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q Institution of Chemical Engineers
Trans IChemE, Vol 78, Part A, July 2000

GAS HYDRATE EQUILIBRIA OF 2,3-DIMETHYLBUTANE

AND BENZENE WITH METHANE AND NITROGEN
K. K. STERGAARD, B. TOHIDI, A. DANESH, A. C. TODD (FELLOW) and R. W. BURGASS
Department of Petroleum Engineering, Heriot-Watt University, Edinburgh, UK

our phase (liquid water, liquid hydrocarbon, vapour, hydrate structure-H) equilibrium
data are presented for 2,3-dimethylbutane in the presence of the help gases methane
and/or nitrogen. Also, further to a previous communication, four phase (liquid water,
liquid hydrocarbon, vapour, hydrate structure-II) equilibrium data are presented for benzene in
the presence of nitrogen, and a mixture of methane and nitrogen. The hydrate equilibrium data
are reported over the seabed temperature range (274288 K). Thermodynamic description and
Kihara potential energy parameters for 2,3-dimethylbutane and benzene are reported for
hydrate prediction purposes.
Keywords: hydrates; experimental; modelling; phase equilibria; state equation; statistical
thermodynamics

INTRODUCTION

data are accompanied by measurements of hydrate dissociation conditions for benzene in the presence of nitrogen and a
mixture of methane and nitrogen.
Structure-H (sH) hydrate dissociation data for 2,3dimethylbutane (2,3-DMB) in the presence of methane
have previously been reported by Mehta and Sloan6 in the
temperature range of 276281 K. This temperature range is
extended up to 287 K and, for the rst time, hydrate
dissociation data are reported for 2,3-DMB in the presence
of nitrogen and a mixture of methane and nitrogen.
The hydrate dissociation data of benzene and 2,3-DMB
with methane have been used in the optimization of the
Kihara potential energy parameters employed in a
thermodynamic model. The Kihara parameters previously
reported for benzene5 have been re-optimized in order to
use similar approaches in calculating hard core diameters
for all our reported HHFs. The experimental data
involving nitrogen have been used in the validation of
the model.

Gas hydrates are an increasingly important topic in oil and

gas industry. Their formation in well-tubing, subsea
pipelines, and production facilities could result in serious
operational and safety hazards. Recently, signicant attention has been given to positive aspects of gas hydrates, i.e.,
the application of gas hydrates in transportation of oil and
gas, the role of natural gas hydrates in sediments as a
potential source of energy, and their impact on global
climate changes.
Gas hydrates are so-called inclusion compounds in which
small gas molecules occupy and stabilize cavities formed by
water molecules. When different sized cavities arrange
themselves into crystals, different gas hydrates structures
appear. Gas hydrates, or more correctly, clathrate hydrates
have been reviewed in depth by Sloan1 .
Until recently, only two hydrate structures, structure-I (sI)
and structure-II (sII), were considered as being potential
hydrate structures in petroleum industry. Molecules not larger
than n-butane were considered as being potential hydrate
formers. This changed in the late 1980s when Ripmeester and
his group2,3 discovered a new hydrate structure, structure-H
(sH), which allows molecules as large as methylcyclohexane
to form gas hydrates. Ripmeester and his group also identied
potential new larger guests for hydrate sII.
Hydrate formers larger than n-butane are referred to as
heavy hydrate formers4. In order to stabilize the hydrate
structures, the majority of Heavy Hydrate Formers (HHFs)
need the presence of a help gas, e.g., methane or nitrogen. It
has been shown that even a small amount of HHF can have a
signicant impact on the hydrate free zone of real reservoir
uids4.
Benzene was included in the list of potential sII hydrate
formers in natural and industrial environments3. Experimental hydrate dissociation data for benzene hydrates were
for the rst time reported by Danesh et al.5 with methane as
the help gas. In this communication the benzene/methane

EXPERIMENTAL
Two different experimental facilities were used for
measuring experimental hydrate dissociation conditions,
enhancing the reliability of the generated data. Both rigs are
described in detail below.
Rig-1
Central to the facility is an equilibrium cell consisting of
a metal body inside which an optically clear quartz glass
tube is housed. A schematic cross section of the cell and
of the rig layout is shown in Figures 1 and 2, respectively.
The volume of the cell can be adjusted by injecting or
withdrawing mercury using a displacement pump. The
maximum effective cell volume is 540 cc and the maximum
working pressure is 69 MPa.
731

STERGAARD et al.

