4 Chemical Bonding

CHEM 1000 3.
0 Chemical Bonding 1
Chemical Bonding
Petrucci, Herring Madura and Bissonnette :
Chapters 10 and 11
Aims:
To look at bonding and possible shapes oI molecules
We will mainly do this through Lewis structures
To look at ionic and covalent bonds
Use valence shell electronic structure to predict shapes oI
molecules
CHEM 1000 3.0 Chemical Bonding 2
Problem set
Chapter 10 questions 3, 4, 11, 17, 18, 21,
22b), 59, 62, 141
Chapter 11 questions 7, 13, 17
Chemical Bonding
Lewis Theory:
Electrons, particularly valence electrons play a
Iundamental role in chemical bonding.
When elements combine to produce compounds
they are attempting to achieve a Iull valence
shell (usually 8 electrons)
Chemical Bonding
Lewis Theory:
Electrons can be transIerred Irom one atom to
another to make ions. The atoms are then held
together by coulombic Iorces in an ionic bond
More oIten the only way an atom can gain
electrons is by sharing. This sharing produces a
covalent bond
Lewis Symbols
This is a way oI representing the valence
electrons in an element
It does not include the inner shell electrons
It does not include the spin oI an electron
e.g. Si (|Ne|3s
2
3p
2
)
N (|He|2s
2
2p
3
)
Si
N
Lewis Structures
These are the combination oI Lewis symbols that
represents the sharing or transIer oI electrons in a
molecule
Ionic bonding examples ( electron transIer)
Na + Cl [Na]
+
[ Cl ]
-
x
x
Mg + 2 Cl [Mg]
2+
2 [ Cl ]
-
x
x
x
Ionic Compounds
We don`t usually see isolated ionic compounds
Normally they are in crystals where one anion
(negative) is attached to several cations (positive)
and vice versa. Electrical neutrality means the total
number oI each ion is the same.
Ionic Compounds
Lewis Structures
These are the combination oI Lewis symbols that
represents the sharing or transIer oI electrons in a
molecule
Covalent bonding example (sharing)
H + Cl H Cl
x
x
Covalent Compounds
Here electrons are shared between two atoms.
Why? Because the energy cost oI making the ions is too
high
Could be more than just a couple oI shared electrons
The electrons are associated with each atom in the
covalent bond
The overall eIIect is that each atom has 'more (usually
a Iull shell oI) valence electrons.
Covalent Compounds
Examples
Single covalent bond HCl
Note that there are 6 electrons around the Cl that
are not involved in bonding. It is normal to talk
about these as lone pairs, in contrast to bond
pairs
Lone pairs
Bond pair
H Cl H Cl
Coordinate Covalent Bonds
Bonds do not have to come Irom equal sharing oI
electrons
In NH
4
there are 8 electrons around the N, but it has 5

