solns21b-ps7-Mar11

# solns21b-ps7-Mar11 - 1a To find the net rate of production...

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Unformatted text preview: 1a) To find the net rate of production of D*, we simply add the rates of all processes that form it and subtract all processes that consume it. At steady state, I a- k 1 [ D * ]- k 2 [ D * ][ A ]- k 3 [ D * ] = 0 I a = ( k 1 + k 2 [ A ] + k 3 )[ D * ] b) Setting [A]=0, I a = [ D * ]( k 1 + k 3 ) . Thus, φ = k 1 [ D * ] I a = k 1 k 1 + k 3 . c) Without assuming [A]=0, φ a = k 1 k 1 + k 2 [ A ] + k 3 . d) Taking the ratio, φ φ a = k 1 k 1 + k 3 · k 1 + k 3 k 1 + k 2 [ A ] k 1 = 1 + k 2 k 1 + k 3 [ A ] 2) The secular equation for cyclobutadiene in H¨uckel theory looks like α- E β β β α- E β β α- E β β β α- E = 0 . The solutions are E = α ± 2 β . In solving the secular equation we find that E = α is a double root, so there are orbitals with energy α , one with energy α + β (the lowest, since β is negative), and one with energy α- β . Hund’s rules tell us to fill these from the bottom up, so we put two in the α + β orbital and two more in the α orbitals. We maximize theorbitals....
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solns21b-ps7-Mar11 - 1a To find the net rate of production...

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