Ikatan Ionik

7 Ionic Bonding
7.1 Formation of Ionic Bonds: Donating and Accepting

Electrons
7.2 Energetics of Formation of Ionic Compounds
7.3 Stoichiometry of Ionic Compounds
7.4 Ionic Crystals
7.5 Ionic Radii
1
Bonding & Structure
2
Lewis Model
 G.N. Lewis in 1916
 Only the outermost (valence) electrons are

involved significantly in bond formation
 Successful in solving chemical problems
3
 Why are some elements so reactive
(e.g.Na) and others inert (e.g. noble gases)?
 Why are there compounds with chemical

formulae H2O and NaCl, but not H3O and
NaCl2?
 Why are helium and the other noble gases

monatomic, when molecules of hydrogen
and chlorine are diatomic?
4
 Chemical bonds are strong
electrostatic forces holding atoms or
ions together, which are formed by
the rearrangement (transfer or
sharing) of outermost electrons
 Atoms tend to form chemical bonds

in such a way as to achieve the electronic
configurations of the nearest noble gases
(The Octet Rule )
5
Q.1 Write the s,p,d,f notation for the ions in the table below
Isoelectronic
Ion s,p,d,f notation
noble gas
Be2+
O2-
Sc3+
Br-
Ba2+
At-
6
Isoelectronic
noble gas
Be2+ 1s2 (2) He
O2- [He] 2s2,2p6 (2,8) Ne
Sc3+ [Ne] 3s2,3p6 (2,8,8) Ar
Br- [Ar] 3d10,4s2,4p6 (2,8,18,8) Kr
Ba2+ [Kr] 4d10,5s2,5p6 (2,8,18,18,8) Xe
At- [Xe] 4f14,5d10,6s2,6p6 (2,8,18,32,18,8) Rn
7
Introduction (SB p.186)
Three types of chemical bonds

1. Ionic bond (electrovalent bond)
Formed by transfer of electrons
8
7.1 Formation of Ionic Bonds: Donating and Accepting Electrons (SB p.187)

1. Ionic bond (electrovalent bond)
Na Cl
Sodium atom, Na Chlorine atom, Cl

1s22s22p63s1 1s22s22p63s23p5
9

1. Ionic bond
Electrostatic attraction between positively
charged particles and negatively charged
particles
10

2. Covalent bond
Formed by sharing of electrons
11

2. Covalent bond
Electrostatic attraction between nuclei and

shared electrons
12

3. Metallic bond
Electrostatic attraction between metallic
cations and delocalized electrons (electrons
that have no fixed positions)
13

3. Metallic bond
Formed by sharing of a large number of
delocalized electrons
14
Ionic bonds and Covalent bonds are only
extreme cases of a continuum.
In real situation, most chemical bonds
are intermediate between ionic and
covalent
15
Ionic Bonds with incomplete transfer
of electrons have covalent character.
Covalent Bonds with unequal sharing

of electrons have ionic character.
16
Electronegativity and Types of Chemical Bonds
Ionic or covalent depends on the electron-

attracting ability of bonding atoms in a
chemical bond.
Ionic bonds are formed between atoms with

great difference in their electron-attracting
abilities
Covalent bonds are formed between atoms with
small or no difference in their electron-
attracting abilities.
17
Ways to compare the electron-attracting
ability of atoms
1. Ionization Enthalpy
2. Electron affinity
3. Electronegativity
18
1. Ionization enthalpy
The enthalpy change when one mole of
electrons are removed from one mole of
atoms or positive ions in gaseous state.
X(g)  X+(g) + e- H 1st I.E.
X+(g)  X2+(g) + e- H 2nd I.E.

Ionization enthalpies are always positive.
19
2. Electron affinity
The enthalpy change when one mole of
electrons are added to one mole of atoms
or negative ions in gaseous state.
X(g) + e-  X-(g) H 1st E.A.
X(g) + e-  X2(g) H 2nd E.A.
Electron affinities can be positive or negative.
20
I.E. and E.A. only show e- releasing/attracting
power of
free, isolated atoms
However, whether a bond is ionic or covalent

depends on the ability of atoms to attract
electrons in a chemical bond.
21
3. Electronegativity
The ability of an atom to attract electrons
in a chemical bond.
22
Mulliken’s scale of electronegativity
1
Electronegativity(Mulliken)  ( IE  EA)
2
Nobel Laureate in Chemistry,

1966
23
Pauling’s scale of electronegativity
Nobel Laureate in Chemistry, 1954

Nobel Laureate in Peace, 1962
24
 calculated from bond enthalpies

 cannot be measured directly
 having no unit
 always non-zero
 the most electronegative element, F, is
arbitrarily assigned a value of 4.00
25
IA IIA IIIA IVA VA VIA VIIA VIIIA
H He
2.1 -
Li Be B C N O F Ne
1.0 1.5 2.0 2.5 3.0 3.5 4.0 -
Na Mg Al Si P S Cl Ar
0.9 1.2 1.5 1.8 2.1 2.5 3.0 -
K Ca Ga Ge As Se Br Kr
0.8 1.0 1.6 1.8 2.0 2.4 2.8 -
Rb Sr In Sn Sb Te I Xe
0.8 1.0 1.7 1.8 2.0 2.1 2.5 -
Cs Ba Tl Pb Bi Po At Rn
0.7 0.9 1.8 1.8 1.9 2.0 2.2 -
26
What trends do you notice about the EN
values in the Periodic Table? Explain.
H He
2.1 -
Li Be B C N O F Ne
1.0 1.5 2.0 2.5 3.0 3.5 4.0 -
0.9 1.2 1.5 1.8 2.1 2.5 3.0 -
0.8 1.0 1.6 1.8 2.0 2.4 2.8 -
0.8 1.0 1.7 1.8 2.0 2.1 2.5 -
0.7 0.9 1.8 1.8 1.9 2.0 2.2 -
27
The EN values increase from left to
right across a Period.
H He
2.1 -
Li Be B C N O F Ne
1.0 1.5 2.0 2.5 3.0 3.5 4.0 -
0.9 1.2 1.5 1.8 2.1 2.5 3.0 -
0.8 1.0 1.6 1.8 2.0 2.4 2.8 -
0.8 1.0 1.7 1.8 2.0 2.1 2.5 -
0.7 0.9 1.8 1.8 1.9 2.0 2.2 -
28
What trends do you notice about the
EN values in the Periodic Table?
Explain.
The EN values increase from left to
right across a Period.
The atomic radius decreases from

left to right across a Period.Thus,the
nuclear attraction experienced by the
bonding electrons increases accordingly.
29
The EN values decrease down a Group.
H He
2.1 -
Li Be B C N O F Ne
1.0 1.5 2.0 2.5 3.0 3.5 4.0 -
0.9 1.2 1.5 1.8 2.1 2.5 3.0 -
0.8 1.0 1.6 1.8 2.0 2.4 2.8 -
0.8 1.0 1.7 1.8 2.0 2.1 2.5 -
0.7 0.9 1.8 1.8 1.9 2.0 2.2 -
30
What trends do you notice about the
EN values in the Periodic Table?
Explain.
The EN values decrease down a Group.
The atomic radius increases down a

