1

1. Introduction to Chemical Reaction

The conversion process of any raw materials to products could pass through a
number of steps. For illustration see the following schematic approach:

Raw 1 2 3 4 Wanted
materials products

Unwanted
products
Figure 1.1 Steps of the conversion process

The steps of conversion can be stated as:

Step 1. Physical preparation of raw materials( Purification,Grinding etc.).

Step 2. Chemical process with partial conversion

Step 3. Separation of non-converted raw material(obtained from step 2)

Step 4. Separation of unwanted and wanted products.

The steps of a chemical process can be simple or complex, depending upon the
purity of the raw material, the desired quality of the products etc. The main objective of
the chemical reaction process is to secure quality of the wanted products with a minimum
cost of production.

In the chemical reaction process stated above, the steps 1, 3 and 4 are physical
treatments and are mainly carried out in unit operations. Step 2 is the chemical treatment,
which is carried out in the reactors. The cost of production depends on step 2. To ensure
good processing result of the chemical treatment under step 2, it needs:

a. Information, knowledge and experience from the different sciences

such as fluid mechanics, heat transfer, mass transfer, economics etc.

b. To answer the following two questions:

• What changes can we expect to occur?

• How quickly will they take place?

2

Introduction to Chemical Reaction

The first question deals with thermodynamics. The second question deals with the
various rates of processes such as chemical kinetics, heat transfer and mass transfer. The
Thermodynamics in chemical treatment is concerned with two main aspects; namely, the
heat liberated (or absorbed) during reaction and the maximum attainable conversion.
Chemical kinetics is the study of the rate of reaction and mechanism. This is the main
concern in this teaching material and as such will be dealt with explicitly.

1.1 Classification of Reactions

There is no specific guideline to classify reactions due to the complexity of the

nature of the reactions. In general, reaction can be classified as follows:

• According to the number of phases involved in the reactions, namely

- Homogeneous Reaction

- Heterogeneous Reaction

• According to the type of reaction, i.e.,

- Simple

- Complex

- Catalyzed

- Noncatalyzed

• According to the process nature of the reaction, i.e., whether the

process of reaction is:

- Reversible

- Irreversible

• According to the conditions of the process of reactions, i.e.,

- Isothermal

- Nonisothermal

- Adiabatic
However, it should be well understood that one reaction may simultaneously belong to
classifications stated above. Example of reaction may be homogenous, simple,
3

The General Mole Balance

irreversible etc. Figure 1.2 illustrates the schematic presentation of classification of

reactions.

Figure 1.2 Schematic presentation of classification of reaction

1.2 The General Mole Balance

A mole balance is the basis for calculating and assessing the quantity of a
particular molecular species (reactant or product) in a given system volume of reaction.

In the process of balance, it takes a small volume of the reactor to observe what
happens there in the small interval of time. A material balance on any reactant species
can be drawn up through the following equations:

Mole entering = Mole leaving + Mole reacting + Change of Moles (1.1)

Input = Output + Disappearance + Accumulation (1.2)

As a basis for further calculation, we select our system volume as represented in Figure
1.3
 4

Introduction to Chemical Reaction

Flow in Flow out

Fj,o Fj
Figure 1.3 Mole balance for a system volume

Conducting a mole balance on species j at any given instant of time which obeys
the following equation format.

Rate of flow of j Rate of flow of j Rate of generation of j Rate of accumulation

into the system - out of the system + by chemical reaction = of j within the system (1.3)
(moles/time) (moles/time) within the system (moles/time)
(moles/time)

or expressed in mathematical form of equation,

dn j
F j ,0 − F j + G j = (1.3.1)
dt

where Fj,o - represents initial molar flow rates of species j, mol / time
Fj - represents final molar flow rates of species j, mol / time
Fj - represents the number of moles of species j in the system of time t.
G j - represents rate of formation at which a component is formed or disappeared
by reaction, and it is given by the product of the reaction volume, V and the
rate of formation of species j, rj

G j = r jV (1.4)

Suppose that the rate of formation of species j for the system volume varies with
the position in the system. That is, it has a value r j ,1 r j , 2 at location 1 and 2 respectively
which is surrounded by a small volume UV1 and UV2, where the rate of formation of
U G j ,1 = r j ,1 UV1 and U G j , 2 = r j , 2 UV2 respectively. Then, the total rate of formation
with in the system volume would be the sum total of all the rates of formation or by
taking the appropriate limits and following the definitions of integral, it can be expressed
for the rate of formation of species j as:
v
G j = ∫ r j .dv ( 1.4.1)
5

The General Mole Balance

In actual, the subject of mole balance is concerned with the evaluation of this
integral replacing Gj in equation (1.3.1). Thus, substituting equations (1.4.1) to (1.3.1)
we get the basic equation of the mole balance for any chemical species j that is entering,
leaving, reacting and or accumulating within any system volume, v.

v dn j
F j ,0 − F j + ∫ r j dv = (1.3.2)
dt

Using this basis of equation, the design equation can be developed for various types of
industrial reactors. Of course one needs to find rj using chemical kinetics.

1.2.1 Batch Reactor

In a batch reactor, no material is supplied to or withdrawn from the reactor during

the reaction. The amounts of individual components may change due to reaction, but not
due to flow in or out of the system. Therefore, for the species j, the mole balance
equation (1.3.2) can be expressed as:

dn v
= ∫ r j dV
j
(1.5)
dt

The rate of formation of species j is uniform and is equal to the system average
rate, every where in the reaction, and therefore, we can take the rate of formation out of
the integral and can rewrite the equation of the mole balance in the form of :

dn j
= r jV (1.5.1)
dt

and for the disappearance of reactant A,

A Product

Multiplying both sides of equation (1.5.1) by (-1), we get

dn A
− = (− rΑ ) V (1.5.2)
dt
6

Introduction to Chemical Reaction

1.2.2 Continuous Flow Reactors

In this type of reactors, the chemical reactions occur while the reacting stream is
flowing through the reactor. The reaction is operated at steady-state and this means that
the variables such as concentration, temperature etc. at each point with in the system do
not vary with time. Thus equation (1.3.2) becomes,
v
F j , 0 = F j − ∫ r j dV (1.6)

[Link] Continuous Stirred Tank Reactor (CSTR)

In this type of reactors, due to continuous stirring, vigorous agitation takes place.
As a result, the contents are thoroughly mixed and the conditions through out the reactor
are the same and equal to the conditions at the outlet. For the same reason, the rate of
formation is constant through out the reactor. Therefore, the rate of formation can be
taken out of integral and the equation can be simplified as
v v
∫ r j dV = r j ∫ dV = r jV

Then the mole balance equation (1.6) becomes,

F j , 0 = F j − r jV (1.6.1)

or
F j ,0 − F j
V = (1.6.2)
− rj

[Link] Plug Flow Reactor

In this reactor type, the content of the reactor is perfectly mixed in the radial
direction. No mixing takes place in axial direction. This condition provides the
concentration, temperature, rate of formation etc to vary continuously in the axial
direction. Hence the material balance has to be applied to a differential element of
volume. This can be shown in the Figure 1.4

F in FA Δ V FA + dFA F out

Figure 1.4 Plug flow reactor

7

Stoichiometric Relationship in Reaction

The differential element of volume can be expressed in equation form as under:

FA − (FA + dFA ) + rA ΔV = 0 (1.7)

and taking the limit as UV l 0, we obtain

UV ∼ dV

− dFA = − rA dV
or
dFA
(− rA ) = − (1.7.1)
dV

1.3 Stoichiometric Relationship in Reaction

It can be seen that the changes in the composition of a reactor are of two types.

