Molecular ordering and phase transitions in alkanol monolayers at the water–hexane interface

Abstract

The interface between bulk water and bulk hexane solutions of n-alkanols (H(CH(2))(m)OH, where m=20, 22, 24, or 30) is studied with x-ray reflectivity, x-ray off-specular diffuse scattering, and interfacial tension measurements. The alkanols adsorb to the interface to form a monolayer. The highest density, lowest temperature monolayers contain alkanol molecules with progressive disordering of the chain from the -CH(2)OH to the -CH(3) group. In the terminal half of the chain that includes the -CH(3) group the chain density is similar to that observed in bulk liquid alkanes just above their freezing temperature. The density in the alkanol headgroup region is 10% greater than either bulk water or the ordered headgroup region found in alkanol monolayers at the water-vapor interface. We conjecture that this higher density is a result of water penetration into the headgroup region of the disordered monolayer. A ratio of 1:3 water to alkanol molecules is consistent with our data. We also place an upper limit of one hexane to five or six alkanol molecules mixed into the alkyl chain region of the monolayer. In contrast, H(CH(2))(30)OH at the water-vapor interface forms a close-packed, ordered phase of nearly rigid rods. Interfacial tension measurements as a function of temperature reveal a phase transition at the water-hexane interface with a significant change in interfacial excess entropy. This transition is between a low temperature interface that is nearly fully covered with alkanols to a higher temperature interface with a much lower density of alkanols. The transition for the shorter alkanols appears to be first order whereas the transition for the longer alkanols appears to be weakly first order or second order. The x-ray data are consistent with the presence of monolayer domains at the interface and determine the domain coverage (fraction of interface covered by alkanol domains) as a function of temperature. This temperature dependence is consistent with a theoretical model for a second order phase transition that accounts for the domain stabilization as a balance between line tension and long range dipole forces. Several aspects of our measurements indicate that the presence of domains represents the appearance of a spatially inhomogeneous phase rather than the coexistence of two homogeneous phases.

Tail Ordering Due to Headgroup Hydrogen Bonding Interactions in Surfactant Monolayers at the Water−Oil Interface

“…7 In contrast, the flexible hydrocarbon n-alkanol tails are disordered and may allow hexane to penetrate the tail region. 5,6 These comparative measurements reported recently highlight the importance of conformational entropy (arising from tail flexibility) and enthalpic contributions (that contribute to the surfactant solubility) in determining the molecular ordering of the surfactant assembly. The surfactant ordering in the example above is dominated by the tails of the surfactants.…”

“…These other data sets for triacontanol have been previously published. 5,6 Additional data for triacontanoic acid, including the temperature and pH dependence, will be presented in future publications. Figure 1 illustrates X-ray reflectivity measured from triacontanoic acid and triacontanol monolayers at the water-hexane interface.…”

“…6,12 The interface between each of these layers and an adjacent layer (or bulk) is roughened by capillary waves such that a single roughness parameter describes all the interfaces. The other fitting parameters include the electron density and thickness of each layer.…”

“…5,6 Two of these layers represent the electron density along the alkyl tail; the third layer represents the region of the -CH 2 OH headgroups. The maximum electron density in the headgroup region, F max ) 1.13(0.01, is comparable for the triacontanol and triacontanoic acid monolayers.…”

“…[5][6][7] On the water surface, these surfactants form ordered monolayers with rigid-rod all-trans tails for both fluorocarbon and hydrocarbon tail surfactants. [5][6][7] Although individual fluorocarbon n-alkanols are rigid by nature, the hydrocarbon n-alkanols have flexible tails. The formation of rigid-rod monolayers for the surfactants with flexible tails indicates that attractive forces between the tails can overcome any disordering tendency resulting from the flexibility of the alkyl tail.…”