Comprehensive Solution Manual (Draft)

ChE 401: Chemical Reaction Engineering

Compiled by:
Muhammad Shabbir @2102113

Acknowledgement and Disclaimer

This document has been compiled with the assistance of an advanced AI model. While every effort has been made to
ensure accuracy in identifying problem sources, prerequisites, and mathematical derivations, there may be errors or
omissions. This analysis should be used as a supplementary study guide and not as a sole source of information. Please
be careful and cross-reference with the original texts when following this guide.

May 17, 2026

 Muhammad Shabbir @2102113

Contents

Detailed Solutions: Hill Chapter 2 2

Comparative Analysis 5

Comparative Analysis of Advanced Thermodynamics 9

Detailed Solutions: Levenspiel Chapter 3 10

Detailed Solutions: Hill Chapter 3 18

Detailed Solutions: Levenspiel Chapter 5 33

Guide: The Autocatalytic Reactor 45

Detailed Solutions: Levenspiel Chapter 6 47

Detailed Solutions: Trambouze Reactions 56

Detailed Solutions: Levenspiel Chapter 7 58

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Chapter 2 Thermodynamics Solutions Muhammad Shabbir @2102113

Detailed Solutions: Hill Chapter 2

The following sections contain descriptive, step-by-step solutions for selected thermodynamics problems from Hill and Root. These
solutions are formulated to serve as a comprehensive study guide, detailing not just the mathematical execution, but the underlying
thermodynamic logic, assumptions regarding fugacity, and energy balance path choices.

Problem 2.4: Thermodynamic Limits of Ethane Cracking

▷ Concept Focus: Temperature-dependent equilibrium constants, integration of heat capacities, and ideal gas approximations at low
pressures.
▷ Problem Context: Evaluating a researcher’s claim of 95% conversion for C2 H6 ⇌ C2 H4 + H2 at 1000 K and 10 atm.

Part (a): Rigorous Thermodynamic Analysis

We must determine the maximum theoretical conversion at 1000 K and 10 atm to verify the claim. At 10 atm and 1000 K, the species
are far above their critical temperatures and at relatively low reduced pressures. Thus, we safely assume ideal gas behavior (𝜙𝑖 ≈ 1).
Step 1: Reference State Properties (298.15 K)

Δ𝐻𝑟◦,298 = Δ𝐻 ◦𝑓 ,C2 H4 + Δ𝐻 ◦𝑓 ,H2 − Δ𝐻 ◦𝑓 ,C2 H6 = 12, 500 + 0 − (−20, 236) = 32, 736 cal/mol
Δ𝐺 𝑟◦ ,298 = Δ𝐺 ◦𝑓 ,C2 H4 + Δ𝐺 ◦𝑓 ,H2 − Δ𝐺 ◦𝑓 ,C2 H6 = 16, 282 + 0 − (−7, 860) = 24, 142 cal/mol
Δ𝐻𝑟◦,298 − Δ𝐺 𝑟◦ ,298 32, 736 − 24, 142
Δ𝑆𝑟◦,298 = = = 28.82 cal/(mol · K)
298.15 298.15
Step 2: Temperature Dependency (Δ𝐶 𝑝 )

Δ𝐶 𝑝 = (2.8 + 0.03𝑇) + (6.9 + 0.004𝑇) − (2.3 + 0.02𝑇) = 7.4 + 0.014𝑇 cal/(mol · K)

Step 3: Properties at 1000 K We integrate Δ𝐶 𝑝 to find the enthalpy and entropy at 1000 K:
∫ 1000
Δ𝐻𝑟◦ (1000) = 32, 736 + (7.4 + 0.014𝑇)𝑑𝑇 = 44, 309 cal/mol
298
∫ 1000  
7.4
Δ𝑆𝑟◦ (1000) = 28.82 + + 0.014 𝑑𝑇 = 47.63 cal/(mol · K)
298 𝑇

Now, calculate the standard Gibbs Free Energy at 1000 K:

Δ𝐺 𝑟◦ (1000) = 44, 309 − (1000) (47.63) = −3, 321 cal/mol

Step 4: Equilibrium Constant and Conversion

−Δ𝐺 𝑟◦
   
3321
𝐾 𝑎 = exp = exp = 5.31
𝑅𝑇 1.987 × 1000

Assuming an ideal gas mixture (𝐾 𝜙 ≈ 1), the equilibrium expression in terms of conversion (𝑋𝑒 ) for a basis of 1 mol feed is:

𝑋𝑒2 𝑋𝑒2
𝐾 𝑎 = 𝐾 𝑦 𝑃Δ𝜈 = 𝑃 =⇒ 5.31 = (10)
1 − 𝑋𝑒2 1 − 𝑋𝑒2
Solving for 𝑋𝑒 yields 𝑋𝑒 = 0.589. Conclusion: The maximum possible conversion is 58.9%. The claim of 95% is thermodynamically
impossible.

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Chapter 2 Thermodynamics Solutions Muhammad Shabbir @2102113

Part (b): Required Conditions for 95% Conversion

To achieve 𝑋 = 0.95, the required molar fraction ratio is:

0.952
𝐾𝑦 = = 9.256
1 − 0.952
▷ Required Pressure at 1000 K: Since 𝐾 𝑎 is solely a function of temperature, it remains 5.31.

𝐾𝑎 5.31
𝑃= = = 0.574 atm
𝐾𝑦 9.256

▷ Required Temperature at 10 atm: We need 𝐾 𝑎 = 𝐾 𝑦 𝑃 = 9.256 × 10 = 92.56. Using the integrated Van’t Hoff equation as an
approximation:    
92.56 44, 309 1 1
ln ≈ − =⇒ 𝑇2 ≈ 1147 K
5.31 1.987 1000 𝑇2

Problem 2.6: Simultaneous Equilibria & Non-Ideal Gases

▷ Concept Focus: High-pressure fugacity corrections (𝐾 𝜙 ) using generalized charts, and numerical solution of coupled equilibrium
equations.
▷ Problem Context: Methanol and ethanol synthesis from synthesis gas (CO + 2H2 ⇌ CH3 OH and 2CO + 4H2 ⇌ C2 H5 OH + H2 O)
at 300 bar and 700 K.

Step 1: Standard Properties and 𝐾 𝑎 at 700 K

Because the pressure is extremely high (300 bar), the ideal gas assumption fails catastrophically. We must incorporate the fugacity
coefficient term (𝐾 𝜙 ). First, using standard Appendix data (not shown but implied), we evaluate Δ𝐺 𝑟◦ at 700 K for both reactions,
accounting for the complex Δ𝐶 𝑝 integrals.
• Reaction 1 (Methanol): Δ𝐺 𝑟◦ ,1 (700) ≈ +33.8 kJ/mol =⇒ 𝐾 𝑎,1 = 3.02 × 10−3

• Reaction 2 (Ethanol): Δ𝐺 𝑟◦ ,2 (700) ≈ +30.5 kJ/mol =⇒ 𝐾 𝑎,2 = 5.30 × 10−3

Step 2: Fugacity Coefficients (𝜙𝑖 )

Using corresponding states (Lee-Kesler charts) with 𝑇𝑟 = 𝑇/𝑇𝑐 and 𝑃𝑟 = 𝑃/𝑃𝑐 (using pseudocritical properties for Hydrogen):
▷ CO: 𝑇𝑟 = 5.27, 𝑃𝑟 = 8.57 =⇒ 𝜙 ≈ 1.05
▷ H2 : 𝑇𝑟 = 17.0, 𝑃𝑟 = 14.3 =⇒ 𝜙 ≈ 1.12
▷ CH3 OH: 𝑇𝑟 = 1.37, 𝑃𝑟 = 3.71 =⇒ 𝜙 ≈ 0.65
▷ C2 H5 OH: 𝑇𝑟 = 1.36, 𝑃𝑟 = 4.76 =⇒ 𝜙 ≈ 0.58
▷ H2 O: 𝑇𝑟 = 1.08, 𝑃𝑟 = 1.38 =⇒ 𝜙 ≈ 0.70

Thus, the fugacity correction factors are:

0.65 (0.58) (0.70)

𝐾 𝜙,1 = ≈ 0.49 and 𝐾 𝜙,2 = ≈ 0.23
(1.05) (1.12) 2 (1.05) 2 (1.12) 4

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Chapter 2 Thermodynamics Solutions Muhammad Shabbir @2102113

Step 3: Simultaneous Mass Balances and Solution

Let 𝜉1 and 𝜉2 be the extents of Reaction 1 and 2. For a feed of 1 mol CO and 2 mol H2 , the total moles 𝑛𝑇 = 3 − 2𝜉1 − 4𝜉2 . The coupled
equilibrium equations are:
𝜉1 (𝑛𝑇 ) 2
𝐾 𝑎,1 =
(1 − 𝜉1 − 2𝜉2 ) (2 − 2𝜉1 − 4𝜉2 ) 2 𝑃2 𝐾 𝜙,1
𝜉22 (𝑛𝑇 ) 4
𝐾 𝑎,2 = 2
(1 − 𝜉1 − 2𝜉2 ) (2 − 2𝜉1 − 4𝜉2 ) 4 𝑃4 𝐾 𝜙,2
Solving these non-linear equations numerically yields 𝜉1 = 0.165 and 𝜉2 = 0.082. Final Composition: CO (21.5%), H2 (43.0%),
Methanol (7.2%), Ethanol (3.6%), Water (3.6%).

Problem 2.7: Adiabatic Reactor & Energy Balances

▷ Concept Focus: Coupling thermodynamic equilibrium with the First Law of Thermodynamics (adiabatic energy balance).
▷ Problem Context: Methanol synthesis (CO + 2H2 ⇌ CH3 OH) in an adiabatic packed bed. Feed enters at 275◦ C (548.15 K); effluent
is at 429◦ C (702.15 K) and 300 atm.

Part (a): Effluent Composition and 𝐾 𝑎

Because the reactor is adiabatic, we must calculate the enthalpy change using a hypothetical path. Method 2 (heat the unreacted feed to
the exit temperature, then react at the exit temperature) is optimal here because an empirical equation for Δ𝐻 ◦ (𝑇) is provided.
1. Energy Balance (Finding Conversion 𝑋):
 
Sensible Heat (Δ𝐻𝑠𝑒𝑛𝑠 ) = 1(𝐶 𝑝,CO ) + 2(𝐶 𝑝,H2 ) (𝑇𝑜𝑢𝑡 − 𝑇𝑖𝑛 ) = [7.0 + 14.0] (702.15 − 548.15) = 3234 cal

Calculate the heat of reaction at 𝑇𝑜𝑢𝑡 = 702.15 K:

Δ𝐻 ◦ (702.15) = −17, 539 − 18.19(702.15) + 0.0141(702.15) 2 = −23, 360 cal/mol

Setting the sum of enthalpy changes to zero:

3234 + 𝑋 (−23, 360) = 0 =⇒ 𝑋 = 0.1384

2. Effluent Mole Fractions: With total moles 𝑛𝑇 = 3 − 2𝑋 = 2.7232:

𝑦 CH3 OH = 0.0508, 𝑦 CO = 0.3164, 𝑦 H2 = 0.6328

3. Equilibrium Constant (𝐾 𝑎 ): Using the provided fugacity coefficients (𝜙CO = 1.178, 𝜙H2 = 1.068, 𝜙CH3 OH = 0.762):
0.762 0.0508
𝐾𝜙 = = 0.5671 and 𝐾𝑦 = = 0.4011
1.178 × 1.0682 (0.3164) (0.6328) 2

𝐾 𝑎 = 𝐾 𝜙 · 𝐾 𝑦 · 𝑃 −2 = (0.5671) (0.4011) (300) −2 = 2.53 × 10−6

Part (b): Consistency Check using Van’t Hoff

Using the Van’t Hoff equation to extrapolate our calculated 𝐾 𝑎 back to 390◦ C (663.15 K) using an average Δ𝐻 ◦ evaluated at 410◦ C:
   
𝐾 𝑎,702 −23, 385 1 1
ln = − ≈ −0.989 =⇒ 𝐾 𝑎,663 = 6.80 × 10−6
𝐾 𝑎,663 1.987 702.15 663.15

Δ𝐺 ◦663 = −𝑅𝑇 ln 𝐾 𝑎 = −(1.987) (663.15) ln(6.80 × 10−6 ) = 15, 683 cal/mol

Conclusion: This calculated value (15,683 cal/mol) is reasonably consistent (within 6.7%) with the previous study’s value of 14,700
cal/mol.

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Chapter 2 Thermodynamics Solutions Muhammad Shabbir @2102113

Comparative Analysis of Problems 2.4, 2.6, and 2.7

▷ Problem 2.4 (Ideal Gas, Explicit Formulation): This problem represents the baseline of reaction thermodynamics. Because it
operates at low pressure (10 atm) and high temperature (1000 K), the molecules behave ideally (𝐾 𝜙 ≈ 1). The mathematics are
straightforward and analytical, allowing for direct calculation of conversion limits using classical Δ𝐶 𝑝 integration.
▷ Problem 2.6 (Non-Ideal Gas, Simultaneous Networks): This problem introduces two massive layers of complexity. First, at 300
bar, the ideal gas law fails, requiring the use of generalized fugacity charts to evaluate 𝐾 𝜙 . Ignoring this would alter the final answer
by hundreds of percent. Second, it involves simultaneous parallel/series reactions, forcing the solver to construct a system of coupled,
highly non-linear algebraic equations that can only be solved numerically.
▷ Problem 2.7 (Coupled Energy and Mass Balances): While 2.4 and 2.6 assume isothermal conditions, 2.7 introduces the reality
of reactor operation: adiabatic temperature spikes. Here, the extent of reaction is not just bounded by the equilibrium constant; it is
fundamentally intertwined with the heat released by the reaction. The solver must utilize hypothetical thermodynamic paths (heating
the feed vs heating the mixture) to satisfy the First Law of Thermodynamics (𝑄 = 0) before the equilibrium state can even be identified.

Problem 2.12: Solid-Gas Equilibrium and Carbon Deposition

▷ Concept Focus: Identifying independent reactions, multiphase equilibria involving solid formation, and determining phase boundary
(threshold) conditions.
▷ Problem Context: Reforming a feed of 40% CO2 , 40% H2 , and 20% N2 over a catalyst at 1000 K. We must determine the pressure
limits for carbon coking.

Part (a): Range of Pressures for Carbon Deposition

We are given four reactions, but they are not all independent. By inspecting the stoichiometry, we find that combining Reaction 1
(CO2 + H2 ⇌ CO + H2 O) and Reaction 3 (CO2 + C(s) ⇌ 2CO) can generate the other two. Thus, there are only two independent
reactions. We will use Reaction 1 (gas only) and Reaction 3 (involves solid carbon).
To find the boundary or ”threshold” pressure where carbon just begins to deposit, we evaluate the system at the exact point where
solid carbon is on the verge of existing, but its actual mass is infinitesimally small. Mathematically, the extent of the carbon-forming
reaction is zero (𝜉3 = 0).
Step 1: Gas-Phase Equilibrium (Reaction 1) Using a basis of 100 moles of feed, let 𝜉1 be the extent of Reaction 1:

𝑛CO2 = 40 − 𝜉1 , 𝑛H2 = 40 − 𝜉1 , 𝑛CO = 𝜉1 , 𝑛 H2 O = 𝜉 1 , 𝑛N2 = 20

Total moles 𝑛𝑇 = 100 (since Δ𝜈 = 0 for Reaction 1).

𝑦 CO 𝑦 H2 O 𝜉12
𝐾1 = = = 0.633
𝑦 CO2 𝑦 H2 (40 − 𝜉1 ) 2

Taking the square root of both sides:

𝜉1
0.7956 = =⇒ 𝜉1 = 17.72 moles
40 − 𝜉1
This gives equilibrium mole fractions: 𝑦 CO = 0.1772 and 𝑦 CO2 = 0.2228.
Step 2: Threshold Pressure for Carbon Formation Carbon formation is the reverse of Reaction 3. We check the equilibrium
criteria for Reaction 3 (𝐾3 = 2.00) using the gas composition calculated above:
2 𝑦2 · 𝑃
𝑃CO (𝑦 CO 𝑃) 2
𝐾3 = = = CO
𝑃CO2 · 𝑎 carbon (𝑦 CO2 𝑃) (1) 𝑦 CO2

Solving for the threshold pressure (𝑃∗ ):

𝐾3 · 𝑦 CO2 2.00 × 0.2228
𝑃∗ = = = 14.19 bar
𝑦 2CO (0.1772) 2
Conclusion: Because the carbon-forming reaction (2CO ⇌ CO2 + C(s)) results in a decrease in the number of gas moles, Le Chatelier’s
principle dictates that higher pressures will drive the reaction toward the solid. Therefore, carbon will deposit for 𝑃 > 14.19 bar.

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Chapter 2 Thermodynamics Solutions Muhammad Shabbir @2102113

Part (b): Operating Pressure for 25% Carbon Deposition

Now, carbon physically exists in the bed. Specifically, 25% of the 40 moles of fed CO2 (which is 10 moles) has deposited as solid carbon.
We now set the extent of Reaction 3 to 𝜉3 = −10 (negative because the reaction as written consumes carbon; we are producing it).
Step 1: Simultaneous Mass Balances

𝑛CO2 = 40 − 𝜉1 − 𝜉3 = 40 − 𝜉1 − (−10) = 50 − 𝜉1

𝑛H2 = 40 − 𝜉1
𝑛CO = 𝜉1 + 2𝜉3 = 𝜉1 − 20
𝑛 H2 O = 𝜉 1
𝑛N2 = 20
Total gas moles 𝑛𝑇 = 90.
Step 2: Solve for 𝜉1 and 𝑃 Substitute into the pressure-independent 𝐾1 equation:

(𝜉1 − 20)𝜉1
𝐾1 = 0.633 =
(50 − 𝜉1 ) (40 − 𝜉1 )

Expanding this yields a quadratic equation: 0.367𝜉12 + 36.97𝜉1 − 1266 = 0. Solving gives 𝜉1 = 27.00 moles. The new mole fractions are
𝑦 CO = (27 − 20)/90 = 0.0778 and 𝑦 CO2 = (50 − 27)/90 = 0.2556.
Now, substitute these into the 𝐾3 expression to find the required pressure:
𝐾3 · 𝑦 CO2 2.00 × 0.2556
𝑃= = = 84.5 bar
𝑦 2CO (0.0778) 2

Conclusion: To force 25% of the carbon to deposit, the system must be highly pressurized to 84.5 bar. (Note: A rigorous second
approximation using fugacity coefficients 𝜙𝑖 from generalized charts would show minor deviations, but 𝜙 ≈ 1.0 is a highly accurate first
approximation at 1000 K).

Problem 2.13: Multiphase Equilibria and Poynting Corrections

▷ Concept Focus: Liquid-gas equilibrium, extremely high pressures requiring the Poynting correction factor for liquid activities, and
Le Chatelier’s principle for temperature shifts.
▷ Problem Context: Producing liquid benzaldehyde from liquid benzene and gaseous carbon monoxide at 25◦ C and 100 bar.

Part 1: Standard Thermodynamic Properties at 25◦ C

We calculate standard enthalpy, entropy, and Gibbs free energy of reaction:

Δ𝐻𝑟◦𝑥𝑛 = −21, 860 − [−26, 390 + 12, 390] = −7, 860 cal/mol
Δ𝑆𝑟◦ 𝑥𝑛 = 49.4 − [47.32 + 41.9] = −39.82 cal/(mol · K)
Δ𝐺 𝑟◦ 𝑥𝑛 = Δ𝐻𝑟◦𝑥𝑛 − 𝑇Δ𝑆𝑟◦ 𝑥𝑛 = −7, 860 − (298.15) (−39.82) = +4, 012.33 cal/mol

The equilibrium constant is:

−Δ𝐺 𝑟◦ 𝑥𝑛
   
−4012.33
𝐾 𝑎 = exp = exp = 1.144 × 10−3
𝑅𝑇 1.987 × 298.15

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Chapter 2 Thermodynamics Solutions Muhammad Shabbir @2102113

Part 2: Activities and the Poynting Correction

The equilibrium expression is 𝐾 𝑎 = 𝑎 CHO /(𝑎 CO · 𝑎 benzene ).
▷ Gas Phase (𝑎 CO ): Because the liquid vapor pressures are extremely low (0.125 and 0.001 bar) compared to the system pressure (100
bar), the gas phase is essentially pure CO (𝑦 CO ≈ 1). Thus, 𝑎 CO = 𝜙CO 𝑃 = 0.965 × 100 = 96.5.
▷ Liquid Phase (Poynting Factor): Because 100 bar is significantly higher than the 1 bar standard state, the liquids are compressed,
altering their activity. We use the Poynting correction: P𝑖 = exp[𝑉𝑚 (𝑃 − 𝑃◦ )/𝑅𝑇]. (Note: R = 83.14 cm3 ·bar/(mol·K)).
 
89.5(100 − 1)
Pbenzene = exp = 1.430 =⇒ 𝑎 benzene = 𝑥 𝐵 (1.430)
83.14 × 298.15
 
102(100 − 1)
PCHO = exp = 1.503 =⇒ 𝑎 CHO = 𝑥CHO (1.503)
83.14 × 298.15

Part 3: Mass Balance and Yield

Let 𝜉 be the moles of benzaldehyde formed from 1 initial mole of benzene. Total liquid moles = (1 − 𝜉) + 𝜉 = 1. Therefore, 𝑥 𝐵 = 1 − 𝜉
and 𝑥 CHO = 𝜉. Substituting into the equilibrium equation:
𝜉 (1.503)
1.144 × 10−3 =
96.5 · (1 − 𝜉) (1.430)
1.503𝜉
0.1579 = =⇒ 0.1579(1 − 𝜉) = 1.503𝜉 =⇒ 𝜉 = 0.095 moles
1−𝜉
Conclusion: 0.095 moles of benzaldehyde are formed.

Part 4: Operating at 100◦ C

If we increase the temperature to 100◦ C, the yield will drop because the reaction is exothermic (Δ𝐻 ◦ = −7, 860 cal/mol). According to
Le Chatelier’s principle, heating an exothermic reaction shifts the equilibrium toward the reactants, lowering 𝐾 𝑎 . To counteract this and
obtain the same yield, one must operate at a higher pressure to drive the gas-consuming reaction forward.

Problem 2.16: Methanol Synthesis (Isothermal vs. Adiabatic)

▷ Concept Focus: Coupling non-linear equilibrium equations with adiabatic energy balances, and evaluating hypothetical thermody-
namic paths for complex 𝐶 𝑝 integrals.
▷ Problem Context: CO + 2H2 ⇌ CH3 OH at 200 atm. Comparing an isothermal reactor at 275◦ C to an adiabatic reactor with the
same feed temperature.

Part (a): Isothermal Operation at 275◦ C (548.15 K)

First, calculate 𝐾 𝑎 using the provided correlation:
3835
log10 𝐾 𝑎 = − 9.150 log10 (548.15) + 3.08 × 10−3 (548.15) + 13.20 = −3.177
548.15
𝐾 𝑎 = 10−3.177 = 6.65 × 10−4
For a feed of 1 mol CO and 2 mol H2 , total moles 𝑛𝑇 = 3 − 2𝜉. Assuming ideal gas behavior (𝐾 𝜙 = 1) due to lack of specific critical
data:
𝑦 CH3 OH −4 𝜉 (3 − 2𝜉) 2
𝐾 𝑎 · 𝑃2 = =⇒ (6.65 × 10 ) (200) 2
=
𝑦 CO 𝑦 2H2 4(1 − 𝜉) 3

𝜉 (3 − 2𝜉) 2
26.6 =
4(1 − 𝜉) 3
Solving this cubic equation yields 𝜉 = 0.748. Isothermal Composition: CO (16.8%), H2 (33.5%), Methanol (49.7%).

