Apchapt 8

Chapter 8
Bonding
What is a Bond?
A force
that holds atoms together.
Why?
We
will look at it in terms of energy.

Bond energy the energy required to
break a bond.
Why are compounds formed?
Because it gives the system the lowest
energy.
Ionic Bonding
An
atom with a low ionization energy

reacts with an atom with high electron
affinity.
The electron moves.
Opposite charges hold the atoms
together.
Coulomb's Law
E=
Q
2.31 x 10-19 J nm(Q1Q2)/r
is the charge.
r is the distance between the centers.
If charges are opposite, E is negative
exothermic
Same charge, positive E, requires
energy to bring them together.
What about covalent

compounds?
The
electrons in each atom are attracted

to the nucleus of the other.
The electrons repel each other,
The nuclei repel each other.
The reach a distance with the lowest
possible energy.
The distance between is the bond length.
Energy
0
Internuclear Distance
Energy
0
Energy
0
Energy
0
Energy
0
Bond Length
Energy
Bond Energy
Covalent Bonding
Electrons
are shared by atoms.

These are two extremes.
In between are polar covalent bonds.
The electrons are not shared evenly.
One end is slightly positive, the other
negative.
Indicated using small delta
+ -
H-F
+
-
H-
-F
F
-
+
-
H-
H
F
F
+
+ -
H-F
+ -
H-F
+ -
+
-
H-
-F
F
-
+
-
H-
H
F
F
+
+
H-F
+ -
H-F
+ -
H-F
+ -
H-F
+ -
H-F
+ -
H-F
+ -
H-F
H-F
+ -
+ -
H-F
+ -
H-F
Electronegativity
The
ability of an electron to attract

shared electrons to itself.
Pauling method
Imaginary molecule HX
Expected H-X energy =
H-H energy
+ X-X energy
2
= (H-X) actual - (H-X)expected
Electronegativity
is known for almost every element

Gives us relative electronegativities of
all elements.
Tends to increase left to right.
decreases as you go down a group.
Noble gases arent discussed.
Difference in electronegativity between
atoms tells us how polar.
Zero
Covalent
Intermediate
Polar
Covalent
Large
Ionic
Covalent Character
decreases
Ionic Character increases
Electronegativity Bond
difference
Type
Dipole Moments
A
molecule with a center of negative

charge and a center of positive charge
is dipolar (two poles),
or has a dipole moment.
Center of charge doesnt have to be
on an atom.
Will line up in the presence of an
electric field.
How It is drawn
+ -
H-F
Which Molecules Have Them?

Any
two atom molecule with a polar

bond.
With three or more atoms there are
two considerations.
There must be a polar bond.
Geometry cant cancel it out.
Geometry and polarity

Three
Linear
shapes will cancel them out.

Three

Planar triangles
120

Three

Tetrahedral

Others
Bent
dont cancel

Others
dont cancel
Trigonal Pyramidal
Ions
Atoms
tend to react to form noble gas

configuration.
Metals lose electrons to form cations
Nonmetals can share electrons in
covalent bonds.
When two non metals react.(more later)
Or they can gain electrons to form
anions.
Ionic Compounds
We
mean the solid crystal.

Ions align themselves to maximize
attractions between opposite charges,
and to minimize repulsion between like
ions.
Can stabilize ions that would be unstable
as a gas.
React to achieve noble gas configuration
Size of ions
Ion
size increases down a group.

Cations are smaller than the atoms
they came from.
Anions are larger.
across a row they get smaller, and
then suddenly larger.
First half are cations.
Second half are anions.
Periodic Trends
Across
the period nuclear charge

increases so they get smaller.
Energy level changes between anions
and cations.
B
Li+1
Be
+2
+3
C+4
N-3
O-2
F-1
Size of Isoelectronic ions

Iso
- same
Iso electronic ions have the same # of
electrons
Al+3 Mg+2 Na+1 Ne F-1 O-2 and N-3
All have 10 electrons.
All have the configuration 1s22s22p6
Size of Isoelectronic ions

Positive
ions have more protons so

they are smaller.
Al
+3
Na+1
Mg+2
Ne
F-1
O-2
N-3
Forming Ionic Compounds
Lattice energy - the energy associated

with making a solid ionic compound
from its gaseous ions.
M+(g)
+ X-(g) MX(s)
This is the energy that pays for

making ionic compounds.
Energy is a state function so we can get
from reactants to products in a round
about way.
Na(s) + F2(g) NaF(s)

sublime Na Na(s) Na(g)
H = 109 kJ/mol
Ionize Na(g) Na(g) Na+(g) + eH = 495 kJ/mol
Break F-F Bond F2(g) F(g)
H = 77 kJ/mol
Add electron to F
F(g) + e- F-(g)
H = -328 kJ/mol
First

