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ENCH 607 Lecture 1

Introduction and Equations of State

Introduction
Natural gas produced from formations is unlikely to be able to be put into a
pipeline and sold for consumption. Depending on the reservoir the gas will
contain water, a mixture of hydrocarbons from methane to C30+, acid gases such
as CO2 and H2S, non-condensable gases such as N2, H2, and He, and trace
sulphur compounds such as mercaptans, COS, and CS2. Some gas streams
may also contain elemental sulphur, asphaltenes, diamonoids, or wax. All
product streams from a gas treating facility are required to meet certain
specifications and as such treatment is required to remove or separate the
various components. In order to treat gas, two critical pieces of information are
required: the gas you are starting with, and the specifications of the products you
are required to make.

Raw Gas Composition


When a project is being conceived, a Reservoir Engineer may have some
indication of the expected gas composition based on well analogues. Once a
well is drilled the composition may be determined by testing the well. If the well
is sweet, a long period of testing may be possible, resulting in an accurate
composition. Production testing of sour wells is problematic due to
environmental considerations and sour gas test results are often less accurate.
Although the plant process flow drawing will show one composition for the raw
gas feed, it should be remembered that this is usually only a best guess, and the
actual feed gas composition will vary. In some reservoirs the gas composition
from individual wells varies and the inlet composition is dependant on the relative
flow rates. Variation may also result if a plant is fed from multiple reservoirs, or
as a result of retrograde condensation in the reservoir as the field is produced.
When adding compression to a field that has been producing for years, the gas
composition can be expected to be accurate. There are a number of important
items to consider when looking at the raw gas.

Water Content
Most reservoirs are saturated with water at reservoir conditions and as the gas is
produced to surface both temperature and pressure decrease. Decreasing the
temperature reduces the ability of the gas to hold water in the vapour phase,
while decreasing the pressure has the opposite effect. The net effect is usually
condensation of water from the gas stream. If the gas composition and reservoir
conditions are known, the amount of water is easy to calculate. Many gas
reservoirs are underlain by an aquifer containing brine. Generally Reservoir and
Production Engineers try to perforate and produce the well to avoid producing
any of this connate water. In reality the total water produced may be a

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combination of water of condensation and connate water, which may also
change over time. Measuring chloride content of the water provides a means to
estimate the ratio of each type of water produced.

Hydrocarbon Content
The hydrocarbon content is usually determined by doing a well test where the
well is produced into a series of test separators operating at different pressures.
The flow rates and compositions of the liquid and gas streams are determined
and then recombined to give the overall composition. Gas and liquid analyses
are done using gas chromatographs. Identification of the lighter components C1
through C5 is strait forward. The heavier components are somewhat trickier, as
there is a difference if the C6 component is hexane or benzene. A good analysis
should identify these individual components. This allows the designer to base
detailed calculations on a detailed analysis, or to lump components when the
details are not required.

Acid Gas Content


The acid gases, H2S and CO2 are usually determined as part of the hydrocarbon
analysis. When the H2S content is in the ppmv range, it is important to take the
sample into a Teflon lined bomb and have the analysis done quickly. Failure to
do this may result in the H2S reacting with the wall of the bomb giving low H2S
results. Believing that there is little or no H2S present in the gas stream may
result in the wrong process design and failure to meet the required produce
specifications.

Trace Sulphurs
Trace sulphurs usually refer to mercaptans (RSH), carbonyl sulphide (COS),
carbon disulphide (CS2), and various disulphides (RSSR). These are more likely
to be found when the gas contains H2S. Identification of these compounds is
important as they behave differently than H2S in various treating processes, and
will impact the total sulphur content of the treated products. Specialized
sampling and analysis is required to obtain an accurate assessment.

