Worked solutions

Chapter 4
Exercises

1 Write the ions with their charges: (a) tin(II) phosphate

lead nitrate; ions present: Pb NO3 , so forms
2+ −
(b) titanium(IV) sulfate
Pb(NO3)2 (c) manganese(II) hydrogencarbonate
barium hydroxide; ions present: Ba OH , so
2+ −
(d) barium sulfate
forms Ba(OH)2
(e) mercury(I) sulfide
potassium hydrogencarbonate; ions present: K+
HCO3−, so forms KHCO3 4 The charges on the positive ions are deduced
from the formulas, again using the information
magnesium carbonate; ions present: Mg2+ CO32−,
on page 142. The guiding principle is that the
so forms MgCO3
overall charge must be zero.
copper sulfate; ions present: Cu2+ SO42−, so
(a) Sn2+ (b) Ti4+
forms CuSO4
(c) Mn2+ (d) Ba2+
calcium phosphate; ions present: Ca2+ PO43−, so
forms Ca3(PO4)2 (e) Hg+

ammonium chloride; ions present: NH4+ Cl−, so 5 A will have a charge of 2+ (Group 2) and B
forms NH4Cl will have a charge of 3– (Group 15). Cross
multiplying we get the formula: A3B2.
2 (a) potassium bromide; ions present: K+ Br–, so
forms KBr 6 Mg, atomic number = 12: electron configuration
(b) zinc oxide; ions present: Zn O , so forms
2+ 2– [Ne]3s2
ZnO Br, atomic number = 35: electron configuration
(c) sodium sulfate; ions present: Na SO4 , 2 ×
+ 2– [Ar]3d104s24p5
1+ with 1 × 2–, so forms Na2SO4 The magnesium atom loses its two electrons
Note: Na does not need to be put in from the 3s orbital to form Mg2+. Two bromine
brackets because it contains a single atom atoms each gain one electron into their 4p sub-
shell to form Br–. The ions attract each other by
(d) copper(II) bromide; ions present: Cu2+ Br–, 1
electrostatic forces and form a lattice with the
× 2+ with 2 × 1–, so forms CuBr2
empirical formula MgBr2.
(e) chromium(III) sulfate; ions present: Cr3+
SO42−, 2 × 3+ with 3 × 2–, so forms Cr2(SO4)3 7 B The most ionic fluoride will contain elements
with the largest difference in electronegativity
(f) aluminium hydride; ions present: Al3+ H−, 1 ×
– i.e. will contain the metal with the lowest
3+ with 3 × 1–, so forms AlH3
electronegativity. From the Periodic Table,
3 The names are deduced directly from the we know this will be the metal the furthest
formulas, referring to the table of ions on page to the left and the lowest, which is Cs. The
142 if needed. Note that where a Roman fluoride will be CsF.
numeral is given in brackets after the name of Note that in multiple-choice questions
the cation, it refers to the oxidation number, on Paper I you will not have access to
which is explained in Chapter 9. This is used the IB data booklet, but you do have a
where an element may form different ions with Periodic Table. You do not need specific
different oxidation states. electronegativity values to answer this

1
 question, but you do need to know the δ δ
(c) Cl F (d) O O
trends.
δ δ δ
(e) H N H
8 D The elements which react most readily
will be those with the largest difference in δ
H
electronegativity, i.e. between those on the
bottom left and those on the top right. From 13 (a) C 2.6 H 2.2 difference = 0.4
the Periodic Table we can see that K is C 2.6 Cl 3.2 difference = 0.6, more polar
below Li and Cl is above Br. (b) Si 1.9 Li 1.0 difference = 0.9
9 ● Test the melting point: ionic solids have high Si 1.9 Cl 3.2 difference = 1.3, more polar
melting points. (c) N 3.0 Cl 3.2 difference = 0.2
●● Test the solubility: ionic compounds usually N 3.0 Mg 1.3 difference = 1.7, more polar
dissolve in water but not in hexane.
F
●● Test the conductivity: ionic compounds in 14 (a) H F (b) F C F
aqueous solution are good conductors, as
Cl
are ionic compounds when they are molten.

10 D All the other substances contain polyatomic H H Cl

ions that contain covalent bonds. (c) H C C H (d) Cl P Cl
H H
H H H H
11 C O C O H C O C H (e) H C C H (f) H C C H
15 The number of valence electrons in a molecule is
H H
the sum of the valence electrons of all the atoms
A B
present.
H O
(a) BeCl2: Be has 2 valence electrons and each
C O H C C O H Cl has 7; 2 + (2 × 7) = 16
(b) BCl3: Be has 3 valence electrons and each
H
Cl has 7; 3 + (3 × 7) = 24
C D
(c) CCl4: C has 4 valence electrons and each Cl
Substances A and D contain carbon–oxygen has 7; 4 + (4 × 7) = 32
double bonds and substance B contains
(d) PH3: P has 5 valence electrons and each H
carbon–oxygen single bonds. Compound C
has 1; 5 + (3 × 1) = 8
(carbon monoxide) contains a triple bond.
Triple bonds are shorter than both single and (e) SCl2: S has 6 valence electrons and each Cl
double bonds. has 7; 6 + (2 × 7) = 20
(f) NCl3: N has 5 valence electrons and each Cl
12 Any bonds between two different atoms will be
has 7; 5 + (3 × 7) = 26
polar: the element which is further to the left
+
and/or lower will be δ+ and the element which H H
is further to the right and/or higher will be δ+. 16 H+ O H H O H
These can be predicted from the Periodic Table
without the need to consult electronegativity 17 
O 
values.
N O
δ δ δ δ δ O N O
(a) H Br (b) O C O
(a) (b)
2
 
