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Chemical Reaction Engineering

Reaction Mechanism and Kinetics


Chemical Transformation
Organic, inorganic, bio-chemistries
Catalysis
Catalysis, advanced material, surface science
Measurements
Physical and analytical chemistries
Analysis
Mathematical modeling
Catalyst and Reactor Design
Material, Energy and Momentum Balances
Chemical engineering processes,
Thermodynamics and fluid mechanics
Transport Kinetics
Mass and heat transfer
Scale-up
Scale-up of technical reactor
Reactor Operation and Control
Control of reactor processes
atomic level pellet level laboratory level production level atomic level pellet level laboratory level production level
Chemical Transformation -1
Free Radical Chain Polymerization
Initiation
(1) thermal or photochemical
(2) chemical initiators
Chemical Transformation -1
Free Radical Chain Polymerization
Propagation
Chemical Transformation -1
Free Radical Chain Polymerization
Termination
Chemical Transformation -1
Magnitude of Reaction Parameters
Chemical Transformation -1
Free Radical Chain Polymerization
Other Reactions
Chain Transfer
(1.1) Give two more reactions that can be found in free-radical
chain polymerization.
Chemical Transformation -2
Sol-gel Process
Silica nanoparticles
Hydrolysis
(1.2) Condensation can be catalyzed by acid or base, please
describe the reaction
Si(OH)
4
Si(OCH
2
CH
3
)
4
+ H
2
O
(HO)Si(OCH
2
CH
3
)
3
(HO)
2
Si(OCH
2
CH
3
)
2
(HO)
3
Si(OCH
2
CH
3
)
Chemical Transformation -2
Sol-gel Process
Silica nanoparticles
Condensation
(1.3) List all possible oligomers for (a) silica and (b) zeolite
2 (HO)Si(OCH
2
CH
3
)
3
(CH
3
CH
2
O)
3
Si-O-Si(OCH
2
CH
3
)
3
(RO)
2
Si-O-Si(OR)
2
O O
S
i
(
O
R
)
2
Si(OR)
2
(RO)
2
Si
(RO)
2
Si Si(OR)
2
Chemical Transformation -2
Sol-gel Process
Silica nanoparticles
Polymerization
Polymerization lead to formation of silica nanoparticles
Si
OSi SiO
S
i
O
S
i
O
Si
OSi SiO
S
i
O
S
i
O
Si
OSi SiO
S
i
O
S
i
O
Si
OSi SiO
S
i
O
S
i
O
3
Si
OSi SiO
S
i
O
S
i
O
Si
OSi SiO
S
i
O
S
i
O
Si
OSi SiO
S
i
O
S
i
O
Si
OSi SiO
S
i
O
S
i
O
Si
OSi SiO
S
i
O
S
i
O
Si
OSi SiO
S
i
O
S
i
O
Si
OSi SiO
S
i
O
S
i
O
Si
OSi SiO
S
i
O
S
i
O
Si
OSi SiO
S
i
O
S
i
O
Si
OSi SiO
S
i
O
S
i
O
Si
OSi SiO
S
i
O
S
i
O
Si
OSi SiO
S
i
O
S
i
O
nanoparticles
agglomerates
powder
Chemical Transformation -2
Sol-gel Process
Silica nanoparticles
Crystallization?
Chemical Transformation -2
Sol-gel Process
Silica nanoparticles
Phase transformation
Chemical Transformation -3
Solar Energy Conversion in Chloroplast
Typical Plant Cell Chloroplast
Chemical Transformation -3
Solar Energy Conversion in Chloroplast
Thylakoid Membrane
h
2 H
2
O + 2 NaDP
+
2 H
+
+ O
2
+ 2 NaDPH
H
+
+ ADP
3-
+ P
i
ATP
4-
+ H
2
O
6 CO
2
+ 18 ATP
4-
+ 12 NaDPH + 12 H
2
O
6 H
+
+ C
6
H
12
O
6
+ 18 ADP
3-
+ 18 P
i
+ 12 NaDP
+
(1.4) Describe ATP production by mitochondrion
Catalysis
Catalyst speed up the rate of reaction by lowering the activation
energy (Ea).
It does not change the thermodynamics of the reaction,
It equally speed up the forward and reverse reactions,
It may undergo transformation during reaction, but is not
consumed by the reaction.
(1.5) What are the other characteristics of a catalyst?
Catalysis
HeterogenousCatalysis
Ziegler-Natta
Group IV or VIII Cocatalyst Group III
Catalysis
Homogenous Catalysis
Metallocene
(1.6) Describe the metallocene catalysts for isotactic, syndiotactic and
atacticpolypropylene.
Heterogenous Catalysis
Surface Processes
Ammonia
NH
3
NH
2
(ads) + H (ads) NH (ads) + 2 H (ads) N (ads) + 3 H (ads)
N
2
H
2
N
2
(ads) + 1.5 H
2
(ads)
N
2
(g) + 1.5 H
2
(g)
Adsorption, diffusion, surface reaction and desorption
Heterogenous Catalysis
HeterogenousCatalysts
Reactions occurs on the catalyst surface, therefore
a large surface area is advantageous
Nickel clusters
SiO
2
Highly dispersed metal on metal oxide
http://brian.ch.cam.ac.uk/~jon/PhD2/node19.html
55 atom cluster surface energy
minimization
highest
lowest
Dispersed Catalysts
Heterogenous Catalysis
Preparation
Characterization Testing
Structure
Bulk: XRD, XAS, NMR
Surface: GA-XRD, FIM, TEM, AFM
Morphology: Microscopies
Chemistry
Bulk: XRD, XRF
Surface: XPS, AES, SIMS, FTIR
Localized: EDXS, EPM
Electronic
ESR, UV-Vis, IR, XPS
Screening
Combinatorial screening
Laboratory Reactor
Batch, differential and integral
In-situ Reaction
Reaction conducted under
direct observation
CENG 511 (Spring 04)
Heterogenous Catalysis
Catalyst Preparation
Metal forming & Alloying
Metal Foil
Raney Nickel
Electroplating
Electroless plating
Precipitation
Co-precipitation
Reduction-Oxidation
Wet impregnation
Incipient Wetness
Ion exchange
Chemical vapor deposition
Physical deposition
Vapor impregnation
Reverse Micelle
Surfactant-Assisted
-Colloidal Synthesis
Thermal Oxidation
Metal Oxide Fuming
Sol-gel Process
Flame Synthesis
Hydrothermal Crystallization
Vapor-phase Hydrolysis
Pyrolysis (carbon-base catalysts)
Nitridation
Sintering
Clay Intercalation
Microfabrication
Thin film processes
Polymerization
Chemical Grafting
Ligand Chemistry
Enzyme and Proteins
Etc
Biological Catalysts
Enzymes
Catalase
(1.7) Give five more enzymes and the
reactions that they catalyzes
Biological Catalysts
Catalase
Material Balances
Conservation of Mass
(input +generation) - (output +depletion) =Accumulation
in
1
in
2
out
1
generation or depletion
accumulation
Surrounding
System
Material Balances
A government population survey of a new town shows that in a year 15,000 people
establish residence in the town but during the same year 5000 people moves to the
surrounding suburbs. 8000 birth and 2000 death was recorded during the year. How
many people live in the city if the last year population is 350,000 people. How
many women in the city if the average male-female ratio is 0.82.
Material Balances
Conservation of Mass
(input +generation) - (output +depletion) =Accumulation
0 0
Assuming: No transmutation (i.e., fission or fusion reactions)
Mole Balance
(input +generation) - (output +depletion) =Accumulation
Accounts for chemical reaction
Material Balances
Note: We assumed no diffusional flux
through the boundary
General Material Balance
Material Balances
Batch Reactor
Material Balances
Batch Reactor
First Order Irreversible Reaction
H
2
O
2
+1-pentene 1-epoxypentene+H
2
O
TS-1
Experiment conducted using methanol solvent,
Large excess of 1-pentene was used,
Reaction conducted at room temperature.
=kc
A
Material Balances
Batch Reactor
First Order Irreversible Reaction
H
2
O
2
+1-pentene 1-epoxypentene+H
2
O
TS-1
k = kc
B0
c
B0
>> c
A0
Material Balances
(1.8) Derive the reaction equation for a second order reversiblereaction (A
to 2B). Plot CA/CA0 vs reaction time.
Material Balances
Determine the concentration of 1-epoxypentene product
Stoichiometry
A + 0.5 B 2 C + 0.75 D
t =0 n
A0
n
B0
n
C0
n
D0
t 0 n
A
n
B
n
C
n
D
X
A
=
n
A0
n
A0
- n
A
X
B
=
n
B0
n
B0
- n
B
Note: X
A
X
B

