CHBE 452 Lecture 28 Mechanism of Catalyst Action 1 Last Time We Introduced Catalysis Homogeneous catalysts Acids and bases Metal salts Enzymes Radical initiators Solvents Heterogeneous catalysts Supported metals Metal oxides, nitrides, sulfides Solid acids and bases Polymer bound species Increase rates by 1020 or more 2 Today: Mechanisms Of Catalyst Action Catalysts can be designed to help initiate reactions. Catalysts can be designed to stabilize the intermediates of a reaction. Catalysts can be designed to hold the reactants in close proximity. Catalysts can be designed to hold the reactants in the right configuration to react. 3 Mechanism Of Catalysts, Continued Catalysts can be designed to block side reactions. Catalysts can be designed to sequentially stretch bonds and otherwise make bonds easier to break. Catalysts can be designed to donate and accept electrons. Catalysts can be designed to act as efficient means for energy transfer. 4 Mechanism Of Catalysis Continued Is is also important to realize that: One needs a catalytic cycle to get reactions to happen. Mass transfer limitations are more important when a catalyst is present. 5 Today: The Role Of Catalysts In Initiating Reactions, Stabilizing Intermediates Catalysts initiate reactions by help creating active centers (i.e. a radical or ion). Active center could be catalyst itself Could be a radical R-O. Catalysts stabilize intermediates. Catalyst binds to intermediate, lowering the free energy of the reactive intermediates. Raises intermediate concentration. Intermediates less reactive. 6 How Could Catalysts Change H2+Br22HBr 50 +H2 +H2 A H+HBr Br B H+HBr +Br2 +Br2 1/2Br2 1/2Br2 Br+2HBr 0 0 Br+2HBr Br 1/2 Br2+2HBr Free energy, kcal/mole of bromine atoms Mechanism Br2→2Br Br+H2→HBr+H H+Br2→HBr+Br 2Br→Br2 50 1/2 Br2+2HBr Initiate Reaction Gas Phase -50 -50 Reaction Progress Reaction Progress 50 50 +H2 C D +H2 1/2Br2 1/2Br2 0 0 +Br2 Br +Br2 Br H+HBr H+HBr Br+2HBr Br+2HBr 1/2 Br2+2HBr Modify Intrinsic Barriers Stabilize Intermediates -50 1/2 Br2+2HBr -50 Reaction Progress Reaction Progress 7 Key Principles Of Catalytic Mechanisms Catalysts bind intermediates at distinct sites. Mechanism often the same in gas phase & on catalyst. Initiation much faster – in effect do not need initiation reacion. 8 Example Of Catalysts Initiating Reactions C2H6C2H4+H2 (12.41) Gas phase mechanism C2H6 2CH3 (12.42) CH3+C2H6C2H5+CH4 (12.43) C2H5C2H4+H H+C2H6C2H5+H2 (12.45) 2CH3C2H6 (12.46) 2c2H5C4H10 (12.47) CH3C2H5 C3H8 (12.48) (12.44) 9 Catalysis By NO2 Consider adding NO2 NO2 C2 H 6 C2 H5 HNO2 (12.50) Catalysts can initiate reactions. The mechanisms are similar to the mechanisms without a catalyst, but the initiation process is much faster with the catalyst. Effect 109 (small for catalysis) 10 Some Examples Of Reactions Initiated By Catalysts Reaction Catalyst Mechanism of Initiation CH3 CH3 C2H4 +H2 NO2 NO2 + CH3CH3 HNO2 + CH3CH2 CH3COH CH4 + CO I2 X+I2 2I+X I + CH3COH HI + CH3CO Ethylene polyethylene R OOR R OOR 2R O R O+CH2=CH2R OCH2CH2 H2 + Br2 