CL324

Chapter 5 –Temperature Effects

Prof. Swati Bhattacharya

• Most reactors do not work isothermally, we need to introduce heat
effects.
• Consider a highly exothermic reaction carried out adiabatically in a
plug flow reactor
𝐴→𝐵

Operation is adiabatic. Temperature will increase with conversion.

 𝑑𝑋 𝑟𝐴
Mole Balance: = −
𝑑𝑉 𝐹𝐴0
Rate Law: Remember Arrhenius equation
𝐸 1 1
𝑘 = 𝑘1 exp −
𝑅 𝑇1 𝑇

Stoichiometry: (liquid phase for simplicity)

𝑣 = 𝑣0 (volumetric velocity)
𝐹𝐴 = 𝐶𝐴 𝑣0

𝐹𝐴0 = 𝐶𝐴0 𝑣0
And 𝐶𝐴 = 𝐶𝐴0 (1 − 𝑋)
 𝐸 1 1
Combining −𝑟𝐴 = 𝑘𝐶𝐴 = 𝑘1 exp − 𝐶𝐴0 1 − 𝑋
𝑅 𝑇1 𝑇

Apply to mole-balance (design eqn):

𝑑𝑋 𝑘 1 − 𝑋
=
𝑑𝑉 𝑣0
Because temperature varies along the length of the reactor, 𝑘 will also
vary.
𝑑𝑋 𝐸 1 1 (1−𝑋)
= 𝑘1 exp −
𝑑𝑉 𝑅 𝑇1 𝑇 𝑣0

So, can we write 𝑇 = 𝑇 𝑋 ?

Energy balance
First Law of Thermodynamics
መ = 𝛿𝑄 − 𝛿𝑊,
𝑑𝐸
𝛿 signifies that these are not exact differentials (i.e, these are path
dependent)

Continuous flow reactors are open systems (mass crosses boundary)

Energy balance for the case of only one species entering and leaving:

𝑑 𝐸෠𝑠𝑦𝑠
= 𝑄ሶ − 𝑊ሶ + 𝐹𝑖𝑛 𝐸𝑖𝑛 − 𝐹𝑜𝑢𝑡 𝐸𝑜𝑢𝑡
𝑑𝑡

𝑑 𝐸෠𝑠𝑦𝑠
= Rate of accumulation of energy within the system
𝑑𝑡

𝑄ሶ =Rate of flow of heat to the system from the surroundings

𝑊ሶ =Rate of work done by the system on the surroundings
𝐹𝑖𝑛 𝐸𝑖𝑛 = Rate of energy added to the system by mass flow into the system
𝐹𝑜𝑢𝑡 𝐸𝑜𝑢𝑡 = Rate of energy leaving the system by the flow of mass out of the
system
Energy Balance
Reactor with no Spatial Variations

Reactor
Energy Balance
Reactor with no Spatial Variations
Q

Reactor

Rate of flow
of heat to
the system
from the
surroundings

Q
(J/s)
Energy Balance
Reactor with no Spatial Variations
Q W

Reactor

Rate of flow
Rate of work
of heat to
the system - done by the
system on the
from the
surroundings
surroundings

Q - W
(J/s) (J/s)
Energy Balance
Reactor with no Spatial Variations
Q W

Fin
Reactor
Ein

Rate of flow Rate of energy

Rate of work
of heat to added to the
the system - done by the
system on the
+ system by
from the mass flow into
surroundings
surroundings the system

Q - W + Fin Ein
(J/s) (J/s) (J/s)
Energy Balance
Reactor with no Spatial Variations
Q W

Fin Fout
Reactor
Ein Eout

Rate of flow Rate of energy Rate of energy

Rate of work
of heat to added to the leaving
the system - done by the
system on the
+ system by - system by
from the mass flow into mass flow out
surroundings
surroundings the system of the system

Q - W + Fin Ein - Fout Eout

(J/s) (J/s) (J/s) (J/s)
Energy Balance
Reactor with no Spatial Variations
Q W

Fin Fout
Reactor
Ein Eout

Rate of Rate of flow Rate of energy Rate of energy

Rate of work
accumulation of heat to added to the leaving
of energy = the system - done by the
system on the
+ system by - system by
within the from the mass flow into mass flow out
surroundings
system surroundings the system of the system

dEˆ sys
dt = Q - W + Fin Ein - Fout Eout
(J/s) (J/s) (J/s) (J/s) (J/s)
Energy Balance in a well mixed open
system
Q
Fi in  Fi out
 
(e.g., FA 0 )  (e.g., FA )
 
H i in  H i out

(e.g., H A 0 ) W S (e.g., H )
 A

dE system
Q − WS +  Fi 0 E i 0 in −  Fi E i out =
  (1)
dt
13
Evaluating the work term
𝑊ሶ is split into flow work and other work, 𝑊ሶ 𝑠 (often called shaft work).
𝑊ሶ 𝑠 can be produced form stirrer (CSTR) or turbine (PFR).
Flow work is work done to get the mass into and out of the system.

