2 Chemical Bondings (S)
2 Chemical Bondings (S)
1 N13/P2/Q4(b)
Describe the structure and bonding in calcium with the aid of a labelled diagram.
Calcium has a giant metallic lattice structures consisting of calcium cations that are arranged
in a lattice and surrounded by a ‘sea’ of delocalised electrons.
The electrostatic attraction between the lattice of Ca2+ ions and the ‘sea’ of delocalised
electrons constitute the metallic bonds found in Ca.
e− e− e−
Ca2+ e− Ca2+ Ca2+ e− Ca2+
e− e−
− e−
e e−
e− e− e− e−
Ca2+ Ca2+ Ca2+ e− Ca2+
e− e− e− e−
e−
e− Ca2+ Ca2+ e− Ca2+ Ca2+ e−
e− e−
2 For each pair of metals, determine which has greater metallic bond strength and electrical
conductivity.
(a) Ca and K
(b) Na and Li
(a) Ca has greater metallic bond strength as there are more delocalised electrons in Ca / Ca
releases more valence electrons than K. Ca2+ has a higher charge and smaller ionic radius
than K+, thus Ca2+ has a higher charge density. As a result there is greater electrostatic
attraction between Ca2+ and the delocalised electrons in Ca and thus stronger metallic bond
strength.
JC1 H2 Chemistry Tutorial 2: Chemical Bonding
Ca also has greater electrical conductivity than K as Ca releases more valence electrons,
thus there are more mobile charge carriers.
(b) Li has greater metallic bond strength as Li+ has the same charge but a smaller ionic radius
than Na+, thus Li+ has a higher charge density. As a result there is greater electrostatic
attraction between Li+ and the delocalised electrons in Li and thus stronger metallic bond
strength.
Li & Na has the same electrical conductivity as they both release the same amount of
valence electrons, so there are the same amounts of mobile charge carriers in both
metals.
(b) For the following pairs of ionic compounds, determine which one has a higher melting
point.
(i) sodium bromide and sodium fluoride (ii) sodium oxide and magnesium oxide
(a)
(b)
(i) NaF has a higher melting point.
Both NaF and NaBr have giant ionic structures.
The charge and size of cation Na+ are the same.
The Br − ion and F− ion have the same charge.
The F− ion has a smaller ionic radius than the Br − ion, thus inter-ionic distance
between Na+ and F− is shorter than that between Na+ and Br−.
Thus NaF has stronger electrostatic attractions between Na+ and F- ions,
requiring more energy to overcome.
4 Sodium conducts electricity both in solid and molten state but sodium chloride conducts
electricity only when in the molten state.
Na has a giant metallic structure with electrostatic attraction between the lattice of Na+ and
sea of delocalised electrons. The sea of delocalised electrons which can act as mobile charge
carriers, in both solid and molten state.
NaCl has a giant ionic structure with electrostatic attraction between oppositely charged
ions. In solid state, Na+ and Cl− ions are held in fixed positions in the giant ionic lattice.
Therefore, there is the absence of mobile charge carriers, hence NaCl does not conduct
electricity in the solid state. In the molten state, the ionic lattice is broken down to form mobile
ions, which can then act as charge carriers.
5 Describe the structure and bonding present and show how they can be used to explain two
characteristic physical properties of each of the following substances.
(a) diamond,
(b) graphite,
(c) iodine.
(a) Diamond has a giant molecular structure with the C atoms held together by strong
electrostatic attraction between the 2 positive nuclei and shared pair of electrons
(covalent bonds).
Each carbon atom is covalently bonded to 4 other carbon atoms arranged in a three-
dimensional tetrahedral arrangement.
Non-conductor of electricity
All the valence electrons of carbon are used to form covalent bonds and are unable to
move freely in the presence of applied electric field, unable to function as mobile charge
carriers and therefore diamond does not conduct electricity.
Very hard
The structure of diamond is mechanically strong and rigid due to strong C−C bonds forming
a three-dimensional network of interlocking hexagons.
Insoluble in water
The interaction between diamond and water molecules does not release sufficient
energy to overcome the large number of strong C−C covalent bonds in diamond.
(b) Graphite has a giant molecular structure with the C atoms held together by strong
electrostatic attraction between the 2 positive nuclei and shared pair of electrons
(covalent bonds). The carbon atoms are arranged in layers of interconnected hexagonal
rings.
