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The behaviour of liquid alkanes near interfaces





Atomistic Simulation Group and Irish Centre for Colloid Science , School of Mathematics
and Physics, The Queen's University , Belfast, BT7 1NN, UK

CCLRC, Daresbury Laboratory , Daresbury, Warrington, WA4 4AD, UK
Published online: 01 Sep 2009.

To cite this article: P. SMITH , R. M. LYNDEN-BELL & W. SMITH (2000) The behaviour of liquid alkanes near interfaces,
Molecular Physics: An International Journal at the Interface Between Chemistry and Physics, 98:4, 255-260, DOI:
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n-heptane and n-dodecane as well as alcohols. The introduction of the surface force apparatus [l] and later the atomic force microscope [2] has allowed the properties of liquids near solids to be probed on a molecular length scale while atomistic simulations can be used to relate these properties to the structure of the liquid near the interface [3.tandf. The CC bond lengths are fixed but bond angles are allowed to vary and a torsional potential allows for conformational changes. Potentials and simulations The alkanes were modelled by a united atom model in which each methylene and methyl group is represented by a Lennard-Jones centre. Films of butane. 2. The parameters used for the alkanes are the same as we used in our earlier work on liquid alkanes [6] and come from the work by Jorgensen et al. revised version accepted 26 October 1999) Simulations of thick films of liquid alkanes supported on a wax-like substrate were carried out at a number of temperatures in order to investigate the structure and dynamics of molecules near the solid-liquid and the liquid-vapour interfaces. The alkanes are a series of similar molecules which differ only in their length and which have weak and non-specific intermolecular forces.lynden-bell@qub. there was no evidence of a frozen layer at this interface even near the bulk freezing temperature. Simulations have also provided some examples of preferential adsorption near the solid surface in liquid mixtures. changes in structure and composition are reflected in the surface tension. Although the liquidvapour interface is technologically less important.98. 61. SMITH. The simplest liquids are composed of nearly spherical molecules such as OCTMS and cyclohexane and their properties can be modelled by spherical Lennard-Jones particles. M. UK 41. The results described in this paper suggest that the solid monolayer is probably the result of the strength of the substrate-liquid interaction and give some interesting insights into the behaviour of mixtures of alkanes near the solid-liquid and liquid-vapour interfaces. octane and a mixture were investigated. In order to provide a non-specific solid substrate we constructed a potential with the same average properties as the liquid. However. particularly rheology and lubrication. ac. The Queen's University.' R. Among the questions which come to mind are whether this is a universal phenomenon or merely the result of specific substrate-liquid interaction. 4. School of Mathematics and Physics. 2000. The mixed liquid showed considerable segregation at both interfaces with preferential absorption of butane at the liquid-vapour interface and octane at the liquid-solid interface. 1. 81 which have shown the existence of a persistent solid monolayer on a graphite surface under a liquid film at temperatures up to about 20" above the bulk melting point for a number of liquids including methane. UK Downloaded by [Texas A&M University Libraries] at 14:51 08 August 2014 (Received 7 September 1999. 255-260 The behaviour of liquid alkanes near interfaces P. Belfast BT7 INN. The next step in complexity is provided by the homologous series of normal alkanes. Daresbury Laboratory. Warrington WA4 4AD. We were also interested in the liquid-vapour interface [6] and in simple liquid mixtures. The results of both simulations and experiments have demonstrated the presence of layering of liquid density and a reduction of mobility near a solid surface. Near the solid surface the liquids were found to be structured and molecular diffusion slowed. No. e-mail: r. [9] with the bond angle potential given by Weber [lo]. SMITH2 'Atomistic Simulation Group and Irish Centre for Colloid Science. * Author for correspondence. VOL. The potential was constructed by averaging the potential of a semi-infinite slab of LennardJones atoms at a uniform density and is given by Moleculur Physics ISSN 002C8976 print/ISSN 1362-3028 online 0 2000 Taylor & Francis Ltd http://www.MOLECULAR Our interest in this topic was rekindled by recent experiments using neutrons [7. Introduction The behaviour of liquids near solid surfaces is important for a range of phenomena. The liquid-vapour interface of long chain alkanes shows a first order surface ordering phase transition just above the bulk melting transition [5.html . LYNDEN-BELL'* and W. which are particularly important as they are used as lubricants.

