ENCH607 F2021 L01 Introduction&Equations of State

Introduction and equations of state
Nashaat Nassar, PhD, PEng, Professor
ENCH 607-Lecture-01
September 9th, 2021

Objectives
By the end of this lecture, students will gain

knowledge of:
q Energy outlook
q Components found in petroleum stream
q Typical gas product specifications
q Units of measurements
q Ideal and real gas equations of state
q Skills in using simple equations of state to
calculate gas volumes and density
ENCH 607-Dr. Nassar 2
Energy outlook
Energy consumption is Energy demand will decline

increasing by 70% by 5%
Most of the projected growth in energy demand will come from developing (non-
OECD) countries.
Image courtesy: CEP August 2015 www.aiche.org/cep

Energy outlook
NG and RE will be the forecast-growing fuel sources for electric power generation
over the 2015-2040 time period.

Energy outlook
U.S. Energy Trends
• The decline in U.S. energy

demand occurs mainly in
the transportation and
electricity generation
sectors.
• Significant efficiency gains

are expected for
passenger vehicles due to
fuel economy mandates.
• The average new U.S. car

in 2040 is expected to get
about 47 mpg on-road,
compare to 24 today.

Energy outlook
U.S. Energy Trends
• Demand for NG
will increase
over 2010-2040
time period, with
the majority of
the growth
coming from the
electricity
generation
sector.

Energy outlook
• Natural gas production is expected to grow in almost all regions of the world.
• Several majors are anticipated:
• Asia Pacific will likely overtake Europe as the world’s largest importer
• North America is expected to emerge as an exporter of NG by 2020
• The Russia/Caspian region is forecast to remain a significant exporter
Access to unconventional gas production will change the import-export

trade balance globally
ENCH 607-Dr. Nassar Image courtesy: CEP August 2015 www.aiche.org/cep 7
NG: Chemical Synthesis
• Plentiful, low-cost natural gas will invigorate the

chemicals industry over the next decade, as
producers look to increase the role of NG as
feedstock in established processes, as well as
develop new processes to convert methane into
chemicals currently derived from petroleum.

• Petrochemicals
derived from
petroleum and NG
are building blocks
for a variety of
important end
products.

Steam cracking
• The two-process approach is inherently inefficient.

• Steam cracking of NGLs produces propylene and
butylene, but not a sufficient quantity of these materials
to meet market demand.

• Technologies are being developed and demonstrated that in the future will allow
many basic building blocks of the chemicals industry to be produced directly and
more efficiently from NG and NGLs.
Natural gas composition and
carbon footprint
Unprocessed natural gas Gas is “the cleanest” hydrocarbon fuel
CO2 emissions per energy unit

Indexed, coal = 100
Sources: Canadian Centre for Energy Information; UK Department for Environment, Food and Rural Affairs; XTO; IPCC
When were gas and oil produced?
Image courtesy: Kjell Aleklett, Unconventional Oil & Gas 2012 TaiYuan 2012-09-24

Natural gas
q Natural gas is defined as gas obtained from a
natural underground reservoir. It generally contains:
q Large quantity of methane along with heavier
hydrocarbons, such as ethane, propane, isobutane,
normal butane, etc (up to C30+)
q Considerable amount of non-hydrocarbons, such as
nitrogen, hydrogen sulfide and carbon dioxide.
q Traces of helium, carbonyl sulfide (COS) and various
mercaptans (CS2).
q Others, such as elemental sulfur, asphaltenes, wax,
etc.
q It is also generally saturated with water

Raw gas compositions
Source: A. H. Younger, Natural gas processing principles and technology

Example Pipeline Quality Natural Gas
Source: Fig 4 (GPSA Engineering Data Book)

Why Natural Gas Processing
q Gas that is sold for commercial use is different in

composition to that given in the previous slide.
From a field From a straddle

plant (mole%) plant (mole%)
N2 0.30 0.35
C1 91.63 98.60
C2 5.72 1.05
C3 1.63 -
iC4 0.29 -
nC4 0.31 -
iC5 0.12 -

