lllll

ELSEVIER Fluid Phase Equilibria 117 (1996) 168-177

F O R M A T I O N AND D E C O M P O S I T I O N OF GAS HYDRATES

P. Raj Bishnoi* and V. Natarajan

Department of Chemical and Petroleum Engineering
University of Calgary
Calgary, Alberta
CANADA - T2N 1N4

ABSTRACT

The kinetics of hydrate formation and decomposition are explained as understood to date. The formation and
decomposition phenomena are complex. Hydrate formation is viewed as a crystallization process that includes the
nucleation and growth processes. Hydrate nucleation is an intrinsically stochastic process that involves the formation and
growth of gas-water clusters to critical sized, stable hydrate nuclei. Hydrate growth process involves the growth of stable
hydrate nuclei as solid hydrates. Hydrate decomposition is a sequence of lattice destruction and gas desorption processes.
The process of heat transfer during hydrate decomposition is analogous to nucleate boiling phenomena. The focus of this
work is to present the various perspectives on the kinetic processes at a conceptual level. Key issues for research in this
area are identified and some possible directions for future work are suggested.

INTRODUCTION

Gas hydrates are crystalline, non-stoichiometric, clathrate compounds. They are formed by certain gases when
contacted with water under favourable temperature and pressure conditions. Natural gas components like CH4. C2H6, C3H8,
i-C4H~o, CO2 and H2S besides other gases like Ne, Ar, Kr, Xe, N2, 02 and hydrocarbons like cyclopropane form hydrates.
The water molecules in the hydrates form a cage-like crystal structure through hydrogen bonding around the entrapped
gas molecules. The gas hydrate structures ~6 are identified as I, II and the recently determined structure H 7'g. Structures
I and II consist of two types of cavities and structure H consists of three types of cavities. Extensive information on gas
hydrates is available as compiled in various sources 9'"~ and from the proceedings" of a recently concluded international
conference on gas hydrates.

The industrial interest in gas hydrates began with the discovery that hydrate formation could plug natural gas
pipelines t2. Initial interest was on the avoidance of hydrate formation in pipelines and other process equipment. Hence
much research was directed to understand the conditions of hydrate formation. As a result of extensive thermodynamic
studies, considerable hydrate phase equilibrium data and methods to predict hydrate formation conditions are available 9' 1.~3-
27. These studies have also focused on the development of chemical agents that inhibit hydrate formation. Substances which
affect the colligative properties of a solution generally inhibit hydrate formation. Methanol is one such commonly used
inhibitor in the industry ~7,~s. Electrolytes are also known to inhibit hydrate formation 2~27. As the focus of this work is on
the kinetics of hydrate formation and decomposition, the studies on the thermodynamics of hydrates are not discussed.
Details on these studies could be obtained from reviews by Holder28 and Englezos 29.

In contrast to the advances made in the thermodynamics of hydrates, the kinetics are less understood. The kinetics

* - Author for correspondence

0378-3812/96/$15.00 © 1996ElsevierScienceB.V. All fights reserved

SSDI 0378-3812(95)02950-8
 P.R. Bishnoi, V. Natarajan / Fluid Phase Equilibria 117(1996) 168-177 169

could be broadly divided into the two categories of formation and decomposition kinetics. Generally hydrate formation
and decomposition processes are studied separately and only recently Bishnoi et al. 3° have shown that a unified treatment
of hydrate formation and decomposition is possible. A good knowledge of the hydrate formation kinetics would allow the
exploitation of the kinetics mechanism favourably to depress the hydrate formation rate. Although hydrate formation may
be unavoidable, the rate of formation could be slowed 3136 to allow gas transport in pipelines without plugging the lines.
Another idea to modify the hydrate particle characteristics to prevent the particles from agglomerating is being explored 37.
This would enable the solid hydrates to be transported through pipelines in slurry form3am. In comparison to hydrate
formation there have been even fewer studies on hydrate decomposition. With the depletion of conventional natural gas
reserves, there would be a need in the future to exploit the vast quantities of natural gas reserves known to occur in
hydrate form9'1°'4~'42.A practical and viable technology to tap this vast source of the gas would require simulation studies 43
52 of the gas recovery processes and could only be developed if hydrate decomposition kinetics are well understood. For
this mason it is expected that hydrate decomposition would be an area of considerable interest in the future.

In this work, the kinetics of hydrate formation and decomposition are explained as understood to date. The
formation and decomposition phenomena are complex. The focus of this work is to present the various perspectives on
the kinetic processes at a conceptual level. Key issues for research in this area are identified and some possible directions
for future work are suggested.

KINETICS OF HYDRATE FORMATION

The hydrate formation process is analogous to the crystallization process 9'1°'53"57.As in crystallization, the hydrate
formation process could be sub-divided into nucleation and growth processes. Hydrate nucleation is the process of forming
critical sized, stable hydrate nuclei, and hydrate growth is the process of growth of these stable nuclei. The available
information on hydrate nucleation and growth have primarily come from the laboratories of Profs. Bishnoi 3°'32"~3~5'57"67and
Sloan 1°'33"56'6s'7°.The nucleation processes are discussed below.

