Atomic Structure

Objectives

► discuss the process of theoretical change with respect to Dalton’s atomic

theory;

► describe the structure of the atom;

► define mass number, isotopic and relative atomic and isotopic masses;

► explain the phenomenon of radioactivity;

► cite the use of radioisotopes

Objectives

► explain how data from emission spectra provide evidence for discrete energy
levels within the atom;
► describe the atomic orbital;
► describe the shapes of the s and p orbitals;
► determine the electronic configuration of atoms and ions in terms of s, p,
and d orbitals;
► derive the electronic configuration of an element from data on successive
ionisation energies;
► state the factors which influence the first ionisation energy of elements;
► explain how ionisation energy data provide evidence for sub-shells.
Dalton Atomic Theory

Dalton's atomic theory was the first complete attempt to describe all
matter in terms of atoms and their properties.
The postulates of Dalton's atomic theory are:

1. all matter is made of atoms, which are indivisible.

2. all atoms of a given element are identical in mass and properties.
3. atoms of different elements have different masses.
4. compounds are combinations of two or more different types of
atoms.
Modifications

Parts of the theory had to be modified based of scientific evidence later

discovered by other scientist.
1. Matter is made up of small indivisible particles called atoms: Atoms
can, however, no longer be regarded as indivisible because according
to Rutherford's discovery, atoms are made up of three main subatomic
particles called protons, neutrons and electrons.
2. Atoms of the same elements are alike in every aspect and differ from
atoms of all other elements: The discovery of isotopes contradicts this
statement. It has shown that all atom of an element are not exactly
alike in all aspects. Example Carbon 12 and Carbon 14
3. Some atoms have the same mass number. The mass number for Argon
is 40 and the mass number of calcium is also 40. Isobars of different
chemical elements have different atomic number but have the same
mass number.
4. Atoms cannot be created or destroyed: This statement is still
acceptable for ordinary chemical reaction but the discovery of
radioactivity has shown that atoms can be created or destroyed.
Sub-Atomic Particles

Atoms are made up of three fundamental particles:

1. Protons
2. Neutrons
3. Electrons
Protons and neutrons are found in the nucleus and are collectively called
nucleons.
Electrons orbit the nucleus in a similar way to that in which planets orbit a
sun.
 Mass and Charges of Sub-Atomic
Particles
Particle Charge Mass

Proton +1 unit Approx 1 unit

Neutron No charge Approx 1 unit

Electron -1 unit Approx 1/1840 units (very small)

► https://www.youtube.com/watch?v=BDtnSUL2Q7o
Definitions

► Atomic Number (Z) – Number of protons in the nucleus

► Mass Number (A) – The sum of neutrons and protons in the nucleus of the
atom
► Isotope – Atoms with the same atomic number but different mass numbers
► Relative atomic mass – Mass of an atom compared to one twelfth the mass
of a carbon-12 isotope
► Relative molecular mass – Ratio of the average mass of that molecule to
1/12th of the mass of an atom of carbon-12
► Relative isotopic mass – Mass of a single isotope compared to one twelfth
the mass of a carbon-12 isotope
Relative Atomic Mass (RAM)

Thus the relative atomic mass of the element can be calculated from its
mass spectrum.
► An example of a simple mass spectrum is shown
Mass
spectrum of Ne
Calculating relative atomic
masses

The relative atomic mass can be calculated by the formula:

Σ (percentage abundance of each isotope x mass of each isotope)
100

Mass Spectrum of Ne
Using the mass spectrum of neon:

► RAM = (90 x 20 + 10 x 22)/100 = 20.2

Calculating relative atomic mass

Calculate the relative atomic mass of chlorine from the data below

Isotope Relative Isotopic Fractional Abundance

Mass
Cl – 35 34.97 0.7533
Cl – 37 36.95 0.2447

Answer: 35.45
Calculating relative atomic mass

Calculate the relative atomic mass of boron given that its two isotopes B –
10 and B – 11 have relative abundances of 18.7% and 81.3% respectively.
Calculating relative atomic mass

The table below gives the relative abundance of each isotope in a mass
spectrum of a sample of magnesium. Use the data to calculate the relative
atomic mass of this sample of magnesium.

m/z 24 25 26
Relative 73.5 10.1 16.4
abundance (%)
Calculating relative atomic mass

Sulphur consists of three isotopes. The table below shows the relative
abundance of each isotope. Using the data calculate the relative atomic
mass, Ar of sulphur, giving your final answer to 1 decimal place

Mass number of 32 33 34
isotope
Relative 95.0 0.8 4.2
abundance/%
Radioactivity
What is it?

