Francis Lowie S.

Buenaflor
BSPE 3C

1.

A phase diagram is a representation of the physical changes of state of a substance can

undergo in a graph form where pressure (p) serves as the y-axis and temperature (T) for x-axis.
The changes of substance do not involve change in chemical composition but focuses on the
substance's physical transformations. It also shows how the vapour pressure of a substance varies
with temperature and how the melting point varies with pressure. The phase diagram of a
substance shows the regions of pressure and temperature at which its various phases are
thermodynamically stable. The lines separating the regions, which are called phase boundaries,
show the values of p and T at which two phases coexist in equilibrium. Having a phase diagram
helps us to identify the critical and boiling points of a particular substance as well as the melting
points and triple points as the substance changes its physical state.
Consider the phase diagram of a carbon dioxide. You will notice that the slope of its
phase diagram is positive. The triple point of carbon dioxide lies above atmospheric pressure (1
atm) and it cannot exist as a liquid at atmospheric pressure while the normal boiling point lies at
194.7 K at 1 atm. The triple point lies at 216.8 Kelvin at 5.11 atm which all the phases of carbon
dioxide exists equilibrium and the critical point lies at 304.2 Kelvin at 72.9 atm where all phases
of carbon dioxide cease to exist but not in
equilibrium.

Phase diagram of carbon dioxide

2.

When any substance at a temperature and pressure reaches above the critical point and its
distinct liquid and gas phases do not exist, it is called a supercritical fluid. Supercritical fluids are
suitable as a substitute for organic solvents in industrial and laboratory processes. Carbon dioxide
and water are the most commonly used supercritical fluids. In extracting supercritical fluids, it is
generally operated in batch mode on milled materials such as pellets and granulates, with carbon
dioxide as solvent and added with a co-solvent which ethanol is the most used to increase its
polarity. The equipment is composed of one or several extractors consisting in high pressure
autoclaves with fast-opening systems in which the material to be treated is set inside a basket
easy to put in and to remove, and a separation section where extract and fluid are separated prior
to fluid recycle through condensation and liquid pumping. As it is operated in batch and requires
manpower to change the solid material at each cycle of extraction, this process is costly compared
to those classical organic solvent extractions. But after the processing, it is found out that no
organic residue in extract and solid residue and no thermal degradation appears and results in
very high quality products.
There are lot of advantages using supercritical fluids and these are the most use of it.
Supercritical fluids are recyclable and non-flammable. It has good solvent characteristics for nonpolar and slightly polar solutes. It can be used in chromatography, allowing analysis immediately
after extraction. Well, extraction of supercritical fluid is expensive but it has a wide range of use.
However, there's a disadvantage when using carbon dioxide in chromatography as a
mobile phase, it does not elute very polar or ionic compounds. Superfluid carbon dioxide is not
soluble.

Extraction of Supercrictical Fluids

3.

The Clapeyron equation is an exact expression for the slope of the phase boundary and
applies to any phase equilibrium of any pure sub- stance. It implies that we can use
thermodynamic data to predict the appearance of phase diagrams and to understand their form. A
more practical application is to the prediction of the response of freezing and boiling points to the
application of pressure. Like the Clapeyron equation, the ClausiusClapeyron equation is
important for understanding the appearance of phase diagrams, particularly the location and shape
of the liquidvapour and solidvapour phase boundaries. It lets us predict how the vapour
pressure varies with temperature and how the boiling temperature varies with pressure.

4.

In isobaric heating, the pressure remains the same and the temperature increased to 6
Kelvin. The helium was in liquid phase (superfluid, He-II) initially and became gas after it
undergone isobaric process. After that, it was on isothermal compression process. The
temperature remains the same and the pressure increased to 10 bar. From gas phase, it turned into
liquid (He-I) phase again but not exactly the liquid phase on isobaric process where it is in
superfluid form. The helium undergone isothermal compression process where the pressure
became 5MPa (50bar) and the temperature was still 6 Kelvin. The helium remains in the liquid
phase (He-I).

Problem Solving

1.

2. a.

b.

3.

Therefore, if

V =V

G is independent of pressure.

4.

Phase Diagram of
Benzene