Chbe 6300 Graduate Kinetics and Reactor Design: Carsten Sievers 8/20/2020

ChBE 6300
Graduate Kinetics and

Reactor Design
Lecture 2
Carsten Sievers
8/20/2020
Announcements
 Homework 1 and solutions are available on Canvas
 Due date: September 1
 Recordings of lectures will be available on Canvas starting
with this one.
Previously in ChBE 6300
 Thermodynamics define constraints for kinetic processes.
 The equilibrium constant defines the end point of a reaction
at a given temperature.
 Today, we will wrap up thermodynamics and start reviewing

key concepts of undergraduate kinetics and reactor design
classes.
Thermodynamics
Equilibrium Constant, K
 The equilibrium constant under standard conditions can be
derived from:
∆𝐺𝐺𝐺𝑟𝑟
𝐾𝐾𝐾 = exp −
𝑅𝑅𝑅𝑅
 The equilibrium constant at another temperature can be
derived using van’t Hoff’s equation:
𝑑𝑑(𝑙𝑙𝑙𝑙𝑙𝑙) ∆𝐻𝐻𝑟𝑟
=
𝑑𝑑𝑑𝑑 𝑅𝑅𝑇𝑇 2
 How does K change qualitatively for an exothermic

reaction when T increases?
 If the heat of reaction is assumed to be constant over a
temperature range, the van’t Hoff equation can be
integrated:
Davis and Davis Appendix A

Caution!
 It is important to verify that the heat of reaction is constant,
𝑇𝑇
otherwise: ∆𝐻𝐻𝑟𝑟,𝑇𝑇 = ∆𝐻𝐻𝑟𝑟,0 + ∫298𝐾𝐾 𝛻𝛻𝐶𝐶𝑝𝑝 𝑑𝑑𝑑𝑑
 Examine thermodynamics before designing a reactor.
 Thermodynamics are not affected by:
 Reaction pathway
 Presence/absence of catalyst
 Ammonia synthesis. 𝑁𝑁2 + 3𝐻𝐻2 ↔ 2𝑁𝑁𝑁𝑁3
 Foreword reaction is thermodynamically favored at low
T
 High T is required for reasonable rate
Davis and Davis Appendix A

Practice Problem
The reaction A + B ↔ C + D is performed in batch reactor. Two experiments were
performed at 400 and 500 °C, respectively. The following data was found for the
concentrations for each compound.
a) Find the enthalpy of reaction assuming that it is independent of the

temperature. State any assumption you are making.
b) Find the standard free energy of reaction.
c) Is the reaction exothermic or endothermic?
Practice Problem
Practice Problem
Rate of Reaction
Rate of Reaction
 Rate of reaction: number of occurrences of stoichiometric
even per unit of time
𝑑𝑑𝜉𝜉 1 𝑑𝑑𝑁𝑁𝑖𝑖
𝑟𝑟𝐴𝐴 = =
𝑑𝑑𝑑𝑑 𝜈𝜈𝑖𝑖 𝑑𝑑𝑑𝑑
 Rate of production of species i:
𝑟𝑟𝑎𝑎 𝑟𝑟𝑏𝑏 𝑟𝑟𝑖𝑖 = 𝜈𝜈𝑖𝑖 𝑟𝑟
=
𝜈𝜈𝑎𝑎 𝜈𝜈𝑏𝑏
 Rates are typically normalized to an intrinsic property of
the system (volume, mass or surface area of catalyst)
1 𝑑𝑑𝜉𝜉 𝑚𝑚𝑚𝑚𝑚𝑚
𝑟𝑟𝑣𝑣𝑣𝑣𝑣𝑣 = 𝑟𝑟 =
𝑉𝑉 𝑑𝑑𝑑𝑑 𝑠𝑠∗𝐿𝐿
𝑟𝑟𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 = 𝑟𝑟𝑟 =
𝑚𝑚 𝑑𝑑𝑑𝑑 𝑠𝑠∗𝑔𝑔
𝑟𝑟𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 = 𝑟𝑟𝑟 =
𝐴𝐴 𝑑𝑑𝑑𝑑 𝑠𝑠∗𝑚𝑚2
Turnover Frequency
 Turnover Frequency (TOF): Rate normalized by number
of surface atoms or specific site.
𝑁𝑁𝐴𝐴𝐴𝐴 𝑑𝑑𝑁𝑁𝑖𝑖
𝑇𝑇𝑇𝑇𝑇𝑇 =
𝐿𝐿∗𝐴𝐴 𝑑𝑑𝑑𝑑
NAV = Avogadro's number (6.023*1023 molecules/mol)
L = number density of sites (cm-2)
A = surface area of catalyst
 TOF allows for comparison of catalysts

