SAMPLE QUESTION AND ANSWER

SCHEME FOR PAST YEAR

QUESTION

CHAPTER 10 – MOLECULAR MASS

SPECTROSCOPY
 DECEMBER 2019

• Firstly, sample need to be vaporized (molecule in gas phase) and enter into a
chamber under vacuum condition.
• In the EI chamber, there is high energy electrons emitted from hot cathode
and accelerated towards/ bombard into target gas phase molecule.
• This will knock off one electron and leads to formation of radical cation

In EI, vacuum environment is required because to allow the electron hit

directly onto target molecule/analyte without any obstacle
• Use negative ESI mode benzoic acid, as the molecule has OH that
easily to form negative species by remove hydrogen
• Use positive ESI mode for benzamide, as the molecule has NH2
which easily likely to form positive molecule by remove the lone
pair electron
[M-H]- = 110 -1 = 109, M = 110

Contribute by the 13C or 17O

At the m/z = 108 is due to [M-2H]- which refers to

removal of 2H from 2OH from that species
 DECEMBER 2018

i) Source of electron – a thin ribbon or filament of metal that is heated electrically to

incandescence or to a temperature at which it emits free electrons. The emitted electrons
are attracted to an anode (trap) situated on the opposite side of the ionization chamber
from the filament or cathode
ii) Ionization chamber – maintained at low pressure (~10-4 Pa). The pressure in the ion volume
(1 cm3, high conductance chamber) of the EI source is ~10-1 Pa, depending on the method
of sample introduction (via GC, batch inlet, or direct insertion probe), to minimize
ion/molecule collisions
- Neutral molecules must be in gas phase, (volatile and thermally stable molecule)
- fast moving free electron at 70 eV (high kinetic energy) knocks an electron out of
neutral molecules to generate a radical cation: M + e-  M+. + 2e
- Since the energy is transferred from the electron to the molecular ions, the generated
ion may break apart into lighter fragments, of which only one will be charged: M+. 
A+ + B.
- The amount of fragmentation that occurs will depend on the energy of the electrons
used in the ionization process
- 482. 3 = [M+H], protonated molecular ion of Rosuvastatin, M is mass of Rosuvastatin in amu
- 483.4 = isotopic peak of protonated molecular ion of Rosuvastatin, [M+H], one of 12C was replaced by 13C
- 484.3 = isotopic peak of protonated molecular ion o Rosuvastatin, [M+H], one 12C was replaced by 13C
and one 1H was replaced by 2H
 Yes, the negative electrospray ionization (ESI) mode will work on this compound
since it has 3 hydroxyl groups

Any ion which is formed in the ion source has no kinetic energy. The energy that is
imposed on the ion by the potential drop E between the accelerating plates is zE. The
kinetic that possessed by an ion with mass, m and velocity, v as it enters the
magnetic field is equivalent to mv2/2.

mv2/2 = zE (Equation 1)

The magnetic field exerts a force, FB on the ions which pass between the magnetic pole,

FB = Bzv (Equation 2)

The forced exerted by the magnetic field must equal the centrifugal force, F C

FC = mv2/r (Equation 3)
That is experienced by the ions as they assume a curve path with a radius in the
magnetic field.

Setting FB = FC, Bzv = mv2/r (Equation 4)

Thus, the velocity of an ion as it passes through magnetic field is

v = Bzr/m (Equation 5)

Substitute Equation 5 into Equation 1

m (BZr/m)2/2= zE

Thus
m/z = B2r2/2E (Equation 6)

r = radius of curvature
B = magnetic field
z = charge of ion

From Equation 6, r, radius of curvature is fixed, therefore the m/z of the ions which strike
onto the detector can be controlled either by varying the magnetic field strength B or the
accelerating potential E.