Thermodynamic Fundamentals of Refrigeration, Cryogenics

and Low Temperature Physics

Problems for colloquium

Zeroth law of thermodynamics what thermodynamic

parameter can be measured on the basis of the Zeroth
Law?

Zeroth law of thermodynamics states that:

,,If in the case of three systems A, B and C, system A is in equilibrium C and B is in
equilibrium with C, then A is in equilibrium with B.
Consequence of this statement is defining temperature as a function, which has to be
identical in case of an arbitrary number of systems divided by heat transferring partitions
remaining in thermal equilibrium. The law permits the construction of thermometer to
measure this property.We can calibrate the change in a thermal property, such as the
length of a column of mercury, by putting the thermometer in thermal equilibrium with
a known physical system at several reference points (ex. boiling and freezing point
of water). If we then bring the thermometer into thermal equilibrium with any other
system, we can determine the temperature of the other system by noting the change in
the thermal property.

First law of thermodynamics.

The existence of thermodynamic function results from the first rule of thermodynamics,
stating that
,,System energy is maintained if heat is taken into account,.
it is the internal energy of a body which may be changed as a result of work performed on
the body or heat transmitted to the body. It follows from the connected first and zeroth
laws of thermodynamics, that the consequence of thermal contact between two bodies,
which are not in the state of thermal equilibrium and thus they differ in temperature,
is the transfer of heat between them leading to a simultaneous change of energy of the
two bodies so that the total energy of the system was constant.
First law of thermodynamics can be also expressed using equation:
1

U = Q W
,,The change in internal energy of a system is equal to the heat added to the system
minus the work done by the system..
Taking dU as an differential change in internal energy, one writes:
dU = Q W
dU = Q pdV
We can also express first law of thermodynamics using enthalpy instead of internal
energy: dH = Q + V dp

Second law of thermodynamics, applicability to refrigeration.

In terms of only the first rule of thermodynamic, we cannot exclude the case of spontaneous heat transfer from the body of lower temperature to the body of higher temperature because then the energy is maintained. The fact that such spontaneous heat transfer
is impossible is indicated by the second rule of thermodynamics which was formulated
by Clausius in the following way:
,,It is not possible to build self-acting equipment working cyclically in such a way that
the only effect of its activity is the transfer of heat from a colder location to a hotter
location.
The second rule of thermodynamics indicates that lowering the temperature of a body
below the environment temperature requires the co-operation of at least three thermodynamic systems: a body whose temperature is to be lowered, environment which is the
source of heat of constant temperature and the source of energy devoid of entropy, i.e.
undergoing unlimited conversion.

Sadi Carnot and his waterwheel analogy. What is the

analogue to water in thermodynamic systems (engines,
refrigerators)?

Water/Heat will not flow spontaneously from a low level/cold object to a high level (hot
object).
The second law of thermodynamics is a general principle which places constraints upon
the direction of heat transfer and the attainable efficiencies of heat engines. In so doing, it
goes beyond the limitations imposed by the first law of thermodynamics. Its implications
may be visualized in terms of the waterwheel analogy (Figure 1) proposed by Sadi
Carnot.

Figure 1: Waterwheel analogy to engines and refrigerators

Ideal Carnot cycle of refrigeration.

Carnot cycle is a cycle with highest possible thermodynamic efficiency. It consist of two
isentropic processes and two isothermal processes. Figure 2 shows graphical representation of Carnot cycle on T-s diagram. Carnot efficiency for refrigerators (COP):
COPCarnot =

Q0
W

Tc
T Tc

Transformation of Carnot cycle into vapour compression

cycle.

The cycle presented on Figure 2 (Carnot cycle in two-phase area) has some drawbacks:
there is no sufficient signal when the evaporation should be finished in point c
3

Figure 2: Carnot cycle representation on T-s diagram

isentropic compression c-d would have to be performed in two-phase region

also isentropic expansion a-b is difficult to be realised in two-phase region
Second version: after moving the compression process to superheated vapor area (Figure
3).

