Physical Properties

Dr. Ibrahim Dubdub

Towler (2008) Chapter 8

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INTRODUCTION

Physical properties of process materials are needed

at all stages of design, from the initial screening of
possible processes to the plant startup and
production.

This chapter covers physical properties, and the

estimation of physical property data.

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When a project is largely a repeat of a previous
project, the data and information required for the
design will be available in the company’s process
files, if proper detailed records are kept.

For a new project or process, the design data must

be obtained from the literature, or by experiment
(research laboratory and pilot plant), or purchased
from other companies.
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The literature on the physical properties of elements and
compounds is extensive, and reliable values for common
materials can usually be found. The principal sources of
physical property data are listed in the references at the
end of this chapter. Where values cannot be found, the
data required must be measured experimentally or
estimated. Methods of estimating (predicting) the more
important physical properties required for design are
given in this chapter.

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GENERAL SOURCES OF PHYSICAL PROPERTIES
In this section, those references that contain comprehensive
compilations of physical property data are reviewed.
International Critical Tables (1933) is still probably the most
comprehensive compilation of physical properties and is
available in most reference libraries. Though it was first
published in 1933, physical properties do not change, except in
as much as experimental techniques improve, and ICT is still a
useful source of engineering data. ICT is now available as an e-
book and can be referenced on the Internet through Knovel
(2003).
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Tables and graphs of physical properties
are given in many handbooks and
textbooks on chemical engineering and
related subjects. Many of the data given
are duplicated from book to book, but the
various handbooks do provide quick, easy
access to data on the more commonly
used substances.
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ACCURACY REQUIRED OF ENGINEERING DATA
The accuracy needed depends on the use to which the data
will be put. Before spending time and money searching for
the most accurate value or arranging for special
measurements to be made, the designer must decide what
accuracy is required; this will depend on several factors:

1. The level of design: Less accuracy is obviously needed

for rough screening calculations made to sort out possible
alternative designs than in the final stages of design, when
money will be committed to purchase equipment.
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2. The reliability of the design methods: If there is some uncertainty
in the techniques to be used, it is clearly a waste of time to search
out highly accurate physical property data that will add little or
nothing to the reliability of the final design.

3. The sensitivity to the particular property: How much will a small

error in the property affect the design calculation? For example, it
was shown in Chapter 5 that the estimation of the optimum pipe
diameter is insensitive to viscosity. The sensitivity of a design
method to errors in physical properties and other data can be
checked by repeating the calculation using slightly altered values.

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It is often sufficient to estimate a value for a
property (sometimes even to make an intelligent
guess) if the value has little effect on the final
outcome of the design calculation. For example,
in calculating the heat load for a reboiler or
vaporizer, an accurate value of the liquid
specific heat is seldom needed, as the latent heat
load is usually many times the sensible heat load
and a small error in the sensible heat calculation
will have little effect on the design. 01/10/2023 9

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If the purity of the acetone product required is less than 95%,
inaccuracies in the VLE plot have little effect on the estimate
of the number of stages required, as the relative volatility is
very high. If a high purity is wanted, say >99%, then reliable
data are needed in this region as the equilibrium line
approaches the operating line (a pinch point occurs). Of the
references cited, none gives values in the region above 95%,
and only two give values above 90%; more experimental
values are needed to design with confidence. There is a
possibility that the system forms an azeotrope in this region.
An azeotrope does form at higher pressure.
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PREDICTION OF PHYSICAL PROPERTIES

Whenever possible, experimentally determined values

of physical properties should be used. If reliable values
cannot be found in the literature and if time or facilities
are not available for their determination, then to proceed
with the design, the designer must resort to estimation.
Techniques are available for the prediction of most
physical properties with sufficient accuracy for use in
process and equipment design.

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Group contribution techniques are based on the
concept that a particular physical property of a
compound can be considered to be made up of
contributions from the constituent atoms,
groups, and bonds, the contributions being
determined from experimental data. They
provide the designer with simple, convenient
methods for physical property estimation,
requiring only a knowledge of the structural
formula of the compound. 01/10/2023 12

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In most cases, the methods described in the following sections, or their
equivalents, are available in commercial process simulation programs
such as AspenPlus, Chem-CAD, Pro II, and UniSim. The easiest way to
estimate mixture properties is usually to set up a stream with the desired
temperature, pressure, and composition in one of the simulators.

The design engineer should always check the results from the simulation
against any available data. If no experimental data are available, then it is
usually a good idea to make an independent estimate of any parameters
that have a strong influence on the design, to be satisfied that the results
from the simulator are credible. If the independent estimate does not
agree with the simulation result, then it may be worthwhile to conduct
some experiments to collect real data.
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DENSITY
Liquids
Values for the density of pure liquids can usually be found in the handbooks. It should
be noted that the density of most organic liquids, other than those containing a halogen or other
‘‘heavy atom,’’ usually lies between 800 and 1000 kg/m3.

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Gas and Vapor Density (Specific Volume)

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VISCOSITY

Viscosity values are needed for any design

calculations involving the transport of fluids
or heat. Values for pure substances can
usually be found in the literature. Liquid
viscosities are given in Appendix C. Methods
for the estimation of viscosity are given in
following sections.
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Liquids

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Variation with Temperature
If the viscosity is known at a particular temperature, the value at another temperature can be estimated with
reasonable accuracy (within+20%) by using the generalized plot.

Effect of Pressure

The viscosity of a liquid is dependent on pressure as well as temperature, but the effect is not significant
except at very high pressures. A rise in pressure of 300 bar is roughly equivalent to a decrease in
temperature of 18C.

