Chemical Reaction Engineering

(CHEN 351)

Lecture 3:
Rate Laws & Stoichiometry
After completing Chapter 3 the students will be able to:
Write the rate of reaction as a function of conversion for both
liquid and gas phase reaction

Set up a stoichiometric table for a given reaction system

Write the rate law for different species involved in a reaction

with respect to the reference species
➢ Types of Reaction
▪ Homogeneous reaction: one phase only
▪ Heterogeneous reaction: more than one phase
▪ Irreversible reaction
𝐴+𝐵 →𝐶

▪ Reversible reaction
𝐴+𝐵 𝐶
➢ Relative rate of reaction
▪ Relate reaction rate of one species to another
▪ Consider the general equation
𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷
▪ We will choose A as our basis of calculation

𝑏 𝑐 𝑑
𝐴+ 𝐵 → 𝐶+ 𝐷
𝑎 𝑎 𝑎
▪ Reaction stoichiometry is then given by:
−𝑟𝐴 −𝑟𝐵 𝑟𝐶 𝑟𝐷
= = =
𝑎 𝑏 𝑐 𝑑
➢ Rate law (or kinetic expression)
Describes behaviour of reaction and given as:
−𝑟𝐴 = 𝑘𝐶𝐴𝑛
Affected by both concentration and temperature
➢ Reaction order
𝛽
−𝑟𝐴 = 𝑘𝐶𝐴𝛼 𝐶𝐵
Overall reaction order
𝑛 =𝛼+𝛽
➢ Reaction rate constant (k)
Units of k depends on reaction order

CA -rA Reaction Order Rate Law k

(mol/dm3) (mol/dm3*s) zero -rA = k (mol/dm3*s)

(mol/dm3) (mol/dm3*s) 1st -rA = kCA s-1

(mol/dm3) (mol/dm3*s) 2nd -rA = kCA2 (dm3/mol*s)

➢ Elementary Rate Laws
A reaction follows an elementary rate law if and only if the
stoichiometric coefficients are the same as the individual reaction
order of each species.
Example:
𝐴+𝐵 →𝐶+𝐷
Rate law for stoichiometric reaction
−𝑟𝐴 = 𝑘𝐶𝐴 𝐶𝐵
➢ Non-elementary reaction includes
Homogeneous reaction in which the overall order of reaction is not an
integer
Example: Gas phase synthesis of phosgene
𝐶𝑂 + 𝐶𝑙2 → 𝐶𝑂𝐶𝑙2
3/2
−𝑟𝐶𝑂 = 𝑘𝐶𝐶𝑂 𝐶𝐶𝑙2
➢ Non-elementary reaction includes
Reaction which proceeds via free radical mechanism

𝐻2 + 𝐵𝑟2 2𝐻𝐵𝑟

1/2
𝑘1 𝐶𝐻2 𝐶𝐵𝑟2
𝑟𝐻𝐵𝑟 =
𝐶
𝑘2 + 𝐻𝐵𝑟
𝐶𝐵𝑟2
➢ Reversible reaction
➢ The net rate of formation of any species is:
𝐴+𝐵 𝐶+𝐷
𝑟𝑛𝑒𝑡 = 𝑟𝑓𝑜𝑟𝑤𝑎𝑟𝑑 + 𝑟𝑟𝑒𝑣𝑒𝑟𝑠𝑒
At equilibrium, 𝑟𝑛𝑒𝑡 and the rate law must reduce to an equation that is
thermodynamically consistent with the equilibrium constant for the
reaction.
➢ Concentration of species at EQUILIBRIUM is related to the
Concentration Equilibrium Constant through:

𝑐 𝑑
𝐶𝐶𝑒 𝐶𝐷𝑒
𝐾𝐶 = 𝑎 𝑏
𝐶𝐴𝑒 𝐶𝐵𝑒

𝑚𝑜𝑙 𝑑+𝑐−𝑏−𝑎
➢ Unite of 𝐾𝐶 =
𝑑𝑚3
➢ Rate Constant, k:
▪ Independent of concentration
▪ Dependent on temperature through Arrhenius Law
▪ Also affected by the presence of catalyst
𝑘𝐴 𝑇 = 𝐴𝑒 −𝐸 Τ𝑅𝑇

kA = specific rate constant

T = absolute temperature, K
A = pre-exponential factor or frequency factor or Arrhenius constant
E = activation energy, J/mol
R = gas constant, 8.314 J/mol.K
➢ Activation energy, E
▪ Refers to the barrier to energy transfer between reacting
molecules that must be overcome before reaction takes place
𝐴 + 𝐵𝐶 𝐴 − 𝐵 − 𝐶 → 𝐴𝐵 + 𝐶
➢ Activation energy, E
▪ Large E (more than 60 kcal/mole) – very sensitive to
temperature change
▪ Determine experimentally
𝑘𝐴 𝑇 = 𝐴𝑒 −𝐸 Τ𝑅𝑇

