MERCURY REACTION CHEMISTRY IN COMBUSTION FLUE GASES
FROM EXPERIMENTS AND THEORY
A DISSERTATION
SUBMITTED TO THE DEPARTMENT OF ENERGY RESOURCES
ENGINEERING
AND THE COMMITTEE ON GRADUATE STUDIES
OF STANFORD UNIVERSITY
IN PARTIAL FULFILLMENT OF THE REQUIREMENTS
FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY
Bihter Padak
June 2011
© 2011 by Bihter Padak. All Rights Reserved.
Re-distributed by Stanford University under license with the author.
This work is licensed under a Creative Commons AttributionNoncommercial 3.0 United States License.
http://creativecommons.org/licenses/by-nc/3.0/us/
This dissertation is online at: http://purl.stanford.edu/ph834px9700
ii
I certify that I have read this dissertation and that, in my opinion, it is fully adequate
in scope and quality as a dissertation for the degree of Doctor of Philosophy.
Jennifer Wilcox, Primary Adviser
I certify that I have read this dissertation and that, in my opinion, it is fully adequate
in scope and quality as a dissertation for the degree of Doctor of Philosophy.
Gordon Brown, Jr
I certify that I have read this dissertation and that, in my opinion, it is fully adequate
in scope and quality as a dissertation for the degree of Doctor of Philosophy.
Anthony Kovscek
Approved for the Stanford University Committee on Graduate Studies.
Patricia J. Gumport, Vice Provost Graduate Education
This signature page was generated electronically upon submission of this dissertation in
electronic format. An original signed hard copy of the signature page is on file in
University Archives.
iii
iv
Abstract
Emissions from coal combustion processes constitute a significant amount of the elemental
mercury released into the atmosphere today. Coal-fired power plants in the United States,
with the capacity of just over 300GW, are the greatest anthropogenic source of mercury
emissions. Mercury exists in coal combustion flue gas in a variety of forms depending on the
coal type and combustion conditions; i.e., elemental, oxidized and particulate. Particulate
mercury in the flue gas can be removed using air pollution control devices such as
electrostatic precipitators and fabric filters. Oxidized mercury is easily captured by wet flue
gas desulfurization scrubbers, while gaseous elemental mercury passes through the scrubbers
readily. Activated carbon, when injected into the gas stream of coal-fired boilers, is effective
in capturing both elemental and oxidized mercury through adsorption processes. However,
the mechanism by which mercury adsorbs on activated carbon is not exactly known and its
understanding is crucial to the design and fabrication of effective capture technologies for
mercury. The objective of the current study is to apply theoretical-based cluster modeling to
examine the possible binding mechanism of mercury on activated carbon. The effects of
activated carbon‟s different surface functional groups and halogens on elemental mercury
adsorption have been examined. Also, a thermodynamic approach is followed to examine the
binding mechanism of mercury and its oxidized species such as HgCl and HgCl 2 on a
simulated carbon surface with and without Cl. Energies of different possible surface
complexes and possible products are compared and dominant pathways are determined
relatively.
v
Since different methods are employed to capture varying forms of mercury, understanding
mercury speciation during combustion and how the transformations occur between different
forms is essential to developing an effective control mechanism for removing mercury from
flue gas. In this study, homogeneous oxidation of mercury via chlorine is examined
experimentally in a simulated flue gas environment. Mercury and chlorine are introduced
into a laminar premixed methane-air flame. Cooled flue gas is sampled and sent to a custombuilt electron ionization quadrupole mass spectrometer specially designed for mercury
measurement on the order of parts per billion (ppb) in flue gas.
The use of a mass
spectrometer allows for distinguishing between the different forms of oxidized mercury (Hg+,
Hg+2). By directly measuring mercury species accurately, one can determine the actual extent
of mercury oxidation in the flue gas, which will aid in further developing mercury control
technologies.
vi
Acknowledgments
The 6 years I have spent in graduate school has provided a lot to me in terms of both my
career and my personal growth. There are many people who contributed to this journey in so
many different ways and I would like to thank them all here for everything they have done.
First of all, I would like to express my gratitude and appreciation to my advisor Prof. Jennifer
Wilcox for all of her advice and guidance throughout my graduate education. She has always
been tremendously supportive, motivating and inspiring. It is an honor and pleasure for me to
be her first PhD student.
I am also thankful to the committee members Prof. Gordon Brown, Prof. Tony Kovscek and
Dr. Shela Aboud for their continuous support and valuable discussions. I would also like to
thank Dr. Stephen Niksa for providing me the opportunity to work with him. During my time
at NEA I have learned a lot from his knowledge and experience in the field.
I am indebted to Dr. Andrew Fry for opening his lab doors to me; sharing all of his
experience and helping me design my experimental system. Thanks for all of your
encouragement and all the fruitful discussions we had. I specially thank to Jack Ferraro and
Doug White from WPI for their assistance in building my experimental setup for the first
time. I am grateful to Kevin Kuchta from Extrel for his help and guidance in the mass
spectrometer work since my first day in the lab.
vii
I would like to express my thanks to all the colleagues, faculty and staff in the ERE
department at Stanford, especially Yolanda Williams and Sandy Costa for their kindness and
assistance all the time. Thanks to everybody in our research group: Ana, Ekin, Ni, Yangyang,
Ondra, Abby, Keith, Mahnaz and Dong-Hee. Special thanks go to Ana for all the hours she
spent in the lab with me and always being positive and motivating.
I would like to thank my friends at WPI, Can, Natalie, Diana, Fede, James, Mike and Hsinyi;
we had great times together. Special thanks go to Didem and Engin Ayturk for making us
feel like we have family in Worcester. All my friends here at Stanford, Ayse, Murat, Ozlem,
Aykut, Turev, Ekin, Naz, Bumin, Nevra, Ezer, Gurer, Ahmet, Duygu, Yusuf and many more,
I will always remember all the fun and laughter we have shared.
I am very grateful to Suren family for their tremendous support from my first day in the U.S
and making me part of their family.
My friends in Istanbul, Yelda, Ozge, Guniz, Canel, Gulin, Emre, Deniz and many more are
acknowledged with love for their unconditional friendship and making me feel not lonely
here. Guniz, thank you for being by my side no matter what all these years since our
childhood. Hatun, you and your Eticins have managed to make me smile at even the worst
times. Yelda, since the day you took me to the airport to come the U.S, I feel like you have
been with me all the time throughout this 6-year time with your daily emails. I missed you all
too much and I am sorry for missing most of the special moments in your lives!
Mom, I cannot express how grateful and lucky I am to have you as my mom. You are the
reason who I am. Saying thank you is never enough for everything you have done for me!
You have opened so many doors in my life that no one ever could. You have been always
been supportive of every decision that I have made, and with your trust I have always made
the right choice. As you always say, “sometimes love means letting it free”. Thank you for
letting me free and be here today and make you proud.
Erdem, canim, my best friend, my family and my love, it has been a long journey and I was
fortunate to share every single second of the past 6 years with you. Not only you have
viii
motivated and encouraged me in so many things even when things looked impossible, but
you also have managed to make me feel happy and joyous no matter what. I am thankful for
your endless love, support, encouragement and most importantly your belief in me. I could
not have done this without you and your love. I humbly dedicate this work to you with my
deepest love.
ix
x
Dedicated to Erdem
xi
xii
Contents
Abstract
v
Acknowledgement
vii
1
Introduction and Literature Review
1
1.1 Behavior of Mercury in Coal-fired Electric Utility Boilers……………………
3
1.2 Mercury Removal by Existing Controls……………………………………….
6
1.2.1
Mercury Capture in PM Controls……….……………………………..
6
1.2.2
Mercury Capture in FGD Systems…………………………………….
7
1.3 Mercury Control by Sorbent Injection………………………………………...
8
2
A Density Functional Study to Understand Mercury Binding on Activated
Carbon
13
2.1 Computational Methodology .............................................................................
13
2.2 Mercury Binding on Activated Carbon – Effects of Halogens and Oxygen
Functional Groups .............................................................................................
15
2.2.1
Introduction ............................................................................................
15
2.2.2
Activated Carbon Model ........................................................................
18
2.2.3
Effect of Halogens on Hg Adsorption Capacity ....................................
20
2.2.4
Effect of Oxygen Functional Groups on Hg Adsorption Capacity ........
21
2.2.5
Conclusions ............................................................................................
25
2.3 Understanding the Binding Mechanism of Mercury on Activated Carbon .......
25
xiii
2.3.1
Introduction ............................................................................................
25
2.3.2
Modeling Activated Carbon Surface .....................................................
27
2.3.3
Binding of Hg on Graphene and Graphene-Cl ......................................
31
2.3.4
Binding of HgCl on Graphene and Graphene-Cl ...................................
35
2.3.5
Binding of HgCl2 on Graphene ..............................................................
39
2.3.6
Conclusions ............................................................................................
41
3 Investigation of Homogeneous Mercury Oxidation
43
3.1 Introduction ........................................................................................................
43
3.2 Kinetic Modeling ...............................................................................................
53
3.2.1
Model Parameters ..................................................................................
53
3.2.2
Chlorine Speciation ................................................................................
54
3.2.3
Mercury Speciation ................................................................................
56
3.3 Experimental Setup ............................................................................................
60
4 Measuring Mercury
63
4.1 Traditional Methods ...........................................................................................
63
4.2 Mass Spectrometer .............................................................................................
65
4.3 Instrument Design ..............................................................................................
67
4.3.1
Supersonic System .................................................................................
71
4.3.2
Orifice Heater.........................................................................................
74
4.3.3
Chopper ..................................................................................................
77
4.4 Instrument Calibration .......................................................................................
78
4.4.1
Calibration of Hg ...................................................................................
78
4.4.2
Calibration of HgCl2 ..............................................................................
83
5 Summary and Future Work
89
Appendix
93
A Chemkin Model Data .........................................................................................
95
B Pump Testing Data .............................................................................................
167
C Laser Alignment Guidelines ..............................................................................
177
xiv
D Flange Drawings ................................................................................................
181
E Supersonic System Installation Guidelines ........................................................
187
Bibliography
191
xv
xvi
List of Tables
2.1
C-Cl bond distances (Å) for different positions of Cl2 ...........................................
18
2.2
C-Cl and C-Hg bond distances (Å) for different positions on the surface .............
20
2.3
Mercury binding energies (kcal/mol) and C-X bond distances associated with the
clusters from Figure 2.3..........................................................................................
2.4
21
C-Hg bond distances (Å) for the clusters associated with the clusters from Figure
2.4 ...........................................................................................................................
21
2.5
Bond distances (Å) of the clusters represented in Figure 2.4 .................................
23
2.6
Binding energies of mercury on halogen-embedded activated carbon with
different oxygen functional groups: lactone, carbonyl, phenol, and carboxyl. ......
23
2.7
Optimized parameters of graphene model .............................................................
29
2.8
Bonding Mulliken population analysis for Graphene, Graphene-Cl and Hg on
Graphene ................................................................................................................
2.9
30
Bonding Mulliken population analysis for Hg on Graphene-Cl and HgCl on
Graphene ................................................................................................................
33
2.10 Bonding Mulliken population analysis for HgCl on Graphene-Cl and HgCl2 on
Graphene ................................................................................................................
38
3.1
Summary of previous experimental studies ...........................................................
45
3.2
Rate parameters for mercury-chlorine reactions ....................................................
57
4.1
Calibration of the orifice heater ..............................................................................
75
4.2
Calibration of the orifice heater under vacuum ......................................................
75
xvii
4.3
Cavkit settings for different Hg concentrations .....................................................
79
4.4
Ionization energies (IE) of mercury and halogen species ......................................
82
4.5
Vapor pressure data of HgCl2 .................................................................................
84
4.6
Appearance potentials and heats of formation for positive ions produced from
4.7
mercuric chloride at 187 °C....................................................................................
85
Relative abundances of ions ...................................................................................
87
xviii
List of Figures
1.1
Pollutant control systems in coal-fired power plants .............................................
1.2
Equilibrium mercury speciation in flue gas as a function of temperature
(Pittsburgh coal) .....................................................................................................
2.1
20
Activated carbon clusters with oxygen functional groups: lactone, carbonyl,
phenol, and carboxyl ..............................................................................................
2.5
19
Cluster models of mercury adsorbed on activated carbon (AC) and halogenembedded activated carbon. X: F, Cl, Br, I ............................................................
2.4
19
Optimized geometries for Hg and Cl on different sites of the cluster (a) armchair
edge; (b)zigzag edge; (c) center .............................................................................
2.3
5
Optimized geometries for Hg and Cl2 on different sites of the cluster (a) armchair
edge; (b) zigzag edge; (c) center ............................................................................
2.2
3
22
Halogen-embedded activated carbon clusters with oxygen functional groups:
lactone, carbonyl, phenol, and carboxyl. X = F, Cl, Br, I .....................................
24
2.6 Optimized geometry of graphene (G) ......................................................................
29
2.7 Graphene models with chlorine ...............................................................................
30
2.8 Binding of Hg at different sites of graphene (G) .....................................................
31
2.9 Binding of Hg at different sites of G-Cl model .......................................................
32
2.10 Energy diagram for different pathways of Hg on G-Cl ...........................................
34
2.11 Binding of HgCl at different sites of G ....................................................................
35
2.12 Energy diagram for different pathways of HgCl on G ............................................
36
xix
2.13 Binding of HgCl at different sites of G-Cl...............................................................
37
2.14 Energy diagram for different pathways of HgCl on G-Cl .......................................
39
2.15 Binding of HgCl2 at different sites of G ..................................................................
40
2.16 Energy diagram for different pathways of HgCl2 on G ...........................................
41
3.1 Chlorine speciation with Roesler and Bozelli mechanisms using 100 ppmv Cl .....
55
3.2 Chlorine speciation with Roesler and Bozelli mechanisms using 100 ppmv Cl and
temperature profile. ..................................................................................................
55
3.3 Mercury oxidation data – comparison of the Wilcox-Roesler model and available
experimental data .....................................................................................................
58
3.4 Mercury oxidation data – comparison of the Wilcox-Bozelli model and available
experimental data .....................................................................................................
59
3.5 Schematic of the experimental system .....................................................................
61
4.1 Schematic of the mass spectrometer ........................................................................
65
4.2 Impact of electron with dynode releasing secondary electrons, etc.........................
67
4.3 Isotope pattern of HgO.............................................................................................
68
4.4 Photograph of the system with the heat blanket ......................................................
68
4.5 Pump configurations: Original configuration on the left, new configuration on the
right. Grey lines illustrate the vacuum hoses given with their sizes. .......................
70
4.6 Schematic of the supersonic system ........................................................................
72
4.7 Mass spectrum of mercury dimer detected with the supersonic system ..................
74
4.8 Photo of the orifice heater on the left and the front flange showing the
feedthroughs (FT) on the right .................................................................................
75
4.9 Effect of temperature on cluster formation ..............................................................
77
4.10 Setup for Hg0 calibration .........................................................................................
79
4.11 Calibration curve for Hg0 .........................................................................................
80
4.12 Hg spectra with the blanket on (bottom) and off (top) ............................................
81
4.13 Isotope pattern of Hg with relative abundances from the literature (experimental
data on the left) ........................................................................................................
82
4.14 Fragmentation pattern of Hg and HgO with relative abundances ............................
83
xx
4.15 Schematic of the HgCl2 setup ..................................................................................
84
4.16 Mass spectrum of HgCl2 adapted from NIST ..........................................................
86
4.17 Calibration curve for HgCl2 .....................................................................................
87
xxi
xxii
Chapter 1
Introduction and Literature Review
Coal is the most abundant fossil fuel, which is sufficient to supply current energy demands
for up to 250 years. [1] The three locations with the highest recoverable coal reserves are the
United States with 27% of the world‟s recoverable reserves, China with 13%, and India with
10%. [2] Currently, within the United States, 50% of electricity is produced from coal, and
there are over five hundred 500-megawatt coal-fired power plants in the country. Coal will
never be a completely sustainable energy source; however, due to its abundance and current
popular use for energy gain worldwide, decreasing coal combustion‟s environmental impacts
are of great importance.
Emissions from coal combustion processes constitute a significant amount of the elemental
mercury released into the atmosphere today. Coal-fired power plants in the United States
(U.S.), with the capacity of just over 300GW, are the greatest anthropogenic source of
mercury emissions in the U.S [3]. Currently, 53 tons of mercury is released in the U.S. into
the atmosphere every year as a result of coal combustion [4] and globally there are 5,000 tons
Hg/year emitted [5]. Reducing the emissions of mercury is a major environmental concern
since mercury is considered to be one of the most toxic metals found in the environment [6]
and additionally is considered a hazardous air pollutant (HAP) by The Clean Air Act (CAA)
of 1990.
1
Oxidized forms of mercury have much shorter atmospheric lifetimes than elemental
mercury because of its enhanced water solubility and ability to readily adsorb onto surfaces.
Oxidized mercury has a residence time of a few days while elemental mercury remains in the
atmosphere up to a year [7,8]. Therefore, elemental mercury can be transported over long
distances whereas oxidized and particulate mercury deposit near the point of emission.
Mercury, once released into the environment, can precipitate into lakes, rivers and estuaries
and can be converted through biological processes into an organic form, methylmercury,
which is a neurotoxin that bioaccumulates in fish, animals, and mammals [9,10]. Humans are
most likely to be exposed to methylmercury through the consumption of fish. Based on the
estimations of the United States Environmental Protection Agency (EPA), each year
approximately 300,000 newborns in the US have the risk of developing disabilities due to
methylmercury exposure related to consumption of contaminated fish [11].
Elemental mercury has adverse effects on the central nervous system and causes pulmonary
and renal failure, severe respiratory damage, blindness and chromosome damage [12,13].
Exposure to HgCl2, the most common oxidized form, is corrosive to the eyes, skin, and
respiratory tract upon short-term exposure and may affect the kidneys upon longer or
repeated exposure [14]. Methylmercury, the form found to bioaccumulate in fish, has a
reference dose of 0.1 μg/kg bw/day, which is the maximum level considered safe by the
United States Food and Drug Administration (FDA). Neurotoxic effects such as a decrease
in motor skills and sensory ability, tremors, the inability to walk, convulsions, and death may
result from higher exposures [8].
In March 2005, the EPA adopted the Clean Air Mercury Rule to reduce mercury emissions
from coal-fired power plants, [5] which will ultimately reduce the US emissions of mercury
to 15 tons a year, constituting an approximate 70% reduction. Although this rule was vacated
by the Courts in February 2008 [5], the EPA recently proposed Mercury and Air Toxic
Standards, the first national standards to reduce emissions of toxic air pollutants from new
and existing coal- and oil-fired power plants, in March 2011 [4]. These standards are
expected to reduce the emissions of metals including mercury (Hg), arsenic (As) and
selenium (Se), acid gases i.e., hydrogen chloride (HCl) and hydrogen fluoride (HF), and
2
particulate matter. For mercury emissions, the standards for the existing sources in the
category must be at least as stringent as the emission reductions achieved by the average of
the top 12% best controlled sources for source categories with 30 or more sources. This new
rule is expected to prevent 91% of mercury in coal from being released to air.
1.1 Behavior of Mercury in Coal-fired Electric Utility Boilers
The primary products of coal combustion are carbon dioxide (CO2) and water (H2O).
Additionally, significant amounts of pollutants such as sulfur dioxide (SO2), nitrogen oxides
(NOx) and trace elements such as mercury are formed. A schematic of a typical coal-fired
power plant with the pollutant control systems of interest is shown in Figure 1.1.
NH3
1400 °C
Stack
Sorbent Injection
Boiler
Flue Gas
ESP
Air Heater
SCR
350°C
100°C
FGD
140 °C
Fan
50°C
Ash &Sorbent
HgCl2
SO2
Adsorbed Hg Gypsum
Figure 1.1: Pollutant control systems in coal-fired power plants
Mercury exists in coal combustion flue gas in a variety of forms depending on the coal type
and combustion conditions, i.e., elemental (Hg0), oxidized (HgCl2 or HgO) and particulate
(Hgp). Most of the mercury particulates, which comprise 10% of the total mercury in the flue
gas can be removed using air pollution control devices (APCD), such as electrostatic
precipitators (ESP) and fabric filters (FF). Oxidized mercury, (Hg+2) is easily captured by
wet flue gas desulfurization scrubbers, while gaseous elemental mercury passes through the
scrubbers readily. It is difficult to capture elemental mercury because of its insolubility in
3
water, higher volatility and chemical inertness [15]. Particulate matter such as fly ash,
unburned carbon and activated carbon can be used to capture elemental and oxidized
mercury through adsorption processes. Interaction of gaseous mercury with particulate matter
can either lead to adsorbed and subsequent retained mercury on the surface, or can serve to
oxidize Hg0 to a water-soluble form for capture in wet scrubbers. Since different methods are
employed to capture different forms of mercury, understanding mercury speciation during
combustion and how the transformations occur between different forms is essential to
developing an effective control mechanism for removing mercury from flue gas.
Mercury is found in coal at an average concentration of 0.1 ppmv. The majority of mercury
in coal is associated with pyrite. Other forms of mercury that have been reported to exist in
coal are organically bound, elemental, and within sulfide and selenide minerals [3]. During
combustion it is released as Hg0 vapor, and then it is oxidized to Hg+2 via homogeneous (gasgas) and heterogeneous (gas-solid) reactions [16]. It is in the thermodynamically favored
elemental form Hg0 in the hot combustion section of the boiler (about 1400 ºC) ranging in
concentration from 1-20 μg/m3. Gas-phase oxidation occurs via chlorine species as the gases
cool down through the air preheater and air pollution control devices [17]. A study consisting
of mercury speciation measurements from fourteen different coal combustion systems
reported anywhere from 30% Hg+2 to 95% Hg+2 upstream of the APCD [18]. The majority of
the measurements fall in the 45-80% range [19,20,7]. In general, 20-50% of mercury
emissions are Hg0 and 50-80% Hg+2 [21]. Although current techniques used in these studies
cannot identify the specific forms of oxidized mercury, it is believed to be HgCl 2
[7,18,22,23]. There appears to be little experimental evidence for the existence of mercurous
compounds in coal combustion flue gases [20].
Based on a study by Senior et al., [7] thermodynamic calculations predict that mercury
oxidation begins to occur at about 700 °C and mercury will be completely oxidized at 450
°C. A plot of equilibrium mercury speciation in flue gas for the Pittsburgh coal (bituminous)
as a function of temperature is shown in Figure 1.2. Between 450 °C and 700 °C the split
between Hg0 and HgCl2 is determined by the chlorine content of the coal. For example,
Sliger et al. [24] reported the 50% equilibrium conversion to HgCl2 occurring around 675 °C
4
in the presence of 500 ppm HCl and around 550 °C in the presence of 50 ppm HCl. Senior et
al. [7] found the 50% conversion point as 830K (557 °C) for coal containing 1000 ppm Cl at
900K (627 °C) with 4000 ppm Cl. Other studies also yielded that the conversion point falls in
the range of 800-900K (527-627 °C) [25]. On the other hand, it was found that the mercury
content of the coal has no effect on the equilibrium distribution of mercury species.
Figure 1.2: Equilibrium mercury speciation in flue gas as a function of temperature
(Pittsburgh coal) [7]
Moreover, the flue gas temperature at the outlet of the air preheater ranges from 127 °C to
327 °C, which implies that mercury should exist entirely as Hg+2 downstream of the air
preheater. However, measurements show that Hg0 also exists in the flue gas at this location.
This gives rise to the conclusion that “the assumption of equilibrium for mercury species in
coal combustion flue gas is not valid.” In other words, mercury oxidation is kineticallycontrolled, not thermodynamically-controlled [7].
Since thermodynamic calculations are limited to represent mercury speciation accurately, a
detailed kinetic model including both homogeneous and heterogeneous oxidation is required
5
to understand mercury speciation in a coal fired power plant and for the development of
better mercury control technologies.
1.2 Mercury Removal by Existing Controls
Mercury removal may be achieved as a co-benefit of SO2 controls and PM controls as well as
through mercury specific control technologies. The degree of this co-benefit depends on the
specific control technology configuration and the type of coal that is burned [3].
Western coals (lignite and subbituminous) on average contain lower levels of mercury,
chlorine, and sulfur than bituminous coals [26]. This has important effects on the quantity
and form of mercury emitted from a boiler and on the capabilities of different control
technologies to remove mercury from flue gas. For eastern bituminous coals having high
chlorine content, the fraction of the more easily removable oxidized form of mercury in the
total mercury emission is higher. Low chlorine content of lignite and subbituminous coals
leads to the emission of predominantly elemental mercury, which is substantially more
difficult to remove. Real field tests done with three different coal types for the same APCD
configuration have revealed that the average mercury removal for bituminous coal is greater
than for other coals. This is associated with the high chlorine content of bituminous coal.
1.2.1 Mercury Capture in PM Controls
Use of a fabric filter (FF) can be very effective for mercury capture for both bituminous and
subbituminous coal, but especially for bituminous [3]. Mercury capture in plants having FF
technology only is more effective than in plants having a cold side ESP (CS-ESP) or hot side
ESP (HS-ESP) since there is less contact between mercury and fly ash in ESP units. In
addition to this, HS-ESPs operate at higher temperatures and mercury capture in fly ash is
effective at low temperatures. However, only less than 5% of the US coal burning capacity
has solely the FF configuration.
6
PM controls for mercury capture is more effective in the case of injecting a sorbent to the
flue gas, which will be discussed later.
1.2.2 Mercury Capture in FGD Systems
Mercury capture can be achieved using either gas or solution-phase remediation processes.
Typically it is desirable for elemental mercury from the flue gas to be converted to the
oxidized water-soluble form for effective capture in wet chemical scrubbers. Depending on
the kind of coal used and the percentage of sulfur burned, combustion facilities may be
equipped with wet or dry scrubber systems. Some coals, such as bituminous have high sulfur
content so that wet chemical scrubber techniques tend to be the more suitable application.
Data from actual facilities have indicated that over 90% of Hg+2 is expected to be removed in
calcium-based wet FGD systems, although there are some cases where it has been found to
be less [16]. One reason for this may be the scrubber equilibrium chemistry [27]. In addition
to limited FGD chemistry, reemission of mercury may result in Hg+2 capture that is
significantly less than 90%. It has been shown that Hg+2 will be reduced to Hg0 under some
conditions and subsequently mercury will be reemitted [28].
In a wet FGD system SO2 is mixed with limestone-based slurry and through forced
oxidation, hydrated gypsum is generated. After generation, these waste products can be
calcined, i.e., dehydrated under high temperature and pressure conditions. It is this stage in
the recycling process in which TEs bound to the calcium-based sorbent can be reemitted and
cause environmental concern and possible contamination. A study conducted in 2005 through
the Department of Energy, NETL, indicated minimal leaching of mercury from FGD
byproducts. However, the study was vague indicating that an „unknown‟ binding agent
present in the SO2-capture reagent was responsible for the minimal leaching and subsequent
stability of mercury at moderate temperatures of 94ºC or less [29]. In fact, a conflicting study
by Heebink and Hassett was published in the same year, indicating that at high-temperature
conditions, which are required for gypsum calcification, mercury leaching should not be
neglected and that “the potential for mercury release during the calcining process of FGD
7
gypsum wallboard production exists.” This publication also states that additives used in the
process of gypsum calcining have yet to be investigated for minimizing potential TE leaching
[30].
Oxidation of Hg0 to Hg+2 by the SCR Catalyst
Since Hg+2 is captured more effectively in wet FGD systems than Hg0, increasing the amount
of Hg+2 upstream of FGD unit should enhance mercury removal. It has been shown that
under some conditions the SCR catalyst promotes the oxidation of Hg0 to Hg+2 [16]. Field
tests have shown that mercury oxidation is greater for bituminous coal than for
subbituminous coal [31,32]. A study by Senior and Linjewile suggests that the oxidation of
Hg0 to Hg+2 by SCR when firing subbituminous coal is limited by equilibrium rather than by
kinetics [33]. Therefore, it is not possible to improve the catalytic oxidation of mercury with
SCR when burning low-rank coals without changing the flue gas chemical composition or
lowering the catalyst temperature.
1.3 Mercury Control by Sorbent Injection
Unlike the technologies previously described, where mercury was removed as a co-benefit of
existing air pollution control devices, specific mercury control via injection of sorbent
materials into the gas stream is currently under development. Many studies have been
performed to determine an effective and affordable sorbent for the removal of elemental
mercury from combustion flue gas. Activated carbon (AC) is one of the most studied
sorbents for capturing mercury. Activated carbon adsorption can be performed through two
different processes, i.e., powdered activated carbon (PAC) injection or fixed-bed granular
activated carbon (GAC) adsorption. The use of PAC involves the direct injection of activated
carbon into the plant‟s flue gas stream where it adsorbs gaseous mercury and is collected in
downstream particulate control devices, such as FFs or ESPs. In the case of using GAC, an
adsorber is placed downstream of the FGD unit along with particulate collectors, which serve
as the final treatment process before the flue gas is discharged into the atmosphere [34]. One
8
drawback of activated carbon injection is that there is some concern about the impacts to
marketing the fly ash for beneficial reuse, especially when the ash is used as a cement
additive [16]. Activated carbon prevents the concrete to meet the freeze-thaw requirement,
which is not desirable. One solution to this problem is segregating the fly ash with a
TOXECONTM system where activated carbon is injected downstream of the ESP unit after
the fly ash is collected. This system has another advantage in that activated carbon is injected
at a lower temperature, which increases its efficiency to capture mercury.
It has been shown that chemically-embedded activated carbon has a higher mercury
adsorption capacity than purely thermally-activated carbon. Specifically, sulfur, chlorine,
bromine and iodine-embedded activated carbon have been found to be effective sorbents for
elemental mercury capture. It has been observed that at 150-260 ºC, activated carbon
embedded with chlorine salt has as much as a 300 times greater elemental mercury removal
capacity than traditional thermally activated carbon [35]. It has also been reported by
Matsumura that oxidized or iodized activated carbon adsorbed mercury vapor 20-160 times
more than untreated activated carbon in nitrogen at 30 ºC [36]. Granite et al. stated that
hydrochloric acid-treated activated carbon yielded a large capacity of mercury in the
experiments carried out in argon at 138 ºC, which makes it one of the most active sorbents
studied to date [37]. However, the cost related to the preparation of chemically-embedded
activated carbon is high. There have been many attempts to find a low-cost alternative
sorbent, but limited success has resulted due to problems associated with removal efficiency
[38]. Therefore, it is essential to develop a novel sorbent for the effective and affordable
removal of elemental mercury.
Krishnan et al. have shown that the type of activated carbon, reaction temperature and inlet
Hg0 concentration affect sorption rates and capacity for elemental mercury. They have found
elemental mercury sorption on thermally activated carbon to be decreasing with increasing
temperature [38]. It has been illustrated by many studies that adsorption process of mercury
on activated carbon surfaces is exothermic, indicating a typical physisorption mechanism
[38-42]. Moreover, sulfur, iodine and chlorine impregnants are thought to provide sites
where the mercury can chemically adsorb onto the carbon surface [43]. For chlorine- and
9
sulfur-impregnated activated carbons the lower the temperature the higher the adsorption
capacity of mercury because of exothermic behavior of mercury reaction with chloride [4346] or elemental sulfur [47,34]. Conversely, in the case of iodine-impregnated activated
carbon the amount of mercury adsorbed by the carbon increases as the temperature increases
[48].
Studies performed at the Energy & Environmental Research Center (EERC) in Grand
Forks, North Dakota have examined the effects of flue gas acid species such as HCl, SO2,
NO, NO2 on mercury capture as well as mercury binding and oxidation mechanisms. In the
model they have proposed, electrons must be accepted by a Lewis acid on activated carbon
and then Hg+2 which is a Lewis acid can bind to Lewis base sites on the surface competing
with other acidic species such as HCl and sulfuric acid [49-52].
Investigations carried out by Carey et al. have found that the type of carbon sorbent and its
associated chemical properties are the most important factors affecting elemental mercury
adsorption for a given flue gas composition [53]. It has been observed that moisture within
the activated carbon matrix plays an important role in promoting elemental mercury
adsorption at room temperature [54]. Lee et al. observed that virgin activated carbon with
large oxygen functional groups was superior in mercury adsorption performance [55]. Li et
al. also studied the effect of activated carbon‟s oxygen surface functional groups such as
lactone, carbonyl, phenol and carboxyl on elemental mercury adsorption [56]. They found
that both lactone and carbonyl groups are the likely active sites for mercury adsorption on an
activated carbon surface. They also investigated whether phenol groups may inhibit mercury
adsorption and whether the activated carbon surfaces having a lower phenol to carbonyl ratio
yield a greater elemental mercury adsorption capacity.
Although there are plenty of studies on mercury removal with activated carbon, there are
still some chemical effects that are not understood well. Some of these effects are listed here
[3]. The effect of chlorine or HCl on the capacity of sorbent to adsorb Hg0 is recognized but
not understood in a quantitative way. This is a concern particularly for coals with low
chlorine levels that produce mostly Hg0. Mercury concentration and speciation may have an
impact on the capture efficiency of the sorbent. However, quantitative data on this effect is
10
lacking because speciation of mercury is not fully understood yet. It is known that SO3
interferes with mercury capture, but a quantitative understanding is lacking. Recent field tests
of mercury removal with activated carbon injection have shown that mercury capture is
limited when concentrations of sulfur oxides are high in the flue gas. The formation of SO3
occurs both in the furnace of a coal-fired boiler and through across SCR systems catalysts
originally intended for NOx emission reduction. Within the last ten years, elevated levels of
SO3 concentrations have been acknowledged as a problem for facilities responsible for the
combustion of high-sulfur fuels [57-60]. In a recent study by DOE investigating the effects of
SO2 and SO3 on mercury capture in simulated flue gas has shown that the final mercury
content of the activated carbons is independent of the SO2 concentration in the flue gas;
however, the presence of SO3 inhibits mercury capture [61]. They suggest two hypotheses to
explain the inhibition of mercury capture by sulfur oxides: (1) depletion of surface chlorine
through the formation of sulfuryl chloride and (2) competitive adsorption between sulfur
oxides, particularly SO3 and Hg.
11
12
Chapter 2
A Density Functional Study to
Understand Mercury Binding on
Activated Carbon
In this chapter, the interaction of mercury with the activated carbon surface is investigated
from a theoretical perspective, employing the tools of computational chemistry.
Computational chemistry allows one to study chemical phenomena by running calculations
on computers rather than by examining reactions experimentally. Not only stable molecules
can be modeled, but also short-lived, unstable intermediates and transitions states can be
modeled.
2.1 Computational Methodology
Ab initio methods are based solely on the laws of quantum mechanics and on the values of
physical constants such as the speed of light, Planck‟s constant and the masses and charges of
electrons and nuclei [62]. Quantum mechanics states that the energy and other related
13
properties of a molecule may be obtained by solving the Schrödinger Wave Equation (SWE)
given below:
H  E
(2.1)
where Ψ is the wave function, E is the electronic energy and H is the Hamiltonian operator; a
differential operator representing the total energy of the system. H consists of kinetic energy
and potential energy operators, which are represented by the first and second terms of
Equation (2.2)
 2

 2m
 2
2
2  
 (r , R, t )
 2  2  2     (r , R, t )  i
t
y
z  
 x
(2.2)
Equation (2.2) is another form of the SWE where m is the mass of the particle, v is the
potential energy operator and  is related to Planck‟s constant (h) with the relation:
  h / 2 . The potential energy operator, v represents the potential energy of nuclearelectron attraction and electron-electron repulsion.
Exact solutions to the SWE are not computationally practical; however, there are various
mathematical approximations to its solution. Ab initio methods compute solutions to the
Schrödinger equation using a series of rigorous mathematical approximations.
The Gaussian03 software package [63] was used for all of the energetic predictions in this
work. Gaussian offers a variety of techniques including variational methods (Hartree Fock
(HF), quadratic configuration interaction (QCI), coupled cluster (CC)), methods employing
perturbation theory (Moller Plesset) and density functional theory (DFT).
There is also a variety of basis sets, which is a mathematical representation of the molecular
orbitals within a molecule. Larger basis sets impose fewer constraints on electrons and more
accurately approximate exact molecular orbitals, thus require more computational time [62].
A combination of the method and the basis set is called “level of theory” and shown as
method/basis set within this work.
In this work DFT was employed due to its balanced computational efficiency and accuracy.
DFT methods require about the same amount of computational time as HF, the least
14
expensive ab initio method, while providing more accurate results compared to HF due to its
inclusion of electron correlation. [62]. Beck‟s three-parameter functional with a Lee-YangParr gradient-corrected correlation functional (B3LYP) is known to produce fairly accurate
bond energies and thermodynamic properties of reactions [64,65]. Also, it has small spin
contamination compared to other methods such as HF [66]. Montoya et al. [66] have
illustrated that spin contamination in the unrestricted B3LYP is reasonably small and has
acceptable minor effects on the energetic properties of graphene layers. They have also
shown that the differences in both adsorption geometry and binding energy between the
unrestricted and restricted open-shell wave function are small. The B3LYP method has been
employed in many studies [64-71], in which a carbonaceous surface is simulated, along with
the 6-31G(d) basis set and has been shown to provide accurate energetic properties of
carbon-oxygen complexes [64,65,67]. According to Radovic et al. [70], this level of theory is
a reasonable compromise that minimizes spin contamination, includes configurational
interaction, and accomplishes the calculations at acceptable computational expense.
In the current study, considering that mercury has eighty electrons, to account for
relativistic effects a basis set with the inner electrons substituted by an effective-core
potential (ECP) was chosen. The B3LYP method with the LANL2DZ basis set, which uses
an all-electron description for the first-row elements and an ECP for inner electrons and
double-ζ quality valence functions for the heavier elements was used for the energy
predictions within this work [72-74].
2.2 Mercury Binding on Activated Carbon – Effects of Halogens
and Oxygen Functional Groups
2.2.1 Introduction
As mentioned in the background chapter, not only have experimental studies been performed
in this area, but theoretical studies have also been carried out to gain an increased
15
understanding of the mechanisms involved in elemental mercury adsorption onto activated
carbon surfaces. To the authors‟ knowledge this is the first ab initio-based investigation
involving the adsorption of elemental mercury on halogen-embedded activated carbon thus
far. However, there have been theoretical investigations involving adsorption on graphite,
which have provided ideas on how to begin modeling a carbon surface.
Chen and Yang [75,76] have investigated different theoretical methods and different
graphite models for describing graphite surface using ab initio methods. Comparing
geometry, frequency and bond parameters calculated at different levels of theory to the
experiment, B3LYP/6-31G(d)//HF/3-21G(d) has been found to be the most accurate and
cost-effective method. Six graphite models with increasing sizes from 1 to 7 seven fused
benzene rings were considered at the chosen level of theory. According to their comparison,
C25H9 is the most suitable model among the others representing a single layer graphite
surface.
Lameon et al. [77] have performed a study on the adsorption of potassium (K) and oxygen
on graphite surfaces based on the Monte Carlo simulations. They have used a periodically
repeated hexagonal supercell of n graphite layers (n = 1,2,3) and showed that the main
physics is correctly described by a single graphite layer. Zhu et al. [78] compared the
adsorption of alkali metals on graphite surfaces modeled as seven, ten, twelve and fourteenfused benzene rings. Since Janiak et al. [79] and Lameon et al. [77] have found that the
difference of K adsorption on single-layer graphite and multilayer graphite is negligible, they
chose single-layer graphite for their studies. Investigating three different sites for adsorption
they showed that the “middle hollow site” above a hexagon is the most stable position for the
adsorptions of Li, K and Na. Their analysis indicated that, comparing two levels of theory,
the results from MP2 are not as reliable as those from B3LYP.The binding energies obtained
at the B3LYP/6-31G(d,p) level of theory are in good agreement with other theoretical
studies.
Ohta et al. [80] investigated the adsorption of hydrogen on graphite using the B3LYP/631G(d) level of theory. Pyrene, which has four closely fused aromatic rings (C16H10) was
used in the calculations for simulating a graphite surface. Pliego et al. [81] studied the
16
chemisorption of SO2 on a graphite surface investigating the adsorption sites as well as the
stability of the adsorbed complexes. The HF/6-31G(d) level of theory was utilized in the
geometry optimization. Frequency and single-point calculations were performed at MP2/631G(d) to obtain reaction energies. The pyrene structure and two dehydrogenated derivatives
corresponding to armchair and zigzag edges were used in modeling the graphite surfaces to
simulate different adsorption sites. They have found adsorption to be favorable on an
armchair edge with binding energies of -5 to -51 kcal/mol and found adsorption on a zigzag
edge to be the most favorable with binding energies ranging from -61 to -100 kcal/mol.
Collignon et al. [82] used ab initio methods to understand the mechanism associated with
water adsorption on hydroxylated graphite surfaces. The graphite surface consisted of thirtyfused benzene rings (C80H22), which represents a nanometer-size graphite crystallite. To
optimize such a large surface, the two-layered ONIOM method was utilized, which divides
the system into two nested regions. These regions are considered with different model
chemistries and then merged into the final predicted results. The central part of the system
that contains the water molecules, the OH group and the closest neighboring C and H atoms
is modeled with B3LYP method while the rest of the system is modeled with the
semiempirical PM3 method so that a balance between accuracy and computational time is
obtained. All of these previous studies have focused on understanding the structure of
activated carbon and its active sites and the role they play in adsorption mechanisms.
Limited theoretical investigations have been performed on the mechanism responsible for the
adsorption of mercury on activated carbon surfaces.
Steckel [83] has investigated the interactions between elemental mercury and a single
benzene ring, which is quite limited in its potential for representing an accurate carbon
surface. However, this previous study is the first to begin the investigations required for
elucidating the mechanism by which elemental mercury binds to carbon. No known research
has been conducted toward understanding the mechanism of mercury adsorption on
simulated halogen-embedded activated carbon surfaces. The objective of the current study is
applying theoretical-based cluster modeling to examine the effects of activated carbon‟s
different surface functional groups and halogens on elemental mercury adsorption. This
17
research will provide direction for further experimental studies that will aid in the
development of a novel sorbent for effective mercury capture.
2.2.2 Activated Carbon Model
For the theoretical model it was assumed that the activated carbon molecular framework is
similar to that of graphite. Pyrene was examined to serve as a representative cluster species
to model the activated carbon surface. A larger cluster, possibly more accurate, would
require greater computational effort. Through comparing the structure predictions of fourand seven-fused benzene rings, the four-fused rings were chosen since the calculations
provide a reasonable balance between accuracy and computational expense.
In order to optimize a halogen-embedded activated carbon surface, halogens were
embedded at different sites along the cluster surface, i.e., the armchair edge, zigzag edge and
center site. Optimization calculations have been carried out using the B3LYP method with
the LANL2DZ basis set. The optimized bond distances of carbon and chlorine atoms are
presented in Table 2.1 with the optimized structures shown in Figure 2.1. The theoretical
geometry predictions convey that there is a minimal difference between the C-Cl bond
distance from either the armchair or zigzag edge sites, while this bond distance is much
greater at the center site. More calculations have been performed using a bromine-embedded
surface at the HF/SDD and HF/6-311G levels of theory and similar results have been
obtained. It has been noted that no stable complex can be formed when halogens are
embedded at the center of the cluster.