Lattice
energy
H = -928 kJ/mol
Calculating Lattice Energy

Lattice
k
Energy = k(Q1Q2 / r)
is a constant that depends on the

structure of the crystal.
Qs are charges.
r is internuclear distance.
Lattice energy is greater with more
highly charged ions.
Calculating Lattice Energy

This
bigger lattice energy pays for

the extra ionization energy.
Also pays for unfavorable electron
affinity.
Bonding
Partial Ionic Character

There
are probably no totally ionic

bonds between individual atoms.
Calculate % ionic character.
Compare measured dipole of X-Y
bonds to the calculated dipole of X+Ythe completely ionic case.
% dipole = Measured X-Y x 100
Calculated X+Y In the gas phase.
% Ionic Character
75%
50%
25%
Electronegativity difference
How do we deal with it?

If
bonds cant be ionic, what are ionic

compounds?
And what about polyatomic ions?
An ionic compound will be defined as
any substance that conducts electricity
when melted.
Also use the generic term salt.
The Covalent Bond

The
forces that cause a group of atoms to

behave as a unit.
Why?
Due to the tendency of atoms to achieve the
lowest energy state.
It takes 1652 kJ to dissociate a mole of CH 4
into its ions
Since each hydrogen is hooked to the carbon,
we get the average energy = 413 kJ/mol
CH3Cl
the
has 3 C-H, and 1 C - Cl
C-Cl bond is 339 kJ/mol

The bond is a human invention.
It is a method of explaining the energy
change associated with forming
molecules.
Bonds dont exist in nature, but are
useful.
We have a model of a bond.
What is a Model?
Explains
how nature operates.

Derived from observations.
It simplifies the and categorizes the
information.
A model must be sensible, but it has
limitations.
Properties of a Model
A human
inventions, not a blown up picture
of nature.
Models can be wrong, because they are
based on speculations and
oversimplification.
Become more complicated with age.
You must understand the assumptions in
the model, and look for weaknesses.
We learn more when the model is wrong
than when it is right.
Covalent Bond Energies
We
made some simplifications in

describing the bond energy of CH4
Each C-H bond has a different energy.
CH4 CH3 + H
H = 435 kJ/mol
CH3 CH2 + H
H = 453 kJ/mol
CH2 CH + H
H = 425 kJ/mol
CH C + H
H = 339 kJ/mol
Each bond is sensitive to its
environment.
Averages
Have
made a table of the averages of

different types of bonds pg. 365
single bond one pair of electrons is
shared.
double bond two pair of electrons are
shared.
triple bond three pair of electrons are
shared.
More bonds, shorter bond length.
Using Bond Energies
can find H for a reaction.

It takes energy to break bonds, and end
up with atoms (+).
We get energy when we use atoms to
form bonds (-).
If we add up the energy it took to break
the bonds, and subtract the energy we get
from forming the bonds we get the H.
Energy and Enthalpy are state functions.
We
Find the energy for this

2 CH2 = CHCH3 + 2NH3 + O2
2 CH = CHC N + 6 H O
2
2
C-H
C=C
N-H
C-C
413 kJ/mol
614kJ/mol
391 kJ/mol
347 kJ/mol
O-H 467 kJ/mol

O=O 495 kJ/mol
CN 891 kJ/mol
Localized Electron Model
1)
2)
3)
Simple model, easily applied.

A molecule is composed of atoms that
are bound together by sharing pairs of
electrons using the atomic orbitals of the
bound atoms.
Three Parts
Valence electrons using Lewis structures
Prediction of geometry using VSEPR
Description of the types of orbitals
(Chapt 9)
Lewis Structure
Shows
how the valence electrons are

arranged.
One dot for each valence electron.
A stable compound has all its atoms
with a noble gas configuration.
Hydrogen follows the duet rule.
The rest follow the octet rule.
Bonding pair is the one between the
symbols.
Sum
Rules
the valence electrons.

