Covalent Bond

Chapter 8

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 Electronegativity ()

- the ability of an atom in a molecule to attract an

electron to itself
Useful parameter for predicting general chemical behaviour
of an element.

Predicting polarities of bonds and molecules

Bond is covalent if EN<1.2,
Polar if 1.2 < EN<1.8
Ionic if EN>1.8

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Polar Covalent Bond & Electronegativity
Discuss the nature of these
bonds:
HF, HCl
HOH (including lone pairs)
Electronegativity: the ability
of an element competing for
bonding electrons.

The variation as a function of

atomic number and its trends on
the Periodic Table has been
discussed previously, and the
Periodic Table showing
electronegativity is shown next.
3
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 Polarizing Power and Polarizability

Consider a bond between two atoms

If the atoms are equally electronegative, both have the same

tendency to attract the bonding pair of electrons, and so it will be
found on average half way between the two atoms
What happens if B is slightly more electronegative than A?

This is described as a polar bond - a covalent bond in which

there is a separation of charge between one end and the other.

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 Covalent and Ionic Bonds
The ionicity of a bond depends on the difference in
electronegativity.
A difference of 1.7 is given as 50% ionic, and
usually considered ionic.

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 Polarizing Power and Polarizability

A nonpolar covalent bond is one in which the electrons are

shared equally between two atoms

A polar covalent bond is one in which one atom has a

greater attraction for the electrons than the other atom.

If this relative attraction is great enough, then the bond

is an ionic bond

Polarization can be used to estimate the relative

importance of covalency in highly polar systems.

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Polarizing Power and Polarizability

Polarization is the distortion of the

electron cloud of one atom by
another. non-polar molecule

Atoms and ions that readily undergo

a large distortion in their electron
clouds are said to be highly slightly polar
polarizable

Those that cause large distortions

have a high polarizing power
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highly polar
10.7.00 6:16 PM
 Polarizing Power and Polarizability

Guidelines summarized by Fajans:

1. Positive ions can have the effect of polarizing

(electrically distorting) nearby negative ions
Polarizing Power increases as the positive ion gets
smaller and the number of charges gets larger.

2. As a negative ion gets bigger and the charge gets

larger it becomes easier to polarize
For example compare the polarizability of I- versus
F-

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 Polarizing Power and Polarizability

Due to trends in polarizability and polarizing

power covalency tends to increase:

1. On ascending a group for cations or

descending a group for anions

2. On going from left to right across a period

for cations and right to left for anions

3. With increasing oxidation state of cations and

decreasing oxidation state for anions.

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 Aluminium bromide is covalent because the electron pair
is easily dragged away from the iodide ion. The high
charge density on the cation can distort the diffuse
electron cloud of the anion.

On the other hand, aluminium fluoride is ionic because

the aluminium ion can't polarize the small fluoride ion
sufficiently to form a covalent bond.

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 Polarizing Power and Polarizability

The polarizing power of a cation can be estimated from

the ratio of its charge to ionic radius (Z/r)

Consider Al3+ which is highly polarizing

Ionic radius = 0.39 in Charge = +3

Z/r = 7.7. This is known as the charge density or ionic

potential

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 Dipole Moment

The product of magnitude of

charge on a molecule and the
distance between two
charges of equal magnitude
with opposite sign is equal to
dipole moment; D (unit is
debye, 1 D = 3.34E30 C m
(coulumb.metre);
representation Cl+H, a HCl = 1.03 D
vector ) HF = 1.9 D, find d
Dipole moment = charge x and % ionic
distance character for
Symbol: = e x d them.
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 Some typical Bond
Dipoles:
Bond Debyes

C-N 0.22
C-O 0.86
C-F 1.51
C-Cl 1.56
C-Br 1.48
C-I 1.29
H-C 0.3
H-N 1.31
H-O 1.53
C=O 2.4
C=N 3.6
-

Q: Why is the C-F bond less polar than the C-Cl, since F is
more electronegative than Cl?