F
O N O O O
O
C
(c) (d) F
F
F
H N N H
Bond angles are 109.5°.
N N
(c) HCN: Lewis structure is H C N
(e)
Two domains of electrons around the carbon
18 The steps to follow: atom, electron domain geometry is linear.
●● work out the Lewis structure (as in All electron pairs are bonded so shape is
question 4) linear (as drawn in Lewis structure). Bond
●● count the number of electron domains angle is 180°.
around the central atom, which gives the F
geometric arrangement of the electron
domains
(d) NF3: Lewis structure is F N
●● determine the numbers and positions of
the bonded atoms within this geometric
F
arrangement to give the shape of the
Four domains of electrons around the
molecule
nitrogen atom, electron domain geometry is
●● adjust bond angles in the case of the
tetrahedral.
presence of non-bonded pairs (lone pairs).
One lone pair and three bonded pairs so
S shape is trigonal pyramidal.
(a) H2S: Lewis structure is H H
N
Four domains of electrons around the F
F
sulfur atom, electron domain geometry is F
tetrahedral.
As lone pairs repel more than bonded
Two lone pairs and two bonded pairs so
pairs the bond angles are less than 109.5°.
shape is bent (as drawn in Lewis structure).
Observed bond angle is 107°.
As lone pairs repel more than bonded
Cl
pairs the bond angles are less than 109.5°.
Observed bond angle is 105°.
(e) BCl3: Lewis structure is Cl B
F
Cl
(b) CF4: Lewis structure is F C F Three domains of electrons around the
boron atom, electron domain geometry is
F trigonal planar.
Four domains of electrons around the All electron pairs are bonded so shape is
carbon atom, electron domain geometry is trigonal planar. Bond angles are 120°.
tetrahedral. 120° bond angle, triangular planar, three
All electron pairs are bonded so shape is domains of electrons around the boron
tetrahedral. atom.

3
 H 2
O

(f) NH2Cl: Lewis structure is Cl N C

O O

H
Bond angles are 120°.
Four domains of electrons around the 
nitrogen atom, electron domain geometry is O
tetrahedral. (b) NO3−: Lewis structure is O N O
One lone pair and three bonded electron
pairs so shape is trigonal pyramidal. Three domains of electrons around the
nitrogen atom, electron domain geometry is
N
Cl trigonal planar.
H
Cl All electron domains are bonded so shape is
trigonal planar.
As lone pairs repel more than bonded

pairs the bond angles are less than 109.5°. O
Observed bond angle is 107°.
N
(g) OF2: Lewis structure is F O F O O
Four domains of electrons around the
oxygen atom, electron domain geometry is Bond angles are 120°.

tetrahedral.
(c) NO2+: Lewis structure is O N O
Two lone pairs and two bonded pairs so
shape is bent. Two domains of electrons around the
nitrogen atom, electron domain geometry is
O
linear.
F F
All electron domains are bonded so shape
As lone pairs repel more than bonded is linear (as drawn in Lewis structure). Bond
pairs the bond angles are less than 109.5°. angle is 180°.
Observed bond angle is 105°. 
(d) NO2−: Lewis structure is O N O
19 Drawing the Lewis structure of these ions will
help you to sort out their structure. Three domains of electrons around the
(a) CO32−: Lewis structure is nitrogen atom, electron domain geometry is
2 trigonal planar.
O
One lone pair and two bonded electron
O C O domains so shape is bent.

Three domains of electrons around the N
O O
carbon atom, electron domain geometry is
trigonal planar. Lone pairs repel more so bond angle will be
All electron domains are bonded so shape is slightly less than 120°.

trigonal planar. (e) ClF2+: Lewis structure is F Cl

4
 Four domains of electrons around the
A
chlorine atom, electron domain geometry is
tetrahedral. B B

Two lone pairs and two bonded pairs so A bent shape can also be obtained from a
shape is bent. trigonal planar electron domain geometry
with three electron domains if one domain

Cl is a lone pair. A bent shape can also be
F F obtained from a trigonal planar electron
domain with three electron domains if two
Lone pairs repel more so bond angle will be domains are bonded and there is one lone
less than 109.5°. Observed angle is 105°. pair.
(f) SnCl3−: Lewis structure is (c) B A B

Cl A linear shape can be obtained from a linear
electron domain geometry with two electron
Cl Sn Cl domains if both domains are bonded.
B
Four domains of electrons around the
tin atom, electron domain geometry is
A
tetrahedral.
One lone pair and three bonded pairs so
B
shape is trigonal pyramidal.
 A linear shape can also be obtained from
Sn a trigonal bipyramidal electron domain
Cl
Cl geometry with five electron domains if two
Cl
domains are bonded and there are three
Lone pairs repel more so bond angle will be lone pairs.
less than 109.5°. Observed angle is 107°.
A
20 Drawing the shapes will help you to visualize them. (d) B B

B B
A trigonal pyramidal shape can be obtained
from a tetrahedral electron domain geometry
(a) A
B with four electron domains if three domains
B
are bonded and there is one lone pair.
B
B
A tetrahedral shape can only be obtained
from a tetrahedral electron domain geometry (e) A
with four electron domains and with all B B
domains bonded. A trigonal planar shape can only be obtained
from a trigonal planar electron domain
A geometry with three electron domains and
(b) Br B with all domains bonded.
A bent shape can be formed from a 21 The polarity of a molecule depends on the
tetrahedral electron domain geometry with presence of polar bonds and whether or not
four electron domains if two domains are those bonds are symmetrically arranged.
bonded and there are two lone pairs.
The steps to follow are:

5
 ●● work out the shape of the molecule (as in (g) Non-polar; F2 is a symmetrical molecule so
question 18) the bonding electrons are shared equally
●● from the relative position of the polar bonds, between atoms.
determine whether or not there is a net (h) Non-polar; although F is more
dipole. electronegative than B, the shape of the
(a) PH3 molecule is trigonal planar, and so all the
δ
dipoles cancel out.
δ
P δ
H H 22 H H H Cl
δ
H
C C C C
This is a pyramidal molecule, it is polar.
Cl Cl Cl H
(b) CF4
cis-dichloroethene trans-dichloroethene
δ
F
The cis isomer has a net dipole moment as both
δ
δ
C the electronegative atoms are on the same side
δ
F F
δ
of the molecule and so there is an overall dipole
F
moment for the molecule. In the trans isomer the
This is a tetrahedral molecule, all bond dipoles cancel out.
dipoles cancel, so it is non-polar.
23 The C–O bond order for each species can be
(c) HCN determined from their Lewis structures.
δ δ
H C N CO: Lewis structure is C O

It contains a C≡O triple bond, bond order = 3.