0 30. The simulation of the mixed system was performed at 223 K.0 50. Figure 2 is a snapshot showing the first layer above the substrate.0 60. The liquid-vapour surface is almost pure butane. The systems were then equilibrated at 300K for 400ps. 198K and 223K. Note two peaks between the first and second layers which arise from bridging butane molecules. The density profile of the mixture of butane and octane is shown in figure 1.0 8. This potential has no cut-off and acts on all the atoms. 3. The situation near the solid surface is somewhat more complex. We simulated octane and butane separately and mixed together. A more detailed study of the properties of the molecules in the layered region near the solid substrate showed that for both substances individual molecules tended to lie parallel to the surface and the percentage of gauche defects was less than in the bulk. p is the atomic density of the substrate and u and E are the Lennard Jones parameters for the atom in question. We used the molecular simulation program DLPOLY [ l l ] with an added hexagonal prism boundary condition. For all our simulations we used a Berendsen thermostat with a time constant of 0. Thus the two interfaces in the system were far enough apart that any interaction between them was negligible. where z is the distance from the substrate.Downloaded by [Texas A&M University Libraries] at 14:51 08 August 2014 256 P. Results The structure of the films of neat liquids near the substrate showed density oscillations extending to about 4 or 5 layers (20-25 above the substrate.5 Figure 1. These temperatures were chosen to give some runs near the freezing point and some at higher temperatures for comparison.0 10.8 m E \ 0) Y 0. Initially the molecules were in the all trans state with their heads distributed on a face-centred cubic (fcc) lattice. The solid substrate causes layering in the liquid out to 25A.0 Distance from substrate in 8. then cooled and further equilibrated for 400ps at each temperature before collecting data over 200 ps. The inset shows the density near the substrate in greater detail.0 . The melting points of octane and butane are 216K and 135K respectively. The solid substrate is on the left and the vapour on the right. which shows interesting features at both the solid-liquid and the liquid-vapour interfaces. with an excess of octane in the region below. The strength of the potential is merely a function of the z position and the density. 6. The resulting films were 55-70A thick.1 ps and a simulation time step of 2fs. Simulations were run for octane at 198 K. Above this region there was a region of bulk liquid about 30-40 wide with uniform density below the liquid-gas interface region. and the sigma and epsilon values used were the same as for methylene and methyl groups. while the boiling points are 399K and 273 K [12].0 40 40. The most major feature to notice is A) A 0. Smith et al. 223 K and 293 K and for butane at 143K.0 20. p was chosen to be equal to the average liquid density in each run. 2. The separate systems contained 240 octane molecules and 480 butane molecules respectively while the mixed system contained 112 octane and 224 butane molecules giving the same number of carbon atoms in each type of molecule.0 10. The partial densities of butane (-) and octane (---) in a mixed film at 223K averaged over 200 ps.

0 . For the mixture two independent runs were performed yielding four sets of data which were used to calculate the uncertainty. A. We can see in every case A. that there is more butane than octane in this layer and that this cannot be due to packing frustrations between regions of ordered octane molecules since there are regions where octane molecules could replace butanes.-0 u) / /# =I E U i (I) C m - Q 5 0. and some of the butane molecules are normal to the view and contain less than four atoms in this slice.- K . the second ordered Second layer I------’-”-’------d 0. A. and in the surface region of the mixture. The boundaries used to define these regions wert: bottom layer ct6 second layer 6-10 bulk 25-35 A and surface 45-55 The mean square displacement was calculated separately in both x and y directions and the two sets of data used to estimate the uncertainty in our results. It also shows some gauche defects in both butane and octane molecules and molecules bridging between the first and second layer which can also be seen by the sharp peaks between the first and second layer in the inset of figure 1 . in the second layer. Note that there are more butane than octane molecules in this layer. 1. The mobility of molecules in the layer nearest the solid substrate provides a good measure of the nature (solid or liquid) of this layer. A slice through a configuration of the system showing tke molecules in the first layer nearest the substrate ( M A ) . We have to seek other explanations for this. for a region with a similar number of molecules in the central part of the film for both neat liquids and for the mixture.5 - Bulk like region i i /# i // f-----------’-’---------~ Figure 3. The lowest layer contains about 25% by mass more butane than 257 octane. These are the molecules that bridge between the first and second layers. Figure 2 gives an idea of the size of the cross-section of the simulation cell in relation to the size of the molecules.0 I I I I I 24 1. Thus overall octane is preferentially adsorbed at the solid-liquid interface while butane is preferentially adsorbed at the liquid-vapour interface. Figures 3 and 4 show the in-plane diffusion constants for different regions of the films of butane and of octane at a number of temperatures. In-plane diffusion coefficients in butane films as a function of ternperature for the first order layer.Downloaded by [Texas A&M University Libraries] at 14:51 08 August 2014 The behaviour of liquid alkanes near interfaces Figure 2. but the next two layers are strongly dominated by octane molecules. We measured the in-plane diffusion constant from the slope of the mean square displacement parallel to the surface as a function of time for molecules: in the first layer.5 Butane 4C 1.0 T - i .

