a dissertation submitted to the department of energy ...ph834px9700/bihter padak... · the...

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

http://creativecommons.org/licenses/by-nc/3.0/us/

This dissertation is online at: http://purl.stanford.edu/ph834px9700

© 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 Attribution-Noncommercial 3.0 United States License.

ii



http://purl.stanford.edu/ph834px9700

I certify that I have read this dissertation and that, in my opinion, it is fully adequatein scope and quality as a dissertation for the degree of Doctor of Philosophy.

Jennifer Wilcox, Primary Adviser


Gordon Brown, Jr


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 inUniversity Archives.

iii

v

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 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.

vi

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 custom-

built 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.

vii

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.

viii

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

ix

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.

xi

Dedicated to Erdem

xiii

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 16

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

xiv

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 16

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 16

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 16

Appendix 93

A Chemkin Model Data ......................................................................................... 95

B Pump Testing Data ............................................................................................. 167

C Laser Alignment Guidelines .............................................................................. 177

xv

D Flange Drawings ................................................................................................ 181

E Supersonic System Installation Guidelines ........................................................ 187

Bibliography 191

xvii

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 .......................................................................................... 21

2.4 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 ................................................................................................................ 30

2.9 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

xviii

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

mercuric chloride at 187 °C.................................................................................... 85

4.7 Relative abundances of ions ................................................................................... 87

xix

List of Figures

1.1 Pollutant control systems in coal-fired power plants ............................................. 3

1.2 Equilibrium mercury speciation in flue gas as a function of temperature

(Pittsburgh coal) ..................................................................................................... 5

2.1 Optimized geometries for Hg and Cl2 on different sites of the cluster (a) armchair

edge; (b) zigzag edge; (c) center ............................................................................ 19

2.2 Optimized geometries for Hg and Cl on different sites of the cluster (a) armchair

edge; (b)zigzag edge; (c) center ............................................................................. 19

2.3 Cluster models of mercury adsorbed on activated carbon (AC) and halogen-

embedded activated carbon. X: F, Cl, Br, I ............................................................ 20

2.4 Activated carbon clusters with oxygen functional groups: lactone, carbonyl,

phenol, and carboxyl .............................................................................................. 22

2.5 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

xx

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

xxi

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

1

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.

2

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

3

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.

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

NH3

SCR

Sorbent Injection

Ash &Sorbent

HgCl2 SO2

Flue Gas

Boiler

ESP Air Heater

Fan

Stack

Adsorbed Hg

1400 °C

Gypsum

FGD

350°C 140 °C

100°C

50°C

4

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 (gas-

gas) 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 HgCl2

[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

5

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 kinetically-

controlled, 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

6

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.

7

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

8

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

9

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

10

sulfur-impregnated activated carbons the lower the temperature the higher the adsorption

capacity of mercury because of exothermic behavior of mercury reaction with chloride [43-

46] 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

11

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.

13

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

14

properties of a molecule may be obtained by solving the Schrödinger Wave Equation (SWE)

given below:

EH (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)

t

tRritRr

zyxm

),,(),,(

2 2

2

2

2

2

22

(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:

2/h . The potential energy operator, v represents the potential energy of nuclear-

electron 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

15

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-Yang-

Parr 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

16

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 fourteen-

fused 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/6-

31G(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

17

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 MP2/6-

31G(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 thirty-

fused 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

18

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 four-

and 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

Armchair edge Zigzag edge Center

C-Cl 1.8137 1.8258 4.5093

19

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

20

Table 2.2: C-Cl and C-Hg bond distances (Å) for different positions on the surface

Armchair edge Zigzag edge Center

C-Cl 1.8461 1.8345 5.7448

C-Hg 2.4613 2.4788 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 halogen-

embedded activated carbon X: F, Cl, Br, I

21

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

Binding energies

(kcal/mol)

C-X Bond

distances (Ǻ)

AC -4.3235 -

AC-F -9.5885 1.4178

AC-Cl -7.7207 1.8461

AC-Br -6.6431 1.9809

AC-I -5.3697 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.

Lactone Carbonyl Phenol Carboxyl

C-Hg 2.4462 2.2586 2.4497 2.5078

22

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.

23

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

X=F X=Cl X=Br X=I

C-Hg C-F C-Hg C-Cl C-Hg C-Br C-Hg C-I

Lactone 2.4096 1.4116 2.4239 1.8395 2.4307 1.9891 2.4382 2.1640

Carbonyl 2.2608 1.4096 2.2671 1.8336 2.2678 1.9809 2.2730 2.1525

Phenol 2.3954 1.4165 2.4150 1.8468 2.4254 1.9959 2.4314 2.1718

Carboxyl 2.4428 1.4220 2.4616 1.8564 2.4690 2.0069 2.4747 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

Binding Energies (kcal/mol)

AC AC-F AC-Cl AC-Br AC-I

Lactone -10.2851 -16.7144 -14.6622 -13.4594 -11.8763

Carbonyl -8.8298 -14.5008 -13.0570 -12.1202 -10.9199

Phenol -6.7242 -12.6310 -10.5091 -9.2009 -7.7716

Carboxyl -1.2231 -7.6798 -4.0432 -2.4707 -0.6746

24

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.

25

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

26

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 Near-

Edge 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 iodine-

activated 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.

27

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 theoretical-

based 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].

28

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].

29

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 Exp92

C-C 1.42 1.42

C-H 1.09 1.07

C-C-C 120 120

C-C-H 119.7 120.0

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

30

is largely covalent, whereas there is no interaction between the two atoms if the bond

population is close to zero [90].

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)

Graphene Graphene-Cl Hg on Graphene

G G-Cl (1) BC A

C(6)-C(5) 0.486 0.516 0.489 0.497

C(5)-C(4) 0.342 0.332 0.336 0.332

C(4)-C(8) 0.393 0.175 0.458 0.408

C(8)-C(9) 0.302 0.038 0.107 0.308

C(9)-C(15) 0.302 0.313 0.108 0.374

C(15)-C(14) 0.393 0.450 0.458 0.187

C(14)-C(20) 0.342 0.339 0.338 0.208

C(20)-C(21) 0.486 0.490 0.490 0.484

Cl-C(8) 0.416

Hg-C(8) 0.251

Hg-C(9) -0.184

Hg-C(15) 0.251 0.252

Hg-C(14) -0.183

Hg-C(20) 0.258

G-Cl(1) G-Cl(2)

G-ClCl(1) G-ClCl(3) G-ClCl(2)

31

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.

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

HgHg Hg

a cb

A BC

32

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.

Figure 2.9: Binding of Hg at different sites of G-Cl model

D E F GH

Hg

d

Hg

f

Hg

e

Hg

g

Hg

h

33

Table 2.9: Bonding Mulliken population analysis for Hg on Graphene-Cl and HgCl on

Graphene (only bonds of interest are reported) *nearest carbon

Hg on Graphene-Cl HgCl on Graphene

D E F GH 1A 1B 1C 1D 2AB 2C 2D 3C

C(6)-C(5) 0.392 0.517 0.498 0.525 0.392 0.432 0.388 0.418 0.490 0.503 0.515 0.437

C(5)-C(4) 0.297 0.331 0.334 0.325 0.298 0.062 0.197 0.081 0.217 0.300 0.332 0.380

C(4)-C(8) 0.128 0.175 0.430 0.227 0.128 0.337 0.363 0.413 0.247 0.263 0.172 0.338

C(8)-C(9) 0.111 0.034 0.250 0.023 0.111 0.253 0.350 0.374 0.377 0.161 0.034 0.209

C(9)-C(15) 0.289 0.311 0.164 0.376 0.289 0.284 0.298 0.298 0.023 0.249 0.310 0.209

C(15)-C(14) 0.470 0.451 0.261 0.247 0.470 0.418 0.417 0.407 0.227 0.430 0.449 0.338

C(14)-C(20) 0.334 0.339 0.300 0.217 0.334 0.327 0.341 0.340 0.325 0.335 0.340 0.380

C(20)-C(21) 0.496 0.492 0.503 0.489 0.496 0.498 0.494 0.494 0.525 0.498 0.490 0.437

Cl-C* 0.367 0.403 0.388 0.367 0.309 0.333 0.388 0.406

Hg-Cl 0.005 0.006 0.265 0.008 0.006 0.005 0.259 0.007 0.008 0.265 0.006 0.252

Hg-C(5) 0.154 0.153 0.389 0.255

Hg-C(15) 0.368 0.255 0.223

Hg-C(8) 0.163 0.255 0.369 0.223

Hg-C(20) 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

34

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.

Figure 2.10: Energy diagram for different pathways of Hg on G-Cl

Reaction Coordinate

Rel

ativ

e E

ner

gy (

kca

l/m

ol)

-20

-10

0

10

20

30

40

50

60

70

G-Cl + Hg(g) G-Cl + Hg(g)

G + HgCl(g)

A,BC + Cl(g)

E

GH

D

F

35

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.

Figure 2.11: Binding of HgCl at different sites of G

(1a)

(1b)

(1c)

(1d)

Hg Cl

Cl Hg

Hg

Cl

Cl

Hg

(2a)

(2b)

(2c)

(2d)

Hg Cl

Cl Hg

Hg

Cl

Cl

Hg

1A 1B 1C 1D

2AB 2C 2D 3C

Hg

Cl (3c)

36

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.

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

Reaction Coordinate

Rel

ativ

e E

ner

gy (

kca

l/m

ol)

-70

-60

-50

-40

-30

-20

-10

0

10

G + HgCl(g)

G-Cl(1,2) + Hg(g)

3C

2D

2C 1B

2AB

G + HgCl(g)

A,BC + Cl(g)

37

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‟.

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

(1a)

(1b)

(1c)

Hg Cl

Cl Hg

Hg

Cl

(2a)

(2b)

(2c)

(2d)

Hg Cl

Cl Hg

Hg

Cl

Cl

Hg

1A2C‟ 1C‟ 1B2B‟ 2D‟

Cl(1) Cl(1) Cl(2)

Cl(2)

Cl(1)

Cl(2)

Cl(1)

Cl(2)

Cl(1)

2A‟

Cl(2)

38

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

HgCl on Graphene-Cl HgCl2 on Graphene

1A2C' 1C' 2A' 1B2B' 2D' 1A'' 1B'' 2A'' 2B'' 3B4B''

C(6)-C(5) 0.531 0.481 0.525 0.520 0.526 0.425 0.365 0.428 0.480 0.524

C(5)-C(4) 0.328 0.348 0.330 0.325 0.333 0.076 0.089 0.086 0.348 0.356

C(4)-C(8) 0.250 0.402 0.219 0.195 0.186 0.365 0.344 0.445 0.399 0.446

C(8)-C(9) -0.042 0.310 0.263 0.000 0.032 0.299 0.294 0.188 0.313 0.309

C(9)-C(15) 0.172 0.317 0.298 0.356 0.035 0.026 0.218 0.186 0.316 0.071

C(15)-C(14) 0.251 0.390 0.367 0.430 0.185 0.216 0.334 0.445 0.388 0.200

C(14)-C(20) 0.293 0.340 0.075 0.186 0.333 0.330 0.379 0.085 0.340 0.314

C(20)-C(21) 0.496 0.488 0.426 0.385 0.527 0.522 0.436 0.428 0.487 0.516

Cl(1)-C* 0.373 -0.002 0.379 0.420 0.430 0.314 0.348 0.324 0.0001 0.357

Cl(2)-C* 0.315 0.417 0.380 0.324

Hg-Cl(2) 0.266 0.248 0.002 0.261 0.006 0.001 0.254 0.010 0.250 0.045

Hg-Cl(1) 0.018 0.237 0.001 0.004 0.001 0.002 0.007 0.010 0.240 -0.005

Hg-C(15) 0.371 0.148 0.218 0.252

Hg-C(8) 0.149 0.213 0.252

Hg-C(20) 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.

39

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.

Reaction Coordinate

Rel

ativ

e E

ner

gy (

kca

l/m

ol)

-50

-40

-30

-20

-10

0

10

20

30

G-Cl + HgCl(g)

1C’

1A2C’, 1B2B’ 2A’

2D’

G-Cl(1) + HgCl(g)

G-ClCl(1) + Hg(g)

2AB + Cl(g)

G+ HgCl2(g)

1B + Cl(g)

1C, 2C + Cl(g)

G-ClCl(2) + Hg(g)

40

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.

Cl(1) Cl(1) Cl(2) Cl(2)

Cl(1) Cl(2)

Cl(2)

Cl(1) Cl(1)

Cl(2)

41

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.

Reaction Coordinate

Rel

ativ

e E

ner

gy (

kca

l/m

ol)

-90

-80

-70

-60

-50

-40

-30

-20

-10

0

10

G + HgCl2(g) 2B”

3B4B”

1B”

1A”

2A”

G-ClCl(3) + Hg(g)

G-Cl(1,2) + HgCl(g)

G+ HgCl2(g)

1B + Cl(g) 2C + Cl(g)

42

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.

43

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,

44

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

45

T (˚C) Mercury oxidation (%)

Residen

ce time

(s)

Chlorine

concentration

(ppm)

Hg

concentration

(μg/m3)

Flue gas

composition Flame?

Sliger et al. 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

880-

420˚C

20-80% with 300ppm HCl

40-98% with 3000ppm HCl 1s 300-3000 ppm HCl 3700 μg/m

3

N2, O2, CO2,

H2O, HCl

Simulated flue

gas (MWC)

Fry et al. 103,104

1100-

300˚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/m

3

N2, O2, CO2,

H2O, Cl2

Natural gas-fired

burner

Fry et

al.106

1100-

300˚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/m

3

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/m

3

N2, O2, CO2,

HCl, Cl2,

SO2

Propane-fired

burner

Mamani-

Paco &

Helble 21

1080-

210˚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/m

3

N2, O2, CO2,

H2O, HCl,

Cl2

Methane-fired

flat flame burner

Sterling &

Helble et

al. 102

1080-

210˚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

3

N2, O2, CO2,

H2O, HCl,

Cl2, NO,

SO2

Methane-fired

flat flame burner

Laudal et

al.101

N/A

0.1-84.8% gas phase

1.3-88.5% with fly ash 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

Table 3.1: Summary of previous experimental studies (*HQ: High quench rate,

**LQ: Low quench rate)

46

above 500 ˚C. Moreover, no reaction was detected with up to 10% O2 at temperatures of 20-

700 ˚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,

47

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/mole

2∙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.

48

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

49

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

50

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).

51

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

52

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

53

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.

54

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.

55

Figure 3.1: Chlorine speciation with Roesler and Bozelli mechanisms using 100 ppmv Cl

Figure 3.2: Chlorine speciation with Roesler and Bozelli mechanisms using 100 ppmv Cl

and temperature profile

0.0E+00

5.0E-07

1.0E-06

1.5E-06

2.0E-06

2.5E-06

3.0E-06

0.0E+00

2.0E-05

4.0E-05

6.0E-05

8.0E-05

1.0E-04

1.2E-04

0 1 2 3 4 5 6 7 8

Mo

le f

ract

ion

Cl 2

Mo

le f

ract

ion

Cl,

HC

l

t (s)

Cl - Bozelli HCl - Bozelli Cl - RoeslerHCl - Roesler Cl2 - Bozelli Cl2-Roesler

0

200

400

600

800

1000

1200

0.0E+00

2.0E-06

4.0E-06

6.0E-06

8.0E-06

1.0E-05

0 2 4 6 8

T (°

C)

Mo

le f

ract

ion

sC

l, C

l 2

t (s)

Cl - Bozelli

Cl - Roesler

Cl2-Roesler

Cl2 - Bozelli

Temperature

56

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.

