Anusha S.

UNIT 1; MODULE 2: ELECTRONS , BONDING & STRUCTURE

1.2.1 EVIDENCE FOR SHELLS

Ionisation energy

1st ionisation energy is energy required to remove one electron from each atom of
a gaseous mole of atoms to produce one 1 mol of gaseous 1+ ions.
Requires less energy than next IE and is a measure to see how easily an atom
loses an e-
Provides model of atom where there is a nucleus and electrons is shells

Factors affecting ionisation energy

Electrons held in shells by attraction to positive nucleus.

To form positive ion, energy supplied to e - to overcome attraction to nucleus. 1st e-
is easiest to get off from the atom. Successive IEs are stronger.
The nuclear attraction is dependent on 3 factors...
1) Atomic radius; the greater the atomic radius, the smaller the nuclear
attraction on outer e-
2) Nuclear charge; the greater the nuclear charge, the greater the attractive
force on the outer e-
3) E- shielding; inner shells repel outer shell e- so the more inner shells, the
smaller the nuclear attraction experienced by outer e-

Successive IEs

This is the measure of energy required to remove each e- after the first e-.

An element has as many IEs as e- on atom

Each successively increases as there is less repulsion by electrons and nuclear
attraction is stronger and each shell is more drawn to the nucleus.
When the e- is taken from next shell, the IE is much lower, significantly

1.2.2 SHELLS AN D ORBITALS

Energy levels

Successive IE provides evidence for; presence of shells and no of e- in each shell

A shell is a group of orbitals w/ same quantum number n

Atomic orbitals

Its a region w/in an atom that can hold up to 2e- w/ opposite spins.

Each shell is made up of atomic orbitals

4 types of orbitals; s, p, d &f
Orbitals hold 2 e- w/ opposite spins
Electrons have duality of nature meaning they act like a wave and particle at the
same time. We never know the exact location of e- but we can predict it and we
know that it is in the orbital.

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This helps chemists when describing behaviour of atoms and how elements
react but also structure of Periodic Table

1.2.3 SUB-SHELLS AND ENERGY LEVELS

Sub-shells

Is a group of the same type of atomic orbitals w/in a shell

An e- shell is made w/ same q p no n. W/in each shell of same type grouped
together as sub-shell

E energy levels
Filling shells and sub-shells
4f_____ o Ec is arrangement of e- in an atom.
4d_____ Worked out using rules.....
4f______ o E- in shells of atom arranged in as follows
3d____ 1) E- added 1 at a time to build up atom
4s______ 2) Lowest available energy level filled
3p____ first
3s_____ 3) Each energy level must be full before
2p____ filling next one
2s____
1s_____
E-s occupy sub-shells in order of increasing energy levels
o Sub-shell is made up of several orbital, each having same energy level
When sub-shell= built up e-, each orbital filled singly before pairing starts
An orbital can hold a max. Of 2 e- w/ opposite spins
1.2.4 ELECTRONS & THE PERIODIC TABLE
E- Shells overlap
After 3p, need to take care as 4s energy level is below 3d energy level and so fill
before the 3d 4th shell filled 1st before the 3rd shell is completed.
SO: 1s22s22p63s23p64s23d10

Sub-shells and the periodic table

Periodic table links to sub-shells and the pattern mirrors sub-shells being filled

1.2.5 INTRO TO CHEM BONDING

The Noble Gases
Atom= smallest particle of element retaining chem. Properties
With noble gases all e- paired w/ opposite spins & outer shells has 2 e - (only He)/8 e-
(everything else)

Outer shell w/ 8 e- = v stable making noble gases v/ unreactive.

