3

CONCEPTS OF
THERMODYNAMICS

3.1 SYSTEM

A system is a part of the universe set aside for study. It must have
enclosing boundaries, outside of which are the surroundings (Fig. 6.1).
Examples of systems are reservoir gas flowing toward a wellbore, gas
undergoing compression by a mechanical compressor, and gas
flowing vertically in a well tubing or horizontally in a pipeline.
First-law analysis is essentially an accounting procedure for
measuring energy transfers to and from a system and changes of
energy inside the system. The two principal accounting procedures are
control-mass analysis and control- volume analysis.
Control mass (Fig. 3.2) is any selected piece of matter. Any assembly
is a control mass. An accounting procedure must be carried out over a
set accounting period, and an essential step is specifying the time base.
This might be a given period of time (the time required for something to
happen) or it might be instantaneous.
Control volume (Fig. 3.3) is any defined region in space. This region
may be moving, and its shape and volume may be changing. In this
case, though, most control volumes have a constant shape and size
 88 Concepts of Thermodynamics

Fig . 3.1 A system and its surroundings

Fig . 3.2 A control mass.

Fig . 3.2 A control volume.

 Energy and Energy Balances 89

and are fixed in the reference frame. Control volume is posed in terms of
property fields, that is, the distribution of the properties through space
and time; the analysis provides information in terms of these fields.
To contrast the control-mass and control-volume perspectives simply,
the control-mass method calculates the properties of given pieces of
matter as functions of time, while the control-volume method gives the
properties of whatever piece of matter happens to be in a given region
of space at any given instant.

3.2 ENERGY AND ENERGY BALANCES

The energy balance is an important consideration in making
engineering calculations. In making a balance of energy, all energy
factors must be expressed in the same units if the calculations are to be
correct. These units may be either foot-pound force or British thermal
units, for example. The relationship of 1 Btu is equivalent to 778.2 ft-1bf,
which is useful.
The general methodology of energy-balance analysis is:
1. Define the control mass or control volume, indicating its boundaries
on a sketch.
2. Indicate what flows of energy across the boundary will be
considered and set up their sign convention on the drawing.
3. Indicate the time basis for the energy balance.
4. Write the conservation of energy in general terms.
5. Make appropriate idealizations and bring in equations of state or
other information necessary to allow solution.
This study centers on energy balances of dynamic systems. Energy is
carried with flowing fluid and may be transferred from the fluid to the
surroundings, and vice versa. Therefore, this chapter deals with the ways
that energy may be interchanged between different forms of energy as
the system moves through a piece of equipment, a processing plant, or
a length of pipe.
Energy carried with the fluid includes the internal energy, U, and all
energy that is the peculiar property of the fluid, regardless of its relative
location or motion, and the energy carried by the fluid because of its
condition of flow or position. This energy carried by the fluid
encompasses three other types of energy: energy of motion (kinetic
2
energy, mu /2gc), which is the energy associated with movement with
respect to a fixed point; energy of position (potential energy, mgZ/gc),
which results from the system’s location in the earth's gravitational field;
 90 Concepts of Thermodynamics

and pressure energy, pV, carried by the system because of its

introduction into or exit from flow under pressure.
Energy transferred between a fluid or system in flow and its
surroundings is of two kinds. First is heat, Q, absorbed by the flowing
material or system as a result of temperature difference between the
system and surroundings. Heat gained by the system is positive in sign,
while heat lost by the system is negative in sign. Second is work, w, done
by the system on the surroundings. This is often called shaft work, ws, and
does not include lost work, lw, caused by friction. Work is positive in sign
when the system performs work on the surroundings. Heat and work are
the only means of transferring energy between the system and the
surroundings.
Consider Fig. 3.4. An energy balance around such a flow system,
between points 1 and 2 and the surroundings, assuming no
accumulation of material and energy at any point in the system, is given
by the equation

(3.1)

Fig. 3.4 Energy balance.

