IB CHEMISTRY

Topic 11 Measurement and data

processing - Spectroscopy

Higher level
 11.3 Spectroscopic identification of
organic compounds
OBJECTIVES
• The degree of unsaturation or index of hydrogen deficiency (IHD)
can be used to determine from a molecular formula the number of
rings or multiple bonds in a molecule.
• Mass spectrometry (MS), proton nuclear magnetic resonance
spectroscopy (1H NMR) and infrared spectroscopy (IR) are
techniques that can be used to help identify compounds and to
determine their structure.
• Determination of the IHD from a molecular formula.
• Deduction of information about the structural features of a
compound from percentage composition data, MS, 1H NMR or IR.
EMS and compound identification
The electromagnetic spectrum (EMS) interacts
with compounds in ways that help us identify
them. These techniques (X-ray crystallography,
UV-vis spectroscopy, IR spectroscopy, nuclear
magnetic resonance NMR) coupled with the
index of hydrogen deficiency and mass
spectrometry are used to determine the
structure, purity and composition of a
substance.
 EMS calculations
Ephoton = hf
E = energy in one photon (J)
h = planks constant (6.63x10-34Js)
f = frequency (Hz)
v = fλ
v = velocity = c = speed of light = (3.00 x 108 m/s)
λ = wavelength (nm)

So E α f (h is constant) also E = hc/λ so E α 1/λ

The interactions of the EMS and electrons via photon
emission/absorption can hence be measured.
 Infrared spectroscopy (IR)
This technique uses
absorption of the IR part
of the EMS. Molecules
will absorb IR radiation if
they can bend so that
their dipole moment is
disrupted. This occurs
only with symmetric
bends, and asymmetric
stretches, but not
symmetric stretches.
 Infrared spectroscopy (IR)
Based on Hooke’s Law, the
greater the stretch, the more
energy is required
F = -kx
Lighter atoms have a higher
frequency.
Stronger bond enthalpies also
give higher frequencies.
Wavenumbers between 300-
1400cm-1 are called the
fingerprint and are unique to
each molecule.
IR spectrum of ethanol
Problem 1:
ANSWER:
 Proton nuclear magnetic resonance
spectroscopy (1H NMR)
This technique uses the radio wave part of the EMS
along with its interactions with magnetic fields.
The proton spins of the hydrogen atoms act as tiny
magnets. When placed in a magnetic field they use
energy to line up with or against this field. The
energy is measured in the radio wave region of the
EMS. The 1H NMR spectrum is the position of this
energy change, the chemical shift, relative to a
standard (tetramethylsilane TMS) measured in ppm
of the proton, symbol δ.
 Proton nuclear magnetic resonance
spectroscopy (1H NMR)
The integration trace
shows the relative
number of hydrogens
present (area under
the graph 1:2:3).
The peaks also show H
in different
environments
determined by looking
up chemical shifts in Three different
your data booklet. H environments
Problem 1:
ANSWER:
Index of hydrogen deficiency (IHD)
The index of hydrogen deficiency is the degree
of unsaturation of a molecule.
It is determined either by structure or the
molecular formula.
Determination by structure:
• A double bond or a ring counts as 1 degree of
unsaturation (IHD = 1).
• Triple bonds count as 2 degrees of
unsaturation (IHD = 2).
 Index of hydrogen deficiency (IHD)
Determination by formula:

For a compound CcHhNnOoXx

For IHD of alkanes to be zero you need to make carbons equal to hydrogens.
For this you need to double the carbons and add 2.
Therefore: 2c + 2 – h

2 + 2 -4 = 0
6+2–8=0
8 + 2 – 10 = 0

Nitrogen adds hydrogens, therefore + n

Halogens reduce hydrogens, therefore – x

Losing a hydrogen and gaining something else has the effect of 2, so all is
divided by 0.5.

Therefore:
Problem 1: Determine the IHD for C6H6
IHD = (0.5)(2c+2-h-x+n)
= (0.5)(2x6+2-6) = 4
The possible solution to this compound C6H6
could be any of:
 Mass spectrometry (MS)
• The molecular ion peak represents the molecular
mass of the compound
• As the ionization breaks up the molecule into parts
it creates a fragmentation pattern. These
fragments can be read to determine the structure
of the molecule.
• Use the data booklet to read which peaks refer to
which fragments to reconstruct your molecule.
Data booklet:
Problem 1:
ANSWER:
 21.1 Spectroscopic identification of

Higher level
organic compounds
OBJECTIVES

• Structural identification of compounds involves several different

analytical techniques including IR, 1H NMR and MS.
• In a high resolution 1H NMR spectrum, single peaks present in low
resolution can split into further clusters of peaks.
• The structural technique of single crystal X-ray crystallography can
be used to identify the bond lengths and bond angles of crystalline
compounds.
• Explanation of the use of tetramethylsilane (TMS) as the reference
standard.
• Deduction of the structure of a compound given information from a
range of analytical characterization techniques (X-ray
crystallography, IR, 1H NMR and MS).
 High resolution 1H NMR

Higher level
Spin-spin coupling creates slightly different
energy levels creating splits in peaks. This is
caused by different combinations of spins.
These split peaks cannot be seen on normal low
resolution NMR.
Tetramethylsilane (TMS) standard

Higher level
A good standard because:
1. Hydrogens are all in the same
environment so only one reference
line is produced given a value δ =
0ppm
2. Si has a lower electronegativity
than C so Si-H lines do not overlap
with C-H ones.
3. Chemically inert, soluble in organic
solvents, and can be easily removed
by boiling.
High resolution 1H NMR

Higher level
Example for ethanal, with
red line showing Low
resolution 1H NMR.
 High resolution 1H NMR

Higher level
Protons on the same atom do not split as they behave
as a group.
Protons on non-adjacent atoms do not interact with
each other.
The proton on a hydroxyl group generally does not
split.
 High resolution 1H NMR

Higher level
Effect of CHO proton on spins of CH3 protons:
 High resolution 1H NMR

Higher level
Effect of CH3 protons on spins of CHO proton:

Hence there are four peaks.

 High resolution 1H NMR

Higher level
Another example:

This splitting does not occur

with equivalent hydrogens.
The interfering magnetic
field called shielding occurs
from nearby hydrogens on
the next carbon, ie. Ha are
split from Hb and vise versa.
 Effects of spin coupling

Higher level
For Hb the effect of Ha is seen
as follows:
(direction of magnetic field is up)
High resolution 1H NMR

Higher level
 Downfield movement
 High resolution 1H NMR rules

Higher level
1. The number of splits in a peak for a particular
hydrogen is determined by counting the
number of neighboring hydrogens (on other
carbons) and adding 1 (ie. n+1).

2. The intensity of the split peaks can be

determined using Pascal’s triangle.
 High resolution 1H NMR

Higher level
Integration is the area under the graph and gives
the relative number of hydrogens in a molecule.
This data helps to determine the molecular
structure.
 Problem 1:

Higher level
 ANSWER:

Higher level
 Problem 2:

Higher level
 Higher level
X-ray crystallography
When a compound is in a
crystalline form, the
diffraction of X-rays
through the structure by
the atoms can be analysed
mathematically to deduce
the bond lengths and
angles in a compound.
This was used to
determine the structure of
DNA and is still being used
to determine many still
unknown protein
structures.