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Conjoint Professor John Mackie

Conjoint Professor

School of Engineering (Chemical Engineering)

Career Summary

Biography

Research Expertise
Focus on Chemical Engineering

Qualifications

  • Doctor of Science, University of Sydney

Keywords

  • Chemical kinetics
  • Physical chemistry
  • chemical kinetics
  • high temperature chemistry
  • quantum chemistry
  • shock waves
  • thermodynamics

Fields of Research

Code Description Percentage
020299 Atomic, Molecular, Nuclear, Particle and Plasma Physics not elsewhere classified 10
090499 Chemical Engineering not elsewhere classified 10
091499 Resources Engineering and Extractive Metallurgy not elsewhere classified 80
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Publications

For publications that are currently unpublished or in-press, details are shown in italics.


(186 outputs)

Year Citation Altmetrics Link
2017 Dharmarathne NK, Mackie JC, Kennedy EM, Stockenhuber M, 'Gas phase pyrolysis of endosulfan and formation of dioxin precursors of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F)', PROCEEDINGS OF THE COMBUSTION INSTITUTE, 36 1119-1127 (2017) [C1]
DOI 10.1016/j.proci.2016.05.001
Citations Scopus - 1
Co-authors Michael Stockenhuber, Eric Kennedy
2017 Dharmarathne NK, Mackie JC, Kennedy EM, Stockenhuber M, 'Mechanism and Rate of Thermal Decomposition of Hexachlorocyclopentadiene and Its Importance in PCDD/F Formation from the Combustion of Cyclodiene Pesticides', Journal of Physical Chemistry A, 121 5871-5883 (2017) [C1]

© 2017 American Chemical Society. Thermal decomposition of hexachlorocyclopentadiene (HCCP) has been studied in inert gas and under oxidative conditions in a silica flow reactor ... [more]

© 2017 American Chemical Society. Thermal decomposition of hexachlorocyclopentadiene (HCCP) has been studied in inert gas and under oxidative conditions in a silica flow reactor at a residence time of 5.0 s between 690 and 923 K and 1 atm pressure. Pyrolysis was initiated by Cl bond fission to form pentachlorocyclopentadienyl radical; two such radicals then combined to undergo a series of intramolecular rearrangements and Cl fissions, producing principally octachloronaphthalene (8ClNP) and Cl 2 . This process has been studied by quantum chemical calculation, and a reaction potential energy surface has been developed. The rate constant of initial Cl atom fission has been calculated by canonical variational transition state theory as k = 1.45 × 10 15 exp(-222 ± 9 kJ mol -1 /RT) s -1 between 500 and 2000 K. A minimal kinetic model was developed to model the decomposition and major products. Oxidative decomposition was studied in nitrogen with O 2 contents of 1, 6, 12, and 20 mol %. Increasing O 2 to 6-8% increased the rate of decomposition of HCCP and decreased the yield of 8ClNP. Above 823 K, hexachlorobenzene (HCB) and CO became major products. The oxidative reaction has also been studied quantum chemically. At high O 2 content ( > ~10%), the rate of decomposition of HCCP declined as did yields of 8ClNP and HCB, but CO yields increased.

DOI 10.1021/acs.jpca.7b05209
Co-authors Michael Stockenhuber, Eric Kennedy
2016 Kundu SK, Kennedy EM, Mackie JC, Holdsworth CI, Molloy TS, Gaikwad VV, Dlugogorski BZ, 'Effect of methane on the conversion of HFC-134a in a dielectric barrier discharge non-equilibrium plasma reactor', Chemical Engineering Journal, 284 412-421 (2016) [C1]

© 2015 Elsevier B.V. The effect of methane on the conversion of HFC-134a (CF 3 CH 2 F) in a dielectric barrier discharge non-equilibrium plasma reactor was examined. Reactions we... [more]

© 2015 Elsevier B.V. The effect of methane on the conversion of HFC-134a (CF 3 CH 2 F) in a dielectric barrier discharge non-equilibrium plasma reactor was examined. Reactions were conducted in an argon bath gas and in the absence of oxygen and nitrogen. The products of the reaction include H 2 , HF, CHF 3 , CH 2 F 2 , C 2 H 6 , C 3 H 8 , C 2 H 3 F, CHF 2 CHF 2 , C 2 H 4 F 2 , C 3 H 7 F as well as a polymeric solid deposit. The polymeric materials are predominantly fluorine containing random copolymers, which can be categorised as fluoropolymers, constituted from various functional groups including CF 3 , CF 2 , CHF, CHF 2 , CH 2 F, CH 2 and CH 3 . While the presence of methane in the feed stream reduces the conversion level of CF 3 CH 2 F, it also modifies the polymer architecture. The addition of 1.25% methane with 12.5% CF 3 CH 2 F in an argon bath gas at 100cm 3 min -1 feed rate reduces the conversion of CF 3 CH 2 F from 74.5% to 46.8% and increases the formation of HF from 1500µmolh -1 to 2640µmolh -1 . The effect of methane addition on the electrical discharge and the reaction pathways are discussed.

DOI 10.1016/j.cej.2015.08.122
Citations Scopus - 3Web of Science - 3
Co-authors Bogdan Dlugogorski, Clovia Holdsworth, Eric Kennedy
2016 Gaikwad V, Kennedy E, Mackie J, Holdsworth C, Molloy S, Kundu S, et al., 'Reaction of dichloromethane under non-oxidative conditions in a dielectric barrier discharge reactor and characterisation of the resultant polymer', Chemical Engineering Journal, 290 499-506 (2016) [C1]

© 2016 Elsevier B.V. This paper presents the results of dichloromethane (DCM) decomposition to polymers utilising dielectric barrier discharge under non-oxidative reaction condit... [more]

© 2016 Elsevier B.V. This paper presents the results of dichloromethane (DCM) decomposition to polymers utilising dielectric barrier discharge under non-oxidative reaction conditions. The conversion levels, mass balance, reaction mechanism and polymer characterisation in relation to DCM reaction are presented in this paper. Reaction pathways describing the decomposition of DCM and subsequent formation of the major products are outlined. Speculation of the mechanism of formation of CHCl 3 and C 2 HCl 3 are supported by quantum chemical calculations. In addition, the effect of introducing methane in the reaction feed on the conversion level of DCM and the polymer structure is also examined in this paper.

DOI 10.1016/j.cej.2015.12.105
Co-authors Clovia Holdsworth, Bogdan Dlugogorski, Michael Stockenhuber, Eric Kennedy
2016 Kundu SK, Kennedy EM, Mackie JC, Holdsworth CI, Molloy TS, Gaikwad VV, Dlugogorski BZ, 'Experimental investigation of the reaction of HCFC-22 and methane in a dielectric barrier discharge non-equilibrium plasma', Chemical Engineering Journal, 301 73-82 (2016) [C1]

© 2016 Elsevier B.V. A dielectric barrier discharge non-equilibrium plasma was employed to study the reaction of HCFC-22 (CHClF 2 ) with methane (in an argon bath gas) at atmosph... [more]

© 2016 Elsevier B.V. A dielectric barrier discharge non-equilibrium plasma was employed to study the reaction of HCFC-22 (CHClF 2 ) with methane (in an argon bath gas) at atmospheric pressure and in the absence of oxygen and nitrogen. The reaction produced a fluorine-containing polymeric product, as well as gaseous species including H 2 , HF, HCl, CHF 3 , C 2 H 3 F, CH 3 Cl, CH 2 ClF, C 2 HClF 4 , CHCl 2 F, CH 2 Cl 2 and CCl 2 F 2 . While the main polymeric fraction is non-crosslinked, a small portion of the solid product is crosslinked. The polymers contain a wide range of functional gro ups including CH 3 , CH 2 , CHCl, CHF, CHClF, CHF 2 , CF 2 and CF 3 . The conversion level of CHClF 2 increased from 53% to 78%, with an increment in input energy density from 3 kJ L -1 to 13 kJ L -1 . A reaction mechanism is proposed explaining the formation of gaseous as well as polymeric products.

DOI 10.1016/j.cej.2016.04.133
Citations Scopus - 1Web of Science - 1
Co-authors Eric Kennedy, Bogdan Dlugogorski, Clovia Holdsworth
2016 Dharmarathne NK, Mackie JC, Kennedy EM, Stockenhuber M, 'Gas Phase Thermal Oxidation of Endosulfan and Formation of Polychlorinated Dibenzo-p-dioxins and Dibenzofurans', ENVIRONMENTAL SCIENCE & TECHNOLOGY, 50 10106-10113 (2016) [C1]
DOI 10.1021/acs.est.6b03280
Citations Scopus - 1Web of Science - 1
Co-authors Michael Stockenhuber, Eric Kennedy
2016 Kundu SK, Kennedy EM, Mackie JC, Holdsworth CI, Molloy TS, Gaikwad VV, Dlugogorski BZ, 'Experimental Study on the Reaction of CCl3F and CH4 in a Dielectric Barrier Discharge Nonequilibrium Plasma Reactor', INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, 55 463-471 (2016) [C1]
DOI 10.1021/acs.iecr.5b04010
Citations Scopus - 1Web of Science - 1
Co-authors Eric Kennedy, Clovia Holdsworth, Bogdan Dlugogorski
2015 Dorado JB, Dlugogorski BZ, Kennedy EM, Mackie JC, Gore J, Altarawneh M, 'S-Nitrosation of Aminothiones.', J Org Chem, 80 6951-6958 (2015) [C1]
DOI 10.1021/acs.joc.5b00313
Citations Scopus - 1Web of Science - 1
Co-authors Bogdan Dlugogorski, Eric Kennedy
2015 Suleiman IA, Radny MW, Gladys MJ, Smith PV, Mackie JC, Kennedy EM, Dlugogorski BZ, 'Thermodynamic stability and structure of cuprous chloride surfaces: A DFT investigation', Physical Chemistry Chemical Physics, 17 7038-7045 (2015) [C1]

This journal is © the Owner Societies 2015. Density functional theory together with ab initio atomistic thermodynamics has been utilized to study the structures and stabilities o... [more]

This journal is © the Owner Societies 2015. Density functional theory together with ab initio atomistic thermodynamics has been utilized to study the structures and stabilities of the low index CuCl surfaces. It is shown that the Cl-terminated structures are more stable than the Cu-terminated configurations, and that the defective CuCl(110)-Cu structure is more stable than the stoichiometric CuCl(110) surface. The equilibrium shape of a cuprous chloride nanostructure terminated by low-index CuCl surfaces has also been predicted using a Wulff construction. It was found that the (110) facets dominate at low chlorine concentration. As the chlorine concentration is increased, however, the contributions of the (100) and (111) facets to the Wulff construction also increase giving the crystal a semi-prism shape. At high chlorine concentration, and close to the rich limit, the (111) facets were found to be the only contributors to the Wulff construction, resulting in prismatic nanocrystals.

DOI 10.1039/c4cp05340k
Citations Scopus - 2Web of Science - 2
Co-authors Eric Kennedy, Phil Smith, Bogdan Dlugogorski, Michael Gladys, Marian Radny
2015 Dorado JB, Dlugogorski BZ, Kennedy EM, Mackie JC, Gore J, Altarawneh M, 'Decomposition of S-nitroso species', RSC ADVANCES, 5 29914-29923 (2015) [C1]
DOI 10.1039/c5ra03292j
Co-authors Eric Kennedy, Bogdan Dlugogorski
2015 Dharmarathne W, Mackie J, Kennedy E, Stockenhuber M, 'Non-Oxidative Thermal Decomposition of Endosulfan', Australian Combustion Symposium 2015 Proceedings (2015) [E1]
Co-authors Eric Kennedy, Michael Stockenhuber
2015 Mackie J, Dharmarathne W, Kennedy E, Stockenhuber M, 'Non-Oxidative Thermal Decomposition of Endosulfan II. Mechanism of Decomposition', Australian Combustion Symposium 2015 Proceedings (2015) [E1]
Co-authors Eric Kennedy, Michael Stockenhuber
2015 Kundu SK, Kennedy EM, Mackie JC, Molloy TS, Gaikwad VV, Dlugogorski BZ, Holdsworth CI, 'REACTION OF CCl3F (CFC-11) WITH CH4 IN A DIELECTRIC BARRIER DISCHARGE REACTOR', 2015 42ND IEEE INTERNATIONAL CONFERENCE ON PLASMA SCIENCES (ICOPS) (2015)
Co-authors Clovia Holdsworth, Eric Kennedy
2014 Kundu SK, Kennedy EM, MacKie JC, Holdsworth CI, Molloy TS, Gaikwad VV, Dlugogorski BZ, 'Nonequilibrium plasma polymerization of HFC-134a in a dielectric barrier discharge reactor: Polymer characterization and a proposed mechanism for polymer formation', IEEE Transactions on Plasma Science, 42 3095-3100 (2014) [C1]

© 2014 IEEE. Nonequilibrium plasma polymerization of hydrofluorocarbon HFC-134a CF 3 CH 2 F in argon bath gas has been studied in a dielectric barrier discharge reactor at atmos... [more]

© 2014 IEEE. Nonequilibrium plasma polymerization of hydrofluorocarbon HFC-134a CF 3 CH 2 F in argon bath gas has been studied in a dielectric barrier discharge reactor at atmospheric pressure and in the absence of oxygen and nitrogen. The reaction resulted in the formation of a polymeric solid fraction and the noncrosslinked properties of this material assisted in its characterization by solution state 13C} and 19F nuclear magnetic resonance spectroscopy. Gel permeation chromatography revealed that the polymers include low (number average molecular weight, M n values between 900 and 3000g~mol -1 and high (M n approximately 60000 g~mol -1 molecular weight fractions. A detailed polymerization mechanism is proposed, based on the published literature and the findings of the current investigation.

DOI 10.1109/TPS.2014.2303485
Citations Scopus - 4Web of Science - 4
Co-authors Eric Kennedy, Bogdan Dlugogorski, Clovia Holdsworth
2014 Suleiman IA, Radny MW, Gladys MJ, Smith PV, Mackie JC, Stockenhuber M, et al., 'Water formation via HCl oxidation on Cu(100)', APPLIED SURFACE SCIENCE, 299 156-161 (2014) [C1]
DOI 10.1016/j.apsusc.2014.01.204
Citations Scopus - 2Web of Science - 2
Co-authors Michael Stockenhuber, Marian Radny, Michael Gladys, Bogdan Dlugogorski, Phil Smith, Eric Kennedy
2014 Gaikwad V, Kennedy E, Mackie J, Holdsworth C, Molloy S, Kundu S, et al., 'Reaction of carbon tetrachloride with methane in a non-equilibrium plasma at atmospheric pressure, and characterisation of the polymer thus formed', Journal of Hazardous Materials, 280 38-45 (2014) [C1]

In this paper we focus on the development of a methodology for treatment of carbon tetrachloride utilising a non-equilibrium plasma operating at atmospheric pressure, which is not... [more]

In this paper we focus on the development of a methodology for treatment of carbon tetrachloride utilising a non-equilibrium plasma operating at atmospheric pressure, which is not singularly aimed at destroying carbon tetrachloride but rather at converting it to a non-hazardous, potentially valuable commodity. This method encompasses the reaction of carbon tetrachloride and methane, with argon as a carrier gas, in a quartz dielectric barrier discharge reactor. The reaction is performed under non-oxidative conditions. Possible pathways for formation of major products based on experimental results and supported by quantum chemical calculations are outlined in the paper. We elucidate important parameters such as carbon tetrachloride conversion, product distribution, mass balance and characterise the chlorinated polymer formed in the process. © 2014 Elsevier B.V.

DOI 10.1016/j.jhazmat.2014.07.049
Citations Scopus - 3Web of Science - 2
Co-authors Bogdan Dlugogorski, Eric Kennedy, Clovia Holdsworth, Michael Stockenhuber
2014 Kundu SK, Kennedy EM, MacKie JC, Holdsworth CI, Molloy TS, Gaikwad VV, Dlugogorski BZ, 'Characterization of polymer synthesized from the nonequilibrium plasma conversion of CFC-12 and methane in a dielectric barrier discharge reactor', Industrial and Engineering Chemistry Research, 53 19380-19386 (2014) [C1]

© 2014 American Chemical Society. A dielectric barrier discharge (DBD) nonequilibrium plasma reactor was employed to polymerize CFC-12 (CCl 2 F 2 , dichlorodifluoromethane) at at... [more]

© 2014 American Chemical Society. A dielectric barrier discharge (DBD) nonequilibrium plasma reactor was employed to polymerize CFC-12 (CCl 2 F 2 , dichlorodifluoromethane) at atmospheric pressure. The plasma polymerization of this saturated halogenated hydrocarbon was conducted in the presence of methane as reactant, in an argon bath gas and where the reaction environment was free from oxygen and nitrogen. The reaction resulted in the formation of non-cross-linked polymer product and whereby the non-cross-linked nature of the polymer enabled its characterization by solution state 13 C and 19 F nuclear magnetic resonance (NMR) spectroscopic analysis. The generated polymer was also analyzed by Fourier transform infrared (FTIR) spectrometry, and the spectra thus obtained were consistent with the analysis by NMR. The analyses of NMR and FTIR spectroscopy reveal the formation of fluoropolymers from the conversion of CFC-12.

DOI 10.1021/ie502564t
Citations Scopus - 4Web of Science - 3
Co-authors Clovia Holdsworth, Eric Kennedy
2014 Opoku MK, Dlugogorski BZ, Kennedy EM, Mackie JC, 'The effect of additive on nox emission during thermal decomposition of nano-recrystallised nitrate salts', Ceramic Transactions (2014) [E1]

In recent years, the use of nitrogenous industrial explosives has come under intense scrutiny by environmental agencies due to emission of toxic fumes to the atmosphere during bla... [more]

In recent years, the use of nitrogenous industrial explosives has come under intense scrutiny by environmental agencies due to emission of toxic fumes to the atmosphere during blasting of ammonium nitrate based explosives. Ammonium nitrate (AN) is a major ingredient in ammonium nitrate fuel oil (ANFO), and emulsion explosives, which are commonly applied in trench or surface mines blasting, and construction operations. It is well known that ammonium nitrate based explosives release toxic fumes (which contains NO and NO 2 emissions) under certain blasting condition, and/or oxygen rich explosive formulations. We investigated the effect of potassium on crystal structure, and thermal behaviour of ammonium nitrate. We observed multiphase structures in co-recrystallised ammonium nitrate containing low (2-4 mol %) and high ( > 25 mol %) concentrations of potassium in the crystallisation solution; mol % is based only on K + and NH 4 + . Co-recrystallised salts were characterise using X-ray diffraction (XRD), Scanning electron microscopy - energy dispersive spectroscopy (SEM-EDS), Inductively coupled plasma - optical emission spectroscopy (ICP-OES), and Thermogravimetric analyser and differential scanning calorimeter (TGA/DSC). In addition, we report concentration profiles of NO during thermal analyses of corecrystallised potassium ammonium nitrates. The results obtained from thermal decomposition of the co-recrystallised potassium ammonium nitrate salts showed decrease in production of NO. and 3-5 mol % K was the optimal concentration when compared with pure AN.

Co-authors Eric Kennedy, Bogdan Dlugogorski
2014 Ahmad K, Kennedy EM, Dlugogorski BZ, Mackie JC, Stockenhuber M, 'CO2 capture by amine-modified materials, tailored for enhanced adsorption capacity and selectivity', CHEMECA 2014 (2014) [E1]
Co-authors Michael Stockenhuber, Bogdan Dlugogorski, Eric Kennedy
2013 Altarawneh MK, Dlugogorski BZ, Kennedy EM, Mackie JC, 'Rate constants for reactions of ethylbenzene with hydroperoxyl radical', Combustion and Flame, 160 9-16 (2013) [C1]

A central step in the low-temperature oxidation of hydrocarbons is the abstraction of H by the hydroperoxyl radical (HO 2 ). In this study, reaction rate constants are derived the... [more]

A central step in the low-temperature oxidation of hydrocarbons is the abstraction of H by the hydroperoxyl radical (HO 2 ). In this study, reaction rate constants are derived theoretically for H abstraction by HO 2 from the three distinct locations of H in ethylbenzene (primary, secondary and aromatic H, with H on the ortho carbon taken as an example of unreactive aromatic H) as well as for the addition of HO 2 at the four possible aromatic sites. Potential energy surface is mapped out based on the results of computations performed with the composite CBS-QB3 theoretical method. Rate constants are fitted to modified Arrhenius forms in the wide temperature range of 300-2000K. The dominant channel at all temperatures is found to be H abstraction from the secondary C of the ethyl chain with a rate constant expression of k=1.28×10-24T3.70exp-5100Tcm3molecule-1s-1. Abstraction from the primary C also contributes significantly at higher temperatures ( > 800K) with a rate constant expression of k=2.90×10-24T3.78exp-8400Tcm3molecule-1s-1. Reasonable agreement was obtained with the limited experimental data available in the literature. Addition at the four sites of the aromatic ring and abstraction of one of the C-H aromatic bonds are relatively unimportant over the temperature range studied. We also investigate the abstraction of H from the secondary C on the ethyl chain by triplet oxygen and report the associated rate expression. The results presented herein should be useful in modelling the oxidation of alkylbenzenes at lower temperatures. © 2012.

DOI 10.1016/j.combustflame.2012.08.008
Citations Scopus - 7Web of Science - 7
Co-authors Bogdan Dlugogorski, Eric Kennedy
2013 Venpin WKPF, Kennedy EM, MacKie JC, Dlugogorski BZ, 'Comparative study of the physicochemical properties of ortho-substituted aromatic nitroso compounds', Journal of Chemical and Engineering Data, 58 1005-1010 (2013) [C1]

C-Nitroso compounds represent a class of chemical species with radical spin trapping capacity. They are widely employed to scavenge nitric oxide (NO) in biological and chemical sy... [more]

C-Nitroso compounds represent a class of chemical species with radical spin trapping capacity. They are widely employed to scavenge nitric oxide (NO) in biological and chemical systems and prospectively could be applied to reduce and control NO formation from important chemical processes. In this study, we examined the physicochemical properties of four ortho-substituted aromatic nitroso compounds, 3,5-dibromo-4-nitrosobenzenesulfonate (DBNBS), 4-nitrosobenzenesulfonate (NBS), 3,5-dimethyl-4-nitrosobenzenesulfonate (DMNBS), and 3,5-dichloro-4-nitrosobenzenesulfonate (DCNBS). These compounds, like most C-nitroso spin traps, exist in a monomer-dimer equilibrium, and only the monomeric form is active as a free radical spin scavenger. The influence of the aromatic ring substituent(s) on the dissociation of the dimer to give the monomer was investigated using UV-vis spectrophotometry. We describe the thermodynamic and kinetic parameters associated with the monomer-dimer equilibria, which allow us to provide a mechanistic understanding of NO trapping by C-nitroso compounds. © 2013 American Chemical Society.

