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Chemical Reaction Engineering

Dr. Yahia Alhamed

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Kinetics and Reaction Rate
What is reaction rate?
It is the rate at which a species looses its
chemical identity per unit volume.
The rate of a reaction can be expressed as:-
- The rate of disappearance of a reactant or
- The rate of appearance of a product.

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Reaction Rate
Consider species A:

-rA = the rate of formation of species A per unit volume


rB = the rate of formation of species B per unit volume
EXAMPLE: If B is being formed at 0.2 moles per decimeter
cubed per second, ie, rB = 0.2 mole/dm3/s
Then A is disappearing at the same rate:
-rA= 0.2 mole/dm3/s
The rate of formation (generation of A) is rA= -0.2
mole/dm3/s

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Slide 3

YA1 Y A, 4/5/2008
Reaction Rate
Consider species j:
rj is the rate of formation of species j per unit
volume [e.g. mol/dm3*s]
rj is a function of concentration, temperature,
pressure, and the type of catalyst (if any)
rj is independent of the type of reaction system
(batch, plug flow, etc.)
rj is an algebraic equation, not a differential
equation
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Rate Law Basics
A rate law describes the behavior of a
reaction. The rate of a reaction is a
function of temperature (through the rate
constant) and concentration.

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Reaction Rate for solid catalytic reactions

For a catalytic reaction, we refer to -rA', which


is the rate of disappearance of species A on a
per mass of catalyst basis.
-r'A = rA/bulk density of the catalyst (b)

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Rate Law Basics
A rate law describes the behavior of a reaction. The rate
of a reaction is a function of temperature (through the
rate constant) and concentration.
Power Law Model
k is the specific reaction rate (constant)
k is given by the Arrhenius Equation:

Where:E = activation energy (cal/mol)


R = gas constant (cal/mol*K)
T = temperature (K)
A = frequency factor (units of A, and k, depend on overall
reaction order)
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General Mole Balance

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Batch Reactor Mole Balance

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Constantly Stirred Tank Reactor Mole Balance
CSTR or MFR

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Plug Flow Reactor (PFR) Mole Balance

FA dF A
The integral form is: V=
FA 0 rA

This is the volume necessary to reduce the entering molar


flow rate (mol/s) from FA0 to the exit molar flow rate of FA.
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Packed Bed Reactor Mole
Balance
PBR

dN A
FA0 FA + rA dW =
dt

FAdFA
The integral form to find the catalyst weight is: W=
FA 0 rA

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Space time and space velocity
FA0 = CAo vo
= is called space time (s) = V/vo
Space velocity = 1/, where;
FA0 = Molar feed rate of key reactant A (mol/s)
CAo= Concentration of key reactant A in the feed
(mol/m3)
vo=Volumetric flow rate of feed to the reactor (m3/s)
V = volume of the reactor
For constant volume systems v = vo where v is
volumetric flow rate leaving the reactor
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Reactor Mole Balance Summary

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Reactor Mole Balance
Summary

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Reactor Mole Balance
Summary

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Reactor Mole Balance
Summary

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Reactor Mole Balance
Summary

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Conversion
Consider the general reaction: aA + bB -cC + dD
We will choose A as bases of calculation (i.e. Key reactant)
The limiting reactant is usually taken as the key reactant
Then: A + (b/a)B (c/a)C + (d/a)D
XA = moles reacted/moles fed

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Batch Reactor Conversion
dN A
= rA V
dt

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CSTR Conversion

Algebraic Form:

There is no differential or integral form for a CSTR.

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PFR Conversion

dF A
PFR
= rA
dV
FA = F A0 (1 X)

Differential Form:

Integral Form:

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Design Equations

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Reactor Sizing (CSTR)
Given -rA as a function of conversion, -rA=f(X), one can size any
type of reactor.
We do this by constructing a Levenspiel plot.
Here we plot either FA0 or 1 as a function of X.
r A r A
volume of a CSTR is: F A0 (X 0 )
V=
rA
EXIT

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Reactor Sizing (PFR)
For PFR th evolume of the reactor needed is
given by the area under the curve
X F
V PFR = 0 rA
A 0
dX

=area

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Summary

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Rate Law Basics
A rate law describes the behavior of a
reaction. The rate of a reaction is a
function of temperature (through the rate
constant) and concentration.

Power Law Model


k is the specific reaction rate (constant)

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Examples of Rate Laws
First Order Reactions
(1) Homogeneous irreversible elementary gas phase reaction
C2H 6 C2H 4 + H 2 82kcal 1

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1 mol 1000 T
rA = kC C 2 H 6 with k = 0.072s e

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Examples of Rate Laws
First Order Reactions
(1) Homogeneous irreversible elementary gas phase reaction
C2H 6 C2H 4 + H 2 82kcal 1

1

1 mol 1000 T
rA = kC C 2 H 6 with k = 0.072s e

(2) Homogeneous reversible elementary reaction


n C 4 H10 i C 4 H10
[
rn = k C nC 4 CiC 4 K C ]
T 360 T 333
k = 31.1exp 7906 K C = 3.03exp 830.3
with 360T
and 333T

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Examples of Rate Laws
First Order Reactions
(1) Homogeneous irreversible elementary gas phase reaction
C2H 6 C2H 4 + H 2 82kcal 1

1

1 mol 1000 T
rA = kC C 2 H 6 with k = 0.072s e

(2) Homogeneous reversible elementary reaction


n C 4 H10 i C 4 H10
[
rn = k C nC 4 CiC 4 K C ]
T 360 T 333
k = 31.1exp 7906 K C = 3.03exp 830.3
with 360T
and 333T

Second Order Reactions


(1) Homogeneous irreversible non-elementary reaction

m3 cal
with k = 0.0017 and E = 11273 At 188C
kmol.min mol

rA = kC ONCBC NH3

This is first order in ONCB, first order in ammonia and overall second order.
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Examples of Rate Laws
Second Order Reactions
(2) Homogeneous irreversible elementary reaction
CNBr + CH 3 NH 2 CH 3 Br + NCNH 2 with 2.2dm 3
k=
s.mol
rA = kC CNBr C CH 3 NH 2

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Examples of Rate Laws
Second Order Reactions
(2) Homogeneous irreversible elementary reaction
CNBr + CH 3 NH 2 CH 3 Br + NCNH 2 with 2.2dm 3
k=
s.mol
rA = kC CNBr C CH 3 NH 2
This reaction is first order in CNBr, first order in CH3NH2 and overall second order.

(3) Heterogeneous catalytic reaction: The following reaction takes place over a solid
catalyst:

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