CHAPTER 2

ATOMIC STRUCTURE
Wilt Gu
2.1 THE NUCLEAR ATOM
 HISTORY OF DISCOVERY
OF ATOMIC STRUCTURE
 Democritus: Idea of particles called “atom”
 John Dalton: Atomic theory
 J.J. Thomson: Cathode ray tube and discovery of electrons
 Ernest Rutherford: Gold foil experiment and the idea of
nucleus in the center of an atom
 Niels Bohr: Atomic model with energy levels (Shells)
 DALTON’S ATOMIC THEORY
 One of the first great achievements of chemistry was to show that all
matter is built from about 100 elements.
 The elements are substances which cannot be broken down into simpler
components by chemical reactions, so they are the simplest substances and
their names are listed in your IB data booklet (section 5).
 Different elements have different chemical properties but gold foil, for
example, reacts in essentially the same way as a single piece of gold dust.
 Indeed if the gold dust is cut into smaller and smaller pieces, the chemical
properties would remain essentially the same until we reached an atom.
 This is the smallest unit of an element.
 There are only 92 elements which occur naturally on earth and they are
made up from only 92 different types of atom.
 The modern idea of the atom dates from the beginning
of the 19th century.
 John Dalton noticed that the elements hydrogen and
oxygen always combined together in fixed proportions.
To explain this observation he proposed that:
 all matter is composed of tiny indivisible particles called
atoms;
 atoms cannot be created or destroyed;
 atoms of the same element are alike in every way;
 atoms of different elements are different;
 atoms can combine together in small numbers to form
molecules.
 Using this model we can understand how elements react
together to make new substances called compounds.
 The compound water, for example, is formed when two
hydrogen atoms combine with one oxygen atom to
produce one water molecule.
 Dalton was the first person to assign
chemical symbols to the different
elements.
 Challenge yourself:
 It is now known that some of these
substances are not elements but
compounds.
 Lime, for example, is a compound of
calcium and oxygen.
 Can you find any other examples in
this list and explain why the elements
had not been extracted at this time?
John Dalton’s symbols for the
elements.
ATOMS CONTAIN ELECTRONS

 The first indication that atoms were destructible came at

the end of the 19th century when the British scientist J. J.
Thomson discovered that different metals produce a
stream of negatively charged particles when a high
voltage is applied across two electrodes.
 As these particles, which we now know as electrons,
were the same regardless of the metal, he suggested that
they are part of the make-up of all atoms.
 As it was known that the atom had no net charge,
Thomson pictured the atom as a ‘plum pudding’, with the
negatively charged electrons scattered in a positively
charged sponge-like substance.
J.J. Thomson’s Cathode
Ray Tube (CRT)
RUTHERFORD’S MODEL OF THE ATOM
 Ernest Rutherford (1871–1937) and his research team working at
Manchester University in England, tested Thomson’s model by ring alpha
particles at a piece of gold foil.
 We now know that alpha particles are helium nuclei, composed of two
protons and two neutrons, with a positive charge.
 They are emitted by nuclei with too many protons to be stable.
 If Thomson’s model was correct, the alpha particles should either pass
straight through or get stuck in the positive ‘sponge’.
 Most of the alpha particles did indeed pass straight through, but a very
small number were repelled and bounced back. Ernest Rutherford recalled
that ‘It was quite the most incredible thing that has happened to me.
 It was as if you had red a (artillery) shell at a piece of tissue paper and it
came back and hit you.’
 The large number of undeflected particles led to the conclusion that the
atom is mainly empty space.
 Large deflections occur when the positively charged alpha particles
collide with and are repelled by a dense, positively charged centre called
the nucleus.
 The fact that only a small number of alpha particles bounce back suggests
that the nucleus is very small.
Gold Foil
Experiment
Rutherford’s Model
Bohr’s Atomic Model
SUB-ATOMIC PARTICLES

Relative
Particle Where in Atom Relative Mass
Charge

Proton Nucleus 1 +1

Neutron Nucleus 1 0

Electron Orbiting the nucleus 1/1836 -1

SYMBOLS WITH SUPERSCRIPTS &
SUBSCRIPTS

𝐴 11
𝑍 𝑋 5 𝐵
 A: Mass number (nucleon number) – sum of proton number and
neutron number

 Z: Atomic number – proton number

ISOTOPES
Atom Protons Neutrons Electrons Relative Mass
12
6 𝐶 6 6 6 12
13
6 𝐶 6 7 6 13
235
92 𝑈 92 143 92 235
238
92 𝑈 92 146 92 238

 Isotopes: Atoms that have same proton number but different neutron
number.

 Abundance: Mole percentage of one isotope in its whole element in

nature.
Mass spectrometry (MS) is an analytical technique that measures
the mass-to-charge ratio of charged particles.

