6.

Multiple Reactions
Selectivity and Yield
Reactions in Series
Algorithm for Multiple Reactions
Applications of Algorithm

6.1 Selectivity and Yield

There are 4 basic types of multiple reactions: series, parallel, complex and independent. These
types of multiple reactions can occur by themselves, in pairs, or all together. When there is a
combination of parallel and series reactions, they are often referred to as complex reactions.

Parallel reactions (also called competing) are reactions where the reactant are consumed by two
different reaction pathways to form different products.

A 
k1
B
A 
k2
C
An example of an industrially significant parallel reaction is the oxidation of ethylene to ethylene
oxide while avoiding complete combustion to carbon dioxide and water

2CO2  2 HO2

CH 2  CH 2  O2 O

CH 2  CH 2

Series reactions (also called consecutive) are reactions where the reactant forms an intermediate
product, which reacts further to form another product. A  B  C
k1 k2

An example of a series reaction is the reaction of ethylene oxide (EO) with ammonia to form mono-,
di-, and triethanolamine:
CH 2  CH 2  NH 3  HOCH 2 CH 2 NH 2 
EO
HOCH 2 CH 2 NH 
EO
HOCH 2 CH 2 3 N
Complex reactions are multiple reactions that involve combination of both series and parallel
reactions.

A B C  D
AC  E
An example of a combination of parallel and series reaction is a formation of butadiene from ethanol:

C 2 H 5 OH 
 C 2 H 4  HO2
C 2 H 5 OH 
 CH 3 CHO  H 2
C 2 H 4  CH 3 CHO 
 C 4 H 6  HO2

Independent reactions are reactions that occur at the same time but neither the products nor reactants
react with themselves or one another.

1
A BC
DEF
An example is the cracking of crude oil to form gasoline where two of many reactions occurring are:

C15 H 32  C12 H 26  C 3 H 6
C8 H 18  C 6 H 14  C 2 H 4

Desired and undesired reactions.

Of particular interest are reactants that are consumed in the formation of a desired product, D, and the
formation of undesired product, U, in a competing or side reaction. In the parallel reaction sequence
A 
kD
D
A 
kU
U

or in the series sequence: A  D 

kD k
U
U
We want to minimize the formation of U and maximize the formation of D because the greater the
amount of undesired product formed, the greater the cost of separating the undesired product U from
desired product D.

Selectivity tells us how one product is favored over another when we have multiple reactions. We can
quantify the formation of D with respect to U by defining the selectivity and yield of the system. The
instantaneous selectivity of D with respect to U is the ratio of the rate of formation of D to the rate
bof formation of U.

rD rate of formation of D
S D /U  
rU
rate of formation of U

Another definition of selectivity used is given in terms of flow rates leaving the reactor. S̃D/U is the
~ F exit molar flow rate of D
S D /U  D 
FU
overall selectivity. exit molar flow rate of U

For a batch reactor, the overall selectivity is given in terms of the number of moles of D and U at the
~ N
S D /U  D
end of reaction time: NU

Reactor yield, like the selectivity, has two definitions: one based on the ratio of reaction rates and one
based on the ratio of molar flow rates. In the first case, the yield at a point can be defined as the ratio
of the reaction rate of a given product to the reaction rate of a key reactant- instantaneous yield:
rD
YD 
 rA

In the case of reaction yield based on molar flow rates, the overall yield, ỸD, as defined as a ratio of
moles of product formed at the end of the reaction to the number of moles of the key reactant, A, that
have been consumed.

2
 ~ ND ~ FD
YD  YD 
Batch system: N A0  N A Flow System: FA 0  FA

As with selectivity, the instantaneous yield and the overall yield are identical for CSTR (YD=ỸD).

Selectivity and Yield

Instantaneous Overall

Selectivit
y

Yield

Example: desired product , rD=k1CA2CB

undesired product , rU=k2CACB

Parallel reactions

A 
kD
D rD  k D C A 1
2
For the competing reactions : A  U the rate laws are: rU  kU C A
kU

The rate of disappearance of A for this reaction sequence is the sum of the rates of formation of D and
U:

-rA=rD+rU

- rA=kDCAα1+ kUCAα2

Where α1 and α2 are positive reaction orders. We want the rate of formation of D, rD, to be high with
respect to the rate of formation of U, rU. Taking the ratio of these rates, we obtain the rate selectivity
parameter, SD/U, which is to be maximized.

rD k D  1 2
S D /U   CA
r U kU

Ways of maximizing instantaneous selectivity, SD/U, for different reaction orders of D and U
products.
3
Case 1: α1 > α2, for such a case let (a) be a positive number that is difference between these reaction
orders (a>0): α1 - α2=a,

rD  k D  a
S D /U    C A
then rU  kU 

To make this ratio as large as possible we want to carry out reaction in a manner that will keep the
concentration of reactant A as high as possible during the reaction. If the reaction is carried out in a
gas-phase, we should run it without inerts and at high pressure to keep CA high. If the reaction is in
liquid-phase, the use of diluents should be kept to a minimum.

The batch or plug-flow reactor should be usedbin this case, because, in these two reactors , the
concentration of A starts at a high value and drops progressively during the cause of the reaction.

In the perfectly mixed CSTR , the concentration of reactant within the reactor is always at its lowest
value(outlet concentration) and CSTR should be not chosen.

