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?

How do catalysts work?

What is the mechanism?

Catalytic cycle.

What is inhibitor and poison?

Catalytic
y reaction rate.
5

What is catalyst?

A catalyst is by definition a substance that increases

the rate of approach to equilibrium of a chemical
reaction without being substantially consumed in the
reaction.

H
How
d
does catalyst
t l t work?
k?

Kinetics

The definition of a catalyst rests on the idea

of reaction rate, and therefore the subject of
reaction kinetics is central, providing the
quantitative framework.

R t determining
Rate
d t
i i

M h i
Mechanisms

The qualitative chemical explanations of

catalysis take the form of reaction
mechanisms.

These are models of reactions.

Accounting for the overall stoichiometry

stoichiometry.

Identifying the sequence of elementary

reaction steps
steps.

Explaining in terms of chemical bond

strength and geometry, the interaction of
the catalyst with reactant.
10

M h i
Mechanisms

The mechanisms commonly

Solutions

involve the transfer of ions

(often hydrogen ions), electrons,
and/or radicals.
radicals

Catalytic reactions take place in

various phases.

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

An inhibitor slows down a catalytic

reaction.

A competitive inhibitor slows down the

reaction by competing with the reactants
in bonding to the catalyst
catalyst.

A very strong inhibitor, one that bonds so

strongly that it virtually excludes the
reactant from bonding with the catalyst, is
called a poison.

14

Quantitative measurement

Activity

Selectivityy

A measure of the catalysts ability to direct the conversion to the desired

products.

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

A deactivated catalyst may be treated to bring back its activity.

15

C t l i iin solutions
Catalysis
l ti

I t d ti
Introduction.

Acid catalysis.

General and specific acid and base catalysis.

y

Stepwise and concerted reactions.

Catalysis in the gas phase.

Catalysis in dilute aqueous solutions.

Catalysis in concentrated strong acid solutions.

Base catalysis.

Catalysis by metal ions.

Catalysis by electron transfer.

Simple redox reactions

Oxidation involving free-radical intermediates.

16

I t d ti
Introduction

Catalysis in solutions is the best understood because of

the uniformity of the catalytic species and of the
environment around the species participating in a reaction.

The structures of reaction species, possibly including

short-lived intermediates, may be determined by methods
s ch as infrared
such
infrared, ultraviolet,
ltra iolet and n
nuclear
clear magnetic
resonance (NMR) spectroscopy.

The dependence
p
of rates of reaction on the
concentrations of reactants and catalysts may be
relatively easy to determine.

17

Collision theory

A collision between two molecules may result in

no more that a transfer of energy
energy, but
occasionally it may lead to the forming or
breaking of chemical bonds or both.

Collision frequencies are predicted by the kinetic

theory of gases, which forms the basis for the
simple collision theory of reaction rates:

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

Transition state theory

It is assumed that the reactants form a

fleeting intermediate referred to as a
transition state or activated complex.

It is assumed that there is single potential

energy surface on which the components
will move as the reactants and products,
there is one path on this surface that
requires the least energy for the
transformation. The position along this
path
th iis called
ll d th
the reaction
ti coordinate.
di t

The rate constant, according to the theory

in its simplest
p
form,, is universally:
y

kT
h

k: Boltzmanns constant.
T: Temperature.
Temperature
h: Plancks constant.
19

W kl structured
Weakly
t t d ionic
i i liliquid
id

Water is unique because the molecules are small and

strongly polar. The structure of water is determined by
the hydrogen bonds
bonds.

It dissolves many ionic compounds, a solution of ions in a

solvent mayy be described as a clustering
g of solvent
molecules forming solvation shells around the ions.
20

Weakly
W kl structured
t t d nonionic
i i liliquid
id

Polar molecules have an affinity for

other polar molecules.

Hydrogen-bonded structures are

typical.

Sometimes the affinity of molecules for

each other are so strong that they form
a separate phase.

The protons in these structures are

highly mobile.

21

Proton transfers

NH4+ + H2O

The essential steps of acid-base catalysis are often proton

transfers
transfers.

The protons in hydrogen-bonded structures are highly mobile

because the protonic mass is so low.

There is a rapid interconversion of related structures as a

proton moves.

The rapid proton jjumping

mping acco
accounts
nts for the electrical
conductivity of water and of ice.

