Doctoral Dissertations

Abstract

"The anodic oxidation of 1-pentyne was studied at 70°C on Pt and Au electrodes in solutions of H₂SO₄, K₂SO₄, K₂CO₃, and KOH. Pt was studied in a pH range of 0.35 - 12.7 and Au in a range of 10.9 - 12.7. Reaction rates were measured as a function of potential, pH, temperature, and 1-pentyne partial pressure. The coulombic efficiencies for the oxidation to CO₂ were 77 percent in 1 N H₂SO₄ and 69 percent in 1 N KOH on Pt and 43 percent in 1 N KOH on Au. The kinetic parameters on Pt were [partial derivative]V/[partial derivative]log i [is approximately equal to] 70 mv; [partial derivative]log i/[partial derivative]pH = 1; [partial derivative]i/[partial derivative]P < ß; [partial derivative]E[subscript a]/[partial derivative]V [is approximately equal to] -23 Kcal/volt The parameters on Au were -[partial derivative]V/[partial derivative]log i [is approximately equal to] 70 mv; [partial derivative]log i/[partial derivative]pH = 2; [partial derivative]i/[partial derivative]P < 0; [partial derivative]E[subscript a]/[partial derivative]V [is approximately equal to] -23 Kcal/volt Reaction sequences that are consistent with the parameters are R(sol) = R(ads) (1); OH⁻ (sol) = OH(ads) + e (2); H₂O (sol) = OH (ads) + H⁺ + e (3); R(ads) + OH (ads) + ROH (ads) (4); ROH (ads) + OH⁻ (sol) [arrow]···[arrow] products (5) Reaction (4) is the r.d.s. on Pt and reaction (5) is the r.d.s . on Au. The rate equation on Pt is i = nFk₄ (K ₃a[subscript H₂O/a[subscript H⁺] + K₂a[subscript OH⁻])[theta subscript p] [superscript (1-theta[subscript p])exp(FV/RT) and on Au is i = nFk₅K₄θ[subscript p] (1-theta[subscript p] a²[subscript OH⁻ exp(FV/RT)"--Abstract, pages ii-iii.

Advisor(s)

James, William Joseph

Committee Member(s)

Hanna, Samir B.
Stoffer, James O.
Johnson, James W., 1930-2002
McDonald, H. O. (Hector O.)

Department(s)

Chemistry

Degree Name

Ph. D. in Chemistry

Sponsor(s)

National Defense and Education Act Title IV Fellowship
University of Missouri--Rolla. Materials Research Center
University of Missouri--Rolla. Department of Chemistry

Publisher

University of Missouri--Rolla

Publication Date

1970

Pagination

xi, 90 pages

Note about bibliography

Includes bibliographical references (pages 88-89).

Rights

© 1970 Michael Jensen Danielson, All rights reserved.

Document Type

Dissertation - Open Access

File Type

text

Language

English

Subject Headings

ElectrochemistryFuel cells -- MaterialsOrganic compounds -- Oxidation -- Evaluation

Thesis Number

T 2376

Print OCLC #

6020196

Electronic OCLC #

855059584

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