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C

H

A

P

T

E

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1 C H A P T E R 1 PART A: Chemical Bonding

PART A: Chemical Bonding

Contents

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Explaining Covalent Bonding

Valence Bond Theory

Hybridization of Atomic Orbitals

sp Hybrid Orbitals

sp 2 Hybrid Orbitals

sp 3 Hybrid Orbitals

sp 3 d Hybrid Orbitals

sp 3 d 2 Hybrid Orbitals

Overlapping of Atomic Orbitals in Single and Multiple Bonds

Delocalized π Bonding

Explaining of Covalent Bonding

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Molecular Formula

Explaining of Covalent Bonding 3 Molecular Formula Lewis Structure VSEPR Model a) b) Electron-domain geometry Molecular

Lewis Structure

of Covalent Bonding 3 Molecular Formula Lewis Structure VSEPR Model a) b) Electron-domain geometry Molecular

VSEPR Model

a)

b)

Electron-domain geometry

Molecular geometry

3 Molecular Formula Lewis Structure VSEPR Model a) b) Electron-domain geometry Molecular geometry Valence Bond Theory

Valence Bond Theory

Valence Bond Theory

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VSEPR Model:

It predicts the geometry/shape of a molecule. It does not explain why bonds exist between atoms in a molecule.

VB Theory

It is a model of covalent bonding.

It explains the bonding together with the geometry of molecule

(VSEPR model) using atomic orbitals (what is atomic orbital?).

It shows the ways of atomic orbitals can mix one another to form a

chemical bond.

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In the Lewis theory, covalent bonding occurs when atoms share electrons. Such sharing concentrates electron density between the nuclei.

sharing concentrates electron density between the nuclei.  In the VB theory, the buildup of electron

In the VB theory, the buildup of electron density between two nuclei is visualized as occurring when valence atomic orbital of one atom overlaps

with that of another atom.

The overlap of these orbitals allows two electrons of opposite spin to share

the common space between the nuclei, forming a covalent bond.

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The overlap of orbitals in a molecule of hydrogen gas :

Orbital diagram of valence electron

of hydrogen gas : Orbital diagram of valence electron 1s H 1s H H – H

1s

H

1s

H

hydrogen gas : Orbital diagram of valence electron 1s H 1s H H – H End
hydrogen gas : Orbital diagram of valence electron 1s H 1s H H – H End
hydrogen gas : Orbital diagram of valence electron 1s H 1s H H – H End

H H

End to end overlap = sigma () bond

1 σ bond

7 The overlap of orbitals in a molecule of hydrogen fluoride: Orbital diagram of valence
7 The overlap of orbitals in a molecule of hydrogen fluoride: Orbital diagram of valence

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The overlap of orbitals in a molecule of hydrogen fluoride:

Orbital diagram of valence electron

of orbitals in a molecule of hydrogen fluoride: Orbital diagram of valence electron 1s H 2s
of orbitals in a molecule of hydrogen fluoride: Orbital diagram of valence electron 1s H 2s

1s

H

of orbitals in a molecule of hydrogen fluoride: Orbital diagram of valence electron 1s H 2s
of orbitals in a molecule of hydrogen fluoride: Orbital diagram of valence electron 1s H 2s

2s

of orbitals in a molecule of hydrogen fluoride: Orbital diagram of valence electron 1s H 2s

F

2p

of orbitals in a molecule of hydrogen fluoride: Orbital diagram of valence electron 1s H 2s

H F

1 σ bond

in a molecule of hydrogen fluoride: Orbital diagram of valence electron 1s H 2s F 2p
8 The overlap of orbitals in a molecule of oxygen gas: Orbital diagram of valence
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The overlap of orbitals in a molecule of oxygen gas:

Orbital diagram of valence electron

molecule of oxygen gas: Orbital diagram of valence electron 2s O 2p Side to side overlap

2s

of oxygen gas: Orbital diagram of valence electron 2s O 2p Side to side overlap =
of oxygen gas: Orbital diagram of valence electron 2s O 2p Side to side overlap =

