Section 2

Atomic Structure
and Bonding
Atomic Structure
Subatomic particles;
Descriptions in terms of s, p, d and f notation for atoms and ions up to 38
electrons;
Make mention of Pauli Exclusion principle, Hund’s rule and the Aufbau building-up
principle;
The absence of 4s electrons in transition metal ions must be noted;
Periodic trends in electronegativity;

Chemical Bonding
Metallic, Ionic and covalent Bonding;
Intermolecular forces;
Four types of solids;
Lewis structures and shapes of molecules and ions;
Examples that break the octet rule are used to demonstrate the concept of an
expanded octet using electrons in d orbitals;

1
The Atom
Atom is considered as the smallest indivisible particle. Atoms are neutral as they contain equal
numbers of protons and electrons. Most of an atom is just empty space as shown by
Rutherford’s model. Almost all of an atom’s mass is contained in the nucleus.

Effect in Electric
Subatomic Particle Mass Charge Found
Field
Proton 1 +1 In the nucleus Deflected

Neutron ≈1 0 In the nucleus Unchanged

Electron 1/1836 -1 Outside the nucleus Greatly deflected

Behaviour of subatomic particles in an electric field:

(a) Different directions of deflection:

(b) Relative extent of deflection:

2
Proton
A particle with positive charge, found in the nucleus of an atom. The number of protons in an
atom is equal to its atomic number.

Electron
A particle with negative charge and almost no mass. Electricity is a flow of electrons.

Neutron
A particle with approximately the same mass as a proton but no charge also found in the
nucleus.

Atomic number (Z)

The atomic number gives both its position on the periodic table and the number of protons in
the nucleus. In a neutral atom the atomic number also equals the number of electrons outside
the nucleus.

Mass number (A)

The total number of protons and neutrons in the nucleus.

The symbol for an atom of an element show mass number at the top left and atomic number at
the bottom left of the symbol of the element.

The number of neutrons can be calculated by subtracting Z from A. So, n=A–Z or n=m–p

(a) For an atom: Z = p = e;

(b) For an ion: Z = p, and e = p – the charge on the ion

e.g. 23Na: p = e = 11; n = 23 – 11 = 12

e.g. 31P3− p = 15; e = 15 – (-3) = 18; n = 31 – 15 = 16

3
Isotopes
Atoms with the same number of protons but different numbers of neutrons are called
isotopes. To find the number of isotopes in a sample a mass spectrometer can be used.
They change the atoms to positive ions by removing one or more electrons, the mass of the
positive ion can then be measured by its deflection in a magnetic field.

Relative Atomic Mass

Atomic masses given in the periodic table are calculated using the average mass of all the
isotopes in a sample of the element then comparing that mass with the mass of 1/12 of a 12C
atom.

e.g. Natural chlorine is composed of two main isotopes,chlorine-35 and chlorine-37. The
following result from a mass spectrometer was obtained for a sample of chlorine in NZ:

Isotope of Chlorine Isotopic mass Abundance percentage (%)

35Cl 35 75.77
37Cl 37 24.23

From these data the relative atomic mass of chlorine in this sample can be calculated.

RAM(Cl) = 35 x 75.77 + 37 x 24.23

100
= 35.45

Story of the Atom: Facts about Atoms

4
Atomic Energy Levels
When an element is converted into a gas and then placed into a discharge tube and
bombarded with an electric current, individual atoms become “excited” to a higher internal
energy level. Electrons absorb the exact energy they need to “jump” from their ground
state location to an empty location in an orbital of higher energy. When electrons fall back
down, this energy is lost as electromagnetic radiation. A spectrograph breaks the emitted
radiation from the atom into its component frequencies.

e.g. Emission Spectrum for Hydrogen

The amount of radiation emitted by an electron when it falls from a higher to a lower
energy level is referred to as a quantum of radiation.

Electronic Orbitals
Electrons in atoms exist in a series of principal energy levels, each of which is described
by an integer called the principal quantum number. The larger the integer, the greater the
distance from the nucleus where the electrons are most likely to be found.

• Each principal energy level is divided into a number of sub-levels, each of which
consists of a set of orbitals.
• The number of sub-levels in any principal energy level is equal to the principal
quantum number of that level.
• The different sublevels are described by the letters s, p, d, f.
• The number of orbitals in any sub-level depends upon the sub-level itself.
• Each orbital can contain a maximum of two electrons.

