Estimation of the Heat Capacities of Organic Liquids as a Function of

Temperature Using Group Additivity: An Amendment

Milan Zabransky and Vlastimil Ruzicka, Jr.a
Department of Physical Chemistry, Institute of Chemical Technology, Technicka 5, 166 28 Prague 6, Czech Republic
Received 4 February 2004; revised manuscript received 17 May 2004; accepted 17 June 2004; published online 12 January 2005

An amendment to a second-order group additivity method for the estimation of the

heat capacity of pure organic liquids as a function of temperature in the range from the
melting temperature to the normal boiling temperature is reported. The temperature dependence of various group contributions and structural corrections is represented by a
series of second order polynomial expressions. The group contribution parameters have
been developed from an extended database of more than 1800 recommended heat capacity values. The present method should be more versatile and more accurate than the
previous one Ruzicka and Domalski, J. Phys. Chem. Ref. Data 22, 597, 619 1993 due
to the use of a larger database and an improved procedure for parameter
calculation. 2005 American Institute of Physics. DOI: 10.1063/1.1797811
Key words: estimation, group contribution approach, heat capacity of liquids, organic compounds, temperature
dependence.

Contents
1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2. Development of the Method. . . . . . . . . . . . . . . . . .
2.1. Additivity Scheme. . . . . . . . . . . . . . . . . . . . . . .
2.2. Temperature Range. . . . . . . . . . . . . . . . . . . . . .
2.3. Group Notation. . . . . . . . . . . . . . . . . . . . . . . . .
2.4. Next-to-Nearest Neighbor Interactions. . . . . . .
3. Determination of Additivity Unit Values. . . . . . . . .
3.1. Database of Liquid Heat Capacities. . . . . . . . .
3.2. Parameter Estimation. . . . . . . . . . . . . . . . . . . .
4. Results and Discussion. . . . . . . . . . . . . . . . . . . . . . .
5. Conclusion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6. Acknowledgment. . . . . . . . . . . . . . . . . . . . . . . . . . .
7. Appendix. Sample Calculations for the Estimation
of the Heat Capacities of Limonene, Ethyl
Benzoate, and 1 Chloro-2-Propanol. . . . . . . . . . . .
8. References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

List of Tables
1. Parameters for the dependence of dimensionless
group contribution c i on temperature. . . . . . . . . .
2. Parameters for the dependence of dimensionless
structural correction c i on temperature. . . . . . . . .
3. List of equivalent groups. . . . . . . . . . . . . . . . . . . . .
4. Survey of available and selected compounds. . . . .
5. Comparison of experimental and estimated heat
capacities for the test set of compounds. . . . . . . . .
a

1. Introduction
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Author to whom correspondence should be addressed; electronic mail:

vlastimil.ruzicka@vscht.cz
2005 American Institute of Physics.

0047-26892004334107111$39.00

Heat capacity is a property required for carrying out many

chemical engineering calculations, establishing energy balances, or evaluating the effect of temperature on phase and
reaction equilibria. As experimental liquid heat capacity data
are available for only a fraction of the total number of compounds encountered in industrial processes 02ZAB/RUZ,
several estimation methods have been proposed.
In 1993 Ruzicka and Domalski published two articles
93RUZ/DOM1, 93RUZ/DOM2 describing a method of estimation of the heat capacity of pure organic liquids as a
function of temperature. The method was based on the second order additivity scheme proposed by Benson and coworkers for ideal gases 58BEN/BUS, 69BEN/CRU and for
liquid hydrocarbons 77LUR/BEN. The papers 93RUZ/
DOM1, 93RUZ/DOM2 were concerned with revision of the
existing group contributions and structural corrections developed by Benson and co-workers 69BEN/CRU, 77LUR/
BEN and with the extension of the method to cover a
broader range of organic liquids containing elements carbon,
hydrogen, oxygen, nitrogen, sulfur, and halogens. Further development of the method was made possible from a large
compilation of critically evaluated calorimetrically measured
heat capacities 96ZAB/RUZ.
An update of the critically evaluated heat capacity data of
organic liquids was published recently 01ZAB/RUZ1. The
entire database 96ZAB/RUZ with Erratum 01ZAB/RUZ2
and 01ZAB/RUZ1 of recommended heat capacity data now
consists of more than 1800 compounds. With the availability
of more data, we have amended the existing group contribution estimation method 93RUZ/DOM1, 93RUZ/DOM2 and
developed new parameters covering a larger number of
groups and structural units that in some cases are applicable
over a broader temperature interval. In addition, a slightly

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modified calculational procedure made it possible to estimate

parameters describing the temperature dependence of all
group contributions and structural units in one step. This
should result in a more generally applicable set of group
contribution and structural units, and also more accurate estimated heat capacities.
Recently, Chickos et al. 93CHI/HES reported a first order group additivity scheme for estimation of heat capacity
values at 298 K. We have compared estimated heat capacities
for some selected compounds using this method by Chickos
et al. with that developed in this work.

2. Development of the Method

2.1. Additivity Scheme
We have used the following expression to estimate the
heat capacity of organic liquids:
k

n c ,
R i1 i i

where R is the gas constant (R8.314 472 JK1 mol1 ),

99MOH/TAY, n i is the number of additivity units of type i,
c i is a dimensionless value of the additivity unit of type i,
and k is the total number of additivity units in a molecule.
The additivity units include groups and structural corrections.
Following the arguments of Ruzicka and Domalski
93RUZ/DOM1, 93RUZ/DOM2 a simple expression has
been chosen for the dependence of c i on temperature
c i a i b i