1. Hydrate Nucleation

The hydrate nucleation process refers to the formation and growth of hydrate nuclei to critical size. The growing
clusters of gas and water molecules could be regarded as precursors to hydrate nuclei formation5.59. If the size of growing
nuclei is less than the critical size then the nuclei are unstable and may grow or break in the aqueous solution. A growing
hydrate nucleus that attains the critical size is a stable nucleus and immediately leads to the formation of crystal hydrate.
The induction period is the time elapsed during the nucleation processes which include formation of gas-water clusters
and their growth to critical sized stable nuclei. Although the view that hydrate nucleation processes involve the formation
and growth of gas-water clusters to critical sized nuclei enjoys considerable support, the precise nature of the clusters and
the mechanisms of their formation and growth are still not understood.

Phenomena that affect the gas-water cluster formation are of interest to understand the hydrate nucleation process.
In particular the structure of water has an important role in the nucleation process. Because of the hydrogen bonding
ability of water there exist hydrogen-bonded structures among the water molecules that connect some of these molecules.
The structure of water7~8grefers to the arrangement of water molecules connected through hydrogen bonds to form these
structures. For example, ice represents a highly structured water with the positions of water molecules fixed in a tetragonal
hydrogen bonded structure. As the temperature increases above the freezing point the structure of water becomes more
loose and disordered compared to the highly organized structure of ice. Hydrate formation experiments using water from
170 P.R. Bishnoi, V. Natarajan / Fluid Phase Equilibria 117 (1996) 168-177

different sources by Vysniauskas and Bishnoi 5~ showed that the mean induction period varied with the source of water
used. In these experiments a lower mean induction period was observed when water obtained from thawed ice was used
as compared to the induction period obtained when hot tap water was used. The mean induction period was also lower
when water obtained from dissociated hydrates was used as compared to the induction period observed when hot tap water
was used 58. This is known as the "memory effect" and has been observed in a number of studies 8993 besides Vysniauskas
and Bishnoi 5s. In addition, studies have found that the structure of water is enhanced around a dissolved gas molecule.
This effect on the water structure around a dissolved solute molecule is referred as the "hydrophobic hydration"
phenomenon as suggested by Frank and Co-workers94'95. The hydrophobic hydration was supported later by Glew 96 who
showed the similarities in the thermodynamic properties of methane hydrates and aqueous methane solutions. Molecular
simulation studies 97'98for the methane-water system indicated that the average co-ordination number of water molecules
around the methane molecule was closer to the co-ordination number of 21 for a structure I smaller cavity. Rahman and
Stillinger 99 have identified the water network around the dissolved solute molecule to be similar to that of a hydrate type
cavity. In addition, thermodynamic analysis shows a large negative entropy of solution which is an evidence of the creation
of a structure within the body of the water ~6.

As mentioned above the gas-water clusters play

an important role in the hydrate nucleation process. The
nucleation process occurs when the solution is in a
supercooled or supersaturated state. The study of
nucleation using the supersaturation and the supercooling
ucleation Processes . approaches are schematically illustrated in Figures 1 and
2 respectively. The supersaturation approach is adopted by
Bishnoi and Co-workers and the supercooling approach is
adopted by Kobayashi and Co-workers 92'1°°and Sloan and
Co-workers.
tb
eq time -- The hydrate formation experiments were
conducted by Bishnoi and Co-workers at constant
temperature and pressure. The experimental pressure was
Figure 1: Typical Gas Consumption Plot higher than the three phase hydrate equilibrium pressure
at the experimental temperature. They used a stirred
reactor in which the hydrate forming gas was contacted in
a semi-batch manner with a known volume of water. Figure 1 shows the cumulative moles of gas consumed due to its
dissolution or hydrate formation with time during an experiment. The moles of gas consumed at point A represents the
amount of gas dissolved corresponding to the three phase hydrate equilibrium pressure at the experimental temperature.
The metastable region between the points A and B is characterized by the hydrate nucleation processes. The point B in
the figure represents the point at which stable critical sized hydrate nuclei appear in a catastrophic manner. Englezos and
Bishnoi 54 found that the moles of gas dissolved just prior to the nucleation point, B, was substantially higher than the
computed two phase (vapor-liquid) metastable equilibrium. The computed value was obtained by extrapolating in the
metastable region. They suggested that the gas-water cluster formation could deplete the hydrate forming gas in the bulk
liquid phase and thus cause the gas to dissolve beyond the two phase value. The critical size of a hydrate nuclei could
be calculated as suggested by Englezos et al. 53'67. The hydrate growth process begins at point B and proceeds along the
line B-C shown in Figure 1.

