Chbe 6300 Graduate Kinetics and Reactor Design: Carsten Sievers 8/18/2020

ChBE 6300
Graduate Kinetics and

Reactor Design
Lecture 1
Carsten Sievers
8/18/2020
Introductions
 Instructor: Prof. Carsten Sievers
 TA: Olivia Williams

Hybrid Class
 A part of the class meets in person in ES&T L1255.
 See group assignments
 The remaining students can follow the class via BlueJeans.
 Olivia will moderate the chat during classes and read
questions at the next opportunity.
 Recorded lectures and slides (with gaps) will be available
on Canvas.
 All exams will be synchronous. Solutions need to be

uploaded as scans or photos on Canvas.
Safety Measures in Class
 You can only attend class on the days your group is
scheduled to attend.
 You must wear a mask to cover your mouth and nose at all
time in the classroom (or other Georgia Tech buildings).
 Only sit in the marked seats.
 Please allow the students at the end of the rows to leave
the classroom first.
Logistics
 Dr. Sievers office hour is only 10:30-11:00 this Wednesday
Kinetics
 How fast does a reaction occur?
 Rate of reaction: aAbB
𝑑𝑑𝐶𝐶𝐴𝐴
𝑟𝑟𝐴𝐴 =
𝑑𝑑𝑑𝑑
 Often written as power law

−𝑟𝑟𝐴𝐴 = 𝑘𝑘𝐶𝐶𝐴𝐴 𝑎𝑎
 Single or multiple steps  Mechanism

 Elementary and non-elementary reactions
 Most reactions non-elementary
Symbols
Irreversible reaction
Reversible reaction
Reaction in equilibrium or quasi-equilibrium
Reaction far from equilibrium
k is rate constant
K is equilibrium constant
kB Boltzmann's constant (sometimes just k)
Thermodynamics and Kinetics
 Thermodynamics impose constraints (limits) on chemical
reactions
 Thermodynamics are:
 Independent of time
 Independent of reaction path
 1st Law:
 Conservation of Energy
 ΔHr is independent of reaction path
Davis and Davis Appendix A

Thermodynamics and Kinetics
 2nd Law:
 Feasibility of reaction (ΔG<0)
 Reactions always occur towards equilibrium under the
given conditions (i.e. temperature)
 Thermodynamics do not tell us how fast we approach
equilibrium 𝐶𝐶 𝑠𝑠 + 𝑂𝑂 𝑔𝑔 → 𝐶𝐶𝐶𝐶 𝑔𝑔 ∆𝐺𝐺 ≪ 0 but very slow
2 2
 A reaction is feasible when the free energy is less than 0

 If a reaction is favored in forward direction (ΔG<0), then
the reverse direction is not favored under the same
conditions (ΔG > 0)
 ΔG is related to operating conditions.
 ΔG = ΔH - TΔS
(∆𝐺𝐺𝐺)𝑟𝑟 = � 𝜈𝜈𝑖𝑖 (𝐺𝐺𝑓𝑓 °)𝑖𝑖

Stoichiometry
 We need to account for the ratios in which reactants
and products are converted/formed:
𝑎𝑎𝑎𝑎 + 𝑏𝑏𝑏𝑏 → 𝑐𝑐𝑐𝑐 + 𝑑𝑑𝑑𝑑
 Stoichiometric coeffects 𝜈𝜈𝑖𝑖 (a, b, c, d) are negative for

reactants, positive for products
 Limiting reactant: whichever reactant runs out first
based on initial concentration (𝐶𝐶𝑖𝑖,0 ) and 𝜈𝜈𝑖𝑖
𝑏𝑏 𝑐𝑐 𝑑𝑑
𝐴𝐴 + 𝐵𝐵 → 𝐶𝐶 + 𝐷𝐷
𝑎𝑎 𝑎𝑎 𝑎𝑎
 Define conversion based on limiting reactant:
𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑜𝑜𝑜𝑜 𝐴𝐴 𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 𝑁𝑁𝐴𝐴,0 − 𝑁𝑁𝐴𝐴

𝑋𝑋𝐴𝐴 = =
𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑜𝑜𝑜𝑜 𝐴𝐴 𝑖𝑖𝑖𝑖 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑁𝑁𝐴𝐴,0
Stoichiometry
 Extent of reaction:
𝑁𝑁𝑖𝑖 − 𝑁𝑁𝑖𝑖,0
𝜉𝜉 𝑚𝑚𝑚𝑚𝑚𝑚 =
𝜈𝜈𝑖𝑖
Example
𝑁𝑁2 + 3𝐻𝐻2 ↔ 2𝑁𝑁𝐻𝐻3
Start: 20 mol N2 , 80 mol H2

End: 15 mol N2, 65 mol H2, 10 mol NH3
𝜈𝜈𝑁𝑁𝑁 = −1
𝜈𝜈𝐻𝐻𝐻 = −3
𝜈𝜈𝑁𝑁𝑁𝑁𝑁 = 2
Which is the limiting reactant?