Eg, in absence of shear stresses:

𝑛 ሶ 𝑛
𝑊ሶ = − ෍ 𝐹𝑖 𝑃𝑉෨𝑖 ቚ + ෍ 𝐹𝑖 𝑃𝑉෨𝑖 ቚ + 𝑊ሶ 𝑠
𝑖𝑛 𝑜𝑢𝑡
𝑖 𝑖
Here, 𝑃 is the pressure (𝑃𝑎), 𝑉෨𝑖 = is the specific molar volume of species 𝑖
(𝑚3 /𝑚𝑜𝑙)
Unit of the flow term: 𝐹𝑖 ⋅ 𝑃 ⋅ 𝑉෨𝑖
𝑚𝑜𝑙 𝑁𝑒𝑤𝑡𝑜𝑛 𝑚3 𝐽𝑜𝑢𝑙𝑒𝑠
⋅ 2
⋅ = = 𝑊𝑎𝑡𝑡𝑠
𝑠 𝑚 𝑚𝑜𝑙 𝑠

Go back to the energy balance:

෠
𝑛 ሶ 𝑛
𝑑 𝐸𝑠𝑦𝑠
= 𝑄ሶ − 𝑊ሶ 𝑠 + ෍ 𝐹𝑖 𝐸𝑖 + 𝑃 𝑉෨𝑖 ቚ − ෍ 𝐹𝑖 𝐸𝑖 + 𝑃 𝑉෨𝑖 ቚ
𝑑𝑡 𝑖𝑛 𝑜𝑢𝑡
𝑖=1 𝑖=1

𝑢𝑖2
Here 𝐸𝑖 = sum of internal energy 𝑈𝑖 , kinetic energy , potential energy 𝑔𝑧𝑖
2
and other energies (electric, magnetic, light if relevant)
𝑢𝑖2
𝐸𝑖 = 𝑈𝑖 + + 𝑔𝑧𝑖 + 𝑜𝑡ℎ𝑒𝑟
2
But, in most chemical reactors, the kinetic , potential and other energy terms
are negligible in comparison with the enthalpy, heat transfer and work terms
and are generally omitted.
So, we take, 𝐸𝑖 = 𝑈𝑖
Note, we define enthalpy as 𝐻𝑖 = 𝑈𝑖 + 𝑃𝑉෨𝑖 ,
𝐽 𝐵𝑡𝑢 𝑐𝑎𝑙
Units of 𝐻𝑖 : or or
𝑚𝑜𝑙 𝑜𝑓 𝑖 𝑙𝑏 𝑚𝑜𝑙 𝑖 𝑚𝑜𝑙 𝑖

The enthalpy carried into or out of the system can be written as sum of
internal energy plus flow work:
𝐹𝑖 𝐻𝑖 = 𝐹𝑖 (𝑈𝑖 + 𝑃𝑉෨𝑖 )
Which simplifies our energy balance:
෠
𝑛 ሶ 𝑛
𝑑 𝐸𝑠𝑦𝑠
= 𝑄ሶ − 𝑊ሶ 𝑠 + ෍ 𝐹𝑖 𝐻𝑖 ቚ − ෍ 𝐹𝑖 𝐻𝑖 ቚ
𝑑𝑡 𝑖𝑛 𝑜𝑢𝑡
𝑖=1 𝑖=1
Conventionally, we use "𝑠𝑢𝑏𝑠𝑐𝑟𝑖𝑝𝑡 0" for inlet conditions.
𝑛 𝑛
𝑑 𝐸෠𝑠𝑦𝑠
𝑄ሶ − 𝑊ሶ𝑠 + ෍ 𝐹𝑖0 𝐻𝑖0 − ෍ 𝐹𝑖 𝐻𝑖 =
𝑑𝑡
𝑖=1 𝑖=1
For steady state conditions:
𝑛 𝑛

