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Problem 3: Given the liquid – vapour phase diagram of a 2 component system below.

Under the constant pressure specified for this diagram,

1. Determine the boiling points of pure liquid A and pure liquid B


2. Comment about values of temperature for liquid-vapour phase equilibrium of all systems (A+B).
3. Mixing 30 kg A with 70 kg B at 30oC to get system Q1, mark system Q1 onto the given phase diagram and state its characteristics.
Determine the compositions of phases in system Q1 (if system Q1 is heterogeneous).
4. Describe the process heating system Q1.
5. Describe the process cooling system Q in the given phase diagram. Identify (mark) the point representing this system at 60oC, denote it as
Q60.
6. Mark the points representing phases in system Q60 and determine their composition. If the system Q weight is 10 kg, calculate the weights
of phases inside system Q60.
7. Comment on the possibility to separate 2 components A and B from their solution by fractional distillation.
8. Suggest an experimental plan to construct a liquid – vapour phase diagram of systems containing 2 components A and B at atmospheric
pressure.

100

P const
Q
80

60
T, C
o

40

20

0
A0 20 40 60 80 100
B
%B

1. Determine the boiling points of pure liquid A and pure liquid B

• When we look at the graph, we can see the boiling point of liquid A is 70°C when the composition of B is 0 (𝑥𝐵 = 0% which is on the X-axis) while
the boiling points of pure liquid B is 10°C when the composition of B is 100 (𝑥𝐵 = 100% which is on the X-axis)

2. Comment about values of temperature for liquid-vapour phase equilibrium of all systems (A+B).

• The systems (A+B) boil at the range of temperature 10°C - 70°C which is the range between the boiling point of pure liquid A (𝑇°𝐴 =
70°𝐶) and pure liquid B (𝑇°B = 80°𝐶).

• By comparing the boiling temperature between the pure liquid A and pure liquid B, it can be pointed out that 𝑇°𝐴 > 𝑇°𝐵. So, pure liquid B
is more volatile than the pure liquid A
• By that, when the systems is heterogeneous, the vapor phase will always have the higher composition of liquid B than the corresponding
liquid phase, and vice versa, the liquid phase will always have the higher composition of liquid A than the corresponding vapor phase.
• If the system is above the dew curve, the composition of the system can only be in gaseous phase and on top of that temperature is not
affecting the percentage of A and B. That can be interpreted that 𝑓 = 1 and composition of the system is independent of temperature. On
the other hand, if the system is below the bubble curve, the system is always in liquid state and independent on temperature also.

3. Mixing 30 kg A with 70 kg B at 30°C to get system Q1, mark system Q1 onto the given phase diagram and state its characteristics. Determine the
compositions of phases in system Q1 (if system Q1 is heterogeneous).

• Q1 is marked below the dew curve and above the bubble curve. The position of Q1 can be determined by calculating the composition of B:
"#
𝑥! = × 100 = 70% and with the given temperature 𝑇 = 30℃.
$#%"#

• The composition of each phase are find by draw a line which is parallel to the horizontal axis (𝑥! axix) through the Q1 and intersect with the dew
curve and bubble curve. Then we will mark the intersection of those 2 line with G1 and L1, respectively. After that, by projecting the points L1 and G1 to the
horizontal axis (%𝑥! ) we can have the composition of each phase separately.
• Compositions of each phase at Q1:
o Liquid phase: 𝑥!" = 63%, 𝑥#" = 37%
$ $
o Vapor phase: 𝑥! = 17%, 𝑥# = 83%

4. Describe the process heating system Q1.

• At Q1 (𝑥# = 70%), the system is heterogeneous. By heating the system, only the temperature of the system increase while the total
composition remained constant. However, the mass in vapour phase is increased because the liquid phase vaporized. Moreover, as
temperature rise composition of B in gas phase increased while the composition of B in liquid phase decreased. To be more specific,
$
composition of liquid phase inside system Q1 varies from 𝑥#" = 37% to 20% and composition of inside system Q1 varies from 𝑥# = 83%
$
to 30%. At 𝑇 = 43℃ or Q1 dew point, all liquid all liquid is vaporized to gaseous phase (𝑥# = 30%). And if we continue heating, the
system composition will not change.

5. Describe the process cooling system Q in the given phase diagram. Identify (mark) the point representing this system at 60°C, and
denote it as Q60.

- System Q is heterogeneous, with composition: 𝑥! = 20% at 80°C. By cooling the system, the total composition will not change. However,
there are changes in the amount of component A and B in vapor phase and liquid phase.

- In the temperature range from 80°C down to approximately 67°C, the system is full in vapor phase.

