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Fluids and Solids Handling

Obtain the Best


Physical Property Data
Kevin G. Joback Physical property values are essential
Molecular Knowledge Systems, Inc.
for many chemical engineering tasks.
This article reviews sources of physical
property data, discusses the use of
experimental methods to measure
properties, and details several
types of estimation techniques.

C
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.

30 www.aiche.org/cep May 2009 CEP


What is the percent crystallinity? Some polymers can International and the Society of Automotive Engineers
solidify over a range of crystalline and amorphous states. (SAE) publish standardized test procedures for measuring
Properties such as density depend on the solids specific form. these properties. Because of the common need for expensive
Consider the National Library of Medicines Hazard- and specialized experimental equipment, many laboratories
ous Substances Data Bank (HSDB) (51). Although the exist that provide standardized testing services (6).
main focus of the HSDB is toxicity data, it also contains
considerable data on environmental fate, regulatory require- Estimation methods
ments, and chemical safety. The specific physical properties Inevitably, the chemical engineer will need physical
include aquatic toxicity, bioconcentration factor, biochemi- property values for chemicals or mixtures for which data are
cal oxygen demand, octanol-water partition coefficient, and not available and experimentation cannot be justified. Fortu-
threshold limiting values. References are always provided nately, many estimation methods can provide fairly accurate
for these values, but information on accuracy and experi- predictions. These estimation techniques are typically based
mental methods are not. on relationships between a physical property and state vari-
The National Institutes of Standards and Technology ables, between one physical property and others, or between
(NIST) Chemistry WebBook website (43) is another exam- a physical property and molecular structure.
ple of an excellent online database. The WebBook contains
a very good compilation of data for approximately 70,000 Table 1. Physical properties can be obtained from a variety
organic and inorganic chemicals. Data for the normal boil- of data compilations.
ing point, melting point, critical properties, heat capacities, Physical Property References
enthalpies of formation, phase change enthalpies, and vapor Aquatic Toxicity 21, 51
pressure are available. Almost all data points are associated Bioconcentration 12, 51
with references, accuracies, and comments. Some values are
Biodegradation 12, 51
estimated but are clearly referenced as such. One caution is
that several values are often given for a single property Critical Properties 4, 16, 43, 74
for example, a search for acetones critical density produces Decomposition Temperature 10
five different values of good accuracy. Enthalpy of Formation 16, 18, 43, 74
Enthalpy of Fusion 14, 16, 43, 74
Experimental methods
Enthalpy of Vaporization 13, 43, 74
Typically, several experimental methods are available
to measure each physical property. For example, Table 2 Flashpoint 16, 51, 74
lists just a few of the numerous methods used to measure Heat Capacity 19, 43
the infinite-dilution activity coefficient of methanol in water Henrys Constants 12, 43, 74
(17). In general, the choice of experimental method depends Mammalian Toxicity 41, 51
on the range of temperatures, pressures and concentrations
Skin and Eye Irritation 51
being measured, as well as the convenience of implementa-
Thermal Conductivity 68
tion and desired accuracy.
For many physical properties, the choice of experimen- Vapor Pressure 43
tal method should not affect the final value obtained. For
example, no matter which experimental method is used Table 2. Several experimental techniques are available to
determine the infinite-dilution activity coefficient.
to measure the normal boiling point of acetone, the result
should be close to 329 K. Experimental Technique Reference
However, the values of some physical properties do Chromatographic Retention Times 55
depend on the experimental procedure. These procedure- Circulation Equilibrium Still 71
dependent properties must be measured by following a pre-
Comparative Tensimetry 71
scribed experimental method, often using specific experimen-
Phase Ratio Variation 27
tal equipment. For example, a pure components flashpoint
must be measured in a specially designed apparatus, e.g., a Rayleigh Distillation 71
Tag closed tester, following a specific procedure that defines Wetted-wall Column 3
the rate of temperature increase and observation criteria. Headspace Analysis 71
Many of the physical properties used to characterize Inert Gas Stripping 25
plastics, foods, paints, lubricants, and cosmetics are classi-
Ebulliometry 35
fied as procedure-dependent. Organizations such as ASTM

