10, CH, cH,cl a bv. pnerrane + HOI The catalyst does not alter the position of equilibrium in a reversible reaction: The catalyst helps in attaining the equilibrium more quickly by increasing the rates of both the forward and the reverse reactions to the same extent, but do not alter the concentration of the reactant and the products at equilibrium. Thus the equilibrium constant remains the same. Its also evident from the Fig. 6.2 that, the activation energy for the reverse reaction is also lowered by exactly the same amount as for the forward reaction, by the addition of the catalyst. Thus, if a catalyst doubles the rate of the forward reaction, it also doubles the rate of the backward reaction. In other words, the catalyst for the forward process in a reaction is also a catalyst for the reverse reaction. A catalyst does not intitiate the reaction: It can only accelerate the rate of the reaction already taking place, even if very slowly. But this subject has been a matter of great controversy. According to W. Ostwald Cd ea cannot initiate the reaction but H.W. Armstrong (1885-1903) and T.M. Lowry (1935-1928) have suggested that there are certain reactions which can occur only if a catalyst-is and will not occur in its absence. For example. perfectly dry Hy and O, do not co even if they are left in contact for years, but in presence of a little water w’ Shjact as a catalysthe reaction proceeds quite rapidly. But still this does not prove that change did not 4t all, but that uncatalyzed combination may be so slow that millions of years would be required for a detectable amount of water to be formed. \ Optimum temperature: There is a particular tempYrature at which the activity of the catalyst is maximum, this temperature is called optimum temperature’ Catalytic promotors: The addition of small amounts of foreign substances which themselves are not catalytically active. inereases the activity of 4 catalyst. Such substances are called promoters. In the manufacture of NH; by Haber's process, finally divided iron acts as a catalyst, while molybdenum acts as a promotor. =! Catalytic poisons: The activity of a catalyst: is inhibited or, completely destroyed by the Presence of even minute traces of foriegn substances called catalytic poisons or anticatalysts. In the manufacture of H,SO,, a trace of As, Os destroys the catalytic efficiency of spongy. platinum, High surface area: Catalysts have high surface areas. Even a small lump (1 em?) of a catalyst can have a surface area ranging to 100 m? because of the presence of pores. _S* TYPE OF CATALYSIS Broadly two types of catalysis are known: 1 2, Homogeneous Catalysis Heterogeneous Catalysis10. CH, cH.ct a The catalyst does not alter the Position of equilibrium in a reversible reaction: The catalyst helps in attaining the equilibrium more quickly by increasing the rates of both the forward and the reverse reactions to the same extent, but do not alter the concentration of the reactant and the products at equilibrium. Thus the equilibriurn constant remains the same. Itis also evident from the Fig, 6.2 that, the activation energy for the reverse reaction is also lowered by exactly the same amount as for the forward reaction, by the addition of the catalyst. Thus, if @ catalyst doubles the rate of the forward reaction, it also doubles the rate of the backward reaction. In other words, the catalyst for the forward process in a reaction is also a catalyst for the reverse reaction, A catalyst does not intitiate the reaction: It can only accelerate the rate of the reaction already taking place, even if very Te this subject has been a matter of great controversy. According to W. Ostwald (1895) catalyst cannot initiate the reaction but FLW. Armstrong (1885-1903) and T.M. Lowry (1935-1928) have suggested that there are certain reactions which can occur only if a catalyst-is-present and will not occur in its absence. For example. perfectly dry H, and O, do not coming to form Water, even if they are left in contact for years, but in presence of a little water whithyact as a catalysthe reaction proceeds quite rapidly. But still this does not prove that change did not t all, but that uncatalyzed Combination may be so slow that millions of year would be required for a detectable amount of water to be formed. Optimum temperature: There is a particular temple at which the activity of the catalyst is maximum, this temperature is called optimum témperature. Catalytic promotors: The addition of small amounts of foreign