Smith et al.-K K ul .5 ..v) 3 E U al C m Q Downloaded by [Texas A&M University Libraries] at 14:51 08 August 2014 = 0.0 270. In these .0 ‘ z . .0 250. - I 0.- C 0 .258 P. the second ordered layer and a bulk-like region. even near the bulk freezing point. The diffusion coefficient for a mixture of octane (. that the diffusion in the two layers nearest the solid substrate is substantially less than in the bulk and that the diffusion rates decrease with temperature. the second layer (B).5 Figure 4. Octane B -4 1. In-plane diffusion coefficient in octane films as a function of temperature for the first order layer.0 - 4 “4 . In runs 1 D ~ C B Layer in System at the same temperature (223K) butane diffuses more rapidly than octane as one would expect. However. 1 - 2- Octane al C m Q -C Figure 5.0 C .0 21 0. ul Q 290.0 Temperature in degrees Kelvin 1 21 4 Mixture 223K 1.0 I I 1 230. Diffusion coefficients for films of mixed alkanes at 223 K are shown in figure 5. I 190.-0 ul 3 E U x-------_-_{ -. We deduce that the lowest layer is behaving as a liquid rather than being frozen. In the second layer and in the bulk the diffusion constants of both types of molecules are similar although in pure liquids they differ by a factor of two (bulk) or more (second layer). The lines are drawn as a guide to the eye.-) and butane (-) in the first layer (A). the diffusion constant in the layer next to the solid does not vanish even at the lowest temperatures. the bulk ( C ) and the surface region (D).

Discussion Layering near the liquid-solid interface is a universal feature of liquids.5 ns so that there should be time for equilibration. As these considerations do not apply to alkanes. suggesting that the viscosity is less than in pure octane. we must look elsewhere for the explanation of our observations. so the probability of gauche defects is reduced compared to bulk liquid and the energy is lowered. The only demonstration of an ordered unmelted monolayer of alkanes at a solid-liquid interface in a simulation that we are aware of is in the simulations of Winkler et al. Segregation of molecules near interfaces is the result of the change in balance between energy and entropy for different types of molecules. The increase in free energy on the introduction of a gauche defect is larger in two dimensions than three as the energetic terms increase and the entropic stabilization decreases. The cause of layering is the packing of the molecules against the surface. This stabilization is greater for longer molecules as there are more possible sites for . which has been demonstrated experimentally [2. This is shown by the existence of layering in simulations of hard particles against hard walls [14]. [15] compared the layering in hexadecane on a corrugated model of graphite with a purely repulsive flat surface and Gupta et al. we always find a measurable diffusion constant. 191 as well as in our own. found that the only effect of using a flat substrate is the loss of correlations in the plane structure in the first layer above the substrate between molecules in the layer and the substrate. The first question we wish to address is how far the increased melting point of the lowest layer observed by Castro et al. reaching the bulk ratio by 20A. When they replaced the graphite by a purely repulsive surface this monolayer melted. The phenomenon is observed both in long chain fluids and in fluids of spherical molecules. Part of this is an entropic effect due to the increase of free volume of individual molecules when the density is layered compared to that in a uniform density. The mobility of butane in the surface (where