Saudi Aramco - Chemical Physical Properties

Engineering Encyclopedia
Saudi Aramco DeskTop Standards
PHYSICAL PROPERTIES
Note: The source of the technical material in this volume is the Professional
Engineering Development Program (PEDP) of Engineering Services.
Warning: The material contained in this document was developed for Saudi
Aramco and is intended for the exclusive use of Saudi Aramcos employees.
Any material contained in this document which is not already in the public
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parties, or otherwise used in whole, or in part, without the written permission
of the Vice President, Engineering Services, Saudi Aramco.
Chapter : Chemical
File Reference: CHE-202.01
For additional information on this subject, contact

PEDD Coordinator on 874-6556
Physical Properties of Gases and Liquids

Physical Properties
Module Component
Page
IMPORTANCE OF PHYSICAL PROPERTIES................................................................ 3

Introduction ................................................................................................................ 3
Basic Data Needs for Design ..................................................................................... 5
Examples from the Literature..................................................................................... 6
Units and Conversions............................................................................................... 8
References .............................................................................................................. 12
CRITICAL CONSTANTS AND CORRESPONDING-STATES METHODS.................... 14
Introduction .............................................................................................................. 14
PT Diagram.............................................................................................................. 14
PV Diagram ............................................................................................................. 16
Introduction to Critical Constants ............................................................................. 18
Critical Constant References ................................................................................... 18
Critical Constant Estimation Methods ...................................................................... 19
Comparison of Estimation Methods ......................................................................... 22
Introduction to Corresponding States....................................................................... 23
Two-Parameter Corresponding States..................................................................... 23
Three-Parameter Corresponding ............................................................................. 24
DENSITY OF GASES AND LIQUIDS............................................................................ 27
Introduction .............................................................................................................. 27
General PVT Behavior ............................................................................................. 28
Summarizing PVT Behavior of Real Fluids .............................................................. 29
For Gases:.......................................................................................................... 29
For Liquids:......................................................................................................... 29
For Supercritical Fluids: ...................................................................................... 29
For the Immediate Critical Region: ..................................................................... 29
Saturated Liquid Density from the Rackett Equation................................................ 32
Equation of State Methods....................................................................................... 33
Mixtures ................................................................................................................... 35
Mixtures (Pitzer/Lee-Kesler) ............................................................................... 35
Mixtures (SRK Equation of State)....................................................................... 36
VAPOR PRESSURE ..................................................................................................... 39
Introduction .............................................................................................................. 39
Typical Vapor Pressure Curve ................................................................................. 39
Antoine Vapor Pressure Equation............................................................................ 40

Physical Properties
Riedel Vapor Pressure Equation.............................................................................. 41

Frost-Kalkwarf Vapor Pressure Equation................................................................. 41
Wagner Vapor Pressure Equation ........................................................................... 42
Lee-Kesler Vapor Pressure Equation....................................................................... 42
Comparison of Vapor Pressure Equations............................................................... 43
Heat of Vaporization from Vapor Pressure .............................................................. 44
Vapor Pressure References..................................................................................... 45
Process Simulator Vapor Pressure .......................................................................... 45
Summary ................................................................................................................. 46
Work Aid 1.1: Using Conversion Factor Tables .................................................. 47
Work Aid 2.1: Estimating Critical Constants; Lydersens Method ....................... 60
Work Aid 2.1 (Contd): Lydersens Method Quantities..................................... 61
Work Aid 3.1: Calculating Compressibility Factors with Pressure Series ........... 62
Work Aid 3.2: Calculating Liquid Density ............................................................ 63
ii

Physical Properties
IMPORTANCE OF PHYSICAL PROPERTIES

Introduction
Physical Properties for Chemical Engineers, Course ChE 202,
is an intermediate-level course that provides a refresher in the
calculation of physical properties, as well as in thermodynamics.
All course participants are presumed to have at least a B.S. in
Chemical Engineering. It is also assumed that the participants
will have some knowledge of the process simulator that is used
by Saudi Aramco.
The course is five days long and is divided into six modules.
These six modules are:
ChE 202.01: Physical Properties.
ChE 202.02: Thermodynamics.
ChE 202.03: Vapor-Liquid Equilibria.
ChE 202.04: Properties of Petroleum Fractions.
ChE 202.05: Secondary Properties.
ChE 202.06: Chemical Equilibria.
This first module discusses why we are interested in physical

properties and then examines critical constants and two
important properties: density and vapor pressure. The first two
laws of thermodynamics and thermal properties are the focus of
the second module, while the third module is devoted to the key
property, vapor-liquid equilibria. The fourth module introduces
the petroleum fractions and their properties. The fifth module
examines surface tension, transport properties, and a variety of
phase equilibria, while the sixth and final module considers
chemical reactions.
The first module is divided into four lectures:
Lecture 1: Importance of Physical Properties.
Lecture 2: Critical Constants and Corresponding-States

Methods.
Lecture 3: Density of Gases and Liquids.
Lecture 4: Vapor Pressure.

Physical Properties
We start with an introduction to physical propertieswhy we

study physical properties and the property needs of process
design. Then, we discuss the various systems of units and
conversions, as well as the references used in this course.
Then, we tackle the gas-liquid critical constants, which are
important in their own right and because they are used in the
so-called corresponding-states methods for property prediction.
Next, we examine the prediction of density, the key physical
property, first for ideal gases, and then for real gases and
liquids. After that, we discuss vapor pressure, which is essential
to predicting vapor-liquid equilibria.
Let us now consider what we mean by physical properties. What
are they and why do we study them? Why are they important?
Included are physical properties such as density,
thermodynamic properties such as enthalpy, and transport
properties such as viscosity. These are the basic data in
carrying out heat and material balance calculations or in
designing process equipment.
The first lecture reviews basic data needs for design: what we
need to know and why. We will learn which properties are the
most important and are, therefore, the ones we need to know
more accurately. When we talk about physical properties we
must also talk about units, which can be very confusing,
because there is no single set of units that everybody uses. We
briefly examine a variety of units: customary engineering or
English and metric; unit conversions; and also the units
available in PROCESS. Finally, there are a few words about
referencesthe textbooks used in the course as well as other
references and data sources available within Saudi Aramco.

Physical Properties
Basic Data Needs for Design

The first and most important use of physical properties is in heat
and material balance calculations. In such calculations, any
uncertainties in the data or in the predictions will directly affect
the results. The three essential properties are:
Vapor-liquid equilibria (VLE).
Enthalpy.
Density or, more generally, P-V-T (pressure-volumetemperature) properties.
Vapor-liquid equilibria, which include the vapor pressure of the

defined compounds or petroleum fractions, are particularly
important because most separations are effected through partial
vaporization of a liquid mixture, such as in distillation. If
separation is by liquid-liquid extraction, then liquid-liquid
equilibria become important. Predicting vaporization is difficult in
multicomponent systems, especially those that are nonideal. As
an example, nearly 60% of the BASF Chemical Companys
budget on basic data goes to measuring vapor pressures and
vapor-liquid equilibria. Another 4% goes to measuring liquidliquid equilibria. About 10% is spent on thermal data, that is,
heat capacity, heat of vaporization, heat of mixing, and, what is
often the most important, heat of reaction.
Although the BASF budget allocation may be more typical of
chemical companies, the interests of petroleum companies are
similar. VLE and enthalpy are the properties of highest priority.
Transport properties and surface tension are of less interest
because they are primarily used in the design of equipment. The
reasons why great accuracy might not be needed in the
properties used for equipment design are summarized below:
A property may have little influence on equipment size

because its value may not vary greatly or it is frequently
raised to a fractional exponent.

Physical Properties
The correctness of a model used in equipment design may

be more important than accuracy of the data. It may be more
correct to say that, if a model has been based on lower
quality data, its use with high-quality data may make
predictions worse.
Fouling of equipment cannot be quantified; therefore, the

size of equipment is less affected by inaccuracies in
thermodynamic and transport property data.
There are many examples in the literature of how uncertainties

in basic data can affect the design of process units. Two such
examples are considered here.
Examples from the Literature

Example 1.1: Butane/Pentane Splitter
The first example concerns the design of a butane/pentane
splitter. In this separation, the light key is n-butane and the
heavy key is isopentane. Essential to the design of this
distillation tower is knowing the volatility, in this case, the vapor
pressure, of the two key components. As shown in Figure 1 (A)
taken from the paper by Nelson et al., Ind. Eng. Chem., 22, 547
(1983), the reflux ratio increases exponentially (for fixed number
of stages and recoveries) as the volatility of n-butane is
reduced. A 10% reduction (or uncertainty) in the volatility
translates into a 50% higher reflux ratio, and therefore a larger
tower.
On the other hand, as shown in Figure 1 (B), if we fix the reflux
ratio, then the number of stages increases rapidly as the
volatility of n-butane decreases. A 5% lower volatility increases
the number of stages by 20%. Clearly, we need to know
volatilities (and vapor pressures) of key components to much
better than 5%.

