EPA-650/2-74-017
August 1972
Environmental Protection Technology Series
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EPA-650/2-74-017
KINETIC MECHANISMS
GOVERNING THE FATE
OF CHEMICALLY BOUND
SULFUR AND NITROGEN
IN COMBUSTION
by
C. V. Sternhng and J. O. L. Wendt
Shell Development Company
Emeryville, California 94608
Contract No. EHSD 71-45 (Task 14)
ROAPNo. 21ADE-10
Program Element No. 1AB013
EPA Task Officer: G. B. Martin
Control Systems Laboratory
National Environmental Research Center
Research Triangle Park, North Carolina 27711
Prepared for
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D. C. 20460
August 1972
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This report has been reviewed by the Environmental Protection Agency
and approved for publication. Approval does not signify that the
contents necessarily reflect the views and policies of the Agency,
nor does mention of trade names or commercial products constitute
endorsement or recommendation for use.
11
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CONTENTS
Pace
Purpose and Scope 1
Conclusions 2
Overall View of Combustion 3
Method of Documenting Arrhenius Constants for
Reactions 7
Equilibrium Considerations 8
Literature Review 13
Experimental Data on Fuel Nitrogen Conversion
in Oil and Coal 13
Combustion of Ammonia 17
Cyanides and Combustion Using Nitrogen Oxides
as the Oxidizer 20
Oxidation of HCN 20
Low-Temperature Mechanisms Involving N-N
Bond Formation 21
Pyrolysis 23
Reactions Involving Sulfur 26
Process Modifications to Reduce SO. Emissions 41
Low Excess Air Combustion 41
Flame Quench 42
Staged Combustion 42
Two-Stage Air Addition 42
Two-Stage Fuel Addition or Reburning 42
The Use of Additives 43
Summary of Literature Review 44
Results of Modeling Studies 46
"Prompt" NO by Cyanide Reactions 46
Fixation of Atmospheric Nitrogen 48
NOX Reduction by Secondary Fuel Injection or
Reburning 54
ill
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CONTENTS (CONT)
Page
Oxidation of Fuel Nitrogen in a Diffusion
Flame 64
S02 Oxidation to SO. in Flames 72
Results Obtained From Merryman and Levy
Kinetics 72
Results With Adjusted Rate Coefficients 77
Conclusions 77
Synergism Between Sulfur and Nitrogen Oxides
(Post-Flame Region) 79
Recommendations for Future Work 82
Nomenclature 83
Appendix I. Library of Reaction Rate Data 85
Appendix II. Literature References Using the CODEN
System 99
Appendix III. Simulation of Flame Fronts by "Point-
Wise" Kinetic Calculations 125
Premixed Flat Laminar Flames 125
Diffusion Flames Modeled by the Whitman Two-
Film Theory 128
Appendix IV. Description of Computer Program EXHAUS
for Integrating Stiff Differential Equations Arising
in Kinetics Problems 131
Abstract 131
Purpose and Scope 131
Output Generated 132
Sample Problem 132
Problem Setup 132
Appendix V. An Exhibit of the Computer Output
Generated by Program EXHAUS 137
iv
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FIGURES
No. Title Page
1 Three Regimes of Particle or Droplet Combustion 4
2 Tentative Diagram Showing Paths Taken by Fuel Nitrogen
in Coal Combustion 5
3 Tentative Diagram Showing Paths Taken by Fuel Nitrogen
in Residual Oil Combustion 6
4 Equilibrium HCN in Combustion Gases 12
5 NOx Concentration as a Function of Excess Combustion
Air 16
6 Effect of Cracking Severity on Product Distribution
in Gas-Oil Cracking 25
7 Equilibria of Sulfur Species in a 10% Excess Air
Flue Gas 27
8 Equilibrium Levels of Plume Forming Species 28
9 The Variation of the Theoretical Equilibrium Yield
and Possible Actual Yield of S03 with Time in a
Boiler 30
10 Effect of Fuel Sulfur Level on S03 Formation 32
11 Effect of Fuel Sulfur Level on 803 Formation 33
12 Effect of Excess Air on 803 Formation 34
13 Effect of Excess Air on 803 Formation 35
14 Flame Formation of 803 as Function of Excess Air
and Sulfur Level of Fuel 36
15 Typical Temperature Profile - Injector Not in
Position 38
16 Effect of Flame Temperature on 803 Formation 40
17 Splitting of N-N Bonds, Lange Run 1 51
18 Production of N-0 Bonds, Lange Run 1 52
19 Predicted and Experimental Temperatures for
Computer Run NFIX4 57
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FIGURES (CONT)
No. Title Page
20 Predicted and Measured NOX Production 58
21 Mechanistic Models of Flame Sheets Occurring in
Diffusion Flames 65
22 Flame Sheet Model for Situation B 66
23 Effect of Temperature on NO Production in H£
Diffusion Flame 70
24 Effect of Temperature Clench on 503 Profiles -
Merryman and Levy Kinetics 75
25 Attempts to Fit Merryman and Levy Mechanism and
Rate Coefficients to Data of Cullis»Henson,and
Trimm 76
AIII-1 Conceptual Sketch of Flame Front in a Laminar
Premixed Flame 126
AIII-2 Conceptual Sketch for Diffusion Flame Front 129
vi
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TABLES
No. Title Page
1 Equilibrium Composition at 1200°K 8
2 Equilibrium for Reaction
HCN + 3/2 C02 >l/2 N2 + 1/2 H20 + 5/2 CO 10
3 Equilibrium for Six-Component System Calculated
by CHEMEQ-90% of Theoretical Air Simulated
No. 2 Fuel Oil 10
4 Equilibrium for 16-Component System Calculated by
CHEMEQ-90% of Theoretical Air-Simulated No. 2
Fuel Oil 11
5 Mechanisms of NH3 Oxidation 19
6 Nitrogen Compounds which Might be Involved in
Linkage Reactions 23
7 Experimental Data on S0-j Formation 37
8 Available Data on the Kinetic Constant of the
Reaction S02 + 0 + M ^ 803 + M 44
9 Reactions Included in the Cyanide Route to Prompt
NO 47
10 Arrhenius Parameters Used in Study of Prompt NO
via Cyanides 47
11 Fixation of Atmospheric Nitrogen—Synopsis of
Computer Runs 50
lla Reactions Used for Combined Methane-Burning and
Nitrogen Fixation 55
12 "Debris" from the Combustion of Methane with Air
in a Premixed Flame 56
13 Reactions Used in Reburning Model 60
14 "NO" Reduction by Hydrogen. No "C02" in Mixture 61
15 NO Reduction in Presence of C02 63
vii
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TABLES (CONT)
No. Page
16 Reactions Used in Hydrogen Diffusion Flame 69
17 Calculated Results-Hydrogen Diffusion Flames
with Fuel Nitrogen Simulated by N Atoms 71
18 Basic Kinetic Scheme for S02 Oxidation 73
19 Results Using Adjusted Rates 78
20 NO-S02 Synergism 80
21 Application of Model for NO/S02 Synergism to
Furnace Flue Gas and Sulfur Plant Incinerator
Emissions 81
AI-1 Listing of IBM Cards for Reaction Rate Library 86
AI-2 Format for Reaction Rate Library 95
AI-3 Reaction Names—Conventions Used and Literature
References 97
AII-1 List of References in Order of Acquisition Number 100
AII-2 Literature References Alphabetized by Author 106
AII-3 Literature References Alphabetized by CODEN 112
AII-4 CODEN Names for Journals, Alph by Name of Journ 118
AII-5 CODEN Names for Journals, Alpha by CODEN 120
AII-6 Complete References to Non-Periodical Literature 122
AIV-1 Format of Control and Data Cards 134
AIV-2 Format of Data Cards 136
viii
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Purpose and Scope
The objective of this work has been to elucidate the mechanisms by which
nitrogen and sulfur which are chemical^ bound in the fuel molecules are converted
into objectionable pollutants. This was attempted through detailed computer
simulations of reaction schemes considered to be relevant. It was expected that
the insights gained into the mechanisms of conversion would lead to ideas for the
control of these pollutants by combustion modification and would help in interpreting
the results of experimental studies. The work was requested by the U- S-
Environmental Protection Agency as Task lU of Contract EHS-D-71-^5-
A review of the literature on the fate of fuel nitrogen and sulfur led to
the formulation of the following critical questions:
1. To what extent does pyrolysis of the fuel occur before combustion?
2. How is the nitrogen bound in the pyrolysis products?
3. How is the nitrogen distributed among the pyrolysis products?
lu What is the environment (temperature and air-to-fuel ratio) at the
flame front in a diffusion flame of finite thickness, and how does this environment
affect the yield of products from the fuel nitrogen?
5- What reactions contribute significantly to the fixation of atmospheric
nitrogen both in the flame front and in the post-flame zone?
6. What are the reactions governing the rate of conversion of SOa to
SOs, both in the flame and in the post-flame region?
T. After NO has been formed, what reactions can reduce it back to N2 and
under what conditions are they effective?
Tentative answers are advanced for some of these questions, either from
the literature survey or from the results of computer simulations. For the latter,
the main tool used is the computer program EXHAUS which is described briefly in
Appendix IV. EXHAUS is a general purpose program for the integration of the material
and heat balance equations for either "point-wise" conditions or for a plug flow
reactor. "Point-wise" calculations can be shown to include the perfectly stirred
reactor and approximate simulations of flame fronts in either premixed or diffusion
flames. Tentative reaction mechanisms were set up for six situations thought to be
important for fuel nitrogen and sulfur conversion and were integrated using these
programs. Valuable insights have been obtained from each simulation. Obviously,
many approximations are required in work of this typej hence, each of the simulations
can be elaborated. In most cases, however, the important features of the mechanisms
can be seen from the current simplified simulations.
Problems simulated were:
1. Fixation of atmospheric nitrogen in premixed methane flames.
2. Formations of "prompt NO" via a reaction scheme involving cyanide
intermediates.
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3. Combustion of fuel nitrogen in a gaseous diffusion name under
various degrees of combustion intensity.
k. Reduction of NO back to N2 by means of flame reactions.
5« Conversion of sulfur to SOa in flames.
6. Catalysis of S02 oxidation by oxides of nitrogen.
Conclusions
From this study, we reached the following conclusions:
1. A large fraction of the nitrogen in the fuel appears in the char
fractions formed by pyrolysis, especially when the fuel is coal but also for residual
oil fuels.
2. Among the gaseous products of pyrolysis, HCN is expected to be the
most important.
3- The rate of fixation of atmospheric nitrogen cannot be predicted with
confidence for all situations. More good data is required.
^. While the Zeldovich reactions (see reactions 19 and 20 in text) usually
account for the bulk of the nitrogen fixed in flames, other reactions are sometimes
important.
5- Two alternative explanations for the "prompt NO" reported by Fenimore
can be advanced—fixation via cyanide intermediates or by reaction with the excess
free radicals produced in the flame front. More data is required especially for
fuels other than methane.
6. Fairly good quantitative predictions of prompt NO can be made by
considering the interaction of the combustion reactions with the fixation reactions
without cyanide intermediates.
?• The trends in the ratio of NO to N2 produced by the combustion of
molecules containing nitrogen as nitrogen content and temperature change can be
predicted by a simple model of the diffusion flame front. The reverse of the
Zeldovich fixation mechanism accounts for the production of N2. A strong effect of
combustion intensity is also predicted by this model.
8. An accurate quantitative description of the catalysis of the post-
flame oxidation of SOa "to SOa by the oxides of nitrogen has been developed. More
data is required before the flame oxidation can be correctly modeled.
9- Reduction of NO by homogeneous gas reactions is possible in fuel-rich
environments. The reaction with H2 can be modeled using some of the reactions from
the schemes of Lange and of Wilde. It was shown that the key reaction is
N + NO = N2 -i- 0 (1)
and that the N atoms are produced from intermediate compounds such as HNO, NH, etc.
Carbon dioxide inhibits the reduction according to this mechanism since it competes
for the reducing agent, H2, forming considerable CO.
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Overall View of Combustion
Only the heavy, dirty fuels contain appreciable amounts of chemically
bound nitrogen and sulfur. Useful models for predicting the conversion products
resulting from combustion must be therefore applicable to such fuels (coal and the
residual fuel oils). Because of their low volatility, these fuels cannot be premized
with the combustion air to form a gaseous mixture; hence, diffusion flames are
universally used for their combustion. The physical processes governing combustion
in diffusion flames of particulate matter are extremely complex and are still the
subject of a large research effort. Modeling of the chemical mechanism of the
combustion depends very strongly on the physical processes and, hence, cannot be
very precise at this time. One needs to abstract the salient features of the
combustion and make drastic simplifications in order to do practical chemical
modeling.
Our view of droplet combustion is in terms of three regimes, which are
illustrated schematically in Figure 1. The first regime occurs during periods of
rapid volatilization and large relative velocities between the drop and the
surrounding gases. Combustion occurs in the wakes trailing the particles; and the
fuel and the oxidizer are premixed, though imperfectly, before combustion starts.
The burning is then accomplished largely by (probably turbulent) flame fronts which
sweep through the gas. The second regime, shown in Figure 1, occurs where the rate
of vaporization is slow enough to allow a flame to attach itself to the particle.
Here most of the combustion occurs in a thin flame sheet surrounding the particle
and its wake. The reactions occurring in this diffusion flame sheet are quite
different from those occurring in the premixed case. In particular, there are hct,
fuel-rich regions where precombustion pyrolysis can occur. In such a flame front
the "fuel" is therefore not the same as the material fed into the furnace. The
third regime occurs after the more volatile materials have been vaporized. Because
of the strong heating, the remnant of the particles containing the heavy ends is
pyrolyzed very strongly and is thereby converted into a char. As the volatiles are
depleted, the flame front approaches the particle until oxygen molecules can attack
the char directly. The carbon is converted at the surface to CO and the nitrogen
to unknown products but probably mostly into NO. In the diffusion flame surrounding
the char particle the CO will burn to completion and the NO may possibly be further
converted into other products.
In a complete model for the combustion process, each of these regimes
should be simulated and the results combined in proper proportions, a problem of
prime concern being to determine the relative importance of the various regimes.
With respect to fuel nitrogen conversion, this will require a knowledge of how
nitrogen is distributed between the volatile fractions and the char.' Unfortunately,
a good, consistent set of data is not available showing how the'fuel nitrogen is
distributed among the pyrolysis products. By the use of fragmentary data, however,
(752), (755), (75*0* we have drawn up the distribution diagrams shown in Figures 2
and 3 to give a rough idea of how the N is distributed. It appears that most of
the nitrogen in coal will appear in the char so that modeling of char combustion
must have highest priority for this fuel. For the case of a residual oil, an
appreciable fraction of the nitrogen will appear in the char, so that even here the
combustion of the pyrolyzed residue will be important. A certain fraction of the
nitrogen from the coal combustion, and even more from residual oils, is volatilized,
however. It is expected that this volatile matter will be strongly pyrolyzed as a
* Reference numbers quoted are the acquisition numbers in the CODEN-oriented list of
references given in Appendix II.
S -llj-129
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^'O^J
cxJl
A. Totally Detached Flame. Rapid Mixing, Rapid Volatilization
Fuel-Rich Regions
Regions for Pyrolysis, Cracking
HCN, N, Pyrolysis Compounds Formed
Flame Front
B. Attached, Diffusion Flame. Pyrolysis Occurs in Fuel-Rich Region
Char is Being Formed
C. Char Burn-Out. Surface Combustion Occurs when Volatiles have Been
Driven Out. CO Formed as Result of Surface Reaction of Carbon and
O2. This CO Burns Externally to the Solid Particle in a Diffusion
Flame.
Figure 1. THREE REGIMES OF PARTICLE OR DROPLET COMBUSTION
S-14129
68275
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00
Ul
ro
Coal
Particle
Volatilization
80% of N
To Char
20% to
Volatile;
Pyrolysis
Oxidation
(Diffusion Flame Front)
HCN,
Cyanides
Post Flame
Reactions
NO,
N,
Figure 2. TENTATIVE DIAGRAM SHOWING PATHS TAKEN BY FUEL NITROGEN IN COAL COMBUSTION
-------
00 I
to —
XI *.
en —
N>
Vaporization
Pyrolysis
Combustion in Diffusion
Flame Front
Post-Flame
Reactions
40% of N
80% of Mass
Vaporized
NO,
N2
Figure 3. TENTATIVE DIAGRAM SHOWING PATHS TAKEN BY FUEL NITROGEN IN
RESIDUAL OIL COMBUSTION
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vapor to form primarily organic cyanides and lesser amounts of ammonia and related
compounds.
For simplicity we have worked mainly with regime 2 mentioned above and
have concentrated our attention on the volatile nitrogen. Nevertheless, some of
the models can be applied to the later stages of char combustion also. Examples
are the "reburning" of NO and the conversion of sulfur compounds beyond the stage
of oxidation represented by SQ2.
Method of Documenting Arrhenius Constants for Reactions
In the course of this work, a great many reactions were considered, and
for some of these several different sets of Arrhenius rate parameters were used.
Appendix I documents the reactions and rates by assigning a distinct name to each
reaction with its sets of forward and reverse rate constants.
S-14129
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Equilibrium Considerations
Combustion normally is carried out with an excess of air. If chemical
equilibrium were reached under such conditions, very low concentrations of pollutants
other than NO, N02, S02, and SOa would be present in the combustion products. Since
some promising techniques of combustion modification envision the use of less than
the stoichiometrically required air, it appears worthwhile to review the equilibrium
concentrations in combustion gases for both fuel-rich and fuel-lean conditions. In
addition to the major species, we are interested in SOa, SOa, COS, CSa, NO, NOa, 0,
OH, H, HaS, SO, HCN, and C2N2.
Two families of calculations were made using the Shell Program CHEMEQ
(Chemical Equilibrium). Equilibrium compositions are determined by minimization of
the system free energy using a modification of Hopf's method (755)« Thermochemical
data were taken from the JANAF (756) tables.
The first set of calculations omitted the cyanides but included all the
other species mentioned above. Calculations were made for 1200°K and l800°K for an
input composition resulting from burning CH4 with excess air and then progressively
enriching the inlet mixture by adding various amounts of CO. Table 1 shows some of
the results. It can be seen that the mole fractions of CS2 are well below 1 ppm
but that COS, HaS, and SO are near or slightly above the i ppm level in some cases.
Table 1. EQUILIBRIUM COMPOSITION AT 1200°K
CO Added
Oa
N2
C02
S02
HaO
S03
CO
COS
CS2
NO
N02
0
OH
H
Ha
HsS
SO
.001
.Ilk x IO-1
.751
.116
.967 x IO-3
.115
•325 X IO-4
.15k x IO-7
.710 x IO-21
< io-34
.6lU x IO-4
.1*08 x IO-6
.325 x 10- 8
.177 x IO-5
.208 x IO-10
.109 x IO-7
.169 x 10" 19
.1*97 x IO-11
.OU
.111 x 10'11
• 735
.li*9
.91*5 x IO-3
.111
.25!* x IO-9
.21*9 x IO-2
.176 x IO-5
.1*80 x 10"11
.1*81* x IO-9
.257 x IO-16
.259 x 10"13
.1*90 x IO-8
.721* x IO-8
.132 x IO-2
•315 x IO-4
.608 x IO-6
The second family of calculations was designed to determine the equilibrium
concentrations of HCN and cyanogen. Hydrogen cyanide has been detected in cigarette
smoke CH5) and in the products of combustion of CH4 with N02 as an oxidizer (757).
It is also found in large concentrations in the products of pyrolysis of nitrogen-
containing fuel components such as pyridine (372), (363). Results of equilibrium
calculations are reported here for a simulated No. 2 fuel oil burned under fuel-rich
conditions. The overall stoichiometry for the major species is represented by
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CASE A - 90$ of theoretical air
CHi.a + 1-17 02 + k'H'f N2 - > 0.6 H20 + 0.7^ C02 + 0.26 CO + k.klk N2
CASE B - 80# of theoretical air
CHi.a + !•<* 02 + 3.92^ N2 - > 0.6 H20 + O.W C02 + 0.52 CO + 3.921* N2
To check the results, the calculations were made by three different
methods.
Method I
Assuming that the concentrations of N2, CO, C02, and H20 are fixed, we
consider the reaction
HCN + |co2 — > |N2 + |n2o + fco (2)
The equilibrium partial pressure, PHCN» of HCN» in atmospheres is then given by
1/2 1/2 5/2
^ r
KP
react
Values of equilibrium constants were taken from the JANAF tables and inserted into
equation 1. Results are shown in Table 2 and are plotted in Figure ^. It appears
that equilibrium HCN concentrations are well below the ppm range. The high
reported values of HCN in combustion products are probably not equilibrium-limited
but rather rate-limited.
Method II
The Shell Development program CHEMEQ was used on the six-species system
N2, CO, C02, H20, 02, HCN. For the case of a fuel gas corresponding to 90% of
theoretical air, the equilibrium 02 and HCN concentrations are shown in Table 3«
Method III
Same as Method II, except that 16 components were considered. Results
are shown in Table k.
The three methods give essentially the same results. When the full 16
species are considered, there is a significant shift in the concentrations of the
major species, N2, CO, C02, and H20. This explains the slightly different HCN
concentration obtained when using this method.
S-HH29
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Table 2. EQUILIBRIUM FOR REACTION
HCN
C02
Temp, °K
2000
1900
1800
1700
1600
1500
i4oo
1300
1200
1100
1000
J Atmospheres
Percent of Theoretical Air
Bo 90
.74149979-08
.85824439-08
.10130031-07
.12193009-07
.15209365-07
.19661250-07
.26583438-07
.38072490-07
.58426704-07
.98312956-07
.18604207-06
.61330169-09
.70986227-09
.83786471-09
.10084957-08
.12579814-08
.16262011-08
.21987420-08
.31490127-08
.48325295-08
.81315601-08
.15387720-07
Table 3. EQUILIBRIUM FOR SIX-COMPONENT SYSTEM CALCUIATED
BY CHEMEQ-90& OF THEORETICAL AIR SIMUIATED NO. 2 FUEL OIL
Feed
Input Composition
Species Mole Frac
N2
CO
C02
02
HCN
.7340+-00
.4320-01
.1230f00
•9977-01
.0000
.0000
Equilibrium Mole Fractions at •
1000°K1400°K1800°K2000°K
.73404-00
.4320-01
.12304-00
•9977-01
.2960-19
.1517-07
. 7340+00
.4320-01
.12304-00
•9977-01
.7684-11
.2166-08
. 73404-00
.4320-01
.12304-00
•9977-01
.3376-06
.8233-09
. 73404- 00
,4323-01
. 12304-00
•9977-01
.1392-04
.6071-09
S-14129
10
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Table k. EQUILIBRIUM FOR 16-COMPONENT SYSTEM CALCUIATED BY CHEMEQ
OF THEORETICAL AIR-SIMULATED NO. 2 FUEL OIL
Feed
Equilibrium Mole Fractions at
11*00 °K
1600°K
1800°K
2000°K
Species Mole Frac _ _ _ _
N2 .73^04-OQ .731*0+00 .731*0+00 .731*0+00 .7338+00
co .1*320-01 .3299-01 .3505-01 .3638-01 .3739-01
C02 .12304-00 .1332+00 .1312+00 .1298+00 .1288+00
-9977-01 .8957-01 .9167-01 .9291-01 .9363-01
.0000 .151*5-10 .51*78-08 .5306-06 .20l*0-Ql*
.0000 .928^-09 .639^-09 .^766-09 .3818-09
-0000 .7671-19 .8259-19 .8700-19 .9266-19
.0000 .368U-11 .1063-08 .8776-07 .2992-05
.0000 .1*909-06 .1*903-05 .2956-01* .l?5l*.03
.0000 .8389-07 .2120-05 .26ll*-0l* .191*2-03
.0000 .3036-09 .2260-09 .1789-09 .11*97-09
.0000 .6551-08 .3260-06 .6833-05 .7756-04
.0000 .1*018-15 .2022-12 .2576-10 .1235-08
.0000 .3507-12 .1661-10 .3379-09 .3771-08
.0000 .7760-07 .3032-07 .11*58-07 .8199-08
.0000 .1021-01 .8151-02 .6831-02 .5957-02
02
HCN
C2N2
0
H
OH
HCHO
NO
N02
NsO
NH3
H2
S-ll*129
11
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io-7
„ io-8
u
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Literature Review
In order to formulate critical questions suitable for study by computer
simulation of chemical mechanisms, the literature was reviewed giving special
attention to pyrolysis of nitrogen compounds, combustion of nitrogen and sulfur
compounds, and mechanisms affecting the formation and breaking of the chemical bonds
C=N, N-H, N=N, and N=0. The literature is very large and cannot be reviewed in
detail here. To facilitate citation of references, we have adopted the CODEN system
of ASTM (758) used, for example, in Hochstim's (759) review of the kinetics^of
elementary reactions. Appendix II gives a complete listing of all the pertinent
references found, alphabetized by author, periodical, and acquisition number.
Experimental Data on Fuel Nitrogen Conversion in Oil and Coal
Summaries of experimental data on the influence of fuel nitrogen are
available in the Esso Report (797) and in papers by Martin and Berkau (790),
Turner et al (Esso) (791), and Fine et al (MIT)(798). In this section, we review
the literature with the following questions in mind:
(a) What is the effect of fuel N in coal combustion?
(b) What is the effect of fuel N in oil combustion?
(c) Can the NO formed by fixation be separated from that coming from
chemically bound N?
(d) What is the effect of excess air on fuel N conversion?
(e) What is the effect of nitrogen level, fuel type, and burner and
furnace design?
(f) What is the effect of the type of compound containing the nitrogen?
There are two contrasting opinions on the effect of fuel nitrogen in coal
combustion. One, supported by Bartok et al (797), maintains that the nitrogen in
coal contributes significantly to NOX under most firing conditions. Data from a
fluid bed combustor with argon/02 substituted for air taken by Jonke et al (799) show
conclusively that at low temperatures the NO is high, comparable to conventional
boilers, and is essentially all derived from the nitrogen in the fuel. The other
view, proposed by Sarofim and his co-workers at MIT (798) views fluid bed combustion
as representative of a premixed system (reaction controlled) which, by analogy, will
have a high conversion of CBN*to NOX, while normal pulverized coal combustion
resembles a diffusion flame in which pyrolysis precedes combustion and prevents
conversion of CBN to NOX- To support their view, they present data which indicate
that methylamine when burned in a diffusion flame will give a 10% conversion to NO
(independent of nitrogen content) compared to an 80$ to ^0% conversion to NO when
burned in a premixed flame. Incidentally, Sarofim and co-workers (798) find that
with no CBN in the fuel their diffusion flame had five times the NOX of their
premixed flame. Interestingly, this trend is contrary to boiler experience as
reported by Foster Wheeler (800) which shows the reverse trend. (Off-stoichiometric
combustion which is known to reduce NOX can be viewed as a change from a more to a
less premixed condition). This suggests that the comparison of Sarofin et al between
* CBN = Chemically Bound Nitrogen
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CBN conversion in premixed and diffusion flames may not be applicable to the real
situation prevailing in boilers and furnaces.
In oil combustion there appears to be little doubt that fuel nitrogen
contributes heavily to NOX emissions. This was shown by Martin and Berkau (790)
who burned No. 2 fuel oil to which was added various nitrogen compounds. The Esso
Report (797) also shows significant increases of NOX with increasing weight percent
nitrogen in fuel oil, although there the comparison is between two different No. 6
oils in the same boiler (175 MW to k80 MW). In a further study with No. 2 fuel oil
with CBN additive, Esso confirmed (qualitatively) the results of Martin and Berkau,
and with No. 6 oils of different nitrogen contents again confirmed that for a given
burner and boiler design nitrogen oxide emissions depend directly on the CBN content
of the fuel. They measured 4 50 ppm with 0.77$ N, 320 with 0.31% N, 290 with 0.25$
N, and 120 with 0.03$ N, on a Cleaver Brooks 50 hp boiler and on a 250 MW utility
boiler. Unpublished Shell data on refinery furnaces, boilers, and small oil field
steam generators firing fuel oils of various CBN contents is in agreement with
Esso's findings. Shell measured 450 ppm with 0.78$ N oil against 30 ppm on gas for
a simple gun-fired unit with no preheat and poor mixing. On a wide variety of
tests on boilers, Shell found that oil flame temperatures (measured by a sodium
injection, light emission technique) were, in general, cooler than gas flames,
that the data could be correlated by assuming that between 30 and ^0$ of the CBN was
converted to NOX and that oil flames fix only 20% to bO% as much N2 from the air
as equivalent gas flames of the same heat release. For a 225 M Ib/hr steam boiler,
Shell found that a low nitrogen oil (0.37$ N) gave 252 ppm NOX or 122 Ib/hr at
21.5$ excess air, while gas firing (refinery gas) produced 38! PI™ or 155 Ib/hr
at 16.5$ excess air. Esso also reported that for large utility boilers gas flames
could give higher NOX than oil. From this data we conclude that (l) NOX emissions
from oil flames depend strongly on CBN content of fuel and (2) oil flames fix less
nitrogen from air than gas flames with preheat and good mixing.
The effect of excess air on NOX emissions from oil flames both with and
without specified CBN contents has been well documented by Bartok et al (797), by
Turner et al (791), and by Martin and Berkau (790). In each case, NOX increases
with excess air although Turner found this increase was small for excess air levels
between 10 and 80%. Shell data for 0.79$ CBN indicate 150 ppm (corrected to 3$ Qs)
at zero percent excess air (with smoke and CO emissions) and 600 ppm (corrected to
3$ Oa) at 70$ excess air. Turner went further substoichiometric on Esso's Cleaver
Brooks boiler burning a residual oil containing 0.35$ CBN and obtained 300 ppm at
10$ excess air, 200 ppm at -10$ excess air, and ^0 ppm at close to -30$ excess air.
All the data shows that for fuel oils containing CBN the total ppm increases as
excess air increases.
It is useful to examine techniques used to separate the thermal NOX from
the CBN derived NOX- In their experiments with No. 2 oil doped with CBN compounds,
Martin and Berkau assumed that at a given excess air the thermal NO in all their
runs was equal to that produced in the run with no additive. In using this method,
care must be taken not to change the fuel properties, such as surface tension,
viscosity, etc., affecting drop size and thermal NO. For example, 2% N as quinoline
requires that compound to be 18$ of the total fuel. Turner et al used a different
approach. They hypothesized that flue gas recirculation (FGR) reduced only thermal
NO and supported this by showing that 30$ recycle reduced NO from No. 2 fuel oil
containing 0.03$ N to to ppm both with high and low atomizing air and that with
added fuel nitrogen FGR reduced NOX by the same amount, 80 ppm. The resulting NO
after 30$ recycle from the 0.03$ fuel oil was exactly the amount that would be
14
-------
obtained from 100# conversion of CBN. They further strengthened their arguments
by showing that for residual fuel oils the reduction of NO obtained by FGR was
independent of CBN content, although it was a strong function of type of fuel
(No. 6 or No. 2). Their method may be valid for fuel oils in their boiler, but it
has been shown by Rreen, et al (801) and others that for gas firing (containing,
presumably, no CBN) 30# FGR will effect only a 1% reduction in a utility boiler
and [by Lange (5 WO ] a 80-90$ reduction in a laboratory burner. Therefore, the
assumption that 30$ FGR eliminates all thermal NO may not always be valid.
The effect of nitrogen content on CBN conversion to NO was studied by
Turner who showed, using his method to separate thermal and fuel NO, that for
residual fuel oil the conversion decreased from 6($ at 0.2$ CBN to kO% at 0.4 and
greater percent CBN in the fuel. This agrees roughly with the results of Martin
and Berkau who observed the same trend in their doped No. 2 oil. Turner, in his
experiments with No. 2 fuel oil, found higher conversion than did Martin, and higher
than he got with No. 6 oil. The conversion of CBN to NOX is therefore also a
strong function of nitrogen content, of type of fuel, and of heater and burner type
(as well as of excess air, as described above). In some tests run by Shell, it was
found that when the same fuel containing 0.78$ N was burned in very similar heaters,
but with different burners, the NOx was 5^3 ppm for one burner against 300 ppm for
the other, at approximately the same excess air. Further experiments by Shell
showed that for a given burner increasing the atomization rate increased the NO by
more than the amount emitted by a gas flame of the same heat release. It is not
clear, however, whether this increase was due to increases in thermal NO or fuel NO
or both. Shell's studies indicate that old, crude burners with inefficient atomiza-
tion tend to give lower NOX than more modern burners, on the same high nitrogen fuel
and at the same excess air. Data in the Esso Report also indicate that at a given
fuel nitrogen content, different boilers give widely different NOX, with tangential
firing giving the lowest NOX emissions. Further discussions with Combustion
Engineering, Inc., disclosed that they had measured only 59 ppm NOX while burning
0.25$ N fuel oil in a 500 M Ib/hr steam boiler. If this is true, this would indicate
a breakthrough in NOX control. It is not at all clear why tangential firing should
have so much lower fuel nitrogen conversion. Possibly the explanation lies in
lower combustion intensity.
The effect of the nature of the nitrogen compound has been examined by
Martin and Berkau and by Turner et al. Martin and Berkau found that quinoline
(CgHyN) gave lower conversions than piperidine (CsHuN) and pyridine (CgHsN). The
latter two gave identical results. Turner found little influence of additive boiling
point on NOX in a series of tests with twenty different nitrogen compounds in No. 2
fuel oil. Only when the additive boiling point fell below 100°C did the conversion
to NOx drop markedly. Turner attributed this to loss in handling, but the effect
may be real.
It is worth mentioning the results of the work by Bienstock (802) et al
in an experimental pulverized coal furnace. The coal had a nitrogen content of
l-3#. At 22$ excess air, they obtained 600 ppm NOX emissions. Reduction of excess
air to stoichiometric reduced NOX to 100 ppm. Two-stage air was also very effective
in NOX reduction. The surprising thing about their data is that in each case there
was a substantial reduction of NOX from the flame exit to the stack. This had not
been observed before. Their data is shown in Figure 5 where the abscissa is
temperature which was measured simultaneously at their sampling point. Although
the oxygen content changed from position to position, indicating dilution, this
change was not large enough to influence the measured ppm of NOX-
15
-------
1200
1000
Q.
Ou
*
C
Q>
800
600
x
D
400
200
O 22% Excess Air. Reduction of NOX
Booed on These Tests
A 5% Excess Air. Reduction of NOX 62%
D 5% Excess Air Plus Injection of 17%
Addition Excess Air. Reduction of NOX 62%
O Stoichiometric Air. Reduction of NOX 81%
0
2800
I
I
2400
Figure 5.
2000
1600
Temperature,
1200
800
400
NO* -CONCENTRATION AS A FUNCTION OF
EXCESS COMBUSTION AIR
S-14129
68275
16
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Combustion of Ammonia
Ammonia is the simplest fuel molecule with chemically bound nitrogen. It
may also be formed in the pyrolysis of the more complex fuel molecules containing N.
For example (760), about 16$ of the nitrogen in coal appears as gaseous ammonia
during conventional coking operations. Ammonia, as the parent compound, may also
serve as a partial model for the combustion of amines. The combustion of ammonia
has also been studied more thoroughly than that of any other fuel nitrogen compound.
This section gives a brief literature review of ammonia combustion.
It is by no means clear what combustion conditions lead to high conversions
to Na and what conditions lead to low conversions; data of both types have been
reported. Several studies indicate that conversion to NOX is high under fuel-lean
conditions [Husain and Norrish (387), Bull (765), Bradley et al (762), Fenimore and
Jones (763), Drummond and Hiscock (76U), MacLean and Wagner (765), Sutton and
Starkman (766), and unpublished studies in Shell laboratories]. Under fuel-rich
conditions, several studies show low conversions to NOX (Fenimore and Jones,
Sutton and Starkman). In contrast to this rather simple picture, Andrews and Gray
(767) in a laminar flame experiment obtained not more than 12$ conversion to NOX
under both fuel-lean and fuel-rich conditions. Also, experiments (unpublished) in
Shell laboratories show a relatively high conversion (37$) at extremely fuel-rich
conditions (39$ of theoretical air). In this experiment, the flame temperature was
kept artificially high.
The most interesting phenomena described in the literature on ammonia
combustion are (l) early formation and subsequent reduction of NO in fuel-rich
flames, (2) decomposition of NHa to Na and Hs before Oa is encountered, and (3)
the overall mechanisms of combustion. Fenimore and Jones found that NO was
formed as an intermediate and then destroyed. They proposed that NHa vras the
reducing agent:
NO + NH2 = N2 + "• (3)
They also found ammonia in the residual gas. MacLean and Wagner found that NO vras
produced in small amounts and decayed slowly and that no residual NH3 appeared in
the burned gas of fuel-rich flames. Similarly, no NH3 passed undecomposed through
the rich flames of Gray, McKniven, and Smith (768) or of Bull (765). Both of
these investigators found NaO as an intermediate. Furthermore, MacLean and Wagner
found that N20 was formed where NO was being produced most rapidly.
Drummond and Hiscock (764), in a shock tube study, found substantial
reduction of NO and conjectured the reaction: *
NO + NH = N2 + OH (k)
Almost complete decomposition of ammonia to Na and Ha was observed in the
diffusion flame experiments described by Gaydon and Wolfhard (769), (770). However,
their flame was very hot since they burned with oxygen. Peaks in NH and NHa
radicals were observed about 1 mm from the flame front on the rich side where the
temperature was about 2500°K suggesting that most of the ammonia was pyrolyzing
there.
As regards overall mechanisms for ammonia combustion, the two leading
contenders are shown in Table 5. Mechanism I, due to Husain and Norrish, is
S-1^129 17
-------
analogous to the most widely accepted mechanism proposed for CH4 combustion at
high temperature. [See Fristrom (775)]. First, a free radical, e.g., OH, abstracts
H from NH3. After that, the key step is in the four-center reaction:
NH2 + 02 = HNO + OH (5)
The HNO subsequently goes to NO. In their flash photolysis experiments, Husain and
Norrish found OH and NH after delays of about 500 microsec but could not detect HNO.
This weakens somewhat the credibility of their mechanism. They mention that NH3 was
converted completely to NO! Mechanism II, by Takeyama et al (772), was suggested
to explain their shock tube studies. Instead of reaction 5, they propose:
NH2 + 02 > NH + H02 (6)
followed by the four-center reaction
NH + 02 = NO + OH (7)
Thus, they introduce, in a new context, the old controversy about the possible
significance of the hydroperoxyl radical, H02, in high-temperature combustion. Both
of the mechanisms described above predict the formation of large amounts of NO, and
neither is able to account for appreciable conversion of NH3 to N2. Based on
present knowledge, Mechanisms I and II appear equally likely although the failure
to detect HNO tells against Mechanism I. Despite this, most investigators prefer
I. It would appear that both mechanisms should be expanded to include N^ as an
intermediate. Any useful mechanism should explain the large yields of N2 and the
formation and subsequent decay of NO under fuel-rich conditions. The scheme of
Wilde (773) looks promising. It was proposed for the reaction of H2 with NO and
involves HNO as a key intermediate. Wilde obtained good agreement with literature
data on the initial rate of the reaction.
We can summarize the discussion of ammonia combustion by the following
unanswered questions:
1. What species is responsible for chain branching: HNO, H02, or other?
2. What is the role of N^; how is it formed and then destroyed?
3. How is NO destroyed in fuel-rich flames?
k. How is the N-to-N bond formed?
18
S-1U129
-------
Table 5. MECHANISMS OF NH* OXIDATION
I. Husain and Norrish (387)
II.
NH3+M=NH2+H+M
NH2 + 02 = HNO + OH
OH + NH3 = NH2 + H20
HNO = H + NO
HNO + HNO = HaO + NaO
HNO + OH = H20 + NO
H + HNO = H2 + NO
Takeyama and Miyama (772)
NH2 + 02 = NH + H02
H02 = OH + 0
OH + NH3 = NH2 + OH
0 + NH3 = NH2 + OH
NH -H 02 = NO + OH
NH + OH = N + H20
N + 02 = NO, etc.
NH + NO = N2 + OH
1
2
3
5
6
7
1
2
3
initiation
key depletion
branching
initiation
branching
k key depletion
5
6
7
8
possibly
19
-------
Cyanides and Combustion Using Nitrogen Oxides as the Oxidizer
A number of investigators have studied combustion of hydrocarbons and
other fuels supported by the oxidizers NaO, NO, or N02 [Gray et al (777), Myerson
et al (778), Patry and Engel (779)]- These studies are of interest for the present
problem from another viewpoint, that of the reduction of nitrogen oxides to N2 by
hydrocarbons in flames. In a number of cases detailed information about the final
products of reaction is not given. Among the products detected are HCN and
formaldoxime (CHO-N=0). For example, Myerson et al find up to 1.1 moles of HCN per
mole of propane consumed in the propane-N02 flame. Patry and Engel found 70$ of
the NO, when reacted with methane, went to form HCN at temperatures up to 1100°C.
