M. Shacham, M. B. Cutlip and M. Elly, " The Role of Physical Property Databases in Ch. E.

Education", paper 148a, Presented at the 11AIChE Annual Meeting, Minneapolis, MN, Oct. 1621, 2011
THE ROLE OF PHYSICAL PROPERTY DATABASES IN CH. E. EDUCATION
Mordechai Shacham, Ben-Gurion University of the Negev, Beer-Sheva, Israel
Michael B. Cutlip, University of Connecticut, Storrs, CT
Michael Elly, Intel Corp., Qiryat Gat, Israel
Introduction
Numerical problem solving in Chemical Engineering typically requires a mathematical
model of the problem along with physical and thermodynamic data and correlations
(equations) of the chemical substances involved. The required pure compound properties are
usually divided into constant properties and temperature and/or pressure dependent
properties. In most ChE textbooks, the preparation of the mathematical model associated with
a particular problem is typically emphasized. The property data required for solution of the
problems are usually provided in tabular or graphical form in the appendix of the textbook
and/or in a CD associated with the book (see for example, Felder and Rousseau, 2000 and
Himmelblau and Riggs, 2004).
Recently, various databases that contain extensive physical property data for a large
number of compounds have become available. Typical examples are the DIPPR database
(Rowley et al., 2010) and the NIST database (http://webbook.nist.gov/chemistry/) databases.
The use of the data available in these databases for problem solving has significant benefits
over the use of the data provided in the textbooks. Some of the more important advantages
are:
1. In current engineering practice, the databases are used as a principal source of
property data and correlations. Thus it is important that students become experienced
with the application of these sources during their educational programs.
2. The databases provide consistent sets of correlations for temperature-dependent
properties enabling the use of solution techniques independent of the format in which
the property data is provided. If temperature-dependent data are provided in tabular or
graphical forms, for example, this prevents the use of standard numerical methods for
problem solution, and data format dependent ad hoc solution techniques have to be
used.
3. The data provided in databases are continuously updated with the new data as they
become available. Property data in textbooks are often taken "as is" from references
that may be as much as half a century old. The textbook data may be incorrect or even
contradictory. It is important that students become accustomed to using reliable data.
4. The data available in the databases are evaluated and in cases when multiple values
are available for the same property, one recommended value is selected by the
database professionals. There may be very substantial differences between property
values reported by different investigators. Brauner et al., 2005, for example mention the
case of the melting point of 4-methyloctane for which the recommended value is 159.95
K while one reported experimental value is 219.62 K. The students must be made
aware of the fact that several property values may be available and learn how to find
and utilize the value with the highest confidence in its correctness.

5. The databases usually provide uncertainty values (upper limit on experimental error)
which enable estimation of the uncertainty of the problem solution using error
propagation analysis. An important goal of chemical engineering education is to impart
to students that the numerical "solution" of a problem almost always has some
associated uncertainty.
A convenient option for chemical engineering educators to incorporate the use of
databases into their teaching has been integrated into the POLYMATH package. This widelyused computational tool for numerical problem solving now contains a "sample database"
subset of the DIPPR Database1. The "sample database" contains 34 constant properties
and 16 temperature dependent property correlations for 112 compounds that are most
frequently used in chemical engineering textbooks. A special interface POLYMATH Database
Interface (PDI) now enables a convenient search of the sample database for selected
compounds. The desired properties can be selected, and the data and correlations outputted
in a format that can be copied and pasted directly into a computer code with all the significant
figures given in the database. The formats that are currently supported are for POLYMATH2,
MATLAB3 and Excel4.
In the following example, the use of the POLYMATH interface to the DIPPR Database will
be demonstrated for an adiabatic reactor design problem that will illustrate and highlight the
database usage.
Production of Acetic Anhydride An Example
Process models based on material and energy balances usually include some constant
and temperature dependent data. A typical example of this type is presented by Fogler (1992).
This example involves the vapor phase cracking of acetone to ketene and methane
CH3COCH3 CH2CO
+
CH4
Acetone (A) Ketene (B) + Methane (C)
as a key step in manufacturing acetic anhydride. The reaction is first order with respect to
acetone (A) and the specific reaction rate can be expresses by
34222
ln(k ) = 34.34
(1)
T
where k is the specific reaction rate (1/s) and T is the temperature (K). It is desired to design a
tubular reactor which yields 20% conversion. The case considered here involves adiabatic
operation of the reactor, feed flow rate of FA0 = 8000 kg/hr acetone, inlet temperature of T0 =
1035 K and pressure P = 162 kPa.
The mole balance equations for this system can be written

