Module- 4

Cryogenics

Dr. G H Pujar
Controller of Examination (CoE),
HoD, Dept. Physics

Dept. Engg. Physics, VTU Research Centre

GM Institute of Technology,
Davangere -06
 Module-4

Syllabus

- Joule Thomson effect (Derivation with 3 cases),

Porous plug experiment with theory, Thermo dynamical 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

2
Introduction: production of low temperature
Cryogenics is defined as that branch of physics which deals with the
production of very low temperatures and their effect on matter,
• Coined From Greek: Cryo - Frost ; genics-to Produce
• It addresses both aspects of attaining low temperatures (do not
naturally occur on Earth) & using it for nature study/ human industry.
• In a more operational way, it is 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 (O2, Ar, H2 , He) as well as
of methane which constitutes the principal component of natural gas.
• Today, liquid natural gas (LNG) represents one of the largest – and
fast-growing – industrial domains of application of cryogenics.
 Joule – Thomson’s effect
Q: Explain Joule – Thomson effect and derive . (8 M)

State.:- “If a gas initially at high pressure is allowed to expand through the porous plug
(silk/wool/cotton), to a region of low pressure adiabatically, a change in temperature of gas (either
cooling or heating) is observed. This effect is called as Joule –Thomson or Joule-Kelvin effect.

• Discovered in 1852 by James Prescott Joule , William Thomson, & Baron Kelvin
 Theory of Joule – Thomson’s effect
We know that, van der Waals equation for gas as;
𝑎 𝑎 𝑎𝑏
P+
𝑉2
∙ 𝑉 − 𝑏 = 𝑅𝑇 or 𝑃𝑉 = 𝑅𝑇 + 𝑃𝑏 −
𝑉 │𝑉 2 X
𝑎 𝑎
If one mole of gas is allowed to expand through a porous → 𝑷𝟏 𝑽𝟏 = 𝑅𝑇1 + 𝑃1 𝑏 −
𝑉1
& 𝑷𝟐 𝑽𝟐 = 𝑅𝑇2 + 𝑃2 𝑏 −
𝑉2
plug from a pressure P1 & volume V1 to a pressure P2 and
volume V2, then temperature changes from T1 to T2 due to Substituting the values of 𝑃1 𝑉1 & 𝑃2 𝑉2 in Eqn. (3), we get;
Joule-Thomson effect.
2𝑎 2𝑎
Net ext. work done by the gas = P2V2 – P1V1 (1) 𝑾 = 𝑅 𝑇2 − 𝑇1 − 𝑏 𝑃1 − 𝑃2 + − (4)
𝑉1 𝑉2
Now, int. work is also done by the gas in overcoming the Since, a & b are very small, then 𝑃𝑉 = 𝑅𝑇 → 𝑽 = 𝑹𝑻
𝑷
forces of molecular attraction (i.e., van der Waals force).
𝑅𝑇 𝑅𝑇 │ as T1 & T2 are nearly equal,
𝒂 Hence, 𝑽 = & 𝑽 =
These attractive forces are  to an int. pressure (P)= 𝑽𝟐 𝟏 𝑃1 𝟐 𝑃2 we may write T1=T2=T
Int. work done by the gas when expands from V1 to V2 is; Putting values 𝑉1 & 𝑉2 and 𝑇1 − 𝑇2 = ∆𝑇 in Eqn. (4), we get;
𝑽𝟐 𝑉2 𝑎 𝑎 𝑉2 𝒂 𝒂
‫𝑽𝒅 𝑷 𝑽׬‬ = ‫ 𝑉 𝑉׬‬2 𝑑𝑉 = − = − (2) 2𝑎
𝟏 1 𝑉 𝑉1 𝑽𝟏 𝑽𝟐
𝑾 = −𝑅 ∆𝑇 − 𝑏 𝑃1 − 𝑃2 + 𝑃 − 𝑃2
𝑅𝑇 1
⸫ Tot. work done by the gas = Ext. work + Int. work
2𝑎
𝑎 𝑎 or 𝑾 = 𝑃1 − 𝑃2 − 𝑏 −𝑅 ∆𝑇 (5)
i.e., 𝑾 = 𝑃2 𝑉2 −𝑃1 𝑉1 + − (3) 𝑅𝑇
𝑉1 𝑉2
 Theory of Joule – Thomson’s effect Contd…….
Eqn (6) gives the fall in temperature or the cooling
2𝑎
or 𝑾 = 𝑃1 − 𝑃2 − 𝑏 −𝑅 ∆𝑇 (5) produced in a van der Waals gas when subjected to
𝑅𝑇
throttling process (i.e, expansion of gas from P1 to P2).
Since the gas is thermally insulated, the consequence of Different Cases:
doing this work (W) is to fall the gas temperature by ∆𝑻 Case (i) : If
𝟐𝒂
>𝒃 then ∆𝑻 is positive.
𝑹𝑻

