Proceedings of the First (1991) International Offshore and Polar Engineering Conference

Edinburgh, United Kingdom, 11-16 August 1991

Copyright © 1991 by The International Society of Offshore and Polar Engineers
ISBN 0-9626104-5-3 (Set); ISBN 0-9626104-6-1 (Vol I)

PREDICTION OF NATURAL GAS HYDRATE DISSOCIATION ENTHALPIES

Fouad Fleyfel and E.D. Sloan
Colorado School of Mines
Golden, CO, USA

ABSTRACT tory (Ullerich et al., 1987; Selim and

Sloan, 1985, 1989). In all of the reported
In this particular paper we propose a dissociation models, the most important
new, and simple technique to predict one physical parameter is (lHd ) , the heat of
of the most important physical properties dissociation, defined as the heat required
of hydrates namely the heat of hydrate to turn the hydrates into flowing phases of
dissociation (lHd ) at temperatures above gas and liquid water. The purpose of this
273.15 K. It is shown that it is possible work is to provide means of quick estimate
to determine lH d by knowledge of the size of the heat of dissociation, if the gas
of the guest gas molecules. To a first composition is known.
approximation, the enthalpy of dissociation
is independent of the type and the
concentration of the guest gas, with the CRYSTAL STRUCTURES, AS A BASIS
size constraint. Also as a notable outcome FOR THE HYPOTHESIS
most natural gases containing appreciable
amounts of methane and propane should have Clathrate hydrates are solid compounds
essentially the same heat of dissociation. in which gas molecules, referred to as
"guests", are encaged inside icy crystal
KEY WORDS: Hydrates, Structures, Enthalpy, lattices, referred to as "hosts". The
Dissociation, Natural Gas rocess of formation of the gas clathrate
hydrates is given by the reaction:
INTRODUCTION water + gas ~ clathrate hydrates (1)
In natural gas production and process- clathrate hydrates are classified in
ing, hydrates are normally considered to be two structures (excluding the much less
nuisances because free water combines with common occurrence of new structure H (SH)
natural gas molecules to form crystals hydrate) . Structure I (SI) posses a 12 A
which plug flow channels and impede flow. cubic cell parameter and structure II (SII)
One recent literature citation (Boniface, has a 17 A cubic cell parameter. Structure
1990) of this particular phenomenon is I contains 46 water molecules per unit
hypothesized to have caused the Piper Alpha cell, whereas Structure II contains 136
platform disaster in the North Sea. Great water molecules per unit cell. Moreover,
efforts have been devoted to prevent the unit cell of SI contains 6 large and 2
hydrates from forming and from dissociating small cavities. The small cavities are
once they are formed. Dissociation is pentagonal dodecahedra (5 1~, and the large
normally affected by depressurizing the cavities are tetrakaidecahedra (5 126 2) ,.
transfer line, before cleaning the line containing 12 pentagonal faces and 2 hexag-
with a device called a "pig". onal faces. The SII unit cell contains 24
ca:ri ~ies of which 16 are small, (5 12) ,
Models for hydrate dissociation have (slmllar tho those found in SI) and 8 are
been proposed by the laboratories of hexakaidecahedra (5 126 4), the largest cage
Bishnoi (Kim et al., 1987; Jamaluddin et found in either of the two structures.
al., 1989), (Holder et al., 1982, 1986),
(Kamath and Godbole, 1987) and this labora- Details of hydrate structures are

