Chemical Engineering Science 80 (2012) 402–408

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Chemical Engineering Science

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A statistical method for evaluation of the experimental phase equilibrium

data of simple clathrate hydrates
Ali Eslamimanesh a, Farhad Gharagheizi b, Amir H. Mohammadi a,c,n, Dominique Richon c,d
a
MINES ParisTech, CEP/TEP-Centre Énergétique et Procédés, 35 Rue Saint Honoré, 77305 Fontainebleau, France
b
Department of Chemical Engineering, Buinzahra Branch, Islamic Azad University, Buinzahra, Iran
c
Thermodynamics Research Unit, School of Chemical Engineering, University of KwaZulu-Natal, Howard College Campus, King George V Avenue, Durban 4041, South Africa
d
Technical University of Denmark, Center for Energy Resources Engineering (CERE), Department of Chemical and Biochemical Engineering, DK-2800 Kgs. Lyngby, Denmark

H I G H L I G H T S

c Leverage method is applied for evaluation of experimental phase equilibrium data.

c Experimental phase equilibrium data of various simple clathrate hydrates are studied.
c 5 hydrate dissociation data are found to be probable doubtful ones.
c 10 data points are designated as out of applicability domain of the correlation.

a r t i c l e i n f o a b s t r a c t

Article history: We, herein, present a statistical method for diagnostics of the outliers in phase equilibrium data
Received 11 March 2012 (dissociation data) of simple clathrate hydrates. The applied algorithm is performed on the basis of the
Received in revised form Leverage mathematical approach, in which the statistical Hat matrix, Williams Plot, and the residuals of
6 June 2012
a selected correlation results lead to define the probable outliers. This method not only contributes to
Accepted 13 June 2012
outliers diagnostics but also identifies the range of applicability of the applied model and quality of the
Available online 27 June 2012
existing experimental data. The available correlation in the literature in exponential form is used to
Keywords: represent/predict the hydrate dissociation pressures for three-phase equilibrium conditions (liquid
Evaluation of data water/ice–vapor-hydrate). The investigated hydrate formers are methane, ethane, propane, carbon
Gas hydrate
dioxide, nitrogen, and hydrogen sulfide. It is interpreted from the obtained results that the applied
Leverage approach
correlation for calculation/estimation of the phase behavior of simple clathrate hydrate systems is
Hat matrix
Williams plot statistically valid and correct, 5 hydrate dissociation data are found to be probable doubtful ones and 10
Outlier diagnostics data points are out of applicability domain of the applied correlation.
& 2012 Elsevier Ltd. All rights reserved.

1. Introduction
Clathrate (gas) hydrates are inclusion compounds composed of
H2O and guest species (Sloan and Koh, 2008). They are normally
stabilized by the guest molecules (can be either gas or special
liquids) enclathrated in the hydrogen-bonded water cages. At
relatively high pressures and low temperatures, water molecules
form various crystalline structures generally depending on the
size and shape of the guest molecule(s) (Sloan and Koh, 2008).
Structures I (sI), II (sII), and H (sH) are known to form as three
common structures of clathrate hydrates.
n
Corresponding author at: MINES ParisTech, CEP/TEP-Centre Énergétique et
Procédés, 35, Rue Saint Honoré, 77305 Fontainebleau, France.
Tel.: þ33 1 64 69 49 70; fax: þ 33 1 64 69 49 68.
E-mail address: amir-hossein.mohammadi@mines-paristech.fr
(A.H. Mohammadi).
The first industrial importance of the gas hydrate formation has
been attributed to the blockage of gas/oil transportation lines in
petroleum industry in the early 1930s (Sloan and Koh, 2008;
Hammerschmidt, 1934). More rigorously, gas hydrate formation
may occur during the steps of production and processing of natural
gas when traceable amounts of associated water exist (even in the
form of very low water content). Furthermore, novel technologies
utilizing gas hydrates have attracted much attention in the recent
years (called positive applications) (Sloan and Koh, 2008;
Eslamimanesh et al., 2012a). For instance, these clathrate structures
may be used as media for the storage and transportation of natural
gas and hydrogen (Sloan and Koh, 2008; Eslamimanesh et al., 2012a).
With respect to the aforementioned points, accurate and reliable
phase equilibrium data are required to design the most efficient
processes (either to prevent gas hydrate formation or to use it as a
promising technique for other applications) and to adjust the para-
meters of the developed models (thermodynamic/numerical ones) for
the corresponding phase equilibrium calculation/prediction.

