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Mass Spectrometry
In mass spectrometry, a substance is converted into rapidly
moving gaseous ions which are then separated on the basis of
their mass-to-charge ratio.

Mass spectrometry is the most widely applicable of all the

analytical tools.

It provides information about:

1) the qualitative and quantitative composition of both
inorganic and organic analytes in complex mixtures.
2) the structures of a wide variety of complex molecular
systems.
3) isotopic ratios of atoms in samples
4) the structure and composition of solid surfaces
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Atomic and molecular weights are generally expressed in terms
of atomic mass unit (amu).

The atomic mass unit is based upon a relative scale in which the
reference is the carbon isotope 126C, which assigned a mass of
exactly 12 amu.

Mass spectroscopists also call the amu the dalton.

1 amu = 1 dalton
1 12g12C / mol12C 
=  23 12 12 
12  6.0221x10 atoms C / mol C 
= 1.66054 x 10-24 g/atom 12C
The atomic weight of an isotope, such as 3517Cl is then related to
that of the reference
€
12 C atom.
6

Chlorine-35 isotope is 2.91407 times greater than the mass of

carbon-12 isotope.
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Atomic mass 3517Cl = 12.0000 dalton x 2.19407
= 34.9688 dalton
Because 1 mol of 126C weighs 12.0000 g, the atomic weight of
35 Cl is 34.9688 g/mol.
17

In mass spectrometry, the exact mass of particular isotopes of

an element or the exact mass of compounds is determined.
The exact mass, m, of particular isotopes of an element or the
exact mass of compounds containing a particular set of
isotopes is measured.

For example a CH4 ion gives the following peaks in the mass
spectrum:
12C1H m = (12.000 x 1) + (1.007825 x 4) = 16.031 amu
4

13C1H m = (13.00335 x 1) + (1.007825 x 4) = 17.035 amu

4

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12C1H 2H m = (12.000 x 1) + (1.007825 x 3) + (2.0140 x 1)
3 1
= 17.037 amu
In mass spectrometry, exact masses are quoted to three or four
decimal places because high-resolution mass spectrometers
have this precision.
Nominal mass is used to imply a whole-number precision in a
mass measurement.

Examples: Nominal mass

12C1H m = 16.031 amu 16 amu
4
13C1H m = 17.035 amu 17 amu
4

Chemical atomic weight (A) of an element is given by the

equation
A = A1p1 + A2p2 + . . . + Anpn

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where A1, A2, ... , An are atomic masses in amu of the n isotopes of A
p1, p2, ... , pn are the fractional abundances the isotopes

Chemical molecular weight is the sum of the chemical atomic

weights of the atoms in the compound.

The mass-to-charge ratio, m/z, of an atomic or molecular ion is

obtained by dividing the atomic or molecular mass of an ion m
by the number of charges z that the ion bears.

Examples:
12C1H + m/z = 16.031/1 = 16.031
4
13C1H 2+ m/z = 17.035/2 = 8.518
4

Because most ions in mass spectrometry are singly charged,

the term mass-to-charge ratio, is often shortened to mass.

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The evolution of Mass Spectrometry is shown in the following
table.
Development Approximate Date Application
Behavior of ions in magnetic field Determination of isotopic
described
1920 abundances of elements

Double focusing 1935 High mass resolution achieved

First commercial mass Quantitative analysis of petroleum

spectrometer
1950 products

Spark source 1955 Quantitative elemental analysis

Theory describing fragmentation of Identification and structural

molecular species 1960 analysis of complex molecules
Interfacing mass spectrometers with Qualitative and quantitative
chromatographs 1965 analysis of complex mixtures
High speed analysis of complex
Tandem mass spectrometers 1970 mixtures
Enhanced capacity for structure
New ionization techniques 1970 elucidation
Fourier Transform applied to mass Improved mass resolution and
spectrometry
1980 signal-to-noise ratios
Improved sources for nonvolatile Analysis of polymeric molecules
species
1980 and surfaces

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Components of a Mass Spectrometer

sample

10-5 to 10-8 torr

Inlet Ion Mass

Detector
system source analyzer

Vacuum Signal
system processor

Readout

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The inlet system introduces a very small amount of sample
(micromole) into the mass spectrometer. It contains a means for
volatilizing solid and liquid samples.

The ion source converts the components of a sample into ions

by bombardment with electrons, molecules, or photons or by
thermal or electrical energy.

The mass analyzer is analogous to that of the grating in an

optical spectrometer. The dispersion is based upon the mass-to-
charge ratios.

Mass spectrometers fall into several categories, depending

upon the nature of the mass analyzer.

The detector converts the beam of ions into an electrical signal.

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Inlet system
Batch Inlet System
The sample is volatilized
externally and then allowed to
leak into the ionization region.
This is applicable to gaseous
and liquid samples having
boiling points up to 500 oC.

External sample introduction system Direct Probe Inlet

Solids and nonvolatile liquids
can be introduced by means of
a probe.
This is used when the quantity
of the sample is limited.
Proximity to ion source makes it
possible to obtain spectra of
A sample probe for inserting a sample thermally unstable compounds.
directly into the ion source
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Detectors This detector is like the PMT
for UV-Vis radiation, with
Electron Multipliers
each dynode being held at a
successively higher voltage.
Cathode and dynodes have
Cu/Be surfaces.
20 dynodes provide a
current gain of 107.
Discrete dynode electron multiplier
This trumpet-shaped device made
of glass is doped with Pb.
A potential of 2 kV is impressed
across the length of the detector.
Ions striking the surface near the
entrance eject electrons, then
skip along the surface, ejecting
more electrons with each impact.
Current gain of 105 is achieved
with this type of detector.
Continuous dynode electron multiplier

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Mass Analyzer
Mass spectrometers are classified based on the nature of the
mass analyzer.