DOI 10.1021/je400016c
Citations Scopus - 2Web of Science - 2
Co-authors Bogdan Dlugogorski, Eric Kennedy
2013 Juita, Dlugogorski BZ, Kennedy EM, Mackie JC, 'Roles of peroxides and unsaturation in spontaneous heating of linseed oil', Fire Safety Journal, 61 108-115 (2013) [C1]

This contribution aims to elucidate the chemical aspects of the autoxidation of linseed oil that may lead to self-heating and fires, especially for linseed oil doped with salts of... [more]

This contribution aims to elucidate the chemical aspects of the autoxidation of linseed oil that may lead to self-heating and fires, especially for linseed oil doped with salts of transition metals, in the presence of an additional fuel, such as cotton. We examine the formation of peroxides, which function as important intermediates in the autoxidation reaction. In particular, we describe the relationship between the formation of peroxides and changes in the degree of unsaturation, together with other structural and compositional modifications occurring in the molecules of unsaturated fatty acid esters. Transition metal salt catalysts were found to decompose peroxides which had built up during the autoxidation reaction of linseed oil, thereby increasing the number of reactive radicals and resulting in higher product yields. Higher temperatures increased the rate of peroxide decomposition. The overall activation energy for peroxide formation corresponds to 71±1 kJ mol -1 . FTIR analysis of oil film demonstrated the progressive decrease in the concentration of cis non-conjugated double bonds, formation of trans conjugated double bonds, appearance of hydroxyl groups and the broadening of the carbonyl peak. The overall rate of disappearance of double bonds follows first order kinetics with a rate constant of 0.030±0.007 h -1 . © 2013 Elsevier Ltd.

DOI 10.1016/j.firesaf.2013.07.005
Co-authors Eric Kennedy, Bogdan Dlugogorski
2013 Venpin WKPF, Kennedy EM, Mackie JC, Dlugogorski BZ, 'Trapping of Nitric Oxide, Generated during Sensitization of Ammonium Nitrate Emulsion Explosive, by Aromatic Nitroso Sulfonates', INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, 52 10561-10568 (2013) [C1]
DOI 10.1021/ie400263t
Co-authors Bogdan Dlugogorski, Eric Kennedy
2013 Altarawneh M, Dlugogorski BZ, Kennedy EM, Mackie JC, 'Theoretical investigation into the low-temperature oxidation of ethylbenzene', PROCEEDINGS OF THE COMBUSTION INSTITUTE, 34 315-323 (2013) [C1]
DOI 10.1016/j.proci.2012.06.066
Citations Scopus - 8Web of Science - 7
Co-authors Eric Kennedy, Bogdan Dlugogorski
2013 Summoogum SL, Wojtalewicz D, Altarawneh M, Mackie JC, Kennedy EM, Dlugogorski BZ, 'Formation of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F) by precursor pathways in oxidation of pesticide alpha-cypermethrin', PROCEEDINGS OF THE COMBUSTION INSTITUTE, 34 3499-3507 (2013) [C1]
DOI 10.1016/j.proci.2012.06.020
Citations Scopus - 4Web of Science - 4
Co-authors Bogdan Dlugogorski, Eric Kennedy
2013 Gaikwad V, Kennedy E, Mackie J, Holdsworth C, Molloy S, Kundu S, Dlugogorski B, 'Non-Oxidative Conversion of 1,2-Dichloroethane in a Non-Thermal Plasma and Characterisation of the Polymer Formed', PLASMA PROCESSES AND POLYMERS, 10 141-149 (2013) [C1]
DOI 10.1002/ppap.201200045
Citations Scopus - 3Web of Science - 1
Co-authors Eric Kennedy, Bogdan Dlugogorski, Clovia Holdsworth
2013 Kundu SK, Kennedy EM, Mackie JC, Holdsworth CI, Molloy TS, Gaikwad VV, Dlugogorski BZ, 'Study on the Reaction of CCl2F2 with CH4 in a Dielectric Barrier Discharge Nonequilibrium Plasma', PLASMA PROCESSES AND POLYMERS, 10 912-921 (2013) [C1]
DOI 10.1002/ppap.201300053
Citations Scopus - 4Web of Science - 4
Co-authors Eric Kennedy, Bogdan Dlugogorski, Clovia Holdsworth
2013 Hou S, Mackie JC, Kennedy EM, Dlugogorski BZ, 'Comparative study on the formation of toxic species from 4-chlorobiphenyl in fires: Effect of catalytic surfaces', Procedia Engineering, 62 350-358 (2013) [C1]

This contribution compares the formation of toxic species, polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F) and their precursors such as polychlorobenz... [more]

This contribution compares the formation of toxic species, polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F) and their precursors such as polychlorobenzenes (PCBz) and polychlorophenols (PCP), during oxidation of 4-chlorobiphenyl (4-CB) in a laboratory-scale apparatus, under conditions similar to those that occur in fires and waste combustion. The experiments were conducted using two gas flow reactors made of 99.5% alumina and high purity quartz, respectively. A sampling system intercepted the gaseous products leaving the reactors, trapping the volatile organic compounds (VOC; i.e., PCBz and PCP) and PCDD/F on a XAD-2 cartridge. The analysis of VOC involved high resolution gas chromatography (HRGC) - quadrupole mass spectrometry (QMS) while HRGC - ion trap (IT) MS/MS quantitated the PCDD/F produced. For the experiments using the alumina reactor, VOC analysis revealed the formation of PCBz and PCP, commencing at temperatures as low as 400 °C. Other products included benzaldehyde, naphthalene, 3-ethylbenzaldehyde, 1-chloro-4-ethynylbenzene and benzofuran. Gaseous species such as CO, CO 2 and HCl were detected and quantitated either by Fourier transform infra-red spectroscopy (FTIR) or ion chromatography (IC). Similar products were found to form in the quartz reactor, however, their formation commenced at 500 °C, with their yields significantly lower than those found for the alumina reactor. The present measurements indicate that surface reactions govern the oxidation of 4-CB between 300 and 650 °C for the alumina reactor, and between 450 and 600 °C for the quartz reactor. At 700 °C, both reactors operate similarly, with the oxidation process dominated by the gas phase reactions. With respect to dibenzo-p-dioxins and dibenzofurans, only isomers of chlorinated monochlorodibenzofuran (MCDF) and chlorinated dichlorodibenzofuran (DCDF) were found at low temperatures (300 to 450 °C), with 3-MCDF as the dominant congener. In our system, they appear to form in gas phase reactions involving 4-CB and singlet oxygen (1A g O 2 ), the latter generated on the reactor walls. The present results indicate that the combustion of 4-CB in fires will be dominated by catalytic surfaces of fly ash below 600 °C, and by gas-phase kinetics above 700 °C. © 2013 International Association for Fire Safety Science.