Mixtures

It is difficult to predict the viscosity of mixtures of liquids. Viscosities are rarely additive, and the shape of
the viscosity-concentration curve can be complex. The viscosity of the mixture may be lower or,
occasionally, higher than that of the pure components. A rough check on the magnitude of the likely error
in a design calculation, arising from uncertainty in the viscosity of a mixture, can be made by using the
smallest and largest values of the pure components in the calculation and noting the result.

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Gases

Reliable methods for the prediction of gas viscosities and the effect of temperature and pressure are given by
Bretsznajder (1971) and Reid et al. (1987). Where an estimate of the viscosity is needed to calculate Prandtl
numbers, the methods developed for the direct estimation of Prandtl numbers should be used.
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8.8 THERMAL CONDUCTIVITY

The experimental methods used for the determination of

thermal conductivity are described by Tsederberg (1965),
who also lists values for many substances. The four volume
handbook by Yaws (1995–1997) is a useful source of thermal
conductivity data for hydrocarbons and inorganic compounds.
Solids

The thermal conductivity of a solid is determined by its form and

structure, as well as composition. Values for the commonly used
engineering materials are given in various handbooks.
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Liquids

The data available in the literature up to 1973 have been

reviewed by Jamieson et al. (1975). The Weber equation
(Weber, 1880) can be used to make a rough estimate of the
thermal conductivity of organic liquids for use in heat
transfer calculations:

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Gases
Approximate values for the thermal conductivity of
pure gases, up to moderate pressures, can be
estimated from values of the gas viscosity, using
Eucken’s equation (Eucken, 1912):

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Mixtures
In general, the thermal conductivities of liquid mixtures and gas
mixtures are not simple functions of composition and the thermal
conductivity of the components. Bretsznajder (1971) discusses the
methods that are available for estimating the thermal
conductivities of mixtures from a knowledge of the thermal
conductivity of the components. If the components are all
nonpolar, a simple weighted average is usually sufficiently
accurate for design purposes:

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8.9. SPECIFIC HEAT CAPACITY
Approximate values can be calculated for solids and liquids by
using a modified form of Kopp’s law, which is given by Werner
(1941). The heat capacity of a compound is taken as the sum of the
heat capacities of the individual elements of which it is composed.
The values attributed to each element for liquids and solids, at room
temperature, are given in Table 8.2
Gases
The dependence of gas-specific heats on temperature was
discussed in Chapter 3, Section 3.5. For a gas in the ideal state
the specific heat capacity at constant pressure is given by
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8.10. ENTHALPY OF VAPORIZATION (LATENT HEAT)
The latent heats of vaporization of the more commonly used
materials can be found in the handbooks and in Appendix C. A very
rough estimate can be obtained from Trouton’s rule (Trouton,
1884), one of the oldest prediction methods:

For organic liquids the constant can be taken as 100. More accurate estimates,
suitable for most engineering purposes, can be made from knowledge of the
vapor pressure-temperature relationship for the substance. Several correlations
have been proposed; see Reid et al. (1987). 28

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Mixtures

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8.11. VAPOR PRESSURE
If the normal boiling point (vapor pressure = 1 atm) and the critical
temperature and pressure are known, then a straight line drawn through
these two points on a plot of log-pressure versus reciprocal absolute
temperature can be used to make a rough estimation of the vapor
pressure at intermediate temperatures.

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8.12. DIFFUSION COEFFICIENTS (DIFFUSIVITIES)
Diffusion coefficients are needed in the design of
mass transfer processes, such as gas absorption,
distillation, and liquid-liquid extraction, as well as
in catalytic reactions where mass transfer can
limit the rate of reaction.
Experimental values for the more common
systems can be often found in the literature, but
for most design work the values must be
estimated.
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8.13. SURFACE TENSION
It is usually difficult to find experimental values for surface tension for any but the more
commonly used liquids. A useful compilation of experimental values is that by Jasper
(1972), which covers over 2000 pure liquids. Othmer et al. (1968) give a nomograph
covering about 100 compounds.
If reliable values of the liquid and vapor density are available, the surface tension can be
estimated from the Sugden parachor, which can be estimated by a group contribution
method (Sugden, 1924):

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8.14. CRITICAL CONSTANTS
Values of the critical temperature and pressure are needed for
prediction methods that correlate physical properties with the
reduced conditions. It is also important to know the critical
conditions when applying equation of state methods, as some of
the equation of state models are unreliable close to the critical
point. Experimental values for many substances can be found in
various handbooks and in Appendix C. Critical reviews of the
literature on critical constants and summaries of selected values
have been published by Kudchadker et al. (1968), for organic
compounds, and by Mathews (1972), for inorganic compounds. An
earlier review was published by Kobe and Lynn (1953).
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8.15. ENTHALPY OF REACTION AND ENTHALPY OF FORMATION

Enthalpies of reaction (heats of reaction) for the reactions used in the

production of commercial chemicals can usually be found in the
literature. Stephenson (1966) gives values for most of the production
processes he describes in his book.
Heats of reaction can be calculated from the heats of formation of the
reactants and products, as described in Chapter 3, Section 3.10. Values
of the standard heats of formation for the more common chemicals are
given in various handbooks; see also Appendix C. Care must be taken
to correct the heat of reaction to the temperature and pressure of the
process. A useful source of data on heats of formation and combustion
is the critical review of the literature by Domalski (1972).
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8.16. PHASE EQUILIBRIUM DATA
Phase equilibrium data are needed for the design of all
separation processes that depend on differences in
concentration between phases.

Experimental Data

Experimental data have been published for several thousand binary and many
multicomponent systems. Virtually all the published experimental data has
been collected together in the volumes comprising the DECHEMA vapor-
liquid and liquid-liquid data collection (DECHEMA, 1977). The books by Chu
et al. (1956), Hala et al. (1968, 1973), Hirata et al. (1975), and Ohe (1989,
1990) are also useful sources.
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