Module 4 - Cryogenics Applied Physics for ME streams 2022 scheme

Module 4 – Cryogenics
Production of low temperature - Joule Thomson effect (Derivation with 3 cases), Porous plug
experiment with theory, Thermodynamical analysis of Joule Thomson effect, Liquefaction of
Oxygen by cascade process, Lindey’s air liquefier, Liquefaction of Helium and its properties,
Platinum Resistance Thermometer, Applications of Cryogenics, in Aerospace, Tribology and
Food processing(qualitative), Numerical Problems.
Pre requisites: Basics of Heat and Thermodynamics Self-learning: Application of Cryogenics in
Food Processing

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 Introduction to Production of Low Temperature:

Cryogenics is defined as a branch of physics that deals with the production of very low
temperatures and their effect on matter. It is a formulation which addresses both aspects of
attaining low temperatures which do not naturally occur on Earth and its application. It is
also defined as the science and technology of temperatures below 120 K.

The limit temperature of 120 K comprehensively includes the normal boiling points of
the main atmospheric gases, as well as of methane. Methane constitutes the principal
component of natural gas. Presently, the liquid natural gas (LNG) represents one of the
largest and fastgrowing industrial domains of application of cryogenics, together with the
liquefaction and separation of air gases.

 Joule-Thomson Effect:
Statement: Joule-Thomson effect is the change in temperature that accompanies
expansion of a gas without production of work or transfer of heat. Explanation: If a gas
initially at constant high pressure is allowed to suffer throttle expansion through the
porous plug of silk, wool or cotton wool having a number of fine pores, to a region of
constant low pressure adiabatically, a change in temperature of gas (either cooling or
heating) is observed. This effect is called as Joule–Thomson or JouleKelvin effect.

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Theory:
Consider a gas which expands through fine pores. Let the initial state and final states of
the gas be (𝑃1, 𝑉1, 𝑇1) and (𝑃2, 𝑉2, 𝑇2). The Change in temperature
𝑇 − 𝑇 = ∂𝑇
is due to Joule-Thomson Effect. The external work done by the gas is given by
𝑊 = 𝑃 𝑇 − 𝑃 𝑇 − − − −1
The internal work done by the gas to overcome the intermolecular gases is given by
𝑎 𝑎
𝑊 =− +
𝑉 𝑉
The total work done is by the gas is given by
𝑎 𝑎
𝑊 = 𝑊 +𝑊 = 𝑃 𝑇 − 𝑃 𝑇 − + − − − −2
𝑉 𝑉
Van der Waals state equation for the gas is given by
𝑎
𝑃+ (𝑉 − 𝑏) = 𝑅𝑇
𝑉
Neglecting 𝑎𝑏/ 𝑉2 the equation could be reduced to
𝑎
𝑃𝑉 = 𝑅𝑇 + 𝑃𝑏 −
𝑉
Thus for the initial and final states of the gas we can write
𝑎
𝑃 𝑉 = 𝑅𝑇 + 𝑃 𝑏 −
𝑉
𝑎
𝑃 𝑉 = 𝑅𝑇 + 𝑃 𝑏 −
𝑉
Substituting above equations in equation 2 and on simplification we get
𝑎 𝑎 𝑎 𝑎
𝑊 = 𝑅𝑇 + 𝑃 𝑏 − − 𝑅𝑇 + 𝑃 𝑏 − − +
𝑉 𝑉 𝑉 𝑉
2𝑎 2𝑎
𝑊 = 𝑅 (𝑇 − 𝑇 ) − 𝑏(𝑃 − 𝑃 ) + −
𝑉 𝑉
For very small values of 𝑎 and 𝑏 in Van der Walls equation it reduces to 𝑃𝑉 = 𝑅𝑇 and
thus 𝑉 = 𝑅𝑇/ 𝑃 . Thus substituting for 𝑉1 and 𝑉2 in above equation we get
2𝑎𝑃 2𝑎𝑃
𝑊 = 𝑅 (𝑇 − 𝑇 ) − 𝑏(𝑃 − 𝑃 ) + −
𝑅𝑇 𝑅𝑇
2𝑎
𝑊 = 𝑅 (𝑇 − 𝑇 ) − 𝑏(𝑃 − 𝑃 ) + (𝑃 − 𝑃 )
𝑅𝑇
Since 𝜕𝑇 = 𝑇1 − 𝑇2 and re-organizing the terms we get