The Design Institute for Physical Properties and its acronym DIPPR are registered trademarks of the American Institute of
Chemical Engineers (AIChE)
2
POLYMATH is a product of POLYMATH Software, http://www.polymath-software.com
3
MATLAB is a trademark of The Math Works, Inc. http://www.mathworks.com
4
Excel is a trademark of the Microsoft Corporation, http://www.microsoft.com

dFA
dF
dF
= rA ; B = rA and C = rA
dV
dV
dV

(2)

where FA, FB and FC are the molar flow rates (in mol/s) of compounds A, B and C, respectively,
V is the volume (m3), and rA is the rate of the reaction mol/(m3*s) with respect to A:
(3)

rA = kC A

Here CA is the concentration of A (mol/m3) and it can be calculated using the ideal gas law.
FA
P
CA =
(4)
(FA + FB + FC ) RT
The enthalpy balance equation yields

{[

]}

0
(TR ) + H Q (T )
rA H Rx
dT
=
dV
FAC PA + FB C PB + FC C PC

(5)

0
where H Rx
(TR ) is the heat of the reaction at a reference temperature (TR, usually 25 C) and
HQ(T) is the enthalpy change that results when the temperature is raised from TR to some
temperature T. CPA, CPB and CPC are the heat capacities (J/mol*K) of components A, B and C,
respectively.

Fogler (1992) rewrote these equations in terms of conversion (X = 1-FA/FA0) as the use of
conversion enables obtaining graphical solution for the adiabatic case. Rewriting the mole
balance equations in terms of the conversion yields:
dX rA
=
(2A)
dV FA0
Since the flow-rates of the various compounds not calculated explicitly, Eq. 4 cannot be
used for calculation of CA as it needs to be expressed in terms of the original concentration of
A in the reactor feed CA0, the conversion in the reactor X, and the temperature change in the
reactor relative to the feed temperature T0.

CA =

C A0 (1 X )T0
(1 + X )T

(4A)

The use of the conversion requires revision of the enthalpy balance equation.

{[

]}

0
dT
rA H Rx
(TR ) + CP (T TR )
=
dV
FA0 (CPA + XC P )
where CP is the overall change in the heat capacity per mol of A reacted.

Solution of the Example Problem Using Traditional Techniques

(5A)

Fogler (1992) used the Simpson graphical technique to find the volume of the reactor and
the exit temperature for conversion of 20% of acetone data. Equations (2A), (3), (4A) and (5A)
were used in the solution. Fogler (1992) provided standard heats of formation and 2nd order
polynomial equations for calculating CP for the three compounds. As the example is based on
Jeffreys (1964) publication, it is assumed that this publication is the source of the data used by
Fogler. The set of equations and data (in POLYMATH format) as presented in the 3rd edition
of the Fogler book is shown in Table 1. The row numbers shown in Table 1 are not part of the
program; they were added as references for the explanations that follow.
The model is in a compact form as many of the calculations were carried out separately. In
line 3 the value of FA0 is given in (mol/s). The value of CA0 in mol/m3, calculated using the ideal
gas law is shown in line 5. The equation for CPA is shown explicitly for compound A (in line 7)
however for the rest of the compounds the equations are not shown and only the calculated
expression for CP is presented in line 8. The heats of formations of the individual compounds
0
are not shown either, only the resultant numerical value of H Rx
(TR ) is presented.
Figures 1 and 2 show the change of the conversion and temperature, respectively, in the
tubular-flow adiabatic reactor as function of the reactor volume. The curves that were obtained
by the model shown in Table 1 are marked as Jeffreys data. The conversion of 20% is
obtained with the reactor volume V = 1.191 m3 and the exit temperature in this case is T = 937
K. Fogler (1992) obtained reactor volume of 1.27 m3 with the very same outlet temperature
using Simpson graphical integration technique.
Extracting Physical Properties from the DIPPR Database Using the POLYMATH
Database Interface (PDI)
The physical property data and correlations that needed for the enthalpy balance include
heat of formation data and equations for calculating heat capacity and enthalpy values at
temperature T for the reactant and the two products. Current, up to date data and equations for
these properties can be found in the DIPPR database (Rowley et al., 2010). This database can
be accessed through the POLYMATH Database Interface (PDI) software.
The interface program enables searching the database for a particular compound, marking
the desired properties and obtaining as output the necessary data and correlations in a format
that can be copied and pasted directly into a computer code.
The information that is provided by the interface program in the POLYMATH format is
demonstrated in Table 2 for the properties of acetone that are required for the example
problem. This table shows most of the information as provided by the interface when the
POLYMATH format output is requested. The code that is generated by the interface program
includes correlation equations, definition of constant values and comments. Lines 1-11 can be
generated at once by selecting the desired Compounds and Properties and the Basic
Report. The Report Level determines the amount of information that is to be included as
comments.
Lines 1 through 4 contain the information related to the heat of formation of acetone. In
line 1, the full name of the property and the full name of the compound are shown (as a
comment: text that starts with the # sign and ends with the end of the line). In line 2, the
family of the compound and in line 3 its chemical formula are presented. In line 4, the property
value related information is displayed. The units of the property and its uncertainty ( < 1% in
this case) are included as comments. The variable into which the value of the property is

