Low-Temperature Combustion and Autoignition

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ISBN: 9780444824851 | 0444824855
Cover: Hardcover
Copyright: 11/1/1997

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Combustion has played a central role in the development of our civilization which it maintains today as its predominant source of energy. The aim of this book is to provide an understanding of both fundamental and applied aspects of low-temperature combustion chemistry and autoignition. The topic is rooted in classical observational science and has grown, through an increasing understanding of the linkage of the phenomenology to coupled chemical reactions, to quite profound advances in the chemical kinetics of both complex and elementary reactions. The driving force has been both the intrinsic interest of an old and intriguing phenomenon and the centrality of its applications to our economic prosperity. The volume provides a coherent view of the subject while, at the same time, each chapter is self-contained.

Introduction

1 Basic chemistry of combustion

(124)

R.W. Walker

C. Morley

1.1 Historical perspective

(1)

1.2 Characteristics of low-temperature combustion

(3)

1.3 Computer modelling and associated problems

(5)

1.4 Overview of alkane oxidation

(8)

1.4.1 Introduction

(1)

1.4.2 Autoignition and engine knock

(3)

1.4.3 Regimes of oxidation chemistry

(5)

1.5 Review of experimental methods for establishing mechanisms and determining rate constants

(7)

1.5.1 Basic difficulties involved

(2)

1.5.2 Review of Hull approaches

(5)

1.6 Primary initiation reactions

(12)

1.6.1 Experimental determination of k(1)

(8)

1.6.2 Database for the primary initiation process (1)

(1)

1.6.3 Experimental determination of k(1A)

(1)

1.6.4 Relative rates of reactions (1) and (1A)

(1)

1.7 Propagation reaction X + RH XXX XH + R (2)

(8)

1.7.1 Introduction

(2)

1.7.2 Kinetic data for X = OH, H, HO(2), CH(3) and CH(3)O(2)

(6)

1.8 Homolysis of alkyl radicals

(4)

1.9 The reaction of alkyl radicals with O(2)

(8)

1.9.1 Reaction between C(2)H(5) and O(2)

(3)

1.10 Reactions of RO(2) radicals

(5)

1.11 Reactions of QOOH and QOOHO(2) radicals

(3)

1.12 Oxidation chemistry of CH(3) radicals

(3)

1.13 Reactions of alkoxy radicals

(2)

1.14 Branching reactions

(4)

1.15 Oxidation of cyclic alkanes

(9)

1.15.1 Oxidation of cyclohexane and cyclopentane

(5)

1.15.2 Formation of benzene

(2)

1.15.3 Mechanism of c-C(5)H(9) decomposition

(1)

1.15.4 Alkyl-substituted cycloalkanes

(1)

1.16 Oxidation of alkenes

(14)

1.16.1 Introduction

(4)

1.16.2 Product formation

(3)

1.16.3 Oxidation of isobutene

(1)

1.16.4 Oxidation of butene-1 and butene-2

(2)

1.16.5 Alkenyl oxidation chemistry

(3)

1.16.6 Oxidation of the smaller alkenyl radicals at high temperatures

(1)

1.17 Atom and radical addition to alkenes

(12)

1.17.1 H atoms

(1)

1.17.2 O atoms

(1)

1.17.3 HO(2) radicals

(5)

1.17.4 OH radicals

103

(4)

1.17.5 CH(3) radicals

107

(1)

1.18 Oxidation of oxygenated compounds

108

(6)

1.18.1 O-heterocycles

108

(3)

1.18.2 Aldehydes

111

(3)

1.19 Oxidation of aromatic compounds

114

(5)

1.20 Conclusions

119

(1)

References

120

(5)

2 Elementary reactions

125

(110)

S.H. Robertson

P.W. Seakins

M.J. Pilling

2.1 Introduction

125

(5)

2.2 Reaction initiation

130

(4)

2.3 Abstraction reactions

134

(19)

2.3.1 Introduction

134

(1)