5
The orbitals available at each principal energy level, and the maximum numbers of
electrons in these levels, are shown in the table:

Shell / Maximum number of

Orbital
Principal Sub-level / electrons in:
Energy Sub-shell
Type Number each sub-level total
Level
1st 1 (1s) s 1 2 2
2 (2s) s 1 2
2nd
(2p) p 3 6 8
3 (3s) s 1 2
3rd (3p) p 3 6
(3d) d 5 10 18
4 (4s) s 1 2
(4p) p 3 6
4th
(4d) d 5 10
(4f) f 7 14 32

• Electrons fill up these orbitals so each lower energy orbital is filled before going
into a higher orbital.

6
 • The order of filling is 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f.
Note: the 4s is filled before the 3d as it has a slightly lower energy value when empty,
E(4s0) < E(3d0).

Or

The first number is the principal quantum number which is the same as the shell number,
the letter indicates the type of orbital, the number and letter together indicates the
subshell/sublevel and the superscript is the number of electrons in each type of orbital.

e.g. Fe: 1s2 2s2 2p6 3s2 3p6 4s2 3d6 or 1s2 2s2 2p6 3s2 3p6 3d6 4s2

e.g. Sr: 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2

7
Electron-in-Box diagrams
An ‘electron-in-box’ diagram can be used to show the electron arrangement for an atom or
an ion. A box represents one orbital and an arrow ‘↑’ or ‘↓’ represents one electron.

e.g. The electronic structure of a nitrogen atom is 1s22s22p3.

The electron-in-box diagram is:
E

n=5 5s
4p
3d
n=4 4s
3p
n=3 3s

2p
n=2 2s

n=1 1s

e.g. The electron-in-box diagram for an iron atom is:

Story of the Atom Part 2: Electron

8
Summary of Rules for Filling Up Orbitals

1. Pauli's Exclusion Principle: No more than two electrons can occupy one orbital, the
electrons will pair up with opposite spins.

If there is only one electron in an orbital, a ‘↑’ should be used not a ‘↓’.

2. Hund's Rule: If an electron has a choice (of equal energy) to enter, it will tend to go
into an empty orbital rather than a half full one.

This is because of the energy increase caused by repulsion between two electrons
occupying the same space since they are both negatively charged. Single electrons
have lower energy than electrons that are paired.

3. Aufbau's Principle: Under normal conditions, electrons will tend to occupy the lowest
available energy levels and orbitals. There are two exceptions in the first 38 elements.

• Chromium (Cr): 1s22s22p63s23p64s13d5

This is because a half-full 3d sub-shell (3d5) has lower energy than 3d4. The atom’s
energy is lower if an electron moves from the 4s orbital into the vacant 3d one. The
lower the energy level, the more stable the electron arrangement.

• Copper (Cu): 1s22s22p63s23p64s13d10

This is because a full 3d sub-shell (3d10) has lower energy than 3d9.The atom’s
energy is lower if an electron moves from the 4s orbital into the 3d. So the stable
electron arrangement is:

9
Electron Configuration of Ions

1. The number of electrons present in an ion can be calculated by the formula below:
Number of electrons = Atomic number - Charge on ion
e = p – the charge
e.g. Number of electrons in an oxide ion, O2- is 8- (-2) = 10
The electronic configuration for O2- is 1s2 2s2 2p6
The rules for filling up orbitals listed above are followed with ions as well as atoms.

2. Transition metal atoms in Period 4 (from Sc to Zn) always lose the 4s electron(s) first
when they form ions because the energy level of an electron occupied 4s orbital is
slightly higher than that of an electron occupied 3d orbital, E(4se) > E(3de).
e.g. Fe: 1s2 2s2 2p6 3s2 3p6 3d6 4s2

Fe2+: 1s2 2s2 2p6 3s2 3p6 3d6

Fe3+: 1s2 2s2 2p6 3s2 3p6 3d5

3. Isoelectronic: Having the same electronic configuration.

e.g. O2-, F-, Ne, Na+ and Mg2+ all have electron configuration
1s2 2s2 2p6

e.g. Fe2+ and Cr are not isoelectronic as they have different electron
configurations although they both have 24 electrons.
Fe2+: [Ar] 3d6
Cr: [Ar] 3d5 4s1

