1.

3 Properties of Cryogenic Fluids

What are the properties for cryogenic fluids that

are important to system engineering?
„ State Properties
„ Phase Diagrams
„ Equations of State (imperfect gases)
„ Condensed phase properties (ρ, β, κ, Cp, hfg, and σ)
„ Optical, electric and magnetic properties
„ Transport properties
„ Thermal conductivity & viscosity (k, μ)
„ Prandtl number (Pr = μCp/k)

These properties depend on the molecular configuration and

inter-molecule interactions
See Chapter 2: Barron, Cryogenic Systems

USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 1

 Phase diagram of common fluid system

„ Phase diagram is a 3D map of

the Equation of State for an
element or compound.
„ Regions and points of interest in
Cryogenics.
„ Critical point (Tc, pc, vc)
„ Phase co-existence
„ Normal boiling point (NBP)
„ Triple point (TP)
„ Subcooled liquid
„ Supercritical gas
„ Solid state

USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 2

 Common Cryogenic Fluids

P
• Methane (NBP = 117.7 K, TP = 88.7 K) CP
CH4, LNG mostly methane
Used as a fuel solid
liquid
• Oxygen (NBP=90 K, TP = 54.4 K)
Light blue, slightly magnetic, reactive 1 Atm
Used as rocket fuel (shuttle), medical gas storage, steel making
• Argon ( NBP = 87 K, TP = 68.6 K) vapor
colorless, non-magnetic, inert TP
Used for inert atmosphere during material processing
• Nitrogen (NBP = 77 K, TP = 63 K) NBP
colorless, non-magnetic, inert, cheap T
Used for cryogenic conditioning, high Tc superconductor cooling
• Neon (NBP = 27 K, TP = 24.6 K)
colorless, non-magnetic, inert, rare
Refrigerant for intermediate temperature; HTS
• Hydrogen (NBP = 20.3 K, TP = 13.8 K) for normal LH2
Isotopes D2 and T2, ortho-para conversion a factor in applications
Used as rocket fuel; materials processing, fusion reactors (D & T)
• Helium (NBP = 4.2 K, no TP, Tλ = 2.178 K)
colorless, inert, superfluid phase; He3 isotope
low temperature coolant; superconductivity; He3 refrigeration

USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 3

 Properties of Cryogenic Liquids

From Timmerhaus and Flynn, Cryogenic Process Engineering

USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 4
 Equation of State for gaseous systems

„ Equation of state is a functional relationship between

state properties (ρ, P, T)
„ For gases, there exist fairly simple relationships
„ ideal gas : pv = RT
“real gases” e.g. Van der Waal gas ⎛ a⎞
⎜ p + 2 ⎟(v − b ) = RT
„

„ a – intermolecular attraction ⎝ v ⎠
„ b – hard core repulsion
⎛ B C ⎞
„ Virial Expansion pv = RT ⎜1 + + 2 + ..⎟
⎝ v v ⎠
„ Models that include quantum effects
„ Quantum virial expansion (helium)
„ H2 gas
„ Compressibility factor (Z = pv/RT) is a measure of the deviation
from ideal gas behavior (Z = 1 for ideal gas)
„ Detailed numerical codes for properties of cryogenic fluids (e.g.
REFPROP) use fits based on equations of state compared to
experimental data
USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 5
 Law of Corresponding States

„ Assumes that the equation of state is universal about the reduced

critical point:
p ⎛T v ⎞
= Φ⎜⎜ , ⎟⎟ Φ is a universal function
„ Assumptions
pc ⎝ c c⎠
T v
„ No quantum effects (poor assumption for He, H2 and Ne)
„ Spherical molecule, neglects polarity effects (H2O, CO2, etc.)
„ The Law is based on assumption: Isobar has an inflection point at Tc
T pc
Mathematically, an inflection
point has the property:
Tc
∂p ∂2 p
= 2 =0
∂v Tc ∂v T
c

v
USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10vc 6
 Van der Waal’s Equation of State

⎛ a⎞
⎜ p + 2 ⎟(v − b ) = RT
⎝ v ⎠
„ This is a simple “real gas model” that can account for some phenomena
such as liquefaction and the Joule Thomson effect
„ From the law of corresponding states, the VdW equation of state
predicts that b = 1/3vc and a = 9/8RTcvc

