Department of Chemical and Biomolecular Engineering

CN2105 Reaction Engineering

Unit 2:
Design Equations for Ideal
Reactors

Prof. Ning Yan, 2024/2025 Sem 1

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Learning Objectives (Unit 2)

1. Mole balance equations for any species
2. Definition of conversion
3. Design equations for ideal reactors (batch, CSTR and PFR)
4. Stoichiometric table analysis
5. Definitions of space time and space velocity
6. Semi-batch reactor
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Recap: balance equations

ṁ𝑜𝑢𝑡
Mass balance

𝑖𝑛 out

ṁ𝑖𝑛

Energy balance
2 2 ( )
𝑖𝑛 𝑖𝑛 𝑖𝑛 𝑖𝑛 𝑜𝑢𝑡 𝑜𝑢𝑡 𝑜𝑢𝑡
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1. Mole Balance
System boundary

Fi0 Reactor Fi

• Mole balance for species i at any time t:

Inflow + Rate of generation = Outflow + Rate of accumulation

where ri is the rate of generation per unit volume (negative if species i is a

reactant that is being consumed), which may vary throughout the reactor of
volume V, and Ni is the amount of species i in the reactor.
• The design equations for all types of reactors can be derived from this general
mole balance expression!
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2. Conversion
• The conversion of reacting species i is defined as:

• For batch reactors:

where Ni0 is the initial amount of species i and Ni is the amount of species i at
any time.

• For flow reactors (CSTR and PFR):

These two simple expressions of conversion will be extensively used later

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3. Ideal Batch Reactor

General mole balance equation:

No inflow and outflow: 𝐹 = 𝐹 = 0

• What are the key characteristics

Check unit: left = mol∙m-3∙s-1 ∙ m3 = mol∙s-1 right = mol∙s-1 for an ideal batch reactor?
T, c
• Steady state?
• Design equation (differential form):

• Design equation (integral form):

𝑁 = 𝑁 (1 − 𝑥 )
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3. Ideal Batch Reactor

• For batch reactors with constant reaction volume V
(constant density):

• For batch reactors with varying V (liquid, variable

density):
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3. Ideal Batch Reactor: graphics

1. What does the area

under the curve represent?

2. For a reaction conducted at the same

temperature, which reactor below first reach
90% conversion? All three can be regarded
as ideal batch reactors.

xi
We can do reactor design completely
based on graphics! (details later)
1 L, 1 stirrer 10 L, 1 stirrer 10 L, 2 stirrers
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3. Ideal Continuous Stirred Tank Reactor (CSTR)

General mole balance equation:

Fi0 Fi
V

• Steady state?
• Well-mixing?

• Mole balance becomes:

• Design equation:
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3. Ideal Plug Flow Reactor (PFR)

• Assumptions:
• No back mixing (axial dispersion) Fi0 V Fi
• Contents are uniform over cross
section • Steady state?
• Concentrations vary continuously in the
axial direction from the reactor inlet to the
reactor outlet due to chemical reactions.

A B C D

Rank the product concentration at

point A, B, C and D
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3. Ideal Plug Flow Reactor (PFR)

pigments PFR

Key messages:
• The residence time for all molecules inside PFR is identical
• Every indefinitely small “packet” inside PFR can be regarded as a ideal batch reactor
• Every indefinitely small “packet” will have the same conversion of reagent
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3. Ideal Plug Flow Reactor (PFR)

General mole balance equation:

Differentiating the mole balance equation with respect to V:

• Design equation (differential form):

• Design equation (integral form):

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3. Constant and Variable Density in Flow Reactors

• For flow reactors, the reaction volume is fixed and is equal to the reactor
volume.

• For a compressible fluid, the volumetric flow rate through the reactor may not
be constant when the number of moles changes due to chemical reactions (e.g.
a gas phase reaction).

̇
• Since (where ρ is the density of fluid, is the mass flow rate and v is the
volumetric flow rate), the reaction system is constant density only if the
volumetric flow rate is constant throughout the reactor:
• If , the system is constant density.
• If , the system is variable density.
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3. Ideal Batch Reactor vs. CSTR vs. PFR

Design equations:

1 𝑑𝑁 𝑁 𝑑𝑥 𝑑𝑁 𝑑𝑥
𝑟 = =− 𝑡= =𝑁
𝑉 𝑑𝑡 𝑉 𝑑𝑡 𝑟𝑉 −𝑟 𝑉

𝐹 𝑥
𝑉=
−𝑟

𝑑𝐹 𝑑𝑥 𝑑𝑥
𝑟 = = −𝐹 𝑉=𝐹
𝑑𝑉 𝑑𝑉 −𝑟

What is your observation? Why is CSTR so different from the other two?
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Quiz 1
1. For batch reactors with varying V, does always hold?
1 𝑑𝑁
𝑟 =
𝑉 𝑑𝑡

2. For the reaction A + B → C + D (where A, B, C and D can be regarded as

ideal gases), if the temperature increases along a PFR, what happens to the
volumetric flow rate?