A schematic of the pressure and temperature trace of hydrate forming experiments conducted by Kobayashi and
Co-workers and Sloan and Co-workers at constant volume is shown in Figure 2. The point A in Figure 2 could be
identified with the point A in Figure 1. At point B a catastrophic formation of stable hydrate particles occurs leading to
a sudden fall in the pressure. Hence the point B in Figure 2 is equivalent to the point B in Figure 1. The metastable state
characterized by the nucleation processes is represented between points A and B. The similarities between the
 P.R. Bishnoi. V. Natarajan / Fluid Phase Equilibria 117(1996) 168-177 171

supersaturation and the supercooling approaches as

illustrated in the Figures 1 and 2 are readily apparent. The
metastable hydrate nucleation region of cluster formation
and growth is represented between the point corresponding
Nucleation to three phase hydrate equilibrium, A, and the point of
stable hydrate particle formation, B, in both the figures.
The appearance of hydrates at point B is sudden and has
been described as catastrophic by Kobayashi and Co-
workers92. Although the size of the hydrate particles is
small, their number is sufficiently large to make the
solution appear turbid in the experiments of Bishnoi and
Co-workers. In the same way the sudden appearance of
hydrates results in the consumption of supersaturation
Temperature --* leading to the dramatic pressure drop in the experiments
by Kobayashi and Co-workers and Sloan and Co-workers.
Figure 2: Experimental Pressure-Temperature Trace

From the above discussion it is clear that

supersaturation and supercooling are equivalent. They are
essential for the hydrate nucleation processes. Many researchers
have modelled the induction period as a function of =o
supercooling9"1°'1°H°4. The supersaturation could also be
translated in terms of the degrees of supercooling 1°5. The
supersaturation at any point in the solution is the excess
dissolved gas concentration over the saturation concentration
value at that point.The availability of supersaturation at a point -l
in the solution dictates the location where stable nuclei of solid
hydrates first appear. For stagnant systems the hydrate formation Figure 3: Induction Period vs Supersaturation
could begin at the gas-liquid interface first since the dissolved
gas concentration would be the highest near the interface. For
stirred systems, the hydrate formation could begin anywhere in the solution depending on the dissolved gas concentration
at that location. Hence the hydrodynamics of the solution and the rate of gas dissolution in solution could be expected
to affect the induction period.

The induction period of hydrate nucleation has been related to supersaturation by Bishnoi and Co-workers 3°'57.
From their analysis supported by experimental data on methane, ethane and carbon dioxide hydrates57 the following points
could be made. The dependence of the induction periods on the supersaturation is observed as shown schematically in
Figure 3. In the figure fm is the fugacity of the gas at the experimental temperature and at hydrate equilibrium pressure.
The fugacity of the gas, fgv, in the figure is at the experimental temperature and pressure. The supersaturation in the figure
is expressed as the excess of the fugacity ratio over unity. The induction periods increase as the supersaturation is
decreased, tending to very large values at low supersaturations. As the supersaturation is increased the induction periods
generally decrease to a small value. The scatter in the induction period data is high at very low supersaturations which
decreases as the supersaturation is increased. The induction period data exhibit random behaviour at lower supersaturations
and increasingly exhibit deterministic behaviour as the supersaturation is increased. Hydrate nucleation is intrinsically
random in nature3°'34"~7'66"1°~.High supersaturations could mask this random nature of the nucleation phenomena thereby
making the observance of the induction periods appear deterministic. In addition, the random nature of the hydrate
nucleation could be masked by the presence of any heterogeneities in the experimental system used for the nucleation
study. The randomness in the induction period data was observed in recent hydrate nucleation studies by Parent and
172 P.R. Bishnoi, V. Natarajan / Fluid Phase Equilibria 117 (1996) 168-177

Bishnoi 66 under pristine experimental conditions.

A molecular mechanism of the hydrate nucleation process has been postulated by Sloan and Co-workers 56"69'7°.
Their mechanism envisages the formation of intermediate structures from the gas-water clusters and the growth of these
structures to stable hydrate nuclei. Through the use of chemical kinetic equations for each of the species postulated in their
mechanism 69'7°, they have modelled the nucleation process. A reaction kinetic mechanism for hydrate formation is also
proposed by Lekvam and RuoW °7'~°8. This approach uses a kinetic rate model for the nucleation and growth processes.
This model does not seem to impose the stability of the hydrate nuclei.

The available information on hydrate nucleation is at a macroscopic level and very little is known experimentally
about the sub-critical nuclei in solution. The mechanism of hydrate nucleation needs to be experimentally studied and
understood before any modelling at a molecular level could be accomplished.