- Advective change due to material brought into the system or

removed from it.

- The internal change due to chemical reactions.

Our interest is to study the structure of chemical reaction chain in the reaction
chain of the reactor system. To understand the phenomena, let us take a well known
reaction,
N2 + 3H2 = 2NH3 (a)

Such type of equations can have two alternative meaning : kinetic and
stoichiometric explanation. In a kinetic explanation, it implies that one molecule of N2
combines directly with three molecules of H2 to form two molecules of [Link] terms of
stoichiometric description of the reaction means that the number of nitrogen and
hydrogen molecules combine to form ammonia in the ratio 1:3. It is clear that if a
reaction expression is true in a kinetic sense, it is also true in stoichiometric sense, but the
converse statement is not [Link] proportions 1:3 in the stoichiometric description are
absolutely definite and an equation such as 3N2 + 3H2 = 3NH3 is non existent.

The stoichiometric relationship explains to us how many molecules of one species

will be formed during a chemical reaction when a given number of molecules of another
species disappear, or in another word, it shows the variation of the amount of individual
species remaining during the course of reaction at time t.
8

Introduction to Chemical Reaction

Let us examine a typical chemical reaction, where the chemicals species present
in the reaction system be represented by the letters A1, A2 - - - - -- etc, assuming there are
other species present, represented by j = 1,2 - - - - - - S. A chemical reaction will not be
split into two sides of an equation, unless as in equation(a) above, are written on one side
and is set equal to zero as expressed below:

2NH3 - N2 - 3H2 = 0 (b)

If we identify A1 with NH3; A2 with N2 and A3 with H2, then S=3 and the reaction
(b) can be expressed as:
2A1-A2-3A3 = 0 (c)
or

∑υ
s

j Aj = 0 (1.8)
j =1

υ υ υ
where 1 =2 ; 2 = -1 ; 3 = -3 is called the stoichiometric coefficient of Aj in the
reaction. The species with positive stoichiometic coefficients are the product of the
reaction and those with negative stoichiometric coefficients are the reactants. The
important thing to observe at this point is that the meaning of the reaction equation is
unchanged if it is multiplied by non-zero constant. The reaction -2 NH3 + 1 N2 +3H2=0
is multiplied by (-1), the same reaction with the decomposition of NH3, can be viewed
from the other side.

Considering the following reaction,

υ A A+ υ B B = υ C C+ υ D D

or
- υ Α A- υ Β B + υ C C+ υ D D =0

As per stoichiometric law, it is true that the change in number of molecules are directly
related to the stoichiometric number, thus

Δn A Δn B Δn C Δn D
= = =
υ A υ B υ C υ D
(1.9)

where Δn j = n j − n j , 0

and can be represented with the common value of

Δn A Δn B Δn C Δn D
= = = =ϕ
υ A υ B υ C υ D
(1.9.1)
9

Stoichiometric Relationship in Reaction

where ϕ is called molar extent or reaction coordinate or degree of advancement of the

reaction. ϕ is an extensive variable measured in moles.
n j − n j ,0
ϕ=
υ j
(1.9.2)

n j = n j ,0 + υϕ j (1.9.3)

Equation (1.9.3) expresses the variation of the amount of species j present during the
course of reaction. If j is limiting reactant (i.e. species present in least amount), the
maximum extent of reaction is found when all j is consumed, i.e. equation (1.9.3)
becomes,
0 = n j , 0 + j ϕ max υ (1.9.4)

For reactant species A, the equation (1.9.2) can be written as:

n A − n A,O − ( n A − n A ,O ) n A, o − n A Δn A
ϕ=
− υ A
=
− (− υ A )
=
υ A
=
υ A
(1.9.5)

n A = n A, 0 − υ A ϕ (1.9.6)

where Δn A = n A,0 − n A

Likewise, for the species C, it can be

nC − nC , 0
ϕ=
υ C
(1.9.7)

nC = nC , 0 + υϕ
C (1.9.8)

1.3.1 Measurement of Concentration for the Batch Systems

In chemical reaction, the composition of the reaction mixture can be expressed in

terms of one variable, the molar extent or conversion of the reaction. The conversion X is
the fraction of a reactant that has been converted into products, in symbols:

n j ,0 − n j Δn j
Χj = = (1.10)
n j ,0 n j ,0
10

Introduction to Chemical Reaction

or in other word the conversion of XA is the number of moles of A that have reacted per
mole of A fed to the system,

Moles of A reacted
ΧA = (1.10.1)
Moles of A fed
n A, 0 − n j Δn A
ΧA = = (1.10.2)
n A, 0 n A, 0

A) Mole as a function of Conversion

Taking the change of moles of composition in the reaction,

Δn j Δn A
=
υj υ A

Δn j =
υ Δn A
υ
j

n j − n j ,0 =
υ (n − n A, 0 )
υ
j
A
A

Using conversion of reactant A

n A, 0 − n A
ΧA =
n A, 0

Rearranging the equations become

n j − n j ,0 =
υ (n − n ) = −υ (n − n A, 0 )
−υ − (−υ )
j j
A A, 0 A

υ (n − n ) = υ n Χ
A A

υ υ
j A, 0 A j
= A, 0 A

υ n Χ
A A

=n +
υ
j
nj j ,0 A, 0 A (1.11)
A

Equation (1.11) expresses the changes in number of moles of j species as a function of

main (limiting) reactant (species A) conversion at any given time.
11

Stoichiometric Relationship in Reaction

The relationship of each species can be rearranged using A as a base of

calculation directly from the equation (1.11) for the reaction.

