UNIVERSITY OF CALIFORNIA

Los Angeles

Combustion Models and the prediction of Polycyclic Aromatic

Hydrocarbons (P AH) in laminar flames of simple hydrocarbons:

Methane, Methyl Chloride, and 1,1 Dichloroethane

A dissertation submitted in partial satisfaction of the

requirements for the degree Doctor of Philosophy

,-

in Chemical Engineering

by

Ivan A. Gargurevich

1997

© Copyright by Ivan A. Gargurevich 1997

The dissertation of Ivan A. Gargurevich is approved

Vasilios Manousiouthakis

J-di~~

Harold G. Monbouquett

Daniel Neuhauser

Selim M. Senkan, Committee Chair

1997

University of California, Los Angeles

11

To my sister Lucia, Captain of us children,

The flower in our mother's garden, For her kindness is our comfort, And her love gives us a new day ...

And to my father and mother.

For they can discern, The true rewards,

Out of the eye of the storm.

1ll

TABLE OF CONTENTS

List of Tables List of Figures Acknowledgment Vita

Abstract Chapters

1. Introduction

1.1 The Driving Force for Studying PAH in Combustion 1.2 Detailed Chemical Kinetic Models (DCKM)

1.3 The General Structure of Premixed Laminar Flames 1.4 P AH Chemistry and Kinetics in Combustion

2. Chemistry and Kinetics of Combustion 2.1 Methane Combustion

2.2 Combustion of Simple Chlorinated Hydrocarbons (CHe) 2.2.1 Flame Inhibition and General Chemistry

2.2.2 Methyl Chloride

2.2.3 1,1 Dichloroethane (1,1 DCE) 2.3 P AH Chemistry and Kinetics

IX

Xlll

XV1ll

XIX

xx:

1 2 15 21 27 34 34 40 41 44 48 51

tV

TABLE OF CONTENTS (cont'd.) 2.3.1 Formation of the First Aromatic Ring

2,3.2 Beyond the First Ring: PAH Formation and Growth 2,3,3 The Role of 5·Carbon Molecules in P AH Formation 2.3.4 The Role of Chlorine in PAR Formation and Growth

2.3,5 The Role ofCl/H atoms in Soot Formation & Growth

3. The Estimation of Thermochemicalffransport Properties and Kinetic Coefficients

3.1 Introduction

3.2 Estimation of Thermochemical Properties 3.2.1 Conventional Methods

3.2.2 Computational Quantum Chemistry

3.2.2.1 Quantum Mechanical Background 3.2.2.2 Self-Consisten Field Theory 3.2.2.3 Semi-empirical Methods

3.2.2.4 Group Equivalent Corrections

3.3 Estimation of Transport Properties 3.4 Estimation of Kinetic Coefficients 3.4.1 Estimation of Rough Magnitude 3.4.2 Transition State Theory

3.4.2.1 TST of Bimolecular Reactions

5S S6 59 63 65 69

69 74 74 87 89 95 102 110 112 117 120 126 127

v

TABLE OF CONTENTS (cont'd.)

3.4.2.2 TST ofUnimolecualr Reactions 128

3.4.3 Unimolecular Reactions 129

3.4.3.1 Lindemann's Approach 129

3.4.3.2 QRRK Treatment ofUnimolecular Reactions 136

3.4.4 QRRK Treatment of Biomolecular Addition Reactions 139

4. Mathematical Modelling of Premixed Laminar Flames 144

4.1 The Numerical Solution Method 148

4.2 The Mathematical Modelling of Thermo dynamicffransp ort Properties 153

4.3 The Structure of The Sandia Flame Code 155

5. Computational Techniques 158

5.1 Solution Tchniques for FLAMECODE 158

5.2 MOPAC Techniques 162

6. Experimental Apparatus 167

6.1 Experimantal Apparatus: An Overview 168

6.2 Laminar Flame Burner 172

6.3 Sampling Probe 174

6.4 GClMS System' 177

6.5 Ancillary Equipment 181

6.6 Data Analysis 184

6.7 Errors Associated with the Experiments 195

VI

TABLE OF CONTENTS (Cont'd.)

7. DCKM Validation & Optimization: Major Features 197

7.1 Methane Oxidation DCKM: Validation and Optimization 197

7.1.1 The Chemistry of Methane Oxidation 201

7.1.2 DCKM Validation & Optimization of Rate Parameters 204

7.1.3 Methane DCKM Results for Major and

Intermediate Species 213

7.1.4 Reaction Paths in very Fuel-Rich Flames of

Methane 219

7.2 CHC Oxidation DCKM: Validation and Optimization 237

7.2.1 The Chemistry of CHC oxidation: Assembly 237

7.2.2 CHC DCKM: Validation and Optimization 240

7.2.3 CHC DCKM Results: Major and Intermediate Species 244

7.2.4 Reaction path Analysis for CHe Flames 256

8. PAH Chemistry & Kinetics Development 294

8.1 Introduction 294

8.2.1 PAH Formation-via Aryl Radicals 296

8.2.2 F ormation of N aphthalenel Azulene via Cyclopentadiene 3 11

8.2.3 H Radical Catalysis ofPAH Isomerization Reactions 323

8.2.4 Formation of Benzyl from Cs Hydrocarbons 328

8.2.S Formation of Naphthalene via Propargyl Radicals 330

vii

__ --==--"'-"--'--"-- .. ==~===---o==--CC------'-_'---'- __ """"' =_=_=_ = ,--------c===-===--,------____==___

TABLE OF CONTENTS (CONT'D.)

8.2.6 The Formation ofCyclopentadiene 337

8.2.7 Aromatic Growths via C .. 's 341

8.2.8 QRRK Analysis of Benzene Formation from Propargyl Radicals 344

8.2.9 Formation of Ph en alene 351

8.2.10 Formation of Azulene via Acetylene Addition 351

8.2.11 Formation ofPyrene via Methyl Radical Addition 352

8.3 Validation ofPAH Chemistry and Kinetics 352

8.3.1 PAR Formation in Methane Flames 352

8.3.2 PAIl Formation in Methyl Chloride Flames 370

9. Summary & Recommendations 382

Appendices 390

A. Thermochemical Properties of Normal Hydrocarbon Species 391

B. Thermochemical Properties ofCHC species 395

C. Themochemical Properties ofP AHand Chlorinated-P AlI 400

D. DCKM: for Methane 407

E. DCKM for 'Simple cnc 448

F. Transport Properties 496

G. Chemical Species Nomenclature and Structure 514

H. QRRK Analysis Input/Output-Results 537

References 600

VIII

LIST OF TABLES

Table Page
1.1 The National Air Quality Standards (NAAQS) 6
1.2 Hazardous Air Pollutants under Title I Section 112 1
1.3 Estimated P AH emissions in the USA 9
1.4 Hazardous Waste Management Methods 12
1.5 Biological Activity of some P AH 14
2.1 Bond Dissociation Energies for CHC 43
2.2 P AH identified in Flames 53
2.3 Forward RateCoefficients for Reactions (2.81), (2.88) 6S
3.1 Enthalpy of Formation of Benzene and Highly Fused Aromatics 80
3.2 The Development of Semi-Empirical Quantum Chemistry Methods 104
3.3 Heats OfFormatio (MOPAC 93 Manual) 111
3.4 Theories for Estimating Rate Coefficients 112
3.5 High Pressure Rate Coefficients for Anagous Reactions 122
3.6 SAR for H-atorn Abstraction by Chlorine Attack on Organic
Molecules 125
6.1 Chlorinated Species Identification and Quantification 189
6.2 Hydrocarbon Species Identification and Quantification 190
6.3 P AlI Identification and Quantification 191 IX

LIST OF TABLES (Cont'd.)
Table Page
7.1 Measured Species in a Fuel-rich Methane Flame 202
7.2 Experimental vs. Computed Concentration Profiles, Methane Flame 207
7.3 Sensitivity Analysis for Methane Flame 211
7.4 Rate Coefficient Optimization for Methane DCKM: 212
7.S Major Reaction Paths for Methane Flame 221
7.6 Species Identified in CHC Oxidation 238
7.7 CHC Species composing the CHC DCK1vf 239
7.8 Rate Coefficient Optimization for CHC DCKM 242
7.9 Major Reaction Paths for CH3CVCHa Oxidation 257
7.10 Radical Concentration in Methyl Choride Flame (Computed) 273
7.11 Radical Concentrations in Methane Flame (Computed) 275
7.12 Major Reaction Paths for 1,1 DCE Combustion 279
8.1 PAH Heats of Formation (MOPAC 93 Manual) 295
8.2 Reaction Paths for Formation of P AH via Aryl Radicals 297
8.3 Rate Coefficients for _Aryl Decomposition 300
8.4 Rate Coefficients for Aryl Stabilization Reactions 301
8.S Aryl Radical Decomposition vs. Stabilization 302
8.6 High Pressure Limit Parameters for Aryl Radical Reactions
QRRK Analysis 303 x-

LIST OF TABLES (cont'd.)
Table Page
8.7 Formation ofNaphthaJene/Azulene from Cyclopentadiene- Paths 315
8.8 Naphthalene form Cyctopentadiene-High Press. Limit
QRRK Parameters 317
8.9 Naphthalene from Cyclopentadiene QRRK Analysis Results
Reaction Path No. -1 318
8.10 Naphthalene from Cyclopentadiene QRRK Analysis Results
Reaction Path No.2 319
8.11 High Press. Limit Parameters for H-Radical Catalyzed Isomerization
of Anthracene to Phenanthrene 327
8.12 QRRK. Analysis for the Formation of Benzyl from C3 333
8.13 High Press. QRRK Input Parameters for Naphthalene Formation
via Propargyl 335
8.14 QRRK Analysis Results for Naphthalene via Propargyl 336
8.15 QRRK Input Parameters and Results for Formation of Cycl a pentadiene
Acetylene/Propargyl 339
8.16 High Pressure Limit QRRK Input Parameters for the Formation of Methyl
Cyclopentadiene Radical from Benzene 342
8.17 QRRK Analysis Results for Methyl CycIopentadiene from Benzene 343 Xl

LIST OF TABLES (Cont'd.)
Table Page
8.18 Nomenclature for QRRK Analysis of Benzene Formation from
Prop argyl 348
8.19 QRRK Input Parameters for Benzene Formation from Propargyl 349
8.20 QRRK Analysis Results for Formation of Benzene from
Prop argyl Radicals 350
8.21 QRRK Analysis and Results for Phenalene Formation via
Acetylene Addition 354
8.22 Reaction Path for Benzene Formation in Methane Flame-Fuel Rich 365
8.23 PAR Activation by Radical Attack- Rate of Reactions 379
8.24 Reaction Path for Benzene Formation in Methyl/Chloride Flame 380 XlI

LIST OF FIGURES
Figure Page
1.1 Emissions of Selected Pollutants by Source category 5
1.2 Hierarchical Structure of Combustion 19
1.3 Laminar Flame Structure 24, 145
1.4 Rough Picture for Soot Formation (premixed Flames) 32
2.1 Reaction Paths for Methane Oxidation 37
2.2 Reaction Paths for CH3Cl oxidation in Fuel-Rich Flames 46
2.3 HACA Mechanism 54
2.4 Cyclopentadiene from Benzene 57
3.1 P AH Group Additivity 72
3.2 Experimental vs. AMI Vibrational Frequencies ofP AH 75
3.3 Group Additivity ofP AH with 5-carbon Rings 77
3.4 Statistical Mechanics of Molecular Properties 85
3.5 Energy Diagram for an Unimolecular Reaction 130
3.6 Pressure Dependence ofkuni 131
3.7 Energy Dependence ofk..ru 137
3.8 Bimolecular Chemical Activation 142
4.1 Starting Estimate for Flame Code 152
4.2 Flow Diagram for SANDIA Flame Code 157
6~1 Experimental Apparatus for Sampling Laminar Flames 169 xiii

LIST OF FIGURES (Cont'd.)
Figure Page
6.2 Laminar Flame Burner 165
6.3 Quartz Microporobe Specifications 167
6.4 GC/MS Valve Arrangement 171
6.5 Gas Delivery System 174
7.1 Major Species Profiles-Methane Flame if> = 2.5 215
7.2 Concentration Profiles for Hydrogen, Water, and Carbon Balance-
Methane Flame $ = 2.5 216
7.3 Concentration Profiles for C2 Hydrocarbons-Methane Flame $ = 2.5 217
7.4 Concentration Profiles for Trace C), C4• Cs, and C6 Hydrocarbons
Methane Flame $ = 2.5 218
7.5 Major Reaction Paths for Methane Oxidation-Fuel Rich Flames 229
7.6 Reaction Paths for Formation of Trace Species in Methane
Fuel-Rich Flames 230
7.7 Major Species Profiles, CH3CIlC~ Flame if> = 2.37 245
7.8 Major Species Profiles for CH3ClICI4Flame 4> = 2.37 246
7.9 C-JCJCs Trace Species CH3ClICH4 Flame 4> = 2.37 247
7.10 Major Species Profiles for 1.1 DCElC&Flame ~ = 2.36 250
7.11 Major Species Profiles for 1,1 DCE/CRa Flames q, = 2.36 251 xiv