⸫ Heat lost by the gas = 𝐶𝑉 ∆𝑻 Hence there will be a cooling effect.

2𝑎 𝟐𝒂
→ 𝐶𝑉 ∆𝑻 = 𝑃1 − 𝑃2 − 𝑏 −𝑅 ∆𝑇 Case (ii) : If <𝒃 then ∆𝑻 is negative.
𝑅𝑇 𝑹𝑻

2𝑎 Hence there will be a heating effect.

or 𝐶𝑉 + 𝑅 ∆𝑻 = 𝑃1 − 𝑃2 −𝑏
𝑅𝑇
𝟐𝒂
2𝑎 Case (iii) : If =𝒃 then ∆𝑻 = 𝟎.
𝑹𝑻
i.e., 𝐶𝑃 ∆𝑻 = 𝑃1 − 𝑃2 −𝑏
𝑅𝑇 Hence there will be neither heating nor cooling effect.
𝑃1 − 𝑃2 2𝑎 Inversion Temperature (Ti): Temperature at which the Joule–
∆𝑻 = −𝑏 (6)
𝐶𝑃 𝑅𝑇 Thomson effect changes its sign is called Inversion temperature
𝟐𝒂 𝟐𝒂
∆𝑻 1 2𝑎 @ T=Ti, = 𝒃 or = 𝑻𝒊
𝑹𝑻𝒊 𝑹𝒃
Joule-Thomson Coefficient 𝜇𝐽𝑇 = = −𝑏
∆𝑷 𝐶𝑃 𝑅𝑇 Hence, above 𝑻𝒊 heating & below 𝑻𝒊 cooling effect
 Porous Plug Experiment
Q: Explain the construction & working of Porous Plug experiment with neat diagram.(8M)
Construction:
• Devised in 1852 by James Prescott Joule , William Thomson, &
Baron Kelvin (as shown in Fig) to study the Joule –Thomson effect.
• It consists of the following main parts:
a) A Porous plug tube B having two perforated -brass discs D. Space
between D is placed with cotton/wool/silk fibers (G).
c) Porous plug tube B is fitted in box-wood W, which is surrounded by a vessel containing cotton
wool. This is to avoid loss or gain of heat from the surroundings.
d) T1 & T2 are two sensitive platinum resistance thermometers and they measure the
temperatures of the incoming and outgoing gas.
e) The gas is compressed to a high pressure with the help of piston P and it is placed
through a spiral tube S immersed in water bath maintained at a constant temperature. If any
heating of the gas due to compression, absorbed by the water bath.
 Porous Plug Experiment
Working:
• Experimental gas is compressed by piston P and is passed slowly and uniformly
through the porous plug @ constant high pressure.
• During the passage through the porous plug, the gas is throttled & hence separation
b/w the molecules increases.
• By passing through porous plug, volume of the gas increases against the atmospheric pressure. As there is no
loss or gain of heat during the whole process, the expansion of the gas takes place adiabatically. Initial & final
temperatures are noted by platinum resistance thermometers T1 & T2
• Experimental Results: Behavior of large no. of gases was studied at various inlet temp. of gas & results are :
(1) At sufficiently low temp., all gases show a cooling effect.
(2) At ordinary temp., all gases (except H2 & He) show cooling effect. H2 & He show heating effect.
(3) Fall in temp. is directly proportional to the difference in pressure on the two sides of porous plug.
(4) Cooling effect decreased with the increase of initial temp. & becomes zero at a certain temp. and at a
temp. higher than that, instead of cooling, heating was observed. This particular temp. at which the Joule
–Thomson effect changes sign is called temperature of inversion
 Theory of Porous Plug Experiment: Thermo dynamical analysis of Joule Thomson effect
Arrangement of the porous plug experiment is equivalently shown in Fig.
Consider one mole of the gas. Let P1 (high), V1 & P2(low) , V2 represent the
pressure & volume of the two sides of the porous plug. Let dx be the
distance through which each piston moves to the right.
Work done on the gas by the piston 1 = P1A1dx = P1V1
Work done by the gas on the piston 2 = P2A2dx = P2V2

