CRITICAL BOOK REPORT

CATALYTIC PROPERTIES OF TRANSITIONAL METAL

ELEMENTS AND COMPOUNDS

Arranged to Fulfill Task of Transitional Metal Chemistry Course

Lecturer: Dr. Iis Siti Jahro, M. Si.

Name: Felix Valentino Sianturi

NIM: 4183131033
Class: Chemistry Education Study Program 2018

STATE UNIVERSITY OF MEDAN

FACULTY OF MATH AND SCIENCE
CHEMISTRY EDUCATION STUDY PROGRAM
 PREFACE

First of all, I express my gratitude to the presence of Almighty God, because I

have given His grace and health, so that I can complete the task of "CRITICAL
BOOK REPORT". This task is made to fulfill one of my courses, namely the
"Transitional Metal Chemistry" course.
The task of this critical book report is arranged in the hope that it can add to
all of our knowledge and insights, especially in terms of catalytic properties of
transitional metal elements and compounds. I realize that this critical book report
assignment is still far from perfection, if in this task there are many shortcomings and
mistakes, I apologize because my knowledge and understanding are still limited.
I am also grateful to have known Ma’am Dr. Iis Siti Jahro, M. Si., who
incessantly encouraged us not to stop reading and writing, because that is the form of
contribution that should be given by academics in addition to other forms of
contribution given. Through conversation and discussion, we have learned a lot from
Ma’am how important the transitional metal elements are.
Therefore, I am looking forward to suggestions and criticisms from readers
who are of a constructive nature to perfect this task. I hope that this critical book
report assignment can be useful for readers and for me in particular. For your
attention I would like to thank.

Medan, February 19th, 2021

Author
CONTENTS
 CHAPTER I
PRELIMINARY

1.1 Background
A catalyst is a substance that increases the rate of a reaction but is not
itself consumed. Catalysts are widely used in nature, in industry, and in the
laboratory, and it is estimated that they contribute to one-sixth of the value of all
manufactured goods in industrialized countries. For example, a key step in the
production of a dominant industrial chemical, sulfuric acid, is the catalytic
oxidation of SO2 to SO3. Ammonia, another chemical essential for industry and
agriculture, is produced by the catalytic reduction of N2 by H2. Inorganic catalysts
are also used for the production of the major organic chemicals and petroleum
products, such as fuels, petrochemicals, and polyalkene plastics. Catalysts play a
steadily increasing role in achieving a cleaner environment, for example, the
destruction of pollutants (as with the catalytic converters found on the exhaust
systems of vehicles), the development of better industrial processes that are more
efficient with higher product yields and fewer unwanted byproducts and in clean
energy generation in fuel cells. Industrially important catalysts are almost
invariably inorganic. Enzymes, a class of biochemical catalysts, often with a
metal ion at the centre of a complex molecule (Shriver)
Catalysts containing d-block metals are of immense importance to the
chemical industry: they provide cost-effective syntheses, and control the
specificity of reactions that might otherwise give mixed products. The chemical
industry (including fuels) is worth hundreds of billions of US dollars per year.
The search for new catalysts is one of the major driving forces behind
organometallic research, and the chemistry in many parts can be understood in
terms of the reaction types. Current research also includes the development of
environmentally friendly ‘green chemistry’, e.g. the use of supercritical CO 2
(scCO2) as a medium for catalysis (Catherine).
Through this CBR assignment, it is hoped that we will be able to identify
the terms of catalyst, reaction catalytic, homogeneous catalyst and heterogeneous
catalyst. We also should be able to describe the workings of homogeneous and
heterogenous catalysts and the kinds of catalytic reactions that use transition
metal elements or compounds.

1.2 Formulation of the Problems

From the explanation above, we can formulate several problems such as:
1. What are the terms of catalyst, reaction catalytic, homogeneous catalyst and
heterogeneous catalyst?
2. How does the working mechanism of homogenous catalysts?
3. What are the types of catalytic reactions in homogeneous catalysts of
transition metal elements or compounds?
4. How does the working mechanism of heterogenous catalysts?
5. What are the types of catalytic reactions in heterogenous catalysts of
transition metal elements or compounds?

