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)
The triple point, however, does not lie exactly at 0° C., for this
temperature is defined as the melting point of ice under atmospheric
pressure. At the triple point, however, the pressure is equal to the vapour
pressure of ice and water, and this pressure, as we see from the tables on
pp. 21 and 23, is very nearly 4.6 mm., or almost 1 atm. less than in the
previous case. Now, we have just seen that a change of pressure of 1 atm.
corresponds to a change of the melting point of 0.0076°; the melting point
of ice, therefore, when under the pressure of its own vapour, will be very
nearly +0.0076°, and the pressure of the vapour will be very slightly
greater than 4.579 mm., which is the pressure at 0° (p. 21). The difference
is, however, slight, and may be neglected here. At the temperature, then,
of +0.0076°, and under a pressure of 4.6 mm. of mercury, ice, water, and
vapour will be in equilibrium; the point in our diagram representing this
particular temperature and pressure is, therefore, the triple point of the
system ice--water--vapour.
Since at the triple point we have three phases of one component, the system
at this point is invariant--it possesses no degrees of freedom. If the
temperature is changed, the system will undergo alteration in such a way
that one of the phases will disappear, and a univariant system will result;
if heat be added, ice will melt, and we shall have left water and vapour;
if heat be abstracted, water will freeze, and we shall have left ice and
vapour; if, when the temperature is altered, the pressure is kept constant,
then we shall ultimately obtain only one phase (see Chap. IV.).
The triple point is not only the point of intersection of the vaporization
and sublimation curves, but it is also the end-point of the fusion curve.
The fusion curve, as we have seen, is the curve of equilibrium between ice
and water; and since at the triple point ice and water are each in
equilibrium with {29} vapour of the same pressure, they must, of course,
also be in equilibrium with one another.
[Illustration: FIG. 4.]
Bivariant Systems of Water.--If we examine Fig. 4, we see that the curves
OA, OB, OC, which represent diagrammatically the conditions under which
water and vapour, ice and vapour, and water and ice are in equilibrium,
form the boundaries of three "fields," or areas, I., II., III. These areas,
now, represent the conditions for the existence of the single phases,
solid, liquid, and vapour respectively. At temperatures and pressures
represented by any point in the field I., solid only can exist as a stable
phase. Since we have here one component in only one phase, the system is
bivariant, and at any given temperature, therefore, ice can exist under a
series of pressures; and under any given pressure, at a series of
temperatures, these pressures and temperatures being limited only by the
curves OB, OC. Similarly also with the areas II. and III.
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