B
=

A0
n
A0
- n
A
X
A
=
n
A0

B0
n
B0
- n
B
X
B
=
n
B0

Extent of Reaction
Stoichiometric coefficient
Stoichiometry
Stoichiometry
Please find the stoichiometric coefficients, extent of reaction
conversion, yield with respect to methane, and selectivity.
t =0 5 15 0.2 3
t 0 1 3.5
0
CH
4
+ H
2
O CO + H
2
C + H
2
3
Energy Balances
Conservation of Energy (First Law of Thermodynamics)
Energy Balances
Work Terms
Compressor
Stirrer
Pump
0
Energy Balances
Energy Terms
Internal Energy Potential Energy
Kinetic Energy
Magnetic and Electrical Energies
Energy Balances
Energy Balances
Batch Reactor
Energy Balances
General Energy Balance Equation for Batch Reactor
Heat of Reaction
Sensible Heat
Expansion term
Latent Heat
Energy Balances
General Energy Balance Equation for Batch Reactor
Heat of Reaction
Sensible Heat
Expansion term
Latent Heat
Energy Balances
Heat of Reactions
Heat associated breaking and forming of chemical bonds in a
molecule
Energy Balances
Standard Heat of Formation (H
f
o
)
C(s) +O
2
(g, STP) CO
2
(g, STP)
The change in enthalpy associated with any chemical reaction that involves the
creation of a molecule from elements in their standard state is called the heat of
formation.
+