Many reactions catalyzed by acids and bases in water proceed

via such proton transfer.
f

NH3 + H3O+

22

St
Stepwise
i and
d concerted
t d reactions
ti

When various bond-breaking and bond-forming steps

take place almost simultaneously, the process is referred
to as a concerted or synchronous reaction.

Reactive intermediates or other unstable high energy

intermediates are not involved

Concerted reactions are common in acid-based catalysis

in the absence of water or other good proton acceptors.

A stepwise reaction is a chemical reaction with at least

one reaction intermediate or reaction intermediates and
involving at least two consecutive elementary reactions
reactions.
23

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

Concerted proton transfer processes are facile in pairs of

molecules that can cycle between two tautomeric states
Tautomers are organic
compounds that are
interconvertible by a
chemical reaction
called tautomerization

The mechanism is often referred to as a push-pull

p
p
mechanism.

Tautomeric catalysis becomes important only when a proper geometric

match exists between the catalyst and reactant.
26

Acid--base catalysis
Acid

27

General and specific acid and

base catalysis
Oximation

r=kobsCR=[k0+kH3O+CH3O++kOH-COH-+kHACHA+kA-CA-]CR
28

When the proton donor is H3O+, the catalysis is referred to as

specific acid catalysis.

When the proton donors include other species, such as HA and

H2O, general acid catalysis occurs.

When the proton acceptor is OH-, specific base catalysis occurs.

When the proton acceptors include other species, such as B and

H2O, general base catalysis occurs.

The occurrence of catalysis by undissociated acids (or bases) leads

to a central question: How does the reactivity of a species in a
catalytic
t l ti cycle
l d
depend
d on some measurable
bl properties
ti off th
the
catalysts?

29

The question can be answered as follows for general acid

catalysis:
t l i Th
The stronger
t
th acid,
the
id th
the more active
ti th
the
catalyst, In other words, the greater the dissociation
constant Ka,
a H + a A
Ka =
aHA
The more active the catalyst HA.
HA Often this statement is
quantitatively expressed by the Brnsted equation:

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:

log k = log C H + + const

isapseudofirstorderrate
constant

P f
Proof

Consider the general acid catalyzed reaction taking place by the

f ll i simple
following
i l sequence: where
h
the
h proton d
donor species
i iis the
h
undissociated acid HA, the reactant is R, the intermediate is I, and
the product are P and H2O.
K19
HA + R

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

For elementaryy steps

p of
a family of reactions, all
involving geometrically
similar reactants (so that
steric effects are about
the same for each),
there is a simple
relationship between the
activation energies
g
and
the energies of reaction.
Eact = const ' q
'

isaconstantbetween0and1

The Bronsted relationship is developed for the sequence

elementary
l
t
steps
t
by
b application
li ti off P
Polanyi
l
i relationship
l ti
hi tto
the rate determining step:
k 20 = constK 20a '
r = k 20C RH + C A = k 20 K19C R C HA
'
r = constK19 K 20
C R C HA

TheequilitriumconstantsK19 andK20 arerelatedtotheacid

dissociationconstantKa
C C +
K19 = A RH
C HAC R

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.

The goal of the development is a relationship between

rate constant and acid strength for a series of acids
catalyzing a particular reaction. Similarly,
C C +
K19 = A RH
C HAC R

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 '

Catalysis in concentrated strong

acid solutions

What explains this

dependence of the rates of
some acid-catalyzed
reactions in aqueous
solution on H0?

Consider
C
id th
the ffollowing
ll i
mechanism as a
hypothetical example:

R + H + RH + * RH +
RH + H + + P

According to the transition theory,

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

Catalysis by acids and bases proceeds via cycles involving

proton transfer reactions, and solvent molecules like water
often play a role.
Reaction can be investigated in the absence of
complicating solvent effects if the catalyst and reactants are
maintained in a gas phase
phase.
Gas phase reactions catalyzed by acids and bases are
unusual.
An example of acid catalysis in the gas phase is the
dehydration of alcohol in the presence of HBr molecules.

38

Both bond breaking and bond

forming involve the motion of
protons.

The catalyst donates a proton

to the reactant at one position
and retrieves a proton from
another position.

As a consequence of the
proton donation, the alcohol
becomes more reactive for
the splitting out of a water
molecule and a proton.

39

Catalysis in dilute aqueous

solutions

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.

The mechanism shown here is

an oversimplification because
the hydration shells around the
species in solution are not
represented.