𝐸 1
ln 𝑘 = ln 𝐴 −
𝑅 𝑇
 Calculate the activation energy for the decomposition of benzene
diazonium chloride to give chlorobenzene and nitrogen using the
following information for 1st order reaction

k(s-1) 0.00043 0.00103 0.018 0.0035 0.00717

T(K) 313 319 323 328 333

Solution
k(s-1) 0.00043 0.00103 0.018 0.0035 0.00717

T(K) 313 319 323 328 333

ln k -7.75 -6.88 -6.32 -5.64 -4.94
1/T (K-1) 0.00320 0.00314 0.00310 0.00305 0.00300
Solution
-4.00000
ln k = -14006/T + 37.084
-5.00000
ln k

-6.00000

-7.00000

-8.00000
0.00295 0.00300 0.00305 0.00310 0.00315 0.00320 0.00325
1/T

➢ From our previous plot we get:

14006
ln 𝑘 = − + 37.12
𝑇
14006
➢ Rearrange ln 𝑘 = 37.12 − 𝑇
➢ From this we know that
ln 𝐴 = 37.12
𝐴 = exp 37.12 = 1.32 × 1016 𝑠 −1
𝐸
= 14006 𝐾
𝑅
𝐸 = 14006𝑅 = 116,445.9 𝑘𝐽/𝑚𝑜𝑙
If this reaction is elementary
1
𝐴+ 𝐵 →𝐶
2
a) What is the reaction rate law 𝑟𝐵 , 𝑟𝐶 and the unite of the rate constant?
b) Calculate the rates of A, B, and C where the concentration are 𝐶𝐴 = 1.5 𝑚𝑜𝑙
1
/𝑑𝑚3 , 𝐶𝐵 = 9 𝑚𝑜𝑙/𝑑𝑚3 and 𝑘 = 2 𝑑𝑚3 Τ𝑚𝑜𝑙 2 (1Τ𝑠)

Solution
1/2
a) −𝑟𝐴 = 𝑘𝐶𝐴 𝐶𝐵
−𝑟𝐴 = −2𝑟𝐵

1 𝑘 1/2
𝑟𝐵 = 𝑟𝐴 = 𝐶𝐴 𝐶𝐵
2 2
−𝑟𝐴 = 𝑟𝐶
1/2
𝑟𝐶 = 𝑘𝐶𝐴 𝐶𝐵
Solution

b)

1/2
−𝑟𝐴 = 𝑘𝐶𝐴 𝐶𝐵

−𝑟𝐴 = 2 × 1.5 × (9)1/2 = 9 𝑚𝑜𝑙 Τ𝑑𝑚3 . 𝑠

𝑟𝐵 = −4.5 𝑚𝑜𝑙 Τ𝑑𝑚3 . 𝑠

𝑟𝐶 = 9 𝑚𝑜𝑙 Τ𝑑𝑚3 . 𝑠
 Rate Law
➢ To relate the concentration of different species to each other for a
single reaction
➢ For heterogeneous reaction the rate law can be expressed in terms
of partial pressures rather than concentrations.
➢ An example of a heterogeneous reaction and corresponding rate
law is the hydrodomethylation of toluene (T) to form benzene (B)
and methane (M) carried out over a solid catalyst.
𝐶𝑎𝑡
𝐶6 𝐻5 𝐶𝐻3 + 𝐻2 𝐶6 𝐻6 + 𝐶𝐻4

𝑘𝑃𝐻2 𝑃𝑇
−𝑟𝑇′ =
1 + 𝐾𝐵 𝑃𝐵 + 𝐾𝑇 𝑃𝑇
where KB and KT are the adsorption constants with units of kPa-I (or
atm-I) and the specific reaction rate has units of (k=mol/kg.kPa2)
➢ To express the rate of reaction in terms of concentration rather than
partial pressure, we simply substitute for P, using the ideal gas law
𝑃𝑖 = 𝐶𝑖 𝑅𝑇
➢ The rate of reaction per unit weight catalyst, −𝑟𝑖′ , and the rate of
reaction per unit volume, −𝑟𝑖 , are related through the bulk density
ρ, (mass of solid/volume) of the catalyst particles in the fluid media:
−𝑟𝑖 = 𝜌𝑏 (−𝑟𝑖′ )
 Batch Reactor

at t = 0 at t = t

NA0 NA
NB0 NB
NC0 NC
ND0 ND
NI
NI0
 Stoichiometry

❑ Stoichiometric relation will help relate the following quantities

▪ Rate of reactions
▪ Concentration
▪ Flows
▪ Conversions
 Stoichiometry

𝑁𝐵0 𝐶𝑗0 𝑦𝑗0

Θ𝑗 = = =
𝑁𝐴0 𝐶𝐴0 𝑦𝐴0
➢ The change in the total number of moles per mole of A reacted.
𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷

𝑑 𝑐 𝑏
𝛿 = + − −1
𝑎 𝑎 𝑎
Valid for constant
𝑁𝑗 volume system
𝐶𝑗 =
𝑉
 Stoichiometry
Stoichiometric Table

Species Symbol Initial Change Remaining

(reacted)
A A NA0 - (a/a) NA0X NA = NA0 (1-X)

B B NB0 = NA0B -(b/a) NA0X NB = NA0[B-(b/a)X]

C C NC0 = NA0C (c/a)NA0X NC = NA0[C+(c/a)X]

D D ND0 = NA0D (d/a)NA0X ND = NA0[D+(d/a)X]

