Ind. Eng. Chem. Fundam.

1980, 19, 33-36 33

A Method for Predicting the Equilibrium Gas Phase Water Content in

Gas-H y drat e EquiIibrium

H.-J. Ng and Donald 6. Robinson*

Department of Chemical Engineering, University of Alberta, Edmonton, Alberta, Canada T6G 2G6

Recent experimental data on the equilibrium water content of the gas phase in gas-hydrate equilibrium have been
used to develop expressions for the fugacity of water over the unfilled hydrate lattice as a function of pressure
and temperature, for both Structure I and Structure I1 hydrates. The predicted water content of the gas phase
using these equations agrees very well with the experimental values and for Structure I1 hydrates indicates that
the parameters in the equations are independent of composition. The general applicability of the proposed equations
to other mixtures can only be evaluated as additional data become available.

Introduction the cavity of type m. The Langmuir constant C,j, de-

Interest in problems related to the formation of hydrates
in natural gas pipelines and related processing equipment
dates back to the mid 1930's. This interest continued for
a period covering more than two decades. During this time
a great deal of expermental information was accumulated
on the formation of hydrates from natural gas components
and their mixtures and the statistical mechanical theory
of hydrate formation was developed. Recently, the dis-
covery of natural gas in the Arctic and near-Arctic regions
has renewed the interest in both the theoretical and ex-
perimental investigation of gas hydrates, particularly in
the ice-gas-hydrate and gas-hydrate regions. Most of the
earlier work was done on the hydrate-gas-liquid water,
liquid hydrocarbon-liquid water-hydrate, and liquid hy-
drocarbon-liquid water-gas-hydrate regions. This work
is extensively reported in the literature, notably in reviews
by van der Waals and Platteeuw (1959), Byk and Fomina
(1968), and Parrish and Prausnitz (1972), and more re-
cently by Ng and Robinson (1976,1977). However, in spite
of these comprehensive studies, information on the for-
mation of hydrates in the gas-hydrate region is scanty. A
knowledge of the water content of natural gas that is
permissible without the formation of hydrates is of tech-
nical as well as economical importance in the transmission
of the gas through cold regions and in low temperature gas
processing. Recent experimental data on the methane-
hydrate system presented by Sloan et al. (1976) and by
Aoyagi et al. (1979) showed that the permissible water
content without hydrate formation in the gas-hydrate
region was considerably lower than that indicated by an
extrapolation of the data in the gas-liquid region as shown
in the Gas Processors Association Engineering Data Book
(1976). In the study undertaken in this work a procedure
is proposed for estimating the water content of natural gas
in equilibrium with hydrate in the gas-hydrate region.
Thermodynamic Relationships. The general equation
relating the properties of gas hydrates to their molecular
parameters as developed by van der Waals and Platteuw
(1959) may be expressed as follows
ApwH = pwMT- pw = RT Cv, In [1+ CC,,fl] (1)
I
where pwm - pw is the difference in the chemical potential
between the empty hydrate lattice and the filled gas-
hydrate lattice, f j is the fugacity of any hydrating com-
ponent j , Y, is the number of type m cavities per molecule
of water, and C , is the Langmuir constant for solute j in
0019-7874/80/1019-0033$01.00/0
scribing the hydrating gas interaction with each type of
cavity, is expressed by
c, -1-exp[-W(r)/kT]4rr2 dr
= 1
(2)
kT o
where W(r) is the spherically symmetric cell potential in
the cavity of radius a, with r measured from the center.
In treating the problem of the water content of methane
gas in equilibrium with hydrates, Sloan et al. (1976) related
the fugacity of water in the filled lattice, fw, to the fugacity
of water in the empty lattice, fWMT, and the chemical po-
tential difference by
fw = fwMT expbw - wMT)/RT (3)
They evidently visualized a process whereby the meta-
stable unfilled hydrate lattice structure initially formed
at PWMT, the vapor pressure of water in the empty lattice.
This lattice then underwent an increase in pressure to the
stable hydrate pressure, P. The fugacity of water in the
empty lattice, fwm, was then expressed in terms of PWm,
a Poynting type correction to get from PWMT to P, and a
fugacity coefficient for the water vapor over the hydrate
lattice a t PWMT. The fugacity of the water in the filled
lattice thus obtained from eq 3 was then equated to the
fugacity of water in the gas phase calculated from
f w g = Yw4 w g p (4)
The gas phase water fugacity coefficient 4Wg was obtained
from a virial relation and hence it was possible to deter-
mine the equilibrium gas phase concentration, yw.
The method of calculation by Sloan et al. (1976) was
limited to estimating the gas phase water content over
Structure I hydrates where methane was the only hydra-
ting component. The use of the virial relation for 4Wp was
awkward in that it required a knowledge or determination
of at least three interaction virial coefficients Bm, C-
and CWMM even for the pure methane system. No mdi-
cation is given on how the calculations could be extended
to other components or mixtures.
The method of calculation proposed in this work is ap-
plicable to the gas phase in equilibrium with both Struc-
ture I and Structure I1 hydrates for pure components and
for mixtures, it uses an equation of state for which the
parameters are already known to calculate the gas phase
fugacity coefficient, and it eliminates the need for specu-
lation regarding the physical process whereby the unstable
0 1980 American Chemical Society
34 Ind. Eng. Chem. Fundam., Vol. 19, No. 1, 1980
10-2
empty lattice structure forms a t one pressure and then
undergoes a change in pressure to the hydrating pressure.
As in the case of Sloan's work, the proposed method
makes use of the basic equations given in eq 1,3, and 4.
Equation 1 is modified according to the work of Ng and
Robinson (1976), and becomes 10'3