The Noble Gas Cores

Helium core: [He] is sometimes used as a short way of writing 1s2
Neon core: [Ne] is sometimes used as a short way of writing 1s2 2s2 2p6
Argon core: [Ar] is sometimes used as a short way of writing 1s2 2s2 2p6 3s2 3p6

Questions 1
Story of the Atom Part 2: Electron configuration

10
Electronegativity

Electronegativity is defined as the relative attraction of nuclei in the atoms to the

electrons in a bond. The table below shows the electronegativity values of some selected
atoms on the Pauling’s scale.

The diagonal relationship:

The Period 2 non-metal atoms are more electronegative than the Period 3 non-metal atoms
diagonally.
EN(O) > EN(Cl) EN(N)> EN(S) EN(C)> EN(P) EN(B)> EN(Si)

Fluorine (F) is the most electronegative atom among the atoms of all elements.

The inert gases in Group 18 were not assigned an electronegativity value because they have 8
electrons in their valence shell and thus do not form bonds with other atoms. Recently, some
oxides and fluorides of krypton and xenon, KrO2, XeF4, etc., have been discovered. Helium,
neon and argon still exist as uncombined elements.

The periodic trends:

 Across a period, the number of protons in the nucleus increases but electrons are being
added to the same shell, no additional shielding. Bonding electrons are held closer and
more tightly to the nucleus. Electronegativity increases.

 Down a group, more shells of electrons are added. Bonding electrons are further from the
nucleus and shielded by increasing number of inner electrons, hence bonding electrons are
less attracted to the nucleus. Electronegativity decreases.

11
Summary:

12
Chemical Bonding
Chemical bonds are electrostatic attractive forces that hold particles together. They usually
form because energy is released. The bonded particles have lower energy than separate energy.

Metallic bonding is a strong attractive force between metal cations and delocalised electrons.

Ionic bonding is a strong attractive force between cations and anions.

A covalent bond is an electrostatic attractive force between the nuclei of two atoms and the pair
of electrons they share.

Bond breaking is endothermic; Bond making is exothermic.

Structure of Solids
There are four different types of structure based on attractive forces between particles. Particles
can be atoms, ions or molecules, held together in a lattice or a 3-dimensional regular
arrangement.

 Metals - Giant metallic lattice

 Ionic compounds - Giant ionic lattice
 Giant covalent or macro-molecular substances - Giant covalent network structure
 Simple molecular substances - simple molecular lattice

13
A – Giant Metallic Lattice
Metals consist of a lattice of ions (metal cations) surrounded by a 'sea' of mobile electrons.
These electrons are the valence electrons although they now do not belong to individual atoms.
The structure holds together because the cations attract the delocallised valence electrons.

e.g.

Physical Properties of Metals:

(a) Metals conduct electricity – because electrons are negatively charged and those electrons
are free to move throughout the lattice structure.

(b) Metals are malleable and ductile – because when a metal is beaten into another shape the
multidirectional delocalised electrons are still able to hold the metal cations together.

(c) Metals usually have high melting points (except Hg) – because a large amount of energy
needed to overcome the strong electrostatic force and hence separate the metal cations
and mobile electrons.

14
B - Giant Ionic Lattice

In general, an ionic lattice is made of (metal) cations and (non-metal) anions held together by
strong electrostatic attractive forces between them.

Ions are charged particles. A cation is positively charged and forms when an atom loses an
electron/electrons. An anion is negatively charged and forms when an atom gains an
electron/electrons.

The 3-D diagram for the ionic lattice in solid sodium chloride is shown below.
(Note: each Na+ is surrounded by 6 Cl- and each Cl- is surrounded by 6 Na+.)

Or

15
Physical properties of ionic compounds:
(a) Ionic compounds do not conduct electricity when solid because all the ions are trapped in
the lattice and cannot move freely, only vibrate about their fixed positions. When molten
or dissolved in water the lattice is broken and ions are free to move and carry charge.

e.g. NaCl(s) cannot conduct but both NaCl(l) or NaCl(aq) can conduct.

