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Historical review

Emergence of quantitative chemistry

The early Greeks, most notably Democritus, argued that matter is


composed of fundamental particles called atoms. The views of
the atomists, however, lacked the authority that comes from
experiment, and evidence of the existence of atoms was not
forthcoming for two millennia until the emergence of
quantitative, empirical science in the 18th century.
The law of conservation of mass

The crucial transformation of chemistry from a collection of vain


hopes and alchemical meddlings to a corpus of reliable quantitative
knowledge hinged on the contributions of the French
aristocrat Antoine-Laurent Lavoisier (and his wife, Marie-Anne),
shortly before he lost his head to the guillotine at the height of
the Reign of Terror. Lavoisier opened the door to quantitative
chemistry by establishing that the transformations of matter, which
until his day had been described largely by a miasma of uncoordinated
reports, could be investigated quantitatively by measuring the masses
of substances consumed and produced in reactions. The most
significant observation he made was that, even though one substance
is transformed into another during the course of a reaction, the total
mass of the products is the same as the total mass of the reactants.
The implication of this observation is that, although the identity of the
substances may change when a reaction occurs, something, at least,
remains unchanged.
The law of definite proportions

Lavoisier’s experimentation inspired further studies that ultimately


resulted in an overthrow of the view that matter is a
structureless continuum. These observations culminated in
the atomic hypothesis developed by the English chemist John Dalton,
which states that matter is composed of indestructible particles which
are unique to and characteristic of each element. Two major sets of
observations helped to establish this view. First, it was found
that compounds always have a fixed composition, regardless of their
origin. Thus, it was determined that 18 grams of water always consists
of 2 grams of hydrogen and 16 grams of oxygen, regardless of how the
sample originated. Such observations overthrew, at least temporarily,
the view held by the French chemist Claude-Louis Berthollet that
compounds have a variable composition. Modern research has shown,
however, that there are in fact certain classes of compounds in which
the composition is variable. Nevertheless, they are a minority, and
the law of definite proportions (also called the law of constant
composition) is the rule rather than the exception.
The law of multiple proportions

The second step toward Dalton’s synthesis was the recognition of the
existence of related series of compounds formed by the same
elements. It was established, for example, that, whereas 28 grams
of carbon monoxide invariably consists of 12 grams of carbon and 16
grams of oxygen, carbon also forms the compound carbon dioxide, and
44 grams of this compound always consists of 12 grams of carbon and
32 grams of oxygen. In this example, the mass of oxygen that
combines with a fixed mass of carbon to form carbon dioxide is exactly
twice the quantity that combines to form carbon monoxide. Such
observations strongly suggested that carbon dioxide contains exactly
twice as many oxygen entities per carbon entity as carbon monoxide
does. Dalton predicted that, when two elements combine in a series of
compounds, the ratios of the masses of one element that combine with
a fixed mass of the second are reducible to small whole numbers; this
is now known as the law of multiple proportions.
Dalton’s atomic theory

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