CRYOGENIC

ENGINEERING 2

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 Properties of Cryogenic Fluids
Saturated Liquid
Liquid
Liquid Unit LHe3 LHe4 Hydroge LN2
Neon
Property n
Normal
K 3.19 4.214 20.27 27.09 77.36
Boiling point
Critical
K 3.32 5.2 33.2 44.4 126.1
temperature
Critical
MPa 0.117 0.229 1.315 2.65 3.39
Pressure
Triple point K - - 13.9 24.53 63.2
Kg/m
Density 58.9 124.8 70.79 1206 807.3
3
Latent Heat KJ/Kg 8.49 20.9 443 85.9 199.3

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 Properties of Cryogenic Fluids
Saturated Liquid Liquid
Unit Liquid Air LOX
Liquid Property Argon methane
Normal Boiling
K 78.8 87.28 90.18 111.7
point
Critical
K 133 150.7 154.6 190.7
temperature
Critical
MPa 3.92 4.89 5.08 4.64
Pressure

Triple point K - 83.8 54.4 88.7

Density Kg/m3 874 1394 1141 424.1

Latent Heat KJ/Kg 205 161.9 213 511.5

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 Cryogenic Fluids-Liquid
Nitrogen (LN2)
Boils at 77.36 K and freezes at 63.2 K.
Resembles water in appearance - 807 kg/m3 at 1 atm.
Exists in 2 stable isotopes - N14 & N15.
Produced by distillation of air.
Used to provide an inert atmosphere in chemical and
metallurgical industries.
It is also used as a liquid to provide refrigeration.
Food preservation, blood, cells preservation.
High temperature superconductivity.
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 Cryogenic Fluids-Liquid Oxygen
(LOX)
Blue in color due to long chains of O4.
Boils at 90.18 K and freezes at 54.4 K at 1 atm.
Has a density of 1141kg/m3.
O2 is slightly magnetic (paramagnetic)
High chemical reactivity
exists in 3 stable isotopes - O16, O17, O18
Produced by distillation of air
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 Cryogenic Fluids-Liquid Argon
It is a colorless, inert and non toxic gas.
It boils at 87.3 K and freezes at 83.8 K.
It has a density of 1394 kg/m3.
Exists in 3 stable isotopes Ar36, Ar38, Ar40.
The property of inertness of argon is used to purge moulds in casting
industry.
It is used in Argon-oxygen decarburization (AOD) process in stainless steel
industry.
It offers inert atmosphere for welding stainless steel, aluminum, titanium
etc.
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 Cryogenic Fluids-Liquid Air
It has a boiling point of 78.9 K and 874 kg/m3 as density.
Liquid air was earlier used as pre-coolant for low
temperature applications.
Liquid air is primarily used in production of pure nitrogen,
oxygen, and rare gases.

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 Cryogenic Fluids-Liquid Neon
It is a clear, colorless liquid with boiling point at 27.1 K.
Neon is commonly used in neon advertising.
Liquid neon is commercially used as cryogenic
refrigerant.
It is compact, inert and less expensive as compared to
liquid helium.

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 Cryogenic Fluids-Liquid
Methane
Clear, colorless
It boils at 111.7 K.
Density 424.1 kg/m
It can be used as rocket fuel.

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Cryogenic Fluids-Liquid Fluorine
Light yellow liquid.
Normal boiling point 85.24K, freezing point 53.5K (yellow
solid, at 45.6K transforms to white solid)
Most dense cryogenic liquid 1507 kg/m.
Highly toxic, sharp pungent odor.

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 Liquid Hydrogen

Hydrogen exists in diatomic form as H2.

It boils at 20.27 K and freezes at 13.95 K.
It has a density of only 70.79 kg/m3 (one of the
lightest).
It has a latent heat of 443 kJ/kg
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 Hydrogen

Exists in 2 stable isotopes hydrogen,

deuterium and tritium.
Tritium is radioactive and is unstable.

