Unique Nature of Carbon

Carbon has two properties that enable it to

form such an extensive range of compounds:

1. Catenation – the ability to form chains of

atoms.
2. The ability to form multiple bonds.
 Catenation
The elements nitrogen and oxygen do not
undergo extensive catenation. Compounds that
contain –O-O- bonds (peroxides) are typically
unstable and explode.
Likewise, compounds containing -N-N-
bonds are often explosive. An example is the
azide ion, N31-.
 Catenation
Carbon readily forms long chains of bonds
with itself. This property is called catenation, and
is fairly unique. It results for several reasons:
1. Carbon can make up to 4 bonds.
2. The carbon-carbon bond is generally as
strong as bonds between carbon and other
elements.
3. The catenated compounds are inert.
 Catenation
Silicon can also make long chains within its
compounds, but, since the silicon oxygen bond
is much stronger than that between two silicon
atoms, the chains typically contain –O-Si-O-Si-
type links, rather than -Si-Si- bonds.
Silicon also has empty low-lying d orbitals
which make its compounds more reactive.
 Typical Bond Energies

C−O 358
 Catenation
Since carbon can undergo extensive
catenation and make as many as four bonds, the
array of compounds is limitless.

The simplest compounds, those with carbon

and hydrogen, are used as the basic structure of
all molecules.
Carbon vs. Silicon
 Carbon vs. Silicon
One of the clearest differences between the
two elements is in their oxides. Carbon dioxide
is a non-polar molecular substance with double
bonds between the carbon and the oxygens.
: :

: :
O=C=O
 Carbon vs. Silicon
Since silicon doesn’t readily make double
bonds, and the silicon-oxygen bond is so stable,
the oxide of silicon is a network solid, in which
each silicon atom is bonded to four oxygen
atoms which are, in turn, bonded to other
silicon atoms.
Carbon vs. Silicon
The oxide of silicon
is found in quartz and
sand.
 Silicates
Silicates, ions containing silicon and oxygen,
are found in most rocks, soils and clays. Their
structures also are based on interconnected SiO4
tetrahedral units.
Silicates
Glass contains
silicates in a more
random pattern than
found in quartz.
 Group 5A
The elements of group 5A may form three,
five or six covalent bonds, except for nitrogen
which cannot expand its “octet.”

Due to its small size, nitrogen readily forms

π bonds. Thus elemental nitrogen, N2, has a
triple bond. The other elements exist as larger
molecules containing single bonds.
 Nitrogen
Elemental nitrogen is an extremely stable
molecule due to the triple bond. As a result,
many nitrogen containing compounds
decompose exothermically (and sometimes
explosively) to form nitrogen gas.
 Explosives
Nitrogen based
explosives such as
nitroglycerin, will rapidly
decompose when ignited or
exposed to a sudden
impact.
 Explosives
4 C3H5(NO3)3(l)  6 N2(g) + 12 CO2(g) +
10 H2O(g) + O2(g) + energy

Note the large number of moles of gaseous

products. Explosives typically involve a very
large volume change, producing many moles of
small gaseous molecules.
 Explosives
Trinitrotoluene, TNT, is another nitrogen
based explosive.

2C7H5(NO3)3(l)  12 CO2(g) + 5 H2(g) +

3N2(g) + 2C(s) + energy
Sodium Azide
Sodium azide,
NaN3(s), is used in air
bags in automobiles.
A small amount of
sodium azide (100g)
yields 56L of
nitrogen gas at 25oC
and 1 atm.
 Sodium Azide
2 NaN3(s)  2Na(l) + 3 N2(g)
This reaction takes place in about 40ms. Other
components are put in the air bag so that the
molten sodium metal is deactivated into glassy
silicates.
10 Na(l) +2KNO3(s) K2O(s) +5Na2O(s)+ N2(g)
2 K2O(s) + SiO2(s)  K4SiO4(s)
2 Na2O(s) + SiO2(s)  Na4SiO4(s)
Isolation of Phosphorus
Phosphorus was
initially isolated in an
attempt to extract
gold from urine.
The element emits
light and glows when
exposed to oxygen.
 Phosphorus
Elemental phosphorus exists as several
allotropes. All differ greatly in structure from
nitrogen due to a lack of multiple bonding
between the larger phosphorus atoms.
Phosphorous can also use d orbitals to
expand its bonding.
 Elemental Phosphorus

white black red

phosphoru phosphorus phosphorus
s
Elemental Phosphorus
White Phosphorus
White phosphorus exists
as discrete P4 molecules.
It is a waxy white solid
that is very poisonous and
reactive. It burns
vigorously in air, and is
stored under water.
 White Phosphorus
The element gets its name from the
phosphorescent glow emitted by white
phosphorus when it is exposed to air in the
dark.
White phosphorus has been used in
weaponry. The pieces of phosphorus in bombs
and grenades get embedded in the skin, where
they burn.
 Red Phosphorus

Red Phosphorus is a polymeric chain of P4

units. It is stable in air to a temperature of
400oC. Red phosphorus is used in “safety”
matches on the striking surface.
 Red Phosphorus

Red phosphorus is used in “safety” matches on

the striking surface.
 Black Phosphorus

Black phosphorus is the most stable of the

allotropes. It is formed from white phosphorus
that is heated under very high pressures.
 Oxygen
Oxygen contains a double bond that is much
stronger than a single bond (494 kJ/mol vs. 142
kJ/mol). The lower elements in the group form
much weaker π bonds due to their larger atomic
size and greater bond length.
 Oxygen
Oxygen is a colorless, odorless gas that
forms a pale blue liquid. The molecule is
paramagnetic due to the presence of two unpaired
electrons, and is attracted to a magnetic field.
 Ozone
Ozone, O3, is an allotrope of oxygen. It
occurs naturally in the upper atmosphere of
earth. The ozone layer absorbs ultraviolet light
and serves to help screen out harmful, cancer
causing, radiation.
Sulfur
Sulfur is found in
large deposits as the
free element, or in a
variety of ores.
Elemental sulfur has a
variety of forms and
structures. At room
temperature, the most
stable form is
rhombic sulfur, S8
rings.
Structure of Sulfur

Sulfur has a tendency

to bond with itself.
This is called catenation.
The sulfur-sulfur bonds
are stable, despite lone
pairs, since the bond
length is relatively long.
 Sulfur
If molten sulfur is cooled slowly, the eight-
membered rings stack into monoclinic sulfur, which
has a needle-like appearance.