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Quantitative Chemical Analysis Seventh Edition Quantitative Chemical Analysis Seventh Edition Chapter 18 Fundamentals of Spectrophotometry Copyright © 2007 by W. H. Freeman and Company Daniel C. Harris
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Light has: Intensity Color (wavelength) Polarization
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Intensity
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Transmittance Absorbance
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Transmittance Absorbance Beer’s Law
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ε = 313 M -1 cm -1 b = 2 cm T = 3.16% = 0.0316 A = -logT = 1.50 c = 1.5/(313 M -1 ) (2 cm -1 ) = 0.0024 M
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dP(x)/dx = -κ P(x) P(x) = exp(-κ x)
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Beer’s law
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Molar extinction Coefficient ~250 L.mol -1 cm -1 Cross section ~10 -18 cm 2
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Absorption of a mixture
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Isosbestic point
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(wavelength) x (frequency) = speed [m/s] λν = c [10 8 m/s]
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436 nm what frequency?
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Visible spectrum
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Your Eyes See the Color that is NOT Absobed
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Hexaquotitanium (III) Solutions Appear Violet Due to Absorption of Yellow and Green Light
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Subtraction of Light by Absorption Leads to Color you See
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What makes a molecule absorb light?
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Electron motion (fs) resonant frequency ~ 300 nm UV-VIS ~ 10 -15 s ν ≈ 10 15 s -1
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What makes a molecule absorb light? Electron motion UV-VIS excites electrons!
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E = h ν
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Electron diffraction pattern from a beryllium atom
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What makes a molecule absorb light? Nuclear motion ~ 3000 nm infrared
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What makes a molecule absorb light? Nuclear motion ~ 300,000 nm microwave
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What makes a molecule absorb light? Oscillating DIPOLE moment
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What makes a molecule absorb light?
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green house gas http://science.widener.edu/svb/ftir/ir_co2.html
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What makes a molecule absorb light? [cm -1 ] = 1/λ = ν/c =E/hc
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What makes a molecule absorb light? 3200 cm −1 broad, strong O-H stretch (alcohols) 3000 cm −1 broad, medium O-H stretch (carboxylic acids) 1200 cm −1 strong, O-H bending 2800 cm −1 strong, C-H stretch 1400 cm −1 variable, C-H bending 1700 cm −1 strong, C=O stretch 1200 cm −1 strong, C-O stretch
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What makes a molecule absorb light?
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E = h ν
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