Applied Chemistry-II

Dr. Payal Joshi

Catalysis
Introduction Ask the average person what a catalyst is, and he or she will probably tell you that a catalyst is what one has under the car to clean up the exhaust. Indeed, the automotive exhaust converter represents a very successful application of catalysis. It does a great job in removing most of the pollutants from the exhaust leaving the engines of cars. However, catalysis has a much wider scope of application than abating pollution. In 1835, J.J. Berzelius studied number of reactions having one factor in common, i.e, in every case, nature of the reaction was influenced by presence of substance which itself remained unchanged in the process. Conversion of starch into sugar in presence of acids, decomposition of hydrogen peroxide in alkaline solutions and combining hydrogen and oxygen on surface of spongy platinum. In these cases, acids, alkaline solutions and spongy Pt were the substances which were found to increase or accelerate the reaction without themselves undergoing any change. Catalysts are the workhorses of chemical transformations in the industry. Approximately 8590% of the products of chemical industry are made in catalytic processes. Catalysts are indispensable in; Production of transportation fuels in one of the approximately 440 oil refineries all over the world. Production of bulk and fine chemicals in all branches of chemical industry. Prevention of pollution by avoiding formation of waste (unwanted byproducts). Abatement of pollution in end-of-pipe solutions (automotive and industrial exhaust).

A catalyst offers an alternative, energetically favorable mechanism to the noncatalytic reaction, thus enabling processes to be carried out under industrially feasible conditions of pressure and temperature. For example, living matter relies on enzymes, which are the most specific catalysts one can think of. Also, the chemical industry cannot exist without catalysis, which is an indispensable tool in the production of bulk chemicals, fine chemicals and fuels. For scientists and engineers catalysis is a tremendously challenging, highly multidisciplinary field. Let us first see what catalysis is, and then why it is so important for mankind. Substances which alter rate of the reaction without themselves undergoing any chemical change are called catalysts and the phenomenon is known as, Catalysis, (Greek: Kata= wholly, lein= to loosen). When a catalyst accelerates the rate of the reaction it is called as positive catalyst whereas when it retards the reaction rate it is called negative catalyst. Positive catalysts examples: Rate of decomposition of KClO3 in presence of MnO2
MnO2

2KClO3

2KCl + 3O2

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Negative catalysis examples: Rate of decomposition of hydrogen peroxide into water and oxygen is decreased in presence of glycerol or dilute acids. Rate of oxidation of CHCl3 is decreased in presence of alcohol catalyst, 2CHCl3 + O2 Poisons
alcohol

2COCl2 + 2HCl

Autocatalysis

Promoters

Characteristics of Catalysis Remains unchanged in amount & chemical composition at the end of the reaction. But can undergo physical change.

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Dr. Payal Joshi

Amount and chemical composition of a catalyst remains same at the end of the chemical reaction. However, physical changes can be observed such as, colour of catalyst, size of catalyst particles, eg, Pt gauze catalyst becomes rough after used for oxidation of ammonia. Small/trace quantity is needed Even a trace amount of catalyst is sufficient to carry out a chemical reaction. Finely divided powdered catalysts provide larger surface area for better catalytic activity. Does not affect the position of equilibrium in a reversible reaction. Use of catalyst hastens the approach of equilibrium

A catalyst acts along both forward and backward reactions. Hence, in a reversible reaction, it does not change the equilibrium state. Since the catalyst remains unchanged chemically at the end if the reaction, it cannot contribute any energy to the system. According to second law of thermodynamics (states that processes occur in a certain direction, not in just any direction), the same position of equilibrium should be attained, whether a catalyst is used or not. However, the catalyst affects the forward and backward reaction to the same extent in reversible reaction. Catalyst helps in attaining equilibrium quickly, but position of equilibrium constant remains unchanged as shown in the above figure. Catalyst can accelerate both the forward and backward reaction to the same extent in an equilibrium process. Does not start the reaction just alters the reaction rate Specific in its action : A particular catalyst can bring about a particular change only. A substance which maya ct as a catayst for one reaction may fail to catalyse the other reaction. Eg, MnO2 can catalyse decomposition of KClO3, but has no effect on combination of SO2 and O2. Cannot alter the nature of products of a reaction : eg, KClO3 on decomposition gives KCl and O2, whether MnO2 is added or not. Catalysts come in a multitude of forms, varying from atoms and molecules to large structures such as zeolites or enzymes. In addition they may be employed in various surroundings: in liquids, gases or at the surface of solids. Preparing a catalyst in the optimum form and studying