entered made up from the symbol of the property (HFOR in this case) and the chemical
formula of the compound involved.
The information provided for ideal gas heat capacity includes the full name of the property
and the compound (line 5), the compounds family (line 6) and its chemical formula (line 7).
For temperature dependent properties DIPPR provides the information regarding range of
validity for the temperature (line 8) and range of validity for the property (line 9).
The ideal gas enthalpy and heat capacity (lines 10 11) deserve special discussion. In
most cases DIPPR provides the coefficients for the Aly and Lee (1981) equation for this
property. The integrated form of this equation, for calculating ideal gas enthalpy is considerably
different than the heat capacity equation. For the benefit of the users, whenever the ideal gas
heat capacity is requested by the user, the equation for ideal gas enthalpy is also included, as
a comment (see line 10). Note that the enthalpy equation includes an integration constant
Hcon. This constant depends on the standard state selected for the enthalpy calculation. For
example, selecting as standard state pure gaseous component at 25 C (298.15 K) yields
Hcon as ideal gas enthalpy at 298.15 K. This value has to be subtracted from the enthalpy of
ideal gas at temperature T.
Solution of the Example Problem Using Basic Model Variables and DIPPR Property Data
The traditional solution technique that includes the use of conversion in the differential
equations, requires extensive manipulation of the equations. This extra effort is not required
when numerical solution techniques are used. Furthermore, in order to provide clear and
complete documentation of the problem, it is preferable to include all the original data and
variables in the model and carry out the calculations, even the simplest ones, with the
computer model. The POLYMATH model for solution of the example problem, using these
principles and data from the DIPPR database is shown in Table 3. For most of the variables
the units are provided in forms of comments.
The principal model equations are shown in lines 2-13. The mole balance equations (Eq.
2) are in lines 2-4 while the enthalpy balance equation (Eq 5) is in line 5. The notation
ICP_C3H6O, ICP_C2H2_O and ICP_CH4 is used for representing CPA, CPB and CPC,
respectively. The division by 1000 is used for converting the CP units from J/kmol*K (as
provided by the DIPPR correlation) to J/mol *K for consistency with the mole balance
equations. The variables rA (Eq. 3), CA (Eq. 4) and k are calculated in lines 6, 8, and 12,
0
(TR ) + H Q (T ) is calculated in line 13. The conversion X is not
respectively and the term: H Rx
required for the solution, using this formulation; however, it is calculated (in line 7) as the
reactor volume is specified in terms of the desired conversion.
In lines 1533, the heat of formation data and the equations for calculating the heat
capacity and enthalpy of the reactant and the products are presented. Only the information
which is essential for the problem solution is shown. This includes the property values, units,
upper limit on the uncertainty of the property values and temperature range of applicability of
the correlation equations. The range of applicability is important in order to ensure that the
solution of the problem does not require the use of one or more of the equations outside of
their range of validity. The uncertainty level of the data is important in order to determine what
size of safety factor has to be added to the calculated reactor volume, so that the desired
conversion can be achieved even in the worst case situation.
The problem specific constants, initial and final values are grouped together in lines 35-44.
The inclusion of all the data and calculations needed for the problem solution and grouping