Use a pair to form a bond between
each pair of atoms.
Arrange the rest to fulfill the octet rule
(except for H and the duet).
H2O
A line
can be used instead of a pair.
A useful equations
(happy-have)
POCl3
/ 2 = bonds
P is central atom
SO4-2
S is central atom
SO3-2
S is central atom
PO4-2
S is central atom
SCl2
S is central atom
Exceptions to the octet

BH3
Be
and B often do not achieve octet

Have less than and octet, for electron
deficient molecules.
SF6
Third row and larger elements can
exceed the octet
Use 3d orbitals?
I3-
Exceptions to the octet

When
we must exceed the octet, extra

electrons go on central atom.
ClF3
XeO3
ICl4 BeCl2
Sometimes
Resonance
there is more than one valid

structure for an molecule or ion.
NO 3
Use double arrows to indicate it is the
average of the structures.
It doesnt switch between them.
NO2 Localized electron model is based on pairs
of electrons, doesnt deal with odd
numbers.
For
Formal Charge
molecules and polyatomic ions

that exceed the octet there are several
different structures.
Use charges on atoms to help decide
which.
Trying to use the oxidation numbers to
put charges on atoms in molecules
doesnt work.
The
Formal Charge
difference between the number of

valence electrons on the free atom and
that assigned in the molecule.
We count half the electrons in each
bond as belonging to the atom.
SO4-2
Molecules try to achieve as low a formal
charge as possible.
Negative formal charges should be on
electronegative elements.
Examples
XeO3
NO4-3
SO2Cl2
VSEPR
Lewis
structures tell us how the atoms

are connected to each other.
They dont tell us anything about
shape.
The shape of a molecule can greatly
affect its properties.
Valence Shell Electron Pair Repulsion
Theory allows us to predict geometry
VSEPR
Molecules
take a shape that puts

electron pairs as far away from each
other as possible.
Have to draw the Lewis structure to
determine electron pairs.
bonding
nonbonding lone pair
Lone pair take more space.
Multiple bonds count as one pair.
VSEPR
The
number of pairs determines

bond angles
underlying structure
The number of atoms determines
actual shape
VSEPR
Electron Bond
pairs Angles
2
180
Underlying
Shape
Linear
120
109.5
Tetrahedral
90 &
120
90
Trigonal
Bipyramidal
Octagonal
Trigonal Planar
Actual shape
NonElectro Bondin Bondin
nPairs gPairs gPairs Shape
2
3
3
4
4
4
2
3
2
4
3
2
0
0
1
0
1
2
linear
trigonal planar
bent
tetrahedral
trigonal pyramidal
bent
Actual Shape

5
5
5
5
5
4
3
2
0
1
2
3
trigonal bipyrimidal
See-saw
T-shaped
linear
Actual Shape

6
6
6
6
6
6
5
4
3
2
0
1
2
3
1
Octahedral
Square Pyramidal
Square Planar
T-shaped
linear
No central atom
Can
predict the geometry of each

angle.
build it piece by piece.
How well does it work?

Does
an outstanding job for such a

simple model.
Predictions are almost always
accurate.
Like all simple models, it has
exceptions.

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Chapter 8

that holds atoms together.

will look at it in terms of energy.

atom with a low ionization energy

2.31 x 10-19 J nm(Q1Q2)/r

What about covalent

electrons in each atom are attracted

are shared by atoms.

ability of an electron to attract

is known for almost every element

molecule with a center of negative

Which Molecules Have Them?

two atom molecule with a polar

Geometry and polarity

shapes will cancel them out.

Geometry and polarity

shapes will cancel them out.

Geometry and polarity

shapes will cancel them out.

Geometry and polarity

Geometry and polarity

tend to react to form noble gas

mean the solid crystal.

size increases down a group.

the period nuclear charge

Size of Isoelectronic ions

Size of Isoelectronic ions

ions have more protons so

Forming Ionic Compounds

Lattice energy - the energy associated

This is the energy that pays for

Na(s) + F2(g) NaF(s)

Na(s) + F2(g) NaF(s)

Calculating Lattice Energy

is a constant that depends on the

Calculating Lattice Energy

bigger lattice energy pays for

Partial Ionic Character

are probably no totally ionic

How do we deal with it?

bonds cant be ionic, what are ionic

The Covalent Bond

forces that cause a group of atoms to

has 3 C-H, and 1 C - Cl

C-Cl bond is 339 kJ/mol

how nature operates.

inventions, not a blown up picture

Covalent Bond Energies

made some simplifications in

made a table of the averages of

Using Bond Energies

can find H for a reaction.

Find the energy for this

O-H 467 kJ/mol

Localized Electron Model

Simple model, easily applied.

how the valence electrons are

the valence electrons.

can be used instead of a pair.