O

2p

of oxygen gas: Orbital diagram of valence electron 2s O 2p Side to side overlap =

Side to side overlap = pi (π) bond

Orbital diagram of valence electron 2s O 2p Side to side overlap = pi ( π

2s

Orbital diagram of valence electron 2s O 2p Side to side overlap = pi ( π

O

2p

Orbital diagram of valence electron 2s O 2p Side to side overlap = pi ( π

O = O

1 σ bond

1 π bond

valence electron 2s O 2p Side to side overlap = pi ( π ) bond 2s
9 The overlap of orbitals in a molecule of nitrogen gas: Orbital diagram of valence
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The overlap of orbitals in a molecule of nitrogen gas:

Orbital diagram

of valence electron

in a molecule of nitrogen gas: Orbital diagram of valence electron 2s N 2p 2s N

2s

in a molecule of nitrogen gas: Orbital diagram of valence electron 2s N 2p 2s N
in a molecule of nitrogen gas: Orbital diagram of valence electron 2s N 2p 2s N
in a molecule of nitrogen gas: Orbital diagram of valence electron 2s N 2p 2s N
in a molecule of nitrogen gas: Orbital diagram of valence electron 2s N 2p 2s N

N

2p

in a molecule of nitrogen gas: Orbital diagram of valence electron 2s N 2p 2s N
in a molecule of nitrogen gas: Orbital diagram of valence electron 2s N 2p 2s N

2s

in a molecule of nitrogen gas: Orbital diagram of valence electron 2s N 2p 2s N
in a molecule of nitrogen gas: Orbital diagram of valence electron 2s N 2p 2s N
in a molecule of nitrogen gas: Orbital diagram of valence electron 2s N 2p 2s N

N

2p

in a molecule of nitrogen gas: Orbital diagram of valence electron 2s N 2p 2s N

O Ξ O 1 σ bond

2 π bonds

of nitrogen gas: Orbital diagram of valence electron 2s N 2p 2s N 2p O Ξ
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Remember:

The space formed by overlapping of orbitals has a maximum capacity

of two electrons that must have opposite spins.

 The space formed by overlapping of orbitals has a maximum capacity of two electrons that
 The space formed by overlapping of orbitals has a maximum capacity of two electrons that
 The space formed by overlapping of orbitals has a maximum capacity of two electrons that

Hybridization of Atomic Orbitals

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The atomic orbitals on an atom mix to form new orbitals called

hybrid orbitals.

The process of mixing atomic orbitals as atoms approach each other to

form covalent bonds is called hybridization.

The hybrid orbitals have different shapes than the original atomic orbitals.

have different shapes than the original atomic orbitals. Atomic orbitals Hybridization H y b r i

Atomic orbitals

Hybridization

different shapes than the original atomic orbitals. Atomic orbitals Hybridization H y b r i d

Hybrid orbital

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Five Types of Hybrid Orbitals:

sp (linear)

sp 2 (trigonal planar)

sp 3 (tetrahedral)

sp 3 d (trigonal bipyramidal)

sp 3 d 2 (octahedral)

We postulate the type of hybrid orbital

after we observe the molecular geometry

using VSEPR model.

How to predict the hybridization of the central atom of a molecule?

Count the electron domains (lone pairs + bonding pairs) around the central atom.

Electron Domains

Hybridization

Examples

2

sp

BeCl 2

3

sp

2

BF 3

4

sp

3

CH 4 , NH 3 , H 2 O

5

sp 3

d

PCl 5

6

sp 3 d 2

SF 6

sp Hybrid Orbitals

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Lewis structure of BeCl 2

sp Hybrid Orbitals 14 Lewis structure of BeCl 2 2 electron domains Central atom (Be): sp
sp Hybrid Orbitals 14 Lewis structure of BeCl 2 2 electron domains Central atom (Be): sp

2 electron domains Central atom (Be): sp

Bond diagram of BeCl 2

Geometry of BeCl 2

It has two bonding pairs. Thus, the geometry of BeCl 2 is a linear.