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Fluids and Solids Handling

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

32 www.aiche.org/cep May 2009 CEP


of four-carbon rings, molecular volume, surface area, where is the viscosity, is the shear rate, and k and n are
energy gaps, polarizability, melting point, boiling point, and the models parameters. For a mixture of 500 ppm xanthan
charge density. gum in water, the parameters are: k = 2.5647 and n = 0.506
Neural network models (58). Like other estimation (39). Figure 1 shows that the model fits the data very well.
techniques, these models relate a predicted physical prop- However, before using any parameterized model, its
erty to one or more molecular structure attributes or basic validity for the given temperature, pressure, concentra-
physical properties. The key advantage of these methods is tion, or shear rate must be checked. The parameters for the
that the algebraic form of this relationship does not need to 500-ppm xanthan mixture were regressed from data in the
be specified it is automatically constructed as part of the 102,500 sec-1 shear rate range. Using those parameters at
modeling process. low shear rates would significantly overestimate the mix-
Estimation techniques have been developed for almost tures viscosity (Figure 2), because this is outside the region
every property chemical engineers encounter in their work. for which the model was designed.
These range from common properties such as boiling Probably the most commonly encountered parameterized
point, flashpoint, aquatic toxicity, and biochemical oxygen models are those used to predict a physical property as a
demand to less-common properties, such as skin permeation function of temperature. A third- or fourth-order polynomial
rate (32), corrosion inhibition (20), and critical micelle is commonly used to model the temperature-dependent
concentration (30). behavior of the heat capacity of an ideal gas. Other proper-
Chemical classes for which estimation techniques ties are modeled by algebraic equations containing loga-
have been developed include organic molecules, inorganic
molecules, electrolytes, natural and synthetic polymers,
10
proteins, surfactants, and ionic liquids. However, this
multitude of estimation techniques should not be taken to
mean all techniques are of high accuracy. Furthermore,
even accurate techniques can produce poor results when 1
Viscosity, cP

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.

Parameterized models 0.01


1 10 100 1,000 10,000
Parameterized models can produce very accurate esti-
Shear Rate, s1
mates. They are useful for interpolating physical property
values over ranges of temperatures, pressures, compositions, S Figure 1. A parameterized model (39) predicts the viscosity of a
and shear rates. Commonly used parameter models include mixture of 500 ppm xanthan gum in water very well.
Antoines vapor pressure equation, polynomial fits of ideal
heat capacity, and Wilsons equation for activity coefficient. 10
Compilations of parameters for thousands of chemicals and
mixtures are available. AIChEs DIPPR project (16) has
compiled parameters values for density, heat capacity, heat
1
Viscosity, cP

of vaporization, second virial coefficient, surface tension,


thermal conductivity, vapor pressure, and viscosity. NISTs
website (43) has compiled parameter values for vapor pres-
sure, heat capacities, and enthalpy of vaporization. 0.1
Parameterized models consist of an equation, a set of
parameters for each chemical or mixture that can be esti-
mated, and a set of limits outside of which the model should
not be used. Equation 1 is a parameterized model, com- 0.01
0.1 1 10 100 1,000 10,000
monly know as the power law, which predicts the viscosity Shear Rate, s1
of a solution as a function of shear rate (39):
S Figure 2. The dangers of extrapolation: verify the range over which the
= k n1 (1) model is valid.

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Fluids and Solids Handling

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

34 www.aiche.org/cep May 2009 CEP


Tc,2 are the pure component critical temperatures of compo- The boiling points for a series of normal paraffins are
nents 1 and 2. plotted in Figure 3. A straight line can be regressed through
As an example, consider a mixture containing 47.8 the data corresponding to paraffins containing between two
mol% acetic acid and 52.2 mol% hexane. Acetic acids and twenty carbons. The slope of this line is 22.9 K and
critical temperature is 592.71 K and its critical volume is
0.171 m3/kmol, and hexanes critical temperature is 507.43
K and its critical volume is 0.3699 m3/kmol (16). With these 700
values, Eq. 4 estimates the mixtures critical temperature to
be 532.79 K. This is in fair agreement with a literature value 600
of 514.2 K (26).

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.