Inert I NI0 = NA0I - NI0 = NA0I

Total NT0 NT = NT0 + [d/a + c/a –

b/a – 1]NA0X
NT = NT0 + NA0X
 Example
A. The saponification reaction for aqueous sodium hydroxide and glyceryl
acetate is given below. Set up the stoichiometric table if the reaction takes
place in a batch reactor system. Take sodium hydroxide as your reference
species.
3𝑁𝑎𝑂𝐻 + 𝐶17 𝐻35 𝐶𝑂𝑂 3 𝐶3 𝐻5 → 3𝐶17 𝐻35 𝐶𝑂𝑂𝑁𝑎 + 𝐶3 𝐻5 (𝑂𝐻)3

B. If the initial mixture consist of 10 mol/L sodium hydroxide (A) and 2

mol/L of glyceryl stearate (B), what is the concentration of glycerine (C)
when the conversion of sodium hydroxide is:
(a) 20%,
(b) 90%
Solution
A. The reaction can be simplified as:

1 1
𝐴+ 𝐵 →𝐶+ 𝐷
3 3
Liquid phase reaction:  is constant,
V is constant, V=V0

𝑁𝐴 𝑁𝐴 𝑁𝐴0 (1 − 𝑋)
𝐶𝐴 = = = = 𝐶𝐴0 1 − 𝑋
𝑉 𝑉0 𝑉0

𝑁𝐵 𝑁𝐴0 𝑏 𝑏
𝐶𝐵 = = (Θ𝐵 − 𝑋) = 𝐶𝐴0 (Θ𝐵 − 𝑋)
𝑉 𝑉0 𝑎 𝑎

𝐶𝐵0 𝑁𝐵0
Θ𝐵 = =
𝐶𝐴0 𝑁𝐴0

𝐶𝐶0
Θ𝐶 =
𝐶𝐴0

𝐶𝐷0
Θ𝐷 =
𝐶𝐴0
Solution

Stoichiometric table for L-phase soap reaction

Species Initial Change (reacted) Remaining

A NA0 - NA0X NA = NA0 (1-X)

B NB0 = NA0B -(1/3) NA0X NB = NA0[B-(1/3)X]

C NC0 = NA0C 1NA0X NC = NA0[C+1X]

D ND0 = NA0D (1/3)NA0X ND = NA0[D+(1/3)X]

Inert NI0 = NI0/NT0 - NI0 = NI0/NT

Total NT0 NT = NT0 + [1/3+ 1 – 1/3 –

1]NA0X
NT = NT0
Solution

B.
At t = 0, CC = CD = 0, C= D
(a) 20% conversion of A: (X=0.2)

𝑋 𝑚𝑜𝑙 0.2
𝐶𝐶 = 𝐶𝐴0 = 10 = 0.67 𝑚𝑜𝑙/𝐿
3 𝐿 3

𝑋 𝑚𝑜𝑙 2 0.2
𝐶𝐵 = 𝐶𝐴0 Θ𝑏 − = 10 − = 1.333 𝑚𝑜𝑙/𝐿
3 𝐿 10 3

(b) 90% conversion of A: (X=0.9)

3𝐴 + 𝐵 → 3𝐶 + 𝐷
90% conversion of A is not possible
B is limiting reactant!!!
 Flow Reactors

FA0 FA
FB0 b c d FB
FC0 A+ B→ C+ D FC
a a a
FD0 FD
FI0 FI

FA0
FB0
b c d FA
FC0 A+ B→ C+ D
a a a FB
FD0
FC
FI0
FD
FI
 Stoichiometry
Stoichiometric Table
Species Symbol Initial Change Remaining

A A FA0 - FA0X FA = FA0 (1-X)

B B FB0 = FA0B -(b/a) FA0X FB = FA0[B-(b/a)X]

C C FC0 = FA0C (c/a)FA0X FC = FA0[C+(c/a)X]

D D FD0 = FA0D (d/a)FA0X FD = FA0[D+(d/a)X]

Inert I FI0 = FA0I - FI0 = FA0I

Total FT0 FT = FT0 + [d/a + c/a – b/a-a]FA0X

FT = FT0 + FA0X

𝐹𝑗0 𝐶𝑗0 𝑣0 𝐶𝑗0 𝑦𝑗0 𝑑 𝑐 𝑏

Θ𝑗 = = = = 𝛿= + − −1
𝐹𝐴0 𝐶𝐴0 𝑣0 𝐶𝐴0 𝑦𝐴0 𝑎 𝑎 𝑎
 Stoichiometry

𝐹𝑗0 𝐶𝑗0 𝑣0 𝐶𝑗0 𝑦𝑗0

Θ𝑗 = = = =
𝐹𝐴0 𝐶𝐴0 𝑣0 𝐶𝐴0 𝑦𝐴0
➢ The change in the total number of moles per mole of A reacted.