Group, thus weakening the forces of
attraction between the nucleus and
the bonding electrons.
31
Why are the E.A. of noble gases not
shown ?
H He
2.1 -
Li Be B C N O F Ne
1.0 1.5 2.0 2.5 3.0 3.5 4.0 -
0.9 1.2 1.5 1.8 2.1 2.5 3.0 -
0.8 1.0 1.6 1.8 2.0 2.4 2.8 -
0.8 1.0 1.7 1.8 2.0 2.1 2.5 -
0.7 0.9 1.8 1.8 1.9 2.0 2.2 -
32
Why are the E.A of noble gases not shown ?
EN is a measure of the ability of an atom to

attract electrons in a chemical bond.
However, noble gases are so inert that they
rarely form chemical bonds with other
atoms.
XeF2, XeF4 and XeF6 are present
33
Formation of Ionic Bond
Atoms of Group IA and IIA elements ‘tend’
to achieve the noble gas structures in the
previous Period by losing outermost
electron(s).
In fact, formations of positive ions from

metals are endothermic and not spontaneous.
I.E. values are always positive
34
Formation of Ionic Bond
Atoms of Group VIA and VIIA elements tend
to achieve the noble gas structures in the
same Periods by gaining electron(s)
First E.A. of Group VIA and VIIA elements
are always negative.
 Spontaneous and exothermic processes
35
The oppositely charged ions are stabilized
by coming close to each other to form the
ionic bond.
Ionic bond is the result of electrostatic

interaction between oppositely charged
ions.
Interaction = attraction + repulsion
36
Dots and Crosses Diagram
37
Notes on Dots & Crosses representation
 Electrons in different atoms are
indistinguishable.
 The dots and crosses do not indicate
the exact positions of electrons.
 Not all stable ions have the noble gas
structures(Refer to pp.4-5).
38
Tendency for the Formation of Ions
An ion will be formed easily if
1. The electronic structure of the ion i
s stable;
2. The charge on the ion is small;
3. The size of parent atom from which
the ion is formed is
small for an anion, or
large for a cation.
39
For cation,
Larger size of parent atom
 less positive I.E. or less +ve sum of
successive I.E.s,
 easier formation of cation,
 atoms of Group IA & Group IIA e

lements form cations easily.
40

Ease of formation of cation Ease of formation of cation 
Li+ Be2+
Na+ Mg2+ Al3+
K+ Ca2+ Sc3+
Rb+ Sr2+ Y3+ Zr4+
Cs+ Ba2+ La3+ Ce4+
41
For anion,
Smaller size of parent atom
 more negative E.A. or more -ve sum of
successive E.A.s,
 easier formation of anion,
 atoms of Group VIA & Group VIIA elem
ents form anions easily.
42
Ease of formation of anion Ease of formation of anion 
N3 O2 F
P3 S2 Cl
Br
I

43
Stable Ionic Structures
Not all stable ions have the noble gas
electronic structures.
Q.2 Write the s,p,d,f notation for each of

the following cations.
Use your answers to identify three types
of commonly occurring arrangement of
outershell electrons of cations other than
the stable octet structure.
44
Q.2 Write the s,p,d,f notation for the following cations

Zn2+
Pb2+
V3+
Cr3+
Fe3+
Fe2+
Co2+
Ni2+
Cu2+
45
Q.2
Zn2+ 1s2,2s2,2p6,3s2,3p6,3d10
Pb2+ 1s2,2s2,2p6,3s23p63d10,4s2,4p6,4d10,4f14,5s2,5p6,5d10,6s2
V3+ 1s2,2s2,2p6,3s23p63d2
Cr3+ 1s2,2s2,2p6,3s23p63d3
Fe3+ 1s2,2s2,2p6,3s23p63d5
Fe2+ 1s2,2s2,2p6,3s23p63d6
Co2+ 1s2,2s2,2p6,3s23p63d7
Ni2+ 1s2,2s2,2p6,3s23p63d8
Cu2+ 1s2,2s2,2p6,3s23p63d9
46
1. 18 - electrons group e.g. Zn2+
Fully-filled s, p & d-subshells
Zn2+ 1s2,2s2,2p6,3s2,3p6,3d10
V3+ 1s2,2s2,2p6,3s23p63d2
Cr3+ 1s2,2s2,2p6,3s23p63d3
Fe3+ 1s2,2s2,2p6,3s23p63d5
Fe2+ 1s2,2s2,2p6,3s23p63d6
Co2+ 1s2,2s2,2p6,3s23p63d7
Ni2+ 1s2,2s2,2p6,3s23p63d8
Cu2+ 1s2,2s2,2p6,3s23p63d9
47
2. (18 + 2 ) - electron group e.g. Pb2+
Fully-filled s, p & d-subshells
Zn2+ 1s2,2s2,2p6,3s2,3p6,3d10
V3+ 1s2,2s2,2p6,3s23p63d2
Cr3+ 1s2,2s2,2p6,3s23p63d3
Fe3+ 1s2,2s2,2p6,3s23p63d5
Fe2+ 1s2,2s2,2p6,3s23p63d6
Co2+ 1s2,2s2,2p6,3s23p63d7
Ni2+ 1s2,2s2,2p6,3s23p63d8
Cu2+ 1s2,2s2,2p6,3s23p63d9
48
3. Variable arrangements for ions of
transition metals.
ns2,np6, nd1 to ns2,np6, nd9
Zn2+ 1s2,2s2,2p6,3s2,3p6,3d10
V3+ 1s2,2s2,2p6,3s23p63d2
Cr3+ 1s2,2s2,2p6,3s23p63d3
Fe3+ 1s2,2s2,2p6,3s23p63d5
Fe2+ 1s2,2s2,2p6,3s23p63d6
Co2+ 1s2,2s2,2p6,3s23p63d7
Ni2+ 1s2,2s2,2p6,3s23p63d8
Cu2+ 1s2,2s2,2p6,3s23p63d9
Ti3+ [Ne] 3s23p63d1 Mn3+ [Ne] 3s23p63d4

49
Electronic arrangements of stable cations
Ionization enthalpy determines the ease o

f formation of cations.
Less positive I.E. or sum of I.E.s
 easier formation of cations
50
Electronic arrangements of stable cations
Octet structure : -
cations of Group IA, IIA and IIIB
IA IIA IIIB
2,8 Na+ Mg2+ Al3+(IIIA)
2,8,8 K+ Ca2+ Sc3+
2,8,18,8 Rb+ Sr2+ Y3+
51
(a) 18 - electrons group
cations of Groups IB, IIB, IIIA and IVA
IB IIB IIIA IVA
2,8,18 Cu+ Zn2+ Ga3+ --
2,8,18,18 Ag+ Cd2+ In3+ Sn4+
2,8,18,32,18 Au+ Hg2+ Tl3+ Pb4+
52
Less stable than ions with a noble gas structure.
IB IIB IIIA IVA
2,8,18 Cu+ Zn2+ Ga3+ --
2,8,18,18 Ag+ Cd2+ In3+ Sn4+
2,8,18,32,18 Au+ Hg2+ Tl3+ Pb4+
53
Cu and Au form other ions because the
nuclear charges are not high enough to hold
the 18-electron group firmly.
IB IIB IIIA IVA
2,8,18 Cu+ Zn2+ Ga3+ --
2,8,18,18 Ag+ Cd2+ In3+ Sn4+
2,8,18,32,18 Au+ Hg2+ Tl3+ Pb4+
54
Cu2+ 2, 8, 17 Au3+ 2, 8, 18, 32, 16
The d-electrons are more diffused and thus
less attracted by the less positive nuclei.
IB IIB IIIA IVA
2,8,18 Cu+ Zn2+ Ga3+ --
2,8,18,18 Ag+ Cd2+ In3+ Sn4+
2,8,18,32,18 Au+ Hg2+ Tl3+ Pb4+
55
(b) (18+2) electrons
Cations of heavier group members
due to presence of 4f electrons.
Tl [2,8,18,32], 5s2, 5p6, 5d10, 6s2, 6p1