Fenimore (721), in his study of the "prompt" NO in hydrocarbon flames,
was led to postulate the formation of cyanides by reactions like
CH + N2 = HCN + N (8)
C2 + N2 = CN + CN (9)
Unpublished experiments at Shell have shown appreciable formation of HCN by the
reaction of nitrogen plasmas with methane. Bockhorn et al (8C4) produced large
yields of HCN in a staged flame.
Oxidation of HCN
The burning of HCN probably plays a central role in combustion of the
pyrolysis products of heterocyclic nitrogen compounds and in the formation of prompt
NO by the method proposed by Fenimore. Little is known about the mechanism of
combustion of HCN: the best available article appears to be that of Ailliet and
van Tiggelen (386). They report burning velocities over a wide range of conditions
and discuss briefly the mechanism of combustion. They suggest that the following
reactions are important.
HCN + H = H2 + CN (10)
CN + 02 = NCO 4- 0 (11)
HCN + 0 = NCO + H (12)
NCO + 02 = CO + NO + 0 (13)
NCO + 0 = NO + CO (14)
To these must obviously be added the reactions for hydrogen combustion and probably
these additional routes for CN formation:
HCN + 0 = OH + CN (15)
HCN + OH - H20 + CN (l6)
Possibly N2 is made by the reaction (72k):
NCO + NCO = N2 + CO + CO (17)
8-14129 20
-------
fiasco (557) has obtained data indicating that
CN + 02 = CO + NO (18)
also occurs. For room temperature, fiasco gives the rate of reaction 11 as
kf = k.6 x 1012 cm3/ (mole, sec)
and he concludes that the rate of reaction 18 is less than 0.15 times the rate of
reaction 11.
Other references discussing reactions connected with HCN combustion are
(358), (559), (360), (579), (385), CH2), (407),
Low-Temperature Mechanisms Involving N-N Bond Formation
The key to understanding the mechanism by which fuel nitrogen is converted
partially into Na lies in understanding how the N-to-N bond is formed. Possibly,
the same reactions are involved as occur in the Na fixation process. For example,
the Zeldovich cycle
N2 + 0 = NO + N (19)
N + 02 = NO + 0 (20)
or the NaO cycle
N2+0 + M = NaO + M (21)
NaO + 0 = NO + NO (22)
can function in reverse. However, if these are the only reactions involved, it is
difficult to explain how yields of NOX much lower than equilibrium values can be
obtained. In the extensive literature [see, for example, (780) ] on reactions of
organic nitrogen compounds, several mechanisms forming N-to-N bonds have been
discussed. Most of these mechanisms have been studied only at low temperature or in
aqueous media and hence may not be directly applicable to flame conditions.
Nevertheless, some insight into possible significant flame reactions can be gained
from this literature.
Nitrogen gas is formed directly by the reaction of nitrous acid with
primary amines [(781), page 160]
+ HONO = CH3OH + N2 + H20 (25)
With secondary amines the first product is a nitrosamine
(CH3)2NH + HONO = (CH3)2NNO + H20
Similar reactions can occur with HNO in place of HONO. For example, Levy (805)
in discussing the formation of Na in flames of hydrocarbons with NOa postulated the
reaction
HNO + HNO = NaO + HaO (25)
S-11H29
21
-------
It is difficult to construct a simple activated complex for this reaction unless
several steps are postulated. Qy analogy with reaction 2k we can, however, picture
the following sequence
X0-H
N
keto-enol ^ „
isomerization
(hyponitrous (26)
acid)
,
N'0-. N °NH
M 'H - > " +
>V ^
(five center
activated
complex)
Credence is lent to this sequence by knowledge that a standard method for formation
of N20 is by decomposition of hyponitrous acid (805), (803, page 66l).
Other methods of forming the N-to-N bond are through linkage reactions
similar to 26 but involving more complex molecules. Thus we may have
NO + NO 4- M = NaOa + M (2?)
N02 + N02 = N204 (28)
NO + NH2 = NH2NO (nitrosamine ) (29)
NH + NH = N2H2 (30)
Species which possibly might be involved in these linkage reactions are shown in
Table 6. On first glance, it seems improbable that these reactions could be
important routes for synthesis of N2. This is shown by considering
NO + NO + M = N202 + M (31)
Using the thermodynamic data of Guggenheim (Uo8), together with an estimate of the
maximum rate we found rates of the order of 2 x 10~12 g moles/sec cm3
which is much too slow to explain N2 formation in furnaces.
Azo compounds, especially the azonitriles (780, page 686), are used widely
as free radical sources because of their tendency to decompose yielding molecular
N2 (and a pair of free radicals)
22
8-11*129
-------
CH3 CH3
t
CH3-C-N=N-C-CH3
CN CN
CH3
•C-CH3
LCN J
N2 (32)
It is possible that collision of the two free radicals (CH3)aCN-N: could lead in
one step to the same products.
Table 6. NITROGEN COMPOUNDS WHICH MIGHT
BE INVOLVED IN LINKAGE REACTIONS
N
NH HNNH (diimine)
NH2 N2H4
NH3 HONNOH
NHsOH CN
MONO C2N2
HON02 HCN
NaO HCNO cyanates
NO HNCO isocyanates
N02 N3~ azides
N03 HN3 hydrazoic acid
NaOa H2N202 nitramide
Na03 H-C=N-O formonitrilioride
-C=NnO fulminate radical formonitrile oxide
Pyrolysis
In the combustion of liquid droplets, an oxygen-deficient region around
the drop will be formed as the vaporized fuel moves outward. Also under fuel-rich
combustion, the entire combustion products are deficient in oxygen. Under these
conditions simple pyrolysis of the fuel molecules may be important.
It is observed that pyridine is partially decomposed by heat at
temperatures above 850°C (372), (363). Products formed are HCN, light gases,
and condensation products of the original molecule and hydrocarbon radical
fragments.
Quantitative data on rates of cracking of nitrogen compounds are scarce.
An approximate idea of the rates can be obtained by comparison with the much more
abundant data for pyrolysis of gas oils. Considerable data is available for these
materials (boiling range 200°C-^00°C) due to commercial interest in olefin
manufacture by gas oil cracking (370), (371).
Hurd, Macon, Simon and Levetan (klk) summarize the severe pyrolysis of
pyridine as follows. "The hetero bond (C-N) in pyridine is the point of initial
rupture into diradicals.
B 7 p a
(33)
S-1^129
23
-------
After this occurs, somewhat random rupture of the other bonds occurs, but rupture
at 7 and 5 should be favored. Rupture at 8 leads to HCN and the C4 diradical
•CH=CH-CH=CH- "
The latter serves to explain the formation of polyaromatic rings, e.g.,
H
X^ st^/^
H2
N'
Ruhemann (78^) stated that at 900°C practically complete cleavage of the
pyridine ring occurred. Among the gaseous products were HCN, H2 at 8U-86#, CH4 at
"* "'1, and olefins at l-2#.
A typical value for the first order rate constant for cracking of a
normal hydrocarbon of molecular weight of about 225 is
k = 1014 exp(-58000/RT) sec-1
With such a rate, one would expect half of the original molecules to be cracked in
about 30 millisec at 1000°K, in 2 microsec at 1500°K, and within 1(T8 sec at
temperatures over 2000°K. This degree of cracking leads to about k molecules for
each molecule cracked and of these three are lighter than molecular weight 80. In
such processes the temperature is lower, the residence time is shorter, and the oil
being pyrotyzed is lighter than for the case of combustion of a residual oil in a
furnace. Despite the differences, the data can be used as an indication of what
molecules will result from pyrolysis. Figure 6 shows the effect of increasing
temperature and residence time on product distribution.
Highly aromatic compounds probably behave quite differently, being more
refractory and also producing fewer small molecules and more polyaromatic material.
Nevertheless, at typical flame temperatures, their life before cracking is probably
also quite short compared to the time required for a molecule to diffuse from drop
surface to flame front, Ityridine, which is an aromatic compound, decomposes
appreciably at 1100°K (363). At such temperatures, fiearly all of the material goes
to form such larger molecules as quinoline although small amounts of HCN have been
detected. In petroleum coking processes, it appears that most of the nitrogen in
the fuel stock goes to the coke rather than to the light molecules formed.
Using the fragmentary data on distribution of nitrogen among the various
pyrolysis products (753), (75^), (760), etc., we have constructed the typical dis-
tribution charts shown as Figures 2 and 3. For coal, most of the nitrogen is
expected to appear in the char phase and for residual fuel oils a substantial
fraction will appear there. If this is so, the details of combustion of the char
phase will be very important in governing the fraction of fuel nitrogen converted
to NOX- Good data is urgently needed on this point. Since analysis of nitrogen
in coke from coal show of the order of 1% by weight (753), it is obviously
fallacious to think of the volatilization as removing most of the nitrogen.
Analyses of petroleum cokes also show high nitrogen, up to 3$ by weight. However,
much less char is made from oils than from coal.
S-1IU29
-------
40
20
10
8
6
1.0
0.8
0.6
0.4
Ethyl ene
Aromatics
Cyclopentediene
Low
Moderate
Severity
High
Figure 6. EFFECT OF CRACKING SEVERITY ON PRODUCT
DISTRIBUTION IN GAS-OIL CRACKING
From Oil and Gas Journal 74 (Jan. 1971)
S-14129
68275
25
-------
Reactions Involving Sulfur
In conventional combustion systems, the presence of sulfur compounds in
the fuel can lead to the formation of sulfur dioxide, S02, and sulfur trioxide, S03.
Sulfur trioxide is the more noxious of the two and can lead to corrosion in air
preheaters and the formation of plumes. Certain operating conditions that may
minimize NOX formation, such as rapid temperature quench, may cause large amounts
of S03 to be formed, and may therefore not be practical because of S03 (or, more
correctly, H2S04) plumes that may violate local air pollution plume opacity
regulations. The formation of sulfur trioxide is also of interest because it
depends strongly on the higher-than-equilibrium concentration of 0 atoms in the
flame; therefore, its study can give insight into the role of superequilibrium 0
atoms in the formation of other- pollutants, especially that of "prompt" NO. In
addition to this, it has been shown that sulfur and nitrogen oxides interact and
that synergisms occur in the formation of both pollutants. A significant effort
was therefore expended to elucidate the kinetic mechanisms of sulfur trioxide
formation and to determine how nitrogen oxides and sulfur oxides interact during
and after the flame.
A review of the literature on S03 formation has shown that the mechanisms
of oxidation can be divided into two categories --homogeneous and heterogeneous.
Homogeneous mechanisms include those reactions occurring both in the flame and in
the high -temperature reaction zone in the flue gas beyond the flame. Heterogeneous
mechanisms involve both suspended fly ash and furnace deposits. In this study, the
heterogeneous mechanisms have been considered only insofar as they affect data and,
thus, may mislead investigators of the homogeneous mechanism.
The relative importance of the homogeneous and the heterogeneous mechanism
of S03 formation almost certainly must depend on the particular furnace, fuel,
operating conditions in question, but sane (6ll), 612), (338) have insisted that
one or the other was the major source.
Studying the effects of S02 injection in various regions of a pilot-plant-
size steam boiler on corrosion probe measurements, Andersen and Manlik (6lj) concluded
that roughly equal amounts of S03 were being foimed in the flame, the high temperature
gas region beyond the flame, the flues, and the stack. All of this seems to
indicate that none of the mechanisms can be ruled out a priori in any situation.
Before discussing the various mechanisms involved, an examination of the
SOx equilibria in flue gas systems is in order. This point was examined using the
Shell program CHEMEQ. The following species were considered to be present in the
gas:
02, N2, C02, H20, CO, COS, CS2, SO, S02, S03,
HaS04, HsS, NO, N02, N03, 0, OH, H, H2
The input mixture was assumed to contain 12$ C02, 12$ H^, 0.1% S0a, and various
levels of 02 with N2 ad justed to make up 100$ gas composition. The JANAF tables were
used as the source of thermodynamic data. Figures 7 and 8 show that at high
temperatures S02 is favored, at low temperatures gaseous H2S04 is favored, with the
maximum S03 levels occurring about 700°K.
S-1M29 26
-------
10% Excess Air
1000 ppm SOX
12%H2O
12% CO,
600
1400
1600
800 1000 1200
Temperature, °K
Figure 7. EQUILIBRIA OF SULFUR SPECIES IN A 10% EXCESS AIR FLUE GAS
S-14129
65854
27
-------
100
Total SOX Concentration
20% O2 in Flue Gas
600
800
1200
1400
1000
Temperature, °K
Figure 8. EQUILIBRIUM LEVELS OF PLUME FORMING SPECIES
1600
S-14129
65854
28
-------
If equilibrium were achieved, almost all the sulfur emitted at stack
temperatures would be in the form of S03 or H^SC^. In fact, less than 20$ of the
sulfur is emitted in this fonn. Evidently we are dealing with a case of frozen
equilibrium, where a moderate amount of S03 is foimed at the high temperature
region where it is not favored thermodynamically and that as the temperature is
dropped a certain concentration is frozen in. This is demonstrated in Figure 9»
taken from Medley (313). This situation is distinguished from that of NOX in that
locally in the flame the S03 is fomed in superequilibrium amounts, and then decays,
while NOX seldom reaches equilibrium in the hot flame zone when its formation is by
fixation only. (Recent experimental data on ammonia combustion, however, has shown
that there NO can be formed in amounts vastly exceeding equilibrium at the peak
flame temperature). Equilibrium considerations in pollutant formation can, therefore,
be grossly misleading.
The basic mechanism controlling the level of S03 in flames involves
oxidation of S02 by atomic oxygen (612), (3^5), (6lU) and decomposition of S03 by
reaction with atomic oxygen or hydrogen
S02 + 0 + M > S03 + M (35)
(36)
(37)
where M is any third body. This mechanism has been shown (615), (333) to occur just
beyond the visible flame, after the combustion reactions are complete and before the
free-radicals levels have decayed. Analysis of available rate data for 35 yields
(see Table 8)
k35 = 2.0 x 101S exp (-1070/RT) cm6/mole2/sec
Nettleton and Stirling (6l6) report
k3e = 1012 cm3/mole/sec at 2150°K
and Merryman and Levy (61?) find
k36 = 2.8 x 1014 exp(-12000/RT) to 6.5 x 1014 exp (-10800/RT)
No estimates for the rate of 37 have been found, but Fenimore and Jones (333)
estimate that the ratio of k35 to the largest of the k36 or k37 is of the order of
104 cm3/mole. Therefore, the slowness of the S03 decay reactions coupled with the
high levels of atomic oxygen in the flame can lead to very high S03 levels. In
fact, observations in oil and gas fired (6lM, (6l6) units indicate that maximum
S03 levels can be higher than those predicted by the S02-02-S03 equilibrium. In the
systems examined thus far, the high S03 levels subsequently decay, but it can be
seen that the flame-gas quench rates can be important for S03 formation. If the
quench is too fast (e.g., by flames impinging on refractory, or poor mixing in the
combustion chamber), the high S03 levels can be "frozen" into the flue gases,
whereas a slow quench favors reduction to the low equilibrium values at high
temperatures..
One other flame mechanism has been noted by Levy and Merryman (6l8). In
probing HaS-02-Ar (or N2) flames, they noted a small level of S03 in the early part
S-14129
29
-------
Increased Time
en
O
o
0)
c
o
O
Theoretical Equilibrium
with 10% Excess Air
20 -
~/\ Furnace
LH
1600 1400
1200 1000 800
Temperature, °K
Figure 9. THE VARIATION OF THE THEORETICAL EQUILIBRIUM YIELD AND
POSSIBLE ACTUAL YIELD OF SO3 WITH TIME IN A BOILER
S-14129
68275
30
-------
of the flame which subsequently disappeared. This was attributed to the reaction
SO + 02 + M - > S03 + M (38)
Since this occurs early in the flame where there are still plenty of reducing
radicals around, the S03 is quickly removed. Hence, this mechanism probably does
not contribute much to the final level of S03 emitted from the flame. This
conclusion appears to be corroborated by experiments in which S02 added just at
the tip of the flame produced the same S03 levels as when the S02 was added with
the fuel
The level of S03 emitted from a flame increases with the sulfur level
cf the fuel (see Figures 10 and ll). However, the percentage of total sulfur
appearing as S03 decreases as the sulfur level of the fuel increases (3^5), (615),
(619), (620). The reason for this is not completely understood, but it is known
that sulfur in flames can be very effective in breaking reaction chains. Halstead
and Jenkins (639) observed the decay of H and OH in H2-02-N2 flames doped with
S02. They found that the free radicals disappeared faster when S02 was present
and interpreted this in terms of the mechanism
H + S02 + M c=£ HS02 + M (39)
H + HS02
OH + HS02
yielding
kask-io = 8.2 t 0.8 x 10~30 cms/molecules2/sec
k39k41 = 1.3 ± 0.3 x 10-30 cms/molecules2/sec
i
at 2000°K. Reactions 39 to Ul coupled with the free-radical generating reactions
in the flame might lead to a reduction of atomic oxygen level in the flame as
sulfur level increases. Durie et al (72?) confirmed these values for k40 and k41.
The main variable determining the S03 level emitted from the flame appears
to be the level of excess air used in combustion. Several studies (3^5), (6lk),
(615), (621), (622) have shown that the level of S03 is very sensitive to excess
air, especially in the region below 10$ excess air (see Figures 12 and 13).
Hedley (6l^) even argues that there is a critical excess air range for S03 forma-
tion near 30-UO$. For high excess air levels it can be argued that the increase
in available oxygen is more than offset by the reduction in flame temperature,
lowering the atomic oxygen available for reaction 35. The effects of excess air
and fuel sulfur level were also examined by Wendt (623) et al (see Figure lU) in
a laboratory flat flame. (For the purposes of modeling these data, the complete
set of conditions and the temperature profile are shown in Table 7 and Figure 15. )
The other variable of importance is the flame temperature. It would
seem that high flame temperatures might increase the atomic oxygen levels and,
hence, increase formation of S03. This effect has been observed by Crumley and
Fletcher (619). They measured the SOs produced by a CS2-doped kerosine flame
while varying the flame temperature by heating the secondary air fed to the
S-11H29
31
-------
Dooley and Whiteingham
0.4 0.8
SO2 in Stream, %
0.008
CO2 Content of Flue Gases = 12%
Furnace Wall Temp., °C
Crumley and Fletcher
S-14129
65854
01234
Percent S in Oil
Figure 10. EFFECT OF FUEL SULFUR LEVEL ON SO3 FORMATION
32
-------
0.010
> 0.008
in
•0
o
X
Q
c
£
5
«•»
O
to
0.006
0.004
0.002
Rendle and Wilsden
I
2 4
Fuel Sulfur Content, %w
80
Srl4129
65854
Q.
Q.
O"
CO
60
40
20
SO3 Equivalent to
]% Conversion of
S to SO3
I/
Range of Values
Fuel: Natural Gas with
Added H2S
Air Level: 114 to 118%
of Stoichiometric
Sampling Position: 24" from
Burner Plate
Barrett et al
I
0 8 16 24
Sulfur in Fuel, Percentage by Weight
Figure 11. EFFECT OF FUEL SULFUR LEVEL ON SO3 FORMATION
33
-------
r»
o
40
32
24
16
Barrett et al
Range of
Values
$03 Equivalent to
1% Conversion of
S to SO3
Natural Gas Con-
taining 5j/2% S
by Weight
Sampling Position: 24"
from Burner Plate
90 100 110 120 130
Total Air, Percentage of Stoichiometric Air
S-14129
65854
Reid
D
O
Levy and Merryman
Hedley
Effect of Oxygen Level on
Percentage of SO2 Oxidized
to S03
i i i
Figure
4 8 12
Oxygen in Products, %
12. EFFECT OF EXCESS AIR ON SO3 FORMATION
34
-------
32
24
Crossley
I
a.
o
16
I
i
0.4 0.8
02, %
1.2
S-14129
65854
!
Q.
o"
48
40
32
24
16
02,
4
I
16 24
Excess Air/ %
32
40
Figure 13. EFFECT OF EXCESS AIR ON SO3 FORMATION
35
-------
1.4
1.2
1.0
0.8
r>
o
to
to
to
0.6
0.4
0.2
S IN FUEL,
%w
8
EXCESS AIR, %
10
12
Figure 14. FLAME FORMATION OF SO3 AS FUNCTION OF EXCESS
AIR AND SULFUR LEVEL OF FUEL
S-14129
67128
36
-------
O)
E-
5
Table 7. EXPERIMENTAL DATA ON S03 FORMATION
Wendt et al (62j)
Ron No.
LR-10667-1B
-4o
-45
-46
-50
-51
-52
-55
-5*
-56
-57
-58
-59
-60
-61
cm
Rate
sec/rain
1475
1475
1475
11*75
' 1475
1475
1475
1475
1475
1475
1475,
1475
1475
1475
1475
80s Rate
scc/ndn
100
45
100
100
1*5
45
^5
100
U5
100
25
25
25
25
U5
^M S
in Ftel
10.7
5.»f
10.7
10.7
5.U
5.*
5.1*
10.7
5.*
10.7
3.2
3.2
3.2
3.2
5.*
Air Rate
scc/ndn
iteoo
1^900
15600
1^900
15600
ll*9OO
1^550
11*900
ll*900
1^550
15600
Ilf900
1^550
11*900
1^*500
% Excess
Air
1.1
6.1
11.1
6.1
11.1
6.1
3.6
. 6.1
6.1
3.6
11.1
6.1
3.6
6.1
3.6
Height of
Probe
Above
Burner
cm
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
2.0
Sfe
Sample
ng S04*
224.7
93.3
166.6
203.4
88.1
91.0
91.0
202.3
93.3
213.1
50.01
54.84
55.56
53.16
95.22
803
Sample
mg S04-
.2
.8
1.73
1.40
.91
.79
.65
1.46
.83
.97
.64
.53
•VT
.55
.72
*s
as
SQs
.09
.85
.92
.68
1.02
.86
.71
.72
.88
.45
1.27
.96
.84
1.02
.75
-------
VJ I
8±
ro
•O
2700
2000
* 1800
§
2
» g 1600
1400
1200
24
3. 2% Sin Fuel
11.1% Excess Air
1475 scc/min CH4 Fuel
" ^WVi (Primary)
D ^^OO o n * *
-* 00000o°ooooooo
o
1,1,1,1,1,1,1,1,1,
.0 24.4 24.8 25.2 25.6 26.0 26.4 26.8 27.2 27.6 28.
Distance, cm
Figure 15. TYPICAL TEMPERATURE PROFILE - INJECTOR NOT IN POSITION
-------
burner. The result was that S03 measured just beyond the flame increased up to a
temperature of 1750°C and then leveled off (see Figure 16). Levy and Merryman
(616) report the opposite effect. However, they were comparing two different
flames, H^-O^Ar and H^-Og-Na; hence, the lower level of S03 in the flame with
the highest temperature (HgS-Oa-Ng) may be attributable to other mechanisms.
The overall conclusion was that S03 can be formed in flames and the
excess air, flame quench rate, and flame peak temperature can have significant
effects. In a variety of combustion rigs, from bunsen burners to small domestic
boilers, the flame produced S03 has been found to be about 1-3$ of the total
sulfur in the fuel.
In the high-temperature gaseous region outside the flame, the S03 level
can decrease or increase depending on which of two mechanisms dominates. If the
quench rate is not too fast, the super-equilibrium flame-produced S03 levels can
decay. Alternatively, S02 can be oxidized to increase the level of S03.
As mentioned above, evidence (6lU), (6l6) does exist for the formation
of super-equilibrium (S02 + 1/2 02 = S03) amounts of S03 in flames. Maximum
values of 15-20 ppm S03 have been observed. The results of Medley (6lU) indicate
that the maximum S03 level occurs within about 30 msec, and the decay to equilibrium
is achieved somewhere around 0.2 sec. Since the experimental rigs are smaller
than industrial furnaces, it was concluded that flame-produced S03 would probably
not significantly affect the S03 levels in industrial flue gases. However, this
conclusion can easily be incorrect if furnace mixing and flame patterns interact
to yield a quick quench.
There are two possible mechanisms for the homogeneous oxidation of S02
in this region. The first is by direct thermal reaction with 02, and the second
involves a catalytic cycle with the nitrogen oxides.
Available evidence indicates that the thermal oxidation
S02 + 1/2 02 = S03 (U2)
proceeds at a very slow rate. Cullis, et al (3^2), and Ladner and Pankhurst (625)
have shown that mixtures of 02 and S02 react at very small rates at about 1000°C.
For example, at 950°C, [S02] = [02] = 2.6 x 10~3 rnole/^, the rate of S03 formation
was found to be ~ 7 x 10"6 mole/£/min in a silica vessel. The rate was shown
insensitive to large surface-to-volume ratio changes. In checking the catalytic
activity of various materials, Barrett et al (615) passed mixtures of air and
0.7$ S02 through a quartz tube. There was no direct data for k2, but the
reaction appeared to be extremely slow. Using the data of Cullis et al (3^2), a
value of
k42f ~ .063 ^ /moles /min
at 950°C is obtained. Assuming a flue gas contains 1000 ppm S02 and 2$ 02, this
yields an S03 formation rate of ~ .02 ppm/sec.
This oxidation of S02 by a catalytic cycle involving nitrogen oxides
appears to be a possible significant contributor to S03 levels of the flue gas.
D. H. Morman of these laboratories, in testing analytical methods for the deter-
mination of S03 in combustion gases, found that additions of 100 ppm N02 to a
39
-------
1
M
Si
10
o
o>
0.008
TZ 0.004
0
co
0)
u
Variation in SO3 Content of Flue Gases Containing
12% CO2 with Flame Temperature
Kerosine; Sulphur Content 2%, added as
Carbon Disulphide
Distillate Fuel Oil; Natural Sulphur Content 3%
I.I.I,
1500
1600
2000
1700 1800 1900
Flame Temperature, °C
Figure 16. EFFECT OF FLAME TEMPERATURE ON SO3 FORMATION
Crumley and Fletcher
2100
S-14129
65854
40
-------
500 ppm S02 stream with a residence time of about 3 sec at 300-UOO°C resulted in an
increase of 5 ppro S03 over that obtained with no N02 added. NO additions were
found to have no effect up to 300 ppm. Shaw and Green (337) found that when NO
(600-900 ppm) plus CO (250-1000 ppm) were simultaneously added to gases with
2000 ppm S02 at ~1000°C, 70-100 ppm S03 resulted after about 1.5 sec. NO additions
by themselves produce no measurable S03. Cullis et al (392), working with high
levels of S02 and 02 (~10~3 moles/^) found that additions of NO of the order of
10~3 moIe/£ increased the rate of formation of S03 by two orders of magnitude.
The basic mechanism for this oxidation is thought to be
S02 + N02 > S03 + NO (U3)
with the N02 being formed by
NO + 0 > N02 (WO
or by
NO + NO + Qs > N02 + N02 (U5)
The chain-branching oxidation of CO in the work of Shaw and Green is presumably the
source of atomic oxygen. Armitage and Cullis (626) obtained a value of
k43 = 1012'8 exp(-27000/RT) cm3/mole/sec for reaction U3. This activation energy
is in excellent agreement with that obtained by Boreskov and Illarionov who find
26500 kcal and show reaction U3 to be extremely rapid. Hence, in furnaces where
the high temperatures preclude high levels of N02, the rate may depend on the
oxidation of NO. Indeed, Cullis et al (3^2) found the rate of S03 formation for
high S02 levels to be given by the rate of oxidation of NO-
Hence, it appears that this mechanism can be a significant source of S03.
At present, furnaces usually produce about 300-600 ppm NO by the fixation of
atmospheric nitrogen in the flame. High peak temperatures and longer residence
times at high temperatures favor NO formation. If one tries to minimize S03
formation by designing for a long, high-temperature soak, this may backfire by
increasing the NO level and thereby the effect of the above S02 oxidation mechanism.
On the other hand, if one tries to minimize NO formation by a quick quench of the
combustion flame, formation of S03 may increase.
Process Modifications to Reduce S03 Emissions
The mechanisms of S03 formation in process heaters described above suggest
several design or operating modifications which might reduce S03 emissions. Some
have been tried; others have not been tried. In any given case, definition of the
specific mechanism leading to the troublesome S03 levels would allow selecting the
best solution.
Low Excess Air Combustion
Since the oxidation of S02 depends on the availability of excess 02 in the
flue gas, reduction of the 02 level should inhibit S03 formation by all the mechan-
isms described above. This has indeed been observed in practice on small burners as
well as large furnaces. Figure 12 shows the effectiveness of 02 reduction on the
41
S-1U129
-------
S03 levels from flames; the S03 level is particularly sensitive below about Wf>
excess air.
Several reports attest to the effectiveness of this operating modification
on large-scale units. Crossley (621) reports that Britain's Central Electricity
Generating Board (C.E.G.B.) has been able to operate oil-fired boilers at 1% 02 in
the flue gas reducing the S03 levels from previous values of JO ppm to about 6 ppm.
Crossley also reports that Deutsche Shell have operated at 0.3$ 02 yielding 10 ppm
S03. Munroe (628) describes the use of 1-5$ excess air in oil-fired forced
converter furnaces. He claims reduction in S03 and nitrogen oxides with clean
(soot-free) combustion. Glaubitz (629) also describes redesign of oil burners to
burn with 1% excess air.
If care is taken to reduce the excess air in the firebox, the work of
Barrett et al (615) indicates that air leakage should be minimized. They found
that if air is injected downstream of a stoichiometric flame appreciable increases
in S03 occur if the gas temperature is still above 2100°F. Of course, any air
leakage will also allow catalytic oxidation and oxidation via the NOX cycle to
occur.
Flame Quench
Although there is no conclusive proof that high S03 levels have been
caused by fast quench of the flame reactions, the possibility still exists. Hence,
it is worthwhile to ensure that extreme quench rates are not obtained. Attention
is directed to the effect of primary and secondary air injection and to the mixing
and flame patterns within the furnace. High S03 levels may be another undesirable
effect of flames impinging upon refractory.
Staged Combustion
Two-Stage Air Addition
Two-stage air addition can minimize the emission of S03 from the flame
region. The major part of the combustion occurs in the flame with a stoichiometric
or sub-stoichiometric atmosphere. The rest of the air needed to complete combustion
is added beyond the flame. Since the oxidizing atmosphere occurs in a region of
lower temperature and lower level of combustion, S03 formation should be minimized.
Reports concerning the effectiveness of this modification conflict.
Austin and Chadwick (630) report no effect on the S03 level, whereas Coykendall (6jl)
reports reductions in S03 level. Both of the above reports indicate substantial
reductions in NOX levels, and it has been reported that NOX levels were substantially
reduced (from lUOO ppm to 250 ppm) at PG&E's Moss Landing power plant by this
technique. In view of the work of Barrett et al (615), who found that significant
increases in S03 occurred if air was added to flue gases above 2100°F, the precise
point of injection of the secondary air is important in determining the S03 emission
reduction achieved by this technique.
Two-Stage Fuel Addition or Reburning
Two-stage air addition minimizes S03 formation in combustion, whereas
two-stage fuel addition would reduce the S03 formed. This could be applied in
situations where it is not possible to burn with sufficiently low excess air to
S-1M29
42
-------
minimize formation. The idea is to add a clean (sulfur free) secondary fuel to the
gases "beyond the flame in sufficient quantities to reduce the resultant flue gas to
0% 02. This should then cause reduction of the S03 emitted from the primary flame.
Recent experiments (623) by Shell indicate that injection of methane and
CO above the flame of a small flat-flame burner in sufficient quantities to reduce
all excess 02 substantially reduces the S03 level.
This idea also forms the basis of U.S. patent No. 3^63599 assigned to
Esso.
The only other report found regarding this technique was a reference (632)
to an attempt by the British C.E.G.B. to reduce S03 levels by injection of CO into
the flue gases. Injection took place at a point where the flue gas temperatures
were 900°F. It is reported that additions of ten times the stoichiometric amount
required to react with all S03 present produced no reduction in the S03 level. The
temperature was probably too low. Perhaps combustion of the added fuel is required.
At 900°F, CO would not be expected to burn.
The Use of Additives
The literature regarding the use of additives to control cold end
corrosion in furnaces and boilers is extensive. However, the results seem unclear
because no one has really performed an exhaustive study of all possible additives
under controlled and comparable conditions.
The basic idea behind the use of additives is to inject into the furnace
environment a component which can
1. Preferentially react with atomic oxygen in the flame to inhibit
S02 oxidation.
2. Chemically react with S03 to remove it from the gas stream.
3. Physically adsorb S03 to remove it from the gas stream.
In some cases, if the additive is fed to the fuel, it can perform more than one of
the above functions. Here, we will restrict discussion to atomic oxygen scavengers,
since the data may give insight into the role of 0 atoms in S02 oxidation.
Several reports (3^5), (6l6), (626) have appeared regarding additions of
constituents to the flame to specifically act as oxygen atom scavengers. Compounds
found capable of lowering S03 levels are ethyl alcohol, benzene, ethyl nitrate,
pyridine, carbon tetrachloride, and nitric oxide (3^5) (in order of increasing
effectiveness) and hydrogen (6l6). Ammonia and steam were also tried (62k) but
found ineffective.
The experiments quoted above (3^5) were performed in a Bunsen burner, where
the SOs levels were measured before the high-temperature oxidation reactions had
time to occur. No tests have been reported for NO additions in furnaces. Until this
is done, the overall effect of NO additions in resultant S03 levels at the stack will
be unclear.
S-11H29 43
-------
Metals in flames can also be good atomic oxygen scavengers. Species
found effective (630), (622), (620), (632), (6jU) as oil-soluble additives, metal
oxide suspensions, or metal suspensions have been Mg, Zn, Ca in order of decreasing
effectiveness. It should be noted that some problems with furnace deposits result-
ing fron these additions have been reported.
In summary, additives may prove useful, but their application on a large
scale has not been demonstrated as problem-free. Indeed, use of gaseous atomic
oxygen scavengers has only been tried on laboratory-scale equipment.
Table 8. AVAILABLE DATA ON THE KINETIC CONSTANT OF THE REACTION
S0
M
M
Source
Jaffe & Klein (635)
Webster & Walsh (636)
Thrush Sc Halstead (63?)
Halstead & Thrush (638)
Kaufman (361)
Mulcahy, Steven £ Ward (3U3)
Levy Sc Merryman (32U)
Merryman 4 Levy (6l?)
Summary of Literature Review
(cms/molesa/sec)
1.U x 1016 (PT = 2 mm He)
0.92 x 1016 (PT = 1 atm]
(M = S02 + N02)
1.0 x 1016 (M = H2 + 02)
3.6 x 1016 (M = Ar)
1».7 * 0.8 x 1015 (M = Ar)
3 x 1016 (M = S02)
2.7 - 0.5 x 1015 (M = 02)
2.U ±0.15 x 1015 (M = Ar)
10 ± k x 1015 (M = S02)
2.2-22 x 1015 exp(-6000/RT)
2.U x 1017 exp(-2500/RT)
Temperature
Room temp
Room temp
293°K
Room temp
300 °K
300 °K
300°K
average value
from literature
The literature review indicates many areas of ignorance and controversy
about the mechanisms by which fuels containing N and S burn and the products
resulting from the combustion. Here we merely reiterate those points which we
think most merit further study.
1. What are the rates and products of pyrolysis of coal and residual oils
and especially how is the nitrogen distributed between the volatile
material and the residual char?
2. What reactions govern the combustion of the nitrogen in chars, and
what is the ratio of N2 to NOX in the products?
3- What reactions govern combustion of cyanides and ammonia^ and what
are the rates of the elementary steps?
S-1U129
44
-------
U. How is the N-to-N bond formed in combustion of fuel nitrogen?
5. How is S03 formed in furnaces?
6. How does the presence of nitrogen oxides affect the oxidation of S02?
7. How does inhibition caused by the presence of S02 affect the formation
of nitrogen oxides?
8. Can the pollutants S03 and NOX be reduced to less noxious forms by
homogeneous gas-phase reactions, and if so, how can this be done
practically?
9. By what mechanism is "prompt" NO formed?
10. What reactions besides the Zeldovich pair contribute significantly
to fixation of atmospheric nitrogen?
11. Finally, how may the complex physical and chemical process occurring
in furnaces be modeled mathematically in a practical fashion?
45
-------
Results of Modeling Studies
Some of the questions listed in the previous section can be answered, at
least partially, through computer-aided modeling of chemical mechanisms. In this
section, we report the results for six such studies. Treated are: (l) Prompt NO
via cyanide intermediates; (2) Fixation of atmospheric nitrogen; (3) Fate of fuel
nitrogen in a gaseous diffusion flame; CO S03 formation by uncatalyzed reactions;
(5) Synergistic reactions of SOX and NOX; and (6) Reduction of NO by H2 in a
secondary flame (reburning). Each of the studies is described in detail below.
"Prompt" NO by Cyanide Reactions
Fenimore (721) noted that substantial amounts of NO were formed very
rapidly in the flame front of methane-air flames but not in CO-air or H2-air
flames. He suggested that reactions such as
CH2 + N2 = HCN + •••
C2 + N2 = CN + CN
might be responsible for the breaking of the N5N bond. Subsequent reactions of HCN
and other molecules containing a single nitrogen atom could easily lead to nitrogen
oxides. An alternative suggestion for the formation of "prompt" NO is that the
chain-branching reactions involved in fuel combustion generate super -equilibrium
concentrations of free radicals, especially 0 atoms, which then react rapidly with
N2. This explanation, treated in more detail in the next section, cannot explain
the observation of Fenimore that CH4 flames made much prompt NO while CO and H2
flames did not.
To test the Fenimore conjecture quantitatively, we have set up a model
for methane combustion involving, in addition to generally accepted reactions, the
following
CH3 + OH = CH2 + Hj.0 PROM 1
CH3 + N2 = HCN + NH2 PROM 3 (50)
CH2 + N2 = HCN + NH PROM 2 (51)
CH2 + 02 = HCO + OH PROM k (52)
With the intention of finding a maximum possible rate of N2 fixation by the cyanide
route, we have taken maximum conceivable rates (steric factor of unity) for
reactions PROM 1, PROM 2, and PROM 3 and a rather low rate for PROM U. Table 9
shows the complete set of reactions considered, and Table 10 gives the reaction
rates used for those reactions not included in our library of Arrhenius parameters
(Appendix l).
(*) Equation 46 intentionally omitted.
-------
Table 9. REACTIONS INCLUDED IN THE CYANIDE ROUTE TO PROMPT NO
1.
2.
3.
k.
5.
6.
7.
8.
9.
10.
11.
12.
13.
1U.
15-
16.
17.
IB.
19.
20.
21.
SBOW 1
SBOW 2
SBOW 3
SBOW ^
SBOW 5
SBOW 6
SBOW 7
SBOW 8
SBOW 9
SBOW 10
SBOW 11
SBOW 12
SBOW 13
SBOW Ik
SBOW 15
SBOW 16
SBOW 18
PROM 1
PROM 2
PROM 3
PROM U
Table 10.
Reaction
CH4 + M +
CRt + 02 +
02 +M +
CH4 + 0 +
CRi + H +
CH4 + OH +
CH3 + 0 +
CH3 + 02 +
HCHO + OH +
CHO + OH +
CO + OH +
H + 02 +
0 + H2 +
0 + HS.O+
H + H20+
H + OH +
CHO + M +
CH3 + OH +
CH2 + N2 +
CH3 + N2 +
CH2 + 02 +
ARRHENIUS PARAMETERS USED IN
PROMPT NO VIA CYANIDES
Rate Expressions^
Forward
= CH3 + H + M
= CH3 + H02
=0 +0 +M
= CH3 + OH
= CH3 + H2
= CH3 + H20
= HCHO + H
= HCHO + OH
= CHO + HsP
= CO + HjjO
= C02 + H
= 0 + OH
= H + OH
= OH + OH
= H2 + OH
M = HaO + M
= H + CO + M
= CH2 + H20
= HCN + NH
= HCN + NH2
= HCO + OH
STUDY OF
cm3A sec, g mole
Reverse
PROM 1 CH3 + OH = CH2 + H^ .771 x 1015 exp(-1060/RT) .296 x 1016 exp(-9210/RT)
PROM 2 CH3 + N2 = HCN + NH2 .U6 x 1016 exp(-19000/RT) .605 x 1015 exp(-26lO/RT)
PROM 3 CH2 + N2 = HCN + NH .20^ x 1016 exp (-^1700/RT) .731* x 1015exp(-l950/RT)
PROM U CH2 + 02 = HCO + OH .758 x 1015exp(-1700/RT) .678 x 1014 exp(-90900/RT)
47
-------
The initial calculations were for a plug flow reactor, isothermal at
2100°K, burning methane at llU.2# of theoretical air. This corresponds to a feed
composition:
Species Mole Fraction
CH4 .081*02
02 .1919
N2 .721*1
Large quantities of HCN, NH, and NH2 were produced indicating that Fenimore's
mechanism can be significant if the rates of reactions PROM 1 to 3 are large enough
and the rate of reaction PROM 1* is low enough. Further work appears justified to
find a set of rates consistent with the yields of prompt NO found by Fenimore and
by others [especially Lange (5UU)]. Such a model, however, will remain conjectural
until a firmer base is found for estimating the rates of reactions PROM 1 to PROM k
and of other rates which might be important.