► Spontaneous emission of radiation

► Henri Bacquerel won the Nobel Prize for Physics in 1903 for him
discovery of radioactivity.
► Ernest Rutherford revealed alpha, beta and gamma as the types of
radiation.
► Isotopes of some elements have nuclei which breakdown (decay)
spontaneously
► They are described as radioactive isotopes
► As the nuclei breaks down, radiation/emissions are given off
 Penetrating Ionising
Symbol Range in air
power power

< 5 centimetre
Alpha α Skin/paper High
(cm)

3 mm aluminium
Beta β Low ≈ 1 metre (m)
foil

Gamma γ Lead/concrete Very low > 1 kilometre (km)

Radioactive Emission in Electric Field

► Alpha particles will move to the

negative plate
► Beta particles will move to the
positive plate because they are like
high speed electrons
► Gamma rays will not be attracted
and will move through the electric
field as they have no charge.
Radioactivity and Nuclear Reactions
Detecting Radioactivity

► All types of radioactive decay can be detected by a Geiger-Muller

tube, or G-M tube. The radiations ionise the gas inside and the
resulting charged particles move across the chamber and get counted
as charges rather like an ammeter.
Uses of Radioisotopes

► Carbon-14 Dating
► Medical Applications
► Radioactive Tracers
► Food irradiation
► Energy Generation
Neutron–proton ratio (N/P ratio)

► Neutron–proton ratio (N/P ratio or nuclear ratio)

of an atomic nucleus is the ratio of its number of
neutrons to its number of protons.
► As atomic number increases the N/P ratio must
increase to keep the atom state. However this is not
always enough.
► Nuclei above the band of stability, those which
have a high N/P ratio emit beta particles and
thereby increase the number of protons in the
nucleus
► Heavy nuclei above atomic number 84, emit
alpha particles to decrease both the number of
neutron and protons
 Arrangement of
Electrons in the Atom
Atomic Emission

► When atoms are excited (given extra energy) they emit light of certain
wavelength.
► Evidence for the arrangement of electrons in the atom comes mainly
from atomic spectra
► The observed spectrum is called an atomic emission spectrum or line
spectrum
► Each element produces a completely individual pattern of lines which
can be used to identify it.
► Emission patterns for elements get more complex as the elements get
heavier
Atomic Emission Spectrum

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Introductory_Chemistry_(CK-12)/05%3A_Electrons_in_Atoms/5.05%3A_Ato
mic_Emission_Spectra
Hydrogen Emission Spectrum

► Within each series of lines in the hydrogen emission spectrum, you will
notice that the lines become increasingly closely spaced until they
converge towards the high frequency end of the spectrum

► Rutherford’s model of the atom could not explain the existence of

spectral lines.
► Neil Bohr, a Danish scientist was able to interpret the lines.
The Bohr Model of the Atom

► Bohr started with Rutherford's idea of electrons moving in circular path

around the nucleus.
► The problem with this model however was the fact that an electrically
charged particle that moving a circular path should continuously lose
energy by admitting electromagnetic radiation.
► As the electron lose energy it should spiral into the nucleus. To
overcome this problem Bohr adapted the idea that energy is
quantized.
► He proposed that only orbits of certain radii corresponding to definite
energies are allowed. Thus an electron in an specific orbit has a specific
energy and is said to be in an ‘allowed’ energy state.
The Bohr Model of the Atom

► The energy levels get closer together towards the

outside of the atom. This is mirrored by the spectral
lines getting closer together.
► In the Bohr model of the hydrogen atom shown
opposite, a quantum of energy moves the hydrogen
electron in the n = 1 level (ground state) to the n = 2
level.
► A further quantum of energy will excite the electron to
the n = 3 level. The more energy an electron has, the
higher the energy level it will be in.
► When the electron loses energy, it will fall down to the
lower energy levels, emitting radiation of characteristic
frequencies.
The principal quantum number

► n is the principal quantum number.

► It is an integer and have values from 1 to infinity.
► Each orbit corresponds to a different value of n and the radius of the
orbit gets larger as n increases.
► The lowest energy state (n = 1) is called the ground state of the
atom.
► When the electron is in a higher energy state the atom is in an excited
state
 Explaining the Line Spectrum of
Hydrogen

► The lines in the spectrum arise as electrons move from orbits of high
quantum to orbits of lower quantum number
► The Lyman series arises when an electron moves to the n = 1 orbit
(ground state) from any of the other orbit
► The Balmer series arises when there is a transition to the n = 2 orbit
from the higher orbit
► In each series as the frequency increases the lines get closer together.
► When the lines in the spectrum converge it means that the atom has
ionized.
 Explaining the Line Spectrum of
Hydrogen

► The energy associated with each

line is found by using the
relationship ΔE = hν.
E – energy, h – Planks Constant
v - frequency
► The greater the frequency (the
smaller the wavelength), the more
energy is released.
► The point where the lines
eventually come together is called
the convergence limit.
Electronic Structure