41

The reaction mechanism is consistent with the observed

kinetics, namely,

r = kCH + Cacetal

The decomposition
p
of the
protonated acetal is slow and
may be assumed to be rate
determining step
step.

From the rate-determining step,

the rate of the overall cycle is
determined to be:

Therefore:

K=

C protonated

acetal

C H + Cacetal

r = k ' C protonated

acetal

r = k ' KC H + Cacetal
42

A commericial process for the manufacture of bisphenol

A (2,2-bis-4-hydroxyphenylpropane), an important
intermediate in the manufacture of epoxy resins and
polycarbonates, involves the acid
acid-catalyzed
catalyzed
condensation reaction of phenol and acetone.

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

The mechanism is almost never determined unequivocally by the

kinetics.

This point is illustrated by the present example. If the rate-determining

step were, for instance, the protonation of the acetal, then the rate
equation would take the same form as that above.

More than one possible mechanism of the catalytic reaction is

consistent with the form of the empirical rate equation for the overall
catalytic cycle.

The conclusion is general: determination of reaction mechanisms

requires much more than determination of kinetics.

45

The kinetics becomes more complicated as the solution

becomes more concentrated in acid.

The hydrolysis of benzamide in solutions of HCl and solutions of

H2SO4.

46

Catalysis in concentrated strong

acid solutions

Catalysis in highly concentrated strong-acid solutions is especially

complex in part because there are various proton donors and they
complex,
are not all identified.

It is not easy to measure the concentration of the proton donors.

Some quite general results have emerged, however, from

correlations of catalytic activity with empirical measures of the
solutions acidity.

The Hammett acidity function, defined as a correlates with the

catalytic activity of the solution in many examples of acid catalysis
that involve protonation of neutral reactant molecules.

47

In dilute aqueous solutions of strong acids, the proton donor

strength of the solution is measured simply by the
concentration
t ti off hydrated
h d t d protons,
t
given
i
by
b pH.
H

This measure is not adequate for highly concentrated acid

solutions in which the solution is no longer predominantly
water.

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

The acid dissociation constant

of AH+ is, by definition,
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

-H
H0

C AH +
CA

C AH +
CA
49

Suppose that in a catalytic cycle taking place in an aqueous

solution of a strong acid, the protonation of a neutral reactant
molecule (base) is a kinetically significant step
step.

A relationship between the reaction

rate and the Hammett acidity
function.

The rate is proportional to the

hydrogen ion concentration only in
the limit as zero acid concentration
pp
is approached.

Can be explained by the transition

state theory.

50

There are many examples of acid-catalyzed reactions in

concentrated strong-acid solutions for which the rate is a
simple
p function of H0.

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

Unfortunately, it is difficult to predict when either of these

dependencies will prevail
prevail, and often neither one describes the
data.

Some of the complications arise from the various roles of

water in the catalytic cycles.

Consideration of the hydrogen of various species leads to a

more general representation.
representation
51

C t l i b
Catalysis
by b
bases

Thus far in this treatment of acid-base catalysis, the

p gap
proton from the
reactant has been the base,, accepting
catalyst, HA, or H+, or other proton donors.

The developments are similar when the roles are

reversed and the catalyst is the base.

Many reactions are catalyzed efficiently in either acidic

or basic
b i solution.
l ti

52

Consider one of the best understood of these reactions

reactions, the
iodination of acetone. In acidic condition,

53

The sequence of elementary steps:

Rate limiting step,

The steps following it

sum up to give,

The overall reaction

stoichiometry,
The kinetics,

r = kC A C protonated

acetone

= kKCacetoneC HA
54

Contrast this mechanism with that prevailing in alkaline

solution. The mechanism of this general-base-catalyzed
reaction can be represented as,

55

C t l i b
Catalysis
by metal
t l iions

Catalysis by hydrogen ions is the most common type of

acid catalysis in solutions, but not the only type. Metal
ions other than hydrogen
h drogen ma
may ffunction
nction similarl
similarly.

Examples are manganese, copper, and zinc ions in

aqueous solutions
solutions.

Metal ions act as catalysts by bonding to organic

reactants, introducing charge into them, and often
polarizing them and inducing formation of carbenium
ions.

56

A metal ions (a Lewis acid) may be superior to a

Bronsted acid (proton donor) in several respects,

It may introduce a multiple positive charge into a

p
can introduce onlyy a single
g
reactant,, whereas a proton
positive charge.