By definition,

and

Therefore,
 Enthalpy Change 91

(3.2)
3.3 ENTHALPY CHANGE, DH
The thermodynamic property enthalpy H is defined as
(3.3)
Thus, the change of enthalpy is given by

(3.4)
Equation 3.2 becomes
(3.5)
where

In calculating DH between two thermodynamic states (pressure and

temperature), use specific enthalpy of the fluid, h', in Btu/lbm or the
molal specific enthalpy, h, in Btu/lb-mol. Thus,
(3.6)
or
(3.7)
where
m = pound-mass of fluid
n = pound-moles of fluid
The units Btu/lb-mol will be used in most of the work in this text.
For natural gas, the molal specific enthalpy is a function of
temperature, pressure, and gas composition:
(3.8)

For a given composition (gas gravity),

Then, taking the differential,

(3.9)

Integrating Eq. 3.9,

(3.10)
3.4 SPECIFIC HEATS
 92 Concepts of Thermodynamics

Consider the functional relation u = u(T, v). The difference in energy

between any two states separated by infinitesimal temperature and
specific-volume differences dT and dv is
(3.11)

The derivative is called the specific heat at constant volume:

(3.12)

In Eq. 3.9, the derivative is called the specific heat at constant

pressure:
(3.13)

The derivatives Cp and Cv constitute two of the most important

thermodynamic derivative functions, and values have been
Fig. 3.5 Specific heat of hydrocarbon gases at 1.0 atm pressure. (After Brown)
 Specific Heats 93

experimentally determined as functions of the thermodynamic state for

many simple compressible substances.
The specific heats of gases and liquids are determined
experimentally in a calorimeter, usually at a pressure of 1 atm. For natural
gases, the specific heat at 1 atm pressure is a function of temperature
and of gas gravity or molecular weight. Figure 3.5 is a graph of specific
heat at constant pressure for natural gases at 1 atm pressure.
The specific heat at constant volume is related to the specific heat
at constant pressure for ideal gases as follows:
(3.14)

The ratio of the specific heats is useful in computing the

adiabatic compression of gases, for which ideal gases follow the
relationship
(3.15)

3.4.1 Effect of Pressure on Specific Heat and Enthalpy

The law of corresponding states can be used to correct specific heat
values measured at 1 atm pressure for pressures other than 1 atm. The
specific heat at constant pressure at pressures greater than
atmospheric is given by
(3.16)
The correction term can be calculated from
thermodynamics. From thermodynamic relations, the effect of pressure
alone is given by

(3.17)

where
v = molal specific volume, cu ft/lb-mol

For real gases,

Differentiating,
 94 Concepts of Thermodynamics

Then,

or,

(3.18)
Using reduced temperature and reduced pressure,

(3.19)

If R = 10.732 psia cu ft/lb-mol °R, P in psia,

(3.20)
or,

(3.21)

where

Figure 3.6 is a graph of prepared on a reduced temperature-

reduced pressure basis, to avoid preparing many charts for gases of
different gravity.
Figure 3.7 is a generalized isothermal pressure correction to enthalpy
of gases. It is a graph of versus reduced pressure,
with lines of constant reduced temperature. This graph uses
pseudocritical temperature instead of the actual temperature when
dividing to find the function.
Figure 3.7 gives Dh above a reference state of 0 psia and 0 °R.
 Entropy, S 95

3.5 ENTROPY, S
The entropy, S, is a property of the system defined as

(3.22)

The change
Fig.3.6
in this property is analogous to the change in energy.
Isothermal pressure correction to heat capacity of vapours. (After Edminster.)
 96 Concepts of Thermodynamics

Hence,

where

In making a number of calculations on fluid behaviour, consider the

changes in Entropy that the system may undergo.

Fig. 3.7 Effect of pressure on enthalpy for natural gases. (After Edminster.)
In general, energy can be defined as the product of an intensive
property of a material and the change in the extensive property.
Intensive property is independent of the amount of material present, for
example, pressure, temperature, density, surface tension, and
chemical potential. Extensive property depends on size or amount of
 Entropy, S 97

material present, for example, mass, area, inertia, and volume.

Example 3.1. Compression of a Quantity of Gas in a Piston.

Incremental work done by piston on gas:

(3.23)
Where

Thus compression work:

(3.24)

Example 3.2. Change in Area of a Gas Bubble. Surface work involved

is given by

(3.25)
where

Example 3.3. Change in Heat Energy

Temperature = intensive property
The extensive property required to go with temperature, in order to
express heat energy as a product of an intensive property and change
in an extensive property is called entropy, S. In the form of Eqs. 3.24 and
3.25,

(3.26)

Change in internal energy, is the sum of changes in all forms of energy

taking place in the material in flow, including heat effects, compression
effects, surface effects, chemical effects, and so on:

(3.27)

where
 98 Concepts of Thermodynamics

The energy term is a complete differential:

(3.28)

Combining Eqs. 3.1, 3.27, and 3.28,

(3.29)
In any process, the increase in internal energy due to heat effects
is equal to the sum of the heat absorbed from the surroundings
and all other energy dissipated into heat effects within the system due to
irreversibilities such as overcoming friction occurring in the process. Thus,

(3.30)
where
lw = "lost work," energy that could have done work but was
dissipated in irreversibilities within the flowing material

If Eqs. 3.29 and 3.30 are combined and rearranged,

(3.31)
These equations contain no limiting assumptions other than no
accumulation of material in the unit and are unrestricted in application
 Entropy, S 99

to material flowing or transferred from state 1 to state 2. The equation

used is mainly a matter of convenience . In natural gas engineering
problems, surface and chemical effects are negligible and these
energy terms are usually dropped from the equation. For example,
surface effects, and so on, and Eq. 3.31 may be written as

(3.32)
Writing Eq. 3.32 fora unit mass of material,

(3.33)

Where

If the flow is also approximately isothermal and the fluid is almost

incompressible, the volume of a unit mass may be assumed to be
constant and Eq.3.33 may be further simplified to

(3.34)
Equation 3.34 is limited to a material of approximately constant density
and is frequently referred to as Bernoulli's equation when and are
zero.
Recall the following equation:

(3.5)
Equation 3.29 (without surface and chemical effects) can be written
as

(3.29a)
Comparing Eqs. 3.5 and 3,29a,

(3.35)

3.5.1 Calculation of Molal Specific Entropy (s)

 100 Concepts of Thermodynamics

As in the case of enthalpy, one can write

(3.36)
where
n = pound moles of fluid considered
s = molal specific entropy, Btu/lb-mol °R
Rewriting Eq. 3.35 in terms of molal values,

(3.37)
where
v = molal specific volume, cu ft/lb-mol
Recall that
(3.9)

(3.13)

(3.17)
Thus Eq. 3.9 can be integrated to give

(3.38)

Solving Eqs. 3.37 and 3.38 for ds yields

(3.39)

Integration of Eq. 3.39 between two pressure-temperature points will

yield the difference in entropy. In Brown's enthalpy-entropy charts, the
reference state at which S° = 0 is selected as 32°F and 14.7 psia. For
illustrative purposes, calculate s using this reference state, using an
average Cp and taking it outside the integral sign.
Thus,
(3.40)

(The constant 144 allows pressure to be in psia and 778.2 converts ft-Ibf/lb-
mol.)
For a given composition gas,
 Entropy, S 101

Therefore,

Substituting this in Eq. 3.40,

(3.41)

n terms of average z and average

(3.42)

When working with reduced parameter z chart, Eq. 3.42 is easier to write
in terms of, reduced variables. Change and
Eq. 3.42 becomes

(3.43)

Equation 3.43 is written for a reference state of 32°F and 14.7 psia. It can
be modified for any reference state. Equation 3.43 contains three
averages. These can be evaluated as follows (Fig. 3.8):

Example 3.4. Calculation of Thermodynamic Properties from

Pressure- Volume - Temperature and Specific Heat Data. Calculate
the molal enthalpy and molal entropy change, and when a
quantity of 0.7 specific gravity natural gas is compressed from 14.7 psia
and 100°F to 800
 102 Concepts of Thermodynamics

psia and 300°F. Check your answers against Brown's enthalpy-entropy

chart for 0.7 gravity natural gas given in Section 3.6.

Solution
Fig. 3.8 Averages used in entropy calculation. (After Standing.)
 Entropy, S 103

Enthalpy Change,
For 0.7 specific gravity natural gas,

Using Eq. 3.9,

The change in enthalpy may be divided into two processes: change

at constant pressure and change at constant temperature. Consider
change from 100°F to 300°F, at a constant pressure of 14.7 psia. The
change in enthalpy is given by

From Fig. 3.5, at an average temperature of 200°F is 11.1 Btu/lb-mol

°F:

Then consider change from 14.7 to 800 psia, at a constant temperature of

300°F.
The change in enthalpy is given by

or

At 800 psia,

At 300°F,

From Table 2.7, z-factor equations,

Thus,
 104 Concepts of Thermodynamics

Total enthalpy change is

From Brown's h-s chart for 0.7 gravity natural gas (Fig. 3.10), at 14.7 psia
and
100°F,