υ A+ υ υ C +υ D
B=
−υ
A B C D

n A = n A, 0 +
υ n Χ =n − n A, 0 Χ A
A
A, 0 A A, 0
A

−υ υ n
n B = n B ,0 +
υ n Χ =n −
υ ΧA
B B
A, 0 A B ,0 A, 0
A A

nC = nC , 0 +
υ n Χ =n +
υ n ΧA
υ υ
C C
A, 0 A C ,0 A, 0
A A

n D = n D ,0 +
υ n Χ =n +
υ n ΧA
υ υ
D D
A, 0 A D ,0 A, 0
A A

n I = n I , 0 ( Inerts)

υ (υ D +υC − υ A −υ B ) n
1
nT = nT 0 + A0 ΧA
A

or

υ Δυ n
1
nT = nT 0 + A0 ΧA (1.11.1)
A

where
Δ υ = ∑
υ − ∑
υ
pr υA r υA
Equation (1.11.1) expresses the change of total moles as a function of conversion for a
batch system. Stoichiometric equation can be illustrated in Table 1.1.

Column 1 The particular species

Column 2 The number of moles of each species initially present.

Column 3 The change in the number of moles brought through

the reaction.

Column 4 The number of moles remaining in the system at time t.

12

Introduction to Chemical Reaction

Table 1.1 Stoichiometric table for the reaction aA + bB → cC + dD

Moles initially Remaining Mole in the system at

Species present Change in mole time t
−a
n A, 0 n A, 0 Χ A n A = n A, 0 − n A, 0 Χ A
A a
−b b
n B,0 n A, 0 Χ A n B = n B ,0 − n A, 0 Χ A
B a a
c c
nC , 0 n A, 0 Χ A nC = nC , 0 + n A, 0 Χ A
C a a

d d
n D,0 n A, 0 Χ A nD = nD,0 + n A, 0 Χ A
D a a
I (Inerts) n I ,0 - n I = n I ,0
⎛d c b ⎞
nT = nT ,0 + ⎜ + − − 1⎟n A,0 Χ A
⎝a a a ⎠

Progress Test 1.1 Write stoichiometric relationship for ammonia synthesis using
V2O5 as catalyst .

For several reactions, the total moles of the process can also be defined as

υi Χ
r
1
nT = nT 0 + n A0 ∑ Δ
υ A i =1
A ,i (1.11.2)

where, r is the number of reaction

B) Concentration as a function of Conversion

The concentration of species j is the number of moles of j per unit volume,
we get by definition.
nj
Cj = (1.12)
Vf
where Vf is the final volume.
13

Stoichiometric Relationship in Reaction

Using the above stoichiometric Table 1.1, we can express the concentration of each
component under conversion.

n A, 0 − n A, 0 Χ A n A, 0 (1 − Χ A )
CA = =
Vf Vf

⎡ n B ,0 b ⎤ ⎡ b ⎤
b
nB , 0 − n A , 0 Χ A n A , 0 ⎢ − X A ⎥ n A, 0 ⎢φ B − X A ⎥
a ⎢ n
⎣ A, 0 a ⎥
⎦ = ⎣ a ⎦
CB = =
Vf Vf Vf

⎡ nC , 0 c ⎤ ⎡ c ⎤
c
nC , 0 + n A,0 Χ A n A , 0 ⎢ + X A ⎥ n A, 0 ⎢φ C + X A ⎥
a ⎢⎣ n A, 0 a ⎥⎦ ⎣ a ⎦
CC = = =
Vf Vf Vf

⎡ n D ,0 d ⎤ ⎡ d ⎤
n D,0 +
c
n A, 0 Χ A n A, 0 ⎢ + X A⎥ n A, 0 ⎢φ D + X A ⎥
CD = a = ⎣⎢ n A,0 a ⎥⎦
= ⎣ a ⎦
Vf Vf Vf

n j ,0 C j ,0 y j ,0
where φ j = = = = ratio parameter
n A, 0 C A, 0 y A, 0

We now need to define the volume as a function of conversion to obtain the

species concentration. This can be achieved under two conditions.

i) Constant Volume Reaction System

V0 = V f = constant, ‫ތ‬m constant, Δυ = 0 ; i.e. equal mole of reactant and
product, like
H 2 + C 2 H 5 CH 3 → C 2 H 6 + CH 4

In such case,
nj nj
Cj = = (1.12.1)
V f V0
To determine concentration as a function of conversion, when there is no volume
change in the reaction, aA + bB → cC + dD , we proceed as,
14

Introduction to Chemical Reaction

n A, 0 − n A, 0 Χ A
CA = = C A,0 − C A,0 Χ A = C A,0 (1 − X A )
V0
b
n B ,0 − n A, 0 Χ A
a b ⎛ b ⎞
CB = = C B , 0 − C A, 0 Χ A = C A, 0 ⎜ φ B − C A, 0 X A ⎟
V0 a ⎝ a ⎠
c
nC ,0 + n A, 0 Χ A
a c ⎛ c ⎞
CC = = C C , 0 + C A, 0 Χ A = C A, 0 ⎜ φ C + C A, 0 X A ⎟
V0 a ⎝ a ⎠
d
nD , 0 + n A, 0 Χ A
a d ⎛ d ⎞
CD = = C D , 0 + C A, 0 Χ A = C A, 0 ⎜ φ D + C A, 0 X A ⎟
V0 a ⎝ a ⎠

In general, the concentration of species j can be expressed as :

C j = C j ,0 +
υ C A, 0 Χ A
υ
j
(1.13)
A

Progress Test 1.2 Write Concentration stoichiometric table for ammonia

synthesis using V2O5 catalyst.

ii) Variable Volume Reaction System

V0 ≠ V f ; Δ υ ≠ 0 , i.e. do not posses an equal number of moles of reactant

and product , like: N 2 + 3H 2 → 2 NH
in such cases total mole is linear
3
function of conversion. The volume change during reaction can be determined using the
following equation of state (Ideal gas): At time t = 0 becomes

P0V0 = nT ,0 RT0 (1.14)

At any given time t,

PV f = nT RT (1.15)

Dividing equation (1.15) by equation (1.14), and rearranging, we obtain

⎛P ⎞⎛ T ⎞ nT
V f = V0 ⎜ 0 ⎟⎜⎜ ⎟⎟ (1.16.1)
⎝P ⎠⎝ T0 ⎠ nT ,0
 15

Stoichiometric Relationship in Reaction

From equation (1.11.1), we get

nT
nT , 0
= 1+ Δ υ nn A, 0
Χ A , for υ A =1 (1.17.1)
T ,0

and the mole fraction is defined by

nj n j ,0
yj = ; y j ,0 = (1.18)
nT nT ,0
Substituting to equation (1.17.1), we get

nT
nT , 0
= 1+ Δ υy A, 0 ΧA (1.17.2)

and the equation (1.16.1) becomes,

⎛P
V f = V0 ⎜ 0
⎞⎛ T
⎟⎜⎜
⎞
⎟⎟(1 + Δ υy A, 0 ΧA) (1.16.2)
⎝P ⎠⎝ T0 ⎠

If we put a new concept,

ε =
Change in total number of moles when the reaction is completed
Total number of moles fed to the reaction

