UNIT 1

MODULE 1 : Fundamentals in Chemistry

1. ATOMIC STRUCTURE AND THE PERIODIC TABLE
1.1 Daltons Atomic Theory
John Dalton (September 6, 1766 July 27, 1844) was an English chemist,
meteorologist and physicist. He is best known for his pioneering work in the
development of modern atomic theory, and his research into color blindness
(sometimes referred to as Daltonism, in his honor). 1
Dalton's Atomic Theory
1) All matter is made of atoms. Atoms are indivisible and indestructible.
2) All atoms of a given element are identical in mass and properties
3) Compounds are formed by a combination of two or more different kinds of
atoms.
4) A chemical reaction is a rearrangement of atoms.
Modern atomic theory is a little more involved than Dalton's theory but the
essence of Dalton's theory remains valid. Today we know that atoms can be
destroyed via nuclear reactions but not by chemical reactions. Also, there are
different kinds of atoms (differing by their masses) within elements that are
known as "isotopes", but isotopes of an element have the same chemical
properties.2
The history of the study of the atomic nature of matter illustrates the thinking
process that goes on in the philosophers and scientists heads. The models
they use do not provide an absolute understanding of the atom but only a
way of abstracting so that they can make useful predictions about them. The
epistemological methods that scientists use provide us with the best known
way of arriving at useful science and factual knowledge. No other method has
yet proven as successful.

In the beginning
Actually, the thought about electricity came before atoms. In about 600 B.C.
Thales of Miletus discovered that a piece of amber, after rubbing it with fur,
attracts bits of hair and feathers and other light objects. He suggested that
this mysterious force came from the amber. Thales, however, did not connect
this force with any atomic particle.
Not until around 460 B.C., did a Greek philosopher, Democritus, develop the
idea of atoms. He asked this question: If you break a piece of matter in half,

and then break it in half again, how many breaks will you have to make
before you can break it no further? Democritus thought that it ended at some
point, a smallest possible bit of matter. He called these basic matter particles,
atoms.
Unfortunately, the atomic ideas of Democritus had no lasting effects on other
Greek philosophers, including Aristotle. In fact, Aristotle dismissed the atomic
idea as worthless. People considered Aristotle's opinions very important and if
Aristotle thought the atomic idea had no merit, then most other people
thought the same also.
For more than 2000 years nobody did anything to continue the explorations
that the Greeks had started into the nature of matter. Not until the early
1800's did people begin again to question the structure of matter.
In the 1800's an English chemist, John Dalton performed experiments with
various chemicals that showed that matter, indeed, seem to consist of
elementary lumpy particles (atoms). Although he did not know about their
structure, he knew that the evidence pointed to something fundamental.

On the basis of his experiments, J.J. Thomson proposed a model of internal atomic
structure according to which atoms consisted of a positively charged substance (positive
electric fluid) distributed uniformly over the entire body of the atom, with negative
electrons

embedded

in

this

continuous

positive charge like seeds in a watermelon, or

raisins in pudding. Since electrons repel each
other but are, on the other hand attracted to
the centre of the positive charge, they were
supposed to assume certain stable positions
inside the body of the atom. Ernest Rutherford (1871-1937) and Hans Geiger together
bombarded thin pieces of gold with alpha particles. Most of the alpha particles passed
right through the foil, and the result was exactly what the experimenters expected based
on Thomson's model of the atom. But some of alpha particles struck the gold foil and
were deflected at a sharp angle often 90 or more (J J Thomson's Model). This amazed
Rutherford, who remarked "It was as though you have fired a 15-inch shell at a piece of
tissue paper and it came back and hit you". Early in 1911 Rutherford exclaimed to
Geiger, "I know what the atoms looks like!". Rutherford put together a new idea of the
atom: what if all the positively charged particles in the atom were not spread like a fluid
throughout the atom as Thomson had thought but were lumped together in the centre in
2

one tiny area, or "nucleus"? Most of the atom's mass would be contained in the nucleus,
and an equal number of negatively charged electrons would be found in motion
somewhere outside the nucleus. Undoubtedly, it was a compelling idea - a sort of tiny
planetary system that resembled the larger solar system we are living in.

In 1900 Max Planck, a professor of theoretical physics in Berlin showed that

when you vibrate atoms strong enough, such as when you heat an object
until it glows, you can measure the energy only in discrete units. He called
these energy packets, quanta.
Physicists at the time thought that light consisted of waves but, according to
Albert Einstein, the quanta behaved like discrete particles. Physicists call
Einstein's discrete light particle, a "photon."

Photoelectric effect
Atoms not only emit photons, but they can also absorb them. In 1905, Albert
Einstein wrote a ground-breaking paper that explained that light absorption
can release electrons from atoms, a phenomenon called the "photoelectric
effect." Einstein received his only Nobel Prize for physics in 1921 for his work
on the photoelectric effect.
A heated controversy occurred for many years on deciding whether light
consisted of waves or particles. The evidence appeared strong for both cases.
Later, physicists showed that light appears as either wave-like or particle-like
(but never both at the same time) depending on the experimental setup.

