Mass Spectrometry

What is Massspectrometer
A Mass Spectrometer is an instrument Which:
 Generates a beam of positively charged ions from the sample under investigation
 Produce ions from the sample in the ionization source
 Separate these ions according to their mass to charge ratio
 Fragment the selected ions and analyze the fragments using a second analyzer
 Detect the ions emerging from the analyzer and measure its abundance

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 Components of MS
Following are the components of a LCMS
1. Sample Inlet
2. Ionization source
3. Mass analyzer
4. Ion detector
5. Vacuum system

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Components Contd

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 Sample Introduction Methods
• Direct vapor inlet
• Gas Chromatography
• Liquid Chromatography
• Direct Insertion Probe (DIP)
• Direct ionization of samples (glow discharge, FAB, MALDI)

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 Ionization Methods

The Different Ionization Methods are as follows

1. Protonation
 Protonation is a method by which a proton is added to the molecule, producing a net charge of +1 for every
proton added
 Almost all the organic molecules gets protonated (eg: amines, alcohols etc)

2. Deprotonation
 Deprotonation is a ionization method by which a proton is removed from the molecule, producing a net charge of
-1 for every proton removed

3. Cationization
 It produces a charged complex by non-covalently adding a positively charged cation to a neutral molecule
 Examples are alkali, Ammonium , Water etc

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 Ionization Methods Contd

4. Transfer of a Charged Phase to a Gas Molecule

 The transfer of compounds already charged in solution is achieved through desorption or ejection of the charged
species from the condensed phase to the gaseous phase
 Commonly achieved through MALDI or ESI

5. Electron Ejection
 Ionization is achieved through the ejection of a electron to form a radical cation
 Generates significantly fragments ions
 Commonly found in non-polar compounds with low molecular weights
 Most commonly achieved through EI

6.Electron Capture
 Ionization is achieved through the capture of electron
 Commonly found in halogenated molecules which have high electron affinity

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 Ion Source
o The main function of the ion source is to produce ions without mass discrimination of the
sample
o Accelerate ions into the mass spectrometer
o The ion source is the part of the mass spectrometer that ionizes the material under analyses
o The minimum energy required to ionize the sample is called the ionization potential
o Molecular ions are formed when the energy of the electron beam reaches 10-15 eV

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 Classification of Ion Sources
1. Desorption Sources a) Electrospray Ionization (ESI)
b) Fast Atom Bombardment (FAB)
c) Field Desorption (FD)
d) Plasma Desorption (PD)
e) Matrix Assisted Laser Desorption(MALDI)

2. Atmospheric Pressure Ionization a) Atmospheric Pressure Chemical Ionization (APCI)

b) Atmospheric Pressure Photoionization (APPI)

3. Gas phase Sources a) Electron Impact Ionization (EI)

b) Chemical Ionization (CI)
c) Field Ionization (FI)

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Mass Analyzer

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Characteristics of Mass analyzer
Following are the characteristics of Mass Analyzer
1. Resolution : describes the ability of the analyzer to separate the adjacent ions
2. Mass accuracy: is the ability of the analyser to assign the mass of an ion close to its
true mass
3. Mass range: is usually defined by the lower and upper m/z value observed by a mass
analyzer
4. Sensitivity: is the ability of a particular instrument to repond to a given amount of
analyte
5. Scan speed: is the rate at which we can acquire a mass spectrum, generally given in
mass units per unit time

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Types of Mass analyzer
 Quadruple Mass analyzer
 Magnetic Sector Mass analyzer
 Time of Flight analyzer
 Quadruple Ion Trap analyzer
 Fourier Transform Ion Cyclotron Resonance Mass analyzer (FTICR/FTMS)

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Detectors
 Faraday Cup
 Electron Multiplier
 Photomultiplier Dynode
 Charge or Inductive detector

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