Sei sulla pagina 1di 81

The Chemical Bond 2

CAMPO - CHEM 14
Theories on Covalent Bonding

1. Valence Bond Theory



a. VSEPR Theory
2. Molecular Orbital Theory

CAMPO - CHEM 14
Valence Bond Theory

- covalent bond formation is due to overlap of atomic orbitals


- electrons reside in the region of overlap of atomic orbitals
- gives a localized electron model of bonding
How does Lewis theory explain the bonds in H2 and F2?

Sharing of two electrons between the two atoms.

Bond Enthalpy Bond Length Overlap Of

H2 436.4 kJ/mol 74 pm 2 1s

F2 150.6 kJ/mol 142 pm 2 2p


CAMPO - CHEM 14
Valence Bond Theory and CH4
CH4:
Experimentally
determined: All C-H
bonds are identical

According to VBT, a covalent bond is formed from the overlap of


the valence orbital containing one e- in one atom with another
valence orbital containing one e- from another atom.

2p

CAMPO - CHEM 14
Valence Bond Theory and CH4

Following VBT, Carbon should only be able to form two bonds from
the overlap of two of its valence orbital containing one e- each with
two H atoms each containing a half-filled valence orbital.

2p

Unstable due to
lack of octet

CAMPO - CHEM 14
Valence Bond Theory and NH3

N – 1s22s22p3

3 H – 1s1

If the bonds form from overlap of 3 2p orbitals on nitrogen with


the 1s orbital on each hydrogen atom, what would the molecular
geometry of NH3 be?
If we use the
3 2p orbitals, we
predict bond
angle at 90o

Actual H-N-H
bond angle is
CAMPO - CHEM 14 107.3o
Atomic Orbital Hybridization

Hybridization – mixing of two or more atomic orbitals to form a


new set of hybrid orbitals.
- VBT uses concept of hybridization to supplement it

1. Mix at least 2 nonequivalent atomic orbitals (e.g. s and p). Hybrid


orbitals have very different shape from original atomic orbitals.
2. Number of hybrid orbitals is equal to number of pure atomic orbitals
used in the hybridization process.
3. Covalent bonds are formed by:
a. Overlap of hybrid orbitals with atomic orbitals
b. Overlap of hybrid orbitals with other hybrid orbitals
4. In general, two steps:
a. Excitation
b. Hybridization
CAMPO - CHEM 14
Valence Bond Theory and CH4

G.S. :
CH4:

E.S. :

E.S. configuration can now allow formation of four bonds, BUT


still insufficient since it can’t explain how all the C-H bonds are
identical and methane’s tetrahedral shape

CAMPO - CHEM 14
Valence Bond Theory and CH4

H.S. :

In hybridization, orbitals are “mixed” to form a set of hybrid


orbitals possessing the properties of its constituents (e.g. sp3:
25% s character and 75% p character

CAMPO - CHEM 14
Formation of sp3 Hybrid Orbitals

Each hybrid orbital contains e-


which tend to stay away as far
from each other as possible to
minimize repulsion

CAMPO - CHEM 14 !10


Formation of Covalent Bonds in CH4

H-C-H bond angle: 109.5o


!11
CAMPO - CHEM 14
sp3-Hybridized N Atom in NH3

Predict correct
bond angle

H-N-H bond angle: 107.3o


CAMPO - CHEM 14
Valence Shell Electron Pair Repulsion (VSEPR) Theory

- provides a method for predicting the shape of molecules, based


on the electrostatic repulsion between electron pairs (bonding and
nonbonding).

According to the VSEPR model, due to e- pair repulsions, molecules adopt


geometries in which valence e- pairs are positioned as far from each other
as possible.

CAMPO - CHEM 14
Valence Shell Electron Pair Repulsion (VSEPR) Theory

Terms:
!

Bond length – distance between nuclei.


Bond angle – angle between adjacent bonds.
Electron group geometry – distribution of e- pairs.
Molecular geometry – distribution of nuclei.