Fluid Tc(K) pc(MPa) a(m6kPa/kmol2) b(m3/kmol) TBo(K)

Helium 5.2 0.227 3.46 0.0237 17.6
Hydrogen 33.2 1.315 24.4 0.0262 112
Neon 44.5 2.678 21.5 0.0173 149
Nitrogen 126.2 3.396 137 0.0386 427
Oxygen 154.6 5.043 138 0.0318 522

USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 7

 Virial Expansion Equation of State
„ The Virial expansion is useful for detailed analysis.
„ General form ⎛ B C ⎞
pv = RT ⎜1 + + 2 + ...⎟
⎝ v v ⎠
„ B is the second virial coefficient and represents corrections
due to 2-body interactions
„ C is the third virial coefficient for 3-body interactions
„ Virial coefficients can be calculated using knowledge of
the interparticle interactions
„ Second classical virial coefficient:
N ∞ ⎡ −φ (r ) k BT ⎤
B=− ∫ − π He He
2
⎢ e 1⎥ 4 r dr
2 0
⎣ ⎦ r
„ Interparticle interactions are given by approximate potentials,
φ(r), which describe the attractive or repulsive force between
two molecules (more later on this)
USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 8
 Compressibility Factor for Real Gases

pv
Z≡
RT
„ Z = 1 for ideal gas but
can be > or < 1 for real
gases.
„ Z > 1, p > p(ideal gas)
as result of finite
particle size
„ Z < 1, p < p(ideal gas)
meaning that the
particle attraction
reduces the pressure
„ Boyle Temperature:
„ Tbo= pv/R
„ where Z = 1

USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 9

 Thermodynamic Properties
„ Tds = dE + pdv (Differential form of 1st and 2nd Law)
„ The heat capacity is defined as the change in the heat content
with temperature.
ds ∂E ∂s
Cv = T = Cp = T
dT v ∂T v ∂T p
„ These two forms of the heat capacity are related through the
following thermodynamic relationship

∂v ⎞ ∂p ⎞ Tvβ 2
2

C p − Cv = −T ⎟ ⎟ = for gases where Cp – Cv ~ R

∂T ⎠ p ∂v ⎠T κ

„ Enthalpy, h, is a useful thermodynamic property for quantifying

heat content of a fluid.
h = E + pv and in differential form, dh = Tds + vdp
∂h
so the specific heat is also given as Cp =
∂T p
USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 10
 State Properties Summary (T-S Diagram)

Nitrogen

p = constant
h = constant

Lines of constant h are called “isenthalps”

Lines of constant p are “isobars”
USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 11
 Transport properties

„ Transport properties (viscosity & thermal conductivity)

are fundamental to cryogenic process engineering
„ Viscosity (μ or ν): involved in mass transport behavior
„ Thermal conductivity (k): heat transport property
„ Most transport properties of fluids are empirically
determined:
dT ΔT
Laminar flow: Fourier’s law: Q = −kA ≈ kA
dx t
πr 4 Δp dV Qloss
Q= where Q =
8μ L dt Q Insulation
T1
t
T2 A

Q
USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 12
 Examples of transport properties (REFPROP)

„ Viscosity
Nitrogen
„ Gas region μ ~ Tn, n ~ 0.5
„ Thermal conductivity
„ Gas region k ~ Tn, n ~ 0.5
„ Prandtl number
„ Gas: γ = Cp/Cv= 7/5 (diatomic)
μC p 4γ
Pr = = = 0.74
k 9γ − 5

„ Liquids
Nitrogen

USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 13

 Hydrogen

„ Diatomic Molecule (H2)

„ Isotopes:
„ Ordinary hydrogen has only one proton in nucleus
„ Deuterium has one p and one n in nucleus and is 1
part in 1600 of all natural occurring H
„ Tritium has one p and two n in nucleus and is
radioactive with a half life of 12.26 years
„ Natural forms (H2, HD, D2); HD much more
abundant than D2. Why?
„ Applications for cryogenic hydrogen
„ Rocket fuel (LH2 + LO2)
„ Transportation (vehicle fuel systems + gO2)
„ Detectors in high energy physics experiments
„ Semiconductor processing (high purity H2 gas)
„ Nuclear fusion reaction processes (D2 and T2)
„ ITER Project

USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 14

 Molecular states of hydrogen

„ Molecular hydrogen can exist is two different states depending

on nuclear spin
1
0
Ortho (s = 1) -1

Para (s = 0) 0

„ Normal hydrogen is in equilibrium at ambient temperature with

75% ortho and 25% para (called nH2). All states equally populated
„ At 20.4 K = NBP, equilibrium concentration is 99.8% para and
0.2% ortho.
„ Equilibrium concentration is a function of temperature.
„ Conversion is exothermic and must be catalyzed to accelerate
conversion
„ Deuterium also has O-P conversion, but n-D2 is 2/3 ortho and 1/3
para-D2
USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 15
 Ortho-Para Conversion of H2

„ Ortho-para conversion is an
exothermic process Equilibrium concentration is a function of temperature
„ ΔEop(20K) ~ 700 kJ/kg
„ Compared to heat of 100

vaporization, hfg ~ 445 kJ/kg % Para Hydrogen

„ Equilibrium concentration is a 80

function of temperature

% Para Hydrogen
„ 25% Para @ 300 K 60

„ ~ 50% Para @ 80 K
„ 99+% @ 20 K 40

„ Conversion is slow as it
depends on 3-body
20

interactions
For long term storage of LH2,
0
„ 0 50 100 150 200 250 300

need to complete O-P Temperature (K)

conversion

USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 16

 Ordinary O-P conversion
„ If the reaction that convert Ortho hydrogen to Para hydrogen is
not catalyzed, then it occurs rather slowly
„ Reaction rate,
dxo
= −C 2 x o2
dt
Where xo is the ortho fraction and C2 = 0.0114 hr-1 is the rate constant

„ Since the rate is proportional to xo2, the reaction will slow as the
conversion proceeds
„ The heat deposited as a result of the conversion is proportional to
this rate
dxo
Qop = hop
dt

Where does the Qop go?

USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 17

 Storage losses of unconverted H2

At t = 0, 100% liquid H2 with the

designated fraction of para-H2.

The fraction lost is due to

conversion from ortho to para
heating and vaporizing the liquid.

USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 18

 Catalysis of O-P Conversion

Catalyst provides medium for O-P

conversion at surface

Examples: Ni powder, Ru/Al2O3,

Fe(OH)3 (ferric oxide)

Chemical reaction

Partial conversion process at 80 K (Why do this?)

80 K heat sink
eH2 eH2
75% O Fe(OH)3 50% O
powder
300 K 80 K
USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 19
 Catalyzed O-P conversion

„ If the reaction that convert Ortho hydrogen to Para

hydrogen is catalyzed, then it occurs much more rapidly
„ Reaction rate,
dxo
= −C1 x o
dt
Where xo is the ortho fraction and C1 is the rate constant that depends
on the type of catalyst used

„ As before, the heat deposited as a result of the conversion

is proportional to this rate
dxo
Qop = hop
dt

Where does the Qop go?

USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 20

 Ortho/Para Conversion of H2
How to know if the o-p conversion is complete?
n-H2
(75% ortho p-H2 900 Souers, P.C., Hydrogen Properties for
+25% para) Fusion Energy, U of California Press,
880
1986
860
Vacuum/Exch. gas 840

Vapor Pressure (torr)

820
800
780

LHe 760
740
Vacuum/Exch. gas
720

Thermometer 700
Catalyst
Heater 680 This research
p-H2 (Souers)
660 n-H2 (Souers)

20 20.5
T (K)
Uses hydrous ferric oxide (Fe(OH)3) catalyst
Ortho/para ratio determined based on ~3% difference in vapor pressures
of p-H2 and n-H2 (75% ortho + 25% para)
USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 21
 T-S Diagram for Para H2

P = constant
ρ = constant

USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 22

 Heat Capacity of Gaseous H2

„ At high temperature
Cv/R ~ 5/2 (diatomic
molecule)
„ 3 translational degrees
of freedom
„ 2 rotation
At low temperature,