Within each layer, each carbon atom is covalently bonded to three other carbon atoms
using 3 of the 4 valence electrons. The 4th valence electron is available for bonding
between the adjacent carbon atoms, resulting in delocalisation throughout the layer.
Insoluble in water
The interaction between graphite and water molecules does not release sufficient
energy to overcome the large number of strong C−C covalent bonds in graphite.
(c) Iodine has a simple molecular structure with the iodine atoms held together by strong
electrostatic attraction between the 2 positive nuclei and shared pair of electrons (covalent
bonds), with weak instantaneous dipole – induced dipole between the I2 molecules.
covalent bonds
between iodine atoms instantaneous dipole-
induced dipole between
iodine molecules
Non-conductor of electricity
There are no mobile charge carriers as the valence electrons are used in the formation of
bonds.
The energy evolved when the iodine molecules form instantaneous dipole-induced
dipole interactions with the water molecules is insufficient to overcome the hydrogen
bonds between water molecules and the instantaneous dipole-induced dipole
interactions between iodine molecules.
The energy evolved when the iodine molecules form instantaneous dipole-induced
dipole interactions with the non-polar solvent molecules is sufficient to overcome the
instantaneous dipole-induced dipole interactions between the non-polar solvent
molecules and the instantaneous dipole-induced dipole interactions between iodine
molecules.
6 (a) The molecule of oxygen contains both -bonds (sigma) and -bonds (pi).
Describes the terms in italics and draw labelled diagrams to show how orbitals overlap
to form
-bond
-bond
A bond is formed when two orbitals overlap head-on. In the case of oxygen molecule, the
head- on overlap is between two p-orbitals.
O
O
O
O
bond is formed when the p orbitals of the two atoms overlap sideways. In the case of
oxygen molecule, the sideway overlap is between two p-orbitals.
(b) Determine the number of -bonds and -bonds in the following compounds.
(i) ethane, C2H6 (ii) ethene, C2H4 (iii) propyne, HCCH (iv) carbon dioxide, CO2
7 (a) N08/P3/Q4(a)
When dry chlorine is passed over heated aluminium foil in a hard glass tube, a vapour
is produced which condenses to a yellow-white solid in the cooler parts of the tube. At
low temperatures, the vapour has the empirical formula AlCl3, and a Mr of 267.
Suggest the molecular formula of the vapour, and draw a dot-and-cross diagram to
describe its bonding.
(b) Beryllium chloride BeCl2 reacts with phosphine PH3 in a 1:2 ratio to yield a single
product.
Explain why this is so.
You may find both a written explanation and a sketch useful in your answer.
BeCl2 has two bond pairs and no lone pair of electrons. Hence, Be has four valence electrons and
is electron-deficient / has two empty 2p orbitals. Each PH3 has a lone pair of electron which
can then donate into the empty 2p orbitals of Be, and 2 PH3 molecules will donate a total of
4 electrons, allowing Be to form a stable octet structure.
H P H
H
Cl Be Cl + 2H P Cl Be Cl
H
H P H
8 N11/P2/Q4(b)
Among the elements of Group 14, those towards the top, carbon to germanium, have very
different properties from these at the bottom, tin and lead.
For example, the melting points show a marked change after germanium,
element C Si Ge Sn Pb
mp / oC >3550 1410 937 232 327
Carbon, silicon and germanium each form a solid with the same type of structure
(a) What type of structure is present in solid carbon, silicon and germanium?
(b) Suggest why the melting points of these elements decrease from carbon to germanium.
