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Interaction of oils with surfactants

MacNab, Jamie Robert


Jamie Robert MacNab


Paul D. I. Fletcher

Robert Aveyard


This thesis is concerned with the interactions of oils with surfactants. The understanding of these interactions is important for a number of practical applications which include perfume delivery in fabric softeners. Both non-ionic surfactants, of the general formula H( CH2)n( OCH2CH2)m-OH, and lome surfactants, of the general formula CnH2n+lW(CH3)3Br were used in the study. Oils of varying polarity were investigated from non-polar alkane oils to moderately polar perfume oils.Initially, the work of adhesions of the perfume oils with water were studied to establish where these oils 'fitted-in' to a range of oils of varying polarity. It was found that the three perfume oils studied (linalool, cineole and eugenol) all exhibited adhesion properties which were fairly typical of moderately polar oils. In order to obtain the enthalpies and entropies of adhesion of the perfume oils with water the surface tensions and interfacial tensions with water were measured as a function of temperature. The enthalpy of adhesion for linalool with water is consistent with values obtained for the enthalpy of hydration of the hydroxyl group.The co-surfactant nature of the perfume oils was investigated by tension measurements of their adsorption to the heptane-water interface. Linalool and eugenol show reasonably high surface activity at this interface and could therefore be expected to act as cosurfactants in systems that contain conventional surfactants.The phase behaviour of the CgE5 + water + octane micro emulsion system was investigated to determine the effect of adding different concentrations of perfume oil on the size, shape and position of the three phase region. It was found that linalool reduces the size of this three phase region and also reduces the temperature at which the three phase region occurs. Although not conclusive, this behaviour suggests the system is approaching a triclitical point.It is of interest also to understand the adsorption of oils at planar surfactant mono layers and then attempt to relate the adsorption data to bulk phase solubilisation of the oils in micelles. The adsorption at a planar interface was attained by measuring the surface pressure of the oil at different activities. The surface concentration of the oils was then calculated from the Gibbs adsorption equation. By measuring these surface pressures as a function of activities at various temperatures, it was possible to derive the adsorption enthalpies and entropies with use of a form of the Van't Hoff equation. It was found that alkane adsorption increases with decreasing alkane chain length and the isotherms show a greater curvature upwards for the shorter chain length alkanes suggesting that the adsorption becomes more favourable as more alkane is added to the mixed alkane/surfactant film.Headspace analysis was employed to measure the solubilisation of oils in bulk surfactant solutions. The results obtained with this technique were preliminary although early indications suggest that more alkane oil is solubilised in bulk aggregates with curved monolayers than is adsorbed at planar monolayer interfaces. However, solubilisation of oil in bulk solutions may either be in the curved monolayer or they could form a 'core' of oil inside the aggregate.


MacNab, J. R. (1996). Interaction of oils with surfactants. (Thesis). University of Hull. Retrieved from

Thesis Type Thesis
Deposit Date Sep 27, 2011
Publicly Available Date Feb 22, 2023
Keywords Solid state physics; Lubrication and lubricants
Public URL
Additional Information Department of Chemistry, The University of Hull
Award Date Nov 1, 1996


Thesis (10.2 Mb)

Copyright Statement
© 1996 MacNab, Jamie Robert. All rights reserved. No part of this publication may be reproduced without the written permission of the copyright holder.

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