l'-S Environment.il Protection A(J«MH:Y lmiiistri.il t nviiuiiMifMt.il Re-.i',itc h E PA~600/7~ 76~028
Office of Research dnd Development I ,it)or,itorv
ResiMn.h Tn.incile P.irk North C.ifol m.i ?//11 OCtObeT 1976
PCB EMISSIONS FROM
STATIONARY SOURCES:
A Theoretical Study
Interagency
Energy-Environment
Research and Development
Program Report
-------
RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S.
Environmental Protection Agency, have been grouped into seven series.
These seven broad categories were established to facilitate further
development and application of environmental technology. Elimination
of traditional grouping was consciously planned to foster technology
transfer and a maximum interface in related fields. The seven series
are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND DEVELOPMENT series. Reports in this series result from
the effort funded under the 17-agency Federal Energy/Environment
Research and Development Program. These studies relate to EPA's
mission to protect the public health and welfare from adverse effects
of pollutants associated with energy systems. The goal of the Program
is to assure the rapid development of domestic energy supplies in an
environmentally—compatible manner by providing the necessary
environmental data and control technology. Investigations include
analyses of the transport of energy-related pollutants and their health
and ecological effects; assessments of, and development of, control
technologies for energy systems; and integrated assessments of a wide
range of energy-related environmental issues.
REVIEW NOTICE
This report has been reviewed by the participating Federal
Agencies, and approved for publication. Approval does not
signify that the contents necessarily reflect the views and
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or commercial products constitute endorsement or recommen-
dation for use.
This document is available to the public through the National Technical
Information Service, Springfield, Virginia 22161.
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EPA-600/7-76-028
October 1976
PCB EMISSIONS
FROM STATIONARY SOURCES
A THEORETICAL STUDY
by
Herman Knieriem, Jr.
Monsanto Research Corporation
Dayton Laboratory
Dayton, Ohio 45407
Contract No. 68-02-1320, Task 26
Program Element No. EHE624A
EPA Task Officer: Robert E. Hall
Industrial Environmental Research Laboratory
Office of Energy, Minerals, and Industry
Research Triangle Park, NC 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
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CONTENTS
Tables iv
1. INTRODUCTION 1
2. CONCLUSIONS 3
3. RECOMMENDATIONS 5
4. THERMODYNAMIC CALCULATIONS 6
A. PCB Formation 6
B. PCB Destruction 9
5. KINETIC AND RELATED CONSIDERATIONS 10
A. The Fossil Fuels 11
B. The Combustion Conditions 12
C. "Unconventional" Fossil Fuel Combustion 15
D. PCB Contamination As An Emission Source 15
E. Environmental Persistence And Impact 15
References 20
Appendices
A. Reaction Thermodynamics, Formation 24
B. Reaction Thermodynamics, Oxidation 27
C. Biphenyl Thermodynamics 30
iii
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TABLES
Number Page
1 Estimated Benzo(a)Pyrene Emissions in
United States, 1972 10
A-l Reaction Thermodynamics, Formation 24
A-2 Reaction Thermodynamics, Formation 25
A-3 Reaction Thermodynamics, Formation 26
B-l Reaction Thermodynamics, Oxidation 27
B-2 Reaction Thermodynamics, Oxidation 28
B-3 Reaction Thermodynamics, Oxidation 29
C-l Biphenyl Thermodynamics 30
C-2 4-Chlorobiphenyl Thermodynamics 31
C-3 4,4-Dichlorobiphenyl Thermodynamics 32
C-4 2,2,4,4-Tetrachlorobenzene Thermodynamics 33
C-5 Hydrogen Chloride Thermodynamics 34
C-6 Chlorine Thermodynamics 35
C-7 Carbon Dioxide Thermodynamics 36
C-8 Water Thermodynamics 37
C-9 Oxygen Thermodynamics 38
iv
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SECTION 1
INTRODUCTION
A report1 prepared for EPA in 1975 tentatively identified the
presence of polychlorinated biphenyl (PCB) isomers in the stack
gas emissions from a pulverized coal-fired utility boiler.
Specifically, materials with gas chromatograph column retention
times comparable to tetrachloro- and hexachloro-biphenyl isomers
(and a commercial PCB standard having a similar degree of chlori-
nation) (personal communication from Dr. Mark Marcus, Midwest
Research Institute, 11 May 1976) were detected in bottom ash,
superheater ash and dust collector ash from the Number 8 unit of
the Tennessee Valley Authority plant at Widow's Creek, Alabama.
Levels detected ranged from 0.02 to 0.16 ppm (by weight of the
ash) and were too low for isolation and positive characterization
by the investigators.
Some PCB isomers tend to accumulate in the environment with an
impact potential not yet completely understood but of significant
concern.2 The indication, however tentative, that persistent
organics of this type may be found in the effluent streams from
fossil fuel fired boilers bears further study and investigation.
The present effort explores some of the theoretical aspects
affecting the likelihood that PCB emissions are possible from
stationary combustion sources firing conventional fossil fuels.
This evaluation considers:
A. Some thermodynamics for the formation and destruction of
PCB isomers for which data are available under controlled
conditions.
B. Some of the directional influences likely to affect reaction
kinetics of PCB formation and destruction in the firebox
(including fuel variables and furnace variables).
Cowherd, C., Jr., M. Marcus, C. M. Cuenther, and J. L.
Spigarelli. Hazardous Emission Characterization of Utility
Boilers. Contract No. 68-02-1324, Task No. 27, U.S. Environ-
mental Protection Agency, 23 June 1975. 185 pp.
2Interdepartment Task Force on PCBs. Polychlorinated Biphenyls
and the Environment. COM-72-10419, Washington, D.C., May 1972.
181 pp.
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C. Peripheral issues which bear on the conclusions and recom-
mendations including:
1. Potential PCB sources other than conventional fossil
fuel fired furnaces.
2. Potential sources of PCB contamination.
3. Variability of PCB biodegradation rate and consequent
environmental accumulation as a function of degree of
chlorination.
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SECTION 2
CONCLUSIONS
Thermodynamic analyses indicate that the reaction of some pre-
cursors to form polychlorinated biphenyls (PCBs) in conventional
fossil fuel fired sources is theoretically possible. The
presence of some precursors (biphenyl and reactive chlorine
species) has been deduced from the structure of known stack gas
effluent contaminants but has not been proven. There are com-
peting reactions within the furnace, uncertain time versus
temperature conditions, highly variable reactant concentrations
and other kinetic uncertainties in the combustion zone. Predic-
tions of the degree of certainty of PCB occurrence in furnace
effluents cannot be made from available data.
The best known reaction which may result in the formation of
PCBs in stationary combustion sources is that between biphenyl
and chlorine (or an active chlorine radical). Complex kinetics
within the reaction zone and lack of thermodynamic data prevent
useful consideration of other possible routes to PCBs at this
time (e.g., rearrangement and chlorination of PAH fragments).
Operating conditions most likely to contribute significant quan-
tities of PCB to the environment are tentatively judged to be
similar to those which maximize polynuclear aromatic hydrocarbon
(PAH) emissions if sufficient chlorine is present. This judgment
is drawn from structural similarities and coincident identifica-
tion of related materials in some combustion emissions.3'1*
While readily measurable aromatic hydrocarbon precursors for PCB
appear ubiquitous in fossil fuel combustion, the other reactant,
chlorine, has a widely variable content in fuels. It is very
low or nominally absent in some cases. Consequently, the likeli-
hood of significant PCB formation in efficiently operated natural
3Girling, G. W., and E. C. Ormerod. Variation in Concentration
of Some Constituents of Tar in Coke-Oven Gas. Benzole Pro-
ducers, Limited (London), Paper 1-1963, April 1963. 13 pp.
^Kubota, H., W. H. Griest, and M. R. Guerin. Determination of
Carcinogens in Tobacco Smoke and Coal-Derived Samples - Trace
Polynuclear Aromatic Hydrocarbons. CONF 750603-3/ Oak Ridge
National Laboratory, Oak Ridge, Tennessee. 9 pp.
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gas or refined oil fired furnaces may be much lower than from
those sources fired with residual oil and coal. Only field
measurements demonstrating the absence of organic chlorine in
the fuel can eliminate them as possible PCB sources, however.
It is possible that PCBs in furnace emissions, if proven, may
have originated from contamination by commercial PCBs either
before or after the combustion zone. PCBs have been shown to
be ubiquitous at very low levels in the environment.
Analyses of PCB contaminated tissue are reported extensively in
the literature and limited degradation studies are available.
Both types of study suggest that highly chlorinated PCB isomers
(four chlorines and higher) are much more likely to accumulate
environmentally with potential adverse impact than trichloro
(and lower) isomers.
One possible technique for reducing the potential for PCB emis-
sions may be the practice of efficient combustion techniques.
Efficient combustion is known to incinerate all organics effec-
tively.5 Reducing biphenyl survival in combustion will reduce
PCB likelihood in the emissions.
5Anonymous. Solving Waste Problem Profitably. Chemical Week,
104(24):38, 1969.
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SECTION 3
RECOMMENDATIONS
Available analysis of stack gas effluents from conventional
combustion sources has shown that hand-stoked and underfeed-
stoked coal furnaces are much more likely to produce polynuclear
aromatic hydrocarbon emissions than other types of coal feeds
(pulverized, spreader stoker, etc.). Rigorous characterization
of stack gas constituents of the former types deserves high
priority in assessing possible PCB output due to this recognized
PAH emissions characteristic.
Analysis of feed streams (air, fuel, auxiliaries), furnace
construction details, and sampling points will help to quantify
the role of commercial product contamination as a potential PCB
source in emissions from fossil fuel fired furnaces.