57

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 “Wilcox-

Roesler” 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

Reaction Level of Theory

Forward

Act En

kcal/mol Preexp (A)

cm3/mol.s

HgCl (+M) → Hg + Cl (+M) QCISD/RECP60VDZ 16.13 4.25x1013

HgCl + HCl → HgCl2 + H QCISD/RECP60VDZ 30.27 4.50x1013

Hg + HCl → HgCl + H B3LYP/RECP60VDZ 82.06 2.62x1012

Hg + Cl2 → HgCl + Cl B3LYP/RECP60VDZ 42.80 1.34x1012

Hg + HOCl → HgCl + OH B3LYP/RECP60VDZ 36.63 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 1.43x109-2.46x10

10

HgCl + HOCl → HgCl2 + OH B3LYP/ECP60MDF 0.485 1.74x109-3.48x10

10

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.

58

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.

0

2

4

6

8

10

12

14

16

18

20

0 100 200 300 400 500 600

% O

xid

atio

n

Chlorine Concentration (ppmv equivalent HCl)

Wilcox - Roesler

Wilcox ab initio

Fry experiment

59

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.

0

2

4

6

8

10

12

14

16

18

20

0 100 200 300 400 500 600

% O

xid

atio

n

Chlorine Concentration (ppmv equivalent HCl)

Wilcox - Bozelli

Wilcox ab initio

Fry experiment

60

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 0-

20 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.

61

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

CAVKIT

Mercury vapor

generator

F

F

CH4

Cl2

in air

FI

Rotameter

UV

Detector

Purge air

Solenoid

valve

Flashback

arrestor

Mass

Spectrometer

vent

Mass flow

controllers

F

u

r

n

a

c

e

air

Temperature

Controllers

Heat

tape

N2

Solenoid

valve

Solenoid

valve

Solenoid

valve

Solenoid

valve

DAQ

system

62

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.

63

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. The

64

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

65

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

66

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].

67

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

68

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

69

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.

70

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

71

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:

)1()2/)1(( G , such that γ, the heat capacity ratio, is defined as ff 2 , 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

72

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 laser-

drilled 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

73

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.

74

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.

75

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.

76

Table 4.1: Calibration of the orifice heater

Voltage (V) T1 (°C) T2 (°C)

0 20.8 18.5

4 51.4 50.1

6 81.4 80.2

8 115.7 115.0

10 154.4 153.9

14 230.6 230.4

16 261.3 260.3

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) T1 (°C)

0 26

4 126

6 174

8 227

10 278

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

77

the experiments have been performed at orifice temperatures of 200 °C or higher to ensure no

clustering.

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 lock-

in amplifier consists of the following four stages: an input gain stage, the reference circuit, a

demodulator and a low-pass filter [146].

3.0E+05

3.5E+05

4.0E+05

4.5E+05

5.0E+05

5.5E+05

6.0E+05

6.5E+05

7.0E+05

7.5E+05

0 50 100 150 200 250 300 350

Hg

Dim

erP

eak

Inte

nsi

ty

Orifice Temperature (°C)

78

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 Hg

0

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

79

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) MFC1

(mlpm)

MFC2

(lpm)

Concentration

(ppbv)

30 3 0.5 22.0

30 5.5 0.5 40.2

40 5 0.5 80.1

30 17 0.5 121.4

40 10 0.5 158.6

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.

80

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.

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

R² = 0.9918

0.0E+00

5.0E+03

1.0E+04

1.5E+04

2.0E+04

2.5E+04

3.0E+04

3.5E+04

4.0E+04

0 20 40 60 80 100 120 140 160 180

Hg

Pea

k In

ten

sity

Concentration (ppbv)

81

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.

82

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

1

st IE (eV) 2

nd IE (eV)

Hg 10.17 (10.44) 18.73 (18.76)

HgCl 9.55 17.34

HgCl2 11.30 (11.38) 17.31

HgBr 9.20 16.56

HgBr2 10.33 (10.56) 16.06

HgO 9.70 17.41

Cl 13.12 (12.97) 23.92 (23.81)

Cl2 11.64 (11.48) 19.66

HCl 12.79 (12.74) 22.87

Br 11.96 (11.82) 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

83

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 Hg

0 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.

84

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 1.00E+00 7.50E-03

94.7 1.00E+01 7.50E-02

130.8 1.00E+02 7.50E-01

174.5 1.00E+03 7.50E+00

228.5 1.00E+04 7.50E+01

304 1.00E+05 7.50E+02

85

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

abundance

at 70eV

Appearance

Potential

(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 17.7±0.3 → Cl

+ + Hg + Cl 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%.

86

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 R

2 values of 0.9938, 0.9929,

0.9927 and 0.987, respectively as shown in Figure 4.17.

87

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+.

R² = 0.9927

R² = 0.987

R² = 0.9929

R² = 0.9938

0.0E+00

5.0E+06

1.0E+07

1.5E+07

2.0E+07

2.5E+07

1.E+04

2.E+04

3.E+04

4.E+04

5.E+04

6.E+04

7.E+04

8.E+04

0 20 40 60 80 100

Pe

ak In

ten

sity

Cl

Pea

k in

ten

sity

Hg,

HgO

, HgC

l

Concentration (ppbv)

Hg

HgO

HgCl

Cl

88

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 Hg

0 versus the dissociation of

HgCl2.

89

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

90

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 custom-

built 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

91

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.

93

Appendix

95

APPENDIX A

CHEMKIN MODEL DATA

96

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

97

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

98

CO 1.40787E-02 4.32330E+16 5.85299E-05 1.63945E-03

11.478 85.918

CO2 7.74710E-02 2.37900E+17 3.22074E-04 1.41745E-02

63.161 472.78

HCO 6.18272E-07 1.89860E+12 2.57037E-09 7.45884E-08

5.04072E-04 3.77313E-03

CH2O 5.90459E-06 1.81319E+13 2.45474E-08 7.37073E-07

4.81396E-03 3.60340E-02

CH2OH 1.26007E-07 3.86945E+11 5.23855E-10 1.62575E-08

1.02732E-04 7.68983E-04

CH3O 6.92071E-09 2.12523E+10 2.87718E-11 8.92917E-10

5.64239E-06 4.22351E-05

CH3OH 1.02707E-07 3.15396E+11 4.26991E-10 1.36818E-08

8.37365E-05 6.26794E-04

C2H 5.05939E-09 1.55365E+10 2.10336E-11 5.26478E-10

4.12488E-06 3.08760E-05

C2H2 7.85503E-07 2.41214E+12 3.26561E-09 8.50307E-08

6.40414E-04 4.79370E-03

C2H3 7.25283E-08 2.22722E+11 3.01526E-10 8.15513E-09

5.91318E-05 4.42619E-04

C2H4 9.52217E-07 2.92409E+12 3.95870E-09 1.11058E-07

7.76334E-04 5.81110E-03

C2H5 1.18955E-07 3.65290E+11 4.94538E-10 1.43723E-08

9.69830E-05 7.25948E-04

C2H6 4.00525E-07 1.22994E+12 1.66512E-09 5.00705E-08

3.26545E-04 2.44429E-03

HCCO 1.37227E-07 4.21399E+11 5.70500E-10 2.34074E-08

1.11880E-04 8.37455E-04

CH2CO 3.89711E-07 1.19673E+12 1.62017E-09 6.81079E-08

3.17728E-04 2.37829E-03

HCCOH 1.69023E-08 5.19038E+10 7.02686E-11 2.95393E-09

1.37803E-05 1.03150E-04

N 2.14595E-08 6.58983E+10 8.92147E-11 1.24960E-09

1.74958E-05 1.30961E-04

NH 1.01026E-08 3.10233E+10 4.20000E-11 6.30616E-10

8.23656E-06 6.16532E-05

NH2 1.22836E-08 3.77207E+10 5.10671E-11 8.18230E-10

1.00147E-05 7.49631E-05

NH3 1.19021E-08 3.65493E+10 4.94813E-11 8.42697E-10

9.70370E-06 7.26352E-05

NNH 3.00604E-09 9.23102E+09 1.24972E-11 3.62685E-10

2.45080E-06 1.83450E-05

NO 1.65332E-04 5.07704E+14 6.87342E-07 2.06244E-05

0.13479 1.0090

NO2 3.04820E-08 9.36048E+10 1.26724E-10 5.83002E-09

2.48517E-05 1.86023E-04

N2O 1.38248E-07 4.24535E+11 5.74746E-10 2.52962E-08

1.12713E-04 8.43688E-04

HNO 1.12683E-08 3.46028E+10 4.68461E-11 1.45289E-09

9.18691E-06 6.87669E-05

CN 1.81262E-09 5.56624E+09 7.53571E-12 1.96063E-10

1.47782E-06 1.10619E-05

HCN 4.20886E-07 1.29247E+12 1.74977E-09 4.72890E-08

3.43145E-04 2.56855E-03

H2CN 7.31937E-12 2.24765E+07 3.04292E-14 8.53045E-13

5.96742E-09 4.46680E-08

99

HCNN 8.68433E-11 2.66680E+08 3.61038E-13 1.48143E-11

7.08026E-08 5.29979E-07

HCNO 4.60373E-08 1.41372E+11 1.91393E-10 8.23473E-09

3.75338E-05 2.80952E-04

HOCN 3.28978E-09 1.01023E+10 1.36768E-11 5.88445E-10

2.68213E-06 2.00766E-05

HNCO 2.09736E-07 6.44062E+11 8.71946E-10 3.75157E-08

1.70996E-04 1.27996E-03

NCO 2.02239E-08 6.21038E+10 8.40776E-11 3.53271E-09

1.64883E-05 1.23420E-04

N2 0.70903 2.17730E+18 2.94768E-03 8.25745E-02

578.07 4327.0

AR 0.0000 0.0000 0.0000 0.0000

0.0000 0.0000

C3H7 2.91098E-08 8.93909E+10 1.21020E-10 5.21464E-09

2.37330E-05 1.77649E-04

C3H8 1.02325E-07 3.14220E+11 4.25399E-10 1.87589E-08

8.34244E-05 6.24457E-04

CH2CHO 3.31595E-09 1.01827E+10 1.37856E-11 5.93408E-10

2.70346E-06 2.02363E-05

CH3CHO 2.29783E-07 7.05621E+11 9.55286E-10 4.20838E-08

1.87340E-04 1.40230E-03

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

100

CH4 3.299E-04 1.520E-07 2.661E-05 3.564E-04

0.00 1.078E-08

CO 0.00 5.853E-05 4.877E-03 4.819E-03

0.00 9.551E-09

CO2 5.341E-06 3.221E-04 4.837E-03 4.520E-03

0.00 -9.697E-09

HCO 0.00 2.570E-09 2.516E-04 2.516E-04

0.00 -2.737E-10

CH2O 0.00 2.455E-08 2.021E-04 2.020E-04

0.00 5.002E-10

CH2OH 0.00 5.239E-10 2.355E-05 2.355E-05

0.00 -1.626E-10

CH3O 0.00 2.877E-11 3.032E-06 3.032E-06

0.00 -7.827E-11

CH3OH 0.00 4.270E-10 3.598E-06 3.597E-06

0.00 1.101E-10

C2H 0.00 2.103E-11 2.367E-06 2.367E-06

0.00 -3.489E-11

C2H2 0.00 3.266E-09 9.443E-06 9.440E-06

0.00 -1.035E-11

C2H3 0.00 3.015E-10 7.918E-06 7.918E-06

0.00 -2.151E-10

C2H4 0.00 3.959E-09 1.119E-05 1.119E-05

0.00 2.749E-10

C2H5 0.00 4.945E-10 1.565E-05 1.565E-05

0.00 -6.190E-10

C2H6 1.602E-05 1.665E-09 1.184E-07 1.614E-05

0.00 1.010E-09

HCCO 0.00 5.705E-10 6.266E-06 6.265E-06

0.00 -5.111E-11

CH2CO 0.00 1.620E-09 2.611E-06 2.610E-06

0.00 -2.464E-12

HCCOH 0.00 7.027E-11 3.588E-07 3.587E-07

0.00 -7.178E-12

N 0.00 8.921E-11 6.296E-07 6.294E-07

0.00 2.766E-11

NH 0.00 4.200E-11 5.364E-07 5.364E-07

0.00 1.241E-11

NH2 0.00 5.107E-11 2.764E-07 2.763E-07

0.00 1.807E-12

NH3 0.00 4.948E-11 7.811E-08 7.806E-08

0.00 -3.345E-13

NNH 0.00 1.250E-11 3.075E-05 3.075E-05

0.00 1.989E-11

NO 0.00 6.873E-07 2.710E-06 2.022E-06

0.00 -3.040E-11

NO2 0.00 1.267E-10 8.762E-07 8.761E-07

0.00 -2.603E-11

N2O 0.00 5.747E-10 1.477E-07 1.472E-07

0.00 -1.853E-12

HNO 0.00 4.685E-11 9.314E-07 9.313E-07

0.00 3.055E-11

CN 0.00 7.536E-12 1.929E-07 1.929E-07

0.00 5.009E-13

HCN 0.00 1.750E-09 5.060E-07 5.042E-07

0.00 1.260E-11

101

H2CN 0.00 3.043E-14 3.362E-09 3.362E-09

0.00 -2.717E-13

HCNN 0.00 3.610E-13 3.553E-08 3.553E-08

0.00 5.200E-14

HCNO 0.00 1.914E-10 7.035E-08 7.016E-08

0.00 -2.211E-12

HOCN 0.00 1.368E-11 5.932E-08 5.931E-08

0.00 -2.507E-12

HNCO 0.00 8.719E-10 4.470E-07 4.462E-07

0.00 5.162E-12

NCO 0.00 8.408E-11 5.687E-07 5.687E-07

0.00 -7.713E-12

N2 2.948E-03 2.948E-03 2.328E-04 2.331E-04

0.00 -2.871E-11

AR 0.00 0.00 0.00 0.00

0.00 0.00

C3H7 0.00 1.210E-10 3.765E-06 3.765E-06

0.00 -1.290E-10

C3H8 4.520E-06 4.254E-10 2.079E-08 4.540E-06

0.00 1.861E-10

CH2CHO 0.00 1.379E-11 1.958E-06 1.958E-06

0.00 1.975E-11

CH3CHO 0.00 9.553E-10 2.078E-06 2.077E-06

0.00 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

102

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



TPRO 0.0 948.0 ! 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 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 CL 0.0001 ! Reactant Fraction (mole fraction)

103

REAC CL2 0.0 ! Reactant Fraction (mole fraction)

REAC CN 1.81262E-9 ! Reactant Fraction (mole fraction)

REAC CO 1.9E-5 ! Reactant Fraction (mole fraction)


REAC H 0.00204604 ! Reactant Fraction (mole fraction)

REAC H2 0.00598842 ! Reactant Fraction (mole fraction)

REAC H2CN 7.31937E-12 ! Reactant Fraction (mole fraction)

REAC H2O 0.16453 ! Reactant Fraction (mole fraction)

REAC H2O2 1.41183E-7 ! Reactant Fraction (mole fraction)

REAC HCCO 1.37227E-7 ! Reactant Fraction (mole fraction)

REAC HCCOH 1.69023E-8 ! Reactant Fraction (mole fraction)

REAC HCN 4.20886E-7 ! Reactant Fraction (mole fraction)

REAC HCO 6.18272E-7 ! Reactant Fraction (mole fraction)

REAC HNCO 2.09736E-7 ! Reactant Fraction (mole fraction)

REAC HNO 1.12683E-8 ! Reactant Fraction (mole fraction)

REAC HO2 2.99285E-6 ! Reactant Fraction (mole fraction)

REAC HOCN 3.28978E-9 ! Reactant Fraction (mole fraction)

REAC N 2.14595E-8 ! Reactant Fraction (mole fraction)


REAC N2O 1.38248E-7 ! Reactant Fraction (mole fraction)

REAC NCO 2.02239E-8 ! Reactant Fraction (mole fraction)

REAC NH 1.01026E-8 ! Reactant Fraction (mole fraction)

REAC NH2 1.22836E-8 ! Reactant Fraction (mole fraction)


REAC NNH 3.00604E-9 ! Reactant Fraction (mole fraction)

REAC NO 3.6E-5 ! Reactant Fraction (mole fraction)

REAC NO2 3.0482E-8 ! Reactant Fraction (mole fraction)

REAC O 0.000641 ! Reactant Fraction (mole fraction)


REAC OH 0.00596883 ! Reactant Fraction (mole fraction)

REAC SO2 0.0 ! Reactant Fraction (mole fraction)

DXMX 0.1 ! Solver Maximum Step Distance (cm)

END

104

Temperature Profile

Distance

(cm)

Temperature

(°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

105

Kinetics Data – Roesler

! HCL REACTIONS (Roesler et al. 1995) (29 reactions)

H+CL+M=HCL+M 7.19E21 -2.0 0.