2.3.2 Time resolved studies of OH abstraction reactions

135

(4)

2.3.3 Transition state theory (TST)

139

(4)

2.3.4 Isotope effects

143

(3)

2.3.5 Additivity of rate coefficients

146

(5)

2.3.6 Other radical abstractions

151

(2)

2.4 Radical decomposition reactions

153

(23)

2.4.1 Introduction

153

(6)

2.4.2 Real time experimental techniques for radical decompositions

159

(3)

2.4.3 Modelling radical decomposition

162

(9)

2.4.4 Microcanonical rate coefficients

171

(3)

2.4.5 Unimolecular dynamics

174

(2)

2.5 Radical recombination and association reactions

176

(23)

2.5.1 Introduction

176

(3)

2.5.2 CH(3) + CH(3) XXX C(2)H(6)

179

(9)

2.5.3 CH(3) + H XXX CH(4)

188

(5)

2.5.4 Theory and discussion

193

(2)

2.5.5 Addition reactions, equilibria and alkyl radical heats of formation

195

(2)

2.5.6 HO(2) self reaction

197

(2)

2.6 R + O(2) XXX RO(2)

199

(15)

2.6.1 Introduction

199

(2)

2.6.2 Experimental

201

(2)

2.6.3 Discussion

203

(2)

2.6.4 High temperature pathways

205

(9)

2.7 Peroxy radical isomerization

214

(8)

2.7.1 Introduction -- Formation of degenerate branching agents

214

(3)

2.7.2 Direct studies of peroxy radical isomerizations

217

(2)

2.7.3 Discussion

219

(3)

2.8 Theoretical and dynamical studies of the hydrogen/oxygen system

222

(8)

2.8.1 Introduction

222

(2)

2.8.2 State specific rate coefficients

224

(1)

2.8.3 Theoretical treatment of biomolecular reactions

225

(4)

2.8.4 Reagent excitation

229

(1)

References

230

(5)

3 Kinetics databases

235

(58)

D. L. Baulch

3.1 Data for combustion modelling

235

(3)

3.1.1 Modelling combustion chemistry

235

(1)

3.1.2 Data needs for modelling

236

(1)

3.1.3 Other uses of kinetic data in combustion

237

(1)

3.2 Primary sources of kinetic data: the need for evaluation

238

(19)

3.2.1 Experimentally measured rate constants

238

(5)

3.3.2 The quality of kinetic data

243

(11)

3.2.3 Critical evaluation

254

(3)

3.3 Evaluation of kinetic data

257

(15)

3.3.1 Evaluation groups

257

(1)

3.3.2 Collecting the information

258

(1)

3.3.3 Evaluation procedures

259

(13)

3.4 Interpolation, extrapolation and estimation procedures

272

(11)

3.5 Data sources for modelling

283

(3)

3.5.1 Collections of critically evaluated data

283

(3)

References

286

(7)

4. Mathematical tools for the construction, investigation and reduction of combustion mechanisms

293

(146)

A. S. Tomlin

T. Turanyi

M. J. Pilling

4.1 Introduction

293

(7)

4.2 Notation

300

(1)

4.3 The construction of combustion mechanisms

300

(12)

4.3.1 Matrix rearrangement

304

(1)

4.3.2 The logical programming approach

305

(1)

4.3.3 Applications to hydrocarbon oxidation

306

(2)

4.3.4 A comprehensive program system

308

(2)

4.3.5 The GRI mechanism

310

(1)

4.3.6 Discussion

311

(1)

4.4 Numerical investigation of complex models

312

(2)

4.4.1 Basic equations

312

(1)

4.4.2 Numerical integration

313

(1)

4.5 Sensitivity and uncertainty analysis

314

(12)

4.5.1 Introduction

314

(2)

4.5.2 Local sensitivities

316

(2)

4.5.3 Principal components

318

(2)

4.5.4 Applications of local concentration sensitivities

320

(3)

4.5.5 Uncertainty analysis

323

(2)