Table 2.1: C-Cl bond distances (Å) for different positions of Cl2
C-Cl
Armchair edge
1.8137
18
Zigzag edge
1.8258
Center
4.5093
Figure 2.1: Optimized geometries for Cl2 on different sites of the cluster (a) armchair edge;
(b)zigzag edge; (c) center
Moreover, a single Hg atom and a Cl atom have been optimized at different sites on the
surface and the optimized geometries are shown in Figure 2.2 while the bond distances are
given in Table 2.2. The same trend has been observed, i.e. that no stable complex can be
formed at the center site and therefore, edge sites were chosen in the further calculations.
Also, comparison of mercury binding energies for zigzag and armchair edge sites shows that
the armchair edge is more favorable for mercury binding with a binding energy of 7.72
kcal/mol while zigzag edge has a binding energy of 3.5 kcal/mol.
Figure 2.2: Optimized geometries for Hg and Cl on different sites of the cluster (a) armchair
edge; (b)zigzag edge; (c) center
19
Table 2.2: C-Cl and C-Hg bond distances (Å) for different positions on the surface
C-Cl
C-Hg
Armchair edge
1.8461
2.4613
Zigzag edge
1.8345
2.4788
Center
5.7448
4.0836
2.2.3 Effect of Halogens on Hg Adsorption Capacity
Previous experimental studies have shown that chemically embedded activated carbon has a
higher elemental mercury removal capacity than thermally activated carbon. In particular,
halogen-embedded activated carbon has been found to be an effective sorbent for elemental
mercury capture [35-38,84]. To understand the interactions between elemental mercury and
halogen-embedded activated carbon, density functional theory calculations have been
performed using different halogens such as fluorine, chlorine, bromine and iodine. The
activated carbon cluster having mercury and halogen at the armchair edge has been modeled
at the B3LYP/LANL2DZ level of theory. Cluster models with and without halogens are
shown in Figure 2.3. Binding energies of elemental mercury on the activated carbon clusters
were calculated using equation (2.3),
Binding Energy = E(AC-Hg) – [E(Hg) + E(AC)]
(2.3)
Figure 2.3: Cluster models of mercury adsorbed on activated carbon (AC) and halogenembedded activated carbon X: F, Cl, Br, I
20
Comparing the binding energies of elemental mercury on the activated carbon surface with
and without a halogen indicates that the use of a halogen promotes mercury binding.
Examination of the binding energies reported in Table 2.3 reveals that fluorine yields the
highest binding energy, i.e. -9.59 kcal/mol, compared to the other halogens considered.
Table 2.3: Mercury binding energies (kcal/mol) and C-X bond distances associated with the
clusters from Figure 2.3
AC
AC-F
AC-Cl
AC-Br
AC-I
Binding energies
(kcal/mol)
-4.3235
-9.5885
-7.7207
-6.6431
-5.3697
C-X Bond
distances (Ǻ)
1.4178
1.8461
1.9809
2.1681
2.2.4 Effect of Oxygen Functional Groups on Hg Adsorption Capacity
Experimental studies conducted by Lee et al. [55] indicate that activated carbon with large
oxygen functional groups were superior for elemental mercury adsorption. To simulate an
activated carbon surface with increased accuracy, oxygen functional groups such as carbonyl,
lactone, carboxyl and phenol groups were also considered on the cluster. Each functional
group has been investigated separately to note the effect of different functional groups on
elemental mercury binding. Carbon-mercury bond distances for the optimized clusters are
given in Table 2.4, with the optimized structures presented in Figure 2.4.
Table 2.4: C-Hg bond distances (Å) for the clusters associated with the clusters from Figure
2.4.
C-Hg
Lactone Carbonyl
2.4462
2.2586
21
Phenol
2.4497
Carboxyl
2.5078
Figure 2.4: Activated carbon clusters with oxygen functional groups: lactone, carbonyl,
phenol, and carboxyl
Lactone and carbonyl groups have been found to be active sites for mercury binding,
yielding binding energies of -10.29 and -9.16 kcal/mol, respectively. The presence of phenol
and carboxyl groups has yielded relatively lower binding energies, -6.72 and -1.22 kcal/mol,
respectively. More specifically, the presence of lactone and carbonyl functional groups
promotes the chemisorption of elemental mercury while phenol and carboxyl functional
groups promote a physisorption mechanism of mercury adsorption. These results agree with
the experimental results of Li et al. [56] where they found both lactone and carbonyl groups
to be the likely sites for mercury adsorption, with the activated carbon surfaces having a
lower phenol to carbonyl ratio yielding a greater elemental mercury adsorption capacity.
22
Since it is known that halogen-embedded activated carbon has higher elemental mercury
adsorption capacities than traditional activated carbon, halogens combined with the oxygen
functional groups have been considered. Halogen-embedded clusters with different oxygen
functional groups have been investigated and are shown in Figure 2.5. For these clusters the
bond distances of carbon-halogen and carbon-mercury are given in Table 2.5. The binding
energies reported in Table 2.6 show that adding a halogen to the cluster increases the
elemental mercury adsorption capacity. It is interesting to note that the mercury binding
energy increases with decreasing halogen distance to the activated carbon cluster surface as it
is seen from Table 2.3.
Table 2.5: Bond distances (Å) of the clusters represented in Figure 2.4
Functional
groups
Lactone
Carbonyl
Phenol
Carboxyl
X=F
C-Hg
C-F
2.4096 1.4116
2.2608 1.4096
2.3954 1.4165
2.4428 1.4220
X=Cl
C-Hg
C-Cl
2.4239 1.8395
2.2671 1.8336
2.4150 1.8468
2.4616 1.8564
X=Br
C-Hg
C-Br
2.4307 1.9891
2.2678 1.9809
2.4254 1.9959
2.4690 2.0069
X=I
C-Hg
2.4382
2.2730
2.4314
2.4747
C-I
2.1640
2.1525
2.1718
2.1824
Table 2.6: Binding energies of mercury on halogen-embedded activated carbon with different
oxygen functional groups: lactone, carbonyl, phenol, and carboxyl
Functional
groups
Lactone
Carbonyl
Phenol
Carboxyl
AC
-10.2851
-8.8298
-6.7242
-1.2231
Binding Energies (kcal/mol)
AC-F
AC-Cl
AC-Br
-16.7144 -14.6622 -13.4594
-14.5008 -13.0570 -12.1202
-12.6310 -10.5091
-9.2009
-7.6798
-4.0432
-2.4707
23
AC-I
-11.8763
-10.9199
-7.7716
-0.6746
Figure 2.5: Halogen-embedded activated carbon clusters with oxygen functional groups:
lactone, carbonyl, phenol, and carboxyl X = F, Cl, Br, I
Using different halogens with surface functional groups, the same trend has been observed
where fluorine yields the highest binding energy of elemental mercury. The best binding
performance has been obtained with the fluorine atom and lactone functional group
combination, which has a mercury binding energy of -16.71 kcal/mol, while the second best
is a carbonyl functional group with fluorine atom having a binding energy of -14.5 kcal/mol.
Although the phenol functional group does not yield a promising adsorption capacity, when
fluorine or chlorine is used, it may exist as an active site for elemental mercury adsorption.
24
2.2.5 Conclusions
Note that these calculations do not represent real flue gas conditions and the calculated
mercury binding energies have yet to be compared directly to experiment since such specific
data is currently lacking in the literature. Effects of other flue gas constituents have not been
considered and the simulations have been performed at room temperature. Density functional
theory calculations have been carried out to provide a possible mechanism associated with
mercury binding on various types of activated carbon. These results can provide a direction
for the further experiments in terms of through the recognition of binding trends and how the
binding capacity changes by modifying the surface. In light of these results, activated carbon
with the best combination of halogen and oxygen surface functional groups yielding the
highest mercury removal capacity can be used in the experiments.
Through comparing the binding energies of elemental mercury on simulated activated carbon
surfaces, it can be concluded that increasing the amount of lactone and carbonyl groups and
decreasing carboxyl group can increase the binding capacity of elemental mercury. In
addition, embedding halogen, especially fluorine, into the activated carbon matrix, can
possibly promote elemental mercury binding.
2.3 Understanding the Binding Mechanism of Mercury on
Activated Carbon
2.3.1 Introduction
Experimental studies have been previously carried out to understand the mechanism of
mercury binding on activated carbon surfaces [85-88] and it has been made clear that the
reaction mechanisms involved in mercury capture are very complex [85,88]. Hutson et al.
[88] reported the factors that play a role in determining the rate and mechanism of mercury
binding, to be gas-phase speciation of mercury, presence of other potentially competing flue
25
gas components, flue-gas temperature, and the presence and type of active binding sites on
the sorbent. They have used X-ray Absorption Spectroscopy (XAS) and X-ray Photoelectron
Spectroscopy (XPS) to characterize mercury binding on various types of activated carbon.
Mercury was found to be bound on carbon at the chlorinated or brominated sites. No
elemental mercury was observed on the activated carbon surface. Considering the fact that
there is no homogeneous mercury oxidation occurring in their system, there must be
heterogeneous oxidation with subsequent binding on the surface. In another X-ray
Absorption Fine Structure (XAFS) study, Huggins and co-workers [86] also observed that
there is little or no elemental mercury present in the sorbent materials and concluded that
physisorption is not involved in the adsorption of mercury at the low temperature conditions
of their experiments. From these results, they infer that an oxidation process, either in the gas
phase or simultaneously as the mercury atom interacts with the sorbent, is involved in the
capture of elemental mercury. In the case of chemically-treated sorbents, mercury sorption is
predicted to occur entirely by chemisorption. Furthermore, XANES (X-ray Absorption NearEdge Structure) spectra indicates the formation of Hg-I, Hg-Cl, Hg-S and Hg-O. According
to Laumb et al. [87], Cl and S are two of the most important elements when dealing with
mercury capture on activated carbon.
Huggins et al. [85] have studied the sorption of Hg and HgCl2 by three different activated
carbon samples using XAFS spectroscopy and found that a different mechanism is
responsible for the mercury sorption by each different type of activated carbon. Activated
carbons used in their experiments were a lignite-derived activated carbon (LAC), an iodineactivated carbon (IAC), and a sulfur-activated carbon (SAC). When the carbons were
exposed to the flue gas containing elemental mercury, Hg-S or Hg-Cl bonding was observed
in SAC and LAC carbons and Hg-I bonding in the IAC carbon. Exposing LAC to the flue gas
containing HgCl2 revealed that mercury chloride is the most likely sorbed mercury species.
In the case of IAC, Hg-I was observed on the carbon. According to the authors, HgCl2 must
have decomposed to an Hg species in the gas phase or reacted at the active site, releasing Cl,
to form the Hg-I complex. These results indicate that the speciation of the sorbed mercury is
controlled by the site-activating agent on the carbon surface.
26
Many experimental studies have been performed to investigate mercury adsorption on
activated carbon. Nonetheless, the mechanism by which mercury adsorbs on activated carbon
is not exactly known and its understanding is crucial to the design and fabrication of effective
capture technologies for mercury. The objective of the current study is to apply theoreticalbased cluster modeling to examine the possible binding mechanism of mercury on activated
carbon.
Binding mechanisms of Hg, HgCl and HgCl2 on simulated activated carbon surfaces and
the effects of adsorbed Cl were investigated by following a thermodynamic approach.
Energies of different possible surface complexes and possible products are compared and
dominant pathways are determined relatively.
Each structure is optimized through the investigation of stable energies at different
multiplicities and the ground state is determined by the lowest energy complex among the
different electronic states.
2.3.2 Modeling Activated Carbon Surface
The activated carbon surface is modeled by a single layer of graphite, i.e., graphene, in which
the edge atoms on the upper side are unsaturated in order to simulate the active sites. This
model has been used in several studies of different applications to simulate carbonaceous
surfaces [64-69,76]. Chen and Yang [75] have compared six graphite models with increasing
sizes using the HF method and found the model C25H9 to be the most suitable model to
simulate the graphite structure, yielding structural parameters close to the experimental data.
On the other hand, Montoya et al. [64] decreased the molecular system and used C18H8 as
their model, employing the B3LYP method. The conclusion was that even at this size, the
structural parameters for the carbon-nitrogen models were in agreement with the
experimental data. Both Chen et al. [75] and Montoya et al. [65] have shown that the
reactivity of the carbon model does not depend strongly on the molecular size. The reactivity
of the active sites, which are the unsaturated carbon atoms at the edge of the graphene layers,
depends mainly on its local shape rather than on the size of the graphene cluster [65].
27
Also, analysis of a single graphene layer is a convenient and reasonable starting point when
studying the reactivity of carbon surfaces [69]. In an early ab initio study, comparison of
two- and three-dimensional models for the graphite lattice predicted a weak interaction
between atoms in adjacent stacking planes, leading to the conclusion that treating graphite as
a two dimensional solid is a reasonable approximation [89]. Yang et al. [71] have conducted
an ab initio molecular orbital study on the adsorption of atomic hydrogen on graphite and
concluded that the strength of chemisorption is higher on the edge planes than the basal
planes, following the order: zigzag edge > armchair edge > basal-plane. Another study on the
adsorption of oxygen on boron-substituted graphite has yielded that zigzag sites are more
reactive than armchair sites, due to the existence of unpaired electrons on zigzag edges, while
no such electrons are found on armchair edges [90]. Armchair sites are of the carbyne type,
while zigzag sites are of the carbene type and they possess two nonbonding electrons [70].
Radovic et al. [70] have studied the chemical nature of the graphene edges and stated that
“complete saturation with H or other heteroatoms is unrealistic and not all graphene edge
sites are saturated with H.” There has also been experimental evidence on the existence of
partially-stabilized radical sites at graphene edges [91]. Although O2 chemisorption is known
to occur readily at room temperature, it has been shown that oxygen-free carbon edge sites
can still exist after exposure to air [70,91]. In addition to these, the existence of the carbene
sites has been supported by another study, where it was proposed that zigzag Lewis basic
carbene reacts with oxidized Hg species [50].
Based on the previous studies, it is a reasonable approximation to use a graphene model
where the zigzag edges are unsaturated to simulate the active sites. The optimized geometry
of the graphene model (G) is shown in Figure 2.6 with the optimized parameters given in
Table 2.7. Bond distances and angles of the optimized structure are in good agreement with
the experimental values of graphite [92].
28
Figure 2.6: Optimized geometry of graphene (G)
Table 2.7: Optimized parameters of graphene model (Bond lengths in Ǻ and angles in
degrees) av: average
Parameter (av) Model
C-C
1.42
C-H
1.09
120
 C-C-C
119.7
 C-C-H
Exp92
1.42
1.07
120
120.0
Another model includes a chlorine atom placed at the edge site to determine the effect of
chlorine on the binding of mercury and its species. XPS studies conducted to examine
chlorinated-activated carbons showed that chlorine was localized at the edges of graphene
layers [92]. Based on this, the optimization of the chlorine atom at different sites of the
graphene model yielded the structures G-Cl(1) and G-Cl(2) as shown in Figure 2.7. Other
models shown in Figure 2.7, which consist of two Cl atoms on the surface, were also
employed.
The binding of Hg, HgCl and HgCl2 at different sites of graphene and graphene-Cl models
described above is studied and a possible binding mechanism is suggested. Binding energies
of mercury species on simulated activated carbon were calculated using Equation (2.3). In
addition, bond populations are calculated by performing a Mulliken population analysis.
Mulliken population is used for charge determination and as a measure of bond strength.
Although absolute values of populations have little physical meaning, their relative values
can be useful. For example, positive and negative values of bond population mean that the
atoms are bonded or antibonded, respectively. A large positive value indicates that the bond
29
is largely covalent, whereas there is no interaction between the two atoms if the bond
population is close to zero [90].
G-Cl(1)
G-ClCl(1)
G-Cl(2)
G-ClCl(2)
G-ClCl(3)
Figure 2.7: Graphene models with chlorine (green atom represents Cl)
Bond populations for the Graphene (G) and Graphene-Cl models are given in Table 2.8.
The populations for only the bonds of interest are reported here.
Table 2.8: Bonding Mulliken population analysis for Graphene, Graphene-Cl and Hg on
Graphene (only bonds of interest are reported)
C(6)-C(5)
C(5)-C(4)
C(4)-C(8)
C(8)-C(9)
C(9)-C(15)
C(15)-C(14)
C(14)-C(20)
C(20)-C(21)
Cl-C(8)
Hg-C(8)
Hg-C(9)
Hg-C(15)
Hg-C(14)
Hg-C(20)
Graphene
G
0.486
0.342
0.393
0.302
0.302
0.393
0.342
0.486
Graphene-Cl
G-Cl (1)
0.516
0.332
0.175
0.038
0.313
0.450
0.339
0.490
0.416
Hg on Graphene
BC
A
0.489
0.497
0.336
0.332
0.458
0.408
0.107
0.308
0.108
0.374
0.458
0.187
0.338
0.208
0.490
0.484
0.251
-0.184
0.251
30
0.252
-0.183
0.258
When Cl is adsorbed on the surface, the C(8)-C(9) bond is elongated. The bond length
increases from 1.401 to 1.415Ǻ and the bond population decreases from 0.302 to 0.038. The
decrease in the bond population shows that a portion of the bonding electrons were
transferred to the adsorbed Cl atom, thus weakening the bond. Similarly, the C(4)-C(8) bond
is also weakened. The bond length increases from 1.388 to 1.401Ǻ and the bond population
decrease from 0.393 to 0.175.
2.3.3 Binding of Hg on Graphene and Graphene-Cl
The interaction of Hg with different sites of graphene was examined. Different locations of
Hg on the graphene model (G) are shown as “a”, “b” and “c” in Figure 2.8. Both “b” and “c”
yielded the same surface complex shown as BC whereas “a” yielded the complex A. The
binding energies of Hg with A and BC are found to be 14.28 kcal/mol and 14.84 kcal/mol,
respectively, indicating that the stabilities of these structures are very similar.
a
Hg
b c
Hg Hg
A
BC
Figure 2.8: Binding of Hg at different sites of graphene (G) (silver atom represents Hg)
The bond populations of Hg on the graphene model are given in Table 2.8. For the structure
BC, the C(8)-C(9) and C(9)-C(15) bonds are weakened by the adsorption of Hg, with their
31
bonding populations decreasing from 0.30 to 0.11. Comparing the bond populations of the
Hg atom with the near C atoms, it becomes clear that Hg is interacting with the two carbon
atoms C(8) and C(15), and there is no significant interaction with C(9). Similarly, for the
structure A, Hg is interacting with the two carbon atoms C(15) and C(20).
Binding of Hg on Graphene-Cl
The G-Cl model is also employed to illustrate the effects of adsorbed chlorine on the surface.
Different locations of Hg are shown in Figure 2.9 with the possible surface intermediates D,
E, F and GH. Bonding populations of these structures are given in Table 2.9. Both g and h
converged to the same minimum energy yielding the intermediate GH. In this case, the
binding energy of Hg is 14.36 kcal/mol, which is similar to the value of Hg on graphene. The
intermediate F is possibly a result of a surface reaction between Hg and Cl yielding HgCl on
the surface.
d
Hg
D
e
Hg
g
f Hg
Hg
h
Hg
E
F
Figure 2.9: Binding of Hg at different sites of G-Cl model
32
GH
Table 2.9: Bonding Mulliken population analysis for Hg on Graphene-Cl and HgCl on
Graphene (only bonds of interest are reported) *nearest carbon
C(6)-C(5)
C(5)-C(4)
C(4)-C(8)
C(8)-C(9)
C(9)-C(15)
C(15)-C(14)
C(14)-C(20)
C(20)-C(21)
Cl-C*
Hg-Cl
Hg-C(5)
Hg-C(15)
Hg-C(8)
Hg-C(20)
Hg on Graphene-Cl
D
E
F
GH
0.392 0.517 0.498 0.525
0.297 0.331 0.334 0.325
0.128 0.175 0.430 0.227
0.111 0.034 0.250 0.023
0.289 0.311 0.164 0.376
0.470 0.451 0.261 0.247
0.334 0.339 0.300 0.217
0.496 0.492 0.503 0.489
0.367 0.403
0.388
0.005 0.006 0.265 0.008
0.154
0.368 0.255
1A
0.392
0.298
0.128
0.111
0.289
0.470
0.334
0.496
0.367
0.006
0.153
1B
0.432
0.062
0.337
0.253
0.284
0.418
0.327
0.498
0.309
0.005
HgCl on Graphene
1C
1D
2AB
2C
0.388 0.418 0.490 0.503
0.197 0.081 0.217 0.300
0.363 0.413 0.247 0.263
0.350 0.374 0.377 0.161
0.298 0.298 0.023 0.249
0.417 0.407 0.227 0.430
0.341 0.340 0.325 0.335
0.494 0.494 0.525 0.498
0.333 0.388
0.259 0.007 0.008 0.265
0.389
0.255
0.163
0.255 0.369
2D
0.515
0.332
0.172
0.034
0.310
0.449
0.340
0.490
0.406
0.006
3C
0.437
0.380
0.338
0.209
0.209
0.338
0.380
0.437
0.252
0.223
0.223
0.255
From these four surface intermediates possible final structures can be suggested as a result
of desorption. One possibility is that Hg can be desorbed and Cl remains on the surface or
vice versa. Another possibility is that HgCl desorbs from intermediate F. The possible
pathways including reactants, intermediates and products are shown in the energy diagram
given in Figure 2.10. All energy values are given relative to the reactants.
From examining the energy diagram, it seems that the stability of the intermediates are in
the order of GH > D > F > E. The most likely structure is complex GH, since its path is more
exothermic than that of the others. It appears from the energy diagram that complex E is not
as likely to form. Although the formation of F is not as exothermic as D and GH, there is
likelihood that F can be formed as well. It is clear from Figure 2.9 that desorption from these
surface complexes is endothermic and not likely to occur without adding energy to the
system. The desorption pathways of Cl and HgCl from the GH complex are highly
endothermic, but there is a possibility that it may go back to the reactants with the desorption
of Hg. Pathways of Cl desorption from D are shown in the energy diagram; however, it is
more probable that these intermediates will go back to the reactants or remain as stabilized
33
intermediates. Careful examination of complex F indicates that once HgCl is on the surface it
does not desorb easily. This can also be concluded from the population analysis. The bond
population of Hg-C in F is higher compared to the Hg-C population in the other structures,
indicating that HgCl is strongly bound to the surface. Although the binding energy for the
structure F is lower compared to GH, the interaction between Hg and C is stronger in F. A
similar phenomena has been observed by Nilsson and Pettersson [93], where they have
concluded that “a small adsorption energy cannot by itself be used to conclude a weak
interaction.” They have shown that there can still be surprisingly large and important
chemical bonding interactions with the surface that are beyond a physical adsorption picture.
70
A,BC + Cl(g)
60
G + HgCl(g)
Relative Energy (kcal/mol)
50
40
30
20
10
0
G-Cl + Hg(g)
E
G-Cl + Hg(g)
F
D
-10
GH
-20
Reaction Coordinate
Figure 2.10: Energy diagram for different pathways of Hg on G-Cl
34
2.3.4 Binding of HgCl on Graphene and Graphene-Cl
In the same manner, the interaction of HgCl with different sites of graphene was examined
allowing HgCl to approach graphene from different directions. Unique locations and
orientations of HgCl on the graphene model (G) are shown in Figure 2.11 with the possible
surface intermediates 1A, 1B, 1C, 1D, 2AB, 2C, 2D and 3C. Depending on the orientation of
HgCl, it may or may not be adsorbed dissociatively.
(1d)
(1c)
(1b)
(1a)
1A
3C
Hg
Hg
Cl
Cl
Cl
Cl
Hg
Hg
Cl
Hg
Hg Cl
Hg (2b)
Cl
Cl
Hg
(2d)
(2c)
Cl
(2a)
(3c)
Hg
1B
1C
2AB
2C
Figure 2.11: Binding of HgCl at different sites of G
35
1D
2D
These surface intermediates and possible final structures are shown in the energy diagram
of Figure 2.12, with the energies relative to the reactants. Bonding populations of these
structures are given in Table 2.9.
Similar surface complexes are obtained to those with Hg on G-Cl, but with higher binding
energies. For example, the complex GH with a binding energy of 14.36 kcal/mol is optimized
with Hg on the G-Cl surface. The same complex is also obtained through the optimization of
HgCl on the G surface with two different orientations, i.e., 2a and 2b, yielding the complex
2AB with a binding energy of 69.70 kcal/mol.
A,BC + Cl(g)
10
Relative Energy (kcal/mol)
0
G + HgCl(g)
G + HgCl(g)
-10
-20
-30
-40
3C
-50
-60
-70
2D
2C
G-Cl(1,2) + Hg(g)
1B
2AB
Reaction Coordinate
Figure 2.12: Energy diagram for different pathways of HgCl on G
The stability of the surface complexes are in the order of 2AB>1B>2C>2D>3C, which
implies that HgCl is likely to adsorb dissociatively. However, it is clear from the energy
36
diagram that Hg can desorb from the surface. On the other hand, desorption of HgCl is highly
endothermic, which shows that once it is adsorbed it remains on the surface. As was
explained in the previous section, the bonding population analysis indicates that HgCl is
strongly bound to the surface.
Binding of HgCl on Graphene-Cl
The interaction between HgCl and the graphene-Cl model was also investigated. Having
HgCl approaching the G-Cl surface with different orientations, shown in Figure 2.13, yielded
the surface intermediates, 1A2C‟, 1C‟, 2A‟, 1B2B‟, 2D‟.
Hg
(1c)
(1b)
(1a)
Cl
Cl
Cl
Hg
Cl
Hg
Hg
Hg Cl
Cl Hg
(2d)
(2c)
Hg (2b)
Cl (2a)
Cl(2)
Cl(2)
Cl(2)
Cl(1)
Cl(1)
Cl(2)
Cl(1)
Cl(1)
1A2C‟
Cl(1)
1C‟
2A‟
1B2B‟
Cl(2)
2D‟
Figure 2.13: Binding of HgCl at different sites of G-Cl
Two different orientations of HgCl, i.e., 1a and 2c, yielded the same surface complex,
1A2C‟, which is the most stable structure, with a binding energy of 55.00 kcal/mol. Similar
to HgCl on the graphene model, when the G-Cl model is used HgCl may or may not adsorb
dissociatively. A similar trend to the adsorption on graphene is observed, such that Hg can be
desorbed in the case of dissociative adsorption, while HgCl remains on the surface. Although
37
2A‟ has similar exothermicity to 1A2C‟ and 1B2B‟, it appears from the bond populations of
Hg-C, provided in Table 2.10, that HgCl in 1A2C‟ and 1B2B‟ is more strongly bound on the
surface than Hg in 2A‟.
Table 2.10: Bonding Mulliken population analysis for HgCl on Graphene-Cl and HgCl2 on
Graphene (only bonds of interest are reported) *nearest carbon
C(6)-C(5)
C(5)-C(4)
C(4)-C(8)
C(8)-C(9)
C(9)-C(15)
C(15)-C(14)
C(14)-C(20)
C(20)-C(21)
Cl(1)-C*
Cl(2)-C*
Hg-Cl(2)
Hg-Cl(1)
Hg-C(15)
Hg-C(8)
Hg-C(20)
HgCl on Graphene-Cl
1A2C'
1C'
2A' 1B2B'
0.531
0.481 0.525 0.520
0.328
0.348 0.330 0.325
0.250
0.402 0.219 0.195
-0.042 0.310 0.263 0.000
0.172
0.317 0.298 0.356
0.251
0.390 0.367 0.430
0.293
0.340 0.075 0.186
0.496
0.488 0.426 0.385
0.373 -0.002 0.379 0.420
0.315
0.266
0.248 0.002 0.261
0.018
0.237 0.001 0.004
0.371
0.148
2D'
0.526
0.333
0.186
0.032
0.035
0.185
0.333
0.527
0.430
0.417
0.006
0.001
1A''
0.425
0.076
0.365
0.299
0.026
0.216
0.330
0.522
0.314
0.380
0.001
0.002
0.149
HgCl2 on Graphene
1B''
2A''
2B''
0.365 0.428 0.480
0.089 0.086 0.348
0.344 0.445 0.399
0.294 0.188 0.313
0.218 0.186 0.316
0.334 0.445 0.388
0.379 0.085 0.340
0.436 0.428 0.487
0.348 0.324 0.0001
0.324
0.254 0.010 0.250
0.007 0.010 0.240
0.218 0.252
0.213 0.252
3B4B''
0.524
0.356
0.446
0.309
0.071
0.200
0.314
0.516
0.357
0.045
-0.005
0.390
Additionally, HgCl can react with a Cl atom on the surface to form HgCl2. From the energy
diagram pictured in Figure 2.14, the latter pathway is not very likely, since it is endothermic.
Even if HgCl2 is formed on the surface it is not stable, and can easily desorb or return to the
reactants. From the bond populations in Table 2.10, it appears that there is no interaction
between the HgCl2 molecule and the surface, since the population of Cl-C is close to zero.
38
30
1C, 2C + Cl(g)
20
1B + Cl(g)
1C’
G+ HgCl2(g)
Relative Energy (kcal/mol)
2AB + Cl(g)
10
0
G-Cl + HgCl(g)
G-Cl(1) + HgCl(g)
-10
-20
-30
-40
2D’
-50
1A2C’, 1B2B’
2A’
G-ClCl(1) + Hg(g)
G-ClCl(2) + Hg(g)
Reaction Coordinate
Figure 2.14: Energy diagram for different pathways of HgCl on G-Cl
2.3.5 Binding of HgCl2 on Graphene
The optimization of HgCl2 with different orientations on the graphene model yielded the
surface intermediates, 1A”, 1B”, 2A”, 2B” and 3B4B” as shown in Figure 2.15. Similar
surface complexes are obtained to those with HgCl on G-Cl, but with higher binding
energies.
39
Cl(2)
Cl(1)
Cl(2)
Cl(2)
Cl(2)
Cl(1)
Cl(1)
Cl(2)
Cl(1)
Cl(1)
Figure 2.15: Binding of HgCl2 at different sites of G
Close examination of the energy diagram provided in Figure 2.16, indicates that complexes
2A” and 1A” are the most likely structures to form. However, it is possible that Hg can
desorb. Especially in the case of 1A‟‟, the interaction of Hg and C is weak and Hg has no
significant interaction with Cl atoms, based on the bond populations given in Table 2.10. In
addition to this, it is clear from the energy diagram that desorption of Hg from 1A‟‟ is
exothermic and is likely to occur.
Another possibility is that HgCl2 can form the surface intermediate 2B” with a very small
binding energy of 0.25 kcal/mol and almost zero bond population of Cl-C, implying that
HgCl2 is not stable on the surface and this surface intermediate can return to the reactants
easily with the desorption of HgCl2. Rather, it is likely that HgCl2 dissociates and adsorbs as
HgCl as in 1B”. Experiments conducted at EERC [85] have revealed that HgCl2 decomposes
at the active sites of carbon. XAFS experiments have showed that, under gas-phase HgCl2,
the most likely sorbed mercury species is HgCl, which agrees with the predictions of the
current simulations.
40
10
0
2C + Cl(g)
G + HgCl2(g)
1B + Cl(g)
2B”
G+ HgCl2(g)
Relative Energy (kcal/mol)
-10
-20
G-Cl(1,2) + HgCl(g)
3B4B”
-30
-40
-50
-60
-70
1B”
1A”
G-ClCl(3) + Hg(g)
-80
-90
2A”
Reaction Coordinate
Figure 2.16: Energy diagram for different pathways of HgCl2 on G
2.3.6 Conclusions
A thermodynamic approach is followed to examine the binding mechanism of mercury and
oxidized mercury species such as HgCl and HgCl2 on a simulated carbon surface with and
without Cl. Energies of different possible surface complexes and possible products are
compared and dominant pathways are determined relatively. It is important to note that
transition states along these pathways are not determined and the current investigation is
solely of a thermodynamic nature.
41
In all of the cases, chlorine is bound strongly on the surface and it does not desorb. Both
HgCl and HgCl2 can be adsorbed dissociatively or non-dissociatively. In the case of
dissociative adsorption, Hg can desorb while HgCl remains on the surface. The compound,
HgCl2 was not found to be stable on the surface. Even if it is formed on the surface, it can
easily desorb or return to the reactant species. The most probable mercury species on the
surface was found to be HgCl, which has also been confirmed by experiments [85].
These observations serve to highlight the complexity of the binding mechanism of mercury
species on activated carbon surfaces. Not only mercury-chlorine species are present in the
flue gas but also mercury-bromine species exist and play a significant role in mercury capture
by activated carbon. Further investigations should be carried out to examine the binding of
HgBr and HgBr2 on the simulated carbon surface combining all dominant pathways to
determine a complete binding mechanism of mercury species on simulated activated carbon
surfaces. Understanding the mechanism by which mercury adsorbs on activated carbon is
useful to the design and fabrication of effective control technologies for mercury.
42
Chapter 3
Investigation of Homogeneous Mercury
Oxidation
3.1 Introduction
Homogeneous oxidation of mercury in the flue gas of coal combustion utility boilers has
been studied for many years to understand the speciation of mercury. In spite of a vast
amount of experimental studies, supported by modeling efforts, there are still many questions
to be answered and the speciation of mercury is not fully understood yet. Not only
homogeneous oxidation, but also heterogeneous oxidation of mercury is taking place, e.g., on
the surfaces of the fly ash, unburned carbon and activated carbon or on the SCR catalyst. As
one can imagine the heterogeneous oxidation of mercury is much more complicated and its
understanding requires a thorough investigation of the chemistry and mechanisms associated
with both homogeneous and heterogeneous oxidation pathways. To elucidate the
homogeneous oxidation of mercury, experimental studies, which are representative of the
real combustion environment, and development of a detailed kinetic model, that predicts the
behavior of mercury, are crucial. Having a thorough understanding of the gas-phase
interactions of mercury can aid in the development of a heterogeneous model, which in total,
43
will be part of a global model that can be employed for improving existing mercury control
technologies. The purpose of this study is to investigate the gas-phase oxidation of mercury
via chlorine in an experimental system simulating the flue gas of a coal-fired power plant and
improve the existing kinetic models to be able to predict the experimental results by the
model.
As mentioned above, there has been great experimental-based effort in the past to study
homogeneous mercury oxidation and a summary of those studies are provided in Table 3.1.
When reviewing these studies, one important thing to note is how the flue gas is simulated,
i.e., whether a flame is employed or not. Having a flame is crucial in order to simulate the
radical-rich environment of combustion, whereas simulating the flue gas with mixing bottled
gases without having combustion lacks the existence of the radical pool, which greatly
affects the speciation of mercury.
One of the first studies in this area was conducted by Hall et al. [94], where they simulated
the flue gas with a propane-fired burner in the presence of HCl, Cl2, SO2 and NO2.
Additionally, isolated reactions of mercury with O2, HCl, Cl2, NO, NO2, NH3, SO2 and H2S
were investigated in the temperature range of 20-900 ˚C at an inlet Hg concentration of 100
μg/m3. Based on their findings, elemental mercury is readily oxidized by Cl2 and HCl both at
room and at elevated temperatures, but not by NH3, N2O, SO2, or H2S. The rate of the
reaction between Hg and HCl has been found to be increasing with increasing temperatures.
It has been observed that more than 90% of mercury is oxidized in less than 1s at 900 ˚C. The
reaction between Hg and Cl2 has been investigated at different Cl2 concentrations and 70% of
Hg has been found to be oxidized, most likely in the form of Hg(I) and Hg(II) chlorides.
Mercury has been found to react with Cl2 even at 20 ˚C; however, experimental results
indicate that heterogeneous reactions are important, especially at low temperatures. In
agreement with results obtained by Medhekar et al. [95], it has been suggested that this could
be due to the formation of a product on the surface of the reaction cell. A slow reaction
between Hg and NO2 has also been noted, where 11% of Hg is oxidized at 340 ˚C with an
initial NO2 concentration of 1000 μL/L. No further oxidation was observed at temperatures
44
Table 3.1: Summary of previous experimental studies (*HQ: High quench rate, **LQ: Low quench rate)
T (˚C)
Mercury oxidation (%)
Residen
ce time
(s)
Chlorine
concentration
(ppm)
Hg
concentration
(μg/m3)
Flue gas
composition
Flame?
24,96,97
860,
922,
1071˚C
0-75%
1.4s
53-638 ppm HCl
53, 137 μg/m3
N2, O2, CO2,
H2O, HCl
Natural gas-fired
burner
Widmer et
al. 98,99
880420˚C
20-80% with 300ppm HCl
40-98% with 3000ppm HCl
1s
300-3000 ppm HCl
3700 μg/m3
N2, O2, CO2,
H2O, HCl
Simulated flue
gas (MWC)
Fry et al.
103,104
1100300˚C
35-95% with 100-600ppm Cl for HQ*,
9.6-87.2% with LQ**
6.55s
5.74s
Cl2: 0-600 ppm
25 μg/m3
N2, O2, CO2,
H2O, Cl2
Natural gas-fired
burner
Fry et
al.106
1100300˚C
35-95% with 100-600ppm Cl for HQ*,
9.6-87.2% with LQ**
6.55s
5.74s
Cl2: 0-600 ppm
25 μg/m3
N2, O2, CO2,
H2O, Cl2,
NO, SO2
Natural gas-fired
burner
Hall et al.94
900 ˚C
62% with HCl 70% with Cl2
1.5s
HCl: 11, 150 ppm
Cl2: 11-150 ppm
140 μg/m3
N2, O2, CO2,
HCl, Cl2,
SO2
Propane-fired
burner
MamaniPaco &
Helble 21
1080210˚C
10% with 50ppm Cl2
92% with 500ppm Cl2
no significant oxidation with HCl
1.4s,
3.6s,
6.2s, 9s
HCl: 100 ppm
Cl2: 50-500 ppm
50 μg/m3
N2, O2, CO2,
H2O, HCl,
Cl2
Methane-fired
flat flame burner
1080210˚C
92%: 500ppm Cl2,
55%: 500ppm Cl2 + 100ppm SO2,
35%: 300ppm HCl (Φ=0.98),
30%: 300ppm HCl + 100ppm
NO(Φ=0.98)
1.4s,
3.6s,
6.2s, 9s
HCl: 100-300 ppm
Cl2: 150-500 ppm
50 μg/m
N2, O2, CO2,
H2O, HCl,
Cl2, NO,
SO2
Methane-fired
flat flame burner
N/A
HCl: 50 ppm
Cl2: 10 ppm
SO2: 1500 ppm
NOx(NO/NO2):
600/30ppm
Hg: 20μg/m3
HgCl2: 20
μg/m3
N2, O2, CO2,
H2O, Cl2,
HCl, SO2,
NO, NO2,
HF, fly ash
Simulated flue
gas
Sliger et al.
Sterling &
Helble et
al. 102
Laudal et
al.101
N/A
0.1-84.8% gas phase
1.3-88.5% with fly ash
45
3
above 500 ˚C. Moreover, no reaction was detected with up to 10% O2 at temperatures of 20700 ˚C, whereas oxidation was observed when activated carbon is added.
Sliger et al. [24] have studied homogeneous mercury oxidation at high temperatures
between 860 and 1071 ˚C where a natural gas-fired burner was employed to simulate the flue
gas. Mercury was injected into the system as a solution of mercury acetate to produce
concentrations of 53 and 137 μg/m3 of Hg in the reactor, along with various concentrations of
HCl from 53 to 638 ppmv. Their experimental data obtained at 922 ˚C showed similar
features to Hall et al.‟s [94] data at 900 ˚C. Higher conversions of elemental to oxidized
mercury were obtained at high temperatures. No oxidation was detected without HCl and
once a threshold value of HCl is passed, higher HCl concentrations did not yield higher
conversions. Within these experiments, up to 75% mercury oxidation was observed, which is
lower than the results presented in Hall‟s [94] work.
In a later study, Sliger et al. [96,97] worked on developing a kinetic model for
homogeneous oxidation of mercury by chlorine species. Based on their experiments, they
found that oxidation increases with increasing HCl concentration, which is consistent with
the other literature experiments [94,98]. They suggested that the direct elementary oxidation
pathway of mercury by HCl will not occur due to the high energy barrier of the Hg + HCl →
HgCl + H reaction, and rather it will occur via an intermediate derived from HCl. Since the
oxidation is temperature-dependent, this intermediate‟s concentration should be promoted by
high temperatures, which is not the case for Cl2, but it could be the case for atomic chlorine;
therefore, the first oxidation step could take place by the reaction of Hg and Cl yielding HgCl
and the subsequent oxidation of HgCl to HgCl2 could occur via several paths including
reactions with Cl, HCl and Cl2. However, the latter reaction suffers from the absence of Cl2
under high temperatures. Therefore a 4-step mercury reaction set was chosen and
incorporated into a global model including a H2/O2/CO/CO2 reaction set from Warnatz and
18 reactions involving Cl, Cl2, HCl, ClO, HOCl from NIST. In their model they have treated
the sampling probe as an extension of their plug-flow reactor (PFR), because of the potential
for continued reaction within the sampling system during the cooling of the gases. Their
temperature profile included a linear variation from 922 to 868 ˚C over 1.4s in the furnace,
46
followed by a quench to room temperature at a rate of 5400 K/s in the probe. Their results
have illustrated that the entire oxidation of mercury is due to the reactions Hg + Cl → HgCl
and HgCl + Cl → HgCl2 and that it is taking place within the quench environment provided
by the sampling probe. They have reached the conclusion that the oxidation occurs within a
window between 700 and 400 ˚C, which is the result of the overlap of a region of
superequilibrium Cl concentration and a region where oxidized mercury is favored by
equilibrium. Also, homogeneous oxidation is governed primarily by the HCl concentration,
quench rate and background gas composition.
Widmer and co-workers [98] have carried out experiments with the simulated flue gas of
municipal waste incinerators, which have higher concentrations of mercury and chlorine
compared to coal combustion flue gases. In these experiments 3700 μg/m3 mercury was
injected into the flue gas with 300 or 3000 ppmv HCl. Mercury was found to be oxidized to
HgCl2 in about 1 second at temperatures around 700 to 800K. An empirical rate equation for
HgCl2 formation that is first order with respect to both Hg and HCl was derived as a global
pathway. Further thermochemical analysis was performed to obtain the elementary reaction
steps involved in this global reaction [99]. They have suggested that the rate-limiting step in
mercury oxidation by chlorine is the attack on the mercury atom by the Cl atom. The rate
constant for this step has been predicted to be about 1016 cm6/mole2∙s in the temperature
range 700-1000K. After this step the HgCl radical can react quickly with even small
concentrations of Cl2. There is also a possibility that the HgCl radical can react with HCl, Cl
or HOCl; however, these reactions appear to be significantly slower in the temperature range
of interest.