Unsupported estimates of reaction stoichiometry seem to favor a
low degree of chlorination of the PCB molecule. The thermal
stability of PCB increases with each additional chlorine,
however. The degree of chlorination of hypothetical PCB emis-
sions is very speculative therefore. Every effort should be
made to measure this distribution in the emission contaminants
which may be analyzed.
The relative environmental impact of PCBs as a function of
degree of chlorination needs further assessment and confirmation.
The environmental significance of possible PCB emissions from
fossil fuel combustion sources, if demonstrated, may be difficult
to assess without data relevant to their rate of survival and
accumulation in the environment.
The development and testing of techniques for tying up the
active chlorine moieties during combustion deserves serious
consideration. It may be feasible to develop washing techniques
to minimize chlorine content in gaseous and liquid fossil fuels.
Coal treatment probably will be more difficult because of diffu-
sion rate limitations of mass transfer in solids.
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SECTION 4
THERMODYNAMIC CALCULATIONS
A. PCB FORMATION
It is possible to write many reactions of fossil fuel components
or known combustion products to form polychlorinated biphenyls
(PCBs). In order to consider whether any such reactions may
take place, it is necessary to have data to evaluate but, for
the formation of polychlorinated biphenyls, little information
of this kind exists in the literature. What data are available
relates to carefully controlled, bench scale reactions of known
components to produce single isomers of known structure. The
reaction most often considered in such experiments is given
below (1). The likelihood that the reactants exist even briefly
in most fossil fuel fired sources is addressed starting in the
second paragraph below.
The reaction investigated is that between biphenyl and chlorine
to form PCB isomers plus HC1:
+ nClo —— KOVXO) + nHCl (1)
When operated on a large scale to produce commercial mixtures
of PCBs this reaction is induced catalytically by various metals
and metal salts.6 Temperatures within commercial reactors are
much lower (150°C or less) than those typically encountered
within a firebox for reasons of processing convenience.
Hot metal and metal salt surfaces which can be useful in PCB
formation are readily available as catalytic surfaces in fossil
fuel fired furnaces. They are present either as components of
the fuels themselves or the heat exchange surfaces within the
furnace or both. At the temperatures encountered, catalysis
may be unnecessary.
6Kirk-Othmer. Encyclopedia of Chemical Technology. 2nd Edition,
Vol. 5. Interscience Publishers, New York, NY, 1964. pp. 289
and following.
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Analysis of coal and oil components7 and the structures of
polynuclear aromatic hydrocarbons which have been positively
identified in the stack gases of combustion sources,8 testifies
to the transient presence, at least, of benzene in most furnaces
(including gas fired). The next step in the logic train con-
siders that the commercial production of biphenyl is" a relatively
straightforward thermal process using only benzene as a raw
material.9 Further, biphenyl is more stable thermally than
benzene10 and has been identified in combustion effluents.3'4
The possibility of the existence of biphenyl within the combus-
tion zone also seems acceptable, therefore.
Little work on chlorine in fossil fuels has been published in
this country because of low levels present in most domestic
fossil fuels.11'12'13 The literature cited does confirm chlo-
rine's presence in many fossil fuels.14 Further, there is ample
evidence for the presence of HCl (at low levels) in stack gas
7Kirk-Othmer. Op. Cit., Vol. 3. pp. 367 and following.
8Hangebrauck, R. P,, D. J. VonLehnden, and J. E. Meeker. Emis-
sions of Polynuclear Hydrocarbons and Other Pollutants from
Heat Generation and Incineration Processes. Journal of the
Air Pollution Control Association, 14:267-278, July 1964.
9Kirk-Othmer. Op. Cit., Vol. 7. pp. 191 and following.
1°Streitwieser, Andrew, Jr. Molecular Orbital Theory for Organic
Chemists. John Wiley and Sons, Inc., New York, NY, 1961.
pp. 271-243.
11Magee, E. M., H. J. Hall, and G. M. Varga, Jr. Potential
Pollutants in Fossil Fuels. NTIS No. PB 225039, Contract No.
68-02-0629, U.S. Environmental Protection Agency, June 1973.
292 pp.
12Smith, W. S., and C. W. Gruber. Atmospheric Emissions from
Coal Combustion - An Inventory Guide. PHS Publ. No. 999-AP-24,
NTIS No. PB 170851, U.S. Department of Health, Education, and
Welfare, April 1966. 112 pp.
13Gordon, G. E., et al. Study of Emissions from Major Air Pollu-
tion Sources and Their Atmospheric Interactions. Two-Year
Progress Report, RANN Program, NSF Grant No. GE-36338X, Nov 72-
Oct 74. 351 pp.
14Nelson, W., et al. Corrosion and Deposits in Coal- and Oil-
Fired Boilers and Gas Turbines. A Review by the ASME Research
Committee on Corrosion and Deposits from Combustion Gases,
1959. pp. 2-6, 13-31, 34, 38, 39, 113, 117-119.
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emissions.15 HC1 plus oxygen can form C12 at elevated tempera-
tures (450°C and up) via a modified Deacon process.16
Reactant existence and reaction conditions for Reaction 1 to take
place have not been proven. An untested rationale to postulate
at least their transient existence, however,- has been proposed.
The equilibrium thermodynamics of Reaction 1 were calculated by
S. R. Auvil of Monsanto Company for three PCB isomers over the
temperature range 50°C to 1500°C (private communication from
Dr. S. R. Auvil, Monsanto Co., St. Louis, Mo., May 24, 1976).
The results are tabulated in Appendix A, Tables A-l, A-2, and
A-3, and summarized below:
Reaction
to form
4-MCB
4,4' -DCB
2 , 2 ' , 4 , 4 • -TCB
Temperature
(°C)
50
1500
50
1500
50
1500
AF
(kcal/gmole)
-28.5
-27.8
-57.0
-55.5
-112.4
-109.5
Ln Kp
44.4
7.9
88.4
15.8
175.2
31.1
To quote from Auvil's discussion:
"... calculations show that the formation of the mono, di,
and tetra chlorinated biphenyls by the reaction path (of
Reaction 1) are very favored over the temperature range
50°C to 1500°C. Hence, if kinetic pathway exists and has
a finite rate under the constraints of the reaction zone,
these compounds would have a tendency to form.
"... the thermodynamic properties of 4-MCB and 2,2',4,4*-TCB
were estimated. It should be clear that even if the esti-
mated free energies for these compounds were in error by
±5 kcal/gmole, which is unlikely, the reactions are still
highly favored and the conclusion is unchanged."
15Piper, J. D., and H. Van Vliet. Effect of Temperature Varia-
tion on Composition, Fouling Tendency, and Corrosiveness of
Combustion Gas from a Pulverized-Fuel-Fired Steam Generator.
Transactions of the ASME, 80;1251-63, August 1958.
16Kirk-Othmer. Op. Cit., Vol. II- pp. 334-36.
8
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B.
PCB DESTRUCTION
Another reaction which bears consideration in assessing possible
PCB existence in effluent stack gases involves the destruction
of PCB if it were formed:
To quote the investigator, S. R. Auvil (private communication):
"The following is a summary of the free energies and
equilibrium constants at 50°C and 1500°C (taken from
Appendix B, Tables B-l, B-2, and B-3) for the combustion
of the mono, di, and tetra chlorinated biphenyls via
the above equation (2):
Combustion of
1 gram mole of
4-MCB
4,4' -DCB
2 , 2 ' , 4 , 4 ' -TCB
Temperature
<°C)
50
1500
50
1500
50
1500
AF
(kcal/gmole)
-1435.0
-1502.2
-1397.8
-1489.2
-1325.0
-1464.9
Ln Kp
2236.1
426.6
2178.1
423.0
2064.7
416.0
Clearly each reaction is extremely favored over the 50°C
to 1500°C temperature range and in a thermodynamically
controlled situation, the chlorinated biphenyls would
react to essentially 'extinction.'"
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SECTION 5
KINETIC AND RELATED CONSIDERATIONS
It has been shown in the thermodynamic calculation section that,
under the conditions existing in fossil fuel combustion systems
PCBs would have a tendency to form. Furthermore, once formed, it
has been shown that "in a thermodynamically controlled situation
the chlorinated biphenyls would react" essentially to extinction.
Another investigator17 of PCB reactions has said,
"... it should be pointed out that results obtained from
equilibrium calculations may not immediately be applicable
in practice because of kinetic conditions but can provide
tendencies of practical interest."
There are inadequate data available at present to address the
kinetic probability of PCB formation or destruction during com-
bustion in conventional fossil fuel fired sources. There are,
however, useful considerations to address in estimating those
sources and conditions which have the highest potential for
contributing PCB emissions which may have environmental impact.
These considerations include (among others):
A. The specific fossil fuels burned and possible
relationships between PCB and polynuclear aromatic
hydrocarbon (PAH) emissions.
B. The influence of combustion parameters.
C. An estimate of the relative PCB emissions from
fundamentally different kinds of stationary
combustion sources.
D. The possibility of PCB contamination of the combustion
system.
E. The likely environmental persistence and impact of
PCB molecules which may form.
17Karlsson, L., and E. Rosen. On the Thermal Destruction of
Polychlorinated Biphenyls (PCB). Some Equilibrium Considera-
tions. Stockholm, 1(2), 1971.
10
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A. THE FOSSIL FUELS
For PCBs to be formed during fossil fuel combustion one necessary
precondition assumed is the simultaneous presence of chlorine
and biphenyl.
Polynuclear aromatic hydrocarbons which may include biphenyl and
its precursors (see PCB/PAH discussion below) are readily formed
in the combustion of all types of fossil fuels during heat gene-
ration or incineration processes.14'8 They are more copiously
emitted from inefficient coal burning sources than those using
other fossil fuels (Table 1). See also PCB/PAH discussion below.
