Reactor Design - Fourth Year Dr. Ali .N.

Khalaf

Chapter Two

Concepts of Kinetics and

Reaction Rate

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Reactor Design - Fourth Year Dr. Ali .N.Khalaf

1- Reaction Rate (Rate Low): (-rA)

The reaction rate (rA) is defined as the change in moles of component A (reactant
consumed) or mole of product formed with respect to time per unit volume of
reaction mixture.

If the rate of change in number of moles of this component due to reaction is dNildt,
then the rate of reaction in its various forms is defined as follows.

Based on unit volume of reacting fluid,

Based on unit mass of solid in fluid-solid systems

Based on unit interfacial surface in two-fluid systems or based on unit surface of

solid in gas-solid systems

Based on unit volume of solid in gas-solid systems

Based on unit volume of reactor, if different from the rate based on unit volume of
fluid,

Suppose a single-phase reaction aA + bB → rR + sS.

The most useful measure of reaction rate for reactant A is then

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Reactor Design - Fourth Year Dr. Ali .N.Khalaf

In addition, the rates of reaction of all materials are related by

If i is a product, the rate is defined in terms of rate of appearance (ri)

If i is a reactant, the rate is defined in terms of disappearance (-ri)
−1 d N A
Batch Reactor: −r A = …………………………… (2.1)
V dt
−d F A
Plug Flow Reactor: −r A = …………………………… (2.2)
dV

NA = number of moles (mol)

FA =molar flow rate (mol/time)
Rate of reaction r A is:

 a function of concentration, temperature, pressure, and the type of catalyst (if

any)

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Reactor Design - Fourth Year Dr. Ali .N.Khalaf
 independent of the type of reaction system (batch, plug flow, etc.) on the
reaction chemistry
 an algebraic equation, not a differential equation
 Rate of reaction per unit weight of catalyst and rate of reaction per unit volume
is related through the bulk density of the catalyst particle in the fluid media.

Rate Law: or kinetic expression is an algebraic equation that relates reaction rate to
species concentration (-rA) = [kA(T) ]·[fn(CA, CB, ..)]

2. Conceptes of Kinetics:
2.1- Stoichiometry

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Reactor Design - Fourth Year Dr. Ali .N.Khalaf

2.2-Chemical Identity:
A chemical species is said to have reacted when it has lost its chemical identity.
There are three ways for a species to lose its identity:

A. Decomposition CH3CH3 à H2 + H2C=CH2

B. Combination N2 + O2 à 2 NO

C. Isomerization C2H5CH=CH2 à CH2=C(CH3)2

2.3- Reaction Rate Constant (k):

A majority of reaction rate constants can be expressed by an empirical relationship
that was developed by Swedish scientist, Svante Arrhenius.

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Reactor Design - Fourth Year Dr. Ali .N.Khalaf
−E
k = A e RT ……………………….. (2.3)

A = Frequency factor or pre-exponential factor

Ea = Activation Energy (cal/mol) or (J/mol)
R = Universal gas Constant (8.314 J/mol.K) (1.987 cal/mol.K)
T= Absolute Temperature (K).

•k is most sensitive to temperature at lower temperatures

• k with higher E is more sensitive to temperature than those with low E

E 1
ln k =¿ ln A− ( )
R T
¿ ……………………………(2.4)

Arrhenius parameters consist of the activation energy E and the frequency factor A.
the value of E may be calculated from the rate constants at two different temperatures
T1 and T2 as follows:

k 1=A e−E / R T 1
At T1

k 2=A e−E / R T 2
At T2

Combining the above two equations,

k2

( )
ln
E k1
=
R 1 1
−
T1 T2

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Reactor Design - Fourth Year Dr. Ali .N.Khalaf
The value of A is calculated from one of the Arrhenius equations shown above.

Sometimes The specific reaction rate at temperature T is commonly written in terms

of the specific reaction rate, k1 , at a reference temperature T1 and the activation
energy E. That is,

2.4- Reaction Order (n):

In the previous example, i.e., aA + bB → cC + dD

The rate law (in terms of the rate of consumption of A) was written as:

(- rA) = k C Aα C B β (Power Law Model)

α = reaction order with respect to A

β= reaction order with respect to B

n= α+ β = overall order of reaction
Now, if α = a and β = b, the reaction is considered to be Elementary Reaction.

Elementary Reaction H2 +I2 →2HI (-rH2) = k CH2 CI2

Non-elementary Reaction CO + Cl2⇋ COCl2 (-rCO) = k CCO CCl2 3/2

Note: The units of k depend on the reaction order. You can find out the overall
order of reaction from units of k.

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 Reactor Design - Fourth Year Dr. Ali .N.Khalaf

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1 2
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T T

3 4
-rA -rA

32
T T

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 Reactor Design - Fourth Year Dr. Ali .N.Khalaf

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-rA -rA

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2.5- Conversion ( x ¿:
Conversion, x, is defined as the fraction (or percentage) of the more important or
limiting reactant that is consumed. With two reactants A and B and a nearly
Stoichiometric feed, conversions based on each reactant could be calculated.

mole A reacted N −N A
x= = AO …………………… (2.6)
initial number of moles N AO

In a constant volume system, the conversion can be expressed as a function of

concentration and thus,
C AO −C A CA
x= =1−
C AO C AO

C A=C AO ( 1−x ) ……………………………. (2.7)

The conversion should always be defined for the limiting reactant of the reaction. The
conversion has no unit, ranging from 0 to 1 for irreversible reactions or from 0 to XAe
for reversible reactions.

