Structure 2.

2
IB CHEMISTRY SL
Structure 2.2.1 and 2.2.2
Understandings:
• A covalent bond is formed by the electrostatic attraction between a shared pair of
electrons and the positively charged nuclei (2.2.1).
• The octet rule refers to the tendency of atoms to gain a valence shell with a total
of 8 electrons (2.2.1).
• Single, double and triple bonds involve one, two and three shared pairs of
electrons respectively (2.2.2).
Learning outcomes:
• Deduce the Lewis formula of molecules and ions for up to four electron pairs on
each atom (2.2.1).
• Explain the relationship between the number of bonds, bond length and bond
strength (2.2.2).
Additional notes:
• Lewis formulas (also known as electron dot or Lewis structures) show all the
valence electrons (bonding and non-bonding pairs) in a covalently bonded
species.
• Electron pairs in a Lewis formula can be shown as dots, crosses or dashes.
• Molecules containing atoms with fewer than an octet of electrons should be
covered.
• Organic and inorganic examples should be used.
Linking questions:
• Structure 1.3 Why do noble gases form covalent bonds less readily than other
elements?
• Structure 2.1 Why do ionic bonds only form between different elements while
covalent bonds can form between atoms of the same element?
• Reactivity 2.2 How does the presence of double and triple bonds in molecules
influence their reactivity?

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The octet rule
• The octet rule states that atoms are stable with eight electrons in their valence
shells with the electron configuration of a noble gas.
• The electron configurations of noble gases He, Ne and Ar are shown below.

• Noble gases are stable because they have full valence shells.
• Atoms can achieve the electron configuration of a noble gas by either sharing
electrons (covalent bonding) or by losing or gaining electrons (ionic bonding).

Exceptions to the octet rule

• Hydrogen and helium are stable with 2 electrons in their outer energy level.
• Beryllium is stable with 4 electrons in its outer energy level.
• Boron is stable with 6 electrons in its outer energy level.
• Elements in period 3 onwards can hold more than 8 electrons in their outer shells
(expanded octets).

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Covalent bonding
• A covalent bond is the electrostatic attraction between positive nuclei and shared
pairs of bonding electrons.
• A covalent bond is an intermolecular bond (bond within a molecule).
• Covalent bonding occurs between non-metal elements only.
• The electronegativity difference between atoms is between 0.0 and 1.7 units.

• Both nuclei are attracted to the shared pair of bonding electrons.

• The electrostatic attraction between the nuclei and shared pair of bonding
electrons is the covalent bond.

Single, double and triple bonds

• Single bonds are longer and weaker, triple bonds are shorter and stronger.

• The carbon-to-carbon bonds in C2H6 are longer and weaker than those in C2H2.
Number of C to C bond C to C bond length
Bond shared electrons strength (kJ mol-1) (10-12 m)
Single 2 347 153
Double 4 614 134
Triple 6 839 120

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Exercises:
1. Describe a covalent bond.

2. Where on the periodic table would you find elements that bond by covalent
bonding?

3. Arrange the following in order of increasing carbon to carbon bond strength

(weakest first).
C2H4, C2H6, C2H2

4. Arrange the following in order of decreasing carbon to carbon bond length

(longest first),
C2H4, C2H6, C2H2

Bond order
• Bond order is the number of bonds between a pair of atoms.
• Single bonds have a bond order of 1, double bonds have a bond order of 2
and triple bonds have a bond order of 3.
• The higher the bond order, the stronger (and shorter) the bond.
• Polyatomic ions such as CO32– and NO3– and molecules such as benzene, C6H6,
can have fractional bond orders.
• Bond order can be calculated by dividing the sum of the individual bond orders by
the number of bonding groups in the molecule or ion.

Example: Calculate the bond order of the bonds in the nitrate ion, NO3–.

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Lewis structures
• Lewis structures show all the valence electrons in a molecule; the bonding
electrons and the lone pairs of electrons (non-bonding electrons).