Chlorine, if detectable, is likely to be present only as chlori-
nated organics in natural gas, LPG, or refined oils. In coal
and residual oils, however, significant quantities of inorganic
chlorides may make a contribution to the availability of reac-
tive chlorine moieties. Corrosion analyses of furnaces firing
natural gas and refined oils imply that chlorine from occasional
traces of chlorinated organic content in fuel gases and refined
oils are at least an order of magnitude lower (or absent) than
the chlorine available from chlorides in much of the domestic
coals.11'12'18
Based on fuel constituents and corrosion analysis the likelihood
that chlorine compounds will be present in sufficient quantity in
the vapor phase to produce reactive chlorine moieties is judged
on the average to be higher with coal than all other conventional
fossil fuels.
1. PCB/PAH and Chlorine Distribution
There is a great deal of data in the literature on PAH emissions
from stationary and other combustion sources and almost none on
PCBs. The following discusses a possible relationship between
PCB and PAH emissions.
The generally accepted definition of polynuclear aromatic hydro-
carbons (PAH) includes those organic compounds in which at least
two aromatic rings share a pair of carbon atoms.19 Such rings
are said to be "fused." The first member and representative
compound of the PAH series so defined is naphthalene:
18Perry, J. H., et al. Chemical Engineers Handbook. 3rd
Edition. McGraw-Hill, New York, NY, 1962. pp. 1576-78.
19Morrison, R. T., and R. N. Boyd. Organic Chemistry. 3rd
Edition. Allyn and Bacon, Inc., Boston, MA, 1973. p. 967.
11
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Consideration of historic and present sources7'20 of benzene and
naphthalene suggests the initial presence and/or the concurrent
formation of both when fossil fuels are burned. Empirical
measurement of resonance energy10 and consideration of annella-
tion principles (primarily developed by E. Clar, University of
Glasgow) indicate greater thermal stability for benzene and
biphenyl than for naphthalene and related PAH. Indeed, biphenyl
has been identified in some combustion source emissions.3'^
Kirk-Othmer6 and others17 attest to the thermal stability of PCB
which exceeds that of chlorinated PAH compounds.21'22
There is no experimental evidence to test the issue of a rela-
tionship between PCB and PAH emissions. However, the known
correlation among PAH emission compounds,23 the likely presence
of related precursor intermediates, and the superior thermal
survival of PCB versus PAH suggests some correspondence. It may
be conjectured that chlorine availability limits the absolute
quantity of PCB formed but that PAH indicates the likelihood of
biphenyl formation and the subsequent possibility of PCB (where
there is chlorine available). If valid, this theory leads to
the projection that sources emitting high levels of PAH are
likely PCB emitters if chlorine is present in the fuel. This
projection can be tested.
The distribution of available chlorine on any organic compounds
surviving combustion may be a random statistical phenomenon.
Chlorine distribution may, however, be related to the thermal
stability of the compounds which would tend to skew statistical
projections. In any case, the degree of chlorination of possible
PCB emissions bears on their relative toxicity and their environ-
mental impact and is not a frivolous issue (see section E).
B. THE COMBUSTION CONDITIONS
Four of the combustion factors which influence both the creation
and destruction of both PCB and PAH are:
20Kirk-Othmer. Op. Cit., Vol. 13. pp. 670 and following.
21Hurd, C. D. Pyrolysis of Carbon Compounds. American Chemical
Society Monograph No. 50, 1929. pp. 143-44.
22Best, B. Great Lakes Carbon Corp., British 894,441,
September 16, 1960.
23Sawicki, E., et al. Polynuclear Aromatic Hydrocarbon Composi-
tion of the Atmosphere in Some Large American Cities.
Industrial Hygiene Association J., 23(2):137-144, 1962.
12
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1. Temperature maximums and temperature range distribution
within the combustion zone.
2. Residence time of the fuels and combustion products in
"active" temperature zones.
3. Mixing efficiency of fuel and air.
4. Particle size distribution of the fuel source introduced.
It is beyond the scope of this paper to exhaustively evaluate
each of these variables for the different fuels in various
stationary combustion sources. Study of selected papers24'25
from the extensive and exhaustive literature which reports on
these variables does allow postulation of useful approximations
of some furnace effects on stack gas emissions and PCB/PAH
structures.
1. Temperatures
Furnace temperatures, per se, are not separable from residence
time in their influence on either production or destruction of
PCB/PAH in conventional combustion sources through available
literature references. There have been reports of organic
chemical incinerators operating at high temperatures (about
3500°F) to ensure complete combustion of the organics.5 There
is no published data, however, which separates the impact of
flame temperature and other combustion parameters in the refer-
enced incinerator.
2. Residence Time
One of the clearest impacts of residence time on PAH formation
(and PCB by prior reasoning) is reported by Cuffe and Gerstle.
Their data indicate that the sudden "quenching" (temperature
drop) of the combustion stream in a cyclone boiler as it passes
rapidly from the cyclone burner into the convective transfer
area leads to high concentrations of PAH emissions (relative to
other steam boiler types). This occurs despite the very high
temperatures encountered in the cyclone area (Figure 1). By con-
trast, a horizontally opposed (HO) wet bottom furnace (Figure 2)
2l+Cuffe, S. T. , and R. W. Gerstle. Emissions from Coal-Fired
Power Plants: A Comprehensive Summary. PHS Publ. No. 999-
AP-35, U.S. Department of Health, Education, and Welfare,
1967. 26 pp.
25Perry, J. H. Op. Cit., pp. 1639-1643.
13
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yielded PAH emissions in line with dry bottom furnaces firing at
lower temperatures. Presumably, the slower rate of cooling and
relatively long residence time of the combustion gases in the
HO furnace (relative to the cyclone) account for the lower PAH
levels. Mixing efficiency and flame zone temperatures are com-
parable in the HO and cyclone furnaces.
3. Mixing Efficiency
The impact of this factor on PCB/PAH formation and destruction
is very significant. Data from Hangebrauck et al.,8 and EPA
(Table 1)* suggest that mixing as a variable in combustion
efficiency may be a major determinant in PAH and PCB emission.
These references contain data and estimates indicating that
hand- and underfeed-stoked coal fired residential warm air fur-
naces, open burning of coal refuse and residential wood burning
fireplaces are each at least an order of magnitude more severe
in emissions of PAH than all the coal fired steam generating
boilers in the United States combined. Of course, the three
severe emitter sources cited all represent broad spectra of flame
temperatures and combustion zone residence times. These worst
offenders have in common, however, the poor mixing of fuel and
air. This is also illustrated in Hangebrauck, et al.,8 data on
copious emissions from poorly regulated oil burners.
4. Particle Size Distribution
Obviously, this variable pertains only to liquid and solid fuels.
Due to rapid convective heat transfer within the droplets, par-
ticle size of liquid fuels is probably only of significance in
PCB/PAH generation when some other factor affecting combustion
efficiency (temperature, residence time, mixing) is out of
control. Poor particle size distribution in that circumstance
can aggravate already poor combustion conditions.
In the case of solid coal particles, the internal heat transfer
rate is relatively slow.26 In a worst case situation, incomplete
combustion of the central core of very large particles can be
envisioned. Thus, particle size can adversely influence other-
wise efficient combustion in pulverized coal (p.c.) furnaces.
Well regulated p.c. burning steam power generating facilities
rarely will be impacted by this factor though it has the poten-
tial to increase PCB/PAH emissions.
*While Table 1 reports benzo(a)pyrene emissions, Sawicki, et
al.23 have shown a correlation between this compound and total
PAH emissions.
26Green, N. W. Synthetic Fuels from Coal - The Garrett Process.
Clean Fuels from Coal Symposium II, Institute of Gas Technol-
ogy, Chicago, June 23-27, 1975. p. 301.
14
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C. "UNCONVENTIONAL" FOSSIL FUEL COMBUSTION
As has already been shown (Table 1), sources of hydrocarbon
emissions other than conventional fossil fuel fired combustion
sources have the potential to generate PAH and PCB. Open
burning of coal refuse may rank as the greatest non-furnace
source of these compounds followed closely by poorly regulated
coke production operations (the latter, strictly speaking, a
pyrolysis rather than combustion process). Even rubber tire
degradation in use has some major potential for PCB/PAH genera-
tion according to Table 1.
D. PCB CONTAMINATION AS AN EMISSION SOURCE
Finite levels of PCB amounting to parts per billion or more have
been detected literally world-wide from penguin eggs in the
Antarctic to anchovies from the Arctic circle.2 PCBs have been
used commercially in heat transfer fluids, hydraulics and lubri-
cants, transformer fluids, capacitors, plasticizers, industrial
solvents and other specialty applications. Additionally, they
have been tested in semi-commercial or developmental quantities
as cutting fluid additives, components of high temperature seal-
ants and high temperature pipe caulking. They have incidental
impact as infrequent components in waste oils used for dust
control on coal piles and temporary corrosion protection of
steel components in furnace construction.
Obviously, several of these uses could result in contamination
of a furnace interior or its fuel supply with PCBs. This possi-
bility could change the picture of PCB stack gas emissions from
one of creation and survival to survival, alone. If the contami-
nating source is in a relatively cool section of the combustion
source the PCB emission may be from continual evaporation of
product until the supply is exhausted. This is likely to be
only a short term phenomenon at worst.
Assessment of contamination as a source of PCB emission would
require rigorous furnace study and characterization of all input
streams (fuel, air, auxiliaries). The relative potential impact
of contamination versus in-situ generation as a PCB emission
source is unknown.
E. ENVIRONMENTAL PERSISTENCE AND IMPACT
There are a large number of references on this subject. Many
are summarized and useful general conclusions are offered on
both aspects (persistence and toxicity27) of the issue in the
27Peakall, D. B., and J. L. Lincer. Polychlorinated Biphenyls.
Bioscience, 20:958-64, Sept. 1970.
