CHAPTER 4 CHEMICAL BONDING

Chemical bond is the force that holds two atoms together in a molecule or compound Valence electrons play an important role in the formation of chemical bonds

CHAPTER 4 CHEMICAL BONDING

4.1 Lewis Structure 4.2 Molecular Shape and Polarity 4.3 Orbital Overlap and Hybridization 4.4 Intermolecular Forces 4.5 Metallic Bond

4.1 Lewis Structure 4.1.1 Lewis Symbol

A Lewis symbol consists of: the symbol of an element dots or cross is used to represent the valence electrons in an atom of the element.

Example The Lewis symbol of atom

Group Valence electron Lewis dot symbol

1 1

2 2

13 3

14 4

15 5

16 6

17 7

18 8

Elements in the same group have the same valence electronic configurations similar Lewis symbols.

4.1.2

Octet Rule

Octet rule states that atoms tend to form bonds to obtain 8 electrons in the valence shell
Atoms combine to achieve stablility to have the same electronic configuration as a noble gas

Atoms achieve noble gas configuration through: i) transferring electrons ii) sharing electron

Bond formation involve transferring or sharing of only valence electrons

Electronic Configuration of Cations and Anions

1) Noble gas configuration Group 1, 2 and 13 elements donate valence electrons to form cations with noble gas configurations Example: Na : 1s22s22p63s1 Na+ : 1s22s22p6 (isoelectronic with Ne)

Ca : 1s22s22p63s23p64s2 Ca2+ : 1s22s22p63s23p6 (isoelectronic with Ar)

Group 15, 16 and 17 elements accept electrons to form anions with noble gas configurations Example: O : 1s22s22p4 O2 : 1s22s22p6 (isoelectronic with neon)
Cl : 1s22s22p63s23p5 Cl : 1s22s22p63s23p6 (isoelectronic with Ar)

2)

Pseudonoble gas configuration

d block elements donate electrons from 4s orbitals to form cations with pseudonoble gas configuration. Example: Zn : 1s22s22p63s23p64s23d10 Zn2+ : 1s22s22p63s23p63d10 (pseudonoble gas configuration )

3) Stability of the half-filled orbitals

d block element can also donate electrons to achieve the stability of half-filled orbitals Example: Mn : 1s22s22p63s23p64s23d5 Mn2+ : 1s22s22p63s23p63d5 (stability of half-filled 3d orbital )

Fe : 1s22s22p63s23p64s23d6 Fe3+ : 1s22s22p63s23p63d5 (stability of half-filled 3d orbital)

4.1.3 Formation of the bonds using Lewis Symbols

i.Ionic (electrovalent) bond ii.Covalent bond iii.Dative (coordinate) bond

4.1.3.1

Ionic bond (Electrovalent bond)

Ionic bond (electrovalent bond) is an electrostatic attraction between positively and negatively charged ions. Ionic compounds are formed when electrons are transferred between atoms (metal to nonmetal) to give electrically charged particles that attract each other .

Example 1: NaCl

Sodium, an electropositive metal, tends to remove its valence electron to obtain noble gas electronic configuration (Ne)

Chlorine, an electronegative element, tend to accept electron from Na to obtain noble gas electronic configuration (Ar)

The electrostatic forces between Na+ and Cl- produce ionic bond These two processes occur simultaneously

Example 2: CaCl2
Ca: 1s2 2s2 2p6 3s2 3p6 4s2 (Has two electrons in its outer shell) Cl: 1s2 2s2 2p6 3s2 3p5 (Has seven outer electrons)

Calcium Chloride
If Ca atom transfer 2 electrons, one to each chlorine atom, it become a Ca2+ ion with the stable configuration of noble gas.

At the same time each chlorine atom to achieve noble gas configuration gained one electron becomes a Cl- ion to achieve noble gas configuration.

The electrostatic attraction formed ionic bond between the ions.

Ionic bond

(Formed by transfer of electrons) Calcium Chloride

+ +

Example 3: LiF
+

Lewis structure and formation of ionic compounds

1) CaCl2
+ +

2) MgO
+

3) CaBr2

Ionic bond is very strong, therefore ionic compounds: 1. Have very high melting and boiling points 2. Hard and brittle 3. Can conduct electricity when they are in molten form or aqueous solution because of the mobile ions

Exercises:

By using Lewis structure, show how the ionic bond is formed in the compounds below. ( a ) KF ( b ) BaO ( c ) Na2O

4.1.3.2 Covalent Bond

Definition of covalent bond

i. Chemical bond in which two or more electrons are shared by two atoms.
ii. The electrostatic force between the electrons being shared the nuclei of the atoms.
Why should two atoms share electrons?

To gain stability by having noble gas configuration (octet)

Example

F 7e-

F 7e-

F F 8e- 8e-

Lewis structure of F2
single covalent bond lone pairs

lone pairs

single covalent bond lone pairs

F F

lone pairs 9.4

Covalent compounds:

Compounds may have these covalent bonds: i. Single bond ii. Double bond iii. Triple bond.

