Chapter 3 Rates Law and Stoichiometry

CHAPTER 3: Rate Laws and Stoichiometry: Part 1
Rate laws and Order of Reaction

Reaction Rate Constant
Elementary Reaction
Reversible Reaction
Nonelementary Rate Laws
Reactor Sizing and Design
1
Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
Topic Outcomes
Week
Topic
Topic Outcomes
Rate laws and stoichiometry
It is expected that students are able to:
Part 1:
Stoichiometric Table
Part 1:
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
2
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)
3
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.
4
Rate Law
rA = k A C C
(Power Law Model)
Order with respect to A =

Order with respect to B =
Reaction order, or overall order, n = +
The stoichiometric coefficient in the balanced equation for a

chemical reaction is usually different from the order.
The units of k depends on the reaction order. You can find out the
overall order of reaction from units of k
5
Rate Law (Example)

Gas phase reaction
2NO + O 2
2NO2
Kinetic rate law
rNO = k NOC C O2
2
NO
6
Order of Reaction
Zero-order
- rA = k A : {k}= mol/dm3 .s
Second-order
- rA = k A C 2A :{k}= dm3 /mol.s
First-order
- rA = k A C A :{k}= s -1
Third-order
2
- rA = k A C 3A :{k}=(dm 3 /mol)
.s
7
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 A .CB ......
Algebraic function
of concentration
T dependent, described
by Arrhenius 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
8
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.
Units of the reaction rate constant

1n
(
Concetration )
[k ] =
time
9
Activation Energy
k A(T)= Ae E/RT
ln kA
E 1
lnk A = lnA
RT
Slope = E/R
1/T (K)
10
Temperature dependence of rate constant Arrhenius Law

A majority of reaction rate constants can be expressed by an empirical relationship
that was developed by Swedish scientist, Svante Arrhenius.
k = A exp(-E/RT)
A = frequency factor or pre-exponential factor

E = Activation Energy
R = Universal gas Constant
Vignette on Svante Arrhenius

Arrhenius studied reaction rates as a function of temperature, and in
1889 he introduced the concept of activation energy as the critical
energy that chemicals need to react. He also pointed out the
existence of a "greenhouse effect" in which small changes in the
concentration of carbon dioxide in the atmosphere could
considerably alter the average temperature of a planet.
For his PhD thesis in 1884 he presented his electrolytic theory of
dissociation , he received the lowest possible passing grade (fourth
class rank). Later this very work would earn him the Nobel Prize in
Chemistry in 1903.
11
Interpretation of parameters in the Arrhenius

equation
k = A exp(-E/RT)
For simple reaction in which two molecules
collide and react, the pre-exponential term in the
Arrhenius equation can be thought of as the
frequency of collision of the molecules.
Also, the exponential term can be thought of as
the fraction of the reactants that posses energy
greater than E.
12
Activation Energy - Ea
Ea
A+B
HR
Reaction Coordinate
Activation Energy: A simple description of Ea would be the energy barrier that reactants
must overcome for a reaction to proceed.
13
Implications of Arrhenius Law

k = A exp(-E/RT)
ln( k) = ln A - (E/R) x 1/T
Rxn1: High Ea
k with higher E is more sensitive

to temperature than those with
low E
Rxn 2: Low Ea
1/T
14
Kinetics of Many Processes in Nature follow

Arrhenius Relationship
Some Examples
Cricket chirping
Ant walking
Tumour growth
Diffusion in solids [D = Do exp (-ED/RT)]
References:
M. I. Masel, Chemical Kinetics and Catalysis
Octave Levenspiel, Chemical Reaction Engineering
Rate of Cricket Chirping
15
The Case of Ant walking:

Can we really represent it with Arrhenius Law?
16
M. I. Masel, Chemical Kinetics and Catalysis
The Case of Ant walking

8
6
5
Raw data
4
3
2
1
0
0
10
15
20
25
30
35
40
45
Temperature (C)
2.5
Processed data
ln (wlaking speed)
Running Speed (cm/s)
2.0
1.5
1.0
0.5
0.0
-0.5
-1.0
3.15
3.20
3.25
3.30
3.35
3.40
3.45
3.50
3.55
3.60
-1
1000/T (K )
17
Elementary Reaction
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 CB2
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.
18
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 CB3
19
Non-Elementary (Example)
Free-radical mechanism
H2 + Br2 2HBr
rHBr =
k 1CH2 C1/2
Br
k 2 + CHBr /CBr2
Vapor-phase decomposition
CH3CHO CH4 + CO
rCH3CHO = kC 3/2
CH3CHO
20
Reversible Reactions
For general reaction,
aA + bB cC + dD
The net rate of formation A
rA,net = rA,forward + rB,reverse

k A C aA CBb
k A C Cc CDd
21
Reversible Reactions (Cont.)

