CONFIDENTIAL

Ernest W. Thiele:
His Impact on Chemical Engineering

Jonathan H. Worstell
Principal Scientist

Shell Global Solutions (US) Inc Westhollow

Technology Center
Houston, Texas
 Overview
First Encounter with Thiele

Disconnect with regard to Thiele

Life in Brief

Graduate School Career

Mc-Cabe-Thiele Diagrams

Thiele Modulus in Catalyst Design

Thiele and Nuclear Engineering

Adsorption

Common Form of Papers

Overview of Career

2
First Encounter with Thiele

Introductory Unit Ops Course

McCabe-Thiele Diagrams

Chemical Engineering Kinetics

Thiele Modulus

3
 Generalist, not Specialist

Generally do not connect these “Thiele’s” as being one and the

same.

Why ?

McCabe-Thiele diagram is used to design distillation columns.

Thiele modulus is used to design porous, solid

catalyzed processes.

Today --- an age of specialists.

Thiele’s day --- an age of generalist.

4
 Life in Brief
• 1895 --- born in Chicago, IL
• 1916 --- earned A.B. from Loyola University (Chicago)
• 1917 --- joined U.S. Army; stationed at University of IL
• 1919 --- earned B.S. in Chemical Engineering from University of IL
• 1920 – 1922 --- worked as chemical engineer at People’s Gas
• 1922 --- matriculated at MIT
• 1925 --- graduated from MIT with a DSc; joined Standard Oil of Indiana (later
Amoco Corp)
• 1942-1943 --- helped design and commission Canadian heavy water separation
plant at Trail, BC
• 1949 --- engaged as consultant by AEC to study possible loss of Ur at Argonne
National Laboratory
• 1960 --- retired as Associate Director R&D for Amoco Corp
• 1970 --- retired as visiting Professor at Notre Dame, South Bend, IN
• 1993 --- died at Presbyterian Nursing Home in Evanston, Il 9 days short of 98th
birthday)

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 First Publication
“Recent Progress in the Field of Fuels and Fuel Technology”
Industrial and Engineering Chemistry, 16, 749 (1924)

• Coal
- Mineralogy
- Storage
- Washing
- Powdered Combustion --- Boiler Technology
• Coke
- Processes
- Combustion
• Liquid Fuels
- Anti-knock and Fuel Efficiency
- Ethanol from Carbohydrates --- Petroleum Fuel Blends
- Motor Fuels
- Synthetic --- Fischer-Tropsch Technology, Hydrogenation of Solid Fuels
• Low-energy Content
- Lignite
- Peat

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 Doctoral Exams
Trials and Tribulations of the Oral Exam

Scientist /
Engineer Ph.D. Exam Accomplishments
Graduated summa cum laude
Nobel Physics Prize
W. Pauli Matriculated with three publications
“Pauli Exclusion Principle”
in relativity at age 18
Nobel Physics Prize
W. Heisenberg Nearly failed exam “Heisenberg Uncertainity
Principle”
J. R. Failed to matriculate at Gottingen “Director” of American
Oppenheimer University theoretical physics
Nobel Physics Prize
No record of taking one
R. Feynman Path Integrals
(Spring 1942)
Quantum Electrodynamics
Feynman gave lecture during exam;
Conservative Replication of
M. Meselson applied path integrals to thesis
DNA
calculation
Comments about McCabe McCabe-Thiele Diagrams
E. Thiele
calculations Thiele Modulus

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 McCabe-Thiele Diagrams

W.L. McCabe and E.W. Thiele

“Graphical Design of Fractionating Columns”

Industrial and Engineering Chemistry, 17, 605 (1925)

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 McCabe-Thiele Diagrams --- Assumptions
• Molar overflow is constant from tray to tray, except for the feed tray.
- Requires formation of a mole of vapor for each condensed mole of
vapor on a tray.
- Requires identical molar heats of vaporization for two
components;
- Requires assumption of Trouton’s Rule;
- Requires all heat effects to be zero.

• Feed enters at temperature equal to the boiling point of the liquid on the
feed tray.

• Total condenser used to recover product.

• Heat enters bottom of column via heat exchanger; ie, “closed steam”
process.

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McCabe-Thiele Diagrams --- Equations

Equilibrium Condition (Curve)

PAv x E
yE =
P

P − PBv
xE = v
PA − PBv

Rectification Section Material Balance

⎛L⎞ Dx D
y n = ⎜ ⎟ x n +1 +
⎝V ⎠ V

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McCabe-Thiele Diagrams --- Equations

Stripping Section Material Balance

⎛ L⎞ Bx
y m = ⎜ ⎟ x m +1 − B
⎝V ⎠ V

⎛V ⎞ Bx
x m +1 = ⎜ ⎟ y m + B
⎝ L⎠ L

Feed Tray Material Balance

⎛ q ⎞ x
y = ⎜⎜ ⎟⎟ x m +1 − F
⎝ q − 1⎠ q −1

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McCabe-Thiele Diagrams

12
McCabe-Thiele Diagrams

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McCabe-Thiele Diagrams

14
 Lub Oil Flash Points
E.W. Thiele
“Prediction of Flash Point of Blends of Lubricating Oils”
Industrial and Engineering Chemistry, 19, 259 (1927)

Derives Flash Point calculation

o
{ ( 1
) (
FFP ,mix = −100 log X 1 10 −0.01( FFP ) + X 2 10 −0.01(
2
FFP
) n(
) + ... + X 10 −0.01( n
FFP ) )}
from Antoine’s Equation

log( v P ) = −
A
+B
T

Observed versus calculated values within 2 oF.

