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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YA1

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 (ρb)

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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
‰θ = is called space time (s) = V/vo
‰Space velocity = 1/θ, 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 -ÆcC + 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 Æ (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
⎜
1⎞
− ⎟
−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 188˚C
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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