Journal of Colloid and Interface Science 225, 494504 (2000)

doi:10.1006/jcis.2000.6764, available online at http://www.idealibrary.com on

Quantitative Determination of Asphaltenes and Resins in Solution

by Means of Near-Infrared Spectroscopy. Correlations
to Emulsion Stability
Harald Kallevik,,1 Olav M. Kvalheim, and Johan Sjoblom
Statoil R&D Centre, Rotvoll, N-7005 Trondheim, Norway; and Department of Chemistry, University of Bergen, Allegaten 41, N-5007 Bergen, Norway
Received May 25, 1999; accepted February 3, 2000

Near-infrared (NIR) spectroscopy in the range 11002250 nm

together with a latent-variable regression technique is used to analyze the content of asphaltene and resins in solution. It is shown that
this technique is capable of determining the amount of these components individually. w/o emulsions were prepared from the separated components of asphaltenes and resins from crude oils. The
stability was directly determined with the critical voltage in a dielectric instrumentation. The emulsion stability decreased linearly with
an increase in the resin/asphaltene ratio. A final linear model correlating the critical voltage and the analytical concentrations (from
the NIR spectra) could be established for this model system.

C 2000

Academic Press

Key Words: near-infrared spectroscopy; experimental design; pca;

pls; multivariate; crude oils; asphaltenes; resins; w/o emulsions;
high electric fields.

INTRODUCTION

Asphaltenes are defined by their solubility characteristics in

light alkanes such as pentane. Depending on their origin, they
can be quite polar and polarizable and can be dissolved in, for
example, toluene. Asphaltenes are known to cause a lot of problems during production, transport, and processing of crude oils
(1, 2). Depending on pressure and temperature conditions in the
reservoir, asphaltenes can either be in solution or be precipitated.
Normally, a reduction in pressure causes precipitation. A precipitation can in many cases jeopardize further exploitation and
field development. The precipitation may be considered as either
a reversible or irreversible process. The controversy in modeling
is due to the description of the ground state of the asphaltenes in
solution. The high-pressure state of the asphaltenes is considered
by several authors to be a true solution containing monomeric
asphaltene entities dissolved in crude oil. Hence, the precipitation will be a thermodynamically reversible process. However, a
competitive approach is to consider the solution of asphaltenes
as a suspension of small asphaltene micelles (2) or particles, i.e.,
a colloidal suspension. According to this approach, the precipitation will be a supersaturation of colloidal particles and hence
1

To whom correspondence should be addressed.

0021-9797/00 $35.00

C 2000 by Academic Press

Copyright
All rights of reproduction in any form reserved.

irreversible. The true nature of the asphaltene solution is most

likely depending on the existence of correct dispersing agents,
i.e., resins (2). The resin fraction can be defined by its solubility
in, For example, liquid propane (2) or by this its adsorption/
desorption characteristics on polar surfaces like hydrophilic silica (3). Without dispersing agents asphaltenes cannot be colloidally suspended in the crude oil. A higher amount of resins
will most likely dissolve the asphaltenes.
Essential for the asphaltene association is the nature of the
association media. Many authors have shown that an increasing amount of aromatic compound (toluene, xylene, etc.) in the
medium will favor monomerization (or oligomerization) of the
agglomerated asphaltenes (1, 2, 4, 5). This is due to a direct
uptake of the aromatic molecules in the agglomerate. At higher
contents of the aromatics the attraction forces in the agglomerate
will be too weak and disintegration will take place. Hence, the
nature of the surrounding media is essential on asphaltene association and the performance of the fluid. A dramatic consequence
of the formation of asphaltene particles is the stabilization of w/o
emulsions (69). It is well-known that very stable water-in-crude
oil emulsions is caused by an accumulation of small asphaltene
particles at the w/o interface, giving rise to particle and/or sterically stabilized w/o emulsions. These colloidal systems might
cause severe problems in the separators (10).
Near-infrared (NIR) spectroscopy in combination with multivariate regression techniques has proven valuable for studying complex chemical mixtures. NIR spectroscopy gives information about the chemical composition of the samples; thus,
multivariate regression can be used for relating the spectra to
properties of interest, e.g., amount of specific components. NIR
spectroscopy is also gaining popularity as a technique for online monitoring of chemical composition, e.g., in crude oil refineries. For an overview of applications and history of the NIR
technique, see McClure (11).
In this paper we investigate near-infrared spectroscopy as
a technique for separately quantifying the amount of both asphaltenes and resins in solution. We also study the emulsion
stability of samples containing asphaltene and resins and make
prediction models for the stability based on the near-infrared
spectra.