Tl3+ [2,8,18,32], 5s2, 5p6, 5d10 (18)
Tl+ [2,8,18,32], 5s2, 5p6, 5d10, 6s2 (18 + 2)
Stability : Tl+ > Tl3+ due to extra stability of
6s electrons (inert pair effect)
56
Tl [2,8,18,32], 5s2, 5p6, 5d10, 6s2, 6p1
Tl3+ [2,8,18,32], 5s2, 5p6, 5d10 (18)
Tl+ [2,8,18,32], 5s2, 5p6, 5d10, 6s2 (18 + 2)
6s electrons are poorly shielded by the inner

4f electrons.
6s electrons experience stronger nuclear
attraction.
57
Tl [2,8,18,32], 5s2, 5p6, 5d10, 6s2, 6p1
Tl3+ [2,8,18,32], 5s2, 5p6, 5d10 (18)
Tl+ [2,8,18,32], 5s2, 5p6, 5d10, 6s2 (18 + 2)
Inert pair effect increases down a Group.

Stability : Sn4+(18) > Sn2+(18+2) moving down
Group IV
Pb2+(18+2) > Pb4+(18)
58
Tl [2,8,18,32], 5s2, 5p6, 5d10, 6s2, 6p1
Tl3+ [2,8,18,32], 5s2, 5p6, 5d10 (18)
Tl+ [2,8,18,32], 5s2, 5p6, 5d10, 6s2 (18 + 2)
Inert pair effect increases down a Group.

Stability : Sb5+(18) > Sb3+(18+2) moving down
Group V
Bi3+(18+2) > Bi5+(18)
59
(c) Cations of transition elements
- variable oxidation numbers
- Electronic configurations from
ns2, np6, nd1 to ns2, np6, nd9
Fe [Ne] 3s2, 3p6, 3d6, 4s2

Fe2+ [Ne] 3s2, 3p6, 3d6
Fe3+ [Ne] 3s2, 3p6, 3d5
60
(c) Cations of transition elements
Fe [Ne] 3s2, 3p6, 3d6, 4s2
Fe2+ [Ne] 3s2, 3p6, 3d6
Fe3+ [Ne] 3s2, 3p6, 3d5
Which one is more stable, Fe2+(g) or Fe3+(g) ?

Fe2+(g) is more stable than Fe3+(g)
Energy is needed to remove electrons from Fe2+
(g) to give Fe3+(g)
61
B. Anions - with noble gas structures
Electron affinity determines the ease of

formation of anions.
More -ve E.A. or sum of E.A.s
 more stable anion
Group VIA and Group VIIA elements for
m anions easily.
62
First Electron Affinity (kJ mol1)
X(g) + e  X(g)
H He
-73 +21
Li Be B C N O F Ne
-60 +18 -23 -122 ~0 -142 -322 +29
-53 +21 -44 -134 -72 -200 -349 +35
K Br Kr
-48 -325 +39
63
E.A. becomes more –ve from Gp 1 to Gp 7 ac
ross a period
H He
-73 +21
Li Be B C N O F Ne
-60 +18 -23 -122 ~0 -142 -328 +29
-53 +21 -44 -134 -72 -200 -349 +35
K Br Kr
-48 -324 +39
64
The electrons added experience stronger
nuclear attraction when the atoms are getting
smaller across the period.
H He
-73 +21
Li Be B C N O F Ne
-60 +18 -23 -122 ~0 -142 -328 +29
-53 +21 -44 -134 -72 -200 -349 +35
K Br Kr
-48 -324 +39
65
+ve E.A. for Gp 2 and Gp 0 because the electron
added occupies a new shell / subshell
H He
-73 +21
Li Be B C N O F Ne
-60 +18 -23 -122 ~0 -142 -328 +29
-53 +21 -44 -134 -72 -200 -349 +35
K Br Kr
-48 -324 +39
66
Goes to a new subshell Goes to a new shell
Be(2s2)  Be(2s22p1)
Ne(2p6)  Ne(2p63s1)
H He
-73 +21
Li Be B C N O F Ne
-60 +18 -23 -122 ~0 -142 -328 +29
-53 +21 -44 -134 -72 -200 -349 +35
K Br Kr
-48 -324 +39
67
More –ve E.A. for Gp 1 because the ions forme
d have full-filled s-subshells.
E.g. Li(1s22s1)  Li(1s22s2)
H He
-73 +21
Li Be B C N O F Ne
-60 +18 -23 -122 ~0 -142 -328 +29
-53 +21 -44 -134 -72 -200 -349 +35
K Br Kr
-48 -324 +39
68
Less –ve E.A. for Gp 5 because the stable half-
filled p-subshell no longer exists.
E.g. N(2s22p3)  N(2s22p4)
H He
-73 +21
Li Be B C N O F Ne
-60 +18 -23 -122 ~0 -142 -328 +29
-53 +21 -44 -134 -72 -200 -349 +35
K Br Kr
-48 -324 +39
69
Q.3 Why are the first E.A.s of halogen atoms more
negative than those of the O atom or the S
atom ?
H He
-73 +21
Li Be B C N O F Ne
-60 +18 -23 -122 ~0 -142 -328 +29
-53 +21 -44 -134 -72 -200 -349 +35
K Br Kr
-48 -324 +39
70
It is because the halide ions formed have full-fi
lled s/p subshells (octet structure).
H He
-73 +21
Li Be B C N O F Ne
-60 +18 -23 -122 ~0 -142 -328 +29
-53 +21 -44 -134 -72 -200 -349 +35
K Br Kr
-48 -324 +39
71
Q.4 Why are the second E.A.s of O(+844 kJmol1)
and S(+532 kJmol1) positive ?
O(g) + e  O2(g)
S(g) + e  S2(g)
The electrons added are repelled strongly

by the negative ions.
72
Why is the E.A. of F less negative than t
hat of Cl ?
Halogen F Cl Br I
E.A.
328 349 325 295
kJ mol1
The size of Fluorine atom is so small that

the addition of an extra electron results in
great repulsion among the electrons.
The 2nd electron shell is much smaller than the
3rd electron shell.
73
Energetics of Formation of Ionic Compounds
A. Formation of an ion pair in gaseous state
Consider the formation of a KF(g) ion pair from K(g) & F(g)
H1
K(g) + F(g) KF(g)
EA1(F)
IE1(K) H2
K+(g) + F(g)
By Hess’s law, H1 = IE1(K) + EA1(F) + H2
74
Q.6
H1 = IE1(K) + EA1(F) + H2
(+)
419.0 103 J mol 1  328.0 103 J mol 1 Q 1Q 2
()
  