HCL+H=H2+CL 1.8E12 0.3 3804.

!298-1500 SENKAN1998

HCL+OH=H2O+CL 2.71E7 1.65 -220.

!HCL+OH=H2O+CL 2.45E12 0.0 1100.

!wANG HAI

HCL+O=OH+CL 4.5E3 3.13 3110.

!350-1480 MKF1990

!HCL+O=OH+CL 3.4E3 2.87 3510.

!Niksa

!HCL+O=OH+CL 5.24E12 0.0 6400.

!WANG HAI

CL+HO2=HCL+O2 1.08E13 0.0 -330.

!CL+HO2=HCL+O2 4.1E13 0.0 -330.

!Edwards

CL2+H=HCL+CL 6.0E10 1.0 191. !298-

1500 SENKAN1998

!CL2+H=HCL+CL 8.59E13 0.0 1170. !wANG

HAI

CL+CL+M=CL2+M 4.68E14 0.0 -

1800.

CL2+O=CLO+CL 2.52E12 0.0 2720.

CLO+O=CL+O2 3.3E8 2.0 191. !300-

1200 ABCHKT 1992

!CLO+O=CL+O2 5.7E13 0.0 364.

HO2+CL=OH+CLO 2.42E13 0.0 2300.

H2O2+CL=HO2+HCL 6.62E12 0.0 1950.

HOCL+CL=CLO+HCL 7.28E12 0.0 180.

CLO+H2=HOCL+H 6.03E11 0.0

14100.

H+HOCL=HCL+OH 9.55E13 0.0 7620.

CL+HOCL=CL2+OH 1.81E12 0.0 260.

O+HOCL=OH+CLO 6.03E12 0.0 4370.

OH+HOCL=H2O+CLO 1.81E12 0.0 990.

HOCL=OH+CL 1.76E20 -3.01 56720.

HOCL=H+CLO 8.13E14 -2.09 93690.

CLCO+M=CO+CL+M 1.30E14 0.0 8000.

CLCO+O2=CO2+CLO 7.94E10 0.0 3300.

CLCO+CL=CO+CL2 4.00E14 0.0 800.

CLCO+H=CO+HCL 1.00E14 0.0 0.

CLCO+O=CO+CLO 1.00E14 0.0 0.

CLCO+O=CO2+CL 1.00E13 0.0 0.

CLCO+OH=CO+HOCL 3.30E12 0.0 0.

CLO+CO=CO2+CL 6.03E11 0.0 7400.

HCO+CL=CO+HCL 1.00E14 0.0 0.

HCO+CLO=CO+HOCL 3.16E13 0.0 0.

106

Kinetics Data – Bozelli

!Bozzelli chlorine chemistry

CL + H2 = HCL + H 4.80E+13 0.0

5000.

CL + CO = COCL 1.95E+19 -3.01 8070.

CL + CL + M = CL2 + M 5.75E+14 0.0 -

1600.

CL + HCO = HCL + CO 1.41E+14 -0.35 510.

CLO + H2 = HOCL + H 1.00E+13 0.0

13500.

CLO + CO = CO2 + CL 6.02E+11 0.0

7400.

!COCL + CL = COCL2 3.40E+28 -5.61 3390.

COCL + CL = CO + CL2 1.49E+19 -2.17 1470.

COCL + H = CO + HCL 3.54E+16 -0.79 1060.

COCL + H = HCO + CL 3.42E+09 1.15

-180.

COCL + O2 = CO2 + CLO 7.94E+10 0.0 3300.

COCL + O = CO2 + CL 1.00E+13 0.0

0.0

O + HCL = OH + CL 5.25E+12 0.0

6400.

O + CL2 = CLO + CL 1.26E+13 0.0

2800.

O + CLO = CL + O2 5.75E+13 0.0

400.

OH + HCL = H2O + CL 2.20E+12 0.0

1000.

!*********************Duplicate Chemistry***********************

!CH3CL + OH = CH2CL + H2O 1.32E+12 0.0 2300.

!CH3CL + O = OH + CH2CL 1.70E+13 0.0 7300.

!CH3CL + H = H2 + CH2CL 6.66E+13 0.0

10600.

!CH3CL + O2 = HO2 + CH2CL 4.00E+13 0.0

52200.

!CH3CL + HO2 = H2O2 + CH2CL 1.00E+13 0.0

16700.

!CH3CL + CLO = HOCL + CH2CL 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.

!CH3CL = CH3 + CL 5.53E+31 -5.63

88810.

!CH3CL = CH2 + HCL 1.82E+25 -4.69

132460.

!CH3CL = CH2CL + H 1.31E+30 5.23

106100.

!CH2CL + O2 = CLO + CH2O 8.46E+13 -1.03 8180.

!CH2CL + H = CH3 + CL 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 0.38 2970.

107

!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.

!CH2O + CL = HCO + HCL 5.00E+13 0.0 500.

!CH2O + CLO = HOCL + HCO 1.20E+13 0.0 2000.

!CH3 + CLO = CH3O + CL 2.28E+07 1.54 -820.

!CH3 + CLO = HCL + CH2O 5.50E+14 -0.51 710.

!CH4 + CLO = CH3 + HOCL 1.40E+13 0.0

15000.

!CH4 + CL = HCL + CH3 2.57E+13 0.0 3850.

!C2H2 + CL = HCL + C2H 1.00E+13 0.0

28800.

!C2H3 + CL = C2H3CL 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 0.0 5100.

!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 + CHCL*CJH 5.00E+12 0.0 5870.

!**************************************************************************

HO2 + CL = HCL + O2 1.58E+13 0.0

0.

HO2 + CL = CLO + OH 3.35E+14 -0.32 1470.

H2O2 + CL = HCL + HO2 1.02E+12 0.0 800.

H2O2 + CLO = HOCL + HO2 5.00E+12 0.0 2000.

108

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






























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 CH 1.5616E-7 ! Reactant Fraction (mole fraction)


REAC CH2CO 3.89711E-7 ! Reactant Fraction (mole fraction)







REAC CL 0.0001 ! Reactant Fraction (mole fraction)

109

REAC CL2 0.0 ! Reactant Fraction (mole fraction)

REAC CN 1.81262E-9 ! Reactant Fraction (mole fraction)

REAC CO 1.9E-5 ! Reactant Fraction (mole fraction)


REAC H 0.00204604 ! Reactant Fraction (mole fraction)

REAC H2 0.00598842 ! Reactant Fraction (mole fraction)

REAC H2CN 7.31937E-12 ! Reactant Fraction (mole fraction)

REAC H2O 0.16453 ! Reactant Fraction (mole fraction)

REAC H2O2 1.41183E-7 ! Reactant Fraction (mole fraction)

REAC HCCO 1.37227E-7 ! Reactant Fraction (mole fraction)

REAC HCCOH 1.69023E-8 ! Reactant Fraction (mole fraction)

REAC HCN 4.20886E-7 ! Reactant Fraction (mole fraction)

REAC HCO 6.18272E-7 ! Reactant Fraction (mole fraction)

REAC HG 2.28795E-9 ! Reactant Fraction (mole fraction)

REAC HNCO 2.09736E-7 ! Reactant Fraction (mole fraction)

REAC HNO 1.12683E-8 ! Reactant Fraction (mole fraction)

REAC HO2 2.99285E-6 ! Reactant Fraction (mole fraction)

REAC HOCN 3.28978E-9 ! Reactant Fraction (mole fraction)

REAC N 2.14595E-8 ! Reactant Fraction (mole fraction)


REAC N2O 1.38248E-7 ! Reactant Fraction (mole fraction)

REAC NCO 2.02239E-8 ! Reactant Fraction (mole fraction)

REAC NH 1.01026E-8 ! Reactant Fraction (mole fraction)



REAC NNH 3.00604E-9 ! Reactant Fraction (mole fraction)

REAC NO 3.6E-5 ! Reactant Fraction (mole fraction)

REAC NO2 3.0482E-8 ! Reactant Fraction (mole fraction)

REAC O 0.000641 ! Reactant Fraction (mole fraction)


REAC OH 0.00596883 ! Reactant Fraction (mole fraction)

REAC SO2 0.0 ! Reactant Fraction (mole fraction)

DXMX 0.1 ! Solver Maximum Step Distance (cm)

END

110

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 CH2O C

H O OH HO2

HCO HCCO N2 AR CN HCN N NH NO HNO

NH2 H2NO NCO N2O NO2 N2H2 HOCN H2CN NNH NH3

N2H3 C2N2 HNCO O3 HONO NO3 HNO3

CLCO NOCL

S

SH H2S SO SO2 SO3 HSO2 HOSO HOSO2 SN S2

CS COS HSNO HSO HOS HSOH H2SO HOSHO HS2

SO2* SCL

CH CH2 CH2(S) CH3 CH4

CH2OH CH3O CH3OH C2H C2H2 C2H3

C2H4 C2H5 C2H6 CH2CO HCCOH CH3CO CH2SING

C3H7 CH2CHO CH3CHO

CH3CL CH2CL CH2CLO. C2H5CL COCL2 CH2CLC.H2

C2H4OCL CHCLC.H C2H3CL CH3C.HCL CH2CLO CHCLO CHO HCO2

END

REACTIONS

!H+O2+M=HO2+M 3.61E17 -0.72 0.

! H2O/18.6/ H2/2.86/

!SH+H+M=H2+M 1.0E18 -1.0

0.

H+H+H2=H2+H2 9.2E16 -0.6 0.

H+H+H2O=H2+H2O 6.0E19 -1.25 0.

!H+OH+M=H2O+M 1.6E22 -2.0 0.

! H2O/5/

!H+O+M=OH+M 6.2E16 -0.6 0.

! H2O/5/

!O+O+M=O2+M 1.89E13 0.0 -

1788.

!H2O2+M=OH+OH+M 1.3E17 0.0

45500.

H2+O2=2OH 1.7E13 0.0

47780.

!OH+H2=H2O+H 1.17E9 1.3 3626.

!O+OH=O2+H 3.61E14 -0.5 0.

!O+H2=OH+H 5.06E4 2.7 6290.

!OH+HO2=H2O+O2 7.5E12 0.0 0.0

!H+HO2=2OH 1.4E14 0.0 1073.

!O+HO2=O2+OH 1.4E13 0.0 1073.

!2OH=O+H2O 6.0E+8 1.3 0.

111

!H+HO2=H2+O2 1.25E13 0.0 0.

!HO2+HO2=H2O2+O2 2.0E12 0.0 0.

!H2O2+H=HO2+H2 1.6E12 0.0 3800.

!H2O2+OH=H2O+HO2 1.0E13 0.0 1800.

! C-H-O Chemistry (PRINCETON--28REACTIONS)

H+O2=O+OH 1.91E+14 0.0

16440.0 !PRINCETON

!H+O2=O+OH 2.65E+16 -0.7

17041.0 !GRI

!H+O2=O+OH 9.76E+13 0.0

14856.0 !Leeds

O+H2=H+OH 5.06E+04 2.7

6290.0 !Roseler

OH+H2=H2O+H 2.16E+08 1.5

3430.0

H2O+O=OH+OH 2.97E+06 2.0

13400.0

H2+M=H+H+M 4.57E+19 -1.4

104000.0

O+O+M=O2+M 6.17E+15 -0.5

0.0

H+O+M=OH+M 4.72E+18 -1.0

0.0

OH+H+M=H2O+M 2.21E+22 -2.0

0.0

H+O2+M=HO2+M 1.48E+12 0.6

0.0

!H+O2+M=HO2+M 1.48E+12 0.6

0.0

HO2+H=H2+O2 1.66E+13 0.0

820.0

HO2+H=OH+OH 7.08E+13 0.0

300.0

HO2+O=O2+OH 3.25E+13 0.0

0.0

HO2+OH=H2O+O2 2.89E+13 0.0

-500.0

HO2+HO2=H2O2+O2 4.20E+14 0.0

12000.0

!HO2+HO2=H2O2+O2 1.3E11 0.0

-1629.

H2O2+M=OH+OH+M 2.95E+14 0.0

48400.0

H2O2+H=H2O+OH 2.41E+13 0.0

3970.0

H2O2+H=HO2+H2 4.82E+13 0.0

7950.0

H2O2+O=OH+HO2 9.55E+06 2.0

3970.0

H2O2+OH=H2O+HO2 1.00E+12 0.0

0.0

!H2O2+OH=H2O+HO2 5.80E14 0.0

9560.0

CO+O+M=CO2+M 1.80E+10 0.0

2830.0 ! (Niksa 2380)

112

CO+O2=CO2+O 2.53E+12 0.0

47700.0

CO+OH=CO2+H 1.40E+07 1.95

-1350.0

CO+HO2=CO2+OH 3.01E+13 0.0

22900.0

HCO+M=H+CO+M 1.85E+17 -1.0

17000.0

HCO+O2=CO+HO2 7.58E+12 0.0

406.0

HCO+H=CO+H2 7.23E+13 0.0

0.0

HCO+O=CO+OH 3.00E+13 0.0

0.0

HCO+OH=CO+H2O 3.00E+13 0.0

0.0

! Hg chemistry (Wilcox) (10 reactions)

HGCL+M=HG+CL+M 4.25e13 0.0

16130. !Wilcox

HGCL2+M=HG+CL2+M 3.19e12 0.0 86980.

!Wilcox

HG+HCL=HGCL+H 2.62e12 0.0

82060. !Wilcox

HG+CL2=HGCL+CL 1.34e12 0.0

42800. !Wilcox

HGCL2+M=HGCL+CL+M 2.87e14 0.0 80550.

!Wilcox

HGCL+HCL=HGCL2+H 4.50e13 0.0 30270.

!Wilcox

HGCL+CL2=HGCL2+CL 2.465e10 0.0 0. !Wilcox

HG+HOCL=HGCL+OH 3.09e13 0.0 36638

!Wilcox

HGCL+HOCL=HGCL2+OH 3.48e10 0.0 485

!Wilcox

!HGO+M=HG+O+M 3.09e10 0.0 8750

!Wilcox

! HCL REACTIONS (Roesler et al. 1995) (29 reactions)

H+CL+M=HCL+M 7.19E21 -2.0 0.

HCL+H=H2+CL 1.8E12 0.3 3804.

!298-1500 SENKAN1998

HCL+OH=H2O+CL 2.71E7 1.65 -220.

!HCL+OH=H2O+CL 2.45E12 0.0 1100.