0009-2509/$ - see front matter & 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ces.2012.06.019
 A. Eslamimanesh et al. / Chemical Engineering Science 80 (2012) 402–408
Experimental phase equilibrium data (mainly dissociation data)
for simple clathrate hydrate systems e.g. CH4, C2H6, C3H8, CO2, N2,
H2S, etc. have been extensively reported in the literature (Sloan
and Koh, 2008). Different experimental techniques have been thus
far applied for obtaining these data (Sloan and Koh, 2008;
Eslamimanesh et al., 2012a).
Although the quantities of these reported data seem to be
adequate for industrial applications, there may be no general
method to check their qualities. However, two methods have
been already employed to check the reliability of phase equili-
brium data of the systems containing gas hydrates as follows:
(1) The sketch of logarithm of dissociation pressure (log(p)) vs.
reciprocal temperature (1/T) generally exhibits a straight line
(which shows the value of the enthalpy of hydrate formation).
Thus, the hydrate dissociation data for any of the simple
hydrate formers can be sketched to observe whether they
show the same trends or not (Eslamimanesh et al., 2011a).
(2) Thermodynamic consistency test is generally applied as a
reliable method for assessment of the phase equilibrium data
quality. Very recently, we performed consistency test method
for the first time on significant systems including water content
of methane in equilibrium with gas hydrate, liquid water or ice,
(Eslamimanesh et al., 2011b), solubility data of carbon dioxide
and methane with water inside and outside gas hydrate forma-
tion region, (Eslamimanesh et al., 2011c) and composition of
vapor phase in equilibrium with gas hydrate and liquid water
for the carbon dioxideþmethane or nitrogenþwater systems
(Eslamimanesh et al., 2012b). However, the preceding method is
generally applicable only in the case of applicability of molar
compositions of equilibrium phases. It is worth pointing out that
the studied phase equilibrium data include the molar composi-
tions of the phases which are not necessarily the hydrate
dissociation conditions. Such data are very scarce in the open
literature. As a consequence, this method may not be an efficient
technique of our concern in this work (Belandria et al., 2011).
Hence, it is of much interest to propose a statistically-correct
method for simultaneous detection of the doubtful data and their
quality along with checking the validity and domain of applicability
of an available correlation (in exponential form) for representation/
prediction of the phase equilibrium data of simple clathrate
hydrates. In the present study, we use the Leverage approach
(Rousseeuw and Leroy, 1987; Goodall, 1993; Gramatica, 2007) for
this purpose. To the best of our knowledge, this is the first time that
a statistical method is used for evaluation of such data.
2. Theory
2.1. Leverage approach
As mentioned in our previous work, outlier diagnostics
(or detection) may be crucial in developing the mathematical
models (Rousseeuw and Leroy, 1987; Goodall, 1993; Mohammadi
et al., 2012). Outlier detection is to identify individual datum (or
groups of data) that may differ from the bulk of the data present in
a dataset (Rousseeuw and Leroy, 1987; Goodall, 1993;
Mohammadi et al., 2012). The proposed methods for this purpose
normally consist of numerical and graphical algorithms
(Rousseeuw and Leroy, 1987; Goodall, 1993; Mohammadi et al.,
2012). One of the efficient and reliable statistical algorithm for
outlier diagnostics is the Leverage approach (Rousseeuw and
Leroy, 1987; Goodall, 1993; Gramatica, 2007). The employed
elements of this method includes the values of the residuals (i.e.
the deviations of a model results from the experimental data) and
403
a matrix known as Hat matrix composed of the experimental data
and the represented/predicted values obtained from a correlation
(model) (Rousseeuw and Leroy, 1987; Goodall, 1993; Mohammadi
et al., 2012). Hence, a suitable mathematical model is also required
to pursue the calculation steps of the algorithm.
The Leverage or Hat indices are determined as a Hat matrix (H)
with the following definition (Rousseeuw and Leroy, 1987; Goodall,
1993; Mohammadi et al., 2012; Gharagheizi et al., 2012):
H ¼ XðX t XÞ1 X t ð1Þ
where X is a two-dimensional matrix composing n chemicals or data
(rows) and k parameters of the model (columns) and t stands for the
transpose matrix. The Hat values of the chemicals in the feasible
region of the problem are, as a matter of fact, the diagonal elements of
the H matrix.
The Williams plot is later sketched for graphical identification
of the suspended data or outliers on the basis of the calculated H
values through Eq. (1). This plot shows the correlation of Hat
indices and standardized cross-validated residuals (R), which are
defined as the difference between the represented/predicted
values and the implemented data (Rousseeuw and Leroy, 1987;
Goodall, 1993; Mohammadi et al., 2012; Gharagheizi et al., 2012).
A warning Leverage (H) is generally fixed at the value equal to 3 n/
p, where n is number of training points and p is the number of
model (correlation) input parameters plus one (Rousseeuw
and Leroy, 1987; Goodall, 1993; Mohammadi et al., 2012;
Gharagheizi et al., 2012). The leverage of 3 is normally considered
as a ‘‘cut-off’’ value to accept the points within73 range (two
horizontal red lines) standard deviations from the mean (to cover
99% normally distributed data) (Rousseeuw and Leroy, 1987;
Goodall, 1993; Mohammadi et al., 2012; Gharagheizi et al.,
2012). Existence of the majority of data points in the ranges
0 r H r Hn and 3 r Rr 3 reveals that both model development
and its representations/predictions are done in applicability
domain, which results in a statistically valid model. ‘‘Good High
Leverage’’ points are located in domain of Hn r H and 3 r Rr 3.
The Good High Leverage can be designated as the ones, which are
outside of applicability domain of the applied model (Rousseeuw
and Leroy, 1987; Goodall, 1993; Mohammadi et al., 2012;
Gharagheizi et al., 2012). In other words, the model is not able
to represent/predict the following data at all. The points located
in the range of R o  3 or 3 oR (whether they are larger or smaller
than the Hn value) are designated as outliers of the model or
‘‘Bad High Leverage’’ points. These erroneous representations/
predictions can be attributed to the doubtful data (Rousseeuw
and Leroy, 1987; Goodall, 1993; Gharagheizi et al., 2012).
2.2. Correlation
As the Leverage approach (Rousseeuw and Leroy, 1987; Goodall,
1993; Gramatica, 2007) seems to have been developed for checking
the applicability domain of the models merely based on the numer-
ical regressions, we have used the following recommended simple
correlation to represent/predict the corresponding phase equilibrium
data (Sloan and Koh, 2008; Kamath, 1984)
p=MPa ¼ 103 expða þ b:T 1 =KÞ ð2Þ
where p stands for the dissociation pressure, T is the dissociation
temperature, and a and b are the parameters of the correlation, which
are reported in Table 1. (Sloan and Koh, 2008; Kamath, 1984). It
should be noted that the range of dissociation temperatures and the
phase equilibrium regions, for which Eq. (2) has been recommended
are also presented in Table 1 (Sloan and Koh, 2008; Kamath, 1984).
404 A. Eslamimanesh et al. / Chemical Engineering Science 80 (2012) 402–408