6.022 10 mol
23 1
6.022 10 mol
23 1
4π 0 R
19
(1.602  10 C)2
 1.511 10 19 J 
 
4π 8.854  10 12 C2 J1m1 2.170  10 10 m 
 1.511 10 19 J  1.063 10 18 J
 9.119  10  19 J
75
H1 = IE1(K) + EA1(F) + H2
= 1.5111019 J  1.0631018 J = 9.1191019 J
H2 = 1.0631018 J
IE1(K) + EA1(F) = +1.5111019 J
19
ΔH1  9.119  10 J
76
When R 
Stability : K+(g) + F-(g) < K(g) + F(g) by +1.511x10-19J
H2 = 1.0631018 J
IE1(K) + EA1(F) = +1.5111019 J
19
ΔH1  9.119  10 J
77
I.E. and E.A. are NOT the driving forces for the
formation of ionic bond.
H2 = 1.0631018 J
IE1(K) + EA1(F) = +1.5111019 J
19
ΔH1  9.119  10 J
78
K+(g) & F(g) tend to come close together in order
to become stable.
H2 = 1.0631018 J
IE1(K) + EA1(F) = +1.5111019 J
19
ΔH1  9.119  10 J
79
Coulomb stabilization is the driving force for the
formation of ionic bond.
H2 = 1.0631018 J
IE1(K) + EA1(F) = +1.5111019 J
19
ΔH1  9.119  10 J
80
When R = 2.1701010 m
The most energetically stable state is reached.
H2 = 1.0631018 J
IE1(K) + EA1(F) = +1.5111019 J
19
ΔH1  9.119  10 J
81
The ions cannot come any closer than Re as it will
results in less stable states
H2 = 1.0631018 J
IE1(K) + EA1(F) = +1.5111019 J
19
ΔH1  9.119  10 J
82
Repulsions between electron clouds and between
nuclei > attraction between ions
H2 = 1.0631018 J
IE1(K) + EA1(F) = +1.5111019 J
19
ΔH1  9.119  10 J
83
1
Potential energy (V) Repulsion : V  12
R
between opposite charges
Minimum V when R = 2.170  1010 m
1
Attraction : V
R
between opposite charges
84
What is the significance of the lowest energy
state of the neutral state of K + F ?
H2 = 1.0631018 J
IE1(K) + EA1(F) = +1.5111019 J
19
ΔH1  9.119  10 J
85
A covalent bond is formed K F


K 
F  

Electrostatic attraction between positive

nuclei and bond electron pair stabilizes
the system
86
A. Formation of Ionic Crystals
Consider the formation of NaCl(s) from Na(s) & Cl2(g)
1 Hf
Na(s) + Cl2(g) NaCl(s)
2
H1 H2
Na+(g) + Cl(g)
By Hess’s law, Hf = H1 + H2
87
H1 is the sum of four terms of enthalpy changes
1. Standard enthalpy change of atomization of Na(s)

Na(s)  Na(g) H = +108.3 kJ mol-1
2. First ionization enthalpy of Na(g)
Na(g)  Na+(g) + e- H= +500 kJ mol-1
3. Standard enthalpy change of atomization of Cl2(g)
1/2Cl2(g)  Cl(g) H = +121.1 kJ mol-1
4. First electron affinity of Cl(g)

Cl(g) + e-  Cl-(g) H = -349 kJ mol-1
88
H2 is the lattice enthalpy of NaCl.
It is the enthalpy change for the forma
tion of 1 mole of NaCl(s) from its const
ituent ions in the gaseous state.
Na+(g) + Cl-(g)  NaCl(s) HLo
89
Direct determination of lattice enthalpy
by experiment is very difficult, but it
can be obtained from
1.theoretical calculation using an ionic

model, Or
2.experimental results indirectly with the
use of a Born-Haber cycle.
90
Q.7 Calculate the lattice enthalpy of NaCl
Hf = H1 +H2

Lattice enthalpy
= H2
= Hf - H1
= [(411)  (+108.3 + 500 + 121.1  349)] kJ mol1
= 791.4 kJ mol1
91
-349
-791.4
92
Lattice enthalpy is the dominant enthalpy term res
ponsible for the -ve Hf of an ionic compound.
More ve HLo  More stable ionic compound
Lattice enthalpy is a measure of the strength

of ionic bond.
93
Determination of Lattice Enthalpy
• From Born-Haber cycle (experimental

method, refers to Q.7)
• From theoretical calculation based on
the ionic model
94
Assumptions made in the calculation
• Ions are spherical and have no distortion

of the charge cloud, I.e. 100% ionic.
• The crystal has certain assumed lattice
structure.
• Repulsive forces between oppositely
charged ions at short distances are
ignored.
95
M is the Madelung constants that
depends on the crystal structure
MLQ Q
H lattice 
4 0 (r  r )
96
L is the Avogadro’s constant
MLQ Q
H lattice 
4 0 (r  r )
97
Q+ and Q- are the charges on the catio
n and the anion respectively
MLQ Q
H lattice 
4 0 (r  r )
98
0 is the permittivity of vacuum
MLQ Q
H lattice 
4 0 (r  r )
99
(r+ + r-) is the nearest distance betwee
n the nuclei of cation and anion
r+ is the ionic radius of the cation
r- is the ionic radius of the anion
MLQ Q
H lattice 
4 0 (r  r )
100
Stoichiometry of Ionic Compounds
 Stoichiometry of an ionic compound is the

simplest whole number ratio of cations
and anions involved in the formation of
the compound.
 There are two ways to predict stoichiometry.
101
1. Considerations in terms of electronic
configurations
Atoms tend to attain noble gas electronic structure

s by losing or gaining electron(s).
The ionic compound is electrically neutral.
total charges on cation = total charges on anions
102
1. Considerations in terms of electronic
configurations
Na + F  [Na]+ [F]-
2,8,1 2,7 2,8 2,8  NaF
Mg + 2Cl  [Cl]- [Mg]2+ [Cl]-