2. Hydrate Growth

The hydrate growth process refers to the growth of stable hydrate nuclei as solid hydrates and has been studied
by several researchers from the early sixties. Knox et al. z°9 studied the propane hydrate growth in a stirred slurry pilot
plant reactor for a desalination process. They indicated that approximate sizes of the crystals obtained by the growth
depends on the degree of supercooling. A higher degree of supercooling produced chiefly smaller particles and resulted
in distinct crystal growth. Studies by Pinder 11° on hydrate formation kinetics with a soluble hydrate former like
tetrahydrofuran showed that the rate of hydrate forming reaction could be diffusion dependent. The kinetics of hydrate
growth from ice has been studied by Barrer and Edge m who observed a distinct induction period for krypton. Later
Falabella 1~2used an apparatus similar to that of Barrer and Edge, and obtained similar results in his study. Falabella also
observed an induction period for methane. He proposed a second-order kinetic model based upon the isothermal, isobaric
conversion of ice for his kinetic data and the data from Barrer and Edge. Sloan and Fleyfe169 have experimentally studied
the growth kinetics of cyclopropane hydrates.

Bishnoi and Co-workers have conducted a

Adsorption
"Reaction" Filmsystematic study of hydrate formation kinetics over many
years 53"55'57"67. The studies were conducted for various
gases and gas mixtures in pure water, electrolyte and
surfactant solutions using a semi-batch stirred reactor. In
these experiments at constant temperature and pressure the
overall gas consumption was obtained as a function of
time. Earlier in their studies a semi-empirical model was
proposed for the gas consumption rate by Vysniauskas
and Bishnoi 5s'59. Later, an intrinsic kinetic model for
Diffusion
Film hydrate growth with only one adjustable parameter was
formulated by Englezos et al. 53. The model is a
mechanistic model based on crystallization and mass
Distancealongfilm transfer theories. It envisages that the solid hydrate
particle is surrounded by an adsorption "reaction" layer
Figure 4: Fugacity profile in the diffusion and adsorption followed by a stagnant liquid diffusion layer. The
"reaction" film around a growing hydrate dissolved gas diffuses from the solution surrounding the
particle. stagnant liquid layer to the hydrate particle-water interface
and then, by an adsorption process the gas molecules are
incorporated into the structured water framework. As the water is in excess the reaction at the interface is considered to
be of first order in gas concentration. The fugacity of the dissolved gas is used in place of its concentration to express
the reaction rates. A schematic of the dissolved gas fugacity profile in the diffusion and the adsorption layers around a
 P.R. Bishnoi, V. Natarajan / Fluid Phase Equilibria 117 (1996) 168-177 173

growing hydrate particle, assumed spherical, in the solution is shown in Figure 4. In the diffusion layer, the dissolved gas
fugacity changes from the value, fb, to the value, f~. In the adsorption layer, the fugacity value falls to f~q, the value at the
three phase hydrate equilibrium pressure and at the particle surface temperature. The driving forces for the diffusion
around the particle is fb-f,, whereas it is f:fm for the "reaction" step. At steady state the rates of the two steps are equal.
Therefore f~ can be eliminated from the individual rate expressions to yield the rate of growth per particle as below.

() (1)

The quantity fb-f~qis the difference in the fugacity of the dissolved gas and its fugacity at the three phase equilibrium. It
defines the overall driving force. K* is the combined rate constant for the diffusion and adsorption "reaction" processes
and Ap is the surface area of each particle. As diffusional limitations are avoided in their well stirred system the K* values
reported by them represent the intrinsic rate constant of the reaction. The K* values were determined from experimental
data on formation kinetics of methane and ethane hydrates. This model was successfully extended to formation kinetics
of mixtures of methane and ethane 67 without any additional parameters. For methane hydrates, with the same K* that was
obtained for hydrate formation from pure water, the model is shown to apply to hydrate formation from electrolyte
solutions t ~3.

A kinetic model for CO 2 hydrate formation at the interface between liquid CO2 and water is reported by Shindo
et al) 14'H5. They assume that the hydrate formation occurs mainly in the liquid CO 2 and not in water. The formation of
CO2 hydrate is considered as a first order homogeneous reaction between CO2 and water.

Recently, Skovborg and Rasmussen t~6have formulated a model for hydrate growth kinetics using the experimental
gas consumption data obtained by Bishnoi et al. ~1'6~.They stated that the formation of hydrates would affect the liquid side
gas-liquid mass transfer coefficient, and used the data to empirically determine the mass transfer coefficient. This
approach does not provide any insight on the hydrate growth process.

Future studies on hydrate growth kinetics should include the determination of the size distribution of the growing
hydrate particles. At present limited results on the size distribution of cyclopropane hydrate particles are available from
Monfort and Nzihou 91. In addition, the agglomeration characteristics of the growing hydrate particles need to be studied.

Hydrate Decomposition

The hydrate decomposition has not been as extensively studied as hydrate formation. Holder and Co-workers m'1~8
have studied the heat transfer during the hydrate decomposition process and drawn its analogy with the nucleate boiling
phenomena. Based on this analogy, Kamath et al. H7 expressed the heat transfer rate during propane hydrate decomposition
to be a power function of AT, which is the temperature difference between the bulk fluid and the hydrate surface. Later
Kamath and Holder 118 generalized the correlation and applied it to methane hydrate decomposition.

