TOPIC 5.

Throttling 1

Topic 5

Throttling

Contents
TOPIC 5:
THROTTLING 1
5.1 INTRODUCTION ....................................................................................................... 2
5.2 JOULE-THOMSON EXPANSION .................................................................................. 2
5.2.1 Isenthalpic Expansion of an Ideal Gas ................................................................................................ 4
3.2.2 Isenthalpic Expansion of a Real Gas ................................................................................................... 9
3.2.3 Joule-Thomson Effect ....................................................................................................................... 10
5.2.4 J-T Effect and VdW Attractive and Repulsive Components .............................................................. 16
5.3 TUTORIAL QUESTIONS TOPIC 5 .............................................................................. 18
5.4 BIBLIOGRAPHY ..................................................................................................... 19

Prerequisite knowledge

• Engineering Mathematics, Y1.

• Engineering Chemistry, Y1.
• Process Industries C, Y2.
• Good understanding of Thermodynamic Principles including definitions
and terminology.
• Good understanding of first law of Thermodynamics for steady-flow
processes including volume work, fluid work and shaft work.

Learning objectives
After studying this topic you should be able to:
• Define all the terms in the steady-flow energy equation for open
systems including kinetic and potential energy terms.
• Apply the steady-flow energy equation to isenthalpic throttling
processes for both ideal and real gases.
• Derive an expression for the Joule-Thomson coefficient and show how
this applies to both ideal and real gases.
• Explain “temperature inversion” and how this relates to the Joule-
Thomson coefficient.

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TOPIC 5. Throttling 2

5.1 Introduction

In this topic two steady-flow applications will be explored: the first is an

“isenthalpic expansion” of a fluid, the second will be “multi-stage” adiabatic gas
compression.

If a gas flows through an orifice, porous plug, or partially closed valve such that
no heat or work are exchanged between the system and its surroundings, then
the process is called a throttling process or a “Joule-Thomson” expansion
(often written “J-T expansion”).

William Thomson, of course, is the same person who was later honoured with
the title “Lord Kelvin”. He laid the basis for the Kelvin scale of temperature as
well as other important advances in science (including thermodynamics).

J.P. Joule was also an important scientist who discovered the “mechanical
equivalence of heat”, which states that heat and work are just different forms of
energy and that work can be converted into an equivalent amount of heat.

On expanding a gas from a higher to a lower pressure (J-T expansion) the

following may be observed:
• The temperature of the gas remains constant, but only if the gas is an
ideal gas.
• The process path follows a line of constant enthalpy. Thus, “throttling”
processes are also called “isenthalpic” processes. This second
observation applies to both ideal and real gases.

Moreover, when a real gas expands isenthalpically from a very high to a very
low pressure its temperature will at first rise and then (at lower pressure) the
temperature will fall. The peak temperature is called the “inversion
temperature” and the study of how these changes, with initial conditions, is
called the “Joule-Thomson Effect”.

5.2 Joule-Thomson Expansion

A fluid is “throttled” if some restriction is placed in the flow path – the restriction
may either be due to the presence of a valve, an orifice, or a porous plug:

• The pressure drops across

Boundary the throttling device, so that:
1 2 P2  P1
P2 = P1 − P
• Where P is pressure drop
across the throttling device.

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A J-T expansion is an adiabatic expansion where no heat or work is

exchanged between the system and the surroundings.

Many important equipment items (and plants) employ “J-T” devices and these
include:
• Refrigerators.
• Liquid and gas flow control using a “throttle” valve.
• Liquid and gas pressure control using a “throttle” valve.
• Gas liquefaction using the cooling effect of J-T expansion (the so-called
Linde process of gas liquefaction).

The first step is to show that a J-T expansion (or throttling process) is
isenthalpic; the process follows a line of constant enthalpy. Such processes
were introduced in Process Industries A and Process Industries B.

