Infrared Spectroscopy (IR) 3.

From molecular formula

 Classic methods for organic structure  Double bond equivalent

determination:
4. Infrared spectroscopy (IR)
o Boiling point
o Refractive index  Identify some specific functional groups
o Solubility tests  e.g. C=O, C–O, O–H, COOH, NH2 … etc.
o Functional group tests
o Derivative preparation 5. UV (Ultraviolet) Spectroscopy
o Sodium fusion (to identify N,
Cl, Br, I & S)  Sometimes useful especially for
o Mixture melting point conjugated systems
o Combustion analysis  e.g. dienes, aromatics, enones
o Degradation
 Require large quantities of sample and
are time consuming 6. 1H, 13C NMR and other advanced NMR
techniques
 Spectroscopic methods for organic structure
determination  Full structure determination

a) Infrared Spectroscopy (IR)

 Characteristic functional groups
 Spectroscopy and the Electromagnetic
b) Ultraviolet Spectroscopy (UV) Spectrum
 Waves are classified by frequency or
 Characteristic chromophore
wavelength ranges
c) Nuclear Magnetic Resonance (NMR)

 Composition of atomic groups within

the molecule.

d) Mass Spectroscopy (MS)

 Molecular Mass & characteristic

fragmentation pattern

●Combination of these spectroscopic

 Electromagnetic radiation seems to
techniques provide a rapid, accurate, and
have dual behavior:
powerful tool for Identification and Structure
 Possesses the properties of a photon
Elucidation of organic compounds
 A photon is the smallest discrete
●Effective in milligram and microgram amount or quantum of electromagnetic
quantities. radiation such as light and radio waves
 It is the basic unit of all light.
 General steps for structure elucidation  The photon is a type of elementary
1. Elemental analysis particle. It is force carrier for the
 Empirical formula electromagnetic force.
 e.g. C2H4O  They are elementary particles despite
lacking rest mass.
 They always move at the speed of light
2. Mass spectrometry in vacuum, 299792458 m/s.

 Molecular weight  Behaves as an energy wave

 Molecular formula  Speed of the wave
 e.g. C4H8O2, C6H12O3 … etc. Wavelength × Frequency = Speed
λ (m) × ν = c
 Characteristic fragmentation pattern for
λ = c/v
certain functional groups
  The unit of electromagnetic energy is
called quanta
 Considering the plank equation and
multiplying ɛ by Avogadro’s number NA:
 These vibrations are quantized, and as
they occur, the compounds absorb IR
energy in particular regions of the IR
portion of the electromagnetic
spectrum.
 A plot of these absorbed frequencies is
called an IR spectrum.

• IR region has lower energy than visible

light (below red - produces heating as with a
heat lamp)

 Absorption Spectrum
 Organic compound exposed to
electromagnetic radiation can absorb
energy of only certain wavelengths (unit
of energy)
 Transmits energy of other wavelengths
 Changing wavelengths to determine
which are absorbed and which are  Wavenumber
transmitted produces an absorption
spectrum
 In infrared radiation, absorbed energy
causes bonds to stretch and bend more
vigorously
 In ultraviolet radiation, absorbed energy
causes electrons to jump to a higher-
energy orbital (electronic transition)

 Worked Example:

Calculate the energy in kJ/mol for a gamma ray

with λ = 5.0×10-11m

 The position of an absorption band (peak) in

an IR spectrum is specified in units of
wavenumbers

 INFRARED SPECTROSCOPY: AN
INSTRUMENTAL METHOD FOR DETECTING
FUNCTIONAL GROUPS
 Absorption of Infrared (IR) radiation
causes atoms and groups of atoms of
organic compounds to vibrate with
increased amplitude about the covalent
bonds that connect them.
 This absorption will occur at specific
frequencies characteristic of the types
of bonds and atoms present in the
specific functional groups of that
molecule.
 Interpreting Infrared Spectra  The actual relative frequency of vibration can
 IR spectrum interpretation is difficult as the be predicted:
arrangement of organic molecules is complex
 Disadvantage - Generally used only in
pure samples of fairly small molecules
 Advantage - Provides a unique
identification of compounds
o Fingerprint region - 1500cm-
1 to 400 cm-1 (approx)
 Complete interpretation of the IR spectrum is  Bonds with lighter atoms vibrate faster
not necessary to gain useful structural than those with heavier atoms.
information
 IR absorption bands are similar  Triple bonds (which are stiffer and stronger)
among compounds vibrate at higher frequencies than double
bonds:
 Region from 4000 to 1500 cm-1 can be
divided into areas characterized by:
• Single-bond stretching motions
• Triple-bond stretching motions
• Absorption by double bonds
• Fingerprint portion of the IR spectrum

