Introduction to Spectroscopy

CHM 243 Organic Chemistry I Dr. Frank Yepez Castillo Misericordia University Fall 2013
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Infrared Spectroscopy

Introduction to Spectroscopy
Organic chemists use several spectroscopic techniques to determine the structure of a compound Most techniques are nondestructive. All of the spectrometric techniques rely on the interaction of matter (your sample) and different sources of energy

Energy Sources: Light (Electromagnetic radiation)

Light has wave-like and particle-like properties
The frequency of a wave is the number of complete cycles that pass a fixed point in a second

c =
Wavelength is the distance between any two peaks (or any two troughs) of the wave
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Energy Sources: Light (Electromagnetic radiation)

Light has wave-like and particle-like properties When viewed as a particle, electromagnetic radiation consists of packets of energy, called photons. The energy of each photon is directly proportional to its frequency.

h is Plancks constant (6.62 x 10-37 kJ.s)

E = h

Energy Sources: Light (Electromagnetic radiation)

E = h

and

These two equations can be combined into the following: hc E = High frequencies and short wavelengths are associated with high energy
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c =

Spectroscopy
Spectroscopy involves an interaction between matter and light (electromagnetic radiation).

IR region ranges from 10,000 100 cm-1

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Types of Spectroscopy
Different regions of the electromagnetic spectrum are used to probe different aspects of molecular structure

Electromagnetic radiation
Molecules can store energy in a variety of ways:
Rotational motion Bond vibrations Electronic transitions

All these forms or energy are quantized

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The IR Region
From right below the visible region to just above the highest microwave and radar frequencies Wavelengths are usually 2.5 x 10-4 to 25 x 10-4 cm More common units are wavenumbers (), or cm-1, the reciprocal of the wavelength in centimeters Wavenumbers are proportional to frequency and energy

The IR Region
The IR region that is of particular interest to organic chemists is the limited portion between 4000 cm-1 and 400 cm-1 Absorption in the IR region corresponds to energy changes in the order of 8 to 40 kJ/mol. These energy levels encompass the stretching and bending vibrational frequencies of the bonds in most covalent molecules.

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IR Spectrum
Intensity of the signals are normally expressed as either transmittance (T) or absorbance (A) Transmittance is the ratio of the radiant power transmitted by a sample to the radiant power incident on the sample Absorbance is the logarithm, to the base 10, of the reciprocal of the transmittance:

A = log10 ( 1 ) T

Each signal on the IR spectrum has three important characteristics: wavenumber, intensity, and shape

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IR Spectrum
Peaks in the IR correspond to a particular kind of bond, and each bond type (such as O-H and C-H) occurs at a characteristic frequency The IR spectrum is divided into two regions: a) The functional group region ( 1500 cm-1) b) The fingerprint region (< 1500 cm-1)

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IR Spectrum
Peaks in the IR correspond to a particular kind of bond, and each bond type (such as O-H and C-H) occurs at a characteristic frequency The IR spectrum is divided into two regions: a) The functional group region ( 1500 cm-1) b) The fingerprint region (< 1500 cm-1)

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IR Selection Rules
Only those vibrations that result in a rhythmical change of the dipole moment of the molecule are observed in the IR Symmetric bonds (i.e. H2 and Cl2) do not absorb IR radiation

The intensity of an absorption band depends on how polar a bond is, and on the number of bonds responsible for the absorption

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Molecular Vibrations
We can model the bonds between two atoms as a quantized harmonic oscillator, a.k.a. ball-and-spring model
If the bond is stretched, a restoring force pulls the two atoms together toward their equilibrium bond length If the bond is compressed, the restoring force pushes the two atoms apart If the bond is stretched or compressed and then released, the atoms vibrate

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http://upload.wikimedia.org/wikipedia/ commons/d/d1/ Circular.Polarization.Circularly.Polarized.L ight_Left.Hand.Animation. 305x190.255Colors.gif

Molecular Vibrations
We can model the bonds between two atoms as a quantized harmonic oscillator, a.k.a. ball-and-spring model

IR radiation will cause vibrations in molecules by the changes in the direction of the electrical field
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Molecular Vibrations
By using the ball-and-spring model we can calculate the approximate frequencies of vibration for a bond between two atoms of mass m1and m2

1 f = 2 c mred m1m2 mred is the reduced mass, mred = m1 + m2

is the force constant (bond strength - stiffness) is ca. 5 x 105 dyne/cm for single bonds and 2x and 3x that for double and triple bonds

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Wavenumbers
An IR spectrophotometer irradiates a sample with all the frequencies of IR light The energy necessary to cause a bond to vibrate depends on the type of bond

The frequencies that are absorbed by the sample tell us the types of bonds (functional groups) that are present
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Wavenumbers
Wavenumber (cm-1) decreases with increasing atomic mass Wavenumber (cm-1) increases with increasing bond energy

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Wavenumbers
Wavenumber (cm-1) decreases with increasing atomic mass Wavenumber (cm-1) increases with increasing bond energy

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Wavenumbers

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Wavenumbers
Effect of resonance

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Wavenumbers
Effect of resonance

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IR Signal Strength - Intensity

IR signals can vary Greater bond polarity = stronger IR signals Multiple bonds of the same type also can cause strong signals to be observed

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IR Signal Shape
IR signals can vary OH signals are often quite broad due to hydrogen bonding

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IR Signal Shape Hydrogen Bonding

IR signals can vary OH signals are often quite broad due to hydrogen bonding

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IR Signal Shape Hydrogen Bonding

H-bonding is often more pronounced in carboxylic acids because they can form H-bonding dimers.

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IR Signal Shape Coupled Interactions

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IR Signal Shape Coupled Interactions

The appearance of two NH signals for the primary amine is NOT simply the result of each N H bond giving a different signal. Instead, the two NH bonds vibrate together in two different ways.

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Sample preparation
IR spectra can be obtained from gas, liquid or solid samples. Liquids may be examined neat or in solution Samples are placed between salt plates For samples in solution: Solvent selected must be dried and transparent in the region of interest, i.e. CCl4 and CS2. Non polar solvents tend to be better for this type of preparation Solids are examined as a mull (suspended in oil, Nujol), as a pressed disk (grind with salt and make a pellet), or as a deposited glassy film

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Analyzing the IR Spectrum

Table 15.2 summarizes some of the key signals that help us identify what functional groups are present in molecules Often, the molecular structure can be identified from an IR spectra:
Focus on the diagnostic region (above 1500 cm-1):
a) b) c) d) 1600-1850 cm-1: check for double bonds. 2100-2300 cm-1: check for triple bonds. 2700-4000 cm-1: check for XH bonds. Analyze wavenumber, intensity, and shape for each signal.

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Analyzing the IR Spectrum

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Analyzing the IR Spectrum

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