!wANG HAI

HCL+O=OH+CL 4.5E3 3.13 3110.

!350-1480 MKF1990

!HCL+O=OH+CL 3.4E3 2.87 3510.

!Niksa

!HCL+O=OH+CL 5.24E12 0.0 6400.

!WANG HAI

CL+HO2=HCL+O2 1.08E13 0.0 -330.

!CL+HO2=HCL+O2 4.1E13 0.0 -330.

!Edwards

113

CL2+H=HCL+CL 6.0E10 1.0 191. !298-

1500 SENKAN1998

!CL2+H=HCL+CL 8.59E13 0.0 1170. !wANG

HAI

CL+CL+M=CL2+M 4.68E14 0.0 -

1800.

CL2+O=CLO+CL 2.52E12 0.0 2720.

CLO+O=CL+O2 3.3E8 2.0 191. !300-

1200 ABCHKT 1992

!CLO+O=CL+O2 5.7E13 0.0 364.

HO2+CL=OH+CLO 2.42E13 0.0 2300.

H2O2+CL=HO2+HCL 6.62E12 0.0 1950.

HOCL+CL=CLO+HCL 7.28E12 0.0 180.

CLO+H2=HOCL+H 6.03E11 0.0

14100.

H+HOCL=HCL+OH 9.55E13 0.0 7620.

CL+HOCL=CL2+OH 1.81E12 0.0 260.

O+HOCL=OH+CLO 6.03E12 0.0 4370.

OH+HOCL=H2O+CLO 1.81E12 0.0 990.

HOCL=OH+CL 1.76E20 -3.01 56720.

HOCL=H+CLO 8.13E14 -2.09 93690.

CLCO+M=CO+CL+M 1.30E14 0.0 8000.

CLCO+O2=CO2+CLO 7.94E10 0.0 3300.

CLCO+CL=CO+CL2 4.00E14 0.0 800.

CLCO+H=CO+HCL 1.00E14 0.0 0.

CLCO+O=CO+CLO 1.00E14 0.0 0.

CLCO+O=CO2+CL 1.00E13 0.0 0.

CLCO+OH=CO+HOCL 3.30E12 0.0 0.

CLO+CO=CO2+CL 6.03E11 0.0 7400.

HCO+CL=CO+HCL 1.00E14 0.0 0.

HCO+CLO=CO+HOCL 3.16E13 0.0 0.

!NO-CL reaction (9 reactions)

CLO+NO=NO2+CL 3.85E12 0.0 140.

!niksa

HNO+CL=HCL+NO 8.99E13 0.0 993.

HONO+CL=HCL+NO2 5.00E13 0.0 0.

NOCL+M=NO+CL+M 2.50E15 0.0

31991. !800-1500 K

NOCL+CL=NO+CL2 2.40E13 0.0 0.

!niksa

NOCL+H=NO+HCL 4.60E13 0.0 890.

!niksa

NOCL+O=NO+CLO 5.00E12 0.0 3000.

!niksa

NOCL+OH=HOCL+NO 5.4E12 0.0 2250.

NOCL+OH=HONO+CL 5.5E10 0.0 -480.

! NOx chemistry (Muller, 2000)

!N-O-H reaction (Muller and Dryer et al,2000) (24 REACTIONS)

NO+O+M=NO2+M 3.00E13 0.0 0.

NO+H+M=HNO+M 1.52E15 -0.41 0.

NO+OH+M=HONO+M 1.99E12 -0.05 -721.

114

NO2+H2=HONO+H 1.30E4 2.76

15000.

NO2+O=O2+NO 1.05E14 -0.52 0.

!niksa

!NO2+O=O2+NO 3.9E12 0.0 -240.

NO2+O+M=NO3+M 1.33E13 0.0 0.

NO2+H=NO+OH 1.32E14 0.0 362.

NO2+OH+M=HNO3+M 4.52E13 0.0 0.

NO2+OH=HO2+NO 1.81E13 0.0 6680.

!NIKSA

!NO+HO2=NO2+OH 2.11E12 0.0 -479.

!MULLER (2000)

NO2+NO2=NO3+NO 9.64E9 0.73

20900.

NO2+NO2=2NO+O2 1.63E12 0.0

26100.

HNO+H=NO+H2 4.46E11 0.72 655.

HNO+O=OH+NO 1.81E13 0.0 0.

HNO+OH=H2O+NO 1.30E7 1.88 -956.

HNO+NO=N2O+OH 2.00E12 0.0

26000.

HNO+NO2=HONO+NO 6.02E11 0.0 1990.

HNO+HNO=H2O+N2O 8.51E8 0.0 3080.

HONO+O=OH+NO2 1.20E13 0.0 5960.

HONO+OH=H2O+NO2 1.70E12 1.0 -520.

N2O+M=N2+O+M 7.91E10 0.0

56000.

N2O+O=N2+O2 1.00E14 0.0

28000.

N2O+O=NO+NO 1.00E14 0.0

28000.

N2O+H=N2+OH 2.23E14 0.0

16800. !NIKSA

!N2O+H=N2+OH 2.53E10 0.0 4550.

N2O+OH=N2+HO2 2.00E12 0.0

40000.

CO+N2O=CO2+N2 5.01E13 0.0

44000.

CO+NO2=CO2+NO 9.03E13 0.0

33800.

HCO+NO=HNO+CO 7.23E12 0.0 0.

HCO+NO2=HONO+CO 1.24E23 -3.29 2350.

HCO+NO2=H+NO+CO2 8.39E15 -0.75 1930.

! SOx chemistry (66 reactions)

SO2+O(+M) = SO3(+M) 9.200E+10 0.0000

2400.

N2/1.3/ SO2/10/ H2O/10/

LOW / 4.000E+28 -4.00 5250. /

SO2+OH(+M) = HOSO2(+M) 7.200E+12 0.0000

715.00 !muller and niksa

N2/1.5/ SO2/10/ H2O/10/

115

LOW / 4.500E+25 -3.30 359.84 /

TROE / 0.7000 1.0e-30 1e+30 /

SO2+OH = HOSO+O 3.900E+08 1.8900

76000.00

SO2+OH = SO3+H 4.900E+02 2.6900

23850.00

SO2+CO = SO+CO2 2.700E+12 0.0000

48300.

SO2*+M = SO2+M 1.300E+14 0.0000

3600.00

SO2*+SO2 = SO3+SO 2.600E+12 0.0000

2430.00

SO3+H = HOSO+O 2.500E+05 2.9200

50300.0

SO+O(+M) = SO2(+M) 3.200E+13 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 /

SO+M = S+O+M 4.000E+14 0.0000

107000.

N2/1.5/ SO2/10/ H2O/10/

SO+H+M = HSO+M 5.000E+15 0.0000

0.00

N2/1.5/ SO2/10/ H2O/10/

2SO = SO2+S 2.000E+12 0.0000

4000.00

HSO+H = HSOH 2.500E+20 -3.1400

920.00

HSO+H = SH+OH 4.900E+19 -1.8600 1560.

HSO+H = S+H2O 1.600E+09 1.3700

-340.

HSO+H = H2SO 1.800E+17 -2.4700 50.

HSO+H = H2S+O 1.100E+06 1.0300

10400.

HSO+O+M = HSO2+M 1.100E+19 -1.7300 -50.

HSO+O = SO2+H 4.500E+14 -0.4000 0.00

HSO+O+M = HOSO+M 6.900E+19 -1.6100 1600.

HSO+O = O+HOS 4.800E+08 1.0200

5340.

HSO+O = OH+SO 1.400E+13 0.1500

300.

HSO+OH = HOSHO 5.200E+28 -5.4400 3170.

HSO+OH = HOSO+H 5.300E+07 1.5700

3750.

HSO+OH = SO+H2O 1.700E+09 1.0300

470.

HSO+O2 = SO2+OH 1.000E+12 0.0000

0.0 !NIKSA, MULLER

HSOH = SH+OH 2.800E+39 -8.7500

75200.

116

HSOH = S+H2O 5.800E+29 -5.6000

54500.

HSOH = H2S+O 9.800E+16 -3.4000

86500.

H2SO = H2S+O 4.900E+28 -6.6600

71700.

HOSO(+M) = HSO2(+M) 1.000E+09 1.0300

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 2.500E+30 -4.8000

119000. !MULLER

HOSO+H = SO+H2O 6.300E-10 6.2900

-1900.

HOSO+OH = SO2+H2O 1.000E+12 0.0000

0.00

HOSO+O2 = HO2+SO2 1.000E+12 0.0000

1000.

HSO2(+M) = H+SO2(+M) 2.000E+11 -0.9000

18361. !muller

N2/1/ SO2/10/ H2O/10/

LOW / 3.500E+25 -3.29 9612.48 /

HOSO2 = HOSO+O 5.400E+18 -2.3400

106300.

HOSO2+H = SO2+H2O 1.000E+12 0.0000

0.00

HOSO2+O = SO3+OH 5.000E+12 0.0000

0.00

HOSO2+OH = SO3+H2O 1.000E+12 0.0000

0.00

HOSO2+O2 = HO2+SO3 7.80E+11 0.0000 656.0

HOSHO = HOSO+H 6.400E+30 -5.8900

73800.

HOSHO+H = HOSO+H2 1.000E+12 0.0000

0.00

HOSHO+O = HOSO+OH 5.000E+12 0.0000

0.00

SO2+NO2=NO+SO3 6.3E12 0.0

27000. !NIKSA

SO+NO2 = SO2+NO 8.432E+12 0.00

0.00

HSO+NO2 = HOSO+NO 5.8E12 0.00

0.00

! modified ( 8 reactions)

SO3+O = SO2+O2 2.000E+12 0.0000

19870.

SO3+SO = 2SO2 1.000E+12 0.0000

10000.00

SO+O2 = SO2+O 7.600E+03 2.3700

3000.00

117

HOSO(+M) = SO+OH(+M) 9.940E+21 -2.5400

76380.00

LOW / 1.156E+46 -9.02 53350.00 /

TROE / 9.5000E-01 2.9890E+03 1.1000E+00 /

SO+OH = SO2+H 1.077E+17 -1.35 0.0

H+SO2(+M) = HOSO(+M) 3.119E+08 1.6100

7200.00

LOW / 2.662E+38 -6.43 11150.00 /

TROE / 8.2000E-01 1.3088E+05 2.6600E+02 /

HOSO2 = SO3+H 1.400E+18 -2.9100

55000.00

HSO+H = SO+H2 1.000E+13 0.0000

0.00

! New ( 7 reactions)

HOSO+H = SO2+H2 3.000E+13 0.0000

0.00

HSO2+H = SO2+H2 3.000E+13 0.0000

0.00

HSO2+OH = SO2+H2O 1.000E+13 0.0000

0.00

HSO2+O2 = HO2+SO2 1.000E+13 0.0000

0.00

HOSHO = SO+H2O 1.200E+24 -3.5900

59500.

HOSHO+OH = HOSO+H2O 1.000E+12 0.0000

0.00

HOSO2+H = SO3+H2 1.0E+12 0.00

0.00

!S-CL-O reactions (quantum chemistry) (3 reactions)

SO+CLO=SO2+CL 1.29E10 0.0 15744.

SCL+O=SO+CL 2.84E11 0.0 12350.

SO+CL2=SCL+CLO 1.63E9 0.0 27320.

! NIST CxHy chemistry ( REACTIONS)

!*** C1 hydrocarbons

***********************************************************

! *** Methane ***

CH4 + 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?

118

! *** Methyl ***

CH3 + H (+M) = CH4 (+M) 6.00E16 -1.00

0. !MBA002 84WAR (up)

LOW/8.00E26 -3.0 0./ !(89STE/SMI2)

SRI/0.45 797. 979. /

H2/2.0/ CO/2.0/ CO2/3.0/ H2O/5.0/

!CH3 + H (+M) = CH4 (+M) 1.21E15 -0.40 0.

!86TSA/HAM

!factor of 2 different, which to use?

CH3 + H = CH2 + H2 9.00E13 0.00

15100. !MBA013 (mb?)

CH3 + O = CH2O + H 8.00E13 0.00 0.

!MBA009 (mb?)

CH3 + OH = CH2 + H2O 7.50E06 2.00

5000. !MBA012 (mb?)

!CH3 + OH = CH3OH 2.24E40 -8.20

11673. !87DEA/WES (1atm)

!CH3 + OH = CH2OH + H 2.64E19 -1.80 8068.

!87DEA/WES (1atm)

!CH2OH+H = CH3+OH 1.00E14 0.00 0.

!MBA010

CH3 + OH = CH3O + H 5.74E12 -0.23

13931. !87DEA/WES (1atm)

!CH3O+H = CH3+OH 1.00E14 0.00 0.

!MBA011

CH3 + OH = CH2SING + H2O 8.90E19 -1.80 8067.

!87DEA/WES (1atm)

!CH3 + O2 = CH3O + O 2.05E18 -1.57

29229. !MBA008 86TSA/HAM

CH3 + O2 <=> CH3O + O 2.05E+19 -1.570

29229. !bozzelli

!CH3 + O2 = CH3O + O 2.88E15 -1.15

30850. !92HO/YU (BOZ)

!CH3 + O2 = CH3O + O 7.20E13 0.00

31600 !92BAU/COB

!CH3 + O2 = CH2O + OH 3.30E11 0. 9000.

!92BAU/COB

CH3 + O2 = CH2O + OH 3.59E09 -0.14

10150. !92HO/YU (BOZ)

!CH3 + O2 = CH3O + O 1.32E14 0.

31600. !92BAU/COB

!CH3 + O2(+M)=CH3OO(+M) 7.80E08 1.2 0.

!92BAU/COB

CH3 + HO2 = CH3O + OH 2.00E13 0.00 0.

!MBA007 86TSA/HAM

CH3 + CH3 = C2H4 + H2 1.00E16 0.

32005. !92EGO/DU

!CH3 + CH3(+M) = C2H6 (+M) 9.03E16 -1.20 654.

!MBA001 88WAG/WAR (ok)

! LOW/3.18E41 -7.0 2762./ !88WAG/WAR

! TROE/0.6041 6927. 132./

!H2/2.0/ CO/2.0/ CO2/3.0/ H2O/5.0/

CH3+CH3<=>C2H6 2.68E+29 -5.0

6130.0 !Bozzelli

!CH3+HCO=CH4+CO 2.648E+13 0.000 0.00

!(GRIMECH11)

119

CH3+HCO=CH4+CO 1.20E14 0. 0.

!86TSA/HAM

C+CH3=H+C2H2 5.000E+13 0.000 0.00

!(GRIMECH1)

! *** 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 ***

!********************

120

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.


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, CH2OH ***

CH3O+M = 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)

121

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 1.00E14 0.00

25000. !MBA015

!CH2OH+O2 = CH2O+HO2 1.48E13 0.00

1500. !MBA023

CH2OH+O2 = CH2O+HO2 2.41E14 0.00

5000. !LAW

!CH2OH+O2 = CH2O+HO2 1.57E15 -1.00 00.

!94BAU/COB

! DUPLICATE

!CH2OH+O2 = CH2O+HO2 7.23E13 0.00

3577. !94BAU/COB

! DUPLICATE

!CH2OH+O2 = CH2O+HO2 1.2E12 0.00

0. !87TSA

!CH2OH+H = CH2O+H2 2.00E13 0.00 0.

!MBA017

CH2OH+H = CH3 + OH 9.64E13 0. 0.

!87TSA

!CH2OH+H = CH2O + H2 6.03E12 0. 0.

!87TSA

!CH2OH+H = CH2O + H2 2.0E13 0. 0.

!Bozzelli

!CH2OH+O = CH2O+OH 1.00E13 0.00 0.