substances which themselves are not catalytically active, inereases the activity of catalyst. Such substances are called prométers. In the manufacture of NH by Haber's process, finally divided iron acts as a catalyst. while molybdenum acts as a promotor. Catalytic poisons: The activity of a catalyst. is inhibited or, completely destroyed by the Presence of even minute traces of foriegn substances called catalytic poisons or anticatalysts In the manufacture of HySOy, a trace of As, Qs destroys the catalytic efficiency of spangy. platinum. High surface area: Catalysts have high surface areas, Even a small lump (1 ¢ can have a surface area ranging to 100 m? because of the presence of pores. of a catalyst * TYPE OF CATALYSIS Broadly two types of catalysis are known: is 2 Homogeneous Catalysis Heterogeneous Catalysis‘ny Chemistry Homogeneous Catal: + In homogeneous catalysis, the catalyst is present in the same phe as the reac istrit as the reactants and is evenly distributed throughtout. The homogeneous catalysis can o, in gaseous or liquid phase 7 (i) Homogeneous Catalysis in gaseous phase: There are only a few cases of homogenec catalysis in gaseous phase e.g. (a) Oxidation of sulphur dioxide (SO,) to sulphur tox: (SO) with nitric oxide as catalyst. 7 CH, CHO+ [I 2S0,+[NO] 1CHOs [2] > 2SQ,+1NO} (b) Decomposition of acetaldehyde with 1, as catalyst H,CHO+ 1, 9 + CHy+CO+1, ‘vapour vapbur ‘gas! gas (ono gas also acts as a catalyst in combination of CO with oxygen. 2c0+0, —2s 2c0, ae (d) NO gas catalyses the combination of moist sulphur dioxide and oxygen in the lea: chamber process for the manufacture of HSO,. [No} 280, +2H,0+0, eas ef es 2H,S0, (ii) Homogeneous catalysis in liquid phase: Most of the reactions under this categ involve the acid or base as the catalyst. @yVydrolysis of an ester in the presence of acid or alkali CH{COOC, Hi +H20q, E> CH,COOH,) +C, HOH, (by Inversion of sucrose in presence of hydrogen ions in aqueous solution Cy Hyp Oy tH, wt, Cg Hy2 0, +CoHi2 % Glucose Fructose (c) The decomposition of hydrogen peroxide is catalyzed in the presence of chiens 2H30, _S_, 20+, (a) Conversion of acetone into diacetone alcohol is catalyzed by hydrogen 10ns oH CH; Sexo + mecocry OH Fe —cn,coom, cH cH The mechanism of homogencous catalysis can be explained on the basis of unstt intermediate compound formation theory (discussed later). ‘ us Catalysis: In heterogeneous catalysis the catalyst is in different phase i In majority of the eases, the catalyst is solid while the reactants are either lia Heterogenc? the reactants.term “Contact Catalysis” is used for this type of catalysis as the reaction tact of the reactants with the catalyst surface. This form of catalysis has Technical importance. The catalyst is usually a metal or metal oxide iquid or gaseous reactants. or gases. Often th occurs by the cont jg number of reactions 0! Heterogeneous catalysis involve solid, li encous Catalysis with gaseous reactants: There are a large number of reactions ‘t be put under the heading of heterogeneous catalysis. Some of them are~ led platinum or vanadium () Heterog which ca {@/Combination of SO, and oxygen in the presence of finely divid penta oxide V, Os (Contact Process). 280,+0, —» 2803 gas gas solid gas (b) Combination of hydrogen and oxygen in presence of finely divided platinum. 2H, +0, 4s. 2H,0 (c) Hydrogenation of oils in presence of Nickel R-CH=CH-R'+H, —“> R-CH,-CH,-R’ unsaturated oil gas (4) Synthesis of petroleum by the combination of CO and Hy in the presence of iron, cobal or nickel xCO+yH> a, Petroleum + H,0. {gy Mamufacture of ammonia by Haber process Fe N, 43H, =eot NMG, (ii) Heterogeneous catalysis with liquid reactants : The common example under this category are- (@) Benzene and ethanoyl cl to form phenyl methyl ketone (CgHCOCH;) Jnloride react in the presence of anhydrous aluminium chloride Cg Heqy +CH3COCI(y AK, CgH,COCH, + HCI (b)ecomposition of aqueous solution of hydrogen peroxide (H,0,) is catalysed by MnO; or platinum in colloidal form. 2H,0, > 2H,0+0, (©) Decomposition of hypochlorites : The decomposition of hypochlorites in aqueous: solutions is catalysed by oxides of cobalt and nickel. ca(clo), —2+ CaCl, +02~Si1ON OF CATALYSIS he following types Positive Catalysis Negative Catalysis Auto Catalysis + Positive Catalysis: When the catalyst used accelerates the speed of a chemical reaction i: Known as a positive catalyst. Initially the term ‘catalyst’ coined by Berzelius was used for Positive catalyst only, but later on