Elemental Sulphur
Reservoirs that contain H2S often contain elemental sulphur that is tied up with
the H2S in the form of hydrogen polysulphides (H2Sx). The maximum amount of
H2Sx that may be present is a function of temperature, pressure, and H2S
concentration. The actual amount of H2Sx present may however be less than the
maximum. As the gas is produced to surface the temperature and pressure
decrease shifting the polysulphide equilibrium. The shift in the equilibrium may
result in the deposition of elemental sulphur if the saturation point is reached.
Sulphur may deposit as a liquid or solid depending on the local temperature.
Deposition may occur in the reservoir or in the production tubing. Deposition is
more like to occur and cause problems when the raw gas is very light and lacks
heavy hydrocarbon components. The heavy hydrocarbon components will
dissolved the sulphur or at least transport it in the tubing. The amount of

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polysulphide present is determination by taking a downhole sample at reservoir
conditions. Alberta Sulphur Research Ltd. (ASRL) has the equipment and skills
to complete this sort of testing and analysis.

Product Specifications
The main product of a treating facility is usually sales gas that is delivered to a
pipeline for transportation to markets. Liquid products may be delivered in a
variety of ways. The lighter streams can be delivered as mixed streams like
Natural Gas Liquids (NGLs), or Liquified Petroleum Gases (LPGs). These lighter
streams might also be delivered as fractionated stream like ethane, propane, or
butane. Ethane and NGLs are delivered by pipeline due to their high vapour
pressure. LPGs, propane, and butane can be delivered by pipeline, truck, or rail
car. The heavy hydrocarbon stream is produced as a condensate stream (C5+)
and can be shipped by pipeline, truck, or rail car.

Sales Gas
The detailed sales gas specifications that must be met are determined by the
particular pipeline company. Standard gas conditions at 15 oC and 101.325
kPa(abs). Typical Alberta sales gas specifications are given below, but one
should always refer to the specific sales gas contract.

Typical Sales Gas Specifications


Specification SI value Traditional value

Higher Heating Value (minimum) 34.5 MJ/Sm3 950 BTU/scf


H2S Content (maximum) 23 mg/Sm3 1 grain/100 scf
Total Sulphur (maximum) 115 mg/Sm3 5 grain/100 scf
Hydrocarbon Dew Point (minimum) -10 oC @ 15 oF @
5500 kPa(abs) 800 psia
Water Content (maximum) 65 mg/Sm3 4 lb/MMscf
Delivery Temperature (maximum) 49 oC 120 oF
Delivery Pressure (minimum) 6200 kPa(g) 900 psig
CO2 2% by volume 2% by volume

Oxygen, and mercaptans might also be specified in some contracts, and there is
usually a clause prohibiting “waxes, gums, and other deleterious substances”.
Contracts may also specify a Wobbe index, which is:

HHV
WobbeIndex =
SpecificGravity

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NGLs
NGLs are a mixture of hydrocarbons, usually in the C2-C4 range that are
recovered at cryogenic temperatures and sent to another location for
fractionation into separate products. A typical NGL specification is:

Ethane
Ethane is a fractionated product containing primarily C2H6. A typical specification
for ethane is:
C2H6 95 mole% minimum
CO2 2.0 mole% maximum
CH4 2.0 mole % maximum
C3H8 2.0 mole % maximum
H2S 100 ppmw maximum
Total Sulphur 200 ppmw maximum

LPGs
LPGs are liquefied petroleum gases recovered by cooling a gas stream with a
refrigerant. The product is a mixture of propane and butane if recovered at a gas
plant, and may contain propylene and butylenes if recovered from a refinery.
LPGs may be fractionated and sold as separate products. Typical specifications
are:

Typical LPG Specifications


Specification Commercial Commercial Commercial B-P
Propane Butane Mixtures
Vapour Pressure 1434 kPa(g) 483 kPa(g) 1434 kPa(g)
at 37.8 oC
Residue 2.5 vol% butane 2.0 vol% C5+ 2.0 vol% C5+
o o
95% boiling point -38.3 C 2.2 C 2.2 oC
Corrosion No. 1 Copper strip No. 1 Copper strip No. 1 Copper strip
Total Sulphur 185 mg/kg 140 mg/kg 140 mg/kg
Water Content No free water No free water No free water

Condensate (C5+)
Condensate or Pentanes plus is usually just the heavy ends recovered from a
gas processing facility. Typical specifications include a Reid vapour pressure
(RVP), a maximum butane content, maximum basic sediment and water
(BS&W), maximum density, and a maximum H2S content. The Reid vapour
pressure is the pressure exerted by a sample at 100 oF. Typical numerical
values are:
RVP 90 kPa(abs) max
BS&W 0.5 vol% max

