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2014-01-2719
Published 10/13/2014
© 2014 SAE International, Shell Global Solutions (US) Inc.
doi:10.4271/2014-01-2719
saefuel.saejournals.org

Computer Simulation Studies of Adsorption of Binary and Ternary

Mixtures of Gasoline Components in Engine Deposits
Alex Harrison
The University of Edinburgh

Roger Cracknell
Shell Global Solutions (UK)

Jens Krueger-Venus
Shell Global Solutions (Deutschland)

Lev Sarkisov
The University of Edinburgh

ABSTRACT
Carbonaceous deposits can accumulate on various surfaces of the internal combustion engine and affect its performance.
The porous nature of these deposits means that they act like a “sponge”, adsorbing fuel components and changing both
the composition and the amount of fuel in the combustion chamber. Here we use a previously developed and validated
model of engine deposits to predict adsorption of normal heptane, isooctane, toluene and their mixtures in deposits of
different origin within a port fuel injected spark ignition engine (Combustion Chamber Deposits, or CCDs, and Intake Valve
Deposits, or IVDs) and under different conditions. We explore the influence of molecular structure of adsorbing species,
composition of the bulk mixture and temperature on the uptake and selectivity behaviour of the deposits. While deposits
generally show high capacity toward all three components, we observe that selectivity behaviour is a more subtle and
complex property.

CITATION: Harrison, A., Cracknell, R., Krueger-Venus, J., and Sarkisov, L., "Computer Simulation Studies of Adsorption of
Binary and Ternary Mixtures of Gasoline Components in Engine Deposits," SAE Int. J. Fuels Lubr. 7(3):2014, doi:10.4271/2014-
01-2719.