G e o m e t r y o f B e C l 2 It
15 Use VB theory to describe the bonding: Orbital diagram of valance electron for central
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Use VB theory to describe the bonding:

Orbital diagram of valance

electron for central atom (Be)

2s

2p

      (ground state)
     

(ground state)

      (ground state)     (excited state) hybridization
    (excited state)
    (excited state)
   

(excited state)

hybridization

hybridization

state)     (excited state) hybridization sp (hybridized state) In order to form two covalent bonds
state)     (excited state) hybridization sp (hybridized state) In order to form two covalent bonds

sp

    (excited state) hybridization sp (hybridized state) In order to form two covalent bonds with
    (excited state) hybridization sp (hybridized state) In order to form two covalent bonds with

(hybridized state)

In order to form two covalent bonds with chlorine atoms, beryllium atom must supply two orbitals which are half-filled. This can be achieved through sp hybridization.

The two chlorine atoms are then covalently bonded to the beryllium atom through the overlap of the p orbital and with the sp hybrid orbitals.

are then covalently bonded to the beryllium atom through the overlap of the p orbital and
A t o m i c o r b i t a l s Two

Atomic orbitals

Two sp hybrid orbitals

A t o m i c o r b i t a l s Two sp
A t o m i c o r b i t a l s Two sp

sp 2 Hybrid Orbitals

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Lewis structure of BF 3

Bond diagram of BF 3

Geometry of BF 3

structure of BF 3 Bond diagram of BF 3 Geometry of BF 3 3 electron domains
structure of BF 3 Bond diagram of BF 3 Geometry of BF 3 3 electron domains

3 electron domains Central atom (B): sp 2

of BF 3 3 electron domains Central atom (B): sp 2 It has three bonding pairs.

It has three bonding pairs. Thus, the geometry of BF 3 is a trigonal planar.

18 Orbital diagram of valance electron for central atom (B) 2s 2p     (ground
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Orbital diagram of valance

electron for central atom (B)

2s

2p

    (ground state)
    (ground state)
   

(ground state)

    (ground state)   (excited state) hybridization
  (excited state)
  (excited state)
  (excited state)
 

(excited state)

hybridization

hybridization

(ground state)   (excited state) hybridization sp 2 (hybridized state) In order to form three covalent

sp 2

state)   (excited state) hybridization sp 2 (hybridized state) In order to form three covalent bonds

(hybridized state)

In order to form three covalent bonds with fluorine atoms, boron atom must supply three orbitals which are half-filled. This can be achieved through sp 2 hybridization.

The three fluorine atoms are then covalently bonded to the boron atom through the overlap of the p orbital and with the sp 2 hybrid orbitals.

then covalently bonded to the boron atom through the overlap of the p orbital and with

sp 3 Hybrid Orbitals

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Lewis structure of CH 4

sp 3 Hybrid Orbitals 20 Lewis structure of CH 4 4 electron domains Central atom (C):
sp 3 Hybrid Orbitals 20 Lewis structure of CH 4 4 electron domains Central atom (C):

4 electron domains Central atom (C): sp 3

Bond diagram of CH 4

domains Central atom (C): sp 3 Bond diagram of CH 4 Geometry of CH 4 It

Geometry of CH 4

It has four bonding pairs. Thus, the geometry of CH 4 is a tetrahedral.

21 Orbital diagram of valance electron for central atom (C) 2s 2p   (ground state)
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Orbital diagram of valance electron for central atom (C)

2s

2p

  (ground state)
  (ground state)
  (ground state)
 

(ground state)

  (ground state) (excited state) hybridization
(excited state)
(excited state)
(excited state)
(excited state)

(excited state)

hybridization

hybridization

  (ground state) (excited state) hybridization sp 3 (hybridized state) In order to form four covalent

sp 3

(hybridized state)

In order to form four covalent bonds with hydrogen atoms, carbon atom must supply four orbitals which are half-filled. This can be achieved through sp 3 hybridization.