 Specific for given T, C or p, ξ
 Definition of rates is straight-forward for homogeneous
catalysts and enzymes
Turnover Frequency
 Ambiguity in defining rates for heterogeneous catalysts
 Sites can consist of ensembles (of number of atoms)
 Sites can have different activity
 Turnover Number (TON): total number f turnovers per site
over the lifetime of the catalyst
Rate of Reaction
 Reaction rates are functions of T and Ci (or pi)
𝑟𝑟 = 𝑘𝑘 𝑇𝑇 ∗ 𝑓𝑓(𝐶𝐶𝑖𝑖 )
 For elementary reactions, the order in i is equal to 𝜈𝜈𝑖𝑖

2𝐶𝐶𝐶𝐶3 𝑂𝑂𝑂𝑂 ⇌ 𝐻𝐻3 𝐶𝐶 − 𝑂𝑂 − 𝐶𝐶𝐻𝐻3 + 𝐻𝐻2 𝑂𝑂
2𝑀𝑀 ⇌ 𝐷𝐷 + 𝑊𝑊
k1 is forward rate constant,
k-1 is the rate constant for the reverse reaction
𝐾𝐾 = 𝑟𝑟𝑓𝑓 =
𝑟𝑟𝑟𝑟 =
Rate of Reaction
𝐶𝐶𝐷𝐷 𝐶𝐶𝑊𝑊 𝑘𝑘1 2
𝑟𝑟𝑓𝑓 = 𝑘𝑘1 𝐶𝐶𝑀𝑀 𝑟𝑟𝑀𝑀,𝑓𝑓 =
𝐾𝐾 = 2 = 𝑘𝑘
𝐶𝐶𝑀𝑀 −1 𝑟𝑟𝑟𝑟 = 𝑟𝑟𝑀𝑀,𝑟𝑟 =
𝑟𝑟𝑀𝑀,𝑛𝑛𝑛𝑛𝑛𝑛 =
 If we want to write the reaction rate in terms of other

species: 𝑟𝑟𝑀𝑀 𝑟𝑟𝐷𝐷 𝑟𝑟𝑊𝑊
= = =
−2 1 1
Rate constant
 Rate law is temperature dependent.
Describe with Arrhenius's Law:
−𝐸𝐸𝐴𝐴
𝑘𝑘 𝑇𝑇 = 𝐴𝐴 ∗ exp
𝑅𝑅𝑅𝑅
 Analogous to van’t Hoff Law:
∆𝐻𝐻𝑟𝑟 1 1
𝐾𝐾 𝑇𝑇 = 𝐾𝐾0 exp −
𝑅𝑅 𝑇𝑇0 𝑇𝑇
𝐸𝐸𝐴𝐴 1 1
𝑘𝑘 𝑇𝑇 = 𝑘𝑘(𝑇𝑇0 ) exp −
𝑅𝑅 𝑇𝑇0 𝑇𝑇
 The pre-exponential factor describes
the frequency of collisions and their
chances of success
http://4.bp.blogspot.com/_Obwvpc-
KSC4/S5RDowaC7GI/AAAAAAAAARk/BUzb5opK
3c8/s400/exothermic+endothermic.JPG
Ideal Reactors
Ideal Reactors
Batch Reactor Continuously Plug Flow