2HBr metalic platinum Br2 + 2S 2Brad Propylene Polypropylene Ti+ Tl+ + propylene CH3CHTiCH2+ C2H5OH C2H4 + H2O H+ C2H5OH + H+ [C2H5OH2]+ [C2H5OH3]+ [C2H5]+ + H2O 2O3 O2 Cl [C2H5]+ C2H4 + H+ O3 + Cl O2 + ClO 11 Gas Phase 50 +H2 H+HBr Br +Br2 0 1/2Br2 Br+2HBr 1/2 Br2+2HBr -50 Reaction Progress Enthalpy, kcal/mole of bromine atoms Enthalpy, kcal/mole of bromine atoms Initiation Often Not Enough. Also Need To Stabilize Intermediates Surface 50 0 1/2Br2 +H2 Br(ad) H(ad)+HBr +Br2 1/2 Br2+2HBr Termination -50 Br(ad)+2HBr Reaction Progress Figure 12.7 The enthalpy changes during the Figure 12.8 The enthalpy changes during the gas phase reaction H2 + Br2 2 HBr assuming Rideal-Eley surface reaction H2 + Br2 2 HBr that the reaction terminates after one cycle on Pt(111) assuming that the reaction terminates after one cycle 12 Stabilization Of Ionic Intermediates RHC CRH RRC CHH (12.63) Possible gas phase mechanism X + RHC CRH RHC CH R X (12.64) R RHC CRH X R2 HCCRH X (12.65) R2 HCCH X R2 C CH H X (12.66) Note big barrier to first step 13 Acid Catalyzed Reaction RHC CRH H RHC CRHH (12.67) RHC CRHH RRHC CHH (12.68) RRC CHH H CHH HC RR (12.69) 14 Stabilization Of Intermediates. Can We Have Too Much of a Good Thing? When we stabilize intermediates we increase the intermediate concentration. We also decrease the reactivity of the intermediates. Which wins? 15 Experimental Evidence HCOOHH2+CO2 H HCOOH HCOO(ad) ad CO H H (ad) HCOOad 2 2 (12.75) 350 Ir Temperature For 50% Conversion Pt 400 Ru Pd Rh 450 Cu Co W Au 550 Fe Ni Ag 500 600 50 60 70 80 90 100 110 120 Heat Of Formation Of Formate 16 Sabatier’s Principle The best catalysts are substances which bind the reactants strongly, but not too strongly. 17 Consider H2+Br2HBr Rideal Eley mechanism Br2 2S 2Brad Brad H 2 HBr H ad Br2 HBr Br H ad Complicated derivation (see text) 1 rHBr 2 k Br exp (1 p,2 ) H ad / B T [H 2 ][S][Br2 ]2 (12.85) (12.76) E 0 H TS / T k Br 2k 0 exp p,2 O ad B 2 a,2 (12.86) 18 For Unlimited Sites 1E+26 2 Rate, Molecules/Cm Sec 1E+31 1E+21 1E+16 1E+11 1E+6 -40 -20 0 20 40 60 80 Heat Of Formation Of Intermediate, Kcal/mole Figure 12.10 The rate of HBr formation as calculated from Equation (12.85), with [S] = 1e14/cm2 and p= 0.5, T = 500K, PH 2 PBr2 1atm. 19 For Finite Number Of Sites So [S] 1 K Br PBr K H PH 2 2 2 2 (12.87) 1E+14 1E+12 2 Rate, Molecules/Cm Sec 1E+16 1E+10 1E+8 1E+6 1E+4 1E+2 1E+0 - 40 - 20 0 20 40 60 80 Heat Of Formation Of Intermediate, Kcal/mole Figure 12.11 The rate of HBr formation calculated from Equation (12.85), with [S] from Equation (12.87) and p= 0.5, T = 500K, PH PBr 1atm. 2 2 20 Common Plots In Literature Sachtler-Frahenfort Tanaka-Tamaru plots: plots: Use heat of oxidation Use heat of oxidation per mole of metal as per mole of oxygen surrogate for heat of as surrogate for formation of product. heat of formation of product. 