At equilibrium, rA, net = 0
Thus,
k A C C = k A C C
a
A
b
B
c
C
kA
= Kequilibrium
k A
d
D
Concentration equilibrium constant
K equlibrium
e
d
C Ce
CDe
= Kc = a b
C Ae CBe
Note: Kc = (mol/dm3)d + c b c
Thermodynamic
equilibrium relationship
22
CHAPTER 3
Rate Laws and Stoichiometry:
Part 2
23
Reactor Sizing and Design

Reactor
Batch
Differential Form
NA
dX
= rA V
dt
PBR
dX
FA0
= rA
dV
dX
F
= r
dW
A0
Integral Form
dX
rA V
t = NA0
V = FA0
X out
V=
CSTR
PFR
Algebraic Form
FA0 (X out X in )
( rA )out
X in
'
W = FA0
X out
X in
dX
rA
dX
- rA'
24
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
25
Relatives Rates of Reaction

rA rB rC rD
=
= =
a
b
c d
Lets see how we can relate

it to the reaction rate for
various types of reactors.
Batch system
Flow system
26
Batch Reactor
t=0
N A0
NB0
NC0
ND0
NI0
t = t'
NA
NB
NC
ND
NI
27
Batch System
b
c
d
A+ B
C + D
a
a
a
XA =
moles of A reacted
moles of A fed
Number of moles A left after conversion:

N A = N A0 - N A0 X = N A0 (1 X )
CA =
N A N A0 (1 X )
=
V
V
Number of moles B left after conversion:

moles of B reacted moles of B reacted b
=
=
moles of A reacted
N A0 X
a
NB = NB0
b
N A0 X
a
NB NB0 (b/a )N A0 X
=
V
V
N A0 ( (b/a )X )
=
V
CB =
i =
Ni0
C
y
= i0 = i0
NA0 C A0 y A0
28
Stoichiometry Table for Batch System

For every component in the reactor we can write after conversion X is achieved:
Species
Initially (mol)
NA0
NB0
I (inerts)
Totals
Change (mol)
(NA0 X )
Remaining (mol)
NA = NA0 NA0 X
b
(NA0 X )
a
b
NB = NB0 NA0 X
a
NC0
c
(NA0 X )
a
c
NC = NC0 + NA0 X
a
ND0
d
(NA0 X )
a
d
ND = ND0 + NA0 X
a
__
N =N
NT0
__
I0
I0
d c b
NT = NT 0 + + 1NA0 X
a a a
29
Stoichiometry Table for Batch System

d c b
+ - 1 =
a a a
- the total molar increase per mole A reacted
NT = NT0 + NA0 X
30
Batch System
Species
Symbol
Initial (mol)
Change (mol)
NA0
(NA0 X )
NB0 = NA0B
NC0 = NA0C
b
(NA0 X )
a
c
(NA0 X )
a
d
(NA0 X )
a
ND0 = NA0D
I (inerts)
N =N
Totals
NT0
i =
Ni0
C
y
= i0 = i0
NA0 C A0 y A0
A0
__
I
Remaining (mol)
NA = NA0 (1 X )
NB = NA0 B X
a
NC = NA0 C + X
a
ND = NA0 D + X
a
N =N
I
__
A0
NT = NT0 + NA0 X
31
Batch Reactor
Now, if we know the number of moles of every component we
can calculate concentration as function of conversion.
NA
V
N
CB = B
V
N
CB = C
V
N
CD = D
V
CA =
NA0 (1 X )
V
N (b/a )NA0 X NA0 ( (b/a )X )
= B0
=
V
V
N ( + (c/a )X )
= A0
V
N ( + (d/a )X )
= A0
V
=
i =
Ni0
C
y
= i0 = i0
NA0 C A0 y A0
However, generally V can be a function of X as well
32
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 ( (b/a )X )
CB =
=
= C A0 ( (b/a )X ), etc.
V
V0
33
Flow System
Equations for flow reactors are the same with
number of moles N changed for flow rate F [mol/s].
Entering
FA0
FB0
FC0
FD0
FI0
Leaving
b
c
d
A+ B
C + D
a
a
a
FA
FB
FC
FD
FI
34
Stoichiometry Table for Flow System

