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On The Correlation Between Isothermal Compressibility and Isobaric Expansivity
On The Correlation Between Isothermal Compressibility and Isobaric Expansivity
On The Correlation Between Isothermal Compressibility and Isobaric Expansivity
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Brett Christie
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Copyright 2014, Pipeline Simulation Interest Group
Isobaric Expansivity
This paper was prepared for presentation at the PSIG Annual Meeting held in Baltimore, Isothermal Compressibility
This paper was selected for presentation by the PSIG Board of Directors following review of
information contained in an abstract submitted by the author(s). The material, as presented,
Acentric factor
does not necessarily reflect any position of the Pipeline Simulation Interest Group, its officers, Ratio of isobaric expansivity to isothermal
or members. Papers presented at PSIG meetings are subject to publication review by Editorial
Committees of the Pipeline Simulation Interest Group. Electronic reproduction, distribution, or compressibility
storage of any part of this paper for commercial purposes without the written consent of PSIG
is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300
words; illustrations may not be copied. The abstract must contain conspicuous Subscripts
acknowledgment of where and by whom the paper was presented. Write Librarian, Pipeline
Simulation Interest Group, P.O. Box 22625, Houston, TX 77227, U.S.A., fax 01-713-586-5955.
Critical
Pressure
Temperature
ABSTRACT
Fluid properties are a critical element to the success of any INTRODUCTION
pipeline simulation. In some cases the pumped fluid or liquid
mixture is so exotic in nature that laboratory data is
The total change in either pressure or specific volume in a
unavailable and an educated guess is the only course of action.
fluid can be described by two important fluid properties:
For transient simulation, knowledge of the isothermal
isobaric expansivity and isothermal compressibility. Isobaric
compressibility is important and some estimate could be made
expansivity is used to express the thermal expansion
by realizing the composition of the mixture. For steady state
experienced by fluids and is defined as the volume change of a
simulation, possibly for a batched system, the flow rates
fluid due to temperature change, while holding pressure
would need to be corrected to standard or pipeline base
constant [3]:
conditions, and these correction factors require knowledge of
1
both the isothermal compressibility and the thermal expansion
properties. If one can estimate the fluid compressibility with
some certainty, can one also estimate the isobaric expansivity?
Laboratory test data tend to show that liquids with high
compressibility also seem to have high isobaric expansivity, This is also referred to as the coefficient of thermal expansion.
indicating a correlation between the two. Hence this paper The isothermal compressibility is the volume change of a fluid
intends to discover what, if any, correlation exists through due to pressure changes at constant temperature is defined by:
1
examination of fluid properties of known pure components,
and application of physical processes and required
thermodynamic stability.
[3] that
0
Attractive force coefficient
Apparent body volume of molecules
Specific volume
Temperature Hence the isothermal compressibility will always be a
Pressure nonnegative number.
2 BRETT CHRISTIE PSIG 1426
This represents the inverse of the isothermal bulk modulus of increasing molar mass, are presented along with some
elasticity for the pipelined fluid. A general observation for observations about those fluids.
liquid phase is that as the compressibility increases, the
thermal expansion also increases. This leads one to wondering Data is graphed with isothermal compressibility as the
if there is a direct correlation between these two fluid independent variable and isobaric expansivity as the
properties, and what that might mean for fluids in general. dependent variable on the Y axis. Each data point has a given
pressure and temperature value, with NIST REFPROP
To arrive at a meaningful relationship this property needs to database [4] providing the specific volume, isothermal
be combined with an appropriate equation of state in order to compressibility and isobaric expansivity for the selected
show the details of the correlation and help explain the hydrocarbon. Pressure is 145 to 1450 psia in steps of 15 psia.
mechanisms involved. This paper uses absolute scales for pressure, and temperature
in degree Rankine.
