ERT 316: REACTION ENGINEERING

CHAPTER 3
RATE LAWS &
STOICHIOMETRY

1 Lecturer: Miss Anis Atikah Ahmad

Email: anisatikah@unimap.edu.my
Tel: +604 976 3245
OUTLINE
PART 1: Rate Laws
Relative Rates of Reaction
Reaction Order & Rate Law
Reaction Rate Constant, k

PART 2: Stoichiometry
Batch System Stoichiometric Table
Flow System Stoichiometric Table
Calculation for Concentration in terms of
Conversion
1. RELATIVE RATES OF REACTION

aA bB cC dD
rA rB rC rD
Reaction
a b c d Stoichiometry

EXAMPLE

2NO O2 2NO2
If NO2 formed at 4 mol/m3/s
(r NO = 4 mol/m3/s), what is
rNO rO2 rNO2 2
the rate of formation of NO?

2 1 2
1. RELATIVE RATES OF REACTION
2NO O2 2NO2
If NO2 formed at 4 mol/m3/s (r NO = 4 mol/m3/s),
2
what is the rate of formation of NO?

rNO rO2 rNO2 rNO rNO2

2 1 2 2 2
3
rNO 4mol / m / s

2 2
4mol / m3 / s
rNO 2 4mol / m3 / s
2
1. RELATIVE RATES OF REACTION

EXERCISE

The Reaction:

2 A 3B 5C
is carried out in a reactor. If at a particular point,
the rate of disappearance of A is 10 mol/dm3/s,
what are the rates of B and C?
 1. RELATIVE RATES OF REACTION

2 A 3B 5C
The relative rates are

rA rB rC

2 3 5
Given, the rate of disappearance of A, -rA, is 10mol/dm3/s
Thus, solving the rates of B & C;
r A= -10 mol/dm3/s

rA rB rA rC

2 3 2 5
3
rB
2

10mol / dm3 / s rC
5
2

10mol / dm3 / s
15mol / dm 3 / s 25mol / dm 3 / s
 Rate law is a kinetic
expression that gives the
2. REACTION ORDER & RATE LAW relationship between
reaction rate, -rA, and
concentration.

The reaction rate (rate of disappearance) depends

on temperature and composition.

It can be written as the product of reaction rate

constant, kA and a function of concentrations
(activities) of the reactants involved in the
reaction:

rA k A T fnCA , CB ...
 Rate law is a kinetic
expression that gives the
2. REACTION ORDER & RATE LAW relationship between
reaction rate, -rA, and
concentration.

For reaction in which the stoichiometric coefficient is 1

for ALL species:

1NaOH 1HCl 1NaCl 1H 2O

we shall delete the subscript on the specific reaction

rate, (e.g.; A in kA) to let

k k NaOH k HCl k NaCl k H 2O

2.1 POWER LAW MODELS & ELEMENTARY RATE LAWS

Power Law Model:

rA kCA CB
The rxn is order wrt reactant A
AND
The rxn is order wrt reactant B

The overall order of the reaction, n;

n
2.1 POWER LAW MODELS & ELEMENTARY RATE LAWS
The unit of the specific reaction, k, will vary with the
order of reaction.
A Products

k
Concentration
1 n

Time
Zero order (n=0) rA k A k mol / dm3 s
First order (n=1) rA k ACA k s 1
Second order (n=2) rA k AC A2 k dm3 / mol s
rA k AC k dm / mol s 1
3 2
Third order (n=3) A
3
2.1 POWER LAW MODELS & ELEMENTARY RATE LAWS
Elementary reaction: a chemical reaction in which one or
more of the chemical species react directly to form products
in a single reaction step and with a single transition
state.
A Products Unimolecular reaction

A B Products Bimolecular reaction

Elementary rate law:

