Introduction to Atomic Theory

Dr Finn Purcell-Milton (fpurcell@tcd.ie)

Dental Science
29/9/16

Useful texts: Peter Atkins and Loretta Jones, Chemical

Principals- The quest for insight (5th edition)
Lecture Outline

• Structure of the Atom

• Electronic Configuration
• The Periodic Table
• Chemical Bonds
 Definitions
• The atom is the smallest particle of an element that retains the
properties of that element
• An element is a pure chemical substance composed of only one
type of atom

“A Boy and His Atom” the first stop-motion movie

created by IBM using atoms by IBM
 The Structure of the Atom
• The atom is composed of three subatomic
particles : the proton, the neutron and the
electron
• The weight of subatomic particles is measured
Neutron in the atomic mass unit (amu) and is equal to
Proton
1.6605×10−27 kg (very small)
+ • The proton is positively charged and has a mass
of 1 amu
• The neutron has no charge and has a mass of 1
Nucleus amu
- • The electron is negatively charged and has a
mass of 0.0005 amu
• The atom is composed of a positively charge
Electron
centre referred to as the atomic nucleus
composed of either protons or protons and
Name Symbol Charge Mass (amu) neutrons which is surrounded by a cloud of
Proton P+ +1 1 negative charge composed of electrons which
can be found at a set distance from the nucleus.
Neutron n 0 1
• The atom is neutral, therefore the number of
Electron e- -1 0.0005 electrons equals the number of protons present
 The Structure of the Atom
Definition: The number of protons in an
atomic nucleus is called the atomic
Atomic Number (Z) 1 number (Z) of the element. This is
characteristic of a chemical element.
Element Symbol
H Definition: The element symbol is an
Element Name Hydrogen
abbreviation used to denote a chemical
Mass Number or element and is one to two letters long
Atomic Mass (A)
1.008
( except when the name temporary, then
its three) , with only the first letter capital
Examples:
Definition: The mass number or atomic
mass (A) is the total number of protons
and neutrons in a nucleus of an atom.
Helium
Note: the mass number or atomic mass
of an element is the larger number
 The Structure of the Atom
Atomic Number (Z) 1 1 1

Element Symbol
H H H
Element Name Protium Deuterium Tritium
Mass Number or
Atomic Mass (A) 1 2 3

Definition: Atoms with the same

atomic number (Z), but different
atomic mass (A) are termed
isotopes
Therefore isotopes have the
Protium Deuterium Tritium
same number of electrons and
protons but a different
number of neutrons
Chemical character is defined by the number of electrons and protons, isotopes have
little to no effect in chemistry , so lets move onto the electronic structure
 Electronic configuration n=4
n=3
• The electrons occupy the space around the nucleus n=2
and are ordered into shells n=1

• These shells are at various distances from the nucleus,

with n=1 being the closest , like layers of an onion

• The number of electrons which can be present in a

shell increases with distance from nucleus

• The atom’s lowest-energy electrons occupy the 1st

shell (n=1) while the highest-energy electrons are
furthest away from the nucleus Nucleus Electron
shell
• Electrons that occupy the outer shell (remember these
are the furthest from the nucleus and the ones at the
highest energy) are called the Valence Electrons.

• Valence electrons participate in bonding (which we will

talk about later) (quick example: Carbon , 4 outer
electrons, 4 potential bonds)
Electronic configuration: Orbitals
• In each electron shell around the nucleus, electrons arrange into
clouds of probability
• This probability is associated with finding an electron in a particular
location around the nucleus
Definition: An orbital is a region of space where the probability of
finding an electron is large, (~90%)

• Each orbital can fit two s

electrons
p
• Four types of orbitals are
present in atoms : s, p, d
and f d

f
Electronic configuration : Atomic Orbital Shape
s - orbital
s-orbitals
• Spherical in shape
• Holds 2 electrons

pZ - sub orbital
p-orbitals
pZ - sub orbital
px - sub orbital • a cloud with two lobes on opposite
sides of the nucleus.
• the two lobes are separated by a
planar region called a nodal plane
• 3 sub orbitals point along the x, y,
and z axes respectively, and are
denoted px, py and pz
• Holds 6 electrons when full

p - orbital
Electronic configuration : Atomic Orbital Shape

d and f – orbitals
• Shapes become more complex
• d- orbital has 5 sub orbitals, holds 10 electrons
• f- orbital has 7 sub orbitals, holds 14 electrons

f
Electronic configuration: rules for filling Orbitals

Wolfgang Pauli
Friedrich Hund’s

Rule 1: Electrons will occupy the orbital of lowest available energy.