Why Natural Gas Processing?
qAll acid gas compounds, H2S and CO2, should be

removed.
qAll the free liquids, both hydrocarbons and water,
should be removed.
qGenerally, hydrocarbons heavier than pentanes
are removed as well as considerable amount of
propane and butane.
qFor gas treatment two important factors need to
be considered:
qThe starting gas specifications (natural gas)
qThe final product specifications
Why Natural Gas Processing
qThe removal of acid gases, water and

hydrocarbon compounds from natural gas
requires an understanding of the followings:
qFluid flow
qThermodynamics
qHeat and mass transfer
qDistillation
qAbsorption
qAdsorption
qOthers ENCH 607-Dr. Nassar 19
Water content
q Most reservoirs are saturated with water at reservoir

conditions. However, as the gas moves to surface both
temperature and pressure decrease.
q Decreasing the tempà reduces the gas ability to hold
water in the vapour phase.
q Decreasing the pressure à increases the gas ability to
hold water in the vapour phase.
q The net effect: condensation of the water in the gas
stream.
q In practice, the total water produced is a compotation of
water of condensation and connate water.
q Measuring the chlorine content of the water provides a
means to estimate the ratio of each type of produced
water. ENCH 607-Dr. Nassar 20
Hydrocarbon content
q Gas and liquid hydrocarbon analyses are performed

using gas chromatographs.
q Identification of lighter components (C1 to C5) is
straightforward.
q Heavier components are trickier and challenging (e.g.,
C6 is it hexane or benzene?)
q Careful and detailed analysis is required.
q Lump components when detailed calculations are not
required.
q Hydrocarbon components of NG are either
q Aliphatic (chain)
q Aromatic (cyclic)

Aliphatic hydrocarbon
q Occurs in two forms:
q Saturated hydrocarbon (Paraffin)
q Unsaturated hydrocarbon (Olefin)
q Paraffinic hydrocarbons are the most common compound in NG
q General formula (CnH2n+2)
q Isomers is likely to present, when the carbon atoms is four or more.

Aliphatic hydrocarbon: Olefin
q Olefins have a single carbon-carbon double bond.

q General formula (CnH2n)
q Occurs only in trace amounts in reservoirs
q Isomers is likely to present, when the carbon atoms is four or more.

Cyclic or Ring Hydrocarbons
q Occurs only in trace amounts in reservoirs
q They are of two kinds:
q Naphthenic: saturated cyclic hydrocarbons with the general formula
(CnH2n)
q Aromatic: unsaturated cyclic hydrocarbons

e.g., BTEX

Acid Gas Content
qAcid gases, H2S and CO2, are usually

determined as part of the hydrocarbon analysis.
qH2S: is poisonous and can cause pipe corrosion
and catalysts decaying.
qSweetening: is the process of removing the H2S
gas, where the H2S content is reduced to < 16
ppmv.
qCO2: is not nearly undesirable, but it can cause
corrosion as well, especially in the presence of
water.

Trace Sulphurs
qThis usually refers to the following compounds:

q Mercaptans (RSH)
qCarbonyl sulphide (COS)
qCarbon disulphide (CS2)
qVarious disulphide (RSSR)
q likely to be found when the gas contains H2S
q Special solvents are required in the sweetening
processes to remove marcaptans.

Elemental Sulphur
qIt is often tied up with H2S in the form of

hydrogen polysulphides (H2Sx).
H2S + (x-1)S « H2Sx
qThe max amount of H2Sx is a function of
temperature, pressure and H2S concentration.
q The actual amount is usually less than the max.
q As the gas is produced to surface the temp and
pressure decrease shifting the H2Sx equilibrium.
q Deposition of elemental sulphur is likely to occur
q Heavy hydrocarbons dissolve sulphur

Other compounds
q Produced gas can also contain: hydrogen, helium,

nitrogen, mercury, diamonoids, asphaltenes, gum
and wax.
q Hydrogen and helium are found in trace amount. No
attempt is made to remove hydrogen, but helium can
be recovered if its in high concentration.
q Small amount of nitrogen is not problem, but at high
concentration it should be removed.
q Mercury has to be removed for occupational health
and materials reasons.
q Diamonoids, asphaltenes gum and wax can cause
pipe plugging.
Product specifications

Product specifications: Sales Gas
Table 1.2: Typical Pipeline Composition (dry basis)

From a field plant From a straddle plant
(mole%) (mole%)
N2 0.30 0.35
C1 91.63 98.60
C2 5.72 1.05
C3 1.63 -
iC4 0.29 -
nC4 0.31 -
iC5 0.12 -
q Straddle plants are specifically designed to recover

components heavier than methane.
q Straddle plant can be part of a gas plant, but also located
on main transmission lines for economic reasons.

