Formaldehyde, a hazardous and toxic substance, can be found in most resin treated durable press fabrics. The current formaldehyde regulations are limited to worker exposure in an industrial setting and the possibility of government regulation of formaldehyde release from textiles is of concern to the textile industry. The most common test of formaldehyde release used by the U.S. textile industry is the AATCC Test Method 112, a colorimetric determination based on the Hantzsh reaction between ammonia, formaldehyde, and acetylacetone. The chromophore formed is 3,5-diacetyl-1,4-dihydrolutidine (DDL). In the AATCC test the ammonia and acetylacetone are in the Nash reagent and the formaldehyde is extracted from the fabric by trapped steam. The formaldehyde in solution and the Nash reagent are mixed and the color developed. The purpose of this study was to determine if a more effective formulation of the Nash reagent than currently used by industry can be produced. The reaction between the Nash reagent and formaldehyde is first order in formaldehyde, therefore pseudo-first order kinetics was used as the basis of the study. Reagent effectiveness was determined by comparisons and calculations based on the molar extinction coefficient, maximum absorbance, and rate constant. The study was set up in phases to investigate the effect of different ammonia sources, the effects of varying concentrations of the reactant components, the effect of ageing, and the effect of different temperatures on the formation of DDL. In the final phase the best reformulated reagent was compared to the Nash reagent under the conditions of the AATCC Test Method 112. Several reformulations were found to be comparable to Nash, but none was found to be more effective in formaldehyde detection. This study has shown some of the complexities of the reaction and that the Nash reagent is not able to obtain 100% conversion of formaldehyde to DDL. Therefore, any test that uses the Nash reagent is underestimating the releasable formaldehyde concentration in the fabric. / Ph. D.

Long chain alkyl pyridinium salts have been used as collectors for the flotation of chalcopyrite and copper-activated sphalerite. For the ores tested in this study, these reagents have demonstrated improved selectivity and recovery in comparison to conventional xanthates. The best flotation results, in terms of both grade and recovery, were achieved with cetyl pyridinium chloride (CpCl). A distinct advantage of using CpCl instead of a conventional xanthate, such as sodium isopropyl xanthate (NaIpX), is that the kinetics of flotation are much faster. This may be explained by the reduction in the negative ζ-potential of the sulfide mineral upon adsorption of cetyl pyridinium ions, which, in turn, minimizes the electrostatic component of the disjoining pressure of the wetting film. CpCl has also demonstrated a remarkable selectivity despite the fact that both chalcopyrite and the silicious gangue minerals present in the ore are negatively charged. This may be explained by the premise that cetyl pyridinium ions adsorb more strongly on chalcopyrite than on the gangue. Analysis of the adsorption isotherms established for chalcopyrite and quartz supports this view. Several possible mechanisms have been suggested to explain the 'high affinity' type of adsorption observed in the CpCl-chalcopyrite system. / Master of Science