Other particles got discovered around this time called alpha rays. These
particles had a positive charge and physicists thought that they consisted of
the positive parts of the Thompson atom (now known as the nucleus of
atoms).
In 1911 Ernest Rutherford thought it would prove interesting to bombard
atoms with these alpha rays, figuring that this experiment could investigate
the inside of the atom (sort of like a probe). He used Radium as the source of
the alpha particles and shinned them onto the atoms in gold foil. Behind the
foil sat a fluorescent screen for which he could observe the alpha particles
impact.

The results of the experiments came unexpected. Most of the alpha particles
went smoothly through the foil. Only an occasional alpha veered sharply from
its original path, sometimes bouncing straight back from the foil! Rutherford
reasoned that they must get scattered by tiny bits of positively charged
matter. Most of the space around these positive centers had nothing in them.
He thought that the electrons must exist somewhere within this empty space.
Rutherford thought that the negative electrons orbited a positive center in a
manner like the solar system where the planets orbit the sun.

Rutherford's atom
Rutherford knew that atoms consist of a compact positively charged nucleus,
around which circulate negative electrons at a relatively large distance. The
nucleus occupies less than one thousand million millionth (10) of the atomic
volume, but contains almost all of the atom's mass. If an atom had the size of
the earth, the nucleus would have the size of a football stadium.

Not until 1919 did Rutherford finally identify the particles of the nucleus as
discrete positive charges of matter. Using alpha particles as bullets,
Rutherford knocked hydrogen nuclei out of atoms of six elements: boron,
fluorine, sodium, aluminum, phosphorus, and nitrogen. He named them
protons, from the Greek for 'first', for they consisted of the first identified
building blocks of the nuclei of all elements. He found the protons mass at
1,836 times as great as the mass of the electron.

But there appeared something terribly wrong with Rutherford's model of the
atom. The theory of electricity and magnetism predicted that opposite
charges attract each other and the electrons should gradually lose energy
and spiral inward. Moreover, physicists reasoned that the atoms should give
off a rainbow of colors as they do so. But no experiment could verify this
rainbow.
In 1912 a Danish physicist, Niels Bohr came up with a theory that said the
electrons do not spiral into the nucleus and came up with some rules for what
does happen. (This began a new approach to science because for the first
time rules had to fit the observation regardless of how they conflicted with
the theories of the time.)
Bohr said, "Here's some rules that seem impossible, but they describe the
way atoms operate, so let's pretend they're correct and use them." Bohr
came up with two rules which agreed with experiment:
RULE 1: Electrons can orbit only at certain allowed distances from the
nucleus.
RULE 2: Atoms radiate energy when an electron jumps from a higher-energy
orbit to a lower-energy orbit. Also, an atom absorbs energy when an electron
gets boosted from a low-energy orbit to a high-energy orbit.

Bohr's atom for Hydrogen

The electron can exist in only one of the orbits. (The diagram shows only five
orbits, but any number of orbits can theoretically exist.)

Light (photons) emit whenever an electron jumps from one orbit to another.
The jumps seem to happen instantaneously without moving through a
trajectory.
The examples above show only two possibilities from Rule 2.
By the 1920s, further experiments showed that Bohr's model of the
atom had some troubles. Bohr's atom seemed too simple to describe

the heavier elements. In fact it only worked roughly in these cases. The
spectral lines did not appear correct when a strong magnetic field
influenced the atoms.

Bohr- Sommerfeld model of the atom

Bohr and a German physicist, Arnold Sommerfeld expanded the original Bohr
model to explain these variations. According to the Bohr-Sommerfeld model,
not only do electrons travel in certain orbits but the orbits have different
shapes and the orbits could tilt in the presence of a magnetic field. Orbits can
appear circular or elliptical, and they can even swing back and forth through
the nucleus in a straight line.

The orbit shapes and various angles to the magnetic field could only have
certain shapes, similar to an electron in a certain orbit. As an example, the
fourth orbit in a hydrogen atom can have only three possible shapes and
seven possible traits. These added states allowed more possibilities for
different spectral lines to appear. This brought the model of the atom into
closer agreement with experimental data.

The conditions of the state of the orbit got assigned quantum numbers. The
three states discussed so far consist of: orbit number (n), orbit shape (l) and
orbit tilt (m).
In 1924 an Austrian physicist, Wolfgang Pauli predicted that an electron
should spin (kind of like a top) while it orbits around the nucleus. The electron
can spin in either of two direction. This spin consisted of a fourth quantum
number: electron spin (s).