Some results from the run described above are:
Residence time, sec 0 10"5 10"3
Mole Fractions
CRt .08U .039 10-10
CH3 0 .0011* 10-10
CH2 0 10-5 10-11
OH 0 .0022 .008
HCN (in ppm) 0 1120 1.0
NH (in ppm) 0 9UO 1.0
NH2 (in ppm) 0 200 0.01
Hence, it appears that the compounds with one nitrogen atom appear at the 1000 ppm
level in periods of 10 microseconds and then decay back to equilibrium. Remember
that in this calculation no means was provided for oxidation of HCN, NH2, and NH.
In a real flame, such oxidation would be expected to convert an appreciable fraction
(say, one-half) of these compounds to NO.
Of the two reactions
CH3 + N2 = HCN + NH2 (53)
CH2 + N2 = HCN + NH
the latter is the more important according to this model.
Fixation of Atmospheric Nitrogen
Basic to any model for the prediction of the NO content of the gases
produced by a combustion process is the mechanism by which the nitrogen in the
atmosphere is converted into NOX. Since the time of Zeldovich (5^2), it has been
known that the most important reactions, at least for normal combustion, are
N2 + 0 = NO + N (55)
N + Oa = NO + 0 (56)
s-11*129
48
-------
It is possible, however, that reactions other than these are sometimes important.
Moreover, the rate constants for 55 and 56 are not known exactly, and there exists
some controversy about how the concentration of oxygen atoms is to be calculated.
We investigated these points by comparing computer-generated solutions for several
mechanisms with the data of Lange (5UU). Since it is the most complete published
to date, the model proposed by Lange was taken as a point of departure.
The successive computer runs were designed to each answer a specific
question.
1. With regard to both N-N bond rupture and NO bond formation, which
reactions in the scheme of Lange are significant?
2. Do the additional reactions suggested by Wilde (753) contribute
to NOX make?
3. What error results from shortening the set of 21 reactions of
Lange to only those found significant on the one hand and to the
Zeldovich reactions on the other hand?
U. Can prompt NO be predicted by eliminating the assumption of
equilibrated radicals and considering the nitrogen fixation
simultaneously with methane combustion?
5. What is the best set of reactions and rate constants for prediction
of fixation?
The results of the runs can best be described in reference to Table 11
which shows the reaction scheme used, the physical conditions, and the answers
obtained for each run. Additional details are discussed below.
In run Lange 2, we added to the 25 reactions of Lange (5^*0 the two
additional reactions suggested by Wilde (773).
HNO + NO = NaO + OH (57)
HNO + HNO = NaO + HaO (58)
The assumption of equilibrium radical concentrations was met by
introducing artificially large rate constants for reactions
02 = 0 + 0 (59)
HaO = OH + H (60)
H + 02 = H02 (61)
In program EXHAUS there is no difficulty in accurately calculating the true
deviation of these species from their equilibrium values; this approximation was
made only to facilitate comparison with Lange's own theoretical results. The
computer printout for run Lange 2 gave directly the rates of each reaction at each
step of the integration. From these rates, Figures 17 and IB were worked up.
These show what fraction of the NO bonds made, or NN bonds broken, can be attributed
to each reaction. For the conditions of this run (llU.2^ theoretical air and no
S-1U129 49
-------
Table 11. FIXATION OF ATMOSPHERIC NITROGEN—SYNOPSIS OF COMPUTER RUNS
Run No.
Lange 2
Purpose of Run
Determine which
reactions contri-
bute to
Reactions Used
LANG 1 to LANG 21
WILD 1 - WILD 2
Equilibrium of
Radicals
Reaction
Conditions
Those of Lange
Expt. No. 2
llU.2£ theo air
110 preheat
plug flow
specified time-
temp history
Results
Conclusions
66 ppm NOX made in 0.1 sec
compared with 300 ppm ob-
served experimentally of
which 100 ppm is "prompt"
See Figures 17 and IB.
I. Only reactions LANG 1, LANG 8, LANG 10
contribute significantly to N=N bond
breakage.
2. Only Reactions LANG 1, LANG 7, LANG
1U, LANG 9, LANG 3, LANG 8, LANG 5
contribute significantly to N-0 bond
production.
Lange 3 What fraction of
the NOX made can be
accounted for by
the Zeldovich
mechanism alone
Fran run Lange 1
delete all N fix-
ation reactions
except LANG 1 and
LANG 7
Same as Lange 2 5U ppm NOX made in 0.1 sec
Roughly 80$ of the NOX produced under the
conditions of this run can be attributed
to reactions LANG 1 and LANG 7.
Lange k Establish base NOX
for Zeldovich
mechanism alone but
for low excess air
Same as Lange 3
102.2$ theo air 136 ppm NOX made (compared
no preheat plug to 6bO ppm NOX experimen-
flow tally found)
specified time-
temp history
Lange 6 Determine how much
other reactions in
Lange model con-
tribute to MDX
Same as Lange 2 Same as Lange k 138 ppm NOX
98$ of NOX is accounted for by the
Zeldovich Mechanism under these
conditions of low excess air (high
temperature)
Fris 8 Test whether prompt See Table 11
NFIX U NO can be predicted Adjusted rates of
by integrating Lange used for
simultaneously LANG 1, LANG 2,
Methane combustion and LANG 9
and fixation
Same as for
run Lange 2
llU.2* theo air
no preheat
adiabatic flame
front and plug
flow
See Figures 19, 20
By considering the interaction of methane
combustion with the nitrogen fixation,
prompt NO can be predicted. The ratio of
prompt NO to post-flame NO is the same as
in the experiments of Lange, but the
absolute values of both are low by about
23*.
-------
I 2
•| i.o
C
_o
u
ID
0)
X
_Q
£ 0.8
o.
CO
c 0.6
u
10
0.4
20
Reaction 10
N2O + O2 = NO + NO2
Reaction 9
N2O + O = NO + NO
Reaction 1
O + N2 = NO + N
I
40
Step Number
60
80
Figure 17. SPLITTING OF N-N BONDS
LANGE RUN 1
S-14129
68275
51
-------
1.0
-o 0.8
£
15
o
TJ
o
"o
ID
£ 0.6
X
_Q
-8
(0
k.
£§ 0.4
O
z
u
ID
£ 0.2
All Others-
N2 + O2 = N2O + O-
N + OH = NO + H
N2 + O + M = N2O + M_
N2O + O = NO + NO
NH+OH =
N + O2 = NO + O
O + N2 = NO + N
1
14
20
40
Step Number
"Reaction
No.
60
80
Figure 18. PRODUCTION OF N-O BONDS
LANGE RUN 1
S-14129
68275
52
-------
preheat) and for the rates used one can conclude that 13 of the 21 reactions of
Lange and both of the reactions of Wilde can be dropped. Of the remaining reactions,
the Zeldovich pair LANG 1, LANG 1, account for about 65$ of the NN bonds broken and
for 60% of the NO bonds made. This conclusion was checked by run Lange 3, similar
in all respects to Lange 2, except that only the Zeldovich reactions were retained
of all the fixation reactions. Only 22# additional NOX results from including the
other 19 reactions of Lange's mechanism.
A similar comparison was made for a run with low excess air (computer runs
Lange U and 6). Here, the temperature is higher. Almost all (98$) of the fixation
is accounted for by the Zeldovich mechanism.
A large discrepancy between theoretically predicted NO and that observed
experimentally is displayed by runs Lange 2 to Lange 6, as shown oelow.
NOx at 0.1 second Residence Time
Percent of Experimental Predicted
Theoretical Air Prompt Total
11U.2
102.2
Thus, the Lange mechanism, using original rate constants, and assuming equilibrium
concentration of free radicals, accounts for none of the prompt NO and for only
one-third or less the post-flame NO. Lange met this problem by arbitrarily
adjusting the rates for three reactions:
Adjustment
Factor
LANG 1 N2 + 0 = NO + N 2.85 (62)
LANG 2 N2 + H02 = NO + HNO 0.2?^ (63)
LANG 9 N.,0 + 0 = NO + NO U.95 (6U)
The adjustment to reaction LANG 1 is not unreasonable. The rates recommended by
Baulch et al (?86) are only 30# lower than the adjusted value of Lange and hence
lie well within the range of uncertainty given by Baulch. The adjustments to
LANG 2 and LANG 9 seem to have no justification other than the good agreement
thereby produced between model and experiment. These values cannot now be
recommended for general use; obviously, more data are urgently required.
A further series of runs were made on nitrogen fixation to determine how
the methane combustion interacts with the fixation reactions. The intent was to
calculate as accurately as is now practicable the entire course of the combustion
including the heat balance and the effects of diffusion in the flame front.
The calculations were made at the conditions of Lange's experiment No. 2
and were made with heat balance assuming that heat is lost by radiation at the
rate 0.9^2 x 10~14cal/sec cm3K4, a value which closely predicts the measured
temperature profile of Lange. Some explanation of the method of calculation is in
order. First, we selected a mechanism for methane combustion which would reproduce
approximately the following types of data: (l) ignition delay data in shock tubes,
S-1U129 3
-------
as measured by, for example, Seery and Bowman (526); (2) free radical and formal-
dehyde concentrations as measured by Fristrom (787); and (3) reaction rates in a
Longwell reactor as measured by Morgan (788). The reaction scheme used is shown in
Table lla. It does agree fairly well with data of the types mentioned (e.g., 0 atom
concentrations within a factor of 2 of Fristrom's values;. A detailed comparison
is outside of the scope of this project; and in fact, the subsequent calculations
show that a very accurate methane burning model is not required. The methane has
been consumed almost completely Before nitrogen fixation starts. Second, we
simulated the flame front by a "point-wise" calculation at the flame section where
the methane conversion is 90$. The method of doing this is explained in Appendix
III. A calculation like this is needed to produce flame ignition, when the feed
temperature is low. Third, we continued the calculation as for a heat balanced
plug flow reactor using the output temperature and composition for the point-wise
calculation. As mentioned above, a radiation heat loss was incorporated to
properly predict the experimental temperature. We noted that the combustion of
CH4, CH3, HCHO, and CHO was substantially completed in a very short time,
approximately 200 microseconds, and in this time almost no nitrogen is fixed, and
negligible heat is lost. In fact, the fixation process can be predicted by
considering only the CO combustion provided that the initial conditions properly
reflect the "debris" left by the combustion of methane (and the short-lived
intermediates, CH3, HCHO, and CHO). The calculated debris for the conditions of
this run is shown in Table 12. In most of our subsequent runs, we started with
this composition and temperature.
Predicted temperature is compared with Lange's measurements in Figure 19,
showing the good agreement attained with the heat loss rate selected. A very
important point revealed by the calculations was that the temperature is fairly low
during the period when prompt NO is being made because the large concentrations of
free radicals absorb much heat on dissociation.
Figure 20 shows predicted and experimental NO profiles. In making these
calculations, only the Zeldovich fixation reactions and the reactions LANG 3, LANG U,
LANG 5, LANG 6, LANG 8, LANG 9, and LANG 10 involving NaO were used. The adjusted
rate constants of Lange were used. If the original rate constants tabulated by
Lange had been used, the predicted NO would have been much lower but the functional
relation with time would have been similarly shaped.
This calculation shows that the formation of prompt NO can be predicted
by considering the combustion concurrently with fixation. Because of the low
temperature prevailing during the formation of prompt NO, the reactions involving
NgO are relatively important compared to the Zeldovich reactions, especially if we
accept Lange's large adjustment to the rate of reaction, LANG 9.
NOY Reduction by Secondary Fuel Injection or Reburning
Much has been published on mechanisms of foraiation of NO in flames. Very
little has been published on reduction of NO in flames. An understanding of NO
reduction mechanisms is important for a number of reasons. First, reburning of NO
to N2 may be a useful NO control method for emissions from coal-fired combustion
units, where the primary coal flame must be operated at excess air in order to main-
tain flame stability and prevent foraiation of soot. Second, in the combustion of
oil droplets and coal particles it appears that much of the chemically bound
nitrogen remains in the char, which is then consumed by a surface reaction with 02
molecules to produce CO. A surface reaction with atoms in the char might similarly
S -1M29 54
-------
Table lla. REACTIONS USED FOR COMBINED
METHANE-BURNING AND NITROGEN FIXATION
Computer Runs FRIS-8. NFIX-^
SBOW 1 CH4 + M = CH3 + H + M
SBOW 2 CH4 + Oa = CH3 + H02
SBOW U CH4 + 0 = CH3 + OH
SBOW 5 CH4 + H = CH3 + H2
SBOW 6 CH4 + OH = CH3 + HaO
SBOW 7 CH3 + 0 = HCHO + H
SBOW 8 CH3 + 02 = HCHO + OH
SBOW 9 HCHO + OH = CHO + HjsO
SBOW 10 CHO + OH = CO + HaO
LDSA 1 CO + OH = C02 + H
SBOW 18 CHO + M = H + CO + M
BROK 18 H2+M = H+H+M
JOHN 11 02+M = 0+0 + M
HOMER 1 H + OH + HaO = HaO + HaO
HOMER 2 H-t-OH+M = HaO+M
BROK ^A H + 02 + HaO = H02 + H20
BROK ^B H + 02 + M = H02 + M
LDSB 1 H2 + 0 = H + OH
LDSB 3 H2 + OH = H20 + H
LDSB 5 HsO + 0 = OH + OH
LDSC 1 02 + H = 0 + OH
BROK 6 H + H02 = OH + OH
THORN 1 H02 + OH = 02 + H^
BROK 8 0 + H02 = OH + 02
BROK 10 H + H02 = H2 + 02
LDSD 3 02 + N = NO + 0
IANG 1 Adj N2 + 0 = NO + N
IANG 3 N2 + 0 + M = N20 + M
LANG k N2 + OH = NsO + H
LANG 5 N2 + 02 = N20 •«• 0
IANG 6 N2 + N02 = N20 + NO
IANG 8 N + OH = NO + H
IANG 9 Adj N20 + 0 = NO + NO
IANG 10 NsO + 02 = NO + N02
55
-------
Table 12. "DEBRIS" FROM THE COMBUSTION OF METHANE WITH AIR
IN A PHEMIXED FLAME
Conditions of Calculation
114. 2# of theoretical air (dry)
298 °K feed temperature
200 pS residence time in flame front and post -flame region
required to destroy 99-99># of methane
1770°K debris temperature
~2100°K adiabatic flame temperature
Combustion Debris Mole Fraction
o .0401
N2
H .00598
H02 -231 x 10-4
0 .00469
OH .00711
H2 .00711
HaO .154
CO .0306
C02 .0534
56
S-14129
-------
2100
2000
V
^
o
S 1900
2
Q>
Q.
E
o>
1800
1700
Calculated with Heat Loss Rate
..934x 10-|4cal/seccm3K4
O Measured Lange's Run No. 2
4000 8000 12000 16000 20000
Reaction Volume, cm3/(gm mole/sec)
Figure 19. PREDICTED AND EXPERIMENTAL TEMPERATURES FOR
COMPUTER RUN NFIX4
S-14129
68275
57
-------
103
Measured Lange's Run No. 2_
Predicted Computer Runs
FRIS-8, NFIX-4
10
20000
4000 8000 12000 16000
Reciprocal Space Velocity, cm3/(gm mole fed/sec)
Figure 20. PREDICTED AND MEASURED NOX PRODUCTION
S-14129
68275
58
-------
form NO. Hence, one explanation of the fact that only about 4o# of the chemically
bound nitrogen is converted to NO may be that much of the NO formed at the char
surface is reduced back, by returning, in the CO diffusion flame surrounding the
particle. An understanding of the mechanisms of returning would help to test this
conjecture. Third, the study of the mechanism of returning should provide insight
into which reactions are necessary for NO formation in diffusion flames, where the
fuel-rich regime is important.
The experimental study of Wendt, Sternling, and Matovich (623) showed that
reburning was effective for NO reduction and that up to 50# reduction in NO was
obtained from flue gases. A recent patent of John Zink Company (6^1) deals with
the homogeneous conversion of NO to N2 by combustion in a fuel-rich environment.
The specific purpose of the study reported here was to answer the following
critical questions:
1. Is the Zeldovich mechanism, or its reverse, adequate to explain the
reduction of NO in fuel-rich combustion?
2. If not, what are the other important reactions, and what are the
intermediate species?
3« What is the effect of the composition of gas mixture? Is reburning
by hydrogen more or less effective than reburning by CO or hydrocar-
bons? What is the effect of C02 in the gas mixture?
U. What is the route through which the N-N bond is formed from NO?
The approach adopted was to use the kinetic mechanism shown on Table 13
as a base. This mechanism is based on the rate coefficients of Lange (5^) and of
Wilde (6k2) except for those reactions that had been investigated in the Leeds
reports (786). Results shown on Table lU indicate that according to this mechanism
NO can be reduced by hydrogen. The reduction takes place in the order of 0.02
seconds.
In order to investigate which reactions and which species played a role
in the NO reduction, we divided the reactions into four groups. Group 1 consisted
of those reactions destroying NO, Group 2 consisted of those reactions that make N2,
Group 3 consisted of those reactions that split the NO bond (this includes the
destruction of HNO), Group k consisted of those reactions that make N atoms. The
relative importance of the reactions is shown below:
Important Reactions
5f, 12r, 14f, 15f, 22r
5f, 22r
5f, 22r, 26r, 32r
5f, 6f, 7f, 26r, 29r, 30r, 31r
The reaction numbers correspond to those on Table 13, and the designation f and r
denote if the reaction is going in the forward or reverse direction. This analysis
led to the conclusion that the mechanism of NO reduction was as follows: Nitrogen
atoms are built up by the "shuffle," or equilibrated, reactions involving HNO, NH,
H, OH, H2. These N atoms then react with NO via the reverse Zeldovich:
S-1^129 59
-------
Table 15. REACTIONS USED IN REBURNING MODEL
1.
2.
3-
1*.
5.
6.
7.
8.
9«
10.
11.
12.
13-
Ik.
15-
16.
17.
18.
19-
20.
21.
22.
23-
21*.
25-
26.
27-
28.
29.
30.
31.
32.
33-
35.
36.
LDSB
LDSB
LDSB
LDSC
LDSD
LDSD
LDSD
LDSE
LDSE
LDSE
SBOW
WILD
WILD
WILD
WILD
WILD
WILD
WILD
1
3
5
1
1
3
11
1
3
6
3
1
5
6
7
9
10
11
HOMER 1
HOMER 2
LDSA
IANG
IANG
IANG
IANG
IANG
IANG
IANG
IANG
IANG
IANG
IANG
IANG
IANG
IANG
IANG
1
2
k
5
6
8
9
10
11
12
13
Ik
15
16
17
21
H2
Ha
HaO
Oa
NO
02
N02
NOa
N02
NO
Oa
Ha
NaO
HNO
H
HNO
HNO
NaO
H
H
CO
Na
N2
Na
N2
N
N20
NaO
N
N
N
NH
NH
NH
NH
HNO
+ 0
+ OH
+ 0
+ H
+ N
+ N
+ N
+ 0
+ M
•»• NO +
+ M
+ NO
+ H
+ OH
+ NO +
+ NO
+ HNO
+ M
+ OH +
+ OH +
+ OH
+ HOa
+ OH
+ 02
+ NOa
+ OH
+ 0
+ 02
+ OH
+ H2
+ H20
+ OH
+ 0
+ OH
+ 02
+ 0
a
=
-
=
=
=
=
=
=
02 =
=
=
=
=
M =
=
=
=
HaO =
M =
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
H +
HaO +
OH +
0 +
N2 +
NO +
NO f
NO +
NO +
N02 +
0 +
HNO +
N2 +
NO +
HNO +
NaO +
NaO +
N2 +
HaO +
H20 +
C02 +
NO +
NaO +
N20 +
NsO +
NO +
NO +
NO +
NH +
NH +
NH +
NO +
NO +
HNO +
HNO +
NO +
OH
H
OH
OH
0
0
NO
Oa
0 + M
NOa
0 + M
H
OH
H20
M
OH
HaO
0 + M
HaO
M
H
HNO
H
0
NO
H
NO
NOa
0
H
OH
H2
H
H
0
OH
S-11H29 60
-------
Table lU. "NO" REDUCTION BY HYDROGEN. NO "CQg" IN MIXTURE
Temperature 1900°K
Run
WILD If
WILD 5
WILD 6
WILD 5A
Time
sees
0
.003
.05
Result
0
• 5
Result
0
.002
1.0
Result
0
1.6
Result
Hg
.62
.1*73
.1*60
: NO
.62
.1*6
Og
• 07
•176(-7)
•76l(-9)
Ng
.29 .
.295 •
.300 .
almost completely
.07
•80(-9)
.29 .
.30 .
NO
02
0105
228 (-1*)
reduced
02
201 (-1*)
: same as previous run
.38
.137
.12
: NO
.62
.1*8
.12
.102(-6)
,ifif5(_7)
reduced
.07
TO/ O \
• .Lt I ™O /
: insignificant
.1*8
.1*82 .
.1*89 .
• 29 .
.29 .
02
0159
5M-10
02
1996(-D
NO reduction
HpO CO COg Notes
Complete 3d.net ic
. 146 mechanism
.160 36 reactions
$ = 8.8
Simplified Mnetic
mechanism; 21
reactions; ffi = 8.8
8 = 1.5 Simplified
mechanism
Zeldovich only.
Conditions same as
WILD 5« fl> = 8.8
61
-------
N + NO = N2 + 0 (66)*
which is faster, under fuel-rich conditions, than
N + 02 = NO + 0 (67)
because of the low Q2 concentration. It appeared, therefore, that under fuel-rich
conditions there is no need for those reactions involving NaO, NOa, etc. A subse-
quent run using only 21 of the original 36 reactions confirmed this (see Table l*f).
The Zeldovich mechanism alone is inadequate (Table I1*) because of the slow rate of
formation of N atoms through
0 + NO = N + 02- (68)
Since an important application of the idea of NO reduction by reburning involves
secondary fuel injection into furnace flue gases, this was simulated in the computer
runs shown on Table 15. Although NO can be reduced, this appears to occur slowly
and only under very fuel-rich conditions. This is in contrast to the data of Wendt
et al (623) who found substantially more NO reduction with reburning in a flue gas
environment. In those experiments the residence times were of the order of 0.1
seconds, indicating that the NO reduction measured was much more rapid than that
predicted by this model when COa is present.
According to our theoretical model of NO reduction, it appears that C02
acts as an inhibitor, due to the conversion of COa to CO which requires consumption
of Ha« Since this has not been observed in practice, it appears that our model is
not complete and that possibly some reactions involving cyanides may play a role.
If this is so, these cyanide reactions would essentially be the reverse of Fenimore's
prompt NO reactions and might lead to substantial cyanide emissions under reburning
conditions.
From this study we can reach the following conclusions:
1. The Zeldovich mechanism alone is not adequate to explain the reduction
of NO under fuel-rich conditions. An expanded kinetic mechanism was
found that predicted this.
2. In the absence of compounds containing carbon, the important reactions
are those that build up nitrogen atoms via intermediate compounds such
as HMO, NH, etc.
3- However, this model does not predict the correct rate of NO reduction
in the presence of C0a« Other reactions involving cyanides may be
important.
4. The N-N bond is formed through N + NO = N2 + 0 (reverse Zeldovich)
where the N atoms are produced through other reactions.
(*) Equation 65 intentionally omitted.
62
-------
Table 15. NO REDUCTION IN PRESENCE OF C03
Temperature 1900°K
Run
WILD 7
Time
sees
0
.02
1.0
HP
.123
.038
.029
COp
.1
.05
.058
HpO OP
.1 .015
.184 .21 (-6)
.194 .21(-6)
NO
.022
.0159
.0036
.64
.643
.651
CO
.05
.042
Notes
$> = 4.1
Result: NO reduced - but more slowly
WILD 3 0 .026 .088 .177 .01 .01 .6890 g = 1.3
.03 .196(-2) .0841 .201 .2l4(-4) .0097 .689 .0039
.87 .126(-2) .0854 .202 -526(-4) .0076 .690 .00256
Result: NO reduced slightly
S-14129 63
-------
Oxidation of Fuel Nitrogen in a Diffusion Flame
The fuels which contain large amounts of chemically bound nitrogen are
coal and residual oils, both of which are usually burned in turbulent diffusion
flames. An idealized mathematical model of the diffusion flame involving both the
physical and chemical aspects is, therefore, expected to be a useful tool in
improving our understanding of the fuel nitrogen reactions. A preliminary version
of a model is described here for hydrogen fuel with bound nitrogen simulated as
free nitrogen atoms. Such a model is based on the idea that reactions such as
CN + 0 = CO + N (69)
may be important in the flame. The model predicts the known result that the
fractional conversion to NO goes up as the weight percent of N in the fuel goes
down. It also predicts that conversion to NO (rather than N2) is favored by high
intensity of combustion and by high temperature.
The simplest model of a diffusion flame [Burke and Schumann (789)] pictures
all the combustion reactions as occurring at a flame sheet of infinitesimal thickness.
The location of the flame sheet adjusts itself so that the rates of diffusion of
fuel and of oxidizer up to the flame sheet are in exact stoichiometric ratio. For
determining overall rates of combustion, flame lengths, flame temperatures, etc.,
this is a reasonably accurate picture when the combustion rates are indeed very fast
compared to rates of diffusion. However, for predicting the products of combustion,
the flame sheet model must be elaborated to take into account the fact that some of
the combustion reactions are faster than others. For example, in burning methane,
it is found that the steps leading to carbon monoxide are much faster than the
combustion of CO to C02«
There are several ways in which the flame sheet model may be extended to
permit the calculation of the products of combustion. Figure 21 shows some of the
mechanistic models for representing various types of laminar and turbulent diffusion
flames, both attached and separated from particles in motion. If proper ignition
has occurred and if the rates of diffusion and stretching are not too great, there
will be a flame sheet of small thickness somewhere between the fuel and oxidizer.
Very rapid mixing can serve to "blow out" the flame so that the mixing is largely
completed before combustion in which case models based on premixed flames are more
appropriate than flame sheet models.
To establish approximately the conditions at a flame sheet, we will
consider Model 21-b in more detail. We picture the combustion up to CO as much more
rapid than the destruction of CO. Then, at the flame sheet, the rates of diffusion
of fuel and of oxygen will be approximately in a ratio to satisfy the equation
m
)2 = nCO + | H20 (70)
The flame sheet will have a finite thickness such that the rate of reaction (70) is
just as fast as the rate of diffusion of reactants up to the flame front and such
that concentration of oxygen within the flame front is that required to make
diffusion and reaction balance within the flame front. These ideas can be expressed
quantitatively as follows. Referring to Figure 22, we consider five zones arranged
parallel to a flame front. The bulk of the fuel and of the oxidizer gas can be
considered to be uniform in composition and temperature due to the fact that the
S-1U129 64
-------
Flame Shee
A. Flame Attached to Particle
Bulk
Fuel
Location of
Flame Sheet
Flame
Front
Bulk
Oxidizer
/ \
Zone where
Diffusive Fluxes
are Significant
B. Microscopic View of
Region Spanning the Flame Front
Initially
After Time St
C. Turbulent Diffusion Flame
with Stretch
Figure 21. MECHANISTIC MODELS OF FLAME SHEETS OCCURRING
IN DIFFUSION FLAMES
S-14129
68275
65
-------
Fuel Gas
(Uniform
Composition,
and Temperature)
Fuel Profile'
Zone
A
Zone
R
Zone
B
(Reaction
Zone)
Oxidizer Gas
(Uniform Composition
and Temperature)
Profile
CO Concentration
(Similar Curve for
H20)
Figure 22. FLAME SHEET MODEL FOR SITUATION B
S-14129
68275
66
-------
influence of the flame has not yet been felt by them. Between these two layers,
the composition and temperature vary due to the diffusion and convection of heat
and mass up to or away from the flame front. In Zone A, there is no oxygen and,
hence, no reaction. Similarly, in Zone B there is no fuel and also no reaction.
In Zone R, of small thickness relative to Zones A and B, there is reaction since
both fuel and oxygen are present. The total thickness, I, of Zones A, B, and R
must be estimated from an appropriate model of mass transfer, such as the
penetration model, the Whitman two-film model, or one of the more precise boundary
layer models. For the present purposes we take i to be known and assume that a
steady-state calculation may be made to determine the reaction zone thickness.
Under these assumptions, the following equations must be satisfied.
dNj_
dx
where yj = mole fraction of species i
x = distance perpendicular to flame front, ft
Nj[ = molar flux of component i in the direction of increasing x,
Ib moles /hr ft2
pm = molar gas density, Ib moles/ft3
DJJ = the binary diffusion coefficient for species i in species j, ft2/hr
Ri = the rate of formation of species i per unit volume due to chemical
reactions
q = the total heat flow, in the direction of increasing x, Btu/ft2 hr
Hi = the molar enthalpy of species i, Btu/lb mole
k = the gas thermal conductivity, Btu/hr ft °F
Neglected in this formulation is thermal diffusion.
Since we do not know the kinetic mechanisms precisely, it seems appropriate
to make several approximations to make the solution to these equations more tractable
and to show more clearly their physical significance. Ultimately, these approxima-
tions will be removed without, we think, altering greatly the main conclusions. We
therefore take DJ.J equal for all i and j, we take the total mass flux Np = EN,- to be
zero, we take DJJ and k to be independent of temperature and composition, and we
set Hi = Hi0 + Cpi(T-To). Inside the reaction Zone R we take the profiles of mole
fraction to be quadratic in x such that the value and the slope of yj are zero at
one edge of R and such that the diffusive flux at the other edge of R matches the
diffusive flux in zone A or B as appropriate. We require the kinetic express! CDS
to be satisfied in the center of the reaction zone. It can be shown with these
assumptions that the thickness and Qs concentration in the reaction zone are
related to an equivalent well-stirred reactor which satisfies the following
conditions
S-14129 67
-------
where tg, the thickness of Zone B, is given by
S.
The other symbols are:
V/Fj = the volume per mole of feed of an equivalent well-stirred reactor
representing the mid-point of the flame front, cm3 sec/g mole
Pm = molar density, g mole/cm3
DQ = diffusion coefficient of oxygen, cm2/sec
!• = thickness of mass transfer boundary layer, cm
n = atoms of carbon in each fuel molecule
m = atoms of hydrogen in each fuel molecule
Df = diffusion coefficient of fuel molecule, cm2/sec
y° = mole fraction of fuel in fuel stream
yj = mole fraction of Og in oxidizer stream
It can be seen from these expressions that the products initially formed at the
flame front will depend on the "intensity" of combustion as defined by
r _ PmD(V/FT)
CI " £
High combustion intensity will lead to thick flame fronts, high 02 concentration in
the flame front, and hence will probably favor such reactions as
N + 02 > NO + 0 (71)
over such reactions as
N + NO > N2 + 0 (72)
Some calculations were made using this idea of the equivalent well-stirred reactor
to investigate the combustion of mixtures of H2 and HCN. The HCN, which is one of
the products of pyrolysis of fuel compounds containing nitrogen, is simulated by N
atoms. The kinetic scheme used is shown in Table 16. The hydrogen combustion
scheme was selected to exhibit most of the known features of hydrogen flames (598).
For conversion of the nitrogen atoms, only the Zeldovich reactions and the direct
three-body recombination of N were used. Future studies would certainly involve
more reactions.
Results are plotted in Figure 23, showing the calculated effects of
combustion intensity and of temperature. Table 17 shows, in addition, the effect
of fuel nitrogen level.
It is seen that the diffusion flame model predicts qualitatively the same
trend of conversion with N level in the fuel as has been observed. FurthernDre, it
predicts an effect of combustion intensity such that more rapid combustion leads to
more NO and less N2>
S-U129 68
-------
This effect can be understood in terms of the competing reactions
N + 02 = NO + 0 (73)
N + NO = N2 + 0 W
Low combustion intensity leads to consumption of almost all of the 02 in the
reaction zone permitting reaction 7^ to compete effectively with reaction 73«
Figure 23 also shows that low temperature favors conversion of fuel nitro-
gen to N2 at least for the very simple mechanism tested. Such an effect was
observed experimentally by Martin and Berkau (790). On the other hand, recirculation
of flue gas, which ought to give lower combustion temperatures, was observed by
Turner (791) to not change the fractional conversion of fuel nitrogen to NO.
Further work on this type of diffusion flame model should consider a more
realistic set of reactions for HCN combustion and should attempt to make
quantitative estimates of combustion intensity.
Table 16. REACTIONS USED IN HYDROGEN DIFFUSION FLAME
Combustion Reactions
1
2
3
U
5
6
7
8
9
10
•
•
BROK
JOHN
IB
11
. HOMER 1
•
•
•
•
•
•
•
11.
12.
13
Ik
•
•
HOMER 2
BROK
BROK
LDSB
LDSB
LDSB
LDSC
BROK
UA
UB
i
3
5
1
6
THORN 1
BROK
BROK
8
10
H2
02
H
H
H
H
H2
H20
02
H
H0a
0
H
+
+
+
+
+
+
+
+
+
+
+
+
+
+
M
M
OH + HaC
OH + M
02 + H^
02 + M
0
OH
0
H
H02
OH
H02
H0a
—
=
) =
=
} =
=
=
=
=
=
=
=
=
=
H
0
HaO
HaO
H02
H0a
H
H20
OH
0
OH
Oa
OH
H2
+
+
+
+
+
+
+
+
+
+
+
+
+
+
H
0
H^
M
H20
M
OH
H
OH
OH
OH
H20
02
02
+ M
+ M
Reactions Involving N
15. LDSD 1 NO + N = N2 + 0
16. LDSD 3 02 + N = NO + 0
17. N + N + M = N2 + M
S-1U129 69
-------
700
[ N] Initial = 2040 ppm
600
500
a.
a.
*.
o
z
400
300
1500
1600
1900
Figure 23.
1700 1800
Temperature/ °K
EFFECT OF TEMPERATURE ON NO PRODUCTION IN
2000
H, DIFFUSION FLAME
S-14129
68275
70
-------
Table 17. CALCULATED RESULTS-HYDRXEN DIFFUSION FLAMES
WITH FUEL NITROGEN SIMULATED BY N ATCMS
Atoms of Fuel N/molecule H2 .001 .01 .03 .10
Values of Fraction of
Temp Vol Fuel Nitrogen Which is
°K cm3/mole sec Converted to NO
2000 300 75.0 21.3 9-06 3.12
9^9 68.8 16.7 6.7^ 2.2U
3000 65.2 12.9 ^.98 1.61
9^90 62.7 10.0 3.68
30000 61.2 7.75 2.72
1875 300 62.7 7.38 2.U9
9^9 55.8 5.38 1.77
3000 U9.0 3.90 1.25
91*90 U2.7 2.82
30000 37-3 5.71* 2.03
1750 300 57.2 5.89 1.95
9^9 W.k U.21 1.36
3000 Uo.8 3.00 0.95
9^90 33.9 5.93 2.13
30000 27.7 1.52
S-1M29
-------
S0a Oxidation to S03 in Flames
From the literature review it was shown that a correct kinetic mechanism
for the oxidation of S02 to S03 must exhibit the following features:
1. It should predict lower conversions at lower excess air;
2. It should predict superequilibrium conversions at the flame zone;
3. It should predict the proper slow decay rate;
k. It should predict negligible reaction in the absence of flames or NO;
5. It should predict the self-inhibition by S02 of its own oxidation;
6. It should predict the inhibition of NO on the oxidation of S02
in the flame zone;
7. It should predict the catalysis by NO of S02 oxidation in the cooler
post-flame zone.
8. It should predict the effect of reburniug (secondary fuel addition)
which is to reduce S03 that has been formed.
9. It should predict typical S03 concentrations measured in furnace
stack gases.
The approach adopted to construct such a model was to begin with the
mechanism suggested by Merryman and Levy (617) as a basis and then to modify it as
needed until all of the above criteria were met. For experimental data against
which a model could be tested, we used the plug flow reactor data of Nettleton and
Sterling (6l6), the flat-flame data of Wendt, Sternling, and Matovich (623), the
low-temperature data of Cullis Henson and Trimm (32U), the combustion data of
Hedley (611*), and typical data obtained from boilers and heaters.
Results Obtained From Merryman and Levy Kinetics
The basic kinetic scheme of combustion with S02 oxidation is shown in
Table 18. Here we have taken the approach that methane fuel can be simulated by a
wet CO air mixture. The rate coefficients for
S02 + 0 + M = S03 + M (75)
S03 + 0 = S02 + 02 (76)
S03 + H = S02 + OH (77)
were those suggested by Merryman and Levy (617) in their studies of COS and HgS
flames. It can be seen that according to this mechanism S02 acts as a recombining
catalyst for 0 atoms, so this route can explain why S02 inhibits its own oxidation,
provided that the final S03 frozen in depends on a superequilibrium concentration of
0 atoms. S02 can also act as a recombination catalyst for H and OH through:
M + S02 + H = HS02 -f M (78)
S-1U129
-------
Table Ifi. BASIC KINETIC SCHEME FOR S03 OXIDATION
Reactions Used
1.
2.
3.
U.
5.
6.
7.
8.
9.
10.
11.
12.
13-
li*.
15.
16.
SBOV 3
LDSA 1
LDSB 1
LDSB 3
LDSB 5
LDSC 1
MERL 1
MERL 3A
MERL 3B
HOMER 1
HOMER 2
BROK llA
BROK IfB
THORN 1
JENKI 1
JENKI 2
02
CO
H2
Ha
H20
02
S02
S03
S03
H
H
H
H
H02
H
HS02
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
M
OH
0
OH
0
H
0 + M
0
H
OH + HjsC
OH + M
02 + H^
02 + M
OH
S02 + M
OH
= 0
= C02
= H
= H20
= OH
= 0
= S03
= S02
= S02
) = H^
= H20
D = H02
= H02
= 02
= HS02
= HsO
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
0 + M
H
OH
H
OH
OH
M
02
OH
H20
M
Hao
M
HaO
M
S02
73
-------
followed by:
HS02 + OH = S02 + HaO (79)
and
HSOa + H = S02 + H2 (80)
where rate coefficients for these reactions were taken from Halstead and Jenkins
(639).
Preliminary computer runs were made to simulate the experiments of
Nettleton and Stirling (6l6) in which the peak S03 and final S03 were measured in
a plug flow reactor. It was shown that S03 does go through a maximum above its
equilibrium concentration, although our calculated transient concentration was
higher than that measured by a factor of three. Also, our 0 atom peak concentra-
tions were suspiciously high. The final S03 calculated was close to that measured,
although it turned out that this was also close to the equilibrium value. In
Run 52 the S02 concentration was increased by a factor of ten, and the peak 0 atom
concentration showed a substantial drop, indicating a substantial catalytic effect.
No inhibition of S03 formation was observed since the final S03 was again at its
equilibrium value. It was therefore decided to simulate the experiments of Wendt
et al (625) in which this self-inhibition effect had been measured.
Attempts to simulate these experiments were unsuccessful, using this set
of rate coefficients. In each case the S03 decayed back to its equilibrium value
instead of being frozen in at a higher value as expected. The problem was
identified as being due to the fact that reaction 75 was equilibrated at the
temperatures involved, causing the S03 concentration to follow the 0 atom concen-
tration until global equilibrium was reached. In other words, it appeared that the
rate coefficients suggested by Merryman and Levy, and, incidentally, supported by
the bulk of the literature, were substantially too high.
In a subsequent run, in which combustion conditions in a furnace were
simulated, the S03 profiles obtained were unreasonable and did not fit measured
plant data. Again, this was attributed to the fact that the rate coefficients
used for reactions 75 through 77 were too high. Typical computed profiles for
various quench rates are shown in Figure 24. These should be compared to Hedley's
Figure 1. It is obvious that a substantial discrepancy exists.
Because of this discrepancy, we next compared the data of Cullis, Henson,
and Triflm (3^-2) with a simple (non-flame) homogeneous non-catalyzed S02 oxidation
mechanism, using the same rates as used above. It was shown that rates suggested
by Merryman and Levy were at least two orders of magnitude too high to agree with
the data. This is demonstrated in Figure 25. Both Ladner and Pankhurst (6Uo) and
Shaw and Green (337) have published data agreeing with Cullis et al that below
1000°C the non-catalyzed S02 oxidation rate is extremely slow. One can only conclude
that much of the data on which Merryman and Levy based their recommendation
actually involved reactions of excited molecules. Such reactions can be expected to
be much more rapid than straight thermal reactions; therefore, estimates for
the rate of reaction 75 are much too high. It can also be argued that in order for
spin conservation rules to be obeyed the forward rates of reactions 75 and 76 must
have substantial activation energies.
