Primary Bonds

Lecture 3
Ionic Bond

Covalent Bond

Metallic Bonding

Bond Length & Bond Energy

What atoms want?
Atoms are most stable when they have no partially-filled electron shells.
All chemical bonds involve electrons and atoms stay close together if they have a
shared interest in one or more electrons; hence they form a chemical bond.

electromagnetic attractive force between opposite charges: between electrons and
nuclei of both atoms that form a bond

If an atom has only a few electrons in a shell, it will tend to lose them to empty the
shell. These elements are metals.
When an atom has a nearly full electron shell, it will try to find electrons from another
atom so it can fill its outer shell. These elements are usually described as nonmetals.
OUTERMOST SHELL CLOSED: 8e
-

Ionisation energy
Ionization energy (ionization potential) is the energy necessary to remove an electron
from the neutral atom.


It is lowest for the alkali metals, which have a single valence electron.
Increases across a period, as the number of valence electrons increases.
Maximum for the noble gases, which have closed shells.
Tends to decrease in a group.

( ) ( )
+
+ e X X
g
E
g
I
Electron affinity
Electron affinity is a measure of the energy change when an electron is added to a
neutral atom to form a negative ion.



Highest for non-metals (17
th
group), as they need only one electron to fill the shell.
Generally increases in a period.
Decreases in a group.
Basically zero for noble gases.
( ) ( )

+
g
E
g
X e X
a
Chemical Bonds
Chemical compounds are formed by the joining of two or more atoms.
The total energy of the combined atoms is lower than the energy of separated atoms.

The various ways in which atoms can be bound together involve:
(1) Primary bonds - ionic, covalent or metallic bonds, which are all relatively strong
(2) Secondary bonds - Van der Waals and hydrogen bonds, which are both relatively weak

Ionic Bonds
Ionic bond - electrostatic attraction between positive and negative charges (ions)
Ionic bonds are formed between a cation = positively charged ion, which is usually a
metal, and an anion = negatively charged ion, which is usually a nonmetal.








Ionisation Energy Electron Affinity = 5.14 - 3.6 = 1.54eV ?!?!
NaCl Cl Na Cl Na
Cl e Cl
e Na Na
+ +
+
+
+

+
E
i
=5.14 eV
E
a
=-3.6 eV
Ionic Bonds
U - potential energy (net force)
q - charge on each ion
r - distance (separation) between the ions (n = 12)
( )
n
i
r
B
r
q
U r U + =
0
2
4tc
attractive part
repulsive part
Covalent Bonds
Covalent bond is characterized by the sharing of pairs of electrons between atoms
(commonly nonmetals), in contrast to the transfer of electrons in ionic bonds.
Such bonds lead to stable molecules (a noble gas configuration for each atom).








Covalent Bonds










( ) n m
r
B
r
A
r U
n m
< + =
Electronegativity
Molecule is an electrically neutral group of at least two atoms held together by
covalent chemical bonds.

Electronegativity is a measure of the ability of an atom in a molecule to draw bonding
electrons to itself.
Linus Pauling has assigned the value 4.0 to fluorine (F), the most electronegative
element. Difference between electronegativities of constituent atoms is used for the
prediction of the polarity of a chemical bond.

Covalent bonds are affected by the electronegativity of the connected atoms.
Two atoms with equal or similar electronegativity will make non-polar covalent bonds.
Otherwise, the covalent bond is polar.





Polar & Non-polar Covalent Bonds
Covalent bonds in which the sharing of the electron pair is unequal, with the electrons
spending more time around the atom with higher electronegativity, are called polar
covalent bonds. If atoms have the same electronegativity non-polar covalent bond.

In a polar covalent bond there is a charge separation with one atom being slightly more
positive and the other more negative, i.e., the bond will produce a dipole moment.
Covalent Bonds in Polymers
A polymer is a large molecule (macromolecule) composed of repeating structural units.
These subunits (monomers) are typically connected by covalent chemical bonds.
Polymerization is a process of reacting monomer molecules together in a chemical
reaction to form polymer chains.


Natural: cellulose, shellac, amber, rubber

Biopolymers: nucleic acids, proteins

Synthetic: polyethylene (PE), polypropylene
(PP), polystyrene (PS), nylon, PVC, epoxy
resins, synthetic rubbers, teflon, etc.
Ionic vs. Covalent Bonds
Property Ionic Compounds Covalent Compounds
Elements metal - nonmetal nonmetal - nonmetal
Phase (at STP) solid (in crystal lattice) solid, liquid or gas
Hardness hard and brittle (salt)
brittle and weak (sugar)
or soft and waxy (butter)
Melting/Boiling Points high low
Solubility mostly soluble in water solubility varies widely
Electrical Conductivity
solid - nonconductor,
liquid or aqueous solution -
conductor
insulators
Metallic Bonding
Metallic bond is the electrostatic attractive force between the delocalized electrons, and
the positively charged metal ions (cations).
The properties of metals : conduction of heat and electricity suggest that electrons can
move freely in all directions in the lattice.
positive ions in a sea of electrons

strength varies from metal to metal
depends on the structure






Bond Lengths & Bond Energy
The length of a chemical bond is the distance between the centres of the two bonded
atoms (the internuclear distance).
Bond lengths have traditionally been expressed in ngstrom units, but
the official unit is a picometer (1pm = 0.01 = 10
-12
m).

Bond lengths depend mainly on the sizes of the atoms,
and secondarily on the bond strengths: stronger bonds are shorter.
Multiply-bonded atoms are closer together than singly-bonded ones.

Bond e
-
Order Strength Length
Single 2 1 weakest longest
Double 4 2
Triple 6 3 strongest shortest
Bond Lengths & Bond Energy
Bond lengths depend mainly on the sizes of the atoms, and secondarily on the bond
strengths; stronger bonds are shorter.
Multiply-bonded atoms are closer together than singly-bonded ones.

The bond energy is the amount of work that must be done to pull two atoms
completely apart (the depth of the well in the potential energy curve).
stronger bond has higher energy and shorter length