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chemical compound
By Steven S. Zumdahl • Article History

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oxide, any of a large and important class of

chemical compounds in which oxygen is
combined with another element. With the
exception of the lighter inert gases (helium
[He], neon [Ne], argon [Ar], and krypton
[Kr]), oxygen (O) forms at least one binary
oxide with each of the elements.

iron oxide

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Key People: Joseph Priestley

Related Topics: water • sulfur oxide • alumina •

titanium dioxide • oxide mineral

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Both metals and nonmetals can attain their

highest oxidation states (i.e., donate their
maximum number of available valence
electrons) in compounds with oxygen. The
alkali metals and the alkaline earth metals, as
well as the transition metals and the
posttransition metals (in their lower oxidation
states), form ionic oxides—i.e., compounds
that contain the O2− anion. Metals with high
oxidation states form oxides whose bonds
have a more covalent nature. Nonmetals also
form covalent oxides, which are usually
molecular in character. A smooth variation
from ionic to covalent in the type of bonding
in oxides is observed as the periodic table is
traversed from the metals on the left to the
nonmetals on the right. This same variation is
observed in the reaction of oxides with water
and the resulting acid-base character of the
products. Ionic metal oxides react with water
to give hydroxides (compounds containing the
OH− ion) and resultant basic solutions,
whereas most nonmetal oxides react with
water to form acids and resultant acidic
solutions (see the table).

Periodic variation of the properties of oxides of th

period

group group
group 13 group 14
1 2

reaction of
oxides
Na2O MgO
with water
gives gives
and the Al2O3 SiO2
NaOH Mg(OH)2
acid-base nonreacting nonreacting
(strong (weak
character
base) base)
of
hydroxides

bonding in Na2O MgO Al2O3 SiO2

oxides ionic ionic ionic covalent

Source: From W. Robinson, J. Odom, and H. Holtzclaw, Jr., Chem

D.C. Heath and Co., 1992.

Certain organic compounds react with oxygen

or other oxidizing agents to produce
substances called oxides. Thus, amines,
phosphines, and sulfides form amine oxides,
phosphine oxides, and sulfoxides, respectively,
in which the oxygen atom is covalently bonded
to the nitrogen, phosphorus, or sulfur atom.
The so-called olefin oxides are cyclic ethers.

Metal oxides

Metal oxides are crystalline solids that contain

a metal cation and an oxide anion. They
typically react with water to form bases or with
acids to form salts.

The alkali metals and alkaline earth metals

form three different types of binary oxygen
compounds: (1) oxides, containing oxide ions,
O2−, (2) peroxides, containing peroxide ions,
O22−, which contain oxygen-oxygen covalent
single bonds, and (3) superoxides, containing
superoxide ions, O2−, which also have oxygen-
oxygen covalent bonds but with one fewer
negative charge than peroxide ions. Alkali
metals (which have a +1 oxidation state) form
oxides, M2O, peroxides, M2O2, and
superoxides, MO2. (M represents a metal
atom.) The alkaline earth metals (with a +2
oxidation state) form only oxides, MO, and
peroxides, MO2. All the alkali metal oxides can
be prepared by heating the corresponding
metal nitrate with the elemental metal.

2MNO3 + 10M + heat → 6M2O + N2

A general preparation of the alkaline earth

oxides involves heating the metal carbonates.

MCO3 + heat → MO + CO2

Both alkali metal oxides and alkaline earth

metal oxides are ionic and react with water to
form basic solutions of the metal hydroxide.

M2O + H2O → 2MOH (where M = group 1

metal)
MO + H2O → M(OH)2 (where M = group 2
metal)

Thus, these compounds are often called basic

oxides. In accord with their basic behaviour,
they react with acids in typical acid-base
reactions to produce salts and water; for
example,

M2O + 2HCl → 2MCl + H2O (where M =

group 1 metal).

These reactions are also often called

neutralization reactions. The most important
basic oxides are magnesium oxide (MgO), a
good thermal conductor and electrical
insulator that is used in firebrick and thermal
insulation, and calcium oxide (CaO), also
called quicklime or lime, used extensively in
the steel industry and in water purification.

Periodic trends of the oxides have been

thoroughly studied. In any given period, the
bonding in oxides progresses from ionic to
covalent, and their acid-base character goes
from strongly basic through weakly basic,
amphoteric, weakly acidic, and finally strongly
acidic. In general, basicity increases down a
group (e.g., in the alkaline earth oxides, BeO <
MgO < CaO < SrO < BaO). Acidity increases
with increasing oxidation number of the
element. For example, of the five oxides of
manganese, MnO (in which manganese has an
oxidation state of +2) is the least acidic and
Mn2O7 (which contains Mn7+) the most acidic.
Oxides of the transition metals with oxidation
numbers of +1, +2, and +3 are ionic
compounds consisting of metal ions and oxide
ions. Those transition metal oxides with
oxidation numbers +4, +5, +6, and +7 behave
as covalent compounds containing covalent
metal-oxygen bonds. As a general rule, the
ionic transition metal oxides are basic. That is,
they will react with aqueous acids to form
solutions of salts and water; for example,

CoO + 2H3O+ → Co2+ + 3H2O.

The oxides with oxidation numbers of +5, +6,

and +7 are acidic and react with solutions of
hydroxide to form salts and water; for
example,

CrO3 + 2OH- → CrO42− + H2O.

Those oxides with +4 oxidation numbers are

generally amphoteric (from Greek
amphoteros, “in both ways”), meaning that
these compounds can behave either as acids or
as bases. Amphoteric oxides dissolve not only
in acidic solutions but also in basic solutions.
For example, vanadium oxide (VO2) is an
amphoteric oxide, dissolving in acid to give the
blue vanadyl ion, [VO]2+, and in base to yield
the yellow-brown hypovanadate ion, [V4O9]2−.
Amphoterism among the main group oxides is
primarily found with the metalloidal elements
or their close neighbours.

