Mass Spectroscopy: Separation of Ions On The Basis of Mass To Charge Ratio

Mass Spectroscopy: Separation of Ions
on the Basis of Mass to Charge Ratio

by
Kymberly Forrest, Olivia Gilbert,
Nicole Griglione, and Mary Jones
Introduction
• Mass spectroscopy is an effective method for determining
the weight and structure of mixtures of compounds.
• It is advantageous to other methods of analysis in its ability
to separate and analyze mixtures of compounds.
• It is an extremely sensitive technique with current levels of
accuracy within the range of one mass unit.
Applications
• General analysis of inorganic, organic, and bio-organic
chemicals
• Geological Sample dating
• Drug analysis and research
• Process studies in the petroleum, chemical, and
pharmaceutical industries
• Surface analysis
• Structural resolution of proteins and genetic material
General Setup
Common to all mass spectrometers are

(1) Sample Inlet (2) Ionization Source (3) Mass Analyzer
(4) Ion Detector (5) Vacuum System
Methods of Separation
This presentation examines different types of Mass Analyzers,

which differ in the physical properties they manipulate.
• Magnetic, which depends on Voltage
• Time of Flight, which depends on Mass
• Electric Quadrupole, which depends on AC/DC Currents
Common to these Mass Analyzers is the separation of particles on
the basis of mass to charge ratios (m/q).
Magnetic-Sector Mass
Spectrometry
Spectrometry
THEORY:
The ion source accelerates ions to a kinetic energy given by:
KE = ½ mv2 = qV
Where m is the mass of the ion, v is its velocity, q is the charge on
the ion, and V is the applied voltage of the ion optics.
Spectrometry
•The ions enter the flight tube and are deflected by the magnetic
field, B.
•Only ions of mass-to-charge ratio that have equal centripetal and
centrifugal forces pass through the flight tube:
mv2 /r = BqV, where r is the radius of curvature
Spectrometry
mv2 /r = BqV
•By rearranging the equation and eliminating the velocity term using
the previous equations, r = mv/qB = 1/B(2Vm/q)1/2
•Therefore, m/q = B2r2/(2V)
•This equation shows that the m/q ratio of the ions that reach the
detector can be varied by changing either the magnetic field (B) or
the applied voltage of the ion optics (V).
Spectrometry
In summary, by varying the voltage or magnetic field of the

magnetic-sector analyzer, the individual ion beams are separated
spatially and each has a unique radius of curvature according to
its mass/charge ratio.
Time of Flight Mass
Spectrometry (TOF-MS)
INTRODUCTION:
•Separates ions based on flight time

•Operates in pulsed mode
•Ions accelerated by an electric field
•Lighter ions reach the detector first
Time of Flight Mass
THEORY:
•KE=qV when electrons are accelerated through an

electric field
•KE of ion is ½mv2, so qV= ½mv2 and velocity is
inversely proportional to mass
•Transit time (t) is L/v, where L is drift tube length
and v is velocity
•So t=L/(2V/m/q)½ can be solved for charge-mass ratio
Time of Flight Mass
HOW IT’S DONE:
• Reflectron is series of rings or grids that serves to focus

ions to improve resolution
• Exact values of L and V do not need to be known if two or
more ions of known mass are used as mass calibration points
• Produces a mass spectrum as a function of time (can be
measured every 10 nsec)
Time of Flight Mass
ADVANTAGES:
•Good for kinetic studies of fast reactions and for use

with gas chromatography to analyze peaks from
chromatograph
•Can register molecular ions that decompose in the flight
tube
Quadrupole Mass Analyzers
Background Info
• been in use since the 1950s

