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Chapter 18
Let There Be Light
O 2 → 2O
     hν
                                           
O2 → O 3   ( ozone )                    UV
                                       absorption




CCl 2F2 → CClF2 + ClO + Cl
         hν


Cl + O 3   ClO + O 2 
          →
                       
O 3 → O + O 2
      hν
                        ⇒ 2O 3 → 3O 2
                       
O + ClO  → Cl + O 2 
Why south pole ?




                   See p.374
18.1 Properties of light -1
• .             1
   E = hν = hc   = hc~
                       ν
               λ
• Electromagnetic Spectrum      (Fig 18.2)
• Absorption vs Emission of light
change of                                                             change of spin
  nuclear       change of e distribution    change of      change of   NMR      EPR
configuration     X-ray                    configuration   orientation
    γ-ray       uv.vis                          IR         microwave
18.2 Absorption of light -1
1) Spectrophotometer
18.2 Absorption of light -2
1) .
                         P
       Transmittance T =
                         P0
                                       Po       P
       Absorbance A = -logT

       Beer' s Law : A = εbc
                        mol    
                 ( cm )      = M
        cm ⋅ mol               
                                            b
• A = εbc
18.2 Absorption of light -3
(ex) How effective is sunscreen ?
     at the peak absorbance near 300 nm ?
A ~ 0.35
  T = 10-A
    = 10-0.35
    = 0.45
    = 45%
⇒ 55%
UV-B is absorbed.
18.3 Practical Matters -1
• Cuvets:
  A glass made of SiO2 : Vis. UV.
  Plastics & ordinary glass: Vis
  NaCl(s) KCl(s) : IR
18.3 Practical Matters -2
1) Good Operating Techniques :

  • Cuvets handle: systematic errors/
    random errors
  • Most accurate at A~0.4–0.9
  • Greatest sensitivity: λmax
  • Baseline correction
18.3 Practical Matters -3
                    Too little light : :
                    high A, P is small


                    Too much light :
                    low A, P ~ P0
18.4 Using Beer’s Law -1
• A Colorimetric Reagent to Detect Phosphate
18.4 Using Beer’s Law -2
Ex.1 : Bezene: find molar absorptivity (ε)
at p.387
                250 mL
 25.8 mg

              + hexane
                             b = 1.000 cm
      ?max = 256 nm          e= ?
18.4 Using Beer’s Law -2
Ex.2 : Nitrite in an aquarium
       (using a standard curve)


                                    
                                  543 nm
18.4 Using Beer’s Law -3
                   NH3 animals & plant
             [O]
18.4 Using Beer’s Law -4
1) Standard Nitrite ex. at p389
18.4 Using Beer’s Law -5




from least square (4.4)
A = 0.1769 [ppm] + 0.0015

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Chapter 18

  • 2. O 2 → 2O hν  O2 → O 3 ( ozone ) UV absorption CCl 2F2 → CClF2 + ClO + Cl hν Cl + O 3   ClO + O 2  →  O 3 → O + O 2 hν  ⇒ 2O 3 → 3O 2  O + ClO  → Cl + O 2 
  • 3. Why south pole ? See p.374
  • 4. 18.1 Properties of light -1 • .  1 E = hν = hc   = hc~ ν λ • Electromagnetic Spectrum (Fig 18.2) • Absorption vs Emission of light
  • 5. change of change of spin nuclear change of e distribution change of change of NMR EPR configuration X-ray configuration orientation γ-ray uv.vis IR microwave
  • 6. 18.2 Absorption of light -1 1) Spectrophotometer
  • 7. 18.2 Absorption of light -2 1) . P Transmittance T = P0 Po P Absorbance A = -logT Beer' s Law : A = εbc     mol   ( cm )  = M  cm ⋅ mol     b
  • 8. • A = εbc
  • 9. 18.2 Absorption of light -3 (ex) How effective is sunscreen ? at the peak absorbance near 300 nm ? A ~ 0.35 T = 10-A = 10-0.35 = 0.45 = 45% ⇒ 55% UV-B is absorbed.
  • 10. 18.3 Practical Matters -1 • Cuvets: A glass made of SiO2 : Vis. UV. Plastics & ordinary glass: Vis NaCl(s) KCl(s) : IR
  • 11. 18.3 Practical Matters -2 1) Good Operating Techniques : • Cuvets handle: systematic errors/ random errors • Most accurate at A~0.4–0.9 • Greatest sensitivity: λmax • Baseline correction
  • 12. 18.3 Practical Matters -3 Too little light : : high A, P is small Too much light : low A, P ~ P0
  • 13. 18.4 Using Beer’s Law -1 • A Colorimetric Reagent to Detect Phosphate
  • 14. 18.4 Using Beer’s Law -2 Ex.1 : Bezene: find molar absorptivity (ε) at p.387 250 mL 25.8 mg + hexane b = 1.000 cm ?max = 256 nm e= ?
  • 15. 18.4 Using Beer’s Law -2 Ex.2 : Nitrite in an aquarium (using a standard curve)  543 nm
  • 16. 18.4 Using Beer’s Law -3 NH3 animals & plant [O]
  • 17. 18.4 Using Beer’s Law -4 1) Standard Nitrite ex. at p389
  • 18. 18.4 Using Beer’s Law -5 from least square (4.4) A = 0.1769 [ppm] + 0.0015