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 Hydrogen

Hydrogen exists in two molecular forms

Ortho and Para.
A H2 molecule has 2 protons and 2 electrons.
The distinction between the two forms of
hydrogen is the direction of the spin of
protons.
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 Hydrogen

The two protons possess a spin which gives

the angular momentum.
If the nuclear spins are in same direction
for both the protons, it is Ortho Hydrogen.
If the nuclear spins are in opposite direction
for both the protons, it is Para Hydrogen.
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 Hydrogen

Ortho- Hydrogen Para- Hydrogen

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 Hydrogen
With the decrease in the temperature, the Ortho
hydrogen is converted to the Para hydrogen.
At 300 K Ortho and Para hydrogen exists in the
ratio 3:1
At 20 K 99.821% of the Hydrogen will be in Para
form

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 Hydrogen

Para form is a low energy form and

therefore heat is liberated during
conversion.
Conversion of ortho to para form of
hydrogen is an exothermic reaction.
This conversion is a very slow process.
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 Hydrogen

During liquefaction, the heat of conversion

causes evaporation of 70% of hydrogen
originally liquefied.
In order to make this conversion faster,
catalysts are added.

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 Deuterium
Deuterium atom has one proton and one neutron.
Two Deuterium atoms make up one D2 which is
called as Heavy Hydrogen.
Similar to hydrogen, it also exists in two
molecular forms Ortho and Para.
Normal deuterium exists in ratio of 2/3 Ortho and
1/3 Para.
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 Deuterium

As temperature decreases, Para D2 gets

converted to Ortho D2.
At 20 K 98 % of D2 will be in Ortho form
Most of the physical properties of
Hydrogen and Deuterium mildly depend on
Ortho Para Composition.
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 Hydrogen-Uses

Cryogenic engines are powered by

propellants like liquid hydrogen.
It is being considered as fuel for
automobiles.
Cryocoolers working on a closed cycle use
hydrogen as working fluid.
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 Helium

In the year 1908, K. Onnes at Leiden

liquefied Helium using Helium gas obtained
by heating Monazite sand from India.
Helium exists in two isotopes- He4 and He3.
The percentage of He3 is 1.3 x 10-4 %. So
mostly it is He4
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 Helium

Liquid Helium is inert, odorless, colorless and exists

in monatomic state.
It boils at 4.2 K.
It has a density of 124.8 kg/m3.
Critical temperature and pressures are 5.25 K and
0.227 Mpa
It has a latent heat of 20.28 kJ/kg.
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 Helium Phase Diagram

It has no triple point.

Saturated liquid Helium
must be compressed to
25.3 bar to solidify. (no
freezing point at 1 atm)

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 Helium Phase Diagram

As Liquid Helium is further cooled

below a particular temperature a new
liquid phase, LHe II, emerges out.
The two different liquids are called as
LHe I and LHe II.
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 Helium Phase Diagram

These liquid phases are distinguished on

the basis of viscosity as follows.
LHeI : Normal fluid
LHeII : Super fluid

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 Helium Phase Diagram

This phase separation line is

called as Lambda Line.
The point of intersection of
phase separation line with
saturated liquid line is called
as Lambda Point (T=2.171 K
at 5.073kPa). 27
 Helium Phase Diagram

LHe II is called as super fluid because it

exhibits properties like zero viscosity and
large thermal conductivity.
This fluid expands on cooling.
The variation of specific heat in Liquid
Helium is abrupt and posses a discontinuity
at the lambda point. 28
Helium Phase Diagram-Variation of
specific heat

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 Helium Phase Diagram

The point is called as lambda point because

shape of the curve resembles the Greek
letter
There is no energy involved in lambda
transition.