DOI 10.1016/j.proeng.2013.08.075
Citations Scopus - 3Web of Science - 3
Co-authors Bogdan Dlugogorski, Eric Kennedy
2013 Ahmad K, Mowla O, Kennedy EM, Dlugogorski BZ, Mackie JC, Stockenhuber M, 'A Melamine-Modified ß-Zeolite with Enhanced CO2 Capture Properties', Energy Technology, 1 345-349 (2013) [C1]
DOI 10.1002/ente.201300027
Citations Scopus - 8Web of Science - 8
Co-authors Bogdan Dlugogorski, Eric Kennedy, Michael Stockenhuber
2013 Altarawneh M, Mackie JC, Hou S, Kennedy EM, Dlugogorski BZ, 'Oxidation of a Model PCB (4-Chlorobiphenyl) in Catalytic and Non-Catalytic Flow Reactors and Formation of PCDF', Proceedings of the Australian Combustion Symposium (2013) [E1]
Co-authors Eric Kennedy, Bogdan Dlugogorski
2013 Holdsworth CI, Gaikwad V, Kennedy E, Mackie J, Molloy T, Kundu S, Dlugogorski B, 'Reaction of chloroform in a non-oxidative atmosphere using dielectric barrier discharge', 2013 19th IEEE Pulsed Power Conference (PPC) (2013) [E2]
DOI 10.1109/PPC.2013.6627401
Citations Scopus - 2
Co-authors Clovia Holdsworth, Eric Kennedy, Bogdan Dlugogorski
2013 Kundu SK, Kennedy EM, Mackie JC, Molloy TS, Gaikwad VV, Dlugogorski BZ, Holdsworth CI, 'Non-thermal plasma polymerization of HFC-134A in a dielectric barrier discharge reactor; polymer characterization and a proposed mechanism for polymer formation', IEEE Conference Publications (2013) [E2]
DOI 10.1109/PPC.2013.6627398
Citations Scopus - 1
Co-authors Clovia Holdsworth, Eric Kennedy, Bogdan Dlugogorski
2013 Kennedy EM, Kundu SK, Gaikwad VV, Molloy TS, King KM, Stockenhuber M, et al., 'Comparative study of the decomposition of CH4 in a nonequilibrium plasma and under high temperature pyrolytic conditions', Proceedings of the Australian Combustion Symposium 2013 (2013) [E1]
Co-authors Eric Kennedy, Michael Stockenhuber, Bogdan Dlugogorski
2012 Kundu SK, Kennedy EM, Mackie JC, Holdsworth CI, Molloy TS, Dlugogorski BZ, 'Conversion of HFC-134A to noncrosslinked fluoropolymer in a nonthermal plasma', Nonequilibrium Processes in Plasma, Combustion and Atmosphere, Torus Press, Moscow 165-173 (2012) [B1]
Co-authors Bogdan Dlugogorski, Clovia Holdsworth, Eric Kennedy
2012 Summoogum S, Altarawneh M, Mackie JC, Kennedy EM, Dlugogorski BZ, 'Oxidation of dibenzo-p-dioxin: Formation of initial products, 2-methylbenzofuran and 3-hydro-2-methylenebenzofuran', Combustion and Flame, 159 3056-3065 (2012) [C1]
Citations Scopus - 4Web of Science - 4
Co-authors Eric Kennedy, Bogdan Dlugogorski
2012 Rayson MS, Mackie JC, Kennedy EM, Dlugogorski BZ, 'Accurate rate constants for decomposition of aqueous nitrous acid', Inorganic Chemistry, 51 2178-2185 (2012) [C1]
Citations Scopus - 17Web of Science - 17
Co-authors Eric Kennedy, Bogdan Dlugogorski
2012 Chen K, Mackie JC, Kennedy EM, Dlugogorski BZ, 'Determination of toxic products released in combustion of pesticides', Progress in Energy and Combustion Science, 38 400-418 (2012) [C1]
Citations Scopus - 13Web of Science - 13
Co-authors Bogdan Dlugogorski, Eric Kennedy
2012 Juita, Dlugogorski BZ, Kennedy EM, Mackie JC, 'Identification and quantitation of volatile organic compounds from oxidation of linseed oil', Industrial & Engineering Chemistry Research, 51 5645-5652 (2012) [C1]
Citations Scopus - 10Web of Science - 5
Co-authors Eric Kennedy, Bogdan Dlugogorski
2012 Juita, Dlugogorski BZ, Kennedy EM, Mackie JC, 'Mechanism of formation of volatile organic compounds from oxidation of linseed oil', Industrial & Engineering Chemistry Research, 51 5653-5661 (2012) [C1]
Citations Scopus - 8Web of Science - 2
Co-authors Bogdan Dlugogorski, Eric Kennedy
2012 Venpin WKPF, Kennedy EM, Mackie JC, Dlugogorski BZ, 'Mechanistic study of trapping of NO by 3,5-dibromo-4-nitrosobenzene sulfonate', Industrial & Engineering Chemistry Research, 51 14325-14336 (2012) [C1]
Citations Scopus - 2Web of Science - 2
Co-authors Bogdan Dlugogorski, Eric Kennedy
2012 Kennedy EM, Kundu SK, Mackie JC, Holdsworth CI, Molloy TS, Gaikwad VV, Dlugogorski BZ, 'Conversion of fluorine-containing ozone-depleting and greenhouse gases to valuable polymers in a nonthermal plasma', Industrial and Engineering Chemistry Research, 51 11279-11283 (2012) [C1]
Citations Scopus - 13Web of Science - 14
Co-authors Bogdan Dlugogorski, Eric Kennedy, Clovia Holdsworth
2012 Juita, Dlugogorski BZ, Kennedy EM, Mackie JC, 'Low temperature oxidation of linseed oil: A review', Fire Science Reviews, 1 (2012) [C1]
DOI 10.1186/2193-0414-1-3
Co-authors Bogdan Dlugogorski, Eric Kennedy
2012 Hou S, Mackie JC, Kennedy EM, Dlugogorski BZ, 'Formation of mono and polychlorinated dibenzo-p-dioxins and furans in oxidation of 4-chlorobiphenyl', Organohalogen Compounds (2012) [E2]
Co-authors Eric Kennedy, Bogdan Dlugogorski
2012 Rahim RAA, Dlugogorski BZ, Kennedy EM, Mackie JC, 'Formation of polychlorinated phenols from photodegradation of 2,4,5-trichlorophenoxyacetic acid herbicide (2,4,5-T)', Organohalogen Compounds (2012) [E2]
Co-authors Eric Kennedy, Bogdan Dlugogorski
2011 Juita, Dlugogorski BZ, Kennedy EM, Mackie JC, 'Oxidation reactions and spontaneous ignition of linseed oil', Proceedings of the Combustion Institute, 33 2625-2632 (2011) [C1]
DOI 10.1016/j.proci.2010.06.096
Citations Scopus - 6Web of Science - 2
Co-authors Eric Kennedy, Bogdan Dlugogorski
2011 Chen K, Wojtalewicz DA, Altarawneh M, Mackie JC, Kennedy EM, Dlugogorski BZ, 'Formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) in oxidation of captan pesticide', Proceedings of the Combustion Institute, 33 701-708 (2011) [C1]
DOI 10.1016/j.proci.2010.07.069
Citations Scopus - 17Web of Science - 12
Co-authors Bogdan Dlugogorski, Eric Kennedy
2011 Suleiman IA, Radny MW, Gladys MJ, Smith PV, Mackie JC, Kennedy EM, Dlugogorski BZ, 'Chlorination of the Cu(110) surface and copper nanoparticles: A density functional theory study', Journal of Physical Chemistry C, 115 13412-13419 (2011) [C1]
DOI 10.1021/jp2036372
Citations Scopus - 13Web of Science - 12
Co-authors Eric Kennedy, Bogdan Dlugogorski, Marian Radny, Michael Gladys, Phil Smith
2011 Balucan RD, Kennedy EM, Mackie JC, Dlugogorski BZ, 'Optimization of antigorite heat pre-treatment via kinetic modeling of the dehydroxylation reaction for CO2 mineralization', Greenhouse Gases: Science and Technology, 1 294-304 (2011) [C1]
DOI 10.1002/ghg.33
Citations Scopus - 10Web of Science - 9
Co-authors Bogdan Dlugogorski, Eric Kennedy
2011 Altarawneh M, Al-Muhtaseb AH, Dlugogorski BZ, Kennedy EM, Mackie JC, 'Rate constants for hydrogen abstraction reactions by the hydroperoxyl radical from methanol, ethenol, acetaldehyde, toluene, and phenol', Journal of Computational Chemistry, 32 1725-1733 (2011) [C1]
DOI 10.1002/jcc.21756
Citations Scopus - 11Web of Science - 9
Co-authors Bogdan Dlugogorski, Eric Kennedy
2011 Suleiman IA, Mackie JC, Kennedy EM, Radny MW, Dlugogorski BZ, 'Quantum chemical study of copper (II) chloride and the Deacon reaction', Chemical Physics Letters, 501 215-220 (2011) [C1]
DOI 10.1016/j.cplett.2010.11.030
Citations Scopus - 7Web of Science - 7
Co-authors Eric Kennedy, Bogdan Dlugogorski, Marian Radny
2011 Chen K, Mackie JC, Kennedy EM, Dlugogorski BZ, 'Air pollutants formed in thermal decomposition of folpet fungicide under oxidative conditions', Environmental Science & Technology, 45 554-560 (2011) [C1]
DOI 10.1021/es102652w
Citations Scopus - 4Web of Science - 2
Co-authors Eric Kennedy, Bogdan Dlugogorski
2011 Rayson MS, Mackie JC, Kennedy EM, Dlugogorski BZ, 'Experimental study of decomposition of aqueous nitrosyl thiocyanate', Inorganic Chemistry, 50 7440-7452 (2011) [C1]
DOI 10.1021/ic102445d
Citations Scopus - 8Web of Science - 8
Co-authors Eric Kennedy, Bogdan Dlugogorski
2011 Summoogum S, Mackie JC, Kennedy EM, Delichatsios M, Dlugogorski BZ, 'Formation of toxic species and precursors of PCDD/F in thermal decomposition of alpha-cypermethrin', Chemosphere, 85 143-150 (2011) [C1]
Citations Scopus - 5Web of Science - 4
Co-authors Eric Kennedy, Bogdan Dlugogorski
2011 Chen K, Mackie JC, Wojtalewicz DA, Kennedy EM, Dlugogorski BZ, 'Toxic pollutants emitted from thermal decomposition of phthalimide compounds', Journal of Hazardous Materials, 187 407-412 (2011) [C1]
DOI 10.1016/j.jhazmat.2011.01.040
Citations Scopus - 3Web of Science - 3
Co-authors Bogdan Dlugogorski, Eric Kennedy
2011 Han W, Kennedy EM, Mackie JC, Dlugogorski BZ, 'Mechanistic study of the reaction of CHF3 with CH4', Chemical Engineering Journal, 166 822-831 (2011) [C1]
DOI 10.1016/j.cej.2010.11.049
Citations Scopus - 8Web of Science - 8
Co-authors Eric Kennedy, Bogdan Dlugogorski
2011 Suleiman IA, Radny MW, Gladys MJ, Smith PV, Mackie JC, Kennedy EM, Dlugogorski BZ, 'An equilibrium ab initio atomistic thermodynamics study of chlorine adsorption on the Cu(001) surface', Physical Chemistry Chemical Physics, 13 10306-10311 (2011) [C1]
DOI 10.1039/c0cp02211j
Citations Scopus - 11Web of Science - 11
Co-authors Eric Kennedy, Marian Radny, Michael Gladys, Bogdan Dlugogorski, Phil Smith
2011 Juita, Dlugogorski BZ, Kennedy EM, Mackie JC, 'Linseed oil and its tendency to self-heat', Fire Safety Science - Proceedings of the Tenth International Symposium (2011) [E1]
DOI 10.3801/iafss.fss.10-389
Co-authors Bogdan Dlugogorski, Eric Kennedy
2011 Chen K, Wojtalewicz DA, Mackie JC, Kennedy EM, Dlugogorski BZ, 'Toxicants formed in fires of captafol pesticide', Fire Safety Science - Proceedings of the Tenth International Symposium (2011) [E1]
DOI 10.3801/iafss.fss.10-227
Citations Scopus - 1
Co-authors Bogdan Dlugogorski, Eric Kennedy
2011 Summoogum S, Wojtalewicz DA, Mackie JC, Kennedy EM, Dlugogorski BZ, 'Formation of Polychlorinated Dibenzo-p-Dioxins and Polychlorinated Dibenzofurans and their precursors in fires of pyrethroid pesticide Alpha-Cypermethrin', Fire Safety Science - Proceedings of the Tenth International Symposium (2011) [E1]
DOI 10.3801/iafss.fss.10-239
Citations Scopus - 3
Co-authors Eric Kennedy, Bogdan Dlugogorski
2011 Alsoufi A, Dlugogorski BZ, Mackie JC, Stockenhuber M, Kennedy EM, 'Predicting the heat of formation of chlorinated phenols and associated chlorine isotopologues', Proceedings of the 11th Australian Combustion Symposium (2011) [E1]
Co-authors Bogdan Dlugogorski, Eric Kennedy, Michael Stockenhuber
2011 Hou S, Wojtalewicz DA, Mackie JC, Kennedy EM, Dlugogorski BZ, 'Formation of toxic species in oxidation of 4-chlorobiphenyl', Proceedings of the 11th Australian Combustion Symposium (2011) [E1]
Co-authors Bogdan Dlugogorski, Eric Kennedy
2011 Summoogum S, Dlugogorski BZ, Kennedy EM, Mackie JC, 'Low temperature oxidation of biphenyl in an alumina reactor: Possible initiation by O2 (1¿)', Proceedings of the 11th Australian Combustion Symposium (2011) [E1]
Co-authors Eric Kennedy, Bogdan Dlugogorski
2011 Altarawneh M, Dlugogorski BZ, Kennedy EM, Mackie JC, 'Rate constants for reactions of ethylbenzene with hydroperoxyl radical and oxygen molecule', Proceedings of the 11th Australian Combustion Symposium (2011) [E1]
Co-authors Bogdan Dlugogorski, Eric Kennedy
2010 Suleiman IA, Radny MW, Gladys MJ, Smith PV, Mackie JC, Kennedy EM, Dlugogorski BZ, 'Interaction of Chlorine and Oxygen with the Cu(100) Surface', The Journal of Physical Chemistry C, 114 19048-19054 (2010) [C1]
DOI 10.1021/jp1078983
Citations Scopus - 7Web of Science - 7
Co-authors Bogdan Dlugogorski, Marian Radny, Michael Gladys, Phil Smith, Eric Kennedy
2010 Altarawneh M, Dlugogorski BZ, Kennedy EM, Mackie JC, 'Theoretical study of reactions of HO2 in low-temperature oxidation of benzene', Combustion and Flame, 157 1325-1330 (2010) [C1]
DOI 10.1016/j.combustflame.2009.12.020
Citations Scopus - 9Web of Science - 9
Co-authors Bogdan Dlugogorski, Eric Kennedy
2010 Chen K, Mackie JC, Kennedy EM, Dlugogorski BZ, 'Thermal decomposition of captan and formation pathways of toxic air pollutants', Environmental Science & Technology, 44 4149-4154 (2010) [C1]
DOI 10.1021/es9037935
Citations Scopus - 9Web of Science - 9
Co-authors Bogdan Dlugogorski, Eric Kennedy
2010 Han W, Kennedy EM, Liu H, Li Y, Adesina AA, Mackie JC, Dlugogorski BZ, 'Catalytic pyrolysis of CHF3 over activated carbon and activated carbon supported potassium catalyst', Journal of Fluorine Chemistry, 131 698-703 (2010) [C1]
DOI 10.1016/j.jfluchem.2010.03.002
Citations Scopus - 8Web of Science - 6
Co-authors Eric Kennedy, Bogdan Dlugogorski
2010 Han W, Kennedy EM, Kundu SK, Mackie JC, Adesina AA, Dlugogorski BZ, 'Experimental and chemical kinetic study of the pyrolysis of trifluoroethane and the reaction of trifluoromethane with methane', Journal of Fluorine Chemistry, 131 751-760 (2010) [C1]
DOI 10.1016/j.jfluchem.2010.03.012
Citations Scopus - 26Web of Science - 20
Co-authors Eric Kennedy, Bogdan Dlugogorski
2010 Alsoufi A, Altarawneh M, Dlugogorski BZ, Kennedy EM, Mackie JC, 'A DFT study on the self-coupling reactions of the three isomeric semiquinone radicals', Journal of Molecular Structure: THEOCHEM, 958 106-115 (2010) [C1]
DOI 10.1016/j.theochem.2010.07.036
Citations Scopus - 4Web of Science - 4
Co-authors Eric Kennedy, Bogdan Dlugogorski
2010 Altarawneh M, Radny MW, Smith PV, Mackie JC, Kennedy EM, Dlugogorski BZ, et al., 'Adsorption of 2-chlorophenol on Cu2O(111)-CuCUS: A first-principles density functional study', Applied Surface Science, 256 4764-4770 (2010) [C1]
DOI 10.1016/j.apsusc.2010.01.101
Citations Scopus - 6Web of Science - 6
Co-authors Eric Kennedy, Marian Radny, Bogdan Dlugogorski, Phil Smith
2010 Han W, Kennedy EM, Mackie JC, Dlugogorski BZ, 'Conversion of CHF3 to CH2=CF2 via reaction with CH4 in the presence of CBrF3: An experimental and kinetic modelling study', Journal of Hazardous Materials, 180 181-187 (2010) [C1]
DOI 10.1016/j.jhazmat.2010.04.011
Citations Scopus - 12Web of Science - 13
Co-authors Bogdan Dlugogorski, Eric Kennedy
2010 Han W, Kennedy EM, Mackie JC, Dlugogorski BZ, 'Conversion of a CFCs, HFCs and HCFCs waste mixture via reaction with methane', Journal of Hazardous Materials, 184 696-703 (2010) [C1]
DOI 10.1016/j.jhazmat.2010.08.095
Citations Scopus - 2Web of Science - 2
Co-authors Bogdan Dlugogorski, Eric Kennedy
2010 Han W, Kennedy EM, Mackie JC, Dlugogorski BZ, 'Effect of methanol on the gas-phase reaction of trifluoromethane with methane', Industrial & Engineering Chemistry Research, 49 8406-8414 (2010) [C1]
DOI 10.1021/ie100349x
Citations Scopus - 6Web of Science - 7
Co-authors Eric Kennedy, Bogdan Dlugogorski
2010 Han W, Kennedy EM, Mackie JC, Dlugogorski BZ, 'Synthesis of vinylidene fluoride via reaction of chlorodifluoromethane (HCFC-22) with methane', Industrial and Engineering Chemistry Research, 49 6010-6019 (2010) [C1]
DOI 10.1021/ie100338j
Citations Scopus - 3Web of Science - 3
Co-authors Eric Kennedy, Bogdan Dlugogorski
2010 Altarawneh M, Dlugogorski BZ, Kennedy EM, Mackie JC, 'Theoretical study of unimolecular decomposition of catechol', Journal of Physical Chemistry A, 114 1060-1067 (2010) [C1]
DOI 10.1021/jp909025s
Citations Scopus - 22Web of Science - 18
Co-authors Eric Kennedy, Bogdan Dlugogorski
2010 Altarawneh M, Dlugogorski BZ, Kennedy EM, Mackie JC, 'Thermochemical properties and decomposition pathways of three isomeric semiquinone radicals', Journal of Physical Chemistry A, 114 1098-1108 (2010) [C1]
DOI 10.1021/jp9091706
Citations Scopus - 19Web of Science - 15
Co-authors Eric Kennedy, Bogdan Dlugogorski
2010 Rayson MS, Altarawneh M, Mackie JC, Kennedy EM, Dlugogorski BZ, 'Theoretical study of the ammonia-hypochlorous acid reaction mechanism', Journal of Physical Chemistry A, 114 2597-2606 (2010) [C1]
DOI 10.1021/jp9088657
Citations Scopus - 17Web of Science - 16
Co-authors Bogdan Dlugogorski, Eric Kennedy
2010 Altarawneh M, Al-Muhtaseb AH, Dlugogorski BZ, Kennedy EM, Mackie JC, 'Theoretical study on the thermodynamic properties and self-decomposition of methylbenzenediol Isomers', Journal of Physical Chemistry A, 114 11751-11760 (2010) [C1]
DOI 10.1021/jp1054765
Citations Scopus - 4Web of Science - 3
Co-authors Eric Kennedy, Bogdan Dlugogorski
2009 Altarawneh M, Radny MW, Smith PV, Mackie JC, Kennedy EM, Dlugogorski BZ, et al., 'A first-principles density functional study of chlorophenol adsorption on Cu2O(110):CuO', Journal of Chemical Physics, 130 184505 (2009) [C1]
DOI 10.1063/1.3123534
Citations Scopus - 11Web of Science - 8
Co-authors Bogdan Dlugogorski, Marian Radny, Phil Smith, Eric Kennedy
2009 Altarawneh M, Carrizo D, Ziolkowski AM, Kennedy EM, Dlugogorski BZ, Mackie JC, 'Pyrolysis of permethrin and formation of precursors of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) under non-oxidative conditions', Chemosphere, 74 1435-1443 (2009) [C1]
DOI 10.1016/j.chemosphere.2008.12.033
Citations Scopus - 18Web of Science - 17
Co-authors Eric Kennedy, Bogdan Dlugogorski
2009 Altarawneh M, Dlugogorski BZ, Kennedy EM, Mackie JC, 'Mechanisms for formation, chlorination, dechlorination and destruction of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs)', Progress in Energy and Combustion Science, 35 245-274 (2009) [C1]
DOI 10.1016/j.pecs.2008.12.001
Citations Scopus - 203Web of Science - 179
Co-authors Eric Kennedy, Bogdan Dlugogorski
2009 Altarawneh M, Dlugogorski BZ, Kennedy EM, Mackie JC, 'Rate constants for hydrogen abstraction reactions by the hydroperoxyl radical from methanol, ethenol, acetaldehyde, toluene and phenol', Proceedings of the Australian Combustion Symposium 2009 (2009) [E1]
DOI 10.1002/jcc.21756
Co-authors Bogdan Dlugogorski, Eric Kennedy
2009 Juita, Dlugogorski BZ, Kennedy EM, Mackie JC, 'Low temperature oxidation reactions of linseed oil and its active components', Proceedings of the Australian Combustion Symposium 2009 (2009) [E1]
Co-authors Bogdan Dlugogorski, Eric Kennedy
2009 Suleiman IA, Radny MW, Gladys MJ, Smith PV, Mackie JC, Kennedy EM, Dlugogorski BZ, 'Dissociative adsorption of molecular oxygen on the Cu(001) surface: A density functional theory study', Proceedings of the Australian Combustion Symposium 2009 (2009) [E1]
Co-authors Eric Kennedy, Marian Radny, Michael Gladys, Bogdan Dlugogorski, Phil Smith
2009 Summoogum S, Mackie JC, Kennedy EM, Dlugogorski BZ, 'Pyrolysis and decomposition pathways of alphacypermethrin under non-oxidative conditions', Proceedings of the Australian Combustion Symposium 2009 (2009) [E1]
Co-authors Eric Kennedy, Bogdan Dlugogorski
2009 Chen K, Wojtalewicz DA, Mackie JC, Kennedy EM, Dlugogorski BZ, 'Formation of toxic species in thermal decomposition of Captan', Proceedings of the Australian Combustion Symposium 2009 (2009) [E1]
Co-authors Bogdan Dlugogorski, Eric Kennedy
2008 Altarawneh M, Dlugogorski BZ, Kennedy EM, Mackie JC, 'Quantum chemical and kinetic study of formation of 2-chlorophenoxy radical from 2-chlorophenol: Unimolecular decomposition and bimolecular reactions with H, OH, Cl, and O-2', Journal of Physical Chemistry A, 112 3680-3692 (2008) [C1]
DOI 10.1021/jp712168n
Citations Scopus - 25Web of Science - 27
Co-authors Eric Kennedy, Bogdan Dlugogorski
2008 Altarawneh M, Kennedy EM, Dlugogorski BZ, Mackie JC, 'Computational study of the oxidation and decomposition of dibenzofuran under atmospheric conditions', Journal of Physical Chemistry A, 112 6960-6967 (2008) [C1]
DOI 10.1021/jp800093j
Citations Scopus - 21Web of Science - 19
Co-authors Bogdan Dlugogorski, Eric Kennedy
2008 Han W, Yu H-S, Kennedy EM, Mackie JC, Dlugogorski BZ, 'Conversion of CHF3 to CH2 = CF2 via reaction with CH4 and CaBr2', Environmental Science & Technology, 42 5795-5799 (2008) [C1]
DOI 10.1021/es8004877
Citations Scopus - 13Web of Science - 13
Co-authors Eric Kennedy, Bogdan Dlugogorski
2008 Altarawneh M, Radny MW, Smith PV, Mackie JC, Kennedy EM, Dlugogorski BZ, '2-chlorophenol adsorption on Cu(100): First-principles density functional study', Surface Science, 602 1554-1562 (2008) [C1]
DOI 10.1016/j.susc.2008.02.029
Citations Scopus - 9Web of Science - 9
Co-authors Eric Kennedy, Bogdan Dlugogorski, Marian Radny, Phil Smith
2008 Altarawneh M, Radny MW, Smith PV, Mackie JC, Kennedy EM, Dlugogorski BZ, 'Adsorption of chlorophenol on the Cu(111) surface: A first-principles density functional theory study', Applied Surface Science, 254 4218-4224 (2008) [C1]
DOI 10.1016/j.apsusc.2008.01.045
Citations Scopus - 16Web of Science - 16
Co-authors Bogdan Dlugogorski, Eric Kennedy, Phil Smith, Marian Radny
2008 Yu H, Kennedy EM, Ong W-H, Mackie JC, Han W, Dlugogorski BZ, 'Experimental and kinetic studies of gas-phase pyrolysis of n-C4F10', Industrial & Engineering Chemistry Research, 47 2579-2584 (2008) [C1]
DOI 10.1021/ie071400z
Citations Scopus - 11Web of Science - 10
Co-authors Bogdan Dlugogorski, Eric Kennedy
2008 Han W, Yu H, Kennedy EM, Mackie JC, Dlugogorski BZ, 'Catalytic pyrolysis of CHF3 over K2-XO/AC catalyst', Chemeca2008 (2008) [E1]
Co-authors Bogdan Dlugogorski, Eric Kennedy
2007 Altarawneh M, Dlugogorski BZ, Kennedy EM, Mackie JC, 'Quantum chemical investigation of formation of polychlorodibenzo-p-dioxins and dibenzofurans from oxidation and pyrolysis of 2-chlorophenol', Journal of Physical Chemistry A, 111 2563-2573 (2007) [C1]
DOI 10.1021/jp065558t
Citations Scopus - 55Web of Science - 51
Co-authors Bogdan Dlugogorski, Eric Kennedy
2007 Altarawneh M, Dlugogorski BZ, Kennedy EM, Mackie JC, 'Theoretical study of reaction pathways of dibenzofuran and dibenzo-p-dioxin under reducing conditions', Journal of Physical Chemistry A, 111 7133-7140 (2007) [C1]
DOI 10.1021/jp071166q
Citations Scopus - 20Web of Science - 18
Co-authors Eric Kennedy, Bogdan Dlugogorski
2007 Sun Q, Mackie JC, Dlugogorski BZ, Kennedy EM, 'Theoretical exploration of the potential energy surface of the HOI -> HIO isomerization reaction', Chemical Physics Letters, 436 68-74 (2007) [C1]
DOI 10.1016/j.cplett.2007.01.049
Citations Scopus - 5Web of Science - 5
Co-authors Eric Kennedy, Bogdan Dlugogorski
2007 Sun Q, Altarawneh M, Dlugogorski BZ, Kennedy EM, Mackie JC, 'Catalytic effect of CuO and other transition metal oxides in formation of dioxins: Theoretical investigation of reaction between 2,4,5-trichlorophenol and NO', Environmental Science & Technology, 41 5708-5715 (2007) [C1]
DOI 10.1021/es062354h
Citations Scopus - 27Web of Science - 26
Co-authors Bogdan Dlugogorski, Eric Kennedy
2007 Yu H, Kennedy EM, Mackie JC, Dlugogorski BZ, 'Simultaneous conversion of CHClF2 and CH3Br to CH2CF2', Chemosphere, 68 2003-2006 (2007) [C1]
DOI 10.1016/j.chemosphere.2007.01.065
Citations Scopus - 8Web of Science - 8
Co-authors Eric Kennedy, Bogdan Dlugogorski
2007 Altarawneh M, Radny MW, Smith PV, Mackie JC, Kennedy EM, Dlugogorski BZ, '2-chlorophenol adsorption on the Cu(001) and Cu(111) surfaces: First principles density functional study', 3rd International Workshop on Surface Physics Nanostructures on Surfaces. Programme and Abstracts (2007) [E3]
Co-authors Eric Kennedy, Marian Radny, Bogdan Dlugogorski, Phil Smith
2007 Altarawneh M, Dlugogorski BZ, Kennedy EM, Mackie JC, 'A theoretical study of the reactions of HO2 in the low temperatures oxidation of benzene', Proceedings of the Australian Combustion Symposium 2007 (2007) [E1]
Co-authors Eric Kennedy, Bogdan Dlugogorski
2006 Yu H, Mackie JC, Kennedy EM, Dlugogorski BZ, 'Experimental and quantum chemical study of the reaction CF2+CH3 CF2CH3 -> CH2=CF2+H: A key mechanism in the reaction between methane and fluorocarbons', Industrial & Engineering Chemistry Research, 45 3758-3762 (2006) [C1]
DOI 10.1021/ie060221z
Citations Scopus - 11Web of Science - 11
Co-authors Eric Kennedy, Bogdan Dlugogorski
2006 Yu H, Kennedy EM, Mackie JC, Dlugogorski BZ, 'An experimental and kinetic modeling study of the reaction of CHF3 with methane', Environmental Science & Technology, 40 5778-5785 (2006) [C1]
DOI 10.1021/es0604212
Citations Scopus - 17Web of Science - 16
Co-authors Eric Kennedy, Bogdan Dlugogorski
2006 Altarawneh M, Dlugogorski BZ, Kennedy EM, Mackie JC, 'Quantum chemical study of low temperature oxidation mechanism of dibenzofuran', Journal of Physical Chemistry A, 110 13560-13567 (2006) [C1]
DOI 10.1021/jp065135r
Citations Scopus - 19Web of Science - 17
Co-authors Eric Kennedy, Bogdan Dlugogorski
2006 Yu H, Kennedy EM, Mackie JC, Dlugogorski BZ, 'Studies of the Reaction of CHF3 with Methane', 16th Halon Options Technical Working Conference (2006) [E2]
Co-authors Bogdan Dlugogorski, Eric Kennedy
2006 Yu H, Kennedy EM, Mackie JC, Dlugogorski BZ, 'A Novel Process for Conversion of Fluorochemicals to Fluoromonomers', 31st International Symposium on Combustion (2006) [E3]
Co-authors Bogdan Dlugogorski, Eric Kennedy
2006 Altarawneh M, Mackie JC, Kennedy EM, Dlugogorski BZ, 'A Quantum Chemical Study of the Low Temperature Oxidation of Dibenzofuran', 31st International Symposium on Combustion (2006) [E3]
Co-authors Bogdan Dlugogorski, Eric Kennedy
2006 Ziolkowski AM, Dlugogorski BZ, Mackie JC, Tame NW, Kennedy EM, 'Experimental Studies on Thermal Behaviour of Permethrin', 31st International Symposium on Combustion (2006) [E3]
Co-authors Eric Kennedy, Bogdan Dlugogorski
2005 Bacskay GB, Mackie JC, 'Oxidation of CO by so2: A theoretical study', Journal of Physical Chemistry A, 109 2019-2025 (2005)

The elementary reaction SO 2 + CO ¿ CO 2 + SO( 3 ¿) (1) and the subsequent reaction SO( 3 ¿) + CO ¿ CO 2 + S( 3 P) (2) have been studied by the application of the Gaussian-... [more]

The elementary reaction SO 2 + CO ¿ CO 2 + SO( 3 ¿) (1) and the subsequent reaction SO( 3 ¿) + CO ¿ CO 2 + S( 3 P) (2) have been studied by the application of the Gaussian-3//B3LYP quantum chemical approach to characterize the potential energy surfaces and transition state kinetic analysis to derive rate coefficients. Reaction 1 is found to take place via two transition states (TS), a cis-OSOCO TS and a trans-OSOCO TS. Reaction via the cis-TS is concerted and takes place on a singlet surface. Intersystem crossing to the final products occurs after passage through the barrier on the singlet surface. The trans-TS leads to a very weakly bound singlet OSOCO intermediate that then passes through a second TS (on the triplet surface) to form the products. Reaction 2 takes place on triplet surfaces. There is a concerted reaction through a cis-SOCO TS and a weakly bound trans-SOCO has also been identified. Reaction 2 is analogous to the reaction CO + O 2 ( 3 ¿) ¿ CO 2 + O( 3 P) (3), and this reaction has been reinvestigated at a similar level of theory and the rate coefficient derived by quantum chemistry is compared with experiment. The sensitive effects of trace impurities such as H 2 , H 2 O, and hydrocarbons on the accurate experimental determination of the rate coefficient of reaction 3 is discussed. Using rate coefficients for reactions 1 and 2 obtained via quantum chemical calculations, we have been unable to model the extent of decomposition of SO 2 measured in a shock tube study of reaction between SO 2 and CO [Bauer, S. H.; Jeffers, P.; Lifshitz, A.; Yadava, B. P. Proc. Combust. Inst. 1971, 13, 417]. In light of the known sensitivity of reaction 3 to trace impurities, we have incorporated trace amounts of H 2 , CH 4 , or H 2 O, together with our rate coefficients for (1) and (2), in a kinetic model of Alzueta et al. [Combust. Flame 2001, 727, 2234], which is then shown to be able to substantially model the SO 2 data of Bauer et al. In the course of this modeling study we also computed heats of formation for a number of sulfur-containing small molecules: HS, HSO, HSOH, HOSO, HS 2 , HSO 2 , HOSO 2 , HOSOH, and HOSHO. © 2005 American Chemical Society.

DOI 10.1021/jp045086n
Citations Scopus - 8
2005 Mackie JC, Bacskay GB, 'Quantum chemical study of the mechanism of reaction between NH (X 3¿-) and H2, H2O, and CO 2 under combustion conditions', Journal of Physical Chemistry A, 109 11967-11974 (2005)

Reactions of ground-state NH ( 3 ¿ - ) radicals with H 2 , H 2 O, and CO 2 have been investigated quantum chemically, whereby the stationary points of the appropriate reaction p... [more]

Reactions of ground-state NH ( 3 ¿ - ) radicals with H 2 , H 2 O, and CO 2 have been investigated quantum chemically, whereby the stationary points of the appropriate reaction potential energy surfaces, that is, reactants, products, intermediates, and transition states, have been identified at the G3//B3LYP level of theory. Reaction between NH and H 2 takes place via a simple abstraction transition state, and the rate coefficient for this reaction as derived from the quantum chemical calculations, k(NH + H 2 ) = (1.1 × 10 14 ) exp(-20.9 kcal mol -1 /RT) cm 3 mol -1 s -1 between 1000 and 2000 K, is found to be in good agreement with experiment. For reaction between triplet NH and H 2 O, no stable intermediates were located on the triplet reaction surface although several stable species were found on the singlet surface. No intersystem crossing seam between triplet NH + H 2 O and singlet HNO + H 2 (the products of lowest energy) was found; hence there is no evidence to support the existence of a low-energy pathway to these products. A rate coefficient of k(NH + H 2 O) = (6.1 × 10 13 ) exp(-32.8 kcal mol -1 /RT) cm 3 mol -1 s -1 between 1000 and 2000 K for the reaction NH ( 3 ¿) + H 2 O ¿ NH 2 ( 2 B) + OH ( 2 ¿) was derived from the quantum chemical results. The reverse rate coefficient, calculated via the equilibrium constant, is in agreement with values used in modeling the thermal de-NO x process. For the reaction between triplet NH and CO 2 , several stable intermediates on both triplet and singlet reaction surfaces were located. Although a pathway from triplet NH + CO 2 to singlet HNO + CO involving intersystem crossing in an HN-CO 2 adduct was discovered, no pathway of sufficiently low activation energy was discovered to compare with that found in an earlier experiment [Rohrig, M.; Wagner, H. G. Proc. Combust. Inst. 1994, 25, 993.]. © 2005 American Chemical Society.

DOI 10.1021/jp0544585
Citations Scopus - 14
2004 Mackie JC, Bacskay GB, 'Oxidation of CO by SO2: A theoretical study', International Symposium on Combustion, Abstracts of Works-in-Progress Posters (2004)

There is recent renewed interest in the high temperature chemistry of sulfur in combustion systems, especially involving coals and petroleum products. Under combustion conditions,... [more]

There is recent renewed interest in the high temperature chemistry of sulfur in combustion systems, especially involving coals and petroleum products. Under combustion conditions, sulfur is largely found as SO 2 and this compound can react with CO especially under moist conditions. An ab initio quantum chemical and RRKM kinetic analysis of the reaction between SO 2 and CO was carried out. Reaction (1) was an endothermic process. The reaction could take place as a concerted process via the cis-transition states initially forming singlet-state SO and ground-state CO 2 . The barrier for this process was ~ 50 kcal/mole. On the trans-surface, the SO 2 + CO association led to a metastable OSOCO intermediate and a small barrier to dissociation. SO produced via reaction (1) could can readily react further with a second CO molecule. Reaction (2) was exothermic. There were two transition states, i.e., a cis- and trans-SOCO. It could take place as a concerted process through the cis-SOCO with a relatively low barrier. This is an abstract of a paper presented at the 30th International Symposium on Combustion (Chicago, IL 7/25-30/2004).