Physical Properties in Chemical Product Design


Although most chemical engineers recognize the need for continuous phase, which lowers the internal pressure of the
physical properties when designing processes, the need for smaller droplets, reducing one driving force for diffusion (57).
physical properties is also critical when designing chemical gas solubility. Blood substitutes must be able to absorb
products. Chemically based blood substitutes are just one large amounts of oxygen and carbon dioxide, as well as
example for which knowledge of physical properties is desorb these gases when flowing through oxygen deficient
essential to the design of a successful product. tissues or through the lungs.
Blood substitutes have the potential for eliminating the liquid viscosity. Increasing the viscosity of the con-
need to collect and store human blood. Being chemically tinuous phase during storage would slow the movement of
based, they could be produced in large quantities and be emulsion droplets, increasing stability. However, the viscosity
inherently free of disease. Substitutes must have high oxygen would need to decrease significantly once the substitute was
solubility, be compatible with the human body, and be more administered to the body. Such a viscosity decrease could
easily stored than human blood. be achieved by changing the concentration or increasing the
Emulsions containing highly fluorinated chemicals are temperature.
currently the most promising blood substitutes (61), although mammalian toxicity. All components of a blood substi-
they still have some deficiencies. A detailed understanding tute must have very low toxicities.
of physical properties is essential to help eliminate these surface viscosity. Adding surfactant-soluble polymers
deficiencies. For example: or proteins would increase droplet rigidity and reduce the
density. As with other emulsified products, density rate of coalescence.
differences can lead to gravitational separation (e.g., cream- The fundamental importance of physical properties in
ing or sedimentation), which can reduce emulsion stability. chemical product design is exemplified by comparing blood
Selecting components to ensure that the density of the substitutes with another chemical product CO2 absorp-
continuous phase is equal to the density of the emulsion tion solvents. For these solvents, the ready absorption and
droplets would prevent separation and thus promote longer- desorption of CO2 is also important. Low toxicity is highly
term stability (48). desirable. Diffusion and viscosity are key properties needed
diffusion. Ostwald ripening, i.e., the diffusion of emulsi- to optimize mass transfer. The two chemical products are
fied material from smaller droplets to larger droplets, has very different, but the properties of importance are similar.
been shown to be a major cause of reduced stability in fluo- (In fact, some researchers are investigating the use of
rinated blood substitutes (57). Using fluorinated surfactants fluorinated chemicals as physical solvents for selective CO2
reduces the interfacial tension between droplets and the capture (29).

CEP May 2009 www.aiche.org/cep 35


Fluids and Solids Handling

represents the contribution of the CH2 group to the normal


boiling point.
Group Tb In a similar manner, multiple linear regression can be
CH3 performed on a dataset of diverse chemicals to generate the

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

COO 81.1 estimation method (56).


O Estimating a physical property using a group contribu-
CO 76.7 tion technique typically requires three steps:
C
O Tb (est) 403.1 K 1. dissecting the molecular structure into the techniques
groups
CH3 Tb (lit) 411.8 K 2. retrieving the contribution for each group
3. totaling the contributions into a final estimate using
3 the techniques model.
Tb = 198.1 + i Figure 4 demonstrates these steps for estimating the
normal boiling point of acetic anhydride using the groups
S Figure 4. A three-step group-contribution procedure determines the
normal boiling point of acetic anhydride.
and contributions from Table 5. The estimated value of
403.1 K is in good agreement with the literature value
of 411.8 K (16).
Step 1, dissecting a molecular structure into groups, is
typically the most troublesome. Many estimation techniques
O O have more than 50 different groups. Some techniques have

CH3C OC CH3 different contributions for a group depending on whether it


is in an acyclic molecule, a cyclic molecule, or an aromatic
molecule. Many techniques require corrections to be used
if certain combinations of groups are present; some of these
CH3 CH3 CH3 CH3 corrections are used in place of group contributions, some
in addition to group contributions. Some techniques use
O
second-order groups that adjust contributions for neighbor-
O O O O ing groups.

C C CO C Molecular structures can often be dissected into more


than one set of groups. Acetic anhydride, for example, can
be dissected two different ways using the groups shown
in Table 5 (Figure 5), resulting in significantly different
S Figure 5. Multiple structural dissections are often possible.
estimated boiling points of 421.1 K and 403.1 K. Unfortu-
nately, estimation techniques seldom give sufficient details
for determining which dissection is correct. In general, we
Table 5. Jobacks boiling point method recommend choosing the dissection that uses the groups of
employs these group contribution values.
largest size.
Group Contribution, K Because group contribution techniques are available for
CH3 23.6 many properties and many different chemical classes, it is
CH2 22.9 difficult to summarize their accuracy. However, it is often
>CH 21.7
>C< 18.3
Table 6. Group contributions for determining the glass
OH 92.9 transition temperature of poly(ether-ether-ketone).
COO 81.1 Group Y Contribution M Contribution
CO 76.7 p-Phenyl 29,500 76.1
O 22.4 CO 19,000 28.0
NH2 73.2 O 4,000 16.0
SH 63.6 Source: (67).

