Modern College AL Chemistry Notes (2009 – 10) Section 4A

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Modern College AL Chemistry Notes (2009 – 10) Section 4A

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 Modern College AL Chemistry Notes (2009 – 10) Section 4A

4.1 Ionic Bonding Revisited

4.1.1. Formation of ionic bond
 Ionic bonding: Interaction (electronic attraction) between oppositely charged ions by
transferring of electrons.
 Ions are formed as a result of the transfer of one or more electrons from the valence shell
of an atom of a metal to the valence shell of an atom of a non-metal.
 Ions often, but not always, have noble gas electronic configurations. The lack of chemical
reactivity of the noble gases is an indication of the great stability of their electronic
structure; and ions with such electronic structure.
 “Dot and Cross” diagram (點叉圖) can be used to show the transfer of electrons from one
atom to another gives ions.
 It should be noted that when drawing ‘Dot and Cross’ diagrams, the dot and cross
only show the number of electrons present; they do not show the positions of the
electrons. The electrons are distributed in space as diffuse negative charged clouds.

Example 1: Formation of sodium oxide

Example 2: Formation of magnesium chloride

4.1.2. Nature of ionic bond

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 Modern College AL Chemistry Notes (2009 – 10) Section 4A
 Ionic bond is a result of balance between attraction and repulsion.
 There are electrostatic attractions among oppositely charged particle and repulsion
among similarly charged particle.
 The ions will come to equilibrium when the attractive and repulsive forces balance
one another and the ions will stay in positions in the crystal lattice.
 The structure of ionic compound is called giant ionic structure or giant ionic lattice.
 The particular arrangement of ions depends on their relative charges and sizes.

 Ionic bonds are non-directional.

 Ionic compounds have very high melting point (m.p.) and boiling point (b.p.).
 Stronger ionic bond, higher m.p. and b.p.
 Size of ions ↑ ; strength of ionic bond ↓
 Charge of ion ↑; strength of ionic bond ↑
 Consider the m.p. of the following two pairs of ionic compounds
KF (858°C) > KCl (711°C) (size: F– < Cl–)
MgO (2825°C) > Na2O (1132°C) (charge: Mg2+ > Na+)

4.2 Energetics of Formation of Ionic Compounds

4.2.1. Formation of cations from Group I and Group II elements
 Group I and Group II elements tend to form cations by losing electrons to attain electronic
configurations of noble gases.
 The ease with which an atom loses an electron to form a positive ion is measured by its
ionization enthalpy.
 For Group I elements (alkali metals)
Element Electronic 1st I.E. / kJmol-1 Electronic
configuration configuration of M+
Lithium [He]2s1 520 Li+: [He]
Sodium [Ne]3s1 496 Na+: [Ne]
Potassium [Ar]4s1 419 K+: [Ar]

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Rubidium [Kr]5s1 403 Rb+: [Kr]
Caesium [Xe]6s1 376 Cs+: [Xe]
 The 1st I.E. of alkali metal atom is the lowest among the elements in the same period.
 The ions have the stable noble gas electronic structure. This shows that alkali metals
form ions easily. They are the most reactive metals and powerful reducing agents.
 Alkali metals do not form M2+ ions. This is because of the very high 2nd I.E. required
and the dipositive ions formed do not have the stable noble gas electronic structure.
 For Group II elements (alkaline earth metals)
Element Electronic 1st I.E. / 2nd I.E. Electronic
–1
configuration /kJmol configuration of M2+
Beryllium [He]2s2 899 / 1757 Be2+: [He]
Magnesium [Ne]3s2 738 / 1451 Mg2+: [Ne]
Calcium [Ar]4s2 590 / 1145 Ca2+: [Ar]
Strontium [Kr]5s2 549 / 1064 Sr2+: [Kr]
Barium [Xe]6s2 502 / 965 Ba2+: [Xe]
 The 2nd I.E. is much greater than the 1st I.E. (∵ Electron is being pulled away from a
positively charged ion ⇒ have to overcome the attraction force)

4.2.2. Formation of anions from Group VI and Group VII elements

 Group VI and Group VII elements tend to form anions by gaining electrons to attain
electronic configurations of noble gases.
 The ease with which an atom gains an electron to form a negative ion is measure by its
electron affinity (電子親合勢).
 The electron affinity for an element is the enthalpy change when 1 mole of electrons
is added to 1 mole of neutral atoms in the gaseous state to form 1 mole of gaseous
anions under standard conditions.