732

test, all four probes and the bath temperature are logged so
that any discrepancy can be detected.
The pressure of the cell is monitored by two strain gauge
pressure transducers mounted on the pump. With these
transducers, calibrated at intervals with a deadweight
tester, the pressure can be measured with an accuracy of
6 0.007 MPa. Pressure readings from the two transducers
are logged and compared, and any drift between calibrations
can be detected. All reported pressure readings are corrected
for any height difference between pressure sensors and test
uids.
The cell is mounted on a frame which allows a rocking
motion around a horizontal axis. Rocking the cell ensures
excellent mixing by ushing mercury through the test uids
from one end of the cell to another. For the tests reported in
this communication, the cell was rocked continuously at a
rate of 8 times per minute. A computer is used to acquire
temperature and pressure data, and to control the system. A
borescope can be passed into the quartz glass tube in order
to view the cell contents. A camera can be attached to the
borescope for recording purposes.
Rig-2
Figure 1. Schematic diagram of equilibrium cell, Rig-1.

The temperature of the cell is controlled by circulating an

aqueous ethylene glycol solution round a jacket surrounding
the cell. The jacket, as well as the connecting pipes, are
insulated in order to maintain good temperature stability,
which makes it possible to keep the temperature constant
to within 0.05 K. The temperature is monitored by four
platinum resistance probes, two implanted in the equilibrium cell (T1, and T2 in Figure 2) and two in the heating
jacket (T3, and T4 in Figure 2). The four temperature probes
are calibrated at intervals using a precision thermometer
with a reported accuracy of 6 0.025 K. Whilst running a

Figure 2. Schematic diagram of Rig-1.

A schematic of Rig-2 (designed and built in this

department) is shown in Figure 3. The system under
investigation is contained inside burnished stainless steel
cylinders between two pistons, the pistons being linked
by a stainless steel rod. The piston assembly is moved up
and down the cell by compressed air, a variable speed
pneumatic switch changes the air supply from end to end.
As the piston assembly moves up and down, the cell contents are forced through a central grid, generating a crushing
mixing action which ensures efcient mixing, reducing the
time required for equilibrium, and ensuring that gas and
liquid hydrocarbon are not trapped within the formed
hydrates.

Figure 3. Schematic diagram of Rig-2.

Trans IChemE, Vol 78, Part A, July 2000

GAS HYDRATE EQUILIBRIA OF 2,3-DIMETHYLBUTANE AND BENZENE

The cell, as for Rig-1, is contained in a bath of aqueous
ethylene glycol which is circulated by a cryostat keeping the
temperature constant within 6 0.05 K. Two probes measure
the temperature, one in the bath and one in the centre of the
cell.
The pressure is measured by a pressure transducer, which
has an accuracy of 6 0.002 MPa, mounted in the centre of
the cell. With the stainless steel cylinders the cell can be
worked at pressures up to 69 MPa. There is also an option of
replacing these with glass cylinders for direct observation of
hydrate formation/dissociation but only for use at pressures
up to 1.7 MPa. The cell volume can be varied according to
the length of the rod connecting the pistons with a maximum
effective volume of 400 cc. As for Rig-1 the temperatures
and pressures are logged and the temperature controlled
using a computer.
Rig-2 has additional capabilities of sampling and
analysing from any uid phase present in the cell. When a
sample is required for analysis, the pistons are positioned so
that the phase to be analysed is opposite a sampling valve
mounted in the centre of the cell. The sample is then passed
directly at the test pressure to a GC for compositional
analysis. While sampling, uid is pumped into the space
below the oating piston in order to maintain the cell
pressure despite sampling.
Procedure
The test procedure was the same for both rigs. Prior to the
tests the equilibrium cell was cleaned and evacuated. Water
and HHF were pumped into the cell using a HPLC pump
from a weighed container giving an accuracy of 6 0.01 g.
The gases were loaded gravimetrically as well, also with an
accuracy of 6 0.01 g. Table 1 summarizes the test uids
used in this work.
Once the cell had been charged with the desired
components the mixing was started and the temperature
lowered to form hydrates, their presence being conrmed
by pressure drop (and visually by use of the borescope in
Rig-1). The hydrate formation caused a rapid decline in the
cell pressure as gas molecules were consumed during the
process. The temperature was then increased stepwise,
slowly enough to allow equilibrium to be achieved at each
temperature step7. As temperature increases inside the
hydrate region, hydrates would dissociate, causing an
increase in the pressure of the cell. This was not the case
when the temperature was increased outside the hydrate
region. Here, only a small pressure increase was seen, due to
thermal expansion. Therefore, the point at which the
pressure plotted as a function of the temperature changed
sharply was considered the hydrate dissociation point. This
is illustrated by Figure 4 which shows a cooling/heating