Pauli's Exclusion principle

Pauli gave a rule governing the behavior of electrons within the atom that
agreed with experiment. If an electron has a certain set of quantum numbers,
then no other electron in that atom can have the same set of quantum
numbers. Physicists call this "Pauli's exclusion principle." It provides an
important principle to this day and has even outlived the Bohr-Sommerfeld
model that Pauli designed it for.
http://www.nobeliefs.com/atom.htm

How do Scientists develop theories, and how are these theories

modified?
Scientific Method
The scientific method is a process for experimentation that is used to explore
observations and answer questions. Scientists use the scientific method to
search for cause and effect relationships in nature. In other words, they
design an experiment so that changes to one item cause something else to
vary in a predictable way.
Just as it does for a professional scientist, the scientific method will help you
to focus your science fair project question, construct a hypothesis, design,
execute, and evaluate your experiment. See PPT Scientific Method

The sub-atomic particles

Protons, neutrons and electrons.

proton
neutron
electron

relative mass
1
1
1/1836

relative charge
+1
0
-1

The nucleus
The nucleus is at the centre of the atom and contains the protons and
neutrons. Protons and neutrons are collectively known as nucleons.
Virtually all the mass of the atom is concentrated in the nucleus, because the
electrons weigh so little.
Working out the numbers of protons and neutrons
No of protons = ATOMIC NUMBER (Z) of the atom
The atomic number is also given the more descriptive name of proton
number.
Number of protons + number of neutrons = MASS NUMBER (A) of
the atom
The mass number is also called the nucleon number.
This information can be given simply in the form:

How many protons and neutrons has this atom got?

The atomic number counts the number of protons (9); the mass number
counts protons + neutrons (19). If there are 9 protons, there must be 10
neutrons for the total to add up to 19.
The atomic number is tied to the position of the element in the Periodic Table
and therefore the number of protons defines what sort of element you are
talking about. So if an atom has 8 protons (atomic number = 8), it must be
oxygen. If an atom has 12 protons (atomic number = 12), it must be
magnesium.
Similarly, every chlorine atom (atomic number = 17) has 17 protons; every
uranium atom (atomic number = 92) has 92 protons.
Isotopes
The number of neutrons in an atom can vary within small limits. For example,
there are three kinds of carbon atom 12C, 13C and 14C. They all have the same
number of protons, but the number of neutrons varies.

carbon-12
carbon-13
carbon-14

protons
6
6
6

neutrons
6
7
8

mass number
12
13
14

These different atoms of carbon are called isotopes. The fact that they have
varying numbers of neutrons makes no difference whatsoever to the chemical
reactions of the carbon.
Isotopes are atoms which have the same atomic number but different mass
numbers. They have the same number of protons but different numbers of
neutrons.
The electrons
Working out the number of electrons
Atoms are electrically neutral, and the positive ness of the protons is
balanced by the negative ness of the electrons. It follows that in a neutral
atom:
number of electrons = number of protons

10

So, if an oxygen atom (atomic number = 8) has 8 protons, it must also have 8
electrons; if a chlorine atom (atomic number = 17) has 17 protons, it must
also have 17 electrons.
The arrangement of the electrons
The electrons are found at considerable distances from the nucleus in a series
of levels called energy levels. Each energy level can only hold a certain
number of electrons. The first level (nearest the nucleus) will only hold 2
electrons, the second holds 8, and the third also seems to be full when it has
8 electrons. At CSEC you stopped there because the pattern gets more
complicated after that.
These levels can be thought of as getting progressively further from the
nucleus. Electrons will always go into the lowest possible energy level
(nearest the nucleus) - provided there is space.
To work out the electronic arrangement of an atom

Look up the atomic number in the Periodic Table - making sure that you
choose the right number if two numbers are given. The atomic number
will always be the smaller one.
This tells you the number of protons, and hence the number of
electrons.
Arrange the electrons in levels, always filling up an inner level before
you go to an outer one.

E.g. to find the electronic arrangement in chlorine

The Periodic Table gives you the atomic number of 17.

Therefore there are 17 protons and 17 electrons.

The arrangement of the electrons will be 2, 8, 7 (i.e. 2 in the first level,

8 in the second, and 7 in the third).

The electronic arrangements of the first 20 elements

11

After this the pattern alters as you enter the transition series in the Periodic
Table.
Two important generalizations
If you look at the patterns in this table:

The number of electrons in the outer level is the same as the group
number. (Except with helium which has only 2 electrons. The noble
gases are also usually called group 0 - not group 8.) This pattern
extends throughout the Periodic Table for the main groups (i.e. not
including the transition elements).
So if you know that barium is in group 2, it has 2 electrons in its outer
level; iodine (group 7) has 7 electrons in its outer level; lead (group 4)
has 4 electrons in its outer level.

Noble gases have full outer levels.

Dots-and-crosses diagrams
In any introductory chemistry course you will have come across the electronic
structures of hydrogen and carbon, for example, drawn as:

The circles show energy levels - representing increasing distances from the
nucleus. You could straighten the circles out and draw the electronic structure
as a simple energy diagram.

Carbon, for example, would look like this:

12

Relative atomic mass

Atoms are so small that their masses, expressed in grams, are difficult to
work with. Some examples are listed in Table 1 below
Table 1
Element
H
He
Li
C
O
Na
Ar
U

Average mass of atom g

1.67355 x 10-24
6.64605 x 10-24
1.15217 x 10-23
1.99436 x 10-23
2.65659 x 10-23
3.81730 x 10-23
6.63310 x 10-23
3.95233 x 10-22

The mass of an atom expressed as relative atomic mass (Ar) is much more
manageable.
By definition, the relative atomic mass, Ar, of an element is the ratio of the
mass of an atom of the element to one twelfth the mass of a 12C atom.