At 800 psi a and 300°F,

From Eq. 3.43, modified to reflect 100°F rather than 32°F,

At constant pressure (14.7 psia), at an average temperature of 200°F is

11.1Btu/lb-mol °F. The average z-factor from ppr = 0.02 to 1.20 at Tpr =
1.94, from the z-factor chart (Fig. 2.4), is

Thus,

From Brown's h-s chart for 0.7 gravity natural gas (Fig. 3.10), at 14.7 psia
and 100°F,
 The Enthalpy-Entopy Diagram 105

At 800 psia and 300°F,

Example 3.5. Calculate the amount of energy involved in taking 1 MMcf

(measured at 14.73 psia and 60°F) of the 0.7 specific gravity gas of
Example 3.4 from 14. 7psiaand 100°F to 800psiaand 300°F, using
Edmister's
Chart and Cp chart.
Solution
6
Number of moles involved = (1 x 10 )/378.6 = 2641.
For a constant pressure process (at 14.7 psia), the energy required to go
from 100 to 300°F is

and

For constant temperature (300°F) compression, using Fig. 3.7, at Tpr =

1.94 and Ppr = 0.02,

at

Thus,

and

The total energy required is

3.6 THE ENTHALPY-ENTROPY DIAGRAM (MOLLIER DIAGRAM)

In the analysis of steady-flow processes, an enthalpy-entropy diagram is
 106 Concepts of Thermodynamics

quite useful. The enthalpy is the important thermodynamic property in

the steady-flow energy balance, and entropy is the principal property of
concern with respect to the second law. Thus, the coordinates of an h-s
diagram represent the two major properties of interest in the first- and
second-law analysis of open systems. The vertical distance between two
states on this diagram is a measure of Dh. The enthalpy change, in turn, is
related through the adiabatic steady-flow energy balance to the work or
kinetic-energy changes for turbines, compressors, nozzles, and so on.
The horizontal distance between two states Ds is a measure of the,11
degree of irreversibility for an adiabatic process. The isentropic process
conveniently appears as a vertical line, allowing the end state of an
idealized adiabatic process to be found easily. As a consequence, the
h-s diagram is helpful in visualizing process changes for control-volume
analyses.

Brown has prepared enthalpy-entropy diagrams for natural gases.

The h-s diagrams of natural gases of 0.6, 0.7,0.8,0.9, and 1.0 gravity are
given
Fig. 3.9 inEnthalpy-entropy
Figs. 3.9 to 3.13. The pseudocritical
diagram temperatures
for 0.6-gravity natural and pressures
gas. (After Brown.)
 The Enthalpy-Entopy Diagram
107

Fig. 3.10 Enthalpy-entropy diagram for 0.7-gravity natural gas. (After Brown.)
 108
Concepts of Thermodynamics

Fig. 3.11 Enthalpy-entropy diagram for 0.8-gravity natural gas. (After Brown.)
 The Enthalpy-Entopy Diagram
109

Fig. 3.12 Enthalpy-entropy diagram for 0.9-gravity natural gas. (After Brown.)
 110
Concepts of Thermodynamics

Fig. 3.13 Enthalpy-entropy diagram for 0.10-gravity natural gas. (After Brown.)
 The Enthalpy-Entropy Diagram
111

Fig. 3.14 Enthalpy-entropy diagram for 0.11-gravity gas contaning 10% nitrogen. (After Brown.)
 112 Concepts of Thermodynamics

used are given on the charts and correspond essentially to hydrocarbon

gases. The datum for each chart is 32°F, 1 atm. A chart for a gas of 0.7
gravity but containing 10 mole % nitrogen is given by Fig. 6.14.
Campbell presents an h-s chart for an average natural gas (0.65-0.75
gravity) in Fig. 3.15. These charts are useful in finding the temperature
change on expanding or compressing gases and for finding the
reversible work of compression or expansion.
Enthalpy-entropy charts apply only to the gaseous state; if a gas is
cooled below its dew point, condensation occurs and heat removal
cannot be determined directly from the charts.
Another presentation of enthalpy information is the pressure-enthalpy
(p-H) diagram with lines of constant entropy (S). This is very useful in
understanding and solving refrigeration and other thermodynamic
problems. Figure 3.16 is a pressure-enthalpy diagram for propane, a
common refrigerant.
Example 3.6. Cooling or Heating a Gas at Constant Pressure.
(a) What is the amount of heat that must be removed in cooling 1Ib-
mol of 0.6 specific gravity natural gas at 200 psia from 600 to 100°F?
(b) If this gas is then heated from 100 to 300°F, how much heat is
required per pound-mole of gas?
Solution
(a) Using Fig. 3.9 for 0.6 gravity natural gas, read the enthalpy at the
intersection of the 600°F line and the 200 \ psia line, which is h =
6100 BtU/lb-mol. Then follow the 200-psia line to its intersection
with the 100°F line and read the enthalpy hz of 500 Btu/lb-mol.