Lewis structure of water

H + O+ H

H O H
2e- 8e- 2e-

or single covalent bonds

Double bond two atoms share two pairs of electrons

O
8e-

C
8e-

O
8e-

or

double bonds

double bonds

Triple bond two atoms share + three pairs of electrons

N
8e-

N
8e-

or

triple bond

triple bond

4.1.3.3 Coordinate Covalent Bond (Dative Bond)

Dative bond is a bond in which the pair of shared electrons is supplied by one of the two bonded atoms Involve overlapping of a full orbital and an empty orbital

Requirement for dative bonds: i. Donor atoms should have at least one lone pair electrons ii. The atoms that accepts these electrons should have empty orbitals.

i.Single bond

i.Double bond
i.Triple bond

Steps in Writing Lewis Structures

1. Count total number of valence e- of atoms involved.

2. Add 1 for each negative charge. Subtract 1 for each positive charge.

3. Draw skeletal structure of the compound. Put least electronegative element in the center.
4. Complete an octet for all atoms except hydrogen 5. If structure contains too many electrons, form double and triple bonds on central atom as needed.

Example
Draw the Lewis structure for each of the following compounds: i. HF ii. CH4 iii. CHCl3 iv. NH3 v. H2O

Total no. of valence electrons H: 1e F: 7e Total : 8e

Number of electrons
C : 4e 4H: 4e Total : 8e

Center atom: N

Count electrons:
C : 4e H : 1e 3Cl: 21e Total: 26 e

Count number of electrons N : 3H : Total : 5e 3e 8e

4.1.5 Bond Length

Compare the bond length between single, double and triple bond
Bond length :

The distance between nuclei of the atoms involves in the bond C C C C C C

1.54

1.34

1.20

As the number of bonds between the carbon increase, the bond length decreases because C are held more closely and tightly together As the number of bonds between two atoms increases, the bond grows shorter and stronger

The sum of formal charge on each atom should equal: i.zero for a molecule ii.the charge on the ion for a polyatomic ion Formal charge is used to find the most stable Lewis structure

EXAMPLE
1) Draw all the possible Lewis structure of COCl2. 2) Predict the most plausible structure.

SOLUTION
1)
2)

The most plausible structure is (2) Formal charge is determined before completing a Lewis structure to predict the most stable structure because formal charge closest to zero.

EXERCISE 1

Draw the possible Lewis structures for HNO2. Determine the most plausible Lewis structures for HNO2.

EXERCISE 2

Suggest the possible Lewis structure for H2SO4. Explain your answer.

EXERCISE 3 1) HCN 1) CO2

1) SCN

Three conditions:

1) Incomplete octet 2) Expanded octet 3) Odd no. electron

Occurs when central atom has less than 8 electrons. Elements that can form incomplete octet are: Boron,B , Beryllium, Be & Aluminium, Al This is due to elements being relatively small in size but having high nuclear charge.

Occurs when central atom has more than 8 electrons. Formed by non-metals that have d orbitals OR Non-metals of the 3rd, 4th, 5th.rows in the periodic table

Nitrogen may form compounds that contain odd number electrons.

Example: Nitric oxide, NO Nitrogen dioxide, NO2

The use of two or more Lewis structures to represent a particular molecule. Requirement: Molecules/ions must have multiple bonds and lone pairs electrons at the terminal atoms.

RESONANCE STRUCTURE FOR NO3-

EXERCISE: Write Lewis structures of the following compounds/ ions:

CCl4 PO43NH4+ CO32C2H4 NF3 HCN C2H2 H2S PCl3 CH2Cl2 N2H4 HNO3 ICl PH3

CS2
SO42-

NO2ICl4-

XeF4
SF6

NH3
O3

HCOOH
NO2

4.2 MOLECULAR SHAPE AND POLARITY

LEARNING OUTCOMES At the end of the lesson, students should be able to;
1. Explain valence shell electron repulsion theory. (VSEPR) 2. Draw the basic molecular shapes : linear, trigonal planar, tetrahedral, trigonal bipyramidal and octahedral. 3. Predict and explain the shapes of molecule and bond angles in a given species. 4. Explain bond polarity and dipole moment. 5. Deduce the polarity of molecules based on the shapes and the resultant dipole moment
63

4.2 MOLECULAR SHAPE AND POLARITY

i. ii. iii. VSEPR theory 5 basic shapes polarity

64

Molecular shape:

Introduction

shows the 3-dimensional arrangement of atoms in a molecule Predicted by using Valence Shell Electron Pair Repulsion (VSEPR) theory

65

4.2.1 VSEPR
The Valence-Shell Electron Repulsion theory states that: The valence electron pairs around the central atom are oriented as far apart as possible to minimize the repulsion between them.

