The Kinetics of Oxidation of Various Organic Substrates by Potassium Ferrate

Authors

Ronald Lee Bartzatt, University of Nebraska-LincolnFollow

First Advisor

James Carr

Committee Members

Gary Hergenrader, Robert B. Johnston, Robert C. Larson, George D. Sturgeon

Date of this Version

7-1982

Document Type

Dissertation

Citation

A dissertation presented to the faculty of the Graduate College of the University of Nebraska in partial fulfillment of requirements for the degree of Doctor of Philosophy

Major: Chemistry

Under the supervision of Professor James Carr

Lincoln, Nebraska, July 1982

Comments

Copyright 1982, Ronald Lee Bartzatt. Used by permission

Abstract

Potassium ferrate is a strong oxidizing agent and highly soluble in water. These properties may allow it to oxidize a wide variety of aqueous organic compounds to simpler organic compounds. The kinetics and final products of typical ferrate oxidations must be studied before conclusions about its efficiency can be drawn.

The ferrate oxidation of diethylsulfide and 2,2-thiodiethanol were studied in a pH range of 8.90 to 9.90. Their plots of Log k_s versus pH are essentially parallel and show mixed-order characteristics. The order of dependence of diethylsulfide on [H⁺] is 0.708. The order of dependence of 2,2-thiodiethanol on [H⁺] is 0.735.

The ferrate oxidation of chloral was studied in a pH range of 7.90 to 9.30. Chloral exists in aqueous solution in its hydrated form. The order of dependence of chloral on [H⁺] is 0.226.

The oxidation of acetaldehyde by potassium ferrate has been studied at three different temperatures (18ºC, 25ºC, and 35ºC). An increase in reaction temperature increases the value of k_1(Obs). Plotting log k_s values of the three temperatures versus pH shows three lines that are essentially parallel. At 25ºC the order of dependence of the reaction to [H⁺] is 0.729.

Neopentyl alcohol has been studied at three different temperatures (15ºC, 25ºC, and 35ºC). An increase in reaction temperature does not bring about an increase in k_1(Obs). At 25ºC the order of dependence of the reaction on [H⁺] is 1.11.

Using the data obtained for acetaldehyde, observations concerning thermodynamics can be made. Calculations for activation energy, ΔH^≠o, ΔG^≠o, ΔS^≠o, K^≠_eq, and Q have been made for acetaldehyde.

A study of water oxidation by potassium ferrate was made. The values of k_1(Obs) for water oxidation by potassium ferrate do not change significantly as temperature of the reaction solutions vary from 35ºC to 18ºC. Graphs of Log k_1(Obs) versus pH and Log k_2(Obs) versus pH are linear.

Advisor: James Carr