INTRODUCTION chemicals can be released (desorbed) at other stages of the

cycle, contributing to higher emissions. Finally, if adsorption is
It has now been widely recognised that the accumulation of
selective towards a particular type of species, it may change
carbonaceous deposits on the internal surfaces of the
the composition of the fuel-air mixture prior to ignition possibly
sparkignition engines can lead to engine performance
changing its knock resistance.
deterioration and higher emissions [1,2,3,4]. Several
mechanisms have been proposed for why these adverse
In a series of recent publications we aimed at establishing the
effects happen and these mechanisms depend on the location
significance and extent of this adsorption mechanism [5,6,7,8].
and origin of the deposits. However, one mechanism that
Transient processes in the engine, which involve rapidly
seems to be both universal for all types of deposits and also is
changing temperature and pressure conditions, as well as
the most important contributor to their adverse influence is the
chemical reactions, can not be reproduced in a laboratory
adsorption of fuel components [1,2,3,4]. According to this
setup. In order to focus specifically on adsorption processes
mechanism, deposits, due to their porous structure, act as a
we considered interaction of fuel components with engine
“sponge” within which fuel components and combustion
deposits under static temperature and pressure conditions, in
products (in case of the combustion chamber deposits) tend to
the absence of chemical reactions. Even in this case,
accumulate. In the case of IVDs this has the result that the
measurement of adsorption from mixtures remains an
engine operates under transient conditions with a lower
experimentally challenging task. Hence the emphasis of this
amount of fuel in the combustion chamber than is intended by
and previous studies has been on predictive molecular
the vehicle's engine management system, while the adsorbed
simulation models. The key idea of these models is to
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represent a porous material as a system of independent slit
pores. Although deposits are in general very complex
materials, this is not a completely unreasonable assumption as
the transmission electron microscopy (TEM) images by Zerda
et al do show regions of lamellar structure within the deposits
[9]. This is also an approach widely adopted in the adsorption
studies of related porous carbon materials [10]. Behavior of a
real sample of the material can be then viewed as a collective
behavior of the ensemble of slit pores. Depending on the
sample, pores of different width will occur with different
frequency within the sample and the property that describes
this frequency is called pore size distribution (PSD).
The idea of the approach is to obtain adsorption isotherms on
real deposit samples using species and conditions amiable for
the experimental measurements. Adsorption in individual slit
pores is linked to the adsorption in whole sample through the
Adsorption Integral Equation (AIE):
(1)
where N(Pi) is the experimentally determined adsorption
isotherm at pressure Pi, ρ(w,Pi) is the single-pore adsorption
isotherm in a model slit pore of a characteristic width w, and
f(w) is the pore size distribution, or PSD. Thus, if adsorption
isotherms in individual slit pores of particular widths are known
(forming so-called adsorption kernel), the AIE equation can be
inverted to obtain PSD and this PSD can then be used for
prediction of adsorption in this material at other conditions or
for other species and mixtures of species.
In our previous studies we used ethane to measure adsorption
at ambient temperature in IVD and CCD samples [5,6]. Grand
Canonical Monte Carlo simulations were used to obtain
adsorption isotherms in individual pores. Details of the
parameters of the simulation and required model optimization
are published elsewhere [5,6]. The model was calibrated to
reproduce adsorption behavior of ethane and was validated by
comparison with the experimental data for adsorption of normal
and iso- butanes.
Employed in the predictive capacity, the model indicated that
both CCDs and IVDs should adsorb substantial amounts of
alkanes under temperature conditions of interest [6,7]. These
observations clearly supported the adsorption mechanism of
engine performance deterioration.
So far our studies have focused on a single component
adsorption. The key advantage of molecular simulations is that
adsorption of multi-component mixtures can be considered as
easily as the single component adsorption, in contrast to
experiments. In addition, one family of components that has
not been considered in our previous publications is aromatic
hydrocarbons. Yet they are an important, high octane
component of the gasoline.
Hence, this article extends our previous studies in two
important aspects. Firstly, in addition to isooctane and normal
heptane considered previously as components of the fuel with
extreme values of octane number (100 and 0 respectively), we
also consider adsorption of toluene as a representative of
aromatic species. Secondly, we consider for the first time
adsorption of binary and ternary mixtures of these components.
METHODOLOGY
This study is based on the same methodology employed in a
series of our previous publication [8]. In particular, a model slit
pore in this study consists of two walls, where each wall is
made of six graphene layers. Within the walls the layers are
separated from each other by 3.35Å.
Single component adsorption of normal heptane (n-heptane),
isooctane (i-octane) and toluene, binary and ternary mixtures
of these components are considered. These species are
modeled using the TraPPE united atom forcefield [11,12]. For
the atoms constituting the walls of the slit pores we adopt
parameters from the previous work of Pinto da Costa et al
[5,6]. Standard Lorenz-Berthelot rules are applied to generate
Lennard-Jones parameters for the interactions between the
adsorbing species and the atoms of the slit pore walls. For
adsorbate-adsorbate interactions potential cut-off distance of
15Å is imposed. The system is placed in periodic boundary
conditions in x and y directions.
All Grand Canonical Monte Carlo simulations are performed
using the Multipurpose Simulation Code, MuSiC [13] and using
the protocol described in our previous publication [8].
An adsorption simulation takes fugacity of adsorbing species
as an input parameter and returns the absolute amount
adsorbed (in terms of number of molecules per simulation cell)
as a result. In the results section the isotherms are reported as
the excess amount adsorbed versus pressure of adsorbing
species. We use the Peng-Robinson equation of state to relate
the fugacity and pressure of adsorbing species, and the
following expression to obtain the excess amount [14]:
(2)
where nex and nabs are excess and absolute amounts
adsorbed, respectively (number of molecules per simulation
cell), ρbulk is the density of the bulk phase at the conditions of
interest, calculated using the Peng-Robinson equation of state,
and Vp = Lx·Ly·(Lz − 6.1Å) is the pore volume, with Lx and Ly
being the dimensions of the pore in x and y directions, Lz its
width in z direction and 6.1Å being the smallest width of the
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pore, where adsorption is still possible. This calculation of the
pore volume is consistent with the previous studies of
adsorption in slit pores [15].
The method procurement of the IVD and CCD samples and
their characteristics, such as the elemental analysis have been
described in our previous work [5,6,16]. The PSDs for IVD and
CCD samples were obtained from the experimental data [5],
also published previously, and highly resolved ethane isotherm
kernel. Specifically, we consider pores with widths in the
following ranges: 6Å - 40Å, with 1Å increment in pore width
40Å - 54Å with 2Å increment and also a 300Å to effectively
represent all pores in the mesoporous region. These PSDs for
the IVD and CCD samples are shown in Figure 1.
analysis, the presented adsorption isotherms can be used to
estimate how much fuel can possibly adsorb in engine deposits
under equilibrium conditions of pressure and temperature. For
example, at 390K and 1 bar (close to the lower bound of
pressure values in the engine) 0.751, 0.633 and 0.826 mmol of
i-octane, n-heptane and toluene can adsorb in a gram of the
IVD deposits, respectively. For a gram of IVD material, this
exceeds the typical amount of fuel introduced at a single stoke
of an internal combustion engine (our calculations are based
on a four cylinder engine with a two litre capacity and an intake
pressure equal to one atmosphere).

