A Generalized Interaction Method for the Prediction of Octane Numbers

for Gasoline Blends

Chorng H. Twu* and John E. Coon

Simulation Sciences Inc., 601 South Valencia Avenue, Brea, CA 92621 (USA)

Keywords: octane number, blending, research octane number, motor octane

number, gasoline

Abstract
This paper presents an interaction method for predicting the research and
motor octane numbers of gasoline blends. The proposed method and
correlation has the following characteristics: (1) The blending correlation blends
exactly the octane numbers of isooctane and n-heptane.(2) The blended octane
number is unchanged when blending identical components. (3) The blending
equation describes blending behavior accurately throughout the entire
composition range. (4) The blending correlation works not only for binaries, but
also for multicomponents. (5) The predicted research and motor octane
numbers for a given blend from the correlation is invariant when a component is
divided into two or more identical subcomponents. The correlation is in a
simple form and the binary interaction parameters can be generalized. A
universal set of binary interaction parameters is developed for the interaction
correlation. The only input data for the correlation developed in this work are
the research or motor octane number of each gasoline cut and its olefins,
aromatics, and saturates contents, which are standard laboratory inspection data
of gasoline cuts. The component type-oriented interaction method is general
and will predict accurately the octane number of gasoline blends.

Introduction
The octane number of a motor gasoline is one of the most important measures
of gasoline quality. It has always been the goal of refiners to predict accurately

*
Corresponding author
the octane ratings of blending gasolines. The research and motor octane
numbers of a gasoline are measurements of its quality of performance as a fuel.
The octane number scale itself is based on the linear blending of isooctane and
n-heptane. The octane number of a gasoline is measured on a scale that ranges
from that equivalent to isooctane (octane number of 100) to that of n-heptane
(octane number of 0). Octane number is affected by the saturates, aromatics,
and olefins contents of gasoline.

When gasoline components are blended together, the octane number of the
blend may have an octane number quite different from that of either component,
even when the two components are of equal octane number. The blend octane
number may be greater than, equal to or less than that calculated from the
volumetric average of the octane numbers of the blend components, which
indicates nonlinear blending. Blending would be linear if octane number of a
blend was equal to that predicted by summimg the octane numbers of the
components in proportion to their concentrations. In practices, the
discrepancies between the octane numbers of blends and the linearly predicted
values have been correlated by specific empirical equations and these have been
used to correct the linear predictions. It is clear, however, that an accurate
octane blending method is needed to optimize the blending of gasoline
components.

Discussion of Previous Methods

Schoen and Mrstik (1955) developed a graphical correlation for predicting
octane numbers of blends as a series of binary systems based on the octane
rating and volumetric olefin contents of the two components being blended.
The blended octane number yields different values depending upon the order of
calculation. Stewart (1959) refined this method to be applicable to
multicomponent blends yielding more self-consistent results. Stewart’s
correlation also required the octane rating and volume percent olefins of the
components being blended.

Auckland and Charnock (1969) developed a blending index to blend octane

number linearly. The blending index is a hypothetical value obtained by
extrapolating from the octane rating at a given concentration to a octane rating at
100 percent concentration of component. Obtaining blend values by blending

2
the blending indices linearly is analogous to obtaining the molar property of a
real solution by a linear combination of the partial molar properties of its
components. Since the partial molar property depends on the composition, so
does the blending index. Therefore, the usage of this approach is limited. The
index method can only be used to find the blending value of a component at a
particular composition and cannot be used to predict its blending values in other
mixtures.

Rusin et al. (1981) presented a rather complicated transformation method for

estimating the octane number of gasoline blends from the octane ratings of the
components, their concentrations, and contents of olefins, aromatics and
paraffins. The method consists of three steps: (a) transformation of component
properties (b) linear blending of these transformed properties, and (c) inverse
transformation of the results. This method is similar to the blending index
method. Due to the back and forth transformation, this method may also cause
inconsistency in data transformation between these three steps.

Healy et al (1959) correlated gasoline component blending with differences in

octane level and hydrocarbon type among components. However, if the
equation of Healy et al. is used to predict the blending behavior of new
components, unreasonable blending values may be obtained, especially if the
hydrocarbon type or octane number of the new component is outside the range
of the component previously tested (Morris, 1975).