494

495

ASPHALTENES AND RESINS IN SOLUTION

It should be pointed out that the validity of our study is to

systems with rather low contents of asphaltenes and resins. A
most straightforward application of the findings in this paper is
the Norwegian and British sector in the North Sea.

to find such selective wavelengths in near-infrared spectra. The

solution to this problem might be multivariate regression where
several wavelengths are used to relate the spectra to the concentration of a specific component. The mathematical expression
for this can be written as

THEORY

y(n1) = f X(nm) + (n1) ,

Absorption and Scattering in the Near-Infrared Region

The NIR region covers the range between 780 and 2500 nm
(11002250 nm is used in this paper). In this region the system with asphaltene aggregates can undergo electronic transitions as well as vibrational overtone transitions. Table 1 gives an
overview of the peaks that correspond to the vibrational overtones and combination bands. In addition, we would expect an
extinction of the transmitted light due to the scattering ability
of the asphaltene particles, even when the sample is exposed
to ultrasonic treatment before the near-infrared measurements.
Mullins (12) showed that electronic transitions dominate the
attenuation of near-infrared light in crude oils. This finding is
strongly dependent on the size of the asphaltene aggregates.
Under the assumptions of slightly lossy particles in the Rayleigh
limit, the ratio between scattering and absorption scales with
r 3 (r = radius of the scattering aggregates). The scattering effect cannot be ruled out in a model system with a 20/80 (w/w)
toluene/decane mixture. In such a system, the aggregation kinetics and the resulting particle sizes may give rise to scattering
in the near-infrared region (13).
Data Analysis
Differentiation. First- and second-order differentiation of
the spectral data is common pretreatment of near-infrared spectra. First-order differentiation will remove additive shifts in the
data, and second-order differentiation will remove straight-line
shifts. The relation between absorbance and concentration is
not altered by differentiation. The increase in optical density
as a result of scattering is greatly reduced by this pretreatment
of the spectra. The optical density is defined here as the sum
of extinction of the transmitted light due to absorption or scattering. The differentiation procedure used in this work is the
Savitzky/Golay differentiation (14) included in the Sirius 6.1
software package (15).
Multivariate regression. The traditional way of relating
spectra to concentration is to determine one selective wavelength
where the absorbance is directly proportional to the concentration of the component of interest. However, it is often impossible
TABLE 1
Assignments and Positions (in nm) for Some Overtone
and Combination Bands
CH second overtone
CH combinations first overtone
CH first overtone
Combinations region

11251225
13501450
16251775
19502450

[1]

where X(nm) is the spectral data matrix, with n as the number

of spectra and m as the number of wavelengths. y(n1) is a vector containing the concentrations related to the corresponding
spectra. (n1) is the residual vector, the unexplained variation.
In multivariate least-squares regression a b(1m) vector is estimated so that the squared residual vector (n1) is minimized.
Equation [1] is then written as
y = Xb + .

[2]

b contains the regression coefficients for the m wavelengths. If

the X matrix is quadratic (n = m), the regression coefficients for
the m wavelengths can be calculated by
b = X1 y.

[3]

Generally, the matrix X is not quadratic, and the inverse of X

does not exist. X1 is then replaced by (XT X)1 XT . Equation [3]
is then written as
b = (XT X)1 XT y.