This is a linear molecule, the two dipoles
(from the H–C bond and the C–N bond) do CO2: Lewis structure is O C O
not cancel (in fact, they add together), so it is
It contains two C=O double bonds, bond
polar.
order = 2.
(d) BeCl2
CO32−: Three resonance structures:
Cl Be Cl
2– 2– 2–
O O O

This is a linear molecule, the two dipoles C C C

O O
cancel, so it is non-polar. O O O O

(e) C2H4
The C–O bonds are delocalized and have a
H H bond order of 1.33.
C C H

H H CH3OH: Lewis structure is H C O H

Each C is trigonal planar, each C–H bond
is slightly polar, the C=C is non-polar, the H
structure is symmetrical, so non-polar. It contains a C–O single bond, bond order = 1.
(f) Polar, due to uneven distribution of electrons
To rank in order of increasing CO bond length
as fluorine is more electronegative than
we need to put the species with the shortest
chlorine.

6
 bond (highest CO bond order) first: CO < CO2 < D is a non-polar molecular solid; it isn’t soluble in
CO32− < CH3OH. water (so isn’t an ionic solid), it doesn’t conduct
electricity when solid (so isn’t a metal) and it has
24 NO3− has three resonance structures and the
the lowest melting point.
N–O bond order is 1.33:
– – –
E is an ionic compound; it is soluble in water,
O O O the aqueous solution conducts electricity while
N N N the solid doesn’t and it has the next to highest
O O O O O O
melting point.

HNO3 has two resonance structures and there 28 A Both methanol and ethanol (D) are soluble in
are two distinct N–O bonds. The N–O(H) bond is water due to hydrogen bonding between the
always a single bond and has a bond order of 1. alcohol and water; however, methanol will be
The N–O bond that resonates has a bond order the more soluble as it has the smaller non-
of 1.5. polar part of the molecule. Neither methane
(B) nor ethane (C) will dissolve in water as
O O
neither have any polar bonds.
N N 29 (a) London dispersion forces, as it is a non-
H O O H O O
polar molecule.

Bond lengths decrease as bond order (and bond (b) H bonds, dipole–dipole, London dispersion
strength) increases, therefore the N–O bonds forces, as it is a polar molecule due to its
in the nitrate(V) ion that all have a bond order of tetrahedral shape and lone pair of electrons.
1.33 will be longer than the two bonds in nitric(V) Nitrogen is sufficiently electronegative to
acid with a bond order of 1.5 and shorter than allow hydrogen bonding to occur.
the N–O bond with a bond order of 1. (c) London dispersion forces, as it is a non-
polar molecule.
25 Similarities: strong, high melting points, insoluble
(d) Dipole–dipole, London dispersion forces, as
in water, non-conductors of electricity, good
the molecule is bent about the oxygen atom
thermal conductors.
due to its two lone pairs of electrons and so
Differences: diamond is stronger and more
has a dipole.
lustrous; silicon can be doped to be an electrical
conductor. 30 (a) C2H6, it is the smaller molecule and so has
fewer London (dispersion) forces between
26 Graphite and graphene have delocalized
adjacent molecules.
electrons that are mobile and so they conduct
(b) H2S, sulfur is less electronegative than
electrical charge. In diamond all electrons are
oxygen (in water) and so the dipole–dipole
held in covalent bonds and so are not mobile.
forces are weaker.
27 A is a metal; it conducts electricity when solid. (c) Cl2, it has the smallest molecule and so
B is giant molecular substance; it doesn’t London dispersion forces are weaker
dissolve in water (so isn’t an ionic solid), it between molecules. (At room temperature,
doesn’t conduct electricity when solid (so isn’t a chlorine is a gas but bromine is a liquid.)
metal) and it has the highest melting point. (d) HCl, chlorine is less electronegative than
C is a polar molecular solid; it is soluble in water fluorine and so the dipole–dipole forces are
but doesn’t conduct (so isn’t an ionic solid); its weaker.
melting point is low (but not the lowest), so it
isn’t the non-polar molecular solid.

7
31 B Metallic bonding is the attraction between 
cations and delocalized electrons. See page (b) ClO3–: Lewis structure is O Cl O
182 for more detail. O

32 (a) Malleability, thermal conductivity, thermal Four domains of electrons around the
stability, insolubility (so no danger of toxicity). chlorine atom, electron domain geometry is
tetrahedral.
(b) Light, strong, forms alloys, thermal stability
(both high temperatures due to friction and One lone pair and three bonded electron
low temperatures high in the atmosphere). pairs so shape is trigonal pyramidal.

(c) Thermal conductivity, thermal stability, non-
Cl
corrosive, insolubility.
O O
(d) Light, strong, non-corrosive. O

33 (i) Anodizing: increasing the thickness of the Lone pair repels more so bond angles are
surface oxide layer helps resist corrosion, less than 109.5°. Observed angle is 107°.
also adds colour and enables designs to be
(c) OF2: Lewis structure is F O F
added to the surface.
(ii) Alloying: mixing Al with other metals such as Four domains of electrons around the
Mg and Cu increases hardness and strength oxygen atom, electron domain geometry is
while retaining lightness. tetrahedral.
Two lone pairs and two bonded pairs so
34 The steps to follow:
shape is bent.
●● work out the Lewis structure
O
●● count the number of electron domains
F
around the central atom, which gives the F
geometric arrangement of the electron Lone pairs repel more so bond angle will be
domains less than 109.5°. Observed angle is 105°.
●● determine the numbers and positions of O
the bonded atoms within this geometric
arrangement to give the shape of the (d) XeO4: Lewis structure is O Xe O
molecule
●● adjust bond angles in the case of the O
presence of non-bonded pairs (lone pairs).
Four domains of electrons around the
F xenon atom, electron domain geometry is
tetrahedral.
(a) XeF2: Lewis structure is Xe All electron domain are bonded so the shape
is tetrahedral.
F
O
Five domains of electrons around the xenon
atom, electron domain geometry is trigonal Xe
pyramidal. O O
O
Three lone pairs and two bonded electron
pairs so shape is linear (as indicated by Bond angles are 109.5°.
Lewis structure). Bond angle is 180°.