1.3 Purposes
From the formulation of problems that have been formulated, the
purposes of this CBR are:
1. To identify the terms of catalyst, reaction catalytic, homogeneous catalyst and
heterogeneous catalyst.
2. To describe the working mechanism of homogenous catalysts.
3. To describe and to explain the types of catalytic reactions in homogeneous
catalysts of transition metal elements or compounds.
4. To describe the working mechanism of heterogenous catalysts.
5. To describe and to explain the types of catalytic reactions in heterogenous
catalysts of transition metal elements or compounds.
 CHAPTER II
SUMMARY OF BOOKS

From 2 books that have been reviewed and summarized specifically on the
material of catalytic properties of elements and transition metal compounds, so I can
compile the information about the terms of catalyst, reaction catalytic, homogeneous
catalyst and heterogeneous catalyst.
2.1 Terms of Catalyst
A catalyst is a substance that increases the rate of a chemical reaction
without itself being consumed (Brian).
The term catalyst is often used to encompass both the catalyst precursor
and the catalytically active species. A catalyst precursor is the substance added to
the reaction, but it may undergo loss of a ligand such as CO or PPh 3 before it is
available as the catalytically active species. Although one tends to associate a
catalyst with increasing the rate of a reaction, a negative catalyst slows down a
reaction. Some reactions are internally catalyzed (autocatalysis, one of the
products is able to catalyze the reaction) once the reaction is under way, e.g. in
the reaction of [C2O4]2- with [MnO4]-, the Mn2+ ions formed catalyze the forward
reaction (Catherine).

2.2 Reaction Catalytic

2.3 Homogenous Catalysts

2.3.1 Terms of Homogenous Catalyst
A homogeneous catalyst is in the same phase as the components of the
reaction that it is catalyzing (Catherine). In homogeneous catalysis, the reactants
and catalyst are dispersed in a single phase, usually liquid. Homogeneous
catalysis has several advantages over heterogeneous catalysis. For one thing, the
reactions can often be carried out under atmospheric conditions, thus reducing
production costs and minimizing the decomposition of products at high
temperatures. In addition, homogeneous catalysts can be designed to function
selectively for a particular type of reaction, and homogeneous catalysts cost less
 than the precious metals (for example, platinum and gold) used in heterogeneous
catalysis (Brian).
2.3.2 Types of Catalytic Reactions in Homogeneous Catalysts of Transition
Metal Elements or Compounds
1. Alkene Metathesis
Alkene metathesis reactions are catalyzed by homogeneous
organometallic complexes that allow considerable control over product
distribution; a key step in the reaction mechanism is the dissociation of a
ligand from a metal center to allow an alkene to coordinate. In recent years, a
number of newer catalysts have been introduced, and the development of the
well-defined ruthenium alkylidene compound by Grubbs in 1992, now known
as Grubbs’ catalyst.

Picture of ruthenium alkylidene (Grubbs’ catalyst).

In the case of Grubbs’ catalyst, it is known that the dissociation of a
PCy3 ligand from the Ru metal center is crucial in allowing the alkene
molecule to coordinate prior to metallacyclobutane formation (Shriver).
Mechanism:
A catalytic cycle for ring-closure metathesis (RCM) showing the
Chauvin mechanism which involves [2+2]-cycloadditions and
cycloreversions (Chaterine).
2. Hydrogenation of Alkenes
Wilkinson’s catalyst, [RhCl(PPh3)3], and related complexes are used
for the hydrogenation of a wide variety of alkenes at pressures of hydrogen
close to 1 atm or less; suitable chiral ligands can lead to enantioselective
hydrogenations (Shriver). The most widely used procedures for the
hydrogenation of alkenes nearly all employ heterogeneous catalysts, but for
certain specialized purposes, homogeneous catalysts are used (Chatarine).

