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
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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
«Applications of the Law of Physical Equilibrium.»—(1) The
law of physical equilibrium may be applied first to the case
of a liquid, say chloroform, in contact with its vapor.
For the condition of equilibrium at a fixed temperature
[CHCl_{3}]_{vap.} : [CHCl_{3}]_{liq.} = ‹k›.
Now, at a fixed temperature, a pure liquid has a fixed concentration,
its specific gravity being a definite one. Hence, for a fixed
temperature, the second term of the constant ratio being definite,
the first term, [CHCl_{3}]_{vap.}, representing the concentration of
the vapor, must also have a fixed, constant value for the condition
of equilibrium, ‹i.e.› when the space above the liquid is saturated
with its vapor. This is in agreement with well-known facts. The
concentration of the vapor is usually expressed in terms of its
[p121] pressure, and is called the ‹vapor pressure› or ‹vapor
tension› of the liquid at the temperature in question. Tables giving
the definite vapor pressures of important liquids at the various
fixed temperatures are in common use.
(2) For oxygen in equilibrium with its saturated solution, say
in water, at a fixed temperature, we have, according to the law,
[O_{2}]_{gas} : [O_{2}]_{solut.} = ‹k›.
If the oxygen is under a given pressure at a definite temperature,
its concentration [O_{2}]_{gas} is fixed, and consequently the
second term, [O_{2}]_{solut.}, of the ratio, the concentration of
the dissolved oxygen, or ‹its solubility, must also be definite›,
‹i.e.› oxygen must have a definite solubility in water at a given
temperature under a given pressure. If the pressure on the gas is
doubled, its concentration is doubled and, to maintain the constant
ratio, its solubility must also be doubled—which is in agreement
with the facts (Henry's law). If air of the same pressure is taken,
in place of pure oxygen, then the concentration of the oxygen (first
term of the above ratio) is only about one-fifth as great as for the
pure gas, and the water must be saturated with oxygen when it has
taken up only one-fifth (second term of the ratio) as much as it
would from the pure gas (Dalton's law): ‹Each gas in a mixture is
soluble in proportion to its own partial pressure› or ‹concentration›.
(3) For sugar in equilibrium with its solution in water, ‹i.e.› in
contact with its saturated solution, at a given temperature, we
should have
[C_{12}H_{22}O_{11}]_{aq.} : [C_{12}H_{22}O_{11}]_{solid} = ‹k›.
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