单分子反应.pdf

Physical Chemistry II Chapter 12 Rate Theories of elementary reaction §12.4 单分子反应 The rate theory of unimolecular reaction 1 Introduction Experimental Observation Gaseous decomposition Isomerization Chemical reaction with light ignition Most of them is of first-order, therefore they are usually called unimolecluar reaction Perhaps, they are contains several elementary reactions. Concept Definition Unimolecular reaction is an elementary reaction with only one reactant molecule Puzzling question 1: According to SCT TST: bimolecular reaction system reactants must collide with each other to acquire enough activation energy Theoretical Conclusion: all gaseous reaction should be second-ordered. Puzzling question 2: A single molecule at ground state will not undergo any reaction except that it was activated by energy of some types. ? * A → A → P How do reactant molecules attain necessary energy of activation ? Perrin’s radiation activation theory 1918 the molecule was activated by absorption of infrared radiation from the container or other molecules radiation * k 1 A ⎯⎯⎯⎯→ A ⎯⎯→ P dP * k [A ] 1 dt unimolecular reaction is of first-order Questions proposed by Langmuir the energy of the infrared radiation of the wall of container is very low and is not sufficient for activation. 设能垒高度 Δε=300 kJ.mol-1=4.98E-19 J.分子-1 辐射能与波长 hν=hc/λ