Principles of General Chemistry, 2nd ed. By M.

Silberberg
Chemistry, 8th ed. by W. Whitten, R. Davis, R., M. L. Peck, and G. Stanley.
to be discussed...
• Ionic Bonds
• Covalent Bonds
Chemical Bonding •
•
Metallic Bonds
Bond Lengths and Bond Energies
• Lewis Formulas for Molecules and Polyatomic Ions
• The Octet Rule
• Formal Charges
• Limitations of the Octet Rule
• Resonance
• Polar and Nonpolar Covalent Bonds
• Dipole Moments

Chemical Bonding Chemical Bonding

o Ionic bonding results from electrostatic
• Attractive forces that hold atoms attractions among ions, which are formed by
together in compounds are called the transfer of one or more electrons from one
chemical bonds. atom to another.

o Covalent bonding results from sharing one or

• The electrons involved in bonding are more electron pairs between two atoms.
usually those in the outermost (valence)
shell.
o Metallic bonding results from a sea of free
flowing electrons in a substance

Chemical Bonding Chemical Bonding

1. Metal with nonmetal:

electron transfer and ionic bonding

2. Nonmetal with nonmetal:

electron sharing and covalent bonding

3. Metal with metal:

electron pooling and metallic bonding
Comparison of Ionic and Covalent Compounds Comparison of Ionic and Covalent Compounds

covalent
property Ionic compound covalent
compound property Ionic compound
compound
gases, liquids, or
Melting usually solids Conductivity
solids (~ < 300oC) conduct electricity
point (~> 400oC) in molten do not conduct
(contain mobile electricity
solids and
Solubility in ions)
liquids
polar generally soluble generally insoluble
solvents Conductivity
generally conduct poor conductors
Solubility in in aqueous
electricity of electricity
nonpolar generally insoluble generally soluble solutions
solvents

Lewis Dot Formulas of Atoms Lewis Dot Formulas of Atoms

• is a convenient bookkeeping method for tracking • elements that are in the same periodic group
valence electrons have the same Lewis dot structures.
- electrons that are transferred or involved in chemical
bonding (represented by dots around the element
• for main group elements
- the group number = number of valence electrons

nitrogen, N, is in Group 5A and therefore, has 5 valence electrons

. . .
:

:N . . N. . . N: . N.
. .
:

Depicting Ionic Bond Formation Depicting Ionic Bond Formation

PROBLEM: PROBLEM:
Use partial orbital diagrams and Lewis symbols to Use partial orbital diagrams and Lewis symbols to
depict the formation of LiF depict the formation of Na2O

SOLUTION: SOLUTION:
Depicting Ionic Bond Formation Formation of Ionic Compound

Be(s) + F2(g) →BeF2(g) • Ionic compounds form

extended three
2s 2p 2s 2p dimensional arrays of
Be [He] ↑↓ → Be2+ oppositely charged ions.
F [He] ↑↓ ↑↓ ↑↓ ↑ → F- ↑↓ ↑↓ ↑↓ ↑↓ • Ionic compounds have
high melting points
because the coulomb
force, which holds ionic
compounds together, is
strong.

Formation of Ionic Compound Formation of Ionic Compound

• Coulomb’s Law describes the attraction of • Small ions with high ionic charges have large
positive ions for negative ions due to the Coulombic forces of attraction.
opposite charges.

F∝
(q )(q )
+ −

d2 Al 32+ O32- > Ca 2+ O2- > K1+ Cl-

where
F = force of attraction between ions
q = magnitude of charge on ions
d = distance between center of ions

Some Properties of Ionic Compound Some Properties of Ionic Compound

 Covalent Bonding
Some Properties of Ionic Compound
•If the atoms share

•2 electrons a single covalent bond is formed.

•4 electrons a double covalent bond is formed.
•6 electrons a triple covalent bond is formed.

The attraction between the electrons is still

electrostatic in nature. The atoms have a lower
potential energy when bound.

Covalent Bonding Bond Length & Bond Energy

• Representation of • for any covalent bond there is an
the formation of an internuclear distance where the attractive
H2 molecule from H and repulsive forces balance
atoms.
this distance is the bond length

• We can use Lewis • at the bond length, the combination of

dot formulas to bonded atoms is more stable than the
show covalent bond separated atoms by an amount of energy.
formation.
this energy difference is the bond
energy.

