Chapter Nine
Chemical Bonding I
Basic Concept
Chapter Nine / Chemical bonding I, Basic Concept
Valence Electrons
Valence electrons: are the outer shell electrons of an atom. The valence
electrons are the electrons that participate in chemical bonding.
Group e- configuration # of valence e-
1A ns1 1
2A ns2 2
3A ns2np1 3
4A ns2np2 4
5A ns2np3 5
6A ns2np4 6
7A ns2np5 7
Chapter Nine / Chemical bonding I, Basic Concept
Lewis Dot Symbols
• Lawis dot symbol consists of the symbol of an element and one dot for
each valence electron in an atom of the element.
• The octet rule: in forming chemical bonds, atoms usually gain, lose or
share electrons until they have 8 electrons in the outer shell to reach the
same electronic configuration of the noble gasses (ns2 np6).
• There are two main types of chemical bonds: ionic bond and covalent
bond.
Chapter Nine / Chemical bonding I, Basic Concept
Lewis Dot Symbols
Lewis dot symbol for representative elements and noble gases
Chapter Nine / Chemical bonding I, Basic Concept
Ionic Bond
There are two type of bonds: Ionic bond and covalent bond.
An ionic bond is the electrostatic force that holds ions together in an ionic
compound.
Ionic bond occurs normally between metal and nonmetal and the electron
transfer from element to another element.
Example:
Li + F Li+ + F -
1S2 2S1 1S22S22P5 1S2 1S22S22P6
Chapter Nine / Chemical bonding I, Basic Concept
Ionic Bond
Example 2
Use Lewis dot symbol to show formation of Al2O3
2 Al + 3 O →
[Ne] 3s2 3p1 1s2 2s2 2p4
2 Al3+ + 3 O -2 (Al2O3)
[Ne] 1s2 2s2 2p6 [Ne]
Chapter Nine / Chemical bonding I, Basic Concept
Ionic Bond
Example:
An atom in the ground state has atomic number Z=5. Choose the correct
electron-dot structure which represents this atom?
a. X The electron configuration Z =5
1s2 2s2 2p1
Valence electrons are 2s2 2p1
b. X VE = 3 e
c. X
d. X
Chapter Nine / Chemical bonding I, Basic Concept
Covalent Bond
Covalent bond, is a bond in which two electrons are shared by two atoms.
Covalent bond occurs normally between nonmetal and nonmetal and the
electron only shared between elements (not transfer from element to
another element).
Example:
F + F F F
7e- 7e- 8e- 8e-
single covalent bond
F F
F F
single covalent bond
Chapter Nine / Chemical bonding I, Basic Concept
Covalent Bond
lone pairs: pairs of valence electrons that are not involved in covalent bond
formation.
single covalent bond lone pairs F F lone pairs
single covalent bond
lone pairs F F lone pairs
A Lewis structure is a representation of covalent bonding in which shared
electron pairs are shown either as lines or as pairs of dots between two
atoms, and lone pairs are shown as pairs of dots on individual atoms.
Chapter Nine / Chemical bonding I, Basic Concept
Covalent Bond
Lewis structure of water
single covalent bonds
H + O + H H O H or H O H
2e- 8e- 2e-
Double bond – two atoms share two pairs of electrons
O C O or O C O
-
8e 8ebonds
double 8e - - double bonds
Triple bond – two atoms share three pairs of electrons
N N or N N
-
8e bond
8e -
triple
triple bond
Chapter Nine / Chemical bonding I, Basic Concept
Valence Electrons
Bond length is defined as the distance between the nuclei
of two covalently bonded atoms in a molecule
Bond Lengths
Triple bond < Double Bond < Single Bond
Chapter Nine / Chemical bonding I, Basic Concept
Electronegativity
Polar covalent bond or polar bond is a covalent bond with greater electron
density around one of the two atoms
electron rich
electron poor
region
region e- poor e- rich
H F H F
d+ d-
Chapter Nine / Chemical bonding I, Basic Concept
Electronegativity
Electronegativity : the ability of an atom to attract toward itself the electrons
in a chemical bond.
Elements with high electronegativity have a greater tendency to attract
electrons than do elements with low electronegativity.
Electron Affinity - measurable, Cl is highest
X (g) + e- X-(g)
Electronegativity - relative, F is highest
Chapter Nine / Chemical bonding I, Basic Concept
Electronegativity
Chapter Nine / Chemical bonding I, Basic Concept
Electronegativity
Classification of bonds by difference in electronegativity
Difference Bond Type
0 Covalent
2 Ionic
0 < and <2 Polar Covalent
Increasing difference in electronegativity
Covalent Polar Covalent Ionic
share e- partial transfer of e- transfer e-
Chapter Nine / Chemical bonding I, Basic Concept
Electronegativity
Example
Classify the following bonds as ionic, polar covalent, or covalent
A) HCl 3-2.1 =0.9
Polar covalent
b) KF 4-0.8 =3.2
Ionic
c) C-C 2.5-2.5 =0
covalent
Chapter Nine / Chemical bonding I, Basic Concept
Electronegativity
Example
Classify the following bonds as ionic, polar covalent, or covalent
A) CsCl 3–1=2
Ionic
b) H2S 2.5 - 2.1 = 0.4
Polar covalent
c) N-N 3-3=0
covalent
Chapter Nine / Chemical bonding I, Basic Concept
Writing Lewis Structures
1. Draw skeletal structure of compound showing which atoms are bonded
to each other. Put least electronegative element in the center.