Typical Alberta Sales Gas Specifications
q Standard gas conditions for System International (SI): 15

oC and 101.325 kPa

q In some contracts:
q Oxygen and mercaptans might also be specified
q Waxes, gums and other substances is usually prohibited
q Wobbe index is specified:
= higher heating value/(square root of gas specific gravity)
𝐻𝐻𝑉
𝑊𝑜𝑏𝑏𝑒 𝐼𝑛𝑑𝑒𝑥 = (𝐸𝑞 1.1)
𝑆𝑝𝑒𝑐𝑖𝑓𝑖𝑐 𝐺𝑟𝑎𝑣𝑖𝑡𝑦
qThe Wobbe Index is a critical factor to minimize the

impact of the changeover when analyzing the use of
substitute natural gas (SNG) fuels.
q HHV (J/m3) is required so that the consumer can properly set
the firing equipment. The producer is paid based on the HV of
the gas ENCH 607-Dr. Nassar 32
q H2S content: Required for safety, corrosion control and
environmental concerns.
q Total Sulphur & Mercaptans: Required primarily for
environmental concerns. Sulphur compounds can also
be catalyst poison for some processes using natural gas
as a feedstock.
q Hydrocarbon Dew Point: This specification is required to
prevent the condensation of liquid hydrocarbons in
pipelines taking the gas to markets.
q Water Content: This specification is required to prevent
the condensation of water in the pipeline. Free water can
lead to corrosion and is conducive to the formation of
hydrates that can block the pipe.
q CO2 Content: Set primarily to prevent corrosion and keep
the Wobbe index and heating value within specification.
q Oxygen Content: This is a holdover specification from
manufactured gas specifications and oxygen is not
normally present in the gas stream. When oxygen does
get into a natural gas stream it can react with any H2S
present and form elemental sulphur.
q Delivery Temperature: This is set to protect pipeline
coatings.
q Delivery Pressure: This is set so that the transmission
company can design the pipeline system. Higher
pressure is better for transmission.

Typical Alberta Sales Gas Specifications:
NGLS
q NGLs: are a mixture of hydrocarbons, usually in the C2-
C4 range that are recovered at cryogenic temperatures
(low-temperature phenomena, from -150oC to absolute
zero temp) and sent to another location for fractionation
into separate products. A typical NGL specification is:
Methane and lighter 1 mol% maximum

H2 S No. 1 copper strip*
CO2 500 mg/kg
Total sulphur 200 mg/kg
Moisture No free water
*Copper strip test: A qualitative method of determining the corrosivity of a
petroleum product by observing its effect on a strip of polished copper
suspended or placed in the product.
Ethane
q Ethane: is a fractionated product containing primarily
C2H6. Atypical specifications for ethane is
C2H6 95 mol% min

CO2 2.0 mol% max
CH4 2.0 mol% max
C3H8 2.0 mol% max
H2S 100 ppmw max
Total Sulphur 100 ppmw max

LPGs
q 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.
q LPGs may be fractionated and sold as separate products.
q Typical specifications are given in Table 1.4

Condensate (C5+)
q Condensate or Pentanes plus is usually just the heavy ends
recovered from a gas processing facility. Typical specifications
include:
q Reid vapour pressure (RVP, common measure of the volatility of the
gasoline). The Reid vapour pressure is the pressure exerted by a
sample at 100 oF, in a specialized instrument.
q Maximum butane content
q Maximum basic sediment and water (BS&W)
q Maximum density
q Maximum H2S content. Typical numerical values are:
RVP 90 kPa max

BS&W 0.5 vol% max
Butane 5 vol% max
Density 927 kg/m3 max
H2 S 20 ppmw max
Sulphur
q 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.
q Sulphur not meeting the specification may be sold at a discount, but more
likely will need to be disposed of an industrial landfill. Typical sulphur
specifications are:
Purity 99.5 wt% (dry basis)

