Spectroscopy Supplement
UV Spectroscopy
The -electrons of a molecule may be promoted to a higher energy level with absorption of
light in the ultra-violet (200-400 nm) or visible (400-800 nm) region of the spectrum. Such
an absorption appears as a broad band in the spectrum and indicates the presence of two or
more conjugated double bonds (i.e. alternating double and single bonds). Figure 1 shows
examples of some conjugated systems.
O
O
A = cl
where c is the concentration of the solute in moll-1 and l is the pathlength in centimetres of the
cell in which the sample is measured. The data from a UV spectrum is recorded in the
following way:
Compound name: max (solvent) wavelength () nm
So for this example:
Ethyl p-aminobenzoate: max (EtOH) 293 (18000) nm
The position of the absorption maximum and its
intensity (which sometimes is recorded as its logarithm
log ) gives information about the constitution of the
organic molecule. In the case of ethyl p-aminobenzoate,
the strong absorption confirms the presence of the
aromatic ring.
OCH2CH3
NH2
Figure 2: UV spectrum of ethyl
p-aminobenzoate.
B.
Spectroscopy Supplement
IR Spectroscopy
Chromophore
(bond absorbing radiation)
OH, NH
Absorption
Region
33003600
CH*
29003000*
C=O
16301850
OCH2CH3
NH
NH
C=O
NH2
Note: 1280 cm-1 absorption is not useful as it lies in the fingerprint region.
3410
3327
1680
1280
C.
Spectroscopy Supplement
NMR Spectroscopy
C NMR Spectroscopy
The frequency (measured in MHz) at which 13C nuclei absorb radiofrequency radiation
depends mainly on the strength of the applied magnetic. The magnetic field experienced by
each nucleus, however, is not exactly the same as the applied magnetic field because the
electrons in the bonds very slightly alter the magnetic field in their immediate vicinity.
Nuclei in different environments thus absorb at different frequencies an effect which is
measured in Hz. Atoms (and therefore their nuclei) in exactly the same surroundings (by
symmetry analysis) are called chemically equivalent.
All chemically equivalent atoms absorb at the same frequency in an NMR spectrum.
In reporting the frequencies where groups of chemically equivalent carbons absorb, all signals
are reported in terms of how far they are shifted from a reference signal. The difference
between the reference signal and the signal of interest is termed the chemical shift and given
the symbol . For 13C NMR spectroscopy, the reference signal is usually the single absorption
of tetramethylsilane (TMS, Si(CH3)4) which is defined as 0.00 ppm Chemical shifts are
reported in dimensionless units of ppm (parts per million) which are independent of the
magnetic field strength at which the spectrum is obtained.
In 13C NMR spectra there is one absorption for each different carbon environment in a
molecule. If more than one carbon is in an identical environment within the molecule, the
signals in the spectrum are coincident. For example, in the spectrum of propane
(CH3CH2CH3), the two CH3 carbons appear as one line which is in a different place to the
signal from the CH2. In the 13C NMR spectrum the frequency of absorption is represented by
the scale which runs from 0 to 200 with units of parts per million (ppm). A particular
carbon environment results in a signal in a characteristic region of the spectrum, summarised
below:
200
100
150
(ppm)
50
0
TMS
C O
C C
(aromatic
rings)
C C
(alkenes)
C O
C C
C H
(alkanes)
Spectroscopy Supplement
H NMR Spectroscopy
~ 510 ppm
~ 05 ppm
~ 3.54.0 ppm
~ 2.02.5 ppm
ii. the area under the signals (as determined by integration of the peak) is proportional to
the relative numbers of hydrogen atoms giving rise to each signal.
iii. the fine structure of signals (the splitting pattern or multiplicity) reveals the number of
hydrogens on adjacent carbon atoms. The number of lines that a signal is split into is
equal to (n + 1) where n is the number of hydrogens on the adjacent carbon atom(s).
iv. OH, CO2H, and NH hydrogen atoms are readily exchanged by deuterium atoms when
the solution is treated with D2O, this means that such signals disappear from the
spectrum, as deuterium is not detected in 1H NMR spectroscopy.
Putting that all into a handy table
Observation
Information
Number of signals:
Number of H environments
Type of H environment
Area of signal:
Splitting of signals:
H of OH, CO2H or NH
Spectroscopy Supplement
H NMR Spectrum
exchanges
with D2O
Signals at 6.57 and 7.80 are both doublets and are due to
the aromatic hydrogens. Because of free rotation around the
bonds as shown on the right, the pair of hydrogens Ha are in
identical chemical environments and appear as one signal. And
the pair of hydrogens Hb are also in identical chemical
environments and hence appear as one signal. Each Ha has one
neighbour (Hb) hence by the (n + 1) rule appears as a doublet.
OCH2CH3
Ha
Ha
Hb
Hb
NH2
The area of each signal (indicated by the height of the integration curve above the
signal) confirms these assignments:
each aromatic signal corresponding to 2 H
the signal at 4.27 also corresponds 2 H
and the signal at 1.30 corresponds to 3 H
Spectroscopy Supplement
D. Mass Spectrometry
A mass spectrum is produced by first ionising a molecule (by expelling an electron from the
molecule at high energy or by protonating the molecule (both of which give positive ions), or
by forcing the molecule to absorb an extra electron, to give a negative ion), and then passing
the ions through a magnetic field which separates them on the basis of their mass:charge ratio
(m/z).
The mass of the heaviest ion usually corresponds to the molecular weight of the compound. If
so, this ion is referred to as the molecular ion, derived from the loss/gain of one electron
from/by the original molecule. The molecular ion can also decompose to give different
fragments, with different masses. The nature of the fragment ions formed depends on the
original bond energies present in the original structure. The intensities of the major peaks in a
mass spectrum are recorded relative to the biggest peak (called the base peak) which is
nominally assigned an intensity of 100%.
When writing up a mass spectrum, precisely how many peaks are recorded depends upon the
complexity of the spectrum and the significance of the peaks. Peaks of less than 10% intensity
are not normally noted, unless they correspond to the molecular ion or other diagnostic
fragments. Isotope peaks are ignored for C,H,N, and O, but are included for halogens.
Example: Mass spectrum of ethyl p-aminobenzoate (Figure 6).
Mass Spectrum
120
M+
165
92
137
OCH 2CH 3
NH2
m/ z = 165
HO
NH 2
m/ z = 137
NH2
m/ z = 120
NH2
m/ z = 92
Spectroscopy Supplement
E. References
Revision References
First Year Chemistry Lecture Notes
First Year Chemistry Laboratory Manual E35 Spectroscopy Workshop
McMurry Chapters 12 (MS & IR), 13 (NMR) and 14 (UV/VIS)
Further Reading
Spectroscopic Methods in Organic Chemistry
Dudley H. Williams, Ian Fleming.
Madsen 547.346 8 B
[Link to book in USyd Library]
[Link to e-Book]
IR Spectroscopy: an Introduction
Helmut Gnzler, Hans-Ulrich Gremlich
Madsen 543.08583 17
[Link to book in USyd Library]