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2𝑎
𝑊 = −𝑅 ∂T − 𝑏(𝑃 − 𝑃 ) + (𝑃 − 𝑃 )
𝑅𝑇
2𝑎
𝑊 = −𝑅 ∂T − 𝑏(𝑃 − 𝑃 ) −𝑏
𝑅𝑇
2𝑎
𝑊 = (𝑃 − 𝑃 ) − 𝑏 − 𝑅 ∂T
𝑅𝑇
Since the gas is thermally insulated the expansion leads to reduction in temperature 𝜕𝑇
and the Heat lost by the gas is given by
𝑊 = 𝐶 ∂T
2𝑎
𝐶 ∂T = (𝑃 − 𝑃 ) − 𝑏 − 𝑅 ∂T
𝑅𝑇
2𝑎
(𝐶 + R) ∂T = (𝑃 − 𝑃 ) −𝑏
𝑅𝑇
The change in pressure 𝑃1 − 𝑃2 = 𝜕𝑃 and 𝐶𝑝 −𝐶𝑣 = 𝑅 the equation 1 could be written as
1 2𝑎
∂T = ∂P −𝑏
𝐶 𝑅𝑇
∂T 1 2𝑎
= −𝑏
∂P 𝐶 𝑅𝑇
Thus The Joule-Thomson Co-efficient is given by
∂T
μ =
∂P
1 2𝑎
μ = −𝑏
𝐶 𝑅𝑇
The above equation gives the change in temperature of Van der Walls gas when subjected
to throttling process.
The Three Cases:
i) if 2𝑎 /𝑅𝑇>𝑏 then 𝜕𝑇 is positive and there will be cooling effect.
ii) if 2𝑎/𝑅𝑇<𝑏 then 𝜕𝑇 is negative and there will be heating effect.
iii) if 2𝑎/𝑅𝑇 = 𝑏 then 𝜕𝑇 = 0 indicating neither cooling and nor heating

 Inversion Temperature
The temperature at which the Joule –Thomson effect changes sign is called the
temperature of Inversion. 𝑇𝑖 . At this temperature 2𝑎𝑅𝑇𝑖 = 𝑏 and hence 𝑇𝑖 = 2𝑎/𝑅𝑏 .

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Above 𝑇𝑖 Joule-Thomson effect produces heating and below 𝑇𝑖 it produces cooling

effect.
 Porous Plug Experiment
Construction: Joule in collaboration with Thomson [Lord Kelvin] devised a very
sensitive technique known as Porous Plug experiment. The experiment set up of porous
plug experiment to study the Joule-Thomson effect is shown in fig.

It consists of the following main parts

i) A Porous plug has two perforated - brass discs 𝐷&𝐷 and the space between is
filled with cotton wool or silk fibers.
ii) The porous plug G is fitted in a cylindrical box-wood which is surrounded by a
vessel L containing cotton wool to avoid heat exchange with surrounding.
iii) 𝑇1&𝑇2 are two sensitive platinum resistance thermometers used to measure the
temperatures of the incoming and outgoing gas.
iv) The gas is compressed to a high pressure with the help of piston P and it is passed
through a spiral tube immersed in water bath maintained at a constant
temperature.
Experimental Procedure
i) The experimental gas is compressed by Pump P and is passed slowly and uniformly
through the porous plug keeping the high pressure constant which read by a pressure
gauge.

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ii) During the passage of the gas through the porous plug it is throttled.
iii) The gas emerging from the pores of the porous plug expands to atmospheric pressure.
iv) Since the expansion of the gas occurs under thermal isolation it is adiabatic.
v) The initial and final temperatures are noted by platinum resistance thermometers
𝑇1&𝑇2.