Acidity < 0.05 wt% (as H2SO4)
Moisture < 1.0 wt%
Ash < 0.1 wt%
Carbonaceous matter < 0.15 wt%
Arsenic < 0.25 ppmw
Selenium < 2.0 ppmw
Tellurium < 2.0 ppmw
Colour Bright yellow at ambient temperature
Note: Currently, there is no North American specification for H2S content in a sulphur
product, but degassing is becoming more common. Many facilities provide sulphur
with an H2S content below 10 ppmw.
Physical Properties:
Fundamental Concepts
The most important fundamental concepts that will be covered are:
q Physical properties of fluids and solids.
q Vapour-liquid-solid behaviour of a substance as a function of pressure,
temperature and composition.
q The concept of equilibrium.
q The use of equations of state to predict the behaviour and properties of
systems.
q The use of mixing rules for the prediction of mixture behaviour from that of
the individual components of the mixture.
q Thermodynamic concepts that govern the conservation laws of energy and
matter.
q Rate equations that express the speed of a process in terms of driving force
and resistance to change.
q The molecular theory of matter.

Amount of a substance
q All matter is composed of elements, which cannot be broken down or

subdivided by ordinary means and still retain the same properties.
q The atom is the basic unit of each element that can combine with
itself or the atoms of other elements to form a compound.
q A compound is a substance composed of more than one atom that
satisfies the followings:
q The atoms have combined chemically
q The compound has properties different from the atoms from
which it is formed
q Chemical compounds form in the simplest possible numerical
proportions, and a molecule is the unit of a compound. A molecule of
water contains two atoms of hydrogen and one atom of oxygen, and
is written as H2O.

The mole concept
q The term “mol” is the historic abbreviation of the words
“gram molecule”. The current definition of the mol is: “the
amount of substance of a system which contains as
many elementary entities as there are atoms in 0.012
kilogram of Carbon-12.” The number of entities is
approximately 6.02 x 1023 (Avogadro's number)
q The concept of the mol is particularly useful for gas
calculations, as at a given pressure and temperature,
equal volumes of different gases contain the same
number of molecules.
q At 15.0 oC and 101.325 kPa, a kmol of gas contains
about 6.02 x 1026 molecules (Avogadro's number) and
occupies 23.64 m3.
Length, area, volume, and density
q The standard unit of length is the meter (m)
q Area is expressed in the same unit squared.
q Volume is expressed in the cubic meter.
q Density: mass/volume
q The usual units are kg/m3
q It is a function of temperature and pressure, so standard density
is required.
q Relative density: is the density of the system divided by the
density of a reference substance at specified conditions.
(Eq 1-2)
q For oil, the relative density is expressed by oAPI
(Eq 1-3)

Mass, force and weight
q If relativistic effects are ignored, the mass of a body is a measure of
the quantity of matter.
q In the SI system the unit of mass is kilogram, with tonnes, grams,
milligrams, and micrograms also being used.
q In the FPS system, tons, pounds, ounces, and grains are commonly
used.
q 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 on Earth is: g =
9.81 m/s2.
q The relationship between mass and force is:
(Eq 1-4)

Physical Properties: Pressure
q Pressure is the force exerted per unit area.

q 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.
q 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).
q In SI, it is common to use no suffix for absolute pressure,
so that P = 150 kPa implies an absolute pressure.
q In some instances absolute pressures are written as
kPa(abs). A gauge pressure would be written as kPa(g).
Physical Properties: Fluid head
q 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:
q The term (g/gc) is called the force equivalent and is

represented by the symbol Fe. The value varies with the
local acceleration due to gravity, but the standard value is
9.81 N/kg. ENCH 607-Dr. Nassar 46
Physical Properties: Temperature
q Is the measure of the average transitional energy of the

molecules.
q The SI units are degrees Celsius (oC) and Kelvin (K).
q K = oC + 273.15 (Eq 1-6a)
q oC = (oF - 32) / 1.8 (Eq 1-6b)
q oF = 1.8 x oC + 32 (Eq 1-6c)
q oR = oF + 459.67 (Eq 1-6d)
q Degrees Fahrenheit (oF) and Rankin (oR) are the units in
the FPS system.
q Absolute temperatures are used in most engineering
calculations. When temperature differences are required,
they are the same whether absolute or Celsius scales
are used.
Physical Properties: Work and Power
qThe units of work are force times distance.

qThe 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.
qPower is the time rate of performing work.
qThe watt (W) and horsepower (hp) are the
most common units.
q1 kW = 3600 kJ/h = 1.34 hp
Physical Properties: Heat energy
qHeat energy must have the same units as work

and power in order to make calculations
involving the conversion between them.
qIn SI the joule is also used for heat energy, while
the British Thermal Unit (Btu) is used in the FPS
system.
q1 kW = 3600 kJ/h = 3412 Btu/h
qEnergy per unit mass is expressed in kJ/kg and
Btu/lbm
q1 Btu/lbm = 2.326 kJ/kg = 6.46 x 10-4 kWh/kg