Bishnoi and C o - w o r k e r s 119 have conducted experiments on methane hydrate decomposition in a semi-batch, well
stirred reactor. In their experiments, hydrates were formed at a pressure above the three phase hydrate equilibrium pressure
at the experimental temperature. Then the decomposition was initiated by a drop in the pressure to a desired pressure
below the three phase equilibrium pressure maintaining the temperature constant. The amount of gas evolved from the
decomposing hydrates was obtained as a function of time. The experiments were conducted at high enough stirring rates
to avoid mass transfer effects. They have suggested that the hydrate decomposition may be viewed as a two step process -
the destruction of the clathrate host lattice at the particle surface followed by the desorption of the guest molecule from
174 P.R. Bishnoi, V. Natarajan / Fluid Phase Equilibria 117(1996) 168-177

the surface. An intrinsic kinetic model for hydrate

decomposition was formulated by Kim et al.ll9. The
decomposing hydrate particle, assumed spherical, was
considered surrounded by a cloud of gas as shown
schematically in Figure 5. In the figure the decomposing
particle is surrounded by a desorption "reaction" layer
followed by a cloud of the evolved gas. The rate of
decomposition for a hydrate particle is given by,

(2)
( m -- a 0% -f,b,

Figure 5: Decomposition of Hydrate Particles where Kd is the decomposition rate constant and Ap is the
surface area of a particle. The three phase equilibrium
fugacity of the gas, f~q, and the fugacity of the gas, fgv, are at the particle surface temperature but at the three phase
equilibrium and the experimental pressure respectively. The decomposition driving force was defined as the fugacity
difference, f~q - fgv.

As mentioned earlier for the hydrate growth, the decomposition studies also should be undertaken to include the
determination of the size distribution of the decomposing particles.

CONCLUDING REMARKS

The study of the kinetics of hydrate formation and decomposition offers considerable challenges. Hydrate
formation is viewed as a crystallization process that includes nucleation and growth processes. The nucleation is an
intrinsically stochastic process that involves the formation and growth of gas-water clusters to critical sized, stable hydrate
nuclei. The stochastic nature of the nucleation could be masked by high nucleation driving forces and the presence of
heterogeneities. At present there are no molecular level measurements of the hydrate nucleation process. Such
measurements are needed to formulate a molecular level mechanism.

Hydrate growth involves the growth of stable hydrate nuclei as solid hydrates. The surface area of the growing
hydrate particles strongly affects the growth rate. Hydrate decomposition is a sequence of lattice destruction and gas
desorption processes. The heat transfer rate during hydrate decomposition is analogous to nucleate boiling phenomenon.
The size distribution of the hydrate particles during the growth and decomposition processes should be studied for use in
the modelling of these processes. The agglomeration characteristics of the hydrate particles should be studied to explore
the possibility of transporting the particles through pipelines in a slurry form.

ACKNOWLEDGEMENTS

The financial assistance provided by the Natural Science and Engineering Research Council of Canada (NSERC)
for this project is gratefully acknowledged.

REFERENCES

1. W.F. Claussen, Journal of Chemical Physics, 19 (1951) 259, 662, 1425.

2. M. von Stackelberg and H.R. Muller, Z. Electrochem., 58 (1954) 215.
 P.R. Bishnoi, V. Natarajan / Fluid Phase Equilibria 117 (1996) 168-177 175