For any device with one inlet and one outlet, the first law was derived in Topic
2 as follows:

E = Q + W S − H − E pot − E kin …………………..(5.1)

For steady-flow processes the energy accumulation term is zero E = 0 and

the first law becomes

0 = Q + W S − H − E pot − E kin

For a throttling process no work is done by the fluid W S = 0 , also the process
is adiabatic so that Q = 0 and the pipe can be horizontal, so that E pot = 0

 H + E kin = 0 …………………………………….(5.2)

The term E kin is usually considered negligible:

• E kin has units (m2/s2) which is easily shown to be equivalent to (J/kg).
Such an energy density is extremely small for typical industrial
throttling situations.
• Even if E kin is taken into account for typical gas expansions then, it
will be shown later, that the result will still be a negligible change in
stream enthalpy H .

For a throttling process E kin may be ignored and equation (5.2) reduces to

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TOPIC 5. Throttling 4

H = 0 ………………………………………………...(5.3)

Thus, J-T expansion processes (throttling processes) are “isenthalpic”; they

follow a line of constant enthalpy.

Apart for the industrial applications, a key experimental result of a J-T

expansion is that is shows that the enthalpy of an ideal gas does not depend
on pressure; it is a function of temperature only (one of our earlier
assumptions).

5.2.1 Isenthalpic Expansion of an Ideal Gas

Equation (5.3) presupposes that E kinetic = 0 . However, it will be shown in

example 5.2.1 (following this section) that this is not exactly true.

This in turn might contradict the conclusion that the enthalpy of an ideal gas is
independent of pressure. Thus, in order to progress it is necessary to
establish, for a J-T expansion, that the change in kinetic energy E kin is
indeed small enough to be negligible.

First we need to know how changes pressure affects changes in volume. It is

known that for an ideal gas, flowing under isothermal steady-flow conditions

P1V1 = P2V2

V1
 P2 = P1
V2
Or,
V2
 P1 = P2
V1
There will be a drop in pressure across a J-T expansion device and this will
result in expansion of the gas. The pressure drop through a throttling device is
given by

P = P2 − P1

Substituting the previous expressions into this pressure drop expression gives

P1V1 P2V2
 P = −
V2 V1

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TOPIC 5. Throttling 5

 1 PV 1 
 P = P1V1  − 2 2 
 
 V2 P1V1 V1 

 1 1  V − V2 
 P = P1V1  −  = P1V1  1 

   
 V2 V1   V1V2 

Which may be further simplified as follows:

P1 
P = − V …………………………………….….(5.4)
V
2

Where
V = V2 − V1

Equation (5.4) links changes in pressure to changes in volume as the gas is

throttled. It shows that, for an ideal gas undergoing an isothermal expansion,
the drop in pressure through the J-T device is proportional to the expansion of
the gas.

This means that for a large pressure drop there must be a correspondingly
large expansion of the gas. If the diameter of the pipe stays the same, then
there must be a large increase in gas velocity as the pressure drops.

This raises the question as to whether or not the kinetic energy is indeed
negligible during throttling of an ideal gas. If it is not negligible, then the
process will no longer be isenthalpic.

Worked Example 5.2.1

Problem:

In view of equation (5.4), the question is whether or not the change in the
kinetic energy term is significant.

Take nitrogen (which behaves approximately as an ideal gas even at a

pressure of several bar) and find the relationship between a change in its
pressure and the corresponding change in its specific kinetic energy.

At some point it will be necessary to choose the pressure ratio and the gas
velocity at the inlet. Assume that the pressure of the gas is halved and that the
inlet velocity is 10 m/s (a very typical value for gas flow through a pipe).

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TOPIC 5. Throttling 6

In the second part of the problem, calculate the change in enthalpy and
temperature of the nitrogen and, from the results, judge whether or not the
assumption of negligible change in kinetic energy is reasonable.

Solution:

For nitrogen the molar mass is M = 28 g/mol.

For nitrogen the molar heat capacity at constant pressure is c P = 29 J/mol K

(the above heat capacity corresponds to a temperature of about 300 K).

