Atomic Structure

and the Periodic

Table

You should be able to:

1.1 discuss the process of theoretical change with
respect to Daltons atomic change;
1.2 describe the structure of the atom;
1.3 define the following terms:
(i) mass number;
(ii) isotopes;
(iii) relative atomic and isotopic masses based
the carbon-12 scale.

on

Specific Objectives
1.4 explain the phenomenon of radioactivity;
1.5 cite the use of radioisotopes;
1.6 calculate the relative atomic mass of an element,
given isotopic masses and abundances;
1.7 explain how data from emission spectra
provide
evidence for discrete energy levels within the atom;

Specific Objectives
1.8 describe the atomic orbitals;
1.9 describe the shapes of the s and p orbitals;
1.10 determine the electronic configurations of atoms and
ions in terms of s, p and d orbitals;
1.11 state the factors which influence the first ionisation
energy of elements;

Specific Objectives
1.12 explain how ionisation energy data
provide evidence for sub-shells;
1.13 derive the electronic configuration of an
element from data on successive ionisation
energies.

Examples of criteria that are considered

when theories are accepted

Fit between evidence and theoretical

constructs
Reliability and accuracy of data
Replicability of experiments

Examples of criteria that are considered

when theories are accepted
Consensus within the scientific community
Societal factors

Electronic
Structure

Summary of Subatomic particles

Name

Mass
numbe
r

Mass/kg

Relativ
e
charge

Charge/
coulom
b

Proton

1.673 x
10-27

+1

+1.6 x
10-19

Neutron

1.675 x
10-27

0
0.911
x of
-1 the protons
-1.6 x and neutron
Note electron
that the accurate
masses
10
10
are not exactly the same. The charges on the proton
and electron are exactly the same.
-30

-19

RADIOACTIVITY
A large number of elements
have unstable atoms which
split to form smaller
particles.
In the process energy is
released. This energy is in
the form of radiation.

RADIOACTIVITY
Three types of radiation are
given off by radioactive
substances. They differ in
their response to an electric
field. The uncharged rays,
(gamma) rays, are similar to X
rays. They have high
penetrating power, being able

RADIOACTIVITY
Measurement of m/z
identified (alpha) rays as
the nuclei of helium and
(beta) rays as electrons.
rays can pass through o.o1
m of metal, and rays can
penetrate no more than

RADIOACTIVITY- Nuclear equations

Alpha-decay

When an atom disintegrates by

losing an alpha-particle (), the
remaining fragment will have a
mass number four less than the
original atom and an atomic
number two units lower.

RADIOACTIVITY- Nuclear equations

Remember that both mass

(indicated by the superscripts)
and charge (indicated by the
subscripts) must be balance in
nuclear equations.
Most radioactive isotopes with
atomic numbers greater than 83
(bismuth) undergo apha-decay.

CLASSWORK
Write nuclear equations
for the alpha-decay of
radium-226 () and
plutonium-238 (), use
the periodic table to find
the symbols of the

RADIOACTIVITY- Nuclear
equations
Beta-decay

Elements with an atomic number less than

83 do not usually exhibit alpha-decay.
Instead, various isotopes of these elements
emit beta-particles. For example, carbon14 () decays by beta particle emission
forming nitrogen (). The decay process can
be represented by the equation:
(See Chemistry in Context- page 78)

RADIOACTIVITY- Nuclear equations

Beta-decay

During beta-decay, mass

number remains constant, so
the number of protons +
neutrons stays constant.
However, the atomic number
increases by one.

CLASSWORK
1. Write nuclear equations for the beta-decay

of strontium-90 () and Iodine-131 ().

2. How do chemical reactions differ from

nuclear reactions such as alpha-decay and

beta-decay?

Rate of radioactive
decay
The rate at which a radioactive isotope decays
cannot be speeded up or slowed down. It
depends only on the identity of the isotope
and the amount of isotope present.
The rate of radioactive decay is proportional to
the number of radioactive atoms present.
Such reactions are described as first-order
reactions.
The time taken for radioactive isotopes to decay
to half the number of radioactive atoms is
called the half-life, t1/2.