Physical Properties: Heat capacity
qHeat capacity is a measure of the amount of

energy required to raise the temperature of a
given quantity of a substance by one degree.
The quantity units can be mass or moles.
qFor liquids and solids there is only one type of
heat capacity.
qFor gases, heat capacity is given at constant
pressure (CP)or a constant volume (CV).
q1 kJ/kgoC = 1 kJ/kgK = 0.23901 BTU/lboF
q1 kJ/kmoloC = 0.23901 BTU/lb-moloF

Physical Properties: Thermal conductivity
and surface tension
qThermal conductivity is a measure of the

ease of heat transfer through a substance.
qThe standard SI units are W/mK of W/moC.
qThe FPS units are BTU/hr ft oF.
q1 W/mK = 0.5782 Btu/hr ft oF
qSurface tension is a measure of the
adhesive force between similar molecules.
Standard units are dynes/cm.

Physical Properties: Viscosity
qViscosity is a measure of the resistance to flow.

There are two types of viscosity:
qThe dynamic viscosity, is a shear force per unit
area. The poise was the original unit; 1 poise = 1
dyne•s/cm2. For petroleum systems the centipoise
(cp) is the most convenient unit. In SI the Pa·s is
the preferred unit.1 cp = 1.0 mPa·s = 0.001 Pa·s
= 0.001 kg/(m·s) = 6.72 x 10-4 lbm/(ft.s)
qKinematic 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/s

Equation of state
qAn equation of state (EOS) is a functional

relationship for a substance (generally
gases and liquid) between:
qPressure
qTemperature
qSpecific or molar volume

Boyle's Law
q The gas volume/pressure

relationship
q The volume occupied by the
gas is inversely proportional to
the pressure
qV µ 1/P
qTemperature and the
amount of the gas are fixed
qV = k1/ P or PV = k1
qk1 is a proportionality
constant
qP1V1=P2V2=k1
Boyle's Law
Source: http://upload.wikimedia.org/wikipedia/commons/1/15/Boyles_Law_animated.gif

Charles’ Law
qDefines the gas

volume/temperature
relationship
qV µ T (constant
pressure and amount
of gas)
qV = k2 T
qk2 ® proportionality
constant
qV1/T1 = V2/T2 Absolute zero, K =0

Charles’ Law
Source: http://upload.wikimedia.org/wikipedia/commons/e/e4/Charles_and_Gay-Lussac%27s_Law_animated.gif
Amonton’s Law
qThe
pressure/temperature
relationship
qFor a given quantity
of gas at a fixed
volume, P µ T
qP = k3 T
qP1 = k3T1
qP2 = k3T2
qP1 / T1 = P2 / T2

Avogadro’s Law
qThe volume of a gas at constant T and P is

directly proportional to the number of moles of
gas.
qV = k4 n, where n = number of moles of gas

All the possible states of an
ideal gas can be represented by
a PVT surface as illustrated. The
behavior when any one of the
three state variables is held
constant is also shown.

The Ideal Gas Equation of State
q We have four relationships
qV µ 1/P; Boyle’s law (T and n constant)
qV µ T; Charles’ law (P and n constant)
qV µ n; Avogadro’s law (P and T constant)
qP µ T; Amonton’s law (V and n constant)
q We combine these relationships into a single fundamental
equation of state ® the ideal gas equation:
PV = nRT
PVm = RT
R is the universal gas constant
R = 0.082057 L.atm/(K.mol)
= 8.314 J/(K.mol)
The Ideal Gas Equation of State
Ideal gas:
q Is an imaginary gas which obeys certain simple rules or
laws.
q Has a mass, but its molecule have (or assumed to have)
zero volume.
q The molecules do not exert any force on the neighboring
molecules (i.e., no attractive or repulsive forces).
q Then, molecules are separated by a large distance from
each other.
q Generally, a gas has to be at high temperatures and low
pressures for it to be approximated as an ideal gas:
q T>>Tc , P<<Pc
The REAL Gas Equation of
State
Real gases:
q Which do not follow ideal gas behaviour
qWhy do they deviate from ideal gas law?
qUse of Tc and Pc
qA compressibility factor is defined
qThe law of corresponding state
qCubic equations of state
qMixtures of non-ideal gas

