The Heat Capacity of Gaseous and Liquid Polychlorinated

Biphenyls, Polychlorinated Dibenzo-N-Dioxins and Dibenzofurans

Kulikova T.V., Mayorova A.V., Shunyaev K.Yu.

Institute of Metallurgy, Ural Branch RAS
Ekaterinburg, Russia
E-mail: kuliko@gmail.com

ABSTRACT
The study deals with analysis and systematization of the known and calculation of the
unknown thermodynamic characteristics (the heat capacity 298, temperature
dependences of the heat capacity (T) ) of widespread hazardous isomers of gaseous
and liquid compounds of polychlorinated biphenyls (PCBs), polychlorinated dibenzo-
n-dioxins (PCDDs), and polychlorinated dibenzofurans (PCDFs).

Introduction
Unique technological and physicochemical properties of polychlorinated
biphenyls (PCBs), a huge volume of their production, considerable volatility and
solubility, and extreme chemical inertness have led to the world-wide spread of PCB-
containing equipment and materials, resulting in the universal contamination with
these substances. The most common method used in Russia for destruction of PCBs is
their incineration with the formation of polychlorinated dibenzo-n-dioxins (PCDDs)
and dibenzofurans (PCDFs), which are among the most hazardous chemical
substances known to the mankind.
As often happens, the hazard of PCBs has long been underestimated. With
respect to their severe toxicological effect, PCBs are identical to substances that are
referred to the high class of hazard. Since these substances are especially toxic, they
have been assigned low toxicological standards, which necessitate special
requirements on the organization of processes assuming formation of these substances
(the so-called dioxinogenic processes) so that industrial emissions meet the norms.
Instrumental investigations of these substances are very expensive and, in this
connection, interest is attracted to calculation methods for simulation of processes by
the data on their thermochemical properties (the standard enthalpy and entropy of
formation, the heat capacity, temperature dependences of the heat capacity, the
enthalpy increment, etc.).
A quality thermodynamic simulation requires the knowledge of
thermodynamic and thermochemical properties of all reliably certified compounds of
the system under study in the gaseous or condensed state. Therefore the present study
deals with the analysis and systematization of the known and calculation of the
unknown the heat capacity of most toxic and hazardous isomers of gaseous PCBs,
PCDDs and PCDFs, and liquid PCBs.

CALCULATION OF THE HEAT CAPACITY

It is known that there are 209 individual PCB congeners, 420 polychlorinated
dibenzo-n-dioxins and polychlorinated dibenzofurans, which differ by the number and
positions of chlorine atoms in a molecule. The most widespread PCB compounds
containing up1 to 10 chlorine atoms were chosen for the study. In deciding on
isomers, preference was given to ortho-unsubstituted PCBs because they are most
toxic and their effect is similar to the effect of PCDDs and PCDFs. Congeners, which

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do not have chlorine atoms in ortho-positions of molecules (ortho-unsubstituted
PCBs), can acquire the planar configuration, which is more favorable in energy terms.
Such congeners are isostereoisomeric to PCDDs and PCDFs and present the greatest
hazard. As to the PCDD and PCDF isomers, of special hazard to humans and the
environment are tri-, tetra-, penta-, and hexa-substituted dioxins and furans
containing halogen atoms in lateral positions 2, 3, 7, and 8.
In this study we analyzed the known and calculated the unknown the heat
capacity of 17 most widespread and hazardous isomers of PCBs, PCDDs and PCDFs
in the gaseous state and 11 compounds of liquid PCBs.
Gaseous PCBs, PCDDs and PCDFs . The literature survey showed that studies
dealing with estimation of the heat capacity, the of gaseous PCB, PCDD and PCDF
compounds are few. Most of them are based on calculations or are semi-empirical. For
example, Saito and Fuwa [1] calculated thermodynamic functions of all PCBs and
some PCDDs and PCDFs on the basis of semi-empirical calculations in terms of the
PM3 model. O.V. Dorofeeva et al. [2-4] used statistical methods. Table 1 presents the
literature data on standard enthalpies and entropies of formation of gaseous and liquid
PCBs, PCDDs and PCDFs. The comparison of results obtained in different studies
reveals a considerable discrepancy between values reported by highly respected
investigators who did very arduous work. In particular, values the heat capacity [1]
are 8-70% larger than the corresponding values in [2-4]; the discrepancy grows with
the number of chlorine atoms in a molecule. So, we thought it reasonable and topical
to attempt an independent result.
Benson's method [5] was used to calculate the heat capacities of the gaseous
PCBs, PCDDs and PCDFs.
. We shall dwell briefly on this method.
Benson's method is the group additivity method involving analysis of the
molecule structure. Atomic or molecular groups are separated and the nearest
neighbors of the atom or the group are considered. Table 2 gives the number of groups
necessary for determination of group increments in structural formulas of PCBs,
PCDFs and PCDDs. Values of the thermodynamic characteristics of group increments
were determined from available reference and literature data [5-6]. Information about
the energy contribution of each group and the number of groups (see Table 3) was
used to calculate the heat capacities of the PCBs, PCDDs and PCDFs.