The rate of change in kinetic energy E kin is known from topic 2 to be

E kin =
1
2
(
m vel 22 − vel12 )
The change in specific kinetic energy e kin may be found from the above
equation by dividing through by the mass flowrate m (kg/s)

ekin =
1
2
(
vel 22 − vel12 )
If the cross sectional area of the pipe A (m2) before and after the throttling
device is the same, it follows that the velocities (m/s) are simple functions of
the volumetric flowrate. The velocity at the outlet is given by

V2
vel 2 =
A
And the velocity at the inlet is given by

V1
vel1 =
A

Substituting these into the change in specific kinetic energy leads to the
following result:

1  V22 V12 
ekin =  − 
2  A 2 A 2 

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TOPIC 5. Throttling 7

1 V12  V22 
 ekin =  2 − 1
2 A2 
 V1 

1 2  P1  
2

 ekin = vel1   − 1 ………………………..(5.5)

2  P2  

From equation (5.5) the change in specific kinetic energy ekin depends on the
initial velocity and the pressure ratio: it depends on each quadratically; the
change in kinetic energy increases quickly with increasing initial velocity and
increasing pressure ratio.

On the other hand, the change in kinetic energy must decrease quickly as the
same two parameters decrease which means that it is possible, in a J-T
expansion, to make the change in ekin increasingly small (for a giving
pressure ratio) by reducing the initial velocity.

It is interesting to note that equation (5.5) applies to any ideal gas undergoing
an isothermal process and is approximately true for any ideal gas undergoing a
process that is approximately isothermal.

Taking equation (5.5) and substituting in the data provided in the example

1 2  P1   1 m 2  2  
2 2

ekin = vel1   − 1 =  10 2 2    − 1

2  P2   2 s  1  

 ekin = 150 J/kg

J  28 g  1 kg 
 ekin = 150    = 4.2 J/mol
kg  1 mol  1000 g 

It is interesting to consider where this energy comes from. Equation (5.2),

developed earlier for a throttling process (before kinetic energy change term
was eliminated), may be written in terms of molar quantities (J/mol).

h + ekin = 0 ………………………………………..…(5.6)

It can be seen immediately that any change in molar kinetic energy must come
from a change in the molar enthalpy of the fluid.

 h = −4.2 J/mol

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Assuming that the gas ideal and the enthalpy is indeed a function of
temperature only, then the heat capacity is constant and this enthalpy change
can be converted into a corresponding temperature change

h = c P T

h 4.2  J  mol K 
 T = − =−   
cp 29  mol  J 

 T = −0.14 K

Under these conditions, the change in kinetic energy causes an enthalpy

change that is equivalent to a drop in absolute temperature of only 0.05%.

Such a small change in temperature means that the change in enthalpy and,
hence the change in kinetic energy (given by equation (5.6)), is negligible.
Thus, throttling of a gas may indeed be taken as isenthalpic.

For an ideal gas, an initial gas velocity of 10 m/s (a typical velocity through a
pipe) gives an actual change in kinetic energy of only 4.2 J/mol and this leads
to only a minor change in temperature.

This shows that for an ideal gas a throttling process may be considered
isenthalpic. If the process for an ideal gas is assumed to be isenthalpic then it
must also be isothermal.

……………………………………………

The previous worked example demonstrates the following relationships:

• Δekin  vel12 .
• h  vel12
• T  vel12

The accuracy of the assumption of constant enthalpy, through a J-T expansion

device, may be progressively improved by reducing this inlet velocity; try
dropping the initial velocity from 10 m/s to 1 m/s to test this assertion.

Later experiments with real gases showed that, at higher pressure, the
temperature changes significantly and more than from the kinetic energy
alone; this is the observed Joule-Thomson effect for real gases.

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3.2.2 Isenthalpic Expansion of a Real Gas

For real gases the specific enthalpy is not only a function of temperature but is
also a function of pressure. Thus, the total change in enthalpy is made up of
two partial changes – one w.r.t. temperature, the other w.r.t. pressure

 h   h 
dh =   dT +   dP …………………………...(5.7)
 T  P  P  T

For an ideal gas only the first term is considered because the second term is
zero.