Case 2. α2 > α1, let b= α2 - α1, b-positive number.

rD k D C A 1 kD k
S D /U   2
  2  1
 Db
rU kU C A kU C A kU C A
rD
For the ratio rU to be high, the concentration of A should be as low as possible. The low CA can be
accomplished by diluting the feed with inert and running the reactor at low CA. A CSTR should be
used.
Because the activation energies of tnhe two reactions are not given, it can not be determined whether
the reaction should be run at high or low temperature. The sensitivity of the rate selectivity
parameter to temperature can be determined from the ratio of the specific reaction rates:
k D AD (( ED  EU ) / RT )
SD   e
U kU AU
A- is the frequency factor
E -activation energy

Case 3: ED>EU, in this case the specific reaction rate of desired reaction kD (and therefore the overall
rate rD) increases more rapidly with increasing T, than does the specific rate of the kU. so, the reaction
system should be operated at the highest possible T to maximize S D U .

Case 4: EU>ED, the reaction should be carried out at a low T to maximize S D U , but not too low that
the desired reaction does not proceed to any significant extent.

6.2 Reactions in Series – Maximizing the Desired Product.

Undesirable product could be minimized by adjusting the reaction conditions (e.g., concentration) and
by choosing the proper reactor. For the series of consecutive reactors, the most important variable is
time: space-time for a flow reactor and real-time for the batch reactor. To illustrate the importance of
the time factor, we consider the sequence: A  B 
k1 K2
C

4
 in which B is the desired product.

If the first reaction is slow and the second is fast, it will be extremely difficult to produce B. If the
first reaction (formation of B) is fast and reaction to form C is slow, a large yield of B can be
achieved. However, if reaction is allowed to proceed for a long time in a batch reactor, or if the
tubular reactor is too long, the desired product B will be converted to the undesired product C. In no
other type of reaction is exactness in the calculation of the time needed to carry out the reaction
more important than in series reactions.

For the reaction: A  B 

k1 K2
C could be written as:
Reaction (1): A 
k1
Reaction (2): B 
k
B 2
C
dC A C A  C A0 exp(k1t )
  rA  k1C A
Species A: dt after integration:

dC B rB  rBnet  r1B  r2 B rB  k1C A  k 2C B

 rB
Species B: dt
dC B dC B
 k1C A0 exp(k1t )  k 2C B  k 2C B  k1C A0 exp(k1t )
dt dt
Using the integration factor i.f.:
i. f .  exp  k 2 dt  exp(k 2t )
d (C B exp(k 2t ))
 k1C A0 exp(k 2  k1 )t
dt

dC B
 k 2 C B  k1C A0 exp(k1t )
Derivation for Series Reaction: dt (1)
If.= exp( k 2 t )
d C B exp(k 2 t )
 k1C A0 exp(k 2  k1 )t
dt (2)
dC B
e k 2t  C B k 2 e k2t  k1C A0 e k1t e k2t
Differentiating the rite hand side of Equation (2) : dt

e k2t dC B
 k 2 C B  k1C A0 exp(k1t )
Dividing by we see we arrive back at Equation (1): dt
d C B exp(k 2 t 
 k1C A0 exp(k 2  k1 )t
Now integrating Equation (2): dt
kC
C B k 2 e k2t  1 A0 e k1t  K1e k2t
k 2  k1

k1C A0
C B  0  K1  
Evaluating the constant of integration K1 : k 2  k1 when t = 0 then

5
 CB  
k1C A0 k1t
k 2  k1
2
e  e k t 
Substituting for K1 and rearranging : at t=0, CB=0
k1C A0
CB  exp(k1t )  exp(k 2t )
k 2  k1

When should you stop the reaction to obtain the maximum amount of B?

dC B  1  k2
t  t opt at 0 t opt    ln
dt
 k 2  k1  k1

Derivation for Optimum Yield with Multiple Reactions:

To maximize the amount of B produced, we need to differentiate our function for CB.
Setting the differential equation equal to zero, we can solve for the time to reach this optimum, topt.
k1C A0
CB  exp(k1t )  exp(k2t )
k 2  k1
dC B
dt
kC

 0  1 A0  k1e k1t  k 2e k2t
k 2  k1

 1  k2
topt    ln CC 
C A0
k 2  k1
   
k 2 1  e k1t  k1 1  e k2t 
Solving for topt gives  k 2  k1  k1

6
Mole Balances

7
 Reactor
Gas Phase Liquid Phase
Type

Batch

Semibatch

CSTR

PFR

PBR

NOTE: We could use the gas-phase mole balance for liquids and then just express the
concentration as:
Flow CA = FA/υ0
Batch CA = NA/V0
NOTE: The reaction rates in the above mole balances are net rates.
Having written the mole balances, the key point for multiple reactions is to write the net
rate of formation of each species (e.g., A). That is we have to sum up the rates of formation
for each reaction in order to obtain the net rate of formation (e.g.,-rA).
If q reactions are taking place:
Reaction1: A  B  3C  D
k1 A

Reaction 2: A  2C  3E
k2 A

Reaction 3: 2 B  3E 
k3 B
4F
…………………………………..
k
Reaction q: E  2 F  qE
G
Reaction rate constant in reaction 1 and 2 are defined with respect to A, while k in
reaction 3 is defined with respect to B. The net rates of reaction of A and B are found by
summing up the rate of formation of A and B for every reaction in which species A and
B occur.
q q
rA  r1 A  r2 A  ...  rqA   riA rB  r1B  r2 B  ...  rqB   riB
i 1 i 1
For those reactions in which a species (e.g., A) does not appear, the rate is zero.

8
 q
rA   riA
For q number of reactions, the net rate of formation of species A: i 1

Relative rates of reaction

We need to relate the rate law for a particular reaction and species to other species
participating in that reaction. To achieve this relationship for a given reaction:
aA  bB  cC  dD  rA  rB rC rD
  
and use of equation; a b c d to relate the rates of
disappearance of A and B to the rates of formation of C and D.

In working with multiple reactions, it is usually more advantageous to relate the rates
of formation of each species to one another. This relationship can be achieved by
rewriting above equation for reaction i in the form:
riA r r r
 iB  iC  iD
 ai  bi ci di