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Dr. Payal Joshi

its precise composition and shape are an important specialism, which we describe in later chapters. It is customary to distinguish the following three subdisciplines in catalysis: homogeneous, heterogeneous and bio catalysis. In this topic we will only study about homogeneous and heterogeneous catalysts. Homogeneous Catalysis In homogeneous catalysis, both the catalyst and the reactants are in the same phase. Manufacture of H2SO4 (Chambers process) Oxidation of SO2 with oxides of nitrogen [NO] + O2 NO2 (gas) (gas) (gas) SO2 + NO2 SO3 + [NO] (gas) (gas) (gas) (gas) Decomposition of Ozone in presence of chlorine atoms
Ozone in the atmosphere decomposes, among other routes, via a reaction with chlorine atoms. Ozone can decompose spontaneously, and also under the influence of light, but a Cl atom accelerates the reaction tremendously. As it leaves the reaction cycle unaltered, the Cl atom is a catalyst. Because both reactant and catalyst are both in the same phase, namely the gas phase, the reaction cycle is an example of homogeneous catalysis.

Example of Homogeneous catalysis in solution phase Hydrolysis of esters catalysed by acid or alkali

Decomposition of Hydrogen peroxide by iodide ions

Heterogeneous Catalysis In heterogeneous catalysis, the catalyst is in different physical state than the reactants. Heterogeneous catalysts find extensive applications in chemical and petrochemical industry.

Applied Chemistry-II In solid phase : Decomposition of potassium chlorate in presence of manganese dioxide

Dr. Payal Joshi

In solution phase : Decomposition of hydrogen peroxide with MnO2 catalyst

In gaseous phase (Contact catalysis) : Synthesis of Ammonia by Habers Process

Importance of Catalysts and Adsorbants The chemical industry of the 20th century could not have developed to its present status on the basis of non-catalytic, stoichiometric reactions alone. Reactions can be controlled on the basis of temperature, concentration, pressure and contact time. Raising the temperature and pressure will enable stoichiometric reactions to proceed at a reasonable rate of production, but the reactors in which such conditions can be safely maintained become progressively more expensive and difficult to make. In addition, there are thermodynamic limitations to the conditions under which products can be formed, e.g. the conversion of N2 and H2 into ammonia is practically impossible above 600 C. Nevertheless, higher temperatures are needed to break the very strong N N bond in N2. Without catalysts, many reactions that are common in the chemical industry would not be possible, and many other processes would not be economical. Catalysts accelerate reactions by orders of magnitude, enabling them to be carried out under the most favorable thermodynamic regime, and at much lower temperatures and pressures. In this way efficient catalysts, in combination with optimized reactor and total plant design, are the key factor in reducing both the investment and operation costs of a chemical processes. Activation Energy and Catalysis Collision Theory Reactant molecules must collide When molecules collide, rearrangement of chemical bonds in reactant molecules take place resulting in formation of product molecules For effective collisions, molecules must collide with sufficient energy Exchange of energy during collisions This energy is called activation energy : Excess energy which the reactant molecules must acquire so that they react upon collision to form an activated complex is called Activation energy

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Dr. Payal Joshi

Whether a reaction is exothermic or endothermic, the reacting molecules absorb certain minimum energy to reach the activated state and form unstable activated complex which immediately decomposes into products. If activation energy is larger, then more enrgy is required for the formation of activated complex. Thus, introduction of a catalyst in such reactions decreases the activation energy, thereby allowing the reaction to take place at lower temperatures. Many biological reactions in living beings occur at atmospheric temperatures because of catalysis by enzymes. Such reactions require higher temperatures which will not be possible without biocatalysts. If the activation energy is smaller, then the reacting molecules may absorb energy from the surroundings to reach an activated state for the reaction to occur. Such reactions do not need excess energy. Eg., reaction between ammonia and HCl gas at room temperature or a lower temperatures. Mechanism of catalysis To explain the mechanism of catalysis, two theories are proposed as under: Intermediate Compound Formation Theory Clement and Desormes (1806) proposed the formation of unstable intermediate compound during the catalyzed reaction. According to this theory, the catalyst reacts with one of the reactants to give an intermediate, which reacts with another reactant to yield products and the catalyst.