3. Experimental data
Selected experimental gas hydrate dissociation data (Mohammadi
et al., 2005; Nakamura et al., 2003; Kharrat and Dalmazzone, 2003;
Yang et al., 2001; Ohmura et al., 2002; Jager and Sloan, 2001; Jager,
2001; Nixdorf and Oellrich, 1997; Hachikubo et al., 2002; Servio et al.,
2000; Guo et al., 1992; Reamer et al., 1952; Roberts et al., 1940;
Englezos, 1991; Clarke and Bishnoi, 2000; Avlonitis, 1988; Deaton and
Frost, 1946; Galloway et al., 1970; Falabella, 1975; Mooijer-van den
Heuvel et al., 2002; Robinson and Mehta, 1971; Verma et al., 1975;
Patil, 1987; Kubota et al., 1984; Englezos and Ngan, 1993; Platteeuw
and van der Waals, 1959; Holder and Kamath, 1982; Wendland et al.,
1999; Fan and Guo, 1999; Fan et al., 2000; Yoon and Lee, 1997; Komai
et al., 1997; Ohgaki et al., 1993; Sugahara et al., 2003; Mohammadi
and Richon, 2010; Selleck et al., 1952; Bond and Russell, 1948; Von
Stackelberg, 1949; Mohammadi and Richon, 2009; Marshall et al.,
1964; Wendland et al., 1999) for the systems containing simple
hydrate formers (CH4, C2H6, C3H8, CO2, N2, H2S) in liquid water–
hydrate–vapor (Lw–H–V) and ice–hydrate–vapor (I–H–V) regions
have been treated in this work. Table 2 reports the ranges of the
experimental data along with their sources.
data are generally acceptable to be used for the Leverage statistical
approach (Rousseeuw and Leroy, 1987; Goodall, 1993; Gramatica,
2007).
To pursue our objectives, the H values have been calculated
through Eq. (1) and the Williams plots have been sketched in
Figs. 1–12. All the calculated H and R values are presented in several
tables in the Supporting Information. The warning Leverages (H*)
have been fixed at 3 n/p for the whole data. In addition, the
recommended cut-off value of 3 has been applied (Belandria et al.,
2011; Rousseeuw and Leroy, 1987; Goodall, 1993).
The following results are interpreted from application of the
aforementioned methodology
(1) Accumulation of the data points in the ranges 0 rH rH* and
3 rR r 3 for each dissociaiton datasets of the investigated
simple hydrate formers reveals that the applied correlation is