to start with. Hence the hydrogens only contribute 3 oI
the 8 bonding electrons.
Multiple Covalent Bonds
OIten the sharing oI one electron does not
'Iill the valence shell oI an atom.
e.g. N
2
N N
N N
N N N N
Multiple Bonds
We use a number oI diIIerent ways to
describe multiple bonds
For 1 bond pair For 3 bond pair
Single bond Triple bond
bond order 1 bond order 3
For 2 bond pairs
Double bond
bond order 2
Bond Length
Bond Length
The distance between two atoms joined by a
covalent bond
As the bond order increases the bond length
decreases
Bond Length/pm Bond Length/pm
C-C 154 N-N 145
CC 134 NN 123
C C 120 N N 110
Bond Energy
To separate two atoms that are joined by a
covalent bond, energy must be supplied. This is
the Bond Dissociation Energy (D).
This is equal to the energy released when the bond
is Iormed.
H
2
(g) 2H(g) H D(H-H) 435.93 kJ mol
-1
Listed bond energies are usually an average over a number
oI compounds
Polarity oI Bonds
In most molecules the bonding is not 100
ionic or 100 covalent (equal sharing)
Start Irom the covalent side
Unequal sharing oI electrons in a bond means
one atom is slightly positive () and the other
slightly negative (-).
This leads to a polar covalent bond.
Charge density (electrostatic potential)
Ionic
100 Covalent
100 covalent
This is a map that shows the surIace that shows
where the charge is located
Polarity oI Bonds
The ability to attract electrons in a bond
appears to be related to electron aIIinity but
we need to use a molecular property to
describe it.
Electronegativity is a quantitative measure
oI an atom`s ability to compete Ior electrons
with other atoms to which it is bonded.
Actually the diIIerence between an atom`s
ionization energy and its electron aIIinity
Polarity oI Bonds:
Electronegativities
Polarity oI Bonds
Thus the diIIerence in electronegativities
between atoms in a bond gives a measure oI
the polarity.
This can also be interpreted as the ionic
character oI a bond
Polarity oI Bonds:
Ionic Character
The larger the
electronegativity
diIIerence between
the atoms, the more
ionic the bond.
1.7
Lewis Structures
Lewis structures are useIul in indicating the
bonding in molecules.
Rules:
All valence electrons must appear
The electrons are usually paired
The valence shells are usually Iilled (2 electrons Ior H,
8 Ior systems with s and p orbitals)
Multiple bonds are oIten needed, especially in C, N, O,
P, S.
Lewis Structures
1. Check iI the compound is ionic. II it is, treat
each ion separately.
2. Add up the number oI valence electrons (that`s
Irom all atoms). Add or subtract electrons to
give the right charge. This is the available
electrons A.
3. Draw a skeletal structure. The central atom will
normally have the lowest electronegativity.
Carbon is always a central atom. Hydrogen is
always terminal.
Lewis Structures
4. Calculate the number oI valence electrons
needed to give all the atoms a Iull shell (2 or 8).
This is the number oI needed electrons N
5. Determine the number oI electrons that must be
shared SN-A
6. Place single bonds in the skeletal structure (2
electrons per). Add extra bonds to satisIy S.
7. Place remaining electrons, in (lone) pairs to
complete the octets Ior each atom.
Lewis Structures
Example C
2
N
2
Carbon has 4 valence electrons, nitrogen 5. A18
Each atom wants an octet, N32
Shared electrons S 32-18 14 (7 bonds)
Skeleton: (Electronegativities C 2.5, N 3.0)
N-C-C-N : Still need 4 more bonds.
N C C N is the only way to add the 4
bonds without having more than 8 electrons
around a carbon.
Lewis Structures
Example C
2
N
2
This uses 14 oI the 18 electrons, so there are only 4
leIt. The carbons have their octet, each nitrogen
is 2 short so we must have one lone pair on each
nitrogen.
N C C N
Formal Charges
The method oI obtaining the Lewis structures
does not keep track oI where the electrons
came Irom.
Hence we can get multiple results. However in
some structures atoms are not contributing equal
numbers oI electrons to the bonds. This is less
likely to result in a stable conIiguration.
Formal Charges
E.g. ONCl
O N Cl O N Cl
Cl donates 3 electrons to the bond
O donates 0 electrons to the bond
Cl and N donate one electron each
O and N donate 2 electrons each
This seems more reasonable.
Formal Charges
The Iormal charge is the apparent charge on
an atom that comes Irom unequal sharing oI
electrons.
It can be used to decide between possible
structures.
Formal Charges
The Iormal charge is the apparent charge on an atom that
comes Irom unequal sharing oI electrons.
It can be used to decide between possible structures.
The Iormal charge on an atom is:
FC # oI valence electrons in Iree atom
# oI lone pair electrons on the atom
(# oI bonding electrons)
Formal Charges
Rules Ior the most plausible Lewis structure:
1. The most plausible is the one where no atoms
have a Iormal charge.
2. Where Iormal charges are required, they should
be as small as possible.
3. Negative Iormal charges should be on the most
electronegative atoms.
4. Same sign Iormal charges on adjacent atoms
are unlikely.
Formal Charges
E.g. ONCl
O N Cl O N Cl
Formal charges
FC(O) 6 -6-1 -1 wrong
FC(N) 5-2-3 0
FC(Cl) 7-4-2 1 (wrong)
2
Formal charges
FC(O) 6 -4-2 0
FC(N) 5-2-3 0
FC(Cl) 7-6-1 0
Formal Charges
Example: HCN
H C N H N C
Remembering that C has 4 valence electrons and N 5
FC(H) 0 FC(H) 0
FC(C) 0 FC(C) 1
FC(N) 0 FC(N) 1
HCN is most likely.
Formal Charges
Formal charges allow us to Iollow electrons
in bonding.
They are not the actual charges on atoms
What is the charge on an atom?
Charges on atoms
Oxidation numbers assume that the
bonds are 100 ionic
ON(S) 6, ON(O) 2
Formal charges assume bonds are 100
covalent
FC(S) 0, FC(O) 0.5
The real charge is somewhere between
and is determined by the polarity oI the
bonds
S O
O
O
O
2-
Lee Allen`s Method
The degree oI polarity in a bond involving
atom 'A and 'B depends on the
electronegativity oI 'A and 'B
IF EN(A) EN(B) then halI the charge is
on atom 'A (the bond is covalent)
EN(A)
polarity
EN(A) EN(B)