Numerous organic reagents of diverse structural composition are employed in the froth flotation process for the beneficiation of non-metallic and sulphide ores. Alkyl xanthates are used as collectors for sulphide ores while amines and fatty acids are used for non-metallic ore beneficiation. Although these collector reagents react preferentially with the concerned minerals in the treated ore pulp, excess and unreacted concentration of these organic collectors end up in the mill process effluents. It has been known that even small concentrations of these organic reagents in water streams are toxic to water life, besides their deleterious influence on end stream processes during recycling. Bioremediation has long been recognised as an inexpensive, flexible and environmentally benign technique for waste water treatment. These organic flotation reagents are amenable to biological degradation. The major objective of this work is the degradation of solubilized collector reagents from aqueous solutions using a microbial technique. Bacillus polymyxa, a Gram-positive, neutrophilic, periflagellated heterotroph that occurs indigenously in soils and certain mineral deposits has been used in the bioremediation studies. Organic flotation reagents namely, dodecyl ammonium acetate (DAA), which is used as a collector for oxides and silicates, sodium isopropylxanthate which finds application in sulphide flotation and sodium oleate, mainly used for oxide and salt-type minerals, have been chosen for the degradation studies. Pure minerals of galena, pyrite, magnetite, quartz and calcite have been typically selected for these investigations. The growth of Bacillus polymyxa in the presence of these organic reagents at different concentrations has been assessed and the degradation of these reagents monitored. Attempts have been made to grow the bacterium in the presence of the organic reagents, both in the absence and presence of sucrose, by adaptation technique. Electrokinetic studies on the chosen minerals namely, galena, pyrite, quartz, calcite and magnetite have been carried out both in the presence of the organic reagents and Bacillus polymyxa cells or metabolite. Biological stripping of the adsorbed collector reagents from the mineral surfaces have been examined through FTIR spectroscopy. The progress of bioremoval of the organic reagents along with the generation of newer reaction products has also been monitored through uv-visible spectroscopic technique. The results of this study highlight that Bacillus polymyxa and its metabolic products bring about the degradation of the chosen organic flotation collectors. Further, the bacteria are able to utilise the collector reagents as carbon source for their growth, in the absence of added organic carbon (sucrose). Electrokinetic studies and examination by FTIR spectroscopy reveal that consequent to interaction with Bacillus polymyxa, significant surface modification on the mineral takes place. Probable mechanisms in the biodegradation processes are illustrated. Biological metabolic products responsible for bringing about the bio-deterioration have been analysed and characterised.

Thesis (Ph. D.)--State University of New York at Binghamton, Department of Chemistry, 2007. / Includes bibliographical references.

by Chan Wai Man. / Thesis (M.B.A.)--Chinese University of Hong Kong, 1988. / Includes bibliographical references.

Call number: LD2668 .T4 1984 T78 / Master of Science

published_or_final_version / abstract / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / abstract / Chemistry / Doctoral / Doctor of Philosophy

No description available.

The group 14 Zintl clusters [E₉]⁴⁻ (E = Ge, Sn, Pb) have been reacted with organometallic reagents in solution in the presence of alkali metal cation sequestering agents. The synthesis, characterisation and reactivity studies of the resultant complexes are reported herein. These negatively charged clusters reductively cleave one of the M–C bonds in the group 12 homoleptic organometallic reagents MR₂ (M = Zn, Cd; R = Ph, mes, ⁱPr) to yield η⁴-coordinated functionalised clusters closo-[E₉MR]³⁻. They can also activate both of the M–C bonds in Cd(mes)₂ to form metal-bridged dimers [Ge₉CdGe₉]⁶⁻ and [Pb₉CdCdPb₉]⁶⁻. Investigating the reactivity of the functionalised cluster [E₉CdPh]³⁻ (E = Sn, Pb) towards HSn(ⁿBu)₃ results in the synthesis of the novel closo-clusters [E₉CdSn(ⁿBu)₃]³⁻. The reaction of K₄Ge₉ with the heteroleptic organometallic reagent Fe(COT)(CO)₃ yields the metalated cluster anion [Ge₈Fe(CO)₃]³⁻, in which the nuclearity of the Zintl anion is altered upon coordination of the [Fe(CO)₃] moiety. Two side products have also been isolated as [K(2,2,2-crypt)]⁺ salts of [Fe(η³-C₈H₈)(CO)₃]⁻ and [Fe₂(η³, η′³-C<sub<16</sub<H₁₆)(CO)₆]²⁻. In the presence of highly reduced Zintl anions, all the M–C bonds in homoleptic mid-row transition metal organometallic reagents can also be cleaved. These ‘naked’ metal atoms have templated the formation of the endohedral clusters [Fe@Ge₁₀]³⁻, [Fe@Sn₁₀]³⁻ and [Mn@Pb₁₂]³⁻. These clusters adopt very different geometries and the electronic origin of their structures has been investigated in-depth by DFT calculations. Structural characterisation of some side products is also reported for: [E₉(mes)]³⁻ (E = Ge, Sn) and [Ge₉Mn(mes)]³⁻.