An interesting equation was proposed by Morris et al. (1975) for describing

nonlinear gasoline blending behavior as follows:

octane number = x1a1 + x2a2 + b12 x1 x2 (1)

where ai and xi are the octane number and the volume fraction of component i,
respectively and b12 is the interaction coefficient for components 1 and 2.

Equation (1), which represents a simple excess octane number function, is

quite effective in correlating the octane numbers of gasoline blends. However,
there are some disadvantages of using this model to describe gasoline blending
behavior. First, the parameter b12 is an empirical constant, which depends on
the characteristics of components 1 and 2. The interaction parameter b12 not
only depends on the component types, but it also depends on the octane levels
3
and octane differences. The values of b12 can vary from large negative to large
positive ones and the interaction parameter b12 must be changed if the
component characteristics change. The set of binary parameters obtained from
eqn.(1) can only be used for the specific set of components where the
parameters were derived. Therefore it would be very difficult to generalize these
interaction parameters as a function of these properties for the purpose of
prediction.

The second disadvantage is that when new components are added to the
gasoline pool, new interaction parameters are required to describe the behavior
of the new component with the present components. Therefore, an additional
blending study with the new component and other components must be carried
out to determine the additional interaction terms. With n components, n(n-1)/2
interaction parameters are required. If four new components are added to an
eight-component gasoline pool, the number of interaction parameters increases
drastically from 28 to 66. This means that, at least, thirty-eight blending studies
with the new components and the other components must be carried out to
determine these additional 38 interaction parameters. Because it is non-trivial to
run a blending study, it is very costly to run additional blending studies
whenever there are new components to be blended into the gasoline pool.

Zahed et al. (1993) proposed a model with five independent variables for
predicting the octane number of gasoline blends. The variables of the model
can be regressed so that the model works well for the blends used in the
regression but it will still perform poorly for other blends. The five variables
derived from this model are internally inconsistent. The octane numbers
predicted from this equation are no longer even close to the original octane
numbers of the gasoline components. The octane number of n-heptane
predicted from this model is 108.77 versus the defined value of zero. Similarly,
the octane number of iso-octane predicted from this model is -108.95 versus the
defined value of 100. The set of variables obtained from this model can only
be used for this specific set of components within the same range of
compositions where the variables were derived. The usefulness of this kind of
approach is very limited. Using this model to predict the octane number of
blend at other conditions will be very unreliable.

4
 Without accurate blending correlations, any attempt to blend different gasoline
cuts can be expected to achieve non-optimum results. The purpose of the work
is to propose a method and to develop an interaction correlation for the
prediction of blending research and motor octane numbers for any number of
gasoline cuts. The correlation would describe the octane blending behavior at
any possible composition.

Proposed Interaction Blending Correlation

In the development of an interaction correlation, we ensure that the correlation
describes blending behavior of identical or different components throughout the
entire composition range, not only for binary but also for multicomponent
blends. By definition, the research or motor octane number of a blend, a, of n-
heptane and iso-octane is given by:

a = x1a1 + x2a2 (2)

where x1 and x2 are the volume fraction of n-heptane and iso-octane in the blend.
a1 is the octane number of pure n-heptane which is equal to zero and a2 is the
octane number of pure iso-octane which is equal to 100. A generalized form of
eqn.(2) for a blend of n components is given by:

a= ∑ xiai
i
(3)

Eqn.(2) provides one logical starting point for any attempt to predict octane
numbers from composition. Because there is no blending effect for blending
identical components, the simplest nontrivial expession which obeys these
conditions is that of eqn.(2) plus the term b12x1x2 as proposed by Morris et al.
(1975). This expression for correction on octane number is symmetrical. For a
general description of blending behavior, this equation is not adequate.
Additional terms are needed to represent adequately the blending behavior of
octane number for a binary. One particularly successful series expansion was
introduced by Redlich and Kister (1948). However, the Redlich-Kister equation
can not be rigorously extended to multicomponent systems. Note that the first-
order term of the Redlich-Kister expansion is term used in the eqn.(1) by Morris
et al. (1975). A correlation of the form given by Morris but extended to a more

5
complex form such as Redlich-Kister expansion would do a more accurate job
of correlating blend octane numbers, but it would still suffer from the limitations
discussed earlier.