Widmer et al. have also developed a mechanism of 8 reactions of mercury with chlorine
species and incorporated it into a global model including chlorine chemistry within a general
combustion chemistry framework. For the mercury-chemistry reactions, the preexponential
factors of all reactions were taken to be near the collision limit, assuming nearly all of the
reactions involve reactions between free radicals or between radicals and molecular species.
Also for two of the reactions, the preexponential factors were taken as those for the
corresponding lead (Pb) reactions.
47
Their modeling results demonstrated that the kinetic mechanism can be used to predict
conversion of mercury within a temperature range of 600 to 1000K in the presence of 3000
ppmv HCl; however, it underpredicts mercury oxidation at higher temperatures where
mercury conversion is thermodynamically-limited. Based on Sliger‟s [97] results, suggesting
that mercury oxidation at these temperatures occurs only in the sampling system, they have
also included a quench zone in their model with the temperature dropping linearly for 0.5s to
500K. A negligible change was observed for temperatures below 1000K, while the mercury
conversion increased from 75 to 86% at 1100K and from 8 to 21% at 1200K, confirming
Sliger‟s hypothesis.
Mamani-Paco and Helble [21] have conducted a bench-scale examination of mercury
oxidation using a methane-fueled flat flame micro diffusion burner to generate 800-1100K
post-combustion gases containing chlorine as HCl or Cl2. Mercury was injected into the gas
stream at the flame exit at a concentration of 50 μg/m3. Samples were taken at four different
locations at temperatures of 793K, 623K, 563K and 483K with the corresponding residence
times of 1.4s, 3.6s, 6.2s and 9s. According to the results of the experiments conducted in the
presence of 100 ppm HCl and 50 μg/m3 mercury, no significant reaction occurred within the
temperature range 750-1150K and at a cooling rate of 400 K/s. Consistent with the literature,
this indicates that high HCl concentrations are required at temperatures above 973K to obtain
measurable mercury oxidation. In the case of experiments with Cl2, nearly complete
conversion could be obtained at high chlorine concentrations. Mercury oxidation was found
to be 92% in the presence of 500 ppm Cl2 and decreased to 10% when the Cl2 concentration
decreased to 50 ppm. A rate constant of 6x1015 cm3/molecule∙s was derived for the global
reaction of Hg and Cl2 for the temperature range of 773-1173K. No reaction was observed at
the temperatures below 773K, suggesting that reported literature of homogeneous oxidation
of mercury with Cl2 at room temperature is possibly influenced by catalytic reactions on
particles or reactor wall surfaces.
In these previous studies discussed, insight into the reaction pathways is gained; however
no information was provided on the effect of other flue gas constituents such as SO2 and NO.
Bench-scale experiments have been carried out by Ghorishi et al.[100] to investigate the
48
effects of SO2 and H2O and temperature on mercury oxidation in a simulated flue gas
mixture. They have found no oxidation by HCl occurred at temperatures below 250 ˚C.
Although oxidation did occur at higher temperatures, with the addition of SO2 an inhibition
of oxidation was observed at 754 ˚C. Laudal et al. [101] have studied the effects of flue gas
constituents on mercury speciation. Their results have made it clear that Cl2 has a significant
impact on the mercury speciation measurement using Ontario Hydro method. They have
illustrated that in the presence of Cl2 all the impinger-based methods measured a statistically
significant amount of Hg+2 even though only Hg0 was added. In addition, SO2 has been found
to have great effect on the speciation of mercury, completely eliminating the effect of Cl2. In
a test with Hg + Cl2, 84.9% of Hg0 is captured in the impinger solution and measured as
oxidized mercury, while this number decreased to 1.9% in the presence of SO2 and HCl.
Also, the addition of fly ash decreased the oxidation to 28.5%. They have also observed an
interaction between NOx (NO-NO2) and fly ash. More than 25% of mercury was oxidized in
the presence of NOx in the flue gas passed through the fly ash, while there was no conversion
to oxidized mercury without fly ash. In addition to these studies, Sterling and Helble [102]
have investigated the effects of SO2 and NO on mercury oxidation in the experimental
system used by Mamani-Paco described above. In the presence of 300 ppm HCl, addition of
100 and 300 ppm NO caused a slight inhibition on mercury oxidation by HCl. In the
presence of 100 ppm HCl, addition of 100 ppm SO2 had a very little effect on oxidation. In
contrast, SO2 had a large inhibition on the oxidation of mercury by Cl2. Moreover, they have
carried out experiments at different flame stoichiometries and found that increasing oxygen
levels contributes to an increase in mercury oxidation.
Fry et al. [103,104] have carried out experiments to evaluate the effects of quench rate and
quartz surface area on mercury oxidation and performed a detailed kinetic modeling analysis
of homogeneous mercury oxidation reactions. In this system elemental mercury and Cl2 are
injected into a natural gas-fired premixed burner to produce a radical pool representative of
real combustion systems and passed through a quenching section following the hot
temperature region in the furnace. Two different temperature profiles were employed
producing quench rates of -210 K/s and -440 K/s. Mercury concentration in the reactor was
49
25 μg/m3, while chlorine concentrations ranged from 100 to 600 ppm (equivalent to HCl
concentrations). Based on kinetic modeling of the post-flame chlorine species, they have
assumed that chlorine molecules are converted to atomic chlorine as they pass through the
flame and then are converted predominantly to HCl.
When looking at the effect of surface area of the quartz reactor, a threefold increase in
surface area resulted in a 19% decrease in mercury oxidation, which can be explained by
chlorine radical termination on those surfaces. They have concluded that quartz surfaces do
not catalyze mercury oxidation reactions, but inhibit them, and that these surface interactions
are negligible.
Two different quench rates were investigated and it was observed that high-quench
temperature profile yielded significantly higher mercury conversion than the low-quench
rate, which can be attributed to longer residence times at low temperatures and possibly
higher concentrations of Cl radicals generated by the higher quench rate as discussed by
Proccacini [105]. In the presence of 300 ppm chlorine, mercury oxidation increased from 34
to 86% when the quench rate was changed from -210 to -440 K/s, implying that mercury was
not in chemical equilibrium with the flue gas and its oxidation was kinetically-controlled.
The fact that the chlorine radical concentration is very sensitive to temperature makes the
oxidation kinetics very dependent on quench rate.
In a different study they have investigated the impact of NO and SO2 on the measurement
of mercury speciation in a wet chemical conditioning system [106]. Laudal et al. [101] have
previously observed a reduction of Hg+2 in a KCl solution by SO2. Similarly in this study
SO2 was shown to eliminate essentially apparent oxidation in the presence of 300 ppm SO2
and 200 ppm Cl when injected into the KCl impingers. The addition of 300 ppm SO2 resulted
in 68% reduction in oxidation, while addition of 500 ppm NO resulted in 44% reduction in
oxidation. The overall effect of SO2 or NO has been found to be reducing Hg+2 in the KCl
solution to Hg0, which will significantly bias the speciated mercury measurements performed
with wet chemical conditioning systems in CEMs (continuous emission monitors).
50
Besides the experimental studies, there have been several studies in the literature that have
focused on developing an elementary kinetic mechanism for homogeneous mercury
oxidation to predict mercury speciation in the coal combustion flue gas. As mentioned
before, Sliger et al. [97] have presented a 4-step mechanism that incorporated a global
reaction with Cl2. Widmer et al. [99] have subsequently proposed an 8-step mechanism
including the reactions of mercury with chlorine species such as Cl, Cl2, HCl and HOCl.
Following these investigations, Edwards et al. [107] have expanded the chlorine chemistry
and Niksa, Helble and co-workers [108] have recalculated several rate constants and
incorporated NOx chemistry. Also, Qiu et al. [109] have further refined the rate constants
and expanded the chlorine chemistry. Hg chemistry used by both Niksa et al. and Qiu et al.
use the framework proposed by Widmer et al. [99] consisting of 8-step elementary reactions.
Fry et al. [103,104] have used the model by Niksa, Helble and co-workers [108,110], which
includes sub-models for Hg chemistry, Cl chemistry, NOx chemistry (including NO-Cl) and
SOx chemistry. The chlorine mechanism used in his model consists of 29 reactions and was
developed by Roesler [111,112]. Chemkin 4 was used to model the mercury oxidation
experiments in a PFR. The experimental data and model predictions were in very good
agreement in terms of predicting the extent of oxidation as well as the effect of quench rate.
The same model was also employed to predict the experimental data of Fry et al. [106] where
they have investigated the effects of NO and SO2 on mercury oxidation. The model results
did not show the effect of NO on mercury oxidation for all NO and chlorine concentrations
investigated. On the other hand, it did predict that SO2 affects the concentrations of certain
free radical species that promote oxidation of elemental mercury by chlorine compounds;
however, the observed reduction in oxidation is much less than that observed in the
experiments.
In addition, Krishankumar and Helble [113] have evaluated the homogeneous mercury
oxidation mechanisms by Niksa and Qiu by modeling three sets of experimental data by
Sliger et al., [97] Sterling et al. [102] and Fry et al. [104] After modeling each experiment
with two different models, their main conclusion was that the Niksa mechanism predicted the
extent of oxidation fairly accurately for one experimental system and less well for others
51
while the Qiu mechanism provided quantitative agreement with the broadest set of
experimental data.
Recent experimental results of Cauch, Fry and co-workers [114] have shown that all of
these experimental studies and the models detailed above can be questioned. Linak et al.
[115] have shown that Cl2 in a simulated flue gas in the absence of SO2 creates a bias in the
Ontario Hydro method and overpredicts the concentrations of oxidized mercury. It has been
shown that as little as 1 ppm Cl2 is enough to create a bias of 10% to 20% in the amount of
oxidized mercury captured in the KCl solution. They were able to eliminate this bias by
adding SO2 to the flue gas or adding sodium thiosulfate (Na2S2O3) to the KCl impinger.
Similarly Ryan et al. [116], in an actual flue gas environment, have demonstrated that 10
ppm Cl2 added to the flue gas without SO2 resulted in 91.5% oxidized mercury, while this
value decreased to 39% when the KCl impingers were spiked with sodium thiosulfate. When
500 ppm of SO2 was added, the results were the same as with adding sodium thiosulfate.
Linak et al. [115] hypothesized that Cl2 gas could dissolve in the KCl impinger solution and
form hypochlorite ion (OCl-), which oxidizes elemental mercury to Hg+2 in the solution.
They have concluded that dissolved SO2 or thiosulfate ion in the solution reduced the
hypochlorite ion and therefore eliminated the measurement bias. In order to further study this
effect, Cauch, Fry and co-workers [114] have injected Cl2 directly into the KCl impinger at a
concentration of less than 10 ppm along with the reactor flue gas. The addition of Cl2 yielded
significant oxidation; however, adding 0.5wt% Na2S2O3 to the KCl impinger completely
removed the oxidation. This gives rise to the conclusion that the decrease in oxidation
observed in Fry et al.‟s [106] previous experiments in the presence of SO2 was in fact an
inhibition of Hg0 oxidation in the KCl solution as SO2 reacted with the Cl2 before the
hypochlorite ion could be formed. Therefore they have stated that the high extents of
oxidation reported by Fry et al. are biased by oxidation in the impinger, suggesting further
homogeneous oxidation experiments need to be performed with the addition of Na2S2O3 to
the KCl impinger to quantify actual levels of oxidation in the gas phase. On the other hand,
the mercury mechanism developed by Niksa, Helble and co-workers was based on the
experimental data of Sliger et al. [97] and Widmer et al. [99] that were obtained at conditions
52
where impinger bias could be important; therefore, they have expressed that the mercury
kinetics in the model of Fry et al. are also questionable.
Given the fact that all of the previous experimental data may be biased by the oxidation in
the impinger solutions, further experimental studies are needed to determine the actual extent
of mercury oxidation, which requires an accurate method for mercury measurement. Also, a
new model is needed, that predicts the experimental data consistently. Having a thorough
understanding of the gas phase interactions of mercury can aid in the development of a
complete and accurate heterogeneous model that ultimately comprises a global model that
can be employed for improving mercury control technologies.
3.2 Kinetic Modeling
The purpose of this study is to improve the existing kinetic models to be able to predict the
behavior of mercury in the flue gas. A new kinetic model to predict the extent of
homogeneous mercury oxidation via chlorine that can validate the experimental results is
presented here. Chemkin 4 [117] was used for the kinetic modeling. The experimental data
from Couch and Fry et al.‟s recent work [114] was used to test the model initially and flue
gas experiments will be conducted in the future for further comparison.
3.2.1 Model Parameters
As mentioned earlier, having a flame is crucial in order to simulate the radical-rich
environment of combustion, since the existence of the radical pool greatly affects [118] the
speciation of mercury. A perfectly stirred reactor (PSR) was used to simulate the flame. A
gas mixture representing natural gas, which consists of a mixture of methane, ethane and
propane, was combusted in the presence of 2% excess O2. For the kinetic and thermodynamic
parameters the GRImech 3.0 [119] mechanism, which has been developed for methane
combustion, was used. The input and output files for the PSR simulation are presented in
Appendix A.
53
The output of the PSR simulation was used as the input for the plug flow reactor (PFR) that
is used to model the experiments of Fry et al. [114], with the input file provided in Appendix
A. In addition to the species that are generated in the PSR, Hg and Cl were also introduced
into the PFR. The temperature profile obtained from the experiments was incorporated along
with the other parameters such as the reactor geometry, flow rate and concentrations of
species. The reactor used was 132 cm long with a diameter of 4.7 cm and operates at a
pressure of 0.85 atm with a flow rate of 408.5 cm3/s. The temperature profile along the PFR
is provided in Appendix A as a function of the distance and was obtained from the
experimental data.
A global mechanism developed by Niksa, Helble and co-workers [108,110] consisting of
sub-models of Hg, NOx, SOx chemistries, including the Cl chemistry by Roesler et al.
[111,112] was employed. The mechanism includes a total of 385 reactions including 110
species. To investigate the Cl speciation, the chlorine mechanism in the original model was
replaced by a mechanism by Procaccini and Bozelli et al. [105]. The Hg chemistry was also
replaced with a new reaction set by Wilcox [120,121]. The reaction rate parameters for all of
the model configurations that were employed are presented in Appendix A.
3.2.2 Chlorine Speciation
Before introducing mercury into the model, chlorine speciation was investigated since the
speciation of mercury depends strongly on the existence of the Cl radicals. Two different
chlorine mechanisms [111,112,105] referred to as “Roesler” and “Bozelli” here were used
with the reaction rate parameters are reported in Appendix A. Chlorine was introduced into
the PFR as Cl atom at the concentrations of 100, 200, 300, 400 and 500 ppmv and Hg was
not included in these initial investigations. For the 100 ppmv case, the concentration profiles
of Cl, HCl and Cl2 along the PFR as a function of the residence time are shown in Figure 3.1
with an expanded view of Cl and Cl2 in Figure 3.2. The temperature profile is also included
in Figure 3.2.
54
HCl - Bozelli
Cl2 - Bozelli
Cl - Roesler
Cl2-Roesler
1.2E-04
3.0E-06
1.0E-04
2.5E-06
8.0E-05
2.0E-06
6.0E-05
1.5E-06
4.0E-05
1.0E-06
2.0E-05
5.0E-07
0.0E+00
0.0E+00
0
1
2
3
4
t (s)
5
6
7
Mole fraction
Cl2
Mole fraction
Cl, HCl
Cl - Bozelli
HCl - Roesler
8
Figure 3.1: Chlorine speciation with Roesler and Bozelli mechanisms using 100 ppmv Cl
1.0E-05
1200
Cl - Bozelli
Cl - Roesler
Cl2-Roesler
Cl2 - Bozelli
Temperature
6.0E-06
1000
800
600
4.0E-06
T (°C)
Mole fractions
Cl, Cl2
8.0E-06
400
2.0E-06
200
0.0E+00
0
0
2
4
t (s)
6
8
Figure 3.2: Chlorine speciation with Roesler and Bozelli mechanisms using 100 ppmv Cl
and temperature profile
55
In the first 0.5 second of the simulation, where the temperature is increasing, the Cl radicals
are converted to HCl, with this concentration remaining fairly uniform at the constant
temperature region in the furnace. The main source of the radical termination is the reaction
of Cl atom with HO2, as shown in Reaction (R1) [105].
HO2 + Cl → HCl + O2
(R1)
As the temperature decreases in the quenching section, the Cl concentration begins to rise
again forming a peak at 586 ˚C. This increase occurs where the concentrations of H, O and
OH toward their maximum values [122]. The Cl atom is formed via the reaction of HCl with
OH, O and H radicals as shown in Reactions (R2)-(R4) [122,111,112,105].
HCl + OH → H2O + Cl
(R2)
HCl + O → OH + Cl
(R3)
HCl + H → H2 + Cl
(R4)
Molecular chlorine Cl2, starts to form at the concentration peak of Cl through a radical
recombination reaction, causing the Cl concentration to decrease again [105, 111].
The experiments of Procaccini and Bozelli et al. [105] have illustrated that the final
concentration of Cl2 and HCl depends strongly on the quench rate of the combustion
products. Therefore the mercury speciation will also depend on this quench rate.
3.2.3 Mercury Speciation
To determine the extent of homogeneous Hg oxidation via chlorine, Hg was introduced into
the PFR at a mole fraction of 2.288x10-9, representing a dry flue gas concentration of 25
μg/m3. The mercury oxidation was investigated as the chlorine concentration was varied from
100 to 500 ppmv. The input file for the Hg oxidation simulation with 100 ppmv Cl is
included in Appendix A. The simulation was carried out at different chlorine concentrations,
with the amount of Hg oxidation at the outlet of the reactor determined for each case.
56
The 8-reaction Hg chemistry included in Niksa‟s model was replaced with a 9-reaction
chemistry set provided in Table 3.2 with the corresponding rate parameters. These rate
parameters have been obtained by Wilcox [120,121] using chemical kinetic parameters
obtained from electronic structure calculations. Two different models were employed using
the chlorine mechanisms by Roesler and Bozelli along with the Wilcox reaction set. The
kinetic parameters are reported in Appendix A for the two configurations named “WilcoxRoesler” and “Wilcox-Bozelli”. The thermodynamic parameters for the species included in
the model are also presented in Appendix A.
Table 3.2: Rate parameters for mercury-chlorine reactions
Forward
Reaction
Level of Theory
Act En
kcal/mol
Preexp (A)
cm3/mol.s
HgCl (+M) → Hg + Cl (+M)
QCISD/RECP60VDZ
16.13
4.25x1013
HgCl + HCl → HgCl2 + H
Hg + HCl → HgCl + H
QCISD/RECP60VDZ
B3LYP/RECP60VDZ
30.27
82.06
4.50x1013
2.62x1012
Hg + Cl2 → HgCl + Cl
Hg + HOCl → HgCl + OH
B3LYP/RECP60VDZ
B3LYP/RECP60VDZ
42.80
36.63
1.34x1012
3.09x1013
HgCl2 (+M) → HgCl + Cl (+M)
B3LYP/ECP60MDF
80.55
2.87x1013
HgCl2 (+M) → Hg + Cl2 (+M)
B3LYP/ECP60MDF
86.98
3.19x1011
HgCl + Cl2 → HgCl2 + Cl
B3LYP/ECP60MDF
0
1.43x109-2.46x1010
HgCl + HOCl → HgCl2 + OH
B3LYP/ECP60MDF
0.485
1.74x109-3.48x1010
Figure 3.3 shows the comparison of the model predictions and the experimental data in
terms of mercury oxidation at different chlorine concentrations using the Wilcox-Roesler
model. As can be seen from the graph, the model predictions are in reasonable agreement
with the bench-scale experiments of Fry et al.
57
Wilcox - Roesler
20
18
Wilcox ab initio
16
Fry experiment
% Oxidation
14
12
10
8
6
4
2
0
0
100
200
300
400
500
600
Chlorine Concentration (ppmv equivalent HCl)
Figure 3.3: Mercury oxidation data – comparison of the Wilcox-Roesler model and
available experimental data [114]
The oxidation data produced by the Wilcox-Bozelli model appears in Figure 3.4. In the
case of the Wilcox-Bozelli model, the predictions yield higher oxidation than the
experiments, which may be attributed to the higher Cl2 concentrations produced by the
Bozelli model at the end of the reactor.
Both the available experimental data and the model predict that homogeneous mercury
oxidation is less than 15%, which implies that not only homogeneous oxidation, but also
heterogeneous oxidation is taking place.
58
Wilcox - Bozelli
20
18
Wilcox ab initio
16
Fry experiment
% Oxidation
14
12
10
8
6
4
2
0
0
100
200
300
400
500
600
Chlorine Concentration (ppmv equivalent HCl)
Figure 3.4: Mercury oxidation data – comparison of the Wilcox-Bozelli model and
available experimental data [114]
Similar analyses will be performed after conducting the simulated flue gas experiments and
the results will be used to validate the model predictions. After studying mercury oxidation
by chlorine, bromine will be investigated as the oxidizing agent and the reactions of mercury
and bromine will be investigated. Similar to those 9 reactions of mercury-chlorine species,
Wilcox and Okano have developed [123] a reaction set for bromine that will be employed in
the model. In total, both chlorine and bromine reaction chemistry will be combined and
incorporated into a global combustion model and used to validate experimental results.
59
3.3 Experimental Setup
An experimental system has been designed and built to simulate coal combustion flue gas to
elucidate the homogeneous mercury oxidation post combustion. This system is similar to the
setup at the Combustion Institute located in the Department of Chemical Engineering at the
University of Utah designed by Dr. Andrew Fry aside from the mercury analyzer used in the
current work. In this system mercury and chlorine are introduced into a laminar premixed
methane-air flame to simulate the flue gas environment. The cooled flue gas is sampled by
the mass spectrometer for flue gas chemical composition analysis, with a special focus on
mercury speciation. A schematic of the system is given in Figure 3.5 and the detailed
explanation follows.
Mercury vapor is generated using a “Cavkit” calibration gas generator (PS Analytical
10.534 Mercury vapor generator), which has a built-in flow controller and is known to
produce accurate concentrations of Hg. It works on the principle of diluting a saturated Hg
vapor at a known temperature. A carrier gas flows over the Hg reservoir at a flow rate of 020 ml/min making the carrier gas saturated with Hg at the set reservoir temperature. The
saturated Hg vapor is then diluted into the concentration range of interest by an additional
carrier gas (0-5 L/min) supplied by a second mass flow controller. The Antoine vapor
pressure relation for mercury is used to calculate the mercury concentration as a function of
temperature. Chlorine is supplied in the form of molecular chlorine, Cl2, in air at a
concentration of 6000 ppmv and is passed through the flame to obtain the radical chlorine
chemistry indicative of that in a real utility boiler, thereby creating an environment that
facilitates mercury oxidation. Methane flow is passed through a solenoid valve connected to
a UV flame sensor mounted atop the burner that opens the valve only when flame is detected.
As a safety measure, the solenoid valve is connected to a burner controller and it will be
closed if the flame extinguishes in the burner so that methane will no longer be fed if there is
no flame sensed by the UV detector. Also, a flashback arrestor is employed as a safety
measure to stop methane flow in case of flashback.
60
UV
Detector
Flashback
arrestor
F
CAVKIT
Mercury vapor
generator
Solenoid
valve
F
Solenoid
valve
Mass flow
controllers
Solenoid
valve
Purge air
FI
CH4
Cl2
in air
Rotameter
Solenoid
valve
F
u
r
n
a
c
e
N2
Solenoid
valve
air
Heat
tape
Temperature
Controllers
DAQ
system
vent
Mass
Spectrometer
Figure 3.5: Schematic of the experimental system
The entire experimental system is placed in a ventilated hood and the chlorine tank is also
kept in a ventilated cabinet since any leak from the system containing mercury and chlorine
could be potentially hazardous. There are gas detectors for Cl2, CO and CH4 both inside and
outside of the hood to monitor possible gas leaks. Each gas cylinder has a normally closed
solenoid valve that is connected to a control panel built to operate the system safely. All of
61
the gas detectors are connected to the control panel, which stops all of the gas flow by
closing the solenoid valves and feeds N2 to purge the system in case of a leak. It also shuts
down all the electronic equipment in the case of an emergency.
The reactor is made of quartz and has a length of 131cm and diameter of 5cm. Quartz was
chosen for the reactor material due to its minimal reactivity with mercury chlorine species
[95]. The quartz reactor is housed in a Thermcraft tube furnace, with heat tape wrapping the
reactor section located outside of the furnace. The furnace temperature is set to 1200 ˚C with
the temperature decreasing down to 350 ˚C in the quenching section of the reactor. There are
four sets of heat tape independently controlled, which allows for variation in the quench rate.
The temperature profile inside the reactor is monitored by a temperature profile probe, which
consists of 20 thermocouples connected to a data acquisition system.
The gas exiting the reactor is sampled by the mass spectrometer after passing through an
orifice of 150 μm. The pressure conditions after the first orifice allow for molecular flow of
the beam, which aids in preventing additional reactions within the sampling line.
62
Chapter 4
Measuring Mercury
One needs to be able to make precise mercury measurements to understand the mercury
speciation and accurately predict the extents of mercury oxidation. As explained above,
currently used measuring methods are problematic and not sufficient in making accurate
predictions. These methods with their shortcomings will be discussed in detail in the
following section.
4.1 Traditional Methods
Commercially available mercury analyzers are able to measure only elemental mercury.
Traditionally “difference” techniques are used, which involves the direct measurement of
elemental mercury. The amount of elemental mercury and the amount of total mercury in the
flue gas stream are determined and the difference between these two yields the amount of
oxidized mercury. These techniques do not allow for distinguishing between the two
different oxidized forms, i.e., Hg+ and Hg+2, which makes it difficult to understand mercury
speciation.
Typically, sampling is performed using a sampling train, where the sample is passed
through a series of aqueous solutions to separate and collect elemental mercury.
63
The
impingers take advantage of the different solubilities of elemental and oxidized mercury.
Oxidized mercury is captured by aqueous solutions, while the elemental mercury is
unaffected and continues through onto the next set of impingers where it is captured by an
oxidizing solution [102].
The Ontario Hydro method (OH) is one of the difference techniques and is the favored
method for measuring mercury species for coal combustion applications. To employ this
method two sample streams are required for mercury speciation. The first stream, which is
representative of total mercury concentrations, is bubbled through an impinger of stannous
chloride (SnCl2) in hydrochloric acid (HCl). In this solution oxidized mercury species are
scrubbed out of the gas and the mercury is reduced to its elemental form. Since elemental
mercury is insoluble in the aqueous solution it returns to the gas phase. All of the mercury
entering the impinger leaves as elemental mercury in concentrations representative of the
total mercury in the flue gas stream. The second stream, which is representative of elemental
mercury concentrations, is passed through a potassium chloride (KCl) solution. In the
impinger, oxidized mercury species are scrubbed out of the gas and Hg2+ is retained in the
solution as a complex with Cl- ions [118]. Elemental mercury passes through the impinger
without having its concentration affected since it is insoluble in water. Mercury in this stream
is now representative of the elemental mercury concentrations in the flue gas. Knowing the
concentrations of elemental mercury and total mercury, the concentration of oxidized
mercury can be determined based on the difference, without distinguishing between different
oxidized forms.
When applying this method, one has to be able to reliably measure the elemental mercury
present. The oxidized mercury must be removed without transforming any oxidized mercury
to elemental or vice versa. Any loss of mercury to surface reactions and side reactions must
be minimized. In the previous section it has been made clear that the mercury measurements
performed with wet chemical conditioning systems are biased, resulting in inaccurate
partitioning between oxidized and elemental mercury species [114].
Given the shortcomings of the difference techniques, it is essential to measure oxidized and
elemental mercury directly and hence separately to have a complete understanding of
64
mercury speciation. In this study a mass spectrometer (MS) is used to directly measure
mercury species in combustion flue gas. A benefit of employing a mass spectrometer is,
unlike traditional impinger methods, the oxidized forms can be isolated and individually
identified because it separates the products based on their mass-to-charge ratio.
4.2 Mass Spectrometer
The mass spectrometer that is used in this work is an electron ionization quadrupole mass
spectrometer (EI-QMS). It consists of the following three main parts: ionizer, mass filter and
detector. A schematic of the system is shown in Figure 4.1.
Figure 4.1: Schematic of the mass spectrometer [Adapted from Ref. 124]
The method of ionization employed in this system is electron ionization (EI). It creates ions
from the gaseous feed through the bombardment of the feed molecules with electrons that are
emitted from a tungsten filament. The molecular beam enters the ionization source at a
ninety-degree angle through a quadrupole deflector to maximize the filtering and elimination
65
of neutrals and photons. This will extend the lifetime of the electron multiplier, which will
be essential when dealing with such reactive mercury species. The energy of the electrons
and the properties of the molecules in the feed determine whether or not ions will be formed
through direct electron-impact ionization, dissociative ionization, or electron attachment.
The ions are then focused and accelerated down a column where they are mass filtered [125].
A quadrupole mass filter with a high mass limit of 500 amu and equipped with the capability
of filtering positive and negative ions is used.
The quadrupole mass filter consists of four parallel electrically isolated electrodes oriented
such that the electric field between them is hyperbolic (i.e., quadrupolar). Ions to be mass
analyzed are focused down the center of the quadrupole with a combination of precise DC
and RF voltages applied to the quadrupole rods. Amplitude of the voltages determines which
mass will have stable trajectories through the quadrupole. Ions having unstable trajectories
are neutralized by striking the quadrupole electrodes and removed [126].
After separated, the particles are measured for their identification. Detectors record the
mass of the ion in relation to its charge. The intensities of various mass-to-charge ratios
(m/z) indicate the concentration of different ions. The mass spectrometer for this research
incorporates a continuous dynode electron multiplier. A particle multiplier, when struck by
an ion, electron or photon at its input, generates a short pulse of charge at its output. Charge
pulses may be treated as counts with the number of output counts per second equal to the
number of input ions per second. Electron multipliers work by increasing the number of
electrons enough so that a voltage signal can be recorded. Electrons come into contact with a
surface, such as a curved surface called a dynode, and the impact releases many electrons,
called secondary electrons, from the surface. The secondary electrons continue until they
impact the next dynode, which in turn releases more secondary electrons. Operating voltages
are such that each stage is more positive than the stage before, allowing for the attraction of
the electrons emitted by one stage to the next (see Figure 4.2) [127]. At the end of the
multiplier, the signal has been increased enough to allow for detection [128].
66
Figure 4.2: Impact of electron with dynode releasing secondary electrons, etc. [Adapted from
Ref. 127]
All stages of the process are held under vacuum to ensure the ions, once created, will not
be destroyed by collisions with other particles before they can be measured. The system
involves three orifices, i.e., a sampling orifice of 0.15 mm, a second aperture of 2 mm, and
the ionizer aperture of 3 mm. The system is pumped using three turbomolecular pumps in
series with two backing mechanical pumps, which allow for a vacuum of 4.5x10-8 Torr to be
achieved.
4.3 Instrument Design
To accurately measure the low concentrations of mercury present in coal combustion flue
gas, the EI-QMS must be sensitive to concentrations in the ppb (parts per billion) range,
which can pose a challenge. The instrument has been modified to increase its sensitivity and
the design has taken several years with a vast amount of trouble shooting. The following
section is going to highlight the key modifications that have been performed.
One of the first challenges was the formation of mercuric oxide (HgO). In the preliminary
calibration experiments, HgO was observed although only elemental Hg was introduced to
67
the system. The HgO peaks are shown in Figure 4.3 along with the isotope pattern available
from the literature [129].
Figure 4.3: Isotope pattern of HgO (pattern from literature on the left, experimental data on
the right) [129]
A heat blanket that was specifically designed from CAD drawings of the instrument to fit
around the vacuum chamber has been used for heating the chamber to prevent HgO
formation on the chamber walls. A photograph of the vacuum chamber with the heat blanket
is shown in Figure 4.4. Heating the chamber to 180 °C prevented the formation of HgO and
its subsequent appearance in the spectra.
Figure 4.4: Photograph of the system with the heat blanket
68
The inlet tube is also heated to 200 °C to prevent the accumulation of mercury in the tube.
However, heating the gas before it enters the chamber leads to a pressure increase in the
chamber. Since the pumps were not able to handle the increased pressure, the experiments
were limited at this time to 5 to 10 minutes depending on the gas temperature. In order to
overcome this challenge, different pump configurations have been tested to determine how
the pressure within the three different stages of the chamber change, as a function of the
temperature and the gas flow rate. Complete pumping data is available in Appendix B with
just a brief summary of the results presented here.
In the original configuration the instrument was equipped with the backing pump, Duo10
from Pfeiffer Vacuum with a pumping speed of 10 m3/hr. Using this pump, several orifices
with different sizes (e.g., 150, 200, 300, 400 and 500 μm) have been tested and the pressure
at three different stages (e.g., P1, P2 and P3) of the chamber have been recorded as a function
of temperature and flow rate. For the continuous operation of the instrument, the pressure at
the second stage P2, should be on the order of 10-4 Torr. In the first set of experiments heat
was not applied and different orifices were tested only. As seen from the pressure data in
Appendix B, using the 500 μm orifice allows for a feed gas with a flow rate of up to 0.9
L/min, whereas the maximum flow with the 300 μm orifice is 0.5 L/min, and at higher flow
rates P2 exceeds 10-3 Torr.
In the following experiments the 500 μm orifice has been used. The flow rate was constant
at 0.15 L/min, and the heat blanket temperature Tb, was 180 °C with an inlet temperature Tin,
ranging from 25 °C to 303 °C. When the inlet temperature was 191 °C, P2 reached 4x10-3
Torr in 5 minutes with an increase in temperature shortening this time further. At 303 °C, P2
reached a pressure of 1.3x10-3 Torr instantaneously. Clearly the pump was not able to handle
the pressure load at elevated temperatures so that a new pump, Duo20, with a higher
pumping speed of 20 m3/hr has been tested. With the Duo20, P2 was in the 10-5 Torr range at
191 °C; however, it increased after 5 minutes at 236 °C ultimately reaching a pressure of
1x10-3 Torr after 7 minutes. At 253 °C, it took 3.5 minutes to reach the same pressure.
69
Switching to the Duo20 pump enhanced the performance just slightly, with the experiments
still limited to several minutes at high temperatures.
The next pump tested was the Penta35 with a pumping speed of 35 m3/hr. This pump was
also not sufficient to handle the load with P2 reaching 1x10-3 Torr at 145 °C in less than 5
minutes. As an alternative solution to testing an additional pump with a higher pumping
speed, two pumps (e.g., Duo10 and Penta35) were connected in parallel as shown in Figure
4.5. During the testing with these pumps, the 150 μm orifice was used. This configuration
performed very well and the pressure was stable at 5x10-5 Torr even after 30 minutes at 415
°C. The remainder of the experiments have been conducted with the two-pump configuration
using the 150 μm orifice.
Figure 4.5: Pump configurations: Original configuration on the left, new configuration on the
right. Grey lines illustrate the vacuum hoses given with their sizes
70
4.3.1 Supersonic System
One of the modifications that have been performed to increase the instrument sensitivity is
the inclusion of a supersonic beam coupled with a new skimmer placed after the first orifice.
The following section reviews the nature and creation of supersonic flow and its relationship
to the EI-QMS‟s sensitivity. As the flow accelerates from a region of relative high pressure,
P0, through an orifice into a region of lower background pressure, Pb, it will reach sonic
speed if the exit pressure ratio (P0/Pb) exceeds a critical value G, defined by:
G  ((  1) / 2) 
( 1)
, such that γ, the heat capacity ratio, is defined as f  2 f , where f is
the number of degrees of freedom within the molecule. If the pressure gradient is great
enough to create supersonic free jet expansion, then the exit pressure of the flow becomes
independent of Pb and equals P0/G, thus exceeding Pb. The flow is considered
underexpanded because it has a pressure higher than the background pressure of Pb;
therefore, the flow expands to meet the necessary boundary conditions imposed by the
background pressure. The core of this supersonic expansion, located in the „zone of silence‟
region, is isentropic and unaware of any external conditions. Flow in the zone of silence is
unaffected by the background gas because flow disturbances cannot propagate upstream
faster than the supersonic speed of the flow [130]. In regard to the EI-QMS design, the
pressure gradient between the inlet and the second stage of the vacuum chamber is defined to
create supersonic expansion. Then, with the skimmer located inside the zone of silence, the
molecular beam is extracted from the radially-confined isentropic flow. In such a setup,
scattering of the molecular beam is avoided and the amount of gas that reaches the ionization
region, and subsequently the ion detector, is maximized, thereby improving the sensitivity of
the instrument.
This modification changed the sample introduction method from an effusive beam to a
supersonic beam by optimizing the distance between the first expansion nozzle and the
skimmer. The shape of the skimmer is optimized as well. In the original configuration, the
first expansion orifice was laser-drilled into a VCR gasket, establishing a super-sonic
expansion into the intermediate chamber. However, pressure in this first expansion chamber
71
was high enough to allow the shock front to collapse upon itself, thus allowing for secondary
collisions and slowing the beam. In the new configuration, the VCR orifice has been
replaced with a 1/8” OD stainless steel tube. This tube has a closed end with an orifice laserdrilled at the end. A schematic of the instrument showing the orifice tube and the skimmer is
given in Figure 4.6. The distance between the tube and skimmer is optimized so that the
center of the cosine distribution is captured while skimming off the shock front of the
expanding gas, thus disallowing it to collapse on the beam. Preceding the supersonic
skimmer is a pressure in the 10-4 Torr range, which maintains free molecular flow,
eliminating the chance of secondary collisions, thus maintaining collimated, supersonic speed
in the beam. The speed is not as important in this application as the collimation is. This
collimated beam, that precisely enters the ionizer, is ionized and the ions are efficiently bent
off-axis through tuning lenses and into the quadrupole. This modification allows for almost a
3-times increase in overall sensitivity of the system. It also produces improved peak
resolution and peak shape with less broadening.
Figure 4.6: Schematic of the supersonic system
72
Supersonic beams tend to concentrate heavy masses in the center of the beam [131-135]
due to pressure diffusion [132-134] in the first three nozzle diameters downstream from the
nozzle and the Mach number focusing [134, 135] downstream from the sudden freeze plane,
where the collision-free zone begins. This is explained by Veenstra et al. [136] in the
following way: “in the first three nozzle diameters, streamlines are curved and large pressure
and temperature gradients exist perpendicular to the streamlines, causing lighter particles to
escape more easily from the beam axis than heavier particles. Once the beam reaches the
collision-free zone, the perpendicular temperature still decreases, and therefore the beam is
more rapidly diluted in the lighter species”. Therefore it is crucial that the skimmer and the
orifice are aligned precisely so that the lighter ions go through the skimmer without escaping.
This alignment is performed using a 670 nm laser beam. The detailed instructions for the
alignment procedure are given in Appendix C.
A perturbing byproduct of the supersonic expansion is the clustering of the gas molecules.
[137] Supersonic expansion of a gas through a small orifice cools the gas adiabatically to
very low temperatures and cluster growth is initiated through three-body collisions. The
supersonic beam technique is used to produce and study clusters of rare gases and small
molecules. Parameters such as nozzle size, shape and backing pressure can be varied to
produce cold clusters and tune cluster size distributions [138].
Supersonic molecular beam systems have been used for studying Hg clusters (Hgn) in the
past [139, 140, 141, 142, 143]. Clusters with the size of up to n=100 have been observed
[141]. Since the detection limit of the instrument is 500 amu, only dimers (n=2) have been
observed in the current study, as shown in Figure 4.7. In fact the creation of Hg clusters is
beyond the scope of this study and is not a desirable phenomenon since it interferes with the
direct measurement of mercury species exiting the reactor. Since the clusters are formed due
to the cooling after the supersonic expansion, heating the orifice directly can eliminate the
cluster formation. Amirav et al. [144] explored the effect of supersonic expansion on cluster
formation and they reported that the cluster formation was negligible when the nozzle was
heated. A heating system has also been employed in this study and the following section
reviews the details of this modification.
73
Figure 4.7: Mass spectrum of mercury dimer detected with the supersonic system
4.3.2 Orifice Heater
A heating system has been designed and fabricated to heat the orifice directly in the vacuum
chamber to prevent the formation of Hg clusters. The stainless steel orifice has also been
replaced with a laser-drilled sapphire orifice for improved thermal conductivity. Sapphire has
a thermal conductivity of 46 W/m∙K at 300 K while stainless steel has a thermal conductivity
of 15.9 W/m∙K [145]. The 150 μm orifice is placed at the tip of a 1/8” OD, 12.1 cm long
stainless steel tube that extends through the front flange of the vacuum chamber as shown in
Figure 4.8. The stainless steel tube is surrounded by a 6 mm OD alumina tube that acts as an
electrical insulator. Alumina is chosen because it has a relatively higher thermal conductivity
for a ceramic material (36 W/m∙K [145]). The heater is made of a 30 cm long 30 AWG
(American Wire Gauge) Nickel/Chromium wire. The resistance of the wire was measured
with a Fluke Multimeter and found to be 7.35 Ω. The wire is wrapped around the alumina
tube with the remaining unwrapped wire beaded with ceramic beads for insulation. The wire
is held around the tube with two aluminum clamps that have been specifically designed for
this purpose. Two K-type thermocouples from Omega are inserted between the alumina and
stainless tubes at both ends, with one directly measuring the temperature of the orifice. A
photograph of the heater with the wire and the thermocouples is shown in Figure 4.8.
74
Figure 4.8: Photo of the orifice heater on the left and the front flange showing the
feedthroughs (FT) on the right
The power to the wire is supplied with a Variable AC (Vari-AC) voltage controller. The
front flange of the vacuum chamber has been redesigned to incorporate the feedthroughs for
both supplying power and the thermocouples. The 8” CF flange includes a weldable 2-pin
power feedthrough that is capable of conducting up to 10 amps and a thermocouple
feedthrough that has three miniature K-type thermocouple connectors on the air-side of the
flange. The flange also includes a Swagelok tube fitting with a tube adapter in the center
through which the orifice tube passes. Below the gas feedthrough is a 25KF half nipple that
is used for the pump connection. All of the components are vacuum-welded on the flange.
The drawing of the flange is given in Appendix D and a photograph is shown in Figure 4.8.
The orifice heater has been tested and calibrated before the front flange was installed on the
vacuum chamber. Different voltages have been applied to the wire and the corresponding
temperature readings from the thermocouples at both ends of the tube are shown in Table 4.1.
75
Table 4.1: Calibration of the orifice heater
Voltage (V)
0
4
6
8
10
14
16
T1 (°C)
20.8
51.4
81.4
115.7
154.4
230.6
261.3
T2 (°C)
18.5
50.1
80.2
115.0
153.9
230.4
260.3
The calibration process was repeated following the flange installation on the vacuum
chamber. As seen from Table 4.2, the results were different under vacuum conditions as
expected, and the temperatures are significantly greater compared to atmospheric conditions
due to the lack of convective heat transfer in the vacuum environment.
