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"Big fleas have little fleas upon their backs to bite them, and little fleas have lesser

fleas, and so
ad infinitum". Jonathan Swift.

Although atoms are said to be the smallest building blocks of matter, they themselves consist of

smaller 'sub-atomic' particles. So what are sub-atomic particles made from? That, happily,
remains the domain of the physicist and, as such, has no place in this book!

Evidence for sub atomic particles

The sub-atomic family

Evidence for sub-atomic particles

Atoms are the fundamental building blocks of matter. However, even atoms are constructed of
smaller, sub-atomic particles. It was originally thought that the atoms were small indivisible

particles (atomos = indivisible), however a paradigm shift occured with the discovery that the

atoms themselves have a sub-structure.

Evidence for this emerged though the experiments conducted in the nineteenth century on

cathode rays, culminating in the experiments of Rutherford (the nuclear atom) and Chadwick

(neutrons) in the early 20th century.

It is now known that even these sub atomic particles themselves have an even deeper sub-

structure - the quarks!

The sub-atomic family

The fundamental sub-atomic particles are protons, neutrons and electrons. The protons and

neutrons are held together by strong nuclear binding forces in the nucleus of the atom. The

electrons may be considered to be tiny particles that exist in regions of space known as orbitals

around the atom.

This model of the atom is precisely that, a model. It is impossible to see atoms and, in order to

be able to describe their properties, we use models representing this microscopic world that is

invisible to us.

Similarly, the sub-atomic world is a strange place with unusual forces acting over infintesimally
small distances. The rules of behaviour that govern the macroscopic world often break down in
this strange environment, and it is important to understand that our representations and

models are necessarily limited here.

The picture of the atom above is easy to discuss and is comfortably familiar. However, if you

consider the actual dimensions of an atom compared to the nucleus you can see just how

inaccurate even this simple picture is.

Hydrogen atomic radius: 3.7 x 10-11 m

Hydrogen nucleus radius: 8 x 10-16 m

You should appreciate that the nuclear radius is much smaller than the atomic radius by a

factor of about 100,000. This means that the atom is mostly empty space with a very solid and
tiny nucleus. This was originally demonstrated by the scattering experiments of Ernst Rutherford.

Particle mass

The actual masses of these sub-atomic particles are very small and to the nearest whole

number measured relative to the mass of a carbon-12 isotope being equal to 12 units:

Particle location mass/amu

Proton nucleus 1

Neutron nucleus 1

Electron energy shells 5 x 10-3

Although these values suggest that the protons and neutrons are identical they do, in fact,

have very slightly different masses, which is only of concern to us when considering changes in

the structure in nuclear chemistry. Compared to the mass of the protons and neutrons the

electrons have negligible mass and can be ignored when carrying out calculations involving


Protons have a mass of 1 atomic mass unit. They are all together in the nucleus, but they

cannot repel one another because of the strong nuclear force exerted by the protons and the

neutrons. You could consider the neutrons to be the nuclear glue that holds the nucleus

A full

description TOK: This picture of the atom is a model to help us understand the
underlying structure. It does not imply that the atom is actually identical to
of the
this description, nor does it suggest that it is a simple arrangement of
electron is particles. It's just a model to help explain observed properties.


as they

behave both

as particles

in some


es and

waves in
others. This

has lead


physicists to

calling them

wavicles -

things that

possess the


cs of both


and waves.

This model allows us to use the atomic theory successfully to explain many observations in the

microscopic world. Its use in modern particular science has been refined by the introduction of

another model, which is rather more difficult to understand, called the quantum model.


Electrical charges

The forces that hold atoms together (and to one another) are largely electrical in nature (apart

from the strong nuclear charge that binds the particles in the nucleus together).
Electrically charged particles have an associated electrostatic field, rather like a magnet has a

magnetic field. If another electrical charge comes into this field it will feel a force of either

attraction or repulsion, depending on whether the charge carried is opposite or the same.

Overall, atoms are neutral, which means that they must have as many positive charges as

negative charges.

Protons carry a single positive charge and the electrons carry a single negative charge, so in

the neutral atom there are always the same number of protons and electrons.

The electrons are tiny in comparison to the protons and neutrons. The overall charge on an

atom is zero, the charges of the electrons cancel out the positive charges of the protons in the


Summary of fundamental particle charge and location

Particle location charge

Proton nucleus 1+ (positive)

Neutron nucleus none

Electron energy shells 1- (negative)

Mass number

The atomic mass number is represented by the symbol (letter) 'A'. This is not to be confused
with the relative atomic mass Ar.

The mass number gives the integral number of nucleons, protons and neutrons found in the

nucleus of an atom.

The relative mass is a value that is not necessarily integral that compares a mass to the mass

of a carbon isotope, assigned a value of exactly 12.0000 units.