2,8,2 2,8,7 2,8,8 2,8 2,8,8
 MgCl2
103
2. Considerations in terms of enthalpy changes
of formation
Based on the Born-Haber cycle & the th
eoretically calculated lattice enthalpy,
enthalpy the valu
es of Hfo of hypothetical compounds (e.g. Mg
Cl , MgCl2 , MgCl3) can be calculated.
The stoichiometry with the most negative
Hfo value is the most stable one.
one
104
2. Considerations in terms of enthalpy changes
of formation
Or, we can determine the true stoichiometry

by comparing the calculated Hfo values of hy
pothetical compounds with the experimentally det
ermined Hfo value.
The stoichiometry with Hfo value closest to

the experimentally determined Hfo value is
the answer.
105
Q.8 Three hypothetical formulae of magnesium chloride
are proposed and their estimated lattice enthalpies
are shown in the table below.
Hypothetical
MgCl MgCl2 MgCl3
stoichiometry
Assumed
NaCl CaF2 AlCl3
structure
Estimated
o -1 -771 -2602 -5440
HL (kJ mol )
106
Hf[MgCl(s)] = Hat[Mg(s)] + 1st IE of Mg + Hat[1/2Cl2(g)]
+ 1st EA of Cl + HL[MgCl(s)]
= (+150 + 736 + 121 - 364- 771) kJ mol-1
= -128 kJ mol-1
107
Mg+(g)+Cl(g)
Enthalpy (kJ mol
Hat[1/2Cl2] 1
Mg+(g)+ Cl (g) 1st EA[Cl]
2 2 Mg+(g)+Cl(g)
1st IE[Mg]

 1 HL[MgCl]
Mg(g)+ Cl2(g)
)
2
1
Hat[Mg] Mg(s)+ Cl (g)
2 2
Hf[MgCl]<0 MgCl(s)
108
Hf[MgCl2(s)]
= Hat[Mg(s)] + 1st IE of Mg + 2nd IE of Mg
+ 2Hat[1/2Cl2(g)] + 21st EA of Cl + HL[MgCl2(s)]
= [150+736+1450+2121+2(-364)+(-2602)] kJ mol-1
= -752 kJ mol-1
109
Mg2+(g)+2Cl(g)
2Hat[1/2Cl2]
Mg2+(g)+Cl2(g) 21st EA[Cl]
Enthalpy (kJ
Mg2+(g)+2Cl(g)
2nd IE[Mg]
Mg+(g)+Cl2(g) HL[MgCl2]
1st IE[Mg]
Mg(g)+Cl2(g)
Hat[Mg] Mg(s)+Cl2(g)
Hf[MgCl2] <0
MgCl2(s)
110
Hf[MgCl3(s)]
= Hat[Mg(s)] + 1st IE of Mg + 2nd IE of Mg + 3rd IE of Mg
+ 3Hat[1/2Cl2(g)] + 31st EA of Cl + HL[MgCl3(s)]
= 150+736+1450+7740+3121+3(-364)+(-5440)
= +3907 kJ mol-1
111
Mg3+(g)+3Cl(g)
3Hat[1/2Cl2] Mg3+(g)+
3 Cl (g)
2 2 31st EA[Cl]
Mg3+(g)+3Cl(g)
Enthalpy ( kJ mol
3rd IE[Mg]
HL[MgCl3]
Mg2+(g)+
3Cl (g) MgCl3(s)
 2 2

)
2nd IE[Mg]
Mg+(g)+ 3 Cl2(g)
2 Hf[MgCl3] >0
1st IE[Mg] Mg(g)+ 3Cl (g)
2 2
Hat[Mg] Mg(s)+3/2Cl2(g)
112
Since the hypothetical compound MgCl2 has the m
ost negative Hf value, and
this value is closest to the experimentally determin
ed one,
the most probable formula of magnesium chloride
is
MgCl2
113
Reasons for the discrepancy between calculated and
experimental results of Hf
 The ionic bond of MgCl2 is not 100% pure.

I,e. the ions are not perfectly spherical.
 MgCl2 has a different crystal structure from CaF2
 Short range repulsive forces between oppositely
charged ions have not been considered.
Check Point 7-2

114
7.2 Energetics of Formation of Ionic Compounds (SB p.196)
Factors affecting lattice enthalpy

• Effect of ionic size:
 The greater the ionic size
 The lower (or less negative) is the lattice
enthalpy
MLQ Q
H lattice 
4 0 (r  r )
115
Factors affect lattice enthalpy

• Effect of ionic charge:
 The greater the ionic charge
 The higher (or more negative) is the
lattice enthalpy
MLQ Q
H lattice 
4 0 (r  r )
Check Point 7-3
116
7.4
Ionic Crystals
117
7.4 Ionic Crystals (SB p.202)
Crystal Lattice( 晶體格子 )
118
In solid state, ions of ionic compounds are

regularly packed to form 3-dimensional str
uctures called crystal lattices( 晶體格子 )
119
The coordination number (C.N.) of a given partic

le in a crystal lattice is the number of nearest
neighbours of the particle.
C.N. of Na+
=6
120
The coordination number (C.N.) of a given partic

le in a crystal lattice is the number of nearest
neighbours of the particle.
C.N. of Cl
=6
121
Identify the unit cell of NaCl crystal lattice
Not a unit cell
122
Identify the unit cell of NaCl crystal lattice
Not a unit cell
123
The unit cell of a crystal lattice is the simplest
3-D arrangement of particles which, when
repeated 3-dimensionally in space, will
generate the whole crystal lattice.
124
125
126
Unit cell
Unit cell
127
A crystal lattice with a cubic unit cell is
known as a cubic structure.
128
Three Kinds of Cubic Structure
• Simple cubic (primitive) structure

• Body-centred cubic (b.c.c.) structure
• Face-centred cubic (f.c.c.) structure
129
Simple cubic structure
Space Space
filling lattice
Unit cell 
View this Chemscape 3D structure

130
Body-centred cubic (b.c.c.) structure
Space Space
filling lattice
Unit cell 

131
Face-centred cubic (f.c.c.) structure
Unit cell
132
The f.c.c. structure can be obtained by stacking the
layers of particles in the pattern abcabc...
133
Interstitial sites
- The empty spaces in a crystal lattice
Two types of interstitial sites in f.c.c. structure
Octahedral site
Tetrahedral site
134
Octahedral site : -
It is the space between the 3 spheres in one
layer and 3 other spheres in the adjacent
layer.
135
When the octahedron is rotated by 45o , the octahedral site can
also be viewed as the space confined by 4 spheres in one layer
and 1 other sphere each in the upper and lower layers
respectively.
45o
before
behind
136
Tetrahedral site : -
It is the space between the 3 spheres of one
layer and a fourth sphere on the upper layer.
137
In an f.c.c. unit cell, the tetrahedral site is th
e space bounded by a corner atom and the thre
e face-centred atoms nearest to it.
138
b a
c
139
Q.9 Label a, b, and c as Oh sites or Td sites
a and b are Td sites
c is Oh site
Top layer
140
Q.10 Identify the Oh sites and Td sites in
the f.c.c. unit cell shown below.
2
1
4
3 13 Oh sites
5 6
1 3 4 Th sites in
5
9
6 the front
8
7 8 7 4 Th sites at
2 4
11 the back
10 12
13
View Octahedral sites and tetrahedral sites

141
Since ionic crystal lattice is made of two
kinds of particles, cations and anions,
the crystal structure of an ionic compound
can be considered as two lattices of cations
and anions interpenetrating with each other.
142
The crystal structures of
sodium chloride,
caesium chloride and
calcium fluoride are discussed.
143
Sodium Chloride (The Rock Salt Structure)
f.c.c. unit cell of larger

