Thesis (Ph. D.)--University of Wisconsin--Madison, 1968. / Typescript. Vita. Includes computer code: leaves 34-47. Description based on print version record. Includes bibliographical references (leaves 22-23).

Thesis (MTech(Chemical engineering))--Cape Technikon, Cape Town,1996 / Metal cyanide complexes are a toxic pollutant in waslewater originating from various industrial and mining activities. The removal/retrieval ofcyanide and metal cyanide complexes has been studiedby researches for many years, leading to the establishment of a variety of patents. The mechanisms used by these patents vary from purely chemical techniques to those using ion exchange Iesins. In this thesis, ,the feasIbility ofthe recovery ofmetal cyanide complexes by using a strong base macroreticular resin, in a fluidized bed configuration, has been investigated. The resin in question is presently used in the sugar indnstry where its main application is the recovery oflarge organic molecules similar in nature to metal cyanides. The selected resin was contacted with synthetic solntions of various metal cyanide complexes. for the purposes of evaluating performance in the adsorption th..."feOf. It was found that polyvalent metal cyanide molecules were adsOlbed efficiently, while divalent metal cyanide molecules were adsorbed satisfactorily. The loaded resin was also evalnated for the ease with which the metal cyanides conId be removed. It was discovered that a brine solntion ofpH 7, conId effectively remove all metal cyanide complexes. This test-work was of particular importance as it is well !moon that the removal ofmetal cyanides from strong base metals is not easily achieved. To distingnish the fluidization characteristics of the selected resin (or any resin for that matter), a method of modelling the expansion of a flnidized resin bed was proposed, that takes into account the diflicnIties associated with the byclrod:)nantic charncteristics of a macroporous resin of this nature. The technique is based on the Serial Afadel which is a discretised application of the Z3ki and Richardson equation. From the interpretation of the resnIts of a matrix of fluidization tests, it was fonnd that the algorithm proposed conId effectively model the expansion of a fluidized bed of ion exchange resin, independently of the dimensions ofthe accomodatiog receptical. Finally. it was shown that the change in the fluidization characteristics of the selected resin, between its chloride and metal cyanide states, could clearly be modelled by the technique referred to above.

ΔH° values are reported for the formation of Fe(CN)_6^4- (-85.77 ± 0.09 kcal/mole), Fe(CN)_6^3- (-70.14 ± 0.10 kcal/mole), Mn(CN)_6^4- (-36.76 ± 0.07 kcal/mole), Co(CN)_5^3- (-61.96 ± 0.15 kcal/mole), Ni(CN)_4^2- (-43.26 ± 0.08 kcal/mole), Zn(CN)_4^2- (-28.53 ± 0.10 kcal/mole), Cu(CN)_n^1-n (n = 2,3,4 - 29.1 ± 0.10, - 40.3 ± 0.10, and - 50.5 ± 0.01 kcal/mole respectively), PdBr_4^2- (-13.11 ± 0.06 kcal/mole), PdCl_4^2- (-5.50 ± 0.05 kcal/mole), Pd(CN)_4^2- (-92.14 ± 0.10 kcal/mole), Cd(CN)_4^2- (-28.50 ± 0.10 kcal/mole), Ag(CN)_2^- (-32.88 + 0.08 kcal/mole), and Ag(CN)_3^2- (-33.45 ± 0.10 kcal/mole) from their respective constituent ions in aqueous solution. A method is discussed for estimating the ligand field stabilization energy for low spin octahedral complexes from the measured ΔH° value. A comparison of the ΔH values for the formation PdX_4^2- (X = CN, Cl, Br) from their respective aqueous ions show that the ΔH value for Pd(CN)_4^2- is 75 kcal/mole more exothermic than the ΔH values for the formation of PdX_4^2- (X = Cl,Br). This large difference in ΔH values is discussed in terms of different bonding properties of the CN^-, Cl^- and Br^- ions. Evidence is presented which suggests that the nonstepwise formation of some cyano complexes results from ligand field effects. The ΔH° values for the formation of soluble Turnbull's and Prussian blue were measured. The resulting values are -15.08 ± 0.05 and +0.65 ± 0.01 kcal/mole, respectively. Soluble Prussian and Turnbull's blue were found to be thermochemically equivalent and to be noncolloidal in aqueous solution. The Co^2+ -CN^- system was investigated in dilute aqueous solution. The heat of interaction of Co^2+ and CN^- was studied as a function of the CN^-/Co^2+ ratio and the H^+ concentration. An enthalpy change of -30 kcal/mole results when the Co(CN)_5^3- ion reacts with one equivalent of H^+. A kinetic study was made of the decay of Co(CN)_5^3- under controlled pH conditions and as a function of Co(CN)_5^3- concentration. The following reactions were postulated as steps in the decay of Co(CN)_5^3- to form Co(CN)_5 H_2O^2- and H_2. Co(CN)_5^3- + H^+ = HCo(CN)_5^2- (1) 2HCo(CN)_5^2- = [ HCo(CN)_5 ]_2^4- (2) [ HCo(CN)_5 ]_2^4- = 2Co(CN)_5^2- + H_2 (3)