X(g) + e– → X–(g) ΔH = E.A.1 (in kJmol–1)

 The 2nd E.A. and 3rd E.A. can be defined as:
X–(g) + e– → X2–(g) ΔH = E.A.2
X2–(g) + e– → X3–(g) ΔH = E.A.3
 The value of the electron affinity depends on the attraction between the incoming
electron and the nucleus and the shielding effect offered by the existing electrons.
 For Group VII elements (halogens)
Element Electronic 1st E.A. / kJmol–1 Electronic
configuration configuration of X–
Fluorine [He]2s22p5 –333 F–: [Ne]
Chlorine [Ne]3s23p5 –348 Cl–: [Ar]
Bromine [Ar]3d104s24p5 –324 Br–: [Kr]

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Iodine [Kr]4d105s25p5 –295 I–: [Xe]
 The halogens are expected to have the most negative 1st E.A. because they complete
their outer energy level by gaining an electron to give the halide ion (X–) with stable
noble gas electronic configuration.
 Going down a group, the atomic radii of the elements increase. The outermost
electrons become further away from the nucleus and so they would experience less
nuclear attraction.
 Besides, as the number of occupied inner electron shells increase, the screening
effect becomes more significant. This also leads to a reduction of nuclear attraction.
 The value for fluorine is anomalous (反常的) because it includes an electron cloud
with high repulsion.
♦ The electron cloud of fluorine is very compact due to its small atomic size.
♦ Requires higher electrostatic energy to force the electron into the region of outer
energy level.
 For Group VI elements
Element Electronic 1st E.A. / 2nd E.A. E.A.1 + E.A.2 / Electronic
configuration /kJmol–1 kJmol–1 configuration of X2–
Oxygen [He]2s22p4 –141 / +791 +650 O2–: [Ne]
Sulphur [Ne] 3s23p4 –200 / +649 +449 S2–: [Ar]
 Formation of X2– ions requires the uptake of a second electron. This will involve the
second electron affinity of an element.
♦ The enthalpy required for adding one mole of electrons to one mole of isolated
uninegative ions in the gaseous state.
 The 1st E.A. of O and S are exothermic because the attraction between the incoming
electron and the nucleus is stronger than the repulsion between the incoming electron
and the existing electrons.
 The 2nd E.A. of O and S are endothermic because in the presence of the extra
electron, the extra electron charge offers a stronger repulsion with the incoming
electron. Also, the electron cloud of O– and S– will expand and the incoming electron
will occupy a position further from the nucleus which reduces the attraction with the
nucleus.
 As a result, both formation of oxide and sulphide ions are endothermic. This
considerable expenditure of energy can be justified if the subsequent bonding in the
ionic compound causes an even greater release of energy.

4.2.3. Energetics of formation of ionic compounds (Part I) –

Lattice enthalpy (晶格焓 ) and its determination
 Ionization enthalpies and electron affinities give us information about the energy changes
involved in the production of ions from neutral atoms, but this is only part of what

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happens when an ionic compound is formed.
 The story is completed by knowledge of the lattice enthalpy of the compound.
 Lattice enthalpy (lattice energy): The enthalpy change when one mole of an ionic crystal
is formed from its constituent ions in the gaseous state under standard conditions. (在
標 準 條 件下 ， 由 相互 分離 的氣 態陽 離子 和氣 態陰 離子 生成 一摩 爾離 子晶 體 時
所釋放的能量。 )
mAn+(g) + nBm–(g) → AmBn(s) ΔH = ∆ Hlattice (in kJmol–1)
 Take sodium chloride as an example, the expression should be:

Na+(g) + Cl–(g) →NaCl(s) ∆ H = ∆ Hlattice[NaCl(s)]

 Lattice enthalpy must be exothermic because it is associated with the formation of

electrostatic attraction between cations and anions (i.e. ionic bond). (由於晶格能涉
及離子鍵的形成，所以晶格能必為負值。)
 The value of lattice enthalpy is proportional to the strength of ionic bonds in an ionic
compound. The more exothermic (more negative) the lattice enthalpy, the more
stable the ionic compound formed. (晶格能負值越大，表示離子鍵越強，該離子
晶體就越穩定。)

