D  D ,0 4 B , 0
 2 4 (9.69.2)
C C 1 K  C  K C K (1  K )    C  
A,0 A,0 1  A,0   1 A,0 1 1    A,0  
 
Multiple reactions with other kinetics in batch reactor 279

In such type of reactions, the values of rate constants play very vital role. For example, for
B in the case where k 3  k 4  k1  k 2 , that is when K1  1 , application of L’Hospital’s rule to
equation (9.67.2), equation (9.68.2), and equation (9.69.2) gives
C C  C B,0 C 
B  A  K 2 ln A (9.67.3)
C A,0 C A,0  C A,0 C A,0 
 
For C and D, it can be given as,
CC C C ,0  C  C B ,0 
  1  A  K 5  K 2 K 3  K 3 
C A,0 C A,0  C A,0   C A,0 
  
 K 
C   5
C C E ,0   C A 
K K A ln A  1   C  (9.68.3)
2 3 C C C 
A,0 A,0 A,0   A,0  
 

C 
C D ,0 C  C B ,0 

D  1  A  K K  K   K K C A ln C A (9.69.3)
C A,0 C A,0  C A,0  2 4 4 C  2 4 C C A,0
  A,0  A,0

It can be seen here that, these general solutions can be reduced to various simple cases.

Progress Test 9.7 Using the above combination reactions, what type of reactions are
obtained for the cases,
k3  k 4  k5  0; k 2  k 3  k 5  0 and k 2  k3  k 4  0

Derive the yield for these types of cases.

Progress Test 9.8 Derive the rate expression for the above reactions for PFR and CSTR

9.5.3 Autocatalytic reactions

Autocatalytic reactions takes place as soon as some product has been formed, or in other
words the product of the reaction are either catalyzed or promotes further reaction of the
reactants. By nature autocatalytic reactions are different from other types of reactions, where
the rate at the start is low because very little amount of product is present which gradually
increases to maximum product formation and then drops again to a low value when the
reactant is consumed. Figure 9.11 shows a typical behavior of such reactions.

Let us consider, an autocatalytic reaction

A  C  P
With an assumed mechanism of

AC 
 2C  P
280 Development of rate equation for homogeneous multiple reactions

Therefore, for a batch system, it can be expressed as,

dC A
  kC A C C (9.70.1)
dt

Some R
in feed

1
-rA
 rA

No R
in feed

CA XA

Figure 9.11 Typical rate-concentration curve for autocatalytic reactions,

A R  R  R ;  r  kC C

A A R
As we know three variables with two equations, integration is not possible, we can reduce the
same by applying stoichiometric relationship for the solution.

C C C C
A A,0 C C ,0

1 1
or
C C C C
C A,0 C ,0 A
 M 0 C A

where M  C  C C,0  Constant

0 A,0
Substituting to the equation, we get
dC A
  kC A ( M 0  C A ) (9.70.2)
dt

After integration, the result can be expressed in the form of

C ( M 0 / C C ,0 ) exp(  M 0 kt)
A  (9.70.3)
C A,0 1  (C A,0 / C C ,0 ) exp(  M 0 kt)

or, can be expressed in terms of conversion

Problems 281

1  exp( M kt)
X  0 (9.71)
A 1  (C A,0 / C C ,0 ) exp( M 0 kt)

Figure 9.12 shows the typical conversion-time behavior for an autocatalytic reaction

XA
 dX A 
 
 dt 
  max

time

Figure 9.12 Characteristic of an autocatalytic reaction

Problems
P9.1 The following mechanism has been proposed for a reaction

A + B C + D k1 and k 1
CB ED k2
2D  F k3

where A and B are the reactant, E and F are the products and C and D are reactive
intermediates. Assume r 2  r 3 and use steady state method to obtain expression for the
rate in terms of A & B. What is the total order ?

P9.2 The following mechanism has been proposed for a reaction

A + B C k1 and k 1
282 Development of rate equation for homogeneous multiple reactions

C BD k2

where C is very reactive intermediate. Using steady state approximation method show that
the reaction is second order overall & obtain its expression in terms of rate constants.

P9.3 The decomposition of a substance A has been studied in batch reactor. The substance A
decomposes to form a product B which itself decomposes to form a product C. Both the
decomposition reactions are first order & irreversible. The feed is pure A, C AO =1 kmol/m3.
Determine the maximum concentration of B, and the time at which it occurs.

P9.4 Consider the decomposition of A in a batch reactor by the following mechanism

k1 k2
A  B 
 C

Both the decomposition reactions are of first order & irreversible. If C is the desired product
develop the equation for the concentration of C as a function of time, and show that if
k1  k 2 the second reaction is the rate determining step, whereas if k1  k 2 the first
reaction is the rate determining step.

P9.5 Two first order reactions are given below.

AR k1
A  2S k2
and is carried out isothermally in a batch reactor. After a reaction time of 50 min, 90% of
reactant A has decomposed and the product is found to contain 9.1 mol of R per mole of S.
Neither R or S present initially in the reaction vessel. Evaluate the rate constants.

P9.6 When the following first order consecutive reaction are carried out in perfectly mixed
flow reactor, show that the concentration of R takes its maximum value at

 F,m  1 /  k1 k 2 
k1 k2
A 
 R 
 S

P9.7 The following liquid phase reactions are carried out isothermally at plug flow condition
in the tubular reactor. The mass density of the mixture remains constant throughout the
reactor
A  2R k
1
A  3S k
2
For a conversion of A of 70% at  F =10s, the moles of R produced per mole of S are 4 to 1.
The feed to the reactor consists of pure A. Calculate the value of k1 and k 2 .
Problems 283

9.8 The research department has come up with a process to produce R & S. Although the
actual path is complicated, the irreversible kinetics can be represented by
k1 k2
A 
 R   S

Without catalyst k1 =0.4/h and k 2 =0.04/h; when a catalyst is used k1 is not affected but k 2
=0.6/h. Although A can be separated from R & S by distillation, no scheme for separating R
&S has been developed. It is believed, however, that the market will accept R if it contains
no more than 4 mole% S, and if it contains no more than 4 mole % R. It is proposed that this
hypothesis be tested with some marketable R&S produced in a l m 3 batch pilot plant reactor.
Reactant A is available as a solution containing 5 mol/lit.

A) How much reaction time will be required to produce a batch of R? What

will be the concentration of A in the solution to be distilled?
B) How much reaction time will be required to produce a batch of S? What
will be the concentration of A in the solution to be distilled?

P9.9 Calculate the overall fractional yield of the desired product C for liquid phase reactions.

A B C rc  k1C A0.5 C B0.8

A B  D rD  k 2 C 1.8 C B
k1 / k 2  1
under the following conditions
A) Plug flow reactor, 70% conversion, equimolar feed
B) Back mix reactor, 70% conversion, equimolar feed
C) Back mix reactor, 70% conversion of limiting reactant, feed containing
90% A & B. What is the total order?
P9.10 The reaction between two species P & Q proceed by the following elementary
reactions:
2P  R
PQ  M
2Q  L
Determine what ratio of P & Q should be maintained in the mixed reactor so as to maximize
the fractional yield of deferred product M.