In symbols,

ε ⎛ d c b ⎞ n A, 0
= ⎜ + − − 1⎟ =Δ υy A, 0
⎝ a d a ⎠ nT ,0 (1.19)

For constant temperature and pressure equation (1.16.2), variable of volume becomes,

V f = V 0 (1 + εΧ A
) (1.16.3)

Therefore, concentration in a variable volume batch system under constant temperature

and pressure, can be expressed combining equation (1.11) and (1.16.3) as,
16

Introduction to Chemical Reaction

υ n Χ
n j ,0 +
υ C
C j ,0 + ΧA
υ υ
j j
A, 0 A A, 0
nj
V (1 + ε Χ )
Cj = = =
1+ε Χ
A A
(1.20)
Vf 0
A A

To determine concentration as a function of conversion, for a change of volume

during reaction aA + bB → cC + dD we proceed as,

n A n A, 0 − n A, 0 Χ A n A,0 (1 − Χ A ) C A, 0 (1 − Χ A )
CA = = = =
Vf Vf V0 (1 + εΧ A ) 1+ εΧ A

b b b
nB , 0 − n A, 0 Χ A nB , 0 − n A , 0 Χ A C B , 0 − C A , 0 Χ A
n a a a
CB = B = = =
Vf Vf V0 (1 + Χ A ) ε 1 + ΧA ε
n c c
nC ,0 + C A, 0 Χ A nC ,0 +
n A , 0 Χ A CC , 0 + C A , 0 Χ A
C a a a
CC = C = = =
Vf Vf V0 (1 + Χ A ) ε 1+ Χ A ε
d d d
nD , 0 + n A, 0 Χ A nD , 0 +
n A, 0 Χ A C D , 0 + C A, 0 Χ A
CD a a a
CD = = = =
Vf Vf V0 (1 + Χ A ) ε 1+ Χ A ε
C n nI , 0 CI ,0
CI = I = I ,0 = =
Vf Vf V0 (1 + ε Χ A ) 1+ Χ A ε

Measurement of Concentration for the Flow System

The flow system used to describe stoichiometric relationships is given in Figure 1.5

FA,0 FA
FB,0 FB

Input Output
FC,0 FC
FD,0 FD
FI,0 FI

Figure 1.5 Flow system

17

Stoichiometric Relationship in Reaction

The general stoichiometric relationship for a flow system of a reaction,

aA + bB → cC + dD can be drawn as,

ΔFA ΔFB ΔFC ΔFD

= = =
υ A υ B υ C υ D
(1.21)

where ΔF j = F j − F j , 0 ; F j , molar flow rate, mole / time, and the conversion for
the flow system can be written as
F A , 0 − FA
ΧA = (1.22)
FA, 0

A) Molar Flow Rate as a function of Conversion for a Flow System

The form of the stoichiometric table for the flow system is identical to that of
a batch system except that we replace n j , 0 by F j ,0 and n j by F j . Taking A as a limiting
reactant we obtain the following stoichiometric table for the system of reaction:
aA + bB → cC + dD

Table 1.3 Stoichiometric Table for the flow system

Species Feed to reactor Change within Effluent from the reactor

(Moles/time) reactor (moles/time)
(Moles/time)
A FA , 0 − FA, 0 Χ A F A = FA , 0 − FA , 0 Χ A
B FB ,0 b b
− FA, 0 Χ A FB = FB ,0 − FA , 0 Χ A
a a
C FC , 0 c c
FA , 0 Χ A FC = FC , 0 + FA, 0 Χ A
a a
D FD , 0 d d
FA, 0 Χ A FD = FD ,0 + FA, 0 Χ A
a a
I FI , 0 FI = FI , 0
F T ,0 ⎛d c b ⎞
- FT = FT ,0 + ⎜ + − − 1⎟ FA, 0 Χ A
⎝a a a ⎠
υ
FT = FT ,0 + Δ FA,0 Χ A

The total molar flow rate can be expressed as

FT = FT ,0 + Δ F υ X
A,0 A
(1.23)
18

Introduction to Chemical Reaction

B) Concentration as a function of conversion for a flow system

In the flow system, the concentration C j at a given point can be determined as

Fj moles / time moles
Cj = = = (1.24.1)
FV , f litres / time litre
where FV , f is the volumetric flow rate and may vary according to the conditions of the
reaction. The volumetric flow rate as a function of conversion can be expressed under
two conditions.
i) Constant Volume Reaction System

This occurs mostly in liquid phase and in some gaseous phase, where the
number of moles of the product equals to the number of moles of the reactant. For
example, it can be seen in the water-gas shift reaction:
CO + H 2 O → CO + H
2 2

The concentration, Cj at a given point can be determined

Fj Fj
Cj = = (1.24.2)
FV , f FV , 0

We can now express the concentration of A,B,C and D for the reaction:

aA + bB → cC + dD

FA F − FA,0 Χ A
CA = = A0 = C A, 0 − C A , 0 Χ A
Fv , f Fv , 0

b
FB ,0 − FA, 0 Χ A
F a b b
CB = B = = C B ,0 − C A,0 Χ A = C A,0 (φB − X A )
Fv , f Fv ,0 a a

c
FC , 0 + FA,0 Χ A
FC a c c
CC = = = CC ,0 + C A,0 Χ A = C A, 0 (φC + X A )
Fv , f Fv ,0 a a

d
FD , 0 + FA , 0 Χ A
FD a d d
CD = = = C C ,0 + C A, 0 Χ A = C A,0 (φ D + X A)
Fv , f Fv , 0 a a
19

Stoichiometric Relationship in Reaction

Generally,
C j = C j ,0 +
υ C A, 0 Χ A
υ
j
(1.24.3)
A

Note that the same concentration expressions are also obtained as those for a constant
volume batch system, equation (1.13).

ii) Variable Volume Reaction System

Using an equation of state (ideal gas) for total concentration at any point, we
get
FT P
CT = = (1.25.1)
FV , f RT
At the entrance of the system, it can be expressed as,

