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Crash Course on Organic Reaction Dynamics

Apr 29, 2025

Crash Course Organic Chemistry: Reaction Kinetics and Thermodynamics

Introduction

  • Presenter: Deboki Chakravarti
  • Organic chemicals are present in many smells around us.
  • Example: Limonene in lemons converts to alpha-terpineol with a lilac smell through enzyme-catalyzed reaction.
  • To understand such reactions, concepts like reaction kinetics, thermodynamics, spontaneity, and free energy are essential.

Key Concepts in Organic Reactions

Useful Chemical Reactions

  • Must have more products than reactants.
  • Reaction should occur at a reasonable speed.
  • Thermodynamics: Relates to energy and reaction progress.
  • Kinetics: Relates to the rate of reaction.

Review of Key Thermodynamics Concepts

  • ΔH (Enthalpy): Change in heat at constant pressure.
    • Exothermic: Reaction gives off heat (Negative ΔH).
    • Endothermic: Reaction absorbs heat (Positive ΔH).
  • ΔS (Entropy): Degree of disorder or randomness in the system.
    • Example: Increase in entropy when a compound changes from a ring to a chain.
  • ΔG (Gibbs Free Energy): Predicts spontaneity of a reaction.
    • Negative ΔG: Spontaneous reaction.
    • Positive ΔG: Non-spontaneous reaction.
  • Equation: ΔG = ΔH - TΔS

Equilibrium and Reaction Rates

  • Equilibrium Constant (K): Ratio of products to reactants at equilibrium.
    • Large K: More products.
    • Small K: More reactants.
  • Relationship: ΔG = -RTlnK
    • Negative ΔG → Large K; Positive ΔG → Small K.

Energy Diagrams

  • Y-axis: Reaction energy (ΔH or ΔG).
  • X-axis: Reaction progress from reactants to products.
  • Transition State: Peak of the diagram.
  • Activation Energy: Energy required to start the reaction.
    • Higher activation energy → Slower reaction.

Reaction Example: But-1-ene and Hydrogen Bromide

  • Endothermic reaction forming primary or secondary carbocations.
  • Secondary carbocations more stable due to less energy needed for formation.

Multi-Step Reactions

  • Example: Reaction between 2-methylprop-2-ene and methanol forming MTBE.
    • Involves sulfuric acid as a catalyst.
    • Path includes multiple intermediates and transition states.
  • Intermediates: Have full charges and bonds.
  • Transition States: Partial charges and bonds.

Catalysts in Reactions

  • Catalysts speed up reactions without being consumed.
  • Lower the activation energy in energy diagrams.

Conclusion

  • Reviewed thermodynamics, enthalpy, entropy, Gibbs free energy.
  • Studied free energy diagrams, intermediates, and transition states.
  • Explained catalysts' role in reducing activation energy.
  • Upcoming episodes to cover more on addition reactions.

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