Mass ofatomic
one atom
of the element
Exercise: Calculate the relative
masses
of the elements listed in table
Relative
atomic
mass
=
x12
1.
1.4
Mass of 1 atom of carbon-12

1.4 What is Radioactivity?

13

Radioactivity is the spontaneous emission of radiation, either directly from

unstable atomic nuclei or as a consequence of a nuclear reaction. 4
Alpha Decay
Alpha decay is usually restricted to the heavier elements in the periodic
table. (Only a handful of nuclides with atomic numbers less than 83 emit an
-particle.) The product of -decay is easy to predict if we assume that both
mass and charge are conserved in nuclear reactions. Alpha decay of the 238U
"parent" nuclide, for example, produces 234Th as the "daughter" nuclide.

The sum of the mass numbers of the products (234 + 4) is equal to the mass
number of the parent nuclide (238), and the sum of the charges on the
products (90 + 2) is equal to the charge on the parent nuclide.
Beta Decay
There are three different modes of beta decay:

electron emission

electron capture
positron emission

For the purposes of your syllabus we will focus on electron emission.

Electron emission is literally the process in which an electron is ejected or
emitted from the nucleus. When this happens, the charge on the nucleus
increases by one. Electron emitters are found throughout the periodic table,
from the lightest elements (3H) to the heaviest (255Es). The product of electron
emission can be predicted by assuming that both mass number and charge
are conserved in nuclear reactions. If 40K is an electron emitter, for example,
the product of this reaction must be 40Ca.

Once again the sum of the mass numbers of the products is equal to the
mass number of the parent nuclide and the sum of the charge on the
products is equal to the charge on the parent nuclide.
Nuclei can also decay by capturing one of the electrons that surround the
nucleus.

14

Gamma Emission
The daughter nuclides produced by -decay are often obtained in an excited
state. The excess energy associated with this excited state is released when
the nucleus emits a photon in the -ray portion of the electromagnetic
spectrum. Most of the time, the -ray is emitted within 10-12 seconds after the
-particle. In some cases, gamma decay is delayed, and a short-lived, or
metastable, nuclide is formed, which is identified by a small letter m written
after the mass number. 60mCo, for example, is produced by the electron
emission of 60Fe.

The metastable 60mCo nuclide has a half-life of 10.5 minutes. Since

electromagnetic radiation carries neither charge nor mass, the product of ray emission by 60mCo is 60Co.

Spontaneous Fission
Nuclides with atomic numbers of 90 or more undergo a form of radioactive
decay known as spontaneous fission in which the parent nucleus splits into
a pair of smaller nuclei. The reaction is usually accompanied by the ejection
of one or more neutrons.

For all but the very heaviest isotopes, spontaneous fission is a very slow
reaction. Spontaneous fission of 238U, for example, is almost two million times
slower than the rate at which this nuclide undergoes -decay.
1.6

The abundance of the isotopes

15

A mass spectrum is used to display the various isotopes of a particular

element in a sample.

The mass spectrum for boron

The number of isotopes

The two peaks in the mass spectrum shows that there are 2 isotopes of boron
- with relative isotopic masses of 10 and 11 on the 12C scale.
The relative sizes of the peaks gives you a direct measure of the relative
abundances of the isotopes. You can find the relative abundances by
measuring the lines on the stick diagram.
In this case, the two isotopes (with their relative abundances) are:
boron10
boron11

23
10
0

Working out the relative atomic mass

The relative atomic mass (RAM) of an element is given the symbol Ar and is
defined as:
The relative atomic mass of an element is the weighted average of the
masses of the isotopes relative to 1/12 of the mass of a carbon-12
atom.
A "weighted average" allows for the fact that there won't be equal amounts
of the various isotopes. The example coming up should make that clear.
Suppose you had 123 typical atoms of boron. 23 of these would be
100 would be 11B.
The total mass of these would be (23 x 10) + (100 x 11) = 1330

16

10

B and

The average mass of these 123 atoms would be 1330 / 123 = 10.8 (to 3
significant figures).
10.8 is the relative atomic mass of boron.
Notice the effect of the "weighted" average. A simple average of 10 and 11
is, of course, 10.5. Our answer of 10.8 allows for the fact that there are a lot
more of the heavier isotope of boron - and so the "weighted" average ought
to be closer to that.

The mass spectrum for zirconium

The number of isotopes

The 5 peaks in the mass spectrum shows that there are 5 isotopes of
zirconium - with relative isotopic masses of 90, 91, 92, 94 and 96 on the 12C
scale.
The abundance of the isotopes
This time, the relative abundances are given as percentages. Again you can
find these relative abundances by measuring the lines on the stick diagram.
In this case, the 5 isotopes (with their relative percentage abundances) are:
zirconium90
zirconium91
zirconium92
zirconium94
zirconium-

17

51.
5
11.
2
17.
1
17.
4
2.8

96

Working out the relative atomic mass

Suppose you had 100 typical atoms of zirconium. 51.5 of these would be
11.2 would be 91Zr and so on.