-------
S-14129
68275
•K
rx
•oi
CO I
if)
102
o.
o.
10
3io-2
lO'3
I I I I I II
io
-4
o
"^
u
ID
o
,-5
10
io-<
10"
io-4 io-3 io-2 io-1
Time, seconds
A. T Decay 2000°K to 1000°K in 0.01 sees
o
O
IO2
Q.
t 10
r>
O Atom
ID'2
o
(D
io-4
10
-5
io-5 io-4 io-3 io-2
Time, seconds
10-'
B. T Decay 2000°K to 1000°K in 2 sees
Figure 24. EFFECT OF TEMPERATURE QUENCH ON
S03 PROFILES - MERRYMAN AND LEVY KINETICS
75
-------
io-
10
,-8
u
-------
Results With Adjusted Rate Coefficients
Attempts were made to simulate results of Wendt et al (623), see
Figure lU, in the literature review, by adjusting the activation energy and pre
exponential factor of the reaction
S02 + 0 + M = S03 + M (81)
It was also assumed that the rate coefficient for the reaction
S03 + 0 = S02 + 02 (82)
could be given by the ratio
= 0.857 x 103 exp(9500/RT)
determined by Merryman and Levy (617). The objective at this point was merely to
predict the measured self -inhibition effect of S02 to its own oxidation. The
values
kai = 0.161 x 1018 exp (-28200/RT)
ks2 = O.l88x 1015 exp (-37700/RT)
did allow the S03 profile to exhibit the proper behavior, and the self -inhibition
effect was observed, as shown in Table 19. The predicted conversions, however,
were low by a factor of two. When the rate coefficients were raised above this
value, the S03 decayed back to equilibrium, which was not observed experimentally.
When the rate coefficients were lowered, too little S03 was predicted at the
frozen value. These rate coefficients have unreasonably high pre -exponential
factors and, as has been mentioned before, are at variance with most of the
published data. Further work is necessary in order to elucidate further the
mechanism of S02 oxidation in flames.
Conclusions
Attempts to construct a realistic model for S02 oxidation were unsuccess-
ful. The rate coefficients suggested by Merryman and Levy were several orders of
magnitude too high.
It was shown that S02 can decrease the 0 atom concentration by acting as
a recombination catalyst.
It was shown that the self -inhibition by SOS on its own oxidation can be
predicted by adjustment of rate coefficients. However, these adjusted rates are
physically unreasonable in other respects and predict S03 concentrations too low by
a factor of two.
More experimental and theoretical work is necessary before the effect of
sulfur in flames is properly understood.
S-1U129 77
-------
CO
I
Table 19. RESULTS USING ADJUSTED RATES (SEE TEXT)
Run
REB 1
REB 2
Time
sec
0
i.o(JO
1.3(-3)
0.1
0
8.6(-5)
l.K-3)
0.1
Temp
°K
1980
1979
1969
1600
1980
1979
1970
1600
Mole Fractions
CO
.082
2.9(-2)
6.5(-3)
1.2(-5)
Final
.082
3.5(-2)
3.96(-3)
8.5(-6)
02
.059
3.M-2)
2.l(-2)
1.8(-2)
S03/SOX
.059
3.6(-2)
1.97(-2)
1Q / f\ \
• O V — fc J
H^O
.165
l.U(-l)
1.6(-l)
1.6(-1)
conversion 0.
.165
l.t(-l)
l.6(-l)
1.6i*8(-l)
0
0
7.9(-3)
9.3(JO
2.K-6)
S03
0
2.2(-6)
7.0(-6)
S02
.ooiU
l.39(-3;
1.39(-3:
1.39 (-3
5% (Measured value = 1%)
0
6.8(-3)
U.77C-6)
0
1. U(-5)
7.97(-5)
3.6(-5)
OlU
l.M-2)
1.39(-2)
1.396(-2)
0° n -\ i£irkf\ i nf c\ i Qf o ^ i £t i } n i I £.\ T r\l £.\ n -xnf i Final
Notes
Initial—low S02
Peak 0 atom
Peak SO3
Initial—high S02
Peak 0 atom
Peak S03
Final
Final S03/SOX conversion 0.26%
-------
Synergism Between Sulfur and Nitrogen Oxides (Post -Flame Region)
The synergism between NO and S02 has been studied by Cullis, Henson, and
Trimm (3^2) and by Armitage and Cullis (626). They found that at high NO concen-
trations (NO is the catalyst) the rate of S02 oxidation was second order with
respect to NO and had a low activation energy. This observation is consistent with
the mechanism
NO + NO + 02 = N02 + N02 (85)
N02 + S02 = S03 + NO (8U)
where the rates of reaction 8U have been independently measured (626), (627) and
shown to be fast. At high NO concentrations (greater than 10-7 mole/cc) reaction
83 is controlling.
At low concentrations of NO, the S02 oxidation process was found to be
first order in NO and to have a high activation energy. This may be explained as
follows. At low NO concentrations reaction 83 is slow. Instead
NO + 02 = N03 (85)
is controlling and is followed by
N03 + S02 = S03 + N02 (86)
and reaction 8U above.
It was the purpose of this study to test this mechanism against the data
of Cullis et al (3^2) without the common steady-state assumptions. The tested model
would then be used to ascertain whether the N0/S02 synergism plays a role in the
stack gases of furnaces and sulfur plant incinerators.
One may conjecture that reaction 85 may occur without a third body, since
£H is merely -U.58 kcal/mole, assuming N03 to be planar and symmetric. For N03 to
be of this form (as compared to 0-0-N-O) it is reasonable to expect the activation
energy of 85 to be high, since the activated complex is three -centered and a
considerable rearrangement of bonds is necessary in order for planar N03 to be
formed. Using the data of Cullis et al, one can fit a rate coefficient for reaction
8^. A value, which fits the data, is:
ke5f = 3.08 1010 exp(-35100/RT)
= 1.88 1013 exp(-35300/RT)
Comparison with the data is shown on Table 20. It should be noted that both
reactions 8U and 86 are important at low NO concentrations. The difference in
reaction order and temperature dependence can be attributed to the relative rates
of reactions 83 and 85. This interpretation is similar to that proposed by
Cullis et al with the difference that we have omitted the reaction
N03 + NO = N02 + N02 (87)
79
-------
since it was shown by our computer runs to contribute little to the overall result.
Instead, the mechanism of N02 formation is either by
NO + NO * 02 = N02 + N02
(88)
or
N03 + S02 = N02 + S03
depending on the NO concentration and the temperature.
(89)
We have applied this synergism model to investigate whether this
mechanism plays a role in the post-flame stack gases of a typical furnace and of a
typical sulfur plant incinerator. For the furnace it was assumed that the flue
gases we_re cooled from l800°K to 600°K in two seconds. Results are shown in
Table 21. Negligible S03 was fonned, showing that this synergism is not important
for this typical furnace. Two cases were considered for the sulfur plant incinera-
tor. Case A was representative of an upset (which can let significant amounts of
ammonia into the incinerator) with 3500 ppm NO in the flue gas. After two seconds,
3.U ppm S03 was formed, which can be significant. At this point the formation of
S03 was constant at 0.373 mole/cc-sec. Further details are shown in Table 21.
Case B was with the sulfur plant operating normally—only 35 PF"1 NO in the flue gas.
Then only 0.02 ppm S03 was formed after two seconds.
Our conclusions are that the data of Cullis, Henson, and Trimm can be
modeled using a simplified mechanism and that this model indicates that the N0/S02
synergism is only important in combustion units when the NO concentration is in
the 1000 ppm range or higher. In practice, this means that the synergism is only
important in the case of upset sulfur plants.
Mechanism
Table 20. N0-S02 SYNERGISM
NO + NO + 02 = N02 + N02
N02 + S02 = NO + S03
NO + 02 = N03
N03 + S02 = N02 + S03
(1)
(2)
(3)
Rate Coefficients
= 1-55 x lO11-' exp -2200/RT
= 6. 31 x 1012 exp -27000/RT
k3f = 3-08 x 1010 exp -35100/RT
= 5-32 x 1012 exp -2050/RT
Reference
Leeds - high temperature range
Armitage and Cullis
See text and data below
Semenov/collision rate times 0.01
Agreement with Data - Cullis, Henson, and Trimm
S02 cone = 3.3 x 10"6 mole/cc 02 = 3.3 x ID"6 mole/cc
Initial NO Temp
cone, mol/cc °K
1.0 x 10-k 1173
1.0 x 10"6 873
0.025 x 10 "6 1173
0.025 x 10"6 873
Time
sec
SO, mole/cc
11.71
22.1
11.58
> x 10-'
0.345 x 10-6
19.93 x 10-9
0.325 x 10~9
Rate
mole/cc sec
4.1 x 10-e
2.9 x 10-8
0.902 x 10"9
2.806 x 10-11
Experimental Value of
Rate, mole/cc sec
2.63 x 10-°
1.32 x 10-8
1.05 x 10-9
2.63 x 1C-11
S-1U129
80
-------
Table 21. APPLICATION OF MODEL FOR N0/S03 SYNERGISM TO
FURNACE FLUE GAS AND SULFUR PLANT INCINERATOR EMISSIONS
1. Typical Furnace (Post-Flame Reactions Only)
Temperature decay: lBOO°K to 600°K in two seconds
Initial Concentration (mole fractions)
S02 1000 ppm
NO 500 ppm
02 3*
Maximum SQ3 obtained 0.01 ppm
Reaction operated at 7Ul°K
Maximum N02 obtained 0.05 ppm after 3-7 seconds
2. Typical Sulfur Plant Incinerator (Post -Flame Reactions Only)
A. Temperature decay: l800°K to 922°K in 0.1 seconds
Initial Concentration
NO 3500 ppm
02 12*
S02 2*
At time 2 sees, temp 922 °K
Rate formation mole/cc-sec
S03 3.U ppm -373 x 10'10
S02 2*
NO 3500 ppm
N02 3-5 ppm -798 x 10 ll
B. Temperature decay: l800°K to 922°K in 0.1 seconcs
Initial Concentrations
NO 35 ppm
02 12*
S02 2*
At time 2 sees, temp 922 °K
Rate formation mole/cc-sec
"12
S03 0.02 ppm 0.15 * 10
S02 2*
NO 35 ppm
N02 0.008 ppm 0.19 x 10
S-14129 81
-------
Recommendations for Future Work
While many insights have been generated by the modeling studies made,
much work remains to be done before a clear idea is obtained about the mechanisms
governing conversion of fuel nitrogen and sulfur to pollutants. Some recommendations
are given here.
1. Diffusion Flames. A mechanism should be set up for combustion of HCN
and tested in the context of diffusional flame combustion to determine if combustion
intensity is as important as the calculations made here indicate and to determine
the roles of combustion temperature and excess air.
2. Data on the distribution of nitrogen between char and volatiles
should be obtained for both coal and residual oil.
3. Model calculations should be made for combustion of nitrogenous
char surrounded by a CO diffusion flame to determine how conversion of the fuel
nitrogen to NOX can be minimized. Also, experimental work is needed in this area.
k. More good data on fixation of nitrogen in premixed flames of methane,
CO, and H2 should be obtained to test the alternative explanations for the origin
of prompt NO and to establish a basis for selection of a working set of rate
constants for the fixation mechanism.
5. Data is required on the role of sulfur in flames and the possible
inhibition of NOx formation by S02. Also, more data is required to elucidate S02
oxidation mechanism in flames.
6. Farther experimental and theoretical studies on NO reduction by H2
and hydrocarbons and possibly ammonia are necessary to determine activation energies
of the process, complete mechanism, and possible harmful emissions—such as HCN.
JOLW/CVS:vsr
S-1U129 82
-------
NOMENCLATURE
a., b.r, CJL constants in quadratic formula for mole fractions
a^ , a-p pre-exponential factors for reaction rates
Cpjn molar heat capacity
CJL concentration of species i
C,- combustion intensity
D.J_J binary diffusion coefficients
D effective diffusion coefficient
Ef, Er activation energy
Fj total molar flux
h zone thickness
HI enthalpy of species i
kf, kj, rate coefficients for reaction in forward and reverse directions
k thermal conductivity
Kp equilibrium constant using partial pressures in atm
H zone thickness
m zone thickness
n.f, n exponent on temperature in rate expression
N^ molar flux per unit area of species i
Nj. total molar flux per unit area
P. partial pressure cf species i
q heat flux
Qf , Qj, steric factor in reaction rate expression
R gas constant
R.^ rate of production of species i per unit volume due to reactions
tg thickness of zone
T absolute temperature
83
-------
V
VOL
x
AEr
m
NOMENCIATURE, contd
volume of reaction zone
volume of reaction zone per unit feed rate
distance
mole fraction of species i
molar flux fraction of species i
activation energy
ratio defined by equation AIII-12
molar density
Subscripts
i
fuel
ox
pertaining to species i
pertaining to the species designated as "fuel"
pertaining to species designated as "oxidizer"
Superscripts
in
e
feed
prod
at the reactor inlet
at the reactor exit
in feed stream
at center of diffusion flame sheet
84
-------
Appendix I. Library of Reaction Rate Data
In order to facilitate the comparison of different chemical mechanisms,
it is useful to put the reaction rate data into a common form. We have, therefore,
punched the rate data pertinent to this study into IBM cards. Table AI-1 is a
listing of all data acquired thus far. A free format system of punching is used
as described in Table AI-2. References to data sources are given in Table AI-J.
85
s-1^129
-------
Table AI-1
LISTING OF IBM CARDS FOR REACTION RATE LIBRARY
STOICHt
STOICH.
STOICHt
STOICHt
STOICHt
STOICHt
STOICHt
STOICHt
STOICHt
STOICHt
STOICHt
STOICH,
STOICHt
STOICHt
STOICHt
STOICH.
STOICH.
STOICHt
STOICHt
STOICHt
STOICHt
FRATCOt
FRATCOt
FRATCOt
FRATCOt
FRATCO.
FRATCOt
FRATCOt
FRATCOt
FRATCOt
FRATCO.
FRATCOt
FRATCO.
FRATCO.
FRATCO.
FRATCOt
FRATCOt
FRATCO.
FRATCOt
FRATCOt
'FRATCOt
FRATCO*
RRATCOt
RRATCOt
RRATCOt
RRATCOt
RRATCOt
RRATCOt
RRATCO.
RRATCO*
•RRATCOt
RRATCOt
LANGlt
LANG2,
LANG3t
LANG4.
LANGS t
LANG6.
LANG7,
LANG8.
LANG9,
LANGlOt
LANGllt
LANG12,
LANG13,
LANG14,
LANG15,
LANG16.
LANG17,
LANGlBt
LANG19,
LANG20.
LANG21,
LANGlf
LANGZt
LANGS.
LANG4t
LANGS.
LANG6.
LANG7.
LANG8.
LANG9,
LANG10.
LANG11.
LANG12.
LANG13.
LANG14,
LANG15,
LANG16.
LANG17.
LANG18*
LANG19.
LANG20,
LANG21.
LANG1.
LANG2.
LANG3.
LANG4t
LANGS t
LANG6,
LANG7,
LANGS.
LANG9,
LANG10.
N2 + 0= NO + Nt
N2 + H02 « NO* HNO,
N2 + 0 + M = N20 + Mt
N2 + OH « N20 + Ht
N2 + 02 « N20 + Ot
N2 + N02 • N20 + NO.
N + 02 « NO + 0.
N + OH = NO *• Ht
N20 + 0 * NO + NOt
N20 + 02 = NO + N02t
N + OH = NH + Ot
N + H2 • NH + Ht
N + H20 « NH -f OH,
NH * OH = NO + H2t
NH + 0 « NO + Ht
NH * OH " HNO + H.
NH + 02 = HNO + 0.
HNO * M • H + NO * M(
HNO + OH « NO + H20.
HNO + H « NO + H2,
HNO + 0 • NO * OH,
6.68E13. 1.0. O.Ot
7.9E10t 1.0, 0.5.
1.62E11. 1.0. 0.0.
1.18E12, 1.0. O.Ot
2.88E1^». 1.0. 0.0.
A.5E14, 1.0.0.0, 84.3.
1.41E13. 1.0. 0.0.
5.3E11. 1.0* 0.5*
6.3E14, 1.0. O.Ot
6.0E14. 1.0. -1.5.
1.29E14, 1.0. 0.0.
1.32E15, 1.0. 0.0.
3.59E15, l.Ot O.Ot
1.6E12, 1.0. 0.56.
5.0E11. l.Ot 0.5t
6.44E11. 1.0, 0.0.
4.38E12. 1*0. 0.0*
1.9E16, 1.0. O.Ot
2.1E12. 1.0. 0.5.
1.4E13. 1.0* O.Ot
5.0E11* 1.0* 0.5.
1.0E13. 1.0* O.Ot
9.59E11. 1.0, 0.0.
7.25E12, 1.0, 0.0.
3.0E13. 1.0. O.Ot
5.3E14, 1.0. 0.0,
2.5E14. 1.0. 0.0.
2.95E12, 1.0. 0.0,
9.53E13. 1.0. 0.0.
1.61E13, l.Ot 0.0,
2.0E8, 1.0, O.Ot
75.230t
41. 81
3.180,
75.8,
107.8.
7.9.
5.62.
26.7,
9.9.
18.0.
22.3.
36.6*
1.5.
5.0,
2.9,
13.0.
50.0,
0.0.
3.0,
0.0,
0.0,
2.501.
40.7.
10.77,
26.7,
50.0,
39.9,
55.0,
64.5,
3.22.
86
-------
Table AI-1 (Cont). Listing of IBM Cards for ReactionJlate_Library
RRATCOt
RRATCO.
RRATCOt
RRATCOi
RRATCO*
RRATCOi
RRATCOt
RRATCOt
RRATCOt
RRATCOt
RRATCOt
LANGllt
LANG12,
LANG13,
LANG14.
LANG15.
LANG16,
LANG17,
LANG18,
LANG19,
LANG20,
LANG21,
1.0E12,
1.0E12,
1.6E12,
2.22E15t
1.84El*t
2.0E11.
l.OEllt
3.1E15,
4.1E14,
9.5E12,
9.3E12,
l.Ot
ItOt
ItOt
l.Ot
l.Ot
1.0,
l.Ot
l.Ot
l.Ot
l.Ot
l.Ot
0.5t
0.68,
0.36.
0.0,
O.Ot
0.5,
0.5,
O.Ot
0.5,
0.0.
O.Ot
0.1,
1.9,
1.5,
69.6,
71.0.
13.0.
7.0*
0.7,
71.5,
58. Ot
54.5,
STOICHtSBOW ltCH4+M«CH3+H+M ,
STOICHtSBOW 2.CH4*02=CH3+H02t
STOICHtSBOW 3t02+M=0+0+Mt
STOICHtSBOW 4,CH4+0=CH3+OH,
STOICH.SBOW 5tCH4*H»CH3+H2,
STOICHtSBOW 6tCH4+OH=CH3+H20,
STOlCHtSBOW 7,CH3+0=HCHO+H,
STOICHtSBOW 8tCH3+02=HCHO+OH,
STOICH.SBOW 9tHCHO+OH»CHO+H20t
STOICHtSBOW10tCHO+OH=CO+H20t
STOICH.SBOWll»CO+OH=C024-Ht
STOICHtSBOW12»H+02=0+OHt
STOlCH,SBOW13tO+H2»H+OHt
STOICH,SBOW14.0+H20«OH*OH »
STOICHtSBOWl5*H+H20*H2+OH.
STQICHtSBOW16tH*OH+M=H20+M,
STOICH,SBOW18tCHO+MsH+CO+M,
FRATCOtSBOW 1t1.5E+19,1..0.,99.!
FRATCOtSBOW 2tl.OE+14.1.0.0..4
FRATCOtSBOW 3t3.6E+18t1.0.-1.0,11^.612,
FRATCOtSBOW 4.1.7E+13,1.,0.,8.672»
FRATCOtSBOW 5t6.3E+13t1.0,0.,12.573,
FRATCOtSBOW 6.2.8E+13tl.0.0.,4.950,
FRATCOtSBOW 7,l.OE+14,1.0.0.,0.,
FRATCOtSBOW 8.l.OE+12.1.0.0..0.,
FRATCOtSBOW 9.1.OE+14,1.0,0.,0.,
FRATCO.SBOW10tl.OE+14,1.0.0.,0.,
FRATCO.SBOW11.3.1E+11.1.0.0.,0.594,
FRATCOtSBOW13t4.0E+14tl.OtO.,9.36!M
FRATCO,SBOWlA,8.4E-H'f»1.0,0.,18.0?8.
FRATCO.SBOW15tl.OE+l*t1.0.0.,20.196,
FRATCOtSBOWl6t2.00E+19tl.O,-1.0,0,
FRATCO,SBOW18.2.0E+13,1.0,0.5,28.51?,
RRATCOtSBOW 1.13.34E+16tl.OtO.t-2.8^6,
2tl.32E-fl2*1.0tO.»-10.724,
3,14.78E-t-16,l.,-1.0,-0.918,
4,2.8E+11.1.C.O.,8.692,
5t23.56E+ll*l*0.0.,14.623,
6,4.72E-fl2tl.t0.t22.140t
7,1.255E-»-15,1.0,0.,67.020,
8,9.55E+lltl.O,0.t50.950,
9, 3.69E+13,1.0,0..43.260,
RRATCOtSBOW
RRATCOtSBOW
RRATCO,SBOW
RRATCO,SBOW
RRATCO,S90W
RRATCO,SBOW
RRATCO.SBOW
RRATCOtSBOW
RRATCO,SBOW10,2.<»5E+15tl.Ot0.t91.590,
87
-------
Table AI-1 (Cont). Listing of IBM Cards for Reaction Rate Library
RRATCO,SBOW11.4.04E+13.1.0,0.,22.924,
RRATCO.SBOW12.0.167E+14,1.0.0..0.38*.
RRATCO.SBOW13.1.762E+14,1.0,0.,7.335,
RRATCO.SBOW14.0.820E+14.1.0,0..0.888.
RRATCO.SBOW15.0.22E+U.I.0,0.* 5.056.
RRATCO.SBOW16.3.79E+20.1.0,-1.0.119.630.
RRATCO.SBOW18.2.58E+13*1.0,0.5.0.472.
STOICH,
FRATCO.
RRATCO.
STOICH,
FRATC3.
RRATCO,
STOICH.
FRATCO,
RRATCO,
STOICH,
FRATCO,
RRATCO.
STOICH,
FRATCO.
RRATCO.
STOICH,
FRATCO.
RRATCO.
STOICH,
FRATCO.
RRATCO.
STOICH,
FRATCO.
RRATCO.
STOICH.
FRATCO.
RRATCO.
STOICH,
FRATCO.
RRATCO.
STOICH,
FRATCO.
RRATCO.
STOICH,
FRATCO.
RRATCO.
STOICH,
FRATCO.
RRATCO.
STOICH,
FRATCO,
RRATCO,
STOICH,
FRATCO,
RRATCO,
STOICH,
FRATCO,
RRATCO,
NEWH1,
NEWH1,
NEWH1,
NEWH2,
NEWH2.
NEWH2,
NEWH3.
NEWH3.
NEWH3.
NEWH4*
NEWH4,
NEWH4.
NEWH5.
NEWH5.
NEWH5.
NEWH6.
NEWH6.
NEWH6,
NEWH7.
NEWH7,
NEWH7,
NEWH8,
NEWH8,
NEWH3,
NEWH9,
NEWH9,
NEWH9,
NEWH10,
NEWH1C,
NEWH10,
NEWH11,
NEWH11,
NEWH11,
NEWH12,
NEWH12,
NEWH12,
NEWH13.
NEWH13,
NEWH13,
NEWHK,
NEWHl^f,
NEWH14,
NEWH15,
NEWH15,
NEWH15,
NEWH16,
NEWH16,
NEWH16.
H20>MnOH+H+M. SYMCA-1969-12-60*
5.4E17.1.0.0.0,123.6.
1.5E16. 1.0. 0.0. 0.0.
H2+M=H+H+M, SYMCA-1969-12-604f
3.1E15* 1.0* 0.0. 110.0.
7.0E17. l.Oi -1.0. 0*0.
NO+M=N+0+M, SYMCA-1969-12-604,
3.989E20. 1.0* -2.5* 150.0*
0.9E15, 1.0. 0.0* 0.0*
N2+M=N+N+M, SYMCA-1969-12-604,
4.754E17, 1.0, -1.5. 224.9.
6.1E14* 1.0* 0.0* 0.0*
SYMCA-1969-12-604,
0.0. 61.0.
0.0. 21.4.
SYMCA-1969-12-604,
-1.0, 74.0*
0.0. 0.0,
SYMCA-1969-12-604,
1.0. -1.0. 118.0.
N20+M=N2+0+M.
1.0E15. 1.0.
1.82E13* 1.0*
N02+M-NO+0+M.
5.4E21* 1.0*
2.0E16* 1.0.
02+M»0>0+M,
3.5&3E18.
1.0E14. 1.0. 0.0. C.O.
OH+H=H2+0» SYMCA-1969-12-604.
1.4E12. 1.0. 0.0. 6.0,
3.3E12. 1.0, 0.0* 8.00,
OH+0«02+H, SYMCA-1969-12-604.
5.5E13. 1.0. 0.0* 1.0,
7.2E14, 1.0,
OH+H2=H20+H,
6.2E13, 1.0,
3.2E14, 1.0,
OH+OH=H20+0»
7.7E12. 1.0,
8.3E13* 1.0.
CO+OH=C02*H.
7.1E12. 1.0.
0.0* 16.9*
SYMCA-1969-12-604,
0.0, 6.0.
0.0. 21.1.
SYMCA-1969-12-604,
0.0, 1.00,
0.0, 18.1,
SYMCA-1969-12-604,
0.0, 7.7,
4.7E14, l.C, 0.0, 27.25.
NO+0=02+N, SYMCA-1969-12-604,
3.2E9* 1.0. 1.0. 39.10.
13.3E9, 1.0, 1.0. 7.08.
NO+N-N2+0, SYMCA-1969-12-604,
1.55E13. 1.0. 0.0, 0.0,
7.0E13, 1.0, 0.0, 75.50.
NO+02=N02+0, SYMCA-1969-12-604,
0.18E11, 1.0. 0.5. 47.0.
0.58E11. 1.0. 0.5, 0.0.
NO+NO=N20+0. SYMCA-1969-12-604,
2.6E12, 1.0, 0.0, 63.8,
1.42E14, 1.0* 0.0* 28.0*
88
-------
Table AI-1 jCont). Listing ofJBl^Cards for Reaction Rate Library
STOICH, NEWH17,
FRATCO, NEWH17,
STOICH, C80W1,
FRATCO, CBOW1,
STOICH, CBOW2,
FRATCO, CBOW2,
STOICH, CBOW3,
FRATCO, CBOW3,
STOICH* CBOW4,
FRATCO, CBOW4,
STOICH, CBOW5,
FRATCO, CBOW5,
STOICH, CBOW6,
FRATCO, CBOW6,
STOICH, CBOW7,
FRATCO, CBOW7,
STOICH, CBOW8,
FRATCO, CBOWB.
STOICH, CBOW9,
FRATCO, CBOW9,
STOICH, CBOW10,
FRATCO, CBOW10,
STOICH, CBOW11,
FRATCO, CBOW11,
STOICH, C80W12,
FRATCO, CBOW12,
STOICH, CBOW13,
FRATCO, CBOW13,
STOICH, CBOW14,
FRATCO, CBOW14,
STOICH, PATT1,
FRATCO, PATT1,
STOICH, LDSB 1,
STOICH, LDSB 3.
STOICH, LDSB 5,
STOICH, LDSB 7,
STOICH, LDSC 1,
STOICH, LDSC 3.
STOICH, LDSC 5,
STOICH. LDSC 7,
STOICH, LDSC 9,
STOICH, LDSC11,
STOICH.LDSD 1,
STOICH, LDSD 3,
STOICH. LDSD 5,
STOICH, LDSD 7,
STOICH, LDSD 9,
STOICH, LDSD11,
STOICH, LOSE 1,
STOICH, LOSE 3*
STOICH, LOSE 5*
FRATCO, LDSB 1,
FRATCO, LDSB 3,
H+02+M=H02+M,
1.3E15, 1.0,
H2 4- 02 «
2.5E12, 1.0,
H + 02 »
2.2E14, 1.0,
0 * H2
1.7E13, 1.0,
H + H20 «
8.4E13, 1.0,
0 + H2O
5.8E13, 1.0,
H 4- H 4-
1.0E18, 1.0,
H 4- H 4-
1.5E18. 1.0,
04-0 +
3.0E17, 1.0,
0 + 0 +
4.0E17, 1.0,
H + OH +
0.20E20. 1.0,
H 4- OH 4-
0.40E20, 1.0,
H + OH +
4.0E20, 1.0,
H 4- 02 +
1.6E15, 1.0.
H + 02 +
3.0E15, 1.0,
CN+CN=C2+N2,
1.6E15, 1.0,
H2 +0
H2 +OH
H20 4-0
H20 +M
02 +H
02 +H
H202 +H
H202 +H
H202 4-OH
H202 4-M
NO +N
02 +N
N 4-0
N2 +02
N20 +0
N02 +N
N02 +0
N02 +M
NO +0
SYMCA-1969-12-604
0*0, 0.0,
OH + OH,
0.0, 19.65,
OH + 0,
0.0, 8.45,
OH + H,
0.0, 4.76.
H2 + OH,
0.0. 10.1.
OH + OH,
0.0, 9.07,
ARGON" H2 +
-1.0, 0.0,
N2= H2 + N2,
-1.0. 0.0.
ARGON* 02 +
-1.0, 0.0,
N2* 02 + N2,
-1.0, 0.0,
ARGON* H20 +
-1.0, 0.0,
N2 = H20 +
-1.0, 0.0,
H20 = H2 +
-1.0. 0.0,
ARGON = H02
0.0. 0.504,
N2 = H02 4-
C.O, 0.504,
,
ARGON ,
ARGON,
ARGON,
N2,
H20,
+ ARGON,
N2,
JCPSA-1962-36-1146
0.0, 43.0
= H 4-OH
=H20 +H
«OH +OH
«H +OH
= 0 4-OH
+M «H02
=H2 +H02
»H20 +OH
=H20 +H02
«OH +OH
oN2 +0
"NO +0
+M =NO
-NO +NO
=NO +NO
= NO 4-NO
=NO +02
= NO +0
=N02 +HV
,
,
,
+M
,
+M
,
,
,
+M
,
,
+M
,
,
,
,
+M
,
1.7 E+13,1.00,0.00,9.45 ,
2.19 £4-13,1.00,
0.00,5.15 *
-------
Table AI-1 (Cont). Listingjrf IBM Cards for Reaction Rate Library
FRATCO.LDSB 5.
FRATCOtLDSB 7.
FRATCO»LDSC li
FRATCOtLDSC 3.
FRATCO.LDSC 5,
FRATCOtLDSC 7.
FRATCO.LDSC 9,
FRATCO.LDSCllt
FRATCO.LDSD 1.
FRATCO.LDSD 3,
FRATCO.LDSD 5,
FRATCO.LDSD 7.
FRATCO.LDSD 9,
FRATCO.LDSD11.
FRATCC.LDSE 1.
FRATCO.LDSE 3.
FRATCO.LDSE 5,
RRATCO.LDSB li
RRATCO.LDSB 3,
RRATCO.LDSB 5.
RRATCO.LDSB 7,
RRATCO.LDSC 1.
RRATCO.LDSC 3,
RRATCO.LDSC 5.
RRATCO.LDSC 7,
RRATCO.LDSC 9,
RRATCO.LDSC11.
RRATCO.LDSD 1.
RRATCO.LDSD 3.
RRATCO.LDSD 5.
RRATCO.LDSD 7,
RRATCO.LDSD 9,
RRATCO.LDSD11*
RRATCO.LDSE 1.
RRATCO.LDSE 3,
STOICH.LDSE 6.
FRATCO.LDSE 6,
RRATCO.LDSE 6.
5.75 E+13.1.00,0.00,18.0
3.4 E+05,1.00.0.00,0.0
2.24 E+14,1.00,0.00*16.8
1.59 E+15,1.00,0.00.1.0
2.34 £+13*1.00,0.00*9.2
3.18 E+14,1.00.0.00,9.0
1.00 F+13,1.00,0.00*1.8
1.17 E+17,1.00,0.00,45.5
3.10 E+13.1.00,0.00*.33*
6.43 E+09,1.00.1.00.6.25
3.9 £+15*1.00,0.00.***•*•*•*
*****£+**,i,00.0.00.*********
6.0 £+14*1.00.0.00.26.7
1.1 E + 13,1.00,0.00.0.0
1.0 E+13,1.00,0.00..6
1.1 E+16.1.00.0.00.65.0
•«***£+«*,1.00,0.00,*********
7.3 E+12,1.00.0.00.7.3
8.41 EM3.1.00.0.00.20.1
5.75 E+i2.i.00.0.00..78
1.17 E+17,1.00,0.00.0.0
1.3 E+13,1.00,0.00.0.00
2.4 E+15,1.00,0.00.45.9
9.6 E+12.1.00.0.00.24.0
5.6 £+13.1.00,0.00*77.9
2.8 E+13.1.00.0.00*32.7
8.4 £+14*1.00.0.00.5.3
1.36 E+14.1.00.0.00.75.4
1.55 E+09.1.00.1.00.38.64
***»»£+**,1.00,0.00,*********
1.00.0.00.*********
1.0 £+14,1.00.0.00.76.0
1.0 E+10.1.00.0.00.88.0
1.0 £+12,1.00,0.00,45.5
1.05 E+15,1.00,0.00.1.87
NO +NO +O2
2.4 E+09,1.00,0.00.-1.05
4.0 E+12,1.00,0.00.26.9
N02
+N02
STOICH.WILD 1«H2+NO=HNO+H»
ST01CH.WILD 3,OH+H2=H20+H,
STOICH.WILD 5.N20+HaN2+OH,
STOICH.WILD 6.HNO+OH*NO+H20.
STOICH.WILD 7»H+NO+M=HNO+M,
STOICH.WILD 9,HNO+NO=N20+OH,
STOICH.WILD10.HNO+HNO=N20+H20.
STOICH,WILD11,N20+M»N2+0+M,
STOICH,WILD12.NO+NO-N20+0,
STOICH.WILD13.0+H2=OH+H,
ST01CH,WILD14,H20+OoOH+OH.
STOlCH,WlLD15,H2+M=H+H+M,
STOICH.WILD17.H+OH+M=H20+M,
STOICH,WILD20,0+NO=N+02,
STOICH,WILD22,N+NO=N2+0,
STOICH,WILD24,H+02=OH+0,
FRATCO.W1LD 1,1.4E+13,1.0.0.0.54.9,
90
-------
Table AI-1 (Cont). Listing of IBM Cards for Reaction Rate Library
FRATCOtWILD
FRATCO.WILD
FRATCOtWILD
FRATCOtWILD
FRATCOtWILD
3t3.9E-t-13tl.OtO.Ot5.49t
5t3.0E+13,1.0tO.Otl0.77»
6t2.0E-t-14,1.0tO.0*3.0.
7t3.2E-fl9tl.O»-1.0.00.0
9i2.OE-i-12tl.OtO.Ot26.Oi
FRATCOtWlLD10t3.OE-t-lltl.OtO.Ot3.5t
FRATCOtWlLDllt5.0E-t-14,1.0tO.Ot58.0t
FRATCOtWlLD12t2.6E-t-12tl.OtO.Ot63.6t
FRATCOtWlLD13.1.3E-t-13tl.OtO.O*9.4*
FRATCOtWlLD14t9.2E-H3tl.OtO.Ot18.0,
FRATCOtWlLD15t4.2E-t-19tl.Ot-0.84tl03.2t
FRATCOtWlLD17.1.8E-t-22.1.0t-1.5tO.Ot
FRATCO.WILD20,3.2E+09,1.0.1.0.39.1.
FRATCOtWlLD22tl.5E*13,1.0tO.0*0.Ot
FRATCO,WlLD24,9.5E-t-13,1.0»O.Otl4.7,
RRATCOtWlLD 1.7.0E+13tl.OtO.Ot3.0t
3tl.8E-t-14,1.0tO.O»20.7t
5il.3E-fl3tl.OtO.Ot76.Ot
6t6.2E-fl4tl.OtO.Ot73.31t
7tl.OE-fl9tl.Ot-l.Ot46.Ot
9t2.4E-fl3tl.OtO.O*41.13t
RRATCO.WlLD10tl.lE-t-13tl.OtO.Ot88.94,
RRATCO»WlLD11.1.2E-fl3,1.0,0.0*20.77,
RRATCO»WlLD12»2.0E-fl4,1.0.0.0,28.0,
RRATCO.WlLD13tl.5E-f 11 * 1.0.0.0.6.95 »
RRATCO.WI LD14. 7. 6E-f 12,1.0.0.0.1.0.
RRATCOtWlLD 15. 5. OE-f 18. l.Ot-l.OtO.Ot
RRATCO.WlLD17.1.0E-f 24,1.0.-1.34 .118.0.
RRATCO,WlLD20»1.6E-fl0.1.0,1.0t7.2,
RRATCOtWlLD22.6.9E-fl3»1.0*0.0.75.25«
RRATCO,WlLD24.2.2E-fl2,1.0.0.0.0.0.
RRATCOtWlLD
RRATCOtWlLD
RRATCOtWlLD
RRATCOtWlLD
RRATCOtWlLD
STOICH,
FRATCOt
STOlCHt
FRATCOt
STOICHt
FRATCO*
STOICH,
FRATCOt
RRATCOt
STOICH,
FRATCOt
RRATCOt
GUTM2.
GUTM2,
FENJ3.
FENJ3,
GUTM1,
GUTM1,
MERL1,
MERL1.
MERL1 ,
MERL3A,
MERL3A.
MERL3A,
N20 -f O
0.85E14,
N20 + 0
1.02E14,
N20 -f
, 1.0.
S02 * 0
»N2
1.0,
NO
1.0,
ARGON*
-4.59,
* M
•f 02.
0.0. 28.0.
•f NO*
0.0. 28.0.
N2 -f 0
60.Ot
SOS -f Mt
ARGONt
2.4E17, 1.0. 0.0* 2.50.
11.538E-fl9, 1.0. 0.0, 83.090.
S03 -f 0 - S02 -f 021
2.8E14, 1.0, 0.0, 12.0,
14.18E-fl2. 1.0, 0.0. 49.930.
STOICH,
FRATCO.
STOICH.
FRATCOt
STOICHt
FRATCO,
STOICH.
STOICHt
FRATCOt
FRATCOt
RRATCOt
DAVllt
DAVIlt
DAVI2,
DAVI2.
D
-------
Table AI-1 (Cont). Listing of IBM Cards for Reaction Rate Library
RRATCO.
STOICH,
FRATCO,
RRATCO*
STOICH,
STOICHt
STOICH,
STOICH,
STOICH,
STOICH,
STOICH,
STOICH,
STOICH,
STOICH,
STOICH,
STOICH,
STOICH,
STOICH,
STOICH,
STOICH,
STOICH,
STOICH,
STOICH,
STOICH,
STOICH,
STOICH,
STOICH,
STOICH,
STOICH.
STOICH,
STOICH,
STOICH,
STOICH,
FRATCO,
FRATCO,
FRATCO,
FRATCO,
FRATCO,
FRATCO,
RRATCO,
FRATCO,
FRATCO,
FRATCO,
FRATCO,
FRATCO,
FRATCO,
FRATCO,
FRATCO,
FRATCO.
FRATCO,
FRATCO,
FRATCO,
FRATCO.
FRATCO,
FRATCO.
HOMER2,
LDSA 1,
LDSA 1,
LDSA 1.
BROK1,
BROK2,
BROK3.
BROK4,
BROK5,
BROK6.
BROK7,
BROK8.
BROK9.
BROK10,
BROK11,
BROK12,
BROK13,
BROKU,
BROK15,
BROK16,
BROK17,
BROK18,
BROK19,
BROK20,
BROK21,
BROK22,
BROK23.
BROK2*.
BROK25,
BROK26.
BROK27,
BROK28,
BROK29,
BROK1,
BROK2.
BROK3,
BROK<»,
BROK5,
BROK6.
BROK6.
BROK7,
BROK8,
BROK9,
BROK10,
BROK11,
BROK12,
BROK13,
BROK.14,
BROK15.
BROK16,
BROK17,
BROK18,
BROK19,
BROK20,
BROK21,
1.4215E+25. 1.