8
(e) PCl6–: Lewis structure is 35 This is similar to question 20.
 The table on page 189 confirms the relationships
Cl between the number of charge centres and the
Cl Cl
shape of the molecule.
P
Cl Cl B B
Cl (a) A
B B
Six domains of electrons around the A square planar shape can be obtained from
phosphorous atom, electron domain an octahedral electron domain geometry
geometry is octahedral. with six electron domains if four domains are
All electron domains are bonded so the bonded and there are two lone pairs.
shape is octahedral. B
– B B
F
(b) A
F F B B
P
B
F F
F An octahedral shape can be obtained from
an octahedral electron domain geometry
Bond angles are 90° and 180°. with six electron domains if all six domains
(f) IF4+: Lewis structure is are bonded.
B
+
F B B
(c) A
F
B B
F I A square pyramidal shape can be obtained
from an octahedral electron domain
F geometry with six electron domains if five
domains are bonded and there is one lone
Five domains of electrons around the iodine pair.
atom, electron domain geometry is trigonal B
bipyramidal. B
One lone pair and four bonded pairs so the (d) B A
shape is see-saw (sawhorse). B
B
+
F A trigonal bipyramidal shape can be
F obtained from an octahedral electron
I domain geometry with five electron domains
F if all five domains are bonded.
F (e) B A B
A linear shape can be obtained from a linear
Bond angles in the equatorial plane are
electron domain geometry with two electron
distorted due to the lone pair and the
domains if both domains are bonded.
observed angle is around 117°. The axial
bond angle is also reduced to around 170°.

9
 B SF6 has 6 charge centres, with all 6 as
bonding pairs (no lone pairs) and so is
A octahedral. The F–S–F bond angle is 90°.
F
B
F F
A linear shape can also be obtained from S
a trigonal bipyramidal electron domain F F
geometry with five electron domains if two F
domains are bonded and there are three
37 (a) H F
lone pairs.
Note that in part (e), linear geometry can arise HF is polar; the F is more electronegative
from two charge centres with no lone pairs (e.g. than H so the HF molecule has a dipole.
BeCl2, C2H2) or from five charge centres with Cl
three lone pairs (e.g. I3−).

36 The bond angles are determined by the overall (b) C net dipole
F F
shape of the molecule, so this must be deduced
F
first.
CF3Cl is polar; both the Cl and the F are
(a) Lewis structure is F F electronegative to different extents so the
Kr C–F bond is more polar than the C–Cl bond.
F F
The dipoles do not cancel so there is a net
KrF4 has 6 charge centres with 4 bonding dipole and the molecule is polar.
pairs and 2 lone pairs, which is octahedral H H
overall. This will be a square planar structure,
with all F–Kr–F bond angles = 90°. (c) H C C H no net dipole
F F
Kr H H
F F C2H6 is non-polar as the molecule is
symmetrical and the dipoles associated with
(b) P the weakly polar C–H bonds cancel.
Cl Cl
Cl P
(d) Cl Cl
PCl3 has 4 charge centres with 3 bonding net dipole
Cl
pairs and 1 lone pair. This will be trigonal
pyramidal with Cl–P–Cl bond angles around PCl3 is polar as it is an asymmetrical
107° (compressed slightly by the lone pair). molecule and the dipoles associated with
the three polar P–Cl bonds do not cancel so
P
Cl there is a net dipole.
Cl
Cl H H

F (e) C C no net dipole

F F
H H
(c) S
F F C2H4 is non-polar as the molecule is
F symmetrical and the dipoles associated with
the weakly polar C–H bonds cancel.

10
 (f) H C C H no net dipole The molecule is symmetrical so the dipoles
created by the polar Te–F bonds cancel and
C2H2 is non-polar as the molecule is
the molecule is non-polar.
symmetrical and the dipoles associated with
the weakly polar C–H bonds cancel. (d) BrF4– is a molecular ion so it is a charged
species. Because it is charged it cannot be
38 (a) Lewis structure of ClBr3: designated as polar or non-polar as these
Br terms only apply to neutral molecules.

Cl Br
F F
Br Br
F F
Five domains of electrons around the
chlorine atom, electron domain geometry is
trigonal bipyramidal. (e) PCl4+ is a molecular ion so it is a charged
species. Because it is charged it cannot be
Two lone pairs and three bonded pairs so
designated as polar or non-polar as these
the shape is T-shaped.
terms only apply to neutral molecules.
Br (f) FCl2+ is a molecular ion so it is a charged
species. Because it is charged it cannot be
Cl Br
net dipole designated as polar or non-polar as these
terms only apply to neutral molecules.
Br
39 BF3 has a trigonal planar shape.
The molecule is non-symmetrical so the
dipoles created by the slightly polar Cl–Br F
bonds do not cancel and the molecule is
polar. B
(b) IO4 is a molecular ion so it is a charged
– F F
species. Because it is charged it cannot be
To determine the formal charge on the boron
designated as polar or non-polar as these
and fluorine atoms we use the formula:
terms only apply to neutral molecules.
formal charge (FC) on atom = valence electrons
F
of atom – (½ bonding electrons + lone pair
F F electrons)
(c) Lewis structure of TeF6: Te
FC (B) = 3 – (½ × 6 + 0) = 0
F F
FC (F) = 7 – (½ × 2 + 6 ) = 0
F
As all the atoms present in the molecule have
Six domains of electrons around the a formal charge of zero this represents a stable
chlorine atom, electron domain geometry is structure even though the central boron atom
octahedral. does not obey the octet rule.
All electron pairs are bonded pairs so the
40 The Lewis structure for SO42– where the sulfur
shape is octahedral.
atom obeys the octet rule is
F
F F
2
Te O
F F O S O
F O