T
T 2
d i
,
100
100

where T is temperature in K and a i , b i , d i are adjustable

parameters. To improve the estimation of heat capacities of
1-alkanols, which exhibit an inflexion point in their dependence of heat capacity with temperature 93ZAB/BUR, a
third order polynomial in Eq. 2 was also tested. Even
though agreement between experimental and estimated heat
capacities for the 1-alkanols improved, the standard residual
deviation and the average absolute percent deviation of the
overall fit of all data deteriorated. We believe that insufficient
accuracy of the heat capacity data and the narrow temperature range of available data for some compounds are the
most probable causes preventing the use of a more extensive
functional form for the dependence of c i with temperature.
2.2. Temperature Range
The present estimation method is applicable from the
melting temperature to the normal boiling temperature,
which is the range of the liquid phase most often required in
chemical engineering calculations. At present, it is not possible to develop a group contribution method to estimate the
heat capacity values of organic liquids over a wider temperature range, as experimental data above the normal boiling
temperature are scarce. The present method can be extrapolated to temperatures above the normal boiling point. HowJ. Phys. Chem. Ref. Data, Vol. 33, No. 4, 2004

ever, the predictive accuracy notably deteriorates as the extent of the temperature extrapolation increases. The present
method fails near the critical point.
Due to the limited temperature range to which the method
is applicable, no distinction is made between the isobaric
heat capacity C p and the saturation heat capacity C sat . At
low saturation pressures below 0.1 MPa, C p and C sat are
nearly equal in magnitude. The difference between C p and
C sat at the normal boiling temperature lies typically below
0.5% and the difference becomes significant only at temperatures far above the normal boiling temperature. When the
method is applied above the normal boiling temperature the
deviations between observed and estimated heat capacities
exceed the differences between C p and C sat .
2.3. Group Notation
We have followed the group notation developed by Benson and co-workers 58BEN/BUS, 69BEN/CRU. The group
is defined as a central atom together with its nearest-neighbor
atoms and ligands. We have adopted the short form of the
notation for multiple bonded atoms (Cd , Ct , CB , CBF, and
Ca) that omits the atom at the other end of the multiple bond.
Cd is a double bonded carbon atom attached to a second
double bonded carbon atom and to two other monovalent
ligands, Ct is a triple bonded carbon atom attached to a second triple bonded carbon atom and to another monovalent
ligand, CB is a carbon atom in a benzene ring attached to two
other benzene ring carbon atoms and to another monovalent
ligand, Ca is the double bonded carbon atom located in the
middle of the allenic group CvCvC , and CBF is an aromatic ring carbon atom in fused ring aromatic compounds
such as naphthalene or phenanthrene in the bridge position
attached to at least one another CBF atom and from zero to
two CB atoms for a sample assignment see the paper
93RUZ/DOM1. Table 1 lists 130 groups with computed parameters: 29 contributions for groups containing atoms of
carbon and hydrogen; 39 contributions for groups containing
atoms of carbon, hydrogen, and oxygen; 20 contributions for
groups containing atoms of carbon, hydrogen, and nitrogen;
27 contributions for groups containing atoms of carbon, hydrogen, and halogens; ten contributions for groups containing atoms of carbon, hydrogen, and sulfur, and five contributions for groups containing C and H and mixed halogens or
halogens and oxygen.
We have adopted the approach proposed by Benson and
co-workers 69BEN/CRU, 76BEN to estimate the heat capacity of saturated and unsaturated cyclic hydrocarbons
with the exception of aromatic hydrocarbons and heterocyclic compounds containing oxygen, nitrogen or sulfur. The
heat capacity of a cyclic compound is estimated by summing
up group contributions developed for acyclic compounds and
then adding a structural correction that is specific for the
particular cyclic compound. As the corrections reflect the
internal ring constraints imposed on a molecule, they are
denoted as ring constraints corrections, or rcc. Table 2 lists
24 structural corrections with computed parameters.

HEAT CAPACITY OF ORGANIC LIQUIDS

Benson et al. 69BEN/CRU and many other authors who
have developed a second-order additivity method for the estimation of thermophysical properties arbitrarily assigned
values to some groups either when groups exist in conjugate
pairs or when data for the calculation of a group are unavailable. We have utilized some of the assignments mainly as it
reduced the colinearity of adjustable parameters 94RUZ/
DOM. The list of equivalent groups is given in Table 3.

2.4. Next-to-Nearest Neighbor Interactions

The second-order additivity method makes no allowance
for next-to-nearest neighbor interactions. Some authors have
found that such interactions have considerable influence on
molecular properties and therefore included corrections to
account for next-to-nearest neighbor interactions. The
gauche, cis, and ortho corrections developed by Benson
et al. 69BEN/CRU or the methyl repulsion correction suggested by Domalski and Hearing 88DOM/HEA are some
examples of the approach.
In this work we have developed cis and trans as well as
ortho and meta corrections as we have used an augmented
calculation procedure as compared with the work by Ruzicka
and Domalski 93RUZ/DOM1, 93RUZ/DOM2. Parameter
evaluations including the parameters listed above were carried out in a single step. Due to their small magnitude, these
corrections were previously neglected 93RUZ/DOM1,
93RUZ/DOM2. The para correction has been found to be
insignificant. For multisubstituted aromatic hydrocarbons,
corrections between all adjacent substituents have been taken
into account. Thus, for example, for 1,2,4-trimethylbenzene
one meta and one ortho corrections have been included, for
1,2,3-trichlorobenzene two ortho corrections have been included. Values for the corrections are given in Table 2.

3. Determination of Additivity Unit Values

A multiple linear least squares method has been used for
the calculation of adjustable parameters in Eq. 2. The minimized objective function has the following form:
m

j1

estd 2
w j C rec
j C j ,

is the recwhere the subscript j denotes jth data point,

is
the
estimated
ommended liquid heat capacity, and C estd
j
heat capacity. The weight w j is equal to the reciprocal of the
variance of the jth data point 2 (C j ). It is estimated for each
jth value on the basis of the assumed accuracy of the recommended heat capacities. The input information is the percentage error of the recommended data, r C. Thus, the weight of
the jth data point is expressed as
w j 1