The four hydrogen atoms are then covalently bonded to the carbon atom through the overlap of the s orbital and with the sp 3 hybrid orbitals.

then covalently bonded to the carbon atom through the overlap of the s orbital and with
The sp 3 hybrid orbitals in NH 3
The sp 3 hybrid orbitals in NH 3
The sp 3 hybrid orbitals in H 2 O
The sp 3 hybrid orbitals in H 2 O

sp 3 d Hybrid Orbitals

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Lewis structure of PCl 5

Bond diagram of PCl 5

Geometry of PCl 5

of PCl 5 Bond diagram of PCl 5 Geometry of PCl 5 5 electron domains Central
of PCl 5 Bond diagram of PCl 5 Geometry of PCl 5 5 electron domains Central

5 electron domains Central atom (P): sp 3 d

of PCl 5 5 electron domains Central atom (P): sp 3 d It has five bonding

It has five bonding pairs. Thus, the geometry of PCl 5 is a trigonal bipyramidal.

26 Orbital diagram of valance electron for central atom (P) 3s 3 p 3d hybridization
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Orbital diagram of valance

electron for central atom (P)

3s

Orbital diagram of valance electron for central atom (P) 3s 3 p 3d hybridization (ground state)
Orbital diagram of valance electron for central atom (P) 3s 3 p 3d hybridization (ground state)

3p

diagram of valance electron for central atom (P) 3s 3 p 3d hybridization (ground state) (excited
diagram of valance electron for central atom (P) 3s 3 p 3d hybridization (ground state) (excited
diagram of valance electron for central atom (P) 3s 3 p 3d hybridization (ground state) (excited
diagram of valance electron for central atom (P) 3s 3 p 3d hybridization (ground state) (excited
diagram of valance electron for central atom (P) 3s 3 p 3d hybridization (ground state) (excited
diagram of valance electron for central atom (P) 3s 3 p 3d hybridization (ground state) (excited
diagram of valance electron for central atom (P) 3s 3 p 3d hybridization (ground state) (excited
diagram of valance electron for central atom (P) 3s 3 p 3d hybridization (ground state) (excited
diagram of valance electron for central atom (P) 3s 3 p 3d hybridization (ground state) (excited

3d

diagram of valance electron for central atom (P) 3s 3 p 3d hybridization (ground state) (excited

hybridization

electron for central atom (P) 3s 3 p 3d hybridization (ground state) (excited state) (hybridized state)
electron for central atom (P) 3s 3 p 3d hybridization (ground state) (excited state) (hybridized state)
electron for central atom (P) 3s 3 p 3d hybridization (ground state) (excited state) (hybridized state)
electron for central atom (P) 3s 3 p 3d hybridization (ground state) (excited state) (hybridized state)

(ground state)

(excited state)

(hybridized state)

sp 3 d In order to form five covalent bonds with chlorine atoms, phosphorus atom must supply five orbitals which are half-filled. This can be achieved through sp 3 d hybridization.

The five chlorine atoms are then covalently bonded to the phosphorus atom through the overlap of the p orbital and with the sp 3 d hybrid orbitals.

covalently bonded to the phosphorus atom through the overlap of the p orbital and with the

sp 3 d 2 Hybrid Orbitals

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Lewis structure of SF 6

Bond diagram of SF 6

Geometry of SF 6

diagram of SF 6 G e o m e t r y o f S F
diagram of SF 6 G e o m e t r y o f S F

6 electron domains Central atom (S): sp 3 d 2

It has six bonding pairs. Thus, the geometry of SF 6 is a octahedral.

domains Central atom (S): sp 3 d 2 It has six bonding pairs. Thus, the geometry
29 Orbital diagram of valance electron for central atom (S) 3s 3 p 3d hybridization
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Orbital diagram of valance electron for central atom (S)

