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Copper Catalyzed Sodium Tetraphenylborate, Triphenylborane, Diphenylborinic Acid and Phenylboronic Acid Decomposition Kinetic Studies in Aqueous Alkaline Solutions

Description: This work studied the kinetics of copper-catalyzed decomposition of tetraphenylborate, triphenylborane, diphenylborinic acid and phenylboronic acid (NaTPB, 3PB, 2PB and 1PB, respectively) in aqueous alkaline solution over the temperature range of 25 to 70 degrees C. The statistically designed test matrices added copper sulfate to maximum concentrations of 10 mg/L. The relative rates of decomposition increase in the order of NaTPB < 1PB {tilde} 3PB < 2PB. Dependence of decomposition on the amount of added copper increases in the order of 3PB {tilde} 2PB < 1PB {tilde} NaTPB. Activation energies ranged from 82 to 143 kJ/mole over the temperature range studied. Final decomposition products predominately involved benzene and phenol. All 3PB, 2PB and 1PB intermediate phenylborate species proved relatively stable (< 8 percent decomposition over {tilde} 500 h) towards thermal hydrolysis in 1.5 M NaOH when contained in carbon-steel vessels sealed under air at ambient temperature (23 - 25 degrees C) with no added copper. Measurable (> 10-7 Mh-1) thermal hydrolysis of the phenylborate species occurs at 55 to 70 degrees C in alkaline (0.6-2.3 M OH-, 2-4.7 M Na+) solution with no added copper. The experiments suggest an important role for oxygen in copper-catalyzed phenylborate decomposition. NaTPB decomposes promptly under anoxic conditions while 3PB, 2PB and 1PB decompose faster in aerobic solutions. Benzene and phenol form as the predominant end-products from alkaline copper catalysis in static systems sealed under air. Both 2PB and 1PB decompose with near equal rates and quantitatively produce phenol under flowing air-purge conditions at 25 to 60 degrees C. Mechanisms for copper-catalyzed phenylborate decomposition likely involve a redox process giving loss of a phenyl group from the phenylborate with reduction of cupric ion, or dephenylation by reduced cuprous ion involving a phenylated copper intermediate.
Date: March 15, 1999
Creator: Crawford, C.L.
Partner: UNT Libraries Government Documents Department

Flash photolysis-shock tube studies

Description: Following earlier investigations on the dissociation rates of CF{sub 3}Cl, CF{sub 2}Cl{sub 2}, CFCl{sub 3}, and CCl{sub 4}, we systematically applied theory to explain the rate behavior for the this homologous series. Three different unimolecular theoretical methods were compared. The inferred results were in good agreement with one another suggesting that the conclusions are not strongly dependent on the degree of theoretical rigor. In all of these cases and in others, we have determined the best mutual values for both threshold energy, E{sub 0}, and energy transfer parameter, ({Delta}E){sub down}. The best fits generally give values for E{sub 0} that are in good agreement with other thermochemical methods. Also, for halogen containing molecules, the derived ({Delta}E){sub down} values are large, giving effective collisional efficiency factors, {beta}{sub c}, between {approx}0.02 and 0.10 at 1300 K.
Date: August 1, 1997
Creator: Michael, J.V.
Partner: UNT Libraries Government Documents Department

Phenyl radical thermolysis and rate constants for phenyl + O{sub 2}

Description: The thermal decomposition of C{sub 6}H{sub 5}I has been used to prepare in-situ known initial concentrations of phenyl radicals at high temperatures. These can be degraded by direct decomposition at T > 1350 K giving H + C{sub 6}H{sub 4}. Using H-atom ARAS, rate constants for C{sub 6}H{sub 5} dissociation have been measured. Using the same ARAS technique, constants for C{sub 6}H{sub 5} dissociation have been measured. Using the same ARAS technique, the H- and O-atoms formed from the reaction, C{sub 6}H{sub 5} + O{sub 2}, have both been measured. The rate constant results are discussed along with lower T measurements in terms of RRKM calculations using published ab initio electronic structure determinations of transition states.
Date: August 1, 1997
Creator: Kumaran, S.S. & Michael, J.V.
Partner: UNT Libraries Government Documents Department

Excess Sodium Tetraphenylborate and Intermediates Decomposition Studies

Description: The stability of excess amounts of sodium tetraphenylborate (NaTPB) in the In-Tank Precipitation (ITP) facility depends on a number of variables. Concentration of palladium, initial benzene, and sodium ion as well as temperature provide the best opportunities for controlling the decomposition rate. This study examined the influence of these four variable on the reactivity of palladium-catalyzed sodium tetraphenylborate decomposition. Also, single effects tests investigated the reactivity of simulants with continuous stirring and nitrogen ventilation, with very high benzene concentrations, under washed sodium concentrations, with very high palladium concentrations, and with minimal quantities of excess NaTPB.
Date: December 7, 1998
Creator: Barnes, M.J.
Partner: UNT Libraries Government Documents Department

Exploring old and new benzene formation pathways in low-pressure premixed flames of aliphatic fuels