ApwH = RT[nI(l
I
+ 3(a, - l)y; - 2(aj - l)yfj] X
[ C u m In (1 + CCc,jfj)I (5)
rn I

In this equation, yj is the mole fraction of component j in

the gas mixture and ai is an interaction parameter between
the least volatile and each of the other hydrating compo-
nents in the gas mixture. Values of these parameters have
been presented by Ng and Robison (1976). In the case of
gas hydrates of Structure I, v l = 1/23 an: v2 = 3/23, and in
the case of Structure I1 hydrates, v1 = and v 2 = lll7
(van der Waals and Platteeuw, 1959). The Langmuir
constant, Cmj,was determined from eq 2 using the Kihara
spherical core cell model as,explained in detail by Parrish t
and Prausnitz (1972). The Kihara parameters were taken
from an earlier paper by Ng and Robinson (1977).
The fugacity of water over the filled hydrate lattice is
expressed by eq 3 slightly rearranged as follows
fw = fWMT exp(-AwH)/RT (34
The phase equilibrium relation for water in the gas-
hydrate region is obtained by equating the fugacities of
water in the gas phase and in the hydrate phase from eq
3a and 4 as follows
YW$ wgP= fWMTeXp(-ApwH/RT) (6)
which may be rearranged to give
10'~ - -

In eq 6a, -ApWH/RTcan be calculated from eq 1 and 2

using the Kihara potential with a spherical core, and the
fugacity coefficients of water and the gas may be calculated
from an equation of state, or from a generalized correlation.
Experimental data on the water content of the gas phase
in a gas-hydrate equilibrium mixture can be used to es- I I I
I
timate fWMTby rearranging eq 6a as follows

Data Reduction. Data on hydrate formation in the

hydrate-gas region for two different gas mixtures have
recently been made available by Aoyagi and Kobayashi
(1978). These data cover a temperature range from 233
to 267 K and a pressure from 27 to 119 atm. Both these
multicomponent systems form hydrates of Structure 11.
The procedure for using these data for calculating fwm,
the fugacity of the water in the unfilled hydrate lattice,
was as follows. At each available experimental data point,
it is possible to determine the fWMT by evaluating the
right-hand side of eq 6b. In this equation, yw and P are
known from the data, ApwH is obtained from eq 1, and 4Wp
may be calculated from an equation of state. In this case
the Peng-Robinson (1976) two-constant equation was used.
The values of In fwm obtained in this manner were then " 220 240 2bO 280 300
plotted against pressure at each of eight constant tem- Temperature, K
peratures as shown in Figure 1. These relationships were Figure 3. Effect of temperature on the rate of change of the fugacity
clearly linear, although the slope was a function of tem- of water with pressure over the unfilled Structure I1 lattice.
perature.
The values of fwom obtained in this manner were then linear relationship. Finally, the slopes of In fWMTfrom
plotted as In fw,om vs. 1/T. Figure 2 shows the resulting Figure 1 were plotted as a function of temperatures,
 Ind. Eng. Chem. Fundam., Vol. 19, No. 1, 1980 35

