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hemical engineers use physical properties every day simulators have typically been checked to ensure consis-
from viscosities and densities for pump selec- tency in calculations.
tion, flashpoints and heats of combustion for process Table 1 lists references for a number of physical property
safety analysis, and aquatic toxicities and Henrys constants data compilations. Although these compilations are pre-
for compliance with environmental regulations, to solubili- sumed to contain good-quality data, several key questions
ties and diffusivities in the design of time-release capsules, should be asked before any value is used:
skin and eye irritation values for cosmetic component evalu- What is the original source of the data? Information
ation, hydrophilic-lipophilic balance values for emulsifier such as how and when the data were measured and the
selection, and non-Newtonian viscosities for optimization of purity of samples used is important in deciding whether to
the mouth-feel of yogurts and ice creams. Values for many accept a particular value. Unfortunately, some extensive data
of these physical properties can be found in reference books, compilations fail to report the original data source.
process simulators, and online databases. Some physical Are the data experimental or estimated? Some com-
properties can be quickly and easily measured experimen- pilations strive to provide an entire set of values for a long
tally. Others can be accurately predicted using a variety of list of chemicals. To achieve this completeness, they often
computational techniques. include interpolated or estimated values. These are typically
This article reviews sources for physical property very good values, but, unfortunately, they are not always
data, comments on experimental methods used to measure clearly denoted as estimates.
physical properties, and discusses several different types What was the temperature and pressure? Surprisingly,
of estimation techniques. Because of the large number of for some temperature-dependent properties (e.g., octanol-
physical properties, chemical classes, and state conditions, water partition coefficient and liquid density), the tempera-
it is intended to provide a starting point for finding values of ture is not always reported. Unfortunately, many data points
needed physical properties. must be assumed to have been measured at room tempera-
ture and atmospheric pressure.
Data compilations What is the molecular weight or molecular weight dis-
Many compilations of physical property data are avail- tribution? Many polymer properties (e.g., solution viscosity)
able today. Online databases provide detailed information are highly dependent on molecular size.
about each data point, including accuracy, original reference, What is the crystal structure? Many molecules can
and experimental method. Printed reference books may con- have several common crystal structures. Certain properties,
tain less information, but often present only higher-quality particularly the enthalpies of phase transitions, are highly
commonly needed data. The data found in many process dependent on the solids crystal structure.
There are several general classes of estimation methods: Equation-oriented techniques (56). These models are
Parameterized models (56,70). These models are typi- based on relationships between physical properties. An
cally used to capture the relationship between a property equation-oriented technique relates a predicted physical
and state variables such as temperature, pressure, concentra- property to more readily available properties such as melting
tion, or shear rate. A set of parameters is regressed for each point, boiling point, or molecular weight. Equation-oriented
chemical or mixture, and then these parameters are inserted techniques are available for a large number of properties and
into one or more equations to compute the property estimate. chemical families.
Parameterized models have the advantage of high accuracy, Group contribution techniques (56,67). These tech-
but the cannot be used if parameters are not available for the niques assume each part of a molecules structure contrib-
chemical or mixture being investigated. utes a certain amount to the molecules physical property
value. The contribution for each of these parts, or functional
groups, is assumed to have the same value even when
Physical Property the group occurs in a different portion of the molecules
Estimation Software structure or even if the group occurs in a different molecule.
Estimating physical properties by hand can involve Estimates are thus obtained by combining the contributions
gathering the required data, choosing estimation for each of a molecules groups. The advantage of group
techniques, recursively estimating physical properties, contribution techniques is that estimates for many properties
performing tedious calculations, and then often repeating can be obtained with only the knowledge of the chemicals
the process for another temperature or pressure. molecular structure.
Fortunately, there are many software programs that Connectivity indices (9,33). Like group contribution
automate this process. Many of these programs include
techniques, these models can also predict property values
useful capabilities such as data storage, automatic
structure dissection, estimation technique evaluation, and from only the knowledge of a chemicals molecular struc-
the ability to add ones own estimation methods. Further ture. Each non-hydrogen atom is first assigned a value based
information is available at the following websites: on its connectivity or bonding configuration. The value
Artist: www.ddbst.de/new. Automatic structure assigned depends on the method. For example, one method
dissection; more than 60 methods for 13 physical assigns a value of 4.0 to the central carbon in 3,3-dimethyl-
properties; pure components. pentane because it is connected to four other carbons,
Cranium: www.molknow.com/cranium/cranium.
whereas another method uses a value of 2.0 because it is
htm. Automatic structure dissection; over 50 properties;
organic and inorganic chemicals, polymers, and electro- connected directly to only two other carbons that are then
lytes; pure components and mixtures. connected to two other carbons. Then the values for all of
DIADEM: dippr.byu.edu/interface.asp. Over 20 the individual atoms are combined into an overall index
physical properties; organic chemicals; pure components. using a prescribed procedure. Each connectivity index
EPI Suite: www.epa.gov/oppt/exposure/pubs/ technique includes one or more equations that relate these
episuitedl.htm. Focused on environmental properties; indices to a predicted physical property.
pure components.
