The oxidation of triethylamine by thallium(III) chloride Public Deposited

http://ir.library.oregonstate.edu/concern/graduate_thesis_or_dissertations/6395wb21b

Descriptions

Attribute NameValues
Creator
Abstract or Summary
  • The oxidation of triethylamine by the two electron oxidant thallium(III) chloride was studied and the results compared to those when triethylamine is oxidized by copper(II) halides. This study requires anhydrous conditions since in an aqueous system thallium(III) chloride is extensively hydrolyzed and triethylamine causes precipitation of thallium(III) oxide. Most of the work was carried out in anhydrous acetonitrile. Synthesis techniques and analytical methods for thallium(III) chloride had to be developed prior to any comprehensive investigations of the oxidation-reduction reaction. The stoichiometry of the reaction was investigated using inert atmosphere techniques and a variety of analytical techniques, including potentiometric and conductometric techniques. In addition, characterization of the reaction products was undertaken by several methods. Thallium(III) chloride reacts vigorously with an excess of triethylamine to give white, solid thallium(I) chloride, triethylammonium chloride, and a red-brown tarry amine oxidation product. The amine oxidation product is thought to be primarily a polymer of N, N-diethylvinylamine. This tarry solid was separated completely from the thallium salts, but always contained some chloride, possibly present as an amine hydrochloride. The physical properties of the polymer were not completely characterized. The reaction is thought to involve an initial complex formation between triethylamine and thallium(III) chloride, with rapid oxidation-reduction occuring within the complex. There is then a net transfer of two electrons, with loss of two protons and two chlorides to produce two moles of hydrogen chloride and one mole each of thallium(I) chloride and N, N-diethylvinylarnine. Subsequent reactions involving polymerization of the vinyl amine and protonation of this vinyl amine polymer and of free triethylamine occur. No secondary reactions between thallium(I) chloride and the polymer, free triethylamine, or triethylammonium chloride occur, but thallium(I) chloride does react with excess thallium(III) chloride to form thallium(I) tetrachlorothallate( III). The oxidation-reduction reaction is rapid and irreversible with no prolonged secondary changes occuring in the reaction mixture upon standing. The secondary reaction of thallium(I) chloride and thallium(III) chloride makes the apparent reaction stoichiometry as determined by potentiometry and conductivity unusual, and not the expected one to one mole ratio of triethylamine to thallium(III) chloride. The reaction of triethylamine and thallium(III) chloride differs from that of triethylamine and free halogens, i.e., chlorine and bromine, in three aspects. First, the halogen reaction appears to occur in two stages. The initial stage is a fast reaction producing large amounts of solid products and a light yellow liquid layer, After separation of the solids, a slower reaction continues in the liquid, with the yellow liquid darkening to brown or black, and with the precipitation of more solid products. This slow reaction continues for days. Secondly, the initial reaction is much more vigorous than that of thallium(III) chloride with triethylamine, Finally, the stoichiometry of the halogen-triethylamine reaction is quite timedependent and variable whereas thalliurn(III) chloride reacts in a single stage at a definite and reproducible mole ratio. It is uncertain from this work whether the interaction between thallium(III) trifluoroacetate and triethylamine in acetonitrile involves any oxidation-reduction.
Resource Type
Date Available
Date Copyright
Date Issued
Degree Level
Degree Name
Degree Field
Degree Grantor
Commencement Year
Advisor
Academic Affiliation
Non-Academic Affiliation
Subject
Rights Statement
Peer Reviewed
Language
Digitization Specifications
  • File scanned at 300 ppi (Monochrome) using Capture Perfect 3.0.82 on a Canon DR-9080C in PDF format. CVista PdfCompressor 4.0 was used for pdf compression and textual OCR.
Replaces
Additional Information
  • description.provenance : Made available in DSpace on 2014-02-19T19:06:24Z (GMT). No. of bitstreams: 1 ArnesonRobertL1974.pdf: 1030402 bytes, checksum: 5270a6196f1dcacff4953401e2067091 (MD5) Previous issue date: 1973-10-20
  • description.provenance : Approved for entry into archive by Katy Davis(kdscannerosu@gmail.com) on 2014-02-19T19:03:55Z (GMT) No. of bitstreams: 1 ArnesonRobertL1974.pdf: 1030402 bytes, checksum: 5270a6196f1dcacff4953401e2067091 (MD5)
  • description.provenance : Submitted by Katy Davis (kdscannerosu@gmail.com) on 2014-02-19T19:03:07Z No. of bitstreams: 1 ArnesonRobertL1974.pdf: 1030402 bytes, checksum: 5270a6196f1dcacff4953401e2067091 (MD5)
  • description.provenance : Approved for entry into archive by Katy Davis(kdscannerosu@gmail.com) on 2014-02-19T19:06:24Z (GMT) No. of bitstreams: 1 ArnesonRobertL1974.pdf: 1030402 bytes, checksum: 5270a6196f1dcacff4953401e2067091 (MD5)

Relationships

Parents:

This work has no parents.

Last modified

Downloadable Content

Download PDF

Items