Chemical Reaction Engineering

Stoichiometry and Rate Laws

(Examples and Practice)

Dr Asad U. Khan
Overview
Objectives

• Write the rate of reaction as a function of conversion for both liquid-

phase and gas-phase reacting systems for all the reactants
Determining Cj=hj(X) for a gas phase reaction
A mixture of 28% SO2 and 72% air is charged to a flow reactor in
which SO2 is oxidized.
2SO2  O2  2SO3
(a) First, set up a stoichiometric table using only the symbols (i.e.,
ΘI, F I ).
(b) Next, prepare a second table evaluating the species
concentrations as a function of conversion for the case when the
total pressure is 1485 kPa (14.7 atm) and the temperature is
constant at 227C.
(c) Evaluate the parameters and make a plot of each of the
concentrations SO2,
Solution
SO 3, N2 as a function of conversion

(a)Stoichiometric table.
Taking SO2 as the basis of calculation, we divide the reaction
through by the stoichiometric coefficient of our chosen basis of
calculation SO  1 O  SO
2 2 2 3
Determining Cj=hj(X) for a gas phase reaction
SO2  1 O2  SO3
2
A B C  rA kCA CB
(a) Stoichiometric table
Determining Cj=hj(X) for a gas phase reaction
(b) Expressing the concentration as a function
of conversion.
From the definition of conversion, we substitute not only for the molar flow
rate of SO2 (A) in terms of conversion but also for the volumetric flow rate
as a function of conversion F F (1  X)
CA  A
 A0

 
P0  T 
  0 (1  X)  
P  T0 
Neglecting pressure drop in the reaction, and If the reaction is also carried
out isothermally
 0 (1  X)
FA0 (1  X)  1 X 
CA  CA0  
 0 (1  X)  1  X 
Similarly for B also with T = T0 and P = P0, (i.e., p
= 1)  b  1 
  B  X  CA0   B  X 
 a   2 
C B C A0 
1  X 1  X
Determining Cj=hj(X) for a gas phase reaction
(c) Parameter evaluation
The inlet concentration of A is equal to the inlet mole fraction of A multiplied by the
total inlet molar concentration. The total concentration can be calculated from an
equation of state such as the ideal gas law. Recall that yA0 = 0.28, T0 = 500 K, and P0 =
1485 kPa.  P 
CA0 y A0CT0 y A0  0 
 RT0 
 1485kPa 
CA0 0.28  3 
 8.314kPa.dm / (mol.K)x500K 
CA0 0.1mol / dm 3
The total concentration at constant temperature and
pressure is F F  y XF F (1  X)
CT  T
 T0 A0 T0
 T0
CT0
  0 (1  X)  0 (1  X)
P0  1485kPa  3
CT0   0.357mol / dm
RT0  8.314kPa.dm3 / (mol.K)x500K 
We now evaluate 
1
 y A0  (0.28)(1  1  )  0.14
2
Determining Cj=hj(X) for a gas phase reaction
(c) Parameter evaluation
Initially, 72% of the total number of moles is air containing 21% O 2 and
79% N2, along with 28% SO2.
FA0 (0.28)(FT0 )
FB0 (0.72)(0.21)(FT0 )
FB0 (0.72)(0.21)
B   0.54
FA0 (0.28)
FI0 (0.72)(0.79)
I   2.03
FA0 (0.28)
(c) Concentrations of a function of conversion

 1 X   1 X  C X 0.1X
C A C A0   0.1   CC  A0 
 1  X   1  0.14X  1  X 1  0.14X

 1   1 

 B  X   0.54  X C A0  I (0.1)(2.03)
2 2
C B C A0   0.1   CI  
1  X 1  0.14X 1  X 1  0.14X
Determining Cj=hj(X) for a gas phase reaction
(c) Table and plot concentrations as a function of
conversion
Convesion(X) CA (SO2) CB (O2) CC (SO3) CI (N2)
0 0.1000 0.0540 0.0000 0.2030 C X 0.1X
CC  A0 
0.1 0.0913 0.0497 0.0101 0.2059 1  X 1  0.14X
0.2 0.0823 0.0453 0.0206 0.2088
0.3 0.0731 0.0407 0.0313 0.2119
CA0 I (0.1)(2.03)
0.4 0.0636 0.0360 0.0424 0.2150 CI  
1  X 1  0.14X
0.5 0.0538 0.0312 0.0538 0.2183
0.6 0.0437 0.0262 0.0655 0.2216
0.7 0.0333 0.0211 0.0776 0.2251
0.8 0.0225 0.0158 0.0901 0.2286
0.9 0.0114 0.0103 0.1030 0.2323
1 0.0000 0.0047 0.1163 0.2360