this term was used for all the substances whic rate of reaction, and hence the substances which inerease the rate of reaction Positive catalysis. Ail the reactions discussed above are the Halter thy are placed under example of positive catalysis, 2. Negative Catalysis: There are a tew cases, where a cata! may actually reduce the rate of reaction. Such a catalyst used is termed as negative ¢ The phenomenon is known as negative calaiysis or inhibition, Negative OF stops altogether an unwanted reaction. For example~ WY CHCL; on oxidation by air forms carbony! chloride (OCI), which is a poisonous substance. The formation of COCI, is suppressed by the adit as a negative catalyst GY Small amount of glycerol or acetanilide retards the decomposition of hydrogen peroside lyst instead of accelerating a reaction atalyst, Catalyst slows down n of ethanol which acts Completion of reaction . Auto Cataly There are certain reactions where one of the products of the reaction acts as the catalyst. Such reactions are known as Auto Catalyzed react auto catalysis the initial rate of the reaction rises as the catalytic product is formed thereby indicating that product accelerates 7 Fig. 6.3. Rive of Rate of reaction with Une Aeneuonitatee (ries Ge) othe Formation of prod Percentage Re Time —> Examples: ') During titration of warm solution of oxalic acid by drops take appreciable time to Gecolou ce the reaction is initially ver some time, the decolourization takes place rapidly as Mn?" ions formed du catalyze the reaction. idified KMnO, solution. the first two slow. But afier jon. 2KMnO4 + $ COOH + 3HySO4 ——> COOH IMASOS + KsSO4 + SHHO + 10CO> is of an ester is autocatalye.t by the acid which is formed during the reaction (ii) HydrolysiCatalysis 331 RCOOR’ +H,0 + RCOOH + R'OH. (iii) The free arsenic produced by the decomposition of arsine (AsH)) auto catalyze the reaction. 2AsH; -» 2As+3H, Catalyst (iv) The action of HNO, on copper is very slow it ly but NO; ions produced during the reaction act as catalyst and the reaction proceeds rapidly. 3Cu+8HNO, -, 3Cu(NO,), +4H,0+2NO Nitric oxide formed above dissolves in H,0 to provide NO3 ions. SS AREORIES OF CATALYSIS Different theories have been put forward to explain the homogeneous and heterogeneous catalysis ‘Theory of Homogeneous Catalysis (Intermediate Compound Formation Theory) This theory was put forward by element and Desormes in 1806. This theory explains satisfactorily the mechanism of homogeneous catalysis. According to this theory, the catalyst combines with one of the reactants to form an intermediate compound which is unstable and hence react immediately With other reactants to form the products and regenerating the catalyst. Consider a reaction between the reactants X and Y to form the product XY in the presence of a catalyst C. X+Y—©, xy According to the intermediate compound formation theory, the reaction may be split up into the following two steps: @ First step — Formation of intermediate X+#C — [XC]intermediate Compound (ii) Second step - Dissociation of intermediate, FXC]+Y XE Gi ACTIVATION ENERGY IN ABSENCE OF CATALYST Infact, the formation of intermediate compound provides an alternative reaction path having lower activation energy and hence Feaction proceeds at an increased rate. tis seen from the Fig. 6.4 that the total Snergies of the reactants Vand ¥, and those of the Product VY are unaffected by the catalyst. The only difference between the two is lowering Of the activation energy in the presence of a ‘atalyst. A number of catalytic reactions can ERMEDIATE COMPOUND ACTIVATION ENERGY IN PRESENCE OF CATALYST ENERGY—> XY (REACTANTS) XY PRODUCTS)332 Engineering Chemistry be explained on the basis of intermediate compound formation theory. A few of them ate disey belo JS Ordinarily, the gas phase reaction of sulphur dioxide with oxygen proceeds slowty 280, +0, + 280, But ifthe same reaction is cartied out in presence of NO as catalyst, the reactions proces relatively faster, 1 NO+—O, -» NO. 302 2 Catalyst Intermediate NO,+SO, + SO, + NO Catalyst Regenerated Ki) In Friedel Craft's reaction, anhydrous aluminium chloride is used as a catalyst for th Preperation of benzene. The mechanism can be discussed on the basis of intermatit formation theory. For example, benzoylation of benzoyl chloride proceeds as follows CoHsCOCI+[AICI,] 4 C,H,COCLAICI, (Reactant) (Catalyst) Intermediate CoH COCLAICI; +CgHe > CyHsCOC,Hs + HCI + AICI, Product atalyst Gi) Decomposition of hydrogen peroxide into water and