15
-------
report of the Interdepartmental Task Force on PCBs, "Polychlori-
nated Biphenyls and the Environment," May 1972. The Task Force
had representation from five Executive Branch departments of the
Federal Government including EPA.
Among their tentative conclusions were:
1. "[PCB] Acute oral LD50 in mammals varies from approximately
2-10 gm/Kg. (Apparent increase in mammalian toxicity with
decrease in chlorine content.)"
2. "The starting materials used in synthesis of PCBs determine
to a large degree the type of impurity or contaminant in
the commercial product. The contaminant variation, of
course, renders some divergence in the LD 50 values or
other toxicologic response of the PCBs. Fractionated
samples of some PCBs of foreign manufacture have shown
them to contain as contaminants the tetra- and penta-
chlorodibenzofurans, the hexa- and heptachloronaphthalenes.
In a report28 prepared specifically for presentation to the
Interdepartmental Task Force on PCBs, Munch presented data indi-
cating the possibility that PCB "homologs containing less than
four chlorine atoms may be degraded at rates approximately
thirty times those for the five and six chlorine homologs."
There is some chance, therefore, that PCB which may show up as
emissions from fossil fuel fired sources are more rapidly de-
graded in the environment than commercial PCB products. Section
A, p. 12, discusses the possibility that potential PCB isomers
in combustion stack gases have a low degree of chlorination.
28Papageorge, W. B., et al. Presentation to the Interdepart-
mental Task Force on PCBs. Washington, D.C., May 15, 1972.
69 pp.
16
-------
^•SAMPLING POINTS. A
, ELECTROSTATIC
/y PRECIPITATOR
SECONDARY SUPERHEATER
AND REHEAT HEADERS
COAL CRUSHERS
FLUE GAS TEMPERING DUCT
Figure 1. Boiler outline for cyclone type unit.24
17
-------
MECHANICAL DUST
COLLECTOR
STACK
SUPERHEAT.
OUTLET HEADER
SUPERHEATER
Figure 2. Boiler outline for horizontally-opposed firing unit.21*
18
-------
Table 1. ESTIMATED BENZO(a)PYRENE* EMISSIONS
IN UNITED STATES, 1972a
Emissions,
Source Type MT/yr
Stationary sources
Coal hand-stoked and underfeed-stoked
residual** furnaces 270
Coal, intermediate-size furnaces 6
Coal, steam power plants <1
Oil, residential through steam power type 2
Gas, residential through steam power type 2
Wood, home fireplaces 23
Enclosed incineration, apartment through
municipal type 3
Open burning, coal refuse 281
Open burning, vehicle disposal 5
Open burning, forest and agriculture 10
Open burning, other 9
Petroleum catalytic cracking 6
Coke production 0.05 to 153
Asphalt air-blowing <1
Mobile sources
Gasoline-powered, automobiles and trucks 10
Diesel-powered, trucks and buses <1
Rubber tire degradation 10
aFrom Preferred Standards Path Report for Polycyclic
Organic Matter. U.S. Environmental Protection Agency,
Office of Air Quality Planning and Standards, Durham,
N.C. October 1974. p. 27-36.
*See footnote on p. 14.
**Misprint - should read residential.
19
-------
REFERENCES
1. Cowherd, C., Jr., M. Marcus, C. M. Cuenther, and J. L.
Spigarelli. Hazardous Emission Characterization of Utility
Boilers. Contract No. 68-02-1324, Task No. 27, U.S.
Environmental Protection Agency, 23 June 1975. 185 pp.
2. Interdepartmental Task Force on PCBs. Polychlorinated
Biphenyls and the Environment. COM-72-10419, Washington,
B.C., May 1972. 181 pp.
3. Girling, G. W., and E. C. Ormerod. Variation in Concentra-
tion of Some Constituents of Tar in Coke-Oven Gas. Benzole
Producers, Limited (London), Paper 1-1963, April 1963.
13 pp.
4. Kubota, H., W. H. Griest, and M. R. Guerin. Determination
of Carcinogens in Tobacco Smoke and Coal-Derived Samples -
Trace Polynuclear Aromatic Hydrocarbons. CONF 750603-3,
Oak Ridge National Laboratory, Oak Ridge, Tennessee. 9 pp.
5. Anonymous. Solving Waste Problem Profitably- Chemical
Week, 104(24):38, 1969.
6. Kirk-Othmer. Encyclopedia of Chemical Technology. 2nd
Edition, Vol. 5. Interscience Publishers, New York, NY,
1964. pp. 289 and following.
7. Op. Cit., Vol. 3. pp. 367 and following.
8. Hangebrauck, R. P., D. J. VonLehnden, and J. E. Meeker.
Emissions of Polynuclear Hydrocarbons and Other Pollutants
from Heat Generation and Incineration Processes. Journal
of the Air Pollution Control Association, 14:267-278, July
1964.
9. Kirk-Othmer. Op. Cit., Vol. 7- pp. 191 and following.
10. Streitwieser, Andrew, Jr. Molecular Orbital Theory for
Organic Chemists. John Wiley and Sons, Inc., New York, NY,
1961. pp.241-243.
11. Magee, E. M., H. J. Hall, and G. M. Varga, Jr. Potential
Pollutants in Fossil Fuels. NTIS No. PB 225039, Contract
No. 68-02-0629, U.S. Environmental Protection Agency,
June 1973. 292 pp.
20
-------
12. Smith, W. S., and C. W. Gruber. Atmospheric Emissions from
Coal Combustion - An Inventory Guide. PHS Publ. No.
999-AP-24, NTIS No. PB 170851, U.S. Department of Health,
Education, and Welfare, April 1966. 112 pp.
13. Gordon, G. E., et al. Study of Emissions from Major Air
Pollution Sources and Their Atmospheric Interactions. Two-
Year Progress Report, RANN Program, NSF Grant No. GI-36338X,
Nov 72-Oct 74. 351 pp.
14. Nelson, W., et al. Corrosion and Deposits in Coal- and
Oil-Fired Boilers and Gas Turbines. A Review by the ASME
Research Committee on Corrosion and Deposits from Combustion
Gases, 1959. pp. 2-6, 13-31, 34, 38, 39, 113, 117-119.
15. Piper, J. D., and H. Van Vliet. Effect of Temperature
Variation on Composition, Fouling Tendency, and Corrosive-
ness of Combustion Gas from a Pulverized-Fuel-Fired Steam
Generator. Transactions of the ASME, 80:1251-63, August
1958.
16. Kirk-Othmer. Op. Cit., Vol. II. pp. 334-36.
17. Karlsson, L., and E. Rosen. On the Thermal Destruction of
Polychlorinated Biphenyls (PCB). Some Equilibrium Considera-
tions. Stockholm, 1(2), 1971.
18. Perry, J. H., et al. Chemical Engineers Handbook. 3rd
Edition. McGraw-Hill, New York, NY, 1962. pp. 1576-78.
19. Morrison, R. T., and R. N. Boyd. Organic Chemistry- 3rd
Edition. Allyn and Bacon, Inc., Boston, MA, 1973. p. 967.
20. Kirk-Othmer. Op. Cit., Vol. 13. pp. 670 and following.
21. Kurd, C. D. Pyrolysis of Carbon Compounds. American
Chemical Society Monograph No. 50, 1929. pp. 143-44.
22. Best, B. Great Lakes Carbon Corp., British 894,441,
September 16, 1960.
23. Sawicki, E., et al. Polynuclear Aromatic Hydrocarbon
Composition of the Atmosphere in Some Large American Cities.
Industrial Hygiene Association J., 23(2):137-144, 1962.
24. Cuffe, S. T., and R. W. Gerstle. Emissions from Coal-Fired
Power Plants: A Comprehensive Summary. PHS Publ. No.
999-AP-35, U.S. Department of Health, Education, and
Welfare, 1967. 26 pp.
25. Perry, J. H. Op. Cit., pp. 1639-1643.
21
-------
26. Green, N. W. Synthetic Fuels from Coal - The Garrett
Process. Clean Fuels from Coal Symposium II, Institute of
Gas Technology, Chicago, IL, June 23-27, 1975. p. 301.
27- Peakall, D. B., and J. L. Lincer. Polychlorinated
Biphenyls. Bioscience, 20:958-64, Sept. 1970.
28. Papageorge, W. B., et al. Presentation to the Interdepart-
mental Task Force on PCBs. Washington, D.C., May 15, 1972.
69 pp.
22
-------
APPENDICES
APPENDIX A. Reaction Thermodynamics, Formation
APPENDIX B. Reaction Thermodynamics, Oxidation
APPENDIX C. Thermodynamic Data to Support Information
Generated in Appendices A and B
23
-------
APPENDIX A
Table A-l. REACTION THERMODYNAMICS, FORMATION
COMPOUND
STOICHIOMETERIC COEFf
TEMHE.KATUKE
(C)
50.0
10U.O
IbO.O
200.0
^ 250.0
30U.O
350.0
100.0
150.0
500.0
550.0
600.0
650.0
700.0
750.0
800.0
850.0
9UO.O
950.0
1UOU.O
1U50.0
1100.0
1150.0
1200.0
1250.0
1300.0
1350.0
1100.0
1150.0
1500.0
1-CHLOROEIPHENYL
HYUKOGLN CHLORIDE
BIPHENYL
CHLURINE
DHR(T)
(KCAL/GMOLE)
-29.311
-29.198
-29.061
-28.910
-28.826
-2fa.720
-28.622
-28.531
-28.117
-28.370
-2B.299
-28.233
-28.172
-28.116
-28.065
-28.017
-27.973
-27.932
-27.891
-27.858
-27.625
-27.793
-27.761
-27.736
-27.710
-27.685
-27.661
-27.639
-Zf.klf
-2f.59f
nsR(T)
(CAL/GMOL/K)
-2.597
-2.175
-1.838
-1.561
-1.331
-1.138
-.971
-.B31
-.711
-.610
-.521
-.113
-.376
-.317
-.265
-.219
-.179
-.113
-.111
-.083
-.057
-.031
-.013
.006
.021
.010
.055
.069
.081
.093
1
1
-1
-1
DFR(T)
(KCAL/GMOLE)
-28.505
-28.386
-28.286
-28.201
-28.129
-28.068
-28.P15
-27.970
-27.931
-27.898
-27.870
-27.816
-27.825
-27.808
-27.791
-27.782
-27.772
-27.761
-27.757
-27.752
-27.719
-27.717
-27.716
-27.715
-27.716
-27.718
-27.750
-27.753
-27.757
-27.761
STATE
IOE.AL GAS
IDEAL GAS
IDEAL GAS
IDEAL GAS
Lhi K
11.119
38.307
33.661
30.011
P7.076
2 "4.660
22.639
20.923
19.150
18.170
17.019
16.059
15.178
11.390
13.679
13.036
12.151
11.917
11.127
10.977
10.561
10.175
9.817
9.181
9.173
8.802
8.609
8.353
8.112
7.881
Biphenyl + C12
4-MCB + HC1
DEFINITIONS
OHR, DSKt AND DFR = HEAT.
