Chapter 12

Infrared Spectroscopy & Mass Spectrometry

12-1 Introduction Spectroscopy is an analytical technique which helps determine structure.

It involves the use of the absorption, emission, or scattering of electromagnetic radiation by matter to qualitatively or quantitatively study the matter or to study physical processes. It destroys little or no sample.

The amount of light absorbed by the sample is measured as wavelength is varied.

Types of Spectroscopy
Infrared (IR) spectroscopy measures the bond vibration frequencies in a molecule and is used to determine the functional group. Mass spectrometry (MS) fragments the molecule and measures the masses. Nuclear magnetic resonance (NMR) spectroscopy detects signals from hydrogen atoms and can be used to distinguish isomers. Ultraviolet (UV) spectroscopy uses electron transitions to determine bonding patterns.

12-2 The Electromagnetic Spectrum

Examples: gamma rays, X rays, microwaves, radio waves, visible light, IR, and UV. Frequency and wavelength are inversely proportional. c = , or = c/, where c is the speed of light. Energy per photon = h, where h is Plancks constant.

Visible light and gamma rays and microwaves are really the same things. They are all electromagnetic radiation; they just differ in their wavelengths.

 Electromagnetic Radiation
Electromagnetic radiation consists of discrete packets of energy called photons. A photon consists of an oscillating electric eld component, E, and an oscillating magnetic eld component, M.

The electric and magnetic elds are orthogonal (perpendicular) to each other, and they are orthogonal to the direction of propagation of the photon. The electric and magnetic elds of a photon ip direction as the photon travels. The number of ips, or oscillations, that occur in one second is called the frequency, . [units of oscillations per second, or s-1 (Hertz)]. The physical distance in the direction of propagation a photon makes one complete oscillation is called the wavelength, , of the electromagnetic radiation.
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The equations summarizing the relationships between energy (E), frequency (v), and wavelength (l): E = hv v = c/ E = hc/

(h = 6.63 x 10-27 erg sec; c = 2.998 x 1010 cm sec-1)

12-3 The Infrared Region

The IR region covers
7.8 x 10-7 m (just above the visible region) to 2.0 x 10-3 m (just below the microwave region)

Organic chemistry uses mainly the vibrational IR, which covers

2.5 x 10-6 m (2.5 m) to 2.5 x 10-5 m (25 m)

Absorption of IR radiation in this region causes bonds to change from a lower vibrational energy level to a higher one
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The frequency of IR radiation is commonly expressed in wavenumbers Wavenumber: the number of waves per centimeter, cm-1 (read reciprocal centimeters) Expressed in wavenumbers, the vibrational IR extends from 4000 cm-1 to 400 cm -1

10,000 m cm-1 2.50 m 10,000 m cm-1 25.0 m

= 4000 cm-1 = 400 cm-1

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12-4 Molecular Vibrations Covalent bonds vibrate at only certain allowable frequencies. Consider two covalently bonded atoms as two vibrating masses connected by a spring

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As the bond vibrates, its energy continually changes from kinetic to potential and vice versa. The total energy (EK + EP) is proportional to the frequency of vibration. The energies associated with these vibrations are quantized; i.e., within a molecule, only specic vibrational energy levels are allowed The energies associated with transitions between vibrational energy levels for most covalent bonds are from 2 to 10 kcal /mol (8.4 to 42 kJ/mol)
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The position of absorption of a stretching vibration depends on

the strength of the vibrating bond and the masses of the atoms connected by the bond

The intensity of absorption depends primarily on the polarity of the vibrating bond
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Stretching Frequencies

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requency decreases with increasing atomic weight. F requency increases with increasing bond energy. F (see p514, Table 12-1)
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For a nonlinear molecule containing n atoms, there are 3n -6 allowed fundamental vibrations. For even a relatively small molecule, a large number of vibrational energy levels exist and patterns of IR absorption can be very complex. The simplest vibrational motions are bending and stretching.

