The Electromagnetic Spectrum

Infrared, ultraviolet, and nuclear magnetic resonance spectroscopies differ from mass spectrometry in that they are nondestructive and involve the interaction of molecules with electromagnetic energy rather than with an ionizing source.
Visible light, X-rays, microwaves, radiowaves,..etc. are all different kinds of electromagnetic radiation. Collectively they make up the electromagnetic spectrum.

 Electromagnetic radiation has dual behavior. - In some respects it has the properties of a particle (called a photon), yet in other respects it behaves as an energy wave.

Like all waves electromagnetic radiation is characterized by a wavelength, a frequency, and an amplitude.

Wavelength, (Greek lambda) is the distance from one wave maximum to the next. Usually given in meters (m) or in nanometers (nm)

Frequency, (Greek nu) is the number of waves that pass by a fixed point per unit time. usually given in reciprocal seconds (s-1), or hertz, Hz (1 Hz =1 s-1)
Amplitude is the height of a wave, measured from midpoint to peak.

Wavelength x Frequency = Speed of light (m) x (s-1) = c (m/s) = c or = c

Electromagnetic energy is transmitted only in discrete amounts called quanta. The amount of energy, (epsilon), corresponds to 1 quantum of Energy (1 photon) of a given frequency, , is expressed by the Plancks Equation: = h = hc Plancks Equation = energy h = Plancks constant = frequency

Most chemists talk about the IR region in terms of wavenumbers. Wavenumber is inversly proportional to wavelength and reported in reciprocal centimeters (cm-1)
Wavenumber, (cm-1) = 1 (cm)

= h = hc
= hc

Plancks Equation

High frequencies, high wave numbers and short wavelengths corresponds to high energy radiation. Low frequencies, lower wave numbers and long wave lengths corresponds to low energy radiation.

The Nature of the energy Absorptions by molecules

Molecules can store energy in a variety of ways. They rotate in space, their bonds vibrate like springs, their electrons can occupy a number of possible molecular orbitalsetc.

Each of these forms of energy is quantized.

eg: A bond in a molecule can only vibrate at specific energy levels for a particular bond. The bond can only absorb energy, when it is irradiated with a radiation that matches the energy gap between its allowed energy levels.

12.6 Infrared Spectroscopy

Absorption of IR radiation by molecules causes changes in their vibrational motions.
Although we usually speak of bond lengths as if they are fixed, the numbers given really are average values. eg: A typical C-H bond with an average bond length of 110 pm is actually vibrating at a specific frequency, alternately stretching and contracting as if there were a spring connecting the two atoms. When a molecule is irradiated with IR radiation, energy is absorbed if the frequency of the radiation matches the frequency of a particular vibrational mode of a bond in the molecule. - This causes the amplitude of the particular bond stretch or bond bend to increase.

Some conmmon vibrational modes

These bond stretching and bending vibrations represent the different vibrational modes available to a molecule.

 Different kinds of bonds vibrate at different frequencies, so they absorb different frequencies of IR radiation. IR spectroscopy distinguishes between different kinds of bonds in a molecule, so it is possible to determine the functional groups present.

IR Spectrum
In an IR spectrometer, light passes through a sample. Frequencies that match vibrational frequencies are absorbed, and the remaining light is transmitted to a detector.
A spectrum plots the amount of transmitted light versus its wave number. The useful infrared (IR) region for organic chemist is from 4000 cm-1 400 cm-1

eg: IR spectrum of ethanol

Horizontal axis Wavenumber Vertical axis percent transmittance. A transmittance of 100% means that all the energy is passing through the sample, where as a lower transmittance means that most of the energy is being absorbed. Each downward spike corresponds to an energy absorption.

12.7 Interpreting Infrared Spectra

Complete interpretation of an IR spectrum is difficult because most organic molecules have dozens of different bond stretching and bending motions, and thus have dozens of absorptions.

On the other hand, the complexity is useful because an IR spectrum serves as a unique fingerprint of a compound.
If two samples have identical IR spectra, they are almost certainly identical compounds. Fortunately we dont have to interpret an IR spectrum fully to get useful structural information. Most functional groups have characteristic IR absorption bands.

IR spectrum can be divided into two main regions:

1. The functional group region (4000 cm-1 - 1500 cm-1) Common functional groups give one or two peaks in this region, at characteristic frequencies.

2. The fingerprint region (1500 cm-1 - 400 cm-1) This region often contains a complex set of peaks and is unique for each compound.

IR absorption trends
The frequency of a bond vibration can be derived from Hookes law, which describes the motion of a vibrating spring.