Table I. Experimental and Predicted Gas Phase Water Table 11. Experimental and Predicted Gas Phase Water
Content for Two Gas Mixtures Content for Methane
YH,O x 10-5 Y H , x~ 10-5
TI K Platm exptl pred TIK Plat m exptl pred
Composition: 75.02% CH,, 7.95% C,H,, 240 34.04 1,226 1.345
3.99% C,H,, 13.04% CO, 68.07 0.559 0.542
267.1 44.4 9.89 9.45 102.1 0.271 0.282
57.8 8.71 8.04 250 34.04 3,209 3.367
119.1 6.30 6.15 68.07 1,541 1.483
260.9 44.0 5.88 5.59 102.1 0.844 0.840
261.2 57.6 5.67 4.86 260 34.04 7.804 7.923
260.9 118.9 4.16 3.68 68.07 3.946 3.8 51
251.8 57.8 2.52 2.06 102.1 2.417 2.395
249.0 44.4 2.06 1.85 270 34.04 17.762 17.689
249.8 119.2 1.84 1.44 68.07 9.419 9.528
243.2 44.2 1.05 1.04 102.1 6.405 6.548
243.7 57.7 1.03 0.953
243.2 118.9 1.05 0.774 predicted values for this system is 2.9%. This is well
237.2 119.3 0.452 0.446 within the reported experimental accuracy.
233.9 119.1 0.250 0.329
Discussion
Composition: 87.06% CH,, 7.96% C,H,,
3.88% C,H,, 1.10% CO, The foregoing analysis of experimental data on the
277.6 102.1 11:8 12.1 equilibrium water content of the gas phase in the gas-
34.0 25.2 25.5 hydrate region has made it possible to express the fugacity
260.9 102.1 2.84 2.82 of water over the unfilled hydrate lattice as a function of
34.0 6.30 6.24 temperature and pressure. The relationships depend on
249.8 102.1 1.00 0.992 hydrate structure but are independent of composition for
34.0 1.97 2.22 the mixtures studied.
yielding the linear relationship shown in Figure 3. Thus Although the development is based on rather limited
for Structure I1 hydrates, the fugacity of water in the data, it is felt that the method is sound. It is believed that
hydrate lattice may be expressed as only minor modifications, if any, may be required in the
numerical coefficients in order to use the equations for
predicting the equilibrium gas-phase water content of any
gas mixture in the gas-hydrate region.
Nomenclature
where BWM= interaction second virial coefficient for water and
methane
= 18.062 - 6512/T
In fW,oMT (7) CWWM, CWMM = interaction third virial coefficient for water
and methane

( In
dp
fWMT
>, = 0.0001109T - 0.03192

The experimental values of the water content of the two

(8)
C , = Langmuir constant for component j in hydrate cavity
f j = fugacity of component j in gas phase
k = Boltzmann's constant
P = pressure
r = radial coordinate
multicomponent systems and the predicted values ob- R = gas constant
tained by using eq 6b, 7, and 8 are presented in Table I. 5" = absolute temperature
The average absolute difference between the experimental W ( r )= spherically symmetric cell potential
and predicted results is 9.1 '70.If three experimental points y, = mole fraction of component j in gas phase
which depart significantly from a smooth curve are re- Greek Letters
moved from the total of 20 points, the average difference CY, = binary interaction parameter
drops to 6.0%. It was reported that the reliability of the AwwH .= chemical potential of water in the unfilled hydrate
experimental results is thought to be about 5%. lattice minus the chemical potential of water in the filled
The results indicate that although fWMT is a function of hydrate lattice
pressure and temperature, it is apparently independent 9, = fugacity coefficient for component j in the vapor phase
of the system composition for Structure I1 hydrates. u, = number of cavities of type m per water molecule in the
Experimental data on the saturated water content of the hydrate
equilibrium gas phase in the methane gas-hydrate region Subscripts
were reported by Sloan et al. (1976) and Aoyagi et al. 0 = denotes zero pressure value
(1979). The revised data were used for obtaining values W = denotes water
of fwMTfor hydrates of Structure I in a manner similar to
that used for Structure 11. Superscripts
g = denotes gas phase
In fW,oMT = 14.269 - 5393/T (9) MT = refers to unfilled hydrate lattice

( 1;2MT)T = 0.00036T - 0.1025 (10)

The experimental and predicted results obtained for the
Structure I system are presented in Table 11. The average
absolute difference between the twelve experimental and
Literature Cited
Aoyagi, K., Kobayashi, R., Proceedings 57th Annual Conventlon, Gas Pro-
cessors Association, New Orleans, La., 1978.
Aoyagi, K., Song, K. Y., Sloan, E. D., Dharmawardhana, P. E., Kobayashi, R.,
Proceedings 58th Annual Convention, Gas Processors Association, Denver,
Colo, 1979.
Byk, S. S.,Fomina, V. I., Russ. Chern. Rev., 37, 469 (1968).
Engineering Data Book, Gas Processors Suppliers Association, Tulsa, Okla,
1977.
36 Ind. Eng. Chem. Fundam. 1980, 19, 36-39

McKoy, V., Sinanoglu, O.,J. Chem. Phys., 38, 2946 (1963). van der Waals, J. H., Platteeuw, J. C., Adv. Chem. Phys., 2, 1 (1959).
Ng, H.J., Robinson, D. B., Ind. €ng. Chem. Fundam., 15, 293 (1976).
Ng, H.J., Robinson, D. B., AIChEJ., 23,477 (1977). Received f o r review January 8, 1979
Parrish, W. R., Prausnitz, J. M., Ind. fng. Chem. Process Des. Dev., 11, 26
(1972). Accepted October 24, 1979
Peng, D.-Y., Robinson, D. B., Ind. Eng. Chem. Fundam., 15, 59 (1976).
Sloan, E. D., Khoury, F. M., Kobayashi, R., Ind. Eng. c&m. Fundam., 15,318 The financid support received from the Alberta Research council
(1976). for this work is sincerely appreciated.

