Significant insight
into the above problem is found by studying different
compounds formed from the same elements. For example,
there are actually three oxides of nitrogen, that is,
compounds composed only of nitrogen and oxygen. For
now, we will call them oxide A, oxide B, and oxide
C. Oxide A has oxygen to nitrogen mass ratio 2.28 :
1. Oxide B has oxygen to nitrogen mass ratio 1.14 : 1,
and oxide C has oxygen to nitrogen mass ratio 0.57 :
1.
The fact that there are
three mass ratios might seem to contradict the
Law of Definite Proportions, which on the
surface seems to say that there should be just one
ratio. However, each mass combination gives rise to a
completely unique chemical compound with very
different chemical properties. For example, oxide A is
very toxic, whereas oxide C is used as an
anesthesia. It is also true that the mass ratio is not
arbitrary or continuously variable: we cannot pick
just any combination of masses in combining oxygen and
nitrogen, rather we must obey one of only three. So
there is no contradiction: we simply need to be
careful with the Law of Definite
Proportions to say that each unique
compound has a definite mass ratio of
combining elements.
These
new mass ratio numbers are highly suggestive in the
following way. Notice that, in each case, we took the
ratio of oxygen mass to a nitrogen mass of 1, and that
the resultant ratios have a very simple relationship:
2.28
:
1.14
:
0.57
=
2
:
1
:
0.5
=
4
:
2
:
1
2.28
:
1.14
:
0.57
2
:
1
:
0.5
4
:
2
:
1
(1)
The masses of oxygen appearing in these compounds are in simple whole
number ratios when we take a fixed amount of nitrogen. The
appearance of these simple whole numbers is very
significant. These integers imply that the compounds contain a
multiple of a fixed unit of mass of oxygen. The simplest
explanation for this fixed unit of mass is that oxygen is
particulate. We call the fixed unit of mass an
atom. We now assume that the compounds have been
formed from combinations of atoms with fixed masses, and that
different compounds have differing numbers of atoms. The mass
ratios make it clear that oxide B contains twice as many
oxygen atoms (per nitrogen atom) as does oxide C and half as
many oxygen atoms (per nitrogen atom) as does oxide A. The
simple mass ratios must be the result of the simple ratios in
which atoms combine into molecules. If, for example, oxide C
has the molecular formula
N
O
N
O
, then oxide B has the formula
N
O
2
N
O
2
, and oxide A has the formula
N
O
4
N
O
4
. There are other
possibilities: if oxide B has molecular formula
N
O
N
O
, then oxide A has formula
N
O
2
N
O
2
, and oxide C has formula
N
2
O
N
2
O
. Or if oxide A has formula
N
O
N
O
, then oxide B has formula
N
2
O
N
2
O
and oxide C has formula
N
4
O
N
4
O
. These three possibilities are listed in the following
table.
Table 2: Possible Molecular Formulae for Nitrogen Oxides
| Assuming that: |
Oxide C is
N
O
N
O
|
Oxide B is
N
O
N
O
|
Oxide A is
N
O
N
O
|
| Oxide A
is |
N
O
4
N
O
4
|
N
O
2
N
O
2
|
N
O
N
O
|
| Oxide B is |
N
O
2
N
O
2
|
N
O
N
O
|
N
2
O
N
2
O
|
| Oxide C is |
N
O
N
O
|
N
2
O
N
2
O
|
N
4
O
N
4
O
|
We don't have a way (from these data) to
know which of these sets of molecular formulae are right. But we
can assert that either one of them or one analogous to them is
right.
Similar data are found for
any set of compounds formed from common elements. For example,
there are two oxides of carbon, one with oxygen to carbon mass
ratio 1.33:1 and the other with mass ratio 2.66:1. The second
oxide must have twice as many oxygen atoms, per carbon atom, as
does the first. The general statement of this observation is the
Law of Multiple Proportions.
When two elements
combine to form more than one compound, the mass of element A
which combines in the first compound with a given amount of
element B has a simple whole number ratio with the mass of
element A which combines in the second compound with the same
given mass of element B.
This sounds confusing, but an example
clarifies this statement. Consider the carbon oxides, and let
carbon be element B and oxygen be element A. Take a fixed given
mass of carbon (element B), say 1 gram. The mass of oxygen which
combines with 1 gram of carbon to form the first oxide is 1.33
grams. The mass of oxygen which combines with 1 gram of carbon
to form the second oxide is 2.66. These masses are in ratio
2.66
:
1.33
=
2
:
1
2.66
:
1.33
2
:
1
, a simple whole number ratio.
In explaining our observations of the Law
of Multiple Proportions for the carbon oxides and the
nitrogen oxides, we have concluded that the simple mass ratio
arises from the simple ratio of atoms contained in the
individual molecules. Thus, we have established the following
postulates of the Atomic Molecular Theory.
- the elements are comprised of
identical atoms
- all atoms of a single element have
the same characteristic mass
- these number and
masses of these atoms do not change during a chemical
transformation
- compounds consist of identical molecules formed of atoms combined in simple whole number ratios
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