447
listed in a recent monograph (Sloan, 1990). of dissociation. While the equation is
A key to hydrate structure is found in the rigorously defined at a single temperature~
relative size of the guest molecule to the the fact that LH d , does not change rapidly
cavity occupied. This fit of molecules enables its use over a narrow temperat~re
within cavities is depicted in Figure 1, range.
which is a correction of an earlier version
(von Stackelberg, 1949). Three points It was argued (Yamamuro and Suga, 1989)
should be made about this figure. First., that the use of the Clausius-Clapeyron
below 3.5 A the guest molecules are too Equation does not provide the most accurate
small to stabilize any cavity, while above estimation of heat of dissociation. Their
7.5 A molecules are too large to fit into argument seems to he an extension of a
any cavity. Second, some molecules can discussion three decades earlier by (Glew,
only stabilize the large cavity of each 1959), (Barrer, 1959) and (vander Waals
structure; as an examp.lepure ethane gas and Platteeuw, 1959) . The consensus
stabilizes the large 5 126 2 cavity oeSI, reached in the earlier three articles was
while pure isobutane stabilzes the large that Equation (2) is valid only for an
5 126 4 cavity of SII. Third, when a univariant system (such as the reaction
molecule stabilizes the small cavity of a shown in Equation (1» with the codicil
structure, it will also enter the large that fractional guest occupation of each
cavities of the structure. cavity does not change appreciably. We
note that Equation (1) may be made
Because natural gas contains small univariant (within the stoichiometric
amounts of large molecules such as prop.ane restrictions) for a gas mixture, by the
or isobutane, the larges cavities (5 126 4) additional specification that the gas
usually form, causing SII to predominate. composition remains constant over a plot of
Smaller molecules normally occupy both the .fln P versus liT. Exacting calorimetric
large and small cavities in SII. Mixtures measurements of the heat of dissociation of
of solid crystal structures (81 + SII) do pure alkane hydrates (Handa ,1986) indicat-
not commonly occur. ed that Equation (2) provides accurate
values to within 2%. A comparison of the
values of LHd obtained for hydrates through
DETERMINING THE HEAT OF hoth methods is found in Table 1.
HYDRATE DISSOCIATION
The use of Equation (2) allows heat of
The most accurate way to determine the dissociation, (LHd ) to be determined by the
heat. of dissociation (LHd,) for the hydrate numerous published pressure-temperature
formation reaction shown ~n Equation .(1) is phase equilibria data for several natural
to measure it calorimetrically. such gas hydrates. Our interest is directed
experimental measurements are painstaking above 273.15K toward the three phase system
and limited; however calorimetry has been (Lw-H-V) where the letters represent liquid
recently performed for pure components and wafer, hydrates and gas respectively. It
a few limited mixtures (Handa, 1986, 1988). was the observation of a number of
different semi logarithmic plots of such
However, there is a second way to data which led us to the below hypothesis.
determine the heat of dissociation, which
enables its rapid estimation for a range of
available hydrate data. For almost a full HYPOTHESIS AND SUPPORT OF THE HYPOTHESIS
century the heat of hydrate dissociation
has been calculated througth the use of Our hypothesis suggests that the heat
thermodynamics. of dissociation above 273.15K depends only
upon the cavity occupied. The cavity which
The method makes use of the Clausius- is occupied by each molecule of the gas can
Clapeyron equation, shown below: be found via referenCe to Figure 1. Below
we ,present the evidence to support the
hypothesis. For ail. OJ: l:ne :rJ.gu:res o:r l:n~s
d .fln P section, data source references are to be
(2)
d(l/'!') found in Tables 2-4.
Single Guest Component Hvdrates
where P and T are the absolute pressures consider first the evidence for the
and temperature of hydrate formation, R is simple, single component hydrate formers
the universal gas constant and z is the gas (water is an implicit additional component
\ compressibility. in all cases). Figure 2 represents a
Equation (2) indicates that the slope semilogarithmic plot for all natural gas
of the logarithm of the hydrate dissocia- component simple hydrates.
tion pressure plotted against reciprocal
temperature wi..ll'give the negative heat of Methane and nitrogen form simple
dissociation divided by the product of the hydrates in both cavities of different
compressibilty factor and the gas constant. structures, 81 and SII respectively. The
If the compressibility doesn't change hypothesis suggests that each component' s
rapdily, Equation (2) will enable the use line should have a different 4fd determined
of commonly available pressure-temperature from the slope, indicated as (-8034 K) for
hydrate formation data to estimate the heat CH A and (-7870 K) for N 2 • At these