Table 2. Number of groups for determination of group increments in structural

formulas of PCBs, PCDFs and PCDDs
Number of groups Number of chlorine
Compound *-H -Cl -O - atoms in a
molecule (n)
PCBs 10 - n n - 2 1 10
PCDFs 8-n n 2 2 18
PCDDs 8-n n 4 - 18

* is the carbon atom in an aromatic ring.

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Table 3. Values of the thermodynamic characteristics determined by the method of
group increments[5],[9].

Group (gas) (liquid)

298 J/ 298 J/(moleK)
(moleK)
*-H 13,61[9] 22,68[9]
13,56[5]
- 13,12[9] 17,07[9]
13,94[5]
-Cl 29,33[9] 35,27[9]
30,98[5]
()2-O - -
orto corr Cl-Cl 30,80[9] -
2,094[5]
meta corr Cl-Cl - -

* is the carbon atom in an aromatic ring

Values presented in Table 1 show the heat capacities of PCBs, PCDDs and
PCDFs calculated in this study and by other investigators. It follows from the
comparison of these results that the values of the heat capacity at T = 298 K obtained
by using statistical methods (O.V. Dorofeeva et al. [2-4, 7,10]) for 17 isomers of
PCBs, PCDDs and PCDFs are in good agreement with the values calculated by other
investigators [9, 11-13] and with the our values.
Benson's method was used to calculate temperature dependences of the heat
capacity.
Values of the thermodynamic characteristics of group increments were
determined from available reference and literature data [5-6]. Information about the
energy contribution of each group and the number of groups (see Table 2 and 4) was
used to calculate the heat capacity dependence of molecules vs temperature. The
obtained results were processed by a polynomial:

= + bx + cx2 + dx3 + e105T-2, (1)

where = T10-3.
Values of the coefficients a, b, c, d and e are given in Table 5.
Liquid PCBs . It should be noted that ample literature data on the heat capacity of
liquid ecotoxicants is only available for biphenyl (C12H10) [9, 14], dibenzo-n-dioxin
(C12H8O2) [7, 15] and dibenzofuran (C12H8O) [5, 15]. The only study dealing with
calculation of the heat capacity for the whole series of liquid PCDD and PCDF
homologues was published by V.S. Iorish et al. [7]. As to liquid PCB compounds, the
literature data on their the heat capacity are scarce [9, 14].
The heat capacity of liquid PCBs were calculated was calculated by two
options: using the group additivity method due to Domalski [9] and from the equation
2. Information about the energy contribution of each group and the number of groups
(see Table 1 and 2) was used to calculate the heat capacity .

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Table 4. Heat capacity of group increments according to Benson [5, 6]
(), cal/(molK)
Group
300 400 500 600 800 1000
*-H 3.24 4.44 5.46 6.30 7.54 8.41
- 3.33 4.22 4.89 5.27 5.76 5.95
-Cl 7.4 8.4 9.2 9.7 10.2 10.4
-O 3.9 5.3 6.2 6.6 6.9 6.9
orto corr -0.50 -0.44 -0.55 -0.53 -0.28 -0.02
Cl-Cl

* is the carbon atom in an aromatic ring.

