Notes from CHE2FCB Lecture on Catalysis

Catalysis Overview

  • Catalysts speed up reactions without undergoing permanent changes.
  • They provide alternative pathways with lower activation energy.

Types of Catalysis

  • Homogeneous Catalysis: Same phase as reactants (e.g., gas-phase catalysts).
  • Heterogeneous Catalysis: Different phase, typically solid catalysts where reactions occur on surfaces (e.g., catalytic converters).
  • Enzymes: Biological catalysts that enhance reaction rates significantly.

Key Concepts

  • Activation Energy (Ea): Energy required to initiate a reaction. Catalysts lower Ea.
  • Turnover Frequency (kcat): Number of substrate molecules converted to product per enzyme molecule per second.
  • Michaelis-Menten Mechanism: Describes enzyme kinetics:
    S+EESP+ES + E ⇌ ES → P + E
    K<em>M=k</em>1+k<em>catk</em>1K<em>M = \frac{k</em>{-1} + k<em>{cat}}{k</em>1}

Reaction Pathway

  • Catalyzed reactions have a lower activation energy compared to uncatalyzed reactions.
  • The graph of energy vs. reaction coordinate displays reactants, products, and transition states (TS).

Rate Laws and Catalysts

  • Rate laws incorporate catalysts but typically not intermediates.
  • Example: For bromide-catalyzed decomposition of peroxide:
    extRate=k[H<em>2O</em>2][H3O+][Br]ext{Rate} = k[H<em>2O</em>2][H_3O^+][Br^-]

Autocatalysis

  • Reaction where the product catalyzes its own formation leading to an increase in reaction rate.

Negative Catalysts (Inhibitors)

  • Slow down reactions, e.g., Tetraethyl lead (TEL).
  • Work by changing the pathway or removing reactive intermediates instead of just providing an alternative pathway.

Summary

  • Catalysts do not alter the equilibrium constant (K). They accelerate both forward and reverse reactions equally.
  • The overall reaction remains unchanged, only the rate changes due to the catalyst present.

Key Equation

  • Enzyme kinetics from Michaelis-Menten:
    <br/>ν<em>max=k</em>cat[E]KM+[S]<br />\nu<em>{max} = \frac{k</em>{cat} [E]}{K_M + [S]}