Chemical Reaction Engineering

Chapter 2
This course focuses on “how to obtain the rate of
reaction as a function of conversion”:

• Define the rate law, which relates the rate of

reaction to the concentrations of the reacting
species and to temperature
• Define concentrations for flow and batch
systems and develop a stoichiometric table
 Relative rates of reaction
• For reaction: 
aA 
bB 
cCdD
Rate of formation of C = c/a (rate of disappearance of A)
c
rC  (rA)
 rA rC 
rA 
rB r
C r
   D
a a c a b c d

• Rate law (rate equation)

– Algebraic equation accurately describes the reaction rate as a
function of concentration and temperature.

r
Af
(T,
C)
k(
T
A)[
f
(C,
C
AB,...)]
– Why functions of concentrations and temperature?
– How do molecules react? By collision
 Concentration and temperature
• Collision frequency  concentration
– Rate of reaction  concentration.
– At constant temperature : r = f(CA, CB, …….)

• As temperature increases, collision frequency increases.

– Rate of reaction = f [( CA, CB, ……), (T)]


rAk
A(
T)[
f(
CA,
C ,...)]
B
Reaction rate constant of A
Questions about the rate of reaction, -rA
• At this point we need to develop means of
expressing reaction kinetics because design
equations allow batch, plug flow and CSTR
reactors to be sized for a given throughput or
conversion
– what does (-rA) depend on?
– How do reactions occur?
– Which parameters determine reaction rate?
 Factors affecting reaction rate

Heat transfer Pressure / Composition Catalyst

Temp. (T) Mass transfer Concentration (C)

rA = f (T, C)

This has been observed empirically - but it will now be examined quantitatively.
 (Specific) rate constant, kA
• It is strongly dependent on temperature.
– In gas-phase reactions
• It depends on catalysts and may be a function of total pressure.
– In liquid system
• It can be a function of total pressure.
• It may depend on ionic strength and choice of solvent.
• Here, we consider the temperature only.
• Unit issue…
 Rate of reaction and temperature
Empirical Observations.
It was the Swedish chemist Svante Arrhenius who first suggested that the
temperature dependence of the specific reaction rate constant, k, could be
correlated by an equation of the type:

Arrhenius Equation

Where :
A= preexponential factor or frequency factor (1/time)
Ea= Activation energy, J/mol or cal/mol
R= Gas constant, 8.314 J/mol K (or 1.987 cal/mol K)
T= Absolute temperature, K
Arrhenius equation has been verified empirically to give the temperature
behaviour of most reaction rate constants (within experimental accuracy)
over fairy large experimental ranges.

Activation energy determined experimentally by carrying out the reaction at

several temperatures. After taking the natural logarithm of the Arrhenius
equation :


E1
ln
kln
A  ln k -E/R

RT

Question : Have these observations

any fundamental basis?
(1) Thermodynamics
1/T
(2) Collision theory
(3) Absolute reaction rate theory
 Activation energy
– Distort or stretch the bonds
– Overcome the steric and electron repulsion force
– Quantum effects can in some cases produce a barrier
– There usually isn’t an active energy needed for free radical
reactant reactions.
Example 3-1 Calculate the activation energy for the first-order decomposition
reaction of benzene diazonium chloride to give chlorobenzene and nitrogen:

ln kA
Arrhenius Equation
 E / RT E1
k A (T)  Ae ln k A  ln A   
R T 
14017 1/T
ln k A  37.12 
T
 kJ  kJ
E  (14017 K ) R  (14017 K ) 8.314 •   116.5•
 mol  K  mol
A  1.32 1016 •s 1
 14017 K 
Arrhenius Equation k A (T)  1.32 10 exp  16

 T 
 Order of reaction
• This reaction has no simple overall order
because it is a complex chain reaction (not
elementary reaction).
• The overall order is not necessarily an integer,
and this is particularly true for free radical and
heterogeneous reactions.
• For simple homogeneous reactions, the order of
reaction, n = 0, 1, 2 or 3 (rare).
One of the most general forms: r ab
kC
C
AB.........

where k = velocity constant or specific rate constant.

If CA, CB , …. = 1; then r = k
a , b … = reaction order with respect to CA , CB .

a + b + ... = overall order (this treatment is only applicable to simple reactions).

Reaction order
• Power to which concentration is raised to make rate proportional to it.
• It can only be determined experimentally.
 Elementary reaction & Elementary rate laws

• Elementary reaction is one that evolves a single step.The

stoichiometric coefficients in an elementary reaction are
identical to the powers in the rate law:

OCH 3OH  CH O
3 OH   r
O kO C OC CH OH
3

• An elementary reaction has an elementary rate law.

