Speeding up the approach to equilibrium Catalysis Speeding up the approach to equilibrium

History Kirchoff in 1814 noted that acids aid hydrolysis of starch to glucose Faraday (and Davy) studied oxidation catalysts in the 1820’s Catalyst defined by Berzelius in 1836 A compound, which increases the rate of a chemical reaction, but which is not consumed by the reaction Deacon, Messel, Mond, Ostwald, Sebatier processes (HCl, SO2 oxidation, water gas shift, ammonia oxidation, ethene hydrogenation) 20th C: ammonia production, cracking reactions, hydrocarbon production, catalytic converters etc. Catalysis science developed by Langmuir, Emmett, Rideal and others. http://dept.chem.polimi.it/~citterio/SilsisMI/Introduction.pdf

Catalysis When we consider a catalytic reaction, we may imagine that the reaction mechanism consists of many different steps. Catalyst must be a reactant in one of the first steps in the mechanism and a product in one of the last steps.

Heterogeneous catalysis Chemisorption and catalysis Diffusion of reactants Adsorption Surface diffusion Reaction Desorption Diffusion of products

2 main mechanisms Langmuir-Hinshelwood Reaction between adsorbates Eley-Rideal Reaction between adsorbate and incoming molecule

LH model for unimolecular reaction Decomposition occurs uniformly across the surface. Products are weakly bound and rapidly desorbed. The rate determining step (rds) is the surface decomposition step. pA QA fast RDS khet A B Rate = k qA For Langmuir adsorption

LH model for unimolecular reaction Two limiting cases Low pressures/ Weak binding Kp<<1 Rate ≈ kKp Rate linearly dependent on gas pressure First order reaction Surface coverage very low High pressures/ Strong binding Kp>>1 Rate ≈ k Rate independent of gas pressure Zero order reaction Surface coverage almost unity

LH model for bimolecular reaction Langmuir-Hinshelwood reaction with surface reaction as rds pA QA fast RDS khet A AB B pB QB Rate = k qA qB

Langmuir adsorption of mixed components

Langmuir adsorption of mixed components

Langmuir adsorption of mixed components

LH model for bimolecular reaction Rate = k qA qB

LH model for bimolecular reaction pA rate For constant PB QB >> QA Rate limited by surface concentration of A QB << QA Rate limited by surface concentration of B

Eley-Rideal bimolecular surface reactions pA QA fast RDS khet A AB B pB An adsorbed molecule may react directly with an impinging gas molecule by a collisional mechanism

Eley-Rideal bimolecular surface reactions rate = k QA pB = k KApA pB / (1+KApA) QA = 1 pA rate For constant PB High pressure Strong binding KApA >> 1 rate = k pB …….. zero order in A kexp Note: For constant pA, the rate is always first order wrt pB Low pressure Weak binding KApA << 1 rate = khet KA pA pB …….. first order in A kexp

Diagnosis of mechanism If we measure the reaction rate as a function of the coverage by A, the rate will initially increase for both mechanisms. Eley-Rideal: rate increases until surface is covered by A. Langmuir-Hinshelwood: rate passes a maximum and ends up at zero, when surface covered by A. B + S  B-S cannot proceed when A blocks all sites.

Transition State Model of Catalyst Activity #hom adsorbed reactants adsorbed products #het Langmuir-Hinshelwood Kinetics Adsorption of reactants and desorption of products are very fast. DEads and DEdes very small. Surface Reaction is RDS: DEhet DEhom DEads DEdes DEhet potential energy reactants products reaction co-ordinate

Principle of Sabatier A “volcano” curve When different metals are used to catalyse the same reaction, it is generally observed that the reaction rate can be correlated with the position of the metal in the periodic table: A “volcano” curve

Catalyst Preparation For a catalyst the desired properties are high and stable activity high and stable selectivity controlled surface area and porosity good resistance to poisons good resistance to high temperatures and temperature fluctuations. high mechanical strength no uncontrollable hazards Once a catalyst system has been identified, the parameters in the manufacture of the catalyst are If the catalyst should be supported or unsupported. The shape of the catalyst pellets. The shape (cylinders, rings, spheres, monoliths) influence the void fraction, the flow and diffusion phenomena and the mechanical strength. The size of the catalyst pellets. For a given shape the size influences only the flow and diffusion phenomena, but small pellets are often much easier to prepare. Catalyst based on oxides are usually activated by reduction in H2 in the reactor.

