Ikatan Ion

7
7.1
7.2
7.3
7.4
7.5
Ionic Bonding
Formation of Ionic Bonds: Donating and Accepting
Electrons
Energetics of Formation of Ionic Compounds
Stoichiometry of Ionic Compounds
Ionic Crystals
Ionic Radii
Bonding & Structure
Lewis Model
G.N. Lewis in 1916
Only the outermost (valence) electrons are

involved significantly in bond formation
Successful in solving chemical problems
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?
Chemical bonds are strong

electrostatic forces holding atoms
ions together, which are formed
the rearrangement (transfer or
sharing) of outermost electrons
or
by
Atoms tend to form chemical bonds

in such a way as to achieve the electronic
configurations of the nearest noble gases
(The Octet Rule )
Q.1 Write the s,p,d,f notation for the ions in the table below
Ion
Be2+
O2Sc3+
BrBa2+
At6
s,p,d,f notation
Isoelectronic
noble gas
Ion
s,p,d,f notation
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
Introduction (SB p.186)
Three types of chemical bonds

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

1. Ionic bond (electrovalent bond)
Na
Cl
Sodium atom, Na
1s22s22p63s1
Chlorine atom, Cl
1s22s22p63s23p5

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 electronattracting 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 electronattracting 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)
X(g)
+
+
ee-
X-(g)
X2(g)
H 1st E.A.
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
Mullikens scale of electronegativity
1
( IE EA)
Electronegativity(Mulliken)
2
Nobel Laureate in Chemistry,

1966
23
Paulings scale of electronegativity
Nobel Laureate in Chemistry, 1954

Nobel Laureate in Peace, 1962
24
25
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

IA
H
2.1
Li
1.0
Na
0.9
K
0.8
Rb
0.8
Cs
0.7
26
IIA
Be
1.5
Mg
1.2
Ca
1.0
Sr
1.0
Ba
0.9
IIIA IVA
B
2.0
Al
1.5
Ga
1.6
In
1.7
Tl
1.8
C
2.5
Si
1.8
Ge
1.8
Sn
1.8
Pb
1.8
VA
N
3.0
P
2.1
As
2.0
Sb
2.0
Bi
1.9
VIA
O
3.5
S
2.5
Se
2.4
Te
2.1
Po
2.0
VIIA VIIIA
F
4.0
Cl
3.0
Br
2.8
I
2.5
At
2.2
He
Ne
Ar
Kr
Xe
Rn
-
What trends do you notice about the EN

values in the Periodic Table? Explain.
IA
H
2.1
Li
1.0
Na
0.9
K
0.8
Rb
0.8
Cs
0.7
27
IIA
Be
1.5
Mg
1.2
Ca
1.0
Sr
1.0
Ba
0.9
IIIA IVA
B
2.0
Al
1.5
Ga
1.6
In
1.7
Tl
1.8
C
2.5
Si
1.8
Ge
1.8
Sn
1.8
Pb
1.8
VA
N
3.0
P
2.1
As
2.0
Sb
2.0
Bi
1.9
VIA
O
3.5
S
2.5
Se
2.4
Te
2.1
Po
2.0
VIIA VIIIA
F
4.0
Cl
3.0
Br
2.8
I
2.5
At
2.2
He
Ne
Ar
Kr
Xe
Rn
-
The EN values increase from left to

right across a Period.
IA
H
2.1
Li
1.0
Na
0.9
K
0.8
Rb
0.8
Cs
0.7
28
IIA
Be
1.5
Mg
1.2
Ca
1.0
Sr
1.0
Ba
0.9
IIIA IVA
B
2.0
Al
1.5
Ga
1.6
In
1.7
Tl
1.8
C
2.5
Si
1.8
Ge
1.8
Sn
1.8
Pb
1.8
VA
N
3.0
P
2.1
As
2.0
Sb
2.0
Bi
1.9
VIA
O
3.5
S
2.5
Se
2.4
Te
2.1
Po
2.0
VIIA VIIIA
F
4.0
Cl
3.0
Br
2.8
I
2.5
At
2.2
He
Ne
Ar
Kr
Xe
Rn
-
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.