Species
Feed rate to
Change within
reactor (mol/time) reactor (mol/time)
I (inerts)
Totals
(FA0 X )
FA0
FB0 = FA0B
b
(FA0 X )
a
FC0 = FA0C
c
(FA0 X )
a
FD0 = FA0D
d
(FA0 X )
a
F =F
__
A0
FT0
Effluent rate from

reactor (mol/time)
FA = FA0 (1 X )
b
FB = FA0 B X
a
FC = FA0 C + X
a
FD = FA0 D + X
a
F =F
I
__
A0
FT = FT0 + FA0 X
35
Flow System
Fi0
Ci0 0
Ci0
y i0
i =
=
=
=
FA0 C A0 0 C A0 y A0
d c b
+ - 1 =
a a a
For a flow system a concentration at any point can be

obtained from molar flow rate F and volumetric flow
FA
moles/time
CA =
=
liter/time
For reaction in liquids, the volume change is
negligible (if no phase change occurred):
CA =
FA
FA0 (1 X )
FA0 (1 X )
= C A0 (1 X )
CB = C A0 X
a
36
Reactions Involving Volume Change

Previous: V or o = constant
Most batch, liquid-phase & some gas-phase systems
This section: V or o = vary
Other systems
N2 + 3H 2NH3
4 moles
2 moles
In a gas phase reaction a molar flow rate might

change as the reaction progresses.
37
Batch Reactor with Variable Volume

Goal: Predict volume as a function of X
As such it would be a rare case (e.g. internal combustion

engine), but a good model case:
PV = ZR T T
Z=Compressibility factor
If we DIVIDE the GAS EQUATION at any moment in time (t)

by the one at moment zero (t0):
Z0 Z
P T Z N
V = V 0 T
0 P T0 Z 0 NT0
NT
N
= 1+ A0 .X = 1+ X
NT0
NT0
P0 T
V = V0 (1+ X )
P T0
Note: function V=g(X)
= y A0
d c b
= + 1
a a a
38
Flow Reactor with Variable Flow Rate

Goal: Predict concentration as a function of X
Using the gas equation we can derive the total concentration as:
P
ZRT
F
P0
= T0 =
0 Z0RT0
Total concentration: C T =
At the entrance: C T0
FT
(3.39 )
(3.40 )
Take the ratio of (3.40) to (3.39), assume negligible change in Z:

Total volume rate:
Cj =
Fj
v
Fj
= v0
FT P0 Z T
v0
FT0 P Z 0 T0
FT P0 T
FT0 P T0
= C T0
For gas phase reaction
Fj P Z 0 T0
FT P0 Z T
Z Z0
=1
For membrane reactor

and multiple reactions
39

In a gas phase reaction a molar flow rate might
change as the reaction progresses
= v0
FT P0 T
FT0 P T0
FT = FT0 + FA0 ..X
P0 T
= v0 (1+ y A0 X )
P T0
= v0 (1+ X )
P0 T
P T0
FA0 ( j + v j X )
Cj =
P T
v0 (1+ X ) 0
P T0
Stoichiometric
coefficient
Gas-phase C as
a function of X
40
41
Summary: Expressing C as a function of X
42
Expressing C in Terms Other Than X

Membrane reactors and gas-multiple reaction
commonly used molar flow rate rather than conversion
C j = C T0
F j P T0
FT P0 T
For j=A, B, C, D, I
With,
FT = FA + FB + FC + FD + FI
43
Reactions with Phase Change

A(g)+ B(g) C(g,l)
Gas-phase condensation
Before condensation, with P=P0 , T=T0 ,=1
= (1
+ X)= (1
0.5X)
0
0
CC =
C A0 X
1 0.5X
Mole fraction of C at which
condensation begin
After condensation, (X>XC)
(1
X)
0
1 y C,e
FC = y CFT
y C,e
PC
=
PT
CC =
Vapor pressure C at T
yC
C A0
y A0
44
Summary: Expressing C as a function of X
45
Examples and Tutorials
46
Example 1 (Specific Reaction Rate)

