Mass Spectrometry

Introduction:

 Mass spectrometry (MS) provides the molecular weight and valuable information
about the molecular formula, using a very small sample, The mass spectrum also
provides structural information that can confirm a structure derived from NMR
and IR spectroscopy.

 Mass spectrometry is fundamentally different from spectroscopy. Spectroscopy

involves the absorption (or emission) of light over a range of wavelengths. Mass
spectrometry does not use light at all.

 In the mass spectrometer, a sample is struck by high energy electrons, breaking

the molecules apart. The masses of the fragments are measured, and this
information is used to reconstruct the molecule. The process is similar to analyzing
a vase by shooting it with a rifle, then weighing all the pieces.
The Mass Spectrometer:

 Mass spectrometer ionizes molecules in a high vacuum, sorts the ions according to
their masses, and records the abundance of ions of each mass.

 Mass spectrum is the graph plotted by the mass spectrometer , with the masses
plotted as the x axis and the relative number of ions of each mass on the y axis.

Several methods are used to ionize samples and then to separate ions according to their
masses.
We will discuss only the most common techniques, electron impact ionization for forming
the ions, and magnetic deflection for separating the ions.

Electron Impact Ionization In the ion source, the sample is bombarded by a beam of
electrons. When an electron strikes a neutral molecule, it may ionize that molecule by
knocking out an additional electron.
 When a molecule loses one electron, it then has a positive charge and one unpaired
electron. The ion is therefore a radical cation.

The electron impact ionization of methane is shown next :

This unusual cation is represented by the formula with the + indicating the positive
charge and the . indicating the unpaired electron.

In addition to ionizing a molecule, the impact of an energetic electron may break it apart. This
fragmentation process gives a characteristic mixture of ions. The radical cation corresponding
to the mass of the original molecule is called the molecular ion, abbreviated M+. the ions of
smaller molecular weight s are called fragments. The electron impact ionization of methane is
shown next :
Separation of Ions of Different Masses:

A beam of electrons causes molecules to ionize and fragment. The mixture of ions is
accelerated and passes through a magnetic field, where the paths of lighter ions are
bent more than those of heavier ions. By varying the magnetic field, the
spectrometer plots the abundance of ions of each mass.
Detailed Explanation:
After ionization, the positively charged ions are attracted to a negatively charged
accelerator plate, which has a narrow slit to allow some of the ions to pass through.

The ion beam enters an evacuated flight tube, with a curved portion positioned
between the poles of a large magnet. When a charged particle passes through a
magnetic field, a transverse force bends its path. The path of a heavier ion bends less
than the path of a lighter ion.

The exact radius of curvature of an ion's path depends on its mass-to-charge ratio,
symbolized by mlz (or by mle in the older literature) .

In this expression, m is the mass of the ion (in atomic weight unit) and z is its charge
in units of the electronic charge. The vast majority of ions have a charge of + 1, so we
consider their path to be curved by an amount that depends only on their mass. At
the end of the flight tube is another slit, followed by an ion detector connected to an
amplifier. At any given magnetic field, only ions of one particular mass are bent
exactly the right amount to pass through the slit and enter the detector. The detector
signal is proportional to the number of ions striking it. By varying the magnetic field,
the spectrometer scans all the possible ion masses and produces a graph of the
number of ions of each mass.
The Mass Spectrum:
In the printed mass spectrum, all the masses are rounded to the nearest whole-number
mass unit. The peaks are assigned abundances as percentages of the strongest peak
which is called the base peak.
Notice that the base peak does not necessarily correspond to the mass of the molecular
ion. It is simply the strongest peak, making it easy for other peaks to be expressed as
percentages.
A molecular ion peak (also called the parent peak) is observed in most mass spectra,
meaning that a detectable number of molecular ions (M+) reach the detector without
fragmenting. These molecular ions are usually the particles of highest mass in the
spectrum.The value of m/z for the molecular ion immediately gives the molecular weight
of the compound.
Mass Spectrometry of Mixtures : The GC-MS
Two analytical tools—gas chromatography (GC) and mass spectrometry (MS)—can be
combined into a single instrument (GC–MS) to analyze mixtures of compounds.The gas
chromatograph separates the mixture, and then the mass spectrometer records a
spectrum of the individual components.

A gas chromatograph consists of a thin capillary column containing a viscous, high-boiling

liquid, all housed in an oven. When a sample is injected into the GC, it is vaporized and
swept by an inert gas through the column.
The components of the mixture travel through the column at different rates, often
separated by boiling point, with lower boiling compounds exiting the column before
higher boiling compounds. Each compound then enters the mass spectrometer, where it is
ionized to form its molecular ion and lower molecular weight fragments.
The GC–MS records a gas chromatogram for the mixture, which plots the amount of each
component versus its retention time—that is, the time required to travel through the
column. Each component of a mixture is characterized by its retention time in the gas
chromatogram and its molecular ion in the mass spectrum. GC–MS is widely used for
characterizing mixtures containing environmental pollutants. It is also used to analyze urine
and hair samples for the presence of illegal drugs or banned substances thought to improve
athletic performance.
Determination of the Molecular Formula by Mass Spectrometry:

A- High-Resolution M ass Spectrometry:

The mass spectra described thus far have been low-resolution spectra; that is, they report
m/z values to the nearest whole number. As a result, the mass of a given molecular ion can
correspond to many different molecular formulas.

High-resolution mass spectrometers measure m/z ratios to four (or more) decimal places.
This is valuable because except for carbon-12, whose mass is defined as 12.0000, the
masses of all other nuclei are very close to—but not exactly—whole numbers.
The exact mass values of a few common nuclei.

Using these values it is possible to determine the single molecular formula that gives rise
to a molecular ion.
For example, a compound having a molecular ion at m/z = 60 using a low-resolution
mass spectrometer could have the following molecular formulas:

If the molecular ion had an exact mass of 60.0578, the compound’s molecular
formula is C3H8O, because its mass is closest to the observed value.

Homework:
The low-resolution mass spectrum of an unknown compound X had a molecular ion
of 151. Possible molecular formulas include C7H5NO3, C8H9NO2, and C10H17N. High-
resolution mass spectrometry gave an exact mass of 151.0640. What is the
molecular formula of X?