The Elements of Qualitative Chemical Analysis, vol. 1, parts 1 and 2.: With Special Consideration of the Application of the Laws of Equilibrium and of the Modern Theories of Solution.Stieglitz, Julius
Science
The Elements of Qualitative Chemical Analysis, vol. 1, parts 1 and 2.: With Special Consideration of the Application of the Laws of Equilibrium and of the Modern Theories of Solution.
Stieglitz, Julius
Chemistry, Analytic -- Qualitative
It is this perfect agreement between the chemical behavior and the
formulæ (as based on these molecular weights and on the analysis of
compounds), which forms the strongest ‹experimental evidence› of the
correctness of the fundamental assumption of Avogadro's hypothesis.
The agreement has been shown to hold for innumerable compounds,
even for those of greatest complexity, and it was such agreement
which finally led to the general acceptance of the hypothesis. The
experimental evidence of this nature is so strong, so extensive and
so completely corroborative of the hypothesis, that many chemists,
rather justly, consider the hypothesis to have been established as a
law, although the evidence is circumstantial rather than direct.
While the application of Avogadro's hypothesis thus gives results
agreeing well with the observed chemical behavior of very many
important compounds, observations have been made which, at first
sight, do not appear to agree with the requirements of the hypothesis
and which seem to raise a doubt as to the ‹universal truth› of its
fundamental assumption. Thus, if equal volumes of hydrogen chloride
and ammonia, of the same temperature and pressure, are brought
together, ammonium chloride is formed, both gases being totally
consumed. Since, according to the hypothesis, equal volumes, under
the conditions obtaining, contain the same numbers of molecules,
the formation of ammonium chloride takes place according to the
equation NH_{3} + HCl → NH_{4}Cl, and we should anticipate that the
molecular weight of [p035] ammonium chloride would be 17 + 36.5 or
53.5. However, when the molecular weight is determined by obtaining
the weight of a measured volume of ammonium chloride vapor, at
a temperature sufficiently high to vaporize the salt, and the
observations are reduced to standard conditions of temperature and
pressure, 26.75 grams is found as the calculated weight of 22.4
liters, and this weight, according to this hypothesis, should be
the molecular weight of the chloride. This contradiction in two
conclusions, each reached by the application of Avogadro's hypothesis
to experimental observations, would, at the first glance, make one
hesitate to accept the hypothesis as representing a universal truth;
it might seem as if in some gases, such as ammonium chloride vapor,
there might be only half as many molecules in a given volume as in
the same volume of the majority of gases.
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