C
O O
CO
2
Energy Balances
Standard Heat of Formation
Energy Balances
Standard Heat of Combustion
Energy Balances
Constant Pressure
Energy Balances
Constant Volume (Ideal Gas)
(2.1) Derive the above equation from the general energy balance equation
for a batch reactor.
Energy Balances
Constant Volume vs Constant Pressure
Energy Balances
Liquid phase batch reactor 1
The exothermic elementary liquid phase reaction:
was carried out in a batch reactor with a cooling coil to keep the reactor
isothermal at 27C. The reactor was filled with 2 mol/L of reactant A.
(a) How long does it take to reach 95 % conversion?
(b) What is the total amount of heat (kcal) removed by the cooling coil
when this conversion is reached?
(c) What is the maximum rate by which the heat must be removed by
the heating coil (kcal/min) and at what time does this maximum occurs?
(d) What is the adiabatic temperature rise for this reactor and its
significance?
Energy Balances
Additional information:
Liquid phase batch reactor 2
(2.2) Repeat the calculation for a second order irreversible reaction:
Energy Balances
First Order Reaction Kinetics
0
0.5
1
1.5
2
0 100 200 300 400
time (s)
C
A

(
M
)
0
0.2
0.4
0.6
0.8
1
0 100 200 300 400
time (s)
C
o
n
v
e
r
s
i
o
n

(
X
)
Energy Balances
Heat Removal by Cooling Coil
400
0
100
200
300
400
500
0 100 200 300
time (s)
-
Q

(
k
c
a
l
/
s
)
0
10000
20000
30000
0 100 200 300 400
time (s)
-
Q

(
k
c
a
l
)
.
Energy Balances
Adiabatic Heating and Temperature Rise
.
0
100
200
300
0 2 4 6 8 10 12 14
time (min)
T
e
m
p
e
r
a
t
u
r
e

(
C
)
Ea =5 kcal/mol
10 20
0
50
100
150
200
250
0 0.2 0.4 0.6 0.8 1
Conversion (X)

T

(
K
)
Energy Balances
Runaway Reaction
.
Ea =5 kcal/mol
10 20
0
0.2
0.4
0.6
0.8
1
0 50 100 150 200 250
time (min)
C
o
n
v
e
r
s
i
o
n

(
X
)
Isothermal
0
0.2
0.4
0.6
0.8
1
0 2 4 6 8 10 12 14
time (min)
C
o
n
v
e
r
s
i
o
n

(
X
)
Thermodynamics
Why study chemical reaction equilibrium when operating reactors
are never at chemical equilibrium?
Chemical Reaction Equilibrium
(1) Determine the limits of reactor performance,
(2) Explore possible design and operation changes that overcomes
these restriction and optimizes reactor performance.
Thermodynamics
Gibbs Energy (G)
Physical and Chemical Precondition for Biochemical Reactions
including Cell Metabolism and Enzymatic Catalysis
UNCATALYZED ENZYMATICALLY CATALYZED
Thermodynamics
G <0 Spontaneous, Energy releasing process Exergonic Process
G =0 Equilibrium process
G >0 Non-spontaneous, Energy consuming process Endergonic Process
Energy (Photon, Heat)
Nutrient (Reduced molecules)
cell
metabolism
STORED
ENERGY
http://www.biologie.uni-hamburg.de/b-online/e18/18.htm
Thermodynamics
Work by using exergonic processes to drive endergonic processes
Cell Metabolism
ATP is an important source of energy
Thermodynamics
Reaction Equilibrium is harnessed in microelectronic fabrications
Semiconductor Processing
Chemical Vapor Deposition
Thermodynamics
Chemical Vapor Deposition
Thermodynamics
Reaction Equilibrium is harnessed in microelectronic fabrications
Chemical Vapor Deposition and Etching
Thermodynamics
Thermodynamic System
The Gibbs free energy of the system (G) is the convenient energy
function of these state variables.
The equilibrium state of the system is completely
defined once the temperature, pressure and moles
of each components are specified.
Thermodynamics
Condition for Reaction Equilibrium
The Gibbs free energy:
Extend of Reaction
Thermodynamics
Condition for Reaction Equilibrium
The Gibbs free energy:
Extend of Reaction
Thermodynamics
Condition for Reaction Equilibrium
Necessary condition for
reaction equilibrium
Standard Gibbs energy
activity fugacity
Thermodynamics
Condition for Reaction Equilibrium
The Gibbs free energy for a reaction system:
Standard Gibbs energy
of change
Equilibrium
constant
Thermodynamics
Ideal Gas Equilibrium 1
High octane fuel additives are produced by reaction of isobutanewith
1-butenehydrocarbons:
Determine the equilibrium composition of the reaction mixture at a
pressure of 2.5 atm and temperature of 400 K. The standard Gibbs
energy change for this reaction at 400 K is 3.72 kcal/mol.
Assume that equimolar amounts of isobutane and 1-butene are present
in the initial mixture.
(2.3) Please repeat the calculation if the initial ratio of I/B =100, 10, 0.1.
Thermodynamics
Modified Gibbs Energy
Single
reaction
Thermodynamics
Modified Gibbs Energy
=0.469

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