Atomic number

This is represented by the symbol (letter) 'Z'. It shows us the number of protons in an atom

(and the number of electrons in a neutral atom.)

Example: How many protons and electrons does an atom of iron contain?

The atomic number of iron is 26 therefore it contains 26 protons

The number of electrons = number of protons, therefore there are 26 electrons

Mass number

The atomic mass number is represented by the symbol (letter) 'A'. This is not to be confused
with the relative atomic mass Ar.

The mass number gives the integral number of nucleons, protons and neutrons found in the

nucleus of an atom.

The relative mass is a value that is not necessarily integral that compares a mass to the mass

of a carbon isotope, assigned a value of exactly 12.0000 units.


Atomic number

This is represented by the symbol (letter) 'Z'. It shows us the number of protons in an atom

(and the number of electrons in a neutral atom.)

Example: How many protons and electrons does an atom of iron


The atomic number of iron is 26 therefore it contains 26 protons

The number of electrons = number of protons, therefore there

are 26 electrons



Any isotope of any element can be defined by using the A value, the Z value and the element
Using the values of A and Z it is possible to calculate the number of sub-atomic particles within

any specific isotope of an element.

Example: Determine the number and type of sub-atomic particles

in the following atom:

The atomic number is 1 therefore there is 1 proton and 1 electron

The mass number is 3 therefore there are (3-1) = 2 neutrons



The system can be extended to cover ions simply by adding the charge onto the element

symbol. It is important to remember that a positive ion has LOST electrons.

Example: Determine the number of electrons in the following


The atomic number is 12 therefore in a neutral atom there would

be 12 protons and 12 electrons.

However, the charge is 2+ therefore the atom has LOST 2


The remaining electrons then = 10 electrons


Isotope definition
Isotopes are atoms of a specific element that have a definite number of neutrons and

consequently a different mass. In effect all atoms are isotopes of one element or another.

Most elements have several isotopes, some of which are stable, and others that spontaneously

break apart releasing radioactivity.

For example, the element hydrogen has three isotopes, 1H, 2H and 3H. 1H is the most common of

the isotopes and makes up 99.99% of any sample of hydrogen. 2H is also called deuterium and

comprises the other 0.01% of naturally occurring hydrogen. The third isotope is called tritium

and is not very common.

Tritium is radioactive and breaks apart spontaneously releasing radioactivity, in this case, a fast

moving electron.

Note that the product of this radioactive process is helium. Effectively, one of the neutrons in

the tritium nucleus has emitted an electron (called a beta particle) and turned into a proton.

Summary of the hydrogen isotopes

name mass protons neutrons

hydrogen 1 1 0

deuterium, heavy hydrogen 2 1 1

tritium, super-heavy hydrogen 3 1 2


Relative abundance

The 'relative abundance' of an isotope means the percentage of that particular isotope that

occurs in nature. Most elements are made up of a mixture of isotopes. Clearly the sum of the

percentages of the specific isotopes must add up to 100%.

Example: Chlorine has two isotopes 35Cl and 37Cl, with relative

abundance of 75% and 25% respectively.

This means that in any naturally occurring sample of chlorine

75% of the atoms are Cl-35 atoms and 25% of the atoms are

chlorine-37 atoms.


Properties of isotopes

Isotopes differ only in their number of neutrons. This means that they have identical electronic

configurations and identical chemical properties. The masses of the isotopes affects any

characteristic that depends on mobility or mass of the particles.

Density is defined as mass/volume therefore isotopes have different densities.

Diffusion is a process that is dependent on the density of the diffusing species. According to

Graham's law, the rate of diffusion is proportional to the square root of the reciprocal density

and hence the reciprocal relative mass (of a gas):

Example: How does the rate of diffusion of hydrogen differ from

the rate of diffusion of deuterium?

Hydrogen, H2, relative mass = 2

Deuterium, D2, relative mass = 4

Applying Graham's law, relative rates of diffusion = 1/2 : 1/4

Therefore 1/1.414 : 1/2 = 0.71 to 0.5

Hydrogen diffuses 1.4 x faster than deuterium

This principle is put to use in the purification of uranium 235 for use in the atomic energy
industry. The uranium occurs naturally as two isotopes 235
U and 238
U with relative abundances of

approximately 0.28% to 99.71% with the remainder due to other isotopes.

Only the uranium 235 can be used for atomic energy and so needs to be concentrated in the

sample. This is done by reacting the uranium with hydrogen fluoride to form uranium
hexafluoride UF6, which is a volatile solid that can be converted to a gas at easily attainable


Once in the gaseous form, use is made of the different diffusion rates of the two compounds.

The relative masses of the two hexafluorides are so similar, the gases must be diffused using a

series of centrifuges, each one increasing the percentage of the required uranium isotope in the


The uranium hexafluoride is then turned into uranium dioxide for use in fuel pellets.