LIST OF FIGURES (Cont'd.)
Figure Page
7.12 Major Intermediate Chlorinated Species for 1, 1 DCElC~
Flame q, = 2.36 252
7.13 Major Intermediate Species Profiles for 1, 1 DCE/Cfu Flame tV = 2.36 253
7.14 Trace Species for 1,1 DeE/Cfu Flame $ = 2.36 254
7.15 Major Reaction Paths for Combustion of CH3ClICfu Fuel-Rich Flames 267
7.16 Formation of Trace Species in CH3CVCIL Fuel-Rich Flames 268
7.17 Major Reaction Paths for the Combustion of Fuel-Rich 1, I DCE Flames 289
7.18 Reaction Paths for Trace Species in Fuel-rich 1,1 DCE Flames 290
8.1 Energy Diagramfor Formation ofBiphenylene via Aryl Radicals 299
8.2 Plot of Rate Coefficients for Biphenyl Formation-Reaction (S.l) 305
8.3 Energy Giagram for Formation ofFluoranthene via Aryl radicals 307
8.4 Energy Diagram for Formation ofBiphenylene via Aryl radicals 308
8.5 Energy Diagram for Formation ofPerylene via Aryl radicals 309
8.6 Energy Diagram for Formation of Flu 0 ranthene via
Hydrogen Elimination 310
S.7A Energy Diagram for Formation of Naphthalene from Cyclopentadiene-
Reaction Path No.1 313
8.7B Energy Diagram for Formation of Naphthalene from Cyclopentadiene-
Reaction Path No.2 314 xv

LIST OF FIGURES (Cont'd.)
Figure Page
8.8 Geometry of Reactant Species (R5~5H·) 320
8.9 Optimized Geometry of Transition State Leading to Naphthalene 321
8.10 Geometry of Product (A2H~) 322
8.11 Energy Diagram for H'Radical Catalysis of Naphthalene Isomerization
to Azulene 325
8.12 Energy Diagram for Formation of Phenanthrene from Anthracene 326
8.13 Energy Diagram for Formation of Benzyl from Cs's 329
8.14 Naphthalene Formation via Propargyl 334
8.15 Energy Diagr~,m for Formation ofCyclopentadine from
Acetyl en/Prop argyl 338
8.16 Energy Diagram for Formation of Methyl Cyclopentadienyl from
Benzene 340
8.17 Energy Diagram for P AH Growth via n-C4HS Radical 345
8.18 Energy Diagram for P AH Growth via n·CJI3 Radical 346
8.19 Energy Diagram for Formation of Benzene from Proipargyl radicals 347
8.20 Energy Diagram for Formation of Ph en alene via Acetylene Addition 353
8.21 One-Ring PAR in Methane Flames q, = 2.50 357
8.22 Two-Ring P AH in Methane Flame 4> = 2.50 358
8.23 Three-Ring PAH in Methane Flame 4> = 2.50 359 XVI

LIST OF FIGURES (Cont'd.)
Figure Page
8.24 Four-Ring PAH in Methane Flames q, = 2.50 360
8.25 Trace Components Methane Flame q, = 2.50 361
8.26 The Effect ofPAH Growth via Prop argyl Addition,
Methane Flame q, >= 2.50 362
8.27 The Effect of Benzene Oxidation on Cyclopentadiene Formation
Methane Flame q, >= 2.50 363
8.28 One-Ring P AH in Methyl Chloride Flame q, = 2.37 372
8.29 Two-Ring PAH in Methyl Chloride Flames q, >= 2.37 373
8.30 Three and Four Ring PAR, Methyl Chloride Flame <p = 2.37 374
8.31 One and Two-Ring Chlorinated PAH, Methyl Chloride Flame <P = 2.37 375
8.32 Trace Species in Methyl Chloride Flame q, = 2.37 376
9.1 Formation of Biphenyl via Propargyl Radicals Addition 388
9.2 Formation of Azulene via Pentadienyl addition 389 xvii

ACKNOWLEDGMENTS

I would like to express my gratitude to my advisor Dr. S. Senkan for his continuous

support and guidance during the performance of this work. I also would like to thank Dr.

H. Wang at Pennsylvania State University for providing the chemistry, thermodynamic and

kinetic data for P AH growth via the Hydrogen Abstraction-Acetylene Addition

mechanism. I also want to thank Mr. M Castaldi (UCLA) for providing the methane

oxidation experimental data to validate a DCKM, and Mr. J Huang (UCLA) for providing

the methyl chloride oxidation experimental data.

XVIII

VITA

May 25,1957

1976

1978

1980

1980-1991

Born, Madrid, Spain

A.A., EI Camino College Torrance, California

B.S., Chemistry University of California . San Diego, California

M.S., Chemical Enginnering UCLA

Los Angeles, California

Senior Process Engineer

Parsons Corp., California Ultrasysterns Engineering, California

PUBLICATIONS

Gargurevich, I. A, Castaldi, M., and Senkan, S. M., Chemical Structures of Fuel-Rich, Premixed, Laminar Flames of I,1-C2H4Cb/CRJOz/Ar, Combust. Sci. and Tech., 106,69- 82,1995.

Senakan, S., Gargurevich, I. A, and Huang, 1., " A review ofCHC Combustion", a manuscript under preparation, 1996.

Gargurevich, I. A, and Senkan,S. M., "The Formation ofPAH via Aryl Radicals", Manuscript under preparation, 1996.

Gargurevich, I A., and Senkan, S. M., "A Study of the kinetics and Thermodynamics of the H-Radical Activated Isomerization of Anthracene and Phenanthrene", Manuscript under preparation, 1996.

Gargurevich, 1. A, and Senkan, S. M., "The Formation of Naphthalene from Cyclopentadiene", Manuscript under Preparation, 1996.

Gargurevich, I. A., and Senkan, S. M., "The Formation of Naphthalene via Propargyl Radical", Manuscript under preparation, 1996.

xix

ABSTRACT OF THE DISSERTATION

Combustion Models and the prediction of Polycyclic Aromatic Hydrocarbons (P AH) in laminar flames of simple hydrocarbons:

Methane, Methyl Chloride and, 1, 1 Dichloroethane

by

I van A. Gargurevich

Doctor of Philo sophy in Chemical Enginnering University of California, Los Angeles, 1997 Professor Selim M. Senkan, Chair

Detailed chemical kinetic models (DCKM) have been assembled for the combustion of methane, methyl chloride and I, I dichloroethane in fuel-rich premixed laminar flames. The methane model consists of over 100 species and 600 elementary chemical reactions, this model was incorporated into the chlorinated hydrocarbon (CRe) model resulting in over 150 species and more than 1500 elementary reactions. The models incorporate known and new chemistry for the formation ofP AH in flames, a major objective and are important building blocks for DCKM of more complex fuels.

xx

The DCKlvI were "optimized" for major, intermediate, trace species and PAH using experimental data generated at UCLA. The optimization procedure involved reaction path and sensitivity analysis for the species of interest. The thermochemistry of PAIl and kinetic coefficients for their reaction were estimated using computational quantum chemistry.

The most important findings of the study can be summarized as follows:

1. The combustion models capture well the major features of combustion of methane, methyl chloride, and 1,1 DCE in laminar flames under fuel-rich conditions. Due to the large size of the CHC model more testing is required for its optimization.

2. For the flames under consideration formation of benzene and naphthalene can not be explained by acetylene addition chemistry alone. To fully explain benzene formation

and growth to naphtahiene reactions involving prop argyl radical must be included in the model.

3. Aryl radicals are involved in the formation ofPAH, and they constitute a new path for P AH formation. The chemistry was developed in the study.

4. Because of low concentration, aromatic growth involving a 4-carbon molecule such as C,JI3 for example is not significant. Chemical paths are proposed.

5. For the formation of cyclopentadiene, a 5 -carbon cyclic molecule, reactions involving the phenoxy radical produced by oxidation of phenyl result in the most significant contribution to its formation. of ormation of cyclopentadiene via reaction of propargyl radical with acetylene and from benzyl radical are minor paths.

xxi

6. Hydrogen atom additions to the aromatic ring, catalize the isomerization of naphthalene to azulene, and isomerization of anthracene to phenanthrene. The chemistry for these reactions was developed in the study.

xxii

CHAPTER!

INTRODUCTION

As stated. on the abstract, this study is concerned with the development and validation of large Detailed Chemical Kinetic Models (DCKh1) for the combustion of simple fuels such as methane, methy I chloride, and 1,1 dichloroethane (1, 1 DCE) in fuelrich premixed laminar flames. Special a ttenti on was given to the fo rmation of polycyclic aromatic hydrocarbons (PAH). It win be shown in the discussion that follows that PAR are known carcinogens, therefore t hey constitute a health ri sk, and are considered precursors to soot _ I~. many instances new chemistry had to be develo peel to explain P AlI formation, and com putational quantum chemistry was used to estimate thermochemical properties of some P AH and kinetic coefficient s for reactions involving P AH_

The motivations for the study will be made dear at the outset. and this wiU lead to a. discussion of important issues regarding DCKM, the general structure of premixed laminar flames, and P AH chemistry and kineti cs in flames of pure hydrocarbons and chlorinated hydrocarbons (CHC). Dealing with these isues here will provide the reader with a better understanding of later chapters.

I

1~1 The Driving Force For Studying PAR in Flames

Combusti on technology is used to generate electricity fo r our chi es, to power our industries and automobiles, to heat our homes, and even for the final disposal of toxic wastes in incinerators. Unfortunately, hydrocarbon combustion generates pollutants which can be catego rized as follows ( Longwell, 1991):

• Combustible:

Unburned fuel

Hydrocarbons from pyrolysis PAR and other mutagens Soot, HCN, CO

• Combustion Products:

SO~S03IHCI NOINOmlO

Inorganic particulates

cO:!

As we shan see, emissions of these poIIutants are impacted by laws and regulations, and our discussion will focus on the role ofPAH and eHe in pol1ution of the environment. Combusti on of fo sst] fuels is likely to remain the most import ant source 0 f energy in the near future (Longwell, 1991), Furthermore, as the supplies of easily obtained crude oil dwindle. the use of heavy oil residu es from crude oil processing, coal, coal-derived fuels,

2

and shale oil will rise in proportion. Heavy oil resi dues are richer in aromatic content and

their usage in combustion devices win result in higher ernissi 0 ns of P AH~ heavy oil s also

have higher carbon to hydrogen ratios, their combustic n will result in greater soot

formation. Coal combusti on is related to emissic ns of sulfu r di oxi de and greater usage will

require technologies to deal with the acid rain problem; coal abo has a greater content of

P AH (Gamrnage~ 1983) than crude oil and its increased use will impact emissions of

PAIl. Incinerat ion is another combusti on technology being used. increasingly, for the total

destruction of toxic wastes containing mixtures of hydrocarbons with a release of trace

pollutants into the enviro nrnent ( S enkan, 1988)_

There are several environmental Jaws or regulations that greatly impact the

emissions, emi ssion controls, and final di sp osal of many toxic chemicaJ s or pollutants into

,.

the environment, be it ambient air or a stream of water, for example: The Clean Air Act as

ammended in 1990. The Clean Water Act, The Resource Conservation and Recovery Act

(ReRA) dealing with hazardous wastes, and The Occupational Safety and Health Act

(OSHA) concerning pollutants in the working environment and worker exposure to those

pollutants. These are also some of the most important regulations that impact combustion

technologies and their emissions ofPAH, the focus of this study, directly or indirectly as

the discussion will show.

The Clean Air Act consists of several titles, Tide I deals with air poIIution through

(1) the National Ambient Air Quality Standards (NAAQS) for criteria pollutants CO, lead,

nitric oxides, ozone, su lfur dioxide, and particular matter (also see Table I_I), (2) the

3

National Emission Standards for Hazardous Pollutants (NESHP) or section 112 including an arnmendment of 189 new pollutants (see Table 1.2) includes P AH)~ and (3) the New Souce Performance Standards (NSPS) or section III for industries having significant potential to emit the criteria po llutants listed ab ove and vola tire organic compounds (VOC). Title II deals with the emission standards for moving sources such as the automobile in order to reduce emissions of VOC~ nitric oxides, and CO. Title IV deals with the acid fain problem and impacts sulfur dioxide and nitric oxide emissio ns from power plants. Title VI deals W] th the d eplition of ozone in the up per atmo sphere, and phase-out of chloroflu orocarbons.

How the Clean Air Act impacts co mbustion and P AlI emissio ns, the main subject of this sudy, can be further elucidated by discussing the contents ofTab1es 1,1 and 1,2. The urban a tmo sphere' is a giant chemical reactor in which po llu tant gases such as hydrocarbons and oxides of nitro gen and sulfu r react under the influenc e of sunlight to create a variety of products) including ozone ( a lung irritant) and submlcrometer particles (Seinfield, 1989). Table I_I depicts the NAAQS as of November 15~ 1990_ Combustion processes account for the majority of these NAA.QS pollutants as inspection of Figure 1.1 reveals. With power plants resulting in most of the emissions of sulfur dioxide ( Cortese) 1990). PAH are impacted by the NAAQS because particular matter (PM) consists mostly of organic carbon (such as P AH) and elemental carbon (soot) emmitted rno stly by automobiles, power plants and other minor sources (Seinfield, 1989).

