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Learn about collision theory, activation energy, and reaction rates. Explore potential energy diagrams and the transition state model. Understand factors affecting reaction rates and draw energy diagrams.
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Chemistry 1011 TOPIC Rate of Reaction TEXT REFERENCE Masterton and Hurley Chapter 11 Chemistry 1011 Slot 5
11.4 Models for Reaction Rate YOU ARE EXPECTED TO BE ABLE TO: • Apply collision theory and the concept of activation energy to explain reaction rates. • Apply the transition state model to explain reaction rates. • Draw a potential energy diagram to show the activation energy, energy change, reactants and products of a chemical system given appropriate data. Chemistry 1011 Slot 5
Collision Theory • Molecules must collide before they can react • In a gas, molecules are traveling with different velocities and have different kinetic energies. The average kinetic energy is dependent on temperature (Kinetic Theory of Gases) • Colliding molecules must together have enough kinetic energy to break existing bonds. • The minimum kinetic energy required for a reaction to occur is the activation energy, symbol Ea Chemistry 1011 Slot 5
Energy diagram Chemistry 1011 Slot 5
Collision Theory • Molecules must also collide with a favorable orientation for reaction to occur • The factors affecting the rate of reaction are: • Fraction of collisions which occur with required orientation (p) • Collision frequency (Z) • Fraction of collisions with required energy (f) • Most collisions do not result in reaction Chemistry 1011 Slot 5
Effective vs. ineffective collisions Chemistry 1011 Slot 5
Collision Theory and the Rate Constant • For elementary processes, where the rate law expression is: Rate = k[A][B] k = pxZxf • It can be shown that the fraction of collisions with sufficient energy is: f = e-Ea/RT • R = gas constant • T = temperature in Kelvin Chemistry 1011 Slot 5
Collision Theory and the Rate Constant • Substitute into the collision theory equation for the rate constant: k = pxZx e-Ea/RT • The larger the activation energy, the smaller the fraction of molecules having enough energy to react, so the slower the rate Chemistry 1011 Slot 5
Limitations of Collision Theory • Collision theory does not provide any prediction of p, the “steric factor” • Calculated values for the rate constant are usually too high compared with measured values • Measured activation energies are lower than the energies of the bonds that have to be broken in reactions Chemistry 1011 Slot 5
Transition State Theory • At the moment of collision, molecules with enough energy and the right orientation combine to form an activated complex • The activated complex can either revert back to reactants or decompose to products • The exact nature of the activated complex is difficult to determine • Less energy is required to form an activated complex than to beak bonds Chemistry 1011 Slot 5
Energy diagram Chemistry 1011 Slot 5