Lee Allen`s Method
In a molecule the charge on A is
G
A
group number (the number oI electrons in the atom)
N
A
Number oI lone pair electrons on 'A
N
AB
is the number oI bonding electrons between 'A
and 'B
A A A AB
B A
EN(A)
q G -N - N
EN(A) EN(B)

Lee Allen`s Method
For a 100 covalent bond EN(A) EN(B)
This is the calculation Ior Iormal charge
A A A AB
B A
A A A AB
EN(A)
q G -N - N
EN(A) EN(B)
1
q G -N - N
2
becomes


Charges on atoms
Oxidation numbers assume that the
bonds are 100 ionic
ON(S) 6, ON(O) 2
Formal charges assume bonds are 100
covalent
FC(S) 0, FC(O) 0.5
Lee Allen`s method (EN(S) 2.5, EN(O) 3.5)
q
S
1.0, q
O
0.75
S O
O
O
O
2-
Resonance
Consider ozone O
3
These are both reasonable Lewis structures
BUT experimental evidence shows the
bonds are the same length.
O O O O O O
Resonance
The real structure is a hybrid oI these two
This is called resonance. The real structure is a
resonance hybrid oI these two structures.
The real structure has bonds which are between
single and double bonds. So what is the bond
order oI the oxygen-oxygen bond in ozone?
O O O O O O
Exceptions/Extensions
Odd electron species: eg NO (11 electrons)
Lewis structures don`t do a good job in this
case.
In general you can produce a Lewis structure
without the last electron and this goes on the
atom to minimize the Iormal charge.
Incomplete octets.
Sometimes when you make a sensible structure you
don`t have enough electrons.
BF
3
All atoms have a zero Iormal charge
Boron only has 6 electrons
B
F
F F
BF
3
Boron has a Iormal charge
oI -1 The double bonded
Iluorine 1
The need to obtain an octet
overrides the rule Ior
minimal Iormal charge
AND the ve Iormal charge
being on the most
electronegative atom.
Note we also have
resonance structures.
B
F
F
F
Expanded valence shells.
To explain the bonding it sometimes seems
necessary to have more than 8 electrons in the
valence shell. This can be done Ior third period
elements by invoking the 'd orbitals.
Expanded Octet Example
S O
O
O
O
2-
Sulphate, SO
4
2-
Octets are complete, but the
Iormal charges are horrible.
Sulphur is in the 3rd period
so d orbitals may be
available Ior expanding the
octet to reduce Iormal
charges.
FC(-O) -1
FC(S) 2
Expanded Octet Example (cont.)
The octet around the S has been expanded to hold 10.
On basis oI Iormal charge this is better.
Would Iormal charges be Iurther reduced by Iurther
expansion?
FC(S) 1
FC( single bonded O) -1
FC(double bonded O) 0
S O
O
O
O
2-
Expanded Octet Example (cont.)
Is this the best possible structure?
Yes because we cannot lower the Iormal charges
Iurther.
FC(S) 0
FC( single bonded O) -1
FC(double bonded O) 0
Since there are resonance
Iorms FC(O) 0.5
S O
O
O
O
2-
Shapes oI Molecules
In this section we will use Lewis structures as an
introduction to the shapes oI molecules.
The key concepts are:
Electron pairs repel each other.
Electron pairs assume orientations to minimize
repulsion
This is the Valence Shell Electron Pair Repulsion
Theory (VSEPR)
VSEPR
Example: Methane CH
4
The 4 bond pairs must orient themselves to
minimize their repulsion.
H C H
H
H
VSEPR Methane
The minimum interaction occurs
when the electron pairs point towards
the vertices oI a tetrahedron.
The carbon is in the centre and the
hydrogen are at the vertices. The
molecule is tetrahedral.
VSEPR Ammonia
Example: Ammonia NH
3
The 4 electron pairs must still orient
themselves to minimize their repulsion.
N H
H
H
VSEPR Ammonia
The minimum interaction still occurs
The nitrogen is in the centre and the
hydrogens are at three oI the vertices.
The lone pair points to the Iourth.
The molecule is trigonal pyramidal.
VSEPR Water
Example: Water H
2
O
The 4 electron pairs must orient themselves to