Molecular modeling methods (2,24). These techniques
PhysProps and MixProps: www.gpengineeringsoft.
com. Over 25 properties; organic and inorganic com- combine the physical laws of motion with models of atomic
pounds; pure components and mixtures. attraction and repulsion to compute the positions and trajec-
PPDS Suite: www.ppds.co.uk/products/default.asp. tories of atoms within molecular structures and molecules
Focused on thermophysical properties; pure components within a substance. Measurements of molecular energies,
and mixtures. velocities, and positions are used to determine various
Predict: www.mwsoftware.com/dragon/desc.html. physical properties. Molecular modeling methods have the
More than 65 methods for 18 physical properties; pure
potential for being the most broadly applicable of estima-
components.
ProPred: www.capec.kt.dtu.dk/software/icas-and- tion techniques. Current research continues to expand the
its-tools. Automatic structure dissection; over 30 proper- number of properties and the classes of chemicals that can
ties; organic chemicals; pure components. be estimated by these techniques.
Simulis Thermodynamics: http://www.prosim.net/ Quantitative structure-property relationships (QSPRs)
en/thermodynamics/simulist.html. More than 300 meth- (28). These techniques combine molecular modeling with
ods for thermophysical properties; pure components and statistical analysis to relate physical properties to one or
mixtures.
more molecular descriptors. Descriptors may include basic
SuperChems: www.iomosaic.com. Focused on
properties for safety analysis; phase equilibrium calcula- properties as well as values calculated from the molecules
tions; pure components and mixtures. connectivity or three-dimensional structure (60, 66). Exam-
ple descriptors include the number of carbons, the number
used incorrectly.
Some of the issues that need to be considered when
using estimation techniques are illustrated by examining the 0.1
three most common model classes: parameterized models;
equation-oriented techniques; group contribution techniques.
rithms and reciprocal functions of temperature. Many of observed linear relationship between the log of the vapor
these models extrapolate poorly. pressure and the reciprocal of the temperature:
Table 3 provides references to parameterized models.
B
Models are available for predicting common properties such ( )
ln Pvp = A
T
(3)
as vapor pressure, heat capacity, and thermal conductivity,
as well as some less-common physical properties, such as The two data points (Tb, 1.01325 bar) and (Tc, Pc), can be
permittivity as a function of temperature and the melting used to solve for the coefficients A and B and obtain Eq. 2.
point as a function of pressure. It is interesting to note that this estimation technique is
very often used for temperatures between the melting point
Equation-oriented techniques and boiling point, but it was derived using temperature
The major limitation of parameterized models is that values for the boiling point and the critical temperature. Not
they require parameters that must be regressed from experi- unexpectedly, at lower temperatures the estimation tech-
mental data. Equation-oriented techniques overcome this nique is less accurate.
limitation by using basic properties as the parameters in Many estimation techniques for mixtures are equation-
the model. For example, Eq. 2 estimates the liquid vapor oriented techniques. For instance, Lis technique (56) can
pressure, Pvp, using only temperature, T, and other pure- predict the critical temperatures of liquid mixtures. Equa-
component physical properties: tion 4 is the techniques model for a binary mixture, in
which the dependent parameters are the physical properties
ln (
Pc
) for each of the mixtures components:
( )
ln Pvp = Tb
1.01325
Tc Tb ( )
1
Tc
T
( )
+ ln Pc ( 2) Tc, mix =
x1Vc,1Tc,1 + x2Vc,2Tc,2
( 4)
x1Vc,1 + x2Vc,2
where Pc is the critical pressure (bar), Tc is the critical tem-
perature (K), and Tb is the normal boiling point (K) (16). For where Tc,mix is the mixtures critical temperature, x1 and x2
example, n-heptanes critical pressure is 27.358 bar, critical are the mole fractions of components 1 and 2, Vc,1 and Vc,2
temperature is 540.26 K, and normal boiling point is 371.58 are the critical volumes of components 1 and 2, and Tc,1 and
K (16). Using these values, Eq. 2 estimates the vapor pres-
sure at 446.25 K to be 5.93 bar. This agrees very well with Table 4. Equation-oriented estimation techniques
an experimental value of 5.99 bar (73). predict a wide range of physical properties.