[4]

The inversion of (XT X)1 requires that the X matrix have full
mathematical rank. This is never the case for spectroscopic data
if we want to use the full spectral profile. Thus, we have to find
a new data matrix with the following properties: (1) It should
contain the spectral information of interest and (2) it should have
full mathematical rank. One technique for finding such a matrix
is briefly presented in the following paragraph.
Latent-variable regression techniques. Due to experimental noise spectroscopic data, matrices have a mathematical rank
equal to the number of spectra or to the number of wavelengths
(depending on which is the lowest). It is obvious that many of
these wavelengths contain the same information about the components in the sample. This dependence between wavelengths
gives the possibility of explaining the systematic spectral information by a small number of latent (underlying) variables.
Performing regression on latent variables solves the rank problem in multivariate linear regression. Partial least-squares (PLS)
regression is a latent-variable regression technique. PLS decomposes the X matrix into a set of uncorrelated latent variables, by
extracting the information in X that is correlated to the information in the y (response) vector. A general overview of latent
regression techniques can be found in the book by Martens and
Naes (16).


KALLEVIK, KVALHEIM, AND SJOBLOM

496

Model validation. The PLS prediction models in this work

are validated by a technique called cross validation (for a review
of this technique, see Efron and Gong (17)). Since we do not
have a supplementary set of test data, we construct one by the
following procedure: (1) Leave the first sample out of the calculation of the model. (2) Use the model to predict the sample
left out. (3) Repeat steps (1) and (2) for all the samples. This
gives a test data set with the same number of samples as the samples in the X matrix. The predicted values are compared with
the measured values and the sum of the squared differences is
a measure for the models predictive ability. The result of the
cross validation is in this work used for selecting the number of
latent variables.
METHODS

Chemicals
The crude oil was supplied from an Elf production field in
France. Decane, n-pentane, dichloromethane (DCM), methanol
(MeOH), and toluene were all of p.a. quality from Merck
Darmstadt, Germany. Silanol was obtained from Waters
Millipore Corp., and the electrolyte solution was prepared by
dissolving NaCl in distilled water, giving a salinity of 3.5%.
Extraction of Asphaltenes and Resins
The asphaltenes and resins were prepared by mixing the crude
and pentane (1 : 5) at room temperature. This mixture was centrifuged at 2400 rpm for 10 min. The precipitate is in the following defined as asphaltenes. The asphaltenes were then removed
and left at 50 C for 2 h. Two grams of silanol particles/milliliter
of crude were then added to the supernatant to adsorb the resin
fraction. The mixture was stirred, centrifuged at 1000 rpm for
3 min, and the supernatant removed. The particles were then
again mixed with pentane, stirred, and centrifuged at 1000 rpm
for 3 min. This procedure was repeated until the supernatant
was almost colorless. The process of desorption was done in
the same way as the washing, except for the use of a blend of
7% MeOH in DCM. The supernatant was collected at each step,
and the removal of the solvent was performed in a rotary evaporator at 70 C and then under a N2 atmosphere at room temperature.
Experimental Design
Table 2 gives the sample composition for the 16 experiments.
This experimental design is called a full factorial design with
two variables and four levels. The amount of asphaltenes is varied between 0 and 1.67 wt% of the total sample mass and the
amount of resins is varied between 0 and 3.33 wt%. The amount
of saltwater (3.5 wt% NaCl) is fixed to 8.0 g and the amount in
the oil phase is fixed to 12.0 g. The oil phase contains a 20/80
toluene/decane mixture (weight relation), in addition to the
asphaltenes and resins. The amount of the toluene/decane mixture is allowed to vary due to the obvious fact that all samples

TABLE 2
Full Factorial Design with Two Variables (Asphaltene and Resin)
and Four Levels (Amount of Asphaltenes and Resins Is Given in %
of the Total Oil Phase)
No.