Picture of Wilkinson’s catalyst.

Mechanism:
Catalytic cycle for the hydrogenation of RCH=CH2 using Wilkinson’s
catalyst.
3. Hydroformylation
In a hydroformylation reaction, an alkene, CO, and H 2 react to form an
aldehyde containing one more C atom than in the original alkene:

The term ‘hydroformylation’ derived from the idea that the product
resulted from the addition of methanal (formaldehyde, HCHO) to the alkene,
and the name has stuck even though experimental data indicate a different
mechanism. A less common but more appropriate name is
hydrocarbonylation. Both cobalt and rhodium complexes are used as catalysts
(Shriver).
Mechanism:
Competitive catalytic cycles in the hydroformylation of alkenes to give
linear (inner cycle) and branched (outer cycle) aldehydes (Chtaerine).
4. Wacker Oxidation of Alkenes
The Wacker process is used to produce acetaldehyde from ethene and
oxygen; the most successful system uses a palladium catalyst to oxidize the
alkene, with the palladium being re-oxidized via a secondary copper catalyst.
C2H4 + ½O2  CH3CHO
Mechanism:
The catalytic cycle for the palladium-catalyzed oxidation of alkenes to
aldehydes (Chaterine).
 The actual oxidation of ethene is known to be caused by a palladium
(II) salt:
C2H4 + PdCl2 + H2O  CH3CHO + Pd (0) + 2HCl
The exact nature of the Pd (0) species is unknown, but it probably is
present as a mixture of compounds. The slow oxidation of Pd (0) back to Pd
(II) by oxygen is catalyzed by the addition of Cu(II), which shuttles back and
forth to Cu (I) (Shriver):
Pd (0) + 2[CuCl4]2-  Pd2+ + 2[CuCl2]- + 4Cl-
2[CuCl2]- + ½O2 + 2H+ + 4Cl-  2 [CuCl4]2- + H2O
5. Methanol Carbonylation
The time-honored method for synthesizing ethanoic (acetic) acid is by
aerobic bacterial action on dilute aqueous ethanol, which produces vinegar.
However, this process is uneconomical as a source of concentrated ethanoic
acid for industry. A highly successful commercial process is based on the
carbonylation of methanol:
CH3OH + CO → CH3COOH
The reaction is catalyzed by all three members of Group 9 (Co, Rh,
and Ir). Rhodium and iridium complexes are highly active and selective in the
 carbonylation of methanol to form acetic acid. Originally a Co complex was
used, but then a Rh catalyst developed at Monsanto greatly reduced the cost
of the process by allowing lower pressures to be used.
Mechanism:
The catalytic cycle for the formation of ethanoic (acetic) acid with a
rhodium-based catalyst.

6. Asymmetric Oxidation
In addition to catalyzing reductions, d-metal complexes are also active
in oxidations. For example, in the Sharpless epoxidation, prop-2-en-1-ol (allyl
alcohol) or a derivative is oxidized with tert-butyl hydroperoxide, in the
presence of a Ti catalyst with diethyl tartrate as a chiral ligand, producing an
epoxide.
Mechanism:
The reaction is thought to go through a transition state in which both
the peroxide and the allyl alcohol are coordinated to a Ti atom through their
O atoms (Shriver).
2.4 Heterogenous Catalysts
2.4.1 Terms of Homogenous Catalyst
A heterogeneous catalyst is in a different phase from the components of
the reaction for which it is acting (Chaterine). In heterogeneous catalysis, the
reactants and the catalyst are in different phases. Usually, the catalyst is a solid
and the reactants are either gases or liquids. Heterogeneous catalysis is by far the
most important type of catalysis in industrial chemistry, especially in the
synthesis of many key chemicals (Brian).
We shall mainly be concerned with reactions of gases over heterogeneous
catalysts. Molecules of reactants are adsorbed on to the catalyst surface, undergo
reaction and the products are desorbed. Interaction between the adsorbed species
and surface atoms may be of two types: physisorption or chemisorption.
Physisorption involves weak van der Waals interactions between the
surface and the adsorbate. Chemisorption involves the formation of chemical
bonds between surface atoms and the adsorbed species (Chaterine).
2.4.2 Types of Catalytic Reactions in Homogeneous Catalysts of Transition
Metal Elements or Compounds
1. Ammonia Synthesis (Haber Process)
Ammonia is an extremely valuable inorganic substance used in the
fertilizer industry, the manufacture of explosives, and many other
applications. Around the turn of the century, many chemists strove to
synthesize ammonia from nitrogen and hydrogen (Brian). Iron metal, together
with small quantities of alumina and potassium salts and other promoters, is
used as the catalyst (Shriver).
Mechanism:
First, the H2 and N2 molecules bind to the surface of the catalyst. This
interaction weakens the covalent bonds within the molecules and eventually
 causes the molecules to dissociate. Second, the highly reactive H and N atoms
combine to form NH3 molecules, which then leave the surface (Brian).