together the model equations, physical property data and problem specific data provide clear
and complete documentation of the model. This in turn enables easy and efficient debugging,
modification and extension of the model of the problem. The POLYMATH problem solution is
obtained after the problem equations are automatically ordered just prior to the solution.
The graphical solution obtained using the model presented in Table 3 is shown in Figures
1 and 2 (the curves marked as DIPPR data). Observe that the temperature and the
conversion in the reactor are significantly lower in this case than when using the Jeffreys data.
The volume required in order to achieve 20% conversion is 2.052 m3, thus the reactor size is
larger by 72% than the size obtained using the Jeffreys data. The model shown in Table 1
cannot be used for locating the causes of difference because most of the original data was
omitted, and it is necessary to consult the detailed description provided by Fogler (1992). It
turns out that they main source of the difference is the heat of formation value of ketene which
is provided by Jeffreys (-61.09 kJ/mol) and the one that provided by DIPPR (-47.5 kJ/mol).
The source of the DIPPR heat of formation is Padley et al. (1986) where Jeffreys publication is
from 1964. This demonstrates the importance of the use of the most up to date physical
property data from reliable sources in process design calculations.
Conclusions
The example presented here demonstrates some of the advantages of the use of property
databases and mathematical models that contain accurate and documented data typically
needed in chemical engineering problem solving. This work demonstrates, in particular, that
using physical property information from dated sources may lead to considerable errors in
design. The inclusion of the original data in the model is shown to make the debugging,
modification and extension of detailed modeling problems more easily accomplished.
It is important for educators to introduce students to available and convenient problem
solving tools. Additionally students should be exposed to:
Use of consistent physical property data with documented uncertainty and range of
applicability values, extracted from reliable property databases.
Documentation of the problem, that includes a complete set of the original equations,
property data and correlations and problem specific data, in the computer model, clearly
marking the units and uncertainties of the variables and temperature range of
applicability of the correlations.
References
1. Aly, F. A., and L. L. Lee, "Self-Consistent Equations for Calculating the Ideal Gas Heat Capacity
Enthalpy, and Entropy". Fluid Phase Equilib. 6, 169 (1981)
2. Brauner, N., Shacham, M., Cholakov, G. St. and Stateva, R. P., Property Prediction by Similarity of
Molecular Structures Practical Application and Consistency Analysis, Chem. Eng. Sci. 60, 5458
5471 (2005)
rd
3. Felder, R. M. and Rousseau, R. W., Elementary Principles of Chemical Processes,3 Ed, John Wiley
& Sons, Inc, Hoboken, New-Jersey, 2000.
nd
4. Fogler, H. S., Elements of Chemical Reaction Engineering, 2 Ed, Prentice Hall, Englewood Cliffs,
New Jersey, 1992.
th
5. Himmelblau D. M., and Riggs, J. B., Basic principles and Calculations in Chemical Engineering, 7
Ed., Prentice-Hall, Upper Saddle River, New-Jersey, 2004.
nd
6. Jeffreys, G.V., A Problem in Chemical Engineering Design: The Manufacture of Acetic Anhydride, 2
ed. (London: Institute of Chemical Engineers, 1964)
7. Pedley, J.B.; Naylor, R.D.; Kirby, S.P.; Thermochemical Data of Organic Compounds; Chapman and
Hall, London, 1986.

8. Rowley, R. L.; Wilding, W. V.; Oscarson, J. L.; Yang, Y.; Zundel, N. A., DIPPR Data Compilation of
Pure Chemical Properties, Design Institute for Physical Properties, (http//dippr.byu.edu), Brigham
Young University, Provo, Utah, 2010.

Table 1. POLYMATH Solution of the Example Problem Using the Equations Presented by Fogler
(1992)
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15

Equation/ # Comment
d(X) / d(V) = -ra/Fao
d(T) / d(V) = -ra*(-deltaH)/(Fao*(Cpa+X*delCp))
Fao = 38.3
To = 1035
Cao = 18.8
Tr = 298 # K
Cpa = 26.63+0.183*T-45.86*10^(-6)*T^2
delCp = 6.8-11.5*10^(-3)*T-3.81*10^(-6)*T^2
k = 8.2*10^14*exp(-34222/T)
ra = -k*Cao*(1-X)/(1+X)*To/T
deltaH = 80770+6.8*(T-Tr)-5.75*10^(-3)*(T^2-Tr^2)-1.27*10^(-6)*(T^3-Tr^3)
V(0) = 0
V(f) =1.191
X(0) = 0
T(0) = 1035

Table 2. Physical properties of acetone as obtained from the DIPPR database by the POLYMATH interface

