MUST DO TOPICS

UNIT-2
• Phase rule

• Degree of freedom

• Eutectic point

• Triple point

• Congruent point

• Pattison's process

• One component system (Water and Sulphur)

• Two component system (Lead-Silver and Zinc-Magnesium)

• Gibb's phase rule

• Polymers

• LDPE and HDPE

• Vinyl plastics

• Nylons

• Glyptal

• Thermoplastics
Phase rule, law relating variables of a system in thermodynamic equilibrium, deduced by the
American physicist J. Willard Gibbs in his papers on thermodynamics (1875–78). Systems in
thermodynamic equilibrium are generally considered to be isolated from their environment in
some kind of closed container, but many geological systems can be considered to obey the phase
rule. The variables are: the number of phases P (forms of matter—i.e., solid, liquid, and gas—not
necessarily of a single chemical component), the number of chemical components C (pure
compounds or elements), and the number of degrees of freedom F of intensive variables, such as
temperature, pressure, and percentage composition. The phase rule states that F = C − P + 2.
Thus, for a one-component system with one phase, the number of degrees of freedom is two, and
any temperature and pressure, within limits, can be attained. With one component and two
phases—liquid and vapour, for example—only one degree of freedom exists, and there is one
pressure for each temperature. For one component and three phases (e.g., ice floating in water
with water vapour above it, in a closed container), there is no degree of freedom, and
temperature and pressure are both fixed at what is called the triple point.

Degree of freedom: N or f = 3A – R. Here, A indicates the number of particles (in this case, gas
molecules) in the system and R represents the number of constraints (or independent relations).
N or f represents the degree of freedom.

The Eutectic point is when a solid solute, a solid solvent, and a liquid mixture all exist in the
same phase. The eutectic point is the lowest temperature at which the liquid phase is stable at a
given pressure.

Congruent point: The congruent melting point of a substance occurs when the substance melts
sharply at a constant temperature into a liquid of the same composition as that of the solid from
which the liquid was created.

Pattinson's process or pattinsonization: It is a method for removing silver from lead,

discovered by Hugh Lee Pattinson in 1829 and patented in 1833. The process is dependent on the
fact that led which has least silver in it solidifies first on liquefaction, leaving the remaining
liquid richer in silver.

One component system(Water): The water system is divided into three phases:

ICE (S), WATER (L), and WATER VAPOUR (G)