Stability of Isotopes
The time taken for an isotope to break down
into a new atom gives an indication as to how
stable the isotope is. The more stable the
isotope the longer or greater its half life.
The rate of natural decay of a radioactive
isotope is not affected by physical or chemical
means. The half life of radioactive isotopes
vary from fraction of a second to millions of
years, e.g. Cobalt have a have life of 5.2yrs.

NOTE TO STUDENTS
1. Read up on gamma

()-rays.
2. Read up and make
notes on the use of
radioisotopes.

When atoms react,

electrons are redistributed.
These electrons may be
transferred from one atom
to another or they may be
shared between the
reacting atoms in a

It is possible to obtain
information about the
arrangement of electrons
in atoms by study the ease
with which atoms lose
electrons.

The energy needed to

remove one electron from
an atom is known as the
ionisation energy
(ionisation enthalpy) and
is given the symbol Hi

Question

What is the first

ionisation energy
of an element?

ANSWER
The energy required to remove one electron from
each atom in a mole of gaseous atoms
producing one mole of ions with one positive
charge.
Thus, the first ionisation energy of sodium is the
energy required for the process
Na(g) ------> Na+(g) + eH = Hi1

The most useful method of

determining the ionisation
energies of elements
involves a study of their
emission spectra

The compounds of some

elements emit light when
heated. For example, the
flame colour of lithium
compounds is red and that of
potassium compounds is lilac.

Some gaseous elements will also

emit light when they are subjected
to large potential differences in
electric discharge tubes. Neon
advertising signs work in this way
and the yellow sodium street
lamps are discharge tubes
containing sodium vapour.

What is a
spectroscope?
A spectroscope is a
device which splits light
into its component
wavelengths or
frequencies.

Line Spectra
If the light emitted by these
substances is examined using a
spectroscope, separate lines of
different colour will be observed. This
kind of spectrum is called a line
emission spectrum. Each element has
its own characteristic set of lines
different from any other element.

Line Spectra

Elements can be
identified from
their line
emission

Line Spectra

Each line in an
emission spectrum
corresponds to light
of a particular
frequency.

Formation of Line
Spectra
Electrons in an atom can
exist only at certain
energy levels. Under
normal conditions, the
electrons in an atom or
ion fill the lowest energy

Formation of Line
Spectra
When sufficient energy is
supplied to the atom, it is
sometimes possible to promote
(excite) an electron from a
lower energy level (the ground
state) to a higher one. This
process is called excitation.

Formation of Line
Spectra
The electron is unstable in
the higher energy level,
so it will emit the excess
energy as radiation and
drop back into a lower
energy level.

Formation of Line
Spectra
The energy difference
between the higher and
lower energy levels can
have only certain fixed
values because the energy
themselves are fixed.

Formation of Line
Spectra
At each drop in level, it gives out a
quantum of energy equal to the
difference in levels, E.
Because of the relationship E =
h, each quantum has a different
frequency and therefore
contributes one line to the line
spectrum.

Formation of Line
Spectra
The radiation emitted when an
electron falls from a higher to a
lower energy level can have only
certain fixed frequencies (i.e.
Certain specific colours) because
the frequency of any radiation is
determined by its energy.

Emission Spectra
The small amount of
radiation emitted by an
electron when it falls from
a higher to a lower energy
level is referred to as a
quantum of radiation.

Electrons and Orbits

Electrons occupy only certain fixed energy
levels around a nucleus. These energy levels
can be visualised as orbits of increasing
radius. Orbits of larger radius have higher
energy.
In the hydrogen atom, which has only one
electron, only one energy level is occupied at
any time. The situation is rather like a set of
shelves with one single object. The object can
only be placed on a shelf (not in the gaps
between) and the shelves still exist even if
they have no object on them.

THE BOHR MODEL

In 1913, Niels Bohr put forward his picture of
the atom. Bohr referred to Max Plancks
recently developed quantum theory,
according to which energy can be absorbed
or emitted in certain amounts, like separate
packets of energy, called quanta. Bohr
suggested:
1. An electron moving in an orbit can have only
certain amounts of energy, not an infinite
number of values: its energy is quantised.