 Mathematically, we have,
Z+Z−
E∝
r+ + r−
Z+ and Z–: Charge of cation and anion
Internuclear
r+ and r–: Internuclear distance = sum of radii of cation and anion
distance
 Lattice enthalpies cannot be determined directly and so they are calculated by using the
Born-Haber cycle (波恩–哈柏循環).
 Take sodium chloride as an example,

 Analysis of the cycle:

 ΔHθatom[Na(s)] /ΔHθatom[Cl2(g)]: Standard enthalpy change of atomization (標準原

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子 化 焓 變 ) – The enthalpy change when 1 mole of gaseous atoms is formed from
its element in the standard state under standard conditions (在 標 準 條 件 下 ，
把元素轉化為一摩爾的氣態原子所涉及的焓變。)
♦ For sodium: Na(s) → Na(g) ΔHθatom [Na(s)] = +109 kJmol–1
1
♦ For chlorine: Cl2(g) → Cl(g) ΔHθatom [Cl2(g)] = +121 kJmol–1
2
♦ Always endothermic (energy is needed for vaporization and bond breaking)
 ΔHI.E.[Na(g)]: 1st I.E. of sodium – Formation of Na+(g)
 ΔHE.A.[Cl(g)]: 1st E.A. of chlorine – Formation of Cl–(g)
 ΔHlattice[NaCl(s)]: Lattice enthalpy of sodium chloride – Ionic bond formation
 ΔHθf[NaCl(s)]: Standard enthalpy change of formation of sodium chloride
♦ Formation of NaCl can be regarded as a combination of the above steps
♦ ΔH of all other steps can be determined experimentally, except L.E.

 So far the whole process can be summarized by the following flow chart:

 The values of these enthalpy terms are given as follows:

Process involved Enthalpy change
Formation of sodium chloride from its ΔHθf [NaCl(s)] = –411 kJmol–1
constituent elements
Na(s) is atomized to form Na(g) ΔHθatom [Na(s)] = +109 kJmol–1
Na(g) loses 1 electron to give Na+(g) (1st I.E.) ΔHI.E. [Na(g)] = +496 kJmol–1
Cl2(g) is atomized to give Cl(g) ΔHθatom [Cl2(g)] = +121 kJmol–1
– st
Cl(g) gains 1 electron to give Cl (g) (1 E.A.) ΔHE.A. [Cl(g)] = –348 kJmol–1
Na+(g) and Cl–(g) combine to give NaCl(s) ∆ Hlattice [NaCl(s)]

 By Hess’s law, we have

Enthalpy change of Route 1 ≡ Enthalpy change of Route 2
∴ΔHθf[NaCl(s)]
= Hθatom[Na(s)] + ΔHI.E.[Na(g)] + ΔHθatom[Cl2(g)] + ΔHE.A.[Cl(g)] + ΔHlattice[NaCl(s)]
∴ΔHlattice[NaCl(s)]
= Hθf [NaCl(s)] – {Hθatom [Na(s)] + ΔHI.E. [Na(g)] + ΔHθatom [Cl2(g)] + ΔHE.A. [Cl(g)]}
= –411 – [109 + 496 + 121 + (–348)]
= –789 kJmol–1

 In general, the sequence of drawing a Born-Haber cycle is as follows:

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 Besides Born-Haber cycle, we may also use an enthalpy level diagram to determine L.E.
of an ionic compound (Again, take NaCl as an example).

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Example 1
(a) Draw a Born-Haber cycle for the formation of magnesium oxide.

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(b) With the following thermochemical data, calculate the lattice enthalpy of magnesium
oxide by using the Born-Haber cycle drawn in (a).
Given: ΔHθatom [Mg(s)] = +150 kJmol–1
ΔHI.E. [Mg(g)] = +736 kJmol–1
ΔHI.E. [Mg+(g)] = +1450 kJmol–1
ΔHθatom [O2(g)] = +248 kJmol–1
ΔHE.A. [O(g)] = –142 kJmol–1
ΔHE.A. [O–(g)] = +844 kJmol–1
ΔHθf [MgO(s)] = –602 kJmol–1

(Ans: –3888 kJmol–1)

Example 2

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 Modern College AL Chemistry Notes (2009 – 10) Section 4A
Calculate the lattice enthalpy of rubidium chloride (RbCl) using the following data:
Standard enthalpy change of formation of rubidium chloride = –431 kJmol–1
Standard enthalpy change of atomization of rubidium (Rb) metal = +82 kJmol–1
First ionization enthalpy of rubidium = +403 kJmol–1
Standard enthalpy change of dissociation of chlorine molecules = +242 kJmol–1
(ΔHθdissociation [Cl2(g)])
Electron affinity of chlorine atoms = –348 kJmol–1