4 -

LEAD 'l'aANSf'ORT A.TION 3 ~

TRANSPORTATION 43~

OTHER.~

FUn. COMeUST. ~3Mo

VOLATILE ORGANIC CHEMICALS ta.ANSPOll'f A'!ION ~

SOLVENTS .& suM:F,l,CE COATINGS 2 .. ,.,

co

TRANS PO R fATI ON ...

OTI-IER22~

FUEL COM BUST. t2,.,

Figure 1.1 Emissions of Selected Pollutants by Source Category (Cortese, 1990)

5

NationaJ Ambient Air Quality Standards (as of November 15, 1990)

Pollutant

Primae' Standards (protective of'Health)'

Ozone

0.120 ppm (235 j.Lglm3) (I hr. average)

Carbon Monoxide

9 ppm (10 J-lg/ m3) (8 hr. average)

35 ppm (40 ~glm3) (1 hr. average)

Particulate Matter (PM-l 0)

150 ~glm}

(24 hr. average) 50 !-lg/m3

(annual arithmetic mean)

Sulfur Dioxide

0.140 ppm (365 ~gJm3) (24 hr. average)

0.03 ppm (80 ug/m') (annual arithmetic mean)

Nitrogen Dioxide

0.053 ppm (100 ug/m') (annual arithmetic mean)

Lead

1.5 IlglmJ

(ari thmeti c mean averaged quarterly)

1. The. Clean Air Act also requires that EPA establish secondary standards, which prol:ec:t against adverse effects on the environment Secondary Standards have been established for most of the listed poUUlanU, and inmost cases the levels are lower than pri nuu:y standards.

Table 1.1 The National Air Quality Standards (NAAQS). (Quarles, 1990)

6

S ejected Lj sLof H azarduus Aj r ponu t ant s

Title I-Section 112 .

Chemical Name

Benzene Benzyl chloride Biphenyl ChIoro benzene Ethyl Benzene Chloroethane

1 ~ 1 Dichloroethane Hydrochloric acid Chloromethane Dichloromethane Naphthalene Styrene

Toluene

V my l chloride

1 ~ 1 Dichloroethylene Xylenes

Polycyclic Organic Matter ( organic compounds with more than one benzene ring, and boiling point> 100 °C)

Table 1.2 Hazardous Air Pollutants under Tide I-Section 112 ( Quarles, 1990)

7

P AH are considered precursors to soot formation and are often emitted adsorbed on the surface of soot particles from combustion sources (Haynes and Wagner, 1981). By 1976 more than 30 PAH compouns and several hundred derivatives orPAH were reponed to have carcinogenic effects (see Table 1.5), making P AH the largest single class of chemical carcinogens known today ( Ramd ahIt 1985)_ The fate of atmospheric P AH is still not well known and determining the detailed reaction pathways of these compounds constitute one of the greatest needs in air pollution chemistry ( Seinfleld, 1989)_

Table 1.2 shows selected pollutants from a list of 189 reguJated under section 112 of the Clean Air Act or NESHP, aromatic s such as naphthalene and P AH (in general) are included in this list, as wen as chlorinated hydrocarbons (CHC) such as vynil chloride, chlorobenzene and 1, i dichloroethane (I, 1 DeE). Section 112 also spells out sources of toxic pollutants to be regulated) some of these sources involve combustion technology such as coal/oil combustion, municipal solid waste incineration, waste gas flare, process heaters, on-site incineration. This study win show that even combustion of simple hydrocarbons such as methane ( Castaldi et al., I995) and methy1 chloride (Huang and Senkan, 1996) can lead to the formation of aU of the pollutants listed in Table 1.2 in concentrations dependent on the combustion conditio ns. Table 1.3 further illustrates the role that combustion plays in the emission ofP AH into the atmosphere (Ramdahl, 1985) with automo bile emissions accounting for the majority of P AH emission in the vapor phase or adsorbed on so at. As Rarndahl (1985) points aut, most of the emissions of P Ali into the atmosphere are the cause of so me type of device using combustion technology.

8

AS;imaled P AH Emission {U. s.Ai

Source

Metric tonslyear

I. Residential combustion Wood, coal

Oil, gas

·700 15

12 0.3

b. Industrial Production Coke manufacturing Carbon black

Asp hal t Production Aluminum Production

630 3

4 1000

11 <0.1 <0,1 17

c. Power Generation

Coal and oil -fired power plants Industrial boilers

1 400

<0,1 7

d. Incineration

Municipal Incineration Open burning

Forest fires

SO 100 1000

0.8 2. 17

e. Mobile Sources

Gasoline Automobiles Diesel

21002 70

35 1

Total

6000

l. Numbers are encumbered with great uncertainty, To be used as an indicator of order of magnitude

2. Approximalely :50% of u.s, cars have: catalytic converters, This is not corrected for in this number.

Ta ble 1.3 Estirnat ed P AH emissions in the U. S ,A (Ramdahl, 1985)

9

RCRA regulates the disposal of hazardous waste and also controls emissions of PAH and CHC from the disposal facilities. RCRA also determines whether the hazardous waste requires pretreatment on-site by the waste generator before "final disposal. Waste include such materials as garbage, refuse, sludge, and other dicarded material, including solid, semisolid. liquid, or contained gaseous material, Waste can be hazardous due to its characteristics or because is listed as such (Davenport, 1992). A characteristic "hazardous waste is reactive, corrosive, ignitable , or toxic. Toxic waste contains metals such as chromium, lead, or mercury, six listed pesticides, and some 25 organic constituents ( such as benzene and chlorinated hydrocarbons) above specified concentrations. Listed hazardous waste can be spent solvents and process wastes such as distillation residues, API separator sludge from petroleum industry, acutely hazardous discarded commercial products, spin residues, or off-specification products to list a few. In 1986, 747.8 million tons of hazardous waste were generated by 12,4"78 large quantity generators (Baker, 1992a). The waste was categorized into seven major categories:

• Waste water 608.2 million tons (mostl y a water rna trix including the
toxic substance)
• Organi c li quid 89.1 minion tons
• Unkown 3 1.3 million tons
• Organic sludge/solid 7.9 million to ns
• Inorganic sludge 6.9 million tons 10

• Inorganic solid

• Other mixtures

3. 7 minion tons 0,2 minion tons

Table L 4 depicts the management method fo r treatment of the above waste. Combustion technolo gies su ch as fu el blending, reuse as fuel, and lncinerati on are important methods of treatment. We have already shown in Table 1,3 that incineration of these wastes will result in the generation ofP AH. Note that waste water treatment results in the generation of secondary biolo gical sludges which could in princip I e be treated by incineration as a final form of dispo sa] (Crumm. 19 86), and storage of waste constitutes a significant method of waste treatment but by no means a final soluti on to the waste problem. As stated above, spent solvents are considered hazardous waste and they often consist of CHC. CHC are used and manufactured in a significant number of chemical industries ( Bozelli, 1990)~ and treatment of wastes from these industries by incineration is an effective method of treatment ( Senkan, 1988) but their incineration wiIl result in the generation of trace toxic p ollutants such as benzyl chJ oride and other chlorine ted-P AlI as well as non-chlorinated PAH (Huang and Senkan, 1996), also simple CHC such as vynil chloride, 1,2 dichloroethene, and trichloroethylene to name a few {Miao, 1990)

Gammage (19 S 3) di scu sses issues related to P.AH in the workplace, Workers in industries generating petroleum, coal. or shale products ma.y become exposed to carcinogenic P AH, Published comparisons give ranges ofP AH composition that are 5~ 15

II

Management Method

Quantity Number
Managed in 1986l of
(minion tons) Facilities
1.44 330
1.18 1470
0.96 243
·0.75 177
1.44 295
1.09 197
0.77 122
0.38 58
732:il 4399
4.61 70
232] 298
3.17 lIB
0_68 71
28.7 63
189 1785
1.98 128 Metal Recovery Solvent Recovery Other Recycling

Fuel Blending

Reuse as fuel Incineration Solidification

Land Treatment Wastewater Treatment Disposal Inpoundment Surface Inpoundment Landfill

Waste Pile

U ndergrou nd Inj ection Storage (RCRA permitted) Other Treatment

L Total wale generated in" 1986 was 747 million tons. Note that some wastes were managed in multiple traetment

2. Includes the wat.c:l' matrix

3 _ Intludes waste entering surface impoundments fur disposal, treatment and storage.

Table 1.4 Hazardous Waste Management Methods (Baker, 1992b)

12

wt.% in coal-derived oils as compared to 1-2 wt% in petroleum derived oils. The PAH content of shale oils appears to fall between that of coal and petroleum. Gammage also points out that chemical analysis indicate that the overall PAH and Benzo(a)pyrene (BaP) contents of natural and synthetic crude are as follows: coal derived oils» shale oils» petroleum oils, From the P AH and BaP content of the above fossil fuels one would rank the potential carcinogenic risk in the same order.

The biological activity of some P AH is depicted in Tab] e 1.5. T ada y. the regulatory standards for worker exposure to PAH-containing materials are minimal in number. This situation arises not so much from the lack of a perceived need as from the difficulties of dealing with large numbers ofP AH in complex mixtures ( Gammage, 1983)' For examp le, the 0 SHA ( 1974) stand ard for 8aP from coke oven emissions has not been promu1 gated because, in general, a standard based onJy on expo sure to BaP is a questionable practice due to the varying composition of sourc es of P AH, and consequently. there is no correlation between PAH and BaP levels. Furthemore, BaP levels cannot ac count entirely fo r the carcinogenic an d mu tageni c activity of organic extracts 0 f suspended particulate matter ( as noted before P AH are often associated with particulate matter).

In summary, because of the adverse health effects associated with trace emissions ofP AH and CHC arising from the use of combustion technologies, current laws and regulations provide for control of these emissions and a strong motivation for research in

13

Compound

Carcino geni c Potential]

Bioactivitf

2-Methylna phthalene

o

TP

Fluoranthene

o

cc

2-Methylfluoranthene

+

c~ TI

Pyrene

o

cc

Benz( a) ant hr ac ene

+

TI

Benzo( c )phenanthrene

+++

c

Benzo(b )fluoranthene

++

C,11

Benzo( a)pyrene

+++

1. Key: ?z uneertain ; 0'" inactive; + to ++++ "" active

2. CC"" cocardnogenic with SaP ~ TP= tumor promoter ~ Ti= Tumor irudator; 0- complete carcinogen,

Table 1.5 Biological Activities of Some P AH (Gammage, 1983)_

14

the mechanisms of formation of these pollutants in order to be able to make better predictions on the ernissio n level s from practical combustion devices,

1.2 Detailed Chemical Kinetic Models (DCKl)

This section will deal with issues that have great bearing on the theoretical and experimental requirements for the develop ment and validation of DCKM with the objective of measuring and modeling P AH in combustion, more specifically, in fuel-rich premix laminar flames of methane and simple CHC_ The DCKM. is only a submodel part of a more complex. description of the process at hand _ Jncinerat or design, for example, rna y also have to include submodel s for fluid mechanics, heat transfer ~ fuel atomization and vaporization in order to properly make predictions on its performance .

...._ In the past, there has been an oversimplification of underlying chemistry and

chemical kineti cs in the development of processes involving chemical reacti ons ( Senkan, 1992) such as in the manufacture of chemicals, through the use of so called empirical or globaJ mechanisms consisting offew reactions with empirically determined reaction rates. For example, the rate of consumption of a fuel would be given by an expression below

d[fuel]/dt = A exp { -EJRT } [fuel] I [02] b

where the pre-exponential factor ~ activati on energy E~ and exponents a and b would be empirically determined to fit experimental data. The consumption of fuel would occur by the following simplified single- step irreversible reaction

15

Fuel + XOl

=>

Today. however, because of increasing concerns over production flexibility, selectivity,

quality control, safety, and environmental pollution, it is no longer acceptable or possible

to relay on simple empirical chemical models. This is specially true of predictions for the

concentration orPAH and other toxic ~ wecies in combustion devices because, fluid

dynamics aside, their formation is strictly a kinetic effect dependi ng on complex: chemistry

involving stable and radical species. and combustion conditions such as temperature and

equivalence ratio.

A DCKM: consi sts of many element ary reactions which tog ether describe the

chemical pro cess, methane oxidat i on, for exarnpl e. T"he elementary reactions describe the

chemical j nteraction between species forming the DCKM~ obviously it may not be

practical to include all possible reactions between sped es or all possible species but

enough reactions and species wiII be included to capture the main features of the proces8,

including reactions leading to relevant trace sp ecles such as P AH for example. (The

number of sp eci es in the mechanism grows rapidl y with fuel molecule size; for N sp ecies, ther would be N 2: reactant pairs, and for each pair there could be a number of possible

products). Thus, the construction of a practical DClQy( involves principally the

" "

identification of those reactions which actually occur and are rapid enough to have an

impact on the overall progress of the combustion event (Westbrook, 1984). Experimental

data obtained in a laboratory is of paramount importance in elucidating both species and

pathways that should be main constituents of the DCKM_ In Chapter 4~ the approach to

" "

16

solve a complex mathematical problem such as the cornbustio n of methane in a premixed laminar flame win be discussed in more detail.