2003 Haworth NL, Mackie JC, Bacskay GB, 'An ab initio quantum chemical and kinetic study of the NNH + O reaction potential energy surface: How important is this route to NO in combustion?', Journal of Physical Chemistry A, 107 6792-6803 (2003)

A detailed study of the NNH + O reaction potential energy surface using coupled cluster [CCSD(T)] and density functional (B3LYP) methods is reported. Three N 2 OH adducts have bee... [more]

A detailed study of the NNH + O reaction potential energy surface using coupled cluster [CCSD(T)] and density functional (B3LYP) methods is reported. Three N 2 OH adducts have been located on this surface: cis- and trans-ONNH and ONHN. The product channels to NO + NH, N 2 O + H, N 2 + OH, and HNO + N have been characterized via the computation of minimum energy paths and of the appropriate transition states Rate coefficients for the reaction of NNH + O to each of these reaction channels have been computed using RRKM techniques. As the reaction flux passing to these channels in combustion systems is very sensitive to the stability of NNH, the heats of formation of this species and of the transition state leading to its formation (NN-H) were also computed via complete basis estimates of the CCSD(T) energetics based on extrapolation of aug-cc-pVxZ results with x = 5, 6 obtaining a value of ¿ f H 298 ° = 60.6 ± 0.5 kcal mol -1 . Additionally, a value of k 4 = 7.80 × 10 10 T 0.642 exp(1380 cal mol -1 /RT) cm 3 mol -1 s -1 for the rate coefficient of the reaction NNH + O ¿ NO + NH (4) between 1000 and 2600 K was obtained. This is approximately a factor of 4 less than the previous estimate of k 4 (Bozzelli, J. W.; Dean, A. M., Int. J. Chem. Kinet. 1995, 27, 1097). The new NNH rate data and thermochemistry are used to predict the level of NO produced in lean combustion in a completely stirred flow reactor. The overall conclusion arrived at on the basis of this work is that, in most combustion systems, the NNH + O pathway represents a very minor route to NO.

DOI 10.1021/jp034421p
Citations Scopus - 22
2002 Mackie JC, Bacskay GB, Haworth NL, 'Reactions of phosphorus-containing species of importance in the catalytic recombination of H + OH: Quantum chemical and kinetic studies', Journal of Physical Chemistry A, 106 10825-10830 (2002)

Four reactions of potential importance in the catalytic recombination of H + OH in the presence of phosphorus compounds have been studied by ab initio quantum chemical and RRKM me... [more]

Four reactions of potential importance in the catalytic recombination of H + OH in the presence of phosphorus compounds have been studied by ab initio quantum chemical and RRKM methods. These are the reactions HOPO + OH ¿ (HO) 2 PO ¿ H 2 O + PO 2 (3), HOPO + H ¿ P(OH) 2 ¿ H 2 O + PO (4), (HO) 2 PO + H ¿ P(OH) 3 ¿ H 2 O + HOPO (5), and HOPO 2 + H ¿ (HO) 2 PO ¿ H 2 O + PO 2 (6). Each of these reactions takes place by recombination with small ( < 5 kcal mol -1 ) or no barrier to form an adduct. The subsequent decomposition of the adducts occurs by the elimination of H 2 O through four-centered transition states. The thermochemistry of these reactions including the heats of formation of each of the adducts and the appropriate transition states was computed by the Gaussian G3X and G3X2 methods. Overall rate coefficients for each of these reactions at temperatures from 1000 to 2000 K and at pressures between 1 and 10 000 Torr were computed by the MultiWell code developed by Barker (Barker, J. R. Int. J. Chem. Kinet. 2001, 33, 232). For each reaction, there is very little stabilization of the adduct; hence the reactions are essentially pressure-independent. For reaction 6, its overall rate coefficient for the addition/decomposition mechanism greatly exceeds that previously derived for an abstraction transition state (Haworth, N.L.; Bacskay, G.B.; Mackie, J.C. J. Phys. Chem. A 2002, 106, 1533-1541).

DOI 10.1021/jp025727j
Citations Scopus - 15
2002 Haworth NL, Bacskay GB, Mackie JC, 'The role of phosphorus dioxide in the H + OH recombination reaction: Ab initio quantum chemical computation of thermochemical and rate parameters', Journal of Physical Chemistry A, 106 1533-1541 (2002)

A theoretical investigation of the effects of PO 2 on the H + OH radical recombination reaction is reported. The focus of the study is the computation of rate coefficients by ab ... [more]

A theoretical investigation of the effects of PO 2 on the H + OH radical recombination reaction is reported. The focus of the study is the computation of rate coefficients by ab initio quantum chemical and RRKM methods for the H + PO 2 and OH + PO 2 recombination reactions and for the H + HOPO ¿ H 2 + PO 2 , OH + H 2 ¿ H + H 2 O, and H + HOPO 2 ¿ H 2 O + PO 2 abstraction reactions, which constitute a catalytic pathway for the H + OH recombination reaction (Twarowski, A. Combust. Flame 1993, 94, 91). These are a subset of Twarowski's reaction model (Twarowski, A. Combust. Flame 1995, 102, 41) that consists of 175 individual reactions and includes 17 phosphorus-containing molecules. The thermochemistry of this complete reaction model was computed using the Gaussian methods: G2, G3, and G3X. While G3X was found to be superior to G2 and G3 for the prediction of heats of formation of phosphorus-containing molecules, it underestimates the heat of formation of HOPO 2 by at least 3.6 kcal mol -1 , when compared with the extensive coupled cluster computations of Bauschlicher (Bauschlicher, C.W., Jr. J. Phys. Chem. 1999, 103, 11126). Consequently, the rate coefficients reported in this work are based on Bauschlicher's thermochemical data for PO 2 , HOPO, and HOPO 2 . The computed rate coefficients are consistent with the available experimental data and the results of modeling studies by Twarowski (Twarowski, A. Combust. Flame 1995, 102, 41) and Korobeinichev et al. (Korobeinichev, O.P.; Ilyin, S.B.; Bolshova, T.A.; Shvartsberg, V.M.; Chernov, A.A. Combust. Flame 2001, 125, 744). The recombination reactions are found to be substantially into the fall-off region at near atmospheric pressures.

DOI 10.1021/jp012649b
Citations Scopus - 15
2002 Mackie JC, Chang JC, Masri AR, Chelliah HK, 'Water mist solutions as effective flame suppressants', International Symposium on Combustion Abstracts of Works-in-Progress Posters (2002)

Water mists of droplet sizes of 10-20 µm dia have attracted attention in addition to various inorganic suppressants as potential new, environmentally friendly alternative flame s... [more]

Water mists of droplet sizes of 10-20 µm dia have attracted attention in addition to various inorganic suppressants as potential new, environmentally friendly alternative flame suppressants. The possibility of combining water mists and inorganic suppressants was studied via the use of mists containing soluble inorganic salts to search for synergistic inhibition effects. Small cupburners burning heptane in co-flowing air were used to study the inhibition process. By measuring the dependence of the flame extinction upon the concentration of the dissolved salt, a relative ranking of suppression efficiency was developed. In addition to the water mist droplet size and the chemical nature of the solute, size of the residual solute particle once the water has evaporated was an important issue. Also of importance were the decomposition temperature of the residual solute and its residence time in the flame. Original is an abstract.

2001 Peters P, Hughes CF, Ikeda E, Mackie JC, 'Toxic fumes from use of cautery on collagen- and gelatin-impregnated polyester vascular grafts', Journal of Thoracic and Cardiovascular Surgery, 121 384-386 (2001)
DOI 10.1067/mtc.2001.109548
Citations Scopus - 1
2001 Guarneri F, Ikeda E, Mackie JC, 'A study of furan as a model oxygenated reburn for nitric oxide reduction', Energy and Fuels, 15 743-750 (2001)

Reduction of NO with furan under pyrolytic and oxidative conditions is investigated. Experiments in a single pulse shock tube are performed under the conditions covering the tempe... [more]

Reduction of NO with furan under pyrolytic and oxidative conditions is investigated. Experiments in a single pulse shock tube are performed under the conditions covering the temperature range of 1210-1950 K, pressures from 12.4 to 15.3 atm, residence times of 570-1140 µs, initial NO concentrations of 300-380 ppm, and initial furan concentration of 1.44 mol % for the pyrolysis series and 0.36 mol % for the two oxidation series with equivalence ratio, f, of 5.0 and 2.4. Furan removed NO at progressively lower temperature as the equivalence ratio decreased. The maximum NO reduction achieved in the temperature range of this study is 50% for pyrolysis and 80% for the oxidation series. The only N-containing products Observed are N 2 and low yields of HCN. A kinetic reaction model which reproduces the experimental data substantially is presented and this is used to compare the efficiency Of NO reduction by furan and other hydrocarbons under shock tube and stirred flow reactor conditions. The efficiency of NO removal by furan is comparable to that by propene. Acetylene is more effective than either fuel. Low-temperature conversion of NO by C 2 H 2 , however, is predicted to lead to the formation of NO 2 . The ability of furan, a major product of thermal decomposition of biomass, to reduce NO in the absence of O 2 suggests that biomass may be an efficient and inexpensive alternative to other reburning fuels.

DOI 10.1021/ef000276s
Citations Scopus - 7
2001 Ikeda E, Mackie JC, 'An experimental and modelling study of ignition delays in shock-heated ethane-oxygen-argon mixtures inhibited by 2H-heptafluoropropane', Zeitschrift fur Physikalische Chemie, 215 997-1009 (2001)

Ignition delay times have been measured behind reflected shock waves in ethane-oxygenargon mixtures at temperatures between 1150 and 1500 K and pre-ignition pressures between 10 a... [more]

Ignition delay times have been measured behind reflected shock waves in ethane-oxygenargon mixtures at temperatures between 1150 and 1500 K and pre-ignition pressures between 10 and 14 atm. Delay times have been measured both by pressure rise and OH absorption at 307 nm. Kinetic modelling of the ignition delays has been made using the GRIMech 3.0 mechanism which with addition of several reactions involving HO 2 radicals and an increase in the barrier for reaction between C 2 H 5 and O 2 can satisfactorily model delays over the studied equivalence ratios of f= 1.7 to 0.68. Addition of 2H-heptafluoropropane up to 13 mol % (of ethane) had little inhibition effect on stoichiometric ethane-oxygen-argon mixtures but inhibited ignition in a mixture of f= 1.5. A kinetic mechanism is presented to model the inhibition process. © by Oldenbourg Wissenschaftsverlag, München.

Citations Scopus - 7
2001 Bacskay GB, Mackie JC, 'The pyrolysis of cyclopentadiene: Quantum chemical and kinetic modelling studies of the acetylene plus propyne/allene decomposition channels', Physical Chemistry Chemical Physics, 3 2467-2473 (2001)

The thermal decomposition of cyclopentadiene to acetylene plus propyne or allene was studied using ab initio CASSCF, CASPT2, G2(MP2) as well as density functional methods. Three d... [more]

The thermal decomposition of cyclopentadiene to acetylene plus propyne or allene was studied using ab initio CASSCF, CASPT2, G2(MP2) as well as density functional methods. Three distinct reaction pathways were explored that involve 1,2-hydrogen transfers, yielding cyclic carbenes or allyl vinylidene as initial intermediates. After ring opening or a second 1,2-hydrogen transfer, the resulting open chain isomers dissociate via 1,5 sigmatropic shifts or by CC bond fission. From the computed CASSCF/CASPT2 data the appropriate RRKM rate constants for these reactions were computed and incorporated into a kinetic model containing the appropriate parameters for the conventional model of acetylene production via cyclopentadienyl, c-C 5 H 5 . The modelling studies, although not achieving quantitative agreement with experiment without some adjustment of the ab initio derived kinetic parameters, demonstrate that the proposed additional mechanism may be a major source of acetylene under a range of shock tube conditions. Consequently, the rate constant for the decomposition of c-C 5 H 5 to C 2 H 2 + C 3 H 3 cannot be derived directly from existing experimental data.

DOI 10.1039/b101317n
Citations Scopus - 31
2000 Ledesma EB, Kalish MA, Nelson PF, Wornat MJ, MacKie JC, 'Formation and fate of PAH during the pyrolysis and fuel-rich combustion of coal primary tar', Fuel, 79 1801-1814 (2000)

The formation and fate of polycyclic aromatic hydrocarbons (PAH) during the pyrolysis and fuel-rich combustion of primary tar generated under rapid heating conditions have been st... [more]

The formation and fate of polycyclic aromatic hydrocarbons (PAH) during the pyrolysis and fuel-rich combustion of primary tar generated under rapid heating conditions have been studied. Experiments were performed using a quartz two-stage reactor consisting of a fluidized-bed reactor coupled to a tubular-flow reactor. Primary tar was produced in the fluidized-bed reactor by rapid coal pyrolysis at 600 °C. The freshly generated tar was subsequently reacted in the tubular-flow reactor at 1000 °C under varying oxygen concentrations covering the range from pyrolysis to stoichiometric oxidation. PAH species present in the tars recovered from the tubular-flow reactor were analyzed by high-performance liquid chromatography (HPLC). Twenty-seven PAH species, varying from 2-ring to 9-ring structures, were identified, including benzenoid PAH, fluoranthene benzologues and indene benzologues. The majority of PAH species identified from pyrolysis were also identified in the samples collected from oxidation experiments. However, three products, 9-fluorenone, cyclopenta[def]phenanthrene and indeno[1,2,3-cd] fluoranthene, were produced only during oxidizing conditions. The addition of a small amount of oxygen brought about measurable increases in the yields of the indene benzologues and 9-fluorenone, but the yields of all PAH products decreased at high oxygen concentrations, in accordance with their destruction by oxidation. Possible formation and destruction mechanisms of PAH under fuel-rich conditions have been discussed.

DOI 10.1016/S0016-2361(00)00044-2
Citations Scopus - 97
2000 Haworth NL, Smith MH, Bacskay GB, Mackie JC, 'Heats of formation of hydrofluorocarbons obtained by Gaussian-3 and related quantum chemical computations', Journal of Physical Chemistry A, 104 7600-7611 (2000)

The heats of formation of ~120 C 1 and C 2 hydrofluorocarbon and oxidized hydrofluorocarbon molecules, as well as of hexafluoropropene and the hexafluoropropyl radical, were com... [more]

The heats of formation of ~120 C 1 and C 2 hydrofluorocarbon and oxidized hydrofluorocarbon molecules, as well as of hexafluoropropene and the hexafluoropropyl radical, were computed using the Gaussian-3 (G3) method, along with two approximations to G3, denoted G3[MP2(full)] and G3(MP4SDQ), and the G2(MP2) method. The performance of G3 is clearly superior to that of the other methods when the heats of formation are computed via atomization energies, and in general, the G3 results agree with the available good-quality experimental and theoretical data to within 2 kcal mol -1 . The use of isodesmic reaction schemes improves the overall accuracy of the computed heats of formation and results in a consistent set of predictions that are largely method-independent. Although, for the majority of molecules, the G3 data agree well with the earlier theoretical predictions of Zachariah et al. (J. Phys. Chem., 1996, 100, 8737), who used the bond-additivity-corrected MP4 (BAC-MP4) method, there are significant discrepancies as well. The heats of formation of a group of small molecules consisting of the fluoroacetylenes (HCCF and C 2 F 2 , as well as C 2 H 2 ) and the C 2 H, C 2 F, and formyloxyl (HCOO) radicals were also computed using the coupled-cluster method with basis sets ranging from cc-pVDZ to aug-cc-pVQZ and cc-pCVQZ, followed by extrapolation to the CBS limit and corrections for core-valence correlation and scalar relativistic effects. The predicted CBS heats of formation (in kcal mol -1 ) are ¿ f H 298 0 (HCCF) = 24.6 ± 1.0, ¿ f H 298 0 (C 2 F 2 ) = 0.5 ± 1.0, ¿ f H 298 0 (C 2 H) = 135.9 ± 1.0, ¿ f H 298 0 (C 2 F) = 109.1 ± 1.0, and ¿ f H 298 0 (HCOO) = -30.1 ± 1.0, in good agreement with the G3 results. The current work on formyloxyl provides strong support for the experimental value of ¿ f H 0 0 = 28.6 ± 0.7 kcal mol -1 obtained by Langford et al. (J. Chem. Soc., Faraday Trans. 1997, 93, 3757). © 2000 American Chemical Society.

Citations Scopus - 51
2000 Sendt K, Bacskay GB, Mackie JC, 'Pyrolysis of furan: Ab initio quantum chemical and kinetic modeling studies', Journal of Physical Chemistry A, 104 1861-1875 (2000)

The kinetics of pyrolysis of furan have been investigated theoretically by ab initio quantum chemical techniques and by detailed chemical kinetic modeling of previously reported e... [more]

The kinetics of pyrolysis of furan have been investigated theoretically by ab initio quantum chemical techniques and by detailed chemical kinetic modeling of previously reported experimental results. [Organ, P. P.; Mackie, J. C. J. Chem. Soc., Faraday Trans. 1991, 87, 815.] The kinetic model, containing rate constants derived from the ab initio calculations, can satisfactorily model the species profiles that had been obtained in shock tube experiments at three initial concentrations of furan. The thermochemistry and rate parameters of a number of key reactions have been obtained by ab initio calculations carried out at CASSCF, CASPT2, and G2-(MP2) levels of theory. The calculations suggest that two parallel processes, initiated by 1,2-H transfers that result in the formation of cyclic carbene intermediates and lead to the decomposition products CO + propyne and C2H2 + ketene (as major and minor channels, respectively), are the dominant pathways and enable the quantitative modeling of the kinetics of furan disappearance and the formation of the major products. Direct ring scission in furan, either on a singlet or triplet surface, is found to be much too energetic to contribute to any appreciable degree. No evidence was found for significant participation of a third channel producing HCO + C 3 H 3 . H atoms and C 3 H 3 radicals arise essentially by CH fission of propyne. Hydrogen abstraction from furan by methyl radicals is, however, significant and represents the principal source of methane in the products.

Citations Scopus - 63
2000 Ikeda E, Nicholls P, Mackie JC, 'A kinetic study of the oxidation of pyridine', Proceedings of the Combustion Institute, 28 1709-1716 (2000)

Oxidation of pyridine has been studied behind reflected shock waves in a single-pulse shock tube. Four mixtures of pyridine and oxygen have been studied diluted in argon. The stud... [more]

Oxidation of pyridine has been studied behind reflected shock waves in a single-pulse shock tube. Four mixtures of pyridine and oxygen have been studied diluted in argon. The studied equivalence ratios were f = 4.82, 2.33, 1.21, and 0.60, ranging from very fuel rich to fuel lean. The temperature range was from 1000 to 2200 K, pressures ranged from 8.0 to 20 atm, and reaction residence times behind the reflected shock front ranged from 600 to 1100 µs. In the richest mixture, non-oxygenated products were similar to those produced in pyrolysis, except that N 2 and pyrrole, products not observed in pyrolysis, were also formed. At the lowest temperatures at which products could be detected (1200 K approximately), CO was the principal product of oxidation. Its yield profile with temperature was strongly dependent on the initial oxygen concentration. Molecular nitrogen was observed at all equivalence ratios, but its yield was maximum in the near stoichiometric mixture. NO was only produced in significant quantities in the near stoichiometric and lean mixtures. From kinetic modeling studies it was concluded that the oxidation is initiated both by unimolecular C-H bond fission and bimolecular reaction with O 2 to form the ortho-pyridyl radical which can further react with oxygenated species to give the pyridoxy radical. Pyridoxy undergoes CO elimination producing pyrrolyl radicals from which pyrrole arises. Other reactions important in the mechanism involve O abstraction and addition reactions with pyridine and ring scission reactions of pyridoxy. The predictions of a kinetic model are tested against experimental product profiles obtained with values of f = 1.21 and 0.60.

Citations Scopus - 20
2000 Hynes RG, Mackie JC, Masri AR, 'A shock tube kinetic study on the reaction of C3F6 and H atoms at high temperatures', Proceedings of the Combustion Institute, 28 1557-1562 (2000)

The high-temperature reaction of H atoms with C 3 F 6 was studied behind reflected shock waves in a single-pulse shock tube over the temperature range 1250-1550 K, pressures ~16-... [more]

The high-temperature reaction of H atoms with C 3 F 6 was studied behind reflected shock waves in a single-pulse shock tube over the temperature range 1250-1550 K, pressures ~16-18 atm, and residence times 500-800 µs. The H atoms were generated by thermal decomposition of C 2 H 5 I. Gas chromatography (GC) analyses of the postshock products revealed the presence of the following species (in order of greatest yield): CF 2 CHF, CF 2 H 2 , CF 3 H, and CF 2 CH 2 . Hydrocarbons recovered in the products include C 2 H 4 , C 2 H 2 , CH 4 , traces of C 2 H 6 , and soot precursors. GC/mass spectrometry analyses of postshock products revealed trace amounts of CF 3 CH = CF 2 and CF 3 CH = CH 2 . Also detected were traces of CF 3 I, CH 3 I, C 2 H 3 I, and CHF 2 I. A kinetic model incorporating most of the above mentioned species was developed to model the experimental product yield profiles as a function of temperature. Thermochemical considerations showed that H-atom addition to the central carbon of the molecule was preferred and the deduced rate coefficient for the process was k = 2 × 10 13 exp (-2.2 kcal mol -1 /RT) cm 3 mol -1 s -1 . Reaction flux analysis showed that CHF 2 I was an important intermediate and that HI was important in the formation of some hydrofluorocarbon species.

Citations Scopus - 5
2000 Ledesma EB, Nelson PF, Mackie JC, 'An experimental and kinetic modeling study of the reduction of NO by coal volatiles in a flow reactor', Proceedings of the Combustion Institute, 28 2345-2351 (2000)

The reduction of NO by reactions with primary coal tar and other volatiles under fuel-rich conditions was investigated using a tubular-flow reactor coupled to a fluidized-bed reac... [more]

The reduction of NO by reactions with primary coal tar and other volatiles under fuel-rich conditions was investigated using a tubular-flow reactor coupled to a fluidized-bed reactor. The primary coal volatiles were generated at high heating rate (10 4 K s -1 ) conditions in the fluidized-bed reactor. The results were compared to those from experiments performed using the same experimental setup but with CH 4 instead of the primary coal volatiles. The experimental results show that reactions of coal volatiles result in greater NO reductions than reactions with CH 4 . In addition, NO reduction by coal volatiles occurs at much lower oxygen concentrations, indicating the higher reactivity of the coal volatiles compared to that of CH 4 . Increases in the yields of HCN and HNCO were found to occur concurrently with the decrease in NO during the experiments with the coal volatiles, suggesting that the NO is reduced to these two species under the conditions employed in this study. Kinetic modeling of the experiments with coal volatiles was performed using a highly simplified model for the coal tars, in which the tar was modeled as structures representative of the major species known to be present in primary tar: n-heptane to represent the longchain aliphatics, toluene and phenol to represent the aromatics, and a pseudospecies, designated as tar-N, to represent the nitrogen-containing components in primary tar. Despite the simplified tar-nitrogen chemistry employed (the nitrogen in tar was assumed to evolve via the first-order global reaction, tar-N ¿ HCN), the modeling results show reasonable predictions of the major gas-phase species. Yields of HNCO and NH 3 however are poorly predicted.

