Call number: LD2668 .T4 1939 D41 / Master of Science

No description available.

No description available.

Thesis (Ph. D.)--Columbia University, 1926. / Vita. Bibliography: [3] p. at end.

Philosophiae Doctor - PhD / Maleic acid (MA) is a key intermediate for the synthesis of polyester resins, surface coatings, lubricant additives, plasticizers, copolymers, pharmaceuticals and agricultural chemicals. The current industrial production of MA is an energy-intensive gas-phase oxidation process of n-butane. The dwindling fossil resources and environmental issues have brought about a worldwide paradigm shift from fossil feedstocks to biomass resources for the sustainable production of fuel and chemicals. Furfural (FFR) and 5-hydroxymethylfurfural (HMF) are excellent biomass-derived platform chemicals, which present an alternative route for the production of renewable bio-based MA. There has been considerable success achieved in the oxidation of furfural and HMF to maleic acid and maleic anhydride with different catalysts in recent years.

Control of weeds is an agricultural problem of great importance. For centuries, only salts, ashes, or mechanical means of eradication such as hoeing, cutting, or burning were used in weed control. A large number of chemicals have been used for this purpose also. With the advent of modern railroads, highways, and power lines, the demand has grown for newer and more effective control of weeds and brush. The initial application of chemical herbicides produced erratic results in many instances. Some herbicides retarded the growth rate of certain forms of vegetation but left other forms unaffected. Likewise, some herbicides killed the entire plant, while others killed only the portion sprayed. Since 19ul, however, the discovery of synthetic growth regulating substances or plant hormones as effective weedkillers has brought about a revolutionary change in the chemical control of weeds. The synthetic hormone substances are greatly superior to ordinary chemicals in that they are highly selective as between plant species and have many other additional advantages. They are now being used in many places throughout the world, but too often with little accurate knowledge of their nature or of the special circumstances under which they should and should not be used. Such information is important because these substances can be very destructive to vegetation when improperly applied. Maleic acid hydrazide is a relatively new herbicide, possessing the hormone—like property of retarding plant growth for long periods of time by preventing the division of cell nuclei. Field applications of the hydrazide have shown good growth retarding ability on many types of weed and shrubs In view of the wide variation in environmental conditions and farming practices in different parts of the world, as well as the great variety of crop and weed plants involved, the control of weeds is essentially a local problem, and instructions for specific regions and for specific purposes cannot be given until results of local tests become available. It is therefore necessary to rely on experimental work conducted locally for information on how to use these substances. / Master of Science

Yes / A green approach has been used for co-crystallization of non-congruent co-crystal pair of caffeine – maleic acid using water. Ultrasound is known to affect crystallization hence the effect of high power ultrasound on the ternary phase diagram has been investigated in detail using a slurry co-crystallization approach. A systematic investigation was performed to understand how the accelerated conditions during ultrasound assisted co-crystallization will affect different regions of the ternary phase diagram. Application of ultrasound showed considerable effect on the ternary phase diagram; principally on caffeine/maleic acid 2:1 (disappeared) and 1:1 co-crystal (narrowed) regions. Also, the stability regions for pure caffeine and maleic acid in water were narrowed in the presence of ultrasound, expanding the solution region. The observed effect of ultrasound on the phase diagram was correlated with solubility of caffeine and maleic acid and stability of co-crystal forms in water.

Este projeto propôs a utilização de eletrodos de óxidos metálicos contendo RuO2 para realizar a eletrooxidacao do ácido maleico visando sua degradação total ou formação de produtos com menor grau de toxicidade. A oxidação de compostos fenólicos, clorados ou não, resultam em alguns produtos que interferem na mineralização completa das estruturas clorofenólicas, o ácido maleico, que é um dos principais intermediários obtidos depois da abertura do anel aromático. Os recobrimentos óxidos foram caracterizados por Microscopia Eletrônica de Varredura e Análise Dispersiva de Raios X. A caracterização eletroquímica por voltametria cíclica foi utilizada para determinação de potenciais de oxidação do acido maleico em função do eletrólito de suporte. As eletrólises foram realizadas a corrente controlada visando à melhor relação entre eficiência de corrente/degradação e melhoria no entendimento do mecanismo de oxidação. As análises quantitativas dos produtos da eletrólise foram feitas através de CLAE e a taxa de mineralização foi determinada pela quantidade de COT. Além destes dois métodos, também foram realizados testes de DQO e AOX. Os resultados mostraram que os métodos de preparação utilizados são apropriados, pois apresentaram estabilidade química, mecânica, eficiência na oxidação do ácido maleico e redução do carbono orgânico total. / This project proposed the use of metallic oxide electrodes containing RuO2 to perform the total degradation or formation of products with less toxicity. The oxidation of phenolic compounds, chlorinated or not, result in some products that interfere with complete mineralization of chlorophenol structures, the maleic acid, which is a important intermediate obtained after opening the aromatic ring. The coatings were characterized by scanning electron microscopy and X-ray dispersive analysis. The electrochemical characterization by cyclic voltammetry was used to determine the potential for the oxidation of maleic acid as a function of electrolyte support. The electrolyses were carried out at controlled current to the best ratio of efficiency of current/degration and improving the understanding of the mechanism of oxidation. The quantitative analysis of the electrolysis products were made by HPLC and the rate of mineralization was determined by the amount of TOC. Besides these two methods were also investigated COD and AOX. The results showed that the electrode preparation methods used are appropriate, showing chemical stability, mechanical efficiency in the oxidation of maleic acid and reduction of total organic carbon

