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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)

Three types of chemical bonds


1. Ionic bond (electrovalent bond)

Na

Cl

Sodium atom, Na
1s22s22p63s1

Chlorine atom, Cl
1s22s22p63s23p5

Introduction (SB p.186)

Three types of chemical bonds


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

10

Introduction (SB p.186)

Three types of chemical bonds


2. Covalent bond
Formed by sharing of electrons

11

Introduction (SB p.186)

Three types of chemical bonds


2. Covalent bond
Electrostatic attraction between nuclei and
shared electrons

12

Introduction (SB p.186)

Three types of chemical bonds


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

13

Introduction (SB p.186)

Three types of chemical bonds


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

Electronegativity and Types of Chemical Bonds


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

Electronegativity and Types of Chemical Bonds


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

Electronegativity and Types of Chemical Bonds


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

Paulings scale of electronegativity

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

Paulings scale of electronegativity


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

(b) (18+2) 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)

6s electrons are poorly shielded by the inner


4f electrons.
6s electrons experience stronger nuclear
attraction.
57

(b) (18+2) 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)

Inert pair effect increases down a Group.


Stability : Sn4+(18) > Sn2+(18+2)
Pb2+(18+2) > Pb4+(18)

58

moving down
Group IV

(b) (18+2) 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)

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 )

7.2 Energetics of Formation of Ionic Compounds (SB p.196)

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

7.4 Ionic Crystals (SB p.202)

In solid state, ions of ionic compounds are


regularly packed to form 3-dimensional
structures called crystal lattices(
)

119

7.4 Ionic Crystals (SB p.202)

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

7.4 Ionic Crystals (SB p.202)

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

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.

125

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.

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

View this Chemscape 3D structure


131

Face-centred cubic (f.c.c.) structure

Unit cell
View this Chemscape 3D structure

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

View this Chemscape 3D structure


146

7.4 Ionic Crystals (SB p.201)

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

Fraction of particles occupied by a unit cell


150

1/8

Body

Face

Edge

Corner

1/2

1/4

1/8

Fraction of particles occupied by a unit cell


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

7.4 Ionic Crystals (SB p.202)

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

7.4 Ionic Crystals (SB p.202)

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

7.4 Ionic Crystals (SB p.203)

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

7.4 Ionic Crystals (SB p.203)

Structure of Calcium Fluoride Link


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

7.4 Ionic Crystals (SB p.203)

Structure of Calcium Fluoride Link


Face-centred
cubic lattice

Co-ordination number of Ca2+ = 8


Co-ordination number of F- = 4
160

8 : 4 co-ordination

7.4 Ionic Crystals (SB p.203)

Q.13 (a)

CaF2
Number of F = 8

1
1
Number of Ca2+ = 8 6 4
8
2

161

7.4 Ionic Crystals (SB p.203)

Q.13 (b) CaF2


Only alternate cubical
sites are occupied by
Ca2+ in order to maintain
electroneutrality.

162

7.4 Ionic Crystals (SB p.203)

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

Factors governing the structures of ionic crystals

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

Factors governing the structures of ionic crystals

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

Factors governing the structures of ionic crystals

Q.16

Is there no limit for the C.N. ?


Explain your answer.

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

Factors governing the structures of ionic crystals

Q.16

Is there no limit for the C.N. ?


Explain your answer.

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

Factors governing the structures of ionic crystals

2. The relative size of cation and anion,


In general, r > r+,

r
0 1
r

r
C.N .
r

177

r
r

Factors governing the structures of ionic crystals

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

7.4 Ionic Crystals (SB p.203)

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

7.4 Ionic Crystals (SB p.203)

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

7.5 Ionic Radii (SB p.206)

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

7.5 Ionic Radii (SB p.206)

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

7.5 Ionic Radii (SB p.206)

Radii of anions > Radii of corresponding parent atoms

Ionicradius
radiusvs
vsatomic
atomicradius
radius
Ionic

205

7.5 Ionic Radii (SB p.206)

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

7.5 Ionic Radii (SB p.206)

Isoelectronic
to He(2)
Isoelectronic
to Ne(2,8)

209

Isoelectronic
to Ar(2,8,8)

7.5 Ionic Radii (SB p.206)

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

Introduction (SB p.186)

Why do two atoms bond together?


Answer
The two atoms tend to achieve an octet
configuration which brings stability.

213

Introduction (SB p.186)

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

7.2 Energetics of Formation of Ionic Compounds (SB p.195)

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

7.2 Energetics of Formation of Ionic Compounds (SB p.195)

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

7.2 Energetics of Formation of Ionic Compounds (SB p.195)

(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

7.2 Energetics of Formation of Ionic Compounds (SB p.195)

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

7.2 Energetics of Formation of Ionic Compounds (SB p.197)

(a)
Draw a Born-Haber cycle for the
formation of magnesium oxide.
(a) The Born-Haber cycle for the formation of MgO:

Answer
219

7.2 Energetics of Formation of Ionic Compounds (SB p.197)

(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

7.2 Energetics of Formation of Ionic Compounds (SB p.197)

(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

7.4 Ionic Crystals (SB p.204)

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

7.4 Ionic Crystals (SB p.205)

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

7.5 Ionic Radii (SB p.208)

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

7.5 Ionic Radii (SB p.208)

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

7.5 Ionic Radii (SB p.208)

(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

7.5 Ionic Radii (SB p.208)

(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

7.5 Ionic Radii (SB p.208)

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