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Organic Spectroscopy UV - Ultraviolet-Visible Spectroscopy

Methods for structure determination of organic compounds: Conjugated compounds absorb energy in the ultraviolet (UV) and
visible (Vis) regions on the electromagnetic spectrum
X-ray Crystallography Crystall structures
Mass spectroscopy Molecular formula ! ! 200- 800 nm
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UV UltraViolet radiation Electron exitation
Lambert-Beer's law : A = " · C · l
IR InfraRed Vibration excitation
NMR Nuclear Magnetic Resonance Nuclear spin excitation
A is the observed absorbance,
Etot = Eelec + Evib + Erot + Ekin " Molar absorptivity Is the intensity of the absorption
E2
C is the molar concentration of the sample and
h" E = h" l is length of the sample cell in centimeters
!E
v=c/ #
E1 E=hc/# The wavelength of maximum absorption (! max) is reported in units of
nanometers (nm).

Example: UV absorption spectrum of 2,5-dimethyl-2,4-hexadiene

Overview of methods: Ethyl propenoat

Use of UV

• Absorbance above 210 gives indication of conjugated systems
• Concentration measurements through calibration curve

Absorption Maxima for Nonconjugated and Conjugated Dienes MS . All this is taken Alkenes and nonconjugated dienes have absorptions below 200 nm because place in an instrument called a mass spectrometer.Mass Spectroscopy In UV-Vis spectroscopy the electrons are excited from lower energy levels to higher ones In mass spectroscopy (MS) a small quantity of a sample is vaporized and The electron is generally excited from the highest occupied molecular orbital ionized to form charged particles – usually an electron is removed from (HOMO) to the lowest unoccupied molecular orbital (LUMO) each molecule to form charge ions. the energy difference between the HOMO and LUMO is large Scheme: In conjugated dienes these energy levels are much closer together and the wavelengths of absorption are longer than 200 nm Example: Butanone Ethene has lmax at 171 nm and 1. the smaller the energy difference between the HOMO and the LUMO A smaller energy gap results in longer !max in the ultraviolet -visible spectrum #-Carotene has 11 conjugated double bonds and an absorbance maximum at 497 nm which is in the blue-green region of the visible spectrum #-Carotene is perceived as red-orange. the complementary color of blue-green See more examples in Tab 13-2 (p. 412) . The charged particles are sorted according to their mass-to-charge ratio (m/z) and detected.3-butadiene has lmax at 217 nm The longer the conjugated system.

and Common example with different isotope distrubution from unity: 79 Br / 81Br is 1:1 Mw = 80 g/mole and 35Cl / 37Cl is 3:1 Mw= 35. e.g. IR . Carbonyl.The molecule is commonly fragmentated into “stable” carbocations at branching points. Bending vibrations Similar summary is presented in Fig 13.1600 cm-1 The fingerprint area gives specified pattern of many peaks (bending vibrations) in the spectra for each organic molecule Strong dipoles gives generally strong absorbance.Infrared spectroscopy Vibration transitions: Streching Each Isotope of an atom gives a specific peak according to its abundance. 416) Stretching vibrations:1000 . Important IR absorptions of fundamental bonding groups E 4000 cm-1 3000 2000 1600 1000 650 cm-1 O-H C H C H C C C O C C C O C N N-H C HBend Ar-HBend O C H C O H Fingerprint area All vibrations streching unless noted.7 For more specified values see Table 13.4000 cm-1 Bendning vibrations: 600 . C=O Dipole moment must be changed if IR-radiation should be absorbed.45 g/mole Bending IR can be used for determination of functional groups in organic compounds. CH3 C C CH3 CH3 C C H No absorbance Absorbance .3 (p.

stronger and stiffer and thus vibrate at higher frequency ! C-H bonds at sp centers appear at 3000-3100 cm-1 ! C-H bonds at sp2 centers appear at about 3080 cm-1 ! C-H bonds at sp3 centers appear at about 2800-3000 cm-1 ! Aromatic Compounds .C-C bond stretching frequencies are only useful for multiple bonds .Interpreting IR Spectra Example: 1-hexene Example: 1.The C-C bond stretching gives a set of characteristic sharp peaks between 1450- ! C-C double bonds give peaks at 1620-1680 cm-1 1600 cm -1.hexyne Generally only certain peaks are interpreted in the IR -Those peaks that are large and above 1400 cm-1 are most valuable Hydrocarbons C-H bonds where the carbon has more s character are shorter. Substitution pattern can be analyzed by peaks at 600-800 cm -1 ! C-C triple bonds give peaks at 2100-2260 cm-1 Example: Methyl benzene Example: octane .

. the hydroxyl groups hydrogen bond to each other and a very broad and large peak occurs at 3200-3550 cm-1. See the spectra above of ethanol as an example. Carboxylic Acids The carbonyl peak at 1710-1780 cm-1 is very characteristic The presence of both carbonyl and O-H stretching peaks (2500-3500 cm-1. very broad due to extensive hydrogen bonding) is a good proof of the presence of a carboxylic acid Example: propanic acid . Amines Functional Groups: Very dilute solution of 1o and 2o amines give sharp peaks at 3300-3500 cm-1 for the N-H stretching ! 1o amines give two peaks and 2o amines give one peak The carbonyl group gives ! 3o have no N-H bonds and do not absorb in this region a strong peak which More concentrated solutions of amines have broader peaks occurs round 1700 cm-1 Amides have amine N-H stretching peaks and a carbonyl peak Example: p-Methylaniline Alcohols and Phenols The O-H stretching absorption is very characteristic In concentrated solutions.

Övning: Identifiera IR-spektra med rätt förening: Table IR A B C .