21 Comparison Of Sachtler-Frahrenfort And Tanaka-Tamaru Sachtler-Frahrenfort Ru 1E+18 Ni 1E+14 W 2 Rh Pd Co Ir Fe 1E+16 Pt Ta 1E+12 Cu 1E+10 -10 -30 -50 -70 -90 -110 0 -20 -40 -60 -80 -100 Heat of formation of oxide per mole of oxygen, Kcal/mol Tanaka-Tamaru 1E+20 Rate, Molecules/cm /sec 2 Rate, Molecules/cm /sec 1E+20 Ru 1E+18 Rh Pd Ir Co 1E+16 Fe Pt Ni 1E+14 W Ta 1E+12 Cu 1E+10 0 -100 -50 -200 -150 -300 -250 Heat of formation of oxide per mole of metal, Kcal/mol Figure 12.13 A Sachtler-Frahrenfort and Tanaka-Tamaru plot for the hydrogenation of ethylene. 22 Summary So Far Catalysts work by initiating reactions, stabilizing intermediates. Leads to 1020 increase in rates – need other effects to get to 1040. Can stabilize too much. 23 Example: Constructing SachtlerFrauhenfort And Tanaka-Tamaru Plots Table 12.E.1 some data for the rate of ethylene hydrogenation on a number of metals 0 C. Next lets construct a Sachtler-Fahrenfort plot of the data. Table 12.E.1 The spreadsheet for example 12.E A 4 Metal 5 6 7 8 9 10 11 12 13 14 15 16 17 Pt Pd Ir Rh Ru Cu Cu Co Ni Fe Fe W Ta B rate 1.0E+16 3.0E+16 3.0E+16 3.0E+17 9.0E+18 8.3E+10 8.3E+10 3.0E+16 1.0E+14 1.0E+16 1.0E+16 3.0E+13 3.0E+13 C D E Hf Of Oxygens Metal Oxide in oxide atoms in oxide -9.7 1 1 -20.4 1 1 -40.1 2 1 -21.7 1 1 -52.5 2 1 -39.8 1 2 -37.1 1 1 -57.2 1 1 -58.4 1 1 -197.5 3 2 -63.7 1 1 -136 2 1 -499.9 5 2 F Hf per mole of oxide G Hf per mole of metal =$C5/D5 =$C6/D6 =$C7/D7 =$C8/D8 =$C9/D9 =$C10/D10 =$C5/E5 =$C6/E6 =$C7/E7 =$C8/E8 =$C9/E9 =$C12/D12 =$C13/D13 =$C14/D14 =$C11/E11 =$C12/E12 =$C13/E13 =$C14/E14 =$C16/D16 =$C17/D17 =$C16/E16 =$C17/E17 24 Solution A 4 Metal 5 6 7 8 9 10 11 12 13 14 15 16 17 Pt Pd Ir Rh Ru Cu Cu Co Ni Fe Fe W Ta B rate 1.0E+16 3.0E+16 3.0E+16 3.0E+17 9.0E+18 8.3E+10 8.3E+10 3.0E+16 1.0E+14 1.0E+16 1.0E+16 3.0E+13 3.0E+13 C D E Hf Of Oxygens Metal Oxide in oxide atoms in oxide -9.7 1 1 -20.4 1 1 -40.1 2 1 -21.7 1 1 -52.5 2 1 -39.8 1 2 -37.1 1 1 -57.2 1 1 -58.4 1 1 -197.5 3 2 -63.7 1 1 -136 2 1 -499.9 5 2 F Hf per mole of oxide G Hf per mole of metal =$C5/D5 =$C6/D6 =$C7/D7 =$C8/D8 =$C9/D9 =$C10/D10 =$C5/E5 =$C6/E6 =$C7/E7 =$C8/E8 =$C9/E9 =$C12/D12 =$C13/D13 =$C14/D14 =$C11/E11 =$C12/E12 =$C13/E13 =$C14/E14 =$C16/D16 =$C17/D17 =$C16/E16 =$C17/E17 25 Comparison Of Sachtler-Frahrenfort And Tanaka-Tamaru Sachtler-Frahrenfort Ru 1E+18 Ni 1E+14 W 2 Rh Pd Co Ir Fe 1E+16 Pt Ta 1E+12 Cu 1E+10 -10 -30 -50 -70 -90 -110 0 -20 -40 -60 -80 -100 Heat of formation of oxide per mole of oxygen, Kcal/mol Tanaka-Tamaru 1E+20 Rate, Molecules/cm /sec 2 Rate, Molecules/cm /sec 1E+20 Ru 1E+18 Rh Pd Ir Co 1E+16 Fe Pt Ni 1E+14 W Ta 1E+12 Cu 1E+10 0 -100 -50 -200 -150 -300 -250 Heat of formation of oxide per mole of metal, Kcal/mol Figure 12.13 A Sachtler-Frahrenfort and Tanaka-Tamaru plot for the hydrogenation of ethylene. 26 Stabilizing Intermediates Not Entire Effect Leads to 1020 increases in rates – -need other effects to get to 1040 Does not lead to selectivity 27 Summary Catalysts work by initiating reactions, stabilizing intermediates. Leads to 1020 increase in rates – need other effects to get to 1040. Can stabilize too much. Other effects connect selectivity. 28 Query What did you learn new in this lecture? 29