15
 Distillation of Complex Mixtures
E.W. Thiele and R.L. Geddes
“Computation of Distillation Apparatus for Hydrocarbon Mixtures”
Industrial and Engineering Chemistry, 25, 289 (1933)

Design of distillation columns for separating complex

hydrocarbon mixtures hampered by lack of method.

Equations similar to McCabe-Thiele method.

Stresses that formulas are designed to maximize slide rule efficiency.

Degree of accuracy is limited by knowledge of

equilibrium relationship
tray efficiencies

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 Densities of Hydrocarbon Mixtures
E.W. Thiele and W.B. Kay
“Densities of Hydrocarbon Mixtures”
Industrial and Engineering Chemistry, 25, 894 (1933)

Density used in
calculations of pressure drop in pipes
design of pipe stills
design of cracking equipment
determining bubble column diameters

Reviews methods available for computing hydrocarbon densities.

Makes recommendations as to which methods to use per phase.

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 Bubble Cap Trays for Distillation
M.C. Rogers and E.W. Thiele
“Pressure Drop in Bubble-cap Columns”
Industrial and Engineering Chemistry, 26, 524 (1934)

Analyzed the components of pressure drop through bubble caps

for bubble caps with teeth, slots, or similar devices along lower edge.

Presented a formula for

calculating opening of teeth on bubble caps;
computing pressure drop for such bubble caps.

Experimental results confirmed proposed theory.

Results
Friction loss through chimney uptake and space under the bubble cap is negligible.
Pressure drop thru slot opening can be calculated per published formula.
Static head above slot tend to be a maximum at low vapor flows.
Location of overflow weir on bubble cap tray important.

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Ponchon Method for Distillation and Extraction
E.W. Thiele
“Application of Graphical Method of
Ponchon to Distillation and Extraction”
Industrial and Engineering Chemistry, 27, 392 (1935)

McCabe-Thiele method assumes constant overflow through a distillation column.

Constant overflow does not occur when

there is a significant temperature change through the column
heat of mixing is not zero.

Presents Ponchon’s method for designing distillation columns

with variable overflow to American engineers.

Extends Ponchon’s method to countercurrent extraction.

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 Liquid-liquid Contact Apparatus
M.C. Rogers and E.W. Thiele
“Bubble-cap Column as a Liquid-liquid Contact Apparatus”
Industrial and Engineering Chemistry, 29, 529 (1937)

Liquid-liquid extraction done by

packed columns;
mixer / settlers.

Liquid-liquid extraction is similar to distillation,

thus bubble-cap trays ought to work for such extractions.

Built and tested a bubble-cap liquid-liquid extraction

column fitted with bubble-cap trays.

Such columns have low efficiencies, due to poor agitation.

Packed columns are better for liquid-liquid extractions.

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 Heterogeneous Catalysis
E.W. Thiele
“Relation between Catalytic Activity and Size of Particle”
Industrial and Engineering Chemistry, 31, 916 (1939)

Ph.D. Thesis --- Water-gas reaction catalyzed by porous carbon (activated carbon).

Obtained peculiar results --- thought the porous carbon contributed to such results.

Ruminated on thesis results for years.

Gradually developed a theory to explain

thesis results during spare time.

Work done independently of Damkohler and Zeldovich.

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 Analysis of Problem
Original Figure from Article

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 Heterogeneous Catalysis --- Results
Thiele Modulus and Effectiveness Factor for Various Catalyst Shapes
Parameter Slab Cylinder Sphere

Thiele Modulus xP k RP k RP k
φ
e e e
DTA DTA DTA

Effectiveness Factor tanh φ 2 I1 (φ ) 3⎡ 1 1⎤

η ⎢ − ⎥
φ φI 0 (φ ) φ ⎣ tanh (φ ) φ ⎦
(Actual Act / Max Act)

Theory distinguishes between

reaction rate limited;
diffusion rate limited.

By-product formation depends upon the Thiele Modulus.

Activation Energy analysis depends upon the Thiele Modulus.

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Results of
Analysis

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Physical Interpretation of Analysis

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 Material and Heat Transfer
E.W. Thiele
“Material and Heat Transfer between
a Granular Solid and Flowing Fluid”
Industrial and Engineering Chemistry, 38, 646 (1946)

Review and analysis of adsorption.

Describes “wave front” adsorption.

Discusses longitudinal diffusion.

Mentions impact of transfer rates on adsorption.

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 Common Form of Thiele Papers

Brief presentation of problem.

Description of physics involved in the problem.

Presentation of assumptions.

Derivation of pertinent equations.

Discussion of pertinent experimental results.

Brief conclusions.

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 Career in Review

Ernest W. Thiele made important contributions to the

theory of distillation

theory of catalytic activity

practice of petroleum refining

foundation of nuclear engineering

foundation of adsorption

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 Summary
First Encounter with Thiele

Disconnect with regard to Thiele

Life in Brief

Graduate School Career

Mc-Cabe-Thiele Diagrams

Thiele Modulus in Catalyst Design

Thiele and Nuclear Engineering

Adsorption

Common Form of Papers

Overview of Career

29