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M.S.

The reactions of atomic hydrogen with methanethiol and that of atomic hydrogen with carbon disulfide were studied experimentally using flash-photolysis resonance-fluorescence techniques. Rate constants were determined over a range of temperatures and pressures, and through analysis and comparison to theoretical work details of the reactions were ascertained.

The interaction between carbon dioxide (CO2) and N-compounds such as 1,8-diazobicyclo[5.4.0]undec-7-ene (DBU) has been extensively studied in the Jessop Lab. Carbon disulfide (CS2) is the sulfur congener of CO2, although it exhibits different reactivity with N-containing compounds. This thesis presents the search for zwitterionic CO2-switchable polarity solvents, new and general reactivity of CS2 with amidines and guanidines, and attempts at using CO2 as a carbonyl source in the synthesis of nitrogen containing compounds. In the second chapter, the reactions of CO2 with various diamines are described. Spectroscopic methods and X-ray crystallography determined the structure of a solid zwitterionic carbamate salt of CO2 and N,N’-dimethyl-1,3-propanediamine. The polarity of the liquid zwitterionic carbamate salt formed with N,N,N’-trimethyl-1,3-propanediamine was measured using UV-Vis and the solvatochromic dye Nile red; its polarity was comparable to previous switchable polarity systems. The CO2 gravimetric uptake of the liquid zwitterionic carbamate salt was 28%, far greater than other solvents for the capture and release of CO2. In the third chapter, it was found that a variety of products can be accessed depending on the structure of the N-base (cyclic or acyclic) upon reaction of the base with CS2 at room temperature. The reaction of CS2 with cyclic amidines produced a cyclic trithioanhydride structure, forming a new C-C bond at a sp2-carbon beta to the imino nitrogen centre. When an amidine was acyclic it led to cleavage and formation of isothiocyanates in near quantitative yields. When a N-base had a N-H bond, CS2 can insert, forming a dimer in the presence of dichloromethane. In the fourth chapter, preliminary investigations are ascribed for synthesis of α-amino acids, amides, and ureas. Carboxylation of ketimines was detected, although the formed carboxylates from a variety of ketimines readily decomposed. Isomerization products of two ketimines were generated with DBU and CO2. Lewis acid catalysts were implemented towards the amidation of benzoylacetic acid and synthesis of ureas. Amidation of benzoylacetic acid did not occur in the presence of Lewis acid catalysts and CO2. Formation of a cyclic tetraalkylurea was afforded in low yields by the use of a diamine, CO2 and Lewis acid catalysts. / Thesis (Ph.D, Chemistry) -- Queen's University, 2013-12-01 19:16:55.257

Momentum vectors of fragment ions produced by the Coulomb explosion of CO2z+ (z = 3 - 6) and CS2z+ (z = 3 - 13) in an intense laser field (~50 fs, 1 x 1015 W/cm2) are determined by the triple coincidence imaging technique. The molecular structure from symmetric and asymmetric explosion channels is reconstructed from the measured momentum vectors using a novel simplex algorithm that can be extended to study larger molecules. Physical parameters such as bend angle and bond lengths are extracted from the data and are qualitatively described using an enhanced ionization model that predicts the laser intensity required for ionization as a function of bond length using classical, over the barrier arguments. As a way of going beyond the classical model, molecular ionization is examined using a quantum-mechanical, wave function modified ADK method. The ADK model is used to calculate the ionization rates of H2, N2, and CO2 as a function of initial vibrational level of the molecules. A strong increase in the ionization rate, with vibrational level, is found for H2, while N2 and CO2 show a lesser increase. The prospects for using ionization rates as a diagnostic for vibrational level population are assessed.

Momentum vectors of fragment ions produced by the Coulomb explosion of CO2z+ (z = 3 - 6) and CS2z+ (z = 3 - 13) in an intense laser field (~50 fs, 1 x 1015 W/cm2) are determined by the triple coincidence imaging technique. The molecular structure from symmetric and asymmetric explosion channels is reconstructed from the measured momentum vectors using a novel simplex algorithm that can be extended to study larger molecules. Physical parameters such as bend angle and bond lengths are extracted from the data and are qualitatively described using an enhanced ionization model that predicts the laser intensity required for ionization as a function of bond length using classical, over the barrier arguments. As a way of going beyond the classical model, molecular ionization is examined using a quantum-mechanical, wave function modified ADK method. The ADK model is used to calculate the ionization rates of H2, N2, and CO2 as a function of initial vibrational level of the molecules. A strong increase in the ionization rate, with vibrational level, is found for H2, while N2 and CO2 show a lesser increase. The prospects for using ionization rates as a diagnostic for vibrational level population are assessed.

