Chemical Bonding

and
Molecular Structure
(Chapter 9)

Ionic vs. covalent bonding

Molecular orbitals and the covalent bond (Ch. 10)
Valence electron Lewis dot structures
octet vs. non-octet
resonance structures
formal charges
VSEPR - predicting shapes of molecules
Bond properties
electronegativity
polarity, bond order, bond strength
20 Oct 97

Bonding and

Rules for making Lewis dot structures

1. Count no. of valence electrons

(- dont forget to include the charge on molecular ions!)

2 for # of PAIRS
2. Place a bond pair (BP) between connected atoms
3. Complete octets by using rest of e- as lone pairs (LP)
4. For atoms with <8 e-, make multiple bonds to complete octets
5. Assign formal charges : fc = Z - (#BP/2) - (#LP)
Indicate equivalent (RESONANCE) structures
6. Structures with smaller formal charges are preferred
- consider non-octet alternatives (esp. for 3rd, 4th row)
OCTET RULE: #Bond Pairs + #Lone Pairs = 4
(except for H and atoms of 3rd and higher periods)

#lone pairs at central atom in AXn = {(#e-) - 8*n}/2

20 Oct 97

Bonding and

Sulfur Dioxide, SO2

Rules 1-3

OS O
OR bring in
right pair

bring in
left pair

S O

O +S O

These equivalent structures

are called:

The proper Lewis structure

is a HYBRID of the two.

RESONANCE
STRUCTURES.

Each atom has OCTET . .

. . . BUT there is a +1 and -1 formal charge
20 Oct 97

Bonding and

SO2 (2)
Alternate Lewis structure for SO2 uses 2 double bonds

O=S=O

Sulfur does not obey OCTET rule

BUT the formal charge = 0

This is better structure than O=S+-Osince it reduces formal charge (rule 6).
3rd row S atom can have 5 or 6 electron pairs
NB: # of central atom lone pairs = (3*6 -8*2)/2 = 1
in both O=S+-O- and O=S=O structures
20 Oct 97

Bonding and

Thiocyanate ion, (SCN)

Which of three possible resonance structures

is most important?

A.

S=C=N

B.

S=C - N

C.

S-C N

Calculated partial charges

ANSWER:

-0.52

20 Oct 97

-0.16

-0.32
Bonding and

C>A>B
5

MOLECULAR GEOMETRY

VSEPR

Valence Shell Electron Pair

Repulsion theory.
Most important factor in
determining geometry is relative
repulsion between electron pairs.

20 Oct 97

Bonding and

Molecule
adopts the
shape that
minimizes the
electron pair
repulsions.
6_VSEPR.mov

No.ofePairs
AroundCentral
Atom
2

Example

Geometry

CAChe
image

linear

FBeF
180o
F

3
F

planartrigonal

120o
H

C
H

20 Oct 97

109o
tetrahedral
H
H
Bonding and

Structure Determination by VSEPR

Ammonia, NH3
There are 4 electron pairs at the corners of a
tetrahedron.
lonepairofelectrons
intetrahedralposition

H N H
H

H
H

The ELECTRON PAIR GEOMETRY is tetrahedral.

20 Oct 97

Bonding and

VSEPR - ammonia
Ammonia, NH3
N
H

lonepairofelectrons
intetrahedralposition
H

Although the electron pair geometry is tetrahedral . . .

. . . the MOLECULAR GEOMETRY
the positions of the atoms
is PYRAMIDAL.
20 Oct 97

Bonding and

AXnEm notation
a good way to distinguish between
electron pair and molecular geometries
is the AXnEm notation
where:
A - atom whose local geometry is of interest
(typically the CENTRAL ATOM)
Xn - n atoms bonded to A
Em - m lone pair electrons at A
NH3 is AX3E system pyramidal
(NB this notation not used by Kotz)
20 Oct 97
Bonding and

10

VSEPR - water
Water, H2O

1. Draw electron dot structure

H-O-H

2. Count BPs and LPs = 4

3. The 4 electron pairs are at the
corners of a tetrahedron.
O
H

20 Oct 97

The electron pair

geometry is
TETRAHEDRAL.
Bonding and

11

VSEPR - water (2)

H-O-H

Although the electron

pair geometry is
H TETRAHEDRAL . . .

