REACTION ENGINEERING I

Chapter 03: RATE LAWS

AQSHA
CHEMICAL REACTION ENGINEERING
[email protected]
SEPTEMBER 2020
SYLLABUS & TIMELINE

WEEK TOPIC ASSESSMENT NOTE

1 Chapter 0: Introduction to reaction engineering
2 Chapter 1: Introduction & mole balances Assignment 1
3 Chapter 2: Conversion and reactor sizing Quiz 1 Pop-Up
4 Chapter 3: Rate laws and stoichiometry Test 1 Will be scheduled
5 Chapter 4: Isothermal Reactor design – Batch & CSTR
6 Chapter 4: Isothermal Reactor design – PFR & PBR Assignment 2
7 Chapter 5: Collection & analysis of rate data Quiz 2 Pop-Up
8 Chapter 6: Multiple reactions - Introduction Test 2 Will be scheduled
9 Chapter 6: Multiple reactions – Series and Parallel
10 Chapter 8: Steady state non-isothermal reactor design Integrated Project Reactor Design
11 Chapter 10: Catalysis & Catalytic Reactor
12 Review – Study Week – Final Exam Prep Project Submission
REACTION ENGINEERING – BUILDING BLOCK

Heat Effects
Isothermal Design

Stoichiometry
Rate Laws
Mole Balance

CRE Algorithm
REACTION ENGINEERING – BUILDING BLOCK
• Block 1
• Mole Balances
• Size CSTRs and PFRs given –rA= f(X)
• Conversion for Reactors in Series
• Block 2
• Rate Laws
• Reaction Orders
• Arrhenius Equation
• Activation Energy
• Effect of Temperature

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MOLE BALANCE SUMMARY
MOLE BALANCE SUMMARY – IN CONVERSION
RATE LAWS
Building Block 2: Rate Laws
Power Law Model

  α order in A
− rA = kC A CB
β order in B
Overall Reaction Order = α + β

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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RATE LAWS
2A + B → 3C
A reactor follows an elementary rate law if the reaction orders just happens to
agree with the stoichiometric coefficients for the reaction as written.
e.g. If the above reaction follows an elementary rate law
− rA = k AC A2 C B
2nd order in A, 1st order in B, overall third order
Non-elementary rate law : The reaction order does not follow the stoichiometry.
Example: 𝐶𝑂 + 𝐶𝑙2 → 𝐶𝑂𝐶𝑙2
3/2
−𝑟𝐶𝑂 = 𝑘𝐶𝐶𝑂 𝐶𝐶𝑙2
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RATE LAWS

2A+B→3C

If − rA = kC
2
A
-rA = kA CA2 CB
› Second Order in A -rB = kB C CB
2
A
› Zero Order in B rC = kC C CB
2
A
› Overall Second Order

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FINDING RATE LAWS – THE ALGORITHM

How to find − rA = f ( X )

Step 1: Rate Law − rA = g (Ci )

Step 2: Stoichiometry (Ci ) = h( X )

Step 3: Combine to get− rA = f ( X )

Keep in mind that the rate laws are determined by

experimental observation (Ch.7).

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RELATIVE RATES OF REACTION

aA + bB → cC + dD

b c d
A+ B → C + D
a a a

rA rB rC rD
= = =
−a −b c d

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RELATIVE RATES OF REACTION

2A + B → 3C
mol
− rA = 10
dm3  s
rA rB rC
= =
− 2 −1 3
− rA mol
− rB = =5
2 dm3  s
−3 mol
rC = rA = 15
2 dm  s
3

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REVERSIBLE REACTION

http://www.youtube.com/watch?v=Lkt0NkEK8CA

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REVERSIBLE ELEMENTARY REACTION

kA
2A+B 3C
k-A

 C 3

− rA = k AC AC B − k − ACC = k A C A C B −
2 3 2 C

 k A k −A 

 2 CC3 
= k A C A C B − 
 K e 

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REVERSIBLE ELEMENTARY REACTION

kA
2A+B 3C Reaction is: Second Order in A
k-A First Order in B
Overall third Order

− rA  = 3
moles
CA =
moles
dm s dm3

 − rA  mole dm3 s dm6

k  =  2  = =
( )(
 C AC B  mole dm mole dm
3 3
)
2
mole2 s
Unit for k in 3rd order
reaction rate
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RATE LAWS - EXAMPLES

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 ARRHENIUS EQUATION

k is the specific reaction rate (constant) and is given by the Arrhenius Equation.
where:

−E RT
k = Ae

T → k → A

k T →0 k →0
A  1013
T

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ARRHENIUS EQUATION

k = Ae −E RT

where:
E = Activation energy (cal/mol)

R = Gas constant (cal/mol*K)
T = Temperature (K)
A = Frequency factor (same units as rate constant k)
(units of A, and k, depend on overall reaction order)

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DETERMINATION OF THE ACTIVATION ENERGY

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REACTION COORDINATE
The activation energy can be thought of as a barrier to the reaction. One way
to view the barrier to a reaction is through the reaction coordinates. These
coordinates denote the energy of the system as a function of progress along
the reaction path. For the reaction:
A + BC  A ::: B ::: C → AB + C

The reaction coordinate is



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WHY THERE IS AN ACTIVATION ENERGY
We see that for the reaction to occur, the reactants must overcome an energy
barrier or activation energy EA. The energy to overcome their barrier comes
from the transfer to the kinetic energy from molecular collisions and internal
energy (e.g. Vibrational Energy).

1. The molecules need energy to disort or stretch their bonds in order to

break them and thus form new bonds
2. As the reacting molecules come close together they must overcome both
stearic and electron repulsion forces in order to react.

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DISTRIBUTION OF VELOCITIES
We will use the Maxwell-Boltzmann Distribution of Molecular Velocities. For a
species af mass m, the Maxwell distribution of velocities (relative velocities) is

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DISTRIBUTION OF VELOCITIES
A plot of the distribution function, f(U,T), is shown as a function of U:

T1
T2 T2>T1

U
Maxwell-Boltzmann Distribution of velocities.
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DISTRIBUTION OF VELOCITIES
f(E,T)dE=fraction of molecules with energies between E+dE
One such distribution of energies is in the following figure:

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