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Vibrational Modes

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In-plane rocking + +

In-plane scissoring +

Out-of-plane wagging

Out-of-plane twisting

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Fingerprint of Molecule
Whole-molecule vibrations and bending vibrations are also quantitized. No two molecules will give exactly the same IR spectrum (except enantiomers). Simple stretching: 1600-3500 cm-1. Complex vibrations: 600-1400 cm-1, called the ngerprint region.
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 General Trends:

Stretching frequencies are higher than corresponding bending frequencies. (It is easier to bend a bond than to stretch or compress it.) Bonds to hydrogen have higher stretching frequencies than those to heavier atoms. Triple bonds have higher stretching frequencies than corresponding double bonds, which in turn have higher frequencies than single bonds. (Except for bonds to hydrogen).
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Characteristic IR absorptions for the types of bonds and functional groups most often seen in organic chemistry
Bond O-H N-H C-H C=O C=C C-O Frequency (cm-1) 3200-3650 3100-3500 2850-3300 1630-1810 1600-1680 1050-1250 Intensity strong and broad medium medium to strong strong weak strong
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12-5 IR-Active & IR-Inactive Vibrations For a molecule to absorb IR radiation, the bond undergoing vibration
must be polar and its vibration must cause a periodic change in the bond moment

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Covalent bonds which do not meet these criteria are said to be IR inactive
the C-C double and triple bonds of symmetrically substituted alkenes and alkynes, for example, do not absorb IR radiation because they are not polar bonds
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Interaction of a molecular dipole moment w/ an electric eld

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12-6 Measurement of the IR Spectrum An Infrared Spectrometer

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FT-IR Spectrometer
Uses an interferometer. Has better sensitivity. Less energy is needed from source. Completes a scan in 1-2 seconds. Takes several scans and averages them. Has a laser beam that keeps the instrument accurately calibrated.
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12-7 Infrared Spectroscopy of Hydrocarbons

12-7A Carbon-Carbon Bond Stretching

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Stronger bonds absorb at higher frequencies:

C-C 1200 cm-1 C=C 1660 cm-1 C=C 2200 cm-1 (weak or absent if internal)

Conjugation lowers the frequency:

isolated C=C conjugated C=C aromatic C=C 1640-1680 cm-1 1620-1640 cm-1 approx. 1600 cm-1

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12-7B Carbon-Hydrogen Bond Stretching

Bonds with more s character absorb at a higher frequency.

sp3 C-H, just below 3000 cm-1 (to the right) sp2 C-H, just above 3000 cm-1 (to the left) sp C-H, at 3300 cm-1

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12-7C Interpretation of the IR Spectra of Hydrocarbons An Alkane IR Spectrum

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Another Alkane IR Spectrum

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An Alkene IR Spectrum

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Compare hexane and hexene

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Alkyne IR Spectra-Terminal Alkynes are readily Identiable with IR

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12-8 Characteristic Absorption of Alcohols and Amines

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Both of O-H and N-H Stretching vibrations occur around 3300 cm-1, but they look different.
Alcohol O-H, broad with rounded tip. Secondary amine (R2NH), broad with one sharp spike. Primary amine (RNH2), broad with two sharp spikes. No signal for a tertiary amine (R3N)
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An Alcohol IR Spectrum

O-H str at 3600-3200 cm-1 C-O str at 1050-1150 cm-1

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Another Alcohol IR Spectrum

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O-H Stretch

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1o Amines

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2-Methylpentanediamine

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o 2

Amine

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Dipropylamine

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12-9 Characteristic Absorption of Carbonyl Compounds

12-9A Simple ketones, aldehydes, & acids
The C=O bond of simple ketones, aldehydes, and carboxylic acids absorb around 1710 cm-1. Usually, its the strongest IR signal. Carboxylic acids will have O-H also. Aldehydes have two C-H signals around 2700 and 2800 cm-1.
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Carbonyl Compounds

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A Ketone IR Spectrum

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An Aldehyde IR Spectrum

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Compare

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O-H Stretch of a Carboxylic Acid

This O-H absorbs broadly, 2500-3500 cm-1, due to strong hydrogen bonding.

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12-9B Resonance Lowering of Carbonyl Frequencies

Conjugation of C=O with C=C lowers the stretching frequency to ~1680 cm-1. The C=O group of an amide absorbs at an even lower frequency, 1640-1680 cm-1.