. . . the molecular
geometry is bent.

H2O - AX2E2 system - angular geometry

20 Oct 97

Bonding and

12

Formaldehyde, CH2O

VSEPR - formaldehyde
1. Draw electron dot structure

2. Count BPs and LPs:

At Carbon there are 4 BP but . . .
3. These are distributed in ONLY 3 regions.
Double bond electron pairs are in same region.
There are 3 regions of electron density
Electron repulsion places them at the corners of a planar triangle.

H C

Both the electron pair geometry and the

molecular geometry are PLANAR TRIGONAL
120o bond angles.

20 Oct 97

H2CO at the C atom is an AX3 species

Bonding and

13

VSEPR - Bond Angles

Methanol, CH3OH
Define bond angles 1 and 2
Angle 1 = H-C-H = ?
Angle 2 = H-O-C = ?
Answer:
o

HCOH

H
Angle1
Angle2

109 because both the C and O

atoms are surrounded by 4 electron pairs.

6_CH3OH.mov

AXnEm designation ?
at C
at O

20 Oct 97

Bonding and

AX4 = tetrahedral
AX2E2 = bent
14

Acetonitrile, CH3CN

VSEPR - bond angles (2)

Define bond angles 1 and 2

H
HCC
1

Angle 2 = 180
? o

Angle 1 = ?109o

Why ? :
The CH3 carbon is surrounded by 4 bond charges
The CN carbon is surrounded by 2 bond charges
AXnEm designation ?
at CH3 carbon AX4 = tetrahedral
AX2 = linear
at CN carbon
20 Oct 97

Bonding and

15

What about:
STRUCTURES WITH
CENTRAL ATOMS
THAT DO NOT OBEY
THE OCTET RULE ?

PF5

BF3
SF4
20 Oct 97

Bonding and

16

Geometry for non-octet species

also obey VSEPR rules

Consider boron trifluoride, BF3

The B atom is surrounded by only 3
electron pairs.
Bond angles are 120o

Molecular Geometry is
planar trigonal
BF3 is an AX3 species
20 Oct 97

Bonding and

17

Compounds with 5 or 6 Pairs

Around the Central Atom

90
F

F
P
F

Trigonalbipyramid
F

120 5 electron pairs

AX5 system
90

6 electron pairs

F
F

20 Oct 97

6_VSEPR.mov

F
S
F

F
F

Bonding and

Octahedron
90

AX6 system
18

Sulfur Tetrafluoride, SF4

F S F

Number of valence e- = 34
No. of S lone pairs =
{17 - 4 b.p. - 3x4 l.p.(F)}
= 1 lone pair on S
There are 5 (BP + LP)
e- pairs around the S
THEREFORE:
electron pair geometry ?
= trigonal bipyramid

F
S
F
OR

AX4E system. Molecular geometry ?

20 Oct 97

Bonding and

F
F

S
F
19

F
F

Sulfur Tetrafluoride, SF4 (2)

90

axial
equatorial

F
S
F

120

Lone pair is in the equatorial position because it

requires more room than a bond pair.
Molecular geometry of SF4 is see-saw

Q: What is molecular geometry of SO2 ?

20 Oct 97

Bonding and

20

Bonding with Hybrid Atomic Orbitals

- Carbon prefers to make 4 bonds as in CH4
But atomic carbon has an s2p2 configuration
Why can it make more than 2 bonds ?

6_CH4.mov

4 C atom orbitals hybridize to form four

equivalent sp3 hybrid atomic orbitals.