it is favoured) is substantially higher than in both the bulk mixture and in pure butane. We believe that the segregation that we observe is due to the relative stabilization of octane versus butane when the solvent becomes layered. but in the first layer the proportion of octane molecules is lower. Considering first the solid-liquid interface. [I51 of hexadecane on graphite. for a wide range of liquids on graphite are the result of the stronger attraction of molecules by the substrate than by the bulk liquid. [I61 studied both the structure and dynamics of liquid octane on a series of corrugated Lennard-Jones surfaces with varying degrees of attraction for the liquid. which is less attractive than either graphite or metals. we note that in Xia and Landman’s [20] simulations the preferential adsorption of the long molecules was strongest in the bottom layer and decreased as theobulk was approached. even at the lowest temperatures. A similar difference between the first and higher layers was seen by Kotelylanskii and Hentschke [I91 in their study of benzene-heptane. 131 and in many simulations. On the other hand a decrease in mobility near the surface has been observed in many simulations [18. These studies show that the magnitude of attraction and to some degree the extent of corrugation of the surface have a large effect on the amplitude of the density oscillations near the surface and the mobility of molecules in various layers. Within the layers the molecules are confined to two dimensions rather than three. [17]. However. We believe that the persistence of mobility in the lowest layers. showing a high proportion of the longer octane molecules. 4.The behaviour of liquid alkanes near interfaces Downloaded by [Texas A&M University Libraries] at 14:51 08 August 2014 regions large molecules diffuse faster. is good evidence that the large increases in melting temperature (about 10%) seen by Castro et al. 223 K in place of 31 5 K) are similar. However we are using comparatively small molecules and simulating for times longer than 0. who performed Monte Carlo simulations of n-hexadecane films ranging from l 4 n m on a featureless flat metal (Au) surface over a range of temperatures from 350K to 650K. it has been observed in previous simulations. [7] is also a universal phenomenon or whether it depends on the strength and degree of corrugation of the substrateliquid potential. There are two difficulties: first we do not know the melting points of our model alkanes (as opposed to the experimental melting points). Our sub- 259 strate has the same average attractive properties as wax. In our simulations we have endeavoured to cover the temperature range down to that of the bulk melting point in order to investigate variations in mobility. Winkler et al. However in that case the explanation is probably that the interaction between benzene molecules does not favour a planar arrangement so that the energy in the first layer can be reduced by adsorbing heptane molecules in preference to benzene molecules. and secondly the time scale of our simulations are limited. Balasubramanian et al. In the second and third layers our results (which are at a much lower temperature. Although the liquid mobility near the substrate is greatly reduced at low temperatures. However the importance of energetic effects is demonstrated by simulations with varying surface potentials. for example in a study of benzene-heptane mixtures in a graphite slit (with no liquid-vapour interface) [ 191 and in simulations of films of hexane-hexadecane mixtures on a gold surface [20] (with both solid-liquid and liquid-vapour interfaces).