(Ans: –689 kJmol–1)

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Example 3
Calculate the lattice enthalpy of calcium fluoride using the following data:
Standard enthalpy change of formation of calcium fluoride = –1203 kJmol–1
Standard enthalpy change of sublimation of calcium metal = +193 kJmol–1
First ionization enthalpy of calcium = +590 kJmol–1
Second ionization enthalpy of calcium = +1145 kJmol–1
Standard enthalpy change of dissociation of fluorine molecules = +158 kJmol–1
Electron affinity of fluorine atoms = –333 kJmol–1

(Ans: –2623 kJmol–1)

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4.2.4. Energetics of formation of ionic compounds (Part II) –

Explaining the stoichiometry of ionic compounds

 General rule: All substances in nature tend to keep their energy content as low as possible.
 It would be expected that the compound which has the most negative standard enthalpy
change of formation would be the most stable.
 For instance, energy calculation can be used to show whether MgCl, MgCl2, or MgCl3
would most likely be the formula for magnesium chloride.
 If it is assumed that MgCl has a sodium chloride lattice structure, and MgCl3 has a
structure similar to AlCl3, then a reasonable estimate of the lattice enthalpies for the
hypothetical crystals MgCl and MgCl3 may be made.
 Born-Haber cycles can then be constructed to estimate the standard enthalpy changes of
formation of these hypothetical crystals.

Enthalpy terms ΔH / kJmol-1

ΔHθatom [Mg(s)] = Standard enthalpy change of atomization of magnesium +148
I.E.1 = 1st I.E. of magnesium +738
I.E.2 = 2nd I.E. of magnesium +1451
rd
I.E.3 = 3 I.E. of magnesium +7733
θ
ΔH atom [Cl2(g)] = Standard enthalpy change of atomization of chlorine +122
ΔHE.A. [Cl(g)] = 1st E.A. of chlorine –349
*∆ Hlattice [MgCl(s)] = Lattice enthalpy of MgCl –753
∆ Hlattice [MgCl2(s)] = Lattice enthalpy of MgCl2 –2526
∆ Hlattice [MgCl3(s)] = Lattice enthalpy of MgCl3 –5440
*Note: Here the given lattice enthalpies are calculated based on the mathematical model.

Cycle 1 (MgCl)
ΔHθatom [Mg(s)]
1 1
Mg(s) + Cl2(g) Mg(g) + Cl2(g)
2 2

I.E.1 ΔHθatom [Cl2(g)]

ΔHθf [MgCl(s)]
Mg+(g) + Cl(g) + e–

ΔHE.A. [Cl(g)]
∆ Hlattice [MgCl(s)]
MgCl(s) Mg+(g) + Cl–(g)

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Cycle 2 (MgCl2)
ΔHθatom [Mg(s)]
Mg(s) + Cl2(g) Mg(g) + Cl2(g)

I.E.1 2 × ΔHθatom [Cl2(g)]

ΔHθf [MgCl2(s)]
Mg+(g) + 2Cl(g) + e–

I.E.2

Mg2+(g) + 2Cl(g) + 2e–

2 × ΔHE.A. [Cl(g)]
∆ Hlattice [MgCl2(s)]
MgCl2(s) Mg2+(g) + 2Cl–(g)

Cycle 3 (MgCl3)
ΔHθatom [Mg(s)]
3 3
Mg(s) + Cl2(g) Mg(g) + Cl2(g)
2 2

I.E.1 3 × ΔHθatom [Cl2(g)]

ΔHθf [MgCl3(s)]
Mg+(g) + 3Cl(g) + e–

I.E.2

Mg2+(g) + 3Cl(g) + 2e–

I.E.3

Mg3+(g) + 3Cl(g) + 3e–

3 × ΔHE.A. [Cl(g)]
∆ Hlattice [MgCl3(s)]
MgCl3(s) Mg3+(g) + 3Cl–(g)
From these three cycles, we have,

