When a liquid is heated in an open vessel, its temperature
and vapour pressure will both increase. At the temperature at
which the liquid's vapour pressure (the pressure at any given
temperature at which both liquid and vapour are in equilibrium)
would be equal to the external pressure, vaporisation can occur
throughout the bulk of the liquid, and free expansion of the
gas into its surroundings may take place. This free vaporisation
of the liquid throughout its bulk is what we call boiling,
and the temperature at which it occurs is called the boiling
temperature or boiling point.
Note the requirement for the external and vapour pressures
to be equal for boiling to occur explains the well-known phenomenon
of liquids boiling at lower temperatures at higher altitudes
(where the atmospheric pressure is less than at sea level).
With a lower external pressure, the vapour pressure of the liquid
does not need to be raised by as much to equal it, and consequently
less heat needs to be supplied to bring about boiling.
It is worth introducing some definitions here:
The normal boiling point, Tb,
is the boiling temperature when the external pressure is one
atmosphere.
The standard boiling point is the boiling temperature when the
external pressure is is one bar .
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Since one bar is slightly less than one
atmosphere, the standard boiling point of a liquid is
slightly less than its normal boiling point. (Note that
the difference in pressure between 1 bar and 1 atm has
been exaggerated in the diagram for clarity.) |
Boiling does not occur when a liquid is heated in a
closed vessel. The vapour pressure of the liquid rises, but
as a consequence of the vaporisation that occurs from the surface
of any liquid while it is being heated, the density of the vapour
in the vessel also increases. (In effect, we may consider
that while the vapour pressure of the liquid is rising, the
extra vapour that evaporates increases the pressure upon
the liquid. The vapour pressure thus never reaches the same
value as the external pressure, because both values are
increasing as a result of the heating. This problem does not
arise in the open vessel because the vapour that evaporates
is free to disperse, and the external pressure upon the liquid
thus remains constant throughout.)
Heating also causes expansion of the liquid, and thus a reduction
in its density, and eventually a point comes where the densities
of the liquid and vapour are equal. At this point, the surface
between the two phases vanishes, and the container is filled
with a single uniform phase called a supercritical
fluid.
The temperature at which the surface between the two phases
disappears is called the critical temperature, Tc,
and the vapour pressure at the critical temperature is called
the critical pressure. The point on a phase diagram corresponding
to the critical temperature and pressure is called the critical
point. Note that at and above the critical temperature, the
liquid phase does not exist - it is replaced by the supercritical
fluid.
The triple point of a substance
marks the set of conditions under which three different phases
of the substance (typically solid, liquid and gas) all exist
in equilibrium with each other. It is the point on a phase diagram
where three phase boundaries meet. The temperature at the triple
point is denoted T3 .
The triple point of a pure substance occurs at a single fixed
pressure and temperature, characteristic of the substance. For
example, the triple point of water occurs at 273.16 K and 611Pa.
Note that the triple point marks the lowest pressure at which
the liquid phase of a substance can exist. If the solid-liquid
phase boundary has a positive gradient, as is almost always
the case, then it also marks the lowest temperature at which
the liquid phase can exist.
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