Data on the heat capacity of liquid PCBs can be found in [7, 9, 14]. Using the
literature data on the heat capacity (0298) of biphenyl and values of the
thermodynamic characteristics of the -H and -Cl groups in Table 2, we calculated
0298 for the series of PCBs compounds:

0298 (PCB) = 0298 (BP) - (10 - n) 0298 ( - H) + n 0298 (-Cl) +(m*orto corr Cl- Cl ) (2)

Values presented in Table 4 show the heat capacities of PCBs, PCDDs and PCDFs
calculated in this study and by other investigators.
Missenar's group additivity method [12] was used to calculate temperature
dependences of the heat capacity of liquid PCBs (heat capacities of group
contributions at different temperatures are given in Table 6). The calculated
temperature dependences were processed by the polynomial (1). Coefficients of the
polynomial (1) are tabulated in Table 5. Data on the heat capacity of liquid PCBs at T
= 298 K are given in Table 5. It is seen that the values of the heat capacity at 298 K,
which were calculated in this study by Missenar's method [12] and the equation (6),
agree well with each other and with those obtained in [9].

Table 6. Heat capacity of group increments according to Missenar [6]

(), cal/(mole)
Group
248 273 298 323 348 373
C6H5- 26.0 27.0 28.0 29.5 31.0 32.5
-H 3.0 3.2 3.5 3.7 4.0 4.5
-Cl 6.9 7.0 7.1 7.2 7.35 7.5

Conclusions
1. The literature data on the heat capacity of 17 most widespread and hazardous
isomers of PCBs, PCDDs and PCDFs in the gaseous state and 11 compounds of
liquid PCBs have been analyzed and systematized for the first time.

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 2. Methods have been developed for calculating of the heat capacity of organic
compounds. Values of the heat capacity of gaseous and liquid PCBs, PCDDs and
PCDFs have been calculated for the first time.
3. The comparison of the calculated values of the heat capacity with the known
literature data demonstrated their good mutual correlation.
4. The obtained data were added to the TERRA database and were used for
thermodynamic simulation of the thermal stability of PCBs, PCDDs and PCDFs.
5. The obtained data can be used for simulating of the behavior of complex
heterogeneous systems, including ecotoxicants, over a wide interval of
temperatures and initial compositions.

This study were supported by RFBR (project No. 08-03-00362-a)

and program for young scientists and graduate students of
Ural Branch RAS.

References
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dioxins for gas phase using semi-empirical molecular orbital method with PM3
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properties of polychlorinated biphenyls in the gas phase. J. Phys. Chem. A.
2004 108 8324-8332.
3. O.V. Dorofeeva: Ideal gas thermodynamic properties of biphenyl.
Thermodynamica Acta. 2001 374 7-11.
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dibenzo-p-dioxin, dibenzofuran and their polychlorinated derivatives in the
gaseous and condensed phases.1. Thermodynamic properties of gaseous
compounds. J. Chem. Eng. Data. 1999 44 516-523.
5. S.W. Benson, F.R. Cruickshank, D.M. Golden, G.R. Haugen, H.E. ONeal,
A.S. Rodgers, R. Shaw, and R. Walsh: Additivity Rules for the Estimation of
Thermochemical Properties. Chem. Rev. 1969 69 279-324.
6. H.K. Eigenmann, D.M. Golden, and S.W Benson: Revised Group Additivity
Parameters for the Enthalpies of Formation of Oxygen-Containing Organic
Compounds. J. Phys. Chem. 1973 77 1687-1691.
7. V.S. Iorish, O.V. Dorofeeva, N.F. Moiseeva: Thermodynamic properties of
dibenzo-p-dioxin, dibenzofuran and their polychlorinated derivatives in the
gaseous and condensed phases. 2. Thermodynamic properties of condensed
phases. J. Chem. Eng. Data 2001 46 286-298.
8. Jung Eun Lee and Wonyong Choi: DFT Calculation on the Thermodynamic
properties of polychlorinated dibenzo-p-dioxins: intramolecular Cl-Cl repulsion
effects and their thermochemical implications. J. Phys. Chem. A 2003 107
2693-2699.
9. Domalski E. S. and Hearing E. D.: Estimation of the Thermodynamic
Properties of C-H-N-O-S-Halogen Compounds at 298.15 K. J. of Phys. and
Chem. Ref. Data. 1993 22 805-1159.