Figure 3: Carnot cycle representation on T-s diagram (compression of superheated vapor)

Advantages:
Point c is now easy to identify using temperature measurements
isentropic compression c-d is performed in superheated vapor area
Disadvantages:
isentropic expansion a-b still has to be realised in two-phase region
isothermal compression d-d needs additional compressor
Moving isentropic expansion to liquid area (Figure 4) moves point a to very high pressure
(technical realization is impossible).

Figure 4: Carnot cycle representation on T-s diagram (expansion of liquid)

SUMMARY: real life refrigerators can not be based on Carnot cycle. Linde cycle is used
in refrigerators instead.

Comparison of ideal and real cycles of refrigerators.

As it was mentioned above, Linde cycle is used in refrigerators. Figure 5 shows the graphical representation of ideal Linde cycle. Superheated vapor is compressed in compressor
in isentropic process (1-2), then it is condensed in condenser (2-3), then throttled in expansion device (valve or capillary tube) - process 3-4, and then evaporated in evaporator
(4-1).

COP of Linde cycle:

COP =

h1 h4
h2 h1

Figure 5: a)Ideal Linde cycle representation on T-s diagram b) on lg p-h diagram

In real refrigerators there are pressure drops in pipelines and heat exchangers, also
compression is not an isentropic process. The real Linde cycle was shown on Figure 6.

Figure 6: Real Linde cycle representation on lg p-h diagram

Nernst theorem. Why the absolute zero is unattainable?

Classical versus Nernst approach.

It is impossible by any procedure, no matter how idealised, to reduce any system to the
absolute zero of temperature in a finite number of operations.
The Nernst heat theorem says that as absolute zero is approached, the entropy change
S for a chemical or physical transformation approaches 0. This can be expressed
mathematically as follow:
limT 0 S = 0
The entropy of all systems and of all states of a system is zero at absolute zero. It is
impossible to reach the absolute zero of temperature by any finite number of processes.

Unavailability of absolute zero can be shown using classical physics, basing on law of
equipartition of energy proposed by Maxwell, saying that energy of the body depends
only on temperature and its is shared equally among all of its independent parts. For
every degree of freedom of particle energy is equal:
= 1 kT ,
E
2
where k is Boltzmann constant, k = 1, 38 1023 JK 1 .
Basing only on energy equipartition law, the specific heat of a body is constant and does
not depend on temperature. So, the entropy difference between finite temperature and
absolute zero reaches infinity:
7

sT s0 =

RT c
T dT = c (ln T ln 0) =
0

In that case isobars will look like in Figure 7. The absolute zero is unavailable because it
would require infinite work: W = h1 h0 T (s1 s0 ), where s0 = . Using classical

Figure 7: Isobars in system in which energy equipartition law is valid.

physics, the absolute zero is unavailable, but it is not a reference point from which one
could calculate all the quantities necessary for thermodynamic calculations (especially
for entropy calculations).
According to quantum mechanics the specific heat of all substances approach 0 when
temperature tend to 0K. Absolute zero can be a thermodynamic reference point. On the
other hand, it may lead to situation, when isobars look like in Figure 8. Nernst approach
both the heat capacity and entropy of any substance must vanish at absolute zero (all
the substances at 0K must have to be in ideal order, which is possible only in quantum
world). Figure 9 shows the isobars according to 3rd law of thermodynamics.

Figure 8: Isobars in system in which absolute zero can be achieved in finite number of
steps.

Figure 9: Isobars according to 3rd law of thermodynamics.

Consequences of the Nernst Theorem (3. Law of thermodynamics) with respect to heat capacity

On the terms of third law of thermodynamics, when approaching to absolute zero, all
s
entropy changes caused by change of any parameter approaches 0: limT 0 ( z
)T = 0.
9

That means, the specific heat cz is vanishing, because:

s
cz = T ( T
so cz 0 when T 0 and (s/T )z 0
z

Also thermal expansion coefficient will be equal 0 at 0K.

10

Relation between temperature and energy. Boltzmann

constant.

The concept of temperature resulting from the Zeroth Thermodynamical Law is intuitive.
The temperature is directly related to energy by the equation describing the gas molecule
energy per one state of freedom (Maxwell equipartition):
= 1 kT ,
E
2
where k is Boltzmann constant, k = 1, 38 1023 JK 1 .
= 3 kT .
For monoatomic gas this value will be equal: E
2
If the temperature is a measure of the energy absorbed by the physical body, there is no
objective need for a dedicated unit describing its (temperature) value. However using of
Joules [J] to desribe typical everyday temperatures would be impractical.