 In order for vibration to occur with the

absorption of IR energy, the dipole moment
of the molecule must change as the vibration
occurs.
 e.g. CH4 symmetric stretching of C-H
doesn’t absorb IR energy
 C-H bonds at sp centers appear at 3000-3100
 The IR spectrum of a molecule usually
cm-1
contains many peaks.
 C-H bonds at sp2 centers appear at about
3080 cm-1
 These peaks are due to the various types of
 C-H bonds at sp3 centers appear at about
vibrations available to each of the different
2800-3000 cm-1 bonds.
 Additional peaks result from overtone
• C-C bond stretching frequencies are only useful
(harmonic) peaks which are weaker and of
for multiple bonds: lower frequency.
 The IR is a “fingerprint” of the molecule
 C-C double bonds give peaks at 1620-1680
because of the unique and large number of
cm-1 peaks seen for a particular molecule.
 C-C triple bonds give peaks at 2100-2260 cm-
1 Characteristic IR absorptions
 These peaks are absent in symmetrical double
and triple bonds.

Interpreting IR Spectra
 IR spectrum of octane
  IR spectrum of 1-octene

IR Spectra of Some Functional Groups

Containing Heteroatoms

 Carbonyl Functional Groups

 Alcohols and phenols

 The IR absorption of an alcohol or
phenol O–H group is in the 3200–
3550 cm-1 range, and most often
Interpreting IR Spectra it is broad.
 IR spectrum of toluene

 Carboxylic Acids
 IR spectrum of propanoic acid

 IR spectrum of 1-heptyne

 Amines
 Primary and 2ndary amines give absorptions to electrons that can be excited to higher
of moderate strength in the 3300–3500 cm-1 energy orbitals
region
 primary amines exhibit two peaks in this  UV spectrum
region due to symmetric & asymmetric
 stretching of the two N–H bonds
 2ndary amines exhibit a single peak
 Tertiary amines show no N–H absorption
because they have no such bond
 A basic pH is evidence for any class of amines

 IR spectrum of 4-methylaniline

Absorption Maxima for Noncon-jugated and

Conjugated Dienes

 Analytical Uses of UV–Vis Spectroscopy

 UV–Vis spectroscopy can be used in the
structure elucidation of organic molecules to
indicate whether conjugation is present in a
given sample
 A more widespread use of UV–Vis
spectroscopy, however, has to do with
determining the concentration of an
unknown sample
 Quantitative analysis using UV–Vis
ULTRAVIOLET–VISIBLE spectroscopy is routinely used in biochemical
studies to measure the rates of enzymatic
SPECTROSCOPY reactions