11
 To determine the formal charge on the sulfur and
41 Lewis structure of oxygen (O2) is O O
oxygen atoms we use the formula:
The O=O double bond has a bond order of 2.
formal charge (FC) on atom = valence electrons
Ozone (O3) has two resonance structures:
of atom – (½ bonding electrons + lone pair
O O O O
electrons) O O
FC (S) = 6 – (½ × 4 + 0) = +2
Ozone resonates between these two structures
FC (O) = 6 – (½ × 2 + 6) = –1 so each O–O bond is between a single and
double bond, with a bond order of 1.5.
(Total formal charge for the one sulfur and four
oxygen atoms = +2 + 4(–1) = –2, which is Bond strength increases with increasing bond
order. With a bond order of 1.5 the O–O bonds
equivalent to the overall 2– charge on the ion).
in O3 are weaker than the double bond in O2
The Lewis structure for SO42– where the sulfur because of the lower bond order, therefore
atom has an expanded octet with 12 electrons is dissociation of ozone occurs with lower energy
2 light (longer wavelength).
O
42 O3 breakdown is catalysed by NOx and CFCs in
O S O
the atmosphere.
O
e.g. CCl2F2(g) → CClF2•(g) + Cl•(g)
Two of the oxygens are singly bonded and two CFCs break down in upper atmosphere
are doubly bonded to the central sulfur atom. Cl•(g) + O3(g) → O2(g) + ClO•(g)
FC (S) = 6 – (½ × 12 + 0) chlorine radical reacts with ozone and another
=0 radical is produced
Singly bonded O: FC (O) = 6 – (½ × 2 + 6) ClO•(g) + O•(g) → O2(g) + Cl•(g)
= –1 chlorine radical is regenerated and so acts a
Doubly bonded O: FC (O) = 6 – (½ × 4 + 4 ) catalyst for ozone destruction
=0
43 Electrons in a sigma bond are most
(Total formal charge for the one sulfur and four concentrated in the bond axis, the region
oxygen atoms = 0 + 2(–1) + 2(0) = –2, which is between the nuclei. Electrons in a pi bond are
equivalent to the overall 2– charge on the ion). concentrated in two regions, above and below
the plane of the bond axis.
Comparing the two structures we see that:
(i) the structure for the expanded octet 44 (a) H–H in H2 H H
contains fewer atoms with a formal charge
(the expanded octet structure has more
atoms where the formal charge = 0) (b) H–F in HF H F

(ii) the formal charges that do exist on atoms in

the expanded octet structure are smaller (all (c) Cl–Cl in Cl2
–1) than those in the octet structure (+2 on
Cl Cl
sulfur).
Both of these are factors that contribute to the
expanded octet being the preferred structure.

12
 
H H

(d) C–H in CH4 C (b) BH4– is tetrahedral: B

H
H H
H H
H
As the boron atom has a tetrahedral electron
(The four orbitals around the central carbon domain geometry it is sp3 hybridized.
are sp3 hybrid orbitals.) O
(e) C–H in C2H4
π (c) SO3 is trigonal planar: S
σ O O
H H As the sulfur atom has a trigonal planar
C C
electron domain geometry it is sp2
H H hybridized.

(Each carbon is sp2 hybridized so has three (d) BeCl2 is linear: Cl Be Cl

sp2 hybrids which form the sigma bonds and As the sulfur atom has a linear electron
an unhybridized p orbital that forms the pi domain geometry it is sp hybridized.
bond.) (e) CH3COOH is trigonal planar around the
(f) C–H in C2H2 carbon highlighted:
π O

σ
H C
C C H
H3C OH

As the carbon atom has a trigonal planar

(Each carbon is sp hybridized so has two electron domain geometry it is sp2
sp hybrids which form the sigma bonds and hybridized.
two unhybridized p orbitals that form the two
pi bonds.) 46 In C6H12 cyclohexane the carbon atoms are
(g) C–Cl in C2H3Cl sp3 hybridized, each forming a tetrahedral
arrangement with two neighbouring carbon
π
Cl atoms and two hydrogen atoms. The bond
σ
H angles of 109.5° give the puckered shape.
C C
H
H H
H
H H

(Each carbon is sp hybridized so has three

2 C C
H C H
sp2 hybrids which form the sigma bonds and H C H
C C
an unhybridized p orbital that forms the pi H H
bond.)
O H H

In C6H6 benzene the carbon atoms are all

45 (a) H2C=O is trigonal planar: C
sp2 hybridized, forming a planar triangular
H H
arrangement with bond angles of 120°.
As the carbon atom has a trigonal planar
electron domain geometry it is sp2
hybridized.

13
 H In diamond carbon atoms are all linked to four
other atoms in a tetrahedral arrangement and
the carbon atoms are sp3 hybridized.
H C H
In graphite the carbon atoms are linked to three
C C
other atoms, forming sheets of interlocked
hexagons and the carbon atoms are sp2
C C hybridized.
H C H
In fullerenes the carbon atoms are linked to three
other atoms, forming interlocked hexagons and
H pentagons that create a closed spherical cage
and the carbon atoms are sp2 hybridized.
Correct answer is A.
Practice questions 5 The structure of propyne is (see Chapter 10 for
structures of organic compounds):
1 The larger the electronegativity difference H
between the two atoms involved in a covalent
bond the more polar that bond will be. H C C C H
H–I H–Br H–Cl H–F
H
Electronegativity
difference
0.4 0.7 0.9 1.9 Each single bond is a σ bond. The triple bond
contains one σ and two π bonds so there are a
Correct answer is C. total of six σ and two π bonds.
2 Carbon forms a covalent network solid where Correct answer is B.
the atoms are all linked to each other by strong
6 Compounds can form hydrogen bonds when:
covalent bonds. It has a high melting point as
the melting of carbon involves breaking these (i) they contain a hydrogen atom covalently
strong bonds. bonded to a highly electronegative atom, N,
O or F
Carbon dioxide, CO2, is a covalently bonded
molecule. Weak intermolecular forces exist (ii) they have a lone pair on a highly
between the molecules and these are easily electronegative atom, N, O or F.
overcome, giving CO2 a very low melting point. The structures of the compounds are
Correct answer is A. (see Chapter 10 for structures of organic
compounds):
3 As these are non-polar or weakly polar H H H
A B
compounds the boiling points will depend on H C C O H H C Cl
the strength of the London dispersion forces
H H H
between the molecules. These increase with the
H O CH3CH2
size of the atoms in the molecules so the order is C D
CH3CH3 < CH3CH2Cl < CH3CH2Br < CH3CH2I. H C C H H3 CH2C N

Correct answer is A. H CH3CH2

Only C2H5OH meets both requirements.

