Chapter 4The Study of Chemical Reactions.ppt

Chapter 4The Study of Chemical Reactions Tools for Study To determine a reaction’s mechanism, look at: Equilibrium constant Free energy change Enthalpy Entropy Bond dissociation energy Kinetics Activation energy Chlorination of Methane Requires heat or light for initiation. The most effective wavelength is blue, which is absorbed by chlorine gas. Lots of product formed from absorption of only one photon of light chain reaction . Free-Radical Chain Reaction Initiation generates a reactive intermediate. Propagation: the intermediate reacts with a stable molecule to produce another reactive intermediate and a product molecule . Termination: side reactions that destroy the reactive intermediate. Initiation Step A chlorine molecule splits homolytically into chlorine atoms free radicals Propagation Step 1 The chlorine atom collides with a methane molecule and abstracts removes a H, forming another free radical and one of the products HCl . Propagation Step 2 The methyl free radical collides with another chlorine molecule, producing the other product methyl chloride and regenerating the chlorine radical. Overall Reaction Termination Steps Collision of any two free radicals Combination of free radical with contaminant or collision with wall. Equilibrium constant Keq [products] [reactants] For chlorination Keq 1.1 x 1019 Large value indicates reaction “goes to completion.” Free Energy Change DG free energy of products - reactants , amount of energy available to do work. Negative values indicate spontaneity. DGo -RT lnKeq where R 1.987 cal/K-moland T temperature in kelvins Since chlorination has a large Keq, the free energy change is large and negative. Problem Given that -X is -OH, the energy difference for the following reaction is -1.0 kcal/mol. What percentage of cyclohexanol molecules will be in the equatorial conformer at equilibrium at 25°C? Factors Determining ?G? Free energy change depends on enthalpy entropy ?H? enthalpy of prod