IA
H
2.1
Li
1.0
Na
0.9
K
0.8
Rb
0.8
Cs
0.7
30
IIA
Be
1.5
Mg
1.2
Ca
1.0
Sr
1.0
Ba
0.9
IIIA IVA
B
2.0
Al
1.5
Ga
1.6
In
1.7
Tl
1.8
C
2.5
Si
1.8
Ge
1.8
Sn
1.8
Pb
1.8
VA
N
3.0
P
2.1
As
2.0
Sb
2.0
Bi
1.9
VIA
O
3.5
S
2.5
Se
2.4
Te
2.1
Po
2.0
VIIA VIIIA
F
4.0
Cl
3.0
Br
2.8
I
2.5
At
2.2
He
Ne
Ar
Kr
Xe
Rn
-
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 ?
IA
H
2.1
Li
1.0
Na
0.9
K
0.8
Rb
0.8
Cs
0.7
32
IIA
Be
1.5
Mg
1.2
Ca
1.0
Sr
1.0
Ba
0.9
IIIA IVA
B
2.0
Al
1.5
Ga
1.6
In
1.7
Tl
1.8
C
2.5
Si
1.8
Ge
1.8
Sn
1.8
Pb
1.8
VA
N
3.0
P
2.1
As
2.0
Sb
2.0
Bi
1.9
VIA
O
3.5
S
2.5
Se
2.4
Te
2.1
Po
2.0
VIIA VIIIA
F
4.0
Cl
3.0
Br
2.8
I
2.5
At
2.2
He
Ne
Ar
Kr
Xe
Rn
-
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
is 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

elements form cations easily.
40
Ease of formation of cation
41
Ease of formation of cation
Li+
Be2+
Na+
Mg2+
Al3+
K+
Ca2+
Sc3+
Rb+
Sr2+
Y3+
Zr4+
Cs+
Ba2+
La3+
Ce4+
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

elements form anions easily.
42
Ease of formation of anion
43
Ease of formation of anion
N3
O2
P3
S2
Cl
Br
I
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
Ion
Zn2+
Pb2+
V3+
Cr3+
Fe3+
Fe2+
Co2+
Ni2+
Cu2+
45
s,p,d,f notation
Q.2
Ion
Zn2+
Pb2+
V3+
Cr3+
Fe3+
Fe2+
Co2+
Ni2+
Cu2+
46
s,p,d,f notation
1s2,2s2,2p6,3s2,3p6,3d10
1s2,2s2,2p6,3s23p63d10,4s2,4p6,4d10,4f14,5s2,5p6,5d10,6s2
1s2,2s2,2p6,3s23p63d2
1s2,2s2,2p6,3s23p63d3
1s2,2s2,2p6,3s23p63d5
1s2,2s2,2p6,3s23p63d6
1s2,2s2,2p6,3s23p63d7
1s2,2s2,2p6,3s23p63d8
1s2,2s2,2p6,3s23p63d9
1.
18 - electrons group
e.g.
Zn2+
Fully-filled s, p & d-subshells

Ion
Zn2+
Pb2+
V3+
Cr3+
Fe3+
Fe2+
Co2+
Ni2+
Cu2+
47
s,p,d,f notation
1s2,2s2,2p6,3s2,3p6,3d10
1s2,2s2,2p6,3s23p63d10,4s2,4p6,4d10,4f14,5s2,5p6,5d10,6s2
1s2,2s2,2p6,3s23p63d2
1s2,2s2,2p6,3s23p63d3
1s2,2s2,2p6,3s23p63d5
1s2,2s2,2p6,3s23p63d6
1s2,2s2,2p6,3s23p63d7
1s2,2s2,2p6,3s23p63d8
1s2,2s2,2p6,3s23p63d9
2.
(18 + 2 ) - electron group
e.g.
Pb2+
Fully-filled s, p & d-subshells