- At approximately 67°C, mass fraction of B and A is 20% and 80% respectively in vapor phase, whereas in liquid phase, mass fraction of B
and A is approximately 2% and 98% respectively.

- In the temperature range from approximately 67°C down to approximately 43°C, the system is a saturated mixture, in both vapor and liquid
phase.

- At approximately 43°C, mass fraction of B and A is 70% and 30% respectively in vapor phase, whereas in liquid phase, mass fraction of B
and A is approximately 20% and 80% respectively.

- In the temperature range from approximately 43°C down to lower temperature, the system is fully condensed into liquid phase.

- To conclude, vapor system Q starts to condense at approximately 67°C and totally condensed into liquid system at approximately 43°C.

- Composition of liquid phase inside system Q varies from 𝑥! = 2% to 20%.

- Composition of vapor phase inside system Q varies from 𝑥! = 20% to 70%.

* To identify the point representing this system at 60°C, draw a vertical line from point Q parallel with the temperature axis. The intersection
of the vertical line with the horizontal line of T=60°C is denoted by 𝑄"# (the green point).

6. Mark the points representing phases in system Q60 and determine their composition. If the system Q weight is 10 kg, calculate the
weights of phases inside system Q60.

- The horizontal line through 𝑄"# intersect the bubble and dew curve, denote them as 𝐿"# and 𝐺"# . Projecting 𝐿"# and 𝐺"# to (%B) axis to have
the composition of each phase separated.

- In liquid phase: 𝑥$% = 95%; 𝑥!% = 5%.

- In vapor phase: 𝑥$& = 60%; 𝑥!& = 40%.

- Calculate the weights of phases inside system, we have 𝑚' = 10𝑘𝑔, the length of the distance from 𝑄"# to 𝐺"# is 20, the length of the
distance from 𝑄"# to 𝐿"# is 15.

- Equations:

𝑚%"# 20
=
3 𝑚&"# 15
𝑚%"# + 𝑚&"# = 𝑚' = 10


40
𝑚%"# = 𝑘𝑔 ≈ 5.714kg
6 7
30
𝑚&"# = 𝑘𝑔 ≈ 4.286kg
7

7. Comment on the possibility of separating 2 components A and B from their solution by fractional distillation.

- It is given in the diagram that pure liquid A boils at 70°C, whereas pure liquid B boils at 10°C. Therefore, component B is more volatile than
component A and each vapour phase contains more component B than the corresponding liquid phase.

- Totally separating A and B from their solutions by fractional distillation is possible. More different boiling points of pure liquids A and B
will make it easier to separate by distillation, as distillation tower is necessary.

- About the principle of separation of 2 components A and B from their solution by fractional distillation, considering distillating the system
𝑄# at 10°C. Increasing the temperature so that the system gets to the point 𝑄# ′, at which there are 2 phases: liquid phase and vapor phase.

- After measuring the weights of phases, we realise that in vapor phase, there is more amount of component B, which is more volatile in system
𝑄# . If we gradually decrease the temperature of the vapor phase, it will condense with more amount of more-volatile component B, until we
get the component B as a pure substance (in the vapor phase after the distillation).

- Continue considering the liquid phase of system 𝑄# . This phase consists of more component A, which is less volatile. If we gradually increase
the temperature of the liquid phase, it will begin to boil and vaporize, and the liquid phase will get more less-volatile component A, until we
get the component A as a pure substance (in the liquid phase after the distillation).

- In the industry, fractional distillation needs the distillation towers to operate.

Figure: Diagram of a typical industrial distillation tower

- As the heat is supplied at the bottom of the tower, the higher the disc is, the lower the temperature. The vapor goes from the bottom
up and the liquid goes from the top down.
- Considering a disc 𝑇( , vapor H and liquid L. Vapor H goes up to the disc having the temperature larger than 𝑇( , whereas liquid L
goes down to the disc having the temperature smaller than 𝑇( . When the vapor phase and liquid phase contact with each other at
disc I, vapor H will cool down and liquid L will increase its temperature.
- As the vapor H decrease its temperature, the amount of more-volatile component B in vapor phase increases and the vapor keeps
getting higher to the discs which have lower temperature, until the vapor phase is condensed and taken out of the tower, containing
highly amount of component B at the top of the tower.
- In contrast, as the liquid L increases its temperature, it vaporizes, taking out the component B and remains the component A in the
liquid. The amount of component A in the liquid increases and the liquid keeps going down to the discs which have higher
temperatures, until there is highly amount of component B at the bottom of the tower.

8. Suggest an experimental plan to construct a liquid–vapour phase diagram of systems containing 2 components A and B at
atmospheric pressure.