𝑑 𝑐 𝑏
𝛿 = + − −1
𝑎 𝑎 𝑎
𝐹𝑗 Valid for constant
𝐶𝑗 =
𝑉 volume system
➢ For liquid phase system (no phase change, constant volume);
𝑣 = 𝑣0
𝐶𝐴 = 𝐶𝐴0 (1 − 𝑋)
➢ For gas phase system, the above is not true; need to account for
volume expansion
 Volume change with reaction (gas
phase): Batch System
➢ Occur when a system does not have an equal no of product and reactant,
(usually involve gas phase system)
➢ Need to take into account the expansion factor, 𝜀

𝑑 𝑐 𝑏
𝑁𝑇 − 𝑁𝑇0 + − − 1 𝑁𝐴0
𝑎 𝑎 𝑎
𝜀= Or ε= = 𝑦𝐴0 𝛿
𝑁𝑇0 𝑋 𝑁𝑇0

➢ If the total number of moles converted per mole of reactant A is 𝛿,

conversion if X, the total number of moles after the reaction is:

𝑁𝑇
𝑁𝑇 = 𝑁𝑇0 + 𝛿𝑁𝐴0 𝑋 𝑂𝑟 = 1 + 𝛿𝑦𝐴0 𝑋
𝑁𝑇0
➢ The real gas law 𝑃𝑉 = 𝑍𝑁𝑇 𝑅𝑇
➢ At initial condition the volume in the reactor is given by:
𝑃0 𝑉0 = 𝑍0 𝑁𝑇0 𝑅𝑇0
 Volume change with reaction (gas
phase)
➢ The reactor volume at any time is given by :

𝑃0 𝑇𝑍𝑁𝑇
𝑣 = 𝑣0
𝑃 𝑇0 𝑍0 𝑁𝑇0
➢ The volume at anytime for an ideal gas (𝑍 = 𝑍0 ) is:

𝑃0 𝑇 𝑃0 𝑇
𝑣 = 𝑣0 1 + 𝛿𝑦𝐴0 𝑋 𝑂𝑟 𝑣 = 𝑣0 (1 + 𝜀𝑋)
𝑃 𝑇0 𝑃 𝑇0
➢ Combining the compressibility factor equation of state (𝑍 = 𝑍0 ) and
𝑃
stoichiometry (𝐶𝑇 = 𝑍𝑅𝑇, 𝐹𝑇 = 𝐶𝑇 𝑣)

𝑃0
𝐶𝑇0 = & 𝐹𝑇0 = 𝐶𝑇0 𝑣0
𝑍0 𝑅𝑇0

𝐹𝑇 𝑃0 𝑇 𝑃0 𝑇
𝑣 = 𝑣0 = 𝑣0 (1 + 𝜀𝑋)
𝐹𝑇0 𝑃 𝑇0 𝑃 𝑇0
 Gas Phase Flow System

𝐹𝑗 𝐹𝑗 𝐹𝑇0 𝐹𝑗 𝑃 𝑇0
𝐶𝑗 = = =
𝑉 𝑉 𝐹𝑇 𝑃0 𝑇 𝑉0 𝐹𝑇 𝑃0 𝑇
0 𝐹
𝑇0 𝑃 𝑇0

𝐹𝑗 𝑃 𝑇0
𝐶𝑗 = 𝐶𝑇0
𝐹𝑇 𝑃0 𝑇

Or

𝐹𝑗 𝐹𝑗 𝐹𝐴0 (Θ𝑗 + 𝑣𝑗 𝑋) 𝐶𝐴0 (Θ𝑗 + 𝑣𝑗 𝑋) 𝑇0 𝑃

𝐶𝑗 = = = =
𝑉 𝑉 (1 + 𝜀𝑋) 𝑃0 𝑇 𝑉 (1 + 𝜀𝑋)
𝑃0 𝑇 (1 + 𝜀𝑋) 𝑇 𝑃0
0 𝑃 𝑇0 0 𝑃 𝑇0

𝐹𝑇 = 𝐹𝐴 + 𝐹𝐵 + 𝐹𝐶 + 𝐹𝐷 + 𝐹𝐼 + ⋯ = ෍ 𝐹𝑗
𝑗=1
 Constant Volume Variable Volume (constant P &T)

Batch System Flow System Batch System Flow System

𝑁𝑗
𝐶𝑗 = 𝐹𝑗
𝑉(𝑅𝑒𝑎𝑐𝑡𝑜𝑟 𝐶𝑗 = 𝑉 = 𝑉0 (1 + 𝜀𝑋) 𝑣 = 𝑣0 (1 + 𝜀𝑋)
𝑣 (𝑣𝑜𝑙𝑢𝑚𝑒𝑡𝑟𝑖𝑐
𝑣𝑜𝑙𝑢𝑚𝑒)
𝑓𝑙𝑜𝑤𝑟𝑎𝑡𝑒)

𝐶𝐵 = 𝐶𝐴0 Θ𝐵 − 𝑏Τ/𝑎 𝑋 𝐶𝐴0 Θ𝐵 − 𝑏Τ/𝑎 𝑋

𝐶𝐵 =
𝑦𝐴0 𝑃0 1 + 𝜀𝑋
𝐶𝐴0 =
𝑅𝑇0
Concentration in Variable Volume Gas Flow System
 Example

A mixture of 28% SO2 and 72% air is changed to a flow reactor in which
SO2 is oxidized
2𝑆𝑂2 + 𝑂2 → 2𝑆𝑂3
a) Set up a stoichiometric table
b) Prepare a second stoichiometric table evaluating numerically as many
symbols as possible for the case when the total pressure is 1485 kPa
and temperature is constant at 227oC
Solution