4 See diagrams on page 169.
Correct answer is A.

14
7 Lewis structures of molecules: +
H
F
O
O
A F B B O S O H H
H C H C O
F
An oxygen atom has two unbonded electrons
that can pair with an electron donated from
Cl F
another atom to form two covalent bonds.
Cl
C Cl P D F Si F O
Cl
Cl F For oxygen to form a third bond this must be
a coordination bond where it donates both the
Only SO2 has a lone pair of electrons on the electrons in one of the lone pairs. H3O+ and
central atom. CO both contain oxygen atoms that have three
Correct answer is B. bonds.
Correct answer is C.
8 Delocalized electrons occur when compounds
have resonance structures. The correct answer 10 Consider the shapes obtained for the
will be the compound that does not have any compounds:
resonance structures. All of the species listed
F Cl
have resonance structures except C3H6.
F F Cl
O
–
O
–
O
–
S P Cl
A N N N
F F Cl
O O O O O O
F Cl
A: SF6 B: PCl5
– –
N N
B F
O O O O
F F
Xe B
O O
C F F F F
O O O O
C: XeF4 D: BF3

H H H Only SF6 is octahedral.

Correct answer is A.
D H C C C H
11 Statements I and III are correct. Statement II
is incorrect as σ bonds can also be formed
H H H
from the axial overlap of p orbitals. (Or from the
Correct answer is D. overlap of s and p orbitals as well as the axial
overlap of hybrid orbitals.)
9 A dative coordinate bond is a coordination
bond. It occurs when one atom donates both Correct answer is B.
of the electrons required to form a covalent 12 Atoms that have a trigonal planar arrangement
bond. Consider the Lewis structures of the of electron domains around them are sp2
compounds: hybridized.

15
 Consider the structures of the compounds H H H H

(see Chapter 10 for structures of organic A H C O C H B H C C O H

compounds):
H H H H
H
H O H H H
H
H C D
C H H H H C C H H C C C H

H H H H

A H O C C C C H
Only CH3CH2OH meets both requirements.
Correct answer is B.
H H H
15 The silicon atoms in SiO2 are surrounded by four
H
bonding pairs so they are sp3 hybridized.
The oxygen atoms in SiO2 are surrounded by
B H C C C H
two bonding and two non-bonding pairs so they
are sp3 hybridized.
H

C D

Correct answer is C.
silicon atoms
13 When a central atom has two bonding and three
oxygen atoms
non-bonding pairs there is a trigonal bipyramidal
arrangement of the electron domains around the Correct answer is A.
central atom but the shape is linear due to the
two bonded atoms. 16 Consider the structures of butan-1-ol and
butanal (see Chapter 10 for structures of organic
F
compounds):
H H H H
Xe
H O C C C C H
F
H H H H
Correct answer is D.
butan-1-ol
14 Compounds can form hydrogen bonds when:
O H H H
(i) they contain a hydrogen atom covalently
bonded to a highly electronegative atom, N, H C C C C H
O or F
(ii) they have a lone pair on a highly H H H
electronegative atom, N, O or F. butanal
Structures of compounds (see Chapter 10 for The intermolecular forces present in butan-
structures of organic compounds): 1-ol are hydrogen bonding as it contains
16
 a hydrogen atom bonded to a highly 

electronegative oxygen as well as a lone pair 

C C
on the highly electronegative oxygen. The H sp sp sp sp H

intermolecular forces present in butanal are 

dipole–dipole interactions due to the polar

C=O bond. Because hydrogen bonding is a σ bonds are formed from the axial
stronger intermolecular force than dipole–dipole overlap of two sp hybrid orbitals and sp
interactions butan-1-ol will have a higher boiling hybrids with 1s hydrogen orbitals. The
point than butanal. electron density in σ bonds is centred
along the inter-nuclear axis (see page
F
198).
F F
17 (a) (i) Br P Br S π bonds are formed by the side-on
F F overlap of the unhybridized p orbitals on
Br F the two carbon atoms and the electron
PBr3 SF6 density of the π bonds is above and
below the inter-nuclear axis (see page
(ii) There are four electron domains around
199).
the central P atom in PBr3. Because
three of these are bonded pairs the (ii) The structure of trans-but-2-ene-1,4-
shape of PBr3 is trigonal pyramidal. dioic acid is given below.
Because the lone pair repels more than O
the bonded pairs the bond angle will be H
<109.5°.(Experimentally observed value O C H
is 101°.) C C
H
There are six electron domains around C O
H
the central S atom in SF6. Because all of O
these are bonded pairs the shape of SF6
is octahedral and the bond angles are all Each single bond is a σ bond. The
90°. double bonds contain one σ and one
π bond so there are a total of 11 σ and
(iii) The P–Br bonds in PBr3 are polar (Δχ
three π bonds.
= 0.7). Because the molecule is not
symmetrical the dipoles created by the (iii) O
three P–Br bonds do not cancel so the H
O C H
molecule has a net dipole and PBr3 is a
C C
polar molecule.
H
The S–F bonds in SF6 are highly polar C O
H
(Δχ = 1.5). However, because the O
molecule is symmetrical the dipoles
trans-but-2-ene-1,4-dioic acid
created by the six S–F bonds cancel so
there is no net dipole and SF6 is a non- H H
O O
polar molecule.
(b) (i) The structure of ethyne showing the O C C O
orbital overlap and formation of σ and π C C
bonds is given below.
H H