In each of the following reactions, determine the specific reaction
rate constant for each of the other species in the reaction.
Assume that kA in each case has a value of 25 with the appropriate
combination of units of mol, dm3, g cat, and s.
a. For the reaction
2A+B C
The rate law is rA = kACA2CB.
b. For the reaction
1/2 A + 3/2 B C
The rate law is rA = kACACB.
47
Solution 1
a. 2 A + B C
rA rB rC rD
=
= =
a
b
c d
rB =
b
( rA ) = 1 k A C 2A CB
a
2
rC =
c
( rA ) = 1 k A C 2A CB
a
2
rB = k BC 2A CB
rC = k CC 2A CB
dm 1

k B = 12.5
mol
sec
dm 1

k C = 12.5
mol
sec
48
Solution 1 (Cont.)
b. 1/2 A + 3/2 B C
b
rB = ( rA ) = 3(k A C A CB )
a
c
rC = ( rA ) = 2(k A C A CB )
a
rB = k BC A CB
rC = k CC A CB
dm3 1
k B = 75
mol sec
dm3 1
k C = 50
mol sec
49
Example 2 (Stoichiometric Table)

Set up a stoichiometric table for each of the following reactions and
express the concentration of each species in the reaction as a function
of conversion evaluating all constant (e.g, , )
a.
The liquid-phase reaction
H2C CH2
H2O
H2SO4
CH2 OH
CH2 OH
The initial concentration of ethylene oxide and water are 1 Ib mol/ft3 and
3.47 Ib-mol/ft3 (62.41 Ib-mol / 18), respectively.
b.
The isothermal, isobaric gas-phase pyrolysis

C2H6 C2H4 + H2
Pure ethane enters the FLOW REACTOR at 6 atm and 1100 K. How would
your equation for the concentration change if the reaction to be carried out
in a constant-volume BATCH REACTOR.
50
Solution 2
a. Liquid-phase reaction
O
H2C CH2
H2O
H2SO4
cat
A + B
C
CH2 OH
CH2 OH
Liquid phase reaction stoichiometric table, batch = flow reactor

NA/V = NA/Vo = CA
Species
Symbol
Initial
Change
Remaining
H2C CH2
C A0 = 1Ibmol/ft 3
C A0 X
C A = 1(1 X )
H2O
CB0 = 3.47Ibmol/ft 3
C A0 X
CB = (3.47 X )
+ C A0 X
CC = X
CH2 OH
CH2 OH
51
Solution 2 (Cont.)
b. Isothermal, isobaric, gas-phase pyrolysis
C2H6 C2H4 + H2
A
B + C
Initial
Change
Species
Symbol
C2H6
FA0
FA0 X
FA = FA0 (1 X )
C2H4
+ FA0 X
FB = FA0 X
H2
+ FA0 X
FC = FA0 X
FT = FA0
Remaining
FT = FA0 (1+ X )
52
Solution 2 (Cont.)
Gas phase, constant T, no P drop
= o (1+ X )
= y AO = 1(1+ 1 1) = 1
= o (1+ X )
CA =
CB =
FA
FB
FA0 (1 X )
(1 X )
= C A0
(1+ X )
O (1+ X )
= CC =
FC
C A0 = y A0C T0 = y A0
FA0 X
X
= C A0
O (1+ X )
1+ X
P0
(1)(6atm)
kmol
mol
=
=
0.067
=
0.067
RT0 0.082m3 .atm
dm3
m3
1100K
kmol.K
53
Example 3 (Reversible Reaction)

For each of the following reactions and rate laws at low
temperatures, suggest a rate law at high temperatures. The
reactions are highly exothermic and therefore reversible at high
temperature .
a. The reaction
AB
Is irreversible at low temperatures, and the rate law is
-rA = kCA
b. The reaction
A + B 2D
Is irreversible at low temperatures, and the rate law is
-rA = kCA1/2CB
54
.
Solution 2 (Cont.)
a. At high temperature
A B
At equilibrium, we know K = CBe
C
from thermodynamics:
C Ae
CB
rA = k1 C A
KC
rA = k1C A k 2CB
k2
k
rA = k1 C A CB K C = 1
k1
k2
55
Solution 2 (Cont.)
a. At high temperature
A + B 2D
Low T: -rA = kCA1/2CB
High T reversible
rA = k 1C1/2
CB k 2CD
A
1/2
k2
k1
rA = k 1 C A CB CD K C =
k1
k2
1/2
CD
rA = k1 C A CB
KC
56
Example 3.6 (V Change)