Physical Properties
FIGURE 1. Butane/Pentane Splitter

Example 1.2: Nitrogen Removal from Natural Gas
The second example was taken from Klotz et al., Hydrocarbon
Process., 62(4), 84 (1983) and concerns nitrogen removal from
natural gas. Figure 2 is a heat exchanger in the nitrogen
rejection unit. We consider here only three changes: a 5% lower
N2 K-value; a 5% lower methane K-value; and a 1 Btu/lb error in
the enthalpy difference between inlet and outlet.

Physical Properties
FIGURE 2. Heat Exchanger in Nitrogen Rejection Unit

A 5% lower K-value for N2 leads to an inoperable situation:
there is a temperature cross in the heat exchanger. When the
methane K-value is lowered by 5%, the minimum temperature
approach is reduced from 6.2 to 3.9 F and the heat exchanger
area must be increased by 33%. Finally, just a 1 Btu/lb error in
the enthalpy difference can reduce the minimum temperature
approach by 0.4 F and increase the heat exchanger area by
7%.
Units and Conversions

Units are inseparable from physical properties. Unfortunately,
we do not have one system of units that everybody uses and
understands. Instead, there are three broad systems or sets of
units, along with many variations:
The English or customary engineering system of units.
The metric system.
The SI (for Systme International) or international metric

system.

Physical Properties
Saudi Aramco uses the English units, but data for properties are
reported in a variety of units. Therefore, it is very important that
you know the units used for the key properties and are able to
convert from one set to another set of units. Conversion tables
for units are available in most references. Work Aid 1.1
contains conversion factor tables for use in this course.
The SI system may one day become accepted by everybody,
but not yet. Figure 3 presents the base units in SI. You are all
familiar with meters, seconds, kilograms, moles, and kelvins. In
this course, we will not use amperes or candelas.
SI BASE UNITS
Quantity
Name
Symbol
Length
metre (or
meter)
Time
second
Mass
kilogram
kg
Amount of Substance
mole
mol
Temperature
kelvin
Electric Current
ampere
Luminous Intensity
candela
cd
FIGURE 3. SI Base Units

The SI unit of force is the newton, N. It is a secondary unit,
because it is related to base units through Newtons second law
of motion:
F=ma
The mass m is expressed in kilograms, while the acceleration a
is in meters per second squared. Thus:
1 N = 1 kg x (m/s2)
In the English engineering system, force is defined
independently as:

Physical Properties
l lbf =
1 lbm x 32.174 ft/s2

gc
To make lbf and lbm numerically equal:

gc = 32.174 lbm (ft/s2)/lbf
(Numerically, gc is equal to the acceleration of gravity at sea
level.)
When the English engineering system is used, whenever both
lbm and lbf are included in an equation, we must not forget to
also use gc for dimensional consistency. The use of SI units
eliminates the need for gc.
Figure 4 gives examples of unit conversions. Only in the case of
temperature have we a complete set: F, R, C, and kelvins are
all the units. The absolute temperature (starts at the absolute
zero) is measured in R or K. The absolute zero in the other
units or temperature scales is -459.67F or -273.15C.
Length:
Mass:
1 ft
0.3048 m
1 lbm =
Temperature:
0.4535924 kg
F, R, C, K (Complete Set!)
R
F + 459.67
C + 273.15
(1.8) (C) + 32
Pressure (Force per Unit Area): pascal, Pa

1 psia (lbf / in2 absolute) =
6894.757 Pa
1 atm
101325.0 Pa
1 kgf / cm2
98066.50 Pa
= 1N / m2
FIGURE 4. Examples of Unit Conversions

The SI unit for pressure is the pascal, Pa = 1 N/m2. It is a very
small quantity, and it is therefore generally used with the prefix k
for kilo (kPa = 1000 Pa) or M for mega
10

Physical Properties
(MPa = 1,000,000 Pa). The standard atmospheric pressure, 1

atm, is 101.325 kPa or 0.101325 MPa. A so-called metric
engineering unit for pressure is kgf /cm2, which is equal to
98.0665 kPa. Finally, another unit you may have come across is
the bar, which is equal to 100 kPa or 0.1 MPa. There will be
more on units when we talk about the properties.
PROCESS has three broad sets of units, defined by the
keywords English, Metric, or SI. If no key word is used, then
by default the English engineering system is used throughout.
However, the user can override the standard set. Furthermore,
the user can specify different units for the output than those
used in the input.
Example 1.3: The Units and the Magnitude of the Gas Constant,
R
To review the units and get an appreciation of the magnitudes
involved, let us consider the gas constant R.
As you probably all remember, all gases obey the ideal-gas law
in the limit as pressure goes to zero:
PV = RT
(Eqn. 1)
In Equation 1, V is the molar volume, the volume of one mole

(6.022 1023 molecules) of the substance, and T is the
absolute temperature.
The pressure - molar volume product of a gas at 0C and zero
pressure is:
(English)
359.039 (ft3)(atm)/(lb-mol)
(Metric)
22.4141 (liters)(atm)/(g-mol)
(SI)
2.27111106 (m3)(Pa)/(kg-mol)
When we substitute into Equation 1, we obtain the values for R

given in Figure 5. Only in the case of the SI units does R have
the same value whether it is expressed in P-V units or in energy
units. When we use Btus or calories for energy, we get the
bottom two values in Figure 5, which frequently are set equal.
11

Physical Properties
R = 10.732 (psia)(ft3/lb-mol)/(R)
= 0.082058 (atm)(L/g-mol)/(K)
= 8314.5 (Pa)(m3/kg-mol)/(K) or (J/kg-mol)/(K)
= 1.9859 (Btu/lb-mol)/(R)
= 1.9872 (cal/g-mol)/(K)
FIGURE 5. The Units and the Magnitude of the Gas Constant, R
References
To complete the introduction to Physical Properties, we need to
talk about the textbooks we have selected for the course, as
well as additional references and data sources that are available
to use.
We selected W. C. Edmisters book, Applied Hydrocarbon
Thermodynamics [2nd Ed., Gulf Publ., Houston; Vol. 1 (with B.I.
Lee): 1984; Vol. 2: 1988], because it focuses on the substances
of special interest to you: defined hydrocarbons and undefined
mixtures or petroleum fractions. There is also a summary of the
key thermodynamic relations in the first volume of Edmisters
book, but there is nothing on surface tension or transport
properties.
Therefore, we have suggested a second textbook, R. C. Reid, J.
M. Prausnitz, and B. E. Poling, The Properties of Gases and
Liquids, (4th Ed., McGraw-Hill, New York, 1987), the classic
reference for property estimation. This book contains very
extensive discussions on the many methods that have been
proposed for predicting physical, thermodynamic, and transport
properties. But Reids book has nothing on thermodynamics and
focuses on defined compounds: there is no mention of
petroleum fractions.
12

Physical Properties
Finally, we mention three additional references of general

interest. Introduction to Chemical Engineering
Thermodynamics, by J. M. Smith and H. C. Van Ness (4th Ed.,
McGraw-Hill, New York, 1987) is the most popular
undergraduate textbook for this topic in the United States. Some
of you may have used it.
The data books of the American Petroleum Institute (Technical
Data Book--Petroleum Refining, 4th Ed., API, Washington, DC,
1987) and the Gas Processors Suppliers Association
(Engineering Data Book, 10th Ed., GPSA, Tulsa, OK, 1987)
provide data and prediction methods for most of the properties
in this course. We are more familiar with the API Data Book, but
we are told that the GPSA Data Book is available to Saudi
Aramco engineers. And, of course, you all have access to the
PRO II, HYSIS and Aspen Plus.
Example 1.4: Properties of Gases and Liquids
Appendix A in Reids book is a very extensive property data
bank. In order to be familiarized with this important data source,
let us together look at the information given for methane,
dodecane, and heptadecane. Notice that not all values are
available for all compounds.
13