It is a model for the Octet Rule BUT other orbitals can be used for bonding s & p
orbitals= perhaps most important esp. for formation of components involving 1 st
18 elements
Bonding
o Noble gases are the only atoms w/ 8 e- in outer shell. These atoms particularly
stable and exist on their own. Other elements; atoms combine so each atom
has 8 e- in outer shell

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o Unpaired e- pair up sharing/transferring e- to form chemical bond and the result

is each atom has e- c of noble gas

Chemical Bonding
Its classified into 3 main types; covalent, ionic and metallic.
A compound formed when atoms of dif elements are in same proportions
Ionic bonding
Occurs in metal and non-metal compounds
If imagined bond formed between atoms, e - is transferred from metal non metal
Forms oppositely charged ions that attract
Covalent Bonding
Is in compounds of 2 non-metals where the e- s shared between the atoms (e.g. O2 ,
H2, H20 & C)
Metallic Bonding
Is in metals where the e- is shared between all atoms
Noble Gas Uses Unreactivity
He used in airships No known compounds
Ne in advancing signs have He/Ne in them
Ar for filament light Compounds of Ar, Xe
bulbs and Kr have been
Kr for lasers in eye made but w/ great
surgery difficulties

1.2.6 IONIC BONDING

Ionic Bonds
o Present in metal and non-metal compounds
o Metal ion is positive and the non-metal ion is negative
o Dot and cross diagrams show this where one is . and the other is x

For Na2O for

K2O
One e- transferred from 2 Na atoms to 1 O2 atom
2 Na 2Na++2e-
1s 2s 2p 3s 1s2 2s22p6
2 2 6 1

O +2e- O2-
1s 2s 2p 1s2 2s22p6
2 2 4

Giant Ionic Lattice

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Each ion in ionic bond is surrounded by oppositely-charged ions and these attract
from all directions and this forms a giant ionic lattice
All ionic compounds exist as giant ionic lattices in solid state
Repulsions are on diagonals whereas attraction is closer on horizontal &
verticals which gives closer attraction which outweighs the repulsions and this
causes the bonds to be very strong

1.2.7 IONS & THE PERIODIC TABLE

Predicting ionic charges
Can predict charges on ion from element in PT
Can find out elements e- so can calculate how many needed to drop or gain to
reach noble gas e.c.
Metals in Grp 1-3: lose e- forming +vely charged ions
Metals in Grp 5-7: gain e- as
Atoms of Be B C and S dont usually form ions as there is too much energy
needed to transfer outer-shell e- to make ion

Some elements form 1+ ions with different charges and this can depend on
oxidation number of the element
Molecular ions
Groups of covalent bonded atoms can also lose/gain electrons to form ions called
molecular ions
Need to know!!!
1+= NH4+ - Ammonium
1- = OH- ; nitrate NO3-; nitrite NO2- ; hydrocarbonate HCO3-
2- = carbonate CO32-; sulphate SO42- ; sulphite SO32- ; dichromate Cr2O7
3- = phosphate PO43-

1.2.8 COVALENT BONDING

Covalent bonding
Bond formed by a shared pair of e-
Occurs in most non-metal compounds
E- pair occupies space between 2 atoms nuclei
-vely charged e- attracted to positive charges of both nuclei attraction overcomes
repulsion between the 2 nuclei resulting attraction is covalent bonding holding the 2
atoms together
Is in contrast to ionic bonds transferring; shared instead
Single covalent bonds
H2 is formed by 2 H atoms which each have an e- on outer shell so each contributes their
electron to the covalent bond.
Or in Cl2, where each contributes 1 e- from
Lone Pairs
the 7 e-s.
o In covalent bonds, the e- pair shared between the 2 atoms
bonding them together but sometimes the pair is not used
in bonding this is known as a lone pair.
o In NH3 and H2O where the ammonia molecule has 1 lone
pair and the water has 2 on the oxygen

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o Gives a concentrated region of negative charge around the

atom which can influence chemistry of the molecule in
several ways; (covered later on)
Multiple covalent bonds
Some non-metallic atoms can share more than one pair of electrons to form multiple
bonds = sharing.

