Course Outline - Lecture Course Outline Lecture
Course Outline - Lecture Course Outline Lecture
Part 1
Elementary principles of catalytic reactions in solutions
Part 2
General background and fundamentals in heterogeneous
catalysis
Heterogeneous catalyst concept
concept, preparation & manufacturing
Characterization of heterogeneous catalysts
Planning, development and testing of catalysts
F partt 1
For
A purely elective course.
No homework assignment
assignment.
No quiz.
Office
Offi h
hour: Th
Thursday,
d
16
16:30-17:30.
30 17 30
C t l ti Ch
Catalytic
Chemistry
i t
Lecture 1
C t t
Content
Review.
Catalysis in solutions.
Acid.
Base.
Metal cations
cations.
Electron transfer.
Review
What is catalyst?
Catalytic cycle.
Catalytic
y reaction rate.
5
What is catalyst?
H
How
d
does catalyst
t l t work?
k?
Kinetics
R t determining
Rate
d t
i i
M h i
Mechanisms
M h i
Mechanisms
Solutions
S f
Surfaces
Cavities
11
M h i
Mechanisms
A full
f ll accountt off how
h
a catalyst
t l t works
k requires
i
a description
d
i ti off ttransport.
t
One phase.
Between phase.
12
C t l ti cycle
Catalytic
l
13
P i
Poison
14
Quantitative measurement
Activity
Selectivityy
Stability
How fast a catalyst works, which is usually defined as the reaction rate.
In practice,
practice catalysts are inevitably involved in side reactions that lead to their
conversion into inactive forms.
Regenerability
g
y
15
C t l i iin solutions
Catalysis
l ti
I t d ti
Introduction.
Acid catalysis.
Base catalysis.
I t d ti
Introduction
The dependence
p
of rates of reaction on the
concentrations of reactants and catalysts may be
relatively easy to determine.
17
Collision theory
k rate
k:
t constant.
t t
Z: collision frequency.
: Steric factor.
Ea: activation
ti ti energy off the
th reaction.
ti
T: Temperature.
R: gas constant.
18
kT
h
k: Boltzmanns constant.
T: Temperature.
Temperature
h: Plancks constant.
19
W kl structured
Weakly
t t d ionic
i i liliquid
id
Weakly
W kl structured
t t d nonionic
i i liliquid
id
21
Proton transfers
NH4+ + H2O
NH3 + H3O+
22
St
Stepwise
i and
d concerted
t d reactions
ti
r = kCacetoneC HAC A
Acetone halogenation
g
reaction,, rate equation:
q
24
The diff
Th
difference b
between
t
concerted
t d and
d stepwise
t
i reactions
ti
are
usually subtle, and distinguishing them experimentally is difficult.
The differences amount to just where the protons, anions, and
solvent molecules are located at particular stages of completion
of the reaction.
It is oversimplification to refer to the stepwise and concerted
reactions as the only two possibilities. These represent limiting
cases, with a whole spectrum between them.
It is often a good approximation that any one mechanism is
uniquely important, but a spectrum of similar mechanisms may
prevail,
il and
d the
th dominant
d i
t mechanism
h i
may change
h
with
ith changing
h
i
reaction conditions.
25
Acid--base catalysis
Acid
27
r=kobsCR=[k0+kH3O+CH3O++kOH-COH-+kHACHA+kA-CA-]CR
28
29
k HA = GHA K a
log k HA = log K a + const
GHA: Constant characteristic of the acid.
: Constant with a value between 0 and 1.
30
B
Bronsted
t d equation
ti
Generalacidcatalyzedreaction.
Correlatetheacidcatalyticactivitywiththecharacteristicsofweakacid(not
completelydisassociated).
Itisagoodapproximationingeneral,butitisempirical.
k HA = GHA K a
log k HA = log K a + const
k HA
isasecondorderrateconstant
Forspecificacidcatalysis,theanalogy:
isapseudofirstorderrate
constant
P f
Proof
RH + + A
K 20
RH + + A
HA + I
I P + H 2O
Ifthesecondstepisratedetermining,then:
r = k 20C RH + C A = k 20 K19C R C HA
The observed rate constant:
Theobservedrateconstant:
kobs = k 20 K19
P l
Polanyi
i relationship
l ti
hi
isaconstantbetween0and1
C H 3O + C A
=
equil C H 2O C HA
C H 2O C RH +
C + CR
equil H 3O
= K a const
equil
This
Thisequalityfollowsbecausetheterminparenthesesonthe
equality follows because the term in parentheses on the
farrightisapropertyofthereactantbutnotofthecatalyst.