Physical Properties
CRITICAL CONSTANTS AND CORRESPONDING-STATES METHODS

Introduction
This lecture provides some of the background that will be used
in later modules for calculating thermodynamic properties. The
first topic is the pressure-volume-temperature (PVT) behavior of
pure components. This is illustrated through pressuretemperature (PT) diagrams and pressure-volume (PV)
diagrams. Next, we look at the critical point. This includes
references to where values for the critical point properties of
pure components can be found as well as prediction methods
for estimating these values when they are not available. Finally,
we discuss the theory of corresponding states, which provides
the basis for many prediction methods. This includes both twoand three-parameter corresponding-states methods.
PT Diagram
A typical PT diagram is shown in Figure 6. The three curves on
this diagram represent the pressure and temperature conditions
where two phases can coexist and thus are the boundaries for
the single phase regions. The most important of these is the
vaporization or vapor pressure curve. Vapor and liquid
phases coexist along this curve, which begins at the triple point
and extends up to the critical point. On the sublimation or solid
vapor pressure curve, vapor and solid phases can coexist.
This curve ends at the triple point. Finally, on the fusion or
melting curve, liquid and solid phases coexist. This curve
begins at the triple point and almost parallels the vertical axis.
14

Physical Properties
FIGURE 6. PT Diagram for a Pure Component

There are two important points in Figure 6: the triple point and
the critical point. The critical point is that temperature and
pressure at the end of the vapor pressure curve, where it is no
longer possible to distinguish between the liquid and vapor
phases. The coordinates of this point are called the critical
temperature, Tc, and the critical pressure, Pc. These
represent the highest temperature and pressure at which a pure
component can exist in either the vapor or liquid phase. Above
this point it is no longer possible for a pure component to
undergo a change in phase. The other important point on the
diagram is the triple point. This is the point where all three
curves meet. Thus, it is the only temperature and pressure
where all three phases, vapor, liquid, and solid, can coexist.
Usually, this point is very close to, but not identical to, the
melting point.
15

Physical Properties
The vapor, liquid, and solid single phase regions shown on the
diagram are defined clearly by the vaporization, sublimation,
and fusion curves. The other single phase regions shown on the
diagram have been defined by the dashed lines. These lines do
not represent phase changes. However, they do show the
usual, but arbitrary, definitions of these regions. The gas region
is the part of the vapor region that is above the critical
temperature, and the compressed liquid region is the part of
the liquid region that is above the critical pressure. Finally, the
fluid region is the region above both the critical temperature
and pressure.
The values of all thermodynamic properties, such as density,
vary smoothly in the single phase regions. However, most
properties vary abruptly between any two phases, that is, across
any of the three curves. Finally, note that a path can be drawn
from the liquid region to the fluid region to the vapor region that
does not cross the vapor pressure curve. This path represents a
gradual change in properties from those of a liquid to those of a
gas with no abrupt change of phase.
PV Diagram
Although the PT diagram displays the phase boundaries, it does
not provide any information on the volume. This is shown on the
PV diagram in Figure 7 (note that the solid region has been
excluded). The dome-shaped curve defined by the thickest line
is the vapor pressure curve. The critical point splits this curve
into a saturated (100%) liquid curve and a saturated (100%)
vapor curve. The area to the left of the dome is the single phase
liquid region, while the area to the right is the single phase
vapor region. The area under the dome is the two phase region.
Several isotherms (constant temperature lines) are shown on
the diagram. The critical isotherm (T = Tc) is shown as a
moderately thick line that intersects the top of the dome at the
critical point, where it exhibits a horizontal inflection, reflecting
the onset of two-phase behavior. The volume at this point is
called the critical volume, Vc. The critical isotherm, together
with the vapor pressure curve and the dashed line, provides the
same boundaries for the single phase regions that were shown
on the PT diagram in Figure 6.
16

Physical Properties
FIGURE 7. PV Diagram for a Pure Component
17

Physical Properties
Two additional isotherms are shown on this diagram as normal

lines. (All isotherms on the PV diagram would be vertical lines
on the PT diagram.) One of these isotherms is a supercritical
isotherm (T>Tc). Because this isotherm does not cross a phase
boundary, it is smooth.The other isotherm is a subcritical
isotherm (T<Tc), which consists of three distinct sections. The
section in the liquid region is very steep, because liquid volume
changes very little with pressure; that is, liquids are nearly
incompressible. The section in the vapor region shows that the
vapor volume depends strongly on pressure, because vapors
are quite compressible. Finally, the horizontal section in the twophase region represents all possible two-phase mixtures,
ranging from 100% liquid at the saturated liquid line to 100%
vapor at the saturated vapor line. The constant pressure at
which this occurs is the vapor pressure. Finally, note that along
all three isotherms in the single phase regions, volume always
increases with decreasing pressure.
Introduction to Critical Constants

Critical temperature (Tc), pressure (Pc), and volume (Vc)
represent three widely used pure component constants. We
have already seen the importance of the critical point on the PT
and PV diagrams. The critical point is also the basis for the
theory of corresponding states, which will be discussed later in
this lecture. In addition, these constants are used in many other
property correlations. Experimental values for the critical
constants are generally available only for the more common
components. (See references below.) For other components, it
will be necessary to estimate the critical values.
Critical Constant References

Perhaps the best compilation of critical constants is a report by
Ambrose:
Ambrose, D., Vapour-Liquid Critical Properties, NPL Report
Chem. 107, National Physical Laboratory, Teddington, UK
(February, 1980).
Only experimentally measured critical constants are given in this
report. Where more than one experimental value were available,
an evaluation was done to select the most reliable value.
18

Physical Properties
Many other references are available that provide values for

critical constants, including:
TRC [Thermodynamics Research Center], TRC
Thermodynamic Tables - Hydrocarbons, Texas A&M
University, College Station, Texas.
TRC [Thermodynamics Research Center], TRC
Thermodynamic Tables - Non-Hydrocarbons, Texas A&M
University, College Station, Texas.
American Petroleum Institute, Technical Data Book - Petroleum
Refining, 4th Ed., API, Washington, DC, 1987.
DIPPR [AIChE Design Institute for Physical Property Data],
Tables of Physical and Thermodynamic Properties of Pure
Compounds, Project 801, Pennsylvania State University, looseleaf sheets extant, 1990.
Generally, these references give a combination of experimental
and estimated values. It is sometimes difficult to distinguish
between them.
Critical Constant Estimation Methods

Most of the generalized methods for estimating critical constants
employ a group contribution approach. There are three popular
methods in use for the critical property estimation. The first one
is the Lydersen (1955) method. It is simple to use and is
available in PRO II, HYSIS and Aspen Plus.
In 1984, Joback reevaluated Lydersens method by using more
recent experimental values. His modified version is only slightly
different from the original Lydersen method.
Another method was developed by Ambrose in 1979-80. The
Ambrose method is slightly more accurate than the Lydersen or
Joback methods, but is more complicated to use.
Generally, the following data are needed in order to use the
critical constant estimation methods:
.
Molecular structure.
Normal boiling point (Tb) in R.
19

Physical Properties
Molecular weight (MW).
Lydersens Method
The three critical properties are estimated by a group
contribution technique using the following equations:
Tc ( R)
Tb ( R)
0.567 + T ( T )2
Pc (atm)
MW
(0.34 + P )2
Vc (cm3/g-mol)
= 40 + V
The quantities are evaluated by summing contributions for

various atoms or groups of atoms as shown in this table:
Nonring Increments:
______
_______
_______
0.020
0.227
55.0
0.012
0.210
51.0
0.0
0.210
41.0
0.013
0.184
44.5
0.012
0.192
46.0
|
CH3, CH2
|
CH
|
|
C
|
Ring Increments:
|
CH2
|
CH
|
20

Physical Properties
|
=CH
0.011
0.154
37.0
0.011
0.154
36.0
|
=C
Values of the quantities for many more increments are available in Reid, Prausnitz,
and Sherwood (the third edition of The Properties of Gases and Liquids).
Example 2.1: Critical Constants for Isooctane
Calculate the critical constants for isooctane (2,2,4-trimethylpentane), C8H18.
C
CCCCC
Tb = 210.6F
MW = 114.23
|
C
|
Nonring increments: 5(CH3), 1(CH2), 1(CH), 1(C)

|
T
= 5(0.020) + 0.020 + 0.012 + 0 = 0.132
= 5(0.227) + 0.227 + 0.210 + 0.210 = 1.782
= 5(55) + 55 + 51 + 41 = 422
Tc =
210 .6 + 459 .67

= 983 R = 524 F
0 .567 + 0 .132 ( 0 .132 ) 2
Pc =
114.23
(0.34 + 1.782)
= 25.4atm = 373psia
Vc = 40 + 422 = 462 cm3/g-mol = 7.4 ft3/lb-mol
21

Physical Properties
COMPARISON OF LYDERSEN PREDICTIONS

Actual
Percent
Value
_____
Error
______
Tc,F
519.4
0.9
Pc, psia
372.4
0.2
Vc, ft3/lb-mol
7.50
-1.3
Comparison of Estimation Methods