CLARKE. INABA. B101.J .. We note that there is no significant ordering of the molecular orientations or change in the percentage of gauche defects near the liquid-vapour interface. Graphics. 328. Appl. Phys. A. INABA. C. E. Am. GROOT. 60. R .. 6638. M.M. and THOMAS. Phys. 1992. Lett. 1993. Chem. W . 62. Soc. Res. Why does this not happen in the lowest layer? Although it is possible that in this layer.N. WINKLER. Phys. I . Science.. We acknowledge financial support from EPSRC (grants GR/K2065 1 and GR/L08427). and LANDMAN.D. L. Thomas for drawing attention to this problem and providing copies of their work before publication. CASTRO. 103.Downloaded by [Texas A&M University Libraries] at 14:51 08 August 2014 260 The behaviour of liquid alkanes near interfaces gauche defects in a long chain. Phys.. A . This still leaves the question as to why the surface tension at a given temperature decreases with chain length.. CASTRO.S. the snapshot shown in figure 2 suggests that this cannot be the sole explanation. S. chem. R . J . which can pack more densely than shorter ones as the shortest intermolecular CC distances are greater than the intramolecular CC bond lengths. . 1999. chem. and REINEKER. 2356. M . J. E. 1993. 100.. Arc. FORESTER T. M. W. Experimentally [ 5 ] . J . 1994. D.M. [4] PATRICK. and ISRAELACHVILI. K . R . and SWENSON. MADURA. 106.R. KOOPMAN. R . 1979.J. C.. 69. H. Chem. Selected Values of Physical and Thermodynamic Properties of Hydrocarbons and Related Compounds (Washington: Carnegie Press). J. and VAN DE ERDE. J . it is also true that surface ordering only occurs in alkanes whose chain length is greater than 15. J. J.. and the consequent increase in free volume for molecules in this region.. Rev. 1310. and THOMAS.. which we have interpreted as suggesting that the strength of the solidliquid interaction is responsible for the experimental observations. Phys. . K . T..J.R. Rev.. and LYNDEN-BELL. R. and HUGHES.. 1998. Rev. K . LANDMAN. K. JORGENSEN. chem. 1992. the optimum packing corresponds to butane molecules filling up interstices between the octane molecules. 1995. and LYNDEN-BELL. the difference of surface free energy between octane and butane at 273 K is 8. FABER. A . G . 910. 4494. 104. D. R . P. KLEIN. 94. Phys. D. 49. 46. and U. GERSRMAIR. J. J.. chem. Surf. M. J. WESTERMANN-CLARKE. phys. 224. 8878.R . 8103. Clarke and R. Chem.. J. 2058. 20. chem. Phys. 10528. M.T. H... . 249. . 1997.8444. .S. .....M.. the IF1 (grant to the Irish Centre for Colloids and Biomaterials). B102. 1996. 1987.L... A . 49. N. J .. D.. N. M..T . J. A.. 1967. 415. and SMITH. Preferential absorption occurs at both the solid-liquid and the liquid-vapour interfaces with longer molecules adsorbed at the solid and shorter ones at the vapour interface. WEBER.3 mJm-2 of energy and 6. W. 4277.. phys.. KOTELYANSKII. which is even flatter than the overlayer.5 mJ mp2 from the -TAS term [21]. 1994. J.T.. G. L. and RAYMENT. B. molec. chem..86 mJ mp2 which is made up of contributions of 2. 1952... M . K. Phys.. 87. 1984. Molec. G . .. I. P.. Lett. GRUEN. Pursuing this argument we would expect octane to be preferred over butane. SCHMID. 1994. . and SMITH. The lowering of the energy due to the intermolecular interactions is also greater for longer molecules. M . 261. . R. 14. To take an example. BALASUBRAMANIAN. and BITSANIS. References [l] ISRAELACHVILI. S.. 70. The segregation of small molecules at the liquidvapour interface can be understood from the thermodynamic point of view as being the result of the lower surface tension (which is equal to the surface free energy for a liquid) of smaller alkanes compared to longer ones. Phys. U. CHRISTENSON. [2] O’SHEA.D. 1997. We thank S. The positive surface entropy is probably the result of the decrease in density across the interface. ..P. T. R. Chem. Phys. A. W.. CLARKE. chem. 1996. Sci.. and HENTSCHKE..R . and SIEPMANN.. K . Handbook of Chemistry and Physics (Boca Raton: CRC Press). RIBARSKY. 136 LIDE.. . J . [5] EARNSHAW. R OSSINI.. 1834. L.W. C . . DEN1 and the Daresbury Laboratory (CAST award to PS).D. . J. A . . M .. XIA. Phys. 1992.A. and the referee for drawing our attention to [21].. Rev. J. . 1987. M. S. Phys. J.. XIA. [3] GELB. . 1987. 1995. OUYANG. WELLAND.. B.. HORN.D. . This is a similar effect to that found in our previous work [6] where the liquid vapour interface encouraged a surface ordered layer.. Phys.. In these simulations we have found no evidence for an immobile layer near the solid substrate. 861. 380. ARNOLD. GUPTA. C .. SMITH. R. Lett.. Thus these short chain alkanes do not show any surface ordering even near the bulk melting transition. LYNDEN-BELL. 3184. . 24.