36 www.aiche.org/cep May 2009 CEP


surprising how even simple techniques can give very accu- Table 7. Numerous group contribution estimation
rate estimates. techniques are available.
For example, in an evaluation of boiling point estimates Physical Property References
for 559 small, low-molecular-weight organic molecules, Acid Dissociation Constant 44
Jobacks method gave an average absolute error of 4.8%; for
Activity Coefficient 44, 56
82% of the compounds, estimation errors were 25 K or less.
Interestingly, chemicals with large estimation errors tended Air-Water Partition Coefficient 60
to be either compounds with very high or very low molecu- Aqueous Solubility 37, 44, 46, 60
lar weights. Figure 3 offers insight into this relationship. The Autoignition Temperature 1
estimation technique was developed to predict properties for Boiling Point 44, 50, 56, 63
those chemicals having 220 carbons. Like parameterized
Bulk Modulus 67
models and equation-oriented techniques, group contribution
techniques are also applicable to a limited range in this Critical Properties 49, 56
case, a limited range of molecular structures. Density 44, 60, 67
Note that this limitation on the range of molecular size Diffusion Coefficient, Liquid 56
does not mean that the properties of larger molecules cannot Enthalpy of Formation 18, 56, 67
be estimated by group contribution techniques only that it
Enthalpy of Fusion 14
is unlikely that the same method can be used for both small
Enthalpy of Vaporization 44, 54
and large compounds.
In fact, many polymer properties can be well estimated Flammability Limits 1
by group contribution techniques. The molecular structure Flashpoint 1, 53
used for these techniques is the polymeric repeat unit. For Gibbs Energy of Formation 56
example, the polymeric repeat unit for poly(ether-ether- Glass Transition Temperature 67
ketone), or PEEK, is:
Heat Capacity 13, 36, 44, 56
O Magnetic Susceptibility 67

[
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

Closing thoughts Model for Predicting the Thixotropy of Paints 5


This brief review is intended to show how physical Phase Equilibrium of Vegetable Oil Components 23
property values for many of the chemicals and mixtures Predicting Drug-Polymer Miscibility and Solubility 47
engineers work with daily can be found in data compilations Predicting the Pleasantness of Odor 40
or predicted by estimation techniques. Table 8 illustrates that
Prediction of -Amyloid Peptide Aggregation 34
even as chemical engineers venture into new materials and
new processes, physical property data will continue to be Supercooling of Aqueous Solutions 31
measured and estimation techniques will continue
to be developed to aid in this work. CEP Article continues on next page