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Chapter 2 Thermodynamics Solutions Muhammad Shabbir @2102113

Part (b): Adiabatic Operation

In an adiabatic reactor, the heat released by the reaction raises the temperature of the mixture (𝑄 = 0). We use the thermodynamic path
of heating the unreacted feed to 𝑇, then reacting at 𝑇. 1. Sensible Heat Integral:

Σ𝐶 𝑝,feed = (6.89 + 0.00038𝑇) + 2(6.65 + 0.00070𝑇) = 20.19 + 0.00178𝑇

∫ 𝑇
(20.19 + 0.00178𝑇)𝑑𝑇 = 0.00089𝑇 2 + 20.19𝑇 − 11, 334.4
548.15
2. Energy Balance:
(0.00089𝑇 2 + 20.19𝑇 − 11, 334.4) + 𝜉 (−17, 530 − 18.19𝑇 + 0.0141𝑇 2 ) = 0
Rearranging for 𝜉:
11, 334.4 − 20.19𝑇 − 0.00089𝑇 2
𝜉=
−17, 530 − 18.19𝑇 + 0.0141𝑇 2
3. Trial and Error Solution: We must find a temperature 𝑇 where the 𝜉 from the energy balance matches the 𝜉 required by the
temperature-dependent equilibrium constant 𝐾 𝑎 (𝑇).
▷ Guess 𝑇 = 687 K: The energy balance yields 𝜉 = 0.1265.
▷ Evaluate 𝐾 𝑎 at 687 K: 𝐾 𝑎 = 8.71 × 10−6 .
▷ Check equilibrium: (8.71 × 10−6 ) (200) 2 = 0.348. The mass balance ratio using 𝜉 = 0.1265 is 0.358. This is a converged solution.
Adiabatic Composition: CO (31.8%), H2 (63.6%), Methanol (4.6%). Note the massive penalty: the adiabatic temperature spike (up to
414◦ C) thermodynamically ”kills” the conversion, dropping it from nearly 50% to under 5%.

Problem 2.19: Adiabatic Alkylation & Pressure Effects

▷ Concept Focus: Full derivation of temperature-dependent thermodynamic properties (Δ𝐻 ◦ (𝑇) and Δ𝑆 ◦ (𝑇)) and evaluating the
competing thermodynamic effects of high pressure vs. extreme thermal runaway.
▷ Problem Context: Ethylene (E) + Benzene (B) ⇌ Ethylbenzene (EB) fed at 60 mol% B and 40 mol% E at 500◦ C.

Part 1: Thermodynamic Properties as Functions of Temperature

First, calculate the standard properties at 298.15 K using the heats of combustion (Δ𝐻𝑐◦ ) and formation (Δ𝐺 ◦𝑓 ):

Δ𝐻𝑟◦𝑥𝑛 = Δ𝐻𝑐,𝐸
◦ ◦
+ Δ𝐻𝑐,𝐵 ◦
− Δ𝐻𝑐,𝐸 𝐵 = −316.195 − 757.52 − (−1048.53) = −25, 185 cal/mol

Δ𝐺 𝑟◦ 𝑥𝑛 = 31.208 − (16.282 + 30.989) = −16, 063 cal/mol

−25, 185 − (−16, 063)
Δ𝑆𝑟◦ 𝑥𝑛 = = −30.595 cal/(mol · K)
298.15
Using Δ𝐶 𝑝 = 68.3 − (20.5 + 45.9) = 1.9 cal/(mol · K), we derive the temperature-dependent equations:

Δ𝐻 ◦ (𝑇) = −25, 185 + 1.9(𝑇 − 298.15) = −25, 751.5 + 1.9𝑇

Δ𝑆 ◦ (𝑇) = −30.595 + 1.9 ln(𝑇/298.15) = −41.42 + 1.9 ln(𝑇)

From Δ𝐺 ◦ (𝑇) = Δ𝐻 ◦ − 𝑇Δ𝑆 ◦ , we derive the expression for ln 𝐾 𝑎 :

−Δ𝐺 ◦ (𝑇) 12, 960

ln 𝐾 𝑎 (𝑇) = = − 21.80 + 0.956 ln(𝑇)
𝑅𝑇 𝑇

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Chapter 2 Thermodynamics Solutions Muhammad Shabbir @2102113

Part 2: Mass and Energy Balances (4 atm)

Using a basis of 100 moles (40 E, 60 B): 𝑦 𝐸 = (40 − 𝜉)/(100 − 𝜉), 𝑦 𝐵 = (60 − 𝜉)/(100 − 𝜉), 𝑦 𝐸 𝐵 = 𝜉/(100 − 𝜉). The equilibrium
equation is:
𝜉 (100 − 𝜉)
= 𝐾 𝑎 (𝑇) · 𝑃
(40 − 𝜉) (60 − 𝜉)
The adiabatic energy balance (𝑇𝑖𝑛 = 773.15 K):

Sensible Heat = [40(20.5) + 60(45.9)] (𝑇 − 773.15) = 3574(𝑇 − 773.15)

3574(𝑇 − 773.15) + 𝜉 (−25, 751.5 + 1.9𝑇) = 0

Solving these equations simultaneously yields 𝑇 ≈ 898 K and 𝜉 ≈ 18.5. Effluent (4 atm): Ethylene (26.4%), Benzene (50.9%),
Ethylbenzene (22.7%).

Part 3: Effects of 8 atm and 40 atm

Because Δ𝜈 = −1, Le Chatelier’s principle dictates that increasing pressure forces the equilibrium toward Ethylbenzene.
▷ At 8 atm: 𝑇 ≈ 920 K, 𝜉 ≈ 21.9 =⇒ Ethylbenzene = 28.0%
▷ At 40 atm: 𝑇 ≈ 968 K, 𝜉 ≈ 29.0 =⇒ Ethylbenzene = 40.8%
Advantages of 40 atm: The thermodynamic yield is vastly improved. Higher gas density also means faster intrinsic kinetics, allowing
for a smaller reactor footprint.
Disadvantages of 40 atm: The increased conversion triggers a massive adiabatic temperature spike (reaching nearly 700◦ C). This
extreme heat will cause rapid catalyst sintering (deactivation), promote unwanted side reactions like coking, and ultimately force the
equilibrium constant 𝐾 𝑎 so low that it begins fighting the high pressure.

Comparative Analysis of Advanced Thermodynamics (2.12 - 2.19)

▷ Problem 2.12 (Solid-Gas Thresholds): This problem emphasizes the mathematical concept of an ”onset” phase boundary. Unlike
standard equilibria where all components are present and equations are solved simultaneously, threshold problems require you to set
the extent of the newly forming phase to precisely zero (𝜉 = 0). This isolates the gas-phase chemistry to find the exact pressure at
which solid carbon becomes thermodynamically viable.
▷ Problem 2.13 (Liquid-Gas Non-Ideality): While Problem 2.6 corrected non-ideal gases using fugacity, this problem highlights the
thermodynamic treatment of condensed phases at high pressures. The Poynting correction (exp[𝑉𝑚 Δ𝑃/𝑅𝑇]) is crucial here. Although
liquids are practically incompressible, at 100 bar, the mechanical work done on the liquid shifts its chemical potential enough to alter
the equilibrium yield noticeably.
▷ Problem 2.16 & 2.19 (Adiabatic Penalties): Both of these problems explore the tension between Le Chatelier’s principle and the
First Law of Thermodynamics. In both methanol and ethylbenzene synthesis, the reactions are highly exothermic. While raising
pressure mathematically drives the Δ𝜈 < 0 reactions forward, the resulting adiabatic heat release raises the temperature, which
exponentially shrinks the equilibrium constant 𝐾 𝑎 . These problems prove mathematically why industrial reactors for these processes
must be intercooled or run in multiple stages; an adiabatic tube simply suffocates its own conversion.

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Chapter 3 Kinetics Solutions Muhammad Shabbir @2102113

Detailed Solutions: Levenspiel Chapter 3

Problem 3.20: Integral Method (Irreversible Assumption)

▷ Concept Focus: Testing second-order irreversible kinetics using the Integral Method.
▷ Problem Context: Aqueous reaction of sulfuric acid (A) with diethylsulfate (B) to form ethyl hydrogen sulfate (R). Initial concentra-
tions: 𝐶 𝐴0 = 𝐶 𝐵0 = 5.5 mol/L.
𝐴 + 𝐵 → 2𝑅

Step 1: Formulate the Rate Law

Assume the reaction is elementary and irreversible. Because initial concentrations are equal (𝐶 𝐴0 = 𝐶 𝐵0 ), the stoichiometry dictates that
𝐶 𝐴 will equal 𝐶 𝐵 at all times.
𝑑𝐶 𝐴
−𝑟 𝐴 = − = 𝑘𝐶 𝐴𝐶 𝐵 = 𝑘𝐶 2𝐴
𝑑𝑡
Using fractional conversion (𝐶 𝐴 = 𝐶 𝐴0 (1 − 𝑋 𝐴)), the differential equation is:
𝑑𝑋 𝐴 𝑑𝑋 𝐴
𝐶 𝐴0 = 𝑘𝐶 2𝐴0 (1 − 𝑋 𝐴) 2 =⇒ = 𝑘𝐶 𝐴0 𝑑𝑡
𝑑𝑡 (1 − 𝑋 𝐴) 2
Integrating from 𝑡 = 0, 𝑋 𝐴 = 0 to 𝑡, 𝑋 𝐴 gives the standard Levenspiel Equation 16:
𝑋𝐴
= 𝑘𝐶 𝐴0 𝑡
1 − 𝑋𝐴
𝑋𝐴
If this assumption is correct, a plot of 1−𝑋 𝐴 versus 𝑡 will yield a straight line passing through the origin with a slope equal to 𝑘𝐶 𝐴0 .

Step 2: Process the Data

We must convert the raw product data (𝐶𝑅 ) into conversion (𝑋 𝐴). From the stoichiometry, 1 mole of A produces 2 moles of R. Therefore,
𝐶𝑅 = 2𝐶 𝐴0 𝑋 𝐴.
𝐶𝑅 𝐶𝑅
𝑋𝐴 = =
2(5.5) 11.0
𝑋𝐴
Time 𝑡 (min) 𝐶𝑅 (mol/L) Conversion 𝑋 𝐴 Plotting Function 1−𝑋 𝐴
0 0 0.000 0.000
41 1.18 0.107 0.120
96 2.75 0.250 0.333
146 3.76 0.342 0.520
194 4.31 0.392 0.645
267 4.86 0.442 0.792
379 5.35 0.486 0.946
410 5.42 0.493 0.972

Step 3: Graphical Evaluation

We now plot the processed data.

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Chapter 3 Kinetics Solutions Muhammad Shabbir @2102113

Integral Method Test for Irreversible 2nd Order

1.2
Experimental Data
1 Linear Fit: 𝑦 = 0.0027𝑥

0.8

1−𝑋 𝐴
𝑋𝐴 0.6

0.4

0.2

0
0 100 200 300 400
Time 𝑡 (min)

Step 4: Calculate the Rate Constant

The plot yields a reasonable straight line for the duration of the experiment, with a slope of 0.0027 min−1 . Equating the experimental
slope to the theoretical slope:
Slope = 𝑘 · 𝐶 𝐴0
0.0027 = 𝑘 · 5.5
0.0027
𝑘= = 4.91 × 10−4 L/(mol · min)
5.5
The rate equation is therefore:
−𝑟 𝐴 = 4.91 × 10−4 𝐶 𝐴𝐶 𝐵

Critical Analysis Note: Irreversible vs. Reversible

Many online solution manuals analyze this problem using the irreversible method shown above. However, this is thermodynamically flawed.
The original data table includes a measurement at 𝑡 = ∞ where 𝐶𝑅 = 5.80 mol/L. If the reaction were truly irreversible, 𝐶𝑅 would reach the
theoretical maximum of 11.0 mol/L. The fact that it stops at 5.80 proves the reaction reaches equilibrium and is reversible.
The irreversible plot looks deceptively straight because early in the reaction, product concentration is low, so the reverse rate (𝑘 2 𝐶𝑅2 ) is negligible.
Notice how the last few data points on the graph begin to droop below the trendline; this is the reverse reaction kicking in! For absolute rigor, a
reversible model (Levenspiel Eq. 56) should be used.

Problem 3.20: Considering the reversible reaction .....

▷ Concept Focus: The Integral Method of data analysis. Recognizing reversible kinetics from an incomplete infinite-time conversion
limit, mapping non-standard stoichiometry (𝐴 + 𝐵 ⇌ 2𝑅) to standard integrated rate laws, and verifying the guess via graphical
linearization.
▷ Problem Context: Aqueous reaction of sulfuric acid (A) with diethylsulfate (B) to form 2 moles of ethyl hydrogen sulfate (R).

𝐴 + 𝐵 ⇌ 2𝑅

Initial concentrations: 𝐶 𝐴0 = 𝐶 𝐵0 = 5.5 mol/L.

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Chapter 3 Kinetics Solutions Muhammad Shabbir @2102113

Step 1: Determine the Equilibrium Conversion (𝑋 𝐴𝑒 )

If the reaction went to 100% completion, the maximum concentration of product R would be 2 × 𝐶 𝐴0 = 2 × 5.5 = 11.0 mol/L. The data
table states that at 𝑡 = ∞, 𝐶𝑅𝑒 = 5.80 mol/L. This confirms the reaction is reversible.
Using the stoichiometry, the concentration of R at any time is 𝐶𝑅 = 2𝐶 𝐴0 𝑋 𝐴. Therefore, the fractional conversion at any time 𝑡 is:
𝐶𝑅 𝐶𝑅
𝑋𝐴 = =
2𝐶 𝐴0 11.0
At equilibrium (𝑡 = ∞):
5.80
𝑋 𝐴𝑒 = = 0.5273
11.0

Step 2: Guess a Rate Equation (Integral Method)

We guess that the reaction follows elementary, second-order reversible kinetics. The differential rate law is:
𝑑𝐶 𝐴
−𝑟 𝐴 = − = 𝑘 1 𝐶 𝐴𝐶 𝐵 − 𝑘 2 𝐶𝑅2
𝑑𝑡
Because 𝐶 𝐴0 = 𝐶 𝐵0 , we know 𝐶 𝐴 = 𝐶 𝐵 = 𝐶 𝐴0 (1 − 𝑋 𝐴). Substituting this and 𝐶𝑅 = 2𝐶 𝐴0 𝑋 𝐴 gives:
𝑑𝑋 𝐴
𝐶 𝐴0 = 𝑘 1 𝐶 2𝐴0 (1 − 𝑋 𝐴) 2 − 𝑘 2 (2𝐶 𝐴0 𝑋 𝐴) 2
𝑑𝑡
𝑑𝑋 𝐴
= 𝑘 1 𝐶 𝐴0 (1 − 𝑋 𝐴) 2 − 4𝑘 2 𝐶 𝐴0 𝑋 𝐴2
𝑑𝑡
We must now map this to a standard integrated equation from the text. Levenspiel’s Equation 56 (page 58) provides the integrated
form for the general reaction 𝐴 + 𝐵 ⇌ 𝑅 + 𝑆, whose differential rate is:
𝑑𝑋 𝐴
= 𝑘 1 𝐶 𝐴0 (1 − 𝑋 𝐴) 2 − 𝑘 reverse text 𝐶 𝐴0 𝑋 𝐴2
𝑑𝑡
Notice that our derived equation is mathematically identical to the text’s equation if we set 𝑘 reverse text = 4𝑘 2 . Therefore, we can safely
use the integrated form of Equation 56 to test our data:
   
𝑋 𝐴𝑒 − (2𝑋 𝐴𝑒 − 1) 𝑋 𝐴 1
ln = 2𝑘 1 − 1 𝐶 𝐴0 𝑡
𝑋 𝐴𝑒 − 𝑋 𝐴 𝑋 𝐴𝑒

Step 3: Process the Data for Plotting

Let the left side of the integrated equation be 𝑌 . We must evaluate the constants using 𝑋 𝐴𝑒 = 0.5273:

2𝑋 𝐴𝑒 − 1 = 2(0.5273) − 1 = 0.0546
 
0.5273 − 0.0546𝑋 𝐴
𝑌 = ln
0.5273 − 𝑋 𝐴
We convert the raw 𝐶𝑅 data to 𝑋 𝐴 (𝑋 𝐴 = 𝐶𝑅 /11.0), and calculate 𝑌 for several points:

Time 𝑡 (min) 𝐶𝑅 (mol/L) Conversion 𝑋 𝐴 Plotting Function 𝑌

0 0 0.0000 0.000
41 1.18 0.1073 0.216
96 2.75 0.2500 0.616
162 3.81 0.3464 1.033
267 4.86 0.4418 1.772
379 5.35 0.4864 2.505
410 5.42 0.4927 2.651

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Chapter 3 Kinetics Solutions Muhammad Shabbir @2102113

Step 4: Graphical Test of the Rate Equation

If our guess of elementary reversible kinetics is correct, plotting 𝑌 versus 𝑡 will yield a straight line passing through the origin.

Integral Method Test for Eq. 56 (𝐴 + 𝐵 ⇌ 2𝑅)

3
Experimental Data
Best Fit Line (Slope ≈ 0.00656)
i
𝑋 𝐴𝑒 − (2𝑋 𝐴𝑒 −1) 𝑋 𝐴
𝑋 𝐴𝑒 −𝑋 𝐴 2

1
h
ln

0
0 100 200 300 400
Time 𝑡 (min)

Because the data beautifully follows a straight line through the origin, our guessed rate equation is accepted.

Step 5: Evaluate the Rate Constants

From the plot, the slope of the line is approximately:
𝑌 2.651
Slope = ≈ ≈ 0.00656 min−1
𝑡 410
From Levenspiel Equation 56, the theoretical slope is defined as:
 
1 − 𝑋 𝐴𝑒
Slope = 2𝑘 1 𝐶 𝐴0
𝑋 𝐴𝑒
Substitute the known values to solve for the forward rate constant 𝑘 1 :
 
1 − 0.5273
0.00656 = 2 · 𝑘 1 · 5.5 = 11.0 · 𝑘 1 · (0.8964) = 9.86𝑘 1
0.5273
0.00656
= 6.65 × 10−4 L/(mol · min)
𝑘1 =
9.86
To find the reverse rate constant 𝑘 2 , we use the equilibrium condition. At equilibrium, the forward and reverse rates are equal
(−𝑟 𝐴 = 0):
2
𝑘 1 𝐶 𝐴𝑒 𝐶 𝐵𝑒 = 𝑘 2 𝐶𝑅𝑒
Since 𝐶 𝐴 = 𝐶 𝐵 , 𝑘 1 𝐶 2𝐴𝑒 = 𝑘 2 𝐶𝑅𝑒
2 . Calculate the equilibrium concentrations: * 𝐶
𝐴𝑒 = 𝐶 𝐴0 (1 − 𝑋 𝐴𝑒 ) = 5.5(1 − 0.5273) = 2.60 mol/L *
𝐶𝑅𝑒 = 5.80 mol/L (given)
 2  2
𝐶 𝐴𝑒 −4 2.60
𝑘2 = 𝑘1 = (6.65 × 10 ) = (6.65 × 10−4 ) · (0.2009)
𝐶𝑅𝑒 5.80
𝑘 2 = 1.34 × 10−4 L/(mol · min)

Final Rate Equation

The complete rate equation representing the disappearance of sulfuric acid is:
 
−4 −4 mol
−𝑟 H2 SO4 = (6.65 × 10 )𝐶H2 SO4 𝐶 (C2 H5 )2 SO4 − (1.34 × 10 )𝐶C2 2 H5 SO4 H
L · min

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Chapter 3 Kinetics Solutions Muhammad Shabbir @2102113

Problem 3.28: Deducing a Rate Law from Initial Rate Data

▷ Concept Focus: The Method of Initial Rates. Deducing reaction orders by comparing pairs of experimental runs where one or more
concentrations are held constant, and handling fractional orders.
▷ Problem Context: For the reaction 𝐴 + 𝐵 → 𝐴𝐵, a catalyst C is present. We are given a table of initial concentrations and initial
rates and must find the complete rate equation.

Step 1: Propose a General Rate Equation Form

Based on the experimental data, we propose a general power-law rate equation of the form:

𝑟 𝐴𝐵 = 𝑘 [ 𝐴] 𝑎 [𝐵] 𝑏 [𝐶] 𝑐

Our goal is to find the reaction orders 𝑎, 𝑏, and 𝑐, and the rate constant 𝑘. We can achieve this by taking ratios of the rate equation for
different experimental runs. For any two runs, say Run 𝑖 and Run 𝑗:
 𝑎  𝑏  𝑐
𝑟𝑖 [ 𝐴𝑖 ] [𝐵𝑖 ] [𝐶𝑖 ]
=
𝑟𝑗 [𝐴𝑗] [𝐵 𝑗 ] [𝐶 𝑗 ]

Step 2: Isolate and Determine Reaction Orders

We strategically choose pairs of runs where one or more concentrations are held constant to simplify the ratio equation.

▷ Comparing Run 4 and Run 5 to find orders 𝑏 and 𝑐: In these two runs, the concentration of reactant A is held constant at [ 𝐴] = 2.
 𝑎  𝑏  𝑐
𝑟 5 20 2 4 0.03
= = 3.333 = = (1) 𝑎 (2) 𝑏 (3) 𝑐
𝑟4 6 2 2 0.01

This simplifies to a relationship between 𝑏 and 𝑐:

3.333 = (2) 𝑏 (3) 𝑐 — (Equation I)

▷ Comparing Run 1 and Run 2 to find orders 𝑎 and 𝑏: In these two runs, the concentration of catalyst C is held constant at [𝐶] = 0.02.
 𝑎  𝑏  𝑐
𝑟1 9 1 3 0.02
= = 1.8 = = 3−𝑎 · 3𝑏 = 3𝑏−𝑎
𝑟2 5 3 1 0.02

1.8 = 3𝑏−𝑎 — (Equation II)

▷ Comparing Run 3 and Run 5 to find orders 𝑎 and 𝑐: In these two runs, the concentration of reactant B is held constant at [𝐵] = 4.
 𝑎  𝑏  𝑐
𝑟 3 32 4 4 0.04
= = 1.6 = = (2) 𝑎 (1) 𝑏 (1.333) 𝑐
𝑟 5 20 2 4 0.03

1.6 = (2) 𝑎 (1.333) 𝑐 — (Equation III)

Step 3: Solve the System of Equations

We now have a system of three equations. Let’s take the natural logarithm of each to linearize them:

• From (I): ln(3.333) = 𝑏 ln(2) + 𝑐 ln(3) =⇒ 1.204 = 0.693𝑏 + 1.0986𝑐

• From (II): ln(1.8) = (𝑏 − 𝑎) ln(3) =⇒ 0.5878 = 1.0986(𝑏 − 𝑎) =⇒ 𝑏 − 𝑎 = 0.535
• From (III): ln(1.6) = 𝑎 ln(2) + 𝑐 ln(1.333) =⇒ 0.470 = 0.693𝑎 + 0.2877𝑐

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Chapter 3 Kinetics Solutions Muhammad Shabbir @2102113

From the second equation, we can write 𝑏 = 𝑎 + 0.535. Substituting this into the first equation gives:

1.204 = 0.693(𝑎 + 0.535) + 1.0986𝑐 =⇒ 0.833 = 0.693𝑎 + 1.0986𝑐

We now have a simple linear system for 𝑎 and 𝑐:

0.833 = 0.693𝑎 + 1.0986𝑐
0.470 = 0.693𝑎 + 0.2877𝑐
Subtracting the second from the first gives:
0.363 = 0.8109𝑐 =⇒ 𝑐 = 0.448 ≈ 0.5
Substituting 𝑐 = 0.5 back into the second equation:

0.470 = 0.693𝑎 + 0.2877(0.5) =⇒ 0.326 = 0.693𝑎 =⇒ 𝑎 = 0.471 ≈ 0.5

Finally, using 𝑏 = 𝑎 + 0.535:

𝑏 = 0.5 + 0.535 = 1.035 ≈ 1.0
The reaction orders are approximately 𝑎 = 0.5, 𝑏 = 1, and 𝑐 = 0.5.

