Reversible and

heterogeneous reactions
Reversible reactions
Consider the reversible gas-phase elementary reaction below
2𝐴 ↔ 𝐵 + 𝐶
• The rate of the forward reaction , −𝑟𝐴,𝑓𝑜𝑟𝑤𝑎𝑟𝑑 = 𝑘𝑎 𝐶𝐴2
• −𝑟𝐴,𝑟𝑒𝑣𝑒𝑟𝑠𝑒 = −𝑘−𝑎 𝐶𝐵 𝐶𝐶
𝑘−𝑎
• −𝑟𝐴,𝑁𝑒𝑡 = 𝑘𝑎 𝐶𝐴2 −𝑘−𝑎 𝐶𝐵 𝐶𝐶 = 𝑘𝑎 𝐶𝐴2 − 𝐶𝐵 𝐶𝐶
𝑘𝑎
𝐶𝐵 𝐶𝐶 𝑘𝑎
• −𝑟𝐴,𝑁𝑒𝑡 = 𝑘𝑎 𝐶𝐴2 − , where 𝐾𝐶 =
𝐾𝐶 𝑘−𝑎
More on reversible reactions
• At equilibrium, −𝑟𝐴,𝑁𝑒𝑡 = 0,𝐶𝐴 = 𝐶𝐴𝐸 , 𝐶𝐵 = 𝐶𝐵𝐸 , 𝐶𝐶 = 𝐶𝐶𝐸
2 𝐶𝐵𝐸 𝐶𝐶𝐸
•0= 𝑘𝑎 𝐶𝐴𝐸 −
𝐾𝐶
𝐶𝐵𝐸 𝐶𝐶𝐸
• 𝐾𝐶 = 2
𝐶𝐴𝐸
• Hence for a general reaction, 𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷
𝐶𝐶𝐸 𝑐 𝐶𝐷𝐸 𝑑
• 𝐾𝐶 =
𝐶𝐴𝐸 𝑎 𝐶𝐵𝐸 𝑏
Example
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 atm). The concentration
equilibrium constant, KC, at 340 K is 0.1 mol /dm3 and the rate constant is
0.5min–1.
N2O4 ↔ 2NO2
• calculate the equilibrium conversion of N2O4 in a constant-volume batch
reactor
• Calculate the equilibrium conversion of N2O4 in a flow reactor
• 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
• Determine the CSTR volume necessary to achieve 80% of the equilibrium
conversion, for a flowrate of 3mol/min
Solution
• A ↔ 2B
𝐶𝐵𝐸 2
• 𝐾𝐶 =
𝐶𝐴𝐸
• 𝐶𝐴𝐸 = 𝐶𝐴0 1 − 𝑋𝐴𝐸 , 𝐶𝐵𝐸 = 2𝐶𝐴0 𝑋𝐴𝐸
4𝐶𝐴0 2 𝑋𝐴𝐸 2
• 𝐾𝐶 =
𝐶𝐴0 1−𝑋𝐴𝐸
• 𝐾𝐶 1 − 𝑋𝐴𝐸 = 4𝐶𝐴0 𝑋𝐴𝐸 2 , 4𝐶𝐴0 𝑋𝐴𝐸 2 + 𝑋𝐴𝐸 𝐾𝐶 − 𝐾𝐶 = 0
𝑦𝐴0𝑃 1×202.6
• 𝐶𝐴0 = = = 0.07𝑘𝑚𝑜𝑙/𝑚3 , 𝑋𝐴𝐸 = 0.44
𝑅𝑇 8.314×340
Solution continued
𝐶𝐴0 1−𝑋𝐴𝐸 2𝐶𝐴0 𝑋𝐴𝐸
b)𝐶𝐴 = , 𝜀 = 1, 𝐶𝐵𝐸 =
1+𝜀𝑋𝐴𝐸 1+𝑋𝐴𝐸
2
4𝐶𝐴0 𝑋𝐴𝐸 2
𝐾𝐶 = , 4𝐶 𝐴0 + 𝐾 𝐶 𝐴𝐸 + 𝐾𝐶 =
𝑋 0
1−𝑋𝐴𝐸 2
𝑋𝐴𝐸 = 0.51
2
𝐶𝐵
c) −𝑟𝐴 = 𝑘𝑎 𝐶𝐴 −
𝐾𝐶
for a constant volume batch reactor
𝐶𝐴 = 𝐶𝐴0 1 − 𝑋𝐴 , 𝐶𝐵𝐸 = 2𝐶𝐴0 𝑋𝐴