oxygen catalyzed by bromide ions is believed to take place as: H20 949) =p aq) ad 120, + Bro Catalyst H,0, +BrO” + H,0q 40x) * Br, ag) Catalyst (oa) Gs) Reaction for the manufacture of chlorine by the reaction of oxygen and hydrochloric ai in the presence of cuprous chloride as catalyst 4CuCl+O, 5 2Cu,0C1, Catalyst Intermediate 2Cu,0Cl, +4HCL dCuCl, +211,0 4CUCL, 4CuCL + 201, Catalyst (YA Formation of ether from excess of ethylalcohol using HySO, as catalyst C,HZOH+H,SO, , ¢ 2HHSO, 4 HO Intermediate C,HsHSO, +C, HOH CyHZOC,H, + Hyso, Uthytether CatalystCatalysis 333 i) An example of homogeneous catalysis from atmos i" of Ozone in the Stratosphere by the is of chloroflourocarbons (CFCs), C140; + ClO + 0, Catalyst Inter- mediate compound Cl0+0 4 Cl + 0, Catalyst et Teaction under homogencous catalysis viz. acid base catalysis sare dealt in detail in section 6.6 and 6.7. fieric chemistry includes, the decompo- Presence of chlorine atoms, resulting ftom the lain the action of catalytic Promoters and poisons. le to homogeneous catalysis. In heterogeneous catalysis,where the catalyst Teactants are gases the formation of intermediate compound is not possible. heterogeneous catalysis is explained on the basis of Adsorption Theory. But s theory it is important to learn what the term adsorption means. to the existence of a higher concentration of the molecules of a substance quid or solid phase than present in the bulk. Iuid is in a state of strain due to strong inward pull, due to which the liquid 3. This property arises due to the presence of unbalanced forces on the surface. fa solid also has unsatisfied valence or residual forces. When a solid surface uid, molecules of the gas or solution phase accumulate or adsorbed on that is adsorbed on the surface is called Adsorbate and the solid on whose ules are adsorbed is called Adsorbent. . : i ds upon surface phenomenon and at a given temperature and pressure depen the adsorbent. Solids in finely divided state, because of large surface area are ee exoth« 3) The phenomenon of adsorption is thermodynamically a a Ere ea Hi a decrease in free energy of the system. When @ adsorbed on the surface ofthe metal, the process is aevompanied with a decrease eis AS is negative. Thus, it is clear from the thermodynamic relation, AG = AH ~ TAS is an exothermic process. categories hi jation between the two categori i i Jhether the association between t ‘of adsorption depending upon wi esac 0 surface is physical or chemical in character, the two types are“adsorption: Physical adsorption is also referred to as Vander Waals adsorption jn ; molecules or atoms are held to the solid surface by weak Vander Waals forces. It is zed by low enthalpy of adsorption of the order of 20 kJ mol, which is of the same 1c heat of condensation. This small enthalpy change is insufficient to lead to breaking of ical adsorption is usually observed at low temperatures or on relatively inert surfaces. ntion: In chemisorption, a term for chemical adsorption, the molecules are adsorbed ‘surface by forming chemical bonds. These bonds may be covalent or ionic in nature, e enthalpy of chemisorption is much greater than that of physiosorption of the order of 200 1-!, The chemisorbed molecules may get completely dissociated into atoms and the these dissociated molecules on the surface is one reason why solid surface catalyze HoH I I | 1 | fen = Ni — Ni - Ni - | x | \ \ — mi - Semon» _ Ni - Ni - Ni C- 1 \ | 1 een the physical adsorption and chemical adsorption is given in Table 6.2. Table 6.2 ‘Chemisorption It involves the chemical forces of attraction like covalent bonds etc. It is characterized by high enthalpy of adsorption of the’ order of 80-200 kJ mol, It is irreversible. Chemisorptions are specific in nature. A gas will be chemisorbed on such solids only with which it can combine chemically. ~ Only monolayer is formed in chemisorption. Chemisorption usually occurs at high temperatures The activation energy of desorption is high as adsorbate molecules are held by comparatively strong valerice forces. Some examples of chemical adsorption are— (a) Adsorption of O, on tungsten. (b) Adsorption of H, on nickel.” rogeneous Catalysis (Adsorption Theory) Dhis theory was postulated by Faraday (1883) and later on modified by others. This theory is based jomenon of adsorption. of various gases on charcoal of nitrogen on mica.The mechanism of heteropencous adsorption of 1 fant molecules, o the surface of the cataly: Catalysis 335 alysis can he explained