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
policies of the Government, nor does mention of trade names
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.

-------
                                   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

-------
                            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

-------
                             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

-------
                            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.

-------
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.

-------
                            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.

-------
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.

-------
                            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.

-------
                            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.

-------
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.

-------
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

-------
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.'"

-------
                            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

-------
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

-------
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

-------
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

-------
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

-------
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

-------