We begin by looking at experimental data provided by the
National Institute for Standards and Technology (NIST) [4] Ammonia
for various hydrocarbons used in the pipeline industry, which
are typically compounds not pure elements. All fluid property Figure 2 has the liquid phase isotherms graphed for ammonia
data presented is taken from NIST. The NIST database uses a at three temperatures. The highest pressure point has the
variety of equations of state, including their “extended lowest compressibility and expansivity values. Following the
corresponding states model” and Helmholtz energy equations isotherm as the compressibility increases, the expansivity also
right. The critical point for this polar molecule is = 729 oR,
of state, including international standard equations for water, increases. As temperature increases the isotherms move to the
= 1636 psia.
carbon dioxide, ammonia and others.
The critical point for water is = 1165 oR, = 3203 psia and
limits. The high limit for temperature was selected to be 580
o
R (or 121 oF). Liquid pipeline operations typically have
pressure in the range 145 to 1450 psi, so that range was
Figure 3 shows water for several temperatures below the
selected for this study.
critical values. At 540 oR the isobaric expansivity decreases
with increasing compressibility. Then as the temperature
Furthermore, we need to make the distinction between polar increases, this behavior changes and isobaric expansivity
and nonpolar molecules. A polar substance has an electric increases as compressibility increases. Water is a polar
dipole or charge on its molecules and it may lead to different molecule.
results from nonpolar substances. Water and ammonia (NH3)
are examples of polar substances and are included in this
Ethane
study. Nonpolar molecules examples include the alkanes, such
as methane and ethane, and alkenes such as ethene.
Figure 4 shows curves for Ethane for three different
temperatures for the range of pressures. The highest pressure
EXPERIMENTAL RESULTS point has the lowest compressibility and expansivity values
and liquid phase. Following each isotherm, left to right, for
NIST [4] provides various databases of fluid properties, which increasing compressibility the pressure drops. High pressures
are based on experimental data. result in liquid phase and linear variation, as compressibility
increases, isobaric expansivity increases, and then
dramatically increases until the phase transition to vapor phase
compressibility linear part of the curve occurs in liquid phase, compressibility and expansivity values.
followed by the transition from liquid to gas and it`s clear that • In liquid phase, they all exhibit a monotonically inceasing
for gas phase one can have as many as three values for relationship between the isobaric expansivity and the
value. The critical point for CO2 is = 547 oR, = 1070 psia.
isobaric expansivity for a single isothermal compressibility isothermal compressibility; for water the relationship is
either increasing or decreasing depending on the
temperature.
Propane • The liquid phase curve appears to extrapolate to indicate
Values for propane ( = 665 oR, = 616 psia) are shown in
that zero compressibility corresponds with zero isobaric
expansivity.
Figure 6. Higher temperatures resolve the curve more fully • The phase change appears to have two or even three
than at lower temperatures, where a break occurs and the values for isobaric expansivity for a single isothermal
transition is not apparent. The curves are very similar as in the compressibility value.
case of the CO2 and ethane data. • For liquids, the less compressible a substance is the more
closely a common isotherm is followed.
Octane
THEORY
= 1024 oR, = 360 psia. Clearly this is liquid phase only for
Figure 7 shows Octane at 540 oR, wich has its critical point at
The next step is to see if theory can predict these results. The
the pressure and temperature range. Expansivity increases as classical thermodynamic perspective is preferred in this paper
isothermal compressibility increases. As temperature increases over the statistical viewpoint.
these curves move to the right. For these temperatures and
pressure range only liquid phase is experienced.
Classical Perspective
Normal Butane
The full or substantive derivative of change in pressure is
Figure 8 has n-Butane values ( =765 R, = 551 psia)
o given by:
+
shows that each isotherm has expansivity increasing as
compressibility increases. The slope of the curve decreases as
temperature increases. If the temperature continued to increase
the phase change from liquid to gas is expected to occur.
Where the total pressure change is a function of change in
Comparisons volume and temperature and the following relationship can be
derived:
Figure 9 shows various hydrocarbons at 540 oR (81oF) for
liquid phase. They all appear to follow the same curve. This is
an interesting result because it implies that a similarity law
exists. However Carbon Dioxide interestingly appears to
follow a different curve. Ethene or Ethylene follows more
closely but also appear to be on a slightly different curve.