 1 X   1 X 
C A C A0   0.1 
 1  X   1  0.14X 

 1   1 
 B  X   0.54  X 
2  2 
C B C A0  0.1 
1  X 1  0.14X
Determining Cj=hj(X) for a gas phase reaction
(c) Reaction rate as a function of conversion

 rA kCA CB

 1 X 
CA CA0  
Convesion(X) CA (SO2) CB (O2) CC (SO3) CI (N2) CT -rA 1/-rA  1  X 
0 0.1000 0.0540 0.0000 0.2030 0.3570 1.0800 0.9259 C   0.5X 
0.1 0.0913 0.0497 0.0101 0.2059 0.3570 0.9072 1.1023 CB  A0 B
1  X
0.2 0.0823 0.0453 0.0206 0.2088 0.3570 0.7451 1.3420
0.3 0.0731 0.0407 0.0313 0.2119 0.3570 0.5949 1.6809  rA kCA CB
0.4 0.0636 0.0360 0.0424 0.2150 0.3570 0.4578 2.1842 (1  X)  B  0.5X 
0.5 0.0538 0.0312 0.0538 0.2183 0.3570 0.3353 2.9824  rA kCA0 2
(1  X) 2
0.6 0.0437 0.0262 0.0655 0.2216 0.3570 0.2288 4.3701
0.7 0.0333 0.0211 0.0776 0.2251 0.3570 0.1401 7.1369 2(1  X) 0.54  0.5X 
 rA 
0.8 0.0225 0.0158 0.0901 0.2286 0.3570 0.0710 14.0811 (1  0.14X) 2
0.9 0.0114 0.0103 0.1030 0.2323 0.3570 0.0236 42.4376
1 0.0000 0.0047 0.1163 0.2360 0.3570 0.0000 -  rA f (X)
Determining Cj=hj(X) for a gas phase reaction
(c) Reaction rate as a function of conversion

 rA kCA CB
45.00
 1 X 
40.00 CA CA0  
 1  X 
35.00
C   0.5X 
CB  A0 B
1  X
Reciprocal Rate (1/-rA)

30.00

25.00  rA kCA CB
20.00 (1  X)  B  0.5X 
 rA kCA0 2
15.00
(1  X) 2
2(1  X) 0.54  0.5X 
10.00  rA 
(1  0.14X) 2
5.00

0.00
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
 rA f (X)
Conversion, (X)
Reversible Reaction and Equilibrium Conversion
The reversible gas-phase decomposition of nitrogen tetroxide, N2O4, to nitrogen
dioxide, NO2, N O  2NO
2 4 2

is to be carried out at constant temperature. The feed consists of pure N2O4

at 340 K and 202.6 kPa (2 atm). The concentration equilibrium constant, KC,
at 340 K is 0.1 mol /dm3 and the rate constant is 0.5min-1.
(a) Set up a stoichiometric table and then calculate the equilibrium
conversion of N2O4 in a constant-volume batch reactor.
(b) Calculate the equilibrium conversion of N2O4 in a flow reactor.
(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.
(d) Determine the CSTR volume necessary to achieve 80% of the
equilibrium conversion.
N 2O4  2NO2
A B
At equilibrium, the concentrations of the reacting species are related by the
relationship
dictated by thermodynamics C 2
Kc  Be

CAe
Reversible Reaction and Equilibrium Conversion
(a) Batch system-constant Volume
V=V0

N A N A N A0 (1  X) N B N B 2N A0 X
CA    CA0 (1  X) CB    2CA0 X
V V0 V0 V V0 V0

y A0 P0 (1)(2atm) 3
CA0   0.07174mol / dm
RT0 (0.082 atm.dm 3 / mol.K)(340 K)

CBe 2 4C A0 2 X e 2 4C A0 X e 2
Kc   
CAe CA0 (1  X e ) (1  X e )

K c (1  X e )
Xe 
4CA0
Reversible Reaction and Equilibrium Conversion
(a) Flow System Polymath Solution

FA FA0 (1  X)  1 X 
CA   CA0  
   1  X 

FB 2FA0 X 2C X
CB    A0
  0 (1  X) (1  X)

CBe 2  2CA0 X e / (1  X e )
2

Kc  
CAe CA0 (1  X e ) / (1  X e )
4CA0 X e 2
Kc 
(1  X e )(1  X e )
K c (1  X e ) = 0.44
Batch Xe 
4CA0