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Dr. Payal Joshi

The theory fails to explain the role of promoters and catalytic poisons. Further, the formation of intermediate compound in heterogeneous catalysis reactions on the surface of solid catalyst are not well understood by the above theory. Adsorption Theory Heterogeneous catalysis, eg, gaseous reaction on the solid surface is explained by this theory as follows,
catalyst

A(g) + B(g)

C(g) + D(g)

Generally, the following four steps are involved in heterogeneous catalysis. Diffusion of reactants at the surface of the catalyst Adsorption of the reactants at the surface Reaction of reactants at the surface Desorption of products from the surface

It can be depicted as follows:

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Dr. Payal Joshi

The reactants are adsorbed on the surface of the catalyst and held by weak vander Waals forces of attraction (physisorption) or by partial chemical bonds (chemisorption). The surface provides chances for the reactant molecules to combine and form activated complex and accelerate the reaction. Finally the activated complex gets decomposed and resulting products formed desorb from the surface of the catalyst and catalyst surface is regenerated for another cycle. Example of Adsorption theory

The above diagram represents mechanism of hydrogenation of ethene to ethane in presence of nickel catalyst. Molecular design of Zeolites They are hydrated crystalline aluminosilicates with a general formula of MIMII[(AlO2)x(SiO2)y(H2O) SiO4 & AlO4 tetrahedra interlinked thro common O atoms to give 3-D network containing molecular sized cavities/pores. Pores contain water molecules and mobile cations to compensate negative charges of anionic framework.

Applied Chemistry-II

Dr. Payal Joshi

Si atom has a valency 4, but Al atom has a valency 3, hence there is a negative charge on Al atom in its tetrahedron (neutralized by metal ions). In the aluminosilicate, oxygen atoms bridge between two silicon atoms or one Si and one Al atom. 3-4 oxygen atoms on each tetrahedron are shared with the neighbouring silicate or aluminosilicate tetrahedra.

Structure of Sodalite cage. Zeolites are molecular sieves: The term molecular sieve is used to describe a class of materials that exhibit selective sorption properties, i.e, they are able to separate compounds of a mixture on the basis of molecular shape and size.

Hence, zeolites are molecular sieves. Important properties of zeolites: Adsorption : Free valancies on surface of zeolite crystals, results in adsorption properties Water, acidic ions get adsorbed on surface, smaller molecules get selectively adsorbed in cavities of zeolites Adsorption due to hydrogen bonding

Catalysis : Good adsorbents hence good catalysts used In isomerization of hydrocarbons ; Cation Exchanger : Used in softening of hard water : hardness causing Ca & Mg ions are strongly held and exchanged with H+ and Na+ ions

Applied Chemistry-II Applications:

Dr. Payal Joshi

Pillared Clays Natural clays are metal aluminosilicates. There are ions like K+, Ca2+, Mg2+, Na+ to neutralize the negative charge on the aluminosilicate anions. Pillared clays are chemically modified clays or synthetic in nature, in which ions like Al3+, Zr2+, Ti4+ are intercalated (sandwiched) between the clay anions layers. In 1955, Barrer & MacLeod first synthesized pillared clay, creating a new class of porous materials to be used as heterogeneous catalysts. They are materials that possess permanent porosity. Obtained by introducing chemical compounds that act as pillars of molecular dimension between the lamellae of the clay, keeping them away and giving rise to micropores. Chemical compounds acting as supports/ molecular pillars between clay lamellae are called agents pilarizantes. Pillars are large inorganic metal oxocations intercalated (caging) between aluminosilicate layers (claylamellar/leaf structure). Polyoxocations are then converted to stable metal oxide pillars thro calcination, holding layers permanently apart------This creates Microporosity.

Types of pillared clays Organic Pillared clays Contains organic cations like C3H7+, C6H5+, carbocations, or polymers sandwiched between clay anions Inorganic Pillared Clays Contains inorganic cations; Al-Pil-Clay, Chromia-Pil-clay, Al-Cu-Pil-clay, Ti-Pil-clay Properties: Act as molecular seives since interlayer and interpillar gallery spacing provides large surface area and pore voids. Cation exchanger. Smaller cations in Pillared clays can be replaced by larger cations. Catalysts for nitration, cyclization, oxidation reactions. Adsorbants : Good adsorbants for acidic, basic compounds, gases. Good thermal stability on wide range of temperatures.