(b) Ionic compounds usually have high melting points. A large amount of energy needed to
overcome the strong electrostatic force and hence separate the cations and anions.

e.g. m.p. of NaCl(s) = 801°C; m.p. of MgO(s) = 2800°C

(c) Ionic compounds are brittle. When an external force is applied on an ionic compound
the lattice structure in the crystal will be distorted. Similarly charged ions line up
next to each other and repel. The crystal breaks.

(d) Ionic compounds are more soluble in polar solvents (e.g. water, ethanol, etc.) than in
non-polar solvents (e.g. cyclohexane and tetrachloromethane, etc.).

Ionic compounds are more soluble in polar solvents like water due to the formation of
ion-dipole attractions.

e g. NaCl(s) is soluble in water; partially soluble in ethanol; insoluble in cyclohexane.

Note:
Ionic compounds such as NH4Cl, NaNO3 and K2SO4 also contain covalent bonds. The
polyatomic ions NH4+, SO42-, NO3- contain more than one atom covalently bonded.

16
C – Giant covalent network structure

A giant covalent network a lattice is made of atoms joined together by strong covalent bonds
e.g. Diamond(C), Graphite(C), Boron (B), Silicon (Si) and Quartz/Silica (SiO2).

Diamond
In a diamond lattice, each carbon atom is covalently bonded to four other carbon atoms
forming a tetrahedral arrangement throughout the network structure.

• Diamond has a very high melting point – because diamond has a giant network structure
held by many strong covalent bonds. A large amount of energy needed to overcome all
those covalent bonds and hence separate all of the carbon atoms.

• Diamond is hard – because each carbon atom is covalently joined to four other carbon
atoms forming a rigid tetrahedral arrangement throughout the network structure.
Diamond is used in cutting and grinding tools.

• Diamond is a non-conductor – because each carbon atom uses all four valence electrons
for bonding. There are no free electrons in the network.

17
Graphite
In graphite the carbon atoms are arranged in layers by strong covalent bonds. Within a layer
each carbon atom is joined to only three other carbon atoms in hexagons leaving one valence
electron freely moving throughout the layers.

• Graphite has a very high melting point because the giant network structure is held
together by many strong covalent bonds. A large amount of energy needed to overcome
all those covalent bonds and hence separate all of the carbon atoms.

• Graphite is soft. The layers are held together by weak (van der Waals’) forces and can
slide over one another. Graphite is often used as a lubricant and in pencils (known as
pencil lead).

• Graphite conducts electricity. Each carbon atom only uses three valence electrons for
bonding and leaves the fourth one to move freely within the layers. Graphite is the only
non-metal that conducts electricity.

Both graphite and diamond are allotropes of carbon. Allotropes are substances made of the
same element but have the different physical forms. Another allotrope of carbon is
Buckminsterfullerene, the “BuckyBall” and has the chemical formula, C60.

18
D - Simple molecular structure
A simple molecular substance is a lattice made of molecules held together by weak
electrostatic attractive forces between the opposite charges on the ends of dipoles. The strength
of these intermolecular forces depends on the polarity of the molecules.
Determining the polarity of a molecule, requires knowledge of the polarity of the individual
bonds and how these polarities interact in the overall shape of the molecule.

Non-polar Covalent Bonds

These are formed between two atoms with the same or very similar electronegativities, usually
non-metals. These two atoms can be same or different. The bond is due to the electrostatic
attraction both nuclei have for the bonding (shared) electrons.

e.g. Cl—Cl, H—H, C—C, O=O, N≡ N, etc.

C—H, Si—H, B—H, etc.

Polar Covalent Bonds

These are formed between two atoms with different electronegativities, usually two different
non-metals. This electronegativity difference results in a bond with a permanent dipole (a
charge separation across the bond). As long as the molecule's symmetry does not cancel out the
polar bonds (dipoles) this will result in a polar molecule. This increases the intermolecular
forces between the molecules hence polar covalent solids will have higher melting and boiling
points than non-polar covalent solids with similar molar mass.

In a non-polar covalent bond electronegativity difference is 0.4 or less.

In a polar covalent bond electronegativity difference is between 0.4 and 1.6.
In an ionic bond electronegativity difference is 1.6 or greater.

e.g. H—O, H—Cl, H—F, C=O, C—Cl, S—F, etc.