cis-but-2-ene-1,4-dioic acid

17
 The two isomers of but-2-ene-1,4-dioic Graphite is a covalent network structure
acid have different intermolecular forces. where the carbon atoms are sp2 hybridized
In the trans-isomer strong intermolecular and each atom is covalently bonded to three
forces exist due to hydrogen bonding other atoms, with bond angles of 120°,
between the molecules and it has a forming sheets of interlinked hexagons.
high melting point. In the cis-isomer London dispersion forces exist between
intramolecular hydrogen bonding occurs the sheets. Electrons are delocalized over
between the acid functional groups. This each sheet so graphite is able to conduct
results in weaker intermolecular forces electricity.
between molecules and a lower melting
point for the cis-isomer.
(iv) The close arrangement of the two acid
functional groups in cis-but-2-ene-
1,4-dioic acid allows for an internal
condensation reaction to occur on
heating and a water molecule is
eliminated to form the cyclic anhydride.
C60 fullerene contains carbon atoms that are
(c) Each oxygen atom with four electron sp2 hybridized and each atom is covalently
domains is sp3 hybridized and each oxygen bonded to three other atoms to form
atom with three electron domains is sp2 interlinked hexagons and pentagons with
hybridized. bond angles between 109.5° and 120°,
sp3 H resulting in a cage-like structure. London
H sp3
dispersion forces exist between the C60
O O
fullerenes. Electrons are delocalized on each
fullerene but limited contact between the
sp2 O C C O sp
2
individual fullerenes makes fullerene a semi-
C C
conductor at room temperature.
H H

18 (a) Diamond is a covalent network structure

where the carbon atoms are sp3 hybridized
and every carbon atom is covalently
bonded to four others, forming a repeating
tetrahedral arrangement with 109.5° bond
angles. Diamond does not have delocalized
electrons so it is not able to conduct (b) (i) SiO2 is a covalent network solid with
electricity. each silicon bonded to four oxygen
atoms and each oxygen atom bonded
to two silicon atoms, giving the empirical
formula SiO2.

18
 2–
O

C
O O

2– 2–
silicon atoms O O
oxygen atoms
C C
(ii) Because SiO2 is a covalent network O O O O
solid it is necessary to break strong
covalent bonds for it to melt. This
requires a large amount of energy and
2–
SiO2 has a high melting point so it is a
O
solid at room temperature.
CO2 is a discrete molecule with weak C
London dispersion forces between the O O
molecules. These intermolecular forces
are weak and easy to overcome so CO2 Because the pi electrons are delocalized
has a low boiling point and is a gas at over the three positions this reduces
room temperature. electron–electron repulsions and increases
(c) The Lewis structure of carbon monoxide is: the stability of the carbonate ion.
(e) Hybridization is the mixing of atomic orbitals
C O
to form new hybrid orbitals. The number of
The carbon and oxygen atoms are both sp hybrid orbitals that are formed is equal to the
hybridized and they form a covalent triple number of atomic orbitals that mix to form
bond. One of these bonds is a coordination the hybrids.
bond where the oxygen atom has donated In carbon dioxide the carbon atom has two
both electrons. electron domains so it is sp hybridized.
(d) The delocalization of pi electrons occurs One p orbital has mixed with the s orbital
when a multiple bond can occur in more to form two sp hybrid orbitals, leaving two
than one position within a molecule. When unhybridized p orbitals able to form the π
this situation occurs two or more equally bonds.
valid Lewis structures (resonance structures) O C O
can be drawn for the molecule. The reality
is that the pi bond is shared over all the In diamond (see picture in Q18(a)) the
positions and is represented as a partial carbon atoms have four electron domains so
bond occurring in all positions. they are sp3 hybridized. The three p orbitals
In the carbonate ion the central carbon atom have mixed with the s orbital to form four sp3
is sp2 hybridized, giving a trigonal pyramidal hybrid orbitals.
shape and there are three resonance In graphite (see picture in Q18(a)) the carbon
structures: atoms have three electron domains so they
are sp2 hybridized. Two p orbitals have

19
 mixed with the s orbital to form three sp2
hybrid orbitals, leaving one unhybridized p
orbital able to form a pi bond.
In the carbonate ion (see picture Q18(d)) the
π-bonding overlap
carbon atom has three electron domains
so it is sp2 hybridized. Two p orbitals have (b)
mixed with the s orbital to form three sp2
C4
hybrid orbitals, leaving one unhybridized p
orbital able to form a pi bond.
C2 C3
19 Consider the Lewis structures (see Chapter 10
for structures of organic compounds): C1

H H

H C O C H C1 has four electron domains so it is sp3

hybridized.
H H C2 has three electron domains so it is sp2
2-methoxymethane hybridized.

H H F
F
H C C O H 21 S S
F F F

H H SF2 F

ethanol SF4

In methoxymethane the intermolecular forces F

present are London dispersion forces and F F
dipole–dipole interactions due to the polar C–O S
bond. These are relatively weak intermolecular F F
forces so methoxymethane will have a low F
boiling point (–24 °C).
SF6
In ethanol hydrogen-bonding intermolecular
In SF2 there are four electron domains around
forces can occur as there is a hydrogen atom
the central atom and two of these are bonded so
bonded to a highly electronegative oxygen
the molecule has a bent shape.
atom and a lone pair of electrons on a highly
electronegative oxygen atom. As hydrogen In SF4 there are five electron domains around the
bonding is significantly stronger than London central atom and four of these are bonded so
dispersion forces and dipole–dipole interactions, the molecule has a see-saw shape.
ethanol will have a much higher boiling point In SF6 there are six electron domains around
(78 °C) than methoxymethane. the central atom and all six are bonded so the
molecule has an octahedral shape.
20 (a) The pi bond is formed from side-on overlap
of p orbitals on C2 and C3:

20
 – (ii) H H
22 (a) Cl P Cl N H
C C H
Cl H H C
PCl3 NH2– H H propene
F All single bonds are σ bonds, double
bonds contain one σ bond and one
F Xe F π bond. Overall propene has eight σ
bonds and one π bond.
F (iii) The bond angles on the carbons of
propene with three electron domains
XeF4
are 120° as this is a trigonal planar
In PCl3 there are four electron domains arrangement. The bond angles on the
around the central atom and three of these carbon with four electron domains
are bonded so the molecule has a trigonal are 109.5° as this is a tetrahedral
pyramidal shape. The bond angles will be arrangement.
<109.5°.
(iv) H
In NH2– there are four electron domains
around the central atom and three of these
are bonded so the ion has a bent shape. H C C C H
The bond angles will be ≈ 105°.
H
In XeF4 there are six electron domains
around the central atom and four of these propyne
are bonded so the molecule has a square A triple bond consists of one σ bond
planar shape. The bond angles will be 90°. and two π bonds. To form a triple bond
(b) (i) Sigma bonds between two carbon the two carbon atoms must be sp
atoms are formed from axial overlap of hybridized; the σ bond forms from the
two s or p orbitals (or spx hybrids). overlap of a sp hybrid on each carbon
atom and the two pi bonds are formed
from the overlap of the two unhybridized
p orbitals on each carbon.