Typical percent errors for estimating the critical constants by various methods are given
below:
Method
Tc
Pc
Vc
__________
_____
_____
_____
2-5
4 - 10
4 - 10
Joback
0.8
5.2
2.3
Ambrose
0.7
4.6
2.8
Lydersen
The numbers for the Joback and Ambrose methods are average errors based on a
comparison to experimental values for several hundred components. The numbers for
the Lydersen method are expected errors because a detailed comparison is not
available. The expected errors for the Joback and Ambrose methods are close to the
Lydersen method. Exercise 2.2 will give you practice using Lydersens Method. Use
Work Aid 2.1.
22

Physical Properties
Introduction to Corresponding States

The theory of corresponding states, as proposed by van der
Waals in 1873, indicates that the value of a reduced property for
all substances is the same at the same reduced conditions.
Stated differently, it indicates that a universal function exists that
relates a property of all substances to the critical constants. This
theory provides the single most important basis for the
development of generalized property prediction correlations.
The major advantage of generalized correlations based on
corresponding states is that they can be used to predict the
properties of substances for which very little experimental
information is available. We will discuss both the two-parameter
theory, as originally proposed by van der Waals, and the threeparameter theory, which is widely used today.
Two-Parameter Corresponding States

Usually the critical constants Tc and Pc are used for the two
parameters. This method was popular until about 1955. As an
example we will consider the gas compressibility factor, Z
(this will be discussed in more detail in the next lecture). Z is
given by:
Z = PV/RT
where R is the universal gas constant. Z indicates the
nonideality of a gas, since it is equal to 1 for an ideal gas. A
generalized function for calculating Z, based on two-parameter
corresponding states, would look like:
Z = f(Tr, Pr)
where Tr = T/Tc and Pr = P/Pc. An example of the function
f (Tr , Pr ) is shown in the generalized compressibility chart
reproduced in Figure 14. Generally, two-parameter correlations
such as this are reliable only for simple molecules. They are
usually not sufficiently accurate even for nonpolar molecules
such as paraffins.
Example 2.2: Compressibility Factor for Hexane
Calculate Z for hexane at 650F and 900 psia.
23

Physical Properties
Tc
= 453.7F
Pc = 436.9 psia
Tr
= (650 + 459.67)/(453.7 + 459.67)
=1.21
Pr
= 900/436.9
=2.06
Value from Edmister and Lee, p.76 (Figure 14): Z = 0.58
Three-Parameter Corresponding
Several third parameters have been proposed to improve twoparameter corresponding states correlations. In 1955, Lydersen
used the critical compressibility factor, Zc, which is defined
as:
PV
Zc = c c
RTc
In 1954, Riedel introduced the critical alpha, c, which is
related to the temperature derivative of the vapor pressure at
the critical point:
s
c =
d ln Pr
dln Tr
at Tr = 1
Ps
, and Ps is the vapor pressure.
Pc
While successful, these two third parameters suffer from having
to be evaluated at the critical point. Since the necessary data
are often not available, these parameters usually have to be
estimated.
where Prs =
The most successful and popular third parameter, the acentric

factor, , was developed by Pitzer in 1955. The acentric factor
is defined in terms of the vapor pressure at a reduced
temperature of 0.7:
s
= -log10Pr 1
(calculated at Tr = 0.7)
24

Physical Properties
One advantage of is that the vapor pressure data are often

available. The temperature at Tr = 0.7 is usually near the normal
boiling point. Values for the acentric factor are available in most
references that give critical constants. As originally proposed,
the acentric factor represented the deviation of the shape of the
molecule from spherical. Thus, for simple spherical molecules
(e.g., argon or methane) the acentric factor is near 0. However,
for larger, nonspherical molecules, the acentric factor increases.
A simple equation for estimating the acentric factor, if the vapor
pressure at Tr = 0.7 is not known, was developed by Edmister in
1961:
=
3 log10 Pc
1
7 Tc / Tb 1
where Pc must be in atmospheres.

As an example, we will again consider Z. A generalized function
for calculating Z, based on three-parameter corresponding
states, would look like:
Z = f(Tr, Pr, )
Pitzer et al., proposed the following function in 1955:
Z = Z0 + Z1
where Z0 = f(Tr,Pr) and Z1 = f(Tr,Pr). Graphs of these functions
are given in Figures 6.5 and 6.6 in Edmister and Lee (pages 72
and 73), reproduced in Figures 14 and 15.
Generally, three-parameter correlations such as this are reliable
for nonpolar and weakly polar molecules such as hydrocarbons
or light gases. However, they are usually not sufficiently
accurate for strongly polar molecules such as alcohols. It is
possible that a fourth parameter may be needed for these
molecules.
Example 2.3: Critical Compressibility Factor for Hexane
Calculate Z for hexane at 650F and 900 psia (same as
previous example).
= 0.2957
25

Physical Properties
Tr
= 1.21
Pr
= 2.06
From Figures 6.5 and 6.6 in Edmister and Lee (pages 72 and
73), or Figures 14 and 15:
Z0
= 0.58
Z1
= 0.58 + 0.2957(0.17)
= 0.17
= 0.630
Actual value for Z = 0.637

Comparison of values for Z:
Z
_______
% Error
_______
Two-parameter
0.58
-8.9
Three-parameter
0.630
-1.1
26

Physical Properties
DENSITY OF GASES AND LIQUIDS

Introduction
This part of the first module takes a closer look at methods to
calculate the density of gases and liquids. Density is needed in
many engineering calculations, such as sizing equipment and
calculating pressure drop. Density is usually given the symbol
in chemical engineering texts. Density is the inverse of the
specific volume. That is, if we designate V as specific volume in
ft3 per lb-mol of material, then , the density in lb-mol/ft3, is
defined as:
1
V
The mass density in lb/ft3 is equal to the molar density times the
molecular weight M, in lb/lb-mol.
The total volume of a substance, like its mass, is an extensive
property. That is, it is proportional to the amount of material
being considered. However, specific volume (or density) is an
intensive property, independent of the amount of the substance
and defined at every point in the substance.
It is an experimental fact that the specific volume, V, of a fluid of
known composition is fixed by two intensive variables:
temperature, T, and pressure, P. It is just as correct to state that
P is fixed once T and V are known. The connection between
these variables is the PVT behavior of a substance. It is
necessary to know the PVT behavior of real fluids to calculate
the variation of thermodynamic properties with temperature and
pressure.
This lecture discusses the calculation of density (or volume)
given the temperature and pressure. ChE 202.02 will discuss
further the connection between PVT behavior and other
thermodynamic properties.
Finally, in calculating PVT properties we often work in terms of
the dimensionless variable Z, the compressibility factor:
Z=
PV
RT
27

Physical Properties
where R is the gas constant. R = 10.732 if P is in psia, V in

ft3/lb-mol, and T in R. Since PV = RT for an ideal gas, the
deviation of Z from unity is a measure of the deviation of the
PVT behavior of a fluid from that of an ideal gas.
General PVT Behavior

Lecture 2 reviewed general PVT behavior based on PT and PV
plots. It is also useful to consider the ZP plot.
Figure 8 shows the PVT behavior as a plot of Z versus P. The
ideal gas state is the point Z = 1 at P = 0. The saturated vapor
line begins near Z = 1, at the triple point, and falls to the critical
compressibility factor, Zc (about 0.3), as temperature increases
from the triple point to the critical point. Over the same range, Z
of the liquid rises from a value well below 0.1 to 0.3. The
subcritical isotherms of Z versus P are vertical in the two phase
region, the critical isotherm has a vertical inflection point at the
critical point, and all of the isotherms have a minimum in Z.
Figure 8. Compressibility Factor for Propane
Finally, in the vicinity of P = 0, the isotherms approach linear

behavior in Z versus P, with the slope varying systematically
with temperature.
28

Physical Properties
Summarizing PVT Behavior of Real Fluids

It is useful to summarize the PVT behavior of real fluids to
emphasize the physical basis for selecting methods to calculate
density. In order of complexity of the methods, we have:
For Gases:
As P approaches zero, all gases approach ideal behavior

(PV = RT).
At low pressures, PV/RT (or Z) is a linear function of P.
At high pressures, more complex equations are needed.
For temperatures well below Tc, V is almost independent of

pressure.
Thus, V = saturated liquid volume to a good approximation in

this region.
For Liquids:
For Supercritical Fluids:

Oversimplified methods are not adequate.
Equations of State (which will be discussed later) work well

in this region.
For the Immediate Critical Region:

Z versus P and P versus V have an infinite slope at the
critical point.
Zc ranges from 0.2 to 0.3 for light hydrocarbons.
Even fairly elaborate methods are subject to substantial

error.
29

Physical Properties
Lee-Kesler Corresponding-States
The Abbott correlation is useful for simple hand calculations at
low pressure, but for more general calculations, we must use
the general version of the Pitzer correlation:
Z = Z(0)(Tr,Pr) + Z(1)(Tr,Pr)
In this general form, Z(0), the simple fluid term, and Z(1), the
correction term, are functions of both Tr and Pr . Pitzers original
correlation (1955) was graphical and tabular and is still used in
some sources. Lee and Kesler in 1975 developed an analytical
form for these functions, suitable for computer calculations,
which is somewhat more accurate than the original correlations,
especially for the correction term. Tables of Z(0) and Z(1)
calculated from the Lee-Kesler equations* are given in Reid,
Prausnitz, and Poling as Tables 3-2 and 3-3 (also Edmister &
Lee Tables 6.2, 6.3, Figures 6.5 & 6.6)
* The computer version of the Lee-Kesler method is actually based on an equivalent formulation in terms
of the simple fluid (essentially methane) and the reference fluid (octane). Since Z is a linear function of
for a particular choice of Tr and Pr , the following is equivalent to the Pitzer form:
(0)
(ref)
Z = Z (Tr,Pr) +[/
where:
(ref)
(Tr,Pr)
ref)
)][Z
(ref)
(Tr,Pr)
- Z(0)(Tr,Pr)]
= compressibility factor of reference fluid

= acentric factor of reference fluid = 0.3978
30

Physical Properties
The Lee-Kesler method is widely used in process simulators

and other computer programs. It is still the most accurate
general purpose method valid over a wide range of conditions.
For pure components, hand calculations with the Lee-Kesler
tables usually will agree with computer calculations to within the
accuracy of the correlation (usually to less than 2%, except in
the immediate critical region).
The Lee-Kesler computer method is reasonably accurate in the
liquid region, but it is not convenient to use the Lee-Kesler
tables for liquids. Rather, we recommend a simple method to
calculate saturated liquid density.
31

Physical Properties
Saturated Liquid Density from the Rackett Equation

The simplest method to calculate density (or volume) for liquids
is based on estimating the volume of a saturated liquid: a liquid
at its vapor pressure for the temperature of interest. Since
liquids are not very compressible (at least for reduced
temperatures below about 0.85), one can usually neglect the
effect of pressure on liquid density, at least up to pressures of
tens of atmospheres.
Reid, Prausnitz, and Poling discuss several liquid density
methods. For general purpose use, the Rackett equation (as
adapted by Spencer and Danner) is simple enough for hand
calculations and reasonably accurate.
If we express liquid density, , in mass units (lb/ft3) and
saturated volume, Vs, in molar units (ft3/lb-mol), then
=
M
Vs
where M is the molecular weight.

The Rackett equation gives saturated volume Vs as a function
of reduced temperature and the Rackett equation parameter
ZRA:
Vs = V* ZRA
where:
V = Z RA
RTc
Pc
= [1 - Tr](2/7)
This equation may also be written in the equivalent form:
Vs =
RTc
Z RA (1 + )
Pc
32

Physical Properties
ZRA is approximately equal to Zc, and V* is approximately equal

to Vc. However, more accurate prediction of liquid density
results if ZRA is determined from experimental data for the
saturated liquid density. Values of ZRA are tabulated in Reid,
Prausnitz, and Poling (Table 3-10) for many light hydrocarbons.
If no data are available, ZRA can be estimated from
ZRA = 0.29056 - 0.08775
There are other methods used by process simulators for
calculating liquid density. Of them, the most noteworthy is the
Hankinson-Brobst-Thomson method, which is discussed
extensively in Reid, Prausnitz, and Poling. This method (also
known as COSTALD, for COrresponding STAtes Liquid Density)
is the most accurate general method for predicting liquid
densities of light hydrocarbon mixtures.
Equation of State Methods

Our emphasis is on methods useful for hand calculations, but
we must also mention the most popular general purpose
computer method: equations of state. A short discussion is
needed to use and interpret process simulator density
calculations.
The term equation of state simply means an explicit equation
connecting P, V, and T. It is usually most useful to calculate
volume (or density) from temperature and pressure. However,
all equations of state useful for wide ranges of conditions are
explicit in pressure, not volume: they give P as a function of V
and T, not V as a function of T and P. The virial equation
volume series is one example, giving P as a function of V and T.
The Lee-Kesler method is based on an 11-constant pressureexplicit equation of state.
Cubic equations are now the most popular equation of state
form for computer calculations because of their usefulness in
calculating VLE (to be discussed in ChE 202.03). The density
calculated by these methods varies in accuracy.
The two most popular cubic equations are SRK (the Soave
modification of the Redlich-Kwong equation of state) and PR
(the Peng-Robinson equation of state).
33

Physical Properties
Consider the SRK equation as an example:

P=
where:
RT
a(T)
V b V(V + b)
= 0.08667
RTc
Pc
2
a(T)
= 0.4275
R Tc 2
Pc
= [1 + (0.48508 + 1.5517 0.156132)(1 Tr0.5)]2
The PR equation is very similar to the SRK equation but has a

somewhat more complex denominator of the second term on
the right, as well as somewhat different coefficients for the a(T)
function.
Both the SRK and PR equations give reasonably accurate
predictions of vapor density. They are generally accurate within
5% outside the critical region. They are, however, somewhat
less accurate than the Lee-Kesler method.
In the liquid region, neither of these methods is as good as the
Lee-Kesler method. The SRK method is especially inaccurate,
even more so for hydrocarbons with carbon numbers of three or
more. PR was specifically developed to improve liquid density
for condensates in gas processing. However, there is a limit to
the improvement one can achieve without introducing more
complex volume dependence, and the PR method can be in
error by as much as 15%. It is generally recommended not to
use SRK or PR for liquid densities.
Exercise 3.2 continues the illustration of density calculations for
propane.
34

Physical Properties
Mixtures
The density of mixtures is examined by considering the
techniques used, in turn, for Pitzer/Lee-Kesler, virial equation,
and equations of state.
Mixtures (Pitzer/Lee-Kesler)
For the Pitzer/Lee-Kesler corresponding-states methods, we
require values of the critical temperature, critical pressure, and
acentric factor to characterize the mixture: Tcm, Pcm, and m.
We then calculate Zm, the mixture compressibility factor, as
Zm = Z(0)(Trm, Prm) + mZ(1)(Trm,Prm)

where:
Tr m
= T/Tcm and Pr m = P/Pcm
Tcm and Pcm are known as the pseudocritical temperature and

pressure. The term pseudocritical means the apparent critical
constant that makes the correlation give the correct value of Zm.
Obviously the pseudocriticals must be a function of the
composition of the mixture expressed as mole fractions x1, x2,
..., xN. These criticals are usually different from the true
criticals of a mixture, which are the conditions for which the
vapor and liquid properties converge.
For hand calculations, it is generally sufficient to use a simple
molar average for Tcm and m:
Tcm
m
= xiTci
= xii
For the critical pressure, however, the simplest realistic rule is

Pcm =
Tcm ( x iZ ci )
x T Z
i ci ci
Pci
35

Physical Properties
Computer versions of the Lee-Kesler method use considerably

more complex mixing rules. Generally, the rules given here yield
densities that agree with the more complex mixing rules when
the ratios Tci / Tcj and Pci / Pcj fall in in the range 0.5 2.0 for all
of the i / j pairs in a mixture. The process simulators allow the
use of two kinds of mixing rules: the original Lee-Kesler and
Lee-Kesler-Plcker. Both of these are discussed by Reid,
Prausnitz, and Poling.
Mixtures (SRK Equation of State)
Mixing rules for the SRK Equation of State used for light
hydrocarbons are:
bm = xibi
a m = xi x ja ij
i j
where aij = (aiaj)0.5(1 - Cij).