(b) At 200 psia and 300 °F the enthalpy h3 = 2600 Btu/lb-mol.

Example 3.7. Adiabatic Reversible Expansion of a Gas. If a 0.7 specific

gravity natural gas at 300°F and 500 psi a is expanded adiabatically
and reversibly to 100 psia, what will be the final temperature of the gas?
Solution
Using the h-s diagram for 0.7 gravity natural gas (Fig. 3.10), at the
intersection of the 300°F and 500 psi a lines, the entropy
In an adiabatic process no heat is added or removed. Since the process
 The Enthalpy-Entropy Diagram 113

is reversible,

or

Thus a reversible adiabatic process is isentropic. To get the properties

at the final state, follow the entropy line for s1 to its intersection with the
100-psia line and read the temperature
Example 3.8. Throttling or Joule - Thomson Effect. If a gas of 0.8
specific gravity at 2000 psia and 200°F expands through a small orifice
without the addition or subtraction of heat and is brought finally to its
initial velocity and a pressure of 50 psia, what will be its temperature?

Solution
Refer to Fig. 3.11 for 0.8 gravity gas. At the intersection of the 2000-
psia and 200°F lines, h1 = 700 Btu/lb-mol. Since the heat content is
constant, follow the 700 Btu/lb-mol to its intersection with the 50-psia line
and read the temperature T2 of 100 °F.
In most cases throttling processes occur so rapidly and in such a small
space, that there is neither sufficient time nor a large enough area for
much heat transfer. Therefore, such processes may be assumed to be
adiabatic. But they are not reversible.
Example 3.9. Adiabatic Reversible Compression. A 0.9 specific gravity
natural gas at 50 psia and 80°F is compressed adiabatically and
reversibly to 1000 psia. What is the temperature of the compressed gas?
Solution
Refer to Fig.3.12 for 0.9 gravity gas. At the intersection of the 50-psia
line and the 80°F line, the entropy s1 = -1.3 Btu/lb-mol°F. Then follow the s1
= -1.3Iine to its intersection with the 1000-psia line and read T2 = 410°F.
Example 3.10. Isothermal Expansion of a Gas
(a) One pound-mole of 1.0 specific gravity natural gas at 2000 psia
and 420°F is expanded through a throttling valve or orifice and is
brought to its initial velocity and a pressure of 100 psia. How
much heat must
 114 Concepts of Thermodynamics

Fig. 3.15 Enthalpy-entropy diagram for a 0.65 to 0.75 specific gravity natural gas.
(After Campbell.)

be added to maintain the temperature of the gas at 420°F?

(b) What would the temperature be if no heat is added?
Solution
(a) h-s diagram for 1.0 gravity gas is given in Fig. 3.13. The enthalpy
at the intersection of the 420°F and 2000-psia lines is h1 = 4700
 The Enthalpy-Entropy Diagram
115

Fig 3.16 Pressure - enthalpy diagram for propane (Shell Development Co.)
 116
Concepts of Thermodynamics

Fig 3.17 Isentropic (DS = 0) and Isentropic (DH = 0) paths on P-H charts
 The Enthalpy-Entropy Diagram 117

Btu/lb-mol. Follow the 420°F line to its intersection with the 100-
psia line and read the enthalpy h2 = 5650 Btu/lb-mol. Since no
external work has been done, the amount of heat added is