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Fluids and Solids Handling

Literature Cited
1. Albahri, T. A., Flammability Characteristics of Pure Hydrocar- ship for Oil Field Corrosion Inhibitors, Journal of the Electro-
bons, Chemical Engineering Science, 58, pp. 36293641 (2003). chemical Society, 146 (5), pp. 17511756 (1996).
2. Allen, M. P., and D. J. Tildesley, Computer Simulation of Liq- 21. U.S. Environmental Protection Agency, ECOTOX Database,
uids, Oxford University Press, Oxford, U.K. (1987). available online at http://cfpub.epa.gov/ecotox/index.html, EPA,
3. Altschuh, J., et al., Henrys Law Constants for a Diverse Set Office of Research and Development.
of Organic Chemicals: Experimental Determination and 22. Fan, T. and L. Wang, A Viscosity Model Based on Peng-Robin-
Comparison of Estimation Methods, Chemosphere, 39 (11), son Equation of State for Light Hydrocarbon Liquids and Gases,
pp. 18711887 (1999). Fluid Phase Equilibria, 247 (12), pp. 5969 (2006).
4. Ambrose, D., and C. L. Young, Vapor-Liquid Critical Properties 23. Fornari, T., Revision and Summary of the Group Contribution
of Elements and Compounds. 1. An Introductory Survey, Journal Equation of State Parameter Table: Application of Edible Oil
of Chemical and Engineering Data, 40, pp. 345357 (1995). Constituents, Fluid Phase Equilibria, 262, pp. 187209 (2007).
5. Armelin, E., et al., A Simple Model to Describe the Thixotro- 24. Frenkel, D., and B. Smit, Understanding Molecular Simulation,
pic Behavior of Paints, Progress in Organic Coatings, 57, pp. Academic Press, San Diego, CA (2002).
229235 (2006). 25. Fukuchi, K., et al., Measurement and Correlation of Infinite
6. ASTM International, ASTM International Directory of Testing Dilution Activity Coefficients of Alkanol or Ether in Aqueous
Laboratories, available online at www.astm.org/labs, ASTM, Solution, Fluid Phase Equilibria, 194197, pp. 937945 (2002).
West Conshohocken, PA. 26. Gammon, B. E., et al., Transport Properties and Related Ther-
7. Babb, S. E., Jr., Parameters in the Simon Equation Relating modynamic Data of Binary Mixtures. Part 2, Design Institute of
Pressure and Melting Temperature, Reviews of Modern Physics, Physical Property Data (DIPPR), American Institute of Chemical
35 (2), pp. 400413 (1963). Engineers, New York, NY (1993).
8. Barratt, M. D., Prediction of Toxicity from Chemical Structure, 27. Gupta, A. K., et al., Henrys Constants of n-Alkanols (Methanol
Cell Biology and Toxicology, 16, pp. 113 (2000). through n-Hexanol) in Water at Temperatures between 40C and
9. Bicerano, J., Prediction of Polymer Properties, Marcel Dekker, 90C, Fluid Phase Equilibria, 170 (2), pp. 183192 (2000).
Inc., New York, NY (2002). 28. Hansch, C., and A. Leo, Exploring QSAR, American Chemical
10. Blake, E. S., et al., Thermal Stability as a Function of Chemical Society, Washington, DC (1995).
Structure, Journal of Chemical and Engineering Data, 6 (1), pp. 29. Heintz, Y. J., et al., Novel Physical Solvents for Selective CO2
8798 (1961). Capture from Fuel Gas Streams at Elevated Pressures and Tem-
11. Catoire, L., and V. Naudet, A Unique Equation to Estimate perature, Energy and Fuels, 22 (6), pp. 38243837 (2008).