Hookes law

= k

f m

f = force constant m = mass k = constant

The force constant (f) is the strength of the bond (or spring). Stronger the bond, larger the f and higher the of vibration. - In general, triple bonds are stronger than double or single bonds between the same two atoms and have higher frequencies of vibrations (higher wavenumbers):

CC ~2200 cm-1

C=C ~1650 cm-1

C-C ~1200 cm-1

Hookes law

= k

f m

f = force constant m = mass k = constant

The mass (m) is the mass of the atoms (or weights). Lighter the atom, higher the of vibration.
eg: Compare the following bonds. The C-H bond involves the smallest atom (H) and therefore has the highest wavenumber.

C-H ~3000 cm-1

Problem:

C-D ~2200 cm-1

C-O ~1100 cm-1

C-Cl ~700 cm-1

Choose the bond in each pair that you would expect to have a higher . 1) C=O or C-O 2) C-N or C-H

 Absorptions for bonds to hydrogen always occur on the left side of the spectrum
(the high wavenumber region). H has so little mass that H-Z bonds (Where Z = C, O, and N) vibrate at high frequencies.
Bond strength decreases in going from C C C=C C-C, so the frequency of vibration decreases that is, the absorptions for these bonds move further to the right side of the spectrum (low wavenumber region)

C-H stretching frequencies in alkynes, alkenes, and alkanes

The frequency of the absorption of C-H bonds is a function mostly of the type of hybridization that is attributed to the bond. Stronger the bond, higher the vibrational frequency.

Bond Hybridization type Strength IR frequency

C-H

=C-H

-C-H

sp -1s
506 kJ 3300 cm-1

sp2 - 1s
444 kJ Above 3000 cm-1

sp3 - 1s
422 kJ below 3000 cm-1

Bonds with more s character absorb at a higher frequency.

Alkanes C-H

just below 3000

medium

Alkenes =C-H C=C Alkynes C-H CC

just above 3000 around 1650

medium medium

around 3300 around 2200

strong medium, sharp

 The C=C absorption frequencies increase as alkyl groups are added to a double bond.

Greater the substitution, stronger the alkene, hence higher the C=C absorption frequency.

Alcohols
O-H C-O 3400 3650 1300 - 1000 strong, broad strong

Carbonyl Compounds
Strong, sharp C=O peak 1800 to 1650 cm1 Exact absorption is characteristic of the type of the carbonyl compound

Carboxylic Acids C=O O-H

1800 1650 3100 2500

strong strong, broad

This O-H absorbs broadly, due to strong hydrogen bonding.

19

Amides C=O N-H 1800 1650 cm-1 around 3400 cm-1 ( sometimes appear as two peaks)

Amides C=O N-H 1800 1650 around 3400 strong medium, sometimes appear

Esters C=O C-O 1800 1650 1300 - 1000

Aldehydes C=O C-H

1800 1650 2900 - 2750

strong weak

Ketones C=O 1800 1650 strong

Effect of Conjugation on the C=O stretching frequencies

The introduction of a C=C bond adjacent to a carbonyl group results in delocalization of the electrons in the C=O and C=C bonds.

This conjugation increases the single bond character of the C=O and C=C bonds in the resonance hybrid resulting in a lowering of the frequencies of carbonyl and double-bond absorption.

Conjugation with triple bonds as well as with aromatic rings have the same effect.

Examples

25

Nitriles

CN

around 2200

medium, sharp

Characteristic IR Absorptions of Some Key Functional Groups

Functional Group Alkanes C-H Absorption (cm-1) Intensity Functional Group Carboxylic Acids C=O O-H Amides C=O N-H Esters C=O C-O Absorption (cm-1) Intensity

just below 3000

medium

1800 1650 3100 2500

strong strong, broad

Alkenes =C-H C=C Alkynes C-H CC

just above 3000 around 1650

medium medium

1800 1650 around 3400

strong medium

around 3300 around 2200

strong medium, sharp

1800 1650 1300 - 1000

strong medium

Alcohols O-H C-O

3400 3650 1300 - 1000

strong, broad strong

Aldehydes C=O C-H

1800 1650 2900 - 2750

strong weak

Amines N-H C-N

Ethers C-O Aromatic rings =C-H C=C

around 3400 around 1100

medium medium

Ketones C=O

1800 1650

strong

1300 - 1000

medium

Nitriles CN Nitro NO2

around 2200

medium, sharp

above 3000 around 1650 around 1500

medium weak medium

around 1540

strong

Problems 1. What functional groups might the following molecules contain? a) A compound with a strong absorptions at 1720 cm-1 and 2500 to 3100 cm-1

b) A compound with a strong absorption at 1710 cm-1

2. Propose a structure for the following compound that meet the following descriptions: C5H8, with a IR absorption at 3300 cm-1

2. Two IR spectra are shown below. One is the spectrum of cyclohexane, and the other is the spectrum of cyclohexene. Identify them and explain your answer.