4.5.6 Discussion

325

(1)

4.6 Mechanism reduction without time-scale analysis

326

(16)

4.6.1 Finding redundant species

327

(2)

4.6.2 Finding redundant reactions

329

(1)

4.6.3 Sensitivity of temperature rates

330

(1)

4.6.4 Application to hydrogen oxidation in a flow system

331

(11)

4.6.5 Discussion

342

(1)

4.7 Formal lumping procedures

342

(16)

4.7.1 Linear lumping

344

(4)

4.7.2 Non-linear lumping

348

(2)

4.7.3 Chemical lumping

350

(4)

4.7.4 Lumping of continuous mixtures

354

(3)

4.7.5 Discussion

357

(1)

4.8 Reduction based on the investigation of time-scales

358

(34)

4.8.1 Low-dimensional systems

359

(1)

4.8.2 Jacobian analysis

359

(2)

4.8.3 Computational singular perturbation (CSP) theory

361

(3)

4.8.4 Slow/inertial manifolds

364

(9)

4.8.5 The quasi-steady-state approximation (QSSA)

373

(18)

4.8.6 Discussion

391

(1)

4.9 Approximate lumping in systems with time-scale separation

392

(11)

4.9.1 Linear lumping in systems with time-scale separation

392

(4)

4.9.2 Approximate non-linear lumping in systems with time-scale separation

396

(1)

4.9.3 Application of approximate non-linear lumping to the hydrogen/oxygen example

397

(4)

4.9.4 Discussion

401

(2)

4.10 Fitted kinetic models

403

(16)

4.10.1 Fitting a system of odes to experimental data

404

(5)

4.10.2 Fitting a system of odes to detailed kinetic simulations

409

(1)

4.10.3 Fitting algebraic equations to detailed kinetic simulations

410

(4)

4.10.4 A fitted algebraic model for wet CO ignition

414

(2)

4.10.5 Discussion

416

(3)

4.11 Conclusions and future directions

419

(20)

5 Global behaviour in the oxidation of hydrogen, carbon monoxide and simple hydrocarbons

439

(106)

S. K. Scott

5.1 Introduction

439

(1)

5.2 Notation

440

(2)

5.3 Non-linearity and feedback in chemical kinetics: stoichiometry and elementary steps

442

(9)

5.4 Chemical feedback: branched-chain ignition

451

(9)

5.5 Thermal feedback: ignition, extinction and singularity theory

460

(10)

5.6 Thermokinetic feedback: oscillations and local stability analysis

470

(17)

5.7 The H(2) + O(2) reaction: p-T(a) ignition limits in closed vessels

487

(7)

5.7.1 First limit

489

(1)

5.7.2 Second limit

490

(2)

5.7.3 Reactions involving HO(2) and the third limit

492

(2)

5.8 Flow reactor studies of the H(2) + O(2) reaction

494

(10)

5.9 Complexity in the oscillatory ignition region

504

(5)

5.10 Mechanistic modelling of complexity in the H(2) + O(2) reaction

509

(5)

5.11 The CO + O(2) reaction

514

(15)

5.11.1 Closed vessel studies

514

(2)

5.11.2 Open systems

516

(10)

5.11.3 Mechanistic interpretation and modelling

526

(3)

5.12 Hydrocarbon oxidation

529

(9)

5.12.1 Oxidation of acetaldehyde

530

(6)

5.12.2 Non-isothermal oxidation of alkanes

536

(2)

5.13 Conclusions and future directions

538

(3)

References

541

(4)

6 Experimental and numerical studies of oxidation chemistry and spontaneous ignition phenomena

545

(116)

J. F. Griffiths

C. Mohamed

6.1 Introduction

545

(1)

6.2 Measurements of reaction rate and its dependence on experimental conditions

546

(16)

6.2.1 Introduction

546

(2)

6.2.2 The overall dependence of reaction rate on temperature

548

(11)

6.2.3 Ignition delay times

559

(3)

6.3 Experimental methods

562

(13)