733

Figure 4. Example of a P vs. T diagram for hydrate dissociation point

determination, methane/nitrogen/2,3-DMB.

cycle of a methane/nitrogen/2,3-DMB test. The procedure

was repeated at different pressures in order to determine
the hydrate phase boundaries over a wide temperature
range.
Five sets of hydrate dissociation data were measured in
this work, namely: 2,3-DMB with methane, 2,3-DMB with
nitrogen, 2,3-DMB with methane and nitrogen, benzene
with nitrogen, and benzene with methane and nitrogen. All
reported hydrate dissociation data are in four phase equilibrium conditions with water (L1), liquid hydrocarbon (L2),
vapour (V), and hydrates (sII or sH) present.
THERMODYNAMIC MODELLING
The experimental hydrate equilibrium conditions measured in this work were modelled by equation of state based
statistical thermodynamics. In general, for a chemical
system to be at thermodynamic equilibrium, the chemical
potential of each component throughout the system must be
uniform:
mi1 = . . . = mij = . . . = mip ,

i = 1, 2, . . . , N

(1)

where mij is the chemical potential of component i in phase j,

N is the number of components and p the number of phases.
For an isothermal system, equation (1) reduces to equality of
fugacity for each component in the different phases:
fi1 = . . . = fij = . . . = fip ,

i = 1, 2, . . . , N

(2)

In the most general case, i.e., when all components are

present in all phases, there will be N(p 1) such equations.

In addition, material balances impose another

set of N + p
equations:
p
X
zi =
Fj xij
(3)
j

and
Table 1. Test uids used in this work.
Component
Methane
Nitrogen
Benzene
2,3-Dimethylbutane
Water

Supplier

Purity

Air Products
BOC
Aldrich
Aldrich

Instrument grade 99.9% pure

99.99% pure
GPR grade 99+% pure
99+% pure
Double distilled

Trans IChemE, Vol 78, Part A, July 2000

N
X

xij = 1

(4)

where zi is the specied composition of the feed, Fj the

fraction in moles of phase j, and xij the mole fraction of
component i in phase j. In total, equations (2) to (4) result in
p(N + 1) equations with an equal number of unknowns.
In the present work, all uid phase fugacities were
calculated using the Valderrama modication of the Patel

STERGAARD et al.

734

and Teja cubic equation of state8 with a non-density

dependent mixing rule9. However, any other appropriate
method of evaluating uid phase fugacities could be
adopted. The modelling of the uid phase behaviour was
improved by optimizing Binary Interaction Parameters
(BIPs) based on Vapour-Liquid Equibria (VLE) and
Liquid-Liquid Equilibria (LLE) data available in the open
literature.
In order to calculate the hydrate phase fugacities, the
solid solution theory by van der Waals and Platteeuw10 was
employed. The fugacity of water in the hydrate phase is
given by:
fwH = fwb exp

D mbw H

RT

(5)

where fwb is the fugacity of water in the empty hydrate lattice,

and R and T are the gas constant and absolute temperature,
respectively. The term, D mbw H , is the difference of the
chemical potential of water between the empty hydrate
lattice, mbw , and the hydrate phase, mHw , and is obtained from
the van der Waals and Platteeuw expression11:
!
X
X
b
H
b
H
D mw = mw mw = RT
vm ln 1 +
Cjm fj

m
j

RESULTS AND DISCUSSION

The four phase (L1-L2-V-sH) hydrate dissociation conditions for 2,3-DMB with methane and nitrogen are given in
Tables 2 and 3, respectively. The compositions of these
systems are not required, as, according to the Gibbs phase
rule, four phase equilibrium points of ternary mixtures are
compositional independent. Likewise, the measured four
phase (L1-L2-V-sII) equilibria data for the nitrogen/benzene/
water systems are given in Table 4.
The hydrate dissociation conditions for 2,3-DMB and
benzene with both methane and nitrogen present are
composition-dependent. Tables 5 and 6 present the feed
composition and hydrate dissociation conditions for these
systems.
Mutual solubility data of benzene and water21, and
2,3-DMB and water22,23 were used for optimization of the
corresponding BIPs. Figures 5 and 6 present experimental
and predicted mutual benzene/water and 2,3-DMB/water
solubility data. The predictions are seen to be in good
agreement with the experimental data.
Binary VLE data were used to optimize the BIPs for
benzene with methane and nitrogen25,26. Examples of
experimental and predicted phase equilibria for these
systems are presented in Figures 7 and 8. There were no

