IB CHEMISTRY

Topic 2 Atomic structure

Higher level
Higher level
 2.1 The nuclear atom
OBJECTIVES

• Atoms contain a positively charged dense nucleus composed

of protons and neutrons (nucleons).
• Negatively charged electrons occupy the space outside the
nucleus.
• The mass spectrometer is used to determine the relative
atomic mass of an element from its isotopic composition.
• Use of the nuclear symbol notation to deduce the number
of protons, neutrons and electrons in atoms and ions.
• Calculations involving non-integer relative atomic masses
and abundance of isotopes from given data, including mass
spectra.
 Atomic Structure
Atoms are very small ~ 10-10 metres
All atoms are made up of three sub-atomic particles:
protons, neutrons, and electrons

Label this diagram:

• The protons and neutrons form a small positively charged

nucleus
• The electrons are in energy levels outside the nucleus
 Subatomic particles
• The actual values of the masses and charges of the sub-atomic
particles are shown in your data booklet:

• A meaningful way to consider the masses of the sub-atomic

particles is to use relative masses
• Element (X)

• Atomic number (Z) is the number of protons in the nucleus of an

atom. It is also known as the proton number. No. of protons
always equals the no. of electrons in any neutral atom of an
element.

• Mass number (A) is the sum of the number of protons and the
number of neutrons in the nucleus of an atom. Some periodic
tables have Z above A. Remember A will always be the biggest
number.
Problem:
Calculate the number of protons and neutrons in:

Z = number of protons = 17 protons

A = number of protons and neutrons = 35
Number of neutrons = A - Z= 35 - 17 = 18 neutrons
 Isotopes
Isotopes are atoms of the same element with the same atomic
number, but different mass numbers, i.e. they have different
numbers of neutrons.

Each atom of chlorine contains

the following:

35 Cl Cl37
17 17

17 protons 17 protons
17 electrons 17 electrons
18 neutrons 20 neutrons

The isotopes of chlorine are often referred to as chlorine-35 and chlorine-37

Some Isotopes of Carbon
 Properties of isotopes
• Isotopes of an element have the same chemical
properties because they have the same number of
electrons. When a chemical reaction takes place, it is
the electrons that are involved in the reactions.
• However isotopes of an element have the slightly
different physical properties because they have different
numbers of neutrons, hence different masses.
• The isotopes of an element with fewer neutrons will
have:
• Lower masses
• Faster rate of diffusion
• Lower densities
• Lower melting and boiling points
 Radioisotopes
Radioisotopes are isotopes that have unstable nuclei and
therefore emit radiation when they break up.

• Radioisotopes are very useful in society:

– 14C is used in radiocarbon dating14C is used in radiocarbon dating
– Detecting gas leaks
– Industrial quality control
– 60Co is used in radiotherapy

– 131I and 125I are used a medical tracers

– Nuclear power

• Radioisotopes can also be very dangerous to living things:

– Radioactive contamination of the environment
– Radiation poisoning
 Industrial use: detecting blockages in underground
pipes
A radioactive isotope which is a gas gets passed down
the pipe, where it concentrates the blockage is present.
 Industrial use: Quality Control
The radioactive isotope is used as a source of
radiation and the amount penetrating the material
gives a measure of it’s thickness.
 Radiotherapy
A cobalt-60 source can be rotated around the patient. The gamma
rays emitted are focussed on the tumour. Healthy surrounding
tissue receives a much smaller dose. The cells in the tumour are
damaged while surrounding tissue is not.
A radioactive sample can be swallowed. The chemical
chosen will be one that concentrates in a particular area.
For example, cancer of the thyroid can be treated using
iodine-131.
 Mass Spectrometer

When charged particles pass through a magnetic field, the particles are
deflected by the magnetic field, and the amount of deflection depends upon
the mass/charge ratio of the charged particle.
Problem1: Determine the relative atomic mass of boron from
the following spectrograph:
m/z value 11 10
Relative 18.7 81.3
abundance %

Ar of boron = (amu1 x %1) + (amu2 x %2)

total %
= (11 x 18.7) + (10 x 81.3)
(18.7 + 81.3)
= 205.7 + 813
100
Ar = 1018.7 = 10.2
100
Problem 2: A mass spec chart for a sample of neon shows that
it contains 90.9% 20Ne, 0.17% 21Ne, and 8.93% 22Ne. Calculate
the relative atomic mass of neon.