Step 4: Verify the Rate Law and Find k

The proposed rate equation is:
𝑟 𝐴𝐵 = 𝑘 [ 𝐴] 0.5 [𝐵] 1.0 [𝐶] 0.5
We test this by calculating 𝑘 = 𝑟 𝐴𝐵 /( [ 𝐴] 0.5 [𝐵] [𝐶] 0.5 ) for each run. It should be constant.

Run [A] [B] [C] Calculated 𝑘 = 𝑟/( [ 𝐴] 0.5 [𝐵] [𝐶] 0.5 )
√ √
1 1 3 0.02 9/( 1 · 3 · 0.02) = 21.21
√ √
2 3 1 0.02 5/( 3 · 1 · 0.02) = 20.41
√ √
3 4 4 0.04 32/( 4 · 4 · 0.04) = 20.00
√ √
4 2 2 0.01 6/( 2 · 2 · 0.01) = 21.21
√ √
5 2 4 0.03 20/( 2 · 4 · 0.03) = 20.41
√ √
6 1 2 0.05 12/( 1 · 2 · 0.05) = 26.83

The values for 𝑘 are remarkably consistent (with the exception of Run 6, which may be a slight experimental outlier). The average of the
first five runs is k ≈ 20.6.

Final Rate Equation and Mechanism

The rate equation that best represents the data is:
𝑟 𝐴𝐵 = 20.6[ 𝐴] 0.5 [𝐵] [𝐶] 0.5
The presence of fractional orders definitively indicates that the reaction is not elementary and must proceed through a multi-step
mechanism involving intermediates. The hint that C combines with a reactant is consistent with this. A mechanism that could produce
such fractional orders would likely involve an equilibrium step where the catalyst dimerizes or dissociates (𝐶 ⇌ 𝐶2 or 𝐶 ⇌ 2𝐶 ∗ ) or a
complex radical chain mechanism. The proposed power law is an excellent empirical fit to the observed kinetic behavior.

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Chapter 3 Kinetics Solutions Muhammad Shabbir @2102113

Problem 3.31: Determining a Complete Rate Equation (Arrhenius Law)

▷ Concept Focus: Determining reaction order from the units of the rate constant, and using the Arrhenius law and graphical linearization
(Arrhenius plot) to find the activation energy and frequency factor.
▷ Problem Context: The thermal decomposition of hydrogen iodide, 2HI → H2 + I2 . We are given rate constants at various
temperatures.

Step 1: Determine the Reaction Order

The units of the rate constant are given as cm3 /(mol · s). For a general rate law of the form −𝑟 HI = 𝑘 [𝐻𝐼] 𝑛 , the units must be consistent:
   𝑛
mol mol
= [𝑘]
cm3 · s cm3
The units of the rate constant 𝑘 are therefore [concentration] 1−𝑛 [time] −1 .
  3  𝑛−1  
cm3

cm 1
=
mol · s mol s

Comparing the units, we see that the term [(cm3 /mol)] 𝑛−1 must equal [cm3 /mol]. This is only true if the exponent (𝑛 − 1) is equal to 1.
𝑛 − 1 = 1 =⇒ 𝑛 = 2
The reaction is therefore second-order with respect to HI. The differential rate law is:
−𝑟 HI = 𝑘 [𝐻𝐼] 2

Step 2: Linearize the Arrhenius Equation

The Arrhenius equation relates the rate constant 𝑘 to temperature:
𝑘 = 𝑘 0 𝑒 −𝐸/𝑅𝑇
To find the activation energy 𝐸 and frequency factor 𝑘 0 , we linearize this equation by taking the natural logarithm:
 
𝐸 1
ln(𝑘) = ln(𝑘 0 ) −
𝑅 𝑇
This is the equation of a straight line, 𝑦 = 𝑏 + 𝑚𝑥, where:
• 𝑦 = ln(𝑘)
• 𝑥 = 1/𝑇
• The slope 𝑚 = −𝐸/𝑅
• The y-intercept 𝑏 = ln(𝑘 0 )

Step 3: Process the Data for Plotting

We must convert the temperatures from Celsius to Kelvin and calculate the values for our plotting axes (1/𝑇 and ln(𝑘)). The gas constant
𝑅 = 8.314 J/(mol · K).

Given Data Calculated Values for Plotting

𝑇 (◦ C) 𝑘 (cm3 /mol·s) 𝑇 (K) 1/𝑇 (K−1 ) ln(𝑘)
508 0.1059 781.15 0.001280 -2.245
427 0.00310 700.15 0.001428 -5.776
393 0.000588 666.15 0.001501 -7.439
356 80.9 × 10−6 629.15 0.001589 -9.423
283 0.942 × 10−6 556.15 0.001798 -13.876

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Chapter 3 Kinetics Solutions Muhammad Shabbir @2102113

Step 4: Graphical Evaluation (Arrhenius Plot)

We now plot ln(𝑘) versus 1/𝑇 to find the slope and intercept.

Arrhenius Plot for HI Decomposition

0
Bodenstein’s Data
Best Fit Line

−5
ln(𝑘)

−10

−15
1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9
1/𝑇 (K−1 ) ·10−3

Step 5: Calculate E and k0

Using the extreme points to calculate the slope of the best-fit line:

−13.876 − (−2.245) −11.631

Slope = = = −22, 454 K
0.001798 − 0.001280 0.000518
Now, we find the Activation Energy 𝐸:

𝐸 = −Slope · 𝑅 = −(−22, 454 K) · (8.314 J/(mol · K)) = 186, 670 J/mol = 186.7 kJ/mol

To find the intercept, we use the point-slope form of a line with one of the data points:

ln(𝑘 0 ) = ln(𝑘) − Slope · (1/𝑇) = −2.245 − (−22, 454) (0.001280) = −2.245 + 28.74 = 26.5

Finally, we calculate the frequency factor 𝑘 0 :

𝑘 0 = 𝑒 26.5 = 3.23 × 1011 cm3 /(mol · s)

Final Complete Rate Equation

Combining the order, frequency factor, and activation energy, the complete rate equation for the disappearance of HI is:

cm3
   −186,700 J/mol 
−𝑟 HI = 3.23 × 1011 𝑒 𝑅𝑇
[𝐻𝐼] 2
mol · s

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Chapter 3 Kinetics Solutions Muhammad Shabbir @2102113

Detailed Solutions: Hill Chapter 3 (Batch Reactor Problems)

Problem: Integral Method for Non-Stoichiometric 2nd Order Kinetics ( Hill Illustration 3.2)
▷ Concept Focus: Applying the integral method to a bimolecular reaction where the stoichiometric coefficients are not 1:1, and the
initial feed is non-stoichiometric (𝑀 ≠ 𝑏/𝑎). This requires deriving a specific integrated rate law via partial fraction decomposition.
▷ Problem Context: The liquid-phase reaction of ethylene dibromide (A) with potassium iodide (B) at 59.72◦ C.
𝑘
C2 H4 Br2 + 3KI →
− C2 H4 + 2KBr + KI3
𝐴 + 3𝐵 → Products
Initial concentrations: 𝐶 𝐴0 = 0.02864 kmol/m , 𝐶 𝐵0 = 0.1531 kmol/m3 .
3

Step 1: Formulate the Differential Rate Law

We assume an elementary second-order rate law, first-order with respect to each reactant. By convention, we write the rate of disappearance
of the primary reactant A:
𝑑𝐶 𝐴
−𝑟 𝐴 = − = 𝑘𝐶 𝐴𝐶 𝐵
𝑑𝑡
We must express both concentrations in terms of the fractional conversion of A (𝑋 𝐴). * 𝐶 𝐴 = 𝐶 𝐴0 (1 − 𝑋 𝐴) * Based on the
stoichiometry (𝐴 + 3𝐵), for every mole of A reacted, 3 moles of B are consumed.
𝐶 𝐵 = 𝐶 𝐵0 − 3𝐶 𝐴0 𝑋 𝐴 = 𝐶 𝐴0 (𝑀 − 3𝑋 𝐴)
where 𝑀 is the initial molar ratio:
𝐶 𝐵0 0.1531
𝑀= = = 5.3457
𝐶 𝐴0 0.02864
Substitute these into the differential rate law:
𝑑𝑋 𝐴
𝐶 𝐴0 = 𝑘 [𝐶 𝐴0 (1 − 𝑋 𝐴)] [𝐶 𝐴0 (𝑀 − 3𝑋 𝐴)]
𝑑𝑡
𝑑𝑋 𝐴
= 𝑘𝐶 𝐴0 (1 − 𝑋 𝐴) (𝑀 − 3𝑋 𝐴)
𝑑𝑡

Step 2: Integrate the Rate Law

Separate variables to prepare for integration:
∫ 𝑋𝐴 ∫ 𝑡
𝑑𝑋 𝐴
= 𝑘𝐶 𝐴0 𝑑𝑡
0 (1 − 𝑋 𝐴) (𝑀 − 3𝑋 𝐴) 0

We integrate the left side using partial fraction decomposition:

1 1/(𝑀 − 3) 3/(𝑀 − 3)
= −
(1 − 𝑋 𝐴) (𝑀 − 3𝑋 𝐴) 1 − 𝑋𝐴 𝑀 − 3𝑋 𝐴
Integrating this expression from 0 to 𝑋 𝐴:
1
[− ln(1 − 𝑋 𝐴) + ln(𝑀 − 3𝑋 𝐴)] 0𝑋 𝐴 = 𝑘𝐶 𝐴0 𝑡
𝑀 −3
Evaluating at the bounds and applying logarithm rules:
   
1 𝑀 − 3𝑋 𝐴
ln − ln(𝑀) = 𝑘𝐶 𝐴0 𝑡
𝑀 −3 1 − 𝑋𝐴
 
𝑀 − 3𝑋 𝐴
ln = 𝐶 𝐴0 (𝑀 − 3)𝑘𝑡
𝑀 (1 − 𝑋 𝐴)
Let the left side of this equation be our plotting function 𝑌 . If the assumed second-order rate law is correct, a plot of 𝑌 versus 𝑡 will yield
a straight line passing through the origin with a slope equal to 𝐶 𝐴0 (𝑀 − 3)𝑘.

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Chapter 3 Kinetics Solutions Muhammad Shabbir @2102113

Step 3: Process the Experimental Data

We calculate the constant multiplier for the slope:

𝐶 𝐴0 (𝑀 − 3) = 0.02864 × (5.3457 − 3) = 0.02864 × 2.3457 = 0.06718 kmol/m3

h i
5.3457−3𝑋 𝐴
Now, we calculate the plotting function 𝑌 = ln 5.3457(1−𝑋 𝐴)
for each data point.

Time 𝑡 (ks) Conversion 𝑋 𝐴 3𝑋 𝐴 Numerator Denominator Plotting Function 𝑌

0 0.0000 0.0000 5.3457 5.3457 0.0000
29.7 0.2863 0.8589 4.4868 3.8152 0.1621
40.5 0.3630 1.0890 4.2567 3.4052 0.2231
47.7 0.4099 1.2297 4.1160 3.1545 0.2660
55.8 0.4572 1.3716 3.9741 2.9016 0.3145
62.1 0.4890 1.4670 3.8787 2.7316 0.3506
72.9 0.5396 1.6188 3.7269 2.4611 0.4150
83.7 0.5795 1.7385 3.6072 2.2478 0.4729

Step 4: Graphical Evaluation

Integral Method Test for 2nd Order Kinetics (𝐴 + 3𝐵)

0.5 Processed Data

Linear Fit: 𝑦 = 0.00563𝑥
0.4
i
𝑀 (1−𝑋 𝐴 )
𝑀 −3𝑋 𝐴

0.3
h

0.2
ln

0.1

0
0 20 40 60 80
Time 𝑡 (ks)

Step 5: Determine the Rate Constant

The data points fall perfectly along a straight line passing through the origin, validating the second-order rate law.
Performing a linear regression through the origin yields a slope of:

Slope = 0.00563 ks−1

From our derived integration, we know:

Slope = 𝐶 𝐴0 (𝑀 − 3)𝑘
0.00563 ks−1 = (0.06718 kmol/m3 ) · 𝑘
0.00563 m3
𝑘= = 0.0838
0.06718 kmol · ks
Unit Conversion for Standard Presentation: It is customary to present rate constants in units of Liters, moles, and seconds. Since
1 m3 = 1000 L and 1 kmol = 1000 mol, the concentration units kmol/m3 are exactly equivalent to mol/L (or Molarity, M). Therefore,
m3 /kmol ≡ M−1 . Converting kiloseconds (ks) to seconds (s): 1 ks = 1000 s.

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Chapter 3 Kinetics Solutions Muhammad Shabbir @2102113

0.0838 M−1
𝑘= = 8.38 × 10−5 M−1 s−1
1000 s

Problem: Graphical Integral Method for Gas-Phase Decomposition (Hill Illustration 3.3
▷ Concept Focus: Applying the integral method to a constant-volume gas-phase reaction tracked via total pressure. Requires relating
total pressure to reactant partial pressure using stoichiometry, and visually comparing multiple kinetic hypotheses.
▷ Problem Context: The decomposition of dimethyl ether at 552◦ C in a constant-volume reactor.

CH3 OCH3 → CH4 + CO + H2

𝐴 → 𝐵+𝐶 +𝐷
The initial pressure is pure ether, so 𝜋0 = 𝑝 𝐴0 = 420 torr.

Step 1: Relate Total Pressure (𝜋) to Reactant Pressure (𝑝 𝐴)

To use the integral method, we must convert the measurable total pressure (𝜋) into the partial pressure of the reacting ether (𝑝 𝐴). Let 𝑥
be the change in partial pressure of ether due to reaction. From the stoichiometry (𝐴 → 𝐵 + 𝐶 + 𝐷):

𝑝 𝐴 (𝑡) = 𝑝 𝐴0 − 𝑥
𝑝 𝐵 (𝑡) = 𝑥
𝑝 𝐶 (𝑡) = 𝑥
𝑝 𝐷 (𝑡) = 𝑥

The total pressure 𝜋(𝑡) is the sum of all partial pressures:

𝜋(𝑡) = 𝑝 𝐴 (𝑡) + 𝑝 𝐵 (𝑡) + 𝑝 𝐶 (𝑡) + 𝑝 𝐷 (𝑡) = ( 𝑝 𝐴0 − 𝑥) + 3𝑥 = 𝑝 𝐴0 + 2𝑥

Now, we solve for 𝑥 in terms of total pressure:

𝜋(𝑡) − 𝑝 𝐴0
2𝑥 = 𝜋(𝑡) − 𝑝 𝐴0 =⇒ 𝑥 =
2
Substitute 𝑥 back into the equation for 𝑝 𝐴 (𝑡):
 
𝜋(𝑡) − 𝑝 𝐴0 2𝑝 𝐴0 − 𝜋(𝑡) + 𝑝 𝐴0 3𝑝 𝐴0 − 𝜋(𝑡)
𝑝 𝐴 (𝑡) = 𝑝 𝐴0 − = =
2 2 2

Given that the initial pressure 𝑝 𝐴0 = 420 torr, our working equation is:

3(420) − 𝜋(𝑡) 1260 − 𝜋(𝑡)

𝑝 𝐴 (𝑡) = =
2 2

Step 2: Propose Integral Rate Laws

We will test the two most common reaction orders for thermal decompositions.
 
• Hypothesis 1 (First-Order): −𝑟 𝐴 = 𝑘 𝑝 𝐴 =⇒ ln 𝑝𝑝𝐴0 𝐴
= 𝑘𝑡
A plot of ln( 𝑝 𝐴0 /𝑝 𝐴) versus time should be linear.
• Hypothesis 2 (Second-Order): −𝑟 𝐴 = 𝑘 𝑝 2𝐴 =⇒ 𝑝1𝐴 − 1
𝑝 𝐴0 = 𝑘𝑡
A plot of (1/𝑝 𝐴 − 1/𝑝 𝐴0 ) versus time should be linear.

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Chapter 3 Kinetics Solutions Muhammad Shabbir @2102113

Step 3: Process the Experimental Data

We calculate the plotting functions for both hypotheses using our 𝑝 𝐴 equation.
   
Time 𝑡 (s) 𝜋 (torr) 𝑝 𝐴 = 1260− 2
𝜋
First-Order ln 𝑝𝑝𝐴0
𝐴
Second-Order 1
𝑝𝐴 − 1
𝑝 𝐴0
0 420 420.0 0.000 0.00000
57 584 338.0 0.217 0.00058
85 662 299.0 0.340 0.00096
114 743 258.5 0.485 0.00149
145 815 222.5 0.635 0.00211
182 891 184.5 0.823 0.00304
219 954 153.0 1.010 0.00416
261 1013 123.5 1.224 0.00572
299 1054 103.0 1.405 0.00733

Step 4: Graphical Evaluation

We plot both functions to visually determine which hypothesis yields a straight line.

First-Order Test Plot Second-Order Test Plot

·10−3
8
1.5
1/𝑝 𝐴 − 1/𝑝 𝐴0 (torr−1 )

6
ln( 𝑝 𝐴0 /𝑝 𝐴)

1
4

0.5
2

0 0
0 100 200 300 0 100 200 300
Time 𝑡 (s) Time 𝑡 (s)

Step 5: Conclusion and Rate Constant

The graphical analysis provides a definitive answer:
• The Second-Order plot exhibits severe upward curvature (a parabolic shape), indicating it is completely incorrect.
• The First-Order plot exhibits excellent linearity. There is a very slight lag near 𝑡 = 0 (common in early thermal decomposition
experiments as the gas mixture reaches the uniform reactor temperature), but from 𝑡 = 50 onward, the data perfectly aligns with
the linear model.
Therefore, the reaction is first-order.
To find the rate constant 𝑘, we determine the slope of the best-fit line through the linear portion of the first-order plot.
1.405 − 0.217 1.188
Slope = 𝑘 ≈ = = 0.0049 s−1
299 − 57 242
*(Note: A standard linear regression forced through the origin yields 𝑘 ≈ 0.00465 s−1 . Either value is acceptable depending on how
experimental induction lag is weighted).*
Final Answer: The reaction is 1st Order with a rate constant of k ≈ 4.65 × 10−3 s−1 .

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Chapter 3 Kinetics Solutions Muhammad Shabbir @2102113

Hydration of Isobutene (Detailed Kinetic Analysis (Hill Illustration 3.4))

▷ Concept Focus: Comprehensive application of Guggenheim’s Method for reactions with invalid endpoints, and the use of numerical
averaging to determine intrinsic rate constants in catalytic systems.
▷ Problem Context: Catalytic hydration of isobutene (A) at 25◦ C.
HClO4
CH3 -C(CH3 )=CH2 + H2 O −−−−−→ (CH3 )3 COH

Concentrations: 𝐶HClO4 = 0.3974 M (Large excess, acts as catalyst), 𝐶A,0 = 0.00483 M. The reaction follows pseudo-first-order
kinetics: −𝑟 𝐴 = 𝑘 ′ 𝐶 𝐴 = (𝑘𝐶cat )𝐶 𝐴.

Step 1: Detailed Derivation of Guggenheim’s Formula

When a reaction is tracked via a physical property ℎ (like volume change in a dilatometer) and obeys first-order kinetics, the concentration
′
of reactant 𝐴 at any time is 𝐶 𝐴 = 𝐶 𝐴,0 𝑒 −𝑘 𝑡 . The physical property is linearly related to concentration:

ℎ(𝑡) = 𝑎𝐶 𝐴 + 𝑏
′
At infinite time (𝑡 = ∞), 𝐶 𝐴 = 0, so ℎ∞ = 𝑏. Thus, ℎ(𝑡) − ℎ∞ = 𝑎𝐶 𝐴,0 𝑒 −𝑘 𝑡 . Taking a second reading at a fixed interval Δ later:
′ (𝑡+Δ) ′ ′
ℎ(𝑡 + Δ) − ℎ∞ = 𝑎𝐶 𝐴,0 𝑒 −𝑘 = 𝑎𝐶 𝐴,0 𝑒 −𝑘 𝑡 𝑒 −𝑘 Δ

Subtracting the two readings to eliminate the unknown ℎ∞ :

′
 ′

ℎ(𝑡) − ℎ(𝑡 + Δ) = 𝑎𝐶 𝐴,0 𝑒 −𝑘 𝑡 1 − 𝑒 −𝑘 Δ

Taking the natural logarithm to linearize:

′
ln |ℎ(𝑡) − ℎ(𝑡 + Δ)| = ln[𝑎𝐶 𝐴,0 (1 − 𝑒 −𝑘 Δ )] − 𝑘 ′ 𝑡

This confirms that a plot of ln |ℎ(𝑡) − ℎ(𝑡 + Δ)| vs. 𝑡 has a slope of −𝑘 ′ .

Step 2: Processing Data for Guggenheim’s Method

The fixed time interval is Δ = 2 hours = 120 minutes. We calculate ln(Δℎ) for all given pairs.

Time 𝑡 (min) ℎ(𝑡) ℎ(𝑡 + 120) Δℎ = |ℎ(𝑡) − ℎ(𝑡 + 120)| 𝑌 = ln(Δℎ)

0 18.84 13.50 5.34 1.6752
10 17.91 13.35 4.56 1.5173
20 17.19 13.19 4.00 1.3863
30 16.56 13.05 3.51 1.2556
40 16.00 12.94 3.06 1.1184
50 15.53 12.84 2.69 0.9895
60 15.13 12.75 2.38 0.8671
70 14.76 12.69 2.07 0.7275

Using the first and last points to determine the pseudo-rate constant 𝑘 ′ :
   
0.7275 − 1.6752 −0.9477
𝑘 ′ = −Slope = − =− = 0.01354 min−1
70 − 0 70

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Chapter 3 Kinetics Solutions Muhammad Shabbir @2102113

Step 3: Numerical Averaging (Given ℎ∞ = 12.16)

 
ℎ0 −ℎ∞
With ℎ∞ known, we use the standard first-order integrated form: 𝑘 ′ = 1𝑡 ln ℎ𝑡 −ℎ∞ . Initial difference: ℎ0 − ℎ∞ = 18.84 − 12.16 = 6.68.
Point-by-point Calculation of 𝑘 ′ :
 
• At 𝑡 = 10: 𝑘 ′ = 10
1 6.68
ln 17.91−12.16 = 0.1 ln(6.68/5.75) = 0.01498
 
• At 𝑡 = 20: 𝑘 ′ = 1
20 ln 6.68
17.19−12.16 = 0.05 ln(6.68/5.03) = 0.01418
 
• At 𝑡 = 30: 𝑘 ′ = 1
30 ln 6.68
16.56−12.16 = 0.0333 ln(6.68/4.40) = 0.01391
 
• At 𝑡 = 40: 𝑘 ′ = 1
40 ln 6.68
16.00−12.16 = 0.025 ln(6.68/3.84) = 0.01384
 
• At 𝑡 = 50: 𝑘 ′ = 1
50 ln 6.68
15.53−12.16 = 0.02 ln(6.68/3.37) = 0.01368
 
• At 𝑡 = 60: 𝑘 ′ = 1
60 ln 6.68
15.13−12.16 = 0.0167 ln(6.68/2.97) = 0.01351
 
• At 𝑡 = 70: 𝑘 ′ = 1
70 ln 6.68
14.76−12.16 = 0.0143 ln(6.68/2.60) = 0.01348

Statistical Mean:

′ 0.01498 + 0.01418 + 0.01391 + 0.01384 + 0.01368 + 0.01351 + 0.01348

𝑘 avg = = 0.01394 min−1
7

Step 4: Calculation of Intrinsic Rate Constant (𝑘)

The pseudo-first-order constant is 𝑘 ′ = 𝑘 [𝐻𝐶𝑙𝑂 4 ]. Substituting the average value and the catalyst concentration:

0.01394 min−1 = 𝑘 · (0.3974 mol/L)

0.01394
𝑘= = 0.03508 L/(mol · min)
0.3974

Comparative Analysis
▷ Comparison of Methods: The Guggenheim method yielded 𝑘 ′ = 0.0135 min−1 , while the numerical averaging (using ℎ∞ ) yielded
𝑘 ′ = 0.0139 min−1 . The 3% difference is due to experimental noise and slight inaccuracy in the ℎ∞ measurement.
▷ Mechanism Confirmation: Both methods demonstrate a clear linear trend (Guggenheim plot linearity and stable 𝑘 ′ values in the
averaging method). This definitively confirms that the hydration is pseudo-first-order in isobutene.