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Butane 5 vol% max
Density 927 kg/m3 max
H2S 20 ppmw max

Sulphur
Sulphur is produced as a liquid product if H2S is present in the feed gas.
Sulphur may be transported as liquid in trucks or rail cars, but most sulphur is
sold as a solid. Typical sulphur specifications are:
Purity 99.5% by weight (dry basis)
Acidity < 0.05% by weight (as H2SO4)
Moisture < 1.0% by weight
Ash <0.1% by weight
Carbonaceous matter <0.15% by weight
Arsenic <0.25 ppmw
Selenium <2.0 ppmw
Tellurium <2.0 ppmw
Colour Bright yellow at ambient temperature.

There is current no North American specification for H2S in a sulphur product, but
degassing is becoming more common. Many facilities provide sulphur with an
H2S content below 10 ppmw.

Water
Water produced from the reservoir usually has to be disposed of by deep well
injection. There is no standard specification for the product but some
specifications may be required depending on the particular disposal option.
Reservoir engineers are likely to want the water to be filtered so that there are no
particles larger than 10 microns. Disposal by off site trucking or storage in
vented atmospheric tanks may require that the H2S content be below 10 ppmw.

Treating Requirements
The treating required by a particular stream is dependant on the raw feed gas
and the product specifications. The feed gas is subject to uncertainty, but the
product specifications should be well defined. There may however be cases
when product specifications may be variable. This may occur when a product
may be sold into two markets with different specifications. The treating scheme
must be able to handle the variation in feed composition to deliver specification
products. If products are not on spec, they must either be flared, reprocessed, or
sold at a discount. Another consideration in determining the treating
requirements is the local infrastructure available. Recovery of a separate LPG
product may not be worthwhile if shipping the product from site is prohibitively
expensive.

Gas not meeting a specification, especially the H2S spec must be flared as there
is no storage or resale option. Flaring means a loss in sales revenue and often
has implications with the public. Although the flared gas may be almost sweet,

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the sight of a large fire ball on the end of a flare stack does not bode well with the
community.

It may be possible to reprocess NGL, LPG, and Condensate streams if a rerun


pump is available to bring the stored product back into the processing train, and if
there is spare capacity in the unit. If reprocessing is not available it may be
necessary to sell the product at a discount.

Sulphur not meeting the specification may be sold at a discount, but more likely
will need to be disposed of in an industrial landfill.

Physical Properties
Engineering problems often require physical properties of the fluids in order to
arrive at a proper design. Most engineering calculations are now done on
computers and there is often little opportunity for the engineer to become
proficient in the application. It is important to understand the fundamentals that
govern the many applications that are employed. When using computer
programs, there are a number of “laws” that are worth remembering:

1. The utility of a computer calculation is limited by the user’s knowledge of


the system and not by the capability of the computer.
2. The precision of an answer can be no better than the worst input data.
3. There is no such thing as a single equation or program that is equally valid
for all compositions and all physical conditions.
4. The validity of a computation is not necessarily proportional to its
complexity.

With the above in mind, it is often worthwhile to perform hand calculations prior to
starting a computer simulation, or to check the validity of results after you have
done some preliminary computer calculations.

Fundamental Concepts
The most important fundamental concepts that will be covered are:
• Physical properties of fluids and solids.
• Vapour-liquid-solid behaviour of a substance as a function of pressure,
temperature. and composition.
• The concept of equilibrium.
• The use of equations of state to predict the behaviour and properties of
systems.
• The use of mixing rules for the prediction of mixture behaviour from that of
the individual components of the mixture.
• Thermodynamic concepts that govern the conservations laws of energy
and matter.
• Rate equations that express the speed of a process in terms of driving
force and resistance to change.
• The molecular theory of matter.

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Units of Measurement
Canada has been using the System International (SI) units in the Oil & Gas
industry since about 1978. Because of close ties with the United States, where
the Imperial system (FPS) is used, there will be many instances where unit
conversions are required. We will use SI for essentially all of our work, but
occasionally data may come in other units. A number of unit conversion
programs and website can easily be found.

