Adsorption of alkyl amides: monolayer structures and mixing behaviour
University of Cambridge
Department of Chemistry
Doctor of Philosophy (PhD)
MetadataShow full item record
Bhinde, T. (2011). Adsorption of alkyl amides: monolayer structures and mixing behaviour (Doctoral thesis). https://doi.org/10.17863/CAM.16279
In this work monolayers of alkyl amides adsorbed on a graphite surface have been successfully identified and investigated using a combination of synchrotron X-ray and neutron diffraction and Differential Scanning Calorimetry (DSC). Exceptionally stable solid layers have been observed at temperatures well above the bulk melting point, at both high multilayer coverages and, very unusually, at sub-monolayer coverages. The molecular structure of the two-dimensional crystals of these alkyl amides has been obtained from diffraction and interpreted in terms of the subtle intermolecular interactions, particularly the contribution of hydrogen bonding in monolayer assembly. Thermodynamic information provides insight on the mixing behaviour in adsorbed amide layers. A systematic study on the variation in monolayer crystal structures with alkyl chain length (between five and sixteen carbon atoms) of saturated alkyl amides using diffraction identifies that all the amide molecules investigated lie flat on the graphite surface. An odd-even variation is observed in the monolayer crystal structures and this is supported by the melting enthalpies of the amides determined by DSC. The structure of the even members is found to support the qualitative monolayer arrangement proposed by an STM report of one member of the series, but with more quantitative insight here. Significantly, a new monolayer symmetry group for odd members of the homologous series has been identified. Characteristics of the hydrogen bond geometry between the molecules in the solid monolayers are reported exploiting the high level of detail available from the diffraction techniques. Secondly, the formation of solid monolayers of unsaturated alkyl amides has been reported and their crystal structures determined. This is believed to be the first report of these monolayer structures. The position and nature of the double bond have an important effect in the stability of the monolayer. Unusually, certain unsaturated amides that have a double bond conjugated with the amide group are found to form considerably more stable layers than their saturated homologues. The abnormally high melting points and enhanced stability of amide monolayers have been attributed to the existence of a network of hydrogen bonds in the layer. Phase diagrams obtained by DSC for binary mixtures of alkyl amides on graphite have been quantitatively analysed using a combination of thermodynamic models (ideal, eutectic and the regular solution models). The determined mixing behaviour is supported by conclusions based on the monolayer crystal structures of the individual components calculated using diffraction. Saturated amide mixtures that have the same plane group symmetry are found to mix non-ideally in the solid layer and phase separate if the symmetry is different, whereas the mixing behaviour of saturated/unsaturated amides considered here was found to depend on the nature of the double bond (cis/trans). Results from an initial investigation into the adsorption of alkyl amides at the polymer/air interface are also presented. This complements the study above and provides an alternative situation where amide monolayers have a central role. A reduction in the coefficient of friction is seen with increasing bulk concentration of the amide and with increasing time indicating migration of the amide to the surface. A powerful combination of surface reflection techniques including neutron and X-ray reflection and ellipsometry have been used to gain uniquely quantitative insight into this system. Initial estimates of the concentration of amides at the polystyrene surface are presented for the first time.
Adsorption, Amides, Diffraction, Thermodynamics
The author wishes to thank the Cambridge Commonwealth Trust and Diamond Light Source for funding support.
This record's DOI: https://doi.org/10.17863/CAM.16279