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Chapter 3
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Chemical Bonding
3.0 Introduction
3.1 Lewis Structure
3.2 Ionic Bond
3.3 Covalent Bond
3.4 Molecular Geometry and VSEPR theory
3.5 Valence bonds theory and hybridizations
3.6 Intermolecular Forces
3.7 Metallic Bonding
2
LiF
1s22s22p5
Li+ + e-
Li
e- +
Li+ +
1s2 1s22s22p6
[He]
[Ne]
F -
F -
Li+ F -
H + H H:H or H-H
6
7e-
F F
7e-
8e- 8e-
Lewis structure of F2
lone pairs
lone pairs
F F
lone pairs
7
O +
H O H
or
or
double bonds
or
triple bond
8
11
Topic
13
N or N or N or N
19
Example 1
Write the Lewis structure for nitrogen trifluoride (NF3) in which
all three F atoms are bonded to the N atom.
Example 1
Solution We follow the preceding procedure for writing Lewis
structures.
Step 1:
Step 2:
Example 1
Step 3:
Because this structure satisfies the octet rule for all the atoms,
step 4 is not required.
Check Count the valence electrons in NF3 (in bonds and in
lone pairs). The result is 26, the same as the total number of
valence electrons on three F atoms (3 7 = 21) and one N
atom (5).
Example 2
Write the Lewis structure for nitric acid (HNO3) in which the
three O atoms are bonded to the central N atom and the
ionizable H atom is bonded to one of the O atoms.
Example 2
Solution We follow the procedure already outlined for writing
Lewis structures.
Step 1:
Step 2:
Example 2
Step 3:
Step 4:
Topic
3.2 Ionic Bond
Example:
Li+ 1s2 + F-
1s22s22p6
Orbital diagram
Li
+
1s
2s
Li+
2p
1s
2s
2p
1s
2s
2p
F-
1s
2s
2p
Formula
Li2O
Na
2Na+
2O
+
Na
Cl
Ca
Ca2+
CaCl2
Cl
Lattice Energy =
910 kJ/mol
Lattice Energy =
3414 kJ/mol
NaCl (s)
NaCl (liquid)
41
CHECKPOINT 3
Which ionic compound below has the highest
melting point?
KBr
KBr (734 C)
CaCl2
CaCl2 (772 C)
MgF2
MgF2 (1261 C)
-+ +- -+ +- -+ +- -+ +
- -+ +- -+ +- -+ +- -+ +- + - + - + - + - +
- + - + - + - + + +
-
Example 4
Strategy We use electroneutrality as our guide in writing
formulas for ionic compounds, that is, the total positive charges
on the cations must be equal to the total negative charges
on the anions.
Solution The Lewis dot symbols of Al and O are
Example 4
Thus, the simplest neutralizing ratio of Al3+ to O2 is 2:3; two
Al3+ ions have a total charge of +6, and three O2 ions have a
total charge of 6. So the empirical formula of aluminum oxide
is Al2O3, and the reaction is
bonding pairs
Electrons that are not shared by atoms but
belong to a particular atom are called lone pairs
or nonbonding pairs
Bonding pairs
.
.
.
.
.
.
.. O .... S .. O ..
..
Lone pairs
H only duet
F
F
H O
H
H O H
O
O
N
N
Step 1
Atom
placement
Step 3
Sum of
valence e-
Remaining
valence e-
Step 4
Lewis
structure
Atom
placement
Sum of
valence e-
Remaining
valence eLewis
structure
1 x N = 1 x 5 = 5e3 x F = 3 x 7 = 21 eTotal
= 28 e-
SOLUTION:
C2H4 has 2(4) + 4(1) = 12 valence e-. H can have only one bond per
atom.
H C N
H always terminal
H O N O
N is central
not H
N=5
H=1
O3 = 36 = 18
Total = 24 e
..
..
..
..
..
..
..
O
..
..
H O.. N O..
..
Electrons
Start
24
Used
8
Left
16
..
..
..
O
1 bond
..
..
..
H O.. N O
..
Electrons
Start
24
Used
8
Left
16
Electrons
Start
16
Used
16
Left
0
..
..
..
..
..
..
..
..
H O.. N O
..
..
O
..
..
H O.. N O
..