11

Equation of State for ideal gases and its assumptions

allowing to derive the equation.

Lets consider a system shown on Figure 10. Assuming that mean particle velocities are

Figure 10: Velocity distribution in volume V

10

the same and equal to v, we can say that 1/6 of the total particle amount N is moving
with a v velocity in the direction of As vessel wall.
During a time t, the wall As [m2 ] is hit by the amount of the particles n equal to:
n=

vtAs N
6V

On the assumption that the collissions of the particles with the wall are ideally elastic,
and the particle energy remains constant before and after the collision, the particle
momentum is changing by the value:
p = 2mv
It results from the second Newton law of dynamics the the momentum change of the
particle interacting with the wall is equal to the force that the particle imposes on the
wall. In time t, the total amount of N particles will collide with the surface As , creating
the pressure P
P =

2mv 2 N
6V

k = mv 2 /2, so after putting this to equation for pressure

Kinetic energy of particle: E
and multiplying by V :
k
P V = 23 N E
P V = N kT
R = k A, A = Avogadra number A = 6, 02 1023
P V = nRT
We have obtain ideal gas equation of state.

12

Statistical interpretation of entropy.

Entropy of individual particle, where is a number of allowable states , in a ground

state = 1 and s = 0 what is in agreement with the Nernst theorem (third law of
thermodynamics):
s = k ln
Entropy of one mole of substance:
s = R ln

13

Zero point (state) energy

Heisenberg uncertainty principle states that certain pairs of physical properties, such as
position and momentum, cannot be simultaneously known to arbitrarily high precision
(px = h). If the position of atom is precisely defined, the uncertainty of its momentum increases. Atom which position is strictly defined by strong interactions with
11

lattice, is still oscillating around this position, even at 0K. At 0K the energy of atom is
equal zero point energy. In higher temperatures, when kT is much higher than zero point
energy, sum of zero point energy and thermal energy converges with energy resulting
from energy equipartition law.

Figure 11: 1 thermal energy resulting from classical equipartition principle 2 thermal
energy taking into account the vanishing heat capacity 3 thermal energy taking into
account zero point energy.

14

General cooling process

Figure 12: Generalized cooling. x - generalized force

Temperature drop (TA TC ) appears when generalized force x goes adiabaticaly to its
initial value: x2 x1 . x - generalized force of conjugate variables: force - displacement.
12

Example: for conjugate variables p V : pressure p is generalize, volume V is generalized

displacement.

15

Examples of conjugate variables generalized force

displacement.

Substance

Force X

Displacement Y

Process of entropy decreasing

(ordering)

Process of temperature lowering

Gas

pressure, p [Pa]

Volume V , [m3]

Gas

pressure, p [Pa]

Volume V , [m3]

Paramagnetic
substance

Magnetic
flux
density H, [A/m]

Isentropic expantion
Isenthalpic
expantion
Adiabatic demagnetization

Dielectric substance
Electron gas

Magnetic
flux
density E, [V/m]
Electrical potential
, [V]
Chemical potential [J/mol]
Mechanical force
F
Mechanical force
F

Magneric
dipol
moment
0 M ,
[Wb m]
Electric dipol moment P, [Cm]
Electric charge Z,
[C]

Isothermal compression
Isothermal compression
Isothermal magnetization
Isothermal
trization
Electron
pacting

Adiabatic
deelectrisation
Electron dilution

Salt
Rod
Polymer

16

eleccom-

Mole number n

Drying

Dissolving

Length l

Compression

Stress relaxation

Length l

Tension
(fiber
elongation)

Tension
ation

Entropy change during isothermal compression.