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Nonmetal oxides
All nonmetals form covalent oxides with
oxygen, which react with water to form acids
or with bases to form salts. Most nonmetal
oxides are acidic and form oxyacids, which in
turn yield hydronium ions (H3O+) in aqueous
solution. There are two general statements
that describe the behaviour of acidic oxides.
First, oxides such as sulfur trioxide (SO3) and
dinitrogen pentoxide (N2O5), in which the
nonmetal exhibits one of its common
oxidation numbers, are known as acid
anhydrides. These oxides react with water to
form oxyacids, with no change in the oxidation
number of the nonmetal; for example,

N2O5 + H2O → 2HNO3.

Second, those oxides in which the metal does

not exhibit one of its common oxidation
numbers, such as nitrogen dioxide (NO2) and
chlorine dioxide (ClO2), also react with water.
In these reactions, however, the nonmetal is
both oxidized and reduced (i.e., its oxidation
number is increased and decreased,
respectively). A reaction in which the same
element is both oxidized and reduced is called
a disproportionation reaction. In the following
disproportionation reaction, N4+ is reduced to
N2+ (in NO) and oxidized to N5+ (in HNO3).

3NO2 + H2O → 2HNO3 + NO

Oxides of nitrogen

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Nitrogen (N) forms oxides in which nitrogen

exhibits each of its positive oxidation numbers
from +1 to +5. Nitrous oxide (dinitrogen
oxide), N2O, is formed when ammonium
nitrate, NH4NO3, is heated. This oxide, which
is a colourless gas with a mild, pleasant odour
and a sweet taste, is used as an anesthetic for
minor operations, especially in dentistry. It is
called laughing gas because of its intoxicating
effect. It is also widely used as a propellant in
aerosol cans of whipped cream. Nitric oxide,
NO, can be created in several ways. The
lightning that occurs during thunderstorms
brings about the direct union of nitrogen and
oxygen in the air to produce small amounts of
nitric oxide, as does heating the two elements
together. Commercially, nitric oxide is
produced by burning ammonia (NH3),
whereas in the laboratory it can be produced
by the reduction of dilute nitric acid (HNO3)
with, for example, copper (Cu).

3Cu + 8HNO3 → 2NO + 3Cu(NO3)2 + 4H2O

Gaseous nitric oxide is the most thermally

stable oxide of nitrogen and is also the
simplest known thermally stable paramagnetic
molecule—i.e., a molecule with an unpaired
electron. It is one of the environmental
pollutants generated by internal-combustion
engines, resulting from the reaction of
nitrogen and oxygen in the air during the
combustion process. At room temperature
nitric oxide is a colourless gas consisting of
diatomic molecules. However, because of the
unpaired electron, two molecules can combine
to form a dimer by coupling their unpaired
electrons.

2NO ⇌ N2O2

Thus, liquid nitric oxide is partially dimerized,

and the solid consists solely of dimers.

When a mixture of equal parts of nitric oxide

and nitrogen dioxide, NO2, is cooled to −21 °C
(−6 °F), the gases form dinitrogen trioxide, a
blue liquid consisting of N2O3 molecules. This
molecule exists only in the liquid and solid
states. When heated, it forms a mixture of NO
and NO2. Nitrogen dioxide is prepared
commercially by oxidizing NO with air, but it
can be prepared in the laboratory by heating
the nitrate of a heavy metal, as in the following
equation,

2Pb(NO3)2 + heat → 2PbO + 4NO2 + O2,

or by adding copper metal to concentrated

nitric acid. Like nitric oxide, the nitrogen
dioxide molecule is paramagnetic. Its
unpaired electron is responsible for its colour
and its dimerization. At low pressures or at
high temperatures, NO2 has a deep brown
colour, but at low temperatures the colour
almost completely disappears as NO2
dimerizes to form dinitrogen tetroxide, N2O4.
At room temperature an equilibrium between
the two molecules exists.

2NO2 ⇌ N2O4

Dinitrogen pentoxide, N2O5, is a white solid

formed by the dehydration of nitric acid by
phosphorus(V) oxide.

P4O10 + 4HNO3 → 4HPO3 + 2N2O5

Above room temperature N2O5 is unstable and

decomposes to N2O4 and O2. Two oxides of
nitrogen are acid anhydrides; that is, they
react with water to form nitrogen-containing
oxyacids. Dinitrogen trioxide is the anhydride
of nitrous acid, HNO2, and dinitrogen
pentoxide is the anhydride of nitric acid,
HNO3.

N2O3 + H2O → 2HNO2

N2O5 + H2O → 2HNO3

There are no stable oxyacids containing

nitrogen with an oxidation number of +4.

Nitrogen dioxide reacts with water in one of

two ways. In cold water NO2 disproportionates
to form a mixture of HNO2 and HNO3,
whereas at higher temperatures HNO3 and NO
are formed. In their chemical activity, the
nitrogen oxides undergo extensive oxidation-
reduction reactions. Nitrous oxide resembles
oxygen in its behaviour when heated with
combustible materials. It is a strong oxidizing
agent that decomposes upon heating to form
nitrogen and oxygen. Because one-third of the
gas liberated is oxygen, nitrous oxide supports
combustion better than air. All the nitrogen
oxides are, in fact, good oxidizing agents.
Dinitrogen pentoxide reacts violently with
metals, nonmetals, and organic materials, as
in the following reactions with potassium (K)
and iodine gas (I2).

N2O5 + K → KNO3 + NO2

N2O5 + I2 → I2O5 + N2

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