4𝐶𝐴0 𝑋𝐴 2
−𝑟𝐴 = 𝑘𝑎 𝐶𝐴0 1 − 𝑋𝐴 −
𝐾𝐶
Solution continued
For flow reactor
𝐶𝐴0 1−𝑋𝐴 2𝐶𝐴0 𝑋𝐴
𝐶𝐴 = , 𝐶𝐵 = 2𝐶𝐴0 𝑋𝐴 𝐶𝐵 =
1+𝑋𝐴 1+𝑋𝐴
2
1 − 𝑋𝐴 4𝐶𝐴0 𝑋𝐴
−𝑟𝐴 = 𝑘𝑎 𝐶𝐴0 − 2
1 + 𝑋𝐴 𝐾𝐶 1 + 𝑋𝐴
d)
𝑋𝐴 = 0.8𝑋𝐴𝐸 = 0.8 × 0.51 = 0.408
−𝑟𝐴 = 0.0064𝑚𝑜𝑙/𝑠𝑑𝑚3
𝐹𝐴0 𝑋𝐴 3 × 0.408
𝑉= = = 191𝑑𝑚3
−𝑟𝐴 0.0064
Accounting for pressure drop
• In liquid-phase reactions, the concentration of reactants is
insignificantly affected by even relatively large changes in the total
pressure
• However the effect of pressure in concentration for gas-phase
reactions is significant
• Hence pressure drop must be accounted for in gas phase reaction
Pressure drop in packed-bed reactors
𝑑𝑃 −𝐺 1−∅ 150𝜇 1−∅
• = + 1.75𝐺
𝑑𝑧 𝜌𝐷𝑃 ∅3 𝐷𝑃
Where 𝐺 = 𝜌𝑢 is superficial mass velocity kg/m2s
𝜌 is the gas density kg/m3
𝜇 is the viscosity of gas in Pa.s or kg/ms
𝑉0ሶ
𝑢= is the superficial velocity in m/s
𝐴
𝐷𝑃 is the diameter of particle in m
∅ is the porosity
More on pressure drop
• 𝜌0 𝑉ሶ0 = 𝜌𝑉ሶ
𝜌0 𝑉0ሶ
• 𝜌= ሶ
𝑉
𝑑𝑃 −𝐺 1−∅ 150𝜇 1−∅ 𝑉ሶ
• = + 1.75𝐺
𝑑𝑧 𝜌0 𝐷𝑃 ∅3 𝐷𝑃 𝑉0ሶ
𝐺 1−∅ 150𝜇 1−∅
• 𝛽0 = + 1.75𝐺
𝜌0 𝐷𝑃 ∅3 𝐷𝑃
𝑑𝑃 𝑉ሶ
• = 𝛽0 ሶ
𝑑𝑧 𝑉0
𝑇 𝑃0
• 𝑉ሶ = 𝑉ሶ0 1 + 𝜀𝑋𝐴
𝑇0 𝑃
More on pressure drop
𝑑𝑃 𝑇 𝑃0
• = 𝛽0 1 + 𝜀𝑋𝐴
𝑑𝑧 𝑇0 𝑃
• 𝑊 = 1 − ∅ 𝐴𝜌𝑐 𝑧
𝑑𝑊
• 𝑑𝑧 =
1−∅ 𝐴𝜌𝑐
𝑑𝑃 𝛽0 1+𝜀𝑋𝐴 𝑇 𝑃0
• =
𝑑𝑊 1−∅ 𝐴𝜌𝑐 𝑇0 𝑃
2𝛽0
• 𝛼=
𝑃0 1−∅ 𝐴𝜌𝑐
𝑑𝑃 𝛼 1+𝜀𝑋𝐴 𝑇 𝑃0 2
• =
𝑑𝑊 2 𝑇0 𝑃
More on pressure drop
For an isothermal process
𝑑𝑃 −𝛼 1+𝜀𝑋𝐴 𝑃0 2
• =
𝑑𝑊 2 𝑃
• If 𝜀 = 0 or 1 ≫ 1
𝑑𝑃 𝛼 𝑃0 2
• =−
𝑑𝑊 2 𝑃
• 𝑃0 2 − 𝑃2 = 𝛼𝑃0 2 𝑊
𝑃 2
• 1 − 𝛼𝑊 =
𝑃0
• 𝑃 = 𝑃0 1 − 𝛼𝑊
Pressure drop
2𝛽0
• 𝛼= , 𝑊 = 1 − ∅ 𝐴𝜌𝑐 𝑧
𝑃0 1−∅ 𝐴𝜌𝑐
2𝛽0 𝐿
• 𝛼𝑊 =
𝑃0
2𝛽0 𝐿 0.5