- To construct a liquid-vapour phase diagram of a system containing two miscible components A and B at atmospheric pressure, an
experimental plan can be followed:

+ Firstly, determine the range of compositions. Since we have the components A and B, knowing their densities, we can select the range
of compositions for the mixture of components A and B, using different molar ratios or weight ratios.
+ Secondly, using methods such as gravimetric or volumetric methods to mix accurately, having the mixture with different compositions.

+ Thirdly, place the mixture in a sealed container and gradually heat it until it reaches equilibrium between the liquid and vapour phases.
Heating can be operated using a temperature-controlled chamber and the temperature should be chosen based on the expected boiling
points of components A and B.

+ After equilibration, observe the mixtures for phase separation. The appearance of two distinct phases (liquid and vapor) indicates that
the mixture has reached its boiling point. Note the temperature at which phase separation occurs for each composition.

+ To measure the boiling points, the temperature and vapor pressure, such devices as thermometer, refractometer, or gas chormatography
can be used.

+ After ploting all the boiling points onto a graph with the composition of the mixtures on the x-axis and the temperature on the y-axis,
connecting the points create a liquid-vapour phase diagram. Repeating the process is recommended to get a more accurate diagram.

+ The line where the vapour pressure is equal to the atmospheric pressure is called the vapour pressure curve or the bubble point curve.
The line where the liquid phase disappears is called the dew point curve. The area between the two curves is called the liquid-vapour
region, where both phases coexist in equilibrium. The area above the dew point curve is the vapour region, where only vapour exists.
The area below the vapour pressure curve is the liquid region, where only liquid exists.

Problem 4: Write a short essay (max. 2 pages) about the critical point of a pure compound, its possible application in food- and
biotechnology.

The Critical Point: A Bridge Between States of Matter in Food and Biotechnology

I.Introduction

The critical point is the highest temperature and pressure at which a pure material can exist in vapor/liquid equilibrium. At temperatures
higher than the critical temperature, the substance can not exist as a liquid, no matter the pressure. It has significant implications across
diverse scientific disciplines. In the realm of food and biotechnology, understanding this critical phenomenon offers fascinating possibilities
for processing, analysis, and product development. This essay delves into the critical point of pure compounds, explores their applications in
food and biotechnology, and highlights potential areas for future exploration.

Every pure substance possesses a unique set of pressure and temperature conditions known as its critical point. The distinction between the
liquid and gas phases ceases to exist at this point, resulting in a single, homogeneous "critical fluid" (Kumar et al., 2021). This fluid exhibits
properties characteristic of both liquids (high density) and gases (low viscosity and high diffusivity) (Kumar et al. 2021).

II. Applications in Food Science and Biotechnology

The unique properties of critical fluids have revolutionized food science and opened doors to exciting possibilities across a spectrum of
industries. Supercritical fluid extraction (SFE) offers unparalleled precision, utilizing CO₂ as a solvent to selectively extract valuable
compounds from food materials while preserving others (Sahena et al., 2019). This environmentally friendly method minimizes solvent
waste (Zhang et al., 2023), and the low temperatures involved ensure that the components retain their desirable quality and functionality
(Sahena et al., 2019). Similarly, supercritical fluid drying (SFD) utilizes supercritical fluid to remove water from food products. This leads
to improved product quality with minimal degradation and preservation of volatile compounds, along with an enhanced shelf life and
retention of desirable structural integrity (Barbosa-Cánovas et al., 2005). Beyond extraction and drying, critical fluids show immense
promise for the fractionation of complex mixtures, carefully separating them based on subtle solubility differences (Mukhopadhyay &
Moulik, 2020). Additionally, they enable the microencapsulation of sensitive food ingredients, allowing for controlled release and improved
functionality (Andrade et al., 2023).

These applications extend far beyond food science and have found groundbreaking applications in biotechnology. In particular, critical
fluids can encapsulate sensitive biomolecules such as enzymes, drugs, or cells within protective shells (Mohamed et al., 2020). It offers
targeted delivery within the body, controlled release mechanisms, and enhanced stability against external degradation (Mohamed et al.,
2020). Furthermore, critical fluids create a precisely controlled environment for cell culturing, which is crucial for tissue engineering in
regenerative medicine and for investigating potential drug effects on cells (Mendes et al., 2015). Critical fluids also hold promise for
biomaterial processing, tailoring materials, such as hydrogels, for specific applications (Pereira and Faria, 2022), and innovative sterilization
approaches that leverage the antimicrobial properties of certain supercritical fluids (Wang et al., 2020). As demonstrated, the unique
properties of critical fluids have transformed various fields, paving the way for advancements in food science, biotechnology, and beyond.

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