Uses of isotopes

Isotopes are used in medicine, industry, and in many other applications. The danger of
radioisotopes revolves around their ability to cause cell damage by ionising the atoms that are

involved in molecules and hence, breaking bonds. Radioisotopes may emit three different

common types of radiation, alpha, beta and gamma radiation, depending on the specific atom.

Alpha radiation consists of particles containing two protons and two neutrons (equivalent to a helium nucleus); is highly
destructive to living tissue, but has very low penetration power and is stopped by a few centimetres of air. It is only
seriously dangerous if ingested in some way.
Beta radiation consists of highly energetic electrons. It has poorer ionising characteristics than alpha radiation, but has
greater penetrating power.
Gamma radiation is electromagnetic in nature and has the lowest ionising ability, but extremely great penetrating power.

14C - radiocarbon dating

Living organisms respire. Plants breathe in carbon dioxide and animals eat plants (and other

animals!). The consequence is that all living things take up carbon throughout their lives. The

percentage of the isotope carbon 14 remains fairly constant in our atmosphere, as it is

produced in the upper atmosphere by cosmic bombardment of naturally occurring carbon-12 in

the form of carbon dioxide. At the same time the carbon 14 nuclei are decaying. There is an

equilibrium between these two processes:

carbon-12 carbon-14

This means that the proportion of carbon-14 compared to carbon-12 found in all living

organisms is also constant. However, when a living organism dies it stops taking up both forms
of carbon. The carbon -14 isotope decays naturally with a half life of about 5,600 years. So, a
simple procedure involving counting the radioemissions due to carbon-14 from a sample of

material that was once alive, can be used to estimate how long ago it died.

Therapeutic applications

Cobalt-60 is used in hospitals as a beta emission source in the treatment of cancer

Beta rays are fast moving electrons. They can be focussed onto cancerous tissue to destroy it

using a cobalt 60 source. This form of treatment is known as radiotherapy.

Iodine-131 and Iodine-125 are used as medical tracers and for treating certain cancers.

In several conditions the body can be scanned for problems using iodine, which is easily taken
up by the body and transported through the lymphatic system. The isotopes 131
I and 125
I are

easy to detect and short lived in the body.

Use is made of the destructive effect on cellular tissue to destroy cancer cells in treatment with

radioisotopes. Radioactive sources are used that have a short lifetime in the body, but which

can be focussed in their effects on tissues.

Technetium-99, for example is used in gammagraphy, a technique where a sample of the

radioisotope is injected into the body. After a few hours the technetium circulates around the

body and binds to areas of bone damage. By detection of areas of unusually high concentration

of radiation, it is possible to identify bone injuries that do not show up on X-rays.

The bone scans of radiation emissions are called gammagrams.

Industrial applications

Detection of leaks in gas pipes by injection of a radioisotope into the pipeline and detecting

where the radiation emerges. Beta emitters are used in measurement of thickness in the paper


Nuclear energy generation

Both uranium-235 and plutonium-239 are neutron emitting radioactive isotopes. The neutrons

emitted cause further events in neighbouring nuclei leading to chain reactions, which release

large amounts of energy as the nuclei break apart (fission). This energy is used to heat up
water into steam to drive turbines for electricity production.
Nuclear energy remains controvertial and there are strong arguments both for and against its


Other applications

Americium-241 is a man-made isotope used in smoke detectors.

Instrumental details

A sample is injected into the mass spectrometer and is vaporised before meeting a stream of

high energy electrons, that turn the atoms into ions (by dislodging electrons) or, if we are

dealing with molecules, causes the molecules to break apart (fragment). The ions that are

produced in each case are deflected by magnetic fields and detected with a high degree of


The final read-out may be graphical or digital and gives information about the relative

abundance of all of the ions produced by the stream of electrons, as well as their exact masses.

In summary a single beam mass spectrometer has the following stages of operation (refer to

diagram below):

Injection -The sample is injected into the vaporisation chamber,either as a gas or in an

inert solution.

Vaporisation - If necessary, the sample is heated to produce a vapour and the gas
diffuses into the...ionisation chamber.

Ionisation - An electron beam knocks electrons off the vaporised particles, producing

positive ions.

Acceleration - The positive ions are attracted towards negatively charged plates.

Deflection - The stream of ions passes through into the magnetic field which deflects

them into a curved path.

Detection - The magnetic field is varied by the controller and ions with different masses

are directed into the detector.

The operating principles are no longer a requirement for core and AHL.

Operating principles

The curved path travelled by each ion depends on its mass (actually the mass:charge ratio, but

as the charge is always the same and equal to the charge on an electron, but positive, then we

can talk about the mass alone). Heavier ions have more momentum and require more force for


The magnetic field strength of the deflector coils is varied and allows detection of all ions

according to their mass to charge ratio.