• 𝑃 = 𝑃0 1 −
𝑃0
Application to first law
𝐴→𝐵
𝐹𝐴0 𝑑𝑋𝐴
• = −𝑟𝐴′
𝑑𝑊
For a first order reaction, −𝑟𝐴′ = 𝑘𝐶𝐴
𝐶𝐴0 1−𝑋𝐴 𝑇0 𝑃
𝐶𝐴 = , for isothermal, with 𝜀 = 0
1+𝜀𝑋𝐴 𝑇 𝑃0
𝑃 0.5
𝐶𝐴 = 𝐶𝐴0 1 − 𝑋𝐴 = 𝐶𝐴0 1 − 𝑋𝐴 1 − 𝛼𝑊
𝑃0
−𝑟𝐴′ = 𝑘𝐶𝐴0 1 − 𝑋𝐴 1 − 𝛼𝑊 0.5
Application to first law
𝐴→𝐵
𝐹𝐴0 𝑑𝑋𝐴
• = −𝑟𝐴′
𝑑𝑊
For a first order reaction, −𝑟𝐴′ = 𝑘𝐶𝐴
𝐶𝐴0 1−𝑋𝐴 𝑇0 𝑃
𝐶𝐴 = , for isothermal, with 𝜀 = 0
1+𝜀𝑋𝐴 𝑇 𝑃0
𝑃 0.5
𝐶𝐴 = 𝐶𝐴0 1 − 𝑋𝐴 = 𝐶𝐴0 1 − 𝑋𝐴 1 − 𝛼𝑊
𝑃0
−𝑟𝐴′ = 𝑘𝐶𝐴0 1 − 𝑋𝐴 1 − 𝛼𝑊 0.5
Application to First law
𝐴→𝐵
𝐹𝐴0 𝑑𝑋𝐴 0.5
• = 𝑘𝐶𝐴0 1 − 𝑋𝐴 1 − 𝛼𝑊
𝑑𝑊
𝐹𝐴0 𝑑𝑋𝐴 0.5 𝑑𝑊
• = 𝑘 1 − 𝛼𝑊
𝐶𝐴0 1−𝑋𝐴
𝛼 𝑉0ሶ 2 1.5 −1]
• 𝑙𝑛 1 − 𝑋𝐴 = [ 1 − 𝛼𝑊
𝑘 3
2𝑘[ 1−𝛼𝑊 1.5 −1]
• 𝑋𝐴 = 1 − 𝑒 3𝛼𝑉ሶ 0
2
3𝛼𝑉ሶ 1 3
1− 2𝑘 0𝑙𝑛 1−𝑋 +1
•𝑊= 𝐴
𝛼
Application to second law
𝐴→𝐵
𝐹𝐴0 𝑑𝑋𝐴
• = −𝑟𝐴′
𝑑𝑊
For a second order reaction, −𝑟𝐴′ = 𝑘𝐶𝐴 2 , under Isothermal conditions
−𝑟𝐴′ = 𝑘𝐶𝐴0 2 1 − 𝑋𝐴 2 1 − 𝛼𝑊
𝑉ሶ0 𝑑𝑋𝐴
= 𝑘𝐶𝐴0 1 − 𝑋𝐴 2 1 − 𝛼𝑊
𝑑𝑊
𝑋𝐴 𝑘𝐶𝐴0 𝑊
= 1 − 0.5𝛼𝑊
1 − 𝑋𝐴 𝑉ሶ0
1 𝑉ሶ0
−1=
𝑋𝐴 𝑘𝐶𝐴0 𝑊 1 − 0.5𝛼𝑊
Application to second law
1 𝑉ሶ0
=1+
𝑋𝐴 𝑘𝐶𝐴0 𝑊 1 − 0.5𝛼𝑊
1 𝑘𝐶𝐴0 𝑊 1 − 0.5𝛼𝑊 + 𝑉ሶ0
=
𝑋𝐴 𝑘𝐶𝐴0 𝑊 1 − 0.5𝛼𝑊
𝑘𝐶𝐴0 𝑊 1 − 0.5𝛼𝑊
𝑋𝐴 =
𝑘𝐶𝐴0 𝑊 1 − 0.5𝛼𝑊 + 𝑉ሶ0
Example 2
A second order reaction, 2𝐴 → 𝐵 + 𝐶 is taking place in 20 meters of 3.81cm
scheduled 40 pipe backed with catalyst. The temperature is constant along
the length of pipe at 260oC. The flow and packed-bed conditions are as
follows:
𝑃0 = 10𝑎𝑡𝑚, 𝑉ሶ0 = 7.15𝑚3 /ℎ, 𝐷𝑃 = 0.006𝑚, 𝜌𝑐 = 1923𝑘𝑔/𝑚3
𝛽0 = 25.8𝑘𝑃𝑎/𝑚,∅ = 0.45
The entering6concentration of A is 0.1 kmol/m3 and the specific reaction rate
𝑚
is 12
𝑘𝑚𝑜𝑙.𝑘𝑔−𝑐𝑎𝑡.ℎ𝑟
• Calculate the conversion in the absence of pressure drop