For reaction below calculate
a. Equilibrium conversion in a constant volume batch
reactor;
b. Equilibrium conversion in a flow reactor;
c. Assuming the reaction is elementary, express the rate of
the reaction as a function of X;
Assume the feed is pure N2O4 at 340K and 202.6 kPa.
Concentration equilibrium constant: KC = 0.1mol/l; kA = 0.5 min-1
N2O 4 2NO2
57
Solution 3.6
(a) Batch reactor
Species
Symbol
N2O4
NO2
Initial
Change
Remaining
NA0
NA0 X
NA = NA0 (1 X )
+ 2(NA0 X )
NB = 2NA0 X
NT0 = NA0
NT = NT0 + NAO X
Equilibrium conversion:
2
CBe
4C 2A0 X 2e
4C A0 X 2e
KC =
=
=
C Ae C A0 (1 X e ) 1 X e
C A0 =
y A0P0
= 0.071mol/dm3
RT0
Xe =
K C (1 X e )
4C A0
Trial & error
Xe = 0.44
58
Solution 3.6 (Cont.)

(b) Flow reactor
FA
FA0 (1 X ) C A0 (1 X )
CA =
=
=
0 (1+ X )
1+ X
CB =
2C A0 X
1+ X
1+
2
CBe
4C 2A0 X 2e
KC =
=
C Ae C A0 (1 X e )(1+ X e )
4C A0 X 2e
=
(1 X e )(1+ X e )
C A0 =
Xe =
y A0P0
= 0.071mol/dm3
RT0
K C (1 X e )(1+ X e )
4C A0
Trial & error

Xe = 0.51
59
Solution 3.6 (Cont.)

(c) Rate laws
CB2
rA = k A C A
K
C
4C 2A0 X 2
Constant volume: rA = k A C A0 (1 X )
K
C
Flow:
C A0 (1 X )
4C 2A0 X 2
rA = k A
2
+
1
X
(
)
+
K
1
X
C
60

Chapter 3 Rates Law and Stoichiometry

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Chapter 3 Rates Law and Stoichiometry

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CHAPTER 3: Rate Laws and Stoichiometry: Part 1

Rate laws and Order of Reaction

Rate laws and stoichiometry

It is expected that students are able to:

Rate Law and Order of Reaction

(Power Law Model)

Order with respect to A =

The stoichiometric coefficient in the balanced equation for a

Rate Law (Example)

Kinetic rate law

Reaction Rate Constant, k

Reaction Rate Constant (Cont.)

Units of the reaction rate constant

Temperature dependence of rate constant Arrhenius Law

A = frequency factor or pre-exponential factor

Vignette on Svante Arrhenius

Interpretation of parameters in the Arrhenius

Implications of Arrhenius Law

ln( k) = ln A - (E/R) x 1/T

k with higher E is more sensitive

Kinetics of Many Processes in Nature follow

Rate of Cricket Chirping

The Case of Ant walking:

M. I. Masel, Chemical Kinetics and Catalysis

The Case of Ant walking

Running Speed (cm/s)

Non-Elementary Rate Laws

The net rate of formation A

rA,net = rA,forward + rB,reverse

Reversible Reactions (Cont.)

Concentration equilibrium constant

Reactor Sizing and Design

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Relatives Rates of Reaction

Relatives Rates of Reaction

Lets see how we can relate

Number of moles A left after conversion:

Number of moles B left after conversion:

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Stoichiometry Table for Batch System

Stoichiometry Table for Batch System

However, generally V can be a function of X as well

Constant volume-system, (V = Vo)

Stoichiometry Table for Flow System

Effluent rate from

For a flow system a concentration at any point can be

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Reactions Involving Volume Change

In a gas phase reaction a molar flow rate might

Batch Reactor with Variable Volume

As such it would be a rare case (e.g. internal combustion

If we DIVIDE the GAS EQUATION at any moment in time (t)

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Flow Reactor with Variable Flow Rate

Take the ratio of (3.40) to (3.39), assume negligible change in Z:

For gas phase reaction

For membrane reactor

Flow Reactor with Variable Flow Rate

FT = FT0 + FA0 ..X

Flow Reactor with Variable Flow Rate

Summary: Expressing C as a function of X

Expressing C in Terms Other Than X

Reactions with Phase Change

Before condensation, with P=P0 , T=T0 ,=1