In this study. we are concerned with the combu stion of a hyd rocarbo n fuel in a laminar premixed flame. There are several aspects of hydrocarbon combustion that are of paramount importance in the development ofDCKM. Hydrocarbon combustion in the high temperature regime (> 100 0 "K) results in the sequential fragmentation of the initial fuel into smalJer fragments, these fragments can react to form heavier molecules, but all are ultimately converted to final products water, and carbon dioxide if the conditions are ideal. In ideal conditions, the oxygen co ntent of the mixtu re everywhere is sufficient to convert the fuel completely according to the formal chemica] reaction

c.n, + (x+y/4) O2

<=>

"C02 + y/2 H2O

Also commo n to hyd rocarbon combustion is the gen eration of hydro gen and carbon monoxide. and radical species H. DB, and D. For combustion under fuel-rich conditions where fuel is in excess rei ative to oxidant, CO, H~, heavy i ntermedi at es, and trace sp ecies may survive the combustion process. Because ofthcse reasons, hydrocarbon combustion results in a hierarchical structure as depicted in Figure 1.2 (Westbrook, 1984) which simplifles the development afDCK]\.{ for any fueL Thus methane oxidation consists of the foUowing oxid a tion subrnechanisrn s: C 2. sp ecies, CH20, CO. Hl- 01- In the case of a simple CHC such as methyl chloride, Figure 2 would have to be modified to incorporate chlorinated species such as C~.lCl and He], because the introduction of chlorine in the

17

molecule introduces a new degree of freedom in terms of chemical species that could be important in the mechanism. The high temperature combustion mechanisms for methane, methy1 chloride, and 1,1 DCE in premixed lami nar flames will be discussed in more length. in Chapter 2_

In addition to the hierarchical structure of high temperature combustion of hydrocarbons, there exists un ~~ imler st ructure" to the combustion mechanism. As Dryer (1991) points out hydrocarbon oxi dation mechanisms are chain reaction mechani srns, The basic premise of chain theory is that act ive centers (free rad i cals and atoms) playa leading role in the destruction of reactant molecules. The chain rection mechanism itself consists of several steps: initiation, propagation, branching (not always present), and termination. This can be illustrated, for certain range of temperature and pressure, by some of the reactions in the following hydrogen oxidation mechanism:

initiation li2; + O2 <-> 20H
prop agation H2+OH < > H2O+H
branching H+02 <=> OH+O
branching H2+0 <=> H+OH
branching H20 + 0 < > OH+OH
termination H+OH+M < > HzO+M
plus others. 18

C. K. WESTBRDOI( anc F. L. DRYER
I
C3 $pl!!cies 1
~
CH4 H ~ C2• .. ei .. 2H CzHsOH I
C2~. - CZH. - CZH2 :
j
I CH:O }4 I
CH']OH

r
co I

[ H2 - 02 I Figure 1.2 Hierarchical Structure of Combustion (Westbrook, 1984)

19

The initiation step is responsible for the initial decomposition of the reactants. Propagation steps involve a radical-molecule reaction with generation of a radical in the product, while branching reactions pro duce two radic als per single radical in the reactants. Flame phenomena is due to the branching step predominating over termination, and the large generation of radicals result in a combustion wave or flame that is responsible for the fast decomposition of the fuel ( see next section).

The experimental conditions have a bearing on the chain mechanism in terms of the relative importance of reaction 5 that are possible in the mechanism. For example, the oxidatio n of hyd rocarbons at low temperatures is ini tiat ed by the fo llowing reactions ( Dryer. 1991) :

<-> R+H02 +M <-> ROz

(1.1) (1.2)

leading to formation of oxygenated species such as alcohols, aldehydes) olefins, and acids. These kind of reactions take place in the urban atmosphere, for example ( Seinfield, 1989). Reaction (1 . I) is endothermic by about 45 to 55 kcal/mol. In shock tubes, however, the temperature of the fuel-oxidizer mixture is raised very rapidly by the shock to the range 1400-2100 ~ and the initiation reaction that predominates is the thermal decomposition of the fuel:

RH+M

<->

R+H+M

(1.3)

Reaction (1.3) is endothermic by about 100 kcal/mol and is significant because of the higher temperatures and generates the necessary radicals for the decomposition of the fuel

20

by chain reactions (one thing to note here is that as the system temperature increases, radical concentrations increase rapidly). We wiU see that in 1aminar premixed flames. because of radical d iffusion phenomena that allows radical concentrations to build in the zone of initial fuel decompo sition, fu el deco rnposes mainly by reactions (1.4) and (1.5) involving radical s:

RH+H RH+OH

< >

(IA) (1.5)

<=>

Also because of the very high temperature of the flame, H, OH radical concentrations can be quite high.

In summary, there are underlying structures to the high temperature oxidation of hydrocarh ons, the hierarchical structure, and chain reaction mechanisms are important ones, which result in the final decomposition of the fuel to CO~ CO2• IiJ, H2O. in concentrations that depend on the fuel-oxidant ratio, through the generation of heavier molecules that may survive the oxidation process if there is excess fuel over oxidant. These structures can be used in the orderly construction of large or small DCKM:.

1.J The G en eral S tru cture of Prem i:l. Lam i n ar Fl ames

As stated before, experimental data provides valuable information for the validation ofDCKM by making available species concentration profiles which can be used to detennine the most pausible paths for fuel decomposition.

21

"Table 1.6 depicts experimental techniques which can be used to validate DCK1v1 (Westbrook. 1984), Shoch tubes can be used to study the kinetics of reactions at very high temperatures. however because 0 f the speed of the reactions in the shock: tube due to the extreme ~nditions, available diagnostic techniques often cannot resolve many of the details of the combustion process. For this reason shock tubes are useful in studying the thermal decompo sitlon or initia tio n reactio n for fuels at high temp eratures, reacti on (1.3) of Section 1,2 for example, but often not useful in the validation ofDCKM:. PFR experiments provide very valuable information for the oxidation of'fuels in the medium temperature regime. The characteristic time for "fuel decorn po siti on is such that concentration profil es can be easily generated for a large numb er of speci es making it possible to validate DCKM:. Finally, flames are also a valuable technique to validate DCKM_ More sp ecificall y ) premix: laminar flames c an be mod elled more easily than say turbuJent diffusion flames 0 r even laminar diffusion flames ( by diffu sion, it is meant that fuel and oxidizer are not premixed) and still present features that are common to many real combustio n device s su ch as furnaces and gas engines ( Westbro ok. 1984).

In this study, the experimental technique used "for DCKM validation was a burnerstabilized one-dimensional premix laminar flame as depicted in Figure 1_3 _ In this set-up) the flat luminous zen e ofthe flame stabilizes ab ave the burner surface, with the burner consisting of a. porous. plug where fuel and oxidizer intimately mix and which produces a very flat velocity profile acres S the burner suface, The bu mer it self is cooled with a

22

P T Dilution Minng Transpert
EI eriment Limits Effects
Sboch Tubes high >1300K yes none no
Plug Flow
Reactor atmospheric 850-1300K yes none no
Fh.mfS low 800-2S00K no flammabili ty yes
limits
Table 1.6 Experimental Regimes for validation ofDCKl\.1 (Westbrook, 1984) coolant. which by removing heat, helps to stabilize the luminous zone further away from

the burner surface, and results in a broadening of the flame structure of Figure 1.3. Flame

broadening makes it p'0ssibte to generate species concentration profiles as function of distance from the burner surface.

The premixed fuel-oxidizer mixture flowing throuh the burner at room temperature

and ambient pressure is unreactive un] ess an ignition source is available. The ignition

source raises. locally the temperatu re and radical ccncentratio n in the mixture such that a

combustion wave or flame is generated that propagates through the reaction mixture if the

mixture is within its flammability limits. On Figure 1.3, the luminous zone of the flame can

be seen stabilized ab ove the burner su rface and 0 ppos ed by the convective flow of the

combustio n mixture. The flame velocity isles s than the speed of sound and controlled by

transport of heat and mass within the flame (G1assman, 1987). As Wamatz ( 1984a)

23

Figure 1.3 Laminar Flame Structure

LUMINOUS

z .i..

ZONE ill

POST REACffON

ZONER REACTION

ZONE T- PRE REACTION

FUEL OXIDANT

24

points out, fully developed burner-stabilized flames, studied in the laboratory, are radicalrich and thi s condition determines thei r chemistry.

Within the flame structure, it is possible to characterize three zones ( see Figure 1.3): ZOne I or preheat zone, zone II 0 r reaction zone, and zo ne m 0 r recombination zone (also known as post-flame zone). Figure 1 J also shows the temperature profile associated with this type of fl arne. Because of the high temperature of the reaction zene, H, OH radical concentration is high. these radicals together with heat are transported by difussion against the convective flow to the preheat zone, where fuel decomposition takes place mainly by reactions (1 _4) and (1 ,5) as stated in Secti on 1.2

RH+H <=> R+H2

(1.4)

RH+OH

<->

(1.5)

In the reaction zone, and due to the high temperatures, radicals are generated mainly due to the branching reaction (1.6)

<->

O+OH

(1.6)

in this zone> fuel decomposition by reaction (L7) also becomes important (because of the high temperature)

RH+M

<=>

R+H+M

(1.7)

generating the much needed" H radical s, I ntermedi ate sp ecies concentrations ri se due to addition reactions such as (1,8), which produces heavier molecules R'. and are responsible for molecular growth specially in fuel-rich flames

R+ R+M <=> R' + M (1.8)

25

In the reaction zone, the co ncentration of cornbustio n products such as CO. H2 , and H20 rise very rapidly with the tina] oxidation of CO by reaction (1.9) delayed until the latter part and into the post-flame region (zone III) where most of the hydrocarbon intermediates have disappeared.

CO+OH

<->

. (1.9)

In the post-flame zone. radicals are terminated by slow termolecular reactions such as reaction (I. 10) below

. H+H+M

< >

H;~+M

(llO)

The chain branching reaction (1.6) and CO-oxidation reaction (1.9) are common to oxidation of all hydrocarbons at high temperature and result in the simmilarity between flames of different hydro carbon fuel ( Warnatz, 1981).

In the high temperature combustion of heavy alkanes such octane, reactions (IA) and (1.5) also initiate decomposition ofthe fuel to form alkyl radicals. These long-chain radicals can easily fragment into smaller fragments du e to the relative weakness of the c-c bond in the alkyl chain leading eventually to C I and Gl species. This observation lead Warnatz ( 1984b) to conclude that in the combustion of higher alkanes is the oxidation of CI and C:,: species that control the rate of oxidation of the fuel

26

1.4 PAR Chern is try and Kin etlcs in Flames

-

As stated in Section 1.2) ideal combust jon conditions lead to total destruction of

the fue1 to carbon dioxide and water. In practical co mbustion devices such as furnaces, gas

turbines. or combustion engines conditions locally deviate from ideallity ( Bockhorn,

1994). The fuel may have to be atomized or vaporized, and because of safety reasons fuel

and oxidant are never premixed. The conditions are such that they corresp end more to the

conditions, prevalent in laboratory diffusion flames (Westbrook, 1984)_ In the turbulent

region of the combustor, mass transport occurs mainly by eddy diffusion. and depending

on the extent of turbulence, the eddies feed flamelets where the decomposition of the fuel

takes place. If the flowis highly turbulent. there could be pockets where the flarnelets are

bown-off In the flamelets there are fuel-rich regions where locally oxygen is not sufficient

to convert aU of the fuel to CO2 and H20 other products of incomplete combustion win

appear such asCO~ H1> heavier hydrocarbons> PAH and soot.

The modelling of benzene formation, the first aromatic ring, and subsequent

growth into heavier P AH is rei ati vely recent. The process of chemical activation, whether

unimolecu lar or bi rno I ecular, is most i mpo rtant to the. modem ng of both benzene and P AH

. .

formation. Chemical active tio n can be described by the simplif ed reaction scheme below:

A+B

< >

M ->

I

excrthe~c (1.11)

I*'

>.

p

(1.12)

M

27

_.