Ion
Zn2+
Pb2+
V3+
Cr3+
Fe3+
Fe2+
Co2+
Ni2+
Cu2+
48
s,p,d,f notation
1s2,2s2,2p6,3s2,3p6,3d10
1s2,2s2,2p6,3s23p63d10,4s2,4p6,4d10,4f14,5s2,5p6,5d10,6s2
1s2,2s2,2p6,3s23p63d2
1s2,2s2,2p6,3s23p63d3
1s2,2s2,2p6,3s23p63d5
1s2,2s2,2p6,3s23p63d6
1s2,2s2,2p6,3s23p63d7
1s2,2s2,2p6,3s23p63d8
1s2,2s2,2p6,3s23p63d9
3.
Variable arrangements for ions of
transition metals.
ns2,np6, nd1 to ns2,np6, nd9
Ion
Zn2+
Pb2+
V3+
Cr3+
Fe3+
Fe2+
Co2+
Ni2+
Cu2+
s,p,d,f notation
1s2,2s2,2p6,3s2,3p6,3d10
1s2,2s2,2p6,3s23p63d10,4s2,4p6,4d10,4f14,5s2,5p6,5d10,6s2
1s2,2s2,2p6,3s23p63d2
1s2,2s2,2p6,3s23p63d3
1s2,2s2,2p6,3s23p63d5
1s2,2s2,2p6,3s23p63d6
1s2,2s2,2p6,3s23p63d7
1s2,2s2,2p6,3s23p63d8
1s2,2s2,2p6,3s23p63d9
Ti3+ [Ne] 3s23p63d1

49
Mn3+ [Ne] 3s23p63d4
Electronic arrangements of stable cations
Ionization enthalpy determines the ease

of 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
51
IA
IIA
IIIB
2,8
Na+
Mg2+
Al3+(IIIA)
2,8,8
K+
Ca2+
Sc3+
2,8,18,8
Rb+
Sr2+
Y3+
(a)
18 - electrons group
cations of Groups IB, IIB, IIIA and IVA
52
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+
Less stable than ions with a noble gas structure.
53
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+
Cu and Au form other ions because the

nuclear charges are not high enough to hold
the 18-electron group firmly.
54
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+
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.
55
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+
(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)
Pb2+(18+2) > Pb4+(18)
58
moving down
Group IV

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)
Bi3+(18+2) > Bi5+(18)
59
moving down
Group V
(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
form anions easily.
62
First Electron Affinity (kJ mol1)

X(g) + e X(g)
63
He
-73
+21
Li
Be
-60
+18
Na
Mg
-53
+21
-23 -122
Al
Si
N
~0
P
-142 -322
S
Cl
-44 -134 -72 -200 -349
Ne
+29
Ar
+35
Br
Kr
-48
-325
+39
E.A. becomes more ve from Gp 1 to Gp 7

across a period
64
He
-73
+21
Li
Be
-60
+18
Na
Mg
-53
+21
-23 -122
Al
Si
N
~0
P
-142 -328
S
Cl
-44 -134 -72 -200 -349
Ne
+29
Ar
+35
Br
Kr
-48
-324
+39
The electrons added experience stronger

nuclear attraction when the atoms are getting
smaller across the period.
65
He
-73
+21
Li
Be
-60
+18
Na
Mg
-53
+21
-23 -122
Al
Si
N
~0
P
-142 -328
S
Cl
-44 -134 -72 -200 -349
Ne
+29
Ar
+35
Br
Kr
-48
-324
+39
+ve E.A. for Gp 2 and Gp 0 because the electron

added occupies a new shell / subshell
66
He
-73
+21
Li
Be
-60
+18
Na
Mg
-53
+21
-23 -122
Al
Si
N
~0
P
-142 -328
S
Cl
-44 -134 -72 -200 -349
Ne
+29
Ar
+35
Br
Kr
-48
-324
+39
Goes to a new subshell
Goes to a new shell
Be(2s2) Be(2s22p1)
67
Ne(2p6) Ne(2p63s1)
He
-73
+21
Li
Be
-60
+18
Na
Mg
-53
+21
-23 -122
Al
Si
N
~0
P
-142 -328
S
Cl
-44 -134 -72 -200 -349
Ne
+29
Ar
+35
Br
Kr
-48
-324
+39
More ve E.A. for Gp 1 because the ions

formed have full-filled s-subshells.
E.g. Li(1s22s1) Li(1s22s2)
H
-73
68
He
+21
Li
Be
-60
+18
Na
Mg
-53
+21
-23 -122
Al
Si
N
~0
P
-142 -328
S
Cl
-44 -134 -72 -200 -349
Ne
+29
Ar
+35
Br
Kr
-48
-324
+39
Less ve E.A. for Gp 5 because the stable halffilled p-subshell no longer exists.
E.g. N(2s22p3) N(2s22p4)
69
He
-73
+21
Li
Be
-60
+18
Na
Mg
-53
+21
-23 -122
Al
Si
N
~0
P
-142 -328
S
Cl
-44 -134 -72 -200 -349
Ne
+29
Ar
+35
Br
Kr
-48
-324
+39
Q.3 Why are the first E.A.s of halogen atoms more

negative than those of the O atom or the S
atom ?
He
-73
Li
Be
+21
Ne
-60
+18
Na
Mg
-53
K
+21
-48
70
-23 -122 ~0 -142 -328

