Atomic Structure

Details of the three Sub-atomic (fundamental) Particles

Particle Position Relative Mass Relative Charge
Proton Nucleus 1 +1
Neutron Nucleus 1 0
Electron Orbitals 1/1840 -1

Behaviour of beams of protons, neutrons and electrons in electric fields

+ The negatively charged electron is

attracted towards the positive plate.
e
n The neutron has no charge and is
unaffected by a charged field

p The positively charged proton is

attracted towards the negative
plate. It is deflected less than an
- electron as it has a larger mass

An atom of Lithium (Li) can be represented as follows:

Nucleon(mass) Number 7

Proton (atomic) Number 3

Li Atomic Symbol

The proton (atomic number) ,Z, is the number of protons in the nucleus.
The Nucleon (mass number) ,A, is the total number of protons and neutrons in the atom.
Number of neutrons = A - Z

Isotopes Isotopes are atoms with the same number of protons, but different numbers of neutrons.

Isotopes have similar chemical properties because they have the same electronic
structure. They may have slightly varying physical properties because they have
different masses.

DEFINITION: Relative isotopic mass is the mass of one atom of an isotope

compared to one twelfth of the mass of one atom of carbon-12

DEFINITION: Relative atomic mass is the average mass of one atom

compared to one twelfth of the mass of one atom of carbon-12

DEFINITION: Relative molecular mass is the average mass of a molecule

compared to one twelfth of the mass of one atom of carbon-12

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There are two sorts of mass spectrometer. The following is the more old fashioned type. The time of flight spectrometer
on the next page is the more modern type.

THE MASS SPECTROMETER – electron bombardment

magnetic field
The mass spectrometer can be
defects the ions
Electric field Path of used to determine all the
accelerates the heavier ion isotopes present in a sample of
ions an element and to therefore
Vacuum identify elements.
Electrons
pump
ionise the
sample
It needs to be under a vacuum
otherwise air particles would
Vaporised ionise and register on the
Path of lighter
sample detector
ion
detector
Learn all these steps
The following are the essential 4 steps in a mass spectrometer.
carefully!
1.Ionisation
•A Vaporised sample is injected at low pressure If the sample is not vaporized
•An electron gun fires high energy electrons at the sample then vaporizing it would be
•This Knocks out an (outer) electron the first step.
•Forming positive ions with different charges E.g. Ti  Ti+ + e–

2. Acceleration
•A negative electric field accelerates the positive ions and makes them into a beam

3. Deflection
•The beam of positive ions is deflected by a strong magnetic field.
The heavier an ion the
•The degree of deflection depends on the mass-to-charge ratio, m/z.
less it is deflected
•The smaller this ratio the larger the deflection.
•By varying the magnetic field ratio, ions of different m/z ratios pass through the centre.

4. Detection
•The ions reach the detector and generate a small current, which is fed to a computer for analysis. The
current is produced by electrons transferring from the detector to the positive ions. The size of the current is
proportional to the abundance of the species

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 The Time of Flight Mass Spectrometer
Ionisation Acceleration Detection The mass spectrometer can be
Ion drift area area
area area used to determine all the
isotopes present in a sample of
an element and to therefore
Ion identify elements.
detector

It needs to be under a vacuum

otherwise air particles would
Heavy Light ionise and register on the
ions ions detector

Time measurement
The following are the essential 4 steps in a mass spectrometer.
1. Ionisation
The sample can be ionised in a number of ways. Two of these techniques are electron
impact and electrospray ionisation
Electron impact is used for elements
Electron impact
and substances with low formula mass.
•A Vaporised sample is injected at low pressure
Electron impact can cause larger organic
•An electron gun fires high energy electrons at the sample
molecules to fragment
•This Knocks out an outer electron
•Forming positive ions with different charges E.g. Ti (g) Ti+ (g)+ e–

Electro Spray Ionisation

• The sample is dissolved in a volatile, polar solvent
Electro Spray Ionisation is used
• injected through a fine hypodermic needle giving a fine mist or aerosol
preferably for larger organic
• the tip of needle has high voltage
molecules. The softer conditions of
• at the tip of the needle the sample molecule, M, gains a proton, H+, from the
this technique mean fragmentation
solvent forming MH+
does not occur
• M(g) + H+  MH+(g)
• The solvent evaporates away while the MH+ ions move towards a negative plate

2. Acceleration Given that all the particles have the same kinetic energy, the
•Positive ions are accelerated by an electric field velocity of each particle depends on its mass. Lighter particles
•To a constant kinetic energy have a faster velocity, and heavier particles have a slower
KE = ½ velocity.