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 Drawing Lewis
Structures

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 Lewis Structure by Bond
Determination
1. Know how to determine the valence electrons for all elements.
2. (Connectivity) From the chemical formula, determine the atom
connectivity for the structure.
i. Given a chemical formula, ABn, A is the central atom and B flanks
the A atom. i.e., NH3, NCl3, NO2. In these examples, N is central in the
structure.
ii. H and F are never central atoms.
2. (# of electrons in Bonding) Determine the number of bonds in
the compound, by calculating the theoretical Octet electrons
(Oe) minus the total valence electrons (TVe) and dividing by 2
(2 electrons = 1 bond).
Oe is the theoretical number of electrons necessary for each
atom in the structure to obtain a Noble Gas electron
configuration, while TVe is the actual number of total valence
electron for each atom in the structure.
3. (Remaining e-) Calculate the number of remaining electrons in
the compound by taking the total valence electron (TVe)
minus the number of electrons that was used to form bonds.

Complete the Lewis structure by drawing atomic

connectivity. Write bonds in the structure and the
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 Valence electrons for Elements
Recall that the valence electrons for the elements can be
determined based on the elements position on the periodic
table.

Lewis Dot Symbol

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 Valence electrons and number of
bonds
Number of bonds elements prefers depending
on the number of valence electrons. In

general -
Family # Covalent Bonds*

1 bond often
Halogens
F, Br, C l, I
X

Calcogens
O, S
O 2 bond often
N itrogen
N, P
N 3 bond often

Carbon
C, Si
C 4 bond always

The above chart is a guide on the number of bonds formed by

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 Lewis Structure, Octet Rule
Guidelines
When compounds are formed they tend
to follow the Octet Rule.
Octet Rule: Atoms will share electrons (e-) until it is
surrounded by eight valence electrons.
Rules of the (VSEPR) game-
i) O.R. works mostly for second period elements.
Manyexceptionsespeciallywith3rdperiodelements(dorbitals)
ii) H prefers 2 e- (electron deficient)
. . ..
iii) ..
:C: N: :O::F:
.
4unpaired 3unpaired 2unpaired
.
1unpaired
up=unpairede
4bonds 3bonds 2bonds 1bond
O=C=O NN O = O F - F
iv) H & F are terminal in the structural formula (Never central)

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 Atomic Connectivity
The atomic arrangement for a molecule is usually given.
CH2ClF HNO3 CH3COOH H2Se H2SO4 O3
Cl
O N O H O O
H Se H O O O
H C F
O
H C C H O S O H
H
H
H O H
O

In general when there is a single central atom in the molecule, CH2ClF,

SeCl2, O3 (CO2, NH3, PO43-), the central atom is the first atom in the
chemical formula.
Except when the first atom in the chemical formula is Hydrogen (H) or
fluorine (F). In which case the central atom is the second atom in the
chemical formula.

Find the central atom for the following:

1) H2O a) H b) O 2) PCl3 a) P b) Cl
3) SO3 a) S b) O 4) CO32- a) C b) O
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 Setting up Bond Table
Setting up the bond table requires the chemical
formula, and determining the number of electrons
around each atom.
A) Chemical Formula I.e., HNO3
B) Oe - Octet Electrons. This is always either 8 or 2
(for H)
C) ChemFormula
Tve - Total Valence
OctetElectron.
e- Tot Val e-
HNO3 Oe Tve
1x2=2 1x1=1
H
1x8=8 1x5=5
N
O 3 x 8 = 24 3 x 6 = 18
34 24

Note
Note this
this recipe
recipe works
works only
only if
if the
the chemical
chemical specie
specie obeys
obeys the
the octet
octet
rule.
rule. For
For chemical
chemical specie
specie which
which violates
violates the
the octet
octet rule,
rule, this
this
method
method must
must bebe modified.
modified.
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 Calculating the Number of Bonds
and the Remaining electrons
After setting up the bond table, calculate the
number of bonds in the chemical specie and the
number of electrons.
The remaining electrons are place around the
atoms in the chemical specie such that each atom
obeys the octet rule

HNO3 Oe Tve # Bonding e-

34 - 24 = 10
Bond Table
# of Bonds 10/2 = 5

Remaining e- Tve(24) - electrons in Bond (10) =

14

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 Putting it Together
1) Chemical formula: 2) Atomic sequence:
HNO3
O N O
O
3) Number of bonds =5 H
4) Remaining electrons = 14