h2 - h1 = 5650 -4700 = 950 Btu/lb-mol

(b) If no heat is added to the gas the final temperature would be
obtained by following the h1 = 4700 Btu/lb-molline to its
intersection with the 100-psia line. This gives T2 = 362 °F.
Example 3. 11. Forty million cubic feet per day (measured at 60°F and
14.73 psia) of an average natural gas at 240°F are flowing freely through
an expansion valve with the pressure dropping from 2000 to 1000 psia.
(a) What is the temperature change across the valve?
(b) What is the maximum work that could be derived from this
expanding gas stream without the use of heat?
(c) What would be the temperature change on the gas when
expanding through an adiabatic reversible engine?
Solution
Refer to the h-s diagram for average natural gas (Fig. 3.15).
(a) At 2000 psia and 240°F,
h1 = 1400 Btu/lb-mol
For the throttling process across the valve the enthalpy is constant. At
1000 psia and h = 1400 Btu/lb-mol,
T 2 = 212°F
(B), (c) Maximum work would be obtained using an adiabatic and
reversible (i.e., isentropic) process. At 2000 psia and 240°F,
s1 = -7 .00 Btu/lb-mol °F
At 1000 psi a and s = -7.00 Btu/lb-mol °F,
T3 = 140 °F
h3 = 560 Btu/lb-mol
Work done by gas = -Dh = h1 - h3 = 1400 - 560 = 840 Btu/lb-mol

1 Ib-mol occupies 378.6 cu ft at 60°F and 14.73 psia

Example 3.12. One hundred pounds of natural gas (mainly methane)

at 500 psia and 50°F passing through
 118 Concepts of Thermodynamics

(a) A choke (a throttling isenthalpic process, Dh = 0)

(b) A turbo expander (an isentropic process, Ds = 0)
undergoes a pressure drop to ISO psia. What are the outlet temperatures
of the two processes? Is any work done by either of the processes? Both
processes are assumed to be ideal and adiabatic (q = 0). Use the
pressure-enthalpy chart for methane (Fig. 3.17).
Solution
In Fig 3.17, path A represents the isenthalpic process (Dh = 0) from 500
psia, 55°F to 150 psia, T = – 30°F. Path B shows the isentropic process (Ds
=0), ending at ISO psia and T =80°F.
Since both processes are adiabatic (q = 0), the work (w) is equal to the
change in enthalpy H.
(a) For the isenthalpic process (Joule-Thomson effect), no work has
been done.
(b) The isentropic process does some work:
Work = flow rate x enthalpy change (L\h)
= (100 Ib)(382 - 320) Btu/lb
= 6200 Btu/(2544.5 Btu/hp.hr)
= 2.437 hp.hr
This is a by-product of expander cooling and could be utilized to spin the
compressor on the side of the expander-compressor units.

3.7 JOULE- THOMSON EFFECT

When pressure in a flowing gas stream is reduced over common ranges
as it passes through a valve, choke or perforations in a casing,
temperature of the gas decreases. This temperature reduction as the
gas throttles is called the Joule-Thomson effect. The change in
temperature is directly related to attraction of molecules for each other.
For small pressure changes in an adiabatic system (no heat transfer), the
change in temperature is given by

(3.44)

Substituting the real gas equation of state into Eq. 3.44 gives

(3.45)

Direction of change in temperature (decreasing or increasing) will

depend on the sign of the quantity on the right hand side of Eq. 3.45. The
 Joule-Thomson Effect 119

terms V, T, z and Cp are positive. Thus Dp and (dz/dT)p will determine

whether the temperature will decrease or increase as the pressure
changes.
In the petroleum industry flow is usually in the direction of decreasing
pressure, thus Dp is negative. Observation of the gas deviation factor
chart shows that at moderate pressures (ppr<6.0) z-factor increases as
temperature increase at constant pressure, thus (dz/dT)p is positive and
temperature decreases as pressure decreases. At high pressures (ppr>
11. 0) z- factor decreases as temperature increases at constant
pressure, thus (dz/dT)p is negative temperature increases as pressure
decrease.

For natural gases the isotherms on the gas deviation factor chart cross
between 5,000 psia and 7,000 psia. At moderate pressures (below
5,000 psia) Joule-Thomson effect is observed. At high pressures (above
7,000 psia) some heating effect is observed. Operators have noticed
hot spots in deep gas wells where high pressure gas flow through
Fig. 3.18 Principles of Refrigerated Liquid Extraction
perforations.
 120 Concepts of Thermodynamics

