CHAPTER 3

Rate Laws and Stoichiometry: Part

2
Reactions Involving Volume Change

In a gas phase reaction a molar flow rate might change

as the reaction progresses.

N2  3H  2NH3
 Batch Reactor with Variable Volume
As such it would be a rare case (e.g. internal combustion engine),
but a good model case:

PV  ZR T T
Compressibility factor

If we divide the gas equation at any moment in time by the one at

moment zero:

 P0  T  Z  NT   NT  N 
V V         1  A0 δ.X  1 εX
0  P  T0  Z 0  NT0   NT0   NT0 

 P  T  d c b 
V  V0  0  1 εX  δ      1
 P  T0  a a a 

ε  y A0 δ
Note: function V=g(X)
 Flow Reactor with Variable Flow Rate

Using the gas equation we can derive the total concentration as:

FT P
Total concentration: CT  
 ZRT

FT0 P0
At the entrance: C T0  
 Z 0RT 0

FT P0 Z T
Total volume rate:   v0
FT0 P Z 0 T0

Fj Fj F j P Z 0 T0
Cj    C T0
v  FT P0 Z T  FT P0 Z T
 v0 
 FT0 P Z 0 T0 
 Flow Reactor with Variable Flow Rate

In a gas phase reaction a molar flow rate might change as the

reaction progresses

P0 T
  v0 1 y A0 δX 
FT P0 Z T P T0
  v0 P0 T
FT0 P Z 0 T0  v0 1 εX 
P T0

FT  FT0  FA0 .δ.X Cj 


F A0 Θ j  b / aX 
P0 T
v0 1  εX 
Gas phase C as
a function of X P T0
Expressing C as a Function of X

Batch system
Liquid
Gas
Constant volume
Useful diagram on
Text book
& Table 3.4
Flow system
Liquid
Gas
 Example 1 (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, Ɛ, Θ)

a. The liquid-phase reaction

O H2S O4 CH2 OH
+ H2O
H2C CH2 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.
 Solution 1
a. Liquid-phase reaction

O H2S O4 CH2 OH
+ H2O
H2C CH2 CH2 OH

A  B 
 C
 Liquid phase reaction → stoichiometric table, batch = flow reactor
NA/V = NA/Vo = CA

Species Symbol Initial Change Remaining

CH2 OH
C A  11 X 
O
H2C CH2
+ HA
2O C A0CH
 1Ibmol/ft
OH
3
 C A0 X
2
CH2 OH
H2C
O
CH2
+ H2O B C B0  3.47Ibmol/ft3  C A0 X C B  3.47  X 
CH2 OH
CH2 OH
H2O C 0  C A0 X CC  X
CH2 OH
 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, Ɛ, Θ)

b. The isothermal, isobaric gas-phase pyrolysis

CH2H6 → 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 were would your
equation to be carried out in a constant-volume BATCH REACTOR.
 Solution 2 (Cont.)
b. Isothermal, isobaric, gas-phase pyrolysis

CH2H6 → C2H4 + H2

A 
 B  C

Species Symbol Initial Change Remaining

CH2H6 A FA0  FA0 X FA  FA0 1 X 

C2H4 B 0  FA0 X FB  FA0 X

H2 C 0  FA0 X FC  FA0 X

FT  FA0 FT  FA0 1 X 

 Solution 2 (Cont.)
Gas phase, constant T, no P drop

   o 1 εX 
ε  y AO δ  11 1 1  1
   o 1 X 

CA 
FA

FA0 X
 C A0
1 X 
  O 1 X  1 X 
FB FC FA0 X X
CB   CC    C A0
   O 1 X  1 X

C A0  y A0 C T0  y A0
P0

16atm  0.067
kmol
 0.067
mol
RT 0 0.82m3 .atm m3 dm3
1100K
kmol.K
Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
 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
A→C
Is irreversible at low temperatures, and the rate law is
-rA = kCA
 Solution 3 (Cont.)
a. At high temperature
A  B  C 
 rA  k1 C A  B 
At equilibrium, we know K  C Be  KC 
C
from thermodynamics: C Ae
At equilibrium, -rA = 0

 rA  k1C A  k 2C B  CB 
0  k1 C A 
 
 KC 
 k2  k
 rA  k1 C A  C B   K C  1 C Be
 k1  k2 KC 
C Ae
 Example 4 (V Change)
For reaction below calculate
a. Equilibrium conversion in a constant batch reactor;
b. Equilibrium conversion in a flow reactor;
c. Assuming the reaction is elementary, express the rate of
the reaction;

Assume the feed is pure N2O4 at 340K and 202.6 kPa.

Concentration equilibrium constant: KC = 0.1mol/l; kA = 0.5 min-1

N2O4  2NO2
 Solution 4
Batch reactor
Species Symbol Initial Change Remaining

N2O4 A NA0  NA0 X NA  NA0 1 X 

NO2 B 0  2NA0 X  NB  2NA0 X

NT0  NA0 NT  NT0  NAO X

Equilibrium conversion:
C Be 4C 2A0 X 2e 4C A0 X 2e K C 1 X e 
2
KC    Xe 
C Ae C A0 1 X e  1 X e 4C A0

y A0P0
C A0   0.071mol/dm3 Xe = 0.44
RT 0
 Solution 4 (Cont.)
Flow reactor
FA0 1 X  C A0 1 X 
FA y A0P0
CA    C A0   0.071mol/dm3
  0 1 εX  1 εX RT 0

C A0 X
CB 
1 εX K C 1 X e 1 εX e 
Xe 
4C A0
C Be
2
4C 2A0 X 2e
KC  
C Ae C A0 1 X e 
4C A0 X 2e

1 X e 1 εX e  Xe = 0.51
 Solution 4 (Cont.)
Rate laws
 C B2 
 rA  k A C A  
 K C 

 4C 2A0 X 2 
• Constant volume:  rA  k A C A0 1 X   
 K C 

 C A0 1 X  4C 2A0 X 2 
• Flow:  rA  k A   2
 1  εX K C 1  εX  