1.2.9 FURTHER COVALENT BONDING

Dative covalent bonding
Is when the covalent bond is formed by one atom donating both electrons in the bond
to the other atom. This is called a dative covalent bond written as A B
In dative covalent bond, 1 atom provides both e - from the lone pair but when formed, it
has the same appearance of all other covalent bonds

How many covalent bonds?

When covalent bonds form, e- pair pairs up so bonded atom can get e.c. of noble gas
obeying Octet Rule, but sometimes:
1) There may be more than 4 e- pairing up during bonding where this is expansion if
the octet
2) There may not be enough e- to reach octet

(1) When there are more than 4 pairs bonded together expansion of octet
For elements in group 5-7, there are more electrons on outer shell able to take
part in bonding so one atom may end up with more than 8 electrons in the shell.
This breaks the Octet Rule.

(2)When there is not enough to reach an octet

Within group 2, Beryllium and B form compounds w/ covalent bonds but dont
have enough electrons to reach the e.c. of a noble as but can pair up with other
paired electrons.

A better rule
A better rule would be that: unpaired e- pair up and the max number of electrons
that can pair up is the number of e - in the outer shell.

1.2.10 SHAPED OF MOLECULES AND IONS

Electron-pair Repulsion Theory
Shape of the molecule/ion determined by no. of e - pairs in the outer shell
surrounding the central atom
Electrons give a negative charge and each e - pair repels each other, trying to push
one another as far apart as possible.
Molecules w/ bonded Pairs
Molecules have different shapes when they have a different no. o bonded e - pairs
around the central atom where the shapes and bond angles = repulsion of
bonded pairs and each bonded e- pair repels each other as far as possible

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The resulting shapes may be 3D:

The next page

Molecules with lone pairs

Lone e- pairs are slightly more edense that bonded pair
where relative strength of repulsion =
Lone pair| Lone pair < lone pair| bonded atom < bonded
pair| bonded pair.
Each lone pair reduces bond angle by 2.5o so there
is extra repulsive effect of each lone pair
Molecules with Double bonds
Double bonds have 4 e- as there are 2 bonded pairs.
Same as when working with single bonds but there is
2X more effect than the single-bonded atoms.

1.2.11 ELECTRONEGATIVITY AND

POLARITY
Polar and Non-Polar Bonds
Covalent bond is a shared e- pair. Each nucleus of each
atom is attracted to the pair.
H-H is non-polar where the electrons are evenly
distributed between atoms in the made bon.
If bonding atoms are different, it is likely that one atom
has a higher attraction to the e- pair and so one atom is
more electronegative than the other.
Electronegativity: measure of attraction of one atom for
the bonded e- pair in a covalent bond.
The charge difference called permanent dipole: small
charge difference across the bond which is the
difference in electronegativities of bonded atoms
Polar molecules
A polar molecule: has overall dipole, when any dipoles
across bonds are taken into account
Molecules that have polar bonds are made up of polar
molecules such as HCl where there is no symmetry so
there is a charge difference across the bond and whole
molecule.
For symmetrical molecules, dipoles of any bonds w/in
the molecule may cancel out.
E.g.) CCl4: it is non-polar but has polar bonds as each C-Cl bond is polar, BUT CCl 4
molecule- symmetrical and so dipoles cancel each other out and so, CCl4 is a
non-polar molecule with polar bonds.

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How is electronegativity measured?

Pauling scale invented to measure en of an atom. Electronegativity increases as

the periodic table goes up and right where F has the most electronegative
atoms.

Electronegativity & bonding type

Bonding between atoms of two different elements with a small difference in

electronegativity. The more en atom will have a little bit more of a share of the
e-s which gives a polar covalent bond.
Bonds with a large difference in en between the 2 atoms of different elements
more en atom effectively takes both e- = gives an ionic bond.
Between 100% ionic and 100% covalent, there are a range of intermediate bonds
with both ionic and covalent contributions.