!MBA021

!CH2OH+OH = CH2O+H2O 1.00E13 0.00 0.

!MBA019

CH2OH + HO2 = CH2O + H2O2 1.20E13 0. 0.

!92EGO/DU

CH2OH + HCO = CH3OH + CO 1.20E14 0. 0.

!92EGO/DU

CH2OH + HCO = CH2O + CH2O 1.81E14 0. 0.

!87TSA

CH2OH + CH3 = C2H5 + OH 1.37E14 -.41 6589.

!92EGO/DU

CH2OH + CH2O = HCO + CH3OH 5.54E03 2.81 5862.

!92EGO/DU

122

CH2OH + CH2OH = CH3OH + CH2O 1.20E13 0. 0.

!92EGO/DU

!CH2OH + H = CH3 + OH 2.39E02 3.353

-2971. !92EGO/DU

CH2OH + O = CH2O + OH 4.20E13 0. 0.

!87TSA

CH2OH + OH = CH2O + H2O 2.40E13 0. 0.

!87TSA

! *** CH2O ***

CH2O+M = 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


***********************************************************

! *** C2H6 ***

C2H6 + H = C2H5 + H2 5.40E02 3.50 5210.

!MBA066 73CAL/DOV (ok)

C2H6 + O = C2H5 + OH 3.00E07 2.00 5115.

!MBA067 84WAR (ok)

C2H6 + OH = C2H5 + H2O 8.70E09 1.05 1810.

!MBA068 83TUL/RAV (ok)

C2H6 + CH3 = C2H5 + CH4 5.50E-1 4.00 8300.

!MBA065 73CLA/DOV (ok)

C2H6 + O2 = C2H5 + HO2 4.03E13 0.

50842. !92EGO/DU

C2H6 + HO2 = C2H5 + H2O2 2.95E11 0.

14935. !92EGO/DU

!QUESTION? What about ignition steps C2H6+O2 & HO2

123

! *** 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 ***

C2H4+M = C2H2+H2+M 1.50E15 0.00

55800. !MBA128 83KIE/KAP (up)

!need 2 check 77JUS/ROT 77TAN 80TAN/GAR (Gardiner) lo (ok) better & self-

consistent

C2H4+M = C2H3+H+M 1.40E16 0.00

82360. !MBA129

!need to check 77JUS/ROT 80TAN/GAR (Gardiner) lo (ok) better & self-

consistent

!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)

124

!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 ***

C2H3+H = 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) 5.54E12 0.00

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 5.04E05 2.30

13500. !MBA088

C2H2+OH = CH2CO+H 2.18E-4 4.50

-1000. !MBA089

125

C2H2+OH = CH3+CO 4.83E-4 4.00

-2000. !MBA090

C2H2+O = CH2+CO 1.02E07 2.00

1900. !MBA076

C2H2+O = HCCO+H 1.02E07 2.00

1900. !MBA077

O+C2H2=OH+C2H 4.600E+19 -1.410

28950.00 !(GRIMECH11)

C2H2+O2 = HCCO+OH 2.00E08 1.50

30100. !MBA126

C2H2 = C2H + H 1.80E41 -7.76

137510. !92EGO/DU

C2H2 + H = C2H + H2 6.02E13 0.

22243. !92EGO/DU

C2H2 + OH = C2H + H2O 1.45E4 2.68

12035. !92EGO/DU

C2H2 + O2 = C2H + HO2 1.20E13 0.

74475. !92EGO/DU

C2H + O = CH + CO 1.81E13 0. 0.

!92EGO/DU

OH+C2H=H+HCCO 2.000E+13 0.000

0.00 !(GRIMECH11)

OH + C2H = CH2 + CO 2.00E13 0. 0.

!86TSA/HAM

C2H + O2 = CO + HCO 2.41E12 0. 0.

!92EGO/DU


*******************************************************

! *** 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

126

HCCO + OH = HCO + CO + H 1.00E13 0. 0.

!92EGO/DU

HCCO + CH2 = C2H + CH2O 1.00E13 0. 2000.

!92EGO/DU

! *** HCCO Reactions ***

HCCO+H = CH2SING+CO 1.00E14 0.00 0.

!MBA101

HCCO+O = H+2CO 1.00E14 0.00 0.

!MBA102

HCCO+O2 = 2CO+OH 1.60E12 0.00 854.

!MBA103

2HCCO = C2H2+2CO 1.00E13 0.00 0.

!MBA105

HCCO+CH2 = C2H3+CO 3.00E13 0.00 0.

!MBA115

! CxHy-Cl chemistry (Bozzelli--68 REACTIONS)

CH4 + CL <=> HCL + CH3 2.57E+13 0.0 3850.

CH4 + CLO <=> CH3 + HOCL 1.40E+13 0.0

15000.

CH3 + CLO <=> CH3O + CL 2.28E+07 1.54 -820.

CH3 + CLO <=> HCL + CH2O 5.50E+14 -0.51 710.

CH3CL <=> CH3 + CL 5.53E+31 -5.63 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 6.66E+13 0.0

10600.

CH3CL + O2 <=> HO2 + CH2CL 4.00E+13 0.0

52200.

CH3CL + HO2 <=> H2O2 + CH2CL 1.00E+13 0.0

16700.

CH3CL + CLO <=> HOCL + CH2CL 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 1.15E24 -3.45

34427. !"

CH2CL + O2 = CHCLO + OH 7.33E13 -0.44

24786. !"

127

CH2CL + HO2 = CHCLO + H2O 1.35E04 2.08 -532.

!"

CH2CL + CLO = CH2CLO + CL 1.34E11 0.40 -672.

!CHEMACT CH2CLC

CH2CL + H <=> CH3 + CL 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 0.38 2970.

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.

CHCLO + H = CHO + HCL 8.33E13 0.00 7400.

!HO

CHCLO + H = CH2O + CL 6.99E14 -0.58 6360.

!"

CHCLO = CHO + CL 8.86E29 -5.15

92920. !"

CHCLO = CO + HCL 1.10E30 -5.19

92960. !"

CHCLO + OH = CCLO + H2O 7.50E12 0.00 1200.

!WON '91

CHCLO + OH = HCO2 + HCL 1.98E07 1.20

-1516. !CHEMACT '94

CHCLO + O = CCLO + OH 8.80E12 0.00 3500.

!WON '91

CHCLO + O2 = CCLO + HO2 4.50E12 0.00

41800. !WON '91

CHCLO + CL = CCLO + HCL 1.25E13 0.00 500.

!"

CHCLO + CH3 = CCLO + CH4 2.50E10 0.00 6000.

!"

CHCLO + CH3 = CHO + CH3CL 1.50E13 0.00 8800.

!"

CHCLO + CLO = CCLO + HOCL 3.00E11 0.00 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 1.00E+13 0.0

28800.

C2H3 + CL <=> C2H3CL 6.50E+34 -6.63 8610.

C2H3 + CL <=> C2H2 + HCL 2.40E+24 -3.22 9070.

128

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 0.0 5100.

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 -6.56 11950.

H + CH3C.HCL <=> C2H5CL 8.01E+11 0.0 -

5090.

H + CH3C.HCL <=> C2H5 + CL 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 0.0 8100.

END

129

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 CH2O C

H O OH HO2

HCO HCCO N2 AR CN HCN N NH NO HNO

NH2 H2NO NCO N2O NO2 N2H2 HOCN H2CN NNH NH3

N2H3 C2N2 HNCO O3 HONO NO3 HNO3

CLCO NOCL

S

SH H2S SO SO2 SO3 HSO2 HOSO HOSO2 SN S2

CS COS HSNO HSO HOS HSOH H2SO HOSHO HS2

SO2* SCL

CH CH2 CH2(S) CH3 CH4

CH2OH CH3O CH3OH C2H C2H2 C2H3

C2H4 C2H5 C2H6 CH2CO HCCOH CH3CO CH2SING

C3H7 CH2CHO CH3CHO

CH3CL CH2CL CH2CLO. C2H5CL COCL2 CH2CLC.H2

C2H4OCL CHCLC.H C2H3CL CH3C.HCL CH2CLO CHCLO CHO HCO2

END

REACTIONS

!H+O2+M=HO2+M 3.61E17 -0.72 0.

! H2O/18.6/ H2/2.86/

!SH+H+M=H2+M 1.0E18 -1.0

0.

H+H+H2=H2+H2 9.2E16 -0.6

0.

H+H+H2O=H2+H2O 6.0E19 -1.25

0.

!H+OH+M=H2O+M 1.6E22 -2.0

0.

! H2O/5/

!H+O+M=OH+M 6.2E16 -0.6

0.

! H2O/5/

!O+O+M=O2+M 1.89E13 0.0

-1788.

!H2O2+M=OH+OH+M 1.3E17 0.0

45500.

H2+O2=2OH 1.7E13 0.0

47780.

!OH+H2=H2O+H 1.17E9 1.3

3626.

130

!O+OH=O2+H 3.61E14 -0.5

0.

!O+H2=OH+H 5.06E4 2.7

6290.

!OH+HO2=H2O+O2 7.5E12 0.0

0.0

!H+HO2=2OH 1.4E14 0.0

1073.

!O+HO2=O2+OH 1.4E13 0.0

1073.

!2OH=O+H2O 6.0E+8 1.3

0.

!H+HO2=H2+O2 1.25E13 0.0

0.

!HO2+HO2=H2O2+O2 2.0E12 0.0

0.

!H2O2+H=HO2+H2 1.6E12 0.0

3800.

!H2O2+OH=H2O+HO2 1.0E13 0.0

1800.

! C-H-O Chemistry (PRINCETON--28REACTIONS)

H+O2=O+OH 1.91E+14 0.0

16440.0 !PRINCETON

!H+O2=O+OH 2.65E+16 -0.7

17041.0 !GRI

!H+O2=O+OH 9.76E+13 0.0

14856.0 !Leeds

O+H2=H+OH 5.06E+04 2.7

6290.0 !Roseler

OH+H2=H2O+H 2.16E+08 1.5

3430.0

H2O+O=OH+OH 2.97E+06 2.0

13400.0

H2+M=H+H+M 4.57E+19 -1.4

104000.0

O+O+M=O2+M 6.17E+15 -0.5

0.0

H+O+M=OH+M 4.72E+18 -1.0

0.0

OH+H+M=H2O+M 2.21E+22 -2.0

0.0

H+O2+M=HO2+M 1.48E+12 0.6

0.0

!H+O2+M=HO2+M 1.48E+12 0.6

0.0

HO2+H=H2+O2 1.66E+13 0.0

820.0

HO2+H=OH+OH 7.08E+13 0.0

300.0

HO2+O=O2+OH 3.25E+13 0.0

0.0

HO2+OH=H2O+O2 2.89E+13 0.0

-500.0

HO2+HO2=H2O2+O2 4.20E+14 0.0

12000.0

131

!HO2+HO2=H2O2+O2 1.3E11 0.0

-1629.

H2O2+M=OH+OH+M 2.95E+14 0.0

48400.0

H2O2+H=H2O+OH 2.41E+13 0.0

3970.0

H2O2+H=HO2+H2 4.82E+13 0.0

7950.0

H2O2+O=OH+HO2 9.55E+06 2.0

3970.0

H2O2+OH=H2O+HO2 1.00E+12 0.0

0.0

!H2O2+OH=H2O+HO2 5.80E14 0.0

9560.0

CO+O+M=CO2+M 1.80E+10 0.0

2830.0 ! (Niksa 2380)

CO+O2=CO2+O 2.53E+12 0.0

47700.0

CO+OH=CO2+H 1.40E+07 1.95

-1350.0

CO+HO2=CO2+OH 3.01E+13 0.0

22900.0

HCO+M=H+CO+M 1.85E+17 -1.0

17000.0

HCO+O2=CO+HO2 7.58E+12 0.0

406.0

HCO+H=CO+H2 7.23E+13 0.0

0.0

HCO+O=CO+OH 3.00E+13 0.0

0.0

HCO+OH=CO+H2O 3.00E+13 0.0

0.0

! Hg chemistry (Wilcox) (10 reactions)

HGCL+M=HG+CL+M 4.25e13 0.0

16130. !Wilcox

HGCL2+M=HG+CL2+M 3.19e12 0.0 86980.

!Wilcox

HG+HCL=HGCL+H 2.62e12 0.0

82060. !Wilcox

HG+CL2=HGCL+CL 1.34e12 0.0

42800. !Wilcox

HGCL2+M=HGCL+CL+M 2.87e14 0.0 80550.

!Wilcox

HGCL+HCL=HGCL2+H 4.50e13 0.0 30270.

!Wilcox

HGCL+CL2=HGCL2+CL 2.465e10 0.0 0. !Wilcox

HG+HOCL=HGCL+OH 3.09e13 0.0 36638

!Wilcox

HGCL+HOCL=HGCL2+OH 3.48e10 0.0 485

!Wilcox

!HGO+M=HG+O+M 3.09e10 0.0 8750

!Wilcox

132

!Bozzelli chlorine chemistry

CL + H2 = HCL + H 4.80E+13 0.0

5000.

CL + CO = COCL 1.95E+19 -3.01 8070.

CL + CL + M = CL2 + M 5.75E+14 0.0 -

1600.

CL + HCO = HCL + CO 1.41E+14 -0.35 510.

CLO + H2 = HOCL + H 1.00E+13 0.0

13500.

CLO + CO = CO2 + CL 6.02E+11 0.0

7400.

!COCL + CL = COCL2 3.40E+28 -5.61 3390.

COCL + CL = CO + CL2 1.49E+19 -2.17 1470.

COCL + H = CO + HCL 3.54E+16 -0.79 1060.

COCL + H = HCO + CL 3.42E+09 1.15

-180.

COCL + O2 = CO2 + CLO 7.94E+10 0.0 3300.

COCL + O = CO2 + CL 1.00E+13 0.0

0.0

O + HCL = OH + CL 5.25E+12 0.0

6400.

O + CL2 = CLO + CL 1.26E+13 0.0

2800.

O + CLO = CL + O2 5.75E+13 0.0

400.

OH + HCL = H2O + CL 2.20E+12 0.0

1000.

!*********************Duplicate Chemistry***********************

!CH3CL + OH = CH2CL + H2O 1.32E+12 0.0 2300.

!CH3CL + O = OH + CH2CL 1.70E+13 0.0 7300.

!CH3CL + H = H2 + CH2CL 6.66E+13 0.0

10600.

!CH3CL + O2 = HO2 + CH2CL 4.00E+13 0.0

52200.

!CH3CL + HO2 = H2O2 + CH2CL 1.00E+13 0.0

16700.

!CH3CL + CLO = HOCL + CH2CL 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.

!CH3CL = CH3 + CL 5.53E+31 -5.63

88810.

!CH3CL = CH2 + HCL 1.82E+25 -4.69

132460.

!CH3CL = CH2CL + H 1.31E+30 5.23

106100.

!CH2CL + O2 = CLO + CH2O 8.46E+13 -1.03 8180.

!CH2CL + H = CH3 + CL 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 0.38 2970.

!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.

133

!CH2CL + O = CH2O + CL 8.31E+13 -0.18 800.

!CH2CLO. = CH2O + CL 2.51E+24 -4.78 10070.

!CH2O + CL = HCO + HCL 5.00E+13 0.0 500.

!CH2O + CLO = HOCL + HCO 1.20E+13 0.0 2000.

!CH3 + CLO = CH3O + CL 2.28E+07 1.54 -820.

!CH3 + CLO = HCL + CH2O 5.50E+14 -0.51 710.

!CH4 + CLO = CH3 + HOCL 1.40E+13 0.0

15000.