Once the kernel of adsorption isotherms has been obtained for

a particular species or mixture, the AIE equation can be used
in combination with the previously obtained PSD to generate a
predicted adsorption isotherms for the whole sample at
required conditions. The isotherms shown in the results section
extend up to the bulk saturation pressure of the mixture at the
specified temperature.

Figure 2. Predicted adsorption isotherm for i-octane (blue), n-heptane

(red) and toluene (green) in IVD at 390K (top panel, a) and CCD
(bottom panel, b).

Binary systems considered in this study correspond to either

75%-25% mixtures on liquid volumetric basis (i-octane -
nheptane and toluene - n-heptane, respectively) or to 50%-
50% composition (i-octane - toluene). Results for these
systems are presented in Figures 3, 4, 5, 6.

Figure 1. Pore size distributions (PSDs) for IVD sample (top panel, a)
and CCD sample (bottom panel, b) obtained from the experimental
ethane adsorption isotherm at 278K and computer simulations, as
described in the text.

RESULTS
We begin our analysis with single component cases. Figure 2
(a) shows predicted adsorption isotherms for i-octane,
n-heptane and toluene in IVD at 390K, while Figure 2 (b)
shows these isotherms in CCD at 420K. We note that all three
species exhibit similar trends and adsorb in comparable
amounts. At higher pressures the isotherms also feature steps
in adsorbed densities, which are particularly pronounced for
i-octane and n-heptane isotherms at 390K (IVD). These steps
Figure 3. Predicted adsorption isotherms for binary mixtures in IVD at
are associated with capillary condensation of adsorbing
390K. From top down a) 75%-25% i-octane and n-heptane, b)
species in pores of particular width [8]. These phenomena are
50%-50% toluene n-heptane, c) 75%-25% toluene and n-heptane. The
well known and extensively described in the physical colour scheme as before: blue is for i-octane, red is for n-heptane and
adsorption literature [17]. Finally, reiterating our previous green is for toluene, respectively.
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In particular Figure 3 shows predicted adsorption isotherms for do not exhibit an overwhelming preference for either of the
binary systems at 390K in the IVD material. Adsorption components. We will return to this issue in the context of
isotherms for individual components resemble in shape and in selectivity in ternary mixtures.
general trends single component isotherms presented in Figure
2. These isotherms also feature steps in the adsorbed density
associated with the condensation of the mixture in pores of a
particular size. These steps occur at the same values of
pressure for both components and the physical reason for this
has been discussed in our previous publication [8].