1*

<=>

II"

> <->

II pp

exothermic - (1.13) (LI4)

II·

In reaction (1.11). reactants A and B react by addition to form an intermediate complex r· that is chemical! y activated, by thi s is meant tha t I· has an excess of energy over its stabilized counterpart I equal to the bond energy. Chemically activated 1* may decompo se to form product P; the reaction could be exothermic or endothermic. In reaction (1.13), I· isomerizes directly to chemically activated isomer Il", which can then be stabilized to n or decompose to product PP. Above) we have refered to a stabilization process. this means the removal of excess energy by collisions with a body M, an exothermic process. This reaction scheme can be treated by quantum mechanical methods (Westmore]and et al., .' 1986) that can account for the dependence of the overall reaction coefficients for product formation on the internal energy of the chemical adduct. More about this win be said in Chap ter 3.4_

The reaction paths leading to the formation of benzene have been extensively studied (Frenklach, 1994a, Westmoreland et al., 1989) and involve chemically activation as described above. The format jon of the first ring involves acetylene ( a most abundant species in flames where there is excess offue1) and follows the scheme below:

=>

Benzene

(1.15) (1.16)

>

where two-carbon species chemically add to acety1ene via reaction (1. 15), and then the four-carbon species in turn react via (1.16) to form benzene. MIner and Melius ( 1992)

28

also ha ve proposed an additional scheme in vel ving propargyl radical, a 3 -carbon radical

species:

C:Jh+C~

=>

Benzene

(1.17)

where propargyl radical is formed by reaction (1. 1 g)

< >

(1.18)

where CH,i!(s) is the excited singlet state ofmethy1ene radical Propargyl is an abundant

free radical in fuel-rich flames due to its thermodynamic stability based on resonance

structure considerations ( MIler & Melius, 1992). Of the two routes to benzene above,

the route invoving acetylene additions, reactions (1.15) and (1.16), seem the most

important route in flames of acetylene and ethylene (Frenklach, 1994a), or fuels

consisting of two-carbon molecules.

After forma don of the benzene ring. the formation and growth of P AH

proceeds mainly through the Heabstracticn-acetylene-addition (HACA) mechanism

proposed by Frenklach and coworkers (1994a), a very recent development. This is

illustrated for the formation of naphthalene from benzene below

[J' +H < > [J + H1
• O+H
~ +Cl~ <=>
5 +H <-> -0' +H1 (1.19)

(L20)

. (1.21)

29

<=>

00

(1.22)

Another route bas been propo sed by Colket ( 1994) in the pyrolysis of toluene and

consists of the addition of propargyl to benzyl radical as illustrated by the overall reaction

(1.23)

<->

+ 2H

(L23)

We shall see in Chapter 2 that an additional route exists for the formation ofP AH

involving aryl rad ical s which has not been investigated by the ab ove authors,

In reactions similar to (1.19)-( 1.23), chlorine radicals produced during the

combustion of CHe can perform the role of H radicals in activating the aromatic ring for

P AlI growth. e.g,

+Cl

<=>

Q

+ Hel

(1.24)

In the combustion of CHC~ chlorinated - P AH can form by reactions such as (1.2 S) below

C1

o

+ Hel

<->

+ .H

(1.25)

More will be said regarding the role of chlorine in combustion and P AH formation in

Chapter 2

30

As stated in Section 1. 1) P AH are considered to be precursors to soot. A rough picture for soot formation in premixed laminar flames is depicted on Figure 1 _4 taken from Bockhorn ( 1994). The conversion 0 f hydrocarbon fuel molecule eonsi sting of few carbon atoms into a carbonaceous material consisting of some millions of carbon atoms is an extermely complicated process involving chemical and physical phenomena. First, fuel decomposition must lead to smal1 hydro carb on radicals which by addition reactions form heavier molecules, specially acetylene. Second, these heavier hydrocarbon intermediates must continue to grow and eventually Iead to the formation ofPAH_ 'Third. the growth in third dimension supposedly happens by the coagulation of larger P AH forming primary soot particles. Particle coagulation determines the final size oftbe soot particles. Surface growth involves first diffusion of gas-phase molecules to the soot surface, and then their addition to soot, and contributes to t he maj or pan of the final so ot concentration in . sooting flames. The irregular aggregate structure of soot panicles is attributed to the coagulation process. In diffusio n flames, all chemical p roc esses of Figure L 4 are overlayed by the laminar or turbulent m.ixing of fuel and oxidizer.

In summary, PAR emissions from combustion devices pose a health risk and their emissions need to be minimized. In order to make predictions of the level of emissions of P AH during combustion, D CKM: have to be assembled. The hierarchical nature of high temperature combustion of hydrocarbons and chain mechanisms are very important underlying structures ofDCK1vf which simplify building larger DCKM for more complex

31

.... - .. : .. - ....

• • •••• • • •

•• a ••• f ••••

. :.! .•.•......... • • ••••• ••••

• •• •

50rwn

eo.QUIB'IIDn

D.5rvn

Figure. 1.4 Rough Picture for Soot Formation (Premixed Flames)

32

- ... -_ .. _--

fuels, In Chapter 2, the chemistry of combust jon of methane and simple CHC win be reviewed. The theoretical background for determination or thermochemistry and kinetics ofPAH formation is presented in Chapter 3. Chapter 4 presents the mathematical approach to solving the governing equations for premixed laminar flames, with Chapter 5 discussing useful computational techniques within the Flame Code and MOPAC framework that allow solving the flame problem for very large DCKM: and the generation of energy barriers for reactions involving P Ali. The last Chapters discuss the validation and optimization of the DCKM" with special attention to the formation orpAH, and the generation of P PJ-l chemistry an d rate coeffi ci ents fo r P AH reacti om.

33

CI-IA_PTER 2

CHE~ilISTRY AND KINETICS OF COl\lBl]STION

This chapter will deal in more detail with the chemistry and kinetics of combustion of methane, methyl chloride, and 1 ,I DeE in fuel-rich premixed laminar flames. As stated in Section L2, because of the hierarchical nature of combustion at high temperatures, DCKi for combustion of these simple fuels can be very important building blocks for the combustion mechanisms of more complex fuels. As mentioned in Section I :1, the conditions for most practical combustion devices correspond more closely to those of diffusion flames with turbulent mixing of the fuel and oxidant. Within the free turbulent flow of the combustor, diffusion flamelets may form and in their fuel-rich zone products of incomplete combustion such as hydrocarbons, PAH and soot can appear These conditions provide the inscntive to study premixed laminar flames (which have SImpler fluid

dynamics) under fuel-rich conditions that result in a richer chcmistrv

2.1 Methane Combustion

Over the years, there has been a lot of material published in literature concerning combustion chemistry and kinetics of methane under different experimental conditions,

34

Wang (1992) lists over 30 references, however. as he points our [he most important

reaction paths for the hiuh temperature combustion of methane 3H': well understood but

- .

there arc differences in the magnitude of the rate constants for some of the reactions.There

are important reasons for the differences in rate constants. The rate coefficients are

estimated under experimental conditions that are seldom the same Conditions of press ure

and temperature have an effect on unimolecular or chemical addition reacuons, 10;:-

example. Furthermore, the rate coefficient for a single elementary reaction must be

discerned from other competing reactions, in other words, the reaction of interest docs not

take place by itself, and this introduces errors in estimates of its magnitude T;lis

discussion refers only to the most I~cer!1 work and surveys dealing with methane

combustion and with the most bearing to the objectives stated in the abstract orthe

dissertation,

In order to assemble the most important chemistry of methane combustion in fU9i-,

rich flames as depicted in the mechanism of Appendix D -r the following uubiications were

reviewed: Gardiner (1994), Baulch et al. (1992), Wang (1992), Miller (\:. Bowman I 19891,

Warnatz, (1984a), and Westbrook & Dryer (19841 The rate coefficients for the reactions

in the mechanism were chosen from the same references iistcd above with more weight

given to the work by Baulch et al, ( 1992). Baulch presents an extensive survey or

chemistry of combustion of simple hydrocarbons with recommendations given for each

rate coefficient. How the mechanism so assembled was validated and optimized wi11 'be

35

described in Chapter 7 The most important paths for methane decomposition in leal] and

moderately rich flames were identified by Wamatz ( 1984a) and these are reproduced in

Figure 2.1, and the discussion that follows refers to this figure As exnlaineu in Section

L3, laboratory burner-stabilized flames are radical-rich because of the high temperatures

and H, OH , and 0 radicals produced in the reaction zone diffuse to the preheat zone to

initiate decomposition of the fuel. Reactions (2.1) predominates over reaction (2.::-'; in the

initial methane decomposition in fuel-rich flames

C~+H

<=>

(2.1)

CRt + OH

<=>

The thermal decomposition of methane or reaction (2.:3) below is an endothermic process

which only will take place to any extent in the high temperature reaction zone. Even at

atmospheric pressures, the reaction rate coefficient is in the fall-off regime of unimoiecular

reactions.

CfL+M

<=>

The reverse of reaction (2.3) is an important radical termination step 1U flames as shown in

Figure 2.1.

The fate ofthc methyl radical CI·h in flames is of the outmost Importance in

hydrocarbon, PAH, and soot formation in flames. The formation of ethane by reacuon

(2.5) below, in fuel-rich flames, effectively comoetes witht the oxidation of methyl radical

~, y ,

by reaction (2.4). The ethane route leads to P AH formation and finally soot.

<=>

(2.4l

36

Jiirgen Warnatz

CH3.CHzO,CHO
1"0,0" l"
-(HO CZH3
,'HO,H 1 ",
j ..
• H I +M.H .... -, -o
I ....
j ...
I ...
....
·OH ~It
co (2HZ ----- .... CHlCO -----_...,. CH,
1.0 r
,
,
, 0011
j

CH ·H CH2
CH1O,CHO
l~,o, 1.0,0,
(0 (0 Figure 2.1 Reaction Paths for Metane Oxidation (Warnatz, 1984a)

37

CH3

M

<=> [C2l-Li] * => C2l-Li

(2.5) (2.6) (2.7)

Reaction (2.5) is in the fall-off regime even at atmospheric pressure. Ethane and ethylene

concentrations build-up in the reaction zone of the flame.

In fuel-rich flames, formaldehyde is consumed mainly by reactions (2.8), (2.9)

<->

(2.8) (2.9)

<=>

CHO+H

CHO is then consumed by H-atom attack or thermally decomposes to form CO.

CHO+M

< >

CO+H+M

(2.10)

Ethane formed by reaction (2.5) above is consumed mainly by the following

reactions in fuel-rich flames

C:Ji6+ H

<=>

(2.11) (2.12)

CA+OH

< >

The above ethyl radical is consumed by the following reactions

<=>

(2.13) (2.14)

C:zHs +H

<->

Ethylene formed by reactions (2.13), (2.14) is consumed mainly by H-radical attack,

reaction (2.15)

<=>

(2.15)

38

Vinyl radical leads to acetylene via the following reactions

< >

(2.16) (2.17)

<=>

Acetylene (Wang, 1992) is oxidized via the following reactions

<=>

CH2 + CO CHCQ+H

(2.18) (2.19)

C2H2 + 0 C~2+0 followed by CHCQ+H

<=>

<=>

(2.20)

where CH2(s) is methylene radical in the excited singlet spin state which is quickly converted to the ground triplet state by collisions .. Methylene radical chemistry is not well established (Wang, 1992), Miller and Bowman (1989) oxidize methylene as follows

CH2 + O2 <=> CO2 + H + H (2.21)

Ethane, ethylene, and acetylene are intermediates whose concentrations rise in the reaction zone of the flame only to be consumed before they reach the post-flame region. Not depicted in Figure 2.1 are the following reactions of acetylene that should be important in fuel-rich flames:

<=> < >

(2.22) (2.23)

As discussed in Section 1.2 of Chapter 1, the hydrogen and carbon monoxides submechanisms are also important in methane oxidation and they have been studied

39

extensively (Westbrook, 1984). In the reaction zone, the most important reaction is the chain-branching reaction (2.24) responsible for flame propagation

<=>

OH+H

(2.24)

Radicals H, OH .and 0 build up in the reaction zone of the flame. Carbon monoxide oxidation takes place mainly by reaction (2.25)

CO+OH

<=>

(2.25)

Reactions (2.24) and (2.25) are common to all hydrocarbon oxidation and result in the simmilarity between flames of different hydrocarbon fuels (Warnatz, 1981).

As we have seen, methane decomposition by radical attack leads to intermediates such as formaldehyde and heavier hydrocarbons such as acetylene; nevertheless paths exist within the mechanism for the ultimate formation of carbon dioxide and water. The existance of such paths gives some validity to the reaction chemistry since this is in accordance with observation.

2.2 Combustion of Simple Chlorinated Hydrocarbons (eRC)

As stated in Chapter 1 Section 1.1, CRC combustion emissions is a very important consideration in the safe destruction of hazardous waste from the chemicals industry. This section will discuss the combustion chemistry of methyl chloride and 1,1 DeE and issues

40

that are very relevant to eRe chemistry such as flame inhibition or radical scavenging. The substitution of chlorine for a hydrogen in the hydrocarbon molecule also introduces some differences in the thermodynamics of eRe as compared to its unsubstituted counterpart.