minimize their repulsion.
O
H
H
VSEPR Water
The minimum interaction still occurs
The oxygen is in the centre, the
hydrogens are at two oI the vertices.
The lone pairs point to the other two.
The molecule is bent.
Bond Angles
This analysis suggests that all three molecules
should have bond angles oI 109.5
o.
The methane bond angle is 109.5
o
but Ior ammonia
it is 107
o
and in water it is 104.5
o
The lone pair electrons are not constrained as much
as the bonding pairs. They spread out thus the
repulsive Iorces are:
Lone pair-lone pair~Lone pair-bond pair~bond pair-bond pair
Molecular Geometry
VSEPR theory can be used to describe the
shapes oI most molecules.
Warnings
When you describe the shape, don`t include the
lone pairs. (water is bent, not tetrahedral)
Molecules have three dimensions (methane is a
tetrahedron not a square)
Be Iamiliar with table 10.1 pg 399-400
Going Beyond Lewis Structures
Lewis structures are very useIul in
explaining the bonding in simple molecules
and in predicting molecular shapes.
They do not explain why electrons in bond
pairs bring nuclei together.
They can not be used to estimate bond
lengths or bond strengths.
Going Beyond Lewis Structures
There are two currently used bonding theories,
valence bond theory and molecular orbital theory.
Valence bond theory envisions bonding as
resulting Irom the overlap oI atomic orbitals.
Molecular orbital theory moves past atomic
orbitals and derives orbitals that belong to the
molecule as a whole.
We will concentrate on valence bond theory as
that is suIIicient to rationalize the structures we
see.
Valence Bond Method
This method considers what happens to the
valence orbitals (the outer shell).
II the atoms start a long way apart, there is no
interaction.
As the atoms move closer together the orbitals
may overlap.
II there is an electron in the orbital then there is a
high probability oI Iinding an electron between the
nuclei.
This is the region where there is a covalent bond.
Valence Bond Method
We cannot ignore the previously developed
rules, so there are only two electrons per
bond
Overlap can only occur Ior 2 halI Iilled orbitals
or one empty and one Iilled orbital.
Valence Bond Method
H
2
S
Not shown
This suggests the bond angle should be 90
o
.
It is 92
o
.
Valence Bond method Ior methane
Chemically methane is stable
We know Irom VSEPR that methane is
tetrahedral
BUT
The valence bond theory (so Iar) would
suggest that the 1s electrons Irom H will be
donated to the p orbitals to 'pair-up the
unpaired electrons.
In this case we would have CH
2
That`s not what is seen. We need CH
4
.
Somehow the carbon needs to have 4
unpaired electrons
This gives 4 unpaired electrons
This costs energy, as it makes an excited
state C atom.
Also iI we try to use these orbitals in
bonding, the orientation is wrong.
II hydrogens attached to the 'p orbitals, they
would be orthogonal.
Where would the overlap with the 's be?
We know the molecule is tetrahedral.
Valence Bond Rethinking
We can no longer assume that the orbitals in a
bonded atom are the same as those oI an isolated
atom.
Remember that the atomic orbitals come Irom
solving an equation assuming a single nucleus. In
a molecule the electron has to respond to more
nuclei.
We should solve the 'new problem, but we
usually say we can combine the atomic orbitals in
some way.
Since the orbitals are wave Iunctions, we can take
the 2s and 2p wave Iunctions and combine them to
give 4 equivalent wave Iunctions. These can be
made to have the same shape and energy.
This is called hybridization and the resulting
orbitals are called hydrid orbitals.
The combination oI one 's and three 'p orbitals
