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Spectroscopy and Chromatography 1 Unit 4 New Specifications

This document discusses mass spectrometry and carbon-13 NMR spectroscopy. It explains that high resolution mass spectrometers can distinguish between compounds that have similar molecular weights by measuring mass to several decimal places, allowing determination of the exact molecular formula. It also describes how carbon-13 NMR spectroscopy provides information about carbon environments in a molecule based on differences in the magnetic field needed to bring each carbon-13 nucleus into resonance.

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Loh Jun Xian
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0% found this document useful (0 votes)
79 views

Spectroscopy and Chromatography 1 Unit 4 New Specifications

This document discusses mass spectrometry and carbon-13 NMR spectroscopy. It explains that high resolution mass spectrometers can distinguish between compounds that have similar molecular weights by measuring mass to several decimal places, allowing determination of the exact molecular formula. It also describes how carbon-13 NMR spectroscopy provides information about carbon environments in a molecule based on differences in the magnetic field needed to bring each carbon-13 nucleus into resonance.

Uploaded by

Loh Jun Xian
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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Spectroscopy and chromatography 1

use data from mass spectra to:


i) suggest possible structures of a simple organic compound given accurate relative
molecular masses
ii) calculate the accurate relative molecular mass of a compound, given accurate relative
atomic masses to four decimal places

Two common categories of mass spectrometry are high resolution mass spectrometry
(HRMS) and low-resolution mass spectrometry (LRMS). Not all mass spectrometers simply
measure molecular weights as whole numbers. High resolution mass spectrometers can
measure mass so accurately that they can detect the minute differences in mass between
two compounds that, on a regular low-resolution instrument, would appear to be identical.

The reason is because atomic masses are not exact multiples of the mass of a proton, as we
might usually think.
12
• An atom of C weighs 12.00000 amu.
16
• An atom of O weighs 15.9949 amu.
14
• An atom of N weighs 14.0031 amu.
1
• An atom of H weighs 1.00783 amu.

As a result, on a high resolution mass spectrometer, octan-2-one, C8H16O, has a molecular


mass of 128.12018 instead of 128. Naphthalene, C10H8, has a molecular weight of 128.06264.
Thus, a high resolution mass spectrometer can supply an exact molecular formula for a
compound because of the unique combination of masses that result.
• In LRMS, the molecular weight is determined to the nearest amu. The type of
instrument used here is more common because it is less expensive and easier to
maintain.
• In HRMS, the molecular weight in amu is determined to several decimal places. That
precision allows the molecular formula to be narrowed down to only a few
possibilities.
HRMS relies on the fact that the mass of an individual atom does not correspond to an
integral number of atomic mass units.

Calculate the high-resolution molecular weights for the following formulae.


1. C12H20O and C11H16O2
2. C6H13N and C5H11N2

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Spectroscopy and chromatography 1
It is possible to distinguish different formulas having Formula C6H12 C5H8O C4H8N2
the same nominal mass. The table on the right
illustrates this important feature, and a double- Mass 84.0939 84.0575 84.0688
focusing high-resolution mass spectrometer easily distinguishes ions having these
compositions. Mass spectrometry therefore not only provides a specific molecular mass
value, but it may also establish the molecular formula of an unknown compound.
Tables of precise mass values for any molecule or ion are will be given in the question paper.
Since a given nominal mass may correspond to several molecular formulas, lists of such
possibilities are especially useful when evaluating the spectrum of an unknown compound.

understand that carbon-13, (13C) NMR spectroscopy provides information about the
positions of 13C atoms in a molecule

Carbon-13, (13C) NMR spectroscopy

Carbon-13 nuclei as little magnets

About 1% of all carbon atoms are the C-13 isotope; the rest (apart from tiny amounts of the
radioactive C-14) is C-12. C-13 NMR relies on the magnetic properties of the C-13 nuclei.

Carbon-13 nuclei fall into a class known as "spin ½" nuclei.

The effect of this is that a C-13 nucleus can behave as a little magnet. C-12 nuclei do not have
this property.

A compass needle normally lines up with the Earth's magnetic field with the north-seeking
end pointing north. Provided it is not sealed in some sort of container, the needle can be
twisted around so that it pointed south - lining it up opposed to the Earth's magnetic field.

It is very unstable opposed to the Earth's field, and as soon as the needle is released, it will
flip back to its more stable state.