However, for a real gas both terms are required and the partial derivatives in
equation (5.7) must be eliminated in favour of measurable properties. The first
one is easy to find, it is the definition of c P and, for a real gas, this is

 h 
c P =   ……………………………………………(5.8)
 T  P

Finding the second partial derivative takes a little more work and, unfortunately
much more understanding of thermodynamics that has yet to be uncovered.
However, bringing the result forward, one finds

 h   v 
   = v − T   ………………………………(5.9)
 P  T  T  P

Now, substitute equation (5.9) and equation (5.8) into equation (3.7) to find a
very general expression of how the enthalpy of any real substance (liquid, gas
or solid) depends on both the temperature and pressure.

  v  
dh = c P dT + v − T    dP ………………......….(5.10)
  T P 

The partial derivative on the RHS is related to the isobaric thermal expansion
coefficient  with units of (1/K).

The thermal expansion coefficient  is defined as

1  v 
=  
v  T  P

Substituting the last expression into the previous one gives

dh = c P dT + v(1 − T )dP ………………..................(5.11)

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TOPIC 5. Throttling 10

If the enthalpy of any substance is needed (at any temperature or pressure)

then equation (5.11) is a convenient starting point. All the properties on the
RHS are all measurable.

For an isenthalpic expansion it has been shown dh = 0 and equation (5.11)

yields the following result

dT = −
v
1 − T dP
cP

This leads directly to the essential relation which shows how the temperature
of a real fluid depends on pressure, whenever the fluid follows a line of
constant enthalpy

 T 
 = − 1 − T 
v

 P  h cP

The partial derivative on the LHS is called the J-T coefficient, usually denoted
as  J −T and has units of (K/Pa). Thus, by definition  J −T is given by

 T 
 J −T =  
 P  h

And  J −T for a real fluid is then linked to the system properties by

 J −T =
v
T − 1 ………………………….……..…(5.12)
cP

The J-T coefficient shows, for a real fluid, how the temperature changes with
pressure as the fluid expands isenthalpically through a J-T device.

3.2.3 Joule-Thomson Effect

It is immediately obvious that there are three distinct cases for  J −T :

1. When T − 1  0 then the J-T coefficient is positive (  J −T = + ).

A positive J-T means that as the pressure drops (as it must during any
throttling process) the gas temperature also drops. This means that the
gas cools down as it expands.

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TOPIC 5. Throttling 11

2. When T − 1  0 then the J-T coefficient is negative (  J −T = − ).

A negative J-T means that as the pressure drops (as it must during any
throttling process) the gas temperature rises. This means that the gas
heats up as it expands.

3. When T − 1 = 0 then the J-T coefficient is zero (  J −T = 0 ).

This is the point where the sign of the J-T coefficient is changing. The
temperature at which the sign changes is Ti = 1 /  and it is known as
the “J-T inversion temperature” Ti .

The J-T coefficient  J −T has units of (K/Pa) and depends both on the type of
gas and on the starting temperature and pressure entering the J-T device:

Nitrogen and oxygen (at 1 atm pressure) have J-T inversion temperatures of
about 350oC and 490oC respectively. If these gases are passed through a J-T
device at room temperature, then they will cool down (they are below their J-T
inversion temperature).

On the other hand, helium and hydrogen (at 1 atm pressure) have J-T
inversion temperatures of about -220oC and -170oC respectively. Expanding
these gases at room temperature causes them to heat up (these gases are
above their J-T inversion temperature).

Industrial gases such as oxygen, nitrogen, argon, neon, helium and hydrogen
must be liquefied before being transported for industrial and medical use
(although they may be generated on-site if necessary).

An important process for liquefying gases is the Linde cycle which uses a
sequence of J-T expansions to successively lower the temperature of the gas
until it is finally liquefied:

For a given gas at given inlet conditions, the gas cannot be liquefied by the
Linde cycle unless it has a positive J-T coefficient under these conditions.

Nitrogen and oxygen both have positive J-T coefficients at ambient

temperature and 1 atm – thus, these gases may be liquefied from ambient
temperature using the Linde cycle.

However, helium, hydrogen and neon have negative J-T coefficients at

ambient temperature and 1 atm. Thus, these gases cannot be liquefied using a
Linde cycle, without some other form of cooling.

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Worked Example 5.2.2

Problem:

Equation (5.12) applies to all gases undergoing an isenthalpic process. It

would be instructive to test it for an ideal gas where it is already known
experimentally that, when such a gas undergoes a throttling process, its
temperature should remain constant.

