2.

16 Interpreting IR Spectra
- IR spectra contain a wealth of information about the structures of compounds.
- recognize the presence of characteristic IR absorption peaks that result from vibrations of alkyl
and functional groups.

2.16A Infrared Spectra of Hydrocarbons

• All hydrocarbons give absorption peaks in the 2800–3300 cm−1 region that are
associated with carbon–hydrogen stretching vibrations.
Explanation: Magamit nato ang peak sa IR spectra kay ang exact location
sa iayng peak kay naka depend sa iyang strength og stiffness sa CH bond which
also depends sa iyang hybridization sa carbon. And always remember the order of
strength sa hybridization, ang sphybridization ang strongest while ang sp3 ang
weakest.
• The carbon–hydrogen stretching peaks of hydrogen atoms attached to sp-
hybridized carbon atoms occur at highest frequencies, about 3300 cm−1.
Explanation: ang terminal alkene sa carbon-hydrogen bond kay gahatag
og absorption nga 3300 cm -1 and Makita na nato sa table below (acetylenic
(alkynyl) c−h bond of 1-heptyne at 3320 cm−1)
• The carbon–hydrogen stretching peaks of hydrogen atoms attached to sp2-
hybridized carbon atoms occur in the 3000–3100 cm−1 region.
Explanation: Dani nga region ga peak ang alkenyl CH bond and CH groups
of aromatic rings.
• The carbon–hydrogen stretching bands of hydrogen atoms attached to sp3-
hybridized carbon atoms occur at lowest frequencies, in the 2800–3000 cm−1
region.
Explanation: very weak ang peak sa single bond nga carbon-carbon then
gamay ra siyag gamit sa pag assign sa structure.
• Carbon–carbon double bonds give absorption peaks in the 1620–1680 cm−1
region, and carbon–carbon triple bonds give absorption peaks between 2100 and
2260 cm−1.
Explanation: dili strong iyang absorption then if absent siya kung
symmetrically substituted ang double og triple bond.
• Absorptions arising from carbon–hydrogen bending vibrations of alkenes occur in
the 600–1000 cm−1 region.
2.16B IR Spectra of Some Functional Groups Containing Heteroatoms
- Infrared spectroscopy is an invaluable method for detecting the presence of
functional group in a molecule.
Carbonyl Functional Groups
- carbonyl group gives a prominent absorption peak in IR spectra.
- this group is present in aldehydes, ketones, esters, carboxylic acids, amides, and
more.
- the carbon oxygen double bond [ -C(=O)- ] stretching frequency of carbonyl
groups gives a strong peak between 1630 and 1780 cm-1.
Alcohols and Phenols
- hydroxyl groups of alcohols and phenols are easy to recognize in IR spectra by
their O-H stretching absorptions.
- the IR absorption of an alcohol or phenol O-H group is in the 3200 - 3550 cm-1
range; most often, it is broad.
Carboxylic Acids:
- Carboxylic acid group can be detected by IR spectroscopy. If both carbonyl and
hydroxyl stretching absorptions are present in an IR spectrum, then there is good
evidence for a carboxylic acid group
- The hydroxyl absorption of a carboxylic acid is often very broad, extending from
3600 cm−1 to 2500 cm−1.
Amines:
- Primary and secondary amines give absorptions of moderate strength in 3300–
3500 cm−1 region.
- Primary amines exhibit two peaks in this region due to symmetric and
asymmetric stretching of the two n−h bonds while secondary amines exhibit a
single peak and tertiary amines show no n−h absorption because they have no
such bond.
- A basic pH is evidence for any class of amine.
- Hydrogen bonding causes N−H stretching peaks of 1° and 2° amines to broaden.
NH groups of amides gives similar absorption peaks and include a carbonyl
absorption.
How to interpret an IR Spectrum without any knowledge of the structure
• To interpret an IR spectrum without any knowledge of the structure, we cannot
use IR spectroscopy by itself to determine complete structure. Thus, an IR
spectrum can point the presence of a certain functional group
• IR spectroscopy cannot be used to determine the complete structure.
- It does not show us the complete structure, it only shows the presence
of a certain bond.
- Infrared spectra correspond to the vibration energy, each structure has
different kinds of bonds. Hence, each compound has different
characteristics that can be used to identify the group present.
• IR Spectrum
- analyses a compound by passing infrared radiation, over a range of
different frequencies, through a sample and measuring the absorptions
made by each type of bond in the compound. This produces a
spectrum, normally a 'plot' of % transmittance against wavenumber.
• Different variations of signal strength
- Strength of the bond determines what functional group is present.
- Strength of a bond between two atoms increases as the number of
electron pairs in the bond increases.
- triple bonds are stronger and shorter than double bonds between the
same two atoms; likewise, double bonds are stronger and shorter than
single bonds between the same two atoms.
“Sa pag determine ani, we need to know the absorption (naa sa table sa top) para ma
identify what functional group to siya.”
• Only c=o stretches tend to have a tight, strong absorbance in the 1630–1780 cm−1
range. We may not be able to identify what kind of carbonyl group is present, but we
can tell that there is at least one carbonyl group.
• Only the stretches of nitrile or alkyne bonds tend to appear between 2000 and
2300 cm−1 , so these can be fairly readily assigned.
• Only hydroxyl groups as in alcohols or carboxylic acids tend to create a large and broad
signal at about 3300 cm−1 ; these groups are easy to identify assuming the sample is not
contaminated with water.
• Only amines tend to produce broad but smaller peaks than hydroxyl peaks around
3300 cm−1 . The number of those peaks can sometimes tell if there is one or two
hydrogens attached to that nitrogen atom
Example
1. The IR spectrum of Unknown 1 (Fig. 2.18) has broad signals centered around
3300 cm−1 and a medium absorption at 2250 cm−1 .
- Base sa given, 3300 cm-1 belong sa Hydroxyl groups and ang 2250 cm-
1 na-belong sa alkyne (triple bond) group. (base sa table above for
further info why alkyne ang na use instead of nitrile)
In this way, ma-determine na nato what functional group is present.