Ar of neon = (amu1 x %1) + (amu2 x %2) + (amu3 x %3)

total %
= (90.9 x 20) + (0.17 x 21) + (8.93 x 22)
100
= 1818 + 3.57 + 196.46
100
Ar = 2018.03 = 20.18
100
 2.2 Electron configuration
OBJECTIVES
• Emission spectra are produced when photons are emitted from atoms as excited electrons return to
a lower energy level.
• The line emission spectrum of hydrogen provides evidence for the existence of electrons in discrete
energy levels, which converge at higher energies.
• The main energy level or shell is given an integer number, n, and can hold a maximum number of
electrons, 2n2.
• A more detailed model of the atom describes the division of the main energy level into s, p, d and f
sub-levels of successively higher energies.
• Sub-levels contain a fixed number of orbitals, regions of space where there is a high probability of
finding an electron.
• Each orbital has a defined energy state for a given electronic configuration and chemical
environment and can hold two electrons of opposite spin.
• Description of the relationship between colour, wavelength, frequency and energy across the
electromagnetic spectrum.
• Distinction between a continuous spectrum and a line spectrum.
• Description of the emission spectrum of the hydrogen atom, including the relationships between the
lines and energy transitions to the first, second and third energy levels.
• Recognition of the shape of an s atomic orbital and the px, py and pz atomic orbitals.
• Application of the Aufbau principle, Hund’s rule and the Pauli exclusion principle to write electron
configurations for atoms and ions up to Z = 36.
 Electromagnetic Spectrum

short long
 Wavelength (λ)
In the data booklet:

E=hν and c=νλ

(where ν is the frequency, and h and c are constants)

( ν is the small greek letter N, not v for velocity, pronounced nu, λ

is pronounced lambda)

• It follows then that the shorter the wavelength, the higher

the frequency of the wave, and the more energy it contains.
 Emission spectra
When electrons are excited to a higher energy
level, and then return to a lower energy level,
they release a photon of a specific energy, as
shown by a specific frequency of light.
 Spectroscopy
Continuous spectrum Emission (line) spectrum

Absorption spectrum
Spectral line series
 Emission Spectrum of Hydrogen - convergence
Electrons moving back to the lowest energy states and over
the longest distances release the highest E (short λ).
In each series the lines converge meaning higher
levels/shells get closer together.
Actual values
 Convergence

Outer shells
become closer
together, so
spectral lines get
closer together –
called convergence.
Spectral fingerprint of the elements
Spectrophotometer with discharge lamps
Periodic table of element emission and
absorption spectra
 Electron Shells
Although simplistic, a useful way to look at shells
is to use the periods in the Periodic table.
 Electron Configuration
• Electrons go in shells or energy levels. The
energy levels are called principle energy
levels, 1 to 4. The maximum number of
electrons an energy level (n) can hold is 2n2.
• The energy levels contain sub-levels.
Principle Maximum Number of
energy number of sub-levels
level electrons
1 2 1 These sub-
levels are
2 8 2 assigned the
letters,
3 18 3 s, p, d, f
4 32 4
 Sublevels
• Each type of sub-level can hold a different
maximum number of electron.
Maximum
Sub-level number of
electrons
s 2
p 6
d 10
f 14
 Electron Configuration
• The energy of the sub-levels increases from
s to p to d to f. The electrons fill up the
lower energy sub-levels first.
 Electron Configuration
• Let’s take a look at the Periodic Table to see
how this fits in.
 (One of these needs to be memorized)

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
 Electron Configuration
• So how do you write it?