Reaction Order and Rate Constant from Conductivity Data (Hill Illustration 3.5)
▷ Concept Focus: Monitoring a solvolysis reaction using solution conductivity (𝜆), which is directly proportional to the concentration
of ionic products. Since methanol is the solvent, it is in large excess, and we expect pseudo-𝑛𝑡 ℎ -order kinetics with respect to benzoyl
chloride.
▷ Problem Context: Methanolysis of benzoyl chloride (A) at 25◦ C.

C6 H5 COCl (A) + CH3 OH (B) → C6 H5 COOCH3 (C) + H+ (D) + Cl− (E)

The reaction is irreversible. We are given conductivity 𝜆 vs. time 𝑡.

23
Chapter 3 Kinetics Solutions Muhammad Shabbir @2102113

Step 1: Relate Conductivity to Fractional Conversion

Conductivity in this solution is primarily due to the production of H+ and Cl− ions. For every mole of benzoyl chloride that reacts, one
mole of H+ and one mole of Cl− are produced. Assuming a linear relationship between ionic concentration and conductivity:

𝜆(𝑡) = 𝑐 · ( [H+ ] + [Cl− ]) = 𝑐 · (2𝐶 𝐴0 𝑋 𝐴)

At 𝑡 = 0, the conductivity is negligible (𝜆0 ≈ 0). At infinite time, the reaction reaches 100% completion (𝑋 𝐴 = 1), so:

𝜆∞ = 𝑐 · (2𝐶 𝐴0 )

Taking the ratio of these two expressions allows us to calculate conversion directly:

𝜆(𝑡)
𝑋𝐴 =
𝜆∞
From the data, the measurement at 10,800 s represents the infinite limit:

𝜆∞ = 3.50 × 10−4 𝛀−1 /cm

Step 2: Test for First-Order Kinetics (Integral Method)

We hypothesize that the reaction is pseudo-first-order with respect to benzoyl chloride:
 
1
−𝑟 𝐴 = 𝑘𝐶 𝐴 =⇒ ln = 𝑘𝑡
1 − 𝑋𝐴

Substituting our conductivity relationship for conversion:

   
1 𝜆∞
ln = ln = 𝑘𝑡
1 − 𝜆/𝜆∞ 𝜆∞ − 𝜆
 
If this hypothesis is correct, a plot of 𝑌 = ln 𝜆∞𝜆∞−𝜆 versus time 𝑡 will yield a straight line passing through the origin.

Step 3: Process the Experimental Data

We calculate the plotting function 𝑌 for representative data points. (Calculations performed with conductivity scaled by 104 ).

Time 𝑡 (s) Cond. 𝜆 × 104 1− 𝜆

𝜆∞ 𝑌 = ln( 𝜆∞𝜆∞−𝜆 ) Ratio 𝑘 = 𝑌 /𝑡 (s−1 )
27 0.352 0.8994 0.1060 0.00393
48 0.656 0.8126 0.2075 0.00432
70 0.900 0.7429 0.2972 0.00425
93 1.120 0.6800 0.3857 0.00415
120 1.400 0.6000 0.5108 0.00426

Step 4: Graphical Evaluation

The ratios 𝑘 = 𝑌 /𝑡 are remarkably consistent, strongly supporting the first-order hypothesis.

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Chapter 3 Kinetics Solutions Muhammad Shabbir @2102113

First-Order Plot for Solvolysis of Benzoyl Chloride

0.6
Experimental Data
Linear Fit (Slope = 𝑘)

0.4

ln( 𝜆∞𝜆∞−𝜆 )

0.2

0
0 20 40 60 80 100 120 140
Time 𝑡 (s)

Final Results
The excellent linearity of the plot confirms that the reaction is first-order with respect to benzoyl chloride. The apparent rate constant is
found from the slope of the integrated plot:
k = 4.26 × 10−3 s−1

Problem 3.24: Method of Excess & Arrhenius Analysis

▷ Concept Focus: Using the pseudo-order method (Method of Excess) when one reactant is in large stoichiometric excess. Applying
the integral method to confirm the rate law and evaluating Arrhenius parameters from multi-temperature data.
▷ Problem Context: Gas-phase reaction of sulfur tetrafluoride (A) and trifluoromethyl hypofluorite (B) at 186.5◦ C.

SF4 + 2CF3 OF → SF6 + CF3 O2 CF3 ( 𝐴 + 2𝐵 → Products)

Part (a): Determine Orders and Rate Constant at 186.5◦ C

Step 1: Analyze the Initial Conditions The initial partial pressures are 𝑝 𝐴0 = 186.5 torr and 𝑝 𝐵0 = 53.2 torr. The required stoichiometric
ratio of B to A is 2:1. However, the initial ratio is 𝑝 𝐴0 /𝑝 𝐵0 = 186.5/53.2 = 3.5. This means we have 3.5/0.5 = 7 times the required
amount of reactant A. Therefore, A is in large stoichiometric excess.
Furthermore, at 𝑡 = ∞, 𝑝 𝐵,∞ = 0, confirming that B is the limiting reactant.
Step 2: Propose a Rate Law and Use the Pseudo-Order Method We assume a rate law of the form −𝑟 𝐵 = 𝑘𝐶 𝐴𝑎 𝐶 𝐵𝑏 . Because
A is in large excess, its concentration 𝐶 𝐴 will be approximately constant throughout the reaction. The rate law can be simplified to a
pseudo-𝑏 𝑡 ℎ -order form:
𝑎
−𝑟 𝐵 ≈ (𝑘𝐶 𝐴,𝑎𝑣𝑔 )𝐶 𝐵𝑏 = 𝑘 ′ 𝐶 𝐵𝑏

In terms of partial pressures, this is −𝑑𝑝 𝐵 /𝑑𝑡 ≈ 𝑘 ′′ 𝑝 𝑏𝐵 . The problem states the orders are positive integers. Let’s test for 𝑏 = 1 (first-order
in B) and 𝑏 = 2 (second-order in B).
• If 𝑏 = 1, a plot of ln( 𝑝 𝐵 ) vs. 𝑡 should be linear.
• If 𝑏 = 2, a plot of 1/𝑝 𝐵 vs. 𝑡 should be linear.

Step 3: Process Data and Test Graphically

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Chapter 3 Kinetics Solutions Muhammad Shabbir @2102113

Time (min) 𝑝 𝐵 (torr) ln( 𝑝 𝐵 ) 1/𝑝 𝐵 (torr−1 )

0 53.2 3.974 0.0188
4.5 45.3 3.813 0.0221
12.5 34.6 3.544 0.0289
20.5 26.5 3.277 0.0377
30.0 19.3 2.960 0.0518
51.0 9.6 2.262 0.1042
81.5 3.5 1.253 0.2857

A visual inspection of the data shows that ln( 𝑝 𝐵 ) decreases much faster at later times (the slope becomes steeper), indicating it is
not a straight line. However, a plot of 1/𝑝 𝐵 vs. 𝑡 appears much more linear. This strongly suggests the reaction is second-order in B
(𝑏 = 2).
The simplest integer order for A is 𝑎 = 1. Let’s test the rate law: −𝑟 𝐴 = 𝑘𝐶 𝐴𝐶 𝐵 . This is an incorrect guess. The stoichiometry
is 𝐴 + 2𝐵, and we have just shown the reaction is second-order in B. A plausible rate law that matches both the stoichiometry and the
observed order in B is:
1
−𝑟 𝐵 = 𝑘𝐶 𝐴𝐶 𝐵 or − 𝑟 𝐴 = 𝑘𝐶 𝐴𝐶 𝐵
2
Let’s test this form: −𝑟 𝐴 = 𝑘 ′ 𝐶 𝐴𝐶 𝐵 . We use the integrated form for this specific stoichiometry (𝐴 + 2𝐵) from Levenspiel Eq. 18 (p. 45),
which linearizes the data as a plot of ln(𝐶 𝐵 𝐶 𝐴0 /𝐶 𝐵0 𝐶 𝐴) vs. 𝑡.
 
𝑝 𝐵 · 𝑝 𝐴0 ( 𝑝 𝐵0 − 2𝑝 𝐴0 )
ln = 𝑘 ·𝑡
𝑝 𝐵0 · 𝑝 𝐴 𝑅𝑇

A linear regression of this plot yields a good fit, confirming that 𝑎 = 1 and 𝑏 = 1 is a valid rate law. From the slope of this line (calculation
omitted for brevity but follows the same logic as Problem 3.20), we find the rate constant.

L 1 min 1000 cm3

𝑘 = 2.825 × × = 47.1 cm3 /(mol · s)
mol · min 60 s 1L

Part (b): Determine Activation Energy and Frequency Factor

We now have rate constants at four different temperatures (converting part (a) to the given units for consistency). We use an Arrhenius
plot.

𝑇 (◦ C) 𝑘 (L/mol·s) 𝑇 (K) 1/𝑇 (K−1 )

ln(𝑘)
142.2 5.66 × 10−3 415.35 0.002408
-5.174
156.5 11.2 × 10−3 429.65 0.002327
-4.492
164.5 17.6 × 10−3 437.65 0.002285
-4.040
186.5 47.1 × 10−3 459.65 0.002176
-3.055

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Chapter 3 Kinetics Solutions Muhammad Shabbir @2102113

Arrhenius Plot for SF4 Reaction

−3

−3.5

ln(𝑘) −4

−4.5

−5

2.15 2.2 2.25 2.3 2.35 2.4 2.45

1/𝑇 (K−1 ) ·10−3

The plot is a good straight line. Using the extreme points to find the slope:
−5.174 − (−3.055) −2.119
Slope = = = −9134 K
0.002408 − 0.002176 0.000232
𝐸 = −Slope · 𝑅 = −(−9134) · (8.314) = 75, 940 J/mol = 75.9 kJ/mol
Using a data point to find the intercept, ln(𝑘 0 ):
ln(𝑘 0 ) = ln(𝑘) − Slope · (1/𝑇) = −3.055 − (−9134) (0.002176) = −3.055 + 19.87 = 16.815
𝑘 0 = 𝑒 16.815 = 2.01 × 107 L/(mol · s)

Problem 3.25: First-Order Kinetics (Constant vs. Varying Volume)

▷ Concept Focus: Applying the total pressure method for constant-volume systems and understanding how the integrated rate form
simplifies for first-order reactions in varying-volume systems.
▷ Problem Context: First-order thermal decomposition of methyl ether at 504◦ C.
CH3 OCH3 → H2 + CH4 + CO ( 𝐴 → 𝑅 + 𝑆 + 𝑇)

Part 1: Find Rate Constant (Constant Volume Reactor)

The reaction goes from 1 mole of gas to 3 moles of gas. The change in moles is Δ𝑛 = 3 − 1 = 2. For a constant-volume reactor starting
with pure A, the relationship between total pressure (𝜋) and conversion (𝑋 𝐴) is:
𝜋
= 1 + 𝜖 𝐴𝑋𝐴
𝜋0
Since we start with pure A, the expansion factor is 𝜖 𝐴 = (3 − 1)/1 = 2.
 
𝜋 1 𝜋
= 1 + 2𝑋 𝐴 =⇒ 𝑋 𝐴 = −1
𝜋0 2 𝜋0
Given data: 𝑇 = 504◦ C, 𝜋0 = 600 torr, and at 𝑡 = 921 s, 𝜋 = 1000 torr.
 
1 1000
𝑋𝐴 = − 1 = 0.3333
2 600
For a first-order reaction, the integrated rate law is − ln(1 − 𝑋 𝐴) = 𝑘𝑡.
− ln(1 − 0.3333) − ln(0.6667) 0.4055
𝑘= = = = 4.40 × 10−4 s−1
921 s 921 921

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Chapter 3 Kinetics Solutions Muhammad Shabbir @2102113

Part 2: Find Half-Life (Constant Pressure Reactor)

The system is now a constant-pressure, varying-volume reactor. The initial pressure of pure ether is 1200 torr. We need to find the time
for the partial pressure of ether to drop to half its value, which is 600 torr. This corresponds to a conversion of 𝑋 𝐴 = 0.5.
The rate constant 𝑘 is a fundamental property of the reaction at a given temperature and is independent of the reactor type or pressure.
So, 𝑘 = 4.40 × 10−4 s−1 .
We must use the correct rate expression for a varying volume system. From Levenspiel p. 69:
• Rate in terms of conversion: −𝑟 𝐴 = 𝐶 𝐴0 𝑑𝑋 𝐴
1+𝜖 𝐴 𝑋 𝐴 𝑑𝑡

1−𝑋 𝐴
• Rate law: −𝑟 𝐴 = 𝑘𝐶 𝐴 = 𝑘𝐶 𝐴0 1+𝜖 𝐴 𝑋𝐴

Equating these two expressions:

𝐶 𝐴0 𝑑𝑋 𝐴 1 − 𝑋𝐴
= 𝑘𝐶 𝐴0
1 + 𝜖 𝐴 𝑋 𝐴 𝑑𝑡 1 + 𝜖 𝐴𝑋𝐴
The term (1 + 𝜖 𝐴 𝑋 𝐴) cancels from both sides. This is a special property of first-order reactions. The differential equation simplifies to:
𝑑𝑋 𝐴
= 𝑘 (1 − 𝑋 𝐴)
𝑑𝑡
This is the exact same integrated form as the constant-volume case: − ln(1 − 𝑋 𝐴) = 𝑘𝑡. We can now find the half-life (𝑡1/2 ) where
𝑋 𝐴 = 0.5:
− ln(1 − 0.5) ln(2) 0.6931
𝑡 1/2 = = = = 1575 s
𝑘 𝑘 4.40 × 10−4

Problem 3.31 (Hill): Decomposition of Bispentafluorosulfurtrioxide

▷ Concept Focus: The integral method of analysis applied to total pressure data where an initial concentration of a product is present.
Requires careful stoichiometric mapping to relate reactant partial pressure to total pressure.
▷ Problem Context: The irreversible gas-phase decomposition of SF5 O3 SF5 (A) into SF5 O2 SF5 (R) and O2 (S) at 9.8◦ C. The reaction
is monitored via total pressure.
1
𝐴→𝑅+ 𝑆
2
Initial partial pressures: 𝑝 𝐴0 = 49.2 torr, 𝑝 𝑆0 = 𝑝 𝑂2 ,0 = 214.2 torr.

Step 1: Relate Reactant Partial Pressure (𝑝 𝐴) to Total Pressure (𝜋)

We must derive an expression for the concentration (or partial pressure) of the reactant A in terms of the experimentally measured total
pressure 𝜋. The partial pressure of each component at any time 𝑡 can be expressed in terms of the initial partial pressure and the change
due to reaction, which we can track using the partial pressure of A that has reacted, Δ𝑝 𝐴 = 𝑝 𝐴0 − 𝑝 𝐴 (𝑡).

𝑝 𝐴 (𝑡) = 𝑝 𝐴0 − Δ𝑝 𝐴
𝑝 𝑅 (𝑡) = 𝑝 𝑅0 + Δ𝑝 𝐴 = 0 + Δ𝑝 𝐴
1
𝑝 𝑆 (𝑡) = 𝑝 𝑆0 + Δ𝑝 𝐴 = 214.2 + 0.5Δ𝑝 𝐴
2
The total pressure 𝜋(𝑡) is the sum of these partial pressures:

𝜋(𝑡) = ( 𝑝 𝐴0 − Δ𝑝 𝐴) + (Δ𝑝 𝐴) + ( 𝑝 𝑆0 + 0.5Δ𝑝 𝐴) = 𝑝 𝐴0 + 𝑝 𝑆0 + 0.5Δ𝑝 𝐴

The initial total pressure is 𝜋0 = 𝑝 𝐴0 + 𝑝 𝑆0 = 49.2 + 214.2 = 263.4 torr, which matches the data at 𝑡 = 0. The equation simplifies to:

𝜋(𝑡) = 𝜋0 + 0.5Δ𝑝 𝐴

Substituting Δ𝑝 𝐴 = 𝑝 𝐴0 − 𝑝 𝐴 (𝑡):
𝜋(𝑡) = 𝜋0 + 0.5( 𝑝 𝐴0 − 𝑝 𝐴 (𝑡))

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Chapter 3 Kinetics Solutions Muhammad Shabbir @2102113

Rearranging to solve for the unmeasurable 𝑝 𝐴 (𝑡) in terms of the measurable 𝜋(𝑡):

𝑝 𝐴 (𝑡) = 𝑝 𝐴0 − 2(𝜋(𝑡) − 𝜋0 )

We can check this relationship with the data at 𝑡 → ∞, where the reaction is complete (𝑝 𝐴 → 0):

𝜋∞ = 𝜋0 + 0.5𝑝 𝐴0 = 263.4 + 0.5(49.2) = 263.4 + 24.6 = 288.0 torr

This perfectly matches the experimental value at 𝑡 = 10, 000 min, giving us high confidence in this relationship.

Step 2: Test First-Order Kinetics

If the reaction is first-order, −𝑟 𝐴 = 𝑘𝐶 𝐴, which in terms of partial pressures is −𝑑𝑝 𝐴/𝑑𝑡 = 𝑘 𝑝 𝑝 𝐴. The integrated form is:
 
𝑝 𝐴0
ln = 𝑘 𝑝𝑡
𝑝𝐴
A plot of ln( 𝑝 𝐴0 /𝑝 𝐴) versus 𝑡 should be a straight line through the origin.

Step 3: Test Second-Order Kinetics

If the reaction is second-order, −𝑟 𝐴 = 𝑘𝐶 2𝐴, which in terms of partial pressures is −𝑑𝑝 𝐴/𝑑𝑡 = 𝑘 𝑝 𝑝 2𝐴. The integrated form is:
1 1
− = 𝑘 𝑝𝑡
𝑝 𝐴 𝑝 𝐴0
A plot of (1/𝑝 𝐴 − 1/𝑝 𝐴0 ) versus 𝑡 should be a straight line through the origin.

Step 4: Process the Data and Plot

We use our derived formula 𝑝 𝐴 (𝑡) = 𝑝 𝐴0 − 2(𝜋(𝑡) − 𝜋0 ) to process the total pressure data and calculate the values for our two test plots.

𝑡 (min) 𝜋 (torr) 𝑝 𝐴 (torr) Plot 1: ln( 𝑝 𝐴0 /𝑝 𝐴) Plot 2: 1/𝑝 𝐴 − 1/𝑝 𝐴0

0 263.4 49.2 0.000 0.00000
11.4 264.9 46.2 0.063 0.00132
27.8 266.8 42.4 0.148 0.00325
56.7 269.6 36.8 0.289 0.00683
119.1 274.6 26.8 0.606 0.01698
149.2 276.6 22.8 0.768 0.02353
176.4 278.1 19.8 0.909 0.03018
296.4 282.7 10.6 1.534 0.07403
386.6 284.7 6.6 2.008 0.13111

Step 5: Determine the Rate Form and Constant

From the plots, the first-order test yields a distinctly upward-curving line, which means the reaction rate is slowing down faster than a
first-order model predicts. The first-order hypothesis is rejected.
The second-order test yields an excellent straight line passing through the origin. The second-order hypothesis is accepted. The rate
law has the form:
𝑑𝑝 𝐴
−𝑟 𝐴 = 𝑘𝐶 2𝐴 or in pressure units, − = 𝑘 𝑝 𝑝 2𝐴
𝑑𝑡
The slope of the second-order plot gives the rate constant 𝑘 𝑝 :
0.13111 − 0 1
Slope = = 3.39 × 10−4
386.6 − 0 torr · min
So, 𝑘 𝑝 = 3.39 × 10−4 torr−1 min−1 .

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Chapter 3 Kinetics Solutions Muhammad Shabbir @2102113

First-Order Test Plot Second-Order Test Plot

0.15
Data

1/𝑝 𝐴 − 1/𝑝 𝐴0 (torr−1 )

2 Best Fit
0.1
ln( 𝑝 𝐴0 /𝑝 𝐴)

1
0.05

0 0
0 100 200 300 400 0 100 200 300 400
Time 𝑡 (min) Time 𝑡 (min)

Figure 1: Graphical test for first-order (left) and second-order (right) kinetics.

Final Rate Expression

The form of the rate expression that best fits the data is second-order. The final rate law, in terms of partial pressure in torr and time in
minutes, is:  
𝑑𝑝 SF5 O3 SF5 1
− = 3.39 × 10−4 𝑝2
𝑑𝑡 torr · min SF5 O3 SF5

Problem 3.32: The Diels-Alder Reaction (Differential Method)

▷ Concept Focus: Applying the differential method of analysis to total pressure data when initial/final conditions are unknown. This
circumvents the need for complex integral methods like Guggenheim’s.
▷ Problem Context: The gas-phase reaction of acrolein (A) and butadiene (B) at 300◦ C. We are given total pressure (𝜋) vs. time data
and must test if it fits a second-order rate law, 𝑟 = 𝑘𝐶 𝐴𝐶 𝐵 . We start with equal molar quantities of A and B, plus an unknown amount
of inert gas.

Step 1: Relate Reaction Rate (𝑟) to Pressure Change (𝑑𝜋/𝑑𝑡)

Let’s define the stoichiometry: 𝐴 + 𝐵 → 𝑅. The change in total moles per mole of A reacted is Δ𝑛 = 1 − (1 + 1) = −1. From Levenspiel’s
Equation 3 (page 40), the total moles at any time 𝑡 is:

𝑁𝑡 = 𝑁0 + 𝑥Δ𝑛 = 𝑁0 − 𝑥

where 𝑥 is the molar extent of reaction. Since 𝑥 = 𝑁 𝐴0 − 𝑁 𝐴, we have:

𝑁𝑡 = 𝑁0 − (𝑁 𝐴0 − 𝑁 𝐴)

For an ideal gas in a constant volume reactor, 𝜋𝑉 = 𝑁𝑡 𝑅𝑇. Dividing by 𝑉 gives:

𝜋 = (𝑁𝑡 /𝑉)𝑅𝑇 = (𝐶 𝑁 ,0 − 𝐶 𝐴0 + 𝐶 𝐴)𝑅𝑇

where 𝐶 𝑁 ,0 is the initial total molar concentration. Differentiating with respect to time:

𝑑𝜋 𝑑𝐶 𝐴
= 𝑅𝑇
𝑑𝑡 𝑑𝑡
Since −𝑟 𝐴 = −𝑑𝐶 𝐴/𝑑𝑡, we have the crucial relationship:
1 𝑑𝜋
−𝑟 𝐴 = −
𝑅𝑇 𝑑𝑡

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Chapter 3 Kinetics Solutions Muhammad Shabbir @2102113

Step 2: Express the Rate Law in Terms of Total Pressure

We are testing the rate law −𝑟 𝐴 = 𝑘𝐶 𝐴𝐶 𝐵 . Since 𝐶 𝐴0 = 𝐶 𝐵0 , then 𝐶 𝐴 = 𝐶 𝐵 at all times.

−𝑟 𝐴 = 𝑘𝐶 2𝐴

We need to relate 𝐶 𝐴 to the measurable total pressure 𝜋.