2.2.1 Flame Inhibition & General Chemistry

Inhibition and extinction of hydrocarbon fuel oxidation in flames and detonations by additivies consisting of halogenated compounds is a practical and theoretical problem which has been studied exp erimentall y for many years ( Westbrook, 1982, and Lewis, 1980). The addition of the halogenated compound results in the reduction offlame speed or "burning velocity" and increase in ignition time of the combustible mixture. In all the cases studied, the halogenated species act by catalyzing the recombination ofH-atoms into relatively non-reactive hydrogen molecules (most effective in the pre-recti on zone), reducing the available radical pool and lowering the overall rate of chain branching reaction (2.24)

H+02

< >

OH+O

(2.24)

In the case of an additive such as Hel, reactions (2.26)-(2.29) are responsible for the overall recombination ofH-atoms to hydrogen

<=>

Hel +Cl H2+Cl

(2.26) (2.27)

H+Cb H+HCI

<=>

41

C1 +Cl +M H+Cl+M

<->

Ch+M HCl+M

(2.28) (2.29)

<=>

Reactions (2.26)-(2.28) add up to the chlorine-catalyzed recombination of hydro gem atoms H + H = H2. However, the real key to this type of inhibition is the regeneration of Ch by reaction (2.28) which allows the entire cycle to be catalytic The rates of reactions (2.26)-(2.28) are fast compared to reaction (2.24), this diminishes the concentration of OH radical and slows the oxidation of CO by reaction 2.25 into CO2 and results in the appearance of a two-stage process (Frenklach, 1990).

For addition of halogenated hydrocarbon species, the general inhibition pattern is

dominated by reactions listed below
H+RCI <=> HCI+R (2.30)
R+Cb <=> RCI + Cl (2.31)
H+HCl <=> H2 + C1 (2.27)
Cl+ ct +M <=> Ch+M (2.28) Like the earlier cycle the net result of these reactions is the recombination ofH-atoms.

It is important to note that in chlorine-containing environments reaction (2.27) regenerates CI atoms from HCL In oxidative environments the regeneration of Cl can also take place via reaction (2.32)

OH+HCl

< >

(2.32)

and to a lesser extent by reactions such as

O+HCI

<=>

OH+Cl

(2.33)

42

Reaction (2.32) also has the effect of reducing OR concentrations and the oxidation of CO by reaction (2.25). In other words HCI is not an irreversible sink for CI atoms, and as the concentartion ofHCI increases, it begins to free the Cl atoms back into the system, thus keeping them at a high concentration (Frenklach, 1990).

In addition to the effect of chlorine on the H-atom radical pool as demonstrated above, there are thermochemical differences between CHC and their pure hydrocarbon co_unterparts ( Senkan, 1993). Table 2.1 shows the C-CI bond to be weaker than its C-H counterpart, furthermore, aC-H bonds are weaker than the ~C-H bonds due to the presence of chlorine in the molecule. As Frenklach ( 1990) points out, the weaker C-CI bond can break more easily in the initial stages of the fuel composition and the easier pyrolisis of chlorinated hydrocarbons leads to higher production of heavy intermediates such as acetylene that are important in P AH and soot formation.

Species

J3C-H

aC-CI

C-C

aC-H

CH4 CH;CI C2l1ti C2HsCI

104 99 100 97

84

84

89 89

102

Table 2.1 Bond Dissociation Energies for CHC (-Senkan, 1994)

43

The easy break-up of the C-CI bond also results in high concentrations ofCI atoms, which promotes hydrocarbon d egradati on by H -abstraction to form HCl. In the attack of 1, 1 DCE by chlorine for example, a-H abstraction is preferred over B-H abstraction because of the weaker bond (as demonstrated for chloroethane on Table 2.1)

1,1 DeE + CI 1,1 DCE + CI

<=>

CH3CCh + H -8.65 kcal/mol (2.34)

CHChCH2 + He! 1.24 kcal/mol (2.35)

<=>

More will be said of the role of chlorine in P AH and soot formation in Sections 2.3.4 and 2.3.5.

The work of'Kassern (1990) with 1,2 DeE highlights some of the phenomena described above. Kassem theorizes that Cl radicals are soon converted to HCl in the prereaction zone of the flame only to be re-released in latter parts of the flame thanks to reactions (2.27) and (2.32). This effectively competes for Hand OH radicals which are so important for fuel decomposition and oxidation. The rate of the chain branching reaction H+ O2 is slowed down until later in the flame. Kassern also found that 1,2 DCE decomposes before the methane fuel as expected due to the weaker C-CI bond energy ..

2.2.2 Methyl Chloride Combustion

As with the discussion of methane combustion in Section 2.1, the literature review for chemistry and kinetics of methyl chloride was restricted to the most recent surveys and works. DCKM for simple CHe have been published only recently as can be seen from the

44

following list of references upon which this discussion and the DCKM for methyl chloride are based: 1, 1 DCE (Gargurevich et al., 1995), Survey of Rate Co nstants by Senkan (1993.4), CHCh (Lee et al., 1993), CCl4 (Xieqi et al., 1993), CH3Cl/CH2Ch (Ho & Bozzelli, 1992), 1,2 DCE (Kassem and Senkan, 1991), CH2Ch (Quo and Senkan, 1990), CH3Cl (Karra and Senkan, 1987, Karra and Senkan 1988a), C2HCh (Chang et al., 1986, and Chang and Senkan, 1988a), and Evaluated Kinetic Data by Baulch et al.(1981). The validation and optimization of the DCKM for CHC in Appendix E is discussed in Chapter 7.

The reaction paths for methyl chloride combustion in flames have been studied by Karra (1988b) in fuel-rich flames ofCHJCH3CI and Jalvy et al. (1994) in fuel-lean CHJCH3CI flames. In addition to the major combustion products (Karra 1988b), intermediate species identified are ethane, ethylene, and acetylene, and CHC species such as CH2Ch, C2HsCl, and C2H3Cl. Trace amounts of benzene were also detected. Figure 2.2 shows the reaction path diagram for a sooting CHJCH3Ci and the discussion that follows refers to this figure. In the radical rich flames, fuel decomposition is initiated mainly by the

following reactions
CH3CI +H <=> CH3 + H2 (2.36)
CH3CI +H < > CH2CI +HCI (2.37)
CH3Cl +Cl < > CH2Ci + Hel (2.38)
CH3Cl +OH < > CH2Cl +OH (2.39) 45

CH4/CH3Cl

I ~,Cl,O,OH

CH3/CH2Cl

1 ~2-

C2H6 C2HSC1 C2H4C12

1 Cl,H

C2H5 M

• CHCIO

l.:1'H'OH CHO +---'"

.,

lOH,C10 cO2

Figure 2.2 Reaction Paths for CH3Cl Oxidation in Fuel-Rich Flames (Karra, 1988b)

46

and for methane in this system in addition to reactions (2.1) and (2.2), we have reaction

(2.40)

ClL + CI

<=>

CH3 +HCl

(2.40)

The relatively abundance of chlorine atoms in the initiation zone of the flame enhances the

rate of reaction (2.40). As discussed in Section 2.2.1 chlorine atoms catalyze the hydrogen

atom recombination to hydrogen molecule which competes with the chain-branching

reaction (2.24) and results in the slow-down offuel oxidation. Nevertheless, the carbon-

chlorine bond is easier to break and leads to relatively large chlorine atom concentrations

which enhances formation of acetylene and other hydrocarbon intermediates. This results

in a greater propensity to form soot and is consistent with the well-known soot promoting

characteristics of chlorine and CHC (Karra and Senkan, 1988a). More about this will be

siad in Sections 2.3.4 and 2.3.5.

As with methane, ethane forms via reaction (2.5) in fuel-rich flames, but the

following channels are available for methyl chloride decomposition involving chemical

addition of methyl and methylene chloride radicals

(2.41)

(2.42)

(2.43)

M

CH2CI + CH2CI <-> [1,2 DCE]* => 1,2 DCE

(2.44)

47

=> C2H3CI + Hel => C214CI +CI

(2.45) (2.46)

Reactions (2.42) and (2.45) involving HCl elimination are the predominant channels. Figure 2.2 shows that hydrogen abstraction by C1 atoms are important in the decay of formaldehyde and ethylene. Vynil chloride decomposes unimolecularly by reaction (2.47)

< >

C:Jf2 +HCl

(2.47)

In the oxidation of CO another channel is now available involving CIO radicals

co + CIO

<=>

(2.48)

Similarly for formaldehyde decomposition a channel involving CI atoms is available or reaction (2.49)

CH20 + CI

<=>

CHO + HC}

(2.49)

As with the combustion chemistry for methane, the methyl chloride mechanism contains chemical paths for the decomposition of the fuel to CO, CO2, H20, HeI, and H2 which gives the mechanism some validity since this is what is observed in an actual flame experiment.

2.2.3 1,1 DeE Combustion

There are few studies concerning the combustion chemistry of two-carbon CHe The chemistry of combustion of 1,2 DeE was studied experimentally by Kassem & Senkan (1991), the results of the experiment were used to validate a DCK}.{ ( Kassem,

48

1990). Experiments were conducted to elucidate the chemistry of combustion ofC2HCh (Chang et al., 1986) wich were then used to validate a DCKM ( Chang and Senkan, 1989). More recently, the chemistry of combustion of 1,1 DCE (Gargurevich et a1. , 1995) was studied in a premixed fuel-rich laminar flame of 1,1 DeE/eIL and the main paths of decomposition for 1,1 DCE were identified. In addition to the main products of combustion two-carbon hydrocarbons such as ethane, ethylene, and acetylene were identified. Major heavy chlorinated hydrocarbonintermediates identified were as follows:

C2H}Cl, CH2CCh, and CH3CL Trace species such as C4Ih CJ-I4, and benzene wre also detected. The fuel decomposition is initiated mainly by Cl, H atom abstraction with the aabstraction more favored based on themodynamic considerations as explained in Section 2.2.1. Reactions involving a-abstraction are as follows

< >

CH)CCb+HCI CH3CCh+H:zO CH2CHCl+H2

(2.50) (2.51) (2.52)

1,1 DeE +CI 1,1 DeE + OH 1,1 DeE + H

< >

<=>

~-abstractions occur as follows

<=>

CHChCH2 + HCl . CHChCH:z + H:zO CH}CCh+H2

(2.53) (2.54) (2.55)

1,1 DeE + CI 1,1 DCE+OH 1,1 DeE + H

<=>

<=>

Clearly then the subsequent reactions of CH3CCb, CHChCH:z, CH3CHCI, and CH3 radicals will determine the nature of the chlorinated intermediates produced in the flames

49

of 1,1 DCE. The following reactions lead to formation of CH2CCb observed in the experiments

CH3CCh +M CH3CCh + O2 CHChCH2+02

<=>

CH2CCh +H+M CH2CCh+ H02 CH2CCh+ H02

<->

<=>

Production ofC2H3CI is likely to take place via the following reactions

CH]CHCI +M CHChCH2+M CH]CHCl +02

<=>

C2H3C1 +M C2H3Cl +M C2H3Cl + H02

(2.56) (2.57) (2.58)

(2.59) (2.60) (2.61)

The formation ofCH3CI is likely to occur via the chlorination of the CH3 radicals in the flame

<=>

<=>

(2.62)

In the previous section decomposition channels for methyl chloride and vinyl chloride leading to CO were presented. A likely path for decomposition of CH2CCb is as follows

CH3 + 1,1 DCE

<=>

CH2CCh + H CH2CCI + O2

<=>

CH2CCI +HCl CH20 + COCI

< >

where formaldehyde leads to CO as previously discussed in Section 2.1 and 2.2.2.

50

(2.63) (2.64)

2.3 PAR Chemistry and Kinetics

Concentration profiles ofP AH have been measured in well-controlled laboratory flames by a number of research groups: Bittner et al. (1981), Bockhom at al. (1983), Westmoreland et al. (1988), and most recenlty Castaldi et al. (1995). Castaldi and Senkan have conducted experiments with the purpose of determining the chemistry of PAH in hydrocarbon flames. The identities and absolute concentrations of over 40 major major and minor species have been estabished, including a large number of aromatics, substituted aromatics, and P AH by the direct analysis of samples withdrawn from the flame without pre-concentration. Mole fractions of the PAR quantified were as low as

2. Ox 10-9. Tne largest P AH identified were species such as b enzo( a )pyrene, peryl ene, and benz( e)-acephenanthry!ene. Haynes (1991) identifies some of the P AH commonly found in flames. These are reproduced in Table 2.2. PAR consisting of two and up to 7 aromatic rings have been detected.

