Supplementary material

Dynamic Wettability Alteration of Calcite, Silica and Illite Surfaces

in Subsurface Environments: A Case Study of Asphaltene

Self-Assembly at Solid Interfaces

Sohaib Mohammed1 and Greeshma Gadikota 1*

1
School of Civil and Environmental Engineering, Cornell University,

220 Hollister Drive, 527 College Avenue, Ithaca, NY 14853

*
Corresponding Author. Phone: +1 607-255-4796. E-mail: gg464@cornell.edu

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Table S1. Lennard-Jones potential and partial charges for calcite, silica and illite surfaces.

Atom type ԑ (kJ/mol) σ (nm) q (e)

Calcite
Ca 2.0000 2.3700 1.668
C 0.3690 3.8200 0.999
O 0.5820 3.0900 -0.889
Silica
Si 3.30203 7.7006 × 10-6 2.1
O 3.16556 0.65017 -1.05
Ohydroxyl 3.16556 0.65017 -0.95
H 0 0 0.425
Illite
Hhydroxyl 0.0000 0 0.4250
Ohydroxel 0.6502 0.31656 -1.0500
Ooctahedral 0.6502 0.31656 -1.1808
Otetrahedral 0.6502 0.31656 -1.1688
Odouble 0.6502 0.31656 -1.2996
Si 7.0076 x 10-6 0.33020 2.1000
Aloctahydral 5.5638 x 10-6 0.42712 1.5750
Altetrahydral 7.7006 x 10-6 0.33020 1.5750
Mg 3.7780 x 10-6 0.52643 1.3600
K 0.4184 0.33340 1.0000

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Table S2. Van der Waals and electrostatic interaction (kcal/mol) of asphaltene with calcite, silica
and illite surfaces to explain the observed distributions and diffusivities of water and hydrocarbons
and the aggregation behavior of asphaltenes. The intermolecular interactions were calculated
during the last 10 ns.

Calcite Silica Illite

Without Asphaltene
Van der Waals
Asphaltene - - -
Toluene -22.2 -16.4 -18.4
Heptane -16.2 -9.3 -13.1
Water -607.3 -592.2 -578.8
Electrostatic
Asphaltene - - -
Toluene -16.5 -13.2 -14.8
Heptane -0.2 -0.1 -0.1
Water -405.7 -388.1 -363.9
With Asphaltene
Van der Waals
Asphaltene -54.4 -49.7 -44.3
Toluene -619.4 -601.1 -608.2
Heptane -589.8 -534.5 -548.3
Water -112.3 -101.5 -99.7
Electrostatic
Asphaltene -150.5 -127.2 -132.2
Toluene -614.8 -593.5 -603.2
Heptane -10.3 -8.9 -9.2
Water -77.2 -67.0 -58.4

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S1. The influence of wettability alterations on surface energy

The profiles of the surface energies of the calcite, silica and illite showed a clear dependency on
the simulation time and asphaltene self-assembly (Figure S1). At time zero, the surface energy of
calcite, silica and illite surfaces are 0.52 ± 0.01, 1.16 ± 0.03 and 0.97 ± 0.02 J/m2, respectively,
which agree with the experimental studies [1, 2]. As the simulation time proceeded, the surface
energy decreased systematically, presumably because of the spreading of water molecules on the
surface that hydrate the active (high energy) sites and reduce the surface free energy. In the absence
of asphaltene, the equilibrium surface energy values of calcite, silica and illite surfaces are 0.25 ±
0.02, 0.48 ± 0.03 and 0.42 ± 0.04 J/m2, respectively. However, as asphaltene introduced to the
system, it limited the water molecules from spreading on the surfaces, due to the deposition on the
surface and accumulation at water-oil interface, which resulted in lower hydration effect of surface
atoms and consequently the surface energy of calcite, silica and illite reduced slightly. The
equilibrium surface energy in the presence of asphaltene are 0.45 ± 0.03, 0.82 ± 0.05 and 0.71 ±
0.04 J/m2, respectively.

Figure S1. The surface energy of the simulated calcite, silica and illite as a function of the
simulation time in heptane and toluene and in the presence and absence of asphaltene.

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S2. Density profile of water droplet

Figure S2. Water density profile on the axis parallel to the water-solid interface (x-axis) on calcite,
silica, and illite in the absence and presence of asphaltene.

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S3. The mechanism of asphaltene aggregation

Asphaltene molecules showed a self-assembly property combined with an accumulation on the

water/oil interface and deposition, as a monomers and aggregates, on the calcite, silica and illite
surfaces. The driving force of the asphaltene self-assembly is the intermolecular interactions
between the aromatic cores and heteroatoms (S, N and O) in the asphaltene structure [3]. It is
believed that the major driving force for the asphaltene self-assembly is the interaction between
the aromatic cores as the self-assembly energy increases with the number of aromatic rings.
Further, the presence of heteroatoms in the aromatic core contribute positively in increasing the
self-assembly energy. The aggregated asphaltenes stack with each other mainly by face-to-face
stacking and less by T-shape stacking (Figure S3).

Figure S3. Snapshots for asphaltene cluster composed of all the simulated molecules. It is clear
from the snapshot that the main stacking mode is the π-π stacking. Carbon, hydrogen, oxygen,
sulfur and nitrogen are shown in cyan, white, red, yellow and blue, respectively.

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References
[1] Y.K. Shchipalov, Surface energy of crystalline and vitreous silica, Glass Ceram. 57(11-12)

(2000) 374-377.

[2] N. de Leeuw, S. Parker, Atomistic simulation of the effect of molecular adsorption of water on

the surface structure and energies of calcite surfaces, Journal of the Chemical Society, Faraday

Transactions 93(3) (1997) 467-475.

[3] M. Sedghi, L. Goual, W. Welch, J. Kubelka, Effect of asphaltene structure on association and

aggregation using molecular dynamics, J. Phys. Chem. B 117(18) (2013) 5765-5776.