Initially 72% of the total number of moles is air containing (21% O2

and 79% N2) along with 28% SO2
𝐹𝐴0 = 0.28 𝐹𝑇0
𝐹𝐵0 = (0.72)(0.21) 𝐹𝑇0

𝐹𝐵0 0.72 × 0.21

Θ𝐵 = = = 0.54
𝐹𝐴0 0.28

𝐹𝐼0 0.72 × 0.79

Θ𝐼 = = = 2.03
𝐹𝐴0 0.28
Solution

Species Symbol Initial Change Remaining

SO2 A FA0 - FA0X FA = FA0 (1-X)

O2 B FB0 = FA0B -(1/2) FA0X FB = FA0[B-(1/2)X]

SO3 C FC0 = FA0C FA0X FC = FA0[C+X]

N2 I FI0 = FA0I - FI0 = FA0I

Total FT0 FT = FT0 + [1-1/2-1]FA0X

FT = FT0 - 1/2FA0X

𝐹𝐴 𝐹𝐴0 (1 − 𝑋)
𝐶𝐴 = =
𝑣 𝑣
𝑃0 𝑇
𝑣 = 𝑣0 (1 + 𝜀𝑋)
𝑃 𝑇0
Solution

Neglecting pressure drop in the reaction, P= P0, and at isothermal

condition, yields
𝑣 = 𝑣0 (1 + 𝜀𝑋)

𝐹𝐴0 (1 − 𝑋) 1−𝑋
𝐶𝐴 = = 𝐶𝐴0
𝑣0 (1 + 𝜀𝑋) 1 + 𝜀𝑋

𝑃0 1485
𝐶𝐴0 = 𝑦𝐴0 𝐶𝑇0 = 𝑦𝐴0 = 0.28 = 0.1 𝑚𝑜𝑙/𝑑𝑚3
𝑅𝑇0 8.314 × 500

𝐹𝑇 𝐹𝑇0 + 𝑦𝐴0 𝛿𝑋𝐹𝑇0 𝐹𝑇0 (1 + 𝜀𝑋) 𝑃0

𝐶𝑇 = = = = 𝐶𝑇0 =
𝑣 𝑣0 (1 + 𝜀𝑋) 𝑣0 (1 + 𝜀𝑋) 𝑅𝑇0

1485
= = 0.357 𝑚𝑜𝑙/𝑑𝑚3
8.314 × 500
Solution

1
𝜀 = 𝑦𝐴0 𝛿 = 0.28 1 − − 1 = −0.14
2

1−𝑋 1−𝑋
𝐶𝐴 = 𝐶𝐴0 = 0.1
1 + 𝜀𝑋 1 − 0.14𝑋

𝑏 1
Θ𝐵 − 𝑎 𝑋 0.54 − 𝑋
𝐶𝐵 = 𝐶𝐴0 = 0.1 2
1 + 𝜀𝑋 1 − 0.14𝑋

𝐶𝐴0 𝑋 0.1𝑋
𝐶𝐶 = =
1 + 𝜀𝑋 1 − 0.14𝑋

𝐶𝐴0 Θ𝐼 0.1(2.03)
𝐶𝐼 = =
1 + 𝜀𝑋 1 − 0.14𝑋

2
1 − 𝑋 Θ𝐵 − 0.5𝑋 2(1 − 𝑋)(0.54 − 0.5𝑋)
−𝑟𝐴 = 𝑘𝐶𝐴 𝐶𝐵 = 𝑘𝐶𝐴0 =
1 + 𝜀𝑋 2 (1 − 0.14𝑋)2
➢ Rate law for reversible reaction must
▪ Satisfy thermodynamic relationships at equilibrium and
▪ Reduce to the irreversible rate law when the concentration of
one or more of the reaction products is zero
𝑎𝐴 + 𝑏𝐵 𝑐𝐶 + 𝑑𝐷
➢ Thermodynamic equilibrium relationship

𝑐 𝑑 𝑐+𝑑−𝑎−𝑏
𝐶𝐶𝑒 𝐶𝐷𝑒 𝑚𝑜𝑙
𝐾𝐶 = 𝑎 𝑏 =
𝐶𝐴𝑒 𝐶𝐵𝑒 𝑑𝑚3

➢ Everything is the same as for the irreversible case, except for the rate
law:

𝐶𝐶 𝐶𝐷
−𝑟𝐴 = 𝑘𝐴 𝐶𝐴 𝐶𝐵 −
𝐾𝐶
 𝑎𝐴 + 𝑏𝐵 𝑐𝐶 + 𝑑𝐷
𝐶𝐶 𝐶𝐷
−𝑟𝐴 = 𝑘𝐴 𝐶𝐴 𝐶𝐵 −
𝐾𝐶
➢ Where:
𝑁0 (1 − 𝑋)
𝐶𝐴 =
𝑉
(𝐹𝐵0 𝑡 − 𝑁0 𝑋)
𝐶𝐵 =
𝑉
𝑁0 𝑋
𝐶𝐶 = 𝐶𝐷 =
𝑉
➢ At equilibrium −𝑟𝐴 = 0, then