2. Count total number of valence e-. Add 1 for each negative charge.
Subtract 1 for each positive charge.
3. Draw single covalent bond between the central atom and each of the
surrounding atom, and complete an octet for all the surrounded atoms
except hydrogen. Count and Compare it with the number of electrons in
step 2 if they are identical stop, if it is less add the remaining electrons to
the central atom.
4. If the central atom still has no octet, use lone pair/s on the one of the
surrounded atom to form double or triple bond with the central atom.
Chapter Nine / Chemical bonding I, Basic Concept
Writing Lewis Structures
Example 1
Write the Lewis structure of nitrogen trifluoride (NF3).
Step 1 – N is less electronegative than F, put N in center
Step 2 – Count valence electrons N - 5 (2s22p3) and F - 7 (2s22p5)
5 + (3 x 7) = 26 valence electrons
Step 3 – Draw single bonds between N and F atoms and complete
octets on N and F atoms.
Step 4 - Check, are # of e- in structure equal to number of valence e- ?
3 single bonds (3x2) + 10 lone pairs (10x2) = 26 valence electrons
F N F
F
Chapter Nine / Chemical bonding I, Basic Concept
Writing Lewis Structures
Example 2
O C O
Write the Lewis structure of the carbonate ion (CO32-).
Step 1 – C is less electronegative than O, put C in center
Step 2 – Count valence electrons C - 4 (2s22p2) and O - 6 O
(2s22p4) -2 charge – 2e-
4 + (3 x 6) + 2 = 24 valence electrons 2 single bonds (2x2) = 4
Step 3 – Draw single bonds between C and O atoms and 1 double bond = 4
complete octet on C and O atoms. 8 lone pairs (8x2) = 16
Step 4 - Check, are # of e- in structure equal to number of Total = 24
valence e- ?
3 single bonds (3x2) + 10 lone pairs (10x2) = 26 valence
electrons
Step 5 - Too many electrons, form double bond and re-
check # of e-
Chapter Nine / Chemical bonding I, Basic Concept
Writing Lewis Structures
Example 3
Write the Lewis structure for nitric acid (HNO3) in which the three O atoms
are bonded to the central N and H atom is bonded to one of the O atoms?
Step 1: put N in center ,surrounded by 3O atoms , H bonded to one of the O.
Step 2: Count the valence electrons 5 + (3 x 6) +1 = 24 valence e-
Step 3: Draw single bonds between N and O atoms and O and H complete
octet on O and N atoms. Use all the valence e (step 2)
Step 4: Check, are # of e- in structure equal to number of valence e- ?
4 single bonds (4x2) + 9 lone pairs (9x2) = 26 valence electrons
Step 5 - Too many electrons, form double bond and re-check # of e-
O N O H
O
Chapter Nine / Chemical bonding I, Basic Concept
Formal Charges and Lewis Structure
formal charge is the difference between the number of valence electrons in
an isolated atom and the number of electrons assigned to that atom in a
Lewis structure.
total number of
formal charge on total number of
valence electrons total number of
an atom in a
Lewis structure
=
in the free atom - nonbonding
electrons
- bond
The sum of the formal charges of the atoms in a molecule or ion must equal the
charge on the molecule or ion.
Chapter Nine / Chemical bonding I, Basic Concept
Formal Charges and Lewis Structure
Example:
Ozone molecule (O3)
Lewis Structure: O–O=O
Formal Charge:
6 - 6 - 1 = -1 6 - 2 - 3 = +1 6 - 4 - 2 =0
-1+1+0=0
total number of
formal charge on total number of
valence electrons total number of
an atom in a
Lewis structure
=
in the free atom - nonbonding
electrons
- bond
Chapter Nine / Chemical bonding I, Basic Concept
Formal Charges and Lewis Structure
Example 2
Write the formal charges for the carbonate ion (CO32-)
6 - 4 - 2 =0
2-
O
O C O -1+0 -1+0=-2
6 - 6 - 1 = -1 4 - 0 - 4 =0 6 - 6 - 1 = -1
Chapter Nine / Chemical bonding I, Basic Concept
Formal Charges and Lewis Structure
Sometimes there is more than one acceptable Lewis structure for a given
species. In such cases, we can often select the most plausible Lewis
structure by using formal charges and the following guidelines:
1. For molecules, a Lewis structure in which there are no formal charges is
preferable to one in which formal charges are present.
