Chemistry at interfaces

As a prelude to the discussion of reactions at micellar interfaces and in the interstices of micelles we should examine what is special about the nature of reactions at liquid-liquid interfaces. Adsorption of substances at interfaces can lead to an ordering of molecules that is not encountered in bulk solution. The topic has been reviewed by Menger [3,4] who has illustrated the possibilities of reactions at interfaces by investigation of the reaction of the water-insoluble ester p-nitrophenyl laurate in heptane with imidazole in an adjacent aqueous phase. Because of the insolubility of the ester in water any reaction between the species must occur at the interface. Migration of the reactants to the interface was partially rate-determining small amounts of laurate ion which adsorb at the interface retarded the interfacial hydrolysis of the ester. The adsorbed laurate ion probably impedes the transport of one or more of the reactants to the interface, suggesting a means of control of reactions not available in normal bulk reactions. 

Where water-insoluble agents have to be reacted with water-soluble reagents, addition of an emulsifier can assist the reaction by increasing the surface area available for reaction [5]. Brij 35 (0.006 m) reduces the reaction time for the hydrolysis of a,a,a-trichlorotoluene to benzoic acid in 20 % NaOH from 60 h to 11 h at 80° C. Polymerization at interfaces is discussed later in the chapter. 

Adsorption of solutes on to micellar surfaces will also affect their reactivity p-nitrophenyl esters bound to the surface of anionic micelles of NaLS do not contribute to the overall reaction rate, probably due to the repulsion of OH ions in contrast ester adsorbed on to cationic micelles is more rapidly broken down as both the ester and the OH ion will accumulate at the micellar surface [6]. 

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Some of the most interesting and important chemical and physical interactions occur when dissimilar materials meet, i.e. at an interface. The understanding of the physics and chemistry at interfaces is one of the most challenging and important endeavors in modem science. 

Jaycock MJ, Parfitt GD (1981) Chemistry at Interfaces, Ellis Horwood, Chichester... 

F MacRitchie. Chemistry at Interfaces. San Diego, CA Academic Press, 1990. 

Molau, G. E., Gordon Research Conference on Chemistry at Interfaces,... 

F. MacRitchie, Chemistry at Interfaces. Academic Press (1990). (Emphasis on the real Interfacial chemistry, i.e. reactions, particularly in monolayers. In passing a variety of monolayer techniques and properties are reviewed. )... 

L.A.Belyakova, A.V.Simurov and V.A.Tertykh, Ukr. Khim. Zhurn., 60 (1994) 201. L.A.Belyakova and A.M.Varvarin, Abstracts of XIII European Chemistry at Interfaces Conference, Kiev, 1994, p.l23. 

V. 1. Bogillo and V. P. Shkilev, Abstr. XIII Europ. Conf. on Chemistry at Interfaces, Kiev, Ukraine, 1994. 

Better computational tools acquiring relevant high-quality datasets enhanced analytical capabilities better models, theory, instrumentation better analytical-theoretical tools to understand chemistry at interfaces... 

Langmuir covers the broad area of surface and colloid chemistry. Topics include micelles, emulsions, surfactants, vesicles, wetting and interfacial films, chemisorption and catalysis, electrochemistry, and physical adsorption on liquid and solid surfaces. Original research articles and letters arc accepted. There are occasional invited review tvpe articles. The journal is intended to provide a comprehensive coverage of the field of chemistry at interfaces. 

Self-assembled monolayers (SAMs) [22-25] are perhaps the most popular model systems for studying chemistry at interfaces under controlled conditions. In the last decade, countless studies have been performed that in-... 

Figure 9.1 Schematic diagram of the free energy of 1 mol of water as a function of temperature at 1 atm pressure. (MacRitchie, F. 1990. Chemistry at interfaces. San Diego, CA Academic Press.)...

Following a career as a research scientist with the Wheat Research Unit (later the Grain Quality Research Laboratory) of the Commonwealth Scientific and Industrial Research Organization (CSIRO) of Australia, Finlay MacRitchie was a professor in the Department of Grain Science and Industry at Kansas State University (1997-2009). He is currently professor emeritus in this department. MacRitchie has worked in two main fields fundamental surface and colloid chemistry and cereal chemistry He has published more than 150 papers in refereed journals and a textbook, Chemistry at Interfaces (Academic Press, 1990). He is listed as an Institute for Scientific Information (ISI) highly cited researcher. 

Bonifazi D, Mohnani S, Llanes-Pallas A (2009) Supramolecular chemistry at interfaces molecular recognition on nanopattemed porous surfaces. Chem Eur J 15 7004—7025... 

Ross PN (1986) Stmcture-property relations in noble metal electrocatalysis. In The Gordon conference on chemistry at interfaces, Lawrence Berkeley Laboratory, Berkeley/Meriden, July 21-25, 1986. p. LBL-21733... 

Yaminski W, Claesson PM, Eriksson JC (1993) J Colloid Interface Sci 161 91 McRitchie F (1990) Chemistry at interfaces. Academic, San Diego p 283 Evans S, Pritchard RG, Thomas JM (1978) J Electron Spectrosc Relat Phe-nom 14 341... 

MacRitchie, F. Chemistry at interfaces-. Academic Press San Diego, 1990. 

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