3. G.A. Jeffrey, Dechema Monograph No.47 (1962) 849.

4. C.W. Wak, Thomas, R.K. McMullan, J. of Chem. Phys., 42 (1965) 2732.
5. G.A. Jeffrey and R.K. McMullan, Prog. Inorg. Chem., 8 (1967) 43.
6. G.A. Jeffrey, Inclusion Compounds; J.L. Atwood, E.D. Davies and D.D. MacNichol (eds.), Vol.1, Acad. Publ., 1984.
7. J.A. Ripmeester, J.S. Tse, C.I. Ratcliffe, B.M. Powell, Nature, 325 (1987) 135.
8. J.A. Ripmeester and C.I. Ratcliffe, J. Phys. Chem., 94 (1990) 8773.
9. Y.F. Makogan, Hydrates of Natural Gas, Translated from Russian by W.J. Cieslesicz, PennWell Books, Tulsa,
Oklahoma, 1981.
10. E.D. Sloan, Clathrate Hydrates of Natural Gases, Marcel Dekker Inc., New York, 1, 1991.
11. E. Dendy Sloan, John Happel and Miguel A. Hnatow (eds.), Annals of New York Academy of Sciences No. 715
(1994).
12. E.G. Hammerschmidt, Ind. Eng. Chem., 26 (1934) 851.
13. J.H. van der Waals, and J.C. Platteeuw, Adv. Chem. Phys., 2 No.1 (1959) 1.
14. W.R. Parrish, and J.M. Prausnitz, Ind. Eng. Chem. Procs. Des. Dev., 11 (1972) 26.
15. G.D. Holder, G. Corbin and K.D. Papadopoulos, Ind. and Eng. Chem., 19 (1980) 282.
16. P.R. Bishnoi, A.K. Gupta, P. Englezos and N. Kalogerakis, Fluid Phase Equilibria, 53 (1989) 97.
17. P. Englezos, Z. Huang, P.R. Bishnoi, Journal of Canadian Petroleum Technology, 30 (1991) 148.
18. F.E. Anderson and J.M. Prausnitz, AIChE J., 32 No.8 (1986), 1321.
19. P. Englezos, and P.R. Bishnoi, Ind. Eng. Chem. Res., 30 (1991) 1655.
20. P. Englezos, Ind. Eng. Chem. Res., 31 (1992) 2232.
21. P.R. Bishnoi and P.D. Dholabhai, Fluid Phase Equilibria., 83 (1993) 455.
22. P.D. Dholabhai, P. Englezos, N. Kalogerakis and P.R. Bishnoi, Can. J. Chem. Eng. 69 (1991) 800.
23. P.D. Dholabhai, N. Kalogerakis and P.R. Bishnoi, J. Chem. Eng. Data, 38 (1993) 650.
24. J.L. Roo, G.J. Peters, R.H. Lichtenthaler and G.A.M. Diepen, AIChE J. 29 No. 4, (1983) 651.
25. P. Englezos, and P.R. Bishnoi, AIChE J., 34 No.10 (1988) 1718.
26. C.W. Tse and P.R. Bishnoi, Can. J. Chem. Eng., 72 (1994) 119.
27. P.D. Dholabhai and P.R. Bishnoi, J. Chem. Eng. Data, 39 (1994) 191.
28. G.D. Holder, S.P. Zetts, N. Pradhan, Rev. in Chem. Engg., 5 (1988) 1.
29. P. Englezos, Ind. Eng. Chem. Res., 32 (1993) 1251.
30. P.R. Bishnoi, V. Natarajan and N. Kalogerakis, Annals of the New York Academy of Sciences, 715 (1994) 311.
31. C.C. Gryte, Annals of New York Academy of Sciences, 715 (1994) 323.
32. N. Kalogerakis, A.K.M. Jamaluddin, P.D. Dholabhai and P.R. Bishnoi, SPE 25188, Presented at the SPE
International Symposium on Oilfield Chemistry held in New Orleansm LA, USA March 2-5 1993.
33. J. Long, J. Lederhos, A. Sum, R. Christiansen and E.D. Sloan, Presented at the 73 ~ Annual GPA Convention, New
Orleans, Louisiana, March 7-9 1994.
34. M.H. Yousif, R.B. Dorshoww and D.B. Young, Annals of New York Academy of Sciences, 715 (1994) 330.
35. A.R. Edwards, Annals of New York Academy of Sciences, 715 (1994) 543.
36. M.A. Kelland, T.M. Svartaas and L.A. Dybvik, SPE 28506, Proceedings of the 1994 SPE Annual Technical
Conference and Exhibition, II Production Operations and Engineering, Vol. 1, p169-177
37. R.B. Forteith, M.Sc Thesis, University of Calgary, Calgary, Canada, 1994.
38. P. Bourgmayer, A. Sugier and E. Behar, 4 ~ International Conference on Multi-Phase Flow, Nice France, 19-21 June
1989 Paper A3.
39. H.F.Nygaard, 4 'h International Conference on Multi-Phase Flow, Nice France, 19-21 June 1989 Paper A1.
40. R.L. Reed, L.R. Kelley, D.L. Neumann, R.H. Oelfke and W.D.Young, Annals of New York Academy of Sciences,
715 (1994) 430.
41. C.F. Pearson, P.M. Halleck, P.L. McGuire, R. Hermes and M.Mathews, J. Phy. Chem., 87 (1983) 4180.
42. Petroleum Economist, November 1994, 37.
43. A.K.M. Jamaluddin, N. Kalogerakis and P.R. Bishnoi, The Third Chemical Congress of North America, Toronto,
Ontario, June 5-10, 1988.
176 P.R. Bishnoi, V. Natarajan / Fluid Phase Equilibria 117 (1996) 160-167