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ΔHθf [MgCl(s)] = 148 + 738 + 122 + (–349) + (–753) = –94 kJmol-1
ΔHθf [MgCl2(s)] = 148 + 738 + 1451 + 2(122) + 2(–349) + (–2526) = –643 kJmol-1
ΔHθf [MgCl3(s)] = 148 + 738 + 1451 + 7733 + 3(122) + 3(–349) + (–5440)
= +3949 kJmol-1
 From the Born-Haber cycles, we can see that:
 Formation of MgCl is just exothermic. The compound is energetically stable with
respect to its elements.
 Formation of MgCl2 is even more exothermic, and so the compound would be more
energetically stable with respect to its elements.
 However, formation of MgCl3 is highly endothermic. Thus MgCl3 would be
extremely unstable with respect to its elements.
 Therefore, it appears that the compound formed is the one whose formation involves the
greatest transfer of energy to the surroundings. (i.e. the most energetically stable one.)
 Besides, the largest contributions in each cycle are made by the ionization enthalpies and
the lattice enthalpy, and that these two are always opposite in sign.
 If it requires more energy to ionize the metal than it is returned as lattice enthalpy,
then the metal ion (and hence the ionic compound) will not be formed.
 To sum up, energetics can help us to understand the stoichiometry of ionic compounds.
 The calculation of the lattice energies and use of Born-Haber cycle can also be used
to explain why group I, II and III metal always form M+, M2+ and M3+ ion
respectively.

4.2.5. More about lattice enthalpy

A. Factors affecting the lattice enthalpies
 As mentioned previously, L.E. can be calculated based on mathematical model, we have,
Z+Z−
E∝
r+ + r−
Z+ and Z–: Charge of cation and anion
r+ and r–: Internuclear distance = sum of radii of cation and Internuclear
anion distance

 Effect of ionic size

 L.E. becomes less negative the size of ion increases (∵ electrostatic attraction ↓)
 Besides, small and similarity in size of ions result in more efficient packing and
more negative lattice energy
 Effect of ionic charge
 L.E. becomes more negative when the charge of ions increase (∵electrostatic
attraction ↑)
 The charge density (電荷密度) of the constituent ions

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 Charge density of an ion is affected by both ionic size and ionic charge
 For ions with the same charge, smaller ion, larger charge density
 For ions with the similar size, greater charge, larger charge density
 The higher the charge density of the ion, stronger will be the electrostatic attraction
and the lattice energy will be more negative.

B. Application of lattice enthalpies

 Lattice enthalpy is an important consideration in prediction of solubility of an ionic
compound.
 When an ionic compound is dissolved, heat energy will be absorbed or evolved because:
 Firstly, the crystal lattice must be broken down and this requires energy.
 This energy will be numerically equal to the lattice enthalpy with the sign reversed
(∵Endothermic step).
 The second step is the solvation ions: Interaction between the ions and the solvent
molecules. Energy is evolved during solvation (∵Exothermic step).
 If water is the solvent the process of solvation is known as hydration and the energy
released is the hydration energy (ΔHhyd) (水合能).
 The standard enthalpy change of solution (ΔHsoln) is the enthalpy change when one mole of
a substance is dissolved in an infinite amount of solvent (usually water) so that further
dilution produces no detectable heat change under standard conditions.
 To some extent, it reflects the solubility of a compound.
 For a salt to be soluble in water, ΔHsoln usually has to be a negative or a small
positive value (Remember: ΔG = ΔH – TΔS).
 For ionic compounds, the value of ΔHsoln can be calculated by the following formula
ΔHsoln = – ∆ Hlattice + [ΔHhyd(cation) +ΔHhyd(anion)]
⇒ ΔHsoln = ΔHhyd – ∆ Hlattice
 Take NaCl as an example,
 Firstly, the sodium chloride solid lattice is broken down to give its constituent ions
in the gaseous state.
NaCl(s) → Na+(g) + Cl–(g) ∆ H = –∆ Hlattice = –(–776) = +776 kJmol–1
 Then the resulting ions are hydrated (i.e. form interaction with water molecules)
Na+(g) + Cl–(g) → Na+(aq) + Cl–(aq) ΔHhyd = –772 kJmol–1
 By Hess’s Law, we have

ΔHsoln = ΔHhyd – ∆ Hlattice = –772 – (776) = +4 kJmol–1

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 For salts which form crystals with water of crystallization (e.g. CuSO4, MgSO4, Na2CO3),
the value of ΔHsoln depends on whether the anhydrous or hydrated salt is used.
 The anhydrous form usually gives out heat on dissolving whilst the hydrated form
may absorb heat on dissolving.
 This is because ions of the hydrated salt are hydrated by the water of crystallization
before the salt dissolves.

