Spectroscopy

Introduction
Spectroscopy is an analytical technique
which helps determine
.
is used for
for monitoring
industrial processes.
It destroys little or no sample.
a variety of spectroscopic techniques are
often needed to determine
.

Types of Spectroscopy
Infrared (IR) spectroscopy measures bond
vibration frequencies in a molecule and is used
to determine the
.
Mass spectrometry (MS) fragments the molecule
and measures the
.
Nuclear magnetic resonance (NMR)
spectroscopy detects signals from atoms (e.g. H,
C, P) and can be used to determine
.
Ultraviolet (UV) spectroscopy uses
to determine bonding patterns.

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

The Electromagnetic Spectrum

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The IR Region
Just below
in the visible region.
Wavelengths usually
m.
More common units are
, or
cm-1, the reciprocal of the wavelength in
centimeters.
Wavenumbers are proportional to
frequency and
.

Molecular Vibrations
Covalent bonds vibrate at only certain
allowable
.

Stretching Frequencies

Frequency decreases with increasing

.
Frequency increases with increasing
.

Vibrational Modes
Nonlinear molecule with n atoms usually has
3n - 6 fundamental vibrational modes.

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

IR-Active and Inactive

A polar bond is usually
A nonpolar bond in a symmetrical
molecule will absorb

.
.

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An Infrared Spectrometer

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FT-IR Spectrometer

Uses an
.
Less energy is needed from source.
Completes a scan in 1-2 seconds.
Takes several scans and averages them.
Has a
that keeps the
instrument accurately calibrated.

Carbon-Carbon Bond Stretching

frequencies:
C-C
C=C
CC

bonds absorb at higher

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

lowers the frequency:

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

Carbon-Hydrogen Stretching
Bonds with more
higher frequency.

absorb at a

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

An Alkane IR Spectrum

An Alkene IR Spectrum

An Alkyne IR Spectrum

O-H and N-H Stretching

Both of these occur around
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)

An Alcohol IR Spectrum

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An Amine
IR Spectrum

Carbonyl Stretching
The C=O bond of simple ketones,
aldehydes, and carboxylic acids absorb
around
.
Usually, its the s
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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A Ketone
IR Spectrum

An Aldehyde
IR Spectrum

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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.

Variations in
C=O Absorption
Conjugation of C=O with C=C
the
stretching frequency to ~1680 cm-1.
The C=O group of an amide absorbs at an
even lower frequency,
cm-1.
The C=O of an ester absorbs at a higher
frequency, ~
cm-1.
Carbonyl groups in small rings (5 Cs or
less) absorb at an even
frequency.

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An Amide
IR Spectrum

Carbon - Nitrogen Stretching

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

Summary of IR
Absorptions

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Strengths and Limitations

IR alone
determine a structure.
Some signals may be ambiguous.
The
is usually indicated.
The
of a signal is definite proof
that the functional group is absent.
Correspondence with a known samples IR
spectrum
the identity of the
compound.

Mass Spectrometry

can be obtained from a

very small sample.
It does not involve the absorption or
emission of light.
A beam of
breaks the
molecule apart.
The
of the fragments and
their
reveal information
about the structure of the molecule.

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Electron Impact Ionization

A high-energy electron can dislodge an electron
from a bond, creating a
(a
positive ion with an unpaired e ).
H H
H C C H
H H

H H

H H
e-

H C C+

H C C H

H H

H H
H
H C+
H

H
C H
H

Separation of Ions
Only the
are deflected by the
magnetic field.
Amount of deflection depends on
.
The
is proportional to
the number of ions hitting it.
By varying the
, ions
of all masses are collected and counted.

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Mass Spectrometer

The Mass Spectrum

Masses are graphed or tabulated according to
their
.

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

Mass Spectra of Alkenes

cations favored.

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NMR
NMR is the most powerful tool available for
determination.
It is used to study a wide variety of nuclei:

The NMR Spectrometer

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Nuclear Spin
A nucleus with an odd atomic number or
an odd mass number has a
.
The spinning charged nucleus generates
a
.

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External Magnetic Field

When placed in an external field, spinning
protons act like
.

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The NMR Spectrometer

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Protons in a Molecule
Depending on their chemical
environment, protons in a molecule are
by different amounts.

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The NMR Graph

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Number of Signals
Equivalent hydrogens have the same
chemical shift.

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Intensity of Signals
The area under each peak is
to the number of protons.
Shown by integral trace.

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MRI
Magnetic resonance imaging, noninvasive
Nuclear is omitted because of publics
fear that it would be radioactive.
Only protons in one plane can be in
resonance at one time.
Computer puts together slices to get 3D.
Tumors readily detected.

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Ultraviolet Spectroscopy

excite electrons
from a bonding orbital to a *
antibonding orbital.
is useful for
.

Obtaining a UV Spectrum
The spectrometer measures the
of a reference beam through solvent only
(Ir) and the intensity of a beam through a
of the sample (Is).
Ir
Absorbance is the log of the ratio

Graph is absorbance vs. wavelength.

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UV Spectrum of Isoprene

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The UV Spectrum
Usually shows
.
Read max from the graph.
Absorbance, A, follows Beers Law:
where is the extinction coefficient or
molar absorptivity, c is the sample
concentration in moles per liter, and l is
the length of the light path in
centimeters.

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Sample UV Absorptions

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