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The potential of inert electrons in sulfurous acid solution

Citation

Steinour, Harold Heiges (1928) The potential of inert electrons in sulfurous acid solution. Dissertation (Ph.D.), California Institute of Technology. http://resolver.caltech.edu/CaltechETD:etd-02232005-154106

Abstract

Certain reducing substances, such as sulfurous acid, formic acid, or oxalic acid, show in their chemical behavior a much smaller reducing power than that calculated from the free-energy changes attending their conversion into their ordinary oxidation products, sulfuric acid or carbon dioxide and water. This fact is especially pronounced in the case of sulfurous acid, where a fairly definite electrode-potential (about -0.4 volts) results, which is in much better agreement with its known chemical behavior than is the potential (-0.14 volts) calculated for the conversion of SO2 (1 atm.) to SO4=(1 m.)

The probable nature of the electrode process has been considered by Carter and James. In view of the apparent discrepancy with the calculated sulfite-sulfate potential, they considered the observed potential to be due to the tendency of the sulfur dioxide to be reduced rather than oxidized, an assumption which is also justified by its chemical behavior, which will be discussed later. Since experiments in which sulfur was added to the electrode vessel did not improve the constancy or reproducibility of the potential (which varied over 0.05 volts), they concluded that the sulfur was without effect, and that an intermediate reduction-product of sulfurous acid was concerned, which their experiments on the cathodic reduction in acid solution led them to believe was hydrosulfurous acid, H2S2O4

The present work is a further contribution to the interpretation of this sulfur dioxide potential. It is concerned chiefly with the potentials exhibited at a platinized platinum electrode in a half-cell containing sulfur dioxide in acid solution under various conditions of concentration, temperature, and agitation, and in the presence of certain other substances.

This investigation was carried on under the supervision of Professor A. A. Noyes to whom the writer is indebted for much helpful advice and cooperation. It was assisted financially by a grant to Professor Noyes from the Carnegie Institute of Washington.

Item Type:Thesis (Dissertation (Ph.D.))
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Noyes, Arthur A.
Thesis Committee:
  • Unknown, Unknown
Defense Date:1 January 1928
Record Number:CaltechETD:etd-02232005-154106
Persistent URL:http://resolver.caltech.edu/CaltechETD:etd-02232005-154106
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:714
Collection:CaltechTHESIS
Deposited By: Imported from ETD-db
Deposited On:24 Feb 2005
Last Modified:26 Dec 2012 02:31

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