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Infrared Spectroscopy:

A students approach to understand why is going on

1 st a diagram of a IR Spectrometer, in the simplest way I have found:

of a IR Spectrometer, in the simplest way I have found: What could this IR stuff

What could this IR stuff tell us?

Well like mass spectroscopy it can tell us what atoms are in a molecule but unlike mas spectroscopy we now can determine through analysis of an IR spectra graph which functional groups are present in the molecule. (Could be present not definitive as we must have a correct

analysis in order to assure we have identified the right functional groups)

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Each molecule has various bonded atoms which make up different functional groups from alkanes to aldehydes. Although we might simply receive a graph and analyze it is important to understand what is occurring and why. We receive this graph from performing IR Spectroscopy on a molecule that plots the stretching frequency (x axis) against the number of photons absorbed (y axis)

While this graph is very useful let’s first understand how this graph is obtained and the concepts behind it:

First let’s ask What’s this Infrared Spectrum?

The Infrared Region

Infrared radiation is of slightly shorter frequency than visible light. Typical IR wavelengths range from 8x10-5 cm to 1x10-2 cm, and this corresponds to energies of around 1-10 kcal. This energy is sufficient to make atoms vibrate, but not enough to cause electronic transitions.

How this relates to IR spectroscopy? Well Infrared spectroscopy uses infrared light. By shooting photons of frequencies within the infrared part of the spectrum different parts of a molecule vibrate at different points within the spectrum. When these molecular vibrations occur at a certain point in the spectrum the atoms within the bond within the molecule

absorb the photons and therefore there are a high number of photons absorbed. In other places of the spectrum where there are no photons absorbed we see smaller or no peaks. These absorption spectrums for the molecule show us what functional groups the molecule might consist of. Remember none of this is definitive as we must account for the fact that there are other forces which effect bond strength, length, and such within a molecule which might increase or decrease the stretching frequency which the particular function group undergoes molecular vibrations at, hence the use of ranges for each functional group. * Note: molecular vibration transitions (ground -> excited state) are NOT synonymous with electronic transitions, these would not occur when using lower frequency/lower energy infrared photons. Electronic transitions would require much higher frequency/energetic photons.

Why would this apply to functional groups? Well each functional group has atoms that are bonded these bonds have different characteristics from bond length, strength, and dipole. Now that we see that bonds differ, understand that in order to cause a molecular vibration or a transition between the ground and excited state requires a specific amount of energy. *remember all the way back from 14a that energy comes in discrete packets, therefore vibration energy is quantized and can only occur if the energy is the specific energy that will cause a molecular vibration.

How does molecular structure control Intensity of the peak/ amount photon absorption?

(Y axis) Intensity of absorption in the IR spectrum relates to the change in dipole movement which occurs during molecular vibrations. A bond that has a large initial dipole will have a greater change in dipole movement and therefore will absorb more of the incoming photons assuming the frequency of these photons corresponds to the stretching frequency of that particular bond. Dipole is greater if and when The atoms bonded have a larger electronegativity difference (delta EN) i.e.: C-H bond less dipole than O-H bond The bond length is longer (distance between the atoms) Makes sense as if the bonded atoms were closer it would be harder to unequally share electrons, therefore decreasing the dipole. If the atoms bonded were farther from each other than it’s easier to isolate electron density to one area and therefore increase the polarity of the bond.

Remember Dipole up, Intensity of Absorption UP

How does molecular structure affect the stretching frequency X AXIS that a particular part of the molecule undergoes molecular vibrations?

1) As the bond strength goes up so does the stretching frequency. Why? Well the stiffer the spring the faster it will vibrate when you stretch it and release it. Same concept, In order to cause a molecular vibration which occurs when bond goes from the ground to the excited state, the bond must vibrate but just like we must put a certain amount of energy into stretching a stiff spring there is also a certain amount of energy that must be receive in a quantized packet by the stiff/strong bond.

2) As the mass of one of the atoms participating in the bond goes up the stretching frequency will go down (must consider change in the bond strength as well) and Vis versa, when there are lighter atoms participating in a bond this requires a higher frequency. I know this analogy has its flaws but it helped me,

If you had a hippo (big, larger) it would jiggle easier If you had a lighter hippo, one that was skinny, lighter, and had a smaller mass it wouldnt jiggle as easy Remember this is just a way to remember not the actual situation

The IR graph notes and important concepts :

Some have asked about the fingerprint region Dr. Hs tutorial on IR explains why we dont analyze past the finger print region and the types of molecular vibrations that occur in this region Please go here

Characteristic IR Absorption Values

Stretching, cm Zone 1: Functional Group 3700 – 3200 cm alcohol alkyne amine, amide Bond
Stretching, cm
Zone 1:
Functional Group
3700 – 3200 cm
alcohol
alkyne
amine, amide
Bond
Intensity
O-H
3650 – 3200
≡C-H
~3300
N-H
3500 – 3300
variable; usually broad
strong
medium, often broad
Zone 2:
3200 – 2700 cm
alkane
aryl, vinyl
aldehyde
carboxylic acid
sp3
C-H
sp2
C-H
sp2
C-H
O-H
2960 – 2850
3100 – 3000
~2900, ~2700
3000 – 2500
variable
variable
medium, 2 bands
strong, broad
Zone 3:
2300 – 2100 cm
alkyne
nitrile
C≡C
variable
C≡N
2260 – 2100
2260 – 2220
variable
Zone 4: 1950 - 1650 cm aldehyde amide aryl ketone carboxylic acid ester ketone enone
Zone 4:
1950 - 1650 cm
aldehyde
amide
aryl ketone
carboxylic acid
ester
ketone
enone (C=C-C=O)
aromatic overtones
C=O
1740 – 1720
C=O
1690
– 1650
C=O
1700
– 1680
C=O
1725
– 1700
C=O
1750
– 1735
C=O
1750
– 1705
C=O
1685
– 1665
1950 – 1750
strong
strong
strong
strong
strong
strong
strong
3 or 4 small peaks
Zone 5:
1680 – 1450 cm
alkene
C=C
1680
– 1620
aromatic
C=C
~1600, 1500-1450
variable
variable; 1600 often 2 bands

Fingerprint region: < 1450 cm

1600 often 2 bands Fingerprint region: < 1450 cm ( ^^Credit to Dr. Hardinger, this is
1600 often 2 bands Fingerprint region: < 1450 cm ( ^^Credit to Dr. Hardinger, this is

( ^^Credit to Dr. Hardinger, this is off his tutorial on IR)