CATALYSIS “He who wishes to fulfill his mission in the world must be a man of one idea, that is of one great overmastering purpose, overshadowing all his aims and guiding and controlling his entire life.” CFendamental Definitions at a Glance 4 Catalyst is defined as a substance, a small amount of which alters (increases or decreases) the velocity of a chemical reaction by its mere presence, without itself undergoing any change in mass and composition at the end of the reaction. + Positive catalyst accelerates the speed of reaction (It is also known as Accelerator). 4 Negative catalyst retards the chemical reaction (It is also known as inhibitor). 4 A catalytic promoter or activator may be defined as a substance which promotes the activity of the catalyst to which it is added (in small amounts) and this process is known as activation. © Catalytic Poisons (anti catalyst) are substances that decrease or inhibit the activity of catalysts. & The phenomenon of altering the velocity of a chemical reaction by the presence of catalyst is called catalysis. ‘ Induced catalysis is the phenomenon in which one reaction influences the speed of other reaction which is not possible under ordinary conditions. 4 In Homogeneous catalysis, the catalyst and the reactants are in same phase. System. consists entirely either of gases or liquids. Reactions involve molecules, ions or free radicals as intermediate. 4 According to intermediate compound formation theory : The catalyst first forms very reactive and unstable intermediate compound with one of the reactants. This intermediate then immediately reacts with other reactants yielding the products of the reaction and liberating the catalyst in its original chemical composition. 275278 A TEXTBOOK OF ENGINEERING CHEMISTRY effective collisions increases with increase in temperature. Evidently, the rate of reaction increases with increase in temperature. Hence one way to increase the rate of reaction is by increasing the temperature. But when we carry out the reaction at higher temperature we do not have good control over reaction. There are side reactions so yield of desired products decreases. Moreover, for attaining higher temperature, energy cost is high. So, it is not an economical way of increasing the rate of reaction. Role of Catalyst We can employ a positive catalyst for increasing the rate of reaction. The catalyst provides an alternative path with less activation energy so more reactant molecules can cross the activation energy barrier at any given concentration and temperature. Reaction (Exothermic) : Reactants —> [Transition state] > Products nee eel a Initial energy content of Reactants: Final energy content of Products : E- (@) Positive (6) Uncatalyzed (O Negative: Activation energies : E, @) energy Increasing. Progress of reaction —> Fig. 2 Illustration of effect of differerit types of catalysts on activation energy and rate of reaction. @ Catalyst provides an alternative path of lower or higher activation energy in and negative catalysis respectively. @ There is no difference in free energy (AG) between uncatalyzed and catalyzed @ Activation energy (E,) determines kinetic feasibility of reaction. ® Free energy change (AG) determines thermodynamic feasibility of reaction. The concentration of the catalytic species will be usually very small compared & concentration of reactant. Consequently, the number of collisions per second between the reactant molecules: catalyst will be much smaller (Usually by a factor of 101) than the collision between the molecules.* Catalyst * Terminologies In 1836, Berzelius realized that there are substances which can increase the rate of a reaction without being consumed in the process. According to him, this was due to loosening of bonds which holds the atoms together. He coined the term catalyst for those substances and called this phenomenon as catalysis (Greek “Kata’—wholly, “lyein"—to loosen). CATALYST Catalyst refers to a substance that is capable of altering the rate of a reaction and is recovered unchanged with respect to composition and amount at the end of the reaction. coieemcage Characteristics 1. A catalyst remains unchanged with respect to composition and amount (mass) at the end of the reaction. However, there might be a change in physical state. For example, the granular MnO, which is used as a catalyst during the decomposition of KCIO, is recovered as powdered MnO, at the end of the reaction. A catalyst is very selective in its action. A small amount of catalyst is enough to catalyze almost an unlimited reaction. Acatalyst does not initiate a reaction rather it only alters the rate of a feasible reaction. o> Every catalyst has its own optimum temperature at which it shows maximum efficiency. 6. A catalyst does not change the position of equilibrium in a reversible reaction as it increases the rate of both forward and reverse reactions in the same proportion. Thus, the approach of equilibrium is quickened. 7. The activity ofa catalyst can be changed by using small amount of foreign substance, i.e., promoter or poison in addition.224 Wi_Engineering Chemistry _ TERMINOLOGIES Promoter ‘A promoter is an additional substance used along with the catalyst to increase the efficiency and life span of a catalyst. It cannot catalyze a process by itself. For example, 1. Mo, in Haber’s process for manufacture of ammonia is an example of promoter. N,+ 3H, => 2NH, C10, in the manufacture of CH,OH CO +2H,0 22> CH,OH Nv Poison , ‘A poison is an additional substance used along with the catalyst that decreases its efficiency. For example, 1. Bromine vapor poisons Ni catalyst during hydrogenation of oil. >. Lead acetate poisons Pd catalyst during preparation of alkene from alkyne. 