Isothermal expansion process is shown on Figure 12 (process A-B). Change of entropy

of gas in reversible compression process can be determined using equations connecting
1st and 2nd law of thermodynamics:
ds =
ds =

du+pdv
T
dhvdp
T

Internal energy and enthalpy of ideal gas are only temperature functions. After substitution of: du = cv (T )dT and dh = cp (T )dT and ideal gas equation of state we get:
dv
ds = cv (T ) dT
T +R v
dp
ds = cp (T ) dT
T R p

13

relax-

After integration:
s2 s1 =

R T2
T1

v2
cv (T ) dT
T + R ln v1 =

R T2
T1

p2
cp (T ) dT
T R ln p1

If the compression is isothermal process, the work of compression is minimal, and entropy
change is equal:
s2 s1 = R ln vv21 = R ln pp21
Change of entropy during isothermal gas compression can be also determined on the basis
of statistical interpretation of entropy. Number of allowable states is proportional to
volume = a V . As effect of compression, the volume will change from the value V1
to V2 . The change of entropy will be equal to:
s = s2 s1 = R(ln 2 ln 1 ) = R(ln(aV2 ln(aV1 )) = R ln( VV12 )
The result is identical with the one determined using phenomenological equations.

17

Entropy change during rubber band elongation.

The example of solid in which one can get entropy change by applying a force is rubber.
In no-stress state polymer fibers can have any position. Rubber elongation causes the
polymer fibers to have identical positions, parallel to force direction. In this way entropy
of rubber becomes equal 0. Assuming that before elongation each of the fibers had 3
allowable positions, one can get:
s/R = ln 3 1.1

18

Isentropic expansion.

Adiabatic (isentropic) gas expansion requires no irreversible processes leading to heat

release during expansion process, that means all energy of expanded gas has to be
received as external work. In that way, the enthalpy and internal energy drop, as well
as temperature drop, are the highest possible. External work of expansion is equal to
enthalpy difference between inlet and outlet of expander: w = h1 h2 . Temperature
drop in isentropic expansion:
S
dS = ( T
)p dT + ( S
p )T dp
dS = 0 - isentropic process
( S )T

p
s = ( dT
dp )s = ( S )

( S
p )T

T p

v
( T
)p - Maxwell
c
S
( T
)p = Tp

equation

After substitution:
v
T ( T
)p
mus = ( dT
)
=
=
s
dp
cp
14

T v
cp

19

Describe and illustrate on the TS diagram a general

process to lower the body temperature.

Figure 13: General process to lower the body temperature

The entropy must be a function of two parameters: temperature T and X, where

X is a generalized force (gas pressure, magnetic field ). At the room temperature
the entropy must be high enough.
The entropy can be lowered by external work done on the body (gas compression,
paramagnetic magnetization) in isothermal process.
By isentropic process the temperature of the body will go down.

After performing isothermally work on system, the number of energy levels decreases
15

and their width is increasing. When after putting the system in order the system will
be isolated thermally from environment and the external force (pressure, magnetic field)
will be removed, the width of energy levels will go back to previous one, but entropy
will be the same (third picture). The temperature of the system will decrease.

20

Explain why we need some minimum storage of entropy

to perform cooling?

Every system used to achieve low temperature should have ability to cool down itself:
cT = T s (c is the heat capacity of system). So:
T
T

s/R
c/R

T
Minimum value of T
T does not depend on temperature and it is equal T 0.1.
In room temperature specific heat of most materials c 3R. Reduced specific heat
c/R 3. After substitution to one of previous equations we get minimum entropy value
s/R 0, 3

If the reduced entropy is lower than lower limit shown on figure above, then the process
in which it may be decreased is not perspective in achieving lower temperatures.

21

Thermodynamic efficiencies of refrigerator and cryogenic coolers.

Independently on the operation principle, the basic features of the refrigerators can be
compared on basis of the Carnot cycle. Thermodynamic efficiency of Carnot cycle is
depending on temperatures:
COP =

Qwe
Wob

Tk
T Tk

, where Tk is cryostating temperature and T - temperature in which the heat is rejected

to environment. In cryogenic temperatures, the thermodynamic efficiency of Carnot
16

cycle is lower than 0.66.

22

Why the efficiency of cryogenic coolers is increasing

with the refrigerator capacity?