From the definitions for thermal expansion and isothermal
compressibility, it can be shown that the ratio of our two
SUMMARY OF RESULTS properties of interest leads to a third property - which is the
pressure change with temperature change at constant volume:
To summaize the discussion of results above:
• A common correlation appears to exist at constant
temperature
• Liquid and gas phases have different behaviors This can be used with an equation of state to show the nature
• Isobaric expansivity appears to increase dramatically of the relationship. In this paper we need to trade state
during the phase change, followed by a decrease. equation accuracy with visibility to the underlying physical
• Liquid phase has one-to-one relationship with isobaric processes. With this in mind we choose the van der Waals
expansivity increasing as compressibility increases, concept buried in every cubic equation of state. The idea that
except for water which exhibits a change of slope. Of the the pressure of fluid results from the sum of repulsive and
hydrocarbons studied here, water has the lowest attractive forces was first expressed by van der Waals in his
4 BRETT CHRISTIE PSIG 1426
0.07780
equation and indeed all cubic equations are of the “van der
Waals” form:
!" + #$$#$" Figure 10 shows comparisons for pressure versus volume
between NIST and Peng Robinson for Ethene at 540 oR (81oF)
The van der Waals equation of state is: – they show very good agreement with the average error less
than 2% and the standard deviation of the differences less than
%
1%.
The first term on the right side represents the repulsion: the PHYSICAL PROCESSES
pressure exerted due to collision and is proportional to the
thermal part of energy (the sum of the translational,
Consider the isothermal compression of ethene at 540 oR. As
vibrational and rotational energies) of all the molecules within
the fluid is compressed the volume decreases while the
unit volume of free space. The second term is the reduction in
intermolecular spacing decreases. At larger volumes and lower
force due to the attractive force exerted on those molecules by
pressures the first term in the van der Waals equation
1
neighbouring molecules.
dominates, the body volume b and
∝
We note this repulsive part of pressure is actually a correction
body volume of the molecules is subtracted from the
over the Ideal Gas equation where the apparent or molecular Figure 11 shows components of the pressure due to repulsion
(first term) and attraction (second term). As the pressure
geometrical volume, resulting in a higher value for the continues to increase a point is reached where the attractive
pressure. Also the ideal gas equation does not account for the forces start to become as strong as the repulsive forces. The
attractive forces that are significant when the molecular repulsive forces are always larger, though, to ensure
spacing is relatively close, like at higher pressures or in liquid thermodynamic stability. Upon compression the body volume
phase. The attractive forces serve to reduce the pressure. effect (which reduces the space available for movement of
molecules) is dominant and results in a higher number density
This gives only a qualitative description of the repulsive so that the first term dominates, although the attractive force
behavior of molecules and the repulsive and attractive serves to reduce the pressure over what it would have been
contributions are not truly separated [1]. Since the van der with only the first term.
Waals equation is not sufficiently accurate for predicting
liquid phase pressures, a more accurate cubic equation can be
achieved based on the work done by Peng and Robinson [5]. It The NIST data appears to only show thermodynamically
8
Benedict Webb Rubin equations can be used to predict with
confidence the PVT behavior of polar molecules [1]. Also a
complex generalized equation of state such as Starling-Han or Figure 12 shows as the pressure increases both NIST and
Benedict Webb Rubin might be more accurate but lack the Peng-Robinson, with the density graphed along side. Both
ability to discern the physical behavour. NIST and Peng-Robinson show a rise in compressibility
followed by a decrease, as the density increases. The phase
change occurs when the density changes fastest.
The Peng-Robinson (1976) [5] equation is:
Figure 13 As the pressure increases both NIST and Peng-
%
such
% %
0.45724 -1 + . /1 0 12
PEAK EXPANSIVITY
And . is a constant characteristic of each substance [5]: values for the attractive coefficient in the van der Waals
Figure 14 shows values for isobaric expansivity for different
.