Description: A modeling study of benzene and phenyl radical formation is performed for three low-pressure premixed laminar flat flames having an unsaturated C{sub 2} or C{sub 3} hydrocarbon fuel (acetylene, ethylene, and propene). Predictions using three published detailed elementary-step chemical kinetics mechanisms are tested against MBMS species profile data for all three flames. The differences between the three mechanisms predictive capabilities are explored, with an emphasis on benzene formation pathways. A new chemical kinetics mechanism is created combining features of all three published mechanisms. Included in the mechanism are several novel benzene formation reactions involving combinations of radicals such as C{sub 2}H+C{sub 4}H{sub 5}, and C{sub 5}H{sub 3}+CH{sub 3}. Reactions forming fulvene (a benzene isomer) are included, such as C{sub 3}H{sub 3}+C{sub 3}H{sub 5},as well as fulvene-to-benzene reactions. Predictions using the new mechanism show virtually all of the benzene and phenyl radical to be formed by reactions of either C{sub 3}H{sub 3}+C{sub 3}H{sub 3} or C{sub 3}H{sub 3}+C{sub 3}H{sub 5}, with the relative importance being strongly dependent upon the fuel. C{sub 5}H{sub 3}+CH{sub 3} plays a minor role in fulvene formation in the acetylene flame. The C{sub 2}H{sub x}+C{sub 4}H{sub 4} reactions do not contribute noticeably to benzene or phenyl radical formation in these flames, sometimes being a major decomposition channel for either fulvene or phenyl radical. The formation pathways for C{sub 3}H{sub 3} and C{sub 3}H{sub 5}are delineated for the three flames; while the key reactions differ from flame to flame, CH{sub 2}+C{sub 2}H{sub 2} {Longleftrightarrow} C{sub 3}H{sub 3}+H is important for all three flames.
Date: December 13, 2000
Creator: Pope, Christopher J. & Miller, James A.
Partner: UNT Libraries Government Documents Department

Reaction of Phenyl Radical with O2: Thermodynamic Properties, Important Reaction Paths and Kinetics

Description: The Phenyl + O{sub 2} association results in a chemically activated phenyl-peroxy radical which can dissociate to phenoxy radical + O, undergo intramolecular addition of the peroxy radical to several unsaturated carbon sites or react back to phenyl + O{sub 2}. The intramolecular addition channels further react through several paths to ring opening (unsaturated + carbonyl moieties) as well as cyclopentadieny radical + CO{sub 2}. Enthalpy ({Delta}H{sub f(298)}{sup o}), Entropy (S{sub 298}), and heat capacities Cp(T) for species in the decomposition of the ring are evaluated using density functional and ab initio calculations and by comparisons to vinyl + O{sub 2} data of Mebel et al, and phenyl + O{sub 2} data of Hadad et al. Isodesmic reaction analysis is used to estimate enthalpy values of the intermediates and well depths of the adducts. High Pressure limit kinetic parameters are obtained from the calculation results using canonical Transition State Theory. Quantum RRK analysis is utilized to obtain k(E) and modified strong collision or master equation analysis is used for evaluation of pressure fall-off in this complex bimolecular, chemical activation, reaction system. Uncertainty in key barriers is discussed, resulting variations in important reaction product ratios are illustrated, and changes in these branching ratios are evaluated with a detailed reaction mechanism.
Date: April 12, 2001
Creator: Bozzelli, J; Sebbar, N; Pitz, W & Bockhorn, H
Partner: UNT Libraries Government Documents Department

Kinetics of elementary processes relevant to incipient soot formation. Final technical report

Description: In order to better understand the mechanism of soot formation (one of the most challenging problems in the study of hydrocarbon combustion chemistry), reliable rate constants for the key reaction steps involved in the formation and polymerization of aromatic hydrocarbons in the inception stage are required for kinetic modeling. In this DOE sponsored work, the authors have developed three new experimental methods: cavity ring-down (CRD) spectrometry, pyrolysis/Fourier transform infrared spectrometry (p/FTIRS) and pulsed laser photolysis/mass spectrometry (PLP/MS) for kinetic measurements of C{sub 6}H{sub 5} reactions pivotal to incipient soot formation chemistry. In addition, the authors have also carried out ab initio molecular orbital (MO) calculations for several key elementary combustion reactions relevant to soot formation. The results are briefly summarized in the report using selected examples for more detailed discussion. 84 refs.
Date: March 9, 1998
Creator: Lin, M.C.
Partner: UNT Libraries Government Documents Department


Description: The three isomeric (5-phenyl-2-oxazolyl)pyridines have been shown to be sensitive fluorescent pH indicators which show a pronounced change to increased visible fluorescence as the pH is lowered. Absorption and fluorescence spectral data and pK values are given. Selective excitation of fluorescence from the conjugate acid in the presence of the free base was found possible. The sensitivity of the 4-isomer was demonstrated to be adequate for determining the small amounts of acid produced in certain chemical dosimeter systems. (auth)
Date: August 1, 1958
Creator: Ott, D.G.
Partner: UNT Libraries Government Documents Department