The ions arriving at the detector constitute a flow of positive charge and can be recorded


In this way, the relative atomic mass of each 'peak' is recorded on the mass spectrum read-

out. The height of the peak represents the abundance of the specific particle.

Mass spectrometer animation


The energy of the electrons in the ionisation chamber of the mass spectrometer not only can

ionise the molecules it encounters, but also cause the ions produced to fragment into smaller

pieces. This is called fragmentation. The smaller pieces, or fragments, themselves may be

detected if they are in the form of ions. The peak that occurs at the highest m/e value is called

the molecular ion. It is the ion produced by removing one electron from the molecule itself and

can be used to determine the relative molecular mass of the species under investigation.

A typical molecular fragmentation pattern may look as follows:

Fragmentation of ethanol, CH3CH2OH

Notice that only ions are shown as only ions can be detected in

the mass spectrometer. When an ion fragments, it makes neutral

species as well, but these cannot be detected, as they can neither

be accelerated nor deflected by the magnetic field.

Example:[CH3CH2OH]+ [CH3CH2]+ + [OH]

In this fragmentation, [OH] is produced but does not cause a

trace on the spectrum.


The mass spectrum of chlorine Cl2

The chlorine spectrum shows several lines, all of which are due to positive ions formed in the

mass spectrometer ioniser stage.

The line with the highest m/e value comes from the molecular ion, it is due to the [Cl 2]+ ion.

Chlorine has two different isotopes, therefore there are three possible molecular ions.

The remaining two lines at m/e 3

[37Cl]+formed by fragmentation o

The heights of the lines ca


In this case, the relative h

is 3:1, showing the natura

to 25% respectively.

Relative mass

The term relative atomic mass refers to the average mass of an atom of a specific element as

compared to the 12 carbon isotope (equal to 12.0000 atomic mass units)

To calculate relative atomic masses from isotopic data you need:

The relative mass of each isotope

The percentage abundance of each isotope

With this data, relative mass calculation is a simple affair:

(mass of isotope1 x % abundance isotope1) + (mass of isotope2 x % abundance isotope2)

AM =



Mr determination from MS
Here we can see that there are two peaks in the

mass spectrum, one at m/e (this means mass to

charge ratio) = 20 and the other at m/e = 22. These

peaks correspond to the ions produced from the

diferent isotopes of Neon.

As neon has two common isotopes 20Ne and 22Ne, any

naturally occurring sample of neon will contain these

two isotopes. The mass spectrum shows that the

peaks are in the ratio 10:1 and so there is 10 times

as much 20Ne as 22Ne in the sample. From this data

the relative atomic mass of neon can be calculated.

RAM = [(10 x 20) + (1 x 22)]/11 =

Relative molecular mass

The mass spectrometer is an instrument used for three main purposes:

1. 1 Measuring the exact relative masses of elements (section 1.22).

2. 2 Measuring exact releative molecular formula mass
3. 3 Measuring the masses of the breakdown products from molecules when they are smashed to pieces by high energy

electrons. This is also called the fragmentation pattern and may be useful in elucidation of the structure of a molecule.


Accurate mass measurement

The ions can be focussed onto the detector electronically. This allows determination of the m/e

of the ion, to an accuracy of 8 decimal places. The mass of the electron that has been lost can

be taken into account, giving masses for the atoms that are very accurate.


Molecular formulae determination

The masses of the atoms can be found to such great accuracy that the mass of each molecule

becomes unique, according to the number and type of each atom present.
Example: The relative molecular mass of carbon monoxide = C +
O = 28 (to two significant figures places)

The relative molecular mass of nitrogen = N + N = 28 (to two

significant figures places)

But, using high resolution mass spectrometry

Mass of 16oxygen = 15.99491

Mass of 14nitrogen = 14.00307
Mass of 12carbon = 12.00000

It should be appreciated that the following peaks are easily


a peak due to 12C16O (carbon monoxide) is found at 27.99491

a peak due to 14N14N is found at 28.00614


Structural information

Spectra of molecules are rather more complex due to the breakup (fragmentation) of the

molecule in the electron beam.

Here we can see that there is a fragmentation pattern caused by the molecule breaking apart in

the electron bombardment.

The molecule is shown on the spectrum and the most important peak is the one at m/e = 116

which gives the relative molecular mass of the molecule. This peak is said to be due to the
"molecular ion" and is caused by the molecule itself losing only one electron before going to the


The m/e value of the molecular ion can be measured to such a degree of accuracy (many

decimal places) that it can be used to determine the exact number of each type of atom within

the molecule.

A full treatment of the fragmentation pattern is possible to give information regarding how the

molecule is bonded together, but not required for this section.

