Physicochemical Analysis II

IR - Infrared Spectroscopy
A general introduction to spectroscopic methods will be followed by a more detailed presentation on the use of IR Spectroscopy in structural analyses of organic compounds. Presence or absence of certain covalent bonds, especially O-H and C=O, can be readily determined from IR spectra. IR Spectroscopy Functional Group Determination

Molecular Dynamics
Total energy of a molecule: Etotal = Etranslation + Eelectronic + Evibration + Erotation Etranslation = kinetic energy, 3-D movement Eelectronic = electronic energy, excitation of electrons: ground state excited state Evibration = vibrational energy, bending and stretching of covalent bonds Erotation = rotational energy

Chemists can use portions of the electromagnetic spectrum (EMS) to selectively manipulate the energies contained within a molecule, to uncover detailed evidence of its chemical structure and bonding.

Introduction to Spectroscopy

spectrum looking

Instrumentally aided studies of the interactions between matter (sample being analyzed) and energy (any portion of the electromagnetic spectrum, EMS) The four most common spectroscopic methods used in organic analysis are: Method Ultraviolet-Visible Spectroscopy Infrared Spectroscopy Nuclear Magnetic Resonance Mass Spectroscopy Abbrev. UV-Vis IR NMR Mass Spec Energy used ultraviolet-visible infrared radio frequencies electron volts Units nm -1 m or cm Hz or amu

Question: What actually happens to the sample during an analysis? {How do the sample and energy interact?}

Matter/Energy Interactions
What happens when a sample absorbs UV/Vis energy? excitation of ground state electrons (typically p and n electrons) Eelectronic increases momentarily UV/Vis
(200 nm)

p*
p p*
transition

sample

What happens when a sample absorbs IR energy?

stretching and bending of bonds (typically covalent bonds) Evibration increases momentarily

-O-H

IR
(3500 cm-1)

- O H

FTIR Instrumentation
Shimadzu 8300 FTIR Spectrometer

Infrared source

Computer Workstation running Hyper IR 1.57

sample port (closed)

IR

Perkin-Elmer 1600 FTIR

FTIR Sample Port

IR
Infrared radiation

organic sample selectively absorbs infrared radiation

salt plates positioned on sample holder calcium chloride (CaCl2) desiccant

to detector

IR Correlation Diagram
Region I 3600-2700 cm-1 100 Region II 1800-1600 cm-1

Transmittance (%)

80 60 40 20

O-H N-H C-H bond stretching

alcohols phenols carboxylic acids
amines amides alkynes alkenes alkanes C-H =C-H -C-H

C=O
acid chlorides anhydrides (below 1500 cm-1) esters ketones aldehydes carboxylic acids amides

Fingerprint Region

0 4000 2.5

3500

3000

3.0

2500 4.0

2000 5.0

1500

6.0

1000 10.0

Frequency (cm-1) / Wavelength (microns, m)

IR Correlation Diagram
Region I 3600-2700 cm-1 100 Region II 1800-1600 cm-1

Transmittance (%)

80 60 40 20 0 4000

O-H N-H C-H bond stretching

alcohols phenols carboxylic acids amines amides alkynes alkenes alkanes C-H =C-H -C-H O=C=O CN CC

C=O
acid chlorides anhydrides (below 1500 cm-1) esters ketones aldehydes carboxylic acids amides C=N C=C

Fingerprint Region

C-F

3500

3000

2500

2000

1500

1000

Frequency (cm-1)