Experimental Results: A simple arrangement of porous plug experiment is shown in

figure below. The behavior of large number of gases was studied at various inlet
temperatures of the gas and the results are as follows:

i) At sufficiently low temperatures, all gases show a cooling effect.

ii) At ordinary temperatures, all gases except Hydrogen and Helium show cooling
effect. The Hydrogen and Helium show heating effect.
iii) The fall in temperature is directly proportional to the difference in pressure on the
two sides of porous plug.
iv) The fall in temperature for a given difference of pressure decreases with rise in
the initial temperature of the gas.
v) It was found that the cooling effect decreased with the increase of initial
temperature and becomes zero at a certain temperature and at a temperature
higher than the temperature instead of cooling heating was observed. This
particular temperature at which the Joule – Thomson effect changes sign is called
temperature of inversion

 Thermodynamic Analysis of Joule Thomson Effect

The arrangement of the porous plug experiment is shown in Fig. The gas passes through
the porous plug from the high pressure side to the low pressure side. Consider one mole

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of the gas. Let (𝑃1, 𝑉1) and (𝑃2, 𝑉2) represent the pressure and volume of the two sides
of the porous plug. Let 𝑑𝑥 be the distance through which each piston moves to the right.

Work done by piston 1 on the gas 𝑃 𝐴 𝑑𝑥 = 𝑃 𝑉 − − − −1

Work done by piston 2 on the gas 𝑃 𝐴 𝑑𝑥 = 𝑃 𝑉 − − − −2
Net external work done = 𝑃 𝑉 − 𝑃 𝑉 − − − −3
Let 𝑤 be the work done by the gas in separating the molecules against their inter-
molecular attraction
Total amount of work done by the gas = (𝑃 𝑉 − 𝑃 𝑉 ) + 𝑤 − − − −4
Three cases could be considered based on the initial temperature of the gas.
i) Below the Boyle temperature:
If 𝑃2𝑉2>𝑃1𝑉1, then 𝑃2𝑉2 − 𝑃1𝑉1 is +ve. 𝑤 must be either positive or zero. Thus, a net
+ve work is done by the gas and there must be a cooling effect.
ii) At the Boyle temperature:
If 𝑃2𝑉2 = 𝑃1𝑉1, then 𝑃2𝑉2 − 𝑃1𝑉1 is 0. The total work done by the gas is 𝑤. Therefore,
cooling effect at this temperature is only due to the work done by the gas in
overcoming inter-molecular attraction.
iii) Above the Boyle temperature:
If 𝑃2𝑉2<𝑃1𝑉1. Then 𝑃2𝑉2 − 𝑃1𝑉1 is -ve. Thus the net work done by the gas and the
observed effect will depend upon whether (𝑃2𝑉2 − 𝑃1𝑉1) is greater than or less than
w.
If 𝑤> (𝑃2𝑉2 − 𝑃1𝑉1), cooling will be observed.
If 𝑤< (𝑃2𝑉2 − 𝑃1𝑉1), heating will be observed.
Thus, the cooling or heating of a gas depends on
1. The deviation from Boyle’s law
2. Work done in overcoming inter-molecular attraction.
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 Liquefaction of Gasses by Cascade Process:

Definition: Liquefaction of gases means the process into which the gas substances are
converted from gases to a liquid state.
Principles of Liquefaction of Gases
Principle 1: When a gas is compressed by a sufficient amount of pressure below its
critical temperature results in the reduction of temperature.
Principle 2: If a gas is allowed to evaporate under reduced pressure results in the
reduction of temperature.
Principle 3: On the basis of the Joule Thomson effect (Porous plug experiment).

 Liquefaction of Oxygen by Cascade Process - Pictet Process

Principle:
When a liquid is allowed to evaporate under reduced pressure, it produces high cooling.
Cascade system or Process:
When a single stage is not enough to produce the desired result, therefore the process
takes place in a number of stages in a sequence.
Construction: The apparatus modified by H K Onnes consists of compression pumps 𝑃1,
𝑃2 and 𝑃3. 𝑇1, 𝑇2 and 𝑇3 are the three tubes which are surrounded by outer jackets A, B
and C.
‘D’ is a Dewar’s flask which collects liquid oxygen.