4. Results and discussion

The absolute relative deviations of the correlation results from the

experimental values are presented in several tables in the Supporting
Information. As can be seen, the deviations of the correlation
representations/predictions from the corresponding experimental

Table 1
Parameters of Eq. (2) (Kamath, 1984) along with the ranges of applicability
(reproduced from (Sloan and Koh, 2008)).

Equilibrium Temperature a b
region range of
applicability/K

Methane Lw–H–V 273.15 to 298.15 38.98  8533.80

Methane I–H–V 248.15 to 273.15 14.717  1886.79 Fig. 1. Detection of the probable doubtful experimental data (Mohammadi et al.,
Ethane Lw–H–V 273.15 to 287.15 44.273  10,424.25 2005; Nakamura et al., 2003; Mohammadi et al., 2003; Kharrat and Dalmazzone,
Ethane I–H–V 248.15 to 273.15 17.511  3104.54 2003; Yang et al., 2001; Ohmura et al. 2002; Jager and Sloan, 2001; Jager, 2001;
Propane Lw–H–V 273.15 to 278.15 67.13  16,921.84 Nixdorf and Oellrich, 1997) and the applicability domain of the applied correlation
Propane I–H–V 248.15 to 273.15 17.156  3269.65 for the CH4 clathrate hydrate system in the Lw–H–V region. The H* value is 0.073.
Isobutane Lw–H–V 273.15 to 274.65 61.74  15,571.43 See the supporting information for references of the out of leverage and
Isobutane I–H–V 248.15 to 273.15 18.95  3887.32 suspended data.
Carbon dioxide Lw–H–V 273.15 to 284.15 44.58  10,246.28
Carbon dioxide I–H–V 248.15 to 273.15 18.594  3161.41
Nitrogen Lw–H–V 273.15 to 298.15 37.808  7688.63
Nitrogen I–H–V 248.15 to 273.15 15.129  1504.28
Hydrogen sulfide Lw–H–V 273.15 to 298.15 34.828  8266.10
Hydrogen sulfide I–H–V 248.15 to 273.15 16.56  3270.41

Table 2
Range of experimental data treated in this work.