A different approach from Morris et al. (1975) is proposed here. Instead of

adding b12x1x2 to eqn.(2), eqn.(3) is rewritten in a more general form as:

a= ∑ ∑ xixjaij
i j
(4)

where
1
aij = ( ai + aj )(1− k ij ) (5)
2
A binary interaction parameter, kij, is introduced into the blending correlation
to correct the assumed mathematic average mean rule for the "aij" parameter in
the eqn.(5). This correlation is very effective in representing the octane blending
behavior of gasoline cuts. If symmetric binary interaction parameters, kij = kji,
are assumed, then the expression of eqn.(5) for correction on octane number is
symmetrical. For asymmetric correction, asymmetric binary interaction
parameters, (i.e. kij ≠ kji), can be used for aij in eqn.(4):
1
aij = ( ai + aj )[(1 − k ij ) + ( kij − k ji ) xi2 ] (6)
2
Eqns.(4) and (6) can be generalized for the blend of a multicomponent system
as follows (Twu et al., 1991):
1 
a = ∑ ∑ xi xj 
2
( ai + aj ) ( 1− kij )

i j

 1 
1/ 3
1 / 3
3

+∑ xi  ∑ xj  (ai + aj )  ( kij − kji )  (7)

i  j 2  

If kij = kji, eqns.(4) and (5) are recovered. By using different values of kij and
kji in eqn.(7), any blending behavior can be correlated using this blending
correlation. Blends made from constitutes of equal or nearly equal octane
ratings are said to be “matched”. Typical blending data will normally fall into
one of the six different types shown in Figs 1 to 6. Figure 1 shows the octane
6
bonus from blending two matched components. The mixing of an olefin and a
paraffin show positive deviation, and belong to this class. Figure 2 shows
negative deviations. As an example, aromatic and olefin blends of varying olefin
concentrations show a slightly negative deviation. The blend deviations can also
be both positive and negative over the range of blend compositions as illustrated
in Fig. 3. The locus of octane numbers of match blends shown in Fig. 1 and 2
is a parabolic curve. However, blending deviations for components show that
these curves do not necessary have a symmetric shape (Fig. 4 and 5). The
order of magnitude of the bonus or negative value and the skewedness of the
curves, which can be simulated by varying values of kij and kji, will vary greatly
from system to system. Finally, isooctane blending linearly with n-heptane is
reproduced in Fig.6 using eqn.(7) with kij = kji = 0.

Binary Interaction Parameters

The selection of either symmetric binary interaction parameters (kij = kji) or
asymmetric binary interaction parameters (kij ≠ kji) for blending the octane
number of gasoline cuts is determined on the basis of a rather empirical analysis
of the goodness of fit. For some mixtures, an accurate description of mixture
behavior requires asymmetric binary interaction parameters. For blending
gasoline cuts, the use of asymmetric binary interaction parameters does not
appear necessary and a very simple blending correlation, eqns.(4) with (5), is
therefore adopted for gasoline blends in this work. Note that this simplification
is still covered by the more general correlation given as eqn.(7).

For octane number blends of gasoline cuts, the use of one symmetric binary
interaction parameter per binary component provides adequate representation
for gasoline blending, based on the quality of the data available. The reason
may be because of complicated mixtures with various types of hydrocarbon in
each gasoline cut. The fact that the contents of blends has so many different
types of hydrocarbons makes it plausible that the sum of the individual blending
deviations may be approximated by a segment of a symmetric parabola over a
limited range of compositions; the results indicate that this assumption is very
satisfactory.

Standard laboratory inspection data of gasoline cuts usually include research

and motor octane numbers and their contents of olefins, aromatics, and

7
saturates. In this paper we shall consider olefins, aromatics, or saturates as
“components” and the gasoline cut as a mixture of these components.
Depending on the laboratory analysis, a gasoline cut may be reported as a
mixture of either three components (olefins, aromatics, and saturates) or four
components (olefins, aromatics, paraffins, and naphthenes), or five, etc. The
more detailed the analysis, the more accurate are the correlated results that can
be achieved.

Although the same name (such as “aromatics”) is given to the component

contained in different gasoline cuts, they are really different components because
gasoline cuts are complicated mixtures with various types of aromatics. This
means that the octane number of the aromatics from one gasoline cut is different
from the octane number of the aromatics from another gasoline cut. Therefore,
if two gasoline cuts containing olefins, aromatics, and saturates components are
blended together, the number of different components in this blend is
considered to be six components, not three.