66

The repulsion may occur either between: a) bonding pair & another bonding pair b) bonding pair & lone pairs or c) between lone pair & another lone pairs
67

The strength of repulsion:

The order of repulsive force is:
Lone pairlone pair repulsion

> Lone pair-bonding > Bonding pair-bonding pair repulsion pair repulsion Decrease of the repulsion force

Note:

The electron pairs repulsion will determine the orientation of atoms in space
68

4.2.2 Shape of a molecule

Basic shapes are based on the repulsion between the bonding pairs. Tips to determine the molecular shape : Step 1 Draw Lewis structure of the molecule Step 2 Consider the number of bonding pairs Step 3 Place bonding pairs as far as possible to minimize repulsion.

69

A.

Molecules with 2 bonding pairs

shape

Example: BeCl2
Lewis structure

Be : 2e
2Cl :14e Total : 16 e .. .. Cl: Cl Be .. ..

180

70

Linear

B.

Molecules with 3 bonding-pairs

Example: BCl3 Repulsive forces Lewis structure between pairs are the B: 3e same
3Cl : 21e

Total: 24e
Cl B
120

: .. .. Cl : .. .. Cl .. .. :
71

Trigonal planar

C. Molecules with 4 bonding pairs

Example: CH4 Lewis structure H H C H H
109.5

Equal repulsion between bonding pairs equal angle

Tetrahedral
72

D. Molecules with 5 bonding pairs

Example: PCl5 Lewis structure
:

Shape:
90

Cl

..

..

Cl ..

.. Cl : ..

Cl

73

..

P
..
:

.. Cl :
120

Trigonal bipyramidal

E. Molecules with 6 bonding pairs

Example: SF6 Lewis structure
S : 6e 6F : 42e Total : 48e

Octahedral
90o 90o

F F F F F
74

2 electron pairs in the valence shell of central atom:

Class of molecules AB2 Number of bonding pairs 2 Number of lone pairs 0 Shape

180

Linear
75

3 electron pairs in the valence shell of central atom:

Class of molecules AB3 Number of bonding pairs 3 Number of lone pairs 0
120

Shape

76

trigonal planar

4 electron pairs in the valence shell of central atom:

Class of molecules AB4 Number of bonding pairs 4 Number of lone pairs 0
109.5o

Shape

77

Tetrahedral

5 electron pairs in the valence shell of central atom:

Class of molecules AB5 Number of bonding pairs 5 Number of lone pairs 0
90

Shape

120

78

Trigonal pyramidal

6 electron pairs in the valence shell of central atom:

Class of molecules AB6 Number of bonding pairs 6 Number of lone pairs 0
90

Shape

90

79

Octahedral

4.2.3 Effect of lone pairs on molecular shape

The geometries of molecules and polyatomic ions, with one or more lone pairs around the central atom can be predicted using VSEPR. The molecular geometry is determined by the repulsions of electron pairs in the valence shell of the central atoms.
80

 Repulsion between electron pairs decreases in the order of:

Lone pairlone pair repulsion > Lone pairbonding pair repulsion > Bonding pairbonding pair repulsion

Stronger to weaker repulsion

81

 Electrons in a bond are held by the attractive forces exerted by the nuclei of the two bonded atoms therefore, they take less space of repulsion. Lone- pair electrons in a molecule occupy more space; therefore they experience greater repulsion from neighboring lone pairs and bonding pairs

82

Number of electron pair : 3

Example : SO2

Class of molecules : AB2E Molecular shape : Bent / V-shaped

83

Number of electron pair : 4

Example : NH3

Class of molecules : AB3E Molecular shape : Trigonal pyramidal

84

Number of electron pair : 4

Example : H2O

Class of molecules : AB2E2 Molecular shape : Bent / V-shaped

85

Number of electron pair : 5

Example : SF4

Class of molecules : AB4E Molecular shape : Distorted tetrahedron / seesaw

86

Number of electron pair : 5

Example : ClF3

Class of molecules : AB3E2

Molecular shape : T-shaped

87

Number of electron pair : 5

Example : I3-

Class of molecules : AB2E4

Molecular shape : Linear

88

Number of electron pair : 6

Example : BrF5 Class of molecules : AB5E

Molecular shape : Square pyramidal

89

Number of electron pair : 6

Example : XeF4

Class of molecules : AB4E2

Molecular shape : Square planar

90

Shape of molecules which the central atom has one or more lone pairs
Class of molecules AB2E Number of bonding pairs 2 Number of lone pairs 1 Shape

Bent / V-shaped
91

Bond angle : < 120o

4 electron pairs in the valence shell of central atom:

Class of molecules AB3E Number of bonding pairs 3 Number of lone pairs 1 Shape

92

Trigonal pyramidal Bond angle : < 109.5o

4 electron pairs in the valence shell of central atom:

Class of molecules AB2E2 Number of bonding pairs 2 Number of lone pairs 2 Shape

Bent / V-shaped Bond angle : < 109.5o

93

5 electron pairs in the valence shell of central atom:

Class of molecules AB4E Number of bonding pairs 4 Number of lone pairs 1 Shape

94

Distorted tetrahedral (see-saw) Bond angle : < 90o

5 electron pairs in the valence shell of central atom:

Class of molecules AB3E2 Number of bonding pairs 3 Number of lone pairs 2 Shape

95

T-shaped Bond angle : < 90o

5 electron pairs in the valence shell of central atom:

Class of molecules AB2E3 Number of bonding pairs 2 Number of lone pairs 3 Shape

96

Linear Bond angle : 180o

6 electron pairs in the valence shell of central atom:

Class of molecules
AB5E

Number of bonding pairs

5

Number of lone pairs

1

Shape

97

Square pyramidal Bond angle :90o and 180o

5 electron pairs in the valence shell of central atom:

Class of molecules AB4E2 Number of bonding pairs 4 Number of lone pairs 2 Shape

98

Square planar Bond angle : 90o

99

COMPARISON OF BOND ANGLE IN CH4, NH3 AND H2O

109.5o

107.3o

104.5o

100

a) CH4 Has 4 bonding pairs electrons.

The repulsion between the bonding pairs electrons are equal. The bond angles are all 109.5o

101

b) NH3

has 3 bonding pairs electron and 1 lone pair electron. according to VSEPR, lone pair - bonding pair > bonding pair - bonding pair repulsion. Lone- pair repels the bonding-pair more strongly, the three NH bonding-pair are pushed closer together, thus HNH angle in ammonia become smaller, 107.3o.
102

c) H2O
Has 2 bonding pairs electrons and 2 lone pair electrons. According to VSEPR, lone pair lone pair > lone pair bonding pair > bonding pair bonding pair repulsion. Lone-pair tend to be as far from each other as possible. Therefore, the two OH bonding-pairs are pushed toward each other. Thus, the HOH angle is 104.5o.
103

4.2.4 POLAR AND NONPOLAR MOLECULES

A quantitative measure of the polarity of a bond is

its dipole moment ( ). = Qr

Where : = dipole moment Q = the product of the charge from electronegativity r = distance between the charges.
Dipole moments are usually expressed in debye units(D)
104

E.g : Polarity of HF
Hydrogen fluoride is a covalent molecule with a polar bond. F atom is more electronegative than H atom, so the electron density will shift from H to F. The symbol of the shifted electron can be represented by a crossed arrow to indicate the direction of the shift.
H
105

The consequent charge separation can be represented by : + : partial positive charge

- : partial negative charge

106

 Diatomic molecules containing atoms of different elements (e.g. : HCl, NO and CO) have dipole moments and are called polar molecules.

Diatomic molecules containing atoms of the same element (e.g. : H2, N2 and Cl2) do not have dipole moments and are called nonpolar molecules.

107

For polyatomic molecules, the polarity of the bond and the molecular geometry determine whether there is a dipole moment.

Even if polar bond are present, the molecules will not necessarily have a dipole moment.

108

Example
Predict the polarity of the following molecules:

Carbon dioxide, CO2 Carbon tetrachloride, CCl4 Chloromethane, CH3Cl Ammonia, NH3

109

(a) Carbon dioxide, CO2

- molecular geometry : linear - oxygen is more electronegative than carbon, - Dipole moment can cancell each other - has no net dipole moment ( = 0) - therefore CCl4 is a nonpolar molecule.
110

(b) Carbon tetrachloride, CCl4

- molecular geometry : tetrahedral - Chlorine is more electronegative than carbon, - Dipole moment can cancell each other - has no net dipole moment ( = 0) - therefore CCl4 is a nonpolar molecule.
111

( c) Chloromethane, CH3Cl

- molecular geometry : tetrahedral - Cl is more electronegative than C, C is more electronegative than H - Dipole moment cannot cancell each other - has a net dipole moment ( 0) - therefore CH3Cl is a polar molecule.
112

(d ) Ammonia, NH3

- molecular geometry : tetrahedral - N is more electronegative than H, - Dipole moment cannot cancell each other - has a net dipole moment ( 0) - therefore NH3 is a polar molecule.
113

Factors that affected the polarity of molecules

molecular geometry electronegativity of the bonded atoms.

114

BOND NON-POLAR POLAR NON-POLAR MOLECULES NON-POLAR MOLECULES Symetrical molecules - basic molecular shape with the same terminal atom - molecules with lone pairs linear (from trigonal bipyramidal) and square planar with the same terminal atom
115

POLAR MOLECULES
Non-symetrical molecules - basic molecules with different terminal atom - molecules with lone pairs except linear and square planar

Exercises :
Predict the polarity of the following molecules:

SO2 ; HBr ; SO3 ; CH2Cl2 ; ClF3 ; CF4 ; H2O ; XeF4 ; NF3 ; Cis-C2H2Cl2 ; trans-C2H2Cl2

116

4.3 ORBITAL OVERLAP AND HYBRIDIZATION

1. Formation Covalent Bond 2. Formation Hybrid orbitals 3. Orbital Overlapping

117

Objectives
At the end of this subtopic, students should be able to: 1. Draw and describe the formation of sigma() and pi() bonds from overlapping of orbitals.