𝑄ሶ − 𝑊ሶ𝑠 + ෍ 𝐹𝑖0 𝐻𝑖0 − ෍ 𝐹𝑖 𝐻𝑖 = 0

𝑖=1 𝑖=1
Now, σ𝑛 𝑛
𝑖 𝐹𝑖0 𝐻𝑖0 = 𝐹𝐴0 σ𝑖 Θ𝑖 𝐻𝑖0
And σ𝑛𝑖 𝐹𝑖 𝐻𝑖 = 𝐹𝐴0 σ𝑛𝑖 Θ𝑖 + 𝜈𝑖 𝑋 𝐻𝑖

Or, σ𝑛𝑖 𝐹𝑖 𝐻𝑖 = 𝐹𝐴0 σ𝑛𝑖 Θ𝑖 𝐻𝑖 + 𝐹𝐴0 𝑋 σ𝑛𝑖 𝜈𝑖 𝐻𝑖

We define

σ𝑛𝑖 𝜈𝑖 𝐻𝑖 = ΔHRx (𝑇) is the heat of reaction at temperature T.

For a reaction: 𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷
𝑑 𝑐 𝑏
Δ𝐻𝑅𝑥 𝑇 = 𝐻 𝑇 + 𝐻𝐶 𝑇 − 𝐻𝐵 𝑇 − 𝐻𝐴 (𝑇)
𝑎 𝐷 𝑎 𝑎

All enthalpies eg. 𝐻𝐴 , 𝐻𝐵 are calculated at the temperature at the outlet of the system.
i.e Δ𝐻𝑅𝑥 𝑇 = σ𝑛𝑖 𝜈𝑖 𝐻𝑖
Energy balance
𝑄ሶ − 𝑊ሶ𝑠 + 𝐹𝐴0 σ𝑛𝑖 Θ𝑖 𝐻𝑖0 − 𝐹𝐴0 σ𝑛𝑖 Θ𝑖 𝐻𝑖 − 𝐹𝐴0 𝑋 σ𝑛𝑖 𝜈𝑖 𝐻𝑖 = 0

Or
𝑛

𝑄ሶ − 𝑊ሶ𝑠 + 𝐹𝐴0 ෍ Θ𝑖 𝐻𝑖0 − 𝐻𝑖 − 𝐹𝐴0 𝑋Δ𝐻𝑅𝑥 (𝑇) = 0

𝑖
If phase change takes place during the course of the reaction, this form
of energy balance must be used.
Revisit the enthalpies
Molal enthalpy of species 𝑖 at some temperature and pressure, 𝐻𝑖 is
usually expressed in terms of enthalpy of formation of species 𝑖 at
some reference temperature 𝑇𝑅 , 𝐻𝑖0 (𝑇𝑅 ) plus change in enthalpy when
the temperature is raised to 𝑇:

𝐻𝑖 (𝑇) = 𝐻𝑖0 𝑇𝑅 + Δ𝐻𝑄𝑖

Explanation: [Enthalpy of species 𝑖 in the gas phase at 𝑇]=

𝐸𝑛𝑡ℎ𝑎𝑙𝑝𝑦 𝑜𝑓
Δ𝐻𝑄 𝑖𝑛
𝑓𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛 𝐻𝑒𝑎𝑡 𝑜𝑓
ℎ𝑒𝑎𝑡𝑖𝑛𝑔 𝑠𝑜𝑙𝑖𝑑
𝑜𝑓 𝑠𝑝𝑒𝑐𝑖𝑒𝑠 𝑖𝑛 + + 𝑚𝑒𝑙𝑡𝑖𝑛𝑔 𝑎𝑡
𝑓𝑟𝑜𝑚 𝑇𝑅
𝑠𝑜𝑙𝑖𝑑 𝑝ℎ𝑎𝑠𝑒 𝑇𝑚
𝑡𝑜 𝑇𝑚
𝑎𝑡 𝑇𝑅