satin is of According to thir wtorily on the + theory () The surface of the catalyst has certain active centres due to the unsaturation of valencies at the surface, Gi) The reactant molecules strike Gli) The exothe of magi molecules may nic tude as in che ature of the take place (iv) The bonds between adsorbate and adsorbent are © of metal oxygen bonds, also, as in the ei (v) Due to the close proximity between interaction to form a (Wi) The activated complex breaks to for the products and the free surface of the cat regenerated. (vi hemisorptive process The molecules of the products diffuse the surface and are chemisorhed on it able to supply energy of the cal reactions and hence the dissociation of bonds of advert J usually covalent but sometimes may be ionic adsorbed molecules on the alyst surface, they undergo activated complex, st lyst is away from the surface Of the catalyst. Hydrogenation of ethene in presence of Nickel can be explained, to illustrate the above points HO ee a Ys Hee Ho Nu f f Hoa The catalyst operates by the following steps— H—H (Reactants) H H (resin renee 1 EL taeti-stbonatis Ni — NN iia Be Ni Ni— Ni Lice lier Reactant Molecules Near the Catalyst Catalyst NNN I | —Ni— Ni Formation of Activated Complex Fig. 6.8 Mecha smaller (0.742 Ni Ni— bod ee Ni N— Ni | | | The weakene Separating the Adsorption of — Reactant Molecules 4 See eas He H ee a re It] | eae ee eres [eta eet | Desvrption of the Products Leaving the Catalyst for Fresh Action ism of Heterogeneous catalysis.Active Centers: As discussed earlier, the activity of the catalyst is due to the presence of residual forces at the surface. X-ray examination has shown that the surface of the catalyst is not uniform, There are a number of edges, peaks and cracks, The catalytic activity at these sites is relatively high due to the presence of more residual forces at these spots Consequently, these are more active in chemisorbing the reacting gases to form the adsorbed activated complex. These are therefore, referred to as the active centres. Catalytic Activit The catalytic | | | activity is inversely related to the strength -—+j— 1-1} — of adsorption of the reactants and directly 1} Proportional to the surface area of the —'!—'—"!— on pistegration catalyst. Metals in a finely divided state —Ni—Ni—ni— ————> | provides large surface area due to the __y jy gh increase in number of active sites. Thus | |] Tota Residual large surface area is available for Total Resicual eeeeeeeea ne adsorption which enhance the activity of _Valencies = 14 the catalyst. rOmoters: It has been shown that the activity of a catalyst can be increased by adding a small amount of another substance, which itself is either anon catalyst or a feeble catalyst. Such a substa is called a promoter. Many examples of promoter action in heterogeneous reac Molybdenum (Mo) or aluminium oxide (4/, 03) promotes the activity of iron catal synthesis for the manufacture of ammonia. Fei Ne + SH, == 2NHs Similarly, the reduction of CO by hydrogen to yield methyl alcohol, a mixt chromium oxide is used as a catalyst. Zn acts as the catalyst and Cry O; acts as promoter. 2 of zine and cO+H, 2105 cH,0H Although there is no satisfactory theory to explain the action of promotes but adsorpion heer Provides some explaination. The increase in the catalytic activity is presumed i S . : a @/__ Change in Lattice Spacing: The lattice spacing of the eas is ine 7 an an of promoters. Because of this, the bond between the be feito of a mo and hence cleaved mote easily thereby making the reaction go faster.338 Engineering Chemistry Lattice spacing Fig. 68 Action of Catalytic Promoter | the number of active sites: It is believed that probably promoters increase the curves and cracks) at the surface of the catalyst thereb: centres. The increase in the active sites results in greater adsorption of the son the interface between the Promoter and the catalyst, where the free Increased adsorption results in higher rate of reaction, ag: The presence of small amount of certain substai Some catalysts. These substances are referred to as icient to retard the rate of the reaction, Y increasing the INCes destroys oF lowers poisons. A small amount preferential adsorption of inactive. For example, a ailable for the adsorption of reactants lyst thereby rendering, it Surface marks the surface unay. ‘Teaction decreases it may combine with the catalyst. Fe is Fe+ HS —> Fes +H, strength of adsorption, poisoned by presence of H,S e extent and m the reaction