Document Type

Thesis

Date of Award

1-31-1990

Degree Name

Master of Science in Engineering Science- (M.S.)

Department

Chemical Engineering, Chemistry and Environmental Science

First Advisor

Lawrence Suchow

Second Advisor

Barbara B. Kebbekus

Third Advisor

George Y. Lei

Abstract

Cupric and ferrous polyacrylates have been prepared and studied. It was thought that partial reduction of Cu2+ or Fe3+ or oxidation of Cu+ or Fe2+ might result in semiconducting behavior but no such effect has been observed. Nevertheless, the results obtained are of considerable interest. Quantitative gravimetric and volumetric studies of cupric polyacrylate precipitation from varying molar ratios of cupric chloride and sodium polyacrylate in aqueous solution have shown that the only product formed is Cu(PA)2 (Where PA represents an acrylate mer in polyacrylate). The insolubility of the product indicates that much of the Cu2+ acts to crosslink molecules rather than simply to replace two adjacent hydrogen ions on the same polymer molecule. The product is blue and hard, though sufficiently brittle to be ground to powder. At high H2 pressure in a Parr bomb, reduction has been achieved at room temperature at which, over a period of ten days, the compound turns black. At 71°C or 91°C, again at high H2 pressure in a Parr bomb, it turns copper brown in two hours. The reduction products, like cupric polyacrylate itself, are electrical insulators. Because the materials reduced at low temperature should still be quite porous and contain extremely finely divided Cu or a mixture of oxidation states, it is quite possible that they would make excellent catalysts. Diffuse reflectance measurements have been used to define the various colors quantitatively. Cu(PA)2 and black material are amorphous to x-rays while the copper-brown product has been found to contain crystalline metallic copper. Ferrous and ferric polyacrylates were also precipitated. The former was found to be blue-green and an electrical insulator and the latter yellowish tan and unfilterable. In another preparation, ferrous polyacrylate was first precipitated and then, while still wet, about 20% of it oxidized to the ferric state by addition of I2. Whereas ferrous polyacrylate is hard and brittle like cupric polyacrylate, the partially I2-oxidized preparation is soft (and yellowish tan). None of the Fe preparations is crystalline to x-rays

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