Mass, force, and weight


If relativistic effects are ignored, the mass of a body is a measure of the quantity
of matter. Most common units are kilograms, with tonnes, grams, milligrams, and
micrograms being common. In the FPS system, tons, pounds, ounces, and
grains are commonly used.

Force is required to accelerate a mass. The relationship between force and


mass is:

ma
F=
g

where: m = mass (kg)


a = acceleration (m/s2)
g = proportionality constant for force (kg·m/N·s2)

In SI unit of force is the Newton.

Weight is a term that should be avoided even though it is often used to denote
mass. Weight is a measure of the attraction of gravity on a given mass. The
standard acceleration of gravity is: gc = 9.81 m/s2.

Length, area, and volume


The standard unit of length is the metre (m). Other units are millimetre (mm),
centimetre (cm), decimetre (dm), and kilometre (km).

1 m = 1000 mm = 100 cm = 10 dm = 0.001 km


1 m = 3.28 ft, 1 ft = 0.305 m

Area is expressed in the same length units squared.


m2, mm2, cm2, dm2,km2

1 m2 = 1x106 mm2 = 100 dm2 = 10.76 ft2

The basic volume term is the cubic metre, m3. The litre (L) is an allowable term
for the cubic decimetre. The API barrel (bbl), which is 42 U.S. gallons is not part
of the SI system but is widely used in the industry.

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1 m3 = 1000 dm3 = 1000 L = 35.31 ft3
1 bbl = 0.159 m3 = 159 L = 5.61 ft3 = 42 U.S. gal = 35 U.K. gal

Density
The usual units are kg/m3 or lbm/ft3. Density is a function of temperature and
pressure, so standard or reference density is usually reported at standard
atmospheric pressure and some temperature like 0 oC, 15 oC, 25 oC, 60 oF, and
77 oF. For most engineering calculations standard density is adequate. For
custody transfer and gases, an actual density is required.

1 kg/m3 = 0.0624 lb/ft3

Relative density is the density of the system divided by that of a reference


substance at specified conditions. Relative density is the SI term for specific
gravity. The reference for liquids is water; for gas it is air.

ρliquid ρ gas M gas


γL = γg = =
ρ water ρ air M air

where: M = molecular mass

The relative density for oil may be expressed in oAPI. The equation is:

141.5 141.5
γL = o
API = − 131.5
131.5+ oAPI γL

Pressure
Pressure is the force exerted per unit area. The standard term for pressure is the
pascal (Pa) = 1 N/m2. This is a small pressure unit, so kilopascal (kPa) and
megapascal (Mpa) are commonly used. In Europe it is common to use the term
bar, which is 100 kPa.

Absolute pressure is used in most engineering calculations. In FPS an “a” is


added to denote absolute pressure (psia) and a “g” is added to denote gauge
pressure (psig). In SI, it is common to use no suffix for absolute pressure, so that
P = 150 kPa implies an absolute pressure. In some instances absolute
pressures are written as kPa(abs). A gauge pressure would be written as 49
kPa(g).

100 kPa = 1 bar =0.987 atm = 14.50 psia


14.696 psia = 1 atm (std) = 101.325 kPa = 1.01 bar

Fluid head
A vertical column of fluid exerts a pressure on the bottom. This head, expressed
as a length can be converted to a pressure by the equation:

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P = A·ρ·H·gc/g

Where: P = pressure (kPa)


A = unit conversion factor (pascal to kilopascal) (0.001)
ρ = density (kg/m3)
H = height (m)
gc = acceleration due to gravity (9.81 m/s2)
g = proportionality constant (1.0 kg·m/N·s2)

Temperature
The SI units are degrees Celsius (oC) and Kelvin (K). The term centigrade is
obsolete.

K = oC + 273.15
o
C = (oF - 32) / 1.8
o
F = 1.8 x oF + 32
o
R = oF + 459.67

Degrees Fahrenheit (oF) and Rankin (oR) are the units in the FPS system.
Absolute temperatures are used in most engineering calculations.

Work and power


The units of work are force times distance. Power is the time rate of performing
work. The standard SI unit of work is the joule (J) = 1 N·m. The joule is a small
unit so kilojoule (kJ) and megajoule (MJ) are normally used.