Because there is no any information available on the octane numbers of the

components in a gasoline cut, we propose in this paper that the same octane
number of the gasoline cut be assigned to its components. For example, if the
research octane number (RON) of the gasoline cut is 97.8, then the RONs of its
component olefins, aromatics, and saturates are all assumed to be 97.8. This
approach is internally consistent because the RON of the gasoline cut is
recovered by blending these three components together with binary interaction
parameters in eqn.(5) set to zero. This methodology results in zero binary
interaction parameters between components inside the same gasoline cut, but
non-zero binary interaction parameters between gasoline cuts. In other words,
to blend two three-component gasoline cuts, A and B, the binary interaction
parameters between components inside gasoline cuts A and B are all zero, but
binary interaction parameters between component i (e.g. aromatics) in cut A and
component j (e.g. olefins) in cut B are non-zero. Furthermore, if i and j are both
the same hydrocarbon type (e.g., aromatics in cut A and aromatics in cut B), the
binary interaction parameter between them is assumed to be zero (i.e., kii=0).
The total number of binary interaction parameters for blending two three-
component gasoline cuts is only 3 (i.e., binary interaction parameters between
aromatics in cut A and olefins in cut B, aromatics in cut A and saturates in cut

8
B, olefins in cut A and saturates in cut B). The advantage of this methodology
is that only three binary interaction parameters are required for the correlation for
blending any number of gasoline cuts having components olefins, aromatics,
and saturates.

The binary interaction parameters between components have been derived

from the regression of blending data of gasoline cuts. These binary interaction
parameters between components are then used to generate internally consistent
binary interaction parameters between gasoline cuts. To obtain the general
relationship of binary interaction parameters between components and gasoline
cuts, let’s assume that gasoline cut X is a mixture of m components with
compositions x1, x2, ..., xm, and the gasoline cut Y is a mixture of the same m
components with compositions y1, y2, ..., ym. For two three-component
gasoline cuts, X and Y, m is equal to 6 with non-zero compositions x1, x2, x3, y4,
y5, and y6 and zero compositions y1, y2, y3, x4, x5, and x6 or vice versa. The
binary interaction parameter between gasoline cuts X and Y, KXY, is related to
the binary interaction parameters between components by
1 
∑ ∑( xiyj + xjyi ) 2 ( ai + aj) (1 − kij )
m m

KXY = 1 −
i j
(8)
m m
1 
∑i ∑j ( xixj + yi yj ) 2 ( ai + aj ) (1 − kij )
where kij is binary interaction parameter between component i (e.g. aromatics) in
cut X and component j (e.g. olefins) in cut Y.

After generating the binary interaction parameters between cuts, the calculation
of octane number of gasoline blends can be simplified greatly. For gasoline
blends, eqns.(4) and (5) become:

a= ∑ ∑ zi zjaij
i j
(9)

where
1
aij = ( ai + aj )(1 − Kij ) (10)
2
zi and ai are volume fraction and octane number of gasoline cut i. Kij is the
binary interaction parameter between gasoline cuts i and j, which is given by

9
eqn.(8). An exception to this occurs if a gasoline cut is split into two identical
gasoline cuts. The Kij between these two gasoline cuts must be set to zero by
the user because they are identical components, rather than being calculated
from eqn.(8). This is to remain consistent with the approach we proposed
earlier, which sets all kijs within a cut to be zero.

Application to Gasoline Blends

Use of the proposed blending correlation in this work is best illustrated by an
example problem. The extensive blend data used to develop the binary
interaction parameters were taken from Healy et al.(1959). The compiled data
covered a wide range of commercial blending stocks and finished gasoline
blends. A total of 161 blends and 157 gasoline cuts were used in this study.

The blending components used were typical refinery gasoline stocks

consisting of straight run, catalytically cracked, thermally cracked, catalytically
reformed, thermally reformed gasolines, natural gasoline, aromatic
concentration, isomer, polymer, alkylate, isopentane, as well as n-pentane and n-
butane. The data required for each gasoline cut are octane number, olefin
contents, aromatic contents, saturated contents, and proportion by volume. For
the example shown here, the properties of the gasoline cuts and blends and
blend compositions are from Healy et al.(1959). Table 1 shows these properties
of the gasoline cuts.