Kinetics of Absorption of Oxygen in Aqueous Solutions of

Ammonium Sulfite

K. Neelakantan and J. K. Gehlawat"

Department of Chemical Engineering, Indian Institute of Technology, Kanpur, Kanpur-2080 16, India

The reaction between oxygen and ammonium sulfite is industrially important. The kinetics of absorption of oxygen
in aqueous solutions of ammonium sulfite was studied in stirred cells. Cobaltous sulfate was used as the soluble
catalyst. The absorption of oxygen in ammonium sulfite solutions was found to conform to the fast pseudenth-order
mechanism. In the range of the reactant concentrations of 0.045to 0.45g-mol/L the reaction was found to be
first order with respect to oxygen and second order with respect to ammonium sulfite. The third-order reaction
rate constant at 30 OC was found to be 2.70 X IO4 [L/g-molI2 s-' and the energy of activation was found to be
14.5 kcal/g-mol.

Introduction of well-defined interface geometry has been used. The

Aqueous solutions of ammonia are used to absorb the
lean mixtures of waste sulfur dioxide to control atmos-
pheric pollution in several fertilizer plants producing SO2
and ammonia. Ammonium sulfite is thus obtained as a
byproduct. It can be easily oxidized to ammonium sulfate,
which is used as a fertilizer.
In the chemical engineering literature the problem of
oxidation of aqueous sodium sulfite has been studied ex-
haustively. On the other hand, the oxidation of ammonium
sulfite has received very little attention. Some preliminary
studies have been reported by Young (19021, Vorlander
and Lainau (1929), and Hori (1937). Recently Grigorayan
(1968) investigated the oxidation of ammonium sulfite by
atmospheric oxygen in the presence of nitrogen oxides.
Matsuura et al. (1969) studied this reaction in a batch
reactor without catalysts. Mishra and Srivastava (1975,
1976) conducted a study for the homogeneous and heter-
ogeneous liquid phase oxidation of ammonium sulfite by
the Hatridge and Roughton method of rapid mixing. A
mechanism of the reaction was proposed.
It may be noted that detailed information on the kinetics
of the heterogeneous reaction between oxygen and am-
monium sulfite under conditions of industrial importance
is not available in the literature. According to the theory
of absorption with chemical reaction, this system is likely
to conform to the fast reaction regime.
It may be erroneous to infer anything about the kinetics
of absorption of oxygen in ammonium sulfite solutions
based on the controversial information available on the
sodium sulfite-oxygen system. An independent study is
needed. The present work was therefore undertaken to
make a systematic study of the kinetics of reaction between
dissolved oxygen and ammonium sulfite. An apparatus
00 19-78741801 1019-0036$0 1.OO/O
theory of absorption accompanied by chemical reaction has
been used to interpret the results obtained.
Experimental Section
Absorption experiments were carried out in stirred cells
of various dimensions. The design features of the appa-
ratus were similar to those employed by Gehlawat and
Sharma (1968). Figure 1shows the schematic diagram for
the experimental setup. A known amount of solution was
added to the stirred cell which was installed in a con-
stant-temperature bath. The absorption of oxygen was
measured by the volumetric uptake method similar to that
employed by Gehlawat and Sharma (1968) and the ana-
lytical method described by Jhaveri and Sharma (1967).
In the volumetric uptake method, pure oxygen was placed
in a balloon which was connected to the stirred cell. The
volumetric uptake of oxygen was measured by a soap-film
meter.
In a few experiments the partial pressure of oxygen was
varied from 12.5% to 99% by using nitrogen as the diluent.
The mixture of oxygen and nitrogen in the desired pro-
portion was passed through the apparatus for sufficient
time so that the partial pressure of oxygen in the apparatus
was the same as that in the incoming stream. The gas
phase in the stirred cell was also agitated by another stirrer
kept a t about 0.5 cm above the gas-liquid interface. A
known amount of solution of known concentration was
then introduced in the cell, the gas flow was stopped, and
the unit was connected to a balloon containing pure oxygen
at essentially atmospheric pressure. After several minutes
the volumetric uptake of oxygen was noted.
In the analytical technique oxygen or mixtures of oxygen
and nitrogen were passed through the apparatus containing
a known amount of solution of prefixed concentration for
0 1980 American Chemical Society