Chemistry, The Central Science, 11th edition

Theodore L. Brown; H. Eugene LeMay, Jr.;

and Bruce E. Bursten

Chapter 22
Chemistry of the
Nonmetals
John D. Bookstaver
St. Charles Community College
Cottleville, MO

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Nonmetals
Except for
hydrogen,
the
nonmetals
are found in
the upper
right-hand
corner of the
periodic
chart.
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Periodic Trends
Within a group,
smaller atoms
are more likely
to form -bonds
because they
can get closer
to other atoms.

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Periodic Trends
As a result, CO2 contains
two -bonds, and SiO2 is
a network solid with only
-bonds.

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Hydrogen:
It was discovered by
Henry Cavendish (1731
1810).
There are three isotopes:
Protium (1H): 99.98% of
all hydrogen.
Deuterium (2H): 0.016% of
all hydrogen
Tritium (3H): Radioactive

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Properties of Hydrogen
Hydrogen is unique.
It does not belong to any group.

It has very low melting (259 C) and

boiling (253 C) points.
It has very large bond enthalpies.
Therefore, it reacts slowly,
And its reactions are generally quite
exothermic.
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Hydrogen Production
Hydrogen is commercially produced from reaction
of methane (CH4) with steam at 1100C or carbon
and steam above 1000C.
CH4(g) + H2O(g)

CO(g) + H2O(g)
C(s) + H2O(g)

CO(g) + 3 H2(g)
CO2(g) + H2(g)
H2(g) + CO(g)

Its production from the electrolysis of water is not

energy efficient.
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Uses of Hydrogen
Most hydrogen is
used to produce
ammonia (NH3) in
the Haber process.
It is also used to
produce methanol
(CH3OH).
CO(g) + 2 H2(g)

CH3OH(g)

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Uses of Hydrogen
2 H2(g) + O2(g)

2 H2O(g) H = 483.6 kJ

Using hydrogen as a fuel would have

many advantages:
It's reaction with water is highly exothermic.
Water is the only product

Problem: How will we make the H2?

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Hydrides
There are three types of hydrides:
Ionic
Metallic
Molecular

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Ionic Hydrides
Ionic hydrides are
formed between
hydrogen and alkali
metals or heavy
alkaline earth metals
(Ca, Sr, Ba).
They are very strong
bases and reducing
agents.
They react readily with
water, so they must be
stored free from
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moisture.

Metallic Hydrides
These are formed between hydrogen
and transition metals, often in unusual
ratios.
TiH1.8, for example.

They retain electrical conductivity and

other metallic properties.
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Molecular Hydrides
These are formed
between hydrogen and
nonmetals or
metalloids.
They are usually gases
or liquids at room
temperature and
normal atmospheric
pressure.
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Noble Gases
Noble gases are
extremely stable and
unreactive.
Liquid He (boiling point
4.2 K) is used as a
coolant.
Ne is used in electric
signs.
Ar is used in light bulbs
and as an insulating
gas between panes in
thermal windows. Nonmetals

Xenon Compounds
Of all noble gases, Xe can
be forced to form
compounds most easily.
KrF2 is also known, but
decomposes at 10C.

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Halogens
The halogens have
outer electron
configurations of
ns2np5.
They have large
electron affinities and
ionization energies.
They tend to accept
one electron to form
anions.
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Halogens
All have a 1
oxidation state.
All but fluorine also
have positive
oxidation states up
to +7 when bonded
to more
electronegative
atoms.
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Properties of Halogens
They tend to be
good oxidizers,
due to their
electronegativity.
They can oxidize
anions of halides
below them on
periodic chart.
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Properties of Halogens
Fluorine has an unusually high reduction potential.
It can easily oxidize water.
F2(aq) + H2O(l)

2 HF(aq) + 1/2 O2(g) E = 1.80 V

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Uses of Halogens
Fluorine reacts to
form fluorocarbon
compounds used as
lubricants,
refrigerants and
plastics.
Teflon is a polymer
of fluorocarbons.
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Uses of Halogens
Chlorine is the most-used halogen.