K c (1  X e )(1  Xe ) K c (1  X e )(1  X e ) = 0.51

Xe  Flow Xe 
4CA0 4CA0
Note that the equilibrium conversion in a flow reactor
(i.e.,0.51 ) is greater than the equilibrium conversion in a
constant-volume batch reactor ( 0.44). Recalling Le
Châtelier's principle, can you suggest an explanation for
this difference in Xe ?
Reversible Reaction and Equilibrium Conversion
(c) If the reaction follows an elementary rate law, then

 CB2 
 rA k A  C A  
 Kc 
Batch system-constant Volume V=V0 X -rA 1/-rA
0 0.036 27.78
 4CA0 2 X 2 
 rA k A  CA0 (1  X)   0.1 0.029 34.97
 Kc  0.2 0.021 47.35
0.3 0.014 72.13
For flow
0.4 0.007 143.58
system  CA0 (1  X) 4CA0 2 X 2 
 rA k A   
 1   X K c (1  X) 2 
Substituting

0.5  mol(1  X) 4(0.072mol / dm3 ) 2 X 2 

 rA  0.072 3 
min  dm (1  X) 0.1mol / dm 3 (1  X) 2 

 (1  X) 2.88X 2   mol 
 rA 0.036    
 (1  X) (1  X) 2   dm 3 .min 
Reversible Reaction and Equilibrium Conversion
(d) CSTR Volume
Just for fun (and this really is fun), let’s calculate the CSTR reactor volume
necessary to achieve 80% of the equilibrium conversion of 51% (i.e., X= 0.8
Xe=(0.8)(0.51) = 0.4) for a molar feed rate of A of 3 mol/min.
 (1  X) 2.88X 2   mol 
 rA 0.036    
 (1  X) (1  X)2   dm3 .min 

 (1  0.4) 2.88(0.4)2   mol 

 rA 0.036    
 (1  0.4) (1  0.4)2   dm3 .min 

 mol 
 rA 0.0070  3 
 dm .min 

FA0 X FA0 (0.4)

VCSTR  
 rA X  rA 0.4

(3mol / min)(0.4)
VCSTR 
0.0070 mol 3
dm .min
VCSTR 171 dm3 or 0.171 m3
The CSTR volume necessary to achieve 40% conversion is 0.171 m3.
Expressing concentration as a function of conversion
b c d
A B C D
a a a
Liquid phase Gas phase

Flow Batch Batch Flow

NB FB
CB  CB 
FB NB V 
CB  CB  N P T F P T
 V V V0 T 0
N T0 P T0
  0 T 0
FT0 P T0
No phase No volume
change change FB FT0 P T0
  0 V V0 N N P T0
C B  B T0 CB 
FT  0 P0 T
N T V0 P0 T
 b  N B P T0 FB P T0
C B C A0   B  X  C B C T0 C B C T0
 a  N T P0 T FT P0 T
P0  T 
 y A0   0 (1  X)  
P  T0 
d c b 
     1  b 
CA0   B  X 
a a a   a   P  T0
P0 CB   
CT0  1  X  P0  T
RT0 b 
  b 
 P  CA0  B  X  C A0    X
CA0 y A0 CT0 yA0  0   a  P  
B
a 
CB    CB 
 RT0  1  X  P0  1  X
 Rate Laws

Power Law Model:

  α order in A
 rA kC A C B
β order in B
Overall Rection Order α  β

17
 Rate Laws

2A  B  3C

A reactor follows an elementary rate law if the

reaction orders just happens to agree with the
stoichiometric coefficients for the reaction as written.
e.g. If the above reaction follows an elementary rate
law 2
 rA k AC AC B
2nd order in A, 1st order in B, overall third order

18
 Rate Laws

2A+B3C
2
If  rA kC A
›Second Order in A
›Zero Order in B
›Overall Second Order

19
Elementary Rate Law Reactions

A reaction follows an elementary rate law if and only if (iff) the

stoichiometric coefficients are the same as the individual reaction order
of each species. For the reaction in the previous example
(A+B  C+D),
the rate law would be:

If 2NO+O2  2NO2

Then
-rNO = kNO (CNO)2 CO2

Example
Non-Elementary Rate Laws

If the rate law for the non-elementary reaction is A+BC+D

found to be

then the reaction is said to be 2nd order in A, 1st order in

B, and 3rd order overall.
Non-Elementary Rate Laws
Heterogeneous Reactions: In many gas-solid catalysed reactions
historically it has been practiced to write Rate law in terms of
partial pressure.