4.3 Ionic Crystals

 The structure of an ionic crystal can be determined by a technique called X-ray diffraction.

 The model of an ionic crystal is a lattice array: a regular three-dimensional arrangement of

cations surrounded by anions and each anion by cations.
 This arrangement gives the maximum attractive force between oppositely charged ions
while minimizing repulsion between like ions.
 A unit cell ( 晶 胞 ) is the smallest basic part of the crystal lattice. It can be repeatedly
stacked together at various directions to fill the space completely, and to reproduce the
whole crystal structure of the compound. (晶胞反映晶體結構中所有特徵的最小單位。若
晶胞在空間內重複地作有規律的無限排列，便構成晶體。晶胞也能清楚顯示出離子
在晶格內的幾何排列。)

4.3.1. Sodium chloride lattice

 Figure (a) shows a space-filling model of the structure of sodium chloride. Although it
only shows a few Na+ and Cl– ions, there will be millions and millions of ions in even the
smallest visible crystals of sodium chloride.
 The positions of Na+ and Cl– ions in the crystal lattice of sodium chloride are emphasized
in figure (b).

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(a) (b)

 Note: Counting ions in a unit cell

 Ion inside the unit cell = 1
1 Question: For NaCl lattice shown on P.17, what
 Ion lies on each face =
2 are the numbers of Na+ and Cl– ions in a unit cell?
1
 Ion lies on each edge =
4
1
 Ion at each corner =
8
 For a face-centred cubic lattice like NaCl, you may refer to the figure below:

 In the crystal lattice of NaCl, ions are placed at each corner and each of the 6 faces.
 Each positive sodium ion is surrounded by 6 Cl– ions and each negative chloride ion is
surrounded by 6 Na+ ions.
 The ions are arranged in a face-centred-cubic (面 心 立 方 ) pattern. The structure of NaCl
is said to have 6:6 coordination because the Na+ ions have a coordination number of 6
and the Cl– ions also have a coordination number of 6.
 Coordination number (配 位 數 ): The number of adjacent atoms or ions which are in
direct contact with a certain atom or ion.

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NaCl: A face-centred cubic lattice

Example 4
The figure below shows a unit cell of NaCl:

X-ray analysis shows that a side of this unit cell has a length of 5.641 × 10–8cm. Given the
density of sodium chloride is 2.165 gcm–3. Calculate a value for the Avogadro constant, L.
(Formula mass of NaCl = 58.44)

Relative formula mass

Density =
Volume of 1 mole NaCl
(5.641 ×10 −8 ) 3
Volume of 1 mole NaCl = L × (∵Each unit cell has 4 units of NaCl)
4
(5.641 ×10 −8 ) 3 58 .44
∴ L× =
4 2.165
L = 6.015 × 1023

4.3.2. Caesium chloride (CsCl) lattice (氯化銫晶體 )

 Figure (c) shows a space-filling model of caesium chloride. The Cs+ ion is similar in size
to the Cl– ion. The general shape of the lattice is simple cubic ( 簡 單 立 方 晶 格 ). The
positions of Cs+ and Cl– ions in the caesium chloride lattice are shown in figure (d).

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(d)
(c)

Question: For CsCl, what are the numbers of Cs+ and Cl– ions in a unit cell?
 In the crystal lattice of caesium chloride, ions are placed at each corner and in the centre.
 There are 8 Cl– ions around each Cs+ ion, so the coordination number of Cs+ ions in the
structure is 8.
 In the same way, the coordination number of Cl– ions is also 8.
 The structure of caesium chloride is therefore said to have 8:8 coordination.

4.3.3. Calcium fluoride (CaF2) lattice

 The figure below shows the unit cell of calcium fluoride

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 In the crystal lattice of CaF2, the calcium ions are arranged in a face-centred-cubic pattern
while the fluoride ions are arranged in a simple cubic pattern.
 Each Ca2+ ion is surrounded by 8 F– ions and each F– ion is surrounded tetrahedrally by 4
Ca2+ ions.
 The structure of calcium fluoride is said to have 8:4 coordination because the Ca2+ ions
have a coordination number of 8 and the F– ions have a coordination number of 4.

Example 5
The following is a unit cell of an oxide of titanium

(a) What are the coordination numbers of titanium and oxygen respectively?
(b) State the number of titanium ions and oxide ions per unit cell. Explain your answer.
(c) Write the formula of the compound.