ENTROPYt AW FREE ENERGY
OF THE KEACTION. RESPECTIVELY.
DFR = DHR - T*DSR/100Q
LN K = DFR*1000/R/T
R = 1.98565 CAL/GMOLE/K
T = DEGKELS CELSIUS + 273.15
-------
Table A-2. REACTION THERMODYNAMICS, FORMATION
COMPOUND
STOICHIOMETERIC COEFF
TEMPEKATUKE
(C)
50,o
1UO.O
1511. 0
200.0
250.0
300.0
to 350.0
01 400.0
450.0
500.0
550.0
6UO.O
650.0
700.0
7&0.0
800.0
850.0
900.0
950.0
1000.0
1050.0
1100.0
1150.0
1200.0
1250.0
1300.0
1350.0
1400,0
1450.0
15UO.O
4.4-DICHLOROBIPHEMYL
HYDROGEN CHLORIDE
BIPHENYL
CHLORINE
DHR < T )
DSR(T)
(KCAL/GMOLE) (CAL/GMOL/K)
-5B.68U
-58.395
-58.127
-57.880
-t)7.6t>l
-57.439
-57.243
-57.062
-56.894
-56.740
-56.597
-56, 46fa
-56.344
-56.232
-56.129
-56.033
-5b.94b
-55.862
-5&.78S
-55,713
-55.646
-55.582
-55,522
-5b.46b
-55.410
-b5.3t>8
-55.309
-55.261
-55.216
-55.172
-5.194
-4.350
-3.675
-3.121
-2.661
-2.274
-1.946
-1.666
-1.426
-1.220
-1.041
-.886
-.751
-.633
-.529
-.438
-.357
-.285
-.221
-.163
-.111
-.064
-.021
.019
.055
.089
.120
.149
.175
.200
1
2
-1
-2
OFR(T)
(KCAL/GMOLE)
-57.010
-56.772
-56.572
-56.403
-36.258
-56.135
-56.030
-55.940
-55.863
-55.797
-55.740
-55.692
-55.651
-55.617
-55.588
-55.564
-55.544
-55.528
-55.515
-55.506
-55.499
-55.495
-55.493
-55.493
-55.494
-55.498
-55.503
-55.510
-55.516
-55.527
STATE
IDEAL GAS
IDEAL GAS
IDEAL GAs
IDEAL GAS
LU K
88.838
76.614
67.323
60.028
54.152
49.320
45.277
41.847
38.900
36.341
34.099
32.119
30.357
28.779
27.359
26.073
24.903
23.835
22.855
21.954
21.122
?0.351
19.635
IS.969
18.347
17.765
17.219
16.707
16.224
15.769
Biphenyl + 2C1
4, 4-DCB + 2HC1
DEFINITIONS .....
DHR, DSR. ftNn DFR = HEATi
ENTROPY. AND FREE ENERGY
OF THE REACTION, RESPECTIVELY.
DFR = 9HR - T*PSR/1000
L'M K = - DFR*1000/R/T
R = 1.98585 CAL/&MOLE/K
T = DLGRELS CELSIUS +• 273.15
-------
Table A-3. REACTION THERMODYNAMICS , FORMATION
COMPOUND
ST01CHIOI-ETERIC COEFF
TLMPEKATUKE
(C)
5U.O
1UO.O
15U.O
200.0
250.0
to 300.0
°* 350.0
400.0
450.0
500.0
55U.O
600.0
650. 0
700.0
750.0
800.0
850.0
900.0
950.0
100U.O
1050.0
1100.0
1150.0
1200.0
125U.O
1300.0
1350.0
1400.0
1450.0
1500.0
2,2,4,4-TETRA CB
HYDROGEN CHLORIDE
BIPHENYL
CHLORINE
DHR ( T )
(KCAL/GMULE)
-115,777
-115.190
-114.653
-114.157
-113.699
-113.275
-112.883
-112.521
-112.187
-111.878
-111.593
-111.331
-111.089
-110.865
-110.657
-110.465
-110.286
-110.119
-109.963
-109.815
-109.676
-109.544
-109.417
-109.296
-109.180
-109.068
-108.959
-108.854
-108.753
-108.654
DSR
-------
APPENDIX B
Table B-l. REACTION THERMODYNAMICS, OXIDATION
COMPOUND
STOICHIOMETERIC COEFF
TtMPLrtATUKE
(C)
50.0
100.0
150.0
2UU.U
250.0
a 3UU.O
^ 3bO.O
400.0
45Q.O
SOU. I)
5bO.O
600.0
6SO.O
700.0
750.0
800.0
BbO.O
900.0
950.0
1000. 0
1050.0
1100.0
1150.0
1200.0
I2b0.0
1300.0
I3t>0.0
140U.U
14bU.O
1500.0
CARbON DIOXIDE
HYDROGEM CHLORIDE
4-CHLORURIPHENYL
OXYGEN
DHR(T)
(KCAL/GMQLE)
-141/.96/
-1417.840
-1417.814
-1417.893
-1418.072
-14U..34U
-1418.687
-1119.101
-1119.571
-1420. 08b
-1120.636
-1121.213
-1421.810
-1422.420
-1423.036
-1423. 65b
-1424.272
-1424.883
-1425. 48fa
-1426.078
-1426.657
-1127.223
-1127.774
-1420.309
-142B.fli!6
-1429.332
-1429.821
-I't30.295
-1430.754
-1431.201
DSR(T)
(CAL/GMOL/K)
52.566
52,937
53.005
52.830
E2.472
51.983
51.103
50.765
f 0,093
49,105
18.715
48,034
47,370
46.727
46,109
15,518
44,956
44.424
43.921
43.446
43.000
42.580
42.186
"1.817
41.170
41.144
40.B39
40.551
40.280
40.025
12
4
1
-1
-11
OFR(T)
(KCAL/GMOLE.J
-1131.951
-1137.593
-1110.212
-1412.889
-1115.522
-1118.131
-1150.719
-1153.271
-1155.795
-1158.283
-1160.736
-1163.151
-1465.539
-1167.892
-1470.212
-1472.503
-1171.765
-1176.999
-1179.203
-1181.392
-1183.553
-1485.692
-11B7.811
-1189,911
-1191.993
-1191.058
-1496.108
-3498. 143
-1500.163
-1502.171
STATE
IDEAL GAS
IDEAL GAS
IDEAL GAs
IDF.AL GAS
IDE.AL GAS
4-MCB + 140.
12C0
2 + 4H20 + HC1
2236.080
1940.019
1733.937
1535.634
1391.101
1272.313
1172.315
1087.11*9
1013.737
893.606
8143.830
799.127
759.570
723.593
690. 95"*
661.209
633.987
608.980
585.927
561.609
544.834
526.442
509.292
193.262
178.246
161.149
150.891
438.398
126.
DEFINITIONS
OHR, HSR, AND OFR = HEATt
ENTROPY, AND FRFE ENERGY
UF THE REACTION, RESPECTIVELY.