Efficiency of cryogenic cooler can be expressed as: =

Qwe

Qwe
(T Tk )
+W
Tk

, where Qwe

k)
- cooling power, Qwe (T T
- minimum work, resulting from Carnot cycle, W Tk
additional work resulting from entropy genereation.
Cooling power of refrigerator is proportional to a3 (a - characteristic dimension of cooler).
Insulation losses are proportional to a2 (surface). Heat flux through the insultation:
Qiz = k a2 (T Tk )
Entropy generation:
Siz = k a2 (T Tk )/Tk
Additional work resulting from Gouya-Stodola law:
Wiz = k a2 Tot (T Tk )/Tk
So the efficiency of cooler:
= (T Tk ) Qwe 2
Tk

(Qwe +ka Tot )

Qwe
Efficiency normalized versus Carnot limitation: C = Qwe
+ka2 Tot
Cooling capacity is proportional
to
third
power
of
the
characteristic
dimension a.

3
Q

a3
a

3
C
a+kTot
a3 +ka2 Tot
Q+kT
ot

17

23

Gouy-Stodola Law (theorem) and its applications

In real cooler there are internal sources of entropy, resulting from irreversibility of processes, that means there is a bigger amount of entropy to remove than the flux which flew
into the refrigerator with the heat flux from the refrigerated object. In case of realisation
of closed thermodynamic cycle, only way of carrying away entropy to the environment
is heat exchange with the environment, real refrigereators carry away much more heat
to the environment than ideal refrigerators. To satisfy the energy conservation rule, it is
necessary to perform additional work at the amount resulting from Gouy-Stodola law:
W = S Tot

24

Entropy generation during heat transfer and fluid flow.

In cryogenic systems the most important sources of entropy generation are

heat transferred or generated at low temperatures
SQ = Q
T
flow with pressure drop
M
dSdp = VT dp = T
dp

25

Please give examples of the systems that can be optimized with entropy minimization method.
Heat exchangers
Cryostats
Thermal insulation

18

 Transfer lines
LHC superconducting magnet support

26

Heat transfer in low temperatures (convection, residual

gas conduction, conduction, radiation)

26.1

Conduction heat transfer

Qs = A Ls (T2 T1 ), where A - material cross-section, - material thermal conductivity,

W/mK, L - length. Conduction heat transfer reduction methods:
Minimum cross-section area
Low conductivity material
Max. material length

1
(T2 T1 ), l0 - mean free path of gas, L - distance
Gas heat conduction: Qg = Ag L+l
0
between walls.

19

26.2

Convection

Qcon = A hcon (Tw Tenv ),

where A - material cross-section area, hcon - convective heat transfer coefficient, W/m2 K,
Tw - wall temperature, Tenv - environment temperature.
hcon L3 , so reduction of natural convection=reduction of characteristic length L.

26.3

Radiation

Qr = A 0 (T14 T24 )
where A - material area, - Stefan-Boltzmann constant, 0 =
the system.
Reduction - radiation shields:

20

1
1
1
+ 2
1
1

- emissivity of

27

Principle of low temperature thermal insulation operation (vacuum, multi-layer screens)

27.1

Gas filled close-cells foams

Foam materials: polyurethanes, polystyrenes, gums, glass. Gases: R22, R23, R134a,
R407C, Carbon dioxide.
Solid conduction reduction:
Low thermal conductivity cells material
2% volumetric fraction of the solid phase
Cell walls are very thin
Gas convection reduction - small cells dimensions
Gas conduction reduction:
Low thermal conductivity gases
In cryogenic temperatures partial condensation or solidification of the gases - vacuum in cells
Thermal radiation reduction - small temperature difference between opposite cell walls.
Low cost, but the thermal conductivity is high. Application - rarely and short term used
cryogenic equipments.

27.2

Vacuum Insulation

Gas conduction reduction - high vacuum

Thermal radiation reduction - cold and warm boundary covered with high emissivity
metal layer.
Advantages:
Relatively easy to create - short time vacuum creation process
Very low heat transfer in low temperature ranges
Disadvantages:
Relatively high heat transfer in high temperature ranges
High vacuum level sensitivity
Very high heat flux in case of sudden vacuum loss
Applications:
Small cryogenic equipments and experimental flasks
Cryogenic elements where distance between boundaries is very small (no other
insulation can be installed)
21