Here Cij is a binary interaction parameter for the SRK equation
of state. This parameter is usually taken as zero for binaries
where both components i and j are hydrocarbons. The process
simulators contain many nonzero default values of Cij for
nonhydrocarbon/hydrocarbon binaries.
Example 3.1: Density Calculation for Mixtures
Consider the propane/pentane binary with equal composition by
weight. What is the density at 240F and 293 psia using the
Lee-Kesler method?
36

Physical Properties
Solution:
Pure component properties are:
(1)
(2)
Propane
Pentane
Tc
206.1F
385.5F
Pc
619.9 psia
488.8 psia
0.1527
MW
0.251
44.096
72.151
Zc
0.281
0.263
Wt. Fraction
0.5
0.5
Mole Fraction,
x1
x1
= 0.6207
x2
= 0.3793
0.5
44.096
=
0
.
5
0.5
44.096 72.151
Tc1 / Tc2 = 0.787

Pc1 / Pc2 = 1.268
Both ratios are in the range 0.5 to 2.0, where simple mixing
rules are reasonably accurate.
Tcm
= (0.6207)(206.1) + (0.3793)(385.8)
= 274.3F
= 733.9R
= (0.6207)(0.1527) + (0.3793)(0.251)
= 0.190
37

Physical Properties
Pcm =
(733.9)[(0.6207 )(0.281) + (0.3793)(0.263)]

(0.6207 )(665.77 )(0.281) + (0.3793)(845.47 )(0.263)
619.9
488.8
Pcm = 559.1 psia
Trm =
Prm =
(240 + 459.67 ) = 0.953

733.9
293
= 0.524
559.1
From Lee-Kesler tables or graphs in Edmister, Vol.1,

Z(0)
= 0.747
Z(1)
= 0.747 + (0.19)(-0.09)
= -0.09
= 0.730
Process simulator methods at the same conditions give

SRK
Lee-Kesler
0.736 (+ 0.8%)
0.728 (- 0.3%)
As expected, SRK and Lee-Kesler gives similar results, and the

Lee-Kesler hand calculation gives reasonably good agreement
with the process simulation methods.
Calculation of mixture density uses Z = PV/RT, so
density
1
P
=
V ZRT
density
293.0
(0.730)(10.732)(699.67)
density = 0.0534 lb-mol/ft3

Using the mixture molecular weight as
MWm = (0.6207)(44.096) + (0.3793)(72.151) = 54.738
gives
mass density = (0.0534)(54.738) = 2.93 lb/ft3
38

Physical Properties
VAPOR PRESSURE
Introduction
This lecture focuses entirely on pure component vapor
pressures. First, we look at a typical vapor pressure curve and
discuss some of its unique features. Next, we discuss several
equations that have been used to represent vapor pressures,
including their advantages and disadvantages. Then we learn
how the heat of vaporization can be determined from vapor
pressure. References that contain vapor pressure data or
equation coefficients will also be presented. Finally, we will
briefly discuss the use of vapor pressure in the process
simulators.
The location of the vapor pressure curve on the PT diagram was
shown in Lecture 2. This curve is the boundary for the vapor
and liquid phases, and thus it represents the combinations of
pressure and temperature at which a pure component can
coexist in the vapor and liquid phases. In ChE 202.03, it will be
shown that vapor pressure is a key property in predicting vaporliquid equilibrium for mixtures.
Typical Vapor Pressure Curve

A typical vapor pressure curve is shown in Figure 10 as the
exaggerated curve (it is actually much closer to the straight
line). In this figure the logarithm of the vapor pressure is plotted
versus reciprocal absolute temperature. The straight line is the
Clausius-Clapeyron equation:
ln Ps = A
B
T
The Clausius-Clapeyron equation has been drawn so that it

passes through the vapor pressure curve at the critical point (Tr
= 1) and at Tr = 0.7. This equation shows that vapor pressure
data generally fall close to a straight line when plotted this way.
However, for accurate predictions, the Clausius-Clapeyron
equation is reliable only when used to represent vapor
pressures over small temperature intervals.
39

Physical Properties
Critical Point
Exaggerated Curve
In P s
Straight Line
(Clausius-Clapeyron)
T r = 0.7
1/ T
Figure 10
FIGURE 10. Typical Vapor Pressure Curve
When compared to a straight line, vapor pressures usually show

a change in curvature (inflection point) between Tr of 0.7 and
1.0. Generally, this occurs between 0.8 and 0.85. In addition,
vapor pressures nearly always fall below a straight line at Tr
below 0.7. Based on experience, it has been found that at least
a four-constant equation is needed to represent vapor pressure
accurately from the critical point to the triple point.
Antoine Vapor Pressure Equation

Perhaps the most popular and widely used equation for
representing vapor pressure is the Antoine equation:
ln Ps = A
B
T+C
40

Physical Properties
Antoine proposed this simple modification of the ClausiusClapeyron equation in 1888. Even today, this equation is widely
used to represent vapor pressure, and Antoine constants are
available in many references. The equation is very reliable from
about 10 to 1500 mmHg; however, the accuracy deteriorates
rapidly beyond this range. It usually underpredicts vapor
pressure at high pressures and overpredicts vapor pressure at
low pressures. One of the convenient features of this equation is
that either the vapor pressure or the temperature can be directly
calculated without iterative calculations. This is not the case with
nearly all other vapor pressure equations. Unfortunately, there
are no reliable generalizations for the Antoine constants.
Therefore, the three constants must always be determined by
regressing experimental data.
Riedel Vapor Pressure Equation

In 1954, Riedel proposed the following vapor pressure equation:
B
ln Ps = A + + Cln T + DT 6
T
In addition, Riedel developed a reduced, generalized form of

this equation where:
Ps = f(Tc, Pc, c)
This equation is an example of a three-parameter corresponding
states equation for vapor pressure. The parameter c is
generally determined from the normal boiling point. Riedel's
equation is very reliable from about 1 atm to the critical point.
However, the accuracy deteriorates below 1 atm, where it
usually underpredicts the vapor pressure. The four constants in
this equation can be determined by regressing experimental
data. However, they are usually determined from the
generalized equation using the critical point and the normal
boiling point.
Frost-Kalkwarf Vapor Pressure Equation

The following vapor pressure equation was proposed in 1953 by
Frost-Kalkwarf:
41

Physical Properties
DP s
B
ln Ps = A + + Cln T + 2
T
T
Later, Thodos and coworkers (1956-1962) developed a

generalized form of this equation. The accuracy and the
determination of the four constants are similar to the Riedel
equation. The equation has been included here only because it
is used extensively in process simulators. It is not used much
elsewhere, because an iterative calculation is needed to
determine the vapor pressure.
Wagner Vapor Pressure Equation

In 1973, Wagner proposed the following vapor pressure
equation:
A(1 Tr ) + B(1 Tr )1.5 + C(1 Tr )3 + D(1 Tr )6
ln Prs =
Tr
This equation is gaining popularity and is currently one of the

most accurate vapor pressure equations. It can accurately
represent vapor pressures from the triple point to the critical
point. A disadvantage of this equation is that there is currently
no generalized method for determining the four constants.
Therefore, it is necessary to determine the four constants by
regressing experimental data. However, if no (or few)
experimental vapor pressure data are available from the triple
point to the critical point, then it is also necessary to constrain
the equation to give a reasonable shape for the vapor
pressure curve. If this is not done, the equation may extrapolate
very poorly. Thus the determination of the constants is more
difficult than for other vapor pressure equations.
Lee-Kesler Vapor Pressure Equation

In 1975, Lee and Kesler proposed the following generalized
corresponding states vapor pressure equation based on the
Riedel functional form:
InPrs = f 0 + f 1
f0 = f(Tr) = 5.92714 6.09648/ Tr 1.28862 ln Tr + 0.169347
Tr6
42

Physical Properties
f1 = f(Tr) = 15.2518 15.6875/ Tr 13.4721 ln Tr + 0.43577

Tr6
This equation is a function of three parameters:
Ps = f(Tc,Pc,)
When vapor pressures are calculated from this equation, it is
recommended that the equation first be used to calculate the
acentric factor, , from Tc, Pc, and the normal boiling point, Tb.
For this purpose, the Lee-Kesler equation is rearranged as
follows:
=
ln
Pc f 0 (Tbr )
f 1(Tbr )
where Tbr = Tb/Tc and Pc must be in atmospheres. This

expression for the acentric factor is more accurate than the
Edmister equation given in Lecture 2. Finally, the accuracy of
this equation in predicting vapor pressures is similar to that of
the Riedel equation.
Comparison of Vapor Pressure Equations

A comparison of the various vapor pressure equations for
predicting the vapor pressure of acetone is shown in Figure 11.
As expected, the Clausius-Clapeyron equation is the least
accurate, especially at lower temperatures. The two constants
were determined from the critical point and the normal boiling
point. The three constants for the Antoine equation were
determined by regressing the experimental data below about 30
psia. Again, as expected, the Antoine equation is the least
accurate at higher temperatures. The four constants from the
Wagner equation were determined by regressing all the
experimental data. The Wagner equation clearly gives the most
accurate predictions. The constants for the Frost-Kalkwarf,
Riedel, and Lee-Kesler equations were determined using their
generalized forms from the critical point and the normal boiling
point. All three of these equations have similar accuracy.
43