2. Draw and explain the formation of hybrid orbitals of a central atom: sp, sp2, sp3, sp3d, sp3d2 using appropriate examples. 3. Draw orbitals overlap and label sigma() and pi() bonds of a molecule.
118

4.3.1

Valence Bond theory

explains the formation of covalent bonds and the molecular geometry outlined by the VSEPR. States that a covalent bond is formed when the neighboring atomic orbitals overlap. Overlapping may occur between: a) orbitals with unpaired electrons b) an orbital with paired electrons and another empty orbitals (dative bond)
119

Example:
H H The s-orbital of the Hydrogen atom

Change in electron density as two hydrogen atoms approach each other.

High electron density as the orbitals overlap (covalent bond formed)
120

10.3

FORMATION OF COVALENT BOND

Valence bond theory - Covalent bond is formed when two neighbouring atomic half-filled orbitals overlap.

Two types of covalent bonds are

a) sigma bond () b) pi bond ()

121

a) bond
formed when orbitals overlap along its internuclear axis (end to end overlapping) Example: i. overlapping s orbitals

bond
122

ii.

Overlapping of s and p orbitals

Px orbital H
+
x

bond

123

 iii. Overlapping of p orbitals

bond

124

b) bond
Formed when two p-orbitals of the same orientation overlap sideways
y y y

125

bond

bond
126

Formation of bonds in a molecule Covalent bonds may form by: a) overlapping of pure orbitals b) overlapping of hybrid orbitals

127

Overlapping of pure orbitals

Example : i. O2 ii. N2

128

O2
Consider the ground state configuration:
O : 1s2 2s2 2p4
1s 2s Two unpaired electrons to be used in bonding.

2p

Overlapping occurs between the p-orbitals of each atom

129

130

N2

131

4.3.2

Formation Hybrid orbitals

Overlapping of hybrid orbitals and the pure orbitals occur when different type of atoms are involved in the bonding. Hybridization of orbitals: mixing of two or more atomic orbitals to form a new set of hybrid orbitals The purpose of hybridisation is to produce new orbitals which have equivalent energy Number of hybrid orbitals is equal to number of pure atomic orbitals used in the hybridization process.

132

Hybridization
Hybrid orbitals have different shapes from original atomic orbitals Types of hybridisation reflects the shape/geometry of a molecule Only the central atoms will be involved in hybridisation

133

10.4

Hybridization of orbitals
i. sp ii. sp2 iii. sp3 iv. sp3d v. sp3d2

134

sp3 hybridization
one s orbital and three p orbitals are mixed to form four sp3 hybrid orbitals the geometry of the four hybrid orbitals is tetrahedral with the angle of 109.5o .

135

sp3 hybrid
Mixing of s and three p orbitals
sp3

sp3

136

Example:
1) CH4
Lewis structure : Valence orbital diagram ; H: C ground state : C excited : C hybrid :

Orbital Overlap :
Molecular Geometry :
137

Example : Methane, CH4

Ground state : C : 1s2 2s2 2p2
1s Excitation: to have 4 unpaired electrons 2s 2p

Lewis Structure

H H C H H
H sp3

Excited state :
1s 2s

2p

C
sp3

sp3
sp3 H

sp3 hybrid

shape: tetrahedral
138

Fig. 10.8

3-Hybridized sp

C atom in CH4

sp3 1s sp3
sp3

sp3

1s

1s
139

Example 2 :

NH3 Lewis structure : Valence orbital diagram ; H: N ground state : N excited : N hybrid : Orbital Overlap : Molecular Geometry :
140

Fig. 10.9

sp3

1s

sp3 sp3

sp3

1s

1s
141

Example:

3) H2O Lewis structure

Valence orbital diagram; O ground state : O hybrid : Orbitals overlap:

142

2 sp

hybridization

one s orbital and two p orbitals are mixed to form three sp2 hybrid orbitals the geometry of the three hybrid orbitals is trigonal planar with the angle of 120o .