Citations Scopus - 4
2000 Nicholls P, Ikeda E, Mackie JC, 'A kinetic study of the oxidation of pyridine' (2000)

Oxidation of pyridine was investigated behind reflected shock waves in a single pulse shock tube. Four mixtures of pyridine and oxygen diluted in argon were studied at equivalence... [more]

Oxidation of pyridine was investigated behind reflected shock waves in a single pulse shock tube. Four mixtures of pyridine and oxygen diluted in argon were studied at equivalence ratios of 4.82:1, 2.33:1, 1.21:1, and 0.60:1, ranging from very fuel-rich to fuel-lean, 1000-2200 K, and 8-20 atm. Reaction residence times behind the reflected shock front ranged from 600 to 1100 µsec. The richest mixture and pyrolysis yielded similar non-oxygenated products, but N 2 and pyrrole were also observed in the first case. CO was the major product of oxidation at the lowest temperatures at which products could be detected (approximately 1200 K), and its yield profile with temperature was dependent on the initial oxygen concentration. Molecular nitrogen was observed in all equivalence ratios but it had a maximum yield in the near stoichiometric mixture. NO was only produced in significant amounts in the near stoichiometric and lean mixtures. Oxidation was initiated by unimolecular C-H bond fission and bimolecular reaction with O 2 to form the ortho-pyridyl radical which further reacted with oxygenated species to produce the pyridoxy radical. Pyrrole was formed from pyrrolyl radicals which were produced when pyridoxy underwent CO elimination.

2000 Hynes RG, Mackie JC, Masri AR, 'A shock tube kinetic study on the reaction of C3F6 and H atoms at high temperatures' (2000)

The high temperature reaction of H atoms with C 3 F 6 was investigated behind reflected shock waves in a single-pulse shock tube at 1250-1550 K, around 16-18 atm, and residence t... [more]

The high temperature reaction of H atoms with C 3 F 6 was investigated behind reflected shock waves in a single-pulse shock tube at 1250-1550 K, around 16-18 atm, and residence times of 500-800 µsec. H atoms were generated by thermal decomposition of C 2 H 5 I. GC analyses of the post-shock products showed the presence of CF 2 CHF, CF 2 H 2 , CF 3 H, and CF 2 CH 2 (in order of greatest yield). Among the hydrocarbons recovered in the products were C 2 H 2 , C 2 H 4 , CH 4 and traces of C 2 H 6 , and soot precursors. Trace amounts of CF 3 CH=CF 2 and CF 3 CH=CH 2 , as well as CF 3 I, CHF 2 I, C 2 H 3 I, and CH 3 I were also observed. H atom addition to the central carbon of the molecule was preferred and the deduced rate coefficient for the process was k = 2 x 10 13 exp (-2.2 kcal/mole/RT) cc/mole/sec. CHF 2 I was an important intermediate, and HI played an important role in the formation of some hydrofluorocarbon species.

1999 Bacskay GB, Martoprawiro M, MacKie JC, 'The thermal decomposition of pyrrole: An ab initio quantum chemical study of the potential energy surface associated with the hydrogen cyanide plus propyne channel', Chemical Physics Letters, 300 321-330 (1999)

An ab initio quantum chemical study of the thermal decomposition of pyrrole to hydrogen cyanide and propyne is reported. Using CASSCF, CASPT2 and G2(MP2) methods three distinct pa... [more]

An ab initio quantum chemical study of the thermal decomposition of pyrrole to hydrogen cyanide and propyne is reported. Using CASSCF, CASPT2 and G2(MP2) methods three distinct pathways are investigated. The crucial step in each is a 1,5 sigmatropic shift that results in the concerted decomposition of an imine intermediate. The lowest energy pathway proceeds via a cyclic carbene, which, by ring opening produces the imine. The critical energy of the reaction is estimated as 75.6 kcal mol -1 which is consistent with the experimental activation energy of 74.1±3 kcal mol -1 .

Citations Scopus - 25
1999 Hynes RG, Mackie JC, Masri AR, 'Sample probe measurements on a hydrogen-ethane-air-2-H-heptafluoropropane flame', Energy and Fuels, 13 485-492 (1999)

This paper describes experiments and numerical modeling of a lean premixed, atmospheric pressure (f = 0.55) hydrogen-ethane-air fiat flame with 1.5 mol% of CF 3 CHFCF 3 . Stable s... [more]

This paper describes experiments and numerical modeling of a lean premixed, atmospheric pressure (f = 0.55) hydrogen-ethane-air fiat flame with 1.5 mol% of CF 3 CHFCF 3 . Stable species concentrations as a function of height above the burner were obtained by sampling with a water-cooled quartz probe; these gases were subsequently analyzed by infrared spectroscopy. Numerical modeling of this flame was performed with a detailed chemical kinetic mechanism. Discrepancies between modeled and experimental concentrations were attributed to external probe-induced distortions. A phenomenological treatment of the external distortion gave reasonable agreement for all species. Plug-flow calculations were performed to determine the extent of sample composition change within the probe. These showed that homogeneous gas-phase reactions did not cause any changes to the sample. A surface oxidation channel was included to simulate CO loss. Reaction flux analyses revealed that flame inhibition arises from H- and O-atom, and to a lesser extent CH 3 radical, consumption by the fluorinated fragments CF 3 , CF 2 , and CFO. Consumption of OH radicals appeared to be relatively inefficient. A concentration sensitivity analysis on the species CO and CF 2 O was performed to show that reactions between CF 3 radicals and the major flame radicals were sensitive. The concentrations of these species were only mildly sensitive to reactions involving larger fluorinated species.

DOI 10.1021/ef980173y
Citations Scopus - 11
1999 Ledesma EB, Kalish MA, Wornat MJ, Nelson PF, Mackie JC, 'Observation of cyclopenta-fused and ethynyl-substituted PAH during the fuel-rich combustion of primary tar from a bituminous coal', Energy and Fuels, 13 1167-1172 (1999)

High-performance liquid chromatography (HPLC) with ultraviolet-visible (UV) diode-array detection was used to analyze the condensed-phase products from the fuel-rich combustion, a... [more]

High-performance liquid chromatography (HPLC) with ultraviolet-visible (UV) diode-array detection was used to analyze the condensed-phase products from the fuel-rich combustion, at 1000 °C, of bituminous coal primary tar. Experiments were performed using a quartz two-stage reactor consisting of a fluidized-bed reactor coupled to a tubular-flow reactor. Eight cyclopenta-fused polycyclic aromatic hydrocarbons (CP-PAH) were identified, four of which have never before been observed as products of a bituminous coal and have also never been observed from the fuel-rich combustion of any coal: cyclopent[hi]acephenanthrylene, cyclopenta[cd] fluoranthene, dicyclopenta[cdjk]pyrene, cylopenta[bc] coronene. In addition to these CP-PAH, two ethynyl-substituted PAH, 2-ethynylnaphthalene and 1-ethynylacenaphthylene, were identified for the first time as bituminous coal products. Yields of individual CP-PAH spanned a range of 4 orders of magnitude. Out of the eight CP-PAH identified, acenaphthylene was found to be the most abundant under all conditions investigated. CP-PAH of higher ring number were present in successively lower amounts, consistent with CP-PAH formation via hydrocarbon growth reactions. CP-PAH yields decreased with increasing oxygen concentration, indicating that rates of CP-PAH oxidation exceeded those of CP-PAH formation under the conditions investigated. Possible mechanisms of CP-PAH formation are discussed, but the complexity of the starting fuel precludes definitive delineation of the reaction pathways leading to CP-PAH and ethynyl-substituted PAH during the fuel-rich combustion of tar.

DOI 10.1021/ef990036g
Citations Scopus - 30
1999 Martoprawiro M, Bacskay GB, Mackie JC, 'Ab initio quantum chemical and kinetic modeling study of the pyrolysis kinetics of pyrrole', Journal of Physical Chemistry A, 103 3923-3934 (1999)

The kinetics of pyrolysis of pyrrole have been investigated theoretically by ab initio quantum chemical techniques and by detailed chemical kinetic modeling of previously reported... [more]

The kinetics of pyrolysis of pyrrole have been investigated theoretically by ab initio quantum chemical techniques and by detailed chemical kinetic modeling of previously reported experimental results. [Mackie, J. C.; Colket, M. B.; Nelson, P. F.; Esler, M. Int. J. Chem. Kinet. 1991, 23, 733.] The overall kinetics can be successfully modeled by a 117 step kinetic model that gives good agreement with temperature profiles of major products and also provides an acceptable fit for minor products. The thermochemistry and rate parameters of a number of key reactions have been obtained by ab initio calculations carried out at CASSCF, CASPT2, and G2(MP2) levels of theory. Several reaction pathways were investigated. The major product, HCN, arises principally from a hydrogen migration in pyrrole to form a cyclic carbene with the NH bond intact. Ring scission of this carbene leads to an allenic imine precursor of HCN and propyne. This is the decomposition pathway of lowest energy. Pyrolysis is preceded by the facile tautomerization of pyrrole to 2H-pyrrolenine. The latter can undergo CN fission to form an open chain biradical species, which is the precursor of the butenenitrile isomeric products, cis-and trans-crotononitrile and allyl cyanide. The biradical can also undergo facile H-fission to form cyanoallyl radical, which is an important precursor of acetylene, acetonitrile, and acrylonitrile. H 2 also arises principally from H-fission of the biradical.

Citations Scopus - 51
1999 Sendt K, Ikeda E, Bacskay GB, Mackie JC, 'Ab Initio Quantum Chemical and Experimental (Shock Tube) Studies of the Pyrolysis Kinetics of Acetonitrile', Journal of Physical Chemistry A, 103 1054-1072 (1999)

The pyrolysis kinetics of acetonitrile dilute in argon has been studied in the temperature range 1400-2100 K at an average pressure of 12 atm in single-pulse shock tube experiment... [more]

The pyrolysis kinetics of acetonitrile dilute in argon has been studied in the temperature range 1400-2100 K at an average pressure of 12 atm in single-pulse shock tube experiments. The principal products are HCN, C 2 H 2 , CH 4 , and H 2 , while the minor products include HCCCN, H 2 CCHCN, C 2 H 4 , and C 4 H 2 . The overall kinetics is successfully simulated by an 87 step kinetic model that accurately accounts for the temperature profiles of the major products and also provides an acceptable fit for the minor products. The thermochemistry and rate parameters of a number of key reactions have been obtained by ab initio quantum chemical calculations carried out at CASSCF, CASPT2, and Gaussian-2 levels of theory. Several distinct reaction pathways were studied, whereby the geometries, vibrational frequencies, and energies of approximately 70 molecular species representing reactants, products, intermediates, and transition states were computed. The pyrolysis of acetonitrile is initiated by CH bond fission, forming a cyanomethyl radical. This reaction is the most sensitive one in the kinetic model. On the basis of sensitivity analyses of the model as well as ab initio calculations, the heat of formation of cyanomethyl has been revised as ¿ f H 298 0 (CH 2 CN) = 263 ± 9 kJ mol -1 . The limiting highpressure value of the corresponding rate constant, as obtained by ab initio variational transition state calculations, is k 1 8 = 1.2 × 101 16 exp(- 413 kJ mol -1 /RT) s -1 , which is in good agreement with our extrapolated experimental measurement. A number of the observed products, including HCCCN and H 2 CCHCN, largely arise from the decomposition of succinonitrile, a key intermediate, that forms by the recombination of two cyanomethyl radicals.

Citations Scopus - 27
1999 Hynes RG, Mackie JC, Masri AR, 'Shock Tube Study of the Oxidation of C3F6 by N2O', Journal of Physical Chemistry A, 103 5967-5977 (1999)

The kinetics of the high-temperature oxidation of C 3 F 6 by O( 3 P) have been studied by experiment, using a single-pulse shock tube, and by kinetic modeling. The O atoms were g... [more]

The kinetics of the high-temperature oxidation of C 3 F 6 by O( 3 P) have been studied by experiment, using a single-pulse shock tube, and by kinetic modeling. The O atoms were generated by the thermal decomposition of N 2 O. Three mixtures, each diluted in argon, were studied: 0.6 mol % of C 3 F 6 with 1.5 mol % N 2 O; 6.2 mol % of C 3 F 6 with 0.6 mol % of N 2 O; and 6.3 mol % of N 2 O and 0.7 mol % of C 3 F 6 . The temperatures were in the range 1300-1600 K, the residence times behind the reflected shock were in the range 550-850 µs, and the pressures were between 16 and 20 atm. Fluorinated products have been quantified with gas chromatography, oxidized products with Fourier transform infrared spectroscopy; identification of unknown fluorocarbons has been performed with gas chromatography-mass spectrometry. The most significant products detected were C 2 F 6 , C 2 F 4 , CF 2 O, CO, CO 2 , and CF 4 . A detailed kinetic scheme is presented to model the experimental reactant and product yields as a function of temperature. Modeling showed that O-addition to either carbon of the double bond of C 3 F 6 occurs. The rate constant for O-addition to the terminal carbon of the double bond, C 3 F 6 + O( 3 P) ¿ 3 CF 3 CF + CF 2 O, was deduced to be k 71 = 10 12.7 T 0.05 exp(-0.4 kJ mol -1 /RT) cm 3 mol -1 s -1 , and for addition to the central carbon, C 3 F 6 + O( 3 P) ¿ CF 3 + CF 2 CF=O, k 72 = 10 12.5 cm 3 mol -1 s -1 . Under oxidizer-rich conditions, ignition of the C 3 F 6 occurred. Rate of production analyses showed that ignition was propagated by an F atom chain involving the CF 2 + O and unimolecular CFO decomposition reactions. Under C 3 F 6 -rich conditions, single- and double-bond pyrolysis were the important destruction routes.

Citations Scopus - 11
1999 Hynes RG, Mackie JC, Masri AR, 'Shock-tube study of the pyrolysis of the halon replacement molecule CF3CHFCF3', Journal of Physical Chemistry A, 103 54-61 (1999)

The kinetics of pyrolysis of CF 3 CHFCF 3 have been studied in dilute mixtures (0.5 and 3 mol %) in argon in a single-pulse shock tube over the temperature range of 1200-1500 K, ... [more]

The kinetics of pyrolysis of CF 3 CHFCF 3 have been studied in dilute mixtures (0.5 and 3 mol %) in argon in a single-pulse shock tube over the temperature range of 1200-1500 K, residence times behind the reflected shock of between 650 and 850 µs, and pressures between 16 and 18 atm. Fluorinated products were quantified with gas chromatography and Fourier transform infrared spectroscopy; identification of unknown fluorocarbons and hydrofluorocarbons was performed with gas chromatography - mass spectrometry. The most significant products detected were C 2 F 6 , CF 2 =CHF, C 2 F 4 , C 3 F 6 , cyclo-C 3 F 6 , and CF 3 CHFCF 2 H. Traces of CF 3 H, CF 4 , C 2 F 5 H C 3 F 8 , C 4 F 6 , and isomers of C 4 F 8 were also identified. A detailed kinetic reaction scheme is presented to model the experimental reactant and product yield profiles as a function of temperature. The results of modeling showed that the major initiation reaction was the C-C bond fission reaction. The abstraction of the secondary H atom by F atoms was also predicted to be important, whereas 1,2-HF elimination was slower. From experiments and modeling, the following initiation rate constants were obtained: CF 3 CHFCF 3 ¿ CF 3 + CF 3 CHF (k 37 = 10 15.9 exp(-355.6 kJ mol -1 /RT) s -1 ), CF 3 CHFCF 3 ¿ C 3 F 6 + HF (k 38 = 10 12.9 exp(-291.2 kJ mol -1 /RT) s -1 ), and CF 3 CHFCF 3 + F ¿ CF 3 CFCF 3 + HF (k 39 = 10 13.6 exp(-10.1 kJ mol -1 /RT) cm 3 mol -1 s -1 ). © 1999 American Chemical Society.

Citations Scopus - 39
1998 Bacskay GB, Martoprawiro M, Mackie JC, 'An ab initio quantum chemical study of the electronic structure and stability of the pyrrolyl radical: Comparison with the isoelectronic cyclopentadienyl radical', Chemical Physics Letters, 290 391-398 (1998)

The electronic structure and stability of pyrrolyl are investigated using CASSCF, CASPT2 and G2(MP2) techniques. The ground state of pyrrolyl is found to be 2 A 2 , with five p-e... [more]

The electronic structure and stability of pyrrolyl are investigated using CASSCF, CASPT2 and G2(MP2) techniques. The ground state of pyrrolyl is found to be 2 A 2 , with five p-electrons, as in cyclopentadienyl. The computed N-H bond energy of pyrrole is 94.8 kcal mol -1 , while the heat of formation ¿ f H 298 o of pyrrolyl is deduced to be 70.5 ± 1 kcal mol -1 . The Arrhenius parameters of N-H and C-H bond fission in pyrrole and cyclopentadiene and hydrogen abstraction reactions (by hydrogen) were also computed, indicating that pyrrolyl forms predominantly by C-H bond fission of pyrrolenine rather than by direct N-H bond fission.

Citations Scopus - 34
1998 Hynes RG, MacKie JC, Masri AR, 'Inhibition of premixed hydrogen-air flames by 2-H heptafluoropropane', Combustion and Flame, 113 554-565 (1998)

The results of an experimental and numerical modeling study on the inhibition chemistry of CF 3 CHFCF 3 are presented. Burner-stabilized, laminar, premixed, hydrogen-air flat fla... [more]

The results of an experimental and numerical modeling study on the inhibition chemistry of CF 3 CHFCF 3 are presented. Burner-stabilized, laminar, premixed, hydrogen-air flat flames with 1.0 and 3.2 mol % inhibitor added were studied as a function of equivalence ratio. The measured concentration profiles of stable species in the postflame gases were modeled with recently developed chemical kinetic mechanisms, augmented with estimated rate and thermochemical data germane to the oxidation of the inhibitor. Agreement between experimental and modeled profiles is adequate for most measured species, thereby partially validating the kinetic data used. Calculated reaction fluxes for 3.2 mol % inhibitor revealed that suppression of H atoms is effected by conversion to HF through reactions with fluorinated species. In contrast, suppression of OH was found to be less effective.

DOI 10.1016/S0010-2180(97)00267-8
Citations Scopus - 45
1998 Ledesma EB, Li CZ, Nelson PF, Mackie JC, 'Release of HCN, NH3, and HNCO from the thermal gas-phase cracking of coal pyrolysis tars', Energy and Fuels, 12 536-541 (1998)

The release of HCN, NH 3 , and HNCO from the thermal cracking of coal tars produced by rapid pyrolysis has been investigated using a quartz fluidized-bed reactor coupled to a quar... [more]

The release of HCN, NH 3 , and HNCO from the thermal cracking of coal tars produced by rapid pyrolysis has been investigated using a quartz fluidized-bed reactor coupled to a quartz tubular-flow reactor. Primary pyrolysis at 600°C in the fluidized-bed reactor generated the tars which were subsequently thermally decomposed in the tubular reactor in the temperature range of 600-1000°C. HNCO was the initial gaseous N-containing species to be evolved, its formation commencing from 600°C. HNCO was found to be a significant N-containing product of tar cracking and some previous measurements of NH 3 yields during coal pyrolysis are probably the sum of the yields of NH 3 and HNCO. Both HCN and NH 3 start to appear from above 7007deg;C. While NH 3 reaches a maximum at 850°C, HCN continues to increase at higher temperatures. It is suggested that NH 3 may be formed from the interactions of N-containing species with donatable H on the soot surface. FTIR analyses of the tars demonstrate that increases in the temperature of pyrolysis result in a decrease in aromatic substitution. Kinetic parameters for the release of tar-N species as HCN were determined by measurement of HCN yields and by assuming that the reaction was first order in tar-N. An overall global rate expression of 10 6 exp[-(140 ± 15)/RT] s -1 was derived from the data. The rate expression suggests that nitrogen release during tar cracking is a complex process.

Citations Scopus - 69
1998 Ledesma EB, Nelson PF, MacKie JC, 'The formation of nitrogen species and oxygenated PAH during the combustion of coal volatiles', Symposium (International) on Combustion (1998)

The combustion of coal volatiles produced by rapid pyrolysis was studied using a two-stage reactor consisting of a fluidized-bed reactor coupled to a tubular-flow reactor. Volatil... [more]

The combustion of coal volatiles produced by rapid pyrolysis was studied using a two-stage reactor consisting of a fluidized-bed reactor coupled to a tubular-flow reactor. Volatiles were generated in the fluidized-bed reactor under high heating rates and at 600 °C such that the major volatile species produced were tars. The freshly generated tars were subsequently oxidized in the tubular-flow reactor at 900 and 1000 °C. Fourier transform infrared (FTIR) analysis showed that, with an increase in oxygen concentration, the recovered tars exhibited an increase in the carbonyl, C=O, functionality. The position of the C=O peak and the presence of absorbances in the aromatic C-H out-of-plane deformation region in the FTIR spectra and GC/MS identification demonstrate that polycyclic aromatic ketones and aldehydes are significant oxygenated polycyclic aromatic hydrocarbons (OPAH) products from coal volatiles combustion. The results indicate that combustion processes are primarily responsible for OPAH formation. HNCO yield was found to increase rapidly with the addition of small amounts of oxygen. The results show that HCN oxidation is not primarily responsible for HNCO formation; reactions of other N-containing species are likely sources. The observation of HNCO suggests that previous measurements of NH 3 in coal combustion probably represent the sum of NH 3 and HNCO yields. The presence of hydrocarbon species (gases and tars) has a significant effect on fuel-N conversion. The experimental results clearly demonstrated that NO production increased significantly once the concentration of hydrocarbons decreased.