CAMPO - CHEM 14
Valence Shell Electron Pair Repulsion (VSEPR) Theory

A molecule can be described with the generic formula:

where A is the central atom, X stands for any atom or group


connected to the central atom, and E represents a group of lone
pair e-

The steric number (SN = m + n) is the number of positions


occupied by atoms or lone pairs around the central atom

NH3

SN = 4 SN = 4
CAMPO - CHEM 14
CAMPO - CHEM 14
Single Bonds
SN = 2

SN = 3

CAMPO - CHEM 14
Single Bonds

SN = 4

SN = 5

CAMPO - CHEM 14
Single Bonds

SN = 6

CAMPO - CHEM 14
Formation of sp Hybrid Orbitals

CAMPO - CHEM 14
Formation of sp2 Hybrid Orbitals

!21
CAMPO - CHEM 14
Geometries with Nonbonding e- (Lone Pairs)

- In predicting the molecular geometry, the extent of separation of


the valence e- is based on the total number of valence e- pairs and
not on the bonding pairs only

- We consider electron group geometry, which depicts distribution


of e- pairs, in determining molecular geometry

repulsion: lone e- pair-lone e- pair > lone e- pair-bonding > bonding-bonding

CAMPO - CHEM 14
Geometries with Lone Pairs
SN = 4

EGG MG

EGG MG
Geometries with Lone Pairs
SN = 5

EGG MG

EGG MG
Geometries with Lone Pairs
SN = 5

EGG MG

CAMPO - CHEM 14
Geometries with Lone Pairs
SN = 6

EGG MG

EGG MG
How do I predict the hybridization of the central atom?

1. Draw the Lewis structure of the molecule.


2. Count the number of lone pairs AND the number of
atoms bonded to the central atom

SN = # of Lone Pairs
+
# of Bonded Atoms Hybridization Examples

2 sp BeCl2

3 sp2 BF3

4 sp3 CH4, NH3, H2O

5 sp3d PCl5

6 sp3d2 SF6
Molecular Geometry as a Function of Electron Group
Geometry : Summary
Bond angle – angle between adjacent bonds.
Electron group geometry – distribution of e- pairs.
Molecular geometry – distribution of nuclei.

Copyright © 2011 Pearson Canada Inc.


CAMPO - CHEM 14
Copyright © 2011 Pearson Canada Inc.
CAMPO - CHEM 14
Copyright © 2011 Pearson Canada Inc.
CAMPO - CHEM 14
Copyright © 2011 Pearson Canada Inc.
CAMPO - CHEM 14
Copyright © 2011 Pearson Canada Inc.
CAMPO - CHEM 14
Replace this part of table 10.1 this format is not
present in the text. Parent table is on page 425
and 426

Copyright © 2011 Pearson Canada Inc.


CAMPO - CHEM 14
Multiple Bonds

- Double and triple bonds have slightly greater repulsive effects


than single bonds because of the repulsive effect of π electrons.
- Multiple bonds tend to occupy the same position as lone pairs

repulsion: lone e- pair > bond pair (multiple bond) > bond pair (single bond)

CAMPO - CHEM 14
sp2 Hybridization of Carbon
C2H4 (ethylene): SN = 3

Only unhybridized p orbitals can form π bonds


CAMPO - CHEM 14
H H
Ethylene has a double bond in its Lewis structure.
C C
VSEPR says trigonal planar at carbon.
H H

Copyright © 2011 Pearson Canada Inc.


CAMPO - CHEM 14
Unhybridized 2pz orbital (gray), which is perpendicular
to the plane of the sp2 hybrid (green) orbitals.

!37
CAMPO - CHEM 14
Bonding in Ethylene, C2H4

Sigma bond (σ) – electron density between the 2 atoms


Pi bond (π) – electron density above and below plane of nuclei
of the bonding atoms !38
CAMPO - CHEM 14
Another View of π Bonding in Ethylene, C2H4

trigonal planar
consequence of double bond: planar molecule

!39
CAMPO - CHEM 14
sp Hybridization of Carbon
C2H2 (ethyne): SN = 2

!40
CAMPO - CHEM 14
Bonding in Acetylene, C2H2

linear

!41
CAMPO - CHEM 14
Describe the bonding in CH2O.

H
C O
H
C – 3 bonded atoms, 0 lone pairs
C – sp2

!42
CAMPO - CHEM 14
Sigma (σ) and Pi Bonds (π)

Single bond 1 sigma bond

Double bond 1 sigma bond and 1 pi bond

Triple bond 1 sigma bond and 2 pi bonds

How many σ and π bonds are in the acetic acid (vinegar)


molecule CH3COOH?

H
O

σ bonds = 6 + 1 = 7
H C C O H
π bonds = 1
H !43
CAMPO - CHEM 14
Molecules with More Than One Central Atom

The geometric distribution of terminal atoms around each central


atom must be determined and the results then combined into a single
description of the molecular shape.

CAMPO - CHEM 14
Applying VSEPR Theory

1. Draw a plausible Lewis structure.


2. Determine the number of e- groups and identify
them as bond or lone pairs.
3. Establish the e- group geometry.
4. Determine the molecular geometry.