What is expected is that the Joule- Thomson coefficient should be  J −T = 0 at

all temperatures.

Solution:

Start with the expression for the J-T coefficient in terms of system properties
(remember, this is a general expression and applies to any fluid)

 J −T =
v
T − 1
cP
Where,
1  v 
=  
v  T  P

It is immediately clear that  J −T = 0 if and only if T − 1 = 0 . Start by finding

 (for an ideal gas)

RT
v=
P

And, therefore

 v 
ig
R
  =
 T  P P

But the definition of  is given by

1  v 
=  
v  T  P

Substituting (v / T ) igP into the above definition leads to the ideal gas
coefficient of expansion  ig

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TOPIC 5. Throttling 13

R
 ig =
Pv

In view of the ideal gas EOS v = RT / P , so that  ig (after cancellation) is

simply given by

1
 ig =
T

Thus, for an ideal gas

T − 1 = 0
 T 
  J −T =   =0
 P  h

This prediction is consistent with experimental observations.

……….………………………………………

Worked Example 5.2.3

Problem:

Equation (5.11) is generally true for any pure substance – it shows how the
enthalpy changes with temperature and pressure:

If it is true for any substance, then it must be true for an ideal gas. Show that,
for an ideal gas, the above expression produces the correct enthalpy
dependence in terms of pressure and temperature.

Solution:

The starting point for finding the enthalpy dependence is to write the total
differential of enthalpy as a function of the two intensive properties,
temperature and pressure.

Thus, the total differential is given by

 h   h 
dh =   dT +   dP
 T  P  P  T

From the definition of heat capacity

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TOPIC 5. Throttling 14

 h 
  = cp
 T  P

It has been shown that for any fluid the isothermal pressure dependence of
enthalpy is given by

 h 
  = vT − 1
 P  T

From the previous worked example it was shown that T − 1 = 0 for an ideal
gas, which means that for an ideal gas

 h 
ig

  =0
 P  T

Thus, for an ideal gas the enthalpy dependence is simply

dh = c P dT

This result clearly confirms previous findings (kinetic theory of gases) that the
enthalpy of an ideal gas is a function of temperature only and is independent of
pressure.

…………………………………………….

Worked Example 5.2.4

Problem:

Starting with the following general expressions that apply to any real fluid:

1  v 
 J −T =
v
T − 1 =  
cP v  T  P

Apply the VdW EOS to the above and find an analytical solution for the J-T
coefficient in terms of inlet conditions and VdW attractive and repulsive
material parameters a & b .
Solution:

The VdW EOS was developed earlier and is given by

 
(v − b ) = RT
a
P + 2
 v 

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TOPIC 5. Throttling 15

a ab
 Pv + − Pb − 2 = RT
v v

Just as the ideal gas law was differentiated to find  , so too the VdW EOS
may be differentiated implicitly to get

 v  a  v  2ab  v 
P  − 2  + 3   =R
 T  P v  T  P v  T  P

 v  R
  =
 T  P P − a 2ab
+ 3
2
v v

1  v  R
 =   = …………………....(5.13)
v  T  P a 2ab
Pv − + 2
v v

From this result it follows that

T − 1 = RT
a 2ab
−1
Pv − + 2
v v

Notice that this reduces to the ideal gas result T − 1 = 0 if a & b are both
zero (as it must). Thus, for any fluid the J-T coefficient  J −T can be expressed
in terms of system properties and VdW material parameters a & b as follows:

 
 
v  RT
 J −T = − 1 ……………………….(5.14)
cP  a 2ab 
 Pv − + 2 
 v v 

For any real gas at its inversion temperature Ti − 1 = 0

1
 Ti =


Applying the VdW EOS to this result gives Ti = Ti (P) for any real gas

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TOPIC 5. Throttling 16

a 2ab
Pv − +
 Ti = v v 2 ………………………………..(5.15)
R

Returning to the pressure dependence for any real fluid

 h 
  = vT − 1
 P  T

Applying the VdW EOS to this result gives (for any real fluid)

 
 
 h  RT
  = v − 1 ………………….….(5.16)
 P  T  a 2ab 
 Pv − + 2 
 v v 

This result indicates that the enthalpy of a VdW gas depends not only on
temperature, but also on pressure. For an ideal gas, the material parameters
are zero and the partial derivative is again zero (as expected).