Asphaltenes

Resins

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16

0.00
0.56
1.11
1.67
0.00
0.56
1.11
1.67
0.00
0.56
1.11
1.67
0.00
0.56
1.11
1.67

0.00
0.00
0.00
0.00
1.11
1.11
1.11
1.11
2.22
2.22
2.22
2.22
3.33
3.33
3.33
3.34

must sum to 100%. The effect of this variation is assumed negligible (3 wt% variation of the total) and will not be further
commented on in this work.
Preparation of the Oil Phase
Asphaltene and toluene were mixed in a sample container
and left to equilibrate for 2 h. The components decane and resin
were added one by one, with the same 2-h delay between each
step. Two days after the preparation, the samples were exposed
to 1 min of ultrasonic treatment just before the near-infrared
sampling. The use of time delays was to ensure equilibrium
conditions.
Near-Infrared Measurements
The near-infrared sampling of the model systems was performed with a NirSystems 6500 spectrophotometer, equipped
with a fiber optic sampling probe for transmission sampling.
The wavelength region was set to 11002250 nm. The total path
length in the cell was 1.2 mm. The sample was stirred during
sampling. The total number of scans per spectrum was set to 32.
Emulsification
The emulsions were prepared by adding 40 wt% water phase
(3.5% NaCl) to the 60 wt% oil phase (including asphaltenes
and resins), followed by mixing at 2400 rpm on a Silverson
Laboratory Mixer Emulsifier Model STD 1, using an emulsor
screen head, for 2 min.
Emulsion Stability Measurements
The emulsion stability toward coalescence was recorded by
the method and instrumentation described by Gestblom and

ASPHALTENES AND RESINS IN SOLUTION

Fordedal (6, 1821). The thickness of the emulsion layer in the

cell was 0.63 mm, and two or three measurements were performed on each sample.
Data Analysis
The spectroscopic data were analyzed using Sirius 6.1 (15)
and Matlab 4.2c.1 (22).
RESULTS AND DISCUSSION

General Spectral Observations

Figure 1 shows the near-infrared spectra of the 16 samples.
The spectra are numbered in accordance with the samples in
Table 2. In the following the spectra are divided in accordance
with composition: Group A (samples 2, 3, and 4) contains the
samples with asphaltenes only and Group R (samples 5, 9, and
13) resins only. Group M (samples 6, 7, 8, 10, 11, 12, 14, 15, and
16) contain both asphaltenes and resins. Sample 1 does not contain asphaltenes nor resins, and the spectral interpretation is in
accordance with Table 1. The addition of resins (group R) gives
rise to only small changes in the near-infrared spectrum. These
variations are further investigated in Fig. 2 where spectrum 1 is
subtracted from the spectra in Group R. The optical density (OD)
of the samples increases weakly with the addition of resins. This
can be explained by an increased absorption due to electronic
transitions (12, 23). The small size of the resin molecules should
imply that scattering is not important for this group. There also
occures some changes in the first CH overtone region and in
the CC combination region.

497

The changes inside Group A are more prominent. Addition

of asphaltenes reduces the optical density, and this is further
visualized in Fig. 3 (spectrum 1 subtracted). The spectra are
shifted toward higher optical density through the whole nearinfrared region. This is a result of the increased absorption due to
electronic transitions (12, 23), in combination with the increased
amount and size of scattering particles.
A study of the changes within Group M shows that addition
of resins reduces the optical density of samples containing asphaltenes (Fig. 1). Addition of resins may alter the absorbing
properties of the asphaltene aggregates, but it is more likely that
the reduction in OD is caused by a reduced size of the scattering
particles (12).
Figure 4 shows the result of second-order differentiation of
the near-infrared spectra. This procedure removes both additive
and linear shifts in the data. The effect of light scattering on the
spectra will be reduced after differentiation. To make a prediction model for the amount of asphaltenes and resins, the particle size/structure giving rise to scattering is of no interest. The
calculation of the prediction model is thereby performed on differentiated data. The differentiation will not influence any linear
relations between the concentration of interest and the spectra.
To illustrate this, Figs. 5 and 6 show the differentiated spectra
of Groups R and A, respectively. The differentiated spectra of
sample 1 is subtracted from the others.
Prediction Models for Amount of Asphaltenes and Resins
The prediction model for the asphaltenes is shown in Fig. 7.
Here, the known asphaltene concentrations are plotted against

FIG. 1. Near-infrared spectra of 16 model oil samples with asphaltenes and resins.

498

KALLEVIK, KVALHEIM, AND SJOBLOM

FIG. 2. Near-infrared spectra with corrected background (Group R).