(Aufbau principle)

Rule 2: Each orbital can accommodate a maximum of two electrons. The

two electrons in an orbital must have opposite spins.
(Pauli Exclusion principle)

Rule 3: Electrons must fill orbitals of the same energy singly, before pairing up.
(Hund’s Rule)
Electronic configuration: Orbital Energy
• The energy of different orbitals increase with
increasing shell number
• The energy of orbitals also increases within a
shell in this order s<p<d<f
• This gives an order in which electrons fill into
orbitals
• This gives rise to a complex filling order as we
need to fit larger and larger amounts of
electrons

Area which
this course is
concerned
with
 Electronic configuration: writing it
This is the method to write the x = the shell number
𝑧
electronic configuration for an
element
 
𝑥𝑌 Y = orbital
z = number of electrons

Example 1. Hydrogen is the first

 𝐻 =1 𝑠1
element on the periodic table and has
one electron

Example 2. Helium is the second

element on the periodic table and has  𝐻𝑒=1 𝑠2
two electrons

Example 3. Lithium is the second

 𝐿𝑖=1 𝑠2 2 𝑠 1
element on the periodic table and has
two electrons
 Electronic configuration: writing it

Example 4. Demonstration of Hund’s Rule

Carbon’s atomic number is 6 and so  𝐶=1 𝑠 2 2 𝑠2 2 𝑝2

has 6 electrons

The 2p orbital fills     Correct

up as follows:
1s2 2s2 2p2

and not as:    Incorrect

1s2 2s2 2p2

Writing the configuration to express  𝐶=1 𝑠 2 2 𝑠2 2 𝑝 1𝑥 2 𝑝 1𝑦

filling of the sublevels of the p-orbital
 Increasing energy Electronic configuration: writing it

a) Nitrogen has 7 electrons, electronic configuration: 1s2 2s2 2p3

(b) Magnesium has 12 electrons, electronic configuration: 1s2 2s2 2p6 3s2

(c) Silicon has 14 electrons, electronic configuration: 1s 2 2s2 2p6 3s2 3p2

(d) Chlorine has 17 electrons, electronic configuration: 1s2 2s2 2p6 3s2 3p5

(e) Potassium has 19 electrons, electronic configuration: 1s2 2s2 2p6 3s2 3p6 4s1
 Electronic configuration: writing it
• As shell number increases, the sublevel energies get closer
together. This results in the overlap of some sublevels and this
begins to happen when one starts looking at the elements with
more than 18 electrons
• The 4s orbital is slightly lower in
energy than the 3d orbital,
therefore this is filled first.
Increasing energy

 𝐾 =1 𝑠 2 2 𝑠 2 2 𝑝6 3 𝑠 2 3 𝑝6 4 𝑠 1

• After the 4s orbital, the 3d begins to

be filled

 𝐹𝑒=1 𝑠2 2 𝑠 2 2 𝑝6 3 𝑠 2 3 𝑝 6 4 𝑠 2 3 𝑑 6
 Quick Reminder : The Structure of the Atom

Definition: The number of protons

in an atomic nucleus is called the
Atomic Number (Z) 1
atomic number (Z) of the element.

Element Symbol
H Definition: The element symbol is
Element Name
an abbreviation used to denote a
Hydrogen
chemical element and is one to two
Mass Number or
Atomic Mass (A)
1.008 letters long ( except when the name
temporary, then its three) , with only
the first letter capital
Examples: Definition: The mass number or
atomic mass (A) is the total number
of protons and neutrons in a nucleus
of an atom.
Note: the mass number or atomic
mass of an element is the larger
number
 The Periodic Table: Group Numbers
1

2
numbers
Period

• Elements are ordered by increasing atomic number

• An elements chemical properties can be predicted by its position on the periodic table.
• The number of occupied shells in an atom is given by its period number in the periodic
table.
 The Periodic Table: Group Numbers
Group Numbers