How to determine a Lewis structure

1. Calculate the number of valence electrons in the molecule.
2. Calculate the number of electrons each atom needs to complete its octet.
3. Subtract 1 from 2 – this will give you the number of bonding electrons in the
molecule.
4. Draw the skeletal structure of the molecule with the least electronegative atom at
the center.
5. Complete the octets of the atoms in the molecule.

Example – CCl4 (carbon tetrachloride)

1. Total number of valence electrons = 4 + (4 × 7) = 32
2. Number of valence electrons needed for each atom to complete its octet (5 × 8) =
40
3. 40 - 32 = 8 bonding electrons
4. Skeletal formula:

One single bond = 2 electrons (total 8 bonding electrons).

5. Complete the octets of all the atoms in the molecule.

Do a final check that all electrons are accounted for.

It should match with the number in part 1 (32).

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Exercises:

1. Draw Lewis structures for the following molecules.

a) Cl2
b) HCl h) N2H4
c) CH3Cl i) H2O
d) CF4 j) CH3OH
e) PF3 k) CO
f) BF3 l) C2H4
g) BeCl2 j) HCN

2. Draw Lewis structures for the following ions.

a) Cl-
b) NH4+
c) OH-

3. Which molecules contain an incomplete octet of electrons?

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Structure 2.2.3
Understandings:
• A coordination bond is a covalent bond in which both the electrons of the shared
pair originate from the same atom.
Learning outcomes:
• Identify coordination bonds in compounds.
Additional notes:
• Include coverage of transition element complexes (HL).
Linking questions:
• Reactivity 3.4 (HL) Why do Lewis acid–base reactions lead to the formation of
coordination bonds?

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Coordinate covalent bonds
• In a coordinate covalent bond, one atom contributes both the bonding electrons to
the bond.

• Draw the Lewis structure of CO, H3O+ and NH4+ in the boxes below.
CO H3O+ NH4+

• Al2Cl6 – the dimer formed between two molecules of AlCl3.

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Structure 2.2.4
Understandings:
• The valence shell electron pair repulsion (VSEPR) model enables the shapes of
molecules to be predicted from the repulsion of electron domains around a central
atom.
Learning outcomes:
• Predict the electron domain geometry and the molecular geometry for species
with up to four electron domains.
Additional notes:
• Include predicting how non-bonding pairs and multiple bonds affect bond angles.

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VSEPR theory
• Valence shell electron pair repulsion theory is used to predict the geometry
(shape) of molecules.
• Electron pairs (bonds or lone pairs) repel each other and spread apart as far as
possible.
• The term electron domain is used to refer to bonds or lone pairs of electrons (non-
bonding electrons) around an atom in a molecule.
• Single bonds, double bonds, triple bonds and lone pairs of electrons (non-bonding
electrons) count as one electron domain.

How many electron domains are

there around the carbon atom?

How many electron domains are

there around the oxygen atom?

How many electron domains are

there around the carbon atom?

The order of repulsion between electron domains is as follows:

lone pair – lone pair > lone pair – bonding domain > bonding domain – bonding domain

most repulsion least repulsion

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Molecules with four electron domains
• Four bonding domains, zero non-bonding domains

electron bonding non-bonding electron molecular bond

domains domains domains domain geometry angle
geometry

4 4 0 tetrahedral tetrahedral 109.5o

• Three bonding domains, one non-bonding domain

electron bonding non-bonding electron molecular bond

domains domains domains domain geometry angle
geometry
4 3 1 tetrahedral trigonal 107.8o
pyramidal

• Two bonding domains, two non-bonding domains

electron bonding non-bonding electron molecular bond

domains domains domains domain geometry angle
geometry
4 2 2 tetrahedral bent 104.5o