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Reactor Design - Fourth Year Dr. Ali .N.Khalaf

3- Stoichiometric Table for Batch Reactors:

For the reaction aA + bB → cC + dD , Species A taken as (limiting reactant)
Then the reaction written as:
b c d
A+ B → C+ D
a a a

 Constant Volume Batch Reactor :

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Reactor Design - Fourth Year Dr. Ali .N.Khalaf
- If the reaction occurs in the liquid phase (negligable change in density) .

V = V0 [volume of liquid in the reactor could be < reactor volume]

- if a gas phase reaction occurs in a rigid (e.g. steel) (no change in the number of
moles (δ=0) .So V = V0 = VR [gas occupies the total volume of the reactor]
Ni
C i=
V

4- Stoichiometric Table for Flow Reactors:

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Reactor Design - Fourth Year Dr. Ali .N.Khalaf

 Constant Volumetric flowrate υ=υ o

- For liquid phase reaction where the change in density is negligable

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Reactor Design - Fourth Year Dr. Ali .N.Khalaf
- For gas phase reaction with no change in the total number of moles(δ=0) .

5- Variable Volume Batch Reactor:

The pressure in such systems may be constant or vary with conversion. At any given
conversion, X, the reactor volume may be related to initial reactor volume (V0) and
other operating parameters (P0, T0, P, and T). Individual concentration can be
determined by expressing the volume for batch system as a function of onversion
using the equation of state:

For gas phase reactions: P V =Z N T RT at any time

Po V o=Z o N ¿ R T 0 at t=0

Dividing thes equations gives

ε =δ y Ao

For ideal gases Z=Zo , then:

V =V o ( 1+ ε x ) ( PP )( TT )
o

o
……………………………………. (2.8)

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Reactor Design - Fourth Year Dr. Ali .N.Khalaf
 For isothermal reactions T=To
Po
V =V o ( 1+ ε x ) ( )
P
……………………………………. (2.9)

 For constant pressure reactions P=Po

T
V =V o ( 1+ ε x ) ( )
To
……………………………………. (2.10)

 For isothermal and constant pressure reactions

V =V o ( 1+ ε x ) ……………………………………. (2.11)

The concentration for gas phase is calculated from :

)2.12( …

P Ao P ¿ y Ao
C Ao= = ……………………………………. (2.13)
R T o RT o

6- Variable Volumetric flowratefor flow reactors(δ ≠0):

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Reactor Design - Fourth Year Dr. Ali .N.Khalaf
 For isothermal reactions T=To
Po
υ=υ o ( 1+ ε x ) ( )
P
……………………………………. (2.14)

 For constant pressure reactions P=Po

T
υ=υ o ( 1+ ε x ) ( )
To
……………………………………. (2.15)

 For isothermal and constant pressure reactions

υ=υ o ( 1+ ε x ) ……………………………………. (2.16)

The concentration for gas phase is calculated from :

P Ao P ¿ y Ao
C Ao= =
R T o RT o

7- Reaction Rates for Reversible Reactions:

All reversible reaction rate laws must reduce to the thermodynamic relationship
relating reacting species concentrations at equilibrium. At equilibrium, the net rate of
reaction is zero for all species involved in the reaction−r ieq =0.

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Reactor Design - Fourth Year Dr. Ali .N.Khalaf

For constant volume batch reactor and elementary reaction, the equlibrium constant
in terms of concentration is given by:
C A=C AO ( 1−x ) and equkibrium concentration is C Aeq=C AO ( 1−x e )

C B=C Ao ( ba ) x and equkibrium concentration is C Beq=C Ao ( ba ) x e

C C =C Ao ( ac ) x and equkibrium concentration is C Ceq =C Ao ( ca ) x e

Where x e is the Equlibrium Conversion.

( ba ) x C ( ca ) x 1 1

)( )(
C Ao
Then K = C Beq C Ceq =
eq 2
( C Aeq
e Ao

C AO2 ( 1−x e )2
e
=
2
C Ao x e C Ao x e
2
C AO ( 1−x e ) 2
2 )
x e2
(
K eq =
4 ( 1−x e )2 )
For elementary reaction the equlibruim constant at 298 K calculated from Standard
Gibss free energy equation .

∆ Go =−RT ln K eq ……………………………………. (2.17)

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Reactor Design - Fourth Year Dr. Ali .N.Khalaf
Or at any temperature from
K eq ∆ H r 1 1
ln
K 298
= ( −
R 298 T ) ……………………………………. (2.18)

Note that ∆ Go =∆ H o −T ∆ So

∆ H o =Enthalpy change

∆ S o=Entropy change

The variation of the reaction rate with the increase in temperature is always positive.
However, depending on whether the reaction is exothermic (∆H0 <0), the variation of
the resulting rate will depend on the difference Eforwaed –Ereverse

Therefore, the resulting rate increases and is always positive, and when the reverse
rate increases, the resulting rate reaches a maximum value and decreases positively
(according to Figurs( 2.1,2.2, and 2.3 ).

.Fig. 2.1 Influence of temperature on the reaction rate

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Reactor Design - Fourth Year Dr. Ali .N.Khalaf

Figure (2.2) show the variation of the concentration equilibrium constant and
equilibrium conversion as a function of temperature for an exothermic reaction.

Fig. (2.3) show the variation of the concentration equilibrium constant and
equilibrium conversion as a function of temperature for an endothermic reaction.

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