Definition of Ea=E(X)-E(X-)

Electron affinity:Where E(X) = energy of neutral X atom

Thus the harder it is to remove an electron (1)

and the more energy you get back by attaching
an extra electron (Ea) the higher the electro negativity.

In Periodic Table: high electro negativity at top right, low

electro negativity at bottom left

Very large electro negativity difference ionic bond (X+Y-)

No electro negativity difference pure covalent bond (X-X).
Small to moderate electro negativity difference polar covalent
bond (X+-Y-, where Y is more electro negative than X).
 We will first concentrate
Lewis Structures on H and first row elements.

Basic rules: 1. Every atom tries to achieve an octet of electrons (2 for H).

2. Each pair of shared electrons one bond symbolized by a

dash (-)
F- O2- N3- C4-
How to achieve an octet
F O- N2- C3-
O N- C2-
Note: if an atom loses an
Electron (giving a positive O+ N C-
Charge), then it needs to
form more bonds to achieve
N2 C
its octet (see extra sheet)
Note: (1) never more than 4 bonds to central atom
(max. 8 electrons)
(2) Keep formal charges to a minimum

In polyatomic molecules distinguish between

central and terminal atoms. Difficult to give general
rule to specify which is which.

Often atom with lowest electro-negativity is

central; also chains of same atoms are very rare.

Lewis structures tell us nothing about shapes of

molecules
Some simple examples:
O needs 2 electrons to achieve octet Each H needs 1
H2O electron to achieve its full shell

(remember each dash

is a pair of shared electrons)
H O

H
N needs 3 electrons to achieve octet Each H
needs 1 electron to achieve octet.

H
NH3 N H

There will also be a lone pair on N

 C needs 4 electrons to achieve octet
CH4 each H needs 1 electron to achieve
its full shell
No lone pairs all C electrons
involved in bonding.
H
Remember Lewis structures
H C H
are 2- dimensional do not give
H correct structures.

C needs 4 electrons to achieve

COCl2 octet Each Cl needs 1 electron to
achieve its octes O needs 2
electrons to achieve octet.
Cl
Therefore to fill all Note double bond
octets we have: C O between C and O
Cl
 CH3CO2H The only way to achieve
octets for C, O, and full
(ethanoic acid, shells for H is
Acetic acid) H O

H C C O H

H
Also works for ions
NH4+
N needs 4 electrons to achieve octets
Each H needs 1 electron to
achieve its full shell
H

H
N H

H
 There are many more simple examples of organic
and inorganic molecules where the drawing of Lewis
structures using the above rules is very straight
forward.

But there are exceptions

1. Some elements (towards left hand side of the

periodic Table) cannot achieve a full octet.
B only has 3 valence electrons
BF3 would need 5 more to fill octet.
But can only form 3 bonds. Thus
BF3 is F

F B

F
2. Elements in second and subsequent rows of the
periodic Table can accommodate >8 electrons (can
expand their octer)
Such elements possess d-orbitals of suitable energy
for bonding so > 4 bonds can be formed (not
restricted to one s + three p orbitals).

Because S can expand its octet, it

SF6 is quite in order to have the Lewis
structure. F
F F
S
F F
F
Expansion of octer very common for compounds of Si, Ge,
P, As, Sb, S, Se, Te, Cl, Br, etc.
3. It is often not possible to draw a single,
unambiguous, Lewis structure for a given
molecule or ion.
C is the central atom; O can achieve its
CO32- octet by forming 2 bonds (=O), or one
bond + picking up an electron (-O-)

Also remember that C cannot form > 4 bonds

One possible Lewis structure would therefore be:
O

But this is not the only

C O
possibility!
O
The structure could equally be
O O

C O C O

O O

Each of these structures would predict one double bond

and two single bonds, i.e one shorter and two longer
bonds.

Experiment shows that all C-O bonds in the carbonate are

the same length.

The correct structure is a blend of all three forms (Not

hopping between them). This phenomenon is called
RESONANCE symbolised by:
 O O O

C O C O C O

O O O

The actual structure is called a resonance hybrid, and the

pair of electrons comprising the second component of the
double bond is said to be delocalized.

Another example of resonance:

Acetate (ethanoate) ion, CH3CO2-

Here there are TWO possible resonance structures:

 O O

H3C C H3C C

O O
Both C-O bond lengths are again the same (and
intermediate between the lengths of a single and a double
bond).
Benzene, C6H6

The bonding in benzene was not properly understood for

many years.

When the possibility of resonance became recognized,

the problem was largely solved.
Simple ideas would give the structure
H
BUT the CC bond lengths
are al the same (intermediate
H
C
C
C
H
between single and double),
C C
and benzene does not
H C H behave chemically like a
H molecule containing isolated
C=C bonds.
Hence we must introduce the second possible
form, in resonance with the first:
H H

H C H H C H
C C C C

C C C C

H C H H C H

H H
This explains the observed physical and chemical
properties of benzene, and it can also be drawn as

With the circle symbolizing the delocalized electrons.

Resonance is also possible with molecules containing

atoms where expansion of the octet has occurred.
 (chlorate ion) oxidizing agent
ClO3 -

O O O

Cl O Cl O Cl O

and O O O
(Perchlorate ion) rocket oxidizer
ClO4 -

O O O O

Cl Cl Cl Cl
O O O O O O O O
Note that
O
in all oxy-anions,
O
the negative
O chargesO
are formally situated on the oxygen atoms
Resonance involves the blending of two or more Lewis
Structures, where the atoms have the same relative
positions, but with different electronic arrangements.
Electrons are delocalized, and the energy of the resonance
Hybrid is lower than for any single component form.

