CHAPTER 3

Rate Laws and Stoichiometry:

Part 1
Contents: Part 1

Rate laws and Order of Reaction

Reaction Rate Constant

Elementary Reaction

Reversible Reaction

Nonelementary Rate Laws

Reactor Sizing and Design

 Topic Outcomes

Week Topic Topic Outcomes

3 Rate laws and stoichiometry It is expected that students are able to:

Part 1: Part 1:
• Stoichiometric Table • Write rate law, define reaction order and
activation energy for elementary reactions
Part 2
• Expressing concentrations • Construct a stoichiometry table for batch
in terms other than and flow systems and express
conversions concentration as a function of conversion

Part 2
• Calculate the equilibrium conversion for gas
and liquid phase reactions

• Write the combined mole balance and rate

law in measures other than conversion
 Types of Reaction
Phases involved
• Homogenous reaction – one phase reaction
• Heterogeneous reaction – multiphase reaction

Equilibrium position
• Irreversible reaction
A  B  C  D (one direction)

• Reversible reaction

A  B  C  D (forward or backward)
Rate Law and Order of Reaction

We need to know the rate law of a reaction in order

to determine:

• The order of the reaction with respect to one

or more reactants.
• The overall order of the reaction.

Rate law or kinetic expression is the algebraic

equation that relate –rA to species concentration.

The relation is postulated from theory, yet

experiments needed for confirmation.
 Rate Law

 rA  k A C C
m
A
n
B

Order with respect to A = m

Order with respect to B = n
Reaction order, or overall order = m + n

Note: the stoichiometric coefficient in the balanced

equation for a chemical reaction is usually different
from the order.
Rate Law (Example)

Gas phase reaction

2NO  O2 
 2NO2

Kinetic rate law

 rNO  kNOC C O2
2
NO
 Order of Reaction
Zero-order First-order

-rA  k A : {k}  mol/dm3 .s -rA  k A C A :{k}  s -1

Second-order Third-order

-rA  k A C 2A :{k}  dm3 /mol.s -rA  k A C 3A :{k} (dm 3 /mol)2 .s 

Reaction Rate Constant, k
The limiting reactant always chosen as basis of calculation
k is not a function of concentration

 rA  k A T fnconcentration

k A(T)  Ae E/RT C αA .C B ......

Algebraic function
of concentration
T dependent, described
by Arhennius equation

Where A = Pre-exponential factor or frequency factor

E = Activation energy, J/mol or cal/mol
R = Gas constant= 8.314 J/mol.K = 1.987 cal/mol.K
T = Absolute temperature, K
Reaction Rate Constant (Cont.)

Reaction rate is found experimentally, data on

frequency factor (A), activation energy (E) and the
order of the reaction can be found in relevant
handbooks.
 Activation Energy

k A(T)  Ae E/RT
Slope = – E/R
ln kA

E  1
lnk A  lnA   
R T 1/T (K–)
 Elementary Reaction
A reaction has an elementary rate law if the
stoichiometry coefficients are the same as the
individual reaction order of each species.
For the reaction
A  2B  C  D

The rate law would be:  rA  kC A C B2

Expresses how actually molecules or ions react

with each other.
The equation in an elementary step represents
the reaction at the molecular level, not the
overall reaction.
Non-Elementary Rate Laws
The reaction rate dependence on the concentration
and temperature will become more complicated when
a reaction comprising several elementary steps is
considered (INCL. CATALYTIC and REVERSIBLE
reactions).

The stoichiometric coefficients are NOT the same

as the individual reaction order of each species.

A  2B  C  D  rA  kC 2A C B3
Non-Elementary (Example)

Free-radical mechanism
k1C H2 C 1/2
H2  Br2  2HBr  rHBr 
Br

k 2  C HBr /CBr 2

Vapor-phase decomposition

CH 3CHO  CH 4  CO  rCH3CHO  kC 3/2

CH3CHO
Reversible Reactions

For general reaction,

aA  bB  cC  dD

The net rate of formation A

rA,net  rA, forward  rA,reverse

 k A C aA C Bb k  A C Cc C Dd
 Reversible Reactions (Cont.)
At equilibrium, rA, net = 0

Thus,
kA
k A C A C  k A C C
a b
B
c
C
d
D
 K equilibriu m
k A

Concentration equilibrium constant

C Ce
c
C De
d
K equlibrium  Kc  a b
Thermodynamic
C AeC Be equilibrium relationship

example
Note: Kc = (mol/dm3)d + c – b – a
Reversible Reactions
All rate law for reversible reactions must satisfy
thermodynamic relationship relating the reacting species
concentrations at equilibrium,

At equilibrium, the rate of reaction is identically zero

for all species;
At equilibrium, rA, net ≡ 0
Reactor Sizing and Design

Reactor Differential Form Algebraic Form Integral Form

dX X dX
NA  rA V t  NA0 
Batch
dt 0  rA V

FA0 X out  X in 
V
 rA out
CSTR

dX X out dX
PFR FA0  rA V  FA0 
dV X in  rA

dX X out dX
PBR FA0  rA' W  FA0 
dW
X in - rA'
• It was shown that the rate law can be expressed as a
function of concentration.
ex:
 rA  kC 2A C B3
• Now we need to express concentration as a function of
conversion in order to carry out calculations similar to
those presented in Chapter 2 to size reactors.