Rate law follows

Reversible Reactions

• The net rate of formation of any species is equal to its rate of

formation in the forward reaction plus its rate of formation
in the reverse reaction:

• ratenet = rateforward + ratereverse

• At equilibrium, ratenet and the rate law must reduce to an

equation that is thermodynamically consistent with the
equilibrium constant for the reaction.
• Example
Relative Rates of Reaction

aA  bB  cC  dD
b c d
A B  C  D
a a a
rA rB rC rD
  
a b c d

24
Relative Rates of Reaction
2A  B  3C
mol
 rA 10
Given dm 3 s
rA rB rC
Then  
 2 1 3
 rA mol
 rB  5
2 dm 3 s
3 mol
rC  rA 15
2 dm 3 s
25
 Reversible Elementary Reaction

Forward: Reverse:

Net:

At Equilibrium: Therefore:
Reversible Elementary Reaction
Reaction is:
kA First Order in A
A+2B
Second Order in B
3C k-A Overall third Order

moles moles
 rA   3 CA 
dm s dm3

  rA  mole dm 3 s dm 6
k   2   
 A B  mole dm mole dm 
2 2
C C 3 3 mole s
27
28
Algorithm

How to find r A  f X 

Step 1: Rate Law  rA  g Ci 

Step 2: Stoichiometry Ci  hX 

Step 3: Combine to get  rA  f X 

29
Arrhenius Equation
k is the specific reaction rate (constant) and is given by the
Arrhenius Equation.
where:
 E RT
k  Ae

T kA
k T 0 k 0
13
A 10
T

30
Arrhenius Equation
where:
E = Activation energy (cal/mol)
R = Gas constant (cal/mol*K)
T = Temperature (K)
A = Frequency factor (same units as rate constant k)
(units of A, and k, depend on overall reaction order)

Units of k

31
 Reaction Coordinate
The activation energy can be thought of as a barrier to the reaction. One
way to view the barrier to a reaction is through the reaction
coordinates. These coordinates denote the energy of the system as a
function of progress along the reaction path. For the reaction:

A  BC  A ::: B ::: C  AB  C

The reaction coordinate is:

32
33
Collision Theory

34
 Why is there an Activation Energy?
We see that for the reaction to occur, the reactants must
overcome an energy barrier or activation energy EA. The energy
to overcome their barrier comes from the transfer of the kinetic
energy from molecular collisions to internal energy (e.g.
Vibrational Energy).

1. The molecules need energy to disort or stretch their

bonds in order to break them and thus form new bonds
2. As the reacting molecules come close together they
must overcome both stearic and electron repulsion
forces in order to react.

35
 Distribution of Velocities

We will use the Maxwell-Boltzmann Distribution of Molecular

Velocities. For a species af mass m, the Maxwell distribution of
velocities (relative velocities) is:

32
 m 
f U , T  dU 4   e  mU 2 2 k BT
U 2 dU
 2 k B T 
f(U,T)dU represents the fraction of velocities between U and
(U+dU).

36
 Distribution of Velocities
A plot of the distribution function, f(U,T), is shown as a
function of U:
T1
T2 T2>T1

𝑓 (𝑈 , 𝑇 )

U
Maxwell-Boltzmann Distribution of velocities.
37
 Distribution of Velocities
32
 m 
Given f U , T  dU 4   e  mU 2 2 k BT 2
U dU
 2 k BT 
Let 1
E  mU 2
2
E
2
f  E , T  dE  1 2 k BT
E e dE
2 k BT 
32

f(E,T)dE represents the fraction of collisions that have energy

between E and (E+dE)

38
f(E,T)dE=fraction of molecules with energies between E+dE

One such distribution of energies is in the following figure:

39
Temperature Dependence of Rate Constant, k

• k is the specific reaction rate (constant) and is given by the

Arrhenius Equation:
•

k  Ae  E RT
Excel: Fitting logarithmic data

Excel Calculations
Excel: Fitting logarithmic data
Excel: Fitting logarithmic data

Activation Energy
Excel: Fitting logarithmic data

Activation Energy
Different Graph papers

Semi Log Graph Paper Log-Log Graph Paper

Thank you
 Rate Laws

• A rate law describes the behavior of a reaction. The rate of a

reaction is a function of temperature (through the rate constant) and
concentration.

• Relative Rates of Reaction

Example Relative Rates of Reaction

The Reaction:

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?
Species A, basic of calculation

The rate of disappearance of A, -ra, is

or the rate of formation of species A is

The relative rates are

 Species B

The rate of formation of species B is

The rate of disappearance of B, -rb, is

 Species C

The rate of formation of C, -rc, is