DOI 10.1016/S0082-0784(98)80008-8
Citations Scopus - 4
1997 Jones J, Bacskay GB, Mackie JC, 'Decomposition of the benzyl radical: Quantum chemical and experimental (shock tube) investigations of reaction pathways', Journal of Physical Chemistry A, 101 7105-7113 (1997)

Decomposition of the benzyl radical at a range of temperatures, ~ 1450-1650 K, has been investigated using ab initio quantum chemical and experimental (shock tube) techniques. Fou... [more]

Decomposition of the benzyl radical at a range of temperatures, ~ 1450-1650 K, has been investigated using ab initio quantum chemical and experimental (shock tube) techniques. Four possible decomposition mechanisms are considered: (a) via a norbornadienyl intermediate, (b) via a cycloheptatrienyl intermediate, (c) via direct ring opening, and (d) via a 6-methylenebicyclo[3.1.0]hex-3-en-2-yl (MBH) intermediate. On the basis of the quantum chemical calculations, mechanisms c and d are found to be the dominant reaction channels. A theoretically derived rate constant for the overall disappearance of benzyl is k = 1016.6±0.3 exp-(-97 ± 3 kcal mol -1 /RT)s -1 , in reasonable agreement with that obtained in previous studies. The experiments were carried out by shock heating benzyl bromide to temperatures between 1050 and 1650 K, followed by analysis of the spectral components of benzyl bromide, benzyl, and benzyl "fragments". The rate constants derived from these experiments by using a simple two-step kinetic model are in good agreement with the theoretical values.

Citations Scopus - 49
1996 Jones J, Bacskay GB, Mackie JC, 'The pyrolysis of 3-picoline: Ab initio quantum chemical and experimental (shock tube) kinetic studies', Israel Journal of Chemistry, 36 239-248 (1996)

The pyrolysis of 3-picoline dilute in argon was investigated using a single-pulse shock tube over the temperature range of 1400-1650 K and total pressures of 12-13 atm. The princi... [more]

The pyrolysis of 3-picoline dilute in argon was investigated using a single-pulse shock tube over the temperature range of 1400-1650 K and total pressures of 12-13 atm. The principal products observed were HCN, acetylene, benzene, cyanoacetylene, methane, and pyridine. Assuming that 3-picoline decomposes according to first-order kinetics, the rate constant for its overall disappearance was determined to be k dis = 10 16.9(±0.8) exp[-99 (±6) kcal mol -1 /RT] s -1 . The principal initial decomposition routes were found to be via the formation of the 3-picolyl and m-pyridyl radicals whose subsequent ring-opening led to the observed products. A 68-step kinetic model was developed that successfully fits the experimental data. The dominant reactions, i.e., the formation of picolyl and pyridlyl radicals and their subsequent chain-opening reactions, were studied using ab initio quantum chemical techniques. The ab initio data were also incorporated into the kinetic model in the form of energies and A-factors for reactions for which no kinetic or thermochemical data were previously available. Optimization of the kinetic model yields a value of 64 ± (3) kcal mol -1 for the heat of formation of 3-picolyl, a value lower than that for 2-picolyl, suggesting that the decomposition of 3-picoline more closely resembles that of toluene, rather than its isomer 2-picoline.

Citations Scopus - 4
1996 Ikeda E, Mackie JC, 'A kinetic study of the oxidation of acetonitrile: A model for NO formation from fuel-bound nitrogen', Symposium (International) on Combustion, 26 597-604 (1996)

The oxidation of acetonitrile dilute in argon has been studied in a single-pulse shock tube over the temperature range 1300-2100 K, at pressures between 1.1 and 2.0 M Pa and resid... [more]

The oxidation of acetonitrile dilute in argon has been studied in a single-pulse shock tube over the temperature range 1300-2100 K, at pressures between 1.1 and 2.0 M Pa and residence times between 700 and 1400 µs. Kinetics and product yields were determined for three mixture ratios of acetonitrile to oxygen, namely, 1:1, 1:2, and 1:3.5 by mole. Nitrogen oxides and carbon oxides were analyzed by FTIR spectroscopy and organonitrogen, and hydrocarbon products together with N 2 , O 2 , H 2 , and HCN were determined by gas chromatography. Ignition temperatures were dependent on the fuel/oxygen ratio and the major oxidation products were CO, CO 2 , H 2 O, N 2 , and NO. The ratio of N 2 to NO in the product gases is very dependent on the fuel/oxygen ratio. Rapid production of NO from acetonitrile takes place at temperatures at least 200 K below that at which HCN becomes rapidly oxidized to NO. In runs where no ignition took place within the residence time, the principal products observed were HCN, methane, acetylene, and hydrogen. Acrylonitrile and cyanoacetylene are also produced in significant yields before ignition. HNCO has also been observed in runs that are quenched rapidly after ignition. A 73 reaction kinetic model for the oxidation of acetonitrile when combined with the Miller-Bowman (Prog. Energy Combust. Sci. 15:287 [1989]) mechanism for HCN-NH 3 oxidation has been found to reproduce substantially the experimental oxidation data. © 1996 Combustion Institute.

DOI 10.1016/S0082-0784(96)80265-7
Citations Scopus - 3
1996 Li CZ, Nelson PF, Ledesma EB, Mackie JC, 'Experimental study of the release of nitrogen from coals pyrolyzed in fluidized-bed reactors', Symposium (International) on Combustion (1996)

Nitrogen release has been measured from a suite of Australian, German, and U.S. coals pyrolyzed under rapid heating conditions in two bench scale reactors. The first reactor was a... [more]

Nitrogen release has been measured from a suite of Australian, German, and U.S. coals pyrolyzed under rapid heating conditions in two bench scale reactors. The first reactor was a single-stage fluidized bed reactor; the second was a two-stage reactor in which a fluidized bed was coupled with a tubular reactor. The two-stage reactor enabled cracking reactions of the volatiles to be studied in isolation from reactions of the char. The results show that the gas-phase N-containing species, HCN and NH 3 , are formed from both brown and bituminous coals. In addition, HNCO is also observed from bituminous coals; HNCO is a plausible precursor for NH 3 formation. At high temperatures, low-volatile coals give lower yields of HCN and NH 3 than high-volatile coals. This observation, however, does not imply that tar cracking is the only source of HCN and NH 3 . In fact, the results obtained in the two-stage reactor suggest that a significant proportion of the HCN is released from the char and that tar cracking is not a significant source of NH 3 . A major part of the NH 3 is produced by interactions of N-containing species with the char. These results, together with previous studies of N release, demonstrate that there is no simple relationship between N functionality in coals and the composition and rate of release of the nitrogen.

Citations Scopus - 21
1995 Ikeda E, Mackie JC, 'Thermal decomposition of two coal model compounds - pyridine and 2-picoline. Kinetics and product distributions', Journal of Analytical and Applied Pyrolysis, 34 47-63 (1995)

The thermal decomposition of two coal model compounds, pyridine and 2-picoline, has been studied in a completely stirred fused-silica reactor over the temperature range 1060-1240 ... [more]

The thermal decomposition of two coal model compounds, pyridine and 2-picoline, has been studied in a completely stirred fused-silica reactor over the temperature range 1060-1240 K at pressures between 8.0 and 13.3 kPa and at reactor residence times between 1 and 5 s. Profiles of major products and kinetics of thermal decomposition of both compounds are given and a detailed investigation by GC/MS of the minor products of decomposition has been made. Profiles of pyridine and its major products of decomposition can be satisfactorily modelled by a homogenous gas phase kinetic model. The rate of decomposition of 2-picoline was faster than predicted by a homogenous gas phase mechanism and the decomposition would appear to be surface-assisted in the silica reactor. Both compounds were found to be useful models for the evolution of fuel-bound nitrogen from decomposition of coals. 2-Picoline, a nitrogen heteroaromatic analogue of toluene, was found, like its hydrocarbon analogue, to have a high propensity for sooting. The presence of the nitrogen atom in the condensed ring products of 2-picoline was found to be a useful chemical marker for unravelling the complex condensation chemistry leading to the formation of soot. © 1995.

DOI 10.1016/0165-2370(94)00873-Y
Citations Scopus - 40
1995 Jones J, Bacskay GB, Mackie JC, Doughty A, 'Ab initio studies of the thermal decomposition of azaaromatics: Free radical versus intramolecular mechanism', Journal of the Chemical Society, Faraday Transactions, 91 1587-1592 (1995)

The energetics of the key reactions in the thermal decomposition of the azaaromatic molecules pyridine, pyrimidine, pyrazine and pyridazine have been investigated using ab initio ... [more]

The energetics of the key reactions in the thermal decomposition of the azaaromatic molecules pyridine, pyrimidine, pyrazine and pyridazine have been investigated using ab initio quantum-chemical techniques. Two distinct mechanisms are considered: (a) intramolecular rearrangement where a bicyclic, Dewar isomer is formed as an intermediate, followed by its fission, producing acetylene and hydrogen cyanide, and (b) the formation of azyl radicals in a CH bond fission initiation reaction followed by decomposition as well as hydrogen abstraction reactions. The calculated energetics of the free radical mechanism are found to be consistent with the results of earlier experimental studies. The estimates of the critical energies associated with the intramolecular Dewar mechanism are, however, such as to rule it out as a viable alternative. A detailed ab initio study of the benzene ¿ Dewar benzene rearrangement is also reported.

DOI 10.1039/FT9959101587
Citations Scopus - 21
1994 Doughty A, Mackie JC, Bacskay GB, 'Experimental and theoretical study of the isomerisation of N-methylpyrrole', Chemical Physics Letters, 221 267-273 (1994)

The isomerisation of N-methylpyrrole to 2-methylpyrrole has been investigated experimentally by means of a single pulse shock tube over the temperature range 1000 to 1350 K and th... [more]

The isomerisation of N-methylpyrrole to 2-methylpyrrole has been investigated experimentally by means of a single pulse shock tube over the temperature range 1000 to 1350 K and theoretically by ab initio calculations. Between 1000 and 1100 K the isomerization is found to occur via an intramolecular methyl shift. The experimental rate constant for this rearrangement was found to be k iso = 10 12.8(±0.4) exp [-56.2(±2.0) kcal mol -1 /RT] s -1 . Ab initio calculations gave Arrhenius parameters for the methyl shift in good agreement with the experimental values. Methyl shifting produces the intermediate 2-methyl-2H-pyrrole which undergoes a hydrogen shift of low activation energy to form the product of isomerisation, 2-methylpyrrole. Above about 1240 K there is a competing free-radical process which produces methane, pyrrole and traces of higher molecular weight products. © 1994.

DOI 10.1016/0009-2614(94)00267-3
Citations Scopus - 6
1994 Doughty A, Bacskay GB, Mackie JC, 'Experimental and ab initio theoretical study of the kinetics of rearrangement of ketene imine to acetonitrile', Journal of Physical Chemistry, 98 13546-13555 (1994)

When heated by reflected shock waves to temperatures between 1400 and 1700 K at pressures of approximately 12-15 atm, mixtures of acetonitrile in argon (0.4-7 mol %) exhibit stron... [more]

When heated by reflected shock waves to temperatures between 1400 and 1700 K at pressures of approximately 12-15 atm, mixtures of acetonitrile in argon (0.4-7 mol %) exhibit strong banded absorption in the ultraviolet region between 320 and 250 nm. The carrier of the absorption spectrum is ketene imine, H 2 C=C=NH. Time-resolved spectra of ketene imine have been recorded with exposure times between 100 and 200 µs using a charge-coupled device (CCD) with an imaging spectrograph. Through the use of the technique of pixel binning, temporal profiles of formation and equilibration of ketene imine have been obtained with a time resolution of 24 µs. The rearrangement of ketene imine ¿ acetonitrile has been studied using ab initio quantum chemical techniques. The calculations predict the rate-determining step in the rearrangement process to be the 1,2-hydrogen transfer of the imine hydrogen to the adjacent carbon atom to produce vinyl nitrene. With the aid of the ab initio results, the experimental rate data for the reaction ketene imine ¿ acetonitrile have been extrapolated to the high-pressure limit, yielding the rate constant expression k 8 = 10 134(±05) exp(-294(±14) kJ mol -1 /RT) s -1 . © 1994 American Chemical Society.

Citations Scopus - 32
1994 Doughty A, Mackie JC, Palmer JM, 'Kinetics of the thermal decomposition and isomerisation of pyrazine (1,4 diazine)', Symposium (International) on Combustion, 25 893-900 (1994)

The isomerisation and decomposition of pyrazine have been studied over the temperature range 1200-1480 K. The major products of decomposition were found to be acetylene and HCN, w... [more]

The isomerisation and decomposition of pyrazine have been studied over the temperature range 1200-1480 K. The major products of decomposition were found to be acetylene and HCN, with cyanoacetylene and acrylonitrile also being significant products, although lower yields of these products were observed. The decomposition has been successfully modeled using a free radical mechanism, with the major chain carriers being CN radicals and H atoms. The initiation reaction was found to be C-H bond fission, to yield H atoms and pyrazyl radicals. Kinetic modeling allowed the rate of initiation to be determined, yielding a first-order rate constant given by the expression k=10 15.7 exp(-96.5 kcal mol -1 /RT) s -1 . The importance of CN radicals as chain carriers appears to be a sigificant difference in the decomposition of the diazines compared with pyridine or 2-picoline. Accompanying the decomposition of pyrazine was the isomerisation of pyrazine to pyrimidine. By kinetic modeling, the isomerisation of pyrazine to pyrimidine was found to occur via a fulvenelike intermediate. The rate and mechanism of the isomerisation are analogous to the isomerisation of fulvene to benzene described by Melius and Miller. © 1994 Combustion Institute.

DOI 10.1016/S0082-0784(06)80724-1
Citations Scopus - 8
1994 Mackie JC, Nelson PF, 'Modelling studies of gas-phase processes in OXCO reactors', Studies in Surface Science and Catalysis, 81 137-142 (1994)

Catalytic oxidative coupling of methane to higher hydrocarbons is an alternative to conversion of methane to synthesis gas (by steam reforming or partial oxidation) and subsequent... [more]

Catalytic oxidative coupling of methane to higher hydrocarbons is an alternative to conversion of methane to synthesis gas (by steam reforming or partial oxidation) and subsequent reaction of the synthesis gas to produce refinery or petrochemical feedstocks. It was recognized early in the development of oxidative coupling that purely gas phase processes could play an important role in determining the composition of the products. An experimental study in a well characterized jet stirred reactor confirmed earlier results and demonstrated that methane was responsible for the inhibition of C 2 oxidation. The experiments in the jet stirred reactor were performed at total pressures of 20-100 Tom, and were successfully modeled with a detailed chemical kinetic model. More recent results have been obtained at somewhat higher pressures, but these are still at considerably lower pressures than would be used in a practical process. However, in view of the likely increased importance of gas-phase reactions at higher pressures, particularly in the conversion of ethane to ethylene and other olefins, a key component of the process concept, and of the success of the model at low pressure, a modeling study of the gas phase processes at higher pressures is justified. © 1994, Elsevier Science & Technology. All rights reserved.

DOI 10.1016/S0167-2991(08)63856-2
1994 Doughty A, Mackie JC, 'Kinetics of thermal decomposition of the diazines: Shock-tube pyrolysis of pyrimidine', Journal of the Chemical Society, Faraday Transactions, 90 541-548 (1994)

The kinetics of pyrolysis of pyrimidine diluted in argon have been studied behind reflected shock waves over the temperature range 1200-1850 K, at uniform gas residence times of 8... [more]

The kinetics of pyrolysis of pyrimidine diluted in argon have been studied behind reflected shock waves over the temperature range 1200-1850 K, at uniform gas residence times of 850-1000 µs and pressures of 13-15 atm. The major products of pyrimidine pyrolysis were found to be acetylene, HCN, acrylonitrile, cyanoacetylene and H 2 . Using both end-product analysis and real-time UV spectrometry the kinetics of pyrimidine disappearance were found to be first order with respect to reactant concentration over the concentration range of 0.07-0.3 mol%. The two techniques yielded a first-order rate constant (k dis ) for the disappearance of pyrimidine given by the expression 10 12.3(±0.4) exp[-275(±13) kJ mol -1 /RT]s -1 . A detailed reaction model incorporating a free-radical mechanism for the decomposition of pyrimidine has been developed, and shown to predict the reactant and product concentrations between 1250 and 1600 K. Important radicals in the mechanism were found to be o- and p-pyrimidyl, with H atoms and CN radicals being radical chain carriers. Sensitivity and flux analysis of the kinetic model has shown the most important initiation pathway to be the loss of an H atom from pyrimidine to yield o-pyrimidyl. Optimisation of the Arrhenius parameters for this initiation reaction yields an activation energy consistent with a heat of formation of the o-pyrimidyl radical of 376(±10) kJ mol -1 .

DOI 10.1039/FT9949000541
Citations Scopus - 23
1993 Freihaut JD, Proscia WM, MacKie JC, 'Chemical and Thermochemical Properties of Heavy Molecular Weight Hydrocarbons Evolved During Rapid Heating of Coal of Varying Rank Characteristics', Combustion Science and Technology, 93 323-347 (1993)

The evolution phenomenology, yields, chemical, and thermochemical properties of heavy hydrocarbons, tars, evolved from a wide range of coal types are presented. Coals varying in r... [more]

The evolution phenomenology, yields, chemical, and thermochemical properties of heavy hydrocarbons, tars, evolved from a wide range of coal types are presented. Coals varying in rank characteristics from lignite to anthracite were rapidly heated to varying extents of devolatilization, the tars isolated from the char stream and subjected to chemical and thermochemical analysis. Systematic variations in the yields, chemical characteristics, thermophysical and thermochemical properties are observed for a given extent of tar evolution from coals of varying rank. Systematic variations are also observed for a given extent of tar evolution from coals of varying rank. Systematic variations are also observed for a given coal but with changing extents of devolatilization. Despite significant variation in the molecular types, yields and temperature-sensitivity of heavy hydrocarbons with coal type, underlying invariances are observed in the evolution sequence of parent coal nitrogen, volatility, functional group distributions, and calorific values of evolved tar species as a function of extent of tar evolution. © 1993, Taylor & Francis Group, LLC. All rights reserved.

DOI 10.1080/00102209308935296
Citations Scopus - 11
1992 Doughty A, Mackie JC, 'Kinetics of pyrolysis of a coal model compound, 2-picoline, the nitrogen heteroaromatic analogue of toluene. 2. The 2-picolyl radical and kinetic modeling', Journal of Physical Chemistry, 96 10339-10348 (1992)

The pyrolysis of 2-picoline, investigated experimentally in our previous paper, 1 has been successfully modeled using a 70-reaction free-radical mechanism. The mechanism includes... [more]

The pyrolysis of 2-picoline, investigated experimentally in our previous paper, 1 has been successfully modeled using a 70-reaction free-radical mechanism. The mechanism includes decomposition pathways for o-pyridyl and 2-picolyl, both of which are formed through the principal initiation reactions of 2-picoline. The proposed mechanism for 2-picolyl decomposition involves the direct ring opening of the 2-picolyl radical. Further reactions of the open chain isomer of 2-picolyl resulted in the formation of the major products HCN and acetylene and the minor products 1-cyanocyclopentadiene and cyclopentadiene. Kinetic modeling confirmed the feasibility of this mechanism by predicting the observed profiles for these species. Optimizing of the heat of formation of 2-picolyl through kinetic modeling resulted in a value of 68 (±5) kcal mol -1 . This value suggests a lower level of resonance stabilization for 2-picolyl compared to benzyl. This inference is supported by the "normal" value of the rate constant for 2-picolyl + H recombination found by modeling to be in the range 1 × 10 13 -6 × 10 13 cm 3 mol -1 s -1 . The reactant and product profiles predicted by the kinetic model were found to be very sensitive to the rate of the initiation reaction yielding methyl and o-pyridyl radicals, allowing the heat of formation of the o-pyridyl radical to be determined. The optimized rate constant for this initiation reaction was found to be 10 16.1(±0.2) exp(-91.5 (±2) kcal mol -1 /RT) s -1 , corresponding to a heat of formation for the o-pyridyl radical of 84.1 (±2) kcal mol -1 . © 1992 American Chemical Society.

Citations Scopus - 16
1992 Doughty A, MacKie JC, 'Kinetics of pyrolysis of the isomeric butenenitriles and kinetic modeling', Journal of Physical Chemistry, 96 272-281 (1992)

Kinetics of pyrolysis of the butenenitrile isomers, cis- and trans-crotononitrile and allyl cyanide, have been studied dilute in argon in a single-pulse shock tube over the temper... [more]

Kinetics of pyrolysis of the butenenitrile isomers, cis- and trans-crotononitrile and allyl cyanide, have been studied dilute in argon in a single-pulse shock tube over the temperature range of 1200-1500 K at uniform gas residence times behind the reflected shock of between 650 and 750 µs and at pressures between 18 and 20 atm. Thermal decomposition was preceded by isomerization of the butenenitriles whose rates are coupled with the rates of thermal decomposition. The decomposition was found to follow a free-radical mechanism with the major chain involving propagation reactions of the cyanomethyl radical to produce acetonitrile and acetylene. Other routes important to the mechanism involve hydrogen atom addition to the butenenitriles. HCN principally arises from this route. A detailed kinetic reaction model is presented to model the experimental reactants and products profiles as a function of temperature. From the modeling and experiment, the following initiation rate constants have been obtained: trans-CH 3 CH=CHCN ¿ CH 3 + HC=CHCN (k -11 = 10 17.45 exp(-96.5/RT) s -1 ), cis-CH 3 CH=CHCN ¿ CH 3 + HC=CHCN (k -12 = 10 17.53 exp(-98.5/RT) s -1 ), CH 2 =CHCH 2 CN ¿ H 2 C=CH + CH 2 CN (k -13 = 10 15.53 exp(-82.6/RT) s -1 ), where the activation energies are in kcal mol -1 . © 1992 American Chemical Society.