• Some reaction follows an elementary rate law is not an
elementary reaction.
2NO + O2 → 2NO2 r k
NO NO
2
C
NOC
O2

H2I22HI r
H2
kH2
CH2
CI2
 Stoichiometric Equation
• This describes the overall reaction but the reaction order cannot
be deduced from it.
Examples:

H
I 2HI
2 2 rf = kfCH CI and rb = kbCHI2
2 2

Forward reaction is 1st order in CH and CI ( 2nd order overall)

2 2
Reverse reaction is 2nd order in CHI

Compare the above reaction with the analogous nonelementary reaction

between H2 and Br2 .
12
k1 kC
1H C
2 Br

H 
Br
 rf 
2HBr 2

2
2 2
k2 k C C
HBr
Br2
 Molecularity
• This is the number of atoms, ions, or molecules
involved (colliding) in the rate-limiting step of a
reaction.

Examples:
(i)

H
I Bimolecular reaction, since two species
2HI
2 2
are involved in the reaction step.
(ii)
U
92 
238
90Th
234 4
He
2
Unimolecular
urianium-238 thorium helium
 
(iii) H
Br
2 22HBr
This is not a bimolecular reaction. Why?
Because the reaction occurs as follows:

2
Br 
2Br Initiation

Br
H2 
HBr
H


HBr
2 
HBr
Br Propagation
H 
BrH
 
H
2B
r
2
BrB
r2
Termination

Each step has a molecularity, which must be an integer.

Thus, order and molecularity are not necessarily identical for a
given reaction.
 Back to reaction rate law…

rAk
A(
T)[
f(
CA,C
B,...)]
• The dependence of the reaction rate -rA on the
concentrations of the species present, f (Cj), is
almost without exception determined by
experimental observations. Hence rate laws are
determined by experimental observation and
they are a function of the reaction chemistry and
not the type of reactor.
 Reversible reaction
• The rate law must satisfy thermodynamic
relationships at equilibrium.
• The rate law must reduce to the irreversible rate
law when the concentration of one or more of
the reaction products is zero.
– The form of the irreversible rate law provides a big
clue as to the form of the reversible reaction rate
expression.
Consider the general reversible reaction:

rfAkfACA
a b
CB


aAbB
 
cCdD At equilibrium –rA=0
rbAk CC c d
bA C D A
r rfAr
bA0

rfA = rbA
Therefore: kCCa b
kCC
fAA B bA
c d
CD

c d
kfA C C
Therefore: K
C C D
a b
kbB CACB

Thermodynamic equilibrium relationship


H 
1 1

    

RX
Thermodynamic equilibrium constant K
(
CT
)K(
T
C)
1exp  
 
R T1 
T
 
H 
1 
1
   
RX
K
(
CT
)K(
T
C)
1exp  
R 
T 
1T

Endothermic Exothermic

KC KC

T T
 Chemical equilibrium
• All reactions are reversible in principle.
• The extent of reversibility depends on -G, the Gibbs
Free Energy change.


G
RTInK
p
Where Kp is the equilibrium constant in terms
of partial pressures.

If Kp is large, reaction is essentially irreversible, which means that

the equilibrium position lies very far to the product side.
 Stoichiometric table
• Stoichiometric relationships between reacting molecules for a
single reaction.

aA
bB
cCdD
t=t
NA NAN0
A NA0X

t=0 NB b
B
N N0 N
B A
0X
a
NA0 c
NC
NB0 Batch reactor C
N N0 N
C A
0X
a
NC0
ND d
ND0 N
DND0 NA0X
a
NI0
NI NI  NI 0
 Species Initial Change Remaining Concentration*
mole mole mole (volume change or not)
A NA0
 N A0 X NAN0
A N0X
A
CA0(1X)
B NB0 b b  b 
 NA0 X B
N N0 N X CA0B X
a
B
a
A
0
 a 
C NC0 c c  c 
 NA0 X NN  N X CA 
0 C X
a
C C
0
a
A
0
 a 
D ND0 d d  d 
 NA0X NN 0 N X CA0D X
a
D D
a
A0
 a 
I NI0 -- NI  NI 0 CI 0
Total NT0 
dcb *constant volume here
N
TN
T
0
1
NAX
0

aa a
d c b T
   1 N NT0
N 0X
A  
Ni0

Ci0

y
i0
i
a a a NA0 C
A 0 y
A0
The change in the total number of moles per mole of A reacted.
• Major objective:
– Rate law -rA as a function of conversion:
– Our experience:

e.g.
Example 3-2 Soap consists of the sodium and potassium salts of various fatty
acids such as oleic, stearic, palmitic, lauric, and myristic acids. The saponification
for the formation of soap from aqueous caustic soda and glyceryl stearate is
3 NaOH (aq )  (C17 H 35COO) 3 C3 H 5  3C17 H 35COONa  C3 H 5 (OH ) 3
Letting X represent 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 X.
A  13 B•
 C•
 13 D liquid phase reaction: V  V0
Example 3-3 Having set up the stoichiometric table in Example 3-2, one can now
readily use it to calculate the concentrations at a given conversion. If the initial
mixture consists solely of sodium hydroxide at a concentration of 10 mol/dm3 (i.e.,
10 mol/L or 10 kmol/m3) and of glyceryl stearate at a concentration of 2 mol/dm3,
what is the concentration of glycerine when the conversion of sodium hydroxide is
(a) 20% and (b) 90% ?