19
Co-ordinate or Dative Bonding
In normal covalent bonds, each atom provides one electron for the bond, but some compounds
involve the sharing of an electron pair originating from one atom. Compounds containing
unshared electron pairs readily form dative covalent bonds. e.g. Al2Cl6, N2O4, etc.
Dative bonding also explains why more than one oxide of an element exists.
e.g. CO2 does not contain dative bonds; CO contains one dative bond so all the atoms acquire
the stable octet valence shell arrangement.

20
Predicting Molecular Shapes
Drawing Lewis Structures
A Lewis structure is a two dimensional drawing of a molecule or an ion. In a Lewis structure,
the valence electrons around the atoms are shown as:

Single bond (2 electrons shared) −

Double bond (4 electrons shared) =
Triple bond (6 electrons shared) ≡
Lone pair of electrons :

Steps:
1. Draw the 'skeleton' of the structure - the arrangement of the atoms with single bonds
between them. Usually the atom with the most incomplete valence shell will be the central
atom.

2. Add up the number of valence electrons of the atoms involved. For ions, take electrons
off for positive ions and add them on for negative ions.

e.g. NH3 = 5+(3 x 1) = 8

SO42- = 6 + (6 x 4) + 2 = 32

3. Each single bond in the structure accounts for two electrons. After subtracting the number
of electrons used in these bonds the rest of the electrons are placed around the molecule or
ion to give each atom a stable structure (usually 8 according to the Octet Rule).

The Octet Rule:

Atoms in a stable molecule usually form bonds so that they have eight electrons in their outer
shell.
e.g. NH3 6 electrons used in bonds, 2 remaining unbonded = a lone pair of electrons

If there are not enough electrons to satisfy all atoms then multiple bonds or a dative bond can
be used. e.g. SO2

21
The Octet Rule
Applies without exception to the 4 atoms carbon(C), nitrogen(N), oxygen(O) and fluorine(F).

Less than 8 electrons

The octet rule does not apply to hydrogen(H), beryllium(Be) and boron(B), which are
ordinarily limited to two, four and six electrons respectively. e.g. H2, BeCl2, BF3, etc.

Octet expansion
In some atoms, from Si onwards, it is possible to expand the valence shell so that it can hold
more than 8 shared electrons. This happens in atoms where the valence electrons are close in
energy to the nearest d orbitals.

e.g. PCl5
The central phosphorus P atom is able to use its vacant 3d subshell in bonding allowing 10
electrons for it to share with the 5 Cl atoms.

At the ground state (the lowest energy state), the electron configuration for the valence shell of
a P atom is shown below.

At the excited state during reactions, the absorption of energy results in an electron ‘jumping’
from a 3s orbital to a vacant 3d one, forming 5 single electrons which enable 5 single covalent
bonds to form.

22
Thus the Lewis structure of PCl5 is:

For phosphorus, sulfur, chlorine, bromine, iodine, krypton and xenon, 10 and 12 shared
electrons in the valence shell are common. In these situations the atoms are using their empty
d subshell to accommodate the extra electrons.

Before silicon, all the non-metal atoms only have one or two shells which means d orbitals are
not available for electrons to be excited into them. So octet expansion does not apply to atoms
before silicon.

Questions 2

23
Shapes of Molecules
The VSEPR (Valence Shell Electron Pair Repulsion) Theory

Electron pair includes shared(=bonded) and unshared(=lone pair)

VSEPR uses the least repulsion between shared(=bonded) electrons and unshared(=lone pair
of) electrons in the valence shell to predict the stable shape.

The number of bonds (including multiple bonds) and lone pairs on the central atom affect the
shape. As lone pairs of electrons are closer to the central atom than the bond pairs they repel
more strongly distorting the shapes listed below, resulting in more molecular shapes.