FT ,0 P0
CT , 0 = = (1.25.2)
FV ,0 RT0

Taking the ratio of equation (1.25.1) to equation (1.25.2) we have

⎛ F ⎞⎛ P0 ⎞⎛ T ⎞
FV , f = FV ,0 ⎜⎜ T ⎟⎜
⎟⎝ P ⎟⎜⎜ ⎟⎟ (1.26.1)
⎝ FT ,0 ⎠ ⎠⎝ T0 ⎠

Substituting the value of FT from equation (1.23) in equation (1.26.1) we get

Fv , f =
υ
FV , 0 FT ,0 + Δ Fv , 0 FA,0 Χ A ⎛ P0
⎜
⎞⎛ T
⎟⎜⎜
⎞
⎟⎟
FT ,0 ⎝P ⎠⎝ T0 ⎠
⎛ FA , 0 ⎞⎛ P0
= Fv ,0 ⎜⎜1 + Δ υΧ A
⎟⎜
⎟⎝ P
⎞⎛ T
⎟⎜⎜
⎞
⎟⎟
⎝ FT ,0 ⎠ ⎠⎝ T0 ⎠

= Fv ,0 (1 + y A, 0 Δ υ Χ )⎛⎜ PP ⎞⎟⎛⎜⎜ TT ⎞⎟⎟

A
0

⎝ ⎠⎝ 0 ⎠

or

FV , f = FV ,0 (1 + εΧ A
⎛⎞
)⎛⎜ P0 ⎞⎟⎜⎜ T
⎟⎟ (1.26.2)
⎝ P ⎠⎝ T0 ⎠
 20

Introduction to Chemical Reaction

Now, for constant temperature and pressure, we can express the concentration of
species j for variable volume flow system as,

F j ,0 +
υ FA, 0 Χ A C j0 +
υ C Χ
υ υ
j j

⎛P ⎞⎛ T0 ⎞
A0 A
Fj
Cj = = = ⎜⎜ ⎟⎟⎜ ⎟
(1 + εΧ )
A A
(1.26.3)
Fv , f FV , 0 A ⎝ P0 ⎠⎝ T ⎠

The concentration of A, B, C & D for the reaction aA + bB → cC + dD of

variable volume flow system under constant temperature and pressure becomes,

FA FA , 0 − F A , 0 Χ A C A , 0 − C A , 0 Χ A
CA = = =
Fv , f FV ,0 (1 + Χ A ) ε1+ ΧA ε
b b
FB , 0 − FA , 0 Χ A C B , 0 − C A , 0 Χ A
FB a a
CB = = =
FV , f FV ,0 (1 + Χ A ) ε 1+ Χ A ε
c c
FC , 0 + FA,0 Χ A C C ,0 + C A,0 Χ A
FC a a
CC = = =
FV , f FV ,0 (1 + Χ A ) 1+ ΧAε ε
d d
FD , 0 + FA,0 Χ A C D , 0 + C A,0 Χ A
FD a a
CD = = =
FV , f FV , 0 (1 + Χ A ) ε
1+ Χ A ε
Generally,

C j ,0 +
υ C ΧA
υ
j
A, 0

Cj =
1+ε Χ
A
(1.24.2)
A
It is to be noted that the concentration as a function of conversion for different
species expression for variable-volume flow system is represented in the same way as for
the concentration expression in the variable-volume batch system, equation (1.20). Figure
1.4 illustrate concentration of a reactant as a function of conversion for different system.

1.3.3 Other measures of Concentration as a function of Conversion

A) Mole Fraction as a function of Conversion

If the total number of moles present is represented as,

s
nT = ∑ n j (1.27)
j =1
21

Stoichiometric Relationship in Reaction

where, the mole fraction is

nj
y j= (1.27.1)
nT

n j ,0
y j ,0 = (1.27.2)
nT , 0

Recalling equation (1.11) and (1.11.1)

n j = n j ,0 +
υ n j ,0 Χ A
υ
j

υ Δυ n
1
nT = nT , 0 A, 0 ΧA
A

By replacing and rearranging, we get

υ y
y j ,0 + ΧA
υ
j
A, 0

=
A
yj (1.27.3)

υ Δυ y
1
1+ A, 0 ΧA
A

Individual mole fraction as a function of conversion can be expressed using equation

(1.27.3)

Progress Test 1.3 Considering C2H4 as a limiting reactant, write the mole
fraction as a function of conversion for the following reaction:

2C2 H4 + O2 → 2C2H4O

B) Extent of Reaction as a function of Conversion

Recalling equation (1.9.2) extent of the reaction can be defined as,

n j − n j0
ϕ=
υ j

The same way it can be defined for reactant A as,

n A − n A, 0 − (n A − n A,0 ) n A, 0 − n A
ϕ= = =
− υ A − (− υ A ) υ A
(1.9.5)
22

Introduction to Chemical Reaction

The conversion of A, has also be defined in equation (1.10.2) as,

n A, 0 − n A
ΧA =
n A, 0
or
n A,0 − n A = Δn A = n A,0 Χ A

Substituting this equation into equation (1. 9.5) we get.

n Χ
ϕ = A, 0 A
υ A
(1.28)

when υ A = 1, the extent of reaction as a function of conversion can be represented as,

ϕ = n A, 0 Χ A (1.29)

Progress Test 1.4 Write mole fraction as a function to the extent of reaction for
ethylene oxidation.

Exercise 1.1 Sulphur dioxide is burned with air at 250C and 1 atm in the
following reaction
1
SO2 +
O2 → SO3
2
The initial mixture contains 7 % SO2, 10 % O2 and 83 % N2 as inert. Determine the
composition of the product in terms of mole fraction of X SO2 =0.85 %.

Solution

From equation (1.27.3) the various mole fraction are calculated

υ y
y j ,0 + ΧA
υ
j
A, 0

=
A
yj

υ Δυ y
1
1+ A, 0 ΧA
A

y j ,0 +
υ y A, 0 Χ A
υ
j

yj =
A
(E.1.1.1)
δ
23

Stoichiometric Relationship in Reaction

here, A = SO2 ; X SO2 = 0.85 % ; Δ υ = 1 − 1 − 12 = − 12 and

υ υy
1 1 1
δ = 1+ Δ A, 0 ΧA = 1+ (− )(0.07)(0.85) = 0.97025 (E.1.1.2)
A 1 2

thus

y SO2 ,0 +
υ SO2
y SO2 , 0 Χ SO2
υ SO2 0.07 − (0.07)(0.85)
y SO2 = = = 0.0108
0.97025 0.97025

y O2 ,0 +
υ O2
y SO2 , 0 Χ SO2
υ SO2
1
0.01 − ( )(0.07)(0.85)
2
y O2 = = = 0.0724
0.97025 0.97025

y SO3 ,0 +
υ SO3
y SO2 , 0 Χ SO2
υ SO2 0 + (0.07)(0.085)
y SO3 = = = 0.0613
0.97025 0.97025

y N 2 ,0 +
υ SO3
y SO2 , 0 Χ SO2
υ SO2 0.83 + (0)(0.07)(0.85)
y N2 = = = 0.8554
0.97025 0.97025

∑y j = y SO2 + y O2 + y SO3 + y N 2 ≈ 1.0000

Exercise 1.2 For a system in which the following reaction occurs

3H 2 + CO → CH + H O
4 2
Develop general expression for the equilibrium constant as a function of extent of
reaction.

