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
polarity, bond order, bond strength
18, 20 Oct 97
Bonding and Structure
Chemical Bonding
Problems and questions
How is a molecule or polyatomic
ion held together?
Why are atoms distributed at
strange angles?
Why are molecules not flat?
Can we predict the structure?
How is structure related to
chemical and physical properties?
18, 20 Oct 97
Bonding and Structure
Forms of Chemical Bonds
There are 2 extreme forms of connecting
or bonding atoms:
Ioniccomplete transfer of electrons
from one atom to another
Covalentelectrons shared between
atoms
Most bonds are somewhere in between.
18, 20 Oct 97
Bonding and Structure
Ionic compounds
- essentially complete electron
transfer from an element of low IE
(metal) to an element of high
electron affinity (EA) (nonmetal)
Ionic
Bonds
Na(s) + 1/2 Cl2(g) Na+ + Cl
NaCl (s)
- primarily between metals
(Grps 1A, 2A and transition metals)
and nonmetals (esp O and halogens)
- NON-DIRECTIONAL bonding
via Coulomb (charge) interaction
18, 20 Oct 97
Bonding and Structure
Covalent Bonding
Covalent bond is the sharing of the VALENCE
ELECTRONS of each atom in a bond
Recall: Electrons are divided between core
and valence electrons.
ATOM
core
Na 1s2 2s2 2p6 3s1
[Ne]
Br [Ar] 3d10 4s2 4p5
[Ar] 3d10
valence
3s1
4s2 4p5
Br Br
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Bonding and Structure
Valence Electrons
1A
2A
3A
4A
5A
6A
8A
7A
Number of valence electrons is
equal to the Group number.
18, 20 Oct 97
Bonding and Structure
Covalent Bonding
The bond arises from the mutual attraction of
2 nuclei for the same electrons.
HA + HB
HA
HB
A covalent bond is a balance
of attractive and repulsive forces.
6_H2bond.mov
18, 20 Oct 97
Bonding and Structure
Bond Formation
A bond can result from a head-to-head overlap
of atomic orbitals on neighboring atoms.
Cl
Cl
Overlap of H (1s) and Cl (2p)
This type of overlap places bonding electrons in a
MOLECULAR ORBITAL along the line between
the two atoms and forms a SIGMA BOND ( ).
18, 20 Oct 97
Bonding and Structure
Sigma Bond Formation by Orbital Overlap
Two s Atomic Orbitals (A.O.s) overlap to form
an s (sigma) Molecular Orbital (M.O.)
H
sigmabond( )
6_H2pot.mov
18, 20 Oct 97
Bonding and Structure
Sigma Bond Formation by Orbital Overlap
H
sigmabond( )
Two s A.O.s overlap to
from an s M.O.
Similarly, two p A.O.s
can overlap end-on to
from a p M.O.
e.g.
F2
18, 20 Oct 97
Bonding and Structure
10
Electron
Distribution in
Molecules
Electron distribution
is depicted with
Lewis electron
dot structures
Electrons are
distributed as:
shared or BOND
PAIRS and
unshared or LONE
PAIRS.
G. N. Lewis
1875 - 1946
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Bonding and Structure
11
Bond and Lone Pairs
Electrons are distributed as shared or BOND
PAIRS and unshared or LONE PAIRS.
Cl
Unshared or
lone pair (LP)
shared or bond pair
This is a LEWIS ELECTRON DOT structure.
18, 20 Oct 97
Bonding and Structure
12
Rules of Lewis Structures
No. of valence electrons of an atom =
Group number
For Groups 1A-4A (Li - C),
no. of BOND PAIRS = group number
For Groups 5A-7A (N - F),
no. of BOND PAIRS = 8 - group No.
Except for H
(and atoms of 3rd and higher periods),
#Bond Pairs + #Lone Pairs = 4
This observation is called the OCTET RULE
18, 20 Oct 97
Bonding and Structure
13
Building a Dot Structure
Ammonia, NH3
1. Decide on the central atom; never H.
Central atom is atom of lowest affinity for electrons.
In ammonia, N is central
2. Count valence electrons
H = 1 and N = 5
Total = (3 x 1) + 5
= 8 electrons or
18, 20 Oct 97
Bonding and Structure
4 pairs
14
Building a Dot Structure
3. Form a sigma bond
between the central atom
and surrounding atoms.
4. Remaining electrons form
LONE PAIRS to complete
octet as needed.
H N H
H
H N H
3 BOND PAIRS and 1 LONE PAIR.
Note that N has a share in 4 pairs (8 electrons), while
each H shares 1 pair.