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Molecules with three electron domains
• Three bonding domains, zero non-bonding domains

electron bonding non-bonding electron molecular bond

domains domains domains domain geometry angle
geometry
3 3 0 trigonal trigonal 120o
planar planar

• Two bonding domains, one non-bonding domain

electron bonding non-bonding electron molecular bond

domains domains domains domain geometry angle
geometry
3 2 1 trigonal bent <120o
planar

Molecules with two electron domains

• Two bonding domains, zero non-bonding domains

electron bonding non-bonding electron molecular bond

domains domains domains domain geometry angle
geometry
2 2 0 linear linear 180o

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Exercise: Determine the molecular geometry and bond angles in the following
molecules:

a) HCN e) C2H2
b) PH3 f) BF3
c) CH2Cl2 g) BeH2
d) Cl2O h) H2S

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Structure 2.2.5
Understandings:
• Bond polarity results from the difference in electronegativities of the bonded
atoms.
Learning outcomes:
• Deduce the polar nature of a covalent bond from electronegativity values.
Additional notes:
• Bond dipoles can be shown either with partial charges or vectors.
• Electronegativity values are given in the data booklet.
Linking questions:
• Structure 2.1 What properties of ionic compounds might be expected in
compounds with polar covalent bonding?

Polar covalent bonds

• Polar covalent bonds occur between atoms that have a difference in
electronegativity.

Difference in Polar or non-polar Example

electronegativity covalent bond
0 non-polar (pure) covalent bond Cl-Cl
0.1− 0.4 non-polar (weakly polar) covalent bond C-H

0.5 −1.7 polar covalent bond C-F

• Bond polarity can be shown by a vector arrow or by 𝛿 + and 𝛿 − as shown below.

Exercises:
1. Draw a diagram showing the bonding polarity in HF (hydrogen fluoride).

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 2. For each bond, find the difference in electronegativity and classify as either pure
covalent, non-polar covalent or polar covalent. Draw bond dipoles or partial
charges on each atom.

Bond Pure covalent, non-polar Bond dipoles

covalent or polar covalent
Br‒Br

C‒Cl

C‒I

C‒O

N‒F

H‒F

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Structure 2.2.6
Understandings:
• Molecular polarity depends on both bond polarity and molecular geometry.
Learning outcomes:
• Deduce the net dipole of a molecule or ion by considering bond polarity and
geometry.
Additional notes:
• Examples should include species in which bond dipoles do and do not cancel
each other.
Linking questions:
• Structure 3.2 (HL) What features of a molecule make it “infrared (IR) active”?

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Polar and non-polar molecules
The polarity of a molecule depends on two factors:
• The presence of polar bonds within the molecule.
• The shape (geometry) of the molecule.

• O2, N2 and CH4 are non-polar molecules.

• O2 and N2 are diatomic; both atoms have the same electronegativity.
• CH4 has non-polar bonds.

Non-polar molecule with polar bonds

• CCl4 is a non-polar molecule that has polar bonds.

• The bond polarities cancel out, therefore, the molecule has no net-dipole moment.

Polar molecules
• CH2Cl2 is a polar molecule.

• The bond polarities do not cancel out, therefore, it has a net-dipole moment.

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Exercises:
1. Outline the two factors that determine the polarity of a molecule.

2. Explain how a molecule can have polar bonds but overall have no net-dipole
moment (is a non-polar molecule).

3. Determine if the molecules below are polar or non-polar, giving a reason.

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Structure 2.2.7
Understandings:
• Carbon and silicon form covalent network structures.

Learning outcomes:
• Describe the structures and explanation of the properties of silicon, silicon
dioxide and carbon’s allotropes: diamond, graphite, fullerenes and graphene.
Additional notes:
• Allotropes of the same element have different bonding and structural patterns,
and so have different chemical and physical properties.
Linking questions:
• Structure 3.1 Why are silicon–silicon bonds generally weaker than carbon–
carbon bonds?