!CH4 + CL = HCL + CH3 2.57E+13 0.0 3850.

!C2H2 + CL = HCL + C2H 1.00E+13 0.0

28800.

!C2H3 + CL = C2H3CL 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 0.0 5100.

!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 + CHCL*CJH 5.00E+12 0.0 5870.

!**************************************************************************

HO2 + CL = HCL + O2 1.58E+13 0.0

0.

HO2 + CL = CLO + OH 3.35E+14 -0.32 1470.

H2O2 + CL = HCL + HO2 1.02E+12 0.0 800.

H2O2 + CLO = HOCL + HO2 5.00E+12 0.0 2000.

!NO-CL reaction (9 reactions)

CLO+NO=NO2+CL 3.85E12 0.0

140. !niksa

HNO+CL=HCL+NO 8.99E13 0.0

993.

HONO+CL=HCL+NO2 5.00E13 0.0

0.

NOCL+M=NO+CL+M 2.50E15 0.0

31991. !800-1500 K

NOCL+CL=NO+CL2 2.40E13 0.0

0. !niksa

NOCL+H=NO+HCL 4.60E13 0.0

890. !niksa

NOCL+O=NO+CLO 5.00E12 0.0

3000. !niksa

NOCL+OH=HOCL+NO 5.4E12 0.0

2250.

NOCL+OH=HONO+CL 5.5E10 0.0

-480.

! NOx chemistry (Muller, 2000)

!N-O-H reaction (Muller and Dryer et al,2000) (24 REACTIONS)

NO+O+M=NO2+M 3.00E13 0.0

0.

134

NO+H+M=HNO+M 1.52E15 -0.41

0.

NO+OH+M=HONO+M 1.99E12 -0.05

-721.

NO2+H2=HONO+H 1.30E4 2.76

15000.

NO2+O=O2+NO 1.05E14 -0.52

0. !niksa

!NO2+O=O2+NO 3.9E12 0.0

-240.

NO2+O+M=NO3+M 1.33E13 0.0

0.

NO2+H=NO+OH 1.32E14 0.0

362.

NO2+OH+M=HNO3+M 4.52E13 0.0

0.

NO2+OH=HO2+NO 1.81E13 0.0

6680. !NIKSA

!NO+HO2=NO2+OH 2.11E12 0.0

-479. !MULLER (2000)

NO2+NO2=NO3+NO 9.64E9 0.73

20900.

NO2+NO2=2NO+O2 1.63E12 0.0

26100.

HNO+H=NO+H2 4.46E11 0.72

655.

HNO+O=OH+NO 1.81E13 0.0

0.

HNO+OH=H2O+NO 1.30E7 1.88

-956.

HNO+NO=N2O+OH 2.00E12 0.0

26000.

HNO+NO2=HONO+NO 6.02E11 0.0

1990.

HNO+HNO=H2O+N2O 8.51E8 0.0

3080.

HONO+O=OH+NO2 1.20E13 0.0

5960.

HONO+OH=H2O+NO2 1.70E12 1.0

-520.

N2O+M=N2+O+M 7.91E10 0.0

56000.

N2O+O=N2+O2 1.00E14 0.0

28000.

N2O+O=NO+NO 1.00E14 0.0

28000.

N2O+H=N2+OH 2.23E14 0.0

16800. !NIKSA

!N2O+H=N2+OH 2.53E10 0.0

4550.

N2O+OH=N2+HO2 2.00E12 0.0

40000.

CO+N2O=CO2+N2 5.01E13 0.0

44000.

CO+NO2=CO2+NO 9.03E13 0.0

33800.

135

HCO+NO=HNO+CO 7.23E12 0.0

0.

HCO+NO2=HONO+CO 1.24E23 -3.29

2350.

HCO+NO2=H+NO+CO2 8.39E15 -0.75

1930.

! SOx chemistry (66 reactions)

SO2+O(+M) = SO3(+M) 9.200E+10 0.0000

2400.

N2/1.3/ SO2/10/ H2O/10/

LOW / 4.000E+28 -4.00 5250. /

SO2+OH(+M) = HOSO2(+M) 7.200E+12 0.0000

715.00 !muller and niksa

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 3.900E+08

1.8900 76000.00

SO2+OH = SO3+H 4.900E+02

2.6900 23850.00

SO2+CO = SO+CO2 2.700E+12 0.0000

48300.

SO2*+M = SO2+M 1.300E+14

0.0000 3600.00

SO2*+SO2 = SO3+SO 2.600E+12

0.0000 2430.00

SO3+H = HOSO+O 2.500E+05

2.9200 50300.0

SO+O(+M) = SO2(+M) 3.200E+13

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 /

SO+M = S+O+M 4.000E+14

0.0000 107000.

N2/1.5/ SO2/10/ H2O/10/

SO+H+M = HSO+M 5.000E+15

0.0000 0.00

N2/1.5/ SO2/10/ H2O/10/

2SO = SO2+S 2.000E+12

0.0000 4000.00

HSO+H = HSOH 2.500E+20 -3.1400

920.00

HSO+H = SH+OH 4.900E+19 -1.8600

1560.

HSO+H = S+H2O 1.600E+09

1.3700 -340.

136

HSO+H = H2SO 1.800E+17 -2.4700

50.

HSO+H = H2S+O 1.100E+06

1.0300 10400.

HSO+O+M = HSO2+M 1.100E+19 -1.7300

-50.

HSO+O = SO2+H 4.500E+14 -0.4000

0.00

HSO+O+M = HOSO+M 6.900E+19 -1.6100

1600.

HSO+O = O+HOS 4.800E+08

1.0200 5340.

HSO+O = OH+SO 1.400E+13

0.1500 300.

HSO+OH = HOSHO 5.200E+28 -5.4400

3170.

HSO+OH = HOSO+H 5.300E+07 1.5700

3750.

HSO+OH = SO+H2O 1.700E+09 1.0300

470.

HSO+O2 = SO2+OH 1.000E+12

0.0000 0.0 !NIKSA, MULLER

HSOH = SH+OH 2.800E+39 -8.7500

75200.

HSOH = S+H2O 5.800E+29 -5.6000

54500.

HSOH = H2S+O 9.800E+16 -3.4000

86500.

H2SO = H2S+O 4.900E+28 -6.6600

71700.

HOSO(+M) = HSO2(+M) 1.000E+09 1.0300

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 2.500E+30 -4.8000

119000. !MULLER

HOSO+H = SO+H2O 6.300E-10 6.2900

-1900.

HOSO+OH = SO2+H2O 1.000E+12 0.0000

0.00

HOSO+O2 = HO2+SO2 1.000E+12 0.0000

1000.

HSO2(+M) = H+SO2(+M) 2.000E+11 -0.9000

18361. !muller

N2/1/ SO2/10/ H2O/10/

LOW / 3.500E+25 -3.29 9612.48 /

HOSO2 = HOSO+O 5.400E+18 -2.3400

106300.

HOSO2+H = SO2+H2O 1.000E+12

0.0000 0.00

HOSO2+O = SO3+OH 5.000E+12

0.0000 0.00

HOSO2+OH = SO3+H2O 1.000E+12 0.0000

0.00

137

HOSO2+O2 = HO2+SO3 7.80E+11 0.0000

656.0

HOSHO = HOSO+H 6.400E+30 -5.8900

73800.

HOSHO+H = HOSO+H2 1.000E+12 0.0000

0.00

HOSHO+O = HOSO+OH 5.000E+12 0.0000

0.00

SO2+NO2=NO+SO3 6.3E12 0.0

27000. !NIKSA

SO+NO2 = SO2+NO 8.432E+12 0.00

0.00

HSO+NO2 = HOSO+NO 5.8E12 0.00

0.00

! modified ( 8 reactions)

SO3+O = SO2+O2 2.000E+12

0.0000 19870.

SO3+SO = 2SO2 1.000E+12

0.0000 10000.00

SO+O2 = SO2+O 7.600E+03

2.3700 3000.00

HOSO(+M) = SO+OH(+M) 9.940E+21 -2.5400

76380.00

LOW / 1.156E+46 -9.02 53350.00 /

TROE / 9.5000E-01 2.9890E+03 1.1000E+00 /

SO+OH = SO2+H 1.077E+17 -1.35

0.0

H+SO2(+M) = HOSO(+M) 3.119E+08 1.6100

7200.00

LOW / 2.662E+38 -6.43 11150.00 /

TROE / 8.2000E-01 1.3088E+05 2.6600E+02 /

HOSO2 = SO3+H 1.400E+18 -2.9100

55000.00

HSO+H = SO+H2 1.000E+13

0.0000 0.00

! New ( 7 reactions)

HOSO+H = SO2+H2 3.000E+13

0.0000 0.00

HSO2+H = SO2+H2 3.000E+13

0.0000 0.00

HSO2+OH = SO2+H2O 1.000E+13

0.0000 0.00

HSO2+O2 = HO2+SO2 1.000E+13

0.0000 0.00

HOSHO = SO+H2O 1.200E+24 -3.5900

59500.

HOSHO+OH = HOSO+H2O 1.000E+12 0.0000

0.00

HOSO2+H = SO3+H2 1.0E+12 0.00

0.00

!S-CL-O reactions (quantum chemistry) (3 reactions)

138

SO+CLO=SO2+CL 1.29E10 0.0

15744.

SCL+O=SO+CL 2.84E11 0.0

12350.

SO+CL2=SCL+CLO 1.63E9 0.0

27320.

! NIST CxHy chemistry ( REACTIONS)


***********************************************************

! *** Methane ***

CH4 + 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?

! *** Methyl ***

CH3 + H (+M) = CH4 (+M) 6.00E16 -1.00

0. !MBA002 84WAR (up)

LOW/8.00E26 -3.0 0./ !(89STE/SMI2)

SRI/0.45 797. 979. /

H2/2.0/ CO/2.0/ CO2/3.0/ H2O/5.0/

!CH3 + H (+M) = CH4 (+M) 1.21E15 -0.40

0. !86TSA/HAM

!factor of 2 different, which to use?

CH3 + H = CH2 + H2 9.00E13 0.00

15100. !MBA013 (mb?)

CH3 + O = CH2O + H 8.00E13 0.00

0. !MBA009 (mb?)

CH3 + OH = CH2 + H2O 7.50E06 2.00

5000. !MBA012 (mb?)

!CH3 + OH = CH3OH 2.24E40 -8.20

11673. !87DEA/WES (1atm)

!CH3 + OH = CH2OH + H 2.64E19 -1.80

8068. !87DEA/WES (1atm)

!CH2OH+H = CH3+OH 1.00E14 0.00

0. !MBA010

CH3 + OH = CH3O + H 5.74E12 -0.23

13931. !87DEA/WES (1atm)

139

!CH3O+H = CH3+OH 1.00E14 0.00

0. !MBA011

CH3 + OH = CH2SING + H2O 8.90E19 -1.80

8067. !87DEA/WES (1atm)

!CH3 + O2 = CH3O + O 2.05E18 -1.57

29229. !MBA008 86TSA/HAM

CH3 + O2 <=> CH3O + O 2.05E+19 -1.570

29229. !bozzelli

!CH3 + O2 = CH3O + O 2.88E15 -1.15

30850. !92HO/YU (BOZ)

!CH3 + O2 = CH3O + O 7.20E13 0.00

31600 !92BAU/COB

!CH3 + O2 = CH2O + OH 3.30E11 0.

9000. !92BAU/COB

CH3 + O2 = CH2O + OH 3.59E09 -0.14

10150. !92HO/YU (BOZ)

!CH3 + O2 = CH3O + O 1.32E14 0.

31600. !92BAU/COB

!CH3 + O2(+M)=CH3OO(+M) 7.80E08 1.2

0. !92BAU/COB

CH3 + HO2 = CH3O + OH 2.00E13 0.00

0. !MBA007 86TSA/HAM

CH3 + CH3 = C2H4 + H2 1.00E16 0.

32005. !92EGO/DU

!CH3 + CH3(+M) = C2H6 (+M) 9.03E16 -1.20

654. !MBA001 88WAG/WAR (ok)

! LOW/3.18E41 -7.0 2762./ !88WAG/WAR

! TROE/0.6041 6927. 132./

!H2/2.0/ CO/2.0/ CO2/3.0/ H2O/5.0/

CH3+CH3<=>C2H6 2.68E+29 -5.0

6130.0 !Bozzelli

!CH3+HCO=CH4+CO 2.648E+13 0.000

0.00 !(GRIMECH11)

CH3+HCO=CH4+CO 1.20E14 0. 0.

!86TSA/HAM

C+CH3=H+C2H2 5.000E+13 0.000 0.00

!(GRIMECH1)

! *** 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

140

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 ***

!********************

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.


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.


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

141

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)


*******************************************************

! *** CH3O, CH2OH ***

CH3O+M = 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 = CH2O+H+M 1.00E14 0.00

25000. !MBA015

142

!CH2OH+O2 = CH2O+HO2 1.48E13 0.00

1500. !MBA023

CH2OH+O2 = CH2O+HO2 2.41E14 0.00

5000. !LAW

!CH2OH+O2 = CH2O+HO2 1.57E15 -1.00

00. !94BAU/COB

! DUPLICATE

!CH2OH+O2 = CH2O+HO2 7.23E13 0.00

3577. !94BAU/COB

! DUPLICATE

!CH2OH+O2 = CH2O+HO2 1.2E12 0.00

0. !87TSA

!CH2OH+H = CH2O+H2 2.00E13 0.00

0. !MBA017

CH2OH+H = CH3 + OH 9.64E13 0.

0. !87TSA

!CH2OH+H = CH2O + H2 6.03E12 0.

0. !87TSA

!CH2OH+H = CH2O + H2 2.0E13 0.

0. !Bozzelli

!CH2OH+O = CH2O+OH 1.00E13 0.00

0. !MBA021

!CH2OH+OH = CH2O+H2O 1.00E13 0.00

0. !MBA019

CH2OH + HO2 = CH2O + H2O2 1.20E13 0.

0. !92EGO/DU

CH2OH + HCO = CH3OH + CO 1.20E14 0.

0. !92EGO/DU

CH2OH + HCO = CH2O + CH2O 1.81E14 0.

0. !87TSA

CH2OH + CH3 = C2H5 + OH 1.37E14 -.41

6589. !92EGO/DU

CH2OH + CH2O = HCO + CH3OH 5.54E03 2.81

5862. !92EGO/DU

CH2OH + CH2OH = CH3OH + CH2O 1.20E13 0.

0. !92EGO/DU

!CH2OH + H = CH3 + OH 2.39E02 3.353

-2971. !92EGO/DU

CH2OH + O = CH2O + OH 4.20E13 0.

0. !87TSA

CH2OH + OH = CH2O + H2O 2.40E13 0.

0. !87TSA

! *** CH2O ***

CH2O+M = 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

143

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


***********************************************************

! *** C2H6 ***

C2H6 + H = C2H5 + H2 5.40E02 3.50

5210. !MBA066 73CAL/DOV (ok)

C2H6 + O = C2H5 + OH 3.00E07 2.00

5115. !MBA067 84WAR (ok)

C2H6 + OH = C2H5 + H2O 8.70E09 1.05

1810. !MBA068 83TUL/RAV (ok)

C2H6 + CH3 = C2H5 + CH4 5.50E-1 4.00

8300. !MBA065 73CLA/DOV (ok)

C2H6 + O2 = C2H5 + HO2 4.03E13 0.

50842. !92EGO/DU

C2H6 + HO2 = C2H5 + H2O2 2.95E11 0.