Table 4.2: Calibration of the orifice heater under vacuum
Voltage (V)
0
4
6
8
10
T1 (°C)
26
126
174
227
278
After the calibration, mercury tests were conducted at different orifice temperatures to
monitor the effect of temperature on cluster formation. The peak intensity of 400 amu
corresponding to the Hg dimer has been plotted as a function of the orifice temperature. As
seen from the plot in Figure 4.9, the peak intensity drops suddenly as the temperature
increases and reaches a plateau at the background concentration after 150 °C, indicating that
the dimer formation can be prevented by heating the orifice. Since no dimer was observed at
high temperatures, it is assumed that larger clusters are not formed either. The remainder of
76
the experiments have been performed at orifice temperatures of 200 °C or higher to ensure no
clustering.
7.5E+05
7.0E+05
Hg Dimer
Peak Intensity
6.5E+05
6.0E+05
5.5E+05
5.0E+05
4.5E+05
4.0E+05
3.5E+05
3.0E+05
0
50
100
150
200
250
300
350
Orifice Temperature (°C)
Figure 4.9: Effect of temperature on cluster formation
4.3.3 Chopper
Another modification that has been performed to increase the instrument sensitivity was to
include a molecular-beam chopper in the system, along with a lock-in amplifier from Boston
Electronics to enhance the signal-to-noise ratio. A tuning-fork chopper from Electro-Optical
Products Corporation was installed in the vacuum chamber and is located directly behind the
skimmer. The instructions for the chopper installation are given in Appendix E.
The purpose of a molecular-beam chopper is to create a pulsed signal by chopping the
beam at a known frequency. Once the signal is modulated by the chopper, it can then be
processed by the lock-in amplifier to filter the noise. The output from a lock-in amplifier is a
DC voltage proportional to the amplitude of the input signal with the noise removed. A lockin amplifier consists of the following four stages: an input gain stage, the reference circuit, a
demodulator and a low-pass filter [146].
77
The tuning-fork chopper interrupts the beam periodically by physically blocking the beam.
When converted to an electrical signal that alternates between full intensity and zero
intensity, a square wave results at the chopping frequency. The noise can be significantly
reduced by the use of an AC amplifier that is tuned to the chopping frequency. The AC
amplifier not only amplifies the signal and discriminates against the noise but also converts
the square-wave signal into a sinusoidal signal. In the next stage, demodulation results in a
DC signal that can then be sent through a low-pass filter to provide the final DC output for
measurement [147]. The use of a low-pass filter allows for the noise to be removed, thus
increasing the signal-to-noise ratio, which makes the instrument more sensitive by lowering
the detection limit.
4.4 Instrument Calibration
Before conducting the combustion experiments two different sets of experiments have been
performed for the calibration of the instrument to be able to detect mercury species
quantitatively in the flue gas environment. Calibration curves have been generated for both
Hg0 and HgCl2 and their fragmentation patterns have been determined at ppb level sensitivity
for the first time.
4.4.1 Calibration of Hg
To generate a calibration curve for Hg0, a stream of air with a known concentration of Hg0
supplied from the mercury vapor generator, Cavkit, was fed into the mass spectrometer
directly without passing through the reactor. As described previously in Section 3.3, the
Cavkit has two mass flow controllers, i.e., MFC1 and MFC2, and by changing the set point
of these controllers and the Hg reservoir temperature, a desired Hg concentration is obtained.
In all of the calibration experiments, the MFC2 controller was set to yield a flow rate of 0.5
L/min and only 0.1 L/min of this flow is fed to the mass spectrometer. There is a needle
valve before the mass spectrometer inlet that controls the flow that goes in with the
78
remainder of the flow exiting the exhaust passing through a tee fitting as shown in the
schematic in Figure 4.10.
Figure 4.10: Setup for Hg0 calibration (heated components are shown in red)
The flow rate of the MFC1 controller and the mercury reservoir temperature have been
changed to obtain different concentrations of Hg. Table 4.3 provides a summary of the
conditions used along with the corresponding Hg concentrations.
Table 4.3: Cavkit settings for different Hg concentrations
T (°C)
30
30
40
30
40
MFC1
(mlpm)
3
5.5
5
17
10
MFC2
(lpm)
0.5
0.5
0.5
0.5
0.5
Concentration
(ppbv)
22.0
40.2
80.1
121.4
158.6
For each Hg concentration, data was acquired for 25 minutes. First, 10 minutes of
background data was collected while the inlet valve was closed. After opening the valve to
feed Hg, 10 minutes of data was collected. This was followed by closing the valve to collect
an additional 5 minutes of background data. During data acquisition, the m/z range between
190-220 amu was scanned. The average of the peak intensity at 200 amu was taken for the
10-minute period when the valve was open.
79
Since the chopper was not operating in the calibration experiments, the noise filtering was
performed manually by subtracting the background signal from the actual data. For this
purpose, a background run was conducted before each experiment collecting data for 20
minutes. The average of the peak intensity at 200 amu was taken for the 20-minute period
and this number was subtracted from the average value of the Hg test. This has been carried
out at various Hg concentrations, ranging from 22 ppbv to 158.6 ppbv, with each experiment
repeated at least 2-3 times at each concentration for data reproducibility. Average intensities
of the 200-amu peak after the background subtraction have been plotted as a function of Hg
concentration with the calibration curve shown in Figure 4.11, which has an R2 value of
0.9918.
4.0E+04
Hg
Peak Intensity
3.5E+04
3.0E+04
2.5E+04
2.0E+04
R² = 0.9918
1.5E+04
1.0E+04
5.0E+03
0.0E+00
0
20
40
60
80
100 120 140 160 180
Concentration (ppbv)
Figure 4.11: Calibration curve for Hg0
In all of the experiments the inlet line was heated to 250 °C with the orifice temperature
held fixed at 250 °C. The heat blanket was off during the experiments due to the noise that
appeared in the signal upon operation. Figure 4.12 shows the mass spectra for Hg with the
blanket on and off. It was quite difficult to detect the Hg signal among the noise when the
blanket is on, possibly due to the electronic noise created by the blanket. However, the heat
80
blanket has been used to heat the chamber overnight after each experiment as a cleaning
measure to prevent any mercury accumulation in the chamber.
Figure 4.12: Hg spectra with the blanket on (bottom) and off (top)
The isotope pattern of Hg was clearly observed in the calibration experiments. Figure 4.13
illustrates the isotope pattern for singly ionized Hg along with the relative abundances of
each isotope. This same pattern was observed in the current study.
The ionization energies of the mercury and halogen species of interest are reported in Table
4.4. The energies have been calculated using Gaussian 03 through electronic structure
calculations. The literature values are also given in parentheses for comparison [149]. In
some cases, the experimental data were not available, which is what motivated the
predictions from first principles.
81
Figure 4.13: Isotope pattern of Hg with relative abundances from the literature (experimental
data on the left [148]
Table 4.4: Ionization energies (IE) of mercury and halogen species
1st IE (eV)
2nd IE (eV)
Hg
HgCl
10.17 (10.44)
9.55
18.73 (18.76)
17.34
HgCl2
11.30 (11.38)
17.31
HgBr
9.20
16.56
HgBr2
10.33 (10.56)
16.06
HgO
Cl
9.70
13.12 (12.97)
17.41
23.92 (23.81)
Cl2
11.64 (11.48)
19.66
HCl
Br
12.79 (12.74)
11.96 (11.82)
22.87
21.54
Br2
10.61 (10.52)
17.77
Although double or triple ionization of Hg may be possible, it was not observed in this
work or the peak intensity was too low with the signal buried under the noise. However, HgO
was detected along with Hg and the peak intensity ratio of Hg/HgO was the same in all of the
82
experiments. The average value of Hg/HgO was 1.2 with the fragmentation pattern shown in
Figure 4.14 with the corresponding relative abundances.
Figure 4.14: Fragmentation pattern of Hg and HgO with relative abundances
4.4.2 Calibration of HgCl2
To measure oxidized mercury species directly in the flue gas, a calibration curve is also
required for the Hg-Cl species. For this purpose, an HgCl2 generator from PS Analytical has
been included in the calibration setup. The HgCl2 generator consists of a catalyst that
converts Hg0 to HgCl2. The stream of Hg0 and air that is generated with the Cavkit, flows
through the heated reservoir of the HgCl2 generator and the outlet is directly fed to the mass
spectrometer. Similar to the Hg0 experiments, the MFC2 controller is set to yield 0.5 L/min
with 0.1 L/min flowing to the mass spectrometer. A schematic of the setup is illustrated in
Figure 4.15.
83
Figure 4.15: Schematic of the HgCl2 setup (heated components are shown in red)
The reservoir is kept constant at 250 °C and both the inlet line and the orifice are heated to
300 °C to prevent condensation of HgCl2 since its boiling point is approximately 304 °C
[150]. When the inlet line was not heated to at least 300 °C liquid droplets were observed in
the tube. Since the vacuum chamber is not heated, it is important to look at the vapor
pressure data of HgCl2 to determine whether the condensation would occur under vacuum in
the chamber. The vapor pressure data in Table 4.5 indicates that the temperature should be 64
°C or higher to prevent HgCl2 condensation at 7.5x10-3 Torr. The vapor pressure data at lower
temperatures was not available; however, considering that the pressure in the vacuum
chamber is on the order of 10-6 Torr with the gas flow, it has been assumed that the
condensation of HgCl2 is not likely at these conditions and heating is not required.
Table 4.5: Vapor pressure data of HgCl2 [150]
Temperature
(°C)
Vapor
Pressure (Pa)
Vapor Pressure
(Torr)
64.4
94.7
130.8
174.5
228.5
304
1.00E+00
1.00E+01
1.00E+02
1.00E+03
1.00E+04
1.00E+05
7.50E-03
7.50E-02
7.50E-01
7.50E+00
7.50E+01
7.50E+02
84
Fragmentation pattern of HgCl2
In an earlier study by Kiser et al. [151] employing a time-of-flight mass spectrometer, the
fragmentation pattern of HgCl2 has been reported along with the appearance potentials of the
ions created. The mass spectra that was obtained with an electron energy of 70 eV and the
corresponding appearance potentials of the ions are given in Table 4.6. The most intense ion
in the fragmentation pattern is Cl+, while the second-most intense is the HgCl2+ ion. The
detection of the Cl+ ion reveals that dissociative ionization is taking place; however, the Hg+
ion that is formed through dissociative ionization could not be determined in this previous
work. The reason for this has been attributed to the mercury background spectra caused by
the use of a mercury diffusion pump.
Table 4.6: Appearance potentials and heats of formation for positive ions produced from
mercuric chloride at 187 °C [151]
Ion
Relative Appearance
abundance
Potential
at 70eV
(eV)
Probable Process
ΔHf (ion)
(kcal/mole)
HgCl2+
72.7
10.06±0.25
HgCl2 → HgCl2+
214
HgCl+
9.2
12.06±0.26
→ HgCl+ + Cl
213
HgCl22+
1.6
28.3±0.5
→ HgCl22+
616
HgCl2+
0.2
32.0±0.5
→ HgCl2+ + Cl
672
Cl
+
100
+
→ Cl + Hg + Cl
17.7±0.3
328
A later study by NIST (National Institute Standards and Technology) [149] also reports the
mass spectrum of HgCl2 by electron ionization. Based on the mass spectrum shown in Figure
4.16, the most intense ion is HgCl2+, while the second-most intense is Hg+. In contrast with
the previous study, the relative abundance of the Cl+ ion is approximately 11%.
85
Figure 4.16: Mass spectrum of HgCl2 adapted from NIST [149]
In the current study, to observe all the ions that are created, several m/z ranges were
scanned with following windows in particular: 33-39 amu for Cl+, 190-220 amu for Hg+ and
HgO+, 225-245 amu for HgCl+ and 265-280 amu for HgCl2+. Similar to the Hg experiments
carried out in this work, double ionization was not observed. Each experiment was carried
out for 45 minutes as follows: 5 minutes for the background with the valve closed, 5 minutes
for the 33-39 amu range, 10 minutes for the 190-220 amu range, 10 minutes for the 225-245
amu range, 10 minutes for the 265-280 amu range and 5 minutes of background with the
valve closed. Following this procedure, the experiments were carried out at different
concentrations of HgCl2 ranging from 22 ppbv to 80 ppbv, and repeated twice at each
concentration. Similar to the Hg experiments described previously, the peak intensity of each
mass was averaged for the 10-minute period. A calibration curve has been generated for each
m/z ratio for the ions Cl+, HgCl+, Hg+ and HgO+ with the R2 values of 0.9938, 0.9929,
0.9927 and 0.987, respectively as shown in Figure 4.17.
86
8.E+04
2.5E+07
Hg
R² = 0.9938
HgO
Peak intensity
Hg, HgO, HgCl
6.E+04
HgCl
R² = 0.9927
5.E+04
2.0E+07
Cl
4.E+04
1.5E+07
1.0E+07
R² = 0.987
3.E+04
Peak Intensity
Cl
7.E+04
5.0E+06
2.E+04
R² = 0.9929
1.E+04
0.0E+00
0
20
40
60
80
100
Concentration (ppbv)
Figure 4.17: Calibration curve for HgCl2
The relative abundances of the ions are reported in Table 4.7 with the Hg+ ion being the
most intense among the Hg species.
Table 4.7: Relative abundances of ions
Relative abundance at 70eV
Hg+
100
HgCl+
45.1
HgO+
83.5
Although the Cl+ ion was the most intense, only the Hg species are reported here. The
HgCl2 species was not observed or its peak intensity is too low and the signal is buried under
the noise, therefore it was not included in Table 4.7. As a result of dissociative ionization of
HgCl2, two possible pathways exist, i.e., one that is forming HgCl+ and Cl+ and the other that
is forming Hg+ and Cl+ as shown below. HgCl+ can also further dissociate and form Hg+ and
Cl+.
87
HgCl2 → HgCl+ + Cl+
Hg → Hg+
→ Cl+ + Hg+ + Cl+
→ HgO+
In addition, a fraction of Hg is converted to HgO similar to the Hg experiments that were
conducted earlier. The ratio of Hg+/HgO+ is 1.2, which is the same as that in the Hg
experiments, indicating that no additional HgO was created in the HgCl2 experiments. This
will be very helpful when performing the flue gas analysis where HgCl2 and Hg0 formation
will likely coexist. Knowing the amount of HgO+ and the ratio of Hg+/HgO+, one can
determine how much Hg+ is sourced from the ionization of Hg0 versus the dissociation of
HgCl2.
88
Chapter 5
Summary and Future Work
This work consists of both theoretical and experimental investigations to elucidate the
mercury reaction chemistry in simulated coal combustion flue gas. On the theoretical front,
the objective was to apply theoretical-based cluster modeling to examine the possible binding
mechanism of mercury on activated carbon to aid in the design and fabrication of effective
capture technologies for mercury. The effects of activated carbon‟s different surface
functional groups and halogens on elemental mercury adsorption were examined. Through
comparing the binding energies of elemental mercury on simulated activated carbon surfaces,
it has been concluded that increasing the amount of lactone and carbonyl groups and
decreasing carboxyl group can increase the binding capacity of elemental mercury. In
addition, embedding halogens into the activated carbon matrix can promote elemental
mercury binding. These results can provide a direction for the further experiments that can
aid in recognizing the binding trends and how the binding capacity changes by modifying the
surface. Also, a thermodynamic approach was followed to examine the binding mechanism
of mercury and its oxidized species such as HgCl and HgCl2 on a simulated carbon surface
with and without Cl. Energies of different possible surface complexes and possible products
were compared and dominant pathways were determined relatively. In all of the cases,
chlorine was bound strongly on the surface and does not desorb. Both HgCl and HgCl2 can
89
be adsorbed dissociatively or non-dissociatively. In the case of dissociative adsorption, Hg
can desorb while HgCl remains on the surface. The compound, HgCl2 was not found to be
stable on the surface. Even if it is formed on the surface, it can easily desorb or return to the
reactant species. The most probable mercury species on the surface was found to be HgCl,
which has also been shown by experiments [85]. These observations serve to highlight the
complexity of the binding mechanism of mercury species on activated carbon surfaces.
Understanding the mechanism by which mercury adsorbs on activated carbon is useful to the
design and fabrication of effective control technologies for mercury.
On the experimental front, the objective was to investigate the gas-phase oxidation of
mercury via chlorine in an experimental system simulating the flue gas of a coal-fired power
plant and improve the existing kinetic models to be able to predict the experimental results
by the model. An experimental system consisting of a plug-flow reactor and burner to
generate a laminar premixed methane flame has been designed and built. In this system
mercury and chlorine are introduced into a flame and cooled flue gas is sampled and sent to
the mass spectrometer for direct measurement, with special focus to mercury species. One
needs to be able to make precise mercury measurements to understand the mercury
speciation and accurately predict the extents of mercury oxidation. As explained previously,
currently used measuring methods are problematic and not sufficient in making accurate
predictions. It is essential to measure oxidized and elemental mercury directly and hence
separately to have a complete understanding of mercury speciation. With this goal, a custombuilt mass spectrometer that can directly measure mercury species on the order of ppb
concentrations in the flue gas has been developed. One of the modifications that has been
performed to increase the instrument sensitivity is the inclusion of a supersonic beam
coupled with a new skimmer placed after the first orifice. In such a setup, scattering of the
molecular beam is avoided and the amount of gas reaching the ionization region, and
subsequently the ion detector, is maximized, thereby improving the sensitivity of the
instrument. Another modification was the inclusion of a molecular beam chopper along with
a lock-in amplifier to enhance the signal-to-noise ratio. In addition, a heating system has been
90
designed and fabricated to heat the orifice directly in the vacuum chamber to prevent the
formation of Hg clusters.
With all of these modifications, the detection of mercury at the level of 5 ppb has been
achieved. To measure oxidized mercury species directly in the flue gas, calibration curves
have been generated for both Hg and Hg-Cl species. A linear curve was fitted to each plot
with an R2 value of 0.99. After calibration of the mass spectrometer for mercury species,
combustion experiments will be conducted to speciate mercury in the flue gas environment.
With this custom-built instrument, mercury species can be directly measured for the first time
for high temperature combustion applications. By directly measuring mercury species
accurately, one can determine the actual extent of mercury oxidation in the flue gas, which
will aid in further developing mercury control technologies.
The future work will include operating the combustion system described earlier to simulate
the flue gas and elucidate the homogeneous oxidation of mercury via chlorine and bromine.
The following parameters should be evaluated in the future experiments: the temperature,
chlorine/bromine concentration and background flue gas composition. The temperature effect
can be investigated by employing different quench rates after the high-temperature region in
the furnace. This low-temperature region represents the flue gas after an air preheater and
throughout the air pollution control devices. The change in temperature will influence the
chlorine chemistry in the reactor, which will eventually affect the oxidation of mercury. Also,
changing the concentration of chlorine or bromine will have an effect on the extent of
mercury oxidation. In addition to chlorine/bromine, the effects of other flue gas constituents
such as SO2 and NO should also be investigated.
With the recent Mercury and Air Toxic Standards put forth by EPA, emissions of other
trace metals, e.g., As and Se from power plants will be of importance. Their speciation in the
flue gas is not yet fully understood, but it can easily be determined by the direct
measurements performed with the mass spectrometer. Future combustion experiments should
include these trace metals as well.
91
92
Appendix
93
94
APPENDIX A
CHEMKIN MODEL DATA
95
PSR Input
ENRG
! Solve Gas Energy Equation
STST
! Steady State Solver
!Surface_Temperature
! Surface Temperature Same as Gas Temperature
PRES 0.85
! Pressure (atm)
QLOS 1.0
! Heat Loss (cal/sec)
SCCM 6000.0
! Volumetric Flow Rate in SCCM (standard-cm3/[email protected])
TAU 0.005
! Residence Time (sec)
TEMP 1500.0
! Temperature (K)
TINL 298.0
! Inlet Temperature (K)
REAC C2H6 0.00392039
! Reactant Fraction (mole fraction)
REAC C3H8 0.00110575
! Reactant Fraction (mole fraction)
REAC CH4 0.08071974
! Reactant Fraction (mole fraction)
REAC CO2 0.0013068
! Reactant Fraction (mole fraction)
REAC N2 0.7212505
! Reactant Fraction (mole fraction)
REAC O2 0.19169682
! Reactant Fraction (mole fraction)
END
96
PSR Output
OUTLET CONDITIONS:
Specified inlet mass flow rate =
0.114
gm/sec
Rate of Mass Loss to the walls =
0.00
gm/sec
Outlet mass flow rate
=
0.114
gm/sec
(which, based on an reactor density =
1.397E-04 gm/cm^3
and on a residence time =
5.000E-03 sec,
produces a reactor volume) =
4.08
cm^3
Outlet and reactor temperature = 2031.4
Kelvin
Outlet and reactor pressure
=
0.850
atm
Outlet and reactor density
= 1.39663E-04 gm/cm^3
Outlet and reactor mean molecular weight = 27.389
gm/mole
Outlet molar flow rate
= 4.15735E-03 moles/sec
Outlet volumetric flow rate
= 815.29
cm^3/sec
(based on reactor pressure and temperature)
= 6102.7
SCCM
= 6.1027
SLPM
OUTLET CONDITIONS FOR GAS PHASE MOLECULAR SPECIES:
Species
mole_frac
#/cm^3
moles/sec
gm/sec
cm^3/sec
SCCM
----------------------------------------------------------------------------------------------------H2
5.98842E-03
1.83894E+16
2.48959E-05
5.01887E-05
4.8823
36.546
H
2.04604E-03
6.28304E+15
8.50612E-06
8.57392E-06
1.6681
12.486
O
1.50378E-03
4.61783E+15
6.25172E-06
1.00024E-04
1.2260
9.1771
O2
1.91550E-02
5.88214E+16
7.96338E-05
2.54819E-03
15.617
116.90
OH
5.96883E-03
1.83292E+16
2.48145E-05
4.22030E-04
4.8663
36.426
H2O
0.16453
5.05236E+17
6.84000E-04
1.23225E-02
134.14
1004.1
HO2
2.99285E-06
9.19050E+12
1.24423E-08
4.10680E-07
2.44004E-03
1.82645E-02
H2O2
1.41183E-07
4.33549E+11
5.86949E-10
1.99649E-08
1.15106E-04
8.61601E-04
C
4.11717E-08
1.26431E+11
1.71165E-10
2.05589E-09
3.35669E-05
2.51259E-04
CH
1.56160E-07
4.79538E+11
6.49210E-10
8.45214E-09
1.27316E-04
9.52996E-04
CH2
1.19769E-06
3.67789E+12
4.97921E-09
6.98439E-08
9.76466E-04
7.30915E-03
CH2(S)
1.12596E-07
3.45761E+11
4.68100E-10
6.56607E-09
9.17983E-05
6.87139E-04
CH3
1.44160E-05
4.42688E+13
5.99322E-08
9.01084E-07
1.17532E-02
8.79764E-02
CH4
3.65698E-05
1.12299E+14
1.52033E-07
2.43907E-06
2.98150E-02
0.22317
97
CO
11.478
CO2
63.161
HCO
5.04072E-04
CH2O
4.81396E-03
CH2OH
1.02732E-04
CH3O
5.64239E-06
CH3OH
8.37365E-05
C2H
4.12488E-06
C2H2
6.40414E-04
C2H3
5.91318E-05
C2H4
7.76334E-04
C2H5
9.69830E-05
C2H6
3.26545E-04
HCCO
1.11880E-04
CH2CO
3.17728E-04
HCCOH
1.37803E-05
N
1.74958E-05
NH
8.23656E-06
NH2
1.00147E-05
NH3
9.70370E-06
NNH
2.45080E-06
NO
0.13479
NO2
2.48517E-05
N2O
1.12713E-04
HNO
9.18691E-06
CN
1.47782E-06
HCN
3.43145E-04
H2CN
5.96742E-09
1.40787E-02
85.918
7.74710E-02
472.78
6.18272E-07
3.77313E-03
5.90459E-06
3.60340E-02
1.26007E-07
7.68983E-04
6.92071E-09
4.22351E-05
1.02707E-07
6.26794E-04
5.05939E-09
3.08760E-05
7.85503E-07
4.79370E-03
7.25283E-08
4.42619E-04
9.52217E-07
5.81110E-03
1.18955E-07
7.25948E-04
4.00525E-07
2.44429E-03
1.37227E-07
8.37455E-04
3.89711E-07
2.37829E-03
1.69023E-08
1.03150E-04
2.14595E-08
1.30961E-04
1.01026E-08
6.16532E-05
1.22836E-08
7.49631E-05
1.19021E-08
7.26352E-05
3.00604E-09
1.83450E-05
1.65332E-04
1.0090
3.04820E-08
1.86023E-04
1.38248E-07
8.43688E-04
1.12683E-08
6.87669E-05
1.81262E-09
1.10619E-05
4.20886E-07
2.56855E-03
7.31937E-12
4.46680E-08
4.32330E+16
5.85299E-05
1.63945E-03
2.37900E+17
3.22074E-04
1.41745E-02
1.89860E+12
2.57037E-09
7.45884E-08
1.81319E+13
2.45474E-08
7.37073E-07
3.86945E+11
5.23855E-10
1.62575E-08
2.12523E+10
2.87718E-11
8.92917E-10
3.15396E+11
4.26991E-10
1.36818E-08
1.55365E+10
2.10336E-11
5.26478E-10
2.41214E+12
3.26561E-09
8.50307E-08
2.22722E+11
3.01526E-10
8.15513E-09
2.92409E+12
3.95870E-09
1.11058E-07
3.65290E+11
4.94538E-10
1.43723E-08
1.22994E+12
1.66512E-09
5.00705E-08
4.21399E+11
5.70500E-10
2.34074E-08
1.19673E+12
1.62017E-09
6.81079E-08
5.19038E+10
7.02686E-11
2.95393E-09
6.58983E+10
8.92147E-11
1.24960E-09
3.10233E+10
4.20000E-11
6.30616E-10
3.77207E+10
5.10671E-11
8.18230E-10
3.65493E+10
4.94813E-11
8.42697E-10
9.23102E+09
1.24972E-11
3.62685E-10
5.07704E+14
6.87342E-07
2.06244E-05
9.36048E+10
1.26724E-10
5.83002E-09
4.24535E+11
5.74746E-10
2.52962E-08
3.46028E+10
4.68461E-11
1.45289E-09
5.56624E+09
7.53571E-12
1.96063E-10
1.29247E+12
1.74977E-09
4.72890E-08
2.24765E+07
3.04292E-14
8.53045E-13
98
HCNN
7.08026E-08
HCNO
3.75338E-05
HOCN
2.68213E-06
HNCO
1.70996E-04
NCO
1.64883E-05
N2
578.07
AR
0.0000
C3H7
2.37330E-05
C3H8
8.34244E-05
CH2CHO
2.70346E-06
CH3CHO
1.87340E-04
8.68433E-11
5.29979E-07
4.60373E-08
2.80952E-04
3.28978E-09
2.00766E-05
2.09736E-07
1.27996E-03
2.02239E-08
1.23420E-04
0.70903
4327.0
0.0000
0.0000
2.91098E-08
1.77649E-04
1.02325E-07
6.24457E-04
3.31595E-09
2.02363E-05
2.29783E-07
1.40230E-03
2.66680E+08
3.61038E-13
1.48143E-11
1.41372E+11
1.91393E-10
8.23473E-09
1.01023E+10
1.36768E-11
5.88445E-10
6.44062E+11
8.71946E-10
3.75157E-08
6.21038E+10
8.40776E-11
3.53271E-09
2.17730E+18
2.94768E-03
8.25745E-02
0.0000
0.0000
0.0000
8.93909E+10
1.21020E-10
5.21464E-09
3.14220E+11
4.25399E-10
1.87589E-08
1.01827E+10
1.37856E-11
5.93408E-10
7.05621E+11
9.55286E-10
4.20838E-08
DETAILED SPECIES BALANCE
(all rates are in moles per sec)
SPECIES
INLET_FR
OUTLET_FR GAS_PROD_RATE GAS_DEST_RATE
SURF_NET_PROD
TOTAL_NET
--------------------------------------------------------------------------------------------------------------------------------H2
0.00
2.490E-05
4.130E-02
4.127E-02
0.00
6.676E-08
H
0.00
8.506E-06
5.580E-02
5.579E-02
0.00
-8.750E-08
O
0.00
6.252E-06
3.612E-02
3.611E-02
0.00
3.362E-09
O2
7.835E-04
7.963E-05
9.322E-03
1.003E-02
0.00
-1.168E-08
OH
0.00
2.481E-05
9.568E-02
9.565E-02
0.00
8.509E-08
H2O
0.00
6.840E-04
5.554E-02
5.486E-02
0.00
-3.546E-08
HO2
0.00
1.244E-08
3.037E-04
3.036E-04
0.00
5.344E-08
H2O2
0.00
5.869E-10
1.290E-04
1.290E-04
0.00
-6.333E-08
C
0.00
1.712E-10
5.588E-06
5.588E-06
0.00
-2.444E-11
CH
0.00
6.492E-10
6.227E-05
6.227E-05
0.00
-7.210E-11
CH2
0.00
4.979E-09
2.134E-04
2.134E-04
0.00
-2.084E-10
CH2(S)
0.00
4.681E-10
2.647E-04
2.647E-04
0.00
2.220E-11
CH3
0.00
5.993E-08
4.425E-04
4.425E-04
0.00
-1.137E-08
99
CH4
0.00
CO
0.00
CO2
0.00
HCO
0.00
CH2O
0.00
CH2OH
0.00
CH3O
0.00
CH3OH
0.00
C2H
0.00
C2H2
0.00
C2H3
0.00
C2H4
0.00
C2H5
0.00
C2H6
0.00
HCCO
0.00
CH2CO
0.00
HCCOH
0.00
N
0.00
NH
0.00
NH2
0.00
NH3
0.00
NNH
0.00
NO
0.00
NO2
0.00
N2O
0.00
HNO
0.00
CN
0.00
HCN
0.00
3.299E-04
1.520E-07
2.661E-05
3.564E-04
5.853E-05
4.877E-03
4.819E-03
3.221E-04
4.837E-03
4.520E-03
0.00
2.570E-09
2.516E-04
2.516E-04
0.00
2.455E-08
2.021E-04
2.020E-04
0.00
5.239E-10
2.355E-05
2.355E-05
0.00
2.877E-11
3.032E-06
3.032E-06
0.00
4.270E-10
3.598E-06
3.597E-06
0.00
2.103E-11
2.367E-06
2.367E-06
0.00
3.266E-09
9.443E-06
9.440E-06
0.00
3.015E-10
7.918E-06
7.918E-06
0.00
3.959E-09
1.119E-05
1.119E-05
0.00
4.945E-10
1.565E-05
1.565E-05
1.665E-09
1.184E-07
1.614E-05
0.00
5.705E-10
6.266E-06
6.265E-06
0.00
1.620E-09
2.611E-06
2.610E-06
0.00
7.027E-11
3.588E-07
3.587E-07
0.00
8.921E-11
6.296E-07
6.294E-07
0.00
4.200E-11
5.364E-07
5.364E-07
0.00
5.107E-11
2.764E-07
2.763E-07
0.00
4.948E-11
7.811E-08
7.806E-08
0.00
1.250E-11
3.075E-05
3.075E-05
0.00
6.873E-07
2.710E-06
2.022E-06
0.00
1.267E-10
8.762E-07
8.761E-07
0.00
5.747E-10
1.477E-07
1.472E-07
0.00
4.685E-11
9.314E-07
9.313E-07
0.00
7.536E-12
1.929E-07
1.929E-07
0.00
1.750E-09
5.060E-07
5.042E-07
1.078E-08
0.00
9.551E-09
5.341E-06
-9.697E-09
-2.737E-10
5.002E-10
-1.626E-10
-7.827E-11
1.101E-10
-3.489E-11
-1.035E-11
-2.151E-10
2.749E-10
-6.190E-10
1.602E-05
1.010E-09
-5.111E-11
-2.464E-12
-7.178E-12
2.766E-11
1.241E-11
1.807E-12
-3.345E-13
1.989E-11
-3.040E-11
-2.603E-11
-1.853E-12
3.055E-11
5.009E-13
1.260E-11
100
H2CN
0.00
HCNN
0.00
HCNO
0.00
HOCN
0.00
HNCO
0.00
NCO
0.00
N2
0.00
AR
0.00
C3H7
0.00
C3H8
0.00
CH2CHO
0.00
CH3CHO
0.00
0.00
3.043E-14
3.362E-09
3.362E-09
0.00
3.610E-13
3.553E-08
3.553E-08
0.00
1.914E-10
7.035E-08
7.016E-08
0.00
1.368E-11
5.932E-08
5.931E-08
0.00
8.719E-10
4.470E-07
4.462E-07
0.00
8.408E-11
5.687E-07
5.687E-07
2.948E-03
2.328E-04
2.331E-04
-2.717E-13
5.200E-14
-2.211E-12
-2.507E-12
5.162E-12
-7.713E-12
2.948E-03
-2.871E-11
0.00
0.00
0.00
0.00
0.00
0.00
1.210E-10
3.765E-06
3.765E-06
4.254E-10
2.079E-08
4.540E-06
0.00
1.379E-11
1.958E-06
1.958E-06
0.00
9.553E-10
2.078E-06
2.077E-06
-1.290E-10
4.520E-06
1.861E-10
1.975E-11
1.063E-11
DETAILED ELEMENT BALANCES
(all rates are in moles per sec)
ELEMENT
INLET_FR
OUTLET_FR
TOTAL_NET
----------------------------------------------------------------------------------------------------------------------O
1.578E-03
1.578E-03
1.889E-14
H
1.452E-03
1.452E-03
-1.143E-14
C
3.809E-04
3.809E-04
-9.218E-16
N
5.896E-03
5.896E-03
-1.996E-14
AR
0.00
0.00
0.00
101
PFR Input – 100ppmv Cl no Hg
MOMEN ON
! Turn on Momentum Equation
PLUG
! Plug Flow Reactor
RTIME ON
! Turn on Residence Time Calculation
TGIV
! Fix Gas Temperature
!Surface_Temperature
! Surface Temperature Same as Gas Temperature
PRES 0.85
! Pressure (atm)
TPRO 0.0 948.0
! Temperature (K)
TPRO 5.08 1187.0
! Temperature (K)
TPRO 10.16 1287.0
! Temperature (K)
TPRO 15.24 1336.0
! Temperature (K)
TPRO 20.32 1347.0
! Temperature (K)
TPRO 25.4 1361.0
! Temperature (K)
TPRO 30.48 1373.0
! Temperature (K)
TPRO 35.56 1374.0
! Temperature (K)
TPRO 40.64 1369.0
! Temperature (K)
TPRO 45.72 1349.0
! Temperature (K)
TPRO 50.8 1319.0
! Temperature (K)
TPRO 55.88 1212.0
! Temperature (K)
TPRO 60.96 1066.0
! Temperature (K)
TPRO 66.04 858.0
! Temperature (K)
TPRO 71.12 769.0
! Temperature (K)
TPRO 76.2 716.0
! Temperature (K)
TPRO 81.28 679.0
! Temperature (K)
TPRO 86.36 673.0
! Temperature (K)
TPRO 91.44 670.0
! Temperature (K)
TPRO 96.52 649.0
! Temperature (K)
TPRO 101.6 637.0
! Temperature (K)
TPRO 106.68 619.0
! Temperature (K)
TPRO 111.76 613.0
! Temperature (K)
TPRO 116.84 608.0
! Temperature (K)
TPRO 121.92 603.0
! Temperature (K)
TPRO 127.0 603.0
! Temperature (K)
TPRO 132.08 603.0
! Temperature (K)
VDOT 408.5
! Volumetric Flow Rate (cm3/sec)
DIAM 4.699
! Diameter (cm)
XEND 132.08
! Ending Axial Position (cm)
REAC AR 0.0
! Reactant Fraction (mole fraction)
REAC C 4.11717E-8
! Reactant Fraction (mole fraction)
REAC C2H 5.05939E-9
! Reactant Fraction (mole fraction)
REAC C2H2 7.85503E-7
! Reactant Fraction (mole fraction)
REAC C2H3 7.25283E-8
! Reactant Fraction (mole fraction)
REAC C2H4 9.52217E-7
! Reactant Fraction (mole fraction)
REAC C2H5 1.18955E-7
! Reactant Fraction (mole fraction)
REAC C2H6 4.00525E-7
! Reactant Fraction (mole fraction)
REAC CH 1.5616E-7
! Reactant Fraction (mole fraction)
REAC CH2 1.19769E-6
! Reactant Fraction (mole fraction)
REAC CH2CO 3.89711E-7
! Reactant Fraction (mole fraction)
REAC CH2O 5.90459E-6
! Reactant Fraction (mole fraction)
REAC CH2OH 1.26007E-7
! Reactant Fraction (mole fraction)
REAC CH3 1.4416E-5
! Reactant Fraction (mole fraction)
REAC CH3O 6.92071E-9
! Reactant Fraction (mole fraction)
REAC CH3OH 1.02707E-7
! Reactant Fraction (mole fraction)
REAC CH4 3.65698E-5
! Reactant Fraction (mole fraction)
REAC CL 0.0001
! Reactant Fraction (mole fraction)
102
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
DXMX
CL2 0.0
! Reactant Fraction (mole fraction)
CN 1.81262E-9
! Reactant Fraction (mole fraction)
CO 1.9E-5
! Reactant Fraction (mole fraction)
CO2 0.077471
! Reactant Fraction (mole fraction)
H 0.00204604
! Reactant Fraction (mole fraction)
H2 0.00598842
! Reactant Fraction (mole fraction)
H2CN 7.31937E-12
! Reactant Fraction (mole fraction)
H2O 0.16453
! Reactant Fraction (mole fraction)
H2O2 1.41183E-7
! Reactant Fraction (mole fraction)
HCCO 1.37227E-7
! Reactant Fraction (mole fraction)
HCCOH 1.69023E-8
! Reactant Fraction (mole fraction)
HCN 4.20886E-7
! Reactant Fraction (mole fraction)
HCO 6.18272E-7
! Reactant Fraction (mole fraction)
HNCO 2.09736E-7
! Reactant Fraction (mole fraction)
HNO 1.12683E-8
! Reactant Fraction (mole fraction)
HO2 2.99285E-6
! Reactant Fraction (mole fraction)
HOCN 3.28978E-9
! Reactant Fraction (mole fraction)
N 2.14595E-8
! Reactant Fraction (mole fraction)
N2 0.70903
! Reactant Fraction (mole fraction)
N2O 1.38248E-7
! Reactant Fraction (mole fraction)
NCO 2.02239E-8
! Reactant Fraction (mole fraction)
NH 1.01026E-8
! Reactant Fraction (mole fraction)
NH2 1.22836E-8
! Reactant Fraction (mole fraction)
NH3 1.19021E-8
! Reactant Fraction (mole fraction)
NNH 3.00604E-9
! Reactant Fraction (mole fraction)
NO 3.6E-5
! Reactant Fraction (mole fraction)
NO2 3.0482E-8
! Reactant Fraction (mole fraction)
O 0.000641
! Reactant Fraction (mole fraction)
O2 0.008159
! Reactant Fraction (mole fraction)
OH 0.00596883
! Reactant Fraction (mole fraction)
SO2 0.0
! Reactant Fraction (mole fraction)
0.1
! Solver Maximum Step Distance (cm)
END
103
Temperature Profile
Distance Temperature
(cm)
(°C)
0
675
5.08
914
10.16
1014
15.24
1063
20.32
1074
25.4
1088
30.48
1100
35.56
1101
40.64
1096
45.72
1076
50.8
1046
55.88
939
60.96
793
66.04
585
71.12
496
76.2
443
81.28
406
86.36
400
91.44
397
96.52
376
101.6
364
106.68
346
111.76
340
116.84
335
121.92
330
127
330
132.08
330
104
Kinetics Data – Roesler
! HCL REACTIONS (Roesler et al. 1995)
(29 reactions)
H+CL+M=HCL+M
HCL+H=H2+CL
!298-1500 SENKAN1998
HCL+OH=H2O+CL
!HCL+OH=H2O+CL
!wANG HAI
HCL+O=OH+CL
!350-1480 MKF1990
!HCL+O=OH+CL
!Niksa
!HCL+O=OH+CL
!WANG HAI
CL+HO2=HCL+O2
!CL+HO2=HCL+O2
!Edwards
CL2+H=HCL+CL
1500 SENKAN1998
!CL2+H=HCL+CL
HAI
CL+CL+M=CL2+M
1800.
CL2+O=CLO+CL
CLO+O=CL+O2
1200 ABCHKT 1992
!CLO+O=CL+O2
HO2+CL=OH+CLO
H2O2+CL=HO2+HCL
HOCL+CL=CLO+HCL
CLO+H2=HOCL+H
14100.
H+HOCL=HCL+OH
CL+HOCL=CL2+OH
O+HOCL=OH+CLO
OH+HOCL=H2O+CLO
HOCL=OH+CL
HOCL=H+CLO
CLCO+M=CO+CL+M
CLCO+O2=CO2+CLO
CLCO+CL=CO+CL2
CLCO+H=CO+HCL
CLCO+O=CO+CLO
CLCO+O=CO2+CL
CLCO+OH=CO+HOCL
CLO+CO=CO2+CL
HCO+CL=CO+HCL
HCO+CLO=CO+HOCL
7.19E21
1.8E12
-2.0
0.3
3804.
2.71E7
2.45E12
1.65
0.0
-220.
1100.
4.5E3
3.13
3110.
3.4E3
2.87
3510.
5.24E12
0.0
6400.
1.08E13
0.0
4.1E13
105
0.
-330.
0.0
-330.
6.0E10
1.0
191.
!298-
8.59E13
0.0
1170. !wANG
4.68E14
0.0
2.52E12
3.3E8
0.0
2.0
2720.
191. !300-
5.7E13
2.42E13
6.62E12
7.28E12
6.03E11
0.0
0.0
0.0
0.0
0.0
364.
2300.
1950.
180.
9.55E13
1.81E12
6.03E12
1.81E12
1.76E20
8.13E14
1.30E14
7.94E10
4.00E14
1.00E14
1.00E14
1.00E13
3.30E12
6.03E11
1.00E14
3.16E13
0.0
0.0
0.0
0.0
-3.01
-2.09
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
7620.
260.
4370.
990.
56720.
93690.
8000.
3300.
800.
0.
0.
0.
0.
7400.
0.
0.
-
Kinetics Data – Bozelli
!Bozzelli chlorine chemistry
CL + H2 = HCL + H
5000.
CL + CO = COCL
CL + CL + M = CL2 + M
1600.
CL + HCO = HCL + CO
CLO + H2 = HOCL + H
13500.
CLO + CO = CO2 + CL
7400.
!COCL + CL = COCL2
COCL + CL = CO + CL2
COCL + H = CO + HCL
COCL + H = HCO + CL
-180.
COCL + O2 = CO2 + CLO
COCL + O = CO2 + CL
0.0
O + HCL = OH + CL
6400.
O + CL2 = CLO + CL
2800.
O + CLO = CL + O2
400.
OH + HCL = H2O + CL
1000.