Case studies Ammonia synthesis (Haber-Bosch) Hydrogenation of CO (Fischer-Tropsch) http://www.uyseg.org/greener_industry/index.htm

Ammonia synthesis A: Steam reforming B: High temperature water-gas shift C: Low temperature water-gas shift D: CO2 absorption E: Methanation F: Ammonia synthesis G: NH3 separation.

Ammonia reactants Steam reforming CH4(g) + H2O(g)  CO(g) + 3 H2(g) 15-40% NiO/low SiO2/Al2O3 catalyst (760-816C) products often called synthesis gas or syngas Water gas shift CO(g) + H2O(g)  CO2(g) + H2(g) Cr2O3 and Fe2O3 as catalyst carbon dioxide removed by passing through sodium hydroxide. CO2(g) + 2 OH-(aq)  CO32-(aq) + H2O(l)

Ammonia Synthesis Fe/K catalyst exothermic

Mechanism 1 N2(g) + * N2* 2 N2* + * 2N* 3 N* + H* NH* + * 4 NH* + H*   N2* 2 N2* + * 2N* 3 N* + H* NH* + * 4 NH* + H* NH2* + * 5 NH2* + H* NH3* + * 6 NH3* NH3(g) + * 7 H2(g) + 2* 2H* Step 2 is generally rate-limiting. Volcano curve is therefore apparent with d-block metals as catalysts. Ru and Os are more active catalysts, but iron is used.

CO+3H2CH4+H2O ( DG298, -140 kJ/mol) Hydrogenation of CO Hydrogenation of CO is thermodynamically favourable; the first example, methanation catalysed by nickel was reported by Sabatier and Senderens in 1902 CO+3H2CH4+H2O ( DG298, -140 kJ/mol) In their classic 1926 papers Fischer and Tropsch showed that linear alkenes and alkanes (as well as some oxygenates) are formed at 200–300°C and atmospheric pressure over Co or Fe catalysts nCO+(2n+1)H2CnH2n+2+nH2O 2nCO+(n+1)H2=CnH2n+2+nCO2 Since syngas (CO + H2) is readily available from a variety of fossil fuels, including coal, the Fischer–Tropsch process became industrially important for economies which had good supplies of cheap coal but which lacked oil

Fischer-Tropsch Iron catalysts give mainly linear alkenes and oxygenates, while cobalt gives mostly linear alkanes. Ruthenium, one of the most active catalysts but one which, owing to its expense is little used industrially, can give high molecular weight hydrocarbons; rhodium catalysts make significant amounts of oxygenates in addition to hydrocarbons, while nickel gives mainly methane. Catalyst can be immobilised on Kieselguhr (diatomaceous silicate earth), alumina, active carbon, clays and zeolites.

FT mechanism adsorption and cleavage of CO and the stepwise hydrogenation of surface carbide giving methylene and other species Maitlis, P. M.; Quyoum, R.; Long, H. C.; Turner, M. L. Appl. Catal. A: General 1999, 186, 363-374. Towards a Chemical Understanding of the Fischer-Tropsch Reaction: Alkene Formation

Other mechanisms? Boudouard reaction. Important in methanation (over Nickel). 2CO C + CO2 Some evidence that hydrogenation of adsorbed carbon leads to formation of hydrocarbons. Also an important side (undesired) reaction in some hydrocarbon conversion reactions (coking)