The rxn is said to follow the elementary rate law if the
stoichiometic coefficients are IDENTICAL to the reaction
order of each species.
Non-
2NO O2 2NO2 elementary
rxn

rNO k NOC CO22

NO
But follows the
elementary rate law!
EXAMPLES OF REACTION RATE LAWS
EXAMPLES OF REACTION RATE LAWS
EXAMPLES OF REACTION RATE LAWS
2.2 NON-ELEMENTARY RATE LAWS
Non-elementary rate laws: reactions that do not
follow simple rate laws (power rate laws).
Example 1: Homogeneous Rxn

Gas phase
synthesis of
CO Cl2 COCl2 phosgene

The kinetic rate law is:

rCO kCCOC 32
Cl 2

Rxn order: first order wrt to CO, three-halves

order wrt Cl2, five-halves order overall.
2.2 NON-ELEMENTARY RATE LAWS
Gas-solid catalyzed
Example 2: Heterogeneous Rxn rxn:
Hydrodemethylation
C6 H 5CH 3 H 2 C6 H 6 CH 4 of toluene (T)
cat
T H2 B M
cat
The rate of disappearance of toluene per mass of
catalyst is:
In terms of partial
kPH 2 PT pressure rather than
r '
concentrations
1 K B PB KT PT
T

where KB & KT is the adsorption constants.

2.3 REVERSIBLE REACTIONS

aA bB cC dD
For reversible rxn, all rate laws must reduce to the
thermodynamic relationship relating the reacting
species concentrations at equilibrium.

Thermodynamic
c d Equilibrium
C C
KC Ce
a
De
b
Relationship

C C Ae Be
2.3 REVERSIBLE REACTIONS
EXAMPLE: combination rxn of 2 mol of benzene to form 1 mol
H2 and 1 mol diphenyl.
kB
2C6 H 6 C12 H10 H 2
k-B
kB
symbolically; 2B k D H 2
-B

The rate of disappearance of benzene;

rB, forward kBC 2
B OR rB, forward k BC 2
B

The reverse rxn btween diphenyl & hydrogen;

k-B
C12 H10 H 2 2 C6 H 6
The rate of formation of benzene (in reverse direction);
rB ,reverse k B CDCH 2
2.3 REVERSIBLE REACTIONS

The net rate of formation of benzene is;

rB rB ,net rB , forward rB ,reverse

kBC k BCDCH 2
2
B

Multiplying both sides by -1, we obtain the rate law of

disappearance of benzene, -rB

rB kBC kBCDCH 2
2
B

2 k B
k B CB CDCH 2
kB
2.3 REVERSIBLE REACTIONS

2 k B
rB k B CB CDCH 2
kB
Replacing the ratio of the reverse & forward rate law
constant by equilibrium constants;

2 CD CH 2
rB k B CB
KC
where
kB Concentration
K C equilibrium constant
kB
 3. THE REACTION RATE CONSTANT

k A T Ae E / RT Arrhenius
equation

A= preexponential 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

A -no of collision

e E / RT -probability that
the collision will
result in a reaction
3. THE REACTION RATE CONSTANT

k A T Ae E / RT

Activation energy is a measure of the minimum

energy that the reacting molecules must have
in order for the reaction to occur (energy required to
reach transition state).
Transition state k - no of collision that
result in a rxn

Energy barier A -total no of collision

probability that
E / RT
e - the collision will
result in a rxn
Reactants Products
 3. THE REACTION RATE CONSTANT

k A T Ae E / RT

Taking a natural logarithm;

E1
ln k A ln A
R T The larger the
activation energy,
the more
E , k , -r = temperature
sensitive k and thus
the reaction rate.
4. BATCH SYSTEMS STOICHIOMETRIC TABLE

Purpose of developing stoichiometric table:

To determine the no of moles of each species

remaining at a conversion of X.
 4. BATCH SYSTEMS STOICHIOMETRIC TABLE
refers to moles of
Components of stoichiometric table: species reacted or
formed

