February 8, 2018 Chemistry 328N
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1 Lecture 7 UV-Vis spectroscopy February 8, 2018
2 First Midterm Exam When: Wednesday, 2/14 When: 7-9 PM (please do not be late) Where: WEL This room!!! What: Covers material through today s lecture Remember: Homework problems!! Practice: Old exams are posted on the web site Please bring pencils, an eraser and a calculator only and.do a good job!!!
3 Mr Hooke says: The position (frequency) of the absorption of a stretching vibration depends on the strength of the vibrating bond (direct) and the masses of the atoms (inverse) The stronger the bond and the lighter the atoms connected by that bond, the higher the frequency (wavenumber) of the vibration The intensity of absorption depends primarily on the polarity of the vibrating bond
4 The energy of electromagnetic radiation l u c = lu u = l (nu-bar) represents wavenumber, the number of wavelengths in 1 cm 1 This is a unit of frequency! units are 1/cm or cm -1 (Kaysers) c E = hn = h = l hc 10 microns (micrometers) = 1000 cm -1
5 Infrared Absorption Frequencies Stretching vibrations (multiple bonds) Structral unit Frequency, cm -1 C C C C C N
6 IR Group Correlation Tables
7 IR Group Correlation Tables Characteristic IR absorptions for some of the functional groups we deal with most often Bond Frequency (cm -1 ) Intensity O-H N-H C-H C=O C=C C-O strong and broad medium medium to strong strong weak strong
8 Hydrocarbon Alkane C-H CH 2 CH 3 Alkene C-H C=C Alkyne C-H C C Vibration stretching stretching Frequency (cm -1) Intensity stretching strong bending 1450 medium bending 1375 and 1450weak to medium weak to medium weak to medium stretching 3300 medium to strong stretching weak
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10 Fingerprint region
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12 IR Infrared spectroscopy
![Summary IR measures vibrational transitions Can be described by classical oscillator theory Frequency proportional to [ bond strength/mass] 1/2](/docs-images/79/79840089/images/13-1.jpg "Characteristic Group Frequencies OH and C=O are particularly easy to identify Know how to read the chart cm -1?? Practice at the online sites nmr, IR.")
13 Summary IR measures vibrational transitions Can be described by classical oscillator theory Frequency proportional to [ bond strength/mass] 1/2 Characteristic Group Frequencies OH and C=O are particularly easy to identify Know how to read the chart cm -1?? Practice at the online sites nmr, IR..Excellent!!
14 UV/Visible Spectroscopy Most UV/visible spectrophotometers cover from 200 to 400 nm (the near ultraviolet) and 400 nm (violet light) to 700 nm (red light) Region of Spectrum ultraviolet visible Wavelength (nm) Energy (kcal/mol) C-C bond Disassociation energy ~ 95Kcal/mol
15 Absorbance (A) Transmission UV/Vis Spectroscopy UV-Vis spectral data are plotted as absorbance (A) versus wavelength (nm) l max Wavelength (nm)
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17 UV/Vis Spectroscopy Transmission: a quantitative measure of the extent to which a compound absorbs ultraviolet-visible radiation at a particular wavelength %Transmission (T) = I Io X 100 Where: I 0 is the intensity of the incident radiation on the sample I is the intensity transmitted through the sample
18 UV/Vis Spectroscopy Absorbance: a quantitative measure of the extent to which a compound absorbs ultraviolet-visible radiation at a particular wavelength Where: Absorbance (A) = log I 0 is the intensity of the incident radiation on the sample I is the intensity transmitted through the sample I o I
19 Beer-Lambert law Beer-Lambert law: the relationship between absorbance, concentration, and length of the sample tube Beer-Lambert Law: A = c l A = absorbance c = concentration (mol liter -1 ) l = length of the sample tube (cm) = molar absorptivity (liter mol -1 cm -1 ). Experimental values of range from 0 to 10 6
20 Some Quantitative Relationships Please read: Pages %Transmission (T) = I I Absorbance (A) = log o X 100 I o I Beer-Lambert Law: A = c l
21 Origin of UV-Vis Absorbance - MO Theory sigma bond conservation of orbitals DE = 65 Kcal/mole
22 Antibonding Bonding
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24 Origin of UV-Vis Absorbance MO Theory LUMO HOMO
25 Bonding and antibonding molecular orbitals in hydrogen (H 2 ). A bonding molecular orbital has lower energy and greater stability than the atomic orbitals from which it was formed. An antibonding molecular orbital has higher energy and lower stability than the atomic orbitals from which it was formed.
26 Hybridization of Atomic Orbitals
27 A good cartoon
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Requests for permission to make copies of any part of the work should be mailed to:permissions Department, Harcourt Brace & Company, 6277 Sea Harbor Drive, Orlando, Florida 32887-6777 William H. Brown
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William H. Brown & Christopher S. Foote
Requests for permission to make copies of any part of the work should be mailed to:permissions Department, Harcourt Brace & Company, 6277 Sea Harbor Drive, Orlando, Florida 32887-6777 William H. Brown
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