448
temperatures ethane and carbon dioxide form
almost exclusivley in the large cavities of
SI (see Fleyfel and Devlin, 1990) for CO 2
in smaller cavities at lower temperatures);
the hypothesis suggests that their ffi d
should be approximately equal and the
slopes of the curves are similar at (-9018
K) for ethane and (-9002 K) for CO 2 . In the
same manner the heat of dissociation, (ffid ) ,
for propane and isobutane, having 11ne
slopes of «-15098.1 K) and (-15688.1 K)
respectively) should be similar because
each component forms in the large cavities
of SII, and the compressibility factor is
-1.
Binary Mixtures of Natural Gas Components.
Data for methane+ethane binary mixtures
have been plotted in Figure 3. These
particular mixtures form exclusively SI,
with ethane fitting only in the large cages
and methane fitting in both cavities. Upon
the (Lw-H-V) data points shown for this
mixture, we have arbitrarily imposed lines
with a constant slope (-9350 K) taken as
the best curve fit for a particular binary
mixture which contains 90.4%CH 4 +9.6%C 2H6 .
Within experimental error, all of the data
points appear to fallon the lines with
constant slope, thereby indicating a
constant heat of dissociation.
Data for binary mixtures which form SII
are shown in Figure 4 (CH ..+c jI 8)' Figure 5
(CH ..+i-C..fI 10) and Figure 6. For the data
plotted in these Figures, the large guest
molecules (C jI 8 and i-C.J:i 10> always fit
into the large 5 126 .. cavities while methane
can fit into either cavity. In Figure 4 we
have arbitrarily imposed lines with a con-
stant slope (-9820 K) taken as the best fit
for themixture containing 95.2%CH ..+ 4.8%
CjIs. Within experimental error, all of the
data points fallon the lines with constant
slope indicating a constant heat of
dissociation.
Figure 5 shows phase equilibria data
points for CH ..+i-c .J:i 10' but the constant
slope of the lines is arbitrarily taken as
(-9820 K) the value from the fit of
95. 2%CH ..+4. 8%C jI 8 in Figure 4. Not only do
the data all fall along the lines of the
constant slope, but the slope itself is
taken from different components (CH ..+C jI s>
than those of the data points.
For clarity, Figure 6 is a combination
of data points for CH ..+c jI 8 and CH ..+i-c .J:i 10
mixtures of different composition. The
arbitrary constant slope drawn is the same
as that in Figures 4 and 5. All data
points fall along the lines plotted.
Therefore, for those mixtures all three
figures indicate a common heat of dissocia-
tion to a first approximation. This
behavior is singular because, while the
methane molecules have been maintained in
all mixtures, we have exchanged propane,
and isobutane without affecting the heat of
dissociation.
449
Multicomponent Mixtures of Natural Gas
Components
Figures 7 and 8 are semilogarithmic
plots of all the available data on mixtures
of mUlticomponent natural gases. For
clarity only two reference bounds are drawn
in each figure, with the same slope
(-9820 K) given for the binary mixtures in
Figures 4, 5, and 6. Since the multicom-
ponent mixtures form SII, the hypothesis
suggests that the slopes should be the same
