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Kinetic Studies of the Reactions of Cl and Br with Silane and Trimethylsilane (open access)

Kinetic Studies of the Reactions of Cl and Br with Silane and Trimethylsilane

The temperature dependence of the reactions of halogen atoms Cl and Br with SiH4 and (CH3)3SiH have been investigated with the flash photolysis-resonance fluorescence technique. CCI4 and CH2Br2 were used as precursors to produce Cl and Br atoms, respectively. Experiments gave {k(Cl + SiH4) (295 - 472 K)} = (1.56 +0.11) x 10-1 exp[(2.0 + 0.2) kJ mol'/RT] cm3 s4, {k(Br + SiH4)(295 - 575 K)} = (9.0 + 1.5) x 10-" exp[-(17.0 + 0.6) Id mol'/RT] cm3 s', {k(Cl + (CH3)3SiH)(295 - 468 K)} = (1.24 0.35) x 104 exp[(1.3 + 0.8) Id mol4/RT] cm3 s', and {k(Br + (CH3)3SiH)(295 - 456 K)} = (7.6 + 3.3) x 1010 exp[-(28.4 + 1.3) Id mol'/RT] cm3 s'. The results were compared with values from earlier work.
Date: May 1992
Creator: Ding, Luying
System: The UNT Digital Library
The Metal-Organic Chemical Vapor Deposition of Cu(II)-bishexafluoroacetylacetonate on a Tungsten Substrate (open access)

The Metal-Organic Chemical Vapor Deposition of Cu(II)-bishexafluoroacetylacetonate on a Tungsten Substrate

Evidence is reported for the formation of carbon-containing contamination products at the copper-tungsten (Cu-W) interface during the metal organic chemical vapor deposition (MOCVD) of copper on tungsten. Cu(II)bishexafluoroacetylacetonate [Cu(hfac)_2] was physisorbed onto lightly oxidized tungsten (WO_x) at 115K, under ultra-high vacuum conditions, and then annealed sequentially to higher temperatures. Copper reduction was observed by 320K. Carbonaceous and carbidic contamination of the WO_x surface was observed, even after sample warming to 625K in UHV. The results indicate that low temperature MOCVD of Cu may be possible, but interfacial contamination from the organic ligand fragmentation is a major concern.
Date: May 1992
Creator: Welton, Theresa E. (Theresa Eilene)
System: The UNT Digital Library
A Study of Intra- and Interaggregate Exchange Processes of Alkyllithium Compounds Using One- and Two- Dimensional NMR Spectroscopy (open access)

A Study of Intra- and Interaggregate Exchange Processes of Alkyllithium Compounds Using One- and Two- Dimensional NMR Spectroscopy

One- and two-dimensional NMR spectroscopy, including 13C{6Li}{1H} triple resonance techniques, were used to characterize a series of mixed alkyllithium aggregates and to study their exchange processes.
Date: May 1992
Creator: Pannell, Daniel K. (Daniel Kirk)
System: The UNT Digital Library
Kinetic Study of the Reactions of Oxygen Atoms with Nitric Oxide and Silane (open access)

Kinetic Study of the Reactions of Oxygen Atoms with Nitric Oxide and Silane

The rate constant for the reactions of oxygen atoms with nitric oxide and silane were determined using a discharge flow apparatus. A microwave discharge through O2N2 and Ar was used to produce oxygen atoms. The rate constant for the reaction O + NO + Ar was determined to be (7.0+0.4) x 10^32 cm^6 s^-1 and is in good agreement with previous measurements. Modeling of the O +SiH₄ reaction was performed to determine the correction to the rate constant due to secondary reactions. The rate constant for the reaction O + SiH₄ was determined to be (3.3 +/- 0.3) x 10⁻¹³ cm³ s⁻¹ and is in good agreement with previous measurements. Previous literature, thermochemistry, and spin conservation were used to determine a probable mechanism for the O + SiH₄ reaction.
Date: August 1992
Creator: Taylor, Craig A. (Craig Allan)
System: The UNT Digital Library
Solution Studies of the Structures and Stability of Mixed Lithium Alkoxide/Alkvllithium Aggregates (open access)

Solution Studies of the Structures and Stability of Mixed Lithium Alkoxide/Alkvllithium Aggregates

New one- and two-dimensional NMR techniques were used to elucidate the solution structures of these complex mixtures. The system, lithium tert-butoxide/tert-butyllithium, was studied as a model system with O/Li ratios varying from 0/1 to 1/1. It was found that at low O/Li ratios, a single mixed tetrameric aggregate was formed. At higher O/Li ratios, mixed hexameric species were formed. Two other systems, lithium isopropoxide/iso-propyllithium and lithium n-propoxide/n-propyllithium were also studied at low O/Li ratios.
Date: December 1992
Creator: DeLong, George T. (George Thomas)
System: The UNT Digital Library
Thermochemical Investigation of Ternary Nonelectrolyte Mixtures (open access)

Thermochemical Investigation of Ternary Nonelectrolyte Mixtures

Excess molar volumes have been determined for four ternary chlorobenzene + dibutyl ether + alkane mixtures at 25°C. Results of these measurements are used to test the applications and limitations of BAB, Redlich-Kister, Kohler and Hwang et al. cubic models. For the systems studied, Redlich- Kister, Kohler and Cubic models were found to provide reasonable predictions. Differences between experimental and predicted ΔV^ex_123 values were about ±0.020 cm^3mol^-1 or less at most ternary compositions. Solubilities are reported for anthracene in binary mixtures containing propanol and butanol with alkanes at 25°C. Results of these measurements are used to test the NIBS/Redlich-Kister expression. The three-parameter form of this expression is found to provide reasonable mathematical representation with deviations between experimental and back-calculated values being less than ±1%.
Date: December 1992
Creator: Teng, I-Lih
System: The UNT Digital Library