HCl
Plastics
Bleaches
Water purification

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Uses of Halogens
Bromine is the anion
for silver in
photographic film.
KI is added to table
salt as a dietary
supplement.

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Hydrogen Halides
Aqueous solutions of HCl,
HBr, and HI are, of course,
strong acids.
HF and HCl can be produced
by reacting salts with H2SO4.
Br and I oxidize too easily,
so one must use a weaker
oxidizing acid, like H3PO4.
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HF
Hydrofluoric acid
reacts with silicates,
components of most
types of glass.
This reaction causes
glass to etch.
Therefore, HF is
usually stored in
plastic containers.
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Oxyacids and Oxyanions

Oxyacid strength increases with the increasing
oxidation number of the central halogen.
Oxyacids are strong oxidizers.
Oxyanions generally more stable than the
corresponding acids.

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Perchlorates
While generally
quite stable,
perchlorates
become exceedingly
strong oxidizers
when heated, and
are used as rocket
fuel.
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Oxygen
Joseph Priestley
discovered oxygen
in 1774.
Lavoisier give it its
name, which means
acid former.
Most commercial
oxygen is obtained
from air.
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Oxygen
It exists as one of two allotropes, O 2
and O3 (ozone).
It forms very strong bonds.
The reactions of oxygen-containing
compounds have high activation energies.
Its reactions can be very exothermic, even
to point of being explosive.
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Uses of Oxygen
Most notably,
oxygen is an
oxidizing agent.
Bleach pulp and
paper
Medical uses
Welding (with
acetylene)
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Ozone
It is a bluish gas with a
sharp odor.
It is extremely irritating to
respiratory system.
It is a stronger oxidizer
than O2.
It is used to purify water

It is used in organic
synthesis.
Of course, it absorbs UV
light in upper atmosphere.

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Oxides
Oxygen is second-most
electronegative element.
It always has a negative
oxidation state except
when bonded to F.

Acidic oxides like SO2

and SO3 form acids
when exposed to water.
Basic oxides like BaO
form hydroxide ion when
they react with water.

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Peroxides
In peroxides oxygen
has oxidation state of
1.
The OO bond very
weak.
The decomposition of
peroxides can be
dangerously exothermic.

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Superoxides
In superoxides oxygen
has oxidation state of
1/2.
The most active metals
(K, Rb, Cs) form
superoxides through
reaction with O2.
They react with H2O to
form O2.
It is the source of O2 in
self-contained breathing
devices.

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Other Group 6A Elements

Elements in this group have oxidation states
of 2 as well as several positive oxidation
states.
They can have expanded octets.

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Selenium and Tellurium

These elements are
anions in minerals with
Cu, Pb, Ag, and Au.
They are naturally found
as helical chains of
atoms.
Selenium is not
electrically conductive in
dark, but quite so in light.
Therefore, it is used in
light meters,
photosensors, and
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photocopiers.

Sulfur
Sulfur is a solid, yellow
compound found as an
8-membered ring in
nature.
As it is heated to
melting, the ring breaks
and the sulfur becomes
a viscous, reddish-brown
liquid.
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Sulfur
Most sulfur is used either for the production of
H2SO4 or for the vulcanization of rubber.

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Pyrites
Pyrites contain the
disulfide ion, S22,
the sulfur analog of
peroxide.
It is found in
minerals like iron
pyrite (fools gold).

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Sulfides
To say that many sulfides have rather
unpleasant odors is a gross
understatement.
H2S is emitted by rotten eggs.

Many minerals like galena (PbS) and

cinnabar (HgS) are sulfides.
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Sulfur Oxides, Oxyacids, and

Oxyanions
SO2 is a poison, particularly to lower
organisms.
It is used to sterilize dried fruit and wine.
It does this by dissolving in H2O to form
H2SO3.

Sulfites and bisulfites are added to

foods and wines to kill bacteria.
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Sulfur Oxides, Oxyacids, and

Oxyanions
Sulfuric acid is a
Strong acid,
Good dehydrating agent, and
Decent oxidizer.