(6)

where vm is the number of cavities of type m per water

molecule in the unit cell, fj is the fugacity of the gas
component j. Cjm is the Langmuir constant, which accounts
for the gas-water interaction in the cavity. Numerical values
for the Langmuir constant can be calculated by choosing a
model for the guest-host interaction10:

4p
w(r) 2
Cjm (T) =
exp
r dr
(7)
kT
kT

Table 2. Dissociation conditions

for methane/2,3-dimethylbutane
sH gas hydrates.
T/K

P/MPa

276.1
280.0
283.1
286.9

2.206
3.613
5.392
8.963

where k is Boltzmanns constant. The function w(r) is the

spherically symmetric cell potential in the cavity, with r
measured from the centre, and depends on the intermolecular potential function chosen for describing the encaged
gas-water interaction. In the present work, the Kihara
potential function12 is used as described in McKoy and
Sinanoglu13.
The fugacity of water in the empty hydrate lattice, fwb in
equation (5) is given by:
fwb = fwL exp

D mbw L
RT

Table 3. Dissociation conditions

for nitrogen/2,3-dimethylbutane
sH gas hydrates.
T/K

P/MPa

275.8
278.4
282.0
285.3

10.177
13.858
20.850
30.358

(8)

where fwL is the fugacity of liquid water and Dmbw L is

the difference in the chemical potential between the
empty hydrate lattice and pure liquid water14.
The simplex optimization algorithm was used to optimize
BIPs as well as Kihara potential function parameters. The
optimization of the Kihara parameters was restricted to
the collision diameter (s) and the energy parameter ( ), as
Holder and Hand, 198215 showed that the results are not
signicantly affected by minor changes in the third Kihara
parameter, i.e., the hard core radius (a). The latter was
instead calculated using correlations by Tee et al.16. Detailed
descriptions can be found in Tohidi17 and Avlonitis18.
Various thermodynamic reference properties for the different
hydrate structures are listed in Tohidi et al.19 and Tohidi
et al.20.

Table 4. Dissociation conditions

for nitrogen/benzene sII gas
hydrates.
T/K

P/MPa

274.0
274.4
275.3
275.6
275.7
276.9
277.3
279.9
283.0
285.3

7.067
7.481
8.489
8.329
8.349
10.280
10.376
13.838
20.718
27.358

Trans IChemE, Vol 78, Part A, July 2000

GAS HYDRATE EQUILIBRIA OF 2,3-DIMETHYLBUTANE AND BENZENE

735

Table 5. Dissociation conditions for

methane/nitrogen/2,3-dimethylbutane
sH gas hydrates.

Table 7. Kihara parameters for methane, nitrogen, 2,3-DMB, and benzene.

Component

a/ A

s*/A

ek-1/K

T/K

P/MPa

277.7
281.4
284.9
287.9

4.095
6.750
11.059
17.333

Methane#
Nitrogen#,
2,3-DMB
Benzene

0.2950
0.3350
1.0981
0.9188

3.2512
3.2171
3.8200
3.5900

153.685
128.390
166.851
264.209

From Tohidi17.
Simple nitrogen hydrates are modelled as sI in the L1-H-V region17.

s = s 2a.

Feed
composition
(mole%):
methane = 15.48, nitrogen = 11.77,
2,3-dimethylbutane= 5.67, water =
67.08.

Table 6. Dissociation conditions

for methane/nitrogen/benzene sII
gas hydrates.
T/K

P/MPa

280.0
282.1
284.6

4.151
5.633
8.253

Feed composition (mole%):

methane = 12.26, nitrogen = 6.34,

experimental binary VLE data available for the methane/

2,3-DMB and nitrogen/2,3-DMB systems, therefore, the
BIPs for these binary systems were set to zero.
The Kihara potential parameters for 2,3-DMB and
benzene were optimized using their hydrate dissociation
data with methane, whereas the data sets including nitrogen
have only been used for validation purposes. Corresponding
Kihara potential parameters for all hydrate formers included
in this work are listed in Table 7.
Figure 9 presents experimental and predicted dissociation
conditions for methane sI, methane/2,3-DMB sH, and
methane/benzene sII gas hydrates. Good agreement between
the methane/2,3-DMB data measured in this work and those

Figure 5. Experimental and predicted mutual solubility of benzene and

Figure 7. Experimental and predicted methane-benzene phase equilibria at

338.71K.