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Working:
i) The methyl chloride gas of critical temperature 145°C is compressed by the pump
𝑃1 through the tube 𝑇1. It is cooled by the cold water circulating in the jacket A.
ii) Here the methyl chloride reaches the temperature lower than its critical
temperature. Then it is liquefied under high pressure. The liquid methyl chloride
is collected in the jacket B and evaporates under reduced pressure lowering the
temperature to -90°C
iii) The ethylene gas of critical temperature 10°C is compressed by the pump 𝑃2
through the tube 𝑇2. It is cooled to -90°C by liquid methyl chloride.
iv) Then it is liquefied under high pressure. The liquid ethylene is collected in the
jacket C and evaporates under reduced pressure lowering the temperature to -
160°C.
v) The oxygen gas of critical temperature - 119°C is compressed to 50 atmospheric
pressure by the pump 𝑃3 and passed through the tube 𝑇3. It is cooled to - 160°C
by liquid ethylene in R. Then it is liquefied and the liquid oxygen is collected in
the Dewar flask D.
vi) Limitations: Cascade method cannot liquefy the gases that have very low critical
temperatures like Hydrogen and Helium.

 Linde’s Air Liquefier:

Principle: Linde’s process is known as Adiabatic expansion of compressed gas.
The process is based upon thecombined effect of Joule – Thomson Effect and
regenerative cooling. The compressed gas is made to expand adiabatically and
repeatedly.

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Construction: The apparatus used is shown in figure and the parts are labeled.
Process:
i) The air is first compressed to about 200 atmospheres in the compressor and then
passed through the condensing coils.
ii) As a result, the air is cooled and the water vapors present condense to form the water
which is removed from receiver.
iii) The dry air is then passed through the spiral copper tube which terminates into a jet.
iv) The air expands through the jet into the chamber where pressure is about 50
atmospheres.
v) Thus, as a result of Joule-Thomson effect, the air is cooled.
vi) As this cooled air moves up, it further cools the incoming air
vii) The cooled air is sent to the compressor again and the process is repeated a number of
times till ultimately the air is cooled to such an extent that it liquefies.
viii) The liquefied air gets collected at the bottom of the outer chamber and can be drawn
off. Any uncondensed air is recirculated.

 Liquefaction of Helium and its Properties:

i) Liquefaction of Helium:
Introduction: Helium is the only substance which remains as fluid at temperatures
below -269 °C (4K) and its inversion point is much lower than that of Hydrogen

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namely around -233 °C(40K). The boiling point of Helium is just around -268.9
°C which is quite close to absolute zero on the Kelvin scale.
Principle: Claude’s method works on two principles. i.e: Joule Thomson effect
and mechanical expansion.
Working:
 Initially Helium is compressed to a pressure of 20 atmospheres which raises
its temperature to the region of 300 degrees Kelvin.
 This compressed high temperature Helium is then split into two streams along
different paths.
 The first part of the stream is cooled in the heat exchanger labeled 𝐻𝐸1 with
the help of Helium vapors
 The second part fo the stream passes through the heat exchanger 𝐻𝐸2 to be
cooled with Nitrogen vapors cooled by liquid Hydrogen.
 The second part is then passed through liquid Hydrogen heat exchanger 𝐻𝐸3.
 Further the first and second streams are combined and then passed through
𝐻𝐸4 and again cooled by Helium vapors.
 Finally, the throttle valve is used to initiate the Joule Thomson effect and
Helium is collected in the liquid state in the Helium separator.

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 Properties and Uses:

Properties:
 There are two main isotopes of Helium used for liquefaction namely Helium-4 and
Helium-3.
 There is a slight difference between the properties of the two in terms of their
boiling point and critical temperature.
 The boiling point of Helium-3 is even one degree lower than Helium-4.
 Liquid Helium exhibits super-fluidity.

Uses:

 Lord KammerlinghOnnes used liquid helium to study superconductivity of mercury.

 Liquid Helium is used extensively for use in superconducting magnets which need to be
cooled to extremely low temperatures. The Superconducting Magnets are in turn used
in Magnetic Resonance Imaging and Nuclear Magnetic Resonance.