 Nitrogen
Calculate the conversion based on the limiting

reactant. 20 − 15
𝑋𝑋𝑁𝑁𝑁 = = 0.25
20
Equilibrium Constant, K
𝛼𝛼𝛼𝛼 + 𝛽𝛽𝛽𝛽 ↔ 𝛾𝛾𝐶𝐶 + 𝛿𝛿𝛿𝛿
𝛾𝛾
𝑎𝑎𝐶𝐶 𝑎𝑎𝐷𝐷𝛿𝛿
𝐾𝐾 = 𝛽𝛽
𝑎𝑎𝐴𝐴𝛼𝛼 𝑎𝑎𝐵𝐵
𝑎𝑎𝑖𝑖 = activity of species i

𝑎𝑎𝑖𝑖𝜈𝜈𝑖𝑖 = active mass of species i
Law of Mass Action (Gouldberg & Waage, 1867):

“At constant T, the product of the active masses on the right
side of the reaction equation divided by the product of the
mass on the left side of the equation is a constant at
equilibrium, regardless of the amount to each species
present at the beginning of the reaction.”

Equilibrium Constant, K
 Does this mean that we will always observe an

equilibrium?
 No, depending on the rate of reaction, the equilibrium
may not be reached in a given time.
How can you determine activities?

𝑓𝑓
𝑎𝑎𝑖𝑖 = 𝑖𝑖
𝑓𝑓°𝑖𝑖
𝑓𝑓𝑖𝑖 = fugacity of species at equilibrium

𝑓𝑓𝑖𝑖 °=fugacity of species at standard conditions

Standard Conditions
 Gasses: pure component at 1 atm, 𝑓𝑓𝑖𝑖 °=1
 Solids: pure solid at 1 atm, 𝑓𝑓𝑖𝑖 ° = 1
 Liquids: pure liquid at its vapor pressure
 Solutions in liquid: 1M solution of such dilute conditions
that 𝑓𝑓𝑖𝑖 ° = 1
 For solids: fugacity variations are negligible

 For liquids: use ideal solutions theory (Lewis & Randall)
 For Gasses:
 Low pressure, ideal gas behavior. 𝑓𝑓𝑖𝑖 °= 𝑝𝑝𝑖𝑖 = 1 atm

Ideal Gas
𝛾𝛾 𝛿𝛿
𝑓𝑓𝐶𝐶 𝑓𝑓𝐷𝐷
𝐾𝐾 =
𝛼𝛼 𝛽𝛽
𝑓𝑓𝐴𝐴 𝑓𝑓𝐵𝐵
𝑓𝑓𝑖𝑖 = 𝑝𝑝𝑖𝑖 𝜈𝜈𝑖𝑖 𝜈𝜈𝑖𝑖 = activity coefficient
𝛾𝛾 𝛾𝛾
𝜈𝜈𝐶𝐶 𝜈𝜈𝐷𝐷𝛿𝛿 𝑝𝑝𝐶𝐶 𝑝𝑝𝐷𝐷𝛿𝛿
𝐾𝐾 = 𝛽𝛽
∗ 𝛽𝛽
= 𝐾𝐾𝜈𝜈 × 𝐾𝐾𝑝𝑝 = 𝐾𝐾𝜈𝜈 × 𝐾𝐾𝑦𝑦 × 𝑃𝑃∆𝑛𝑛
𝜈𝜈𝐴𝐴𝛼𝛼 𝜈𝜈𝐵𝐵 𝑝𝑝𝐴𝐴𝛼𝛼 𝑝𝑝𝐵𝐵
where ∆𝑛𝑛 = 𝛾𝛾 + 𝛿𝛿 − 𝛼𝛼 − 𝛽𝛽
Kp can be written with relative pressures (unitless) or in

