Mass spectrometry

Mass spectrometry

 It is a analytical technique which allow us to determine the molecular

mass and molecular formula of a compound.
 The instrument use in such studies are called mass spectrometer and
mass spectrograph.
 Principle of mass spectrometry

1. The basic principle of mass spectrometry to generate ions from organic or

inorganic compound by any method.
2. To separate these ions by their mass to charge ratio.
3. To detect them qualitatively and quantitatively by their respective mass to
charge ratio and abundance.
4. The analyte ionized thermally by electric field or by impacting energetic
electron, ions or photons.
5. The ions can be single ionized atoms, clusters, molecules or their fragments or
associates.
6. Ions separation is effected by static or dynamics, electric or magnetic fields.
 Instrumentation

The mass spectrometer has five components

1. Sample inlet
 Which bring the sample from the laboratory environment.

2. Ion source
 Where the sample molecule is transform into gas phase ions.
3. Accleralator
 Once the sample has been ionize the beam of ion is accelerated by electric
field and then pass into analyzer.
4. Mass analyzer
 The region of the mass spectrometer where the ions are separated
according to m/z.
5. Detector
 The ions are counted by the detector.
6. Data system
The signal is recorded and process by the data system by pc.
 Sample introduction

• Sample inlet system

• Provide the stream of molecule .
• Sample may be liquid, gas or solid
• Sample is converted into liquid state that must flow in ionization
chamber.
• For less volatile sample the system can be design to fit an oven.
• Not to heat to a temperature at which it might decompose.
• Other system must be used for non volatile sample is direct probe
method.
.
Ionization methods
A. Electron Ionization
• Once the stream of sample molecules has enter the mass spectrometer the sample molecule must be converted to
charge particles by the ion source.
• In EI-Ms, a beam of high-energy electrons is emitted from a filament that is heated to several thousands degree
Celsius.
• The electron molecule strike strips the electron from the molecule creating the cation.

A repelar plate
Which carries a positive electric potential directs the newly created ions toward a series of accelerating plates
Accelerating plates
A large potential difference ranging from 1-10 k volts applied across the accelerating plate produces a beam of rapidly
traveling positive ions.
B.Chemical ionization
 The sample molecules are combine with reagent gas .
 When the sample molecule collide with the pre-ionized reagent gas
 some sample molecules are ionized by various mechanisms proton transfer, electron transfer
 Volatile liquid or gas can be use as reagent gas.
 Common reagent gas are methane, ammonia gas, iso-butane and methanol
 The choice of reagent gas should be made carefully to match the proton affinity of the reagent with that of
sample.
 Mass Analyses
 The region of the mass spectrometer where ions are separated according to their m/z .
 There are several types of mass analyzer are
 Magnetic sector Mass analyzer
 Double focusing Mass analyzer
 Quadruple Mass analyzer
 Time of flight Mass analyzer
 Detection
 The detector of a typical mass spectrometer consist of a counter that produces a current that is proportional to
the number of ions that strike it.
 Through the use of electron multiplier circuits, this current can be measured accurately.
 Current cause by just one ion striking the detector can be measured.
 When an ions strike the surface of the electron multiplier 2 electrons are ejected.
 The approximately 2 k volts potential difference between the opening and end of the detector.
 This draws the electron further into the electron multiplier.
 Each electron strike the surface again.
 This process continues until the end of electron multiplier is reached.
 Electrical current analyzed and detected.
termination of molecular weight
The user observe the m/z that correspond to the molecular ion to determine the molecular weight of the sample molecule.
The masses that are observed for molecular ions are the masses of the molecules in which every atom is present .
One method of confirming that a particular peak corresponds to a molecular ion is to vary the energy of the ionizing electron beam
If the energy of the beam is lowered, the tendency of the molecular ion to fragment lessens.
The peak must correspond to the ion of highest mass in the spectrum, excluding isotopic peaks that occur at higher masses. The iso
peaks are usually of much lower intensity then the molecular ion peak.
The ion must have odd number of electrons.
The ion must be capable of forming the important fragment ions in the spectrum, particularly the fragments of relatively high mass,
of logical neutral fragments.