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Spectroscopy and chromatography 1
Because a C-13 nucleus behaves like a little magnet, it means that it can also be aligned with
an external magnetic field or opposed to it.

Again, the alignment where it is opposed to the field is less stable (at a higher energy). It is
possible to make it flip from the more stable alignment to the less stable one by supplying
exactly the right amount of energy.

The energy needed to make this flip depends on the strength of the external magnetic field
used but is usually in the range of energies found in radio waves - at frequencies of about 25
- 100 MHz.

It's possible to detect this interaction between the radio waves of just the right frequency
and the carbon-13 nucleus as it flips from one orientation to the other as a peak on a graph.
This flipping of the carbon-13 nucleus from one magnetic alignment to the other by the radio
waves is known as the resonance condition.

The importance of the carbon's environment

The above explanation would apply to an isolated carbon-13 nucleus, but real carbon atoms
in real bonds have other things around them - especially electrons. The effect of the electrons
is to cut down the size of the external magnetic field felt by the carbon-13 nucleus.

Suppose a radio frequency of 25 MHz is used, and the size of the magnetic field is adjusted
so that an isolated carbon-13 atom was in the resonance condition.

A carbon being surrounded by bonding electrons wouldn't be feeling the full effect of the
external field anymore and so would stop resonating (flipping from one magnetic alignment

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Spectroscopy and chromatography 1
to the other). The resonance condition depends on having exactly the right combination of
external magnetic field and radio frequency.

To bring it back into the resonance condition again the external magnetic field would have
to be increased slightly to compensate for the shielding effect of the electrons.

If the carbon is attached to something more electronegative, the electrons in the bond would
be further away from the carbon nucleus, and so would have less of a lowering effect on the
magnetic field around the carbon nucleus.

The external magnetic field needed to bring the carbon into resonance will be smaller if it is
attached to a more electronegative element, because the C-13 nucleus feels more of the
field. Even small differences in the electronegativities of the attached atoms will make a
difference to the magnetic field needed to achieve resonance.

Summary

For a given radio frequency (say, 25 MHz) each carbon-13 atom will need a slightly different
magnetic field applied to it to bring it into the resonance condition depending on what exactly
it is attached to - in other words the magnetic field needed is a useful guide to the carbon
atom's environment in the molecule.

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Spectroscopy and chromatography 1
Features of a C-13 NMR spectrum

The C-13 NMR spectrum for ethanol

A simple example of a C-13 NMR spectrum.

There are two peaks because there are two different environments for the carbons.

The carbon in the CH3 group is attached to 3 hydrogens and a carbon. The carbon in the CH2
group is attached to 2 hydrogens, a carbon and an oxygen.

The two lines are in different places in the NMR spectrum because they need different
external magnetic fields to bring them in to resonance at a particular radio frequency.

The C-13 NMR spectrum for a more complicated compound

This is the C-13 NMR spectrum for 1-methylethyl propanoate (also known as isopropyl
propanoate or isopropyl propionate).

This time there are 5 lines in the spectrum. That means that there must be 5 different
environments for the carbon atoms in the compound.

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There are 6 carbon atoms. So why only 5 lines? In this case, two of the carbons are in exactly
the same environment. They are attached to exactly the same things. Look at the two CH3
groups on the right-hand side of the molecule.

Why is the carbon in the CH3 on the left isn't also in the same environment. Just like the ones
on the right, the carbon is attached to 3 hydrogens and another carbon. But the similarity
isn't exact – look for the similarity along the rest of the molecule as well to be sure.

The carbon in the left-hand CH3 group is attached to a carbon atom which in turn is attached
to a carbon with two oxygens on it - and so on down the molecule.

That is not exactly the same environment as the carbons in the right-hand CH3 groups. They
are attached to a carbon which is attached to a single oxygen - and so on down the molecule.

As such each line in a C-13 NMR spectrum recognises a carbon atom in one particular
environment in the compound. If two (or more) carbon atoms in a compound have exactly
the same environment, they will be represented by a single line.

The need for a standard for comparison - TMS

The horizontal scale has a zero point - at the right-hand end of the scale. The zero is where a
peak due to the carbon-13 atoms in tetramethylsilane - usually called TMS. Everything else
is compared with this.

Some NMR spectra show the peak due to TMS (at zero), and others leave it out. Essentially,
when analysing of a spectrum which has a peak at zero, the peak can be ignored because
that's the TMS peak.