Net external work done by the gas = P2V2 – P1V1

Let w be internal work done by the gas in separating the molecules against their inter-molecular attraction.
⸫Total amount of work done by the gas = (P2V2 – P1V1) + w Boyle temp: is the temp. range at which a
real gas starts to behave like an ideal gas
There are three cases depending upon the initial temperature of gas.
i. Below Boyle temp: P2V2 < P1V1. Then P2V2 – P1V1 is +ve. Hence, w must be +ve. Thus, a net +ve work is done by the gas.
Hence, there must be a cooling effect. i.e., If w > (P2V2 – P1V1,), cooling will be observed.
ii. At Boyle temp: P2V2 = P1V1 , Then P2V2 – P1V1 =0. The total work done by the gas in this case is w.
Hence, cooling effect at this temperature is only due to the work done by the gas in overcoming inter-molecular attraction.

iii. Above Boyle temp: P2V2 > P1V1 .Then P2V2 – P1V1 is –ve. Hence, w must be negative. Thus, a net -ve work is done by the gas.
Hence, there must be a heating effect. i.e., If w < (P2V2 – P1V1,), heating will be observed.
Thus, the observed effect will depend upon whether (P2V2 – P1V1) is greater than or less than w.
 Liquefaction of gases

Def: “It is the process in which the gases are converted to a liquid state” -Liquefaction of gases

Principles of Liquefaction of gases

• Principle1: In which when a gas is compressed by a sufficient amount of pressure below its

critical temperature, as a result liquefaction starts.

• Principle2: When we reduce the pressure, and the gas or the liquid is allowed to evaporate,

then due to evaporations, it causes cooling.

• Principle3: On the basis of the Joule Thomson effect (Porous plug experiment)
 Liquefaction of Oxygen gas by cascade process (Pictet process)
• First used by Pictet in 1878, obtained Liquid Oxygen using pressure & other liquefied gases.
• Cascade system:: A process is called as Cascade, 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:
1. In this apparatus, three compressors
C1, C2, C3 are used to fulfill the
requirement of sufficient pressure.
Also, the C1, C2, and C3 have a suction
side which is used during the process.

2. Three condensers R1, R2, R3 are

used, into which three refrigerants
cold water, methyl chloride &ethylene
are used to get desired result.

3. The Liquid oxygen is collected in the

last, into a Dewar flask.
Working: Liquefaction of Oxygen by cascade process
• Gaseous CH3Cl is pumped by C1 into the spiral tube. Refrigerant in R1 starts liquefying CH3Cl as its Tc is
143°C, which is more than room temperature.
• Now, the liquid CH3Cl comes into condenser R2 through the tube. Here one portion of R2 is connected with
the suction side of compressor C1.
• Here, due to the evaporation of liquid CH3Cl in reduced pressure, more cooling is produced, and the
temperature of condenser R2 decreases more. Evaporated CH3Cl return back to C1.
• Now, gaseous C2H4 is pumped by C2 into next spiral tube. Here refrigerant liquid CH3Cl converts this gas into
liquid C2H4 as its critical temperature is around 9.2°C
• Now, this liquid C2H4 comes into R3 & one portion of R3 is connected
with the suction side of C2.
• Here, due to the evaporation of liquid C2H4 in reduced pressure, more
cooling is produced, and the temp. of R3 decreases more (of around
−160°C). Evaporated C2H4 return back to C2.
• Now, gaseous oxygen is pumped by C3 into the next spiral tube.
• Here, due to the very low temp. inside R3, the oxygen gas converts into
liquid and later collected into a Dewar flask as Tc of oxygen is −118°C. Limit: cannot liquefy
gases of very low Tc
• Then, likewise the previous stages, the evaporated oxygen return back such as H2 (-240°C)
to the C3 through the suction side of the compressor. & He (-267.8°C)
 Lindey’s Air Liquefier
• First succeeded by Hampson-Linde in 1895, obtained Liquid air using regenerative cooling and
the Joule Thomson effect.