Bond Bond Length & Bond Energy

Length
& Bond
Energy
Bond Length & Bond Energy Bond Length & Bond Energy
PROBLEM: Rank the bonds in each set in order of decreasing bond length
and bond strength:

(a) S─F, S─Br, S─Cl (b) C = O, C─O, C O

SOLUTION:
(a) Atomic size increases going down a group.

Bond length: S─Br > S─Cl > S─F Bond strength: S─F > S─Cl > S─Br

(b) Using bond orders we get,

• bond length: single > double > triple Bond length: C─O > C = O > C O Bond strength: C O > C = O > C─O
• bond energy: triple > double > single

Writing Lewis Formula : Writing Lewis Formula :

The Octet Rule
• The octet rule states that representative
elements usually attain stable noble gas
electron configurations in most of their
compounds.
• Lewis dot formulas are based on the octet rule.
• We need to distinguish between bonding (or
shared) electrons and nonbonding (or
unshared or lone pairs) of electrons.
The Octet Rule
• N - A = S rule
• N = number of electrons needed to achieve a noble gas
configuration.
– N usually has a value of 8 for representative elements.
– N has a value of 2 for H atoms.
• A = number of electrons available in valence shells of the
atoms.
– A is equal to the periodic group number for each element.
– A is equal to 8 for the noble gases.
• S = number of electrons shared in bonds.
• A-S = number of electrons in unshared, lone, pairs.

Writing Lewis Formula : Writing Lewis Formula :

The Octet Rule The Octet Rule
i. Count the total number of electrons ii. Count the total number of available or
needed to achieve octet rule: valence electrons:

Total needed electrons = Total valence =

Σ (# atoms x # needed e- for the atom) Σ (# atoms x # valence e- for the atom)

e.g.: H2 O 2H: 2x2 =4 e.g.: H2 O 2H: 2x1 =2

1O: 1x8 =8 1O: 1x6 =6
total needed = 12 total valence = 8
Writing Lewis Formula :
The Octet Rule
iii. Apply the N-A = S rule
N = Total # of needed electrons
A = Total # of available electrons
N–A=S 12 – 8 = 4
S = Total # of shared electrons
4 electrons shared = two bonds
Writing Lewis Formula :
The Octet Rule
iv. Determine the central atom and
connect the atoms using the calculated
= 12
number of bonds
=8
• The central atom in a molecule or polyatomic ion is
determined by:
– The atom that requires the largest number of electrons
to complete its octet goes in the center.
– For two atoms in the same periodic group, the less
electronegative element goes in the center.

Writing Lewis Formula : Writing Lewis Formula :

The Octet Rule
v. Calculate the remaining electrons
after the bonding process (Remember:
1 bond = 2 e- shared). Subtract the # of
e- used in the bonds from the calculated
total valence electron
The Octet Rule
vi. Distribute the remaining electrons:
“Outside going In”
-This is followed because the atoms at the periphery are
usually the most electronegative
- If H atoms at the periphery, no need to add electrons to
them

total valence
8
– 2 x # of bonds
- 4
remaining e- = 4

Writing Lewis Formula : Writing Lewis Formula :

The Octet Rule The Octet Rule
vii. Lastly, check for if the octet rule is NF3
followed and the lowest formal CCl2F2
charges (next slides) are considered.
:

: F: : F:
:

:Cl :
:

N
: :
: :

:Cl C F:

: F: :F:
:
:
Formal Charge Formal Charge

• The formal charge is the hypothetical
charge on an atom in a molecule or
polyatomic ion.
• Calculation of a formal charge on a
molecule is a mechanism for determining
correct Lewis structures
• The best Lewis structures will have formal
charges on the atoms that are zero or
nearly zero.
Rules for Assigning Formal Charge
1. Formal Charge = group number – (number
of bonds + number of unshared e-)
2. a. The formal charges of all atoms must sum
to 0 in molecules.
b. The formal charges must sum to the ion’s
charge for a polyatomic ion.