Physical Properties
PERCENT ERROR
T, F
Tr
Ps (exp.),
psia
ClausiusClapeyron
Antoine
Wagner
FrostKalkwarf
Riedel
LeeKesler
6.9
0.510
0.619
24
1.6
0.2
-6.2
-7.2
-7.9
32.5
0.538
1.38
15
0.3
-0.1
-4.5
-5.6
-6.2
62.5
0.571
3.12
8.3
-0.1
0.2
-2.3
-3.3
-3.7
117.2
0.631
10.8
1.5
-0.7
0.1
-0.3
-0.2
172.0
0.691
29.2
-1.0
-0.6
1.1
1.6
1.9
242.9
0.768
82.0
-1.5
0.1
0.2
0.9
1.8
2.2
343.9
0.878
256
-0.3
-0.5
-0.2
0.4
0.7
387.4
0.926
386
0.5
-1.5
-0.1
-0.1
0.2
0.3
454.9
1.0
682
-4.5
FIGURE 11. Comparison of Vapor Pressure Equations for Acetone
Heat of Vaporization from Vapor Pressure

The heat of vaporization is the difference in enthalpy between
the saturated vapor and saturated liquid at the same
temperature. The Clapeyron equation (which will be derived in
ChE 202.02) relates the heat of vaporization to the temperature
derivative of the vapor pressure:
dPs
Hv
=
dT TV v
where Hv is the heat of vaporization and Vv is the volume

change upon vaporization.
Often Vv is replaced by Zv, which results in the following
equation:
dln Ps
Hv
=
d(1/T)
RZ v
44

Physical Properties
where Zv is the difference in compressibility factor between the

vapor and liquid phases. Below the normal boiling point it is
generally safe to assume that Zv is approximately one. This
gives the following expression for the heat of vaporization:
H v
Rd1nP s
d(1 / T )
By taking the temperature derivative of a vapor pressure

equation, it is possible to use this equation to obtain fairly
reliable estimates of the heat of vaporization below the normal
boiling point. If an appropriate estimate is made for Zv, then
the heat of vaporization can be calculated above the normal
boiling point. Indeed, many so-called experimental heat of
vaporization data given in references have actually been
calculated by this method.
Vapor Pressure References

Vapor pressure data and equation constants are given in many
references. Two of the best and most comprehensive are the
TRC tables and the DIPPR tables. The TRC tables give Antoine
constants that are valid from 10 to 1500 mmHg for several
thousand components. In addition, vapor pressures, calculated
from the Antoine constants, are given in tables for the same
pressure range. In most cases, the Antoine constants have
been determined from a critical evaluation of the available
experimental data. For a few components, tables are given for
lower or higher pressures.
The DIPPR tables give equation constants for a modified Riedel
equation:
ln Ps = A +
B
+ CInT + DT E
T
E is usually 1, 2, or 6. This equation can give reliable predictions

from the critical point to somewhere below the normal boiling
point. Equation constants are given for more than 1300
components.
Process Simulator Vapor Pressure
45

Physical Properties
The process simulators use an extended Antoine equation to

calculate the vapor pressure for its library components. The
equation constants have been obtained from PPDS or DIPPR.
Although rarely necessary, the user can override the constants
for any component.
For nonlibrary components it is recommended that the user
supply vapor pressure data, if necessary. This can be done by
supplying tabular data or equation coefficients. Tabular data can
be input for 2 to 10 temperatures. These data are then fit to a ln
Ps versus 1/T equation.
If possible, it is recommended that the user input equation
coefficients instead of tabular data. Coefficients can be supplied
for either of the following two equations:
ln Ps = C1 +
C Ps
C2
+ C4T + C5T2 + C6 ln T + 7 2
C3 + T
T
ln Ps = C1 +
C2
+ C3 ln T + C4TC5 + C6T3 + C7T6
T
These two equations allow direct input of the coefficients for all
of the popular vapor pressure equations, except Wagners.
Summary
In this module we have reviewed the importance of physical
properties in predicting vapor-liquid equilibria, enthalpy, and the
pressure-volume-temperature relationships. Frequently the
necessary calculations require conversion of units between
measurement systems.
We discussed the concepts of gas-liquid critical constants, and
showed how they are used in the corresponding-states methods
for property prediction. These methods were demonstrated for
the prediction of density and vapor pressure.
46

Physical Properties
Work Aid 1.1: Using Conversion Factor Tables

There are 12 tables in this Work Aid, one for each of the
following properties:
1.
Length
7.
Flow
2.
Area
8.
Energy
3.
Volume
9.
Power
4.
Mass
l0.
Absolute viscosity
5.
Density
11.
Kinematic viscosity
6.
Pressure
12.
Thermal conductivity
To convert the numerical value of a property expressed in one

of the units in the left column of a table to the value expressed
in units found in the top row, multiply the initial value by the
factor in the intersecting cell.
47

Physical Properties
Table 1. Length Conversions
48

Physical Properties
Table 2. Area Conversions
49

Physical Properties
Table 3. Volume Conversions
50

Physical Properties
Table 4. Mass Conversions
51

Physical Properties
Table 5. Density Conversions
52

Physical Properties
Table 6. Pressure Conversions
53

Physical Properties
Table 7. Flow Conversions
54

Physical Properties
Table 8. Energy Conversions
55

Physical Properties
Table 9. Power Conversions
56

Physical Properties
Table 10. Absolute Viscosity Conversions
57

Physical Properties
Table 11. Kinematic Viscosity Conversions
58

Physical Properties
Table 12. Thermal Conductivity Conversions
59

Physical Properties
Work Aid 2.1: Estimating Critical Constants; Lydersens Method

Given a pure hydrocarbon compound with a known molecular
structure, its molecular weight, MW, and its normal boiling point
temperature, Tb, estimate its critical temperature, Tc, critical
pressure, Pc, and critical volume, Vc, by following these steps:
1. Divide the molecular structure into groups of atoms,

corresponding to the groups
(Nonring Increments and Ring Increments) given in the table
on the next page.
2. For each group, find the corresponding value of T in the
table and add it to the other
values, to give T.
3. Calculate Tc:
Tc (o R) =
Tb (oR)
0.567 + T ( T )2
4. For each group, find the corresponding value of P and add

it to give P.
5. Calculate Pc:
Pc (atm) =
MW
2
(0.34 + P )
6. For each group, add the corresponding value of V to give

V.
7. Calculate Vc:
Vc (cm3/g-mol) = 40 + V
60

Physical Properties
Work Aid 2.1 (Contd): Lydersens Method Quantities
Nonring Increments:
|
CH3, CH2
|
CH
|
|
C
|
Ring Increments:
|
CH2
|
CH
|
|
=CH
|
=C
T
______
P
_______
V
_______
0.020
0.227
55.0
0.012
0.210
51.0
0.0
0.210
41.0
0.013
0.184
44.5
0.012
0.192
46.0
0.011
0.154
37.0
0.011
0.154
36.0
Values of the quantities for many more increments are available in Reid, Prausnitz,
and Sherwood (the third edition of The Properties of Gases and Liquids).
61

Physical Properties
Work Aid 3.1: Calculating Compressibility Factors with Pressure Series

Given the critical temperature, Tc, critical pressure, Pc, and the
acentric factor, , of a compound, calculate its compressibility
factor, Z, at temperature T and pressure P by following these
steps:
1. Calculate reduced temperature, Tr, and pressure, Pr:
Tr = T
Tc
Pr = P
Pc
2. Calculate approximations to B(0) and B(1):

0
B( ) = 0.083 0.422
Tr1.6
1
B( ) = 0.139 0.172
Tr 4.2
3. Calculate BPc /RTc:
BPc
RTc
= B(0) (Tr) + B(1)(Tr)
4. Calculate Z:
Z=1+
P r BP c
Tr RT c
62

Physical Properties
Work Aid 3.2: Calculating Liquid Density

Given a liquid, its molecular weight, MW, critical temperature,
Tc, critical pressure, Pc, and its Rackett equation parameter,
ZRA, calculate its saturated liquid density at temperature T as
follows:
1. Calculate the reduced temperature (R):
Tr = T
Tc
2. Calculate :
(2/ 7)
= [1 Tr ]
3. Calculate the saturated volume, VS:
VS = RTc ZRA(1+)
Pc
4. Calculate the liquid density, :
= MW
VS
63

Physical Properties
FIGURE 13. Generalized compressibility factor for simple fluid
64

Physical Properties
FIGURE 14. Generalized compressibility factor correction from deviation from simple
fluid
65

