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Molecular Dynamics and Interactions in Liquids (open access)

Molecular Dynamics and Interactions in Liquids

Various modern spectroscopies have been utilized with considerable success in recent years to probe the dynamics of vibrational and reorientational relaxation of molecules in condensed phases. We have studied the temperature dependence of the polarized and depolarized Raman spectra of various modes in the following dihalomethanes: dibromomethane, dichloromethane, dichloromethane-d2, and bromochloromethane. Among other observed trends, we have found the following: Vibrational dephasing times calculated from the bend) and (C-Br stretch) lineshapes are of the same magnitude in CI^B^. The vibrational dephasing time of [C-D(H) stretch] is twice as long in CD2Cl2 as in CH-^C^, and the relaxation time of (C-Cl stretch) is greater in CI^C^ than in CD2CI2. Isotropic relaxation times for all three stretching vibrations are significantly shorter in C^BrCl than in CI^C^ or CI^B^. Application of the Kubo model revealed that derived modulation times are close to equal for equivalent vibrations in the various dihalomethanes. Thus, the more efficient relaxation of the A^ modes in CE^BrCl can be attributed almost entirely to the broader mean squared frequency perturbation of the vibrations in this molecule.
Date: May 1985
Creator: Chen, Jen Hui
Object Type: Thesis or Dissertation
System: The UNT Digital Library
The Study of Low Temperature Silene Generation (open access)

The Study of Low Temperature Silene Generation

The reactions of tert-butyl-, sec-butyl-, and n-butyllithium with dimethylfluorovinylsilane include addition to the double bond to give both silene and silenoid intermediates, fluorine substitution, and a novel vinyl substitution. For the tert-butyllithium reaction, product stereochemistry and trapping experiments using both cyclopentadiene and methoxytrimethylsilane show that silenes are not formed in THF. In hexane about 67% of the 1,3-disilacyclobutanes obtained arise from silene dimerization while 33% are formed by silenoid coupling. In hexane the order of reactivity for addition, t-Bu > sec-Bu > n-Bu, is opposite that for fluorine substitution. The vinyl substitution is most significant with secondary alkyllithium reagents including the tert-butyllithium adduct to dimethylfluorovinylsilane and with sec-butyllithium itself. Evidence for the formation of vinyllithium or ethylene in the process could not be obtained.
Date: August 1985
Creator: Cheng, Albert Home-Been
Object Type: Thesis or Dissertation
System: The UNT Digital Library
Temperature Dependence of the Absolute Third-order Rate Constant for the Reaction between Na + O₂ + N₂ over the Range 571 - 1016 K Studied by Time-resolved Atomic Resonance Absorption Spectroscopy (open access)

Temperature Dependence of the Absolute Third-order Rate Constant for the Reaction between Na + O₂ + N₂ over the Range 571 - 1016 K Studied by Time-resolved Atomic Resonance Absorption Spectroscopy

Article on temperature dependence of the absolute third-order rate constant for the reaction between Na + O₂ + N₂ over the range 571-1016 K studied by time-resolved atomic resonance absorption spectroscopy.
Date: 1985
Creator: Husain, David; Marshall, Paul & Plane, John M. C.
Object Type: Article
System: The UNT Digital Library
Determination of absolute rate data for the reaction of atomic sodium, Na (3²S(1/2)), with CF₃Cl, CF₂Cl₂, CFCl₃, CF₃Br and SF₆ as a Function of Temperature by Time-resolved Atomic Resonance-absorption Spectroscopy at λ = 589 nm [Na(3²Pᴊ) ← Na(3²S(1/2)) (open access)

Determination of absolute rate data for the reaction of atomic sodium, Na (3²S(1/2)), with CF₃Cl, CF₂Cl₂, CFCl₃, CF₃Br and SF₆ as a Function of Temperature by Time-resolved Atomic Resonance-absorption Spectroscopy at λ = 589 nm [Na(3²Pᴊ) ← Na(3²S(1/2))

Article on a kinetic study of the reactions of ground-state sodium atoms with the molecules CF₃Cl, CF₂Cl₂, CFCl₃, CF₃Br and SF₆ over the temperature range 644-918 K.
Date: 1985
Creator: Husain, David & Marshall, Paul
Object Type: Article
System: The UNT Digital Library
Determination of the Absolute Second-order Rate Constant for the Reaction Na + O₃ → NaO + O₂ (open access)

Determination of the Absolute Second-order Rate Constant for the Reaction Na + O₃ → NaO + O₂

Article on the determination of the absolute second-order rate constant for the reaction Na + O₃ → NaO + O₂.
Date: 1985
Creator: Husain, David; Marshall, Paul & Plane, John M. C.
Object Type: Article
System: The UNT Digital Library
Octanol-Water Partition Coefficients of Substituted α,N-Diphenylnitrones and Benzonitrile N-Oxides (open access)

Octanol-Water Partition Coefficients of Substituted α,N-Diphenylnitrones and Benzonitrile N-Oxides

Article on octanol-water partition coefficients of substituted alpha and N-diphenylnitrones and benzonitrile N-oxides.
Date: October 1, 1985
Creator: Kirchner, James J.; Acree, William E. (William Eugene); Leo, Albert J. & Gelli, Gioanna
Object Type: Article
System: The UNT Digital Library
Excess Molar Volumes of Binary Mixtures of Cyclohexane and y-Butyrolactone with Aromatic Hydrocarbons (open access)

Excess Molar Volumes of Binary Mixtures of Cyclohexane and y-Butyrolactone with Aromatic Hydrocarbons

This article discusses excess molar volumes of binary mixtures of cyclohexane and y-butyrolactone with aromatic hydrocarbons.
Date: April 1985
Creator: Acree, William E. (William Eugene); Gholami, Kheirollah; McHan, Danny R. & Rytting, J. Howard
Object Type: Article
System: The UNT Digital Library
Solubility of Phenylacetic Acid in Binary Solvent Mixtures (open access)

Solubility of Phenylacetic Acid in Binary Solvent Mixtures

Article on the solubility of phenylacetic acid in binary solvent mixtures.
Date: January 1985
Creator: Acree, William E. (William Eugene)
Object Type: Article
System: The UNT Digital Library