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Basic Concepts
Chapter 9
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
Valence electrons are the outer shell electrons of an
atom. The valence electrons are the electrons that
particpate in chemical bonding.
Group e- configuration # of valence e-
1A ns1 1
2A ns2 2
3A ns2np1 3
4A ns2np2 4
5A ns2np3 5
6A ns2np4 6
7A ns2np5 7
2
Lewis Dot Symbols for the Representative Elements &
Noble Gases
3
The Ionic Bond
Ionic bond: the electrostatic force that holds ions together in an
ionic compound.
Li + F Li+ F -
1s22s1s
1 22s22p5 1s2[2Ne]
[He]
1s 2s22p6
Li Li+ + e-
LiF e- + F F -
Li+ + F - Li+ F -
4
Electrostatic (Lattice) Energy
Lattice energy (U) is the energy required to completely separate
one mole of a solid ionic compound into gaseous ions.
E is the potential energy
Q+ is the charge on the cation
Q+Q -
E=k Q- is the charge on the anion
r
r is the distance between the ions
LiF 1036
r F- < r Cl-
LiCl 853 5
Born-Haber Cycle for Determining Lattice Energy
o
DHoverall = DHo1 + DHo2 + DHo3 + DHo4 + DHo5 6
7
Chemistry In Action:
Sodium Chloride: A Common
and Important Compund
8
A covalent bond is a chemical bond in which two or more
electrons are shared by two atoms.
F + F F F
7e- 7e- 8e- 8e-
Lewis structure of F2
9
Lewis structure of water single covalent bonds
H + O + H H O H or H O H
2e-8e-2e-
O C O or O C O
8e- 8ebonds
double - 8e- double bonds
N N or N N
8e-8e
triple -
bond
triple bond
10
Lengths of Covalent Bonds
Bond Lengths
11
Triple bond < Double Bond < Single Bond
12
Polar covalent bond or polar bond is a covalent
bond with greater electron density around one of the
two atoms
electron rich
electron poor
region
region e- poor e- rich
H F H F
d+ d-
13
Electronegativity is the ability of an atom to attract
toward itself the electrons in a chemical bond.
X (g) + e- X-(g)
14
The Electronegativities of Common Elements
15
Variation of Electronegativity with Atomic Number
16
Classification of bonds by difference in electronegativity
18
Writing Lewis Structures
F N F
20
Write the Lewis structure of the carbonate ion (CO32-).
Step 1 – C is less electronegative than O, put C in center
Step 2 – Count valence electrons C - 4 (2s22p2) and O - 6 (2s22p4)
-2 charge – 2e-
4 + (3 x 6) + 2 = 24 valence electrons
Step 3 – Draw single bonds between C and O atoms and complete
octet on C and O atoms.
Step 4 - Check, are # of e- in structure equal to number of valence e- ?
3 single bonds (3x2) + 10 lone pairs (10x2) = 26 valence electrons
Step 5 - Too many electrons, form double bond and re-check # of e-
H
H C O H C O
H
formal charge
on O
= 6 -2 -½ x 6 = +1
23
H 0 0 C – 4 e- 2 single bonds (2x2) = 4
C O O – 6 e- 1 double bond = 4
H 2H – 2x1 e- 2 lone pairs (2x2) = 4
12 e- Total = 12
formal charge
on O
= 6 -4 -½ x 4 = 0
24
Formal Charge and Lewis Structures
1. For neutral molecules, a Lewis structure in which there
are no formal charges is preferable to one in which
formal charges are present.
2. Lewis structures with large formal charges are less
plausible than those with small formal charges.
3. Among Lewis structures having similar distributions of
formal charges, the most plausible structure is the one in
which negative formal charges are placed on the more
electronegative atoms.
Which is the most likely Lewis structure for CH2O?
-1 +1 H 0 0
H C O H C O
H
25
A resonance structure is one of two or more Lewis structures
for a single molecule that cannot be represented accurately by
only one Lewis structure.
+ - - +
O O O O O O
- - - -
O C O O C O O C O
O O O 26
- -
Exceptions to the Octet Rule
Be – 2e-
BeH2 2H – 2x1e- H Be H
4e-
27
Exceptions to the Octet Rule
Odd-Electron Molecules
N – 5e-
NO O – 6e- N O
11e-
The Expanded Octet (central atom with principal quantum number n > 2)
F
F F
S – 6e- 6 single bonds (6x2) = 12
SF6 6F – 42e- S 18 lone pairs (18x2) = 36
48e- Total = 48
F F
F
28
Chemistry In Action: Just Say NO
29
The enthalpy change required to break a particular bond in
one mole of gaseous molecules is the bond enthalpy.
Bond Enthalpy
H2 (g) H (g) + H (g) DH0 = 436.4 kJ
Cl2 (g) Cl (g) + Cl (g) DH0 = 242.7 kJ
HCl (g) H (g) + Cl (g) DH0 = 431.9 kJ
O2 (g) O (g) + O (g) DH0 = 498.7 kJ O O
N2 (g) N (g) + N (g) DH0 = 941.4 kJ N N
Bond Enthalpies
Single bond < Double bond < Triple bond
30
Average bond enthapy in polyatomic molecules
31
Bond Enthalpies (BE) and Enthalpy changes in reactions
Imagine reaction proceeding by breaking all bonds in the reactants and
then using the gaseous atoms to form all the bonds in the products.
exothermic 32
endothermic
H2 (g) + Cl2 (g) 2HCl (g) 2H2 (g) + O2 (g) 2H2O (g)
33
Use bond enthalpies to calculate the enthalpy change for:
H2 (g) + F2 (g) 2HF (g)