CAMPO - CHEM 14
Practice

Determine the electron group geometry and molecular


geometry of :
a. ICl4-
b. H2CO

CAMPO - CHEM 14
Properties of Covalent Bonds

1. Bond polarity
- nonpolar bond: EN difference ≤ 0.4!
- polar bond: 0.4 < EN difference < 1.7!
- ionic bond: 1.7 ≤ EN diffrerence!
! ! ex: H-F> H-Cl> H-Br>HI (bond polarity)

One can determine a molecule’s polarity by looking at the presence or


absence of a dipole moment based on the magnitude and direction of the
bond dipoles.

CAMPO - CHEM 14
Which of the following molecules have a dipole moment?
H2O, CO2, SO2, and CF4

O H S O
H O
dipole moment dipole moment
polar molecule polar molecule
F

C
O C O
F F
no dipole moment F
nonpolar molecule no dipole moment
nonpolar molecule

Not all molecules with polar bonds are polar molecules.


Does BF3 have a dipole
moment?

CAMPO - CHEM 14
Does CH2Cl2 have a
dipole moment?

CAMPO - CHEM 14
Properties of Covalent Bonds

2. Bond dissociation energy/ Bond enthalpy

- energy needed to destroy a covalent bond!


- is a measure of the strength of a covalent bond

In general, !
↑bond polarity ↑bond dissociation energy

CAMPO - CHEM 14
Properties of Covalent Bonds

3. Bond order
- number of bonds present between two atoms
Single bond, bond order = 1
Double bond, bond order = 2
Triple bond, bond order = 3

In general, !
↑bond order ↓bond length ↑bond dissociation energy

CAMPO - CHEM 14
Properties of Covalent Bonds

4. Bond length
- internuclear distance

In general, !
↑size of atom ↑bond length!
↑bond polarity ↓bond length!
↑bond order ↓bond length

CAMPO - CHEM 14
Properties of Covalent Bonds

5. Bond angle
- becomes smaller due to presence of lone pairs!
! -deviation from ideal value!
- comparing different bond angles:

difference in central atoms ↑size of central atom ↓bond angle formed

e.g. H2O > H2S > H2Se > H2Te

difference in ligand atoms ↑size of ligand ↑bond angle formed

e.g. I2Se > Br2Se > Cl2Se > F2Se

CAMPO - CHEM 14
Practice

Determine the Lewis structure, molecular geometry and


polarity:
a. SNF3
b. XeOF4

Arrange accdg to increasing bond angle:


a. PH3, NH3, AsH3
b. OSF2, OSCl2, OSBr2

CAMPO - CHEM 14
How can VBT explain this observation?

Experiments show O2 is paramagnetic

O
O

No unpaired e-
Should be diamagnetic

CAMPO - CHEM 14
Molecular Orbital Theory (MOT)

- although VBT provides a simple description of bonding and structures, it fails to


describe some observed properties of some molecules!
! e.g. paramagnetism of O2; existence of the stable species H2+

Molecular orbital theory – bonds are formed from


interaction of atomic orbitals to form molecular
orbitals.

- The theory assigns the e- in a molecule to a series of orbitals that belong to the
molecule as a whole.

- MO are spread over the entire molecule as opposed to in VBT where e- from !
atomic overlap are localized in the region of overlap

CAMPO - CHEM 14
Constructive and Destructive Interference
Formation of bonding and antibonding 

molecular orbitals in hydrogen (H2)

The interaction of two hydrogen atoms according to molecular theory


Copyright © 2011 Pearson Canada Inc.

a.) The addition of two 1s orbitals in phase to form a σ1s molecular orbital. This
orbital produces electron density between the nuclei, leading to a chemical bond.

b.) The addition of two orbitals 1s out of phase to produce a σ*1s antibonding orbital.
This orbital has a nodal plane where there is zero e- density.

CAMPO - CHEM 14
Energy levels of bonding and antibonding molecular
orbitals in hydrogen (H2).

A bonding molecular orbital has lower energy and greater


stability than the atomic orbitals from which it was formed.

An antibonding molecular orbital has higher energy and


lower stability than the atomic orbitals from which it was
formed.
H2 Overlap of two 1s orbitals leads to
formation of two molecular orbitals:

destructive interference forms


antibonding molecular orbital (σ*1s)
- higher in energy than the two
atomic orbitals due to repulsion of
exposed (+) charged nucleus

constructive interference forms


bonding molecular orbital (σ1s)
-lower in energy than the two
atomic orbitals

Because the σ1s MO is lower in energy than the 1s AO, H2 is more stable
than its separate H atoms.
H2

VBT: 1s AO of two H atoms overlap


to form a chemical bond, that these
AO do not change but only simply
overlap

MOT: 1s AO of two H atoms not only


overlap, but also simultaneously
transformed into two MO with new
energies and e- distributions

CAMPO - CHEM 14
Molecular Orbital (MO) Configurations
!

