Chemical Bonding -- Lewis Theory (Chapter 9)

Ionic Bonding

1. Ionic Bond
Electrostatic attraction of positive (cation) and negative (anion) ions

e- transfer
Neutral Atoms cation + anion
(IE and EA)

(Lattice Energy)
Ionic Compound

Lattice Energy: energy released when gaseous ions combine to form

crystalline solid (an ionic compound)

e.g., LE of NaCl is 787 kJ/mole:

Na+ (g) + Cl- (g) → NaCl (s) + 787 kJ

2. Octet Rule
In forming ionic compounds, atoms tend to gain or lose electrons
in order to achieve a stable valence shell electron configuration of
8 electrons.

Group I metals → +1 cations (Li+, Na+, etc.)

Group II metals → +2 cations (Mg2+, ca2+, etc.)

Al (group III) → Al3+

Group VII (17) → -1 anions (F-, Cl-, Br-, etc.)

Group VI (16) → -2 anions (O2-, S2-, etc.)

Group V (15) → -3 anions (N3-, P3-)

e.g., Na 2s2 2p6 3s1 → Na+ 2s2 2p6 {∼ Ne}

Cl 3s2 3p5 → Cl- 3s2 3p6 {∼ Ar}

Page 1
3. Lewis Symbols
simple notation for showing number of valence electrons

Cl O
group VII (7 valence e-) group VI (6 valence e-)

3s2 3p5 2s2 2p4

.. ..
: Cl . .O.
.. ..

e.g., Use Lewis Symbols to illustrate the formation of a compound of sodium

and sulfur

Na2S Na+ combined with S2-

.. .. 2-
Na . . S. . Na +
+
.. + 2 Na .. :
:S

Covalent Bonding

1. Covalent Bond Formation

results from sharing of one or more pairs of electrons between 2 atoms

Examples:

H. + H. H:H or H H
.. .. ..
H. + : F... H : F..: or H F..:

2. Octet Rule -- for covalent bonding

In forming covalent bonds, atoms tend to share sufficient
electrons so as to achieve a stable outer shell of 8 electrons
around both atoms in the bond.

Page 2
 Examples:

. H
.. H
.C. 4 H. H :C
.. : H H C H
+ or
.
H H

.. ..
.N. + 3 H. H N H
.
H unshared e- pairs
or "lone pairs"
.. ..
.O. 2 H. H O
.. H
+
..

3. Multiple Bonds -- "double" and "triple" bonds

double bond: sharing of 2 pairs of electrons between two atoms
triple bond: sharing of 3 pairs of electrons between two atoms

Bond Energy / Bond Strength

Type of Bond: single double triple

Bond Order: 1 2 3
Bond Distance

Examples: O2 { O=O double bond }

N2 { N≡N triple bond }

CO2 { two C=O double bonds }

Page 3
4. Coordinate Covalent Bond
Both electrons in the bond formally come from the same atom.
(Once formed, however, the bond is just like any other covalent bond!)

H H H H
H N: + B H H N: B H
H H H H

H H
or H N B H
H H

5. Electronegativity and Bond Polarity

electronegativity tendency of an atom in a molecule to attract
electrons to itself

Electronegativity Increases

Periodic Table

e.g., Cl is more electronegative than H, so there is

partial charge separation in the H-Cl bond:

δ+ δ−
H Cl or H Cl
the H-Cl bond is described as "polar" and is said to have a "dipole"

the entire HCl molecule is also polar as a result

more complex molecules can be polar or nonpolar, depending on

their 3-D shape (Later)

Page 4
Lewis Electron Dot Formulas

1. General Procedure -- stepwise process

• Write the skeletal structure (which atoms are bonded?)

• Count all valence electrons (in pairs)

• Place 2 electrons in each bond

• Complete the octets of the terminal atoms

• Put any remaining electron pairs on the central atom, or

• Use multiple bonds if needed to complete the octet of the central atom

• Show formal charges and resonance forms as needed

Apply the OCTET RULE as follows:

• H never has more than 2 electrons (i.e., one bond)
• 2nd row elements (e.g., C, N, O) almost always have an octet and
never have more than 8 electrons (sometimes Boron has only 6)
• 3rd row and higher elements can have more than 8 electrons but only
after the octets of any 2nd row elements are completed

2. Formal Charge -- the "apparent" charge on an atom in a covalent bond

= (# of valence e- in the isolated atom) − (# of bonds to the atom)

− (# of unshared electrons on the atom)

{ minimize formal charges whenever possible }

Write Lewis Dot Formulas: NH3 NH4+ SF2 SF4

Page 5
3. Resonance
When multiple bonds are present, a single Lewis structure may not
adequately describe the compound or ion -- occurs whenever there is
a "choice" of where to put a multiple bond.

e.g., the HCO2- ion is a "resonance hybrid" of two "contributing

resonance structures"

.. - .. -
O: : O : O-
H C H C

.. : O-
:O .. :
O

the C-O bond order is about 1.5 (average of single and double bonds)

Examples

Write Lewis Electron Dot Structures (including formal charges and/or

resonance as needed) for the following compounds and ions.

PF3 HCN SF5- NO2- SOCl2 O3

HNO3 H2CO N3-

Page 6
Bond Energies and Heats of Reaction (∆
∆H)

Bond Energy is the energy required to break a chemical bond.

Tabulated values (Table 9.3) are average bond energies

in units of kJ / mole.

Bond-breaking is endothermic, bond-making is exothermic.

∆H for a reaction can be estimated from bond energies as follows.

(Counting ALL bond energies as positive values!)

∆H°° ≈ ∑ BE (bonds broken) - ∑ BE (bonds formed)

Problem
Use data in Table 9.3 to estimate ∆H° for the reaction.
CH2=CH2 + H2O → CH3-CH2-OH

Bonds Broken Bonds Formed

C=C 612 C-C 348
H-O 463 C-H 412
∑ = 1,075 C-O 360
∑ = 1,120
∴ ∆H° ≈ 1,075 - 1,120 ≈ - 45 kJ/mole

This estimate compares well with the value calculated from

Standard Heats of Formation (Chapter 6).

Use tabulated ∆H°f values from textbook:

∆H° = ∑ ∆H°f (products) - ∑ ∆H°f (reactants)

∆H° = (- 278) - [ (+ 51.9) + (- 285.9) ] = - 43 kJ/mole

Page 7