Cl- ions, with all Oh site
s occupied by the small
er Na+ ions
Oh sites of f.c.c.
lattice of Cl- ions
144
A more open f.c.c. u
nit cell of smaller Na
+
ions with all Oh sit
es occupied by the la
rger Cl- ions.
Oh sites of f.c.c.
lattice of Na+ ions
145
F.C.C. Structure of Sodium Chloride
146
Structure of Sodium Chloride Unit cell of NaCl
Co-ordination number of Na+ = 6

6 : 6 co-ordination
Co-ordination number of Cl = 6
-
147
Only the particles in the centre (or body)
of the unit cell belong to the unit cell
entirely. Particles locating on the faces,
along the edges or at the corner of a unit
cell are shared with the neighboring unit
cells of the crystal lattice.
148
1/2
Body Face Edge Corner
1 1/2
Fraction of particles occupied by a unit cell
149
1/4
1 1/2 1/4
150
1/8
1 1/2 1/4 1/8
151
Q.11 Calculate the net nos. of Na+ and Cl-
ions in a unit cell of NaCl.
1 1
No. of Cl- ions = 8    6    4
8  2
8 corners 6 faces
1
No. of Na ions =
+
12     1  4
4
12 edges 1 body
Example 7-4
152
Structure of Caesium Chloride  Link

Cs+ ions are too large to fit Simple cubic lattice
in the octahedral sites.
Thus Cl ions adopt the mor
e open simple cubic structu
re with the cubical sites oc
cupied by Cs+ ions.
153
A cubical site is the space confined
by 4 spheres in one layer and 4 other
spheres in the adjacent layer.
154
Size of interstitial sites : -
Cubical > octahedral > tetrahedral
In f.c.c. structure
In simple cubic structure
155
Structure of Caesium Chloride  Link

Simple cubic lattice
Co-ordination number of Cs+ = 8

8 : 8 co-ordination
Co-ordination number of Cl- = 8
156
Q.12
Number of Cs+ = 1
1
Number of Cl = 8   1
8
157
Structure of Calcium Fluoride  Link

Fluorite structure
It can be viewed as a
simple cubic structure
of larger fluoride ions
with alternate cubical
sites occupied by
smaller calcium ions.
158
Alternately, it can be viewed as

an expanded f.c.c. structure
of smaller calcium ions with all
tetrahedral sites occupied by
larger fluoride ions.
159

Face-centred c
ubic lattice
Co-ordination number of Ca2+ = 8

8 : 4 co-ordination
Co-ordination number of F- = 4
160
Q.13 (a)
CaF2
Number of F = 8
1 1
Number of Ca2+ = 8   6   4
8 2
161
Q.13 (b) CaF2
Only alternate cubical si

tes are occupied by Ca2+
in order to maintain elec
troneutrality.
162
Structure of Sodium oxide  Link

Antifluorite structure
Na2O vs CaF2
fluorite structure
163
Q.14(a)
Zinc blende s
tructure -
Link
164
Q.14(a)
ZnS
Number of Zn2+ = 4
1 1
Number of S2 = 8  6  4
8 2
165
Q.14(b)
Zinc sulphide, ZnS
r 0.074
  0.402  0.414
r 0.184
 tetrahedral site
S2 ions adopt f.c.c. structure
Alternate Td sites are occupied by Zn2+
ions to ensure electroneutrality.
166
Q.15 Rutile structure - Link
The unit cell is not a cube

167
Q.15(a) Ti4+
O2
1
Number of Ti4+ = 1  8   2
8 TiO2
1
Number of O2 = 2  4   4
2
168
Q.15(a)
C.N. of Ti4+ = 6
 6 : 3 coordination
C.N. of O2 = 3
169
Q.15(b)
Titanium(IV) oxide, TiO2
r 0.068
  0.486  0.414
r 0.140
 octahedral site
O2 ions adopt distorted h.c.p.(not f.c.c.) st
ructure with alternate Oh sites occupied b
y Ti4+ ions to ensure electroneutrality.
170
hexagonal close-packed
a
171
Factors governing the structures of ionic crystals
1. Close Packing Considerations
Ions in ionic crystals tend to pack as closely as

possible. (Why ?)
To strengthen the ionic bonds formed
To maximize the no. of ionic bonds formed.
172
1. Close Packing Considerations
The larger anions tend to adopt face-centred

cubic structure (cubic closest packed, c.c.p.)
The smaller cations tend to fill the interstitial
sites as efficiently as possible
173
Q.16 Is there no limit for the C.N. ?

Explain your answer.
The anions tend to repel one another when th
ey approach a given cation.
The balance between attractive forces and re
pulsive forces among ions limits the C.N. of th
e system.
174

If the cations are small, less anions can appro

ach them without significant repulsions.
Or, if the cations are small, they choose to fi
t in the smaller tetrahedral sites with smaller
C.N. to strengthen the ionic bonds formed.
175

If the cations are large, they choose to fit in

the larger octahedral sites or even cubical sit
es with greater C.N. to maximize the no. of io
nic bonds formed.
176
r
2. The relative size of cation and anion,
r
In general, r > r+,
r
0  1
r
r
 C.N . 
r
177
r
If the cations are large, 1
r
more anions can approach the cations withou
t significant repulsions.
Or, the large cations can fit in the larger int
erstitial sites with greater C.N. to maximize
the no. of bonds formed.
178
Summary : -
Interstitial
Tetrahedral Octahedral Cubical
site
Coordination 4:4 6:6 8:8

r
0.225 – 0.414 0.414 – 0.732 0.732 – 1.000
r
Alkali metal ha CsCl, CsBr
ZnS, most co
Examples lides except C
pper(I) halides CsI, NH4Cl
sCl
NH4+ is large
179
Summary : -
Interstitial
Cubical
site
Coordination 8:4
r
0.732 – 1.000
r
Examples *CaF2, BaF2, BaCl2, SrF2
180
Q.17 BA r
cos ABC    cos 45 
BC r  r
r
 0.414
r r
A B
45 °
r
r
C +
181
r
 0.414
r
r
0.732   0.414
r
the range of ratio that favours octa
hedral arrangement.
182
r
 0.732
r
the optimal ratio for cations and anio
ns to be in direct contact with each
other in the cubical sites.
Q.18
183
Q.18(a)
Silver chloride, AgCl
r 0.126
  0.696  0.414
r 0.181
 octahedral site
Cl ions adopt f.c.c. structure
All Oh sites are occupied by Ag+
ions to ensure electroneutrality.
184
Q.18(a)
Silver chloride, AgCl
r 0.126
  0.696  0.414
r 0.181
 octahedral site
Ag+ ions adopt an open f.c.c. structure
All Oh sites are occupied by Cl ions to
ensure electroneutrality.
185
Q.18(b)
Copper(I) bromide, CuBr
r 0.074
  0.379  0.414
r 0.195
Br ions adopt f.c.c. structure
Only alternate Td sites are occupied by C
u+ ions to ensure electroneutrality.
186
Copper(II) bromide, CuBr2
r 0.071
  0.364  0.414
r 0.195
Br ions adopt f.c.c. structure
Only 1/4 Td sites are occupied by Cu+ ions t
o ensure electroneutrality.
Some Br may form less bonds than others
 Not favourable. Q.18(c)
187
Q.18(c)
Copper(II) bromide, CuBr2
Or, Cu2+ ions adopt a very