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 Platinum Resistance Thermometer – PRT

Introduction: The Platinum Resistance Thermometer uses platinum for determining the
temperature. It works on the principle of positive temperature coefficient of resistance.
Hence, the resistance of platinum increases with increase in temperature. The platinum is
a chemically inert metal and can easily be drawn into fine wires. Because of these
properties of platinum, it is used as a sensing element in thermometer.
Construction: The PRT consists of pure platinum wire wound on hollow pipe made up of
insulating mica or ceramic, which is placed in porcelain sheath. Free ends of platinum
wire are attached to long leads of low resistance copper wires (Fig.1). To measure change
in resistance, Wheatstone bridge is used. Two long extension leads form one arm of
Wheatstone bridge connect to the copper leads of encapsulated platinum wire(fig.2).
Advantages:
 Linear relationship of resistance with temperature
 The meter gives the precise reading of temperature.
 The thermometer has a wide range from -200°C to 1200°C.
 The thermometer is quite sensitive and possess high accuracy (0.01 °C).
 Platinum possess stable value of resistance at the given temperature.
 Platinum is chemically inert

Disadvantages:

 The thermometer gives the slow response.

 The melting point of the thermometer is 1800°C.
 But, if platinum measures the temperature higher than 1200°C it starts
evaporating.

 Applications of Cryogenics:
i) Aerospace:
 For critical components in the aerospace industry the cryogenic hardening
can be used to strengthen metal parts in communications systems,
guidance systems, landing gear, and more.

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 Using cryogenic hardening to prep critical components may help the rover
survive these bitter cold conditions of lunar night.
 Cryogenics is used to design the multi-layer insulation blankets to insulate
the spacecraft.
 Cryogenic engine makes use of Liquid Oxygen (LOX) and Liquid
Hydrogen (LH2) as propellants which liquefy at -183 deg C and -253 deg
C respectively.
ii) Tribology - Cryogenic Treatment of Metals:
 Cryogenic processing (Cryogenic Treatment) typically entails a slow
cooling to cryogenic temperatures, a dwell period at this low temperature
followed by a slow return to room temperature and finally a first stage
tempering.
 The cryogenic hardening for steel induces a phase transformation from
austenite to marten site, among other changes. This improves qualities
such as hardness, electrical conductivity, wear resistance, lowering friction
and susceptibility to corrosion.
 Cryogenic treatment works in creases life of the tools like n Reamers,
Tool bits, Tool punches, Carbide Drills, Carbide Cutters, Milling Cutters,
Files, Knives, Reciprocating Blades, Dies and cutting tools.
 Stress relieved ferrous and non-ferrous castings and forgings for enhanced
dimensional stability and surface finish.

The following are the types of cryogenic treatment

 Shallow Treatment: The objects are cooled down to temperature of approximately

-85 °C.
 Flooding: First the object is taken to -85°C, then the chamber is flooded with
liquid nitrogen to reduce the temperature further.
 Deep Cryogenic Treatment (DCT): Subjects the objects to the temperature of
approximately -185 °C

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 Food Processing:
 Cryogenic quick freezer is widely used in the food cold chain resulting from the
better quality of frozen food
 Due to the rapid freezing rate, water in food will become total or partial
vitrification with cryogenic technology
 Liquid nitrogen (LN2) is used in the freezing process of food.
 Cryogenics is also used transportation of large masses of frozen food.
 Cryogenic food freezing is also helpful for large scale food processing industries.

___________________________________________________________________________

Model Questions
 Define Cryogenics and explain the selection of 120K as the reference temperature in
cryogenics
 State and Explain Joule-Thomson Effect.
 Define Joule-Thomson effect and hence discuss the theory.

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 Derive the expression for Joule-Thomson Coefficient

 Explain Joule-Thomson effect and interpret the cases in Joule-Thomson effect.
 Describe Porus Plug Experiment with the help of neat sketches.
 Discuss the Thermodynamical Analysis of JouleThomson Effect.
 Explain the three principles of Liquefaction of Gasses.
 Discuss the Liquefaction of Oxygen by Cascade process with the help of a neat sketch.
 Explain the construction and working of Linde’s Air Liquefier with the help of a neat
diagram.
 Describe the Liquefaction of Helium using Claude’s Method
 Explain the properties of Liquid Helium and its uses.
 With the help of neat sketches explain the construction and working of Platinum
Resistance Thermometers
 Discuss the applications of Cryogenics in aerospace, Tribology and Food processing.
 Explain the application of Cryogenics in Aerospace.
 Explain the applications of Cryogenics in Cryogenic Treatment of metals and advantages.
 Mention the applications of Cryogenics in food processing.

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