Lectures 19-21 Itkulova S.S.

Acid base and redox catalysis

-General characteristics and basic concepts

- Redox / Electron Catalysis
-Acid-base / ion catalysis
- Bronsted and Lewis Acid Centers
-

Лекция 16
Classification of catalytic reactions according
to the mechanism of catalyst action
For a general orientation in selection of the catalysts it is useful to
classify the catalytic processes according to the mechanism of action of
the catalysts.

According Roginsky, the catalytic reactions can be divided into two

broad classes:
- the oxidation-reduction (electron), and
- acid-base (ionic).
 Classification of catalytic reactions :
The first class
The first class includes the processes related to the transition of
electrons: oxidation, reduction, hydrogenation, dehydrogenation,
decomposition of some oxygen-containing compounds as H2O2, N2O,
KClO4.

Typical catalysts for these are metals and semiconductors, i.e.

substances having a movable and easily excited electrons (or holes).
The most common catalysts of this class are transition metals,
particularly Group VIII metals (Pt, Pd, Rh, Rh, Fe, Co, Ni) and 1b group
(Cu, Ag, Au); transition metal compounds: simple oxides of V2O5,
MnO2, Cr2O3, MoO3, Nb2O5), mixed oxides, spinels (Fe3O4, CuCr2O4,
ZnCr2O4), perovskite (CaTiO3, NaNbO3, NiLaO3 etc.), sulphides (MoS2,
WS2, NiS, Co9S8. ), as well as some semi-conductors without transition
elements in their composition (ZnO, ZnS).
Homolytic and heterolytic reactions
This classification, in general, corresponds to the classification of homogeneous
reactions in organic chemistry by the mechanism of an elementary act:
• homolytic and
• heterolytic.
In the elementary act of the homolytic reaction, the electrons of the two-electron pair
forming a chemical covalent bond are separated
A∙|∙B.

In heterolytic reactions, the formation and destruction of chemical bonds proceed

without separation of an electron pair.
For example, for a water molecule, a homolytic O–H bond cleavage leads to the
formation of free radicals:
H2O → H∙ + OH∙,

and a heterolytic one leads to the formation of the proton and hydroxyl ion:
H2O →H+ + OH–.

Metals and semiconductors can supply the electrons necessary for homolytic bond
cleavage and the reaction running through the redox path. In solids, the surface atoms
can be donors (bases) or acceptors (acids) of an electron pair, and interact with reagents
by the heterolytic (donor-acceptor) mechanism and accelerate acid-base reactions.
The second class of catalytic reactions
according to the mechanism of action
The second class includes reactions of acid-base
interaction: catalytic cracking, hydration, dehydration,
hydrolysis, many reactions of isomerization, polymerization,
condensation of organic substances.
Typical catalysts of this class are solids with acidic
(amorphous and synthetic aluminosilicates, Al2O3, ThO2,
superacids: high silicon zeolites, heteropolyacids) and
basic (MgO, CaO) properties.
Most often, these are ionic dielectric crystals or
amorphous non-conductive solids.
 The third class of catalytic reactions
according to the mechanism of action
The third class - the catalysis by coordination compounds may be
separated. Coordination bond is a donor-acceptor bond, which is occur in
complex compounds. The number of links (n) of the central (metallic) M atom
with other atoms or groups – ligands L – MLn in the complex is greater than the
formal valence of the metal
Catalysis by coordination compounds at low temperature is typical, in
particular, for homogeneous catalysis.
 Coordination compounds
Ammonia, water, and many other Lewis bases react
with metal ions to form a group of species known
as coordination compounds. The reaction to form these
species is another example of a Lewis acid-base
reaction.
For example, the light blue colour of a solution of
Cu2+ ions in water is due to the [Cu(H2O)6]2+ ion. If
ammonia is added to this solution, the water molecules
attached to copper are replaced by ammonia
molecules, and the beautiful deep blue ion
[Cu(NH3)4]2+ is formed.
Change in reaction mechanism depending
on the type of catalyst
Actual rules for catalysts selection are often more complicated. The
same reaction in different conditions and over different catalysts can
occur through the oxidation-reduction (homolytic) and acid-base
(heterolytic) mechanisms. For example, dehydrogenation of isopropyl
alcohol reaction
(CH3)2CHOH → (CH3)2CO + H2
catalyzed by metals and semiconductors.