90

Zr,

The total mass of these 100 typical atoms would be

(51.5 x 90) + (11.2 x 91) + (17.1 x 92) + (17.4 x 94) + (2.8 x 96) = 9131.8
The average mass of these 100 atoms would be 9131.8 / 100 = 91.3 (to 3
significant figures).
91.3 is the relative atomic mass of zirconium.
1.7
What is an emission spectrum?
Observing hydrogen's emission spectrum
A hydrogen discharge tube is a slim tube containing hydrogen gas at low
pressure with an electrode at each end. If you put a high voltage across this
(say, 5000 volts), the tube lights up with a bright pink glow.
If the light is passed through a prism or diffraction grating, it is split into its
various colors. What you would see is a small part of the hydrogen emission
spectrum. Most of the spectrum is invisible to the eye because it is either in
the infra-red or the ultra-violet.
The photograph shows part of a hydrogen discharge tube on the left, and the
three most easily seen lines in the visible part of the spectrum on the right.
(Ignore the "smearing" - particularly to the left of the red line. This is caused
by flaws in the way the photograph was taken. See note below.)

18

This photograph is by courtesy of Dr Rod Nave of the Department of Physics

and Astronomy at Georgia State University, Atlanta.
Extending hydrogen's emission spectrum into the UV and IR
There is a lot more to the hydrogen spectrum than the three lines you can
see with the naked eye. It is possible to detect patterns of lines in both the
ultra-violet and infra-red regions of the spectrum as well.
These fall into a number of "series" of lines named after the person who
discovered them. The diagram below shows three of these series, but there
are others in the infra-red to the left of the Paschen series shown in the
diagram.
The diagram is quite complicated, so we will look at it a bit at a time. Look
first at the Lyman series on the right of the diagram - this is the most spread
out one and easiest to see what is happening.

19

The Lyman series is a series of lines in the ultra-violet. Notice that the lines
get closer and closer together as the frequency increases. Eventually, they
get so close together that it becomes impossible to see them as anything
other than a continuous spectrum. That's what the shaded bit on the righthand end of the series suggests.
Then at one particular point, known as the series limit, the series stops.
If you now look at the Balmer series or the Paschen series, you will see that
the pattern is just the same, but the series have become more compact. In
the Balmer series, notice the position of the three visible lines from the
photograph further up the page.

Complicating everything - frequency and wavelength

You will often find the hydrogen spectrum drawn using wavelengths of light
rather than frequencies. Unfortunately, because of the mathematical
relationship between the frequency of light and its wavelength, you get two
completely different views of the spectrum if you plot it against frequency or
against wavelength.

The relationship between frequency and wavelength

The mathematical relationship is:

Rearranging this gives equations for either wavelength or frequency.

What this means is that there is an inverse relationship between the two - a
high frequency means a low wavelength and vice versa.

20

The Planck constant (denoted ) is a physical constant used to describe the

sizes of quanta. It plays a central part in the theory of quantum mechanics,
and is named after Max Planck, one of the founders of quantum theory. The
Planck constant divided by
is called the reduced Planck constant (also
known as the Dirac constant) and is denoted , pronounced "h-bar".
The Planck constant is the proportionality constant between the energy of a
photon and its frequency . The relation between energy and frequency is
known as Planck's relation:

Drawing the hydrogen spectrum in terms of wavelength

This is what the spectrum looks like if you plot it in terms of wavelength
instead of frequency:

. . . and just to remind you what the spectrum in terms of frequency looks
like:

21

1.8 1.9
What is an atomic orbital? ( see PPT Atomic Orbital Theory)
Orbitals and orbits
When the a planet moves around the sun, you can plot a definite path for it
which is called an orbit. A simple view of the atom looks similar and you may
have pictured the electrons as orbiting around the nucleus. The truth is
different, and electrons in fact inhabit regions of space known as orbitals.
Orbits and orbitals sound similar, but they have quite different meanings. It is
essential that you understand the difference between them.
The Principle quantum number describes the size of the orbital. Since the
distance from of an electron from the nucleus is directly proportional to the
energy of the electron (as described in the Bohr model), the principle
quantum number is also a measure of the orbital. The lowest energy levels
are numbered (n=1, n=2, n=3, etc).
The impossibility of drawing orbits for electrons
To plot a path for something you need to know exactly where the object is
and be able to work out exactly where it's going to be an instant later. You
can't do this for electrons.
The Heisenberg Uncertainty Principle says - loosely - that you can't know
with certainty both where an electron is and where it's going next. (What it

22

actually says is that it is impossible to define with absolute precision, at the

same time, both the position and the momentum of an electron.)
That makes it impossible to plot an orbit for an electron around a nucleus. Is
this a big problem? No. If something is impossible, you have to accept it and
find a way around it.