for the binary gas mixtures which fill both
the large and small cavities of SII.
Figure 9 shows data by (Wilcox et ale
1942) for a natural gas which contains 1.6%
C jI 8 as its heaviest component. Using the
statistical thermodynamic method suggested
by van der Waals and Platteeuw, pressure
and temperature conditions were predicted
for a similar gas, except that i-C.J:i 10 was
substituted for C jI 8. The results for both
the experimental data and the predictions
in Figure 9 suggest that there is no change
in the heat of dissociation between the two
natural gases.
DISCUSSION AND CONCLUSION
The above hypothesis and the supporting
evidence suggest a subtle interaction
between the guest and host molecules.
Since the heat of dissociation depends
largely upon the cavity occupied, it is
clear that the water hydrogen bonds in the
host cages play a predominant role in the
heat of dissociation. However, the guest
molecules are able to change the slope of
the pressure-temperature curves slightly
simply by their interactions (van der Waals
forces) within the cavities. This unusual
relation should be studied further.
References
1.Barrer, R.M, (1959). Nature, Vol
183,p.463.
2.Boniface, A (1990). "Hydrates- a Factor
In Piper Alpha?," The Chemical Engineer,
p. 12.
3.Deaton, W.M., and Frost, E.M,
Jr., (1946)."Gas Hydrates and Their
Relation To The Operation Of Natural Gas
Pipelines," U.S. Bureau of Mines
Monograph, VolB. - ---
4.Fleyfel, F. and Devlin, J.P (1991).
"Carbon Dioxide Clathrate Hydrate
Epitaxial Growth: Spectroscopic
Evidence For Formation of The Simple
~ype II CO 2 Hydrates," ~. Phys. Chern.,
ln press.
5.Glew, D.N, (1959). "Some stoichiometric
Gas Hydrates," Nature,Vol 184,P. 545 .
6.Handa,Y'.P,(1986) . "compositions, Enthalpies
of Dissociation,and Heat Capacities in
The Range 85 to 270K For Clathrate
Hydrates of CH4,C2H6,C3H8'" ~. Chem.
Thermo,Vol 18,p.15 .
7.Handa~ Y.P, (1988)."A Calorimetric study
of Naturally Occuring Gas Hydrates," Ind.
Eng. Chem. Res.,Vol 27,p.872. ---
8.Holder, G.D., Angert, P.E., John, V.T.,
and Yen, S, (1982)."A Thermodynamic
Evaluation of Thermal Recovery of Gas
From Hydrates in The Earth," ~. Pet
Tech,Vol 34,p.1127.
9.Jamaluddin, A.K.M., Kalogerakis, N., and
Bishnoi,P.R, (1989)."Modelling of
Decomposition of a Synthetic Core of
Methane Gas Hydrates By Coupling
Intrinsic Kinetics with Heat Transfer
Rates," Can. ~. Chem. Eng.,Vol 67,P.948.
10.Jhaveri,J.,and Robinson,D.B, (1965).
"Hydrates in The Methane - Nitrogen
system," Can. ~ Chem. Eng.,Vol43,p.75.
Rec. Trav. Chim.,Vol 79, p.582.
21.van der Waals, J.H., and Platteeuw,
J.C,(1959). "Validity of Clapeyron's
Equation for Phase Equilibria Involving
Clahrates," Nature, Vol 183, p.462
22.von Stackelberg, M,(1949) . "Feste Gas
Hydrates,"Naturwiss,Vol 36,p. 327.
23.Wilcox, W.I., Carson, D.B., and Katz,
D.L, (1941). "Natural Gas Hydrates," Ind.
Eng.Chem.,Vol 33,p. 662.
24.Wu,B.J.,Robinson,D.B.,and Ng,H.J, (1976).
"The Role of n-Butane in Hydrate
Formation, It ~. Chem. Thermodyn., Vol 8
p.46L
25.Yamamuro,O.,andSuga,H, (1989)."Thermodyna-
mic Studies of Clathrate Hydrates," J.
Therm. Anal.,Vol 35,p.2025 -
HYDRATE FORMER