Thesis (Ph. D.)--York University, 2000. Graduate Programme in Chemistry. / Typescript. Includes bibliographical references (leaves 370-416). Also available on the Internet. MODE OF ACCESS via web browser by entering the following URL: http://wwwlib.umi.com/cr/yorku/fullcit?pNQ59143

The intensity dependent refractive index change of a medium is frequently described in terms of the product n₂ · I where n₂ is the nonlinear refractive index and I the light intensity. The nonlinear refractive index is often treated as constant which is a reasonable assumption if the light interacts only with bound electrons. In the case of carbon disulfide (CS₂) however, nuclear motions contribute to n₂. These motions occur on the sub picosecond time scale and thus become especially relevant for ultrashort laser pulses. The neat liquid CS₂ is studied because it exhibits a large nonlinear refractive index in comparison to other liquids. Therefore, it is employed in optical switching, optical limiting, and beam filamentation applications. This thesis presents effective n₂ values for Gaussian shaped linearly polarized pulses with central wavelength at [lambda]= 700nm. A theoretical model describing the time evolution of the material response is applied to distinguish between the instantaneous electronic, the ultrafast nuclear and the slow nuclear origins of the nonlinear refractive index. Moreover, the tensor nature of the material response function is studied by means of circularly polarized light. The relative magnitudes of bound electronic and nuclear contributions to n₂ are experimentally determined. Eventually, the dispersion of the instantaneous electronic response is measured in the spectral range between 390nm and 1064nm.

The nonlinear refractive index (n2) of room temperature liquid CS2 in the wavelength range of 9 to 11 micrometers is measured. A line tunable hybrid C02 TEA laser and amplifier system is used for the experiments. In these measurements the well known photoacoustic method is utilized to observe the onset of whole beam self-focusing. The photoacoustic signal in a CS2 cell, much longer than the confocal parameter, is monitored. The departure of the acoustic signal from linear growth marks the critical power for the onset of nonlinearity. It is experimentally verified that the phenomenon is power dependent as expected from self-focusing theory. The value of n2 is then calculated from the theoretical model of self focusing. Measurements of the on-axis irradiance transmitted through the nonlinear material as well as the measurements of beam distortion are used to verify the validity of the photoacoustic method. In all the measurements the on-axis intensity was smaller than the calculated threshold intensity for stimulated Brillouin scattering. The back reflection was monitored to make sure that stimulated Brillouin scattering was not playing a role in the phenomenon.