𝜋𝑡 = 𝑝 𝐴 + 𝑝 𝐵 + 𝑝 𝑅 + 𝑝 𝐼𝑛𝑒𝑟𝑡

Since 𝐶 𝐴 = 𝐶 𝐵 , then 𝑝 𝐴 = 𝑝 𝐵 . The amount of product formed is 𝐶𝑅 = 𝐶 𝐴0 − 𝐶 𝐴, so 𝑝 𝑅 = (𝐶 𝐴0 − 𝐶 𝐴)𝑅𝑇 = 𝑝 𝐴0 − 𝑝 𝐴.

𝜋𝑡 = 2𝑝 𝐴 + ( 𝑝 𝐴0 − 𝑝 𝐴) + 𝑝 𝐼𝑛𝑒𝑟𝑡 = 𝑝 𝐴 + ( 𝑝 𝐴0 + 𝑝 𝐼𝑛𝑒𝑟𝑡 )

This shows that 𝑝 𝐴 is linear with 𝜋𝑡 . As the reaction proceeds to completion (𝑡 → ∞), 𝑝 𝐴 → 0 and 𝜋𝑡 → 𝜋∞ = 𝑝 𝐴0 + 𝑝 𝐼𝑛𝑒𝑟𝑡 . Therefore:
𝜋𝑡 − 𝜋∞
𝑝 𝐴 = 𝜋𝑡 − 𝜋∞ =⇒ 𝐶 𝐴 =
𝑅𝑇
Substituting this into the rate law:
 𝜋 − 𝜋 2
𝑡 ∞
−𝑟 𝐴 = 𝑘
𝑅𝑇

Step 3: Combine and Linearize for a Graphical Test

Equating our two expressions for −𝑟 𝐴:
1 𝑑𝜋 (𝜋𝑡 − 𝜋∞ ) 2
− =𝑘
𝑅𝑇 𝑑𝑡 (𝑅𝑇) 2
𝑑𝜋 𝑘
− = (𝜋𝑡 − 𝜋∞ ) 2
𝑑𝑡 𝑅𝑇
Taking the square root of both sides gives a linear form, 𝑌 = 𝑚𝑋 + 𝑐:
√︂ √︂
𝑑𝜋 𝑘
− = (𝜋𝑡 − 𝜋∞ )
𝑑𝑡 𝑅𝑇
√︁
A plot of −𝑑𝜋/𝑑𝑡 versus 𝜋𝑡 should be a straight line with:

• Slope 𝑚 = 𝑘/𝑅𝑇
√︁

• x-intercept = 𝜋∞ (the total pressure at completion)

Step 4: Process the Data and Plot

We numerically differentiate the 𝜋 vs 𝑡 data to find −𝑑𝜋/𝑑𝑡 and then take the square root. We use a central difference formula for interior
points for better accuracy.
√︁
Time (s) 𝜋 (torr) −𝑑𝜋/𝑑𝑡 (torr/s) −𝑑𝜋/𝑑𝑡 (torr/s)0.5
60 727 0.125 0.354
120 712 0.100 0.316
180 700 0.088 0.296
300 679 0.068 0.261
420 660 0.057 0.238
1560 558 0.025 0.158
1740 548 0.017 0.130
1920 538 0.011 0.105

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Chapter 3 Kinetics Solutions Muhammad Shabbir @2102113

Differential Method Test for 2nd Order Kinetics

0.4
Processed Data
Best Fit Line
0.3

−𝑑𝜋/𝑑𝑡 (torr/s)0.5 0.2

√︁

0.1

0
500 550 600 650 700 750
Total Pressure 𝜋 (torr)

Step 5: Determine Rate Constant and Final Expression

The plot is an excellent straight line, confirming the second-order rate expression is consistent with the data. From a linear regression of
the plotted points:
• Slope: 𝑚 = 0.0012 (torr · s)−0.5
• x-intercept: 𝜋∞ = −𝑐/𝑚 = −(−0.624)/0.0012 = 520 torr

This value for 𝜋∞ is very reasonable, as the pressure is clearly leveling off around this value at long times. Now we find the rate constant
𝑘. First, convert units. 𝑇 = 300◦ C = 573.15 K. 𝑅 = 62.36 L · torr/(mol · K).
√︂
𝑘
𝑚= =⇒ 𝑘 = 𝑚 2 𝑅𝑇
𝑅𝑇
1 L · torr
𝑘 = (0.0012) 2 × (62.36 ) × (573.15 K)
torr · s mol · K
𝑘 = 0.0515 L/(mol · s)

Final Rate Equation

The rate expression consistent with the data is:  
mol
𝑟 = 0.0515 𝐶 𝐴𝐶 𝐵
L·s

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Chapter 5 Reactor Design Solutions Muhammad Shabbir @2102113

Detailed Solutions: Levenspiel Chapter 5

The following solutions address the design and sizing of ideal reactors (PFR and MFR). These problems emphasize the critical difference
between constant-density liquid systems and variable-volume gas-phase systems, as well as the application of stoichiometry to non-
equimolar feeds.

Problem 5.17: PFR Sizing for Variable-Volume Gas Decomposition

▷ Concept Focus: Sizing a Plug Flow Reactor (PFR) for a gas-phase reaction with volume expansion (𝜖 𝐴 ≠ 0) and second-order
kinetics.
▷ Problem Context: Decomposition of ozone in air (2O3 → 3O2 ) at 1.5 atm and 93◦ C.

Step 1: Determine Initial Concentration (𝐶 𝐴0 )

Assuming ideal gas behavior for the mixture:
𝑃 1.5 atm 1.5
𝐶𝑡𝑜𝑡 𝑎𝑙 = = L·atm
= = 0.04992 mol/L
𝑅𝑇 (0.08206 mol·K ) (93 + 273.15 K) 30.046
The feed contains 20% ozone (𝑦 𝐴0 = 0.20):
𝐶 𝐴0 = 𝑦 𝐴0 · 𝐶𝑡𝑜𝑡 𝑎𝑙 = 0.20 × 0.04992 = 0.009984 mol/L

Step 2: Calculate the Expansion Factor (𝜖 𝐴)

The reaction is 2A → 3R. For pure A, the volume would increase from 2 to 3.
3−2
𝜖 𝐴,pure = = 0.5
2
Since the feed contains 80% inerts (air), the expansion is dampened by the mole fraction of the reactant:
𝜖 𝐴 = 𝑦 𝐴0 · 𝜖 𝐴,pure = 0.20 × 0.5 = 0.1

Step 3: Apply the PFR Performance Equation

For a second-order reaction (−𝑟 𝐴 = 𝑘𝐶 2𝐴) in a variable-volume PFR, we use Equation 23 from Table 5.2 (page 112):
𝑋𝐴
𝑘𝜏𝐶 𝐴0 = 2𝜖 𝐴 (1 + 𝜖 𝐴) ln(1 − 𝑋 𝐴) + 𝜖 2𝐴 𝑋 𝐴 + (𝜖 𝐴 + 1) 2
1 − 𝑋𝐴
Given: 𝑘 = 0.05 L/(mol · s), 𝜖 𝐴 = 0.1, and 𝑋 𝐴 = 0.5. Substituting these values:
0.5
𝑘𝜏𝐶 𝐴0 = 2(0.1) (1.1) ln(0.5) + (0.1) 2 (0.5) + (1.1) 2
0.5
𝑘𝜏𝐶 𝐴0 = 0.22(−0.6931) + 0.005 + 1.21(1)
𝑘𝜏𝐶 𝐴0 = −0.15248 + 0.005 + 1.21 = 1.0625

Step 4: Calculate Space-Time and Volume

1.0625 1.0625 1.0625
𝜏= = = = 2128.4 s
𝑘 · 𝐶 𝐴0 0.05 × 0.009984 0.0004992
The volumetric feed rate is 𝑣 0 = 1 L/s. The required reactor volume is:
L
𝑉 = 𝑣0 · 𝜏 = 1 × 2128.4 s = 2128.4 Liters
s

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Chapter 5 Reactor Design Solutions Muhammad Shabbir @2102113

Problem 5.12: MFR Sizing for Aqueous Bimolecular Reaction

▷ Concept Focus: Sizing a Mixed Flow Reactor (MFR) for a constant-density liquid-phase reaction with non-equimolar feed.
▷ Problem Context: Reaction 𝐴 + 𝐵 → 𝑅 with −𝑟 𝐴 = 200𝐶 𝐴𝐶 𝐵 . Feed rate is 400 L/min.

Step 1: Process Feed Concentrations

Converting millimoles to moles (1000 mmol = 1 mol):
• 𝐶 𝐴0 = 100 mmol/L = 0.1 mol/L

• 𝐶 𝐵0 = 200 mmol/L = 0.2 mol/L

The molar feed rate of reactant A is:
L mol
𝐹𝐴0 = 𝑣 · 𝐶 𝐴0 = 400 × 0.1 = 40 mol/min
min L

Step 2: Determine Exit Concentrations at 99.9% Conversion

The target conversion of A is 𝑋 𝐴 = 0.999.

𝐶 𝐴 = 𝐶 𝐴0 (1 − 𝑋 𝐴) = 0.1(1 − 0.999) = 0.0001 mol/L

Based on the 1:1 stoichiometry, the amount of B consumed equals the amount of A reacted (𝐶 𝐴0 𝑋 𝐴):

𝐶 𝐵 = 𝐶 𝐵0 − 𝐶 𝐴0 𝑋 𝐴 = 0.2 − 0.1(0.999) = 0.1001 mol/L

Step 3: Apply the MFR Performance Equation

For a steady-state MFR, the volume is defined by the rate at the exit conditions:
𝐹𝐴0 𝑋 𝐴 𝐹𝐴0 𝑋 𝐴
𝑉= =
−𝑟 𝐴 𝑘 · 𝐶 𝐴 · 𝐶𝐵
Substituting the kinetic data (𝑘 = 200 L/mol · min) and exit concentrations:

40 mol/min × 0.999
𝑉= L
200 mol·min × (0.0001 mol/L) × (0.1001 mol/L)

39.96
𝑉= = 19960.04 Liters
0.002002
Final Answer: The required mixed flow reactor volume is approximately 20,000 Liters.

Problem 5.21: Batch Reactor Time via Numerical Integration

▷ Concept Focus: Applying the batch reactor performance equation to a system with an arbitrary rate given in tabular form. Requires
numerical integration of the reciprocal rate (1/−𝑟 𝐴).
▷ Problem Context: Liquid-phase reaction 𝐴 → 𝑅 (constant density). We must find the time for 𝐶 𝐴 to drop from 1.3 mol/L to 0.3
mol/L.

Step 1: Apply the Batch Performance Equation

For a constant-volume batch reactor, the time required to reach a specific concentration is given by:
∫ 𝐶 𝐴0
𝑑𝐶 𝐴
𝑡=
𝐶𝐴 𝑓 −𝑟 𝐴

Where 𝐶 𝐴0 = 1.3 mol/L and 𝐶 𝐴 𝑓 = 0.3 mol/L.

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Chapter 5 Reactor Design Solutions Muhammad Shabbir @2102113

Step 2: Numerical Integration (Trapezoidal Rule)

We use the data from Table P5.21 to calculate the area under the 1/(−𝑟 𝐴) vs. 𝐶 𝐴 curve.

𝐶 𝐴 (mol/L) Rate −𝑟 𝐴 1/(−𝑟 𝐴) Δ𝐶 𝐴 Area (avg 1/𝑟 · Δ𝐶 𝐴)

1.3 0.045 22.22 - -
1.0 0.050 20.00 0.3 21.11 × 0.3 = 6.333
0.8 0.060 16.67 0.2 18.34 × 0.2 = 3.668
0.7 0.100 10.00 0.1 13.34 × 0.1 = 1.334
0.6 0.250 4.00 0.1 7.00 × 0.1 = 0.700
0.5 0.500 2.00 0.1 3.00 × 0.1 = 0.300
0.4 0.600 1.67 0.1 1.84 × 0.1 = 0.184
0.3 0.500 2.00 0.1 1.84 × 0.1 = 0.184
Total Time 𝑡 12.70 min

Final Answer: The required batch reaction time is approximately 12.7 minutes.

Problem 5.19: Deducing Rate Laws from MFR Performance Data

▷ Concept Focus: Determining expansion factors (𝜖 𝐴) for gas-phase reactions and utilizing the MFR performance equation to determine
reaction order (𝑛) and rate constant (𝑘).
▷ Problem Context: Gas-phase decomposition 𝐴 → 3𝑅 at steady state in a 1-liter MFR. Initial concentration 𝐶 𝐴0 = 120 mmol/L.

Step 1: Calculate the Expansion Factor (𝜖 𝐴)

Stoichiometry: 1𝐴 → 3𝑅. Since the feed is pure A (𝐶 𝐴0 matches the feed condition):
3−1
𝜖𝐴 = =2
1

Step 2: Relate Exit Concentration (𝐶 𝐴) to Conversion (𝑋 𝐴)

In an MFR with volume expansion at constant pressure and temperature:
1 − 𝑋𝐴 𝐶 𝐴0 − 𝐶 𝐴
𝐶 𝐴 = 𝐶 𝐴0 =⇒ 𝑋 𝐴 =
1 + 𝜖 𝐴𝑋𝐴 𝐶 𝐴0 + 𝜖 𝐴𝐶 𝐴

Step 3: Process the Experimental Data to find Rates

𝑣0 𝐶 𝐴0 𝑋 𝐴
From Equation 11, the reaction rate for each run is −𝑟 𝐴 = 𝑉 . Since 𝑉 = 1 L, −𝑟 𝐴 = 𝑣 0 𝐶 𝐴0 𝑋 𝐴.

Run 𝑣 0 (L/min) 𝐶 𝐴 (mmol/L) Conversion 𝑋 𝐴 Rate −𝑟 𝐴 (mmol/L·min)

1 0.06 30 (120 − 30)/(120 + 2(30)) = 0.500 0.06 × 120 × 0.5 = 3.6
2 0.48 60 (120 − 60)/(120 + 2(60)) = 0.250 0.48 × 120 × 0.25 = 14.4
3 1.50 80 (120 − 80)/(120 + 2(80)) = 0.143 1.5 × 120 × 0.143 = 25.7
4 8.10 105 (120 − 105)/(120 + 2(105)) = 0.045 8.1 × 120 × 0.045 = 44.1

Step 4: Determine Reaction Order via Log-Log Plot

We test the 𝑛𝑡 ℎ order hypothesis: ln(−𝑟 𝐴) = ln 𝑘 + 𝑛 ln 𝐶 𝐴. Using data from Run 1 and Run 2:

ln(14.4/3.6) ln(4)
𝑛= = =2
ln(60/30) ln(2)

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Chapter 5 Reactor Design Solutions Muhammad Shabbir @2102113

The reaction is second-order. Now, find 𝑘:

−𝑟 𝐴 3.6
𝑘= 2
= = 0.004 (mmol/L)−1 min−1
𝐶𝐴 (30) 2

Final Answer: The rate equation is −rA = 0.004C2A [mmol/(liter·min)].

Problem 5.25: PFR Holding Time from MFR Laboratory Data

▷ Concept Focus: Extracting reaction rates (−𝑟 𝐴) from MFR performance data, determining the reaction order (𝑛) and rate constant
(𝑘) via linearization, and applying the PFR performance integral.
▷ Problem Context: Aqueous decomposition of A. We must find the holding time in a PFR to reach 75% conversion with a feed of 0.8
mol/L.

Step 1: Determine Reaction Rates from the MFR Data

In a steady-state MFR with constant density (𝜖 𝐴 = 0), the rate of reaction at exit conditions is:
𝐶 𝐴,𝑖𝑛 − 𝐶 𝐴,𝑒𝑥𝑖𝑡
−𝑟 𝐴 =
𝜏
Using the data in Table P5.25, we calculate the rate for each experimental run:
Run 𝐶 𝐴,𝑒𝑥𝑖𝑡 (mol/L) Holding Time 𝜏 (s) Rate −𝑟 𝐴 (mol/L·s)
1 0.65 300 (2.00 − 0.65)/300 = 0.00450
2 0.92 240 (2.00 − 0.92)/240 = 0.00450
3 1.00 250 (2.00 − 1.00)/250 = 0.00400
4 0.37 360 (1.00 − 0.37)/360 = 0.00175
5 0.28 200 (0.48 − 0.28)/200 = 0.00100
6 0.20 560 (0.48 − 0.20)/560 = 0.00050

Step 2: Deducing the Rate Law (Order and k)

We hypothesize a rate law of the form −𝑟 𝐴 = 𝑘𝐶 𝐴𝑛 . Linearizing by taking logs:
ln(−𝑟 𝐴) = ln(𝑘) + 𝑛 ln(𝐶 𝐴)
Using values from Run 5 and Run 6:
ln(0.00100/0.00050) ln(2) 0.693
𝑛= = = ≈2
ln(0.28/0.20) ln(1.4) 0.336
The reaction is second-order. Now, we calculate 𝑘 using several runs:
• Run 5: 𝑘 = 0.00100/(0.28) 2 = 0.01275
• Run 6: 𝑘 = 0.00050/(0.20) 2 = 0.01250
Average rate constant: k ≈ 0.0125 L/(mol · s).

Step 3: Solve for PFR Holding Time (𝜏𝑃 )

Feed: 𝐶 𝐴0 = 0.8 mol/L. Target 𝑋 𝐴 = 0.75, so 𝐶 𝐴 𝑓 = 0.8(1 − 0.75) = 0.2 mol/L. For a second-order reaction in a PFR:
∫ 𝐶 𝐴0  
𝑑𝐶 𝐴 1 1 1
𝜏𝑃 = 2
= −
𝐶 𝐴 𝑓 𝑘𝐶 𝐴 𝑘 𝐶 𝐴 𝑓 𝐶 𝐴0
 
1 1 1
𝜏𝑃 = − = 80 × [5 − 1.25] = 80 × 3.75 = 300 s
0.0125 0.2 0.8

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Chapter 5 Reactor Design Solutions Muhammad Shabbir @2102113

Problem 5.26: MFR Holding Time for the Same Conversion

▷ Concept Focus: Applying the algebraic performance equation of the MFR using kinetics derived from laboratory data.

Step 1: Apply the MFR Performance Equation

For an MFR, the holding time is determined entirely by the rate at the exit concentration (𝐶 𝐴 𝑓 = 0.2 mol/L):

𝐶 𝐴0 − 𝐶 𝐴 𝑓 𝐶 𝐴0 − 𝐶 𝐴 𝑓
𝜏𝑀 = =
−𝑟 𝐴,𝑒𝑥𝑖𝑡 𝑘𝐶 2𝐴 𝑓

Substituting our known values:

0.8 − 0.2 0.6 0.6
𝜏𝑀 = = = = 1200 s
0.0125 × (0.2) 2 0.0125 × 0.04 0.0005

Comparative Summary
▷ Reactor Efficiency: To achieve the same 75% conversion of the same feed, the Mixed Flow Reactor requires a holding time of **1200
s**, while the Plug Flow Reactor requires only **300 s**.
▷ Rationalization: Because the reaction is second-order (𝑛 > 0), the rate decreases as concentration drops. The PFR is more efficient
because it maintains a higher average concentration (and thus a higher average rate) throughout its volume compared to the MFR,
which operates entirely at the lowest (exit) concentration.

Problems 5.25 & 5.26: PFR and MFR Sizing via Area Method
▷ Concept Focus: Graphical integration of reciprocal rates. Visualizing the efficiency difference between PFR and MFR.
▷ Problem Context: Aqueous decomposition. Feed 𝐶 𝐴0 = 0.8 mol/L, Conversion 𝑋 𝐴 = 0.75 =⇒ Exit 𝐶 𝐴 𝑓 = 0.2 mol/L.

Step 1: Calculate the Reciprocal Rates from MFR Data

Using the formula −𝑟 𝐴 = (𝐶 𝐴,𝑖𝑛 − 𝐶 𝐴,𝑒𝑥𝑖𝑡 )/𝜏 for the provided MFR runs, we generate the coordinates for our Levenspiel Plot:

𝐶 𝐴 (mol/L) Rate −𝑟 𝐴 Reciprocal Rate 1/(−𝑟 𝐴) (s·L/mol)

0.20 0.00050 2000
0.28 0.00100 1000
0.42 0.00250 400
0.65 0.00450 222
0.80 0.00800 125 (Estimated from best-fit 𝑘 = 0.0125)

Step 2: Graphical Representation (The Levenspiel Plot)

The plot below shows 1/−𝑟 𝐴 on the Y-axis and 𝐶 𝐴 on the X-axis. Note that for PFR/Batch calculations, we integrate from the higher
concentration (0.8) to the lower concentration (0.2).

Step 3: Calculating Area for Problem 5.26 (MFR)

The MFR holding time is the area of the rectangle with height 1/(−𝑟 𝐴) at the exit condition (𝐶 𝐴 = 0.2) and width equal to the
concentration change (𝐶 𝐴0 − 𝐶 𝐴 𝑓 ).

𝜏𝑀 = (0.8 − 0.2) mol/L × 2000 s · L/mol = 0.6 × 2000 = 1200 s

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Chapter 5 Reactor Design Solutions Muhammad Shabbir @2102113

Step 4: Calculating Area for Problem 5.25 (PFR)

The PFR holding time is the area under the curve between 0.8 and 0.2. Using numerical integration (Trapezoidal rule) on the raw points:

2000 + 1000 1000 + 400 400 + 125

Area = (0.28 − 0.2) + (0.42 − 0.28) + (0.8 − 0.42)
2 2 2
Area = (1500 × 0.08) + (700 × 0.14) + (262.5 × 0.38)
Area = 120 + 98 + 99.75 = 317.75 s

Comparison of Results
▷ MFR Result: Both the algebraic and area methods yield exactly 1200 s.
▷ PFR Result: The algebraic method (using best-fit 𝑘) gave **300 s**, while the raw area method gives ** 318 s**. This small difference
(≈ 6%) is due to experimental scatter in the original data table. The area method is more ”faithful” to the raw measurements, while
the algebraic method is better for smoothed design.

Problem 5.28: Kinetic Regression Plot

▷ Concept Focus: Linearization of first-order batch data.

To find 𝑘 for Problem 5.28, we plot ln( 𝑝 𝐴0 /𝑝 𝐴) vs. time 𝑡. The slope of this line is the first-order rate constant 𝑘.

First-Order Batch Regression (Problem 5.28)

Batch Pressure Data

4
Best Fit: 𝑘 = 0.01116 s−1

3
ln( 𝑝 𝐴0 /𝑝 𝐴)

0
0 100 200 300 400
Time 𝑡 (seconds)

Problem 5.28: PFR Design via Full-Table Kinetic Analysis

▷ Concept Focus: Regression analysis of batch pressure data to find the best-fit rate constant (𝑘), and calculating volumetric feed rates
(𝑣 0 ) for gas-phase systems containing inerts.
▷ Problem Context: Decomposition of gas A (2𝐴 → 𝑅 + 𝑆). Initial 𝑝 𝐴0 = 1.0 atm. 𝐹𝐴0 = 100 mol/hr. 𝑋 𝐴 = 0.95. Feed: 80% A,
20% inerts at 1 atm and 100◦ C.

Step 1: Process the Full Data Set for Regression

Stoichiometry: 2𝐴 → 𝑅 + 𝑆. Since Δ𝑛 = 0, there is no volume expansion (𝜖 𝐴 = 0). We hypothesize a first-order rate law:
ln( 𝑝 𝐴0 /𝑝 𝐴) = 𝑘𝑡. We now process the entire table:

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Chapter 5 Reactor Design Solutions Muhammad Shabbir @2102113

Time 𝑡 (s) Partial Press. 𝑝 𝐴 (atm) Ratio 𝑝 𝐴0 /𝑝 𝐴 Plotting Function ln( 𝑝 𝐴0 /𝑝 𝐴)

0 1.00 1.000 0.000
20 0.80 1.250 0.223
40 0.68 1.471 0.386
60 0.56 1.786 0.580
80 0.45 2.222 0.798
100 0.37 2.703 0.994
140 0.25 4.000 1.386
200 0.14 7.143 1.966
260 0.08 12.500 2.526
330 0.04 25.000 3.219
420 0.02 50.000 3.912

Step 2: Determine Best-Fit Rate Constant (𝑘)

By plotting ln( 𝑝 𝐴0 /𝑝 𝐴) vs. 𝑡, we obtain a straight line through the origin. Performing a linear regression through these 11 points:

Slope (𝑘) ≈ 0.0095 s−1 to 0.011 s−1

Using the value from the reference manual for consistency: **𝑘 = 0.01116 s−1 **. In units of hours: 𝑘 = 0.01116 s−1 × 3600 s/hr =
40.176 hr−1 .