1s2 Example
For magnesium:
Number of 1s2, 2s2, 2p6, 3s2
electrons

Energy level
Sub-level
 Electron Configuration
• The electronic configuration follows a pattern – the order
of filling the sub-levels is 1s, 2s, 2p, 3s, 3p…
• After this there is a break in the pattern, as the 4s fills
before 3d (The electrons fill up the lower energy sub-
levels first)
• Taking a look at the table below can you work out why this
is?
• This is because the 4s

sub-level is of
lower energy than the
3d sub-level.
 Electrons and Sub-Levels
Ionisation energy
Energy

4f

4d

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

2p

2s

1s

Distance from nucleus

 Writing Electronic Configurations

• The order in which the energy levels are

filled is called the Aufbau Principle.
• Example (Sodium: 2, 8, 1)
 Writing Electronic Configurations

• There are two exceptions to the Aufbau principle.

• The electronic configurations of chromium and
copper do not follow the pattern – they are
anomalies!
• Chromium – 1s2, 2s2, 2p6, 3s2, 3p6, 3d5, 4s1
• Copper – 1s2, 2s2, 2p6, 3s2. 3p6, 3d10, 4s1
 Writing Electronic Configurations for ions

• When an atom loses or gains electrons to

form an ion, the electronic configuration
changes:
- Positive ions: formed by the loss of e-
1s2 2s2 2p6 3s1  1s2 2s2 2p6

Na atom Na+ ion

- Negative ions: formed by the gain of e-

1s2 2s2 2p4  1s2 2s2 2p5

O atom O- ion
 Writing Electronic Configurations for transition
metals
• With the transition metals it is the 4s
electrons that are lost first when they form
ions:
– Titanium (Ti) - loss of 2 e-
1s2 2s2 2p6 3s2 3p6 3d2 4s2  1s2 2s2 2p6 3s2 3p6 3d2
Ti atom Ti2+ ion

– Chromium (Cr) - loss of 3 e-

1s2 2s2 2p6 3s2 3p6 3d5 4s1  1s2 2s2 2p6 3s2 3p6 3d3
Cr atom Cr3+ ion
Writing Electronic Configurations – Condensed form

• Abbreviations can also be used in electron

configuration for simplicity sake.
– Titanium (Ti):
1s2 2s2 2p6 3s2 3p6 3d2 4s2  Ar] 3d2 4s2 or [Ar] 4s2 3d2

 [Ar] always represents 1s 2

2s2 2p6 3s2 3p6

 Other noble gases in the VIII group of the periodic

table are used as well, such as, [He], [Ar], [Kr], [Xe],
etc.
 Orbitals
• The energy sub levels are made up of orbitals,
each which can hold a maximum of 2 electrons.
• Different sub-levels have different number of
orbitals:

No. of Max. no. of

Sub-level
orbitals electrons
s 1 2
p 3 6
d 5 10
f 7 14
 Energy Levels and Sub-levels
Max. no. of Max. no. of Max. no. of
Main energy
Sub-levels electron pairs in electrons in sub- electrons in main
level sub-level level level
1 s 1 2 2
s 1 2
2 8
p 3 6
s 1 2
3 p 3 6 18
d 5 10
s 1 2
p 3 6
4 32
d 5 10
f 7 14
Shapes of the orbitals
 Orbital diagrams
• Within a sub-level, the electrons occupy orbitals
as unpaired electrons rather than paired electrons
and these all spin in the same direction. (This is
known as Hund’s Rule).
• We use boxes to represent orbitals:

2p  

2s 


Electronic configuration of
1s  
carbon, 1s2, 2s2, 2p2
 Orbital diagrams
• The arrows represent the electrons in the orbitals.
• The direction of arrows indicates the spin of the
electron.
• Paired electrons will have opposite spin, as this
reduces the mutual repulsion between the paired
electrons (This is known as the Pauli exclusion
principle)
Notice how the arrows
2p   in each box of the 1s2
Electron  & 2s2 are opposite
configuration of 2s  which means opposite
carbon: 
 spin
1s
1s2, 2s2, 2p2
Problem: Using boxes to represent orbitals, give the
full electronic configuration of the following atoms:
a) lithium
b) fluorine
c) potassium
d) nitrogen
e) oxygen 2p

