TECHNICAL NOTE

294

METASTABLE EQUILIBRIUM in the DEW POINT

DETERMINATION of NATURAL GASES in the HYDRATE REGION
RIKI KOBAYASHI

JUNIOR MEMBER AIME

DONALD L. KATZ

MEMBER AIME

INTRODUCTION
The dew point of natural gas which has been in
equilibrium with gas hydrates has been reported to be
lower than that obtained for natural gas in equilibrium
with water"'. Hammerschmidt' reports a lowering of
the dew point of 13 F for a natural gas in equilibrium
with hydrate at 38 F and 525 psi. Records and Seely'
likewise show that the dew point of gas leaving hydrate
separators' is as mueh as 15 F below the separator
temperature.
This paper presents the reasons for the observed
differences between the equilibrium temperatures and
the dew point temperatures. Descriptions of the dew
point determination by the Bureau of Mines and ASTM
tester' indicate that the dew point is taken as the temperature at which liquid water droplets first begin to
appear on the cooled mirror surface even though the
temperatures involved are below that required for the
formation of gas hydrates or ice.

THE RICI: INSTITUTE

HOUSTON, TEX.
UNIVERSITY OF MICHIGAN

ANN ARBOR, MICH.

point determination and gas-hydrate equilibria. Thermodynamics place certain restrictions on the location of
line DE', namely, that (1) the concentration of water
along the line DE be greater than the concentration of
water along EF or that the metastable line split the
angle formed by the intersection of line GE and EF

PRESSURE IS BETWEEN THE CRITICAL

PRESSJRES Of' PURE METHAP AND PURE WATER
A
8
C

BOILING POINT OF PURE WATER

FREEZING PONT OF PURE WATER
FREEZING POINT OF METHANE

GAS

PRESSURE-TEMPERATURE DIAGRAM FOR

METHANE-WATER SYSTEM

iii

Fig. 1 presents a schematic pressure-temperature diagram for the methane-water system' for some constant
pressure between the critical pressures of pure methane
and pure water i.e., pressures frequently encountered
in pipeline operations. The possible equilibrium relations are shown by the heavy solid lines. Curve AE
represents the saturated water content or dew point of
gas in equilibrium with a water-rich liquid solution
while curve EF represents the dew point of gas in
equilibrium with hydrates. In addition the dotted line
DE labelled "metastable dew point" is introduced to
explain the apparent discrepancy hetween the dew

iii

a: 200
::>

~
a:

GAS

+ WATER-RICH

WOUlD

100

Q.

~
iii

I-

HYDRATE FORMATION TEMPERATURE

o
z

1iI-

!(~

GAS

+ HYDRATE

~~

>-~

ICE

HYDRATE

xo

P'~P------'~~~~~~"'~~~~----~PU~RE
METHAJI

Original manuscript received in PetroieUtn Branch offi('e on Dec.

13. 1954. Revised manuscript received on June 30. 1955.
lReferences given at end of paper.

SPE 456-G

FIG.

WATER

1 -- SCHEMATIC TEMPERATURE-COMPOSITION
DIAGRAM FOR METHANE-WATER SYSTEM.
PETROLEUM TRANSACTIONS, AIME

20 0 -

METHANEWATER SY3TEM

I~ 0 -

gOO LBS/SQ IN A B i ; / "

/'

0010

/
V-

0012
0014

0018
C>

10 0

;;7

E~

O. 0018
HYDRATE

TEMPERAT

'E

o __l. __ -~~"':/
~T&..

<

r, ... O ~/""'"

0.000001

"'"

0.00001

0.0001
MOL

0.001
FRACTION

0.01
WATER

0.10

."

0 .0020-'"

Consider the process of contacting a gas in equilibrium with hydrate at temperature T, followed by a dew
point determination. The water content of the equilibrium vapor at T, (OF) is X" (.000024 mole fraction)
from the hydrate-vapor equilibrium curve. This water
content, X" is present in the gas which shows a dew
point of T, (-15F). For the metastable equilibrium
curve DE, T" the water dew point would be lower than
T" the equilibrium hydrate temperature.

O. 0022
0 .0024
100

FIG. 2 - TEMPERATURE COMPOSITION DIAGRAM OF

METHANE-WATER SYSTEM AT 900 PSI.
and (2) that line DE be a smooth extension of line
AE. Although the section shown in Fig. 1 is for the
methane-water system, a similar one could be drawn
for ethane-water or propane water. A lean natural gas
would be expected to approach the behavior described
for the methane-water system. Corresponding to extension DE of line AE there should exist a metastable
extension of line AG, which is not shown.
At temperatures below line GE, at the pressure for
which the phase diagram is drawn, vapor and hydrate
are in equilibrium along EF when methane is in excess of the theoretical amount required to form the
hydrate.
The existence of liquid water on the mirror of the
dew point tester below EG where gas and hydrate are
in equilibrium and the reproducibility of the dew point
require a metastable equilibrium.

CONCLUSIONS
It should be noted that charts which give the equilibrium water content of natural gases as a function of
temperature and pressure'" are for liquid water-gas equilibria, including the metastable equilibrium when such
occurs. Hammerschmidt' calculated the fugacity of
water over hydrate but no other relationship has been
presented to show the water content of gases in equilibrium with hydrate. Such data along with the water
content charts of natural gas in equilibrium with liquid
water would give a quantitative verification of the metastable relationship described.

ACKNOWLEDGMENT
Acknowledgment is made of the contribution of
Professor L. O. Case to the phase rule analysis of this
problem.
REFERENCES
1.

QUANTITATIVE DIAGRAM
A quantitative diagram of the methane-water system
has been drawn at 900 psi, Fig. 2, to illustrate the
difference in the water concentration of the methane
or natural gas when in contact with hydrate at equilibrium and in contact with liquid water under metastable
conditions. The actual temperatures are indicated on a
reciprocal temperature scale. Curve AED represents the
dew point conditions at 900 psia'. It shOUld be noted
that the dew point concentrations below the hydrate
formations temperature correspond to the metastable
equilibrium. Curve EF of Fig. 2 was obtained by
applying to the methane-water system the depression
of the dew point observed by Records and Seely for
natural gas.

VOL. 201., 19.">5

2.

3.

4.

5.

6.

Hammerschmidt, E. G.: "Formation of Gas Hydrates in Natural Gas Transmission Lines," Ind.
Eng. Chern. (1934) 26, 851.
Records, L. R. and Seely, D. H.: "Low Temperature
Dehydration of Natural Gas," Trans. AI ME (1951)
192, 61.
Deaton, W. M. and Frost, E. M.: "Gas Hydrates
and their Relation to the Operation of Natural Gas
Pipe Lines," Bureau of Mines Mon. 8 (1946).
McCarthy, E. L., Boyd, W. L., and Reid, L. S.:
'The Water Vapor Content of Essentially Nitrogenfree Natural Gases," Trans. AIME (1950) 189, 241.
Kobayashi, Riki and Katz, D. L.: "Methane Hydrate at High Pressure," Trans. AIME (1949) 186,
66.
Ricci, John E.: The Phase Rule and Heterogeneous
Equilibria, D. Van Nostrand Co., Inc. (1951).

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