4.80E+13
0.0
1.95E+19
5.75E+14
-3.01
0.0
1.41E+14
1.00E+13
-0.35
7.94E+10
1.00E+13
510.
0.0
6.02E+11
3.40E+28
1.49E+19
3.54E+16
3.42E+09
8070.
-
0.0
-5.61
-2.17
-0.79
3390.
1470.
1060.
1.15
0.0
3300.
0.0
5.25E+12
0.0
1.26E+13
0.0
5.75E+13
0.0
2.20E+12
0.0
!*********************Duplicate Chemistry***********************
!CH3CL + OH = CH2CL + H2O
!CH3CL + O = OH + CH2CL
!CH3CL + H = H2 + CH2CL
10600.
!CH3CL + O2 = HO2 + CH2CL
52200.
!CH3CL + HO2 = H2O2 + CH2CL
16700.
!CH3CL + CLO = HOCL + CH2CL
!CH3CL + CL = HCL + CH2CL
!CH3CL + CH3 = CH4 + CH2CL
!CH3CL + H = HCL + CH3
!CH3CL = CH3 + CL
88810.
!CH3CL = CH2 + HCL
132460.
!CH3CL = CH2CL + H
106100.
!CH2CL + O2 = CLO + CH2O
!CH2CL + H = CH3 + CL
!CH2CL + HO2 = CH2CLO. + OH
!CH2CL + OH = CH2O + HCL
!CH2CL + OH = CH2OH + CL
1.32E+12
1.70E+13
6.66E+13
0.0
0.0
0.0
4.00E+13
0.0
1.00E+13
0.0
5.00E+12
3.16E+13
3.31E+11
5.40E+13
5.53E+31
0.0
0.0
0.0
0.0
-5.63
1.82E+25
-4.69
1.31E+30
5.23
8.46E+13
1.68E+16
5.19E+14
4.10E+21
9.24E+11
106
-1.03
-0.68
-0.51
-2.57
2300.
7300.
8700.
3300.
9400.
6500.
8180.
1020.
840.
3740.
0.38
2970.
!CH2CL + CH3 = C2H5CL
!CH2CL + CH3 = C2H4 + HCL
!CH2CL + O = CH2CLO.
!CH2CL + O = CH2O + CL
!CH2CLO. = CH2O + CL
!CH2O + CL = HCO + HCL
!CH2O + CLO = HOCL + HCO
!CH3 + CLO = CH3O + CL
!CH3 + CLO = HCL + CH2O
!CH4 + CLO = CH3 + HOCL
15000.
!CH4 + CL = HCL + CH3
!C2H2 + CL = HCL + C2H
28800.
!C2H3 + CL = C2H3CL
!C2H3 + CL = C2H2 + HCL
!C2H4 + CLO = CH2CL + CH2O
!!C2H4 + CLO = C2H4OCL
!C2H4 + CL = HCL + C2H3
!C2H5 + CL = C2H5CL
!C2H5 + CL = C2H4 + HCL
!C2H5 + CL = CH3 + CH2CL
!C2H6 + CL = HCL + C2H5
!!CL + C2H3CL = HCL + CHCL*CJH
8.47E+34
4.80E+24
2.55E+15
8.31E+13
2.51E+24
5.00E+13
1.20E+13
2.28E+07
5.50E+14
1.40E+13
-6.75
-3.44
-2.02
-0.18
-4.78
8080.
7690.
1230.
800.
10070.
0.0
0.0
1.54
500.
2000.
-820.
-0.51
710.
0.0
2.57E+13
1.00E+13
0.0
0.0
6.50E+34
2.40E+24
-3.22
9.26E+18
-1.98
1.75E+32
-6.32
3.00E+13
8.39E+36
6.12E+24
-3.38
1.50E+21
-1.94
7.00E+13
5.00E+12
-6.63
3850.
8610.
9070.
8430.
7900.
0.0
-7.38
5100.
9550.
9040.
17720.
0.0
0.0
1000.
5870.
!**************************************************************************
HO2 + CL = HCL + O2
0.
HO2 + CL = CLO + OH
H2O2 + CL = HCL + HO2
H2O2 + CLO = HOCL + HO2
1.58E+13
3.35E+14
1.02E+12
5.00E+12
107
0.0
-0.32
0.0
0.0
1470.
800.
2000.
PFR Input with 100 ppm Cl, 25 μg/m3 Hg
MOMEN ON
! Turn on Momentum Equation
PLUG
! Plug Flow Reactor
RTIME ON
! Turn on Residence Time Calculation
TGIV
! Fix Gas Temperature
!Surface_Temperature
! Surface Temperature Same as Gas Temperature
PRES 0.85
! Pressure (atm)
TPRO 0.0 948.0
! Temperature (K)
TPRO 5.08 1187.0
! Temperature (K)
TPRO 10.16 1287.0
! Temperature (K)
TPRO 15.24 1336.0
! Temperature (K)
TPRO 20.32 1347.0
! Temperature (K)
TPRO 25.4 1361.0
! Temperature (K)
TPRO 30.48 1373.0
! Temperature (K)
TPRO 35.56 1374.0
! Temperature (K)
TPRO 40.64 1369.0
! Temperature (K)
TPRO 45.72 1349.0
! Temperature (K)
TPRO 50.8 1319.0
! Temperature (K)
TPRO 55.88 1212.0
! Temperature (K)
TPRO 60.96 1066.0
! Temperature (K)
TPRO 66.04 858.0
! Temperature (K)
TPRO 71.12 769.0
! Temperature (K)
TPRO 76.2 716.0
! Temperature (K)
TPRO 81.28 679.0
! Temperature (K)
TPRO 86.36 673.0
! Temperature (K)
TPRO 91.44 670.0
! Temperature (K)
TPRO 96.52 649.0
! Temperature (K)
TPRO 101.6 637.0
! Temperature (K)
TPRO 106.68 619.0
! Temperature (K)
TPRO 111.76 613.0
! Temperature (K)
TPRO 116.84 608.0
! Temperature (K)
TPRO 121.92 603.0
! Temperature (K)
TPRO 127.0 603.0
! Temperature (K)
TPRO 132.08 603.0
! Temperature (K)
VDOT 408.5
! Volumetric Flow Rate (cm3/sec)
DIAM 4.699
! Diameter (cm)
XEND 132.08
! Ending Axial Position (cm)
REAC AR 0.0
! Reactant Fraction (mole fraction)
REAC C 4.11717E-8
! Reactant Fraction (mole fraction)
REAC C2H 5.05939E-9
! Reactant Fraction (mole fraction)
REAC C2H2 7.85503E-7
! Reactant Fraction (mole fraction)
REAC C2H3 7.25283E-8
! Reactant Fraction (mole fraction)
REAC C2H4 9.52217E-7
! Reactant Fraction (mole fraction)
REAC C2H5 1.18955E-7
! Reactant Fraction (mole fraction)
REAC C2H6 4.00525E-7
! Reactant Fraction (mole fraction)
REAC CH 1.5616E-7
! Reactant Fraction (mole fraction)
REAC CH2 1.19769E-6
! Reactant Fraction (mole fraction)
REAC CH2CO 3.89711E-7
! Reactant Fraction (mole fraction)
REAC CH2O 5.90459E-6
! Reactant Fraction (mole fraction)
REAC CH2OH 1.26007E-7
! Reactant Fraction (mole fraction)
REAC CH3 1.4416E-5
! Reactant Fraction (mole fraction)
REAC CH3O 6.92071E-9
! Reactant Fraction (mole fraction)
REAC CH3OH 1.02707E-7
! Reactant Fraction (mole fraction)
REAC CH4 3.65698E-5
! Reactant Fraction (mole fraction)
REAC CL 0.0001
! Reactant Fraction (mole fraction)
108
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
REAC
DXMX
END
CL2 0.0
! Reactant Fraction (mole fraction)
CN 1.81262E-9
! Reactant Fraction (mole fraction)
CO 1.9E-5
! Reactant Fraction (mole fraction)
CO2 0.077471
! Reactant Fraction (mole fraction)
H 0.00204604
! Reactant Fraction (mole fraction)
H2 0.00598842
! Reactant Fraction (mole fraction)
H2CN 7.31937E-12
! Reactant Fraction (mole fraction)
H2O 0.16453
! Reactant Fraction (mole fraction)
H2O2 1.41183E-7
! Reactant Fraction (mole fraction)
HCCO 1.37227E-7
! Reactant Fraction (mole fraction)
HCCOH 1.69023E-8
! Reactant Fraction (mole fraction)
HCN 4.20886E-7
! Reactant Fraction (mole fraction)
HCO 6.18272E-7
! Reactant Fraction (mole fraction)
HG 2.28795E-9
! Reactant Fraction (mole fraction)
HNCO 2.09736E-7
! Reactant Fraction (mole fraction)
HNO 1.12683E-8
! Reactant Fraction (mole fraction)
HO2 2.99285E-6
! Reactant Fraction (mole fraction)
HOCN 3.28978E-9
! Reactant Fraction (mole fraction)
N 2.14595E-8
! Reactant Fraction (mole fraction)
N2 0.70903
! Reactant Fraction (mole fraction)
N2O 1.38248E-7
! Reactant Fraction (mole fraction)
NCO 2.02239E-8
! Reactant Fraction (mole fraction)
NH 1.01026E-8
! Reactant Fraction (mole fraction)
NH2 1.22836E-8
! Reactant Fraction (mole fraction)
NH3 1.19021E-8
! Reactant Fraction (mole fraction)
NNH 3.00604E-9
! Reactant Fraction (mole fraction)
NO 3.6E-5
! Reactant Fraction (mole fraction)
NO2 3.0482E-8
! Reactant Fraction (mole fraction)
O 0.000641
! Reactant Fraction (mole fraction)
O2 0.008159
! Reactant Fraction (mole fraction)
OH 0.00596883
! Reactant Fraction (mole fraction)
SO2 0.0
! Reactant Fraction (mole fraction)
0.1
! Solver Maximum Step Distance (cm)
109
Kinetics Data - Wilcox-Roesler
ELEMENTS
HG CL O
H
N C S AR END
SPECIES
HG HGCL HGCL2 HGO CL CL2 HCL HOCL CLO CLO2 H2
CCLO COCL
O2
H2O
H2O2
CO
CO2
H
O
OH
HCO
HCCO
N2
NH2
H2NO
NCO
N2H3
C2N2
HNCO
CLCO NOCL
S
SH
H2S
SO
CS
COS
HSNO
SO2* SCL
CH CH2 CH2(S) CH3 CH4
CH2OH CH3O
CH3OH
C2H4
C2H5
C2H6
C3H7
CH2CHO
CH2O
C
HO2
AR
CN
HCN
N2O
NO2
N2H2
O3 HONO NO3 HNO3
SO2
HSO
SO3
HOS
C2H
CH2CO
C2H2
HCCOH
HSO2
HSOH
C2H3
CH3CO
N
HOCN
NH
H2CN
NO
NNH
HNO
NH3
HOSO
H2SO
HOSO2
HOSHO
SN
HS2
S2
CH2SING
CH3CHO
CH3CL CH2CL CH2CLO.
C2H4OCL
CHCLC.H
C2H5CL
C2H3CL
COCL2 CH2CLC.H2
CH3C.HCL
CH2CLO
CHCLO CHO HCO2
END
REACTIONS
!H+O2+M=HO2+M
! H2O/18.6/ H2/2.86/
!SH+H+M=H2+M
0.
H+H+H2=H2+H2
H+H+H2O=H2+H2O
!H+OH+M=H2O+M
! H2O/5/
!H+O+M=OH+M
! H2O/5/
!O+O+M=O2+M
1788.
!H2O2+M=OH+OH+M
45500.
H2+O2=2OH
47780.
!OH+H2=H2O+H
!O+OH=O2+H
!O+H2=OH+H
!OH+HO2=H2O+O2
!H+HO2=2OH
!O+HO2=O2+OH
!2OH=O+H2O
3.61E17
-0.72
1.0E18
110
0.
-1.0
9.2E16
6.0E19
1.6E22
-0.6
-1.25
-2.0
0.
0.
0.
6.2E16
-0.6
0.
1.89E13
0.0
-
1.3E17
0.0
1.7E13
0.0
1.17E9
3.61E14
5.06E4
7.5E12
1.4E14
1.4E13
6.0E+8
1.3
-0.5
2.7
0.0
0.0
0.0
1.3
3626.
0.
6290.
0.0
1073.
1073.
0.
!H+HO2=H2+O2
!HO2+HO2=H2O2+O2
!H2O2+H=HO2+H2
!H2O2+OH=H2O+HO2
1.25E13
2.0E12
1.6E12
1.0E13
0.0
0.0
0.0
0.0
0.
0.
3800.
1800.
! C-H-O Chemistry (PRINCETON--28REACTIONS)
H+O2=O+OH
16440.0
!H+O2=O+OH
17041.0
!H+O2=O+OH
14856.0
O+H2=H+OH
6290.0
OH+H2=H2O+H
3430.0
H2O+O=OH+OH
13400.0
H2+M=H+H+M
104000.0
O+O+M=O2+M
0.0
H+O+M=OH+M
0.0
OH+H+M=H2O+M
0.0
H+O2+M=HO2+M
0.0
!H+O2+M=HO2+M
0.0
HO2+H=H2+O2
820.0
HO2+H=OH+OH
300.0
HO2+O=O2+OH
0.0
HO2+OH=H2O+O2
-500.0
HO2+HO2=H2O2+O2
12000.0
!HO2+HO2=H2O2+O2
-1629.
H2O2+M=OH+OH+M
48400.0
H2O2+H=H2O+OH
3970.0
H2O2+H=HO2+H2
7950.0
H2O2+O=OH+HO2
3970.0
H2O2+OH=H2O+HO2
0.0
!H2O2+OH=H2O+HO2
9560.0
CO+O+M=CO2+M
2830.0
1.91E+14
0.0
!PRINCETON
2.65E+16
-0.7
!GRI
9.76E+13
0.0
!Leeds
5.06E+04
2.7
2.16E+08
1.5
2.97E+06
2.0
!Roseler
! (Niksa 2380)
111
4.57E+19
-1.4
6.17E+15
-0.5
4.72E+18
-1.0
2.21E+22
-2.0
1.48E+12
0.6
1.48E+12
0.6
1.66E+13
0.0
7.08E+13
0.0
3.25E+13
0.0
2.89E+13
0.0
4.20E+14
0.0
1.3E11
0.0
2.95E+14
0.0
2.41E+13
0.0
4.82E+13
0.0
9.55E+06
2.0
1.00E+12
0.0
5.80E14
0.0
1.80E+10
0.0
CO+O2=CO2+O
47700.0
CO+OH=CO2+H
-1350.0
CO+HO2=CO2+OH
22900.0
HCO+M=H+CO+M
17000.0
HCO+O2=CO+HO2
406.0
HCO+H=CO+H2
0.0
HCO+O=CO+OH
0.0
HCO+OH=CO+H2O
0.0
2.53E+12
0.0
1.40E+07
1.95
3.01E+13
0.0
1.85E+17
-1.0
7.58E+12
0.0
7.23E+13
0.0
3.00E+13
0.0
3.00E+13
0.0
! Hg chemistry (Wilcox) (10 reactions)
HGCL+M=HG+CL+M
16130. !Wilcox
HGCL2+M=HG+CL2+M
!Wilcox
HG+HCL=HGCL+H
82060.
!Wilcox
HG+CL2=HGCL+CL
42800.
!Wilcox
HGCL2+M=HGCL+CL+M
!Wilcox
HGCL+HCL=HGCL2+H
!Wilcox
HGCL+CL2=HGCL2+CL
HG+HOCL=HGCL+OH
!Wilcox
HGCL+HOCL=HGCL2+OH
!Wilcox
!HGO+M=HG+O+M
!Wilcox
4.25e13
3.19e12
0.0
0.0
86980.
2.62e12
0.0
1.34e12
0.0
2.87e14
0.0
80550.
4.50e13
0.0
30270.
2.465e10
0.0
3.09e13
! HCL REACTIONS (Roesler et al. 1995)
0.
0.0
!Wilcox
36638
3.48e10
0.0
485
3.09e10
0.0
8750
(29 reactions)
H+CL+M=HCL+M
HCL+H=H2+CL
!298-1500 SENKAN1998
HCL+OH=H2O+CL
!HCL+OH=H2O+CL
!wANG HAI
HCL+O=OH+CL
!350-1480 MKF1990
!HCL+O=OH+CL
!Niksa
!HCL+O=OH+CL
!WANG HAI
CL+HO2=HCL+O2
!CL+HO2=HCL+O2
!Edwards
7.19E21
1.8E12
-2.0
0.3
3804.
2.71E7
2.45E12
1.65
0.0
-220.
1100.
4.5E3
3.13
3110.
3.4E3
2.87
3510.
5.24E12
0.0
6400.
1.08E13
0.0
4.1E13
112
0.
-330.
0.0
-330.
CL2+H=HCL+CL
1500 SENKAN1998
!CL2+H=HCL+CL
HAI
CL+CL+M=CL2+M
1800.
CL2+O=CLO+CL
CLO+O=CL+O2
1200 ABCHKT 1992
!CLO+O=CL+O2
HO2+CL=OH+CLO
H2O2+CL=HO2+HCL
HOCL+CL=CLO+HCL
CLO+H2=HOCL+H
14100.
H+HOCL=HCL+OH
CL+HOCL=CL2+OH
O+HOCL=OH+CLO
OH+HOCL=H2O+CLO
HOCL=OH+CL
HOCL=H+CLO
CLCO+M=CO+CL+M
CLCO+O2=CO2+CLO
CLCO+CL=CO+CL2
CLCO+H=CO+HCL
CLCO+O=CO+CLO
CLCO+O=CO2+CL
CLCO+OH=CO+HOCL
CLO+CO=CO2+CL
HCO+CL=CO+HCL
HCO+CLO=CO+HOCL
6.0E10
1.0
191.
!298-
8.59E13
0.0
1170. !wANG
4.68E14
0.0
2.52E12
3.3E8
0.0
2.0
2720.
191. !300-
5.7E13
2.42E13
6.62E12
7.28E12
6.03E11
0.0
0.0
0.0
0.0
0.0
364.
2300.
1950.
180.
9.55E13
1.81E12
6.03E12
1.81E12
1.76E20
8.13E14
1.30E14
7.94E10
4.00E14
1.00E14
1.00E14
1.00E13
3.30E12
6.03E11
1.00E14
3.16E13
0.0
0.0
0.0
0.0
-3.01
-2.09
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
7620.
260.
4370.
990.
56720.
93690.
8000.
3300.
800.
0.
0.
0.
0.
7400.
0.
0.
3.85E12
0.0
140.
8.99E13
5.00E13
2.50E15
0.0
0.0
0.0
993.
0.
2.40E13
0.0
0.
4.60E13
0.0
890.
5.00E12
0.0
3000.
5.4E12
5.5E10
0.0
0.0
2250.
-480.
-
!NO-CL reaction (9 reactions)
CLO+NO=NO2+CL
!niksa
HNO+CL=HCL+NO
HONO+CL=HCL+NO2
NOCL+M=NO+CL+M
31991.
NOCL+CL=NO+CL2
!niksa
NOCL+H=NO+HCL
!niksa
NOCL+O=NO+CLO
!niksa
NOCL+OH=HOCL+NO
NOCL+OH=HONO+CL
!800-1500 K
! NOx chemistry (Muller, 2000)
!N-O-H reaction (Muller and Dryer et al,2000) (24 REACTIONS)
NO+O+M=NO2+M
NO+H+M=HNO+M
NO+OH+M=HONO+M
3.00E13
1.52E15
1.99E12
113
0.0
-0.41
-0.05
0.
0.
-721.
NO2+H2=HONO+H
15000.
NO2+O=O2+NO
!niksa
!NO2+O=O2+NO
NO2+O+M=NO3+M
NO2+H=NO+OH
NO2+OH+M=HNO3+M
NO2+OH=HO2+NO
!NIKSA
!NO+HO2=NO2+OH
!MULLER (2000)
NO2+NO2=NO3+NO
20900.
NO2+NO2=2NO+O2
26100.
HNO+H=NO+H2
HNO+O=OH+NO
HNO+OH=H2O+NO
HNO+NO=N2O+OH
26000.
HNO+NO2=HONO+NO
HNO+HNO=H2O+N2O
HONO+O=OH+NO2
HONO+OH=H2O+NO2
N2O+M=N2+O+M
56000.
N2O+O=N2+O2
28000.
N2O+O=NO+NO
28000.
N2O+H=N2+OH
16800.
!NIKSA
!N2O+H=N2+OH
N2O+OH=N2+HO2
40000.
SO2+O(+M) =
2400.
1.05E14
-0.52
3.9E12
1.33E13
1.32E14
4.52E13
1.81E13
0.0
0.0
0.0
0.0
0.0
2.11E12
0.0
9.64E9
0.73
1.63E12
0.0
4.46E11
1.81E13
1.30E7
2.00E12
0.72
0.0
1.88
0.0
655.
0.
-956.
6.02E11
8.51E8
1.20E13
1.70E12
7.91E10
0.0
0.0
0.0
1.0
0.0
1990.
3080.
5960.
-520.
1.00E14
0.0
1.00E14
0.0
2.53E10
2.00E12
0.
-240.
0.
362.
0.
6680.
-479.
0.0
0.0
0.0
5.01E13
9.03E13
0.0
7.23E12
1.24E23
8.39E15
0.0
-3.29
-0.75
4550.
0.0
0.
2350.
1930.
(66 reactions)
SO3(+M)
N2/1.3/ SO2/10/ H2O/10/
LOW / 4.000E+28 -4.00
SO2+OH(+M) =
715.00
2.76
2.23E14
CO+N2O=CO2+N2
44000.
CO+NO2=CO2+NO
33800.
HCO+NO=HNO+CO
HCO+NO2=HONO+CO
HCO+NO2=H+NO+CO2
! SOx chemistry
1.30E4
9.200E+10
0.0000
5250. /
HOSO2(+M)
!muller and niksa
7.200E+12
N2/1.5/ SO2/10/ H2O/10/
114
0.0000
LOW /
TROE /
4.500E+25
0.7000
-3.30
359.84 /
1.0e-30 1e+30 /
SO2+OH = HOSO+O
76000.00
SO2+OH = SO3+H
23850.00
SO2+CO = SO+CO2
48300.
SO2*+M = SO2+M
3600.00
SO2*+SO2 = SO3+SO
2430.00
SO3+H = HOSO+O
50300.0
3.900E+08
1.8900
4.900E+02
2.6900
2.700E+12
0.0000
1.300E+14
0.0000
2.600E+12
0.0000
2.500E+05
2.9200
SO+O(+M) = SO2(+M)
0.00
!niksa, leeds
N2/1.5/ SO2/10/ H2O/10/
LOW / 1.200E+21 -1.54
0.00 /
TROE /
0.5500
1.0e-30 1e+30 /
3.200E+13
0.0000
SO+M =
S+O+M
107000.
N2/1.5/ SO2/10/ H2O/10/
4.000E+14
0.0000
SO+H+M = HSO+M
0.00
N2/1.5/ SO2/10/ H2O/10/
5.000E+15
0.0000
2SO =
2.000E+12
0.0000
SO2+S
4000.00
HSO+H = HSOH
920.00
HSO+H = SH+OH
HSO+H = S+H2O
-340.
HSO+H = H2SO
HSO+H = H2S+O
10400.
HSO+O+M = HSO2+M
HSO+O = SO2+H
HSO+O+M = HOSO+M
HSO+O = O+HOS
5340.
HSO+O = OH+SO
300.
HSO+OH = HOSHO
HSO+OH = HOSO+H
3750.
HSO+OH = SO+H2O
470.
HSO+O2 = SO2+OH
0.0
!NIKSA, MULLER
HSOH = SH+OH
75200.
2.500E+20
-3.1400
4.900E+19
1.600E+09
-1.8600
1560.
1.3700
1.800E+17
1.100E+06
-2.4700
50.
1.0300
1.100E+19
4.500E+14
6.900E+19
4.800E+08
-1.7300
-50.
-0.4000
0.00
-1.6100
1600.
1.0200
1.400E+13
0.1500
5.200E+28
5.300E+07
-5.4400
3170.
1.5700
1.700E+09
1.0300
1.000E+12
0.0000
2.800E+39
115
-8.7500
HSOH =
S+H2O
54500.
HSOH = H2S+O
86500.
H2SO = H2S+O
71700.
HOSO(+M) = HSO2(+M)
50000.
N2/1/ SO2/10/ H2O/10/
LOW / 1.700E+35 -5.64
27881.23 /
TROE /
0.4000
1.0e-30 1e+30 /
HOSO+M = O+HOS+M
119000.
!MULLER
5.800E+29
-5.6000
9.800E+16
-3.4000
4.900E+28
-6.6600
1.000E+09
1.0300
2.500E+30
-4.8000
HOSO+H = SO+H2O
-1900.
HOSO+OH = SO2+H2O
0.00
HOSO+O2 = HO2+SO2
1000.
6.300E-10
6.2900
1.000E+12
0.0000
1.000E+12
0.0000
HSO2(+M) = H+SO2(+M)
18361.
!muller
N2/1/ SO2/10/ H2O/10/
LOW / 3.500E+25 -3.29
HOSO2 = HOSO+O
106300.
HOSO2+H = SO2+H2O
0.00
HOSO2+O = SO3+OH
0.00
HOSO2+OH = SO3+H2O
0.00
HOSO2+O2 = HO2+SO3
HOSHO = HOSO+H
73800.
2.000E+11
-0.9000
5.400E+18
-2.3400
9612.48 /
0.0000
5.000E+12
0.0000
1.000E+12
0.0000
7.80E+11
6.400E+30
HOSHO+H = HOSO+H2
0.00
HOSHO+O = HOSO+OH
0.00
SO2+NO2=NO+SO3
27000.
!NIKSA
SO+NO2 = SO2+NO
0.00
HSO+NO2 = HOSO+NO
0.00
! modified ( 8
1.000E+12
0.0000
-5.8900
1.000E+12
0.0000
5.000E+12
0.0000
6.3E12
0.0
8.432E+12
0.00
5.8E12
0.00
2.000E+12
0.0000
1.000E+12
0.0000
7.600E+03
2.3700
reactions)
SO3+O = SO2+O2
19870.
SO3+SO = 2SO2
10000.00
SO+O2 = SO2+O
3000.00
116
656.0
HOSO(+M) = SO+OH(+M)
76380.00
LOW / 1.156E+46 -9.02
53350.00 /
TROE /
9.5000E-01 2.9890E+03 1.1000E+00
SO+OH = SO2+H
H+SO2(+M) = HOSO(+M)
7200.00
LOW / 2.662E+38 -6.43
11150.00 /
TROE /
8.2000E-01 1.3088E+05 2.6600E+02
HOSO2 = SO3+H
55000.00
HSO+H = SO+H2
0.00
! New ( 7 reactions)
HOSO+H = SO2+H2
0.00
HSO2+H = SO2+H2
0.00
HSO2+OH = SO2+H2O
0.00
HSO2+O2 = HO2+SO2
0.00
HOSHO = SO+H2O
59500.
HOSHO+OH = HOSO+H2O
0.00
HOSO2+H = SO3+H2
0.00
9.940E+21
-2.5400
/
1.077E+17
3.119E+08
-1.35
/
1.400E+18
0.0
1.6100
-2.9100
1.000E+13
0.0000
3.000E+13
0.0000
3.000E+13
0.0000
1.000E+13
0.0000
1.000E+13
0.0000
1.200E+24
-3.5900
1.000E+12
0.0000
1.0E+12
0.00
!S-CL-O reactions (quantum chemistry) (3 reactions)
SO+CLO=SO2+CL
SCL+O=SO+CL
SO+CL2=SCL+CLO
!
NIST
1.29E10
2.84E11
1.63E9
0.0
0.0
0.0
15744.
12350.
27320.
CxHy chemistry ( REACTIONS)
!*** C1 hydrocarbons
***********************************************************
!
CH4
!CH4
CH4
CH4
CH4
*** Methane ***
+ H
= CH3 + H2
2.20E04
3.00
+ H
= CH3 + H2
1.32E04
3.00
+ O
= CH3 + OH
1.02E09
1.50
+ OH
= CH3 + H2O
1.60E06
2.10
+ O2
= CH3 + HO2
7.90E13
0.00
56000.
!CH4 + HO2
= CH3 + H2O2
1.80E11
0.00
18700.
!CH4 + O2
= CH3 + HO2
3.92E13
0.00
56894.
!92BAU/COB
CH4 + HO2
= CH3 + H2O2
1.13E13
0.00
24641.
!88BAL/JON (ok)
!CH4+O2 shows factor of two different, CH4+HO2 shows lots different
!which value to use?
117
8750.
8040.
8604.
2460.
!
CH3
*** Methyl ***
+ H (+M) = CH4 (+M)
0.
!MBA002 84WAR (up)
LOW/8.00E26
-3.0
0./
SRI/0.45 797. 979. /
H2/2.0/ CO/2.0/ CO2/3.0/ H2O/5.0/
!CH3 + H (+M) = CH4 (+M)
!86TSA/HAM
!factor of 2 different, which to use?
CH3 + H
= CH2
+ H2
15100.
!MBA013 (mb?)
CH3 + O
= CH2O + H
!MBA009 (mb?)
CH3 + OH
= CH2
+ H2O
5000.
!MBA012 (mb?)
!CH3 + OH
= CH3OH
11673. !87DEA/WES (1atm)
!CH3 + OH
= CH2OH + H
!87DEA/WES (1atm)
!CH2OH+H
= CH3+OH
!MBA010
CH3 + OH
= CH3O + H
13931. !87DEA/WES (1atm)
!CH3O+H
= CH3+OH
!MBA011
CH3 + OH
= CH2SING + H2O
!87DEA/WES (1atm)
!CH3 + O2
= CH3O + O
29229. !MBA008 86TSA/HAM
CH3 + O2 <=> CH3O + O
29229.
!bozzelli
6.00E16
-1.00
!(89STE/SMI2)
1.21E15
-0.40
9.00E13
0.00
8.00E13
0.00
7.50E06
2.00
2.24E40
-8.20
2.64E19
-1.80
8068.
1.00E14
0.00
0.
5.74E12
-0.23
1.00E14
0.00
0.
8.90E19
-1.80
8067.
2.05E18
-1.57
2.05E+19
!CH3
+ O2
= CH3O + O
30850. !92HO/YU (BOZ)
!CH3 + O2
= CH3O + O
31600
!92BAU/COB
!CH3 +
O2
= CH2O +
OH
!92BAU/COB
CH3
+
O2
= CH2O +
OH
10150. !92HO/YU (BOZ)
!CH3
+
O2
= CH3O +
O
31600.
!92BAU/COB
!CH3
+
O2(+M)=CH3OO(+M)
!92BAU/COB
CH3 + HO2
= CH3O + OH
!MBA007 86TSA/HAM
CH3
+
CH3
= C2H4 +
H2
32005.
!92EGO/DU
!CH3 + CH3(+M) = C2H6 (+M)
!MBA001 88WAG/WAR (ok)
! LOW/3.18E41
-7.0 2762./
! TROE/0.6041 6927. 132./
!H2/2.0/ CO/2.0/ CO2/3.0/ H2O/5.0/
CH3+CH3<=>C2H6
6130.0
!Bozzelli
!CH3+HCO=CH4+CO
!(GRIMECH11)
0.
0.
-1.570
2.88E15
-1.15
7.20E13
0.00
3.30E11
0.
3.59E09
-0.14
1.32E14
0.
7.80E08
1.2
0.
2.00E13
0.00
0.
1.00E16
0.
9.03E16
-1.20
9000.
654.
!88WAG/WAR
2.68E+29
2.648E+13
118
-5.0
0.000
0.00
CH3+HCO=CH4+CO
!86TSA/HAM
C+CH3=H+C2H2
!(GRIMECH1)
1.20E14
0.
0.
5.000E+13
0.000
0.00
!
*** CH2 (triplet) ***
C+CH2=H+C2H
5.000E+13
0.000
0.00
!(GRIMECH1)
H+CH2(+M)=CH3(+M)
2.500E+16
-0.800
0.00
!(GRIMECH11)
LOW / 3.200E+27
-3.140
1230.00/
!(GRIMECH11)
TROE/ 0.6800
78.00 1995.00 5590.00 /
!(GRIMECH11)
H2/2.00/ H2O/6.00/ CH4/2.00/ CO/1.50/ CO2/2.00/ C2H6/3.00/ AR/0.70/
!(GRIMECH11)
CH2+OH = CH2O+H
2.50E13
0.00
0.
!MBA026
CH2+O = CO+2H
5.00E13
0.00
0.
!MBA043
CH2+CO2 = CH2O+CO
1.10E11
0.00
1000.
!MBA042
CH2+O = CO+H2
3.00E13
0.00
0.
!MBA044
CH2+O2 = CO2+2H
1.60E12
0.00
1000.
!MBA045
CH2+O2 = CH2O+O
2.00E14
0.00
10000. !MBA046*x
!(above match to c2h2 Taka)
!$CH2+O2 = CH2O+O
5.00E13
0.00
9000.
!MBA046
CH2+O2 = CO2+H2
6.90E11
0.00
500.
!MBA047
CH2+O2 = CO+H2O
1.90E10
0.00
1000. !MBA048
CH2+O2 = CO+OH+H
8.60E10
0.00
-500.
!MBA049
CH2+O2 = HCO+OH
4.30E10
0.00
-500.
!MBA050
CH2+CH3 = C2H4+H
3.00E13
0.00
0.
!MBA072
2CH2 = C2H2+H2
4.00E13
0.00
0.
!MBA114
CH2
+
HO2
= CH2O +
OH
3.01E13
0.
0.
!92EGO/DU
CH2
+
H2O2 = CH3O +
OH
3.01E13
0.
0.
!92EGO/DU
!CH2
+
CO2
= CH2O +
CO
1.10E11
0.
1000.
!92EGO/DU
CH2
+
CH2O = CH3
+
HCO
1.20E12
0.
0.
!92EGO/DU
CH2
+
HCO
= CH3
+
CO
1.81E13
0.
0.
!92EGO/DU
!QUESTION? Does CH2 or CH2SING react w/ HO2 H2O2 CH2O HCO
!
!*** CH Reactions ***
!********************
119
CH2+H = CH+H2
1.00E18
-1.56
0.
!MBA024
CH2+OH = CH+H2O
1.13E07
2.00
3000.
!MBA025
CH+O2 = HCO+O
3.30E13
0.00
0.
!MBA027 82BER/FLE (ok)
CH+O = CO+H
5.70E13
0.00
0.
!MBA028 83MES/FIL
H+CH=C+H2
1.100E+14
0.000
0.00
!(GRIMECH1)
CH+OH = HCO+H
3.00E13
0.00
0.
!MBA029
CH+CO2 = HCO+CO
3.40E12
0.00
690.
!MBA030 82BER/FLE (ok)
CH+H2O = CH2O+H
1.17E15
-0.75
0.
!MBA032 89MIL/BOW
CH+CH2O = CH2CO+H
9.46E13
0.00
-515.
!MBA033 88ZAB/FLE (up)
CH+CH2 = C2H2+H
4.00E13
0.00
0.
!MBA035
CH+CH3 = C2H3+H
3.00E13
0.00
0.
!MBA036
CH+CH4 = C2H4+H
6.00E13
0.00
0.
!MBA037 80BUT/FLE (up)
C2H3+CH = CH2+C2H2
5.00E13
0.00
0.
!MBA086
HCCO+CH = C2H2+CO
5.00E13
0.00
0.
!MBA104
CH+CO(+M)=HCCO(+M)
5.000E+13
0.000
0.00
!(GRIMECH1)
LOW / 2.690E+28
-3.740
1936.00/
!(GRIMECH1)
TROE/ 0.5757 237.00 1652.00 5069.00 /
!(GRIMECH1)
H2/2.00/ H2O/6.00/ CH4/2.00/ CO/1.50/ CO2/2.00/ C2H6/3.00/ AR/0.70/
!(GRIMECH1)
!*** C1 oxy-hydrocarbons
*******************************************************
!
CH3O+M
*** CH3O, CH2OH ***
= CH2O+H+M
!MBA014
= CH2O+HO2
!MBA022
= CH2O+HO2
!92BAU/COB
= CH2O+HO2
!bozzelli
= CH2O+H2
25000.
!CH3O+O2
2600.
CH3O+O2
2140.
!CH3O+O2
1500.
CH3O+H
!MBA016
H+CH3O=H+CH2OH
!(GRIMECH11)
H+CH3O=CH2SING+H2O
0.00
!(GRIMECH11)
H+CH3O(+M)=CH3OH(+M)
0.00
!(GRIMECH11)
LOW / 8.600E+28
-4.000
3025.00/
120
1.00E14
0.00
6.30E10
0.00
4.00E10
0.00
1.48E13
0.00
2.00E13
0.00
0.
3.400E+06
1.600
0.00
1.600E+13
0.000
5.000E+13
0.000
!(GRIMECH11)
TROE/ 0.8902 144.00 2838.00 45569.00 /
!(GRIMECH11)
H2/2.00/ H2O/6.00/ CH4/2.00/ CO/1.50/ CO2/2.00/ C2H6/3.00/
!(GRIMECH11)
CH3O+O
= CH2O+OH
1.00E13
0.00
0.
!MBA020
CH3O+OH
= CH2O+H2O
1.00E13
0.00
0.
!MBA018
CH3O +
HO2
= CH2O + H2O2
3.01E11
0.
0.
!92EGO/DU
CH3O +
CO
= CH3
+ CO2
1.57E13
0.
11797. !92EGO/DU
CH3O +
C2H5
= CH2O + C2H6
2.41E13
0.
0.
!92EGO/DU
CH3O +
C2H3
= CH2O + C2H4
2.41E13
0.
0.
!92EGO/DU
CH3O +
C2H
= CH2O + C2H2
2.41E13
0.
0.
!92EGO/DU
CH3O +
CH3
= CH4
+ CH2O
2.40E13
0.
0.
!86TSA/HAM
!QUESTION? What about reaction w/ HO2 CO C2H5 C2H3 CH3
CH2OH+M
= CH2O+H+M
25000.
!MBA015
!CH2OH+O2
= CH2O+HO2
1500.
!MBA023
CH2OH+O2
= CH2O+HO2
5000.
!LAW
!CH2OH+O2
= CH2O+HO2
!94BAU/COB
!
DUPLICATE
!CH2OH+O2
= CH2O+HO2
3577.
!94BAU/COB
!
DUPLICATE
!CH2OH+O2
= CH2O+HO2
0.
!87TSA
!CH2OH+H
= CH2O+H2
!MBA017
CH2OH+H
= CH3 + OH
!87TSA
!CH2OH+H
= CH2O + H2
!87TSA
!CH2OH+H
= CH2O + H2
!Bozzelli
!CH2OH+O
= CH2O+OH
!MBA021
!CH2OH+OH
= CH2O+H2O
!MBA019
CH2OH +
HO2 = CH2O +
!92EGO/DU
CH2OH +
HCO = CH3OH +
!92EGO/DU
CH2OH +
HCO = CH2O +
!87TSA
CH2OH +
CH3 = C2H5 +
!92EGO/DU
CH2OH +
CH2O = HCO
+
!92EGO/DU
1.00E14
0.00
1.48E13
0.00
2.41E14
0.00
1.57E15
-1.00
7.23E13
0.00
1.2E12
0.00
2.00E13
0.00
0.
9.64E13
0.
0.
6.03E12
0.
0.
2.0E13
0.
0.
1.00E13
0.00
0.
1.00E13
0.00
0.
H2O2
1.20E13
0.
0.
CO
1.20E14
0.
0.
CH2O
1.81E14
0.
0.
OH
1.37E14
-.41
6589.
CH3OH
5.54E03
2.81
5862.
121
00.
CH2OH
+
CH2OH = CH3OH +
!92EGO/DU
!CH2OH +
H
= CH3
+
-2971. !92EGO/DU
CH2OH +
O
= CH2O +
!87TSA
CH2OH +
OH
= CH2O +
!87TSA
CH2O
1.20E13
0.
0.
OH
2.39E02
3.353
OH
4.20E13
0.
0.
H2O
2.40E13
0.
0.
!
CH2O+M
*** CH2O ***
= HCO+H+M
3.31E16
0.00
81000.
!MBA053 80DEA/JOH (ok)
CH2O+H
= HCO+H2
2.19E08
1.77
3000.
!MBA052 86TSA/HAM
CH2O+O
= HCO+OH
1.80E13
0.00
3080.
!MBA054 80KLE/SOK (up)
CH2O+OH
= HCO+H2O
3.43E09
1.18
-447.
!MBA051 86TSA/HAM
CH2O+HO2
= HCO+H2O2
1.99E12
0.00
11665. !86TSA/HAM
!HCO+H2O2
= CH2O+HO2
1.02E11
0.00
6927.
!86TSA/HAM(rev)
!QUESTION? need to check CH2O+HO2=HCO+H2O2 missing from MB mechanism
CH2O+O2
= HCO+HO2
2.04E13
0.00
38900.
!74BAL/FUL (ok)
!QUESTION? need to check CH2O+O2=HCO+HO2 missing from MB mechanism
CH2O+CH3
= HCO+CH4
5.54E03
2.81
5862.
!86TSA/HAM (ok)
!CH2O+CH3
= HCO+CH4
4.09E12
0.00
8843.
!92BAU/COB
H2+CO(+M)=CH2O(+M)
4.300E+07
1.500
79600.00
!(GRIMECH11)
LOW /
5.070E+27
-3.420
84350.00/
!(GRIMECH1)
TROE/ 0.9320 197.00 1540.00 10300.00 /
!(GRIMECH1)
H2/2.00/ H2O/6.00/ CH4/2.00/ CO/1.50/ CO2/2.00/ C2H6/3.00/ AR/0.70/
!(GRIMECH1)
!QUESTION? need to check CH2O+CH3=HCO+CH4 missing from MB mechanism
!*** C2 hydrocarbons
***********************************************************
!
*** C2H6 ***
C2H6 + H
= C2H5 + H2
5.40E02
!MBA066 73CAL/DOV (ok)
C2H6 + O
= C2H5 + OH
3.00E07
!MBA067 84WAR (ok)
C2H6 + OH
= C2H5 + H2O
8.70E09
!MBA068 83TUL/RAV (ok)
C2H6 + CH3
= C2H5 + CH4
5.50E-1
!MBA065 73CLA/DOV (ok)
C2H6 +
O2
= C2H5 +
HO2
4.03E13
50842.
!92EGO/DU
C2H6 +
HO2
= C2H5 +
H2O2
2.95E11
14935.
!92EGO/DU
!QUESTION? What about ignition steps C2H6+O2 & HO2
122
3.50
5210.
2.00
5115.
1.05
1810.
4.00
8300.
0.
0.
!
