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)
As we have already learned (p. 16), the Phase Rule takes no account of the
molecular complexity of the substances participating in an equilibrium. A
dissociating substance, therefore, in contact with its vaporous products of
dissociation (_e.g._ ammonium chloride in contact with ammonia and hydrogen
chloride), will likewise constitute a univariant system of one component,
provided the composition of the vapour phase as a whole is the same as that
of the solid or liquid phase (p. 13). For all such substances, therefore,
the conditions of equilibrium will be represented by a curve of the same
general form as the vapour pressure curve of a non-dissociating
substance.[112] The same behaviour is also found in the case of substances
which polymerize on passing into the solid or liquid state (_e.g._ red
phosphorus). Where such changes in the molecular state occur, however, the
time required for equilibrium to be established is, as a rule, greater than
when the molecular state is the same in both phases.
From an examination of Figs. 13 and 14, it will be easy to predict the
effect of change of pressure and temperature on the univariant systems S-V
or L-V. If the volume is kept constant, addition of heat will cause an
increase of pressure, the system S-V moving along the curve AO until at the
triple point the liquid phase is formed, and the system L-V moving along
the curve OB; so long as two phases are present, the condition of the
system must be represented by these two curves. Conversely, withdrawal of
heat will cause condensation of vapour, and therefore diminution of
pressure; the system will therefore move along the vaporization or
sublimation curve to lower temperatures and pressures, so long as the
system remains univariant.
{65}
If transference of heat to or from the system is prevented, increase of
volume (diminution of pressure) will cause the system L-V to pass along the
curve BO; liquid will pass into vapour and the temperature will fall.[113]
At O solid may appear, and the temperature of the system will then remain
constant until the liquid phase has disappeared (p. 57); the system will
then follow the curve OA until the solid phase disappears, and we are
ultimately left with vapour. On the other hand, diminution of volume
(increase of pressure) will cause condensation of vapour, and the system
S-V will pass along the curve AO to higher temperatures and pressures; at O
the solid will melt, and the system will ultimately pass to the curve OB or
to OC (p. 57).
Addition or withdrawal of heat at constant pressure, and increase or
diminution of the pressure at constant temperature, will cause the system
to pass along lines parallel to the temperature and the pressure axis
respectively; the working out of these changes may be left to the reader,
guided by what has been said on pp. 60 and 61.
Public-domain text, read in full here on John Shaqi.
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