CO* OH= C02+
5.6E+11. 1.0*
7.29E+13* 1.0*
OH+H2cH20+H,
H+02*OH+0,
0+H2-OH+H,
H-f02+M-H02+M,
CO+OH-C02+H,
H+H02-OH+OH,
OH+H02-H20+02,
0+H02»OH+02.
0+H20*OH+OH»
H+H02»H2+02,
H02+H2»HOOH-»-H,
HOOH*M«OH*OH-fM,
H02+H02=HOOH+02»
H-I-HOOH-H20+OH,
0+HOOH-OH+H02,
OH+HOOH=H20-»-H02 ,
CO+02»C02*0,
H2+M-H+H-»-M,
H+OH+M«H20*M.
0+0+M=02-t-M,
NO-t-H02 = N02+OH,
N02+HBNO+OH*
0+N02-NO+02 ,
H+NO-»-M=HNO-»-M,
H4-HNO=H2-»-NO.
OH+HNO>>H20+NO,
0+HNO=OH+NO.
H02*NO=HNO*02.
0+NO+M«N02+M,
2.3E13, 1.0,
2.04E4 , 1.0,
<»*OE13* 1*0,
1.0E15, 1.0,
6.6E11. 1.0.
7.0E13* 1.0.
0.6623E13, 1.0.
6.0E12. 1.0.
6.0E12, 1.0,
8.4E13, 1.0.
2.3E13, 1.0.
1.66E13, 1.0.
3.19E17, 1.0,
1.8E12, 1.0.
<».16E14, 1.0.
8.0E13, 1.0,
3.6E12, 1.0,
2.5E12, 1.0.
1.12E13. 1.0,
1.0E19, 1.0,
8.15E18, 1.0*
1.0E13, 1.0,
0, -2.6* 119.
H
0.0*
0.0,
0.0,
0.0*
o.o.
0.0.
0.0,
O.C,
0.0,
0.0,
0.0,
0.0,
0.0,
0.0,
O.C,
0.0*
o.o.
0.0*
0.0,
0.0.
0.5,
-1.0.
-1.22
0.0.
1.080*
23.410,
5.2,
16.50,
10.2,
-1.3,
1.03,
0.0,
39.62,
0.0,
0.0,
18.0,
0.0,
25.0.
*7.0.
0.0*
9.00*
1.00*
0.0,
48.0,
92.6,
0.0,
* 0.0,
0.0,
92
-------
Table_AM (Cont)._Listing_of IBM Cards for Reaction Rate Library
FRATCO.
FRATCO.
FRATCO.
FRATCO.
FRATCO.
FRATCO.
FRATCO.
FRATCO.
STOICH.
FRATCO.
RRATCO,
STOICH.
FRATCO.
RRATCO.
STOICH,
FRATCO,
RRATCO.
STOICH,
FRATCO,
RRATCO.
STOICH.
FRATCO.
RRATCO,
STOICH,
FRATCO.
RRATCO.
STOICH,
FRATCO,
RRATCO.
STOICH,
FRATCO.
RRATCO,
STOICH,
FRATCO.
RRATCO.
STOICH,
FRATCO.
RRATCO.
STOICH,
FRATCO,
RRATCO,
STOICH,
FRATCO,
RRATCO,
STOICH,
FRATCO,
STOICH,
FRATCO,
RRATCO,
STOICH,
FRATCO.
RRATCO.
STOICH.
FRATCO.
BROK22.
BROK23,
BROK24,
BROK25,
BROK26.
BROK27,
BROK28,
BROK29,
JOHN1.
JOHN1,
JOHN1,
JOHN2,
JOHN2,
JOHN2.
JOHN 3,
JOHN3,
JOHN3,
JOHN4 ,
JOHN*.
JOHN4,
JOHNS,
JOHN5.
JOHN5,
JOHN6,
JOHN6,
JOHN6,
JOHN7,
JOHN 7,
JOHN7,
JOHNS,
JOHNS.
JOHNS,
JOHN9 ,
JOHN9,
JOHN9,
JOHN10,
JOHN 10*
JOHN10,
JOHN11.
JOHN11,
JOHN11,
JOHN 12,
JOHN12,
JOHN12.
PATT1,
PATT1,
JENKI1,
JENKI1,
JENKI1.
JENKI2,
JENKI2,
JENKI2.
ARCUL1.
ARCULl.
7.2E14. 1.0. 0.0. 1.93*
1.9E13, 1*0. 0.0. 1.06,
4.0E13, 1.0, 0.0, -0.60*
5.0E13, 1.0. 0.0. 0.0.
3.6E13* 1.0, 0.0* 0.0*
3.0E13* 1.0* 0.0* 0.0*
1.0E13, 1.0, 0.0* 0*0*
9.4E14, 1*0. 0.0* -1.93*
02+02-0+0+02 »
27.52E18, 1.0, -1.0, 118.7,
13.78E17, 1.0. -1.0. 0.340*
02+ARGON=0+0+ARGON,
2.548E18. 1.0* -1.0. 116.7,
1.276E17, 1.0, -1.0, 0.340.
03+03=0+02+03.
9.938E14, 1.0* 0.0* 22.72*
16.79E12, 1.0* 0.0* -2.10*
0+03-02+02,
12.046E12, 1.0, 0.0* 4.79*
12.77E12* 1.0. 0.0, 100.6*
33+02=0+02+02.
4.373E14. 1.0* 0.0* 22.72*
7.388E12. 1.0. 0.0, -2.10*
03+HE=0+02+HE,
3.379E14. 1.0, 0.0. 22.72,
5.709E12. 1.0* 0.0, -2.10,
03+ARGON-0+02+ARGON,
2.485E14, 1.0, 0.0* 22.72.
4.198E12* 1.0, 0.0* -2.10*
03+N2«0+02+N2t
3.876E14. 1.0* 0.0. 22.72.
6.548E12. 1.0. 0.0* -2.10*
03+C02-0+02+C02.
9.540E14, 1.0. 0.0. 22.72,
16.12E12. 1.0* 0.0* -2.10*
03+H20-0+02+H20.
38.16E14, 1.0, 0.0, 22.72,
64.48E12* 1.0* 0.0* -2.10*
02+M«0+0+M.
51.19E18, 1.0* -1.0* 118.7*
25.63E17* 1.0, -1.0. 0.340*
03+M-0+02+M.
7.233E14, 1.0* 0.0, 22.72*
12.22E12. 1.0, 0.0, -2.10*
CN+CN=C2+N2, JCPSA-1962-36-1146
1.6E15* 1.0, 0.0* 43.0
H +S02 +M =HS02 +M
7.256E+16* 1.0, 0.0, 0.0
7.990E+16, 1.0. 0.0, 46.3,
HS02 +OH *H20 +S02
0.6789E+14* 1.0, 0.0* 1.760
0.1169E+16, 1.0, 0.0, 75.09
N02 +S02 =NO +S03*
6.31E+12* 1.0. 0.. 27.0.
93
-------
Table AI-1 (Cont). Listing of IBM Cards forjleaction Rate Library
RRATCO. ARCULlf 38.24E+12, 1.0* 0.* 35.980*
STOICH. PYDY16t NO +02 +M »N03 +M»
FRATCO. PYDY16. 3.697E+08. 1.0* 0.» 4.220*
RRATCO. PYOY16. 2.26E+11. 1.0. 0.* *.420»
STOICH* PYDY29, N03 +NO >N02 +N02 »
FRATCO. PYOY29. 9.216E+11* 1.0, 0.0* -0.6.
RRATCO* PYDY29* 3.9E+11. 1.0* 0.* 23.9,
STOICH* SEMN03, N03 +S02 «S03 +N02*
FRATCO* SEMN03, 0.5325E+13, 1.0. 0.0. 2.050.
RRATCO. SEMN03. 0.1365E+14, 1.0* 0.0, 35.530.
94
-------
Table AI-2
FORMAT FOR REACTION RATE LIBRARY
General Conventions;
1. Free format is used. That is, separate data fields on a card are
enclosed within commas. A comma at the end of the card is implied.
2. Card Columns 1-6 of each card are reserved for field No. 1 which is
a six-character identification word. The following three identifiers are
recognized:
a. STOICH identifies the card as containing the chemical reaction
written symbolically.
b. FRATCO identifies the card as containing rate data for the
forward reaction.
c. pRATCO identifies the card as containing rate data for the
reverse reaction.
3. Field No. 2 of each data card whether of types STOICH, FRATCO,
RRATCO is used for a unique six-character name for the reaction. Blank card
columns in Field No. 2 are ignored and the characters are left adjusted with blanks
filling out the name on the right if fewer than six characters are used. The
literature source for the rate data may be found under the reaction name in
Table AI-J.
U. In punching numerical fields, the FORTRAN I, E, and F conventions are
accepted but with all blank columns ignored.
S-1IU29
-------
.'able AI-2 (Cont). Format for Reaction Rate Library
Data Card Type STOICH
Column 1-6 The characters STOICH constitute field No. 1.
Field No. 2 - the unique reaction name - up to six characters (no comma
or blanks allowed).
Field No. 3 - the chemical reaction written symbolically as, for example:
N2 + 0 = NO + N ,
Up to three reactants and up to three products can be named. Reactants and products
separated by equal sign. Reactants separated from each other by + sign. Products
separated from each other by + sign. Field terminated by comma. Each species name
may have up to six characters (any characters allowed except + , =)• When a species
occurs more than once, the name must be repeated. For example, complete decomposi-
tion of ozone would be
03 = 0 + 0 + 0 ,
Species names are considered left adjusted with blanks ignored and with right hand
side filled in with blanks. The species name M is reserved for the generalized
gaseous third body.
Data Card Type FRATCO (mnemonic for Forward Rate Constants)
Field No. 1 - the six characters FRATCO
Field No. 2 - the reaction name
Fields 3, U, 5, and 6 are used for the rate coefficients af, Q^>, nf, and
Ef, respectively, where
af = pre-exponential factor, units used are cm3, g mole, sec, °K
Of = steric factor, often incorporated into a^ and hence punched as 1.0,
dimensionless
nj = an exponent on the absolute temperature, dimensionless
Ef = the activation energy, units kcal/g mole
Hence, the reaction rate for the forward reaction is calculated from
kf = afQfTnf exp(-Ef/RT)
with T in °K and units cm3, sec, and g moles used as appropriate.
Data Card Type RRATCO (mnemonic for Reverse Rate Constants)
Comments are the same as for FRATCO except that reference is to the
reverse reaction throughout.
96
S-1^129
-------
Table AI-3
REACTION NAMES—CONVENTIONS USED AND
LITERATURE REFERENCES
General Comments
The reaction names used consist of 1 to 6 alpha-
numeric characters mnemonically suggestive of the
authors responsible for the reaction rated followed
by 1 or 2 arbitrary digits. Thus, IANG 1 is the first
reaction used by Lange, H. B., Jr., preprint 28B,
Sixty-Fourth Annual Meeting AIChE, San Francisco,
November 28, 1971* The mnemonics and corresponding
references are:
CBOW (792) G17IM (I
LANG (5^) FENJ (333)
LDSB (786) MERL (793)
LDSC (786) DAVI (385)
LDSD (786) HOMER (1*19)
SBOW (526) PATT (360)
WILD 773) BROK (602
LOSE 786) NEWH (720)
JOHN 806) ARCUL (626)
PYDY 729)-(7^7)
The mnemonic THORN refers to unpublished Shell
data while SEMN refers to estimates made using the
Semenov rule and collision theory.
97
-------
Appendix II. Literature References Using the CODEN System
In our literature search, a great many papers were found which are
certainly relevant to a study of the fate of fuel nitrogen and sulfur but which
were not used directly in the modeling studies. To facilitate reference to these
papers, we have adopted the CODEN system of the ASTM (758). This system was used
by Hochstim (759) in preparing his extensive compilation of reaction rate data.
Given below are listings of IBM cards containing (l) an arbitrary acquisition
number, (2) the periodical reference in CODEN, (3) the first author, and (U) an
abbreviated title. Also given are translations of the CODEN names.
Table II-l gives references by acquisition number
Table II-2 gives references alphabetized by author
Table II-3 gives references alphabetized by CODEN
Table 11-^ gives CODEN names alphabetized by periodical name
Table I1-5 gives CODEN names alphabetized by CODEN
In the case of books, preprints, etc., there is insufficient space for the full
reference. Table 11-6 gives these references in full; the CODEN is given simply as
BOOK, PREPRINT, REPORT, etc.
In Tables II-U and II-5 a few periodical CODEN names are assigned arbi-
trarily pending formal assignments by ASTM. These have * after the fifth character.
99
-------
Table AH-1
LIST OF REFERENCES IN ORDER OF ACQUISITION NUMBER
ACQ NO
00312
00313
00314
00315
00316
00317
00318
00319
00320
00321
00322
00323
00324
00325
00326
00327
00328
00329
CC330
00331
00332
00333
00334
00335
00336
00337
00338
00339
00340
00341
00342
00343
00344
00345
00346
00347
00348
00349
00350
00351
00352
00353
00354
00355
00356
00357
00358
00359
00360
00361
00362
CODEN REF
CBFMA-1965- ~335
JIFUA-1967-40-142
AICPA-1968-6A
IJCEA-1969-9-396
JCPSA-1963-39-275
DKPCA-1967-175-647
CBFMA-1967-11-150
ESTHA-1969-3-63
JIFUA-1969- -188
KINFA-1969
JCPAA-1967-17-800
JPCHA-1968-72
CBFMA-1965-9-229
BUPAA-237
JIFUA-1970-43-187
PAPWA-1968-30-786
CBFMA-1970-15-157
CBFMA-1970-15-211
PRLAA-1968- -380
CBFMA-1971-16-125
PPTIA-1969-49-615
JPCHA-1965-10-
TFSOA-1967-63-2442
PSRIA-1961
PICMA-1963- 216
NATUA-1966- -1171
BBCUA-1963-27-
JIFUA-1962-35-502
PRLAA- -276-461
PRLAA-1958-247-123
PRLAA-1966-295-72
SYMCA- -12-323
ZFKHA-1940-14-1428
TFSOA-1946-42-354
CBFMA-1969-13-324
JIFUA-1970- -234
ESTHA-1970-4-653
IJCEA-1969-9-317
JACSA-1947-69-3143
PCSLA-1964- 410
TFSOA-1953-49-1312
HCACA-1930-13-629
JACSA-1959-81-6190
PRLAA-1963-272-147i
JACSA- 1942-64- 1880
PRLAA-1965-283-302
PRLAA-1965-283-291
CBFMA-1957-1-60
JCPSA-1962-36-1146
IEPOA-1969-8-206
IECFA-1969-8-374
AUTHOR TITLE(ABBREVIATED)
ANON. PARAGRAPH QUATATION FROM CONF NEWS
HEDLEYt FORMATION OF S03 IN FLAME GASES
COLLINS. REVIEW OF SULFUR FLAME TECHNOLOGY
WEYCHERT ET, KINTEICS OF CAT CONVERSION OF S02
BERKOWITZ ET, EQUIL COMPOSITION OF SULFUR VAPOR
SACHYAN ET, COMB OF DILUTE H2S FLAMES
CULLIS ET, REACTION OF S02 AND OXGENATED RADICALS
LEVY ET, SOX FORMATION IN COS FLAMES
SNOWDON ET. H2S04 CONDENSATION FROM FLUE GASES
ANON, REACTIONS OF SO.S02. S03 WITH HtO»OH*NO,N02
LEVY ET, SOX FORM IN LOW P H2S FLAMES
WHEELER, RADICAL RECOMBINATION IN S02 DOPED FLAMES
LEVY ET, MICROSTRUCTURE OF H2S FLAMES
WEINER ET. AIR POLLUTION IN THE PULP AND PAPER IND
GUNTHER, MEAUSERMENTS OF FLAME TURBULENCE
TERRY ET, 002 BOILER AT SCUYLKULL STATION
DURIE ET. CATALYTIC FORM OF S03 IN FUEL RICH PROPA
ANON. S SPECIES IN BURNT GAS OF PROPANE AIR FLAMES
HALSTEAD ET, CHEM ILUM1NESCENT REACTION OF SO
CULLIS* REACTIONS BETWEEN S02 AND N02
TUCKER. SOX STACK EMISSIONS-REACTIONS AND CONTROL
FENIMORE ET, S IN THE BURNT GAS OF H2-02 FLAMES
KALLEND S02 ON CHEMlLUM AND ATOM RECOMBINATION
SUGDEN ET, OXIDES AND HYDRIDES OF N AND S IN FLAME
DEMARDAUCHE ET, REACTION OF S CMPDS IN FLAMES
SHAW ET, OXID OF 502 IN AIR EFFECT OF CO AND NO
PANKHURST ET, FORMATION OF S03 IN COMBUSTION
MACFARLANE. FORMATION OF 503 IN COMBUSTION PRODUCT
GAYDON ET, SHOCK TUBE DECOMPOSITION OF S02
KAUFMAN, USE OF AIR AFTERGLOW IN REACTIONS OF 0
CULLIS ET, HOMOGENEOUS GAS OXIDATION OF 502
MULCAHY ET, KINETICS OF 0 WITH SOX
ANON. GENERAL PHYSICAL CHEM
DOOLEY ET, OXIDATION OF 502 IN GAS FLAMES
KALLEND, EFFECT OF S02 ON EQUlL IN H2 FLAMES
ANON, REVIEW CHEM ASPECTS OF FIRESIDE CORROSION
LEVY ET, FORMATION OF SOX IN COMBUSTION
AVERBUCH ET, ELEMENTAL S BY REDUCTION WITH NAT GAS
FENIMORE. HOMOGENEOUS REACTION OF NO AND CO
CAMPBELL ET, BEHAVIOR OF CN IN ACTIVE N
MADLEY ET, KINETICS OF OXID OF CHARCOAL WITH N20
BRINER ET. L'ACTION DES DISCH. ELECT-C2N2
GRAVEN, KINETICS OF DECOMP OF N20 AT HIGH T
BASCO ET, CYANOGEN RADICALS BY FLASH PHOTOL
ROBERTSON ET, THERM REACTION OF H2 AND C2N2
BASCO, REACTION OF C2N2 WITH 02
BASCO ET* REACTION OF C2N2 WITH NO
COHEN ET. BURNING VELOC OF HCN IN AIR AND 02
PATTERSON ET, KINETICS OF CN IN SHOCK WAVES
BLAKEMORE ET, PYROLYSIS OF N-BUTANE
KUNUGI ET, KINETICS OF THERMAL REACT IONOF C2H4
100
-------
Tabie_An-l (Cont). List of References in Order of Acquisition Number
00363
00365
00366
00367
00368
00369
00370
00371
00372
00373
00374
00375
00376
00377
00378
00379
00380
00381
00382
00383
00384
00385
00386
00387
00388
00389
00390
00391
00392
00393
00354
00395
00396
00397
00398
00399
00400
004C1
00402
00403
00404
00405
00406
00407
00408
00409
00410
00411
00412
00413
00414
00415
00416
00417
00418
00419
JACSA-1962-84-4519
AICEA-1972-18-84
CJCHA-1953-31-30
OIGJA-1971-1-74
CEPRA-1969-7-71
IECHA-1942-34-567
CEPRA-1969-65-UU.65
01GJA-1971-9-94
TOSCA- -6-106
IECHA-1942-34-567
JAHSA-1971-28-1C95
JAHSA-1971-28-847
JAHSA-1971-28-833
JAHSA-1971-28-1058
INCEA-1971-11-739
PRLAA-1965-288-275
JPCAA-1971-21-713
JPCAA-1971-21-702
SYMCA-1960-8-127
SYMCA-1965-10-435
SYMCA-1965-10-377
TFSOA-1968-64-1836
BSCBA-1968-77-433
PRLAA-1963-273-145
CBFMA-1971-17-55
CBFMA-1971-16-243
ESTHA-1971-5-333
CBSTA-1971-4-17
CBSTA-1971-4-59
CBSTA-1971-4-73
CBFMA-1971-17-31
CBFMA-1971-16-237
CBSTA-1971-4-9
JPCHA-1962-66-366
ESTHA-1971-5-39
JCPSA-1970-52-5718
CHREA-1958-58-173
CBFMA-1966-10-287
SC1EA-1971-171-1013
JPCHA-1966-70-1793
MOPHA-1966-1 1-403
RIFPA-1964-19-523
JACSA-1963-85-539
PRLAA-1968-305-93
MOPHA-1965-10-401
TFSOA-1967-63-1687
BCHEA-1967-12-388
JCPSA-1967-47-228
CJCEA-1967-45-61
CBSTA-1971-3-37
JACSA-1962-84-4509
JOCRA-1969-45-256
CPENA-1971-79
JCPSA-1966-45-338
SYMCA-1965-10-473
PRLAA-1970-314-585
KURD ET, PYROLYSIS OF PYRIOINEi PICOLINES AND
HERRIOTT ET, KINETICS OF PROPANE PYROLYSIS
INGOLD ET. THERMAL DECOMPOSITION OF BENZENE DERIVA
ANON, PROFITABILITY FACTORS IN GAS OIL CRACKING
KITZEN ET, GAS OIL PYROLYSIS IN TUBULAR REACTORS
FUCHS ET, THEORY OF COAL PYROLYSIS
MARSHALL ET, GAS OIL FEEDSTOCKS FO C2H4 PRODUCT I
BROOKS ET, CRACKING GAS OILS
LINNELL, THERMAL DECOMPOSITION OF PYRID1NE
FUCHS ET, THEORY OF COAL PYROLYSIS
MCELROY ET, N2O, A NATURAL SOURCE OF STRAT NO
CLARK. CHEMICAL KINETICS OF C02 ATMOSPHERES
JULIENNE ET, TEMP DEP OF C02 ABSORPTION
PR1NN. PHOTOCHEMISTRY OF HCL IN ATM OF VENUS
AK1TA, FLAME PROPAGATION BASIC THEORY
SETSER ET, REACTION OF 0 WITH C2N2
STOCKHAM, COMPOSITION OF GLASS FURNACE EMISSSIONS
BAGWELL ET, BOILER OPERATING MODE FOR RED NOX
FENIMORE ET, RATE OF REACTION 0+N20-NO+NO
GRAY ET, H-ATOM ABSTRATION FROM N-H BONDS
ASHMORE, REVIEW ELEMENTARY COMB REACTIONS
DAVIES ET, REACTION OF 0 WITH HCN, CNCL AND CNBR
AILLIET ET, BURN VEL OF C2N2 OR HCN WITH 02
HUSAIN ET. OXIDATION OF NH3 AND N2H4
SPALDING ET, CALC PROCEDURE FOR LAMINAR FLAME SPEE
CRAMAROSSA ET, OZONE DECOMP IN STEADY FLAMES
BUFAL1NI ET, OXlD OF N-BUTANE BY PHOT OF N02
MELV1N ET, REACTION BROADENED DIFFUSION FLAME
WESTENBERG, KINETICS OF NO AND CO IN HC FLAMES
BLUMBERG ET, NO FORMATION IN SPARK IGNITED ENGINES
HOLLAND ET, FLAME SPEED IN H2-ETHANE-N20 SYSTEM
HAY ET, OXIDATION OF GASEOUS FORMALDEHYDE
LIVESEY ET, FORMATION OF NOX IN OXY/PROPANE FLAMES
MOBERLY, SHOCK TUBE FOR HYDRAZINE DECOMPOSITION
ALTSHULLER ET, PHOTO CHEM ASPECT OF AIR POLLUTION
GELBART ET. VIBRATIONAL RELAXATION AND DISSOSIATI
CAMPBELL ET, THE HYDROGEN BROMINE SYSTEM
ROSSER ET, QUENCHING OF FLAMES BY INHIBITORS
WESTBERG ET, CO ROLE IN PHOTCHEM1CAL SMOG
GUTMAN ET, THERMAL DECOMP OF N20
GOGGENHEIM, DIMER1ZATION OF NO, CORRECTION
JANIN ET, LA FLAMME CH4-NH3-02
STREITWIESER ET, TOLUENE IN MICROWAVE DISCHARGES
BODEN ET, EXCITATION OF CN IN ACTIVE NITROGEN
GUGGENHEIM, DIMERIZATION OF GASEOUS NO
CERCEK ET, REACTION OF H AND OH WITH PYRIDINE
METCALFE, KINETICS OF COKE COMB IN REGENERATION
SNELLING ET, DECOMPOSITION OF N20 BY 0(10) N2
RAO ET, SHOCK TUBE STUDY OF REACT OF N2 WITH HCA
BOWMAN, NO FORMATION KINETICS* THE H2-N2-02 REACTI
HURD ET, PYROLYTIC FORM OF ARENES, I SURVEY
BARTLE ET, TOBACCO SMOKE BY GAS CHROMATOGRAPHY
WARD ET, OPEN FLAME FURNACE DESIGN
WESTENBERG ET, ESR AND KINETICS OF THE OD RADICAL
WESTENBERG ET, H AND 0 ATOM PROFILES BY ESR
HOMER ET, DISSOCIATION OF H20 IN SHOCK WAVES
101
-------
Table An-1 (Cont). List of References in Order of Acquisition Number
00420
00421
00422
00413
00424
00425
00426
00427
00426
00429
00430
00431
00432
00433
00501
00502
00503
00504
00505
00506
00507
00508
00509
00510
00511
00512
00513
00514
00515
00516
00517
00519
00520
00521
00522
00523
00524
00525
00526
00527
00528
00529
00530
00533
00534
00535
00536
00537
00538
00539
00540
00541
00542
00544
00545
00546
CBSTA-1971-3-83
SYMCA-1965-10-311
SCIEA-1971-171-1C13
SYMCA-1960-8-487
JPCHA-1968-72-3305
SYMCA-1960-8-496
NATUA-1964-204-988
NATUA-1964-203-619
JPCHA-1969-73-2555
CENEA-1971-6-15
FUELS-1969-48-297
ACIEA-1970-9-181
SC1EA-1971-174-1341
RADCA- -2-142
TFSOA-1956-52-1475
TFSOA-1956-52-1465
PRLAA-1956-235-89
IJCKA-1969-1-105
JCPSA-1962-36-2582
JCPSA-1955-23-2399
PYDYA-1965-3-197
ARPLA-1967-18-261
PYDYA-1966-4-119
CESCA-1963-18-177
IECHA-1955-47-972
JCPSA-1958-29-456
TFSOA-1967-63-662
CHREA-1960-93-3014
JCPSA-1965-43-3237
JCPSA-1965-43-3371
JCPSA- 1967-46-4843
SYMCA-1965-10-43
JPCHA-1959-63-1834
JCPSA-1969-50-2512
JACSA-1951-73-15
TFSOA-1957-53-1102
JACSA-1959-81-769
CBFMA-1971-16-311
CBFMA-1970-14-37
ZFKHA-1959-33-572
PRLAA-1970-316-539
PRLAA-1970-316-575
CBSTA-1970-1-461
PRLAA- -276-324
CBSTA-1970-1-313
SYMCA-1969-12-603
NATUA-1960-186-551
APMPA-1968-20
PLSSA-1967-15-643
5AUPA-1969-690518
PYDYA-1967-5-74
JPCAA-1971-21-702
ACPYA-1946-21-576
AICPA-1971-SF-28B
CBSTA-1971-4-59
JPCAA-1970-20-377
D'SOUZA ETf METHANE OXID IN A STEADY FLOW REACTOR
CLYNE. REACTIONS OF THE HNO MOLECULE
WESTBERG ET, C0» ROLE IN PHOTOCHEMICAL SMOG
HICKS. DECOMP FLAME OF ETHYL NITRATE
SAFRANY ET, REACTION OF H AND N WITH C2N2 HCN AND
GRAY ET. FLAME OF METHYL NITRITE
HERZBERG ET. IDENT OF FREE RAD IN FLASH PHOTOL
MCGRATH ET. UV ABS SPECTRUM OF FREE FULMINATE
ASMUS ET, PYROLYS1S KINETICS OF ACETONITRILE
ANON, DMN IN CIGARETTE SMOKE
KARN ET, COAL PYROLYSIS USING LASER IRRADIATION
BROWN ET, CHEM BEHAVIOR OF ACTIVE NTTROGEN
ARCHER ET, ENVIRONMENTAL NITROSO CMPDS
MANI ET, REACTION OF 0 WITH BENZENE AND OTHER CMPD
BULEWICZ ET, DISSOCIATION CONSTS BY FLAME PHOTOMET
SUGDEN, DISSOCIATION CONSTS BY FLAME PHOTOMETRY I
BULEWICZ ET, HYDROGEN ATOMS IN BURNT GAS MIXTURES
KONDRATIEV ET, INTERACTION OF CO AND 0
WRAY ET, KINETICS OF NO AT HIGH TEMPERATURE
BROMBERG ET, OXIDATION OF CH4 WITH N02
CHINITZ, ANALYSIS OF CH4 AIR COMBUSTION
FRANKLIN, KINETICS OF HYDROCARBON COMBUSTION
CHINITZ ET, NON EOUIL HYDROCARBON AIR COMBUSTION
BOWEN ET, OSS APPROXIMATION IN CHEMICAL KINETICS
GERHARD ET, PHOTOCHEMICAL OXIDATION OF S02
ANON,
GILES ET, REACTIONS OF RF3 RADICALS WITH ORGANIC H
ECKLING ET, KIN STUD. PHOTOCHLORINATION
GETZINGER ET, RECOMBINATION H+02+M*H02+M
WONG ET, REACTIONS OF 0 ATOMS WITH H2 AND NH3
STUCKEY ET, REACTIONS OF O ATOMS WITH CYCLO PARAFF
WESTENBERG ET, H AND 0 ATOM PROFILES BY ESR IN C2
FENIMORE ET. CONSUMPTION OF 02 IN HC FLAMES
WESTENBERG ET, RATE COEFFICIENTS OF 0 + H2 AND
RALEY ET, OXIDATION OF FREE CH3
HOARE ET, REACTION OF CH3 WITH 02 AND COMPARISON
SLEPPY ET, METHYL 02 AND METHYL NO REACTIONS
LIFSHITZ ET, SHOCK TUBE FOR IGN OF CH4-02-ARGON MI
SEERY ET, METHANE OXIDATION BEHIND SHOCK WAVES
N1KITIN, THERMAL DISSOCIATION OF DIATOMIC MOLECULE
CLARK ET, KINETICS OF N WITH 02(356-) AND (IDG)
HALSTEAD ET, REACTION OF H WITH C2H4
MARTENEY, KINETICS OF FORM OF NO IN HC AIR COMBUST
SEAKINS ET, KINETICS OF GAS PHASE HC OXIDATIONS
LAVOIE ET, NO FORMATION IN 1C ENGINES
NEWHALL, ENGINE GENERATED NOX AND CO
SIMONS, VIBRATlONALLY HOT MOLECULES IN RADICAL REA
BERGER ET, REACTIONS OF SOX IN STACK PLUMES
SCHOF1ELD, KINETIC RATE DATA OF ATM INTEREST
TRUMPY ET, PREKNOCK KINETICS IN AN SI ENGINE
BAHN ET, REACTIONS INVOLVING N AND 0
BAGWELL ET, BOILER OPERATING MODES FOR REDUCED NOX
ZELDOVICH, OXIDATION OF N2 IN COMB AND EXPLOSIONS
LANGE NOX FORMATION IN PREMIXED COMBUSTION
WESTENBERG, KINETICS OF NO AND CO IN LEAN FLAMES
HARDISON, CONTROLLING OXIDES OF NITROGEN
102
-------
Table AII-1 (Cont). List of References in Order of Acquisition Number
00547 ASMSA-1959-A-308
00550 SAUPA-1970-700470
00551 CBSTA-1971-3-53
00552 JEPOA-1971- -333
00554 ESTHA-1971-4-320
00555 AGPTA-1964
00556 JEPOA-1971- -293
00557 PAPWA-1970-32-683
00558 C1EAA-1970
00559 CEPRA-1971-67-62
00560 SAUPA-1970-7007C8
00561 SAUPA-1971-710158
00562 SAUPA-1971-710009
00563 SAUPA-1969-69001B
00564 SAUPA-1971-710011
00565 CBFMA-1970-15-97
00566 CBFMA-1970-14-325
00567 JIFUA-1970- -295
00568 J1FUA-1970- -301
00569 IEPDA-1971-10-297
00570 IEPDA-1971-10-357
00571 J1FUA-1970- -517
00572 JIFUA-1970- -397
00573 J1FUA-1971- -196
00574 JIFUA-1971- -38
00575 CEPRA-1971-67-57
00576 CESCA-1970-25-623
00577 ICONA-1970- -314
00579 NAFTA-1970- -11.1
00580 CEPRA-1965-61-A56
00582 JFLSA-1970-40-401
00583 SCPOA-1970-58-161
00584 SYMCA-1953-4-267
00585 SYMCA-1971-13-997
00586 SYMCA-1967-11 -1057
00587 CBFMA-1960-4-161
00588 SYMCA-1956-6-20
00589 CBFMA-1961-5-11
00590 CBFMA-1960-4-325
00591 JASCA-1952-74-739
00592 C8FMA-1964-8-343
00593 PRLAA-1957-240-83
00594 SYMCA-1958-7-475
00595 JCPSA-1955-23-1360
00596 NACRA-1954-H58
00597 PRLAA-1970-317-227
00598 PRLAA-1970-317-235
00599 PTRSA-1956-A249-1
00600 PRLAA- -298-495
00601 PRLAA-1968-307-111
00602 NASCA-1970-TND7C24
00611 TASMA-195B-80-225
00612 REGTA-1965-4-1117
00613 TASMA-1958-80-1231
00614 BOOK-1963-204
00615 JEFPA-1966-88-165
JEFFERlStET, EFFECT OF OPERATING VARB ON EMISSION
CARR ET, INFLUENCE OF FUEL COMPOSITION ON CO AND
CARETTO ETt ROLE OF KINETICS IN EMISSION OF NO
STARKMAN ET, ROLE OF CHEMISTRY IN GAS TURBINE EMIS
HALL ET, NOX CONTROLFROM STATIONARY SOURCES
WEIL. STUDY OF POROUS PLATE FLAMEHOLDERS
TOMANY ET, NOX CONTROL TECHNOLOGY AND DEVELOPMENT
BAGWELL ET, NOX REDUCTION PROGRAM FOR OIL AND GAS
BOWMAN, NOX FORMATION IN COMB, THE H2-02-N2 REACT
BART QIC ET* CONTROL OF NOX EMISSIONS FROM STATION A
CORNELIUS ET, FORMATION AND CONTROL OF NOX
MUZ 10 ET, EFFECT OF T ON FORMATION OF NOX
QUADERi INTAKE CHARGE DILUTION AND NOX EMISSION
NICHOLLS ET, WATER INJECTION FOR CONTROL OF NOX
KEYUOOD ET* PREDICTION OF NOX IN SI ENGINE EMJSS1
LAVOIE, SPECTROSCOPIC MEAS OF NO IN SI ENGINES
OPSAHL ET, OSCILLATORY COMBUSTION AND POLLUTANTS
SAKA1 ET, COMB OF ATOMIZED FUEL OIL DROPS
NURUZZAMAN ET, COMB OF MONOSIZED DROP STREAMS
SATCUNANATHAN, IGNITION DELAY OF DROPS
KUMAR ET, PNEUMATIC ATOMIZATION
GIBSON, COMB OF SOLID PART IN STREAM WITH RECIRCU
ARCHER ET, MULTISTAGE COMBUSTION PART 1
SPALDING, COMBUSTION AS APPLIED TO ENGINEERING
HEDLEY ET, COMBUSTION OF SINGLE DROPS ANS SPRAYS
DEMAREST, STATUS OF REACTOR FURNACES
LONG ET, SELF-IGNITION OF FUEL DROPS IN HOT GASES
RAO ET, STIRRING BY COLD MODEL SIMULATION
CHERADAME, THE AERODYNAMICS OF FLAMES
KARLOVITZ, FLOW PHEN AND FLAME TECHNOLOGY
WILLIAMS, APPROACH TO FLAME TURBULENCE
COTTON, THE STRUCTURE OF FLAMES
FRISTROM ET, T PROFILES IN PROPANE-AIR FLAMES
TSUJI ET, COUNTERFLOW DIFFUSION FLAMES
GRAY ET, PRESENT POSITION IN EXPLOSION THEORY
WESTENBERG ET, THEORY OF LAMINAR SPHERICAL PREM
LINNETT ET, LIMITS OF INFLAMMABILITY
SPALDING ET, PROPAGATION OF STEADY LAM FLAMES
BERLAD ET, THEORY OF FLAME EXTINCTION LIMITS
COOLEY ET, BURNING VELOCITY IN H2 BR2 FLAMES
VAN TIGGELEN ET. FLAMMABILITY LIMITS
SPALDING, FLAMM LIMITS AND FLAME QUENCHING
DIXON-LEWIS ET, LIMITS OF INFLAMMABILITY
FRISTROM, ONE-DIMENSIONAL FLAME FRONT MODELS
DUGGER ET, PREDICTION OF FLAME VELOCITIES
DIXON-LEWIS ET, EXPT FUEL RICH H2 02 N2 FLAME
DIXON-LEWIS, MECHANISM H2 02 N2 FLAME
SPALDING* THEORY OF FLAMES WITH CHAIN REACION
DIXON LEWIS* CONSERVATION EQUATIONS FOR FLAMES
DIXON-LEWIS, TRANSPORT PHEN IN FLAMES
BROKAW ET, CO OXIDATION IN AUTO EXHAUST
MARLOW,
DE LACHAUXo
ANDERSON ET«
JOHNSON, MECHANISM OF CORROSION BY FUEL IMPURITIES
BARRET ET,
103
-------
Table AIM (Cont). List of References in Order_of Acquisition Number
00616
00617
00618
00619
00620
00621
00622
00623
00624
00625
00626
00627
00628
00629
00630
00631
00633
00634
00635
00636
00637
00638
00639
00641
00701
00702
00703
007C4
00705
00706
00707
00708
00709
00710
00711
00712
00713
00714
00716
00717
00718
00719
00720
00721
00722
00723
00724
00725
00726
00727
00729
00730
00731
00732
00733
00734
SYMCA-
SYMCA'
JIFUA'
JIFUA'
JIFUA'
JIFUA'
BOOK-
SYMCA'
JEFPA-
BOOK-
CBFMA-
ZFKHA'
OIGTA
COMBA
MEENA'
MEENA
JIFUA
JIFUA
TFSOA-
SYMCA'
SYMCA
PRLAA'
TFSOA'
FRXXA
IJCKA
IJCKA
IJCKA'
IJCKA'
IJCKA
VGBGA'
JAMCA'
JHTRA'
SYMCA-
JIFUA'
JIFUA-
JIFUA'
SYMCA-
TASMA'
THENA-
JIFUA'
ERKOA-
JPCAA-
SYMCA'
SYMCA'
JCPSA'
JPCHA-
CJCEA-
TORFA-
JIFUA-
CBFMA-
PYDYA-
PYDYA'
PYDYA'
PYDYA-
PYDYA-
PYDYA-
-1969-12-635
-1971-13-427
-1965-87-374
-1965-29-322
-1956-29-372
-1967-40-342
1963- -228
-1972
,-1967-89-283
1963- -195
-1971-16-125
-1940-14-1428
-1966-NOV-66
-1963-JAN-MAR
-1960-82-93
-1960-82-92
-1953-26-122
-1969-42-67
-1966-62-2150
-1965-10-463
-1965-10-473
-1966-295-363
-1969-65-3013.
-2040117
-1969-1-89
-1969-1-29
-1969-1-3
-1971-3-467
-1971-3-381
-1969-1133
-1971- -756
-1971- -365
-1963-9-7
-1961- -494
-1970- -517
-1970- -301
-1952-4-789
-1957-79-1727
-1968-15-44
-1968- -195
-1971-7-171
-1971- -52
-1969-12-604
-1971-13-373
-1969-50-3377
-1965-69-2111
-1963-41-826
-1963-40-28
-1971- -599
-1971-17-197
-1967-5-375
-1968-6-101
-1968-6-187
-1968-6-355
-1964-1-147
-1965-3-245
NETTLETON ET, FORMATION AND DECOMP OF S03
MERRYMAN ET , 503 FLAME CHEMISTRY- H2S/COS FLAMES
LEVY ET,
CRUMLEY ET.
RENDLE ET.
CROSSLEY
JOHNSON. MECHANISM OF CORROSION BY FUEL IMPURIITES
WENDT ET. REDUCTION OF S03 AND NOX BY SEC FUEL
REID*
JOHNSON. MECHANISM OF CORROSION BY FUEL IMPURIITES
ARMITAGE ET. STUDIES OF REACTION OF N02 AND S02
BOREKOV ET. KINETICS OF REACTION OF N02 AND S02
MUNROE.
GLAUBITZ.
AUSTEN ET.
COYKENDALL.
FLINT. METAL ADDITIVES
LEE ET,
JOFFE ET.
