MASS SPECTROSCOPY

MODULE 2 – LESSON 7

Prepared by: Sasha Rampersad-James 1

At the end of the lesson you should be able to;

• 7.1. Explain the basic principles of mass spectrometry; Include block

diagram. (Simple schematic diagram of the process).

• 7.2. Explain the significance of the (M+1) peak in mass spectra; and,

• 7.3. Use mass spectral data to:

• (a) determine relative isotopic masses; and relative isotopic
abundance; and,
• (b) distinguish between molecules of similar relative molecular mass.
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 Introduction
(Chemistry for cape, suzan maraj & Arnold samai, 2011)

• What is Mass Spectroscopy?

• Mass spectrometry is an analytical tool useful for measuring the mass-to-
charge ratio (m/z) of one or more molecules present in a sample. These
measurements can be used to calculate the exact molecular weight of the
sample components.

• What the mass spectrometer?

• The mass spectrometer is a device used to determine the relative atomic
mass and the relative abundance of isotopes.

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SCHEMATIC DIAGRAM OF MASS
SPECTROSCOPY

4
 Basic principle of mass spectroscopy (Chemistry
for cape, suzan maraj & Arnold samai, 2011)

• A sample to be analysed is vaporized and bombarded with a stream of high

intensity electrons – electron ionization.

• Multiple positive ions or fragments are accelerated in an electric field.

• The high speed positive ions are deflected in a magnetic field and separated
according to their mass to charge ratio.

• Ions with a particular mass to charge ratio are detected and recorded as a mass
spectrum.

• The relative heights of the peaks in the mass spectrum give a measure of the relative
amounts of the different ions present.
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OTHER EXAMPLES OF SCHEMATICS OF
MASS SPEC.

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 FRAGMENTATION1
• Mass spectroscopy is also used to analyse organic molecules.

• The beam of electrons used for ionization in the mass spectrometer may
also cause the molecular ions to break into fragments.

• Fragmentation of the molecular ion occurs readily at positions that give the
most stable carbocation fragment.

• When fragmentation occurs one fragment retains the positive charge while
the other fragment is often electrically neutral.

• Only the positively charged fragments appear in the spectrum.

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 FRAGMENTATION2

• The fragments give information about the structure of the original

molecule.

• The fragments in the greatest quantity produces the tallest peak and is the
called the BASE PEAK.

• All the other peaks in the spectrum are measured as a percentage of the
abundance of the base peak.

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•PEAKS IN THE MASS SPECTRUM

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 BASE PEAK
•Remember the BASE PEAK is the fragments in the
greatest quantity and it produces the tallest peak.

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 MOLECULAR ION PEAK (m)
• When one electron is lost from the complete molecule, the peak produced is
called the molecular ion peak.

• The mass of this peak represents the relative formula mass of the molecule.

• The molar ion peak is usually found among the peaks of greatest mass in the
spectrum but is not necessarily the peak with the highest mass since various
isotopes may be present in the molecule.

• In cases where the molecular ion is not stable, the peak may appear weak or
may event be absent. This is because the molecular ion fragments into more
stable carbocation fragments and does not exist long enough for a peak to
appear. 11
 M+1 Peak1
• A peak with a mass 1 unit heavier than the molecular ion is called
the M+1 Peak.

• This may be due to the presence of 13C or 2H isotopes in some of the

molecules.

• The 13C isotope is considered to be the major contributor to the

M+1 peak because the relative abundance of 13C in nature is 1% of
that of 12C while that of 2H is 0.01% of that of 1H.

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 M+1 Peak2
• Example using C4H10 – butane.

• The occurrence of a mass 1 unit heavier than the molecular ion will be 4×1 or
4% of the time for 13C and 10×0.01 or 0.1% of the time for 2H. This means that
if the M+1 peak was caused by an isotope of carbon, it would have a relative
abundance of 4% of that of the molecular ion peak.

• On the other hand, if it was caused by an isotope of H then it would have a

relative abundance of 0.1% of the molecular ion peak.

• In the M+1 peak is about 4% of that of the molecular ion peak with suggests
that the M+1 peak may be due to one of the 12C atoms being replaced by a 13C
atom. 13
 M+1 Peak3
• The presence of the M+1 peak can be used to determine the number of
carbon atoms present in a molecule.

• This is significant in distinguishing between unknown molecules which have

similar relative molecular masses.

• For example, both C3H8O and CH4N2O have similar relative molecular masses
but both have a different number of carbon atoms.

• The relative abundance of the M+1 peak can be used to determine the number
of carbon atoms in each molecule and hence distinguish between the two
molecules. 14
 M+2 Peak
• Some compounds produce a peak with a mass 2 units heavier than the
molecular ion. This is called the M+2 peak and it is often caused by the
presence of Cl or Br atoms.

• The relative abundance of 37Cl in nature is 33% that of 35Cl so that the mass
spectrum of a compound containing a chlorine atom produces an M+2 peak
that is about one third the relative abundance of the molecular ion peak.

• Similarly the natural abundance of 81Br is 98% of that of 79Br, thus the mass
spectrum of a compound containing a bromine atom produces an M+2 peak
that is almost equal to the molecular ion peak.
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 Fragmentation Patterns
• The mass spectrum of an organic compound gives different
information from the mass spectrum of an element.

• The mass spectrum of an element, each line represents a different

isotope of that element.

• In organic compounds, each line represents a different fragment

produced when the molecular ion breaks up.

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 Fragmentation Patterns2
• The fragmentation pattern of butane: produces peaks with mass/charge ratio
15, 27, 28, 29, 39, 41, 42, 43, 58 and 59.

• The most stable ion C3H7+ occurs at m/e = 43 which is the base peak.
• The molecular ion C4H10+ is present at m/e = 58
• The M+1 peak is at 59
• The peaks at m/e ratio 15 and 29 are the CH3+ and C2H5+ ions respectively.

• These are produced by fragmentation:

• C4H10+ CH3+ + .C3H7
• C4H10+ C2H5+ + .C2H5 17
 Fragmentation Patterns 3

• The other peaks in the spectrum are produced by the loss of one or
more hydrogen atoms from these fragments.

• Occasionally unexpected peaks appear in the mass spectrum.

• This is usually an indication that some form of molecular

rearrangement has occurred within the instrument.

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Mass Spectrum of Butane

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 APPLICATION OF MASS SPECTROSCOPY
• Note: a combination of mass spectrometry and gas chromatography makes a
powerful tool for the detection of trace quantities of substances in forensic
science.

• Mass Spectroscopy is used:

To determine relative isotopic masses and relative isotopic abundance.
To distinguish between molecules of similar relative molecular mass
To identify compounds based on their fragmentation patterns
In carbon and other radioactive dating processes
By satellites and spacecrafts to identify particles intercepted in space.
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Examples of Mass Spectrums

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At the end of the lesson you should be able to;

• 7.1. Explain the basic principles of mass spectrometry; Include block

diagram. (Simple schematic diagram of the process).

• 7.2. Explain the significance of the (M+1) peak in mass spectra; and,

• 7.3. Use mass spectral data to:

• (a) determine relative isotopic masses; and relative isotopic
abundance; and,
• (b) distinguish between molecules of similar relative molecular mass.
22
 ASSESSMENT

Let’s answer the questions

at the end of chapter 27 in
your text.

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