mixture. For exampl d as a catalyst. Water Vapour or oxyge rm an oxide of iron. If the poison (#;0 Teduced to iron by the hydrogen preset! restored, om the gas the iron oxide is and its catalytic activity is oisoning, the Poisons affect the catalyst © ged. It is not easy to reactivate the a cal treatment for removal Of poison often regenerates 5 aking i Permancly Poisons the catalytic power of latin ongrilut trioxide from sulphur dioxide. Table (6-3) si me of the catalyzed reactions along with the a Sulphur dioxide. Table (6. alyst used and substances which pols” ie catalyst. aCame a9 Table 6.3: Poisons in Various Catalytic Reactions Reacti ‘eaction Catalyst Poison S02+02 + so3 Pt As,0. 20, No +3Hy + 2NH, Fe Hs 2H) +0, + 2H,0 Pt co 1 1,0, > H, +10. 1,0, 2 +30, Glass CoHs ~ NHCOCH, H,0; + H, +10, Pt L a | In some cases one of the products of a reaction j thus the rate ofthe reaction falls considerably and the phenomecey Hed autocatalytie poisoning The decomposition of ammonia catalyzed by platinum is retarded after sometime on account of the adsorption of one of the products i.e hydrogen on the surface Of platinum which is used a Strongly adsorbed by the catalyst surface: Sa catalyst ificity or Selectivity: The specific action of the catalyst is due to the fact that the extent of adsorption of the reactant molecules on the catalyst depend upon the ch catalyst for the reactant molecules. In other words, the adsorption depends 0 the adsorbent i.e. catalyst, and adsorbate i.e. reactants. So a catalyst under - H;0 + Oz Reaction Progress ——> ‘atalysed and Uncatalysed Reaction Fig. 6.11 Comparison of Activation Energy of C: Enzymes are highly specifie: The important characteristic of enzymes is their extreme that the conformation or overall chain folding, specificity. This is quite evident from the fact tl of the enzyme confers a specific conformation to the active site. The substrate molecule which this shape otherwise not, (Lock & key model), have the complementary shape would fit into It has been suggested that each biochemical process has its own specific enzyme, Examples * the enzyme urease catalyzes the hydrolysis of urea and no other amide, not even methy! urea. * the enzyme lactate dehydrogenase catalyzes the dehydrogenation of lactic acid to yield Pyruvic acid but does not catalyze the dehydrogenation of other acids. * the enzyme fumerase catalyzes the reaction of fumaric acid with water to form malic ach! but the cis isomer of fumaric acid is not catalyzed. * Where the compound can exist in optically active isomers, an enzyme can act on cone of the isomers and is unable to act on the other. The enzyme present in Pencillium glaucum, ordinary mould, when added to + tartaric acid, decomposes the (+) form only.348 Engineering Chemistry ¢ folding pattern depending upon +, substrate molecule can fit, thus makin (Ener are proteins which form a type of specifi f Lock and Key model given confStmation of protein molecule, in which only specific sub: enzymes highly specific. This concept is explained on the basis 0} Emil Fischer. k & Key Model Kemil Fischer proposed this model in (1894) 10 exp! of this hypothesis are— sy’ An enzyme is ordinarily a very large protein mole‘ the enzyme a specific geometry having cavities 0 (ii) The reaction with the substrate takes place at their active sites whereas rest of the proteiy molecule remains undisturbed. yo ‘A substrate molecule which has got complemen- tary structure to the active centre may fit into it. In other words the rigid structure of active sites on protein molecules can be compared to a lock into which the substrate molecule having complemen- tary shape can fit, just as key fits into a lock. ain the specificity of enzymes. The main poin, cule coiled in a definite pattern which give: n the surface called active. sites. (iv) As the substrate molecules are drawn into the active site, they are activated and undergo the catalysed reaction forming the products. (v)_ The product seperate from the enzyme, readying the active sites for fresh action. Fig, 6.10 gives the schematic illustration of lock Fig. 6.9 The Solid State Conformation of the and key model. Enzyme Lysozyme. Shaded Area Depicts the Active Site. + Product (9) Gray E Hing (©) Substrate Molecule (©) Enzyme is Acta 8 Eis into he Acve Ready for Fresh Action Fig. 6.10 Lock and Key Model _Aharacteristics of Enzyme Catalysis 1, Enzymes constitute a class of most effi i icient catalysis. They inc iochemi<# reactions by factors ranging from 10° to 