σ bonding overlap of s orbitals (top) H sp
C
sp sp
C
sp H
and p orbitals (bottom) 

Pi bonds between two carbon atoms

are formed from side-on overlap of two
23 (a) (i) 2–
F
p orbitals. F F
Si
F F
F
π-bonding overlap
SiF62–

21
 (ii) + O
O N O
H C N H
NO2+
SiF62– has six electron domains and all six H
are bonded pairs so it has an octahedral
shape. All bond angles will be 90° and 180° (ii) Hybridization is the mixing of atomic
(for atoms on the same axis). orbitals to form new hybrid orbitals. The
number of hybrid orbitals that is formed
NO2+ has two electron domains and both are
is equal to the number of atomic orbitals
bonded pairs so the shape is linear and the
that mix to form the hybrids.
bond angle is 180°.
(iii) Sigma bonds between atoms are
(b)
formed from axial overlap of two s or p
N orbitals (or spx hybrids).
O O O C O

NO2 has a bent shape and the dipoles

created by the polar N–O bonds do not
cancel so NO2 has a net dipole and it is
therefore a polar molecule.
σ bonding overlap of s orbitals (top)
CO2 is a linear molecule and the dipoles and p orbitals (bottom)
created by the polar C–O bonds cancel each
other so CO2 does not have a net dipole and Pi bonds between two atoms are
is therefore a non-polar molecule. formed from side-on overlap of two p
orbitals.
(c) SiO2 is a covalent network solid with each
silicon covalently bonded to four oxygen
atoms and each oxygen atom covalently
bonded to two silicon atoms, giving the
empirical formula SiO2.
π-bonding overlap

(iv) In HCONH2 there are three electron domains

around the carbon atom so it is sp2 hybridized.
There are four electron domains around the
nitrogen atom so it is sp3 hybridized.

24 Formal charge (FC) on atom = valence electrons

–( 1
2
bonding electrons + lone pair electrons )
(a) (i) H
silicon atoms
oxygen atoms C N N

(d) (i) The name of HCONH2 is methanamide H

(see Chapter 10 for naming and
structures of organic compounds). FC (H) = 1 – ( 12 × 2) = 0
FC (C) = 4 – ( × 8) = 0
1
2

22
 FC (N1) = 5 – ( 12 × 8) = +1 between Al and O. Al2O3 has some partially
covalent character, which means the comparison
FC (N2) = 5 – ( × 4 + 4) = –1
1 with more ionic oxides is not fully valid.
2
2 F2 has lower bond enthalpy (158 kJ mol–1) than
(ii) H expected based on its atomic radius due to
C N N repulsion between the non-bonding lone pairs
on the two F atoms. The F–F bond length is so
H short (0.142 nm) that the lone pairs on the two
FC (H) = 1 – ( 12 × 2) = 0 atoms are close enough to repel each other and
weaken the bond.
FC (C) = 4 – ( × 6) = +1
1
2 3 Oxygen will have a partial positive charge when it

FC (N1) = 5 – ( × 6 + 2) = 0
1 is covalently bonded to the more electronegative
2 element fluorine, e.g. in the compound OF2.
FC (N2) = 5 – ( × 4 + 4) = –1
1 4 Run each solution out from separate burettes,
2 and see whether the stream of liquid is deflected
Although both structures only contain
in the presence of a charged rod. Only the polar
two atoms with small formal charges
solution will show deflection.
the first structure will be preferred as the
carbon in the second structure only has Test the solubility of ionic and covalent solutes
six electrons and an incomplete valence in the two solutions. The polar solution will be a
shell. better solvent (more solute will dissolve) for polar
and ionic solutes; the non-polar solution for non-
–
(b) (i) O Cl O polar covalent solutes.
5 The high thermal conductivity of diamond is
FC (O1) = 6 –
1
2 (
× 2 + 6 = –1 ) because of its strong covalent bonds. When
heated the bonds become vibrationally excited
FC (Cl) = 7 –
1
2 (
× 4 + 4 = +1 ) and, as they are all connected, heat energy is

( )
1 readily transferred through the network from
FC (O2) = 6 – × 2 + 6 = –1
2 one bond to the next. Silicon is similarly a good
– thermal conductor, which is why computer chips
(ii) O Cl O need to be cooled to prevent overheating.

FC (O1) = 6 – ( 12 × 2 + 6) = –1 6 Diamonds are kinetically stable with respect

to graphite, as the conversion has a very high
FC (Cl) = 7 – ( × 6 + 4) = 0
1 activation energy (see Chapter 6), so the reaction
2 generally occurs too slowly to be observed.
FC (O2) = 6 – ( × 4 + 4) = 0
1
7 One problem is that it is difficult to know exactly
2
The second structure will be preferred as how many valence electrons to assign to a
it has fewer atoms with a formal charge. transition metal when it forms a complex ion.
The calculation of formal charges also involves
treating the metal–ligand bonds as being purely
covalent, but in reality these bonds often have
Challenge yourself some ionic character. Formal charge values
obtained for the central metal in complex ions
1 Aluminium oxide, Al2O3, is less ionic than MgO can be negative, which implies this model may
due to the smaller difference in electronegativity not be appropriate for complex ions.
23
8 In the polar winter small amounts of water
vapour freeze into ice crystals in the atmosphere.
Reactions that occur on the surface of these
crystals produce species such as Cl2•, which
later dissociates into Cl•, which is an ozone-
depleting substance.

24