3. For the reaction A + B → C + D (where A, B, C and D can be regarded as

ideal gases), if the pressure decreases along a PFR, what happens to the
volumetric flow rate?
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4. Stoichiometric Table: why?

See the following scenario:
A catalytic converter (PFR) conducts the following reaction to remove trace amount of CO under
constant T and P.
2CO (g) + O2 (g) → 2CO2 (g)

Per design specification, we know 𝐹 = 20 𝑚𝑜𝑙/𝑚𝑖𝑛; 𝐹 = 100 𝑚𝑜𝑙/𝑚𝑖𝑛; 𝐹 = 400 𝑚𝑜𝑙/𝑚𝑖𝑛;

𝑥 = 95%.
What is the percentage/concentration of CO and CO2, respectively, in the exist?
Need to know the correlation between concentration of CO and CO2 as a function of CO conversion.

• The stoichiometric table is used to facilitate calculations by:

 expressing concentrations of all species in a reaction in terms of a common
variable, the conversion of the limiting reactant (useful for single reactions).
 establishing the relations between concentrations of different species, e.g. for the
reaction A → B → C, it can be shown that cA + cB + cC = constant.
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4. Stoichiometric Table: why?

Take one more look at the design equations:

𝑑𝑥 𝐹 𝑥 𝑑𝑥
𝑡=𝑁 𝑉= 𝑉=𝐹
−𝑟 𝑉 −𝑟 −𝑟 𝑟 = 𝑓(𝑇, 𝑐 )

Take first order reaction as an example: 𝑟 = 𝑘𝑐

𝑑𝑥 𝐹 𝑥 𝑑𝑥
𝑡=𝑁 𝑉= 𝑉=𝐹
−𝑘𝑐 𝑉 −𝑘𝑐 −𝑘𝑐
Need to know the correlation between 𝑐 and 𝑥 .

• This section also helps to establish the correlation between c and x

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4.1 Stoichiometric Table for Batch Reactors

• Consider reaction: aA + bB → cC + dD where A is the limiting reactant.
• Taking A as the basis, rewrite the reaction as: A + B → C + D
• The stoichiometric table can be constructed for a batch reactor:

Species t=0 Δ t>0

A NA0 −xANA0 NA0 − xANA0
B NB0 − xANA0 NB0 − xANA0 What if two reactions are involved?
C NC0 + xANA0 NC0 + xANA0 a1A + bB → cC + dD
a2A + c2C → eE
D ND0 + xANA0 ND0 + xANA0
Hint: define the molar extent of the
Inert NI0 0 NI0 two reactions 𝜉1, 𝜉2
Total N0 N0 + (
𝒂 𝒃 𝒄 𝒅
) xANA0
𝒂
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4.1 Stoichiometric Table for Batch Reactors

• Define θi and δ:

• Then:
xA

For a batch reactor with constant V (constant density)

• An expression for ci can be obtained:
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4.1 Stoichiometric Table for Batch Reactors

For a batch reactor with varying V (variable density)
• A relationship between V and V0 is required. For gas phase reactions, this takes
the form of an equation of state:

• where z is the compressibility factor.

• The relationship between V and V0 can be derived:

• Divide the earlier expression for N by N0 and define :

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4.1 Stoichiometric Table for Batch Reactors

For a batch reactor with varying V (variable density) (cont’d)
• Substitute into the expression for V:

• An expression for ci can now be derived:

• For the special case of low pressure operations (z0, z ≈ 1), negligible pressure drop (P =
P0) and isothermal system (T = T0), the expression for ci is simplified:

For species A, it Why do we bother to express 𝑐 in

further simplifies to: such a complicated way?
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4.2 Stoichiometric Table for Flow Reactors

• Consider the same reaction: A + B → C + D where A is the limiting reactant.
• The stoichiometric table can be similarly constructed for a flow reactor:
Species Inflow Δ Outflow
A FA0 −xAFA0 FA0 − xAFA0
B FB0 − xAFA0 FB0 − xAFA0
C FC0 + xAFA0 FC0 + xAFA0
D FD0 + xAFA0 FD0 + xAFA0
Inert FI0 0 FI0
Total F0 (1 + εAxA)F0
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4.2 Stoichiometric Table for Flow Reactors

For a flow reactor with constant v (constant density)
• An expression for ci can be similarly obtained:

For a flow reactor with varying v (variable density)

• For gas phase reactions, the equation of state now takes the form:

• The corresponding expression for ci can be derived:

• For isothermal low pressure systems with negligible pressure drop:

Compare these with the
For species A, it
equivalent equations for batch
further simplifies to:
reactor. What do you find?
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Revisit: can you solve it now?