1 kJ = 0.001 MJ = 737 ft-lbf

Engineers are concerned with the rate of doing work, or power. The watt (W)
and horsepower (hp) are the most common units.

1 W = 1 J/s 1 kW = 3600 kJ/h = 1.34 hp


1 hp = 0.746 kW = 2686 kJ/h

Heat energy
Heat energy must have the same units as work and power in order to make
calculations involving the conversion between them. In SI the joule is also used
for heat energy, while the British Thermal Unit (Btu) is used in the FPS system.

1 kW = 3600 kJ/h = 3412 Btu/h

Energy per unit mass is expressed in kJ/kg and Byu/lbm

1 Btu/lbm = 2.326 kJ/kg = 6.46 x 10-4 kWh/kg

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Viscosity
The dynamic viscosity is a shear force per unit area. The poise was the original
unit; 1 poise = 1 dyne-sec/cm2. For petroleum systems the centipoises (cp) is
the most convenient unit. In SI the Pa·s is the preferred unit.

1 cp = 0.001 Pa·s = 0.001 kg/(m·s) = 6.72 x 10-4 lbm/(ft-sec)

Kinematic viscosity is dynamic viscosity divided by density with the primary unit
being centistokes (cSt).

1 cSt = 1 mm2/s = 1.08 x 10-5 ft2/sec

Equations of State
Any equation that relates pressure, temperature, and volume is called an
equation of state. This all started with the Boyle-Charles law that stated pressure
times volume is proportional to temperature.

Ideal gas law


Adding a proportionality constant (R) normally called a universal gas constant
gives a practical form:

PV = nRT

Where: P = pressure (kPa)


V = volume (m3)
n = amount of substance (kmol)
T = temperature (K)

This is known as the ideal gas law and is valid for pressures up to about 400
kPa. If n = 1, the “V” is the molar volume and is designated as “v”. If “V” is a
mass specific volume (reciprocal density), then “n” is the reciprocal of molecular
mass.
P/ρ = RT/MW

The value of R is 8.3145 kPa·m3/kmol·K

The ideal gas law is used to calculate the standard volume of a gas (Sm3). SI
standard conditions are 15 oC and 101.325 kPa. Some gas volumes are given at
normal conditions, which are 0 oC and 101.325 kPa.

Compressibility factor
Because of its simplicity, the ideal gas law is often corrected by using a
compressibility factor, z. The equation then becomes:

PV = znRT

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One must then determine z for the gas. A number of methods are applicable, but
the concept of corresponding states must first be addressed.

Corresponding states
The corresponding states concept states that physical and thermodynamic
properties are related to the critical properties in a universal way.
Mathematically, if an equation of state for any fluid is written in terms of reduced
properties, that equation is also valid for any other fluid. The reduced properties
are defined as:

Tr = T/Tc Pr = P/Pc vr = v/vc

Where “r” denotes the reduced property and “c” denotes the critical property.
Critical properties can be found for many hydrocarbons in Chapter 23 of the
GPSA Engineering Data Book.

The concept of corresponding states is illustrated by the charts below.

10000

1000 Pressure kPa

Methane
100
Propane

10

1
-200 -150 -100 -50 0 50 100
Temperature C

When the vapour pressure curves for methane and propane are plotted, they
show a large deviation as shown above.

If the same curves are plotted on reduced parameter scales they align much
more closely as shown below.

The correlation is not perfect, and a third parameter, the Pitzer acentric factor, ω,
is often used. The parameter ω is defined as:

ω = -log(Pr) - 1

where: Pr = P*/Pc; P* is the vapour pressure at T = 0.7 Tc

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The acentric factor is a measure of the difference between the reduced vapour
pressure of a component at Tr = 0.7 and the reduced vapour pressure of an ideal
molecule at Tr = 0.7, which is Pr = 0.1

