The Phase Rule and Its ApplicationsFindlay, Alexander
Science
The Phase Rule and Its Applications
Findlay, Alexander
Chemistry, Physical and theoretical; Phase rule and equilibrium; Solution (Chemistry)
Real and Apparent Equilibrium.--In discussing equilibria, also, a
distinction must be drawn between real and {6} apparent equilibria. In the
former case there is a state of rest which undergoes continuous change with
change of the conditions (_e.g._ change of temperature or of pressure), and
for which the chief criterion is that _the same condition of equilibrium is
reached from whichever side it is approached_. Thus in the case of a
solution, if the temperature is maintained constant, the same concentration
will be obtained, no matter whether we start with an unsaturated solution
to which we add more solid, or with a supersaturated solution from which we
allow solid to crystallize out; or, in the case of water in contact with
vapour, the same vapour pressure will be obtained, no matter whether we
heat the water up to the given temperature or cool it down from a higher
temperature. In this case, water and vapour are in _real_ equilibrium. On
the other hand, water in contact with hydrogen and oxygen at the ordinary
temperature is a case only of _apparent_ equilibrium; on changing the
pressure and temperature continuously within certain limits there is no
continuous change observed in the relative amounts of the two gases. On
heating beyond these limits there is a sudden and not a continuous change,
and the system no longer regains its former condition on being cooled to
the ordinary temperature. In all such cases the system may be regarded as
undergoing change and as tending towards a state of true or real
equilibrium, but with such slowness that no change is observed.
Although the case of water in contact with hydrogen and oxygen is an
extreme one, it must be borne in mind that the condition of true
equilibrium may not be reached instantaneously or even with measurable
velocity, and in all cases it is necessary to be on one's guard against
mistaking apparent (or false) for real (or true) equilibrium. The
importance of this will be fully illustrated in the sequel.
* * * * *
{7}
CHAPTER II
THE PHASE RULE
Although the fact that chemical reactions do not take place completely in
one direction, but proceed only to a certain point and there make a halt,
was known in the last quarter of the eighteenth century (Wenzel, 1777;
Berthollet, 1799); and although the opening and subsequent decades of the
following century brought many further examples of such equilibria to our
knowledge, it was not until the last quarter of the nineteenth century that
a theorem, general in its application and with foundations weakened by no
hypothetical assumptions as to the nature or constitution of matter, was
put forward by Willard Gibbs;[5] a generalization which serves at once as a
golden rule by which the condition of equilibrium of a system can be
tested, and as a guide to the similarities and dissimilarities existing in
different systems.
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