A catalytic converter (PFR) conducts the following reaction to remove trace amount of CO under
constant T and P.
2CO (g) + O2 (g) → 2CO2 (g)

Per design specification, we know 𝐹 = 40 𝑚𝑜𝑙/𝑚𝑖𝑛; 𝐹 = 100 𝑚𝑜𝑙/𝑚𝑖𝑛; 𝐹 = 400 𝑚𝑜𝑙/𝑚𝑖𝑛;

𝑥 = 95%.
What is the percentage/concentration of CO and CO2, respectively, in the exist?
𝜈
Species Inflow Δ Outflow 𝜃 −𝜈 𝑥
𝑐 = 𝑐
A (CO) 40 -38 2 1+𝜀 𝑥
B (O2) 100 -19 81 𝐹 −2 − 1 + 2 40
C (CO2) 0 38 38 𝜀 =𝛿 = × = −0.037
𝐹 2 540
Inert (N2) 400 0 400 1 − 0.95
cCO: = ×𝑐
Total 540 521 1 − 0.037 × 0.95
𝐹 2 0.95
Percentage CO: = = = 0.38% cCO2: = ×𝑐
𝐹 521 1 − 0.037 × 0.95
𝐹 38
Percentage CO2: = = = 7.29% Based on pV = NRT cCO0 = RT/p
𝐹 521
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5. Space Time and Space Velocity

• The space time is defined as:

• Space time is the time necessary to process one reactor volume of fluid based
on the inlet conditions.

• The space velocity is defined as:

• where v can be the inlet or outlet volumetric flow rate or their equivalent values
at other operating conditions.
• If v0 is used to calculate SV, the value obtained is equal to .
• SV is also known as the dilution rate in biochemical reactors (where v = v0 often
holds).
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Quiz 2
1. The following gas-phase reaction is conducted in a PFR. Is the ε positive,
negative or zero? 𝑁
𝜀 =𝛿
CO(g) + O2(g) → CO2(g) 𝑁
−𝑎 − 𝑏 + 𝑐 + 𝑑
𝛿=
𝑎
2. For the same reaction in 1, what happens to the volumetric flow rate?

3. What are the units of the space velocity?

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Q1
For gas phase reaction A + B → 2C + D, what can be said about εA ?
A. εA is positive
B. εA is negative
C. εA is zero
D. εA has a fixed value since we know the reaction stoichiometry
𝑁
𝐵𝑎𝑡𝑐ℎ: 𝜀 = 𝛿
𝑁
𝐹
𝐹𝑙𝑜𝑤: 𝜀 = 𝛿
𝐹

−𝑎 − 𝑏 + 𝑐 + 𝑑
aA + bB → cC + dD 𝛿=
𝑎

−1 − 1 + 2 + 1
𝛿= =1
1
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Q2
Gas phase reaction A + B → 2C + D is conducted in a PFR and a CSTR under
the same isothermal and isobaric conditions. A, B has first and zeroth order,
respectively. Reaction rate r = -rA = kcA. Two reactors achieve the same
conversion. Which reactor is bigger?
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Q3
Gas phase reaction A + B → 2C + D is conducted in a PFR under isothermal
and isobaric conditions. A, B has first and zeroth order, respectively.
Reaction rate r = -rA = kcA. What would the graph look like?

1
𝑐 −𝑟
−𝑟

1 1 1 1
−𝑟 −𝑟 −𝑟 −𝑟

A 𝑐 B 𝑐 C 𝑐 D 𝑐
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Q4
Gas phase reaction A + B → 2C + D is conducted in a PFR under isothermal
and isobaric conditions. A, B has first and zeroth order, respectively.
Reaction rate r = -rA = kcA. Find
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6. Semi-Batch Reactor

v0, cB0
where V, cA and cB vary with time. V, cA, cB

• Semi-batch reactors can be very effective in maximising selectivity in liquid phase

reactions.
• The reactant that starts in the reactor is always the limiting reactant (assume
supplying of B is unlimited).
• Consider a liquid phase reaction (constant density) between A and B, where A is
initially present in the reactor while B is fed through the inlet.
The reaction volume is given by:

where V0 is the initial reaction volume (at t = 0) and t is time. Self-study, not
required.
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6. Semi-Batch Reactor
• Mole balance for A (no inflow and outflow, well-mixed reactor contents):

• Mole balance for B (no outflow, well-mixed reactor contents):

• For second order kinetics (e.g. rA = rB = −kcAcB), the simultaneous ODEs are
best solved numerically. Self-study, not required.
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Appendix 1: Common Space Velocities

• Liquid Hourly Space Velocity (LHSV) uses the equivalent volumetric flow rate of
the reactant at a standard temperature (usually 15°C) where the reactant is a
liquid, even though the reactant may be a gas under the actual operating
conditions.

• Gas Hourly Space Velocity (GHSV) uses the equivalent volumetric flow rate of
the gaseous reactant measured at a standard temperature and pressure.
Different industries may have their own definitions of standard temperature and
pressure.
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Appendix 2: Residence Time

• Residence time (RT) is the actual time spent in the reactor.

• For CSTR, since the prevailing flow rate is vout, RT is calculated as:

• For PFR, RT can be shown to be:

Try to prove it yourself

• RT is equal to space time only for constant density systems where v = v0 = vout.

• RT is not a useful parameter for reactor design.