The arrangement of 2 bonds with no lone pairs on the central atom is linear
The arrangement of 3 bonds with no lone pairs on the central atom is trigonal planar
The arrangement of 4 bonds with no lone pairs on the central atom is tetrahedral
The arrangement of 5 bonds with no lone pairs on the central atom is trigonal bipyramidal
The arrangement of 6 bonds with no lone pairs on the central atom is octahedral

e.g. CH4, methane

The total number of electrons = 4 + (4 x 1) = 8

All the 8 electrons are shared (4 bonds) and there are no lone pairs of
electrons on the central C atom, therefore it has a tetrahedral shape.

e.g. IF5, iodine pentafluoride or iodine(V) fluoride

The total number of electrons = 7 + (5 x 7) = 42

Although the base shape with six areas of negative charge is

octahedral, one of them is a lone pair for the central I atom distorting
the octahedral, instead it has a square pyramidal shape.

Chemical Bonding 5: Lewis Structures

Chemical Bonding 6: Shapes of Molecules

24
Predicting the Polarity of a Molecule

For a molecule to be polar, two conditions must be met

 It must have at least one polar bond

 It must have an unsymmetrical shape that does not allow the polarities of two or more
polar bonds to cancel.

Examples:

Would you expect a tetrachloromethane CCl4 molecule to be polar or non-polar?

A CCl4 molecule has a tetrahedral shape which is symmetrical in 3-dimensions,

so the 4 dipoles Cδ+—Clδ− can cancel each other. Thus, it is a non-polar molecule.

Chemical Bonding 7: Polar Molecules

25
26
Forces between Molecules (Intermolecular Forces)

Breaking intermolecular forces causes a state change while breaking intramolecular force (like
covalent bonds) will generate a chemical reaction.

(a) Temporary dipole–dipole attraction

Temporary dipole–dipole attraction is present between all covalent molecules. The temporary
dipole exists for an instant in time when electrons are unevenly distributed. The strength of
temporary dipole–dipole attraction depends on the number of electrons or the size of the
electron cloud or the molar mass of a covalent molecule.

Non polar covalent solids have very strong intramolecular forces (covalent bonds) and
relatively weak intermolecular forces. Most are gases at room temperature.

The diagram below shows the formation of temporary dipole-dipole attraction between atoms
in neighboring molecules.

27
(b) Permanent dipole–dipole attraction
Permanent dipole–dipole attraction is present between only polar molecules. Polar molecules
have both temporary and permanent dipole–dipole attractions.

The strength of permanent dipole–dipole attraction is directly proportional to the polarity of a

covalent molecule. The polarity of a covalent molecule depends on the electronegativity of the
atoms in that molecule. The greater the difference of electronegativities between the atoms the
more polar is the molecule.

Temporary and permanent dipole–dipole attractions are called van der Waals’ forces.

The diagram below shows the formation of permanent dipole–dipole attraction between
hydrogen chloride molecules.

(c) Hydrogen bonding

Hydrogen bonding is a special type of dipole-dipole attraction. In general, hydrogen bonding is
stronger than van der Waals’ forces. It is the strongest form of intermolecular attraction but
much weaker than an average covalent bond.
Hydrogen bonds occur only when hydrogen is in a molecule where it is bonded to a nitrogen,
oxygen or fluorine atom. These three atoms are very electronegative and small in size, so their
attraction for the shared electron pair in the covalent bond is very strong, exposing the bonded
hydrogen atom so positively charged that it becomes like a proton, looking for a lone pair of
electrons from a neighbouring F, O, N atom to full its practically empty valence shell.

Among these three atoms (N, O, F), the more polar the bond with H, the more polarised is the
H atom and the stronger the hydrogen bond. So the hydrogen bond F:|||||H is stronger than
O:|||||H stronger than N:|||||H as fluorine is the most electronegative.

28
The diagrams below show the formation of hydrogen bonding in water, hydrogen fluoride and
ammonia.
e.g. H-bonding between H2O molecules

e.g. H-bonding between HF molecules

e.g. H-bonding between NH3 molecules

Some important examples, in their solid or liquid state, are:

Inorganic compounds: HF, H2O, H2O2, NH3, N2H4, etc.
Organic compounds:
Alcohols (ROH), e.g. ethanol (CH3CH2OH);
Carboxylic acids (RCOOH), e.g. ethanoic acid (CH3COOH);
Amines (RNH2), e.g. aminoethane (CH3CH2NH2);
Amides (RCONH2), e.g. ethanamide (CH3CONH2), etc.