11.Kamath, V.A.,and Godbole, S.P, (1987).

"Evaluation of Hot - Brine stimulation
Technique For GaS Production From
Natural Gas Hydrates," ~. Petro Tech,Vol CAViTIES OCCUPIED
39,p.1379.
NO HYDRATES
12.Kim, H.C., and Bishnoi, P.R., Heidemann,
and R.A., Rizvi, S. S.H, (1987) . "Kinetics
Ar ~
of Methane Hydrate Decomposition," Chem.
Eng. Sci., Vo142, p.1645. ---- Kr
5.66 H20
N2
13.Kobayashi, R, (1951) Vapor-Liquid 02
Equilibrium in Binary Hydrocarbon-Water
Systems, Ph.D. Dissertation, u.Mich. CH4
XE,H2S
14.Ng, H.J., and Robinson, D.B, (1976) • liThe
Measurement and Prediction of Hydrate
Formation in Liquid Hydrocarbon CO2
Systems, "I&EC. Fundam.,Vol 15,p.293. 5,75 H20

15.Reamer, H.H.,and Selleck, F.T., and

Sage, B.H,(1952)."Some Properties of
Mixed Paraffinic and Olefinic Hydrates," C2H6
~ Petrol. Tech.,VOL 4(8),P. 197.

16. Schneider, G.R., and Farrar, J, (1968).

"Nucleation and Growth of Ice Crystals," 7.66 H2O (5 1262.81)
C-C3H6
U.S. Dept. of Interior, Rsch. Dev. Rpt.
VOL 292, P.37. 6Ao ~
(CH2}30
17.Sloan, E.D,(1990). Clathrate Hydrates 03Ha
of Natural Gases,P. 641.Marcel Dekker,
Inc., New York. I-C4H10
17.0 H2O
18.Selim, M.S., and Sloan, E.D,(19S5). (5 126 4,811)
"Modeling and Dissocation of an In-Situ
Hydrates," SPE 13597, SPE California
Regional Meeting, Bakersfield ~
CA, March 27-29. 7Ao
N-C4H10
19.5elim,M.S.,and Sloan, E.D, (1987) . "Theory
and Measurement of Hydrate Dissociation
Enthalpies," AIChE. ~,Vol 33,p.747.
Figure 1.Comparison of guest molecule sizes
20.van Cleeff,A.,andDiepen,G.A.M, (1960). andcavities occupied as simple
"Gas Hydrates of Nitrogen and Oxygen, " hydrates.

450
 27 33

100000

~ 10000
0....
:::::;:::::
............, l~

w W
n:::: 0:::
::::>
~ 1000.
(()

(J) ~ 1000
w 0:::
n:::: 0....
0....

100
~C02
00000 CH4!C3H8 36.255 CH4
~i-C4H10 00000 CH4!C3H8 88.355 CH4
~C3H8 CH4!C3HS
t1t1AlJ.lJ. 95.2>11 CH4
000<}1) C2H6 00000 CH4/C3HS 97.4>11 CH4
'1>**** N2 o ***** CH4!C3H8 99.055 CH4
~CH4

10 --+-'-,--,--,--,-.,-,-rr-r-'-"'-'-'--rrlrrr-rr-.-rrTl""rrrrr-rr-.--rl
3.70 3.60 3.50 3.40 3.30 3.63 3.60 3.58 3.55 3.53 3.50
TENIPERATURE (1000/f<) TEMPERI\TURE(1000/f<)
Figure 2.A Clausius-clapeyron plot showing Figure 4.A Clausius-Clapeyron plot showing
the hydrate single component guest the hydrate's binary component
mixtures in the (Lw-H-V) phase. guest mixtures of CH 4 +C 3H8 in the
(Lw-H-V) phase having different
concetrations. The reference slope
is for a CH~(95.2%)+C~H~(4.8%).
TEMPERATURE (oF)
33 5 6
14 4 5 7

:?
0.... :?
2S 0....
~
w
0:::
::::>
W
(()
0::: 1000
(()
::::>
(()
lJ.J (()
0::: W
0.... 0:::
0....