Δ𝐻𝑄 𝑖𝑛 ℎ𝑒𝑎𝑡𝑖𝑛𝑔 𝐻𝑒𝑎𝑡 𝑜𝑓 Δ𝐻𝑄 𝑜𝑓

+ 𝑙𝑖𝑞𝑢𝑖𝑑 𝑓𝑟𝑜𝑚 + 𝑣𝑎𝑝𝑜𝑟𝑎𝑡𝑖𝑜𝑛 + ℎ𝑒𝑎𝑡𝑖𝑛𝑔 𝑡ℎ𝑒
𝑇𝑚 𝑡𝑜 𝑇𝑏 𝑎𝑡 𝑇𝑏 𝑔𝑎𝑠 𝑓𝑟𝑜𝑚 𝑇𝑏 𝑡𝑜 𝑇

𝐻𝑖 𝑇 = 𝐻𝑖0 𝑇𝑅

𝑇𝑚 𝑇𝑏 𝑇
+න 𝐶𝑃𝑠𝑖 𝑑𝑇 + Δ𝐻𝑚𝑖 𝑇𝑚 + න 𝐶𝑃𝑙𝑖 𝑑𝑇 + ΔH𝑣𝑖 𝑇𝑏 + න 𝐶𝑃𝑔𝑖 𝑑𝑇
𝑇𝑅 𝑇𝑚 𝑇𝑏
If no phase changes:
𝑇
𝐻𝑖 𝑇 = 𝐻𝑖0 𝑇𝑅 + න 𝐶𝑃𝑖 𝑑𝑇
𝑇𝑅
Where 𝐻𝑖0 𝑇𝑅 is the enthalpy of formation at 𝑇𝑅
Assuming that 𝐶𝑃𝑖 is constant over the temperature range.
𝐻𝑖 𝑇 = 𝐻𝑖0 𝑇𝑅 + 𝐶𝑃𝑖 (𝑇 − 𝑇𝑅 ) -outlet
𝐻𝑖 𝑇0 = 𝐻𝑖0 𝑇𝑅 + 𝐶𝑃𝑖 𝑇0 − 𝑇𝑅 - inlet

Or, 𝐻𝑖 (𝑇) − 𝐻𝑖0 (𝑇0 ) = 𝐶𝑃𝑖 (𝑇 − 𝑇0 )

And σ𝑛𝑖 𝐻𝑖 𝜈𝑖 = σ𝑛𝑖 𝜈𝑖 𝐻𝑖0 (𝑇𝑅 ) + σ𝑛𝑖 𝜈𝑖 𝐶𝑃𝑖 (𝑇 − 𝑇𝑅 )

Calculate the change in enthalpy when the reacting fluid is heated without
phase change from its entrance temperature 𝑇0 to a temperature 𝑇 (at
outlet),
𝑇 𝑇0
𝐻𝑖 (𝑇) − 𝐻𝑖0 (𝑇0 ) = 𝐻𝑖0 𝑇𝑅 + න 𝐶𝑃𝑖 𝑑𝑇 − 𝐻𝑖0 𝑇𝑅 + න 𝐶𝑃𝑖 𝑑𝑇
𝑇𝑅 𝑇𝑅

= 𝐶𝑃𝑖 (𝑇 − 𝑇𝑖0 )
Put back in Energy Balance:𝑛
𝑄ሶ − 𝑊ሶ𝑆 − 𝐹𝐴0 ෍ Θ𝑖 𝐶𝑃𝑖 𝑇 − 𝑇𝑖0 − Δ𝐻𝑅𝑋 𝑇 𝐹𝐴0 𝑋 = 0
𝑖
 0
Relating Δ𝐻𝑅𝑋 𝑇 , Δ𝐻𝑅𝑋 (𝑇𝑅 ) and Δ𝐶𝑃
The heat of reaction at a temperature 𝑇. In terms of enthalpy of each
species at temperature 𝑇:
𝑑 𝑐 𝑏
Δ𝐻𝑅𝑋 (𝑇) = 𝐻𝐷 𝑇 + 𝐻𝐶 𝑇 − 𝐻𝐵 𝑇 − 𝐻𝐴 (𝑇)
𝑎 𝑎 𝑎

With the enthalpy of each species

𝑇
𝐻𝑖 𝑇 = 𝐻𝑖0 𝑇𝑅 + න 𝐶𝑃𝑖 𝑑𝑇 = 𝐻𝑖0 𝑇𝑅 + 𝐶𝑃𝑖 (𝑇 − 𝑇𝑅 )
𝑇𝑅
Or,
Δ𝐻𝑅𝑋 𝑇
𝑑 0 𝑐 0 𝑏 0
= 𝐻𝐷 𝑇𝑅 + 𝐻𝐶 𝑇𝑅 − 𝐻𝐵 𝑇𝑅 − 𝐻𝐴0 (𝑇𝑅 )
𝑎 𝑎 𝑎
𝑑 𝑐 𝑏
+ 𝐶𝑃𝐷 + 𝐶𝑃𝐶 − 𝐶𝑃𝐵 − 𝐶𝑃𝐴 (𝑇 − 𝑇𝑅 )
𝑎 𝑎 𝑎