The REAL Gas Equation of
State
Reasons:
q Diverse shape of molecule (not close to
spherical)
qIntermolecular forces
qVolume of molecules
qElectrical forces
qQuantum effects

Virial equation of state
q An important EOS class that has a rigorous basis in molecular theory (may
be derived from statistical mechanics)
q The compressibility is expressed as a polynomial in volume
PVm B C
Z= = 1 + + 2 + ! = 1 + Br + Cr 2
RT Vm Vm
q Or as a polynomial expansion in pressure
Z = 1 + B¢P + C ¢P 2 + D¢P 3 + !
q Where
B C - B2 D - 3BC - 2 B 3
B¢ = C¢ = D¢ =
RT (RT )2 (RT )3
q The coefficients B, C, D, … are termed the second, third, fourth, … virial
coefficients ENCH 607-Dr. Nassar 65
Virial equation of state
dZ
=0 For a perfect gas
dP
dZ
= B'+2 PC '+ ! ® B' as P ® 0 For a real gas
dP
There may be a temperature at which Z®1 with
zero slope at low pressure. (Boyle T)
Z
The properties of the real gas do
Higher T coincide with those of a perfect gas
as P®0.
T
oyle
B
Perfect gas
1
Pressure
Lower T
virial equation of state
Z
Higher T
le T
y
Bo
Perfect gas
1
Pressure
Lower T
The compression factor approaches 1 at low P, but does
so with different slopes. For a perfect gas, the slope is
zero, but real gases may have either positive or negative
slopes, and the slope may vary with T. At the Boyle T, the
slope is zero and the gas behaves perfectly over a wider
range of conditions than that at other T.
EOS: Benedict-Webb-Rubin
q Another example of a virial-type EOS

q Has eight parameters
q Frequently used for modeling the PVT behavior of light
hydrocarbons and gases in petroleum and natural gas
applications
RT æ Co ö 1 (bRT - a )
P= + ç Bo RT - Ao - 2 ÷ 2 + 3
+
Vm è T ø Vm Vm
+
(
aa c 1 + g Vm 2
exp - g Vm
2) ( )
Vm 6 Vm 3T 2
The Theorem of Corresponding States
Compressibility Factor
q The volumetric PVT behavior of a material is often
characterized by the compressibility factor Z
PV PVm
Z= =
nRT RT
q Typical values: ideal gas, Z = 1.0; liquids, Z ~ 0.01 to 0.2;
critical point, Zc ~ 0.27 to 0.29
Theorem of Corresponding States
q This theorem suggests that values of thermodynamic
properties of different fluids can be compared when
properties are normalized by their values at the critical point
Z = f (Z c , Tr , Pr )
The Theorem of Corresponding States
q The reduced temperature and

pressure are simply
Tr = T Tc and Pr = P Pc
q If Zc is assumed to be a constant
for all materials
Z = f (Tr , Pr )
q Experimental observations provide
strong evidence to support this
approach
q The relation above indicates that all
fluids have the same reduced
volume Vr (as well as other
properties) at a specified Tr and Pr

The Theorem of Corresponding States:
Generalized Coexistence Curve
q The theorem of corresponding states can be used to obtain a

generalized phase diagram
q “Law of rectilinear diameters” – states that the average density in
the L-V region varies linearly over a wide temperature range
below the critical point
q Zero line – the Z = 1.0 line on
the phase diagram
q For states with Z > 1.0 (hard fluid),
repulsive forces dominate and
conversely, for states where
Z < 1.0 (soft fluid) attractive forces
are dominant

The Theorem of Corresponding States:
Acentric Factor
q To improve the accuracy of property predictions, Pitzer and Curl
introduced the acentric factor w as a third correlating parameter
Z =Z (0 )
(Tr , Pr ) + ωZ (Tr , Pr )
(1)
q The acentric factor was developed
as a measure of the difference in
structure between the material of
interest and a spherically symmetric
gas such as argon
q Therefore, the parameter is related
to a molecular property
q The parameter is defined using the
reduced vapor pressure
ω = - log10 ( Pvp ,r ) -1
Tr = 0.7
Pitzer and Curl Generalized Z