Species Initially Change Remaining

(mol) (mol) (mol)
A
B
C
D
I
Totals
4. BATCH SYSTEMS STOICHIOMETRIC TABLE

aA + bB cC + dD

Recall from Chapter 2:

X
N A0 N A
N A0
moles of A reacted

N A N A0 N A0 X
Factorizing; moles of A remaining

N A N A0 1 X
in the reactor at a
conversion
of X
4. BATCH SYSTEMS STOICHIOMETRIC TABLE

Moles B Moles B reacted

reacted, NB Moles A reacted
Moles A reacted

N A0 X
b
a

N A0 X
Moles C c
formed, NC
a

N A0 X
Moles D d
formed, ND
a
4. BATCH SYSTEMS STOICHIOMETRIC TABLE

moles B remaining N
b
B 0 N A0 X
in the system, NB a
moles of B moles of B
initially in the reacted
system

c
NC N C 0 N A0 X
a moles of C
formed
d
ND N D 0 N A0 X moles of D
a formed
4. BATCH SYSTEMS STOICHIOMETRIC TABLE
Species Initially Change Remaining (mol)
(mol) (mol)
A
N A0 N A0 X N A N A0 N A0 X

B
N A0 X
b b
N B0 N B N B 0 N A0 X
a a
C NC 0
c
N A0 X c
N C N C 0 N A0 X
a a
D d
N A0 X d
N D0 N D N D 0 N A0 X
a a
I NI0 - NI NI 0
Totals d c b
NT 0 N T N T 0 1 N A 0 X
a a a

4. BATCH SYSTEMS STOICHIOMETRIC TABLE

Total no of moles per mole of A reacted can be

calculated as:
d c b
N T N T 0 1 N A 0 X
a a a
N T 0 N A0 X

Change in the total number of moles per

where mole of A reacted
d c b
1
a a a
4. BATCH SYSTEMS STOICHIOMETRIC TABLE

rA kCA rA kCA
2
rA k AC 3
A

Can we express concentration of each species??

Species Initially Change Remaining Concentration

A
B
C
D
I
Totals
4. BATCH SYSTEMS STOICHIOMETRIC TABLE
Concentration of each species in terms of
conversion can be expressed as:
Recall from
N A N A0 1 X stoichiometric
CA table
V V
Remaining (mol)

N B N B 0 b / a N A0 X
CB A N A N A0 N A0 X
V V b
B N B N B 0 N A0 X
N C N C 0 c / a N A0 X a
CC c
N C N C 0 N A0 X
V V C
a

N D N D 0 d / a N A0 X D
d
N D N D 0 N A0 X
CD a
V V
 4. BATCH SYSTEMS STOICHIOMETRIC TABLE
N B 0 b / a N A0 X
CB
V

N A0 N B 0 / N A0 b / a X N A0 B b / a X

V V

N C 0 c / a N A0 X
CC
V
N A0 N C 0 / N A0 c / a X N A0 C c / a X

V V
 4. BATCH SYSTEMS STOICHIOMETRIC TABLE
N D 0 d / a N A0 X
CD
V

N A0 N D 0 / N A0 d / a X

V

N A0 D d / a X

V

N i 0 Ci 0 yi 0
i
N A0 C A0 y A0
 4. BATCH SYSTEMS STOICHIOMETRIC TABLE
Species Initially Change Remaining Concentration
A N A0 1 X
N A0 N A0 X N A N A0 N A0 X CA
V
B N B0
b
N A0 X N B N B 0 b N A0 X N A0 B b / a X
CB
a a V
C NC 0 c
N A0 X N C N C 0 c N A0 X N c / a X
CC A0 C
a a V
D N A0 D d / a X
N D0 d
N A0 X N D N D 0 d N A0 X CD
a a V
I NI0 - NI NI 0 C IO