Solution

Equilibrium constant to the partial pressure is given by

PCH 4 PH 2O y CH 4 P y H 2O P y CH 4 y H 2O
K eq , P = 3
= 3
= 3
P −2 (E1.2.1)
P H2 PCO y H2 P y CO P y H2 y CO

where, Pj , partial pressure of species j

24

b c d
A+ B→ C+ D
a a a

Batch Flow

FA FA, 0 (1 − Χ A )
CA = =
n A n A,0 (1 − Χ A ) FV , f FV , f
CA = =
Vf Vf FA FA,0 (1 − Χ A )
CA = =
FV ,, f FV , f

Constant Volume Variable Volume Constant Volume Variable Volume

V f = V0 V f ≠ V0 FV , f = FV ,0 FV , f ≠ FV ,0
n A, 0 (1 − Χ A ) FA, 0 (1 − Χ A )
CA = CA =
V0 Fv ,0
C A = C A, 0 (1 − Χ A ) C A = C A, 0 (1 − Χ A )

V f = V0 (1 + εΧ A
⎛
)⎜⎜ T
⎞⎛ P0 ⎞
⎟⎟⎜ ⎟
⎝ T0 ⎠⎝ P ⎠

FV , f = FV ,0 (1 + εΧ A
⎛
)⎜⎜ T
⎞⎛ P0 ⎞
⎟⎟⎜ ⎟
⎝ T0 ⎠⎝ P ⎠

Constant
Constant temperature &
temperature& presure
pressure
ε
V f = V0 (1 + Χ A ) FV , f = FV ,0 (1 + X )
A
ε

n A,0 (1 − Χ A ) FA, 0 (1 − Χ A )
CA = CA =
V0 (1 + εΧ A ) FV ,0 (1 + εΧ A )
C A,0 (1 − Χ A ) C A, 0 (1 − Χ A )
CA = CA =
1+ Χ ε A
1+ Χ ε A

Figure 1.4 Expressing concentration of a reactant A as a function of conversion

for different system
25

Stoichiometric Relationship in Reaction

To find the expression for mole fraction as a function of extent of reaction, we use
stoichiometric relationship,

n H 2 − n H 2 ,0 nCO − nCO ,0 nCH 4 − nCH 4 ,0 n H 2 O − n H 2O , 0

= = = = ϕ (E1.2.2)
−3 −1 1 1
thus,
n H 2 = n H 2 , 0 − 3ϕ
nCO = nC 0 , 0 − ϕ
nCH 4C = nCH 4 , 0 + ϕ
n H 2O = n H 2O , 0 + ϕ

nT = nT , 0 − 2ϕ (E1.2.3)

thus, various mole fractions are

nCH 4 ϕ
y CH 4 = (E1.2.4)
nT nT ,0 − 2ϕ
nCO nCO , 0 − ϕ
y CO = (E1.2.5)
nT nT ,0 − 2ϕ
n H 2 n H 2 ,0 − 3ϕ
yH2 = (E1.2.6)
nT nT , 0 − 2ϕ
n H 2O ϕ
y H 2O = (E1.2.7)
nT nT ,0 − 2ϕ
Solving the equilibrium constant,
ϕ 2 (nT , 0 − 2ϕ ) 2
K equ , P = P −2 (E1.2.8)
(n H 2 − 3ϕ ) 2 (nCO ,0 − ϕ )

1.3.4 Measurment of Concentration in Multiple Reaction

When more than one reaction takes place in the reactor system like,
CO + 2H 2 → CH 3 OH
CO 2 + H 2 → CO + H 2 O
It is more convenient to write the equation in terms of modified conversion, which can be
defined as follows:
τ j ,i =
ϕi
nT ,0
(1.30)
26

Introduction to Chemical Reaction

where, τ j,i - is the modified conversion of species j in the reaction i. It might be

different for different reactions. From equation (1.9.2) we have

n j − n j ,0 n j ,0 − n j Δn j
ϕj = = =
υ υ υ
m ,i

j j j

where, Δn j m ,i - is the change of the mole of the main reactant in reaction i, then,

Δn j
τ j ,i =
υ nT , 0
i (1.31.1)
j

Analogically the modified conversion can also be defined as,

τ j ,i =
ϕi
V0
(1.31.2)

τ j ,i =
ϕi
mT , 0
(1.31.3)

Relationship between the modified conversion and the reaction conversion can be shown
as,

τ j ,i nT ,0 = ϕ i = n j ,0 Χ j for υj = 1

τ j ,i =
n j ,0
nT , 0
Χ j = y j ,0 Χ j (1.32)

Taking moles as a function of conversion for a single reaction, the expression of modified
conversion can be replaced by:

n j = n j ,0 +
υ n A, 0 Χ A
υ
j

υ y n Χ
A

= y j ,0 nT ,0 +
υ
j
A, 0 T , 0 A
A

⎡
= nT ,0 ⎢ y j ,0 +
υ y Χ⎤
υ
j
⎥ A, 0 A
⎢⎣ ⎥⎦
A

⎡
∴ n j = nT ,0 ⎢ y j ,0 +
υτ ⎤
υ ⎥
j
A (1.33)
⎢⎣ A ⎥⎦
27

Stoichiometric Relationship in Reaction

For several reactions moles of species j can be written as,

⎡
n j = nT , 0 ⎢ y j , 0 + ∑
r υ τ ⎤
A ,i ⎥
j ,i

⎢⎣ L =1 υ A ,i ⎥⎦
(1.34.)

where, τ A,i - selected as reference reactant in the reaction i. It might be different for
different reactions; r number of independent reactions.