The first set of terms on RHS is the heat of reaction at the reference
temperature 𝑇𝑅 :
𝑑 0 𝑐 0 𝑏 0
Δ𝐻𝑅𝑋 𝑇𝑅 = 𝐻𝐷 𝑇𝑅 + 𝐻𝐶 𝑇𝑅 − 𝐻𝐵 𝑇𝑅 − 𝐻𝐴0 (𝑇𝑅 )
0
𝑎 𝑎 𝑎
Finally: write
𝑑 𝑐 𝑏
Δ𝐶𝑃 = 𝐶𝑃𝐷 + 𝐶𝑃𝐶 − 𝐶𝑃𝐵 − 𝐶𝑃𝐴
𝑎 𝑎 𝑎

And combining
0
Δ𝐻𝑅𝑋 𝑇 = Δ𝐻𝑅𝑋 𝑇𝑅 + Δ𝐶𝑃 (𝑇 − 𝑇𝑅 )
How to use energy balance in a problem

1. Replace Ui by Ui=Hi-PVi
2. Express Hi in terms of heat capacities
3. Express Fi in terms of either conversion or rates
of reaction
4. Define ΔHRx
5. Define ΔCP
6. Manipulate so that the overall energy balance
is in terms of the User Friendly Equations.

27
Calculate the heat of Reaction for the synthesis of ammonia from
hydrogen and nitrogen at 150℃ in kcal/mol of 𝑁2 reacted and also
kJ/mol of 𝐻2 reacted.
Solution:
𝑁2 + 3𝐻2 → 2𝑁𝐻3

Hint: Use Perry’s Handbook or Handbook of Chemistry and Physics to

get heats of formation.

0 0 0 0
Δ𝐻𝑅𝑋 𝑇𝑅 = 2𝐻𝑁𝐻3
𝑇𝑅 − 3𝐻 𝑇
𝐻2 𝑅 − 𝐻𝑁2 (𝑇𝑅 )

Heat of formation of the elements (𝐻2 , 𝑁2 ) are zero at 25℃.

 0 0 0
So, Δ𝐻𝑅𝑋 𝑇𝑅 = 2𝐻𝑁𝐻3
𝑇𝑅 − 3 0 − 0 = 2𝐻𝑁𝐻3
𝑐𝑎𝑙
= 2 −11020
𝑚𝑜𝑙 𝑁2 𝑟𝑒𝑎𝑐𝑡𝑒𝑑
𝑐𝑎𝑙
= −22040
𝑚𝑜𝑙 𝑜𝑓 𝑁2 𝑟𝑒𝑎𝑐𝑡𝑒𝑑
Minus sign shows that the reaction is exothermic.
If heat capacities are constant or if it is available over the range 25-
150℃, we can calculate Δ𝐻𝑅𝑋 at 150℃
 𝑐𝑎𝑙
Given, 𝐶𝑃𝐻2 = 6.992
𝑚𝑜𝑙 𝐻2 ⋅𝐾
𝑐𝑎𝑙
𝐶𝑃𝑁2 = 6.984
𝑚𝑜𝑙 𝑁2 ⋅ 𝐾

𝑐𝑎𝑙
𝐶𝑃𝑁𝐻3 = 8.92
𝑚𝑜𝑙 𝑁𝐻3 ⋅ 𝐾

So, Δ𝐶𝑃 = 2𝐶𝑃𝑁𝐻3 − 3𝐶𝑃𝐻2 − 𝐶𝑃𝑁2

𝑐𝑎𝑙
= 2 8.92 − 3 6.992 − 6.984 = −10.12
𝑚𝑜𝑙 𝑁2 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 ⋅ 𝐾
 0
Δ𝐻𝑅𝑋 𝑇 = Δ𝐻𝑅𝑋 𝑇𝑅 + Δ𝐶𝑃 (𝑇 − 𝑇𝑅 )

