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Kinetic studies and computational modeling of atomic chlorine reactions in the gas phase.

Description: The gas phase reactions of atomic chlorine with hydrogen sulfide, ammonia, benzene, and ethylene are investigated using the laser flash photolysis / resonance fluorescence experimental technique. In addition, the kinetics of the reverse processes for the latter two elementary reactions are also studied experimentally. The absolute rate constants for these processes are measured over a wide range of conditions, and the results offer new accurate information about the reactivity and thermochemistry of these systems. The temperature dependences of these reactions are interpreted via the Arrhenius equation, which yields significantly negative activation energies for the reaction of the chlorine atom and hydrogen sulfide as well as for that between the phenyl radical and hydrogen chloride. Positive activation energies which are smaller than the overall endothermicity are measured for the reactions between atomic chlorine with ammonia and ethylene, which suggests that the reverse processes for these reactions also possess negative activation energies. The enthalpies of formation of the phenyl and β-chlorovinyl are assessed via the third-law method. The stability and reactivity of each reaction system is further rationalized based on potential energy surfaces, computed with high-level ab initio quantum mechanical methods and refined through the inclusion of effects which arise from the special theory of relativity. Large amounts of spin-contamination are found to result in inaccurate computed thermochemistry for the phenyl and ethyl radicals. A reformulation of the computational approach to incorporate spin-restricted reference wavefunctions yields computed thermochemistry in good accord with experiment. The computed potential energy surfaces rationalize the observed negative temperature dependences in terms of a chemical activation mechanism, and the possibility that an energized adduct may contribute to product formation is investigated via RRKM theory.
Date: August 2009
Creator: Alecu, Ionut M.
Partner: UNT Libraries

A Kinetic Study of the Recombination Reacton Na + SO₂ + Ar

Description: The recombination reaction Na + S02 + Ar was investigated at 787 16 K and at pressures from 1.7 to 80 kPa. NaI vapor was photolyzed by an excimer laser at 308 nm to create Na atoms, whose concentration was monitored by time-resolved resonance absorption at 589 nm. The rate constant at the low pressure limit is ko = (2.7 0.2) x 10-21 cm6 molecule-2 s~1. The Na-SO 2 dissociation energy E0 = 170 35 kJ mol1 was calculated with RRKM theory. The equilibrium constant gave a lower limit E0 > 172 kJ mol~ 1. By combination of these two results, E0 = 190 15 kJ mol~ 1 is obtained. The high pressure limit is k, = (1 - 3) x 10-10 cm3 molecule 1 s~1, depending on the extrapolation method used. Two versions of collision theory were employed to estimate k,.. The 'harpoon' model shows the best agreement with experiment.
Date: December 1990
Creator: Shi, Youchun
Partner: UNT Libraries

Kinetic mechanism of NAD-malic enzyme from Ascaris suum in the direction of reductive carboxylation of pyruvate

Description: For this pseudoquadreactant enzymatic reaction (Mn2+ is a psuedoreactant), initial velocity patterns were obtained under conditions in which two substrates were maintained saturating while one reactant was varied at several fixed concentrations of the other.
Date: December 1990
Creator: Mallick, Sushanta
Partner: UNT Libraries

Kinetics of Reactions of Substituted Group VI B Metal Carbonyls with Phosphites

Description: The problem with which this investigation is concerned is twofold. The initial part of the problem was to prepare a non-sterically demanding bidentate phosphine ligand, 1,2-bis-(Phosphino)ethane, (P-en), and to determine the kinetics of (P-en)Mo(CO)4 with phosphites via spectrophotometric methods in an attempt to determine if steric effects are directing the type of mechanism followed.
Date: August 1972
Creator: Rettenmaier, Albert J.
Partner: UNT Libraries

Tables of Chemical Kinetics : Homogeneous Reactions (Supplementary Tables)

Description: From Preface: "A brief description of the method used in compiling these tables and the limitation of coverage are given in the preface to Supplement 1 of the NBS Circular 510. The present volume contains information pertaining to substitution, exchange, and elimination reaction types and extends the material on these types found in NBS Monograph 34, Volume 1. The date on each page gives the year and month to which the literature had been surveyed."
Date: July 1, 1964
Creator: United States. Bureau of Standards.
Partner: UNT Libraries Government Documents Department

Tables of Chemical Kinetics : Homogeneous Reactions (Supplementary Tables)

Description: From Preface: "A brief description of the method used in compiling these tables and the limitation of coverage is given in the preface to Supplement 1. A description of the numbering system used is classifying reactions for the tables is given in Supplement 2. The present supplement contains information pertaining to Substitution, Exchange and Elimination reaction types. It is not complete as still more material falling groups is being prepared."
Date: September 15, 1961
Creator: United States. Bureau of Standards.
Partner: UNT Libraries Government Documents Department

