CHEMICAL REACTION

ENGINEERING (SKF3223)

Chapter 3: Rate Laws and

Stoichiometry

WAN NORHARYATI WAN SALLEH

hayati@petroleum.utm.my
RAFIZIANA MD. KASMANI
rafiziana@petroleum.utm.my
 TYPES OF REACTION
• Homogenous reaction – one phase reaction
• Heterogeneous reaction – more than one phase
• Irreversible reaction:
A B C D
(one direction)
• Reversible reaction:

A B C D
(foward or backward)
 Relative rates of reaction
aA bB cC dD
b c d
A B C D
a a a
For every mole of A that is consumed/reacted, c/a moles of C appear

rA rB rC rD rA rB rC rD
or
a b c d a b c d
 RATE LAWs Zero order :
- rA k A : {k} mol/(dm)3 .s
The rate law:
First - order
rA k AC A C B - rA k AC A : {k} s -1
• Order with respect to A = α
• Order with respect to B = β Second - order
• Overall reaction order, - rA k AC A2 : {k} (dm) 3 / mol.s
n=α+β
• k = (Concentration)1-n
Third order
Time
rA k AC A3 : {k} (dm 3 / mol ) 2 .s 1
 Elementary rate laws
• 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:

2
rA k AC AC B
 NonElementary rate laws
• The stoichiometric coefficients are not the same as
the individual reaction order of each species.

 For the reaction: A B C D

 The rate law would be:

rA k AC A2 C B
Then the reaction is said to be 2nd order in A, 1st order in B,
and 3rd order overall.
 REVERSIBLE
REACTIONS
• For general reaction: aA bB cC dD
• The net rate of formation A
rA rA,net rA, forward rA,reverse
a b c d
rA, forward k AC A C B and rA,reverse k AC C C D

• At equilibrium, rnet=0. Thus,

a b c d kA
k AC A C B k AC C C D
K equilibrium
k A
K = thermodynamic equilibrium constant
 rA rA,net rA, forward rA,reverse

rA k AC aA CBb k ACCc CDd

• Multiplying both sides of equation by (-1), we obtain the rate law for the rate of
disappearance of A:

rA k AC aA CBb k ACCc CDd

kA k A 1
• Replacing with K K equilibrium
k A kA K

a b k A c d CCc CDd
rA kA C C A B CC CD rA k A C AaCBb
kA K
• At equilibrium, -rA = 0:

CCc CDd
k A C AaCBb 0
K

CCc CDd
C AaCBb 0
K
CCc CDd
C AaCBb
K

CCc CDd
K
C Aa CBb
 k
• Specific reaction rate or the rate constant
• k is temperature dependent, described by Arrhenius
equation:

E / RT
k A (T ) Ae
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

 The activation energy is a measure of the minimum energy a that the

reacting molecules must have in order for the reaction to occur.
 E / RT
 From Arrhenius equation: k A (T ) Ae

 Activation energy is High E

determined experimentally:
E
Slope
In kA R
E 1
ln k A ln A Low E
R T

1/T
 b c d
A B C D
STOICHIOMETRY TABLE - BATCH SYSTEMS
a a a

Species Initially (mol) Remaining (mol)

Change (mol)

A NA0 ( N A0 X ) NA N A0 N A0 X

B NB0 b b
( N A0 X ) NB N B0 N A0 X
a a
C NC0 c c
( N A0 X ) NC NC 0 N A0 X
a a
D ND0 d d
( N A0 X ) ND N D0 N A0 X
a a
I (inerts) NI0 NI NI0
-

TOTALS NT0 d c b
NT NT 0 N A0 X , 1
a a a
* -ve = disappearing from the system
 3. Simplify,

1. To express the concentration of each

component in terms of the conversion X:
Ni0 Ci 0 yi 0
i
N A0 C A0 y A0
NA
CA
V N B0 b
2. Therefore, N A0 ( X)
N A0 a
CB
V
NA N A0 N A0 X N A0 (1 X )
CA N B0
V V V B
N A0
NB N B 0 (b / a) N A0 X
CB NC 0 c
V V N A0 ( X)
N A0 a
CC
NC N C 0 (c / a ) N A 0 X V
CC
V V N D0 d
N A0 ( X)
ND N D 0 ( d / a ) N A0 X N A0 a
CD CD
V V V
 CONSTANT-VOLUME
BATCH SYSTEMS
V V0