2. Sulfur Dioxide Oxidation (Contact Process)

Contact process, modern industrial method of producing sulfuric acid.
Sulfur dioxide and oxygen, passed over a hot catalyst, unite to form sulfur
trioxide, which in turn combines with water to make sulfuric acid. The
oxidation of SO2 to SO3 is the first step in the Contact process, and the yield
of SO3 depends on temperature and pressure. At ordinary temperatures, the
reaction is too slow to be commercially viable, while at very high
temperatures (Chaterine).
Mechanism:
Concentrated sulfuric acid is manufactured by the contact process.
The first stage is the oxidation of a sulfur compound to SO2.
S(s) + O2(g)  SO2(g)
The second stage is the oxidation of SO 2 to SO3. This reaction is
carried out at high temperatures and pressures over a V2O5 catalyst supported
on silica beads:
2SO2(g) + O2(g)  2SO3(g)
The SO3 is then passed into the bottom of a packed column and
washed by running oleum, H2S2O7, from the top of the column. The gas is
 then washed in a second column with 98 per cent by mass H 2SO4. The SO3
reacts with the 2 per cent of water to produce sulfuric acid, H2SO4:
SO3(g) + H2O(l)→ H2SO4(l)
3. Catalytic Converters
Catalytic convertors are used to reduce toxic emissions from internal
combustion engines, which include nitrogen oxides, carbon monoxide, and
unburnt hydrocarbons (Shriver).
An efficient catalytic converter serves two purposes: It oxidizes CO
and unburned hydrocarbons to CO2 and H2O, and it reduces NO and NO2 to
N2 and O2. Hot exhaust gases into which air has been injected are passed
through the first chamber of one converter to accelerate the complete burning
of hydrocarbons and to decrease CO emission. However, because high
temperatures increase NO production, a second chamber containing a
different catalyst (a transition metal or a transition metal oxide such as CuO
or Cr2O3) and operating at a lower temperature is required to dissociate NO
into N2 and O2 before the exhaust is discharged through the tailpipe.

Mechanism:
The beads contain platinum, palladium, and rhodium, which catalyze
the combustion of CO and hydrocarbons (Brian).
 Whereas CO and hydrocarbons are oxidized, the destruction of NO x
involves its reduction. Modern catalytic converters have a ‘three-way’ system
which promotes both oxidation and reduction. Pd and Pt catalyze reactions:
2CO + O2  2CO2
C3H8 + 5O2  3CO2 + 4H2O
while Rh catalyzes reactions:
2NO + 2CO  2CO2 + N2
2NO + 2H2  N2 + 2H2O
and Pt catalyzes reaction:
C3H8 + 10NO  3CO2 + 4H2O + 5N2
4. Manufacture of Nitric Acid (Ostwald Process)
Nitric acid is one of the most important inorganic acids. It is used in
the production of fertilizers, dyes, drugs, and explosives. The major industrial
method of producing nitric acid is the Ostwald process (Brian).