𝑐 𝑑
𝐶𝐶𝑒 𝐶𝐷𝑒 𝑁𝐶𝑒 𝑁𝐷𝑒
𝐾𝐶 = 𝑎 𝑏 =
𝐶𝐴𝑒 𝐶𝐵𝑒 𝑁𝐴𝑒 𝑁𝐵𝑒

𝑁𝐴0 𝑋𝑒2
𝐾𝐶 =
(1 − 𝑋𝑒 )(𝐹𝐵0 𝑡 − 𝑁𝐴0 𝑋𝑒 )
Example
 Example

The reversible gas-phase decomposition of nitrogen tetroxide, N2O4,,

𝑁2 𝑂4 2N𝑂2

is 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.
a) Express the equilibrium conversion of N2O4 in a constant-volume
batch reactor, in term of CA0 and KC.
b) Express the equilibrium conversion of N2O4 in a flow reactor, in
term of CA0 and KC
c) Assuming the reaction is elementary, express the rate of reaction
solely as a function of conversion for a constant-volume batch and a
flow system.
d) If kA is 0.5 min-1and feed rate is 3 mol/min, determine the CSTR
volume necessary to achieve 80% of the equilibrium conversion
Solution
a. 𝑁2 𝑂4 2N𝑂2

𝐴 2B
2
𝐶𝐵𝑒
𝐾𝐶 =
𝐶𝐴𝑒
Batch system-constant volume, V = V0
Species Initial Change (reacted) Remaining

A NA0 - NA0X NA = NA0 (1-X)

B 0 2NA0X NB = 2NA0X

NT=NA0 NT=NT0+NA0X

𝑁
For batch system 𝐶𝑖 = 𝑉𝑖
𝑁𝐴 𝑁𝐴 𝑁𝐴0 (1 − 𝑋)
𝐶𝐴 = = = = 𝐶𝐴0 (1 − 𝑋)
𝑉 𝑉0 𝑉0
𝑁𝐵 𝑁𝐵 2𝑁𝐴0 𝑋
𝐶𝐵 = = = = 2𝐶𝐴0 𝑋
𝑉 𝑉0 𝑉0
Solution

𝑦𝐴0 𝑃0 (1)(2 𝑎𝑡𝑚)

𝐶𝐴0 = = 3 = 0.07174 𝑚𝑜𝑙 Τ𝑑𝑚3
𝑅𝑇0 (0.082 𝑎𝑡𝑚. 𝑑𝑚 Τ𝑚𝑜𝑙. 𝐾)(340 𝐾)
At equilibrium X=Xe

2 2 2
𝐶𝐵𝑒 4𝐶𝐴0 𝑋𝑒 4𝐶𝐴0 𝑋𝑒2
𝐾𝐶 = = =
𝐶𝐴𝑒 𝐶𝐴0 (1 − 𝑋𝑒 ) 1 − 𝑋𝑒

𝐾𝐶 (1 − 𝑋𝑒 )
𝑋𝑒 = = 0.44
4𝐶𝐴0
Solution

𝐹𝑖
For flow system 𝐶𝑖 = 𝑉

𝐹𝐴 𝐹𝐴0 (1 − 𝑋) 𝐹𝐴0 (1 − 𝑋) 𝐶𝐴0 (1 − 𝑋)

𝐶𝐴 = = = =
𝑣 𝑣 𝑣0 (1 + 𝜀𝑋) 1 + 𝜀𝑋

𝐹𝐵 2𝐹𝐴0 𝑋 2𝐶𝐴0 𝑋
𝐶𝐵 = = =
𝑣 𝑣0 (1 + 𝜀𝑋) 1 + 𝜀𝑋

2
𝐶𝐵𝑒 (2𝐶𝐴0 𝑋𝑒 Τ1 + 𝜀𝑋𝑒 )2 4𝐶𝐴0 𝑋𝑒2
𝐾𝐶 = = =
𝐶𝐴𝑒 𝐶𝐴0 (1 − 𝑋𝑒 )Τ(1 + 𝜀𝑋𝑒 ) (1 − 𝑋𝑒 )(1 + 𝜀𝑋𝑒 )
𝑋𝑒 = 0.51
Solution
c. Rate laws. Assuming that the reaction follows an elementary rate law, then

𝐶𝐵2
−𝑟𝐴 = 𝑘𝐴 𝐶𝐴 −
𝐾𝐶

1. For a constant volume (V= V0) batch system.

2 2
𝐶𝐵2 4𝐶𝐴0 𝑋
−𝑟𝐴 = 𝑘𝐴 𝐶𝐴 − = 𝑘𝐴 𝐶𝐴0 1 − 𝑋 −
𝐾𝐶 𝐾𝐶

2. For flow system

2 2
𝐶𝐴0 1 − 𝑋 4𝐶𝐴0 𝑋
−𝑟𝐴 = 𝑘𝐴 −
1 + 𝜀𝑋 𝐾𝐶 (1 + 𝜀𝑋)2

0.072 1 − 𝑋 4(0.0722 )𝑋 2
−𝑟𝐴 = 0.5 −
1+𝑋 0.1(1 + 𝑋)2

1−𝑋 2.88𝑋 2
−𝑟𝐴 = 0.0036 −
1+𝑋 (1 + 𝑋)2
Solution

We can now form our Levenspiel plot.

