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AS 91164 Bonding, structure, properties and energy changes

LEWIS DIAGRAMS, SHAPES OF MOLECULES, POLAR AND NON-POLAR MOLECULES

Lewis diagrams: use dots (or x) to represent electrons, show only outer electrons.
Multiple bonds: some atoms e.g. C, O and N can form double or triple bonds. (In drawing Lewis
structures introduce = and ≡ only if there are unpaired electrons remaining and there are
atoms which don’t have a share in 8 electrons).
Bond polarity: when identical atoms are covalently bonded the electron pair is attracted
equally by the 2 nuclei. The bond is non-polar. When the two atoms are different one nucleus
will have a greater attraction for the electron pair in the bond than the other. The result is a
polar covalent bond. One end is slightly negative with respect to the other. E.g. HCl. δ+H-Clδ- .
Electronegativity: Is a measure of the attraction of an atom for the electron pair in a covalent
bond. The most electronegative atom is fluorine. Electronegativity values increase across any
period and decrease down a group. A polar bond results when there is a difference in
electronegativity between the 2 atoms forming the bond. The more electronegative atom is
the negative end of the bond. The bigger the difference in electronegativity between the 2
atoms forming the bond, the more polar the bond is.
Covalent or ionic? There is no distinct split between covalent and ionic bonding. (It may help to
think of ionic bonds as the extreme of polar bonds where one atom takes over complete
control of the electron pair).
Cl-Cl (non polar) ------------ δ+H-Clδ- (polar) ------------ Na+ Cl- (ionic)

Shapes of molecules: Covalent bonds are “directional”. The rule is that regions of negative
charge around the central atom repel each other as far as possible. The shape of a molecule or
ion depends on the number of regions of negative charge around the central atom.
Double and triple bonds count as a region of negative charge for the purpose of determining
shape. Don’t draw the nonbonding (NB) pairs as part of the final shape of the molecule. Below
they are shown as just to remind you they are there.
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Polarity of molecules: This depends on (1) whether the molecule has polar bonds (2) the
symmetry of the molecule. Assuming the atoms bonded to the central atom are the same,
symmetrical shapes are linear, trigonal planar and tetrahedral.
CO2: has two regions of negative charge around the central atom. It has no unshared electron
pairs and is therefore linear.
H2CO: has three regions of negative charge around the central atom. It has no unshared
electron pairs and is therefore trigonal planar. Having one very polar C=O bond and 2 virtually
non-polar C-H bonds, it will be polar.
SO2 has three regions of electron density (electron clouds) around the central atom (or S) and
repulsions between them result in a bond angle of 120o. SO2 is a polar molecule because the O
atoms will attract bond pairs in the O – S bonds more closely. The two polar bonds are
asymmetrically arranged, (therefore the dipoles will not cancel,) resulting in a polar molecule
overall.
CH4 has four regions of electron density around the central atom (C) and repulsions between
them result in a bond angle of 109.5o.
NH3: the molecule has four regions of negative charge around the central atom. These are
arranged tetrahedrally. Three are bonding regions and there is one non-bonding region which
results in the trigonal pyramid shape, bond angle approx. 109o. The lone pair of electrons on
the N causes the asymmetry. The effect of the polar bonds is not cancelled out, making the
molecule polar overall.
PCl3: 3 polar bonds and unsymmetrical arrangement (trigonal pyramidal) of P–Cl bonds around
central atom so polarities do not cancel out therefore polar.
H2O has four regions of electron density around the central atom (O). 2 are bonding and 2 are
non-bonding. Repulsions between them result in a bond angle of approx. 109O. H2O is also a
polar molecule for the same reasons as given above.
Polar molecules will dissolve in a polar solvent; therefore, SO2 is soluble in water. There is
attraction between positive end of one molecule and negative end of other in solution. PCl3
and H2S also dissolve in water. ('like' dissolves 'like'.) On the other hand non-polar CO2 and CH4
are virtually insoluble in water.

Practice explaining shape and polarity.

Remember:
Lewis diagram ⇒ shape of molecule (depends on electron repulsions around central atom) ⇒
consider polarity (if any) of bonds using idea of electronegativity (F O N/Cl S C H) ⇒ consider
overall molecular shape ⇒ predict if molecule is polar or non-polar overall in terms of dipoles
cancelling out or not.
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Why is CCl4 tetrahedral? Is it polar or non-polar?

The molecule is tetrahedral, due to 4 regions of electron density around the central C atom.

The C–Cl bond is polar (has a dipole), due to the difference in electronegativity of C and Cl. As
these 4 identical dipoles are arranged symmetrically about the C atom in CCl4, the dipoles
cancel out, so the molecule is non-polar.

So why is CH2Cl2 the same shape but this molecule is polar?

The molecule is tetrahedral due to 4 regions of electron density around the

central C atom. The C–Cl bonds are polar due to the difference in
electronegativity of C and Cl, while the C–H bonds are almost non–polar.
Although the bond arrangement around the C atom in CH2Cl2 is symmetrical, the differing
dipoles of the C–H and C–Cl bonds means the effect of the polar bonds does not cancel out, so
the molecule is polar overall.

And CO2?
CO2 has non-polar molecules. The C−O bonds of CO2 are polar due to the different
electronegativities of C and O.
As there are only 2 regions of electron density about the central C atom, the polar bonds are
arranged symmetrically about the C atom giving the molecule a linear
shape.

