Full set of Notes with Fill-Ins - San Jose State University

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AbsorbanceChem 155 Unit 11 196 of 316.Spectral Assignments15 . 10 4 2 30200 250 300 350 400Wavelength / nmUV spectrum & energy levels of a fictitiouscarbonyl:If: π π* σ σ* n π* n σ* are allowed,assign peaks 1, 2 and 3 to specific transitions:Transition EnergyFrom DiagramFrom SpectrumPossible Energy / Peak # λ / nm ν / cm -1Transitions arbitrary unitsσ σ* 10-0 = 10 1 200 50,000n σ* 10-4 = 6 2 250 40,000π π* 9-1 = 8 3 330 30,000n π* 9-4 = 5ΔE (spectrum) ΔE (digram) λ / nm Assignment50,000 10 200 σ σ*40,000 8 250 n σ*30,000 6 330 π π*n π*Page 196 of 316Energy10 σ*9 π*87654 n321 π0 σ
Chem 155 Unit 11 197 of 316Classification of Electronic TransitionsThe following simplified classifications apply toorganic molecules:1. σ σ*1.1. Highest energy!1.2. Shortest wavelength λ < 200 nm1.3. O 2 , N 2 , all molecules have σ-bonds so: thisradiation is absorbed by air and SiO 2 sospectroscopy must be done in vacuum and isvery difficult – called VUV or vacuumultraviolet spectroscopy2. n σ*2.1. 150-250nm – most all transitions are foundin the ultraviolet2.2. Molecules with lone (nonbonding) pairs ofelectrons participate such as: O, N, Halogens2.3. ε ∼ 100 to 1000 “medium” strength absorbers3. n π*, π π*3.1. Longest wavelength transitions 200-700 nm3.2. Strongest absorbers ε ∼ 100 to 100,0003.3. Limited to molecules with π-bonds – e.g.alkenes, alkynes, aromatics, carbonyls, azidesetc.Page 197 of 316
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Full set of Notes with Fill-Ins - San Jose State University

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