It can exist in a neutral solution, not just acidic solutions.

It can coordinate to several donor atoms simultaneously.

Whereas the proton usually coordinates to only one.

A metal ions may act as a catalyst without changing its

oxidation state.
57

Cations catalyze numerous reactions,

Ester and amide hydrolysis

y
y
reactions.
Decarboxylation reaction (forming CO2).
Phosphate cleavage reactions.
Cations in enzymes play roles similar to those in solutions.

58

C t l i b
Catalysis
by electron
l t
ttransfer
f

The preceding sections illustrated a rich chemistry in

which many of the elementary steps are transfers of
protons.
protons
These steps are often rapid because the mass of the
y g atom is so low.
hydrogen
Another kind of elementary transfer process is also
rapid: the transfer of single electron.
Th
There
are the
th predominant
d i
t processes iin redox
d reactions,
ti
that is, the reactions that involve changes in reactant
oxidation states.
59

C t l i iin solutions
Catalysis
l ti

Catalysis
y
by
y electron
transfer.
Simple

redox reactions

Oxidation

involving freeradical intermediates.

60

Simple redox reactions

An example
p of a redox reaction taking
gp
place in aqueous
q
solutions is:

V 3+ + Cu 2+ V 4+ + Cu +

This is a transfer of one electron and an example of one

of the simplest kinds of redox reaction.
It can result from the collision of the two cations, with the
transfer of an outer-sphere electron.
The collisions of ions of the same charge are not very
likely, and water of hydration may hinder the process.
Water may serve as an intermediary, receiving an
electron to form a hydrated electron and then donating
an electron to another ion.
61

A more complex redox reaction is , for example,

Tl + + 2Ce 4+ Tl 3+ + 2Ce 3+

It involves a change of two units in the oxidation state of

thallium ions.
Elementary step to involve two Ce4+ ions and one Tl+
ions to proceed relatively slowly because of the
infrequency of three-body collisions of species all having
the same charge.
A more efficient
ffi i t way to
t carry outt reaction
ti is
i to
t take
t k
advantage of an intermediary, a redox pair such as
Cu2+/Cu+ or Ag2+/Ag+, which can be involved in rapid
one-electron
l
transfer.
f
62

Ce 4+ + Ag + Ce 3+ + Ag 2+
Ag 2+ + Tl + Tl 2+ + Ag
A
A +
Tl 2+ + Ce 4+ Tl 3+ + Ce 3+

Kinetics data show that second

step is rate determining.
determining

r = kC Ag 2+ CTl +

63

The intervention of the Cu+/Cu2+ redox pair can even

accelerate redox reactions that otherwise might take
place via a simple one-electron
one electron transfer, such as,
2+

F +V
Fe

4+

3+

Fe
F +V

3+

The reason for the catalytic activity in this example is

that the one-electron transfers involving copper are more
rapid the one-electron
one electron transfer involving iron and
vanadium, which is hindered by the solvation shells of
the ions.
64

O id ti iinvolving
Oxidation
l i ffreefree-radical
di l
intermediates

Electron transfer processes are also important in organic

chemistry.

The organic redox reactions often involve free-radical

i t
intermediates,
di t
and
d many occur iin catalytic
t l ti oxidation.
id ti
65

Reactions leading to the formation of organic free

radicals are common, and often organic peroxides may
form.
form
The catalytic site typically plays a role in the initiation
process, helping to generate free radicals and start a
chain reaction.
Often free radicals are generated by metal-catalyzed
p
of organic
g
hydroperoxides.
y p
decomposition
Metal complexes differ greatly in their abilities to catalyze
oxidation reactions selectively.
Many oxidations of organic reactants in the liquid phase
take place almost spontaneously and called
autoxidations.
66

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

2 RO2 RO4 R O2 + nonradical products

67

The hydroperoxide product may be obtained in high yield.

It may also be an intermediate, undergoing further
conversion.

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

The role of the metal in this scheme is that of a redox

initiator rather than a catalyst
y in the traditional sense.
Only appropriate metals are those that undergo electron
transfer giving changes of one unit in the oxidation state.
The rate of the overall process depends on the redox
potential of the Mn+/M(n-1)+ couple.
68

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

RO + RO2 H RO2 + ROH

69

Most liquid phase transitionmetal-catalyzed

metal
catalyzed oxidations of
organic compounds is
autoxidation.

Nonetheless, there are some

that do not involve free radicals.

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