C H O + C A
= 3
equil C H 2O C HA
'
r = constK19 K 20
C R C HA
C H 2O C RH +
C + CR
equil H 3O
= K a const
equil
C I C H 3O +
C + CH O
2
RH
equil const
K 20 =
=
Ka
C A C H 3O +
C HAC H O
2
equil
r = const K a1 'C R C HA
k = const K a
= 1 '
Consider
C
id th
the ffollowing
ll i
mechanism as a
hypothetical example:
R + H + RH + * RH +
RH + H + + P
kT
r=
C(RH + )*
h
H + CR R
K* =
C(RH + )* (RH + )*
kT
R
r=
H + CR
hK *
(RH + )*
kT
r=
C R h0
hK *
Ka =
aH + a A
a AH +
aH + A C A
=
AH + C AH +
log K a = pK a = H 0 + log
H 0 = pK a log
C AH +
CA
C AH +
CA
Thisresultaccountsforalineardependenceofthelogarithm
oftheobservedrateconstantontheHammettacidity
functionH0.
C t l i iin th
Catalysis
the gas phase
h
38
As a consequence of the
proton donation, the alcohol
becomes more reactive for
the splitting out of a water
molecule and a proton.
39
In 1850 Wilhelmy reported that the rate of sucrose inversion in the presence
of dilute aqueous mineral acids to be proportional to the concentration of
acid and independent of which acid was used, provided that it was a dilute
strong acid,
acid that is,
is one fully dissociated in water
water.
C12H22O11 (sucrose) + H2O (water) = C6H12O6 (glucose) + C6H12O6 (fructose).
The results demonstrated that the sucrose inversion reaction was catalyzed
by protons, which were produced equally from all the strong acids.
Ester hydrolysis
Dehydration of
tertiary alcohols
Esterification
40
As is
A
i the
h typical
i l off these
h
reactions,
i
the
h fi
first step iis a protonation
i off the
h
reactant, which is a base. The protonation of the oxygen provides a much
better leaving group, that is , an alcohol.
The proton
Th
t are consumed
d in
i
one step of the catalytic cycle
and released in another.
41
r = kCH + Cacetal
The decomposition
p
of the
protonated acetal is slow and
may be assumed to be rate
determining step
step.
Therefore:
K=
C protonated
acetal
C H + Cacetal
r = k ' C protonated
acetal
r = k ' KC H + Cacetal
42
Bisphenol A
Acetone
Phenol
The reaction
Th
ti kinetics
ki ti
has been reported to
be the following
g where
A refers to acetone
and P to phenol
r = kCH + CACP
and,alternatively
r = kCH + CAC P
The kinetics has been inferred here from the known mechanism, but a
much more difficult and common challenge is to infer a mechanism
p
y determined kinetics.
from experimentally
45
46
47
Since the p
proton donors include numerous species
p
other than
hydrated protons. A more general measure of the protondonor strength of strongly acidic solutions was developed by
Hammett and Deyrup.
y p Solutions are characterized by
y their
tendency to protonate neutral basic indicators (A):
+
H + A AH
+
48
H
Hammett
tt acidity
idit function
f
ti
aH + a A
a AH +
aH + A C A
AH + C AH +
log K a = pK a = H 0 + log
H 0 = pK a log
-H
H0
C AH +
CA
C AH +
CA
49
50
Just as there are many examples for which the rate in a dilute
solution is a simple function of the hydrogen ion
concentration.
t ti
C t l i b
Catalysis
by b
bases
52
53
r = kC A C protonated
acetone
= kKCacetoneC HA
54
55
C t l i b
Catalysis
by metal
t l iions
56
58
C t l i b
Catalysis
by electron
l t
ttransfer
f
C t l i iin solutions
Catalysis
l ti
Catalysis
y
by
y electron
transfer.
Simple
redox reactions
Oxidation
60
An example
p of a redox reaction taking
gp
place in aqueous
q
solutions is:
V 3+ + Cu 2+ V 4+ + Cu +
Tl + + 2Ce 4+ Tl 3+ + 2Ce 3+
Ce 4+ + Ag + Ce 3+ + Ag 2+
Ag 2+ + Tl + Tl 2+ + Ag
A
A +
Tl 2+ + Ce 4+ Tl 3+ + Ce 3+
r = kC Ag 2+ CTl +
63
F +V
Fe
4+
3+
Fe
F +V
3+
O id ti iinvolving
Oxidation
l i ffreefree-radical
di l
intermediates
G
General
l scheme:
h
Initiation
In2 2 In
Propagation
p g
R +O2 RO2
Termination
R + RO2 RO2 R
In + RH InH + R
RO2 + RH RO2 H + R
RO2 H + M ( n 1) + RO + M n + + OH
RO2 H + M n + RO2 + M ( n 1) + + H +
2 RO2 2 RO +O2
RO + RO2 H RO2 + ROH
In2 2 In
RO2 H + M ( n 1) + RO + M n + + OH
In + RH InH + R
RO2 H + M n + RO2 + M ( n 1) + + H +
R +O2 RO2
2 RO2 2 RO +O2
RO2 + RH RO2 H + R
69
Experiments to distinguish
these possibilities are
sometimes done with added
free-radical scavengers.
70
F th reading
Further
di
To understand catalysis, we should know
the principles of reaction kinetics.
Most importantly, we should know the
principles of thermodynamics.
71