(a) CS2 (b) SO3 (c) SnCl2 (d) CHCl3 (e) H3O+
(f) H2S (g) AsCl5 (h) SF4 (i) ClF3 (j) I3
O xx S xx O
xx trigonal trigonal
SO3 3 3 0 120o
planar planar
O
xx trigonal Sn
SnCl2 Cl x Sn x Cl 3
planar
2 1 bent 118o
Cl Cl
Cl
x
CHCl3 Cl x C x H 4 tetrahedral 4 0 tetrahedral 109.5o
x
Cl
+
H +
x trigonal O
x
H3O+ Hx
xO x
4 tetrahedral 3 1
pyramidal
107o H
x H
H
H
xx
104.5o S
H2S Hx S xH 4 tetrahedral 2 2 bent
xx H H
JC1 H2 Chemistry Tutorial 2: Chemical Bonding
number number of
molecule ‘dot-and-cross’ of basic bond
bond lone final shape structure
/ ion diagram electron shape angle
pairs pairs
pairs
Cl
x Cl 120o
x trigonal trigonal
AsCl5 Cl x As 5 5 0 and
x x bipyramidal bipyramidal
Cl 90o
Cl
F F
x F
F trigonal
S x
x
SF4 5 4 1 see-saw NA S
xx x bipyramidal
F F
F
F
F F
x
xx x
Cl x F trigonal
x
ClF3 5 3 2 T-shaped NA Cl F
x bipyramidal
F F
- -
I I
x x
xx x
I trigonal
I3
x
x x 5 2 3 linear 180o I
bipyramidal
I
I
number number of
molecule ‘dot-and-cross’ of basic bond
bond lone final shape structure
/ ion diagram electron shape angle
pairs pairs
pairs
-
Cl
Cl Cl
P x
PCl6
x
x xx 6 octahedral 6 0 octahedral 90o
Cl Cl
Cl
F
F
F x F square F F
BrF5 Br xx 6 octahedral 5 1 NA
x
x pyramidal Br
F xx F
F F
F xx F F F
Xe x square
x
(a) Outline the principles of the Valence Shell Electron Pair Repulsion (VSEPR) theory.
(b) Although they have similar formulae, the following three compounds have differently
shaped molecules.
(a) Electron pairs in the valence shell around a central atom repel each other and orientate
themselves in space as far apart as possible so as to minimise the repulsion between them.
The repulsion between lone pair-lone pair of electrons is greater than those between lone
pair-bond pair of electrons which is in turn greater than bond pair-bond pair of electrons.
(b) F F
N
B Cl F
F F
F F
F
F
no. of electron pairs around no. of electron pairs around no. of electron pairs around
central atom = 3 central atom = 4 central atom = 5
basic shape = trigonal planar basic shape = tetrahedral basic shape = trigonal
no. of b.p. = 3 no. of b.p. = 3 bipyramidal
no. of l.p. = 0 no. of l.p. = 1 no. of b.p. = 3
final shape = trigonal planar final shape = trigonal no. of l.p. = 2
pyramidal final shape = T-shaped
11 For the pairs of ionic compounds in Question 3b, predict which one has greater covalent
character.
Explain your answer.
Mg2+ has a higher charge and a smaller ionic radius than Na+. Hence, it has a higher
charge density and polarising power, which could polarise the O2− electron cloud to a
larger extent, causing some overlap between the Mg2+ and O2− orbitals. This gives MgO
covalent character.
12 (a) Explain what is meant by the terms electronegativity and bond polarity.
(b) Certain covalent molecules are said to be polar (having ionic character). State the two
conditions for a covalent molecule to be polar.
(d) Which of the following substances in each pair is more polar? Explain your choice.
(i) HCl and HI (ii) H2O and H2S (iii) CCl4 and SCl4 (iv) BF3 and NF3
(a) Electronegativity refers to the ability of an atom in a covalent bond to attract electrons
to itself. The greater the electronegativity of an atom, the greater its ability to attract
electrons to itself.
Bond polarity occurs when the covalent bond formed between atoms of different
electronegativities (polar covalent bond).
SF6 no
H2S yes
BF3 no
OF2 yes
CS2 no
SO2 yes
SO3 no
NH3 yes
CO yes
HCN yes
XeF4 no
(d) (i) HCl is more polar. Since chlorine is more electronegative than iodine, the difference
in electronegativity between hydrogen and Cl is greater than between hydrogen and
iodine, and hence the dipole moment is larger.
(ii) H2O is more polar. Since oxygen is more electronegative than sulfur, the difference
in electronegativity between hydrogen and oxygen is greater than between hydrogen
and sulfur, and since both molecules are bent, the resultant dipole moment is larger for
H2O
(iii) SCl4 is more polar. Since CCl4 is tetrahedral in shape, the dipole moments of the
bonds cancel each other completely, and therefore it is non-polar. There are 4 bond
pairs and 1 lone pairs of electrons around the sulfur atom in SCl4, hence the molecular
geometry for SCl4 is see-saw. Hence the dipole moments of the bonds do not
cancel out, and therefore SCl4 is a polar molecule.
(iv) NF3 is more polar. Since BF3 is trigonal planar, the dipole moments of the bonds
cancel each other completely, and therefore it is non-polar. There are 3 bond pairs
and 1 lone pairs of electrons around the nitrogen in NF3, hence the molecular geometry
for NF3 is trigonal pyramidal. Hence the dipole moments of the bonds do not
cancel out, and therefore NF3 is a polar molecule.