1.2.12 INTERMOLECULAR FORCES

Strength of bonds and forces

Ionic and covalent bonds are strong

Ionic bonds are held together in a giant ionic lattice so at room temp, its a solid.
The bonds are strong electrostatic attractions between oppositely-charged ions
Covalent bonds hold atoms together sharing e - pair. Many covalent compounds
exist as small molecules and the atoms in the small molecule are bonded v.
strongly together.
Intermolecular forces are really weak when acting between dif. molecules are
much weaker than ionic + covalent bonds. The intermolecular forces are caused
by weak attractive forces between v. small dipoles in dif molecules.
3 common types of intermolecular forces; hydrogen bonds, permanent dipole-
dipole forces; van der Waals forces.
Intermolecular force = attractive force between neighbouring molecules
Permanent dipole-dipole forces = weak attractive forces between permanent
dipoles in neighbouring polar molecules.
Van der Waals forces= attractive forces between induced dipoles in neighbouring
molecules.
Permanent dipole-dipole interactions
Polar molecules have permanent dipoles where neighbouring ones are attracted to
each other to form the force.

An example of it in action!
Van der Waals forces
Exists between all molecules, whether polar/non-polar.

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They are weak intermolecular attractions between v. small, temporary dipoles in

neighbouring molecules.
What causes Van Der Waals forces?
Van der Waals forces caused by movement of e - in shells and this movement
unbalances the distribution of charge w/in e - shells
At any moment, there can be instantaneous dipoles across the molecule, which
induces dipoles in neighbouring molecules, which induces more dipoles on more
neighbouring molecules etc.
Small induced dipoles attract on another causing the weak van der Waals forces.

Van der Waals forces increase as e- increases. The greater no. of e-, the larger the
induced dipoles, the greater the attractive forces between molecules, which are
the van der Waals forces.
Boiling points and van der Waals forces
Van der Waals forces are only attractive intermolecular forces acting between
non-polar molecules.
As no. of electrons increases, van der Waals forces increases causing boiling point
to increase as more energy is required to break the forces.
If there were no van der Waals forces, we could not liquefy noble gases

1.2.13 HYDROGEN BONDING

A hydrogen bond

Its a strong dipole-dipole attraction between electron-deficient hydrogen atom on

1 molecule and a lone pair of e-s on highly electronegative atom.
In H-bond, e- deficient H+ on 1 molecule attracts lone pair on O- or even N- on
different molecule
It occurs between water molecules:

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Note that the lone pair is essential for hydrogen

bonding!
In ice lattice, there is hydrogen bonding holding H-
2O molecules apart where the O in the H 2O has 4

bonds: 2 covalent and 2 H.

The water is in open structures made of rings of 6
O atoms (snow-flake shape)
Almost no. of possible 6-sided arrangements so every snowflake has unique
shape

Special properties of water

H-bond in H2O has strength enough to affect properties in unexpected ways:
1. Ice is less dense than water as it has an open lattice with h-bonds
holding H2O molecules apart whereas when melted, the H-bonds
collapse and the H2O moves closer together so, ice is less dense.
2. It has a relatively high b.p and m.p due to strong H-bonds
between H2O molecules. The H-bonds are extra forces, over & above
van der Waals forces and this has to be overcome to melt/boil H 2O so
H2O has a high b.p and m.p. This would be expected from van der
Waals forces anyways.
3. Other properties include high surface tension and high
viscosity due to intermolecular bonding from H-bonds between H 2O
molecules.