10'2. For example, saith nich _ : ws ae s e eat as rice or bres gets broken down in the body cells in about twenty steps to finally form CO, and H0. and HyCatalysis 35° is maximum at OPTIMUM optimum pH : The rate of Teaction and hence pH. activity of an enzyme is maximum at a given pH called optimum pH. The enzymes of the body exhibit their maximum activity at pH close to 2.4, Change in conformation of the enzyme with change in external conditions, again explains the depend, ence of enzyme catalysis on pH. Since enzymes are proteins which are inturn made up of a large number of amino acids. Change in pH markedly affects the amino and carboxylic acid groups of the oH Protein, which results in change in the tertiary Fig. 6.14 Effet of pH on Rate of Reaction of structure of the protein. Thus the catalytic site of Enzyme Catalyzed Reaction the enzyme is affected. Also pH change can cause denaturation of the enzyme protein, reducing the catalytic efficiency. The pH dependence of the rate of an enzyme catalyzed reaction is shown in Fig, 6.14 Enzymes also have valuable industrial and medical applications. The fermenting of wine curdling of cheese, brewing of beer have been practised from earlier times. Since then enzymes have assumed an increasing importance in industrial processes that involve organic che reactions, The uses of enzymes in medicine include, killing disease causing miero organi promoting wound healing and diagnosing certain diseases. iple of Enzyme Catalysis Chymotrypsin is a digestive enzyme which hydrolyse certain peptide links in proteins. Its conformation and sequence of amino acids have been determined. It is a soluble globular protein folded in suc ® Way that its lipophilic parts are turned inwards, away from water, forming maximum intramolecu! hydrogen bonding, Chymotrypsin not only cause hydrolysis of proteins, but also of certain amides and esters. The action of chymotrypsin is illustrated below in the hydrolysis of amide linkage in proteins 1 Step: The enzyme acts as an alcohol and protein undergoes nucleophilic acyl substitution Reaction Rate. —> ical CNH + E-0H —> ~~ C—O E + NH Part of Protein Enzyme ‘Acyl Enzyme met Thus an enzyme ester is formed. ; TI Step: In this step, the ester is hydrolyzed to form carboxylic acid, the remaining portion ag molecule. The enzyme is regenerated. netics of Enzyme Catalyzed Reactions The mechanism of enzyme catalyzed reactions was proposed by L. Michael's and M.L. Menten. This "echanism is known as Michaclis-Menten mechanism, The mechanism can be explained as followsain compounds: Inhibition occ, i nzyme to substrate molecules bind to the et - Substrap, a racer a the use of penicillin is based on the competi, al substrate ae of the enzyme which is used by bacteria to construe, he action of inhibitor. of cert: 4. Enzyme activity can be inhibited by the presence when molecules, very sim bi of the actt and prevent binding inhibition. Pt bl active si n. Penicillin blocks t of th their c ‘ wall, Fig. (6.12) represents schematically i . Fig. > y ENZYME INHIBITOR COMPLEX ENZYME ‘SUBSTRATE INHIBITOR Fig. 6.12 Competitive Inhibition 5. Catalytic activity of enzyme is greatly enhanced by the presence of een Enzymes are frequently associated with activators called coenzymes. Coenzymes promote the catalytic action of the enzymes. Metal ions like Na’, Co’, Cu?*, Mg?" ete can act as coenzymes of sometimes vitamins form a part of the structure of coenzymes. Adenosine triphosphate (ATP) is an important coenzyme which participate in energy producing process in cell membranes 6. Catalytic activity of the enzyme is maximum OPTIMUM TEMPERATURE at the optimum temperature-The maximum efficiency of a catalyst is exhibited at an opti- mum temperature. It is a well known fact that rate of a reaction increases with increase in temperature, but this is not the case with enzyme catalyzed reactions. The rate of a enzyme catalyzed reaction is increased upto a certain Point with rise in temperature thereafter it de- creases and eventually approaches zero. The temperature at which the reaction rate is maxi- mum is called optimum temperature, The effect Fig. 6.13 Effect of Temperature on the rate of ch temperature on enzyme catalyzed reactions is Reaction of Enzyme Catalyzed Reaction illustated in Fig, 6.13, Rate —> Temperature ——> The above can be explained on the basis of conformational degree of folding ofthe protein is altered and this affects the forma In other words the enzyme is det destroyed. At temperatures