b N B0 b
N B N B 0 N A0 X N A0 X
a N A0 a
b
i
N i 0 Ci 0

y
i0
N A0 B X
a N A0 C A0 y A0
 4. BATCH SYSTEMS STOICHIOMETRIC TABLE
Species Initially Change Remaining Concentration
A N A0 1 X
N A0 N A0 X N A N A0 N A0 X CA
V
B N B0
b
N A0 X N B N A0 B b X CB N A0 B b / a X
a a V
C NC 0 c
N A0 X NC N A0 C c X CC N A0 C c / a X
a a V
D N D0 d
N A0 X N D N A0 D d X CD N A0 D d / a X
a a V
I NI0 - NI NI 0 C IO
4. BATCH SYSTEMS STOICHIOMETRIC TABLE

EXAMPLE

Given the saponification for the formation of soap

from aqueous caustic soda & glyceryl stearate is:

3NaOH aq C17 H 35COO 3 H 5 3C17 H 35COONa C3 H 5 OH 3

Letting X the conversion of sodium hydroxide, set up a

stoichiometric table expressing the concentration of
each species in terms of its initial concentration and the
conversion.
4. BATCH SYSTEMS STOICHIOMETRIC TABLE
EXAMPLE

We know that this is a liquid-phase reaction.

Therefore, V=V0

3NaOH aq C17 H 35COO 3 H 5 3C17 H 35COONa C3 H 5 OH 3

3A B 3C D a 3 b 1 c 3 d 1

N A0 1 X N A0 1 X
CA C A0 1 X
V V0

N A0 B b / a X 1
CB C A0 B X
V0 3
 4. BATCH SYSTEMS STOICHIOMETRIC TABLE
EXAMPLE

Species Initially Change Remaining Concentration

A N A0 N A0 X N A N A0 1 X C A C A0 1 X

B N B0
1
N A0 X N B N A0 B 1 X 1
C B C A0 B X
3 3 3
C NC 0 CC C A0 C X
N A0 X NC N A0 C X

D 1 1
N D0 1
N A0 X D A0 D 3 X
N N C D C A0 D X
3
3
I NI0 - NI NI 0 C IO

Total NT 0 0 NT NT 0
5. FLOW SYSTEMS STOICHIOMETRIC TABLE

Purpose of developing stoichiometric table:

To determine the effluent flow rate of each species at

a conversion of X.
 5. FLOW SYSTEMS STOICHIOMETRIC TABLE

Components of stoichiometric table:

Species Feed rate to Change within Effluent rate

reactor the reactor from reactor
(mol/time) (mol/time) (mol/time)
A
B
C
D
I
Totals
5. FLOW SYSTEMS STOICHIOMETRIC TABLE

Species Feed rate Change Effluent rate from Concentration

to reactor within the reactor (mol/time) (mol/L)
(mol/time) reactor
(mol/time)
A FA0 1 X
FA0 FA0 X FA FA0 FA0 X CA

B b
FB 0 B FA0 b F X FB FA0 B X FA0 B b / a X
A0 a CB
a
C c
FA0 X FC FA0 C X C FA0 C c / a X
c
FC 0 C FA0
a a C

D d
FD 0 D FA0
d
FA0 X D A0 D a X CD FA0 D d / a X
F F
a
I - FI FA0 I F
FI 0 i FA0 C I A0 I

Totals FT 0 FT FT 0 FA0 X
QUIZ 5
Given a liquid phase reaction:
A+ 2B C + D

The initial concentration of A and B are 1.8 kmol/m3

and 6.6 kmol/m3 respectively. Construct a
stoichiometric table for a flow system considering A as
the basis of calculation.
 Fi 0 Ci 0 yi 0
ANSWER FOR QUIZ 5 i
FA0 C A0 y A0
A+ 2B C + D
Given:
C A0 1.8kmol / m3 CC 0 0kmol / m3 Since C & D are
products.
CBO 6.6kmol / m3 CDO 0kmol / m3
From stoichiometry, we know that,
a 1 b 2 c 1 d 1 d c b
1 1
a a a
Ci 0
i
C A0
6.6 0 0
B 3.67 C 0 D 0
1.8 1 .8 1 .8
ANSWER FOR QUIZ 5