Al
Si
Cl
+29
Ar
-44 -134 -72 -200 -349

Br
+35
Kr
-324
+39
It is because the halide ions formed have fullfilled s/p subshells (octet structure).
71
He
-73
+21
Li
Be
-60
+18
Na
Mg
-53
+21
-23 -122
Al
Si
N
~0
P
-142 -328
S
Cl
-44 -134 -72 -200 -349
Ne
+29
Ar
+35
Br
Kr
-48
-324
+39
Q.4
Why are the second E.A.s of O(+844 kJmol1)

and S(+532 kJmol1) 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

that of Cl ?
Halogen
E.A.
kJ mol1
Cl
Br
328
349
325
295
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)
K(g)
F(g)
IE1(K)
H1
EA1(F)
K+(g)
KF(g)
H2
F(g)
By Hesss law, H1 = IE1(K) + EA1(F) + H2

74
Q.6
H1 = IE1(K) + EA1(F) + H2
(+)
()
Q
1Q 2
419.0 103 J mol 1 328.0 103 J mol 1
23
1
23
1
6.022 10 mol
6.022 10 mol
4 0 R
19 2
(1.602
10
C)
19
1.511
10 J
4 8.854 1012 C2J1m1 2.170 1010m
1.511
1019J 1.063
1018J
19
9.119
10
J
75
H1 = IE1(K) + EA1(F) + H2
= 1.5111019 J 1.0631018 J = 9.1191019 J
H2 = 1.0631018 J
IE1(K) + EA1(F) = +1.5111019 J
19
H1 9.119 10 J
76
When R
Stability : K+(g) + F-(g) < K(g) + F(g) by +1.511x10-19J
H2 = 1.0631018 J
IE1(K) + EA1(F) = +1.5111019 J
19
H1 9.119 10 J
77
I.E. and E.A. are NOT the driving forces for the
formation of ionic bond.
H2 = 1.0631018 J
IE1(K) + EA1(F) = +1.5111019 J
19
H1 9.119 10 J
78
K+(g) & F(g) tend to come close together in order

to become stable.
H2 = 1.0631018 J
IE1(K) + EA1(F) = +1.5111019 J
19
H1 9.119 10 J
79
Coulomb stabilization is the driving force for the

formation of ionic bond.
H2 = 1.0631018 J
IE1(K) + EA1(F) = +1.5111019 J
19
H1 9.119 10 J
80
When R = 2.1701010 m
The most energetically stable state is reached.
H2 = 1.0631018 J
IE1(K) + EA1(F) = +1.5111019 J
19
H1 9.119 10 J
81
The ions cannot come any closer than Re as it will

results in less stable states
H2 = 1.0631018 J
IE1(K) + EA1(F) = +1.5111019 J
19
H1 9.119 10 J
82
Repulsions between electron clouds and between

nuclei > attraction between ions
H2 = 1.0631018 J
IE1(K) + EA1(F) = +1.5111019 J
19
H1 9.119 10 J
83
Potential energy (V)
1
Repulsion : V 12
R
between opposite charges
Minimum V when R = 2.170 1010 m

R
Attraction :
1
V
R
between opposite charges
84
What is the significance of the lowest energy

state of the neutral state of K + F ?
H2 = 1.0631018 J
IE1(K) + EA1(F) = +1.5111019 J
19
H1 9.119 10 J
85
A covalent bond is formed
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
Na(s) +
Cl2(g)
2
Hf
H1
NaCl(s)
H2
Na+(g)
Cl(g)
By Hesss 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)
4.
First electron affinity of Cl(g)
Cl(g) + e- Cl-(g)
88
H = +121.1 kJ mol-1
H = -349 kJ mol-1
H2 is the lattice enthalpy of NaCl.