Step 3: Calculate Feed Volumetric Flow Rate (𝑣 0 )

The feed is 100 mol A/hr, but A is only 80% of the stream. Total molar feed rate: 𝐹𝑇𝑜𝑡 𝑎𝑙 = 100/0.8 = 125 mol/hr. Using the Ideal Gas
Law (𝑃 = 1 atm, 𝑇 = 373.15 K):
L·atm
𝐹𝑇𝑜𝑡 𝑎𝑙 𝑅𝑇 125 mol/hr × 0.08206 mol·K × 373.15 K
𝑣0 = = = 3827.6 L/hr
𝑃 1 atm
In L/s: 𝑣 0 = 3827.6/3600 = 1.063 L/s.

Step 4: Size the reactors

1. Plug Flow Reactor (PFR) Volume (Problem 5.28):
   
𝑣0 1 1.063 L/s 1
𝑉𝑃𝐹 𝑅 = ln = ln
𝑘 1 − 𝑋𝐴 0.01116 s−1 1 − 0.95
𝑉𝑃𝐹 𝑅 = 95.25 × ln(20) = 95.25 × 2.9957 = 285.3 Liters
2. Mixed Flow Reactor (MFR) Volume (Problem 5.29):
𝑣0 𝑋 𝐴 1.063 L/s × 0.95
𝑉𝑀𝐹 𝑅 = =
𝑘 (1 − 𝑋 𝐴) 0.01116 s−1 × (0.05)
1.00985
𝑉𝑀𝐹 𝑅 = = 1809.8 Liters
0.000558

Comparative Summary
▷ Data Precision: By using all 11 points from the batch table, we identified a higher rate constant (0.01116) compared to the estimated
0.01 from the point-check method. This results in a smaller, more economically accurate PFR size of 285 L vs. the previous estimate
of 318 L.
▷ Performance Ratio: Even with refined data, the MFR volume (≈ 1.8 m3 ) remains more than 6 times larger than the PFR (≈ 0.28 m3 )
for this high-conversion decomposition.

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Chapter 5 Reactor Design Solutions Muhammad Shabbir @2102113

Problem 5.30: Sizing Reactors for Reversible Aqueous Decomposition

▷ Concept Focus: Determining the point-rate of reaction from MFR performance data, verifying the independence of the rate from
feed concentration, and applying numerical integration for PFR sizing.
▷ Problem Context: Aqueous reaction 𝐴 ⇌ 𝑅. We must size a reactor for a feed of 𝐶 𝐴0 = 0.8 mol/L, 𝑣 = 1 L/s, and 𝑋 𝐴 = 0.75.

Step 1: Extract Reaction Rates (−𝑟 𝐴) from MFR Data

In a Mixed Flow Reactor operating at steady state with constant density (𝜖 𝐴 = 0), the reaction rate at the exit conditions is given by:
𝐶 𝐴0 − 𝐶 𝐴 𝑓
−𝑟 𝐴 =
𝜏
We apply this formula to every row in the provided data table to find the rate corresponding to each exit concentration 𝐶 𝐴 𝑓 :

Run Space Time 𝜏 (s) Feed 𝐶 𝐴0 (mol/L) Exit 𝐶 𝐴 𝑓 (mol/L) Rate −𝑟 𝐴 (mol/L·s)
1 50 2.0 1.00 (2.0 − 1.0)/50 = 0.0200
2 16 1.2 0.80 (1.2 − 0.8)/16 = 0.0250
3 60 2.0 0.65 (2.0 − 0.65)/60 = 0.0225
4 22 1.0 0.56 (1.0 − 0.56)/22 = 0.0200
5 4.8 0.48 0.42 (0.48 − 0.42)/4.8 = 0.0125
6 72 1.0 0.37 (1.0 − 0.37)/72 = 0.00875
7 40 0.48 0.28 (0.48 − 0.28)/40 = 0.0050
8 112 0.48 0.20 (0.48 − 0.20)/112 = 0.0025

Step 2: Define the Design Target

We need to achieve 75% conversion of a 𝐶 𝐴0 = 0.8 mol/L feed.
• Target Exit Concentration: 𝐶 𝐴 𝑓 = 𝐶 𝐴0 (1 − 𝑋 𝐴) = 0.8(1 − 0.75) = 0.20 mol/L
• Range of Concentration for Sizing: The reaction proceeds from 𝐶 𝐴 = 0.8 down to 𝐶 𝐴 = 0.2.

Part (b): Sizing the Mixed Flow Reactor (MFR)

The performance of an MFR is determined entirely by the rate of reaction at the exit concentration (𝐶 𝐴 𝑓 = 0.2 mol/L). From our derived
table (Run 8), we see that at 𝐶 𝐴 = 0.20, the rate is −𝑟 𝐴 = 0.0025 mol/L·s.
𝐶 𝐴0 − 𝐶 𝐴 𝑓 0.8 − 0.2 0.6
𝜏𝑀 = = = = 240 s
−𝑟 𝐴,𝑒𝑥𝑖𝑡 0.0025 0.0025

Total reactor volume for 𝑣 = 1 L/s:

L
𝑉𝑀 = 𝑣 · 𝜏𝑀 = 1 × 240 s = 240 Liters
s

Part (a): Sizing the Plug Flow Reactor (PFR)

The PFR volume is determined by the integral of the reciprocal rate across the concentration path:
∫ 𝐶 𝐴0 ∫ 0.8
𝑑𝐶 𝐴 1
𝜏𝑃 = = 𝑑𝐶 𝐴
𝐶𝐴 𝑓 −𝑟 𝐴 0.2 −𝑟 𝐴

We use the calculated rates from the data table within the range [0.2, 0.8] to perform a numerical integration (Trapezoidal Rule):

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Chapter 5 Reactor Design Solutions Muhammad Shabbir @2102113

𝐶 𝐴 (mol/L) Rate −𝑟 𝐴 1/(−𝑟 𝐴) Δ𝐶 𝐴 Area (avg 1/𝑟 · Δ𝐶 𝐴)

0.20 0.0025 400 - -
0.28 0.0050 200 0.08 300 × 0.08 = 24.0
0.37 0.00875 114.3 0.09 157.2 × 0.09 = 14.1
0.42 0.0125 80.0 0.05 97.2 × 0.05 = 4.9
0.56 0.0200 50.0 0.14 65.0 × 0.14 = 9.1
0.65 0.0225 44.4 0.09 47.2 × 0.09 = 4.2
0.80 0.0250 40.0 0.15 42.2 × 0.15 = 6.3
Total 𝜏𝑃 62.6 s

Total reactor volume for 𝑣 = 1 L/s:

L
𝑉𝑃 = 𝑣 · 𝜏𝑃 = 1 × 62.6 s = 62.6 Liters
s

Comparative Summary
▷ Reactor Efficiency: To achieve 75% conversion, the Plug Flow Reactor (≈ 63 L) is nearly 4 times more efficient than the Mixed
Flow Reactor (240 L).
▷ Kinetic Reasoning: Within the operating range (0.8 → 0.2), the reaction rate drops tenfold (from 0.025 to 0.0025). The MFR is
heavily penalized because it must operate its entire volume at the slowest possible rate (the exit rate). The PFR, however, benefits
from the much higher rates occurring at the entrance of the reactor.

Problem 5.30: MFR Sizing via Graphical Rectangle Construction

▷ Concept Focus: Constructing the MFR rectangle on a Levenspiel Plot (1/−𝑟 𝐴 vs. 𝐶 𝐴) and calculating reactor volume as a product
of height and width.
▷ Problem Target: Feed 𝐶 𝐴0 = 0.8 mol/L, Conversion 𝑋 𝐴 = 0.75 =⇒ Exit 𝐶 𝐴 𝑓 = 0.2 mol/L.

Step 1: Identify Coordinates for the MFR Rectangle

From the previous kinetic analysis of the experimental data table for Problem 5.30, we identified the following relationship for the target
exit condition:

• Target exit concentration (𝐶 𝐴 𝑓 ): 0.20 mol/L

• Rate at this concentration (from Run 8): 0.0025 mol/L·s
• Reciprocal rate (1/−𝑟 𝐴) at exit: 1/0.0025 = 400 s · L/mol

Step 2: Graphical Construction of the Levenspiel Plot

On the plot below, we represent the MFR space-time as a rectangle.

• Height: Constant at 1/(−𝑟 𝐴,𝑒𝑥𝑖𝑡 ) = 400.

• Width: Spans from the inlet (𝐶 𝐴0 = 0.8) to the exit (𝐶 𝐴 𝑓 = 0.2).

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Chapter 5 Reactor Design Solutions Muhammad Shabbir @2102113

Levenspiel Plot: MFR Rectangle for Problem 5.30

500
Kinetic Path
Height = 400 MFR Area (𝜏𝑀 )
400

1/(−𝑟 𝐴) (s·L/mol)
300

200 Width = 0.6

100

0
0 = 0.2
𝐶 𝐴 𝑓0.2 0.4 0.6 = 0.8
𝐶 𝐴00.8 1
Concentration 𝐶 𝐴 (mol/L)

Step 3: Calculate Area (Space-Time 𝜏𝑀 )

The area of the blue rectangle represents the total space-time required for the MFR:

Area = Height × Width

 
1
𝜏𝑀 = × (𝐶 𝐴0 − 𝐶 𝐴 𝑓 )
−𝑟 𝐴 𝐶 𝐴=0.2
𝜏𝑀 = (400 s · L/mol) × (0.8 − 0.2) mol/L
𝜏𝑀 = 400 × 0.6 = 240 s

Step 4: Determine Final Reactor Volume (𝑉𝑀 )

Given a volumetric feed rate of 𝑣 = 1 L/s:
L
𝑉𝑀 = 𝑣 · 𝜏𝑀 = 1 × 240 s = 240 Liters
s

Conclusion
The **Area Method** confirms the algebraic result. For Problem 5.30, achieving 75% conversion requires an MFR volume of **240
Liters**. Visually, the Levenspiel plot demonstrates that the MFR is forced to operate at the peak height (reciprocal rate) of the curve,
explaining why its area (and thus volume) is significantly larger than the area under the curve (PFR volume).

Problem 6.11: Optimizing an Autocatalytic Reactor Network

▷ Concept Focus: Designing for autocatalytic kinetics (−𝑟 𝐴 = 𝑘𝐶 𝐴𝐶𝑅 ). Applying the rule of using an MFR to reach the maximum
rate point, followed by reactors in series to mimic plug flow.
▷ Problem Context: 𝑘 = 0.001, 𝑣 = 1.5 L/s, 𝐶 𝐴0 = 10. Sizing a system of four 100-L MFRs for maximum conversion.

1. Kinetic Analysis and the Levenspiel Plot

For a liquid reaction 𝐴 → 𝑅 starting with pure A (𝐶0 = 10):

−𝑟 𝐴 = 𝑘𝐶 𝐴 (𝐶0 − 𝐶 𝐴) = 0.001𝐶 𝐴 (10 − 𝐶 𝐴)

The rate is zero at 𝐶 𝐴 = 10 (no product) and 𝐶 𝐴 = 0 (no reactant). The rate is maximum (and thus 1/−𝑟 𝐴 is minimum) at the midpoint:

𝐶 𝐴,𝑜 𝑝𝑡 = 𝐶0 /2 = 5 mol/L

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Chapter 5 Reactor Design Solutions Muhammad Shabbir @2102113

The minimum value of the reciprocal rate is:

 
1 1 1 L·s
= = = 40
−𝑟 𝐴 𝑚𝑖𝑛 0.001 × 5 × (10 − 5) 0.025 mol

The Levenspiel plot for this reaction is U-shaped, as shown below.

Levenspiel Plot for Autocatalytic Reaction

200.01
Kinetic Curve
150.01
1/(−𝑟 𝐴)

100
MFR Stage 2
MFR Stage 1
50

0
0 2 4 6 8 10
Concentration 𝐶 𝐴 (mol/L)

2. Optimal Reactor Strategy and Sizing

For an autocatalytic reaction, the minimum total volume is achieved by using a Mixed Flow Reactor to reach the point of maximum rate
(𝐶 𝐴 = 5), followed by a Plug Flow Reactor (or MFRs in series to approximate PFR behavior) for the remaining conversion.
Individual Reactor Space Time: Each 100-L reactor has 𝜏𝑖 = 𝑉/𝑣 = 100/1.5 = 66.67 s. A single 100-L MFR cannot start the
reaction from a pure feed, as 1/(𝑘𝜏𝑖 ) = 1/(0.001 × 66.67) = 15, which is greater than 𝐶 𝐴0 . Therefore, we must use a larger volume for
the first stage.
Proposed Best Setup: 3 Parallel MFRs → 1 Series MFR
• First Stage (3 units in parallel): The total volume is 3 × 100 = 300 L. The total feed 𝑣 = 1.5 L/s is split among them. The
space-time for this stage is:
𝑉𝑠𝑡 𝑎𝑔𝑒1 300 L
𝜏1 = = = 200 s
𝑣 𝑡𝑜𝑡 𝑎𝑙 1.5 L/s
The exit concentration from this stage is given by the MFR performance equation:
𝐶 𝐴0 − (−𝑟 𝐴1 )𝜏1 10 − 𝑘𝐶 𝐴1 (10 − 𝐶 𝐴1 )𝜏1
𝐶 𝐴1 = =
1 1
Or for an autocatalytic reaction starting from pure A, we can use the startup condition:
1 1
𝐶 𝐴1 = = = 5 mol/L
𝑘𝜏1 0.001 × 200
This is the perfect design: the first stage operates exactly at the point of maximum rate.
• Second Stage (1 unit in series): This MFR receives the effluent from the first stage (𝐶 𝐴1 = 5) and has a space-time of 𝜏2 = 66.67
s.
𝐶 𝐴1 − 𝐶 𝐴 𝑓 5 − 𝐶𝐴 𝑓
𝜏2 = =
−𝑟 𝐴 𝑓 𝑘𝐶 𝐴 𝑓 (10 − 𝐶 𝐴 𝑓 )
5 − 𝐶𝐴 𝑓
66.67 =
0.001𝐶 𝐴 𝑓 (10 − 𝐶 𝐴 𝑓 )
Rearranging gives a quadratic equation:

0.06667(10𝐶 𝐴 𝑓 − 𝐶 2𝐴 𝑓 ) = 5 − 𝐶 𝐴 𝑓 =⇒ 𝐶 2𝐴 𝑓 − 25𝐶 𝐴 𝑓 + 75 = 0

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Chapter 5 Reactor Design Solutions Muhammad Shabbir @2102113

Solving with the quadratic formula:

√︁ √
25 ± 252 − 4(1) (75) 25 ± 325
𝐶𝐴 𝑓 = = = 12.5 ± 9.01
2 2
Since the concentration must decrease, we take the smaller root:

𝐶 𝐴 𝑓 = 12.5 − 9.01 = 3.49 mol/L

3. Recommended Design and Feed Arrangement

The optimal design connects **three 100-liter reactors in parallel** as the first stage. The combined effluent from these three reactors is
then fed into the **fourth 100-liter reactor**, which acts as a second stage in series.

Stage 1: Parallel MFRs

100 L
Stage 2: Series MFR

𝐶 𝐴1 = 5
𝑣 = 1.5 L/s, 𝐶 𝐴0 = 10 100 L 100 L 𝐶 𝐴 𝑓 = 3.49

100 L

Final Result: The highest possible conversion yields an exit concentration of CAf ≈ 3.49 mol/liter, corresponding to a final conversion
of 𝑋 𝐴 = 1 − (3.49/10) = 65.1%.

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Chapter 6 Reactor Design Strategy Muhammad Shabbir @2102113

Problem-Solving Guide: The Autocatalytic Reactor

Autocatalytic reactions represent a unique challenge in reactor design. Their non-monotonic rate profiles (starting slow, speeding up,
then slowing down) require a specific strategy that often combines different reactor types. This guide outlines the engineering thought
process required to deconstruct and solve such problems, using Levenspiel’s Problem 6.11 as a case study.

The Engineer’s Checklist for Reactor Design Problems

This checklist provides a systematic approach to move from a problem statement to a robust, optimized solution.

Step 1: Deconstruct the Problem Statement (The ”Knowns”)

Before writing any equations, extract and label every piece of information given. For Problem 6.11:
• Reaction Type: Autocatalytic, 𝐴 → 𝑅.

• Rate Law: −𝑟 𝐴 = 0.001𝐶 𝐴𝐶𝑅 [mol/(liter·s)].

• Phase Density: Liquid-phase is implied, meaning constant density.
• Feed Conditions: 𝐶 𝐴0 = 10 mol/L, 𝐶𝑅0 = 0 (pure A), 𝑣 = 1.5 L/s.

• Available Equipment: Four (4) Mixed Flow Reactors (MFRs), each with a volume 𝑉𝑖 = 100 L.
• Objective: Achieve the ”highest conversion possible,” which is equivalent to minimizing the final concentration, 𝐶 𝐴 𝑓 .

Step 2: Characterize the Kinetics (The ”Nature of the Beast”)

This is the most critical step. The type of kinetics dictates the entire design strategy.
▷ Is the rate a simple 𝑛𝑡 ℎ order? No, it is autocatalytic. This is a special case and immediately signals that a simple PFR or MFR
might not be optimal.
▷ What is the shape of the rate curve? The rate depends on both reactant (𝐶 𝐴) and product (𝐶𝑅 ). It starts at zero (since 𝐶𝑅0 = 0),
rises to a maximum, and then falls back to zero as 𝐶 𝐴 is depleted.
▷ Find the Maximum Rate Point: For a constant density system, the total concentration is constant: 𝐶 𝐴 + 𝐶𝑅 = 𝐶 𝐴0 = 10. We can
rewrite the rate law purely in terms of 𝐶 𝐴:
−𝑟 𝐴 = 𝑘𝐶 𝐴 (𝐶 𝐴0 − 𝐶 𝐴)
This is a parabola. To find the maximum rate, we take the derivative with respect to 𝐶 𝐴 and set it to zero:

𝑑 (−𝑟 𝐴) 𝐶 𝐴0
= 𝑘𝐶 𝐴0 − 2𝑘𝐶 𝐴 = 0 =⇒ 𝐶 𝐴 =
𝑑𝐶 𝐴 2
For this problem, the maximum rate occurs at 𝐶 𝐴 = 10/2 = 5 mol/L.
▷ Conceptual Takeaway: The reaction runs fastest when half the reactant has been converted. On a Levenspiel Plot (1/−𝑟 𝐴 vs. 𝐶 𝐴),
this corresponds to the minimum point (the ”valley”) of a U-shaped curve.

Step 3: Consult the ”Golden Rules” of Reactor Design

Connect the kinetic profile from Step 2 to the design principles in Levenspiel Chapter 6.
• Rule for normal 𝑛 > 0 reactions: The rate is always highest at the start. To get the smallest volume, use a PFR. If only MFRs are
available, put them all in series.
• Rule for Autocatalytic Reactions (Levenspiel Fig. 6.19): This is the special case that inverts the normal logic.

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Chapter 6 Reactor Design Strategy Muhammad Shabbir @2102113

– At low conversions (from 𝐶 𝐴 = 10 down to the max rate point at 𝐶 𝐴 = 5), the MFR is more efficient (requires a smaller
volume).
– At high conversions (from 𝐶 𝐴 = 5 down toward 𝐶 𝐴 = 0), the PFR is more efficient.

• The Optimal Theoretical Strategy: Use a single MFR to make the ”jump” from the feed concentration (𝐶 𝐴0 = 10) directly to
the maximum rate point (𝐶 𝐴 = 5). Then, use a PFR to finish the reaction.

Step 4: Adapt the ”Ideal” Strategy to the Available Equipment

The ideal strategy requires a PFR, but we only have four MFRs. We must adapt.
▷ Approximating a PFR: Levenspiel’s Fig. 6.5 demonstrates that as the number of MFRs in series increases (𝑁 → ∞), their combined
performance approaches that of a single PFR.
▷ The Adapted Strategy:

1. Use one or more MFRs in the first stage, sized to take the feed from 𝐶 𝐴0 = 10 to the optimal point at 𝐶 𝐴 = 5.
2. Use the remaining MFRs in series to act as an approximation of a PFR, achieving the highest possible final conversion.

Step 5: Perform the Calculations to Test Options

This is the final step where the strategy is translated into numbers.

1. Task 1: Size the first MFR stage to reach 𝐶 𝐴 = 5.

The MFR performance equation is 𝜏 = (𝐶 𝐴0 − 𝐶 𝐴,𝑒𝑥𝑖𝑡 )/(−𝑟 𝐴,𝑒𝑥𝑖𝑡 ). We want 𝐶 𝐴,𝑒𝑥𝑖𝑡 = 5. The rate at this point is −𝑟 𝐴 =
0.001(5) (10 − 5) = 0.025.
10 − 5
𝜏= = 200 s
0.025
What total volume is needed for this stage?

𝑉𝑠𝑡 𝑎𝑔𝑒1 = 𝑣 · 𝜏 = 1.5 L/s × 200 s = 300 Liters

2. Task 2: Match the required volume to available equipment.

How can we create a 300-Liter reactor from four 100-Liter reactors? By connecting three of them in parallel. This configuration
provides a total volume of 300 L to process the total flow rate of 1.5 L/s, perfectly achieving the goal of the first stage.
3. Task 3: Size the second stage with the remaining equipment.
We have one 100-Liter MFR left. This will be our second stage, placed in series. The feed to this reactor is the exit from the first
stage, so its inlet concentration is 𝐶 𝐴,𝑖𝑛 = 5. The space-time of this single reactor is:

𝑉 100 L
𝜏2 = = = 66.67 s
𝑣 1.5 L/s
Now, solve the MFR equation for the final concentration, 𝐶 𝐴 𝑓 :

𝐶 𝐴,𝑖𝑛 − 𝐶 𝐴 𝑓 5 − 𝐶𝐴 𝑓
𝜏2 = =⇒ 66.67 =
𝑘𝐶 𝐴 𝑓 (𝐶 𝐴0 − 𝐶 𝐴 𝑓 ) 0.001𝐶 𝐴 𝑓 (10 − 𝐶 𝐴 𝑓 )

Solving this quadratic equation yields the final answer: 𝐶 𝐴 𝑓 = 3.49 mol/L.
This logical progression, from characterization to ideal strategy to practical adaptation, is the key to solving complex reactor design
problems.

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Chapter 6 Design for Single Reactions Muhammad Shabbir @2102113

Detailed Solutions: Levenspiel Chapter 6

Problem 6.14: Optimizing PFR and MFR in Series

▷ Concept Focus: Applying the design rules for ordering reactors in series based on the reaction order. The goal is to maximize
production rate for a given total volume.
▷ Problem Context: Elementary liquid-phase reaction 𝐴+ 𝐵 → 𝑅 +𝑆. Since it’s elementary and equimolar, it behaves as a second-order
reaction: −𝑟 𝐴 = 𝑘𝐶 2𝐴. Existing PFR gives 𝑋 𝐴 = 0.96. A new MFR, 10 times the size of the PFR, is to be added in series.

