RATE LAWS &

STOICHIOMETRY
1

LECTURER

: SLAMET
PRASWASTI PDK WULAN

REFERENCE : FOGLER (CHAPTER 3)

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

a b c
d

Reaction
Stoichiometry

EXAMPLE

2 NO O2 2 NO2
rNO rO2 rNO2

2 1
2

If NO2 formed at 4 mol/m3/s (r

3
NO2= 4 mol/m /s), what is the
rate of disappearance of NO?

1. Relative Rates of Reaction

2 NO O2 2 NO2
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

2 1
2

rNO rNO 2

2
2

rNO 4mol / m / s

2
2
rNO

4mol / m 3 / s
4mol / m 3 / s
2
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 r A= -10 mol/dm3/s

rA
rB rC
Thus, solving the rates of B & C;

rB
10mol / dm3 / s
2

15mol / dm3 / s

rC
10mol / dm3 / s
2
25mol / dm3 / s

2. Reaction Order & Rate Law

Rate law is a kinetic

expression that gives the
relationship between
reaction rate, -rA, and
concentration.

The reaction rate (rate of disappearance)

depends on temperature and concentration.

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 fnC A , CB ...

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;

2.1 Power Law Models & Elementary Rate Laws

The unit of the specific reaction, k, will vary with

the order of reaction.

A Products

Concentration
k

1 n

Time

rA k A

k mol /(dm3 s)

Second order (n=2)

rA k AC A
rA k ACA2

Third order (n=3)

rA k AC

k s 1
k (dm3 / mol ).s 1
2
3
k dm / mol s 1

Zero order (n=0)

First order (n=1)

3
A

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.
Unimolecular reaction
A Products

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.

2 NO O2 2 NO2
rNO k NO C C
2
NO

1
O2

Nonelementary
rxn
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

CO Cl2 COCl 2

Gas phase
synthesis of
phosgene

The kinetic rate law is:

rCO kCCO C

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

Example 2: Heterogeneous Rxn

C6 H 5CH 3 H 2 C6 H 6 CH 4

Gas-solid catalyzed
rxn:
Hydrodemethylation
of toluene (T)

cat

T H2 B M
cat
The rate of disappearance of toluene per mass of
catalyst is:

r
'
T

kPH 2 PT
1 K B PB KT PT

In terms of partial
pressure rather than
concentrations

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.
c
Ce
a
Ae

d
De
b
Be

C C
KC
C C

Thermodynamic
Equilibrium
Relationship

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

symbolically;

2B

k-B
kB

k D H 2
-B

The rate of disappearance of benzene;

rB , forward k BC

2
B

OR

rB , forward k BCB2

The reverse rxn between diphenyl & hydrogen;

k-B

C12 H 10 H 2 2C6 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

k BCB2 k BCDCH 2
Multiplying both sides by -1, we obtain the rate law of
disappearance of benzene, -rB

rB k BCB2 k BCDCH 2
2 CDCH 2
2 kB

rB k B C B
C D C H 2 k B C B
kB
KC

KC = Concentration equilibrium constant

2.3 Reversible Reactions

At equilibrium, -rB = 0

2 C DeC H 2e

rB 0 k B C Be
KC

C DeC H 2e
KC
2
C Be
For Cp = 0, then:

H Rx
K C (T ) K C (T1 ) exp
R

1 1

T1 T

3. The Reaction Rate Constant

k A T Ae

Arrhenius
equation

E / RT

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

A
e

-number of collision

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

E Energy barier
HRx
Reactants

e
Products

- no of collision that
result in a rxn

-total no of collision

E / RT

probability that
- the collision will
result in a rxn

3. The Reaction Rate Constant

k A T Ae

E / RT

Taking a natural logarithm;

E1
ln k A ln A
R T

T , k , -r =

Example 3-1: determination of E & A

k T k (T0 )e

The larger the

activation energy, the
more temperature
sensitive k and thus
the reaction rate.

E 1 1

R T0 T If k known at T
0

4. Batch Systems Stoichiometric Table

Purpose of developing stoichiometric table:

To determine the number of moles of each species

remaining at a conversion of X.
To express concentration as a function of
conversion, in order to carry out calculations of
reactor sizing.