Flash Points of Selected Pure Liquids, Journal of Physical and 30. Huibers, P. D. T., et al., Prediction of Critical Micelle
Chemical Reference Data, 33 (4), pp. 10831111 (2004). Concentration Using a Quantitative Structure-Property Relation-
12. Syracuse Research Corp., CHEMFATE Chemical Database, ship Approach. 1. Nonionic Surfactants, Langmuir, 12, pp.
www.syrres.com/what-we-do/free-demos.aspx, Syracuse 14621470 (1996).
Research, Syracuse, NY. 31. Kanno, H., et al., Additivity Rule Holds in Supercooling of
13. Chickos, J. S., and W. E. Acree, Enthalpies of Vaporization Aqueous Solutions, Journal of Physical Chemistry A, 108 (28),
of Organic and Organometallic Compounds, 18802002, pp. 60796082 (2004).
Journal of Physical and Chemical Reference Data, 32 (2), pp. 32. Katritzky, A. R., et al., Skin Permeation Rate as a Function of
519878 (2003). Chemical Structure, Journal of Medicinal Chemistry, 49, pp.
14. Chickos, J. S., et al., Estimating Solid-Liquid Phase Change 33053314 (2006).
Enthalpies and Entropies, Journal of Physical and Chemical 33. Kier, L. B. and L. H. Hall, Molecular Connectivity in Structure-
Reference Data, 28 (6), pp. 15351673 (1999). Activity Analysis, John Wiley and Sons, Hoboken, NJ (1986).
15. Cogn, C., et al., Experimental Data and Modelling of the Ther- 34. Kim, J. R., et al., Predicting Solvent and Aggregation Effects of
mal Properties of Ice Creams, Journal of Food Engineering, 58, Peptides using Group Contribution Calculations, Biotechnology
pp. 331341 (2003). Progress, 22 (2), pp. 605608 (2006).
16. Daubert, T. E., and R. P. Danner, Physical and Thermodynamic 35. Kojima, K., and M. Kato, Measurements of Isobaric Boiling
Properties of Pure Chemicals, Hemisphere Publishing Corpora- Point Curves at High and Low Pressures, Kagaku Kogaku, 33 (8),
tion, Washington, DC (1992). pp. 769775 (1969).
17. Dohnal V., et al., Temperature Dependences of Limiting Activity 36. Kolsk, Z., et al., Estimation of the Heat Capacity of Organic
Coefficients, Henrys Law Constants, and Derivative Infinite Liquids as a Function of Temperature by a Three-Level Group
Dilution Properties of Lower (C1C5) 1-Alkanols in Water, Contribution Methods, Industrial and Engineering Chemistry
Journal of Physical and Chemical Reference Data, 35 (4), pp. Research, 47 (6), pp. 20752085 (2008).
16211651 (2006). 37. Khne, R., et al., Group Contribution Methods to Estimate
18. Domalski, E. S., and E. D. Hearing, Estimation of the Thermo- Water Solubility of Organic Chemicals, Chemosphere, 30 (11),
dynamic Properties of C-H-N-O-S-Halogen Compounds at pp. 20612077 (1995).
298.15 K, Journal of Physical and Chemical Reference Data, 38. Lalibert, M., Models for Calculating the Viscosity of Aqueous
22 (4), pp. 8051159 (1993). Solutions, Journal of Chemical and Engineering Data, 52 (2), pp.
19. Domalski, E. S., and E. D. Hearing Heat Capacities and En- 321335 (2007).
tropies of Organic Compounds in the Condensed Phase. Volume 39. Lapasin, R., and S. Pricl, Rheology of Industrial Poly-
III, Journal of Physical and Chemical Reference Data, 25 (1), pp. saccharides, Blackie Academic and Professional, Glasgow, U.K.,
1525 (1996). p. 337 (1995).
20. Durnie, W., et al., Development of a Structure-Activity Relation- 40. Lapid, H., et al., Prediction Models for the Pleasantness of