Cv/R
„

rotation is suppressed,
Cv/R ~ 3/2

From Barron, Cryogenic Systems

USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 23
 Transport properties of H2 (Refprop)

„ Transport
properties
similar to other
diatomic
molecular
liquids

USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 24

 Liquid Hydrogen

„ e-H2 properties:
„ Tnbp = 20.3 K
„ Density = 70.8 kg/m3
„ hfg = 446 kJ/kg
„ Tc = 33 K
„ Pc = 1.3 MPa
„ T(Triple pt) = 13.8 K
„ P(Triple pt) = 7 kPa
„ Vapor pressure depends
on fraction ortho-para
(about 5% effect)
„ Other phases (HD & D2)

USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 25

 Specific heat of liquid hydrogen

„ Isotopes (H2, HD, D2) have

different transition
temperatures. Example, freezing
point of H2, D2 and HD

USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 26

 Hydrogen Summary

„ Liquid hydrogen is the lowest density liquid (SG = 0.07)

„ Ortho-para conversion process is unique in fluids
„ Three isotopes of interest (H, D, T)
„ Easily oxidized to produce significant energy
H2 + O 2 H2O + energy

„ Safety issues (to be discussed later)

USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 27

 Helium

„ Inert, spherical molecule is the closest approximation to an ideal gas

„ Helium is about 0.1 ppm in the atmosphere
„ Obtained in separation process in natural gas (~ 0.2% concentration)
„ Two stable isotopes (He4 and He3, which is 0.1 ppm of natural helium)
„ Quantum effects are important at low temperatures (T < 20 K)
„ He4 obeys Bose-Einstein statistics (nuclear spin = 0)
„ He3 obeys Fermi-Dirac statistics (nuclear spin = ½)
„ Approximate forms of the equation of state
„ Van der Waal’s gas model not suitable at low temperature due to quantum
effects
„ Virial expansion including quantum phenomena
„ Tabulated properties for He4 (Refprop® or HEPAK®)
„ History of helium discovery (R. Longsworth)

USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 28

 Compressibility Factor for Helium

Tboil ~ 20 K

USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 29

 Equations of State
„ Helium is the closest approximation to an ideal gas (pv =RT)
„ Helium is not well described by the “Law of Corresponding States”
because at low temperature it is not a classical fluid
„ Virial expansion is a popular approximate equation of state

⎛ B C ⎞
pv = RT ⎜1 + + 2 + ..⎟
⎝ v v ⎠
B is the 2nd virial coefficient resulting from two body interactions
C is the 3rd virial coefficient resulting from three body interactions
∞

∫ [e ]
N −φ ( r ) / k BT
Classical 2nd Virial coefficient: BCL =− − 1 4πr 2 dr
2 0

where φ(r) is the effective particle interaction

USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 30

 Molecular Potentials
- -- - -
+ - -
- +-
-

„ Oscillating dipole moment

due to electron
distribution in molecule
„ Momentary weak
attraction
„ Hard core repulsion
„ For helium:
„ ε0/kb = 10.22 K
„ r0 = 0.255 nm
„ rm = 0.287 nm

Lennard Jones potential

USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 31

 Quantum Gas Models
„ Quantum fluids (like He, H2) have
behavior that deviates from
classical making ordinary
equations of state unusable
„ Quantum Virial expansion requires
solution to wave equations and
scattering theory
„ Difficult calculation
„ Beyond scope of course
„ Example: Second virial coefficient
for helium
„ Empirical fit to data
Bqu (T ) = a − b ∞

∫ [e ]
N −φ ( r ) / k B T
T BCL =− − 1 4πr 2 dr
2 0

a = 23.05 cm3/mole
b = 421.77 cm3K/mole

USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 32

 Example: Pressure of He gas

„ Consider a container with a known mass of helium gas.

Calculate the pressure.

