Kofahl, Robert Eugene (1954) Part I. Exploratory investigation of the autoxidation and hydration of 3-hexyne catalyzed by mercuric sulfate and sulfuric acid. Part II. The effect of mercuric nitrate and other electrolytes upon the aqueous solubility of benzene. Part III. Coordination of polycyclic aromatic hydrocarbons with silver ion; correlation of equilibrium constants with relative carcinogenic potencies. Dissertation (Ph.D.), California Institute of Technology. http://resolver.caltech.edu/CaltechETD:etd-12042003-094412
The addition of water to the triple bond of 3-hexyne catalyzed by sulfuric acid and mercuric sulfate was studied. The aqueous hexyne was found to undergo mercury-catalyzed autoxidation. The product of the hydration reaction, 3-hexanone, was shown by spectrophotometric methods to react with mercuric sulfate to form a stable complex. The production of 3-hexanone was followed spectrophotometrically and the rate was found to be approximately first order with respect to 3-hexyne, hydrogen ion, and mercuric sulfate.
The solubility of benzene was measured in aqueous solutions of mercuric nitrate and several other electrolytes. Only salting effects were observed. The evidence indicates that mercuric ion does not form a coordination complex with benzene in aqueous solution.
The relative nucleophilic character with respect to silver ion was determined for twenty-four polycyclic aromatic hydrocarbons. This was accomplished by measuring the solubilities of each hydrocarbon in equimolal aqueous methanol containing silver nitrate and sodium nitrate at constant ionic strength. From the variation of solubility with silver concentration the argentation or equilibrium constants for coordination of each hydrocarbon with the first and second silver ions were calculated. The argentation constants for the series of hydrocarbons were correlated with an index of relative carcinogenic potenc
|Item Type:||Thesis (Dissertation (Ph.D.))|
|Degree Grantor:||California Institute of Technology|
|Division:||Chemistry and Chemical Engineering|
|Thesis Availability:||Public (worldwide access)|
|Defense Date:||1 January 1954|
|Default Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Imported from ETD-db|
|Deposited On:||10 Dec 2003|
|Last Modified:||26 Dec 2012 03:11|
- Final Version
See Usage Policy.
Repository Staff Only: item control page