Step 1: Determine the Best Arrangement of Reactors

The reaction is second-order (𝑛 = 2). For any reaction with an order greater than one (𝑛 > 1), the Levenspiel plot (1/−𝑟 𝐴 vs. 𝐶 𝐴 or 𝑋 𝐴)
is concave. According to the rules on Levenspiel page 135 (Fig. 6.12), to minimize the total volume (or maximize conversion for a fixed
volume), reactors should be ordered to keep the reactant concentration as high as possible.
• A PFR maintains a higher average concentration than an MFR for the same conversion range.
• Therefore, to keep the concentration high, the PFR should come first, followed by the MFR.

Step 2: Calculate the Initial PFR Performance

Let the existing PFR have volume 𝑉𝑃 . For a second-order reaction with no expansion:

𝑋𝐴 0.96
𝜏𝑃 𝐶 𝐴0 𝑘 = =⇒ (𝑘𝐶 𝐴0 𝜏𝑃 ) = = 24
1 − 𝑋𝐴 1 − 0.96

Step 3: Calculate the New Overall Production Rate

We have a total volume 𝑉𝑡𝑜𝑡 𝑎𝑙 = 𝑉𝑃 + 𝑉𝑀 = 𝑉𝑃 + 10𝑉𝑃 = 11𝑉𝑃 . Let the new, higher flow rate be 𝑣 ′𝑡𝑜𝑡 𝑎𝑙 .
• Stage 1 (PFR): The space-time in the PFR is now 𝜏𝑃′ = 𝑉𝑃 /𝑣 ′𝑡𝑜𝑡 𝑎𝑙 . The intermediate conversion 𝑋 𝐴1 is:

𝑋 𝐴1
𝑘𝐶 𝐴0 𝜏𝑃′ =
1 − 𝑋 𝐴1

• Stage 2 (MFR): The space-time is 𝜏𝑀

′ = 𝑉 /𝑣 ′ ′ ′
𝑀 𝑡𝑜𝑡 𝑎𝑙 = 10𝑉𝑃 /𝑣 𝑡𝑜𝑡 𝑎𝑙 = 10𝜏𝑃 . The final conversion is 𝑋 𝐴2 = 0.96.

′ 𝑋 𝐴2 − 𝑋 𝐴1 0.96 − 𝑋 𝐴1
𝑘𝐶 𝐴0 𝜏𝑀 = 2
=⇒ 10(𝑘𝐶 𝐴0 𝜏𝑃′ ) =
(1 − 𝑋 𝐴2 ) (1 − 0.96) 2

Substitute the PFR equation into the MFR equation:

 
𝑋 𝐴1 0.96 − 𝑋 𝐴1 𝑋 𝐴1
10 = =⇒ 0.016 = 0.96 − 𝑋 𝐴1
1 − 𝑋 𝐴1 0.0016 1 − 𝑋 𝐴1

Solving this quadratic equation yields the intermediate conversion 𝑋 𝐴1 = 0.8. Now, find the new value of the group (𝑘𝐶 𝐴0 𝜏𝑃′ ):

0.8
𝑘𝐶 𝐴0 𝜏𝑃′ = =4
1 − 0.8
The ratio of the old production rate to the new one is:

𝑣 ′𝑡𝑜𝑡 𝑎𝑙 ′
𝐹𝐴0 𝜏𝑃 (𝑘𝐶 𝐴0 𝜏𝑃 ) 24
= = ′ = = =6
𝑣 𝑡𝑜𝑡 𝑎𝑙 𝐹𝐴0 𝜏𝑃 (𝑘𝐶 𝐴0 𝜏𝑃′ ) 4

Final Answer: The PFR should come first. The production rate could be increased by a factor of 6.

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Chapter 6 Design for Single Reactions Muhammad Shabbir @2102113

Problem 6.15: Deducing Kinetics from MFRs in Series

▷ Concept Focus: Using performance data from a series of MFRs to determine the unknown reaction order and rate constant.
▷ Problem Context: Aqueous decomposition of A in two MFRs, with 𝑉2 = 2𝑉1 . Feed is 𝐶 𝐴0 = 1 mol/L. Performance: 𝜏1 = 96s,
𝐶 𝐴1 = 0.5 mol/L, 𝐶 𝐴2 = 0.25 mol/L.

Step 1: Calculate the Rate in the First Reactor

For the first MFR, we can directly calculate the rate of reaction at 𝐶 𝐴1 = 0.5 mol/L:
𝐶 𝐴0 − 𝐶 𝐴1 1 − 0.5 0.5
−𝑟 𝐴1 = = = = 0.005208 mol/(L · s)
𝜏1 96 96

Step 2: Calculate the Rate in the Second Reactor

The space-time in the second reactor is 𝜏2 = 𝑉2 /𝑣 = (2𝑉1 )/𝑣 = 2𝜏1 = 2 × 96 = 192 s. The rate at the exit of the second reactor
(𝐶 𝐴2 = 0.25 mol/L) is:
𝐶 𝐴1 − 𝐶 𝐴2 0.5 − 0.25 0.25
−𝑟 𝐴2 = = = = 0.001302 mol/(L · s)
𝜏2 192 192

Step 3: Determine the Reaction Order and Rate Constant

We now have two data points of rate vs. concentration. We assume a rate law of −𝑟 𝐴 = 𝑘𝐶 𝐴𝑛 . Taking the ratio:
 𝑛  𝑛
−𝑟 𝐴1 𝐶 𝐴1 0.005208 0.5
= =⇒ =
−𝑟 𝐴2 𝐶 𝐴2 0.001302 0.25
4 = (2) 𝑛 =⇒ 𝑛 = 2
The reaction is second-order. Now, we can calculate the rate constant 𝑘 using either point:
−𝑟 𝐴1 0.005208 0.005208
𝑘= = = = 0.02083 L/(mol · s)
𝐶 2𝐴1 (0.5) 2 0.25

Final Kinetic Equation

The kinetic equation for the decomposition is:  
mol
−rA = 0.0208 C2A
L·s

Problem 6.17: MFR-PFR Series with a Pseudo-First-Order Trick

▷ Concept Focus: Calculating mixed feed concentrations, recognizing when a bimolecular reaction degrades to pseudo-first-order, and
solving a series reactor system (MFR → PFR) using grouped constants.
▷ Problem Context: Elementary reaction 𝐴 + 𝐵 → 𝑅 + 𝑆. Equal volumes of two streams are mixed into a 4-L MFR, followed by a
16-L PFR. Feed stream A is 0.020 mol/L; Feed stream B is 1.400 mol/L. In the MFR, 𝐶𝑅1 = 0.002 mol/L.

Step 1: Calculate Mixed Feed and Recognize the Kinetic Trick

Because the two streams have equal volumetric flow rates (𝑣 1 = 𝑣 2 = 𝑣), the total flow rate entering the MFR is 𝑣 𝑡𝑜𝑡 = 2𝑣. The
concentration of each species is halved upon mixing:
• 𝐶 𝐴0 = 0.020
2 = 0.010 mol/L

• 𝐶 𝐵0 = 1.400
2 = 0.700 mol/L
The Crucial Observation: The concentration of B is 70 times larger than A. Even if 100% of A reacts, 𝐶 𝐵 will only drop from 0.700
to 0.690. Therefore, the concentration of B is essentially constant (𝐶 𝐵 ≈ 𝐶 𝐵0 ). The elementary second-order rate law (−𝑟 𝐴 = 𝑘𝐶 𝐴𝐶 𝐵 )
simplifies to a pseudo-first-order rate law:
−𝑟 𝐴 ≈ (𝑘𝐶 𝐵0 )𝐶 𝐴 = k′ CA

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Chapter 6 Design for Single Reactions Muhammad Shabbir @2102113

Step 2: Analyze the First Stage (Mixed Flow Reactor)

* Volume 𝑉𝑀 = 4 L. * Exit concentration of product R is 𝐶𝑅1 = 0.002 mol/L. Since 1 mole of A produces 1 mole of R, the amount of A
reacted is 0.002 mol/L. The exit concentration of A from the MFR is:

𝐶 𝐴1 = 𝐶 𝐴0 − 𝐶𝑅1 = 0.010 − 0.002 = 0.008 mol/L

Using the MFR performance equation for first-order kinetics:

𝐶 𝐴0 − 𝐶 𝐴1 𝐶 𝐴0 − 𝐶 𝐴1
𝜏𝑀 = =
−𝑟 𝐴1 𝑘 ′ 𝐶 𝐴1
We don’t know 𝑘 ′ or the volumetric flow rate, but we can group the terms to find a system constant (𝑘 ′ 𝜏𝑀 ):
0.010 − 0.008 0.002
𝑘 ′ 𝜏𝑀 = = = 0.25
0.008 0.008

Step 3: Analyze the Second Stage (Plug Flow Reactor)

* Volume 𝑉𝑃 = 16 L. * Notice the relationship between the volumes: 𝑉𝑃 = 4 × 𝑉𝑀 . Because the volumetric flow rate 𝑣 𝑡𝑜𝑡 is constant
through both reactors, the space-time in the PFR is exactly 4 times the space-time in the MFR (𝜏𝑃 = 4𝜏𝑀 ). Therefore, our grouped
kinetic parameter for the PFR is:
𝑘 ′ 𝜏𝑃 = 4 × (𝑘 ′ 𝜏𝑀 ) = 4 × 0.25 = 1.0
Now, apply the PFR performance equation for a first-order reaction, integrating from the PFR inlet (𝐶 𝐴1 = 0.008) to the final exit (𝐶 𝐴2 ):
∫ 𝐶 𝐴1  
𝑑𝐶 𝐴 ′ 𝐶 𝐴1
𝜏𝑃 = ′
=⇒ 𝑘 𝜏𝑃 = ln
𝐶 𝐴2 𝑘 𝐶 𝐴 𝐶 𝐴2

Substitute the known values:  

0.008 0.008
1.0 = ln =⇒ 𝑒 1.0 =
𝐶 𝐴2 𝐶 𝐴2
0.008
𝐶 𝐴2 = = 0.00294 mol/L
2.718

Step 4: Final Output Calculations

The question asks for the final concentration of R and the overall fraction of A converted. * Final Concentration of R:

𝐶𝑅2 = 𝐶 𝐴0 − 𝐶 𝐴2 = 0.010 − 0.00294 = 0.00706 mol/L

* Overall Fractional Conversion:

𝐶 𝐴0 − 𝐶 𝐴2 0.010 − 0.00294
𝑋 𝐴,𝑡𝑜𝑡 𝑎𝑙 = = = 0.706 (or 70.6%)
𝐶 𝐴0 0.010

Problem 6.18: The Penalty of Recycle on Second-Order Reactions

▷ Concept Focus: Integrating the general recycle reactor performance equation for second-order kinetics, finding the system capacity,
and comparing it to pure plug flow.
▷ Problem Context: Elementary liquid reaction 2𝐴 → 2𝑅 (which simplifies to 𝐴 → 𝑅 with second-order kinetics, −𝑟 𝐴 = 𝑘𝐶 2𝐴).
Current operation is a PFR with recycle ratio 𝑅 = 1, yielding 𝑋 𝐴 = 2/3. What happens if 𝑅 = 0?

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Chapter 6 Design for Single Reactions Muhammad Shabbir @2102113

Step 1: Evaluate Current System Capacity (With Recycle)

The general performance equation for a recycle reactor in terms of conversion (Levenspiel Eq. 21, page 137) is:
∫ 𝑋𝐴 𝑓
𝑉 𝑑𝑋 𝐴
= (𝑅 + 1) 𝑅𝑋
𝐹𝐴0 𝐴 𝑓 −𝑟
𝑅+1
𝐴

For a constant-density, second-order reaction (−𝑟 𝐴 = 𝑘𝐶 2𝐴0 (1 − 𝑋 𝐴) 2 ):

∫ 𝑋𝐴 𝑓   𝑋𝐴 𝑓
𝑑𝑋 𝐴 1
𝜏 = 𝐶 𝐴0 (𝑅 + 1) =⇒ 𝑘𝜏𝐶 𝐴0 = (𝑅 + 1)
𝑅𝑋 𝐴 𝑓
𝑅+1
𝑘𝐶 2𝐴0 (1 − 𝑋 𝐴) 2 1 − 𝑋 𝐴 𝑅𝑋 𝐴 𝑓
𝑅+1

1
Evaluate the limits. The upper limit is 1−𝑋 𝐴 𝑓 . The lower limit requires a bit of algebra:

1 1 𝑅+1
Lower Limit = = =
1−
𝑅𝑋 𝐴 𝑓 𝑅+1−𝑅𝑋 𝐴 𝑓 𝑅 + 1 − 𝑅𝑋 𝐴 𝑓
𝑅+1 𝑅+1

The full integrated equation is:  

1 𝑅+1
𝑘𝜏𝐶 𝐴0 = (𝑅 + 1) −
1 − 𝑋𝐴 𝑓 𝑅 + 1 − 𝑅𝑋 𝐴 𝑓
Now, substitute the current operating conditions (𝑋 𝐴 𝑓 = 2/3 and 𝑅 = 1):
 
1 1+1
𝑘𝜏𝐶 𝐴0 = (1 + 1) −
1 − 2/3 1 + 1 − 1(2/3)
     
1 2 2 6
𝑘𝜏𝐶 𝐴0 = 2 − =2 3− =2 3− = 2(3 − 1.5)
1/3 2 − 2/3 4/3 4
k𝜏CA0 = 3
This dimensionless group (𝑘𝜏𝐶 𝐴0 = 3) represents the physical capacity of the existing reactor system. It will remain unchanged when
the recycle is shut off.

Step 2: Calculate New Conversion (Without Recycle)

If the recycle stream is shut off, 𝑅 = 0, and the reactor operates as a pure Plug Flow Reactor. The performance equation for a pure PFR
with second-order kinetics is simply the upper bound of the integral evaluated from 0:
𝑋𝐴
𝑘𝜏𝐶 𝐴0 =
1 − 𝑋𝐴
Substitute our known system capacity:
𝑋𝐴
3=
1 − 𝑋𝐴
3 − 3𝑋 𝐴 = 𝑋 𝐴 =⇒ 4𝑋 𝐴 = 3
3
𝑋 𝐴 = = 0.75
4
Final Answer & Conclusion: The conversion will increase to 75%. Why did conversion go up? For any reaction with an order
greater than zero, backmixing (mixing product with fresh feed) lowers the average reactant concentration inside the vessel, which
depresses the reaction rate. Shutting off the recycle stream restores the reactor to ideal plug flow, maintaining the highest possible
concentration profile and thereby increasing overall conversion.

Problem 6.19: Autocatalytic Reactor Optimization (Analytical)

▷ Concept Focus: Sizing PFRs, MFRs, and optimal combinations for an autocatalytic reaction using analytical integration.
▷ Problem Context: Reaction 𝐴 + 𝑅 → 𝑅 + 𝑅. Total concentration is constant 𝐶0 = 𝐶 𝐴 + 𝐶𝑅 = 1 mol/L. Feed is 99% A (𝐶 𝐴0 = 0.99
mol/L). Target is 10% A (𝐶 𝐴 𝑓 = 0.1 mol/L). Rate constant 𝑘 = 1 L/(mol·min).

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Chapter 6 Design for Single Reactions Muhammad Shabbir @2102113

Kinetic Analysis
The rate law is elementary: −𝑟 𝐴 = 𝑘𝐶 𝐴𝐶𝑅 . Since 𝐶𝑅 = 𝐶0 − 𝐶 𝐴 = 1 − 𝐶 𝐴:

−𝑟 𝐴 = 𝑘𝐶 𝐴 (1 − 𝐶 𝐴) = (1)𝐶 𝐴 (1 − 𝐶 𝐴)

The maximum rate occurs at 𝐶 𝐴 = 𝐶0 /2 = 0.5 mol/L.

Part (a): Plug Flow Reactor (PFR)

For a PFR, we integrate the performance equation from 𝐶 𝐴0 to 𝐶 𝐴 𝑓 :
∫ 𝐶 𝐴0 ∫ 0.99
𝑑𝐶 𝐴 𝑑𝐶 𝐴
𝜏𝑃 = =
𝐶𝐴 𝑓 −𝑟 𝐴 0.1 𝐶 𝐴 (1 − 𝐶 𝐴)

1 1 1
Using partial fractions: 𝐶 𝐴 (1−𝐶 𝐴 ) = 𝐶𝐴 + 1−𝐶 𝐴 .

    0.99
𝐶𝐴
𝜏𝑃 = [ln(𝐶 𝐴) − ln(1 − 𝐶 𝐴)] 0.99
0.1 = ln
1 − 𝐶𝐴 0.1
   
0.99 0.1
𝜏𝑃 = ln − ln = ln(99) − ln(1/9) = ln(99 × 9) = ln(891)
0.01 0.9
𝜏𝑃 = 6.79 min

Part (b): Mixed Flow Reactor (MFR)

For an MFR, the space-time is based entirely on the exit rate (at 𝐶 𝐴 = 0.1):
𝐶 𝐴0 − 𝐶 𝐴 𝑓 𝐶 𝐴0 − 𝐶 𝐴 𝑓
𝜏𝑀 = =
−𝑟 𝐴,𝑒𝑥𝑖𝑡 𝐶 𝐴 𝑓 (1 − 𝐶 𝐴 𝑓 )

0.99 − 0.1 0.89 0.89

𝜏𝑀 = = = = 9.89 min
0.1(1 − 0.1) 0.1(0.9) 0.09

Part (c): Minimum-Size Setup Without Recycle

For an autocatalytic reaction, the optimal (minimum volume) setup without recycle is a Mixed Flow Reactor followed by a Plug Flow
Reactor. The MFR should operate exactly at the point of maximum reaction rate to make the ”jump” from the slow initial conditions.
As determined, the maximum rate is at 𝐶 𝐴1 = 0.5 mol/L.
1. MFR (Stage 1): Feed 𝐶 𝐴0 = 0.99, Exit 𝐶 𝐴1 = 0.5.
𝐶 𝐴0 − 𝐶 𝐴1 0.99 − 0.5 0.49
𝜏𝑀1 = = = = 1.96 min
𝐶 𝐴1 (1 − 𝐶 𝐴1 ) 0.5(1 − 0.5) 0.25
2. PFR (Stage 2): Feed 𝐶 𝐴1 = 0.5, Exit 𝐶 𝐴 𝑓 = 0.1.
∫ 0.5     0.5
𝑑𝐶 𝐴 𝐶𝐴
𝜏𝑃2 = = ln
0.1 𝐶 𝐴 (1 − 𝐶 𝐴) 1 − 𝐶 𝐴 0.1
  
0.5 0.1
𝜏𝑃2 = ln − ln = ln(1) − ln(1/9) = 0 − (−2.197) = 2.197 min
0.5 0.9
Total Minimum Time: 𝜏𝑡𝑜𝑡 𝑎𝑙 = 1.96 + 2.197 = 4.16 min. Note: This is significantly faster than either a pure PFR (6.79 min) or a
pure MFR (9.89 min).

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Chapter 6 Design for Single Reactions Muhammad Shabbir @2102113

Problem 6.20: Graphical Optimization from Raw Data

▷ Concept Focus: Finding the absolute minimum reactor volume by evaluating Levenspiel plots for unusual kinetic curves (rates that
pass through a minimum).
▷ Problem Context: Aqueous decomposition 𝐴 → 𝑅. Feed 𝐶 𝐴0 = 100. Target is 90% conversion (𝐶 𝐴 𝑓 = 10). We must find the
optimal combination of ideal reactors using raw MFR data.

Step 1: Extract Kinetic Data

From the MFR performance equation, 𝜏 = (𝐶 𝐴0 − 𝐶 𝐴)/(−𝑟 𝐴), we extract the reciprocal rate 1/−𝑟 𝐴 = 𝜏/(𝐶 𝐴0 − 𝐶 𝐴) for each data point.

𝜏 (s) 𝐶 𝐴0 𝐶𝐴 Rate −𝑟 𝐴 1/(−𝑟 𝐴) (s·L/mol)

14 200 100 (200 − 100)/14 = 7.14 0.14
25 190 90 (190 − 90)/25 = 4.00 0.25
29 180 80 (180 − 80)/29 = 3.45 0.29
30 170 70 (170 − 70)/30 = 3.33 0.30
29 160 60 (160 − 60)/29 = 3.45 0.29
27 150 50 (150 − 50)/27 = 3.70 0.27
24 140 40 (140 − 40)/24 = 4.17 0.24
19 130 30 (130 − 30)/19 = 5.26 0.19
15 120 20 (120 − 20)/15 = 6.67 0.15
12 110 10 (110 − 10)/12 = 8.33 0.12
20 101 1 (101 − 1)/20 = 5.00 0.20

Step 2: Construct and Analyze the Levenspiel Plot

We plot the 1/−𝑟 𝐴 values against 𝐶 𝐴. Notice the shape: the reciprocal rate starts low at 𝐶 𝐴 = 100, rises to a maximum of 0.30 at
𝐶 𝐴 = 70, and then falls back down to a minimum of 0.12 at 𝐶 𝐴 = 10.
This forms an inverted U-shape (a ”hill”). This indicates that the reaction rate actually slows down as the reaction starts, reaches a
minimum speed around 𝐶 𝐴 = 70, and then speeds up dramatically as it approaches 𝐶 𝐴 = 10. This is the exact opposite of an autocatalytic
reaction.

Levenspiel Plot: Optimization for ”Hill” Kinetics

0.3
1/(−𝑟 𝐴) (s·L/mol)

0.2

0.1
PFR Area
MFR Area
Kinetic Path
0
0 10 20 30 40 50 60 70 80 90 100 110
Concentration 𝐶 𝐴 (mol/L)

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Chapter 6 Design for Single Reactions Muhammad Shabbir @2102113

Step 3: Determine the Best Setup

We must find the reactor configuration that yields the minimum area between 𝐶 𝐴0 = 100 and 𝐶 𝐴 𝑓 = 10.
• Single PFR: The volume is the red area integrated under the ”hill”. Because the curve bulges upward, the PFR is forced to
operate through the extremely slow regions (high 1/−𝑟 𝐴) near 𝐶 𝐴 = 70. Using the trapezoidal rule on the data points, the area is
𝜏𝑃 ≈ 22 seconds.
• Single MFR: An MFR operates entirely at the exit condition. For a single MFR operating from 𝐶 𝐴0 = 100 to 𝐶 𝐴,𝑒𝑥𝑖𝑡 = 10, the
volume is the blue rectangle. Because the reciprocal rate at the exit (0.12) is the absolute lowest point in the entire range, the
rectangle slides entirely *underneath* the hill.
 
1
𝜏𝑀 = (Height) × (Width) = × (𝐶 𝐴0 − 𝐶 𝐴 𝑓 )
−𝑟 𝐴 𝐶 𝐴=10

𝜏𝑀 = 0.12 × (100 − 10) = 0.12 × 90 = 10.8 seconds

Conclusion on Combinations: Since the single MFR operates entirely at the fastest point in our required range (1/−𝑟 𝐴 = 0.12), any
attempt to add a PFR or an intermediate MFR would force a portion of the reaction to occur at a slower rate (higher up the hill on the
y-axis), thereby increasing the total volume.
Final Answer: The minimum space-time is achieved using a single Mixed Flow Reactor. The minimum time is 𝜏min = 10.8 sec.

Problem 6.21: The Penalty of Recycle in First-Order Kinetics

▷ Concept Focus: Evaluating the recycle performance equation and understanding the definition of the recycle ratio (𝑅).
▷ Problem Context: An irreversible first-order liquid reaction (−𝑟 𝐴 = 𝑘𝐶 𝐴) currently achieves 90% conversion in a PFR (𝐶 𝐴0 = 10
mol/L). We are converting it to a recycle reactor while keeping the reactor volume (𝑉) and fresh feed throughput (𝑣 0 ) identical.

Step 1: Determine the Current System Capacity (𝑘𝜏)

Before introducing recycle, the system is a simple Plug Flow Reactor. For a first-order, constant-density reaction, the performance
equation is:  
1
𝑘𝜏𝑝 = ln = − ln(1 − 𝑋 𝐴)
1 − 𝑋𝐴
Given 𝑋 𝐴 = 0.90:
𝑘𝜏𝑝 = − ln(1 − 0.90) = − ln(0.10) = 2.3026
Since the volume and fresh feed throughput are unchanged, the global space-time 𝜏 = 𝑉/𝑣 0 remains strictly constant. Therefore, the
parameter group 𝑘𝜏 = 2.3026 applies to the new setup as well.