Citations Scopus - 14
1992 Terentis A, Doughty A, Mackie JC, 'Kinetics of pyrolysis of a coal model compound, 2-picoline, the nitrogen heteroaromatic analogue of toluene. 1. Product distributions', Journal of Physical Chemistry, 96 10334-10339 (1992)

The pyrolysis of 2-picoline in dilute mixtures with argon has been investigated using the single-pulse shock tube and was found to decompose over the temperature range 1300-1550 K... [more]

The pyrolysis of 2-picoline in dilute mixtures with argon has been investigated using the single-pulse shock tube and was found to decompose over the temperature range 1300-1550 K, at an average residence time of 800 µs and uniform pressure of 14-16 atm. The major products observed were acetylene, methane, hydrogen, HCN, and cyanoacetylene. Over the studied range of mixture compositions (0.06-0.20 mol % of 2-picoline) the overall rate of disappearance of 2-picoline obeyed first-order kinetics. Arrhenius parameters for disappearance of picoline were found to be A dis = 10 17.4±1.1 s -1 and E a,dis = 98 ± 7 kcal mol -1 . From the distribution of observed products it is concluded that the principal initiation reactions were analogous to those known to occur in toluene, the hydrocarbon analogue of 2-picoline, and were found to be C-C bond fission to yield the o-pyridyl and methyl radicals and C-H fission to yield H atoms and 2-picolyl, the N-containing analogue of benzyl. Major products were observed from decomposition of both the o-pyridyl and the 2-picolyl radicals. Cyanoacetylene arises principally from secondary reactions of o-pyridyl. A product with m/z = 91 was observed at the lowest temperatures at which 2-picoline decomposition could be detected. It has been identified as 1-cyanocyclopentadiene and arises from loss of H from the 2-picolyl radical. Other products arising from secondary decomposition of 2-picolyl at higher temperatures include HCN and cyclopentadienyl radicals. © 1992 American Chemical Society.

Citations Scopus - 24
1991 Mackie JC, 'Partical Oxidation of Methane: The Role of the Gas Phase Reactions', Catalysis Reviews, 33 169-240 (1991)
DOI 10.1080/01614949108020299
Citations Scopus - 105
1991 Mackie JC, Colket MB, Nelson PF, Esler M, 'Shock tube pyrolysis of pyrrole and kinetic modeling', International Journal of Chemical Kinetics, 23 733-760 (1991)

The kinetics of pyrolysis of pyrrole dilute in argon have been studied in a single pulse shock tube, using capillary column GC, together with GC/MS and FTIR for product identifica... [more]

The kinetics of pyrolysis of pyrrole dilute in argon have been studied in a single pulse shock tube, using capillary column GC, together with GC/MS and FTIR for product identification, over the temperature range 1200¿1700 K, total pressures of 7.5¿13.5 atm and nominal mixture compositions of pyrrole of 5000 and 700 ppm (nominal concentrations of 5 × 10 -7 and 7 × 10 -8 mol cm -3 ). Time-resolved measurements of the rate of disappearance of pyrrole behind reflected shock waves have been made by absorption spectroscopy at 230 nm, corresponding to the lowest 1 p* ¿ 1 p transition of pyrrole at pressures of 20 atm and mixture compositions between 1000¿2000 ppm pyrrole (1.7¿3.0 × 10 -7 mol cm -3 ) over the temperature range of 1300 to 1700 K. At the lower end of the studied temperature range, the isomers of pyrrole, allyl cyanide and cis- and trans-crotononitrile, were the principal products, together with hydrogen cyanide and propyne/allene. At elevated temperatures, acetylene, acetonitrile, cyanoacetylene, and hydrogen became important products. The rate of overall disappearance of pyrrole, as measured by absorption spectrometry, was found to be first order in pyrrole concentration, with a rate constant k dis (pyrrole) = 10 14.1±0.7 exp(-74.1 ± 3.0 kcal mol -1 /RT) s -1 between 1350¿1600 K and at a pressure of 20 atm. First order dependence of pyrrole decomposition and major product formation was also observed in the single pulse experiments over the range of mixture compositions studied. A 75-step reaction model is presented and shown to substantially fit the observed temperature profiles of the major product species and the reactant profile. In the model the initiation reaction is postulated to be the reversible formation of pyrrolenine, (2H-pyrrole). Pyrrolenine can undergo ring scission at the C2¿N bond forming a biradical which can rearrange to form allyl cyanide and crotononitrile or undergo decomposition to form HCN and C 3 H 4 or acetylene and a precursor of acetonitrile. The model predicts an overall rate of disappearance of pyrrole in agreement with the experimental measurements. Copyright © 1991 John Wiley & Sons, Inc.

DOI 10.1002/kin.550230807
Citations Scopus - 90
1991 Organ PP, Mackie JC, 'Kinetics of pyrolysis of furan', Journal of the Chemical Society, Faraday Transactions, 87 815-823 (1991)

The kinetics of pyrolysis of furan vapour diluted in argon have been studied behind reflected shock waves in a shock tube both by time-resolved infrared CO 2 laser absorption spe... [more]

The kinetics of pyrolysis of furan vapour diluted in argon have been studied behind reflected shock waves in a shock tube both by time-resolved infrared CO 2 laser absorption spectrometry and by single pulse shock techniques of product analysis over the temperature range 1100-1700 K, at pressures of ca. 20 atm and at uniform residence times of ca. 300 µs. The rate of overall disappearance of furan, as measured by absorption spectrometry, was found to be first order in furan concentration, with a rate constant of k overall = 10 15.3±0.3 exp[-326(±8) kJ mol -1 /RT] s -1 in agreement with a previous determination by Lifshitz et al. (A. Lifshitz, M. Bidani and S. Bidani, J. Phys. Chem., 1986, 90, 5373). Principal products were carbon monoxide, C 3 H 4 (propyne and allene) and acetylene. Ketene was identified in the products by FTIR spectroscopy. A detailed chemical reaction model for the pyrolysis was developed and shown to give good predictions of the concentration profiles of furan and the major products. Modelling and thermochemical considerations led to the postulate that the initiation of pyrolysis takes place by C-O bond scission to a biradical which can undergo decomposition, via parallel reaction paths, to the observed products.

DOI 10.1039/FT9918700815
Citations Scopus - 53
1990 Mackie JC, Colket MB, Nelson PF, 'Shock tube pyrolysis of pyridine', Journal of Physical Chemistry®, 94 4099-4106 (1990)

The kinetics of pyrolysis of pyridine dilute in argon have been studied in a single-pulse shock tube, using capillary column GC together with GC/MS and FTIR spectroscopy for produ... [more]

The kinetics of pyrolysis of pyridine dilute in argon have been studied in a single-pulse shock tube, using capillary column GC together with GC/MS and FTIR spectroscopy for product determination, over the temperature range of 1300-1800 K and total pressures of 7-11 atm. At the lower end of the studied temperatures, cyanoacetylene was found to be the principal nitrogen-containing product. At elevated temperature hydrogen cyanide predominated. Other major products were acetylene and hydrogen. Thermochemical estimates of the isomeric cyclic pyridyls produced in the pyrolysis indicate that the ortho isomer is unique in being able to undergo facile cleavage to an open-chain cyano radical from which cyanoacetylene is produced. Several sources of HCN were identified in the system. The m- and p-pyridyls may eliminate HCN in a molecular process. An important source of HCN at high temperatures is the addition of H atoms to cyano compounds, especially cyanoacetylene, but also acetonitrile and acrylonitrile which are produced in the pyrolysis. The pyrolysis is a chain process initiated principally by C-H bond fission to form o-pyridyl. A 58-step reaction model is presented and shown to substantially fit the observed profiles of the major product species. From this model we derive a value for the rate constant of the principal initiation reaction, C5H5N ¿ o-C 5 H 4 N + H (1), of k 1 = 10 15.9±0.4 exp(-98 ± 3 kcal mol -1 /RT) s -1 between 1300 and 1800 K and at a total pressure of about 10 atm. © 1990 American Chemical Society.

Citations Scopus - 126
1990 Mackie JC, Smith JG, Nelson PF, Tyler RJ, 'Inhibition of C2 Oxidation by Methane under Oxidative Coupling Conditions', Energy and Fuels, 4 277-285 (1990)

The gas-phase partial oxidation of ethane and ethylene have been studied in a completely stirred tank reactor over the temperature range of 920¿1220 K, at total pressures from 40... [more]

The gas-phase partial oxidation of ethane and ethylene have been studied in a completely stirred tank reactor over the temperature range of 920¿1220 K, at total pressures from 40 to 100 Torr, and at residence times between 0.1 and 1 s. Methane was found to have a pronounced inhibiting effect upon the partial oxidation of both C 2 species. Ethylene is the principal carbon-containing product of partial oxidation of ethane. The ratio of the selectivities to ethylene and carbon monoxide depends only on the extent of conversion of the ethane and not on the presence of methane in the reactants. Carbon monoxide is the principal product of partial oxidation of ethylene. Selectivity to CO is reduced and selectivity to propene is enhanced when methane is present in the reaction mixtures. A detailed chemical kinetic reaction model has been developed to simulate the partial oxidation of the C 2 species and to model the inhibiting effect of the methane on C 2 oxidation. © 1990, American Chemical Society. All rights reserved.

DOI 10.1021/ef00021a011
Citations Scopus - 22
1990 Mackie JC, Hart MG, 'Partial Oxidation of Methane by Nitrous Oxide', Energy and Fuels, 4 285-290 (1990)

Partial oxidation of methane by nitrous oxide has been studied behind reflected shock waves in a single-pulse shock tube over the temperature range of 1400¿1940 K, at a pressure ... [more]

Partial oxidation of methane by nitrous oxide has been studied behind reflected shock waves in a single-pulse shock tube over the temperature range of 1400¿1940 K, at a pressure of 15 atm, and with uniform gas residence time of 0.4 ms. Mixtures of N 2 O and CH 4 , each of mole fraction 0.01 in Ar, commenced decomposition at temperatures above 1400 K. Ethane and ethylene are the principal carbon-containing products of partial oxidation below 1580 K. At higher temperatures, acetylene and carbon monoxide predominate. High conversions and selectivities to C 2 hydrocarbons have been obtained with N 2 O, and at 1532 K, methane conversion of 45.8% with selectivity to C 2 ¿s of 81% has been recorded. The experimental concentration profiles of reactants and major products in the N 2 O partial oxidation of CH 4 have been modeled satisfactorily by a detailed chemical kinetic reaction model. Sensitivity and rate of production analyses of the model have been used to identify the rate-determining reactions in both N 2 O and O 2 partial oxidations of methane. The model has been used to predict methane conversions and products¿ selectivities at reactant mole fractions up to 0.5. © 1990, American Chemical Society. All rights reserved.

DOI 10.1021/ef00021a012
Citations Scopus - 3
1989 Mackie JC, Doolan KR, Nelson PF, 'Kinetics of the thermal decomposition of methoxybenzene (anisole)', Journal of physical chemistry, 93 664-670 (1989)

The thermal decomposition of anisole vapor dilute in argon has been studied in a perfectly stirred reactor over the temperature range 850-1000 K and at total pressures of (16-120)... [more]

The thermal decomposition of anisole vapor dilute in argon has been studied in a perfectly stirred reactor over the temperature range 850-1000 K and at total pressures of (16-120) × 10 -3 atm. Decomposition of anisole takes place principally by the reaction C 6 H 5 OCH 3 ¿C 6 H 5 O+CH 3 , for which the rate constant k 1 was found to be (2.9±1.0) ×10 15 exp(-64.0±0.6 kcal mol -1 /RT)s -1 . Phenoxy radicals thus generated may decompose unimolecularly to cyclopentadienyl radicals and CO or react with methyl radicals to form cresols. Phenol is also an important secondary product. Most of the product oxygen originally contained in anisole is found in phenolic compounds rather than in carbon monoxide.

Citations Scopus - 46
1988 Nelson PF, Smith IW, Tyler RJ, Mackie JC, 'Pyrolysis of Coal at High Temperatures', Energy and Fuels, 2 391-400 (1988)

Pyrolysis of coal and of tar produced by the rapid pyrolysis of coal has been studied in small fluidized-bed reactors and in a shock tube. Kinetic parameters determined for the fo... [more]

Pyrolysis of coal and of tar produced by the rapid pyrolysis of coal has been studied in small fluidized-bed reactors and in a shock tube. Kinetic parameters determined for the formation of light hydrocarbon gases from the rapid pyrolysis of coal suggest that rate-limiting coupled processes, such as internal mass transfer, have an influence on the formation rates. However, when this limitation is removed, by studying the gas-phase cracking of tar free from the influences of the original coal or char, only the light olefins that apparently arise from a single type of functional group give activation energies indicative of bond-breaking reactions. Other products, which appear to have several different chemical sources, exhibit low activation energies of formation (110-140 kJ/mol). Results of a detailed study of tar composition as a function of temperature in the fluid-bed reactor were consistent with the proposal that long-chain polymethylene groups are the source of the olefins and that secondary cracking reactions of the tar are an important source of simple aromatics, polycyclic aromatic hydrocarbons, and carbon oxides. Results are also presented to show the effect of preparation conditions on the combustion kinetics of chars produced by rapid pyrolysis. At combustion temperatures of 700 °C, the reactivities of the chars show an inverse relationship to their preparation temperatures, but at higher combustion temperatures, these differences largely disappear. © 1988, American Chemical Society. All rights reserved.

DOI 10.1021/ef00010a004
Citations Scopus - 53
1987 Doolan KR, Mackie JC, Tyler RJ, 'Coal flash pyrolysis: secondary cracking of tar vapours in the range 870-2000 K', Fuel, 66 572-578 (1987)

Tar free from influences of the original coal or char was cracked in two reaction systems, one using tar vapour in tubular quartz reactors at 900-1400 K and reactor residence time... [more]

Tar free from influences of the original coal or char was cracked in two reaction systems, one using tar vapour in tubular quartz reactors at 900-1400 K and reactor residence times of ¿ 0.2 and ¿ 1 s, the other using tar aerosol in a shock tube at 1100-2000 K and residence time ¿ 1 ms. In the latter system the aerosol evaporated rapidly after passage of the shock front and the tar behaved kinetically as a vapour. Yields of light hydrocarbons including C 6 H 6 and CO from tar cracking were determined as a function of temperature. Maximum yields of individual species agreed well between the two reactors but the temperatures of maximum yield depended on residence time. Hydrocarbon yields on a daf coal basis were very similar to those obtained previously by direct flash pyrolysis of the same coal at 870-1270 K. Kinetic analyses of the formation of C 2 H 4 , C 3 H 6 and C 2 H 2 gave activation energies of 220-260 kJ mol -1 , similar to those for formation of the same hydrocarbons from n-hexadecane. The precursors of the alkenes could be polymethylene groups in the tar. CH 4 , C 6 H 6 and CO all had low activation energies of formation, reflecting the many different functional groups capable of eliminating these molecules. © 1987.

DOI 10.1016/0016-2361(87)90166-9
Citations Scopus - 45
1986 Doolan KR, Mackie JC, Reid CR, 'High temperature kinetics of the thermal decomposition of the lower alkanoic acids', International Journal of Chemical Kinetics, 18 575-596 (1986)

The thermal decomposition of propanoic acid dilute in argon has beenstudied in a single-pulse shock tube over the temperature range of 1100-1500 K and over the pressure range of 1... [more]

The thermal decomposition of propanoic acid dilute in argon has beenstudied in a single-pulse shock tube over the temperature range of 1100-1500 K and over the pressure range of 14-18 atm. The decomposition kinetics have been satisfactorily computer modelled by means of afree radical mechanism involving H and OH chains. Recent single-pulse shock tube product analyses of acetic acid decomposition have been computer modelled using a free radical mechanism for decarboxylation coupled to a unimolecular dehydration reaction. A comparison between the thermal decomposition kinetics of the C 1 ¿C 3 alkanoic acids is made. The present studies do notprovide evidence for the participation of transition states involving a pentavalent carbon atom in the pyrolyses of the lower alkanoic acids. Copyright © 1986 John Wiley & Sons, Inc.

DOI 10.1002/kin.550180508
Citations Scopus - 1
1985 Doolan KR, Mackie JC, 'Products from the rapid pyrolysis of a brown coal in inert and reducing atmospheres', Fuel, 64 400-405 (1985)

Yallourn brown coal and its calcium form have been pyrolysed in three different gas mixtures: 23% methane in argon, 50% hydrogen in argon, and 9.4% toluene in argon, at heating ra... [more]

Yallourn brown coal and its calcium form have been pyrolysed in three different gas mixtures: 23% methane in argon, 50% hydrogen in argon, and 9.4% toluene in argon, at heating rates of 10 7 Ks -1 and residence times of ¿2 ms. The products have been compared with those obtained in pure argon. The highly reactive molecule, ketene, was detected in the pyrolysate gases from both the 'raw' and calcium-form coals when pyrolysed in the above mixtures. Ketene was not detected in the pyrolysate gases, however, when the coals were pyrolysed in argon alone. When pyrolysed in 23% methane/argon the maximum yield of carbon monoxide from the 'raw' coal was found to be much lower than when pyrolysed in pure argon. The fully exchanged calcium-form coal when pyrolysed in pure argon, gave a maximum yield of carbon dioxide of oxygen content equal to the total oxygen content of the carboxyl groups originally present in the coal; the C0 2 yield from the 'raw' coal was about half that from the calcium-form in pure argon. © 1985.

DOI 10.1016/0016-2361(85)90431-4
Citations Scopus - 19
1985 Doolan KR, Mackie JC, 'Kinetics of rapid pyrolysis of a calcium-exchanged brown coal and of a calcium model compound', Symposium (International) on Combustion, 20 1463-1469 (1985)

The pyrolysis of calcium exchanged Yallourn brown coal has been carried out under rapid heating conditions in a shock tube which generated heating rates of 10 7 K s -1 . The resu... [more]

The pyrolysis of calcium exchanged Yallourn brown coal has been carried out under rapid heating conditions in a shock tube which generated heating rates of 10 7 K s -1 . The results are compared with the pyrolysis of untreated Yallourn brown coal and with calcium acetate chosen as a model for carboxylate group decomposition. Light hydrocarbon yields from the two coals were the same within experimental error. It is suggested that these products arise from secondary decomposition of tars of similar composition. Compared to the untreated coal, increased CO 2 and decreased CO were found for the calcium-exchanged coal. The primary products of thermal decomposition of calcium acetate were found to be acetone, carbon dioxide, methane and ketene for temperatures in the range 900-1500 K. The overall rate of decomposition and primary product yields were fitted by means of a detailed model consisting of 16 chemical reactions. For the initial decomposition reactions of the calcium acetate low Arrhenius parameters were found. These parameters were similar to those found for formation of volatile products from the coals when based on a first order kinetic coal decomposition model. © 1985 Combustion Institute.

DOI 10.1016/S0082-0784(85)80639-1
Citations Scopus - 4
1985 Doolan KR, Mackie JC, Tyler RJ, 'SECONDARY DECOMPOSITION OF TAR VAPOURS PRODUCED BY FLASH PYROLYSING COAL.' (1985)

Tar from the flash pyrolysis at 870 K of Millmerran sub-bituminous coal has been pyrolysed free from influences of char or coal in a shock tube between 1100 K and 1900 K at 1 ms r... [more]

Tar from the flash pyrolysis at 870 K of Millmerran sub-bituminous coal has been pyrolysed free from influences of char or coal in a shock tube between 1100 K and 1900 K at 1 ms residence time. Maximum yields of light volatiles from the tar are equal to those obtained from pyrolysis of the original coal, demonstrating that under these pyrolysis conditions, tar is the source of the light products. Kinetic analyses of product formation are reported.

Citations Scopus - 3
1984 Cliff DI, Doolan KR, Mackie JC, Tyler RJ, 'Products from rapid heating of a brown coal in the temperature range 400-2300 °C', Fuel, 63 394-400 (1984)

The devolatilisation behaviour of Yallourn brown coal was investigated under rapid heating conditions using two different flash pyrolysers: a fluid-bed reactor giving coal particl... [more]

The devolatilisation behaviour of Yallourn brown coal was investigated under rapid heating conditions using two different flash pyrolysers: a fluid-bed reactor giving coal particle heating rates of 10 4 °Cs -1 with a gas residence time of about 0.5 s and a shock tube which generated heating rates of the order of 10 7 °Cs -1 and a 1 ms reaction time. Yields of products are reported covering pyrolysis temperatures in the range 400-2300 °C. Hydrocarbon gas yields reached maximum values which were remarkably similar for both reactors although occurring at different temperatures. Carbon oxide production was also similar for both reactors with CO yields reaching 30% wt/wt daf coal. These high yields of CO are very different from those reported for slow heating conditions. It appears that on flash heating, coal decomposition pathways change in a manner which increases CO yields at the expense of H 2 0 and to a lesser extent C0 2 , resulting in the volatilisation of additional carbon from the coal. © 1984.

DOI 10.1016/0016-2361(84)90018-8
Citations Scopus - 46
1984 Mackie JC, Doolan KR, 'High-temperature kinetics of thermal decomposition of acetic acid and its products', International Journal of Chemical Kinetics, 16 525-541 (1984)

Kinetics of the thermal decomposition of acetic acid vapor dilute in argon have been studied over the temperature range of 1300¿1950 K in a single-pulse shock tube. The acid was ... [more]

Kinetics of the thermal decomposition of acetic acid vapor dilute in argon have been studied over the temperature range of 1300¿1950 K in a single-pulse shock tube. The acid was found to decompose homogeneously and molecularly via two competing firstorder reaction channels at nearly equal rates, to form methane and carbon dioxide on the one hand, and ketene and water on the other. Fall-off behavior has been taken into account and limiting high-pressure rate constants for both channels have been derived. Ketene was found to decompose both unimolecularly to methylene radicals and carbon monoxide and also by a radical reaction with CH 2 to form ethylene and carbon monoxide. The rate constant derived for the unimolecular reaction was found to be in good agreement with an earlier shock tube measurement by H. G. Wagner and F. Zabel [Ber. Bunsenges Phys. Chem., 75, 114 (1971)]. The bimolecular reaction of ketene to produce allene and carbon dioxide, important in lower temperature reaction systems, has been found to be unimportant under the present conditions. A computer model for the decomposition kinetics involving 46 reactions of 21 species has been found to simulate the experimental yield data substantially. Sensitivity analyses have been used to identify reactions which make important contributions to the overall mechanism and yields of major products. Methylene radicals play important roles in determining yields of major species. Copyright © 1984 John Wiley & Sons, Inc.

DOI 10.1002/kin.550160504
Citations Scopus - 6
1983 Doolan KR, Mackie JC, 'Kinetics of pyrolysis of octane in argonhydrogen mixtures', Combustion and Flame, 50 29-39 (1983)

The pyrolysis kinetics of n-octane dilute in both argon and 50 mol% mixtures of argon and hydrogen have been studied in the temperature range 1000-1400K in a single-pulse shock tu... [more]

The pyrolysis kinetics of n-octane dilute in both argon and 50 mol% mixtures of argon and hydrogen have been studied in the temperature range 1000-1400K in a single-pulse shock tube. In the inert gas pyrolyses principal products of reaction are ethylene, methane, and propene. Yields of methane and ethane are increased in pyrolyses in 50 mol% mixtures of argon and hydrogen and the rate of decomposition of octane is approximately an order of magnitude larger than that in inert gas pyrolyses. Methyl radical and hydrogen atom attack on the parent octane determines the octane decomposition kinetics and methyl, and ethyl radical attack on hydrogen have been found to be important in determining product distributions in pyrolyses containing hydrogen. Both overall kinetics and product distributions can be simulated by a reaction model based on a modified Kossiakoff-Rice mechanism involving coupled isomerization and unimolecular decomposition of large alkyl radicals. © 1983.