However, substituting equation (5.15) into equation (5.16) leads to the result
that, even for real gases (h / P )T = 0 , (this applies only along the J-T
inversion curve). Obviously for real gases away from the inversion point
(h / P)T  0 and this leads to either a positive or a negative  J −T .

5.2.4 J-T Effect and VdW Attractive and Repulsive Components

It has been shown that for an ideal gas the J-T coefficient is always zero and
that as an ideal gas expands through a J-T device, it follows a line of constant
enthalpy and, since enthalpy is a function of temperature only (ideal gas), the
temperature also remains constant.

It has also been shown that for a VdW gas, equation (5.14) defines the J-T
coefficient and this may be positive, negative or zero (at the inversion
temperature).

It is instructive to consider what microscopic factors within VdW gas lead to

this behaviour. The factors obviously depend on the material parameters
a & b , which in turn depend on attractive and repulsive interactions between
gas particles.

Whenever gas pressure falls, as with a J-T throttling, the gas particles move
further apart and the potential energy of the gas particles will increase:

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TOPIC 5. Throttling 17

• For a throttling process, there is no external exchange of energy

between the system and surroundings.
• If the potential energy of the gas particles increases, then the kinetic
energy of the gas particles must decrease.
• A decrease in kinetic energy must lead to a decrease in gas
temperature (see Process Industries C, Topic 6, Kinetic Theory of
Gases). This leads to the observation that a VdW gas may cool down
as its pressure drops.

However, there is another phenomenon which occurs in parallel, but produces

the opposite effect:
• Whenever a gas expands, say during a throttling process, the particle-
particle collision frequency must decrease.
• During any collision kinetic energy is temporarily converted into
potential energy.
• Thus, a decrease in the particle collision frequency must decrease this
conversion of kinetic energy into potential energy.
• As a result the kinetic energy of the gas may increase.
• This opposing effect may lead to the observation that a VdW gas can
heat up as its pressure drops.

The two competing effects occur at the same time and whether the gas cools
down or heats up depends on which effect dominates:
• If the inlet conditions are such that the J-T coefficient is positive (see
equation (5.14)), then the gas will cool down during a throttling process.
• If the inlet conditions are such that the J-T coefficient is negative (see
equation 5.14)), then the gas will heat up during a throttling process.

Lighter gases such as hydrogen, helium and neon have much higher root-
mean-square velocities than heavier gases such as nitrogen and oxygen.
Thus, lighter gases have a higher collision frequency at the same temperature:
• This higher collision frequency causes hydrogen and helium to have
negative J-T coefficients at ambient temperature and high-pressure
inlet conditions.
• Thus, the Linde process cannot be used alone to liquefy these gases.

On the other hand, nitrogen and oxygen are heavier, with lower root-mean-
square velocities at the same temperature. These gases have a lower collision
frequency and a positive J-T coefficient at ambient temperature and high
pressure (so long as pressure is not excessive). These gases can be liquefied
by a simple Linde cycle.

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TOPIC 5. Throttling 18

5.3 Tutorial Questions Topic 5

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TOPIC 5. Throttling 19

5.4 Bibliography

Eastop, T.D., McConkey, A., Applied Thermodynamics for Engineering

Technologists, 5th. Ed., 1996, Prentice-Hall.

Felder, Richard M. and Rousseau, Ronald W. 2008. Elementary Principles of

Chemical Processes. 3rd ed. India: Wiley

Perry, Robert H. and Green, Don W. 2008. Perry’s Chemical Engineers’

Handbook. 8th ed. New York: McGraw-Hill.

Rogers, G.F.C., Mayhew, Y.R., Thermodynamic and Transport Properties of

Fluids-SI Units, 4th. Ed., 1992, Blackwell Publishing Ltd.

Smith, J.M., van Ness, H.C., Abbott, M.M., Introduction to Chemical

Engineering Thermodynamics, 7th Ed., 2000: McGraw-Hill.

©HERIOT-WATT UNIVERSITY B48BC November 2016 v3