Wave definitions

Waves are defined by velocity, wavelength, frequency and amplitude. This is shown in the

following diagram:

1. The wavelength is represented by the Greek letter lambda -

2. The frequency is the number of wavelengths that pass per second - f (sometimes the Greek letter 'nu', ). This is

measured in Hertz (Hz) or cycles per second.

3. The velocity of the wave in the case of electromagnetic radiation is the speed of light 'c' (3 x 10 8 ms-1 [data booklet])

4. The amplitude of the wave is represented by the letter 'a'. It is a measure of the intensity and is relatively


These wave properties are related by the equation:


Electromagnetic energy

The energy carried by an electromagnetic wave depends on the wavelength - they are inversely

proportional, i.e. the shorter the wavelength the higher the energy.

However, as the speed of the electromagnetic radiation is always constant, the energy is also

directly proportional to the frequency of the wave. Higher frequency = greater energy. This can

be shown by the following equation:

Where 'h' is called Planck's constant (6.63 x 10-34 Js [data booklet])

Example: Calculate the frequency of radiation emitted by an IR

source with a wavelength of 1500 nm.

The speed of light, c = f

Hence: f = c/ = 3 x 108/1500 x 10-9

Hence frequency of radiation = 2 x 1014 Hz


The electromagnetic spectrum

The wavelength of electromagnetic radiation varies according to its energy. The table below

shows the terms used for different regions of electromagnetic radiative energy and their

approximate wavelength and frequency ranges.

Frequency Wavelength Type of electromagnetic radiation Energy

1024 3 x 10-16 Gamma rays
1021 3 x 10-13 far X-rays
1018 3 x 10-10 X-rays high
1015 < 3 x 10-7 Ultraviolet
1015 3.6 - 7.6 x 10-7 Visible to
1015 > 3 x 10-7 Infrared
1012 3 x 10-4 Microwaves
109 3 x 10-1 UHF television low
106 3 x 102 Radio waves
Note that the visible region of the spectrum, i.e. the region that human eyes are able to detect,

is incredibly small when compared to the whole range.

Effectively, there is no upper or lower limit to the wavelength and the energy.

The visible spectrum

The region of the electromagnetic spectrum that humans are able to see is very limited, called

the visible spectrum. We are all familiar with the colours of the visible spectrum:

Red, orange, yellow, green, blue, indigo and violet.

We may not be quite so familiar with the wavelength range covered:

Red light begins at wavelength 760 nm (1nm = 1 x 10 -9 metres)

Blue light ends the high energy region of the visible spectrum at 360 nm

Use the slider on the animation below to see the relationship between colour, wavelength,

frequency and energy of visible light.

The term 'ultra violet' (literally, beyond violet) refers to electromagnetic waves with energy

greater than the visible range. The term infra-red refers to wavelengths with lower energy than

the visible range.

A visible spectrum is produce when a light source (sunbeam, torch, laser etc) passes through a

refracting prism (piece of glass, or a Diffraction grating) and the light is bent through an angle

that depends on the wavength of the light passing through.

If the light wavelength is long ( for instance, red light, wavelength 700nm) it is not deviated as

much as a short wavelength (e.g. blue light, wavelength 400nm).

Hence, any source of light consisting of several different wavelengths may be separated and

displayed on a screen or the different wavelengths may be detected electronically and


If the light source contains all possible wavelengths (e.g. white light) then a continuous

spectrum results (eg a rainbow)

Continuous spectra

A spectrum may be continuous, or may comprise bright lines (an emission spectrum), or dark

lines (an absorption spectrum) superimposed on a background.

A continuous spectrum results when the gas pressures are higher, so that lines are broadened

by collisions between the atoms until they are smeared into a continuum. We may view a

continuum spectrum as an emission spectrum in which the lines overlap with each other and

can no longer be distinguished as individual emission lines.


Line spectra

These, as would be imagined, are spectra that appear as specific discrete lines on a

background. They may be either emission or absorption.

Emission spectra are produced by passing electrical or thermal energy through gases in which

the atoms do not experience many collisions (because of the low density). The emission lines

correspond to photons of discrete energies that are emitted when excited atomic states in the

gas make transitions back to lower-lying levels.

As shown, emission spectra result from electrons within a sample becoming excited and moving

to higher energy levels. They cannot stay at the higher level for very long and they fall back to

the ground state, releasing energy equivalent to the difference between the energies of the two



Absorption spectra

An absorption spectrum occurs when light of all wavelengths passes through a cold, dilute gas and

atoms in the gas absorb at characteristic frequencies. As the re-emitted light is unlikely to be

emitted in the same direction as the absorbed photon, this gives rise to dark lines (absence of

light) superimposed on the continuous spectrum.

This phenomenon is used in Atomic Absorption Spectrophotometry (AAS) for trace analysis of

ions in solution.