It is the enthalpy change for the
formation of 1 mole of NaCl(s) from its
constituent ions in the gaseous state.
Na+(g) + Cl-(g) NaCl(s)
89
HLo
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 mol1
= 791.4 kJ mol1
91
-349
-791.4
92
Lattice enthalpy is the dominant enthalpy term

responsible 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
H lattice
96
MLQ Q
4 0 (r r )
L is the Avogadros constant
H lattice
97
MLQ Q
4 0 (r r )
Q+ and Q- are the charges on the

cation and the anion respectively
H lattice
98
MLQ Q
4 0 (r r )
0 is the permittivity of vacuum
H lattice
99
MLQ Q
4 0 (r r )
(r+ + r-) is the nearest distance

between the nuclei of cation and anion
r+ is the ionic radius of the cation
r- is the ionic radius of the anion
H lattice
100
MLQ Q
4 0 (r r )
Stoichiometry of Ionic Compounds
101
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.
1.
Considerations in terms of electronic
configurations
Atoms tend to attain noble gas electronic
structures 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
2,8,1
Mg
2,8,2
F
2,7
+ 2Cl
2,8,7
MgCl2
103
[Na]+ [F]2,8 2,8
NaF
[Cl]- [Mg]2+ [Cl]2,8,8 2,8
2,8,8
2.
Considerations in terms of enthalpy changes

of formation
Based on the Born-Haber cycle & the

theoretically calculated lattice enthalpy,
enthalpy the
values of Hfo of
hypothetical compounds
(e.g. MgCl , 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
hypothetical compounds with the
experimentally determined 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
stoichiometry
MgCl
MgCl2
MgCl3
Assumed
structure
NaCl
CaF2
AlCl3
Estimated
-771 -2602 -5440
o
-1
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]
Mg+(g)+
1
Cl (g)
2 2
Mg+(g)+Cl(g)
1st IE[Mg]
1
Mg(g)+ Cl2(g)
2
Hat[Mg]
Mg(s)+
HL[MgCl]
1
Cl (g)
2 2
Hf[MgCl]<0
108
1st EA[Cl]
MgCl(s)
Hf[MgCl2(s)]
= Hat[Mg(s)] + 1st IE of Mg + 2nd IE of Mg
+ 2Hat[1/2Cl2(g)] + 21st EA of Cl + HL[MgCl2(s)]
= [150+736+1450+2121+2(-364)+(-2602)] kJ mol-1
= -752 kJ mol-1
109
Mg2+(g)+2Cl(g)
2Hat[1/2Cl2]
Mg2+(g)+Cl2(g)
Enthalpy (kJ mol )
Mg2+(g)+2Cl(g)
2nd IE[Mg]
HL[MgCl2]
Mg+(g)+Cl2(g)
1st IE[Mg]
Hat[Mg]
Mg(g)+Cl2(g)
Mg(s)+Cl2(g)
Hf[MgCl2] <0
110
21st EA[Cl]
MgCl2(s)
Hf[MgCl3(s)]
= Hat[Mg(s)] + 1st IE of Mg + 2nd IE of Mg + 3rd IE of Mg
+ 3Hat[1/2Cl2(g)] + 31st EA of Cl + HL[MgCl3(s)]
= 150+736+1450+7740+3121+3(-364)+(-5440)
= +3907 kJ mol-1
111
Mg3+(g)+3Cl(g)
3Hat[1/2Cl2]
Mg3+(g)+
3 Cl (g)
2 2
Enthalpy ( kJ mol )
3rd IE[Mg]
2nd IE[Mg]
3Cl (g)
2 2
Mg+(g)+ 3 Cl2(g)
1st IE[Mg]
Hat[Mg]
112
Mg3+(g)+3Cl(g)
HL[MgCl3]
Mg2+(g)+
31st EA[Cl]
Mg(g)+
3Cl (g)
2 2
Mg(s)+3/2Cl2(g)
MgCl3(s)
Hf[MgCl3] >0
Since the hypothetical compound MgCl2 has the

most negative Hf value, and
this value is closest to the experimentally
determined 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
H lattice
115
MLQ Q
4 0 (r r )
Factors affect lattice enthalpy