Table 1. Laboratory Inspection of Gasoline Cuts

----------------------------------------------------------------------------------------------
Hydrocarbon-type analysis, volume %
---------------------------------------------------
Gasoline cuts RON MON Olefins (O) Aromatics (A) Saturates (S)
----------------- ------ ------- ------------- ----------------- ----------------
Reformate (1) 97.8 87.0 1.4 63.1 35.5
Thermally
cracked (2) 70.4 65.1 32.5 9.8 57.7
Catalytically
cracked (3) 92.6 80.2 53.3 23.9 22.8
Polymerized (4) 96.8 82.3 100.0 0.0 0.0
Light straight
run I (5) 58.0 58.0 1.3 3.8 94.9
10
Light straight
run II (6) 61.9 62.0 0.7 2.4 96.9
---------------------------------------------------------------------------------------------

We have assigned component numbers O, A, and S to olefins, aromatics, and

saturates, which are the components contained in the gasoline cuts, respectively.
We also assign gasoline cut number 1, 2, 3, 4, 5, and 6 to reformate, thermally
cracked, catalytically cracked, polymerized, light straight run I, and light straight
run II, respectively. Eleven blends with blend compositions were made from
these six gasoline cuts.

The three binary interaction parameters between components, which are

derived from the regression of these 11 blending data of 6 gasoline cuts, are
shown in Tables 2A and 2B. As mentioned previously, these three binary
interaction parameters between components are then used to generate binary
interaction parameters between gasoline cuts through eqn.(8), which are given in
Tables 3A and 3B. These binary interaction parameters between cuts are then
used in eqns.(9) and (10) to predict the octane numbers of gasoline blends. The
predicted results for these 11 blends are given in Tables 4A and 4B. The
accuracy of prediction of the blend octane numbers obtained isexcellent with an
average absolute deviation percent (AAD%) less than 0.5% for both research
octane number (RON) and motor octane number (MON). Note that the
deviations of the research octane numbers of the last two blends containing light
straight run II are much larger than the others exhibited in Table 4A, indicating a
possible data inconsistency in the light straight run II gasoline cut. If these last
two blends are excluded, the deviation of the prediction of the octane number of
the blends of this group will be much less than 0.5%.

Table 2A
The binary interaction parameters between components for RON
-------------------------------------------------------------------------------
kOA = 0.0364
kOS =-0.0891 kAS = -0.0954
-------------------------------------------------------------------------------

11
Table 2B
The binary interaction parameters between components for MON
-------------------------------------------------------------------------------
kOA = 0.1479
kOS =-0.1571 kAS = -0.0760
-------------------------------------------------------------------------------

Table 3A
The binary interaction parameters between gasoline cuts for RON
------------------------------------------------------------------------------------------------
K12 = -0.0416
K13 = -0.0266 K23 = -0.0446
K14 = -0.0087 K24 = -0.0479 K34 = -0.0116
K15 = -0.0597 K25 = -0.0386 K35 = -0.0670 K45 = -0.0832
K16 = -0.0604 K26 = -0.0385 K36 = -0.0683 K46 = -0.0855 K56 = -0.0074
------------------------------------------------------------------------------------------------

Table 3B
The binary interaction parameters between gasoline cuts for MON
------------------------------------------------------------------------------------------------
K12 = -0.0192
K13 = 0.0026 K23 = -0.0529
K14 = 0.0375 K24 = -0.0762 K34 = -0.0005
K15 = -0.0480 K25 = -0.0563 K35 = -0.0944 K45 = -0.1435
K16 = -0.0489 K26 = -0.0571 K36 = -0.0973 K46 = -0.1487 K56 = -0.0075
------------------------------------------------------------------------------------------------
Table 4A
The predicted RON for gasoline blends from the binary interaction parameters
between components.
--------------------------------------------------------------------------------------------------
volume fractions of gasoline cuts in blends RON
------------------------------------------------------ ------------------
I z1 z2 z3 z4 z5 z6 Expt. Calc. Dev%
-- ----- ----- ----- ----- ----- ----- ------- ------- --------
1 0.41 0.04 0.32 0.09 0.14 0.00 91.80 91.62 -0.19
2 0.23 0.03 0.52 0.09 0.12 0.00 91.40 91.22 -0.19
3 0.26 0.03 0.52 0.07 0.12 0.00 91.80 91.36 -0.47
4 0.41 0.03 0.35 0.07 0.14 0.00 91.40 91.70 0.33
5 0.41 0.03 0.44 0.00 0.12 0.00 91.50 91.98 0.53