OFR = OHR - T*OSR/1000
LN K = - OFR*1000/R/T
R = 1.96585 CAL/GMOLE/K
T = DECKELS CELSIUS * 273.15
-------
Table B-2. REACTION THERMODYNAMICS, OXIDATION
COMPOUND STOiCHIO^FTFRIC COEFF STATE
TLMPE.KATUKE
(C)
50.0
100.0
IbO.O
200.0
25U.O
» 300.0
350.0
100.0
450.0
500.0
550.0
600.0
650.0
700.0
TbO.O
800.0
850.0
900.0
9bO.O
1000. 0
1050. 0
1100. n
llbO.O
1200.0
1250.0
13CO.O
1350,0
1400.0
1450.0
1500.0
CARBON DIOXIDE
HYDKOGEN CHLOKIOE
WATER
4,4-OICHLORGBIPHENYl
OXYGEN
DHR(T)
DSR
-------
Table B-3. REACTION THERMODYNAMICS, OXIDATION
COMPOUNU
STOICHIOMETERIC COEFF
TLMPLKATUKE
(C)
50.0
100.0
IbU.O
200.0
to 250.0
to 300.0
350.0
400.0
450.0
50U.O
550.0
600.0
650.0
700.0
750.0
800.0
850.0
900.0
950. 0
1000. 0
lUbO.O
110U.O
ll&n.o
12UO.O
1.JSU.O
1300. C
13^0.0
14UC'.0
14bU.O
1500.0
CARBOfJ DIOXIDE
WATLR
HYURPGLN CHUORIDF
2,2.4,4-TETRA CB
OXYGEN
DHH (TJ
(KCAL/GKOLE)
-P580.851
-P5B1.161
-2b81.655
-2b«i:.330
-2583.170
-P584.155
-?be5.26U
-25P6.462
-2587.740
-2b«9.07fe
-?590.451
-?591.8b^
-?b94.26fe
-2594.683
-?5yb.oyi;
-2597.488
-?598.863
-?600.213
-2601.534
-?60k'.823
-2604.079
-2bOb.299
-2606. 463
-2607.631
-2fa()b.742
-?hJ'J.ttlfe
-P61U.855
-2611. 85y
-261i!.fl29
-2613.766
CSR(T)
(CrtL/GMOL/K)
3J3.742
212.655
?11.619
P10.115
208.429
?T6.633
204.787
202.932
201.101
199.315
197.591
195.939
194.364
192.870
191.458
190.126
1P8.073
107.697
166.594
IPS. 561
1P4.594
183.688
1P2.341
1P2.P49
1P1.307
lfO.613
179.963
179.353
178.762
178.246
24
2
a
-2
-25
OFR(T)
(KCAL/GMOLE)
-P649.922
-2660.588
-2671.201
-26B1.746
-2692.210
-2702.587
-2712.872
-2723.065
-2733.166
-2743.176
-2753.098
-2762.936
-2772.694
-27B2.374
-2791.982
-P801.521
-2610.996
-2820.410
-2829.767
-2839.071
-2848.324
-2857.531
-2866.694
-2875.816
-28B4.900
-£893.947
-2902.962
-2911.945
-2920.898
-2929.823
STATE:
IDtAL GAS
IDEAL GAS
IUE.AL GAS
IDtAL GAS
IDEAL GAS
LM K
4129.357
3590.1*1+1
3173.319
2854.121
2591.411
2374.460
2192.251
2037.OM1
1903.230
1786.66b
1684.210
1593.440
1512.457
1439.757
1374.127
1314.580
1260.306
1210.632
1164.996
1122.923
1064.012
1047.916
1014.342
9B3.032
953.765
9?6.348
900.609
876.399
853.58b
832.050
2 2,2',4,^-TCB + 250,
24C0
+ 8HC1
DEFINITIONS
OHF. , OSR. AND DFR = HEAT,
ENTROPY. AMD FREE ENERGY
OF THE REACTION, RESPECT IVFLY.
OFR = DHR - T*DSR/1000
LN K = - DFR*1000/R/T
R = 1.9B5B5 CAL/GMOLE/K
T = DEGREES CELSIUS + 273.15
-------
APPENDIX C
Table C-l. BIPHENYL THERMODYNAMICS
BIPHENYL
( IDEAL GAS ) MOLECULAR WT. 1^4.200
TEMPERATUKE
(C)
50.0
100.0
150.0
200.0
250.0
300.0
350.0
•400.0
450.0
500.0
550.0
600.0
f ^s
o 650.0
700.0
750.0
600.0
850.0
900.0
950.0
1000.0
1050.0
1100.0
1150.0
1200.0
1250.0
1300.0
1350.0
moo.o
1450.0
1500.0
CP
(CAL/RMOL/K)
42.528
49.506
55.796
61. 465
66.576
71.182
75.334
79.077
8?. 451
85.492
88.233
90.704
92.931
94.939
96.748
98.379
99.850
101.175
102.370
103.446
104.417
105.292
106.081
106.792
107.432
lOf.010
108.531
109. COO
109.423
109.8014
H-H<25 C)
(KCAL/GMOLE )
l.Olf
3.320
5.956
8.890
12.093
15.539
19.203
23.065
27. 1C?
31.305
35.649
40.1?4
44.715
49.413
54.206
59.085
64.041
69.067
74.157
79.302
84.499
89.743
95.027
100.3it9
105.705
111.092
116.505
121.944
127.405
132. 865
S-S
-------
Table C-2. 4-CHLOROBIPHENYL THERMODYNAMICS
4-CHLOROBIPHENYL
( IDEAL GAs )
MOLECULAR WT. 188.661
TEMPERATUKE
(C)
50.0
100.0
150.0
200.0
250.0
300.0
350.0
400.0
450.0
500.0
550.0
600.0
650.0
700.0
JS 750.0
800.0
850.0
900.0
950.0
1000.0
1050.0
1100.0
1150.0
1200.0
1250.0
1300.0
1350.0
1400.0
1450.0
1500.0
CP
(CAL/GMOL/K)
46.858
53.736
59.907
65.444
70.413
74.871
78.872
82.461
85.682
88.571
91.164
93.491
95.579
97.452
99.133
100.641
101.994
103.208
104.297
105.275
106.152
106.939
107.645
108.279
108.848
109.358
109. «15
110.226
110.595
11C. 925
H-H<25 C)
(KCAL/GvOLE)
1.125
3.643
6.487
9.623
13.022
16.656
20.501
24.536
28.741
33.099
37.594
42.211
46.939
51.765
56.681
61.676
66.742
71.873
77.061
82.301
87.587
92.914
98.279
103.678
109.106
114.562
120.041
125.542
131.063
136.601
S-S(25 C)
< CAL/GMOL/K)
3.622
10.855
17.999
24.999
31.623
38.454
44.885
51.111
57.135
62.961
68.593
74.038
79.303
84.394
89.319
94.086
96.700
103.169
107.499
111.698
115.770
119.722
123.560
127.288
130.912
13H.436
137.865
141.203
144.454
147.622
DHF(T)
(KCAL/GMOLE)
35.761
35.032
34.39?
33.833
33.350
32.934
32.579
32.279
32.028
31.823
31.656
31.531
31.438
31.377
31.344
31.337
31.352
31.387
31.438
31.501
31.573
31.648
31.722
31.790
31.844
31.878
31.885
31.856
31.783
31.655
DSF(T)
(CAL/GMOL/K)
-85.084
-37.185
-88.798
-90.047
-91.020
-91.780
-92.375
-92.839
-93.198
-93.473
-93.680
-93.830
-93.933
-93.998
-94.031
-94.028
-94.0?4
-93.994
-93.952
-93.901
-93.846
-93.790
-93.737
-93.690
-93.654
-93.632
-93.627
-93.645
-93.668
-93.761
nFF3.«56
1PB.538
193.221
107.907
LN K
-98.572
-91.179
-85.643
-81.353
-77.935
-75.152
•72.843
•70.897
•69.234
•67.796
•66.541
•65.434
•64.450
•63.570
•62.777
•62.059
•61.404
-60.804
-60.253
•59.744
•59.273
•58.835
•58.427
•58.045
•57,688
•57.354
-57.039
•56.744
•56.466
•56.204
DEFINITIONS
CP = HEAT CAPACITY AT CONSTANT PRESSURE. H = F.NTHALPY, S = FNTROPY,
AND DHF, DSF. AND OFF ARE THE HEAT. ENTROPY. AND FREE ENEROY OF FORMATION, prsPECTIVFLY.
OFF = DHF - T*DSF/1000 AND LM K = - QFr*10nO/R/T, WHERE
R = 1.98585 CAL/GMOLE/K ... AND ... T = DEGREES CELSIUS + 373.15
-------
Table C-3. 4,4-DICHLOROBIPHENYL THERMODYNAMICS
4,4-OICHLOROBIPIIEMYL ( IDEAL GAS ) MOLECULAR WT. 2P3.110
TEMPERATURE
(C)
5C.O
100,0
150.0
200.0
250.C
300.0
35C.O
i+OO.O
450.0
500.0
550.0
600.0
650.0
co 700.0
INS 750.0
800.0
850.0
900.0
950.0
1000.0
1050.0
1100.0
1150.0
1200.0
1250.0
1300.0
1350.0
140C.O
1450.0
1500.0
CP
(CAL/GMOL/K)
51.188
57.968
64.021
69.426
74.25?
78.561
82.408
85.843
88.910
91.649
94.094
96.277
98.226
99.966
101.520
102.908
104.146
105.252
106.240
107.122
107,909
108.612
109.239
109.800
110.300
110.747
111.146
111.502
111 .820
112.104
H-H(25 C)
(KCAL/GMOLE)
1.234
3.966
7.019
10.357
13.952
17.774
21.800
26.008
30.378
34.894
39.538
44.299
49.162
54.118
59.156
64.267
69.444
74.679
79.967
85.302
90.678
96.091
101.538
107.014
112.517
118.043
123.590
129.157
134.740
140.338
S-S
-------
Table C-4. 2,2,4,4-TETRACHLOROBENZENE THERMODYNAMICS
2,2,4t4-TETRA CB
( IDEAL GAS ) MOLECULAR WT. 292.00%
TEMPERATURE
(0
50.0
100.0
150.0
200.0
250.0
300.0
350.0
400.0
450.0
500,0
550.0
600.0
650.0
700.0
750.0
800.0
850.0
900.0
950.0
1000.0
1050.0
1100.0
1150.0
1200.0
1250.0
1300.0
1350.0
1400.0
1450.0
1500.0
CP
(CAL/GMOL/K)
59.851
66.442
72.261
77.399
81.936
85.942
89.479
92.602
95.360
97.795
99.945
101.843
103.519
104.999
106.306
107.460
108.479
109.378
110.172
110.874
111.493
112.040
112.523
112.949
113.325
113.658
113.951
114.210
114.439
114.641
H-H(25 C)
(KCAL/GWOLE)
1.452
4.612
8.083
11.827
15.813
20.012
24.399
28.953
33.653
38.4R3
43.428
48.474
53.609
58.822
64.106
69.450
74.849
80.296
85.786
91.312
96.872
102.460
108.074
113.711
119.368
125.043
130.734
136.438
142.154
147. 8P1
S-S<25 C)
(CAL/GMOL/K)
4.673
13.756
22.477
30.835
3d. 839
46.502
53.839
60.866
67.601
74.058
80.255
86.205
91,923
97.423
102.717
107.817
112.734
117.479
122.061
l?fa.489
130.772
134.918
13fl,934
142.827
146.603
150.269
153.830
157.291
160.657
163.934
PHFm
(KCAL/GMOIC)
15.561
15.37?