open f.c.c. structure
All the Td sites are occupied by Br ions t
o ensure electroneutrality.
However, this structure is too open to
form strong ionic bonds.
 non-cubic structure is preferred.
188
Q.18(c)
4 : 2 coordination
Cu2+
Br
189
Copper(II) chloride, CuCl2
Layer structure
0.295nm
0.230 nm
190
Copper(II) chloride, CuCl2
6 : 3 coordination
191
7.5
Ionic Radii
192
Ionic Radii
Ionic radius is the approximate radius
of the spherical space occupied by the
electron cloud of an ion in all directions
in the ionic crystal.
193
Q.19
Why is the electron cloud of an ion always
spherical in shape ?
Stable ions always have fully-filled electron shel

ls or subshells. The symmetrical distribution of
electrons accounts for the spherical shapes of i
ons.
194
Q.19 spherical Symmetrical distribution
along x, y and z axes 
 almost
Li+ 1s2 spherical
Na+ [He] 2s2, 2px2, 2py2, 2pz2
Cl [Ne] 3s2, 3px2, 3py2, 3pz2

2 2
Zn 2+
[Ar] 3d , 3d , 3d ,
2 3d
2 x 2 2
 y 2
, 3dz2
xy xz yz
Symmetrical distribution along xy, xz, yz planes

and along x, y and z axes  almost spherical
195
Determination of Ionic Radii
Pauling Scale
Interionic distance (r+ + r) can be de

termined by
X-ray diffraction crystallography
196
7.5 Ionic Radii (SB p.205)
Na+ Cl
Electron density Contour having
map for NaCl same electron
density
r++ r
Cl Na+
r++ r
Electron density plot for sodium chloride crystal

197
By additivity rule,
Interionic distance = r+ + r
For K+Cl,
r+ + r = 0.314 nm (determined by X-ray)
Since K+(2,8,8) and Cl(2,8,8) are isoelectro
nic, their ionic radii can be calculated.
r+(K+) = 0.133 nm, r(Cl) = 0.181 nm
198
For Na+Cl,
r+ + r = 0.275 nm (determined by X-ray)
Since r(Cl) = 0.181 nm(calculated)
r+(Na+) = (0.275 - 0.181) nm = 0.094 nm
199
Limitation of Additivity rule
In vacuum, the size of a single ion has no li

mit according to quantum mechanics.
The size of the ion is restricted by other i
ons in the crystal lattice.
Interionic distance < r+ + r
200
Evidence :
Electron distribution is not perfectly spherical at
the boundary due to repulsion between electron cl
ouds of neighbouring ions.
201
Ionic radius depends on the bonding envir
onment.
For example, the ionic radius of Cl ions in
NaCl (6 : 6 coordination) is different from
that in CsCl (8 : 8 coordination).
202
Radii of cations < Radii of corresponding parent atoms

cations have one less electron shell than the parent
atoms
Ionicradius
Ionic radiusvs
vsatomic
atomicradius
radius
203
p/e of cation > p/e of parent atom  Less shielding effect
 stronger nuclear attraction for outermost electrons
 smaller size
Ionicradius
Ionic radiusvs
vsatomic
atomicradius
radius
204
Radii of anions > Radii of corresponding parent atoms
Ionicradius
Ionic radiusvs
vsatomic
atomicradius
radius
205
p/e of anion < p/e of parent atom  more shielding effect
 weaker nuclear attraction for outermost electrons
 larger size
Ionicradius
Ionic radiusvs
vsatomic
atomicradius
radius
206
Periodic trends of ionic radius
1. Ionic radius increases down a Group

Ionic radius depends on the size of the
outermost electron cloud.
On moving down a Group, the size of
the outermost electron cloud increases
as the number of occupied electron
shells increases.
207
Periodic trends of ionic radius
2. Ionic radius decreases along a series of isoele

ctronic ions of increasing nuclear charge
The total shielding effects of isoelectronic io
ns are approximately the same.
 Zeff  nuclear charge (Z)
 Ionic radius decreases as nuclear charge

increases.
208
Isoelectronic
to He(2) Isoelectronic
to Ar(2,8,8)
Isoelectronic
to Ne(2,8)
209
H is larger than most ions, why ?
210
Q.20 H > N3
The nuclear charge (+1) of H is too

small to hold the two electrons which
repel each other strongly within the
small 1s orbital.
Or,
p/e of H (1/2) < p/e of N3 (7/10)
211
The END
Example 7-5 Check Point 7-5

212
Why do two atoms bond together?
Answer
The two atoms tend to achieve an octet
configuration which brings stability.
213
How does covalent bond strength

compare with ionic bond strength?
They are similar in strength.

Both are electrostatic attractions between
charged particles.
Answer Back
214
Given the following data:

ΔH (kJ mol–1)
First electron affinity of oxygen –142
Second electron affinity of oxygen +844
Standard enthalpy change of atomization of oxygen +248
Standard enthalpy change of atomization of
aluminium +314
Standard enthalpy change of formation of
aluminium oxide –1669
215
Answer
ΔH (kJ mol–1)
First ionization enthalpy of aluminium +577
Second ionization enthalpy of aluminium +1820
Third ionization enthalpy of aluminium +2740
(a) (i) Construct a labelled Born-Haber cycle for the
formation of aluminium oxide.
(Hint: Assume that aluminium oxide is a purely ionic
compound.)
(ii) State the law in which the enthalpy cycle in (i) is
based on.
(b) Calculate the lattice enthalpy of aluminium oxide.
216
(a) (i)
(ii)The enthalpy cycle in (i) is based on Hess’s law which states that
the total enthalpy change accompanying a chemical reaction is
independent of the route by means of which the chemical
reaction is brought about.
217
Back
(b) ΔHf [Al2O3(s)] = 2 × ΔHatom[Al(s)] + 2 × (ΔHI.E.1 [Al(g)]

ø
ø
+ ΔHI.E.2 [Al(g)] + ΔHI.E.3 [Al(g)])
+ 3 × ΔHatom [O2(g)] + 3 × (ΔHE.A.1 [O(g)]
ø
+ ΔHE.A.2 [O(g)]) + ΔHlattice[Al2O3(s)]
ø
ΔHf [Al2O3(s)] = 2 × (+314) + 2 × (+577 + 1 820 + 2 740)

+ 3 × (+248) + 3 × (–142 + 844)
ø
+ ΔHlattice [Al2O3(s)]
ø
ø
ΔHf [Al2O3(s)] = + 628 + 10 274 + 744 + 2 106 + ΔHlattice[Al2O3(s)]
ø
ΔHlattice[Al2O3(s)] = ΔHf [Al2O3(s)] – (628 + 10 274 + 744 + 2 106)

= –1 669 – (628 + 10 274 + 744 + 2 106)
218 = –15 421 kJ mol–1

(a) Draw a Born-Haber cycle for the formation of magnesium

oxide.
(a) The Born-Haber cycle for the formation of MgO:
Answer
219
(b) Calculate the lattice enthalpy of magnesium oxide by mea

ns of the Born-Haber cycle drawn in (a).
Given: ΔHatom [Mg(s)] = +150 kJ mol–1
ø
ΔHI.E. [Mg(g)] = +736 kJ mol–1

