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Chemical Bonding

Principles of General Chemistry, 2


nd
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
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
Attractive forces that hold atoms
together in compounds are called
chemical bonds.
The electrons involved in bonding are
usually those in the outermost (valence)
shell.
o Ionic bonding results from electrostatic
attractions among ions, which are formed by
the transfer of one or more electrons from one
atom to another.
o Covalent bonding results from sharing one or
more electron pairs between two atoms.
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
Chemical Bonding
Comparison of Ionic and Covalent Compounds
generally soluble generally insoluble
Solubility in
nonpolar
solvents
generally insoluble generally soluble
Solubility in
polar
solvents
gases, liquids, or
solids (~ < 300
o
C)
usually solids
(~> 400
o
C)
Melting
point
covalent
compound
Ionic compound property
Comparison of Ionic and Covalent Compounds
poor conductors
of electricity
generally conduct
electricity
Conductivity
in aqueous
solutions
do not conduct
electricity
conduct electricity
(contain mobile
ions)
Conductivity
in molten
solids and
liquids
covalent
compound
Ionic compound property
is a convenient bookkeeping method for tracking
valence electrons
- 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
Lewis Dot Formulas of Atoms
nitrogen, N, is in Group 5A and therefore, has 5 valence electrons
N :
.
.
.
:
N
. .
.
.
N:
.
.
:
N
. .
.
Lewis Dot Formulas of Atoms
elements that are in the same periodic group
have the same Lewis dot structures.
Depicting Ionic Bond Formation
PROBLEM:
Use partial orbital diagrams and Lewis symbols to
depict the formation of LiF
SOLUTION:
Depicting Ionic Bond Formation
PROBLEM:
Use partial orbital diagrams and Lewis symbols to
depict the formation of Na
2
O
SOLUTION:
Be
(s)
+ F
2(g)
BeF
2(g)
2s 2p 2s 2p
Be [He] Be
2+
F [He] F
-

Depicting Ionic Bond Formation
Ionic compounds form
extended three
dimensional arrays of
oppositely charged ions.
Ionic compounds have
high melting points
because the coulomb
force, which holds ionic
compounds together, is
strong.
Formation of Ionic Compound
Coulombs Law describes the attraction of
positive ions for negative ions due to the
opposite charges.
( )( )
ions of center between distance d
ions on charge of magnitude q
ions between attraction of force F
where