18, 20 Oct 97
Bonding and Structure
15
Sulfite ion, SO32Step 1. Central atom = S
Step 2. Count valence electrons
S= 6
3 x O = 3 x 6 = 18
Negative charge = 2
TOTAL = 6 + 18 + 2 = 26 eor 13 pairs
Step 3. Form sigma bonds
10 pairs of electrons are left.
18, 20 Oct 97
Bonding and Structure
O
16
Sulfite ion, SO32- (2)
Remaining pairs become lone pairs,
first on outside atoms
then on central atom.
Each atom is surrounded by an octet of electrons.
NOTE - must add formal charges (O-, S+) for complete dot diagram
18, 20 Oct 97
Bonding and Structure
17
Carbon Dioxide, CO2
1. Central atom = __C____
2. Valence electrons = _16_ or _8_ pairs
3. Form sigma bonds.
This leaves __6__ pairs.
4. Place lone pairs on outer atoms.
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Bonding and Structure
18
Carbon Dioxide, CO2 (2)
4. Place lone pairs on outer atoms.
5. To give C an octet, form DOUBLE BONDS
between C and O.
The second bonding pair forms a pi
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Bonding and Structure
() bond.
19
H2CO
Double and even
triple bonds are
commonly
observed for C,
N, P, O, and S
SO3
C2F4
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Bonding and Structure
20
Sulfur Dioxide, SO2
1. Central atom = S
2. Valence electrons = 6 + 2*6 = 18 electrons
or 9 pairs
3. Form pi () bond so that S has an octet
note that there are two ways of doing this.
OR bring in
right pair
bring in
left pair
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Bonding and Structure
21
Sulfur Dioxide, SO2
bring in
left pair
Equivalent structures
called:
OR bring in
right pair
S O
RESONANCE
STRUCTURES
S O
The proper Lewis structure
is a HYBRID of the two.
A BETTER representation of SO2
is made by forming 2 double bonds
O=S=O
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Bonding and Structure
Each atom has
- OCTET
- formal charge = 0
22
Urea (NH2)2CO
1. Number of valence electrons = 24 e2. Draw sigma bonds.
H N
Leaves 24 - 14 = 10 e- pairs.
N H
H
3. Complete C atom octet with double bond.
4. Place remaining electron pairs on oxygen
and nitrogen atoms.
O
H N
H
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N H
H
Bonding and Structure
23
Violations of the Octet Rule
Usually occurs with:
Boron
BF3
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elements of higher periods.
SF4
Bonding and Structure
24
Boron Trifluoride
Central atom = B
Valence electrons = 3 + 3*7 = 24
or electron pairs = 12
Assemble dot structure
The B atom has a share
in only 6 electrons (or 3
pairs). B atom in many
molecules is electron
deficient.
18, 20 Oct 97
Bonding and Structure
25
Sulfur Tetrafluoride, SF4
Central atom = S
Valence electrons = 6 + 4*7 = 34 eor 17 pairs.
Form sigma bonds and distribute
electron pairs.
5 pairs around the S
S
F
atom. A common
occurrence outside the
F
F
2nd period.
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Bonding and Structure
26
Formal Atom Charges
Atoms in molecules often bear a charge (+ or -).
Formal charge = Group no.
- 1/2 (no. bond electrons)
- (no. of LP electrons)
The most important dominant resonance structure
of a molecule is the one with formal charges
as close to 0 as possible.
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Bonding and Structure
27
Carbon Dioxide, CO2
At OXYGEN
6 - (1/ 2)(4) - 4 = 0
At CARBON
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4 - (1/ 2)(8) - 0 = 0
Bonding and Structure
28
Carbon Dioxide, CO2 (2)
An alternate Lewis structure is:
6 - (1/ 2)(2) - 6 = -1
C atom
charge is 0.
6 - (1/ 2)(6) - 2 = +1
AND the corresponding
resonance form
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Bonding and Structure
29
Carbon Dioxide, CO2 (3)
Which is the predominant resonance structure?
OR
Answer ?
Form without formal charges is
BETTER - no +ve charge on O
REALITY: Partial charges calculated
by CAChe molecular modeling
system (on CD-ROM).
18, 20 Oct 97
Bonding and Structure
C
C
-0.73
+1.46
-0.73
30
Boron Trifluoride, BF3
What if we form a BF double
bond to satisfy the B atom octet?
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Bonding and Structure
31
Boron Trifluoride, BF3 (2)
fc = 7 - 2 - 4 = +1
Fluorine
fc = 3 - 4 - 0 = -1
18, 20 Oct 97
Boron
To have +1 charge on F, with its very
high electron affinity is not good.
-ve charges best placed on atoms
with high EA.
Similarly -1 charge on B is bad
NOT important Lewis structure
Bonding and Structure
32
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
18, 20 Oct 97
-0.16
-0.32
Bonding and Structure
C>A>B
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