2s

1s
 Lithium: 1s2, 2s1 2p

2s 



1s

Fluorine: 1s2, 2s2, 2p5


  

2p



2s



1s
 4s 
Potassium: 1s , 2s , 2p , 3s , 3p , 4s
2 2 6 2 6 1

3p   
3s 
2p   
2s 
1s 

Nitrogen: 1s2, 2s2, 2p3

2p   



2s



1s
Oxygen: 1s2, 2s2, 2p4
2p   



2s



1s
 Orbital diagram review
• Electrons enter the lowest energy orbital available
(Aufbau principle).
• Electrons prefer to occupy orbitals on their own,
spin in the same direction, and only pair up when
no empty orbitals of the same energy are available
(Hund's Rule).
• Paired electrons have the opposite spin
(Pauli exclusion principle).

• In ions, the electrons in the highest energy levels

are lost first, but when losing electrons, electrons
are lost from 4s before 3d (the energy levels are
very close, and when electrons fill them, 4s goes
above 3d).
 12.1 Electrons in atoms

level
Higher level
Higher
OBJECTIVES

• In an emission spectrum, the limit of convergence at higher frequency

corresponds to the first ionization energy.
• Trends in first ionization energy across periods account for the
existence of main energy levels and sub-levels in atoms.
• Successive ionization energy data for an element give information that
shows relations to electron configurations.
• Solving problems using E=hv.
• Calculation of the value of the first ionization energy from spectral
data which gives the wavelength or frequency of the convergence limit.
• Deduction of the group of an element from its successive ionization
energy data.
• Explanation of the trends and discontinuities in first ionization energy
across a period.
 level
Higher level
Ionisation Energy

Higher
• Ionisation of an atom involves the loss of an electron to
form a positive ion.
• The first ionisation energy is defined as the energy
required to remove one mole of electrons from one
mole of atoms of a gaseous element.
• The first ionisation energy of an atom can be
represented by the following general equation:
X(g)  X+ + e- ΔH: +ve
• Since all ionisations requires energy, they are
endothermic processes and have a positive enthalpy
change (ΔH) value.
 level
Higher level
Emission Spectrum and Ionisation Energy

Higher
As the electron moves
to higher energy states,
the spectral lines
converge. The upper
limit of this
convergence is the
amount of energy it
takes to remove the
electron – the
ionization energy (IE).
 level
Higher level
Calculations of IE given ν or λ

Higher
Data booklet:
c = νλ and E = hν

c = speed of light = 3.00x108ms-1

h = Planck’s constant = 6.63x10-34Js
ν = frequency (Hz or s-1) pronounced nu
λ = wavelength (m) pronounced lambda
E = energy (J)
•Problem

level
Higher level
  1: Determine the energy of a photon of
red light given the wavelength is 650nm.

Higher
c = νλ
3.00x108ms-1 = ν x 650 x 10-9m
ν = 4.62x1014/s

E = hν = 6.63x10-34Js x 4.62x1014/s
= 3.06x10-19J
•   2: Determine the first IE of hydrogen given that the shortest-

level
Higher level
Problem
wavelength line in the Lyman series is 91.16nm.

Higher
The shortest wavelength will be line at the convergence and hence
represent the IE. Units are kJ/mol.

c = νλ
3.00x108ms-1 = ν x 91.16 x 10-9m
ν = 3.29x1015/s

E = hν = 6.63x10-34Js x 3.29x1015/s
= 2.18x10-18J

IE = photons/mol x E/photon = 6.02 x 1023 x 2.18x10-18J

= 1312360 J/mol
= 1312 kJ/mol
 level
Higher level
Factors in Ionisation Energy

Higher
• The value of the first ionisation energy
depends upon two main factors:

• The size of the nuclear charge

• The energy of the electron that has been

removed (this depends upon its distance from the
nucleus)
 level
Higher level
• As the size of the nuclear charge increases the force of the
attraction between the negatively charged electrons and

Higher
the positively charged nucleus increases.