12
 6 0.34 0.03 0.43 0.05 0.14 0.00 91.20 91.23 0.03
7 0.00 0.11 0.46 0.00 0.43 0.00 78.00 77.88 -0.16
8 0.41 0.12 0.00 0.00 0.47 0.00 78.20 78.22 0.03
9 0.35 0.12 0.00 0.05 0.48 0.00 77.60 77.98 0.49
10 0.16 0.11 0.20 0.09 0.00 0.44 80.00 80.85 1.06
11 0.23 0.10 0.29 0.00 0.00 0.38 84.00 82.73 -1.52
---- ------
AAD% 0.45
Table 4B
The predicted MON for gasoline blends from the binary interaction parameters
between components.
--------------------------------------------------------------------------------------------------
volume fractions of gasoline cuts in blends MON
------------------------------------------------------ ------------------
I z1 z2 z3 z4 z5 z6 Expt. Calc. Dev%
-- ----- ----- ----- ----- ----- ----- ------- ------- --------
1 0.41 0.04 0.32 0.09 0.14 0.00 81.40 80.66 -0.90
2 0.23 0.03 0.52 0.09 0.12 0.00 79.60 80.03 0.54
3 0.26 0.03 0.52 0.07 0.12 0.00 80.20 80.16 -0.04
4 0.41 0.03 0.35 0.07 0.14 0.00 80.80 80.73 -0.09
5 0.41 0.03 0.44 0.00 0.12 0.00 80.40 80.96 0.70
6 0.34 0.03 0.43 0.05 0.14 0.00 80.50 80.32 -0.22
7 0.00 0.11 0.46 0.00 0.43 0.00 72.70 72.29 -0.56
8 0.41 0.12 0.00 0.00 0.47 0.00 72.40 72.62 0.30
9 0.35 0.12 0.00 0.05 0.48 0.00 73.00 72.41 -0.80
10 0.16 0.11 0.20 0.09 0.00 0.44 74.40 74.97 0.76
11 0.23 0.10 0.29 0.00 0.00 0.38 75.80 75.98 0.24
---- ------
AAD% 0.47

To develop a universal set of binary interaction parameters between

components, a total of 161 blends from 157 gasoline cuts from Healy et
al.(1959) were used. The binary interaction parameters between components for
research and motor octane number derived from this large databank of gasoline
blends are given in Tables 5A and 5B. The overall average absolute deviation
percent (AAD%) for all 161 blends from 157 gasoline cuts is only 1.00% for
research octane number and 1.19% for motor octane number. These results
indicate that the proposed methodology enables the new correlation to
accurately predict octane number of a large number of very different gasoline
blends using only 3 generalized binary interaction parameters.

13
Table 5A
The universal set of the binary interaction parameters between components for
RON
--------------------------------------------------------------------------------------------------
kOA = 0.0670
kOS =-0.1021 kAS = -0.0232
--------------------------------------------------------------------------------------------------

Table 5B
The universal set of the binary interaction parameters between components for
MON
--------------------------------------------------------------------------------------------------
kOA = 0.0354
kOS =-0.0800 kAS = 0.0271
--------------------------------------------------------------------------------------------------

The increase of the AAD% of predicted research octane number from 0.5%
for blends from one group to 1.00% for all blends from all groups was not
unexpected. The contents of each gasoline cut are very complex and each cut
contains many different types of hydrocarbons. In spite of this complexity, the
laboratory analysis lumps the contents of each gasoline cut into only three
hydrocarbon types. The slight AAD% increase for all blends from all groups
may be due to this insufficient data analysis for gasoline cuts or data
inconsistency between groups. If the contents of the gasoline cut can be
analyzed in more detail in the laboratory analysis, the accuracy of prediction of
the octane number of the blends is expected to increase. Due to this data
inconsistency between groups, it is advised that it would be advantageous to re-
evaluate the binary interaction parameters for the specific group of blends by
optimization techniques if increased accuracy is desired. However, considering
the minimum information used in the equation, the accuracy of the prediction of
octane number from this work for any kind of gasoline blends is excellent.