Kinetics of the Fischer-Tropsch Synthesis on Iron Catalysts

Description: From Introduction: "The first of this Bulletin describes rate studies on iron catalysts and the second part the influence of catalyst geometry on rate. The appendix describes special experiments at higher pressure than those usually employed in the synthesis on iron catalysts."
Date: unknown
Creator: Anderson, R. B.; Karn, F. S. & Shultz, J. F.
Partner: UNT Libraries Government Documents Department

Kinetics of Sulfur: Experimental Study of the Reaction of Atomic Sulfur with Acetylene and Theoretical Study of the Cn + So Potential Energy Surface

Description: The kinetics of the reaction of atomic sulfur with acetylene (S (3P) + C2H2) were investigated experimentally via the flash photolysis resonance fluorescence method, and the theoretical potential energy surface for the reaction CN + SO was modeled via the density functional and configuration interaction computational methods. Sulfur is of interest in modern chemistry due to its relevance in combustion and atmospheric chemistry, in the Claus process, in soot and diamond-film formation and in astrochemistry. Experimental conditions ranged from 295 – 1015 K and 10 – 400 Torr of argon. Pressure-dependence was shown at all experimental temperatures. The room temperature high-pressure limit second order rate constant was (2.10 ± 0.08) × 10-13 cm3 molecule-1 s-1. The Arrhenius plot of the high-pressure limit rate constants gave an Ea of (11.34 ± 0.03) kJ mol-1 and a pre-exponential factor of (2.14 ± 0.19) × 10-11 cm3 molecule-1 s-1. S (3P) + C2H2 is likely an adduct forming reaction due to pressure-dependence (also supported by a statistical mechanics analysis) which involves intersystem crossing. The potential energy surface for CN + SO was calculated at the B3LYP/6-311G(d) level and refined at the QCISD/6-311G(d) level. The PES was compared to that of the analogous reaction CN + O2. Notable energetically favorable products are NCS + O, CO + NS, and CS + NO. The completed PES will ultimately be modeled at the CCSD(T) level (extrapolated to infinite basis set limit) for theoretical reaction rate analysis (RRKM).
Date: May 2013
Creator: Ayling, Sean A.
Partner: UNT Libraries

Moving in a New Direction: An Exploration in Kinetics

Description: Movement, whether conveyed through an actual motion or a gestured implication, remains an underlying theme in my creative process that started with my earliest works. I explored different aspects of kinetic sculpture, because I am seeking new ways to create motion such as experimenting with circulating air, wind, and the use of water features. I created a series consisting of three to five kinetic sculptures which do not rely on sound or direct viewer manipulation.
Date: August 2004
Creator: Illy, Etienne
Partner: UNT Libraries

Thermodynamics, Kinetics, and Mechanism of (silox)3M(olefin) to (silox)3M(alkylidene) Rearrangements (silox = tBu3SiO; M = Nb, Ta)

Description: Article discussing the thermodynamic, kinetic, and mechanism of (silox)3M(olefin) to (silox)3M(alkylidene) rearrangements (silox = tBu3SiO; M = Nb, Ta).
Date: March 10, 2005
Creator: Hirsekorn, Kurt F.; Veige, Adam S.; Marshak, Michael P.; Koldobskaya, Yelena; Wolczanski, Peter T.; Cundari, Thomas R., 1964- et al.
Partner: UNT College of Arts and Sciences

Kinetics and Mechanism Study of Diphenylketene Cycloadditions

Description: From a review of the published work in the field of cycloadditions, it is evident that further research is needed to establish the mechanism of ketene cycloadditions. This work was initiated with the intent of obtaining kinetic data which will contribute to the elucidation of the mechanism of ketene cycloadditions.
Date: August 1967
Creator: O'Neal, Hubert Ronald
Partner: UNT Libraries

Fumarate Activation and Kinetic Solvent Isotope Effects as Probes of the NAD-Malic Enzyme Reaction

Description: The kinetic mechanism of activation of the NAD-malic enzyme by fumarate and the transition state structure for the oxidation malate for the NAD-malic enzyme reaction have been studied. Fumarate exerts its activating effect by decreasing the off-rate for malate from the E:Mg:malate and E:Mg:NAD:malate complexes. The activation by fumarate results in a decrease in K_imalate and an increase in V/K_malate by about 2-fold, while the maximum velocity remains constant. A discrimination exists between active and activator sites for the binding of dicarboxylic acids. Activation by fumarate is proposed to have physiologic importance in the parasite. The hydride transfer transition state for the NAD-malic enzyme reaction is concerted with respect to solvent isotope sensitive and hydride transfer steps. Two protons are involved in the solvent isotope sensitive step, one with a normal fractionation factor, another with an inverse fractionation factor. A structure for the transition state for hydride transfer in the NAD-malic enzyme reaction is proposed.
Date: December 1992
Creator: Lai, Chung-Jeng
Partner: UNT Libraries