Atkins’PhysChem 26-1.pptVIP

Chapter 26The Kinetics of complex Reactions Chain reactions 26.1 The rate laws of chain reactions Consider the thermal decomposition of acetaldehyde 26.1 The rate laws of chain reactions The net rates of change of the intermediates are: 26.1 The rate laws of chain reactions Sum of the above two equations equals: 26.1 The rate laws of chain reactions Example: The hydrogen-bromine reaction has complicated rate law rather than the second order reaction as anticipated. 26.1 The rate laws of chain reactions The following mechanism has been proposed to account for the above rate law. 26.1 The rate laws of chain reactions The net rates of formation of the two intermediates are 26.1 The rate laws of chain reactions The steady-state concentrations of the above two intermediates can be obtained by solving the following two equations: 26.1 The rate laws of chain reactions Substitute the above results to the rate law of [HBr] 26.2 Explosions A thermal explosion is a very rapid reaction arising from a rapid increase of reaction rate with increasing temperature. 26.2 Explosions 2H2(g) + O2(g) → 2H2O(g) 26.2 Explosions 2H2(g)+O2(g)→2H2O(g) 26.2 Explosions Analyzing the reaction of hydrogen and oxygen (see preceding slide), show that an explosion occurs when the rate of chain branching exceeds that of chain termination. 26.2 Explosions 26.2 Explosions Applying the steady-state approximation to ·OH and ·O· 26.2 Explosions Therefore 26.2 Explosions At low O2 concentrations, termination dominates branching, so kterm kbranch. Then 26.2 Explosions At high O2 concentrations, branching dominates termination, kbranch kterm. Then 26.3 Stepwise polymerization Stepwise polymerization: any 2 monomers in the reaction mixture can link together at any time and growth of the polymer is not confined to chains that are already forming. 26.3 Stepwise polymerization Because the condensation reaction can occur between molecules containing any number