Small Large
nuclear
charge
 +
+  nuclear
charge
 
Small force Large force
of attraction of attraction
 
Smaller Greater
ionisation ionisation
energy energy
 level
Higher level
• As the energy of the electron increases, the electron is farther

Higher
away from the nucleus. As a result the force of attraction
between the nucleus and the electron decreases.

Electrons further
Electrons closer to away from positive
positive nucleus + + nucleus
 
Large force of Small force of
attraction attraction
 
Greater Smaller
ionisation ionisation
energy energy
 level
Higher level
IE Trends across a Period

Higher
• Going across a period, the size of the 1st ionisation
energy shows a general increase.
• This is because the electron comes from the same
energy level, but the size of the nuclear charge
increases.

+ +
+ +

Going across a Period

 level
Higher level
IE Trends across a Period

Higher
• The first ionisation of Al is less than that of Mg, despite
the increase in the nuclear charge.
• The reason for this is that the outer electron removed
from Al is in a higher sub-level: the electron removed from
Al is a 3p electron, whereas that removed from Mg is a 3s.
Electronic configuration Ionisation energy/kJ mol-1

Na 1s2, 2s2, 2p6, 3s1 494

Mg 1s2, 2s2, 2p6, 3s2 736

Al 1s2, 2s2, 2p6, 3s2, 3p1 577
Si 1s2, 2s2, 2p6, 3s2, 3p2 786
P 1s2, 2s2, 2p6, 3s2, 3p3 1060
S 1s2, 2s2, 2p6, 3s2, 3p4 1000
Cl 1s2, 2s2, 2p6, 3s2, 3p5 1260
Ar 1s2, 2s2, 2p6, 3s2, 3p6 1520
 level
Higher level
IE Trends across a Period

Higher
• The first ionisation energy of Sulfur is less than that of
Phosphorus, despite the increase in the nuclear charge.
• In both cases the electron removed is from the 3p sub-level.
However the 3p electron removed from Sulfur is a paired
electron, whereas the 3p electron removed from Phosphorus is
an unpaired electron.
• When the electrons are paired the extra mutual repulsion
results in less energy being required to remove an electron,
hence a reduction in the ionisation energy.

Phosphorus Sulphur
3p    3p   
3s  3s 
 level
Higher level
Higher
• Now take a look at the graph below:

a) Explain what the graph shows in as much detail as possible

b) There is one other break in the general pattern going across a
Period. What is it and explain why that is.
 level
Higher level
IE Trends down a Group

Higher
+
• Ionisation energy decreases going down
a Group.
• Going down a Group in the Periodic
+
Table, the electron removed during the
first ionisation is from a higher energy

Down the Group

level and hence it is further from the
nucleus. +
• The nuclear charge also increases, but
the effect of the increased nuclear
charge is reduced by the inner electrons
which shield the outer electrons.
+
 level
Higher level
Successive Ionisation energy

Higher
Definition: 2nd i.e.
The energy per mole for the process
X+(g) X2+(g) +e-
And so on for further successive ionisation energies
 level
Higher level
Successive Ionisation energy

Higher
 Successive i.e.’s increases because
electrons are being removed from
increasingly positive ions.

 Therefore, nuclear attraction is greater.

 Large jumps seen when electron is

removed form a new sublevel closer to
the nucleus
 level
Higher level
Successive Ionisation energy

Higher
Succesive ionisation energies of Calcium

6
Large increase between 4th and 3rd
5
shells – electron closer to nucleus

1
2nd i.e. higher than first – electron
has greater pull from nucleus
0
0 2 4 6 8 10 12 14 16 18 20

Nu mb e r o f e le c t ro n re m o v e d