Physical Properties
TABLE 13. Compressibility Factors, Values of Z(0)
66

Physical Properties
TABLE 13. Compressibility Factors, Values of Z(0) (continued)
67

Physical Properties
TABLE 14. Compressibility Factors, Values of Z(1)
68

Physical Properties
TABLE 14. Compressibility Factors, Values of Z(1) (continued)
69

Physical Properties
acentric factor
A corresponding-states parameter that measures the

noncentral nature of intermolecular forces ().
binary interaction
parameter
A correction for the deviation of the equation-of-state

parameter aij from the geometric mean, (aiaj)0.5.
Clapeyron equation
An equation governing phase transitions of a

substance, dP/dT = H/(TV), in which P is the
pressure, T is the temperature at which the phase
transition occurs, H is the change in heat content
(enthalpy), and V is the change in volume during the
transition.
Clausius-Clapeyron
equation
A simplification of the Clapeyron equation.
compressed liquid
region
The liquid region under a pressure higher than its vapor

pressure.
compressibility
factor
The product of the pressure and the volume of a gas,

divided by the product of the temperature of the gas
and the gas constant; this factor, Z, may be inserted in
the ideal gas law to take into account the departure of
real gases from ideal gas behavior.
corresponding
states
The condition when two or more substances are at the

same reduced pressure, temperature, volume.
correspondingstates correlation
A correlation relating reduced properties.
critical alpha
A corresponding-states parameter, related to the

temperature derivative of the vapor pressure at the
critical point (c).
critical
compressibility
factor
Defined as Zc = Pc Vc /RTc, where R is the gas

constant and Pc, Vc, Tc, are, respectively, the critical
pressure, volume, and temperature.
critical point
The point at which two phases become identical.
critical pressure
The highest pressure at which a pure component can

exist in either the vapor or liquid phase.
critical region
The region in the neighborhood of the critical point.
70

Physical Properties
critical temperature
The highest temperature at which a gas can be

liquefied by increasing the pressure.
critical volume
The volume of a substance at the critical point, that is,

at the critical temperature and pressure.
density
Concentration of matter, measured by the mass per unit

volume.
enthalpy
The sum of the internal energy of a system plus the

product of the systems volume multiplied by the
pressure exerted on the system by its surroundings.
Also called heat content (fully described in ChE
202.02).
equation of state
A mathematical expression which defines the physical

state of a homogeneous substance (gas, liquid, or solid)
by relating volume to pressure and absolute
temperature for a given mass of the material.
extensive property
A property which is additive: if we have two identical

systems, an extensive property (such as volume or
mass) of the two is double that of each one.
fusion curve
A curve in P,T space along which liquid and solid

phases coexist.
gas constant
The constant of proportionality, R, appearing in the

equation of state of an ideal gas, equal to the pressure
of the gas times its molar volume divided by the
temperature.
heat capacity
The quantity of heat required to raise the system one

degree in temperature in a specified way, usually at
constant pressure or constant volume.
heat of mixing
The difference between the enthalpy of a mixture and

the sum of the enthalpies of its components at the same
pressure and temperature.
heat of reaction
The heat evolved or absorbed in a chemical reaction.
heat of vaporization
The quantity of heat required to evaporate one mole, or

a unit mass, of a liquid, at constant pressure and
temperature. Also known as enthalpy of vaporization.
71

Physical Properties
ideal-gas law
The equation of state for an ideal gas: PV = RT.
isotherm
A set of conditions at constant temperature.
K-value
Ratio of the vapor to the liquid mole fraction of i.
liquid-liquid
equilibria
Conditions describing the equilibrium between two liquid

phases.
melting curve
Fusion curve.
melting point
The temperature at which a solid component changes

to a liquid.
mixing rules
Equations that relate equation-of-state parameters for

mixtures to those for pure components.
normal boiling point The boiling point of a substance is the temperature at

which it boils. It varies with pressure. The normal
boiling point is the the boiling point at atmospheric
pressure.
normal fluid
A fluid that conforms to the three-parameter

corresponding-states theory (in particular, when the
third parameter is the acentric factor).
petroleum fraction
A narrow petroleum cut that is treated as a pure

component with a single boiling point and density.
pseudocritical
pressure
The critical pressure of a mixture used in

corresponding-states correlations.
pseudocritical
temperature
The critical temperature of a mixture used in

corresponding-states correlations.
reduced pressure
The ratio of the pressure of a substance to its critical

pressure.
reduced property
The ratio of the property of a substance to its value at

the critical point.
reduced
temperature
The ratio of the temperature of a substance to its critical

temperature.
72

Physical Properties
reflux ratio
Ratio of reflux rate (liquid recycled to the distillation

tower) to vapor product.
saturated liquid
A liquid pure component that is in equilibrium with its

vapor (under its vapor pressure).
second virial
coefficient
The coefficient in the viral equation accounting for twobody interactions.
second virial cross

coefficient
The coefficient in the viral equation accounting for

interactions between two different bodies i and j.
simple fluid
A fluid with simple spherical molecules (conforms to the

two-parameter corresponding-states theory).
specific volume
The inverse of density.
subcritical
Anything that is or takes place below the critical

temperature.
sublimation curve
The vapor pressure of a solid as a function of

temperature.
supercritical
Anything that is or takes place above the critical

temperature.
surface tension
The force acting on the surface of a liquid, tending to

minimize the area of the surface; quantitatively, the
force that appears to act across a line of unit length on
the surface.
third virial
coefficient
The coefficient in the virial equation accounting for

three-body interactions.
transport properties Properties of a compound or material associated with

momentum (fluid flow), heat transport or mass; for
example, viscosity and thermal conductivity.
triple point
A particular set of temperature and pressure at which

three different phases of one substance can coexist in
equilibrium.
vaporization curve
A curve in P,T space along which vapor and liquid

phases coexist. It begins at triple point and extends up
to the critical point.
73

Physical Properties
vapor-liquid
equilibria
The equilibrium relationship between the liquid and its

vapor phase for a partially vaporized compound or
mixture at specified conditions of pressure and
temperature.
vapor pressure
For a liquid or solid, the pressure of the vapor in

equilibrium with the liquid or solid.
virial coefficients
Coefficients in the virial equation.
virial equation
An equation of state in the form of a series of terms that

account for the deviation from ideal-gas behavior due to
two-body, three-body, and so on, interactions.
volatility
The tendency of a liquid to vaporize.
74

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Physical Properties of Gases and Liquids

IMPORTANCE OF PHYSICAL PROPERTIES................................................................ 3

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Physical Properties of Gases and Liquids

Riedel Vapor Pressure Equation.............................................................................. 41

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Physical Properties of Gases and Liquids

IMPORTANCE OF PHYSICAL PROPERTIES

ChE 202.01: Physical Properties.

ChE 202.02: Thermodynamics.

ChE 202.03: Vapor-Liquid Equilibria.

ChE 202.04: Properties of Petroleum Fractions.

ChE 202.05: Secondary Properties.

ChE 202.06: Chemical Equilibria.

This first module discusses why we are interested in physical

Lecture 1: Importance of Physical Properties.

Lecture 2: Critical Constants and Corresponding-States

Lecture 3: Density of Gases and Liquids.

Lecture 4: Vapor Pressure.

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Physical Properties of Gases and Liquids

We start with an introduction to physical propertieswhy we

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Physical Properties of Gases and Liquids

Basic Data Needs for Design

Vapor-liquid equilibria (VLE).

Density or, more generally, P-V-T (pressure-volumetemperature) properties.

Vapor-liquid equilibria, which include the vapor pressure of the

A property may have little influence on equipment size

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Physical Properties of Gases and Liquids

The correctness of a model used in equipment design may

Fouling of equipment cannot be quantified; therefore, the

There are many examples in the literature of how uncertainties

Examples from the Literature

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Physical Properties of Gases and Liquids

FIGURE 1. Butane/Pentane Splitter

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Physical Properties of Gases and Liquids

FIGURE 2. Heat Exchanger in Nitrogen Rejection Unit

Units and Conversions

The English or customary engineering system of units.

The metric system.

The SI (for Systme International) or international metric

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Physical Properties of Gases and Liquids

FIGURE 3. SI Base Units

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Physical Properties of Gases and Liquids

1 lbm x 32.174 ft/s2

To make lbf and lbm numerically equal:

Pressure (Force per Unit Area): pascal, Pa

FIGURE 4. Examples of Unit Conversions

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Physical Properties of Gases and Liquids

(MPa = 1,000,000 Pa). The standard atmospheric pressure, 1

In Equation 1, V is the molar volume, the volume of one mole

When we substitute into Equation 1, we obtain the values for R

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