• most commonly used mass spec today
• sometimes referred to as “mass filters” because
ions of only a single mass to charge (m/q) ratio pass
through the apparatus
• separate ions based on oscillations in an electric
field (the quadrupole field) using AC and DC
currents
Benefits
• easy to use
• simple construction
• fast
• low cost
• can achieve unit to 0.1 m/q resolution
More Benefits
• tolerant of relatively poor vacuums (~5 x 10-5torr),

which make them well suited to electrospray ionization
(because these ions are produced under atmospheric
conditions)
• quadrupoles are now capable of routinely analyzing up
to a m/q ratio of 3000, which is useful in electrospray
ionization of biomolecules, which commonly produces a
charge distribution below m/z 3000
Basis of Quadrupole Mass Filter
• consists of 4 parallel metal
rods, or electrodes
• opposite electrodes have
potentials of the same sign
• one set of opposite electrodes
has applied potential of
[U+Vcos(ωt)]
• other set has potential of
- [U+Vcosωt]
• U= DC voltage, V=AC voltage,
ω= angular velocity of
alternating voltage
Operation of Quadrupole Mass
Filter
• voltages applied to electrodes affect
trajectory of ions with the m/q ratio
of interest as they travel down the
center of the four rods
• these ions pass through the electrode
system
• ions with other m/z ratios are thrown
out of their original path
• these ions are filtered out or lost to
the walls of the quadrupole, and then
ejected as waste by a vacuum system
• in this manner the ions of interest are
separated
Obtaining A Spectrum
• a mass spectrum is obtained by varying the voltages on the rods

and monitoring which ions pass through the filter
• two methods for varying rod voltages:
– vary ω while holding U and V constant
– vary U and V but keep the ratio U/V fixed
– remember: U= DC voltage, V=AC voltage, ω= angular
velocity of alternating voltage
• The resolution is determined by the magnitude of U/V ratio
• beam currents for individual m/q ratios may be as low as 10-13 A
and so electron multipliers are usually used
Applications
• partial pressure analyzers

• GC/MS
• upper atmosphere and space research
• separation of proteins and other
biomolecules with electrospray
• plasma diagnostics
• multielement and isotopic analyses
Summary
• Magnetic Mass Spectroscopy shows the relationship between
voltage and mass to charge ratio:
m/q = B2r2/(2V)
• Time of Flight Mass Spectroscopy shows the relationship
between tube time and mass to charge ratio:
m/q = 2Vt2/L2
• Electric Quadrupole shows the relationship between AC/DC
currents and mass to ratios.
Sources
Dean, John A., et al. Instrumental Methods of Analysis. Belmont, CA: Wadsworth Company, 1988.
465-485.
De Laeter, John R. Toronto: John Wiley and Sons, Inc., 2001. 68-70
Sparkman, O. David. Mass Spec Desk Reference. Pittsburg: Global View, 2000. 47-48.
http://elchem.kaist.ac.kr/vt/chem-ed/ms/ms-intro.htm
http://masspec.scripps.edu/information/intro/
http://ms.mc.vanderbilt.edu/tutorials/ms/ms.htm
http://www.abrf.org/ABRFNews/1996/September1996/sep96iontrap.html
http://www.chem.arizona.edu/massspec/intro_html/intro.html

Mass Spectroscopy: Separation of Ions On The Basis of Mass To Charge Ratio

Uploaded by

Copyright:

Available Formats

Mass Spectroscopy: Separation of Ions On The Basis of Mass To Charge Ratio

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Mass Spectroscopy: Separation of Ions On The Basis of Mass To Charge Ratio

Uploaded by

Copyright:

Available Formats

Mass Spectroscopy: Separation of Ions

on the Basis of Mass to Charge Ratio

Common to all mass spectrometers are

This presentation examines different types of Mass Analyzers,

In summary, by varying the voltage or magnetic field of the

•Separates ions based on flight time

•KE=qV when electrons are accelerated through an

• Reflectron is series of rings or grids that serves to focus

•Good for kinetic studies of fast reactions and for use

• been in use since the 1950s

• tolerant of relatively poor vacuums (~5 x 10-5torr),

• a mass spectrum is obtained by varying the voltages on the rods

• partial pressure analyzers

You might also like