* * * * * CH4!C2H6 56.455 CH4

<><><><><> CH4!C2H6 90.4%
CH4
00000 CH4!C2H6 95.0>11 CH4
CH4!C2H6 97.855 CH4
,;"t1AAA
00(01) CH4!C2H6 98.855 CH4
DDDDD CH4!iC4H10 97.5% CH4
.to..to. .to..to..to. CH4/iC4H 10 99.1855 CH4
00000 CH4!iC4H1D 98.8% CH4
.......... CH4!iC4H 10 75.8% CH4
1000 DD.!.J,tJ.tJ. CH4!iC4H 10 72.4% CH4

3.65 3.60 3.55 3.50 3.45 100 -t-"",-r-r.--r"-,,--,,-.,.,-r-r.--r,,-,-r-r,,--,---I

3.80 3.70 3.60 3.50 3.40 3.30 3.20
TENIPERATURE (1000/f<)
TENIPERATURE (1000/K)
Figure 3.A Clausius-Clapeyron plot showing Figure 5.A Clausius-Clapeyron plot showing
the hydrate's binary component the hydrate's binary component
guest mixtures of CH 4 :C 2 H6 in guest mixtures of CH 4 +i-C 4 H10 in
the (Lw-H-V) phase havlng the (Lw-H-V) phase liaving
different concentrations. The different concentrations.The
reference slope is for a reference slopeis for CH 4 (95.2%) +
CH 4 (90.4%)+C 2 H6 (9.6%). C 3H 8 (4.8%).

451
 27 :2
86

.0

10000
10000 9
8

,.,--...
-:;;(
0--
<C ~
0.. "---"
~ 4
W W
0::
0:: ::::)
::::)
VI VI
VI VI
W' W
0:: 0::
0--
0-- ** * H NAT. GAS B
........... NAT. GAS D
DOODO NAT. GAS E
AAAAA NAT, GAS F
***** NAT. GAS G
CH4!C3H8 88.356 CH4
1000 OQOOO NAT. GAS H
1000 ODOOO
AAAAA CH4!C3HB 95.256 CH4
9 EOO3EOO*13 NAT. GAS I
u~u CH4!iC4H10 97.4 CH4 8 ttttt NAT. GAS J
***** CH4!iC4H1 0 99.1856 CH4
oo.oooCH4!hC4H10 98.36 CH4
NAT. GAS K
NAT. GAS L

3.70 3.65 3.60 3.55 3.50 3.45 3.40 3.70 3.60 3.50 3.40 3.30

TEMPERATURE (1 OOO/f<) TEMPERATURE (1000/f<)

Figure S.A Clausius-Clapeyron plot showing
Figure 6.A Clausius-Clapeyron plot showing
the natural gas. hydrate's
for clarity purposes a combination
multicomponents mixtures. The
of figures 5 and 6 plus a binary
reference slopes are for a
mixture of CH 4 + n- C4 H10 in the
CH 4 (95.2%)+ C3 HS (4.S%).
(!.w-H-V) phase. The reference slope
is for a CH 4 (95.2%)+ C3 HS (4.S%).

14
27 8

10000

10000
-:;;(
9
8
-:;c
CL
0-- 7 ~
~
"---"
W
0:::
::::::>
(f)
(f)
w
0:::
CL

"' .. "' ..... NAT. GAS A

D DOD D NAT. GAS C
*****
00000
NAT.
NAT.
GAS
GAS
WGB
WGe
OOO<H NAT. GAS WGD
1000 .. " **" NAT. GAS KHG D..oo.o.o. WGE
9
8
***** NAT. GAS KMG * * • * ~ WGC
EllEOOJEOOJ NAT. GAS B
7 NAT. GAS J
1000 -t--.--r---,-""-,--'--'-,---.---,---,-....,--,---,--,---r-r--r-r-r-r-..--r--1
3.80 3.70 3.60 3.50 3.40 3.30
3.70 3.60 3.50 3.40 3.30 TEMPERATURE (1 OOO/f<)
TEMPERATURE (1000/f<) Figure 9.A Clausius-Clapeyron plot showing
Figure 7.A Clausius-Clapeyron plot showing Wilcox natural gas (C) having a
the natural gas hydrate's 1.61% C3 HS (data points are star
multicomponent mixtures. The shaped), and Wilcox gas (E) where
reference slopes are for a the C3 HS is substituted by
CH 4 (95.2%)+ C3 HS (4.S%). 1. 61% i-C 4 H10 •