3.1. Database of Liquid Heat Capacities

The recommended heat capacity values were obtained
from an extensive compilation that contains all currently
available calorimetrically measured heat capacities of more
than 1800 liquid organic compounds 96ZAB/RUZ, 01ZAB/
RUZ1. The compilation includes parameters of a smoothing
equation obtained from a critical assessment of experimental
data. Parameters are accompanied by a rating that represents
the expected overall accuracy of the data. The rating was
expressed as a percentage error and served as the input information for the calculation of weights in the least squares
parameterization refer to Eq. 4.
3.2. Parameter Estimation
The adjustable parameters were calculated by simultaneous minimization of the recommended heat capacity values for all selected compounds in one step. Table 4 gives a
survey of number of compounds available and those selected, the number of group values evaluated, and the number of ring corrections evaluated. Group values for a total of
nine families of compounds were evaluated. Altogether, 555
compounds hereafter called a basic set of compounds
have been selected out of 1836 compounds available in the
database 96ZAB/RUZ, 01ZAB/RUZ1. The remaining 1281
compounds were rejected for the following reasons: the uncertainty as given in compilations 96ZAB/RUZ, 01ZAB/
RUZ1 was above 3%; the recommended values were available only over a limited temperature interval or at a single
temperature; and a group or structural contribution would
have been calculated from data for only one compound
there were several exceptions to this rule which are given as
footnotes under Tables 1 and 2.
In the first step of the calculational procedure all compounds having reliable heat capacity data available over a
temperature range of 50 K minimum were selected. Discrete
data were generated over a temperature step of 10 K for all
selected compounds. The standard deviation SD and standard percent deviation SPD have been calculated after the
minimization procedure:
SD

SPD100
C rec
j

C j . rC
100

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tot
1
C recC estd 2 ,
n totn par i1

tot
1
C recC estd 2
,
n totn par i1
C rec

where n tot is the total number of data points and n par is the
number of adjustable parameters in Eq. 2.
All compounds exhibiting large systematic deviations
were rejected in the subsequent step of the minimization.
Also, for some compounds deviations increased at the beginning or at the end of the temperature interval. This is attributed to the atypical dependency of heat capacity on temperature for some compounds as explained by Zabransky et al.
93ZAB/BUR. For such compounds we have either limited
the temperature interval of data used in the minimization or
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rejected the compound. In the final step, group contribution

parameters were calculated using data from the basic set of
compounds.

4. Results and Discussion

To evaluate the quality of the group and structural contributions developed, we have used the reliable data from two
sources:
1 data from the database 96ZAB/RUZ, 01ZAB/RUZ1
for those compounds that were not included in the basic set
because of a limitation in the temperature range available.
2 recent data published in the literature following
completion of the work by Zabransky et al. 01ZAB/RUZ1.
Experimental data for a total of 46 compounds coming from
the above two sources hereafter called a test set of compounds were collected and compared to estimated heat capacities using parameters developed in this work. Since selection of compounds in the test set was arbitrary and based
mainly on the availability of data, it was impossible to make
a relevant statistical evaluation of the results of comparison.
We have also made a comparison with the estimated data
by the first order contributions by Chickos et al. 93CHI/
HES, in this case at 298 K only. Table 5 presents results of
the comparison and shows that our percent deviations PDs
are generally smaller than those of Chickos et al. It has been
demonstrated that the method by Chickos et al., despite its
simplicity of a first order group contribution method, provides reliable estimations.
In previous work 93RUZ/DOM1, 93RUZ/DOM2 the authors have compared the estimated heat capacity values with
those calculated by the group contribution method developed
by Luria and Benson 77LUR/BEN. Luria and Benson provided contributions only for aliphatic, cyclic, and aromatic
hydrocarbons. For these families of hydrocarbons, the SPD
see Eq. 6 between experimental heat capacities and those
estimated by the Luria and Benson method ranged from
1.6% to 3.3%, whereas SPD between experimental heat capacities and those estimated using parameters from Ruzicka
and Domalski 93RUZ/DOM1 ranged from 1.1% to 3.8%.
The present method results in SPDs ranging from 0.7% to
1.9% for the same families of compounds. For nine aromatic
and cyclic hydrocarbons compounds, there is a lack of group
and structural parameters in Luria and Benson; application of
the present method has resulted in average deviations ranging from 2.7% to 2.9%.
Some general conclusions have been drawn from the comparison with the test set of compounds. For the majority of
compounds the method error lies below 2% at temperatures
below the normal boiling temperature and increases with increasing temperature. For alkanols, acids and aldehydes, the
error is greater than 3% and rises significantly with increasing temperature. For alkanols the inflexion point in the dependence of heat capacity with temperature rises in the direction of higher temperatures as the number of carbon
atoms in the molecule increases. This behavior is difficult to
describe using a simple additivity scheme Eqs. 1 and 2.
J. Phys. Chem. Ref. Data, Vol. 33, No. 4, 2004

A sharp maximum in the liquid heat capacity curve observed

as a function of temperature for some aldehydes cannot be
predicted with the present method at all. The estimated heat
capacities of some diols are in error by more than 10% for
example 1,6-hexanediol. Moreover, for some diols the estimated heat capacities decrease with increasing temperature
or exhibit a maximum in the dependence of heat capacity
with temperature, which was not observed experimentally.
For these compounds the group contribution method developed in this work should be used for estimating the heat
capacity values at and around room temperature only.
Reliable estimations have been obtained for esters with the
method error usually below 2%. For halogenated hydrocarbons, the method error was below 1% as shown in Table 5
for a set of 13 compounds. For organic compounds containing sulfur, such as thiols, sulfides, and certain cyclic compounds, the agreement between experimental and estimated
heat capacity values is about 1% over a wide temperature
range as found for the basic set of compounds the largest
average deviation of 1.8% was obtained for benzenethiol.
For amines no recent reliable data were available for comparison. We have therefore used some older data for evaluation where the method error was up to 5%.
It has been found that the accuracy of the present group
contribution method deteriorates when applied to multifunctional compounds, i.e. a compound containing functional
groups from two or more different families. This is particularly true for multifunctional compounds containing a hydroxyl group e.g., see N,N -diethanolamine or 1-chloro-2propanol in Table 5.