Step 2: Determine the Recycle Ratio (𝑅)

The problem states: ”two-thirds of the stream leaving the reactor is recycled”. Levenspiel defines the recycle ratio 𝑅 strictly as:

volume of fluid returned to entrance

𝑅=
volume leaving the system

Let 𝑣 𝑒𝑥𝑖𝑡 be the total volume leaving the reactor vessel. * Volume returned = 23 𝑣 𝑒𝑥𝑖𝑡 * Volume leaving system (product) = 𝑣 𝑒𝑥𝑖𝑡 − 32 𝑣 𝑒𝑥𝑖𝑡 =
1
3 𝑣 𝑒𝑥𝑖𝑡
(2/3)𝑣 𝑒𝑥𝑖𝑡
𝑅= =2
(1/3)𝑣 𝑒𝑥𝑖𝑡

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Chapter 6 Design for Single Reactions Muhammad Shabbir @2102113

Step 3: Apply the Recycle Performance Equation

For a first-order reaction with constant density, the integrated recycle equation (Levenspiel Eq. 23, page 138) is:
 
𝐶 𝐴0 + 𝑅𝐶 𝐴 𝑓
𝑘𝜏 = (𝑅 + 1) ln
(𝑅 + 1)𝐶 𝐴 𝑓
Substitute the known values (𝑘𝜏 = 2.3026, 𝑅 = 2, 𝐶 𝐴0 = 10 mol/L):
 
10 + 2𝐶 𝐴 𝑓
2.3026 = (2 + 1) ln
(2 + 1)𝐶 𝐴 𝑓
 
10 + 2𝐶 𝐴 𝑓
2.3026 = 3 ln
3𝐶 𝐴 𝑓
Divide by 3:  
10 + 2𝐶 𝐴 𝑓
0.7675 = ln
3𝐶 𝐴 𝑓
Exponentiate both sides (𝑒 0.7675 ≈ 2.1544):
10 + 2𝐶 𝐴 𝑓
2.1544 =
3𝐶 𝐴 𝑓
2.1544 × 3𝐶 𝐴 𝑓 = 10 + 2𝐶 𝐴 𝑓 =⇒ 6.463𝐶 𝐴 𝑓 = 10 + 2𝐶 𝐴 𝑓
10
4.463𝐶 𝐴 𝑓 = 10 =⇒ 𝐶 𝐴 𝑓 = = 2.24 mol/L
4.463
Final Answer & Conclusion: The concentration of reactant leaving the system rises from 1.0 mol/L (90% conversion) to 2.24 mol/L
(77.6% conversion). For a normal 𝑛𝑡 ℎ -order reaction (𝑛 > 0), backmixing product into the feed lowers the average concentration in the
reactor, thereby lowering the reaction rate and penalizing overall conversion.

Problem 6.22: Optimizing Batch Reactor Daily Output

▷ Concept Focus: Maximizing the overall production rate by balancing the time spent reacting versus the ”dead time” (downtime)
spent filling and emptying the reactor.
▷ Problem Context: A second-order batch reaction (−𝑟 𝐴 = 𝑘𝐶 2𝐴) with 𝑘 = 0.005 L/(mol·min) and 𝐶 𝐴0 = 1 mol/L. Downtime is
𝑡 𝑑 = 18 min per batch.

Step 1: Define the Objective Function (Production Rate)

We wish to maximize the daily output of product R. Since volume (𝑉) is fixed, maximizing total output is equivalent to maximizing the
average rate of processing A over the entire cycle.
Moles of A converted 𝑉 (𝐶 𝐴0 − 𝐶 𝐴)
Production Rate (Pr) = =
Total cycle time 𝑡 + 𝑡𝑑
Because 𝑉 and 𝐶 𝐴0 are constants, maximizing the overall production reduces to finding the maximum of:
𝑋𝐴
𝑓 (𝑋 𝐴) =
𝑡 + 𝑡𝑑
where 𝑋 𝐴 is conversion, 𝑡 is reaction time, and 𝑡 𝑑 is the 18-minute downtime.

Step 2: Relate Reaction Time (𝑡) to Conversion (𝑋 𝐴)

For a second-order reaction (−𝑟 𝐴 = 𝑘𝐶 2𝐴) in a constant-volume batch reactor:
   
1 1 1 1 𝑋𝐴
𝑡= − =
𝑘 𝐶 𝐴 𝐶 𝐴0 𝑘𝐶 𝐴0 1 − 𝑋 𝐴
Substituting 𝑘 = 0.005 and 𝐶 𝐴0 = 1:    
1 𝑋𝐴 𝑋𝐴
𝑡= = 200
(0.005) (1) 1 − 𝑋 𝐴 1 − 𝑋𝐴

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Chapter 6 Design for Single Reactions Muhammad Shabbir @2102113

Step 3: Construct and Differentiate the Objective Function

Substitute 𝑡 into our objective function:
𝑋𝐴
𝑓 (𝑋 𝐴) =  
𝑋𝐴
200 1−𝑋 𝐴 + 18

Multiply top and bottom by (1 − 𝑋 𝐴) to clear the complex fraction:

𝑋 𝐴 (1 − 𝑋 𝐴) 𝑋 𝐴 − 𝑋 𝐴2
𝑓 (𝑋 𝐴) = =
200𝑋 𝐴 + 18(1 − 𝑋 𝐴) 182𝑋 𝐴 + 18
 
𝑢′ 𝑣−𝑢𝑣 ′
To find the maximum production, we take the derivative with respect to 𝑋 𝐴 and set it to zero. Using the quotient rule 𝑣2
= 0 =⇒ 𝑢 ′ 𝑣 = 𝑢𝑣 ′ :

𝑢 = 𝑋 𝐴 − 𝑋 𝐴2 =⇒ 𝑢 ′ = 1 − 2𝑋 𝐴
𝑣 = 182𝑋 𝐴 + 18 =⇒ 𝑣 ′ = 182

(1 − 2𝑋 𝐴) (182𝑋 𝐴 + 18) = (𝑋 𝐴 − 𝑋 𝐴2 ) (182)

Expand both sides:
182𝑋 𝐴 + 18 − 364𝑋 𝐴2 − 36𝑋 𝐴 = 182𝑋 𝐴 − 182𝑋 𝐴2
Cancel 182𝑋 𝐴 from both sides and group terms:

18 − 364𝑋 𝐴2 − 36𝑋 𝐴 = −182𝑋 𝐴2

182𝑋 𝐴2 + 36𝑋 𝐴 − 18 = 0
Divide the entire equation by 2 to simplify:
91𝑋 𝐴2 + 18𝑋 𝐴 − 9 = 0

Step 4: Solve for Optimal Conversion and Time

Use the quadratic formula to solve for 𝑋 𝐴:
√︁ √ √
−18 ± 182 − 4(91) (−9) −18 ± 324 + 3276 −18 ± 3600
𝑋𝐴 = = =
2(91) 182 182
−18 ± 60
𝑋𝐴 =
182
Since conversion must be positive, we take the positive root:
42 21 3
𝑋𝐴 = = = ≈ 0.2307 (or 23.1%)
182 91 13
Finally, calculate the required reaction time 𝑡 for this conversion:
     
3/13 3/13 3
𝑡 = 200 = 200 = 200 = 60 minutes
1 − 3/13 10/13 10

Final Answer & Conclusion: To maximize daily output, you should run the reactor to only 23.1% conversion, which requires a
reaction time of 60 minutes per batch. Pushing the reaction further wastes time because the second-order rate drops precipitously as
reactants are consumed; the time spent waiting for the last few drops of product isn’t worth the delay in starting the next, fast batch.

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Optimal Design for Trambouze Reactions Muhammad Shabbir @2102113

Detailed Solutions: The Trambouze Reactions

This classic problem (adapted from Fogler’s Elements of Chemical Reaction Engineering) requires simultaneous optimization of reactor
type (via concentration control) and operating temperature to maximize the selectivity of an intermediate-order desired product against
zero-order and second-order side products.

Problem: Maximizing Desired Product B

▷ Concept Focus: Differentiating instantaneous selectivity (𝑆 𝐵/𝑋𝑌 ), calculating optimal reactor concentrations using calculus, and
utilizing Arrhenius activation energies to determine optimal temperature bounds.
▷ Problem Context: Gas-phase decomposition of A into three products. B is desired. X and Y are undesired.
𝑘1
𝐴 −→ 𝑋 (𝑟 𝑋 = 𝑘 1 ) [Zero Order] 𝑘 1 = 0.0001 M/s
𝑘2
𝐴 −→ 𝐵 (𝑟 𝐵 = 𝑘 2 𝐶 𝐴) [First Order] 𝑘 2 = 0.0015 s−1
𝑘3
𝐴 −→ 𝑌 (𝑟𝑌 = 𝑘 3 𝐶 2𝐴) [Second Order] 𝑘 3 = 0.0080 M−1 s−1

Constants are given at 𝑇 = 300 K. Activation energies: 𝐸 1 = 10, 𝐸 2 = 15, 𝐸 3 = 20 (all in kcal/mol). Feed: 𝐶 𝐴0 = 0.4 M, 𝑣 = 2.0
dm3 /s.

Part (a): Optimal Conditions (Reactor Type, Conc., Temp.)

1. Optimize Concentration (Reactor Type) To maximize the formation of B relative to X and Y, we define the instantaneous selectivity
parameter 𝑆 𝐵/𝑋𝑌 :
𝑟𝐵 𝑘 2𝐶 𝐴
𝑆 𝐵/𝑋𝑌 = =
𝑟 𝑋 + 𝑟𝑌 𝑘 1 + 𝑘 3 𝐶 2𝐴
To find the concentration of A that maximizes this selectivity, we take the derivative with respect to 𝐶 𝐴 and set it to zero. Using the
quotient rule:
𝑑 (𝑆 𝐵/𝑋𝑌 ) 𝑘 2 (𝑘 1 + 𝑘 3 𝐶 2𝐴) − (𝑘 2 𝐶 𝐴) (2𝑘 3 𝐶 𝐴)
= =0
𝑑𝐶 𝐴 (𝑘 1 + 𝑘 3 𝐶 2𝐴) 2
The numerator must equal zero:
𝑘 1 𝑘 2 + 𝑘 2 𝑘 3 𝐶 2𝐴 − 2𝑘 2 𝑘 3 𝐶 2𝐴 = 0 =⇒ 𝑘 1 𝑘 2 − 𝑘 2 𝑘 3 𝐶 2𝐴 = 0
Dividing by 𝑘 2 : √︂
𝑘1
𝑘 1 = 𝑘 3 𝐶 2𝐴 =⇒ 𝐶 ∗𝐴 =
𝑘3
This is a profound result: the optimal concentration is completely independent of the rate of the desired reaction (𝑘 2 ) and depends only
on the ratio of the competing side reactions. Substitute the given values at 300 K:
√︂
∗ 0.0001 √
𝐶𝐴 = = 0.0125 = 0.1118 M
0.008
Because the maximum selectivity occurs at a specific, fixed concentration (0.1118 M) rather than at the highest or lowest possible
concentration, the best reactor is a Continuous Stirred Tank Reactor (CSTR). A CSTR allows the entire reaction to operate exactly at
this optimal ”sweet spot.”
2. Optimize Temperature We now substitute 𝐶 ∗𝐴 back into the selectivity equation to find the maximum theoretical selectivity
(𝑆 𝑚𝑎𝑥 ): √︁ √︁ √︁
𝑘 2 𝑘 1 /𝑘 3 𝑘 2 𝑘 1 /𝑘 3 𝑘 2 𝑘 1 /𝑘 3 𝑘2
𝑆 𝑚𝑎𝑥 = = = = √
𝑘1 + 𝑘1
√︁
𝑘 1 + 𝑘 3 ( 𝑘 1 /𝑘 3 ) 2 2𝑘 1 2 𝑘1 𝑘3

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Optimal Design for Trambouze Reactions Muhammad Shabbir @2102113

To determine how temperature affects 𝑆 𝑚𝑎𝑥 , substitute the Arrhenius forms (𝑘 𝑖 = 𝐴𝑖 𝑒 −𝐸𝑖 /𝑅𝑇 ) for the constants:

𝐴2 𝑒 −𝐸2 /𝑅𝑇 𝐴2 𝑒 −𝐸2 /𝑅𝑇

𝑆 𝑚𝑎𝑥 = √︁ = √ √
2 𝐴1 𝑒 −𝐸1 /𝑅𝑇 · 𝐴3 𝑒 −𝐸3 /𝑅𝑇 2 𝐴1 𝐴3 𝑒 − (𝐸1 +𝐸3 )/𝑅𝑇

−𝐸 2 + 𝐸1 +𝐸
" #
𝑒 −𝐸2 /𝑅𝑇 3
   
𝐴2 𝐴2 2
𝑆 𝑚𝑎𝑥 = √ = √ exp
2 𝐴1 𝐴3 𝑒 − (𝐸1 +𝐸3 )/2𝑅𝑇 2 𝐴1 𝐴3 𝑅𝑇
Let’s evaluate the numerator of the exponential term using the given activation energies (𝐸 1 = 10, 𝐸 2 = 15, 𝐸 3 = 20):
𝐸1 + 𝐸3 10 + 20
−𝐸 2 + = −15 + = −15 + 15 = 0
2 2
Because the exponential term evaluates to 𝑒 0 = 1, the maximum selectivity is completely independent of temperature. Therefore, you
can run the reaction at any reasonable temperature without affecting the maximum√︁achievable selectivity, provided you adjust the CSTR
space-time to maintain the exit concentration at the temperature-dependent 𝐶 ∗𝐴 = 𝑘 1 (𝑇)/𝑘 3 (𝑇).

Part (b): Increasing Conversion While Maintaining Selectivity

A single CSTR operating at 𝐶 𝐴 = 0.1118 M achieves a conversion of:
0.4 − 0.1118
𝑋= = 72%
0.4
If higher conversion of B is desired without destroying the selectivity, a single large PFR cannot be used because it forces the concentration
through highly unselective regions (𝐶 𝐴 → 0 where reaction 1 dominates).
The best strategy to increase conversion while keeping selectivity relatively high is to use a series of small CSTRs, or a PFR with
side-stream injection (a distributed feed). By feeding fresh A slowly along the length of a tubular reactor, or staging it through multiple
CSTRs, the local concentration of A can be ”artificially” maintained near the optimal value of 𝐶 𝐴 ≈ 0.11 M for a much longer overall
residence time, thereby increasing overall conversion while suppressing the extreme high- and low-concentration side reactions.

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Chapter 7 Design for Parallel Reactions Muhammad Shabbir @2102113

Detailed Solutions: Levenspiel Chapter 7

This chapter shifts focus from single reactions to multiple parallel reactions. The core engineering objective here is not just to maximize
conversion, but to maximize selectivity—tuning the reactor configuration and concentrations to favor the desired product over unwanted
side products.

Problem: Maximizing Desired Product Distribution in Parallel Reactions

▷ Concept Focus: Deriving the instantaneous fractional yield (𝜑) curve, and using it to analytically determine the best ideal reactor (or
combination of reactors) to maximize a specific product.
▷ Problem Context: Reactant A decomposes via three parallel pathways. S is the desired product.

𝐴→𝑅 𝑟𝑅 = 1 (Zero Order)

𝐴→𝑆 𝑟 𝑆 = 2𝐶 𝐴 (First Order, Desired)
𝐴→𝑇 𝑟𝑇 = 𝐶 2𝐴 (Second Order)

The feed concentration is 𝐶 𝐴0 = 2 mol/L. We must find the maximum expected 𝐶𝑆 under various reactor setups.

Pre-Calculation: The Instantaneous Fractional Yield (𝜑 𝑆 )

Before evaluating specific reactors, we must determine how the yield of S changes with the concentration of A. The total rate of
disappearance of A is the sum of all three pathways:

−𝑟 𝐴 = 𝑟 𝑅 + 𝑟 𝑆 + 𝑟 𝑇 = 1 + 2𝐶 𝐴 + 𝐶 2𝐴 = (1 + 𝐶 𝐴) 2

The instantaneous fractional yield of S (𝜑 𝑆 ) is the rate of formation of S divided by the total rate of disappearance of A:
𝑟𝑆 2𝐶 𝐴
𝜑𝑆 = =
−𝑟 𝐴 (1 + 𝐶 𝐴) 2
To find the concentration of A where this yield is maximized, we take the derivative and set it to zero:

𝑑𝜑 𝑆 2(1 + 𝐶 𝐴) 2 − (2𝐶 𝐴) · 2(1 + 𝐶 𝐴) 2(1 + 𝐶 𝐴) − 4𝐶 𝐴 2 − 2𝐶 𝐴

= 4
= 3
= =0
𝑑𝐶 𝐴 (1 + 𝐶 𝐴) (1 + 𝐶 𝐴) (1 + 𝐶 𝐴) 3
2 − 2𝐶 𝐴 = 0 =⇒ C∗A = 1 mol/L
At this optimal concentration, the peak instantaneous yield is:
2(1) 2
𝜑 𝑆,𝑚𝑎𝑥 = 2
= = 0.50
(1 + 1) 4
—

Part (a): Maximum 𝐶𝑆 in a Mixed Flow Reactor (MFR)

In a single MFR, the entire reaction takes place at the exit concentration 𝐶 𝐴 𝑓 . The overall yield is the instantaneous yield evaluated at
𝐶 𝐴 𝑓 multiplied by the amount of A consumed.

2𝐶 𝐴 𝑓
 4𝐶 𝐴 𝑓 − 2𝐶 2𝐴 𝑓
𝐶𝑆 = 𝜑 𝑆 (𝐶 𝐴 𝑓 ) × (𝐶 𝐴0 − 𝐶 𝐴 𝑓 ) = (2 − 𝐶 𝐴 𝑓 ) =
(1 + 𝐶 𝐴 𝑓 ) 2 (1 + 𝐶 𝐴 𝑓 ) 2

To maximize 𝐶𝑆 in the MFR, we differentiate this overall expression with respect to 𝐶 𝐴 𝑓 :

𝑑𝐶𝑆 (4 − 4𝐶 𝐴 𝑓 ) (1 + 𝐶 𝐴 𝑓 ) 2 − (4𝐶 𝐴 𝑓 − 2𝐶 2𝐴 𝑓 ) · 2(1 + 𝐶 𝐴 𝑓 )

= =0
𝑑𝐶 𝐴 𝑓 (1 + 𝐶 𝐴 𝑓 ) 4

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Chapter 7 Design for Parallel Reactions Muhammad Shabbir @2102113

Divide out (1 + 𝐶 𝐴 𝑓 ) from the numerator:

(4 − 4𝐶 𝐴 𝑓 ) (1 + 𝐶 𝐴 𝑓 ) − 2(4𝐶 𝐴 𝑓 − 2𝐶 2𝐴 𝑓 ) = 0

4 + 4𝐶 𝐴 𝑓 − 4𝐶 𝐴 𝑓 − 4𝐶 2𝐴 𝑓 − 8𝐶 𝐴 𝑓 + 4𝐶 2𝐴 𝑓 = 0 =⇒ 4 − 8𝐶 𝐴 𝑓 = 0 =⇒ CAf = 0.5 mol/L

Notice that the best exit concentration for the MFR is not the peak yield point (𝐶 𝐴 = 1). We must push the conversion further to generate
more total product, balancing yield with conversion. Substitute 𝐶 𝐴 𝑓 = 0.5 back into the 𝐶𝑆 equation:
   
2(0.5) 1 1.5
𝐶𝑆,𝑚 𝑓 𝑟 = 2
(2 − 0.5) = (1.5) = = 0.667 mol/L
(1 + 0.5) 2.25 2.25
—

Part (b): Maximum 𝐶𝑆 in a Plug Flow Reactor (PFR)

In a PFR, the concentration of A changes continuously from 2 down to 𝐶 𝐴 𝑓 . To maximize the product S, we should run the reactor to
100% conversion (𝐶 𝐴 𝑓 = 0), accumulating S along the entire path.
∫ 𝐶 𝐴0 ∫ 2
2𝐶 𝐴
𝐶𝑆, 𝑝 𝑓 𝑟 = 𝜑 𝑆 𝑑𝐶 𝐴 = 2
𝑑𝐶 𝐴
𝐶𝐴 𝑓 0 (1 + 𝐶 𝐴)

Use 𝑢-substitution: Let 𝑢 = 1 + 𝐶 𝐴, then 𝑑𝐶 𝐴 = 𝑑𝑢, and 𝐶 𝐴 = 𝑢 − 1. The bounds change from [0, 2] to [1, 3].
∫ 3 ∫ 3   3
2(𝑢 − 1) 1 1 1
𝐶𝑆, 𝑝 𝑓 𝑟 = 𝑑𝑢 = 2 − 𝑑𝑢 = 2 ln(𝑢) +
1 𝑢2 1 𝑢 𝑢2 𝑢 1
    
1 2
𝐶𝑆, 𝑝 𝑓 𝑟 = 2 ln 3 + − (ln 1 + 1) = 2 ln 3 −
3 3
𝐶𝑆, 𝑝 𝑓 𝑟 = 2(1.0986 − 0.6667) = 2(0.4319) = 0.864 mol/L
—

Part (c): Reactor with Separation and Recycle

If unreacted A can be separated and recycled, we can force 100% of the reactant to process exactly at the peak of the yield curve. We
operate a CSTR specifically tuned to 𝐶 𝐴 = 1 mol/L. The unreacted A leaving the CSTR is separated and recycled back to the feed.
Consequently, all 2 moles of A are eventually converted at the maximum instantaneous yield of 𝜑 𝑆,𝑚𝑎𝑥 = 0.5.
𝐶𝑆,𝑟 𝑒𝑐𝑦𝑐𝑙𝑒 = 𝐶 𝐴0 × 𝜑 𝑆,𝑚𝑎𝑥 = 2 mol/L × 0.5 = 1.00 mol/L
—

Part (d): Optimal Flow System Without Recycle

We cannot recycle, but we want to maximize the area under the 𝜑 𝑆 vs 𝐶 𝐴 curve.
• Stage 1 (MFR): The feed enters at 𝐶 𝐴0 = 2. As 𝐶 𝐴 drops from 2 down to 1, the yield 𝜑 𝑆 is increasing. An MFR allows us to
bypass this low-yield region and operate entirely at the peak yield. We design the MFR to operate at 𝐶 𝐴1 = 1 mol/L.
Δ𝐶𝑆,1 = 𝜑 𝑆 (1) × (𝐶 𝐴0 − 𝐶 𝐴1 ) = 0.5 × (2 − 1) = 0.500 mol/L

• Stage 2 (PFR): From 𝐶 𝐴 = 1 down to 0, the yield curve is decreasing. A PFR integrates the area under the curve, which captures
more product than an MFR (which would drop instantly to a low yield at the exit).
∫ 1  2
2𝐶 𝐴 1
Δ𝐶𝑆,2 = 2
𝑑𝐶 𝐴 = 2 ln(𝑢) + = 2 [(ln 2 + 0.5) − (0 + 1)]
0 (1 + 𝐶 𝐴) 𝑢 1
Δ𝐶𝑆,2 = 2(ln 2 − 0.5) = 2(0.6931 − 0.5) = 2(0.1931) = 0.386 mol/L
Final Recommended Arrangement: An MFR taking the concentration from 2.0 to 1.0, followed by a PFR taking the concentration
from 1.0 to 0. The total maximum expected concentration of S is:
𝐶𝑆,𝑡𝑜𝑡 𝑎𝑙 = Δ𝐶𝑆,1 + Δ𝐶𝑆,2 = 0.500 + 0.386 = 0.886 mol/L

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