In case of i-octane - n-heptane and toluene - n-heptane binary

mixtures, the amount of i-octane and toluene adsorbed
substantially exceeds the amount of n-heptane adsorbed as
i-octane and toluene are the prevailing species in their
respective binary mixtures (75%). From the point of view of the
deposit effect on engine performance it is also very important
to understand whether there is a selective adsorption of a
particular type of species, leading to a possibly adverse
change in the effective fuel composition prior to ignition.

The extent of selective adsorption effects can be characterized Figure 4. Selectivity in binary systems as a function of pressure for IVD
with binary selectivity, which for species i and j is defined as: at 390K showing i-octane / n-heptane (filled circles), toluene / i-octane
(filled squares) and toluene / n-heptane (filled triangles).

In Figures 4 and 5 this analysis is extended to CCD at 420K.

The results follow the general trends presented earlier, with the
(3)
selectivity showing less deviation from one for all systems as
expected at higher temperatures.
where xi and xj are the mole fractions of the components in the
adsorbed phase and yi and yj are mole fractions of the same
components in the bulk gas phase. Essentially, selectivity
characterizes how the composition of the binary mixture
changes upon adsorption in a porous material, compared with
the bulk composition. Values of selectivity above one indicate
selectivity of the material towards species i (in other words
component i is preferentially adsorbed).

These selectivity analyses for binary systems of Figure 3 are

shown in Figure 4. From this figure it is evident that this
property exhibits quite complex patterns, depending on binary
mixture and the combined pressure of the components.

Specifically, there is some preference of both i-octane over

n-heptane throughout the pressure range. In toluene -
n-heptane system, the initial selectivity (up to about 0.5 bar) is
toward n-heptane, with the trend reversing above 0.5 bar. Figure 5. Predicted adsorption isotherms for binary mixtures in CCD at
Finally, i-octane shows slight preference for adsorption over 420K. From top down a) 75%-25% i-octane and n-heptane, b)
toluene up to 1.2 bar, when the selectivity also reverses for this 50%-50% toluene i-octane, c) 75%-25% toluene and n-heptane. The
system. It is important to note however, that the magnitude of colour scheme as before: blue is for i-octane, red is for n-heptane and
green is for toluene, respectively.
selectivities shown in Figure 4 is rather small. For comparison,
selectivity of carbon dioxide over methane is about 4, while
Finally, we consider the ternary mixture of i-octane, toluene
carbon dioxide over nitrogen selectivity can be more than 20 in
and n-heptane. The composition of the mixture is 42.9%
a typical activated carbon at room temperature. We also note
i-octane, 42.9% toluene and 14.2% n-heptane. Adsorption
that, in general, selectivity is a property quite sensitive to the
isotherms for IVD at 390K and CCD at 420K are shown in
pore size distribution [8] and given the simplifications of the
Figure 7, panels a) and b), respectively.
model, a conservative conclusion would be that IVD deposits
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Figure 8. Selectivity of combined i-octane and toluene species over

Figure 6. Selectivity in binary systems as a function of pressure for
n-heptane in ternary systems for IVD at 390K (filled circles) and CCD
CCD at 420K showing i-octane / n-heptane (filled circles), toluene /
at 420K (filled squares) as a function of pressure. The upper limit of the
i-octane (filled squares) and toluene / n-heptane (filled triangles).
pressure values is defined by the bulk condensation pressure of the
mixture at a particular temperature (1.41 bar at 390K and 2.96 bar at
420K).

Figure 7. Predicted adsorption isotherms for a ternary mixture of

i-octane (blue, 42.9%), n-heptane (red, 14.3%) and toluene (green,
42.9%) in IVD at 390K (top panel, a) and in CCD at 420K (bottom Figure 9. Selectivity for i-octane over n-heptane in binary (filled circles)
panel, b). and ternary (filled diamonds) in CCD at 420K.