In this reaction, electrons and a holes are of solid body involved in

homolytic breaking of C–H and O–H bonds. However, the catalysts of
this reaction are also solid base: CaO, MgO, on which the breaking of
bonds C–H and O–H occurs by heterolytic way.
 1. ACID–BASE CATALYSIS

Acid–base catalysis - acceleration of a chemical reaction

by the addition of an acid or base, the acid or base itself
not being consumed in the reaction.

The catalytic reaction may be acid-specific

(acid catalysis), as in the case of decomposition of the
sugar sucrose into glucose and fructose in sulfuric acid;
or base-specific (base catalysis), as in the addition
of hydrogene cyanide to aldehydes and ketones in the
presence of sodium hydroxide.

Many reactions are catalyzed by both acids and bases.

 Acid catalysis

Acid catalysis is employed in a large number of industrial

reactions, among them the conversion of
petroleum hydrocarbons to gasoline and related products. Such
reactions include decomposition of high-molecular-weight
hydrocarbons (cracking) using alumina–
silica catalysts (Brønsted–Lowry acids), polymerization of
unsaturated hydrocarbons using sulfuric acid or hydrogen
fluoride (Brønsted–Lowry acids), and isomerization of aliphatic
hydrocarbons using aluminum chloride (a Lewis acid).

Among industrial applications of base-catalyzed reactions is

the reaction of diisocyanates with polyfunctional alcohols in the
presence of amines, used in the manufacture of polyurethane
foams.
 The mechanism of acid- and base-
catalyzed reactions

The mechanism of acid- and base-catalyzed reactions is

explained in terms of the Brønsted–Lowry concept of acids and
bases as one in which there is an initial transfer of protons from
an acidic catalyst to the reactant or from the reactant to a
basic catalyst. In terms of the Lewis theory of acids and bases,
the reaction entails sharing of an electron pair donated by a
base catalyst or accepted by an acid catalyst.
 Brønsted–Lowry theory

Brønsted–Lowry theory, also called proton theory of

acids and bases, a theory, introduced independently in 1923 by
the Danish chemist Johannes Nicolaus Brønsted and the English
chemist Thomas Martin Lowry, stating that any compound that
can transfer a proton to any other compound is an acid, and the
compound that accepts the proton is a base.

A proton is a nuclear particle with a unit positive electrical

charge; it is represented by the symbol H+ because
it constitutes the nucleus of a hydrogen atom.
 The Brønsted-Lowry theory

A somewhat more general acid-base theory,

the Brønsted-Lowry theory, named after Danish
chemist Johannes Nicolaus Brønsted and English chemist
Thomas Martin Lowry, defines an acid as a proton donor
and a base as a proton acceptor.

In this theory, the reaction of an acid and base is

represented as an equilibrium reaction.

acid (1) + base (2) ⇌ base (1) + acid (2)

(The double arrows, ⇌, indicate that the products can re-

form the reactants in a dynamic process.)
 Brønsted–Lowry scheme
According to the Brønsted–Lowry scheme a substance
can function as an acid only in the presence of a base;
similarly, a substance can function as a base only in the
presence of an acid. Furthermore, when an acidic
substance loses a proton, it forms a base, called
the conjugate base of an acid, and when a basic substance
gains a proton, it forms an acid called the conjugate acid of
a base. Thus, the reaction between an acidic substance,
such as hydrochloric acid, and a basic substance, such
as ammonia, may be represented by the equation:
 Brønsted–Lowry theory

In the equation the ammonium ion (NH+4 ) is the

acid conjugate to the base ammonia, and the
chloride ion (Cl-) is the base conjugate to
hydrochloric acid.