gives Iour 'sp
3
hybrid orbitals.
Generation oI sp
3
hybrid orbitals
Same shape but
diIIerent orientation to
minimize interaction
Methane
Energy and Hybrid Orbitals
What about the energy?
The energy oI the orbitals is conserved because
the sp
3
orbitals have an energy between the s and p
orbitals.
C
Energy and Hybrid Orbitals
However there will be an energy cost in making the
sp hybrids with one electron in each.
The orbitals are generated assuming only one electron
So why would the molecule do something that will
cost energy?
Once the molecule is Iormed you release the bond
energy. II this is greater than the 'cost then it is
worthwhile.
Ammonia
Now we have a pair oI electrons in one oI
the sp
3
hybrid orbitals, so it can`t bond with
hydrogen.
N
Ammonia
NH
3
versus PH
3
NH
3
has sp
3
bonding and a bond angle oI
~109.
PH
3
has a bond angle oI 93 so it looks like it
does not hybridize.
It still hybridizes but the angle is 93
The lone pair on the P is larger than that on the N
Thus the bond pair-bond pair angle is even
smaller in PH
3
The sp
3
hybrid orbitals don`t explain the
bonding Ior Boron (group 13) or Ior
Beryllium (group 2)
The problem appears to be that there are
insuIIicient electrons to even halI Iill the 4
sp
3
orbitals.
In these case we need to consider diIIerent
hybridization schemes.
We deIine hybrids such that the number oI
hybrids is the same as the number oI
valence electrons.
sp
2
and sp hybrid orbitals
Boron
Beryllium
The number oI orbitals is
conserved.
sp
2
hybrid orbitals (BCl
3
)
sp hybrid orbitals (BeCl
2
)
Multiple bonds
How do we deal with the Lewis structures
that have multiple bonds?
Consider ethylene C
2
H
4
C C
H
H H
H
Multiple bonds: ethylene (C
2
H
4
)
The geometry suggests sp
2
hybrid orbitals
are involved.
There is still an electron in the remaining 2p orbital.
2
H
4
)
The sp
2
hybrid
orbitals are in
purple.
The 'p
orbital is
blue/red
2
H
4
)
The orbitals that overlap along the axis oI the
nuclei are called sigma bonds - bonds.
Those where the overlap is side-to-side are pi
bonds - bonds.
Multiple bonds: ethylene
The bonds determine the shape oI the molecule,
the bonds restrict the rotation about the C-C
axis.
The orbital overlap is more extensive Ior the bonds
so the bond is weaker than the bond.
Bond strengths
C-C 347 kJ mol
-1
CC 611 kJ mol
-1
diIIerence 264 kJ mol
-1
Multiple bonds: acetylene (ethyne)
The geometry suggests sp hybrid orbitals
are involved.
There is still an electron in each oI the
remaining 2p orbitals.
C C H H
Multiple bonds: acetylene (ethyne)
Multiple bonds: d orbitals
S O
O
O
O
2-
In sulphate we needed pi
bonding and to use the 'd
orbitals on the sulphur.
Without worrying about
resonance structures, can we
explain the bonding?
Multiple bonds: d orbitals sulphate
S O
O
O
O
2-
S O
O
O
O
2-
8 electrons
6 orbitals
S O
O
O
O
2-
8 electrons
6 orbitals
Why 6 orbitals?
For the resonant structures
Delocalization
This is an alternative method oI describing
molecules that have resonant structures.
Eg Ozone
We can describe the pi bonding as being
delocalised
The pi electrons are delocalised among 3 atoms
O O O O O O
Delocalization
Eg Ozone
O O O O O O
Multiple Bonds: Benzene
This structure is planar and suggests sp
2
.
In this case the 6 pi electrons are
delocalized over all 6 atoms oI the
molecule.

4 Chemical Bonding

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4 Chemical Bonding

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CHEM 1000 3.

there are 8 electrons around the N, but it has 5

CHEM 1000 3.0 Chemical Bonding 38

CHEM 1000 3.0 Chemical Bonding 39

CHEM 1000 3.0 Chemical Bonding 40

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