Cubic Equations of State
Relating EOS Parameters to Experimental Data

q Empirical models have parameters that must be determined
to calculate PVT data
q A common way to determine these parameters is to relate
the model parameters to a fluid’s critical properties
q By adopting this approach we are utilizing the theorem of
corresponding states
q The critical point criteria for a single-component system
require
æ ¶P ö æ ¶2P ö
ç ÷ =0 ç 2÷ =0
è ¶V øTc è ¶V øTc

q A cubic algebraic equations

always has three roots.
q Above the critical temperature
Tc, two of the roots are complex
numbers, one will be a real
number.
q At the critical temperature Tc,
three equal real roots.
q Below the critical temperature
Tc, three unequal real roots.
q A cubic equation of states
isotherm in the two-phase
region below Tc will resemble
the dotted line in the figure to
the right.

q Since the pioneering work of van der Waals, numerous

modifications of the original vdW EOS have been published
(
q Most are pressure-explicit cubic forms, i.e., P = f T , V , n )
van der Waals EOS
RT a
P= - 2
Vm - b Vm
27 R 2Tc2 RTc
a= b=
64 Pc 8 Pc
Zc = 0.375 76
ENCH 607-Dr. Nassar
Redlich-Kwong (RK)
RT a
P= -
Vm - b T Vm(Vm + b )
W a R 2Tc2.5 W a = [(9)(2 - 1)] = 0.42748!

13 -1
a= with
Pc
b=
W b RTc
with Wb =
(2
13
- 1)
= 0.08664!
Pc 3
Zc = 0.333

Soave-Redlich-Kwong (SRK)
q The attractive term is made temperature dependent and the

acentric factor is introduced with a = ac f (ω, Tr ) = aca
RT aa ( ( ))
2
P= - , where a = 1 + k 1 - Tr
Vm - b Vm(Vm + b )
k = 0.48508 + 1.55171ω - 0.15613ω 2
W a R 2Tc2.5
a= with W = [(9)(21 3 - 1)]-1 = 0.42748!
Pc a
b=
W b RTc
with W b =
(213
- 1)
= 0.08664!
Pc 3
Zc = 0.333
Peng-Robinson (PR)
RT aa
P= - Zc = 0.307
Vm - b Vm(Vm + b ) + b(Vm - b )
0.45724 R 2Tc2 0.07780 RTc

ac = b=
Pc Pc
a(ω, Tr ) = (1 + k(1 - Tr )) k = 0.37464 + 1.54226ω - 0.26992ω 2

2

Gas mixtures
q Gas mixtures have properties which are different from the

individual constituents
q Basically, two methods are usually employed:

q Pseudo-critical method (Kay’s rule)
q The mixing rule method

Katz correlation and Kay’s rule
q This is the simplest method

to calculate Z.
q This figure (FIG. 23-4 in the
GPSA Engineering Data
Book) is used for lean sweet
natural gas.
q To use the correlation, the
pseudo-critical properties of
the gas mixture are used to
determine the pseudo-
reduced properties (Kay’s
rule)

Kay’s rule
q Kay’s rule is a mole weighted average and states:
q Kay’s rule also applies to the MW and w:

n n
MW ' = å yi MWi w ' = å yi w i
i =1 i =1
Modifications for sour gas
q When the gas contains appreciable quantities of H2S or CO2, the Katz
correlation is modified by applying one of two methods proposed by
Robinson et al., 1960 and Wichert and Aziz, 1972.
q The method applies a correction factor (ε) to the pseudo-critical
parameters calculated using Kay’s rule. ε is function of the mole
fraction and is calculated as follows:
B: is the mole fraction of H2S
A: is the mole fraction of H2S
and CO2.
q Once ε is determined, adjusted critical parameters are calculated as

follows:
where,

Estimation of
e graphically
q (FIG. 23-8 in the

GPSA Engineering
Data Book).

Mixing Rules
q For mixtures of components, mixing rules must be applied to

the constants.
q For Van der Waals and RK
n n n
bm = å xi bi am = åå xi x j aij (1 - kij )
i =1 i =1 j =1
aij = (ai a j ) 2
1
where,

Mixing Rules
q For simplicity, Van der Waals and RK
n 2
" %
bm = å xi bi
n
am = $ ∑ xi ai '
i =1 # i=1 &

References
1. M.B. Standing, and D. Katz, Trans AIMS, 140, p.146, 1942.