4. Batch Systems Stoichiometric Table

Components of stoichiometric table:

Species
A
B
C
D
I

Totals

Initially
(mol)

Change
(mol)

refers to moles of
species reacted or
formed

Remaining
(mol)

4. Batch Systems Stoichiometric Table

aA + bB cC + dD

Recall from Chapter 2:

N A0 N A
X
N A0

moles of A reacted

N A N A 0 N A0 X
Factorizing:

N A N A0 1 X

moles of A remaining
in the reactor at a
conversion
of X

4. Batch Systems Stoichiometric Table

Moles B
reacted, NB

Moles C
formed, NC

Moles D
formed, ND

Moles B reacted
Moles A reacted

b
N A0 X
a
c
N A0 X
a

d
N A0 X
a

Moles A reacted

4. Batch Systems Stoichiometric Table

moles B remaining
in the system, NB

b
N B 0 N A0 X
a

moles of B
initially in the
system

NC

ND

c
N C 0 N A0 X
a
d
N D 0 N A0 X
a

moles of B
reacted

moles of C
formed

moles of D
formed

4. Batch Systems Stoichiometric Table

Species
A
B

C
D
I
Totals

Initially
(mol)

Change
(mol)

Remaining (mol)

N A0

N A0 X

N A N A 0 N A0 X

b
N A0 X
a
c
N A0 X
a
d
N A0 X
a

b
N A0 X
a
c
N C N C 0 N A0 X
a
d
N D N D 0 N A0 X
a
NI NI 0

N B0
NC 0
N D0

NI 0
NT 0

N B N B0

d c b
NT NT 0 1 N A0 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
NT NT 0 1 N A0 X
a a a

NT 0 N A0 X

where

Change in the total number of moles per

mole of A reacted

d c b
d c ba
1
a a a
a

4. Batch Systems Stoichiometric Table

rA kCA

rA kC A

rA k ACA3

Can we express concentration of each species??

Species

A
B
C
D
I
Totals

Initially

Change

Remaining Concentration

4. Batch Systems Stoichiometric Table

Concentration of each species in terms of

conversion can be expressed as:

N A N A0 1 X
CA

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

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

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

V
V

Recall from
stoichiometric
table
Remaining (mol)
A

N A N A 0 N A0 X
b
N B N B 0 N A0 X
a
c
N C N C 0 N A0 X
a
d
N D N D 0 N A0 X
a

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

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

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

N A0 D d / a X

N i 0 Ci 0
yi 0
i

N A0 C A0 y A0

4. Batch Systems Stoichiometric Table

Species Initially

Change

Remaining

N A0 X

N A N A 0 N A0 X

N A0

N B 0 b N A0 X

NC 0

N D0

NI 0

N B N B0

N B N B0

b
N A0 X
a

a
c
N A0 X NC NC 0 c N A0 X
a
a
d
N A0 X N D N D0 d N A0 X
a
a
NI NI 0
-

N B0 b
b
N A0 X N A0
X
a
N A0 a

N A0 B X
a

Concentration

CA

N A0 1 X
V

N A0 B b / a X
V
N c / a X
CC A0 C
V

CB

CD

N A0 D d / a X
V
CIO

N i 0 Ci 0
y

i0
N A0 C A0 y A0

4. Batch Systems Stoichiometric Table

Species Initially

N A0

N B0

NC 0

N D0

NI 0

Change

N A0 X

Remaining

N A N A 0 N A0 X

Concentration

CA

N A0 1 X
V

b
N A0 X N B N A0 B b X CB N A0 B b / a X
a
a

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

d
N A0 X N D N A0 D d X CD N A0 D d / a X
a
a
V

CIO
NI NI 0
-

4. Batch Systems Stoichiometric Table

EXAMPLE 3-2

Given the saponification for the formation of soap

from aqueous caustic soda & glyceryl stearate is:
3NaOH aq C17 H35COO 3 H 5 3C17 H35COONa 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 3-2

For a liquid-phase reaction, or gas-phase constant

volume V=V0
3NaOH aq C17 H35COO 3 H 5 3C17 H35COONa C3 H 5 OH 3

3 A 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 A 0 B X
V0
3

4. Batch Systems Stoichiometric Table

Species Initially

N A0

N B0

NC 0

N D0

NI 0

Total

NT 0

Change

Remaining

N A0 X

N A N A0 1 X

1
N A0 X N B N A0 B 1 X
3
3

N A0 X

NC N A0 C X

1
1
N A0 X N D N A0 D 3 X
3
NI NI 0
-

NT N T 0

Concentration

CA CA0 1 X
1

C B C A0 B X
3

CC CA0 C X
1

C D C A0 D X
3

CIO

4. Batch Systems Stoichiometric Table

EXAMPLE 3-3

Limiting reactant
The basis of calculation should
be the limiting reactant

5. Flow Systems Stoichiometric Table

Purpose of developing stoichiometric table:

To determine the effluent flow rate of each

species at a conversion of X.
To express concentration as a function of
conversion, in order to carry out calculations of
reactor sizing.