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An Amide IR Spectrum

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12-9C Carbonyl Absorptions Above 1720 cm-1

The C=O of an ester absorbs at a higher frequency, ~1730-1740 cm-1. Carbonyl groups in small rings (5 Cs or less) absorb at an even higher frequency.

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12-10 Characteristic Absorption of C-N Bonds C-N absorbs around 1200 cm-1. C=N absorbs around 1660 cm-1 and is much stronger than the C=C absorption in the same region. C=N absorbs strongly just above 2200 cm-1. The alkyne C=C signal is much weaker and is just below 2200 cm-1 .
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A Nitrile IR Spectrum

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12-11 Simplied Summary of IR Stretching Frequencies

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Strengths and Limitations of IR

IR alone cannot determine a structure. Some signals may be ambiguous. The functional group is usually indicated. The absence of a signal is denite proof that the functional group is absent.

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Correspondence with a known samples IR spectrum conrms the identity of the compound.
Review p533-534
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12-12 Reading and Interpreting IR Spectra (Solved problem)

An extremely useful review section. p534-539

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12-13 Introduction to Mass Spectrometry Molecular weight can be obtained from a very small sample. It does not involve the absorption or emission of light. A beam of high-energy electrons breaks the molecule apart. The masses of the fragments and their relative abundance reveal information about the structure of the molecule.
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12-13A The Mass Spectrometer

Electron Impact Ionization A high-energy electron can dislodge an electron from a bond, creating a radical cation (a positive ion with an unpaired e-).
H H H H
H H e+ H C C H H H
H H C+ H H C H
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H C C H
H H H C C+ H H H

Separation of Ions
Only the cations are deected by the magnetic eld. Amount of deection depends on m/z. The detector signal is proportional to the number of ions hitting it. By varying the magnetic eld, ions of all masses are collected and counted.
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Mass Spectrometer

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The GC-MS
A mixture of compounds is separated by gas chromatography, then identified by mass spectrometry.

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12-13B The Mass Spectrum

Masses are graphed or tabulated according to their relative abundance.

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12-13C Mass Spectrometry of Mixtures: The GC-MS

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Reading assignment.

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Glossary
Molecular ion - The ion obtained by the loss of one electron from the molecule (m+) Base peak - The most intense peak in the MS, assigned 100% intensity Radical cation - positively charged species with an odd number of electrons Fragment ions - Lighter cations (and radical cations) formed by the decomposition of the molecular ion. These often correspond to stable carbcations. m/z - mass to charge ratio
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12-14 Determination of the Molecular Formula by Mass Spectrometry

12-14A High Resolution MS
Masses measured to 1 part in 20,000. A molecule with mass of 44 could be C3H8, C2H4O, CO2, or CN2H4. If a more exact mass is 44.029, pick the correct structure from the table:
C3H8

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C2H4O 44.02620

CO2

CN2H4 44.03740
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44.06260

43.98983

12-14B Use of Heavier Isotope Peaks

Isotopes: present in their usual abundance.

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Hydrocarbons contain 1.1% C-13, so there will be a small M +1 peak. If Br is present, M+2 is equal to M+. If Cl is present, M+2 is one-third of M+. If iodine is present, peak at 127, large gap. If N is present, M+ will be an odd number. If S is present, M+2 will be 4% of M+.
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Isotope abundance

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Mass Spectrum with Sulfur

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Mass Spectrum with Chlorine

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Mass Spectrum with Bromine

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12-15 Fragmentation Patterns in Mass Spectrometry

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Fragmentation of a molecular ion, M, produces a radical and a cation. Only the cation is detected by MS
R

R R'

Radical
R

R'+ Cation
R

Molecular ion (a radical cation)

Cation

Radical

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12-15A Mass Spectra of Alkanes

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More stable carbocations will be more abundant.

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12-15B Fragmentation Giving ResonanceStabilized Cations

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Resonance-stabilized cations favored.

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12-15C Fragmentation Splitting out a Small Molecule; Mass Spectra of Alcohols Alcohols usually lose a water molecule. M+ may not be visible.

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Important topics:
pectroscopy S R-active vibrations I haracteristic IR absorptions C asic principles of mass spectrometry B ragmentation patterns in mass spectrometry F

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