<p> I viskosprocessens inledande merceriseringssteg behandlas cellulosa (dissolvingmassa) med natriumhydroxid (NaOH) varvid cellulosan omvandlas till alkalicellulosa. Därpå följer en sulfidering med koldisulfid (CS₂) som omvandlar alkalicellulosa till natriumxantogenat. Xantatet löses i en alkalisk lösning och en trögflytande vätska, viskos, bildas. Vid tillverkning av spinnviskos är sista steget i processen en surgörning där koldisulfiden spjälkas av och cellulosan återbildas i form av en tråd. Vid tillverkning av högviskös viskos (Freudenberg HP) sker regenereringen i basisk miljö men vid förhöjd temperatur (100°C), och återbildningen av cellulosa ger då en cellulosabaserad bädd. Genom att öka dissolvingmassans reaktivitet skulle förbrukningen av koldisulfid i sulfideringssteget kunna minskas. Med en ökad reaktivitet menas att fler hydroxylgrupper på cellulosan blir tillgängliga för vidare reaktioner med natriumhydroxid och koldisulfid. Detta skulle kunna möjliggöras med en enzymatisk förbehandling av massan.</p><p>Det första delmålet i projektet var att producera en viskos med hög viskositet i laboratorieskala. Projektets andra mål var att undersöka effekterna av en enzymatisk behandling, med enzymet Carezyme^®, på massans viskositet och reaktivitet.</p><p>En studie gjordes för att se hur olika tider i viskosprocessens andra steg, pressteget, påverkade cellulosahalten och luthalten för alkalicellulosa. Resultaten tydde på att en längre presstid gav en högre cellulosahalt upp till en viss tidpunkt. Vid 195 sekunder avklingade kurvan och effekten av en längre presstid minskade. Resultatet visade också på att mängden lut i alkalicellulosaprovet var relativt konstant och att luthalten inte påverkas nämnvärt av pressningen.</p><p>Vidare genomfördes försök kring viskosprocessens sulfideringssteg. Det fanns under projektets gång stora svårigheter i att uppnå samma höga nivå på gammatalet vid produktion av viskos i laborativ skala (52-58 %) som vid produktion i fabriksskala (68-70 %). Gammatalet är ett mått på hur väl koldisulfid har reagerat med cellulosa under sulfideringen. I ett försök att öka gammatalet satsades en större mängd koldisulfid, med förhoppningen att kunna kompensera för den relativt stora andel koldisulfid som befann sig i gasfas under reaktionen och som därmed inte var aktiv under sulfideringen. Den ökade mängden koldisulfid resulterade dock inte i en ökning av gammatalet. I ett annat försök tillsattes en svag natriumhydroxidlösning direkt till sulfideringskärlet vid avslutad reaktion, utan att någon effekt på gammatalet kunde påvisas. Det undersöktes även om ett ökat förhållande mellan luthalt och cellulosahalt i alkalicellulosan kunde ge någon positiv effekt på gammatalet. Denna förändring gav dock inget ökat gammatal.   </p><p>Dissolvingmassaprover behandlades med enzymet Carezyme^® för att kunna studera dess inverkan på massans reaktivitet och viskositet.  Resultaten visade på en tydlig nedgång i viskositet med högre koncentrationer av enzym. Reaktiviteten på den enzymbehandlade massan ökade i jämförelse med den obehandlade massan. Då viskos producerades med en enzymbehandlad massa kunde ingen effekt av enzymbehandlingen noteras, med avseende på gammatalet.</p><p> </p> / <p>In the first step of the conventional viscose process, called mercerization, cellulose (dissolving pulp) is treated with sodium hydroxide (NaOH) in which the cellulose is converted to alkali cellulose. Alkali cellulose is then treated with carbon disulphide (CS₂) to be converted into a sodium xanthate.  This xanthate is dissolved in an alkali solution and a viscous liquid, called viscose, is formed. The last step in the process is an acidification where the carbon disulphide is splinted off and the cellulose is regenerated in the shape of threads. When producing high viscosity viscose (Freudenberg HP) the regeneration takes place in an alkaline environment and the re-formation of cellulose gives a cellulosic based bed. By increasing the reactivity of the dissolving pulp the amount of carbon disulphide could be reduced, compared at the same degree of substitution. An increase in reactivity means that a larger amount of hydroxyl groups on the cellulose molecule are available to react with sodium hydroxide and carbon disulphide. This could be enabled by an enzymatic pretreatment of the pulp prior to the mercerization step.</p><p>The first aim of this project was to produce a high viscosity viscose in a laboratory scale, comparable to the viscose quality that is produced by Freudenberg HP. The second aim of the project was to investigate the effects of an enzymatic treatment (with the enzyme named Carezyme^®) on the viscosity and reactivity of the dissolving pulp. </p><p>A study was made to examine the influence of the time in the pressing step (after the mercerization) on the cellulose and sodium hydroxide content in the alkali cellulose. The results indicated a linear correlation between the cellulose content and the pressing time up to 195 seconds. At this point the correlation declined and the effects of a longer pressing time decreased. The results also showed that the amount of lye in the alkali cellulose sample was nearly constant and therefore not effected by the pressing time.</p><p>Tests were also carried out concerning the sulphidation step in the process. During the whole project there were difficulties in reaching the same gamma value of the viscose in a laboratory scale (52-58 %) compared to large-scale production (68 - 70%). The gamma value is a measurement of the degree of substitution for carbon disulphide on the cellulose backbone. In one attempt to enhance the gamma value the carbon disulphide charge was increased. The expectation was to compensate for the relatively high amounts of inactive carbon disulphide expected to be found in the gaseous phase in the reactor. However, this did not result in a higher gamma value. In another experiment a weak solution of sodium hydroxide was added directly to the sulphidation vessel after the reaction was completed, but no change in the gamma value was obtained. It was also investigated if an increased relation between the cellulose- and sodium hydroxide content in the alkali cellulose could affect the gamma value positively.  Unfortunately, this modification did not give an increased gamma value.</p><p>Samples of dissolving pulp were treated with the enzyme Carezyme^® to see its impact on viscosity and reactivity of the pulp. The results showed a distinct loss in viscosity with an increased enzyme concentration. The reactivity of the pulp increased compared to the untreated pulp. No effects of the enzymatic treatment could be seen on the final viscose when it was produced from an enzyme treated pulp.</p>