WEBSTER ET.
THRUSH ET,
HALSTEAD ET,
HALSTEAD ET,
PATENT TO JOHN ZINK CO
MCGRAW ET, CH30NO PHOTOLYSIS AND DECT ION OF HNO
BENSON ET. ICL AS SOURCE OF CL. CL WITH H2
FRANKLIN ET, BOND ENERGIRES IN CHLOROETHANES
KREZEN5KI ET, REACTIONS OOP) WITH 03 AND COS
BATTEN ET. REACTION FO N20 AND N02
NIEPENBERG, DESIGN FEATURES OF GAS BURNERS
PLATTEN ET, DEFLECTED TURBULENT JET FLOWS
RAMSEY ET, HEATED JET IN DEFLECTING STREAM
BECKER ET, MIXING AND FLOW DUCTED TURBULENT JETS
THRING, TURBULENT DIFFUSION COMBUSTION, SURVEY IJ
GIBSON ET, MODEL OF COMBUSTION OF SOLID PARTICLES
NURUZZAMAN ET. FLAMES ON MONOSIZED DROPLET STREAMS
THRING ET. LENGTH OF ENCLOSED TURBULENT FLAMES
SHERMAN, HEAT TRANSFER BY RADIATION FROM FLAMES
IVANOV, FLOW SECTION OF VORTEX BURNERS
HAKLUYTT ET. DESIGN OF AIR REGISTERS FOR OIL-FIRED
NARASIMHAN. BERECHNUNG D FLAMMENLANGE INDUSTRIEOFE
SCHLUCHMANN ET, N COMPUNDS OTHER THAN NO IN AUTO E
NEWHALL, KINETICS OF ENGINE GENERATED NOX AND CO
FENIMORE, FORMATION OF NO IN PREMIXED HC FLAMES
LIN ET, REACTION OF N20 WITH CO AND 0 WITH CO
MODICA, KINETICS OF N20 DECOMPOSITION BY MASS SPEC
MUI ET, PHOTOLYSIS OF HNCO VAPOR
RAKOVSKI] £T, PYROLYSIS OF PYRIDINE AND QUINOLINE
GODRIDGE ET, CARBON FORMATION IN LARGE BURNERS
DURIE ET, EFFECT OF S02 ON H ATOM RECOMBINATION
BAHN, CHEMICAL KINETICS N 0 AND H
H+C02»OH+CO AND
C02 CO HCO
CO AND HCO
N2 02 NO N AND 0
H20 H02 H202 03
BAHN, CHEMICAL KINETICS
BAHN, CHEMICAL KINETICS
CHEMICAL KINETICS
CHEMICAL KINETICS
CHEMICAL KINETICS
BAHN,
BAHN,
BAHN*
104
-------
Table AH-1 (Cont). List of References in Order of Acquisition Number
00725
00736
00737
00738
00739
00740
00741
00743
00744
00746
00747
00748
00749
00750
00751
00752
00752
00753
00754
00755
00756
00758
00759
00760
00761
00762
00763
00764
00765
00766
00767
00768
00769
00771
00772
00773
00778
00779
00780
007C1
00784
00786
00787
00788
00790
00791
00794
00795
00796
00797
00798
00799
00800
00801
00802
00803
00804
00805
00806
PYDYA-1965-2-315
PYDYA-1965-2-197
PYDYA-1965-2-91
PYDYA-1967-5-221
PYDYA-1966-4-211
PYDYA-1966-4-63
PYOYA-1966-4-57
PYDYA-1966-4-371
PYDYA-1966-4-305
PYDYA.1964-1-271
PYDYA-1964-1-335
CBFMA-1971-17-131
CBFMA-1971-17-139
MTURA-1968-20-567
PYDYA-1966-3-235
CBSTA-1970-2-161
BOOK-1965
BOOK-1963
BOOK-1949
REPORT-1966
REPORT
BOOK-1966
BOOK.-1969
BOOK-1945
CBFMA-1968-12-603
TFSOA-1968-64-71
JPCHA-1961-65-298
AJCHA-1967-20-825
SYMCA-1967-11-871
REPORT
CBFMA-1964-8-113
CBFMA-1967-11-109
BOOK-1960
BOOK-1965
BCSJA-1966-39-2352
CBFMA-1969-13-173
SYMCA
BAHNt CHEMICAL KINETICS H20 H02 03 WITH
BAHNt CHEMICAL KINETICS H2 02 OH H AND 0
BAHN. CHEMICAL KINETICS N03 N20 N02 03 02 NO N
BAHNt CHEMICAL KINETICS REACTIONS OF 0 AND H
BAHNt CHEMICAL KINETICS N2H4 N2H3 N2H2
BAHNt CHEMICAL KINETICS N2 N H2 H NH NH2 NH3
WECKER ETt ON THE FOUR CENTER AIR REACTION
BAHNt CHEMICAL KINETICS F CL H 0 N SYSTEM
BAHNt CHEMICAL KINETICS N2H4 N2H3 N2H2
BAHN. CHEMICAL KINETICS N20 N02 03
BAHNt CHEMICAL KINETICS N20 N02 03
SHAHEO ETt NO FORMATION IN PROPANE AIR AND H2 AIR
ALDRED ET. MECH OF COMB OF DROPLETS ON HEPTANE
MAZUR ETt INFLUENCE OF TEMP ON COKING
HILL ETt MONOETHYLAMINE COMBUSTION
BOWMANt HIGH TEMP OXIDATION OF HYDROCARBONS
LATHAM ETt HYDOCARBON ANALYSIS ASTM STP 389
LOWREYt CHEMISTRY OF COAL UTILIZATION
KIRK ETt ENCYCLOP OF CHEMICAL TECHNOLOGY
HOPFt REPORT FOR ADVANCED RESEARCH PROJECTS AG
STULL t JANAF THERMOCHEMICAL TABLES
KUENTZELt CODEN FOR PERIODICAL TITLES
HOCHSTlMt BIBLIOGRAPHY OF CHEMICAL KINETICS AND
SHREVEt THE CHEMICAL PROCESS INDUSTRIES
BULLt SHOCK TUBE STUDY OF OX ID OF AMMONIA
BRADLEY ETt OXIDATION OF NH3 IN SHOCK WAVES
FENIMORE ETt OXIDATION OF AMMONIA IN FLAMES
DRUMMOND ETt SHOCK INITIATED EXO REACTIONS
MACLEAN ETt AMMONIA AND HYDRAZINE DECOMPOSITION F
SUTTON ETt OXIDES OF NITROGEN IN ENGINE EXHAUST P
ANDREWS ETt COMB OF NH3 WITH 02 N20 AND NO
GRAY ETt COMB OF H2 AND 02 WITH NH3 AND N20
GAYDON ETt FLAMESt CHAPMAN AND HALL, LONDON. P151
FR1STROM ETt FLAME STRUCTUREt MCGRAW HILL NY 1965
TAKEYAMA ETt AMMONIA OXIDATION IN SHOCK WAVES
WILDEt ROLE OF HNO IN THE H2-NO REACTION
MYERSON ET, IGNITION L1NITS PROPANE-N02 FLAMES
CRADA-1950-231-1302 PATRY ETt
BOOK-1970
BOOK-1939
ERKOA-1929-5-455
REPORT1968
SYMCA-1963-9-560
THESIS-1967
PREPRINT-1971
PREPRINT-
ESTHA-1969-3-63
RAPPOPORT, CHEMISTRY OF THE CYANO GROUP
CONANTt THE CHEMISTRY OF ORGANIC COMPOUNDS MACMIL
RUHEMANNt THERMIC BEHAVIOR OF PHENOLS AND BASES
BAULCH ETt RATE DATA FOR HOMOGENEOUS GAS REACT
FRISTROMtRADlCAL CONC AND REACT IN CH4 02 FLAME
MORGANt COMB OF CH4 IN A JET STIRRED REACTOR
MARTIN ET, CONVERSION OF UEL NITROGEN TO NOX
TURNER ETt COMB MOD AND FUEL NITROGEN CONTENT
LEVY ET, SOX FORMATION COS FLAME
REPORT-9840-6002-RUOTYSONt IMPLICIT INTEGRATION FOR CHEMICAL KINETICS
REPORT
REPORT-1969
REPORT
REPORT-1969
PREPRINT-1971
SYMCA-1971-13-
REPORT
BOOK-1962
CBSTA-1971-2-329
SYMCA-1956-6-198
REPORT
BAILEY ET*INTEGRATION OF ONE DIM FLOW EQUATIONS
BARTQK ETt SYSTEMS STUDY OF NOX CONTROL METHODS
FINE ET, NITROGEN IN COAL AS AOURCE OF NOX
JONKE ETt REDUCTION OF POLLUTION BY FLUIDIZED
SOMMERLAD ETt NOX EMISSIONS-ANALYTICAL EVAL OF T
BREEN ETt NOX CONTROL UTILITY POWER
BIENSTOCK ETt FORMATION OF NOX IN PULV COAL COM
DURRANT ETt INTOOD TO ADV INORGANIC CHEMIASTRY
BOCKHORN ETt SYNTHESIS OF HCN IN A FLAME REACTION
LEVY, DISCUSSION
JOHNSON t GAS PHASE KINETICS OF NEUTRAL 0 SPECIES
105
-------
Table AH-2
LITERATURE REFERENCES ALPHABETIZED BY AUTHOR
ACQ NO
00386
00378
00749
00398
00613
00767
00312
00321
00329
00344
00347
00367
00429
00512
00432
00572
00626
00384
00428
00630
00349
00381
00541
00557
00540
00729
00730
00731
00732
00733
00734
007S5
00736
00737
00738
00739
00740
00743
00744
00746
00747
00796
00415
00559
00615
00797
00355
00357
00358
00705
00786
COOEN REF
BSCBA-1968-77-433
INCEA-1971-11-739
CBFMA-1971-17-139
ESTHA-1971-5-39
TASMA-1958-80-1231
CBFMA-1964-8-113
CBFMA-1965- -335
KINFA-1969
CBFMA-1970-15-211
ZFKHA-1940-14-1428
JIFUA-1970- -234
OIGJA-1971-1-74
CENEA-1971-6-15
JCPSA-1958-29-456
SCIEA-1971-174-1341
JIFUA-1970- -397
CBFMA-1971-16-125
SYMCA-1965-10-377
JPCHA-1969-73-2555
MEENA-1960-82-93
IJCEA-1969-9-317
JPCAA-1971-21-702
JPCAA-1971-21-702
PAPWA-1970-32-683
PYDYA-1967-5-74
PYDYA-1967-5-375
PYDYA-1968-6-101
PYDYA-1968-6-187
PYDYA-1968-6-355
PYDYA-1964-1-147
PYDYA-1965-3-245
PYDYA-1965-2-315
PYDYA-1965-2-197
PYOYA-1965-2-91
PYDYA-1967-5-221
PYDYA-1966-4-211
PYDYA-1966-4-63
PYDYA-1966-4-371
PYDYA-1966-4-305
PYDYA, 1964-1-271
PYDYA-1964-1-335
REPORT
JOCRA-1969-45-256
CEPRA-1971-67-62
JEFPA-1966-88-165
REPORT-1969
PRLAA-1963-272-147t
PRLAA-1965-283-302
PRLAA-1965-283-291
IJCKA-1971-3-381
REPORT1968
AUTHOR TITLE! ABBREVIATED)
AILL1ET ET, BURN VEL OF C2N2 OR HCN WITH 02
AKITA* FLAME PROPAGATION BASIC THEORY
ALDRED ETi MECH OF COMB OF DROPLETS ON HEPTANE
ALTSHULLER ET. PHOTO CHEM ASPECT OF AIR POLLUTION
ANDERSON ET,
ANDREWS ET* COMB OF NH3 WITH 02 N20 AND NO
ANON* PARAGRAPH QUATATION FROM CONF NEWS
ANON* REACTIONS OF SO*S02* S03 WITH H»0*OH»NO»N02
ANON* S SPECIES IN BURNT GAS OF PROPANE AIR FLAMES
ANON, GENERAL PHYSICAL CHEM
ANON* REVIEW CHEM ASPECTS OF FIRESIDE CORROSION
ANON* PROFITABILITY FACTORS IN GAS OIL CRACKING
ANON* DMN IN CIGARETTE SMOKE
ANON*
ARCHER ET* ENVIRONMENTAL NITROSO CMPDS
ARCHER ET. MULTISTAGE COMBUSTION PART 1
ARMITAGE ET, STUDIES OF REACTION OF N02 AND S02
ASHMORE, REVIEW ELEMENTARY COMB REACTIONS
ASMUS ET. PYROLYSIS KINETICS OF ACETONITRILE
AUSTEN ET,
AVERBUCH ET. ELEMENTAL S BY REDUCTION WITH NAT GAS
BAGWELL ET, BOILER OPERATING MODE FOR RED NOX
BAGWELL ET, BOILER OPERATING MODES FOR REDUCED NOX
BAGWELL ET, NOX REDUCTION PROGRAM FOR OIL AND GAS
BAHN ET, REACTIONS INVOLVING N AND 0
BAHN. CHEMICAL KINETICS N 0 AND H
BAHN, CHEMICAL KINETICS H+C02-OH+CO AND
BAHN, CHEMICAL KINETICS C02 CO HCO
BAHN, CHEMICAL KINETICS CO AND HCO
BAHN* CHEMICAL KINETICS N2 02 NO N AND 0
BAHN* CHEMICAL KINETICS H20 H02 H202 03
BAHN* CHEMICAL KINETICS H20 H02 03 WITH
BAHN, CHEMICAL KINETICS H2 02 OH H AND 0
BAHN* CHEMICAL KINETICS N03 N20 N02 03 02 NO N
BAHN* CHEMICAL KINETICS REACTIONS OF 0 AND H
BAHN* CHEMICAL KINETICS N2H4 N2H3 N2H2
BAHN* CHEMICAL KINETICS N2 N H2 H NH NH2 NH3
BAHN, CHEMICAL KINETICS F CL H 0 N SYSTEM
BAHN, CHEMICAL KINETICS N2H4 N2H3 N2H2
BAHN, CHEMICAL KINETICS N20 NO 2 03
BAHN, CHEMICAL KINETICS N20 N02 03
BAILEY ET, INTEGRATION OF ONE DIM FLOW EQUATIONS
BARTLE ET, TOBACCO SMOKE BY GAS CHROMATOGRAPHY
BARTOK ET* CONTROL OF NOX EMISSIONS FROM STATIONA
BARRET ET,
BARTOK ET, SYSTEMS STUDY OF NOX CONTROL METHODS
BASCO ET* CYANOGEN RADICALS BY FLASH PHOTOL
BASCO* REACTION OF C2N2 WITH 02
BASCO ET. REACTION OF C2N2 WITH NO
BATTEN ET. REACTION FO N20 AND N02
BAULCH ET. RATE DATA FOR HOMOGENEOUS GAS REACT
106
-------
Table An-2 (Cont). Literature References Alphabetized by Author
00709 SYMCA-1963-9-7
00702 IJCKA-1969-1-29
00316 JCPSA-1963-39-275
00537 APMPA-1968-20
00590 CBFMA-1960-4-325
00802 REPORT
00361 1EPDA-1969-8-206
00393 CBSTA-1971-4-73
00804 CBSTA-1971-2-329
004C7 PRLAA-1968-305-93
00627 ZFKHA-1940-14-1428
00413 CBSTA-1971-3-37
00510 CESCA-1963-18-177
00558 CIEAA-1970
00752 CBSTA-1970-2-161
00762 TFSOA-1968-64-71
00801 5YMCA-1971-13-
00353 HCACA-1930-13-629
00371 OIGJA-1971-9-94
00431 ACIEA-1970-9-181
00506 JCPSA-1955-23-2399
00602 NASCA-1970-TND7024
00390 ESTHA-1971-5-333
00501 TFSOA-1956-52-1475
00503 PRLAA-1956-235-89
00761 CBFMA-1968-12-603
00351 PCSLA-1964- 410
00400 CHREA-1958-58-173
00550 SAUPA-1970-700470
00551 CBSTA-1971-3-53
00409 TFS3A-1967-63-1687
00579 NAFTA-1970- -11,1
00507 PYDYA-1965-3-197
00509 PYOYA-1966-4-119
00375 JAHSA-1971-2B-847
00528 PRLAA-1970-316-539
00421 SYMCA-1965-10-311
00359 CBFMA-1957-1-60
00314 AICPA-1968-6A
00781 BOOK-1939
00591 JASCA-1952-74-739
00560 SAUPA-1970-700708
00583 SCPOA-1970-58-161
00631 MEENA -1960-82-92
00389 CBFMA-1971-16-243
00621 JIFUA-1967-40-342
00619 JlFUA-1965-29-322
00318 CBFMA-1967-11-150
00331 CBFMA-1971-16-125
00342 PRLAA-1966-295-72
00420 CBSTA-1971-3-83
00385 TFSOA-1968-64-1836
00612 REGTA-1965-4-1117
00336 PICMA-1963- 216
00575 CEPRA-1971-67-57
00594 SYMCA-1958-7-475
BECKER ETt MIXING AND FLOW DUCTED TURBULENT JETS
BENSON ETt ICL AS SOURCE OF CL. CL WITH H2
BERKOWITZ ET, EQUIL COMPOSITION OF SULFUR VAPOR
BERGER ET. REACTIONS OF SOX IN STACK PLUMES
BERLAD ET. THEORY OF FLAME EXTINCTION LIMITS
BIENSTOCK ET, FORMATION OF NOX IN PULV COAL COM
BLAKEMORE ET, PYROLYSIS OF N-BUTANE
BLUMBERG ET, NO FORMATION IN SPARK IGNITED ENGINES
BOCKHORN ET, SYNTHESIS OF HCN IN A FLAME REACTION
BODEN ET, EXCITATION OF CN IN ACTIVE NITROGEN
BOREKOV ET, KINETICS OF REACTION OF NO2 AND S02
BOWMAN, NO FORMATION KINETICS. THE H2-N2-02 REACTI
BOWEN ET, OSS APPROXIMATION IN CHEMICAL KINETICS
BOWMAN, NOX FORMATION IN COMB. THE H2-02-N2 REACT
BOWMAN, HIGH TEMP OXIDATION OF HYDROCARBONS
BRADLEY ET, OXIDATION OF NH3 IN SHOCK WAVES
BREEN ET, NOX CONTROL UTILITY POWER
BR1NER ET. L'ACTION DES DISCH. ELECT-C2N2
BROOKS ET, CRACKING GAS OILS
BROWN ET, CHEM BEHAVIOR OF ACTIVE NTTROGEN
BROMBERG ET, OXIDATION OF CH4 WITH N02
BROKAW ET. CO OXIDATION IN AUTO EXHAUST
BUFALIN1 ET, OXID OF N-BUTANE BY PHOT OF N02
BULEW1CZ ET, DISSOCIATION CON5TS BY FLAME PHOTOMET
BULEWICZ ET* HYDROGEN ATOMS IN BURNT GAS MIXTURES
BULL, SHOCK TUBE STUDY OF OXID OF AMMONIA
CAMPBELL ET, BEHAVIOR OF CN IN ACTIVE N
CAMPBELL ET. THE HYDROGEN BROMINE SYSTEM
CARR ET, INFLUENCE OF FUEL COMPOSITION ON CO AND
CARETTO ET. ROLE OF KINETICS IN EMISSION OF NO
CERCEK ET. REACTION OF H AND OH WITH PYRIDINE
CHERADAME. THE AERODYNAMICS OF FLAMES
CHINITZ. ANALYSIS OF CH4 AIR COMBUSTION
CH1NITZ ET, NON EOUIL HYDROCARBON AIR COMBUSTION
CLARK, CHEMICAL KINETICS OF C02 ATMOSPHERES
CLARK ET, KINETICS OF N WITH 02(3SG-I AND (IDG)
CLYNE, REACTIONS OF THE HNO MOLECULE
COHEN ET, BURNING VELOC OF HCN IN AIR AND 02
COLLINS, REVIEW OF SULFUR FLAME TECHNOLOGY
CONANT, THE CHEMISTRY OF ORGANIC COMPOUNDS MACMIL
COOLEY ET. BURNING VELOCITY IN H2 BR2 FLAMES
CORNELIUS ET, FORMATION AND CONTROL OF NOX
COTTON, THE STRUCTURE OF FLAMES
COYKENDALL,
CRAMAROSSA ET, OZONE DECOMP IN STEADY FLAMES
CROSSLEY
CRUMLEY ET,
CULLIS ET, REACTION OF S02 AND OXGENATED RADICALS
CULLIS, REACTIONS BETWEEN S02 AND N02
CULLIS ET. HOMOGENEOUS GAS OXIDATION OF S02
D'SOUZA ET, METHANE OXID IN A STEADY FLOW REACTOR
DAVIES ET, REACTION OF 0 WITH HCN. CNCL AND CNBR
DE LACHAUX.
DEMARDAUCHE ET. REACTION OF S CMPDS IN FLAMES
DEMAREST, STATUS OF REACTOR FURNACES
DIXON-LEWIS ET. LIMITS OF INFLAMMABILITY
107
-------
Table AH-2 jCpnt)._ Literature References Alphabetized by Author
00597
00598
00600
00601
003^5
00764
00596
00328
00727
00803
00514
00333
00350
00382
00520
00721
00763
00798
00633
00508
00703
005£4
00595
C0771
00787
00369
00373
00340
00769
00399
00511
00515
00571
00711
00513
C0629
00726
00404
00354
00363
00425
00586
00768
00408
00326
00403
00717
00330
00529
00554
00638
00639
00546
00395
00313
00574
PRLAA-1970-317-227
PRLAA-1970-317-235
PRLAA- -298-495
PRLAA-1968-307-111
TFSOA-1946-42-354
AJCHA-1967-20-825
NACRA-1954-1158
CBFMA-1970-15-157
CBFMA-1971-17-197
BOOK-1962
CHREA-1960-93-3014
JPCHA-1965-10-
JACSA-1947-69-3143
SYMCA-1960-8-127
JPCHA-1959-63-1834
SYMCA-1971-13-373
JPCHA-1961-65-298
REPORT
J1FUA-1953-26-122
ARPLA-1967-18-261
IJCKA-1969-1-3
SYMCA-1953-4-267
JCPSA-1955-23-1360
BOOK-1965
SYMCA-1963-9-560
IECHA-1942-34-567
IECHA-1942-34-567
PRLAA- -276-461
BOOK-1960
JCPSA-1970-52-5718
IECHA-1955-47-972
JCPSA-1965-43-3237
JIFUA-1970- -517
JIFUA-1970- -517
TFSOA-1967-63-662
COMBA-1963-JAN-MAR
JIFUA-1971- -599
MOPHA-1966-11-403
JACSA-1959-81-6190
SYMCA-1965-10-435
SYMCA-1960-8-496
SYMCA-1967-11 -1057
CBFMA-1967-11-109
MOPHA-1965-10-401
JIFUA-1970-43-187
JPCHA-1966-70-1793
J1FUA-1968- -195
PRLAA-1968- -380
PRLAA-1970-316-575
ESTHA-1971-4-320
PRLAA-1966-295-363
TFSOA-1969-65-3013,
JPCAA-1970-20-377
CBFMA-1971-16-237
JIFUA-1967-40-142
JIFUA-1971- -38
DIXON-LEWIS ET, EXPT FUEL RICH H2 02 N2 FLAME
DIXON-LEW1S. MECHANISM H2 02 N2 FLAME
OIXON LEWIS i CONSERVATION EQUATIONS FOR FLAMES
DIXON-LEWISt TRANSPORT PHEN IN FLAMES
DOOLEY ETf OXIDATION OF S02 IN GAS FLAMES
DRUMMOND ETf SHOCK INITIATED EXO REACTIONS
DUGGER ETt PREDICTION OF FLAME VELOCITIES
DURIE ETt CATALYTIC FORM OF S03 IN FUEL RICH PROPA
DURIE ET* EFFECT OF S02 ON H ATOM RECOMBINATION
DURRANT ET, INTOOD TO ADV INORGANIC CHEM1ASTRY
ECKLING ET* KIN STUD. PHOTOCHLORINATION
FENIMORE ET* S IN THE BURNT GAS OF H2-02 FLAMES
FENIMORE* HOMOGENEOUS REACTION OF NO AND CO
FENIMORE ET* RATE OF REACTION 0+N20-NO+NO
FENIMORE ET, CONSUMPTION OF 02 IN HC FLAMES
FENIMORE* FORMATION OF NO IN PREMIXED HC FLAMES
FENIMORE ET. OXIDATION OF AMMONIA IN FLAMES
FINE ET. NITROGEN IN COAL AS AOURCE OF NOX
FLINT* METAL ADDITIVES
FRANKLIN* KINETICS OF HYDROCARBON COMBUSTION
FRANKLIN ET» BOND ENERGIRES IN CHLOROETHANES
FRISTROM ET* T PROFILES IN PROPANE-AIR FLAMES
FRISTROM* ONE-DIMENSIONAL FLAME FRONT MODELS
FRISTROM ET* FLAME STRUCTURE. MCGRAW HILL NY 1965
FRISTROM,RADICAL CONC AND REACT IN CH4 02 FLAME
FUCHS ET, THEORY OF COAL PYROLYSIS
FUCHS ET, THEORY OF COAL PYROLYSIS
GAYDON ET, SHOCK TUBE DECOMPOSITION OF S02
GAYDON ET, FLAMES* CHAPMAN AND HALL* LONDON* P151
GELBART ET. VIBRATIONAL RELAXATION AND DISSOSIATI
GERHARD ET, PHOTOCHEMICAL OXIDATION OF S02
GETZINGER ET, RECOMBINATION H+02+M-H02+M
GIBSON, COMB OF SOLID PART IN STREAM WITH RECIRCU
GIBSON ET, MODEL OF COMBUSTION OF SOLID PARTICLES
GILES ET. REACTIONS OF RF3 RADICALS WITH ORGANIC H
GLAUBITZ.
GODRIDGE ET. CARBON FORMATION IN LARGE BURNERS
GOGGENHEIM. DIMERIZATION OF NO. CORRECTION
GRAVEN. KINETICS OF DECOMP OF N20 AT HIGH T
GRAY ET* H-ATOM ABSTRATION FROM N-H BONDS
GRAY ET, FLAME OF METHYL NITRITE
GRAY ET, PRESENT POSITION IN EXPLOSION THEORY
GRAY ET, COMB OF H2 AND 02 WITH NH3 AND N20
GUGGENHEIM. DIMERIZATION OF GASEOUS NO
GUNTHER* MEAUSERMENTS OF FLAME TURBULENCE
GUTMAN ET* THERMAL DECOMP OF N20
HAKLUYTT ET* DESIGN OF AIR REGISTERS FOR OIL-FIRED
HALSTEAD ET* CHEMILUMINESCENT REACTION OF SO
HALSTEAD ET* REACTION OF H WITH C2H4
HALL ET* NOX CONTROLFROM STATIONARY SOURCES
HALSTEAD ET*
HALSTEAD ET,
HARDISON* CONTROLLING OXIDES OF NITROGEN
HAY ET* OXIDATION OF GASEOUS FORMALDEHYDE
MEDLEY, FORMATION OF S03 IN FLAME GASES
MEDLEY ET* COMBUSTION OF SINGLE DROPS ANS SPRAYS
108
-------
Table AII-2 (Cont). Literature References Alphabetized by Author
00365 AICEA-1972-18-84
00426 NATUA-1964-204-9B8
00564 SAUPA-1971-710011
00423 SYMCA-1960-8-487
00751 PYOYA-1966-3-235
00523 TFSOA-1957-53-1102
00759 BOOK-1969
00394 CBFMA-1971-17-31
00419 PRLAA-1970-314-585
00755 REPORT-1966
00363 JACSA-1962-84-4519
00414 JACSA-1962-84-4509
00387 PRLAA-1963-273-145
00366 CJCHA-1953-31-30
00716 THENA-1968-15-44
00405 RIFPA-1964-19-523
00547 ASMSA-1959-A-308
00635 TFSOA-1966-62-2150
00614 BOOK-1963-204
00622 BOOK-1963- -228
00625 BOOK-1963- -195
00806 REPORT
00799 REPORT-1969
00376 JAHSA-1971-28-833
00334 TFSOA-1967-63-2442
00346 CBFMA-1969-13-324
00430 FUELS-1969-48-297
00580 CEPRA-1965-61-A56
00341 PRLAA-1958-247-123
00754 BOOK-1949
00368 CEPRA-1969-7-71
00504 UCKA-1969-1-105
00704 IJCKA-1971-3-467
00758 B00<-1966
00570 IEPDA-1971-10-357
00362 IECFA-1969-8-374
00544 A1CPA-1971-SF-28B
00752 BOOK-1965
00534 CBSTA-1970-1-313
00565 CBFMA-1970-15-97
00634 JIFUA-1969-42-67
00319 ESTHA-1969-3-63
00322 JCPAA-1967-17-800
00324 CBFMA-1965-9-229
00348 ESTHA-1970-4-653
00618 JIFUA-1965-87-374
00794 ESTHA-1969-3-63
00805 SYMCA-1956-6-198
00525 CBFMA-1971-16-311
00372 TOSCA- -6-106
00588 SYMCA-1956-6-20
00722 JCPSA-1969-50-3377
00396 CBSTA-1971-4-9
00576 CESCA-1970-25-623
00753 BOOK-1963
00339 JIFUA-1962-35-502
HERRIOTT ET, KINETICS OF PROPANE PYROLYSIS
HERZBERG ET» IDENT OF FREE RAD IN FLASH PHOTOL
HEYWOOD ET, PREDICTION OF NOX IN SI ENGINE EMISSI
HICKS* DECOMP FLAME OF ETHYL NITRATE
HILL ET, MONOETHYLAMINE COMBUSTION
HOARE ET, REACTION OF CH3 WITH 02 AND COMPARISON
HOCHSTIM, BIBLIOGRAPHY OF CHEMICAL KINETICS AND
HOLLAND ET, FLAME SPEED IN H2-ETHANE-N20 SYSTEM
HOMER ET, DISSOCIATION OF H20 IN SHOCK WAVES
HOPF, REPORT FOR ADVANCED RESEARCH PROJECTS AG
HURD ET, PYROLYSIS OF PYRIDINE, PICOLINES AND
HURD ET, PYROLYTIC FORM OF ARENES, 1 SURVEY
HUSAIN ET, OXIDATION OF NH3 AND N2H4
INGOLD ET* THERMAL DECOMPOSITION OF BENZENE DERIVA
IVANOV, FLOW SECTION OF VORTEX BURNERS
JANIN ET, LA FLAMME CH4-NH3-02
JEFFER1S.ET, EFFECT OF OPERATING VARB ON EMISSION
JOFFE ET,
JOHNSON, MECHANISM OF CORROSION BY FUEL IMPURITIES
JOHNSON, MECHANISM OF CORROSION BY FUEL IMPURIITES
JOHNSON, MECHANISM OF CORROSION BY FUEL IMPURIITES
JOHNSON , GAS PHASE KINETICS OF NEUTRAL 0 SPECIES
JONKE ET, REDUCTION OF POLLUTION BY FLUID1ZED
JULIENNE ET, TEMP DEP OF C02 ABSORPTION
KALLEND S02 ON CHEMILUM AND ATOM RECOMBINATION
KALLEND, EFFECT OF S02 ON EQUIL IN H2 FLAMES
KARN ET, COAL PYROLYSIS USING LASER IRRADIATION
KARLOVITZ, FLOW PHEN AND FLAME TECHNOLOGY
KAUFMAN, USE OF AIR AFTERGLOW IN REACTIONS OF 0
KIRK ET, ENCYCLOP OF CHEMICAL TECHNOLOGY
KITZEN ET, GAS OIL PYROLYSIS IN TUBULAR REACTORS
KONDRATIEV ET, INTERACTION OF CO AND 0
KREZEflSKI ET, REACTIONS OOP) WITH 03 AND COS
KUENTZEL, CODEN FOR PERIODICAL TITLES
KUMAR ET* PNEUMATIC ATOMIZATION
KUNUGI ET, KINETICS OF THERMAL REACTIONOF C2H4
LANGE NOX FORMATION IN PREMIXED COMBUSTION
LATHAM ET, HYDOCARBON ANALYSIS ASTM STP 389
LAVOIE ET, NO FORMATION IN 1C ENGINES
LAVOIE, SPECTROSCOPIC MEAS OF NO IN SI ENGINES
LEE ET,
LEVY ET, SOX FORMATION IN COS FLAMES
LEVY ET, SOX FORM IN LOW P H2S FLAMES
LEVY ET, MICROSTRUCTURE OF H2S FLAMES
LEVY ET, FORMATION OF SOX IN COMBUSTION
LEVY ET,
LEVY ET, SOX FORMATION COS FLAME
LEVY, DISCUSSION
LIFSHITZ ET, SHOCK TUBE FOR IGN OF CH4-O2-ARGON MI
LINNELL, THERMAL DECOMPOSITION OF PYRIDINE
LINNETT ET, LIMITS OF INFLAMMABILITY
LIN ET, REACTION OF N20 WITH CO AND 0 WITH CO
LIVESEY ET, FORMATION OF NOX IN OXY/PROPANE FLAMES
LONG ET, SELF-IGNITION OF FUEL DROPS IN HOT GASES
LOWREY, CHEMISTRY OF COAL UTILIZATION
MACFARLANE, FORMATION OF S03 IN COMBUSTION PRODUCT
109
-------
Table An-2 (Cont). Literature References Alphabetized by Author
00765 SYMCA-1967-11-871
00352 TFSOA-1953-49-1312
00433 RADCA- -2-142
00370 CEPRA-1969-65-UU.65
00530 CBSTA-1970-1-461
00611 TASMA-1958-80-225
00750 PREPRINT-1971
00750 MTURA-1968-20-567
00374 JAHSA-1971-28-1095
00427 NATUA-1964-203-619
00701 IJCKA-1969-1-89
00391 CBSTA-1971-4-17
00617 SYMCA-1971-13-427
00410 BCHEA-1967-12-388
00397 JPCHA-1962-66-366
00723 JPCHA-1965-69-2111
00788 THES1S-1967
00724 CJCEA-1963-41-826
00343 SYMCA- -12-323
00628 OIGTA-1966-NOV-66
00561 SAUPA-1971-710158
00778 SYMCA
00718 ERKOA-1971-7-171
00616 SYMCA-1969-12-635
00535 SYMCA-1969-12-603
00720 SYMCA-1969-12-604
00563 SAUPA-1969-690018
00706 VGBGA-1969-1133
00527 ZFKHA-1959-33-572
00568 JIFUA-1970- -301
00712 JIFUA-1970- -301
00566 CBFMA-1970-14-325
00338 BBCUA-1963-27-
00360 JCPSA-1962-36-1146
00641 FRXXA-2040117
00779 CRADA-1950-231-1302
00707 JAMCA-1971- -756
00377 JAHSA-1971-28-1058
00562 SAUPA-1971-710009
00725 TORFA-1963-40-28
00522 JACSA-1951-73-15
00708 JHTRA-1971- -365
00412 CJCEA-1967-45-61
00577 ICONA-1970- -314
00780 BOOK-1970
00624 JEFPA-1967-89-283
00620 JIFUA-1956-29-372
00356 JACSA-1942-64-1880
00401 CBFMA-1966-10-287
00784 ERKOA-1929-5-455
00317 DKPCA-1967-175-647
00424 JPCHA-1968-72-3305
00567 JIFUA-1970- -295
00569 IEPDA-1971-10-297
00538 PLSSA-1967-15-643
00719 JPCAA-1971- -52
MACLEAN ET, AMMONIA AND HYDRAZINE DECOMPOSITION F
MADLEY ET, KINETICS OF OXID OF CHARCOAL WITH N20
MANI ET, REACTION OF 0 WITH BENZENE AND OTHER CMPD
MARSHALL ET, GAS OIL FEEDSTOCKS FO C2H4 PRODUCTI
MARTENEY, KINETICS OF FORM OF NO IN HC AIR COMBUST
MARLOW,
MARTIN ET, CONVERSION OF U£L NITROGEN TO NOX
MAZUR ET, INFLUENCE OF TEMP ON COKING
MCELROY ET, N20, A NATURAL SOURCE OF STRAT NO
MCGRATH ET, UV ABS SPECTRUM OF FREE FULMINATE
MCGRAW ET, CH30NO PHOTOLYSIS AND DECT ION OF HNO
MELVIN ET, REACTION BROADENED DIFFUSION FLAME
MERRYMAN ET, SOS FLAME CHEMISTRY- H2S/COS FLAMES
METCALFE, KINETICS OF COKE COMB IN REGENERATION
MOBERLY, SHOCK TUBE FOR HYDRAZINE DECOMPOSITION
MODICA, KINETICS OF N20 DECOMPOSITION BY MASS SPEC
MORGAN, COMB OF CH4 IN A JET STIRRED REACTOR
MUI ET, PHOTOLYSIS OF HNCO VAPOR
MULCAHY ET, KINETICS OF 0 WITH SOX
MUNROE,
MUZ 10 ET, EFFECT OF T ON FORMATION OF NOX
MYERSON ET, IGNITION LINITS PROPANE-N02 FLAMES
NARAS1MHAN, BERECHNUNG D FLAMMENLANGE INDUSTRIEOFE
NETTLETON ET, FORMATION AND DECOMP OF S03
NEWHALL, ENGINE GENERATED NOX AND CO
NEWHALL, KINETICS OF ENGINE GENERATED NOX AND CO
NICHOLLS ET, WATER INJECTION FOR CONTROL OF NOX
NIEPENBERG, DESIGN FEATURES OF GAS BURNERS
NIKITIN, THERMAL DISSOCIATION OF DIATOMIC MOLECULE
NURUZZAMAN ET, COMB OF MONOSIZED DROP STREAMS
NURUZZAMAN ET, FLAMES ON MONOSIZED DROPLET STREAMS
OPSAHL ET, OSCILLATORY COMBUSTION AND POLLUTANTS
PANKHURST ET, FORMATION OF S03 IN COMBUSTION
PATTERSON ET, KINETICS OF CN IN SHOCK WAVES
PATENT TO JOHN ZINK CO
PATRY ET,
PLATTEN ET, DEFLECTED TURBULENT JET FLOWS
PRINN, PHOTOCHEMISTRY OF HCL IN ATM OF VENUS
QUADER* INTAKE CHARGE DILUTION AND NOX EMISSION
RAKOVSKII ET, PYROLYSIS OF PYRIDINE AND QUINOLINE
RALEY ET, OXIDATION OF FREE CH3
RAMSEY ET, HEATED JET IN DEFLECTING STREAM
RAO ET, SHOCK TUBE STUDY OF REACT OF N2 WITH HCA
RAO ET, STIRRING BY COLD MODEL SIMULATION
RAPPOPORT, CHEMISTRY OF THE CYANO GROUP
REID,
RENDLE ET,
ROBERTSON ET, THERM REACTION OF H2 AND C2N2
ROSSER ET, QUENCHING OF FLAMES BY INHIBITORS
RUHEMANN, THERMIC BEHAVIOR OF PHENOLS AND BASES
SACHYAN ET, COMB OF DILUTE H2S FLAMES
SAFRANY ET, REACTION OF H AND N WITH C2N2 HCN AND
SAKAI ET, COMB OF ATOMIZED FUEL OIL DROPS
SATCUNANATHAN, IGNITION DELAY OF DROPS
SCHOFIELD, KINETIC RATE DATA OF ATM INTEREST
SCHLUCHMANN ET, N COMPUNDS OTHER THAN NO IN AUTO E
110
-------
Table An-2 (Cont). Literature References Alphabetized by Author
00533
00526
00379
00337
00748
00714
00760
00536
00524
00411
00320
00800
00388
00573
00589
00593
00599
00552
00360
00406
00517
00756
00335
00502
00766
00772
00327
00637
00710
00713
00556
00539
00585
00332
00791
00795
00592
00416
00636
00741
00325
00555
00623
00392
00402
00417
00418
00422
00519
00521
00545
00587
00315
00323
00773
00582
00516
00505
00542
PRLAA- -276-324 SEAKINS ET, KINETICS OF GAS PHASE HC OXIDATIONS
CBFMA-1970-14-37 SEERY ET. METHANE OXIDATION BEHIND SHOCK WAVES
PRLAA-1965-288-275 SETSER ET. REACTION OF 0 WITH C2N2
NATUA-1966- -1171 SHAW ET, OX ID OF S02 IN AIR EFFECT OF CO AND NO
SHAMED ET, NO FORMATION IN PROPANE AIR AND H2 AIR