Continuous, Emission, and Absorption Spectra

Continuous spectrum showing all the wavelengths of visible light

Emission spectrum showing only those discrete wavelengths that are emitted

Absorption spectrum showing a continuous spectrum with some specific wavelengths removed

The Hydrogen emission series

The electron in the ground state energy level of the hydrogen atom receives energy in the form

of heat or electricity and is promoted to a higher energy level.

It cannot remain at a higher level (excited state) for very long, and falls back to a lower level.

When the electron falls back down (relax) it must lose the energy difference between the two

energy levels. This loss of energy is performed by releasing electromagnetic energy in the form

of infrared, visible light or ultraviolet radiation.

Movement of electrons between the shells is called electron transitions.

When electron transitions take place the energy emitted can be detected and its wavelength

measured. This provides information about the relative energies of the shells.
In the hydrogen atom (the simplest case with only one electron to 'jump' between shells) the

energy emitted appears in several series of lines, each series corresponding to electrons falling

back to different levels. This is shown in the diagram below.

The Lyman series corresponds to transitions between the higher shells and the lowest shell

(ground state). The energy of these transitions produces radiation in the ultra-violet region of

the spectrum

The energy shells are usually given a letter 'n' to describe the specific energy level. The lowest

level is n=1, the second level is n=2 etc.

Transitions from higher shells (n>2) to n=2 produce radiation in the visible region of the

spectrum. It can be seen by splitting the light using a prism or diffraction grating and

projecting it onto a screen.



As the energy levels increase in energy they get closer together. In other words level 2 and

level 3 are further apart than level 3 and level 4. The levels converge towards a limit.
Transitions that occur in any series must also converge towards a high energy limit, as the

largest transition is between the highest energy level and the level that is characteristic of the

specific series.

The highest level is sometimes refered to as the 'infinite' level, as the levels get so close

together where they converge that they are impossible to count.



When dealing with the Lyman series in the ultraviolet, the transitions are down to
the ground state (level 1). The largest transition must represent a fall from the
infinite level, , to level 1. Viewed in reverse it can be considered to be equal to
the ionisation energy, as this is the energy required to move an electron from the
ground state to the infinite level (Note: Ionisation energy is usually expressed per
mole of electrons).

M(g) M+(g) + 1e

Consequently, the ionisation energy may be found by examining the Lyman series
at the convergence limit. The wavelength of light corresponding to the
convergence limit may be converted to energy using the relationship E = hc/
Example: Calculate the ionisation energy of hydrogen, if the

lines of the Lymann series converge to a limit at a

wavelength of 90.1 nm. h, (Planck's constant) = 6.63 x 10-34,
c, speed of light = 2.99 x 108 ms-1

E = hc/

wavelength 90.1 nm = 9.01 x 10-8 m

Therefore Energy = (6.63 x 10-34 x 2.99 x 108)/9.01 x 10-8

E = 2.17 x 10-18

Energy/mole = 2.17 x 10-18 x 6.02 x 1023

Energy/mole = 1.308 x 106 Joules

Energy = 1308 kJ mol-1

Ionisation energy of hydrogen = 1308 kJ mol-1

This method may be used to find the first ionisation energy of any element.

The wavelength (or wavenumber) values corresponding to the convergence limits

are available in data books or in the excellent NIST physics resource.

Electron arrangement
The electrons in atoms are arranged in energy levels. The lowest energy (most stable) energy

level is the one closest to the nucleus. The first energy level can hold up to two electrons. Once

it is full, the next energy level may then start to fill up.

However, each energy level itself is subdivided into subshells containing regions of space in

which there is a 0.99 probability of finding electrons of a specific energy. These regions are

called orbitals.


Atomic orbitals

The regions of space in which electrons are found were defined by Ernst Schredinger in the

early part of the 20th century, by solving equations relating their energy and the electrostatic

forces to which they are subject. These regions of space are termed 'orbitals'

Electrons behave like particles in some respects and waves in others, but in all cases they

behave as negative charges. They are very difficult to pin down in terms of location, however it

is possible to define a region of space in which the probability of finding the negative charge is

very close to certainty - about 99%. This region of space is called an orbital.

Each energy level is divided into sub-levels each of which in turn has a certain number of


One atomic orbital can house up to two electrons, each with a different 'spin'. The word 'spin' is
used to differentiate between the two different electrons. It does not imply that they actually

spin, but studies show that they do have slightly different energies and the idea of spinning

electrons allows us an easy image with which to differentiate between them. The first electron

to enter an orbital spins up and the second spins down.


1st Energy level

This is the first (lowest) energy level. It has no sub divisions and consists of only one orbital

with a spherical shape - called a 1s orbital. (the '1' refers to the energy level).

Like other orbitals, it can house a maximum of two electrons.


2nd Energy level

This is the first energy level to be split into sub-levels, 's' and 'p'. The 's' sub-level once again

has only one spherical orbital which is much larger than the 1s orbital from the 1st level. The

'p' sub-shell consists of three atomic orbitals shaped a bit like double headed balloons. Each of

the orbitals is designated a letter x, y or z to indicate the axis that it lies along.

