Chapter 8: The Basics

of Chemical Bonding
 Electronegativity ()
 Relative attraction of atom for es in bond
 Ability of bonded atom to attract es to itself
 Quantitative basis
 Table of electronegativities - fig 8.5
 Difference in electronegativity
 = estimate of bond polarity
  = |1  2|
 Ex. N—H Si—F
 + + 

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

Electronegativity Table

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

 Learning Check
 Calculate the bond polarity of the following
 HCl (H)~2 (Cl)~3  = 3 – 2 = 1

 CO (C)~2.5 (O)~3.5  = 3.5 – 2.5 = 1

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

 Your Turn!
Which of the following species has the least
polar bond?

A. HCl
B. HF
C. HI
D. HBr

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

 Lewis Structures
 Many nonmetals form more than 1 covalent bond

C N O
Needs 4 e-’s Needs 3 e-’s Needs 2 e-’s
Forms 4 bonds Forms 3 bonds Forms 2 bonds
H
H N H O H
H C H
H H
H H
H C H H N H O H
H H H
methane ammonia water
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E
 Double Bonds
 2 pairs of e–’s shared between 2 atoms
Ex. CO2

O C O O C O O C O
Triple bond
 3 pairs of e–’s shared between 2 atoms
Ex. N2

N N N N N N
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E
 Your Turn!
Which species is most likely to have multiple
bonds ?
A. CO
B. H2O
C. PH3
D. BF3
E. CH4

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

 Drawing Lewis Structures
 Not all molecules obey the Octet Rule.
 Holds rigorously for 2nd row elements like C, N,
O, and F
 B and Be sometimes have less than octet
BeCl2, BCl3
 2nd row can never have more than 8 e’s
 3rd row and below, atoms often exceed octet
 Why?
 n = 3 shell can have up to 18 e’s as now
have d orbitals in valence shell

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

Method for Drawing Lewis Structure

1. Decide how atoms are bonded

 Skeletal structure = arrangement of atoms.
 Central atom
 Usually given first
 Usually least electronegative
2. Count all valence es. (All atoms)
3. Place 2 es between each pair of atoms
 Draw in single bonds

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

Method for Drawing Lewis Structure
4. Complete octets of terminal atoms
(atoms attached to central atom) by
adding es in pairs
5. Place any remaining e’s on central atom
in pairs
6. If central atom does not have octet
 Form double bonds
 If necessary, form triple bonds

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

 Ex. N2F2
2 N = 2  5e = 10 e Skeletal Structure
2F = 2  7e = 14 e
Total = 24 e F N N F
single bonds  6 e Complete terminal
18 e atom octets
F lone pairs  12 e
F N N F
6 e
N electrons  6 e Put remaining es on
0 e central atom

F N N F
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E
 Ex. N2F2

 Not enough electrons to complete N octets

 Must form double bond between N’s to
satisfy both octets.

F N N F F N N F

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

 Ex. SiF4 Skeletal Structure
F
1 Si = 1  4e = 4 e
 

4F = 4  7e = 28 e F Si F
Total = 32 e
single bonds  8 e F
24 e Complete terminal
atom octets
F lone pairs  24 e
0 e F
F Si F
F
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E
 Ex. PCl5
1 P = 1  5 e = 5 e Cl
5 Cl = 5  7e = 35 e Cl Cl
Total = 40 e
P
single bonds  10 e Cl Cl
30 e
Cl lone pairs  30 e
Cl
0 e Cl Cl
P
 P has 10 e Cl Cl
 OK as 3rd row element
 Can expand its shell
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E
 Ex. BBr3
Br
1 B = 1  3 e = 3 e 
3 Br = 3  7e = 21 e B
Total = 24 e Br Br
single bonds  6 e
18 e
Br lone pairs  18 e
Br
0 e

 B has only 6 e B
 Does not form double bond Br Br
 Has incomplete octet
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E
 Ex. H2SO4 O