3. _As,O, poisons Pt catalyst in contact during the process for manufacture of sulfuric acid. 280, *D > 280, 4. Tron catalyst in Haber’s process of’ manufacture of ammonia can be poisoned by hydrogen sulphide. N, +3H, —="5> 2NH, Negative Catalyst or Retarder ‘The catalyst that retards the rate ofa reaction is referred to as negative catalyst. For example, 1. Glycerol can be used to control the rate of decomposition of H,0,, H,0, > H,0 +0, 2. Ethyl alcohol can be used to control the rate of decomposition of CHCI,, CHCl, 2ealeoholtit_, COCI, + Cly Self-Catalyst Sometimes one of the reactants or products formed catalyzes the processes and such a proces: is known as self-catalysis. The corresponding substance is known as self-catalyst. For example |. During acid hydrolysis of ester, the acid formed in the processes operates 2S self catalyst. CH,COOC,H, + H,0 5°, CH,COOH + CHO Catalyst Ag” acts as a self-catalyst during decomposition of arsine. 2AsH, ——> 2As + 3H, Catalyst 2. | Mn** ions catalyze the reaction between KMnQ, and oxalic acid.Catalysist ype 450,0/- + 16H* ——>2 Mn’ 2+ + 10 CO, + 8 HjO Catalyst CATALYSIS z Catalysis is the phenomenon by virtue of which catalyst is able to alter the rate of a reaction. Types of Catalysis Homogeneous catalysis Here, a catalyst remains in the same phase as that of the reactants and is uniformly distributed throughout. For example, - NO, 280545 + Ong ae mS 2(8) 3@) lw “ CH,CHO) > CHlyy* Cw C,3H,,0, + HO ESCs CeH20, +C,H20, 124404 ,s01tiom + He ,20¢ sorsion + CoF12s csotiation Heterogeneous catalysis Here, a catalyst remains in different phase than that of the reactants. It is also known as contact catalysis as the reaction occurs by contact of reactants with the catalyst surface. For example, Pe 280 x¢g) * Org) 280 x) ZY Fe Nag + Haye) 2NH3 Fe 2B, Oi aren ® Or) MnO MnO 2KCIO x) 2KCly) + 302 THEORIES OF CATALYSIS ear ee This is the mechanism by virtue of which a catalyst operates. In general, a catalyst provides an alternate path with much less activation energy (Fig, 6.1). This path modulation in the presence of a catalyst can be discussed with respect to two theories. Without catalyst With catalyst Product Reaction progress —> Fig, 6.1 Lowering of activation energy in the presence of a catalyst226 f]_Engineering Chemistry Intermediate Compound Formation Theory This theory is successful in explaining homogeneous catalysis. According to this theory, the complete process occurs via the following steps: Step I: The catalyst reacts with the prime reactant to form an intermediate compound. Step Il: The intermediate compound subsequently reacts with the other reactant to yield the products. This step is the slowest one and regarded as the rate determining step. Step The catalyst released in step [I participates further in the reaction as per steps I and IT. Mathematical treatment Let us consider a hypothetical process, A+B —“@O 5 ap With respect to the theory, the different steps are ky A+C — AC Intermediate compound AC+B —> AB +C (slow) Released Rate = k, [AC] [B] [6.1] d{ AC At steady state, see ork, [A] [C]—&, [AC]—&; [AC] [B] = 0 or [AC] {k, +k, [B]} =, [AIC] _ AIAIC) ot A= BT 6.2] Substituting [AC] in relation [6.1], we get _ ‘A TAIBIIC] Rate BT [6.3] Case I: If k <<; [B], Rate =k, [A] [C] : [6.4] Case I: If k; [B] << ky Rate 4 SANA Waite [6.5] ky) Therefore, thé rate of a catalyzed reaction is directly proportional to the concent a catalyst, though it is neither produced nor consumed in the process.ms Catalysis 227 Illustration Let us illustrate this theory with a specific example of oxidation of sulfur dioxide. 20, + 0) ——? 280s Steps NO +0, <= NO, (Intermediate compound) 80, +NO, =? 80am NO Limitations ‘The limitations of the theory are as follows: 1, It cannot be applied in heterogencous catalysis. 2, It fails to explain the increase or the decrease of efficiency of a catalyst in the presence of a foreign substance, 3, It fails to account for the negative catalysis. Adsorption Theory This theory is successful in explaining heterogeneous catalysis. The process takes place in the following steps: Step I: As the reacting molecules are allowed to react in the presence of @ catalyst, they get diffused on the surface of the catalyst Step Hi: The reactant molecules get adsorbed on the surface of a catalyst. This is through the development of van der Waals forces with the active centers or free valencies present ‘on the surface of a catalyst. Step III: The adsorbed reactant molecules then get transferred into an energy-rich activated - complex. Step IV: The activated complex decomposes to yield the product which diffuses away from the catalyst. ‘The complete process is explained schematically in Fig. 6.2. heir jerk —_ 9-005, nacre te a... ae ae Wel ® teats | Catalyst surface having rk \ Adsorption of oe aoa ae eo eels eo ee a 20g tet \ \ l ee 1 \ _= 9-0-0 — —0-0-O—8 \ Catalyst Intermediate Fig. 6.2 Schematic presentation of different steps in adsorption theory228 ll Engineering Chemistry _ Mathematical treatment ad Rate = a « fraction of the surface of catalyst which is occupied (0) or ze or ee dt 1+kP where k; is the coefficient of adsorption; © = k,P/(1-+k,P) is the result of Langmuir adsorption isotherm; and P is the pressure due to reactant molecules. Note: The Langmuir adsorption isotherm can be shown as follows: Reactants + Surface = Adsorbed surface Rate of adsorption, R, * fraction of unoccupied surface (1 ~ ©) and R, P. Thus, R, « P(1—©), or R,=k,P(1-®) Rate of desorption, Ry x ©, or Ry=kyO At equilibrium, R, = Ry or. k,P(1-)=k,® or @fky+k]=k,P Advantages It successfully explains 1, Efficiency of finely divided catalysts: ‘Smaller is the particle size more is the surfac area which ultimately makes available relatively larger number of free valencie (active sites). Therefore, finely divided catalysts are more effective than lumps.