Lecture 3

Chemical Reaction Engineering (CRE) is the field

that studies the rates and mechanisms of chemical
reactions and the design of the reactors in which
they take place.

Reactor General Mole Balance Equations (GMBE)

(Lecture 1 Review)
The GMBE applied to the four major reactor types
(for the general reaction AB):
Reactor

Batch

Differential

PBR

Integral
NA

dN A
t
rV
N A0 A

dN A
rAV
dt

CSTR
PFR

Algebraic

dFA
rA
dV

dFA
rA
dW

FA 0 FA
rA

FA

dFA
V
drA
FA 0
W

FA

FA 0

dFA
rA

NA
t
FA

FA

(Lecture 2 Review)

a A bB
c C d D
Choose limiting reactant A as basis of calculation
b
c
d
A B
C D
a
a
a
moles A reacted
X
moles A fed

Reactor Mole Balances in terms of

conversion
Reactor

Batch

Differential

PBR

Integral
X

dX
rA V
0

dX
FA 0
rA
dV

dX
FA 0
rA
dW

t N A0

dX
NA0
r AV
dt

CSTR

PFR

Algebraic

FA 0 X
rA

t
X

V FA 0
0

dX
rA

W FA 0
0

X
dX
rA

Levenspiel Plots

Todays lecture
Rate Laws

Reaction Orders

Arrhenius Equation

Activation Energy

Effect of Temperature

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

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
dm3 s

Lecture 3
Rate Laws
For many reactions, the reaction rate can be written as
the product of a reaction rate constant, kA and a
function of the concentration of the various species
involved in the reaction.

-rA =kA(T) * fn(CA,CB....)

Lecture 3
Rate Laws - Power Law Model

rA kC C
order in A
order in B

Overall Rection Order

2A+B3C

If rA kC2A
Second Order in A
Zero Order in B
Overall Second Order

rA kA CA2 CB

rB kB CA2 CB
rC kC CA2 CB

Lecture 3
Rate Laws - Power Law Model

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 A C2A CB

2nd order in A,
1st order in B,
overall 3rd order

Lecture 3
Rate Laws - Power Law Model

2CO Cl2 COCl2

Many reaction orders many involve values other than
integer values for a reaction order.
e.g.

rCO kcoCCO CCl3 /22

1st order in CO,

3/2 order in Cl2,
Overall 5/2 order

Lecture 3
Rate Laws - Power Law Model

2 N 2O 2 N 2 O2
Many reactions can have complex rate expressions
that cannot be separated into temperature-dependent
and concentration dependent portions.
e.g.

rN 2O

k N 2O C N 2O
1 kCO2

For this reaction, the overall reaction order cannot be

stated. Here, we can only refer to the reaction order
under certain conditions.

Reversible Reactions

A 2B
3C
Elementary

rA, forward k AC AC B2
rA, forward k AC AC B2
rA,reverse k ACC3
rA,net rA, forward rA,reverse
rA,net k AC AC k AC
2
B

3
C

rA,net k AC AC k AC
2
B

3
C

Reversible Reactions

A 2B
3C
Elementary

rA k A C A C 2B k A C3C
3

C
2
C
k A C A C B

k A k A

C
2
C
k A C A C B

Ke

Reversible Reaction
A+2B

kA
k-A

3C

rA k AC AC B2 k ACC3
3

C
2
C
k A C AC B

Ke

When: concentration of Reactants >>Products

Reaction is: First Order in A
Second Order in B
Overall third Order
When: concentration of Reactants <<Products
Reaction is: Third Order in C
Overall third Order

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

k Ae E RT
T k A
T 0 k 0

A 1013
T

Arrhenius Equation
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)

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

Why is there 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.

Distribution of Velocities: Maxwell-

Boltzmann Distribution

For a species af mass m, the Maxwell distribution

of velocities (relative velocities) is
32

m mU 2 2 k BT 2
e
f U , T dU 4
U dU
2k BT

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.

f(E,T) dE=fraction of molecules with energies between E+dE