KE = kinetic energy of particle (J)

m = mass of the particle (kg) You don’t need to learn these equations but
= velocity of the particle (ms–1) may be asked to use them in a calculation

Rearranged
gives

3. Flight Tube
•The positive ions with smaller m/z values will have the same kinetic energy as those with larger m/z and will move
faster.
•The heavier particles take longer to move through the drift area.
•The ions are distinguished by different flight times

= / Combining the two equations

t = time of flight (s) gives you
d = length of flight tube (m)
= velocity of the particle (m s–1)

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4. Detection
•The ions reach the detector and generate a small current, which is fed to a computer for analysis. The current is
produced by electrons transferring from the detector to the positive ions. The size of the current is proportional to the
abundance of the species

For each isotope the mass spectrometer can Sometimes two electrons may be
measure a m/z (mass/charge ratio) and an removed from a particle forming a 2+ ion.
24Mg2+ with a 2+ charge would have a
abundance
m/z of 12

Example A sample of Nickel was analysed and one of the isotopes found was 59Ni. The ions were
accelerated to have 1.000 x 10-16 J of kinetic energy and travelled through a flight tube that was
0.8000 m long.
How long would one ion of 59Ni+ take to travel along the flight tube?
The Avogadro constant L = 6.022 × 1023 mol–1

Mass of one ion of 59Ni+ = mass of one mole of 59Ni+

The Avogadro constant

= 59/ 6.022 × 1023

= 9.797X10-23 g
= 9.797X10-26 kg

t= 0.8000 √( 9.797X10-26/(2x 1.000 x 10-16))

t=1.771X10-5 s

Uses of Mass spectrometers

• Mass spectrometers have been included in planetary space probes so that elements on other
planets can be identified. Elements on other planets can have a different composition of
isotopes.
• Drug testing in sport to identify chemicals in the blood and to identify breakdown products
from drugs in body
• quality control in pharmaceutical industry and to identify molecules from sample with
potential biological activity
• radioactive dating to determine age of fossils or human remains

Radioactive Carbon Dating

All living things have small amounts of the radioactive Carbon-14 isotope. When a
living thing dies no more 14C is produced and its starts to decay. The object becomes
less radioactive over time.

Measure the abundance of 14C in the material to be tested. By use of the half-life of
14C work out how old the object is by working out how much it has decayed.

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Calculating Relative Atomic Mass
The relative atomic mass quoted on the periodic table is a weighted average of all the isotopes

Fig: spectra for

100
Magnesium from mass
80 78.70% spectrometer
% abundance

60
24Mg+
If asked to give the species for a peak
40 in a mass spectrum then give charge
25Mg+ 26Mg+ and mass number e.g. 24Mg+
20 10.13%
11.17%

m/z
24 25 26

R.A.M =  (isotopic mass x % abundance) Use these equations to

work out the R.A.M
100

For above example of Mg

R.A.M = [(78.7 x 24) + (10.13 x 25) + (11.17 x 26)] /100 = 24.3

R.A.M =  (isotopic mass x relative abundance)

If relative abundance is used instead of
total relative abundance percentage abundance use this equation

Example: Calculate the relative atomic mass of Tellurium from the following abundance data:
124-Te relative abundance 2; 126-Te relative abundance 4; 128-Te relative abundance 7;
130-Te relative abundance 6

R.A.M = [(124x2) + (126x4) + (128x7) + (130x6)]

19
= 127.8

Example: Copper has two isotopes 63-Cu and 65-Cu. The relative atomic mass of copper is 63.5.
Calculate the percentage abundances of these two isotopes.
63.55 = yx63 + (1-y)x65
63.55 = 63y +65 -65y
63.55 = 65 -2y
2y = 1.45
y = 0.725

%abundance 63-Cu =72.5% %abundance 65-Cu = 27.5%

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 Mass spectra for Cl2 and Br2
Cl has two isotopes Cl35 (75%) and Cl37(25%) Br has two isotopes Br79 (50%) and Br81(50%)

These lead to the following spectra caused by the diatomic molecules

Br79Br81 +
Br81Br79 +
Cl35Cl35 + relative
relative abundance
abundance Cl35Cl37 + Br79Br79 + Br81Br81 +
Cl37Cl37 +

70 72 74 m/z m/z
158 160 162

The 160 peak has double the abundance of the other

two peaks because there is double the probability of
160 Br79-Br81 + as can be Br79-Br81 and Br81-79

Mass spectrometers have been included in planetary space probes so that elements on other planets can
be identified. Elements on other planets can have a different composition of isotopes

Measuring the Mr of a molecule

Spectra for C4H10

If a molecule is put through a mass spectrometer with
an Electron impact ionisation stage it will often break Mass spectrum for butane
up and give a series of peaks caused by the
fragments. The peak with the largest m/z, however, 43
will be due to the complete molecule and will be Molecular ion
equal to the relative molecular mass , Mr ,of the C4H10+
molecule. This peak is called the parent ion or
molecular ion 29

58

If a molecule is put through a mass spectrometer with Electro Spray Ionisation then
fragmentation will not occur. There will be one peak that will equal the mass of the MH+ ion. It
will therefore be necessary to subtract 1 to get the M r of the molecule. So if a peak at 521.1 is
for MH+, the relative molecular mass of the molecule is 520.1.

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