27.3

Powder gas filled/vacuum insulation

Perlite
Hollow glass bubbles
Glass fibers
Aerogels
Solid conduction reduction
Low thermal conductivity powders and glass fibers
High length and very small cross-section area of the fibers
Thin walls of the hollow glass bubbles
High thermal contact resistance between powder grains/fibers
Gas convection reduction (gas filled insulations) - small dimension of the spaces between
powder grains/fibers
Gas conduction reduction (vacuum insulations) - high vacuum.
Thermal radiation reduction
Low temperature difference between adjacent powder grains/fibers
Opacifier agents: Al, Cu, Au.
Advantages:
Low thermal conductivity (in good vacuum conditions)
Does not require HV conditions
Relatively good insulation properties in gas filled conditions
Mechanical support properties
Relatively low costs of materials and production
Sorption properties of the powders slow vacuum degradation in case of vacuum
container leaking
Disadvantages:
Very thigh vacuum pump sieves are required long time vacuum creation process
Powder self-compaction due thermal shrinking of the vacuum container
Applications:
Large and very large cryogenic systems (gas liquefiers and gas separation installations), tanks for low evaporated and cheap cryogens (LNG, N2, O2, Air, Ar)
Application, where high vacuum creating and/or maintaining is very difficult or
impossible
22

27.4

MLI - Multilayer Vacuum Insulation

Radiation shields - shield: single or double side metal plated Mylar, Kapton, Dracon.
Pleating materials: Al, Ag, Cu, Au. Perforated (0,1-0,3% of total area). Spacers: silky
or nylon nets, glass fibers mats Solid conduction reduction
Low thermal conductivity materials for spacers
Special design of spacers - point contacts between solids
Small contact area between spacers and radiation shields or between crinkled/dimpled
shields
Gas conduction reduction - high vacuum.
Thermal radiation reduction
Radiation shields
Very low emissivity of the shield surface
.
Advantages:
The best thermal insulation in very large temperature range
Does not require HV conditions
Weak sensitivity for slow vacuum degradation
Good thermal behavior in case of the sudden vacuum lose
Disadvantages:
Relatively expensive
Long time vacuum creation process due to material outgassing
Need additional support elements (additional heat transfer paths are creating)
Applications:
Small, middle and some large scale cryogenic systems, cryogen storage tanks (He
and H2 tanks included), experimental equipments, cryocoolers ... .

23

28

Please give the examples of engineering solutions to

limit heat flux to low temperatures regions of cryogenic
devices.
Vacuum insulation to reduce convection
Thermal shields to reduce radiation
Elongation of some elements (ex. valve stems) to reduce conduction
Avoiding thermal bridges, applying low thermal conductivity materials

29

Definition of cogeneration and trigeneration.

Cogeneration - simultaneous production of mechanical (electrical) energy and heat.

24

30

Minimum work of gas mixture separation.

Entropy of gas mixture is higher than sum of entropies of components under the same
pressure and temperature. From second law of thermodynamics one know that it is
necessary to perform external work to separate the gas mixture. Minimum work of gas
separation is equal to work of isothermal compression of components from partial pressure to pressure p.
WA = R xpA p pdv = nA RT ln xA
WB = xpB p pdv = nB RT ln xB
For two component mixture: W = WA + WB = nA RT ln xA + nB RT ln xB
P
For multicomponent mixture: W = zi=1 ni RT ln xi
R

31
31.1

Technologies of gas mixture separation cryogenic, adsorption and membrane.

Cryogenic gas separation technology

Single or double Linde rectification column. Highest gas quality (purity), biggest capacity. Only technology for big industrial applications. Capacities up to 3500 tones/day.

25

O2 purity up to 99%

31.2

Membrane technology

Purity of oxygen up to 40 %, low capacities (to 20 tons/day). Membrane is a continuous

phase between two other phases, that allow some of one phase components to permeate
to another. Advantages of this technology is that system is made of modules, which
allows to scale the process.

26

Membranes can be used for nitrogen production (high purity of N2).

31.3

Adsorption technology

Purity of oxygen up to 95%, capacities of installations up to 250 tons/day. During

operation only one of adsorbing tanks is active, other one is being regenerated by opening
the outlet directly to the atmosphere (PSA) or by creating pressure below atmospheric
in it by using vacuum pump (VPSA).

27