5. Conclusion
Parameters for a group contribution method that permits
estimation of heat capacity values of organic liquids have
been determined. Summation of group contributions and
structural corrections represented by second order polynomials enables the user to obtain an analytical expression for the
heat capacity as a function of temperature. The method is
applicable for the estimation of heat capacities of liquid organic substances containing atoms of carbon, hydrogen, oxygen, nitrogen, sulfur, and halogens.
The present method cannot be used for the first members
of a homologous series; this limitation is typical of a majority of group contributions methods.
It has been demonstrated in previous work 93RUZ/
DOM1, 93RUZ/DOM2 that the method can be used to estimate heat capacity values from the melting temperature to
the normal boiling temperature; in this range the present
group and structural contribution parameters give an overall
standard deviation of 6.1 JK1 mol1 and overall standard
percent deviation of 1.7% calculated from comparison of
recommended and estimated data for the basic set of compounds.
Each group or structural contribution was calculated from
the heat capacities for at least two different compounds, with
29 exceptions. Still, there are many group and structural con-

HEAT CAPACITY OF ORGANIC LIQUIDS

tributions missing as heat capacity data are not available for
their evaluation. A short account of the missing heat capacity
data for some specific families of compounds is given in
Zabransky and Ruzicka 02ZAB/RUZ.

6. Acknowledgments
This work was supported by the Ministry of Education of
the Czech Republic under Grant No. CB MSM 223400008.
Our thanks are due to Pavel Moravek for his help in the
parameter estimation program development and to Dr. Eugene S. Domalski for his helpful comments.

Group additivity representation for 1-chloro-2-propanol: 1

C (H) 3 (C) 1C (H)(C) 2 (O)(alcohol) 1
C (H) 2 (C)(Cl) 1O (H)(C) .
Equations 1 and 2 are used to performed the calculation of parameters a24.3205, b11.1055, and d
3.505 57 in the temperature range 188.4 520.0 K. Estimated heat capacity of 1-chloro-2-propanol at 315 K,
C estd/R24.800 and C estd200.7 JK1 mol1 . Experimental value from 02STE/CHI4 is 206.2 JK1 mol1 ,
PD2.7%.

8. References
47OSB/GIN

7. Appendix. Sample Calculations for the

Estimation of the Heat Capacities of
Limonene, Ethyl Benzoate, and
1-Chloro-2-Propanol
The structural formula for limonene 1-methyl-4-1methylethenylcyclohexene CAS RN 5989-27-5 is:

54FIN/GRO
58BEN/BUS
68GOU/WES
69BEN/CRU

69PAU/LAV
71PAU/RAK

Group additivity representation for limonene: 2

C (H) 3 (C) 1C (H) 2 (C) 2 1C (H)(C) 3 2
C (H) 2 (C)(Cd) 1Cd (H) 2 1Cd (H)(C)
2Cd (C) 2 1cyclohexene(rcc) .
Equations 1 and 2 are used to performed the calculation of parameters a18.8512, b0.757 816, d1.041 75
valid in the temperature range 171.2 483.1 K. Estimated
heat capacity of limonene at 300 K, C estd/R30.532 and
C estd253.9 JK1 mol1 . Experimental value from
02STE/CHI1 is 250.3 JK1 mol1 , PD1.4%.
The structural formula for ethyl benzoate CAS RN 9389-0 is:

76BEN
77BEL/BUB
77LUR/BEN
79FUC/PEA
88DOM/HEA
90MES/TOD

91ASH/SOR
91BEN/GAR
91LIC
91PES/NIK

Group additivity representation for ethyl benzoate:

1C (H) 3 (C) 5CB (H)(CB) 2
1CB (CB) 2 (CO) 1C (H) 2 (C)(O)
1CO (CB)(O) 1O (C)(CO) .
Equations 1 and 2 are used to performed the calculation of parameters a22.6571, b0.715 298, and d
0.572 327 valid in the temperature range 185.0 630.0 K.
Estimated heat capacity of ethyl benzoate at 300 K, C estd/R
29.916 and C estd248.7 JK1 mol1 . Experimental
value from 02STE/CHI3 is 244.4 JK1 mol1 , PD
1.7%.
The structural formula for 1-chloro-2-propanol CAS RN
127-00-4 is:

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91STE/CHI
93CHI/HES
93FUJ/OGU1
93FUJ/OGU2
93RUZ/DOM1
93RUZ/DOM2
93SHE
93ZAB/BUR
94LEB/SMI

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02STE/CHI3

99MOH/TAY

Mohr, P. J. and B. N. Taylor, J. Phys. Chem. Ref. Data

28, 1713 1999.

Steele, W. V., R. D. Chirico, A. B. Cowell, S. E.

Knipmeyer, and A. Nguyen, J. Chem. Eng. Data 47,
725 2002.

02STE/CHI4

99ZIJ/WIT

Zijlema, T. G., G.-J. Witkamp, and G. M. van

Rosmalen, J. Chem. Eng. Data 44, 1335 1999.

Steele, W. V., R. D. Chirico, S. E. Knipmeyer, and A.

Nguyen, J. Chem. Eng. Data 47, 648 2002.

02STE/CHI5

00PAL/SZA

Palczewska-Tulinska, M. and A. M. Szafranski, J.

Chem. Eng. Data 45, 988 2000.

Steele, W. V., R. D. Chirico, S. E. Knipmeyer, and A.

Nguyen, J. Chem. Eng. Data 47, 689 2002.

02STE/CHI6

01BEC/GME

Becker, L. and J. Gmehling, J. Chem. Eng. Data 46,

1638 2001.

Steele, W. V., R. D. Chirico, S. E. Knipmeyer, and A.

Nguyen, J. Chem. Eng. Data 47, 715 2002.

02TSV/KUL

01DI/LI

Di, Y.-Y., Z.-N. Li, S.-H. Meng, Z.-C. Tan, and S.-S.
Qu, Thermochim. Acta 373, 31 2001.

Tsvetkova, L. Ya., T. G. Kulagina, and B. V. Lebedev,

Vysokomol. Soedin., Ser. A 44, 474 2002.

02ZAB/RUZ

01KOZ/BLO

Kozyro, A. A., A. V. Blokhin, G. J. Kabo, and Y. U.

Paulechka, J. Chem. Thermodyn. 33, 305 2001.

Zabransky, M., and V. Ruzicka, Fluid Phase Equilib.

194-197, 817 2002.

03CHI/KNI

01VAN/OON1

van Miltenburg, J. C., H. A. J. Oonk, and G. J. K. van

den Berg, J. Chem. Eng. Data 46, 84 2001.

Chirico, R. D., S. E. Knipmeyer, and W. V. Steele, J.

Chem. Thermodyn. 35, 1059 2003.