Taking the total initial mole fraction as,

y j ,01 + y j ,02 + y j ,03 + − − − − − − − − − = 1

then, the total moles of the process can be expressed as

⎛ r
nT = nT ,0 ⎜1 + ∑
Δ υτ ⎞
⎟
υ
i
(1.35)
⎜ L =1 A ,i
⎟
⎝ A ,i ⎠

From the equations (1.34.) and (1.35), it is evident for several reactions that

r υ j ,i
y j ,0 + ∑υ
i =1
τ A, i
yj =
υτ
A ,i
(1.36)
r
Δ
1+ ∑
υ
i
A ,i
L =1 A ,i

For constant volume, ρ m =constant, concentration of species j is equal to

Cj = C j ,0 + CT , 0 ∑
r υ τ
υ
j ,i
A ,i (1.37)
L =1 A ,i

For variable volume, ρ m ≠ constant, concentration of species j becomes

r
P
( y j , 0 + ∑ υ j ,i )
RT
Cj =
υ
τ A ,i
i =1
(1.38)
r
Δ i
1+ ∑
L =1 υ A ,i
28

Introduction to Chemical Reaction

Exercise 1.3 Given that, for the synthesis of Methanol, the following reactions
take place:
CO + 2H 2 → CH 3 OH (1)
CO 2 + H 2 → CO + H 2 O (2)
5
The reaction is carried out at T = 493 K and P = 51x10 Pa with initial mole fraction of
y H 2O ,0 = 0.7438 ; y CO2 ,O = 0.1000 ; y CO ,O = 0.1180 ; and y In,0 = 0.0382 . The outlet
composition of the mixtures contain y CO = 0.1044 ; y CO2 = 0.0902 ; y H 2 = 0.7045 ,
y CH 3OH = 0.0414 ; y H 2O = 0.0181 ; and y In = 0.0413 . Using reference substances CO
and CO2, find modified conversion and conversion of CO and CO2.

Solution

The mole fraction of each species will be computed using equation (1.36)
r υ j ,i
y j ,0 + ∑υ
i =1
τ A, i
yj =
υτ
Ai
r
Δ
1+ ∑
υ
i
A ,i
L =1 A ,i

The common denominator is given by

r
1+ ∑
Δ i υτ
A, i = 1 − 2τ 1 − 2τ 2
L =1 υ A, i
(E.1.3.1)

thus
y CO , 0 − τ 1
y CO = (E.1.3.2)
1 − 2τ 1 − 2τ 2

y CO2 , 0 − τ 2
y CO2 = (E.1.3.3)
1 − 2τ 1 − 2τ 2

y H 2 , 0 − 2τ 1 − 3τ 2
yH2 = (E.1.3.4)
1 − 2τ 1 − 2τ 2

τ1 + τ 2
y CH 3OH = (E.1.3.5)
1 − 2τ 1 − 2τ 2
29

Stoichiometric Relationship in Reaction

τ2
y H 2O = (E.1.3.6)
1 − 2τ 1 − 2τ 2

y In, 0
y In = (E.1.3.7)
1 − 2τ 1 − 2τ 2

Equations ( E1.3.5 ) and (E.1.3.6) give

y CH 3OH τ1 + τ 2
= (E.1.3.8)
yH O 2
τ2
Taking equation ( E.1.3.7 ) and rearrange, we have

1 y In,0
τ1 + τ 2 = (1 − ) (E.1.3.9)
2 y In

Substituting equation ( E.1.3.9 ) in equation ( E.1.3.8 ) and rearranging gives

1 y H 2O y In, 0
τ2 = (1 − ) (E.1.3.10)
2 y CH 3OH y In

Equation ( E.1.3.8 ) gives

y C H 3OH
τ1 = τ 2 ( − 1) (E.1.3.11)
y H 2O

then in equation ( E.1.3.10 ) and ( E.1.3.11 )

1 0.0184 0.0383
τ2 = ( )(1 − ) = 0.01668
2 0.0414 0.0413

0.0414
τ 1 = 0.01668( − 1) = 0.02147
0.0181

The relationship between conversion and modified conversion is given by equation (1.32)

X =
n j ,0
τ =
τ j ,i
j ,i
j nT ,0 y j ,0
30

Introduction to Chemical Reaction

thus,
X CO =
τ 1
=
0.02147
= 0.1819
y CO ,0 0.1180

X CO2 =
τ 2
=
0.01668
= 0.1668
y CO2 ,0 0.1000

[Link] Conversion in Multiple Reactions

Consider the following reactions

aA + bB → cC + dD (1)

gA + fC → eE (2)

We defined XA,1 as the conversion of A to form C and D in reaction 1

moles of A consumed by reaction 1

X A,1 = (1.39)
moles of A initially

and we define XA,2 as the conversion of A to form E in reaction 2

moles of A consumed by reaction 2

X A, 2 = (1.40)
moles of A initially

A form of modified equation ( 1.34) expresses the number of moles of species j at any
time
υ
r
n j = n j , 0 + n A, 0 ∑ j ,i Xi (1.41)
L =1

where, υ ji is the stoichiometric coefficients for species j in the ith - reaction and Xi is the
conversion for ith - reaction i. Equation (1.41) can be used to develop the stoichiometric
relationship for the above multiple reactions. This is given in Table 1.4

Concentration as a function of conversion can be computed for variable volume

nj
Cj =
Vf
31

Stoichiometric Relationship in Reaction

From equation (1.16.1) and (1.11.2), we obtain

nT ⎛P ⎞⎛ T ⎞
Vf = V0 ⎜ 0 ⎟⎜⎜ ⎟⎟
nT ,0 ⎝ P ⎠⎝ T0 ⎠

nT n
= T ,0 + Δ
nT ,0 nT ,0 1
υ
n A, 0
nT ,0
Χ A,1 + Δ
2
n A, 0
nT ,0
Χ A, 2 υ
= 1 + Δυ y A, 0 Χ A,1 + Δυ y A, 0 Χ A, 2
1 2
+τ Χ τ2 Χ
nT
= 1 A,1 + A, 2
nT , 0 1

Table 1.4 Stoichiometric relationship for multiple reactions

aA + bB → cC + dD (1)
gA + fC → eE (2)

Moles
initially
present Change in mole Remaining Mole in the system at time t
− (n A, 0 Χ A,1 + n A,0 X A, 2 )
A n A, 0 nA = nA, 0 − nA, 0 Χ A,1 − nA, 0 Χ A, 2
−b b
n B,0 n A,0 Χ A,1 nB = nB0 − n A,0 Χ A,1
B a a
c f
nA, 0 Χ A,1 − nA,0 Χ A, 2
a g c f
nC = nC , 0 + n A,0 Χ A,1 − n A,0 Χ A, 2
C nC , 0 a g
d d
n D,0 n A, 0 Χ A,1 n D = n D , 0 + n A,0 Χ A,1
D a a
Error! Objects cannot e
be created from editing n E = n E , 0 + n A, 0 Χ A, 2
E n E ,0 field codes. g
I (Inerts) n I ,0 - n I = n I ,0