TMS is chosen as the standard for several reasons. The most important are:

• It has 4 carbon atoms all of which are in exactly the same environment. They are joined
to exactly the same things in exactly the same way. That produces a single peak, but
it's also a strong peak (because there are lots of carbon atoms all doing the same thing).

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• The electrons in the C-Si bonds are closer to the carbons in this compound than in
almost any other one. That means that these carbon nuclei are the most shielded from
the external magnetic field, and so you would have to increase the magnetic field by
the greatest amount to bring the carbons back into resonance.

The net effect of this is that TMS produces a peak on the spectrum at the extreme
right-hand side. Almost everything else produces peaks to the left of it.

The chemical shift

The horizontal scale is shown as (ppm). is called the chemical shift and is measured in parts
per million - ppm.

A peak at a chemical shift of, say, 60 means that the carbon atoms which caused that peak
need a magnetic field 60 millionths less than the field needed by TMS to produce resonance.

A peak at a chemical shift of 60 is said to be downfield of TMS. The further to the left a peak
is, the more downfield it is.

Solvents for NMR spectroscopy

NMR spectra are usually measured using solutions of the substance being investigated. A
commonly used solvent is CDCl3. This is a trichloromethane (chloroform) molecule in which
the hydrogen has been replaced by its isotope, deuterium.

CDCl3 is also commonly used as the solvent in proton-NMR because it doesn't have any
ordinary hydrogen nuclei (protons) which would give a line in a proton-NMR spectrum. It
does, of course, have a carbon atom - so why doesn't it give a potentially confusing line in a
C-13 NMR spectrum?

In fact it does give a line, but the line has an easily recognisable chemical shift and so can be
removed from the final spectrum.

Note

Newer NMR machines actually fix the magnetic field and vary the radio frequency instead. In
fact, the most modern machines send a pulse covering a wide spectrum of radio frequencies,
and use a computer to sort it all out afterwards.

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Spectroscopy and chromatography 1
Interpreting Carbon-13 Spectra

Page 3 of Data Booklet.

Working out structures from C-13 NMR spectra

Example 1

By just a quick look at a C-13 NMR spectrum (and without worrying about chemical shifts)
and deciding whether it is propanone or propanal (assuming those were the only options)

Because these are isomers, each has the same number of carbon atoms, but there is a
difference between the environments of the carbons which will make a big impact on the
spectra.

In propanone, the two carbons in the methyl groups are in exactly the same environment,
and so will produce only a single peak. That means that the propanone spectrum will have
only 2 peaks - one for the methyl groups and one for the carbon in the C=O group.

However, in propanal, all the carbons are in completely different environments, and the
spectrum will have three peaks.

Example 2
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Thare are four alcohols with the molecular formula C4H10O.

Which one produced the C-13 NMR spectrum below?

This can be done without referring to chemical shift tables.

In the spectrum there are a total of three peaks - that means that there are only three
different environments for the carbons, despite there being four carbon atoms.

In A and B, there are four totally different environments. Both of these would produce four
peaks.

In D, there are only two different environments - all the methyl groups are exactly equivalent.
D would only produce two peaks.

That leaves C. Two of the methyl groups are in exactly the same environment - attached to
the rest of the molecule in exactly the same way. They would only produce one peak. With
the other two carbon atoms, that would make a total of three. The alcohol is C.

Example 3

This follows on from Example 2, and also involves an isomer of C4H10O but which isn't an
alcohol. Its C-13 NMR spectrum is below. Work out what its structure is.

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Spectroscopy and chromatography 1

Since we do not know the structure, we will have to look at the chemical shift values. The
approximations are perfectly good, and we will work from this table:

carbon environment chemical shift (ppm)


C-C 0 - 50
C-O 50 - 100
C=C 100 - 150
C=O 150 - 200

There is a peak for carbon(s) in a carbon-oxygen single bond and one for carbon(s) in a
carbon-carbon single bond. That would be consistent with C-C-O in the structure.

It is not an alcohol (as mentioned in the question), and so there must be another carbon on
the right-hand side of the oxygen in the structure in the last paragraph.

The molecular formula is C4H10O, and there are only two peaks. The only solution to that is
to have two identical ethyl groups either side of the oxygen.

The compound is ethoxyethane (diethyl ether), CH3CH2OCH2CH3.

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Spectroscopy and chromatography 1
Questions
1.

2.

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