Hydrate former Equilibrium Range of Range of

region temperature/K pressure/MPa

Methane (Lw þH þ V) 273.49–298.68 2.716–50.54

Methane (I þH þ V) 268.4–271.28 2.324–2.513
Ethane (Lw þH þ V) 273.4–287.61 0.545–3.244
Ethane (I þH þ V) 200.8–272 0.008–0.457
Propane (Lw þH þ V) 273.25–278.55 0.172–0.547
Propane (I þH þ V) 251.4–272.9 0.058–0.172
Carbon dioxide (Lw þH þ V) 273.36–283.05 1.31–4.1
Carbon dioxide (I þH þ V) 263.17–271.23 0.774–1.037
Nitrogen (Lw þH þ V) 273.67–309.43 16.93–439
Nitrogen (I þH þ V) 261.7–270.2 11.25–13.8
Hydrogen sulfide (Lw þH þ V) 272.8–302.7 0.093–2.239 Fig. 2. Detection of the probable doubtful experimental data (Hachikubo et al.,
Hydrogen sulfide (I þH þ V) 250.5–272.8 0.034–0.093 2002) and the applicability domain of the applied correlation for the CH4 clathrate
hydrate system in the I–H–V region. The H* value is 1.500.
 A. Eslamimanesh et al. / Chemical Engineering Science 80 (2012) 402–408
Fig. 3. Detection of the probable doubtful experimental data (Servio et al., 2000;
Galloway et al., 1970) and the applicability domain of the applied correlation for
the C2H6 clathrate hydrate system in the Lw–H–V region The H* value is 0.077. See
the supporting information for references of the out of leverage and suspended
data.
Fig. 4. Detection of the probable doubtful experimental data (Roberts et al., 1940;
Deaton and Frost, 1946; Falabella, 1975) and the applicability domain of the
applied correlation for the C2H6 clathrate hydrate system in the I–H–V region. The
H* value is 0.545.
statistically correct and valid for representation/prediction of
these experimental values.
(2) The whole hydrate dissociation data points can be declared to
within the applicability domain of the correlation except one
point in the corresponding data of carbon dioxide clathrate
hydrates in LwþV þH region, three points of ethane hydrate
dissociation data in LwþV þH region, one point of hydrogen
sulfide hydrate dissociation data in Lw þVþH region, and five
points of methane hydrate dissociation data in Lw þV þH
region. In addition, good high leverage points are accumu-
lated in the domains of H* rHand 3 rR r 3. These points
may be declared to be outside of applicability domain of the
applied correlation though cannot be assigned as doubtful
experimental data. It should be noted that, in the case of
encountering with good high leverage points, it is
405
Fig. 5. Detection of the probable doubtful experimental data (Nixdorf and
Oellrich, 1997; Reamer et al., 1952; Deaton and Frost, 1946; Mooijer-van den
Heuvel et al., 2002; Robinson and Mehta, 1971; Verma et al., 1975; Patil, 1987;
Kubota et al., 1984; Englezos and Ngan, 1993) and the applicability domain of the
applied correlation for the C3H8 clathrate hydrate system in the Lw–H–V region.
The H* value is 0.088.
Fig. 6. Detection of the probable doubtful experimental data (Deaton and Frost,
1946; Platteeuw and van der Waals, 1959; Holder and Kamath, 1982) and the
applicability domain of the applied correlation for the C3H8 clathrate hydrate
system in the I–H–V region. The H* value is 0.316.
recommended to use/develop other models or correlations on
the basis of different theoretical concepts for their calcula-
tions/estimations in order to avoid estimation through biased
model calculations (Mohammadi et al., 2012).
(3) The data points located in the range of Ro  3 or 3oR (ignoring
their H values) are designated as outliers or bad high leverage
points, as already mentioned. All the hydrate dissociation data
for the investigated simple hydrate formers are valid (not
outliers) except one point in the corresponding data of carbon
dioxide clathrate hydrates in LwþVþH region, two points of
ethane hydrate dissociation data in LwþVþ H region, one point
of methane hydrate dissociation data in LwþVþH region, and
one point of nitrogen hydrate dissociation data in LwþVþ H
region. These erroneous representations/predictions can be
attributed to the doubtful hydrate dissociation data.
406 A. Eslamimanesh et al. / Chemical Engineering Science 80 (2012) 402–408
Fig. 7. Detection of the probable doubtful experimental data (Hachikubo et al.,
2002; Fan and Guo, 1999; Fan et al., 2000; Yoon and Lee, 1997; Komai et al., 1997;
Ohgaki et al., 1993) and the applicability domain of the applied correlation for the
CO2 clathrate hydrate system in the Lw–H–V region. The H* value is 0.857. See the
supporting information for references of the out of leverage and suspended data.
Fig. 8. Detection of the probable doubtful experimental data (Hachikubo et al.,
2002; Wendland et al., 1999) and the applicability domain of the applied