Only the reactants NaOH and (C17H35COO)3C3H5 are initially present:

C=D=0.
 1   0.2 
C D  C A0   D  X   10   0.67 •mol / L  0.67 •mol / dm
3

 3   3 
X = 20%
 1   2 0.2 
C B  C A0   B  X   10    1.33•mol / dm
3

 3   10 3 
 1   0.9 
C D  C A0   D  X   10   3•mol / dm
3

 3   3 
X = 90%
 1   2 0.9 
C B  C A0   B  X   10    1•mol / dm
3

 3   10 3 
Stoichiometric table (flow system)

aA
bB
cCdD

entering Leaving
FA0 FA
FB0 FB
FC0 FC
FD0 Continuous-flow reactor FD
FI0 FI
Species Feeding rate Change Effluent rate
mole/t mole/t mole/t
A FA0

B FB0=ΘBFA0

C FC0=ΘCFA0

D FD0=ΘDFA0

I FI0=ΘIFA0 --
Total FT0
• Major objective:
– Rate law -rA as a function of conversion:rA  f (X)
– Our experience: e.g. rA kC ACB
FA
CA 
v
– Liquid phase:
• Volume change with reaction is negligible when no
phase changes are taking place.
v  v0
CA
FA F
 A0(1X)CA 1X)
0(
rA kC
ACB
v v0
...
 b 
CB CA 
0 B X
 a 
...
– Gas-phase:
• The reaction volume (V) or volumetric flow rate (v)
most often changes during the course of the reaction
because of a change in the total number of moles or in
temperature or pressure
• e.g. N 2 3H 2 2 NH 3

4 mol 2 mol

rA kC
ACB CA
NA F
 A
V v
 – Variable volume
• Equation of state
PV ZN TRT

t=0
 PTZN
PV0Z0N
T0RT
V
V
0
0
 
 

T

 00
0 0
P T Z NT
0

T
from stoichiometri table N NT0
N 0X
A

N
T
N

1
N
A
N
0
X

1y
A0X

1
X  
T
0 T0 1
  yA0
   

VV0
P

0 T

Z



1
X
 PT
0Z
0
 – Variable volumetric flow rate
F P
T 
T
C
entering v ZRT 1
F P F PT
Z
0      
 
T0 0
C v v T 0
T
v Z RT 0   
 
0 0 0 T
F0 0
P T0
Z

T
From stoichiometri table F FT0FA
0X


v v
0
1y
A
0X
P0 T
 

P 0
T

C( j
vjX
)P
T

A
0
 

0
  yA0 C
j

1  
X 
0
PT
 
Stoichiometric coefficient
vv
1
X  
P
0 T
 
 F 
0( jvjX)
j
0 A
C
P0
T
Fj T
v01X 
For species j C j 
P
0
 

v FjF
j 
v(
F
0 j A
0X
)
F(
A
0 jv
X
j ) PT0
Species Feeding rate Change Effluent rate
mole/t mole/t mole/t

A 1X)
A FA0
 FA0 X F FA0(

B FB0=ΘBFA0 b  b
 FA0 X B
F F
A
0 
BX
a  a
C FC0=ΘCFA0 c  c 
 FA0 X C
F F
A
0 
CX 
a  a
D FD0=ΘDFA0 d  d
 FA0 X F
DF
A
0 
D X
a  a
I FI0=ΘIFA0 -- FI FA0I
Total FT0 dcb
F
TF
T
0
1F
AX
0
aaa
T
F F 0
F 0X
  
T A
F C rA f(
X )
Example 3-5 A mixture of 28% SO2 and 72% air is charged to a flow reactor in which SO2
is oxidized: SO 2  12 O 2  SO3
First, set up a stoichiometric table using only the symbols (i.e., Θi, Fi) and then prepare a
second stoichiometric table evaluating numerically as many symbols as possible for the case
when the total pressure is 1485 kPa (14.7 atm) and the temperature is constant at 227 C.