20 Oct 97

Bonding and

21

Orbital Hybridization
BONDS

SHAPE

HYBRID REMAIN

linear

s2p2
{2 x sp &2 ps}

C2H2

trigonal
planar

{3 x sp2 & 1 p}

C2H4

tetrahedral {4 xsp3 }

20 Oct 97

Bonding and

e.g.

CH4

22

Multiple Bonds

and Bonding in C2H4

2s
2p
C atom orbitals are COMBINED
(= re-hybridized) to form orbitals
better suited for BONDING
The 3 sp2 hybrid orbitals
are used to make the C-C
and two C-H bonds
6_C2H4-sg.mov
6_C2H4-pi.mov

6_C2H4.mov

20 Oct 97

3sp2
hybrid
orbitals

120

p
orbital

The extra p orbital

electron on each C atom
overlaps the p orbital on
the neighboring atom to
form the bond.

H
H

Bonding and

H
H

sp2
23

Consequences of Multiple
Bonding

Restricted rotation around C=C bond in

1-butene = CH2=CH-CH2-CH3.

E (kJ/mol)

See Butene.Map in ENER_MAP in CAChe models.

233

27
-180

0
180
C-C=C angle (o)

20 Oct 97

P. 475 - Photo-rotation
about double bonds
lets us see !!

Bonding and

24

Bond Properties
What is the effect of bonding and structure on molecular
properties ?
- bond order
- bond length
- bond strength
- bond polarity
- MOLECULAR polarity

Buckyball in HIV-protease, see page 107

20 Oct 97

Bonding and

25

Bond Order
the number of bonds between a pair of atoms.

single
BO=1
1

20 Oct 97

triple,BO=3
1 and2
C

CH2CHCN
Acrylonitrile

double,BO=2
1 and1

Bonding and

26

Bond Order (2)

Fractional bond orders occur in molecules with resonance
structures.
Consider NO2
O

Bond order =

Total # of e - pairs used for a type of bond

Total # of bonds of that type

Bond order in NO2- =

3 (e - pairs in N-O bonds)

2 (N - O bonds)

N-O bond order in NO2- = 1.5

20 Oct 97

Bonding and

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Bond Order and Bond Length

Bond order is related to two important bond properties:

(a) bond strength

as given by DE

110 pm
745 kJ

(b) Bond length

- the distance between
the nuclei of two bonded
atoms.
20 Oct 97

414 kJ 123 pm

Bonding and

Formaldehye
28

Bond Length
- depends on size of bonded atoms:
Molecule
H- F
H- Cl
H- I
- depends on bond order.
Molecule
CH3C- OH
O=C=O
C O
20 Oct 97

R(H-X)
104 pm
131 pm
165 pm
R(C-O)
141 pm
132 pm
119 pm
Bonding and

29

Bond Strength
Bond Dissociation energy (DE) - energy required to
break a bond in gas phase.
See Table 9.5

BOND
HH

STRENGTH (kJ/mol)
436

LENGTH (pm)
74

CC
C=C
CC

347
611
837

154
134
121

NN

946

110

The GREATER the number of bonds (bond order)

the HIGHER the bond strength and the SHORTER the bond.
20 Oct 97

Bonding and

30

Bond Strength
(2)
Bond

Order

Length

Strength

HOOH

149 pm

210 kJ/mol

O=O

121

498 kJ/mol

128

? kJ/mol
303

1.5

O

HOW TO CALCULATE ?

O3 (g) 3 O(g)

Hrxn = {3xHf(O) - Hf(O3)} = {3x249.2 - 142.7} = 605 kJ/mol

2 O-O bonds in O3 DE (O3) = 605/2 = 302.5 kJ/mol
20 Oct 97

Bonding and

31

Bond Polarity
+

Cl

HCl is POLAR because it has a positive

end and a negative end (partly ionic).
Polarity arises because Cl has a greater
share of the bonding electrons than H.
Calculated charge by CAChe:
H (red)
is +ve (+0.20 e-)
Cl (yellow) is -ve (-0.20 e-).
(See PARTCHRG folder in MODELS.)