Species Feed rate to Change Effluent rate from

reactor within the reactor (mol/time)
(mol/time) reactor
(mol/time)
A FA FA0 1 X
FA0 FA0 X
B
FB 0 FA0 B 2FA0 X FB FA0 B 2 X

C FA0 X
FC 0 FA0C FC FA0 X

D
FD 0 FA0 D FA0 X FD FA0 X

Totals FT 0 FT FT 0 FA0 X
ANSWER FOR QUIZ 5
Substituting the numerical values;
Species Feed rate to Change Effluent rate from
reactor within the reactor (mol/time)
(mol/time) reactor
(mol/time)
A FA0 FA0 X FA FA0 1 X

B FB FA0 3.67 2 X
FB 0 3.67 FA0 2 FA0 X

C
FC 0 0 FA0 X FC FA0 X

D FD 0 0 FD FA0 X
FA0 X

Totals FT 0 FT FT 0 FA0 X
 6. CONCENTRATION IN TERMS OF CONVERSION
1. For liquid phase:
Batch System: V V0
N A N A0 1 X
CA
V V

N B N A0 B b / a X N A0 B b / a X
CB C A0 B b / a X
V V V0

NC N A0 C c / a X N A0 C c / a X C A0 C c / a X
CC
V V V0

ND N A0 D d / a X N A0 D d / a X C d / a X
CD A0 D
V V V0
 6. CONCENTRATION IN TERMS OF CONVERSION
1. For liquid phase:
Flow System - 0

FA FA0 1 X
CA

FA0 B b / a X FA0 B b / a X
C A0 B b / a X
FB
CB
0

CC
FC

FA0 C c / a X

FA0 C c / a X C A0 C c / a X
0

CD
FD

FA0 D d / a X FA0 D d / a X
C A0 D d / a X
0
6. CONCENTRATION IN TERMS OF CONVERSION
2. For gas phase:
Batch System
NA
CA Need to substitute V
V from gas law equation

From equation of state;

At any time t, T= temperature, K

P= total pressure, atm (1 atm= 101.3 kPa)
PV ZNT RT (1) Z= compressibility factor
R= gas constant = 0.08206 dm3-atm/mol-K

At initial condition (t=0)

P0V0 Z 0 NT 0 RT0 (2)

 6. CONCENTRATION IN TERMS OF CONVERSION
2. For gas phase:
Batch System

PV ZNT RT (1)

P0V0 Z 0 NT 0 RT0 (2)

Recall from stoichiometric table

Dividing (1) by (2);
NT NT 0 N A0 X (4)
P0 T Z NT
V V0 (3)
P T0 Z 0 NT 0

Dividing (4) by NT0 ;

NT N A0
1 X
NT 0 NT 0
1 y A0 X
 6. CONCENTRATION IN TERMS OF CONVERSION
2. For gas phase: Applies for both
batch and flow
Batch System
systems
NT
1 y A0 X
NT 0 d c b NT
1
a a a NT 0
NT
1 X y A0
NT 0
Will be substitute
in (3)
Rearranging;
NT NT 0

NT 0 X
At complete conversion (for irreversible rxn): X=1, NT=NTf
N Tf N T 0

NT 0
 6. CONCENTRATION IN TERMS OF CONVERSION
2. For gas phase:
Batch System

P0 T Z NT
V V0 (3)
P T0 Z 0 NT 0

Substituting the expression for NT/NT0 in (3),

P0 T Z
V V0 1 X If the compressibility factor are not change
P T0 Z 0 significantly during rxn, Z0Z

P
V V0 0 1 X
T
(5)
P T0
6. CONCENTRATION IN TERMS OF CONVERSION
2. For gas phase:
Flow System
Fj Need to substitute
Cj from gas law equation