Since H2O is the only chemical compound present, as a result, it is a one-component system.
Curves:
OA- Water & Vapor
OA is the vaporization curve. The curve OA comes to an end at A. It has a critical pressure of
218 atm and a temperature of 374℃. It represents the vapor pressure of a liquid at various
temperatures.
Along the curve, two phases of water and water vapors coexist in equilibrium.
The vapor pressure is one atmosphere. The corresponding temperature in degrees Celsius is the
boiling point of water, which is 100℃.
OB- Ice and Vapor
The OB curve is a sublimation curve. The curve OB comes to an end at B, which is the absolute
zero temperature of -273℃. It depicts the vapour pressure of solid ice at various temperatures.
In equilibrium, the two phases of solid ice and water vapour coexist.
OC- Ice & Water
The OC curve is the fusion curve. The OC curve comes to an end at C, the critical pressure.
In equilibrium, the two phases of solid ice and liquid water coexist. The curve shows that the
melting point of ice decreases as pressure increases. At one atm, the line intersects the curve at
0℃.
Areas:
The area AOC, AOB, and BOC the curves or areas between the curves represent the conditions
at temperature and pressure under which a single phase, i.e., ice, water, and water vapour, can
exist indefinitely.
BOC- Ice- denotes the solid phase.
COA- Water- denotes the liquid phase.
AOB- Vapor- denotes the gaseous phase
Triple Point:
All three curves, OA, OB, and OC, meet at point O, which is known as the triple point, where all
three phases, solid, liquid, and vapor, are in simultaneous equilibrium.
At 0.0075℃- and 4.58-mm Hg pressure, the triple point occurs.
One component system(Sulphur): The phase diagram of an element or a compound tells the
inter-conversion properties or relation between the solid phase, liquid phase, and gas phase of
that substance. The graph is drawn between the temperature and pressure.
Sulfur is the element of group 16 of the p-block and it is the element of period 2. There is one
gas phase, one liquid phase, and two solid phases of sulfur. The two solid phases of the sulfur
atom are monoclinic and rhombic form. The phase diagram of sulfur is given below:
There are three triple points of sulfur and it is indicated in the diagram with numbers 1, 2, and 3.
The most stable form of a sulfur element is the rhombic form and when it is heated slowly then
the rhombic form will convert into monoclinic form at temperature around 114∘C. This solid
form will convert into liquid form at 119−120∘C because the solid form melts at this
temperature. As the pressure decreases the gas form dominates. At the first triple point the
rhombic solid, monoclinic solid, and the gas form co-exist and the temperature is 95.31∘C at 5.1
x 10−6 atm. At the second triple point, the monoclinic solid, the gas form, and the liquid form
co-exists and the temperature is 115.18∘C at 3.2 x 10−5 atm. At the third triple point, the
monoclinic solid form, the rhombic solid form, and the liquid form co-exist and the temperature
is 153∘C at 1420 atm.
Note: The elemental form of sulfur is S8 which means that there are 8 atoms of sulfur in one
molecule. More than one solid form is not common and when there is more than one solid form
the phase diagram becomes a little complicated.
Two component system(Lead-Silver): Two elements lead and silver are completely miscible in
all proportion in their molten state and give rise to a single homogenous phase containing two
components lead and silver.
The co- existence of different phases in equilibrium at different set of conditions is as shown:
AREA ACB:
Within this area, a homogenous single phase of molten liquid of two components in aall
proportions exists.
Applying the phase rule, P + F= C + 1
We have, P =1 and C = 2; which gives F = 2 (T and C)
MELTING POINT CURVES AC AND BC:
In phase diagram of lead and silver, A and b denotes the melting point of pure lead and silver
respectively.
The curve AC denotes the variation of melting point of silver in Pb, while the curve BC indicates
decrease in the melting point of silver with the addition of lead.
The curves AC and BC represent two phase equilibrium:
Solid lead ↔ molten liquid
Solid silver ↔ molten liquid
Eutectic point of lead and silver is denoted by point C in the diagram where all the three phases
solid lead, solid silver and molten liquid coexist at a definite composition and temperature.
Applying reduced phase rule,
P = 3, C = 2, therefore, F = 2=1-3 = 0
Thus, the eutectic point C of lead silver system is invariant which implies that a homogenous
mixture of lead and silver of constant composition (2.6% Ag and 97.4% Pb) melts at a definite
lowest temperature of 303 centigrade. This is known as the eutectic point of lead and silver.
According to the Gibb's Phase rule, a two-component one-phase material, e.g., a binary
crystalline compound, at fixed temperature enjoys one independent degree of freedom.
Polymer is any of a class of natural or synthetic substances composed of very large molecules,
called macromolecules, which are multiples of simpler chemical units called monomers.
Polymers make up many of the materials in living organisms and are the basis of many minerals
and man-made materials.
HDPE is a type of polyethylene with a linear structure. Since its molecules are packed together
tightly, HDPE is an incredibly strong polyethylene with high tensile strength, rigidity, and
impact resistance. HDPE is also resistant to chemicals and can be UV-resistant. Along with its
durability, HDPE is quite a versatile material and easy to fabricate.
Due to its malleability and dimensional stability, HDPE is often used in outdoor furniture and
equipment, including structures like playgrounds. HDPE is also used in industrial applications,
such as pipe flanges and chemical tanks, as well as consumer goods like food and beverage
bottles, cutting boards, and even toys.
Some disadvantages of HDPE include a susceptibility to stress cracking under intense pressure
and low-to-moderate heat resistance. There is also a risk of shrinkage while molding HDPE and
for this reason, HDPE is best suited for CNC machining and additive manufacturing. Processing
HDPE with CNC machining is especially popular, as this manufacturing method can yield tight
tolerances.
One massive benefit to HDPE is its recyclability and reusability. Recycled HDPE is often just as
versatile and weldable as new. HDPE, making recycled HDPE an excellent material choice for
reducing your ecological footprint.
LDPE is a branched version of polyethylene, meaning its molecules are more loosely packed. As
a result, LDPE is less dense than other linear polyethylene’s like HDPE. This doesn’t mean
LDPE isn’t strong, though.
Along with boasting impact resistance, LDPE is also stain-resistant, electrically insulating, and
waterproof. LDPE is also naturally transparent and reflects light well.
Common LDPE consumer components include grocery bags, plastic film or wrap, flexible
packaging material, and food and beverage containers. LDPE is also used in medical device
manufacturing for orthotics and prosthetics.
Design teams should be mindful of some of LDPE’s limitations — LDPE is more prone to stress
cracking than HDPE, less heat resistant than HDPE, and highly permeable to gases like carbon
dioxide. LDPE is also highly flammable, which greatly limits its use in high-temperature
applications.
One upside to LDPE’s lessened heat resistance is its low melting point, which improves heat
sealing. This makes LDPE easy to process using injection molding, which opens up many
manufacturing possibilities in this realm.
Vinyl plastics: In polymer chemistry, vinyl polymers are a group of polymers derived from
substituted vinyl (H2C=CHR) monomers. Their backbone is an extended alkane chain [−CH
2−CHR−]. In popular usage, "vinyl" refers only to polyvinyl chloride (PVC).
Nylons: The term nylon points towards a polymer family known as linear polyamides. There are
two approaches to making nylon for fibre applications. In the first approach, the molecules that
consist of an acidic group (COOH) on every end react with molecules that contain amino (NH2)
groups at each end.