0.37464 + 1.5422
0.26922
% equation for a hypothetical substance with
Like the van der Waals equation, this implies that the isobaric
van der Waals was selected for this part of the study due to its expansivity and isothermal compressibility are related to each
here using,
1 1 & '
Figure 15 shows comparisons with NIST and the Peng
2
achieved at higher temperature (Figure 16).
For a liquid at high pressure as the pressure is dropped the
compressibility increases and the isobaric expansivity
increases as well. This increase in expansivity continues until
the phase starts to change where it reaches a maximum value
2 2 . 3
0.45724 2 <1 + . =1 > ?@ = 2?
and then begins to decrease. The phase change is characterized
2A
by a sudden drop in both repulsive and attractive forces (see
TABLES
FIGURES
Figure 1 - Isobaric expansivity versus isothermal compressibility for different hydrocarbons at 540 oR
Figure 4 - Ethane for several isotherms, pressures ranging from 145 to 1450 psia
10 BRETT CHRISTIE PSIG 1426
Figure 5 - CO2 for four isotherms and pressures ranging from 145 to 1450 psia
PSIG 1426 On the Correlation between Isothermal Compressibility and Isobaric Expansivity 11
Figure 6 - Propane. Added higher temperature isotherms resolve the curve fully (oR)
12 BRETT CHRISTIE PSIG 1426
1.00E-02
8.00E-03
Isobaric Expansivity (1/°R)
Butane
6.00E-03
Ethane
Propane
Octane
0.9 Ethane 0.1 N Butane
4.00E-03
0.8 Ethane 0.2 N Butane
CO2
Ethylene
2.00E-03
0.00E+00
0.00E+00 1.00E-04 2.00E-04 3.00E-04 4.00E-04
Isothermal Compressibility (1/psia)
Figure 9 - Comparisons for various hydrocarbons at 540 oR for Liquid Phase only.
14 BRETT CHRISTIE PSIG 1426
Figure 11 – Peng-Robinson attractive (all values are negative; hence the absolute values are plotted only) and repulsive
components of pressure. The attractive values try to cancel the repulsive effect, but the repulsive values are always more than
the attractive values.
PSIG 1426 On the Correlation between Isothermal Compressibility and Isobaric Expansivity 15
2.50E-03
2.00E-03
Isobaric Expansivity (1/R)
0
1.50E-03
14561
16987
19414
21841
1.00E-03 24268
26694
29121
31548
5.00E-04
0.00E+00
9.750
8.352
7.040
5.823
4.806
4.145
3.769
3.538
3.380
3.264
3.174
3.099
83.032
57.760
43.696
34.708
28.449
23.818
20.241
17.379
15.018
13.020
11.290
Figure 14 - Isobaric Expansivity versus Specific Volume, for different attraction force coefficients (Van Der Waals) for a
hypothetical substance. Units of a are psia.ft6.oR1/2/kmol2
PSIG 1426 On the Correlation between Isothermal Compressibility and Isobaric Expansivity 17
Figure 15 - Comparisons for Ethene at 540 oR (81.3 oF), NIST versus Peng-Robinson. NIST density is shown as well.
Figure 16 - Comparisons for Ethene at 567 oR (107 oF), NIST versus Peng-Robinson. NIST density is shown as well.
18 BRETT CHRISTIE PSIG 1426
Figure 17 - N-Butane Correlation – shows liquid and gas phase data, but no intermediate values (585 oR).
Figure 18 - N-Butane zoom in on liquid phase shows linear behavior (585 oR)
PSIG 1426 On the Correlation between Isothermal Compressibility and Isobaric Expansivity 19
Figure 19 - Isotherm for Ethene at 540 oR (81 oF) and pressure (right axis) graphed against isothermal compressibility. Low
pressure corresponds with high isothermal compressibility. As pressure increases the isobaric expansivity slowly increases in
gas phase, then as the phase transitions to liquid, increases dramatically.
END OF PAPER