*** C2H5 ***
H+C2H5(+M)=C2H6(+M)
5.210E+17
-0.990
1580.00
!(GRIMECH11)
LOW / 1.990E+41
-7.080
6685.00/
!(GRIMECH11)
TROE/ 0.8422 125.00 2219.00 6882.00 /
!(GRIMECH11)
H2/2.00/ H2O/6.00/ CH4/2.00/ CO/1.50/ CO2/2.00/ C2H6/3.00/ AR/0.70/
!(GRIMECH11)
C2H5+H
= CH3+CH3
1.00E14
0.00
0.
!MBA074
C2H5 +
H
= C2H4 +
H2
1.81E12
0.
0.
!92EGO/DU
!C2H5+H
= CH3+CH3
3.60E13
0.00
0.
!92BAU/COB
!C2H5
+ O = CH3CHO
+ H
8.00E12
0.
0.
!86TSA/HAM (review)
!C2H5
+ O = CH2O
+ CH3
1.60E13
0.
0.
!86TSA/HAM (review)
C2H5
+ O = CH3CHO
+ H
5.50E13
0.
0.
!94BAU/COB
C2H5
+ O = CH2O
+ CH3
1.10E13
0.
0.
!94BAU/COB
!C2H5+O2
= C2H4+HO2
2.56E19
-2.77
1977.
!90BOZ/DEA (250-1200)
!C2H5+O2
= C2H4+HO2
8.43E11
0.00
3875.
!MBA075 80BAL/PIC (ok)
C2H5 +
OH
= C2H4 +
H2O
2.41E13
0.
0.
!92EGO/DU
C2H5 +
HO2
= CH3
+ CH2O + OH
2.40E13
0.
0.
!92EGO/DU
!QUESTION? What about C2H5+HO2= [C2H5O]+OH = CH3+CH2O+OH
!QUESTION? What about C2H5+OH=C2H4+H2O
!
C2H4+M
*** C2H4 ***
= C2H2+H2+M
1.50E15
0.00
55800. !MBA128 83KIE/KAP (up)
!need 2 check 77JUS/ROT 77TAN 80TAN/GAR (Gardiner) lo (ok) better & selfconsistent
C2H4+M
= C2H3+H+M
1.40E16
0.00
82360. !MBA129
!need to check 77JUS/ROT 80TAN/GAR (Gardiner) lo (ok) better & selfconsistent
!C2H4+H(+M)
= C2H5(+M)
8.40E08
1.5
990.
!86TSA/HAM (ref)
!
LOW/6.37E27
-2.8
-54./
!MBA073
!
H2/2.0/ CO/2.0/ CO2/3.0/ H2O/5.0/
!MBA073
!C2H4+H
= C2H3+H2
1.10E14
0.00
8500.
!MBA069 73PEE/MAH (up)
H+C2H4(+M)=C2H5(+M)
1.080E+12
0.454
1820.00 !(GRIMECH11)
LOW / 1.200E+42
-7.620
6970.00/
!(GRIMECH11)
TROE/ 0.9753 210.00
984.00 4374.00 /
!(GRIMECH11)
H2/2.00/ H2O/6.00/ CH4/2.00/ CO/1.50/ CO2/2.00/ C2H6/3.00/ AR/0.70/
!(GRIMECH11)
H+C2H4=C2H3+H2
1.325E+06
2.530
12240.00
!(GRIMECH11)
123
!C2H4+H
= C2H3+H2
5.42E14
14904. !92BAU/COB
!need to check 92BAU/COB lo (ok)s best
C2H4+O
= CH3+HCO
1.60E09
!MBA070 84WAR (up)
!need to check and compare with more recent numbers
!C2H4+OH
= C2H3+H2O
2.02E13
5955.
!MBA071 88TUL
C2H4+OH
= C2H3+H2O
4.50E06
2850.
!(k19fit)
CH3+C2H4=C2H3+CH4
2.270E+05
9200.00
!(GRIMECH11)
C2H4 +
O2
= C2H3 +
HO2
4.22E13
57594.
!92EGO/DU
C2H4 +
CO
= C2H3 +
HCO
1.51E14
90562.
!92EGO/DU
0.00
1.20
746.
0.00
2.00
2.000
0.
0.
!
C2H3+H
*** C2H3 ***
= C2H2+H2
1.20E13
0.00
0.
!92BAU/COB
! C2H3+H
= C2H2+H2
4.00E13
0.00
0.
!MBA080
C2H3+OH
= C2H2+H2O
5.00E12
0.00
0.
!MBA083
!need to check 86TSA/HAM says 3.0E13 0.
C2H3+CH2
= C2H2+CH3
3.00E13
0.00
0.
!MBA084
!****** New Value ***
C2H3+O2
= CH2O+HCO
1.05E38
-8.22
7030.
!92WES (k-a/s)
DUP
C2H3+O2
= CH2O+HCO
4.48E26
-4.55
5480.
!92WES (direct)
DUP
!C2H3+O2
= CH2O+HCO
4.00E12
0.00
-250.
!MBA082 84SLA/PAR (ok)
!********************
C2H3+O
= CH2CO+H
3.00E13
0.00
0.
!MBA081 84WAR
C2H3 +
O2
= C2H2 +
HO2
1.20E11
0.
0.
!92EGO/DU
C2H3 +
HO2
= CH2CO + OH + H
3.00E13
0.
0.
!92EGO/DU
!QUESTION? What about C2H3 + HO2 = C2H3O + OH = CH2CO + H + OH
!QUESTION? What about C2H3 + HO2 = C2H4 + O2? or reverse (initiation step)
!QUESTION? What about C2H3 + HCO = C2H4 + CO
!
*** C2H2 ***
C2H2+H(+M)
= C2H3(+M)
2410.
!MBA079 76PAY/STI (ok)
LOW/2.67E27 -3.5 2410./
H2/2.0/ CO/2.0/ CO2/3.0/ H2O/5.0/
C2H2+OH
= HCCOH+H
13500.
!MBA088
C2H2+OH
= CH2CO+H
-1000.
!MBA089
124
5.54E12
0.00
5.04E05
2.30
2.18E-4
4.50
C2H2+OH
-2000.
C2H2+O
1900.
C2H2+O
1900.
O+C2H2=OH+C2H
28950.00
C2H2+O2
30100.
C2H2
137510.
C2H2 +
H
22243.
C2H2 +
OH
12035.
C2H2 +
O2
74475.
= CH3+CO
!MBA090
= CH2+CO
!MBA076
= HCCO+H
!MBA077
4.83E-4
4.00
1.02E07
2.00
1.02E07
2.00
4.600E+19
!(GRIMECH11)
= HCCO+OH
!MBA126
= C2H
+
H
!92EGO/DU
= C2H
+
H2
!92EGO/DU
= C2H
+
H2O
!92EGO/DU
= C2H
+
HO2
!92EGO/DU
C2H
+
O
= CH
+
CO
!92EGO/DU
OH+C2H=H+HCCO
0.00
!(GRIMECH11)
OH + C2H = CH2 + CO
!86TSA/HAM
C2H
+
O2
= CO
+
HCO
!92EGO/DU
-1.410
2.00E08
1.50
1.80E41
-7.76
6.02E13
0.
1.45E4
2.68
1.20E13
0.
1.81E13
0.
2.000E+13
0.
0.000
2.00E13
0.
0.
2.41E12
0.
0.
!*** C2 oxy-hydrocarbons
*******************************************************
!
*** HCCOH, CH2CO ***
HCCOH+H
= CH2CO+H
1.00E13
0.00
!MBA091
CH2CO+H
= CH3+CO
1.13E13
0.00
3428.
!MBA094
CH2CO+H
= HCCO+H2
5.00E13
0.00
8000.
!MBA095
CH2CO+O
= CO2+CH2
1.75E12
0.00
1350.
!MBA093
CH2CO+O
= HCCO+OH
1.00E13
0.00
8000.
!MBA096
!Dryer&Yetter have 3 chans CH2CO+O = HCO+HCO & CH2O+CO & HCCO+OH
!QUESTION? who is right?
CH2CO+OH
= HCCO+H2O
7.50E12
0.00
2000.
!MBA097
!QUESTION? Dyer&Yetter have also CH2CO+OH=CH2O+HCO (86GLA/MIL)
CH2CO(+M)
= CH2+CO(+M)
3.00E14
0.00
70980.
!MBA098
LOW/3.60E15
0.0 59270./
CH2CO +
O
= HCO
+
HCO
2.00E13
0.
!92EGO/DU
CH2CO +
O
= CH2O +
CO
2.00E13
0.
!92EGO/DU
CH2CO +
OH
= CH2O +
HCO
2.80E13
0.
!92EGO/DU
125
0.
2293.
0.
0.
HCCO
HCCO
+
OH
!92EGO/DU
+
CH2
!92EGO/DU
!
HCCO+H
= HCO
+
CO + H
1.00E13
0.
0.
= C2H
+
CH2O
1.00E13
0.
2000.
*** HCCO Reactions ***
= CH2SING+CO
1.00E14
0.00
0.
= H+2CO
1.00E14
0.00
0.
= 2CO+OH
1.60E12
0.00
854.
= C2H2+2CO
1.00E13
0.00
0.
= C2H3+CO
3.00E13
0.00
0.
!MBA101
HCCO+O
!MBA102
HCCO+O2
!MBA103
2HCCO
!MBA105
HCCO+CH2
!MBA115
! CxHy-Cl
chemistry (Bozzelli--68 REACTIONS)
CH4 + CL <=> HCL + CH3
CH4 + CLO <=> CH3 + HOCL
15000.
CH3 + CLO <=> CH3O + CL
2.57E+13
1.40E+13
0.0
0.0
3850.
2.28E+07
1.54
-820.
CH3 + CLO <=> HCL + CH2O
CH3CL <=> CH3 + CL
5.50E+14
5.53E+31
-0.51
-5.63
710.
88810.
CH3CL <=> CH2 + HCL
1.82E+25
-4.69
132460.
CH3CL <=> CH2CL + H
1.31E+30
-5.23
106100.
CH3CL + OH <=> CH2CL + H2O
1.32E+12
0.0
2300.
CH3CL + O <=> OH + CH2CL
1.70E+13
0.0
7300.
CH3CL + H <=> H2 + CH2CL
10600.
CH3CL + O2 <=> HO2 + CH2CL
52200.
CH3CL + HO2 <=> H2O2 + CH2CL
16700.
CH3CL + CLO <=> HOCL + CH2CL
6.66E+13
0.0
4.00E+13
0.0
1.00E+13
0.0
5.00E+12
0.0
8700.
CH3CL + CL <=> HCL + CH2CL
3.16E+13
0.0
3300.
CH3CL + CH3 <=> CH4 + CH2CL
3.31E+11
0.0
9400.
CH3CL + H <=> HCL + CH3
5.40E+13
0.0
6500.
CH2CL + O2 <=> CLO + CH2O
8.46E+13
-1.03
8180.
CH2CL + O2 = CH2CLO + O
34427.
!"
1.15E24
-3.45
CH2CL + O2 = CHCLO + OH
24786.
!"
7.33E13
-0.44
126
CH2CL + HO2 = CHCLO + H2O
!"
1.35E04
2.08
-532.
CH2CL + CLO = CH2CLO + CL
!CHEMACT CH2CLC
CH2CL + H <=> CH3 + CL
1.34E11
0.40
-672.
1.68E+16
-0.68
1020.
CH2CL + HO2 <=> CH2CLO. + OH
5.19E+14
-0.51
840.
CH2CL + OH <=> CH2O + HCL
4.10E+21
-2.57
3740.
CH2CL + OH <=> CH2OH + CL
9.24E+11
CH2CL + CH3 <=> C2H5CL
8.47E+34
-6.75
CH2CL + CH3 <=> C2H4 + HCL
4.80E+24
-3.44
7690.
CH2CL + O <=> CH2CLO.
2.55E+15
-2.02
1230.
CH2CL + O <=> CH2O + CL
8.31E+13
-0.18
800.
CH2CLO. <=> CH2O + CL
2.51E+24
-4.78
10070.
CHCLO + H = CHO + HCL
!HO
CHCLO + H = CH2O + CL
!"
CHCLO = CHO + CL
92920.
!"
CHCLO = CO + HCL
92960.
!"
CHCLO + OH = CCLO + H2O
!WON '91
CHCLO + OH = HCO2 + HCL
-1516.
!CHEMACT '94
CHCLO + O = CCLO + OH
!WON '91
CHCLO + O2 = CCLO + HO2
41800.
!WON '91
CHCLO + CL = CCLO + HCL
!"
CHCLO + CH3 = CCLO + CH4
!"
CHCLO + CH3 = CHO + CH3CL
!"
CHCLO + CLO = CCLO + HOCL
!DEMORE '87
CH2O + CL <=> HCO + HCL
0.38
2970.
8080.
8.33E13
0.00
7400.
6.99E14
-0.58
6360.
8.86E29
-5.15
1.10E30
-5.19
7.50E12
0.00
1.98E07
1.20
8.80E12
0.00
4.50E12
0.00
1.25E13
0.00
500.
2.50E10
0.00
6000.
1.50E13
0.00
8800.
3.00E11
0.00
7000.
5.00E+13
0.0
500.
CH2O + CLO <=> HOCL + HCO
1.20E+13
0.0
2000.
C2H2 + CL <=> HCL + C2H
28800.
C2H3 + CL <=> C2H3CL
1.00E+13
0.0
6.50E+34
-6.63
8610.
C2H3 + CL <=> C2H2 + HCL
2.40E+24
-3.22
9070.
127
1200.
3500.
C2H4 + CLO <=> CH2CL + CH2O
9.26E+18
-1.98
8430.
C2H4 + CLO <=> C2H4OCL
1.75E+32
-6.32
7900.
C2H4 + CL <=> HCL + C2H3
3.00E+13
C2H5 + CL <=> C2H5CL
8.39E+36
-7.38
9550.
C2H5 + CL <=> C2H4 + HCL
6.12E+24
-3.38
9040.
C2H5 + CL <=> CH3 + CH2CL
1.50E+21
-1.94
17720.
C2H6 + CL <=> HCL + C2H5
7.00E+13
0.0
1000.
CL + C2H3CL <=> HCL + CHCLC.H
5.00E+12
0.0
5870.
CL + C2H5CL <=> HCL + CH2CLC.H2
1.12E+13
0.0
1500.
CHCLC.H <=> CL + C2H2
8.23E+29
-5.99
25760.
CH2CLC.H2 <=> CL + C2H4
6.24E+36
-8.05
26340.
H + C2H3CL <=> HCL + C2H3
1.00E+13
0.0
9800.
H + C2H3CL <=> H2 + CHCLC.H
1.55E+13
0.0
4730.
H + C2H3CL <=> C2H4 + CL
3.01E+13
0.0
4223.
H + C2H3CL <=> CH3C.HCL
5.50E+34
H + CH3C.HCL <=> C2H5CL
5090.
H + CH3C.HCL <=> C2H5 + CL
8.01E+11
3.39E+21
-2.42
8880.
H + CH3C.HCL <=> CH3 + CH2CL
6.67E+19
-1.55
9430.
H + CH3C.HCL <=> C2H4 + HCL
3.72E+30
-5.10
9330.
H + C2H5CL <=> HCL + C2H5
1.00E+13
END
128
0.0
-6.56
5100.
11950.
0.0
0.0
-
8100.
Kinetics Data – Wilcox-Bozelli
ELEMENTS
HG CL O
H
N C S AR END
SPECIES
HG HGCL HGCL2 HGO CL CL2 HCL HOCL CLO CLO2 H2
CCLO COCL
O2
H2O
H2O2
CO
CO2
H
O
OH
HCO
HCCO
N2
NH2
H2NO
NCO
N2H3
C2N2
HNCO
CLCO NOCL
S
SH
H2S
SO
CS
COS
HSNO
SO2* SCL
CH CH2 CH2(S) CH3 CH4
CH2OH CH3O
CH3OH
C2H4
C2H5
C2H6
C3H7
CH2CHO
CH2O
C
HO2
AR
CN
HCN
N2O
NO2
N2H2
O3 HONO NO3 HNO3
SO2
HSO
SO3
HOS
C2H
CH2CO
C2H2
HCCOH
HSO2
HSOH
C2H3
CH3CO
N
HOCN
NH
H2CN
NO
NNH
HNO
NH3
HOSO
H2SO
HOSO2
HOSHO
SN
HS2
S2
CH2SING
CH3CHO
CH3CL CH2CL CH2CLO.
C2H4OCL
CHCLC.H
C2H5CL
C2H3CL
COCL2 CH2CLC.H2
CH3C.HCL
CH2CLO
CHCLO CHO HCO2
END
REACTIONS
!H+O2+M=HO2+M
! H2O/18.6/ H2/2.86/
!SH+H+M=H2+M
0.
H+H+H2=H2+H2
0.
H+H+H2O=H2+H2O
0.
!H+OH+M=H2O+M
0.
! H2O/5/
!H+O+M=OH+M
0.
! H2O/5/
!O+O+M=O2+M
-1788.
!H2O2+M=OH+OH+M
45500.
H2+O2=2OH
47780.
!OH+H2=H2O+H
3626.
3.61E17
-0.72
0.
1.0E18
-1.0
9.2E16
-0.6
6.0E19
-1.25
1.6E22
-2.0
6.2E16
-0.6
1.89E13
0.0
1.3E17
0.0
1.7E13
1.17E9
129
0.0
1.3
!O+OH=O2+H
0.
!O+H2=OH+H
6290.
!OH+HO2=H2O+O2
0.0
!H+HO2=2OH
1073.
!O+HO2=O2+OH
1073.
!2OH=O+H2O
0.
!H+HO2=H2+O2
0.
!HO2+HO2=H2O2+O2
0.
!H2O2+H=HO2+H2
3800.
!H2O2+OH=H2O+HO2
1800.
3.61E14
-0.5
5.06E4
2.7
7.5E12
0.0
1.4E14
0.0
1.4E13
0.0
6.0E+8
1.3
1.25E13
0.0
2.0E12
0.0
1.6E12
0.0
1.0E13
0.0
! C-H-O Chemistry (PRINCETON--28REACTIONS)
H+O2=O+OH
16440.0
!H+O2=O+OH
17041.0
!H+O2=O+OH
14856.0
O+H2=H+OH
6290.0
OH+H2=H2O+H
3430.0
H2O+O=OH+OH
13400.0
H2+M=H+H+M
104000.0
O+O+M=O2+M
0.0
H+O+M=OH+M
0.0
OH+H+M=H2O+M
0.0
H+O2+M=HO2+M
0.0
!H+O2+M=HO2+M
0.0
HO2+H=H2+O2
820.0
HO2+H=OH+OH
300.0
HO2+O=O2+OH
0.0
HO2+OH=H2O+O2
-500.0
HO2+HO2=H2O2+O2
12000.0
1.91E+14
0.0
!PRINCETON
2.65E+16
-0.7
!GRI
9.76E+13
0.0
!Leeds
5.06E+04
2.7
2.16E+08
1.5
2.97E+06
2.0
!Roseler
130
4.57E+19
-1.4
6.17E+15
-0.5
4.72E+18
-1.0
2.21E+22
-2.0
1.48E+12
0.6
1.48E+12
0.6
1.66E+13
0.0
7.08E+13
0.0
3.25E+13
0.0
2.89E+13
0.0
4.20E+14
0.0
!HO2+HO2=H2O2+O2
-1629.
H2O2+M=OH+OH+M
48400.0
H2O2+H=H2O+OH
3970.0
H2O2+H=HO2+H2
7950.0
H2O2+O=OH+HO2
3970.0
H2O2+OH=H2O+HO2
0.0
!H2O2+OH=H2O+HO2
9560.0
CO+O+M=CO2+M
2830.0
! (Niksa 2380)
CO+O2=CO2+O
47700.0
CO+OH=CO2+H
-1350.0
CO+HO2=CO2+OH
22900.0
HCO+M=H+CO+M
17000.0
HCO+O2=CO+HO2
406.0
HCO+H=CO+H2
0.0
HCO+O=CO+OH
0.0
HCO+OH=CO+H2O
0.0
1.3E11
0.0
2.95E+14
0.0
2.41E+13
0.0
4.82E+13
0.0
9.55E+06
2.0
1.00E+12
0.0
5.80E14
0.0
1.80E+10
0.0
2.53E+12
0.0
1.40E+07
1.95
3.01E+13
0.0
1.85E+17
-1.0
7.58E+12
0.0
7.23E+13
0.0
3.00E+13
0.0
3.00E+13
0.0
! Hg chemistry (Wilcox) (10 reactions)
HGCL+M=HG+CL+M
16130. !Wilcox
HGCL2+M=HG+CL2+M
!Wilcox
HG+HCL=HGCL+H
82060.
!Wilcox
HG+CL2=HGCL+CL
42800.
!Wilcox
HGCL2+M=HGCL+CL+M
!Wilcox
HGCL+HCL=HGCL2+H
!Wilcox
HGCL+CL2=HGCL2+CL
HG+HOCL=HGCL+OH
!Wilcox
HGCL+HOCL=HGCL2+OH
!Wilcox
!HGO+M=HG+O+M
!Wilcox
4.25e13
3.19e12
0.0
0.0
86980.
2.62e12
0.0
1.34e12
0.0
2.87e14
0.0
80550.
4.50e13
0.0
30270.
2.465e10
0.0
3.09e13
131
0.
0.0
!Wilcox
36638
3.48e10
0.0
485
3.09e10
0.0
8750
!Bozzelli chlorine chemistry
CL + H2 = HCL + H
5000.
CL + CO = COCL
CL + CL + M = CL2 + M
1600.
CL + HCO = HCL + CO
CLO + H2 = HOCL + H
13500.
CLO + CO = CO2 + CL
7400.
!COCL + CL = COCL2
COCL + CL = CO + CL2
COCL + H = CO + HCL
COCL + H = HCO + CL
-180.
COCL + O2 = CO2 + CLO
COCL + O = CO2 + CL
0.0
O + HCL = OH + CL
6400.
O + CL2 = CLO + CL
2800.
O + CLO = CL + O2
400.
OH + HCL = H2O + CL
1000.
4.80E+13
0.0
1.95E+19
5.75E+14
-3.01
0.0
1.41E+14
1.00E+13
-0.35
7.94E+10
1.00E+13
510.
0.0
6.02E+11
3.40E+28
1.49E+19
3.54E+16
3.42E+09
8070.
-
0.0
-5.61
-2.17
-0.79
3390.
1470.
1060.
1.15
0.0
3300.
0.0
5.25E+12
0.0
1.26E+13
0.0
5.75E+13
0.0
2.20E+12
0.0
!*********************Duplicate Chemistry***********************
!CH3CL + OH = CH2CL + H2O
!CH3CL + O = OH + CH2CL
!CH3CL + H = H2 + CH2CL
10600.
!CH3CL + O2 = HO2 + CH2CL
52200.
!CH3CL + HO2 = H2O2 + CH2CL
16700.
!CH3CL + CLO = HOCL + CH2CL
!CH3CL + CL = HCL + CH2CL
!CH3CL + CH3 = CH4 + CH2CL
!CH3CL + H = HCL + CH3
!CH3CL = CH3 + CL
88810.
!CH3CL = CH2 + HCL
132460.
!CH3CL = CH2CL + H
106100.
!CH2CL + O2 = CLO + CH2O
!CH2CL + H = CH3 + CL
!CH2CL + HO2 = CH2CLO. + OH
!CH2CL + OH = CH2O + HCL
!CH2CL + OH = CH2OH + CL
!CH2CL + CH3 = C2H5CL
!CH2CL + CH3 = C2H4 + HCL
!CH2CL + O = CH2CLO.
1.32E+12
1.70E+13
6.66E+13
0.0
0.0
0.0
4.00E+13
0.0
1.00E+13
0.0
5.00E+12
3.16E+13
3.31E+11
5.40E+13
5.53E+31
0.0
0.0
0.0
0.0
-5.63
1.82E+25
-4.69
1.31E+30
5.23
8.46E+13
1.68E+16
5.19E+14
4.10E+21
9.24E+11
8.47E+34
4.80E+24
2.55E+15
132
-1.03
-0.68
-0.51
-2.57
2300.
7300.
8700.
3300.
9400.
6500.
8180.
1020.
840.
3740.
0.38
-6.75
-3.44
-2.02
2970.
8080.
7690.
1230.
!CH2CL + O = CH2O + CL
!CH2CLO. = CH2O + CL
!CH2O + CL = HCO + HCL
!CH2O + CLO = HOCL + HCO
!CH3 + CLO = CH3O + CL
!CH3 + CLO = HCL + CH2O
!CH4 + CLO = CH3 + HOCL
15000.
!CH4 + CL = HCL + CH3
!C2H2 + CL = HCL + C2H
28800.
!C2H3 + CL = C2H3CL
!C2H3 + CL = C2H2 + HCL
!C2H4 + CLO = CH2CL + CH2O
!!C2H4 + CLO = C2H4OCL
!C2H4 + CL = HCL + C2H3
!C2H5 + CL = C2H5CL
!C2H5 + CL = C2H4 + HCL
!C2H5 + CL = CH3 + CH2CL
!C2H6 + CL = HCL + C2H5
!!CL + C2H3CL = HCL + CHCL*CJH
8.31E+13
2.51E+24
5.00E+13
1.20E+13
2.28E+07
5.50E+14
1.40E+13
-0.18
-4.78
800.
10070.
0.0
0.0
1.54
500.
2000.
-820.
-0.51
710.
0.0
2.57E+13
1.00E+13
0.0
0.0
6.50E+34
2.40E+24
-3.22
9.26E+18
-1.98
1.75E+32
-6.32
3.00E+13
8.39E+36
6.12E+24
-3.38
1.50E+21
-1.94
7.00E+13
5.00E+12
-6.63
3850.
8610.
9070.
8430.
7900.
0.0
-7.38
5100.
9550.
9040.
17720.
0.0
0.0
1000.
5870.
!**************************************************************************
HO2 + CL = HCL + O2
0.
HO2 + CL = CLO + OH
H2O2 + CL = HCL + HO2
H2O2 + CLO = HOCL + HO2
1.58E+13
3.35E+14
1.02E+12
5.00E+12
0.0
-0.32
0.0
0.0
1470.
800.
2000.
!NO-CL reaction (9 reactions)
CLO+NO=NO2+CL
140. !niksa
HNO+CL=HCL+NO
993.
HONO+CL=HCL+NO2
0.
NOCL+M=NO+CL+M
31991.
!800-1500 K
NOCL+CL=NO+CL2
0.
!niksa
NOCL+H=NO+HCL
890. !niksa
NOCL+O=NO+CLO
3000. !niksa
NOCL+OH=HOCL+NO
2250.
NOCL+OH=HONO+CL
-480.
3.85E12
0.0
8.99E13
0.0
5.00E13
0.0
2.50E15
0.0
2.40E13
0.0
4.60E13
0.0
5.00E12
0.0
5.4E12
0.0
5.5E10
0.0
! NOx chemistry (Muller, 2000)
!N-O-H reaction (Muller and Dryer et al,2000) (24 REACTIONS)
NO+O+M=NO2+M
0.
3.00E13
133
0.0
NO+H+M=HNO+M
0.
NO+OH+M=HONO+M
-721.
NO2+H2=HONO+H
15000.
NO2+O=O2+NO
0.
!niksa
!NO2+O=O2+NO
-240.
NO2+O+M=NO3+M
0.
NO2+H=NO+OH
362.
NO2+OH+M=HNO3+M
0.
NO2+OH=HO2+NO
6680.
!NIKSA
!NO+HO2=NO2+OH
-479.
!MULLER (2000)
NO2+NO2=NO3+NO
20900.
NO2+NO2=2NO+O2
26100.
HNO+H=NO+H2
655.
HNO+O=OH+NO
0.
HNO+OH=H2O+NO
-956.
HNO+NO=N2O+OH
26000.
HNO+NO2=HONO+NO
1990.
HNO+HNO=H2O+N2O
3080.
HONO+O=OH+NO2
5960.
HONO+OH=H2O+NO2
-520.
N2O+M=N2+O+M
56000.
N2O+O=N2+O2
28000.
N2O+O=NO+NO
28000.
N2O+H=N2+OH
16800.
!NIKSA
!N2O+H=N2+OH
4550.
N2O+OH=N2+HO2
40000.
1.52E15
-0.41
1.99E12
-0.05
1.30E4
2.76
1.05E14
-0.52
3.9E12
0.0
1.33E13
0.0
1.32E14
0.0
4.52E13
0.0
1.81E13
0.0
2.11E12
0.0
9.64E9
0.73
1.63E12
0.0
4.46E11
0.72
1.81E13
0.0
1.30E7
1.88
2.00E12
0.0
6.02E11
0.0
8.51E8
0.0
1.20E13
0.0
1.70E12
1.0
7.91E10
0.0
1.00E14
0.0
1.00E14
0.0
2.23E14
0.0
2.53E10
0.0
2.00E12
0.0
CO+N2O=CO2+N2
44000.
CO+NO2=CO2+NO
33800.
5.01E13
0.0
9.03E13
0.0
134
HCO+NO=HNO+CO
0.
HCO+NO2=HONO+CO
2350.
HCO+NO2=H+NO+CO2
1930.
! SOx chemistry
SO2+O(+M) =
2400.
0.0
1.24E23
-3.29
8.39E15
-0.75
9.200E+10
0.0000
(66 reactions)
SO3(+M)
N2/1.3/ SO2/10/ H2O/10/
LOW / 4.000E+28 -4.00
SO2+OH(+M) =
715.00
7.23E12
5250. /
HOSO2(+M)
7.200E+12
!muller and niksa
0.0000
N2/1.5/ SO2/10/ H2O/10/
LOW / 4.500E+25 -3.30
359.84 /
TROE /
0.7000
1.0e-30 1e+30 /
SO2+OH = HOSO+O
1.8900
SO2+OH = SO3+H
2.6900
SO2+CO = SO+CO2
48300.
SO2*+M = SO2+M
0.0000
SO2*+SO2 = SO3+SO
0.0000
SO3+H = HOSO+O
2.9200
3.900E+08
76000.00
4.900E+02
23850.00
2.700E+12
1.300E+14
3600.00
2.600E+12
2430.00
2.500E+05
50300.0
SO+O(+M) = SO2(+M)
0.0000
0.00
!niksa, leeds
N2/1.5/ SO2/10/ H2O/10/
LOW / 1.200E+21 -1.54
0.00 /
TROE /
0.5500
1.0e-30 1e+30 /
3.200E+13
SO+M =
4.000E+14
SO+H+M = HSO+M
0.0000
0.00
N2/1.5/ SO2/10/ H2O/10/
5.000E+15
2SO =
2.000E+12
S+O+M
0.0000
107000.
N2/1.5/ SO2/10/ H2O/10/
SO2+S
0.0000
HSO+H = HSOH
920.00
HSO+H = SH+OH
1560.
HSO+H = S+H2O
1.3700
0.0000
4000.00
2.500E+20
-3.1400
4.900E+19
-1.8600
1.600E+09
-340.
135
HSO+H = H2SO
50.
HSO+H = H2S+O
1.0300
10400.
HSO+O+M = HSO2+M
-50.
HSO+O = SO2+H
0.00
HSO+O+M = HOSO+M
1600.
HSO+O = O+HOS
1.0200
5340.
HSO+O = OH+SO
0.1500
300.
HSO+OH = HOSHO
3170.
HSO+OH = HOSO+H
3750.
HSO+OH = SO+H2O
470.
HSO+O2 = SO2+OH
0.0000
0.0
!NIKSA, MULLER
HSOH = SH+OH
75200.
HSOH = S+H2O
54500.
HSOH = H2S+O
86500.
H2SO = H2S+O
71700.
HOSO(+M) = HSO2(+M)
50000.
N2/1/ SO2/10/ H2O/10/
LOW / 1.700E+35 -5.64
27881.23 /
TROE /
0.4000
1.0e-30 1e+30 /
HOSO+M = O+HOS+M
119000.
!MULLER
HOSO+H = SO+H2O
-1900.
HOSO+OH = SO2+H2O
0.00
HOSO+O2 = HO2+SO2
1000.
HSO2(+M) = H+SO2(+M)
18361.
!muller
N2/1/ SO2/10/ H2O/10/
LOW / 3.500E+25 -3.29
HOSO2 = HOSO+O
106300.
HOSO2+H = SO2+H2O
0.0000
0.00
HOSO2+O = SO3+OH
0.0000
0.00
HOSO2+OH = SO3+H2O
0.00
1.800E+17
-2.4700
1.100E+06
1.100E+19
-1.7300
4.500E+14
6.900E+19
-0.4000
-1.6100
4.800E+08
1.400E+13
5.200E+28
-5.4400
5.300E+07
1.5700
1.700E+09
1.0300
1.000E+12
2.800E+39
-8.7500
5.800E+29
-5.6000
9.800E+16
-3.4000
4.900E+28
-6.6600
1.000E+09
1.0300
2.500E+30
-4.8000
6.300E-10
6.2900
1.000E+12
0.0000
1.000E+12
2.000E+11
0.0000
-0.9000
9612.48 /
5.400E+18
-2.3400
1.000E+12
5.000E+12
1.000E+12
136
0.0000
HOSO2+O2 = HO2+SO3
656.0
HOSHO = HOSO+H
73800.
7.80E+11
HOSHO+H = HOSO+H2
0.00
HOSHO+O = HOSO+OH
0.00
SO2+NO2=NO+SO3
27000.
SO+NO2 = SO2+NO
0.00
HSO+NO2 = HOSO+NO
0.00
1.000E+12
0.0000
5.000E+12
0.0000
! modified ( 8
SO3+O = SO2+O2
0.0000
SO3+SO = 2SO2
0.0000
SO+O2 = SO2+O
2.3700
0.0000
6.400E+30
-5.8900
6.3E12
0.0
!NIKSA
8.432E+12
0.00
5.8E12
0.00
reactions)
2.000E+12
19870.
1.000E+12
10000.00
7.600E+03
3000.00
HOSO(+M) = SO+OH(+M)
76380.00
LOW / 1.156E+46 -9.02
53350.00 /
TROE /
9.5000E-01 2.9890E+03 1.1000E+00
SO+OH = SO2+H
0.0
H+SO2(+M) = HOSO(+M)
7200.00
LOW / 2.662E+38 -6.43
11150.00 /
TROE /
8.2000E-01 1.3088E+05 2.6600E+02
HOSO2 = SO3+H
55000.00
HSO+H = SO+H2
0.0000
0.00
! New ( 7 reactions)
HOSO+H = SO2+H2
0.0000
0.00
HSO2+H = SO2+H2
0.0000
0.00
HSO2+OH = SO2+H2O
0.0000
0.00
HSO2+O2 = HO2+SO2
0.0000
0.00
HOSHO = SO+H2O
59500.
HOSHO+OH = HOSO+H2O
0.00
HOSO2+H = SO3+H2
0.00
9.940E+21
-2.5400
/
1.077E+17
3.119E+08
-1.35
1.6100
/
1.400E+18
-2.9100
1.000E+13
3.000E+13
3.000E+13
1.000E+13
1.000E+13
1.200E+24
1.000E+12
1.0E+12
!S-CL-O reactions (quantum chemistry) (3 reactions)
137
-3.5900
0.0000
0.00
SO+CLO=SO2+CL
15744.
SCL+O=SO+CL
12350.
SO+CL2=SCL+CLO
27320.
!
NIST
1.29E10
0.0
2.84E11
0.0
1.63E9
0.0
CxHy chemistry ( REACTIONS)
!*** C1 hydrocarbons
***********************************************************
!
CH4
*** Methane ***
+ H
= CH3 + H2
2.20E04
3.00
8750.
!CH4 + H
= CH3 + H2
1.32E04
3.00
8040.
CH4 + O
= CH3 + OH
1.02E09
1.50
8604.
CH4 + OH
= CH3 + H2O
1.60E06
2.10
2460.
CH4 + O2
= CH3 + HO2
7.90E13
0.00
56000.
!CH4 + HO2
= CH3 + H2O2
1.80E11
0.00
18700.
!CH4 + O2
= CH3 + HO2
3.92E13
0.00
56894.
!92BAU/COB
CH4 + HO2
= CH3 + H2O2
1.13E13
0.00
24641.
!88BAL/JON (ok)
!CH4+O2 shows factor of two different, CH4+HO2 shows lots different
!which value to use?
!
CH3
*** Methyl ***
+ H (+M) = CH4 (+M)
0.
!MBA002 84WAR (up)
LOW/8.00E26
-3.0
0./
SRI/0.45 797. 979. /
H2/2.0/ CO/2.0/ CO2/3.0/ H2O/5.0/
!CH3 + H (+M) = CH4 (+M)
0.
!86TSA/HAM
!factor of 2 different, which to use?
CH3 + H
= CH2
+ H2
15100.
!MBA013 (mb?)
CH3 + O
= CH2O + H
0.
!MBA009 (mb?)
CH3 + OH
= CH2
+ H2O
5000.
!MBA012 (mb?)
!CH3 + OH
= CH3OH
11673.
!87DEA/WES (1atm)
!CH3 + OH
= CH2OH + H
8068.
!87DEA/WES (1atm)
!CH2OH+H
= CH3+OH
0.
!MBA010
CH3 + OH
= CH3O + H
13931.
!87DEA/WES (1atm)
6.00E16
-1.00
!(89STE/SMI2)
1.21E15
-0.40
9.00E13
138
0.00
8.00E13
0.00
7.50E06
2.00
2.24E40
-8.20
2.64E19
-1.80
1.00E14
0.00
5.74E12
-0.23
!CH3O+H
= CH3+OH
1.00E14
0.
!MBA011
CH3 + OH
= CH2SING + H2O
8.90E19
8067.
!87DEA/WES (1atm)
!CH3 + O2
= CH3O + O
2.05E18
29229.
!MBA008 86TSA/HAM
CH3 + O2 <=> CH3O + O
2.05E+19
29229.
!bozzelli
!CH3
0.00
-1.80
-1.57
-1.570
+ O2
= CH3O + O
2.88E15
30850.
!92HO/YU (BOZ)
!CH3 + O2
= CH3O + O
7.20E13
31600
!92BAU/COB
!CH3 +
O2
= CH2O +
OH
3.30E11
9000.
!92BAU/COB
CH3
+
O2
= CH2O +
OH
3.59E09
10150.
!92HO/YU (BOZ)
!CH3
+
O2
= CH3O +
O
1.32E14
31600.
!92BAU/COB
!CH3
+
O2(+M)=CH3OO(+M)
7.80E08
0.
!92BAU/COB
CH3 + HO2
= CH3O + OH
2.00E13
0.
!MBA007 86TSA/HAM
CH3
+
CH3
= C2H4 +
H2
1.00E16
32005.
!92EGO/DU
!CH3 + CH3(+M) = C2H6 (+M)
9.03E16
654.
!MBA001 88WAG/WAR (ok)
! LOW/3.18E41
-7.0 2762./
! TROE/0.6041 6927. 132./
!H2/2.0/ CO/2.0/ CO2/3.0/ H2O/5.0/
CH3+CH3<=>C2H6
2.68E+29
6130.0
!Bozzelli
!CH3+HCO=CH4+CO
2.648E+13
0.00
!(GRIMECH11)
CH3+HCO=CH4+CO
1.20E14
0.
!86TSA/HAM
C+CH3=H+C2H2
5.000E+13
0.000
!(GRIMECH1)
-1.15
0.00
0.
-0.14
0.
1.2
0.00
0.
-1.20
!88WAG/WAR
-5.0
0.000
0.
!
*** CH2 (triplet) ***
C+CH2=H+C2H
5.000E+13
0.000
!(GRIMECH1)
H+CH2(+M)=CH3(+M)
2.500E+16
-0.800
0.00
!(GRIMECH11)
LOW / 3.200E+27
-3.140
1230.00/
!(GRIMECH11)
TROE/ 0.6800
78.00 1995.00 5590.00 /
!(GRIMECH11)
H2/2.00/ H2O/6.00/ CH4/2.00/ CO/1.50/ CO2/2.00/ C2H6/3.00/ AR/0.70/
!(GRIMECH11)
CH2+OH = CH2O+H
2.50E13
0.00
!MBA026
CH2+O = CO+2H
5.00E13
0.00
!MBA043
CH2+CO2 = CH2O+CO
1.10E11
0.00
!MBA042
CH2+O = CO+H2
3.00E13
0.00
!MBA044
139
0.00
0.00
0.
0.
1000.
0.
CH2+O2 = CO2+2H
1.60E12
!MBA045
CH2+O2 = CH2O+O
2.00E14
10000.
!MBA046*x
!(above match to c2h2 Taka)
!$CH2+O2 = CH2O+O
5.00E13
9000.
!MBA046
CH2+O2 = CO2+H2
6.90E11
!MBA047
CH2+O2 = CO+H2O
1.90E10
1000.
!MBA048
CH2+O2 = CO+OH+H
8.60E10
!MBA049
CH2+O2 = HCO+OH
4.30E10
!MBA050
CH2+CH3 = C2H4+H
3.00E13
!MBA072
2CH2 = C2H2+H2
4.00E13
!MBA114
CH2
+
HO2
= CH2O +
OH
3.01E13
0.
!92EGO/DU
CH2
+
H2O2 = CH3O +
OH
3.01E13
0.
!92EGO/DU
!CH2
+
CO2
= CH2O +
CO
1.10E11
1000.
!92EGO/DU
CH2
+
CH2O = CH3
+
HCO
1.20E12
0.
!92EGO/DU
CH2
+
HCO
= CH3
+
CO
1.81E13
0.
!92EGO/DU
!QUESTION? Does CH2 or CH2SING react w/ HO2 H2O2 CH2O
!
!*** CH Reactions ***
!********************
CH2+H = CH+H2
!MBA024
CH2+OH = CH+H2O
!MBA025
CH+O2 = HCO+O
!MBA027 82BER/FLE (ok)
CH+O = CO+H
!MBA028 83MES/FIL
H+CH=C+H2
!(GRIMECH1)
CH+OH = HCO+H
!MBA029
CH+CO2 = HCO+CO
!MBA030 82BER/FLE (ok)
CH+H2O = CH2O+H
!MBA032 89MIL/BOW
CH+CH2O = CH2CO+H
!MBA033 88ZAB/FLE (up)
CH+CH2 = C2H2+H
!MBA035
CH+CH3 = C2H3+H
!MBA036
0.00
1000.
0.00
0.00
0.00
500.
0.00
-
0.00
-500.
0.00
-500.
0.00
0.
0.00
0.
0.
0.
0.
0.
0.
HCO
1.00E18
-1.56
0.
1.13E07
2.00
3000.
3.30E13
0.00
0.
5.70E13
0.00
0.
1.100E+14
0.000
0.00
3.00E13
0.00
0.
3.40E12
0.00
690.
1.17E15
-0.75
0.
9.46E13
0.00
-515.
4.00E13
0.00
0.
3.00E13
0.00
0.