ΔHI.E. [Mg+(g)] = +1 450 kJ mol–1
ø
ΔHatom [O2(g)] = +248 kJ mol–1

ΔHE.A. [O(g)] = –142 kJ mol–1
ΔHE.A. [O–(g)] = +844 kJ mol–1
Answer
ø
220
ΔHf [MgO(s)] = –602 kJ mol–1
(b) ΔHlattice [MgO(s)]

ø
= ΔHf [MgO(s)] – ΔHatom [Mg(s)]
ø
ø
– ΔHI.E. [Mg(g)] – ΔHI.E. [Mg+(g)] – ΔHatom [O2(g)]
ø
– ΔHE.A. [O(g)] – ΔHE.A. [O–(g)]
= [–602 – 150 – 736 – 1 450 – 248 –(–142) – 844] kJ mol–1
= –3 888 kJ mol–1
Back
221
7.3 Stoichiometry of Ionic Compounds (SB p.201)
Give two properties of ions that will affect the value of the
lattice enthalpy of an ionic compound.
Answer
The charges and sizes of ions will affect the value of the lattice enthalpy.
The smaller the sizes and the higher the charges of ions, the higher (i.e.
more negative) is the lattice enthalpy.
Back
222
Back
Write down the formula of the compound that possesses the

lattice structure shown on the right:
To calculate the number of each type of

particle present in the unit cell:
Number of atom A = 1 Answer
(1 at the centre of the unit cell)
1
Number of atom B = 8 × =2
1 4
(shared along each edge)
4 1
Number of atom C = 8 × =1
1 8
(shared at each corner)
8
∴ The formula of the compound is AB2C.
223
Back
The diagram on the right shows a unit cell of titanium oxide.

What is the coordination number of
(a) titanium; and
(b) oxygen?
Answer
(a) The coordination number of
titanium is 6 as there are six
oxide ions surrounding each
titanium ion.
(b) The coordination number of
oxygen is 3.
224
The following table gives the atomic and ionic radii of some
Group IIA elements.
Element Atomic radius (nm) Ionic radius

Be 0.112 0.031
Mg 0.160 0.065
Ca 0.190 0.099
Sr 0.215 0.133
Ba 0.217 0.135
225
Explain briefly the following:

(a) The ionic radius is smaller than the atomic radius in each
element.
(b) The ratio of ionic radius to atomic radius of Be is the
lowest.
(c) The ionic radius of Ca is smaller than that of K
(0.133 nm).
Answer
226
(a) One reason is that the cation has one electron shell less than the cor
responding atom. Another reason is that in the cation, the number of
protons is greater than the number of electrons. The electron cloud o
f the cation therefore experiences a greater nuclear attraction. Henc
e, the ionic radius is smaller than the atomic radius in each element.
(b) In the other cations, although there are more protons in the nucleus,
the outer most shell electrons are further away from the nucleus, an
d electrons in the inner shells exhibit a screening effect. Be has the s
mallest atomic size. In Be2+ ion, the electrons experience the greates
t nuclear attraction. Therefore, the contraction in size of the electron
cloud is the greatest when Be2+ ion is formed, and the ratio of ionic r
adius to atomic radius of Be is the lowest.
227
(c) The electronic configurations of both K+ and Ca2+ ions are

1s22s22p63s23p6. Hence they have the same number and
arrangement of electrons. However, Ca2+ ion is doubly charged while
K+ ion is singly charged, so the outermost shell electrons of Ca2+ ion
experience a greater nuclear attraction. Hence, the ionic radius of
Ca2+ ion is smaller than that of K+ ion.
Back
228
Arrange the following atoms or ions in an ascending order of

their sizes:
(a) Be < Mg < Ca < Sr < Ba < Ra
(a) Be, Ca, Sr, Ba, Ra, Mg (b) C < Si < Ge < Sn < Pb
(b) Si, Ge, Sn, Pb, C (c) F– < Cl– < Br– < I–
(c) F–, Cl–, Br–, I– (d) Al3+ < Mg2+ < Na+ < F– < O2– < N3–
(d) Mg2+, Na+, Al3+, O2–, F–, N3–

Answer
Back
229

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7 Ionic Bonding

7.1 Formation of Ionic Bonds: Donating and Accepting

 Only the outermost (valence) electrons are

 Successful in solving chemical problems

 Why are there compounds with chemical

 Why are helium and the other noble gases

 Atoms tend to form chemical bonds

Three types of chemical bonds

Three types of chemical bonds

Sodium atom, Na Chlorine atom, Cl

Three types of chemical bonds

Three types of chemical bonds

Three types of chemical bonds

Electrostatic attraction between nuclei and

Three types of chemical bonds

Three types of chemical bonds

Covalent Bonds with unequal sharing

Ionic or covalent depends on the electron-

Ionic bonds are formed between atoms with

X+(g)  X2+(g) + e- H 2nd I.E.

Electron affinities can be positive or negative.

free, isolated atoms

However, whether a bond is ionic or covalent

Nobel Laureate in Chemistry,

Nobel Laureate in Chemistry, 1954

 calculated from bond enthalpies

The atomic radius decreases from

The atomic radius increases down a

EN is a measure of the ability of an atom to

XeF2, XeF4 and XeF6 are present

In fact, formations of positive ions from

Ionic bond is the result of electrostatic

Interaction = attraction + repulsion

 atoms of Group IA & Group IIA e

Q.2 Write the s,p,d,f notation for each of

Ion s,p,d,f notation

Ti3+ [Ne] 3s23p63d1 Mn3+ [Ne] 3s23p63d4

Ionization enthalpy determines the ease o

2,8 Na+ Mg2+ Al3+(IIIA)

2,8,8 K+ Ca2+ Sc3+

2,8,18,8 Rb+ Sr2+ Y3+

IB IIB IIIA IVA

2,8,18 Cu+ Zn2+ Ga3+ --

2,8,18,18 Ag+ Cd2+ In3+ Sn4+

2,8,18,32,18 Au+ Hg2+ Tl3+ Pb4+

IB IIB IIIA IVA

2,8,18 Cu+ Zn2+ Ga3+ --

2,8,18,18 Ag+ Cd2+ In3+ Sn4+

2,8,18,32,18 Au+ Hg2+ Tl3+ Pb4+

IB IIB IIIA IVA

2,8,18 Cu+ Zn2+ Ga3+ --

2,8,18,18 Ag+ Cd2+ In3+ Sn4+

2,8,18,32,18 Au+ Hg2+ Tl3+ Pb4+

IB IIB IIIA IVA

2,8,18 Cu+ Zn2+ Ga3+ --

2,8,18,18 Ag+ Cd2+ In3+ Sn4+

2,8,18,32,18 Au+ Hg2+ Tl3+ Pb4+

Tl [2,8,18,32], 5s2, 5p6, 5d10, 6s2, 6p1

6s electrons are poorly shielded by the inner