The Brønsted–Lowry theory enlarges the number

of compounds considered to be acids and bases to include not only
the neutral molecules (e.g., sulfuric, nitric, and acetic acids, and
the alkali metal hydroxides) but also certain atoms and molecules
with positive and negative electrical charges (cations and anions).
The ammonium ion, the hydronium ion, and some hydrated metal
cations are considered acids. The acetate, phosphate, carbonate,
sulfide, and halogen ions are considered bases.
 The Brønsted-Lowry theory

Acid (1) and base (1) are called a conjugate acid-

base pair, as well as acid (2) and base (2).

The advantage of this theory is its predictive capacity.

Whether the equilibrium lies toward the reactants

(reactant-favoured) or the products (product-favoured)
is determined by the relative strengths of the acids
and bases.
 The Brønsted-Lowry theory
The Brønsted-Lowry theory is often closely associated with the solvent water.
Dissolution of acid in water to form the hydronium ion and the anion of the acid is
an acid-base reaction. Acids are classified as strong or weak, depending on whether the
equilibrium favours the reactants or products.
Hydrochloric acid, a strong acid, ionizes completely in water to form the hydronium
and chlorine (Cl−) ions in a product-favoured reaction.

HCl(aq) + H2O (l) → H3O+(aq) +Cl−(aq)

Using the Brønsted-Lowry theory, the reaction of ammonia and hydrochloric acid in
water is represented by the following equation:

NH3(aq) + HCl(aq) → NH4+(aq) + Cl−(aq)

Hydrochloric acid and the chlorine ion are one conjugate acid-base pair, and the
ammonium ion and ammonia are the other. The acid-base reaction is the transfer of
the hydrogen ion from the acid (HCl) to the base (NH3). The equilibrium favours the
weaker acid and base, in this case the products.
Note that the hydroxide ion does not appear in this equation, a
point differentiating the Arrhenius and Brønsted-Lowry theories.
 Lewis theory
Lewis theory, generalization concerning acids and bases
introduced in 1923 by the U.S. chemist Gilbert N. Lewis, in which
an acid is regarded as any compound which, in a chemical
reaction, is able to attach itself to an unshared pair of electrons
in another molecule. The molecule with an available electron pair
is called a base. The reaction between an acid and a base
(neutralization) results in the formation of an addition compound,
in which the electron pair that constitutes the chemical bond
comes from only one reactant. Included in the Lewis definition of
acids are the metal ions; the oxides of certain nonmetallic
elements, such as sulfur, phosphorus, and nitrogen; substances
able to donate hydrogen ions or protons; and certain
solid compounds, such as aluminum chloride, boron trifluoride,
silica, and alumina.
 Lewis acids

In practice, substances that are considered as acids by

the Lewis definition, other than those associated with
hydrogen ions and protons, are specifically referred to as
Lewis acids. Lewis bases include ammonia and its organic
derivatives, the oxides of the alkali and alkaline earth
metals, and most atoms and molecules with negative
electric charges (anions).
 ACID AND BASE THEORY
Even general acid and base theory was proposed by American
physical chemist Gilbert Newton Lewis. In the Lewis theory, bases are
defined as electron-pair donors and acids as electron-pair acceptors.
Acid-base reactions involve the combination of the Lewis acid and base
through sharing of the base’s electron pair.
Ammonia is an example of a Lewis base. A pair of electrons located
on the nitrogen atom may be used to form a chemical bond to a Lewis
acid such as boron trifluoride (BF3).
(In the following equation, the colon represents an electron pair.)