Mechanism:
 The starting materials, ammonia and molecular oxygen, are heated in
the presence of a platinum-rhodium catalyst to about 800 oC to produce nitric
acid:
4NH3(g) + 5O2(g)  4NO(g) + 6H2O(g)
The nitric oxide readily oxidizes (without catalysis) to nitrogen dioxide:
2NO(g) + O2(g)  2NO2(g)
When dissolved in water, NO2 forms both nitrous acid and nitric acid:
2NO2(g) + H2O(l)  HNO2(aq) + HNO3(aq)
On heating, nitrous acid is converted to nitric acid as follows:
3HNO2(aq)  HNO3(aq) + H2O(l) + 2NO(g)
The NO thus generated can be recycled to produce NO 2 in the second step
(Brian).
5. Fischer-Tropsch Synthesis
The conversion of syngas, a mixture of H2 and CO, to hydrocarbons
over metal catalysts was first discovered by Franz Fischer and Hans Tropsch
at the Kaiser Wilhelm Institute for Coal Research in Müllheim in 1923. In the
Fischer–Tropsch reaction, CO reacts with H2 to produce hydrocarbons and
water. Several catalysts have been used for the Fischer–Tropsch synthesis; the
most important are based on Fe and Co. Cobalt catalysts have the advantage
of a higher conversion rate and a longer life (of over 5 years). The cobalt
catalysts are in general more reactive for hydrogenation and produce fewer
unsaturated hydrocarbons and alcohols than iron catalysts. Iron catalysts have
a higher tolerance for sulfur, are cheaper, and produce more alkene products
and alcohols. The lifetime of the iron catalysts is short, however, and in
commercial installations generally limited to about 8 weeks (Shriver).
Mechanism:
Hydrogen and carbon monoxide can be converted to hydrocarbons
and water by reaction over iron or cobalt catalysts. The process is exothermic.
The distribution of the products depends on the catalyst and the temperature,
pressure, and residence time. Typical conditions for the Fischer–Tropsch
synthesis are a temperature range of 200–350oC and pressures of 15–40 atm.
 The product range consists of aliphatic straight-chain hydrocarbons
that include methane (CH4) and ethane, LPG (C3 to C4), gasoline (C5 to C12),
diesel (C13 to C22), and light and heavy waxes (C23 to C32 and >C33,
respectively). Side reactions include the formation of alcohols and other
oxygenated products (Shriver).
6. Alkene Polymerization
Heterogeneous Ziegler–Natta catalysts are used in alkene
polymerization. Polyalkenes, which are among the most common and useful
class of synthetic polymers, are most often prepared by use of organometallic
catalysts, either in solution or supported on a solid surface. The development
of alkene polymerization catalysts in the second half of the twentieth century,
producing polymers such as polypropene and polystyrene, ushered in a
revolution in packaging materials, fabrics, and constructional materials. K.
Ziegler, working in Germany, developed a catalyst for ethene polymerization
based on a catalyst formed from TiCl4 and Al(C2H5)3, and soon thereafter G.
Natta in Italy used this type of catalyst for the stereospecific polymerization
of propene (Shriver).
Mechanism:
A schematic representation of alkene polymerization on the surface of
a Ziegler–Natta catalyst
 Alkene polymerization is catalyzed at a surface Ti (III) center in
which there is a terminal Cl atom and a vacant coordination site. The Cossee–
Arlman mechanism is the accepted pathway of the catalytic process.
Coordinatively unsaturated TiCl5 units are the catalytically active sites. In the
first step, the surface Cl atom is replaced by an ethyl group. In the second
step, the alkene binds to Ti (III) and this is followed by alkyl migration. The
repetition of these last two steps results in polymer growth. Heterogeneous
TiCl3/Et3Al or MgCl2/TiCl4/Et3Al catalysts are used industrially for the
manufacture of isotactic polymers, e.g. polypropene.
 CHAPTER III
CLOSING

3.1 Conclusion

3.2 Suggestion
REFERENCES
ATTACHMENT