Effect of ionic charge:
The greater the ionic charge
The higher (or more negative) is the
lattice enthalpy
H lattice
MLQ Q
4 0 (r r )
Check Point 7-3

116
7.
4Ionic Crystals
117
7.4 Ionic Crystals (SB p.202)
Crystal Lattice( )
118
In solid state, ions of ionic compounds are

regularly packed to form 3-dimensional
structures called crystal lattices(
)
119
The coordination number (C.N.) of a given

particle 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

particle 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
filling
Space
lattice
Unit cell
View this Chemscape 3D structure

130
Body-centred cubic (b.c.c.) structure

Space
filling
Space
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

the space bounded by a corner atom and the
three face-centred atoms nearest to it.
138
b
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
5
1
5
8
13 Oh sites
6
3
9
7
4
11
10
13
4 Th sites in
the front
4 Th sites at
the back
7
12
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
sites occupied by the
smaller Na+ ions
Oh sites of f.c.c.
lattice of Cl- ions
144
A more open f.c.c.

unit cell of smaller
Na+ ions with all Oh
sites occupied by the
larger 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
Co-ordination number of Na+ = 6

Co-ordination number of Cl = 6
-
147
Unit cell of NaCl
6 : 6 co-ordination
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
1/2
Edge
Corner
Fraction of particles occupied by a unit cell

149
1/4
Body
Face
Edge
1/2
1/4
Corner

150
1/8
Body
Face
Edge
Corner
1/2
1/4
1/8

151
Q.11 Calculate the net nos. of Na+ and Clions in a unit cell of NaCl.
No. of Cl- ions =
1
1
8 6 4
8
2
8 corners 6 faces
No. of Na ions =
+
1
12 1 4
4
12 edges
Example 7-4
152
1 body
Structure of Caesium Chloride Link

Cs+ ions are too large to fit
in the octahedral sites.
Thus Cl ions adopt the
more open simple cubic
structure with the cubical
sites occupied by Cs+ ions.
153
Simple cubic lattice
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

Co-ordination number of Cl- = 8
156
8 : 8 co-ordination
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
cubic lattice
Co-ordination number of Ca2+ = 8

Co-ordination number of F- = 4
160
8 : 4 co-ordination
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
sites are occupied by
Ca2+ in order to maintain
electroneutrality.
162
Structure of Sodium oxide Link

Antifluorite structure
Na2O
vs
CaF2
fluorite structure
163
Q.14(a)
Zinc blende
structure
- Link
164
Q.14(a)
ZnS
Number of Zn2+ = 4
Number of S2 =
165
1
1
8 6 4
8
2
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
1
Number of O2 = 2 4 4
2
168
TiO2
Q.15(a)
C.N. of Ti4+ = 6
C.N. of O2 = 3
169
6 : 3 coordination
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.)
structure with alternate Oh sites occupied
by 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

they approach a given cation.
The balance between attractive forces and
repulsive forces among ions limits the C.N. of
the system.
174
Q.16

If the cations are small, less anions can

approach them without significant repulsions.
Or, if the cations are small, they choose to
fit in the smaller tetrahedral sites with
smaller C.N. to strengthen the ionic bonds
formed.
175
Q.16

If the cations are large, they choose to fit in

the larger octahedral sites or even cubical
sites with greater C.N. to maximize the no. of
ionic bonds formed.
176
2. The relative size of cation and anion,

In general, r > r+,
r
0 1
r
r
C.N .
r
177
r
r
If the cations are large,
r
1
r
more anions can approach the cations