Taking SO2 as the basis of calculation:

FA0  (0.28) FT 0
FB 0  (0.72)(0.21) FT 0
FI 0  (0.72)(0.79) FT 0

FB 0 (0.72)(0.21) FI 0 (0.72)(0.79)
B    0.54 I    2.03
FA0 0.28 FA0 0.28
 SO 2  12 O 2  SO 3

  y A0  (0.28)(1  1  12 )  0.14

 P0  T 
v  v0 1  X   
FA FA0 (1  X )  P  T0  FA0 (1  X )  1 X 
CA   CA   C A0  
v v v0 (1  X )  1  X 
 P   1 X 
C A0  y A0CT 0  y A0  0  C A  C A0  
 RT0   1  X 
 1485•kPa 
 0.28   1 X 
 8 .314 •kPa  dm 3
/( mol  K )  500 •K   0.1  •mol / dm
3

 0.1•mol / dm 3
 1  0.14 X 
…
  1 X   1 X  FT FT 0  y A0XFT 0
C A  C A0    0.1  •mol / dm
3
CT  
 1  X   1  0.14 X  v v0 (1  X )
  B  12 X   0.54  0.5 X  FT 0 (1  X )
C B  C A0    0.1  •mol / dm 3

 1  X   1  0.14 X  v0 (1  X )
C A0 X 0.1X P0
CC   mol / dm 3  CT 0 
1  X 1  0.14 X RT0
C A0  I (0.1)(2.03) 1485•kPa
CI   mol / dm 3 
1  X 1  0.14 X [8.314 •kPa  dm 3 / mol  K ](500 •K )
 0.357 •mol / dm 3

Change concentration!!
If the rate law for this reaction were first order in SO2 (i.e., A) and in O2 (i.e., B)
with k=200 dm3/mol.s:

 rA  kC AC B
 1 X   0.54  0.5 X 
C A  0.1  •mol / dm
3
C B  0.1  •mol / dm
3

 1  0.14 X   1  0.14 X 
2(1  X )(0.54  0.5 X )
 rA 
(1  0.14 X ) 2
Example 3-6 The reversible gas-phase decomposition of nitrogen tetroxide, N2O4, to
nitrogen dioxide, NO2, is to be carried out at constant temperature. The feed consists
of pure N2O4 at 340 K and 202.6 kPa (2 tam). The concentration equilibrium
constant, Kc, at 340 K is 0.1 mol/dm3.
N 2O4  2NO2 A  2B

2
C Be
concentration equilibrium constant: Kc  at equilibrium
C Ae
!!
 P0 
C A0  y A0CT 0  y A0  
 RT0 
 2 •atm 
 (1)    0.07174 •mol / dm 3

 0.0821•atm  dm 3
/(mol  K )  340 •K 
(a) Calculate the equilibrium conversion of N2O4 in a constant-volume
batch reactor.
2
C Be
at equilibrium Kc 
!! C Ae

N A N A N A0 (1  X )
CA     C A0 (1  X )
V V0 V0
N B N B 2 N A0 X
CB     2C A0 X
V V0 V0
 P0 
C A0  y A0CT 0  y A0    0.07174 •mol / dm 3
 RT0 
2
C Be 4C A0 X e2
Kc  
C Ae 1 X e

X e  0.44
(b) Calculate the equilibrium conversion of N2O4 in a flow reactor.

2
C Be
at equilibrium Kc 
!! C Ae
FA FA0 (1  X ) FA0 (1  X ) C A0 (1  X )
CA    
v v v0 (1  X ) 1  X
FB 2 FA0 X 2C A0 X
CB   
v v0 (1  X ) 1  X
 P0 
C A0  y A0CT 0  y A0    0.07174 •mol / dm 3
 RT0 
2
C Be 4C A0 X e2
Kc   X e  0.51
C Ae (1  X e )(1  X e )   y  (2  1)(1)  1
A0
(c) Assuming the reaction is elementary, express the rate of reaction solely
as a function of conversion for a flow system and for a batch system.
Elementary reaction:  C B2 
A  2B  rA  k A C A  
 K c 

 C A0 (1  X ) 4C A2 0 X 2 
for flow system：  rA  k A   2
 1  X K c (1   X ) 
 4C 2
X 2

for batch system： rA  k A C A0 (1  X )  A 0

 K c 

(d) Determine the CSTR volume necessary to achieve 80% of the equilibrium
conversion.
 (1  0.4) 2.88(0.4) 
2
mol
 rA  0.0036   2 
 0.0007 • 3
X  0.8 X e  0.4  (1  0.4) (1  0.4)  dm  min

FA0 X (3•mol / min)(0.4)

CSTR design equation V    1714 •dm 3
 1.71•m 3

 rA X 0.0007 •mol / dm 3  min