143

Fig. 10.12

sp2

px

py

sp2

sp2

144 one s orbital + two p orbitals

three sp2 orbitals

 simplified drawing of sp2 orbitals:

Shown together (large lobes only)

145

Example:

1) BF3 Lewis structure

Valence orbital diagram; F: B ground state : B excited : B hybrid :

Orbital overlap:
146

Example: BF3
Pure p orbital

sp2 sp2

F : 1s22s22p5
sp2

Shape : trigonal planar

147

Example:

2) C2H4 Lewis structure

Valence orbital diagram; C ground state : C excited : C hybrid :

Orbital overlap:

148

Fig. 10.16a-c

bonds

bond
149

150

10.5

sp hybridization
one s orbital and one p orbital are mixed to form two sp hybrid orbitals the geometry of the two hybrid orbitals is linear with the angle of 180o

151

Types of hybrid orbitals

Formation of sp Hybrid Orbitals

sp

sp

Produces linear shape

152

10.4

Example:

1) BeCl2 Lewis structure

Valence orbital diagram; Cl : Be ground state : Be excited : Be hybrid :

Orbital overlap:
153

Fig. 10.11

154

Example:

2) C2H2 Lewis structure

Valence orbital diagram; C ground state : C excited : C hybrid :

Orbital overlap:

155

Fig. 10.19a-c

156

Example:

3) CO2 Lewis structure

Valence orbital diagram; O: C ground state : C excited : C hybrid :

Orbital overlap:
157

3d sp

hybridization

one s orbital, three p orbitals and one d orbital are mixed to form five sp3d hybrid orbitals. the geometry of the five hybrid orbitals is trigonal bipyramidal with the angle of 120o and 90o

158

 simplified drawing of sp3d orbitals:

159

Example:

1) PCl5 Lewis structure

Valence orbital diagram; Cl : P ground state : P excited : P hybrid :

Orbital overlap:
160

Example:

2) ClF3 Lewis structure

Valence orbital diagram; F: Cl ground state : Cl excited : Cl hybrid :

Orbital overlap:
161

3d2 sp

hybridization

one s orbital, three p orbitals and two d orbitals are mixed to form six sp3d2 hybrid orbitals the geometry of the six hybrid orbitals is octahedral with the angle of 90o

162

 Simplified drawing of sp3d2 orbitals:

163

Example:

1) SF6 Lewis structure

Valence orbital diagram; F: S ground state : S excited : S hybrid :

Orbital overlap:
164

Example:

2) ICl5 Lewis structure

Valence orbital diagram; Cl : I ground state : I excited : I hybrid :

Orbital overlap:
165

How do I predict the hybridization of the central atom? Count the number of lone pairs AND the number of atoms bonded to the central atom No of Lone Pairs + No of Bonded Atoms 2 3 4 5
166

Hybridization sp sp2 sp3 sp3d sp3d2

Examples BeCl2 BF3 CH4, NH3, H2O PCl5 SF6

10.4

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

167

Exercise:
For each of the following, draw the orbital overlap to show the formation of covalent bond a) XeF2 b) O3 c) ICl4 d) OF2
168

4.4 Intermolecular forces

LEARNING OUTCOMES At the end of the lesson, students should be able to;
1.

2. 3.

1.

Describe intermolecular forces i. van der Waals forces : - dipole-dipole interactions or permanent dipole - London forces or dispersion forces ii. Hydrogen bonding Explain factors that influence the strength of van der Waals forces Explain the effects of hydrogen bonding on i. boiling point ii. Solubility iii. Density of water compared to ice Explain the relationship between : i. intermolecular forces and vapour pressure ii. Vapour pressure and boiling point

4.4 Intermolecular forces

4.4.1 Types of intermolecular forces 4.4.2The effect of intermolecular forces on the physical properties.

171

Intermolecular Forces

Intermolecular forces are the attractive forces between molecules

172

Effects of intermolecular forces on physical properties

Have effects on these physical properties: a) boiling point b) melting point c) solubility d) density e) electrical conductivity
173

Intermolecular Forces Van der Waal Forces Hydrogen Bond

Between covalent molecules

Between covalent molecules with H covalently bonded to F, O or N

174

4.4.1.1

van der Waal Forces

Forces that act between covalent molecules Three types of interaction: i. Dipole-dipole attractive forces - act between polar molecules ii. London Dispersion forces - act between non-polar molecules

175

Dipole-dipole forces (permanent dipole forces)

Exist in polar covalent compounds Polar molecules have permanent dipole due to the uneven electron distributions Example:

+
+

Cl

Cl

Chlorine is more electronegative, thus it has higher electron density

Dipole-dipole forces; the partially positive end attracts the partially negative end

176

4.4.1.2. London Dispersion Forces

attractive forces that exist between non-polar molecules result from the temporary (instantaneous) polarization of molecules The temporary dipole molecules will be attracted to each other and these attractions is known as the London Forces or London Dispersion forces
177

The formation of London forces

At any instant, electron distributions in one molecule may be unsymmetrical. The end having higher electron density is partially negative and the other is partially positive. An instant dipole moment that exists in a molecule induces the neighboring molecule to be polar.

178

Example: London forces in Br2

Electrons in a molecule move randomly about the nucleus At any instant, the electron density might be higher on one side
+

Br

Br The temporary dipole molecule induce the neighboring atom to be partially polar

Temporary dipole molecule

Br

Br

Br

Br

London forces

179

Factors that influence the strength of the van der Waals forces.