E Additional Questions
13 Copper is widely used to make electrical wires due to its high electrical conductivity and its
ductility.
Copper has a high electrical conductivity as the sea of delocalised electrons act as mobile
charge carriers.
Copper is ductile because when one plane of the metal cations slips over another, the mobile
electrons can move easily between the planes to maintain the metallic bond in copper.
2- 3- xx 2-
2 xNx xO x O
2[Al]3+ 3 x Ox 3[Mg]2+ x
2 [Na]+ x
xx
15 Using the VSEPR Theory, suggest an explanation for each of the following observations.
Even though methane, ammonia and water have the same basic tetrahedral electronic
geometry, their bond angles vary.
16 N10/P3/Q4(c)(ii)
(a) Draw dot-and-cross diagrams to show the bonding in the molecules of NO2 and O3.
Each molecule contains a dative covalent bond, and in the NO2 molecule the central
atom is nitrogen.
In each case you should distinguish carefully between electrons originating from the
central atom and those from the two outermost atoms.
Include all lone pairs in your diagrams.
(b) Suggest a value for the bond angle in each of these two molecules in (a), giving reasons
for your choice.
(a)
NO2 O3
(b) Bond angle of NO2: any value between 130o to 160o [actual is 134o]
Bond angle of O3: any value between 110o to 120o [actual is 117o]
NO2 has one lone electron whereas O3 has one pair of electrons. The repulsion between lone
electron and a bond pair is weaker than lone pair-bond pair repulsion
17 N10/P3/Q4(c)(ii)
The compound FO2 does not exist, but ClO2 does.
By considering the possible types of bonding in the two compounds, suggest reasons for this
difference. (Assume that the halogen atom occupies a central position in each of these
molecules.)
There are 9 electrons around the central chlorine atom, which is possible for chlorine, as it can
expand its octet configuration due to the presence of energetically accessible empty 3d orbitals in
Cl. However, fluorine is a Period 2 element which does not have energetically accessible d orbitals
for expanding octet.
18 Why is it that the “first” bond is inevitably the sigma bond and not the pi bond when a bond is
formed between 2 atoms in any structures?
The extent of overlap of a sigma bond is usually greater than that of a pi bond.
This is because the two atoms can approach closer for a “head-on” overlap, rather than a
“sideways” overlap. Hence, a sigma bond is stronger, and leads to the formation of a compound.
Since the driving force behind the formation of a bond is to form stable products, a sigma bond is
inevitably formed.
19 N06/P3/Q2(a)
Boron forms simple trihalides of formula BX3 with all halogens. BF3 and BCl3 are the most
common. Both find uses as Friedel Crafts catalysts since they readily react with electron pair
donors.
(b) BF3 and trimethylamine, (CH3)3N, react in a 1 : 1 ratio to give a white crystalline solid.
Draw a diagram to show the bonding within a molecule of this solid, explaining the type
of bonding involved.
(b) B has six valence electrons and is electron-deficient with one empty 2p orbitals. (CH3)3N
has a lone pair of electron on the N atom which can then donate into the empty 2p
orbitals of B forming a dative bond.
20 N11/P2/Q2(b)
Phosphorus(V) chloride dissolves in some polar solvent without reaction and such solutions
conduct electricity. This is due to the present of the two ions [PCl4]+ and [PCl6]−.
Draw the structure and suggest the shape of each of these ions, [PCl4]+ and [PCl6]− .
[PCl4]+ [PCl6]−
tetrahedral octahedral
(b) Draw ‘dot-and-cross’ diagrams showing the electrons (outer shell only) in, and use the
VSEPR (valence shell electron pair repulsion) theory to predict their shapes.
You may find both written description and a 3-dimensional sketch useful in your
answer.
(a) +3
22 N17/P3/1(c)
The halogens form many interhalogen compounds, such as ClF3 and BrCl.
The central atom in ClF3 is surrounded by five pairs of electrons arranged in a trigonal
bipyramidal shape. A trigonal bipyramidal arrangement is shown in Fig 1.1.
Fig. 1.1
(a) Draw clear diagrams of these three molecular arrangements, each showing the five
pairs of electrons. State which arrangement, if, any, would result in a molecule with no
dipole moment.
(b) Apply the principles of the VSEPR theory to discuss the relative stabilities of these
three possible arrangements.