20 Oct 97

Bonding and

32

Bond Polarity
(2)

Cl

Due to the bond polarity, the HCl bond

energy is GREATER than expected for a
pure covalent bond.
BOND
ENERGY
pure bond
339 kJ/mol calculated
real bond
432 kJ/mol measured
Difference
92 kJ/mol.
This difference is the contribution of IONIC bonding
It is proportional to the difference in

ELECTRONEGATIVITY, .
20 Oct 97

Bonding and

33

Electronegativity,
is a measure of the ability of an atom in a
molecule to attract electrons to itself.

Concept proposed by
Linus Pauling (1901-94)
Nobel prizes:
Chemistry (54), Peace (63)
See p. 425; 008vd3.mov (CD)

20 Oct 97

Bonding and

34

4
3.5

3
2.5

Si

Cl

Electronegativity,
Figure 9.7

1.5
1
0.5
0

10 11 12 13 14 15 16 17 18

F has maximum .
Atom with lowest is the center atom in most
molecules.
Relative values of determines BOND
POLARITY (and point of attack on a molecule).
20 Oct 97

Bonding and

35

Bond Polarity
Which bond is more polar ? (has larger bond DIPOLE)
OH
OF
(A) - (B) 3.5 - 2.1
3.5 - 4.0
0.5

1.4
(O-H) > (O-F)
Therefore OH is more polar than OF

H
2.1
O F
3.5 4.0

Also note that polarity is reversed.

OH
+
20 Oct 97

OF
+
Bonding and

36

Molecular Polarity
Moleculessuch as HCl and H2O
can be POLAR (or dipolar).
They have a DIPOLE MOMENT.
Polar molecules turn to align their
dipole with an electric field.
POSITIVE
POSITIVE

20 Oct 97

HCl
HCl

NEGATIVE
NEGATIVE

Bonding and

37

Predicting molecular
polarity
A molecule will be polar ONLY if
a) it contains polar bonds
AND
b) the molecule is NOT symmetric
Symmetric molecules

20 Oct 97

Bonding and

38

Molecular Polarity: H2O

H
polar

O
H

Water is polar because:

a) O-H bond is polar
b) water is non-symmetric

H
+

The dipole associated with polar H2O

is the basis for absorption of microwaves
used in cooking with a microwave oven

20 Oct 97

Bonding and

39

Carbon Dioxide

-0.73 +1.46 -0.73

CO2 is NOT polar even

though the CO bonds
are polar.
Because CO2 is
symmetrical the BOND
polarity cancels

The positive C atom is why

water attaches to CO2
CO2 + H2O H2CO3
20 Oct 97

Bonding and

40

Molecular Polarity in
NON-symmetric molecules

F
F

B +ve
F -ve

BF bonds are polar

molecule is symmetric
BF3 is NOT polar

20 Oct 97

Chg.
+ve
+ve
-ve

Atom

B
H
F

2.0
2.1
4.0

BF, BH bonds polar

molecule is NOT symmetric
HBF2 is polar

Bonding and

41

Fluorine-substituted Ethylene: C2H2F2

CF bonds are MUCH more polar than CH bonds.
(C-F) = 1.5, (C-H) = 0.4
CIS isomer
both CF bonds on same side
molecule is POLAR.

TRANS isomer
both CF bonds on opposite side
molecule is NOT POLAR.
20 Oct 97

Bonding and

42

Chemical Bonding
and
Molecular Structure
(Chapter 9)

Ionic vs. covalent bonding

Molecular orbitals and the covalent bond (Ch. 10)
Valence electron Lewis dot structures
octet vs. non-octet
resonance structures
formal charges
VSEPR - predicting shapes of molecules
Bond properties
electronegativity
polarity, bond order, bond strength
20 Oct 97

Bonding and

43