6.3.1 Introduction

562

(1)

6.3.2 Closed, constant volume reaction vessels

562

(1)

6.3.3 Flow systems

563

(2)

6.3.4 Shock tubes

565

(3)

6.3.5 Rapid compression machines

568

(4)

6.3.6 Motored engines

572

(1)

6.3.7 Chemical analysis

573

(2)

6.4 Global combustion phenomena associated with hydrocarbon oxidation

575

(19)

6.4.1 Introduction

575

(1)

6.4.2 Spontaneous ignition and oscillatory cool-flames in closed vessels

575

(3)

6.4.3 Spontaneous ignition in flowing gases

578

(1)

6.4.4 Ignition diagrams for selected hydrocarbons

579

(10)

6.4.5 Ignition delays of alkanes and other hydrocarbons

589

(5)

6.4.6 Spontaneous ignition in supercritical fluids

594

(1)

6.5 Product distributions during hydrocarbon oxidation and its kinetic interpretation

594

(35)

6.5.1 Introduction

594

(1)

6.5.2 Oxidation of propane and propene

595

(12)

6.5.3 Oxidation of hydrocarbons containing four carbon atoms

607

(5)

6.5.4 Oxidation of isomers of C(5) and C(6) alkanes

612

(8)

6.5.5 Oxidation of n-heptane and 2,2,4-trimethylpentane (i-octane)

620

(6)

6.5.6 Oxidation of C(n) alkanes and C(n) alkenes of (n Greater than 8)

626

(2)

6.5.7 Oxidation of aromatics

628

(1)

6.6 Detailed numerical modelling of alkane oxidation and spontaneous ignition

629

(11)

6.6.1 Introduction

629

(4)

6.6.2 Validation of comprehensive kinetic models for low-temperature oxidation

633

(5)

6.6.3 Application of comprehensive kinetic models

638

(2)

6.7 Conclusions

640

(3)

References

643

(10)

Appendix

653

(8)

7 Autoignition in spark-ignition engines

661

(100)

D. Bradley

C. Morely

7.1 Introduction

661

(3)

7.2 Fuels for spark-ignition engines

664

(20)

7.2.1 Composition and manufacture

664

(4)

7.2.2 Knock propensity and octane number

668

(2)

7.2.3 Research and motor octane numbers

670

(3)

7.2.4 Chemical cause of sensitivity

673

(2)

7.2.5 Blending

675

(4)

7.2.6 Anti-knocks

679

(5)

7.3 Chemical modelling of autoignition

684

(12)

7.3.1 Introduction

684

(2)

7.3.2 Comprehensive models

686

(2)

7.3.3 Reduced mechanisms

688

(1)

7.3.4 Simplified models

688

(8)

7.4 Combustion in engines

696

(13)

7.4.1 Laminar and turbulent burning velocities

696

(6)

7.4.2 Engine diagnostics and computational fluid dynamics

702

(4)

7.4.3 Parametric influences on burn rate

706

(3)

7.5 Autoignition in engines: modelling and experiments

709

(16)

7.5.1 Carry-over of combustion products between cycles

710

(3)

7.5.2 Cylinder wall deposits

713

(3)

7.5.3 End gas reactions: basic modelling considerations

716

(3)

7.5.4 Autoignition models applied to the end gas

719

(4)

7.5.5 Complete engine models

723

(2)

7.6 Development of pressure pulses and knock

725

(22)

7.6.1 Inhomogeneity, autoignition centres, and hot spots

725

(2)

7.6.2 Propagation of reaction from a hot spot and modes of autoignition

727

(3)

7.6.3 Propagation of autoignition: basic modelling considerations

730

(10)

7.6.4 Influence of the fuel

740

(4)

7.6.5 Multiple autoignition centres

744

(2)

7.6.6 Knock damage

746

(1)

7.7 Conclusions

747

(2)

References

749

(12)

Author Index

761

(24)

Subject Index

785

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Low-Temperature Combustion and Autoignition

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