That (I/-rA) goes to infinity as X approaches Xe.
Solution

(d) CSTR volume. let's calculated the CSTR reactor volume necessary to
achieve 80% of the equilibrium conversion of 50% {i.e., X = 0.8Xe)
X = 0.4 for a feed rate of 3 mol/min.

2
1 − 0.4 2.88 0.4
−𝑟𝐴 = 0.0036 − 2
= 0.00070
1 + 0.4 1 + 0.4

𝐹𝐴0 𝑋 3 (0.4)
𝑉= = = 1.714 𝑑𝑚3
−𝑟𝐴 0.00070
➢ Given –rA as a function of conversion, -rA= f(X), one can size any type
of reactor.

➢ We do this by constructing a Levenspiel plot.

➢ Here we plot either (FA0/-rA) or (1/-rA) as a function of X.

➢ For (FA0/-rA) vs. X, the volume of a CSTR and the volume of a PFR can
be represented as the shaded areas in the Levenspiel Plots.
Sizing CSTRs
❑ We can determine the volume of the CSTR required to achieve a specific
conversion if we know how the reaction rate rA depends on the conversion XA

𝑋
𝑉𝐶𝑆𝑇𝑅 = 𝐹𝐴0 Volume is product
−𝑟𝐴
of FA0/-rA and X A
• Plot FA0/-rA vs XA (Levenspiel plot)
• VCSTR is the rectangle with a base of XA,exit and a height of FA0/-rA

Area = Volume of CSTR

FA0
-r A

X1
X
 Sizing PFRs
❑ We can determine the required volume of a PFR to achieve a specific
conversion if we know how the reaction rate −𝑟𝐴 depends on the conversion
XA
𝑋𝐴,𝑒𝑥𝑖𝑡 𝐹𝐴0
Volume is product
𝑉𝑃𝐹𝑅 = ‫׬‬0 𝑑𝑋 of FA0 /-rA and XA
−𝑟𝐴

• Plot FA0/-rA vs XA (Experimentally determined numerical values)

• VPFR is the area under the curve FA0/-rA vs XA,exit

Area=Volume of PFR
FA
-rA

X1
X
Numerical Evaluation of Integrals
 Example
The gas phase reaction 𝐴 → 𝐵 is carried out in a PFR. Using data in
the following Table calculate the volume required to achieve 40%
conversion. Shade the area on the Levenspiel plot that corresponds to
this conversion.

XA 0 0.1 0.2 0.4 0.6 0.7 0.8

FA0/-rA 0.89 1.08 1.33 2.05 3.56 5.06 8

We do not have an expression for –rA as a

function of XA

We need to Numerically evaluate the area under

the curve
Solution

VPFR for XA = 0.4?

𝑋 𝐹
𝑉𝑃𝐹𝑅 = ‫׬‬0 𝐴,𝑒𝑥𝑖𝑡 −𝑟𝐴0 𝑑𝑋
𝐴

Use Simpson’s one-third rule (3-point):

𝑋2 − 𝑋0 0.4 − 0
ℎ= = = 0.2
2 2

𝑋1 = 0 + 0.2 = 0.2

ℎ 𝐹𝐴0 𝐹𝐴0 𝐹𝐴0

𝑉𝑃𝐹𝑅 = +4 +
3 −𝑟𝐴 (𝑋 = 0) −𝑟𝐴 (𝑋 = 0.2) −𝑟𝐴 (𝑋 = 0.4)

0.2
𝑉𝑃𝐹𝑅 = 0.89 + 4(1.33) + 2.05 = 0.55 𝑚3
3
 Example

The gas phase reaction 𝐴 → 𝐵 is

carried out in a CSTR and the entering 𝑿𝑨 −𝒓𝑨 (𝒎𝒐𝒍/𝒎𝟑 .s)
molar flow rate of A is 0.4 mol/s.
0.0 0.45
Using data in the following Table
0.1 0.37
a) Calculate the volume required to
0.2 0.30
achieve 80% conversion. Shade the
0.4 0.195
area on the Levenspiel plot that
0.6 0.113
corresponds to this conversion.
0.7 0.079
b) Re-do the problem if the reaction is
0.8 0.05
carried out in a PFR.
c) Any comment on the reactor size
Solution

Design equation of CSTR

𝑋
𝑉 = 𝐹𝐴0 න
−𝑟𝐴

𝑿𝑨 −𝒓𝑨 (𝒎𝒐𝒍 𝟏Τ 𝟑 𝑭𝑨𝟎

−𝒓𝑨 (𝒎 . 𝒔 ൗ−𝒓𝑨 (𝒎𝟑 . 𝒔 10
/𝒎𝟑 .s) /𝒎𝒐𝒍) /𝒎𝒐𝒍)
8

0.0 0.45 2.22 0.89 6

FA0/-rA
0.1 0.37 2.70 1.08
4
0.2 0.30 3.33 1.33
2
0.4 0.195 5.13 2.05

0.6 0.113 8.85 3.54 0

0 0.5 1
0.7 0.079 12.70 5.06 XA

0.8 0.05 20.00 8.00

𝑉 = 0.8 ∗ 8 = 6.4 𝑚3
Solution
Design equation of PFR
0.8
𝑑𝑋
𝑉 = 𝐹𝐴0 න
0 −𝑟𝐴
Use 5 point quadrature formula:

𝑿𝑨 −𝒓𝑨 (𝒎𝒐𝒍 𝑭𝑨𝟎

ൗ−𝒓𝑨 (𝒎𝟑 . 𝒔 𝑋𝐴
ℎ
𝟑
/𝒎 .s) න 𝑓 𝑋 𝑑𝑋 = (𝑓 + 4𝑓1 + 2𝑓2 + 4𝑓3 + 𝑓4 )
/𝒎𝒐𝒍)
𝑋0 3 0

𝑋4 − 𝑋0 0.8 − 0
0.0 0.45 0.89 ℎ= = = 0.2
4 4
0.2 0.30 1.33 9

8
0.4 0.195 2.05 7

0.6 0.113 3.54 6

5
0.8 0.05 8.00
4

𝑋𝐴 1

𝑉 = න 𝑓 𝑋 𝑑𝑋 = 2.18 𝑚3 0
0 0.2 0.4 0.6 0.8 1
𝑋0
 Design Equations
Summary

Reactor Differential Algebraic Integral

𝑑𝑋 𝑋
Batch 𝑑𝑋
𝑁𝐴0 = −𝑟𝐴 𝑉 t = 𝑁𝐴0 න
𝑑𝑡 0 −𝑟𝐴 𝑉
CSTR 𝐹𝐴0 𝑋
𝑉=
−𝑟𝐴
PFR 𝑑𝑋
𝐹𝐴0 = −𝑟𝐴
𝑑𝑉

PBR 𝑑𝑋
𝐹𝐴0 = −𝑟𝐴 ′
𝑑𝑊
 Design for Single Reactor

Comparison of performance of mixed flow and plug flow reactors

for any reaction kinetics
➢ For a given duty the ratio of sizes of mixed and plug flow reactors will
depend on the extent of reaction, the stoichiometry, and the form of the
rate equation.
➢ Let us make this comparison for the large class of reactions
approximated by the simple nth-order rate law

1 𝑑𝑁
−𝑟𝐴 = − = 𝑘𝐶𝐴𝑛
𝑉 𝑑𝑡
➢ For mixed flow reactor

𝑛−1
𝑋𝐴 (1 + 𝜀𝐴 𝑋𝐴 )𝑛
𝐶𝐴0 𝜏𝑚 =
(1 − 𝑋𝐴 )𝑛
➢ For plug flow reactor

𝑋𝐴
𝑛−1
(1 + 𝜀𝐴 𝑋𝐴 )𝑛 𝑑𝑋𝐴
𝐶𝐴0 𝜏𝑝 න=න
0 (1 − 𝑋𝐴 )𝑛
 1 + 𝜀𝐴 𝑋𝐴 𝑛
𝑛−1
(𝜏𝐶𝐴0 )𝑚 𝑛
(𝐶𝐴0 𝑉/𝐹𝐴0 )𝑚 [𝑋𝐴 ( ) ]𝑚
1 − 𝑋𝐴
𝑛−1 = 𝑛 =
(𝜏𝐶𝐴0 )𝑝 (𝐶𝐴0 𝑉/𝐹𝐴0 )𝑝 𝑋 1 + 𝜀𝐴 𝑋𝐴 𝑛
[‫׬‬0 𝐴( ) 𝑑𝑋𝐴 ]𝑝
1 − 𝑋𝐴

With constant density, or 𝜀 = 0, this expression integrates to

𝑋𝐴
𝑛−1 [ ]
(𝜏𝐶𝐴0 )𝑚 (1 − 𝑋𝐴 )𝑛 𝑚
𝑛−1 = 𝑛≠1
(𝜏𝐶𝐴0 )𝑝 (1−𝑋𝐴 )1−𝑛 −1
[ ]𝑝
𝑛−1

𝑋
𝑛−1
(𝜏𝐶𝐴0 )𝑚 [1 −𝐴𝑋 ]𝑚
𝐴
𝑛−1 = 𝑛=1
(𝜏𝐶𝐴0 )𝑝 − ln(1 − 𝑋𝐴 )𝑝
➢ The ordinate becomes the volume ratio 𝑉𝑚 Τ𝑉𝑝 or space-time ratio if the same
quantities of identical feed are used.
➢ Identical feed composition 𝐶𝐴0 and flow rate 𝐹𝐴0 , the ordinate of this figure
gives directly the volume ratio required for any specified conversion
➢ For any particular duty and for all positive reaction orders the mixed reactor
is always larger than the plug flow reactor. The ratio of volumes increases
with reaction order.
➢ When conversion is small, the reactor performance is only slightly affected
by flow type.
➢ The performance ratio increases very rapidly at high conversion;
consequently, a proper representation of the flow becomes very important in
this range of conversion.
➢ Density variation during reaction affects design; however, it is normally of
secondary importance compared to the difference in flow type.
Stoichiometry

Rate Law

Mole balance