Kinetics of a pseudo first order reaction for dehydrogenation of Isopropanol

THEORY

The rate at which a chemical reaction occurs depends on several factors: the nature of the
reaction, the concentrations of the reactants, the temperature, and the presence of possible
catalysts. All of these factors can markedly influence the observed rate of reaction.

In this experiment, we will study a reaction which, proceeds under moderate temperature
(350°C), at a relatively easily measured rate. For the first order irreversible reaction,

(CH3)2CHOH (CH3)3CO + H2

Isopropanol Acetone Hydrogen

the rate can be expressed by the following equation, which is called the rate law,

rate = k*C(CH3)2CHOH

where, k is the specific rate constant for the reaction.

As with the concentration, there is a quantitative relationship between reaction rate and
temperature. This relation is based on the idea that in order to react, the reactant species must
have a certain minimum amount of energy present at the time the reactants collide in the
reaction step. This amount of energy, which is typically furnished by the kinetic energy of the
species present, is called the activation energy of the reaction.

For a first order, isothermal, irreversible reaction at constant pressure we have the following
expression for the conversion of component A,XA

dCA
Rate = -rA= - = k*CA -----(1)
𝑑𝑡

When the volume of reaction system mixture changes linearly with conversion, we have
V = Vo(1+ƐA*XA)
𝐶𝐴 1−XA
= (1+ƐA∗XA) ------(2)
𝐶𝐴𝑜

Put equation (2) in equation (1)

dCA 1−XA
-rA= - = k*CAo*(1+ƐA∗XA)
𝑑𝑡
We have, space time equation
𝑋𝐴 𝑑𝑋𝐴
τ = CAo*∫0 −𝑟𝐴

Substituting for (--rA) gives,

𝑋𝐴 𝑑𝑋𝐴
τ= CAo*∫0 1−XA
k∗CAo∗
(1+ƐA∗XA)

Rearranging yields,
𝑋𝐴 (1+ƐA∗XA)∗𝑑𝑋𝐴 𝑋𝐴 𝑑𝑋𝐴 𝑋𝐴 (XA)∗𝑑𝑋𝐴
τ *k = ∫0 = ∫0 +ƐA ∫0
(1−XA) (1−XA) (1−XA)

τ *k = -ln(1-XA) + ƐA*I1 ------(3)

Where,
𝑋𝐴 (XA)∗𝑑𝑋𝐴
I1 = ∫0 (1−XA)

Put, (1- XA) = Y

d XA = -dY

At, XA = 0; Y = 1

At, XA = XA; Y = 1- XA

And, XA = 1- Y
𝑋𝐴 (XA)∗𝑑𝑋𝐴 1−𝑋𝐴 (1−Y)∗𝑑𝑌
I1 = ∫0 = -∫1
(1−XA) Y
1−𝑋𝐴 𝑑𝑌 1−𝑋𝐴 𝑑𝑦
I1 = − ∫1 + ∫1
1 𝑌

I1 = -ln(1-XA) + (1- XA-1)

I1 = -ln(1-XA) + XA
Substituting for I1 in equation (3) gives,

τ *k = -ln(1-XA) - ƐA*ln(1-XA) - ƐA*XA

τ *k = - (1+ƐA)*ln(1-XA) - ƐA* XA ------(5)
Equation (5) is the integrated rate equation for first order reaction for variable density system.

From the kinetics expression, at a reactor temperature of 350C, we have:

k=k0exp[-Ea/RT] =3.51×105exp[72,380/ (8.314)(273+350)]

=0.2996m3gas/m3bulk catalyst
ԑA= (number of mole if completely reacted – number of moles initially)/ number of moles
initially

from reaction,

= (2-1)/(1)=1

Using above values and 90% conversion we get:

Kτ = -(1+1)*ln (1-0.9)-(1)(0.9)=3.7052

τ =(3.7052)/(0.2996) =12.36 m3bulk catalyst s/ m3gas

VReactor = υgas * τ

Where, υgas = Volumetric flow rate of gas

Now the volumetric flow rate of gas from inlet feed flow rate, υgas =0.19949 m3/min

VReactor = (0.19949)(12.36) =2.4656 m3

Volume of reactor required to achieve 90% conversion with gas flow rate of 0.19948 m3/min
is 7.5 m3