All of the examples of resonance shown so far

involve two or more equivalent structures. It is
quite possible to have resonance between non-
equivalent forms.
 Non-equivalent resonance hybrids

e.g. thiocyanate ion, (NCS)- N C S

N C S N C S
-
N
- C S

Two forms the one with the negative charge on N will be more important
(electronegativity N>S), although both will contribute to the final hybrid.

This introduces the idea of preferred Lewis structures, and this will help us to predict
relative stabilities of isomers.

Note do not confuse the resonance forms shown so far with isomers, where the
spatial arrangements of the atoms differ.
Why is carbon dioxide OCO and not COO?

O C O
Lewis structures:

Compared to 2-
C O2+ O

The latter has (i) large formal charges, and (ii)

negative charge on less electronegative atom.

Another Example:
The ion (NCO)- is stable; the ion (CNO)- is known,
but very unstable. Why is this?
Lewis structures for the two isomers are:

N C O- N- C O

C2 N+ O- respectively.
This again explains the observed properties.

Note that in the former, the negative charge will be

predominantly on O rather than N, from their relative
electronegativities.

Summaries requirements for a preferred Lewis structure:

1. Keep formal charges to a minimum.

2. Where formal charges are necessary, they

should be consistent with relative
elctonegativities (ve charge on more
electronegative atom), and
3. Keep like charges as far apart as possible

Two final examples (more in tutorial work):

 H2O2 and F2O2

For H2O2 the only realistic Lewis structure is

H O O H
Because F is so electronegative, in the other case we can
have: O F-
F O F O +
O F

+ O
F O F-

This accounts for the observation that the O-O distance

in H2O2 is much longer than in F2O2.
 Dinitrogen tetroxide

N2O4 is an unusual molecule it has an N-N bond, but this

is very long (weak) and the molecule readily splits into
two NO2 fragments. Can Lewis structures explain this?
O O
There are several equivalent
N N
possible Lewis structures,
but they are all of the form O O

Repulsion between the +Ve charges on the N atoms leads

to the N-N bond being very weak.
Before moving on to the actual shapes of molecules, we must
recognize that not all
Covalent bonds are formed by taking one electron from each of two
atoms.

Dative (coordinate) bonds

Sometimes a covalent bond is formed by one atome (DONOR)

giving both electrons to another (ACCEPTOR).

Ammonia (NH3) has a LONE PAIR of electrons on the N atom.

Boron trifluoride (BF3) only has 6 electrons associated with the B

atom. It can complete the octet by accepting the lone pair from NH 3.
 H
F

F : N H
B

F H

Now both B and N have effectively completed their octets. The arrow
is the standard symbol for such a dative (or coordinate or
donor/acceptor) bond. - +
F3B N H3
In abbreviated form this is:

Note that, once formed, this type of bond behaves just like any other
covalent bond.

Another way of writing these bonds is:

F 3B NH3
 SHAPES OF COVALENT MOLECULES

Need a method for predicting shapes of molecules.

Here is one which works very well for compounds of s- and
p-block elements (not for d- and f-block see later
lectures)
Valence {page;307}
Shell
Electron
Pair
Repulsion
VSEPR tells us that the preferred structure of a
molecule minimizes repulsions between
electrons.

Repulsions between nuclei are assumed to be

negligible.

Core electrons (close to nuclei) are also

neglected, i.e. valence electrons only.

Electrons will form pairs (lone or bonding)

wherever possible.
Standard procedure:
1.Determine Lewis structure (s) for the molecule as
above.
2.Count valence electrons according to well-defined
rules see later.

All structures are based on a few fundamental

geometries

Start off with simple examples only one

CENTRAL ATOM, with ALL of its valence electrons
used to form SINGLE BONDS.
ABn
General formula
 AB2 Two pairs of valence electrons around A

Repulsions minimized by a LINEAR arrangement

B A B
Bond angle exactly 1800 any change increases
repulsions.
E.g. BeCl2: Valence electrons at Be 2
two Be-Cl bonds 2
Total valence electrons
at Be 4
TWO pairs therefore AB2, linear:
Cl Be Cl Note equal bond lengths
 Three pairs of valence electrons around A
AB3 B

A
Repulsions minimized by a B B
TRIGONAL PLANAR arrangement

Bond angles all 1200; bond lengths equal

E.g. BF3: Valence electrons at B 3
three B-F bonds 3
Total valence electrons
at B F 6
Three pairs therefore
AB3, trigonal planar.
B
F F
 AB4 Four pairs of valence electrons around
A B
Repulsions minimised by a
B
TETRAHEDRAL arrangement A
Bond angles all 109028; bond B B
lengths equal

E.g. CH4: Valence electrons at C 4

four C-H bonds 4
Total valence electrons at C 8
H

Four pairs therefore H

AB4, tetrahedral: C
H H
 AB5 Five pairs of valence electron
around A
B

B
Trigonal
B A
B Bipyramid
B

Accurate calculations show that the TRIGONAL

BIPYRAMID is slightly favored hence this is the
predicated geometry.

Note: In the trigonal bipyramid not all angles are

equal, some 90 , some 1200.
E.g. PF5: -Valence electrons at P,,,,,,,,,5
-Five P-F bonds ,,,,,,,,,5
-Total valence electrons
at P ,,,,,,,,,10

- FIVE pairs therefore AB5. Trigonal bi-

pyramidal:

F(ax)

F(eq) Note <F(eq)PF(eq) = 1200

(eq)F A <F(ax)PF (eq) = 900
F(eq)

F(ax)
 AB6 Octahedral

B
All angles 90
B
B
A
B
B
B