Table 1. Research octane number (RON) as a function of ternary

To assess the possible effect of selective adsorption on engine
mixture composition from MLbV model.
operation, we perform selectivity analysis of these isotherms by
grouping toluene and i-octane in one, high octane species.

Adsorption selectivity of this species over n-heptane is shown

in Figure 8 for IVD at 390K and CCD at 420K. It is interesting
to note that the deposits exhibit slight selectivity towards the
higher octane species in both types of samples. In particular, the table indicates that an increase in n-heptane
concentration from 14.2% to 20% in the mixture prior to ignition
In principle, although these selectivity effects are not leads to about 6% drop in the RON (from 96.1 to 90.3).
particularly large in magnitude compared to other adsorption
It is also important to compare selectivity observed in the ternary
processes, they may still substantially affect the performance
system to the binary systems, as this would indicate whether
of the engine by changing the effective octane number of the
consideration of more complex, multi-component mixtures is
fuel. To illustrate this point in Table 1 we show research octane
indeed required or the behaviour of the system can be incepted
number (RON) as a function of ternary composition calculated
simply from the analysis of binary systems of different types. As
using the modified linear-by-volume model (MLbV) [18].
an example, Figure 9 compares selectivity for i-octane over
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Harrison et al / SAE Int. J. Fuels Lubr. / Volume 7, Issue 3 (November 2014)
n-heptane in binary and ternary systems for CCD at 420K, and it
is quite clear that this property indeed changes as more
components are added to the mixture. This is a very interesting
observation as it implies that there are some cooperative and
packing effects among molecules in the ternary system that can
not be deduced from the analysis of binary systems. On the
other hand as the selectivity effects become more visible in
multi-component systems, this suggests that the composition of
the mixture prior to ignition may indeed be influenced by
selective adsorption in the deposits.
SUMMARY
In this study we apply molecular simulations to investigate
adsorption of fuel components in experimentally calibrated
models of engine deposits. We focus on adsorption of i-octane,
toluene and n-heptane, representing different classes of fuel
components. Single, binary and ternary mixtures are
considered and the results can be summarized as follows.
All three species adsorb in engine deposits in appreciable
amounts, comparable to the amount of fuel introduced at a
single stroke (as estimated for a 4-cyl, 2L internal combustion
engine). An important new result presented here is the
comparable and substantial adsorption of aromatic species
under conditions of interest in different types of deposits.
Studies of more realistic, binary and ternary mixtures reinforce
this picture of deposits acting as porous sponges with respect
to fuel vapors.
Although, the deposits do not show an overwhelming
preference for a specific component, they exhibit slight
selectivity towards high octane components in binary systems
(i-octane and toluene) at pressures above 1 bar, with selectivity
towards i-octane further enhanced in ternary systems.
In the process of obtaining these results we also noted general
sensitivity of the selectivity results to the details of the PSD and
this is a clear limitation of the model based on a simplified
representation of the structure of the deposits as a collection of
independent slit pores. This will be investigated further and
presented in a separate study. Nevertheless, analysis of the
ternary systems suggests the composition of the fuel will be
affected by the presence of the deposits, and further analysis is
needed to better understand how exactly it will change.
ACKNOWLEDGMENTS
This work has made use of the resources provided by the
Edinburgh Compute and Data Facility (ECDF) (http://www.ecdf.
ed.ac.uk/). The ECDF is partially supported by the DIKT
© 2014 Shell Global Solutions (US) Inc.; Published by SAE International. This Open Access article is published under the terms of the Creative Commons Attribution
License (http://creativecommons.org/licenses/by/4.0/, which permits use, distribution, and reproduction in any medium, provided that the original author(s) and the
source are credited.
Positions and opinions advanced in this paper are those of the author(s) and not necessarily those of SAE International. The author is solely responsible for the content
of the paper.
initiative (http://www.edikt.org.uk). The authors would like to
thank Shell Global Solutions for providing the CCD and IVD
samples and for funding this project.
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