FIG. 3. Background-corrected near-infrared spectra for Group A.

ASPHALTENES AND RESINS IN SOLUTION

FIG. 4. Second-order differentiated spectra for the 16 samples.

FIG. 5. Second-order differentiated spectra (Group R).

499

500

KALLEVIK, KVALHEIM, AND SJOBLOM

FIG. 6. Second-order differentiated spectra (Group A).

the predicted ones. This should give a straight line with an intercept equal to 0 and a slope equal to 1. Figure 8 shows the
regression coefficients (the b vector from Eq. [4]). The regression coefficients give weight to some of the regions with large
variation in Fig. 6, as expected. Figure 9 gives the prediction

FIG. 7. Prediction model for the amount of asphaltenes. Statistics: R 2 =

0.969; intercept = 0.03; total variance explained (2 PLS components) X, 98.8%
and Y, 96.8%.

model for the amount of resins in each sample. The regression

coefficients are given in Fig. 10, and they also follow the pattern
of the differentiated data in Fig. 4. The statistics of the regression
models are given in the figure captions. The R 2 is the multiple
regression coefficient. Both models have a high coefficient and
the intercepts are close to 0.

FIG. 8. Regression coefficients for the asphaltene prediction model.

501

ASPHALTENES AND RESINS IN SOLUTION

TABLE 3
The Design, the Resin/Asphaltene Ratio, and the Emulsion Stability

FIG. 9. Prediction model for the amount of resins. Statistics: R 2 = 0.904;

intercept = 0.16; total variance explained (2 PLS components) X, 98.9% and Y,
90.4%.

Emulsion Stability
The results of the emulsion stability measurements are listed
in Table 3. Figure 11 shows the stability as a function of the
amount of asphaltene in the oil phase. The general trend is that
the stability increases with the amount of asphaltenes. An increased amount of asphaltenes results in a larger number of
surface-active aggregates (and possible bigger aggregates). The
explanation for the increased emulsion stability is that a larger

FIG. 10. Regression coefficients for the resin prediction model.

No.

Asphaltenes

Resins

Res/Asp

E cr

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16

0.00
0.56
1.11
1.67
0.00
0.56
1.11
1.67
0.00
0.56
1.11
1.67
0.00
0.56
1.11
1.67

0.00
0.00
0.00
0.00
1.11
1.11
1.11
1.11
2.22
2.22
2.22
2.22
3.33
3.33
3.33
3.34

2.0
1.0
0.7

4.0
2.0
1.3

6.0
3.0
2.0

0.00
0.10
0.35
0.49
0.00
0.20
0.42
0.47
0.00
0.31
0.40
0.52
0.00
0.25
0.41
0.46

number of aggregates at the surface hinders the coalescence of

the water droplets. In Fig. 12 the emulsion stability is plotted as
a function of resin content in the oil phase. The general trend is
that addition of resins does not influence the emulsion stability in
this concentration region. The exception from this is the samples
with 0.56% asphaltene content where we observe an increase in
the stability from 0 to 2.22% resins, followed by a weak decrease
from 2.22 to 3.33% resins. To further investigate the reason for
this, the emulsion stability was plotted as a function of the ratio
between resins and asphaltenes. We had to exclude the samples
with 0% asphaltene and 0% resin content. The result is shown in
Fig. 13. The emulsion stability is generally decreasing with an
increasing resin/asphaltene ratio. However, sample 6 does not
follow this pattern and the results from the individual parallels
give no indications regarding the reason for this. The conclusion
must thus be that further investigations are required to conclude
on the overall relation between the resin/asphaltene ratio and the
emulsion stability.

FIG. 11. Emulsion stability as a function of asphaltene content.


KALLEVIK, KVALHEIM, AND SJOBLOM

502

FIG. 12. Emulsion stability as a function of resin content.