..
..
..
..
H O.. N O
..
CHECKPOINT 4
Draw Lewis Structures of the Following
CO2
H3PO4
SeOF2
SO32
NO2
P2H4
CO2
16 e
H3PO4
32 e
SeOF2
SO32
26 e
26 e
NO2
18 e
P2H4
14 e
total number
of valence
electrons in
the free atom
total number
of nonbonding
electrons
1
2
total number
of bonding
electrons
-1
+1
formal charge
on an atom in
a Lewis
structure
total number
total number
of valence
of nonbonding
electrons in electrons
the free atom
total number
of bonding
electrons
formal charge
= 4 - 2 - x 6 = -1
on C
formal charge
= 6 - 2 - x 6 = +1
on O
71
H
H
0
C
formal charge
on an atom in
a Lewis
structure
0
O
total number
total number
of valence
of nonbonding
electrons in electrons
the free atom
total number
of bonding
electrons
formal charge
= 4 - 0 - x 8 = 0
on C
formal charge
= 6 - 4 - x 4 = 0
on O
72
Example 10
Strategy The Lewis structure for the carbonate ion was
developed as below:
Example 10
The C atom: The C atom has four valence electrons and there
are no nonbonding electrons on the atom in the
Lewis structure. The breaking of the double bond
and two single bonds results in the transfer of four
electrons to the C atom. Therefore, the formal
charge is 4 4 = 0.
The O atom in C=O: The O atom has six valence electrons and
there are four nonbonding electrons on
the atom. The breaking of the double
bond results in the transfer of two
electrons to the O atom. Here the formal
charge is 6 4 2 = 0.
Example 10
The O atom in CO: This atom has six nonbonding electrons
and the breaking of the single bond
transfers another electron to it.
Therefore, the formal charge is
6 6 1 = 1.
Thus, the Lewis structure for
Check Note that the sum of the formal charges is 2, the same
as the charge on the carbonate ion.
76
Example 11
Formaldehyde (CH2O), a liquid with a disagreeable odor,
traditionally has been used to preserve laboratory specimens.
Draw the most likely Lewis structure for the compound.
Example 11
Strategy A plausible Lewis structure should satisfy the octet
rule for all the elements, except H, and have the formal charges
(if any) distributed according to electronegativity guidelines.
Example 11
First we draw the Lewis structures for each of these possibilities
Example 11
In (b) the C atom has a total of four electrons from the breaking
of two single bonds and a double bond, so its formal charge is
4 4 = 0. The O atom has a total of six electrons (two lone
pairs and two electrons from the breaking of the double bond).
Therefore, the formal charge on the atom is 6 6 = 0. Although
both structures satisfy the octet rule, (b) is the more likely
structure because it carries no formal charges.
CHECKPOINT 5
Assign formal charges
CO2
H3PO4
SeOF2
SO32
NO2
P2H4
CHECKPOINT 5 (answers)
CO2
H3PO4
all 0
P = +1
rest 0
SeOF2
SO32
S = +1
Se = +1
NO2
P2H4
all 0
2. Expanded octet
many elements may end up with more than eight valence
electrons in their structure if they can use their empty d
orbitals for bonding
3. Odd number electron species e.g., NO
- Will have one unpaired electron, free radical & very
reactive
BF3
B 3e3F 3x7e24e-
Be 2e2H 2x1e4e-
Be
F
85
A molecule with an
odd number of
electrons is called a
free radical.
Odd-Electron Molecules
NO
N 5eO 6e11e-
SF6
S 6e6F 42e48e-
S
F
Example 13
Draw the Lewis structure for aluminum triiodide (AlI3).
Example 13
Strategy We follow the procedures used in Examples 11 and
12 to draw the Lewis structure and calculate formal charges.
Solution The outer-shell electron configurations of Al and I are
3s23p1 and 5s25p5, respectively. The total number of valence
electrons is 3 + 3 7 or 24. Because Al is less electronegative
than I, it occupies a central position and forms three bonds with
the I atoms:
Example 13
Check Although the octet rule is satisfied for the I atoms, there
are only six valence electrons around the Al atom.
Thus, AlI3 is an example of the incomplete octet.