5) Lewis Structure with 5 bonds:

6) Complete Lewis Structure
O with
N 14O remaining electrons
O
O N O
H
O
H
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 Lewis Dot Structure of CO2 by Bonds
Table
A. Calculate Octet electrons (Oe-) and B. Calculate the number of bonds in
Total Valence electrons to determine compound structure.
number of bonds # bonds = (Oe - TVe)
CO2 Oe TVe 2

1 C 1(8)= 8 1(4) = 4 = (24- 16) = 8 = 4

bonds
2 O 2(8)=16 2(6)=12 2 2
Chg C. Calculate the remaining electrons to
24 16 add to structure to complete Lewis dot
structure.
Remaining e- = TVe - e- used in
Writing Lewis Structure: bonding.
First determine atom connectivity keeping in mind = that
16 - H8 and
= 8 e-
F can
Remaining
never be central atoms. Generally when given the formula, ABn, A is
the central atom in the structure (but not always), and B atoms flank
the central atom. Next use information from the above calculations.
Total of 16e- in CO2, of which 8 electrons are used to form 4 bonds and
8 remaining electrons are used to complete Lewis structure.
O C O O C O O C O
1,2. Write atom 3,4,5. Draw the four 6. Place the remaining 8 electrons in
connectivity for CO2. bonds in the structure. the structure to complete the Lewis
Structure
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 Lewis Dot Structure of ClO4- by Bonds
Table
A. Calculate (Oe-) and
(TVe) B. Number of Bonds.
ClO4- Oe TVe # bonds = (40- 32) =8 = 4
bonds
1 Cl 1(8)= 8 1(7) = 7 2 2
4 O 4(8)= 32 4(6)= C. Remaining electrons.
24 Remaining e- = 32 - 8 = 24 e-
Remaining
Chg 1
40 32
Writing Lewis Structure:
6. Place the remaining 24
1,2. Write atom 3.4.5. Draw the
electrons in the structure such
connectivity for ClO4-. four bonds in the
that each atom has an octet to
structure.
complete the Lewis Structure
O O O
O Cl O
O Cl O O Cl O
O
O O
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 Lewis Structures: Examples
Example

a) CH2ClF b) SO2
Cl
H C F O S O
H

c) SO42- d) H3PO4
O O
O S O H O P O H
O O
H
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 Summary
Summary
Lewis Structure Determination:
Molecular Formula
Atomic Sequence (H and F are terminal)
Determine the # of bonds
Oe- and TVe-
# of Bonds = (Oe - TVe-) / 2
Determine remaining electrons
Re = (TVe-) - (# e- in bonding)
Make sure all atoms satisfy octet rule (Except H
which is satisfied with 2 electrons)

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 Formal Atom Charges
Atoms in molecules often bear a charge
(+ or -).
Formal charge = Group no.
- 1/2 (no. bond electrons)
- (no. of LP electrons)

The most important dominant resonance structure

of a molecule is the one with formal charges
as close to 0 as possible.

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 Carbon Dioxide, CO2

At OXYGEN 6 - (1/ 2)(4) - 4 = 0

O C O

At CARBON 4 - (1/ 2)(8) - 0 = 0

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 Carbon Dioxide, CO2 (2)

An alternate Lewis structure is:

6 - (1/ 2)(2) - 6 = -1

O C O


C atom
charge is
6 - (1/ 2)(6) - 2 = +1 0.
+
AND the corresponding
O C O


resonance form

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 Carbon Dioxide, CO2 (3)
Which is the predominant resonance structure?
+

O C O

O C O

OR
+
O C O

Answer ?
Form without formal charges is
BETTER - no +ve charge on O

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 Boron Trifluoride, BF3

F

B
F

What if we form a BF double

bond to satisfy the B atom
octet?
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 Boron Trifluoride, BF3 (2)

+
F

fc = 7 - 2 - 4 = +1 Fluorine

F B

fc = 3 - 4 - 0 = -1 Boron

F To have +1 charge on F, with its

very high electron affinity is not
good. -ve charges best placed
on atoms with high EA.
Similarly -1 charge on B is bad
NOT important Lewis structure

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