THE BOHR MODEL

(Contd)
2. The energy that an electron needs in order to
move in a particular orbit depends on the
radius of the orbit. An electron in an orbit
distant from the nucleus requires higher
energy than an electron in an orbit near the
nucleus.
3. If the energy of the electron is quantised, the
radius of the orbit also must be quantised .
There is a restricted number of orbits with
certain radii, not an infinite number of orbits.

THE BOHR MODEL

(Contd)
4. An electron moving in one of these orbits
does not emit energy. In order to move to an
orbit farther away from the nucleus, the
electron must absorb energy to do work
against the attraction of the nucleus. If an
atom absorbs a photon (a quantum of light
energy), it can promote an electron from an
inner orbit to an outer orbit. If sufficient
photons are absorbed, a black line appears in
the absorption spectrum.

Energy and Frequency

The relationship between the energy (E) of a
quantum of radiation and its frequency () is:
E=hX
h is a constant, called Plancks constant. The
value of h is 4 x 10-13 kJ s mol-1

BRAIN EXERCISE
What is the value of
Plancks constant with
unit
kJ s
-1
molecule ?

HYDROGEN SPECTRUM
The electronic energy levels
are numbered (n=1, n=2,
n=3, etc.). The numbers are
sometimes referred to as the
principal quantum numbers
for the energy levels which
corresponds to the shells of
electrons.

THE HYDROGEN
SPECTRUM
The colours in the visible region of the hydrogen
spectrum are caused by electron transitions
from higher levels to the n=2 and not the
lowest energy level (n=1).
Lines which
result from
transitions to the
n=2 level in an
atom are known
as the Balmer
series

Lines which result from

transitions to the lowest
energy level in an atom
are known as the Lyman
Series

THE HYDROGEN
SPECTRUM
As the energy levels get
closer and eventually
come together, it follows
that the spectral lines
also get closer and
eventually come

If sufficient energy is given

to an atom, it is possible to
excite an electron just
beyond the highest energy
level. In this case the
electron will escape and
the atom becomes an ion.
Ionisation has taken place.

In an atom, the highest possible

energy level corresponds to the
frequency at which the lines in
the spectrum come together. So,
by determining the frequency at
which the converging spectral
lines come together, the
ionisation energy of an element
can be determined. This
particular frequency is called the

CLASS ACTIVITY
Frequencies of the Lyman Series for hydrogen
Frequency
Hz

/ 1o

14

Transition to which
frequency
corresponds

24.66

n=2 to n=1

29.23

n=3 to n=1

30.83

n=4 to n=1

31.57

n=4 to n=1

31.97

n=4 to n=1

32.21

n=4 to n=1

32.37

n=4 to n=1

CLASS ACTIVITY
1. Work out the difference in frequency

() between successive lines in the

Lyman Series for hydrogen.
2. Plot a graph of (vertically)
against frequency, . (Use the value
of the lower frequency for plotting
.)
3. Use your graph to estimate the
frequency when becomes 0.

 becomes 0 when difference in

energy between the electronic
energy levels becomes 0. Use the
relationship E=h to find the energy
which corresponds to the frequency
when becomes 0. This energy is
the ionisation energy (ionisation
enthalpy) for hydrogen.

4.

An accurate value for the frequency

at the convergence limit for
hydrogen is 32.7 x 1014 Hz. Using
E=h, the energy of radiation with
this frequency
= 4 x 10-13 x 32.7 x 1014 kJmol-1
= 1308 kJmol-1

Using ionisation energies to predict

electronic structures- evidence for shells

If an atom containing
several electrons is
provided with sufficient
energy it will lose one
electron. Additional
supplies of energy will
result in the removal of a

A succession of ionisations is therefore possible, each of

which has its associated ionisation energy. For example,
the first ionisation energy of sodium corresponds to
Na(g) ------> Na+(g) + eH = +494kJmol-1
Whereas the second ionisation energy of sodium
corresponds to
Na(g) ------> Na+(g) + eH = +4564kJmol-1
(see page 67 of chemistry in context)

Electrons occupy atomic orbitals in pairs.