The 16 experiments can also be used for response surface

modeling. The known concentrations of asphaltene and resin,
together with the emulsion stability, provide us with the following second-order least-squares regression model:
E Critical = 0.06 + 0.48X asp + 0.07X res 0.10X asp asp
0.01X res res 0.01X asp res

[5]

E Critical are the estimated responses. X asp and X res are the
amounts of asphaltene and resin, respectively. X asp asp and
X res res are the second-order effects of adding the two components, and X asp res is the interaction term between them. The constant term, the interaction term between asphaltenes and resins,
and the second-order effect of adding resins are not significant
at a 90% confidence level. The multiple regression coefficient
(R 2 ) for this model is 0.9679, which indicates a good fit of the
experimental data. The response surface is shown in Fig. 14.
The general trend is a curved increase in the stability with the
addition of asphaltenes. The presence of resins gives rise to a
minor curvature of the response surface.

General DiscussionObserved Changes in Optical Density

and Emulsion Stability
Asphaltenes and resins form surface-active aggregates that
accumulate at the interface between water and oil. The size, the
structure, and the polarity of these aggregates will strongly influence the emulsion stability. Asphaltene aggregates are dissolved
upon addition of resins. The size of the aggregates will thereby be
a function of the resin-to-asphaltene ratio. Completely dissolved
asphaltene molecules or solutions with only resin present do not
give rise to stable emulsions. This means that the emulsion stability should decrease with the resin-to-asphaltene ratio. Addition
of resins to a solution with asphaltenes leads to an adsorption
of resin molecules to the asphaltene aggregates, followed by a
solvation effect. Less polar resin molecules will shield the polar
asphaltene aggregates. This effect influences the attraction of
asphaltenes to the water/oil interface and keeps them in the oil
phase. Fewer aggregates at the surface lower the resistance of the
surface film toward coalescence and thereby lower the emulsion
stability.
Prediction Models of Emulsion Stability Based
on NIR Spectra

FIG. 13. Emulsion stability as a function of the resin/asphaltene ratio.

The NIR spectra contain information on the amounts of asphaltenes and resins and also on the state of the asphaltene aggregates. Since these properties are important for emulsion stability,
we tried to model the stability from the original NIR spectra (not
from the differentiated spectra where information about the state
of the aggregates is deliberately removed). The result is shown in
Fig. 15 and the regression coefficients for the model are plotted
in Fig. 16. R 2 for this model is 0.784 and the intercept is 0.061.
The variance of the residuals is not uniform since we clearly see
a nonlinear structure relative to the regression line in Fig. 15.
This is no surprise since we already have shown that the relation
between the surface-active components and the emulsion stability is given by a second-order model (Eq. [5]). Reduction of
the nonlinear structure of the residuals was attempted by several

ASPHALTENES AND RESINS IN SOLUTION

503

FIG. 14. Response surface model. Statistics: R 2 = 0.9679.

y x transformations of the response. The results were not much

better than those of the original model and are therefore left out
of this manuscript. Instead, we have utilized the fact that we can
estimate the amounts of asphaltenes and resins from the NIR

spectra. These values can then be used to predict the emulsion

stability according to Eq. [5]. The result of this procedure is
shown in Fig. 17 and clearly this model is much better than the
one proposed in Fig. 15.

FIG. 15. Near-infrared prediction model for the emulsion stability. Statistics: R 2 = 0.784; intercept = 0.06; total variance explained (2 PLS components)
X, 99.7% and Y, 78.4%.

FIG. 16. Regression coefficients for the emulsion stability prediction model.


KALLEVIK, KVALHEIM, AND SJOBLOM

504

FIG. 17. NIR prediction model for the emulsion stability. Statistics: R 2 = 0.9406; intercept = 0.06.

CONCLUSIONS

In this work, we have shown that near-infrared spectroscopy

can give fast and reliable information about a fluid model system
containing asphaltenes and resins. NIR spectroscopy provides
both chemical and structural information, and this can be used
for predictions of the ability of the fluid to form stable emulsions.
ACKNOWLEDGMENTS
Harald Kallevik would like to acknowledge the Norwegian Research Council
(NFR) for a Ph.D. grant. The near-infrared spectrophotometer and the dielectric
instrumentation were also financed by NFR. Financial support from the industrial
participants in the Flucha program is also highly appreciated. Elf Aquitaine is
thanked for providing us with the crude.

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