Given:
P=? m = mass of helium gas
T = absolute pressure (K)
V = volume of container (m3)

„ Solution using suitable equation of state

USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 33

 T-S Diagram for Helium

p = constant
h = constant

USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 34

 Liquid Helium
Phase diagram
„ Two Liquid phases
„ He I – Neutonian fluid
„ Tλ < T < Tc = 5.2 K, Pc = 0.226
MPa
„ He II – quantum fluid
„ T < Tλ = 2.176 K @ SVP
„ Tλ (solid line, 3 MPa) = 1.76 K
„ Solid phase only under
external pressure P > 2.5 MPa
„ Important point: no triple
point

USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 35

 Density of Liquid Helium

„ Density (ρ)
„ ρcritical = 70 kg/m3
„ ρNBP, 4.2 K = 125 kg/m3
„ ρmax, 2.2K = 146 kg/m3
„ ρ ~ constant (T < 2.2 K)
„ Co-existing vapor
density
„ The density of helium
vapor is high compared
to co-existing vapor for
other fluids. Why?
„ ρvapor(4.2 K) ~ 15 kg/m3
NBP

USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 36

 Thermal Properties

„ Heat Capacity
„ Entropy
„ Heat of Vaporization (hfg)

dp ⎞ h fg
⎟ =
dT ⎠ svp T (v g − vl )

USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 37

 Transport properties of normal helium
„ Viscosity, (μ)
„ Thermal conductivity (k)
„ Prandtl number, Pr = μCp/k

Transport properties much

different in He II regime
USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 38
 Unique properties of superfluid helium (He II)

„ State properties (C, s, hfg)

„ Unique behavior in the transport peoperties
„ Viscosity
„ Heat conductivity
„ Sound propagation
„ Film flow
„ Fountain effect

USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 39

 Viscosity of He II

„ Viscosity depends on method

of measurement
„ As measured by a rotating
disk, μ is finite
m
„ As measured by flow through Δp ~ 0
a capillary, μ ~ 0
„ Physical explanation
„ Viscosity of the normal fluid
component drags with disk
Viscosity of “normal fluid”
„ Superfluid is invisid, so it can
flow through the capillary
„ The explanation of this
behavior is integral to the
“Two Fluid” model for He II

USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 40

 Heat Conductivity of He II
„ Anomalous heat transport q
„ Effective heat conductivity ΔT
comparable to that of high
purity metals
„ Low flux regime dT/dx ~ q
„ High flux regime dT/dx ~ q3
„ Transition between two
regimes depends on diameter
of channel
„ Heat transport in He II can be
understood in terms of the
motion of two interpenetrating
fluids. This “Two Fluid” model
effectively describes the
transport properties

USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 41

 Sound Propagation in He II
„ First sound (ordinary sound)
propagates in liquid helium ~ 200
m/s
„ Second sound (thermal wave)
propagates ~ 20 m/s
„ Unique quantum mechanism
„ Sound propagation associated with
variations in the two fluid
components
T

Q
x
t/c2

USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 42

 He II Film Flow

„ Rollin film (1937): Film thickness d

„ Saturated film K
d~ y
exists on all
yn
surfaces above the
liquid n ~ 0.4
K ~ 3 x 10-6 cm0.6
„ Unique aspect of He
II is that the film is
mobile (flows)
„ Siphon driven by
hydrostatic head
difference
„ Two containers with
different levels will
tend to equalize

USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 43

 Fountain Effect

„ Due to the invisid nature of the

superfluid, it can flow through
microscopic channels without friction
„ Ideal “superflow” conserves chemical
potential, Δp = ρsΔT
„ Components to Fountain pump:
„ Heater provides chemical potential
difference
„ Porous plug allows only invisid superfluid
component to flow
„ With the heater on, the superfluid flows
into the bulb through the porous plug
„ Normal fluid can not flow out through plug
since it is viscous
„ Normal fluid builds pressure and leaves the
top
USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 44
 Summary: Cryogenic Fluid Properties

„ Cryogenic fluid properties are mostly known and

available
„ Refprop (NIST database)
„ HEPAK (commercial data base for helium)
„ Properties of cryogenic fluid mixtures are not as well
known, but are of technical interest (cryocoolers)
„ Superfluid helium (He II) properties are unique
„ Inviscid flow
„ Very high heat conductivity

USPAS Cryogenics Short Course Boston, MA 6/14/10 to 6/18/10 45