3s

Orbital diagram of valance electron for central atom (S) 3s 3 p 3d hybridization sp 3

3p

diagram of valance electron for central atom (S) 3s 3 p 3d hybridization sp 3 d
diagram of valance electron for central atom (S) 3s 3 p 3d hybridization sp 3 d
diagram of valance electron for central atom (S) 3s 3 p 3d hybridization sp 3 d
diagram of valance electron for central atom (S) 3s 3 p 3d hybridization sp 3 d

3d

diagram of valance electron for central atom (S) 3s 3 p 3d hybridization sp 3 d
diagram of valance electron for central atom (S) 3s 3 p 3d hybridization sp 3 d
diagram of valance electron for central atom (S) 3s 3 p 3d hybridization sp 3 d
diagram of valance electron for central atom (S) 3s 3 p 3d hybridization sp 3 d
diagram of valance electron for central atom (S) 3s 3 p 3d hybridization sp 3 d
diagram of valance electron for central atom (S) 3s 3 p 3d hybridization sp 3 d
diagram of valance electron for central atom (S) 3s 3 p 3d hybridization sp 3 d
diagram of valance electron for central atom (S) 3s 3 p 3d hybridization sp 3 d

hybridization

electron for central atom (S) 3s 3 p 3d hybridization sp 3 d 2 (ground state)
electron for central atom (S) 3s 3 p 3d hybridization sp 3 d 2 (ground state)
electron for central atom (S) 3s 3 p 3d hybridization sp 3 d 2 (ground state)
electron for central atom (S) 3s 3 p 3d hybridization sp 3 d 2 (ground state)

sp 3 d 2

(ground state)

(excited state)

(hybridized state)

In order to form six covalent bonds with fluorine atoms, sulphur atom must supply six orbitals which are half-filled. This can be achieved through sp 3 d 2 hybridization.

The six fluorine atoms are then covalently bonded to the sulphur atom through the overlap of the p orbital and with the sp 3 d 2 hybrid orbitals.

bonded to the sulphur atom through the overlap of the p orbital and with the sp

Overlapping of Atomic Orbitals in

Single and Multiple Bonds

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Sigma () bond = end-to-end overlap

Overlapping of Atomic Orbitals in Single and Multiple Bonds 31 Sigma (  ) bond =
Overlapping of Atomic Orbitals in Single and Multiple Bonds 31 Sigma (  ) bond =
Overlapping of Atomic Orbitals in Single and Multiple Bonds 31 Sigma (  ) bond =
Overlapping of Atomic Orbitals in Single and Multiple Bonds 31 Sigma (  ) bond =
32 Pi () bond = side-by-side overlap ONLY p orbitals
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Pi () bond = side-by-side overlap
ONLY p orbitals
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C

- C

1 bond

C

= C

1 bond

1 bond

C

C

1 bond 2 bonds

33 C - C 1  bond C = C 1  bond 1  bond

The σ bonds in ethane(C 2 H 6 )

The σ bonds in ethane(C 2 H 6 ) b o t h C a r

both C are sp 3 hybridized

s-sp 3 overlaps to  bonds All single bonds are sp 3 -sp 3 overlap
s-sp 3 overlaps to  bonds
All single bonds are
sp 3 -sp 3 overlap to form a  bond
sigma bonds.

The σ and π bonds in ethylene (C 2 H 4 )

The σ and π bonds in ethylene (C 2 H 4 ) overlap in one position
The σ and π bonds in ethylene (C 2 H 4 ) overlap in one position
overlap in one position - 
overlap in one position - 

p overlap -

The half-filled unhybridized 2p orbitals of C are close enough to overlap side-to-side (pi bond).

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The σ and π bonds in acetylene (C 2 H 2 ) overlap in one
The σ and π bonds in acetylene (C 2 H 2 )
overlap in one position - 
p overlap - 
The half-filled unhybridized of two 2p orbitals of C are close enough to overlap side-to-side
(pi bond).
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How many sigma and pi bonds are in the acetic acid (vinegar) molecule CH 3

How many sigma and pi bonds are in the acetic acid (vinegar) molecule CH 3 COOH?