pressure units like bar
Ideal Gas
for ideal gasses, 𝐾𝐾𝜈𝜈 =1.0
𝛾𝛾
𝑝𝑝𝐶𝐶 𝑝𝑝𝐷𝐷𝛿𝛿 (𝑃𝑃 ∗ 𝑦𝑦𝐶𝐶 )𝛾𝛾 (𝑃𝑃 ∗ 𝑦𝑦𝐷𝐷 )𝛿𝛿
𝐾𝐾 = 𝛽𝛽
= 𝛼𝛼 (𝑃𝑃 ∗ 𝑦𝑦 )𝛽𝛽
𝑝𝑝𝐴𝐴𝛼𝛼 𝑝𝑝𝐵𝐵 (𝑃𝑃 ∗ 𝑦𝑦𝐴𝐴 ) 𝐵𝐵
𝛾𝛾 𝛿𝛿 𝛾𝛾 𝛿𝛿
𝑦𝑦𝐶𝐶 𝑦𝑦𝐷𝐷 (𝛾𝛾+𝛿𝛿−𝛼𝛼−𝛽𝛽) 𝑦𝑦𝐶𝐶 𝑦𝑦𝐷𝐷 Δ𝑛𝑛
= 𝛼𝛼 𝑦𝑦 𝛽𝛽 𝑃𝑃 = 𝛼𝛼 𝑦𝑦𝛽𝛽 𝑃𝑃
𝑦𝑦𝐴𝐴 𝐵𝐵 𝑦𝑦𝐴𝐴 𝐵𝐵

Example: Equilibrium Conversion
𝐶𝐶𝐶𝐶 + 3𝐻𝐻2 ↔ 𝐻𝐻2 𝑂𝑂 + 𝐶𝐶𝐶𝐶4
Initial 1 mol 3 0 mol 0 mol 4 mol
Change -X -3X +X +X
Final 1-X 3-3X X X 4-2X mol
1 − 𝑋𝑋 𝑋𝑋
𝑦𝑦𝐶𝐶𝐶𝐶 = 𝑦𝑦𝐻𝐻𝐻𝐻𝐻 =
4 − 2𝑋𝑋 4 − 2𝑋𝑋
3(1 − 𝑋𝑋) 𝑋𝑋
𝑦𝑦𝐻𝐻𝐻 = 𝑦𝑦𝐶𝐶𝐶𝐶𝐶 =
4 − 2𝑋𝑋 4 − 2𝑋𝑋
𝑋𝑋 𝑋𝑋
𝑦𝑦𝐶𝐶𝐶𝐶𝐶 𝑦𝑦𝐻𝐻𝐻𝐻𝐻 ∗ 𝑋𝑋 2 (4 − 2𝑋𝑋)2
𝐾𝐾𝑦𝑦 = 3 = 4 − 2𝑋𝑋 4 − 2𝑋𝑋 3 =
𝑦𝑦𝐶𝐶𝑂𝑂 𝑦𝑦𝐻𝐻𝐻 1 − 𝑋𝑋 3 1 − 𝑋𝑋 27(1 − 𝑋𝑋)4
∗
4 − 2𝑋𝑋 4 − 2𝑋𝑋

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ChBE 6300

Graduate Kinetics and

 TA: Olivia Williams

 All exams will be synchronous. Solutions need to be

 Often written as power law

 Single or multiple steps  Mechanism

Reaction in equilibrium or quasi-equilibrium

Reaction far from equilibrium

Davis and Davis Appendix A

 A reaction is feasible when the free energy is less than 0

Davis and Davis Appendix A

 Stoichiometric coeffects 𝜈𝜈𝑖𝑖 (a, b, c, d) are negative for

𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑜𝑜𝑜𝑜 𝐴𝐴 𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 𝑁𝑁𝐴𝐴,0 − 𝑁𝑁𝐴𝐴

Start: 20 mol N2 , 80 mol H2

Which is the limiting reactant?

Calculate the conversion based on the limiting

𝑎𝑎𝑖𝑖 = activity of species i

Law of Mass Action (Gouldberg & Waage, 1867):

Davis and Davis Appendix A

 Does this mean that we will always observe an

How can you determine activities?

𝑓𝑓𝑖𝑖 = fugacity of species at equilibrium

Davis and Davis Appendix A

 For solids: fugacity variations are negligible

Davis and Davis Appendix A

Kp can be written with relative pressures (unitless) or in

Davis and Davis Appendix A

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