5. Flow Systems Stoichiometric Table

Components of stoichiometric table:

Species

A
B
C
D
I
Totals

Feed rate to
reactor
(mol/time)

Change within
the reactor
(mol/time)

Effluent rate
from reactor
(mol/time)

5. Flow Systems Stoichiometric Table

Species

A
B
C
D

I
Totals

Feed rate
to reactor
(mol/time)

FA0
FB 0 B FA0

FC 0 C FA0
FD0 D FA0

FI 0 i FA0

FT 0

Change
within the
reactor
(mol/time)

FA0 X

Effluent rate from

reactor (mol/time)

FA FA0 FA0 X

Concentration
(mol/L)

CA

FA0 1 X

b
F

FA0 X B A0 B a X C FA0 B b / a X
B
a

c
FA0 X FC FA0 C ac X CC FA0 C c / aX

d
F

FA0 X D A0 D a X CD FA0 D d / a X
a

F
FI FA0I
C I A0 I

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.

Answer For

Fi 0
Ci 0
yi 0
Quiz 5i F C y
A0
A0
A0

A+ 2B C + D
Given:
3
C A0 1.8kmol / m

CC 0 0kmol / m

C BO 6.6kmol / m 3

C DO 0kmol / m 3

Since C & D are

products.

From
d c b
a 1 bstoichiometry,
2 c 1 d we
1 know that,
1 1
a a a
Ci 0
i
C A0
0
0
6.6
C
0
D
0
B
3.67
1.8
1.8
1.8

Answer for quiz 5

Species

Feed rate to
reactor
(mol/time)

Change
within the
reactor
(mol/time)

FA0

FA0 X

Effluent rate from

reactor (mol/time)

FA FA0 1 X

FB 0 FA0 B

FC 0 FA0C

FA0 X

FC FA0 X

FD0 FA0D

FA0 X

FD FA0 X

Totals

FT 0

2FA0 X FB FA0 B 2 X

FT FT 0 FA0 X

Answer for quiz 5

Substituting the numerical values;
Species

Feed rate to
reactor
(mol/time)

Change
within the
reactor
(mol/time)

FA0

FA0 X

FA FA0 1 X

FB0 3.67FA0

2FA0 X

FB FA0 3.67 2 X

FC 0 0

FA0 X

FC FA0 X

FD0 0

FA0 X

FD FA0 X

Totals

FT 0

Effluent rate from

reactor (mol/time)

FT FT 0 FA0 X

6. Concentration in terms of conversion

1. For liquid phase:
Batch System: V V0
CA

N A N A0 1 X

V
V

CB

N B N A0 B b / a X N A0 B b / a X
CA0 B b / a X

V0
V
V

NC
N A0 C c / a X CA0 C c / a X
N A0 C c / a X
CC

V0
V
V

ND
N A0 D d / a X N A0 D d / a X C d / a X
CD
A0
D

V0
V
V

6. Concentration in terms of conversion

1. For liquid phase:
Flow System - 0
CA

FA

CB

FB

CC

FC

CD

FD

FA0 1 X

FA0 B b / a X
FA0 B b / a X
CA0 B b / a X

FA0 C c / a X
0

CA0 C c / aX

FA0 D d / a X FA0 D d / a X

CA0 D d / a X

FA0 C c / a X

6. Concentration in terms of conversion

2. For gas phase:

Batch System

CA

NA
V

Need to substitute V
from gas law equation

From equation of state;

At any time t,

PV ZNT RT

(1)

At initial condition (t=0)

P0V0 Z0 NT 0 RT0

(2)

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

6. Concentration in terms of conversion

2. For gas phase:

Batch System

PV ZNT RT

P0V0 Z0 NT 0 RT0

(1)
(2)
Recall from stoichiometric table

Dividing (1) by (2);