without significant repulsions.
Or, the large cations can fit in the larger
interstitial sites with greater C.N. to
maximize the no. of bonds formed.
178
Summary : Interstitial
site
Tetrahedral
Octahedral
Cubical
Coordination
4:4
6:6
8:8
0.225 0.414
0.414 0.732
0.732 1.000
ZnS, most
copper(I)
halides
Alkali metal
halides except
CsCl
CsCl, CsBr
CsI, NH4Cl
r
r
Examples
NH4+ is large
179
Summary : -
180
Interstitial
site
Cubical
Coordination
8:4
r
r
0.732 1.000
Examples
*CaF2, BaF2, BaCl2, SrF2
Q.17
BA
r
cos ABC
cos 45
BC r r
A
r
C +
181
45
r
0.414
r
r
0.414
r
r
0.732 0.414
r
the range of ratio that favours
octahedral arrangement.
182
r
0.732
r
the optimal ratio for cations and
anions 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
tetrahedral site
Br ions adopt f.c.c. structure
Only alternate Td sites are occupied by
Cu+ ions to ensure electroneutrality.
186
Copper(II) bromide, CuBr2
r 0.071
0.364 0.414
r 0.195
tetrahedral site
Br ions adopt f.c.c. structure
Only 1/4 Td sites are occupied by Cu+ ions
to ensure electroneutrality.
Some Br may form less bonds than others
Not favourable.
187
Q.18(c)
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
to 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
0.230 nm
190
0.295nm
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
shells or subshells. The symmetrical distribution
of electrons accounts for the spherical shapes
of ions.
194
Q.19
Li+
spherical
1s2
Symmetrical distribution
along x, y and z axes
almost
spherical
Na+ [He] 2s2, 2px2, 2py2, 2pz2
Cl [Ne] 3s2, 3px2, 3py2, 3pz2

Zn
2+
3d
3d
2
2
x
y
z2
[Ar] 3d , 3d , 3d ,
,
2
xy
2
xz
2
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
determined by
X-ray diffraction crystallography
196
7.5 Ionic Radii (SB p.205)
Cl
Na+
Electron density
map for NaCl
Contour having
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
isoelectronic, 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
limit according to quantum mechanics.
The size of the ion is restricted by other
ions in the crystal lattice.
Interionic distance < r+ + r
200
Evidence :
Electron distribution is not perfectly spherical at
the boundary due to repulsion between electron
clouds of neighbouring ions.
201
Ionic radius depends on the bonding

environment.
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
radiusvs
vsatomic
atomicradius
radius
Ionic
203
p/e of cation > p/e of parent atom Less shielding effect

stronger nuclear attraction for outermost electrons
smaller size
Ionicradius
radiusvs
vsatomic
atomicradius
radius
Ionic
204
Radii of anions > Radii of corresponding parent atoms
Ionicradius
radiusvs
vsatomic
atomicradius
radius
Ionic
205
p/e of anion < p/e of parent atom more shielding effect

weaker nuclear attraction for outermost electrons
larger size
Ionicradius
radiusvs
vsatomic
atomicradius
radius
Ionic
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
isoelectronic ions of increasing nuclear charge
The total shielding effects of isoelectronic
ions are approximately the same.
Zeff nuclear charge (Z)
Ionic radius decreases as nuclear charge
increases.
208
Isoelectronic
to He(2)
Isoelectronic
to Ne(2,8)
209
Isoelectronic
to Ar(2,8,8)
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
212
Check Point 7-5
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
214
Back
Given the following data:

H (kJ mol1)
First electron affinity of oxygen
Second electron affinity of oxygen
142
+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
H (kJ mol1)
First ionization enthalpy of aluminium
+577
Second ionization enthalpy of aluminium +1820

Third ionization enthalpy of aluminium
+2740
(a)
(i)
Construct a labelled BornHaber 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
216
in (i) is
(a) (i)
(ii)The enthalpy cycle in (i) is based on Hesss 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) Hf [Al2O3(s)] = 2 Hatom[Al(s)] + 2 (HI.E.1 [Al(g)]

+ HI.E.2 [Al(g)] + HI.E.3 [Al(g)])
+ 3 Hatom [O2(g)] + 3 (HE.A.1 [O(g)]
+ HE.A.2 [O(g)]) + Hlattice[Al2O3(s)]
Hf [Al2O3(s)] = 2 (+314) + 2 (+577 + 1 820 + 2 740)

+ 3 (+248) + 3 (142 + 844)
+ Hlattice [Al2O3(s)]
Hf [Al2O3(s)] = + 628 + 10 274 + 744 + 2 106 + Hlattice[Al2O3(s)]

Hlattice[Al2O3(s)] = Hf [Al2O3(s)] (628 + 10 274 + 744 + 2 106)
= 1 669 (628 + 10 274 + 744 + 2 106)
218
= 15 421 kJ mol1
(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 means of the Born-Haber
cycle drawn in (a).
Given: Hatom [Mg(s)] = +150 kJ mol1
HI.E. [Mg(g)] = +736 kJ mol1
HI.E. [Mg+(g)] = +1 450 kJ mol1