In each pair, the electrons are spinning in

opposite directions.
Chemist believe that paired electrons can only
be stable when they spin in opposite
directions so that the magnetic attraction
which results from their opposite spins can
counterbalance the electrical repulsion which
results from their identical negative charges.

Evidence for sub-shells of electrons

By studying ionisation energies and atomic

spectra, scientists have concluded that:

the n=1 shell can have 2 electrons in the
same sub-level (sub-shell)
the n=2 shell can have 2 electrons in one sublevel, and 6 electrons in a slightly higher sublevel.
the n=3 shell can have 2 electrons in one sublevel, 6 electrons in a slightly higher sub-level
and 10 electrons in a still slightly higher sublevel

Evidence for sub-shells of electrons

(Continuation)

The n =4 shell can have 2

electrons in one sub-level,

6 electrons in a still slightly
higher sub-level, 10
electrons in a still slightly
higher sub-level, and 14
electrons in a still slightly

Evidence for sub-shells of electrons

(continuation)
The sub-shells (or sub-levels) containing 2
electrons are called s sub-shells (s electrons).
The sub-shells (or sub-levels) containing 6
electrons are called p sub-shells (p electrons).
The sub-shells (or sub-levels) containing 10
electrons are called d sub-shells (d electrons).
The sub-shells (or sub-levels) containing 14
electrons are called f sub-shells (f electrons)

When energy sub-levels are being filled,

electrons always occupy the lowest available
energy sub-level first and the electrons pairup as soon as each sub-level is filled.
The electron structure of an atom can be
described in terms of its sub-shells occupied
by electrons . A number (1, 2, 3, 4 etc.) is
used to denote the quantum shell, a letter (s,
p, d or f) to denote the sub-shell and a
superscript to indicate the number of
electrons in the sub- shell.

Electron Configuration
The electronic structure for argon can be
written in terms of energy levels as
2,8,8; and more precisely in terms of
energy sub-shells as 1s2 , 2s2 , 2p6 , 3s2
, 3p6
Note: The 4s sub-shell is lower in energy
than the 3d sub-shell and thus is
occupied first.

Electron Configuration
Calcium, with 20 electrons, would be:

1s2 , 2s2 , 2p6 , 3s2 , 3p6 , 4s2

Sometimes it simplifies things to refer back
to the previous noble gas structure. So the
electron arrangement of calcium, Ca, could
be written
[Ar] 4s2 as a shorthand for 1s2 , 2s2 , 2p6 ,
3s2 , 3p6 , 4s2 , since 1s2 , 2s2 , 2p6 , 3s2 ,
3p6 is the electron arrangement of argon.

The filling of the 3d subshells is very important in

chemistry of the elements
from Sc to Zn. These are
known as the transition
elements (commonly
referred to as the d-block

Electrons and orbitals

Orbitals are regions in which there is the
greatest probability of finding particular
electrons, although the electrons are
not confined to these regions.
Each orbital can hold either one or a
maximum of two electrons. If the orbital
contains two paired-up electrons they
will be spinning in opposite directions.

Electrons and Orbitals

The following simple rules are followed when
writing electronic configuration:
1. Aufbau principle: Orbitals are filled so that
those of lowest energy are filled first.
(Aufbau is German for building up.)
2. Pauli exclusion principle: no two electrons
in an atom can have the same four quantum
numbers. In other words, only two electrons
may occupy the same atomic orbital, and
these must have opposite spins.

Electrons and Orbitals

3. Hunds rule: When we come to orbitals of
equal energy (degenerate orbitals) such as
the p orbitals, we add one electron with their
spins unpaired until each of the degenerate
orbitals contains one electron. (This allows the
electrons, which repel each other, to be
farther apart.) Then we begin adding a second
electron to each degenerate orbital so that
the spins are paired.