2. Lewis structures with large formal charges (+2, +3, and/or -2, -3, and so
on) are less plausible than those with small formal charges.
3. Among Lewis structures having similar distributions of formal charges,
the most plausible structure is the one in which negative formal charges
are placed on the more electronegative atoms.
Chapter Nine / Chemical bonding I, Basic Concept
Formal Charges and Lewis Structure
Example
Draw the most likely Lewis structure for formaldehyde (CH2O).
a b
- +
H
H–C=O-H C=O
H
4 - 2 - 3 = -1 6 - 2 - 3 = +1 4 - 0 - 4 =0 6 - 4 - 2= 0
(b) is the more likely structure
because it carries no formal charges
Chapter Nine / Chemical bonding I, Basic Concept
The Concept of Resonance
A resonance structure is one of two or more Lewis structures for a single
molecule that cannot be represented accurately by only one Lewis
structure.
Example
What are the resonance structures of the carbonate (CO3)-2 ion?
- - - -
O C O O C O O C O
O O O
- -
Chapter Nine / Chemical bonding I, Basic Concept
The Concept of Resonance
Example
What are the resonance structures of Ozon (O3)?
- + + -
O–O=O
O–O=O
Example
What are the resonance structures of benzene molecule (C6H6)?
Chapter Nine / Chemical bonding I, Basic Concept
The Concept of Resonance
Example
Draw three resonance structures for the molecule nitrous oxide, N2O (the
atomic arrangement is NNO). Indicate formal charges. Rank the structures
- + + - 2- + +
N=N=O N N O N N O
a b c
Structure (b) is the most important one because the negative charge is on the
more electronegative oxygen atom. Structure (c) is the least important
one because it has a larger separation of formal charges. Also, the positive
charge is on the more electronegative oxygen atom.
Chapter Nine / Chemical bonding I, Basic Concept
Exceptions to the Octet Rule
Incomplete octet
The number of electrons surrounding the central atom in stable molecule is
less than 8.
Example coordinate covalent bond
BeH2 (also referred to as a dative
bond ),
defined as a covalent bond
H Be H in which one of the atoms
donates both electrons.
The electron configuration of beryllium is 1 s2 2s2 ; it has two valence
electrons in the 2s orbital.
Also group 3A (Al, B).
F–B–F
F
Chapter Nine / Chemical bonding I, Basic Concept
Exceptions to the Octet Rule
Incomplete octet
Example
Draw the Lewis structure for aluminium triiodide (AlI3)
The outer-shell electron configurations of Al and I are 3s2 2p1 and 5s2 5p5
respectively. The total number of valence electrons is 3 + 3 x 7 or 24.
Because Al is less electronegative than I, it occupies a central position and
forms three bonds with the I atoms:
I – Al -I
I
there are only six valence electrons around the Al atom. Thus, AlI3 is an
example of the incomplete octet.
Chapter Nine / Chemical bonding I, Basic Concept
Exceptions to the Octet Rule
Odd-Electron Molecules
molecules contain an odd number of electrons also called radical.
Radical: atom has one electron alone
Example are nitric oxide (NO) and nitrogen dioxide (NO2)
+ -
N=O O=N O
Chapter Nine / Chemical bonding I, Basic Concept
Exceptions to the Octet Rule
The Expanded Octet
3rd period and beyond (4th, 5th, 6th, 7th ) may form molecules in which the
central atom is surrounded by more than 8 electrons
Example
The electron configuration of sulfur is [Ne]3s2 3p4. In SF6 , each of sulfur’s six
valence electrons forms a covalent bond with a fluorine atom, so there are
12 electrons around the central sulfur atom:
F
F F
F F
F
Chapter Nine / Chemical bonding I, Basic Concept
Exceptions to the Octet Rule
The Expanded Octet
Example
Draw Lewis structure for phosphorus pentaflouridde (PF5), in which all five F
atoms are bounded to the central P atom.?
Valance electrons = 5 + (7 x 5 ) = 40 e
5x6=30 electron (lone pair)
5x2=10 electron (bond)
F
Total is 40 electron
F F
P has 10 electron (5x2) P
Thus it expanded octet
F
F
Chapter Nine / Chemical bonding I, Basic Concept
Exceptions to the Octet Rule
Exceptions to the Octet Rule
Example
Draw Lewis structure for sulphate ion (SO42-), in which all four O atoms are
bounded to the central S atom.
O O
- - - -
O S2+ O O S O
O- O
This structure has an expanded octet on S, BUT it
is more correct because, it has less formal
charges.
Chapter Nine / Chemical bonding I, Basic Concept
Exceptions to the Octet Rule
Example
When acting as a central atom, which of the following cannot expand its
octet?
a- P b-C c-Cl d-Xe e-S