H3N: + BF3 → H3N–BF3

 Ion (Acid-base) catalysis
Acid-base, or ion, catalytic reactions are such catalytic reactions,
which are described by eliminating or addition of a hydrogen ion
(proton), and reactions in which free electron pair of the reactants or
catalyst moves without separation of electrons, forming a coordination
bond in the complex compound. According to the Lewis theory, acids
are compounds whose molecules are able to attach a pair of electrons,
i.e. to include it in the electron shell of one of its atoms.
The bases are compounds in which the molecule has a lone pair of
electrons that can be introduced into the electronic layer of acid. This is
the most common treatment of acids and bases concepts. From this
viewpoint, the group of acids other than conventional acid substances
fall and those compounds not containing hydrogen as Al2O3, FeCl3,
ZnCl2, BF3. All of these substances - complexing catalysts.
Acid-base catalytic reactions include catalytic cracking,
polymerization, isomerization, hydration of hydrocarbons and a number
of other transformations.
 Ion catalysis. Acids and bases
Ion catalysis. In the ion (heterolytic) catalysis catalysts are
acids and bases. The catalytic activity of acid and base is
determined by their capacity to exchange with reacting molecule
the ions or a pair of electrons to form an intermediate compound
of ionic type, having high reactivity.
Since there is currently no unambiguous definition of acids
and bases, let us consider briefly the basic provisions of the
proposed theories of acids and bases.
Early theories, as acids, assumes substances containing
oxygen (oxygen theory Lavoisier) or hydrogen (hydrogen
Liebig's theory). In Arrhenius theory of electrolytic dissociation
there are following definition: the acids and bases are
substances which dissociate in aqueous solution to form H+ and
OH– ions, respectively. This theory was fully confirmed though, it
is a special case of a more general theory.
Brønsted–Lowry protonic theory of acids
and bases

According to the protonic theory of Brønsted–Lowry,

acid and base are substances (neutral molecules or ions)
which are donor or acceptor of the proton respectively, i.e.

HA ↔ H+ + A–.
acid proton base
Disadvantages of Brønsted-Lowry protonic
theory:
AH + H 2O ↔ H 3O+ + A–;
acid acid base
NH3 + H 2O ↔ NH4+ + OH–,
base acid acid base
wherein pairs of conjugate acid and base are in a first reaction AH and
A–, H3O+ and H2O, and the second – NH4+ and NH3, H2O and OH–.
As seen from these examples, water and ammonia can act as a
base and as an acid. Substances capable of both giving and attach a
proton, called amphiprotic. Acids and bases are not only molecules but
can be also ions.
Thus, in Brønsted-Lowry theory acid hallmark is the presence of a
proton in its molecule. This theory does not consider the existence of
acidic substances not containing hydrogen, e.g., SnCl4, BF3, AlCl3,
ZnCl2, aluminosilicate, zeolite, and others. Disadvantages of proton
theory corrected and supplemented in the electronic Lewis theory of
acids and bases.
 Lewis electron theory
From the Lewis theory, the acid and the base are the
substances that are respectively donor and acceptor of electron
pairs. Lewis acid (L-acid) and bases may not contain protons
and are therefore aprotic. The acid-base interaction is the
formation of a donor-acceptor type bond