The modelling ofbenzene formation and P AH formation and growth is a recent development. The formation of benzene has been extensively examined by Westmoreland et al. ( 1989), and rigorous modelling work with the purpose of determining the most important steps has been carried out by Wang (1992). Similarly, PAH formation and growth has been studied extensively by Wang (1992), and Frenklach (1994a, 1994b) from Penn State University. The chemistry of formation and growth ofPAH via acetylene addition and kinetic coefficients included in the DCKM: of Appendix D were made

51

PoIyrydic: Al'OIIIatic "rdmc:ubons Tvpically Found in Fl_"
Name SInICture N_ StnlCtun::
@6! Beuzacmaphtbylene ~
Naphtbaienl: 00 ~e ~
0
H.
Methylnaphtbalcne ©@-C~l B=ttuorenc ~
Biphenyl @-@ Methyilluotanthrenc rn,$=©
Bipbenylcne @o§J Methylpyrcnc ~
CH, Table 2.2 P AH Identified in Flames

52

Accnaphthylenc:

ACCDaphthme

Bemo( gil; ]ftllOfal!.thme

Cyclopmta/ ed lpyrene

MethylhiphenyJ

lOIQrOC CH1

@-@CH, Metbyicydopmta/cd]pyrme cgrg:(}

Methylacmaphthylme

Table 2.2 P AH Identified in Flames

.......... __ ....... __ .. _---

53

Name

Struerure

Structure

Name

Methylpbcnantilrme

. H

-~-~

Z.phenylnapbthaknr

Table 2.2 P AlI Identified in Flames

Perylcne

Indenoj 1,2,3 -cd [pyrene

Beam[ ghi [peryleae + AathaDthrene

54

N ~

~i6ioroJ ~CgIgIgJ

available to the author by Dr. Wang from Penn Sate (1992). This section will present the

most recent and important conclusions concerning benzene formation and P AH formation

and growth in flames,

2.3.1 Formation of the First Aromatic Ring

The formation of the first aromatic ring in flames of non-aromatic fuels begins

usually with vinyl radical addition to acetylene (Frenklach, 1994a, 1994b)

high temperature

CZH3 + CzHz <=> [C,J-IsJ* > CJL + H

(2.65)

M, low temperature

-> n-CJ-Is

(2.66)

the chemical adduct decomposes at high temperatures to vinylacetylene, reaction (2.65),

while at relatively low temperatures, the stabilization channel predominates or reaction

(2.66). The structures of these species are described in Appendix G. Formation of benzene

then proceeds as follows
CJl4+H <=> n-eJ-I3 (2.67)

n-CJ-I3 + C2H2 +M <=> Q +M (2.68)
n-C.J-Is + CZH2 <=> Q +H (2.69) 55

The modelling work by Wang (1992) includes paths for the isomerization ofn-CJI3 and n-CJ-I5 as pointed out by Miller and Melius (1992), nevertheless Wang's results indicate that reactions (2,69) and (2.68) are the main paths for benzene formation in acetylene flames. Miller and Melius (1992) have proposed formation of benzene involving the chemical addition of prop argyl radicals

<=>

+M

(2.70)

However, the modelling work of Wang (1992) shows t~at reaction (2.70) is not an important channel for benzene fonnati on in acetyl ene flames. AI so as F renklack (1994b) points out, the precise mechanism for the reaction remains unclear, and the QRRK tratment of the mechanism proposed by Miller and Melius (1992) leads to linear C6It. species as the main product of reaction. Wang (1992) and Miller and Melius (1992) identify the main paths forformation of C3Hx species as

<=>

C3H3 +H C3H3 +H C3H2 + H

. (2.71) (2.72) (2.73)

C:zHz + CHz(s) CzHz + CHz CzHz + CH

<=>

<=>

The reaction paths for the decomposition of C3H" species in flames arc not well known.

2.3.2 Beyond the First Ring: PAR Formation & Growth

After formation of the first ring, aromatic growth takes place through the Habstraction-acetylene-addition (HACA) reaction sequence of Section 1.4 depicted in

56

Figure 2.3 from Frenklach (1994b)~ Acetylene is an abundant intermediate in fuel-rich

flames of hydrocarbons. As Frenklach (1994b) points out, some of the acetylene addition

reactions in the HAeA sequence form particularly stable aromatic molecules, like pyrene,

coronene, etc. The equilibrium constant for these reactions are so large that they are

practically irreversible. This has the effect of "pulling" the reaction sequence forward,

towards formation oflarger PAH molecules. Other acetylene addition steps are not so

favored thermodynamically, in which case the rate of the forward reaction is nearly

balanced by the rate of the reverse. These reversible steps create a thermodynamic barrier

to P AH growth.

Another route for P AH growth has been proposed by Colket (1994) who studied

the pyrolysis of toluene in shock tubes. In order to explain formation of naphthalene in the

pyrolysis experiments, the following overall reaction was proposed involving propargyl

and benzyl radical

<=>

+ 2H

(1.23)

Colket did not present the detailed mechanism for the reaction.

Sarofim et al. (1994) point out that aromatic growth involving aryl radicals are

believed to be important in diffusion flames, where P AH and soot formation are favored in

57

... H C ... H
~C a.~
0 +H O· +C2H2 ere' +H
-Hz -H -Hz •
'C2H2 ~
C6 00 •
... +H +<:2H2 00
~
-H2 -H
h
• Figure 2.3 HACA Mechanism (Frenklach, 1994b)

58

the fuel-rich side of the flame front. For example, the formation ofperylene is preceded by

reaction (2.74) involving naphthyl radical

<=>

+H

(2.74)

followed by reaction (2.75) after Hvabstraction from the aromatic ring

<=>

+

H

(2.75)

Reactions involving aryl radicals are also found to be important in the initial stages of

benzene pyrolisis (Frenklach, 1994b).

2.3.3 The Role of 5-Carbon Molecules in PAR Formation

Wang (1992) points out the lack ofinfonnation concerning 5-carbon chemistry in

flames and the role of odd-carbon compounds in the formation ofPAH. Colket (1994)

proposes the following reaction for formation of cyclopentadienyl radical starting from

acetylene

M

C3H3 + C2H2 <==> [1-CsHs-]* => I-CsHs-

(2.76)

59

[I-CsHs-]* <=>

{G· }' + (M)

(2.77)

==>

the activated adduct [1-CsHs-]* that forms by the addition reaction can isomerize to

cyclopentadienyl radical, reaction (2.77). Cyclopentadiene is then produced mainly by the

following reaction

O· +H

<=>

(2.78)

Another route for formation of cyclopentadiene in flames involves the oxidation of

benzene (Brezinsky, 1992). Phenoxy radical C6H50 is formed by the reaction of benzene

with oxygen atoms via reaction (2.79)

CJL; + 0

<=>

(2.79)

followed by reaction (2.80) forming cyclopentadienyl radical

< >

(2.80)

reaction (2.80) is then followed by reaction (2.78).

Another path proposed for the formation of cyclopentadiene is depicted in Figure

2.4 from the work of Louw et al. (1984) on the pyrolysis of benzene in a hydrogen

atmosphere. The addition of hydrogen atom to the benzene ring initates a series of

molecular isomerizations leading to cyclopentadienyl derivatives 3, 4 on Figure 2.4, and

finally by hydrogenation and loss of a methyl group to cyc1opentadiene. The overall

reaction is exothermic by -6.0 kcal.mole.

60

~o

[481 14

(lib) H:

CH,

6

Ill}

-. ., -:

{ll)O-------o- (41)0

! 8

.RLo~

c..H.+W __ (.j

( - 3) 44 - ----::0'"

[20) [521 [J I

(lla) H:

[731~ (II)

[Sl)U

,

H,

ScMmt! ( I: M; in kcaiimol, taken from Ihe iileralUre10 or cak:Jaled via group additivity"'"

Figure 2.4 Cylopentadiene from Benzene (Louw 1984)

61

CH,

(II) P CH,+

(34) (J

1

That a 5-carbon species may lead to the formation of aromatics was proposed by Louw and Manion (1989) based on experimental observations on the gas-phase hydrogenolysis of phenol. According to Louw, the overall reactions for phenol (ca. 6 vol %) in hydrogen at temperatures slightly over 1000 1< in a flow reactor with residence times not much longer than 3.5 sec. are as follows:

<=>

(2.81)

<=>

CJIsOH

(2.82)

In reaction (2.81) phenol is hydrogenated to benzene, and by reaction (2.82), phenol decomposes to cyclopentadiene. Minor species identified were P AH such as naphthalene, styrene, fluorene, phenanthrene, and anthracene. Of the PAH quantified, naphthalene constituted the main product In the experiments ofLouw, the hydrogenolysis ofa mixture of phenol and deuterated benzene (C6D6) also resulted inPAH formation but none of the P AlI contained deuterium. This important fact lead Louw to conclude that naphthalene could not form from benzene and was formed from cyclopentadiene according to the following overall reaction

<=>

+ 2Hz

(2.83)

No mechanism was given for reaction (2.83).

62

Baulch et al. (1992) based on the work of Smith (1979) on the high temperature

pyrolysis of toluene give the following reactions as major decomposition products of

benzyl radical (also proposed by Rao et al., 1986)

<==>

(2.84)

<==>

(2.85a)

The reverse of reaction (2.85a) is highly exothermic and constitues a route for the

formation of benzyl radical, an aromatic species, from a 5-carbon radical species and

acetylene. Colket and Seery (1994) proposed a low temperature route for the thermal

decomposition of benzyl radical involving a norbornadienyl intermediate as follows

(2.85b)

Colket' s route results in direct formation of cyclopentadicnyl radicals.

2.3.4 The Role of Chlorine in PAH Formation and Growth.

Chlorine radicals play an important role in P i\H formation and growth:

(1) Chlorine does not participate in the HACA growth mechanism for PAH nor it

participates in reaction (2.70) for example. However, chlorine effects PAH growth, first

63

indirectly, as a result of the weaker C-Cl bond that leads to easier pyrolysis ofCRC as

stated in Section 2.2.1. The lower temperature of pyrolysis results in higher stability of the

critical intermediate radicals such as CZH3 and n-CJI3 (Frenklach, 1990). The weaker C-

Cl bond also results in relatively high concentrations of chlorine atoms, which promotes

hydrocarbon degradation by Il-abstracrion.

(2) Kassem (1990) observed the earlier formation of vinyl acetylene and biacetylene with

increasing ClIH ratio of the unburned fuel. These are important intermediates in the

formation of benzene. As previously explained the flame i nhibi ting effects of chlorine delay

the oxidation of hydrocarbon intermediates that are important for PAH formation.

(3) A most important effect of chlorine occurs primarily through the activation of the

P AH by the following H-abstraction reaction

Aryl-H + Cl

<=>

(2.86)

Aryl- + Hel I

Table 2.3 shows a comparison of the foward rate coefficient for. reaction type (2.86) when

the aryl species is benzene versus the coefficient of reaction type (2.87)

Aryl-H + H

<=>

(2.87)

The rate coefficient expressions are given in the DCK1v1 of Appendix E. Inspection of

Table 2.2 reveals that kinetically there is very little difference between the two types ofH-

abstraction reactions. Furthermore, as Frenklach (1990) points out, the magnitude of the

equilibrium constants for both reactions is also very similar and the concentrations of Hz

and Hel can be expected to be of the same order of magnitude. It can be concluded,

therefore, that in order for reaction (2.86) to significantly affect PAH formation and

64

k1.86 kl.87

Aryl = benzene

Temperature "K

Forward Rate Coefficient (gmo/ cc-sec)

500

1000

1500

2.6 exp+7 3.4exp+7

8.0exp+lO 1.gexp+l0

1.1exp+12 I.Sexp+ 11

Table 2.3 Forward Rate Coefficients for Reactions (2.87), (2.88).

growth, the concentration of CI atoms must be larger than that ofH-atoms, and Frenklach

(1990) observes that the sooting tendency of flames increases with ClIH ratio in the

unburned fuel.

2.3.5 The Role of CIIH atoms in Soot Formation & Growth

In his experiments with methane and methane/methyl chloride flames with same

equivalence ratios, carbon density, and similar flame temperatures Huang and Senkan

(1996) found the surprising results that the methyl chloride flame produced less PAH but

nevertheless was more sooting. The methane and methane/methyl chloride mixtures had a

c/o ratio 0[0.63 and 0.75 respectively, and CIH ratios 0[0.25 and 0.286. Also, the post

flame concentrations of acetylene was about the same for both flames. In this section we

will try to explain this result and expand on the process for soot formation and the role CI

and H atoms play:

65

~RI~IUIWiiiAIII_''''''''''U'''''''IIiIRiiWIIiR_'IU_''''IIIR''AaTTR-.urtJl _

Soot consists mainly of elemental carbon but also contains 10 mol% and more of hydrogen. Soot emitted from typical pyrolysis and combustion systems is found to consist of a number (ranging from unity to many hundred) of "primary spheres" whose diameter are tipicall y in the range of 10-40 nm, The structure of soot particles has been examined with electron microscopy. Near the edge of the particle, bent carbon layers follow the shape of the particle surface. Inside the particles, lattice structure seems to be located more or less regularly around certain centers between which the structure is less ordered. Soot particle density is less than 2 glec due to large interplanar spacing. Finally, heat treatment improves the internal order of the soot particle, and the interplanar spacing approaches that of graphite.

As Mauss et al. (1994) explain H radicals playa crucial role in activating soot in flames via the reaction

soot + H

<=>

soot" + H2

(2.88)

Chlorine can also be said to playa similar role through an equivalent reaction

soot + Cl

<=>

soot* + He!

(2.89)

As discussed previously PAHare also activated by Hand Cl radicals as follows

PAH+H PAH+Cl

<=>

PAH* + H2 PAH* + Hel

(2.90) (2.91)

<=>

Soot particle inception takes place in the vicinity of the reaction zone of premixed laminar flames by the coagulation of large P AH molecules or

P AH + P AH* + _ repeats <=> SOOT

(2.92)

66

~--:;:~~ ::-.~ ac.ivated PAH molecule is fanned by the above reactions. For the first soot

: ::....-::.::~ :0 form, it is also necessary that there be a departure from planar geometry with :;.t Erst particle having a diameter of about 1.5-2.0 run.