Figure 3.18 is a pressure-enthalpy diagram illustrating different

cooling processes. Consider natural gas at pressure p2 and temperature
T1 (Point 1). If this gas at is cooled at constant pressure to Point 2, liquid
products begin to condense.
The pressure is reduced at constant enthalpy to p1 (point 7), the
temperature is further reduced and the amount of liquid products is
formed is increased. This change is adiabatic (no heat removed
between points 2 and 7) and is Joule-Thomson expansion. If temp were
reduced isentropically (without change of entropy) from p2 at Point 2 to
p1 at Point 8, maximum temperature reduction and liquid recovery
would occur. This is theoretically possible but impractical. An expander
process (line 2-3) is a practical approach to isentropic expansion. Line 7-
3 is work removed from system by the turbo expander.
Straight refrigeration with expansion involves refrigerating at const
pressure to Point 12 (latent is heat removed, additional condensation).
This is followed by adiabatic Joule- Thomson expansion, which reduces
the pressure to Point 3 (decreases temperature, increases
condensation). Compression followed by Joule-Thomson expansion
involves compression from p2 at Point 1 to p3 at Point 9. The temperature
is then reduced at constant pressure to Point 11. Finally, the gas
undergoes adiabatic expansion from p3 to p1 (process 11-3).

REFERENCES

Brown, G. G. "A Series of Enthalpy-Entropy Charts for Natural Gases."

Trans. AIME 60, p. 65, 1945.
Brown, G. G., et al. Unit Operations. New York: Wiley, 1950.
Campbell, J. M. Gas Conditioning and Processing. Norman, Okla:
Campbell Petroleum Series, 1978.
Edminster, W. C. "Application of Thermodynamics to Hydrocarbon
Processing." Petroleum Engineering Series 27-28; 11, p. 129; 12, p.
116; 1, p. 128; 2, p. 137. 1948-1949.
Katz, D. L., et al. Handbook of Natural Gas Engineering. New York;
McGraw Hill, 1959.
Katz, D. L., and R. L. Lee. Natural Gas Engineering, Production and
Storage. New York: Mc Graw- hill, 1990
Standing, M. B. "Natural Gas Engineering Notes." Stanford University,
1977.
 Joule-Thomson Effect 121

PROBLEMS

3.1 Calculation of Thermodynamic Properties from Pressure- Volume-

Temperature and Specific Heat Data
Calculate the molal enthalpy and molal entropy change, dh and
~, when a quantity of 0.8 specific gravity natural gas is
compressed from 50.0 psia and 100°F to 800 psia and 300°F.
Check your answers against Brown's enthalpy- entropy chart for 0.8
gravity natural gas.
3.2 Calculate the amount of energy involved in taking 1 MMcf
(measured at 14.73 psia and 60°F) of the 0.8 specific gravity gas of
Problem 1 from 14.7 psia and 100°F to 800 psia and 300°F, using
Edmister's Dh/Tc, chart and Cp chart.
3.3 Cooling or Heating a Gas at Constant Pressure
(a) What is the amount of heat that must be removed in cooling
lIb-mol of 0.8 specific gravity natural gas at 200 psi a from 600
to 100°F?
(b) If this gas is then heated from 100 to 300°F, how much heat is
required per pound-mole of gas?
3.4 Adiabatic Reversible Expansion of a Gas
If a 0.8 specific gravity natural gas at 300°F and 500 psia is
expanded adiabatically and reversibly to 100 psia, what will be the
final temperature of the gas?
3.5 Throttling or Joule- Thomson Effect
If a gas of 0.6 specific gravity at 2000 psia and 200°F expands
through a small orifice without the addition or subtraction of heat
and is brought finally to its initial velocity and a pressure of 50 psia,
what will be its temperature?
3.6 Adiabatic Reversible Compression
A 0.8 specific gravity natural gas at 50 psia and 80°F is compressed
adiabatically and reversibly to 1000 psia. What is the temperature
of the compressed gas?
3.7 Isothermal Expansion of a Gas
(a) One pound-mole of 0.8 specific gravity natural gas at 2000
psia and 420°F is expanded through a throttling valve or orifice
and is brought to its initial velocity and a pressure of 100 psia.
How much heat must be added to maintain the temperature
of the gas at 420°F?
(b) What would the temperature be if no heat is added?
3.8 Forty million cubic feet per day (measured at 60°F and 14.73 psia)
of an average natural gas at 320°F is flowing freely through an
 122 Concepts of Thermodynamics

expansion valve with the pressure dropping from 4000 to 1000

psia.
(a) What is the temperature change across the valve?
(b) What is the maximum work that could be derived from this
expanding gas stream without the use of heat?
(c) What would be the temperature change on the gas when
expanding - through an adiabatic reversible engine?