ENERGY LEVELS
► Electrons do not orbit the nucleus randomly; they occupy certain
fixed energy levels.
► Each atom has its own unique set of energy levels, which are
difficult to calculate but which depend on the number of protons
and electrons in the atom.
► Energy levels in an atom can be numbered 1,2,3, etc.
► 1 is the lowest energy level (closest to the nucleus)
Orbitals and Subshells
► Electrons do not in fact orbit the nucleus in an orderly way.
► They occupy areas of space known as orbitals.
► The exact position of an electron within an orbital is impossible to
imagine; an orbital is simply an area of space in which there is a high
probability of finding an electron.
► Orbitals can have a number of different shapes.
► The most common of which are as follows:
1. s orbital - these are spherical and have no preferred direction.
2. p orbital - these are shaped like a 3D figure of eight. They are no
symmetrical. The probability of finding an electron is concentrated.
There are three p orbitals
Atomic Orbitals Video

► https://www.youtube.com/watch?v=6jKTbT81jY8&list=PL9IouNCPbCxXq
cP3rJvu4_IqOf1Z_fWDJ
 The Electronic Configuration Of
Atoms
There are three rules which determine the way in which electrons fill the
orbitals
1. Aufbau/building principle: electrons always fill the lowest energy
orbitals first.
2. Hund's rule: electrons never pair up in the same orbital until all
orbitals of the same energy are singly occupied, and all unpaired
electrons have parallel spin.
3. Pauli exclusion principle: only two electrons may occupy the same
orbital, and they must do so with opposite spin.
The arrangement of electrons in an atom is known as its electronic
configuration.
The Electronic Configuration Of
Atoms

It can be represented in two ways:

1. The arrow and box method represents each orbital as a box and each
electron as an arrow. The direction of spin is shown by the orientation of
the arrow.

2. The orbital method indicates the number of electrons in each orbital

with a superscript written immediately after the orbital
Oxygen - 1s2 2s2 2p4 or 1s2 2s2 2px2 2py1 2pz1
The Electronic Configuration Of Ions

The electronic configuration of ions can be

deduced by simply adding or removing the
appropriate number of electrons. The order in
which electrons are to be removed can be
deduced from the following rules:
► remove outer shell electrons first
► remove p-electrons first, then s-electrons
and then d-electrons
► remove paired electrons before unpaired
electrons in the same sub-level
EC video

► https://www.youtube.com/watch?v=9ogq50CBgCg&list=PL9IouNCPbCx
XqcP3rJvu4_IqOf1Z_fWDJ&index=2
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qcP3rJvu4_IqOf1Z_fWDJ&index=3
Ionization Energies
First Ionisation Energy

The first ionisation energy of an element is the energy required to remove

one electron from each of a mole of free gaseous atoms of that element.
M(g) 🡪 M+(g) + e
► The state symbols - (g) - are essential. When we are talking about
ionisation energies, everything must be present in the gas state.
► Ionisation 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 a first ionisation energy
Trends

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

repetitive way as you move through the Periodic Table.
Trends

► Increases across a period

► Reason - the nuclear charge
increases but the shielding remains
the same.
► Decreases down a group
► Reason - on descending a group,
the effective nuclear charge stays
the same but the number of inner
shells increases.
► The repulsion between these inner
shells and the outer electrons
makes them less stable, pushes
them further from the nucleus and
makes them easier to remove
Factors Affecting Ionisation Energy

When considering trends in ionisation energies, it is thus necessary to

consider 4 factors:

1. Nuclear charge
2. Shielding
3. effective nuclear charge
4. electron repulsion
Nuclear Charge

► Energy is required to remove electrons from atoms in order to

overcome their attraction to the nucleus.
► The greater the number of protons, the greater the attraction of the
electrons to the nucleus and the harder it is to remove the electrons.
► The number of protons in the nucleus is known as the nuclear charge.
Shielding

► The effect of this nuclear charge, however, is cancelled out to some

extent by the other electrons in the atom.
► Each inner shell and inner sub-shell electron effectively cancels out one
unit of charge from the nucleus.
► This is known as shielding.
Effective Nuclear Charge

► The outermost electrons in the atom thus only feel the residual positive
charge after all inner shell and inner sub-shell electrons have cancelled
out much of the nuclear charge.
► This residual positive charge is known as the effective nuclear
charge.
Repulsion

► Electrons repel each other, particularly when they are in the same
orbital.
► The degree of repulsion between the outermost electrons affects the
ease with which electrons can be moved.
Ionization Energy Video

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qcP3rJvu4_IqOf1Z_fWDJ&index=8
► https://www.youtube.com/watch?v=NTH9J_hlAVI&list=PL9IouNCPbCxXq
cP3rJvu4_IqOf1Z_fWDJ&index=10
► https://www.youtube.com/watch?v=1O-BuIf7Zqs&list=PL9IouNCPbCxXq
cP3rJvu4_IqOf1Z_fWDJ&index=11