03GOR/TKA

01VAN/OON2

van Miltenburg, J. C., H. A. J. Oonk, and L. Ventola, J.

Chem. Eng. Data 46, 90 2001.

Goralski, P., M. Tkaczyk, and M. Chorazewski, J.

Chem. Eng. Data 48, 492 2003.

03VAN/GAB

01VAR/DRU

Varushchenko, R. M., A. J. Druzhinina, A. Yu.

Churkina, and C.-T. Zhi, Zh. Fiz. Khim. 75, 1351
2001.

van Miltenburg, J. C., H. Gabrielova, and K. Ruzicka,

J. Chem. Eng. Data 48, 1323 2003.

03VAN/VAN

van Miltenburg, J. C., G. J. K. van den Berg, and M.

Ramirez, J. Chem. Eng. Data 48, 36 2003.

01ZAB/RUZ1

Zabransky, M., V. Ruzicka, Jr., and E. S. Domalski, J.

Phys. Chem. Ref. Data 30, 1199 2001.

J. Phys. Chem. Ref. Data, Vol. 33, No. 4, 2004

HEAT CAPACITY OF ORGANIC LIQUIDS

1077

TABLE 1. Parameters for the dependence of dimensionless group contribution c i on temperature, c ia ib i(T/100)d i(T/100) 2 , T/K
Adjustable parameters
Group
C (H) 3 (C)
C (H) 2 (C) 2
C (H)(C) 3
C (C) 4
Cd (H) 2
Cd (H)(C)
Cd (C) 2
Cd (H)(Cd)
Cd (C)(Cd)
C (H) 2 (C)(Cd)
C (H) 2 (Cd) 2
C (H)(C) 2 (Cd)
C (C) 3 (Cd) a
Ct (H)
Ct (C)
Ct (CB)
Ca
CB (H)
CB (C)
CB (Cd)
CB (CB)
C (H) 2 (C)(CB)
C (H) 2 (CB) 2
C (H)(C) 2 (CB)
C (H)(CB) 3 a
C (C) 3 (CB)
CBF (CBF)(CB) 2
CBF (CBF) 2 (CB)
CBF (CBF) 3
C (H) 3 (O)
C (H) 2 (O) 2
C (H) 2 (C)(O)
C (H) 2 (C)(CO)
C (H) 2 (CO) 2 a
C (H) 2 (CB)(O)
C (H)(C) 2 (O) ether
C (H)(C) 2 (O) alcohol
C (H)(C) 2 (CO)
C (C) 2 (O) 2 a
C (C) 3 (O) ethera
C (C) 3 (O) alcohol
C (C) 3 (CO)
Cd (H)(CO)
Cd (C)(CO)
CB (CB) 2 (O)
CB (CB) 2 (CO)
COHC
CO (H)(Cd)
CO (C) 2
CO (C)(Cd)
CO (C)(CB) a
COHO
COCO
CO (Cd)(O)
CO (CB)(O)
COOCO
CO (O) 2
OHC
OHC diol
O (H)(CB)
OHCO
O (C) 2
O (C) 2 alcohol
O (C)(Cd) a
O (C)(CB)
O (CB) 2

ai
4.198 45
2.734 5
1.353 93
5.747 77
3.730 72
4.315 38
0.777 280
3.972 88
0.815 385
1.522 45
1.895 53
2.230 10
5.625 56
9.667 42
1.128 84
3.455 50
3.204 31
2.216 10
0.168 065
5.217 53
5.129 97
2.127 21
3.825 17
2.415 45
15.135 7
3.493 41
4.932 52
5.341 45
23.397 4
3.703 44
0.633 479
0.517 007
2.571 78
15.927 3
31.731 8
2.325 91
4.644 39
1.348 04
9.669 43
5.558 59
62.739 9
5.771 66
15.001 6
33.196 5
11.708 9
12.835 5
13.365 6
17.137 8
6.315 05
3.476 65
17.868 8
13.319 3
8.081 78
13.702 0
17.748 1
2.059 55
14.452 8
16.155 5
3.914 14
6.132 29
2.037 28
6.353 42
0.328 815
6.724 03
12.521 7
29.686 4

b i /K

0.312 709
0.122 732
1.392 18
2.807 27
0.213 303
1.713 40
4.086 61103
1.709 97
0.445 281
0.481 876
0.296 854
2.082 99
2.905 40
4.949 89
1.049 79
0.528 223
0.444 284
0.202 639
0.644 814
4.873 13
4.032 44
0.214 915
3.966 78
1.314 92
7.790 76
2.005 27
3.534 66
3.205 83
9.995 61
1.128 84
0.951 097
1.266 31
0.054 121 0
8.871 01
25.099 7
1.949 30
2.389 89
1.104 64
8.452 10
2.736 81
42.483 7
2.892 98
2.386 63
15.545 1
4.327 18
8.669 59
5.293 94
6.898 75
0.347 175
0.307 623
7.096 95
0.803 329
0.089 984 5
6.873 82
7.855 02
1.839 94
4.954 51
11.938 0
5.372 48
7.340 47
0.661 816
0.969 836
5.509 07
1.808 59
11.579 5
16.166 3

Temperature range
2

d i /K

0.178 609
0.123 482
0.101 118
0.314 392
0.143 503
0.390 372
0.051 210 2
0.473 699
0.222 630
0.035 342 1
0.092 5396
0.240 244
0.220 860
1.220 90
0.178 614
0.061 362 7
0.136 136
0.112 750
0.078 899 1
0.886 240
0.595 745
0.070 961 5
0.449 402
0.403 035
0.855 579
0.186 897
0.483 297
0.375 158
1.152 91
0.512 390
0.057 928 4
0.093 971 3
0.125 804
0.755 096
4.325 61
0.183 551
0.172 814
0.388 707
1.344 17
0.295 802
6.519 40
0.347 793
0.502 618
1.768 77
0.534 999
1.283 13
1.096 33
1.061 18
0.179 791
0.816 128
0.981 906
1.701 59
1.824 52
1.766 44
3.214 63
1.794 33
4.792 74
2.851 17
0.725 920
0.950 215
1.582 48
0.037 828 5
1.456 65
0.275 264
2.072 31
2.206 94