SHERMAN, HEAT TRANSFER BY RADIATION FROM FLAMES
SHREVE. THE CHEMICAL PROCESS INDUSTRIES
SIMONS, VIBRATIONALLY HOT MOLECULES IN RADICAL REA
SLEPPY ET, METHYL 02 AND METHYL NO REACTIONS
SNELLING ET, DECOMPOSITION OF N20 BY 0<1DI N2
SNOWDON ET, H2SO<* CONDENSATION FROM FLUE GASES
SOMMERLAD ET, NOX EMISSIONS-ANALYTICAL EVAL OF T
SPALD1NG ET, CALC PROCEDURE FOR LAMINAR FLAME SPEE
SPALDING, COMBUSTION AS APPLIED TO ENGINEERING
SPALDING ET, PROPAGATION OF STEADY LAM FLAMES
SPALDING, FLAMM LIMITS AND FLAME QUENCHING
SPALDING. THEORY OF FLAMES WITH CHAIN REACION
STARKMAN ET. ROLE OF CHEMISTRY IN GAS TURBINE EMIS
STOCKHAM, COMPOSITION OF GLASS FURNACE EMISSSIONS
STREITWIESER ET. TOLUENE IN MICROWAVE DISCHARGES
STUCKEY ET, REACTIONS OF 0 ATOMS WITH CYCLO PARAFF
STULL , JANAF THERMOCHEMlCAL TABLES
SUGDEN ET. OXIDES AND HYDRIDES OF N AND S IN FLAME
SUGDEN, DISSOCIATION CONSTS BY FLAME PHOTOMETRY I
SUTTON ET, OXIDES OF NITROGEN IN ENGINE EXHAUST P
TAKEYAMA ET, AMMONIA OXIDATION IN SHOCK WAVES
TERRY ET, OD2 BOILER AT SCUYLKULL STATION
THRUSH ET,
THRING, TURBULENT DIFFUSION COMBUSTION. SURVEY IJ
THRING ET, LENGTH OF ENCLOSED TURBULENT FLAMES
TOMANY ET, NOX CONTROL TECHNOLOGY AND DEVELOPMENT
TRUMPY ET, PREKNOCK KINETICS IN AN SI ENGINE
TSUJI ET, COUNTERFLOW DIFFUSION FLAMES
TUCKER. SOX STACK EMISSIONS-REACTIONS AND CONTROL
TURNER ET, COMB MOD AND FUEL NITROGEN CONTENT
CBFMA-1971-17-131
TASMA-1957-79-1727
BOOK-1945
NATUA-1960-186-551
JACSA-1959-81-769
JCPSA-1967-47-228
J1FUA-1969- -188
PREPRINT-1971
CBFMA-1971-17-55
JIFUA-1971- -196
CBFMA-1961-5-11
PRLAA-1957-240-83
PTRSA-1956-A249-1
JEPOA-1971- -333
JPCAA-1971-21-713
JACSA-1963-85-539
JCPSA-1967-46-4843
REPORT
PSRIA-1961
TFSOA-1956-52-1465
REPORT
BCSJA-1966-39-2352
PAPWA-1968-30-786
SYMCA-1965-10-473
JIFUA-1961- -494
SYMCA-1952-4-789
JEPOA-1971- -293
SAUPA-1969-690518
SYMCA-1971-13-997
PPTIA-1969-49-615
PREPR1NT-
REPORT-9840-6002-RUOTYSON, IMPLICIT INTEGRATION FOR CHEMICAL KINETICS
CBFMA-1964-8-343
CPENA-1971-79
SYMCA-1965-10-463
PYDYA-1966-*-57
BUPAA-237
AGPTA-1964
SYMCA-1972
CBSTA-1971-4-59
VAN T1GGELEN ET, FLAMMABILITY LIMITS
WARD ET* OPEN FLAME FURNACE DESIGN
WEBSTER ET,
WECKER ET, ON THE FOUR CENTER AIR REACTION
WEINER ET, AIR POLLUTION IN THE PULP AND PAPER IND
WEIL, STUDY OF POROUS PLATE FLAMEHOLDERS
WENDT ET, REDUCTION OF S03 AND NOX BY SEC FUEL
WESTENBERG, KINETICS OF NO AND CO IN HC FLAMES
SCIEA-1971-171-1013 WESTBERG ET, CO ROLE IN PHOTCHEMICAL SMJG
JCPSA-1966-45-338 WESTENBERG ET, ESR AND KINETICS OF THE OD RADICAL
SYMCA-1965-10-473 WESTENBERG ET, H AND 0 ATOM PROFILES BY ESR
SCIEA-1971-171-1013 WESTBERG ET, CO. ROLE IN PHOTOCHEMICAL SMOG
SYMCA-1965-10-43 WESTENBERG ET, H AND 0 ATOM PROFILES BY ESR IN C2
JCPSA-1969-50-2512 WESTENBERG ET, RATE COEFFICIENTS OF 0 + H2 AND
WESTENBERG, KINETICS OF NO AND CO IN LEAN FLAMES
WESTENBERG ET, THEORY OF LAMINAR SPHERICAL PREM
WEYCHERT ET, KINTEICS OF CAT CONVERSION OF S02
WHEELER, RADICAL RECOMBINATION IN S02 DOPED FLAMES
WILDE. ROLE OF HNO IN THE H2-NO REACTION
WILLIAMS, APPROACH TO FLAME TURBULENCE
CBSTA-1971-4-59
CBFMA-1960-4-161
IJCEA-1969-9-396
JPCHA-1968-72
CBFMA-1969-13-173
JFLSA-1970-40-401
JCPSA-1965-43-3371 WONG ET, REACTIONS OF 0 ATOMS WITH H2 AND NH3
JCPSA-1962-36-2582 WRAY ET, KINETICS OF NO AT HIGH TEMPERATURE
ACPYA-1946-21-576 ZELDOVICH, OXIDATION OF N2 IN COMB AND EXPLOSIONS
111
-------
Table AH-3
LITERATURE REFERENCES
ALPHABETIZED BY CODEN
AGO NO
00431
00542
00555
00314
00365
00544
00764
00537
00508
00547
00328
00410
00772
00614
00622
00625
00752
00753
00754
00758
00759
00760
00769
00771
00760
00781
00803
00386
00325
00312
00318
00324
00328
00329
00331
00346
00359
00773
00388
00389
00394
00395
00401
00525
00526
00565
00566
00587
00589
00590
00592
CODEN REF
ACIEA-1970-9-181
ACPYA-1946-21-576
AGPTA-1964
AICPA-1968-6A
AICEA-1972-18-84
AICPA-1971-SF-28B
AJCHA-1967-20-825
APMPA-1968-20
ARPLA-1967-18-261
ASMSA-1959-A-30B
BBCUA-1963-27-
BCHEA-1967-12-388
BCSJA-1966-39-2352
BOOK-1963-204
BOOK-1963- -228
BOOK-1963- -195
BOOK-1965
BOOK- 196 3
BOOK-1949
BOOK-1966
BOOK-1969
BOOK-1945
BOOK-1960
BOOK-1965
BOOK-1970
BOOK-1939
BOOK-1962
BSCBA-1968-77-433
BUPAA-237
CBFMA-1965- -335
CBFMA-1967-11-150
CBFMA-1965-9-229
CBFMA-1970-15-157
CBFMA-1970-15-211
CBFMA-1971-16-125
CBFMA-1969-13-324
CBFMA-1957-1-60
CBFMA-1969-13-173
CBFMA-1971-17-55
CBFMA-1971-16-243
CBFMA-1971-17-31
CBFMA-1971-16-237
CBFMA-1966-10-287
CBFMA-1971-16-311
CBFMA-1970-14-37
CBFMA-1970-15-97
CBFMA-1970-14-325
CBFMA-1960-4-161
CBFMA-1961-5-11
CBFMA-1960-4-325
CBFMA-1964-8-343
AUTHOR TITLE(ABBREVIATED)
BROWN ETt CHEM BEHAVIOR OF ACTIVE NTTROGEN
ZELDOVICH, OXIDATION OF N2 IN COMB AND EXPLOSIONS
WEIL. STUDY OF POROUS PLATE FLAMEHOLDERS
COLLINS. REVIEW OF SULFUR FLAME TECHNOLOGY
HERRIOTT ET. KINETICS OF PROPANE PYROLYSIS
LANGE NOX FORMATION IN PREMIXED COMBUSTION
DRUMMOND ET. SHOCK INITIATED EXO REACTIONS
BERGER ET, REACTIONS OF SOX IN STACK PLUMES
FRANKLIN. KINETICS OF HYDROCARBON COMBUSTION
JEFFERIS.ET. EFFECT OF OPERATING VARB ON EMISSION
PANKHURST ET, FORMATION OF S03 IN COMBUSTION
METCALFE, KINETICS OF COKE COMB IN REGENERATION
TAKEYAMA ET. AMMONIA OXIDATION IN SHOCK WAVES
JOHNSON. MECHANISM OF CORROSION BY FUEL IMPURITIES
JOHNSON. MECHANISM OF CORROSION BY FUEL IMPURIITES
JOHNSON, MECHANISM OF CORROSION BY FUEL IMPURIITES
LATHAM ET. HYDOCARBON ANALYSIS ASTM STP 389
LOWREY, CHEMISTRY OF COAL UTILIZATION
KIRK ET, ENCYCLOP OF CHEMICAL TECHNOLOGY
KUENTZEL, CODEN FOR PERIODICAL TITLES
HOCHSTIM. BIBLIOGRAPHY OF CHEMICAL KINETICS AND
SHREVE. THE CHEMICAL PROCESS INDUSTRIES
GAYDON ET, FLAMES, CHAPMAN AND HALL, LONDON, P151
FRISTROM ET, FLAME STRUCTURE, MCGRAW HILL NY 1965
RAPPOPORT, CHEMISTRY OF THE CYANO GROUP
CONANT, THE CHEMISTRY OF ORGANIC COMPOUNDS MACMIL
DURRANT ET, JNTOOD TO ADV INORGANIC CHEMIASTRY
AILLIET ET, BURN VEL OF C2N2 OR HCN WITH 02
WEINER ET. AIR POLLUTION IN THE PULP AND PAPER IND
ANON. PARAGRAPH QUATATION FROM CONF NEWS
CULLIS ET, REACTION OF S02 AND OXGENATED RADICALS
LEVY ET, MICROSTRUCTURE OF H2S FLAMES
DURIE ET, CATALYTIC FORM OF 503 IN FUEL RICH PROPA
ANON, S SPECIES IN BURNT GAS OF PROPANE AIR FLAMES
CULLIS, REACTIONS BETWEEN S02 AND N02
KALLEND, EFFECT OF S02 ON EOUIL IN H2 FLAMES
COHEN ET, BURNING VELOC OF HCN IN AIR AND 02
WILDE. ROLE OF HNO IN THE H2-NO REACTION
SPALDING ET, CALC PROCEDURE FOR LAMINAR FLAME SPEE
CRAMAROSSA ET, OZONE DECOMP IN STEADY FLAMES
HOLLAND ET, FLAME SPEED IN H2-ETHANE-N20 SYSTEM
HAY ET. OXIDATION OF GASEOUS FORMALDEHYDE
ROSSER ET. QUENCHING OF FLAMES BY INHIBITORS
LIFSHITZ ET, SHOCK TUBE FOR IGN OF CH4-02-ARGON MI
SEERY ET, METHANE OXIDATION BEHIND SHOCK WAVES
LAVOIE, SPECTROSCOPIC MEAS OF NO IN SI ENGINES
OPSAHL ET, OSCILLATORY COMBUSTION AND POLLUTANTS
WESTENBERG ET, THEORY OF LAMINAR SPHERICAL PREM
SPALDING ET, PROPAGATION OF STEADY LAM FLAMES
BERLAD ET, THEORY OF FLAME EXTINCTION LIMITS
VAN TIGGELEN ET, FLAMMABILITY LIMITS
112
-------
Table AH-3 (Cont). Literature References Alphabetized by CODEN
00626
00727
00748
00749
00761
00767
00768
00391
00392
00393
00396
00413
00420
0053*
00534
00545
00551
00752
00804
00429
00368
00370
00559
00575
00580
00510
00576
004CO
00514
00556
00366
00412
00724
00629
00416
00779
00317
00718
00784
00319
00348
00390
00398
00554
00794
00641
00430
00353
00577
00362
00369
00373
00511
00361
00569
00570
CBFMA-1971-16-125
CBFMA-1971-17-197
CBFMA-1971-17-131
CBFMA-1971-17-139
CBFMA-1968-12-603
CBFMA-1964-8-113
CBFMA-1967-11-109
CBSTA-1971-4-17
CBSTA-1971-4-59
CBSTA-1971-4-73
CBSTA-1971-4-9
CBSTA-1971-3-37
CBSTA-1971-3-83
CBSTA-1970-1-461
CBSTA-1970-1-313
CBSTA-1971-4-59
CBSTA-1971-3-53
CBSTA-1970-2-161
CBSTA-1971-2-329
CENEA-1971-6-15
CEPRA-1969-7-71
CEPRA-1969-65-UU.65
CEPRA-1971-67-62
CEPRA-1971-67-57
CEPRA-1965-61-A56
CESCA-1963-18-177
CESCA-1970-25-623
CHREA-1958-58-173
CHREA-1960-93-3014
CIEAA-1970
CJCHA-1953-31-30
CJCEA-1967-45-61
CJCEA-1963-41-826
COMBA- 1963- JAN-MAR
CPENA-1971-79
CRADA- 1950-23 1-1 302
DKPCA-1967-175-647
ERKOA-1971-7-171
ERKOA-1929-5-455
ESTHA-1969-3-63
ESTHA-1970-4-653
ESTHA-1971-5-333
ESTHA-1971-5-39
ESTHA-1971-4-320
ESTHA-1969-3-63
FRXXA-2040117
FUELS-1969-48-297
HCACA-1930-13-629
ICONA-1970- -314
IECFA-1969-8-374
IECHA-1942-34-567
IECHA-1942-34-567
IECHA-1955-4 7-972
IEPDA-1969-8-206
IEPDA-1971-10-297
IEPDA-1971-10-357
ARM ITAGE ET, STUDIES OF REACTION OF N02 AND S02
DURIE ET. EFFECT OF 502 ON H ATOM RECOMBINATION
SHAMED ETt NO FORMATION IN PROPANE AIR AND H2 AIR
ALDRED ET, MECH OF COMB OF DROPLETS ON HEPTANE
BULL, SHOCK TUBE STUDY OF OX ID OF AMMONIA
ANDREWS ET, COMB OF NH3 WITH 02 N20 AND NO
GRAY ET, COMB OF H2 AND 02 WITH NH3 AND N20
MELVIN ET, REACTION BROADENED DIFFUSION FLAME
WESTENBERG, KINETICS OF NO AND CO IN HC FLAMES
BLUMBERG ET, NO FORMATION IN SPARK IGNITED ENGINES
LIVESEY ET. FORMATION OF NOX IN OXY/PROPANE FLAMES
BOWMAN, NO FORMATION KINETICS, THE H2-N2-02 REACT I
D'SOUZA ET, METHANE OXID IN A STEADY FLOW REACTOR
MARTENEY. KINETICS OF FORM OF NO IN HC AIR COMBUST
LAVOIE ET, NO FORMATION IN 1C ENGINES
WESTENBERGi KINETICS OF NO AND CO IN LEAN FLAMES
CARETTO ET, ROLE OF KINETICS IN EMISSION OF NO
BOWMAN. HIGH TEMP OXIDATION OF HYDROCARBONS
BOCKHORN ET, SYNTHESIS OF HCN IN A FLAME REACTION
ANON* DMN IN CIGARETTE SMOKE
KITZEN ET, GAS OIL PYROLYSIS IN TUBULAR REACTORS
MARSHALL ET, GAS OIL FEEDSTOCKS FO C2H4 PRODUCT!
BARTOK ET, CONTROL OF NOX EMISSIONS FROM STATIONA
DEMAREST, STATUS OF REACTOR FURNACES
KARLOV1TZ, FLOW PHEN AND FLAME TECHNOLOGY
BOWEN ET, OSS APPROXIMATION IN CHEMICAL KINETICS
LONG ET, SELF-IGNITION OF FUEL DROPS IN HOT GASES
CAMPBELL ET, THE HYDROGEN BROMINE SYSTEM
ECKLING ET, KIN STUD. PHOTOCHLORINATION
BOWMAN, NOX FORMATION IN COMB, THE H2-02-N2 REACT
INGOLD ET, THERMAL DECOMPOSITION OF BENZENE DFRIVA
RAO ET, SHOCK TUBE STUDY OF REACT OF N2 WITH HCA
MUI ET, PHOTOLYSIS OF HNCO VAPOR
GLAUBITZ.
WARD ET, OPEN FLAME FURNACE DESIGN
PATRY ET,
SACHYAN ET, COMB OF DILUTE H2S FLAMES
NARASIMHAN, BERECHNUNG D FLAMMENLANGE INDUSTRIEOFE
RUHEMANN, THERMIC BEHAVIOR OF PHENOLS AND BASES
LEVY ET. SOX FORMATION IN COS FLAMES
LEVY ET, FORMATION OF SOX IN COMBUSTION
BUFALINI ET. OXlD OF N-BUTANE BY PHOT OF N02
ALTSHULLER ET, PHOTO CHEM ASPECT OF AIR POLLUTION
HALL ET, NOX CONTROLFROM STATIONARY SOURCES
LEVY ET, SOX FORMATION COS FLAME
PATENT TO JOHN ZINK CO
KARN ET, COAL PYROLYSIS USING LASER IRRADIATION
BRINER ET, L'ACTION DES DISCH. ELECT-C2N2
RAO ET, STIRRING BY COLD MODEL SIMULATION
KUNUGI ET. KINETICS OF THERMAL REACTIONOF C2H4
FUCHS ET, THEORY OF COAL PYROLYSIS
FUCHS ET, THEORY OF COAL PYROLYSIS
GERHARD ET, PHOTOCHEMICAL OXIDATION OF S02
BLAKEMORE ET, PYROLYSIS OF N-BUTANE
SATCUNANATHAN, IGNITION DELAY OF DROPS
KUMAR ET, PNEUMATIC ATOMIZATION
113
-------
e^n-^S (Cont)_._Literature References Alphabetized by CODEN
00315
00349
00504
00701
00702
00703
00704
00705
00378
00350
00354
00356
00363
00406
00414
00522
00524
00374
00375
00376
00377
00707
00591
00316
00322
00360
00399
00411
00417
00505
00506
00512
00515
00516
00517
00521
00595
00722
00615
00624
00552
00556
00582
00708
00313
00320
00326
00339
00347
00567
00568
00571
00572
00573
00574
00618
IJCEA-1969-9-396
IJCEA-1969-9-317
IJCKA-1969-1-105
IJCKA-1969-1-89
IJCKA-1969-1-29
IJCKA-1969-1-3
1JCKA-1971-3-467
1JCKA-1971-3-381
INCEA-1971-11-739
JACSA-1947-69-3143
JACSA-1959-81-6190
JACSA-1942-64-1880
JACSA-1962-84-4519
JACSA-1963-B5-539
JACSA-1962-84-4509
JACSA-1951-73-15
JACSA-1959-81-769
JAHSA-1971-28-1095
JAHSA-1971-28-847
JAHSA-1971-28-833
JAHSA-1971-28-1058
JAMCA-1971- -756
JASCA-1952-74-739
JCPSA-1963-39-275
JCPAA-1967-17-800
JCPSA-1962-36-1146
JCPSA-1970-52-5718
JCPSA-1967-47-228
JCPSA-1966-45-338
JCPSA-1962-36-2582
JCPSA-1955-23-2399
JCPSA-1958-29-456
JCPSA-1965-43-3237
JCPSA-1965-43-3371
JCPSA-1967-46-4843
JCPSA-1969-50-2512
JCPSA-1955-23-1360
JCPSA-1969-50-3377
JEFPA-1966-88-165
JEFPA-1967-89-283
JEPOA-1971- -333
JEPOA-1971- -293
JFLSA-1970-40-401
JHTRA-1971- -365
J1FUA-1967-40-142
JIFUA-1969- -188
JIFUA-1970-43-187
JIFUA-1962-35-502
JIFUA-1970- -234
JIFUA-1970- -295
JIFUA-1970- -301
JIFUA-1970- -517
JIFUA-1970- -397
J1FUA-1971- -196
JIFUA-1971- -38
JIFUA-1965-87-374
WEYCHERT ET. KINTEICS OF CAT CONVERSION OF S02
AVERBUCH ETt ELEMENTAL S BY REDUCTION WITH NAT GAS
KONORATIEV ET, INTERACTION OF CO AND 0
MCGRAW ET, CH30NO PHOTOLYSIS AND DECTION OF HNO
BENSON ET, ICL AS SOURCE OF CL, CL WITH H2
FRANKLIN ET, BOND ENERGIRES IN CHLOROETHANES
KREZENSKI ET, REACTIONS OOP) WITH 03 AND COS
BATTEN ET, REACTION FO N20 AND N02
AKITA* FLAME PROPAGATION BASIC THEORY
FENIMORE* HOMOGENEOUS REACTION OF NO AND CO
GRAVEN, KINETICS OF DECOMP OF N20 AT HIGH T
ROBERTSON ET, THERM REACTION OF H2 AND C2N2
HURD ET, PYROLYSIS OF PYRIDINE, PICOLINES AND
STREITW1ESER ET, TOLUENE IN MICROWAVE DISCHARGES
HURD ET, PYROLYTIC FORM OF ARENES, I SURVEY
RALEY ET, OXIDATION OF FREE CH3
SLEPPY ET, METHYL 02 AND METHYL NO REACTIONS
MCELROY ET, N20t A NATURAL SOURCE OF STRAT NO
CLARK, CHEMICAL KINETICS OF C02 ATMOSPHERES
JULIENNE ET, TEMP DEP OF C02 ABSORPTION
PRINN, PHOTOCHEMISTRY OF HCL IN ATM OF VENUS
PLATTEN ET, DEFLECTED TURBULENT JET FLOWS
COOLEY ET, BURNING VELOCITY IN H2 BR2 FLAMES
BERKOWITZ ET, EQUIL COMPOSITION OF SULFUR VAPOR
LEVY ET, SOX FORM IN LOW P H2S FLAMES
PATTERSON ET, KINETICS OF CN IN SHOCK WAVES
GELBART ET, VIBRATIONAL RELAXATION AND DISSOSIATI
SNELLING ET, DECOMPOSITION OF N20 BY OllD) N2
WESTENBERG ET, ESR AND KINETICS OF THE OD RADICAL
WRAY ET, KINETICS OF NO AT HIGH TEMPERATURE
BROMBERG ET, OXIDATION OF CH4 WITH N02
ANON,
GETZINGER ET, RECOMBINATION H+02+M=H02+M
WONG ET, REACTIONS OF 0 ATOMS WITH H2 AND NH3
STUCKEY ET, REACTIONS OF 0 ATOMS WITH CYCLO PARAFF
WESTENBERG ET, RATE COEFFICIENTS OF 0 + H2 AND
FRISTROM, ONE-DIMENSIONAL FLAME FRONT MODELS
LIN ET, REACTION OF N20 WITH CO AND 0 WITH CO
BARRET ET, '
REID,
STARKMAN ET, ROLE OF CHEMISTRY IN GAS TURBINE EMIS
TOMANY ET, NOX CONTROL TECHNOLOGY AND DEVELOPMENT
WILLIAMS, APPROACH TO FLAME TURBULENCE
RAMSEY ET, HEATED'JET IN DEFLECTING STREAM
HEDLEY, FORMATION OF S03 IN FLAME GASES
SNOWDON ET, H2S04 CONDENSATION FROM FLUE GASES
GUNTHER, MEAUSERMENTS OF FLAME TURBULENCE
MACFARLANE, FORMATION OF 503 IN COMBUSTION PRODUCT
ANON* REVIEW CHEM ASPECTS OF FIRESIDE CORROSION
SAKAI ET, COMB OF ATOMIZED FUEL OIL DROPS
NURUZZAMAN ET, COMB OF MONOSIZED DROP STREAMS
GIBSON, COMB OF SOLID PART IN STREAM WITH RECIRCU
ARCHER ET, MULTISTAGE COMBUSTION PART 1
SPALDING, COMBUSTION AS APPLIED TO ENGINEERING
HEDLEY ET, COMBUSTION OF SINGLE DROPS ANS SPRAYS
LEVY ET,
114
-------
ablj^An^a (Cont)^ Literature_Reference£_Alphabetized by CODEN
-517
-301
-195
-599
00619 JIFUA-1965-29-322
00620 JIFUA-1956-29-372
00621 JIFUA-1967-40-342
00633 JIFUA-1953-26-122
00634 JIFUA-1969-42-67
00710 JIFUA-1961-
00711 JIFUA-1970-
00712 JIFUA-1970-
00717 JIFUA-1968-
00726 JIFUA-1971-
00415 JOCRA-1969-45-256
00323 JPCHA-1968-72
00333 JPCHA-1965-10-
00380 JPCAA-1971-21-713
00381 JPCAA-1971-21-702
00397 JPCHA-1962-66-366
00403 JPCHA-1966-70-1793
00424 JPCHA-1968-72-3305
00428 JPCHA-1969-73-2555
00520 JPCHA-1959-63-1834
00541 JPCAA-1971-21-702
00546 JPCAA-1970-20-377
00719 JPCAA-1971- -52
00723 JPCHA-1965-69-2111
00763 JPCHA-1961-65-298
00321 KINFA-1969
00630 MEENA-1960-82-93
00631 MEENA -1960-82-92
00404 MOPHA-1966-11-403
00408 MOPHA-1965-10-401
00750 MTURA-1968-20-567
00596 NACRA-1954-1158
00579 NAFTA-1970- -11.1
00602 NASCA-1970-TND7024
00337 NATUA-1966- -1171
00426 NATUA-1964-204-98B
00427 NATUA-1964-203-619
00536 NATUA-1960-186-551
00367 01GJA-1971-1-74
00371 OIGJA-1971-9-94
00628 OIGTA-1966-NOV-66
00327 PAPWA-1968-30-786
00557 PAPWA-1970-32-683
00351 PCSLA-1964- 410
00336 PICMA-1963- 216
00538 PLSSA-1967-15-643
00332 PPT1A-1969-49-615
00790 PREPRINT-1971
00791 PREPRINT-
00800 PREPRINT-1971
00330 PRLAA-1968- -380
00340 PRLAA- -276-461
00341 PRLAA-1958-247-123
00342 PRLAA-1966-295-72
00355 PRLAA-1963-272-147,
00357 PRLAA-1965-283-302
CRUMLEY ET,
RENDLE ET,
CROSSLEY
FLINT. METAL ADDITIVES
LEE ET.
THRING. TURBULENT DIFFUSION COMBUSTION. SURVEY U
GIBSON ET, MODEL OF COMBUSTION OF SOLID PARTICLES
NURUZZAMAN ET, FLAMES ON MONOSIZED DROPLET STREAMS
HAKLUYTT ET, DESIGN OF AIR REGISTERS FOR OIL-FIRED
GODRIDGE ET, CARBON FORMATION IN LARGE BURNERS
BARTLE ET, TOBACCO SMOKE BY GAS CHROMATOGRAPHY
WHEELER, RADICAL RECOMBINATION IN S02 DOPED FLAMES
FENIMORE ET, S IN THE BURNT GAS OF H2-02 FLAMES
STOCKHAM, COMPOSITION OF GLASS FURNACE EMISSSIONS
BAGWELL ET, BOILER OPERATING MODE FOR RED NOX
MOBERLY, SHOCK TUBE FOR HYDRAZINE DECOMPOSITION
GUTMAN ET. THERMAL DECOMP OF N20
SAFRANY ET, REACTION OF H AND N WITH C2N2 HCN AND
ASMUS ET, PYROLYSIS KINETICS OF ACETON1TRILE
FENIMORE ET, CONSUMPTION OF 02 IN HC FLAMES
BAGWELL ET. BOILER OPERATING MODES FOR REDUCED NOX
HARDISON. CONTROLLING OXIDES OF NITROGEN
SCHLUCHMANN ET, N COMPUNDS OTHER THAN NO IN AUTO E
MODICA. KINETICS OF N20 DECOMPOSITION BY MASS SPEC
FENIMORE ET. OXIDATION OF AMMONIA IN FLAMES
ANON. REACTIONS OF SO.S02. S03 WITH H.O.OH.NO.N02
AUSTEN ET,
COYKENDALL,
GOGGENHEIM, DIMERIZATION OF NO. CORRECTION
GUGGENHEIM, DIMERIZATION OF GASEOUS NO
MAZUR ET, INFLUENCE OF TEMP ON COKING
DUGGER ET, PREDICTION OF FLAME VELOCITIES
CHERADAME, THE AERODYNAMICS OF FLAMES
BROKAW ET, CO OXIDATION IN AUTO EXHAUST
SHAW ET, OX ID OF 502 IN AIR EFFECT OF CO AND NO
HERZBERG ET, IDENT OF FREE RAD IN FLASH PHOTOL
MCGRATH ET, UV ABS SPECTRUM OF FREE FULMINATE
SIMONS. VIBRATIONALLY HOT MOLECULES IN RADICAL REA
ANON* PROFITABILITY FACTORS IN GAS OIL CRACKING
BROOKS ET. CRACKING GAS OILS
MUNROE *
TERRY ET. OD2 BOILER AT SCUYLKULL STATION
BAGWELL ET. NOX REDUCTION PROGRAM FOR OIL AND GAS
CAMPBELL £T, BEHAVIOR OF CN IN ACTIVE N
DEMARDAUCHE ET. REACTION OF S CMPDS IN FLAMES
SCHOFIELD, KINETIC RATE DATA OF ATM INTEREST
TUCKER* SOX STACK EMISSIONS-REACTIONS AND CONTROL
MARTIN ETjf CONVERSION OF UEL NITROGEN TO NOX
TURNER ET, COMB MOD AND FUEL NITROGEN CONTENT
SOMMERLAD ET, NOx EMISSIONS-ANALYTICAL EVAL OF T
HALSTEAD ET, CHEMILUMINESCENT REACTION OF SO
GAYDON ET, SHOCK TUBE DECOMPOSITION OF S02
KAUFMAN, USE OF AIR AFTERGLOW IN REACTIONS OF 0
CULL IS ET. HOMOGENEOUS GAS OXIDATION OF S02
BASCO ET* CYANOGEN RADICALS BY FLASH PHOTOL
BASCO* REACTION OF C2N2 WITH 02
115
-------
Table_An-3 (Cont). Jntei^ture_References_Alphabetized by CODEN
00358
00379
00387
00407
00419
00503
00528
00529
00533
00593
00597
00598
00600
00601
00638
00335
00599
00507
00509
00540
00729
00730
00731
00732
00733
00734
00735
00736
00737
00738
00739
00740
00741
00743
00744
00746
00747
00751
00433
00612
00755
00756
00766
00786
00795
00796
00797
00798
00799
00802
00806
00405
00539
00550
00560
00561
PRLAA-1965-283-291
PRLAA-1965-288-275
PRLAA-1963-273-145
PRLAA-1968-305-93
PRLAA-1970-314-585
PRLAA-1956-235-89
PRLAA-1970-316-539
PRLAA-1970-316-575
PRLAA- -276-324
PRLAA-1957-240-83
PRLAA-1970-317-227
PRLAA-1970-317-235
PRLAA- -298-495
PRLAA-1968-307-111
PRLAA-1966-295-363
PSRIA-1961
PTRSA-1956-A249-1
PYDYA-1965-3-197
PYDYA-1966-4-119
PYDYA-1967-5-74
PYDYA-1967-5-375
PYDYA-1968-6-101
PYDYA-1968-6-187
PYDYA-1968-6-355
PYOYA-1964-1-147
PYDYA-1965-3-245
PYDYA-1965-2-315
PYDYA-1965-2-197
PYDYA-1965-2-91
PYDYA-1967-5-221
PYDYA-1966-4-211
PYDYA-1966-4-63
PYDYA-1966-4-57
PYDYA-1966-4-371
PYDYA-1966-4-305
PYDYAtl964-l-271
PYDYA-1964-1-335
PYDYA-1966-3-235
RADCA- -2-142
REGTA-1965-4-1117
REPORT-1966
REPORT
REPORT
REPORT1968
BASCO ET, REACTION OF C2N2 WITH NO
SETSER ET. REACTION OF 0 WITH C2N2
HUSAIN ETt OXIDATION OF NHS AND
BODEN ET, EXCITATION OF CN IN ACTIVE NITROGEN
HOMER ET. DISSOCIATION OF H20 IN SHOCK WAVES
BULEWICZ ET, HYDROGEN ATOMS IN BURNT GAS MIXTURES
CLARK ET. KINETICS OF N WITH 02OSG-) AND (IDG)
HALSTEAD ET. REACTION OF H WITH C2H4
SEAKINS ET, KINETICS OF GAS PHASE HC OXIDATIONS
SPALDING. FLAMM LIMITS AND FLAME QUENCHING
DIXON-LEWIS ET, EXPT FUEL RICH H2 02 N2 FLAME
DIXON-LEWIS, MECHANISM H2 02 N2 FLAME
DIXON LEWIS, CONSERVATION EQUATIONS FOR FLAMES
DIXON-LEWIS, TRANSPORT PHEN IN FLAMES
HALSTEAD ET,
SUGDEN ET, OXIDES AND HYDRIDES OF N AND S IN FLAME
SPALDING, THEORY OF FLAMES WITH CHAIN REACION
CHINITZ, ANALYSIS OF CH4 AIR COMBUSTION
CHINITZ ET, NON EQUIL HYDROCARBON AIR COMBUSTION
BAHN ET, REACTIONS INVOLVING N AND 0
BAHN. CHEMICAL KINETICS N 0 AND H
BAHN,
BAHN,
BAHN,
BAHN,
BAHN,
BAHN,
CHEMICAL KINETICS H+C02«OH+CO AND
CHEMICAL KINETICS C02 CO HCO
CHEMICAL KINETICS CO AND HCO
N2 02 NO N AND 0
H20 H02 H202 03
H20 H02 03 WITH
H2 02 OH H AND 0
CHEMICAL KINETICS N03 N20 N02 03 02 NO N
CHEMICAL KINETICS REACTIONS OF 0 AND H
CHEMICAL KINETICS N2H4 N2H3 N2H2
CHEMICAL KINETICS N2 N H2 H NH NH2 NH3
CHEMICAL KINETICS
CHEMICAL KINETICS
CHEMICAL KINETICS
BAHN, CHEMICAL KINETICS
BAHN,
BAHN,
BAHN,
BAHN,
WECKER ET, ON THE FOUR CENTER AIR REACTION
BAHN, CHEMICAL KINETICS F CL H 0 N SYSTEM
BAHN, CHEMICAL KINETICS N2H4 N2H3 N2H2
BAHN, CHEMICAL KINETICS N20 N02 03
BAHN, CHEMICAL KINETICS N20 N02 03
HILL ET, MONOETHYLAMINE COMBUSTION
MANI ET, REACTION OF 0 WITH BENZENE AND OTHER CMPD
DE LACHAUX,
HOPF, REPORT FOR ADVANCED RESEARCH PROJECTS AG
STULL , JANAF THERMOCHEMICAL TABLES
SUTTON ET, OXIDES OF NITROGEN IN ENGINE EXHAUST P
BAULCH ET, RATE DATA FOR HOMOGENEOUS GAS REACT
REPORT-9840-6002-RUOTYSON. IMPLICIT INTEGRATION FOR CHEMICAL KINETICS
REPORT
REPORT-1969
REPORT
REPORT-1969
REPORT
REPORT
RIFPA-1964-19-523
SAUPA-1969-690518
SAUPA-1970-700470
SAUPA-1970-700708
SAUPA-1971-710158
BAILEY ET,INTEGRATION OF ONE DIM FLOW EQUATIONS
BARTOK ET, SYSTEMS STUDY OF NOX CONTROL METHODS
FINE ET, NITROGEN IN COAL AS AOURCE OF NOX
JONKE ET, REDUCTION OF POLLUTION BY FLU1DIZED
BIENSTOCK ET, FORMATION OF NOX IN PULV COAL COM
JOHNSON , GAS PHASE KINETICS OF NEUTRAL 0 SPECIES
JANIN ET, LA FLAMME CH4-NH3-02
TRUMPY ET, PREKNOCK KINETICS IN AN SI ENGINE
CARR ET, INFLUENCE OF FUEL COMPOSITION ON CO AND
CORNELIUS ET, FORMATION AND CONTROL OF NOX
MUZ10 ET, EFFECT OF T ON FORMATION OF NOX
116
-------
Table_An-3 (Cont]L_ Literature References Alphabetized by CODEN
00562
00563
00564
00402
00422
00432
00583
00343
00362
00383
00384
00418
00421
00423
00425
00519
00535
00584
00585
00586
00588
00594
00616
00617
00623
00636
00637
00709
00713
00720
00721
00765
00778
00787
00801
00805
00611
00613
00714
00334
00345
00352
00385
00409
00501
00502
00513
00523
00635
00639
00762
00716
00788
00725
00372
00706
00344
00527
00627
SAUPA-1971-710009
SAUPA-1969-690018
SAUPA-1971-710011
SCIEA-1971-171-1013
SCIEA-1971-171-1013
SCIEA-1971-174-1341
SCPOA-1970-58-161
SYMCA- -12-323
SYMCA-1960-8-127
SYMCA-1965-10-435
SYMCA-1965-10-377
SYMCA-1965-10-473
SYMCA-1965-10-311
SYMCA-1960-8-487
SYMCA-1960-8-496
SYMCA-1965-10-43
SYMCA-1969-12-603
SYMCA-1953-4-267
SYMCA-1971-13-997
SYMCA-1967-11 -1057
SYMCA-1956-6-20
SYMCA-1958-7-475
SYMCA-1969-12-635
SYMCA-1971-13-427
SYMCA-1972
SYMCA-1965-10-463
SYMCA-1965-10-473
SYMCA-1963-9-7
SYMCA-1952-4-789
SYMCA-1969-12-604
SYMCA-1971-13-373
SYMCA-1967-11-871
SYMCA
SYMCA-1963-9-560
SYMCA-1971-13-
SYMCA-1956-6-198
TASMA-1958-80-225
TASMA-1958-80-1231
TASMA-1957-79-1727
TFSOA-1967-63-2442
TFSOA-1946-42-354
TFSOA-1953-49-1312
TFSOA-1968-64-1836
TFSOA-1967-63-1687
TFSOA-1956-52-1475
TFSOA-1956-52-1465
TFSOA-1967-63-662
TFSOA-1957-53-1102
TFSOA- 1966-62-2 150
TFSOA-1969-65-3013 ,
TFSOA-1968-64-71
THENA-1968-15-44
THESIS-1967
TORFA-1963-40-28
TOSCA- -6-106
VGBGA-1969-1133
ZFKHA-1940- 14-1428
ZFKHA-1959-33-572
ZFKHA-1940-14-1428
QUADER. INTAKE CHARGE DILUTION AND NOX EMISSION
NICHOLLS ET. WATER INJECTION FOR CONTROL OF NOX
HEYWOOD ET. PREDICTION OP NOX IN SI ENGINE EMISSI
WESTBERG ET. CO ROLE IN PHOTCHEMICAL SMOG
WESTBERG ET, CO. ROLE IN PHOTOCHEMICAL SMOG
ARCHER ET. ENVIRONMENTAL NITROSO CMPDS
COTTON, THE STRUCTURE OF FLAMES
MULCAHY ET. KINETICS OF 0 WITH SOX
FEN1MORE ET, RATE OF REACTION 0+N20=NO+NO
GRAY ET, H-ATOM ABSTRATION FROM N-H BONDS
ASHMORE, REVIEW ELEMENTARY COMB REACTIONS
WESTENBERG ET, H AND 0 ATOM PROFILES BY ESR
CLYNE, REACTIONS OF THE HNO MOLECULE
HICKS. DECOMP FLAME OF ETHYL NITRATE
GRAY ET, FLAME OF METHYL NITRITE
WESTENBERG ET, H AND 0 ATOM PROFILES BY ESR IN C2
NEWHALL, ENGINE GENERATED NOX AND CO
FRISTROM ET, T PROFILES IN PROPANE-AIR FLAMES
TSUJI ET, COUNTERFLOW DIFFUSION FLAMES
GRAY ET, PRESENT POSITION IN EXPLOSION THEORY
LINNETT ET, LIMITS OF INFLAMMABILITY
DIXON-LEWIS ET, LIMITS OF INFLAMMABILITY
NETTLETON ET, FORMATION AND DECOMP OF S03
MERRYMAN ET, S03 FLAME CHEMISTRY- H2S/COS FLAMES
WENDT ET, REDUCTION OF S03 AND NOX BY SEC FUEL
WEBSTER ET.