15.248
IS. 181
15.162
15.185
15.243
15.330
15.442
15.575
15.726
15.893
16.075
16.268
16.472
16.685
16.906
17.133
17.363
17.594
17.824
18.048
18.263
18.464
IP. 645
18.801
18.924
19.008
19.043
19.021
Dsrm
(CAL/GMOL/K)
-99.932
-100.476
-100.790
-1 00.942
-100.980
-100.938
-100.842
-100.708
-100.547
-100.370
-100. IPO
-99.9f>3
-99.762
-99.578
-99.373
-99.170
-98.969
-98.771
-98.579
-96.394
-98.217
-9B.051
-97.897
-97.758
-97.637
-97.536
-97.459
-97.408
-97.387
-97.400
nFF(T)
(KCftL/GMf)LF)
U7.854
^2.f.*5
•S7.FJ97
A?. 941
^7.990
73.03P
76.0*3
«3.122
f-fi.153
<53. I7fe
9P.190
ln3.194
me.iee
113.172
IIP. 14ft
1P3.109
1PP.063
1 -*3.n06
1?7.940
m2.f-.64
147. 7PO
1=12.686
1S7.585
ic.2.476
167.361
172.240
177.115
181.987
1P6.856
1^1.726
LN K
-74.570
-71.341
-68.900
-65.4U4
-64.170
-63.098
-6?. 181
-61.385
-60.687
-60.068
-59.514
-59.015
-58.148
-57,768
-57.1*17
-57.092
-56.789
-56.506
-56,242
-55.993
-55.759
-55.539
-55.331
-55.134
-b4.948
-54.772
-54.606
-54.449
DEFINITIONS
CP = HEAT CAPACITY AT CONSTANT PRESSURE. H = FMTHALPY, S = ENTROPY,
AMD DHFi OSF, ANO OFF ARE THE HEAT. ENTROPY. AMD FREE ENERGY OF FORMATION, RESPECTIVELY.
OFF = DHF - T*DSF/1000 AND LN K = - DFF*1000/R/T, hHEKE
R = 1.98585 CAL/GMOLE/K ... AND ... T = DEGREES CELSIUS + 373.15
-------
Table C-5. HYDROGEN CHLORIDE THERMODYNAMICS
HYDROGEN CHLORIDE ( IOEAL GAS ) MOLECULAR WT. 36.490
TLMPERATUKE
(C)
50.0
100.0
150.0
200.0
250.0
300.0
350.0
400.0
450.0
500.0
550.0
600.0
650.0
70C.O
750.0
800.0
850.0
900.0
950.0
1000.0
1050.0
1100.0
1150.0
1200.0
1250.0
1300.0
1350.0
1100.0
i<+50.n
1500.0
CP
(CAL/GMOL/K)
6.957
6. 946
6.957
6.982
7.016
7.058
7.105
7.156
7.210
7.267
7.327
7.387
7. 449
7.512
7.575
7.639
7.702
7.765
7.827
7.888
7.948
8.006
£.063
B.117
8.169
8.218
E.264
8.308
6.348
8.384
H-H(25 C)
(KCAL/GMOLE)
.174
.522
.869
1.218
1.567
1.919
2.273
2.630
2.9B9
3.351
3.716
4.084
4.454
4.829
5.206
5.586
5.970
6.356
6.746
7.139
7.535
7.934
8.335
8.740
9.147
9.557
9.9&9
10.383
10.800
11.21*
S-S<25 C)
(CAL/GMOL/K)
.561
1.561
.2.435
3.213
3.916
4.558
5.150
5.701
6.215
6.699
7.156
7.59D
8.003
8.398
&. 776
9.139
9.480
9.825
10.150
10.465
10.770
11.066
11.353
11.633
11.904
12.169
lii.427
12.678
12.924
13.163
DHF(T)
(KCAL/GMOlE)
-22.077
-22.111
-22.14T
-22.188
-22.229
-22.P69
-22.309
-2?. 347
-22.384
-22.420
-22.454
-22.487
-22.518
-22. ^46
-22.574
-22.599
-22.623
-22.644
-22.665
-22.683
-22.701
-22.717
-22.731
-22.745
-22.757
-22.768
-22.779
-22.789
-22.799
-22.f-.08
DSF(T)
(CflL/GMOL/K)
2.352
2.256
2.161
2.072
1.991
1.918
1.851
1.792
1.738
1.690
1.64Q
1.609
1.575
1.545
1.517
1.493
1.472
1.453
1.436
1.421
1.407
1.396
1.385
1.376
1.368
1.360
1.3?4
1.347
1.342
1.337
HFF(T)
(KCftL/GMOLF)
-52.837
-92.953
-93.063
-93.169
-33.270
-93.^68
-93.462
-S3. 553
-P*.641
-23.727
-93.811
-P3.892
-33.972
-P4.050
-24,126
-P4.201
-P4.276
-P4.349
-24.421
-94.492
-94.563
-P4.633
-94.7P2
-P4.772
-P4.840
-94.908
-94.976
-P5.044
-95.111
-P5.178
LN K
35.587
30.974
27.446
24.658
22.399
20.531
18.960
17.619
16.463
15.454
14.566
13.779
13.076
12.445
11.874
11.356
10.«84
10.451
10.054
9.687
9.348
9.033
8.741
8.468
8.212
7.973
7.749
7.537
7.338
7.150
DEFINITIONS CP = HEAT CAPACITY AT CONSTANT PRESSURE. H = FNTHALPY. S = ENTROPY,
AND DHF, DSF. AMP OFF ARE THE HfAT« FmROPY, AMD FREE ENERGY OF FORMATION, PFsPECTlVELY.
DFF = DHF - T*DSF/1000 AND LN K = - DFF*1000/R/Tt *HERE
R = 1.98585 CAL/GMOLE/K ... AMD ... T = DEGREES CELSIUS + 973.15
-------
Table C-6. CHLORINE THERMODYNAMICS
CHLORINE
( IDEAL GAS )
MOLECULAR WT. 70.910
TEMPERATUNE
(C)
50.0'
100.0
150.0
ann.o
850.0
300.0
350-.0
400.0"
150.0
500»0
550.0
600.0
700.0
750.0*
800.0
650.0
900.0
950vO
1000.0
1050,'Q
1100.0
115C.O
1200.0
1250.0
1300.0
1350.0
1400.0
1450.0
1500.0
CP
(CAL/GMOL/K )
I .216
P. 378
C.495
fv.'5B4
P. 653
fi.710
P. 757
8.7^7
6.B32
t . 862
8.PR8
6.912
8.932
f .951
6.967
e.9B2
P. 996
9.008
9.019
9.C29
9.039
9.047
9.056
9.064
9.071
9.079
9.086
9.094
9.101
9.109
H-H<25 C)
(KCAL/GMOLE)
.204
.619
1.041
1.468
1.699
2.333
2.770
3'. 209
3.650
4.092
4.536
4.981
5.427
5.874
6.322
6.771
7.2PO
7.670
8.1?1
8.572
9.024
9.476
9.9?9
10.382
10.835
11.289
11.743
12.197
12.652
13.107
S-S(?5 C)
(CAL/GMOL/K)
.657
1.851
2.912
3.86*
4.732
5.525
6.255
6.933
7.564
8.156
8.712
y.237
9.733
10.205
10.654
11.082
11.492
11.684
12.260
12.621
12.969
13.305
13.629
13.941
14.244
14.537
14.621
15.097
15.365
15.635
OHF(T)
(KCAL/GMOLD
0.000
o.noo
0.000
0.000
0.000
0.000
o.coo
0.000
0.000
0.000
0.000
0.000
0.000
0.000
O.noo
0.000
0.000
0.000
0.000
0.000
0.000
o.ooo
o.nuo
o.ono
0.000
o.oco
0.000
0.000
0.000
0.000
DSF(T)
(CAL/GMOL/K)
0.000
0.000
0.000
0.000
0.000
0.000
o.cno
0.000
O.OCO
o.nuo
0.000
0.000
0.000
0.000
o.ocu
0.000
o.noo
o.ono
0.000
o.oco
o.ono
0.000
O.ono
0.000
0.000
0.000
0.000
0.000
O.POO
0.000
OFF(T)
(KCftL/GMOLE)
o.nno
0.000
o.ono
n.onc
O.OPO
o.rno
o.noo
o.ono
o.oro
o.nno
0.000
o.oco
O.noo
0.000
o.ooo
0.000
o.ono
o.oco
P. 000
o.oco
o.ono
0.000
o.ooo
0.000
o.ooc
o.oco
o.ono
o.noo
o.ooo
o.ooo
LN K
o.noo
o.noo
o.oco
o.ooo
o.ooo
0.000
0.000
o.ooo
0.000
0.000
o.ono
0.000
0.000
0.000
o.ooo
0.000
0.000
0.000
o.ooo
0.000
0.000
0.000
o.oco
0.000
0.000
0.000
o.noo
Q.OOO
0.000
o.ooo
DEFINITIONS
CP = HEAT CAPACITY AT CONSTANT PRESSURE. H = FijTHALPY, S = ENTROPY.
AND DHFi DSF. AMD OFF ARE THE HEAT. ENTROPY, AMD FKF!E ENERGY OF F03MATIOM RESPECTIVELY.