A mass spectrometer is the instrument which separates particles

according to their masses and records the relative proportions of
these.
A: Convert substance in vapor phase by heating
B: Turn atom/molecules into positive ions by electron bombardment
C: Accelerate positive ions by electrical field
D: Deflect ions by magnetic field: lighter the particle / bigger the charge the greater
the deflection (deflection depends on m/z ratio)
E: Detector record ions of a particular mass: greater the # of particles the greater
the signal
F: High vacuum maintained by a pump preventing sample particles colliding w/
other particle
 RELATIVE ATOMIC MASS (AR)

Relative atomic mass, Ar, is the weighted average of

one atom of an element relative to one-twelfth of an
atom of carbon-12.
Practice:

Calculate the Ar for chlorine.

 RELATIVE ATOMIC MASS OF AN
ELEMENT
Determine the natural abundances of the isotopes of an element and
hence allow calculation of its atomic mass.
Relative Abundance

Practice:

Natural abundances?
Atomic mass?
Solution:
 IONS

 To make atoms neutral, the number of electrons should equal to atomic

number
 But during chemical reactions, electrons could transfer from one to
another to make both atoms become no longer neutral.
 Atoms with charge (by gaining or losing electron(s)) are called ions
EXERCISES ABOUT THE COMPOSITION
OF ELEMENTS

Element Symbol Number of particles Mass Number

Proton Neutron Electron

28
Si 14 14 14 28
52
Cr3+ 24 28 21 52
79_Br - 35 44 36 79

108_ Ag 47 61 47 108
133
Ba2+ 56 77 54 133
261_ Rf 104 157 104 261
2.2 ELECTRON CONFIGURATION
 Atomic Emission Spectra

• The study of the emission of light by atoms and ions is

the most effective technique for deducing the electronic
structure of atoms.

• The best evidence for the fact that e- in an atom

surround the nucleus in certain allowed energy
levels/orbitals comes from the study of the emission
spectra of elements. ---Textbook P54
Flame test
When an element is excited it will often emit light of a
characteristic color.
Or Prism
Each element has its own characteristic line spectrum that can be
used to identify it.
Frequency (ƒ), color of light, depends on the amount of
energy lost (ΔE) by the electron.

Color of light also defined by wavelength (λ),

c = ƒ λ c = 3 × 108 m/s velocity of light
The greater the frequency, the shorter the wavelength.
• By studying the frequencies of the lines in the emission spectrum
of an element, the energies of the various energy levels in its
atoms many be found.

• It is found that the energy levels are not evenly spaced, like the
rungs of a ladder, but that the higher the energy, the smaller the
difference in energy b/w successive energy levels becomes.

This means that the lines in a spectrum will converge (get closer
together) with increasing frequency.

• The limit of this convergence indicate the ionization energy: the

energy required to completely remove the electron from the atom
(to ionize it)
 The Atomic Emission Spectrum of Hydrogen
Simplest emission spectrum, having only one electron, no e -- e- repulsion causing the
principal energy levels to split into different sub-levels.

• Line spectrum,
indicating only
certain allowed e-
E levels exist.

• Convergence in
higher F in
spectrum,
indicating
convergence of
higher E levels
 The reverse: Absorption spectrum

H atom: only Lyman series in UV is observed due to only one e- in n=1 level.
 Electronic Structure of the atom
----The # of electron in each orbital
• Electrons fill from the lowest E level (most stable, closest to the
nucleus) to higher levels.

• There’s a maximum # of e- that each energy level can hold. 2 in 1st

level, 8 in 2nd level, and so on.

• Isotopes have same electronic structure, thus identical chemical

properties.

• The outermost shell, or valence shell determine the physical and

chemical properties of the element. E.g. most elements with 3 valence
e- or less are metals

• Electronic structure of an element is closely related to its position in

the periodic table—memory aid for electronic structure.
 Shells, sub-shells & orbitals

 Electrons are arranged in electrons shells (energy levels).

 The shells have sub-shells (sub-levels).

 Each shell/sub-shell is made up of electron orbitals which can

each hold 2 electrons.
 Orbitals

 Each sub-level consists of electron orbitals (region of

space in which the electron spends most of its time).
 Each orbital can hold 2 electrons with opposite spins
(one electron spins clockwise and one anticlockwise).
(Pauli Exclusion Principle)
 Orbitals are regions of space that electrons are most
likely to be in.
 Orbitals
Maximum
Number of
Sub- number of
orbitals in Shape (no need to learn)
level electrons in
sub-level
sub-level

s 1 2

p 3 6

d 5 10

f 7 Even more complicated! 14

 Ionisation energy
Energy

4f

4d

4p
3d
4s
3p
4s of "lower"
3s energy than 3d

2p

2s

1s

Distance from nucleus

 Aufbau Principle

Electrons enter the lowest energy orbital available.

This diagram helps you to work out the order in which orbitals fill:
1s 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, …..

2s 2p However, it can be easier to read across the periodic table, but remember
that the first transition metal row is 3d:
3s 3p 3d

4s 4p 4d 4f
1s 1s
5s 5p 5d 5f 2s 2p

6s 6p 6d 3s 3p

4s 3d 4p
7s 7p
 Hund’s Rule

Electrons prefer to occupy orbitals on their own, and only pair up

when no empty orbitals of the same energy are available .
e.g. silicon 14 e- 1s2 2s2 2p6 3s2 3p2
Ionisation energy
Energy

4f

4d

4p
3d
4s
3p ↑ ↑
4s of "lower"
3s ↑? energy than 3d

2p ↑? ↑? ↑?