correlation for the CO2 clathrate hydrate system in the I–H–V region The H* value
is 0.857.
(4) The data points in the ranges H* r H and R o  3 or 3oR may
be designated as neither within the applicability domain of
the applied correlation nor valid data. In other words, these
data cannot be well calculated/estimated by the correlation
and meanwhile attributed as suspended data points. There is
one point of ethane hydrate dissociation data in Lw þV þH
region, one point of methane hydrate dissociation data in
LwþV þH region, and one point of corresponding data for
hydrogen sulfide clathrate hydrates in Lw þV þH region can
be categorized in this group.
(5) The quality of the treated data (even different data in the same
dataset) are different. The data with lower absolute R values
(near R¼0 line) and lower H values may be declared as the
more reliable experimental data (Mohammadi et al., 2012).
One element should not be omitted from our discussion.
In this work, we have studied selected phase equilibrium data
Fig. 9. Detection of the probable doubtful experimental data (Nixdorf and
Oellrich, 1997; Mohammadi et al., 2003; Sugahara et al., 2003; Marshall et al.,
1964) and the applicability domain of the applied correlation for the N2 clathrate
hydrate system in the Lw–H–V region The H* value is 0.109. See the supporting
information for references of the out of leverage and suspended data.
Fig. 10. Detection of the probable doubtful experimental data (Mohammadi and
Richon, 2010) and the applicability domain of the applied correlation for the N2
clathrate hydrate system in the I–H–V region. The H* value is 1.000.
available in open literature for the systems of interest. However,
we are well aware that perhaps not all of the experimental data
are fully trustable from an experimental point of view. This may
be due to the inaccuracy of the used experimental techniques,
as already mentioned. Furthermore, calibration of the pressure
transducers and temperature probes are significant factors in
defining the uncertainties of the experimental data, as explained
previously. As a matter of fact, the results also suggest that new
experimental techniques may lead to obtaining more reliable
compositional data. In the present work, as we were interested in
defining only the data quality (and the range of applicability of a
correlation), consequently, we have focused on assessment tests
while our objective has not been a comparison between the
different experimental methods. More meticulous investigations
should be made on the validity of the applied experimental
techniques in future works.
 A. Eslamimanesh et al. / Chemical Engineering Science 80 (2012) 402–408
Fig. 11. Detection of the probable doubtful experimental data (Selleck et al., 1952;
Mohammadi and Richon, 2009) and the applicability domain of the applied
correlation for the H2S clathrate hydrate system in the Lw–H–V region. The H*
value is 0.194.
Fig. 12. Detection of the probable doubtful experimental data (Platteeuw and van
der Waals, 1959; Selleck et al., 1952) and the applicability domain of the applied
correlation for the H2S clathrate hydrate system in the I–H–V region. The H* value
is 0.545.
5. Conclusion
A statistical method to evaluate the dissociation data for the
CH4, C2H6, C3H8, CO2, N2, H2S clathrate hydrates was proposed on
the basis of the Leverage statistical approach (Rousseeuw and
Leroy, 1987; Goodall, 1993; Gramatica, 2007). 12 hydrate dis-
sociation datasets from the literature were represented/predicted
by a recommended simple correlation (Kamath, 1984) to pursue
the calculation steps of the evaluation method (Rousseeuw and
Leroy, 1987; Goodall, 1993; Gramatica, 2007). The results show
that
(1) The applied correlation is valid and statistically correct.
(2) 10 points from the whole investigated hydrate dissociation
data are found to be out of the applicability domain of the
employed correlation.
407
(3) 5 hydrate dissociation data are designated as suspended
(probable doubtful) experimental data.
The aforementioned results can be further used to conclude
about the quality of the data points, which are supposed to be
applied in tuning the thermodynamic models to predict the phase
equilibrium of the treated hydrate formers.
Acknowledgment
Ali Eslamimanesh is grateful to MINES ParisTech for providing
him with a PhD scholarship.
Appendix A. Supporting information
Supplementary data associated with this article can be found in
the online version at http://dx.doi.org/10.1016/j.ces.2012.06.019.
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