THRUSH ET,
BECKER ET, MIXING AND FLOW DUCTED TURBULENT JETS
THRING ET, LENGTH OF ENCLOSED TURBULENT FLAMES
NEWHALL, KINETICS OF ENGINE GENERATED NOX AND CO
FENIMORE. FORMATION OF NO IN PREMIXED HC FLAMES
MACLEAN ET. AMMONIA AND HYDRAZINE DECOMPOSITION F
MYERSON ET. IGNITION UNITS PROPANE-N02 FLAMES
FRISTROM, RADICAL CONC AND REACT IN CH4 02 FLAME
BREEN ET, NOX CONTROL UTILITY POWER
LEVY. DISCUSSION
MARLOW.
ANDERSON ET,
SHERMAN, HEAT TRANSFER BY RADIATION FROM FLAMES
KALLEND S02 ON CHEM1LUM AND ATOM RECOMBINATION
DOOLEY ET, OXIDATION OF S02 IN GAS FLAMES
MADLEY ET, KINETICS OF OXID OF CHARCOAL WITH N20
DAVIES ET, REACTION OF O WITH HCN, CNCL AND CNBR
CERCEK ET, REACTION OF H AND OH WITH PYRIDINE
BULEWICZ ET, DISSOCIATION CONSTS BY FLAME PHOTOMET
SUGDEN, DISSOCIATION CONSTS BY FLAME PHOTOMETRY I
GILES ET. REACTIONS OF RF3 RADICALS WITH ORGANIC H
HOARE ET, REACTION OF CH3 WITH 02 AND COMPARISON
JOFFE ET.
HALSTEAD ET,
BRADLEY ET, OXIDATION OF NH3 IN SHOCK WAVES
IVANOV, FLOW SECTION OF VORTEX BURNERS
MORGAN, COMB OF CH4 IN A JET STIRRED REACTOR
RAKOVSKII ET, PYROLYSIS OF PYRIDINE AND QUINOLINE
LINNELL, THERMAL DECOMPOSITION OF PYRIDINE
NIEPENBERG, DESIGN FEATURES OF GAS BURNERS
ANON* GENERAL PHYSICAL CHEM
NIKIT1N, THERMAL DISSOCIATION OF DIATOMIC MOLECULE
BOREKOV ET. KINETICS OF REACTION OF N02 AND S02
117
-------
Table AH-4
COOEN NAMES FOR JOURNALS» ALPH BY NAME OF JQURN
APMPA AIR POLLUTION CONTROL ASSN, PAPER
AICEA AM INST OF CHEM ENGINEERS* JOURNAL
ARPLA ANN REVIEW OF PHYSICAL CHEMISTRY
AICPA AM INST OF CHEM ENG, PAPAER
AAPRA AM INST OF AERONAUTICAL AND ASTRONAUT ENG* PAPER
AIAJA AM INST OF AERONAUT ANS ASTRONAUT ENG. JOURNAL
ACPYA ACTA PHYSICOCHIM URSS
AGPTA AMERICAN GAS ASSN PAPER
PAPGA AMERICAN PETROLEUM INST PROCEEDINGS SECTION 1
ACIEA ANGEWANDETE CHEMIE (INT ED)'
ASMSA ASME PREPRINT
AJCHA AUSTRALIAN JOURNAL OF CHEMISTRY
PPTIA AMERICAN PETROLEUM INSTITUTE. PROCEEDINGS
BRWKA BRENNST-WARME-KRAFT
BCHEA BRITISH CHEMICAL ENGINEERING
BCSJA BULL CHEM SOC JAPAN
BSCBA BUL SOCIETE CHIE BELGES
BBCUA BRITISH COAL UTILIZATION RES ASSN* BULLETIN
CHBEA CHEMISCHE BERICHTE
CEPRA CHEMICAL ENGINEERING PROGRESS
CESCA CHEMICAL ENGINEERING SCIENCE
C1TEA CHEMIE-ING-TECH
CIEAA* COMBUSTION INSTITITE. EASTERN SECTION. PAPERS
CRADA COMPTES RENDUS DE L/ACADEMIE DES SCIENCES. PARIS
CENEA CHEMICAL AND ENGINEERING NEWS
CJCEA CANADIAN JOURNAL OF CHEMICAL ENGINEERING
CPENA CHEMICAL AND PROCESS ENFINEERING
CHREA CHEMICAL REVIEWS
CBFMA COMBUSTION AND FLAME
CBSTA COMBUSTION SCIENCE AND TECHNOLOGY
WCIPA COMBUSTION INSTITUTE. WESTERN STATES SECT, PREPRINT
WSCPA COMBUSTION INSTITUTE, WESTERN STATES SECT, PAPER
CJCHA CANADIAN JOURNAL OF CHEMISTRY
DKPCA DOKLADY, PHYSICAL CHEMISTRY SECTION* ENGLISH
ELWOA ELECTRICAL WORLD
ESTHA ENVIRONMENTAL SCIENCE AND TECHNOLOGY
ERKOA ERDOL UND KOHLE
FUELA FUEL
RLBUA GENERAL ELECTRIC RESEARCH LAB BULLETIN
HCACA HELVETIA CHIMICA ACTA
IJCKA* INTERNATIONAL JOURNAL OF CHEMICAL KINETICS
IEPDA INDUSTRIAL AND ENGINEERING CHEM, PROCESS DESIGN
ICONA* INCINERATION CONFERENCE, 1970
IECHA INDUSTRIAL AND ENGINEERING CHEMISTRY
IENAA IND ENG CHEM, ANALYTICAL ED
IERSA IND ENG CHEM, ANN REV SUPP
IECFA IND ENG CHEM* FUNDAMENTALS
IECIA IND ENG CHEM* INDUSTRAIL ED
IEIEA IND ENG CHEM* INTERNATIONAL ED
IEPRA IND ENG CHEM, PRODUCT RESEARCH AND DEV
IJCEA INTERNATIONAL JOURNAL OF CHEMICAL ENGINEERING *
INCEA INTERNATIONAL CHEMICAL ENGINEERING
BUPAA INSTITUTE OF PAPER CHEMISTRY, BULLETIN
118
-------
Table AII-4 (Cont). CODEN Names for Jiournals_,_Alph by_Name of Journ
JFLSA JORUNAL OF FLUID MECHANICS
JPLRA JET PROPULSION LAB TECH REPT
JPCAA JOURNAL OF THE AIR POLLUTION CONTROL ASSN
JACSA JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
JAMCA JOURNAL OF APPLIED MECHANICS* ASME i SERIES E
JCPSA JOURNAL OF CHEMICAL PHYSICS
JOCRA JOURNAL OF CHROMATOGRAPHY
JEPOA JOURNAL OF ENGINEERING FOR POWER
JFIRA* JOURNAL OF FIRE AND FLAME
JIFUA JOURNAL OF THE INTlTUTE OF FUEL
JPCHA JOURNAL OF PHYSICAL CHEMISTRY
JAHSA JOURNAL OF THE ATMOSPHERIC SCIENCES
JHTRA JOURNAL OF HEAT TRANSFER
JNBAA JOURNAL OF RESEARCH OF THE NATIONAL BUREAU OF STANDARDS
MECCA* MECHANISM OF CORROSION BY FUEL IMPURITIES
MEENA MECHANICAL ENGINEERING (ASME)
MTURA METALURGIA, BUCHAREST
MOPHA MOLECULAR PHYSICS
NACRA NAT AD COMM FOR AERONAT, REPT
NAFTA* NORTH AMERICAN FUEL TECH CONF
NATUA NATURE
NASCA NATIONAL AERONAUTICS ANS SPACE ADMIN. TECH NOTE
PLSSA PLANETARY AND SPACE SCIENCE
PCSLA PROCEEDINGS OF THE CHEMICAL SOCIETY. LONDON
PYDYA PYRODYNAMICS
PAPWA PROC OF THE AMERICAN POWER CONFERENCE
PTRSA PHIL TRANS OF THE ROY SCOIETY
PAPWA PROCEEDINGS OF THE AMERICALN POWER CONF
PRLAA PROC OF THE ROYAL SOCIETY (LONDON) SERIES A
PICMA* PROCEEDINGS OF THE INTERNATIONAL CONF ON THE MECH OF CORROSION
PSRIA* PROCEEDINGS OF AN INTERN SYMP ARRANGED BY STANFORD RES INSTITUE
RADCA* RADIATION CHEMISTRY
RIFPA REVUE DE L'INSTITUT FRANCAISE DE PETROLE
SCPOA» SCIENCE PROGRESS/OXFORD
SCIEA SCIENCE
SAUPA SOCIETY OF AUTOMOTIVE ENGINEERS PAPER
SYMCA SYMPOSIUM ON COMBUSTION IINTL)
THENA THERMAL ENGINEERING* USSR
TASMA TRANSACTION S OF THE AMERICAN SOCIETY OF MECHANICAL ENGINEERS
TFSOA TRANACTIONS OF THE FARADAY SOC1EITY
TOSCA TOBACCO SCIENCE
OIGJA THE OIL AND GAS JOURNAL
KINFA* US DEPT COMM. NAT BUR STDS. KINETICS INFO CENTER
VGBGA* VGB CONVENTION ON GAS HEATING
ZFKHA ZHURNAL FIZ KHIM
ZPKHA ZHURNAL PRIK KHIM
119
-------
Table AH-5
CODEN NAMES FOR JOURNALS, ALPHA BY CODEN
AAPRA AM INST OF AERONAUTICAL AND ASTRONAUT ENGt PAPER
ACIEA ANGEWANDETE CHEMIE (INT ED)
ACPYA ACTA PHYSICOCHIM URSS
AGPTA AMERICAN GAS ASSN PAPER
AIAJA AM INST OF AERONAUT ANS ASTRONAUT ENGt JOURNAL
AICEA AM INST OF CHEM ENGINEERSt JOURNAL
A1CPA AM INST OF CHEM ENGt PAPAER
AJCHA AUSTRALIAN JOURNAL OF CHEMISTRY
APMPA AIR POLLUTION CONTROL ASSN. PAPER
ARPLA ANN REVIEW OF PHYSICAL CHEMISTRY
ASMSA ASME PREPRINT
BBCUA BRITISH COAL UTILIZATION RES A3SN, BULLETIN
BCHEA BRITISH CHEMICAL ENGINEERING
BCSJA BULL CHEM SOC JAP.\
BRWKA 8RENNST-WARME-KRAFT
BSCBA BUL SOCIETE CHIE BELGES
BUPAA INSTITUTE OF PAPER CHEMISTRY, BULLETIN
CBFMA COMBUSTION AND FLAME
CBSTA COMBUSTION SCIENCE AND TECHNOLOGY
CENEA CHEMICAL AND ENGINEERING NEWS
CEPRA CHEMICAL ENGINEERING PROGRESS
CESCA CHEMICAL ENGINEERING SCIENCE
CHBEA CHEMISCHE BERICHTE
CHREA CHEMICAL REVIEWS
CIEAA* COMBUSTION INSTITITEt EASTERN SECTION, PAPERS
CITEA CHEMIE-ING-TECH
CJCEA CANADIAN JOURNAL OF CHEMICAL ENGINEERING
CJCHA CANADIAN JOURNAL OF CHEMISTRY
CPENA CHEMICAL AND PROCESS ENFINEERING
CRADA COMPTES RENDUS DE L/ACADEMIE DES SCIENCESt PARIS
DKPCA DOKLADYt PHYSICAL CHEMISTRY SECTIONt ENGLISH
ELWOA ELECTRICAL WORLD
ERKOA ERDOL UNO KOHLE
ESTHA ENVIRONMENTAL SCIENCE AND TECHNOLOGY
FUELA FUEL
HCACA HELVETIA CHIMICA ACTA
ICONA* INCINERATION CONFERENCE, 1970
IECFA IND ENG CHEM, FUNDAMENTALS
IECHA INDUSTRIAL AND ENGINEERING CHEMISTRY
IECIA IND ENG CHEM, INDUSTRAIL ED
IEIEA IND ENG CHEM, INTERNATIONAL ED
IENAA IND ENG CHEM, ANALYTICAL ED
IEPDA INDUSTRIAL AND ENGINEERING CHEM, PROCESS DESIGN
IEPRA IND ENG CHEM, PRODUCT RESEARCH AND DEV
IERSA IND ENG CHEM, ANN REV SUPP
IJCEA INTERNATIONAL JOURNAL OF CHEMICAL ENGINEERING *
IJCKA* INTERNATIONAL JOURNAL OF CHEMICAL KINETICS
INCEA INTERNATIONAL CHEMICAL ENGINEERING
JACSA JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
JAHSA JOURNAL OF THE ATMOAPHERIC SCIENCES
JAHSA JOURNAL OF THE ATMOSPHERIC SCIENCES
JAMCA JOURNAL OF APPLIED MECHANICS, ASME, SERIES E
JCPSA JOURNAL OF CHEMICAL PHYSICS
120
-------
Table AH-5 (Cont). CODEN Names for Journals^Alpha by_CODEN
JEPOA JOURNAL OF ENGINEERING FOR POWER
JFIRA* JOURNAL OF FIRE AND FLAME
JFLSA JORUNAL OF FLUID MECHANICS
JHTRA JOURNAL OF HEAT TRANSFER
JIFUA JOURNAL OF THE INTITUTE OF FUEL
JNBAA JOURNAL OF RESEARCH OF THE NATIONAL BUREAU OF STANDARDS
JOCRA JOURNAL OF CHROMATOGRAPHY
JPCAA JOURNAL OF THE AIR POLLUTION CONTROL ASSN
JPCHA JOURNAL OF PHYSICAL CHEMISTRY
JPLRA JET PROPULSION LAB TECH REPT
K1NFA* US DEPT COMMt NAT BUR STDSi KINETICS INFO CENTER
MECCA* MECHANISM OF CORROSION BY FUEL IMPURITIES
MEENA MECHANICAL ENGINEERING (ASME)
MOPHA MOLECULAR PHYSICS
MTURA METALURGIA, BUCHAREST
NACRA NAT AD COMM FOR AERCNAT, REPT
NAFTA* NORTH AMERICAN FUEL TECH CONF
NATUA NATURE
NASCA NATIONAL AERONAUTICS ANS SPACE ADMIN. TECH NOTE
OIGJA THE OIL AND GAS JOURNAL
PAPGA AMERICAN PETROLEUM INST PROCEEDINGS SECTION 1
PAPWA PROCEEDINGS OF THE AMERICALN POWER CONF
PCSLA PROCEEDINGS OF THE CHEMICAL SOCIETY. LONDON
PICMA* PROCEEDINGS OF THE INTERNATIONAL CONF ON THE MECH OF CORROSION
PLSSA PLANETARY AND SPACE SCIENCE
PPTIA AMERICAN PETROLEUM INSTITUTE. PROCEEDINGS
PRLAA PROC OF THE ROYAL SOCIETY (LONDON) SERIES A
PSRIA* PROCEEDINGS OF AN INTERN SYMP ARRANGED BY STANFORD RES INSTITUE
PTRSA PHIL TRANS OF THE ROY SC01ETY
PYDYA PYRODYNAMICS
RADCA* RADIATION CHEMISTRY
RIFPA REVUE DE LMNSTITUT FRANCAISE DE PETROLE
RLBUA GENERAL ELECTRIC RESEARCH LAB BULLETIN
SAUPA SOCIETY OF AUTOMOTIVE ENGINEERS PAPER
SCIEA SCIENCE
SCPOA* SCIENCE PROGRESS/OXFORD
SYMCA SYMPOSIUM ON COMBUSTION (INTL)
TASMA TRANSACTION S OF THE AMERICAN SOCIETY OF MECHANICAL ENGINEERS
TFSOA TRANACTIONS OF THE FARADAY SOCIEITY
THENA THERMAL ENGINEERING. USSR
TOSCA TOBACCO SCIENCE
WCIPA COMBUSTION INSTITUTE. WESTERN STATES SECT, PREPRINT
VGBGA* VGB CONVENTION ON GAS HEATING
WSCPA COMBUSTION INSTITUTE. WESTERN STATES SECT, PAPER
ZFKHA ZHURNAL FIZ KHIM
ZPKHA ZHURNAL PR IK KHIM
121
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Table AH-6
COMPLETE REFERENCES TO NON-PERIODICAL LITERATURE
Johnson, "Mechanism of Corrosion by Fuel Impurities," esp. p. 20*4-, 195, 228.
752 Latham, Okuno, and Haines, "Hydrocarbon Analysis," ASTM STP 389, ASTM,
Philadelphia, 1965, esp. p. 394.
753 Lowrey, Ed., "Chemistry of Coal Utilization," Supplementary Vol, Wiley, NY,
1963, esp. p. U98.
Kirk, R. E. , and Othmer, D. F. , Eds., "Encyclopedia of Chemical Technology,"
Vol 3, p. 156, Interscience , NY,
755 Hopf, H., Report for Advanced Research Projects Agency, Washington, DC, 1966.
756 Stull, D. R. , dir, "JANAF Thermochemical Tables," Dow Chemical Company, Air
Force Contract AF C4(6ll)-75S^-
758 Knentzel, L. E. , ed., "COD::N for Periodical T-tles," A5""M ^z. Seizes DSLjA,
Air. Soc. for Testing Mat Is, Philadelphia, 1966.
759 Hochstim, A. F. , ed. , "Bibliography of Chemical Kinetics and Collision
Processes," IFI/Plenum, NY, 1969.
760 Shreve, R. N. , "The Chemical Process Industries," McGraw Hill, NY, 19^5,
esp. p. 78.
769 Gaydon, A. G. , and Wolfhard, H. G. , "Flames," Chapman and Hall, London, 1960,
esp. p. 151.
771 Fristrom, R. M. , and Westenberg, A. A., "Flame Structure," McGraw Hill, NY,
1965.
780 Rappopont, ed., "Chemistry of the Cyano Group," Interscience, NY, 1970.
781 Conant, J. R. , "The Chemistry of Organic Compounds," MacMillan, NY, 1939 »
esp. p. 160.
786 Bauleh, D. L. , Drysdale, D. D. , Lloyd, A. C., "Critical Evaluation of Rate
Data for Homogeneous Gas Phase Reactions in High Temperature Systems,"
School of Chem. , The University, Leeds, Vol 1-5, 1968-1969.
788 Morgan, A. C. , Ph.D. Thesis, MIT 1967, "Combustion of Methane in a JetnStirred
Reactor."
790 Martin, G. B. and Berkau, E. E., "An Investigation of the Conversion of Various
Fuel Nitrogen Compounds to the Nitrogen Oxides in Combustion," Preprint,
Environmental Protection Agency, Cincinnati, 1971*
791 Turner, D. W. , Andrews, R. L. Siegmund, C. W. , "Influence of Combustion
Midification and Fuel Nitrogen Content on Nitrogen Oxides Emissions," Preprint
Esso Res. and Eng. , Linden, NJ.
(continued)
S-1^129 122
-------
Table_An-6JCont)._Complete References to Non-Periodical Literature
795 Tyson, T. J., "An Implicit Integration Method for Chemical Kinetics,"
Paper 98^0-6002^0000, Sept. 1964, TRW Space Tech. Lab., Redondo Beach, Calif.
796 Bailey, H. E., Integration of the Equations Governing the One-Dimensional
Flow of a Chemically Reacting Gas," Preprint, Ames Research Center, Moffett
Field, Calif.
798 Fine, D. H., Slater, S. M., Sarofim, A. F., Williams, G. C., "The Importance
of Nitrogen in Coal as A Source of Nitrogen Oxide Emission From Furnaces, MIT,
Fuels Res. Lab. Report
797 Bartok, W. et al, "Systems Study of Nitrogen Oxides Control Methods for
Stationary Sources," Esso Res. and Eng. Co- Final Report, GR-2-NOS-69(l969),
Clearinghouse PB 192-789.
799 Jonke, A. A., et al, "Reduction of Atmospheric Pollution by the Application of
Fluidized Bed Combustion," Argonne Nat. Lab. report ANL/ES-CEN-1001, 1969.
800 Sommerlad, R. E., Welden, R. P. Rai, R. H., "Nitrogen Oxides Emissions—An
Analytical Evaluation of Test Data," Preprint, 33rd Annual Meeting Am. Pow.
Conf., Chicago, April 22, 1971.
802 Brenstock, D,., Amster, R. L. Bauer, E. R., Preprint, "Formation of NOX in
Pulverized Coal Combustion/' Bur. Mines, Pittsburgh.
S-14129 123
-------
Appendix HI. Simulation of Flame Fronts by "Point-Wise" Kinetic Calculations
The flame in a premixed or diffusion flame of a highly combustible system,
is very thin but of finite thickness. The thickness can be regarded as the distance
over which convectional, diffusional and reaction mechanisms, are all significant so
that none can be neglected. The exact solution of the governing equation for any
but the simplest kinetics schemes is very formidable involving as it does an
elliptic set of differential equations and (possibly) stiff kinetics. Only for
very simple systems ( See 789) have "exact" solutions been obtained.
In this Appendix we describe methods by which the diffusional processes
can be taken into account in a rough manner so as to provide estimates of flame
thickness, flame speed, and the concentrations of all species at a representative
point in the flame front. While for many systems the approximations that have to
be made are not valid, e.g., CDS flames where multiple flame fronts are observed
(7914-), there are also many systems where they probably are permissible. For ex-
ploratory calculations it is not advisable to expend a great deal of effort in
supposedly exact simulation of diffusional effects when the kinetic mechanism is
known only very approximately.
Premixed Flat Laminar Flames
For this case we approximate the flame front by a reactor with back diffusion
with the Wehner-Wilhelm boundary conditions.
A^ the inlet, the total flux of each component is specified.
At the outlet, the diffusive flux of each component is zero.
A sketch of the reactor is shown in Figure AIII-1, with a typical concentration
gradient for one of the components. We approximate the concentration profile by
the quadratics
yi = ai + bix
Conditions are imposed to permit evaluation of the undertermined constants
., c±, h, and N^f the total flux.
These conditions are:
p
(l) Mole fraction at the outlet is y±. For the "fuel" specie -the exit -mole
fraction is specified (yfuei)>
(2) Gradient of mole fractions at the outlet are zero for all components.
(3) Flux of each species at the inlet section is N^ z i •
00 Mole fraction of the "fuel" species at the inlet is y fuei-
(5) The "point-wise" rate of reaction at the exit section matches the material
balance for each component, i. e. , equation A III -2 is satisfied at the exit
section.
The governing equations for the case where the fluxes of all components are
parallel are the Maxwell Stefan equations.
125
-------
I
Idealized Porous Plugs,
Feed
Flux = Nj
Concentration
Profile
(Typical)
Zero Gradient
at Exit
Figure AI1I-1. CONCEPTUAL SKETCH OF FLAME FRONT IN A
LAMINAR PREMIXED FLAME
S-14129
68275
126
-------
and the material balance for the species i is
dx = % A III-3
In these approximate calculations we assume that the product of density and binary
molar diffusivities for all component sand for all x can be replaced by a single
average value. We also neglect the change in the total number of moles flowing
past any section. With these approximations the governing equations become:
yiNt A Ill-lt-
A III-5
Using the equations and the boundary conditions we find after some manipulation;
/h + hf R? + yf = z }* A III-7
This may be compared with the governing equations for a perfectly stirred reactor.
CTOL) R± = yf - zf1 A in-8
Hence the "point-wise" material balance is the same as for a perfectly stirred
reactor with reciprocal space velocity VOL where
VOL = - + —
VUIj *
And now using the imposed conditions, the length of the reactor h and the throughput
Nt, which lead to the specified inlet and exit concentrations for the "fuel"
species are found to be
D(VOL) A 111-10
Nt = ' A III-ll
where
/
/ VOL
1 - yfuel/ ZfSel I A 111-12
1 - afuel/ zfuel^
S1U129 127
-------
At this stage the concentrations yfuel and zfuel of ^e fuel a-t ^^ i^let and
exit of the reactor are arbitrary. We must select values which can be expected to
give a fair representation of the conditions at the flame front. The exit section,
for a good simulation, ought to coincide approximately with the section where the
rate of consumption of fuel is a maximum, and the inlet section should be placed
where the reaction is very slow and yet the quadratic approximation to the concen-
tration profiles is not seriously in error. Tentatively we take the make the
following assignments.
e ia
zfuel " O'1 zfuel A 111-15
yfuel = 0.5 Zfuel A III-lU
Therefore the "equivalent" Wehner-Wilhelm reactor encompasses the region
from the midpoint of the flame front to the point where the conversion of the fuel
is ninety percent. The validity of these assignments can only be justified by
comparison of the predicted results with data.
Inserting these values for yfuel ao^L zfuel into equations A 111-10 and
A III-ll we find:
h = 0.9Vfy) (VOL) A 111-15
A 111-16
To calculate Nt and h we need to select an appropriate average diffusion co-
efficient. In the expectation that diffusion of heat is more important that than
diffusion of active species we suggest talcing pmD to be equal to k/Cpm evaluated
at the exit temperature and composition in the Wehner-Wilhel'n reactor.
Diffusion Flames Modeled by the Whitman Two-Film Theory
In real diffusion flames, the physical conditions near the flame front are
influenced in a very complex way by the turbulence in the system. We cannot hope
to model these processes very exactly. Instead we adopt the conventional chemical
engineering approach of using equivalent f iLn thicknesses in tho Whitman two film
model with filjn thicknesses the same as for the case where chemical reactions
do not occur. This theory then can be regarded as a means for correcting for the
effects of the chemical reactions.
We consider the steady state system sketched in Figure A III-2. On the right
is fuel gas with a composition specified at the boundary, X=c. Similarly, on the
left is the oxidizer gas with composition specified at x=0. Between these two
sections the concentration varies because of diffusion alone in zones A and B
and because of combined diffusion and reaction in zone R.
As in the case of the premixed flame model we take the diffusion coefficients
Dil-, for all species to be the same and to be independent of position.
We also assume that there is no net generation of moles at the reaction front.
128
-------
Zone A
Zone R
Zone B
Oxidizer
Gas
Mole Fraction
= Zero
Fuel
Gas
x = 0
x = a
= b
X = C
Figure AI1I-2. CONCEPTUAL SKETCH FOR DIFFUSION FLAME FRONT
S-14129
68275
129
-------
1th these approximations the governing equations are
PmD d^ = -Ni A III- 17
dx
dN A 111-18
and the solutions for the zones where reaction can be neglected are
N. = PmD (y± - yj) / m A 111-19
In zone R, reactions can not be neglected. We take them into account by a"point-
wise" calculation. In the reaction zone the concentration profiles for all species
are assumed to follow the quadratic equations
y± - Ai + Bjx + Cjx2 A 111-20
Boundary conditions are imposed on these equations at both edges of zone R to
match the concentrations and slope on the side where the reactant is being supplied
and to make the value and slope of that species zero at the opposite boundary. The
fluxes entering the reaction zone must also be specified. Appealing to the
Burke-Schumann model of the diffusion flame we take the fuel and oxidizer fluxes
to be equal to that corresponding to stoichiometric combustion to a specified set
of products. For example when burning methane we may assume that the products
are CO and HgO rather than COa since the rate of reaction to the CO stage is much
faster than that to the COa stage. The assumption of arbitrary products can not
be removed from the model at this stage of sophistication. To do this would re-
quire a more elaborate model. We also assume that the reaction zone R is very thin
compared to zones A and B.
With these approximations we find for the oxidizer (for example) the following
relations:
n /feed prod % f eed
D _ -PmD(ynT - ypx Wox
"ox - — ' '"
Comparing this with the governing equations for a perfectly stirred reactor, we see
that we can identify the rate at which re act ants diffuse up to the reaction front
(combustion intensity) with the following function of the equivalent reciprocal
space velocity:
_feed__prcd
>ox = V (VOL)
S1M29
-------
Appendix IV. Description of Computer Program EXHAUS for Integrating
Stiff Differential Equations Arising in Kinetics Problems
Abstract
A computer program, EXHAUS, for integrating sets of differential
equations arising from kinetics problems is described. This program, which uses
"a cantilevered implicit method" is especially suitable for systems of "stiff"
equations such as result from problems with great disparity in characteristic
reaction times, for example, combustion problems. Use of free format and internal
tables of thermochemical and rate constant data make the program especially easy
to use. Either well -mixed stages or plug flow reactors or combinations of these
types can be simulated with specified temperature histories or under heat balanced
conditions. The integration method, TYSON, can be used independently of the
chemical reaction features for difficult-to- integrate problems.
Purpose and Scope
Program EXHAUS integrates the conservation equations for individual
chemical species for a stirred-tank or plug-flow reactor. Temperature and pressure
may be specified as functions of residence time in the reactor or a heat-balanced
solution may be obtained. Up to 35 species may be handled. The reactions (up to
70 in number) may be unimolecular, bimolecular or termolecular provided they can
be represented by
A + B + C5*D + E + F
where A, B, C, D, E, F represents a molecule or molecular fragment. One of two
of the reactants or products can be missing. If a species is mentioned on both
sides of the ^ sign it is taken to represent a non- reacting third body. The
species name "M" represents a generalized third body. The program treats all
species as ideal gases; however, liquid phase reactions can be simulated by use
of a (large) effective pressure.
The method of integration used is based on the paper "An Implicit Inte-
gration Method for Chemical Kinetics" by T. J. Tyson (795). It is also discussed
in reference (796). This method of integration, which we call a "cantilevered
inplicit method" is especially suited to the integration of "stiff" equations such
as arise when some of the species react very much faster than some other species as,
for example, in combustion. No special precautions need be taken when formulating
the equations to eliminate nearly equilibrated reactions as must be done, for
example, when using explicit (predictor-corrector or Runge Kutta) methods. For
reaction systems which are not "stiff" the program described is somewhat slower
than explicit methods but it will often be found useful because of its convenient
input and its general reliability. Since it is an implicit method, the program
must calculate the partial derivatives of the rate expressions with respect to
temperatures and the concentrations. This is done "analytically" under the
assumption that the reactions are of integral order as implied by the way in which
they are written and that the reaction rates can be calculated from
rf = af Zf T^exp [-Ef/rt]
C
c
rr = ar Zp T^exp [-Er/AT] Cd Ce Cf
S1M29 131
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.* less than three reactants or products are involved, the corresponding concen-
.ration in these equations are replaced by unity.
Output Generated
After printing out the input data the program calcuates, prints and
plots (on the line printer) the temperature, pressure, gas density and species
mole fractions as a function of residence tijne. A time step of variable size is
used in the integration to reduce calculation time. The program also prints out
the forward and reverse rates for each of the reactions considered at a number of
time steps. This permits one to readily assess the importance of particular
reactions and to determine which reactions are at equilibrium.
Sample Problem
Appendix V shows input and output for one of the simulations described
in this report.
Problem Setup
The user will go through five phases in setting up a problem to be run
on EXHAUS. First he must specify the type and size of reactor, whether plug flow,
series of well mixed stages, or a series of well mixed stages followed by a plug
flow reactor. Second, he must specify the kinetic mechanism, components and
reactions with their rate constants. Third, he must specify amount and type of
output. Fourth, he may wish to alter the normal accuracy criterion and other
integration control parameters. The last phase is program execution.
This program uses a "free-format with control word" type of data card.
Columns 1-6 of each card contain a control word (for example: VOLUME, EXECUT....)
which functions as a machine instruction, directing the setting of a set of data
or the use of a particular option. Card order in the data deck is immaterial (with
certain minor and obvious exceptions e.g. the EXECUT card is the last in each
data deck). Below we describe briefly the function of each type of data card under
the five phases of data preparation. Precise statements of the format of each
type of card are given in Tables AIV-1 and AIV-2.
Phase I Reactor Configuration and Size
NUMWSS Sets number of well stirred stages, may be zero.
PLUGFLOW Calls for a plug flow reactor following the (NUMW3S)well stirred
stages-
FLAME
or
IGNITE Selects method used to calculate the well stirred stages.
We recommend FIAME.
VOLUME Determines the reciprocal space velocity of the well stirred
stages.
TIMEIN
and
TIMOUT Sets the range of the independent variable (time or reciprocal
space velocity) for the plug flow reactor.
132
31^129
-------
HTLOSS Determines the factors governing heat loss.
HEATBAIANCE Selects aheat balanced case as contrasted with specified
temperature and pressure.
PDECAY Sets the pressure or pressure-time profile.
TDECAY Sets the temperature-time profile.
Phase II Defines the reacting system in terms of species and reactions.
SPECIE Defines a chemical species and sets its mole fraction in the
feed and estimate of mole fraction in product.
HSFQRM Feeds in heat of formation, entropy of formation and other
molecular properties.
CPCONS Feeds in specific heat data.
STOICH Defines an elementary chemical reaction.
FRATCO Feeds in Arrhenius rate parameters for the forward direction
of a reaction.
RRATCO Feeds in Arrhenius rate parameters for the reverse direction
of a reaction.
For certain species and reactions the HSFQRM, CPCONS, FRATCO and RRATCO
cards are not needed. Internally stored data will be used.
Phase III Output Control
PRINTP Determines the maximun change in independent variable
tolerated without output.
NRITE Determines the frequency of detailed output. Suggested
- value 10.
DEBUGl) Determine degree of debug printout called for. For normal
DEBUG2I" printout omit these cards.
BUGPRV
Phase IV Integration Control
If not placed in the data deck, standard values for these parameters will
be used.
SSCONT Sets a parameter controlling step size.
STEPIN Gives an initial step size. If a value greater than 1000.0 is
given the program calculates step size automatical]^
MAJCTRY Gives the maximum allowed number of trials in program IGNITE.
Phase V The Execute Card
EXECUT Turns control over to the machine to solve the problem and
prints out the answer.
133
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Table AIV-1
FORMAT OF CONTROL AND DATA CARDS
Program EXHAUS
(l) To acquire and execute program
- your run card -
@ XQT CUR
FSTIN COMBFU/^09560
@N XQT EXHIGN
data deck for your
problem
ends with an EXECUTE card
stacked data deck for
second case - with selected
variables reset
ends with an EXECUTE card
XQT EXHIGN
stacked data deck with
all variables reset
ends with an EXECUTE card
(2) General comments on data cards
(a) Columns 1-6 are ordinarily for an identifier wordO»#«**, BUGPRI,
SSCONT, STEPIN, TIMEBI, TIMOUT, PRINTD, TDECAY, FDECAY, FRATCO,
RRATCO, STOICH, SPECIE, CONSTR, DEBUG1, DEBUG2, NUMWSS, HSFQRM,
CPCONS, FLAME, PLUGFL, HEATBA, MAXTRY, NRITE or EXECUT.
(b) The card is punched free format with fields delimited by commas
(or in the case of STOICH cards by + and = also). Blanks are not
significant. Decimal points need not be punched. Large (or small
numbers) may be represented by a magnitude multiplied by a power of
10. e.g. 123.UE-7.
(c) Card order is not significant except for the following points.
(cl) The FRATCO and RRATCO cards must follow the STOICH cards for
the corresponding reaction.
(c2) The HSFORM and CPCONS cards must follow the (SPECIE or STOICH)
card which first introduces the corresponding species.
(cj) The EXECUT card must be the last in the deck for that run.
(d) Certain "default" variables are built into the program. If the
user does not insert a card to set these the following cards are
'"understood" to be present;
311*129
134
-------
Table AIV-1 (Cont). Format_of jCpntrol and Data Cards
PDECAY, 1.0, 1.0, 0.0
STEPIN, 1000.0
SSCONT, 0.05
TIMEIN, 0.0
DEBUG1, 1
DEBUG2, 1000
MAXTRY, 200
NUMWSS, 1
(e) The program has built-in libraries of thermochemical constants
and Arrhenius rate parameters. Data cards CPCONS and HSFORM
have precedence over the internally stored data and likewise
FRATCO and RRATCO take precedence over the internally stored rates .
(f) Species names are left adjusted using the first 6 characters
only and filling In on the right with blanks if there are
fewer than 6 characters.
(g) Reactions are written with , + and a. signs to delimit fields;
the =i sign separates the reactants from the products. By
convention M represents a general gaseous third body.
135
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Table AIV-2. FORMAT OF DATA CARDS
w (Identifier Word in
First Field
ON
TIMEIN,
TIMOUT,
TDECAY,
PDECAY,
HJGPRI,
SSCONT,
STEPIN,
PRINTD,
SPECIE,
STOICH,
FRATCO,
PRATCO,
CPCONS,
HSFOKM,
VOLUME,
DEBUG1,
DEBUG2,
NUMWSS,
FLAME ,
PLUGFL,
HEATBA,
MAXTRY,
EXECUT,
NRITE ,
IGNITE,
FUEL ,
OXIDIZ,
DILUEN,
HTLOSS,
cm3 >
Successive fields are separated by commas, e.g. , < >, < >,
< title of problem >
< starting time, sec or starting volume,
< final time, sec, or final volume, cm3
< feed temperature, °K >, < temp, °Kat instant of starting >, < time interval, TIMP
sec >, < not used >.
< system pressure, atm, or, for liquid systems the effective pressure >
« use this card if debug printout is required, otherwise omit »
< the step size control parameter, usually 0.05; >
< the starting step size, sec or cm3 >
< minimum printout interval, sec >
< name of a species >, < mole fraction in feed>, < guess as to mole fraction in pro-
duct of stirred reactor >
< a 6 character identifier >,< reaction written symbollically, e.g. A+BKJsEH-E+F >
< a 6 character identifier >,< af >, < Qf >, , < Ej >
< a six-character identifier >, < a >, < Qj. >, < n^ >, < E >
< name of a species >, < ACP >, < BCP >, < CCP > , < DCP >
< name of a species >, < ^Kf >, < Sf >
< volume of well stirred reactor, cm3 /(g mole/sec) >
< number of consecutive steps to be printing with debug printout >
< number of consecutive steps to be skipped before debug printout >
< number of well stirred reactors in series >
« insert this card to force use of program FLAME >
« insert this card to force calculation of a plut flow reactor following the stirred
tank reactor »
« insert this card to force a heat balance, or omit for specified temp or pressure »
< maximum number of trials allowed in solving stirred tank reactor >
Causes program to execute the case described by the above cards.
< number of steps between successive detailed printouts, recommend 10 >
« insert this card if method IGNITE is to be used for well stirred stage calculation»
< species number of species identified as fuel >
< species number of species identified as oxidizer >
< species number of species identified as diluent >
< ambient temperature °K >, < radiative heat loss coefficient, cal/sec cm3(°K4>,
< convective heat loss coefficient, cal/sec, cm 3 (°K) >
-------
Appendix V. An Exhibit of the Computer Output Generated by Program EXHAUS
In order to show how EXHAUS is used and what types of output information
are generated, we give here a copy of the entire output for a typical modelling
problem. The problem displayed is that described in the section entitled "NO
Reduction by Secondary Fuel Injection (Reburning)." The problem name is WILD 6.
Because of its size, the complete listing is not included herein, but is
available through the U.S. Environmental Protection Agency.
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
PORT NO
.PA-650/2-74-017
3 RECIPIENT'S ACCESSION-NO.
TLE AND SUBTITLE
^inetic Mechanisms Governing the Fate of Chemically
Bound Sulfur and Nitrogen in Combustion
5 REPORT DATE
August 1972
6 PERFORMING ORGANIZATION CODE
7 AUTHOR(S)
C. V. Sternling and J.O. L. Wendt
8 PERFORMING ORGANIZATION REPORT NO
9 PERFORMING ORGANIZATION NAME AND ADDRESS
Shell Development Company
Emeryville, California 94608
10 PROGRAM ELEMENT NO
1AB013; ROAP 21ADE-10
11 CONTRACT/GRANT NO
EHSD 71-45 (Task 14)
12 SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
NERC-RTP, Control Systems Laboratory
Research Triangle Park, North Carolina 27711
13 TYPE OF REPORT AND PERIOD COVERED
Final (Through 8/72)
14 SPONSORING AGENCY CODE
15 SUPPLEMENTARY NOTES
16 ABSTRACT
The report gives the results of an investigation of kinetic mechanisms governing
the fate of chemically bound nitrogen and sulfur in combustion. A literature review
led to several critical questions which were investigated using detailed computer
simulations of reaction schemes considered to be relevant. The problem areas
examined included the role of pyrolysis, mathematical modeling of a turbulent
diffusion flame, kinetic mechanisms of NO formation and NO reduction, and
kinetic mechanisms of the oxidation of SO2 to SOS. The report tentatively answers
some of these questions, either from the literature survey or from the results of
the computer simulations. The insights gained may lead to control of air
pollutant emissions by combustion modifications.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b IDENTIFIERS/OPEN ENDED TERMS
c COS AT I Field/Group
Air Pollution Oils Stoichiometry
Kinetics Ammonia Additives
Sulfur Cyanides Quenching
Nitrogen Pyrolysis (Cooling)
Combustion Catalysis
Coal Mathematical Models
Air Pollution Control
Staged Combustion
EXHAUS
CODEN
CHEMEQ
13B
07D
20M
21B
8 DISTRIBUTION STATEMENT
Unlimited
19 SECURITY CLASS (Thu Report)
21 NO OF PAGES
146
20 SECURITY CLASS (Thispage)
22 PRICE
EPA Form 2220-1 (9-73)
138
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