Construction:
1. It consists of two compressors C1 at (25
atm pressure) & C2 (200 atm pressure).
2. Heat exchangers/condensers R1 and R2
are used in which cold water and a
freezing mixture is used as a refrigerant.
3. A Liquid solution of KOH (Potassium
Hydroxide) chamber is required to get
pure air.
4. There are two chambers E1 & E2 and P1
& P2 are the two small nozzles.
5. At last, the liquid air is collected into a
Dewar flask.
Working: Lindey’s Air Liquefier
• Air is pumped at a pressure of 25 atm into the spiral tube & gets cooled after passing through R1. Here, air
becomes cool because of cool water inside R1. This cooled air then passes through KOH solution.
• Here, KOH separates air from water vapors & absorbs CO2 present in the air. After this, the air further moves to C2.
• In C2, air is pumped at a pressure of 200 atm into the next spiral tube. Now, the air becomes cool again, after passing
through R2. Here, the air is cooled because of Freezing mixture inside R2.
• Now, temp of this air decreases to around −20°C. Then it is allowed
to expand through nozzle P1 in chamber E1 & suffers Joule
Thomson effect. Due to this effect, more cooling is produced in E1,
and pressure reduces to about 50 atm.
• This cooled air then returns back to C2 & where it is again pumped
into the spiral tube. This air again suffers Joule Thomson effect, and
more cooling is produced in E1.
• Repeating some cycles of this process, more and more cooling is
produced in E1. After getting sufficient temperature, the cooled air
is allowed to expand through nozzle P2 in E2 and again suffers the
Joule Thomson effect, and pressure reduces to about 1 atm.
• Now the temperature decreases to around −188°C in E2 and the air
gets liquefied. This liquefied air is collected into the Dewar flask.
• Also, in E2 the un-liquefied air is returned back to C1, this further
cooled the air &again pumped at pressure of 25 atm into spiral tube.
Liquefaction of Helium (Claude’s method)
• First succeeded by Claude and obtained Liquid He
using Joule Thomson effect & mechanical
expansion.
Construction:
1. It consists of a compressor C (300 K at 20 atm
pressure) & four heat exchangers HE1, HE2,
HE3 & HE4

2. Heat exchangers are being used in which

liquid/vapour He/H2 are used as a refrigerant.

3. At last, the liquid He is delivered from Helium

Separator chamber.
Liquefaction of Helium (Claude’s method)
Working:
• Initially He is compressed to a pressure of 20 atm
which raises its temperature to 300 K.
• This compressed He is then split into two paths.
• First part is cooled in HE1 with help of He vapours.
• Other part passes through HE2 to be cooled with
H2 vapours.
• Both these streams combine to be passed through
the liquid H2 heat exchanger HE3.
• Then again getting cooled in HE4 by Helium vapours.
• Finally the throttle valve is used to initiate the Joule
Thomson effect and Helium is collected in the liquid
state in the Helium separator.
 Properties and uses of Helium
Properties of Helium:
• Isotopes: There are nine known isotopes of He of which two, He-3 and He-4, are stable. There
is a slight difference between the properties of the two in terms of their boiling point, critical
temperature and so forth.
• Physical: It is a colorless, odorless, insipid and non-toxic gas.
• Chemical: It's less soluble in water than any other gas. It's the less reactive element and doesn't
essentially form chemical compounds.
• The density and viscosity of He are very low.