Figure 6. Experimental and predicted mutual solubility of 2,3-dimethylbutane and water.

Figure 8. Experimental and predicted nitrogen-benzene phase equilibria at

348.15K.

Trans IChemE, Vol 78, Part A, July 2000

STERGAARD et al.

736

Figure 9. Dissociation conditions of methane, methane/2,3-DMB and

methane/benzene hydrates.

Figure 11. Dissociation conditions of methane/nitrogen/2,3-DMB and

methane/nitrogen/benzene hydrates.

measured hydrate phase boundary for 2,3-dimethylbutane

with methane agrees well with previously reported data. The
Kihara potential energy parameters for benzene and 2,3dimethylbutane, based on the hydrate dissociation conditions in the presence of methane, have been optimized for
use in hydrate prediction models. Very good agreement is
obtained when applying the model on independent data,
i.e., hydrate dissociation conditions for benzene and 2,3dimethylbutane in the presence of nitrogen, and nitrogen
and methane.
REFERENCES

Figure 10. Dissociation conditions of nitrogen, nitrogen/2,3-DMB and

nitrogen/benzene hydrates.

reported by Mehta and Sloan6 is observed. Furthermore, the

thermodynamic model is successful in predicting the
reduction in the methane hydrate free zone, caused by
2,3-DMB and benzene.
The hydrate dissociation conditions for nitrogen and for
2,3-DMB and benzene with nitrogen are shown in Figure
10. The presence of the heavy hydrate formers is seen to
have a signicant impact on the hydrate phase boundary,
reducing the hydrate free zone of nitrogen by as much as 9 K
for benzene and 6 K for 2,3-DMB in the tested temperature
range. Although the 2,3-DMB and benzene data presented
in Figure 10 have not been used in optimization of the
thermodynamic model, good agreement between experimental data and predictions is observed.
Finally, the composition-dependent hydrate dissociation
conditions for 2,3-DMB and benzene in the presence of
methane and nitrogen are presented in Figure 11. Excellent
agreement between experimental measurements and predictions is demonstrated.
CONCLUSIONS
Experimental hydrate dissociation data for benzene and
2,3-dimethylbutane in the presence of methane and/or
nitrogen have been measured at seabed temperatures. The

1. Sloan, E. D., 1998, Clathrate Hydrates of Natural Gases (2nd ed.)

(Marcel Dekker Inc., New York).
2. Ripmeester, J. A., Tse, J. S., Ratcliffe, C. I. and Powell, B. M., 1987, A
new clathrate hydrate structure, Nature, 325: 135136.
3. Ripmeester, J. A. and Ratcliffe, C. I., 1990, 129Xe NMR studies of
clathrate hydrates: New guests for structure II and structure H, J Phys
Chem, 94: 87738776.
4. Tohidi, B., Danesh, A., Burgass, R. W. and Todd, A. C., 1996, Effect of
heavy hydrate formers on the hydrate free zone of real reservoir uids,
SPE 35568, Presented at Europe Production Operations Conf & Exhib,
1617 April, Stavanger, Norway.
5. Danesh, A., Tohidi, B., Burgass, R. W. and Todd, A. C., 1993, Benzene
can form gas hydrates, Trans IChemE, 71(A4): 457459.
6. Mehta, A. P. and Sloan, E. D., 1994, Structure H hydrate phase
equilibria of parafns, naphthenes, and olens with methane, J Chem
Eng Data, 39: 887890.
7. Tohidi, B., Burgass, R. W., Danesh, A., stergaard, K. K. and Todd,
A. C., 1999, Improving the accuracy of gas hydrate dissociation point
measurements, Presented at 3rd Int Conf on Gas Hydrates, 1822 July,
Salt Lake City, Utah, USA.
8. Valderrama, J. O., 1990, A generalised Patel-Teja equation of state for
polar and non polar uids and their mixtures, J Chem Eng Japan, 23(1):
8791.
9. Avlonitis, D., Danesh, A. and Todd, A. C., 1994, Prediction of VL and
VLL equilibria of mixtures containing petroleum reservoir uids and
methanol with a cubic EoS, Fluid Phase Equilibria, 94: 181216.
10. van der Waals, J. H. and Platteeuw, J. C., 1959, Clathrate solutions, Adv
Chem Phys, 2(1): 157.
11. Parrish, W. R. and Prausnitz, J. M., 1972, Dissociation pressures of gas
hydrates formed by gas mixtures, Ind Eng Chem Proc Des Dev, 11(1):
2635.
12. Kihara, T., 1953, Virial coefcients and models of molecules in gases,
Rev Modern Phys, 25(4): 831843.
13. Mckoy, V. and Sinanoglu, O., 1963, Theory of dissociation pressures
of some gas hydrates, J Chem Phys, 38: 2946.
14. Tohidi, B., Danesh, A. and Todd, A. C., 1995, Modelling single and
mixed electrolyte solutions and its applications to gas hydrates. Trans
IChemE, 73(A4): 464472.