Hydrogen's electron - the 1s orbital

Suppose you had a single hydrogen atom and at a particular instant plotted
the position of the one electron. Soon afterwards, you do the same thing, and
find that it is in a new position. You have no idea how it got from the first
place to the second.
You keep on doing this over and over again, and gradually build up a sort of
3D map of the places that the electron is likely to be found.
In the hydrogen case, the electron can be found anywhere within a spherical
space surrounding the nucleus. The diagram shows a cross-section through
this spherical space.
95% of the time (or any other percentage you choose), the electron will be
found within a fairly easily defined region of space quite close to the nucleus.
Such a region of space is called an orbital. You can think of an orbital as
being the region of space in which the electron lives.
What is the electron doing in the orbital? We don't know, we can't know, and
so we just ignore the problem! All you can say is that if an electron is in a
particular orbital it will have a particular definable energy.
Each orbital has a name.
The orbital occupied by the hydrogen electron is called a 1s orbital. The "1"
represents the fact that the orbital is in the energy level closest to the
nucleus. The "s" tells you about the shape of the orbital. s orbitals are
spherically symmetric around the nucleus - in each case, like a hollow ball
made of rather chunky material with the nucleus at its centre.
The orbital on the left is a 2s orbital. This is similar to a 1s orbital except
that the region where there is the greatest chance of finding the electron is
further from the nucleus - this is an orbital at the second energy level.
If you look carefully, you will notice that there is another region of slightly
higher electron density (where the dots are thicker) nearer the nucleus.

23

("Electron density" is another way of talking about how likely you are to find
an electron at a particular place.)
2s (and 3s, 4s, etc) electrons spend some of their time closer to the nucleus
than you might expect. The effect of this is to slightly reduce the energy of
electrons in s orbitals. The nearer the nucleus the electrons get, the lower
their energy.
3s, 4s (etc) orbitals get progressively further from the nucleus.

p orbitals
Not all electrons inhabit s orbitals (in fact, very few electrons live in s
orbitals). At the first energy level, the only orbital available to electrons is the
1s orbital, but at the second level, as well as a 2s orbital, there are also
orbitals called 2p orbitals.
A p orbital is rather like 2 identical balloons tied together at the nucleus.
Unlike an s orbital, a p orbital points in a particular direction - the one drawn
points up and down the page.
At any one energy level it is possible to have three absolutely equivalent p
orbitals pointing mutually at right angles to each other. These are arbitrarily
given the symbols px, py and pz. This is simply for convenience - what you
might think of as the x, y or z direction changes constantly as the atom
tumbles in space.
The p orbitals at the second energy level are called 2p x, 2py and 2pz. There
are similar orbitals at subsequent levels - 3p x, 3py, 3pz, 4px, 4py, 4pz and so
on.
All levels except for the first level have p orbitals. At the higher levels the
lobes get more elongated, with the most likely place to find the electron more
distant from the nucleus.

d and f orbitals
In addition to s and p orbitals, there are two other sets of orbitals which
become available for electrons to inhabit at higher energy levels. At the third
level, there is a set of five d orbitals (with complicated shapes and names) as
well as the 3s and 3p orbitals (3px, 3py, 3pz). At the third level there are a
total of nine orbitals altogether.

24

At the fourth level, as well the 4s and 4p and 4d orbitals there are an
additional seven f orbitals - 16 orbitals in all. s, p, d and f orbitals are then
available at all higher energy levels as well.
For the moment, you need to be aware that there are sets of five d orbitals at
levels from the third level upwards, but you probably won't be expected to
draw them or name them. Apart from a passing reference, you won't come
across f orbitals at all.
Fitting electrons into orbitals
You can think of an atom as a very bizarre house (like an inverted pyramid!) with the nucleus living on the ground floor, and then various rooms (orbitals)
on the higher floors occupied by the electrons. On the first floor there is only
1 room (the 1s orbital); on the second floor there are 4 rooms (the 2s, 2p x, 2py
and 2pz orbitals); on the third floor there are 9 rooms (one 3s orbital, three 3p
orbitals and five 3d orbitals); and so on. But the rooms aren't very big . . .
Each orbital can only hold 2 electrons.
A convenient way of showing the orbitals that the electrons live in is to draw
"electrons-in-boxes".
"Electrons-in-boxes"
Orbitals can be represented as boxes with the electrons in them shown as
arrows. Often an up-arrow and a down-arrow are used to show that the
electrons are in some way different.
A 1s orbital holding 2 electrons would be drawn as shown on the right, but it
can be written even more quickly as 1s 2. This is read as "one s two" - not as
"one s squared".
You mustn't confuse the two numbers in this notation:

The order of filling orbitals

Electrons fill low energy orbitals (closer to the nucleus) before they fill higher
energy ones. Where there is a choice between orbitals of equal energy, they
fill the orbitals singly as far as possible.
This filling of orbitals singly where possible is known as Hund's rule. It only
applies where the orbitals have exactly the same energies (as with p orbitals,
for example), and helps to minimize the repulsions between electrons and so
makes the atom more stable.

25

The diagram (not to scale) summarizes the energies of the orbitals up to the
4p level.

Notice that the s orbital always has a slightly lower energy than the p orbitals
at the same energy level, so the s orbital always fills with electrons before the
corresponding p orbitals.
The real oddity is the position of the 3d orbitals. They are at a slightly higher
level than the 4s - and so it is the 4s orbital which will fill first, followed by all
the 3d orbitals and then the 4p orbitals. Similar confusion occurs at higher
levels, with so much overlap between the energy levels that the 4f orbitals
don't fill until after the 6s, for example.