Δ𝐻𝑅𝑋 𝑇 = 423𝐾 = −22040 + −10.12 423 − 298

𝑐𝑎𝑙 𝑘𝑐𝑎𝑙
= −23310 = −23.31
𝑚𝑜𝑙 𝑁2 𝑚𝑜𝑙 𝑁2
𝑘𝑐𝑎𝑙 𝑘𝐽
Convert units Δ𝐻𝑅𝑋 𝑇 = 423𝐾 = −23.31 × 4.184
𝑚𝑜𝑙 𝑁2 𝑘𝑐𝑎𝑙
𝑘𝐽
= −97.5
𝑚𝑜𝑙 𝑁2
The heat of reaction in terms of the number of moles of 𝐻2 reacted:
1 𝑚𝑜𝑙 𝑜𝑓 𝑁2 𝑘𝐽
Δ𝐻𝑅𝑋 𝑇 = (−97.53 )
3 𝑚𝑜𝑙 𝑜𝑓 𝐻2 𝑚𝑜𝑙 𝑜𝑓 𝑁2
𝑘𝐽
= −32.51 𝑎𝑡 423𝐾
𝑚𝑜𝑙 𝑜𝑓 𝐻2 𝑟𝑒𝑎𝑐𝑡𝑒𝑑
Adiabatic operation
Reactions in industry are often carried out adiabatically with heating or
cooling carried out either upstream or downstream.
Energy balance

𝑄ሶ − 𝐹𝐴0 σΘ𝑖 (𝐶𝑝𝑖 𝑇 − 𝑇0 − Δ𝐻𝑅𝑥

0
𝑇𝑅 + Δ𝐶𝑃 𝑇 − 𝑇𝑅 𝐹𝐴0 𝑋 = 0

We are ignoring the shaft work 𝑊ሶ𝑆 .

For adiabatic operation 𝑄ሶ = 0
Giving
σΘ𝑖 𝐶𝑝𝑖 (𝑇 − 𝑇0 )
𝑋= 0
−[Δ𝐻𝑅𝑥 (𝑇𝑅 ) + Δ𝐶𝑃 𝑇 − 𝑇𝑅 ]

0
In some cases, Δ𝐶𝑃 𝑇 − 𝑇𝑅 can be negligible wrt Δ𝐻𝑅𝑥 𝑇𝑅 .
Adiabatic tubular Reactor
σΘ𝑖 𝐶𝑝𝑖 (𝑇−𝑇0 )
Rearrange: 𝑋 = 0 (𝑇 )+Δ𝐶 𝑇−𝑇 ]
−[Δ𝐻𝑅𝑥 𝑅 𝑃 𝑅

To get
0
𝑋[−Δ𝐻𝑅𝑥 𝑇𝑅 +σΘ𝑖 𝐶𝑃𝑖 𝑇0 +𝑋Δ𝐶𝑃 𝑇𝑅 ]
𝑇=
σΘ𝑖 𝐶𝑃𝑖 +𝑋Δ𝐶𝑃
Which can be coupled to
𝑑𝑋
𝐹𝐴0 = −𝑟𝐴 (𝑋, 𝑇)
𝑑𝑉
 Assumptions:

𝐴𝑑𝑖𝑎𝑏𝑎𝑡𝑖𝑐: 𝑄ሶ = 0
𝑊ሶ𝑆 = 0
𝑋𝐸𝐵 0
Also Δ𝐶𝑃 𝑇 − 𝑇𝑅 ≪ Δ𝐻𝑅𝑥 𝑇𝑅

T
Algorithm for Adiabatic PFR/PBR
Consider reversible 𝐴 ⇄ 𝐵 in a PFR where we neglect pressure drop
and suppose 𝐴 enters in pure phase

𝑑𝑋 𝑟𝐴
1. Mole Balance: − = −
𝑑𝑉 𝐹𝐴0
𝐶𝐵
2. Rate Law: Suppose −𝑟𝐴 = 𝑘 𝐶𝐴 −
𝐾𝐶

𝐸 1 1
With temperature dependence: 𝑘 = 𝑘1 𝑇1 exp −
𝑅 𝑇1 𝑇
 0
Δ𝐻𝑅𝑥 1 1
Also, 𝐾𝐶 = 𝐾𝐶2 𝑇2 exp −
𝑅 𝑇2 𝑇

3. Stoichiometry:
Gas phase with 𝜀 = 0, 𝑃 = 𝑃0
𝐶𝐴 = 𝐶𝐴0 1 − 𝑋 ( 𝑇0 /𝑇)
𝑇0
𝐶𝐵 = 𝐶𝐴0 𝑋
𝑇

Combine with Rate Law:

