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Ch1b09Lecture17

Ch1b09Lecture17 - Ch1b Lecture 17 Past 6 weeks introduction...

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Ch1b Lecture 17 February 17, 2009 Past 6 weeks: •introduction to organic chemistry •spectroscopy •thermodynamics Preview of coming attractions: •kinetics (week 7) •organic reactions (week 8) •intermolecular interactions, polymers (week 9) •bio-organic chemistry (week 10) 1
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chemical kinetics: the rates and mechanisms of chemical processes OGC chapter 18 Caltech reaction kinetics related Nobel Prizes Rudy Marcus, 1992, "for his contributions to the theory of electron transfer reactions in chemical systems" Ahmed Zewail, 1999, “f or his studies of the transition states of chemical reactions using femtosecond spectroscopy” 2
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http://upload.wikimedia.org/wikipedia/commons/a/a0/Ozone_cycle.jpg practical relevance of kinetics: the ozone layer depletion Cl + O 3 ! ClO + O 2 ClO + O 3 ! Cl + 2 O 2 photodissociation and recombination O 2 ! 2O O+O 2 ! O 3 O 3 ! O 2 + O O + O 3 ! 2O 2 3
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Watson lecture Harry B. Gray Wednesday, February 18 “Powering the Planet with Solar Fuel” practical relevance of kinetics: solar energy 4
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•reaction rate •rate law •reaction order •elementary step •equilibrium constants •derivation of rate laws •half life of reaction Kinetics outline: 5
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reaction rate the reaction rate describes the rate of appearance of products or the rate of disappearance of reactants reaction rate according to reactant v A = " d A [ ] dt reaction rate according to product v B = d B [ ] dt are these rates equivalent? A B YES! 6
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A 2B reaction rate according to reactant v A = " d A [ ] dt reaction rate according to product v B = d B [ ] dt are these rates equivalent? NO! A [ ] + 1 2 B [ ] = constant " d A [ ] = # 1 2 d B [ ] v A = 1 2 v B 7
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The following convention is used to uniquely define the numerical value for the reaction rate: a A b B v = " 1 a d A [ ] dt = 1 b d B [ ] dt 8
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rate law the rate law describes the dependence of the reaction rate on the concentrations of reactants and products A+B C one possible rate law is: v = d C [ ] dt = k A [ ] B [ ] where k is the “rate constant” is this rate law generally correct? NO 9
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The rate law cannot be determined from the overall stoichiometry of a reaction - it must be determined experimentally In general, the rate law for A+B ! C can be written in the following form: v = d C [ ] dt = k A [ ] " B [ ] # " + #
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