From gas law, at any point in the reactor,
FT P (1)
CT
ZRT

At the entrance of reactor;

FT 0 P0
CT 0 (2)
0 Z 0 RT0
Dividing (1) by (2)

FT P0 T (3)
0
FT 0 P T0
6. CONCENTRATION IN TERMS OF CONVERSION
2. For gas phase:
Flow System
Recall from stoichiometric table
FT FT 0 FA0X
FT P0 T
0
FT 0 P T0
Substituting for FT;
FT 0 FA0X P0 T
0
FT 0 P T0
FA0 P0 T
0 1 X
FT 0 P T0
P0 T P0 T
0 1 y A0X 0 1 X (4)
P T0 P T0
 6. CONCENTRATION IN TERMS OF CONVERSION
2. For gas phase:
Flow System

Fj Need to substitute
Cj from gas law equation

P0 T
0 1 X (4) F j F j 0 j v j X (5)
P T0
Substituting & Fj;
Stoichiometric
FA0 j v j X coefficient
Cj (d/a, c/a, -b/a, -a)
P0 T
0 1 x
P T0

C A0
v j X P T0
j

1 x P0 T
 6. CONCENTRATION IN TERMS OF CONVERSION
2. For gas phase:
Flow System aA + bB cC + dD
Concentration for each species: T
0 1 X
P0

FA FA0 1 X 1 X T0 P P T0
CA C A0
1 x T P0

FA0 B b / a X C B b / a X T0
FB P
CB

A0
1 x T P0

CC
FC FA0 C c / a X C C c / a X T0 P



A0
1 x T P0

FD FA0 D d / a X C D d / a X T0 P
CD

A0
1 x T P0
FI FI 0 I C A0 I T0 P
CI
1 x T P0
SUMMARY
Relative rate of reaction:

aA bB cC dD
rA rB rC rD

a b c d
Power Law Model:

rA kCA CB
SUMMARY
Elementary rate law:
The rxn that in which its stoichiometic coefficients are IDENTICAL to the
reaction order of each species.

Non-elementary rate laws:

The reactions that do not follow simple rate laws (power rate laws) in
which its stoichiometic coefficients are NOT IDENTICAL to the reaction
order of each species.

Reversible reaction:
All rate laws must reduce to the thermodynamic relationship relating the
reacting species concentrations at equilibrium.
SUMMARY
Reaction Rate Constant, k

k A T Ae E / RT
E , k , -r

The larger the activation energy,

the more sensitive k is, (towards
the change in temperature)
SUMMARY

Stoichiometric Table for Batch Systems

Species Initially Change Remaining
A N A0 N A0 X N A N A0 N A0 X

B N B0
b
N A0 X N B N B 0 b N A0 X
a a
C NC 0 c
N A0 X N C N C 0 c N A0 X
a a
D N D0 d
N A0 X N D N D 0 d N A0 X
a a
I NI0 - NI NI 0
 SUMMARY
Stoichiometric Table for Flow Systems

Species Feed rate to Change within the Effluent rate from

reactor reactor (mol/time) reactor (mol/time)
(mol/time)
A FA0 FA0 X FA FA0 FA0 X

B b
FA0 X
FB 0 B FA0 b FB FA0 B X
a a
C c
FA0 X c
FC 0 C FA0 FC FA0 C X
a a
D FD 0 D FA0
d
FA0 X d
FD FA0 D X
a a
I FI 0 i FA0 - FI FA0 I

Totals FT 0 FT FT 0 FA0 X
SUMMARY
Expression of V and in calculating the concentration
of each species:
Batch systems
Liquid phase:

V V0
Gas phase:
T P0
V V0 1 X
T0 P
Flow systems
Liquid phase:
0
Gas phase:

T P0
0 1 X
T0 P
QUIZ 6
Derive a concentration for each species for the
isothermal gas phase reaction below, neglecting
the pressure drop:

A+BC