History of Chemistry, Volume 2 (of 2): From 1850 to 1910Thorpe, T. E. (Thomas Edward)
History
History of Chemistry, Volume 2 (of 2): From 1850 to 1910
Thorpe, T. E. (Thomas Edward)
Chemistry -- History
As regards the molecular volumes of gases it has been shown that
simple relations are obtained when quantities represented by their
respective molecular weights are compared under identical conditions of
temperature and pressure—that is, under circumstances in which equal
numbers of molecules form the basis of comparison. The investigation
of the molecular volumes of liquids is complicated by the uncertainty
as to what constitutes in their case a valid condition of comparison.
Kopp’s assumption that a comparable condition was the temperature
at which the vapour pressures of the liquids are equal to the mean
atmospheric pressure was justified by the fact that the boiling-points
of liquids are approximately two thirds of their respective critical
temperatures. His conclusions have been confirmed and extended by
Lossen, Thorpe, and Schiff. It has been shown that the molecular
volume of a liquid—that is, the product of its relative density at the
boiling-point into its molecular weight—is in the main an additive
function modified by constitutive influences. Definite values have
thus been obtained for a number of the elements from a comparison of
homologous or similarly constituted compounds; and in certain cases
these are found to be practically identical with the values of the
elements in the uncombined state.
Considerable light has been gained during the last two decades
concerning the nature of _solution_. In its most comprehensive sense
solution means the homogeneous mixture of two or more substances: thus
the gases which exert no chemical action on each other are mutually
soluble; gases, liquids, and solids may be soluble in liquids; and,
lastly, solids maybe soluble in solids, forming what are known as
_solid solutions_. The mutual solubility of gases was studied by Dalton
who enunciated the _law of partial pressures_, which states that the
total pressure of a mixture of gases is the sum of the pressures
exerted by the individual components. This, like all the so-called
gaseous laws, is necessarily not strictly accurate under ordinary
conditions, but approximates to truth in proportion as the gases are
rarefied. Van ’t Hoff pointed out that the true partial pressures of
the components of a gaseous mixture might be experimentally ascertained
by the use of a membrane capable of effecting their separation, and on
this principle Ramsay measured the partial pressures of a mixture of
hydrogen and nitrogen contained in a palladium vessel connected with
a manometer. The palladium, at a sufficiently high temperature, is
permeable to hydrogen to the exclusion of the nitrogen. The conditions
affecting the solubility of gases in liquids were experimentally
studied by Dalton and Henry, and what is known as Henry’s law implies
that the volume of a gas dissolved by a definite volume of a liquid
is independent of the pressure; or, in other words, the density
(concentration) of the gas in solution is proportional to that in
the space above the liquid.
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