1. The number of molecular orbitals (MOs) formed is always


equal to the number of atomic orbitals combined.
2. The more stable the bonding MO, the less stable the
corresponding antibonding MO.
3. The filling of MOs proceeds from low to high energies
(Aufbau Process).
4. Each MO can accommodate up to two electrons (Pauli
Exclusion Principle).
5. Use Hund’s rule when adding electrons to MOs of the same
energy (degenerate orbitals).
6. The number of electrons in the MOs is equal to the sum of
all the electrons on the bonding atoms.

CAMPO - CHEM 14
Bond Order

Stable species have more electrons in


bonding orbitals than antibonding.

Bond Order = 1/2 (No. e- in bonding MOs - No. e- in antibonding MOs)

So long as BO > 0, a bond would still exist

Copyright © 2011 Pearson Canada Inc.


CAMPO - CHEM 14
He2

BO = 0, meaning no bond is formed

Effect of bonding e- is cancelled by


antibonding e-

He2 is not expected to exist.

CAMPO - CHEM 14
Bond Order = 1/2 (No. e- in bonding MOs - No. e- in antibonding MOs)

bond
½ 1 ½ 0
order
MOT is able to predict and explain the existence of H2+ and He2+. A
BO = 1/2 would still indicate that a bond exists, although it would be
less than that of a single bond. VBT is not able to explain this.
CAMPO - CHEM 14
Orbital energy-level diagrams for Second Period elements
Li2

BO = 1
CAMPO - CHEM 14 Li2 can exist!
Orbital energy-level diagrams for Second Period elements
Be2

Be Be
Be-Be
BO = O
Be2 can’t exist!
CAMPO - CHEM 14
Two Possible Interactions Between Two Equivalent p Orbitals

CAMPO - CHEM 14
Orbital energy-level diagrams for Second Period elements

σ MOs are expected to have lower energy than π MOs due to more extensive/more
efficient overlap in head-to-head 2p overlap than side-to-side 2p overlap .

Possible molecular orbital energy-level schemes for diatomic molecules of the second-period elements
Copyright © 2011 Pearson Canada Inc.
CAMPO - CHEM 14
Experiment shows C2 to be diamagnetic, supporting a
modified energy-level diagram

Expected MO Diagram for C2

Modified MO Diagram for C2


Copyright © 2011 Pearson Canada Inc.
CAMPO - CHEM 14
Orbital energy-level diagrams for Second Period elements

modified order
expected order of σ and π MO
of σ and π MO due to 2s-2p
mixing

O2,F2,Ne2 and all other Z≥8 will follow B2, C2, N2 and all other Z ≤ 7 will follow the modified
the expected energy diagram energy diagram as a result of 2s-2p mixing
The modified energy diagram for the elements below
Oxygen is a result of 2s-2p mixing.

2s-2p mixing is due to the interaction of σ1s and σ2p


MOs whose energies are close enough (for Z ≤ 7) to
each other such that they are able to interact.

Consequence: Destabilization of σ2p causing it to lie


above π2p in the energy diagram.
Orbital energy-level diagrams for Second Period elements

with 2s-2p mixing

Molecular orbital occupancy diagrams for the homonuclear diatomic molecules of the second-period
elements

Copyright © 2011 Pearson Canada Inc.


CAMPO - CHEM 14
Orbital energy-level diagrams for Second Period elements

with no 2s-2p mixing

Molecular orbital occupancy diagrams for the homonuclear diatomic molecules of the second-period
elements

Copyright © 2011 Pearson Canada Inc.


CAMPO - CHEM 14
Orbital energy-level diagrams for Second Period elements

with 2s-2p mixing with no 2s-2p mixing

CAMPO - CHEM 14
There is no single “best” theory to explain covalent
bonding. Each has its own strengths and weaknesses. The
choice of which theory to use depends on which property
you want to explain.

CAMPO - CHEM 14
Bonding in the Benzene Molecule
Delocalized molecular orbitals are not confined between
two adjacent bonding atoms, but actually extend over three
or more atoms.
Example: Benzene, C6H6

Delocalized π orbitals

$78
FIGURE 11-29
Bonding in benzene, C6H6, by the valence-bond method

Copyright © 2011 Pearson Canada Inc.


CAMPO - CHEM 14
Electron density above and below the plane of the
benzene molecule.

Polycentric molecular orbital : obtained by having pi


electrons delocalize around the molecule continuosly in
loops (continuos delocalization)