Example 14
Draw the Lewis structure for phosphorus pentafluoride (PF5), in
which all five F atoms are bonded to the central P atom.
PF5 is a reactive
gaseous compound.
Example 14
Strategy Note that P is a third-period element. We follow the
procedures given in Examples 11 to draw the Lewis structure
and calculate formal charges.
Example 14
The Lewis structure of PF5 is
Example 15
Draw a Lewis structure for the sulfate ion
in which all
four O atoms are bonded to the central S atom.
Example 15
Strategy Note that S is a third-period element. We follow the
procedures given in Example 11 to draw the Lewis structure
and calculate formal charges.
Solution The outer-shell electron configurations of S and O
are 3s23p4 and 2s22p4, respectively.
Step 1: The skeletal structure of
is
Example 15
Step 2:
Step 3:
Example 15
Next we show formal charges on the S and O atoms:
Example 15
Example 15
Thus, the following structure would give formal charges on
S(2) and O(0) that are inconsistent with the electronegativities
of these elements and should therefore not be included to
represent the
ion.
Example 16
Draw a Lewis structure of the noble gas compound xenon
tetrafluoride (XeF4) in which all F atoms are bonded to the
central Xe atom.
Example 16
Strategy Note that Xe is a fifth-period element. We follow the
procedures in Example 11 for drawing the Lewis structure and
calculating formal charges.
Solution
Step 1: The skeletal structure of XeF4 is
Step 2:
Example 16
Step 3:
CHECKPOINT 6
Show the resonance forms of NCO- and
predict which resonance structure is the
most stable structure.
104
Answer:
NCO has 3 possible resonance forms:
N C
N C
N C
formal charges
2 0 +1
N C
1 0
N
0
O
0 1
N C
2)
108
ENCl = 3.0
3.0 3.0 = 0
Pure Covalent
ENCl = 3.0
ENH = 2.1
E = 3.0 2.1
= 0.9
Polar Covalent
ENCl = 3.0
ENNa = 0.9
E = 3.0 0.9
= 2.1
Ionic
HF
EN = 2.1
EN = 4.0
d+ H
F d-
Difference
Bond Type
Covalent
Ionic
Polar Covalent
Polar Covalent
share e-
partial transfer of e-
Ionic
transfer e113
Example
Classify the following bonds as ionic, polar covalent, or
covalent:
(a) the bond in HCl
(b) The bond in KF
(c) the CC bond in H3CCH3
Excercise
Strategy We follow the 2.0 rule of electronegativity difference.
Solution
(a) The electronegativity difference between H and Cl is 0.9,
which is appreciable but not large enough (by the 2.0 rule)
to qualify HCl as an ionic compound. Therefore, the bond
between H and Cl is polar covalent.
(b) The electronegativity difference between K and F is 3.2,
which is well above the 2.0 mark; therefore, the bond
between K and F is ionic.
(c) The two C atoms are identical in every respectthey are
bonded to each other and each is bonded to three other H
atoms. Therefore, the bond between them is purely
covalent.
Bond Lengths
Covalent compounds
Ionic Compounds
121
122
Molecular Geometry
3-dimensional arrangement of atoms in a
molecules
Molecular geometry affects its physical and
chemical properties
We often describe the shape of a molecule
with terms that relate to geometric figures
The geometric figures also have
characteristic angles that we call bond
angles
125
VSEPR Theory
The geometric arrangement of electron pairs around a
central atom by minimize the electrostatic repulsion
between electron pairs.