• Elements with the same group number (column) have similar chemical
properties
• Elements within the same group have the same electron configurations
in their valence shell
 The Periodic Table: Orbitals
The periodic table can be broken up into sections based upon the type
of orbital in which its outer most electron occupies (valence electron)
which in fact strongly defines the properties of the specific element

• s-block group includes

the alkaline metals and
the alkaline earth metals
• p-block group includes a
range of non metals,
metalloids and metals
• d-block group covers the
transition metals
• f-block group covers the
lanthanides and
actinides
Compounds and Chemical Reactions
Compounds consists of two or more elements
chemically combined in a defined ratio

Compounds are formed via chemical reactions

Chemical reactions are the processes by which

chemicals interact to form new chemicals with
different compositions

Chemical reactions always involve the breaking

and/or forming of chemical bonds
Chemical Bonds

• In compounds, the attractive forces which hold entities

together are called bonds.

• A chemical bond forms if the resulting arrangement of

atoms has a lower energy than the separate atoms.

• Change in energy during bonding occurs due to the

change in locations of the valence electrons (remember,
the ones in the outermost shell).
• Therefore the electronic configuration is essential to the
understanding of bond formation!

• Chemists generally distinguish between ionic bonds,

covalent bonds and polar covalent bonds.

• But first we need to talk about the Octet Rule

 Chemical Bonds :The Octet Rule
Group 8

• The elements of group 8

have a electronic
configuration in which
they have a full outer
shell
• This group is described as
the noble gases since
they are completely inert
and form nearly no
known compounds

• Octet rule - Atoms react/combine to lower their energy to reach an electron

arrangement with 8e- in their valence shell.
• In other words they all try to reach the electron configuration of a noble gas,
with a full outer shell
 Chemical Bonding:
Electronegativity
Increasing

Electronegativity
values

Increasing
• The power of attraction an atom has for the shared pair of electrons is
called its electronegativity.
• This value increase from left to right on the periodic table due to
increased nuclear charge
• This values also decrease down the periodic table. This because as new
electron shells are filled, they are further away from the nucleus and
also experience a screening effect from inner electrons
 Chemical Bonds: Ionic Bonds

• If
  a neutral atom loses or gains one or more electrons it becomes an ion.
• Atom loses a negatively charged electron, it has an overall positive charge
(called a cation) e.g.
• Atom gains a negatively charged electron, it has an overall negative charge
(called a anion) e.g.
• An Ionic bond is the attraction between the opposite charges of cations
and anions. This force is described as electrostatic which holds the ions
together
• Examples include: NaCl, KBr and Ca(F)2
• Also defined as
“the bond formed by the transfer of electrons from one atom to another
and the consequent attraction between the atoms formed.”
• Ionic bonds are formed when there is large difference between the
electronegativity of the elements reacting (larger than 1.7)
 Chemical Bonds: Ionic Bonds
Formation of Sodium Chloride (Table Salt)

2 2 6 1 2 6
 𝑁𝑎=1 𝑠 2 𝑠 2 𝑝 3 𝑠  𝑁𝑎 2 𝑠 2 𝑝 ¿
¿

− 2 2 6 2 6
𝐶𝑙=1
  𝑠 2 2 𝑠2 2 𝑝 6 3 𝑠2 3 𝑝 5 𝐶𝑙
  =1 𝑠 2 𝑠 2 𝑝 3 𝑠 3 𝑝
 Chemical Bonds: Covalent
Bonds
• Covalent bonds are characterised by the sharing of
electrons between two or more atoms so that the discrete
nature of the atoms is lost.
• Examples : CH4 , N2 , O2 , H2
• Octet rule again: In covalent bond formation, atoms share
electrons completing their octets by sharing electron
pairs, to gain a full electron shell
• For a fully covalent bond to form , the difference in
electronegativity between the elements must be generally
less than 0.4
• Polar covalent bond is characterised as unequal sharing of
Methane electrons between two atoms
• This takes place when the electronegativity difference
between the two atoms is between 0.4 and 1.7
• Examples: H2O and NH3
• This also results in a polar molecule, or in other words a
molecule with an inherent area of partial positive charge
and an area of partial negative charge