DOI 10.1016/0010-2180(83)90046-9
Citations Scopus - 26
1983 Doolan KR, Mackie JC, Weiss RG, 'Heat transfer to fine coal particles in flash pyrolysis', Combustion and Flame, 49 221-233 (1983)

Heat transfer to fine bituminous coal particles suspended in argon has been studied by recording infrared emission from the coal as a function of time at wavelengths 3.42 and 2.26... [more]

Heat transfer to fine bituminous coal particles suspended in argon has been studied by recording infrared emission from the coal as a function of time at wavelengths 3.42 and 2.26 µm when the coal was subjected to very rapid heating by a shock wave. The rate of particle heating was found to fit a Nusselt model of conductive heat transfer. Light extinction studies on coal suspensions showed that particles of diameters =5 µm undergo velocity relaxation behind the shock front in less than 30 µs. Allowance for forced convective heat transfer to the coal particles in the velocity relaxation zone was made in the heat transfer analysis but forced convection was found to be unimportant in these studies. The Nusselt heat conduction model has been found to hold for heat transfer to micron-sized coal particles up to 1200K; above this temperature infrared emission from soot produced from products of devolatilization of the coal becomes important. © 1983.

DOI 10.1016/0010-2180(83)90165-7
Citations Scopus - 8
1982 Doolan KR, Mackie JC, Mulcahy MFR, Tyler RJ, 'Kinetics of rapid pyrolysis and hydropyrolysis of a sub-bituminous coal', Symposium (International) on Combustion, 19 1131-1138 (1982)

Coal pyrolysis in both argon and hydrogen atmospheres has been investigated in the temperature range 1100-2300K using a shock tube. Particles of size < 10 µm diameter were studi... [more]

Coal pyrolysis in both argon and hydrogen atmospheres has been investigated in the temperature range 1100-2300K using a shock tube. Particles of size < 10 µm diameter were studied. Particle heating rates of 10 7 Ks -1 were achieved giving particle heating times of < ~150 µs. This high rate of heating enabled the devolatilisation kinetics to be decoupled from particle heat-up effects. Particle cooling rates due to the rarefaction wave in the shock tube were 5×10 5 Ks -1 . Residence times ranged from 0.25-1.3 ms and total pressures from 17-35 atmospheres. C 1 -C 7 hydrocarbons and benzene, toluene and xylene yields were determined for pyrolysisin both argon and hydrogen/inert gas mixtures. Major gaseous products included CH 4 , C 2 H 4 , C 3 H 6 , 1, 3-butadiene and benzene. C 2 H 2 only became important at temperatures above 1500K and was attributed to secondary gas phase decomposition of the volatilised species. In the presence of hydrogen the major effect observed was an increase in the yields of CH 4 and C 6 H 6 . C 2 H 2 yields were markedly lower in H 2 . The results were fitted by a first order evolution and secondary decomposition model which included equations to allow for particle heatup and quench. The model enabled kinetic parameters for volatile species evolution and decomposition to be evaluated. The implications of these results to coal pyrolysis are discussed. © 1982 Combustion Institute.

DOI 10.1016/S0082-0784(82)80289-0
Citations Scopus - 17
1981 Hodgson AW, Mackie JC, 'Double-diaphragm shock tube: Comparison between theory and experiment', AIAA Journal, 19 405-406 (1981)
DOI 10.2514/3.7781
1981 Mackie JC, Nicholls J, 'Supersonically expanding reacting flows: The chemiluminescent sn/n20 reaction', Australian Journal of Chemistry, 34 271-282 (1981)

A supersonic flow reactor comprising a shock tube and convergent-divergent expansion nozzle has been developed and used to study the chemiluminescent reaction between tin atoms an... [more]

A supersonic flow reactor comprising a shock tube and convergent-divergent expansion nozzle has been developed and used to study the chemiluminescent reaction between tin atoms and nitrous oxide. The reaction has been found to excite the a-X, b-X and A-X transitions of SnO and rate constants for formation of the three excited states have been found to have the same activation energy, 25 + 5 kJ mol-'. Estimates of branching ratios have been made on the basis of experimental measurement and kinetic modelling and an assessment of the Sn/N2O reaction as a possible electronic chemical laser is made. © 1981 ASEG.

DOI 10.1071/CH9810271
1981 Hodgson AW, Mackie JC, 'Homogeneous nucleation of cyclohexane: A double-diaphragm shock tube study', Journal of Colloid And Interface Science, 83 547-557 (1981)

The double-diaphragm shock tube technique was applied to the study of homogeneous nucleation for the first time. The condensation of 1% cyclohexane vapor in argon carrier gas was ... [more]

The double-diaphragm shock tube technique was applied to the study of homogeneous nucleation for the first time. The condensation of 1% cyclohexane vapor in argon carrier gas was observed by light scattering. The measured "end of condensation" point was shown to yield information similar to that for the "onset of condensation" point observed in nozzle and shock tube driver expansion experiments. The data were fitted to a classical-type nucleation equation by means of an adjustable preexponential factor K. Definitive analysis is not possible at this stage as the surface free energy of small cyclohexane clusters is uncertain under our conditions (temperatures of about 160°K). Experimental nucleation rates were therefore determined for a range of surface free energy values. © 1981.

DOI 10.1016/0021-9797(81)90349-0
Citations Scopus - 3
1979 Hodgson A, Mackie JC, 'A shock-tube study of the kinetics of evaporation and oxidation of magnesium', Combustion and Flame, 35 323-334 (1979)

Oxidation kinetics of magnesium have been studied by shock heating dilute magnesium aerosol suspended in argonoxygen and argon-air carrier gas to gas temperatures of around 2000°... [more]

Oxidation kinetics of magnesium have been studied by shock heating dilute magnesium aerosol suspended in argonoxygen and argon-air carrier gas to gas temperatures of around 2000°K. Magnesium vapour profiles have been recorded using atomic absorption spectrometry. Oxidation of magnesium occurs via a homogeneous gas-phase reaction Mg+O 2 ¿MgO+O, and the rate coefficient for oxidation has been measured as (5 ± 3) × 10 10 cm 3 mole -1 sec -1 at 2000°K. The evaporation rate of particulate magnesium has been determined by shocking the aerosol in pure argon, and the rate has been measured by both light-extinction and atomic-absorption techniques. The evaporation rate can be expressed in terms of a simple first-order evaporation-rate coefficient k 1 = (3 ± 1.5) × 10 4 sec -1 . This value is suggestive of a surface oxide coating on the magnesium particles. © 1979.

DOI 10.1016/0010-2180(79)90037-3
Citations Scopus - 8
1978 Evans PJ, Mackie JC, 'Comment on "Shock-wave chemistry in dusty gases and fogs: A review," by M. A. Nettleton', Combustion and Flame, 32 321-322 (1978)
DOI 10.1016/0010-2180(78)90107-4
Citations Scopus - 1
1978 Beck WH, MacKie JC, 'Application of the shock tube unsteady expansion wave technique to the study of chemical reactions', Journal of Physics D: Applied Physics, 11 1249-1262 (1978)

An unsteady expansion wave was generated through rupture of a secondary diaphragm by an incident shock wave in a shock tube to study the three-body recombination of iodine atoms. ... [more]

An unsteady expansion wave was generated through rupture of a secondary diaphragm by an incident shock wave in a shock tube to study the three-body recombination of iodine atoms. The application to chemical reaction studies has been made possible through an extension of the usable flow time, and a theoretical treatment enables the effect of coupling of chemical reaction to gas flow to be taken into account. Species concentrations along different particle paths in the expansion wave are given to show the three types of flow regime (frozen, nonequilibrium and equilibrium) which can be accessed by this technique. Using these results, theoretical and experimental I 2 concentration profiles are compared as a function of time in the nonequilibrium regime.

DOI 10.1088/0022-3727/11/9/003
Citations Scopus - 3
1977 Evans PJ, Mackie JC, 'MgO triplet-triplet transitions and intensities', Journal of Molecular Spectroscopy, 65 169-170 (1977)
DOI 10.1016/0022-2852(77)90371-X
Citations Scopus - 11
1976 Beck WH, Mackie JC, 'Recombination of iodine atoms in an unsteady expansion', Chemical Physics Letters, 44 444-448 (1976)

Recombination of iodine atoms generated by shock heating I 2 in Ar is studied in an unsteady expansion. The three-body recombination rate coefficient has been measured as 3 × 10... [more]

Recombination of iodine atoms generated by shock heating I 2 in Ar is studied in an unsteady expansion. The three-body recombination rate coefficient has been measured as 3 × 10 15 (T/298) -1.56 cm 6 mol -2 s -1 between 500 and 1450 K. Coupling of vibrational and chemical relaxation is found to occur in the expansion. © 1976.

DOI 10.1016/0009-2614(76)80701-4
Citations Scopus - 4
1976 Jones DG, Mackie JC, 'Evaluation of C2 resonance fluorescence as a technique for transient flame studies', Combustion and Flame, 27 143-146 (1976)

Resonance fluorescence from C 2 in flames induced by the 514.53 nm line of a cw argon ion laser has been studied experimentally and theoretically using computer-generated spectra... [more]

Resonance fluorescence from C 2 in flames induced by the 514.53 nm line of a cw argon ion laser has been studied experimentally and theoretically using computer-generated spectra. An assessment is made of the feasibility of resonance fluorescence techniques for making real-time measurements of C 2 number density fluctuations in atmospheric hydrocarbon flames. © 1976.

DOI 10.1016/0010-2180(76)90018-3
Citations Scopus - 13
1976 Gaynor BJ, Gilbert RG, King KD, Mackie JC, 'The isomerization of cycloheptatriene at high temperatures', International Journal of Chemical Kinetics, 8 695-707 (1976)

The isomerization of cycloheptatriene at high temperatures (800¿1250°K) has been studied experimentally using a shock tube at high pressures and by very low-pressure pyrolysis i... [more]

The isomerization of cycloheptatriene at high temperatures (800¿1250°K) has been studied experimentally using a shock tube at high pressures and by very low-pressure pyrolysis in the intermediate-pressure region (the first direct use of the latter technique for an isomerization). Rate coefficients obtained are in accord with previous results at lower temperatures. The results are examined theoretically to account for weak-collision nonequilibrium effects. These corrections are found to be appreciable at the temperatures studied. Copyright © 1976 John Wiley & Sons, Inc.

DOI 10.1002/kin.550080506
Citations Scopus - 13
1975 Beck WH, MacKie JC, 'Formation and dissociation of C2 from high temperature pyrolysis of acetylene', Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, 71 1363-1371 (1975)

Kinetics of formation and decay of C 2 produced by passing shock waves through dilute C 2 H 2 +Ar mixtures were studied at temperatures in the range 4860-6920 K. The kinetics of ... [more]

Kinetics of formation and decay of C 2 produced by passing shock waves through dilute C 2 H 2 +Ar mixtures were studied at temperatures in the range 4860-6920 K. The kinetics of formation of C 2 were in essential agreement with a postulated simple two-step dissociation of C 2 H 2 by Ar. The rate constant for the dissociation of C 2 by Ar was found to be k C2,Ar = 10 -(9.21±0.27) exp(-581±59 kJ mol -1 /RT) cm 3 molecule -1 s -1 .

DOI 10.1039/F19757101363
Citations Scopus - 19
1974 Evans PJ, Mackie JC, 'Energy levels of gaseous magnesium monoxide and the bond dissociation energy', Chemical Physics, 5 277-282 (1974)

Absorption and emission spectra of gaseous magnesium monoxide produced by shock-heating MgO particles suspended in Ar/O 2 mixtures have been studied as a function of temperature.... [more]

Absorption and emission spectra of gaseous magnesium monoxide produced by shock-heating MgO particles suspended in Ar/O 2 mixtures have been studied as a function of temperature. The green B 1 S + -X 1 S + system has been observed in absorption for the first time and the X state is found to lie lower by 3200 ± 1000 cm -1 than the lower state of the strong ultraviolet system at 372.1 nm which is attributed to a triplet-triplet transition in MgO. A strong continuum has been observed in absorption by MgO vapour. A discussion of the bond dissociation energy of MgO is given which suggest that the appropriate value D 0 0 (MgO) = 390± 35 kJ mol -1 . © 1974.

DOI 10.1016/0301-0104(74)80025-X
Citations Scopus - 11
1973 Cathro WS, MacKie JC, 'Oscillator strength of the C2-B2S-X2S transition: A shock-tube determination', Journal of the Chemical Society, Faraday Transactions 2: Molecular and Chemical Physics, 69 237-245 (1973)

Comparative intensity measurements of C 2 and C 2 - molecular spectra have been made using a shock tube technique. From these measurements the absorption electronic oscillator s... [more]

Comparative intensity measurements of C 2 and C 2 - molecular spectra have been made using a shock tube technique. From these measurements the absorption electronic oscillator strength of the C 2 - Herzberg-Lagerqvist bands has been determined as 0.017±0.008 at the (0,0) band origin.

DOI 10.1039/F29736900237
Citations Scopus - 15
1973 Evans PJ, MacKie JC, 'Relaxation of an alkali-metal halide aerosol in a shock wave', Journal of the Chemical Society, Faraday Transactions 2: Molecular and Chemical Physics, 69 224-236 (1973)

The interaction of a shock wave with an alkali-metal halide aerosol has been studied over a temperature range of 900-3600 K. The particle velocity relaxation and evaporation of ae... [more]

The interaction of a shock wave with an alkali-metal halide aerosol has been studied over a temperature range of 900-3600 K. The particle velocity relaxation and evaporation of aerosols of known size distribution were monitored with a light transmission technique. Times for complete velocity relaxation were found to be comparable with total evaporation times. At temperatures above 1550 K, the total evaporation times were independent of the gas temperatures. At temperatures below 1550 K, an activation phenomenon was observed in the evaporation times. Results were analysed using theoretical expressions for particle drag, heat transfer and particle evaporation. Expressions for the transition region in Knudsen number gave the best agreement with experiment.

DOI 10.1039/F29736900224
Citations Scopus - 4
1972 Cathro WS, MacKie JC, 'Lithium hydroxide and the dissociation kinetics of water vapour', Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, 68 150-159 (1972)

The chemical relaxation of shock-heated water vapour in 8-10% mixtures with argon has been studied over a temperature range of 2000-2400 K. The growth of H atom concentration was ... [more]

The chemical relaxation of shock-heated water vapour in 8-10% mixtures with argon has been studied over a temperature range of 2000-2400 K. The growth of H atom concentration was followed by introducing LiOH particles into the sample gas and observing the Li concentration profile by atomic absorption spectroscopy. By comparing H concentration profiles with computer simulations, values of the rate constant for H 2 O+M ¿ H+OH+M were obtained. The results represent an activation energy of 439±42 kJ mol -1 (105±10 kcal mol -1 ) and a pre-exponential factor of (1.8±0.6) × 10 16 cm 3 mol -1 s -1 for the case M = H 2 O. The kinetic assumptions of the LiOH method for measuring H concentrations in flames were thereby confirmed experimentally down to relatively short times after thermal excitation. Deviations in the early stages of the experimental profiles were attributed to the reaction LiOH+M ¿ Li+OH+M and the magnitude of the deviations indirectly suggests an activation energy for this reaction of about 377 kJ mol -1 (90 kcal mol -1 ).

DOI 10.1039/F19726800150
Citations Scopus - 20
1971 Evans PJ, Mackie JC, 'Shock-wave interaction with an evaporating aerosol', Physics of Fluids, 14 539-540 (1971)

The interaction of a shock wave with a gas containing suspended participate matter of finite thermal conductivity is considered theoretically. Mass, energy, and momentum equations... [more]

The interaction of a shock wave with a gas containing suspended participate matter of finite thermal conductivity is considered theoretically. Mass, energy, and momentum equations specifically including the effects of particle drag and heat transfer are solved simultaneously together with the rate equation for thermal evaporation of the solid to determine the relaxation in flow properties.

Citations Scopus - 3
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Grants and Funding

Summary

Number of grants 8
Total funding $3,691,080

Click on a grant title below to expand the full details for that specific grant.


20131 grants / $382,671

Non-destructive process for treatment of fluorinated greenhouse gases$382,671

Funding body: ARC (Australian Research Council)

Funding body ARC (Australian Research Council)
Project Team Professor Eric Kennedy, Conjoint Professor John Mackie
Scheme Discovery Projects
Role Investigator
Funding Start 2013
Funding Finish 2015
GNo G1200124
Type Of Funding Aust Competitive - Commonwealth
Category 1CS
UON Y

20091 grants / $560,000

Fires of pesticides: New source of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) in the environment$560,000

Funding body: ARC (Australian Research Council)

Funding body ARC (Australian Research Council)
Project Team Conjoint Professor Bogdan Dlugogorski, Professor Eric Kennedy, Conjoint Professor John Mackie, Associate Professor Marian Radny, Professor Michael Stockenhuber, Professor Michael Delichatsios, Professor George Hadjisophocleous
Scheme Discovery Projects
Role Investigator
Funding Start 2009
Funding Finish 2013
GNo G0188729
Type Of Funding Aust Competitive - Commonwealth
Category 1CS
UON Y

20081 grants / $1,225,000

Process for treatment of fluorine-containing synthetic greenhouse gases$1,225,000

Funding body: ARC (Australian Research Council)

Funding body ARC (Australian Research Council)
Project Team Professor Eric Kennedy, Conjoint Professor Bogdan Dlugogorski, Conjoint Professor John Mackie, Doctor Hai Yu, Professor Adesoji Adesina
Scheme Discovery Projects
Role Investigator
Funding Start 2008
Funding Finish 2012
GNo G0187485
Type Of Funding Aust Competitive - Commonwealth
Category 1CS
UON Y

20061 grants / $549,282

20051 grants / $600,000

Formation of organic pollutants in fires of treated and contaminated wood$600,000

Funding body: ARC (Australian Research Council)

Funding body ARC (Australian Research Council)
Project Team Conjoint Professor Bogdan Dlugogorski, Professor Eric Kennedy, Conjoint Professor John Mackie, Professor Michael Delichatsios
Scheme Discovery Projects
Role Investigator
Funding Start 2005
Funding Finish 2007
GNo G0184423
Type Of Funding Aust Competitive - Commonwealth
Category 1CS
UON Y

20043 grants / $374,127

Facility for Analysis of Thermal Decomposition of Solid Materials at High Pressures$314,127

Funding body: ARC (Australian Research Council)

Funding body ARC (Australian Research Council)
Project Team Conjoint Professor Bogdan Dlugogorski, Professor Eric Kennedy, Professor Behdad Moghtaderi, Emeritus Professor Terry Wall, Professor Scott Donne, Professor Adesoji Adesina, Professor R Burford, Dr A Green, Conjoint Professor John Mackie, Assoc. Prof A Masri, Assoc. Prof R Creelman, Dr P Wormell, Professor I Thomas
Scheme Linkage Infrastructure Equipment & Facilities (LIEF)
Role Investigator
Funding Start 2004
Funding Finish 2004
GNo G0183025
Type Of Funding Scheme excluded from IGS
Category EXCL
UON Y

Facility for analysis of thermal decomposition of solid materials at high pressure$45,000

Funding body: University of New South Wales

Funding body University of New South Wales
Project Team Conjoint Professor Bogdan Dlugogorski, Professor Eric Kennedy, Professor Behdad Moghtaderi, Emeritus Professor Terry Wall, Professor Scott Donne, Professor Adesoji Adesina, Professor R Burford, Dr A Green, Conjoint Professor John Mackie, Assoc. Prof A Masri, Assoc. Prof R Creelman, Dr P Wormell, Professor I Thomas
Scheme Linkage Infrastructure Equipment & Facilities (LIEF) Partner Funding
Role Investigator
Funding Start 2004
Funding Finish 2004
GNo G0183842
Type Of Funding Not Known
Category UNKN
UON Y

Facility for Analysis of Thermal Decomposition of Solid Materials at High Pressures$15,000

Funding body: University of Sydney

Funding body University of Sydney
Project Team Conjoint Professor Bogdan Dlugogorski, Professor Eric Kennedy, Professor Behdad Moghtaderi, Emeritus Professor Terry Wall, Professor Scott Donne, Professor Adesoji Adesina, Professor R Burford, Dr A Green, Conjoint Professor John Mackie, Assoc. Prof A Masri, Assoc. Prof R Creelman, Dr P Wormell, Professor I Thomas
Scheme Linkage Infrastructure Equipment & Facilities (LIEF) Partner Funding
Role Investigator
Funding Start 2004
Funding Finish 2004
GNo G0183843
Type Of Funding Not Known
Category UNKN
UON Y
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Research Supervision

Number of supervisions

Completed4
Current0

Past Supervision

Year Level of Study Research Title Program Supervisor Type
2016 PhD Development of Organic Modified Zeolites and Metal Organic Frameworks (MOFs) for Carbon Dioxide (CO2) Capture from Humid Flue Gas Streams PhD (Chemical Engineering), Faculty of Engineering and Built Environment, The University of Newcastle Co-Supervisor
2015 PhD Thermal Studies of Chlorinated and Mixed Halogenated Biphenyls PhD (Chemical Engineering), Faculty of Engineering and Built Environment, The University of Newcastle Co-Supervisor
2011 PhD Catalytic Mechanism of the Deacon Reaction PhD (Chemical Engineering), Faculty of Engineering and Built Environment, The University of Newcastle Co-Supervisor
2008 PhD Theoretical Investigation on Formation and Destruction of Polychlorinated Dibenzo-p-Dioxins and Dibenzofurans (PCDD/Fs): Thermodynamic and Kinetic Studies PhD (Chemical Engineering), Faculty of Engineering and Built Environment, The University of Newcastle Co-Supervisor
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Conjoint Professor John Mackie

Position

Conjoint Professor
Priority Research Centre for Energy
School of Engineering
Faculty of Engineering and Built Environment

Focus area

Chemical Engineering

Contact Details

Email john.mackie@newcastle.edu.au
Phone (02) 4985 4439

Office

Room ATC Building
Location Callaghan
University Drive
Callaghan, NSW 2308
Australia
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