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5_60_lecture32

5_60_lecture32 - MIT OpenCourseWare http/ocw.mit.edu 5.60...

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MIT OpenCourseWare http://ocw.mit.edu 5.60 Thermodynamics & Kinetics Spring 2008 For information about citing these materials or our Terms of Use, visit: http://ocw.mit.edu/terms .
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5.60 Spring 2008 Lecture #32 page 1 Complex Reactions and Mechanisms (continued) III) Reversible Reactions k 1 [ B ] A B K = eq k -1 eq [ ] eq A If 1 st order, R forward = R f = k 1 [A] R backward = R b = k -1 [B] At Equilibrium, R f = R b k 1 [A] eq = k -1 [B] eq K eq = k 1 k 1 a) 1 st order reversible reactions k 1 d[A] B = k 1 [A] k 1 [B] dt [B] = [B] o + ([A] o – [A]) [ ] [ ] [ ] So… d[A] = k 1 [A] k 1 ( B o + A o A ) dt A k -1
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5.60 Spring 2008 Lecture #32 page 2 d[A] At Equilibrium, = 0 dt [ ] = k 1 [ ] + [ ] A o ) A eq ( B o k 1 + k 1 d A ) ( ) ( ( [ ] [ ] A eq = − d [ ] A = k 1 + k 1 ) ( [ ] [ ] A eq ) A dt dt 1 [ ] [ ] eq = [ A ] o [ ] eq ) e ( k 1 + k ) t A A ( A ln (|[A] - [A] eq |) Conc [A] 0 > [A] eq Slope = -(k 1 +k -1 ) [A] eq [A] 0 < [A] eq time time Can measure: K eq = k 1 and k 1 + k 1 k obs k 1 And extract k 1 and k -1
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5.60 Spring 2008 Lecture #32 page 3 b) Higher order reactions k 2 e.g. A + B C 2 nd order forward, k -1 1 st order backward d[A] [ C ] eq k dt = k 2 [A][B] k 1 [C] , K = [ ] A eq [ ] eq , K = 2 1 B k After much calculation, get… A mess!
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