1 S = 1  6e = 6 e H O S O H
4 O = 4  6e = 24 e O
2 H = 2  1e = 2 e
O
Total = 32 e
single bonds  12 e H O S O H
20 e O
O lone pairs  20 e
O
0 e
H O S O H
 n=3, has empty d orbitals
 Could expand it's octet O
 Could write structure with double bonds.
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E
 Bond Order, Bond Length and Bond
Energy
Greater Bond Order = Greater e density
 Nuclei held together more tightly
 Larger bond energy, D
 Larger D means
 Nuclei drawn closer together
 Shorter bond length
 As bond order , bond length , and
bond energy 
 Assumes comparing bonds between same 2
elements
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E
 Formal Charge (FC)
 Apparent charge on atom
 Does not represent real charges
FC = # valence e  # lone pair e  ½ (#
bonding e)
FC = # valence e  [# bonds to an atom + #
unshared e ]
 Indicate Formal charges by placing them in
circles around atoms

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

FC = #valence e  [#bonds to atom
+ # unshared e ]
-1 Structure 1
O FCS = 6  (4 + 0) = 2
+2 FCH = 1  (1 + 0) = 0
H O S O H
FCO(s) = 6  (1 + 6) =  1
O -1 FCO(d) = 6  (2 + 4) = 0

O Structure 2
FCS = 6  (6 + 0) = 0
H O S O H
FCH = 1  (1 + 0) = 0
O FCO(s) = 6  (2 + 4) = 0
Jespersen/Brady/Hyslop
FC Molecular=Nature
Chemistry: The O(d)
6 (2 + 4) = 0
of Matter, 6E
 H2SO4
 No formal charges on any atom in Structure 2
Conclusion:
 When several Lewis Structures are possible
 Those with smallest formal charges
 Most stable
 Preferred
Most Stable Lewis Structure
1. Least number of FC's best
2. All FC  1
3. Any negative FC on most electronegative element
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E
Can Use FC to Explain B Chemistry
 BCl3
 Why doesn’t a double bond form here?
 FCB = 3 – 0 – 3 = 0
 FCCl = 7 – 6 – 1 = 0
 All FC's = 0 so stable, doesn't need to form
double bond

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

 Your Turn!
What is the formal charge on Xe for the
following ?
O O

O Xe O O Xe O

O O

A. +2, +4
B. +2, +3
C. +4, 0
D. +4, +2
D is the answer
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E
 Resonance: When Single Lewis
Structure Fails

O
N = 3 O = 3.5
N
1 N = 1  5e = 5 e
 

3 O = 3  6e = 18 e
O O
1 charge = 1 e
Total = 24 e

O
single bonds  6 e
18 e N
O lone pairs 18 e O O
0 e
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E
 Ex. NO3 O 
 Lewis structure predicts
1 bond shorter than N
other 2 O O
Experimental observation:
 All 3 N—O bond lengths are same
 All shorter than N—O single bonds
 Have to modify Lewis Structure
 e can't distinguish O atoms
 Can write 2 or more possible structures
simply by moving where e are
 Changing placement of e
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E
What are Resonance Structures?
 Multiple Lewis Structures for single molecule
 No single Lewis structure is correct
 Structure not accurately represented by any 1 Lewis
Structure
 Actual structure = "average" of all possible structures
 Double headed arrow between resonance structures
used to denote resonance

O  1 O  1
O 
+1
+1
N N+1 N
O O O O O O
1
1 1 1
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E
 Three Equivalent Resonance
Structures
1
O  O
1  O 

C C C
O O O O O O
1 1 1 1
 All have same net formal charges on C and O’s
 FC = 1 on singly bonded O’s
 FC = O on doubly bond O and C

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

 Ex. NCO
1
FCN = 5 – 2 – 3 = 0 
FCC = 4 – 0 – 4 = 0 N C O
FCO = 6 – 6 – 1 = –1 Best

1
FCN = 5 – 4 – 2 = –1

FCC = 4 – 0 – 4 = 0 N C O OK
FCO = 6 – 4 – 2 = 0

FCN = 5 – 6 – 1 = –2 2 +1
Not

FCC = 4 – 0 – 4 = 0 N C O Accept-
FCO = 6 – 2 – 3 = able
+1 Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E
 Learning Check
Ex. What is the best Lewis Structure for
HClO4?

XeF4

I3–

BrF5

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E