The 'p' orbitals are of slightly higher energy than the 's' orbital, consequently the 's' orbital fills

up before the 'p' orbitals become occupied.


3rd energy level

The third energy level is split into three sub-levels, 's', 'p' and 'd' sub-shells. Each of these has

corresponding atomic orbitals.

The 3s sub-shell consists of one 3s orbital, spherical in shape, like the 1s and 2s orbitals, but much larger.

The 3p sub-shell contains 3 separate 'p' orbitals, the same shapes and orientations as the 2'p' orbitals but, once again,

larger in volume.

The 'd' sub-shell consists of five 'd' orbitals with specific shapes.

The energies of the orbitals is in the order s<p<d


4th energy level

Contains 's', 'p', 'd', and 'f' orbitals (7 of them), with relative energies s<p<d<f


The energy levels are split into sub-levels, each with orbitals that have shapes corresponding to

the type of sub-shell.

Energy level sub-shells type orbitals

1 1 s s

2 2 s,p s, px,py,pz

3 3 s,p,d s,px,py,pz,dxy,dxz,dyz,d(x2-y2), dz2

4 4 s,p,d,f as above plus 7 'f' orbitals

Atomic orbitals

Each energy level is split into sub-levels (except energy level 1). The sub-levels in turn, contain

orbitals that can hold a maximum of two electrons per orbital.

Level 1 contains only 1 's' orbital

Level 2 contains 1 's' and three 'p' orbitals

Level 3 contains 1 s, three p and five 'd' orbitals

Level 4 contains one 's', three 'p', five 'd' and seven 'f' orbitals

As stated above the electrons fill up the orbitals in order of increasing energy from the lowest

energy orbitals upwards. This process is subject to certain 'rules


Pauli's exclusion principle

This states that no two electrons can be identical within an atom. Simply stated, it means that

only two electrons can fit into each atomic orbital and they must have opposite spins. By

convention, we say that one electron spins up, and the other down , represented by up and

down arrows.


Hund's rule
This states that electrons entering orbitals that have the same energy (degenerate orbitals,

represented by boxes on the same level) must be filled by parallel electrons (unpaired

electrons), before the electrons become paired up.

allowed forbidden

Example: In the electronic configuration of carbon 1s2 2s22p2, the electrons fill up in the

following way:

level 's' orbitals 'p' orbitals



Anomalous configurations

The Aufbau principle works fairly well for the first 38 elements, but after that it starts to break

down. Even so, there are two configurations that do not seem to fit into the pattern. These are

chromium and copper.

Chromium (24 electrons) has an expected configuration of [Ar] 4s2 3d4. However, the actual

configuration is [Ar] 4s1 3d5.

This is explained by suggesting that there is some energetic advantage to the atom to have a

half-full set of 'd' orbitals, and that this is enough to cause one of the 4s orbital electrons to

occupy the last orbital in the 3d series.

Copper (29 electrons) also has an anomalous configuration with the expected [Ar]
4s2 3d9 giving way to [Ar] 4s1 3d10.

Once again, this is explained by the extra stability due to a full set of 3d orbitals, providing the

incentive for the 4s electron to be housed in the last 3d orbital.

The Aufbau Principle

Example: Which of the following atoms has/have one or more
unpaired electrons?

1. I. Iron
2. II. Copper
3. III. Zinc

To answer the question it is necessary to look at the electronic

configuration of each atom.

Iron [Ar] 4s2 3d6

Copper [Ar] 4s1 3d10

Zinc [Ar] 4s2 3d10

Iron has 6 'd' electrons to fit into 5 'd' orbitals. As the first five
must enter with parallel spin it has 4 unpaired electrons

Copper has a single unpaired electron in the 4s orbital and all the
'3d' orbitals are full

Zinc has a full set of 4s and 3d orbitals

Therefore, of the three elements, only iron and copper have

unpaired electrons.


Electronic configuration of ions

Ions are formed from atoms by the addition or removal of electrons depending on whether the

atom is a metal or a non-metal.

Metals lose electrons forming positive ions. The number of electrons lost depends on the metal

atoms. Group 1, 2 and 3 elements lose 1, 2 and 3 electrons respectively to give a noble gas


The 'd' block (transition) metals have variable oxidation states and may lose a variable number

of electrons. The first electrons lost by the first row 'd' block metals are the 4s electrons. After

these have been removed the '3d' electrons are successively removed until the required ion is

Example: Show the electronic configuration of iron(II) and
iron(III) ions.

iron(II) has a charge of 2+ and has consequently lost 2 electrons.

Iron (III) has a charge of 3+ and has lost 3 electrons.