29
Properties of Water and Ice
Water has unexpectedly high values for its melting point, boiling point, molar heat of fusion
and molar heat of vaporisation. These values result from extra attractions between water
molecules due to the formation of hydrogen bonds. The extra bonding between water
molecules also causes high surface tension and high viscosity.

There are two hydrogen atoms and two lone electron pairs in each water molecule resulting in a
three-dimensional tetrahedral structure in ice. Each oxygen atom in ice is surrounded
tetrahedrally by four H atoms.

This creates a very open structure accounting for the fact that ice is less dense than water
at 0 °C. When ice melts, some hydrogen bonds are broken, the regular lattice partially breaks
up and the water molecules pack more closely, so water has a higher density than ice.

Chemical Bonding 8: Solids Summary

30
Some examples of intermolecular forces affecting boiling points:
1) Why the boiling point of chlorine (Cl2) is lower than that of bromine (Br2)?
Because both bromine and chlorine are non-polar. A Br2 molecule has more
electrons than a Cl2 molecule. This means Br2 molecules would have more chance
to form temporary dipoles. Therefore, the temporary dipole-dipole attraction
between Br2 molecules would be stronger, requiring more energy to break down. In
fact, bromine is a liquid at room temperature while chlorine is a gas.
2) Why the boiling point of hydrogen fluoride (HF) is much higher than that of
hydrogen chloride (HCl)?
This is because HF has hydrogen bonding, temporary and permanent dipole-dipole
attractions while HCl does not have hydrogen bonding, only has temporary and
permanent dipole-dipole attractions. Hydrogen bond is the strongest type of
intermolecular force. So HF has stronger intermolecular forces which require more
energy to break them and hence HF has a higher boiling point.
3) Would you expect the boiling point of fluorine (F2) to be lower than, the same as or
higher than that of hydrogen chloride (HCl)? Explain your choice
Lower
This is because F2 is non-polar while HCl is polar. Both have the same number of
electrons (18e−s) so both have the same (very similar) temporary dipole-dipole
attraction. HCl also has permanent dipole-dipole attraction which means HCl has
stronger intermolecular forces requiring more heat energy to break down.
4) Would you expect the boiling point of hydrogen chloride (HCl) to be lower than,
higher than that of hydrogen bromide (HBr) or undetermined? Explain your choice.
Undetermined
Both HBr and HCl are polar molecules. HBr has more electrons (36e−s) than HCl
(18e−s) so HBr has stronger temporary dipole-dipole attraction. On the other hand,
HCl is more polar than HBr as Cl is more electronegative than Br, so HCl has
stronger permanent dipole-dipole attraction. Therefore this is an undetermined
situation. To find which one has a higher boiling point carry out experiments.
5) Would you expect the boiling point of hydrogen fluoride (HF) to be lower than, the
same as or higher than that of water (H2O)? Explain your choice
Lower
This is because each molecule of HF has three lone pairs of electrons but only one H
atom while each water molecule H2O has two lone pairs of electrons and two H
atoms. So water can form more hydrogen bonds than HF, which means water has
stronger intermolecular forces requiring more heat energy to break down.

31
Questions 1

1. Write out the electron configuration of atoms of each of the following elements using s, p and d notation.

a. Hydrogen b. Beryllium

c. Scandium d. Bromine

2. Identify the elements whose atoms have the electron configuration of:

a. 1s2 2s2 2p6 3s2 3p5 b. 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p3

3. Write out the electron configuration of the following ions using s, p and d notation:

a. Li+ b. F-

c. Ca2+ d. Mn2+

e. Se2- f. Cr3+

4. Identify by symbol the elements whose atom and monatomic ions have the electron configuration as
shown below. Identify all the possible isoelectronic species in each case.

a. 1s2 (3 species)

b. 1s22s22p63s23p6 (7 species)

c. 1s22s22p63s23p64s23d104p6 (7 species)

5. Draw an ‘e-in-box’ diagram for each of the following species.

a Si

b Ni2+

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Questions 2

1 How many lone pair electrons are held by each of the underlined atoms?

(a) CS2 (b) H2S

(c) HCl (d) BCl3

2 Draw the Lewis diagram for each of the following species:

(a) NH3 (b) NO3-

(c) SO42- (d) PCl5

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