 Note: The unit cell also gives us hints about the stoichiometry of an ionic compound.
 No. of ions in a unit cell
 Coordination number

 In general, there are two factors governing the packing of ions in a giant ionic lattice:
 Close packing consideration
♦ Each ion tends to have the highest number of neighbors of opposite charge, as
this would increase the lattice stability
 Relative size of ions

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♦ If the cation has a larger size than the anion, then more anions can be packed
around the cation.
♦ On the other hand, if the cation is much smaller than the anion, then before the
anions come close together, the anions already repel each other.

(Correct packing for NaCl) (Incorrect packing of CsCl)

 In figure (a), the Na+ ion is small enough to fit into the empty space
between the 4 larger Cl– ions.
 Since the Cs+ ion is much larger, there would be a large wastage of space
if CsCl still packs in the NaCl type lattice in (b).
 The arrangement of the ions in an ionic crystal is determined by the ionic radii ratio (r+/r–):
Type of structure Coordination Ionic radii Examples
ratio (r+/r–)
Simple cubic 8:8 >0.73 CsCl, CsBr, CsI, NH4Cl and NH4Br
Face centered cubic 6:6 0.41 – 0.73 Halides of Li+, K+, Na+, Rb+ (e.g.
KCl, NaBr); Oxides and sulphides of
Ca2+, Mg2+ and Ba2+; Silver halides
(AgF, AgCl, AgBr and AgI)

4.4 Ionic Radii (離子半徑)

4.4.1. Some general discussion
 Similar to atomic radius, the size of an ion is mainly governed by the strength of the
effective nuclear charge (有效核電荷).
 In general, ionic radii increase down a group because of increased number of occupied
electron shells. (同一族的元素的離子半徑呈現遞增的趨勢。)
 As the inner electrons can effectively screen the outermost electron and number of
inner electrons increase, the outermost electrons are less attracted by the nucleus.
 Going across a period, both cationic and anionic radius decrease. (不論是陽離子還是陰
離子，同一週期的元素的離子半徑呈現遞減的趨勢。)
 As the number of protons increase, the effective nuclear charge increases.
 The electrostatic attraction between outer electrons and positively charged nucleus
increases. As a result, the electrons are pulled closer towards the nucleus, causing a

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reduction in ionic radius.
 For cations, the size of a cation is always smaller than the size of its parent atom as
electron is removed. (陽離子的半徑較母原子的半徑小。)
 The proton to electron ratio increases. The nuclear charge will have a greater effect
on the fewer remaining electrons, which makes the electron cloud contracts. (由於質
子數目較電子數目多，所以原子核對電子雲的吸引力（有效核電荷）必定較母
原子的大。)
 Besides, for a metal cation, it has 1 less occupied electron shell than its parent atom.
(原子形成正離子時，會失去最外層電子，所以電子層數較原先的減少了。)
 For anions, the size of an anion is always bigger than the size of its parent atom as electron
is added. (陰離子的半徑較母原子的半徑大。)
 The additional electron enters the highest energy level without an increase in nuclear
charge. This causes greater repulsion among the electrons (repulsion between the
existing electrons and the newly added electron). (新加入的電子與原先存在的電
子互相排斥，令電子雲分佈較遠。)
 Since the number of protons becomes less than that of electrons, the nuclear
attraction becomes less effective and so there is an expansion of the electron cloud.
(由於陰離子所含的質子數目較電子數目小，以致原子核對電子雲的吸引力減
弱，使電子雲變大。)

4.4.2. Isoelectronic species (等電子體 / 等電子數粒子 )

 For example, O2– ion, F– ion, Na+ ion and Mg2+ ion are isoelectronic because they contain
the same number of electron and have the same electronic configuration: 1s22s22p6.
 Constant number of electrons
 Number of proton increase across this isoelectronic series
 ∴ Nuclear charge ↑
 ∴ Attraction between the nucleus and the electrons ↑
 ∴ Ionic radius decrease across the series.
 For a series of isoelectronic anions (e.g. N3–, O2– and F–), the ionic size increases as the
number of negative charge increases.
 There will be repulsion between electrons of a negative ion which causes an increase
in size and the more electrons in an anion the larger it is.
 The variation is ionic size of different series of isoelectronic species is shown below:

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 Comparison between atomic and ionic radii in nanometers (nm) is shown below:

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