1.4 1.10 .
Defining first ionization energy
Definition
The first ionization energy is the energy required to remove the most loosely
held electron from one mole of gaseous atoms to produce 1 mole of gaseous
ions each with a charge of 1+.

This is more easily seen in symbol terms.

It is the energy needed to carry out this change per mole of X.

Things to notice about the equation
The state symbols - (g) - are essential. When you are talking about ionization
energies, everything must be present in the gas state.

26

Ionization energies are measured in kJ mol -1 (kilojoules per mole). They vary
in size from 381 (which you would consider very low) up to 2370 (which is
very high).
All elements have first ionization energy - even atoms which don't form
positive ions in test tubes. The reason that helium (1st I.E. = 2370 kJ mol -1)
doesn't normally form a positive ion is because of the huge amount of energy
that would be needed to remove one of its electrons.

Patterns of first ionization energies in the Periodic Table

The first 20 elements

First ionization energy shows periodicity. That means that it varies in a

repetitive way as you move through the Periodic Table. For example, look at
the pattern from Li to Ne, and then compare it with the identical pattern from
Na to Ar.
These variations in first ionization energy can all be explained in terms of the
structures of the atoms involved.
Factors affecting the size of ionization energy
Ionization energy is a measure of the energy needed to pull a particular
electron away from the attraction of the nucleus. A high value of ionization
energy shows a high attraction between the electron and the nucleus.
The size of that attraction will be governed by:
The charge on the nucleus.
The more protons there are in the nucleus, the more positively charged the
nucleus is, and the more strongly electrons are attracted to it.

27

The distance of the electron from the nucleus.

Attraction falls off very rapidly with distance. An electron close to the nucleus
will be much more strongly attracted than one further away.
The number of electrons between the outer electrons and the
nucleus.
Consider a sodium atom, with the electronic structure 2,8,1. (There's no
reason why you can't use this notation if it's useful!)
If the outer electron looks in towards the nucleus, it doesn't see the nucleus
sharply. Between it and the nucleus there are the two layers of electrons in
the first and second levels. The 11 protons in the sodium's nucleus have their
effect cut down by the 10 inner electrons. The outer electron therefore only
feels a net pull of approximately 1+ from the centre. This lessening of the pull
of the nucleus by inner electrons is known as screening or shielding.
Whether the electron is on its own in an orbital or paired with
another electron.
Two electrons in the same orbital experience a bit of repulsion from each
other. This offsets the attraction of the nucleus, so that paired electrons are
removed rather more easily than you might expect.

Explaining the pattern in the first few elements

Hydrogen has an electronic structure of 1s1. It is a very small atom, and the
single electron is close to the nucleus and therefore strongly attracted. There
are no electrons screening it from the nucleus and so the ionization energy is
high (1310 kJ mol-1).
Helium has a structure 1s2. The electron is being removed from the same
orbital as in hydrogen's case. It is close to the nucleus and unscreened. The
value of the ionization energy (2370 kJ mol -1) is much higher than hydrogen,
because the nucleus now has 2 protons attracting the electrons instead of 1.
Lithium is 1s22s1. Its outer electron is in the second energy level, much more
distant from the nucleus. You might argue that that would be offset by the
additional proton in the nucleus, but the electron doesn't feel the full pull of
the nucleus - it is screened by the 1s 2 electrons.

28

You can think of the electron as feeling a net 1+ pull from the centre (3
protons offset by the two 1s2 electrons).
If you compare lithium with hydrogen (instead of with helium), the hydrogen's
electron also feels a 1+ pull from the nucleus, but the distance is much
greater with lithium. Lithium's first ionization energy drops to 519 kJ mol -1
whereas hydrogen's is 1310 kJ mol-1.
The patterns in periods 2 and 3
Talking through the next 17 atoms one at a time would take ages. We can do
it much more neatly by explaining the main trends in these periods, and then
accounting for the exceptions to these trends.
The first thing to realize is that the patterns in the two periods are identical the difference being that the ionization energies in period 3 are all lower than
those in period 2.

29

Explaining the general trend across periods 2 and 3

The general trend is for ionization energies to increase across a period.
In the whole of period 2, the outer electrons are in 2-level orbitals - 2s or 2p.
These are all the same sort of distances from the nucleus, and are screened
by the same 1s2 electrons.
The major difference is the increasing number of protons in the nucleus as
you go from lithium to neon. That causes greater attraction between the
nucleus and the electrons and so increases the ionization energies. In fact the
increasing nuclear charge also drags the outer electrons in closer to the
nucleus. That increases ionization energies still more as you go across the
period.
In period 3, the trend is exactly the same. This time, all the electrons being
removed are in the third level and are screened by the 1s 22s22p6 electrons.
They all have the same sort of environment, but there is an increasing
nuclear charge.
Why the drop between groups 2 and 3 (Be-B and Mg-Al)?
The explanation lies with the structures of boron and aluminum. The outer
electron is removed more easily from these atoms than the general trend in
their period would suggest.
Be
B

1s22s2
1s22s22px
1

1st I.E. = 900 kJ

mol-1
1st I.E. = 799 kJ
mol-1

You might expect the boron value to be more than the beryllium value
because of the extra proton. Offsetting that is the fact that boron's outer
electron is in a 2p orbital rather than a 2s. 2p orbitals have a slightly higher

30

energy than the 2s orbital, and the electron is, on average, to be found
further from the nucleus. This has two effects.
The increased distance results in a reduced attraction and so a reduced
ionization energy.
The 2p orbital is screened not only by the 1s 2 electrons but, to some
extent, by the 2s2 electrons as well. That also reduces the pull from the
nucleus and so lowers the ionization energy.

