Vince Jian G.

Gelacio BSPE-3C PET 31 Take Home Exam September 28, 2016

Concepts

1. Define and describe a phase diagram. Draw an example of a phase diagram, label its parts, and discuss
the significance of each part.

A phase diagram is a graphical interpretation of pressure and temperature. Basically if you know the
pressure and temperature of a substance, you can figure out what phase it is using a phase diagram.

So what it is showing is that there are 3 different phases. Solid (S), liquid (L), and gas (G).

The lines separating the regions are called phase boundaries. It shows the values of p and T at which
two phases coexist in equilibrium. Triple point a point at which the three phase boundaries meet where
a set of conditions under which three different phases of a substance (typically solid, liquid, and vapour)
all simultaneously coexist in equilibrium.Critical point is the point on a phase diagram at which the
substance is indistinguishable between liquid and gaseous states.

The liquid–vapour phase boundary in a phase diagram shows how the vapour pressure of the liquid
varies with temperature. Similarly, the solid–vapour phase boundary shows the temperature variation
of the sublimation vapour pressure, the vapour pressure of the solid phase. The vapour pressure of a
substance increases with temperature because at higher temperatures more molecules have sufficient
energy to escape from their neighbours. The solid-liquid phase boundary is just a melting (fusion). It
implies that as the pressure is raised, the melting temperature increased.

2. Define, discuss, and illustrate critical fluid extraction. Include in your discussion he advantages and
disadvantages of the process, as well as the latest developments.

Supercritical fluid extraction is the separation and extraction of chemical compounds of interest from
samples of products such as coffee tea and spices by using supercritical fluid as an extracting solvent on
mobile phase. This technique resembles Soxhlet extraction except the fact that the solvent used here is
the supercritical fluid. The supercritical fluid state occurs when the fluid is above its critical temperature
and critical pressure that is between the typical gas and liquid state during which the solventing power of
mobile phase will be at its peak.
The supercritical fluid extraction process consists mainly of a pump, a trapping vessel and an oven with
extraction vessel. A pump is used to pressurize the solvent which in this case is CO2. The liquid (CO2) is
pumped to a heating zone, where it is heated to supercritical conditions. It then passes into the extraction
vessel. The extraction vessel rapidly diffuses the liquid into solid matrix and dissolves the materials to be
extracted. The first recorded observation on the occurrence of supercritical phase was mad by Baron
Cagniard de la Tour on 1822. In 1970 a significant development in the field of supercritical fluid extraction
occurred by decaffeination of green coffee with CO2 as supercritical fluid. The advantage of SCFE is that
the dissolving power of supercritical fluid is adjustable with T and P. Some SCF are inexpensive and non-
toxic which help reduce pollution. Suitable for extraction and purification of compounds having low
volatility present in solids and liquids. The main advantage of SCFE is that it’s green technology. Which
means it is very safe for the environment and now there is the tendency to use the environment-friendly
solvent. Supercritical fluid extraction disadvantage is that even though some SCF are inexpensive, the
apparatus necessary for the extraction is expensive and also the cost may prohibit large scale applications.
Also scale is not possible due to the absence of fundamental, molecular based model of solutes in SCF.

3. Differentiate the Clapeyron equation from the Clausius-Clapeyron equation.

The temperature dependence of the vapour pressure is given by the Clapeyron equation,

The temperature dependence of the vapour pressure of a condensed phase is given by the Clausius-
Clapeyron equation,

The difference between Clapeyron equation to the Clausius-Clapeyron equation is that during the liquid-
vapour boundary, the molar volume of a gas is so much greater than the molar volume of a liquid. Thus
we can write vapV ≈Vm(g). Moreover, if the gas behaves perfectly, Vm(g) = RT/p. If we assume that the
vapour is ideal and work only with molar quantities, we can write

These two approximations turn the exact Clapeyron equation into Clausius-Clapeyron equation.
4. Using the phase diagram for helium, describe the phase changes it undergoes in the following
conditions initially at 1 bar and 1 K: (a) isobaric heating to 6K; (b) isothermal compression to 10 bar; (c)
isothermal expansion to 5 bar

a) The phase change of helium when it’s condition is at 1 bar and 1K would be a superfluid phase.

b) The phase change of helium when its condition is isobaric (1 bar and 6K) would be gas phase.

c) The phase change of helium when its condition is isothermal compression to 10 bar would be a super
critic phase.

d) The phase change of helium when its condition is isothermal expansion to 5 bar would be liquid phase

REFERENCES:

Atkins Physical Chemistry 8th edition, P. Atkins and J. de Paula

Supercritical Fluid Extraction 2nd edition, M. Mchugh and V. Krukonis

Clapeyron and Clausius-Clapeyron Equations by W.R. Salzman

http://cbc.arizona.edu/~salzmanr/480a/480ants/clapeyro/clapeyro.html

PROBLEM SOLVING

1. Consider the following table which contains the mole fraction of methylbenzene (A) in liquid and
gaseous mixtures with butanone at 303.15 K, and total pressure p. Assuming the vapor to be perfect,
calculate the partial pressures of the two components, sketch the graph, and plot them against the mole
fractions. Also, determine Henry’s law constants for methylbenzene and butanone.
2. The vapor pressure, p, of nitric acid varies with temperature as follows:

ϴ / °C 0 20 40 50 50 80 90 100

P / kPa 2.00 6.40 17.7 27.7 62.3 89.3 125 171

Determine: (a) the normal boiling point, (b) the enthalpy of vaporization of nitric acid.
3. Show that ΔG is independent of pressure for the transition of two incompressible solid phases.
4. Sketch the phase diagram for benzene near its triple point at 36 Torr and 5.5°C using the following
data: ΔfusH = 10.6 kJ/mole; ΔvapH = 30.8 kJ/mole; ρ (s) = 0.891 g/mL; ρ (l) = 0.879 g/mL