Uses of Helium:
• Liquid Helium is used extensively in superconducting magnets which need to be cooled to
extremely low temperatures during their use.
• In medical instruments such as Magnetic Resonance Imaging & Nuclear Magnetic Resonance.
 Platinum Resistance Thermometer
• It uses platinum for determining the temperature & works on the principle of positive
temp coefficient of resistance;- resistance of platinum increases with increase in temp.
• platinum is a chemically inert metal & can easily be drawn into fine wires. Due to these
properties, it is used as a sensing element in thermometer.
Construction:
1. PRT consists of pure platinum wire wound on hollow pipe of insulating mica or
ceramic, which is placed in porcelain sheath (Chromium+A2O3).
2. Free ends of platinum wire are attached to long leads of
low resistance copper wires.
3. 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)
Working:
• When PRT subjected to temperature variation, the
wheatstone bridge gets unbalanced due to change in
resistance Rt of platinum resistance.
• This makes the pointer move over circular scale of
galvanometer, which is directly calibrated to give measured
value of temperature.
 Platinum Resistance Thermometer

Advantages:
 Linear relationship of resistance with temperature.
 Meter gives the precise reading of temperature.
 Thermometer has wide range from -260 to 1200°C.
 It is quite sensitive and possess high accuracy.
 Platinum is chemically inert & possess stable
value of resistance at the given temperature

Disadvantages:
• The thermometer gives the slow response.
• The melting point of the thermometer is 1800°C. i.e., if platinum measures the temperature
higher than 1200°C it start evaporating.
 Applications of Cryogenics
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, etc.
• Using cryogenic hardening to prepare critical components may help the rover to survive under
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 O2 & Liquid H2 as propellants.

Food Processing:
• Cryogenic quick freezer is widely used in food cold chain resulting from better quality of frozen food.
• Due to rapid freezing rate, water in food will become total/partial vitrification with cryogenic technology.
• Liquid N2is 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.
 Applications of Cryogenics
Tribology - Cryogenic Treatment of Metals:
• Cryogenic Treatment typically entails a slow cooling to cryogenic temperatures, a dwell period at this low
temp. 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 martensite, among
other changes. This improves qualities such as hardness, electrical conductivity, wear resistance, lowering
friction and susceptibility to corrosion
• Cryogenic treatment works increase life of the tools like n Reamers, Tool bits, Tool punches, Carbide Drills,
Carbide Cutters, Milling Cutters, Files, Knives, Reciprocating Blades, Dies & cutting tools.
• Cryogenic treatment in castings & forgings enhances the dimensional stability & surface finish.
Following are the types of cryogenic treatment:
1. Shallow Treatment: The objects are cooled down to temperature of approximately -85 °C.
2. Flooding: First the object is taken to -85°C, then the chamber is flooded with liquid nitrogen to
reduce the temperature further.
3. Deep Cryogenic Treatment (DCT): Subjects the objects to the temperature of approximately -185 °C
 Numerical Problems
Joule Thomson Effect

Example 1. In Joule Thomson experiment Temperature changes from 100 °C to 150 °C for
pressure change of 20 Mpa to 170 MPa. Calculate Joule Thomson Coefficient.
Ans: 𝜕𝑇/𝜕𝑃 = 0.333𝜇𝐾𝑃𝑎−1

Given Data: T1 =100 + 273 = 373 K ; T2 = 150 + 273 = 423 K

P1 = 20 Pa P2 =170 pa

Change in temperature, (T2- T1 ) = 50 K

Change in pressure, (P2 - P1) = 150 MPa
∆𝑻 𝟓𝟎 𝟏
Joule Thomson Coefficient, 𝝁𝑱𝑻 = ∆𝑷 = 𝟏𝟓𝟎 = 𝟑 = 𝟎. 𝟑𝟑𝟑
 Numerical Problems
Example 2. Calculate inversion temperature of gas. Given: a=0.244 atm L2/mol2,
b=0.027 L/mol& R=0.0821 L atm/K/mol.

Given Data: a = 0.244 atm L2/mol2, b = 0.027 L/mol, R = 0.0821 L atm/K/mol

2a
Inversion Temperature, Ti 
Rb
2  0.244
= 0.0821 0.027

Ti = 220.14K