base acid salt

Most cations are the L-acids, and anion - Lewis bases. Salt -
typical acid-base complexes. As can be seen, the Lewis electron
theory considers acids and bases more widely than any other
theory.
 Types of acid-base catalysis
1. Specific acid catalysis contains reactions catalyzed by
hydrogen ions.
2. Specific basic catalysis includes reactions catalyzed by
hydroxyl ions. Intermediates are anions formed as a result of
the addition of a base or as a result of the elimination of a
proton by a catalyst from a reactant.
3. General acid - base catalysis includes reactions catalyzed by
Bronsted acids and bases. Electrophilic particles and Lewis
acids, which act as a proton, take part in the activation of the
reagent molecule.
4. Electrophilic - nucleophilic catalysis contains reactions
catalyzed by donors or acceptors of electron pairs.
 Activity of protic and aprotic acids
Aprotic Lewis acids (AlCl3, BF3, ZnCl2, SbF5) often catalyze
the same reaction as the protic Brønsted acid, wherein the
aprotic acid activity is sometimes higher than proton. This is due
to the fact that in aqueous media (e.g., catalytic cracking in the
presence of steam) aprotic acids are converted into protic ones:
AlCl3 + H2O → AlCl3 (OH)–H+,
and in the coexistence of the two types of acids the acidity is
amplified, and hence the catalytic activity by the formation of a
strong protic Brønsted acids (superacids):
AlCl3 + HCl HAlCl4 ↔ H+ + AlCl4–,
BF3 + HF HBF4 ↔ H+ + BF4–,
SbF5 + HF HSbF6 ↔ H+ + SbF6–,
(the strongest acid known, is dissolved SbF5 in HF).
Type of super-acid
 Carbocations: carbenium ions, carbonium ions.
Сarbenium ion catalysis
In oil refining initial (intermediate) compound formed by reacting of
hydrocarbon with an acid catalyst commonly called carbenium ion or
carbocation and catalysis, correspondingly, carbenium ion.
Carbocations are most easily formed by proton transfer from the
Brønsted acid catalyst to the olefin molecule, which may be formed by
thermolysis of hydrocarbons:
RCH=CH2 + H+A- → RCH-CH2H+ + A- → RC+HCH3 + A–
Carbocation formed by the interaction of a proton with an olefin,
called carbenium ion. The term "carbonium ion" is often incorrectly
used in the literature refers to carbocations resulting from proton
addition to paraffin:
CH4 + H+ → CH5+, C2H6 + H+ → C2H7+, etc.
Carbocation formation may also occur directly from an alkane by
removal of a hydride ion under protic or aprotic center of the catalyst:
R-H + H+ → R+ + H2,
RH + L → R+ + LH–.
 Formation of carbenium ions
When olefin attacked by proton π-electrons of the double bond are used to
form a new (σ-bond between the proton and one of the carbon atoms forming
the double bond while the second carbon atom of hydrocarbon is positively
charged. Thus, the carbenium ion is an intermediate structure between the
olefin having π-bond, and paraffin, which has only σ-bond.
During reaction of olefin with proton, the formation of two different
carbenium ions is possible:
RCH2–CH+ – primary carbenium ion
RCH=CH2 + H+
RC+H–CH3 – secondary carbenium ion
Calculations indicate that the heat of formation of primary carbenium ions
is 81 kJ/mol higher than that for the secondary one and +61 kJ/mol higher than
that for the tertiary. Consequently, the primary carbenium ions transforms
rapidly into tertiary ones.
The main reactions of carbocations as well as for radicals are unimolecular
decay according to the β-rule and bimolecular reactions of substitution and
addition. The essential difference of carbocations from radicals – the capability
of the first for isomerization, due to a significant decrease in free energy during
the transition from primary to secondary and tertiary carbocations.
 REDOX CATALYSIS
(electron catalysis)
Redox catalysis is a special class of catalytic reaction wherein a
chemical transformation (usually organic chemical reaction) is
catalyzed by an inorganic reagent.

They usually show net change in oxidation state after a cycle

of reactions is complete, but catalyze two or more organic molecules
to react via.

A redox catalyst is a compound that has at least two oxidation

states that are kinetically more facile than the oxidation states of the
reactants and products upon which the catalyst is operating.
A redox (or oxidation-reduction) reaction is a type of chemical
reaction that involves a transfer of electrons between two species.

Redox reactions are reactions where a transfer of electrons occurs,

by other words there is a disconnection of electron pair. There is a
transfer of electrons if there is any change in the oxidation number
between the reactants and the products.
 REDOX REACTIONS
(electron catalysis)
Oxidation-reduction reaction, also called redox reaction, any chemical
reaction in which the oxidation number of a participating chemical species
changes. The term covers a large and diverse body of processes. Many
oxidation-reduction reactions are as common and familiar as fire, the rusting
and dissolution of metals, the browning of fruit,
and respiration and photosynthesis—basic life functions.

Redox reactions:
➢ Oxydation,
➢Hydrogenation
➢Dehydrogenation
➢ etc (Combustion reactions, Disproportionation reactions, Single
replacement reactions)
 The chemical reactions involve movement of electrons from one atom to another.
Therefore, it is appropriate to characterize the chemical reactions as redox reactions,
and all catalysis as redox catalysis.

However, redox catalysis is a special class of catalytic reaction wherein a chemical

transformation (usually organic chemical reaction) is catalyzed by an inorganic reagent.

There is a class of reactions called atom-transfer reactions (also known as free

radical chain reactions) where odd-electron species (free radicals) are reaction
intermediates.