P T Z N
V V0 0 T
P T0 Z 0 N T 0
Dividing (4) by NT0 ;

N A0
NT
1
X
NT 0
NT 0
1 y A0 X

NT NT 0 N A0 X
(3)

(4)

6. Concentration in terms of conversion

2. For gas phase:

Applies for both

batch and flow
systems

Batch System

NT
1 y A0 X
NT 0

NT
1 X
NT 0
Rearranging;

d c b
NT
1
a a a
NT 0
y A0

Will be substitute
in (3)

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

P T Z N
V V0 0 T
P T0 Z 0 N T 0

(3)

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

P T Z
V V0 0 1 X
P T0 Z 0
T
P0
V V0 1 X
T0
P

(5)

If the compressibility factor are not change

significantly during rxn, Z0Z

6. Concentration in terms of conversion

2. For gas phase:
Flow System
Need to substitute
Fj
Cj
from gas law equation

From gas law, at any point in the reactor,

CT

FT

P
ZRT

(1)

At the entrance of reactor;

CT 0

FT 0

P0

0 Z 0 RT0

(2)

Dividing (1) by (2)

FT P0 T

0
FT 0 P T0

(3)

6. Concentration in terms of conversion

2. For gas phase:

Flow System

Recall from stoichiometric table

FT P0 T

0
FT 0 P T0

FT FT 0 FA0X

Substituting for FT;

FT 0 FA0X
0
FT 0

P0 T

P T0

FA0
P0 T
0 1
X
FT 0
P T0
P0
P0 T

X
0 1 y A0X
0
P
P T0

T

T0

(4)

6. Concentration in terms of conversion

2. For gas phase:

Flow System

Cj

Fj

Need to substitute
from gas law equation

P0 T
0 1 X
P T0
Substituting & Fj;
FA0 j v j X
Cj

P T
0 1 x 0
P T0

C A0

v j X P T0

1 x P0 T
j

(4)

F j F j 0 j v j X

(5)

Stoichiometric
coefficient
(d/a, c/a, -b/a, -1)

6. Concentration in terms of conversion

2. For gas phase:

aA + bB cC + dD

Flow System
Concentration for each species:
F 1 X
F
1 X T0 P
C A A A0
C A0

1 x T P0

0 1 X

CB

FB

FA0 B b / a X C B b / a X T0
A0

1 x T

CC

FC

FA0 C c / a X C C c / a X T0

A0
1 x T

P

P0

P

P0

FA0 D d / a X C D d / a X T0 P
CD
A0

1 x T P0

FD

FI FI 0 I C A0 I T0 P
CI
1 x T P0

P0
P

T0

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.
Power Law Model:

Summary
Reaction Rate Constant, k

E / RT

k A T Ae

T , 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

N A0 X

N A N A 0 N A0 X

N A0

N B 0 b N A0 X

NC 0

N D0

NI 0

N B N B0

b
N A0 X
a

a
c
N A0 X NC NC 0 c N A0 X
a
a
d
N A0 X N D N D0 d N A0 X
a
a
NI NI 0
-

Summary
Stoichiometric Table for Flow Systems
Species

A
B
C

D
I
Totals

Feed rate to
reactor
(mol/time)

FA0
FB 0 B FA0

FC 0 C FA0
FD0 D FA0

FI 0 i FA0

FT 0

Change within the

reactor (mol/time)

FA0 X
b
FA0 X
a
c
FA0 X
a
d
FA0 X
a
-

Effluent rate from reactor

(mol/time)

FA FA0 FA0 X
b

FB FA0 B X
a

FC FA0 C X
a

FD FA0 D X
a

FI FA0I

FT FT 0 FA0 X

SUMMARY
Expression of V and in calculating the

concentration of each species:

Batch systems

Liquid phase (& gas-phase V constant):

V V0

Gas phase (& V not-constant):

V V0 1 X

T P0

T0 P

Flow systems

Liquid phase:

Gas phase:

T P0
0 1 X
T0 P

Concentration
vs
Conversion

Quiz
Derive a concentration as a function of conversion

for each species for the isothermal gas phase reaction

below in the flow system, neglecting the pressure
drop:
A+BC

Problem P3-7 : (a) & (b)