d
q q
F
2
=
=
=

+
Formation of Ionic Compound
Small ions with high ionic charges have large
Coulombic forces of attraction.
- 1 - 2 2 - 2
3
3
2
Cl K O Ca O Al
+ + +
> >
Formation of Ionic Compound
Some Properties of Ionic Compound Some Properties of Ionic Compound
Some Properties of Ionic Compound
Covalent Bonding
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
Representation of
the formation of an
H
2
molecule from H
atoms.
We can use Lewis
dot formulas to
show covalent bond
formation.
Bond Length & Bond Energy
for any covalent bond there is an
internuclear distance where the attractive
and repulsive forces balance
this distance is the bond length
at the bond length, the combination of
bonded atoms is more stable than the
separated atoms by an amount of energy.
this energy difference is the bond
energy.
Bond
Length
& Bond
Energy
Bond Length & Bond Energy
Bond Length & Bond Energy
bond length: single > double > triple
bond energy: triple > double > single
Bond Length & Bond Energy
SOLUTION:
PROBLEM: Rank the bonds in each set in order of decreasing bond length
and bond strength:
(a) SF, SBr, SCl (b) C = O, CO, C O
(a) Atomic size increases going down a group.
Bond length: SBr > SCl > SF Bond strength: SF > SCl > SBr
(b) Using bond orders we get,
Bond length: CO > C = O > C O Bond strength: C O > C = O > CO
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.
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 :
The Octet Rule
i. Count the total number of electrons
needed to achieve octet rule:
Total needed electrons =
(# atoms x # needed e
-
for the atom)
e.g.: H
2
O
2 H : 2 x 2 = 4
1 O : 1 x 8 = 8
total needed = 12
Writing Lewis Formula :
The Octet Rule
ii. Count the total number of available or
valence electrons:
Total valence =
(# atoms x # valence e
-
for the atom)
e.g.: H
2
O
2 H : 2 x 1 = 2
1 O : 1 x 6 = 6
total valence = 8
Writing Lewis Formula :
The Octet Rule
iii. Apply the N-A = S rule
N = Total # of needed electrons = 12
A = Total # of available electrons = 8
N A = S 12 8 = 4
S = Total # of shared electrons
4 electrons shared = two bonds
Writing Lewis Formula :
The Octet Rule
Writing Lewis Formula :
The Octet Rule
iv. Determine the central atom and
connect the atoms using the calculated
number of bonds
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 :
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
total valence 8
2 x # of bonds - 4
remaining e
-
= 4
Writing Lewis Formula :
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
Writing Lewis Formula :
The Octet Rule
vii. Lastly, check for if the octet rule is
followed and the lowest formal
charges (next slides) are considered.
Writing Lewis Formula :
The Octet Rule
NF
3
N
F F
F
:
: :
: :
::
:
:
:
C
Cl
Cl F
F
:
:
:
:
:
:
:
:
: :
:
:
CCl
2
F
2
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.
Formal Charge
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 ions
charge for a polyatomic ion.
Formal Charge
Formal Charge
Cl N O Cl N O
Cl : 7 (2+4) = +1
N: 5 (3+2) = 0
O: 6 (1+6) = -1
Cl : 7 (1+6) = 0
N: 5 (3+2) = 0
O: 6 (2+4) = 0
e.g. Consider nitrosyl chloride, NOCl
This is the most probable
structure
for ions we must adjust the calculation of total
valence electrons involved
Add the numerical value of charge if negative (anion)
Subtract if positive (cation)
Writing Lewis Formulas for
Polyatomic Ions
e.g.:
Hydronium
cation, H
3
O
+
3H : 3 x 1 = 3
1O : 1 x 6 = 6
positive cation = - (+1)
total valence = 8
Writing Lewis Formulas for
Polyatomic Ions
total needed = (3x2) + (1x8) = 14
S = 6 = 3 bonds
again connect the atoms using three
bonds
Writing Lewis Formulas for
Polyatomic Ions
then, calculate the remaining electrons
not included in bond formation
(nonbonding electrons)
REMEMBER: single bonds = 2 e- shared
total valence 8
3 x # of bonds - 6
remaining e
-
= 2
Writing Lewis Formulas for
Polyatomic Ions
distribute the remaining (nonbonding)
electrons
again, outside going in, except for
hydrogen (H)
1. The covalent compounds of Be.
2. The covalent compounds of the IIIA Group.
3. Species which contain an odd number of
electrons.
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
In those cases where the octet rule does
not apply, the substituents attached to the
central atom nearly always attain noble
gas configurations.
The central atom does not have a noble
gas configuration but may have fewer than
8 or more than 8.
Exemptions to Octet Rule Exemptions to Octet Rule
Reduced Octet
e.g. BBr
3
Expanded Octet
e.g. PCl
5
Odd-electron molecules
e.g. NO
2
Consider SO
3
; there are three possible lewis
structures (*all atoms have zero formal charges)
The double bond can be placed in one of three places.
When two or more Lewis formulas are necessary to show the
bonding in a molecule, we must use equivalent resonance
structures to show the molecules structure.
Double-headed arrows are used to indicate resonance
formulas.
O S
O
O

O S
O
O

O S
O
O

Resonance Resonance
Resonance is a flawed method of
representing molecules.
There are no single or double bonds in
SO
3
.
In fact, all of the bonds in SO
3
are equivalent.
The best Lewis formula of SO
3
that can
be drawn is:
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

N N

or
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
bond polar very 1.9 Difference
4.0 2.1 ativities Electroneg
F H
1.9
=
43 42 1
Electron Density Maps Electron Density Maps Electron Density Maps Electron Density Maps
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 Bond Polarity
Polar molecules can be attracted by
magnetic and electric fields.
Bond Polarity
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 .
is the product of the distance,d, separating
charges of equal magnitude and opposite sign,
and the magnitude of the charge, q.
Dipole Moment
Molecules that have a small separation of
charge have a small .
Molecules that have a large separation of
charge have a large .
For example, HF and HI:
units Debye 0.38 units Debye 1.91
I - H F - H

- -

+ +
a a
Dipole Moment
There are two conditions that must be true for
a molecule to be polar.
1. There must be at least one polar bond
present or one lone pair of electrons.
2. The polar bonds, if there are more than one,
and lone pairs must be arranged so that
their dipole moments do not cancel one
another.
Dipole Moment
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