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10. L.V. Gurvich, O.V. Dorofeeva, V.S. Iorish.: Thermodynamic simulation of
formation of 2,3,7,8-tetrachlordibenzo-p-dioxin during combustion processes.
Zh. Fiz. Khimii 1993 67 (10) 2030-2032.
11. W.-Y. Shiu and K.-C. Ma. Temperature Dependence of Physical: Chemical
Properties of Selected Chemicals of Environmental Interest. II. Chlorobenzenes,
Polychlorinated Biphenyls, Polychlorinated Dibenzo-p-dioxins, and
Dibenzofurans. J. Chem. Ref. Data 2000 29 (3) 387-462.
12. P. Reid, J. Prausnitz, T. Sherwood: Properties of Gases and Liquids.
Leningrad, Khimiya, 1982, 592 (in Russian).
13. V.A. Lukyanova, V.P. Kolesov: Standard formation enthalpy of dibenzo-p-
dioxin. Zh. Fiz. Khimii. 1997 71 (3) 406-408. (in Russian).
14. Richard, Laurent and Helgeson Harold C.: Calculation of the thermodynamic
properties at elevated temperatures and pressures of saturated and aromatic high
molecular. Geochimica et Cosmochimica Acta, 1998 62 (23/24) 3591 - 3636.
15. I. Barin: Thermochemical Data of Pure Substances. Weinheim, Federal
Republic of Germany: VCH Verlagsgesellschaft mbH, 1997.
16. "Cambridgesoft" database, ver. 8.0.6, December 31, 2003.

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 Table 1. Heat capacities of gaseous and liquid PCBs, PCDDs and PCDFs at T = 298 K
p298, J/(mole ) p298, J/(mole )

Compound (gas) (liquid)

Our study [9, 14] Our study Eq. (6)
[1] [2, 4] [9] [16] (Benson's (Missenar's
method) method)
C12H10 260.94 [9] 236.63 250.7
132.90 166.40[2] 161.20 162.34 162.10
(biphenyl) 250.7 [14]
C12H9Cl 273.53 [9] 251.76 263.29
141.10 183.50 [4] 176.40 178.06 179.60
(3-monochlorbiphenyl)
C12H8Cl2 286.12 [14] 266.86 275.88
164.70 199.00 [2] 191.70 193.78 197.20
(4,4-dichlorbiphenyl)
C12H7Cl3 298.71 [9] 281.96 288.47
172.40 215.00 [2] 206.90 209.5 214.50
(3,4,4-trichlorbiphenyl)
C12H6Cl4 311.3 [14] 297.07 301.06
188.40 231.00 [2] 222.10 225.22 232.10
(3,3,4,4-tetrachlorbiphenyl)
C12H5Cl5 323.9 [9] 312.53 313.65
196.20 246.90 [2] 237.40 240.94 249.50
(3,3,4,4,5-pentachlorbiphenyl)
C12H4Cl6 336.48 [14] 327.86 326.24
205.80 262.60 [2] 252.60 256.66 266.90
(3,3,4,4,5,5-hexachlorbiphenyl)
C12H3Cl7 349.07 [9] 342.71 338.83
(2,3,3,4,4,5,5- 214.00 275.10 [2] 267.80 272.38 284.30
heptachlorbiphenyl)
C12H2Cl8 361.66 [14] 357.49 351.42
(2,2,3,3,4,4,5,5- 221.60 290.80 [2] 283.10 288.1 301.70
octachlorbiphenyl)
C12HCl9 374.25 [9] 372.59 364.01
(2,2,3,3,4,4,5,5,6- 229.30 306.30 [2] 298.30 303.82 319.20
nanochlorbiphenyl)
C12Cl10 386.84 [9] 387.70 376.60
(2,2,3,3,4,4,5,5,6,6- 236.40 321.10 [2] 313.60 319.54 336.60
decachlorbiphenyl)