14935. !92EGO/DU

!QUESTION? What about ignition steps C2H6+O2 & HO2

! *** 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

144

!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 ***

C2H4+M = C2H2+H2+M 1.50E15 0.00

55800. !MBA128 83KIE/KAP (up)

!need 2 check 77JUS/ROT 77TAN 80TAN/GAR (Gardiner) lo (ok) better & self-

consistent

C2H4+M = C2H3+H+M 1.40E16 0.00

82360. !MBA129

!need to check 77JUS/ROT 80TAN/GAR (Gardiner) lo (ok) better & self-

consistent

!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 ***

C2H3+H = C2H2+H2 1.20E13 0.00

0. !92BAU/COB

! C2H3+H = C2H2+H2 4.00E13 0.00

0. !MBA080

145

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) 5.54E12 0.00

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 5.04E05 2.30

13500. !MBA088

C2H2+OH = CH2CO+H 2.18E-4 4.50

-1000. !MBA089

C2H2+OH = CH3+CO 4.83E-4 4.00

-2000. !MBA090

C2H2+O = CH2+CO 1.02E07 2.00

1900. !MBA076

C2H2+O = HCCO+H 1.02E07 2.00

1900. !MBA077

O+C2H2=OH+C2H 4.600E+19 -1.410

28950.00 !(GRIMECH11)

C2H2+O2 = HCCO+OH 2.00E08 1.50

30100. !MBA126

C2H2 = C2H + H 1.80E41 -7.76

137510. !92EGO/DU

C2H2 + H = C2H + H2 6.02E13 0.

22243. !92EGO/DU

C2H2 + OH = C2H + H2O 1.45E4 2.68

12035. !92EGO/DU

C2H2 + O2 = C2H + HO2 1.20E13 0.

74475. !92EGO/DU

C2H + O = CH + CO 1.81E13 0.

0. !92EGO/DU

OH+C2H=H+HCCO 2.000E+13 0.000

0.00 !(GRIMECH11)

146

OH + C2H = CH2 + CO 2.00E13 0.

0. !86TSA/HAM

C2H + O2 = CO + HCO 2.41E12 0.

0. !92EGO/DU


*******************************************************

! *** 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 + OH = HCO + CO + H 1.00E13 0.

0. !92EGO/DU

HCCO + CH2 = C2H + CH2O 1.00E13 0.

2000. !92EGO/DU

! *** HCCO Reactions ***

HCCO+H = CH2SING+CO 1.00E14 0.00

0. !MBA101

HCCO+O = H+2CO 1.00E14 0.00

0. !MBA102

HCCO+O2 = 2CO+OH 1.60E12 0.00

854. !MBA103

2HCCO = C2H2+2CO 1.00E13 0.00

0. !MBA105

HCCO+CH2 = C2H3+CO 3.00E13 0.00

0. !MBA115

! CxHy-Cl chemistry (Bozzelli--68 REACTIONS)

CH4 + CL <=> HCL + CH3 2.57E+13 0.0 3850.

CH4 + CLO <=> CH3 + HOCL 1.40E+13 0.0

15000.

147

CH3 + CLO <=> CH3O + CL 2.28E+07 1.54 -820.

CH3 + CLO <=> HCL + CH2O 5.50E+14 -0.51 710.

CH3CL <=> CH3 + CL 5.53E+31 -5.63 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 6.66E+13 0.0

10600.

CH3CL + O2 <=> HO2 + CH2CL 4.00E+13 0.0

52200.

CH3CL + HO2 <=> H2O2 + CH2CL 1.00E+13 0.0

16700.

CH3CL + CLO <=> HOCL + CH2CL 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 1.15E24 -3.45

34427. !"

CH2CL + O2 = CHCLO + OH 7.33E13 -0.44

24786. !"

CH2CL + HO2 = CHCLO + H2O 1.35E04 2.08

-532. !"

CH2CL + CLO = CH2CLO + CL 1.34E11 0.40

-672. !CHEMACT CH2CLC

CH2CL + H <=> CH3 + CL 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 0.38 2970.

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.

148

CHCLO + H = CHO + HCL 8.33E13 0.00

7400. !HO

CHCLO + H = CH2O + CL 6.99E14 -0.58

6360. !"

CHCLO = CHO + CL 8.86E29 -5.15

92920. !"

CHCLO = CO + HCL 1.10E30 -5.19

92960. !"

CHCLO + OH = CCLO + H2O 7.50E12 0.00

1200. !WON '91

CHCLO + OH = HCO2 + HCL 1.98E07 1.20

-1516. !CHEMACT '94

CHCLO + O = CCLO + OH 8.80E12 0.00

3500. !WON '91

CHCLO + O2 = CCLO + HO2 4.50E12 0.00

41800. !WON '91

CHCLO + CL = CCLO + HCL 1.25E13 0.00

500. !"

CHCLO + CH3 = CCLO + CH4 2.50E10 0.00

6000. !"

CHCLO + CH3 = CHO + CH3CL 1.50E13 0.00

8800. !"

CHCLO + CLO = CCLO + HOCL 3.00E11 0.00

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 1.00E+13 0.0

28800.

C2H3 + CL <=> C2H3CL 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 0.0 5100.

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.

149

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 -6.56 11950.

H + CH3C.HCL <=> C2H5CL 8.01E+11 0.0 -

5090.

H + CH3C.HCL <=> C2H5 + CL 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 0.0 8100.