 The absorption of UV–Vis radiation is caused  Ultraviolet Spectroscopy

by transfer of energy from the radiation beam
 generally refers to electronic transitions
occurring in the ultraviolet ( range 200-380
nm) region of the electromagnetic spectrum
 Electronic transitions are also responsible in
the visible region (lambda range 380-800 nm)
which is easily accessible instrumentally but
are of less importance in the solution of
structural problems since most organic
compounds are colorless.
 An extensive region at wavelengths shorter
than ~200 nm (“vacuum UV”) also
corresponds to electronic transitions but this
region is not accessible with standard
instruments.
Types of Electronic Transition
 the transitions are brought about by the
presence of chromophores in the molecule
( a part of the molecule which can be a
functional group or a single atom or group of
atoms in a molecule which may not be
associated with chemical functionality)
 In practice, double-beam instruments are
used where the absorption of a reference cell,
containing only solvent, is subtracted from
the absorption of the sample cell.
 The energy source, the materials from which
the dispersing device and detector are
constructed must be appropriate for the
range of wavelength scanned as transparent
as possible to the radiation.
 For UV measurements, the cells and optical
components are typically made of quartz and
ethanol, hexane, water or dioxane are usually
chosen as solvents.
 Quantitative aspects
 The y-axis of a UV spectrum may be
calibrated in terms of the intensity of
transmitted light (% transmission or
absorption) or on a logarithmic scale i.e., in
terms of Absorbance A:
 Beer’Lambert law: Absorbance, A is
proportional to the concentration and path
length; intensity is usually expressed as molar
absorbance or molar extinction coefficient E.
Where M = molecular weight
C = concentration (g/L) l = path length (cm)
 UV absorption bands are characterized by the
wavelength of maximum absorption (l max)
and E.
 The values of E vary from 10 and 105 and are
conveniently tabulated as log10(E).
 The presence of small amounts of strongly
absorbing impurities may lead to errors in the
interpretation of UV data.
Classification of UV Bands
 UV absorption bands have fine structures due
to the presence of vibrational sub-levels but
are rarely observed in solution due to
collisional broadening.
 As transitions are associated with changes of
electron orbitals, they are often described in
terms of the orbitals involved or by another
classification method:
 A molecule may give rise to more than one
band because it contains more than one
chromophore or because more than one
transition of a single chromophore is
observed.

Table 1. The Effect of Conjugation on UV

Absorption

 UV spectra typically contain far fewer

features than IR, NMR or MS spectra and thus
have a lower information content.

Special Terms in UV Spectroscopy
 Auxochromes (auxillary chromophores):
groups which have little UV absorption by
themselves, but which often have significant
effects on the absorption (both max and )
of a chromophore to which they are attached;
are atoms with one or more lone pairs ( -OH, -
OR, -NR2, -halogen)
 bathochromic shift: shift of absorption
maximum to longer wavelength
 hypsochromic shift: shift of absorption
maximum to shorter wavelength
 Hyperchromic effect: an increase in
absorption intensity
 Hypochromic effect: a decrease in absorption
intensity
 When there are more than 8 conjugated double
bonds, the absorption maximum of polyenes is
such that they absorb light strongly in the visible
region.
 Empirical rules (Woodward Rules) of good
predictive value are available to estimate the
positions of max in conjugated polyenes and
conjugated carbonyl compounds.
Woodward-Fieser Rules for Calculating the λmax
of
I. Conjugated Dienes and Polyenes

Important UV Chromophores

 Most of the reliable and useful data is due to

relatively strongly absorbing chromophores (
> 200) which are mainly indicative of
conjugated or aromatic systems

(1) Dienes and Polyenes

 Extension of conjugation in C chain is always

associated with a pronounced shift towards
longer wavelength (bathochromic shift) and
towards greater intensity (hyperchromic
shift).

 A diene is either:
 homoannular with both double bonds
contained in one ring

 heteroannular with two double bonds

distributed between two rings.

II. α, β UNSATURATED CARBONYL COMPOUNDS

OR KETONES:
Examples
Example

Examples

 Carbonyl compounds

 All carbonyl derivatives exhibit weak (E< 100)

absorption between 250 and 350 nm, and this
is only of marginal use in determining
structure.

 Conjugated carbonyl derivatives always exhibit

strong absorption.

III. Aromatic Compounds

Table 2. UV Absorption Bands in Common Carbonyl

Compounds

 Benzene derivatives
 exhibit medium to strong absorption with
bands having characteristic fine structure and
 the intensity of the absorption being strongly
influenced by substituents:
 Weak auxochromes: -CH3, -Cl, -OCH3
 Groups which increase conjugation:
-CH=CH2, -C(=O)-R, -NO2
 Auxochromes whose absorption is pH
dependent: -NH2 and -OH

 The added conjugation in naphthalene,

anthracene and tetracene causes
bathochromic shifts of these absorption
bands.