Hatom [O2(g)] = +248 kJ mol1
HE.A. [O(g)] = 142 kJ mol1
HE.A. [O(g)] = +844 kJ mol1

220
Answer
(b) Hlattice [MgO(s)]
= Hf [MgO(s)] Hatom [Mg(s)]
HI.E. [Mg(g)] HI.E. [Mg+(g)] Hatom [O2(g)]

HE.A. [O(g)] HE.A. [O(g)]
= [602 150 736 1 450 248 (142) 844] kJ mol1
= 3 888 kJ mol1
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
Answer
compound.
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
4
1
(shared along each edge)
4
1
Number of atom C = 8
=1
8
1
(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
Answer
(a) titanium; and
(b)
oxygen?
(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.
225
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
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
Answer
(0.133 nm).
226
(a) One reason is that the cation has one electron shell less than the
corresponding atom. Another reason is that in the cation, the number
of protons is greater than the number of electrons. The electron
cloud of the cation therefore experiences a greater nuclear
attraction. Hence, 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,
and electrons in the inner shells exhibit a screening effect. Be has
the smallest atomic size. In Be2+ ion, the electrons experience the
greatest nuclear attraction. Therefore, the contraction in size of the
electron cloud is the greatest when Be2+ ion is formed, and the ratio
of ionic radius 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 Ca 2+ 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)
(b)
Be, Ca, Sr, Ba, Ra, (b)

Mg
C < Si < Ge < Sn < Pb
Si, Ge, Sn, Pb, C (c) F < Cl < Br < I
(c)F, Cl, Br, I

(d)
(d) Al3+ < Mg2+ < Na+ < F < O2 < N3
Mg2+, Na+, Al3+, O2, F, N3
Answer
Back
229

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7

Bonding & Structure

G.N. Lewis in 1916

Only the outermost (valence) electrons are

Successful in solving chemical problems

Why are some elements so reactive

Why are there compounds with chemical

Why are helium and the other noble gases

Chemical bonds are strong

Atoms tend to form chemical bonds

[He] 2s2,2p6 (2,8)

[Ne] 3s2,3p6 (2,8,8)

[Ar] 3d10,4s2,4p6 (2,8,18,8)

[Kr] 4d10,5s2,5p6 (2,8,18,18,8)

[Xe] 4f14,5d10,6s2,6p6 (2,8,18,32,18,8)

Introduction (SB p.186)

Three types of chemical bonds

Three types of chemical bonds

Introduction (SB p.186)

Three types of chemical bonds

Introduction (SB p.186)

Three types of chemical bonds

Introduction (SB p.186)

Three types of chemical bonds

Introduction (SB p.186)

Three types of chemical bonds

Introduction (SB p.186)

Three types of chemical bonds

Ionic bonds and Covalent bonds are only

Ionic Bonds with incomplete transfer

Electronegativity and Types of Chemical Bonds

Ways to compare the electron-attracting

Electronegativity and Types of Chemical Bonds

Ionization enthalpies are always positive.

Electronegativity and Types of Chemical Bonds

Electron affinities can be positive or negative.

I.E. and E.A. only show e- releasing/attracting

free, isolated atoms

Electronegativity and Types of Chemical Bonds

Mullikens scale of electronegativity

Nobel Laureate in Chemistry,

Paulings scale of electronegativity

Nobel Laureate in Chemistry, 1954

Paulings scale of electronegativity

calculated from bond enthalpies

cannot be measured directly

the most electronegative element, F, is

Paulings scale of electronegativity

What trends do you notice about the EN

The EN values increase from left to

What trends do you notice about the

The atomic radius decreases from

left to right across a Period.Thus,the

The EN values decrease down a Group.

What trends do you notice about the

Why are the E.A. of noble gases not

Why are the E.A of noble gases not shown ?

EN is a measure of the ability of an atom to

XeF2, XeF4 and XeF6 are present

Formation of Ionic Bond

Formation of Ionic Bond

The oppositely charged ions are stabilized

Dots and Crosses Diagram

Notes on Dots & Crosses representation