Applied Chemistry-II Carbon membranes

Dr. Payal Joshi

Layer of carbon nanotubes on Si chip. As we know, carbon nanotubes are cylinders of graphene sheets Supersmooth inner side of nanotubes can allow free flow of gases & liquids Larger molecules are blocked by the pores Membrane is prepared by arranging carbon nanotubes on a silicon chip in single alignment direction. Gaps between nanotubes are filled with ceramic matrix material. The pores are too small that six water molecules can fit across the diameter of the tube. Applications Desalination Water flows easily thro carbon nanotube pores, blocking the salt ions Molecular transport Due to its nanometer size and smooth inner surfaces, CMs allow separations of molecules of different sizes in gaseous & liquid mixture Useful in hydrocarbon gas separations CMs designed for adsorption-desorption study of molecular seives Metal complex catalysts There are a large number of organic manufacturing processes, carried out by using metal complexes as a catalyst. Most of the homogeneous catalytic reactions like, hydrogenation of alkenes, hydroformylation of alkenes, dimerisation and oxidation of alkenes require metal complexes as a catalyst. Metal complexes are composed of metal ion such as Fe, Co, Ni, etc coordinated to a ligand, thereby forming a metal-ligand bond. Empty d-orbitals of transition metals complexes with filled p-orbitals of a ligand as shown below,

The molecular structure of a metal complex with co-ordination number 4,5,6 or 8 ligand atoms assume tetrahedral, square planar, trigonal bipyramidal or octahedral structures as shown below,

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Dr. Payal Joshi

Tetrahedral Complex

Square planar Trigonal bipyramidal

Octahedral Complex The catalytic mechanism involves replacement of weaker ligands by stronger ligands. The next step involves rearrangement of organic ligands when water ligand attacks to form an intermediate (unstable). Finally, the decomposition of the intermediate leads to formation of products and recovered easily from the catalyst. Examples: Conversion of ethylene to acetaldehyde (Wacker Process) [PdCl4]2- 110C, 5 Atm H2C=CH2 +1/2O2 H3CCHO

Here, the catalyst is tetrachloropallidimate ion, [PdCl4]2-

Metal Cluster catalysis Contains Metal-Metal bond formation Bond is due to overlapping of d-d orbitals Low oxidation state of the metal ion allows for the overlap

These metal clusters are classified into two groups viz, Metal clusters containing polynuclear carbonyls, nitrosyls and related compounds (low oxidation state of metal -1 to +1). Metal clusters containing chloride, oxide complexes (higher oxidation state of metal +2 to +3) which are relatively less stable than other cluster compounds.

Binuclear clusters are represented as [M2X8]-2 ions, where M is the transition metal atom and X is Cl, Br, I. The metal to metal distance is very short. [ReCl8]-2 octachloro dirhenate (II) anion is one of the examples of such cluster and is shown below.

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Dr. Payal Joshi

Trinuclear clusters: Clusters containing three metal atoms such as rhenium (III) trinuclear cluster as shown below,

Hexanuclear clusters: [Mo6Cl8]Cl4 is an example of such a cluster. Mo atoms are placed in an octahedral manner, i.e, four in a plane, one above the plane and one below the plane. Each Mo (II) atom has four bonds with adjacent Mo atoms and has four coordinate bonds with Cl ligands. There is a cubic arrangement of Cl ligands around Mo atoms. Metal oxide catalysis Partial oxidation reactions catalyzed by surfaces of transition metal oxides Used for conversion of hydrocarbons to valuable intermediates like CHO, --COOH, epoxides, nitriles Catalyst for partial oxidation is so designed to provide a limite amount of oxygen to a reactant, allowing formation of desired product but restricting further oxidation to CO or CO2. Catalysts are complex solid oxides Surfaces donate oxygen to adsorbed organic reactant Restricted temperature conditions to avoid byproduct formation Catalysts, hence are selective in particular group conversion reactions

Structure of oxide surfaces If a crystal of transition metal oxide is cleaved along a certain plane, one of the face will have O2- ion vacancies (positively charged surface) and other face will have metal ion vacancies. Thus now the surface can adsorb reactants. A metal ion is attracted from all sides by oxide ions inside the crystal but, the metal ion at the surface is not having balanced forces of attraction, hence the metal ion on the surface will have strong adsorption nature. Similarly, the oxide ions on the surface have unbalanced forces of attraction and hence the nature of adsorption is observed.

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Dr. Payal Joshi

Mechanism: Catalytic oxidation involves single electron transfers and protons via intermediates like oxide ions, peroxides and transition metal ions. Oxygen (O atom) of adsorbed molecule can form bonds with vacant anion position on a catalyst surface or the H can form hydroxide ion on the surface of metal oxide catalyst as intermediates.

Example: Conversion of propene to acrolein via oxide catalyst