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 Table 5, cont'd
C12H8O2 180.04
153.90 180.20 [4] - 172.33 - - -
(dibenzo-n-dioxin)
C12H4Cl4O2 240.97
(2,3,7,8,-tetrachlordibenzo-n- 201.50 241.20 [4] - 245.18 - - -
dioxin)
12H3Cl5O2
(1,2,3,4,6-pentachlordibenzo-n- 217.38 257.62 [4] - - 259.45 - - -
dioxin)
12H2Cl6O2
(1,2,3,4,7,8-hexachlordibenzo-n- 195.76 273.89 [4] - - 321.56 - - -
dioxin)
12HCl7O2
(1,2,3,4,6,7,8-heptachlordibenzo- 205.23 289.69 [4] - - 338.98 - - -
n-dioxin)
C12H8O
148.06 163.65 [4] 167.30 - 169.07 - - -
(dibenzofuran)
C12H4Cl4O
195.59 225.90 [4] 228.20 - 234.56 - - -
(1,2,3,4 tetrachlordibenzofuran)
12H3Cl5O
(1,2,3,7,8- 195.02 241.22 [4] - - 249.88 - - -
pentachlordibenzofuran)
12H2Cl6O
(1,2,3,4,7,8- 202.74 257.50 [4] - - 267.30 - - -
hexachlordibenzofuran)
12HCl7O
(1,2,3,4,6,7,8,- 210.41 273.29 [4] - - 284.72 - - -
heptachlordibenzofuran)

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 Table 5. Temperature dependences of the heat capacity PCBs, PCDDs and PCDFs compounds
Compound = a + b10-3 + c10-6 2+d10-93 +e105 2 J/(moleK)
a b c d e

C12H10(*) -120.7 1178.6 -963.5 306.7 8.1

C12H9Cl(*) -111.4 1217.7 -1034.5 333.5 9.9
C12H8Cl2(*) -102.5 1257.9 -1107.0 369.0 11.9
C12H7Cl3(*) -93.1 1296.3 -1177.2 399.5 13.6
C12H6Cl4(*) -84.4 1337.5 -1250.8 431.5 15.6
C12H5Cl5(*) -74.9 1375.6 -1320.7 461.9 17.3
C12H4Cl6(*) -65.9 1415.5 -1392.8 493.2 19.2
C12H3Cl7(*) -57.0 1455.7 -1465.2 524.7 21.1
C12H2Cl8(*) -47.2 1492.8 -1533.9 554.7 22.7
C12HCl9(*) -38.4 1533.2 -1606.5 586.2 24.7
C12Cl10(*) -28.8 1571.2 -1676.2 616.5 26.4
C12H8O2(*) 132.71 425.30 -134.146 0.0007 -60.92
C12H4Cl4O2(*) 221.68 351.55 -115.33 -0.0007 -66.99
C12H3Cl5O2(*) 243.66 333.46 -110.76 0.0007 -68.05
C12H2Cl6O2(*) 265.68 315.42 -106.23 -0.0008 -68.72
C12HCl7O2(*) 271.65 286.58 -98.03 0.0013 -67.53
C12H8O(*) 116.72 414.53 -130.51 0.0002 -58.69
C12HCl7O(*) 287.66 297.33 -101.65 -0.0016 -69.77
C12H4Cl4O(*) 205.67 340.801 -111.71 0.0020 -64.76
C12H3Cl5O(*) 227.65 322.69 -107.12 -0.0007 -65.81
C12H2Cl6O(*) 249.68 304.66 -102.60 -0.0003 -66.49
C12H10(**) 109.83 425.51 -0.0010 0.0002 0
C12H9Cl(**)C12H 133.42 397.12 0.0011 0 -0.0002
8 Cl2(**) 156.99 368.67 0.0001 0 -0.0004
C12H7Cl3(**) 180.579 340.20 -0.0014 0.0005 0
C12H6Cl4(**) 204.170 311.75 0.0015 -0.00012 -0.0010
C12H5Cl5(**) 227.75 284.51 0.0010 -0.0003 0.0002
C12H4Cl6(**)C12 251.47 255.41 0 0 0
H3Cl7(**) 275.13 226.09 0 0 0
C12H2Cl8(**) 298.50 197.95 0.0004 0.00011 0
C12HCl9(**) 322.08 169.51 -0.0006 0.0002 0
C12Cl10(**) 345.66 141.06 -0.0032 0.0008 0

(*) gas
(**) liquid

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