• Calculate the conversion accounting for pressure drop
Example 3
Calculate the catalyst weight necessary to achieve 60% conversion when ethylene oxide is to be
made by the vapour phase catalytic oxidation of ethylene with air.
𝐶2 𝐻4 + 0.5𝑂2 → 𝐶2 𝐻4 𝑂
Ethylene and oxygen are fed in stoichiometric proportions to a packed-bed reactor operated
isothermally at 2600C. Ethylene is fed at a rate of 136.21 mol/s at a pressure of 10 atm (1013 kPa). It
is proposed to use 10 banks of -inch-diameter schedule-40 tubes packed with catalyst with 100
tubes per bank. Consequently, the molar flow rate to each tube is to be 0.1362 mol/s. The
properties of the reacting fluid are to be considered identical to those of air at this temperature and
pressure. The density of the 1/4-inch-catalyst particles is 1925 kg/m3, the bed void fraction is 0.45,
1/3 2/3
and the gas density is 16 kg/m3. The rate law is −𝑟𝐴′ = 𝑘𝑃𝐴 𝑃𝐵 mol/kg-cats with 𝑘 =
𝑚𝑜𝑙
0.00392 at 260oC. The catalyst density, particle size, gas density, void fraction, pipe
𝑠,𝑎𝑡𝑚𝑘𝑔−𝑐𝑎𝑡
cross-sectional area, entering pressure, and superficial velocity are the same as in example 3.
Assignments
• Assignment 1:
a)Using a Matlab script, evaluate the effect of catalyst weight on the
conversion for example 2, when pressure drop is ignored and when
pressure drop is accounted for.
b)Plot a concentration profile for all the species involved in the reaction
Assignment 2:
Using a Matlab script, evaluate the effect of catalyst weight on the
conversion for example 3