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 Helium Phase Diagram
Also, heat transfer in super fluid helium (LHe II)
is very special. When the pressure above LHe - I is
reduced by pumping, the fluid boils vigorously.
During pumping, the temperature of liquid
decreases and a part of the liquid is boiled away.
When T < (LHe-1 to LHe-II) point temperature,
the apparent boiling of the fluid stops .
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 Helium Phase Diagram
Liquid becomes very clear and quiet, even
though it is vaporizing rapidly.
Thermal Conductivity of He II is so large
(86500 W/m-K), that the vapor bubbles do
not have time to form within the body of
the fluid before the heat is quickly
conducted to the surface.
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Thermal Conductivity of He I is 0.024

 Super Fluid
LHe II, called as super fluid, exhibits properties like
zero viscosity and large thermal conductivity.
At lambda point liquid composition is 100% normal
fluid.
At absolute zero liquid composition is 100% superfluid
It flows through narrow slits and channels very rapidly.

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 Super Fluid

The peculiar properties of Liquid Helium

II give rise to interesting thermal and
mechanical effects as listed below.
Thermomechanical Effect
Mechanocaloric Effect
Fountain Effect
Rollin Film Effect 34
Thermomechanical Effect
Consider a flask filled with super fluid
helium (LHe II) and a heating coil
placed inside a differential container
as shown in the figure.
When the heat is applied to the fluid in
the inner container, the concentration
of normal fluid increases.
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 Thermomechanical Effect

The Super fluid component tends to move

towards this region to equalize the
concentration.
Super fluid being less viscous, can flow
rapidly through the narrow channel.
Normal fluid being more viscous, its flow is
impeded by the channel resistance 36
 Thermomechanical Effect
As a result, due to the induced pressure difference, a
pressure head called as Thermo Mechanical Pressure
Head is developed.
Because of thermal action, one mechanical head is getting
generated or the flow of fluid is happening from outside
container to inside container through a thin little channel,
and this is what we call as thermomechanical effect
This head is proportionate to the temperature rise of the
fluid.

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Mechanocaloric Effect

The apparatus consists of a round

flask filled with a fine powder and
Super fluid Helium (LHe II).
The flask has an opening at the
bottom.
The Super fluid Helium (LHe - II)
being less viscous flows through
the fine powder easily. 38
 Mechanocaloric Effect
As a result, the concentration of normal fluid
increases above the powder.
Hence, the temperature increases inside the flask,
which is sensed by resistance thermometer.
Higher temperature is created at this point and
lower temperature below this flask and this is
what we call as mechanocaloric effect.
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Fountain Effect

The U-tube is filled with a

fine powder and is immersed
in Super fluid Helium (LHe
II) bath.
When heat is added to the
powder, the concentration of
normal fluid increases due 40

to rise in the temperature

 Fountain Effect
As a result, the Super fluid rushes
in, to equalize the concentration.
Normal fluid, being more viscous
cannot flow through the fine powder.
The inflow of super fluid builds up
with time and finally squirts out (25
to 30 cm) through the fine capillary
opening at the top.
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Rollin Effect

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 Rollin Effect

The Liquid Helium II exhibits a

property of clinging to the walls of the
container called as Creeping effect.
The thickness of the film is in the
order of 30 nm.
Consider a test tube filled with Liquid43

Helium II as shown in the figure.

 Rollin Effect
When the test tube is lowered into the Liquid
Helium - II bath, the Rollin film clings to the tube
and gradually fills the tube.
On the other hand, if the tube is raised above the
bath level, it empties out slowly.
In these films, the capillary forces dominate the
gravity and viscous forces.
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 Rollin Effect

The enclosure or the container has to

be designed properly otherwise
Helium II creeps to the warmer side
through valves and openings and will
evaporate.
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 Second Sound
Due to difference in concentrations of normal
helium and super fluid in LHe 4, there exists a
temperature gradient. This gradient causes
oscillations of Normal fluid and Super fluid
which are called as Second sound.
The velocity of Second sound varies from zero at
lambda point to 239 m/s at near 0 K.
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 Second Sound
Second sound consists of temperature
waves or oscillations in temperature rather
than pressure waves in ordinary sound.
If only the super fluid component in Second
sound oscillates, then it is called as Third
sound.
The velocity of propagation of Third sound 47

is around 0.5 m/s.