The explanation for the drop between magnesium and aluminum is the same,
except that everything is happening at the 3-level rather than the 2-level.
Mg
Al

1s22s22p63s2
1s22s22p63s23p
1
x

1st I.E. = 736 kJ

mol-1
1st I.E. = 577 kJ
mol-1

The 3p electron in aluminum is slightly more distant from the nucleus than
the 3s, and partially screened by the 3s 2 electrons as well as the inner
electrons. Both of these factors offset the effect of the extra proton.

Why the drop between groups 5 and 6 (N-O and P-S)?

Once again, you might expect the ionization energy of the group 6 element to
be higher than that of group 5 because of the extra proton. What is offsetting
it this time?
1s22s22px12py12p 1st I.E. = 1400 kJ
1
mol-1
z
2
2
2
1
1s 2s 2px 2py 2p 1st I.E. = 1310 kJ
O 1
mol-1
z
N

The screening is identical (from the 1s 2 and, to some extent, from the 2s2
electrons), and the electron is being removed from an identical orbital.
The difference is that in the oxygen case the electron being removed is one of
the 2px2 pair. The repulsion between the two electrons in the same orbital
means that the electron is easier to remove than it would otherwise be.
The drop in ionization energy at sulphur is accounted for in the same way.
Trends in ionization energy down a group
As you go down a group in the Periodic Table ionization energies generally
fall. You have already seen evidence of this in the fact that the ionization
energies in period 3 are all less than those in period 2.

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Taking Group 1 as a typical example:

Why is the sodium value less than that of lithium?

There are 11 protons in a sodium atom but only 3 in a lithium atom, so the
nuclear charge is much greater. You might have expected a much larger
ionization energy in sodium, but offsetting the nuclear charge is a greater
distance from the nucleus and more screening.
Li

1s22s1

Na

1s22s22p63
s1

1st I.E. = 519 kJ

mol-1
1st I.E. = 494 kJ
mol-1

Lithium's outer electron is in the second level, and only has the 1s 2 electrons
to screen it. The 2s1 electron feels the pull of 3 protons screened by 2
electrons - a net pull from the centre of 1+.
The sodium's outer electron is in the third level, and is screened from the 11
protons in the nucleus by a total of 10 inner electrons. The 3s 1 electron also
feels a net pull of 1+ from the centre of the atom. In other words, the effect of
the extra protons is compensated for by the effect of the extra screening
electrons. The only factor left is the extra distance between the outer
electron and the nucleus in sodium's case. That lowers the ionization energy.
Similar explanations hold as you go down the rest of this group - or, indeed,
any other group.
Trends in ionization energy in a transition series

Apart from zinc at the end, the other ionization energies are all much the
same.

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All of these elements have an electronic structure [Ar]3d n4s2 (or 4s1 in the
cases of chromium and copper). The electron being lost always comes from
the 4s orbital.
As you go from one atom to the next in the series, the number of protons in
the nucleus increases, but so also does the number of 3d electrons. The 3d
electrons have some screening effect, and the extra proton and the extra 3d
electron more or less cancel each other out as far as attraction from the
centre of the atom is concerned.
The rise at zinc is easy to explain.
Cu
Zn

[Ar]3d104
s1
[Ar]3d104
s2

1st I.E. = 745 kJ

mol-1
1st I.E. = 908 kJ
mol-1

In each case, the electron is coming from the same orbital, with identical
screening, but the zinc has one extra proton in the nucleus and so the
attraction is greater. There will be a degree of repulsion between the paired
up electrons in the 4s orbital, but in this case it obviously isn't enough to
outweigh the effect of the extra proton.
Ionization energies and reactivity
The lower the ionization energy, the more easily this change happens:

You can explain the increase in reactivity of the Group 1 metals (Li, Na, K, Rb,
Cs) as you go down the group in terms of the fall in ionization energy.
Whatever these metals react with, they have to form positive ions in the
process, and so the lower the ionization energy, the more easily those ions
will form.
The danger with this approach is that the formation of the positive ion is only
one stage in a multi-step process.
For example, you wouldn't be starting with gaseous atoms; nor would you
end up with gaseous positive ions - you would end up with ions in a solid or in
solution. The energy changes in these processes also vary from element to
element. Ideally you need to consider the whole picture and not just one
small part of it.
However, the ionization energies of the elements are going to be major
contributing factors towards the activation energy of the reactions.
Remember that activation energy is the minimum energy needed before a
reaction will take place. The lower the activation energy, the faster the

33

reaction will be - irrespective of what the overall energy changes in the

reaction are.
The fall in ionization energy as you go down a group will lead to lower
activation energies and therefore faster reactions. 5

34