These reactions are, by nature, redox reactions. There is usually a free radical
initiator that kicks off the chain of reactions, and propagation reactions (this is a
reduction reaction for the organic molecule) of reactions occur with the intermediacy of
free radicals. Reaction termination occurs by “quenching” the organic free radical by
either oxygen or a metal that can accept an electron (this is an oxidation reaction for the
organic molecule) resulting in a neutral product.

Transitions metals (e.g. Cu, Fe, Cr, Ni) are all capable of initiating and terminating
(reduction and oxidation, or redox) organic reactions. They usually show net change in
oxidation state after a cycle of reactions is complete, but catalyze two or more organic
molecules to react via. atom transfer reactions. Kharasch reaction (anti-Markovnikov
addition of HBr or CHCl3 using peroxide initiators and a metal catalyst) is a good
example of a redox catalytic reaction. See reference below for details….
 Electron catalysis
 Electron catalysis. In case of the electron (redox) catalysis
accelerating effect of catalysts achieved by relief of electron
transitions in homolytic reactions due to the free electrons of
the transition metals.
 The transition metals are active catalysts in the vast majority
of redox reactions. Iron, for example, is a classic ammonia
synthesis catalyst. Cobalt, nickel, copper and platinum group
metals are highly active in the processes of hydrogenation and
dehydrogenation, and oxidation. Silver is virtually the only
catalyst for the partial oxidation (for example ethylene to its
oxide).
 A characteristic feature of the transition metals is
incompleteness of electron d-shell defining their specific
chemical (variable valency propensity for complexation), many
physical (formation of a metal-type crystals, the work function
of the metal electron, conductivity, magnetic properties, and
others) and catalytic properties.
 Electron catalysis
In the crystalline state part of the electrons of the d-shell
passes to the conduction band, and there is the possibility
of electron exchange between the d- and outer s-shell.
Energy ease of such a transition (determined by the
electron work function metal) leads to that certain number
of free electrons is produced on the outer surface of the
crystal. Their presence leads to the appearance of free
valences on the surface – positive in the case of a free
electron (electron-donor conductivity) and negative in the
case of absence of an electron (electron-acceptor, the so-
called "hole" conductivity) in the particle on the surface of
the crystal. The number of free valencies will increase
exponentially with increasing temperature.
Simultaneous occurrence of both mechanisms
Under certain conditions, the same molecule can be
both of electron donors or acceptors. Alternatively, at the
surface of the catalyst both types of chemisorption
mechanisms can occur simultaneously: at the some sites
surface is a donor, and at another ones – electron acceptor.
As an example, a simplified reaction scheme of CO
oxidation in excess oxygen on platinum (Eley-Rideal
model) can be provided:
1.O2 + 2Pt ↔ 2OPt (Pt – e– donor).
2.OPt + CO ↔ COOPt.
3.COOPt ↔ CO2 + Pt (Pt – e– acceptor),
 Bifunctional catalysis
bifunctional catalysis occurs in other important industrial
processes, in which some stages of complex reaction proceeds
by an ionic, and others by electronic mechanism. By such ion-
electron mechanism, reaction of aromatization
(dehydrocyclization) of normal alkanes and five-membered
naphthenes in the catalytic reforming of gasoline, destructive
hydrogenation reaction during hydrocracking and isomerization
of C4–C6 alkanes are carried out.
Naturally, catalysts for bifunctional catalysis should contain
both types of catalytic sites – metallic (m.s.) and acidic (a.s.) at
the same time. Thus, polymetallic alumina platinum reforming
catalyst is a platinum modified by rare earth metal (e.g., Re), on
a support – alumina promoted by acid (chlorine). The
hydrocracking catalyst, e.g., (or alumina nickel molybdenum
zeolite), Co + Mo or Ni + Mo perform a hydro-dehydrating
function, and zeolite is an acidic component.
Examples of bifunctional catalysis
Reaction of dehydrocyclization of n-hexane

Reaction of hydrocracking of n-C16H34

Reaction of isomerization of n-butane

*Error in equation 2!! ** м.ц. – metallic center (m.c.)

***к.ц. – acidic center (a.c)