𝑋 𝑇0
−𝑟𝐴 = 𝑘𝐶𝐴0 1−𝑋 −
𝐾𝐶 𝑇
Energy Balance
To relate temperature and conversion, apply energy balance in
adiabatic case to PFR. All species enter at the same given initial
temperature 𝑇𝑖0 = 𝑇0
0
𝑋[−Δ𝐻𝑅𝑥 𝑇𝑅 + σΘ𝑖 𝐶𝑃𝑖 𝑇0 + 𝑋Δ𝐶𝑃 𝑇𝑅 ]
𝑇=
σΘ𝑖 𝐶𝑃𝑖 + 𝑋Δ𝐶𝑃

Here, we assume pure 𝐴 enters and iff Δ𝐶𝑃 = 0,

0
𝑋 −Δ𝐻𝑅𝑥 𝑇𝑅
𝑇 = 𝑇0 +
𝐶𝑃𝐴
Numerical Method
A. Integrating PFR mole balance
𝑋3
𝐹𝐴0
𝑉=න 𝑑𝑋
0 −𝑟𝐴

(i) Set 𝑋 = 0
0
𝑋 −Δ𝐻𝑅𝑥 𝑇𝑅
(ii) Calculate 𝑇 using 𝑇 = 𝑇0 + or
𝐶𝑃𝐴
0
𝑋[−Δ𝐻𝑅𝑥 𝑇𝑅 +σΘ𝑖 𝐶𝑃𝑖 𝑇0 +𝑋Δ𝐶𝑃 𝑇𝑅 ]
𝑇=
σΘ𝑖 𝐶𝑃𝑖 +𝑋Δ𝐶𝑃
 𝐸 1 1
(iii) Calculate 𝑘 using 𝑘 = 𝑘1 𝑇1 exp −
𝑅 𝑇1 𝑇
0
Δ𝐻𝑅𝑥 1 1
(iv) Calculate 𝐾𝐶 using 𝐾𝐶 = 𝐾𝐶2 𝑇2 exp −
𝑅 𝑇2 𝑇
𝑇0
(v) Calculate (gas phase)
𝑇
𝑋 𝑇0
(vi) Calculate −𝑟𝐴 using −𝑟𝐴 = 𝑘𝐶𝐴0 1−𝑋 −
𝐾𝐶 𝑇
 𝐹𝐴0
(vii) Calculate
−𝑟𝐴
(viii) If 𝑋 < 𝑋3 , prepare increment 𝑋𝑖+1 = 𝑋𝑖 + Δ𝑋 and go to Step (ii)

𝐹𝐴0
(ix) Prepare table of 𝑋 𝑣𝑠
−𝑟𝐴
(x) Use numerical integration formula
𝑋3
𝐹𝐴0 3 𝐹𝐴0 3𝐹𝐴0 3𝐹𝐴0 𝐹𝐴0
𝑉=න 𝑑𝑋 = ℎ[ + + + ]
0 −𝑟𝐴 8 −𝑟𝐴 𝑋 = 0 −𝑟𝐴 𝑋1 −𝑟𝐴 𝑋2 −𝑟𝐴 𝑋3

ℎ = 𝑋3 /3
ODE solver
𝑑𝑋 𝑘𝐶𝐴0 𝑋 𝑇0
1. 𝑑𝑉
=
𝐹𝐴0
1−𝑋 −
𝐾𝐶 𝑇

𝐸 1 1
2. 𝑘 = 𝑘1 𝑇1 exp 𝑅 𝑇1
−
𝑇
0
Δ𝐻𝑅𝑥 1 1
3. 𝐾𝐶 = 𝐾𝐶2 𝑇2 exp 𝑅 𝑇2
−
𝑇
0
𝑋 −Δ𝐻𝑅𝑥 𝑇𝑅
4. 𝑇 = 𝑇0 + 𝐶𝑃𝐴
0
5. Enter parameter values 𝑘1 , 𝐸, 𝑅, 𝐾𝐶2 , Δ𝐻𝑅𝑥 𝑇𝑅 , 𝐶𝑃𝐴 , 𝐶𝐴0 , 𝑇0 , 𝑇1 , 𝑇2
6. Enter initial values 𝑋 = 0, 𝑉 = 0
And final reactor volume 𝑉 = 𝑉𝑡

In any real problem, you will use an ODE solver rather than simple
techniques.