452
TABLE 1. ENTHALPIES OF DISSOCIATON OF HYDRATES SINGLE
AND BINARY COMPONENT MIXTURES OF METHANE, ETHANE,
PROPANE, AND i-BUTANE AT 273.15 K.

GAS lHd (kjjmol) lH d (kjjmol)

(our prediction) (Handa)
CH 4 55.9 54.19
C2 H6 71. 08 71.8
C3H8 126 129.2
i-C 4 H10 130.4 133.2
90.4%CH 4 +9.6%C 2 H6 73.88

95.2%CH 4 +4.8%C 3 H8 79.2

TABLE 2. LIST OF THE PRESSURE-TEMPERATURE MEASUREMENTS FOR

SINGLE COMPONENT GUESTS (Lw-H-V) PHASE.

SYSTEM NAME P(KPA) T(oF)

CH Deaton, Frost 2000-20000 32-55

c2 6A Reamer 400-2000 32-70
32-40
~3H8 Deaton, Frost 200-500
l-C 4 H10 Shneider, Farrar 100-200 32-40
CO 2 Deaton,Frost 1000-10000 32-55
N2 Van Cleef,Diepen 10000-100000 32-70

Table 3. LIST OF PRESSURE-TEMPERATURE MEASUREMENTS FOR

BINARY COMPONENT GUESTS (Lw-H-V) PHASE

SYSTEM NAME P(KPA) T(oF)

CH 4 +C 2 H6 Deaton,Frost 900-7000 33-55

CH 4 +C 3 H8 Deaton,Frost 300-5000 33-50
CH 4 +i-C 4 H10 Wu et al. 200-8000 32-70
CH 4 +n-C 4 H10 Ng,Robinson 2000-20000 33-62

TABLE 4. LIST OF ALL THE GAS MIXTURES FOR MULTICOMPONENT

GUESTS (Lw-H-V) PHASE. (MOL PER CENT)

NAME GAS N2 C1 C2 C3 i-C 4 n-C 4 C5 C6

Kobayashi KHG 15 73.29 6.7 3.9 0.36 0.55 0.2 0.0

KMG 6.8 79.64 9.38 3.22 0.18 0.58 0.15 0.05

Wilcox GAS N2 CO 2 C1 C2 C3 i-C 4 n-c 4 C5

B 0.64 86.41 6.47 3.57 0.99 1.14 0.78

C 0.43 0.51 93.2 4.25 1. 61
D 88.36 6.82 2.54 0.38 0.89 1. 01
E 0.43 0.51 93.2 4.25 1. 61

Deaton, GAS N2 CO2 C1 C2 C3 C4 H2 S

Frost
A 7.7 0.2 65.4 12.7 10.3 3.7
B 1.1 0.2 87.9 4.4 4.9 1.5
C 9.4 0.2 78.4 6.0 3.6 2.4
D 9.5 0.3 79.4 5.8 3.6 1.4
E* 1.1 3.25 87.8 4.0 2.1 1.5 0.25
F 0.3 0.4 91.0 3.2 2.0 3.1
G 1.0 90.8 3.0 2.1 3.2
H 14.3 0.2 75.2 5.9 3.3 1.1
I 3.4 88.5 4.3 2.0 1.7
J 1.2 0.9 90.6 3.8 1.5 2.0
K 25.0 0.8 67.4 3.7 1.9 1.2
L 0.2 0.6 96.5 0.9 1.8

* Gas E has not been considered due to the presence of H2 S

in the mixture.

453