Trans IChemE, Vol 78, Part A, July 2000

GAS HYDRATE EQUILIBRIA OF 2,3-DIMETHYLBUTANE AND BENZENE

15. Holder, G. D. and Hand, J. H., 1982, Multiple-phase equilibria in
hydrates from methane, ethane, propane and water mixtures, AIChE J,
28(3): 440447.
16. Tee, L. S., Gotoh, S. and Stewart, W. E., 1966, Molecular parameters
for normal uids, Ind Eng Chem Fundam, 5(3): 363367.
17. Tohidi, B., 1995, Gas hydrate equilibria in the presence of electrolyte
solutions, PhD Thesis (Heriot-Watt University, Edinburgh, UK).
18. Avlonitis, D., 1992, Thermodynamics of gas hydrate equilibria, PhD
Thesis (Department of Petroleum Engineering,Heriot-Watt University,
Edinburgh, UK).
19. Tohidi, B., Danesh, A., Todd, A. C., Burgass, R. W. and stergaard, K.
K., 1997, Equilibrium data and thermodynamic modelling of cyclopentane and neopentane hydrates, Fluid Phase Equilibria, 138: 241
250.
20. Tohidi, B., Danesh, A., Burgass, R. W. and Todd, A. C., 1996, Hydrate
equilibrium data and thermodynamic modelling of methylcyclopentane
and methylcyclohexane, Presented at 2nd Int Conf on Gas Hydrates,
26 June, 1996, Toulouse, France, 109115.
21. Tsonopoulos, C, & Wilson, G. M., 1983, High-temperature mutual
solubilities of hydrocarbons and water, AIChE J, 29(6): 990999.
22. Yaws, C. L., Pan, X. and Lin, X., 1993, Water solubility data for 151
hydrocarbons, Chem Eng, February, 108111.
23. IUPAC, 1989, Hydrocarbons with Water and Seawater, Part 1,
Hydrocarbons C5 to C7, Solubility Data Series, 37 (Pergamon,
Oxford, UK).
24. Deaton, W. M. and Frost, E. M., 1946, Gas hydrates and their relation

Trans IChemE, Vol 78, Part A, July 2000

25.
26.
27.
28.

737

to the operation of natural gas pipelines, US Bur Mines Monograph, 8:

101.
IUPAC, 1982, Nitrogen and air, Solubility Data Series, 10 (Pergamon,
Oxford, UK).
IUPAC, 1987, Methane, Solubility Data Series, 27/28 (Pergamon,
Oxford, UK).
Jhaveri, J. and Robinson, D. B., 1965, Can J Chem Eng, 43: 75. Also
reported in Sloan1.
van Cleeff, A. and Diepen, G. A. M., 1960, Rec Trav Chim, 79:
582. Also reported in Sloan1.

ACKNOWLEDGEMENTS
This work has been supported by the Engineering and Physical Sciences
Research Council (EPSRC), Amerada Hess Ltd., Deminex UK Oil and Gas
Ltd., Health and Safety Executive, Marathon Oil UK Ltd., and Shell UK
Exploration and Production, which is gratefully acknowledged.

ADDRESS
Correspondence concerning this paper should be addressed to Dr B.
Tohidi, Department of Petroleum Engineering, Heriot-Watt University,
Edinburgh EH14 4AS. (E-mail: bahman.tohidi@pet.hw.ac.uk).
The manuscript was received 11 October 1999 and accepted for
publication after revision 28 March 2000.