140
CH+CH4 = C2H4+H
6.00E13
0.00
!MBA037 80BUT/FLE (up)
C2H3+CH = CH2+C2H2
5.00E13
0.00
!MBA086
HCCO+CH = C2H2+CO
5.00E13
0.00
!MBA104
CH+CO(+M)=HCCO(+M)
5.000E+13
0.000
0.00
!(GRIMECH1)
LOW / 2.690E+28
-3.740
1936.00/
!(GRIMECH1)
TROE/ 0.5757 237.00 1652.00 5069.00 /
!(GRIMECH1)
H2/2.00/ H2O/6.00/ CH4/2.00/ CO/1.50/ CO2/2.00/ C2H6/3.00/ AR/0.70/
!(GRIMECH1)
0.
0.
0.
!*** C1 oxy-hydrocarbons
*******************************************************
!
CH3O+M
*** CH3O, CH2OH ***
= CH2O+H+M
1.00E14
0.00
25000.
!MBA014
!CH3O+O2
= CH2O+HO2
6.30E10
0.00
2600.
!MBA022
CH3O+O2
= CH2O+HO2
4.00E10
0.00
2140.
!92BAU/COB
!CH3O+O2
= CH2O+HO2
1.48E13
0.00
1500.
!bozzelli
CH3O+H
= CH2O+H2
2.00E13
0.00
0.
!MBA016
H+CH3O=H+CH2OH
3.400E+06
1.600
0.00
!(GRIMECH11)
H+CH3O=CH2SING+H2O
1.600E+13
0.000
0.00
!(GRIMECH11)
H+CH3O(+M)=CH3OH(+M)
5.000E+13
0.000
0.00
!(GRIMECH11)
LOW / 8.600E+28
-4.000
3025.00/
!(GRIMECH11)
TROE/ 0.8902 144.00 2838.00 45569.00 /
!(GRIMECH11)
H2/2.00/ H2O/6.00/ CH4/2.00/ CO/1.50/ CO2/2.00/ C2H6/3.00/
!(GRIMECH11)
CH3O+O
= CH2O+OH
1.00E13
0.00
0.
!MBA020
CH3O+OH
= CH2O+H2O
1.00E13
0.00
0.
!MBA018
CH3O +
HO2
= CH2O + H2O2
3.01E11
0.
0.
!92EGO/DU
CH3O +
CO
= CH3
+ CO2
1.57E13
0.
11797.
!92EGO/DU
CH3O +
C2H5
= CH2O + C2H6
2.41E13
0.
0.
!92EGO/DU
CH3O +
C2H3
= CH2O + C2H4
2.41E13
0.
0.
!92EGO/DU
CH3O +
C2H
= CH2O + C2H2
2.41E13
0.
0.
!92EGO/DU
CH3O +
CH3
= CH4
+ CH2O
2.40E13
0.
0.
!86TSA/HAM
!QUESTION? What about reaction w/ HO2 CO C2H5 C2H3 CH3
CH2OH+M
25000.
= CH2O+H+M
!MBA015
1.00E14
141
0.00
!CH2OH+O2
= CH2O+HO2
1500.
!MBA023
CH2OH+O2
= CH2O+HO2
5000.
!LAW
!CH2OH+O2
= CH2O+HO2
00.
!94BAU/COB
!
DUPLICATE
!CH2OH+O2
= CH2O+HO2
3577.
!94BAU/COB
!
DUPLICATE
!CH2OH+O2
= CH2O+HO2
0.
!87TSA
!CH2OH+H
= CH2O+H2
0.
!MBA017
CH2OH+H
= CH3 + OH
0.
!87TSA
!CH2OH+H
= CH2O + H2
0.
!87TSA
!CH2OH+H
= CH2O + H2
0.
!Bozzelli
!CH2OH+O
= CH2O+OH
0.
!MBA021
!CH2OH+OH
= CH2O+H2O
0.
!MBA019
CH2OH +
HO2 = CH2O +
0.
!92EGO/DU
CH2OH +
HCO = CH3OH +
0.
!92EGO/DU
CH2OH +
HCO = CH2O +
0.
!87TSA
CH2OH +
CH3 = C2H5 +
6589.
!92EGO/DU
CH2OH +
CH2O = HCO
+
5862.
!92EGO/DU
CH2OH +
CH2OH = CH3OH +
0.
!92EGO/DU
!CH2OH +
H
= CH3
+
-2971.
!92EGO/DU
CH2OH +
O
= CH2O +
0.
!87TSA
CH2OH +
OH
= CH2O +
0.
!87TSA
1.48E13
0.00
2.41E14
0.00
1.57E15
-1.00
7.23E13
0.00
1.2E12
0.00
2.00E13
0.00
9.64E13
0.
6.03E12
0.
2.0E13
0.
1.00E13
0.00
1.00E13
0.00
H2O2
1.20E13
0.
CO
1.20E14
0.
CH2O
1.81E14
0.
OH
1.37E14
-.41
CH3OH
5.54E03
2.81
CH2O
1.20E13
OH
0.
2.39E02
3.353
OH
4.20E13
0.
H2O
2.40E13
0.
!
CH2O+M
*** CH2O ***
= HCO+H+M
3.31E16
0.00
81000.
!MBA053 80DEA/JOH (ok)
CH2O+H
= HCO+H2
2.19E08
1.77
3000.
!MBA052 86TSA/HAM
CH2O+O
= HCO+OH
1.80E13
0.00
3080.
!MBA054 80KLE/SOK (up)
CH2O+OH
= HCO+H2O
3.43E09
1.18
-447.
!MBA051 86TSA/HAM
CH2O+HO2
= HCO+H2O2
1.99E12
0.00
11665.
!86TSA/HAM
!HCO+H2O2
= CH2O+HO2
1.02E11
0.00
6927.
!86TSA/HAM(rev)
!QUESTION? need to check CH2O+HO2=HCO+H2O2 missing from MB mechanism
142
CH2O+O2
= HCO+HO2
2.04E13
0.00
38900.
!74BAL/FUL (ok)
!QUESTION? need to check CH2O+O2=HCO+HO2 missing from MB mechanism
CH2O+CH3
= HCO+CH4
5.54E03
2.81
5862.
!86TSA/HAM (ok)
!CH2O+CH3
= HCO+CH4
4.09E12
0.00
8843.
!92BAU/COB
H2+CO(+M)=CH2O(+M)
4.300E+07
1.500
79600.00
!(GRIMECH11)
LOW /
5.070E+27
-3.420
84350.00/
!(GRIMECH1)
TROE/ 0.9320 197.00 1540.00 10300.00 /
!(GRIMECH1)
H2/2.00/ H2O/6.00/ CH4/2.00/ CO/1.50/ CO2/2.00/ C2H6/3.00/ AR/0.70/
!(GRIMECH1)
!QUESTION? need to check CH2O+CH3=HCO+CH4 missing from MB mechanism
!*** C2 hydrocarbons
***********************************************************
!
*** C2H6 ***
C2H6 + H
= C2H5 + H2
5.40E02
5210.
!MBA066 73CAL/DOV (ok)
C2H6 + O
= C2H5 + OH
3.00E07
5115.
!MBA067 84WAR (ok)
C2H6 + OH
= C2H5 + H2O
8.70E09
1810.
!MBA068 83TUL/RAV (ok)
C2H6 + CH3
= C2H5 + CH4
5.50E-1
8300.
!MBA065 73CLA/DOV (ok)
C2H6 +
O2
= C2H5 +
HO2
4.03E13
50842.
!92EGO/DU
C2H6 +
HO2
= C2H5 +
H2O2
2.95E11
14935.
!92EGO/DU
!QUESTION? What about ignition steps C2H6+O2 & HO2
3.50
2.00
1.05
4.00
0.
0.
!
*** C2H5 ***
H+C2H5(+M)=C2H6(+M)
5.210E+17
-0.990
1580.00
!(GRIMECH11)
LOW / 1.990E+41
-7.080
6685.00/
!(GRIMECH11)
TROE/ 0.8422 125.00 2219.00 6882.00 /
!(GRIMECH11)
H2/2.00/ H2O/6.00/ CH4/2.00/ CO/1.50/ CO2/2.00/ C2H6/3.00/ AR/0.70/
!(GRIMECH11)
C2H5+H
= CH3+CH3
1.00E14
0.00
0.
!MBA074
C2H5 +
H
= C2H4 +
H2
1.81E12
0.
0.
!92EGO/DU
!C2H5+H
= CH3+CH3
3.60E13
0.00
0.
!92BAU/COB
!C2H5
+ O = CH3CHO
+ H
8.00E12
0.
0.
!86TSA/HAM (review)
!C2H5
+ O = CH2O
+ CH3
1.60E13
0.
0.
!86TSA/HAM (review)
C2H5
+ O = CH3CHO
+ H
5.50E13
0.
0.
!94BAU/COB
C2H5
+ O = CH2O
+ CH3
1.10E13
0.
0.
!94BAU/COB
143
!C2H5+O2
= C2H4+HO2
2.56E19
1977.
!90BOZ/DEA (250-1200)
!C2H5+O2
= C2H4+HO2
8.43E11
3875.
!MBA075 80BAL/PIC (ok)
C2H5 +
OH
= C2H4 +
H2O
2.41E13
0.
!92EGO/DU
C2H5 +
HO2
= CH3
+ CH2O + OH
2.40E13
0.
!92EGO/DU
!QUESTION? What about C2H5+HO2= [C2H5O]+OH = CH3+CH2O+OH
!QUESTION? What about C2H5+OH=C2H4+H2O
-2.77
0.00
0.
0.
!
C2H4+M
*** C2H4 ***
= C2H2+H2+M
1.50E15
0.00
55800.
!MBA128 83KIE/KAP (up)
!need 2 check 77JUS/ROT 77TAN 80TAN/GAR (Gardiner) lo (ok) better & selfconsistent
C2H4+M
= C2H3+H+M
1.40E16
0.00
82360.
!MBA129
!need to check 77JUS/ROT 80TAN/GAR (Gardiner) lo (ok) better & selfconsistent
!C2H4+H(+M)
= C2H5(+M)
8.40E08
1.5
990.
!86TSA/HAM (ref)
!
LOW/6.37E27
-2.8
-54./
!MBA073
!
H2/2.0/ CO/2.0/ CO2/3.0/ H2O/5.0/
!MBA073
!C2H4+H
= C2H3+H2
1.10E14
0.00
8500.
!MBA069 73PEE/MAH (up)
H+C2H4(+M)=C2H5(+M)
1.080E+12
0.454
1820.00
!(GRIMECH11)
LOW / 1.200E+42
-7.620
6970.00/
!(GRIMECH11)
TROE/ 0.9753 210.00
984.00 4374.00 /
!(GRIMECH11)
H2/2.00/ H2O/6.00/ CH4/2.00/ CO/1.50/ CO2/2.00/ C2H6/3.00/ AR/0.70/
!(GRIMECH11)
H+C2H4=C2H3+H2
1.325E+06
2.530
12240.00
!(GRIMECH11)
!C2H4+H
= C2H3+H2
5.42E14
0.00
14904.
!92BAU/COB
!need to check 92BAU/COB lo (ok)s best
C2H4+O
= CH3+HCO
1.60E09
1.20
746.
!MBA070 84WAR (up)
!need to check and compare with more recent numbers
!C2H4+OH
= C2H3+H2O
2.02E13
0.00
5955.
!MBA071 88TUL
C2H4+OH
= C2H3+H2O
4.50E06
2.00
2850.
!(k19fit)
CH3+C2H4=C2H3+CH4
2.270E+05
2.000
9200.00
!(GRIMECH11)
C2H4 +
O2
= C2H3 +
HO2
4.22E13
0.
57594.
!92EGO/DU
C2H4 +
CO
= C2H3 +
HCO
1.51E14
0.
90562.
!92EGO/DU
!
C2H3+H
0.
! C2H3+H
0.
*** C2H3 ***
= C2H2+H2
!92BAU/COB
= C2H2+H2
!MBA080
144
1.20E13
0.00
4.00E13
0.00
C2H3+OH
= C2H2+H2O
5.00E12
0.00
0.
!MBA083
!need to check 86TSA/HAM says 3.0E13 0.
C2H3+CH2
= C2H2+CH3
3.00E13
0.00
0.
!MBA084
!****** New Value ***
C2H3+O2
= CH2O+HCO
1.05E38
-8.22
7030.
!92WES (k-a/s)
DUP
C2H3+O2
= CH2O+HCO
4.48E26
-4.55
5480.
!92WES (direct)
DUP
!C2H3+O2
= CH2O+HCO
4.00E12
0.00
-250.
!MBA082 84SLA/PAR (ok)
!********************
C2H3+O
= CH2CO+H
3.00E13
0.00
0.
!MBA081 84WAR
C2H3 +
O2
= C2H2 +
HO2
1.20E11
0.
0.
!92EGO/DU
C2H3 +
HO2
= CH2CO + OH + H
3.00E13
0.
0.
!92EGO/DU
!QUESTION? What about C2H3 + HO2 = C2H3O + OH = CH2CO + H + OH
!QUESTION? What about C2H3 + HO2 = C2H4 + O2? or reverse (initiation step)
!QUESTION? What about C2H3 + HCO = C2H4 + CO
!
*** C2H2 ***
C2H2+H(+M)
= C2H3(+M)
2410.
!MBA079 76PAY/STI (ok)
LOW/2.67E27 -3.5 2410./
H2/2.0/ CO/2.0/ CO2/3.0/ H2O/5.0/
C2H2+OH
= HCCOH+H
13500.
!MBA088
C2H2+OH
= CH2CO+H
-1000.
!MBA089
C2H2+OH
= CH3+CO
-2000.
!MBA090
C2H2+O
= CH2+CO
1900.
!MBA076
C2H2+O
= HCCO+H
1900.
!MBA077
O+C2H2=OH+C2H
28950.00
!(GRIMECH11)
C2H2+O2
= HCCO+OH
30100.
!MBA126
C2H2
= C2H
+
H
137510.
!92EGO/DU
C2H2 +
H
= C2H
+
H2
22243.
!92EGO/DU
C2H2 +
OH
= C2H
+
H2O
12035.
!92EGO/DU
C2H2 +
O2
= C2H
+
HO2
74475.
!92EGO/DU
C2H
+
O
= CH
+
CO
0.
!92EGO/DU
OH+C2H=H+HCCO
0.00
!(GRIMECH11)
145
5.54E12
0.00
5.04E05
2.30
2.18E-4
4.50
4.83E-4
4.00
1.02E07
2.00
1.02E07
2.00
4.600E+19
-1.410
2.00E08
1.50
1.80E41
-7.76
6.02E13
0.
1.45E4
2.68
1.20E13
0.
1.81E13
0.
2.000E+13
0.000
OH + C2H = CH2 + CO
0.
!86TSA/HAM
C2H
+
O2
= CO
0.
!92EGO/DU
+
HCO
2.00E13
0.
2.41E12
0.
!*** C2 oxy-hydrocarbons
*******************************************************
!
*** HCCOH, CH2CO ***
HCCOH+H
= CH2CO+H
1.00E13
0.00
0.
!MBA091
CH2CO+H
= CH3+CO
1.13E13
0.00
3428.
!MBA094
CH2CO+H
= HCCO+H2
5.00E13
0.00
8000.
!MBA095
CH2CO+O
= CO2+CH2
1.75E12
0.00
1350.
!MBA093
CH2CO+O
= HCCO+OH
1.00E13
0.00
8000.
!MBA096
!Dryer&Yetter have 3 chans CH2CO+O = HCO+HCO & CH2O+CO & HCCO+OH
!QUESTION? who is right?
CH2CO+OH
= HCCO+H2O
7.50E12
0.00
2000.
!MBA097
!QUESTION? Dyer&Yetter have also CH2CO+OH=CH2O+HCO (86GLA/MIL)
CH2CO(+M)
= CH2+CO(+M)
3.00E14
0.00
70980.
!MBA098
LOW/3.60E15
0.0 59270./
CH2CO +
O
= HCO
+
HCO
2.00E13
0.
2293.
!92EGO/DU
CH2CO +
O
= CH2O +
CO
2.00E13
0.
0.
!92EGO/DU
CH2CO +
OH
= CH2O +
HCO
2.80E13
0.
0.
!92EGO/DU
HCCO
HCCO
+
OH
= HCO
+ CO + H
0.
!92EGO/DU
+
CH2
= C2H
+
CH2O
2000.
!92EGO/DU
!
HCCO+H
0.
HCCO+O
0.
HCCO+O2
854.
2HCCO
0.
HCCO+CH2
0.
! CxHy-Cl
1.00E13
0.
1.00E13
0.
*** HCCO Reactions ***
= CH2SING+CO
1.00E14
!MBA101
= H+2CO
1.00E14
!MBA102
= 2CO+OH
1.60E12
!MBA103
= C2H2+2CO
1.00E13
!MBA105
= C2H3+CO
3.00E13
!MBA115
0.00
0.00
0.00
0.00
0.00
chemistry (Bozzelli--68 REACTIONS)
CH4 + CL <=> HCL + CH3
CH4 + CLO <=> CH3 + HOCL
15000.
2.57E+13
1.40E+13
146
0.0
0.0
3850.
CH3 + CLO <=> CH3O + CL
2.28E+07
1.54
-820.
CH3 + CLO <=> HCL + CH2O
CH3CL <=> CH3 + CL
5.50E+14
5.53E+31
-0.51
-5.63
710.
88810.
CH3CL <=> CH2 + HCL
1.82E+25
-4.69
132460.
CH3CL <=> CH2CL + H
1.31E+30
-5.23
106100.
CH3CL + OH <=> CH2CL + H2O
1.32E+12
0.0
2300.
CH3CL + O <=> OH + CH2CL
1.70E+13
0.0
7300.
CH3CL + H <=> H2 + CH2CL
10600.
CH3CL + O2 <=> HO2 + CH2CL
52200.
CH3CL + HO2 <=> H2O2 + CH2CL
16700.
CH3CL + CLO <=> HOCL + CH2CL
6.66E+13
0.0
4.00E+13
0.0
1.00E+13
0.0
5.00E+12
0.0
8700.
CH3CL + CL <=> HCL + CH2CL
3.16E+13
0.0
3300.
CH3CL + CH3 <=> CH4 + CH2CL
3.31E+11
0.0
9400.
CH3CL + H <=> HCL + CH3
5.40E+13
0.0
6500.
CH2CL + O2 <=> CLO + CH2O
8.46E+13
-1.03
8180.
CH2CL + O2 = CH2CLO + O
34427.
!"
1.15E24
-3.45
CH2CL + O2 = CHCLO + OH
24786.
!"
CH2CL + HO2 = CHCLO + H2O
-532.
!"
7.33E13
-0.44
1.35E04
2.08
CH2CL + CLO = CH2CLO + CL
-672.
!CHEMACT CH2CLC
CH2CL + H <=> CH3 + CL
1.34E11
0.40
1.68E+16
-0.68
1020.
CH2CL + HO2 <=> CH2CLO. + OH
5.19E+14
-0.51
840.
CH2CL + OH <=> CH2O + HCL
4.10E+21
-2.57
3740.
CH2CL + OH <=> CH2OH + CL
9.24E+11
CH2CL + CH3 <=> C2H5CL
8.47E+34
-6.75
8080.
CH2CL + CH3 <=> C2H4 + HCL
4.80E+24
-3.44
7690.
CH2CL + O <=> CH2CLO.
2.55E+15
-2.02
1230.
CH2CL + O <=> CH2O + CL
8.31E+13
-0.18
800.
CH2CLO. <=> CH2O + CL
2.51E+24
-4.78
10070.
147
0.38
2970.
CHCLO + H = CHO + HCL
7400.
!HO
CHCLO + H = CH2O + CL
6360.
!"
CHCLO = CHO + CL
92920.
!"
CHCLO = CO + HCL
92960.
!"
CHCLO + OH = CCLO + H2O
1200.
!WON '91
CHCLO + OH = HCO2 + HCL
-1516.
!CHEMACT '94
CHCLO + O = CCLO + OH
3500.
!WON '91
CHCLO + O2 = CCLO + HO2
41800.
!WON '91
CHCLO + CL = CCLO + HCL
500. !"
CHCLO + CH3 = CCLO + CH4
6000.
!"
CHCLO + CH3 = CHO + CH3CL
8800.
!"
CHCLO + CLO = CCLO + HOCL
7000.
!DEMORE '87
CH2O + CL <=> HCO + HCL
5.00E+13
0.0
500.
CH2O + CLO <=> HOCL + HCO
1.20E+13
0.0
2000.
C2H2 + CL <=> HCL + C2H
28800.
C2H3 + CL <=> C2H3CL
1.00E+13
0.0
6.50E+34
-6.63
8610.
C2H3 + CL <=> C2H2 + HCL
2.40E+24
-3.22
9070.
C2H4 + CLO <=> CH2CL + CH2O
9.26E+18
-1.98
8430.
C2H4 + CLO <=> C2H4OCL
1.75E+32
-6.32
7900.
C2H4 + CL <=> HCL + C2H3
3.00E+13
C2H5 + CL <=> C2H5CL
8.39E+36
-7.38
9550.
C2H5 + CL <=> C2H4 + HCL
6.12E+24
-3.38
9040.
C2H5 + CL <=> CH3 + CH2CL
1.50E+21
-1.94
17720.
C2H6 + CL <=> HCL + C2H5
7.00E+13
0.0
1000.
CL + C2H3CL <=> HCL + CHCLC.H
5.00E+12
0.0
5870.
CL + C2H5CL <=> HCL + CH2CLC.H2
1.12E+13
0.0
1500.
CHCLC.H <=> CL + C2H2
8.23E+29
-5.99
25760.
CH2CLC.H2 <=> CL + C2H4
6.24E+36
-8.05
26340.
148
8.33E13
0.00
6.99E14
-0.58
8.86E29
-5.15
1.10E30
-5.19
7.50E12
0.00
1.98E07
1.20
8.80E12
0.00
4.50E12
0.00
1.25E13
0.00
2.50E10
0.00
1.50E13
0.00
3.00E11
0.00
0.0
5100.
H + C2H3CL <=> HCL + C2H3
1.00E+13
0.0
9800.
H + C2H3CL <=> H2 + CHCLC.H
1.55E+13
0.0
4730.
H + C2H3CL <=> C2H4 + CL
3.01E+13
0.0
4223.
H + C2H3CL <=> CH3C.HCL
5.50E+34
H + CH3C.HCL <=> C2H5CL
5090.
H + CH3C.HCL <=> C2H5 + CL
8.01E+11
3.39E+21
-2.42
8880.
H + CH3C.HCL <=> CH3 + CH2CL
6.67E+19
-1.55
9430.
H + CH3C.HCL <=> C2H4 + HCL
3.72E+30
-5.10
9330.
H + C2H5CL <=> HCL + C2H5
1.00E+13
END
149
-6.56
11950.
0.0
0.0
-
8100.
Thermodynamic Parameters
THERMO
300.000 1000.000 5000.000
! FRY
HG
HG 1
G
300.000 5000.000 1000.00
1
0.25045713E+01-0.10042876E-04 0.74827338E-08-0.22836905E-11 0.24538335E-15
2
0.66388916E+04 0.67756441E+01 0.25032515E+01-0.22565086E-04 0.52967960E-07
3
-0.50408449E-10 0.16726892E-13 0.66400456E+04 0.67864615E+01
4
HGCL
0HG 1CL 1
0
0G
300.000 5000.000 1000.00
0 1
0.44341239E+01 0.16758895E-03-0.29461214E-07 0.53348203E-11-0.34933979E-15
2
0.80888310E+04 0.59002004E+01 0.39410364E+01 0.22935256E-02-0.34487462E-05
3
0.24384448E-08-0.64702350E-12 0.81797692E+04 0.82406659E+01
4
HGCL2
81292CL 2HG 1
G 0300.00
5000.00 1000.00
1
0.07251461E+02 0.03082143E-02-0.14475549E-06 0.02958294E-09-0.02201214E-13
2
-0.01981231E+06-0.06061846E+02 0.06249130E+02 0.03221572E-01-0.02109668E-04
3
-0.07713536E-08 0.08526178E-11-0.01958242E+06-0.10156133E+01
4
HGO
81292HG 1O
1
G 0300.00
5000.00 1000.00
1
0.04192035E+02 0.04176083E-02-0.16589761E-06 0.03318184E-09-0.02429647E-13
2
0.03713109E+05 0.04621457E+02 0.03235991E+02 0.03067170E-01-0.01992628E-04
3
-0.04378690E-08 0.06018340E-11 0.03950193E+05 0.09495331E+02
4
CL
BSN
0
0CL 1
0G
300.000 5000.000 1000.000
01
2.67717410E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00
2
1.37463401E+04 4.62575672E+00 2.67717410E+00 0.00000000E+00 0.00000000E+00
3
0.00000000E+00 0.00000000E+00 1.37463401E+04 4.62575672E+00
4
CL2
BSN
0
0CL 2
0G
300.000 5000.000 1397.000
01
4.86663723E+00-4.27533115E-04 2.65504141E-07-6.16817522E-11 4.72527060E-15
2
-1.58647220E+03-1.10732522E+00 3.49829374E+00 3.33683585E-03-3.85118987E-06
3
2.01995152E-09-3.97416564E-13-1.16110737E+03 6.05172653E+00
4
HCL
SWS
0H
1CL 1
0G
300.000 5000.000 1373.000
01
150
2.87058959E+00 1.20602815E-03-3.36411393E-07 4.17407765E-11-1.91161478E-15
2
-1.19362061E+04 5.90574234E+00 3.38377335E+00 1.04695081E-04 5.42156795E-07
3
-2.69132581E-10 3.95531545E-14-1.21249989E+04 3.11351022E+00
4
HOCL
BSNH
1O
1CL 1
0G
300.000 5000.000 1407.000
01
4.63073493E+00 1.82743163E-03-5.91974327E-07 8.85941948E-11-5.01022568E-15
2
-1.05866588E+04 1.17812957E+00 3.27354781E+00 5.07695043E-03-3.52654957E-06
3
1.27324311E-09-1.84939019E-13-1.01311633E+04 8.42570443E+00
4
CLO
BSN
0
0CL 1O
1G
300.000 5000.000 1367.000
01
4.66991971E+00-3.45228132E-04 2.73802910E-07-7.07613242E-11 5.76861407E-15
2
1.05992288E+04 2.80538308E-01 2.72051679E+00 5.08265197E-03-5.64133130E-06
3
2.88660485E-09-5.58829788E-13 1.11865347E+04 1.04375162E+01
4
CLO2
J 3/61CL 1O
2
0
0G
300.000 5000.000 1000.
1
5.72497580E+00 1.46452300E-03-5.99843510E-07 1.13887500E-10-7.97947760E-15
2
1.06062640E+04-2.57902748E+00 2.88781660E+00 9.28760080E-03-7.08240400E-06
3
6.34533760E-10 9.68016050E-13 1.13673770E+04 1.20200293E+01 1.25803228E+04
4
H2
JANAFH
2
0
0
0G
300.000 5000.000 1371.000
01
2.92711775E+00 9.38198091E-04-2.54588177E-07 3.01839684E-11-1.29301236E-15
2
-8.22037143E+02-1.05415412E+00 3.48423345E+00-1.91470103E-04 5.72602870E-07
3
-2.26565015E-10 2.65808613E-14-1.03493758E+03-4.11107518E+00
4
CCLO
BSNC
1O
1CL 1
0G
300.000 5000.000 1388.000
01
5.29025323E+00 1.86455397E-03-8.18991106E-07 1.57570950E-10-1.04739618E-14
2
-3.75854091E+03 1.10255549E+00 4.31449594E+00 4.60124364E-03-3.75235512E-06
3
1.57415699E-09-2.68996759E-13-3.47379488E+03 6.16707655E+00
4
COCL
7/89
C
1O
1
0CL 1G
300.000 5000.000 1408.000
01
5.24641991E+00 1.76396175E-03-5.74948629E-07 8.62275006E-11-4.87758593E-15
2
-3.71996281E+03 1.41885375E+00 4.37395792E+00 4.67339186E-03-4.34062946E-06
3
2.24737895E-09-4.60611987E-13-3.49077277E+03 5.81728759E+00
4
O2
JANAF
0
0
0O
2G
300.000 5000.000 1390.000
01
151
3.45788989E+00 1.02435264E-03-3.30260481E-07 4.90534060E-11-2.75575300E-15
2
-1.14354180E+03 4.52865496E+00 2.98068876E+00 2.10208645E-03-1.27174431E-06
3
4.30830997E-10-6.35978893E-14-9.71709049E+02 7.10866957E+00
4
H2O
BSNH
2O
1
0
0G
300.000 5000.000 1418.000
01
2.44865478E+00 3.34158952E-03-1.03546264E-06 1.49314276E-10-8.19237589E-15
2
-2.97915999E+04 8.17152630E+00 4.03077288E+00-4.37681163E-04 2.08022971E-06
3
-8.54696476E-10 8.44880999E-14-3.02881298E+04-2.22764921E-01
4
H2O2
JANAFH
2O
2
0
0G
300.000 5000.000 1415.000
01
4.92094996E+00 3.75949626E-03-1.17870736E-06 1.72023417E-10-9.54244632E-15
2
-1.81632052E+04-1.50733475E+00 3.06215675E+00 9.08350700E-03-7.11768908E-06
3
3.17838605E-09-5.83509439E-13-1.76161528E+04 8.12619713E+00
4
CO
JANAFC
1
0
0O
1G
300.000 5000.000 1431.000
01
3.14302870E+00 1.10897666E-03-3.11852147E-07 3.91407304E-11-1.81490465E-15
2
-1.42847633E+04 5.52861597E+00 3.18332593E+00 9.30096224E-04-8.30531731E-08
3
-7.72357660E-11 1.92126888E-14-1.42859979E+04 5.34915683E+00
4
CO2
JANAFC
1O
2
0
0G
300.000 5000.000 1522.000
01
5.19219058E+00 2.08207843E-03-7.46940320E-07 1.19723628E-10-7.10225158E-15
2
-4.93236792E+04-5.26637695E+00 3.33327011E+00 4.63797114E-03-8.15411572E-07
3
-9.82474064E-10 3.68118309E-13-4.85085503E+04 5.33658959E+00
4
CH2O
THERMC
1H
2O
1
0G
300.000 5000.000 1394.000
01
4.47583934E+00 4.23962300E-03-1.55245998E-06 2.68157901E-10-1.69952201E-14
2
-1.50524744E+04-2.04530824E+00 7.34376261E-01 1.36954200E-02-1.08823979E-05
3
4.51850802E-09-7.64645923E-13-1.38251488E+04 1.77943168E+01
4
C
C
1
0
0
0G
300.00
5000.00 1000.00
0 1
2.60208700E+00-1.78708100E-04 9.08704100E-08-1.14993300E-11 3.31084400E-16
2
8.54215400E+04 4.19517700E+00 2.49858500E+00 8.08577700E-05-2.69769700E-07
3
3.04072900E-10-1.10665200E-13 8.54587800E+04 4.75345900E+00
4
H
H
1
0
0
0G
300.00
5000.00 1000.00
0 1
152
2.50000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00
2
2.54716300E+04-4.60117600E-01 2.50000000E+00 0.00000000E+00 0.00000000E+00
3
0.00000000E+00 0.00000000E+00 2.54716300E+04-4.60117600E-01
4
O
O
1
0
0
0G
300.00
5000.00 1000.00
0 1
2.54206000E+00-2.75506200E-05-3.10280300E-09 4.55106700E-12-4.36805200E-16
2
2.92308000E+04 4.92030800E+00 2.94642900E+00-1.63816600E-03 2.42103200E-06
3
-1.60284300E-09 3.89069600E-13 2.91476400E+04 2.96399500E+00
4
OH
H
1O
1
0
0G
300.00
5000.00 1000.00
0 1
2.88273000E+00 1.01397400E-03-2.27687700E-07 2.17468400E-11-5.12630500E-16
2
3.88688800E+03 5.59571200E+00 3.63726600E+00 1.85091000E-04-1.67616500E-06
3
2.38720300E-09-8.43144200E-13 3.60678200E+03 1.35886000E+00
4
HO2
H
1O
2
0
0G
300.00
5000.00 1000.00
0 1
4.07219100E+00 2.13129600E-03-5.30814500E-07 6.11226900E-11-2.84116500E-15
2
-1.57972700E+02 3.47602900E+00 2.97996300E+00 4.99669700E-03-3.79099700E-06
3
2.35419200E-09-8.08902400E-13 1.76227400E+02 9.22272400E+00
4
HCO
H
1O
1C
1
0G
300.00
5000.00 1000.00
0 1
3.55727100E+00 3.34557300E-03-1.33500600E-06 2.47057300E-10-1.71385100E-14
2
3.91632400E+03 5.55229900E+00 2.89833000E+00 6.19914700E-03-9.62308400E-06
3
1.08982500E-08-4.57488500E-12 4.15992200E+03 8.98361400E+00
4
HCCO
H
1O
1C
2
0G
300.00
4000.00 1000.00
0 1
6.75807300E+00 2.00040000E-03-2.02760700E-07-1.04113200E-10 1.96516500E-14
2
1.90151300E+04-9.07126200E+00 5.04796500E+00 4.45347800E-03 2.26828300E-07
3
-1.48209500E-09 2.25074200E-13 1.96589200E+04 4.81843900E-01
4
N2
N
2
0
0
0G
300.00
5000.00 1000.00
0 1
2.92664000E+00 1.48797700E-03-5.68476100E-07 1.00970400E-10-6.75335100E-15
2
-9.22797700E+02 5.98052800E+00 3.29867700E+00 1.40824000E-03-3.96322200E-06
3
5.64151500E-09-2.44485500E-12-1.02090000E+03 3.95037200E+00
4
AR
AR 1
0
0
0G
300.00
5000.00 1000.00
0 1
153
2.50000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00
2
-7.45375000E+02 4.36600100E+00 2.50000000E+00 0.00000000E+00 0.00000000E+00
3
0.00000000E+00 0.00000000E+00-7.45375000E+02 4.36600100E+00
4
CN
C
1N
1
0
0G
300.00
5000.00 1000.00
0 1
3.72012000E+00 1.51835100E-04 1.98738100E-07-3.79837100E-11 1.32823000E-15
2
5.11162600E+04 2.88859700E+00 3.66320400E+00-1.15652900E-03 2.16340900E-06
3
1.85420800E-10-8.21469500E-13 5.12811800E+04 3.73901600E+00
4
HCN
H
1C
1N
1
0G
300.00
4000.00 1000.00
0 1
3.42645700E+00 3.92419000E-03-1.60113800E-06 3.16196600E-10-2.43285000E-14
2
1.48555200E+04 3.60779500E+00 2.41778700E+00 9.03185600E-03-1.10772700E-05
3
7.98014100E-09-2.31114100E-12 1.50104400E+04 8.22289100E+00
4
N
N
1
0
0
0G
300.00
5000.00 1000.00
0 1
2.45026800E+00 1.06614600E-04-7.46533700E-08 1.87965200E-11-1.02598400E-15
2
5.61160400E+04 4.44875800E+00 2.50307100E+00-2.18001800E-05 5.42052900E-08
3
-5.64756000E-11 2.09990400E-14 5.60989000E+04 4.16756600E+00
4
NH
H
1N
1
0
0G
300.00
5000.00 1000.00
0 1
2.76024900E+00 1.37534600E-03-4.45191400E-07 7.69279200E-11-5.01759200E-15
2
4.20782800E+04 5.85719900E+00 3.33975800E+00 1.25300900E-03-3.49164600E-06
3
4.21881200E-09-1.55761800E-12 4.18504700E+04 2.50718100E+00
4
NO
O
1N
1
0
0G
300.00
5000.00 1000.00
0 1
3.24543500E+00 1.26913800E-03-5.01589000E-07 9.16928300E-11-6.27541900E-15
2
9.80084000E+03 6.41729400E+00 3.37654200E+00 1.25306300E-03-3.30275100E-06
3
5.21781000E-09-2.44626300E-12 9.81796100E+03 5.82959000E+00
4
HNO
H
1O
1N
1
0G
300.00
5000.00 1000.00
0 1
3.61514400E+00 3.21248600E-03-1.26033700E-06 2.26729800E-10-1.53623600E-14
2
1.06619100E+04 4.81026400E+00 2.78440300E+00 6.60964600E-03-9.30022300E-06
3
9.43798000E-09-3.75314600E-12 1.09187800E+04 9.03562900E+00
4
NH2
H
2N
1
0
0G
300.00
5000.00 1000.00
0 1
154
2.96131100E+00 2.93269900E-03-9.06360000E-07 1.61725700E-10-1.20420000E-14
2
2.19197700E+04 5.77787800E+00 3.43249300E+00 3.29954000E-03-6.61360000E-06
3
8.59094700E-09-3.57204700E-12 2.17722800E+04 3.09011100E+00
4
H2NO
H
2O
1N
1
0G
300.00
4000.00 1500.00
0 1
5.67334600E+00 2.29883700E-03-1.77444600E-07-1.10348200E-10 1.85976200E-14
2
5.56932500E+03-6.15354000E+00 2.53059000E+00 8.59603500E-03-5.47103000E-06
3
2.27624900E-09-4.64807300E-13 6.86803000E+03 1.12665100E+01
4
NCO
O
1C
1N
1
0G
300.00
4000.00 1400.00
0 1
6.07234600E+00 9.22782900E-04-9.84557400E-08-4.76412300E-11 9.09044500E-15
2
1.35982000E+04-8.50729300E+00 3.35959300E+00 5.39323900E-03-8.14458500E-07
3
-1.91286800E-09 7.83679400E-13 1.46280900E+04 6.54969400E+00
4
N2O
O
1N
2
0
0G
300.00
5000.00 1000.00
0 1
4.71897700E+00 2.87371400E-03-1.19749600E-06 2.25055200E-10-1.57533700E-14
2
8.16581100E+03-1.65725000E+00 2.54305800E+00 9.49219300E-03-9.79277500E-06
3
6.26384500E-09-1.90182600E-12 8.76510000E+03 9.51122200E+00
4
NO2
O
2N
1
0
0G
300.00
5000.00 1000.00
0 1
4.68285900E+00 2.46242900E-03-1.04225900E-06 1.97690200E-10-1.39171700E-14
2
2.26129200E+03 9.88598500E-01 2.67060000E+00 7.83850100E-03-8.06386500E-06
3
6.16171500E-09-2.32015000E-12 2.89629100E+03 1.16120700E+01
4
N2H2
H
2N
2
0
0G
300.00
5000.00 1000.00
0 1
3.37118500E+00 6.03996800E-03-2.30385400E-06 4.06278900E-10-2.71314400E-14
2
2.41817200E+04 4.98058500E+00 1.61799900E+00 1.30631200E-02-1.71571200E-05
3
1.60560800E-08-6.09363900E-12 2.46752600E+04 1.37946700E+01
4
HOCN
H
1O
1C
1N
1G
300.00
4000.00 1400.00
0 1
6.02211200E+00 1.92953000E-03-1.45502900E-07-1.04581100E-10 1.79481400E-14
2
-4.04032100E+03-5.86643300E+00 3.78942400E+00 5.38798100E-03-6.51827000E-07
3
-1.42016400E-09 5.36796900E-13-3.13533500E+03 6.66705200E+00
4
H2CN
H
2C
1N
1
0G
300.00
4000.00 1000.00
0 1
155
5.20970300E+00 2.96929100E-03-2.85558900E-07-1.63555000E-10 3.04325900E-14
2
2.76771100E+04-4.44447800E+00 2.85166100E+00 5.69523300E-03 1.07114000E-06
3
-1.62261200E-09-2.35110800E-13 2.86378200E+04 8.99275100E+00
4
NNH
H
1N
2
0
0G
250.00
4000.00 1000.00
0 1
4.41534200E+00 1.61438800E-03-1.63289400E-07-8.55984600E-11 1.61479100E-14
2
2.78802900E+04 9.04288800E-01 3.50134400E+00 2.05358700E-03 7.17041000E-07
3
4.92134800E-10-9.67117000E-13 2.83334700E+04 6.39183700E+00
4
NH3
H
3N
1
0
0G
300.00
5000.00 1000.00
0 1
2.46190400E+00 6.05916600E-03-2.00497700E-06 3.13600300E-10-1.93831700E-14
2
-6.49327000E+03 7.47209700E+00 2.20435200E+00 1.01147600E-02-1.46526500E-05
3
1.44723500E-08-5.32850900E-12-6.52548800E+03 8.12713800E+00
4
N2H3
H
3N
2
0
0G
300.00
5000.00 1000.00
0 1
4.44184600E+00 7.21427100E-03-2.49568400E-06 3.92056500E-10-2.29895000E-14
2
1.66422100E+04-4.27520500E-01 3.17420400E+00 4.71590700E-03 1.33486700E-05
3
-1.91968500E-08 7.48756400E-12 1.72727000E+04 7.55722400E+00
4
C2N2
C
2N
2
0
0G
300.00
5000.00 1000.00
0 1
6.54800300E+00 3.98470700E-03-1.63421600E-06 3.03859700E-10-2.11106900E-14
2
3.49071600E+04-9.73579000E+00 4.26545900E+00 1.19225700E-02-1.34201400E-05
3
9.19229700E-09-2.77894200E-12 3.54788800E+04 1.71321200E+00
4
HNCO
H
1O
1C
1N
1G
300.00
4000.00 1400.00
0 1
6.54530700E+00 1.96576000E-03-1.56266400E-07-1.07431800E-10 1.87468000E-14
2
-1.66477300E+04-1.00388000E+01 3.85846700E+00 6.39034200E-03-9.01662800E-07
3
-1.89822400E-09 7.65138000E-13-1.56234300E+04 4.88249300E+00
4
O3
121286O
3
G 0300.00
5000.00 1000.00
1
0.05429371E+02 0.01820380E-01-0.07705607E-05 0.14992929E-09-0.10755629E-13
2
0.15235267E+05-0.03266386E+02 0.02462608E+02 0.09582781E-01-0.07087359E-04
3
0.13633683E-08 0.02969647E-11 0.16061522E+05 0.12141870E+02
4
HONO
31787H
1N
1O
2
G 0300.00
5000.00 1000.00
1
156
0.05486892E+02 0.04218064E-01-0.16491426E-05 0.02971876E-08-0.02021148E-12
2
-0.11268646E+05-0.02997002E+02 0.02290413E+02 0.14099223E-01-0.13678717E-04
3
0.07498780E-07-0.01876905E-10-0.10431945E+05 0.13280769E+02
4
NO3
121286N
1O
3
G 0300.00
5000.00 1000.00
1
0.07120307E+02 0.03246228E-01-0.01431613E-04 0.02797053E-08-0.02013008E-12
2
0.05864479E+05-0.01213730E+03 0.01221076E+02 0.01878797E+00-0.01344321E-03
3
0.01274601E-07 0.01354060E-10 0.07473144E+05 0.01840203E+03
4
HNO3
121286H
1N
1O
3
G 0300.00
5000.00 1000.00
1
0.07003844E+02 0.05811493E-01-0.02333788E-04 0.04288814E-08-0.02959385E-12
2
-0.01889952E+06-0.10478628E+02 0.13531850E+01 0.02220024E+00-0.01978811E-03
3
0.08773908E-07-0.16583844E-11-0.01738562E+06 0.01851868E+03
4
CLCO
40992C
1 O 1CL 1
G 0300.00
4000.00 1500.00
1
0.06134826E+02 0.05369293E-02-0.07583742E-06-0.15145565E-10 0.03376079E-13
2
-0.05363338E+05-0.03198171E+02 0.04790425E+02 0.03165209E-01-0.02098200E-04
3
0.07703306E-08-0.13463511E-12-0.04812905E+05 0.04257479E+02
4
NOCL
0N
1O
1CL 1
0G
300.000 1700.000 1000.00
0 1
0.44662266E+01 0.39218174E-02-0.23816098E-05 0.65394836E-09-0.57884269E-13
2
0.37226990E+05-0.21423084E+02 0.39786872E+01 0.62832156E-02-0.65405679E-05
3
0.38378277E-08-0.95666425E-12 0.37303935E+05-0.19173798E+02
4
S
S
1
0
0
0G
300.00
5000.00 1000.00
0 1
2.90214800E+00-5.48454600E-04 2.76457600E-07-5.01711500E-11 3.15068500E-15
2
3.24942300E+04 3.83847100E+00 3.18732900E+00-1.59577600E-03 2.00553100E-06
3
-1.50708100E-09 4.93128200E-13 3.24225900E+04 2.41444100E+00
4
SH
H
1S
1
0
0G
300.00
5000.00 1000.00
0 1
3.05381000E+00 1.25888400E-03-4.24916900E-07 6.92959100E-11-4.28169100E-15
2
1.58822500E+04 5.97355100E+00 4.13332700E+00-3.78789300E-04-2.77785400E-06