T min/KT max/K
85705
85700
85 483
146 423
100580
100530
140580
130553
130580
109530
128 375
111 460
166 296
150330
150284
228 330
140315
170770
170700
228 580
273770
170700
268 440
180 671
365596
170 600
248 700
332510
386 592
130380
171308
137 630
177530
255360
260 462
130520
188 630
184 510
273334
168 308
220 453
226 370
205580
199 428
277 600
185705
177 428
218 428
184 383
273580
298 680
275342
189510
199 415
185705
318 347
270510
153590
240 630
285 490
241510
130520
273 460
320500
277520
191570

J. Phys. Chem. Ref. Data, Vol. 33, No. 4, 2004

1078

BRANSKY
AND V. RU
ZIC
KA, JR.
M. ZA
TABLE 1. Continued
Adjustable parameters

Group
OCCO
O (Cd)(CO) a
C (H) 3 (N)
C (H) 2 (C)(N)
C (H)(C) 2 (N)
C (C) 3 (N)
CB (CB) 2 (N)
N (H) 2 (C)
N (H) 2 (N)
N (H)(C) 2
N (H)(C)(CB) a
NHCN
N (H)(CB)(N) a
N (H)(CB) 2 pyrrole
N (C) 3
N (C) 2 (CB) a
N (C) 2 (N)
NB (CB) 2
C (H) 2 (C)(CN)
C (C) 3 (CN) a
Cd (H)(CN) a
CB (CB) 2 (CN)
CB (NCO) isocyanate
CB (CB) 2 (NO2 )
C (H) 2 (C)(NO2 ) a
O (C)(NO2 )
C (H) 2 (C)(Br)
C (H) 2 (C)(Cl)
C (H) 2 (CB)(Cl) a
C (H) 2 (C)(F)
C (H) 2 (C)(I)
C (H)(C) 2 (Br)
C (H)(C) 2 (Cl)
C (H)(C)(Cl) 2
CHCClFa
CHCClOa
C (H)(C)(F) 2
C (C)(Br)(F) 2
C (C) 3 (Cl)
C (C) 2 (Cl) 2 a
C (C)(Cl) 3
C (C)(Cl)(F) 2
C (C)(Cl) 2 (F)
C (C) 2 (F) 2
C (C)(F) 3
C (CB)(F) 3
Cd (H)(Cl) a
Cd (Cl)(F) a
Cd (Cl) 2
Cd (F) 2
CB (CB) 2 (Br)
CB (CB) 2 (Cl)
CB (CB) 2 (F)
CB (CB) 2 (I) a
C (H) 3 (S)
C (H) 2 (C)(S)
C (H)(C) 2 (S)
C (C) 3 (S)
CB (CB) 2 (S)
SHC
S (C) 2
S (CB)(C) a
S (CB) 2 thiophene
SCS
a

ai
1.948 51
2.374 55
6.666 28
5.657 28
3.276 77
0.104 392
5.723 48
9.769 72
6.691 10
8.479 43
8.672 23
2.911 50
5.304 32
22.444 0
5.184 09
15.723 4
2.832 75
0.664 604
10.219 5
1.517 27
9.516 81
1.004 35
5.350 72
35.655 1
17.940 8
15.999 8
10.339 4
8.610 93
18.649 9
5.649 21
0.758 309
7.037 71
5.146 01
6.998 87
6.232 24
5.976 73
13.180 3
9.140 28
5.327 42
7.007 61
10.260 4
9.509 84
13.889 1
1.114 36
5.155 30
16.263 5
7.453 74
7.996 76
10.415 8
7.461 38
1.936 83
7.395 60
1.724 66
2.769 62
12.508 3
9.826 04
6.938 21
4.527 61
2.228 65
2.054 73
8.988 55
3.041 52
5.778 42
1.516 60

b i /K

0.039 677 5
1.285 61
3.047 69
1.814 84
3.322 81
0.334 373
2.183 15
0.787 001
0.535 766
13.729 3
9.648 76
2.655 01
6.363 28
15.416 5
7.145 55
13.261 7
6.326 87
1.293 87
1.195 19
3.439 98
1.130 73
4.620 53
2.012 31
14.442 6
5.313 96
4.748 18
1.288 15
1.244 70
7.808 96
0.221 284
5.813 19
0.513 121
0.208 322
2.512 47
0.236 507
5.529 10
5.548 67
0.464 167
0.615 941
1.656 18
1.176 06
1.506 26
2.691 96
5.200 58
0.810 691
6.372 27
0.909 389
0.931 574
2.215 28
1.818 50
1.961 56
1.951 70
1.339 75
2.816 71
4.370 48
3.380 11
2.427 95
1.852 76
0.466 465
1.182 07
6.242 28
3.496 85
1.044 58
2.448 92

Adjustable parameters were calculated from heat capacity data on a single compound only.

J. Phys. Chem. Ref. Data, Vol. 33, No. 4, 2004

Temperature range
d i /K

2.007 56
1.952 13
0.803 453
0.312 81 5
0.505 009
0.031 8456
0.317 372
0.029 084 4
0.116 779
2.839 67
1.684 57
0.604 121
0.997 913
1.984 31
1.555 46
2.488 03
1.338 94
0.194 972
0.303 634
0.535 832
0.287 598
0.659 838
0.246 140
1.957 94
1.035 48
1.077 20
0.189 034
0.302 973
1.408 52
0.284 400
0.933 958
0.114 302
0.053 585 2
0.498 986
0.286 196
0.380 660
1.341 16
0.297 157
0.096 141 2
0.357 188
0.141 100
0.535 196
0.554 294
0.911 666
0.352 253
1.259 70
0.169 918
0.272 285
0.589 100
0.739 347
0.261 815
0.368 160
0.149 748
0.563 751
1.117 39
1.321 66
1.465 61
1.568 62
1.966 73
1.739 90
2.831 03
3.221 18
0.184 344
1.519 85