Giant covalent structures

• Giant covalent structures do not form discrete molecules.
• Examples include diamond, Si and SiO2

• Giant covalent structures do not conduct electricity (no free moving electrons).
• They are insoluble in polar and non-polar solvents.
• They have high melting and boiling points due to the strong covalent bonds
between atoms.
• They are very hard substances.

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Exercises:
1. Classify the following covalent compounds as simple molecular or giant covalent
based on their properties:

Property Simple molecular Giant covalent

High melting and boiling point

Insoluble in polar and non-polar

solvents
Liquids and gases under
standard conditions
Do not form discrete molecules

Poor electrical conductors

Soluble in polar or non-polar

solvents
Form discrete molecules

Very hard substances

2. Explain the following properties of the covalent compounds.

a. Pentane (C5H12) is insoluble in water but soluble in hexane (C6H14).

b. Diamond does not conduct electricity.

c. CO2 is a gas under standard conditions.

d. SiO2 has a melting point of 1600 oC

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Allotropes of carbon
• Allotropes are different forms of the same element in the same physical state.
• Carbon has 4 allotropes – graphite, diamond, Fullerene C60 and graphene.
• Different bonding within the structures gives the allotropes different properties.

Graphite

• Graphite has a layered structure.

• The layers are held together by weak intermolecular forces.
• The layers can slide over one another (because of weak intermolecular forces).
• Each carbon atom is bonded to 3 other carbon atoms.
• The bond angle between carbon atoms is 120o, trigonal planar.
• Graphite is a good conductor of electricity because of the delocalised electrons
that are free to move within the structure.

Diamond
• Giant covalent structure.
• High melting and boiling point.
• Very hard (strong covalent bonds between
atoms).
• Each carbon is bonded to 4 other carbon
atoms.
• Bond angle is 109.5o, tetrahedral.
• Does not conduct electricity (no delocalised
electrons).
• Used in jewellery and for cutting glass.

Fullerene C60
• Each carbon atom is bonded to 3 other carbon atoms.
• Structure consists of 12 pentagons and 20 hexagons.
• Poor electrical conductor (better than diamond but
worse than graphite).

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Graphene

• Each carbon atom is bonded to 3 other

carbon atoms.
• Bond angle between carbon atoms is
120o.
• Very good heat and electrical conductivity.
• Very thin (one layer thick) but very strong.

Allotropes of carbon and their uses

Allotrope Uses
Graphite dry lubricant, electrode rods, pencils
Diamond jewellery, tools for cutting glass
Fullerene C60 lubricant, nanotubes
Graphene lightweight, thin, flexible, yet durable display screens,
electric/photonics circuits, solar cells

Exercises:
1. Outline why graphite is a good conductor of electricity but diamond is not.

2. Give one reason for the high melting and boiling point of diamond.

3. State and explain the bond angles of graphite and diamond.

4. Explain why graphite is a very soft substance.

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Structure 2.2.8 and 2.2.9
Understandings:
• The nature of the force that exists between molecules is determined by the size
and polarity of the molecules.
• Intermolecular forces include London (dispersion), dipole-induced dipole, dipole–
dipole and hydrogen bonding.
• Given comparable molar mass, the relative strengths of intermolecular forces are
generally: London (dispersion) forces < dipole–dipole forces < hydrogen bonding.
Learning outcomes:
• Deduce the types of intermolecular force present from the structural features of
covalent molecules.
• Explain the physical properties of covalent substances to include volatility,
electrical conductivity and solubility in terms of their structure.
Additional notes:
• The term “van der Waals forces” should be used as an inclusive term to include
dipole–dipole, dipole- induced dipole, and London (dispersion) forces.
• Hydrogen bonds occur when hydrogen, being covalently bonded to an
electronegative atom, has an attractive interaction on a neighbouring
electronegative atom.
Linking questions:
• Structure 1.5 To what extent can intermolecular forces explain the deviation of
real gases from ideal behaviour?
• Structure 3.2 To what extent does a functional group determine the nature of the
intermolecular forces?