2s ↑?

1s ↑?

Distance from nucleus

e.g. calcium 20 e- 1s2 2s2 2p6 3s2 3p6 4s2
Ionisation energy
Energy

4f

4d

4p
3d
4s ↑?
3p ↑? ↑? ↑?
4s of "lower"
3s ↑? energy than 3d

2p ↑? ↑? ↑?

2s ↑?

1s ↑?

Distance from nucleus

e.g. Ca2+ 18 e- 1s2 2s2 2p6 3s2 3p6

Ionisation energy
Energy

4f

4d

4p
3d
4s
3p ↑? ↑? ↑?
4s of "lower"
3s ↑? energy than 3d

2p ↑? ↑? ↑?

2s ↑?

1s ↑?

Distance from nucleus

 Ions
 The highest energy electrons are lost when an ion is formed.

 Once the 4s and 3d orbitals are occupied, 4s moves above 3d in

energy, the transition metals then lose there ‘s’ electrons before their
‘d’ electrons.
 IONS IN PERIOD 4

 Manganese 2+ would be

1s2 2s2 2p6 3s2 3p6 3d5

 Cu & Cr

 Cu and Cr do not have the expected electron structure.

Cr = 1s2 2s2 2p6 3s2 3p6 4s1 3d5

NOT 1s2 2s2 2p6 3s2 3p6 4s2 3d4

Cu = 1s2 2s2 2p6 3s2 3p6 4s1 3d10

NOT 1s2 2s2 2p6 3s2 3p6 4s2 3d9
 ELECTRONIC CONFIGURATION AND
THE PERIODIC TABLE

 We are now in a position to understand the structure of the Periodic Table:

 elements whose valence electrons occupy an s sub-level make up the s
block;
 elements with valence electrons in p orbitals make up the p block;
 the d block and the f block are similarly made up of elements with outer
electrons in d and f orbitals.
 ELECTRONIC CONFIGURATION AND
THE PERIODIC TABLE

 The position of an element in the Periodic Table is based on the occupied sub-
level of highest energy in the ground-state atom. Conversely, the electron
configuration of an element can be deduced directly from its position in the
Periodic Table.
 Here are some examples.
 Caesium is in Group 1 and Period 6 and has the electronic configuration: [Xe]6s 1.
 Iodine is in Group 17 and in Period 5 and has the configuration: [Kr]5s24d105p5.
 Placing the 4d sub-level before the 5s gives [Kr]4d105s25p5.
12.1 ELECTRONS IN ATOMS
 Ionisation Energy

 Evidence for how the electrons are arranged in atoms

comes from ionisation energies.
 1st ionisation energy = energy required to remove
one electron from each atom in a mole of gaseous
atoms producing one mole of 1+ gaseous ions.
 Note that 2nd ionisation energy is the energy required
to remove the second electron (not both electrons).
e.g. 1st IE of Na: Na(g) → Na+(g) + e–
2nd IE of Na: Na+ (g) → Na2+(g) + e-
 Ionisation Energy

_
e
1) distance from nucleus

+ 3) shielding (repulsion) by electrons

in inner shells between nucleus
2) nuclear charge
and outer electron
 1ST IONISATION ENERGY
(DOWN GROUP)

 Longer distance between nucleus and

outer shell electrons (atoms get bigger)

 Same effective nuclear charge (more

shielding)

 Therefore weaker attraction from nucleus

to electron in outer shell
1ST IONISATION ENERGY (DOWN GROUP)

1000
1st ionisation energy

800

600

400

200

0
Be Mg Ca Sr Ba
1ST IONISATION ENERGY (ACROSS
PERIOD)

General trend

 Increased effective nuclear charge (i.e. more protons)

 Shorter distance between nucleus and outer shell

electrons (atoms get smaller)

 Therefore stronger attraction from nucleus to electron

in outer shell
1ST IONISATION ENERGY (ACROSS PERIOD)
1st ionisation energy (kJ/mol)

1600
1400
1200
1000
800
600
400
200
0
Na Mg Al Si P S Cl Ar
1ST IONISATION ENERGY (ACROSS
PERIOD)
Energy
Group 2 → 3 Ionisation energy

 Electron lost from 4f

4d
Group 3 element is 4p
from p orbital, while 3d
4s
that lost from Group 2 3p
3s
element is from s 2p
orbital. 4s of "lower"
2s energy than 3d

 p orbital is higher
energy than s orbital, so 1s
easier to lose electron.
Distance from nucleus
1ST IONISATION ENERGY (ACROSS
PERIOD)
Group 5 → 6

 Group 6 element loses electron from orbital with 2

electrons (p4   ).
 Group 5 element loses electron from orbital with 1
electron (p3   ).
 Extra electron-electron repulsions make it easier to lose
electron from p4 than p3.
1ST IONISATION ENERGY
SUCCESSIVE IONISATION ENERGIES OF K