The effect of these polar bonds / bond dipoles cancel out so that the molecule is non polar.

So, what about SO2 – is that the same?

SO2 has polar molecules. The S−O bonds of SO2 are polar due to the differing electronegativities
of S and O. There are 3 regions of electron density about the central S atom
(which repel to a trigonal planar arrangement), however, the lone pair of
electrons on the S atom causes the S−O bonds to occupy a bent or V shape
around the central S atom. Therefore the effect of these polar bonds / bond dipoles is does not
cancel out, so that overall the molecule is polar.
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EXPLAINING SOME PROPERTIES IN TERMS OF STRUCTURE & BONDING

ELECTRICAL CONDUCTIVITY OF IONIC SUBSTANCES E.g. NaCl, MgCl2

Explain - Solid sodium chloride does not conduct electricity. However, if it is melted, sodium
chloride will conduct electricity.
In the solid state, sodium chloride consists of a 3–D lattice of Na+ and Cl– ions. Although charged
particles are present, they are held in position by strong ionic bonds. As there is no charged
particles able to move, the solid will not conduct electricity.
When the solid is melted (molten) the ions become free moving, and the free moving chargd
particles means the liquid will conduct electricity. When molten, the charged ions are separated
and free to move and conduct electricity.

THE HIGH MELTING POINT OF IONIC SUBSTANCES E.g. NaCl, KCl

Explain - NaCl has a high melting and boiling point
Sodium chloride consists of a 3–D lattice of Na+ and Cl– ions. The ions are held in position by
strong ionic bonds. As a lot of energy is required to overcome these strong forces and separate
the ions, the substances have high melting and boiling points.

THE SOLUBILITY OF (MANY) IONIC SUBSTANCES IN WATER E.g. KCl, NaCl

Explain - Potassium chloride will not dissolve in non-polar solvents, but will dissolve in water.
KCl is soluble in water as the polar water molecules are attracted towards the ions, and the
attraction is sufficient to pull the ions from the lattice. The molecules of a non–polar solvent are
not attracted towards the ions and so KCl is insoluble, for example, in cyclohexane.

METALS ARE EASILY SHAPED (MALLEABLE) OR CAN BE DRAWN INTO WIRES (DUCTILE) E.g.
Cu, Ag, Zn
Explain - Copper is easily shaped to form wires.
Copper consists of Cu atoms held together in a 3D lattice by metallic bonding, in which valence
electrons are attracted to the + nuclei of neighboring atoms. As this is a non-directional force,
layers of atoms can slide over each other without breaking the metallic bond and disrupting the
structure and breaking the metal.

METALS ARE GOOD CONDUCTORS OF ELECTRICITY

Explain - Copper (Cu) is a good conductor of electricity and is used for electrical wires.
Copper atoms are held together in a 3-D lattice by metallic bonding, in which delocalised
valence electrons are attracted to the + nuclei of neighbouring atoms. Conduction of electricity
requires free moving charges - the delocalised valence electrons.
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COVALENT MOLECULAR SUBSTANCES HAVE LOW MELTING AND BOILING POINTS E.g. PCl3, SCl2
Explain - PCl3 and SCl2 both have low melting and boiling points.
These are molecular substances. They consist of molecules and the molecules are attracted to
each other by weak intermolecular (or van der Waals) forces. As not much energy is required to
overcome these weak forces and separate the molecules, the substances have low melting and
boiling points.

SILICON DIOXIDE HAS A HIGH MELTING POINT & DOESN’T CONDUCT ELECTRICITY
Explain - Silicon dioxide has a high melting point
Silicon dioxide consists of silicon and oxygen atoms held together by covalent bonds in a
tetrahedral arrangement, so that a 3D network exists. As the covalent bonds are strong, they
are difficult to overcome and break, making it difficult to separate the atoms, so the structure
has a high melting point.
Strong covalent bonds hold the Si and O atoms together in a 3D arrangement. As all valence
electrons are involved in forming covalent bonds there are no free moving charges and so no
electrical conduction.

EXPLAIN SOME PROPERTIES OF IODINE – SUBLIMATION & SOLUBILITY

Explain - Iodine sublimes when gently heated.
Iodine consists of I2 molecules and weak intermolecular forces / weak Van der Waals forces
exist between the molecules. As these attractions are weak, the molecules are easily separated,
and the melting point is low.

Explain - It is soluble in cyclohexane.

Iodine molecules are non-polar, therefore iodine is soluble in a non-polar solvent such as
cyclohexane. Since both molecules have similar weak intermolecular forces, then the same weak
forces will exist between the two different molecules and this is why it will dissolve in
cyclohexane.

EXPLAINING SOME PROPERTIES OF CARBON DIOXIDE

Explain - CO2 sublimes at -78oC, is a poor conductor as a solid and is brittle as a solid.
CO2 exists as molecules. As the intermolecular forces between molecules are weak these are
easily overcome hence little energy is required to separate the molecules (therefore has a low
MP/sublimes at -78°C).
As all valence electrons are involved in forming covalent bonds there are no free moving
charges and so no electrical conduction.
Since the weak intermolecular forces allow the molecules to be easily separated this makes it
brittle / (easy to break the solid).