No description available.

Carbohydrate research remains one of the most exciting endeavors in the field of organic chemistry. The importance of carbohydrates needs little elaboration. Quite literally, without glucose, cellulose, and starch, the necessities of life such as food, clothing, and shelter would be missing. In our laboratory, we have for some time been interested in one particular class of carbohydrate derivatives - the aldohexopyranosyl cyanides.

Thesis (M.S.)--University of North Texas, May, 2009. / Title from title page display. Includes bibliographical references.

Diss. (sammanfattning) Uppsala : Uppsala universitet, 2005. / Härtill 4 uppsatser.

Thesis (Ph. D.)--Montana State University--Bozeman, 2005. / Typescript. Chairperson, Graduate Committee: David M. Dooley. Includes bibliographical references (leaves 121-133).

Photochemical properties of sulphonated phthalocyanine complexes of aluminium, zinc, tin and silicon, and octa-carboxyphthalocyanine complexes of aluminium and zinc have been investigated. These water-soluble metallophthalocyanine (MPc) complexes, especially the sulphonated aluminium and zinc phthalocyanines, were found to be good photosensitisers for the transformation of the toxic mono-, tri- and penta-chlorophenols in aqueous solutions. The efficiency of MPc sensitiser towards photo-transformation of chlorophenols depends on its effectiveness to generate singlet oxygen as well as its photostability. Octa-substituted thiol-derivatised phthalocyanine complexes of cobalt, iron and zinc were synthesized and their spectral and electrochemical properties investigated. The photochemical properties ofthe zinc phthalocyanine complexes in non-aqueous solutions were comparable to those in literature. Ultrathin films of the octasubstituted thiol-derivatised phthalocyanine complexes of cobalt, iron and zinc were, for the first time, immobilized onto gold electrodes using the self-assembling technique. Surface electrochemistry indicates that the ultrathin films are surface-confined self-assembled monolayer (SAM) species. Gold electrodes modified with the redox-active SAMs of cobalt and iron phthalocyanine complexes proved to be potential electrochemical sensors for the detection of thiols (L-cysteine, homocysteine and penicillamine) and thiocyanate in aqueous solutions (pH 4). The limits of detection for the thiols and thiocyanate were in the range of ∼ 10⁻⁷ and 10⁻⁶ mol dm⁻³, respectively. The modification process was reproducible and the modified electrodes showed good stability and, if stored in pH 4 buffer solutions, could be used for the analysis of thiols and thiocyanate for about a month without the need for recalibration. Etching of gold marred electrochemical detection of cyanide with the MPc-SAM-modified gold electrodes. Interestingly, however, kinetic and equilibria studies revealed strong interaction of octabutylthiophthalocyaninatoiron (II), FeOBTPc, with cyanide in both DMF and DMSO solutions.

No description available.