No.
1
2
3
4
5
6
7
8
9
10
11

Equation/ # Comment
# Enthalpy of Formation of Ideal gas at 298.15 K and 100000 Pa of ACETONE
# Compounds Family: KETONES
# Compounds Structure: CH3COCH3
HFOR_C3H6O = -215700000 # J/kmol (Uncertainty < 1%)
# Ideal Gas Heat Capacity of ACETONE
# Compounds Family: KETONES
# Compounds Structure: CH3COCH3
# Valid Temperature Range: 200K to 1500K
# Valid Value Range: 60487 to 188200 (J/kmol*K)
# HIG_C3H6O = 57040*T+163200*1607*coth(1607/T)-96800*731.5*tanh(731.5/T)
+HCON_C3H6O # J/kmol
ICP_C3H6O = 57040 + 163200 * (1607 / T / sinh(1607 / T)) ^ 2 + 96800 * (731.5 / T /
cosh(731.5 / T)) ^ 2 # J/kmol*K (Uncertainty < 1%)

Table 3. POLYMATH Solution of the Example Problem Using DIPPR Physical Properties
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44

Equation/ # Comment
# Model equations
d(FA)/d(V) = rA
d(FB)/d(V) = -rA
d(FC)/d(V) = -rA
d(T)/d(V) = (-(deltaH)) * (-rA) / ((FA * ICP_C3H6O + FB * ICP_C2H2O + FC * ICP_CH4 )/1000)
rA = -k * CA
XA = (FA0 - FA) / FA0
CA = yA * P / (8.31 * T)
yA = FA / (FA + FB + FC)
yB = FB / (FA + FB + FC)
yC = FC / (FA + FB + FC)
k = 8.2E14 * exp(-34222 / T)
deltaH = (HFOR_C2H2O +HFOR_CH4 -HFOR_C3H6O+HIG_C2H2O +HIG_CH4 -HIG_C3H6O)/1000 #J/mol
#
# Thermodynamic data and correlations from the DIPPR database
# ACETONE
HFOR_C3H6O = -215700000 # J/kmol (Uncertainty < 1%)
HCON_C3H6O = 57040*Tref+163200*1607*coth(1607/Tref)-96800*731.5*tanh(731.5/Tref) # J/kmol
HIG_C3H6O = 57040*T+163200*1607*coth(1607/T)-96800*731.5*tanh(731.5/T)-HCON_C3H6O # J/kmol
# Valid Temperature Range:200K to 1500K
ICP_C3H6O = 57040 + 163200 * (1607 / T / sinh(1607 / T)) ^ 2 + 96800 * (731.5 / T / cosh(731.5 / T)) ^ 2 #
J/kmol*K (Uncertainty < 1%)
# KETENE
HFOR_C2H2O = -47500000 # J/kmol (Uncertainty < 5%)
HCON_C2H2O = 36940*Tref+68650*1490*coth(1490/Tref)-45240*640*tanh(640/Tref) # J/kmol
HIG_C2H2O = 36940*T+68650*1490*coth(1490/T)-45240*640*tanh(640/T)-HCON_C2H2O # J/kmol
# Valid Temperature Range:150K to 1500K
ICP_C2H2O = 36940 + 68650 * (1490 / T / sinh(1490 / T)) ^ 2 + 45240 * (640 / T / cosh(640 / T)) ^ 2 #
J/kmol*K (Uncertainty < 1%)
# METHANE
HFOR_CH4 = -74520000 # J/kmol (Uncertainty < 1%)
HCON_CH4 = 33298*Tref+79933*2086.9*coth(2086.9/Tref)-41602*991.96*tanh(991.96/Tref) # J/kmol
HIG_CH4 = 33298*T+79933*2086.9*coth(2086.9/T)-41602*991.96*tanh(991.96/T)-HCON_CH4 # J/kmol
# Valid Temperature Range: 50K to 1500K
ICP_CH4 = 33298 + 79933 * (2086.9 / T / sinh(2086.9 / T)) ^ 2 + 41602 * (991.96 / T / cosh(991.96 / T)) ^ 2 #
J/kmol*K (Uncertainty < 1%)
#
# Constants, initial and final values
Tref=298.15 #K
P = 162 * 1000 # Pa
FA0 = 38.3 # mol/m^3
FB(0) = 0
FA(0) = 38.3
FC(0) = 0
T(0) = 1035 #K
V(0) = 0
V(f) = 2.052 # m^3

0.25
Jeffreys data

DIPPR data

Conversion (X)

0.2

0.15

0.1

0.05

0
0

0.2

0.4

0.6

0.8

1.2

Volum e (m ^3)

Figure 1 Conversion of acetone as function of reactor volume

1060
1040

Jeffreys data

DIPPR data

Temperature (K)

1020
1000
980
960
940
920
0

0.2

0.4

0.6

0.8

1.2

Volum e (m ^3)

Figure 2 Temperature change in the reactor as function of volume