Iron (at no. 26) has an electronic configuration =

1s2 2s22p6 3s2 3p6 4s2 3d6

iron(II) has a configuration of 1s2 2s2 2p6 3s2 3p6 4s03d6

iron(III) has a configuration of 1s2 2s2 2p6 3s2 3p6 4s03d5

Evidence for the existence of energy levels.

Scientists deal with a microscopic world that can never be seen. So how do they "know" the

structure of an atom?

It is rather like a birthday present that arrives well wrapped. The recipient may try to guess the

contents of the package without actually opening it. Many people shake the box, listen to the

movement of the contents, try to gauge the weight and how the contents move around in the


What they are doing is putting energy into the box and by sensing the response from the box

they hypothesise (guess) what the contents are.

Its the same procedure with scientists and the microscopic world.

Energy is given to the particles (atoms, molecules or ions) and the response from the unseen

world is detected. Hypotheses are formulated which are then tested by all available means. If

the experimental evidence seems to fit the hypothesis then a theory is proposed which in time

comes to be accepted as the "truth".

The three pieces of evidence are as follows:

1 Spectra
2 Successive ionisation energies
3 Ist ionisation energies of the different elements


Different types of spectra have already been covered in section 1.31. These may be

summarised as:

1 continuous emission
2 continuous absorption
3 line emission
4 line absorption

Line emissions arise from energy being emitted by the atom as a result of electrons in high

energy levels returning to their ground states. The electrons must emit the difference in energy

and this is seen as light (electromagnetic radiation) of a specific wavelength. They first arrive

at the higher level by absorbing energy in the form of either heat or electricity.


An electron absorbs heat or electrical energy and is promoted to a higher level

The electron returns to the original level and emits the difference as a specific electromagnetic radiation.

The wavelength seen is related to the energy of the emission by Plancks equation E=h


E = energy of the emission

h = Plancks constant (6.63 x 10-34)
= frequency of the radiation (the frequency is related to the wavelength by c = , c is the speed of light and is the


Successive ionisation energies

The ionisation energy of the elements can be determined by several means. These
are beyond the scope of the Syllabus. Students must understand the definitions of
1st and successive ionisation energies and also the factors that affect them,
specifically electrostatic forces.

The first ionisation energy

The first ionisation energy is defined as the energy required to remove one mole
of electrons from one mole of gaseous atoms to provide one mole of gaseous
single charged ions.
Na(g) Na+(g) + 1e

Subsequent ionisation energies are defined in a similar way only by removing

electrons from already charged ions.

The second ionisation energy

Na+(g) Na2+(g) + 1e

Successive electrons can be stripped from an atom until there is only the nucleus
left. If the energy required to achieve this for each ionisation is plotted on a graph
(with a log scale) against the ionisation number, the 'jumps' in the required
energy clearly show the main and sub energy levels.

In this example, it may be seen that removal of the first electron requires
(relatively) less energy than removal of the next (eight) electrons - there is a
distinct inflexion (change of direction) in the otherwise fairly linear graph.
Consequently the element concerned must be in group I.

Many exam questions focus on the ability of a student to recognise this inflexion
from purely numerical data and then ask for details of its group in the periodic

Example: In the following table identify the groups to which the elements X, Y and Z belong (all
values in kJ mol-1).

element 1st I.E. 2nd I.E. 3rd I.E 4th I.E.

X 496 4562 6912 9543
Y 738 1451 7732 10540
Z 578 1817 2745 11577

It may be seen that the inflection (relatively bigger jump) for element X occurs between 1st and

2nd ionisation energies. It is therefore in group 1. Similarly the inflection for Y occurs between

the 2nd and 3rd ionisation energies and so it is in group 2.


1st ionisation energies of successive elements

The first ionisation energy of an element is defined as the energy required to

remove 1 mole of electrons from one mole of gaseous atoms under standard

M(g) M+(g) + 1e

A graph of first ionisation energy against atomic number shows how the first
ionisation energy varies moving from element to element in the periodic table.
The outermost electron is being removed in each case and so the amount of
energy needed to remove it is a function of the force holding the electron in
position around the atom.
This force is dependent on two main factors and is 'fine-tuned' by a third factor.

1. 1 The charge on the nucleus

2. 2 The distance of the outer electron from the nucleus
3. 3 Inter-electron repulsions

As the charge on the nucleus increases so the energy required to remove the
electron increases.

As the distance between the outermost electron and the nucleus increases so the
energy required to remove it decreases.

The graph is probably best understood by referring to specific examples. Click on

the element values on the graph below to find out more.



Spectral lines give evidence of electrons moving from one energy level to another
within the atom.

Successive ionisations of an atom suggest that there are energy shells with large
energy differences between them.

The 1st ionisation energies of the first 36 elements suggests that the energy
shells are split up into sub-shells and that some of these sub-shells have further
divisions (orbitals).