Hydrogen bonding in biological molecules

Is important in organic compounds containing O-H/ N-H bonds/

The H-bonds have many essential roles in biological molecules:
Responsible for shape of many molecules
DNA they are responsible for holding together the double-helix structure.
The h bonds make sure bases link correctly as well

1.2.14 METALLIC BONDING AND STRUCTURE

Metallic bonding and structure

Metallic bonding: electrostatic attraction between metal positive ions and

delocalised electrons.
Giant metallic bonding: 3-d structure of positive ions and delocalised e -
bonded together by strong metallic bonds.
Delocalised e- are shared between 2+ atoms
Atoms in solid metal are held by metallic bonding in metallic bonding,
atoms ionised. The +ve ions occupy fixed lattice & outer-shell e - delocalised
and are shared between all atoms in metallic structure.
The metal is held by attraction between +ve ions and e -
In giant metallic lattice:

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Delocalised e- spread throughout the metallic structure so it is impossible to

know where each e- originated from so charges must overall balance
Giant metallic lattice often referred to as lattice of positive ions fixed in
position surrounded by a sea of e- where these are delocalised and can
more. The model helps us understand electrical conductivity of metal.

Properties of giant metallic lattices

Most metals have high melting and boiling points as the attraction
between the fixed positive ions and the free, delocalised e - are very strong.
This means that a high amount of energy is needed to break the metallic
bonds and dislodge ions from fixed position in lattice.
Good electrical conductivity as there are free-moving delocalised e- that
can move freely w/in the metallic lattice. The metal can conduct electricity
even in its solid state.
They are ductile and malleable, where ductile means that the metal can
be stretched- can be drawn into wire and malleable means that the metal
can be hammered into shape. Many cannot be pressed into shape. The
delocalised e- are mainly responsible as they can move, so the metal can
give to an extent. This allows atom layers to slide past each other easily.

Alloys

Mixture of metals
The metals mix in dif. proportions where positive ions of one element
replace ions of the other(s).
Alloys modify the properties of the metals. Each metal ion will be of a
different size so when some a replaced, the metal becomes more hard
which creates a barrier so, prevents some atoms sliding past each other.

1.2.15 STRUCTURES OF IONIC COMPOUNDS

Giant ionic lattices

Each ion attracts oppositely charged ions from all directions and so, each
are surrounded by the oppositely-charged ions. The attraction creates a
giant ionic lattice
All ionic compounds are in giant ionic lattices in a solid state.

Properties of ionic compounds

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High m.p and b.p as there is a large amount of energy required to break
strong electrostatic forces holding oppositely charged ions in solid lattice.
The greater the charge, the stronger the electrostatic forces between the
ions, the more energy required to break the ionic lattice when melting.
Electric conductivity varies. In a solid state, the ions are fixed and cannot
move and so the ionic compound is non-conductive. However, when melted
or dissolved, the ions are free to move and so, can conduct electricity well.
The ionic lattice is soluble in polar solutions e.g.) H2O. Polar H2O
molecules can break down the lattice, surrounding each ion, forming a
solution
These are Na+ and Cl- surrounded by H2O. The
positive sodium attracts the - of the O in the
water and the Cl- attracts the + charges on
the H-atoms of the water. This is when they are
dissolved and the ionic lattice has broken down.

1.2.16 STRUCTURE OF COVALENT COOMPOUNDS

Types of structure

Elements and compounds w/ covalent bonds either have structure of a simple,

molecular lattice or a giant covalent lattice
Simple molecular structures
Made of small, simple molecules.
In simple molecular lattice, molecules are held together by weak forces
between molecules and the atoms in each molecule which are bonded
strongly by covalent bonds.
Properties of simple molecular structures
Low b.p and melting point as the intermolecular force, van der Waals is
v. weak so not much energy is needed to break them.
Simple molecular structures are non-conductors as there are no free
moving, charged particles.
Simple molecular structures are soluble in non-polar solvents as
there are weak van der Waals forces between the solvent and the
structure.

Giant covalent structure

Diamond and graphite are examples of giant covalent lattice

Properties of giant covalent structures
High b.p and m.p as there is a lot of energy needed to break strong
covalent bonds in lattice
Not good conductor as there are no free charged particles except in
graphite.

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It is insoluble as the covalent bonds in the lattice are too strong to be

broken down by either polar/non-polar solvent

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