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Intermolecular forces
• Intermolecular forces are forces of attraction between molecules.
• The three types of intermolecular force are:
London dispersion forces, dipole-dipole forces and hydrogen bonding.
• London dispersion forces and dipole-dipole forces are collectively known as van
der Waals forces.

London dispersion forces

• London dispersion forces are the weakest type of intermolecular force.
• They exist between all atoms or molecules (both polar and non-polar).
• Due to the constant motion of electrons, an atom or molecule can develop a
temporary (instantaneous) dipole.

• An instantaneous dipole in one molecule can cause an induced dipole in a nearby

molecule.

Instantaneous dipole Induced dipole

• London dispersion forces have a significant effect on the physical properties of

molecules, such as boiling point.

Exercises:
1. State the types of intermolecular forces that are van der Waals forces.

2. Outline the formation of London dispersion forces.

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Boiling point of the halogens

Molar mass (g mol-1) Boiling point (oC)

F2 30.8 -188

Cl2 70.9 -34.0

Br2 160 58.0

I2 254 193

• The boiling points of the halogens increase as their molar masses increase.
• The strength of London dispersion forces increases with increasing molar mass.
• Stronger London dispersion forces result in a higher boiling point (more energy is
required to overcome the attractive forces between molecules).

Exercise: Explain why the boiling points of the halogens increase down the group.

Dipole-dipole forces
• Dipole-dipole forces occur between polar molecules that have a permanent dipole.
• They are the second strongest type of intermolecular force.
• There is an electrostatic attraction between the partial positive charge in one
molecule and the partial negative charge on another.
• The dipole-dipole attractions between HCl molecules are shown below.

Exercises:
1. State the type of molecules that dipole-dipole forces occur between.

2. Outline the formation of the dipole-dipole forces in HCl.

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Hydrogen bonding
• Hydrogen bonding occurs when a hydrogen atom is bonded to either a nitrogen,
oxygen or fluorine atom.
• It is the strongest type of intermolecular force.
• Example of compounds that have hydrogen bonding between their molecules are
H2O, NH3 and HF.

• Hydrogen bonds between water molecules are shown below. These are
responsible for the high boiling point of water.

• The hydrogen bond is between the partial positive charge on the hydrogen atom
and the partial negative charge on the oxygen atom
• Water has a much higher boiling point compared to other molecules with similar
molar masses because of the effect of hydrogen bonding.

Exercises:
1. Which groups of atoms are necessary for the formation of a hydrogen bond?

2. Outline the formation of a hydrogen bond between water molecules.

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Boiling points of group 14 and group 16 hydrides

Exercise: From the above graph, describe and explain the trend in boiling point of the
group 14 and group 16 hydrides.

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Exercises:

1. Arrange the following in terms of increasing strength.

Hydrogen bonding London dispersion forces Dipole-dipole forces

2. Identify the strongest type of intermolecular forces in the following molecules.

a) Cl2 f) CH3Cl
b) HCl g) H2O
c) HF h) CH3OH
d) CH4 i) C2H6
e) CCl4 j) NH3

3. Explain why, at room temperature, F2 and Cl2 are gases, Br2 is a liquid and I2 is a
solid.

4. The structures of butane, propanone, and ethanol can be seen below. They have
similar molar masses, but different boiling points. Explain the difference in boiling
point between the three molecules.

butane B.P. -1oC propanone B.P. 56oC ethanol B.P. 78oC

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Structure 2.2.10
Understandings:
• Chromatography is a technique used to separate the components of a mixture
based on their relative attractions involving intermolecular forces to mobile and
stationary phases.
Learning outcomes:
• Explain, calculate and interpret the retardation factor values, RF.
Additional notes:
• The use of locating agents is not required.
• The operational details of a gas chromatograph or high-performance liquid
chromatograph will not be assessed.

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