Formal Charge Writing Lewis Formulas for

Polyatomic Ions
e.g. Consider nitrosyl chloride, NOCl • for ions we must adjust the calculation of total
valence electrons involved
Cl N O Cl N O • Add the numerical value of charge if negative (anion)
• Subtract if positive (cation)

Cl : 7 – (2+4) = +1 Cl : 7 – (1+6) = 0
N: 5 – (3+2) = 0 N: 5 – (3+2) = 0 e.g.: 3H : 3 x 1 = 3
O: 6 – (2+4) = 0 Hydronium 1O : 1 x 6 = 6
O: 6 – (1+6) = -1
cation, H3O+ positive cation = - (+1)
This is the most probable total valence = 8
structure

Writing Lewis Formulas for Writing Lewis Formulas for

Polyatomic Ions Polyatomic Ions

• total needed = (3x2) + (1x8) = 14 • then, calculate the remaining electrons

• S = 6 = 3 bonds not included in bond formation
• again connect the atoms using three (nonbonding electrons)
bonds
REMEMBER: single bonds = 2 e- shared
total valence
8
– 3 x # of bonds
- 6
remaining e- = 2
Writing Lewis Formulas for Exemptions to Octet Rule
Polyatomic Ions
1. The covalent compounds of Be.
• distribute the remaining (nonbonding) 2. The covalent compounds of the IIIA Group.
electrons 3. Species which contain an odd number of
– again, outside going in, except for electrons.
hydrogen (H) 4. Species in which the central element must
have a share of more than 8 valence
electrons to accommodate all of the
substituents.
5. Compounds of the d- and f-transition metals.

Exemptions to Octet Rule Exemptions to Octet Rule

• In those cases where the octet rule does • Reduced Octet

not apply, the substituents attached to the e.g. BBr3
central atom nearly always attain noble • Expanded Octet
gas configurations. e.g. PCl5

• The central atom does not have a noble • Odd-electron molecules

gas configuration but may have fewer than e.g. NO2
8 or more than 8.

Resonance Resonance

• Consider SO3; there are three possible lewis • Resonance is a flawed method of
structures (*all atoms have zero formal charges) representing molecules.
• The double bond can be placed in one of three places. – There are no single or double bonds in
·· ·· ·· ··
SO3.
·· O S O ·· ·· O S O ·· ·· O S O ··
·· ·· ·· ·· ·· ·· • In fact, all of the bonds in SO3 are equivalent.
·· O · ·· O ·· ·· O ··
·· · ··
• The best Lewis formula of SO3 that can
• When two or more Lewis formulas are necessary to show the be drawn is:
bonding in a molecule, we must use equivalent resonance
structures to show the molecule’s structure.
• Double-headed arrows are used to indicate resonance
formulas.
Bond Polarity
• Covalent bonds in which the electrons
are shared equally are designated as
nonpolar covalent bonds.
– Nonpolar covalent bonds have a
symmetrical charge distribution.
H .. H or H H
·· N ·· ·· ·· N ·· or ·· N N ··
Bond Polarity
• Shown below is an electron density map
of HF.
• Polar molecules have a separation of
centers of negative and positive charge,
an asymmetric charge distribution.
Bond Polarity
• Polar molecules can be attracted by
magnetic and electric fields.
Bond Polarity
• Covalent bonds in which the electrons
are not shared equally are designated as
polar covalent bonds
– Polar covalent bonds have an asymmetrical
charge distribution
H F
Electroneg ativities 2.1
14244.0
3
1.9
Difference = 1.9 very polar bond
Electron Density Maps
Bond Polarity
Dipole Moment
• Molecules whose centers of positive and
negative charge do not coincide, have an
asymmetric charge distribution, and are polar.
– These molecules have a dipole moment.
• The dipole moment has the symbol µ.
• µ is the product of the distance,d, separating
charges of equal magnitude and opposite sign,
and the magnitude of the charge, q.
Dipole Moment Dipole Moment

• Molecules that have a small separation of • There are two conditions that must be true for
charge have a small µ. a molecule to be polar.
• Molecules that have a large separation of
1. There must be at least one polar bond
charge have a large µ. present or one lone pair of electrons.
• For example, HF and HI: 2. The polar bonds, if there are more than one,
a a and lone pairs must be arranged so that
their dipole moments do not cancel one
δ H - Fδ
+ -
δ H -Iδ -
+
another.
1.91 Debye units 0.38 Debye units

questions?

“Diamond and graphite are

nothing but carbon.

But only the material that was subjected to

tremendous temperatures and pressures exude the
highest degree of beauty and worth.”
worth.”