Electron groups around the central atom of a molecule will
be most stable when they are separated as far apart as
possible we call this valence shell electron pair
repulsion theory (VSEPR)
The resulting geometric arrangement will allow us to predict
the shapes and bond angles in the molecule
VSEPR formula: ABaEb
A = central atom; B = surrounding atoms
E = lone pairs on central atom; a, b = integers (1,2,3)
Electron Groups
The Lewis structure predicts the number of
valence electron pairs around the central atom(s)
Each lone pair of electrons constitutes one
electron group on a central atom
Each bonding pair constitutes one electron group
on a central atom
regardless of whether it is single, double, or
triple
O N O
AB2
# lone
pairs on
central
atom
Arrangement Molecular
of electron Geometry
pairs
linear
linear
B
128
VSEPR
# of atoms
bonded to
central
Class
atom
AB2
AB3
2
3
# lone
pairs on
central
atom
Arrangement
of electron Molecular
Geometry
pairs
linear
linear
trigonal
planar
trigonal
planar
129
Boron Trifluoride
130
VSEPR
# of atoms
bonded to
Class
central
atom
AB2
# lone
pairs on
central
atom
Arrangement Molecular
of electron Geometry
pairs
linear
linear
trigonal
planar
AB3
trigonal
planar
AB4
tetrahedral
tetrahedral
131
Methane
132
VSEPR
# of atoms
bonded to
central
Class
atom
AB2
# lone
pairs on
central
atom
Arrangement Molecular
of electron Geometry
pairs
linear
linear
trigonal
planar
AB3
trigonal
planar
AB4
tetrahedral
AB5
trigonal
bipyramidal
tetrahedral
trigonal
bipyramidal
133
Phosphorus Pentachloride
134
VSEPR
# of atoms
bonded to
central
Class
atom
AB2
# lone
pairs on
central
atom
Arrangement
of electron Molecular
Geometry
pairs
linear
linear
trigonal
planar
tetrahedral
AB3
trigonal
planar
AB4
tetrahedral
AB5
AB6
trigonal
bipyramidal
octahedral
trigonal
bipyramidal
octahedral
135
Sulfur Hexafluoride
136
137
VSEPR
# of atoms
bonded to
Class
central
atom
# lone
pairs on
central
atom
AB3
AB2E
Arrangement Molecular
of electron Geometry
pairs
trigonal
planar
trigonal
planar
trigonal
planar
bent
139
VSEPR
# of atoms
bonded to
central
atom
Class
AB4
AB3E
# lone
pairs on
central
atom
Arrangement
of electron
Molecular
pairs
Geometry
tetrahedral
tetrahedral
tetrahedral
trigonal
pyramidal
140
VSEPR
# of atoms
bonded to
central
atom
Class
AB4
# lone
pairs on
central
atom
Arrangement
of electron Molecular
pairs
Geometry
tetrahedral
tetrahedral
trigonal
pyramidal
bent
AB3E
tetrahedral
AB2E2
tetrahedral
141
VSEPR
# of atoms
bonded to
central
atom
Class
# lone
pairs on
central
atom
AB5
AB4E
Arrangement
of electron Molecular
Geometry
pairs
trigonal
bipyramidal
trigonal
bipyramidal
trigonal
bipyramidal
distorted
tetrahedron
142
# of atoms
bonded to
central
Class
atom
AB5
AB4E
AB3E2
4
3
# lone
pairs on
central
atom
1
2
Arrangement
of electron Molecular
pairs
Geometry
trigonal
bipyramidal
trigonal
bipyramidal
trigonal
bipyramidal
trigonal
bipyramidal
distorted
tetrahedron
T-shaped
143
# of atoms
bonded to
central
Class
atom
# lone
pairs on
central
atom
Arrangement
of electron Molecular
Geometry
pairs
AB5
AB4E
trigonal
bipyramidal
AB3E2
trigonal
bipyramidal
AB2E3
trigonal
bipyramidal
trigonal
bipyramidal
trigonal
bipyramidal
distorted
tetrahedron
T-shaped
linear
144
VSEPR
# of atoms
bonded to
central
Class
atom
AB6
AB5E
6
5
# lone
pairs on
central
atom
Arrangement
of electron Molecular
pairs
Geometry
octahedral
octahedral
octahedral
square
pyramidal
145
# of atoms
bonded to
central
Class
atom
AB6
AB5E
AB4E2
6
5
4
# lone
pairs on
central
atom
Arrangement
Molecular
of electron
Geometry
pairs
octahedral
octahedral
octahedral
square
pyramidal
octahedral
square
planar
146
147
Predicting Molecular
Geometry
1. Draw Lewis structure for molecule.
2. Count number of lone pairs on the
central atom and number of atoms
bonded to the central atom.
3. Use VSEPR to predict the geometry of
the molecule.