3
5.37011200E-09-2.39400600E-12 1.55586200E+04 1.61153500E-01
4
H2S
H
2S
1
0
0G
300.00
5000.00 1000.00
0 1
157
2.88314700E+00 3.82783500E-03-1.42339800E-06 2.49799900E-10-1.66027300E-14
2
-3.48074300E+03 7.25816200E+00 3.07102900E+00 5.57826100E-03-1.03096700E-05
3
1.20195300E-08-4.83837000E-12-3.55982600E+03 5.93522600E+00
4
SO
O
1S
1
0
0G
300.00
5000.00 1000.00
0 1
4.02107800E+00 2.58485600E-04 8.94814200E-08-3.58014500E-11 3.22843000E-15
2
-7.11962000E+02 3.45252300E+00 3.08040100E+00 1.80310600E-03 6.70502200E-07
3
-2.06900500E-09 8.51465700E-13-3.98616300E+02 8.58102800E+00
4
SO2
O
2S
1
0
0G
300.00
5000.00 1000.00
0 1
5.25449800E+00 1.97854500E-03-8.20422600E-07 1.57638300E-10-1.12045100E-14
2
-3.75688600E+04-1.14605600E+00 2.91143900E+00 8.10302200E-03-6.90671000E-06
3
3.32901600E-09-8.77712100E-13-3.68788200E+04 1.11174000E+01
4
SO3
O
3S
1
0
0G
300.00
5000.00 1000.00
0 1
7.05066800E+00 3.24656000E-03-1.40889700E-06 2.72153500E-10-1.94236500E-14
2
-5.02066800E+04-1.10644300E+01 2.57528300E+00 1.51509200E-02-1.22987200E-05
3
4.24025700E-09-5.26681200E-13-4.89441100E+04 1.21951200E+01
4
! from glarborg
HSO2
H
1O
2S
1
0G
300.000 5000.000 1409.000
11
8.08048825E+00 1.33060394E-03-4.88933631E-07 7.96224125E-11-4.77570051E-15
2
-2.00218170E+04-1.59181319E+01 1.42680581E+00 2.13913839E-02-2.35694506E-05
3
1.19520863E-08-2.28851344E-12-1.82010558E+04 1.81504319E+01
4
HOSO
H
1O
2S
1
0G
300.00
2000.00 1000.00
0 1
9.60146992E+00-2.53592657E-02 6.76829409E-05-6.34954136E-08 1.95893537E-11
2
-3.12540147E+04-1.56740934E+01 9.60146992E+00-2.53592657E-02 6.76829409E-05
3
-6.34954136E-08 1.95893537E-11-3.12540147E+04-1.56740934E+01
4
HOSO2
H
1O
3S
1
0G
300.00
2000.00 1000.00
0 1
7.62277304E+00-4.19908990E-03 3.52054969E-05-4.12715317E-08 1.40006629E-11
2
-4.69478133E+04-7.80787503E+00 7.62277304E+00-4.19908990E-03 3.52054969E-05
3
-4.12715317E-08 1.40006629E-11-4.69478133E+04-7.80787503E+00
4
SN
N
1S
1
0
0G
300.00
5000.00 1000.00
0 1
158
3.88828700E+00 6.77842700E-04-2.72530900E-07 5.13592700E-11-3.59383600E-15
2
3.04449600E+04 4.19429100E+00 3.40734600E+00 1.79788700E-03-2.01897000E-06
3
2.10785700E-09-9.52759200E-13 3.06237300E+04 6.82148100E+00
4
S2
S
2
0
0
0G
300.00
5000.00 1000.00
0 1
3.90444300E+00 6.92573300E-04-1.23309700E-07 8.78380900E-13 1.37466200E-15
2
1.42569300E+04 4.95683400E+00 3.15767300E+00 3.09948000E-03-1.56074600E-06
3
-1.35789100E-09 1.13744400E-12 1.43918700E+04 8.59606200E+00
4
CS
C
1S
1
0
0G
300.00
5000.00 1000.00
0 1
3.73743100E+00 8.18045100E-04-3.17891800E-07 5.35680100E-11-2.88619500E-15
2
3.24772500E+04 3.57655700E+00 2.93862300E+00 2.72435200E-03-2.39770700E-06
3
1.68950100E-09-6.66505000E-13 3.27399200E+04 7.84872000E+00
4
COS
O
1C
1S
1
0G
300.00
5000.00 1000.00
0 1
5.19192500E+00 2.50612300E-03-1.02439600E-06 1.94391400E-10-1.37080000E-14
2
-1.84621000E+04-2.82575500E+00 2.85853100E+00 9.51545800E-03-8.88491500E-06
3
4.22099400E-09-8.55734000E-13-1.78514500E+04 9.08198900E+00
4
HSNO
H
1O
1N
1S
1G
300.00
5000.00 1000.00
0 1
2.90214800E+00-5.48454600E-04 2.76457600E-07-5.01711400E-11 3.15068400E-15
2
3.24942300E+04 3.83847100E+00 3.18732900E+00-1.59577630E-03 2.00553100E-06
3
-1.50708140E-09 4.93128200E-13 3.24225900E+04 2.41444100E+00
4
HSO
H
1O
1S
1
0G
300.000 5000.000 1404.000
01
5.60653294E+00 1.28334834E-03-4.66454491E-07 7.54200960E-11-4.50135500E-15
2
-4.81162778E+03-4.00613348E+00 2.36341863E+00 9.50396518E-03-8.36764005E-06
3
3.48648058E-09-5.61436742E-13-3.77743698E+03 1.31369204E+01
4
! from glarborg
HOS
H
1O
1S
1
0G
300.000 5000.000 1436.000
01
4.48812484E+00 1.82829854E-03-5.65521100E-07 8.16662597E-11-4.49316905E-15
2
-1.53636177E+03 2.39785536E+00 2.75556471E+00 7.31007463E-03-7.08551557E-06
3
3.50361758E-09-6.69410871E-13-1.09048921E+03 1.11726880E+01
4
HSOH
H
2O
1S
1
0G
300.000 5000.000 1407.000
11
159
6.92917693E+00 2.24452779E-03-7.90979097E-07
2
-1.70625997E+04-1.17716986E+01 2.10449581E+00
3
5.11270771E-09-8.13184236E-13-1.55220641E+04
4
! from glarborg, different thermodynamics
H2SO
H
2O
1S
1
0G
11
6.05713665E+00 3.34805040E-03-1.26811609E-06
2
-8.10888022E+03-7.74337887E+00 1.67605472E+00
3
3.40878662E-09-4.36976254E-13-6.69202687E+03
4
HOSHO
H
2O
2S
1
0G
11
9.02485610E+00 3.14966096E-03-1.13339516E-06
2
-3.60374633E+04-2.14761309E+01 1.64768512E+00
3
1.11468033E-08-2.06841918E-12-3.38188221E+04
4
HS2
burc94H
1S
2
0
0G
0 1
0.46552282E+01 0.29202531E-02-0.11010941E-05
2
0.16492900E+04 0.27987542E+01 0.40214995E+01
3
-0.48650943E-08 0.21391804E-11 0.18942796E+04
4
SO2*
pg00 S
1O
2
G
1
0.05254498E+02 0.01978545E-01-0.08204226E-05
2
-0.08300578E+04-0.01146056E+02 0.02911439E+02
3
0.03329016E-07-0.08777121E-11-0.01400178E+04
4
SCL
CL 1S
1
G
1
0.45818029E+01 0.21947902E-06-0.40124896E-08
2
0.17447034E+05 0.23937794E+01 0.43257799E+01
3
0.13136131E-08-0.35151127E-12 0.17493485E+05
4
CH
JANAFC
1H
1
0
0G
01
2.52630635E+00 1.80332526E-03-4.84589067E-07
2
7.07726347E+04 7.35584439E+00 3.36517755E+00
3
-4.22584668E-10 5.86289093E-14 7.04631376E+04
4
CH2
JANAFC
1H
2
0
0G
01
160
1.25463837E-10-7.39419240E-15
1.44325666E-02-1.24381307E-05
1.37425593E+01
300.000
5000.000 1683.000
2.11370265E-10-1.28989945E-14
1.36703075E-02-1.00346844E-05
1.56138164E+01
300.000
5000.000 1394.000
1.82050134E-10-1.08158633E-14
2.36621687E-02-2.33383665E-05
1.69561663E+01
298.150
5000.000 2000.00
0.18878697E-09-0.12318000E-13
0.31961918E-02 0.21507270E-05
0.64213003E+01 0.32457475E+04
0300.00
5000.00
1000.00
0.01576383E-08-0.01120451E-12
0.08103022E-01-0.06906710E-04
0.01111740E+03
300.000
5000.000 1000.00
0.42919972E-11-0.41192556E-15
0.11193879E-02-0.18253796E-05
0.36051734E+01
300.000
5000.000 1362.000
5.68080160E-11-2.40047828E-15
1.94434021E-05 9.12668865E-07
2.78685063E+00
300.000
5000.000 1409.000
3.71545549E+00 2.79298692E-03-8.73945386E-07 1.27374469E-10-7.05908213E-15
2
4.51374664E+04 1.13325113E+00 3.10563747E+00 4.03144515E-03-1.78816805E-06
3
4.13320881E-10-3.75171289E-14 4.53718718E+04
4
CH2(S)
H
2C
1
0
0G
0 1
3.09732461E+00 2.80331155E-03-7.10881104E-07
2
4.95090024E+04 4.31246006E+00 3.32929383E+00
3
-1.04565889E-10 2.51400070E-14 4.94285310E+04
4
CH3
H
3C
1
0
0G
0 1
2.84405200E+00 6.13797400E-03-2.23034500E-06
2
1.64378100E+04 5.45269700E+00 2.43044300E+00
3
1.62182900E-08-5.86495300E-12 1.64237800E+04
4
CH4
JANAFC
1H
4
0
0G
01
1.78092211E+00 9.74452639E-03-3.42930517E-06
2
-1.00945292E+04 9.16546733E+00 3.19715119E+00
3
-6.00052219E-09 1.24529966E-12-1.01110356E+04
4
CH2OH
THERMC
1H
3O
1
0G
11
6.19306234E+00 5.07058138E-03-1.69091931E-06
2
-3.94142242E+03-9.38725416E+00 1.88250578E+00
3
3.74863620E-09-5.37480607E-13-2.45553760E+03
4
CH3O
THERMC
1H
3O
1
0G
01
4.74429408E+00 6.60354819E-03-2.61174475E-06
2
-4.04799242E+02-3.05593859E+00-1.17225816E+00
3
7.80307444E-09-1.34408591E-12 1.47975243E+03
4
CH3OH
THERMC
1H
4O
1
0G
11
4.59418840E+00 8.84373788E-03-2.95933831E-06
2
-2.65062563E+04-1.06630729E+00 1.56247567E+00
3
4.31728248E-12 2.32389755E-13-2.51856083E+04
4
C2H
Field87C
2H
1
0
0G
01
161
4.48071530E+00
300.00
5000.00 1360.00
8.36924323E-11-3.81270428E-15
2.26625413E-03-2.38920714E-07
3.06576550E+00
300.00
5000.00 1000.00
3.78516100E-10-2.45215900E-14
1.11241000E-02-1.68022000E-05
6.78979400E+00
300.000
5000.000 1706.000
5.43903042E-10-3.20521160E-14
2.00818162E-03 8.06603744E-06
3.22246966E+00
300.000
5000.000 1392.000
2.58276720E-10-1.48215984E-14
1.51099762E-02-1.05243599E-05
1.37504657E+01
300.000
5000.000 1396.000
4.77928742E-10-3.13974103E-14
2.20349833E-02-1.82975276E-05
2.81336104E+01
300.000
5000.000 1387.000
4.52531299E-10-2.59724665E-14
1.35883881E-02-4.67956911E-06
1.61012691E+01
300.000
5000.000 2024.000
4.50481687E+00 2.31752772E-03-8.52834683E-07 1.39468167E-10-8.39945729E-15
2
6.48215191E+04-1.80015167E+00 3.36614004E+00 4.30862263E-03-1.77961296E-06
3
1.16375577E-10 5.69561595E-14 6.52622191E+04
4
C2H2
JANAFC
2H
2
0
0G
01
5.58079185E+00 4.13414447E-03-1.41744388E-06
2
2.49557217E+04-9.70120474E+00 3.17826088E+00
3
1.95230262E-10 1.36601029E-13 2.59408845E+04
4
C2H3
MGC
2H
3
0
0G
01
5.54192160E+00 5.83527734E-03-1.90937796E-06
2
3.33365935E+04-6.00049099E+00 2.02995091E+00
3
2.48655305E-09-2.99971920E-13 3.46030855E+04
4
C2H4
JANAFC
2H
4
0
0G
01
5.04902709E+00 9.03240832E-03-3.05663601E-06
2
3.67830603E+03-6.49864284E+00 6.53934711E-01
3
2.41508271E-09-2.30958678E-13 5.38196410E+03
4
C2H5
BLPC
2H
5
0
0G
11
5.55775601E+00 1.08697043E-02-3.72234659E-06
2
1.12858008E+04-7.27721884E+00 1.75409028E+00
3
-3.71126053E-10 3.32382683E-13 1.30432122E+04
4
C2H6
JANAFC
2H
6
0
0G
11
5.79770134E+00 1.30844142E-02-4.45782896E-06
2
-1.34692940E+04-1.12190298E+01 4.74260078E-01
3
1.42821577E-09 3.69083854E-14-1.12169150E+04
4
CH2CO
THERMC
2H
2O
1
0G
01
7.56655849E+00 4.38618679E-03-1.46608341E-06
2
-8.94777853E+03-1.65449287E+01 1.53866880E+00
3
9.12485651E-09-1.66311280E-12-7.15400366E+03
4
HCCOH
32387H
2C
2O
1
G
1
162
4.52636079E+00
300.000
5000.000 1376.000
2.20442432E-10-1.28056651E-14
8.28386242E-03-3.41250852E-06
3.72841870E+00
300.000
5000.000 1390.000
2.87787492E-10-1.63580788E-14
1.35234576E-02-8.13106656E-06
1.30360744E+01
300.000
5000.000 1394.000
4.70995771E-10-2.71778308E-14
1.78307866E-02-9.42052861E-06
1.76768137E+01
300.000
5000.000 1379.000
5.78205207E-10-3.35527708E-14
1.62227919E-02-4.99070479E-06
1.45429900E+01
300.000
5000.000 1384.000
6.90057114E-10-3.99465946E-14
2.22846672E-02-9.49503792E-06
1.86523474E+01
300.000
5000.000 1407.000
2.24243208E-10-1.28796340E-14
2.12191771E-02-1.96411582E-05
1.48116548E+01
0300.00
4000.00
1000.00
0.07328324E+02 0.03336416E-01-0.03024705E-05-0.01781106E-08 0.03245168E-12
2
0.07598258E+05-0.14012140E+02 0.03899465E+02 0.09701075E-01-0.03119309E-05
3
-0.05537732E-07 0.02465732E-10 0.08701190E+05 0.04491874E+02
4
CH3CO
T 9/92C
2H
3O
1
0G
200.000 6000.00 1000.0
1
0.59447731E+01 0.78667205E-02-0.28865882E-05 0.47270875E-09-0.28599861E-13
2
-0.37873075E+04-0.50136751E+01 0.41634257E+01-0.23261610E-03 0.34267820E-04
3
-0.44105227E-07 0.17275612E-10-0.26574529E+04 0.73468280E+01-0.12027167E+04
4
CH2SING
L S/93C
1H
2
00
00G
200.000 3500.000 1000.000
1
2.29203842E+00 4.65588637E-03-2.01191947E-06 4.17906000E-10-3.39716365E-14
2
5.09259997E+04 8.62650169E+00 4.19860411E+00-2.36661419E-03 8.23296220E-06
3
-6.68815981E-09 1.94314737E-12 5.04968163E+04-7.69118967E-01 9.93967200E+03
4
C3H7
API53C
3H
7
0
0G
300.000 5000.000 1391.000
21
9.15074687E+00 1.45922018E-02-4.91333492E-06 7.54837953E-10-4.34754801E-14
2
7.31350879E+03-2.43964893E+01-6.78379210E-01 3.73998985E-02-2.54421540E-05
3
9.32383949E-09-1.44268250E-12 1.07751694E+04 2.85014328E+01
4
CH2CHO
12/94THERMC
2H
3O
1
0G
300.000 5000.000 1380.000
11
7.60819764E+00 6.87037690E-03-2.40937632E-06 3.80385280E-10-2.23286251E-14
2
-1.88833365E+03-1.67475792E+01 1.69212880E+00 1.96084313E-02-1.27422618E-05
3
4.17166950E-09-5.59542594E-13 2.98762212E+02 1.54509311E+01
4
CH3CHO
THERMC
2H
4O
1
0G
300.000 5000.000 1416.000
11
7.74389357E+00 8.24524584E-03-2.65935827E-06 3.96779966E-10-2.23897706E-14
2
-2.32123342E+04-1.66062009E+01-8.35980986E-01 3.15729942E-02-2.70192582E-05
3
1.18998609E-08-2.07905711E-12-2.06158008E+04 2.82159715E+01
4
CH3CL
RDGC
1H
3CL 1
0G
300.000 5000.000 1386.000
01
4.76112984E+00 6.88813584E-03-2.35191472E-06 3.64610423E-10-2.11289668E-14
2
-1.20879947E+04-2.03072265E+00 1.74022083E+00 1.22225030E-02-5.36875160E-06
3
8.44256529E-10 1.83766212E-14-1.08301327E+04 1.48651691E+01
4
CH2CL
ROUX,RADIC
1H
2CL 1
0G
300.000 5000.000 1421.000
01
163
5.71482502E+00 3.31632237E-03-1.07732089E-06 1.61593503E-10-9.15465420E-15
2
1.24026565E+04-4.91796614E+00 1.92490517E+00 1.33892352E-02-1.12999805E-05
3
4.83763733E-09-8.18227430E-13 1.35668346E+04
4
CH2CLO.
7/89
C
1O
1H
2CL 1G
01
6.23016634E+00 5.85335042E-03-2.04343616E-06
2
-3.01375514E+03-6.13215836E+00 2.69730811E+00
3
6.29748948E-10 9.22568674E-14-1.54332205E+03
4
C2H5CL
JANAFC
2H
5CL 1
0G
11
8.42602350E+00 1.08670043E-02-3.69875171E-06
2
-1.75817705E+04-2.02070663E+01 3.66148399E-01
3
7.32637257E-09-1.10750593E-12-1.47415074E+04
4
COCL2
BSNC
1O
1CL 2
0G
01
8.37356642E+00 1.45611397E-03-5.20810326E-07
2
-2.94214218E+04-1.48380786E+01 4.47662819E+00
3
5.66457278E-09-1.03108770E-12-2.82550178E+04
4
CH2CLC.H2
ROUX87
C
2
0H
4CL 1G
11
8.54612636E+00 8.70530333E-03-3.06156397E-06
2
6.34576886E+03-1.90781271E+01 3.05624191E-01
3
8.39568397E-09-1.40542189E-12 9.24856407E+03
4
C2H4OCL
7/89
C
2O
1H
4CL 1G
31
1.10145297E+01 8.15790219E-03-2.83847077E-06
2
-6.00681870E+02-2.65698041E+01-1.53127350E+00
3
2.43865270E-08-4.83222322E-12 2.96342754E+03
4
CHCLC.H
BBB
C
2
0H
2CL 1G
01
1.06526620E+01 3.61331241E-03-1.53803006E-06
2
2.57639738E+04-3.33173153E+01 4.19961326E+00
3
-1.65976891E-08 4.20107817E-12 2.95916757E+04
4
C2H3CL
MAN,LOUWC
2H
3CL 1
0G
01
164
1.49532259E+01
300.000
5000.000 1373.000
3.21614950E-10-1.88374791E-14
1.19860671E-02-5.26850873E-06
1.36469449E+01
300.000
5000.000 1392.000
5.72375356E-10-3.31331698E-14
2.94578293E-02-2.02144179E-05
2.31928787E+01
300.000
5000.000 1398.000
8.33827599E-11-4.94460050E-15
1.22362568E-02-1.20349900E-05
5.46450425E+00
300.000
5000.000 1382.000
4.84249575E-10-2.84616389E-14
2.80849016E-02-2.10736532E-05
2.52245042E+01
300.000
5000.000 1396.000
4.45765276E-10-2.60698167E-14
4.60006810E-02-4.75639250E-05
3.78839199E+01
300.000
5000.000 1511.000
2.74591563E-10-1.75187824E-14
3.01912456E-03 1.75440170E-05
6.94137452E+00
300.000
5000.000 1404.000
8.12532976E+00 6.32279870E-03-2.10889293E-06
2
-1.07821872E+03-1.83168402E+01 2.65621701E-01
3
8.75943199E-09-1.42117873E-12 1.44275080E+03
4
CH3C.HCL
ROUX87
C
2
0H
4CL 1G
01
7.56228919E+00 9.78512691E-03-3.39196568E-06
2
4.81011272E+03-1.39885482E+01 1.12828446E+00
3
6.28310091E-09-1.04458965E-12 7.17099543E+03
4
CH2CLO
THERMC
1H
2O
1CL 1G
01
6.44020663E+00 5.56800020E-03-1.92136661E-06
2
-3.26090898E+03-7.43338025E+00 8.93635756E-01
3
5.99701589E-09-9.84844641E-13-1.40140300E+03
4
CHCLO
BSNC
1H
1O
1CL 1G
01
6.27872759E+00 3.15667555E-03-1.08913544E-06
2
-2.22087864E+04-6.45495503E+00 2.84949067E+00
3
3.76997592E-09-6.21893307E-13-2.10716929E+04
4
CHO
ESTC
1H
1O
1
0G
01
3.69472521E+00 3.18594296E-03-1.08841412E-06
2
3.82240388E+03 4.69145660E+00 3.53025733E+00
3
-1.72919680E-09 3.98120351E-13 4.08521632E+03
4
HCO2
3/29/94 THERMC
1H
1O
2
0G
01
6.31449894E+00 3.34548164E-03-1.20507137E-06
2
-2.20255876E+04-9.44753566E+00 1.18876543E+00
3
1.67146402E-09 1.99537242E-14-2.01415371E+04
4
H2S2
burc94H
2S
2
0
0G
0 1
0.65731735E+01 0.25619139E-02-0.69109315E-06
2
-0.24677791E+03-0.72991840E+01 0.21128554E+01
3
0.28468801E-07-0.95576325E-11 0.67951055E+03
4
OCS
121286C
1O
1S
1
G
1
165
3.22338516E-10-1.85123802E-14
2.62518050E-02-2.13968077E-05
2.32522142E+01
300.000
5000.000 1385.000
5.31268607E-10-3.10097278E-14
2.43449415E-02-1.65723496E-05
2.08663440E+01
300.000
5000.000 1396.000
3.00102093E-10-1.74854992E-14
1.91814651E-02-1.48947039E-05
2.21205362E+01
300.000
5000.000 1396.000
1.70121699E-10-9.91319183E-15
1.16574562E-02-9.25161808E-06
1.17804371E+01
300.000
5000.000 1367.000
1.68761454E-10-9.77966305E-15
1.88364239E-03 1.78452098E-06
6.23492345E+00
300.000
5000.000 1455.000
1.93694895E-10-1.15132236E-14
1.37389141E-02-8.14389853E-06
1.85517814E+01
298.150
5000.000 2000.00
0.94286242E-10-0.52907210E-14
0.21398828E-01-0.33893856E-04
0.14205983E+02 0.20128667E+04
0300.00
5000.00
1000.00
0.05191924E+02 0.02506123E-01-0.10243963E-05 0.01943914E-08-0.13707999E-13
2
-0.01846210E+06-0.02825755E+02 0.02858530E+02 0.09515458E-01-0.08884915E-04
3
0.04220994E-07-0.08557340E-11-0.01785144E+06 0.09081989E+02
4
166
APPENDIX B
PUMP TESTING DATA
167
Test 1: DUO 10 with different orifice sizes (150, 200, 300, 400 and 500μm)
Pressure
(Torr)
valve
closed
P1
P2
P3
3.80E-04
6.30E-08
8.10E-08
open
valve
150μ
0.108
L/min
0.273
L/min
close
valve
2.70E-01
4.30E-05
2.70E-07
3.00E-01
6.00E-05
3.40E-07
3.80E-04
1.10E-07
9.30E-08
300μ
Pressure
(Torr)
valve
closed
open
valve
0.185
L/min
0.385
L/min
0.522
L/min
0.585
L/min
P1
P2
P3
3.80E-04
5.70E-08
8.70E-08
1.80E-01
2.40E-05
2.60E-07
1.70E-01
2.30E-05
2.20E-07
2.50E-01
4.10E-05
2.80E-07
4.60E-01
3.10E-04
1.10E-06
6.60E-01
4.40E-03
1.30E-05
0.766
L/min
0.834
L/min
0.926
L/min
Pressure
(Torr)
valve
closed
open
valve
0.185
L/min
0.385
L/min
400μ
0.585
L/min
P1
P2
P3
3.80E-04
9.10E-08
9.40E-08
6.00E-03
1.00E-06
1.30E-07
1.30E-02
1.90E-06
1.20E-07
2.30E-02
3.10E-06
1.20E-07
5.60E-02
7.40E-06
1.30E-07
2.30E-01
3.50E-05
2.30E-07
5.30E-01
7.40E-04
2.30E-06
6.00E-01
2.00E-03
6.00E-06
close valve
3.80E-04
1.60E-07
9.50E-08
0.766
L/min
0.926
L/min
0.975
L/min
1.094
L/min
1.10E-01
1.50E-05
1.50E-07
3.70E-01
1.10E-04
5.00E-07
5.40E-01
8.30E-04
2.60E-06
6.00E-01
3.00E-03
9.00E-06
Pressure
(Torr)
open
valve
0.185
L/min
0.385
L/min
500μ
0.585
L/min
P1
P2
P3
5.70E-03
1.00E-06
1.50E-07
1.20E-02
1.70E-06
1.10E-07
2.20E-02
3.10E-06
1.20E-07
4.50E-02
5.90E-06
1.20E-07
168
Test 2: Heating test with DUO 10 (500 μm, 0.15 L/min)
Pressure (Torr) valve closed
P1
3.80E-04
P2
4.50E-07
P3
2.60E-07
Tin=25C, Tb=180C
open valve
after 5 min.
3.60E-01
8.90E-05
6.60E-07
3.70E-01
1.00E-04
6.20E-07
close valve
3.80E-04
5.50E-07
6.20E-07
Tin=119C, Tb=180C
Pressure (Torr) valve closed
P1
3.80E-04
P2
4.30E-07
P3
2.60E-07
Pressure (Torr) valve closed
P1
3.80E-04
P2
3.60E-07
P3
2.70E-07
Pressure (Torr) valve closed
P1
3.80E-04
P2
3.50E-07
P3
2.60E-07
open valve
3.60E-01
8.50E-05
6.40E-07
3.60E-01
8.90E-05
6.00E-07
open valve
3.70E-01
1.70E-04
8.90E-07
3.70E-01
1.20E-04
6.40E-07
3.80E-01
1.70E-04
8.40E-07
Tin=191C, Tb=180C
after 5 min.
open valve
3.50E-01
8.20E-05
6.00E-07
3.60E-01
9.20E-05
6.00E-07
3.60E-01
1.10E-04
6.40E-07
3.70E-01
1.40E-04
7.50E-07
3.90E-01
4.30E-03
1.70E-06
Tin=230.2C, Tb=180C
after 3:20 min. 3:22 min.
3.80E-01
2.10E-04
1.00E-06
4.00E-01
5.80E-04
2.20E-06
169
close valve
4.20E-01
1.00E-03
3.30E-07
close valve
4.00E-01
1.10E-03
4.00E-06
3.90E-01
2.70E-04
1.00E-06
3.80E-04
4.70E-07
2.80E-07
3.80E-04
5.30E-07
2.80E-07
Pressure (Torr) valve closed
P1
3.80E-04
P2
3.50E-07
P3
2.60E-07
open valve
3.90E-04
2.40E-04
1.10E-06
Tin=265.5C, Tb= 180C
after 1 min.
3.90E-01
3.10E-04
1.30E-06
4.00E-01
4.80E-04
1.90E-06
2 min.
close valve
4.10E-01
1.10E-03
3.50E-06
3.80E-04
4.80E-07
2.80E-07
Tin=303C, Tb=180C
Pressure (Torr) valve closed
P1
3.80E-04
P2
3.90E-07
P3
2.70E-07
open valve
4.30E-01
1.40E-03
5.60E-06
after 1 min. close valve
4.40E-01
3.10E-03
1.10E-06
4.60E-01
6.80E-03
2.30E-06
170
3.80E-04
6.20E-07
3.40E-07
Test 3: DUO 20 with 500 μm, 0.15 L/min
Pressure
(Torr)
P1
P2
P3
Pressure
(Torr)
P1
P2
P3
Pressure
(Torr)
P1
P2
P3
valve
closed
3.80E-04
9.10E-07
5.30E-07
valve
closed
3.80E-04
7.00E-07
4.00E-07
Tin=25C, Tb=180C
open
after 2
valve
min.
3.50E-01
3.50E-01
8.40E-05
8.50E-05
1.00E-06
8.50E-07
close valve
3.80E-04
1.00E-06
5.10E-07
Ton=105C, Tb=180C
open
after 3
valve
min.
3.50E-01
7.80E-05
8.70E-07
valve
closed
open
valve
3.80E-04
5.00E-07
3.30E-07
3.60E-01
7.90E-05
7.50E-07
3.50E-01
8.20E-05
7.30E-07
close
valve
3.50E-01
8.40E-05
7.20E-07
3.80E-04
8.60E-07
4.00E-07
Tin=156C, Tb=180C
after 1
3 min.
5 min.
min.
3.50E-01
8.00E-05
6.80E-07
3.50E-01
8.30E-05
6.60E-07
3.60E-01
8.70E-05
6.60E-07
6 min.
close
valve
3.60E-01
8.80E-05
6.60E-07
3.80E-04
6.50E-07
3.40E-07
Tin=191C, Tb=180C
Pressure
(Torr)
P1
P2
P3
valve
closed
open
valve
3.80E-04
4.90E-07
3.20E-07
3.60E-01
9.10E-05
7.70E-07
3.50E-01
8.10E-05
7.10E-07
after 1 min.
3 min.
4 min.
5 min.
7 min.
close
valve
3.50E-01
8.10E-05
6.70E-07
3.50E-01
8.50E-05
6.60E-07
3.00E-01
8.70E-05
6.60E-07
3.60E-01
8.90E-05
6.60E-07
3.60E-01
9.00E-05
6.70E-07
3.80E-04
6.70E-07
3.40E-07
171
Tin=230C, Tb=180C
Pressure
(Torr)
P1
P2
P3
valve
closed
open
valve
3.80E-04
4.70E-07
3.30E-07
3.60E-01
8.40E-05
7.00E-07
3.50E-01
8.20E-05
6.70E-07
valve
closed
open
valve
after 1
min.
2 min.
3.80E-04
4.50E-07
3.30E-07
3.60E-01
1.10E-04
8.60E-07
3.60E-01
1.20E-04
8.20E-07
3.70E-01
1.60E-04
9.30E-07
after 2min.
4 min.
5 min.
6 min.
7 min.
3.60E-01
8.40E-05
6.60E-07
3.60E-01
8.80E-05
6.60E-07
3.60E-01
9.50E-05
6.90E-07
3.70E-01
1.30E-04
7.90E-07
4.00E-01
4.50E-04
1.90E-06
3 min.
3.5 min.
5 min.
close
valve
3.80E-01
2.60E-04
1.30E-06
4.10E-01
1.00E-03
3.80E-06
4.40E-01
5.00E-03
Tin=253C, Tb=180C
Pressure
(Torr)
P1
P2
P3
172
3.8-4
8.00E-07
4.20E-07
close
valve
4.20E-01
1.00E-03
3.60E-06
3.80E-04
7.10E-07
3.60E-07
Test 4: PENTA35 with 500 μm, 0.15 L/min
Pressure
(Torr)
P1
P2
P3
valve
closed
open
valve
after 1
min.
2 min.
5 min.
6 min.
12 min.
15 min.
close
valve
3.80E-04
1.20E-07
1.10E-07
3.00E-01
5.80E-05
4.10E-07
3.20E-01
6.70E-05
4.20E-07
3.40E-01
8.20E-05
4.50E-07
3.50E-01
9.30E-05
4.70E-07
3.50E-01
9.70E-05
4.70E-07
3.60E-01
9.80E-05
4.70E-07
3.60E-01
1.00E-05
4.80E-07
3.60E-01
1.00E-05
4.80E-07
3.80E-04
2.20E-07
1.00E-07
Pressure
(Torr)
P1
P2
P3
valve
closed
3.80E-04
3.10E-07
4.70E-07
open
valve
1.90E-01
2.50E-05
5.30E-07
after 2
min.
3.20E-01
6.40E-05
6.70E-07
open
valve
2.20E-01
2.90E-03
3.30E-07
heat cord 0, blanket 180C
after 2
3 min.
4 min.
min.
3.30E-01
3.50E-01 3.70E-01
6.90E-05
9.00E-05 1.00E-04
4.40E-07
5.10E-07 5.40E-07
heat cord 0, blanket 180C
Pressure
(Torr)
P1
P2
P3
valve
closed
3.80E-04
2.10E-07
1.90E-06
3 min.
3.50E-01
8.90E-05
7.50E-07
5 min.
7.5 min.
8.5 min.
9.5 min.
close valve
3.50E-01
1.10E-04
8.10E-07
3.90E-01
2.60E-04
1.30E-06
4.10E-01
4.90E-04
2.20E-06
4.20E-01
1.00E-03
3.60E-06
3.80E-04
6.80E-07
4.70E-07
5 min.
3.80E-01
1.50E-04
7.20E-07
close
valve
3.80E-04
4.60E-07
1.80E-07
Tin=145C, Tb=180C
Pressure
(Torr)
P1
P2
P3
valve
closed
3.80E-04
2.30E-07
1.90E-07
open
valve
3.50E-01
8.10E-05
6.50E-07
after 2
min.
3.60E-01
1.10E-04
5.90E-07
3 min.
4 min.
4:20 min.
3.70E-01
1.70E-04
8.20E-07
3.90E-01
4.90E-04
1.90E-06
4.10E-01
1.00E-03
3.40E-04
173
close
valve
3.80E-04
5.90E-07
2.00E-07
Test 5: DUO 10 +PENTA35 with 150 μm, 0.15 L/min
Tin=25C, Tb=180C
Pressure
(Torr)
P1
P2
P3
valve
closed
open
valve
after
1min.
2 min.
3 min.
4 min.
5 min.
10 min.
15 min.
close
valve
1.00E-03
3.00E-07
1.90E-07
3.20E-01
3.40E-05
3.50E-07
4.00E-01
4.30E-05
3.90E-07
4.60E-01
4.90E-05
4.20E-07
4.90E-01
5.20E-05
4.30E-07
4.90E-01
5.30E-05
4.40E-07
4.90E-01
5.40E-05
4.40E-07
4.90E-01
5.40E-05
4.40E-07
4.90E-01
5.30E-05
4.40E-07
1.10E-03
4.00E-07
1.90E-07
Pressure
(Torr)
P1
P2
P3
valve
closed
1.00E-03
3.00E-07
1.80E-07
open
valve
5.10E-01
5.30E-05
4.30E-07
after
1min.
4.70E-01
5.00E-05
4.30E-07
Pressure
(Torr)
P1
P2
P3
valve
closed
1.00E-03
3.00E-07
1.80E-07
open
valve
5.00E-01
5.20E-05
4.30E-07
after
1min.
4.70E-01
5.00E-05
4.20E-07
Tin=147.2C, Tb=180C
2 min.
3 min.
4 min.
5 min.
10 min.
4.70E-01
5.00E-05
4.20E-07
4.70E-01
5.00E-05
4.20E-07
4.70E-01
5.00E-05
4.20E-07
4.70E-01
5.00E-05
4.20E-07
4.80E-01
5.10E-05
4.30E-07
close
valve
1.10E-03
4.00E-07
1.90E-07
heat cord 40% => 193.1, blanket 180C
2 min.
3 min.
4 min.
5 min.
10 min.
4.70E-01
5.00E-05
4.20E-07
4.70E-01
4.90E-05
4.20E-07
4.70E-01
5.00E-05
4.20E-07
4.70E-01
5.00E-05
4.20E-07
4.70E-01
5.10E-05
4.20E-07
close
valve
1.10E-03
4.10E-07
1.90E-07
Tin=235.3C, Tb=180C
Pressure
(Torr)
P1
P2
P3
valve
closed
1.00E-03
3.00E-07
1.00E-07
open
valve
5.50E-01
5.60E-05
4.40E-07
after
1min.
4.80E-01
5.00E-05
4.20E-07
2 min.
3 min.
4 min.
5 min.
10 min.
4.70E-01
5.00E-05
4.20E-07
4.70E-01
5.00E-05
4.20E-07
4.70E-01
5.00E-05
4.20E-07
4.70E-01
5.00E-05
4.20E-07
4.80E-01
5.10E-05
4.20E-07
174
close
valve
1.00E-03
4.00E-07
1.80E-07
Tin=282.5C, Tb=180C
Pressure
(Torr)
P1
P2
P3
valve
closed
open
valve
after
1min.
2 min.
3 min.
4 min.
5 min.
10 min.
15 min.
close
valve
1.00E-03
2.90E-07
1.70E-07
5.10E-01
5.40E-05
4.30E-07
4.70E-01
5.00E-05
4.10E-07
4.70E-01
4.90E-05
4.20E-07
4.70E-01
4.90E-05
4.10E-07
4.70E-01
4.90E-05
4.10E-07
4.70E-01
5.00E-05
4.10E-07
4.80E-01
5.00E-05
4.10E-07
4.80E-01
5.00E-05
4.20E-07
1.00E-03
4.00E-07
1.80E-07
valve
closed
open
valve
after
1min.
5 min.
10 min.
15 min.
20 min.
25 min.
30 min.
35 min.
close
valve
1.00E-03
2.90E-07
1.70E-07
5.00E-01
5.20E-05
4.20E-07
4.70E-01
4.90E-05
4.10E-07
4.70E-01
4.90E-05
4.10E-07
4.70E-01
5.00E-05
4.10E-07
4.80E-01
5.10E-05
4.20E-07
4.80E-01
5.10E-05
4.10E-07
4.80E-01
5.10E-05
4.20E-07
4.80E-01
5.00E-05
4.10E-07
4.80E-01
5.00E-05
4.20E-07
1.00E-03
4.50E-07
1.80E-07
valve
closed
open
valve
after
1min.
2 min.
3 min.
4min.
5min.
10 min.
15 min.
close
valve
1.00E-03
2.40E-07
1.70E-07
5.50E-04
5.40E-05
4.40E-07
4.70E-01
5.00E-05
4.00E-07
4.60E-01
4.90E-05
4.00E-07
4.60E-01
4.90E-05
4.00E-07
4.70E-01
4.90E-05
4.00E-07
4.70E-01
4.90E-05
4.00E-07
4.70E-01
5.00E-05
4.00E-07
4.80E-01
5.00E-05
4.00E-07
1.10E-03
3.30E-07
1.70E-07
valve
closed
open
valve
after
1min.
5 min.
10 min.
15 min.
20 min.
25 min.
30 min.
close
valve
1.00E-03
2.40E-07
1.70E-07
5.50E-01
5.70E-05
4.30E-07
4.60E-01
4.90E-05
4.00E-07
4.60E-01
4.90E-05
4.00E-07
4.70E-01
4.90E-05
4.00E-07
4.70E-01
5.00E-05
4.00E-07
4.70E-01
5.00E-05
4.00E-07
4.70E-01
5.00E-05
4.00E-07
4.80E-01
5.00E-05
4.00E-07
1.00E-03
4.00E-07
1.70E-07
Tin=322-327C, Tb=180C
Pressure
(Torr)
P1
P2
P3
Tin=365-373C, Tb=180C
Pressure
(Torr)
P1
P2
P3
Tin=411-415C, Tb=180C
Pressure
(Torr)
P1
P2
P3
175
176
APPENDIX C
LASER ALIGNMENT GUIDELINES
177
Remove the rear flange of the main chamber.
Remove the cover plate loosening the 3 screws shown below.
178
[152]
179
[152]
180
APPENDIX D
FLANGE DRAWINGS
181
Flange with Feedthroughs
182
Gas Feedthrough
183
Power Feedthrough
184
Thermocouple Feedthrough
185
186
APPENDIX E
SUPERSONIC SYSTEM INSTALLATION GUIDELINES
Removing the chopper and installing the skimmer flange assembly
187
Remove the front flange of the main chamber.
Disconnect the ceramic-beaded wires and remove the intermediate focusing lens
assembly by loosening the 4 screws on the plate shown below.
You will see the chopper once you remove the intermediate focusing lens
assembly. It is attached to the back with 3 screws. Simply remove those screws
and disconnect the wires that are green, red, black and white.
188
Install intermediate focusing lens assembly and connect ceramic-beaded wires
appropriately according to the configuration file. Check all connections with an
ohmmeter for continuity and short circuits.
189
With the intermediate aperture flange aligned with the ionizer aperture, locate the
Skimmer flange assembly.
Connect the final ceramic beaded wire to the rear of the skimmer mounting plate
as shown and install the skimmer flange assembly onto the front of the main
chamber. Secure with several nut and washers and copper gaskets as shown.
Follow the laser alignment procedure before attaching the front flange.
190
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