Like parameterized models, equation-oriented tech- Physical Property References
niques also have limits on their region of applicability. Aqueous Solubility 44, 60
Unfortunately, these limits are seldom reported and not eas-
Bioconcentration Factor 44, 45
ily determined. For example, Eq. 2 is based on the generally
Biological Oxygen Demand 59
Boiling Point 44, 56, 60
Table 3. Parameterized models
predict many common properties. Critical Properties 56
Physical Property References Density, Liquid 44, 56, 60, 65
Density, Liquid 16, 60, 65, 74 Diffusion Coefficient, Vapor 44, 56
Enthalpy of Vaporization 16, 43, 74 Enthalpy of Vaporization 44, 56, 60
Heat Capacity, Ideal Gas 16, 43, 56, 74 Flashpoint 11, 44
Heat Capacity, Liquid 16, 43, 56, 74 Heat Capacity, Liquid 56
Melting Point Pressure 7 Interfacial Tension 44, 64
Relative Static Permittivity 42 Surface Tension, Liquid 56, 60
Surface Tension, Liquid 16, 74 Skin Sensitization 8
Thermal Conductivity, Liquid 16, 68, 74 Tensile Strength 62
Thermal Conductivity, Vapor 16, 68, 74 Thermal Conductivity 44, 56, 67
Vapor Pressure, Liquid 16, 43, 56, 74 Vapor Pressure, Liquid 44, 56, 60, 69
Viscosity, Liquid 5, 16, 38, 70, 74 Viscosity, Liquid 56, 70
Viscosity, Vapor 16, 74 Viscosity, Vapor 22, 56
Boiling Point, K
500
Table 4 gives references to some equation-oriented
techniques. Methods are available for predicting common 400
properties, such as vapor pressure, viscosity, and diffusion Slope = 22.9
coefficient, as well as some less-common physical proper- 300
ties, such as tablet tensile strength and skin sensitization.
200
Group contribution techniques
100
If the basic, pure-component physical properties needed 0 5 10 15 20 25
by equation-oriented techniques are not available, they must Number of Carbon Atoms
also be estimated. Group contribution estimation techniques
are widely used and can provide good estimates for proper- S Figure 3. The straight-line regression of the boiling points of normal
ties given only a chemicals molecular structure. paraffins is an example of a group contribution method.
1 CH3 23.6 contributions for many different groups. Table 5 shows some
C
O CH3 23.6 2 of the groups and contributions for Jobacks boiling point
[
O O C
] Melting Point
Octanol/Water Partition Coefficient
56, 67
28, 44, 46, 60
Shear Modulus 67
The group contributions for determining the glass transi-
Surface Tension, Liquid 44, 60, 67
tion temperature of PEEK are given in Table 6 (67). Insert-
ing these contributions into the equation: Thermal Conductivity, Liquid 44, 56
Thermal Expansion Coefficient 67
Tg = Y/M Viscosity 44, 56, 60
yields an estimate of 400.6 K. Literature values range from Table 8. Not just for alkanes anymore chemical
414 to 433 K (67). engineers physical property needs continue to expand.
Table 7 lists references to group contribution techniques. Physical Property References
These represent only a small sample of the hundreds of tech- Equation of State for Gas Solubility 72
niques available for predicting physical properties ranging in Ionic Liquids
from melting point and heat capacity to aquatic toxicity and Estimating Ozone Depletion Potentials 52
hydrophilic-lipophilic balance.
Model for the Heat Capacity of Ice Creams 15
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KEVIN G. JOBACK, PhD, is president of Molecular Knowledge Systems (MKS; P.O. Box 10755, Bedford, NH 03110; Phone: (603) 472-5315; E-mail: kevin@molknow.
com). He has been with MKS since its founding in 1989. He has worked in the areas of physical property estimation and chemical product design for more
than 25 years, and has developed several group-contribution estimation techniques now widely used in industry. He has designed numerous chemical
products, including environmentally friendly cleaning and separation solvents, new lubricants, enhanced thermal-storage materials, improved jet and rocket
fuels, and nonhazardous aircraft-deicing uids. His current responsibilities also include managing the development and marketing of MKSs CRANIUM and
SYNAPSE software products. He holds a BS from Stevens Institute of Technology, and an MS and PhD from MIT, all in chemical engineering.