149
Example 1
Use the VSEPR model to predict the geometry
of the following molecules and ions:
(a) AsH3
(b) OF2
(c)
(d)
(e) C2H4
Example 1
Strategy The sequence of steps in
determining molecular geometry is as follows:
Solution
(a) The Lewis structure of AsH3 is
Example 1
Recall that the geometry of a molecule is determined
only by the arrangement of atoms (in this case the As
and H atoms). Thus, removing the lone pair leaves us
with three bonding pairs and a trigonal pyramidal
geometry, like NH3. We cannot predict the HAsH
angle accurately, but we know that it is less than
109.5 because the repulsion of the bonding electron
pairs in the AsH bonds by the lone pair on As is
greater than the repulsion between the bonding pairs.
(b) The Lewis structure of OF2 is
Example 1
Recall that the geometry of a molecule is determined only
by the arrangement of atoms (in this case the O and F
atoms). Thus, removing the two lone pairs leaves us with
two bonding pairs and a bent geometry, like H2O. We
cannot predict the FOF angle accurately, but we know that it
must be less than 109.5 because the repulsion of the
bonding electron pairs in the OF bonds by the lone pairs
on O is greater than the repulsion between the bonding
pairs.
(c) The Lewis structure of
is
Example 1
There are four electron pairs around the central atom;
therefore, the electron pair arrangement is tetrahedral.
Because there are no lone pairs present, the
arrangement of the bonding pairs is the same as the
electron pair arrangement. Therefore,
has a
tetrahedral geometry and the ClAlCl angles are all
109.5.
(d) The Lewis structure of
is
Example 1
Recall that the lone pairs preferentially occupy the
equatorial positions in a trigonal bipyramid. Thus,
removing the lone pairs leaves us with a linear geometry
for, that is, all three I atoms lie in a straight line.
(e) The Lewis structure of C2H4 is
Example 1
Thus, the predicted bond angles in C2H4 are all 120.
Comment
(1) The ion is one of the few structures for which the
bond angle (180) can be predicted accurately even
though the central atom contains lone pairs.
(2) In C2H4, all six atoms lie in the same plane. The overall
planar geometry is not predicted by the VSEPR model, but
we will see why the molecule prefers to be planar later. In
reality, the angles are close, but not equal, to 120
because the bonds are not all equivalent.
CHECKPOINT 7
Predict the geometries of the following species using the
VSEPR method:
a) PCl3
b) H2O
c) CHCl3
d) ClF3
e) TeCl4
trigonal pyramidal
bent shape
Tetrahedral
t-shape
seesaw
CHECKPOINT 8
Which of the following species are tetrahedral?
SiCl4, SeF4, XeF4, Cl4, CdCl42-
electron poor
region
electron rich
region
d+
d-
m=Qxr
Q is the charge
r is the distance between charges
1 D = 3.36 x 10-30 C m
* Note to students: You will not be
tested on DP calculation
field off
field on
160
vector addition
ENN = 3.0
ENH = 2.1
3.0 2.1 = 0.9
therefore the bonds
are polar covalent
169
170
Example 2
Predict whether each of the following
molecules has a dipole moment:
(a) BrCl
(b) BF3 (trigonal planar)
(c) CH2Cl2 (tetrahedral)
Example 2
Strategy
Keep in mind that the dipole moment of a
molecule depends on both the difference in
electronegativities of the elements present and
its geometry.
A molecule can have polar bonds (if the
bonded atoms have different
electronegativities), but it may not possess a
dipole moment if it has a highly symmetrical
geometry.
Example 2
Solution
(a) Because bromine chloride is diatomic, it has a
linear geometry. Chlorine is more
electronegative than bromine. so BrCl is polar
with chlorine at the negative end
Example 2
(b) Because fluorine is more electronegative than
boron, each BF bond in BF3 (boron trifluoride) is
polar and the three bond moments are equal.
However, the symmetry of a trigonal planar shape
means that the three bond moments exactly cancel
one another:
B-F
Example 2
(c) The Lewis structure of CH2Cl2 (methylene
chloride) is
Example 2
Because chlorine is more electronegative than
carbon, which is more electronegative than
hydrogen, the bond moments do not cancel and
the molecule possesses a dipole moment:
Example 3
Explain why CO2 is nonpolar, but OCS is polar.
CHECKPOINT 9
List the following molecules in order of
decreasing dipole moment: H2O, HF, CO2