Stirred Tank Reactor
Reactor (PFR)
(CSTR)
Batch Reactor
Mole balance for the limiting component A:
Input = Output + Generation/Consumption + Accumulation
𝑟𝑟𝐴𝐴 =
With:
𝑁𝑁𝐴𝐴 = 𝑁𝑁𝐴𝐴𝐴 1 − 𝑋𝑋 with X based on limiting reactant
𝑑𝑑𝑁𝑁𝐴𝐴 𝑑𝑑𝑑𝑑
= −𝑁𝑁𝐴𝐴𝐴
𝑑𝑑𝑑𝑑 𝑑𝑑𝑑𝑑
Batch Reactor
𝑟𝑟𝐴𝐴 =
𝑡𝑡
� 𝑑𝑑𝑑𝑑 =
0
Where Xi is initial conversion, and Xf is final conversion
General design equation for a batch reactor:
If volume is constant:
𝑡𝑡 =
Expansion Factor
 Volume may change due to p, N, or T
 For an ideal gas:
𝑛𝑛𝑛𝑛𝑛𝑛
𝑉𝑉 =
𝑝𝑝
But when handling reactions with mole change, need more
equations:
𝑃𝑃𝑃𝑃 𝑁𝑁𝑇𝑇 𝑅𝑅𝑅𝑅
=
𝑃𝑃0 𝑉𝑉0 𝑁𝑁𝑇𝑇,0 𝑅𝑅𝑇𝑇0
𝑃𝑃 𝑇𝑇 𝑁𝑁𝑇𝑇
𝑉𝑉 = 𝑉𝑉0 0
𝑃𝑃 𝑇𝑇0 𝑁𝑁𝑇𝑇,0
𝑁𝑁𝑇𝑇 = 𝑁𝑁𝑇𝑇,0 + 𝛿𝛿𝑁𝑁𝐴𝐴𝐴 𝑋𝑋
Where δ is the change in # of moles over moles of A reacted
(δ= d/a + c/a - b/a - 1)
Expansion factor
𝑁𝑁𝑇𝑇 = 𝑁𝑁𝑇𝑇,0 + 𝛿𝛿𝑁𝑁𝐴𝐴𝐴 𝑋𝑋
𝑁𝑁𝑇𝑇 𝑁𝑁𝐴𝐴𝐴
= 1 + 𝛿𝛿 𝑋𝑋
𝑁𝑁𝑇𝑇,0 𝑁𝑁𝑇𝑇,0
𝑁𝑁𝑇𝑇
= 1 + 𝜖𝜖𝑋𝑋
𝑁𝑁𝑇𝑇,0
Where ε= 𝑦𝑦𝐴𝐴𝐴 𝛿𝛿
𝑝𝑝0 𝑇𝑇
𝑉𝑉 = 𝑉𝑉0 1 + 𝜖𝜖𝜖𝜖
𝑝𝑝 𝑇𝑇0
ε is called expansion factor

Space Time
 Space-time, τ, is the time required to process one reactor
volume of feed measured at specific inlet conditions.
𝐶𝐶𝐴𝐴0 𝑉𝑉 𝑉𝑉
𝜏𝜏 = =
𝐹𝐹𝐴𝐴𝐴 𝜈𝜈0
 Space-velocity, s, is the number of reactor volumes
treated in a certain time.
1
𝑠𝑠 =
𝜏𝜏
𝑋𝑋𝐴𝐴 𝑑𝑑𝑑𝑑
̅
 Mean residence time, 𝑡𝑡 = 𝐶𝐶𝐴𝐴𝐴 ∫0
(−𝑟𝑟𝐴𝐴 )(1+𝜖𝜖𝑋𝑋𝐴𝐴 )
𝑉𝑉
 For liquids and constant density gasses, 𝜏𝜏 = 𝑡𝑡̅ =
𝜈𝜈0
CSTR
Often XA0 is zero, so the input is just FA0. Run at steady

state, so accumulation is zero.
More general: feed enters in partially converted state:

CSTR
 The rate inside the reactor is representative of the exit
stream conditions
 For constant V,
𝐶𝐶𝐴𝐴
𝑋𝑋𝐴𝐴 = 1 −
𝐶𝐶𝐴𝐴𝐴
𝑉𝑉 𝑋𝑋𝐴𝐴 𝐶𝐶𝐴𝐴𝐴 − 𝐶𝐶𝐴𝐴

= =
𝐹𝐹𝐴𝐴𝐴 −𝑟𝑟𝐴𝐴 𝐶𝐶𝐴𝐴𝐴 (−𝑟𝑟𝐴𝐴 )
PFR
𝑑𝑑𝐹𝐹𝐴𝐴 = 𝑑𝑑 𝐹𝐹𝐴𝐴𝐴 1 − 𝑋𝑋𝐴𝐴 = −𝐹𝐹𝐴𝐴𝐴 𝑑𝑑𝑋𝑋𝐴𝐴
𝐹𝐹𝐴𝐴0 𝑑𝑑𝑋𝑋𝐴𝐴 = −𝑟𝑟𝐴𝐴 𝑑𝑑𝑑𝑑
For any ε
PFR
 PFRs are often used for gas phase reactions
 Need to watch for volume change (need 𝜖𝜖 term)
−𝑟𝑟𝐴𝐴 = 𝑘𝑘𝐶𝐶𝐴𝐴 2
𝑑𝑑𝑑𝑑
𝐹𝐹𝐴𝐴0 = −𝑟𝑟𝐴𝐴
𝑑𝑑𝑑𝑑
𝐶𝐶𝐴𝐴𝐴 (1−𝑋𝑋)
𝐶𝐶𝐴𝐴 = isothermal, isobaric
(1+𝜖𝜖𝜖𝜖)
𝐹𝐹𝐴𝐴𝐴 𝑋𝑋 (1+𝜖𝜖𝜖𝜖)2
𝑉𝑉 = 2 = ∫0 𝑑𝑑𝑑𝑑
𝑘𝑘𝐶𝐶𝐴𝐴𝐴 (1−𝑋𝑋)2
Use integral tables to solve. Folger Appendix A.1

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ChBE 6300

Graduate Kinetics and

 Today, we will wrap up thermodynamics and start reviewing

 How does K change qualitatively for an exothermic

Davis and Davis Appendix A

Davis and Davis Appendix A

a) Find the enthalpy of reaction assuming that it is independent of the

 TOF allows for comparison of catalysts

 For elementary reactions, the order in i is equal to 𝜈𝜈𝑖𝑖

 If we want to write the reaction rate in terms of other

Batch Reactor Continuously Plug Flow

Input = Output + Generation/Consumption + Accumulation

Where Xi is initial conversion, and Xf is final conversion

General design equation for a batch reactor:

ε is called expansion factor

Input = Output + Generation/Consumption + Accumulation

Often XA0 is zero, so the input is just FA0. Run at steady

More general: feed enters in partially converted state:

𝑉𝑉 𝑋𝑋𝐴𝐴 𝐶𝐶𝐴𝐴𝐴 − 𝐶𝐶𝐴𝐴

𝑑𝑑𝐹𝐹𝐴𝐴 = 𝑑𝑑 𝐹𝐹𝐴𝐴𝐴 1 − 𝑋𝑋𝐴𝐴 = −𝐹𝐹𝐴𝐴𝐴 𝑑𝑑𝑋𝑋𝐴𝐴

𝐹𝐹𝐴𝐴0 𝑑𝑑𝑋𝑋𝐴𝐴 = −𝑟𝑟𝐴𝐴 𝑑𝑑𝑑𝑑

Use integral tables to solve. Folger Appendix A.1

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