44. M.S. Selim and E.D. Sioan, SPERE (May 1990) 245; Trans AIME 289.
45. J.W. Ullerich, M.S. Selim and E.D.Sloan, AIChE J., 33 No.5 (1987), 747.
46. D.K. Das and V. Srivastava, J. Energy Engg., 119 No.3 (1993), 180.
47. M.H. Yousif and E.D. Sloan, SPE Reservoir Engineering, November 1991, 452.
48. M.H. Yousif, H.H. Abbas, M.S. Selim and E.D. Sloan, SPE Reservoir Engineering, February 1991, 69.
49. V.A. Kamath, P. Sanjay, J. Godbole, Petroleum Tech. , November 1987, 1379.
50. V.A. Kamath, P.N. Mutalik, J.H. Sira, S.L. Patil, SPE Formation Evaluation, December 1991, 477.
51. R.D. Roadifer, S.P. Godbole and V.A. Kamath, SPE paper 16361 presented at the 1987 SPE California Regional
Meeting, Bakersfield, March 27-29 1987.
52. G.G. Tsypkin, J. Engineering Physics and Thermophysics, 63 No.6 (1992), 1221.
53. P. Englezos, N. Kalogerakis, P.D. Dholabhai and P.R. Bishnoi, Chem. Eng. Sci., 42 (1987) 2647.
54. P. Englezos and P.R. Bishnoi, Fluid Phase Equilibria, 42 (1988) 129.
55. P. Englezos, N. Kalogerakis and P.R. Bishnoi, Journal of Inclusion Phenomena and Molecular Recognition in
Chemistry, 8 (1990) 89.
56. R. Muller-Bongartz, T.R. Wildeman and E.D. Sloan, Jr., Proceedings of the Second (1992) International Offshore and
Polar Engineering Conference, San Francisco USA, 14-19 June 1992, p628-635
57. V. Natarajan, P.R. Bishnoi and N. Kalogerakis, Chem. Eng. Science., 49 No.13 (1994) 2075.
58. A. Vysniauskas and P.R. Bishnoi, Chem. Eng. Sci., 38 (1983) 1061.
59. A. Vysniauskas and P.R. Bishnoi, Chem. Eng. Sci., 40 (1985) 299.
60. P.R. Bishnoi, A.A. Jeje, N.E. Kalogerakis and R. Saeger, Annual Report. Energy Mines and Resources, Ottawa,
Canada, 1985.
61. P.R. Bishnoi, N.E. Kalogerakis, A.A. Jeje, P.D. Dholabhai and P. Englezos, Final Report. Energy Mines and
Resources, Ottawa, Canada, 1986.
62. P.R. B ishnoi and P.D. Dholabhai, Annual Report 1991, Contract #5091-260-2138 for Gas Research Institute, Chicago,
IL. and Gas Processors Association, Tulsa, OK, 1991
63. P.R. Bishnoi and P.D. Dholabhai, Annual Report 1992, Contract #5091-260-2138 for Gas Research Institute, Chicago,
IL. and Gas Processors Association, Tulsa, OK, 1992
64. P.R. Bishnoi and P.D. Dholabhai, Annual Report 1993, Contract #5091-260-2138 for Gas Research Institute, Chicago,
IL. and Gas Processors Association, Tulsa, OK, 1993
65. P.R. Bishnoi, N.E. Kalogerakis and P. Englezos, Invited Paper at the Norwegian Petroleum Society Annual
Conference on Multiphase Flow - Technology & Consequences for Field Development '89, Stavenger, Norway,
1989.
66. J.S. Parent and P.R. Bishnoi, Accepted for publication in Chem. Eng. Commun., (1994).
67. P. Englezos, N. Kalogerakis, P.D. Dholabhai and P.R. Bishnoi, Chem. Eng. Sci. 42 (1987) 2659.
68. E.D. Sloan, Jr., Presented at the 69 th Annual GPA Convention, March 12-13 1990, Phoenix, Arizona.
69. E.D. Sloan and F. Fleyfel, AIChE J., 37 No.9 (1991) 1281.
70. R.L. Christiansen and E.D. Sloan Jr., Annals of New York Academy of Sciences, 715 (1994) 283.
71. H.M. Chadwell, Chem. Rev., 4 (1927) 375.
72. J. Frenkel, Kinetic Theory of Liquids, Oxford University Press, 1946.
73. L. Hall, Phys. Rev., 73 (1948) 775.
74. L. Grunberg and H.A. Nissan, Trans. Faraday Soc., 45 (1949) 125.
75. G.H. Haggis, J.B. Hasted and T.J. Buchanan, J. Chem. Phys., 20 (1952) 1452.
76. L. Pauling and R.E. Marsh, Proc. Nat. Acad. Sci. U.S., 38 (1952) 112.
77. H.S. Frank and W.Y. Wen, Disc. Faraday Soc., 24 (1957) 133.
78. C.L. Eck, P. van, H. Mendel and J. Fahrenfort, Proc. Roy. Soc., A247 (1958) 472.
79. L. Pauling, in Hydrogen Bonding; D. Hadzi and H.W.Thompson (eds.), Pergamon Press, London, 1959.
80. D.J. Hughes, W.K. Palevsky and E. Tunkelo, Phys. Rev., 119 (1960) 872.
81. L. Pauling, The Nature of Chemical Bond, 3rd ed.; Cornell University Press: Ithaca; New York, Chapter 7, 1960.
82. R.J. Ginell, Chem. Phys., 34 (1961) 992.
 P.R. Bishnoi, V. Natarajan / Fluid Phase Equilibria 117 (1996) 160-167 177