Este projeto propôs a utilização de eletrodos de óxidos metálicos contendo RuO2 para realizar a eletrooxidacao do ácido maleico visando sua degradação total ou formação de produtos com menor grau de toxicidade. A oxidação de compostos fenólicos, clorados ou não, resultam em alguns produtos que interferem na mineralização completa das estruturas clorofenólicas, o ácido maleico, que é um dos principais intermediários obtidos depois da abertura do anel aromático. Os recobrimentos óxidos foram caracterizados por Microscopia Eletrônica de Varredura e Análise Dispersiva de Raios X. A caracterização eletroquímica por voltametria cíclica foi utilizada para determinação de potenciais de oxidação do acido maleico em função do eletrólito de suporte. As eletrólises foram realizadas a corrente controlada visando à melhor relação entre eficiência de corrente/degradação e melhoria no entendimento do mecanismo de oxidação. As análises quantitativas dos produtos da eletrólise foram feitas através de CLAE e a taxa de mineralização foi determinada pela quantidade de COT. Além destes dois métodos, também foram realizados testes de DQO e AOX. Os resultados mostraram que os métodos de preparação utilizados são apropriados, pois apresentaram estabilidade química, mecânica, eficiência na oxidação do ácido maleico e redução do carbono orgânico total. / This project proposed the use of metallic oxide electrodes containing RuO2 to perform the total degradation or formation of products with less toxicity. The oxidation of phenolic compounds, chlorinated or not, result in some products that interfere with complete mineralization of chlorophenol structures, the maleic acid, which is a important intermediate obtained after opening the aromatic ring. The coatings were characterized by scanning electron microscopy and X-ray dispersive analysis. The electrochemical characterization by cyclic voltammetry was used to determine the potential for the oxidation of maleic acid as a function of electrolyte support. The electrolyses were carried out at controlled current to the best ratio of efficiency of current/degration and improving the understanding of the mechanism of oxidation. The quantitative analysis of the electrolysis products were made by HPLC and the rate of mineralization was determined by the amount of TOC. Besides these two methods were also investigated COD and AOX. The results showed that the electrode preparation methods used are appropriate, showing chemical stability, mechanical efficiency in the oxidation of maleic acid and reduction of total organic carbon

In the investigation the effects of excess maleic anhydride, hydrazine hydrate-solvent reagent addition time, volume of reaction mass after concentration by heating at 100 °C, mixing of reactants, and the solvent selected were studied for the heterogeneous reaction of maleic anhydride and hydrazine hydrate. A reaction time of 12 minutes was employed with the ratio of solvent to reactants held constant at 75 weight per cent throughout the tests. Solvents employed in the investigation included ethanol, methanol, isopropanol, glacial acetic acid, water, hydrachloric acid, and benzene. Atmospheric drying tests at 25 to 88 °C were employed on hydrazide slurries of free moisture content from 1.258 to 1.515 pounds of water per pound of hydrazide. Centrifuge tests at 2000 to 4700 revolutions per minute and a rotary filtration test under a 10 inch vacuum were employed on 13 weight per cent hydrazide slurries. Hydrazide filtrate evaporation tests at 100 °C were performed on samples of 18 to 1715 milliliters to determine the approximate hydrazide content in the slurries. Field applications of 0.10 to 0.22 weight per cent hydrazide solutions in water were made on "wild" varieties of briers, bermuda grass, johnson grass, milkweed, red pine, ragweed, and honey locust in the Blacksburg, Virginia, area from May to August, 1956. The yield of maleic acid hydrazide was increased from 42.6 to 67.0 per cent when the maleic anhydride excess was increased to 20 per cent in the reaction. The optimum addition time for the ethanol-hydrazine hydrate reagent to the maleic anhydride was found to be 3.8 seconds, while the optimum volume of reaction mass after concentration by beating at 100 °C was 10 to 15 milliliters for the non-agitated reactions. Agitation of the reaction mass and the solvent chosen were determined to increase the yield of the hydrazide. The optimum drying temperature and time for the drying of the hydrazide slurries were determined to be 88 °C and 75 minutes, respectively. Rotary vacuum filtration of the hydrazide slurries was determined to produce a cake free moisture of 1.33 pounds of water per pound of hydrazide as compared with 1.38 for the centrifuge test at 4700 revolutions per minute. The hydrazide content of the filtrate samples was determined to be approximately 10 to 15 per cent. Field applications on "wild" plots indicated that 40 to 80 per cent control of briers, bermuda grass, ragweed, johnson grass, and red pine could be achieved from one application of 0.10 to 0.22 weight per cent hydrazide solutions in early spring. On milkweed and honey locust growth, the spraying solution would not adhere to the leaf. A total fixed plus working capital of $1,151,740 was determined to be necessary to build a plant for the production of 242 tons of 95.5 percent pure maleic acid hydrazide per year. On this basis, a selling price of $3.00 per pound ($0.05 per gallon) would yield a 13.7 percent return as new earnings on total fixed plus working capital. / Ph. D.