 

H

  H O  
  H O  

O

O
O
O
O
 
 bonds = 6 + 1 = 7

bonds = 6 + 1 = 7

 

H

H

C

C

C

C O H

O

C O H

H

C O H
C O H

bond = 1

 
H

H

Describe the types of bonds and orbitals in acetone,

Describe the types of bonds and orbitals in acetone,

(CH 3 ) 2

CO.

 

sp 2

sp 2

sp 3 hybridized
sp 3 hybridized

H

H

sp 3 hybridized H H sp 2 O 2 2 C O C C C H
sp 3 hybridized H H sp 2 O 2 2 C O C C C H

sp 2

O

sp 3 hybridized H H sp 2 O 2 2 C O C C C H

2

2

C

O C C C
O
C C C

H

H

H
H

C

sp 3 hybridized
sp 3 hybridized

H

H
H

C

sp 3

sp

sp

2 O 2 2 C O C C C H H H C sp 3 hybridized

H

sp 3

H
H

sp 2

sp 3

C C C H H H C sp 3 hybridized H H C sp 3 sp

sp 3

C C C H H H C sp 3 hybridized H H C sp 3 sp

sp 3

H
H
H
H

sp 3

sp 2 hybridized
sp 2 hybridized
H
H

sp 3

sp 3

H

O C
O
C
O C C 3 C  bond

C

O C C 3 C  bond

3 C

 bond

H 3

 

 bonds

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Delocalized π Bonding

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Localized electrons:

The sigma and pi electrons are associated totally with the two atoms that form the bond. These bonding electrons are localized.

Delocalized electrons:

Electrons that are spread over a number of atoms in a molecule rather than

localized between a pair of atoms.

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Remember:

In many molecules, however, we cannot adequately describe the

bonding as being entirely localized.

This situation arises particularly in molecules that have two or more resonance structures involving π bonds.

situation arises particularly in molecules that have two or more resonance structures involving π bonds. Benzene
situation arises particularly in molecules that have two or more resonance structures involving π bonds. Benzene

Benzene

Ozone

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Delocalized π bonding in benzene:

Resonance structure of benzene is

π bonding in benzene: Resonance structure of benzene is  If the resonance structures involve the

If the resonance structures involve the placement of the double bonds in

different locations, that suggests that the π component of the double bonds is

actually delocalized in a way suggested by the resonance.

In each of the structures the geometry at C atom is trigonal planar, which implies sp 2 hybridization of the C atom.

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The sp 2 hybrid orbitals are used to construct the six localized C C σ bonds and six localized C H σ bonds that are present in each of the resonance structures.

bonds that are present in each of the resonance structures.  The unhybridized 2p orbital on

The unhybridized 2p orbital on the C atom could be used to make π bonds.

in each of the resonance structures.  The unhybridized 2p orbital on the C atom could
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These π electrons are delocalized over the six C C bonds as shown in figure below.

over the six C – C bonds as shown in figure below.  As conclusion, there

As conclusion, there are three delocalized C C π bonds in each of the

resonance structures.

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Delocalized π bonding in ozone:

Resonance structure of ozone is

' '
'
'

If the resonance structures involve the placement of the double bonds in

different locations, that suggests that the π component of the double bonds is

actually delocalized in a way suggested by the resonance.

In each of the structures the geometry at O' atom is trigonal planar, which implies sp 2 hybridization of the O' atom.

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The sp 2 hybrid orbitals are used to construct the two localized O O σ bonds that are present in each of the resonance structures.

The unhybridized 2p orbital on the O atom could be used to make π bonds.

These π electrons are delocalized over the three O O bonds as shown in figure

below.

over the three O – O bonds as shown in figure below.  As conclusion, there

As conclusion, there is a delocalized O O π bonds in each of the resonance

structures.

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