The molecular size/molecular mass Molecules with higher molar mass have stronger van der Waals forces as they tend to have more electrons involved in the London forces. Example: CH4 has lower boiling point than C2H6 Note: However if two molecules have similar molecular mass, the dipole-dipole interaction will be more dominant. Example: H2S has higher boiling point than CH3CH3

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4.4.1.3 Hydrogen intermolecular bond

Dipole-dipole interaction that acts between a Hydrogen atom that is covalently bonded to a highly electronegative atom ; F, O ,N in one molecule and F,O or N of another molecule. Example:

Hydrogen intermolecular bond

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Other examples:
NH3 liquid ..
N Hydrogen intermolecular bond O

H2O
Hydrogen intermolecular bond O

..
N

O Covalent bond Hydrogen intermolecular bond

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Consider ethanol, CH3OH

CH3OH
CH3OH and methane

Hydrogen bond C O in

Not a hydrogen bond

H is not bonded to either F, O or N

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Example: H2O

H O H H O H H H

___ covalent bond ----- hydrogen bond

H O H O H

O H

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Properties of compounds with Hydrogen intermolecular forces

Boiling point

Have relatively high boiling point than compounds having dipole-dipole forces or London forces - the Hydrogen bond is the strongest attraction force compared to the dipoledipole or the London forces.
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Solubility
A. Dissolve in polar solvent The molecules that posses Hydrogen bonds are highly polar. They may form interaction with any polar molecules that act as solvent. B. Dissolve in any solvent that can form Hydrogen bonds
187

Example

NH3 dissolves in water because it can form Hydrogen intermolecular bond with water.

Hydrogen bond ..
N

..
N

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Problem:

Explain the trend of boiling point given by the graph below:

T/oC HF

HI
HBr HCl

Molecular mass

189

Answer

HF can form hydrogen bonds between molecules while HCl, HBr and HI have van der Waals forces acting between molecules. Hydrogen intermolecular bond is stronger that the van der Waals forces. More energy is required to break the Hydrogen bond. Boiling point increases from HCl to HI. The strength of van der Waals forces increases with molecular mass. Since molecular mass increases from HCl to HI, thus the boiling point will also increase in the same pattern.
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The effect of Hydrogen bond on water molecules

The density of water is relatively high compared to other molecules with similar molar mass. Reason: Hydrogen intermolecular bonds are stronger than the dipole-dipole or the London forces. Thus the water molecules are drawn closer to one another and occupy a smaller volume.
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Density
Ice (solid H2O) has lower density compared to its liquid. Refer to the structure of ice

Ice form tetrahedral arrangement

Hydrogen bond takes one of the tetrahedral orientation and occupy some space

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H2O(l) is denser than H2O(s) because the hydrogen bond in ice arrange the H2O molecules in open hexagonal crystal H2O molecules in water have higher kinetic energy and can overcome the hydrogen bond V-shaped water molecules slide between each other.

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195

196

Fig. 11.13

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Boiling points of substance with Hydrogen intermolecular bonds

The boiling points of these substances are affected by: a) the number of hydrogen bonds per molecule b) the strength of H intermolecular forces which directly depends on the polarity of the hydrogen bond
Example: Explain the trend of boiling points given below: The order of the increase in boiling point is: H2O > HF > NH3 > CH4
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Answer:

by looking at the polarity of the bond, we have (Order of polarity: HF > H2O > NH3) but H2O has the highest boiling point. For H2O, the number of hydrogen bonds per molecule affects the boiling point. Each water molecule can form 4 hydrogen bonds with other water molecules. More energy is required to break the 4 Hydrogen bonds. HF has higher boiling point than NH3 because F is more electronegative than Nitrogen. CH4 is the lowest - it is a non polar compound and has weak van der Waals forces acting between molecules.

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Effects of intermolecular forces on physical properties

1)Boiling point For molecules with similar size, the order of intermolecular strength: Hydrogen bond > dipole-dipole forces > London dispersion forces Strength of intermolecular forces boiling point

200

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Why boiling point H2O > HF and HF > NH3?

Fluorine is more electronegative than oxygen, therefore stronger hydrogen bonding is expected to exist in HF liquid than in H2O. However, the boiling point of H2O is higher than HF because each H2O molecules has 4 hydrogen bonds.

202

On the other hand, H-F has only 2 hydrogen bonds. Therefore the hydrogen bonds are stronger in H2O rather than in H-F.

203

Boiling point HF > NH3

Fluorine is more electronegative than nitrogen ,thus the hydrogen bonding in H-F is stronger than H-N.

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Vapour Pressure

Molecules can escape from the surface of liquid at any temperature by evaporation

in a closed system :

vapour molecules which leaves the surface cannot escape from the system the molecules strike the container wall and exert some pressure

Fig. 11.34

The pressure exerted by those molecules is called vapour pressure (or maximum vapour pressure)

Vapour pressure is the pressure exerted by a vapour in equilibrium with its liquid phase.