Total nT ,0 nT = nT , 0 + Δυ1 n A, 0 X A,1 + Δυ 2 n A, 0 X A, 2

For constant pressure and temperature,

V f = V 0 (1 + τ1 Χ A ,1 + τ2 Χ A,2 ) (1.42)
32

Introduction to Chemical Reaction

The concentration of each species is

n n A,0 − n A, 0 Χ A,1 − n A,0 Χ A, 2
CA = A =
Vf V f = V0 (1 + Χ
1 A,1
τ + τ
Χ )
2 A, 2

C A,0 ( 1 − Χ A,1 − Χ A, 2 )
CA =
1 + τ1 Χ A,1 + τ2 Χ A, 2
(1.43)

Analogy
b
C A, 0 ( φ B −
Χ A,1 )
CB = a
1 + Χτ
1 A,1
+ Χ
2 A, 2
τ
c f
C A, 0 ( φ C +Χ A,1 − Χ A, 2 )
a g
CC =
1 + τ
Χ
1 A,1
+ Χ
2 A, 2
τ
d
C A, 0 ( φ D +
Χ A,1 )
CD = a
1 + Χτ
1 A,1
+ Χ
2 A, 2
τ
e
C A, 0 ( φ E +
Χ A, 2 )
g
CE =
1 + Χτ
1 A,1
+ Χτ
2 A, 2
C j ,0
where, φ j =
C A, 0

1.4 Selectivity and Yield

Invariably, in a reaction from a reactant, both the desired and undesired products are
obtained simultaneously. For an example,

P---------- Desired Product

Reacant A
X--------- Undesired Product

In the complexity of such types of reactions, only conversion factor is not important but
to have the reaction to be controlled through two parameters i.e., selectivity and yield.
33

Stoichiometric Relationship in Reaction

1.4.1 Selectivity

Selectivity can be defined in many ways, as illustrated below:

• Selectivity is the ratio of the moles of desired product formed per

mole of undesired product formed:

nP
SP = (1.44.1)
nΧ

• Selectivity is the ratio between the amount of desired product P

obtained and the key reactant A converted.

SP =
υ nP
υ (n
A ,i

A, 0 − n P )
(1.44.2)
P

• Selectivity is the ratio between the changes of mole of the main

reactant in the main reaction and the total main reactant mole
changes in the process

Δn A
SP = m
(1.44.3)
Δn A

Equation is simply derived from stoichiometric relationship and it is our interest. Let us
develop the stoichiometric relationship for the following complex reactions :

υ A ,1 A→ υP P desired
υ A, 2 A →υ Χ Χ
product (1)
undesired
Product (2)

For such reactions we can write

Δn A,1 Δn P
=
− υ A,1 υ P

where, Δn A = n A − n A,0 ; Δn P = n p − n p ,0
34

Δn A,1 = − υ υ
Δn
A,1
P

P
Introduction to Chemical Reaction

(n − n A, 0 ) 1 = −
υ Δn P
υ
A,1
A
P

(−n + n A, 0 ) 1 =
υ Δn p
υ
A,1
A
P

Δn A =
υ Δn p
υ
A,1
m
(1.45)
P

Substituting equation (1.45) in to equation (1.44.3) we have the combination equation for
selectivity,

SP =
Δn A
=
υ A,1 Δn P
=
υ (n
A,1 − n P ,0 )
υ υ (n
m P

− nA )
(1.46.1)
Δn A P Δn A P A, 0

When we have pure reactant, n p ,0 = 0, the equation (1.46.1) becomes,

SP =
υ nP
υ (n
A,1

A, 0 − n A )
(1.47)
P

1.4.2 Yield

It refers to the amount of a specific product formed in a given reaction process per
mole of entering reactant.

A → P

Υp =
υ A,1 np
υ P n A, 0
(1.48)

It should be noted that both the selectivity and yield vary between 0 and 1. Both
factors are considered when complex reactions take place and where reactions are
competing with each other. However, in the reactor's product separation section, the key
reactant A can be recovered and recycled to the reactor section, where the selectivity
35

which is based on the amount of reactant A converted in the reactor. It is the key factor
in the economic operation of the plant.

Stoichiometric Relationship in Reaction

If on the other hand, reactant A cannot be recovered from the product stream and
the non-converted A is wasted in the operation, then the yield, which is based on the
amount of feed, is the economic factor. Yield and selectivity are usually more important
than total conversion for complex reaction systems. The relationship between these
parameters is described in the following equations.

From the equations (1.48) and (1.46.1) for equal stoichiometric coefficient of
reactant and product by combining and rearranging the equations gives us,

nP np np
ΥP = and S P = =
n A, 0 n A, 0 − n A Δn A

S P Δn A S P (n A, 0 − n A )
ΥP = =
n A, 0 n A, 0

ΥP = S P Χ (1.49)

For a single reaction, since Δn A m

= Δn A , then conversion is identical to the
yield and automatically the selectivity will be unity.

YP = Χ A
(1.50)
S P = 1

1.0

SP

0.5 ΥP

0 0.5 1
36

Figure 1.5 Selectivity and Yield profiles for consecutive reactions:

A →B → C
Introduction to Chemical Reaction

Problems
P1.1 Soap is composed of the sodium and potassium salts of various fatty
acids such as oleic, stearic, palmitic, and myristic acids. The saponification for the
formation of soap from aqueous caustic soda and glyceryl stearate is

3NaOH ( aq ) + (C17 H 35 COO ) 3 C 3 H 5 → 3C H COONa + C H (OH )

17 35 3 5 3
a. Set up a stoichiometric table expressing the concentration of the each species
in terms of its original concentration and the conversion of sodium hydroxide.

b. If the initial mixture consists solely of sodium hydroxide at a concentration of

10K mol/m3 and of glyceryl stearate at a concentration of 2 K mol/m3, what is
the concentration of glycerine when the conversion of sodium hydroxide is

i) 20 %
ii) 90 %

P1.2 A mixture of 28% SO2 and 72% air is charged to a flow reactor in
which SO2 is oxidized for sulphuric acid production,

2SO2 + O2 → 2SO3

Taking SO2 as the base of calculation for the case when the total pressure is 1485 K Pa
and the temperature is constant at 227oC express:

i) The concentration of different species at various conversion.

ii) (− rA ) as function of conversion if the rate law for this reaction were first
order, in SO2 and in O2, with k= 200 m3/mol.S.
iii) For the condition ii) determine for a final conversion of 80%.

a. Time of a reaction for a batch reactor is CAO is 0.1 g mole/lit.

b. The volume of a plug-flow reactor for an FAO of 1 g mole/s
c. The volume of C.S.T.R reactor for the same FAO

P1.3 Consider a vessel which initially contains only n H 2 0 , o moles of water

vapour. If dissociation occurs according to the following reaction.

H2O → H2 + ½ O2
37

Find expression which relate the mole fraction of each chemical species & conversion of
H2O to the extent of reaction.
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