NA N A0 N A0 X N A0 (1 X ) N A0 (1 X )
CA C A0 (1 X )
V V V V0

NB N B 0 (b / a) N A0 X N A0 ( B (b / a ) X ) b
CB C A0 B X
V V V0 a

NC N C 0 (c / a ) N A 0 X N A0 ( C (c / a ) X ) c
CC C A0 C X
V V V0 a

ND N D 0 (d / a ) N A0 X N A0 ( D (d / a) X ) d
CD C A0 D X
V V V0 a
 EXAMPLE

rA kCACB
CA C A0 (1 X )

b
CB C A0 B X
a

b
rA kCA0 (1 X )C A0 B X
a

2 b
rA kCA0 (1 X ) B X
a
 b c d
A B C D
STOICHIOMETRY TABLE - FLOW SYSTEMS
a a a
Feed rate to Change within Effluent rate from reactor
Species reactor (mol/time) reactor (mol/time) (mol/time)

A FA 0 ( FA0 X ) FA FA0 (1 X )
B FB 0 b b
B FA 0 ( FA0 X ) FB FA0 B X
a a
C c c
FC 0 C FA0 ( FA0 X ) FC FA0 C X
a a
D d d
FD 0 D FA0 ( FA0 X ) FD FA0 D X
a a
I (inerts) FI 0 FA0 FI FA0
I - I

TOTALS FT 0 d c b
FT FT 0 FA0 X , 1
a a a
To express the concentration of each component in terms of the
entering molar flow rate, F, the conversion X, and the volumetric
flow rate, v:

FA FA0 FA0 X FA0 (1 X )

CA
v v v
FA moles / time moles
CA
FB FB 0 (b / a) FA0 X v liters / time liter
CB
v v

FC FC 0 (c / a) FA0 X FB 0 CB 0v0 CB 0 yB 0
CC B
v v FA0 C A0v0 C A0 y A0

FD FD 0 (d / a) FA0 X
CD
v v
 LIQUID-PHASE
REACTIONS
v v0

FA FA0 (1 X ) FA0 (1 X )
CA C A0 (1 X )
v v v0

b
CB C A0 B X
a

c
CC C A0 C X
a

d
CD C A0 D X
a

*similar with constant-volume batch systems

 BATCH REACTORS with
VARIABLE VOLUME
 Equation of state:
NT
1 X
PV ZNT RT NT 0

P=total pressure (atm)

V=volume d c b N A0
Z=compressibility factor 1 y A0
a a a NT 0
NT=total number of moles
R=gas constant=0.08206
dm3.atm/mol.K  At any time t, the volume of gas (Z0=Z):
T=temperature (K)
P0 T Z NT
 At t=0: V V0
P T0 Z 0 NT 0
P0V0 Z 0 N T 0 RT0
P0 T
V V0 (1 X)
P T0
 FLOW REACTORS with
VARIABLE VOLUMETRIC
FLOW RATE
 Total concentration found from
the gas law:
FT P  At t=0:
CT
v ZRT
FT 0 P0
CT 0
 At any time t, the volume of gas (Z0=Z): v0 Z 0 RT0

FT P0 T
v v0
FT 0 P T0

P0 T
v v0 (1 X)
P T0
 CONCENTRATION IN
TERMS
OF THE CONVERSION X
Fj , Fj FA0 ( P0 T
Cj j vj X ) , v v0 (1 X)
v P T0

FA0 ( j vj X )
Cj
P0 T
v0 (1 X)
P T0

C A0 ( j v j X ) P T0
Cj
(1 X) P0 T
We now have –rA as a function of X and
can use the methods in Chapter 2 to design
reactors.
 Expressing concentration in terms
other than conversion
• Membrane reactors and gas-multiple reaction:

Fj P T0
Cj CT 0
FT P0 T

For j = A,B,C,D,I

FT FA FB FC FD FI
 REFERENCES
Main Reference:

1. Fogler,H.S., “Elements of Chemical Reaction Engineering”, 4th

Edition,Prentice Hall, New Jersey, 2006.

Other References:

1. Davis, M.E and Davis, R.J, “Fundamentals of Chemical Reaction

Engineering”, Mc-Graw-Hill, New York, 2003
2. Schmidt, L.D, “The Engineering of Chemical Reactions”, Oxford,
New York, 1998
3. Levenspiel,O., “Chemical Reaction Engineering”, 3rd Edition,
Wiley,New York, 1998
4. Smith,J., “Chemical Engineering Kinetics”, 3rd Edition, McGraw-
Hill, New York, 1981