In a close system .
Liquid molecules vapourise Vapour molecules are trapped in the close container Volume of liquid becomes less Rate of vaporisation is faster than the rate of condensation Molecules have enough energy to overcome intermolecular forces

Some of the vapour molecules may collide and lose their energy. They re-enter the liquid surface

System reaches equilibrium dynamic equilibrium Volume of liquid remains constant

Rate of vapourisation is equal to the rate of condensation Pressure exerted by the vapour molecules is known as the vapour pressure

Dynamic equilibrium and vapour pressure

Number of liquid molecules leaving the surface is the same as the number of vapour molecules entering the liquid surface. The vapour pressure at this stage is constant and known as the equilibrium vapour pressure.

Dynamic equilibrium is reached when: Rate of evaporation = rate of condensation Note: Equilibrium vapour pressure = saturated vapour pressure = vapour pressure

Factors that affects vapour pressure

i. Intermolecular forces Molecules with weak intermolecular forces can easily vapourise. More vapour molecules will be present and exert higher pressure. the weaker intermolecular forces the higher is the vapour pressure. ii. Temperature Heating causes more molecules to have high kinetic energies that are higher than their intermolecular forces. More liquid molecules will form vapour. vapour pressure increases with temperature.

Fig. 11.35

Boiling the process

Increasing the temperature will increase in the vapour pressure. As heat is applied, the vapour pressure of a system will increase until it reaches a point whereby the vapour pressure of the liquid system is equal to the atmospheric pressure. Boiling occurs and the temperature taken at this point is known as the boiling point. At this point, the change of state from liquid to gas occurs not only at the surface of the liquid but also in the inner part of the liquid.

Bubbles form within the liquid.

Boiling Point: the temperature at which the vapour pressure of a liquid is equal to the external atmospheric pressure. Normal Boiling Point: the temperature at which a liquid boils when the external pressure is 1 atm (that is the vapour pressure is 760 mmHg)

Factors affecting the boiling point:

1. Intermolecular forces

A substance with weak intermolecular forces can easily vapourise and the system requires less heat to achieve atmospheric pressure, thus it boils at a lower temperature. 2. Atmospheric pressure When the external atmospheric pressure is low, liquid will boil at a lower temperature.

4.5 Metallic bond

LEARNING OUTCOMES At the end of the lesson, students should be able to;
1. 2. Explain the formation of metallic bond by using electron sea model. Relate metallic bond to the properties of metal: i. malleability ii. Ductility iii. Electrical conductivity iv. Thermal conductivity Explain the factors that affect the strength of metallic bond Relate the strength of metallic bond to boiling point

3. 4.

Metallic bond
An electrostatic force between positive charge metallic ions and the sea of electrons. Bonding electrons are delocalized over the entire crystal which can be imagined as an array of the ions immersed in a sea of delocalized valence electron.

217

Metallic bonds
Positive ions are immersed in the sea of electrons
e e e e

Free moving electrons

e

218

Electrostatic force in a metal

Metallic Bond (Electron-sea Model) Metals form giant metallic structure Each positive ion is attracted to the sea of electrons. These atoms are closely held by the strong electrostatic forces acting between the positive ions and the sea of electrons. These free moving electrons are responsible for the high melting point of metals and the electrical conductivity.
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Physical properties of metals

metals have high melting point high energy is required to overcome these strong electrostatic forces between the positive ions and the electron sea in the metallic bond
+ e + e + e e + e + e e + e + e + e + e + e

+ e + e + e e

+ e + e

Metallic bonds formed by the electrostatic forces exist between positive ions and the free moving electrons

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The strength of the metallic bonds

The strength of the metallic bond increases with the number of valence electrons and the size of ions. The smaller the size of positive ions the greater is the attractive force acting between the ions and the valence electrons

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Boiling points in metals

Na
+1 e
+1 e +1 e +1 Mg

+1
e

+1
e +1

+1
e +1

+1
e +1

+1
+1

e e +1 +1

e e e +1 +1 +1

ee ee ee ee ee +2 +2 +2 +2 +2 ee ee ee ee ee +2 +2 +2 +2 +2 ee ee ee ee ee ee +2 +2 +2 +2 +2

ee ee ee +2 +2 +2 ee ee ee +2 +2 +2 ee ee ee +2 +2 +2

Has one valence electron

Has 2 valence electrons

the electrostatic force acting between positive ions and free moving electrons form metallic bonds

Stronger metallic bond due to the size of Mg being smaller than Na and the strong electrostatic force between +2 ions and the two valence electrons,

Mg has higher boiling point than Na

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Example:
Explain the difference in the boiling point of the two metals given: Magnesium 11300 oC Aluminum 24500 oC

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Answer

The cationic size of Al is smaller compared to magnesium and its charge is higher (+3). Mg has two valence electrons Al has three valence electrons involved in the metallic bonding. The strength of metallic bond in Aluminium is greater than that of Magnesium Al has higher boiling point
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The strength of metallic bond is directly proportional to the boiling point. The stronger metallic bond,the higher the boiling point.

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