END

150

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

151

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

152

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

153

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

154

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

155

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

156

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

157

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

158

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

159

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

160

6.92917693E+00 2.24452779E-03-7.90979097E-07 1.25463837E-10-7.39419240E-15

2

-1.70625997E+04-1.17716986E+01 2.10449581E+00 1.44325666E-02-1.24381307E-05

3

5.11270771E-09-8.13184236E-13-1.55220641E+04 1.37425593E+01

4

! from glarborg, different thermodynamics

H2SO H 2O 1S 1 0G 300.000 5000.000 1683.000

11

6.05713665E+00 3.34805040E-03-1.26811609E-06 2.11370265E-10-1.28989945E-14

2

-8.10888022E+03-7.74337887E+00 1.67605472E+00 1.36703075E-02-1.00346844E-05

3

3.40878662E-09-4.36976254E-13-6.69202687E+03 1.56138164E+01

4

HOSHO H 2O 2S 1 0G 300.000 5000.000 1394.000

11

9.02485610E+00 3.14966096E-03-1.13339516E-06 1.82050134E-10-1.08158633E-14

2

-3.60374633E+04-2.14761309E+01 1.64768512E+00 2.36621687E-02-2.33383665E-05

3

1.11468033E-08-2.06841918E-12-3.38188221E+04 1.69561663E+01

4

HS2 burc94H 1S 2 0 0G 298.150 5000.000 2000.00

0 1

0.46552282E+01 0.29202531E-02-0.11010941E-05 0.18878697E-09-0.12318000E-13

2

0.16492900E+04 0.27987542E+01 0.40214995E+01 0.31961918E-02 0.21507270E-05

3

-0.48650943E-08 0.21391804E-11 0.18942796E+04 0.64213003E+01 0.32457475E+04

4

SO2* pg00 S 1O 2 G 0300.00 5000.00 1000.00

1

0.05254498E+02 0.01978545E-01-0.08204226E-05 0.01576383E-08-0.01120451E-12

2

-0.08300578E+04-0.01146056E+02 0.02911439E+02 0.08103022E-01-0.06906710E-04

3

0.03329016E-07-0.08777121E-11-0.01400178E+04 0.01111740E+03

4

SCL CL 1S 1 G 300.000 5000.000 1000.00

1

0.45818029E+01 0.21947902E-06-0.40124896E-08 0.42919972E-11-0.41192556E-15

2

0.17447034E+05 0.23937794E+01 0.43257799E+01 0.11193879E-02-0.18253796E-05

3

0.13136131E-08-0.35151127E-12 0.17493485E+05 0.36051734E+01

4

CH JANAFC 1H 1 0 0G 300.000 5000.000 1362.000

01

2.52630635E+00 1.80332526E-03-4.84589067E-07 5.68080160E-11-2.40047828E-15

2

7.07726347E+04 7.35584439E+00 3.36517755E+00 1.94434021E-05 9.12668865E-07

3

-4.22584668E-10 5.86289093E-14 7.04631376E+04 2.78685063E+00

4

CH2 JANAFC 1H 2 0 0G 300.000 5000.000 1409.000

01

161

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 4.48071530E+00

4

CH2(S) H 2C 1 0 0G 300.00 5000.00 1360.00

0 1

3.09732461E+00 2.80331155E-03-7.10881104E-07 8.36924323E-11-3.81270428E-15

2

4.95090024E+04 4.31246006E+00 3.32929383E+00 2.26625413E-03-2.38920714E-07

3

-1.04565889E-10 2.51400070E-14 4.94285310E+04 3.06576550E+00

4

CH3 H 3C 1 0 0G 300.00 5000.00 1000.00

0 1

2.84405200E+00 6.13797400E-03-2.23034500E-06 3.78516100E-10-2.45215900E-14

2

1.64378100E+04 5.45269700E+00 2.43044300E+00 1.11241000E-02-1.68022000E-05

3

1.62182900E-08-5.86495300E-12 1.64237800E+04 6.78979400E+00

4

CH4 JANAFC 1H 4 0 0G 300.000 5000.000 1706.000

01

1.78092211E+00 9.74452639E-03-3.42930517E-06 5.43903042E-10-3.20521160E-14

2

-1.00945292E+04 9.16546733E+00 3.19715119E+00 2.00818162E-03 8.06603744E-06

3

-6.00052219E-09 1.24529966E-12-1.01110356E+04 3.22246966E+00

4

CH2OH THERMC 1H 3O 1 0G 300.000 5000.000 1392.000

11

6.19306234E+00 5.07058138E-03-1.69091931E-06 2.58276720E-10-1.48215984E-14

2

-3.94142242E+03-9.38725416E+00 1.88250578E+00 1.51099762E-02-1.05243599E-05

3

3.74863620E-09-5.37480607E-13-2.45553760E+03 1.37504657E+01

4

CH3O THERMC 1H 3O 1 0G 300.000 5000.000 1396.000

01

4.74429408E+00 6.60354819E-03-2.61174475E-06 4.77928742E-10-3.13974103E-14

2

-4.04799242E+02-3.05593859E+00-1.17225816E+00 2.20349833E-02-1.82975276E-05

3

7.80307444E-09-1.34408591E-12 1.47975243E+03 2.81336104E+01

4

CH3OH THERMC 1H 4O 1 0G 300.000 5000.000 1387.000

11

4.59418840E+00 8.84373788E-03-2.95933831E-06 4.52531299E-10-2.59724665E-14

2

-2.65062563E+04-1.06630729E+00 1.56247567E+00 1.35883881E-02-4.67956911E-06

3

4.31728248E-12 2.32389755E-13-2.51856083E+04 1.61012691E+01

4

C2H Field87C 2H 1 0 0G 300.000 5000.000 2024.000

01

162

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 4.52636079E+00

4

C2H2 JANAFC 2H 2 0 0G 300.000 5000.000 1376.000

01

5.58079185E+00 4.13414447E-03-1.41744388E-06 2.20442432E-10-1.28056651E-14

2

2.49557217E+04-9.70120474E+00 3.17826088E+00 8.28386242E-03-3.41250852E-06

3

1.95230262E-10 1.36601029E-13 2.59408845E+04 3.72841870E+00

4

C2H3 MGC 2H 3 0 0G 300.000 5000.000 1390.000

01

5.54192160E+00 5.83527734E-03-1.90937796E-06 2.87787492E-10-1.63580788E-14

2

3.33365935E+04-6.00049099E+00 2.02995091E+00 1.35234576E-02-8.13106656E-06

3

2.48655305E-09-2.99971920E-13 3.46030855E+04 1.30360744E+01

4

C2H4 JANAFC 2H 4 0 0G 300.000 5000.000 1394.000

01

5.04902709E+00 9.03240832E-03-3.05663601E-06 4.70995771E-10-2.71778308E-14

2

3.67830603E+03-6.49864284E+00 6.53934711E-01 1.78307866E-02-9.42052861E-06

3

2.41508271E-09-2.30958678E-13 5.38196410E+03 1.76768137E+01

4

C2H5 BLPC 2H 5 0 0G 300.000 5000.000 1379.000

11

5.55775601E+00 1.08697043E-02-3.72234659E-06 5.78205207E-10-3.35527708E-14

2

1.12858008E+04-7.27721884E+00 1.75409028E+00 1.62227919E-02-4.99070479E-06

3

-3.71126053E-10 3.32382683E-13 1.30432122E+04 1.45429900E+01

4

C2H6 JANAFC 2H 6 0 0G 300.000 5000.000 1384.000

11

5.79770134E+00 1.30844142E-02-4.45782896E-06 6.90057114E-10-3.99465946E-14

2

-1.34692940E+04-1.12190298E+01 4.74260078E-01 2.22846672E-02-9.49503792E-06

3

1.42821577E-09 3.69083854E-14-1.12169150E+04 1.86523474E+01

4

CH2CO THERMC 2H 2O 1 0G 300.000 5000.000 1407.000

01

7.56655849E+00 4.38618679E-03-1.46608341E-06 2.24243208E-10-1.28796340E-14

2

-8.94777853E+03-1.65449287E+01 1.53866880E+00 2.12191771E-02-1.96411582E-05

3

9.12485651E-09-1.66311280E-12-7.15400366E+03 1.48116548E+01

4

HCCOH 32387H 2C 2O 1 G 0300.00 4000.00 1000.00

1

163

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

164

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 1.49532259E+01

4

CH2CLO. 7/89 C 1O 1H 2CL 1G 300.000 5000.000 1373.000

01

6.23016634E+00 5.85335042E-03-2.04343616E-06 3.21614950E-10-1.88374791E-14

2

-3.01375514E+03-6.13215836E+00 2.69730811E+00 1.19860671E-02-5.26850873E-06

3

6.29748948E-10 9.22568674E-14-1.54332205E+03 1.36469449E+01

4

C2H5CL JANAFC 2H 5CL 1 0G 300.000 5000.000 1392.000

11

8.42602350E+00 1.08670043E-02-3.69875171E-06 5.72375356E-10-3.31331698E-14

2

-1.75817705E+04-2.02070663E+01 3.66148399E-01 2.94578293E-02-2.02144179E-05

3

7.32637257E-09-1.10750593E-12-1.47415074E+04 2.31928787E+01

4

COCL2 BSNC 1O 1CL 2 0G 300.000 5000.000 1398.000

01

8.37356642E+00 1.45611397E-03-5.20810326E-07 8.33827599E-11-4.94460050E-15

2

-2.94214218E+04-1.48380786E+01 4.47662819E+00 1.22362568E-02-1.20349900E-05

3

5.66457278E-09-1.03108770E-12-2.82550178E+04 5.46450425E+00

4

CH2CLC.H2 ROUX87 C 2 0H 4CL 1G 300.000 5000.000 1382.000

11

8.54612636E+00 8.70530333E-03-3.06156397E-06 4.84249575E-10-2.84616389E-14

2

6.34576886E+03-1.90781271E+01 3.05624191E-01 2.80849016E-02-2.10736532E-05

3

8.39568397E-09-1.40542189E-12 9.24856407E+03 2.52245042E+01

4

C2H4OCL 7/89 C 2O 1H 4CL 1G 300.000 5000.000 1396.000

31

1.10145297E+01 8.15790219E-03-2.83847077E-06 4.45765276E-10-2.60698167E-14

2

-6.00681870E+02-2.65698041E+01-1.53127350E+00 4.60006810E-02-4.75639250E-05

3

2.43865270E-08-4.83222322E-12 2.96342754E+03 3.78839199E+01

4

CHCLC.H BBB C 2 0H 2CL 1G 300.000 5000.000 1511.000

01

1.06526620E+01 3.61331241E-03-1.53803006E-06 2.74591563E-10-1.75187824E-14

2

2.57639738E+04-3.33173153E+01 4.19961326E+00 3.01912456E-03 1.75440170E-05

3

-1.65976891E-08 4.20107817E-12 2.95916757E+04 6.94137452E+00

4

C2H3CL MAN,LOUWC 2H 3CL 1 0G 300.000 5000.000 1404.000

01

165

8.12532976E+00 6.32279870E-03-2.10889293E-06 3.22338516E-10-1.85123802E-14

2

-1.07821872E+03-1.83168402E+01 2.65621701E-01 2.62518050E-02-2.13968077E-05

3

8.75943199E-09-1.42117873E-12 1.44275080E+03 2.32522142E+01

4

CH3C.HCL ROUX87 C 2 0H 4CL 1G 300.000 5000.000 1385.000

01

7.56228919E+00 9.78512691E-03-3.39196568E-06 5.31268607E-10-3.10097278E-14

2

4.81011272E+03-1.39885482E+01 1.12828446E+00 2.43449415E-02-1.65723496E-05

3

6.28310091E-09-1.04458965E-12 7.17099543E+03 2.08663440E+01

4

CH2CLO THERMC 1H 2O 1CL 1G 300.000 5000.000 1396.000

01

6.44020663E+00 5.56800020E-03-1.92136661E-06 3.00102093E-10-1.74854992E-14

2

-3.26090898E+03-7.43338025E+00 8.93635756E-01 1.91814651E-02-1.48947039E-05

3

5.99701589E-09-9.84844641E-13-1.40140300E+03 2.21205362E+01

4

CHCLO BSNC 1H 1O 1CL 1G 300.000 5000.000 1396.000

01

6.27872759E+00 3.15667555E-03-1.08913544E-06 1.70121699E-10-9.91319183E-15

2

-2.22087864E+04-6.45495503E+00 2.84949067E+00 1.16574562E-02-9.25161808E-06

3

3.76997592E-09-6.21893307E-13-2.10716929E+04 1.17804371E+01

4

CHO ESTC 1H 1O 1 0G 300.000 5000.000 1367.000

01

3.69472521E+00 3.18594296E-03-1.08841412E-06 1.68761454E-10-9.77966305E-15

2

3.82240388E+03 4.69145660E+00 3.53025733E+00 1.88364239E-03 1.78452098E-06

3

-1.72919680E-09 3.98120351E-13 4.08521632E+03 6.23492345E+00

4

HCO2 3/29/94 THERMC 1H 1O 2 0G 300.000 5000.000 1455.000

01

6.31449894E+00 3.34548164E-03-1.20507137E-06 1.93694895E-10-1.15132236E-14

2

-2.20255876E+04-9.44753566E+00 1.18876543E+00 1.37389141E-02-8.14389853E-06

3

1.67146402E-09 1.99537242E-14-2.01415371E+04 1.85517814E+01

4

H2S2 burc94H 2S 2 0 0G 298.150 5000.000 2000.00

0 1

0.65731735E+01 0.25619139E-02-0.69109315E-06 0.94286242E-10-0.52907210E-14

2

-0.24677791E+03-0.72991840E+01 0.21128554E+01 0.21398828E-01-0.33893856E-04

3

0.28468801E-07-0.95576325E-11 0.67951055E+03 0.14205983E+02 0.20128667E+04

4

OCS 121286C 1O 1S 1 G 0300.00 5000.00 1000.00

1

166

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

167

APPENDIX B

PUMP TESTING DATA

168

Test 1: DUO 10 with different orifice sizes (150, 200, 300, 400 and 500μm)

150μ

Pressure (Torr)

valve closed

open valve

0.108 L/min

0.273 L/min

close valve

P1 3.80E-04 2.70E-01 3.00E-01 3.80E-04 P2 6.30E-08 4.30E-05 6.00E-05 1.10E-07 P3 8.10E-08 2.70E-07 3.40E-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 3.80E-04 1.80E-01 1.70E-01 2.50E-01 4.60E-01 6.60E-01 P2 5.70E-08 2.40E-05 2.30E-05 4.10E-05 3.10E-04 4.40E-03 P3 8.70E-08 2.60E-07 2.20E-07 2.80E-07 1.10E-06 1.30E-05

400μ

Pressure (Torr)

valve closed

open valve

0.185 L/min

0.385 L/min

0.585 L/min

0.766 L/min

0.834 L/min

0.926 L/min close valve

P1 3.80E-04 6.00E-03 1.30E-02 2.30E-02 5.60E-02 2.30E-01 5.30E-01 6.00E-01 3.80E-04

P2 9.10E-08 1.00E-06 1.90E-06 3.10E-06 7.40E-06 3.50E-05 7.40E-04 2.00E-03 1.60E-07

P3 9.40E-08 1.30E-07 1.20E-07 1.20E-07 1.30E-07 2.30E-07 2.30E-06 6.00E-06 9.50E-08

500μ

Pressure (Torr)

open valve

0.185 L/min

0.385 L/min

0.585 L/min

0.766 L/min

0.926 L/min

0.975 L/min

1.094 L/min

P1 5.70E-03 1.20E-02 2.20E-02 4.50E-02 1.10E-01 3.70E-01 5.40E-01 6.00E-01

P2 1.00E-06 1.70E-06 3.10E-06 5.90E-06 1.50E-05 1.10E-04 8.30E-04 3.00E-03

P3 1.50E-07 1.10E-07 1.20E-07 1.20E-07 1.50E-07 5.00E-07 2.60E-06 9.00E-06

169

Test 2: Heating test with DUO 10 (500 μm, 0.15 L/min)

Tin=25C, Tb=180C

Pressure (Torr) valve closed open valve after 5 min. close valve


Tin=119C, Tb=180C

Pressure (Torr) valve closed open valve

P1 3.80E-04 3.60E-01 3.60E-01 3.60E-01 3.70E-01 3.80E-01 3.90E-01

P2 4.30E-07 8.50E-05 8.90E-05 9.20E-05 1.20E-04 1.70E-04 2.70E-04

P3 2.60E-07 6.40E-07 6.00E-07 6.00E-07 6.40E-07 8.40E-07 1.00E-06

Tin=191C, Tb=180C


P1 3.80E-04 3.50E-01 3.60E-01 3.70E-01 3.90E-01 4.20E-01 3.80E-04

P2 3.60E-07 8.20E-05 1.10E-04 1.40E-04 4.30E-03 1.00E-03 5.30E-07

P3 2.70E-07 6.00E-07 6.40E-07 7.50E-07 1.70E-06 3.30E-07 2.80E-07

Tin=230.2C, Tb=180C

Pressure (Torr) valve closed open valve after 3:20 min. 3:22 min. close valve

P1 3.80E-04 3.70E-01 3.80E-01 4.00E-01 4.00E-01 3.80E-04 P2 3.50E-07 1.70E-04 2.10E-04 5.80E-04 1.10E-03 4.70E-07

P3 2.60E-07 8.90E-07 1.00E-06 2.20E-06 4.00E-06 2.80E-07

170

Tin=265.5C, Tb= 180C

Pressure (Torr) valve closed open valve after 1 min. 2 min. close valve

P1 3.80E-04 3.90E-04 3.90E-01 4.00E-01 4.10E-01 3.80E-04 P2 3.50E-07 2.40E-04 3.10E-04 4.80E-04 1.10E-03 4.80E-07 P3 2.60E-07 1.10E-06 1.30E-06 1.90E-06 3.50E-06 2.80E-07

Tin=303C, Tb=180C


P1 3.80E-04 4.30E-01 4.40E-01 4.60E-01 3.80E-04 P2 3.90E-07 1.40E-03 3.10E-03 6.80E-03 6.20E-07

P3 2.70E-07 5.60E-06 1.10E-06 2.30E-06 3.40E-07

171

Test 3: DUO 20 with 500 μm, 0.15 L/min

Tin=25C, Tb=180C

Pressure (Torr)

valve closed

open valve

after 2 min.

close valve


Ton=105C, Tb=180C

Pressure (Torr)

valve closed

open valve

after 3 min.

close valve

P1 3.80E-04 3.50E-01 3.50E-01 3.50E-01 3.80E-04 P2 7.00E-07 7.80E-05 8.20E-05 8.40E-05 8.60E-07

P3 4.00E-07 8.70E-07 7.30E-07 7.20E-07 4.00E-07

Tin=156C, Tb=180C

Pressure (Torr)

valve closed

open valve

after 1 min.

3 min. 5 min. 6 min. close valve

P1 3.80E-04 3.60E-01 3.50E-01 3.50E-01 3.60E-01 3.60E-01 3.80E-04 P2 5.00E-07 7.90E-05 8.00E-05 8.30E-05 8.70E-05 8.80E-05 6.50E-07

P3 3.30E-07 7.50E-07 6.80E-07 6.60E-07 6.60E-07 6.60E-07 3.40E-07

Tin=191C, Tb=180C

Pressure (Torr)

valve closed

open valve

after 1 min. 3 min. 4 min. 5 min. 7 min. close valve

P1 3.80E-04 3.60E-01 3.50E-01 3.50E-01 3.50E-01 3.00E-01 3.60E-01 3.60E-01 3.80E-04 P2 4.90E-07 9.10E-05 8.10E-05 8.10E-05 8.50E-05 8.70E-05 8.90E-05 9.00E-05 6.70E-07 P3 3.20E-07 7.70E-07 7.10E-07 6.70E-07 6.60E-07 6.60E-07 6.60E-07 6.70E-07 3.40E-07

172

Tin=230C, Tb=180C

Pressure (Torr)

valve closed

open valve

after 2min. 4 min. 5 min. 6 min. 7 min.

close valve

P1 3.80E-04 3.60E-01 3.50E-01 3.60E-01 3.60E-01 3.60E-01 3.70E-01 4.00E-01 4.20E-01 3.80E-04

P2 4.70E-07 8.40E-05 8.20E-05 8.40E-05 8.80E-05 9.50E-05 1.30E-04 4.50E-04 1.00E-03 7.10E-07

P3 3.30E-07 7.00E-07 6.70E-07 6.60E-07 6.60E-07 6.90E-07 7.90E-07 1.90E-06 3.60E-06 3.60E-07

Tin=253C, Tb=180C

Pressure (Torr)

valve closed

open valve

after 1 min.

2 min. 3 min. 3.5 min. 5 min. close valve

P1 3.80E-04 3.60E-01 3.60E-01 3.70E-01 3.80E-01 4.10E-01 4.40E-01 3.8-4 P2 4.50E-07 1.10E-04 1.20E-04 1.60E-04 2.60E-04 1.00E-03 5.00E-03 8.00E-07 P3 3.30E-07 8.60E-07 8.20E-07 9.30E-07 1.30E-06 3.80E-06 4.20E-07

173

Test 4: PENTA35 with 500 μm, 0.15 L/min

Pressure (Torr)

valve closed

open valve

after 1 min.

2 min. 5 min. 6 min. 12 min. 15 min. close valve

P1 3.80E-04 3.00E-01 3.20E-01 3.40E-01 3.50E-01 3.50E-01 3.60E-01 3.60E-01 3.60E-01 3.80E-04

P2 1.20E-07 5.80E-05 6.70E-05 8.20E-05 9.30E-05 9.70E-05 9.80E-05 1.00E-05 1.00E-05 2.20E-07

P3 1.10E-07 4.10E-07 4.20E-07 4.50E-07 4.70E-07 4.70E-07 4.70E-07 4.80E-07 4.80E-07 1.00E-07

heat cord 0, blanket 180C

Pressure (Torr)

valve closed

open valve

after 2 min.

3 min. 5 min. 7.5 min. 8.5 min. 9.5 min. close valve


heat cord 0, blanket 180C

Pressure (Torr)

valve closed

open valve

after 2 min.

3 min. 4 min. 5 min. close valve

P1 3.80E-04 2.20E-01 3.30E-01 3.50E-01 3.70E-01 3.80E-01 3.80E-04 P2 2.10E-07 2.90E-03 6.90E-05 9.00E-05 1.00E-04 1.50E-04 4.60E-07 P3 1.90E-06 3.30E-07 4.40E-07 5.10E-07 5.40E-07 7.20E-07 1.80E-07

Tin=145C, Tb=180C Pressure

(Torr) valve

closed open valve

after 2 min.

3 min. 4 min. 4:20 min. close valve

P1 3.80E-04 3.50E-01 3.60E-01 3.70E-01 3.90E-01 4.10E-01 3.80E-04 P2 2.30E-07 8.10E-05 1.10E-04 1.70E-04 4.90E-04 1.00E-03 5.90E-07

P3 1.90E-07 6.50E-07 5.90E-07 8.20E-07 1.90E-06 3.40E-04 2.00E-07

174

Test 5: DUO 10 +PENTA35 with 150 μm, 0.15 L/min

Tin=25C, Tb=180C

Pressure (Torr)

valve closed

open valve

after 1min.

2 min. 3 min. 4 min. 5 min. 10 min. 15 min. close valve

P1 1.00E-03 3.20E-01 4.00E-01 4.60E-01 4.90E-01 4.90E-01 4.90E-01 4.90E-01 4.90E-01 1.10E-03 P2 3.00E-07 3.40E-05 4.30E-05 4.90E-05 5.20E-05 5.30E-05 5.40E-05 5.40E-05 5.30E-05 4.00E-07 P3 1.90E-07 3.50E-07 3.90E-07 4.20E-07 4.30E-07 4.40E-07 4.40E-07 4.40E-07 4.40E-07 1.90E-07

Tin=147.2C, Tb=180C

Pressure (Torr)

valve closed

open valve

after 1min.



heat cord 40% => 193.1, blanket 180C

Pressure (Torr)

valve closed

open valve

after 1min.



Tin=235.3C, Tb=180C

Pressure (Torr)

valve closed

open valve

after 1min.



175

Tin=282.5C, Tb=180C

Pressure (Torr)

valve closed

open valve

after 1min.



Tin=322-327C, Tb=180C

Pressure (Torr)

valve closed

open valve

after 1min.

5 min. 10 min. 15 min. 20 min. 25 min. 30 min. 35 min. close valve

P1 1.00E-03 5.00E-01 4.70E-01 4.70E-01 4.70E-01 4.80E-01 4.80E-01 4.80E-01 4.80E-01 4.80E-01 1.00E-03

P2 2.90E-07 5.20E-05 4.90E-05 4.90E-05 5.00E-05 5.10E-05 5.10E-05 5.10E-05 5.00E-05 5.00E-05 4.50E-07

P3 1.70E-07 4.20E-07 4.10E-07 4.10E-07 4.10E-07 4.20E-07 4.10E-07 4.20E-07 4.10E-07 4.20E-07 1.80E-07

Tin=365-373C, Tb=180C

Pressure (Torr)

valve closed

open valve

after 1min.

2 min. 3 min. 4min. 5min. 10 min. 15 min. close valve


Tin=411-415C, Tb=180C

Pressure (Torr)

valve closed

open valve

after 1min.



177

APPENDIX C

LASER ALIGNMENT GUIDELINES

178

Remove the rear flange of the main chamber.

Remove the cover plate loosening the 3 screws shown below.

179

[152]

180

[152]

181

APPENDIX D

FLANGE DRAWINGS

182

Flange with Feedthroughs

183

Gas Feedthrough

184

Power Feedthrough

185

Thermocouple Feedthrough

187

APPENDIX E

SUPERSONIC SYSTEM INSTALLATION GUIDELINES

Removing the chopper and installing the skimmer flange assembly

188

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.

189

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.

190

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.

191

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