38 www.aiche.org/cep May 2009 CEP


Literature Cited
Binary Mixtures in Olfaction, Chemical Senses, 33 (7), Issue, Artificial Cells, Blood Substitutes, and Immobilization
pp. 599609 (2008). Biotechnology, 22 (4), pp. 9911005 (1994).
41. Lewis. R. J., Saxs Dangerous Properties of Industrial Materi- 58. Prasad, J., and S. S. Bhagwat, Simple Neural Network
als, John Wiley and Sons, Hoboken, NJ (2000). Models for Prediction of Physical Properties or Organic Com-
42. Lide, D. R., CRC Handbook of Chemistry and Physics, CRC pounds, Chemical Engineering and Technology, 25 (11), pp.
Press, Boca Raton, FL (2008). 10411046 (2002).
43. Linstrom, P. J., and W. G. Mallard, eds., NIST Chemistry 59. Raymond, J. W., et al., A Review of Structure-Based Biodegra-
WebBook, NIST Standard Reference Database No. 69 available dation Estimation Methods, Journal of Hazardous Materials, 84
online at http://webbook.nist.gov, National Institute of Standards (23), pp. 189215 (2001).
and Technology, Gaithersburg, MD. 60. Reinhard, M., and A. Drefahl, Estimating Physicochemical
44. Lyman, W. J., et al., Handbook of Chemical Property Estimation Properties of Organic Compounds, John Wiley and Sons, Inc.,
Methods, American Chemical Society, Washington, DC (1990). Hoboken, NJ (1999).
45. Mackay, D., and A. Fraser, Bioaccumulation of Persistent 61. Riess, J. G., Oxygen Carriers (Blood Substitutes) Raison
Organic Chemicals: Mechanisms and Models, Environmental dEtre, Chemistry, and Some Physiology, Chemical Reviews, 101,
Pollution, 110 (3), pp. 375391 (2000). pp. 27972919 (2001).
46. Marrero, J., and R. Gani, Group-Contribution-Based Estima- 62. Roberts, R. J., et al., The Relationship between the Fracture
tion of Octanol/Water Partition Coefficient and Aqueous Solubil- Properties, Tensile Strength and Critical Stress Intensity Factor
ity, Industrial Engineering and Chemistry Research, 41 (25), pp. of Organic Solids and Their Molecular Structure, International
66236633 (2002). Journal of Pharmaceutics, 125, pp. 157162 (1995).
47. Marsac, P. J., et al., Theoretical and Practical Approaches for 63. Sanghvi, R., and S. H. Yalkowsky, Estimation of the Normal
Prediction of Drug-Polymer Miscibility and Solubility, Pharma- Boiling Point or Organic Compounds, Industrial Engineering and
ceutical Research, 23 (10), pp. 24172426 (2006). Chemistry Research, 45 (8), pp. 28562861 (2006).
48. McClements, D. J., Food Emulsions. Principles, Practices, and 64. Sivaraman, A., et al., Correlation for Prediction of Interfacial
Techniques, CRC Press, Boca Raton, FL (2005). Tensions of Pure Alkane, Naphthenic and Aromatic Compounds
49. Nannoolal, Y., et al., Estimation of Pure Component Properties between their Freezing and Critical Points, Fluid Phase Equilib-
Part 2. Estimation of Critical Property Data by Group Contribu- ria, 18, pp. 225235 (1984).
tion, Fluid Phase Equilibria, 252 (12), pp. 127 (2007). 65. Spencer, C. F., and R. P. Danner, Improved Equation for
50. Nannoolal, Y., et al., Estimation of Pure Component Properties Prediction of Saturated Liquid Density, Journal of Chemical and
Part 1. Estimation of the Normal Boiling Point of Non-Electrolyte Engineering Data, 17 (2), pp. 236241 (1972).
Organic Compounds via Group Contributions and Group Interac- 66. Todeschini, R., and V. Consonni, Handbook of Molecular De-
tions, Fluid Phase Equilibria, 226, pp. 4563 (2004). scriptors, Wiley-VCH Verlag GmbH, Weinheim, Germany (2002).
51. U.S. National Library of Medicine, The Hazardous Substances 67. van Krevelen, D. W., Properties of Polymers, Elsevier, Amster-
Data Bank (HSDB), available online at http://toxnet.nlm.nih.gov/ dam, The Netherlands (1997).
cgi-bin/sis/htmlgen?HSDB, National Library of Medicine Toxicol- 68. Vargaftik, N. B., et al., Handbook of Thermal Conductivity of
ogy Data Network, Bethesda, MD. Liquids and Gases, CRC Press, Boca Raton, FL (1994).
52. Nimitz, J. S., and S. R. Skaggs, Estimating Tropospheric Life- 69. Velasco, S., et al., A Predictive Vapor-Pressure Equation, Jour-
times and Ozone-Depletion Potentials of One- and Two-Carbon nal of Chemical Thermodynamics, 40 (5), pp. 789797 (2008).
Hydrofluorocarbons and Hydrochlorofluorocarbons, Environmen- 70. Viswanath, D. S., et al., Viscosity of Liquids, Springer, Dor-
tal Science and Technology, 26 (4), pp. 739744 (1992). drecht, The Netherlands (2007).
53. Pan, Y., et al., Quantitative Structure-Property Relationship 71. Vrbka, P., et al., Measurement of Infinite Dilution Activity
Studies for Predicting Flash Points of Organic Compounds using Coefficients of 1-Alkanols (C1 C5) in Water as a Function of
Support Vector Machines, QSAR and Combinatorial Science, 27 Temperature (273373K), Fluid Phase Equilibria, 237 (12), pp.
(8), pp. 10131019 (2008). 123129 (2005).
54. Pankow, J. F., and W. E. Asher, SIMPOL 1: A Simple Group 72. Wang, T., et al., Description of the PVT Behavior of Ionic Liq-
Contribution Method for Predicting Vapor Pressures and Enthalpies uids and the Solubility of Gases in Ionic Liquids Using and Equa-
of Vaporization of Multifunctional Organic Compounds, Atmo- tion of State, Fluid Phase Equilibria, 250, pp. 150157 (2006).
spheric Chemistry and Physics, 8 (10), pp. 27732796 (2008). 73. Weber, L. A., Vapor Pressure of Heptane from the Triple Point to
55. Pecsar, R. E., and J. J. Martin, Solution Thermodynamics from the Critical Point, Journal of Chemical and Engineering Data, 45
Gas-Liquid Chromatography, Analytical Chemistry, 38 (12), pp. (2), pp. 173176 (2000).
16611669 (1966). 74. Yaws, C., Chemical Properties Handbook: Physical, Thermo-
56. Poling, B. E., et al., The Properties of Gases and Liquids, dynamics, Environmental, Transport, Safety, and Health Related
McGraw-Hill, New York, NY (2001). Properties for Organic and Inorganic Chemicals, McGraw-Hill,
57. Postel, M., et al., Fluorocarbon Emulsions The Stability New York, NY (1999).

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.

CEP May 2009 www.aiche.org/cep 39

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