The salt which is formed by two compounds is known as nylon that has an exact ratio of 1:1 acid
to base. This salt is dried and then heated under vacuum to remove water and form the polymer.
In the other approach, a compound that contains an amine at one end and acid at the other are
polymerized to produce a chain with repeating units of (-NH-[CH2]n-CO-)x. The nylon is
referred to as nylon 6 if n = 5 which is another common form of this polymer. The commercial
production of nylon 6 starts with caprolactam that use an open-ring polymerization.
In both the approaches, the polyamide is melt and drawn after cooling to obtain the desired
properties of every intended use.
Properties of Nylon

• Lustrous

• Elastic

• Very strong

• Damage resistant to oil and many chemicals

• Resilient

• Does not absorb water

• Dries quickly
Nylon 6 – It was developed by Paul Schlack. It is formed by ring-opening polymerization.
Nylon 66 – Wallace Carothers patented nylon 66 with the use of amide.
Uses of Nylon

• Clothing – Shirts, Foundation garments, lingerie, raincoats, underwear, swimwear and

 cycle wear.

• Industrial uses – Conveyer and seat belts, parachutes, airbags, nets and ropes, tarpaulins,
thread, and tents.

• It is used to make a fishnet.

• It is used as plastic in manufacturing machine parts

Glyptal: Glyptal is an alkyl resin. Alkyd resins are polyesters that contain dibasic acids, polyols,
and fatty acids. They belong to a thermosetting polymer. Glyptal is a polyester of ethylene glycol
and phthalic acid.

Therefore, glyptal is a alkyd resin which is a polymer of ethylene glycol and phthalic acid.
Thermoplastics are polymers that can be softened through heating before being processed and
then left to cool and harden. Once cooled, they show no changes in chemical properties, meaning
they can be re-melted and re-used several times.
Thermoplastic Polymers Properties
Many thermoplastic polymers are reinforced with fibres. Reinforcement is used to improve
physical properties – specifically heat deflection temperature. Glass fibres are the most
commonly used reinforcing material. The wear resistance and abrasion resistance of
thermoplastic polymers are improved by the use of aramid reinforcing. Although fibres can be
used with any thermoplastic polymer, the following are the most important.
Polyamide polymers use glass fibres to control brittleness. Tensile strengths are increased by a
factor of three, and heat deflection temperature increases from 150 to 500oF.
Polycarbonate compounds using 10, 20, 30 and 40% glass fibre loading have their physical
properties greatly improved.
Other polymers benefiting from the addition of glass fibres include polyphenylene sulfide,
polypropylene and polyether sulfone.
Polymers chosen for structural application are usually selected as a replacement for metal.
Usually a like replacement of a polymer section for a metallic section will result in a weight
saving. In addition polymers can be easily formed into shapes that are difficult to achieve with
metals. By using a polymer, the engineer can design an attractive shape that favours plastic
forming and achieve a saving in cost and weight and a cosmetic improvement.
An additional cost saving is realized since the polymer part does not require painting for
corrosion protection as would the comparable metal part. Selection of the specific polymer will
be based on mechanical requirements and the temperature and chemical end-use environment.
MUST DO QUESTIONS
UNIT-2
•State Gibb's phase rule. OR Derive Gibb's phase Rule.
•Draw and explain the phase diagram of water system.
•What is Pattinson's process for desilverisation of lead? Draw its phase diagram also. (6.5)
•Draw the phase diagram of C02 system and explain how it is different from water system. (6)
•Draw the phase diagram of water system and explain the importance of a triple point.
•Draw and explain the phase diagram of Pb-Ag system. What is Pattinson's Process?
•Find out the number of phases, component and degree of freedom in the following:
(1)NH3(g) at 420C (2) Crystal of Cu SO,. 5H20 (3) An aqueous solution of glucose.
•Define the terms Phase, Component and Degree Of Freedom.
•Write condensed Phase rule and explain why is it used for two component systems.
•Discuss the applications of Eutectic mixtures. (at least 3). (3)
•Define order and molecularity of a reaction with suitable example.
•What is an eutectic mixture? (2.5)
•Explain what is happening at the triple point of water. How many phases are there in the system
at this point? (2.5)
•What are cooling curves? (2.5)