OFF = DHF - T*DSF/1000 ANP Lf-' K = - DFF*inOO/R/T ,
R = 1.98585 CAL/GMOLE/K ... AND ... T = OEtREES CELSIUS
?73.15
-------
Table C-7. CARBON DIOXIDE THERMODYNAMICS
CARBON DIOXIDE
( IDEAL GAS )
MOLECULAR WT. 44.010
TEMPERATURE
(C)
50.0
100.0
150.0
200.0
250.0
300.0
350.0
1*00.0
450.0
500.0
550.0
600.0
650.0
700.0
co 750.0
°> 800.0
850.0
900.0
950.0
1000.0
1050.0
1100.0
1150.0
120C.O
1250.0
1300.0
1350.0
1400.0
1150.0
1500.0
CP
(CAL/GMOL/K)
9.150
9.643
1C. 078
10.468
10.822
11.144
11.439
11.708
11.955
12.181
12.388
12.576
12.749
12.906
13.049
13.180
13.300
13.409
13.510
13.603
13.689
13.770
13.846
13.920
13.991
14.062
14.133
14.205
14.280
14.359
H-H<25 C)
(KCAL/GMOLE)
.225
.695
1.189
1.703
2.235
2.784
3.349
3.928
4.519
5.123
5.737
6.361
6.995
7.636
8.265
8.941
9.603
10.270
10.943
11.621
12.304
12.990
13.681
14.375
15.072
15.774
16.479
17.187
17.899
18.615
S-S(25 C)
(CAL/GMOL/K)
.726
2.076
3.317
4.465
5.534
6.537
7.481
8.374
9.222
50.029
10.799
11.535
12.240
12.917
13.567
14.193
14.796
15.377
15.939
16.48?
17.008
17.517
18.011
16.490
16.956
19.409
19.850
20.280
20.699
21.109
DHF(T)
(KCAL/GMOl E)
-94.058
-94.066
-94.074
-94.085
-94.098
-94.115
-94.134
-94.155
-94.178
-94.202
-94.228
-94.254
-94.2B1
-94.307
-94.333
-94.359
-94.385
-94.409
-94.433
-94.457
-94.480
-94.502
-94.525
-94.548
-94.571
-94.596
-94.622
-94.650
-94.681
-94.716
DSF(T)
(CAL/GMOL/K)
.694
.673
.652
.628
.601
.571
.539
.506
.473
.441
.409
.378
.348
.320
.294
.269
.246
.225
.205
.186
.168
.151
.135
.119
.104
.088
.072
.054
.036
.016
HFF
-------
Table C-8. WATER THERMODYNAMICS
WATER
( IDEAL GAS )
MOLECULAR WT. 18.020
TEMPERATUKE
(C)
50.0
100.0
150.0
200.0
250.0
300.0
350.0
400.0
450.0
500.0
550.0
600.0
650.0
700.0
^ 750.0
800.0
850.0
900.0
950.0
1000.0
1050.0
1100.0
1150.0
1200.0
1250.0
1300.0
1350.0
1400.0
1450.0
1500.0
CP
(CAL/GMOL/K)
8.055
8.136
8.236
8.349
8.472
8.601
8.737
8.877
9.021
9.168
9.317
9.467
9.618
9.770
9.921
10.071
10.219
10.365
10.509
10.649
10.786
10.919
11.047
11.169
11.286
11.396
11.500
11.596
11.684
11.764
H-H(25 C)
(KCAL/GVOLE)
.201
.606
1.015
1.430
1.850
2.277
2.710
3.151
3.598
4.053
4.515
4.984
5.462
5.946
6.439
6.938
7.446
7.960
8.482
9.011
9.547
10.090
10.639
11.194
11.756
12.323
12.895
13.473
14.055
14.641
S-SC25 C)
(CAL/GMOL/K)
.647
1.812
2.841
3.767
4.611
5.390
6.115
6.795
7.436
8.044
8.623
9.177
9.708
10.220
10.713
11.190
11.65?
la.ioo
12.536
12.960
13.372
13.775
14.168
14.551
14.926
15.292
15.651
lb.001
16.344
16.679
DHF(T)
(KCAL/GMOLE)
-57.858
-57.977
-58.096
-58.213
-58.328
-58.440
-58.549
-58.654
-58.756
-58.854
-58.947
-59.037
-59.122
-59.203
-59.280
-59.352
-59.421
-59.485
-59.546
-59.603
-59.657
-59.706
-59.755
-59.800
-59.843
-59.884
-59.923
-59.961
-59.999
-60.036
OSF(T)
-------
Table C-9. OXYGEN THERMODYNAMICS
OXYGEN
( IDEAL fi»S ) MOLECULAR WT. 32.000
TEMPERATUKE
(C)
50.0
100.0
150.0
200.0
250.0
300.0
350.0
400.0
450.0
500.0
550.0
600.0
650.0
700.0
fA _
oo 750.0
800.0
850.0
900.0
950.0
1000.0
1050.0
1100.0
1150.0
1200.0
1250.0
1300.0
1350.0
1400.0
1450.0
1500.0
CP
(CAL/GMOL/K)
7.048
7.136
7.248
7.369
7.490
7.609
7.721
7.827
7.925
8.016
8.099
8.175
8.244
8.306
8.363
8.415
8.462
8.506
8.546
8.583
8.619
8.653
8.6S7
8.721
8.757
8.794
8.833
8.876
8.922
8.973
H-H(25 C)
(KCAL/GMOLE)
.176
.530
.890
1.255
1.627
2.004
2.387
2.776
3.170
3.569
3.971
4.378
4.789
5.203
5.619
6.039
6.461
6.885
7.311
7.740
8.170
8.601
9.035
9.470
9.907
10.346
10.786
11.229
11.674
12.121
S-S(25 C)
(CAL/GMOL/K)
.566
1.586
2.490
3.306
4.052
4.741
5.383
5.983
6.547
7.080
7.585
8.064
8.522
8.958
9.376
9.776
10.160
10.530
10.886
11.229
11.560
11.880
12.191
12.491
12.783
13.066
13.34?
13.611
13.873
14.128
DHF(T)
(KCAL/GMOLE)
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
DSF(T)
(CAL/GMOL/K)
0.000
0.000
0.000
0.000
0.000
o.oco
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
c.ooo
o.ono
0.000
0.000
OFF(T)
0,000
o.ono
o.ooo
0.000
0.000
0.000
0.000
c.uoo
o.coc
0.000
0.000
0.000
0.000
0.000
c.ono
0.000
0.000
c.ooo
0.000
o.ono
o.ono
o.ooc
o.ono
o.ono
0.000
o.coo
0.000
0.000
o.ono
o.ooo
LN K
o.noo
o.ooo
0.000
0.000
0.000
n.ooo
o.ooo
o.ooo
0.000
0.000
o.ooo
o.ooo
0.000
o.ooo
o.ooo
0.000
o.noo
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
o.ooo
o.ooo
o.noo
0.000
DEFINITIONS CP = HEAT CAPACITY AT CONSTANT PRESSUREi H = FNTIIALPY. S = ENTROPY,
AND DHFt DSF. AND OFF ARE THE HEATt ENTROPYi AND FREE ENERGY OF FORMATION. RESPECTIVELY•
OFF = DHF - T*DSF/1000 AND
R = 1.98585 CAl/GMOLE/K ,
LN K = - DFF*1000/R/T, WHERE
>. ANP ... T = DEGREES CELSIUS ••• 973.15
-------
TECHNICAL REPORT DATA
(Please read lusirucnons on the reverse before completing)
\. REPORT NO.
EPA-600/7-76-028
2.
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
PCB Emissions from Stationary Sources: A
Theoretical Study
5. REPORT DATE
October 1976
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Herman Knieriem, Jr.
8. PERFORMING ORGANIZATION REPORT NO.
MRC-DA-577
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Monsanto Research Corporation
Dayton Laboratory
Dayton, Ohio 45407
10. PROGRAM ELEMENT NO.
EHE624A
11. CONTRACT/GRANT NO.
68-02-1320, Task 26
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final; 3-6/76
14. SPONSORING AGENCY CODE
EPA-ORD
15. SUPPLEMENTARY NOTES JJERL-RTP task officer for this
Ext 2477, Mail Drop 65.
report is R.E. Hall, 919/549-8411
is. ABSTRACT The report gives results of a theoretical assessment of polycnlorinatea bi-
phenyl (PCB) formation and destruction in conventional fossil fuel fired sources.
Results suggest a small but finite possibility that PCB isomers may be found in their
emissions. The study was the result of concern caused by tentative identification of
PCB isomers in ash and flyash from a utility steam generating boiler. The theoret-
ical assessment concluded that: (1) PCB emissions are more likely from higher-
chlorine content coal or residual oil combustion than from refined oil or natural gas;
(2) PCB isomers with four or more chlorine atoms per molecule are more of an
environmental hazard than those with three or less; (3) the probability of forming PCB
isomers with four or more atoms of chlorine per molecule during combustion is
restricted by the short residence times and low concentrations of chlorine available
in many fossil fuels; (4) the amount of PCB emissions, if any, may be related to poly-
nuclear aromatic hydrocarbon emissions; (5) based on the above, inefficient combus-
tion control is more likely to produce PCB emissions than optimum conditions; and
(6) the highest priority for field sampling and analysis of PCB from combustion
sources should be for small- and medium-sized, hand- and underfeed-stoked coal
furnaces.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. CCS AT I Field/Group
Air Pollution
Combustion
Fossil Fuels
Polycyclic Compounds
Aromatic Polycyclic
Hydrocarbons
Coal
Fuel Oil
Natural Gas
Boilers
Stokers
Air Pollution Control
Stationary Sources
Polychlorinated Biphenyl
Isomers
Stoker Fired Boilers
13B
21B
21D
07C
13A
13. DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS (ThisReport)
Unclassified
21. NO. OF PAGES
43
20. SECURITY CLASS (Thispage)
Unclassified
32. PRICE
EPA Form 2220-1 (9-73)
39
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