ATOMIC STRUCTURE

negatively charged electrons revolving around the nucleus

ee
positively charged protons
ee
nucleus
++
ee ++
ee
neutral neutrons

ee

diameter of atom around 10-5 m

=
diameter of nucleus around 10-10 m
= 105
so, an atom is hundred thousand times larger than a nucleus

if a golf ball represents a nucleus, the atom would be about 5 km in diameter!

nucleus is an unimaginably small and positively charged centre in the atom
• if the number of protons changes, the element changes from one to another
The characteristic features of an element or its atoms are determined by the number of protons
- a significant factor for the properties of an atom of a particular element

Atomic number, Z : Number of protons in the nucleus

• if the number of electrons changes , positively charged cation or negatively charged anion of the element is
formed
• if the number of neutrons changes , isotopes of the element are formed
Isotopes : atoms having the same number of protons and different number of neutrons

note: the isotopes of the same element will have different masses
eg - hydrogen

p=1 p=1 p=1

n=0 n=1 n=2

protium, H deuterium, D tritium, T

oxygen

p=8 p=8 p=8

n=8 n=9 n=10

chlorine

p=17 p=17
n=18 n=20

carbon

p=6 p=6 p=6

n=6 n=7 n=8
mass number : sum of the protons and neutrons in the nucleus

in order to identify or distinguish the isotopes, nuclear symbols are used.

nuclear symbols will be in the form of:

mass no
Atomic
Symbol
atomic no

isotopes of hydrogen

1 2 3
H H H
1 1 1

isotopes of oxygen
16 17 18
O O O
8 8 8

isotopes of chlorine
35 37
Cl Cl
17 17
relative isotopic mass: mass of an isotope relative to 1/12th of the mass of a carbon-12

or
mass of an isotope

1/12th of the mass of a carbon-12

so, relative isotopic mass of carbon-12:

mass of an isotope of carbon-12

1/12th of the mass of a carbon-12

= exactly 12

relative isotopic mass of the other isotopes are determined by mass spectrometer
mass spectrometer
1. Vaporization chamber
Sample is injected into this chamber and is vaporized. Sample must be in gaseous state so that the
atoms or molecules can move through the machine

2. Ionization chamber
The sample is bombarded with high energy electrons so that one or more electrons of the atoms or
molecules are knocked off to produce positively charged ions

animation

3. Accelerating chamber
The positive ions are accelerated by an electric field produced by negatively charged electric plates

4. Velocity selector
This makes sure that the ions pass through to the next magnetic chamber are travelling at the same
velocity
5. Magnetic chamber
Positive ions enter a magnetic field produced by an electric coil. The direction of this magnetic field is
perpendicular to the direction of the travelling path of the ions. So, the ions are deflected towards the
third perpendicular direction.

The degree of the deflection depends on the following factors:

i. velocity of the ions (greater the velocity lesser the deflection)
ii. number of charges present on the ions (greater the charge more the deflection)
iii. mass of the ions (greater the mass lesser the deflection)
iv. strength of the magnetic field (greater the strength more the deflection)
Note: The first 3 factors belong to the properties of ions whereas the fourth is an external

• velocity selector makes sure to select only particles with a particular velocity and allow them to pass
through so the velocity factor does not have any effect on the deflection
• at later stage recording is done only for unipositive charges
• so, the only factor (belongs to the particles) affects the amount of deflection is the mass of the particles;
Heavier ions are deflected less than lighter ions
• The strength of the magnetic field is steadily increased by increasing the current through the coil so that at
any moment only a single path of positive ions having the same mass enters the detector
- other paths of the ions having different masses will be deflected too much or too little to the
path that enters the detector.
6. Detector/Amplifier/Recorder

The detector produces electric pulses when it is hit by positive ions and the pulses are amplified and
recorded as peaks to produce the mass spectrum.

Particles with different m/e (mass of unipositive isotope) values produce different peaks which are
spanned across the x axis of the spectrum

Number of the ions having a particular mass will determine the magnitude of the current of the pulse.
The magnitude of the current of the pulse, in turn, will determine the height of the peak.

X-axis consists the spanned values of m/e which are calibrated to represent the relative isotopic masses
of the corresponding isotopes that produce the peaks
Y-axis is calibrated to show the relative abundance in percentage of each isotope
mass spectrum of chlorine

peak due to [Cl35]+

peak due to [Cl37]+

 relative isotopic masses of the isotopes of chlorine
isotope m/e abundance/%

Cl35 34.97 75.5

Cl37 36.97 24.5

relative atomic mass

weighted mean of the masses of the isotopes of an element compared to the 1/12th of the mass of a carbon - 12

  (relative ¿ isotopic mas s X abundance ( % ) )¿

∑ 𝑖 𝑖
𝑖
=
100
relative atomic mass of chlorine:
consider a sample consists 100 atoms of chlorine

(34.97 x 75.5) + (36.97 x 24.5)

total mass of Cl35 isotopes + total mass of Cl37 isotopes
100

= 35.5 (rounded off to 1 decimal place) total mass of 100 atoms

total mass of 100 atoms

100

= average
Peaks due to molecular ions
As you are aware, except inert gases, other gaseous elements like H2, O2, N2 F2, Cl2, Br2 and I2 exist as diatomic
molecules – unlike other elements which consist atoms. When these diatomic elements are injected into the mass
spectrometer, along with positively charged isotopes, their whole molecules can be ionized by knocking off one or
more electrons.
In the case of chlorine, since it has two stable isotopes, the following 3 combinations of isotopes could be seen in their
diatomic molecules:

Cl35 – Cl35 Cl35 – Cl37 Cl37 – Cl37

So, the following 3 molecular ions are produced after knocking off the electrons:

[Cl35 – Cl35]+ [Cl35 – Cl37]+ [Cl37 – Cl37]+

animation
Since the mass of these molecular ions are greater than the corresponding isotopes, the peaks due to the molecular ions
appear in far-right side of the spectrum.

peak due to [Cl35

– Cl35]+

peak due to [Cl35

– Cl37]+

peak due to [Cl37

– Cl37]+
Other applications of mass spectrometer

Refer page 55 - 59

animation of mass spectrometer

2010 June, question No 16

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