T min/KT max/K
185705
189330
161388
190590
181398
210398
235770
181770
216 464
185590
240379
205298
293358
256 441
161590
283388
205298
207 610
185370
296 346
197347
265 480
242 480
250 415
189300
191300
222360
140520
246 347
173308
243345
190 475
182520
123330
105328
300335
163360
166 413
189306
240267
240310
123 420
105 420
126 380
126 380
211365
119300
120240
157291
120240
243369
230 437
211 490
250320
167369
130 440
135 490
172364
239700
130375
166 700
261321
207344
168 352

HEAT CAPACITY OF ORGANIC LIQUIDS

1079

TABLE 2. Parameters for the dependence of dimensionless structural correction c i on temperature, c ia ib i(T/100)d i(T/100) 2 , T/K
Adjustable parameters
ai

Structural correction
a

Cyclopropane
Cyclobutane
Cyclopentane
Cyclohexane
Cycloheptanea
Cyclooctanea
Cyclopentene
Cyclohexene
Cyclohexadiene
Indan
1H-indenea
Hexahydroindan
Tetrahydronaphthalenea
Decahydronaphthalene
Ethylene oxide
1,3-Dioxolane
Furan
Tetrahydrofuran
Tetrahydropyran
Pyrrolidine
Piperidine
Thiacyclobutanea
Thiacyclopentane
Thiacyclohexanea
CisTransOrthoMetaa

4.266 04
3.603 13
0.256 206
1.423 09
11.018 2
11.581 4
0.137 841
3.571 80
8.828 41
0.481 775
3.287 73
0.366 075
8.874 95
5.976 05
10.327 6
3.189 59
33.969 2
0.975 198
34.549 2
12.637 6
25.660 7
0.952 952
3.067 25
1.094 44
0.368 104
2.082 09
0.553 312
2.421 14

b i /K

3.843 65
3.925 27
1.255 79
0.688 726
5.423 84
6.220 87
1.099 12
1.084 91
7.250 33
0.555 782
2.482 45
1.900 51
5.046 17
1.261 83
8.257 74
0.855 281
17.457 1
2.139 99
22.483 3
11.787 8
20.598 0
1.984 37
0.779 155
1.385 72
0.427 315
1.873 29
0.419 661
1.460 18

Temperature range
2

d i /K

0.918 892
0.896 841
0.213 503
0.164 691
0.864 357
0.987 897
0.279 412
0.044 809 0
1.533 56
0.112 688
0.442 470
0.374 255
0.707 983
0.175 636
1.719 76
0.016 283 9
2.537 50
0.633 211
3.810 53
2.411 12
3.794 22
0.485 018
0.010 520 9
1.865 79
0.119 276
0.378 337
0.069 9794
0.225 513

T min /K T max /K
154 315
140301
140 460
144 490
269300
295322
141 460
171700
170300
170394
280375
212 483
248 660
234 483
150520
176 350
191307
190 410
265327
190 400
267370
202321
180389
296 342
129 423
170553
185 600
214 705

Adjustable parameters were calculated from heat capacity data on a single compound only.

TABLE 3. List of equivalent groups

C (H) 3 (C)wC (H) 3 (Cd)wC (H) 3 (Ct)wC (H) 3 (CB)wC (H) 3 (CO)wC (H) 3 (S)
C (H) 2 (C)(Ct)wC (H) 2 (C)(Cd)
CB (Ct)wCB (Cd)
Cd (H)(CB)wCd (H)(Cd)
Cd (C)(CB)wCd (C)(Cd)
CB (C)(CB)(CBF)wCB (C)
CB (Ct)(CB) 2 wCB (Cd)(CB) 2
N (H) 2 (CB)wN (H) 2 (C)
S (H)(CB)wS (H)(C)
O (H)(CB) (diol)wO (H)(C) (diol)
CO (H)(CB)wCO (H)(Cd)
C (H) 2 (Cd)(Cl)wC (H) 2 (C)(Cl)
C (H) 2 (CB)(N)wC (H) 2 (C)(N)
N (C)(CB) 2 wN (C) 3
C (H) 2 (Cd)(O)wC (H) 2 (CB)(O)
S (CB)(S)wS (C) 2
S (CB) 2 wS (C) 2

J. Phys. Chem. Ref. Data, Vol. 33, No. 4, 2004

1080

BRANSKY
AND V. RU
ZIC
KA, JR.
M. ZA
TABLE 4. Survey of available and selected compounds

Family of
compounds

Number of
compounds in
the database

Number of selected
compounds used in
the parameter
calculation

Number of
developed group
contributions

Number of
developed
structural rcc
corrections

377
552

163
183

29
39

14
5

165

57

20

63

45

10

229

78

27

55

215

24

172

1836

555

130

24a

Hydrocarbons
Compounds of
C, H, and O
Compounds of
C, H, and N
Compounds of
C, H, and S
Compounds of
C, H, and
halogens
Compounds of
C, H, O, and
halogens
Compounds of
C, H, O, N and F
Compounds of
C, H, O and S
Other
compounds
Total
a

Four more structural corrections cis, trans, ortho, meta have been developed.

TABLE 5. Comparison of experimental and estimated heat capacities for the test set of compounds

Compound
3,3-Dimethylhexane
Tridecane
1-Nonene
4-Methyl-1-pentene
Ethylidenecyclohexane
1,1-Dimethylethylbenzene
1-Methylpropylbenzene
Limoneneb
2-Methyl-2-1-methyloxypropane
2-Methyl-2-propoxypropane
2-Methoxy-2-methylbutane
Dibutoxymethane
1,2-Dimethoxybenzene
Triglymed
1-Hexanol
1-Octanol
1-Dodecanol
1-Heptadecanol
1-Eicosanol
1,2-Propanediol
1,3-Propanediol
1,6-Hexanediol
trans-2-Butenale
5-Hexen-2-one
2-Ethylhexanal
1,5-Pentanedioic acid
Cyclohexyl formate

PDa at 298 K
%

Reference to
experimental
data

Temperature
range for
comparison/K

PDa/%

47OSB/GIN
54FIN/GRO
90MES/TOD
94LEB/SMI
79FUC/PEA
02STE/CHI4
02STE/CHI4
02STE/CHI1
01VAR/DRU
01VAR/DRU
02STE/CHI1
00PAL/SZA
01BEC/GME
01BEC/GME
03VAN/GAB
03VAN/GAB
03VAN/VAN
03VAN/VAN
01VAN/OON2
02STE/CHI5
02TSV/KUL
91STE/CHI
02STE/CHI1
02STE/CHI6
01BEC/GME
02STE/CHI3
01KOZ/BLO

