The kinetics and mechanism of the place exchange reaction(PER) of alkylthiols with alkylthiol-protected gold nanoparticles(AuNP) are investigated. Using chemically similar alkylthiols it was possible to study the reaction in the absence of perturbing factors, enabling detailed mechanistic and kinetic studies to be explored. It is found that the reactions are zero order in incoming ligand and overall follow a second order diffusion limited Langmuir rate law. In the case where there is little chemical distinction between the incoming and capping ligands, the reactions proceed to an endpoint consistent with a Keq=1. The rate of the reaction is dependent on the chain length of the capping ligand and the AuNP core size. The related dialkyldisulphide for-alkylthiol AuNP exchange reaction is consistent with the same rate law and also proceeds to a well-defined endpoint. However, the rate constant is 20-fold less than the alkylthiol case. These results lead to a convergent model of PERs where the rate limiting process involves both incoming and outgoing ligands, with diffusion of the incoming ligand to the AuNP surface as the major controlling factor of the reaction rate.

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Thesis (Ph. D.)--University of Missouri-Columbia, 2007. / The entire dissertation/thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file (which also appears in the research.pdf); a non-technical general description, or public abstract, appears in the public.pdf file. Title from title screen of research.pdf file (viewed on March 11, 2008) Includes bibliographical references.

Thesis (M.S.)--Texas State University-San Marcos, 2007. / Vita. Includes bibliographical references (leaves 80-85).

Thesis(M.S.)--Auburn University, 2005. / Abstract. Vita. Includes bibliographic references.

Thesis (M.Sc.) - Carleton University, 2002. / Includes bibliographical references (p. 92-95). Also available in electronic format on the Internet.

Thesis (Ph. D. in Chemical Engineering)--Vanderbilt University, May 2006. / Title from title screen. Includes bibliographical references.

Thesis (Ph. D.)--University of Oregon, 2008. / Typescript. Includes vita and abstract. Includes bibliographical references (leaves 164-192). Also available online in Scholars' Bank; and in ProQuest, free to University of Oregon users.

Thesis (M.Eng.). / Written for the Dept. of Chemical Engineering. Title from title page of PDF (viewed 2009/06/15). Includes bibliographical references.

Thesis (Ph. D.)--Worcester Polytechnic Institute. / Keywords: nanotechnology; thin films; nanotubes; Molecular Self Assembly. Includes bibliographical references (p. 277-280).