1.0000
Reduced Pressure

0.1000

Methane
0.0100
Propane

0.0010

0.0001
0.00 0.20 0.40 0.60 0.80 1.00
Reduced Temperature

Katz correlation and Kay’s rule


This is the simplest method to calculate z. The correlation of Katz et al for lean
sweet natural gas is given in FIG. 23-4 in the GPSA Engineering Data Book. To
use the correlation the pseudo-critical properties for the gas mixture are used to
determine the pseudo-reduced properties. Kay’s rule is a mole weighted
average and states:

Pc' = ∑ yi Pci and Tc' = ∑ yiTci

where: yi = mole fraction of component in gas phase


Pci and Tci are the critical values for each component

The pseudo-reduced pressure and temperature are then:

Pr' = P / Pc' and Tr' = T / Tc'

Kay’s rule also applies to the molecular mass:

MW ' = ∑ yi MWi

An example calculation is presented in FIG. 23-3 of the GSPA Engineering Data


Book.

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Modifications for sour gas
When the gas contains appreciable quantities of H2S or CO2 the Katz correlation
is modified by applying one of two methods:
• Robinson et. al
• Wichert and Aziz

Robinson’s approach was an earlier work based on limited data, and the work by
Wichert and Aziz is usually used. The method applies a correction factor to the
pseudo-critical parameters calculated using Kay’s rule. The correction factor, ε is
a function of the mole fraction of H2S and CO2 in the gas and is presented in FIG.
23-8 in the GPSA Engineering Data Book. Once ε is determined, adjusted
critical parameters are calculated as follows:

Pc'Tc''
Tc'' = Tc' + ε Pc'' =
Tc' + B(1 − B )ε

where: Tc'' and Pc'' are adjusted pseudo-critical values


Tc' and Pc' are pseudo-critical values calculated from Kays rule
ε is from FIG. 23-8
B is the mole fraction of H2S in the gas

The value of ε in figure 23-8 can be estimated by the equation:

ε = 66.67( A0.9 − A1.6 ) + 8.33( B 0.5 − B 4 )

where A is the mole fraction of H2S plus CO2 in the gas

Benedict-Webb-Rubin (BWR) Equation


The BWR equation was developed in 1940 and modified by Starling (BWRS) in
1970. It is rather cumbersome because of all the terms and is suitable only for
computerized calculations. The form of the equation is:

cρ 3
⎛ C D E ⎞ ⎛ d⎞ ⎛ d⎞
( )
P = RTρ + ⎜ B0 RT − A − 02 + 30 − 04 ⎟ ρ 2 + ⎜ bRT − a − ⎟ ρ 3 + ⎜ a + ⎟αρ 6 + 2 1 − χρ 2 e − χρ
T⎠
2

⎝ T T T ⎠ ⎝ T⎠ ⎝ T

Coefficients for the equation can be found in Younger’s notes.

Cubic equations of state


Cubic equations of state have in them a volume term raised to the third power.
They are widely used due to their ease of use and the performance they provide.
When the roots of a cubic equation of state are found, one real root is the volume
of the vapour, while the other is the volume of the liquid. Three of the most used
cubic equations of state are given below. The constants used are functions of
the critical temperature and pressure, and usually a third parameter, ω, the

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acentric factor. For mixtures of gases, mixing rules must be applied to the
constants. For cubic equations of state the mixing rules are:

am = ∑∑ xi x j (ai a j ) (1 − k ) bm = ∑ xibi
1/ 2
ij

where: am and bm = the a anb parameters for the mixture


ai, aj, bi = a and b parameters for any component
xi, xj = mole fraction for any two components
kij = binary interaction parameter

Once am and bm are determine the calculations are done as if a and b were for a
pure component. The binary interaction parameters kij has no theoretical basis,
but is regressed from experimental data.

van der Waals

RT a
P= − 2
v−b v

where: a and b = correlation constants


v = molar volume

Redlich-Kwong

RT a
P= − 0.5
v − b T v (v + b)

Peng-Robinson

RT aT
P= −
v − b v (v + b) + b(v − b)

Homework Assignment
Younger’s 607 Notes – Chapter 1 – Introduction
GPSA Engineering Data Book – Section 1 – Introduction
GPSA Engineering Data Book – Section 2 – Product Specifications
GPSA Engineering Data Book – Section 23 – Physical Properties, pages 23-1 to
23-17
Problem Assignment #1

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