The above reactions show. that as far as soot and P AH activation is concerned, the H and Cl atom chemistry is very similar, but in the activation of soot by chlorine via reaction (2.89) in comparison with reaction (2.88), one must recognize that the transport of chlorine radicals to the soot surface must be accounted for in the overall mechanism and be slower than the diffusion ofH atoms to the same surface. Similarly, the different sticking coefficients of chlorine and H atoms on the the soot surface need to be considered.

In reactions (2.88) and (2.90), high pressures of hydrogen gas would affect the position of equilibrium and the net rates of reaction, diminishing the production of both activated soot and P AH that are so important for soot growth. This effect has been recognized in the work by Mauss et al. (1994) which conclude that acetylene flames with higher product hydrogen partial pressures result in less soot formation.

The above observation may be able to explain the experimental results of Huang (1996). The methane flame results in a postflame hydrogen partial pressure 0[0.28 atm versus 0"12 atm for the methane/methyl chloride flame. Thus according to reaction (2.88), the methane flame should be less sooting in accordance to experiment since activation of soot needed for soot growth is impeded. Also note that activation ofPAH is affected via reaction (2.90).

67

Once soot and P AH are activated, P AH can add to soot growth via the following

condensation reactions
PAH* +- soot <==> soot*;+PAH (2.93)
PAH + soot* <--> soot*;+PAH (2.94)
PAH* + soot" < > soot;+PAH (2.95) In Huang's methyl chloride flame, the P AH is more effective! y activated due to the lower H2 concentrations and reaction (2.91), moreover reactions (2.93)-(2.95) above can provide an effective sink for the P AH perhaps leading to lower P AH concentrations in the gas phase as compared to the pure methane flame.

Mauss et al. also found that in the acetylene flames studied, soot growth (after inception) takes place mainly via acetylene addition in the later parts of the flame or

<=>

soot*;+1 + H

(2.96)

which is expected due to the large post-flame concentration of acetylene in their flames.

Beacause of the high post-flames temperatures (above 2000 1<.), Mauss et al. also found soot pyrolysis taking place to a large extent via the overall reaction

<=>

(2.97)

Because of the fuel-rich conditions of the flame, soot oxidation in their flame via the reactions below was only minor.

soot + OH

<=>

soot" +H20 500t;_1 + 2eo

(2.98) (2.99)

<=>

68

CHAPTER 3

mE ESTlMATION OF mERMOCHEMICALITRANSPORT PROPERTIES AND KINETIC COEFFICIENTS

3.1 Introduction

In Chapter 4, the mathematical treatment of a premixed laminar flame will be

presented. WIthin the flame structure, there are large concentration and temperature

gradients as a consequence of fast chemical reactions (see Figure 1_3). As we shall see in

Chapter 4~ because of the pres encc of such large gradien I 5, the sp eci es and energy balance

equations include transport properties such as the species diffusivities; thermochemical

properties, in the case of the energy balance, such as the species enthalpy also have to be

included to account for chemical reactions.To properly calculate the heat of reaction due

to a reversible reaction, a knowledge of the forward and reverse rate coefficients is

required, Similarly) the species balance requires a knowledge of the net rates of chemical

reactions within the flame structure to account for composition changes,

Thus, there are some fundamental thermochemical relations that are relevant in the

mat hemat ical treatment 0 f the laminar flame structu re. For an i deal gas, if the na tu ral

elements are taken as reference, the specific enthalpy for the kth species can be written as

follows

69

HP(D == M!~ (25) + f c" dT

I- J,r J p,1:

2~

(3.1)

where standard conditions are at LO atmosphere of pres sur c) mi,~(25)is the species heat

of formation at 25 °C, and Cp.k is the specific heat at constant pressure. The standard heat

of reactio n at temp erature T can th en be written as (5 and I er, 1989)

!:Jl:m(1) = L viMfi,~ (25) + L Vt f c;,idT

l" .t !s

(3.2)

where V,-:: is the stoichiometric coefficient for the kth species participating in the reaction,

and it is nega t ive fa r reactants.

Similarly, the standard entropy change for a chemical reaction is given by equation

(3.3)

(3_3)

where S; (25) is the absolute entropy for the kth species in the chemical reaction at 25 "C.

The properties given by equations (3,2) and (3.3) are important because from them

the standard free energy for the reaction at temperature T can be obtained as follows

AG::m (7) = !ill;" - TUS':" (T)

(3.4)

and the equilibrium constant for the reaction can then be estimated by equation (3.5)

(Sandler, 1989)

AG~(11;;;; -RT1nKa.;:ti"~

(3.5)

70

--~~-----~--. . .. _-_ ...

F urthermore, if the fo rward rate co effiei ent kr of a chemical re act io n is known. the reverse

rate coefficient k, is calculated as follows (by the princip Ie 0 f mi croscop ic reversibility)

(3_6)

(3.7)

where K, is the reaction equilibrium constant in concentration units.

To account for the change in species concentrations within the flame. the net rate

of formation for a given species has to be estimated. Consider J elementary reversible (or

irreversible) chemical reactions (Kee, 1993) involving K chemical species that can be

represented in the following general form

K K

L VkXk = L v~X k (i ... 1, , I)

k ... l h.1

(3.8)

where Xk is the chemical symbol for the kth species. The production rare rkofthe kth

species can be written in terms of the rate-of-progress variables qi for all reactions

invol ving the kth species

1

l1.t ~ L vkiq.. (k=L.,.; K)

j",l

(3.9)

where

. .

vAl ::::; VJ,j - v}d

(3_10)

and qi for the ith reaction is given by the difference of the forward and reverse rates as

K ... ~ K v;

qi .., k fi IT[ X~J - krin[ Xk]

k"'l k=,d

(3_11)

71

where [Xi] is the molar concentrati 0 n 0 f the kth speci es and klj and k, are the forward and

reverse nne c onstants of the it h react ion _

Finally, because of steep gradients in concentration for some species within the

flame, consideration of mass transport leads to the following expression for the ordinary

diffusion velocity of the kth species in the Curtis-Hirschfelder approximation (Kee, 1983)

(3.12)

where x.:. is the mole fraction, and where the mixture-averaged diffusion coefficient Daw,1.:

is given explicitly in terms of the binary diffusion coefficient Dj;; by

(3_l3)

More will be said concerning the binary difusion coefficient in Section 3.3,

In Appendices A-C, the thermochemical properties of the chemical species found

in the DCKlvl for methane and simple CHC are presented, These properties were taken for

the major part from the folIowing references:

(1 ) N Qnn al H ydroc arb on s

• IANAF Thermochemical Tables of Stull et al (1971)~ with much of the required data

for hydrocarbon species available in the form of polynomial coefficients in the

CHEl\.1KIN computer code of Sandia National Lab. (Kee et at 1993)_

(2) ChlQrinated Hydrocarbons (CHO

72

• Mostly from the works ofKarra (1988b)) Chang (l988b) and for trace species from Kassem (1990).

(3) PAH and chorinated·PAH

• From the work of Wang (1992) at Penn State University and the NIST DATABASE 25 (1991)_

• New Estimates were al so made as part 0 f thi s d esserta tion (see di s cession below)

As discussed above, it is also necessary to have estimates for transport properties of the chemical species composing the DCKM. The transport properties of Appendix. F were taken from the following references:

(1) Nanna! Hydrocarbons

• Kee et al (1983). Karra (1988b), and Chang (J 988b) (2) ChlQrinated Hydrocarbons (CHC)

• Karra (1988b), Chang (1988b) and for trace species from Kassem (1990) (3) PAH and chlorinated-PAH

• From the work of Wang (1992)

• New est i mar es were made in the cow rse of the wo r k present ed in this dissertation

In summary, the mathematical treatment of the premixed laminar flame structure requires knowledge 0 f therrn odynamic prop ert i es su ch 35 species heat of formati on) heat capacity, entropy, transport properties such as the binary diffusion coefficient, and kinetic coefficients for chemical reactions. If experimental or estimated values for these properties

73

were not available in the literature, it becomes necessary to make sound estimates by methods described in the sections that follow this introduction.

3.2 Estim a ti 0 n 0 f Th erm O( h em i c a] Pro pe rt ies

A most important objective of this dissertation has been the development of chemistry and kinetic parameters for the formation of P AH in flames. The emphasis on this section wiii be on methods that were used to estimate the thermochemistry of P AH in order to be able to model mathematically experiments conducted at UCLA dealing with simple hydrocarbons such as methane and CHC such as 1,1 DeE. The discussion is not meant to be comprehensive sin ce this is beyond the scope of thl s dissertation (only the main result s are presen ted), but enough references are given to rna ke it possible fo r the reader to find more extensive treatment of methods. used for estimating thermochemistry.

3.2.1 Conventional Methods

As the introduction in Section 3.1 shows, there are three important thermochemical properties of stable molecules that are required input in the mathematical models of premixed laminar flames: heat of formation, absolute entropy, and specific heat. Conventional methods of estimating themcchernical properties include methods that are highly empirical in nature, such as those based on various forms of additivity principles, as

74

well as those that arc based on the use of statistical mechanical calculations (Senkan, 1992). Statistical mechanics however is of no use in estimating the heat of formation of molecules.The discussion that follows is based mostly on the works of Benson (1916), Senkan (1992) ~ and Golden (1991).

There are empiricaJ metho ds based on add it i vi t y p rinci p les, The first level in the hierarchy of addit ivi ty methods is the bo n dad d i fiv i tv, r n thi s approach, the molecular properties can be considered as being made up of additive contributions from the individual bonds in the molecule, For example, the heat of formation of CH~C1 (Senkan, 1992) at 298 1( can be calculated as follows:

MJ.{298) = JMIrt:C~H) + lilliC-el)

= 3(-3.8) + (-7.4) = -] 8,8 kcal/rnol

where the bond contributions C-H and C-Cl can be found in Benson ( 1976), (A similar procedure would be used to estimate the heat capacity and absolute en tro py). Thi s estimate is within ·5% of the experimentally measured value of -19,6 kcal/mol. It has been found that bond additivity rules reproduce experimental heat capacity and entropy values within ± 1 caVmol-K on the average, but the error is greater for heavily branched compounds. Values of heat formation are generally estimated to be within z 2 kcal/mol but again are subject to large errors in heavily branched compounds. Bond additivity methods can not be employed to distinguish differences in properties of isomers such as nbutane and isobutane , for example.

7S

The next level in additivity hierarchy is group additivity. Properties are associated with groups making up the molecule, a group consisting of a polyvalent atom in a molecule together with all its ligands. For exampIe (Benson, 1976). the mo1ecule C}hCHOHCH} contains four groups as follows

2 C~-{C)(H)~

I C~-{C)2(O)(H)

I O-(C)(H)

Values of heat capacity and entropy estimated by group additivity are on the average within ±OJ cal/mol-K of the measured values, whereas heat of formation estimates are within iO.5 kcal/mol. For heavily substituted species, deviations in heat capacity and entropy may go as high as: ±l.S cal/mol-K, and the heat of formation may deviate by ±3 kcallmoL

Group additivity makes it possible to estimate the intrinsic entropy Sim of a chemical species. The absolute entropy is then given by

s~ ;;;; Sint + Rln(l]) - Rln(a) + Rln(gJ

(3.14)

where 11, c, and ~ (Sc "" 2s + I ) where s is the total spin) are the number of optical isomers, the total symmetry number. and electronic degeneracies, respectively. The symmetry number e is the total number of independent permutations of identical atoms or groups in a molecule that can be arrived by simple rotations. Both the internal (aim) and external (O'«et) symmetries must be considered in establishing the total symmetry number or

16

(3.15)

Group values of'hydrocarbcns and halogen-containing compounds for estimating heat capacity, intrinsic entropy, and heats of formation can be found in Benson (1976). Total symmetry number for common molecules can be found in Senkan (1992). The properties calculated by group additivity often need to be corrected for next-nearest-neighbor interactions such as cis) trans or gauche interactions, as well as nongroup interactions such as corrections due to ring-strain in cyclic molecules. Values for these corrections can be found in Benson (1976).

Grou p ad di ti vi t y has been us ed su ccesfun y to estirn ate the therrnod ynamic properties ofPAH by Stein and Benson (1977), Stein and Fahr (1985» and Wang (1992)' More recently group additivity was used to estimate the properties of fullerene precursors by Pope et al (1993) who used groups developed by Moiseeva (1990) to estimate the properties ofP i\H containing 5-carbon rings such as fluoranthene. Figure 3.1 shows the various groups existing in a P.A.H and the group additivity values taken from Stein and Benson (1977). Stein and Benson (1977) show that the average difference between predicted and measured heats 0 f fo [Ina tion for eleven P AH including pyrene, for example is <2 kcal/rnol, with the only exception being perylene for wich the error was 6.7 kcaIJmol and may be due to the inability of group additivity to account for "destabilization" of aromatic systems due to the presence of rings that contain only exo-type bonds. The average error for estimates of entropy and heat capacity wass less than 1 cal/mol-K. They

77