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Sulfur Oxides, Oxyacids, and

Oxyanions

Sulfate

Thiosulfate ion resembles sulfate ion

(an S replaces one of the Os in
sulfate).
Sodium thiosulfate pentahydrate
(Na2S2O3 5 H2O) is used in
photography to remove unexposed
AgBr from film as a soluble complex of
thiosulfate.
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Thiosulfate

Nitrogen
Nitrogen was
discovered in 1772 by
Daniel Rutherford.
It makes up 78% of
Earths atmosphere.
It can exist in oxidation
states from 3 to +5.
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Nitrogen

Many nitrogen-containing compounds are

strong oxidizers.
N2 is made into NH3 in the Haber process.
NH3 is a precursor to many other compounds.
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Ammonia
Hydrazines are made from
ammonia.
One intermediate in the
process is chloramine
(NH2Cl), the poisonous
compound produced when
household ammonia and
hypochlorite ion in bleach are
mixed.

Hydrazines are strong

oxidizers used in rocket
fuels.

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Nitrogen Oxides and Oxyacids

Nitrous oxide (N2Olaughing gas) was
the first general anesthetic.
It is also used in aerosol products such
as whipped cream.

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Nitrogen Oxides and Oxyacids

Nitric oxide (NO) is a slightly toxic, colorless gas.
It has recently been shown to be a neurotransmitter
involved in vasodilation in humans.

It reacts with O2 in the air to produce nitrogen

dioxide, NO2.

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Nitrogen Oxides and Oxyacids

Nitric acid is
A strong acid and
oxidizer.
Used in fertilizer and
explosive production
(TNT, nitrocellulose,
nitroglycerine).

Nitrous acid is
A less stable, yet weaker
acid than HNO3.

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Other Group 5A Elements

This group contains nonmetals (N and P),
a metal (Bi), and metalloids (As and Sb).

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Phosphorus
There are two allotropes
of phosphorus:
White phosphorus (P4),
which
Is highly strained, and
Bursts into flames if
exposed to O2 in the air.

Red phosphorus,
Which is very stable.
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Oxyphosphorus Compounds
Phosphorus(III) oxide
(P4O6) and
phosphorus(V) oxide
(P4O10) are anhydride
forms of phosphorous
(H3PO3) and phosphoric
(H3PO4) acids.

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Carbon
Carbon has four allotropes:

Graphite,
Diamond,
Fullerenes, and
Carbon nanotubules.

Graphite is converted to
diamond (at 100,000 atm and
3000C) for industrial uses.
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Carbon Oxides
Carbon monoxide (CO)
This is an odorless, colorless gas.
CO binds preferentially to iron in hemoglobin,
inhibiting O2 transport.
It is used as a fuel, a reducing agent in metallurgy,
and a precursor to organic compounds.

Carbon dioxide (CO2)

This common gas is used to carbonate beverages,
decaffeinate products (in its supercritical form), and
as a refrigerant (as Dry Ice ).
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Carbonic Acid and Carbonates

Dissolved CO2 in water
is in equilibrium with
carbonic acid, H2CO3.
Carbonates are found
as minerals like calcite,
CaCO3, the primary
constituent of
limestone.
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Silicon
Silicon is the second
most abundant
element in Earths
crust.
It is a semiconductor
used in making
transistors and solar
cells.
It is purified by a
process known as
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zone-refining.

Silicates
Silicates have a
central silicon atom
that is surrounded
by four oxygens.
In disilicate, two
tetrahedral
structures share one
oxygen.

Silicate

Disilicate

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Silicates
These units can
further connect into
sheets or strands.
Talc and asbestos
are two examples of
molecules
containing these
structures.
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Boron
Boron is the only
nonmetallic Group 3A
element.
Compounds of boron and
hydrogen are called
boranes.
Because boron does not
have a filled octet,
structures such as diborane,
in which two borons share
one hydrogen, are possible.
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Boron
Borane anions, such
as borohydride,
BH4, are good
reducing agents and
sources of hydride
ion.

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