83. G. Wada, Bull. Chem. Soc. Japan, 34 (1961) 955.

84. I.Z. Fisher, J. Struct. Chem., 3 (1962) 604.
85. G.G. Malenkov, J. Struct. Chem., 3 (1962) 206.
86. E.M. Arnett, W.B. Kover and J.V. Carter, J. Amer. Chem. Soc. 91 (1969) 4028.
87. F. Franks and D.S. Reid, in Water: A Comprehensive Treatise; F. Franks, (ed.), Plenum Press, New York, 1973.
88. A. Geiger, F.H. Stillinger and A. Rahman, J. Chem. Phys., 70 (1979) 4185.
89. R.A. Nerheim, T.M. Svartaas and E.K. Samuelsen, Proceedings of the Second (1992) International Offshore and Polar
Engineering Conference, San Francisco USA, 14-19 June 1992 Pages 620-626
90. J.P. Monfort and A. Nzihou, J. Crystal Growth, 128 (1993) 1182.
91. J.P. Monfort and A.Nzihou, Annals of New York Academy of Sciences, 715 (1994) 555.
92. F. Fleyfel, K.Y. Song, A. Kook, R. Martin and R. Kobayashi, Annals of New York Academy of Sciences, 715 (1994)
212.
93. A.L. Baez, and P. Clancy, Annals of New York Academy of Sciences, 715 (1994) 177.
94. H.S. Frank, and M.W. Evans, J. Chem. Phys., 13 (1945) 507.
95. H.S. Frank, and A.S. Quist, J. Chem. Phys., 34 (1961) 604.
96. D.N. Glew, J. Phys. Chem., 66 (1962) 605.
97. J.C. Owicki and H.A. Scheraga, J. Amer. Chem. Soc., 99 (1977) 7413.
98. S. Swaminathan, S.W. Harrison and D.L. Beveridge, J. Amer. Chem. Soc., 100 (1977) 5705.
99. A. Rahman and F.H. StiUinger, J. Chem. Phys., 60 (1974) 1545.
100. J.P. Schroeter, R. Kobayashi and M.A. Hildebrand, Ind. Eng. Chem. Fundam., 22 (1983) 361.
101. M.H. Yousif, SPE 28479 , Proceedings of the 1994 SPE Annual Technical Conference and Exhibition, II
Production Ol/erations and Engineering, Voi. 1, p169-177
102. P. Skovborg, H.J. Ng, P. Rasmussen, and U. Mohn, Chem. Eng. Sci., 48 No.3 (1993) 445.
103. M.N. Lingelem, A.I. Majeed and E. Stange, Annals of New York Academy of Sciences, 715 (1994) 75.
104. D. Lippmann, D. Kessel and I. Rahiman, Annals of New York Academy of Sciences, 715 (1994) 525.
105. V. Natarajan, Ph.D Dissertation, University of Calgary, Calgary, Canada, 1993.
106. B. Kvamme, Annals of the New York Academy of Sciences, 715 (1994) 306.
107. K. Lekvam and P. Ruoff, J. Am. Chem. Soc., 115 No.19 (1993) 8565.
108. K. Lekvam and P. Ruoff, Annals of New York Academy of Sciences, 715 (1994) 558.
109. W.G. Knox, M. Hess, G.E. Jones and H.B. Smith, Chem. Eng. Prog., 57 No. 2 (1961) 66.
110. K.L. Pinder, Can. J. Chem. Eng., (1965) 271.
111. R.M. Barrer and A.V. Jr. Edge, Proc. Roy. Soc. (London) A300 (1967) 1.
112. B.J. Falabella, Ph.D. Dissertation, Univ. of Mass., Amherst, Mass., USA, 1975.
113. P.D. Dholabhai, N. Kalogerakis and P.R. Bishnoi, Can. J. Chem. Eng., 71 (1993) 68.
114. Y. Shindo, P.C. Lund, Y. Fujioka and H. Komiyama, Int. J. of Chem. Kin., 25 (1993) 777.
115. Y. Shindo, P.C. Lund, Y. Fujioka and H. Komiyama, Energy Conversion and Management, 34 No.9-11 (1993) 1073.
116. P. Skovborg and P. Rasmussen, Chem. Eng. Sci., 49 No.8 (1994) 1131.
117. V.A. Kamath, G.D. Holder and P.F. Angert, Chem. Engg. Sci., 39 No. 10 (1984), 1435.
118. V.A. Kamath and G.D. Holder, AIChE J., 33 (1987), 347.
119. H.C. Kim, P.R. Bishnoi, R.A. Heidemann and S.S.H. Rizvi, Chem. Engg. Sci., 42 No.7 (1987) 1645.