• If the rate law depends on more than one species, we

must relate the concentrations of the different species to
each other with the aid of a stoichiometric table.

• Now we develop the stoichiometric relationships for

reacting species that give the change in the number of
moles of each species. (A,B,C,D).
Relatives Rates of Reaction
Consider of the reaction

aA  bB 
 cC  dD

b c d
A B
 C  D
a a a

moles of A reacted
XA 
moles of A fed
Relatives Rates of Reaction

 rA  rB rC rD
  
a b c d

Let’s see how we can relate Batch system

it to the reaction rate for
various types of reactors. Flow system
 Batch Reactor
t0
NA0
NB0
NC0
t  t'
ND0
NA Number of moles
NI0
NB of A,B,C,D,I
remaining/left in
NC
the reactor after
ND conversion X
NI
 Batch System
b c d moles of A reacted
A B
 C  D XA 
a a a moles of A fed

Number of moles A left after conversion:

NA NA0 1 X 
NA  NA0 - NA0 X  NA0 1 X  CA  
V V

Number of moles B left after conversion:

b
NB  NB0  NA0 X
a
 Batch System
Every mole of A that reacts, b/a moles of B must react
Therefore ;
moles of B reacted
moles of B reacted   moles of A reacted
moles of A reacted

b
NBreacted  NA0 X
a

Number of moles B left after conversion:

NB  NB0  NA0
b
X NB NB0  b/aNA0 X
CB  
a V V
NA0 Θ  b/aX 

V
Stoichiometry Table for Batch System
For every component in the reactor we can write after conversion X is achieved:

Species Initially (mol) Change (mol) Remaining (mol)

A NA0  NA0 X  NA  NA0  NA0 X

b b
B NB0  NA0 X  NB  NB0  NA0 X
a a
c c
C NC0 NA0 X  NC  NC0  NA0 X
a a
d d
D ND0 NA0 X  ND  ND0  NA0 X
a a

I (inerts) NI0 __ NI  NI0

__ d c b 
Totals NT0 NT  NT 0      1NA0 X
a a a 
Stoichiometry Table for Batch System

d c b 
   -1  δ
a a a 
δ - the total molar increase per mole A reacted

NT  NT0  δNA0 X
The total number of moles
 Batch Reactor
Now, if we know the number of moles of every component we
can calculate concentration as function of conversion.

NA NA0 1  X 
CA  
V V
N N  b/aNA0 X NA0 Θ  b/aX 
C B  B  B0 
V V V
N N Θ  c/aX 
C C  C  A0
V V
N N Θ  d/aX 
C D  D  A0
V V
 Batch System
Species Symbol Initial (mol) Change (mol) Remaining (mol)

A A NA0  NA0 X  NA  NA0 1 X 

b  b 
B B NB0  NA0ΘB  NA0 X  NB  NA0  ΘB  X 
a  a 
c  c 
C C NC0  NA0 ΘC NA0 X  NC  NA0  ΘC  X 
a  a 
d  d 
D D ND0  NA0 ΘD NA0 X  ND  NA0  ΘD  X 
a  a 

I (inerts) I NI  NA0 ΘI __ NI  NA0 ΘI

Totals T NT0 __ NT  NT0  δNA0 X

Ni0 C y
Θi   i0  i0
NA0 C A0 y A0
Constant volume-system, (V = Vo)

In a constant volume reactor (e.g. batch reactor,

liquid reactor):

NA NA0 1  X 
CA    C A0 1  X 
V V0

NB NA0 Θ  b/aX  C A0 Θ  b/aX 

CB    , etc.
V V0
 Flow System

Equations for flow reactors are the same with

number of moles N changed for flow rate F [mol/s].

Entering Leaving
F A0 FA
FB0 b c d FB
A B
 C  D
FC0 a a a FC
FD0 FD
FI0 FI
Stoichiometry Table for Flow System
Feed rate to Change within Effluent rate from
Species
reactor (mol/time) reactor (mol/time) reactor (mol/time)

A FA0  FA0 X  FA  FA0 1 X 

b  b 
B FB0  FA0 ΘB  FA0 X  FB  FA0  ΘB  X 
a 
a 
c  c 
C FC0  FA0ΘC FA0 X  FC  FA0  ΘC  X 
a  a 
d  d 
D FD0  FA0 ΘD FA0 X  FD  FA0  ΘD  X 
a  a 

I (inerts) FI  FA0ΘI __ FI  FA0ΘI

Totals FT0 __ FT  FT0  δFA0 X

 Flow System
Fi0 C i0 0 C i0 y i0 d c b 
Θi        -1  δ
FA0 C A0 0 C A0 y A0 a a a 
For a flow system a concentration at any point can be
obtained from molar flow rate F and volumetric flow

FAmoles/time
CA  
 liter/time

For reaction in liquids, the volume change is

negligible (if no phase change occurred): v   0

FA  b 
CA   C A0 1 X  C B  C A0  Θ  X 
  a 