Magnetic Sector Analyzer

Magnetic sector analyzers employ a permanent magnet or an
electromagnet to cause the beam from the ion source to travel
in a circular path of 180, 90, or 60 deg.
The next figure shows a 90-deg sector instrument.

The ions formed by electron impact are accelerated through slit

B into the metal analyzer tube maintained at 10-7 torr.

Ions of different mass can be scanned across the exit slit by

varying the field strength of the magnet or the accelerating
potential.

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passing throughOF THE
the exitPHILIPPINES
slit fall on a MANILA
collector
electrode, resulting in an ion current that is amplified and
recorded.
Schematic of a Magnetic Sector Spectrometer

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The capability of a mass spectrometer to differentiate between
masses is expressed in terms of its resolution, R
R = m/Δm
where Δm is the mass difference between two adjacent peaks resolved,
and m is the nominal mass of the first peak (sometimes mean mass)

Two peaks are considered to be separated if the height of the

valley between them is no more than 10% of their height.

Thus, a spectrometer with a resolution of 4000 would resolve

peaks occurring at 400.0 and 400.1 (or 40.00 and 40.01).

Example
What resolution is needed to separate C2H4+ (m = 28.0313) and
CH2N+ (m = 28.0187) ions.
Δm = 28.0313 - 28.0187 = 0.0126
R = m/Δm = 28.025/0.0126 = 2.22 x 103
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It can be shown that the mass-to-charge ratio is related to the
voltage in the ionization chamber (V), magnetic field strength
(B), radius of the curvature (r), and the charge of the ion (e =
1.60 x 10-19C) according to the equation

2 2
m Bre
=
z 2V

Most modern sector mass spectrometers contain an

electromagnet in which ions are sorted by holding V and r
constant while varying the current in the magnet and thus B.
€
In sector spectrometers that use photographic recording, B and
V are constant and r is the variable.

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What accelerating potential will be required to direct a singly
charged water molecule through the exit slit if the magnet has a
field strength of 0.240 tesla and the radius of curvature of the
ion through the magnetic field is 12.7 cm?

First convert variables into SI units.

charge per ion, ez = 1.60 x 10-19 C
radius, r = 0.127 m
mass, m = 18.02 g H2O+/mol x 10-3 kg/g = 2.99 x 10-26 kg H2O+
6.02 x 1023 H2O+/mol
magnetic field, B = 0.240 T = 0.240 W/m2 (W= Weber)
V = B2r2ez/2m = [0.240 W/m2]2[0.127 m]2[1.60 x 10-19 C]
2 x 2.99 x 10-26 kg
V = 2.49 x 103 W2C/m2kg (or V)
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Double-Focusing Spectrometers
The magnetic sector instruments are sometimes called single-
focusing spectrometers.
Magnetic field is used to act on ions with diverging distribution in order to
produce converging distribution of ions leaving the field.

The term double focusing is

applied to mass
spectrometers in which the
directional and energy
aberrations are minimized.

This is achieved by the use of

combinations of electrostatic
and magnetic fields.

The ion beam is first passed through an electrostatic

analyzer (ESA) which limits the kinetic energy of the
ions reaching a magnetic sector.
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Quadrupole Mass Filters

Quadrupole mass spectrometers are more compact, less

expensive, more rugged than their magnetic sector
counterparts.

They offer advantage of low scan times (<100 ms). They are the
most common mass analyzers used today.

Quadrupole is analogous to variable, narrow-band filter

because it transmits only ions with small range of m/z ratios.

Quadrupoles function by selective removal of ions. Thus they

are called mass filters.

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A Quadrupole THE
Mass PHILIPPINES MANILA
Spectrometer

The heart of the

instrument is the set
of four cylindrical
metal rods that serve
as the electrodes of
the mass filter.

Ions having energies larger than average strike the upper side
of the ESA slit and are lost to ground.
Ions having energies less than average strike the lower side of
the ESA slit and are thus removed.
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 Ion Trap
UNIVERSITY OFAnalyzers
THE PHILIPPINES MANILA
Ion trap analyzers are more compact, less expensive, more
rugged than sector or quadrupole instruments.

An ion trap is a device in which gaseous anions or cations can

be formed and confined for extended periods by electric or
magnetic field.

Time-of-flight Analyzers
In TOF instruments, cations are produced periodically by
bombardment with brief pulses of electrons, secondary ions, or
laser generated photons.
The particles are accelerated and allowed to pass to a field-free
drift tube.
Because the ions have the same KE, their velocities must vary
inversely with their masses, the lighter particles arriving at the
detector earlier than the heavier ones.

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Molecular Spectra from Various Ion Sources

The appearance of mass spectra

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Molecular Spectra from Various Ion Sources

Name Abbreviatio
n Type Ionizing Agent Date of
Use

Electron Ionization EI Gas phase Energetic electrons 1920

Chemical ionization CI Gas phase Reagent ions 1965
Field Ionization FI Gas phase High-potential electrode 1970
Field Desorption FD Desorption High-potential electrode 1969
Fast Atom Bombardment FAB Desorption Energetic atoms 1981
Secondary ion mass SIMS Desorption Energetic atoms 1977
Laser desorption LD Desorption Laser beam 1978
High-E fission fragments
Plasma desorption PD Desorption from 252Cf 1974
Thermal desorption Desorption Heat 1979
Electrohydrodynamic ionization EHMS Desorption High field 1978
Positive charges imparted to fine
Thermospray ionization ES droplets of sample soln
1985

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Molecular Spectra

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