Conclusion
We have shown that an interaction based correlation using the proposed
approach can be used to predict the research or motor octane numbers of

14
gasoline blends. An ultimately detailed analysis of gasoline cut is not necessary.
The correlation can describe blending behavior over the entire composition
range of gasoline cuts. The component type-oriented interaction approach is
general and will predict accurately, without doing additional blending study,
blending behavior for new gasoline cut.

The correlation proposed in this work has been found to fit the data quite
closely for blends of many gasoline cuts. The regression gives realistic values
for the binary interaction parameters between components. A unique set of
binary interaction parameters was found for the equation for the prediction of
octane number of any gasoline blends. The binary interaction parameters
between components contained in gasoline cuts have been converted to binary
interaction parameters between gasoline cuts through a general equation to
simplify the calculations of gasoline blends.

Because of the accuracy of the proposed method in the prediction of octane

numbers, the optimum allocation of components among gasoline grades can be
obtained and the predicted values can be used for quality control of the octane
number of marketed gasolines.

References
Auckland, M.H.T. and Charnock, D.J., “The Development of Linear Blending
Indices for Petroleum Properties”, J. of the Inst. of Petroleum, 55(545), 322-
329 (1969).
Healy, Jr.W.C., Maassen, C.W., and Peterson, R.T., “A New Approach to
Blending Octanes”, API Division of Refining, 24th midyear meeting, New
York, May 27, 1959.
Morris, W.E., “Interaction Approach to Gasoline Blending”, NPRA Paper AM-
75-30, National Petroleum Refiners Association annual meeting, March 1975.
Redlich, O. and Kister, A.T., “Thermodynamics of Nonelectrolytic Solution.
Algebraic Representation of Thermodynamic Properties and Classification of
Solutions”, Ind. Eng. Chem. 40, 345-348 (1948).
Rusin, M.H., Chung, H.S., and Marshall, J.F., “A Transformation Method for
Calculating the Research and Motor Octane Numbers of Gasoline Blends”,
Ind. Eng. Chem. Fundam., 20(3), 195-204 (1981).

15
Schoen, W.F. and Mrstik, A.V., “Calculating Gasoline Blend Octane Ratings”,
Ind. and Engr. Chem., 47(9), 1740-1742 (1955).
Stewart, W.E., “Predict Octanes for Gasoline Blend”, Petroleum Refiner,
38(12), 135-139 (1959).
Twu, C.H., Bluck, D., Cunningham, J.R., and Coon, J.E., 1991. "A Cubic
Equation of State with a New Alpha Function and a New Mixing Rule", Fluid
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Zahed, A.H., Mullah, S.A., and Bashir, M.D., “Predict Octane Number for
Gasoline Blends”, Hydrocarbon Processing, 85-87, May 1993.

16
 96

Octane Number of Blend

94

92

90
0.00 0.20 0.40 0.60 0.80 1.00
Volum e Frac tion of Component 1
Figure 1. The blending c orrelation in this work simulates the symmetrically
pos itive deviation of blending behav ior with k12 = -0.12 and k 21 =-0.12

90
Octane Number of Blend

88

86

84
0.00 0.20 0.40 0.60 0.80 1.00
Volume Fraction of Component 1
Figure 2. The blending correlation in this work simulates the symmetrically
negative deviation of blending behavior with k12 =0.12 an d k =0.12
21

96

94
Octane Number of Blend

92

90

88

86
0.00 0.20 0.40 0.60 0.80 1.00
Volume Fraction of Component 1
Figure 3. The blending c orrelation in this w ork sim ulates the pos itive and
negative deviation of blending behavior with k12 =- 0.25 an d k21 =0.18

17
 98

96
Octane Number of Blend

94

92

90
0.00 0.20 0.40 0.60 0.80 1.00
Volume Fraction of Component 1

Figure 4. The blending correlation in this work simulates the asymmetrically

positive deviation of blending behavior with k =-0.30 and k =0.00
12 21

90

88
Octane Number of Blend

86

84

82
0.00 0.20 0.40 0.60 0.80 1.00
Volume Fraction of Component 1

Figure 5. The blending correlation in this work simulates the asymmetrically

negative deviation of blending behavior with k =0 .30 and k =0.00
12 21

100

80
Octane Number of Blend

60

40

20

0
0.00 0.20 0.40 0.60 0.80 1.00
Volume Fraction of Component 1

Figure 6. The blending correlation in this work reproduces exactly the blending
behavior of isooctane and n-heptane binary with k =0 a nd k =0
12 21

18