Born-haber cycle for monolayer self-assembly at the liquid-solid interface: Assessing the enthalpic driving force

Wentao Song, Natalia Martsinovich, Wolfgang M. Heckl, Markus Lackinger

Publikation: Beitrag in FachzeitschriftArtikelBegutachtung

73 Zitate (Scopus)

Abstract

The driving force for self-assembly is the associated gain in free energy with decisive contributions from both enthalpy and entropy differences between final and initial state. For monolayer self-assembly at the liquid-solid interface, solute molecules are initially dissolved in the liquid phase and then become incorporated into an adsorbed monolayer. In this work, we present an adapted Born-Haber cycle for obtaining precise enthalpy values for self-assembly at the liquid-solid interface, a key ingredient for a profound thermodynamic understanding of this process. By choosing terephthalic acid as a model system, it is demonstrated that all required enthalpy differences between well-defined reference states can be independently and consistently assessed by both experimental and theoretical methods, giving in the end a reliable value of the overall enthalpy gain for self-assembly of interfacial monolayers. A quantitative comparison of enthalpy gain and entropy cost reveals essential contributions from solvation and dewetting, which lower the entropic cost and render monolayer self-assembly a thermodynamically favored process.

OriginalspracheEnglisch
Seiten (von - bis)14854-14862
Seitenumfang9
FachzeitschriftJournal of the American Chemical Society
Jahrgang135
Ausgabenummer39
DOIs
PublikationsstatusVeröffentlicht - 2 Okt. 2013

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