2. Robinson, D.F., et al., Trans AIME, Vol. 219 (1960), p. 54.
3. Wichert, E. and Aziz, K., Hydrocarbon Processing (May 1972), p. 119.
4. K. E. Starling and M. S. Han, “Thermo Data Refined for LPG, Part 14”,
Hydrocarbon Processing, (May 1972), p. 129.
5. K. E. Starling and M. S. Han, “Thermo Data Refined for LPG, Part 15”,
Hydrocarbon Processing, (June 1972), p. 129.
6. S.W. Hopke and C.J.Lin, “Application of the BRSW Equation to Natural Gas
Systems”, 76th National AIChE Meeting, March 10-13, 1974, Tulsa, OK.
7. P.R. Bishnoi and D.B. Robinson, “New Mixing Rules for the BWR Parameters
to Predict Mixture Properties”, Can. J. Ch. E., Vol. 5, February 1972, p. 101.
8. O. Redlich and J.N.S. Kwong, Chem. Review, Vol.44 p. 233, 1949.
9. G. Soave, Chemical Engineering Science, Vol. 27, 1972, p. 1197.
10. D.Y. Peng and D.B. Robinson, Industrial and Engineering Chemistry
Fundamentals, Vol. 15, p. 59, Feb. 1976.

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Introduction and equations of state

Nashaat Nassar, PhD, PEng, Professor

September 9th, 2021

By the end of this lecture, students will gain

Energy consumption is Energy demand will decline

ENCH 607-Dr. Nassar 3

ENCH 607-Dr. Nassar 4

• The decline in U.S. energy

• Significant efficiency gains

• The average new U.S. car

Image courtesy: CEP August 2015 www.aiche.org/cep

ENCH 607-Dr. Nassar 5

Image courtesy: CEP August 2015 www.aiche.org/cep

ENCH 607-Dr. Nassar 6

Access to unconventional gas production will change the import-export

• Plentiful, low-cost natural gas will invigorate the

ENCH 607-Dr. Nassar Image courtesy: CEP August 2015 www.aiche.org/cep 8

ENCH 607-Dr. Nassar Image courtesy: CEP August 2015 www.aiche.org/cep 9

• The two-process approach is inherently inefficient.

ENCH 607-Dr. Nassar Image courtesy: CEP August 2015 www.aiche.org/cep 10

Unprocessed natural gas Gas is “the cleanest” hydrocarbon fuel

CO2 emissions per energy unit

ENCH 607-Dr. Nassar 13

ENCH 607-Dr. Nassar 14

Source: A. H. Younger, Natural gas processing principles and technology

ENCH 607-Dr. Nassar 15

Source: Fig 4 (GPSA Engineering Data Book)

ENCH 607-Dr. Nassar 16

q Gas that is sold for commercial use is different in

From a field From a straddle

ENCH 607-Dr. Nassar 17

qAll acid gas compounds, H2S and CO2, should be

qThe removal of acid gases, water and

q Most reservoirs are saturated with water at reservoir

q Gas and liquid hydrocarbon analyses are performed

ENCH 607-Dr. Nassar 21

ENCH 607-Dr. Nassar 22

q Olefins have a single carbon-carbon double bond.

ENCH 607-Dr. Nassar 23

q Aromatic: unsaturated cyclic hydrocarbons

ENCH 607-Dr. Nassar 24

qAcid gases, H2S and CO2, are usually

ENCH 607-Dr. Nassar 25

qThis usually refers to the following compounds:

ENCH 607-Dr. Nassar 26

qIt is often tied up with H2S in the form of

ENCH 607-Dr. Nassar 27

q Produced gas can also contain: hydrogen, helium,

ENCH 607-Dr. Nassar 29

Table 1.2: Typical Pipeline Composition (dry basis)

q Straddle plants are specifically designed to recover

ENCH 607-Dr. Nassar 30

q Standard gas conditions for System International (SI): 15

ENCH 607-Dr. Nassar 31

qThe Wobbe Index is a critical factor to minimize the

ENCH 607-Dr. Nassar 34

Methane and lighter 1 mol% maximum

C2H6 95 mol% min

ENCH 607-Dr. Nassar 36

ENCH607 F2021 L01 Introduction&Equations of State

ENCH607 F2021 L01 Introduction&Equations of State

ENCH607 F2021 L01 Introduction&Equations of State