abov, aspects. At high temperatures the tion of enzyme substrate complex. natured at high temperatures and its protein structure is gradually ¢ 45°C the thermal denaturation is quite significant whereas at 55° Protein completely destroys the catalytic activity, The optimum temperatures of enzyme reactions occuring in human body is 37° C. If the temperature becomes higher the enzymatic activity is reduced i :326 Engineering Chemistry decomposition of hydrogen peroside. This is true in the case of heteroxencous catalysis In case of homo, neons catalysis, however, the rate of reaction is proportional to the concentration of the catalyst. For the acid and alkaline hydrolysis of an ester. the rate of 5. a5 an catalyst reaction is proportional fo the concentration of the acid, which a RCOOR’ +H,0 RCOOH + R'OH In Friedel Crafts reaction, anhydrous aluminium chloride function as a catalyst effectively if present to the extent of 30% of the mass of benzene which is appreciably large amount ch, : CyHg+ CH scl 85 C,HJC)H, +HICI Ip certain heterogeneous reactions, the rate of the reaction is proportional to the area of the ‘atalytic surfac&)This explains why the finely divided state of a solid catalyst is much more effective ing the rate of reaction. J creas A catalyst is specific in its action: A particular substance can act as a catalyst only ir Particular reaction. For example MnO, may catalyze the decomposition of KC1O,, but no: of KCIO,. Highly specific action of a catalyst can be compared to the specifi which can open a particular lock. Enzymes are also highly specific in thelr a the other hand, the transition metals like iron, cobalt, nickel, platinum and palladium can catalyze various reactions. 4. Nature of the products is unaltered by the presence of the catalyst: The combination o N, and H under suitable conditions will give NH, in presence or absence of catalyst. Simi: SO, and O, will always combine to form SO, whether a catalyst is present or aot However there are some exceptions also. For example CO and Hy combine to give three different products when different catalysts are used. CO+3H, %, CH,+H,0 co+H, —*y HCHO 200+ C0, CO+2H, BO cH on Similarly chlorination of toluene absence of sunlight takes place n the presence of a hal the benzene ring en carrier such as iron in the cn, cn, oH : or a, But chlorine is substituted in the side chain in the absence of a catalyst but in presence of sunlight.the reaction, which is of varying magnitude for different reactionsUIf the activation Catalysis 1e-6.1 [Reaction Activation Energy E, (kJ mol) | In Absence Tin Presence -—ol Catalyst | —of Catalyst @ 2HIH, +1, Ate ied Ws 1 5 Pt ; Ws 184 59 (i) 2NH; 9 N, +3H, Woy 350 162 (ii) 2N,042N) +0, Aug 245 121 Pty 245 134 (iv) (C2H5)30 pyrolysis Lye) 224 laa | Thus whether rate of a given reaction is fast or slow depends upon the activation energy o: ; energy is less fe and vice versa. S2CRITERIA OR CHARACTERISTICS OF CATALYSIS The following features are common to all catalytic reactions A catalyst remains unchanged mass and composition at the end of the reaction: although it frequently undergoes a physical change. For example platinum gauze car in the oxidation of ammonia, becomes quite rough after some weeks, Sen dioxide employed to catalyze the decompos ion of potassium chlorate, is in the forms of lanes crystals in the beginning of the reaction but changes to a fine powder in the emi Since the catalyst undergoes a Physical change, it implies that it is involved in the mec hanism of the reaction but regenerated in the end. The Participation of MnO, in the decomposition of KCIO, is believed to be as explained below ; 2KCIO, +2Mn0, > 2KMnO, +Cl; +05 2KMnO, > K)MnO, + MnO, +O, K)MnO, +Cly > 2KCL+ MnO, +O, The evidence for the above mechanism is provided by the fret, that oxygen ps epared by the above method contains traces of chlorine, Moreover the reaction mixture st cooled ait carly Stages appear pink due to the formation of KMaO, cof the am: Since the catalyst A small amount of catalyst is sufficient to alter the rte of the reaction: S I i is sufficient to briny, appreciable change SRO Used up in the chemical reaction, « small inouat bation to bing apc ms in the sate of reaction. For example, Fem of copper (ll) ions in 10° | r r hite ” en. Sit y colloidal pl. m, Satalyze appreciably the oxidation of sodium sulphite by ossgen. Similarly col litres, is enough to awcelerate the Present in low concentration to the estent of | mole 11 10" litres, is enoug!