290305
270310
200380

1.9 to 1.6
4.3 to 1.8
2.9 to 3.7

298 380
298 400
298 360
190320
190320
300500
298 310
310360
310 410
240380
260380
298 380
330370
340360
300540
250298
313 413

1.8 to 3.0
0.3 to 5.6
1.3 to 1.7
1.6 to 1.5
3.6 to 0.4
0.8 to 3.7
1.0 to 5.5
3.4 to 2.4
1.2 to 3.5
1.9 to 0.4
4.7 to 3.8
8.0 to 4.6
9.4 to 7.1
9.6 to 8.1
2.9 to 4.7
2.4 to 2.0
3.8 to 15.6

300380
310380
370 480
270310

0.1
1.2
2.9
6.4

J. Phys. Chem. Ref. Data, Vol. 33, No. 4, 2004

to
to
to
to

0.3
8.3
9.6
2.1

This
work

Method
93CHI/HES

0.1
2.2
0.2
0.5
1.7
1.8
0.3
1.3
1.3
0.4
0.8c
1.0

1.1
3.4
3.5
2.5
4.7
0.8
2.0
3.8
2.2
1.4
0.3
9.3

3.1
5.5
8.0

2.8
1.0
0.7

2.9c
2.0

2.3
14.3

0.1
0.1c

1.5
0.1

3.0

HEAT CAPACITY OF ORGANIC LIQUIDS

1081

TABLE 5. Continued

Compound
Cyclohexyl acetate
Cyclohexyl pentanoate
Methyl benzoate
Methyl 2-methylbenzoate
Methyl 3-methylbenzoate
Ethyl trimethylacetate
Ethyl benzoate
Diethyl carbonate
Octyl acetate
Triethylene glycole,g
N-Methylethyl-2-propanamine
N-Propyl-1-propanamine
1-Decanamine
N,N-Dimethylbenzenamine
4 -Propylbiphenyl-4-carbonitrile
Pyrazine
4-Bromotoluene
1,2-Dichloroethane
1,3-Dichloropropane
1,4-Dichloropropane
1,5-Dichloropentane
1,6-Dichlorohexane
2-Chlorobutane
4-Chlorotoluene
1,4-Difluorobenzene
Decafluorobiphenyl
4-Iodotoluene
1,4-Bromoiodobenzene
1-Chloro-2-propanol
Dicambai
N,N -Diethylethanolamine
1-Nitropropane
2-2-Aminoethoxyethanol
Pentafluoroaniline
2-Bromothiophene
2-Chlorothiophene
Thiazolej

PDa at 298 K
%

Reference to
experimental
data

Temperature
range for
comparison/K

PDa/%

01KOZ/BLO
01KOZ/BLO
02BLO/PAU
02BLO/PAU
02BLO/PAU
02STE/CHI2
02STE/CHI3
01BEC/GME
01BEC/GME
02STE/CHI5
99ZIJ/WIT
91PES/NIK
77BEL/BUB
96ZAB/RUZ
91ASH/SOR
03CHI/KNI
96VAN/ALV
03GOR/TKA
03GOR/TKA
03GOR/TKA
03GOR/TKA
03GOR/TKA
93SHE
96VAN/ALV
91LIC
71PAU/RAC
96VAN/ALV
01VAN/OON1
02STE/CHI4
01DI/LI
02STE/CHI6
96TAN/TOY
99CHI/LIU
69PAU/LAV
93FUJ/OGU1
93FUJ/OGU2
68GOU/WES

240298
230310
270298
230298
280298
300360
300500
310 410
310 420
300320
278

3.7 to 1.7
4.1 to 4.2
0.1 to 1.5
2.2 to 2.5
0.9 to 0.8
2.4 to 1.4
1.8 to 2.6
2.2 to 0.4
1.8 to 1.4
1.4 to 4.5
4.7

340380
330540
300320
284 328
284 328
284 328
284 328
284 328

3.6
2.3
0.9
2.3
1.1
0.0
0.1
0.4

349
310330
365h
315355
392 402
298 450

0.1
1.1 to 0.3
2.0
2.7 to 11.4
2.2 to 0.8
12.3 to 3.8

303353
318
240298
230298
240340

3.1 to 0.9
3.4
0.1 to 1.9
2.5 to 1.44
3.7 to 2.9

to
to
to
to
to
to
to
to

3.8
3.2
1.0
2.1
3.0
0.3
0.2
0.7

This
work

Method
93CHI/HES

1.7
4.4
1.5
2.5
0.8
2.4c
1.8c

1.1
6.3
2.8
6.1
3.5
0.1
4.4

1.7c
1.4c

3.9
6.9

1.6
5.8
0.1

1.7
0.2
2.1

0.9c
2.1
1.2
0.1
0.0
0.4
0.2
0.2c
0.5

7.4
2.8
0.2
3.0
4.0
5.2
3.7
3.9
5.5

12.3
1.7
3.2c

5.7
1.9
4.4

1.9
1.4
2.7

5.4
6.2
4.4

Percent deviation PD100 (C expCestd)/C exp, where C exp is the experimental liquid heat capacity, C estd is the estimated heat capacity.
1-Methyl-4-1-methylethenylcyclohexene.
c
Experimental data extrapolated to 298 K.
d
1,2-Bis 2 -methoxyethoxy ethane.
e
The estimation method may be used around 300 K only. The estimated heat capacities decrease with increasing temperature contrary to experimental data
which monotonically increase.
f
The method by 93CHI/HES does not include a group value required for the estimation.
g
2,2 -Ethylenedioxydiethanol.
h
Upper limit of the estimated value valid to 320 K only; extrapolated to 365 K.
i
3,6-Dichloro-2-methoxybenzoic acid.
j
The estimated heat capacity was obtained by summing up three CB (H) and one NB (CB) 2 and one S (CB) 2 thiophene contributions.
a

J. Phys. Chem. Ref. Data, Vol. 33, No. 4, 2004